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ORGANIC CHEMISTRY
(Vol. II I

Dr. Jagdamba Singh Dr. L.D.S Yadav


MSc., 0 Phil M Sc, Ph 0
Professor, Department of Chemistry Professor, Department of Chemistry
University of Allahabad, University of Allahabad,
ALLAHABAD ALLAHABAD

~ PHAGATI PHAKASHAI'I
PRAGATI PRAKASIIMI
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1 SPECTROSCOPY 1-68
1.1 introduction 1
1.2 Electromagnetic spectrum 1
1.3 Absorption spectroscopy 2
1.4 Origin of absorption spectra 2
1.5 Classification of molecular spectra 5
1.6 Ultraviolet and visible spectroscopy 5
1.7 The UV spectrum 8
1.8 Types of electronic transitions 10
1.9 Formation of absorption bands 12
1.10 Designation of absorption bands 12
1.11 Transition probability 13
1.12 Terminology used in UV spectroscopy 14
1.13 Effect of conjugation on absorption maximum 15
1.14 Solvent effects 17
1.15 Electronic spectra; structure relationships 19
1.16 Important chromophores 21
1.17 Woodward-Fieser rules for conjugated polyenes 21
1.18 Woodward-Fieser rules for a, p-unsaturated carbonyl compounds 28
1.19 Angular distortion and cross-conjugation 30
1.20 UV Spectroscopy in structure identification 31
1.21 Infrared spectroscopy 31
1.22 Measurement in IR spectrum 32
1.23 Physical basis of IR spectroscopy 33
1.24 Selection rules 35
1.25 Molecular vibrations 36
1.26 Calculation of fundamental stretching frequencies 38
1.27 Factors affecting vibrational frequencies 40
1.28 Examination of an infrared spectrum 46
1.29 Characteristic group frequencies of some organic molecules 47
Very short answer questions 53
Problems with solutions 54
Problems for self assessment 57
Answers to very short answer questions 62
Solutions of problems 63

2 ALCOHOLS 69-116

2.0 Introduction 69
2.1 Classification of alcohols 69
2.2 Nomenclature of alcohols 70
2.3 Methods of preparation of monohydric alcohols 70
2.4 Physical properties 72
2.5 Chemical reactions 74
2.6 O-H bond cleavage 74
2.7 C-O bond cleavage 77
2.8 Dehydration of alcohols 81
2.9 Mechanism of dehydration of alcohols 81
2.10 Dehydrogenation 83
2.11 Oxidation 83
(vi)

2.12 Summary of reactions of monohydric alcohols 85


2.13 Distinction between primary, secondary and tertiary alcohols 86
2.14 Alcohol industry 87
2.15 Dihydric alcohols 89
2.16 Methods of formation of vicinal diols 90
2.17 Physical properties of vicinal glycols 92
2.18 Structure of ethylene glycol 99
2.19 Trihydric alcohols 99
2.20 Properties of glycerol 100
2.21 Structure of glycerol 103
Very short answer questions 104
Problems with solutions 105
Problems for self assessment 107
Answers to very short answer questions 111
Solutions of problems 112

3 PHENOLS 117-150
3.0 Introduction 117
3.1 Nomenclature 117
3.2 Methods of preparation 118
3.3 Physical propertie~ 119
3.4 Acidic character 119
3.5 Chemical reactions 129
3.6 Other electrophilic substitution reactions 139
Very short answer questions 141
Problems with solutions 142
Problems for self assessment 144
Answer to very short answer questions 145
Solutions of problems 147

4 ETHERS AND EPOXIDES 151-167


4.1 Ethers 151
4.2 Methods of preparation 151
4.3 Physical properties 153
4.4 Chemical reactions 154
4.5 Misce"aneous reactions 159
4.6 Epoxides 160
4.7 Preparation of epoxides 160
4.8 Reactions of epoxides 161
Very short answer questions 163
Problems with solutions 163
Problems for self assessment 164
Answer to very short answer questions 165
Solutions of problems 166

5 ALDEHYDES AND KETONES 168-251


5.0 Introduction 168
5.1 Nomenclature 168
5.2 Methods of preparation of aldehydes and ketones 169
5.3 Physical properties 176
5.4 Structure and nature of aldehydes and ketones 177
5.5 Nucleophilic addition reactions 179
(vii)

5.6 Addition of carbon nucleophiles 184


5.7 Addition of oxygen nucleophiles 188
5.8 Addition of sulphur nucleophiles 193
5.9 Addition of nitrogen nucleophiles 196
5.10 Reduction of aldehydes and ketones 203
5.11 Oxidation reactions 208
5.12 Reactions involving alpha hydrogens 210
5.12.1 (I) Keto-enol equilibria 210
5.12.2 (11) Enolate ions 212
5.12.3 (111) Haloform reaction 213
5.13 Condensation Reactions 214
5.13.1 Aldol addition 215
5.13.2 Aldol condensation 219
5.13.3 Claisen-Schmidt reaction 219
5.13.4 Perkin reaction 220
5.13.5 Knoevenagel reaction 221
5.13.6 Mannich reaction 222
5.13.7 Reformatsky reaction 223
5.13.8 Benzoin condensation 226
5.13.9 Cannizzaro reaction 226
5.13.10 Tischenko reaction 229
5.14 Wittig reaction 230
5.15 a, ('\-Unsaturated aldehydes and ketones 232
Very short answer questions 236
Problems with solutions 237
Problems for self assessment 238
Answers to very short answer questions 245
Solutions of problems 246

6 CARBOXYLIC ACIDS 252-314


6.1 Nomenclature 252
6.2 Aliphatic carboxylic acids 254
6.3 Substituted acids 263
6.4 Halo acids 264
6.5 Hydroxy acids 266
6.6 Malic acid 269
6.7 Tartaric acid 270
6.8 Citric acid 274
6.9 Dicarboxylic acids 277
6.10 Unsaturated monocarboxylic acids 282
6.11 Unsaturated dicarboxylic acids 284
6.12 Aromatic carboxylic acids 287
6.13 Reactions of Aromatic carboxylic acids 294
6.14 Substituted Aromatic Acids 296
6.15 Phenolic Acids 299
6.16 Salicylic acid derivatives and drugs 301
Very short answer questions 302
Problems with solutions 303
Problems for self assessment 306
Answers to very short answer questions 310
Solutions of problems 311
(viii)

7 CARBOXYLIC ACID DERIVATIVES 315-354


7.0 Introduction 315
7.1 Nomenclature 315
7.2 Reactivity of acyl derivatives 319
7.3 Relative reactivities and stabilities of acyl derivatives 319
7.4 Acid chlorides 321
7.5 Acid anhydrides 323
7.6 Esters 325
7.7 Amides 336
Very short answer questions 342
Problems with wolutions 343
Problems for self assessment 344
Answer to very short answer questions 347
Solutions of problems 348

8 ORGANIC COMPOUNDS OF NITROGEN 355-473


8.1 Nitroalkanes 355
8.2 Aromatic nitro compounds 360
8.3 Halonitroarenes 368
8.4 Picric acid 370
8.5 Amines 372
8.6 Nomenclature of amines 372
8.7 Preparation of amines 373
8.8 Geometry and Basicity of amines 379
8.9 Basicity of monosubstituted anilines 387
8.10 Properties of amines 392
8.11 Reactions of amines with nitrous acid 396
8.12 Carbylamine reaction 379
8.13 Action of carbon disulphide 399
8.14 Condensation with aldehydes 399
8.15 Ring substitution reactions of aromatic amines 400
8.16 Oxidation 401
8.17 Quaternary Ammonium salts 402
8.18 Amine salts as Phase-transfer catalysts 404
8.19 Aromatic Diazonium salts 405
8.20 Replacement reactions 406
8.21 Reactions proceeding without loss of nitrogen 413
8.22 Structure of benzene diazonium salts 417
8.23 Diazoalkanes 418
8.24 Diazomethane 419
8.25 Reactions in which N2 is lost 420
8.26 Reactions in which Nitrogen is retained 423
8.27 a-Diazoketones 424
Very short answer questions 426
Problems with solutions 427
Problems for self assessment 429
Answers to very short answer questions 431
Solutions of problems 432
1.1 Introduction

Structure elucidation of organic compounds by classical methods is a tedious and time consuming
process. Further, large quantity of compound is needed. This makes the structural elucidation of
many organic compounds more difficult. However, with the development in spectroscopic methods,
particularly ultraviolet (UV), infrared (IR), nuclear magnetic resonance (NMR) and mass (MS) the
task has become relatively easier. Thus fundamental to modern techniques of structure determination
is the field of spectroscopy: the study of the interaction of matter and electromagnetic radiation. In
fact, spectroscopy is the measurement of the amount of light absorbed by a compound as a function
of the wavelength of light. In general, the sample is irradiated by a light source, and the amount of
light transmitted at variolls wavelengths is measured by a detector. Unlike chemical tests, spectroscopic
techniques are nondestructive; that is, none of the sample is destroyed.
1.2. Electromagnetic Spectrum

V'isible light is one form of energy generally known as electromagnetic radiation. Other common
forms of electromagnetic radiation are X-rays; ultraviolet radiation (UV, the radiation from the
sun); infrared radiation (lR, the radiation from a heat,source); microwaves (lJsed in radar and in the
microwave oven); and radio waves (used to carry radio and television signals). Electromagnetic
radiations can be characterised by their frequency or wavelength. The wavelength is a more
convenient description of waves with higher frequencies. The wavelength (A) of a wave is defined by
the equation

~A=.f ... (i)


v
=
in which c the velocity of light = 3 x IO lD cm/sec, and v = frequency of radiation.
The energy associated with a particular electromagnetic radiation is given by the expression:
hc
E = flv = J: ... (ii)
where E = energy of radiation in ergs
It = Planck's constant (6.62 x 10-27 ergs sec)
v = frequency of radiation (in hertz or cps)
Equation (ii) shows that the energy, frequency and wavelength of electromagnetic radiation are
simply related. Thus, when the frequency or wavelength of electromagnetic radiation is known, its
energy is also known. The total range of electromagnetic radiation is called the electromagnetic
spectrum. The types of radiation within the electromagnetic spectrum are shown in Fig. 1.1. All
electromagnetic radiations are fundamentally the same, the various forms differ only in energy.
2 UNDERGRADUATE ORGANIC CHEMISTRY

Wavelength (A) Energy per mole Molecular effects


10- 10 meter gamma rays 106 kcal
10-8 meter X-rays 104 kcal ionization
vacuum UV 102 kcal
near UV electronic transition~

10- 6 meter visible 10 kcal


10-4 meter infrared (IR) 1 kcal molecular vibrations
10-2 kcal rotational motion
10-2 meter microwave
10-4 kcal
I QO (1 meter) radio nuclear spin transitions
10-6 kcal
102 meters
Fig. 1.1 Electromagnetic spectrum

electromagnetic radiation (light)


1.3 Absorption Spectroscopy

Thesepctroscopy
most common type of
used for structure
determination is absorption
spectroscopy. The basis of absorption
spectroscopy is that substance can
absorb energy from celtain wavelengths
incident sample light not
of electromagnetic radiation. In an
light absorbed by
absorption spectroscopy experiment,
sample
this absorption is determined as a
function of wavelength, frequency or Fig. 1.2 An absorption spectroscopy experiment
energy in an instrument called
spectrophotometer or spectrometer (Fig. 1.2).
The experiment requires, first a source of electromagnetic radiation. We place the material to be
examined (known as sample), in the radiation beam. A detector measures the intensity of radiation
that passes through the sample unabsorbed; when this intensity is subtracted from the intensity of the
source, the amount of radiation absorbed by the sample is known. We then vary the wavelength of
the radiation falling on the sample, and the radiation observed at each wavelength is recorded as a
graph of either radiation transmitted or radiation absorbed versus wavelength or frequency. This graph
is commonly known as a spectrum of the sample (Figs. 1.3 and 1.4).
There are many types of spectroscopy. The three types of greatest use to organic chemists for
structure determination are NMR, IR and UV-visible spectroscopy. These types of spectroscopy differ
conceptually only in the type of radiation used, although the kinds of spectrometers required for each
are quite different. Mass spectrometry is fourth physical technique but it is not a type of absorption
spectroscopy and is thus fundamentally different from NMR, IR and UV spectroscopy.
1.4 Origin of Absorption Spectra
he energy (E) of molecule, besides translational and nuclear energies (which do not interfere in
T spectroscopic analysis) can be considered to be made up of:
(i) Electronic or transitional energy: This is the energy which is associated with motion of
electrons in the molecule.
SPECTROSCOPY 3

2.62.B 3 3.5 4 4.5 5 5.5 6 7 B 9 10 11 12 13141516


100.---------------------------~1---------------------------,

~
~ BO
.~ 60
c:
~
~ 40
~
~ 20
Q.

3BOO 3400 3000 2600 2200 2000 1BOO 1600 1400 1200 1000 900 BOO 600
Wavenumber cm- 1

Fig. 1.3 Infrared spectrum of nonane

1.0r----------------------,
0.9 -
Amax = 222
0.8 -
0.7 -
~ 0.6-
c
C\l
eo CH 2 =CH-C =CH 2
I
Cl)
.c CH 3
C\l
(solvent = methanol)

0-
200210220230240250260270280290300310 320330340350
A (nm)

Fig. 1.4 The UV spectrum of isoprene dissolved in methanol


shows Amax =222 nm, e =20,000

(ii) Vibrational energy: This is the energy which is associated with the vibrations of the
constituent atom in the molecule.
(iii) Rotational energy: This is the energy which is associated with the rotation of the molecule
as a whole.
Thus the total energy of the molecule for spectoscpic purpose can be written as:
Etotal = Eelectronic + Evibrational + Erotational
Each of tnese energies is quantised and can exist with some discrete values. This means that
these energies have to follow quantum restrictions. The discrete values (quanti sed) of these energies
depend on the properties of the moleculs, i.e., shape, size, flexibility as well as on the type of the
motion.
If a molecule is placed in an electromagnetic radiation, a transfer of energy from the
electromagnetic radiation to the molecule occurs when,
I1E= hv
4 UNDERGRADUATE ORGANIC CHEMISTRY

where h == Planck's constant


v == frequency of light
!1E = Difference in energy between two quanti sed states.
The molecule absorbs energy when it is excited from the lower energy state E I to higher energy
'.;tate £2. Hence,

when molecule absorbs energy, there may be three types of changes in the molecule.
(i) There may be change in rotational levels.
(ii) There may also be a change in vibrational levels on which rotational change may be
supelimposed.
(iii) An electronic state may change simultaneously with changes in both vibrational and
rotational energies.
As a result, even with a simple diatomic molecule, there is posibility of a large number of
changes in energy states producing many spectral lines.
The various energy levels in the molecule are shown in Fig. 1.5. Suppose A and B are two
electronic states (energy state n) of a molecule. In each electronic state there are vibrational energy
levels, indicated by virbational quantum number V (== 0, 1,2,3,4,5, ... ). Again, for each vibrational
state (energy level), there exist several rotational energy levels, indicated by quantum number
J (== 0, 1, 2, 3,4, 5, ... ). A possible transition in anyone of these energy levels will lead to a charge in
energy content and hence give rise to spectral lines.

J
------3
t -----------2
------1
V=3------------------------0
------3
-------2
-------1
V=2---------------------0
-------3
-------2
--------1
V=1----------------------0
-------~
------1
V=O 0 Electronic Trans ition (t.n = 1)
B (n = 2)

i
.--------- J
3
2
1
V=3 o
Vibrational- rotational ~
Transitions (t. V = 1, t. J = 2) 1
V=2 o
3
Rotational Transition (t. J = 1) 2
V=1 6
~
1
V=O o
A (n = 1)

Fig. 1.5 Molecular energy level diagram


SPECTROSCOPY 5

1.5 Classification of Molecular Spectra


here are following types of molecular spectra, correspnding to the types of energy changes in a
Tmolecule.
(1) Rotational Spectra: Rotational spectra are produced due to change in energy in rotational
quantum levels within a vibrational level. The rotational energy levels are relatively close to each other
and hence energy changes taking place in rotational transitions are of small amounts. [hat is why pure
rotational spectra appear in far infrared and microwave region (i.e., 104 ).l to 102 ).l range).
(2) Vibrational-Rotational Spectra: The separation of vibrational energy levels is greater as
compared to the rotational levels. Thus the vibrational spectra would appear in the mid-infrared regions
(10 2 ).l to 1 ).l range). During a vibrational change, the rotational energy also changes and the energy
absorbed is the sum of two energy changes.
(3) Electronic Spectra: The electronic energy levels (denoted by the quantum number 11) are
far apart. Hence a change in electronic state is associated with a larger difference in energy. The
electronic spectra appear in the visible and ultraviolet region Cl ).l to 0.1 ).l range). That is why
electronic spectra are also called ultraviolet and visible spectroscopy.
(4) Nuclear Magnetic Resonance (NMR) Spectra: Nuclear magnetic resonance spectroscopy
is concerned with the study of interaction of electromagnetic radiation in' the radio frequency region
(3 MHz to 30,000 MHz) with spinning nuclei. NMR spectroscopy measures the energy necessary to
bring about transitions between spin states of nuclei in molecules. This depends on the magl1etic
property of atomic nuclei. The absorption of electromagnetic radiation takes plac~ under the influence
of an applied magnetic field.
(5) Electron Spin Resonance (ESR) Spectra: ESR spectroscopy is an absorption
spectroscopy which involves the absorption of radiation in the microwave region (104 - 106 MHz) by
substances containing one or more unpaired electrons which display characteristic magnetic properties
arising from the spin properties of unpaired electrons. This absorption of microwave radiation takes
place under the influence of an applied magnetic field. The substances with one or more unpaired
electrons are paramagnetic and exihibit ESR, thus ESR spectroscopy is also called electron
paramagnetic resonance (EPR) spectroscopy or el,l!ctron magnetic resonance spectroscopy.
(6) Mass Spectrometry (MS): Besides the above types of spectroscopic techniques using
electromagnetic radiations, another technique is mass spectrometry which has major structural and
analytic applications. It is not a type of absorption spectroscopy and is thus fundamentally different
from DV, IR, NMR and ESR spectroscopy. Mass spectrometry is based on the principle that molecules
in the vapour phase are converted, by bombarding with high energy electron beams, into parent (initial
formula) and daughter (fragment) positive (or less often negative) ions which are sorted and recorded
according to their mle (m = mass, e = charge) by passing through a combination of magnetic andlor
electric fields.
1.6 Ultr,aviolet and Visible Spectroscopy
ltraviolet spectroscopy measures the absorption of ultraviolet lig~t by ~ sam~le. Die~es and oth~r
U conjugated compounds give useful DV spectra. Thus, before dlscussmg thIS techmque we wIll
.first discuss molecular orbital picture of conjugated polyenes.
1.6.1 Construction of pi molecular orbitals of polyenes
A conjugated polyene contains either 411 or (4n + 2) n electrons. The simplest 4n system is 1,
3-butadiene where 11 = 1. The simplest (4n + 2) n electron system is 1, 3, 5-hexatriene where 11 = 1.
The pi molecular orbitals of conjugated molecules can be constructed according to following
generalisations:
(1) A pi electron system derived from the interaction of say m p-atomic orbitals contains 111
6 UNDERGRADUATE ORGANIC CHEMISTRY

molecular orbitals that differ in energy. Thus the number of pi molecular orbitals is the same as the
number of p-atomic orbitals ovedapping in the conjugated system.
(2) Half of the molecular orbitals (i.e., half of m = ml2) have lower energy than the isolated
p-orbitals. These are called bonding molecular orbitals and are represented by 1t or ",. The remaining
half (i.e., m12) have higher energy than the isolated p-orbitals. These are called antibonding molecular
orbitals and are represented by 1t* or ",*.
(3) The bonding molecular orbital of lowest energy, "'1or 1t) has no nodes. Each molecular
orbital of increasingly higher energy has one additional node. In 1, 3-butadiene "'1
has no node,"'2
has one node, "'3* has two nodes and "'4* has three nodes.
(4) The nodes occur between atoms and are arranged symmetrically with respect to the centre
of the 1t electron system.
1.6.2 Construction of molecular orbitals of ethylene and 1,3-butadiene
Pi molecular orbitals of ethylene from the two p atomic orbitals of the two carbons can be
constructed as follows:
Each p orbital consists of two lobes, with opposite phases of the wave function of the two lobes.
The plus and minus signs used in drawing these orbitals indicate the phase of the wave function.
In the bonding orbital of ethylene, there is overlap of similar signs (+ with + and - with -) in
the bonding region between the nuclei. This reinforcement of the wave function is called constructive
overlap. In the anti bonding orbital there is cancelling of opposite signs (+ and -) in the bonding
region. This cancelling of the wave function is called destructive overlap. (Fig. 1.6).
In butadiene, we have a system of four p orbitals on four adjacent carbons. These four atomic
p orbitals will overlap to produce four 1t molecular orbitals. We can get four new MO's in a number
of equivalent ways. One of the ways to obtain four new molecular orbitals is by linear combination

H-
- +
destructive
overlap
n* (antibonding)

w --~-----------------~-- isolated
p-orbital

U
u_ +_ n (bonding)

constructive
overlap

Fig. 1.6 The combination of two p orbitals results in the formation


of two molecular orbitals
of two molecular orbitals of ethylene. Linear combination always takes place between two orbitals
having minimum energy difference. This means that we need to look only at the result of the 1t ± 1t
and 1t* + 1t* interactions and do not have to consider 1t ±1t* (Fig. 1.7).
SPECTROSCOPY 7

H-
- +
/
1t*
'¥4*=1t*-1t*
anti bounding
interaction
~
otJBG 1t*

~ bonding interaction/

~ ~ ~ ~~
re'
0_G'-
/ '¥2=1t-1t

antibonding
InteractIon

Ethylene ~ bonding interaction/EthYlene


• n
0~

'¥1=1t+1t
1,3-Butadiene

Fig. 1.7 The schematic formation of the 1t molecular orbitals of


1,3-butadiene from the 1t molecular orbitals of ethylene
The lowest energy orbital ('If 1) of 1, 3-butadiene is exceptionally stable for two reasons: there
are three bonding interactions, and the electrons are delocalised over four nuclei.
Bonding Bonding Bonding

\jI1 = 1t + Tt
All
(bonding interaction between two ethylene bonding MO's)

The second molecular orbital ('lf2) of 1, 3-butadiene is obtained from the antibonding interaction
between two bonding molecular orbitals of ethylene. The 'lf2 orbital has two bonding and one
8 UNDERGRADUATE ORGANIC CHEMISTRY

antibonding interaction, so we would expect it to be a bonding orbital (two bonding-one antibonding


= one bonding). Thus energy of \112 is more than that of \11 I. \112 molecular orbital has one node between
C2 - C3' A node is a plane where the wave function drops to zero.
Bonding Antibonding Bonding
8\:i-~OO

rs-rs-n
'\112 = n - n (antibonding interaction betw'een two ethylene n molecular orbitals)

The third butadiene MO, \113* bas two nodes. This molecular orbital is obtained from the bonding
interaction between 11:* and 11:* of two ethylene molecules. There is a bonding interaction at the
c2 - C3 bond and there are two antibonding interactions: one at Cl - C2 bond and the other at the
c3 - q bO;1d. This is an antibonding orbital (one bonding-two antibonding = one anti bonding MO)
having two nodes. Thus energy of this orbital is more than the energy of \112 MO.

~
-
---n----~
Antibonding Bonding Antibonding

-
+
-
+ -

\113 = n* + n* (bonding interaction between two antibonding MO's of ethylene)

The fourth molecular orbital (\114*) is obtained from the antibonding interaction between
and 11:* of two ethylene molecules. This molecular orbital has three nodes and is totally anti bonding.
11:*
This MO has the highest energy.
Antibonding Antibonding Antibonding

~--!--~---~
\Ill = n* - n* (antibonding interaction between n* and n* of ethylene)
Two 11: molecular orbitals are of particular importance in understanding UV spectroscopy. One
is the occupied molecular orbital of highest energy, known as highest occupied molecular orbital
(HOMO). The other is the unoccupied molecular orbital of lowest energy known as lowest unoccupied
molecular orbital (LUMO). The energy difference between HOMO and LUMO is minimum. (Fig. 1.8
on next page)
1.7 The UV Spectrum
bsorption of radiations in UV-visible range 1 nm to 800 nm) causes electronic excitations. The
(t.,
A electrons are excited from their ground state to higher excitation states by absorbing the proper
radiations. Since UV-visible spectroscopy involves electronic transitions, it is often called electronic
spectroscopy. The intensity of absorption of radiations as a function of wavelength of light absorbed
is plotted and the graph gives an idea 'of electronic transitions taking place in the molecule. From
these electronic transitions information is obtained about the structure of the molecule.
Most of the organic compounds absorb UV light having wave length of 200-400 nm. The
coloured compounds usually absorb the light of wavelength 400-800 nm but they may also absorb the
SPECTROSCOPY 9

\{f
4
*-

U- LUMO
tnJ
UJ
~ ~ ~ ~ ~;- LUMO

\{f2tf- HOMO

~ ~ it- HOMO

Ethylen ~~~~
1.3-Butadiene

Fig. 1.8 HOMO and LUMO of ethylene and 1.3-butadiene

light of sholter wavelengths, the radiations having wavelength shorter than 200 nm are also absorbed
by atmospheric gases. Therefore, in order to study the transitions brought about by these radiations in
a molecule, the study should be conducted in vacuum.
Most UV-visible spectrophotometers are double beam instruments as shown schematic ally in
Fig. 1.9. The caption of this figure briefly describes the working of the spectrophotometer. For
recording an UV spectrum. The sample is dissolved in a suitable organic solvent and placed in a cell
while pure solvent is placed in another similar cell called the reference cell. The most common solvents
used for recording UV spectra are methanol, ethanol, hexane and water, which are transparent to UV
Reference cell
with solvent
UV source ~
I r Reference beam 1---;::d..,........J::::--------~
~

!
Monochromator
,
Is Sample beam

Sample dissolved
Recorder
plot of log
in solvent
Fig. 1.9 In the ultraviolet spectrometer, the UV source produces a continuum of light in the UV region. The
monochromator selects one wavelength of light, which is split into two beams. One beam passes through
the sample cell, while the other passes through the reference cell. The detector measures the ratio of the
two beams, and the chart recorder plots this ratio as a function of wavelength.
10 UNDERGRADUATE ORGANIC CHEMISTRY

radiation. The light source is usually a hydrogen lamp, and the opticals and cells are made of quartz
because most other clear materials absorb UV radiation.
The absorption of energy is recorded as absorbance (not transmittance).
Two empirical laws have been formulated about absorption intensity.
(1) Lambert's Law: Lambert's law states that the fraction of the incident monochromatic
radiation absorbed by a homogeneous medium is independent of the intensity of the incident radiation.
(2) Beer's Law: Beer's law states that the absorption of a monochromatic radiation by a
homogeneous medium is proportional to the number of absorbing molecules.
The absorption at a particular wavelength is defined by the equation:
Ir
A =log~

where A = absorbance
I r = intensity of the reference radiation
l\, = intensity of the beam coming out of sample cell.
The absorbance by a compound at a particular wavelength increases with an increasing number
of molecules undergoing transitions. Therefore, absorbance depends upon the electronic structure of
the compound and also upon the concentration of the sample and the length of the sample cell. For
this reason energy absorption is reported as molar asborptivity E, also known as molar extinction
coetfcient, rather than as the actual absorbance. Often UV spectra are reported to show E or log E
instead of A, as the ordinate. The log E value is specially useful when values for E are very large.
AccC
A cc I
Therefore:
A cc Cl
A = constant Cl
A = E. Cl
A
E=-
Cl
where E= molar absorptivity
A = absorbance
C = concentration in mole/litre
I = cell length in cm
If absorbance, concentration and cell length are known, the molar absorptivity can be calculated.
It is a valuable information that can be used in connection with UV spectra. Spectra are often redrawn
by plotting E against A, expressed in nm. (One nanometer equals to 10-9 meter). The molar absorptivity
ranges from 10 to 100,000. The typical UV spectrum plot is shown in Fig. 1.10. UV absorption bands
are thus characterised by the wavelength of the absorption maxima (Amax) and E.
1.8 Types of Electronic Transitions
consider the different types of electronic tr~nsitions which ta~e place on absorption .of light
L etin usUV-visible range. The ground state of organIc molecule contams valence electrons m three
principal types of molecular orbitals: Sigma (a) orbitals. pi (n) orbitals and filled, but nonbonded
orbitals (n). Both a and n orbitals are formed from the overlapping of two atomic or hybrid orbitals.
Each of these molecular orbitals, therefore, has an antibonding a* to n* orbital associated with it. An
orbital containing nonbonding (n) electrons does not have an antibonding orbital because nonbonding
SPECTROSCOPY 11

182 200 250 300 500

105

104

w
103
o
11
H, /C-H
/
C=C
CH 3 C
,
(Solvent; hexane)
102

10
50,000 45,000 40,000 35,000 30,000 25,000

Fig. 1.10 Typical UV spectrum

electrons present in them do not form bonds. Electron transitions involve the promotion of an electron
from one of the three
ground states (cr,1t or n)
0'*
to one of the two excited 11-0'*
states (cr* or 1t*). The ~E <150 kcal
four important transitions >185 nm
0
and their relative energies 1t

are shown in Fig. 1.11. 11-1t*


The most useful ~E <105 kcal ~E 0 ' - 0'* > 175 kcal
region of the UV >270 nm <165 nm
spectrum is at 11
wavelengths longer than ~---+1t*

200 nm. The following E ~E <170 kcal


>165 nm
transitions give rise to
absorption in the
1t
non-useful 100-200 nm
range: 1t ~ 1t* for an
isolated double bond and
cr ~ cr* for an ordinary 0'.

carbon-carbon bond. The


useful transitions
Fig. 1.11 Energy requirement for different electronic transitions
12 UNDERGRADUATE ORGANIC CHEMISTRY

(200-400 nm) are n ~ n* for compound with conjugated double bonds and some
11 ~cr* and 11 ~ n* transitions.
1.9 Formation of Absorption Bands

Since the energy required for each electronic transition is quanti sed, the UV spectrum is expected
to exhibit a single, discrete line corresponding to each electronic transition. In practice, broad.
absorption bands are usually observed. In a molecule, each electronic energy level (either in ground
state or in excited state) is accompanied by large number of vibrational (e.g., Vo, VI> V2, .•. etC'.) ~nd
rotational (e.g., 10,11> h, h ...etc.) energy levels which are also quantised (Fig. 1.5). In complex
molecules having many atoms, there are still a large number of closer vibrational energy levels.
The radiation' energy that passes through a sample is sufficient to induce various electronic
transitions as well as transitions in accompanying vibrational and rotational energy levels. However,
these transitions have very small energy difference, but the energy. required to induce an electronic
transition is larger than that required to cause transition in the accomparying vibrational and rotational
energy levels. Thus, electronic absorption is superimposed upon the accompanying vibrational and
rotational absorptions resulting in the formation 9f broad bands. In other words, not only a single but
a large number of very close wavelengths are absorbed and the closeness of the resulting discrete lines
causes them to coalesce to give broad absorption bands in case of complex molecules.
1.10 Designation of Abs~rption Bands
UV-visible absorption bands may be designated by the type of electronic transition from which they
originate, e.g., cr ~ cr* band, n ~ n* band, etc., or by the letter designation. The following letter
designation was proposed because more than one band may arise due to the same type of electronic
transition.
(1) K-bands (German: Konjugierte = conjugated): These bands originate from n - n*
transitions in compounds having a n - n conjugated system. The intensity of K-band is usuaUy 104 .
K-band is exihibited by conjugated enes and enones. Some K bonds attributed to n ~ n* transitions
are given in Table 1.1.

'tit:"." K Bands attributed to n ~ n* transitions

Compound Amax nm Emax

1, 3-Butadiene 217 21,000

Acrolein 210 11,500

Acetophenone 240 13,000

2, 3-Dimethylbutadiene 226 21,400

Styrene 244 12,000

I, 3, 5-Hexatriene 258 35,000

(2) R-Bands (German: Radikalartig = Radical-like): These bands ongmate from n ~ n*


transitions of a single chromophoric group, e.g., carbonyl or nitro group. These bands are also called
forbidden bands. R bands are less intense with cmax value below 100. Some R bands attributed to
n ~ n* transitions are given in the Table 1.2.
SPECTROSCOPY 13

MM:"••" R Bands attributed to n ~ 11: * transitions

Compound Amax, nm Emax

Acetaldehyde 290 17
Acetone 279 15
Acrolem
.
Methyl vinyl ketone
315
320
14
14
Acetophenone 319 50

(3) B-Bands (Benzenoid bands): These bands originate from 11: ~ 11:* transitions in aromatic
or hetero aromatic compounds. Some B bands due to 11: ~ 11:* transitions are given in the Table 1.3.

'm:"." B-Bands due to 11: ~ 11:* transitions

Compound Amax, nm Emax

Be1)zene 256 200


Toluene 262 174
Naphthalene 312 289
Phenol 270 1450

(4) E or Ethylenic Bands: Such bands originate due to the electronic tranSitIOns in the
benzenoid system of three ethylenic bands which are in closed cyclic conjugation. These are further
characterised as El and E2 bands. The El band of benzene, which appears at lower wavelength (180
nm) is more intense than E2 band that occurs at longer wavelength (200 nm). Some El and E2 bands
due to 11: ~ 11:* transitions are given in Table 1.4.

'm:".,' E-Bands due to 11: ~ 11:* transitions

El band E2 band
Compound
Arnax Emax Arnax Ernax

Benzene 180 60,000 200 7,900


Naphthalene \ 221 133,000 286 9,300
Anthracene 256 180,000 375 9,000

1.11 Transition Probability: Allowed and Forbidden Transitions


n exposure to UV or visible radiation a molecule mayor may not absorb the radiation, i.e., it may
Oor may not undergo electronic excitation. The molar absorptivity at maximum absorption has been
found to be:
Cmax = 0.87 x 1020 P.a.
where P = transition probability with value from 0 to 1
a = Target area of the absorbing system, i.e., a chromophore
A chromophore with a length of the order of 10 A or 10-7 cm and with unit probability will
have cmax value of z 105. Thus there ·is a direct relationship between the area of chromophore and its
4
absorption intensity (cmax)' Transitions with cmax values greater than 10 are called allowed transitions.
14 UNDERGRADUATE ORGANIC CHEMISTRY

These are generally caused by n -7 n* transtions, e.g., in 1, 3-butadiene, the absorption at 217 nm,
cmax 21,000 results from the allowed transitions. Transitions with cmax less than 104 are called
forbidden transitions. These are generally caused by n -7 n* transitions, e.g., in carbonyl compounds,
the absorption near 300 nm with cmax values 10-100 results from the forbidden transition.
In addition to the area of a chromophore, there are some other factors also which govern the
transition probability. However, the prediction of their effects on the transition probability is
complicated because they involve geometries of the lower and higher energy molecular orbitals as
well as symmetry of the molecule as a whole. Symmetrical molecules have more restrictions on their
transitions than comparatively less symmetrical molecules. Consequently, symmetrical molecules like
benzene have simple electronic absorption spectra as compared to less symmetrical molecules. There
is much less symmetry restriction for a highly unsymmetrical molecule, thus it will exhibit a complex
electronic absorption spectrum.
1.12 Terminology used in UV Spectroscopy
he following terms are commonly used in DV spectroscopy:
T 1.12.1 Chromophore: A covalently unsaturated group responsible for absorption in the DV or
visible region is known as a chromophore. For example:
EB
C=C, C=C, C=O, C=N, N=N, -N=O, etc.
\09
Molecules containing the same chromophores can usually be expected to have similar DV
spectra.
1.12.2 Auxochrome (Auxilliary chromophore): A covalently saturated group, which, when
attached to a chromophore, changes both the wavelength and intensity of the absorption maximum is
known as an auxochrome. Generally auxochromes are atoms or groups with one or more lone pairs,
e.g., -~H, -~R, -.S.H, -NH2' -NR2' -~:, etc.
1.12.3 Bathochromic shift or Effect: The shift of the absorption maximum to longer
wavelength caused by either substitution on to the chromophore (by an auxochrome), or by a change
in the solv~nt is called a bathochromic shift or red shift.
For example, benzene shows Amax 256 nm and aniline shows Amax 280 nm. Thus there is a

bathochromic shift of 24 nm in the Amax of benzene due to the presence of the auxochrome -NH 2·
Similarly, a bathochromic shift of n -7 n* band is observed in carbonyl compounds on decreasing
solvent polarity, e.g., Amax of acetone is at 264.5 nn is water as compared to 279 nm in hexane.
1.12.4 Hypsochromic shift or Effect: The shift of an absorption maximum to a shorter
wavelength as a result of removal of conjugation, or change in solvent polarity. For example, aniline-
shows Amax 280 nm, whereas anilinium ion (acidic solution of aniline) shows Amax 254 nm. This
hypsochromic shift is due to the removal of n - n conjugation of the lone pair of electrons of the
nitrogen atom of aniline with the n-bonded system of the benzene ring on protonation because the
protonated aniline (anilinium ion) has no lone pair of electrons for conjugation. Similarly, there is a
hyprochromic shift of 10-20 nm in the Amax of n -7n* bands of carbonyl compounds on going from
ethanol as solvent to hexane, i.e., on decreasing solvent polarity.
1.12.5 Hyperchromic Effect: An effect which leads to an increase in absorption intensity
(cmax) is called hyperchromic effect (Fig. 1.12). The introduction of an auxochrome usually causes
hyperchromic shift. For example, benezene shows B-band at 256 nm, cmax 200, whereas aniline shows
B-band at 280 nm, cmax 1430. The increase of 1230 in the value cmax of aniline compared to that of
benzene is due to the hyperchromic effect of the auxochrome NH2·
SPECTROSCOPY 15

Hyperchromic

emax Hypsochromic --+----::0-+-:::---+ Bathochromic

I
I
I

HypoJhromic / Absorption band


I
I
I
I
I
Aniax

-----------Wavelenght------+..
Fig. 1.12 Shifts in absorption position and intensity

1.12.6 Hypochromic effect: An effect which leads to a decrease in absorption intensity,


(cmax) is called hypochromic effect (Fig. 1.12). This is caused by reduction in conjugation. For
example, aniline shows Amax 280 nm and cmax 1430 whereas the anilinium ion shows Amax 254 nm
and cmax 160.
Amax of some isolated chromophoric groups are given in Table 1.5.

'm=II." Amax of some isolated chromophoric groups

Chromophore Example "'max Emax Transition Solvent

/ -
'C-C/ , Ethylene 171 15,530 1t -7 1t* Vapour
-C==C- Acetylene 150 10,000 1t -7 1t* Hexame
)C=O Acetaldehyde 160 20,000 n -7 0* Vapour
180 10,000 1t -71t* Vapour
290 17 n -71t* Hexane
Acetone 166 16,000 n -7 0* Vapour
188 900 1t -7 1t* Hexane
279 15 n -71t* Hexane
-COOH Acetic acid 204 60 n -71t* Water
-COOR Ethyl acetate 211 57 n -71t* Ethanol
-CONH 2 Acetamide 178 9500 1t -71t* Hexane
220 63 n -71t* Water
-C==N Acetonitrile 167 Weak 1t -7 1t* Vapour

1.13 Effect of Conjugation on Absorption Maximum


The 1t -1t* transition of ethylene requires absorption of light at 171 nm (164 kcal/mole), slightly
into the vacuum ultraviolet region. In conjugated system, however, there are electronic transtitions
with lower energies that correspond to wavelengths longer than 200 nm. Let us compare the energy
levels of ethylene and 1, 3-butadiene.
16 UNDERGRADUATE ORGANIC CHEMISTRY

In ethylene there is only one occupied MO and only one unoccupied MO. The only possible
transition is the excitation of an electron from the occupied MO to the unoccupied MO. In butadiene
there are four possible transitions, involving excitation of an electron from either of the field orbitals
into either of the empty ones. The lowest energy transition, corresponding to absorption of light of
the longest wavelength, is the excitation of an electron from the HOMO to the LUMO. This is a
11:2 ~ 11:3* transition.
Notice in Fig. 1.13 that the HOMO of butadiene is higher in energy than the HOMO of ethylene.
Also, the LUMO of butadiene is lower in energy than the LUMO of ethylene. Both of these differences
reduce the relative energy of the 11: ~ 11:* transition in butadiene. The reSUlting absorption is at 217
nm (129 kcal (mole).

+
, ,, + , *
-, + -,, + 1t4

! !

+ I _

1
*
, ,
--!- +,

+
_I LUMO
1t - -
, ,+
I]
1 1
1 *
1t3
>.
e>
-1+ -I
1
+ + 1
1
-
Q)
c: 164 kcal hv
ID
(171 nm) .:.::c:
E
~
Olr-...
217nm C\j ....
HOMO .... C\j
1

+
+ + + +'1 -

*
1t2
-- 1t -I
1
+ +
!

ethylene + + + +
1t1
it it
ground excited
state state

1 1, 3-butadiene 1

Fig. 1.13 In 1,3-butadiene, the 1t ~ 1t* transition absorbs at a wavelength of 217 nm (129 kcal/mole or 540
kJ/mole), compared with 171 nm (164 kcal/mole or 686 kJ/mole) for ethylene. This longer-wavelength
(lower-energy) absorption results from a smaller energy difference between the HOMO and LUMO in butadiene
than in ethylene

Just as conjugated dienes absorb at longer wavelengths than simple alkenes, the conjugated
trienes absorb at even longer wavelengths. In 1,3,5-hexatriene, for example, (Fig. 1.14), the HOMO
is 11:3 and the LUMO is 11:4*. The lowest energy transition is the excitation of an electron from 11:3 into
11:4*. The HOMO in 1,3,5-hexatriene is slightly higher in energy than that for I, 3-butadiene, and the
hexatriene LUMO is slightly lower in energy. Once again, the narrowing of the energy between the
HOMO and the LUMO gives a lower energy, longer wavelength absorption. The principal 11: ~ 11:*
transition in 1,3,5-hexatriene occurs at 258 nm (108 kcallmole).
Similar to the conjugated alkenes, other conjugated compounds such as aldehydes, ketones, etc.
also absorb at longer wavelengths as compared to the simple unconjugated compounds.
Another way to point out the narrowing of the HOMO-LUMO energy as the conjugated system
grows is to look at the number of. nodes in the molecular orbitals. In general, the HOMO of a
SPECTROSCOPY 17

I I I I I

+:-:+:-:+:- i I i
.
1ts -- --
-:+:-:+:-:+
I I

I I I I

+:-:++:-:+r
I i I
*
1ts -- --
-:+:--:+:-
.. .

LUMO 1 1 1
+:--:++:- * LUMO
--
-I 129 kcal
I

-:++:--:+
i i 1C4

hv
~
T
217 nm 1 1 HOMO 258nm
HOMO
++:--:++
tt
* 1-
1 1 1t3
--1++1--
1 1

1
+++:---

* *-tt
1 1t2
---:+++
++++++

*
butadiene energies
(for comparison)
ground excited
state state
1, 3, 5-hexatriene

Fig.1.14 1,3,5-hexatriene has a smaller energy difference (108 kcal/mole or 452 kJ/mole) between its HOMO
and LUMO than does 1,3-butadiene (129 kcal/mole or 540 kJ/mole). The n ~ n* transillon corresponding to
this energy difference absorbs at a longer wavelength: 228 nm, compared with 217 nm for 1,3-butadiene

conjugated system with N pi electrons has NI2 - 1 nodes: none for ethylene, one for butadiene, two
for 1.3,5-hexatriene and so on. The LUMO always has one more node. Usually the more nodes an
orbital already has, the less additional energy is involved in adding one more node. In other words,
the longer the conjugated system, lesser is the difference between HOMO and LUMO energy
and hence the higher are the values of Amax and cmax.
In general, the longer the conjugated system, the higlzer are the values of Amax and Cmax'
1.14 Solvent Effects
he polarity of the solvent has a significant influence on the position as well as intensity of
T absorption. Compounds like dienes and conjugated polyenes do not experience any appreciable
shift on increasing the polarity of the solv.ent. In general, the absorption maximum for the non-polar
compounds is same in polar (like alcohol) as well as in non-polar (like hexane) solvents. The
absorption maximum for the polar compounds is usually shifted with the change in polarity of the
solvent. Following two rules are used for the effect of solvents on the absorption maxima.
(a) If the absorbing substance is non-polar, the effect of solvent is mainly determined by the
refractive index of the solvent.
(b) For polar light absorbing substances in polar solvents, the dipole moment of the solvent is
mainly responsible for the change in the position of the absorption band.
These rules are. however. not valid in cases where complex formation occurs between solvent
and solute because in such cases the band may appear in an entirely new position. Moreover. polar
18 UNDERGRADUATE ORGANIC CHEMISTRY

solvents such as water, alcohols, ketones and esters tend to obliterate spectral fine structure arising
from vibrational effects. Let us consider solvents' effects in the following transitions:
(i) n ~ 11:* transitions: If a group is more polar in the ground state than in the excited state;
the non-bonded electrons in the ground state are stabilised relative to the excited state due to hydrogen
bonding or dipole-dipole interactions with the polar solvents. As a result, the energy difference between
the excited state and the ground state increases and hence the absorption shifts towards shorter wave
length as shown below:

ll*E
"N""-pol~
LlE,
- - .... - ... -

~>
t.E
1t*

solvent
-,--_
'~n
Polar solvent
. .,

Effect of polarity of solvent on n ~ n* transition

A carbonyl group is more polar in the ground state than in the excited state.
5+ 0- Ii+ Ii-
)C:.::..:O )C-O
Ground state Excited state
more polar (less polar)
As a result hydrogen bonding or dipole-dipole interactions will lower the energy of the ground
state more than that of the excited state and hence the absorption shifted to shorter wavelength. For
example, the absorption maximum of acetone which appears at 279 nm in hexane (non-polar solvent)
shifts to shorter wave length as the polarity of the solvent increases.
Solvent C6H14 CHCl3 C2HSOH CH30H H20
Amax (nm) 279. 277 272 270 265
(ii) 11: ~ 11: transition: If a group is more polar in the excited state than in the ground state, the
hydrogen bonding and dipole-dipole interactions with the solvent will stabilise the excited state more
than the ground. As a result, the energy gap between the ground state and the excited state decreases
and the absorption shifted towards longer wavelength as shown below:
n*--r--" ,

M, ------~"'
_~<AEI
_---- n
n Non-po1ar- so
- -Iven t Polar solvent

Effect of polarity of solvent on n ~ n* transition

Consider for example, ethylene molecule. In the ground state, the molecule is non-polar. But in
the excited state, one of the carbon atoms becomes electron deficient and the other electron rich. As
a result, the molecule is more polar in the excired state.

"c=c/
/"
,,8+ 0-/
/C--C"
Ground state Excited state
(non-polar) (more polar)
Consequently, in a polar solvent, 11:* orbitals will be stabilised relative to 11: Drbitals and hence
absorption shifts to longer wavelength.
SPECTROSCOPY 19

It has been found that an increase in solvent polarity usually shifts 11 ~ n* and n ~ 0'* bands
to shorter wavelengths. and n ~ n* bands of polar compounds to longer wavelengths.
1.15 Electronic Spectra: Structure Relationships

T he(1)following structural effects have remarkable influence on the electronic spectra:


Resonance effect
(2) Hyperconjugative effect
(3) Hydrogen bonding effect
(4) Steric effect
1.15.1 Resonance effect on electronic spectra: Resonance stabilises both the ground state
and the excited state of a species; the stabilisation effect may be greater in one than in the other. If
resonance stabilises the excited state more in comparison to the ground state, the electronic excitation
energy (I1E) will be lower than what it would have been if the resonance had stabilised the g,ound
state more relative to the excited state; and consequently, the Amax value in the former case will be
greater than that of the later case. Thus, it is not the magnitude of the resonance energy but whether
resonance stabilises primarily the excited state or the ground state that decides the effect of resonance
on UV spectra. For example, naphthalene and azulene are two isomeric aromatic compounds.

Naphthalene
DJ Azulene

Resonance stabilises the ground state of napththalene more relative to its excited state. while it
stabilises the excited state of azulene less in comparison to its ground state. As a consequence the
I1E of azulene is less than the M of naphthalene. Since the wavelength of absorption depends on the
I1E value, azulene absorbs light at a longer wavelength than naphthalene does. Accordingly, azulene
is deep blue in colour while naphthalene is colourless.
Conjugated systems have increased resonance stabilisation in the excited states. Greater number
of charge separated structures that can be written for the excited state perhaps brings about the
resonance stabilisation of the state. Thus a conjugated system has lower I1E value and hence longer
Amax value than a similar non-conjugated system. In fact, as the conjugation of the chromophores
increases, usually deepening of colour also increases. Thus. the longer the length of the conjugation
ill system, the longer is the wavelength of absorption and larger is the molar absOlptivity.
For example :

Amax = 319 nm Amax = 377 nm


colourless pale yellow

C6H,-(CH=CH)s-C 6Hs
Amax = 425 nm
orange
Equivalent resonance, amongst polar structures, stabilises the excited state relative to the ground
state, as a result of which absorption occurs at a longer wavelength in the case of a polar species with
respect to its non-polar counterpart. For this reason phenol is colourless in the solid state wh:!c j', i~
yellow in alkaline medium.
20 UNDERGRADUATE ORGANIC CHEMISTRY

6+-+ 6
e
(More stable)
8

Thus, more resonance stabilisation of the excited state leads to the bathochromic shift, and the
hypsochromic shift occurs if the ground state is more resonance stabilised.
1.15.2 Hyperconjugative Effect: Since hyperconjugation too brings stability to the excited as
well as to the ground state, it has the same effects on Arnax and Ernax as resonance shows. Alkyl group
present on the conjugated carbon stabilises its excited state than its ground state through
hyperconjugation. Thus bathochromic shift occurs if the hydrogen atoms on a chromophoric system
are substituted by alkyl group I
(10 or 2°). Thus 3-methyl-3-penten-2-one absorbs at 236 nm but
3-penten-2-one absorbs at 224 nm for 11: -711:* transition.
o o
11
CH3-CH=C-C-CH3 CH3-CH=CH-C-CH3
I
CH3
" 3-Penten·2-one
"'max 224 nrn

3-Methyl-3-penten-2-one
"'max 236 nrn

1.15.3 Hydrogen bonding effect: Owing to greater polarity, the strength of an intramolecular
hydrogen bonding increases in the excited state relative to the ground state. Therefore, intramolecular
hydrogen bonding stabilises the excited state than its ground state and thus decreases the energy
content of the excited state. Hence the 11£ value of the electronic transition of a molecule having
intramolecular hydrogen bonding will be lower than what would have been if there were no
intramolecular hydrogen bonding. For example, o-nitrophenol is yellow in colour while its isomer
p-nitrophenol is a pale yellow coloured substance.
1.15.4 Steric Effect on UV spectra: We know that the position and intensity of absorption
depend on the length of the conjugation; the longer the length of the conjugation, the longer is the
wavelength of absorption and the larger is the Ernax. If the steric effect hinders the coplanarity of a
system, delocalisation of pi electrons will be hindered; and as a consequence, the length of conjugation
will decrease.
For example, trans-cinnamic acid absorbs at a longer wavelength
(Arnax = 272 nm, Ernax = 15,900) than eis-cinnamic acid (Arnax = 268 nm, Ernax = 10,700). This is
because the former has a coplanar structure and delocalisation of pi electrons occurs completely across
the molecule while in eis isomer the delocalisation is hindered because it loses coplanarity owing to
the overlap of ortllO hydrogen of the phenyl group and the carboxylic group as shown below:
SPECTROSCOPY 21

H" /H

<Roo"iy
C=C

7rans-cinnamic acid Cis-cinnamic acid

1.16 Important Chromophores


Systems: If two or more similar chromophores are present in a molecule and they
Conjugated
are not in conjugation with each other, the effect on the spectrum is usually not additive. There is
little electronic interaction between isolated chromophoric groups. However, if two chromophoric
groups are in conjugation with each other, a large effect on the spectrum results because the n electron
system is spread over atleast four atomic centres. When two chromophoric groups are conjugated, the
high intensity (n ~ n* transition) absorption band is generally shifted 15-45 nm to longer wavelength
with respect to the simple unconjugated chromophore. Examples of various conjugated chromophoric
groups are given in Table 1.6.

'm:!!- Amax of simple conjugated chromophoric groups

Chromophore Example Amax (om) Transition Emax Solvent

I I
)C=C-C=C<
Butadiene 217 1t ~ 1t* 21,000 Hexane

I I I I
)C=C-C=C-C=C< 1, 3, 5-Hexatriene 258 1t ~ 1t* 35,000 Hexane

I
)C=C-C=C- Vinylacetylene 219 1t ~ 1t* 7,600 Hexane
228 1t ~ 1t* 7,800 Hexane

)c=~J=o Acrolein 210 1t ~ 1t* 11,500 Ethanol


315 n~1t* 14 Ethanol

I I
)C=C-C=O Crotonaldehyde 218 1t ~ 1t* 18,000 Ethanol
320 n~1t* 30 Ethanol

I I
O=C-C=O Glyoxal 195 1t ~ 1t* 35 Hexane
280 n~1t* 3 Hexane

The UV spectra of et, 13 unsaturated aldehydes, ketones and conjugated dienes l~p.a themselves
to an excellent numerical correlation depending on the number of alkyl, alkyoxyl. acetoxy, etc.
substituent groups attached to the ethylenic linkages present. The rules have been formulated by
L. Fieser and R.B. Woodward.
1.17 Woodward-Fieser rules For calculating Amax
of Conjugated Dienes and polyenes
ase value for fransoid dienes and heteroannular dienes 214 nm
B Base value for cisoid dines and homoannular dienes 253 nm
22 UNDERGRADUATE ORGANIC CHEMISTRY

Add for each substitutent attached to the conjugated system


(i) Double bond extending conjugation 30 nm
(ii) Alkyl substitutents or ring residues on double bond 5 nm
(iii) OR (alkoxy) 6 nm
(iv) Cl, Br 5 nm
(v) Exocyclic conjugated double bond
-5-nm- - -
Calculated Amax of the compound = Total nm
It must be noted that acyclic dienes exist in the preferred (strainless) transoid conformation. In
compounds containing both homoannular and heteroannular diene systems, the caIc~lations are based
on the longer wavelength (253 nm), i.e., the homoannular diene system. The calculated and observed
values of Amax usually match within ± 5 nm. Let us clear the terms which are used in Woodward-Fieser
rules for conjugated dienes.
1.17.1 Homoannular Dienes: In homoannular dienes, conjugated double bonds are present in
the same ring and there have s-cis (cisoid) configuration (s = single bond joining two double bonded
carbon atoms) as illustrated below:

o co
(I) (II)
00 (Ill)

The s-cis-configuation causes strain which raises the ground state energy level of the molecule
leaving the higher energy excited state relatively unchanged. Thus the transition energy is lowered
resulting in the shift of absorption to a longer wavelength.
1.17.2 Heteroannular Dienes: In heteroannular dienes, conjugated double bonds are not
present in the same ring and these have s-trans (transoid) configuration as shown below:

co (IV)
00 0-0
(V) (VI)

1.17.3 Exocyclic Conjugated double bonds: The carbon-carbon double bonds projecting
outside a ring are called exocyclic double bonds, e.g.,

Endocyclic/Q
double bond

CH 2
~ExocycJic
double bond
(VII)

In bicyclic and polycyclic polyenes exocyclic double bonds are always present on the bridgehead
carbons.
Note that the same double bond may be exocyclic to one ring, while endocycIic to the other
(structures VIII and IX) and sometimes the same double bond may be exocyclic to two rings
simultaneously (structure X).
1.17.4 Double Bonds extending conjugation: The parent compound for Woodward-Fieser rule
is 1, 3-butadiene which contains only two conjugated double bonds. Total number of conjugated double
bonds in a given polyene minus two is the number of double bonds extending conjugation.
SPECTROSCOPY 23

Exocyclic to ring A

~':":.".

~
Exocyclic to ring A
but endocyclic to
ringB A B
Endocyclic ~

~
double bond
(IX) Exocyclic to ring B
(VIII) but endocyclic to
(one exocyclic double bond) ring A
(Two exocyclic double bonds)

Exocyclic to two
rings,A and C
(Equivalent to two exocyclic double bonds)
-::?
A

(X)

For example: CH2=CH-CH=CH-CH=CH2


3 - 2 = 1; One double bond extending conjugation
CH2=CH-CH=CH-CH=CH-CH=CH2
4 - 2 = 2; Two double bonds extending conjugation

4 - 2 = 2; Two double bonds extending conjugation.


1.17.5 Alkyl Substituents and Ring residues: Only the alkyl substituents and ring residues
attached to the carbon atoms constituting the conjugated system of the compound are taken into
account.
Number of alkyl substituents or ring residues of the given compound can be known by comparing
it with parent compound (having no alkyl substitutents).
Suppose we want to know the alkyl substituents in compound (XI):
CH 3-CH=CH-C=C-CH3
I I
CH3CH3
(XI)
Parent diene of the compound (XI) is 1, 3-betadiene, i.e., (XII):
CH2=CH-CH=CH2
(XII)

Let us compare (XII) with (XI):

CH2=CH-CH=CH2
432
(XII)
24 UNDERGRADUATE ORGANIC CHEMISTRY

4 3 2 1
CH3-CH=CH-C=C-CH3
1 I I
CH3CH3
2
(XI)

Match carbon-I, 2, 3 and 4 of parent compound (XII) with carbon-I, 2, 3 and 4 respectively of
the compound (XI). Number of subs'tituents on carbon-I, 2, 3 and 4 are indicated by numbers in circle.
Thus carbon-I has two alkyl substituents carbon-2 has one alkyl substituent, carbon-3 has no alkyl
substituents and carbon-4 has one alkyl substituent. Thus total number of alkyl substituents is four.
Number of alkyl substituents and ring residues in some conjugated polyenes
6 5 4 3 2 1
Example 1. CH 3-C=CH-C=C-CH=CH-CH2-CH3
I I I
CH3 CH3C2H5
CD 0 CD 0=5
Parent triene is:
6 5 4 3 2 1
CH2=CH-CH=CH-CH=CH2

Example 2.

(j)'I~
3UJ n Total number of
ring residues = 3

o
Parent compound is diene
CH2=CH-CH=CH2
4 3 2 4

Example 3. Total number of


ring residues = 6

The following examples illustrate how these general rules may be applied.

Example 4.

2,3·Dimethyl-l.3-butadiene
SPECTROSCOPY 25

Base value for acyclic diene 214 nm


Two alkyl substitutents (2 x 5) 10 nm
Calculate Amax 224 nm
Observed Amax = 223 nm
Example 5. @-CH=CH-CH=CH2
I, 3-Pentadiene

Base value for acyclic diene 214 nm


One alkyl substituent 5nm
Calculated Amax 219 nm
Observed Amax = 220 nm
Example 6.

Since the two double bonds occur in two different rings, the diene is heteroannular, and the base
value is 214 nm. There are four ring residues attached to the double bonds, increasing the Amax by
4 x 5 or 20 nm. Finally, each double bond is exo to the other ring, adding 2 x 5 or 10 nm. Thus the
predicted Amax is 214 + 20 + 10 = 244 nm. The observed value is 245 nm.

Example.7.

Since the double bonds occur in the same ring, the base value of 253 nm (homoannular diene)
is used. There are two alkyl substituents and two ring residues attached to the double bonds, increasing
the Amax 5 x 4 or 20 nm. Thus the predicted Amax = 253 + 20 = 273 nm; the observed value is 262 nm.

Example 8.

Base value =253 nm


Three ring residues = 3 x 5 = 15 nm
One exocyclic double bond to ring B = 5 nm
Predicted Amax = 273 nm
Observed Amax = 275 nm
Example 9.
CH 2=CH-CH=CH-CH=CH-CH=CH2
26 UNDERGRADUATE ORGANIC CHEMISTRY

Base value = 214 nm


Two double bonds extending conjugation = 60 nm
Amax = 274 nm
Example 10.

~
Base value =214 nm
Two alkyl substituents = 10 nm
One double bond extending conjugation =30 nm
--'-X-- -=--="2"=5""-4-n-m-
mux

Example 11.

Base value = 253 nm (for homoannular and not for hetero because
base value of homo is greater)
Three ring residues = 15 nm
One double bond extending conjugation = 30 nm
One exocycJic double bond =5 nm
Amax = 303 nm

,/ -:?" ./
Example 12.
00 ./ l

\ •...•• ~ \ .•....

Base value =253 nm


Four ring residues = 20 nm
Two exocycJic double bonds = 10 nm
Amax = 283 nm

Example 13. ~
~
Base value = 214 nm
Three ring residues = 15 nm
One exocycJic double bond to ring A = 5 nm
Predicted Amax = 234 nm
Observed Amax = 235 nm
SPECTROSCOPY 27

Example 14.

Base value = 214 nm


One alkyl substituent = 5 nm
Calculated Arnax = 219 nm
Observed Arnax = 224 nm

Example 15.

Base value for heteroannular diene = 214 nm


Two ring residues = 10 nm
One exocyclic double bond = 5 nm
Arnax (calculated) = 229 nm
Arnax (observed) = 232 nm

Example 16.

1 _ _ Exocyclic double bond for ring C

Exocyclic double bond for ring B

(i) Base value for homoannular deiene =253 nm


(ii) Six ring residues =30nm
(iii) One double bond extending conjugation =30nm
(iv) Two exocyclic double bonds =10nm
(v) One double bond exocyclic to two rings simultaneously = 10 nm
Calculated Amax = 333 nm
28 UNDERGRADUATE ORGANIC CHEMISTRY

1.18 Woodward-Fieser Rules for calculating Amax of


a, ~ unsaturated carbonyl compounds (en ones)
ompounds containing a carbonyl group in conjugation with a double bond are called enones.
C. Spectra of en ones are characterised by an intense absorption band in the 215-250 nm region
(cmax usually 10,000-20,000) and a weak n ~ n* band at 310-330 nm.
Woodward and Fieser have derived the following empirical rules for calculating the position of
Amax of a, ~-unsaturated carbonyl compounds (enones).

I I I I I I
C=C--C=O C=C-C=C-C=O
~ ex 8 Y ~ ex
Enone Dienone
Base values :
Acyclic a, ~-unsaturated ketones 215 nm
Six-membered cyclic a, ~-unsaturated ketones 215 nm
Five-membered cyclic a, (3-unsaturated ketones 202 nm
a, (3-unsaturated aldehydes 207 nm
Add for each :
(i) Double bond extending conjugation 30 nm
(ii) Alkyl group, ring residue on:
a-carbon 10 nm
(3-carbon 12 nm
y and higher carbon 18 nm
(iii) Polar substituents Position in conjugated system
-OH a 35 nm
(3 30 nm
y 50 nm
-OAc a,(3,<5 6nm
-OMe a 35 nm
(3 30 nm
y 17 nm
<5 31 nm
-Cl a 15 nm
(3 12 nm
-Br a 25 nm
(3 30 nm
Exocyclic carbon-carbon double bond 5 nm
Homoannular diene comP9nent* 39 nm
Calculated Amax for ethanolic solution = Total nm

*Two conjugated double bonds in the same ring.


SPECTROSCOPY 29

Example 1.

The following examples illustrate how these rules may be applied.


Base Value 215 nm
One a-ring residue 10 nm
One B-ling residue 12 nm
One B-alkyl group 12 nm
~------
Calculated Amax = 249 nm
Observed Amax = 245 nm

Example 2.

o
Six-membered ketone, base value =215 nm
Two B-ring residues = 24 nm
One exocyclic double bond to ring B = 5 nm
Calculated Amax = 244 nm
Observed Amax = 241 nrn

Example 3.

Six-membered enone, base value = 215 nm


One B-ring residue = 12 nm
One 8-ring residue = 18 nm
One exocyclic double bond to ring B Snm
One double bond extending conjugation = 30 nm
~~----~~----
Calculated Amax = 280 nm
Observed Amax = 281 nm

Example 4.
30 UNDERGRADUATE ORGANIC CHEMISTRY

Six-membered enone, base value = 215nm


One 13-ring, residue = 12 nm
One ring residue on higher than y carbon = 18 nm
Two double bonds extending conjugation 60nm
Homoannular diene component = 39 nm
Exocyclic double bond to ring B 5 nm
Calculated Amax ' =349 nm
Observed Amax =348 nm
1.19 Angular Distortion and Cross-Conjugation:
Steric Inhibition of Resonance
The Woodward-Fieser rules for conjugated dienes and carbonyl compounds give reliable results
only where there is absence of strain around the chromophore. Thus the rules are successful for
acyclic and most six-membered ring systems. Well authenticated violations of these rules are abundant
in compounds in which the chromophore distortion is due to either the ring strain or due to the cross
conjugation. * Examples of systems whose DV spectra could not satisfactorily be predicted by
Woodward-Fieser rules are shown below:

(1) (2)

The strained molecule (1) has a Amax at 246 nm whereas the usual calculation gives a value of
229 nm. The diene (2) might be expected to have Amax at 234 nm but the distortion of the chromophore
resulting in the loss of coplanarity of the double bonds with consequent loss of conjugation causes
the Amax to be as low as 220 nIl?

Amax (Calc.) 244 nm


(Obs.) 244 nm

Since (3) is a cross conjugated dienone, the calculation is based on the enone system giving the
higher Amax value, namely, that extending to Cs and having two 13-ring residues and one exocyclic
double bond. The L11 bond is ignored in calculating the maximum. The calclated value and observed
value in this case are identical. In compound (4) the L11 bond is similarly ignored in calculating the
absorption maximum, but the calculated value in this case is not very close to the observed value.

*Cross conjugated systems have the structures (i) and (ii). In (ii) the main chromophore is dienone which
is part of the longest conjugated system.

(i)
c& (11)
o
SPECTROSCOPY 31

2~ Amax (Calc.) 280 nm


o~ 4
(4)
(Obs.) 298 nm

1.20 UV Spectroscopy in Structure Identification

Oisne uncertain
principal use of UV spectroscopy is to identify structure when the position of a double bond
on the basis of either IR or other spectroscopic methods. There are many examples
where the structure of an organic compound can be determined only by UV spectroscopy.
For example, the following two isomeric compounds can be distinguished on the basis of their
UV spectra:

Compound I contains a conjugated diene system, which shows an absorption maxima at 232
nm; the calculated value is also 232 nm. Compound II absorbs near 175 nrn, the value for a single
double bond, because its two double bonds are not conjugated.
Sometimes all possible compounds contain conjugated system (diene, enone, etc.) but in different
positions. By knowing the possible structures and using Woodward-Fieser rules, the structure of
unknown compound may be determined on the basis of its UV spectra.
1.21 Infrared Spectroscopy
nfrared spectrum gives information about the structural details of organic compounds. It allows the
I detection and identification of a large number of organic functional groups because they show
specific and characteristic absorption in the ifrared region. Infrared spectroscopy observes the
vibrations of molecular bonds. This information is used to infer the nature of the bonding and the
functional groups present. Of the spectral methods, IR is the only one that allows for direct
indentification of the functional groups.
Spectral Region: The infrared region of the spectrum extends from 4000 cm- I to 625 cm-I.
The infrared region is split up into three pmts:
(i) the near infrared 12,820 cm- 1 - 3333 cm- I
(ii) the middle infrared 3333 cm-I - 333 cm- 1
(iii) the far infrared 333 cm- 1 - 33 cm- 1
The near infrared region conesponds to energies in the range 37 - 10 kcallmole. Since very few
organic molecules absorb radiation in this range, it is seldom used for spectroscopic purposes.
Radiation in the middle infrared region has energies ranging from 10 to 1 kcallmole. This energy is
associated with molecular vibrations. Spectroscopy in this region is extremely useful to the organic
chemists. The far infrared region has energy 1.0 to 0.1 kcal/mole. This region has been little used for
organic spectroscopy, again because few useful absorptions occur here.
The position of an infrared absorption band is specified by its wavelength <A) measured in
microns ()..tm). A micron (or micrometer) cones ponds to 10-6 of a meter or 10-4 cm, i.e.,
1 !..lm = 10-6 m or l!..lm = 10-4 cm
32 UNDERGRADUATE ORGANIC CHEMISTRY

A more common unit, however, is the wavenumber scale. The wavenumber is simply the
reciprocal of the wavelength (in cm). Since 1 cm = 10,000 /-tm, the wavenumber can be calculated by
dividing 10,000 by the wavelength in microns. The unit of the wavenumber is cm-I. For example, an
absorption at a wavelength 4/-tm conesponds to a wavenumber of 2500 cm-I.
- -I i
v (cm ) = A (cm)

= 10,000 /-tm/cm
A(/-tm)
A (/-tm) = 1O,000/-tm/cm
v (cm-I)
v = 10,000 /-tm/cm
4/-tm
= 2500 cm-I.

1.22 Measurement of IR spectrum


he instrument used for measuring the absorption of infrared radiatron by a molecule is called an
Tinfrared spectrophotometer. A diagram of a typical instrument is shown in/Fig. 1.15. The instrument
is a typical double-beam IR spectrophotometer. It is called a double beam instrum'ent because two
beams of radiation are generated, one of which passes through a cell containing the sample dissolved
in a solvent and the other passes through a cell containing only the solvent. The sample cells and
various optical parts such as prism of the IR spectrophotometer are made of fused rock salt (NaCI)
because NaCI is completely transparent to IR radiations. As a result, great care must be taken in
handling the cells and contact with moisture must be avoided at all times.
Mirro~_ _~_ _ 1

Focussing \
slits
Radiation

e~ Beam
~i.
/ Splitter
Infrared source NaCI.
(heated filament) prism \. Mirror~ ~
\.\ Solvent
\. Rotations of
'. recorder drum
and prism
are synchronized
..................•
IRecorderl +-_ _-1

Fig. 1.15 Schematic diagram of a double-beam infrared spectrophotometer

At one end of the instrument is the IR source which emits all wavelengths of infrared radiation.
The light from this source is split by NaCI prism. The prism is then rotated to let radiation of increasing
wavelength pass through the slits. This gives a single wavelength (monochromatic light) beam that is
then split into two beams and focussed by the min'ors. One beam passes through the compound being
SPECTROSCOPY 33

studied (often dissolved in a solvent) and the other beam passes through solvent alone. The intensities
of the two beams are determined by the IR detector which combines them to produce net transmittance.
This transmittance signal is recorded on a graph paper as a function of wavelength. The rotations of
the prism and recording drum are synchronised so that wavelength (or frequency) and transmittance
are correlated on the graph paper. AIt~ough absorbance could be plotted, most infrared instruments
plot the percent transmittance (% T) which is the ratio of the intensity of the light passing through
the sample (I) to the intensity of light striking the sample (10) times 100. The % T is plotted versus
the wavelength (or frequency) of radiation. The relationship is:

%T=~x 100
10
IR spectra are obtained by irradiation of the sample with light from IR region
(5000 cm- I to 500 cm-I) of the electromagnetic spectrum. The units most commonly used are
wavenumbers. The wavenumber associated with a given wavelength is obtained by taking reciprocal
of the wavelength in centimeter.
1.23 Requirement for the Absorption of Infrared Radiation
(Physical Basis of IR Spectroscopy)
for a molecule to absorb IR radiation, it has to fulfil the following two requirements:
1.23.1 Correct wavelength of Radiation: The absorptions that are observed in an IR spectrum
are the result of vibraLions within a molecule. Atoms within a molecule are not stationary, but are
constantly in motion. Consider, for example. the C-H bonds in a typical organic compound. These
bonds undergo various stretching and bending motions. A useful analogy to the C-H stretching
motion is the stretching and compression of a spring (Fig. 1.16). This vibration takes place with a
. f requency v.
celtam I
'
It is clear from Fig. 1.16 that the stretching of the C-H bond describes a wave motion. A wave
of electromagnetic radiation can transfer its energy to the vibrational wave motion of the C-H bond
only if the following very important condition is fulfilled: There must be an exact match between
the frequency of radiation and the frequency of vibration. This is due to the wave character of atoms

•.
bond at average bond length

~
bond
compressed
J
e=c ~
bond
stretched
.._ _ _ _ _ time required =
o =H for one cycle v

time

Fig.1.16 Chemical bonds undergo a variety of vibrations. The one illustrated here is a stretching vibration.
The bond, represented as a spring, is shown at various times. The bond stretches and compresses about its
average length over time. The time required for one complete cycle of vibration is the reciprocal
of the vibrational frequency
34 UNDERGRADUATE ORGANIC CHEMISTRY

that requires equality between wavelength of the radiation and wavelength of the bond vibration in
order for energy absorption to occur. Each functional group has its own wavelength. Due to this reason
each functional group absorbs different wavelength and thus functional groups are characterised by
IR spectroscopy. On the basis of the above discussion, we can conclude two important points:
(i) Bonds vibrate with characteristic frequencies, and
(ii) Absorption of energy from infrared radiation can occur only when there is match between
the wavelength of the radiation and the wavelength of the bond vibration.
Thus if C-H vibration has a frequency of 9 x 10 13 sec, then it will absorb energy from radiation
with the same frequency. Wavelength and wavenumber of this absorbed frequency can be calculated
as follows:
c
)..------
3 x 1010
- v - 9 x 10 13
= 3.33 x 10-4 cm
= 3.33 x 10-6 m

= 3.331..l
The corresponding wavenumber
v 9 x 1013
v=-=
c 3 x 1010
= 3000 cm-I

When radiation of this wavelength (i.e., 3.33 I..l) interacts with vibrating C-H bond, radiant energy
is absorbed and the bond vibration excited. After energy absorption, bond vibrates with the same
wavelength but with a larger amplitude (a large stretch and tighter compression) (Fig. 1.17). This
absorption gives rise to the peak in the IR spectrum.

Light

Ql frequency v
E
:;::; energy hv

amplitude amplitude

Fig. 1.17 Light absorption by a bond vibration causes the bond (spring) to vibrate at the same wavelength but
with a larger amplitude. The frequency of the light must
exactly match the frequency of the bond vibration
SPECTROSCOPY 35

1.23.2 Electric Dipole: A molecule can absorb IR radiation when its absorption causes a
change in its electric dipole (dipole moment).
A bond with a dipole moment can be visualised as a positive charge and a negative charge
separated by a spring. If this bond is placed in an electric field (Fig. 1.IS), it is either stretched or
compressed depending on the direction of the field.

0--0 represented as ~
force on +
r in direction of field
E ! force on +
in direction of field

molecule stretched mOlecule stretched


dipole moment decreased dipole moment increased
electric
field r force on-
electric
field
opposite to direction
of field
(a)
! force on...;.
opposite t~ .direction
of field
(b)

Fig. 1.18 A bond Wit:l a dipole moment (as in HF, for instance) is either stretched or compressed by an
electric field, depending on the direction of the field. Notice that
the force on the positive charge is in the direction of the electric field (E)
and the force on the negative charge is in the opposite direction

All electromagnetic radiations are associated with oscillating electric and magnetic vectors- at
right angles to the direction of propagation. The electric field of the electromagnetic radiation
alternately stretches and compresses a polar bond as shown in Fig. US. When the electric field is in
the same direction as the dipole moment, the bond is compressed and its dipole moment decreases
(Fig. I.ISa)
When the field is opposite to the dipolemoment, the bond stretches and its dipole moment
increases (Fig. 1.1Sb). If this alternate stretching and compressng of the bond (and the periodic cr.:!nge
in its dipole moment) occurs at the frequency of the molecules' natural rate of vibration, energy may
be absorbed. Vibrations of bonds with non-zero dipole moments ge,nerally result in IR absorptions and
are said to be IR active.
If bond is symmetrical and has zero dipole moment, the electric field of electromagnetic radiation
does not interact with the bond. For example, the tnple bond of acetylene has zero dipole moment.
and the dlpolemoment resmains zero If the bond IS stretched or compressed. Since the Vibration
produces no change in the dipole moment, there can be no absorption of energy. This vibration is Said
to be IR inactive and its char~teristic frequency is not seen in the IR spectrum. Thus the key to an
IR active vibration is that the vibration must change the dipole moment Jof the molecule.
1.24 Selection Rules
nfrared light IS absorbed when the oscillating dipole moment (due to molecular vibration) interacts
I with the oscillating electric vector of the infrared radiation. For this absorption to occur is It
necessary that the dipole moment at one extreme (say stretch position) of a vibration must be different
from the dipole moment at the other extreme (compress pOSition) of the position. .
This point can be illustrated by comparing the C=C stretching vibrations of two alkenes
isobutene and 2. 3-dimethyl-2-butene.
Because of the electron donating characteristics of the methyl group, isobutene has a dipole
moment along the C = C double.
36 UNDERGRADUATE ORGANIC CHEMISTRY

c=c bond in C=C bond in


compressed position stretched position
ll=exl ll'=exl'
when double bond
stretched the dipole
moment increases, because
dipole moment is the
product of both charge and distance

(J.!:;t: J.!' =} J.!' > J.!) .


Because isobutene is associated with a change in dipole moment, the C=C stretching vibration
occurs at 1640 cm-I.
The alkene 2, 2-dimethyl-2-butene, however, has no dipole moment hence double bond of 2,
2-dimethyl-2-butene does not show IR peak in IR spectrum.

CH3\ l /
CH3
C-C
CH/ - \CH3
double bond is not polar, i.e., e =0 double bond is not polar. J..l = e xl' = 0
J..l=exl=O (stretched positions)
(compressed position)

1.25 Molecular Vibrations

I nfrared spectroscopy measures the changes in the stretching and bending vibrations of covalent
bonds, which occur when a molecule absorbs electromagnetic energy in the IR region of the
electromagnetic spectrum. The specific bond being stretched or the specific angle being bent depends
upon the frequency of radiation being absorbed. A stretching vibrational mode con'esponds to change
(positive or negative) in bond distance between bonded atoms along the intermolecular axis. (Fig.
1.19a).


..
___ . - I - .
l'----_JI
n_. ,,
,,
, ,,

Bond stretching
(a)
Bond angle bending
(b)

Fig. 1.19
A bending vibration may consist of a change in bond angle between bonds with a common atom
or the movement of a group of atoms with respect to the remainder of the molecules without movement
of the atoms in the group with respect to one another (Fig. 1.19b). ,
Stretching a bond increases the distance between the two nuclei in the bond. If the energy of
the system as a function of the distance between the nuclei is plotted, following plot is obtained (Fig.
1.20).
SPECTROSCOPY 37

In Fig. 1.20 re is the


equilibJium distance between
the. nuclei. As the energy of w
the system increases, the bond
can exist in various vibrational
excited states Vb V2, V3, etc.
1
The vibrational ground state is
Vo. Most molecules exist in
the Vo level at room
temperature. Since the distance_
absorption of energy is re
supposed to excite a bond to
the next higher energy level, Fig 1.20
most excitations are from Vo
to VI' In this level the amplitude of the molecular vibration is greater. In general, such absorption of
an infrared light quantum can occur only if the dipole moment of the molecule is different in two
vibrational levels.
The vibrational energy of a chemical bond is quantised and can have the value,

Evib = [ V + ~] hv
where V is the vibrational level (V = 0, 1,2) and V is the vibrational frequency of the bond. Absorption
of radiation with energy equal to the difference between two vibrational energy levels (t:.Evib) will
cause a vibrational transition to occur. Transition from the ground state (V = 0) to the first excited
state (V = 1) absorbs light strongly and gives rise to intense bands called the fundamental bands. The
energy difference (t:.Evib) between the lowest possible energy level of a bond and the next higher
energy level is given as :

=hv
This gives the frequency of a fundamental band. Transitions from the ground state (V = 0) to the
second excited state (V = 2) with the absorption of infrared radiation gives rise to weak bands, called
overtones. Overtones are always weaker absorptions than corresponding fundamental vibration. An
overtone occurs at a frequency that is multiple of the fundamental.
t:.Evib = EVib (V = 2) - Evib (V = 0)

=[2+ ~}zv -[0 + ~] hv


=2hv
Polyatomic molecules may exibit more than one fundamental vibrational absorptioIl bands. The
number of these fundamental bands is related to the degree of freedom in the molecule. The number
of degree of freedom is equal to the sum of the co-ordinates necessary to locate all the atoms of a
molecule in space. Each atom has three degrees of freedom corresponding to the three cartesian
38 UNDERGRADUATE ORGANIC CHEMISTRY

co-ordinates (x, y, z) necessary to describe its position relative to other atoms in a molecule. Thus, the
total number of degrees of freedom in a molecule will be equal to 3n, where n is the number of atoms
in a molecule. A molecule which is of finite dimensions will, thus, be made up of rotational, vibrational
and translational degree of freedom.
3n Degree of freedom = Translational + Rotational + Vibrational
Fundamental bands for the linear molecules
Total degree of freedom for linear molecule = 3n
Translational degree of freedom =3
Rotational degree of freedom =2
Vibrational degree of freedom = 3n - (3 + 2)
=3n-5
Each vibrational degree of freedom corresponds to the fundamental mode of vibration and each
fundamental mode corresponds to a band. Hence, there will be 3n - 5 possible fundamental bands for
linear molecules.
Fundamental bands for non-linear molecules
Total degree of freedom = 3n
Translational degree of freedom = 3
Rotational degree of freedom =3
Vibrational degree of freedom = 3n - (3 + 3)
=3n-6
(3n - 5) and (3n - 6) vibrations are called a normal mode. Out of these vibrations
(3n - 5 or 3n - 6), (n - 1) vibrations are stretching vibrations and remaining vibrations are bending
vibrations.
Bending vibrations for linear molecule = 3n - 5 - (n - 1)
= 3n - n - (5 - 1)
=(2n - 4)
Bending vibrations for non-linear molecule = 3n - 6 - (n - 1)
=2n - 5.
The stretching and bending vibrations in a methylene group are given in Fig. 1.21.
Many of these vibrations occur at the same frequency (i.e., same vibrations are degenarated) and
not all of the possibile bands are generally seen ..." IlIdependent absorptions. However, additional
bands, usually of low intensity, may occur as overtones.
As a result, the IR spectrum of organic compound is usually complex.
1.26 Calculation of Fundamental Stretching Frequencies

Thethebond between two atoms is like a vibrating spring. The vibrations of the bond are governed by
laws of physics which govern the motion of a spring.
This approximation, called the "Hooke's Law" pennits the calculation of fundamental stretching
frequency of a bond between two atoms A and B, using the following equation:
1 K(ml + m2)
v=-
2nc ml m2

where V = vibrational frequency in cm- l (wavenumber)


c = Velocity of light in cm/sec
SPECTROSCOPY 39

Average position

XXX symmetrical
stretch

unsymmetrical
stretch

.v
?rb ~
V CV i
~"-pI~""'d(~i~')
'Yffi_~1

~
V V Unsymmetncal
c;~~ut.of.Planebend (twist)

+-- time ---+


Fig. 1.21 Typical vibrations of a -CHr- group in an organic compound. Start at the centre figure in each
case and move left and right to see how the bonds change
with time. The white atoms are hydrogen, the black atoms are carbon
and the grey groups are the other groups attached to carbon
ml = mass of atom A in g

m2 = mass of atom B is g

K = force constant in dyne cm- l


ml m2
--=--~ = m0 (Il) = Reduced mass of the atoms
ml +m2
40 UNDERGRADUATE ORGANIC CHEMISTRY

The force constants for some bonds are given below:


Bond Kin dyne/cm bond length
c-c 5 X 105 L56
C=C 10 X 105 1.33
C=C 15 X 105 1.21
C=O 12.3 x 10S 1.20
Hence K gives useful information regarding the type of bond present in a compound.
From the relationship it is apparent that the frequency of vibration is directly proportional to
the square root of the force constant of the bond. We also know that the force constant is also
related to the bond length. The longer the bond, the smaller the force constant. Thus
v cc -VI:
1
or Vcc-----
Bond length
Thus there is direct correlation between the nature of a covalent bond and the IR absorption
frequency associated with it. For example, the decreasing force constant (i.e., increasing bond length)
of carbon-carbon bond is: triple > double > single. Accordingly the stretching frequency of
-C==:C- is greater than that of -C=C- which, in turn, is greater than C-C as shown:
I I
v= 2200 cm-l 1650 cm- 1 1200 cm- 1
C=C C=C C-C
decreasing bond strength
increasing bond length
decreasing wa venumber,
i.e., absorption frequency.

From the above relationship it is also clear that the frequency of vibration is inversely
proportional to the square root of the reduced mass. Larger mO (IJ.) implies a smaller wavenumber. For
example, bond dissociation energies indicate that a C-H bond (104 kcal/mole) is not much stronger
than a C-C bond (88 kcallmole). Yet the stretching frequencies for these two bonds are 3000 cm-I
and 1200 cm-I, respectively. This can be explained by the fact that the reduced mass of the C-H
bond is much less than the reduced mass of the C-C bond. Thus, vibrations of higher heavier atoms
occur at lower frequency or wavenumber than vibrations, of lighter atoms. The C-H and C-D
bonds have essentially the same force constant. Thus the difference in the IR absorption frequencies
of these two bonds is due to the mass difference between Hand D.

1.27 Factors Affecting Vibrational Frequencies


The vibrational Frequency or wavenumber of absorption can be calculated by Hooke's law. It
has been found that the calculated value of frequency of absorption for a particular bond is never
exactly equal to its experimental value. The difference is due to the fact that vibration of each group
is influenced by the structure of the molecule in the immediate neighbourhood of the bond. The value
of absorption frequency is also shifted since the force constant of a bond changes with its electronic
state. Following are some of the factors responsible for the shifting of vibrational frequencies from
their normal values.
1.27.1 Vibrational coupling (or coupled vibrations): An isolated C-H bond exibits only one
SPECTROSCOPY 41

stretching frequency but in case of methylene group (-CH2-) two absorptions occur which
correspond to symmetric and asymmetric vibrations as shown below :

H H H H

-V Symmetnc
~
Asymmetnc

In such cases, asymmetric vibrations always occur at higher wavenumber than symmetric
vibrations. These vibrations are known as coupled vibrations since these vibrations occur at different
frequencies than that required for an isolated C-H stretching. Similarly, coupled vibrations of methyl
group occur at different frequencies compared to -CH2- group.
Vibrational coupling takes place between two bonds vibrating with similar frequency provided
the bonds are reasonably close in the molecule. Vibrational coupling is a feature ofAX2 groups.
The coupling vibrations may both be fundamentals or a fundamental vibration may couple with the
overtone of some other vibrations. The latter coupling is frequently called Fermi resonance, after
Enrico Fermi who first described it.
Carboxylic acid anhydrides show two C=O stretching absorptions between 1850 - 1800 cm-I
and 1790-1740cm- 1 with a difference of about 50 cm-I. This can be explained due to symmetric
and asymmetric stretching. Coupling occurs between two CO groups which are linked through
-0-.
Vibration coupling of some AX2 groups are given in Table 1.7.

Typical asymmetric and symmetric strectching


frequencies for some common AX2 groups

Group Vantilcm- 1 Vsymlcm- 1


-CHz- 3000 2900
-NH2 3400 3300
-N02 1550 1400
-802 1350 1150
0- 112
-C/ 1600 1400
""0- 112

1.27.2 Hydrogen Bonding: Hydrogen bonding brings about remarkable downward frequency
shifts of the groups involved in it. Stronger the hydrogen bonding, greater is the absorption shift
towards lower wavenumber than the normal value. Generally, bands due to intramolecular hydrogen
bonds are sharp whereas intermolecular hydrogen bonds give rise to broad bands and these depend
on concentration.
Free O-H [Sroup of alcohols and phenols show sharp and strong absorption bands in the region
3590 - 3650 cm- . Sharp, non-hydrogen bonded O-H bands are observed only in the vapour phase,
in very dilute solution, in non-polar solvents or when hydrogen bonding is prevented by steric
hindrance. Pure sample and concentrated solutions of alcohols and phenols show broad O-H
stretching bands in the region about 3200 - 3600 cm-I due to intermolecular hydrogen bonding. The
N-H stretching frequencies of amines are also affected by hydrogen bonding in the same way as
those of the hydroxyl group but frequency shifts for amines are lesser than those for hydoxyl
42 UNDERGRADUATE ORGANIC CHEMISTRY

compounds. This is because nitrogen is less electronegative than oxygen and so the hydrogen bonding
in amines is weaker than that in hydroxyl compounds. For example, non-hydrogen bonded primary
amines exhibit two bands one near 3400 cm- I and the other near 3500 cm- l due to symmetrical and
asymmetrical N-H stretching modes respectively. In pure amines these bands respectively appear in
the range 3250 - 3330 cm- l and 3330 - 3400 cm- I due to intermolecular hydrogen bonding.
Why does hydrogen bonding lower the absorption frequency?
Let us take the example of hydroxy compounds. On hydrogen bonding th'e original O-H bond
is lengthened (weakened) due to electrostatic attraction between the hydrogen atoms of one molecule
and oxygen atoms of the other, and thus the force constant of the O-H bond is reduced resulting in
a decrease in its stretching frequency.
Hydrogen R,,- . +0 -8 /H
2R-0-H --~)
free -O-H
Bonding I
"() --H"""'O
""-R
(i) increase in bond length
(ii) decrease in force constant
(iii) decrease in V
Further, the hydrogen bond can be regarded as a resonance hybrid of the following resonating
structures, so that hydrogen bonding involves a lengthening of the original O-H bond. This bond is
consequently weakened, so the stretching frequency is lowered.
H H
I e I
R-O-H O-R~R-O H-O-R
ffi

I 8-
H
I
R-O-H""""'" O-R
/ 8+
Increase in O--H bond length

Distinction between Inter- and Intramolecular Hydrogen Bondings


In very dilute solution (in non-polar solvents) intermolecular distances are too large to form
intermolecular hydrogen bonds. On the otherhand, in pure liquids, solids and concentrated solutions,
the molecules are closer to form intermolecular hydrogen bonds. Thus intermolecular hydrogen
bonding is concentration dependent. On dilution with non-polar solvents, intermolecular hydrogen
bonds are broken, hence there is decrease in intensity or disappearance of the hydrogen bonded
O-H band and increase in jntensity or appearance of free O-H stretching absorption. The effect of
concentration on intermolecular hydrogen bonding is illustrated in Fig. 1.23 (Section 1.29) in which
the absorption bands in the O-H stretching region are shown for two different concentratins of
cyclohexylcarbinol in CCI4. The band at 3623 cm- l results from the monomer, whereas broad
absorption near 3333 cm- I arises from the polymeric structures due to the intermolecular hydrogen
bonding.
Intramolecular hydrogen bonding is within the same molecule, hence it is not affected by
dilution, and so the absorption band is also unaffected.
Thus a compound with intramolecular hydrogen bonding shows almost the same O-H
stretching in the concentrated solution as in the very delute solution, this means O-H stretching value
SPECTROSCOPY 43

does not change with dilution in the cases of intramolecular hydrogen bonding while the same changes
with dilution in the case of intermolecular hydrogen bonding. Thus dilution can be used to distinguish
between inter- and intramolecular hydrogen bondings.
1.27.3 Electronegativity: As the e1ectronegativity of a bonded atom increases, the shortening
of bond length occurs and the large force constant leads to increased vibrational frequency. Again, as
the electronegativity of a bonded atom changes, the dipole moment of the bond changes. The
absorption intensity being 'proportional to the square of the change in dipole moment as the dipole
moment changes, absorption intensity changes. For example, the decreasing order of electronegativity
of carbon in alkane, alkene and alkyne is :
alkyne> alkene> alkane
the C-H stretching frequencies of these compounds are also in the same order:
I I
C=C-H
-<r-r-H
3300 cm-I 3000-31oocm- 1 2800 - 3000 cm- I

(i) Electronegativity of carbon of the C-H bonds in increasing order.


(ii) Force constant is in decreasing order.
(Ui) v max is also in decreasing order.
1.27.4 Inductive Effect: Inductive effect has profound influence on vibrational frequencies of
groups with multiple bonds.
For example, a carbonyl compound may be considered as a resonance hybrid of .the following
structures :

R"
R'
/C=O ~
(I)
R"Ea

R'
/C-O
(lI)
e

The stretching frequency of a carbonyl group decreases with increasing number of alkyl groups
attached to carbonyl carbon. This is due to +1 effect of alkyl groups which favours the structure (1I)
and lengthens (weakens) the carbon-oxygen double bond. and hence its force constant is decreased
resulting in the lowering of the C=O stretching frequency. Let us take the following examples :

Vmax 1750 cm-I 1745 cm-I 1720 cm-I

(i) carbon-oxygen bond lengths in increasing order (structure II)


(ii) Force constant in decreasing order
(iii) vrnax is in decreasing order
It should be noted why aldehydes absorb at higher frequency than ketones. Similarly, when a
group with -I effect is attached to a C=O group, it favours the structure (I) and its stretching
frequency is increased due to decrease in bond length or increase in the force constant of the
carbon-oxygen double bond. For example, CH3COCH3, CH3COCF3 and CF3COCF3 show vC=O
bands at 1720, 1769 and 1810 cm-I, respectively.
1.27.5 Resonance Effect: We know that owing to p - re and re - re conjugation single bonds
get partial double bond character and double bonds get partial single bond character. It is also known
44 UNDERGRADUATE ORGANIC CHEMISTRY

to us that single bonds are weaker than the corresponding double bonds. So, when a single bond
acquires a partial double bond character through r'esonanc:e, the vibrational frequency of the bond is
expected to be greater than the normal value because of the shortening of bond length. On the other
hand, when a double bond possesses a partial single bond character. the vibrational frequency IS
expected to be lower than the normal value because of the weakening of the bond strength through
resonance. Consider the following examples:
(i) C=O stretching frequency of saturated and a, ~-unsaturated carbonyl compounds.
In an a, ~-unsaturated carbonyl compound 1t - 1t conjugation takes place. Due to this conjugation
C=O group has a partial singk bond character. Thus the C=O bond becomes longer than that In a
saturated carbonyl compound; as a result the C=O bond strength decreases and ItS vibrational
frequency becomes less than that of the C=O group In the saturated carbonyl compound.
e
'" I 11 '" I I
CO °
/c~c---- /C-C=C-

o o
11 11
R-C-R C=C-C-
VmdX 1725 - 1705 cm-I 1

VllIdX 1685 - 1665 cm-I

(ii) C=O stretching frequency of acid derivations.


The absorption frequency of saturated aliphatic keto group of a neat sample is 1715 cm-I.
Replacement of an alkyl group of a saturated aliphatic ketone by a heteroatom (X) shifts the carbonyl
absorption. The direction of the shift depends on whether the inductive effect (a) or resonance effect
(b) predominates.
e

41n·
R-C-X: -
?
R-C=X:
®

(a) (b)

The inductive effect reduces the length of C=O bond and thus increases its force constant and
the frequency of the absorption. The resonance effect increases the C=O bond length and reduces its
force constant and the frequency of absorption (Table 1.8). X
I
The carbonyl absorption of R-C=O
TABLE 1.8
cOf11pounds

X V mllX c=o
Cl 1815 - 1785 cm-I

Br 1812 Cm-I Inductive effect


OH 1760 cm-I predomInates

OR 1750 - 1735 cm-It


NH2 1695 - 1650 cm-I Resonance effect
predomInate,
SR 1620 - 1690 cm-I!
SPECTROSCOPY 45

An NH2 group has -I effect as well as +R effect but the latter predominates. Due to the +R
effect, the C=O group in an amide gets a partial single bond character and possesses lower vibrational
frequency (vrnax C=O, 1650 cm-I) than that in the corresponding ester (C=O, 1750 - 1735 ems-I).
In the case of an ester the -I effect of the alkoxy group predominates over its +R effect.
1.27.6 Steric effect: Steric effects such as steric inhibition of resonance, transannular effect.
etc. intluence stretching frequencies of bonds. For example, the -OH stretching (VO-H) frequency
of phenol is 3330 cm-I. This frequency is due to the intermolecular hydrogen bonding. In contrast to
phenol 2, 6-di-tert-butylphenol, in which steric hindrance prevents intermolecular hydrogen bonding
absorption band is obtained at 3600 cm-I. Similarly the C=O stretching frequency of
2,7 -dimethylene-4,5-benzo tropone is 1596 cm-I, whereas tetramethylene-4,5-benzo-tropone has a
C=O stretching vc=O at 1724 cm-I.

CH 2 CH 2
I . . ~---i
. .... I . . .~-. .
CH 2 CH 2
2,7 -Dimethylene-4,5-benzotropone

r H2
?H2 . . . ~---i
. ....

CH2

2,7-Tetramethylene-4,5-benzotropone

In the later compound, the C=O group is forced qut of the plane of the molecule and being
non-planar, steric inhibition of resonance occurs and the compound shows normal value for vc=o.
Whereas in the former case C-O double bond lengthens owing to conjugation of the C=O Tt bond
with the rest of the molecule and as a consequence vc=o comes down.
1.27.7 Field effects: Electrostatic or steric through space interaction between two groups
within a molecule is called field effect. This field effect often influences the vibrational frequencies
of both the groups. It has been observed that the vC=o is higher when the Cl atom of
a-chlorocyclohexanone occupies the equatorial position than when it is in the axial position. In the
equatorial position, the electron cloud of the Cl atom and that of the oxygen atom experience
electrostatic repulsion and as a result of which carbon-oxygen bond does not acquire a partial single
bond character, if it does so, it will have to face a greater repulsion.

00
°C)o~
00

/
0 0

Repulsion 0

Cl Cl

.. .
o
46 UNDERGRADUATE ORGANIC CHEMISTRY

1.27.8 Ring Size: v max also depends on the size of the ring. For example, carbonyl stretching
frequency in cyclic ketones having ring strain is shifted to higher value. The C-CO-C bond angle
in strained rings is reduced below the normal value of 120°C (acyclic and six membered cyclic ketones
have the normal C-CO--C) angle of 120°C). This leads to an increase in s-character in the sp2
orbital of carbon involved in the C=O bond. Hence, the C=O bond is shortened (strengthened)
resulting in an increase in the vc=o frequency. This increase in the s-character of the outside sp2
orbital is there because it gives more p character to the sp2 orbitals of the ring bonds which relieves
some of the strain, as the preferred bond angle of p orbitals is 90°.

C)=o 0=0 (>=0


No strain _\ Moderate strain Highly strained
-I -I
vc - o 1715 cm 1745 cm 1780 cm

Similar to the ketones, as ring strain in lactones increases, the carbonyl stretching frequency also,
increases.

No strain Moderate strain Highly strained


o-valerolactone y-butyrolactone /3-Propiolactone
v - 1735 cm-I 1770 cm-I 1800 cm-I
c o
The C=O frequency in lactams too depends on the ring size. Similar to that of ketones and
lactones, as the ring strain in lactams increases, the s-character of sp2 carbon of C=O also increases
and thus the carbonyl stretching frequency also increases.
o

o-valerolactam
CN-H
y-butyrolactam
[(u
/3-propiolactam
No strain Moderate strain Highly strained
1
vc_ o 1670 cm- 1700 cm- 1 1745 cm- 1
1.28. Examination of an Infrared Spectrum

A n (1)infrared spectrum consists of :


The functional group region (4000 - 1500 cm-I) and
(2) The fingerprint region (1500 - 667 cm-I)
1.28.1 Examination of the functional group region
(A) 3600 - 3200 cm-I; The appearance of bands in this region shows the presence of
-OH, -NH2 and -NH group in the compound. The ==C-H stretching also shows a medium band
near 3300 cm-I. .
(B) 3200 - 3000 cm-I: Absorption due to =C-H stretching and Ar-H stretching occurs in
this region.
r
(C) 3000 - 2500 cm-I: The absorption due to C-H stretching of CH and CH3 groups occurs
in this region. A broad, moderately intense band between 3000 - 2500 cm- shows the presence of
carboxylic acid dimers. Two weak bands at 2720 cm-I and near 2820 cm-I are most characteristic of
C-H stretching in aldehydes.
(D) 2300 - 2100 cm-I: In this region alkynes, cyanides, cyanates and isocyanates give
SPECTROSCOPY 47

absorption. The -C=C- stretching occurs between 2140 - 2100 cm-I, -C=N stretching shows a
variable band between 2260 - 2200 cm-I. Isocyanates exhibit strong band near 2280 - 2250 cm-I.
(E) 1900 -1750 cm-I: Strong bands due to C=O stretching in aldehydes, ketones, carboxylic
acid, amides, esters and lactones occur in this region. Anhydrides show two strong bands in the region
1850-1740cm- I. Amides exibit doublet around 1700 cm-I. It is important to note that the
a, B-unsaturation in there compounds lowers the frequency of absorption by 15 - 40 cm-I.
(F) 1750 -1600 cm-I: Monosubstituted olefins absorb near 1640 cm-I. Disubstituted trans
olefins, tri and tetrasubstituted olefins absorb near 1670 cm-I. Disubstituted cis olefins and vinylidenne
olefins absorb near 1650 cm-I. Saturated aliphatic ketones show a band at 1700-1720 cm-I.
(G) 1650 -1515 cm-I: Primary and secondary amides and a few lactams display bands in the
region 1650 - 1515 cm-I.
1.28.2 Fingerprint region: It is not possible for any two different compounds (except
enantiomers) to have exactly the same IR spectrum. Therefore, the IR spectrum of a compound is
called its Fingerprint. The region between 1500 - 667 cm- I is called fingerpoi.·t.,'r~gion because every
compound has unique absorption pattern in this region, just as every person han:mique fingerprints.
The fingerprint region contains many absorption bands caused by bending vibrations as well as
absorption bands caused by C-C, C-O and C-N stretching vibrations. Since the number of bending
vibrations [(2n - 5 or (2n - 4)] in a molecule is much greater than its stretching vibrations (n - 1),
the fingerprint region is rich in absorption bands and shoulders. Thus the superimposability of IR band
of the spectra of any two different compounds becomes impossible in this region. However, similar
compounds may show very similar spectra above 1500 cm- .
Fingerprint region is subdivided into following regions:
(A) 1500 -1350 cm-I: The appearance of a doublet near 1380 Cm) and 1365 Cc) cm- l shows
the presence of tertiary butyl group in the compound. Gem dimethyl shows a medium band at
1380 cm-I.
(B) 1300 - 1000 cm-I: All classes of compounds, viz., alcohols, ethers, esters, lactones, acid
anhydrides show strong bands in this region due to C-O stretching. Esters exibit two strong bands
between 1380 - 1050 cm-I. Primary alcohols absorb near 1350 - 1260 cm-I. Appearance of bands
between 1150 - 1070 cm- l due to C-O stretching in C-O-C group is characteristic of ethers.
Phenols absorb at 1200 cm-I. .
(C) Below 1000 cm-I: This region is very useful in identifying the type of subtitution on the
aromatic ring (i). A strong band no - 730 cm- l shows monosubstitution.
(ii) Ortho and para disubstituted compounds show one band each. (735-700 cm- I for ortllO and
800-860 cm- I for para)
(iii) Meta disubstituted compounds are recognised by two medium bands in the region
850 -710 cm-I.
1.29. Characteristic Group Frequencies of Some Organic Molecules

A CHcommon featUre of infrared spectra of many organic compounds is that certain groups like
CH CH, CHO, CO, etc. have, more or less, the same frequencies irrespective of molecular
3, 2,
environment. This shows that these groups must vibrate independently from the rest of the molecules.
On comparing the spectra of related series of compounds one may associate certain vibrational bands
with particular group in the molecule. The presence or absence of certain bands in the spectrum may
be used to indicate whether a particular functional group is present or absent in the molecule. These
frequencies are known as group frequencies and have proved to be very useful for structural
identification.
Chemists have studied thousands of IR spectra and have correlated the absorption frequencies
to the functional groups. Correlation given in Table 1.9 provides summaries of this information.
48 UNDERGRADUATE ORGANIC CHEMISTRY

'n!:!'." IR Absorption Frequencies of Functional Groups

Compound type Bond Type Wavenumber (intensity*)


.....
Alkanes
-~-H
2850-2970 (s)
1340-1470 (s)

-~-{- 1100-1300 (w)

-~-D 2200 (s)

3010-3095 (m)
=t-H 675-995 (.\)
Alkanes
C=C 1610-1680 (v)
Alkynes =C-H 3200-3300 (5)
-C=C- 2100-2260 (v)
Aromatic Ar-H 3010-3100 (m)
690-900 (5)
Aromatic ring C=C 1500-\600 Cu)
Monohydric alcohols and phenols -O-H 3590-3650 (v)
Hydrogen bonded alcohols and -O-H 3200-3600 (v)
phenols
Monomeric carboxylic acids -O-H 3500-3650 (m)
Hydrogen bonded carboxylic acids -O-H 2500-3000 (v, broad)
Amines and ami des -N-H 3300-3500 (m)
I
-N 1180-1360 (5)
Nitriles -C==N 2210-2280 (5)
Alcohols, esters and carboxylic I
-C-O-
acids 1050-\300 (5)
I
Aldehydes, ketones carboxylic C=O \690-1760 (5)
acids and esters
Nitro compounds -NO z \500-1570 (5)
1300-1370 (5)
*Abbreviations: 5 = strong, m = medium, W = weak, v = variable
The region from 1400 - 4000 cm- 1
is specially useful for identification of various functional
groups. This region shows absorption arising from strecthing modes.
The region from 1400 cm- 1 to 600 cm- 1 is often quite complex because both strecthing and
bending modes give rise to absorption in this region. In this region correlation of an individual band
with a specific functional group usually cannot be made with accuracy. However, each organic
compound has its own unique absorption in this region. This part of the spectrum is, therefore, called
the fingerprint region. Although 1500 - 4000 cm- 1 region may appear same for the similar compounds,
the fingerprint region must be different for them.
In the following sections, we will discuss the characteristic IR absorption of compounds
containing C-C and C-H bonds and a few functional groups.
SPECTROSCOPY 49

1.29.1 Carbon-carbon and carbon-hydrogen bonds: Bonds between sp3 carbon atoms give
rise to weak absorption bands in the IR sj:>ectrum. These. absorption bands are not very useful for
structure identification. Bonds between sp2 carbons (C=C) often exibit characteristic absorption
around 1600-1700 cm-I. Aromatic C C bands show absorption at slightly lower frequencies
(1450-1600 cm-I). Bonds between sp carbon atoms (C==C) show weak but extremely characteristic
absorption at 2100 - 2250 cm-I, a region of the spectrum where most other groups show no
absorption.
Almost all organic compounds contain CH bonds. Absorption due to this bond is seen at a.bout
2800 - 3300 cm-I. The CH stretching peaks are often useful in determining the hybridisation of the
carbon atom.
Sp3 C-H 2800 - 3000 cm- I
sp2 C-H 3000 - 3100 cm- I
sp C-H "'" 3300 cm- I
1.29.2 Gem-Dimethyl Groups: The gem-dimethyl grouping often exhibits distinctive
absorption in the C-H bending region. This group shows a strong doublet, with peaks of .almost
equal intensity at 1385 - 1380 cm- I and at 1370 - 1365 cm-I. (Fig. 1.22). Doublets are observed for
gem-dimethyl groups because of interaction between the in-phase and out-of-phase symmetrical
CH3 bending of the two methyl groups attached to a common carbon atom. This absorption is quite
Wavelength (!lm)

-----'"--
3 4 5
100
6
80

60

40

20 CH

o 2000 1800 1600 14 0 1200 1000 800


4000 3500 3000 2500
Waavenumber (cm-I) t=====::.====::=!
Fingerprint region

Fig. 1.22
characteristic of compounds containing gem-dimethyl group.
1.29.3 Alcohols and Phenols: The characteristic bands observed in the spectra of a1cohols and
phenols result from O-H stretching and C-O stretching.
--O-H free
--O-HIIIIIIII O-HIIIIIIII 0
I I I
Hydrogen bonding increases bond distance of O-H and thus decreases bond strength. Decrease
in bond strength means decrease in v rnax .
1.29.4 O-H Stretching vibrations: The free hydroxyl group of a1cohols and phenols absorbs
strongly in the 3650 - 3584 cm- I region. Sharp free hydroxyl bands are observed only in the vapour
phase or in very dilute solution in non-polar solvents. Intermolecular hydrogen bonding increases as
50 UNDERGRADUATE ORGANIC CHEMISTRY

the concentration of the solution increases, and additional bands start to appear at lower frequencies
3550 - 3200 cm-I, at the expense of the free hydroxyl group (Fig. 1.23a and 1.23b). The effect of
concentration on intermolecular hydrogen bonding is illustrated in Fig. 1.23 in which the absorption
bands in the O-H stretching region are shown for two different concentrations of cyclohexylcarbinol
in CCI 4 . The band at 3623 cm- I (Fig. 1.23a) results from the monomer, whereas broad absorption
near 3333 cm-I (Fig. 1.23b) arises from polymeric structures.
4000 3000 4000 3000
4000 3000 4000 300G
0.0- 0,0

~ 1/ ~ -
''[.1
A B
Q) 0.2- ~ 0.2
o z !
c: cl
Cl! aJ
.0 0::
o
CIl
o
(I)
aJ 0.4
~ O. - cl

0.6
0.8
Inter oleculary 1.0
hydro en bonded 1,5
3 3-5 3 3.5
2.5 3 2.5 3
(a) (b)

Fig. 1.23 Infrared spectrum' of the O-H stretching Fig. 1.24 A portion of the infrared spectra of
region of cyclohexylcarbinol in CCI4' (a) 0.03 M o-hydroxyacetophenone. A. 0.03 M, cell thickness: 0.41
(0.406 mm cell). (b) 1.00 M (0.014 mm cell) mm. B. 1.0 M, cell thickness: 0.015 mm
\

In the case of o-hydroxyacetophenone, due to intramolecular hydrogen bonding O-H frequenty


appears at 3077 cm- I as broad, shallow peak and this value is independent of concentration (Fig. 1.24).
In contrast, p-hydroxyacetophenone shows a sharp free hydroxyl peak at 3600 cm- I in dilute CCI 4,
but a neat sample of the compound shows a broad band at 3100 cm- I due to intermolecular hydrogen
bonding involving the -OH group.
/CH3
6YC~~
~ofi
In structures such as 2, 6-di-t-butylphenol. in which steric hindrance prevents intermolecular
hydrogen bonding absorption band at 3600 cm- I is obtained in IR. The C-O stretching vibrations in
alcohols and phenols produce a strong band in the 1200 - 1000 cm-I. These bands are of little
diagnostic value.
1.29.5 Ethers: Ethers have a C-O-C stretching band that falls in the fingerprint region at
1050 - 1260 cm-I. Because oxygen is electronegative, the stretching causes a large' change in bond
moment, therefore C-O absorption is usually strong.
1.29.6 Carbonyl compounds: One of the most distinctive bands in an IR spectrum is the one
arising from the carbonyl strecthing mode. This is a strong peak observed in the region between 1640
and 1820 cm-I. The carbonyl group is it part of many functional groups. The exact position of the
SPECTROSCOPY 51

carbonyl absorption, the positions of other absorption bands in the IR spectrum, and other spectral
techniques may be needed to identify the functional group. The positions of carbonyl group absorption
for different compounds are given in Table 1.10.
TABLE 1.10 Stretching vibrations for some C=O group

Compound vmax in cm- 1

H
I
R-C=O Aldehydes 1720-1740
R
I
R-C=O Ketones 1705-1750
OH
I
R-C=O Acids 1700-1725
OR Esters 1735-1750
I
R-C=O
Amides 1630-1700
Acid halides 1750-1815
Within the range, the (1640 - 1820 cm-I) exact position of the C=O stretching band is
dependent on the following factors : (i) the physical state, (ii) electronic and mass effects of the
neighbouring substitutents, (iii) conjugation, and (iv) hydrogen bonding.
Conjugation of C=C bond results in delocalisation of the 1t electrons of both groups
(C=C and C=O). Delocalisation of the electrons of the C=O group reduces its double bond
character thereby causing absorption at lower wavenumbers. Conjugation with an olefinic or phenyl
group causes absorption in the 1685 - 1666 cm- 1 region. Additional conjugation may cause a slight
further reduction in frequency.
B-Diketones usually exist as mixtures of tautomeric keto and enol forms. The enolic form does
not show the normal absorption of conjugated ketones. Instead, a broad band appears in the
1640 - 1580 cm- 1 region, many times more intense than normal carbonyl absorption. The intense and
displaced absorption results from the intramolecular hydrogen bdnding, the bonded s~:ucture is
stablised by resonance. Et} E>
O-H 0 O-H 0
1 11, 11 I,
R-C=CH-C-R ~ R-C-CH=C-R
Aldehydes C=O stretching vibrations
The carbonyl groups of aJdehydes absorb at slighty higher frequencies than those of the
corresponding methyl ketones. Aliphatic aldehydes absorb near 1740 - 1720 cm-I. Aldehydic carbony I
absorption responds to structural changes in the same manner as ketones. Electronegative substitution
on a-carbon atom increases the frequency of carbonyl absorption. Acetaldehyde absorbs at
1730 cm- l trichloroacetaldehyde absorbs at 1768 cm-- 1. Conjugation reduces the frequency of carbonyl
absorption. a, B-unsaturated acetaldehyde and benzaldehydes absorb in the region 1710 - 1685 cm-I.
Intramolecular hydrogen bonding, as in salicylaldehyde, shifts the absorption (1666 cm-I in
salicylaldehyde) to lower wavenumbers.
52 UNDERGRADUATE ORGANIC CHEMISTRY

C-H stretching vibrations


Aldehydes show aldehydic C-H stretching absorption in the 2830 - 2695 cm- I region. Some
aromatic aldehydes with strong electronegative groups in the ortho position may give aldehydic
C-H strecthing band as high as 2900 cm-I. This absorption is not present in ketones.
(vii) Carboxylic Acids: Carboxylic acids exhibit typical C=O absorption and also show a
very distinctive O-H band.
O-H stretching vibrations
In liquid and solid phase, carboxylic acids exist as a dimer due to strong intermolecular hydrogen
bonding.
e c±)
/o--HIIIIIIIIO~ /OIlIlIlIlH-o~
R-C~ ~C-R- R-C~ ~ C-R
~OIlIlIlIlH-O/ ~o--HIIIIIIIIO/
c±) e
Carboxylic acid dimer display very broad intense O-H stretching absorption in the region
3300 - 2500 cm-I. .
Other structures with strong hydrogen bonding such as f3-diketones (enol form) also absorb in
the region 3300 - 2500 cm-I, but the absorption is usually less intense.
C=O stretching. vibrations
Carboxylic acid dimers display C=O strecthing absorption in the region 1720 - 1705 cm-I.
Intramolecular hydrogen bonding reduces the frequency of the carbonyl stretching absorption to
a greater degree than does intermolecular hydrogen bonding. For example:

~
,-AyOH
~COOH
V max c=o 1665 cm- l COOH
V lllax C=O 1680 cm- l

a, f3-Unsaturated and aryl conjugated acids show absorption for the dimer in the
1710 - 1680 cm- I region. Extension df conjugation beyond the a, f3 position results in very little
change.
Substitution in a-position with electronegative groups, such as the halogens, brings about a slight
increase in the C=O absorption frequency (10 to 20 cm-I).
As mentioned earlier, carbonyl groups of ketones generally absorb in the region
1640 - 1820 cm-I. The position of absorption is also senstitive to ring size. The carbonyl groups of
cyclohexanones generally absorb at the same position as the carbonyl groups of saturated aliphatic
ketones (hex an one vmax 1715 cm-I)

TABLE 1.11

Compound Vmax in cm- 1


Cyclohexanone 1700cm 1
Cyclopentanone 1740 cm- 1
Cyclobutanone 1800 cm- 1
SPECTROSCOPY 53

Table 1.11 shows that highest C=O frequencies arise in the strained cylobutanone and this can
o
11
be explained in terms of bond angle strain; the C-C-C bond angle is reduced below the normal
0
120 leading to increased s character in the C=O bond. The C=O bond is Shortened and therefore
strengthened and so vc=o is increased. If the bond is pushed forward above 120 the opposite effect
0
,

operates, and for this reason di-tert-butyl ketone has very low vc=o (1697 cm-I). Thus ring strain in
cyclic compound causes a relatively large shift to higher frequency. This phenomenon provides a
remarkably reliable test of ring size, distinguising clearly between four, five and larger membered ring
ketones lactones and lactams.
. When the carbonyl group of an ester is present in a five membered ring, absorption owing to
stretching vibration occurs at about 30 cm- 1 higher wavenumber. Thus saturated y-Iactones absorb
higher wavenumber than cS lactones.

VERY SHORT ANSWER QUESTIONS


1. Arrange the folowing electromagnetic radiations in order of their decreasing frequencies:
Radio waves, UV, visible, IR, X-rays, y-rays, microwaves.
2. Arrange the following electronic transitions in order of their decreasing energy:
n ----7 n*, n ----7 n*, 0 ----7 0 *, n ----7 0 *
3. What happens when an organic compound is subjected to UV irradiation ?
4. Can a molecule undergo more than one electronic excitation ?
5. The UV spectrum of acetone shows absorption maxima at 166, 189 and 279 nm. What type of
electronic transition is responsible for each of these ?
6. What type of electronic transitions are possible for each of the following compounds:
(a) CycIopentene (b) Cyclohexane (c) Dimethyl ether (d) CH30H (e) CH3CHO. List then in order
of increasing energy (dE).
7. Are all the molecules of a substance that are exposed to a specific radiation excited ?
8. Arrange the following compounds in order of their increasing Amax in the UV region:
C6Hs-CH=CH-C6Hs CH2=CH-CH=CH2 CH2=CH-CH 2-CH= CH2
(A) (B) (C)
9. Can ionisation of a molecule or breaking of a 0 bond occur in the UV region ?
10. Which of the following compounds would be suitable as a solvent for recording UV spectra of organic
compounds?
(a) Ethanol (b) CycIohexane (c) Benzene (d) Diethyl ether Ce) Acetone
11. What happens to the excited molecules when radiation is cut off?
12. There are antibonding orbitals 0* and n* but not n*. Explain why?
13. What is essential condition for a molecule to be IR active, Le., to absorb IR radiation ?
14. What is main difference between UV and IR spectroscopy ?
15. Why ethanol is a good solvent for UV but not for IR spectroscopy ?
16. Give the wavelength, frequencey and energy changes involved in the normal IR region of the
spectrum.
17. Which of the following molecules are IR active and which are IR inactive?
02, H2, HCI, C12, H20, CH2=CH2, N2
18. What is effect of hybridisation of carbon on the stretching frequency of C-H bonds ?
19. Arrange the following bonds in order of their decreasing vibrational frequencies:
54 UNDERGRADUATE ORGANIC CHEMISTRY

C-CI, C-C, C-Br, C-H, C-I, C-O


20. Which of the following has the highest vc=o frequency?
o

21.
GNH
(I) (11)
cC(III)

Which of the following has the highest carbonyl stretching frequency:


CH3COOH, CH3COCH3, CH3CHO, CH3COCI, CH3CONH2
22. In which of the following the O-H absorption band will be shifted to a higher frequency on dilution
with CCl4 ?

rQYNOCHO

©r ~OH
o ' Z

OH
23. Arrange the following in order of their decreasing stretching frequencies:
O-H, C-C, O-D.

PROBLEMS WITH SOLUTIONS


1. Determine the concentration of a solution of the compound which is kept in 1.00 cm cell having
, absorbance 1.18, absorption maximum 235 nm and Emax is 1.26 X 104 L mole-] cm-I.
2. Determine the molar absorptivity of the solution which is kept in 1.00 cm cell having concentration
7.6 X 10-5 molellitre and absorption coefficient is 0.96.
3. Why is absorbance the function of the concentration of the solution and length of the cell ?
4. Hydrogenation of the triene, (X) with one equivalent of hydrogen gives three isomeric dienes CA),
(B) and Cc). What will be the structures of CA), CB) and (C) and how could the expected Amax values
distinguish among these isomers?

(X)

5. Dehydration of compound CA), can give three isomeric conjugated dienes. What will be structures of
these dienes? Give a mechanism to account for the formation of these dienes. Can these isomers be
distinguished by DV?

(A)

6. The DV spectrum of acetone in hexane shows two absorption maxima O"max = 279 nm, Emax = 15 and
SPECTROSCOPY 55

Amax = 189 nm Emax =900). Identify the electronic transitions associated with each Amax and identify
the more intense band. Name the bands of the transitions.
7. The IR spectrum of ethyl benzoate differs from that of methyl phenylacetate in many ways. Guess at
least one point of difference and give reason for the same.
8. The O-H stretching value does not change with dilution in the case of 1, 2-ethanediol in carbon
tetrachloride but that increases in the case of ethanol on dilution. Explain.
9. Which of the following has a higher DV absorption maximum (Amax) and why?

<;r-N N~N~ < ;r-~H N~NH2


(1) (II)

10•.. Arrange the following compounds in order of their increasing wavelength of DV absorption m·axima
(Amax)
(a) Ethylene (b) Naphthalene (c) Anthracene (d) 1, 3-Butadiene
11. How will you distingnish between each of the following pairs of compounds by DV spectroscopy:
(a) 1, 3-pentadiene and 1, 4-pentadiene
(b) benzene and anthracene
(c) 1, 3-hexadiene and 1, 3-cyc1ohexadiene.
12. Write down the electronic transitions reponsible for the following bands in the DV spectrum of
acrolein:
(i) Amax 210 nrn (Emax 11,500)
(ii) Amax 315 nrn (Emax 14)
13. An organic compound can have one of the following structures:

(a)
00 (b) (c)

The Amax of tpe compound is 236 nm. Which is the most likely structure of the compound? Explain
your choice".
14. Which of the following compounds is expected to have higher value of Amax and why?

OCH-CH 3

(a) (b)

15. The following dienes have the experimental Amax 243 and 265 nm in ethanol. Giving reasons, correlate
the Amax values of the structures (a) and (b):

( a) (b)
56 UNDERGRADUATE ORGANIC CHEMISTRY

16. Giving reasons arrange the following compounds in order of decreasing frequency of carbonyl
absorption in their IR spectra:
H,. . . H. . . . . H. . . . .


c=o c=o
OOH 6
~I
Ca) Cb) Cc)
17. How will you distingnish o-hydroxybenzaldehyde (salicylaldehyde) and m-hydroxybenzaldehyde with
the help of IR spectroscopy?
18. How will you distingnish maleic acid and fumaric acid by their IR spectra?
19. Deduce the structures of isomeric compounds (A) and (B) having molecular formula C3H60 and the
following IR spectral data:
(A) 1710 cm- 1 (B) - 3300 cm- l and 1640 cm- 1
20. Giving reasons arrange the following in increasing order of their vO-H frequency:
Ethanol, trichloroacetic acid, acetic acid and chloroacetic acid.
21. Indicate which of the following vibrations will be IR active or inactive?
Molecule Mode of vibration
(i) CHz=CH z C=C .stretching
(ii) CHz=CHz C-H stretching
(iii) Nz N==N strectching
(iv) SOz Symmetrical stretcling
(v) CO z Symmetrical stretching
(vi) CH3-CH3 C-C stretching

22. Explain why vC=O frequency for m-chlorobenzoic acid is higher than that for p-chlorobenzoic acid?
23. Draw conclusions about the relationship of Amax to the structure of the absorbing molecule from the
following Amax values (in nm):
Ethylene (170); 1, 3-butadine (217); 2, 3-dimethyl-l, 3-butadiene (226); 1,3-cyclohexadiene (256);
1, 3, 5-hexatriene (274).
24. How will you distinguish the following pairs of compounds with the help of their IR spectra:
(i) o-Hydroxybenzoic acid and p-hydroxybenzoic acid.
(ii) Acetone and propionaldehyde.
25. How can UV and IR spectroscopy be used to determine the completion of the following reaction:
o OH
"
CH3-r=CH-CH=CH-C-CH3 ~CH3-r=CH-CH=CH-CH-CH3
NaBH4 I
CH3 CH3
26. How would you distingnish between the N-H stretching absorption of a primary amine (I) and a
secondary amine (11).
H
R-N/
(I)\H
SPECTROSCOPY 57

27. Assign each of the following pairs of absorptions to one of the given compounds:
1865. 1780; 1815, 1750; 1775, 1720 cm- i
o 0
o o
©JC'o/c,,©11 11
11 11
CH3-C-O-C-CH3
(I)
11 c> o
III
28. Which of the following compounds would give the lowest value of vc=o absorption frequency:

11 III
29. Arrange the following compounds in decreasing order of vc=o frequency:

30. The carbonyl stretching absorptions for the following lactones are 1720, 1745 and 1760 cm -I. Match
the absorption with the appropriate structure and give reason for your choice.

0=0 0=0 0 11 III


0

31. Give suitable explanation for the observation that the vO-H band appears near 3570 cm-I whereas
the vO-D band near 2630 cm-I.
32. Using IR spectroscopy, how will you distingnish the following isomeric compounds:
(a) CH3-CHr-C==CH and CH3C==CCH3
(b) CH3CH20H and CH3OCH3
(c) (CH3hN and CH3CH2NHCH3

PROBLEMS FOR SELF ASSESSMENT

1. Most primary ami des show two absorptions in the N-H stretching region (about
3300 cm-I). Consider the resonance structures of amide and suggest a reason for this double peak.
2. Describe the characteristic IR absorption frequencies that would allow you to distinguish between the
following pairs of compounds.
(a) Cyclohexanol and cyclohexanone
(b) Pentanol and 2-pentanone
(c) Benzaldehyde and l-cyclohexene carboaldehyde
(d) 2, 3-Dimethyl-2-butene and 2, 3-dimethyl-l-butene
58 UNDERGRADUATE ORGANIC CHEMISTRY

(e) Butanoic acid and 3-hydroxybutanal


(t) Butanamide and 3-pentanone
3. Calculate absorption maxima (j"max) for the following compounds:
o
(a)o:) (c)
OH

o
4. The absorption maximum of methyl chloride O"max = 173 nm) is less than that of methyl iodide
(Amax = 259 nm). Explain why?
5. The position of absorption of acetone in different solvents (279 nm in hexane, 272 nm in ethanol and
265 nm in water) is different. Explain why?
6. The band due to n ~ 1t* transition in amine disappears -in acid solution. Explain why?

(A)
Cr03/Pyridine
~
ro
7. How would you use IR spectroscopy to tell if preparation of (B) from (A) by oxidation method is
comptete?

(8)
8. Distinguish the following pairs of compounds by IR :
(a) CH3-CHZ-C==CH and CH3-C=C-CH3
(b) CH2=CH-OCH3 and CH3-CH2-CHO
CH3",- /CH3 CH3"" /H
(c) /C=C, and /C=C,
H/ 'H H/ C~
H
(d) H"C=C/COOH and H"C=C/
HOOC/ "" H HOOC""""'" "CPOH
9. How will you distinguish each of the following pairs of compounds by their infrared spectra :
o
11
(a) CH3CH 2CH2COOH and CH3CH 2COOCH3 (b) CH3-CH2-C-CH3 and CH3"CH2 COOCH3
CHO

~CHO ~ COOH

(')~OH Md ~ (d)
@r
0
OH
and

OH
o
(0)6
o

(g) 6
SPECTROSCOPY 59

10. Using the Hooke's law, calculate V for each of the following stretching vibrations. As force constants
use 5 x 105 , 10 x 105 , 15 x 105 dynes cm- l for single, double and triple bonds, respectively.
(a) O-H (b) O-D (c) C=O (d) C=C (e) C-O
11. Indicate how UV spectroscopy can be used to distinguish between the members of each of the
following pairs of compounds?

om '" om
(a) CH2=CH-CH2-CH=CH2 and CH3-CH=CH-CH=CH2

(b)

o 0
11 11
(c) CH3-CH=CH-CH2-C-CH3 and CH3-CH2-CH=CH-C-CH3
12. Using Woodward-Fieser rules, predict the Amax of each of the following chromophores:

C6 qCH' x: d=b d=o


(a) (b) (c) (d) (e)
13. The labels fell off of four flasks of ketones known to have the structures given below. Measurement
of the UV spectra of the contents of the four flasks gave Amax at 221, 233, 249 and 258 nm. Assign
the Amax values to the appropriate structures.

14. Compounds (A) to (D) have Amax values of 177, 217, 232 and 277 nm. Match the Amax with the
appropriate structure.
(a) CH2=CH-CH=CH-CH=CH-CH=CH2
(b) CH3-CH2-CH=CH2
(c) CH2=CH-CH=CH2

(d) Q=CH-CH=CH2

15. Using Woodward-Fieser rules, calculate the Amax of ethanolic solution of each of the following:

II III IV
60 UNDERGRADUATE ORGANIC CHEMISTRY

16. Hydrogenation of one mole of the triene (A) with one mole of H2 gives three isomeric dienes having
molecular formula CIOH I4 . Show how the expected Amax values could distinguish these isomers:

CD (A)

17. How can 1R and UV spectroscopy be used to determine when the following reaction is completed?
CH3
O I OH
11 (CHr-CH-%AI I
~H3-i=CH-C-CH3 --'------=~) CH34=CH-CH-CH3

CH3 CH3
18. An organic compound can have one of the following structures :

mC;OQ) o 0
The Arnax of the compound is 242 nm. Which is the most likely structure of the compound. Give
reason for your choice.
19. Using IR spectroscopy, how will you distinguish between the members of each of the following pairs
of compounds?
(a) RNH2 and RCONH2
F
~COOH
(b)lQj ~d ~
eo OH
(c) CH3CH2CHO and CH2=CH-CH20H
20. Identify the geometrical isomers of stilbene from their UV absorption Arnax 294 and 274 nm.
21. Explain why 1, 3-butadiene exhibits a higher value of Arnax for 1t -71t* transition than that of ethylene.
22. Give the equation for calculating stretching frequency a diatomic molecule.
23. Concentrated solutions of ethanol and 1, 2-glycol in CCl4 exhibit broad vO-H band near
3350 cm- I in their 1R spectra. On dilution with CCI 4, the spectrum of 1, 2-glycol does not change
but that of ethanol exhibits a sharp band at 3600 cm- I in addition to the broad band at 3350 cm-I.
Explain the observation.
[Hint: Intermolecular hydrogen bonding is concentration dependent whereas intramolecular
hydrogen bonding is not affected on dilution].
24. Giving suitable reason, arrange the following lac tones in order of their decreasing vc=o frequency:

c:((a) (c)
SPECTROSCOPY 61

25. Giving suitable reason, arrange the following ketones in decreasing order of their vc=o frequency:

26. Write notes on :


@-~-@
o

(a)
6 (b)
©O=o
(c)

(a) Fingerprint region (b) Fermi resonance (c) Stretching and bending vibrations
27. Calculate the fundamental vibrations of the following molecules:
(a) Methane (b) Ethanol (c) Acetylene (d) Benzene (e) Carbon dioxide
28. Giving reasons arrange the following compounds in order of increasing wavenumber of carbonyl
absorption in their IR spectra :
(a) Acetophenone, p-nitroacetophenone and p-aminoacetophenone
(b) Cyclobutanone, cyclopentanone and cyclohexanone
29. Deduce the structure of isomeric compounds (A) and (B) having molecular formula C3H60 and the
following IR spectral data:
(A) 1710 cm-l
(B) - 3300cm- 1 and 1640 cm- 1
30. Ethyl acetate shows vc-o absorption at 1735 cm- 1 whereas phenyl acetate at 1770 cm-I. Explain.
31. Arrange the following compounds in order of increasing absorption frequency of their carbonyl
groups. Give reason for your answer.
C6HSCHO, CH3CHO, CH3COCI and CH3COCH3
32. Explain how conjugation increases "max
of UV absorption.
33. The 1R spectrum of methyl salicylate (I) fives the following peaks at :
3460, 3010, 1710, 1595 and 1450 cm-
~OH

0 - C - OCH3
11
o
(I)
Attribute these peaks to the following groups :
(i) -O-H (ii) ')C=O (Hi) C-H benzene ring
34. Assign the following IR absorption bands to a particular carboxylic acid derivative in each case:
(i) 1715-1750 cm- 1 (ii) 1750-1815 cm- 1
(iii) 1630-1690 cm- l (iv) 1740-1790 and 1800-1850 (two bands)
35. Match the following IR absorption bands with the appropriate given compounds:
IR absorption bands :
(i) 1715 cm-l (ii) 1730 cm-l (Hi) 1740 cm- 1 (iv) 1680 cm- 1
Given compounds :
(a) CH3COOC2Hs (b) CH3CHO (c) CH3CONH2 (d) CH3COCH3

ANSWERS TO VERY SHORT ANSWER QUESTIONS


1. y-rays > X-rays> UV > visible> 1R > microwaves> radiowaves
2. 0' - 7 0'* > n - 7 0'* > 1t - 7 1t* > n - 7 1t*
62 UNDERGRADUATE ORGANIC CHEMISTRY

3. Electrons are excited from bonding molecular orbitals (0 or n) or non-bonding molecular (n) to
uncoupied anti bonding molecular orbital (0'* or n*).
4. Yes, Depending on the wavelength of light used, a molecule can undergo all the possible electronic
excitations. For example, formaldehyde (HzC=O) can undergo n ----? n*, n ----? n*, 0' ----? n*,
n ----? 0'*, 1t ----? 0'* and 0' ----? 0'*.
5. 166 nm: n----?O'*; 189 nm: 1t----?n*; 729 nm: n----?n*.
6. (a) 1t----71t*; 0'----71t*, 1t----70'*' 0'----70'* (b) 0'----70'*,
(c) n ----7 0'*, 0' ----7 0'* (d) n----7 0'*,0'----70'*
(e) n ----7 1t*, 1t ----7 1t*; 0' -~ 1t*, n ----7 0'*, 0' ----7 0'*
7. No. absorption of radiation is a random event. Relatively few molecules may be excited.
8. (C) < (B) < (A)
9. The energy required for ionisation is provided by only in the high frequency X-ray and y-ray regions
of the electromagnetic spectrum. However-, bonds with low bond dissociation energies, i.e., bonds
•••• ••••
....
between atoms which contain at least one lone pair of electrons such as -0-0-, : X-X :, ....
•••• ••••
-O-X,
••••
-N-X
I •• '
: may break.

10. Ethanol, cyclohexane and diethyl ether do not absorb above 200 om, hence can be use as solvents.
In contrast, benzene and acetone absorb above 200 nm, hence cannot be used as solvents.
11. The excited molecules give off energy and return to the ground state and the process is called
deactivation. Alternatively, the excited molecules may undergo a chemical change depending on their
nature. For example, alkenes may undergo eis-trans isomerisation.
12. Since n (non-bonding) electrons are not engaged in bonding, there are no corresponding antibonding
(n*) orbitals.
13. In order to be IR active, i.e., to absorb IR radiation, the vibrational mode of the molecule must be
accompained by a dipole moment change.
14. Absorption of UV and visible light involves electronic transitions while absorption of IR radiations
involves vibrational transition, i.e., the molecule to excited from lower vibrational level to higher
vibrational level.
15. Ethanol does not absorb in the UV region but absorbs strongly in the IR region (3200-3600 cm-I).
16. Wavelength range: 2·5-15·0 !lm; frequency range: 400~67 cm-I; the corresponding energy range:
2-10 KcaUmole.
17. Molecular vibrations of homoatomic molecules 0z, Hz, Clz and Nz are not accompained by any dipole
moment change, hence are IR inactive, i.e., they do not absorb in the IR region whereas the molecular
vibrations of HCI, HzO and CHz=CHz are accompained by a dipole moment change, hence they
are IR active, i.e., they absorb in the IR region.
18. As the hybridisation changes from sp3 ----? spz ----? sp, force constant of the bond increases, hence
the stretching frequency of the C-H bond increases.
~p3 si sp
C-H =C-H =:C-H
2840-3000 cm-I 3000-3100 cm-I 3300-3310 cm-I

19. C-H > C-C > C-O > C-CI > C-Br > C-I
20. (Ill)
SPECTROSCOPY 63

21. CH3COCI
22. CH30H
23. O-H > O-D > C-C

A
1. Emax = Cl

A
C=--
Emax 1
A = 1.18

C= 1.18
1.26 X 104 X 1.0

= 9.37 X 10-5 M
A
2. Emax = Cl
where A=0.96
C =7.6 X 10-5 mole/litre
1= 1.00 cm
0.96
Therefore,
Cmax 7.6 X 10-5 xl
= 1.26 X 104
= 1.26 x 104 litre/mol cm- 1
3. Absorption in fact is- the function of the number of excited molecules. Thus greater the number of
excited molecules, the larger is A. The higher the concentration of the solution, the more molecules
are exposed to and excited by the radiation. Similarly, the longer the path, the greater is the chance
for the radiation to impact and excite molecules.
4. (X) on partial hydrogenation will give three isomers whose structures are as follows :

09+ (A)
+

(C)
.
64. UNDERGRADUATE ORGANIC CHEMISTRY

Expected Amax of these three isomers can be calculated from Woodward-Feiser rules as follows:

(A) (C) (B)


Base value 253 214 < 200 (non-conjugated)
Ring residues (five) = 25 five = 25
Exocyclic bonds (three) = 15 two = 10
Amax =293 nm 249 nm < 200 nm
Thus the compound having Amax « 200 nm) will be (B), the compound having Amax 240 nm will be
(C) and the compound having Amax 293 nm will be (A). Therefore, these three isomers can be
distingenished by their DV spectra.
5. Dehydration of (A) takes place as shown on page 70:

1
e
1,2H
I ...
shift

I '\ +
I- H
$

+
(1) (2)
(non-conjugated)

1-~

(3)
SPECTROSCOPY 65

Expected absorption maxima of these three isomers, namely (1), (2) and (3) can be calculated by
using Wood ward-Feiser rule as follows:
Compound 1 2 3
Base value 253 214 253
Ring residues 15 (5 X 3) 20 (5 X 4) 20 (5 X 4)
Exocyclic bonds 5 (one)
Amax 268 nm 239 nm 273 nm
Difference in values of 5 nm or more makes the isomers distinguishable experimentally. Thus the
three conjugated dienes can be distinguished by Uv.
6. Usual electronic transitions that occur in ketones are 1t -71t* and n -71t*. n -7 1t* transition requires
less energy than 1t - 1t* transition. We know that smaller energy is associated with longer wavelength
of absorption. Hence Amax = 279 nm, E max = 15 is due to n -7 1t* transition and Amax = I7} nm,
E max = 900 is for 1t -7 1t* transition.
E max determines the intensity of absorption. Higher E max means more intense is the absorption.
Therefore, the 1t -7 1t* transition (E max = 9JO) is more intense than the n -7 1t* transition
(Emax = 15).
1t -7 1t* transitions give rise to K-bands where there is conjugation in the system. Acetone does not
possess conjugated structure. So the peaks that arise from the 1t -7 1t* transition should not be
designated as K-band. n -71t* transition produces R-band. Hence Amax = 229 nm is for the R-band.
o
7.
~-~--O--CH
~ 2
-CH
3

Ethyl benzoate Methyl phenylacetate


In ethyl benzoate C=O group is in conjugation to benzene ring but in methyl phenyl acetate this
group is not in conjugation to benzene ring. As a consequence the C=O group of ethyl benzoate
acquires a single bond character and thus the C=O stretching frequency will occur at a wavenumber
lower than that in methyl phenylacetate though they are isomeric compounds.
8. Ethane-I, 2-diol has intramolecular hydrogen bond but ethanol forms intermolecular hydrogen bonds.
When a solution of ethane-I, 2-diol is diluted with carbon terachlotide, intramolecular hydrogen
bonds do not break and so the O-H stretching does not change with delution. In the case of ethanol,
the intermolecular hydrogen bonds of the associated complex break with dilution. So in the dilute
solution of ethanol in carbon tetrachloride, the O-H stretching occurs for the free -OH group. Thus
O-H stretching frequency changes from hydrogen bonded to free -O-H on dilution.
9. We know that the longer the conjugated system, the higher is the value of Amax. The compound I has
a longer conjugated system than the 11 because in the 11 the protonation of nitrogen has removed one
benzene ring from the conjugation with the ring containing the NH2 group. Thus the compound I
has a higher Amax than compound 11.
10. (a) < (d) < (b) < (c)
11. (a) 1, 4-Pentadiene is an unconjugated diene whereas 1, 3-pentadiene is a conjugated diene, thus the
latter will have a higher Amax than the former.
(b) Anthracene has a longer conjugated system than benzene, thus anthracene will have a higher
Amax than benzene.
(c) We know that cisoid dienes have a higher Amax than transioid dienes. Acyclic dienes exist in more
stable transoid form. Thus 1, 3-cyclohexadiene which can exist only in cisoid form will have a higher
Amax than 1, 3-hexadiene.
66 UNDERGRADUATE ORGANIC CHEMISTRY

12. (i) The band at ~ax 210 nm (Emax 11,500) is a band due toa higher energy allowed transition, and
in acrolein it must be due to 1t ~ 1t* transition.
(ii) The band at Amax 315 nm is a band due to a lower energy transition. The E max 14 indicates that
it is a forbidden transition.
Thus this band is due to n ~ 1t* transition.
13. First of all calculate Amax for each given compound.
The structure (a) is a homoannular diene with two ring residues and one alkyl substituent, hence its
calculated Amax = 253 + 3 X 5 = 268 nm.
The structure (b) represents a heteroannular diene with four ring residues, hence its calculated
Amax = 214 +4 x 5 =234 nm.
Since the given Ama:'C of the compounds is 236 nm, its most likely structure is (b) because the
calculated Amax (234 nm) for this structure is very close to the given value (236 nm).
14. The compound (a) is an unconjugated diene, hence it will have Amax < 200 nm. The compound (b) is
a heteroannular conjugated diene with two ring residues, one alkyl substituent and one exocyclic
double bond, hence it is expected to have Amax (214 + 2 x 5 + 5 + 5) = 234 nm, i.e., higher than that
of compound (a).
15. The calculated Amax for :
(a) (b)
Base value ,253 nm 214 nm
Ring residues (2 x5) =10 nm (2 x5) = 10 nm
Alkyl substituent (2x5) = 10 nm (2 x5) = 10 nm
Exocyclic double bond one 5 nm
Total = 273 nm 239 nm
Thus the structure (b) is the diene having the experimental Amax 243 om because this value is in
agreement with the calculated Amax for (b). Similarly, the structure (a) is the diene having the
experimental Amax 265 run.
16. The following is decreasing order of frequency of carbonyl absorption
(c) > (a) > (b)
Cyclohexane carboxaldehyde (a) is an unconjugated aldehyde and will absorb around 1730 cm-I.
Due to conjugation of C=O group with the double bonds of the benzene ring, the vc=o absorption
of benzaldehyde (a) will be shifted to lower frequency (:::: 1700 cm-I). In salicylaldehyde the lowering
is due to conjugation as well as intramolecular hydrogen bonding (chelation), thus the vc=o
absorption frequency is further lowered (:::: 1665 cm-I).
17. In salicylaldehyde due to intramolecular hydrogen bonding, vO-H and vc=o bands are shifted to
lower wavenumbers. Since it is intramolecular. change in concentration does not cause any shift in
vO-H and vc=o bands. In the case of m-hydroxybenzallehyde also vO-H and vc=o bands occur
at a lower wavenumber due to intermolecular hydrogen bonding. In this case vO-H and vc=o bands
shift to higher wavenumbers on dilution with a nonpolar solvent.

~
~<yH
o-hydroxybenza\dehydc
6:0H
m-hydroxybenzaldehyde
SPECTROSCOPY

H-C-COOH H-C-COOH
18. 11 11
H-C-COOH HOOC-C-H
maleic acid fumaric acid
VC=O 1720 cm-I (s) vc=o 1680 cm-I (s)

In maleic acid the bulky COOH groups are on the same side of double bond. Henc.e due to repulsive
interaction the C=O group is forced out of the plane of C=C bond. Thus the conjugation is
diminished resulting in the appearance of vc=o band at a higher frequency as compared to that in
fumaric acid where the C=O group is in conjugation with the C=C bond.
19. The IR band at 1710 cm- l is indicative of a C =0 (ketonic) group. Thus the compound (A) is
o
11
CH3-C-CH3·
The band at - 3300 cm-l is indicative of an -OH group, arid a band at 1640cm-1 shows the
presence of a C =C. Thus the compound (B) is CH2=CH-CH20H.
20. Due to strong - I effect of CCl 3 group, the vO-H frequency of Cl3CCOOH will be lowest. Due to C

+1 effect of ethyl group the VO-H frequency of ethanol will be highest. CICH2 group in chloroacetic
acid has -I effect and CH3 group in acetic acid has +1 effect, hence vO-H of chloroacetic acid will
be lower than that of acetic acid. Thus the increasing order ofvO-H frequency is:
trichloroacetic acid < chloroacetic acid < acetic acid < ethanol
21. (i) Inactive (ii) Active (iii) Inactive (iv) Active (v) Inactive (vi) Inactive
22. Due to +M effect, Cl decreases the force constant of C=O bond from the para position but not from
the Ifleta position.
23. From the given Amax values of various alkenes the following conclusions can be drawn:
(i) C;onjugated alkenes have higher Amax than the unconjugatedalkenes, thus ethylene has lower
Amax 170 om than the other given alkenes which are conjugated.
(ii) Longer the conjugated system, the higher is the value of Amax. For example. 1. 3. 5~hexatriene
has Amax 274 nm and the given conjugated dienes have Amax 217-256 nm.
(iii) The presence of an alkyl substituent on a conjugated system increases the Amax e.g .• 2.
3-dimethyl-1, 3-butadiene having two methyl substituents has a higher Amax (226 nm) than 1.
3-butadiene Amax 217 nm.
(iv) cis conjugated dienes (e.g., 1. 3-cyclohexadiene (Amax 256 nm) have a higher Amaxthan the
trans dienes (e.g .• 1, 3-butadiene, Amax 217 nm and 2, 3-dimethyl-1, 3-butadiene. Amax 226 nm). It
should be noted that acyclic conjugated dienes exist in transoid form because it is less strained (more
stable) than the cisoid form.
24. In o-hydroxybenzoic acid (salicylic acid), due to intramolecular hydrogen bonding VO-H and
vc=o bands are shifted to lower wavenumbers. Since it is intramolecular. change in concentration
does not cause any shift in vO-H and vc=o absorption bands. On the other hand. in the case of
p-hydroxybenzoic acid VO-H and vc=o bands also occur at lower wavenumber due to
OH

~H
I
r(YC~
~O/H
o-hydroxybenzoic acid
OH
68 UNDERGRADUATE ORGANIC CHEMISTRY

intermolecular hydrogen bondng, but in this case VO-H and vc=o bands shift to higher wavenumbers
on dilution of the sample with a nonpolar solvent.
(ii) Acetone will show a strong vc=o band at - 1715 cm- I whereas this band appears at - 1730 nm
in propionaldehyde. In addition, propionaldehyde will show a doublet in the range 2700-2900
cm-I due to aldehydic C-H stretching. This doublet generally appears in the case of aldehydes due
to Fermi resonance.
25. After completion of the reaction Amax of UV absorption will shift to a considerably lower value
because the length of conjugation is decreased in the product as compared to the starting ketone. In
the IR spectrum, the band due to vc=o will disappear and a new band due to VO-H will appear (in
the region 3200-3600 cm- I ) after the completion of the reaction.
26. N-H stretching absorption of a primary amine would appear as a doublet, the two components
corresponding to asymmetric and symmetric, modes. The separation is usually 100 cm- I . N-H
stretching absorption of a secondary amine would generally have a single absorption maximum.
27. I, 1815, 1750; II, 1775, 1720; III, 1865, 1780 cm- I .
28. Due to decrease in strain, the vc=o frequency decreases as the size of the ring increases, hence the
compound I would give the lowest value of Vc 0 frequency.
29. (d) > (b) > (a) > (c)
30. I, 1745; II, 1720 and III, 1760 cm- I . The highest vc=o frequency of III is due to conjugation of the
carbon-carbon double bond with the oxygen p-orbital which gives partial positive charge on the
oxygen resulting in an increase in the double bond character of the carbonyl group and consequently
an increase in vc=o frequency as compared to lactones I and II. The I is a saturated lactone whereas
in II the C=O group is in conjugation with the carbon-carbon double bond which reduces the double
bond character of C=O group in II and consequently its vc=o frequency is lowered as compared
to that of the I.
31. According to Hooke's law (Section 1.26), the stretcing frequency of a bond increases as the reduced
mass of the bonded atoms decreases. Since hydrogen has lesser atomic mass than deuterium, the
vO-H frequency (near 3570 cm- I ) is higher than the vO-D frequency (near 2630 cm- I ).
32. (a) CH3CH2C==CH will show strong absorption bands at - 3300, 2100 and 625 cm- I due to
= C-H stretching, C=C stretching and =C-H bending vibrations, respectively. All these bands
will be absent in the IR spectrum of CH3C=CCH3 because the symmetrical substitution makes the
C=C stretching IR inactive.
(b) CH3CH20H will show absorption bands in the region 3200-3600 cm-1 due to vO-H of
intermolecularly hydrogen bonded O-H group and at - 1050 cm- 1 due to vc-o. These bands will
be absent in the IR spectrum of CH30CH3. It will show an absorption band around 1100 cm- I due
to C-O-C stretching.
(c) CH3CH2NHCH3 will show a medium band in the region 3310-3550 cm- I due to N-H stretching.
This band will be absent in the IR spectum of (CH3hN.
33. (i) -O-H, 3460 cm-I (ii) ;C=O, 171 0 cm- I
(iii) C-H benzene ring, 3010 cm- I
34. (i) Esters (ii) Acid halides (iii) Amides (iv) Anhydrides
35. (i) (d); (ii) (b); (iii) (a); (iv) (c)

DDD
2.0 Introduction
lcohols are compounds of the general formula ROH where !?- is any alkyl group or substituted
A alkyl group. The hydroxyl group (-OH) is the functional group of alcohols.
The hydroxyl group in alcohol is usually attached to a carbon atom whose other valencies are
satisfied by hydrogen or other carbon atoms and not by any other atom or group.
2.1 Classification of alcohols

A lcohols containing one hydroxyl group are called monohydric alcohols. Alcohols with two, three
or more hydroxyl groups are known as dihydric, trihydric and poly hydric alcohols, respectively.
For example,
R--CH-OH
R-TH-OH I
R-OH R'-C-OH
Monohydric alcohol R'-CH-OH I
Dihydric alcohol R"-CH-OH
Trihydric alcohol
We know that a carbon atom is designated as primary (l0), secondary (2°) or tertiary (3°) when
one, two or three substitutents are attached to it, respectively. Thus a monohydric alcohol is classified
according to the kind of carbon that bears the -OH group.
H H R"
I I
R-C-OH
I
R-C-OH R-C-OH
I I I
R'
H R'
Primary (1°) alcohol Secondary (2°) alcohol Tertiary (3°) alcohol

2.2 Nomenclature of alcohols

T here2.2.1are Common
following three systems of nomenclature of alcohols:
naming system: This system is useful for naming simple alcohols. In this
system alcohols (R-OH) are named as alkyl alcohols. The alkyl group attached to the -OH group
is named and 'alcohol' is added as a separate word. For example:
CH3-0H CH3CH2-0H CH3CH2CH2-0H
Methyl alcohol Ethyl alcohol Il-propyl alcohol
70 UNDER GRADUATE ORGANIC CHEMISTRY

c.:H3~fH-CH 3 C6HsCH2-OH
Benzyl alcohol
.. eH
. !sopr6pyl akoi).ol Sec-butyl alcohol t-butyl alcohol

"2.2:2 Carbinol naming system: In this system alcohols are considered as derivatives of
metnyLal~oi:which is called carbinol. The alkyl groups attached to the carbon bearing the ~OH
group are named in alphabetical order before the suffix carbinol and the whole name is written as one
word. For example:

Carbmol Dlmethylcru binol . Ethylmethylcarbinol Methylcarbmol Tnphenylcarbtnol


2.2.3 IUPAC naming system: In this system the suffix 'e' in the name of the hydrocarbon is
replaced by the suffix 'o/'. Thus, in general. alcohols are named as alkanols, akenols, alkynols, etc.
Some of the important IUPAC rules followed for naming alcohols are as foHows:
(a) The longest continuous carbon chain bearing -OH group is selected and the alcohol is
considered to be the derivative of hydrocarbon corresponding to the selected chain.
(b) the carbon atoms of the selected cham are numbered from one end to the other in such a
way that the carbon atom bearing the -OH group is assigned the lowest number.
(c) The name of the alcohol is written as one word by writing the names of substttuents in
alphabetical order as prefix.
(d) The positions of substituents or multiple bonds are indicated by numbers.
The examples given below illustrate these rules:
CH3-0H CH3CH2-0H CH3-CH-CH3 CH2=CH-CH20H
Methanol Ethanol I 2-Propen-l-ol
OH
2-Propanol

CICH2CH 2CH 20H C6HsCli2CH20H


3-Chloro-l-propanol 2-Phenylethanol

2.3 Methods of preparation of monohydric alcohols


2.3.1 Hydration of alkenes
(i) Addition of water to alkenes: Most of the alkenes are absorbed 10 conc. H2S04 to give
alkyl hydrogen sulphates which on hydrolysis from alcohols.
OS03H
I .
R-CH=CH 2 + H2S04 ~ R-CH-CH3
IHOH
OH
I
R-CH-CH:; .
Secondary alcohol
It is not possible to prepare primary alcohol by this method (except ethyl alcohol).
AlCOHOlS 71

(ii) Hydroboration~Oxidation: Alkenes react with diborane to form trialkyl boranes. Trialkyl
boranes on oxidation with alkaline H202 give primary alcohols. This method is very useful for the
preparation of primary alcohols.
6 RCH=CH2 + B2H6 ~ 2(R-CH2-CH2 hB
e
IHP2I OH
6 R-CH2-CH20H
2.3.2 Nucleophilic substitution
(i) From alkyl halides: Hydrolysis of alkyl halides with aqueous NaOH or KOH yields
alcohols.
H20
R-X + NaOH - - - 4 ) R-OH + NaX
t1

H20
C2H5-Br + NaOH ) C2H5-0H + NaBr
t1

This is not a very good method for the formation of alcohol becauses the tertiary and secondary
alkyl halides undergo competitive elimination reaction resulting in the formation of alkenes as side
products.
2.3.3 Reduction of aldehydes and ketones
(I) Catalytic hydrogenation: Addition of hydrogen to aldehydes and ketones, catalytically and
under pressure results in the formation of primary and secondary alcohols respectively.
o
11 Ni
R-C-H + H2 - - - - - 4 ) R-CH20H
Pressure

°
11
R-C-R' + H2
Ni
) R-CH-OH
Pressure I
R'
Oi) Reduction with LiAlH4 and NaBH4: A more convenient method for the preparation of
alcohols is the reduction of carbonyl compounds with complex metal hydrides, like LiAIH4 or
NaB~, LiAIH4' is a more powerful reductant than NaBH4·
LiAlH4 is widely used for the reduction of aldehydes, ketones, acids, acid chlorides and esters
into alcohols. The solvent used for the reaction is generally dry ether, THF or dichloromethane.
LiAIH4
R-CHO ) R-CH20H
LiAIH4
R-COOH - - - - - 4 ) R-CH20H
LiAIH.t
R-COOC2H5 - - - - - 4 ) R-CH20H + C2HSOH
o
11 LiAI14
R-C-R' - - - - - 4 ) R-CH-OH
IR'
72 UNDER GRADUATE ORGANIC CHEMISTRY

NaBH4 in a milder reducing agent and does not reduce acids and acid derivatives. However, it
reduces aldehydes and ketones into corresponding alcohols.
o
" NaBH4
R-C-H---4) R-CH20H
o OH
" NaBH4 1
R-C-R' ) R-CH-R'
The advantages of these metal hydrides are that they are soluble in organic solvents like ether,
THF and dichloromethane and they do not generally reduce carbon-carbon double bond.
(Hi) Grignard reaction: Grignard reagents react with aldehydes and ketones to form an
addition product which, on hydrolysis with dilute acid, gives corresponding alcohol.
E±l
o 08MgX OH
GY
11 1 HJO 1
R-C-H + R/MgX -~) R-C-H ) R-CH
1 1
R' R'
Primary alcohols are obtained by treating Grignard reagents with formaldehyde.
o
11 ( .) RM X
H-C-H 1 g) R-CH20H
GY
(ii) Hp
Secondary alcohols are obtained by treating Grignard reagents with aldehydes other than
formaldehyde.
o OH
11 (i) R'MgX 1 I
R-C-H -----7) R--CH-R
(ii) H30GY

Teliiary alcohols are obtained by treating Grignard reagents with ketones.


o OH
R-1_RII_(i)_R_/M_g_X--7) R-~-R"
(ii) H30 $ 1
R'
2.4 Physical Properties
2.4.1 Boiling point: The melting and boiling point of alcohols generally increase with increasing
molecular weight within a homologous series (Table 2.1) as they do in other classes of organic
compounds. However, a1cohols exhibit unusually high boiling points. The following table shows the
boiling points of three pairs of compounds, each pair having approximately the same molecular weight:
'm:"#,' BOiling point of compounds
Compound H2 O CH4 CH30H CH3CH3 CH3CH20H CH3CH2CH3
M.Wt. 18 16 32 30 46 44
bpoC 100 -164 65 -89 78.5 -42
The large difference in boiling points of the three pairs can be explained as follows. In liquid
ALCOHOLS 73

phase, the molecules of a compound are in a continuous


motion, but attractive forces between the molecules
restrict their movement within a certain volume (Fig.
Heat
--"

melting
'- ,--~
° °
<,-,0 'I'
01,";:1:: Olt, :,1 ,,0
2.1).
Liq LJ Id phase
In the gas phas~, the molecules are in a constant, Solid phase
I heat '
random motion with no intermolecular attractive forces. t boiling
Each molecule is independent of others. To convert
liquid into a gas, enough energy must be provided to
overcome the intermolecular forces of attraction. The Gas phase
stronger the attraction between molecules, the greater
the energy required to break them, and higher the boiling Fig. 2.1
point.
Methane, ethane and propane are composed of nonpolar carbon-carbon and carbon-hydrogen
bonds (hydrophobic). As such the attractive forces between molecules are very weak van der Waals
forces. However, in water, methanol and ethanoL there are highly polar oxygen hydrogen bonds
8- 0+
(-O-H). Because of this polarisation, electrostatic force exists between these molecules (force
between the hydrogen of one moJecule and oxygen of another) that are not possible in nonpolar
compounds. Further, due to minute size of hydrogen, close intermolecular association is possible
providing maximum attraction (Fig. 2.2). This phenomenon is called hydrogen bonding and occurs in
molecules where hydrogen is bonded to a strong electronegative element such as nitrogen, oxygen or
fluorine.
H

H-C-H
I CH3 CH 3
I I I
/OIIlIlIlH-Q
H
O"IIIH §

H IIIIIIIH/ "CH -
3
I
H-C-H
I
H
Fig. 2.2

Thus, methane is a nonpolar compound with only weak intermolecular attractions. Consequently
it has a very low boiling point. Water, methanol and ethanol have strong attraction between molecules
owing to their capacity of hydrogen bonding and thus have a relatively high boiling points.
2.4.2 Solubility: Low molecular weight alcohols are water soluble, owing to their ability to
form hydrogen bond with water (Fig. 2.3). As molecular weight increases, however, water solubility
decreases. The rule "like dissolve like" applies here. An alcohol has a water like portion (-OH,
hydrophilic) and a hydrocarbon like portion (hydrophobic, the alkyl group). As the molecular weight
of alcohol increass, the hydrophobic character of alcohol increases. The alcohol becomes more like
an alkane, which is less soluble in water.

/CH 3
H", /0 CH 3
/OIIlIlIlH ~ I
H H-O 1111111 H-o"111
I
H

Fig. 2.3
74 UNDER GRADUATE ORGANIC CHEMISTRY

TABLE 2.2

Compound Mol. Wt. m.p. CC) bp Cc) water solubility


CH 30H 32 -94 65 S
CH 3CH 2OH 46 -117 78.5 S
CH 3CH2CH 2OH 60 -127 97 S
CH 3-CH2-CH 2-CH 2OH 74 -90 118 7.5 g/IOO m!
2.5 Chemical Reactions

The(-OH).
alcohol molecules contain two groups an alkyl group and (ii) the functional hydroxyl group
(i)
Thus the properties of alcohols are the properties of an alkyl group and functional group
-OH. The alkyl group exhibits the properties of alkane. However, the C-O and O-H bonds of
alcohols are polar since oxygen is highly electronegative. Moreover, oxygen has two un shared lone
pairs of electrons.
3
OSp
SP-S,,/ 0 ~S
3 3 3

c OSp3 H
Thus alcohols are reactive compounds and they are attacked by polar reagents. The reaction of
the hydroxyl group consists of (i) cleavage of C-O bond, resulting in either a nucleophilic substitution
or elimination and (ii) cleavage of O-H bond resulting usually in substitution.
In general, the chemical behaviour of the alcohols also depends on their type. In the reactions
involving cleavage of C-O bond, the order of reactivity is:
Tertiary alcohol> Secondary alcohol> Primary alcohol
As an alkyl group has +1 effect, it will increase the electron density over the carbon atom of the
C-O bond. The greater the electron density on carbon atom, greater will be the electron repulsion
towards oxygen atom (oxygen is electronegative) and consequently weaker will be the bond. Because
primary has one, se~ondary two and tertiary alcohol has three alkyl groups, their order of reactivity
is Tertiary alcohol> Secondary alcohol> Primary alcohol
Whereas in the reactions involving cleavage of O-H bond the order of reactivity, including the
acidity of alcohols, is:
Primary> Secondary> Tertiary alcohol
The fission of O-H bond is suppressed with increase in electron density on oxygen, as hydrogen
tends to separate as a proton. This is clearly the minimum in primary alcohols and maximum in tertiary
alcohols.
2.6 O-H Bond Cleavage
2.6.1 Reaction with Alkali Metals: . Formation of Alkoxides
Because of the presence of lone pair of electrons on the oxygen of the -OH group, alcohols
behave as bases. However, they also behave as weak acids. The acidity of alcohols can be explained
on the basis of the fact that hydrogen atom is attached to electronegative oxygen atom, which attracts
the pair of electrons of the O-H bond, hence there is tendency for the loss of hydrogen as proton.
In other words, the acidic nature of alcohols is due to the ability of oxygen to accommodate the
negative charge after the loss of proton. Thus alcohols react with strongly electropositive metals like,
Na, K, Li with evolution of hydrogen to form alkoxides.
ALCOHOLS 75

2ROH + 2Na-~) RONa + H2

Alkoxides are also obtained from alcohols and metal hydride. With the relatively unreactive
tertiary alcohols, KH is particularly effective.

® ) But OK+"21 H2
ButOH + KH--~) ButOK + H2
These alkoxides are important poth as reactants (nucleophiles) and as reagents (as base).
Among other alkoxides (PrlOhAl and (ButOhAI are the classical reagents for the
Meerwein-Ponndorf-Verley reduction and the Oppenauer oxidation.

CH3 CH3
I I
3 CH3-C-OH + AI-~) CH3-C-O Al
I I
H H
Aluminium iso-prop oxide

Al

3
Aluminium tert-butoxide

2.6.2 Reaction with carboxylic acids: Esterification


Alcohols react with acids in the presence of catalyst (conc. H2S04) to form esters. This reaction
is known as esterification reaction.

o
H2 S0 4 11
R-OH + R'COOH r= R-O-C-R' + H20
o
H 2S04 11
C2HSOH + CH3COOH r= C2Hs-O-C-CH3 + H20
Ethyl acetate

The esterification is a reversible process and is carried out in the presence of dehydra.ting reagent.

o
11
R-C-OH "
q'
~
conjugate acid <±l
OH OH QH OH 0
~. 1 <±l .. -H20 11 ~ -H® 11
R-i +H-g-R'~ R-T-?-R'~ R-X-Q-R' ~ R-C-O-R' ~ R-C-o-R'
OH OHH ~H2 .
76 UNDER GRADUATE ORGANIC CHEMISTRY

The reaction is acid catalysed, the function of the strong acid is to convert carboxylic acid into
its conjugate acid. the mechanism of the reaction IS as follows:
Isotopic tracer technique has established that esterification involves the cleavage of O-H bond
of the alcohol. The reaction is carried out with alcohol having 0 18 and the resultIng ester contains
this radioactive isotope of oxygen. This confirms that ester formation is taking place due to the
breaking of O-H bond. If the C-O bond of alcohol would have cleaved during esterification, 0 18
should have not been pr~sent in ester, it would have gone to the resulting water.
o o
11 18
R-C-OH
" + H-O-R'
18 R-C-O-R' + H 20
2.6.3 Reaction with acid chloride and acid anhydride: Acetylation
With acid chloride or acid anhydride alcohols form esters:
o
11
R-OH + R'COCI---4) R-O--C-R'
o
11
CH3COCI + C2HSOH ---4) CH3-C-0--C2Hs
o
R'-CO" 11
R-OH + /0---4) R-O-C-R' + R'COOH
R'-CO

When alcohols are treated with acetyl chloride or acetic anhydride, the hydrogen of the -OH
group is replaced by an acetyl group (-COCH3) and the reaction is known as acetylatIOn reaction.
This reaction is catalysed by pyridine. The mechanism of the acetylation reactIOn is as follows:

o
11 e
- - - - + . R-O-C-CH) + CH) COO

2.6.4 Reaction with para-toluenesulphonyl chloride: When an alcohol reacts with


ALCOHOLS 77

para-toluenesulphonyl chloride, the product is an alkyl para-toluenesulphonate ester, called a


"tosylate" ester. The tosyl group is often abbreviated "Ts" and the tosylate ester group is abbreviated
"OTs". In the formation of a tosylate ester, pyridine is used as solvent because it reacts with the HCl
that is produced, preventing acid from accumulating and promoting side reactions .

.,
R-O: + CI-S
?~V CH
I~II

H .'!\ 1 TsCl
3

~j?J
R-~-Ti-@-CH3
H: 1
R-O-~ IQ\--CH3 +HCI
II~
o or
R-OH + TsCl pyridine ~ R-OTs

2.6.5 Reaction with dialkyl sulphate: Alkylation


With dialkyl sulphates alcohol forms ether.
,
R--OH + R2S04 -~) R-O-R'
C2HSOH + (CH3hS04 -~) C2H SOCH3

2.7 C-O bond cleavage


Ca) In the reactions involving cleavage of C-O bond the order of reactivity is as follows:
Tertiary alcohol> Secondary alcohol> Primary alcohol
(b) Cleavage of C-O resulting in either nucleophilic substitution or elimination reaction.
2.7.1 Reaction with HX: Alcohols react with HX to form the corresponding alkyl halides.
The order of reactivity of HX is HI> HBr > HC!. Hence HCl reacts only in the presence of a catalyst
(anhydrous AlCl3 or ZnCI2). No catalyst is required in the case of HI and HBr.
R-OH+HI· ) R-I + H 20

ZnCI 2
R-OH + HCl--) R-Cl + H20
Reaction with HCI in the presence of anhydrous ZnCl2-Lucas reaction
Primary and secondary alcohols are less reactive and require the help of catalyst before they can
undergo reaction with less reactive HCl in a reasonable period of time.
78 UNDER GRADUATE ORGANIC CHEMISTRY

CH3 CH3
I 25'C I
CH3-C-OH + HCI--4) CH3-C-CI + H20
I I
CH3 CH3

H H
I ZnCl I 2
CH3-C-OH + HCI--4) CH3-C-CI + H20
I I
CH3 CH3

Anhydrous zinc chloride is a powerful Lewis acid with empty orbitals that can accept electrons
from oxygen. The formation of complex, Zinc chloride with the oxygen of alcohol, weakens the
C-O bond and thus enhances the leaving ability of the oxygen group. The mechanism of the reaction
is SNI for tertiary alcohols and SN2 for primary alcohols. Secondary alcohols have mixed mechanism
(SNl and SN2) .

.( \ (f) e
(i) CH:rCH2-Q-H + ZnCl2 • C2HS - 0 - ZnCl2
I
H
complex
e (f) e
Cl \ SN2 OH e
CH:rCHiTJ.)-ZnCI2 • CH~H2CI + Zn <Cl + Cl
I
H
CH3 CH3
I .. I (f) e
(ii) CH-C-O-H + ZnCI • CH -C - 0 -ZnCI
3 I" 2 3 I I 2
CH3 CH3H
1
lSN

CH3 CH3
I C19
CH-C(f)
I
CH-C-CI •
3 I 3 I
CH3 CH3

Neopentyl alcohol though a primary alcohol forms tertiary pentyl chloride. The formation of this
product may be rationalised through a carbocation rearrangement. The reason for a primary alcohol
reacting through a carbocation mechanism (SNI) is quite easy to understand, as the presence of a
bulky t-butyl group blocks the back side attack by the nuc1eophiIe halide.
ALCOHOlS 79

CH3 CH3 CH3


I H$ ~ I I ~
CH3-C-CH20H-~) CH3-C-CH20H2-~) CH3-C-CH2
I· I I
CH3 CH3 CH3·
Primary carbo1atlOn (less stable)
1.2 shift rearrangement

Cl
I CI 6 ~
CH3-C-CH2-CH3 ~(--CH3-C-CH2-CH3
I I
CH3 CH3
Tertiary pentyl chloride (Tertiary carbocauon)
2.7.2 Reaction with PCls, PBr3 and SOCI2: These reagents are halogenating reagents which
convert alcohols into the corresponding alkyl halides.
Phosphorus pentachloride is the mixed anhydride of phosphoric acid and HCI, PBr3 is the mixed
anhydride of phosphorus acid and HBr, and thionyl chloride is the mixed anhydride of sulphurous
acid and RCI.
PCls + 4H20 -~) SHCI + H3P03
PBr3 + 3H20 ) 3HBr + H3P03
SOCl2 +H20 ) 2HCI + S02
These compounds react readily with alcohols to form products that are esters of inorganic adds.
Since the inorganic acids are strong acids, their anions are· good leaving groups for subsequent SN 1
and SN2 reactions.
The mechanism for the reaction involves an initial attack by the alcohol upon the phosphorus
tribromide (or phosphorus pentachloride).
Br
.r;--.... I ~ ......-Br e
R-?: +":r-\jr .. R-?-P'BT + Br-
H Br H Inorganic ester of alcohol

This is followed by either SNl or SN2 displacement of a phosphorus·containing leaving group


by the bromide ion. Primary a1cohols react by the SN2 process, while tertiary alcohols react by SN 1
process.
80 UNDER GRADUATE ORGANIC CHEMISTRY

2.7.3 Reaction with SOCI2: Reaction between alcohol and thionyl chloride is rapid and
relatively free of side reactions. Also the by-products of the reaction are gases.
Ether
R-OH + SOCI 2 ---t)R-CI + S02 + HCI
~
The first step is the formation of an inorganic ester.
o 0
.~"
HIIIIII HIIIIII et> 11
e
CH3CH2 7 - QH +. . . . . S - - - . CH3CH27-tf-S-CI + Cl
CH3 Cl tCI CH3 H

o
H II1111 11
CH3CH27-0-S-CI
CH3 ChJorosulphite
This chlorosulphite can be isolated from the reaction mixture if the temperature is kept low.
When the reaction is carried out in tertiary amine solvent an amine solvent reacts with HCI formed
in this reaction to yield an amine salt.

The chloride from this salt attacks the chlorosulphite in a typical SN2 reaction, which results in
an alkyl chloride with an inverted configuration.
o
~/II SN 3 ""H e
CH 3CH2 ~C-O-ST P -..:.:--+. Cl- C '-'- CH 2CH 3 + S02 + Cl-
"
Cl +
CH~ 'vi amine 'CH
3
Inverted product
The reaction is rather interesting when carried out in nonpolar and inert solvent. In this case the
reaction occurs with retention of configuration. When chiral alcohol is treated with thionyl chloride,
formation of chlorosulphite takes place. This chJorosulphite has the same relative configuration as has
the alcohol. When the chlorosulphite is heated, it cleaves to form oppositely charged ions. These ions
cannot dissociate completely in an ether solution, but remain very close to each other as an ion pair.

Ion pair
These pairs are surrounded by common group of solvent molecules or solvent shell. This ion
pair then collapses to an alkyl chloride with the same 'configuration as the chlorosulphite because the
CIS02" anion can react with only one face of the cation.
H 111111$ O~ H",
CH3CH2~S=0 CH3CH2 -;;r:,-Cl + S02
C3H 7 Cl C3H7
ALCOHOLS 81

This type of substitution mechanism is called the SN i mechaism, where i stands for internal
return. SN i reactions are quite rare in organic chemistry.
2.8 Dehydration of Alcohols
(1) Secondary and tertiary alcohols always give El reaction. Primary alcohols whose ~-carbon is 3°
or 4° also give E\ reaction.
(2) Primary alcohols whose ~-carbon is 1° or 2° give E2 reaction.
(3) Dehydrating reagents for alcohols are:
cone. H2S04/L1. KHS04/L1, H3P04/L1, Anhy. A12031L1
Anhy. PCI s 1L1, Anhy. ZnCl2 1L1, BP3 /L1 and P20S / L1.
(4) Reactivity of alcohols for elimination reaction is as follows:
fer. alcohol> sec. alcohol> prim. alcohol

Reactivity in decreasing order

2.9 Mechanism of Dehydration of Alcohols


2.9.1 Mechanism of El reaction:
Step-I
CH3 CH3
. ~
\.. \ ~
CH3-C-O-H :::;;;=~==>"~CH3-C-O-H
\.., \ \
CH3 CH3 H
Step-II Protonated alcohol

CH3
\ ~ >.. ~
CH - C - O - H ::::;;"""'==~ CH3 -C-CH3 + HOH
3 \ U\ \
CH3 H" CH3
Step-Ill

.~ ~ ~
H-Q+H-~ C-CH3 ~ H-O-H+CH3-C=CH2

H
\ \
CH3 r
\

~
HOH +H
2.9.2 Mechanism of E2 reaction

.(\ Fast G) e
CH 3-CH 2- Q- H + Hl:::J ----!>-
CH 3-CH 2- 0- H + A
~
I Conjugate base

t
Strong acid,
H

e.g., Conc. H 2S0 4 or


H 3 P04
82 UNDER GRADUATE ORGANIC CHEMISTRY

e~ El Slow step .....


A H-~CH2UI-H ...... AH+CH2 =CH2 +H-O-H
••

. H
(5) Rearrangement occurs in El as well as in E2 reactions.
2.9.3 Rearrangement in El reactions: Consider the following El reaction.
CH30H CH3 CH3
I I 85%H3P0 4 I I
CH3-C-CH-CH3 ) CH3-C=C-CH3 + CH2=C-CH-CH3
I tJ. I I Minor product
CH3 CH3CH3
Major product
This reaction takes place as follows:
CH30H CH3
I I HEll I €f)
CH3-C-CH-CH3- CH3-C-CH-CH3
I I
CH3 CH3

2.9.4 Rearrangement in E2 reactions: The given reaction is £2 reaction:


HA
CH3-CH2-CH2-CH2-0H-~) CH3-CH2-CH=CH2 + HOH
tJ.,E2

-
CH3-CH=CH-CH3
In £2 reactions rearrangement takes place after the formation of alkene because alkene reacts
e
with H of acid to give carbocation. This carbocation gives rearranged product.
e Er>
Step I: CH3-CH2-CH=CH2 + H ~ CH3-CH2-CH-CH3
Step 11:
er-")
A H
I~ Er>
---.~ CH3-CH=CH-CH3
CH3 -CH-CH-CH2-CH2
Rearranged product

~)
Er>
CH3 -CH2- C H \ 5 H ---.~ CH3- CHZ--CH=CH2
(Normal product)
ALCOHOLS 83

Thus the overall reaction is:


Conc. H2S04 It!.
CH3-CH2-CH2-CH2-0H ) CH3-CH2-CH=CH2 + CH3-CH=CH-CH3
Minor product Major product
(6) On the basis of the mechanism, one can conclude that product formation takes place
according to Saytzeff rule in El as well as in E2 reaction.
(7) Tertiary alcohols are so reactive that they undergo dehydration on strong heating even in the
absence of dehydrating agent. In this process Cu works as catalyst.
CH3
I _ I!
CH3-C-OH -~) CH3-C=CH2
I 300'C I
CH3 CH 3
(8) (a) -/ group present in an alcohol increases its reactivity for dehydration, and reactivity
cc - / power of the group present in the alcohol.
(b) Alcohols having -/ group undergo dehydration in the presence of acids as well as bases.
2.10 Dehydrogenation
rimary and scondary alcohols undergo dehydrogenation in vapour phase in the presence of copper
P catalyst, forming carbonyl compounds.
CU
R-CH20H ) RCHO + H20
300'C

R", - CU R",
CHOH I C=0+H2 )
R' I 300'C R'
Tertiary alcohols are not dehydrogenated. They undergo dehydration to give alkene.
CH3
I CU R",
R-C-OH--4) IC=CH2 + H20
I . 300'C R'
R'
Thus dehydrogenation is used to distinguish between primary, secondary and tertiary alcohols.
2.11 Oxidation
he compound that is formed by oxidation depends upon the nature of alcohol. The main oxidising
T agents are acidic and alkaline KMn04, dil. HN03' K2Cr207 and er03.
2.11.1 Primary alcohols are oxidised to aldehydes which are, in turn, easily oxidised to
carboxylic acid containing the same number of carbon atoms as the parent alcohol.
R-CH2-0H [0]) R-CHO [0]) RCOOH
2.11.2 Secondary alcohols are oxidised to ketone containing the same number of carbon atoms.
This, on further oxidation under drastic condition, forms mixture of acids each having lesser number
of carbon than the alcohol.
OH 0
I I
R-CH-R ---+) R- -R
[0] ell I
--4)
[0] . f'd
lTI1xture 0 act s
84 UNDER GRADUATE ORGANIC CHEMISTRY

OF $ 0
1 H 1 Cr20~- 11 H$
C2H5-CH-CH3 ) CH3-C-C2H5 ) CH3CH2COOH + CH3COOH + HCOOH
K2CrZ0 7 C-3 C-2 C-J
2.11.3 Tertiary alcohols do not undergo oxidation, rather in the presence of acid along with the
oxidising agent they undergo dehydration forming alkenes which are oxidised to acids having fewer
number of carbon atoms than the parent alcohol.
OH
1 H$I Cr20~- CH3" H$I Cr20~-
CH3-C-CH3 ---~) /C=CH2 ) CH3COOH + HCOOH
1 CH3
CH3
The oxidation of the primary alcohol with chromic acid begins with the formation of chromic
ester,
H 0 H 0
1 e "
R-C-O-H + 0 ~ -er-OH --~) R-C-O-Cr-OH + H20
H(f) 1 11

1 11 1 11
H 0 H 0
Chromic ester
In the next step this chromic ester undergoes an elimination reaction. This elimination reaction
forms a carbon-oxygen double bond instead of carbon-carbon double bond.

I ~ ~
o
11 Efl
R-C-Our-O-"-H---'~ R-C-H + GCr-OH+H3 0
fJ 11
~
C.~ 0
/9"
H H
The aldehyde which is formed is hydrated to produce a 1, I-diol,
o OH
11 1
R-C-H + H20 R-C-H
1
OH
This gem-diol is then oxidised to carboxylic acid as follows:
OH 0 OH 0
(i)
I G
R-C-OH+O-Cr-OH
11 H®
~
I
R-C-O-Cr-OH+H?O
11

I 11 I 11 -
H 0 H 0

OH 0 OH

(ii)
I
R-C-Od;r-OH
11
----+~
I
R-C =0 +
fJ 11

C:. I
0

H
/9"H
ALCOHOLS 85

Aldehyde can also be produced in exceIlent yield by the oxidation of a primary alcohol with
Sarett leagent. This reagent is prepared as follows:

Cr03 + 2 @
N
- Cr03· (CsHsN}z
Sarett reagent

The oxidation is done in CHzCl 2 solvent at 2S·C

R-CHzOH + Cr03(CsHsN)z
CH2Cl2 11
25" ) R-C-H
°
Sarett
CH3-(CH2)s-CH20H --~) CH3-(CH2)S-C-H
° 11

Reagent 93%

Sarett
C6HS-CH=CH-CHZOH - - - 4 ) C6HS-CH=CH-CHO
Reagent
81%
This reagent also oxidises secondary alcohols to ketones.
OH
1 Sarett
°
11
R-CH-R' ) R-C-R'
Reagent

2.12 SUMMARY OF REACTIONS OF MONOHYDRIC ALCOHOLS


(HERE ALCOHOL IS CH3-CH20H)

CH3-CH2-0-CH2-CH3
Ether formation

H 2S04• 180'C
CH2=CH2
~-elimination

Na or NaH
Salt formation

(CH3hS04/NaOH or
CH 3-CH2-O-CH3
CH3I
(Methylation)

(CH 3C0)z0/Pyor
CH3-CH2'-':O-C-CH3
°
11

CH3COCIIPy
Acetylation

TsCI/Py
CH3-CH2-0-Ts
HX

PCl s or PCI 3 or SOCI 2


CH3-CH2-0.T.T )

COlltd.
86 UNDER GRADUATE ORGANIC CHEMISTRY

:,Contd.
PBr3 or P/Brzl~
r------~ CH3-CH2-Br
PI 3 or P/I2/~
I-------~ CH3-CH2-I
OC2HS
R-CH=CH 2/H2S0 4 I
I-------~ R-C-CH3
Mild oxidising
t-------~ CH3-CHO
Agent

Strong oxidising
) - , - , - - - - - 0 - .~ CH3-COOH
Agent, KMnOiOH/~

HI or
'-------~ R-H
Ci) TsCIIPy Cii) LiAIH4

2.13 Distinction between Primary, Secondary and Tertiary alcohols


he following tests are used to distinguish between primary, secondary and tertiary alcohols.
T 3.13.1 Lucas test: When an alcohol is treated with Lucas reagent (mixture of conc. HCI and
anhy. ZnCI 2; for detailed reactions see Section 2.7) at room temperature, tertiary alcohol reacts
immediately to form an oily layer or turbidity of alkyl chloride (alkyl chloride is insoluble in the
reaction medium). Secondary alcohol reacts within ten minutes to form an oily layer or turbidity of
alkyl chloride while primary alcohol does not react at room temperature.
R' R'
j ZnCI 2 I
R-C-OH + HCI-~)R-C-CI + H20
I
R"
I
R"
Ter. alkyl chloride. fast appearance
of turbidity or oily layer

OH OH
I ZnCI 2 I
R-CH-R' + HCI ) R-CH-R' + H20
Sec. alkyl chloride. slow appearance
of turbidity or oily layer
ZnCI 2
R-CH2-0H + HCI ) No reaction at room temperature
The oil produced in these reactions is the alkyl chloride. Since oil formation is the most
recognisable sign of the reaction, it follows that the alcohol must be soluble in the Lucas reagent in
order to detect a positive reaction. Actually most simple alcohols are soluble in the Lucas reagent,
probably because of the formation of an oxonium salt.
H

R-OH + HCl-~) R-6EfJ Cl0


I
H
This is most convenient method of distinction between three types of alcohols.
ALCOHOLS 87

2.13.2 Victor Meyer test: This test is based on the different behaviour of the corresponding
nitroalkanes towards nitrous acid. The test consists of the following steps:
1. Alcohol is converted into alkyl iodide by treatment with I21P.
2. Alkyl iodide is then treated with AgN02 to form corresponding nitroalkane.
3. Nitroalkane is finally treated with mixture of NaN02 and H2S04 and made alkaline with
alkali (NaOH or KOH).
If blood red colour is produced in this way, the original alcohol is primary. If a blue colour is
produced, the alcohol is secondary and if no colour is produced the alcohol is tertiary.
Tertiary alcohol Secondary alcohol Primary alcohol

~)CH-OH R-CH 20H

fiP lIt"
R
R~-I
IV
R'CHI
R/ RT21 AgN0 2

1 jAgN02

I
AgN0 2

~)CH-N02
RJc-
R

R1
N02
NaNOzIH2S04 I N.rIDtH,SO,
R-,.CH2N02
NoN<J,IH,SO.

No reaction. No colour with


R'C/NO R-C~NO
alkali R/ ........N02 ........N02
Pseudonitrol Nitrolic acid
Colourless
1 NaOH
Blue colour
INaoH
Red colour

2.13.3 Oxidation: Oxidation of alcohol followed by identification of the product formed, gives
an idea of the nature of alcohol.
(i) Primary alcohol on oxidation first gives an aldehyde and this on further oxidation, gives an
acid. Both aldehyde and acid contain the same number of carbon atoms as the original alcohol.
R-CH20H [0) R-CHO [0) R-COOH
(ii) Secondary alcohol, on oxidation, first gives a ketone with the same number of carbon atoms
as the original alcohol. Oxidation of ketone is fairly difficult but prolonged action of the oxidising
reagent results in the formation of an acid or mixture of acids having lesser number of carbon atoms
than alcohol.
(iii) Tertiary alcohols are resistant to oxidation in neutral or alkaline solution but are readily
oxidised by acidic oxidising agents to a mixture of ketone and acid, each containing fewer number of
carbon atoms.
2.14 Alcohol Industry
(1) Beverage Alcohol: Ethyl alcohol is commonly referred to as beverage alcohol because it is
produced by the fermentation of the natural sugars. In alcohol industry these sugars for fermentation
are obtained either from fruit juices or molasses. Alternatively, sugars may be obtained by the
hydrolysis of starch (source-potatoes, barley, maize, etc.) or by the hydrolysis of cellulose
(source-sawdust).
88 UNDER GRADUATE ORGANIC CHEMISTRY

(i) From Sugars: Sugars like glucose and cane sugar when fermented in the presence of
enzyme are converted to ethyl alcohol. Enzymatic fermentation of sucrose and glucose is as follows:
Sucrase
C 12H 220 1l + H 20 ) C6H 120 6 + C6H 12 0 6
Sucrose (From yeast) Glucose

Zymase
C6 H 1206 ) 2C2HsOH + 2C02
(From yeast)

A solution containing not more than 14% alcohol can be produced by fermentation, because
yeast cells die or cease production at this concentration due to the aforementioned antiseptic action
of alcohol.
Alcoholic beverage can be divided into three categories-beers, wines and spirits. All involve
fermentation of sugars. In addition, beverage can acquire other alcohols, carboxylic acids, esters,
aldehydes, ketones through fermentation or absorption. These are called congeners and contribute to
the taste, aroma and colour.
Beer is the fermentation product of barley and hops. The alcohol content varies from 2%-12%
although in most beers the alcohol content is about 4%-5%.
Wines are fermented from the juice of grapes and are classified as natural or sparkling wines
and fortified or aromatic wines. Natural and sparkling wines like champagne contain less than 14%
alcohol. Fortified wines (Sherry) and aromatic wines (vermouth) contain about 15%-23% alcohol.
Since fermentation cannot naturally produce this concentration, these beverages must be fortified by
alcohol from other sources.
Distilled spirits include rums, whisky, gins and vodkas. In the production of these a carbohydrate
mash is allowed to ferment and is then distilled to produce beverages with a 40%-50% alcohol content.
(ii) Ethyl alcohol from starch: Starchy materials (like potatoes) are cut into slice and crushed.
The crushed mass is then steamed at 140°-150°C under pressure. In this way starch is brought into
solution. This solution is called Mash.
The mash is treated with malt from germinating barley and containing the enzyme diastase. This
enzyme converts starch into maltose.
Diastase
2 (C~IOOS)n + nH20 ) n CI2H2201l
(From malt) Maltose
The resulting mixture is then subjected to fermentation with yeast. Yeast provides enzymes
Maltase, and Zymase.

Glucose Glucose

Zymase
C~1206----7) 2C2HsOH + 2C02
The fermented liquid is known as Wash.
The crude alcohol (wash) obtained above is subjected to fractional distillation whereby 95%
ethanol called rectified spirit is obtained.
Rectified spirit is a mixture of 95% ethanol and 5% water. This. mixture cannot be separated by
further distillation. Such a solution is called Azeotropic solution or Azeotrope. A method used for
obtaining absolute alcohol (100% pure) is based on azeotropic distillation. In this method excess of
benzene is added to the rectified spirit. Benzene fOlms tertiary mixture with water and ethanol (7.4 :
18.4 : 74.1 : : H20: EtOH : C6H6) and binary mixture with ethanol (32.4 : 67.6 : : EtOH: C6H6). The
tertiary and binary mixtures are azeotropic mixtures having the bp 64.8°C and 68.2°C respectively.
ALCOHOLS 89

When benzene and rectified mixture is distilled, the tertiary mixture is distilled at 64.8°C
removing all the water and then the binary mixture is distilled at 68.2°C removing all the beJlzene.
Finally 100% pure ethanol or absolute alcohol is distilled at 78.3°C.
2.15 Dihydric Alcohols

T heknown
compounds containing two hydroxyl groups are known as dihydric alcohols. They are also
as glycol (Greek: glykus = sweet) because they are sweet in taste. The two hydroxyl groups
of dihydric al.::ohol must be attached to two different carbon atoms because the compounds having
two hydroxyl groups on the same carbon atom (gem-diols) are usually unstable. They undergo
spontaneous dehydration to give the corresponding carbonyl compound and water.
OH 0
1 11
R-C-R' -~ R-C-R' + H20
1
OH
For example, the simplest gem-diol, methylene glycol is known only in aqueous solution
(formalin) and attemp,ts to isolate it always yield formaldehyde.
OH 0
1 11
H-C-H ) H-C-H + H20
1
OH
Methylene glycol
Certain gem-diols are stable whose structure and name is given below:
OH
1
CCI3-C-H
1
OH
2, 2, 2-Trichloro-I, I-ethanediol
OH
1
CF3-C-H
1
OH
2,2, 2-Trifluoro-l, I-ethanediol
OH
1
CF:\-C-CF3
- 1
OH
1, 1, 1,3,3, 3-Hexafluoro-2, 2-propanediol

o
11

(JCI
~
CXOH
C OH
11
o
Ninhydrin
90 UNDER GRADUATE ORGANIC CHEMISTRY

Note: Gem diols are stable due to two factors:


(i) Presence of strong - I groups on a-carbon which holds both hydroxyl groups tightly on the
same carbon atom.
(ii) Intramolecular hydrogen bonding stabilises gem diols.
Glycols having -OH groups on adjacent carbon atoms are called vicinal diols.
2.15.1 Nomenclature of diols
In common (trivial) naming system these are named by adding the suffix glycol to the common
name of the corresponding alkene. The relative position of the -OH group in the molecule is
designated by a(l, 2), /3(1, 3) and y(l, 4), etc. /3-, y- and other glycols are also called polymethylene
glycols.
In IUPAC nomenclature the longest straight carbon chain containing -OH groups is selected
and the compound is named as the hydroxy derivative of the corresponding alkane. The chain is
numbered from one end to the other so that the sum of the numbers assigned to carbon atoms bearing
various substitutents, including the -OH groups, is minimum. The name of the parent alkane is
prefixed by the names of the substituents preceded by the numbers indicating their positions, and
suffixed by the term diol, the numbers indicating the position of the hydroxyl groups are written just
before the name of the parent alkane. Both these systems of nomenclature of diols are illustrated below
with common names in parentheses.
HO-CH2-CH2-0H HO-CH2-CH-CH3
I, 2-Ethanediol I
(Ethylene glycol; I, 2-ethylene glycol) OH
1,2-Propanediol
(a-propylene glycol;
I, 2-propylene glycol)
HO-CH2-CH2-CH2-0H
1,4-Butanediol I, 3-Propanediol
(y-butylene glycol; ([3-propylene glycol;
I, 4-butylene glycol: trimethylene glycol)
Tetramethylene glycol)

CH3 CH3 OH OH
I I I I
H3C-C - C-CH 3 CJIs-CH-CH-CJIs
I I 1, 2-Diphenyl-l, 2-ethanediol
(hydrobenzoin)
OH OH
2, 3-Dimethyl-2, 3-butanediol
(pinacol)
2.16 Methods of Formation of Vicinal Glycols
2.16.1 From a1kenes:
(i) Hydroxylation: When alkenes are treated with cold alkaline solution of KMn04 or
OS04, glycols are formed

)C=C ( _ _KM_n_O_i_HzO_o_r_-t) '-.. C-C/


" (i) OS04 /' I I "-
(ii) aq. ethanolic NaHS03 OH OH
ALCOHOLS 91

Q (}!HOH
Os -1, 2-cyc1opentanedio1
(ii) Alkene is first converted into alkene oxide (epoxide). e.g.,
Ag/I).
CH2=CH2 + O2 ) CH2-CH2
Under pressure "/
or per-acid (RCOOOH) 0

Ethylene oxide is then hyrolysed with dilute H2S04 to give glycol.

The carbon-oxygen bond is broken very easily compared to such a linkage in an open chain
system. This is because of the presence of strain due to angle distortion. The mechanism is as follows:

CH 2 -
H$
CH 2 ~_•• CH 2 -
n o..-
CH2
.:,
H
H. CH2 -CH2 -
+

5:
H
• CH 2 -CH 2
"0/ ""~O I H I I
I OH OH OH
H
(iii) Alkene is first converted into vicinal dihalide or alkene halohydrin. Hydrolysis of these with
aqueous alkali results in the formation of glycol, e.g.,

Br Br
OH OH
I I I I
CH2=CH2 + Br2 --~) CH2-CH2 aq. Na2C03
f-----~ CH2-CH2
OH Cl
I I
CH2=CH2 + HOCI-~) CH~CH2
Hydrolysis of ethylene chlorohydrin (haloalkanols) should be carried out in mild conditions. In
the presence of strong alkali they undergo ring closure through nucleophilic displacement forming
epoxide.

CH 2 -CH 2 -Cl
8\ I
OH \Hd

Hydrolysis of dihaloalkenes with NaOH or KOH leads to the formation of vinyl halides. For
better result the alkene bromide is first converted to glycol acetate by silver acetate. The acetate on
hydrolysis with NaOH gives glycol, e.g.,
o R R
11 I I ~HlH20
R-CH-CH-R + Ag-O-C-CH3 --4 CH-CHOCOCH3 ---+. R-CH-CH-R + 2CH3COOH
I I I I I
Br Br OCOCH3 OH OH
92 UNDER GRADUATE ORGANIC CHEMISTRY

2.16.2 From carbonyl compounds


Reduction of aldehydes and ketones with metals in inert solvents such as benzene, ether, etc.,
or under alkaline conditions give 1, 2-diols. These reductions are commonly called bimolecular
reductions, e.g.,
o OH OH
" (i) Mg/benzene
CH3-C-CH3 ----~) H3C-C - C-CH3
I I
(it) H20 I I
CH3 CH 3
Pinacol

o OH OH
" (i) MglMgI/benzene
C6HS-C-C6HS-----~) C6HS-C - C-C~s
I I
(ii) H20 I I
C6HsC~S
Benzopinacol
(hydrobenzoin)
The mechanism of the reaction is outlined below:
/Mg"
o 0 0 Radical
"
2H3C-C-CH3 + 2e (Mg) ~ H3C-C
I. •C-CH3
I coupling

I I

Pinacol
1, 2-Diols can also be obtained by action of Grignard reagent on 1, 2-diketones.
o 0 oeoe OH OH
Ell
""
CH3-C-C-CH3
2RMgX I I
) H3C-C-C-CH3
H30
) H3C-C-C-CH3
I I
Biacetyl I I I I .
R R R R

2.17 Properties of vicinal glycols


2.17.1 Physical Properties: Ethylene glycol and other dihydroxy alcohols are more soluble in water
than monohydric alcohols. This is because of the fact that in the case of diols more than one site is
available for intermolecular hydrogen bonding. This hydrogen bonding is also ,responsible for their
higher melting and boiling points as compared to monohydric alcohols.
2.17.2 Chemical Reactions: The chemical reactions of glycol are those which might have been
expected of a monohydric primary alcohol. However, in most of the reactions both of these groups
are not equally reactive. Thus one hydroxyl group reacts completely before the other one participates
in the reaction and the second group reacts under more vigorous conditions. In other words, when one
ALCOHOLS 93

hydroxyl group has undergone the chemical reaction, it modifies the reactivity of the other hydroxyl
group. The important reactions of vicinal glycols are given below:
(i) Reaction with Alkali Metals: Acidic Character: Ethylene glycol reacts with alkalI metal
at 50'C to form monoalkoxide and at 160'C it gives dialkoxide.

CH2-0H
1 +Na
CH2-0H

Thus one -OH group is attacked completly before the other reacts and more vigorous condition
is needed for the reaction of second -OH group. The reason for this is obvious. Initially the -I
effect of one hydroxyl group makes the other more acidic or reactive. But once this hydroxyl group
has reacted with the metal to form alkoxide ion, it adversely effects the acidity of the other hydroxyl
group because of the +1 effect of alkoxide ion. This renders the second hydroxyl less acidic.
(ii) Reaction with Hydrogen Halides: Glycols form the corresponding dihalogen derivatives
with hydrogen halides. The reaction takes place in two stages. For example, ethylene glycol forms
ethylene chlorohydrin at 160'C but at higher temperature (200'C) it gives ethylene chloride.

i
H20H
HCl) iH2Ci

CH20H 160°C CH 20H 200°C CH 2Ci


HCl) i
H2Ci

(iii) Reaction with Phosphorus Halides: Glycols react with PBr3 or PCl s to form the
corresponding dihalides.
CH20H CH 2Br CH 2Br
PBr3
1 + PBr3 ) 1 ) 1
CH20H CH20H CH 2Br
CH20H CH2Cl PCl s CH 2Cl
I +PCls )I )I
CH20H CH20H CH2Ci
With P1 3 , It first forms the ethylene iodide which IS unstable and decomposes to form ethylene.
CH20H CH J CH2
1 + PI3 ) 1 ) 11 + 12
CH20H CH21 CH2
(iv) Reaction with Carbonyl Compounds: Aldehydes and ketones form nng compounds
(cyclic acetals and ketals) with glycols. The reaction is catalysed by acid.
H H
CH 20H I H(f) CH2-0\ I
I +O=C-R )1 C-R
CH 20H ~ CH2-0/
Cyclic acetal

Cyclic ketal
This reaction offers a means of protecting a carbonyl group in reaction carried out In basic
medium. The carbonyl compound may be regenerated by the addition of periodic acid to an aqueous
solutIOn of the cyclIc acetal or ketal (dioxolan).
94 UNDER GRADUATE ORGANIC CHEMISTRY

R
~ ) C=O + 2HCHO
R'
(v) Dehydration: Different products are obtained under different conditions, e.g., dehydration
of ethylene glycol is given below:
(a) When heated alone upto 500'C it forms epoxIde.
CH20H 000 CH2\
5 C
--~)
1
0
1
CH20H ~ CH2/
(b) When heated with anhydrous ZnCI 2, It forms acetalydehyde.
H
I
ZnCl z i
) C-OH
-H 20
11
CH2
(c) When heated with conc. phosphoric acid, it forms diethylene glycol.
HO/CH2-CH2'OH /CH 2CH 20H
H3P04
---~)O

HO'CH 2- CH t / OH "CH2CH20H
Diethylene glycol
(d) When heated with conc. H2S04 it gives a cyclic ether dioxane
/CH 2-CH 2,
HO OH conc. H2S0 4 /CH2-CH2\
--~-~) 0" /0
HO'CH2-CH2/0H CH2-CH2
Dioxane
(I A-Dioxane)
(vi) Oxidation: On oxidation, glycols give a variety of products whIch depend on the nature
of oxidising agent and other reaction conditions. The product may anse with or without the breaking
of carbon-carbon bond. This has been illustrated below by taking the example of ethylene glycol.
(a) When nitric aCId or alkaline potassium permanganate is used as oXIdising reagent, the
following products are obtamed.
CH20H [0] CHO [0] COOH [0] COOH [0] COOH
1 )1 -~)I -~)I -~)I
CH20H CH20H CH 20H CHO COOH
Glycolaldehyde Glycollic aCId OxalIc aCId

jror
[0]
CHO
1
CHO
Glyoxal
(b) Oxidation with periodic acid: When treated with aqueous HI04, glycols undergo
carbon-carbon bond fission to give aldehydes and/or ketones. This IS the specIfic reactIon of I. 2-diols.
The reactIOn proceeds through the formatIOn of a cyclic ester of para periodIc aCId (HsI06 ) whIch IS
AlCOHOlS 95

formed by the reaction of water with meta periodic acid (H104)' Aqueous H104 or HS106 is called
Malaprade reagent and this reaction is referred to as Malaprade reaction.
The active species of HI04 in aqueous solution is H4IO~. .
The mechanism of oxidative cleavage of vicinal glycols with aqueous HI04 is as follows:
OH Q(-H °
OH, I . . . . . OH 2HOH CH 2;- 0 , 1.......-9H -HOH CH 2 ,0>-...11
+ I - ~ 1 I:"'V • \--../ ~I - 0 8
OH"/~ '2 CH2-0"""""~ ~2 CH 2 ~ ~

!
o
11 H-C-H
°
11

1-08+ +
11 H-C-H
° o11

(c) Oxidation with Lead tetraeetate: Similar to periodic acid, with Pb(OAc)4 also the
oxidation of 1, 2-diols takes place via the formation of cyclic ester.
OCOCH3
CH2-OH 1 .......... OCOCH3
1 + Pb ~
CH2 -OH I ' OCOCH3 -2CH3COOH
OCOCH3

o11
°
11 .......... OCOCH 3
H-C-H +H-C-H+ Pb
'OCOCH3
(vii) Reaction with cone. HN03: On heating with conc. HN03 in the presence of conc.
H2S04, ethylene glycol form ethylene dinitrate which is highly explosive liquid.
CH20H H S0 CH2-0-N02
2 4
I + 2HN03 ) I + 2H20
CH20H CH2-O-N02
(viii) Acid-Catalysed rearrangement of glyeols-Pinaeol-Pinaeolone Rearrangement: 1, 2
Glycols on treatment with acid rearrange to form carbonyl compounds, the classical example bemg
the acid catalysed rearrangement of pinacol to pinacolone.
CH3 CH3 CH30
I I
CH3-C - C-CH3 ---"7) CH3-C - C-CH3
·H
e I"
I I I
OH OH CH3
Pmacol Pmacolone
96 UNDER GRADUATE ORGANIC CHEMISTRY

Step-II: Carbocation (I) undergoes rearrangement in this step.


(±)
O-H CH3
Methyl migration~ 11 I
CH3-C--C-CH3
I
CH3
(11)
(I)

We know that carbocations rearrange by hydrogen or alkyl shift to get as stable as they can be
but carbocation (1) is already tertiary and there is no ring strain, so why should it rearrange?
Due to migration of methyl group, positive charge moves on oxygen thus giving oxonium cation.
In carbocation (I) carbon has incomplete octet but in cation (ll) every atom has complete octet. Hence
(Il) is more stable than (I). Thus stability is the driving force for rearrangement.

fFH rH
@

CH3-C---<C-CH 3
I
CH3
3

- Et>
-H

This reaction is intramolecular rearrangement; thus actual mechanism can be written as follows:
(±)
OH OH 0 - H(OH2
~ '-1
CH3- yI - yI -CH3 ~CH3-y--
I
Y- CH3
Slow step ~
-Hp
CH3 CH3 CH3 CH3

o CH
11 I 3
CH3-C - C- CH3
I
CH3
Migration of a bond may also occur in this rearrangement whereby ring expansion. and ring
contraction reactions may take place.
ALCOHOLS 97

Benzyl carbocation
(more stable)

~
OH

~-CH
U ~ 65
C6HS
Alkyl carbocation
(less stable)

(Ring expansion)
Ring Contraction

G __ Cf
<±l
O- H CH =9TH
_ _+~ C9.~O-H C,r..
CX O-H
<±l
+~

I
.. CHO
V

C(
Migratory preference of the group: Consider the following examples:
OH OH 0
I I H2S0 4 11
C6HS-C-C-CH3 -~) C~s-CH2-C-CH3
I I
H H
OH OH CH3 0
I I H2S0 4 I 11
CH3-C - C-H -~) CH3-CH-C-H
I I
CH3 H
98 UNDER GRADUATE ORGANIC CHEMISTRY

These examples show that migratory prference of CJI5 is more than H which is more than alkyl
group.
The usual migratory preference order in most stable carbocation in this reaction is as follows:

CH3-O-@- > CH3-@->~> Cl-@->


CH3

~> <Q(-> <Q(-> CoR, > H>. R


OCH3 CH3 Cl
Pinacol halohydrin also gives pinacolone with Ag 20. Similarly, {3-amino alcohol gives
pinacolone with NaN0 2/conc. He!.

In these reactions, intermediate is carbocation in which {3-carbon has hydroxyl group which gives
pinacolone.
In cyclic vie-diols it has been found that the migrating group is always Irans to the leaving
group.
Me

(a)~OH
'FT- OH~
CH3

Me and OH
are trans
Eil
This bond is frans to H20
OH hon" th, bond W~H Botl"" ~

Ff
(b)
CH
,CH
OH
3
3
~
~
OH
(.i) 2
.
CH3 ~ cis hence
CV~ -:CH3 group -
WIth
migrate
not
~C-CH3
L-J"CH3
ALCOHOLS 99

Epoxides also rearrange with Lewis acids in a pinacol fashion. In this case, the best result is
obtained with MgBr2'
~Mg_Br
I et}
~ C6Hs WHC6HS

2.18 Structure of ethylene glycol


1. Molecular formula: The molecular formula, as determined by elemental analysis and molecular
weight determination is C2H602.
2. Nature of two oxygen atoms:
(i) Ethylene glycol forms diacetate with acetic anhydride or acid chloride.
(ii) Ethylene glycol forms ethylene chloride with PCIs.
'These two reactions indicate that both the oxygen atoms are present in the form of hydroxyl
groups.
3. Since the compuond is. stable, the two -OH groups must be present on different carbon
atoms. Considering the valency of carbon atom and molecular formula, the structure of glycol can be
written as follows:
H H
I I
H-C-C-H
I I
OH OH
Finally, the structure has been confirmed by its synthesis:

2.19 Trihydric Alcohols

TheIUPAC
simplest and most important trihydric alcohol is commonly known as glycerol or glycerine. Its
name is 1, 2, 3-propanetriol. It is present in almost all the animal and vegetable fats and
oils in the form of esters (glycerides) of higher fatty acids.
Glycerol is prepared by the following methods:
(i) From Fats and Oils: Glycerol is obtained as a by-product in the manufacture of soap.
Hydrolysis of glycerides with sodium hydroxide yields glycerol and sodium salt of fatty acids. This
hydrolysis reaction is known as a saponification.
CH2-O-COR 0 CH20H
I HzO 11 I
CH-O-COR + 3NaOH----~) 3R-C-08 Naet} + CH OH
I Saponification I
CH2-O-COR CH20H
Glycerol

(ii) From candle industry: In the manufacture of candles higher fatty acids, like stearic acid
are fixed with paraffin wax. The higher fatty acids required for this purpose are obtained by the
hydrolysis of fats and oils with superheated steam using dilute H2S04 as catalyst. These fatty acids
100 UNDER GRADUATE ORGANIC CHEMISTRY

are generally insoluble and are removed by filtration. The glycerol is recovered from the aqueous
solution.

(iii) From propene: Glycerol is prepared synthetically from propene which is obtained during
the cracking of petroleum.

CH2 CH2 CH2 CH20H CH20H


11
CH--~)
CI2 "
CH
Na2C03
~ CH
11 HOCI I dil.NaOH
CHCI----?) CHOH
I
I 500·C I 150· Under pressure I I I
CH3 CH2Cl CH20H CH20H CH20H
Allyl alcohol Glycerol-l3-monochlorohydrin

2.20 Properties of glycerol


(1) Physical properties: Glycerol is colourless, odourless, sweet and syrupy liquid having bp 290°C.
On cooling it crystallises slowly, mp 18°C. It is miscible with water and alcohol in all proportions
due to the availibality of three hydroxyl groups for hydrogen bonding with water and alcohol. It is
immiscible with ether, benzene and hexane. It absorbs moisture from air because it is hygroscopic.
The molecule contains two' primary and one secondary alcoholic groups. It undergoes many of
the reactions characteristic of these groups. Generally, primary alcoholic groups are more reactive than
secondary hydroxyl group.
(2) Chemical reactions:
(i) Reaction with electropositive metals-acidic character
Glycerol shows acidic behaviour towards electropositive metals. When treated with sodium
metal, it forms monosodium and disodium salt in which hydrogen atoms of both the primary groups
are displaced one after the other but secondary alcoholic group remains unaffected.
,
CH20H CH20 e NaEi3 CH20eNaEi3
I
CHOH
Na
)CHOH
I Na I
)CHOH
I 25°C I High temperature I
CH20H CH20H CH20eNaEi3
(ii) Reaction with hydrogen halides: When dry HCI gas is passed through glycerol at 110°C,
glyceryl a- and /3-chloro hydrins are formed. When excess of HCI is passed, aa'- and
a/3-dichlorohydrins are produced.
CH20H CH2C1 CH2C1
I HCI I +
HCI I
CHOH --7 CHOH -----t) CHOH +
I lWC I Excess
I
CH20H CH20H CH2CI
Glycerol a-chloro- Glyceroll3-chloro- a, a' -dichloro- a, l3-dichloro-
hydrin hydrin hydrin hydrin
ALCOHOLS 101

When glycerol or any glycerol chlorodihydrin is treated with PCIs, glyceryl trichlorohydrin is
formed.
CH20H CH2CI
1 PCl 5 1
CHOH--~)CHCI
1 1
CH20H CH2CI
Glycerol trichlorohydrin
(iii) Reaction with hydrogen iodide: Glycerol reacts with HI in two ways.
(a) When glycerol is treated with HI or PI 3 in small amount, it forms glycerol tri-iodide. This
compound being unstable looses two iodine atoms from vicinal positions to form allyl Iodide.
CH20H CH2I CH2
1 Warm 1 11
CHOH+3HI ) CHI )CH
1 -3H20 1 -12 1
CH20H CH2I CH2I
Unstable Allyl iodide
(b) When glycerol is heated with excess amount of HI, allyl iodide is produced first. In the
presence of excess HI, allyl iodide adds a molecule of HI to give 2-iodopropane. The addition takes
place according to Markownikov rule.
CH2 CH3 CH3
11 HI -12 1 HI 1
CH--~ --~) CH--~) CHI

1 11 1
CH2I CH2 CH3
Unstable Propene 2-lodopropane
(iv) Reaction with oxalic acid: Glycerol reacts with oxalic acid under different conditions to
give different products.
(a) When heated at BO°C, glycerol reacts with oxalic acid to form glyceral monoxalate which
on decarboxylation forms glycerol monoformate. Glycerol monoformate on hyrolysis gives formic
acid and glycerol is regenerated.

110°C 1HzO
CH20H
1
CHOH + HCOOH
1 Formic acid
CH20H
102 UNDER GRADUATE ORGANIC CHEMISTRY

(b) When heated to 260°C it first forms glycerol dioxalate which decomposes at high temperature
to give allyl alcohol.
0 0
CH2
OH-C
11 -.CL
0
11
CH20H CH2 C 11

~o'1=O
260°C 260°C + 2C02
1
CHOH +HO-C
1
- 2H20 • • CH
I
I 11 I CH20H
CH20H CH20H
0 Allyl alcohol
Glycerol dioxalate

(v) Dehydration: When heated alone or with nonvolatile strong acid such as KHS04. glycerol
eliminates two moles of water to' form acrolein.

CH20H CH2 CH 2
1 KHS04 11 11
CHOH ) C ~CH
,1
1 11 1
CH20H CHOH CHO
Acrolein

(vi) Reaction with conc. HN03: Treatment of glycerol with cone. HN03 in the presence of
cone. H2S04 at 10°C results in the formation of glyceryl trinitrate commonly known as trinitroglyerine
(TNG).

TNG is highly poisonous oil and an explosive.


(vii) Esterification: Glycerol on heating with acetyl chloride or acetic anhydride forms a
triacetyl derivative.

Glyceryl triacetate
(viii) Oxidation: Glycerol is oxidised to give a variety of oxidation products because primary
alcoholic groups are oxidised to aldehyde and then to acid while secondary alcoholic group is oxidised
to ketone which resists further oxidation. The nature of products depends on the nature of oxidising
agents. The following reaction sequence depicts various oxidation products of glycerol.
CH20H CHO COOH
1 [0) 1 [0) 1
CHOH ~CHOH ~CHOH
1 1 1
CH20H CH20H CH20H
Glyceraldehyde Glyceric acid

1[0] 1[0]
ALCOHOLS 103

CH20H COOH COOH


I
C=O --~)
[0] I
C=O ~(---CHOH
[0] I
I I I
CH20H COOH COOH
Dihydroxyacetone Mesoxalic acid Tartonic acid
(ix) Oxidation with periodic acid or lead tetraacetate: When treated with periodic acid or
lead tetra acetate, glycerol undergoes carbon-carbon bond fission to give carbonyl compound and acid.
This oxidation reaction is stoichiometric, with one mole of oxidant being consumed for each vicinal
dihydroxy group. When two adjacent C-C bonds are cleaved, the central carbon is oxidised to
-COOH.
CH20H 0
- - -j - - - 2HIO~ "
CHOH --~) 2H-C-H + HCOOH
---1---
CH20H

2.21 Structure of glycerol (1, 2, 3-propanetriol)


1. Molecular formula: The molecular formula, as determined by elemental analysis and
molecular weight determination, is C3Hg03.
2. Nature of three oxygen atoms: Glycerol forms triacetate with acetic anhydride or acetyl
chloride, which shows the presence of three ~droxyl groups.
3. Since the compound is stable, the two -OH groups cannot be present on the same carbon
atom. Thus all the hydroxyl groups must be present on different carbon atoms. The structure of
glycerol thus can be written as:
H H H
I I I
H-C-C-C-H
I I I
OH OH OH
This structure is further supported by periodate oxidation. One molecule of glycerol consumed
three moles of periodate liberating two moles of formaldehyde and one mole of formic acid.
Finally, the structure of glycerol is confirmed by its synthesis.
CH20H
Cl 2 Cl2 Na2C03 I
CH3-CH=CH2--~) CH2CI-CH=CH2 --~) CH2CI --~) CHOH
500°C I I
CHCI CH20H
I
CH2CI
104 UNDER GRADUATE ORGANIC CHEMISTRY

VERY SHORT ANSWER QUESTIONS


1. Complete the following reactions:
CH20H
CH20H ZnCl z ! CH20H
Ca)! ~ Cb) CHOH Cc) !
CH20H ! CH20H
CH 20H

r- r
El
KMn0 4 /0H
Cd) (CH3h (CH 3h Ce) trans-2-butene
cold
OH OH
2. Which of the following is stable gem-diol ?
CH3CH(OH)z, CH3C(OH)zCH3, CI3CCH(OH)z
3. Which of the following can be used for trans-hydroxylation of an alkene?
Ca) OS04 Cb) Alk. KMn04
Cc) Perbenzoic acid followed by hydrolysis
4. Glycol when heated with phosphoric acid, gives:
Ca) 1,4-Dioxane (b) Ethylene oxide (c) Diethylene glycol
5. Glycol is converted into a synthetic fibre dacron when heated with :
Ca) Phthalic acid + HEB (b) Isophthalic acid + HEB Cc) Terephthalic acid + H$
6. Malaprade reagent used to detect vicinal diols is:
Ca) H5106 Cb) Alk. KMn04 Cc) OS04
7. Suggest a reagent to convert a carboxylic acid into the corresponding primary alcohol.
8. Give products CA) and CB) in the following reactions:

(A) • UAIH, 6
o
,,"H2• (B)

9. Why are alcohols weaker acids than water?


10. Arrange the following in increasing order of basicity:
e e
H20, OH, CH30, CH30H
11. Give the reagent to distinguish between 1,2-propanediol and 1,3-propanediol.
12. What happens when ethylene glycol is treated with (i) P + 12 CH) HI?
13. Give the product of catalytic reduction of CH3CH=CHCHO. Can CH3CH=CHCH20H be isolated?
14. Explain why acid-catalysed dehydration of tert-butyl alcohol occurs faster than n-butyl alcohol?
15. Complete the following reaction and indicate whether it would proceed with inversion of
configuration or racemisation?
H
D""::C-OH ~
HC"
3
16. Which of the following gives positive iodoform test?
Ca) I-Propanol Cb) 2-Propanol Cc) 3-Pentanol
ALCOHOLS 105

PROBLEMS WITH SOLUTIONS


1. R-OH reacts with NaBr in the presence of H2S04 to give RBr. Why is H 2S04 required? What is
the mechanism of the reaction?
2. When the reaction of an alcohol and thionyl chloride is carried out in the presence of pyridine, an
alkyl halide forms with inversion of configuration. What is the mechanism of the reaction?
3. How the following conversions can be done?
Ca) CH3-CHOH-CH2-CH3 to CH3-CH2-CH2-CH20H
(2 0 alcohol to 1a-alcohol)

Cb) CH3-CH2-CH2-CH20H to CH3-CHOH-CH2-CH3


(l 0 -alcohol to 20 -alcohol)

OH
Cc) CH3-CH-CH20H to CH3-t-CH3
I I
CH3 CH3

4. Convert
Ca) CH3-OH to CH3-CH 2-OH
(step-up number of carbons)
Cb) CH3-CH2-CH20H to CH3-CH2-OH
(step-down number of carbons)
5. Complete the following reactions:
CH2-CH 2 !1
Ca) ' " I + HO-CH2-CH2-0H ~ CA)

o Jro~
(ii) CH3l
CB)
CH2-CH 2 Hd~
Cb) "'I +CNe~(A)~B
o
RCOOOH HBr
Cc) CH3-CH=CH-CH3 ) (A) --~) (B)
HOCl NaOH CH3MgBr H3 0 (j)
Cd) 2-Butene~CA)~(B) ) (C)~(D)
6. Given below is the list of carbonyl compounds obtained by action of periodic acid on different
unkown glycols. Deduce the structure of the glycol in each case.
106 UNDER GRADUATE ORGANIC CHEMISTRY

7. Predict the stereochemistry of products when (R)-2-pentanol is treated with the following reagents:
(a) Lucas reagent (b) SOCl2 (c) PC13
8. In the following sequence of reactions, identify products (A), (B) and (C):

HO C.H 3
(a)
CS OH
H2S04
~ (A)
B2H6
~ B

I K2Cr20lH$ Mg H2S0 4
(b) CH3--CH-CH3 ) (A). ) (B) ) (C)
MOIst benzene

e
B H 1600 HP2/0H
(d) CH3CH=CHCH3 2 6 ) (A) ) (B) ) (C)
9. Predict the product in the following reactions:
OH OH
~~H~h I
(a)~
(b) ~C-Ph
LJ "Ph
Ph Me
If' I I
.. (d) Ph-C -C-Ph
I I
OH OH

10. Convert

(a) 0 -~oo
Cl
I
(b) CHr -CH-CH2-CI ~ CH3-CH-CH20H
. I
OH
11. Give the synthesis of each of the following alcohols from an alkene with the same number of carbons.
ALCOHOLS 107

12. Hydration of 3-phenyl-l-butene in dilute H2S04 is not a satisfactory method fc- preparing
3-phenyl-2-butanol because 2-phenyl-2-butanol is obtained instead. Explain.

PROBLEMS FOR SELF ASSESSMENT


1. Show how you might bring about the following conversions. For any conversion involving more than
one step, show each intermediate compound formed.
CH3 CH3
I I
• (a) CH3-CH-CH20H ----7 CH3-C=CH2
OH
I
(b) CH3-CH-CH20H----7 CH3-C-CH3
I I
CH3 CH3

(c) C)< CH
OH3
. O::CH
" ""OH
3

(d) (rC CH
OH3
.. CH3 - C -
11
(CH2)4 - CHO

(e) O = C H2 .. o - C H2-Br

0
11
(f) O=CH-CH3 " O - C - C H3

CH20H CHO
(g) ..

(h) CH3-(CH2)4-C=CH ----7 CH3-(CH2)60H


2. Give the product of each of the following reactions:
108 UNDER GRADUATE ORGANIC CHEMISTRY

CH3
I cone. H 2S04
(i)
(h) CH3-CH2-C--C-CH3 - - - 4 )
I I t1
OH CH3

3. Using the given starting material and necessary inorganic reagents and any carbon compound with
no more than two carbon atoms, indicate how the following synthesis could be carried out:

6 -" 0 "()CH,
OH

(al ~<5
(c) CH3-CH2-C==CH----7 CH3-CH2-C=C-CH2-CH20H
(d) CH3-CH-CH20H ----7 CH3-CH-CH2-CH2-CH20H
. I I
CH3 CH3
4. Propose a mechanism for the following reaction:

5. When the given seven membered ring alcohol is dehydrated with conc. H2S04' three isomeric alkenes
are formed. Propose a mechanism for their formation.

6. Indicate how each of the following compounds could be prepared using given starting material:

(alO -
ALCOHOLS 109

(d) Y'" -
OH
Y'"
D
7. Propose a mechanism for the following reaction:

(d)4.. CH 2-CH 2-CH 2-Br


U o CH2-O-CH3

8. Propose a mechanism for the following reaction:

9. Outlined below is a synthesis of the gypsy moth sex attractant (E). Give the structure of (E) and the
intermediates A-D in the synthesis.

10. Synthesise the compound shown below from methylcyclopentane and 2-methyl propane using these
compounds as the source of the carbon atoms and any other reagents necessary. Synthetic tools you
may need to use could include Markownikov or anti-markownikov hydration and
dehydrobromination, radical halogenation, elimination and nucleophilic substitution reactions.

r--<CH 3

VIIIIIIO~
11. The alcohol shown below is used in making perfumes. Outline a synthesis of this alcohol from
bromobenzene and I-butene.

12. Show how a Grignard reagents might be used in the following synthesis.

~OH _
~OH
13. Use Grignard synthesis to prepare the following compound from I-bromo-4-hydroxymethyl
cyclohexane and any other reagent necessary.

TTA.
110 UNDER GRADUATE ORGANIC CHEMISTRY

14. Starting from glycerol how will you obtain the following:
(a) Acrolein (b) Allyl alcohol (c) Dichloroacetone
(d) Formic acid (e) Isopropyl alcohol (d) Tartonic acid
15. Arrange each of the following four series of compounds in order of increasing reactivity towards
Lucas reagent. If two or more compounds are expected to have comparable reactivity, indicate that,
OH
I
(a) (CH3)zCHOH; (CH3hC-OH; CH3-CH2-CH-CH3; CH3-(CH2h-CH20H
(b) (CH3hC-OH; CH3-CH2-OH; CH3-0H;
OH

CH3-CH2-CH2-CH-CH3
I
16. Indicate how the following transformations can be carried out in good yield.
(a) 2-Propanol ) n-propanol (b) 2-Propanol ) n-propyl iodide
(c) I-Butanol ) 1, 2-butanediol (d) i-Butanol ) i-Butene
17. Explain each of the following, using structural formulae and equations as needed.
(a) Ethanol is soluble in water, whereas propane is insoluble.
(b) Ethanol boils at a much higher temperature than propane (bp -42°C).
(c) Benzyl alcohol, reacts instantly with Lucas reagent even though it is a primary alcohol.
(d) Tertiary alcohols react less readily with Na while they react more readily with HX, as compared
to primary alcohols.
18. Vinyl alcohol (CH2=CHOH) is unstable and spontaneously forms acetaldehyde. Suggest a
mechanism for this reaction.
19.-:ompollnd (A) C6H1202 on oxidation with periodic acid followed by oxidation with permanganate
gave adipic acid. What is the structure of A? Explain the reactions.
20. Indicate the products or reactants, as required, to complete the following reactions:

(a)
cS
• K(metal)
?

?
OH OH
? I I K2Cr207/HEil
(b) CH3-CH=CH-CH3 ----») CH3-CH-CH-CH3 ) C4H602
E

(c)

? ?
(d) CH2=CH2 ~ HOCH~CH2Cl ~ CH2=CHCI

/O
-, e
OH " Hl0
4
(e) L-.:::.. ------7? )?
H2 0

21. Provide starting material A which will lead to the i icated product in the following reactions:
ALCOHOLS 111

OH OH CH3
(i) CH3MgBr I (i) CH3Li I I
(a) A ) CH3-C-CH2CH3 (b) A---~) CH3-CH-CH-CH3
(ii) H 20 I (ii) H 20
CH3
OH OH

(c) A
(i) MglBenzene I I
) Ph-C-C-Ph
(ii) H20 I I
Ph Ph
o
aq. HI04 "
(e) A --~) 2CH3-C-CH3 (only)

ABSWERS TO VERY SHORT ANSWER QUESTIONS

o
1. (a) CH3CHO (b) CH3=CH-CHO
CH 3
(c) Co)
I
H-C-OH
(e) I + enantiomer
HO-C-H
I
d/ mixture
3. (c) 4. (c) 5. (c) 6. (a)

6
OH
LiAlH4
7. RCOOH-----7) RCH 20H 8. (a)

9. Because of + I effect of alkyl groups, the electron density on the hydroxylic oxygen increases in
alcohols which decreases the electronegativity of oxygen and makes alcohols weaker acid~ than water.
e e
10. CH30H < H 20 < OH < CH30 11. Aqueous HI04 or Pb(OAc)4
12.
. CH2-OH Pt + 12
(1) I • [ClH2-I] __-...;;12__ CIIH2 r

CH2-OH CH2-1 CH2


Unstable Ethylene

(ii) I
CH OH

CHzOH
2
2 mole HI
• [fH2 1
- ]
CH 2-1
-12

CHry
11
CH 2
-

~2 mole HI

[f
H2 1
- ]
CH2-1
-12

CH 2
11
CH2
HI

CH3
I
CH 21
112 UNDERGRADUATE ORGANIC CHEMISTRY

Ni
13. CH3CH=CHCHO + 2H2~ CH3CH2CH2CH20H
CH3CH=CHCH20H cannot be isolated because a C=C bond is reduced faster than C=O.
14. Acid catalysed dehydration of a1cohols occurs through intermediate formation of carbocations. Since
tel1-butyl carbocation is more stable and forms faster than n-butyl carbocation, theretore,
acid-catalysed dehydration of tert-butyl alcohol is faster than n-butyl alcohol.
The above reaction proceeds through SN2 mechanism which is always accomparied by inversion of
configuration.

15.

B~~'cnH --. Br-c(.~\D


,. 2 "
H3C CH 3
Inversion of configuration
16. (b)
rc~-'--~
LOLUTIONS OF PR=--:.::::J
8
1. OH being a stronger nucleophile than Br8, the latter cannot displace the former. H2S04 protonates
El1
ROH to form R-O-H. H20 being a weaker nucleophile than Br8, it is easly displaced by the latter.
I
H
•• El1 El1
(i) R-O-H + HEl1 ~ R-O-H (ii) R-O-H + Br8 ~ R-Br + HOH
•• I I
H H
If R is tertiary alkyl group, it will follow the SN 1 pathway; if it is primary one, the SN2 reaction will
occur.
2. When an alcohol and thionyl chloride react, an alkyl chlorosulphite and HCI are formed as usual.
Pyridine is a base and reacts with HCI to form pyridine chloride salt.
Chloride ion from the salt then attacks the involved carbon atom of the alkyl chlorosulphite from the
back since it is strong and free nucleophile.
RI RI 0
I I 11
(i) R-C-O-H + SOCl2 ~ R-C-O-S-CI + HCI
I I
R2 R2

(ii) ,0 .0
~ + HCI ---+ I(+~
,~CI
e

1
H
~RI 0 RI
e \1 1 Slow step 1 e
Cl + R-YU-S-CI • CI-C-R
I
+ S02CI
ALCOHOLS 113

Since the TS of the slow step involves Cl 8 and the alkyl chlorosulphite, the rate of the reaction
follows the second order kinetics and the reaction follows the SN2 path. Naturally inversion of
configuration occurs.
OH Cl
I S02CI I
3. (a) CH3-CH-CH2-CH 3 .. ) CH 3-CH-CH 2-CH3
Pyndme

(i) BH3 e
1 (CH3hCOK

(ii) H20:zl0H
CH3-CH2-CH2-CH2-OH • CH2=CH-CH2-CH3

AIP3/~
(b) CH3-CH2-CH2-CH20H--~) CH3-CH2-CH=CH2

I
(i) Hg(OAc)2
(ii) NaBH4

OH
I
CH3-CH2-CH-CH3
OH
(i) Hg(OAc)2 I
(c) CH3-CH-CH20H ) CH3-C=CH2 ) CH3-C-CH3
I I (ii) NaBH4 I
9H 3 CH3 CH3
CH3
I conc. H 2S04 (i) BH3
(d) CH 3-C-OH----t) CH3-C=CH2 ) CH3-CH-CH20H
1
~ I
(ii) H 20 2/0H0 I
CH3 CH3 CH3

o
K2Cr20iHEll NH,/il 11
(b) CH3-CH2-CH20H----4) CH3-CH2-COOH---~) CH3-CH2-C-NH2
IBr2/KoHl~
NaN02/HCI
CH3-CH20H ( CH3-CH2-NH2
or
conc. H2S04 (i) 0,
CH3-CH2-CH20H ) CH3-CH= CH2 -) CH1CHO + CH 20
~ (ii) Zn/HOH -

1NaBH4
CH3-CH2-0H
114 UNDERGRADUATE ORGANIC CHEMISTRY

5. (a) HO-CH2-CH2-Q2-CH2----.HOCH2 -CH2-~_-CH2-CH2-8


.. :-..... /
CO 1
I...)
H

® e e® N
NaO-CH2-CH2-0-CH2-CH2-0Na~ HO-CH2-CH2-O-CH2- CH2-OH
1 CH3I (A)

CH3-0 - CH2- CH2-O -CH2- CH2-O - CH3


(B)
Diglyme; used as solvent

(b)

RCOOOH /0, HBr


(C) CH3-CH=CH-CH3 ) CH3-CH--CH-CH3 -~) CH3-CH-CH-CH3
(A) I I
Br OH
(B)

(d) CH3-CH-CH-CH3 CH3-CH-CH-CH3


I I ...... 0 .....
OH Cl (B)
(A)
CH3-CH-CH-CH3 CH3-CH-CH-CH3
I I I I
CH3 OMgBr CH3 OH
(C) (D)

CH3
I
6. (a) CH3-CH-C-CH2CH3
I I
OH OH
CH2CH3
I / C 6H5
(c) C6H5-C-C~
I I
OH OH
C6H 5

7. (a) Racemic chloride because the reaction proceeds through a carbocation (SNl);
(b) Retention of configuration (SNl); (c) Inversion of configuration (SN2)
ALCOHOLS 115

8. (a) 8(A) (B)

o OH OH
11 1 1
Cb) CH3-C-CH3 Cc) CH3-C-C-CH3
(A) I I
CH3 CH3
(8)
Cc) CH3-CH=CH2 H3C-CH-CH2 CH3-CH-CH2
(A) I
OH
I
OH
(C)
(d) It is an example of hydroboration of a nonterminal double bond. The alkylborane so formed
changes to terminal alkylborane by contrathermodynamic isomerisation because of steric reasons.

B
H H
(A)
CH3CH2CH2CH2 --7 CH3CH2CH2CH20H
1 (C)
B
H H
(8)

~ ~
9. (a) U"-' U (b)
JvPh
~Ph (c) CP 0 1h
(d) Ph-?-C-MC
Ph
o
~Ph
(e) U .. Ph

COOOH

10. Ca)

o _~~B~r~ cJo
116 UNDERGRADUATE ORGANIC CHEMISTRY

11. (a) 2-Butanol can be prepared from I-butene or 2-butene as follows:


OH
CH3-CH2-CH=CH2 (i) Hg(OAch I
or ) CH3-CH-CH2-CH3
CH -CH=CH-CH (ii) NaBH4
3 3
(b) I-MethyIcyclohexanol can be prepared from methylenecyclohexane or I-methylcyclohexene.

C)=CH2 or o - C H3

j (i) Hg (OAch
(ii) NaBH4

/ V OH
~CH3
(c) Cyclopentylcarbinol can be prepared from methylenecyclopentane as follows:

12. Hydration of 3-phenyl-l-butene takes place as follows:

® ®
CH3 -CH-CH-CH 3 CH3- C- CH2 -CH3
I I (3°benzyl carbocation)
C6HS C6Hs
~HOH
OH
I
CH3-C-CH2-CH3
I
C6H S

Although phenyl is a better migrator than H, migration of H occurs leading to a more stable 3D -benzyl
carbocation.

ODD
3.0 Introduction

Phenols are aromatic compounds containing hydroxyl group/groups directly attached to the aromatic
nucleus. According to the number of hydroxy groups present, the compounds are termed as
monohydric, dihydric, trihydric and polyhydric phenols.
3.1 Nomenclature
he simplest member of the series is called phenol. Phenol derivatives are usually named as
Tderivatives of this parent compound.

@ @rCI
OH OH OH

Phenol o-chorophenol
(2-chlorophenol)
c$JN02
p-nitrophenol 4-chloro-2-nitrophenol
(4-nitrophenol)
If more than two groups are present, then numerals are used

c$YCHl
Cl
4-chloro-2-methylphenol 3, 5-<1ichlorophenol

Most of the phenols are known by their trivial names, e.g.,

CH3

c&0H
a-cresol
©tOH
m-cresol
$ OH
p-cresol
118 UNDERGRADUATE ORGANIC CHEMISTRY

OH OH OH

@J 0H

©lOH c$JOH
Catechol Resorcinol Hydroquinone

OH

©t
Pyrogallol
0H

OH
HO~OH

OH
Phloroglucinol

3.2 Methods of Preparation


3.2.1 From coal-tar: The middle oil fraction of coal-tar contains phenol and cresols in addition to
other compounds. This fraction is treated with alkali. The alkaline layer is separated and carbon dioxide
gas is bubbled through it. The mixture of phenols that separates out is subjected to fractional
distillation to isolate individual phenols.
3.2.2 From aryl halides: Aryl halides when heated with NaOH at high temperature and
pressure give phenols. This is an important industrial method for the production of phenol.
Cl OH

~+
l8J NaOH !.,"","=,
(ii) HEt">
~
l8J
3.2.3 From sulphonic acids: Fusion of an aromatic sulphonic acid with NaOH at 300°C gives
the corresponding phenol in good yield.
e @

.@a_H@-+.~
3.2.4 From diazonium salts: Hydrolysis of diazonium salts in acidic medium gives
corresponding phenols.
OH

@
3.2.5 From phenolic acids: Wh~n phenolic acids are heateG with sodalime they undergo
decarboxylation to form phenols.
OH OH

~COO:
l8J NaOHlCaO _t.--+.
Sodalime
~.
l8J
PHENOLS 119

3.2.6 From isopropylbenzene (cumene): This is the most important commercial method for
the preparation of phenol, and is known as cumene-phenol process. In this method cumene is oxidised
to its hydroperoxide, which is then decomposed by acid into phenol and acetone (which is sold as a
by-product).

C~s C~s
~ I ~~ I $
C6HsCH(CH3h e ) (CH3hC-O-OH - - - - + ) (CH3hC ~ 9-0H2
Cumene OH,1300C lOO°C_

I-H,o

3.3 Physical Properties


(i) Pure phenols are colourless liquids or low melting solids. They turn pink or red on exposure to
air and light due to oxidation. All phenols have a peculiar carbolic odour. Phenols have higher boiling
point and solubility than corresponding a1cohols of comparable molecular weights. The higher boiling
points and solubility are explained by the higher polarity of O-H bond and consequent stronger
intermolecular hydrogen bonding in phenols relative to a1cohols.
Mol. Wt. mp (QC) bp (QC) Solubility

Phenol 94 43 182 9.3 g/l00 g of H20


n-hexanol 102 -52 157 0.59 g/100 g of H20
CycJohexanol 100 25 161 3.6 g/l00 g of H20
3.4 Acidic Character
Alcohols and phenols both possess acidic properties (reaction with electropositive metals).
ROH + Na ) ROE>Na$ + t H2 ... (i)

Ar-OH + Na ) ArO~aEB + t H2 ... (ii)


But phenols are more acidic than alcohols. Phenol turns blue litmus paper red and forms sodium
salt with NaOH, whereas a1cohols do not give these two tests.
C6HSOH + NaOH ~ C6HsOE>Na$ + H20

R-OH + NaOH ~ RO~a$ + H20


This is indicated by the order of acidity constants of phenols (pka is about 10).
In phenols the hydroxyl group is directly attached to an aromatic ring, allowing resonance
interaction between a lone pair of electrons on oxygen and the aromatic 1t cloud (Fig. 3.1). Due to
this, the ring becomes more negative and the hydroxyl group more positive. Because of this resonance,
the O-H bond is more polar in phenols than in alcohols and consequently more acidic.
120 UNDERGRADUATE ORGANIC CHEMISTRY

~H (a)

(b)
III

/1-
(c)
Fig. 3.1 (a) Bonding picture (b) Resonance forms (c) Resonance hybrid

p-Orbital of oxygen (which has lone pair of electrons) overlaps the 1t cloud of benzene ring.
This strengthens the C-O bond, which is, therefore, more difficult to break. In addition, this
resonance makes the ring more negative and polarises the O-H bond.
Besides examining the reactants, we should also examine the products (equations (i) and (ii») in
order to fully explain the acidity of phenols.
The salt of phenol is a negative phenoxide ion, whereas the salt of an alcohol would be a negative
alkoxide ion.

Phenoxide ion Alkoxide ion


Due to resonance, the phenoxide ion is more stable than the alkoxide ion. The negative charge
is delocalised over the entire molecule. On the other hand, in the alkoxide ion, no resonance is possible
and the negative charge is localised on a single oxygen atom (Fig. 3.2).

~e (a)

&. ,()"~.·6~·,"6 -[~J


(b) (c)
Fig. 3.2 (a) Bonding picture; (b) Resonance stabilisation of phenoxide ion; (c) Resonance hybrid
PHENOLS 121

This delocalisation of the charge


stabilises the phenoxide ion to the greater
extent than the phenol itself, and thus
shifts the ionisation equilibrium to favour
the formation of anion, i.e., the phenoxlde
ion. The phenoxide ion is more stabilised ·ArC8
by resonance than the phenol itself E
because in the former dispersal of the
same charge (negative) takes place while i Extent of resonance stabilisation
- __--r- of phenol as compared
in the latter separation of charge occurs. I to alcohol
The stability of phenoxide ion and ArCH
alkoxide can be shown by the Fig. 3.3. Reaction coordinate
3.4.1 Effect of substituents on Fig. 3.3
the acidity of phenols
The acid strength of phenols is affected considerably by the presence of substitutents on the ring.
Electron-withdrawing substitutents (such as -N0 2 , -eN. -S03H, etc.) particularly in the arrha
and/or para pOSItions enhance the acidic character of phenols whereas electron-donatmg groups
(-OH, -NH2' etc.) suppress the acidic character of phenols. The electron-releasing groups destabilise
the anion relative to phenol due to +1 or +R or both effects. This makes the compound less acidic
than phenol. The electron-withdrawing group assIsts the delocalisauon of negatIve charge by -I or
-R or both effects. Thus anion is more stabilised than the phenol.
The following illustrates thIS relative effect, compared with phenol as the standard:

:O-H :OH

~ @
G Jf Jf
&9

~~ +H

Phenol: standard
e
~+~ G
G No special stability G-electron-donating group,
G-electron-withdrawing or instability such as R-, Ar-, RC--
groups, such as -N0 2,
e G makes anion less stable
-X, --CHO, NR3 due to donating electrons
G makes anion more to negative charge
stable due to affinity
of G for electrons

In some cases the phenols having electron-withdrawing substituent at the artha position are
weaker acid than the para isomer. In these cases the acidic hydrogen is involved in the formation of
intramolecular hydrogen bonding with electronegative element, like fluorine or oxygen.
122 UNDERGRADUATE ORGANIC CHEMISTRY

H3COF O-~

< ~.
no intramolecular
I
Intramolecular
hydrogen bonding §
hydrogen bonding,
stronger aCId
Weaker acid
F
O/H /////

6-
~;oe
Intramolecular
hydrogen bonding
I '\ < QH
§ 0
no intramolecular
hydrogen bonding,
stronger acid
Weaker acid
N02
'6':"*,' The acidity constants of some phenols

Ka(H20) x 10-10
Compound Structure
(at 25°C)

Phenol
@-OH J.3

p-Nitrophenol 690

0- Nitrophenol 600

m-Nitrophenol 50

NH2
0- Aminophenol d
\QjOH
2.00

m-Aminophenol 69

@-OH
p-Aminophenol
HN-@-OH
2

o-Fluorophenol F

@-OH 1.5
PHENOLS 123

Ka(H20) x 10-10
Compound Structure
(at 25°C)

F
m-Flurophenol
@-OH 5.2

p-F1uorophenol 1.1
F-@-OH

0.63
o-Cresol

@-'
o OH

m-Cresol 0.9

@-OH
0.62
p-cresol
CH3-@-OH

OH
Catechol @rOB 1.0

OH

Resorcinol
~B OH
3.0

~
Hydroquinone 2.0

OH

o/
OH

2, 4-Dinitrophenol N0
1000000
2

N02
124 UNDERGRADUATE ORGANIC CHEMISTRY

Let us discuss the acidity of some monosubstituted phenols:


3.4.2 Acidity of nitrophenols
Nitro group has a powerful -I as well as -R effect, therefore, irrespective of the positi4ln of
the nitro group, all nitrophenols are stronger acids than phenol because electron withdrawing group
increases stability of substituted phenoxide more than the phenoxide ion. Although inductive effect
(-I effect of -N02) decreases with distance, -R effect is pronounced at arrha and para positions.
Thus acidity of nitrophenoIs" increases with respect to phenol due to inductive as well as
resonance effect.
0- Nitrophenol e
OH o
&N02~
O
NO
~ 2 ID
I h
+ H

e
o
$,0
&I ~ N,e
h

group decreases
magmtude of negative
0
Inductive effect of nitro

charge and hence


o 0 e
increases stability of
e,O 6=$/0
anion.

Or
I e N,e ..... I
h 0
(2) Especially stable
due to unlike
h
N,
(5)
0
e
Resonance stabIlised

t charges adjacent to
one another
structure. negatIve
charge delocahsed
over nitro group
0 $,0

6-N,g
I I
e
(3)
Resonance structures (3) and (4) have comparable stability because in each the negative charge
is on the carbon bearing a hydrogen. Structure (2) is specially stable because of the adjacent positive
and negative charges on nitrogen and carbon respectively; an additional resonance structure (5) can
be drawn to show how that negat~ve charge can be dilocalised over larger area of the molecule due
to the nitro group.
This extra resonance stabilisation (structure 5) explains the a more acidity of a-nitrophenol over
phenol. Thus acidity of a-nitrophenol is enhanced by -I and -R effect of nitro group.
e
o

9
p- Nitrophenol

+ ~
N0 2
PHENOLS 125

e
o

N
o~S'0
(6)
e (7)

Inductive effect of
nitro group decreases
magnitude of negative
charge and thus increases
stability.

N
o~s'0
e
(8)
Especially stable
due to unlike
charges adjacent to one another

to

Q/N,
0$0
e e
(10)
Resonance stabilised
structure, negative
charge delocalised over
larger area of molecule

Thus acidity of p-nitrophenol is enhanced by inductive as well as resonance effect.

m-Nitrophenol
OH

0 .. Ne
"-o
0

e
126 UNDERGRADUATE ORGANIC CHEMISTRY

e
o

6. N-O
11
e

o
Inductive effect of nitro
group decreases magnitude
of negative charge and thus
o

0.;0'0
stabilises anion

e N
(13)
e

Structures (12), (13) and (14) have comparable stability because in each the negative charge is
present on carbon bearing a hydrogen.
• It is evident from the above resonating structures that both 0 and p-nitrophenoxide ions are
stabilised by five resonating structures. In one of the structures in each case [(5) and (10)]
delocalislltion is extended upto oxygen atom of the nitro group. No such resonating structure is
possible for m-nitrophenoxide ion. Similarly, structure (2) and structure (8) are specially stable due to
unlike charges are present on adjacent atoms.
Thus anion of m-nitrophenol is the least stable. Thus acidity of m-nitrophenol is less than the
o and p-nitropheno}s.
Accoding to inductive effect anion of o-nitrophenol is more stable than the p-nitrophenol. Thus
according to inductive effect o-nitro phenol should be more acidic than the p-nitrophenol.
Experimentally it has been found that p-nitrophenol is little more acidic than the o-nitro phenol. This
experimental result can be explained by intramolecular hydrogen bonding. Intramolecular hydrogen
bonding in o-nitrophenol makes loss of a proton little more difficult. Thus, the acidity of nitrophenols
relative to phenol in decreasing order is as follows:
p-nitrophenol, o-nitrophenol, m-nitrophenol, phenol
Further greater the number of electron withdrawing groups at 0- and p-positions, more stable IS
the phenoxide ion and hence more acidic is the phenol. Thus 2,4,6-trinitrophenol is more acidic than
2,4-dinitrophenol which is more acidic than 2 or 4-nitrophenol.
3.4.3 Acidity of cresols
Methyl group is electron donating inductively from all positions. Thus three isomers are weaker
acids than phenol. m-cresol is the strongest beacuse its acidity is not weakened by hyperconjugation
PHENOLS 127

OH OH OH

@-CH ©-CH 3

o -cresol c9J
I
m-cresol
3

p-cresol

whereas that of 0- and p-cresol is weakened by hyperconjugation. Out of ortho and para cresol,
p-crosol is more acidic than o-cresol due to inductive effect.
o-cresol

(i
+ H

e e
o

[04-H
H 0

++ 6'CH2~
(\) (2)
Anion is destabilised Especially unstable due
by inductive effect to like charges adjacent
of methyl group to each other: hyperconjugation
of -CH3 group destabilises anion

Thus acidity of o-cresol is decreased due to the + I effect and hyperconjugation effect.
p-cresol

+ H •
128 UNDERGRADUATE ORGANIC CHEMISTRY

e
o e e e

H-C-H
I
[H~H-~;~~~
H
I (6) - (7) -
EspecIally unstable due to like
H (5) charges adjacent to each other;
Inductive effect of
methyl group increases
magnitude of negative
t
hyperconjugation destabilises
anion

charge and destabilises


anion.

eQ. CH 2H
(8)

Thus acidity of p-cresol is descreased due to +I effect and hyperconjugation.


m-cresol
e
o

ollACH ollACH
OH

+ H •
e 3 3
o

Ii:
U C H3
Inductive effect of methyl group (9) H
increases magnitude of negative
charge and destabilises anion
e
o

~CH2~
e
(12)

Anion of 0- and p-cresols are more destabilised by hyperconjugation than the anion of m-cresol.
Especially one very unstable resonating structure [structure (2) and (7)] is pOSSible in these two cases.
This type of structure is not pOSSible in m-cresol because methyl group is not at the conjugate position
with respect to the -OH group.
PHENOLS 129

Thus m-cresol is the most acidic among 0, m and p-cresols. Among 0 and p-cresol. the anion of
p-cresol is more stable than the o-cresol because of the + I power of methyl group which depends on
the distance. Thus the order of acidity in decreasing order is as follows:
m-cresol, p-cresol, o-cresol
3.4.4 Acidity of Halo phenols
Although halo group is electron-donating by resonance, its electron-withdrawing inductive effect
predominates over the + R effect. Therefore, all halo phenols are more acidic than phenol. Since -I
effect decreases with distance, therefore, acidic strength of halophenols in decreasing order is as
follows:
o-halophenol, m-halophenol, p-halophenol
In case of p-fluorophenol, + R effect and - I effect of fluoro group balance each other and hence
it is almost as acidic as phenol itself.
Acidity of different o-halophenols in decreasing order is as follows:
o-chlorophenol, o-bromophenol, o-iodophenol, o-fluorophenol
This is because -I power of Cl is more than the Br which is more than the I.
Amongst o-halophenols, o-fluoro phenol is weakest due to the strong intramolecular hydrogen
bonding.
3.5 Chemical Reactions
3.5.1 Ester formation (acylation): Phenols form esters by the action of acetic anhydride or
acid chloride. This reaction is catalysed by base.

~ + (CH,CO),O B",. ~OCH'


The mechanism of the reaction is as follows:

6+8H ~~ +H,O

+
O'
HOH 11 e
. " - - CH3 C - O
The phenolic esters are converted into 0- and p-hydroxy ketone in the presence of anhydrous
aluminium chloride.
OH OH
&COCH3
~L8J +
c$J
130 UNDERGRADUATE ORGANIC CHEMISTRY

This reaction is known as Fries rearrangement. Generally, low temperature favours the
formation of p-isomer and higher temperature favours the o-isomer.
OH

@_CH_3----1
161l'C ~COCH'
OH

~
60·C

COCH 3
The exact mechanism of the Fires rearrangement is somewhat uncertain as it is sometimes a
one-step and sometimes a two-step process.
Mechanism of two step process
First step
e
AICl3 .
.0AIC13 I
o O~ e
<\.\ //~. 'oCII-CH, =
;~==~ ~ .....
< #~ "'COCH,
--+ ~
OO-AICI
#
3
EEl
+ CH3CO
Second step

This mechanism is supported by the following facts:


The two different esters (I) and (HI) give the rearranged product (II) and (IV).

OH
CI'$COCH' Mh
Y
;C1, CI~COCH3
.~
CH3 CH3
(I) (II)
PHENOLS 131

~"'5
OH

mhY.A1C1, • ~COC"'5
CH3 CH3
(Ill) (IV)
Rearrangement of a mixture of (I) and (Ill) gives cross products (V) and (VI) also.
Isolation of crossover products confirms that the rearrangement is intermolecular.
OH OH .
C~COC6H5 ~COCH'
(I) + (Ill) ---+. (11) + (IV) + ~ +

CH 3 CH 3
(V) (VI)
One step (intramolecular) mechanism:

e~+
CI3AI_o
<.:. W
-CH
3
et)
~ICI3
e

'I b
---~ U~OCH3
1- H
"
e

o-tH'
O-AICI3

_Cia

Photo-Fries rearrangement: Fries rearrangement can also be carried out in the presence of
UV light in the absence of a catalyst, then this is called photo-Fries rearrangement. It involves the
following mechanism:

·[0' ~-al-+&rH
o
0
0
~-R
+
6I I

O
I b
so1vent cage
tautomerisation

1
R-C=O
l' .
H

tautamensatiOn

&-R ~
C=O
I
R
132 UNDERGRADUATE ORGANIC CHEMISTRY

The free radicals fonned are held in a solvent cage and they are not free to move far apart. The
attack of the acyl radical takes place at ortho and para positions to give the product. The ortho product
predominates at high temperature.
3.5.2 Alkylation: Formation of phenolic ethers takes place when phenols are treated with alkyl
halides or alkyl sulphates. The reaction is catalysed by base.
OH O-R

@ +R-X 8H. @ + HX

This reaction takes place as follows:


6
OH 0 \ O-R

~_8H--.. ~ .L} .~ +XS


l8J l8J x = halogen
or
l8J
-O-SOz-OR group
Examples:
OCH3

8H • @ +CH,-O-So,OH

Anisole or methoxybenzene

OCzH s

8H • @ +C,R,-O-SO,OH

phenetole

When phenol is treated with allyl bromide in the presence of NaOH fonnation of aryl allyl ether
takes place.

lIH • ~ CH,-CH~CH,
OH

@ B,H,c-CH~,
+

AlIylphenyl ether (Allyl


ether of phenol)
PHENOLS 133

Claisen rearrangement: Allyl ether of phenol, rearrange to o-allyl phenol when heated at
zoooe.
~ CH2-CH~CH2

This rearrangement is known as Claisen rearrangement. If ortho position is free, only ortho
rearrangement occurs. However, if both ortho positions are substituted, rearrangement takes place at
para position.
OH
CH
200·C CH* 3

CH2-CH=CH2
4-Allyl-2,6-dimethylphenol

The Claisen rearrangement is an intramolecular rearrangement as evidenced by heating a mixture


of ethers (i) and (ii), having two different allyl groups, where no cross products (v) and (iv) are
obtained.

(ii)

OH

OO-CH2-CH~H2
(Hi) (iv) )

OH

~;-CH~CH2
(v) (vi)
(not fonned) (not formed)

An interesting feature of the rearrangement is that when migration takes place at the ortho
position, the y-carbon of allyl group attaches itself to benzene nucleus. In other words, there is
inversion of the allylic chain. However, no such inversion of allylic chain takes place with p-migration.
134 UNDERGRADUATE ORGANIC CHEMISTRY

Cl J3 y

~CH'-CH~H-CH' "

reversal of allyl group ~.

L§r OH
0-CH2-CH=CH-CH3

H3
c CH
3
O b.

H'Co/CH'

CH2 - CH =CH-CH3
OH

H'C~CH'
LY CH 2-CH=CH2
14

Mechanism: On the basis of the above facts the mechanism can be represented as follows:
Ortho migration:
CH 2
CcH
6-' ,
OH
o
I
U *" H2 -+ (d-;I CH,-CH~CH,
H
*
-+
~
*CH -CH=CH

Para migration:

1
PHENOLS 135

The above mechanism indicates that the overall para migration takes place in two stages.
3.5.3 Formylation: Gattermann Reaction: When phenol is treated with a mixture of
hydrogen cyanide and hydrogen chloride in the presence of anhydrous aluminium chloride. an
aldehydic group is introduced in the para position to -OH.

c£ +H-C=N+HCl AlCI
3

CHO
• ~
If para position is blocked then -CHO group goes to ortho position.
This reaction is electrophilic aromatic substitution reaction and proceeds as follows:
Cl
I
H-C=N+HCI ~ H-C=NH
Imidoformyl chloride
H H
I I
HN=C-CI + AICl3 :;,,==='>-~ HN-C·_····_··CI········-AICI3
6+ 6-

Ji
® e
HN=CH + AlCl 4
e ®
OH 0 AlCh

6~# 6~
+ AICl3 - - +... . - , / ,

CgfIC1, ~ OH
Q .Q+
OH

QJ=NH-~ • H,O NH
3

H CH NH CHNH CHO
Aldimine
3.5.4 Houben-Hoesch reaction: This is the extension of Gattermann synthesis and involves
acylation of highly reactive polyhydric phenols. When a polyhydric phenol is treated with an alkyl
cyanide and hydrogen chloride gas in the presence of anhydrous ZnCl2 or Alel3. ketimine
hydrochloride is formed. which on hydrolysis with hot water gives acyl derivative of phenol. Acyl
group is generally introduced at ortho position with respect to the -OH group.
OH OH 0

~ + CH,--C=N + HCl _. ~~-CH'


HO~OH HO~OH
136 UNDERGRADUATE ORGANIC CHEMISTRY

Mechanism:

CH OH CH
HI3 ~13
C=NH ~ I ~ C=NH
HO ~ OH

3.5.5 Kolbe-Schmitt reactio: When phenoxide is heated with carbon dioxide under pressure,
a carboxylic group is introduced arboxylation) in ortho position to the -OH group. This reaction
is known as Kolbe-Schmitt react on.
e

6+ ~C~O
o OH

A. 6-c(~e
At lower temperature the art 10 isomer predomina~s whereas para isomer is obtained at higher
temperature.

3.5.6 Reimer-Tiemann reac ·on: When phenol is refluxed with chloroform in the presence of
base, ortho-hydroxybenzaldehyde is formed. Small amount of p-isomer is also obtained. This reaction
is known as Reimer Tiemann reaction.
OH OH

@
o + CBC!3
(i)
(ii)
e
OH
H® •
@-CHO
major product
+

CHO
minor product

Similarly, when phenol is heated with carbon tetrachloride 0- and p-hydroxybenzoic acids are
obtained.
OH OH OH

~
@+CC4 (t)
(n)
e
OH
H
®. @-COOH +
major product
COOH
minor product

(a) Reaction with chloroform: The reaction is base catalysed condensation of chloroform with
phenol. The reaction proceeds via electrophilic attack of dichlorocarbene on a phenoxide ion.
PHENOLS 137

6~ HO 6 -Cl6
(i) OH + H \JCl3 - 2 • CCl3 • :CCl2
dichlorocarbene

(ii)
3->
I ~ + :CCl, •
(.0
a~C12
~ 6
+H
$
6-
•I
OH

~ <Cl
CH Cl

06

6-~
OH

(iii)
6c
I~n0
6H
OH
Cl
-Cls
• 6cF~?
~ (Q;H
• I: C-H

(b) Reaction with carbon tetrachloride: In this reaction carbon of carbon tetrachloride is
electron deficient (due to -I effect of four Cl), and behaves as a neutral electrophile. The mechanism
is as follows:

OH 06

Ac(° ~ ff> A-c(0 4

VOH V OH
Salicylic acid

3.5.7 Coupling with diazonium salts: Phenols couple with diazonium salts in alkaline solution
to form hydroxyazo compounds. Coupling reaction takes place at p-position. If p-position is
substituted, coupling may occur at o-position.

6
@-N@=NCI +H-@-OH OHS.@-N=N-@-OH

p-hydroxyazobenzene

3.5.8 Condensation with formaldehyde: Phenol reacts with formaldehyde (40% aq.
formaldehyde) in the presence of dilute alkali or acid to give a mixture of 0- and p-hydroxybenzyl
alcohol. The main product is always p-isomer with small amount of o-isomer.
OH OH OH

@
o
@-
o
~
11 NaOH. CH 0H
+H-C-H + 2

CH20H
major product
138 UNDERGRADUATE ORGANIC CHEMISTRY

This reaction is known as the Lederer-Manasse reaction. Its mechanism may be as follows:
(a) Base catalysis

(b) Acid catalysis


(£) (£) (£)
(i) CH2=O+H ~ CH2=OH ,.. ~ CH2-0H

(ii)
~H'-OH_~ ~Q H CH20H CH20H
In the presence of excess amount of formaldehyde this reaction does not stop at this stage.
Phenolic alcohol condenses with formaldehyde to give bishydroxy-methyl-phenol and
p, p'-dihydroxy-diphenyl-methane.

OH

@ 2HCHO ~

OH

2 @ +HCHO----+ HO--@-CH,--@-OH

Such condensation is repeated and finally polymeric product Bakelite resin is obtained.
PHENOLS 139

3.5.9 Condensation with phthalic anhydride: When phenols are heated with phthalic acid
or phthalic anhydride (2 : 1 molar ratio) in the presence of catalyst (Lewis aciu or conc. H2S04),
phthaleins are formed. This phthalein shows characteristic colour reaction in alkaline solution.
o 0
11 11

@C'o ©('o
C/ ~~~S04. ~c~
OH OH
Phenolphthalein
(Pink in alkaline medium)
OH OH
(xi) Reduction: Phenols on zinc dust distillation form the corresponding aromatic
hydrocarbons.

+ Zinc dust ---+.@+zno

3.6 Other electrophilic substitution reactions:


3.6.1 Halogenation: When bromine water is added to the phenol, 2, 4, 6-tribromophenol is
formed.
OH

+ Br2 / H 20 ---+~
b Br~O
~
Br

Br
If deactivating groups (-S03H, -N02, -eOOH) are present in 0- and p-positions to the
phenolic group, they may be replaced by halogen atoms.

Br~OH
OH

-co,.6-Br Br2
~
Br

Br
140 UNDERGRADUATE ORGANIC CHEMISTRY

QBr,lH,O+ ---+. BrVBr


Br
When bromination is carried ()ut at lower temperature and in the presence of nonpolar solvent
(CS2 or CCI4) 0- and p-bromophenols are formed.
OH OH

@-Br +c9J
Br
3.6.2 Nitration: At Iow temperature and with dil. HN0 3 phenol gives a mixture of 0- and
p-nitrophenols.

OH

"1 HNO,. 6-NO'


On treatment with conc. H2S04 followed by cone. HN03, phenol gives 2, 4, 6-trinitrophenol
(picric acid).

6 + oonc. H,SO, --+ & Q- * so': HNO, 02•


N
I
OH

N02
N0
2

The yields are generally poor due to loss by oxidation of phenols by HN03.
3.6.3 Nitrosation: Phenol undergoes nitrosation with nitrous acid (NaN02 + HCI) in the
para position.

Q N-OH
Quinone oxime

3.6.4 Sulphonation: Phenols react with conc. H2S04 to form a mixture of 0- and p-sulphonic
acid derivatives. At lower temperature main product is o-isomer whereas at higher temperature the
main product is p-isomer.
PHENOLS 141

OH OH OH

6 H2 S<4
lS-20"C
~ OSO'
I~
H +
Q
major product

'OO"ClH,SO, S03H
minor product

minor
product
QS03H
minorproduct

3.6.5 Friedel-Crafts alkylation: Phenol undergoes this reaction to form 0- and p-isomers.

+RCI
minor
product

-Hel ~
6
The yields are generally poor because phenol reacts with aluminium chloride to form salt.
0+ 0-
AIel,

This salt is less reactive than phenol.

VERY SHORT ANSWER QUESTIONS


1. Explain why phenol has higher b.p. than toluene?
2. What happens when phenol is heated with CCl4 in the presence of NaOH solution followed by
treatment with dil. HCI?
3. How is picric acid prepared?
4. Complete the following reactions:
OH

(A) ... Br2


water
~O ~dust~
lSJ Zn (B)

5. Write the structure of the phenol with molecular formula C7H80 which readity gives a precipitate of
C7HSOBr3 on treatment with Br2 water.
6. Phenol is an acid but does not react with sodium bicarbonate. Explain.
142 UNDERGRADUATE ORGANIC CHEMISTRY

7. Complete the following reaction and give the name of the reaction involved in the formation of
Band C from A.
OH
~ + C H COCI - - . (A)
LgJ AlCl
~ (B)
-C-S:2.;;:.:3.. + (C)
s 6

8. Phenol is a strong acid than:


(a) o-Cresol (b) Carbonic acid (c) o-Nitrophenol
9. Arrange the following compounds in order of thei,t increasing acidity:
phenol. cyclohexanol. p-bromophenol. p-methoxyphenol
10. Explain why 2.6-di-tert-butylphenol is a much weaker acid than phenol?
11. Arrange the following in increasing order of their solubility in water:
C6HsCH20H. C 2HsOH. C 6HsOH
12. Give the reagent to convert phenol into:
(a) Salicylaldehyde (b) Phenolphthalein
13. Explain why dipole moments of phenol (1.7 D) and methanol (1.6 D) are in opposite directions?
14. How will you convert phenol into quinol?
15. Predict the final product (Z) in the following sequence of reactions:
NaOH (ii) CO2/Pressure (iii) H3dll
p-Cresol - - - - 4 -----~) ) (Z)

PROBLEMS WITH SOLUTIONS


1. Complete the following reactions:

OH

(b)
©l NH2
---.;--=---...
(i) C02/NaOHlA
(ii)H3d~
(A)

(c)
6<: e
°2/0H/A
--=---+. (A) + (B)

2. Predict the products in the following reactions:


(i) NaOH
(a) p-cresol )
(ii) CO2, lOO°C'jressure
(iii) H 30
PHENOLS 143

e
OH
(C) p-bromophenol + (CH3hS04 ~
HzO
Br2/H20
(d) o-cresol.---~

HNO/H20
(e) p-chlorophenol . )
3. Arrange the following compounds in decreasing order of acidity.
phenol, cyclohexanol, p-bromophenol, p-methoxyphenol
4. What are the principal ions in solution when the following reagents are mixed?
(a) Sodium ethoxide and phenol
(b) Sodium phenoxide and ethanol
S. Predict the product in the following reactions:

6. Give the structural formula and name of the principal organic product (if any) from the reaction of
p-cresol with:
(a) hot conc. HCI (b) SOCl 2 (c) C 6Hs S02CI (d) benzyl chloride/aq. NaOH
(e) CH3COOHlH2S04 (f) 2, 4-dinitrochlorobenzene/aq. NaOH
7. Account for the increasing acidity order of p-halophenols as shown below:
Phenol pka
10.0

9.91

9.42

9.42

9.31
144 UNDERGRADUATE ORGANIC CHEMISTRY

8. Give a laboratory method for converting PhH into PhOH via PhN0 2.
9. Arrange the following compounds in order of decreasing acidity and justify your answer:
Phenol, o-chlorophenol, p-chlorophenol, m-chlorophenol
10. Arrange the following phenols in decreasing order of acidity and justify your answer: Phenol,
o-nitrophenol, p-nitrophenol, m-nitrophenol
11. Arrange the following phenols in decreasing order of acidity and justify your answer: Phenol, o-cresol,
p-cresol, m-cresol.
12. Explain why a substituent such as nitro bonded ortho or para has a much greater effect on the acidity
of a phenol than a benzoic acid.
13. Explain why resorcinol is more acidic than hydroquinone which is more acidic than catechol?
14. Explain why m-methoxyphenol is more acidic than m-aminophenol?

PROBLEMS FOR SELF ASSESSMENT


1. How will you accomplish the following transformations?
(a) Phenol--7 Aspirin (b) Phenol--7 Salol
(c) Phenol--7 oil of wintergreen (d) Salicylic acid - - 7 Phenol
(e) Salicylic acid - - 7 Benzene
2. Discuss the mechanism of the following reactions:
(a) Claisen rearrangement (b) Reimer-Tiemann reaction
(c) Fries Rearrangement (d) Houben-Hoesch reaction
(e) Gattermann reaction (f) Kolbe-Schmitt reaction
3. Give suitable explanation for the following:
(a) Phenol is more acidic than alcohol.
(b) o-Nitrophenol is weaker acid than p-nitrophenol.
(c) Picric acid is stronger than 2, 4-dinitrophenol.
4. Treatment of phenols with alkyl halides in the presence of KOH results in the formation of ether by
an SN2 process initiated by the nucleophilic attack of phenoxide ion. But 2, 4-ditert-butylphenol
gives a mixture of C-alkylated (p-alkyl derivative) and o-alkylated products. The amount of
C-alkylated product increases with increase in the size of alkyl group of alkyl halide. Explain.
S. Arrange the following compounds in order of increasing acidity explaining the reason thereof.
(a) Phenol, o-nitrophenol, 2, 4-dinitrophenol and 2, 4, 6-trinitrophenol.
(b) Phenol, p-chlorophenol, p-aminophenol and p-nitrophenol.
6. Metaproterenol, 1 is a /3-adrenoreceptor stimulant used therapeutically as a bronchodilator. In the
synthesis of 1, outlined below, supply the appropriate reagents.
PHENOLS 145

7. Explain why m-tert-butylphenol reacts with CI2 to give a trichloro derivative, whereas with 12 it forms
only monoiodo derivative.
8. Show the steps in industrial preparation of phenol starting with cumene (isopropylbenzene).
9. Explain why:
(a) The C-O bond in phenol is shorter than that in alcohol.
(b) The dipole moments of phenol (1.7 D) and methanol (1.6 D) are in opposite directions.
(c) The dipole moment of p-nitrophenol (5.0 D) is greater than that of phenol (1.7 D) and
nitrobenzene (4.0 D).
(d) Phenol has higher bp and water solubility than toluene.
10. In each of the following pairs of compounds which will be more acidic and why?

~ ~)~ &
F

~OH
(a) LQJ Md and
N0
2

OH N0 2

(C)~ and
6l0H
OH
ANSWERS TO VERY SHORT ANSWER QUESTIONS
1. For breaking intermolecular hydrogen bonding existing in phenol more energy is required than that
for weak van cler Waal's forces of attraction existing in toluene.
2. Salicylic acid is formed.
3. By the reaction of phenol with conc. H 2S04 followed by conc. HN0 3.

Picric acid (2.4,6-Trinitrophenol)

4. (A) (B)@
Br
2,4,6-Tribromophenol
5. Since the phenol with molecular formula C 7H sO forms a tribromo derivative on treatment with Br2
water, it must have both the ortho and one para position free. Thus, the phenol is:

~CH
m-cresol
3
146 UNDERGRADUATE ORGANIC CHEMISTRY

6. Phenol is weaker acid than carbonic acid (H2C03)' hence does not liberate CO2 by decomposing
NaHC03. a salt of carbonic acid. A weaker acid cannot decompose a salt of stronger acid.

The name of the reaction is Fries rearrangement.


8. (a)
9. Cyclohexanol < p-methoxyphenol < phenol < p-bromophenol
10. The bulky o-tert-butyl groups prevent solvation of the corresponding phenoxide ion. thus making it
less stable than phenoxide ion.
11. Solubility decreases as the length of the carbon chain or the size of the hydrocarbon part increases.
Thus. the increasing order of solubility is:
C6HsCH20H < C6HSOH < C2HsOH

°
11

12. (a) CHCl3/KOH (b) rQYC'o/conc. H2S04


~C/
11
o
13. Delocalisation of electron density from oxygen to benzene ring makes the oxygen of phenol to be the
positive end of the molecular dipole. In methanol. the strongly electron-withdrawing oxygen is the
negative end of the dipole due to +1 effect of the methyl group. Thus. the two dipoles act in opposite
directions.
..

14. By Elbs persulphate oxidation.

~ OH
Quinol

15. (Z)
PHENOLS

110f,1,un·U;j·Bt.J=B¥4JI
OH

(blHOOC~
~NH2
1. (a)

(A)

2. (al ~COOH (b) CoH,o-GH,COOC,H, (cl ~3 (d)


Br~OOH
¥
CH 3

CH3 Br Br

(el ~NO'
Cl
3. p-bromophenol > phenol > p-methoxyphenol > cyclohexanol
4. Phenoxide ion in both the cases.

6. (a) No reaction (b) No reaction


(c) ~'CoH'
CH3
p-Tolyl benzenesulphonate
148 UNDERGRADUATE ORGANIC CHEMISTRY

~2C~'
(d)
(e)~CH3
CH 3 CH3 2,4-Dinitrophenyl p-tolyl ether

Benzyl p-tolyl ether p- Tolyl acetate

7. F, Cl, Br and 1 atoms have -I and +R effects; both the effects have one and the same order which is
F> Cl > Br > I; the -I effect, however, predominates over the +R effect; for this reason the
p-halophenoxide ions, specially p-fluorophenoxide are more stable than the phenoxide ions and hence
they are less basic than the latter. So the p-halophenols are more acidic than phenol. However, in the
cases of p-chloro, p-bromo and p-iodophenoxide ions Cl, Br and 1 atoms act as d - 1t acceptor (-R
effect) and thereby the negative charge on the oxygen atoms gets delocalised to a larger extent and
this effect being predominant, the stability of the pbenoxides increases. Since d - 1t accepting ability

O-H c~

9 ~
~
~
+ H(f)

F F

t
0

QF

c~

Q g
O-H
X=Cl,Br,I
~
~

X
+ H(f)

t
0

y--~-~
X
e
PHENOLS 149

order is I> Br > Cl, p-iodophenoxide is the most stable base among the three. The greater -I effect
of Cl than that of Br and the greater d -1t acc:!pting ability of Br than that of Cl make their
phenoxides equally stable. Naturally p-halophenols; the stability of p-chlorophenoxide and
p-bromophenoxide being equal the corresponding phenols have identical pka values. F atom being
unable to act as a d -1t acceptor because of the absence of d-orbital, the p-lluoxophenoxide ion is
the least stable among p-halophenoxides. So the p-fluorophenol is the least acidic among
p-halophenols and possesses the highest pka value.
HN0 3/H 2S04
8. PhH----~) PhN02 0) SnlHCl ) PhNH
(ii) NaOH 2

O°C 1
NaNOiaq. HCl

HO
PhOH ~ PhNEBCl e
/). 2

9. Although Cl is electron-donating by resonance, its electron-withdrawal inductive effect predominates


and decreases with increasing separation of Cl and OH. This makes the chlorophenols more acidic
than phenol. The decreasing order of acidity is:
o-chlorophenol > m-chlorophenol > p-chlorophenol > phenol
10. N0 2 group is an electron-withdrawing and acid strengthening by both -I and -R effects. Its -R effect
is effective from only the ortho and para positions to about an equal extent. It predominates over
the inductive effect which operates from all positions but at decreasing effectiveness with increasing
separation of N0 2 and OH groups. Hence, all the nitrophenols are more acidic than phenol with
m-nitrophenol being the weakest of the three (0-, m- and p-nitrophenols). Since the inductive effect
from the closer o-position is the strongest, one might expect o-nitrophenol to be stronger than
p-nitrophenol. However, the intramolecular hydrogen bonding in o-nitrophenol must be broken for
exhibiting acidity and this requires energy. Thus, the decreasing order of acidity is:
p-nitrophenol > o-nitrophenol > m-nitrophenol > phenol
11. Methyl group is electron-donating inductively from all positions and hyperconjugatively from the
ortho and para positions. The three isomers are weaker acids than plenol. m-cresol is the strongest
among the isomers because its acidity is not weakened by hyperconjugation. The decreasing order
of acidity is:
phenol > m-cresol > o-cresol '" p-cresol.
12. Charge delocalisation in the nitrophenolate ion is much more effective because of the direct interaction
e e
between 0 and N0 2. This interaction is not possible in the p-nitrobenzoate anion because -COO
and nitro groups are not in the same plane.
150 UNDERGRADUATE ORGANIC CHEMISTRY

o
Q
,®,N
0
e e

e
-COO and benzene ring are not in the same plane.
13. In resorcinol, the two -OH groups are present at the m-position and hence one -OH cannot enter
into resonance with the other -OH. Instead -/ effect of one -OH on the other, makes resorcinol
more acidic than catechol and hydroquinone.
e

& OH
~OH
Anion is stabilised by
-I effect of -OH
In catechol, the two -OH groups are involved in intramolecular hydrogen bonding, which makes
the loss of a proton little difficult as compared to that in hydroquinone. In other words, hydroquinone
is more acidic than catechol.
14. A meta methoxy group or a meta amino group cannot enter into resonance with the hydroxyl group
but can exert -/ effect from this position. Since the -/ effect of OCH3 is more than that of -NH2
group, therefore, m-methoxy phenol is stronger acid than m-aminophenol.
ODD
4.1. Ethers

Compounds of the type R-O-R are called ethers, R may be aliphatic or aromatic and the groups
may be identical or different. The common name of ethers is derived by naming the alkyl groups
and adding the word ether. The smaller group is written first, for example :
CH3-CH2-0-CH2-CH3 CH3-O-CH2CH3
Diethyl ether Methyl ethyl ether
In naming the symmetrical ether "it is not necessary to write the prefix di.
CH3-0-CH3
Dimethyl ether
or
Methyl ether
In IUPAC naming system ethers are named as alkoxy derivatives of hydrocarbons. The term
alkoxy is retained with the group having lesser number of carbon atoms. The parent name corresponds
to the hydrocarbon with larger number of carbon atoms. The name of ethers is written as one word,
e.g. as alkoxyalkane.
For example :
CH3
I
CH3-0-CH2CH3 CH3-0-CH-CH3
Methoxyethane 2-Methoxypropane
(not ethoxymethane)

CH3CH2CH2CH20CH3 CH3-CH-CH2-CH3
I-Methoxybutane
I
OCH2CH3
Methoxybenzene Ethoxybenzene
2-Ethoxybutane (anisole) (phenetole)

4.2. Methods of preparation


4.2.1 From alcohols : Symmetrical ethers are prepared by heating excess of alcohol with cone.
H2S04 at 140-180·C. Primary alcohols undergo dehydration to give ethers. Secondary and tertiary
alcohols undergo dehydration to give a mixture of ether and alkene.
cone. H2S04
152 UNDERGRADUATE ORGANIC CHEMISTRY

The reaction proceeds by either SN i or SN2 mecha'nism.


SN2 mechanism: The scheme of the mechanism is given below:
Efl
R-CH2-0H + HEfl R-CH2-0H2

H
•• Efl 8+ 8+ I
R-CH20H + RCH20H2 -~) R-CH2-0----C----OH2
•• I /\
H H R
T.S,
H201
-He ®
R-CH 2-O-CH 2-R .....t - - - R-CH2~H2-R
Ether
H
SN mechanism: The scheme of SN mechanism is given below:
1 i

R' R' R'


(i) I He ::.. I ® slow I
R-C-OH '" R-C-OH 2 --+ R-C®
I I I
R" R" R"

R' R' R' R' R'


I~. I I Efl I I
(ii) R-O~ + :O-C-R
fast
.. R-C-O-C-R
fast
.. R-C-O-C-R
I I I IG I -~
I I
R" H R" R" H R" R" R"

4.2.2 Williamson Ether Synthesis : In this method an alkyl halide is allowed to react with
sodium alkoxide or sodium phenoxide. This method is a laboratory method for the synthesis of
symmetrical and unsymmetrical ethers.
e
R-X + R'ONaEfl ) R-O-R' + NaX
e Efl
R-X + ArONa -~) R-O-Ar + NaX
This reactions is the typical SN 2 displacement reaction. The general mechanism is as follows :

R' oe:1 () Slow. [R'-tuuUR'_u~ ]


fast
- -..... R/-O-R + X
e

Ca) In this reaction sodium alkoxide may be alkoxide of primary or secondary alcohols.
(b) Alkyl halide should only be prima~ because secondary and tertiary alkyl halides undergo
dehydrohalogenation in the presence of R-O which is strong base for elimination reaction.
0Gl
CH)-CH 2-CH z-ONa
CH3-CH2-Br ) CH3-CH2-CH2-0--CH2-CH3
(c) Sodium or potassium tertiary butoxide always gives eliminatIOn reactIOn with primary.
secondary and tertiary alkyl halides. It forms ether only with CH3X because it has no ~-carbon.
ETHERS AND EPOXIDES 153

CHj
CHj I
. - - - - - - 4 CHj-C-O-CHj
I ee I
CHj-C-ONa CHj
I
CHj

'------~ CH2=CH2
Only product

4.2.3 From alkenes : (a) Alcohols can be added to alkenes under acidic conditions to give ethers.
This reaction, involves protonation of alkene to give a carbocation followed by nucleophilic addition.
The addition takes place according to Markownikov rule.
CHj" HBF4 CHj"
/C=CH2+CHjOH ---~ /C-OCHj
CHj CHj I
CHj
(b) Alkenes react with mercuric trifluoroacetate in the presence of alcohol to give
alkoxymercurial compounds which on reduction yield ether.
CH ../OCOCF3
~ H!S'-...OCOCF3 CHj"
CH3 / C-CH=CH2 + CHjOH ) CHj /C-CH-CH2
CH} CHj/ I I
OCHj Hg-O-CO
I
I
CFj

_K_OO N'B....

CHj"
CHj/C-CH-CHj
CHj I
OCHj
4.2.4 By heating alkyl halides with Ag20 : Symmetrical ethers may be obtained by heating
alkyl halides with silver oxide.

4.2.5 By action of diazomethane on a1cohols : Methyl ethers can be obtained by treatment of


primary or secondary alcohols with diazomethane. Fluoroboric acid (HBF4) is used as catalyst.

R-O-H + CH2N2 -----7) R-O-R + N2


4.3. Physical Properties

T hehomologous
simple ethers are colourless compounds with characteristic smell. The first member of the ether
series is gas and the lower ethers are liquid at room temperature. The boiling points
of ethers are usually similar to those of alkanes from which these can be formally derived and lower
than isomeric primary alcohols. The lower bp of ethers in comparison to alcohols is due to the absence
of intermolecular hydrogen bonding. There is little dipolar association in ethers due to their dipole
154 UNDERGRADUATE ORGANIC CHEMISTRY

moment caused by the C-O bond. Thus ehters have slightly higher bp than the hydrocarbons of the
corresponding molecular weight.
4.4. Chemical Reactions

I nthough
general, ethers are much less reactive, as the cleavage of the C-O bond does not occur readily,
it is not as stable as C-C bond. Thus it shows some cleavage reactions.
Ethers form ether-soluble complexes with a number of Lewis acids, they dissolve a veriety of
organic compounds and they are also unreactive under various reaction conditions. These properties
make ethers useful solvents for organic reactions.
4.4.1 Reaction with Acids: Ethers react with Lewis acids to form co-ordinate complexes.
R" Er> e
R-O-R' +BF3 ) /O-BF3
R'
Thus ethers have the basic character. This basic character of ethers is due to the presence of lone
pair of electrons on sp3 orbitals of oxygen atom. They also form salts with proton acids.
R, R, Er>
"O+HX ) "Oxe
R' / R' / I
H
These complex ethers become more susceptible to nucleophilic attack at the a-carbQn atom or
attack by base at a l3-hydrogen, leading to the cleavage of the original C-O bond. Thus the essential
requirements for reagents to cleave ethers are an acid to form complex with the ether oxygen and
provide electrophilic assistance to the C-O bond breaking. and a nucleophile or base that is affective
under the acidic condition.

R- g-R' + HEr> _ _-+~ R- ~- R'


I
H
Electrophilic in nature

X
e'-'R"v?-R' --.~
Ef)
R-X +R'-OH
H
Concentrated hydroiodic acid, which is strongly acidic solution containing powerful nucleophile
r, is probably the most effective reagent for cleavage of ethers in aqueous solution.
Cleavage of C-O bond is the example 9f SN2 reaction. However, when the ether is
unsymmetrical and one of the alkyl groups is tertiary, the reaction proceeds by SN I mechanism and
alkyl halide is always tertiary alkyl halide.
CH3 H CH3
I H$ 10..1 Slow
CH3 -O-C-CH3 --.~ CH3 -O C -CH3
I Er> I
CH3 CH3

CH3
I
CH3-C-x
I
CH3
Tertiary alkyl halide
ETHERS AND EPOXIDES 155

If excess of acid is used. the alcohol initially produced is also converted IOto alkyl halide.
R-OH + HX ) R-X + H20
Apart from these two reagents (BF3 and HI) there are a number of other reagents used for
cleavage of ether linkage. Most of these reagents have a halide ion as the nucleophile. The reagents
are (i) thionyl chloride -SnCI4. (ii) CH3COCI-ZnCI2. (iii) Phosphoryl chloride-
dimethylformamide. (iv) Pyridine-iodoborane. (v) Iodine-NaBH4.
4.4.2 Nucleophilic Substitution Reaction of Unsymmetrical Ethers
Nucleophilic substitution reactions of ethers take place due to the breaking of C-O bond. Ether
has two C-O bonds (say bond-l and bond-2). Thus breaking of C-O bonds takes place in two ways:
1 2 H-Nu
R-O-R' ) R-Nu + R'-OH; breaking of bond-l
or
R-OH + R'-Nu; breaking of bond-2
In the above reaction cleavage of bonds-l and -2 depends on the nature of R and R'.
Case 1. If both alkyl groups are primary then reaction is SN 2 and nucleophile of the reagent
attacks on the alkyl group having lesser number of carbons.
I
I H-Nu/~
CH3-CH2-l-1 O-CH2-CH2-CH3 ----t) CH3-CH2-Nu + CH3-CH2-CH2-0H
SN 2
I
1$
Nu~H
Case 2. If one of the alkyl groups is tertiary then mechanism is SN 1. Negative part of the reagent
attacks on tertiary alkyl group.
CH3 CH3
I I H-Nu/~ I
CH3-C-+O-CH2-CH3 ---4) CH3-C-Nu + CH3-CH2-0H
I I SN
i
I
CH3 I CH3
le
Nue : H
Case 3. If one group is alkyl and the other is aryl then reaction may be SN 1 or SN2; this depends
on the nature of alkyl group. In this case negative part of the reagent attacks only on alkyl group.
I H-Nu/~
Ar-0t--R ) Ar-OH + R-Nu
e l
HINu e
I
Some examples are :
I conc. H2S04
I
(1) CH 3-CH2i-O-CH2-CH2-CH3 U
I e e
I
I H+OS0 3H

Ethyl hydrogen sulphate Propyl alcohol


156 UNDERGRADUATE ORGANIC CHEMISTRY

o
11
CH3-CH2-Cl + CH3-CH2-O-C-CH3

o 0
11 11
R-C-O-C-RIAnly. ZnCl 2
(4) CH3-CH2-0-CH:2-CH2-CH3 :u: )
Et> e
R-C+ O-C-R
11 11
o 0

2 moles HIlA
(5) CH3-CH2-O-CH2-CH3 ) CH3-CH2-I + CH3-CH2-0H

lHI/A
CH3-CH2-I
PC1slA
(6) CH3-CH2-O-CH2-CH3 ) CH3-CH2-Cl + CH3-CH2-Cl + POCl3
ETHERS AND EPOXIDES 157

Some common nucleophilic substitution reactions


conc. HZS04 (I mole)
) R-OH + R-O-S03H
Warm

conc. HZS04 (2 moles)

Warm

HOHI d/High pressure


R-OH+R-OH
Et>
H

0- 0+ HI (1 mole)
R-O-R R-I+R-OH
Cold

2H1 (l mole)
R-I+R-I
Cold

3 moles HI/red P
R-H+R-H
d

° 0-
11
R/-C~l/ Anhy. ZnClz o
0+ 11
R-CI + R-O-C-R

° °Il
11 0-
R/-C-O~-R'
o 0
11, 11,
R-O-C-R + R-O-C-R

PClsld
R-CI + RCI + POCl3
Reaction of ether with HI is used for the estimation of alkoxy group (mainly methoxy and ethoxy
groups) in organic compounds and method is known as Zeisel method.
AgN03
R-OCH3 + HI -~) ROH + CH31 ) AgI + CH3N03
ppt

In this reaction :
- OCH3==AgI
_ 31 x wt. of AgI x 100
Thus % of methoxy group - MW of Ag I xwt.of ether
= 31 x wt. of AgI x 100
234·88 x wt. of ether
Here 31 = mass of methoxy group.
4.4.3 Dehydration: Ether undergoes dehydration reaction in the presence of cone. H2S04/ Ll
and anhy. A1203/Ll.
158 UNDERGRADUATE ORGANIC CHEMISTRY

Case I : When both alkyl groups have l3-hydrogen


a f3
C:3-C~2-0-TH-CH2-CH3

CH3
conc·l H2S04//l

CH2=CH2 + CH3-CH=CH-CH3 + HOH


Care 11 : When only one alkyl group has l3-hydrogen
CH3 CH3
I conc. H 2S04/A I
CH3-C-O-CH3 CH2=C + CH30H
f3 a I
a I
CH3 CH3
4.4.4 Oxidation Reactions :
(1) Ether having at least one a-hydrogen forms peroxide on standing in air in the presence of
DV light.
R' airlhv R'
/'
R-O-CH, /'
R-O-C,
'R' I 'R'
O-O-H
Ether peroxide
Poisonous and explosive
(a) To avoid the formation of peroxide ether is always kept in brown coloured bottle with small
amount of CU20 and H2S04' CUS04 or FeS04'
(b) CU20 works as ~ative catalyst for the reaction and H 2S04, CuS04 or FeS04 converts ether
peroxide into ether.
R' H2S0 4 R'
R-O-C/' ---~) R-O-CH( + H202
I"'-R' Cus040r
FeS0 4
'R'
O-O-H
(c) Formation of ether peroxide is confirmed by the identification of H 20 2 because H202 can
only be obtained by addition of H2S04' CUS04 or FeS04 if ether converts into ether peroxide.
H 2S04 KI/starch
(i) Ether peroxide --~) Ether + H202 ---~) Blue colour
Thus formation of blue colour confirms the formation of H 20 2, i.e., ether peroxide.
FeS04 Fe++ KCNS
(ii) Ether peroxide ) Ether + H202 ) Fe+++ ) Red colour
[0]

In this Fe++ will only convert into Fe+++ if there is formation of H202, i.e., ether peroxide.
4.4.5 Oxidation with K2Cr207/HE9
a a' /,R'
R-CH2-0-CH,
'R'
(a) Oxidation of ether can only be possible if anyone of the alkyl groups of ether has hydrogen
\ on a-carbon.
ETHERS AND EPOXIDES 159

(b) a-carbon having two hydrogens converts in carboxylic group and a-carbon having only one
hydrogen converts into keto group.

4.5 Miscellaneous reactions :


4.5.1 Halogenation: Ether undergoes free radical halogenation under UV light.
Case I : When chlorine is present in small amount, chlorination takes place only at a-carbon
and monochloro derivative is formed.
Cl
CI 2lhv I
CH3-CH2-O-CH2-CH3 ) CH3-CH-O-CH2-CH3
Excess

Case 11 : When chlorine is in excess amount, all the hydrogens are replaced by chloro group.
CI 2lhv
CH3-CH2-O-CH2-CH3 -----t) C2Cls-O-C2Cls
(Small)
4.5.2 Reaction with CO : Ether converts into ester with CO in the presence of BF3.
12S-180·C
R-O-R + CO ----~) RCOOR
200 atm, BF3

4.5.3 Wittig rearrangement: The base catalysed rearrangement of an ether to an alcohol via
a I, 2-shift is known as Wittig rearrangement.
This rearrangement is given by benzyl and allyl ethers whose carbamon is stabilised by
resonance. Rearrangement takes place in the presence of a strong base such as RLi and NaNH 2.
Rearrangement takes paIce by radical pair mechanism.
CH3
(i) PhLI I
C~S-CH2-0-CH3 ----~) C6Hs-CH-OH
E&
(ii) H

e • •
[C 6Hs-CH-o + CH~

t
C6Hs~~
Ee
H
C6H s-CH-oH .....t - -_ _ C6H s-CH-O .....t - - -
I I •
CH 3 CH 3 CH 3
Radical pair

4.5.4 Electrophilic Substitution in Aromatic Ethers Alkoxybenzenes undergo aromatic


160 UNDERGRADUATE ORGANIC CHEMISTRY

substitution in the benzene ring. The OR group is less powerful as an activator than the -OH group.
The alkoxybenzenes are also 0- and p- directing group like -OH.

4.6 Epoxides :
Three membered cyclic ethers are called epoxides or oxiranes.
CH2-CH2 CH3-CH-CH2
'0/ '0/
Epoxyethane (ethylene oxide) Epoxypropane (propylene oxide)

2.3-Epoxybutane
or
2.3-Dimethyloxirane

4.7 Preparation of epoxides :


4.7.1 From balobydrins : Alkenes form halohydrin with suitable reagents. The halohydrins are
converted into epoxides by strong base.
e
Cl 2/HP OH
R-CH=CH2 ) R1H-CH2Cl ---4) R-C~-fH2

OH 0
The mechanism of the reaction is as follows :

e
R-CH-CH 2Cl +OH ~ R-CH-CH 2Cl + H 2 0
I
OH ale

R-CH-CH 2 Q l - -.. ~ ~R-CH- CH 2 •·••• __ •• tt~ - -..~ R-CH-CH 2 + ct'


60 I #
0'"
0---
i!o.\\'\~
'0/

4.7.2 Epoxidation of alkenes : The carbon-carbon double bond of alkenes may be oxidised
directly to the epoxide group by per-acids, e.g., perbenzoic acid. The reaction generally takes place
in CH2Cl2 or CHCl3 and is called Prileschaiev's reaction.
CH 2C1 2
) C=C<+ RCOOOH --~) )C C<
per-acid '--/
U
ETHERS AND EPOXIDES 161

4.8 Reactions of epoxides

Thenormal
epoxide (three membered ring structure) suffers acute angle strain because of the distortion of
bond angles from 109S to approximately 60°. Opening of the ethylene oxide ring releases
strain of the molecule and provides a driving force for the reaction.
Epoxides undergo acid catalysed reactions with extreme ease and unlike ordinary ethers, can
even be cleaved by base.
4.8.1 Mechanism of Acid-catalysed reaction: The reaction is always a SN2 reaction
Step I :

Protonated epoxide
In protonated epoxide carbon-2 and carbon-3 both acquire some positive charge (i.e., carbocation
EB
character) due to the highly electronegative atom O. Thus nucleophile (generally weak in character)
attacks on the carbon of epoxide which i~ more hindered (where carbocation will be more stable).
Step 11 : ' '

Note:
(1) In the presence of acid, nucleophile attacks on more hindered carbon.
(2) -OH and -Nu are always trans to each other.
(3) Reaction is favoured by neutral nucleophiles.
Examples are :

4.8.2 Mechanism of Base-Catalysed Reactions: This reaction is also a SN 2 reaction in which


nucleophile attacks on less hindered carbon of the ring. I
162 UNDERGRADUATE ORGANIC CHEMISTRY

R" r1
C-CH-R +Nu
R
I
Nu
I H$
R - C - CH- R -..::.:...-... R -
R
I
Nu
I
C - CH - R
R/"oj I I
o
G
OH
Note:
(1) In the presence of base a catalyst nucleophile attacks on less hindered carbon of the ring.
(2) Reaction is favoured by charged nucleophiles.
(3) Nuc\eophile of the reactIOn behaves as base catalyst.
e OCH3
(1) CH30 I
CH3-CH-CH2 ----~) CH3-CH-CH2
(il) CH 30H I
\ /
o OH

Some reactions of oxirane are given below:


(j)
CH 30H/H

I------~ CH20H-CH2NH2
OCH3
CH 30Na I
CH2-CH2 --+-----~ CH2-CH20H
'\ / CH 30H
o
&-8+
(I) RMgX
I------~ R-CH2-CH2-0H
(ii) HOH

(ii) R2CuLi
I----(i-i)-H-O-H-~ R-:-CH2-CH2-OH
8+ 0-
(11) LIAIH4
'-----$--1) CH3-CH2-0H
(ii) HOH/H
ETHERS AND EPOXIDES 163

VERY SHORT ANSWER QUESTIONS


1. Why does CJiSOCH3 (anisole) cleave to give CH3I and C6HsOH rather than C6HSI and CH30H?
2. Why HI is a better reagent than HBr in the cleavage of ethers?
3. Which of the following groups is estimated by Ziesel method?
amino, alcoholic, alkoxy
4. Why are ethers insoluble in water?
5. Why do ethers have relatively low boiling points as compared to alcohols which are their functional
isomers?
6. What is the basis of Ziesel method for estimation of methoxy group?
7. Predict the product formed where I-butene oxide is treated with Hi 80 in the presence of an acid.
S. Explain why methanol reacts with epoxyethane in the presence of an acid but not in its absence.
9. Explain why epoxyethane reacts with CH30Na but diethyl ether does not.
10. Give one example of intramolecular Williamson synthesis.
11. In the Williamson synthesis we can add the alkoxide to alkyl halide or vice-versa. What actually
should be done to obtain good yield of an ether?
12. Name the alkyl halide and sodium alkoxide used to synthesise tert-butyl ethyl ether.
13. Name the major product obtained when tert-butyl bromide is treated with sodium ethoxide.
\

PROBLEMS WITH SOLUTIONS


1. Complete the following reactions:

(a) V He
+Hp--'
OH

(c) V
"\7
+ ©
(i) CH)MgBr
(d) V +NH3 --'

(e) \d (ii) HEll to

2. Identify (A), (B) and (C) in the following sequence of reactions:


C1 2/H 20 ale. KOH
CH2=CH2 ----7) (A) C2HSOC1 ) (B) C~80C12--~) (C) C4H60

3. Which of the following combinations of reagents is suitable for the synthesis of ethyl tert-butyl ether.
Give reason for your choice.
CH3 CH3
I I
(a) CH3CH2Br + NaO-C-CH3 (b) CH3-j-C1 + NaOCH2CH3
I
CH3 CH3
4. Complete the following reactions :
140T
(a) C6HSOC2HS + hot cone. HBr --7 (b) Ethyl alcohol + H2S04 --7

HN031H2S04
(c) C6HS-OC2HS )
164 UNDERGRADUATE ORGANIC CHEMISTRY

/CH3 /CH3
(e) CH30CH" + cold HI ~ (f) CH30C " CH3 + cold HI ~
CH3 'CH3
5. Give the missing reactants, reagents, or products to complete the following reactions :
o
(a) D

conc.HI

©
OCH3

Conc. HBr
(e) -----~) ? + ? ----~) ?

6. Complete the following reactions :

Me" MeOH/HEi)
(a) /C-CH2
Me \ /
o

Me H
(e) "C=C/ e
H/ "Me (ii)OH
(iii) Hp(j)

PROBLEMS FOR SELF ASSESSMENT


1. Identify (A), (B) and (C) in the following sequence of reactions:
NOCl
ClCH2CH-CH2 + CH30H + H2S04 ~ (A) C4H902Cl ~ (B) C3H603
\ / -CHCI 2
o
aq. NaOH
(A) -~ (C) C4H g0 2
2. Complete the following reactions :
e
o OH/H20
(b) D
e
o anhy. HBr (i) CH3-C=CNa(j)
(c) Q )
ETHERS AND EPOXIDES 165

o
(e) Me, F'\
Me~
3. Write notes on the following :
(a) Williamson Synthesis (b) Zksel method
(c) Wittig rearrangement (d) Ring opening reactions of epoxides
(e) Prileschaiev's reaction
4. Give the structures of the product from (A) to (E) in the following reactions :
(a) CICH2CH2CH20H + KOH ) (A) C3H60

(b) 00 +anhy. HCl , (B) C,;IIllOCl

(c) @ + D + BF3 ) (C)CsHlOO

("yCH 3
(d) 0 +OHC020H ) (D) C7 H 140 2
,/ \ (i) cold alkaline KMn04
(e) CH2=CH-CH-CH2 ) (E) C4HlO04
(ii) dilute acid

5. Predict the chief product of each of the following reactions :


(a) Styrene oxide + dry HCI )
(b) Styrene oxide + CH30H + small amount of CH30Na --~
(c) Propylene oxide + aniline --~
(d) Trimethylethylene oxide + HCI )
(e) I-Methylcyc1ohexene + t-butyl alcohol + mercuric trifluoroacetate --~

ANSWERS TO VERY SHORT ANSWER QUESTIONS


Ell
1. SN2 attack of iodide ion does not occur readily on a carbon of benzene ring. Also, C6HS does not
form in SN 1 reaction, Therefore, phenyl iodide cannot be a product in the following cleavage reaction:
OH

@ +CH,l

Ell
2. Since HI is a stronger acid, it gives a greater concentration of oxonium ion R-O-R to facilitate
I
H
the cleavage. Also, t>
is a better nucleophile than Br8 in the SN2 reaction.
3. Alkoxy.
4. They do not form hydrogen bond with water.
5. Alcohols form intermolecular hydrogen bonds which raise boiling points but ethers do not form
hydrogen bonds.
6. The reaction of methyl aryl ethers with HI forms the basis of estimation of OCH3 groups.
166 UNDERGRADUATE ORGANIC CHEMISTRY

0, 180H
/ '\. Hj80 e I
7. CH3-CH2-CH--CH2 ) CH3-CH2-CH-CH20H
8. Methanol being a weak nucleophile cannot displace strongly basic alkoxide ion. However. in the
presence of an acid the expoxide oxygen gets protonated, thus becomes a good leaving group.
Therefore, even weak nucleophiles such as CH30H can easily cleave the ring.
9. Epoxyethane is a highly strained molecule. hence it undergoes cleavage to form 2-methoxyethanol.
On the other hand, diethyl ether is a stable molecule and being a Lewis base it does not react with
another base, e.g., CH30Na.
10. Synthesis of epoxides by treatment of halohydrins with a base.
e
OH
R-CH-CH2CI ~ R-CH-CH2
I
OH
' '0/
11. The alkoxide ion should never present in excess otherwise it can bring about dehyrohalogenation of
alkyl halides to alkenes. Therefore. it is advisable to add alkoxide ion to alkyl halides.
12. Ethyl bromide and sodium tert-butoxide.
13. 2-Methylpropene.

1. (a) HOCH2CH20H (b) C2HsOCH2CH20H

(c) @-O-CH2CH20H (d) H2N-CH2CH20H

(e) CH3CH2CH20H
2. (A) CICH2CH20H (B) CICH2CH2-0-CH2CH2CI
(C) CH2=CH-O-CH=CH2
3. The combination (a) is suitable because in combination (b) there is tertiary butyl chloride which will
give elimination product in the presence of a strong base CH3CH20Na instead of the substitution
product (ether).
4. (a) C6HSOH, C2HSBr (b) CH3CH20CH2CH3

(c) c6Y N02


+ ~H5
N0 2
(e) CH31 + (CH3hCHOH (t) CH30H + (CH3hCI
S. (a) He1H20; BrCH2CH2Br (b) (CH3hC=CH2
(c) (CH3hC-O-CH3 (d) (CH3hCHCH2I + (CH3hCI
ETHERS AND EPOXIDES 167

(e) LQJ -
1::NO,
+
LNO,
LQJ
~
qJ+

6. (a) M,/ C-CH2-0H (b) M~/C-CH2-NHMe (c) 11


Me I Me I H3CAo ./
OMe OH
Me
I
H-C-OH
(d) CH3CHO, CH30S0 3H (e) I
H-C-OH
I
Me
Mesa

ODD
flLD€HYD€S

5.0 Introduction
ldehydes and ketones are structurally very much similar, both have a carbon-oxygen double bond,
A often called a carbonyl group. Like any double bond, the carbonyl group is composed of a cr
bond and a n bond, but unlike carbon-carbon double bond it is polar due to greater electronegativity
of oxygen. In an aldehyde, the carbon of the C=O is bonded to either two hydrogens or to a Hand
an alkyl/aryl group while in a ketone it is bonded to two alkyl/aryl groups or an alkyl and an aryl
group.
R R
\'C=O R)C=O
HI
[R-H or alkyl or aryl] [R = alkyl and/or aryl]
Aldehydes Ketones
o o o
11 11 11
CH3-C-H, H-C-H CH3-C-CH3
o o
11
C6HS-C-CH3 C6Hs-C-C6HS
5.1 Nomenclature
"
ldehydes: In common naming system, the aldehydes are named with reference to the acid, which
A they yield on oxidation. In the name of acid the ending ic acid is replaced by the suffix aldehyde .
....
Formic acid Formaldehyde
Acetic acid Acetaldehyde
Propionic acid Propionaldehyde
Benzoic acid Benzaldehyde
In IUPAC naming system, the names of aldehydes are derived from the parent alkanes by
replacing the suffix e by al. For example:
o
11
H-C-H CH3CHO CH3CH2CHO
Methanal Ethanal Propanal
In the common names of aldehydes, the positions of side chains or substitutents are indicated
by Greek letters, et, 13, y, etc. whereas in IUPAC naming system, it is indicated by numbers, for
example:
ALDEHYDES AND KETONES 169

Br-CH2-CH2-C-H
° 11

rUPAC name: 3-bromopropanal


Common name: B-bromopropionaldehyde

Ketones
In common naming system ketones are named on the basis of the alkyl groups attached to the
carbonyl group. For example:

° °11 °11
CH3-C-CH3 CH3-C-CH2CH3 CH3-C-CH2CH2CH3
"
Dimethyl ketone, acetone Ethyl methyl ketone Methyl propyl ketone

The positions of side chains or substitutents are indicated by Greek letters, the a-carbon atom
being the one adjacent to the keto group, for example:
CH3CHCOCH2CH2CI
1
Cl
ex, W-dichlorodiethyl ketone

In IUPAC naming system ketones are designated by the suffix -one, which is added to the name
of the hydrocarbons from which they are derived. The longest carbon chain containing the keto group
is chosen as the parent hydrocarbon; the positions of side chains or substitutents are indicated by
numbers, and the keto group is given the lowest number posible. For example:

°11
CH3-C-CH2CH2CH3
° 11
(CH3hCH-C-CH(CH3)CH2CH3
2-pentanone 2,4-dimethyl-3-hexanone 2,4-pentanedione
Prefix for aldehydes is oxo, aldo or formyl, and for ketones oxo or keto.
5.2 Methods of Preparation of Aldehydes and Ketones
5.2.1 Preparation of aldehydes
Aliphatic and aromatic aldehydes can be prepared by the following general methods.
(i) Oxidation of primary alcohols: Primary alcohols on oxidation with KMn04, K2Cr207 or
Mn02 yied aldehydes. K Cr20 7/H6l
2
R-CH20H ) R-CHO
K 2Cr 20 7/HEIl
Ar-CH 20H ) Ar-CHO
However, when the alcohol has poor solubility in water a solution of chromic anhydride in water,
acetone and H2S04 (Jones reagent) is commonly used.
(ii) Oxidation of alkenes: Ozone reacts with alkene to form ozonide which, on hydrolysis,
gives aldehydes.
R, /R (i) 0 3 R,
'C=C )2 'C=O
HI \H (ii) HOHlZincdust HI
170 UNDERGRADUTE ORGANIC CHEMISTRY

o
CH3,\ (i) 0 3 CH3,\ 11
C=CH2 ) /C=O + H-C-H
H/ (ii) HOHlZinc dust H

(ill) Hydration of acetylene: Hydration of acetylene in the presence of H2S04 and HgS04
forms an aldehyde.
H2S04
CH==CH + H20~ CH3CHO
HgS04

(iv) Hydroboration of alkynes: Alkynes undergo hydroboration faster than alkenes and the
vinylboranes thus obtained give aldehydes (if the double bond is located at the end of the chain) on
treatment with alkaline hydrogen peroxide.
R2BH
CH3(CH 2hC==CH ~ CH3(CH2hCH=CHBR2
Vinylborane

CH3(CH2hCH2CHO
Tautomerisation I
• CH3(CH2hCH=CHOH
H202/~H

(v) From Acid chloride: Reduction of acid chloride in the presence of palladized barium
sulphate or carbonate partially deactivated by sulphur or quinoline results in the formation of aldehyde.
PdlBaS04
R-COCI + H2 ) RCHO + HCI
The following mechanism seems to operate

o r-:OIH ~OH
11
R-C -Cl + H2 --.....,.~ R-?Ul --... R-? -
'- 11 _H6l °11
R-C-H
H H
This reaction is known as Rosenmund Reduction.
Acid chloride can also be converted into aldehyde on reduction with lithium tri-t-butoxy
alumnium hydride (LTBA)

RCOCI LTBA) RCHO

COCI

c9J N02
This reagent reduces only -COCl into CHO. There is no effect on nitro group.
The mechanistic course of these reductions can be shown as follows:
ALDEHYDES AND KETONES 171

O-But
e e
O-But
I
H-Al-O-Bu
t _ _~)LiE!:l I
+ H-Al-O-Bu t

1 1
O-But O-But

O-But e

But-o-t1 H +
[
O-But - - -

Aldehyde

(vi) By Stephen's method: In this method an alkyl cyanide is dissolved in ether (or ethyl
formate or ethyl acetate) and reduced with stannous chloride and HC!. The reaction takes place through
aldimine hydrocloride or imino chloride as follows:
HCI E!:l SnCI 2IHCI H0
R-C=N-~) [R-C=NH]Cl e ) [RCH=NH2]rSnCl~- 2) RCHO
Aldimine stannic chloride

5.2.2 Specific methods for the preparation of Aromatic aldehydes


(i) Oxidation of alkylbenzenes: Oxidation of the side chain can be interrupted by trapping
the aldehyde in the form of non-oxidisable derivative, the gem, diacetate.
o
CrO,, /OCOCH3 HOH / OH 1J 0
-'2
11
Ar-CH3 + (CH3CO)zO . ) Ar-CH\ ----t) Ar-CH ---4) Ar-C-H
OCOCH3 \OH
When methylbenzene (toluene) is treated with acetic anhydride and chromic anhydride,
formation of gem diacetate takes place which, on hydrolysis, gives aldehyde.
(ll) When methyl benzene is oxidised by chromyl chloride in CCl4 solution formation of
aldehyde takes place.
Cr02CI2 H20
Ph-CH3 ) Ph-CH(OCrCI20Hh ) PhCHO
CCI 4 Toluene chromyl chloride complex
This reaction is known as Etard reaction.
(iii) Gattermann-Koch aldehyde reaction: Benzaldehyde and many other aldehydes are
conveniently synthesised by treating benzene (or other aromatic hydrocarbons) with a mixture of
carbon monoxide and HCl gas in the presence of anhydrous AICI3. The proposed mechanism is as
follows:
e E!:l E!:l E!:l e
HCI + C==O + AICl3 -~) [H-C=O ~(--~) H-C==O]AlCI4
172 UNDERGRADUTE ORGANIC CHEMISTRY

~ -J-~ ~H e4 ~CHO
~H=O----'~ CH=O AICI • ~ +HCI+AICI3

cr complex

(iv) Gattermann aldehyde reaction: When benzene or substituted benzene (substituent


should be ring activating), generally phenols, are treated with dry HCI and HCN in the presence of
anhydrous AICl3 and the complex so produced decomposed with water, gives aromatic aldehydes.
~CHO

(v)
O I: + HCN + HCI Alel,_ ~
Reimer-Tiemann reaction: When phenol is treated with CHCl 3 in the presence of alkali,
formation of o-hydroxybenzaldehyde takes place.

~ +CHCI, _ _o=If:...-..__ ~CHO +

major product
CRO
minor product

5.2.3 Preparation of Ketones


(i) Oxidation of Secondary alcohols: Secondary alcohols on oxidation with acidic
K2Cr207, Mn02 or chromic anhydride in H2S04 yield ketones.

R-CHOH-R' [0] ) RJ-R'


°
Oxidation of secondary alcohol by Cr(VI) is believed to involve formation of a chromate ester.
This ester on decomposition gives ketone.
o 0
R"/
R' I
11
C-O-H+HO-Cr-OH-~)
11
R"
R' I
11
/C-O-Cr-OH
11
H 0 H 0
Alkylchromic acid
The oxidation step is an elimination reaction of alkyl ester of chromic acid. For the elimination
reaction a base is required to accept the carbinal hydrogen atom. In most cases in aqueous solution,
the base is presumably water.

R
I
°11 @ R e
R'-9TO,.,Cr-O-H ---.. BR + )C=O+HOCr0 2
. :""\. tJ 1I11 R'
B ~R °
Ketones can be obtained in good yield by Oppenauer oxidation of secondary alcohols using
aluminium tertiary butoxide in excess of acetone.
ALDEHYDES AND KETONES 173

In this reaction acetone (or other ketones) is employed as hydride acceptor. The Oppenauer
oxidation involves use of aluminium tertiary butoxide and acetone or cyclohexanone as oxidant and
solvent. Since the reaction is reversible, the oxidant is usually present in large excess (solvent) so that
the equilibrium mixture favours the desired product. Since AI(OButh is not a powerful base, the
reaction conditions are rather mild and this oxidation is of great value for the reactions of
polyfunctional compounds that contain sensitive functional groups.

Mechanism:

OH CH3
I I
Step I R-CH-R+ CH3-i-O- Al

CH3
3

JI Exchange reaction
OH

'CH-O] Al + CH3-~-CH3
( R/ 3 I
(A) CH3
174 UNDERGRADUTE ORGANIC CHEMISTRY

Step 11

Solvent (B)
This new complex (B) is set up for an intramolecular transfer of hydrogen in the form of hydlide
ion which simultaneously reduces acetone and oxidises secondary alcohol into ketone.

~9 ~l~-CH~~)
/.1c~~
<

~ 2

H37CH C
3 1 :-.....
reduced
H R \R
\
Oxidised

Thus three moles of acetone (solvent) react with one mole of the new complex (A) to give three
moles of the product and a new alkoxide ion.

Aldehydes are not satisfactorily prepared by this reaction in the presence of aliphatic ketones
because the basic nature of reagent induces reaction between aldehyde and ketone.
In the presence of p-benzoquinone this is not possible because aldehyde does not react with
p-benzoquinone,
AI-tert-butoxide/Ll
CH3-CH=CH-CH20H • CH3-CH=CH-CHO
p-benzoquinone
(ii) From alkenes: Ozonolysis: Tetrasubstituted alkenes when treated with ozone yield
ozonides which on subsequent treatment, give ketones.

(ii) H20lZinc dust

(iii) From alkynes:


(a) Hydration: Alkynes other than acetylene, when treated with water in the presence of
dil. H2S04 and HgS04, give ketones.

R-C==CH+HOH--~)
H2S04
R-CH=CH2 ~<==
°11
R-C-CH 3
HgS04 1
OH
ALDEHYDES AND KETONES 175

o
H2S04 11
C6H5-C=CH + H20 ) C6H5-C-CH3
HgS04

(b) Hydroboration: Ketones can be prepared by the hydroboration of appropriate alkynes.

R2BH R-CH2,\ / CH2R


R-CH2-C=C-CH2R ) /C=C,\
H BR2
IHOH
o
11 R-CH 2,\ / CH2R
R-CH2-CH2-C-CH2R ~ /C=C,
H 'OH
(iv) Friedel-Crafts Acylation: Aromatic hydrocarbons when treated with an acid halide or
acid anhydride in the presence of anhydrous AICl3 form ketones.
COR

@'+ RCOCl
AlCl3
.@ + HCI

COR

@+ (RCO),O
AlCl3
@
~ + RCOOH

(v) Fries Rearrangement: Esters of phenol when heated with anhydrous aluminium chloride,
formation of 0- and p-acyl derivative of phenols takes place.
o
11
OH
@C-R Aiel,
@rCOR +

COR
(vi) From Grignard Reagent: Reaction of Grignard reagent with nitriles gives ketones.

H3d~ R,\
ArMgBr + R-C=N-~) R-C=NMgBr ) /C=O
1 Ar
Ar
(vii) By reaction of acid chlorides with organocadmium compounds:
Dialkyl cadmium reacts with acid chlorides to give ketones. Dialkylcadmium is prepared from
Grignard reagents.
176 UNDERGRADUTE ORGANIC CHEMISTRY

2RMgX + CdC1 2 ---'» R2Cd + 2MgXCl


(R =aryl or primary alkyl)

R2Cd + 2R'COCl---'» 2R-C-R' + CdC12


11
o
Secondary and tertiary alkyl cadmium reagents decompose spontaneously, hence this reaction is
limited to organocadmium compounds containing aryl or primary alkyl groups (R = aryl or primary
alkyl) which are stable enough for use. Because of their low reactivity, organocadmium compounds
do not react with many of the functional groups, e.g., > CO, -CN, -N02, -COOR. Therefore, the
presence of these groups in the acid chloride molecule does not interfere with the synthesis.
(viii) From carboxylic acids: By passing the vapours of any carboxylic acid other than formic
acid over MnO a ketone is obtained. .

Mixture of carboxylic acids gives mixed ketones:


MnO/A
RCOOH + R'COOH --~) RCOR' + C02 + H20

o ~ OLi
11 YI R'L· 1 H3~
R-C-oH + R'Li- R'H + R-C~ R-r-oLi - - . R-~-R'
R' o
RCOR and R'COR' are obtained as by-products. If R or R' is H then an aldehyde is obtained
in addition to ketone.
Reaction of alkyIlithium with carboxylic acids also gives ketones.
(ix) By pyrolysis of calcium salts of carboxylic acids:
A
(RCOOhCa -~) R2CO + CaC03
(R =alkyl or aryl)
Salts of Ba, Mn or Th have also been used.
Pyrolysis of calcium formate gives HCHO, a mixture of calcium saIt of formic acid and anyone
of its homologues gives aldehydes.

(RCOOhCa + (HCOOhCa---,» 2RCHO + 2CaC03


5.3 Physical Properties

T heattraction.
carbonyl compounds are strongly polar in nature, which results in appreciable intermolecular
Therefore, their boiling points are higher than those of the nonpolar substances of
comparable molecular weights. Their boiling points are, however, lower than those of the
corresponding alcohols because of the absence of intermolecular hydrogen bonding. Boiling points
increase with increase in molecular weight. Lower members of carbonyl compounds are freely
miscible with water but the solibility decreases rapidly with rise in molecular weight. Cs onward
members are sparingly soluble or insoluble in water. The boiling points of some carbonyl compounds
are given in Table 5.1.
ALDEHYDES AND KETONES 177

III=!II-I.
Name Formula B.P. cC

Formaldehyde HCHO -21


Acetaldehyde CH3CHO 21
Propionaldehyde CH3CH2CHO 49
Acrolein CH 2=CH-CHO 52.5
Benzaldehyde C6HsCHO 179
Acetone CH3COCH3 56
Methyl ethyl ketone C2HsCOCH3 80
2-Pentanone CH3COCH 2-CH 2-CH3 102
Acetophenone C6HsCOCH3 203
Benzophenone C6HsC06Hs 305.4

5.4 Structure and Nature of Aldehydes and Ketones

O'bond O'bond

"-c~ 0 "-C~ C",


", t ", t "-
1t bond 1t bond
The carbonyl group, like carbon-carbon double bond of alkenes, is composed of one er bond and
one 1t bond. Both the carbon and oxygen are sp2 hybridised, and the 0' bond is formed by the
overlap of an sp2 hybridised orbital of carbon with an sp2 hybridised orbital of oxygen, each containing
an electron. The unhybridised p-orbitals of carbon and oxygen, each containing one electron, overlap
sideways to form the 1t bond. The two other sp2 hybridised orbitals of oxygen contain a pair of
electrons each, which are non-bonding. The two sp2 hybrid orbitals on carbon are utilised for the
formation. of two 0' bonds with hydrogen or alkyl groups. Since carbonyl carbon and oxygen are
sp2 hybridised, the carbonyl group and the two other atoms attached to carbon by 0' bond lie in one
plane. The bond angles are nearly 120°.

'" vv.
"'C-O:
/o.Jy

The photochemical reactions of carbonyl group are best explained by considering its carbon in
sp2 and oxygen in sp hybrid state.
178 UNDERGRADUTE ORGANIC CHEMISTRY

5.4.1 Nature of Carbonyl Compound


Ketones and aldehydes are amphoteric. Thus they can react both as acids and bases. The
carbonyl group itself serves both as electrophilic and nucleophilic site.
The carbonyl group as a Base
The carbonyl oxygen has two nonbonded pairs of electrons, either of these can attack a proton
or other electrophile to form a new bond. In an attack on a proton, the carbonyl acts as a proton base,
in attacking another electrophile, the carbonyl acts as a Lewis base.

R/\C=O +
R . . proton acid
If±l~[R/'C=~_H~
R
R\~-OHl
R/
proton base protonated ketone

R\..
/C=O + ~El>~
[R\ El> R\ El>
/C=O-E~ /C-O-E
]
R •• Lewls aCid R R
Lewis base acid-base adduct

Protonated carbonyl compounds are important in the acid-catalysed reaction of carbonyl


compounds because protonation enhances the positive charge of the carbonyl carbon so that it is more
easily attacked by weak nucleophiles.
The carbonyl group as an acid
Carbonyl compounds can also act both as Lewis acids and proton acids. The polarisation of the
carbonyl group creates a partial positive charge on the carbonyl carbon. This atom is electrophilic,
and it can accept a pair of electrons from a strong nucleophile. The adduct has a new bond between
the carbon and the nucleophile, with a negative charge on the oxygen atom.
Basic condition
R,s+ 0- e R, e
C-O
R/~U R/I
strong Nu
electrophile nucJeophile
....
Under acidic conditions, the carbon of the protonated carbonyl group is much more
electrophilic, reacting even with weak nucleophile.
Acidic condition
R\ .. El>
/C=O+H
R

e
Nu

Jf weak
nucJeophile
ALDEHYDES AND KETONES 179'"

5.5 Reactions of Aldehydes and Ketones


Aldehydes and ketones undergo many reactions. Their reactivity arises from the electronegativity"
of the oxygen atom and the polarisation of the carbon-oxygen double bond. The carbonyl carbon atom,
bearing a partial positive charge, is electrophilic. Because it is sp2 hybridised and flat, this carbon is
relatively unhindered and open to attack from either face of the double bond. If the nucleophile attacks
the carbonyl group, the hybridisation state of carbon changes from sp2 to sp3. The electrons of the
pi bond shift out to the oxygen, giving an intermediate with a negative charge on oxygen. If this
oxygen atom becomes protonated, the overall reaction is nucleophilic addition: the addition of
nucleophile and a proton across the C=O double bond.

R/t r:J..
R,s+

e
0-

R,
R/T- NuNu
e
O
H-Nu

R,
R/I
C-O-H + Nu
e

Nu
It is to be noted that in addition reactions of C=O bond the nucleophilic attack precedes the
electrophilic attack because the anion produced is more stable than the cation which would result if
the electrophilic attack were to precede the nucleophilic attack.
Nucleophilic addition can take place either under acidic or basic conditions.
R\ C=O + H-Nu H$
or )
R\ C-OH
R/ ~H R/I
Nu
adduct
For nucleophilic additions to carbonyl groups:
(i) Acid catalysts work by making the carbonyl group more electrophilic and
(ii) Base catalyst work by making the nucleQphile more nucleophilic.

5.5.1 Mechanism of acid catalysed addition


R
\C=O+H-Nu H$ ) R/\C_OH
R/ R I
Nu
Mechanism
R ): Et> fast R ' " Et>
Step-I =O+H ~ r=O-H
R R
protonation makes carbonyJ.carbon
more electrophiIic
Step-II

..
R/{rJ-H
R......... et)
.,

Nu-H
! slow stcp

et)
R. . . . . -H R
C-O-H . . . . . C-OH
R/lf) R/I
Nu-H Nu
et)
adduct
180 UNDERGRADUTE ORGANIC CHEMISTRY

We~ nucleophiles such as water and alcohols often add to carbonyl group under acidic
conditions. Weak nucleophiles cannot attack unactivated carbonyl groups, but a protonated carbonyl
group is more electrophilic, allowing attack by weak nucleophile.

5.5.2 Mechanism of base catalysed additions

Mechanism
Step-I
.n
B+H0u
~
~
9
BH+Nu
e

Thus base catalyst converts weak nucleophile into strong nucleophile.


Step-II
R, R, •.
slow .. fast slow
.. /C-OH+B
R/[rJ step
R. I
Nu
e intermediate adduct
Nu
An example of this mechanism is the addition of organometallic compounds.

5.5.3 Effect of nature of nucleophile in nucleophilic addition reactions


of carbonyl compounds
(i) If the nucleophile is a good nucleophile, it will readily attack the carbonyl carbon. the
resulting anion can be protonated either by the solvent or by added acid. For example:

OH
H30El> 1
- - 7 ) CH3-C-CH3
1
CH3

e
o 0 OH
11 Ell e 1 HOHIHEI> 1
(ii) H-C-H + CH3-C==CNa~ H-C-C==C-CH3 --~) H-C-C=C-CH3
1 1
H H
(ii) A poor nucleophile requires an acid catalyst to make the nucleophilic addition reaction occur
at a reasonable rate. The acid protonates the carbonyl oxygen which increases the susceptibility of the
carbonyl carbon to the nucleophilic attack. Some examples are:
ALDEHYDES AND KETONES 181

o Et>
11 ~OH
(i) CF3--C-H + H" <=" CF3-t~H

OH2 (Weak
•• nuclpophile)

(ii) oc/~o + H,O

o
(iii) If the attacking atom of the nucleophile (such as oxygen nucleophile and nitrogen
nucleophile) has a pair of nonbonding electrons in the addition product, water will be eliminated from
the addition product. This is called a nucleophilic addition-elimination reaction.
o O-H <t>
11.. 1 H--D-H
~
HG>
R-C-R + Z-H~ R-C-R~ ~R-C-R+HOH
1
R-C-R 11
C~ z
Z
Efl
Example is:
Et>
o O-H H--D-H
11 .. HG> 1 HG> tI ~
_HG>
R-C-R' + NH2-G~ R - i -R' ~ R-C-R' R-C-R' - - 4 ) R-C-R'

C~-G
11 11
NH-G EflN-G N-G
1
H

5.5.4 Reactivity of Aldehydes and Ketones for Nucleophilic Addition Reactions


The reactivity of the carbonyl group for nucleophilic addition depends mainly on three factors.
(1) Ability of carbonyl oxygen to carry a negative charge.
(2) Nature of the groups attached to the carbonyl carbon atom.
(3) Size of the substitutent groups (steric factor).
The reactivity of the carbonyl group depends upon the nature of groups attached to the carbonyl
group. Any group that increases the positive charge over carbonyl carbon atom increases the reactivity
of carbonyl group.
Electron releasing group/groups when attached to the carbonyl carbon tend to neutralise the
positive charge of carbonyl carbon and thereby decrease the reactivity of the carbonyl group.

,,~ 5" ,,~ 5"


~ (T/
R =electron-donating group G =electron-attracting group
(+) charge over carbonyl carbon (+) charge over carbonyl carbon
atom will be neutralised. Attack by atom will be increased, attack by
nucleophile will be retarded. nucleophile will be facilitated.
Reactivity decreased. Reactivity increased.
182 UNDERGRADUTE ORGANIC CHEMISTRY

This is the reason why formaldehyde is more reactive than other aldehydes.
Aldehydes, in general, are more reactive than ketones and halo aldehydes and halo ketones
exhibit maximum reactivity.
o
Cl 11 R
Cl)C-CHO )H-C-H )CH3CHO )RCHO) "'/c=o
Cl R'
Furthermore, greater the size of the substituents attached to the carbonyl carbon, the less is the
r(",activity of the carbonyl group because the larger groups around the carbonyl carbon hinder the
attacking reagent from reaching the positively charged carbon (steric hindrance).
The carbonyl carbon atom is in sp2 hybridised state and bond angles are 120° approximately,
while in the adduct this carbon becomes sp3 hybridised and the bond angles on it are around 109.5°.
The transition state of such an addition reaction being more similar to the adduct than to a substrate,
it suffers from the steric strain and this strain increases with the increasing bulk of the groups already
present on the carbonyl carbon. The steric strain, in its turn, wiIl slow down the reaction. Thus ketones
are less reacti"e than the aldehydes. Ketones bearing very bulky hydrocarbon groups practically do
not undergo addition reaction with bulky nucleophiles. Thus the rate of addition will go on increasing
with the following compounds:

Me3C\
/C=O
< <
Me3C
Me

Me
)C=O < H

H
)C=O

Aromatic carbonyl compounds are less reactive than the corresponding aliphatic carbonyl
compounds. This is because delocalisation neutralises the partial positive charge on the carbonyl
carbon by resonance effect.
Neutralisation of partial positive change by resonance

0- J e e e
R~C~O R........ C/O R........ C/O R........ C/O

6 .. •
a .. )10

Q .. • @6
Electron-withdrawing group(s), present in the benzene ring of aromatic carbonyl compound,
increase the reactivity for nucleophilic addition reactions.

e 0
O........ @~
e/N~-R
o -- 1"'-- electron deficiency increases due to the
positive change on a-carbon

electron deficient
carbon. i.e, -/ group
ALDEHYDES AND KETONES 183

Similarly, electron releasing group(s) decreases reactivity of carbonyl compounds for


nucleophilic addition reaction.

ry
O- 0-
o
CH3-~o ~_ 11
+-R .. (f)~,1I
CH3-O~_e(f+-R

electron deficiency of carb. carbon decreases


(i.e. electrophilic chata~ter decreases)
due to the negative charge present on a-carbon
Reactivity of different carbonyl compounds in decreasing order is as follows:
HCHO > C6Hs-CH2-CHO > RCHO > C6Hs-CHO >
o 0 0
11 11 11
R-C-R > R-C-C6H5 > C~5-C-C~5
reactivity in decreasing order
Note: (i) -I group increases reactivity
(ii) Reactivity oc: -I power of the group
(Hi) +1 group decreases reactivity

~f
(iv) Reactivity oc: + I power the group
(iv) -R group present in benzene ring at 0 and/or p-position increases reactivity
(vi) +R group present in benzene ring at 0 and/or p-position decreases reactivity

Reactivity of cyclic ketones


In case of cyclic ketones the reactivity order is as follows:
o o

[>0>0=0> 6 6 >
Thus more is the angle strain in the cyclic ketones, more is its reactivity for nucleophilic addition
reactions.
Steric hindrance and more alkyl substitutents make carbonyl compounds less
reactive towards any nucleophile, electron-withdrawing groups and small rings
make them more reactive.

5.5.5 Stability and Reactivity of carbonyl compounds


The stability of carbonyl compounds can be understood by considering the resonating structures
of the carbonyl group:
e
o 0
11 1
R-C-R' ~(--7) R-C-R'
(I) Ell
(II)
184 UNDERGRADUTE ORGANIC CHEMISTRY

Although structure (II) is not a major contributor but stability can be known by this resonating
structure in which carbonyl carbon has carbocation character. Therefore, any thing that stabilises
carbocations also tends to stabilise carbonyl compounds. The following factors stabilise carbocations
and stabilise carbonyl compounds:
(i) +/ group present on carbonyl carbon will stabilise the carbonyl compound and
stability oc + l power of the group.
(ii) -/ group present near by carbonyl group destabilises the carbonyl compound and

Stability oc 1 .
-/ power of the group present 10 the compound
o 0
Thus CCI3-C-H" 11
is less stable than CH3-C-H
(iii) Groups that are conjugated with the carbonyl group, such as the phenyl group of
benzaldehyde, stabilise the carbocation by resonance, and hence stabilise carbonyl compounds.
e e
41 0 ® 0

<}=LH -- <?-~H -- O=LH


e
o
t e
o
0~.
(±)
1
C-H (±)
0=
_
1
C-H

Thus those factors which stabilise carbonyl compounds, reduce the reactivity of carbonyl
compounds for nucleophilic addition reaction. Thus

Reactivity of carbonyl compounds bT f :


oc I d
sta 1 Ity 0 car ony compoun
Aldehydes and ketones give nucleophilic addition reactions with wide variety of nucleophiles.
These nucleophile includes carbon nucleophiles, oxygen nucleophiles, nitrogen nucleophiles sulphur
nucleophiles etc.

5.6 Addition of Carbon Nucleophiles


The addition of a carbon nucleophile to a carbonyl group is an example of a reaction that forms
a new carbon-carbon bond and, therefore, increases the number of carbon atoms in the starting
material. Thus these reactions are very important to synthesise larger molecules from smaller
molecules.
5.6.1 Addition of hydrogen cyanide: Hydrogen cyanide adds to carbonyl compounds to form
a class of compounds known as cyanohydrins or gem-hydroxy cyanide.
Hydrogen cyanide is too weak an acid to add directly to a carbonyl group. Successful addition
requires slightly alkaline reaction conditions. In this way the concentration of cyanide ion is increased
and addition proceeds by nucleophilic attack of CN0 on the carbonyl carbon.
ALDEHYDES AND KETONES 185

o OH
11 1
R~-H+HCN~R-C-H
1
CN
Aldehyde cyanohydrin

o OH
11 1
R~-R/+HCN~R-C-R'
1
CN
Ketone cyanohydrin

(fast)
(i) HCN + B: ~ BHE9 + CN8 (ii)
cw
R~-R'
(slow)
.........
.........
06
1
R-C-R'
(6 I
CN CN
08 OH
1 (fast) 1
(iii) R~-R/+B~ ~R~-R/+B:
1 1
CN CN
Cyanohydrins are useful synthetic intermediates. The ~N group can be hydrolysed to a
carboxylic group, or it can be reduced to a ~H2NH2 group.
OH
1
R~~OOH

OH I
R'
1
R~-R'
1 OH
CN I
R~~H2NH2
1
R'
As HCN is very poisonous substance (cyanide ion binds to blood haemoglobin and respiratory
cytochrome in preference to oxygen), the reaction is often performed by mixing the carbonyl
compound with aqueous NaCN or KCN and then slowly acidifying the solution by adding conc.
H2S04 or HCl.
5.6.2 Reaction with Grignard Reagents: The reaction of a Grignard reagent with a carbonyl
compound is another example of a nucleophilic addition to the positive carbon of a carbonyl group.
o OMgX
11 1
R-C-R '+ R "MgX ~ R-C-R"
1
R'
186 UNDERGRADUTE ORGANIC CHEMISTRY

Reaction of a Grignard reagent with an aldehyde or a ketone provides an excellent method for
the synthesis of alcohols.
The reaction sequence consists of two separate steps:
(i) The reaction of Grignard reagent with the carbonyl compounds.
(ii) Hydrolysis of the resulting magnesium alkoxide to yield alcohol.
e(D
~ ,MgX OH
HOE!> 1
R '-C-R" + RMgX ~ R'-C-R" 3 ) R'--C-R"
1 1
R R

o OMgX
11
H-C-H 1
H--C-R
I
H

OMgX
RMgX ~_ _---=R~'C~H;.:,:O::.....-_ _ 1
R--C-R'·
I
H
o OMgX OH"
11
R~C-R" I I
R'-C-R R--C-R'
I I
R" R"
y or B-Halo ketones when treated with Grignard reagent formation of five or six membered cyclic
ether results. The reaction takes place as follows:

RMgBr.
.intramolecular SN
_ reaction
___ ---;.~ He
3
D
R 0

... (i)

intramolecular SN
reaction

... (ii)

5.6.3 Addition of Terminal Alkynes: Sodium salt of terminal alkynes reacts with carbonyl
compounds to give alkynol. This reaction is known as Ethinylation.
ALDEHYDES AND KETONES 187


ONa OH
CII
R-C==C~-R"
e ®

- R-C == C-C-R"
1

I
RI
HOH/H
$

. 1
R-C== C-C-R"
I
RI
Some examples are:
0$ (I) HCHO
CH3-C==CNa - - - - $ 4 ) CH3-C=C-CH20H
(11) HOH/H
OH
0$ (I) CH)CHO 1
CH3-C=CNa - - - - 4 ) CH3-C=C-CH-CH3
(ii) HOH/H$

$
(11) HOH/H

5.6.4 Addition of diazomethane


Diazomethane gives three types of reaction with carbonyl compounds. In these reactons nitrogen
is not retained in the product.
(i) Reaction with aldehydes: Aldehydes convert into methyl ketones by the reaction with
diazomethane.

- 11
R-C-CH3 + N== N

(ii) Aldehydes and kelones react with diazomethane to form oxiranes.

/\
R-
CWf'e
r+
RI
CH 2-N == N
®

- - R-y-CH 2
RI
(iii) Cyclic ketones (mainly five and six membered) form two products. One is epoxide and the
other is ketone with ring expansion

ft ® 0,
CHl
(i)
2s
0
~
e
+ CH2-N == N
®

- OH \1=N
C9 ®
l

'- cS 0

(ii) 0+ CHN - 2 2
Cj'\1=N
- 6+ N=N
188 UNDERGRADUTE ORGANIC CHEMISTRY

Similar reaction is also given by open chain ketones where the product is next homologous
ketone.

~ C? o
R-C + CH2N 2

k
- R-C-CH

dJ 2V
®
:=N
- 11
R-C-CH 2-R

5.7 Addition of Oxygen Nucleophile


5.7.1 Addition of water: Aldehyde or ketone reacts with water to form gem-diols.
Water is a poor nucleophile and therefore adds relatively slowly to the carbonyl group, but the
rate of reaction can be increased by an acid catalyst.
Mechanism
®
o
11
R-C-H+H
®
c:
R-C-H
O-H
11
~ R-C-H
OH
1

C..o ®

H/"'H

11
OH
G>

.. +H
G> ..
1
R-C-H
-H 1
OH

The extent to which an aldehyde or a ketone is hydrated in an aqueous solution depends on the
aldehyde or ketone. For example, only 0.2% acetone is hydrated at equilibrium, but 99.9% of
formaldehyde is hydrated.
o OH k eq.
11 1
CHr-C-CH3 + H 20 ~ CHr -C-CH 3 2 X 10-3
99.8% 1
OH
0.2%

0 OH
11
CH3-C-H + H 2O ~
~
CH3--1-H 1.4
42% 1
OH
58%

0 OH
11 1
H-C-H+H2O ~
~
H-C-H
0.1%
bH
99.9%
ALDEHYDES AND KETONES 189

o OH
11 1
CC1 3-C-H + H20 CC1 3-C-H
0.01%
6H
99.99
OH
CF3--t-CF3

6H
Why is there such a great difference?
The equilibrium constant depends on the relative stabilities of the carbonyl compound and the
hydrate. The electron donating alkyl groups make the carbonyl compound more stable where as
electron withdrawing substituent makes the carbonyl compound less stable than HeHO. From the
equilibrium constant it is clear that unstable carbonyl compounds form more stable hydrate and
stable carbonyl compounds form unstable hydrate.
In other words, steric hindrance and more alkyl substituents make carbonyl compounds less
reactive towards hydration; electron withdrawing groups and small rings make them more reactive.
o OH
11 1
CH 3-C-CH 3 CH 3-C-CH 3

6H

o OH
1
'HJ-H H-C-H
1
OH

Stability in decreasing order Stability in increasing order

.u.
reactivity for nucleophilic
addition is in increasing order
190 UNDERGRADUTE ORGANIC CHEMISTRY

5.7.2 Addition of alcohol


Carbonyl compounds give addItion reaction with alcohols. This reaction is catalysed by acid and
base. Nature of product depends on the nature of catalyst.
Case I. Addition catalysed by base
In the presence of base, one equivalent of an alcohol reacts with only one equi valent of the
carbonyl compound. The product of the reaction is called hemiacetal (in case of aldehyde) or hemiketal
(in case of ketone). The reaction is reversible. There is always equilibrium between reactant and
product.
o OH
11 8H 1
R-C-H + CH3-0-H R-C-H
1
OCH3
hemiacetal

o OCHJ
11 5H 1
R-C-R' + CH3-0-H R-C-R'
1
OH
hemlketal

Mechanism

o OH
11 e -I e
CH3-C-H + CH3--O ...... CH3-C-H + CH 3-O
1
OCH 3
hOO1iacetal
The essential structural features of hemiacetals or hemiketals are an -OH and -OR group
attached to same carbon atom.
Like the hydrates simple hemiacetals and hemiketals are generally not sufficiently stable for
isolation. Hemiacetals are stabilised by the same special structural features as those of hydrates.
However, heiacetals or hemiketals gain stability by being cyclic-when the carbonyl group and the
attacking hydroxyl group are part of the same molecule. The cychc hemiacetal or ketal may be either
five membered or six membered. Cyclic hemiacetal or hemiketal formation takes place by y or
8-hydroxy carbonyl compounds.

(~'r'.
H
~

~O R
- Lf

e
°
R - Cyclic hemiketal

r~
~ -
" H
- Cyclic hell)iketal
ALDEHYDES AND KETONES 191

Case 11. Addition catalysed by acid


In the presence of acid one equivalent of carbonyl compound reacts with two equivalents of
alcohol. Product of the reaction is acetal or ketal. The acid catalyst in most of the cases is
p-toluenesulphonic acid (Ts-OH).
Mechanism
(f)
o ~I-H
11 (f)
R-C-H+H R-C-H

~..
CHg-O-H ..
Ji
(f)
~OH,
(f) -H 0
'--I -
R-C-H R-C-H .. 2 • R-C-H
1 11
OCH 3 O-CH 3 (6CH
•• 3
(f)

OCH 3
1
R-C-H
1
OCH 3
The essential structural features of an acetal or ketal are the presence of two -OR groups
attached to the same carbon atom.
High yield of acetals and ketals is obtained if the water eliminated from the hemiacetal (or
hemiketal) is removed as it is formed. The formation of acetals and ketals requires an acid catalyst
because the tetrahedral intermediate readily eliminates water (the leaving group in the presence of
e
acid). It is difficult for the tetrahedral intermediate to eliminate the basic OH group (the leaving group
in the absence of an acid catalyst).
Because acetal (or ketal) formation is reversible, an acetal or ketal can be transformed back to
the aldehyde or ketone in an acidic aqueous solution.
OR' 0
1 11
R-C-R + H20 .....,! R-C-R + 2R '-OH
1 (excess)
OR'
Acetals and ketals are stable in basic conditions.
192 UNDERGRADUTE ORGANIC CHEMISTRY

Formation of cyclic acetals and ketals


1,2-diols form five membered cyclic acetals or ketals whereas 1,3-diols form six membered
acetal or ketals. These acetals and ketals are more stable than the open chain acetals and ketals.
CH 2-CH 2
I -t---:- five membered
o

6 - (5
e
H
. ..-

o
~ six membered ketal

6
Use of Ketals and acetals as protecting groups
- 6$
H
. ..-

Ketals and acetals are hydrolysed under acidic conditions, but they are stable toward strong bases
and nucleophiles under neutral or basic conditions. They are easily made from the aldehydes and
ketones, and hydrolysis converts them back to the parent carbonyl compound. This easy
interconversion makes ketals and acetals as protecting groups to prevent ketones and aldehydes from
reacting with strong bases and nucleophiles. Examples are as follows:
11

(i) 6- o
COOCH, + HOH,c-CH,OH ~
o 0
o-COOCH,

j(i) CH3MgBr (excess)rrHF


(ii) NH4ClIHOH

6)
Hp/H
...

(ii) A
U + HOCH,-CHPH
(Iequiv)
TsOH ..

CRO

..
ALDEHYDES AND KETONES 193

HOCH 2-CH 20HrrsOH


.. CH3~" CH 2-CH 2-Br
o 0
L-.J

CH 3 /C~H2-CH2-C55C-CH3
o 0
L-.J

5.8 Addition of Sulphur Nucleophiles


5.8.1 Addition of Sodium bisulphite: When aldehydes, aliphatic methyl ketones and some
cyclic ketones are shaken with saturated aqueous solution of sodium bisulphite (NaHS03) they form
bisulphite addition compound. These adducts are water soluble salts that are insoluble in common
organic solvents.

e
o OH OH
Cti I I I
R-C-H 55 R-C-H
R~~H - R-C-H
I® e®
-
® e I I
H--.0-r-S-O Na NaD-S=O S03Na
HD-S=O \.JIII 11
I® o o
ONa
e
The adduct when treatedwith acid, base or formaldehyde, gives corresponding carbonyl
compound.
o
HClfH20 11
.-----~R-C-H

~ 0
H-C-H 11
L...--_ _~ R-C-H

Use of bisulphite adduct formation


(i) This reaction can be used for differentiation between ketones and aliphatic methyl ketones.
(ii) Mixture of aliphatic methyl ketones and other ketones can be separated by the use of sodium
bisulphite.
194 UNDERGRADUTE ORGANIC CHEMISTRY

o 0
11 11
CH3-CH2-C-CH2-CH3 + CH3-C-CH2-CH3
1 Saturated solution of NaS03H

~ OH
CH3-CHz-C-CH2-CH3 + CH3-t-CH2-CH3
insoluble in water 1
S03Na
soluble in water
Separated by filtration

Precipitate Solution

o OH 0
11 1 H20/HCI 11
CH3-CH2-C-CHz-CH3 CH3-C-CHz-CH3--~) CH3-C-CH2-CH3
1
S03Na
(iii) Mixture of aldehyde and ketones other than aliphatic methyl ketones can be separated by
the use of NaS03H.
For example, the given two compounds can be separated by the use of NaS03H
o
11
CH3-CH2-CHO and CH3-CH2-C-CHz-CH3
(iv) Liquid aldehydes and methyl ketones can be purified by recrystallisation
o OH
11 HS03Na 1
CH3-C-H - - - 4 ) CH3-C-H
liquid 1
S03Na
crystalline solid
(v) Sodium bisulphite adduct when treated with sodium cyanide forms cyanohydrin
OH OH
1 NaCN 1
R-C-H ) R-CH-CN
1
S03Na
5.8.2 Addition of thioalcohols: Thiols react more rapidly than alcohols with aldehydes and
ketones to give thioacetals and thioketals.
ALDEHYDES AND KETONES 195

R"" CH2SH
/
C=O+ I
R' CH2SH
These substances are readily hydrolysed by aqueous HgCl2

R"" /SC2HS
/C\ + H20
HgCh
e)
R"" /C=O+Hg/\
S-C2Hs
+2HCI
R' SC2Hs H R' S-C2Hs
This reaction may also be used for protection of a carbonyl group.
One of the most important reactions of this category is the formation of thioacetals or thioketals
with a 1,3-propanedithiol. The car~onyl group of both aldehydes and ketones reacts with this
compound in the presence of an acid catalyst to form cyclic thioacetals which are called 1,3-dithianes.

('l+HOH
S"C)
~ "H
I, 3-dithiane
Normall:,', the carbonyl carbon atom of an aldehyde is partially positive. It is electrophilic and
consequently, reacts with nucleophiles. When the aldehyde is converted to 1,3-dithiane and treated
with strong base (like alkylithium), this same carbon atom becomes negatively charged and reacts
with electrophiles. This reversal of polarity of the carbonyl carbon atom is called umpolung (means
polarity reversal). Thus the term umpolung refers to the reversal of the normal polarity of a functional
group (i.e., electrophilic into nucleophilic and nucleophilic into electrophilic transformation).
The hydrogen atom of carbon-2 of 1,3-dithiane is weakly acidic (pKa = 31). In the presence of
a strong base, it forms carbanion which is stabilised by delocalisation of negative charge due to the
vacant d-orbitals of two sulphur atoms.

(i) Hs-(CH2hSWIf •
(ii) BuLi

umpolung
Nuc1e philic
Carbon
A 1,3-dithiane anion is an excellent nucleophile and reacts by SN2 pathway with primary and
secondary alkyl halides to give a disubstituted dithiane. Hydrolysis of this product in the presence of
HgC12, either in methanol or in aqueous acetonitrile, gives a ketone.

0;"
Ca
R'-CH 2-X
SN2·"
0/s
/c
RI R: " CH 2-R'

!
HgCI/HOH/CH 30H
196 UNDERGRADUTE ORGANIC CHEMISTRY

Thus formaldehyde can be converted into other aldehydes and ketones whereas aldehydes other
than formaldehyde are converted into ketones by this sequence of reactions of 1,3-dithiane.
o
H-C-H
" BuLi

o
, "
! HgCI 2IHOHlCHPH

o
R-CH 2 -C-H
"
Aldehyde
When 1,3-dithiane is treated with H2iNi desulphonation reaction takes place. Desulphonation
replaces C-S bonds with C-H bond. Thus C=O group finally converts into -CH2- group in
neutral condition.

o
6 + Hs-{CH,),-8H

1,3 dithane

5.9 Addition of Nitrogen Nucleophiles


Addition of ammonia, primary amines and other mono substituted ammonia derivatives
(~2---<;) .
Aldehydes and ketones react will ammonia, primary amines and with other mono substituted
ammonia derivatives to form imines. An imine is a compound with a carbon-nitrogen double bond.
This reaction is catalysed by a trace of acid (PH 3-4).

~
eJ
" •• " HOHlH
/C=O+NH2-Z~ /C=N-Z !!" )/C=O

The first step of reaction is the addition of the free, nonprotonated ammonia, amine or ammonia
derivative to the protonated carbonyl group. If the solution is too acidic, the concentration of the
ammonia derivative becomes negligible. If this happens, the usually fast addition step becomes slow.
•• $ $
R-NH2 + H30 ~ R-NH3 + H20
Nucleophilic nitrogen Non-nucleophilic nitrogen

•• $ $
NH2-Z+ H30 NH3-Z+H20
Nucleophilic nitrogen Non-nucleophilic nitrogen
ALDEHYDES AND KETONES 197

Unlike the first step (ammonia derivative addition) the rate of the elimination step increases with
increasing acid concentration (OHS is a strong base and a poor leaving group, while H20 is a weak
base and a good leaving group). Thus an increase in acidity causes elimination step to be faster, but
addition step becomes slower and the decrease ir acidity causes the addition step to go fast but the
elimination step becomes slow. .
In between these two extremes is the optimum pH at which the rate of the overall reaction is
greatest. At the appropriate pH, some of the ammonia derivative is protonated, but some is free to
initiate nucleophilic addition. At this pH (PH 3-4), too, enough acid is present so that elimination can
proceed at a reasonable rate. While many aldehyes and ketones are liquids, most of the derivatives of
NH2-Z are solids with sharp melting points. Therefore, these derivatives are frequently used as aids
in identifying carbonyl compounds. Since the condensation products can be hydrolysed to yield back
the original compound, such reactions also can serve to isolate and purify the carbonyl compounds
from a reaction mixture.

R, )C=O+NH2G
He
~
[R' iH )C-NHG
]_H~02
R, /C=N-G
R' R' R'
imine derivative

G = H; ammonia
G =R or Ar; primary amine
G=OH, NH2 etc.
Mechanism
Step I:

OH
I
R-C-R'

Hcl-H
@'G

!t-H*
OH
I
R-C-R'
I
NHG
carbinalamine
198 UNDERGRADUTE ORGANIC CHEMISTRY

Step 11:
O-H (tl/H
1 Ci'H
R-C-R' + H61 ~..==:;:.. R-C-R'

kHG C:~G
o-protonated
carbinolamine

R-C-R'
11 R-C-R'
$

11
E9NHG
1
NHG
(conjugated acid of imine) Nitrogen stabiliesed carbocation

ll-H$
R-C-R'
11
NHG
imine or N-substituted imine
This type of two-step reaction is often referred as addition elimination reaction. This reaction is
pH dependent reaction and best result is obtained when pH of the reaction is between 3 and 4.

5.9.1 Reaction with Ammonia


Aldehydes and ketones react with ammonia to form unsubstituted imines.

R"
R' /
C=O+H2NH~ R"
R'
/C=NH+H20

-0 -H2
Unsubstituted imines of aldehydes are unstable and polymerise on standing.
For example: formaldehyde reacts with ammonia to give urotropine.
o
11 HEll POlymerisation) N
H-C-H + NH3 ~ CH2=NH ) (CH2 6 4
Hexamethylenetetramine
or
urotropine
Formation of urotropine takes place as follows:

o
11
Trimerisation .. 3H-C-H ..

Acetaldehyde forms aldimine with ammonia. This aldimine on trimerisation gives cyclic amine
ALDEHYDES AND KErONES 199

OH
CHr
I
CH-NH 2
!J.
~ CH:rCH=NH Trimerisation..
/NH,
H C-CH CH-CH
3 3
Aldiminc
I
NH NH
I
"-.CH/
I
CH 3
Acetone reacts with ammonia to form adduct. The adduct further reacts with acetone to form
diacetone ammonia.

5.9.2 Reaction with primary amines


Aldehydes and ketones react with primary amines to give N-alkyl or N-aryl imines. These imines
are more stable than un substituted imines. Aromatic aldehydes or arylamines give the most stable
imines. These imines are called Schiff base
o
11 He
CH3-CH + C6Hs-NH2 ~ CH3-CH=N-C6Hs
Schiff base

He
C6Hs-CHO + CH3-CH2-NH2' • C6Hs-CH=N-CH2-CH3
Schiff base

Imines are crystalline compounds. On hydrolysis they regenerate carbonyl compounds because
formation of imine is a reversible reaction.
o
R" " H20 !He 11 , "
C=N-R. • R-C-R + R -NH2
/
R'
Schiff base is pink in colour. This can be decolourised by passing S02 gas. The colourless
solution obtained is known as Schiff reagent.
Schiff reagent is again converted into Schiff base by addition of aldehyde.
sOz
Schiff base ) Colourless solution (Schiff reagent)
!aldehYde ~ne
Schiff base no reaction
(pink colour)
200 UNDERGRADUTE ORGANIC CHEMISTRY

Thus. Schiff reagent can be used for the differentiation between aldehydes and ketones.

5.9.3 Reaction with Monosubstituted Ammonia Derivatives (NH2-G)


A number of compounds of the general type NH2-G react with aldehydes and ketones. The
product in these cases is N-substituted imines. The imine obtained from reaction with NH 20H
(hydroxyl amine) is called an oxime; the imine obtained from reaction with hydrazine is called a
hydrazone; and the imine obtained from reaction with semicarbazide is called a semicarbazone.
Imine type compounds formed from carbonyl compounds and a NH2-G (a reagent with an
electronegative group attached to the nitrogen) are quite stable. Table given below lists the variety of
nitrogen compounds (NH2-G) that undergo reaction with carbonyl compounds to form stable imine
type products
Substrate NHa-G Product
R
R,-C=O NHz-OH ')C=N-OH
Hydroxylamine R'
R'/
oxime

R R
'-C=O NHz-NHa '-C=N-NHa
R' / hydrazine R'/
Hydrazone

R R
'-C=O NHz-NH-C6f{, ')C=N-NH-C6H,
R' / Phenylhydrazine R'
Phenylhydrazone

R . . . . . C=O
RV NH'-NH~N02 ;>=N-NH~NO'
N02 NOz
2. 4-dinitrophenyl- 2, 4-dinitrophenyl-
hydrazine hydrazone
(2,4-DNPH)
0
0
R R')C=N-NHJ-NH2
'-C=O NHz-NHJ-NHa R'
R' / Semicarbazide Semicarbazone

The imine type compounds obtained from NH2-G (where G is -/ group) are very stable and
are not easily hydrolysed. Hence. oximes. hydrazones. Phenylhydrazones and semicarbazones are very
stable compounds.
Phenylhydrazones and 2,4-dinitrophenyl hydrazones are crystalline and coloured substances.
Thus phenylhydrazine and 2,4-DNPH can be used as laboratory reagents for the identification of CO
group in aldehydes and ketones.
5.9.4 Addition of Secondary Amine.: Formation of enamlnes
The reaction of aldehyde or ketone having at least one a-hydrogen with a secondary amine
produces an enamine. An enamine is an CX. ~-unsaturateu tertiary amine. The reaction is carried out
ALDEHYDES AND KETONES 201

in the presence of a suitable dehydrating agent. Enamine formation is also catalysed by the presence
of a trace of an acid.

R
o"
\CH-C+H-N\I
I
R" R"
~ /\CH-C-N\I ---
R
®
~9H2
~R,CH-C..!..N
OH
-H 0 R,I
"-l n./Rn -----....
H
rJJ/R" 2
Ql
R/
C C-l'lI
I R" R I , R " RV I 'R" RV I\j'R"
R' R R R
Tautomerisallon
R l1 R"
\C=rC-N1
R'/ I \R"
R
enumine

Notice that in enamine the double bond is present between carbonyl carbon and a-carbon of
carbony I compound part.
CH3\ /CH3
/C=O+NH\ ...( i)
CH3 CH3

a-carbon with respect to CO of the substrate


~ I C."'ony1 ,,"'on of th. CO gro,p

OO+H-NJ .. TsOH (YO


The secondary amines most commonly used to prepare enamines are cyclic amines such as
pyrrolidine. piperidine and morpholine.

QN
I
H
o C)
I
H H
I
Enamines are ambident nucleophile in which nitrogen and carbon both are nucleophilic centres.

R, •• /R" R e ® R"

RV
C-C-N
1 t'R" ~ ' C i N/
RV, R 'R"
nitrogen nucJeophile
carbon nucJeophile

The nucleophilicity of carbon is more than that of nitrogen. The nucleophilicity of the carbon
of enamines makes them particularly useful reaction intermediates in organic synthesis because they
can be acylated. alkylated. and used in Michael addition.
Reaction, given by Enamlne.
<a> Alkylation of enamlne: Enamines can be alkylated mainly by primary alkyl halides
because reaction is SN2.
202 UNDERGRADUTE ORGANIC CHEMISTRY

G
- 6-
-xe
C
H,-R

Iminium ion
The product iminium ion is readily hydrolysed.

6- 0 CH2
-
R
+

I
H
Thus the given sequence of reactions can be used for alkylation of ketones at a-carbon.
o o

6 (i) O-H/TSOH

(ii) R-CH 2-X


(iii) HzO/If
.. 6- CH2 R
-

(b) Acylation of enamines: Enamines can be acylated either by the use of acyl halides or by
the use of acid anhydrides.

o o Q
6- CH
,-R
11
R-C-Cl ..

6-
The over all reaction can be represented as follows:
CH2 R
-

6
(c) Michael Addition:
(i)O-H/TSOH

(ii)R-C-X
11
o
(iii) H20flf
..
Enamines behave as carbon nucleophile for Michael addition reactions.

Q e

conjugate addition
.. ~I
U _Hr-CH=C~R
ALDEHYDES AND KETONES 203

W N 0

~H,-CH,J-R .. Tautomerisation

o
t
HPJi
0

~H,-CH,--LR
The over all reaction can be represented as follows:

6
o
(i)OHffSOH

(ii) CH2= CH-)i-R


(iii) H20nf 0
• 6-
o
CH,-CH,J-R
0

5.10 Reduction of Aldehydes and Ketones: An aldehyde or a ketone can be reduced to an


alcohol, a hydrocarbon or an amine. The product of the reaction depends on the reducing agent and
on the structure of the carbonyl compound.
OH
H21Pt or Metal hydride 1
r-------~ R-CH-R'
Ana1cohol

CH3
I e (9
o NH2NH2 + CH34-OK

11 CH3
R-C-R'f-----------~ R-CH2-R'
or Zo/Hg + HCl An alkane

NH2
NH3 + [H] R-CH I R'
~------~ -
An amine
5.10.1 Hydrogenation: The pi bond of a oorbonyl group can undergo catalytic hydrogenation,
just as the pi bond in an alkene. Alkene can be hydrogenated at low pressure and at room temperature,
but for hydrogenation of a carbonyl group, heat and pressure are usually required. A ketone is reduced
to a secondary alcohol by catalytic hydrogenation, while an aldehyde yields a primary alcohol. Yields
are excellent (95-100%).
204 UNDERGRADUTE ORGANIC CHEMISTRY

0 H
11
R-C-H
H2INi
)R-C-H
I
Primary alcohol
A/pressure
I
OH
0 H
11
R-C-R'
H2/Ni
)R-C-R'
I
Secondary alcohol
~/pressure
I
OH

6 0
--.;;...----..
/j.
H2/Ni
I pressure
cS Secondary alcohol

If both a double bond and a carbonyl group are present in a structure, the double bond may be
hydrogenated, leaving the carbonyl group intact, or both may be hydrogenated. However, the carbonyl
group cannot be hydrogenated independently of the double bond.
o 0
11 Ni/H2 11
R-CH=CH-CH2-C-H---+) R-CH2-CH2-CH2-C-H
25°C
o
11 Ni/H2
R-CH=CH-CH2-C-H ) R-CH2-CH2-CH2-CH20H
Alpl'essure
If it is desired to reduce a carbonyl group while leaving a double bond intact, a metal hydride
reduction is the method of choice.
S.10.2 Metal hydride: A more convenient method for reduction of aldehydes and ketones to
aIcohols involves the use of two valuable reducing agent lithium aluminium hydride (often abbreviated
as LAH) and sodium borohydride. (NaBH4)
H H
e I
Li H-Ala_H Na
e
H-B~-H
la
I I
H
H
Lithium aluminium hydride Sodium borohydride
+1 +3-4 +1 +3-4
LiAl~ NaBH4
OH
(i) LAH
.------+ R-C-R
I,
o (ii) H 0IH
e I
2
11 , H
R-C-R
OH
(i) NaBH4 I,
' - - - - - - + R-C-R
(ii) H 0/H
2
e I
H
ALDEHYDES AND KETONES 205

These two metal hydrides are quite different in their reactivity. LAH is a powerful reducing agent
that reduces not only aldehydes and ketones but also carboxylic acids, esters, amides and nitriles. LAH
undergoes violent reaction with water, reduction is usually carried out in a solvent such as anhydrous
ether or THF.
NaBH4 is a milder reducing agent than LAH. Its reaction can be carried out in water or alcohol
as the solvent. For the reduction of an aldehyde or ketone, NaBH4 is the preferred reagent. It is more
convenient to use because of its lack of reactivity toward water. While NaBH4 reduces aldehydes and
ketones rapidly, it reduces esters very slowly. Therefore, an aldehyde or ketone carbonyl group can
be reduced without the simultaneous reduction of an ester group in the same molecule. This selectivity
is not possible with LAH.
0 0 0
" " (i) NaBH4
H-C-CH2-CH2-C-OC2H5---~) "
HOCH2-CH2-CH2-C-OC2H5
e
(ii) H /H 20

Neither NaBH4 nor LiAlH4' reduces isolated carbon-carbon double bonds but C=C in
conjugation with a carbonyl group is sometimes reduced.
Metal hydrides (NaBH4' LAH) react by transferring a hydride ion to the positive carbon of the
carbonyl group, just as Grignard reagent transfers Re to the carbonyl group.

~~ fe ?e
R-C~-H • R-Z-R' t + AlH3

three more H's


Each hydride ion can reduce one carbonyl group. Therefore, one mole of LAH or NaBH4 can
reduce four moles of aldehyde or ketone theoretically. After the reduction is completed, treatment with
water or aqueous acid liberates the alcohol from its salt. (If water, methanol or ethanol is used as a
solvent for a borohydride reduction, this step occurs spontaneously). In the hydrolysis, the aluminium
and boron portion of the reagent are converted to AI(OHh and boric acid, respectively.
The formula of lithium aluminium hydride is usually written as LiAlH4 but interpreted as
e
Lie [AlH4]e or Lie AlH4' Thus in ether solution it exists as aggregate of solvated lithium ions and
aluminohydride ions. The first step in the reaction with aldehyde or ketone is transfer of hydride ion
to give the complex (I). Since this has three more hydrogen atoms available it can react with three
more moles of aldehyde or ketone to give the alcoholate (II), which on decomposition with water
affords the alcohol, aluminium hydroxide and lithium hydroxide.
o H R' H
11 lee I lee
R-C-R' + H-AI -H Li ) R-C-O-AI -H Li

H
I I
H H
I
(I)

I,RJ-R'
R
OH O-CH<R'
I H e IH20 R"
4 R-C-R' + AI(OHh + Li(OH) ~(- - /CH-O-Al-O-CH \
/R I)
I
H
R'
(11)
RR'
O-CH <R'
I
206 UNDERGRADUTE ORGANIC CHEMISTRY

Similarly. NaBH4 reacts as follows:

~
+ H
R-C J '-HNa----·
Ye ~ R, Ye
CH-O-B-HNa
~
R'/ I
(1) H

!3RJ_R
/R
HI , °l-CH'R'
H20 I HEfJ R, e /R ~
4R-C-R + H 3B03 + NaOH .. CH-O-B-O-CH Na
I ~/ I /R
,~
OH 0 -CH'R'
5.10.3 Metal alkoxide: Meerwein-Ponndorf-Verley reduction: This is a common
procedure for the reduction of carbonyl compounds. particularly of unsaturated aldehydes and ketones.
This reagent attacks only carbonyl compounds.
When ketone is dissolved in a solution of isopropyl alcohol containing aluminium isopropoxide.
the ketone is reduced to the corresponding alcohol. An equimolar amount of isopropyl alcohol is
converted to acetone. This procedure. which is extremely selective in that it reduces only carbonyl
compounds, is called the Meerwein-Ponndorf-Verley (MPV) reduction.

CH
RJ-R' + CH3--CHOH--CH3 + AI-{O-CH ( 3] -=== R--CHOH-R' + CH3J--CH3
Solvent CH3 Product
3
In this reaction metal salt of secondary alcohols (generally aluminium isopropoxide) can transfer
hydride to carbonyl group of aldehyde and ketone. Since metal alkoxides undergo rapid
hydrogen-metal exchange reaction, an alcohol may be used as the source of hydrogen in the presence
of catalytic amount of aluminium isopropoxide. Isopropano.l and aluminium isopropoxide are
frequently used. Reaction Gan be forced to high conversion by continuous removal of acetone by
distJilation.
Mechanism

OH (j)
I CH,
R-C-R' .. H IHzO
+ 3 C=O
CH /
I 3 (acetone)
H
Product
ALDEHYDES AND KETONES 207

5.10.4 Reduction to Hydrocarbons:


(a) Clemmensen reduction: This is the classical method for the reduction of carbonyl group
to a methylene group using zinc amalgam and hydrochloric acid.
o
11 ZnlHg ,
R-C-R'--~) R-CH2-R
Hel
The mechanism of the reaction is summarised below:
(tJOH
:0:
ql OH
® ~H2
11 H(tJ 1 H
R-C-R' .. R-C-R' .. R-C-R'
• RC-R' I . I
:znrc? ZnCI ZnCI

!-H2O

fncI ZnCI
e e I
R-y-R' .. +Cl
R-q-R' .. R-C-R'
re
ZnCI

!H$
-ZnCI2
ZnCI Cl
C:.:a
H H
I e e $ I
+Cl H
R~-R' • R-y-R' .. R-y-R'
r-e
ZnCI Cl
-ZnCI2
H H
(b) Wolff-Kishner reduction: Aldehydes and ketones are reduced to hydrocarbons on heating
in the presence of excess hydrazine and a strong base.
o
11, Strong base ,
- R-C-R + NH2NH2 ) R-CH2-R
A convenient solvent for the reduction is diethylene glycol (DEG) whose bp is 245°C.
The mechanism of the reaction is given below:
o
11
(i) R-C-R' + NH2NH2 r=
OH
I -H20
R-C-NHNH2 - - 7 ) /C=NNH2
R"
I R'
R' Hydrazone

(ii) ~ C=N-NH
R'/ q - [~e
C-N-NH -
R'/
~eC-N
R./
NH ]
(~ IHOH
OH +
208 UNDERGRADUTE ORGANIC CHEMISTRY

When alkoxides are used as base in the presence of polar solvents (DMSO), the reaction takes
place at room temperature. The best result is obtained with potassium t-butoxide.
5.11 Oxidation Reactions
5.11.1 Aldehydes can be oxidised with K2Cr207 and KMn04 in acidic medium to form
.
carboxylic acids containing the same number of carbon atoms.
o
11 K2Cr207M~
Ar-C-H ~ Ar-COOH
o
11 K2Cr20 7/H$
R-C-Ij ) RCOOH
Aldehydes can also be oxidised by much milder oxidising agents such as TolIens' reagent,
Fehling's solution and Benedict's solution.
Tollens'reagent: Aldehydes when warmed with a solution of ammonical silver nirate (Tollens'
reagent) produce a precipitate of metallic silver which deposits on the walls of the test tube giving a
silver mirror. This is called the silver mirror test.
RCHO + 2Ag(NH3hN03 + H20 ~ RCOONH4 + NH3 + 2NH4N03 + 2Ag (mirror)
Fehling's solution: Fehling's solution is an alkaline solution of Cu 2+ complexed with sodium
potassium tartrate ions. When this solution is used to oxidise an aldehyde the complex cupric ion
(deep blue) is reduced to cuprous oxide (red).
o 0
11 11 ge
R-C-H + Fehling's solution (Cu 2+) + NaOH--~) R-C-ONa + "/'CU20 + H20
red
Since ketones do not undergo oxidation under mild conditions, these reagents are also used for
differentiating them from ketones. These reagents also do not attack olefinic bonds and hence the
reaction provides valueable method for the synthesis of a, ~ unsaturated acids from a, ~-unsaturated
aldehydes.
Agf£>
R-CH=CH-CHO ) R-CH=CH-COOH
Ketones can be oxidised with strong oxidising agents, they breakup to give acids having lesser
number of carbon atoms.
o
11 K2Cr207/Hf£>
CH3-C-CH3 ) CH3COOH + C02 + H20
In the case of mixed ketones the oxidation takes place according to Popoff's rule. According to
this rule the cleavage takes place in such a manner that the carbonyl group goes along with the smaller
alkyl group.

[0]
CH3-CH2-CH2-CH2r--c-CH3-~)
I~ CH3CH2CH2COOH + CH3COOH
I
5.11.2 Oxidation with Se02: Selenium dioxide is a valuable reagent for the oxidation of a
methylene group adjacent to the carbonyl group of aldehydes and ketones. If carbonyl compound has
no a-CH2- group then in that case it oxidises a-CH3 into CHO group.
ALDEHYDES AND KETONES 209

o
se0 2 11
R-CH2-CHO ) R-C-CHO + Se + H20
o 0 0
11 Se02 11 11
R-CH:z-C-CH3 ) R-C-C-CH3 + Se + H20

Soo, • ~-CHO
o 0
11 Se02 11
CH3-C-CH3 ) CH3-C-CHO
5.11.3 Baeyer-Villiger oxidation: Oxidation of ketones to esters by peracids is called B.V.
Oxidation. The reaction is catalysed by acids.
o 0 0
11 11 11 0
R-C-R' + R"-C-O-O-H ----4) R-C-O-R' + R"-C-f'
Ester "OH
Mechanism of Baeyer-Villiger Oxidation:
o
o 0 4,-H 0
11
R-C +C_u-C-O-O-H
1
U
6 S
11
~ R-~-O-~-CJIs
1
R R
OH 0 0
Nucleophilic. 1 11 11 e
addition reaction R-Vlj-C-C,H, - - -.. . . . C,H,-C+-O
Adduct of ketone and peracid
(?-H
I ..
R--C-O-R
o ..
o
11
R-C-O-R 1l
o
+ III O-H
o 11 ••
11 R-C-O-R
C6HS-C-O-H

1lO-H
I 0
R-C=O-R ..
210 UNDERGRADUTE ORGANIC CHEMISTRY

For unsymmetrical ketones the approximate order of migration (R') is tertiary alkyl> secondary
alkyl> aryl> primary alkyl> methyl.
5.12 Reactions Involving a-hydrogens:
5.12.1 Keto-Enol EquiIibria: Hydrogens on a carbon directly attached to a carbonyl group
are referred to as a-hydrogens.
o
1 1 11
-C-C-C-
1 1
H ~a-hydrogen

Aldehydes and ketones having a-hydrogen atom(s) exist in solution as an equilibrium of two
isomeric forms, the keto form and the enol (from ene + 01, unsaturated alcohol) form. For simple
aliphatic ketones there is very little of the enol form present at equilibrium, as shown by the following
examples:
o OH
11 1
CH3-C-CH3 ~ CH3-C=CH2
(0.01%)
o OH
11 1
CH3-C-CH2-CH3 ~ CH3-C=CH-CH3
(0.12%)

o OH

6 6 (1.2%)

This type of isomerism, where the isomers exist in equilibrium and are rapidly interconvertible,
is referred to as tautomerism, and the isomers are known as tautomers. The phenomenon of
tautomerism is of importance in the presence of a heteroatom such as nitrogen, oxygen or sulphur in
the system. In such cases the rate of interconversion of the isomers (tautomers) is relatively rapid.
o OH
11 ~O 1 ~O
CH3-C-CH2-C" ~ CH3-C=CH-C"
OEt OEt
N-C6HS NHC6HS
11 1
CH3-C-CH3 ~ CH2=C-CH3
tfJ #0 tfJ/OH
CH3-N( ~ CH2=N,
"0<0 'OE>
On the other hand, simple isomerisation of double bond is not considered a case of tautomerism.
CH3-CH=CH-CH3 ~ CH3-CH2-CH=CH2
ALDEHYDES AND KETONES 211

Even though the percentage of enol tautomer at equilibrium is quite small, the enol is important
in many reactions. Many reactions of aldehydes and ketones occur by way of the unstable enol form.
Enolisation is subject to both acid and base catalysis. Hydrogens, ex to a carbonyl group are
acidic in nature due to strong electron-withdrawing effect of the carbonyl group. These hydrogens can
be abstracted by strong bases to give an anion called enolate anion. This enolate anion is resonance
stabilised. The negative charge is delocalised between ex carbon and carbonyl oxygen. The enolate
anion may be protonated on carbon, which will regenerate the keto form, or on oxygen to yield the
enol form.

OH
I
CH 2 = C-CH3 + OH
e
The first step of the base catalysed enolisation is an acid-base reaction, with ketone acting as a
protonic acid. The pKa of acetone is approximately 20. Although acetone is an extremely weak acid
as compared to HCI (pJ!a =-2.2), acetic acid (pKa = +5) or water (pKa = 15.7), we must remember
that acidity is relative. If we compare acetone to ethane (pKa = +50) we see that C-H bond in acetone
is much more acidic than the C-H bond of alkanes.
The reason for this enhanced acidity is apparent from a consideration of the conjugate base
produced by ionisation of the two carbon acids.
e
CH3-CH3~ CH3-CH2+H$

The anion produced from ethane has its negative charge localised on carbon. Since carbon is a
fairly electropositive element, a carbanion is a high energy species and the ionisation that produces it
is highly-endothermic. On the other hand, the anion produced by ionisation of acetone is not really a
carbanion but resonance hybrid of two structures. In one resonating structure, the negative charge is
on carbon as in the ethyl anion. On the other, the negative charge is on the more electronegative
oxygen. Although both structures contribute to the resonance hybrid, that in which the negative charge
is on oxygen is clearly dominating. The anion derived from acetone is neither (I) nor (Il), it has
character of both. An alternative symbol that gives a better picture of the electron distribution is
p.o
CH3-C~,e
" CH2
The negative charge is divided between carbon and oxygen. When this anion reacts with water,
it can undergo protonation either on carbon, in which case the keto form results, or on oxygen, in
which case the enol form is produced.
In neutral solution the principal base is H20. Since H20 is a much weaker base than OHe proton
212 UNDERGRADUTE ORGANIC CHEMISTRY

transfer for an aldehyde or ketone is not as rapid, and consequently enolisation is slow. However, in
acidic solutions, the weakly basic carbonyl groups are protonated. The protonated carbonyl compound
loses a proton from a-carbon with much greater ease, even to a weaker base, H20. A carbonyl group
is not very basic, and only a small amount of the protonated structure is present at equilibrium. The
presence of a positive charge, however, greatly increases the rate of proton loss from a-carbon to the
solvent.

(ii)

OH
1l
I
CH2=C- CH3 + H30~
5.12.2 Enolate ions: The keto-enol equilibrium can be almost completely shifted towards enol
form by the use of strong bases such as lithium diisopropylarnide and potassium triphenylmethide.
e~
o OLi

6
pKa = 16.7
Lithiumdiisopropyl
amide
(LOA)
--6 pKa = 40

o OeK~
11 e I
CH3-C-CH3 + (C6HShCK~ - - - - + . CH3C=CH2 + (Ct#shCH
Potassium triphenylmethide
An unsymmetrical ketone such as 2-methylhexanone can form two possible enolates.
e e
0 0 0

6 CH3
Base
~

6 CH3
+ (r CH
3

more stable less stable


enolate enolate
(I) (Il)
ALDEHYDES AND KETONES 213

Enolate (I) is more stable because the double bond is more highly substituted. Enolate (II) is
less stable because the double bond is less substituted.
Just, which enolate is formed predominantly depends on the base used and on the conditions
employed. NaH in the presence of aprotic solvent forms stable enolate (thermodynamic enolate)
whereas LDA in the presence of aprotic solvent forms less stable (kinetic enolate).
o 0
I NaH II E>
CH3-C-CH2-CH3 -~) CH3-C-CH-CH3
I
o
l LDAIDMF

E>
0
e I I
CH1~H2---013 ~",:~~;:3

o
I
CH2=C-CH2-CH3
Kinetic enol ate
In many cases these enolate anions have proved valuable synthetic intermediates.
Enolates are ambident anions (anions which can react at two different positions are called
ambident anions). Just as they may undergo protonation on either carbon or oxygen, they may also
react with other electrophiles at either of these two centres. Two examples that illustrate this ambident
character are the reactions with chlorotrimethyl silane and methyl iodide.

6
a.-hydrogen acidity is responsible for a significant part of the chemistry of carbonyl compounds.
We consider some of the reactions in this group.
5.12.3 Haloform reaction: Acetaldehyde, methyl ketones and methylcarbinols
(CH3CHOHR) react rapidly with halogens (CI2, Br2, 12) in the presence of alkali to form haloform.
Mechanism
o 0
I gH I
(i) R-C-CH3 + X2----t) R-C-OE> + CHX3
Haloform
214 UNDERGRADUTE ORGANIC CHEMISTRY

o
~ f\ 11
OH+H..LCH2-C-R

o
11
CH2X-C-R
In the haloform reaction, the a-hydrogens of an aetaldehyde or a methyl ketone are initially
replaced by halogens. Each substitution is a two-step process commencing with the formation of
carbanion. The carbanion displaces a halide from a halogen molecule, completing the substitution.
The acidity of the remaining a-hydrogens is enhanced by the electronegativity of the halogen
and they subsequently undergo abstraction and replacement with increasing facility.
x 0
~ I11
(ii) OH + H\JH -C-R

o
11
CHX2 -C-R

x 0 X 0 X 0
~ I 11 1 11 x-x I 11
(iii) OH+H"Cf-C-R--"~e?-C-R - - -.. X-?-C-R

X X X
The trihalogenated ketones and aldehydes are unstable to base and are attacked at the carbonyl
carbon, with the displacement of a trihalomethyl anion.
e
f41
X-C-C-R
e
+ OH - - -.... X-SJ-C-R
fG
~ ~ * 6H
X X
!
/0 le
R-C ......e+
o X-CH
1
.. X-C +
1 I
X X
Haloform
5.13 Condensation Reactions
The carbonyl carbons of aldehydes and ketones are electrophilic in character and therefore reacts
with nucleophiIe. We also know that when a proton is removed from the a-carbon of a compound
ALDEHYDES AND KETONES 215

having electron withdrawing group (group containing carbon hetero double bond), the resulting anion
is nucleophile. Thus this anion can give nucleophilic addition reaction with carbonyl compounds.
Step 1. Formation of carbanion
e
0 0 0
11 Base e 11 1
CH3-CH2-C-R-~) CH3-CH-C-R ~~ CH 3-CH=C-R
Enolate ion

Step 2. Nucleophilic addition to carbonyl group

?i ~Q?
R-C-CH2 + R'- -R'
0
11
~
1 h.$
0
11
OH·
1
R-C-CH2-,-R' - R-C-CH 2-,-R'
1e~
1 -
(an electrophile) R' R'
o
I
R-C=CH2
(a nucleophile)

These two steps are common in every condensation reaction given by carbonyl compounds.
5.13.1 The Aldol Addition: An aldol addition is a reaction between two molecules of
aldehydes or two molecules of ketone having at least one alpha hydrogen. When the reactant is an
aldehyde, the addition product is a f3-hydroxy aldehyde also known as aldol. When the reactant is a
ketone, the addition product is a f3-hydroxy ketone. Because the addition reaction is reversible, good
yields of the addition product are obtained only if it is removed from the solution as it is formed.
The aldol reaction is carried out in the presence of dilute base (NaOH or KOH) below lO°e.
The aldehyde reaction works well when one drop of dilute NaOH is added to aldehyde. The ketone
reaction is best seen with Ba(OHh-
Mechanism: The mechanism of the aldol addition illustrates two important characteristics of
carbonyl compounds: the acidity of their alpha hYdrogens and the tendency of their carbonyl groups
to undergo nucleophilic addition.
Step I: In the first step, a base removes an alpha proton from the carbonyl compound, creating
an enolate.
e
o 0
{;)/Y 11 e I
HO + HL-CH2-C-H ~ HOH + CH 2-CHO - CH2=C-H
Enolate ion
216 UNDERGRADUAE ORGANIC CHEMISTRY

Step 11: The enolate anion then acts as nudeophile-as a carbanion-and attacks the carbonyl
carbon of a second molecule of carbonyl compound producing an alkoxide anion.
e
00 0 0
G~
CHr-C + CH2- C -H -
?i CH2=C-H
1
~ CH3-CH-CH2-C-H
1 11

I An alkoxide anion
H
Step Ill: The alkoxide anion removes a proton from the solvent to form the aldol

e
o 0 OH
1 11 1 0
CH3-CH-CH2-C-H + HOH----.7) CH3-C-CH2-CHO + OH
Aldol
Ketones are less reactive than aldehydes for nucleophilic addition reaction, hence aldol addition
occurs more slowly with ketones.
o 0 OH 0
11 &r &- 11 Ba(OHh 1 11
CH3-, + H-CH2-C-CH3 ~ CH3-,-CHz-C-CH3
CH3 CH3
~-Hydroxyketone

Notice that the product of an adol addition has twice as many carbons as the reacting aldehyde
or ketone.
The Mixed Aldol Addition or Crossed Aldol Addition (or Reaction)
An aldol addition that starts with two different carbonyl compounds is called a crossed or mixed
aldol reaction. If both carbonyl compounds have alpha hydrogens, four products can be formed,
because each carbonyl compound can react with itself as well as with the other carbonyl compound.
The four products have similar physical and chemical properties, making it difficult to separate them.
Consequently, a crossed aldol addition that forms four products is not a useful reaction.
s
OH
CH3-CHO + CH3-CH2-CHO ---+) four aldols
Formation of four aldol products takes place as follows:
o OH
11 &r &- 1
(i) CH3-C + H-CH2-CHO ) CH3-CH-CH2-CHO
1
H
o OH
11 &r &- 1
(ii) CH3-CH2-C + H-CH-CHO ----.7) CH3-CHz-CH-CH-CHO
1 1 1
H CH3 CH3
ALDEHYDES AND KETONES 217

o OH
11 &t 5- I
(iv) CH3-C + H-CH-CHO-~) CH3-CH-CH-CHO
I I I
H CH3 CH3
Under certain conditions, a mixed aldol addition can lead primarily to one product. If one of the
carbonyl compounds does not have any alpha hydrogens, it cannot form an enolate. This reduces the
number of possible products from four to two.
e
OH
C~s-CHO + CH3-CHO -~) Two products

• o OH
11 &r 5- I
(i) CH34+H-CH2-CHO-~) CH3-CH-CH~CHO

H
o OH
11 S+ 5- I
(ii) C6Hs4 + H-CH2-CHO -~) C~s-CH-CH2-CHO

H
A greater amount of cross product will be formed if the compound without alpha hydrogen is
always present in excess.

(Excess)
A commo1l'method used to obtain a single aldol product is to use LDA to remove the a-hydrogen
when creating the enolate. Because LDA is a strong base, all the carbonyl compound will be converted
into an enolate so there will be no carbonyl compound left with which to react. Addition will occur
when the second carbonyl compuond is added slowly to the reaction mixture.
OH
LOA e (i) CH3-CH2-CHO I
CH3-CHO -~) CH2-CHO ) CH3-CH2-CH-CH2-CHO
(ii) HOH
100% yield

Intramolecular Aldol Additions


Intramolecular aldol addition is given by a, ro-dicarbonyl compounds. Five and six membered
rings are often formed by the intramolecular adol additions of a, ro-diketones. Aldol cyclisations of
rings larger than six and smaller than five are much less common, because the formation of larger
and smaller rings is less favoured by their instability.
Because a 1,4-diketone has two different sets of a-hydrogens, two different intramolecular
addition products can be formed: one product would contain a five membered ring and the other a
218 UNDERGRADUAE ORGANIC CHEMISTRY

three membered. The five membered ring product is the only product formed from the intramolecular
addition of a 1,4-diketone.

~\\

~ ?i
CH3-~CH2

1 CH3 .• c;CH3
c;6 cf:Y
---
HOH

0
OH

not formed

An intramolecular aldol addition of a 1,6-diketone can lead to either a seven or a five membered
ring product. Again the five-membered ring product is the only product of the reaction.
o 0
11 11
CH3-C-CH2-CH2-CH2-CH2-C-CH3
El
OH

~
y~3
o
~HOH

y~:3
o
(Small amount)
ALDEHYDES AND KETONES 219

1,5-Diketones and 1,7-diketones undergo intramolecular adol addition to form six membered
ring products.

1,5-Dlketone

5.13.2 Aldol condensation: Aldol addition followed by dehydration is known as aldol


condensation. A condensation reaction is a reaction that combines two molecules while removing a
small molecule (usually water or an alcohol). Dehydration of aldol occurs readily because of the
acidity of the a-hydrogen and also because the double bond formed as the result of dehydration is
conjugated with a carbonyl group.
Dehydration of aldol occurs in basic as well as acidic conditions. So heating the aldol addition
product in either acid or base leads to dehydration. Product of the reaction is a,f:3-unsaturated carbonyl
compound.

NaOH/~ [~H
CH3-CHO + CH3-CHO--~) CH3-CH-CH2-CHO
1 -HOH
----7) CH3-CH=CH-CHO
a,l3-unsaturated aldehyde

S: >[ C6 HJ:-CHr -CHOl_-_HO_H~) C~5-CH=CH-CHO


5

5.13.3 Claisen-Schmidt Reaction: Crossed oldol condensation between aromatic aldehyde and
aliphatic ketone (or mixed ketone) is known as Claisen-Schmidt reaction. This reaction is useful when
bases such as sodium hydroxide are used because under these conditions ketones do not undergo se\f-
condensation. Some examples are:
o 0
11 e 11
C6H 5-CHO + CH3-C-CH3 I~OJ;IC ' C6H5-CH=CH-C-CH3
4-Phenyl-3-buten-2-one
(Benzalacetone)
220 UNDERGRADUAE ORGANIC CHEMISTRY

o 0
11 8H/30°C 11
C~S-CHO + CH3-C-C~S • C6Hs-CH=CH-C-C6Hs
1.3-Diphenyl-2-propen-I-one
(Benzalacetophenone)

5.13.4 Perkin Reaction: The condensation of aromatic aldehydes, with acid anhydrides having
at least two a-hydrogen atoms in the presence of a weak base, usually the sodium or potassium salt
of the acid corresponding to the anhydride, is called the Perkin Reaction. The product of the reaction
is a,~ unsaturated carbonylic acid.
The reaction has been used frequently for preparation of cinnamic acid and its derivatives.
Weak base
C~sCHO + (CH3COhO ) C~S-CH=CH-COOH + CH3COOH
CH 3COOK Cinnamic acid
The first two steps of the reaction are similar to aldol type reaction. The basic catalyst removes
an a-proton from the anhydride and the resulting carbanion then adds to the carbonyl group of the
aromatic aldehyde. Protonation followed by dehydration and hydrolysis yields the a, ~ unsaturated
acid.

First step
o
8~n ~
CH3CO + H CH2 - C ' 0 ~,=='>=: CH COOH +

y/
3
CH3 -

Second step

Step III
oe 0 0 OH 0 0
I "" 3
C6Hs-CH-CH2-C-O-C-CH3 CH COOH~ C6Hs-CH-CH2-C-O-C-CH3 I ""
-CH3COO
Step IV

GH Y ?i ?i
C~s-CH-CH-C-O-C-CH3 ---+ C~s-CH=CH-C-0-C-CH3
?i ?!
~ 2!:. +~3COOH+H20
e
0 - COCH3
!
H201H

C~s - CH = CH - CO OH + CH3COOH
a. f3-unsaturated acid
ALDEHYDES AND KETONES 221

5.13.5 Knoevenagel Reaction: The condensation of aldehydes or ketones, not containing any
a-hydrogen, with compound having active methylene group is called Knoevenagel reaction. This
reaction is catalysed by weak bases like amines. .
/COOEt B: /COOEt
(i) C~5CHO + CH2\ ) C6HS-CH=C\
COOEt COOEt
(i) H201H$

j(ii) tJ.

CJfs-CH=CH-COOH
a,~ unsaturated acid
COCH3 COCH
3
C~sCHO + CH2(
B: /
(ii) ) C6Hs-CH=C\
COOEt COOEt

j
(i) H201H$
(ii) tJ.

C6Hs-CH=CH-COCH3

The mechanism of the reaction is very similar to Perkin reaction.


Step I: Removal of acidic hydrogen by base:

.("\ f""\./ COOC2HS $ e./ COOC 2Hs


R 2NH+H-l-CH'COOC H ~ R 2NH2 + CH'COOC2H s
2 s
Step 11: Nucleophilic addition reaction:

Step Ill: Dehydration reaction:


OH
q COOC 2HS
C6Hs-CH~<COOC2H5
C~./R
H-N'R
222 UNDERGRADUAE ORGANIC CHEMISTRY

Ketones undergo this reaction only with those compounds which contain highly activated
a-hydrogen

0 +0 0
Base/ll
oa
o
5.13.6 Mannich Reaction: In the Mannich reaction formaldehyde is condensed with
ammonia, a primary amine, or a secondary amine and a compound containing at least one active
hydrogen atom. The reaction is acid as well as base catalysed.
The following are some of the compounds which have the active hydrogen atom(s):
Ketones, ~-ketoesters, ~-cyanoesters, nitroalkanes alkynes, phenols, etc.
The product in this reaction is a ~-amino carbonyl compound known as the Mannich base.
The initial step of the reaction involves the formation of the imminium salt by the reaction of
formaldehyde with amine which is subsequently attacked by the carbanion or the enol.
Mechanism
Step-I

R .........Efl H20
R/ N =CH2 .....
Imminium ion
Step-I1
o o
~n 11 e 11
OH + H-CH2-C-R' :;;;:,==.~
. . HOH + CH2 -C-R'
Carbanion
Step-Ill
o
11 /R
• R'-C-CH2-CH2 -N .........
R
Mannich base
ALDEHYDES AND KETONES 223

Nett reaction:

(ii)

H (active hydrogen)
(iii)
O:1
~
I N
I
H
I + CH 0 + NH/ CH3
2 'CH
3

The mechanism of acid catalysed reaction

Step I

OH OH
I "/R
H-C-N
I
H
'R -
-H
®
I
H-C-NH/
I
H
G) R
'R

Step II

5.13.7. Reformatsky Reaction:


(1) This reaction takes place between aldehydes and a-haloesters in the presence of zinc metal.
(2) Product of the reaction after acid hydrolysis is ~-hydroxy ester.
224 UNDERGRADUAE ORGANIC CHEMISTRY

(3) The f3-hydroxy ester produced in this reaction is easily dehydrated to ex, f3-unsaturated ester
or acid because dehydration yields conjugated system which is stable due to resonance.
OH
(i) Zn I
(i) C@fs-CHO + Br-CHz-COOC2H S (ii) HOHINH Cl ) C@fs-CH-CH 2-COOC2H s
4 ~-Hydroxy ,~ster

(i) Zn
(ii) C6H s-CHO + Br-CH2-COOC2Hs (ii) NH CIIHOHld) C6Hs-CH-CH2-COOC2Hs
4
[,H ]
J-HOH
C6H s-CH=CH-COOC2HS
~-phenyl ex, [3-unsaturated ester

This ex, f3-unsaturated ester undergoes hydrolysis to give ex, f3-unsaturated acid
Ell
HOH/H1d
C@fs-CH=CH-COO~Hs ) C@fs-CH=CH-COOH + C2HSOH
Mechanism:

O-Zn-Br
If' I
(i) --... CH2-C-OC2H s
Zinc enolate

OH o-Zn-Br 0
I HOHINH4CI I 11
R-CH-CH2-COOC2H s .... ---=--- R -CH - CH2- C- C2HS
J3 -Hydroxy ester
Zinc enolate does not react with ester, hence self condensation reaction does not take place
between ester and ester. Zinc enolate reacts with carbonyl compounds to give zinc alkoxide which,
on hydrolysis, gives f3-hydroxy ester.
Examples:
(i) ZnlC 6H s
(i) CH3-CH2-CH2-CHO + Br-CH2-COOC2H S )
(ii) NH4ClIHOH

OH
I
CH3-CH~CH2-CH-CH~COOC2Hs
ALDEHYDES AND KETONES 225

CH3 OH CH3
I roWC~ I I
(ii) CH3-CHO + Br-C-COOC2HS ) CH3-CH-C-COOC2Hs
I (ii) NH4CIJHOH I
CH3 CH3
CH3 OH CH3
I (i) ZnlC 6H 6 I I
(iii) C6HS-CHO + Br-CH-COOC2HS .. ) C6HS-CH-CH-COOC2HS
(n) NH4CIJHOH

CH3
I (i) ZnlC6Hs
(iV) C~S-CHO + Br-CH-COOC2Hs ----~)
(ii) itHOHlA

In this reaction c:>.rbonyl compounds may be aldehydes or ketones.


The haloester of the reaction in most of the cases is a-bromoester or its vinylog i.e.,
Br
I
R-CH-CH=CHCOOC 2Hs
However, the reaction may be carried out with a-halo nitriles and a-halo N, N-disubstituted
amides in place of a-halo ester. Sirnilary, nitrile can be used in place of carbonyl compound.
NZnBr
Znlether 11
(v) Br-CH2-COOC2HS + CH3-C==N ,) CH3-C-CH2-COOC2Hs

1
H20 :
o
11
CH3-C-CH2-COOC2Hs
~-keto ester
OH

(vi) C6HS-CHO +
(i) Znlether/A
CI-CH2-C==N----$~) C~s-CH-CH2-C==N
I
(ii) HOHlH
226 UNDERGRADUAE ORGANIC CHEMISTRY

5.13.8 Benzoin condensation


Aromatic aldehydes when refluxed with alcoholic solution of potassium cyanide, undergo self
condensation to form an a-hydroxy ketone. For example: OH 0
KCN/HOH/C2H j OH 1 11
C6H 5-CHO + C6H5CHO • C6H5-CH--C--C6H5
a-Hydroxyketone or Benzoin
The reaction is specifically catalysed by cyanide ion.

oe
Step-I EtOH I EtOH >-
~ C6Hs-C-CN <;; EtOS
I
H
(IT)

OH OH
I e I
C~s-C=C=N~(---+) C~s-~-CN

(IV)

Step-II

We know that the hydrogen of the -CHO group (structure I) is not acidic. However, cyanide
ion when attached to this carbonyl carbon atom by nucleophilic addition boosts the acidity of this
hydrogen atom (structure (11) and (III». The a-hydrogen atom of this cyanohydrin (III) becomes
similar in character to the a-hydrogens of nitriles and is removed by base (CN-). Thus the following
three properties make CN0 a specific catalyst for the reaction.
(a) Sufficient nucleophilicity to add to carbonyl group ((1) to (ll».
(b) A marked acid strengthening effect on a-hydrogen atom of the cyanohydrin (III).
(c) The ability of cyanide ion to depart from the cyanohydrin in the last step.
This reaction is unsuccessful with aliphatic aldehydes.
5.13.9. Cannizzaro Reaction
When an aldehyde that has no hydrogen a to the carbonyl group is treated with concentrated
aqueous base, a disproportionation reaction occurs. One-half of the aldehyde is reduced to a primary
alcohol, and the other half is oxidised to the corresponding carboxylic acid.
o
R
\
11
conc.OH
eRR
\ \
2 R-C-C-H - - - - 7 ) R/C-CH20H + R/C-COO
°
R/t H 20 R R
No a-hydrogen Primary alcohol Salt of carboxylic acid
For example, formaldehyde is converted into methyl alcohol and sodium formate on treatment
with concentrated sodium hydroxide solution.
ALDEHYDES AND KETONES 227

The reaction is called Cannizzaro reaction. The aldehyde is both oxidised (to a salt of formic
acid) and reduced (methyl alcohol) a general reaction that is sometimes called auto-oxidation or
disproportionation.
The mechanism of the Cannizzaro reaction starts with addition of hydroxide ion to the carbonyl
group to give alkoxide ion. This alkoxide ion then transfers a hydride ion to the carbonyl carbon of
the second molecule of the aldehyde. Thus one molecule of aldehyde acts as a hydride donor and the
other functions as an acceptor. The mechanism of the Cannizzaro reaction is as follows:
Step I: Nucleophilic addition of hydroxide ion to carbonyl group.
cf3
Gb(Je
R-C-H +OH ::;;::::=='>.~
" I
I
R-C-H

OH
Step 11: Intermolecular hydride ion transfer

?e
Slow
~ R-~-OH + H-C-R
I
H
anion of gem diol
Step Ill: Acid-base reactions yielding observed products
o 0
11 11
R-C-OH + NaOH - - - - t ) R-C-OeNaEf) + H20
019 OH
I ,
R-C-H + H20 - - - - t ) R-C-H
I
H H
I
When the Cannizzaro reaction is performed in D20 instead of H20, the alcohol formed has no
carbon-deuterium bond thereby establishing that the transfer of hydrogen in the form of hydride ion
from one molecule of aldehyde to the other molecule of aldehyde is intramolecular transformation.
The Cannizzaro reaction is suitable only for the aldehyde without an a-hydrogen because this
He transfer process is slow and difficult. Any a-hydrogen present would react to give enolate ions
and aldol condensation products far more rapidly than the Cannizzaro reaction.
Crossed Cannizzaro Reaction
Cannizzaro reaction between two different aldehydes having no a-hydrogens gives a mixture of
four products. This type of Cannizzaro reaction is known as crossed Cannizzaro reaction.

NaOH ~ C H CH 0H +
6 s 2
~COONa
0
H2 OCH)
(I)
OCH:\ (11)
228 UNDERGRADUAE ORGANIC CHEMISTRY

o
~OCH3
OH + C,;H,COON.

OCH3
(Ill) (IV)
However, when an aldehyde is treated with aqueous base and formaldehyde, it is the
formaldehyde, rather than the other aldl;hyde, that is oxidised.

CH20H

r&
~OCH3
+ HCOON.

OCH3
Oxidation of formaldehyde can be explained on the basis of the following facts:
(i) It is most reactive aldehyde for oxidation.
(ii) In aqueous basic solution it exists mainly as the conjugate base of its hydrate.
o OH OH
" + HOH
H-C-H I
~H-C-OH -----+)
gH I El
H-C-O
I I
H H
This is one of the intermediates of the reaction.
(iii) It has two hydrogens on carbonyl carbon which are available for transfer as hydride ion in
step 11. The other aldehyde hydrate anion has only one hydrogen.
Intramolecular Cannizzaro reaction: This reaction is given by dialdehydes in which
a-hydrogen is not present.
CHO ©rCH,oH
(i) conc. NaOHla
(jj •
(ii) H COOR
© r CHO

Co/CHO (i) conc. NaOHla Co/CH'OH


(jj •
(ii)H

CRO COOR
(i) conc. NaOHla
ORC-CRO (jj • CR2OH-COOR
(ii) H

Internal cross-Cannizzaro Reaction


a-keto aldehydes also give Cannizzaro reaction known as internal crossed-Cannizzaro
reaction. In this case, aldehyde group undergoes oxidation and keto group undergoes reduction. In
this case, keto group should have no a-hydrogen.
ALDEHYDES AND KETONES 229

o OH
11 (i) conc. NaOHl~ I
C6HS-C-CHO ) C~S-CH-COOH
"(ii) He
An interesting example of such a crossed Cannizzaro reaction combined with aldol condensation
is known as Tollens reaction and this reaction is used for the preparation of pentaerythritol from
acetaldehyde and formaldehyde.
CH20H
gH HCHO I
CH3-CHO + HCHO -~) HOCH2-CH2-CHO e ) CH-CHO
OH I
CH2CHO
e
HCHOIOH

CH20H
I HCHO
HOH2C4-CH20H + HCOONa ( 8H
CH20H
Pentaerythritol
This reaction involves three successive aldol condensations of acetaldehyde with formaldehyde.
The product has no a-hydrogens left and is reduced by the formaldehyde to give pentaerythritol.
Pentaerythritol is a synthetic intermediate in the manufacture of many dish washer detergents.
5.13.10. Tlschenko Reaction Or Tischenko condensation
(1) This reaction takes place between two molecules of aldehydes (same or different). Best result
is obtained when both aldehydes are same.
(2) Reaction is catalysed by aluminium ethoxide. Reaction is also catalysed by A1 203' Aromatic
aldehydes give this reaction in the presence of Na2[Fe(CO)4]'
(3) Reaction is two-step reaction. i.e., redox reaction followed by ester formation. Thus this

_tion is ..ren::,of::::::" (C~~"AV' ) [CHJ-DH +CH,-~H20H1


Oxidation Reduction 1E~r formation

11
CH3-C-O-CH2-CH3
Ethyl acetate
o
Na2[Fe(CO)4]1~ 11
C6HSCHO + C6HSCHO ) C6Hs-C-O-CH~C6Hs
Mechanism:
o
(C 2HsOh AI " 11
R-CHO + R-CHO---~) R-CH2-O-C-R
~
230 UNDERGRADUAE ORGANIC CHEMISTRY

Step-Ill:
H H o
I~.r-.... e Hydride ion "
R-C-O-C-LO....lAl(OC2Hs)3 tranfer ,. R-CH2-0- C-R + Al (OC2H s)3
(i) I Ester
R
5.14 Wittig Reaction
(1) The reaction of carbonyl compounds with phosphorus ylide to produce an alkene is known
as Wittig reaction.
(2) Phosphorus ylide is obtained from triphenylphosphine and primary or secondary alkyl
halides in the presence of strong base (NaH, NaNH2, R-Li, etc).
(i) Ph3P / R'
R-CH2-X ) R-CH=C
(ii) Base
R' Alkene
\R'
(iii) /\C=O
R'
Product from the substrate can be written as follows:
- Remove one hydrogen and halogen from the a-carbon of alkyl halide.
- Also remove oxygen of the carbonyl group and then join a-caroon of alkyl halide and
carbonyl carbon of carbonyl compound by double bond, e.g.
CH3
I (i) (C6HshP
C6Hs-CHX----~) C6H S-C=CH-CH3
i (ii) NaH I
remove (iii) CH3-CHO CH
3
Hand X i Product
Remove
Oxygen
Mechanism:
R, (i) (C6Hsh P RI, /R
'CH-X----~) 'C=C
R/ (ii) R-Li R/ \R
(iii) R[-C-R 2 2
11
o
ALDEHYDES AND KETONES 231

The first step is a nucleophilic substitution reaction. Triphenylphosphine is an excellent


nucleophile and a weak base. It reacts with primary and secondary alkyl halides by an SN2 mechanism
to give an alkyl phosphonium salt.

SN2
~ L
[ . Et)
C6H 5)3P-CH'R
/RJe X
An alkyl triphenyl
phosphonium halide

A strong base (usually R-Li, C6H5-Li, NaH or NaNH2) removes a proton from the carbon that
is attached to phosphorus to give ylide.
R
(±)
(C6Hs)3P -rfJ.
I
R
Hd- Li -
(l
(±) t 5-
(C6Hsh - P-?-R + RH
~ R
~./R Phosphorus ylide
(C 6H S)3 P =L..'R
The carbon of the ylide is a nucleophile and gives nucleophilic addition with carbonyl compound
to form betaine which leads to the formation of a four membered ring, an oxaphosphetane.
Oxaphosphetane is strained and unstable and gives alkene and triphenylphosphine oxide.

Alkene Triphenyl phosphine oxide

The Wittig reaction is applicable to a wide variety of compounds and although a mixture of
(E) and (Z) isomers may result, the Wittig reaction gives a great advantage over most other alkene
. syntheses in that no ambiguity exists as to the location of the double bond in the product. This is in
oontrast to f)-elimination reaction of alkyl halides which gives multiple alkene products either by
rearrangement or by I3--C'S.

(ii) RLi

(iii)Q=O

A widely used variation of the Wittig reaction is the Horner-Wadsworth Emmons modification.
232 UNDERGRADUAE ORGANIC CHEMISTRY

The Borner Wadsworth-Emmons reaction involves the use of phosphonate ester instead of

0
triphenylphosphonium salt.
(i) (C2H sO)3 P
(ii)RLi· =CH-CH3

(iii)O=O

(i) (C 2H sO h P• ~CH - COOC2H 5


(ii)R-Li V
(iii)Q=O

5.15 a, f3-unsaturated Aldehydes and Ketones


carbonyl group and a carbon-carbon double bond in conjugation act as a single functional group.
AThe electronic structure of such subtances may be represented by the following resonance forms:
e
o 0
11 I
CH2=CH-C-R ~(--+) CH2=CH-C-R ~(--+
I /EI:)
Electrophilic site
11

e
o 0
El:) e 11 El:) I
CH2-CH-C-R ( ) CH2-CH=C-R
(Ill) El&trophilic site IV
The most significant changes in the chemical properties of a, f3-unsaturated carbonyl functions
relative to isolated carbonyl and carbon-carbon double bond is a modification of the reactivity of the
carbon-carbon double bond. The addition of electrophilic reagents is greatly retarded. Such addition
can be made to occur only under vigorous conditions and with prolonged reaction times. For example:
o 0
11 Brz 11
CH2=CH-C-R ) CH2-CHBr--C-R
!!,. I
Br
On the other hand, the ease of nucleophilic addition to the carbon-carbon double bond is greatly
enhanced. Thus a, f3-unsaturated carbonyl compounds mainly give nucleophilic addition reactions.
Nucleophilic Addition
The contributing resonance structures (II) and (IV) for a, f3-unsaturated carbonyl compound
show that the molecule has two electrophilic sites the carbonyl carbon (11) and the f3-carbon (IV).
Thus a nucleophile can add either to the carbonyl carbon or to the f3-carbon. Nucleophilic addition to
the carbonyl carbon is called direct addition or carbonyl addition.
s
qOI °I He
OH
I
CH2 =CH-C-R ---.~-.. CH2=CH-?-R - CH 2=CH-C-R

~
Nu
Nu
I
Nu
ALDEHYDES AND KETONES 233

NucleophiIes that are relatively strong bases such as alkyllithium, LiA1H4 and NaBH4 usually
form direct addition product.
o OH
11 (i) CH3-Li 1
CH2=CH-C-R ) CH2=CH-C-R
(ii) HOHIH(£! 1
CH3

j<i) LiAIH4
(ii) HOH
OH
1
CH2=CH-C-R
1
H
Nucleophilic addition to the ~-carbon is called conjugate addition because addition occurs to a
double bond conj~gated with the carbonyl group. The initially formed product of conjugate addition
is an enol that immediately tautomerises to a carbonyl compound. The overall reaction amounts to
addition to the carbon-carbon double bond, with the nucleophiIe adding to the ~-carbon and a proton
from the reaction mixture adding to the a-carbon.

~ ~ ~H
~CH -CH
Nu
~IC-R -.. Nu-CH2-CH=C-R
I --+-
He
Nu-CH2
ClI
-CH-C-R
2
enol tautomer

! Tautomerisation
o
11
Nu-CH 2-CH2-C-R
Keto tautomer
Thus in the conjugate addition reaction addition is 1,4 but the product is 1,2-addition.
NucleophiIes that are relatively weak bases, such as cyanide ion, amines, thiols and halide ions
usually form conjugate addition products.
o 0
11 (i) C~ 11
CH2=CH-C-CH3 ---~) CH2-CH2-C-CH3
(ii) HOlIlH(£! 1
CN
Conjugate addttion may be achieved either by base or acid catalysis.
Base catalysed conjugate addition
e e
H-Nu + OH--~) HOH + Nu e
o O-H
Q4) 1 HOH 1
~ ~ 11-' - Nu-CH2-CH=C-R-Nu-CH2-CH=C-R
Nu + CH2-CH-C-R
1Tautomeris~on
11
Nu-CH2-CH2-C- R
234 UNDERGRADUAE ORGANIC CHEMISTRY

Acid catalysed conjugate addition of H-Nu


o
11 $
CH2=CH-C-R + H

> Nu-CH2-~C-R
cr H

1T
-,"
o
11
Nu -CH2-CH2-C-R
Conjugate addition (i.e., 1,4-addition) of enolate ion to et, l3-unsaturated carbonyl compounds is
. e e
called Michael addition. This reaction takes place in the presence of base, (OH, R-O, sec. amines,
etc).

Some ~hemists refer to all nucleophilic conjugate additions as Michael addition.


The substrates of the reaction, which give conjugate addition, are the compounds containing
activated double bonds, i.e., et, l3-unsaturated carbonyl compounds, esters, cyanides, quinones
et, l3-unsaturated nitro compounds. Reagents of the reaction are those compounds which have at least
one acidic hydrogen and convert into nuc1eophile in the presence of base. Such compounds are
compounds having active methylene group, nitroalkane, sulphones, indenes, fluorenes, alcohols, thio
alcohols and terminal alkynes.
o 0
11/COOC2HS KOHlMeOH HSC200C\ 11
CH2=CH-C-R + CH2" ----7) / CH-CH2-CH2-C-R
COOC2Hs HSC200C

Mechanism:
Step I.
e
~
OH e /COOC2HS
~
CH" +HOH
COOC2Hs
Nuc\eophile
ALDEHYDES AND KETONES 235

Step 11.

Michael addition reaction is conjugate addition, i.e., 1,4-addition reaction but overall product 6f"
the reaction is 1,2 addition product which takes place on C=C bond due to tautomerisation.
Michael addition of vinyl cyanide is also known as cyanoethylation reaction because it
introduces the -CH2-CH2-CN fragment into a molecule.
conjugate 'addition with nitroalkane having at least one a-hydrogen is known as Nef reaction.
Examples: 0 °
11 iPr2NHlCHC13 11
(1) CH3-N02 + CH2=CH-C-CH3 ) 02N-CH2-CH~CH2-C-CH3
(2) I-CH~H~CH2-CH2-CH=CH-COOC2H5 + CH3-N02

lK C0 IDMF
2 3

I-CH~H~H2-CH2-CH-CH2-COOC2H5
1
CH2
1
N02
o
°11 iPr NHlCHC1
2 3
11
CH~CH2-C-CH3
(3) CH2=CH-C-CH3 + CH3-CH2-N02 ) 1
CH-N02
1
CH3

(4)6 o
236 UNDERGRADUAE ORGANIC CHEMISTRY

(6)6 o

(excess)
o

m6 (Small)

VERY SHORT ANSWER QUESTIONS


1. Why are a-hydrogens of aldehydes and ketones acidic in nature?
2. Which of the following compounds will give positive Fehling's solution test?
C@fsCHO, CH3COCH3, CH3CHO
3. What happens when acetone is added slowly to formaldehyde in the presence of an alkali?
4. Name the reagent which can be used to convert acetophenone into phenyl acetate.
5. What is a Wittig reagent? How is it prepared?
6. Given the structure of a compound in each case with the formula C4HSO that satisfies the given
criteria:
(a) gives a negative haloform test but gives 2,4-DNP derivative.
(b) gives a positive haloform test and a 2,4-DNP derivative.
(c) gives a positive haloform test but no 2,4-DNP derivative.
7. Give the IUPAC name of (a) the only aldehyde and (b) the only primary alcohol that give a positive
iodoform test.
8. Why are aldehydes stronger reducing agents than ketones?
9. What is Corey's reagent? For what purpose is it used?
10. Give the product(s) of the following reactions:
LiAIH4 NaBH4
(a) C6HsCH=CHCHO --~ (b) CHz=CHCOCH3---4
(c) C@fsCOCH3+NaIO~
11. Match the reagents in List A with the names of reactions in List B.
List A List B
(i) Aluminium isopropoxide (i) Reimer-Tiemann reaction
(ii) Chromyl chloride (ii) Benzoin condensation
(iii) CHCl3 + KOH (Hi) Oppenauer oxidation
(iv) Hydrazine + Potassium tert-butoxide (iv) Etard reaction
(v) Cyanide ion (v) Wolf-Kishner reduction
12. Explain why benzaldehyde gives a positive test with Tollens' reagent but not with Felling's solution?
13. Predict the product of the following reactions:
ALDEHYDES AND KETONES 237

(i) CH 30Na
(a) C6HsCOCHO El> )
(ii) H30

14. How will you prepare deuterated benzaldehyde (C6HSCDO) from benzaldehyde?
15. Give the product(s) of the following reactions:
CRO
(a) O-CRO dil.alkali ...
o
o
(b)
©r O (i) cone. NaOH/~

CRO (ii)H
$"

(0)6 (i) Mg-Hg


Cl)
(ii) H30
..

PROBLEMS WITH SOLUTIONS


1. Explain why ketones are less reactive than aldehydes for nucleophilic addition reactions.
2. Giving reasons. arrange the compounds in order of increasing reactivity toward nucleophilic reagents.

°
11
(a) CH3CHO. CH3-C-CH3•

°
11 °11
Cb) Ar-C-Ar. Ar-C-R. R-C-R and Ar-CH2-C-R
°
11 °11

3. When a mixture of one mole of benzaldehyde and one mole of cyclohexanone is treated with one
mole of semicarbazide. cyclohexanone semicarbazone precipitates only. but after a few hours the
precipitate is the semicarbazone of benzaldehyde. Explain this experimental result.
4. Hydrated acetaldehyde is unstable but hydrated trichloroacetaldehyde is stable. explain.
5. Explain why: (a) a base catalysed halogenation of acetone cannot be stopped at monohalo stage.
(b) The acid catalysed halogenation of R-CH2-CO-CH3 gives
R-CHX-CO-CH3 and not R-CHr-C0-CH2X.
6. Explain why only the alpha hydrogen atoms in saturated carbonyl compounds take part in the aldol
condensation reaction.
7. The condensation between 1 mole of acetaldehyde and one mole of crotonaldehyde gives sorbic
aldehyde. Explain the reaction.
e
OH
CH3-CHO + CH3-CH=CH-CHO~ CH3-CH=CH-CH=CH-CHO
Sorbic aldehyde
8. Aldehydes having a-hydrogen atoms usually do not undergo the Cannizzaro reaction under its
reaction condition; give an explanation.
9. Why does LiAII4 usually fail to reduce a C. C mUltipule bond? Why does such a bond in conjugation
with an aromatic system on one side and a carbonyl group on the other side get reduced by the same
reagent?
10. 'Why do the following compounds give iodoform test?


238 UNDERGRADUAE ORGANIC CHEMISTRY

(b) R-C-CH2-C-R
11 11
o 0
11. Why does a base fail to remove the hydrogen of carbonyl carbon ()f the aldehyde when there is
a-hydrogen?
12. Why is formaldehyde always oxidised in the cross Cannizzaro reaction between formaldehyde and
other aldehyde.

PROBLEMS FOR SELF ASSESSMENT


1. Starting with cyciohexanone and any thing else you need, provide preparation of the following:

(a)
()OH (b)
()D (cl 0
C)<~D
(d)
0 (e) (f) HOOC-(CH2)4-COOH

(glCX: (h) ()B' (i)


C)<CJIlOH

C)<OCH3 6-6 (1)0


OH OH

(j) OCH3
(kl

(m)
()CHO
0
2. Starting with cyclohexanone suggest reasonable synthesis for the following:

(alQo
DD

(b) 00 (cl 0 CH3

0
D D

Cd) 6CH3 (e) OD


,
ALDEHYDES AND KETONES 239

3. How will you differenciate the following pairs of compounds by simple chemical tests?

(a) HCHO and CH3CHO


o
11
(c) HCHO and CH3-C-CH3 (d) Cyclohexanone and cyclohexanol
(e) 2-Pentanone and 3-Pentanone (t) Pentanal and 2-Pentanone
(g) 2-Pentene and 2-Pentanone
4. Show how to bring about the following conversions using triphenylphophene as one of the reagents:
CH
/ 3
(a) CH3-(CH2h-CH2-Br~ CH3-(CH2h-CH=C\
CH3

(c) 0 0

(d) ~CHO_ _ _~ ~CH=CHY(3I

~CHO ~CH=CH~
5. Suggest a method for the conversion of:
o
11
(a) C6HS-CH2-C-CH3 ~ C6Hs-CH2-C00H

(b)
Cl
o CHO
·D-CHOH-cD
o 11 0
0
0

(c)
60

cS
0

(d)
60
.& 0

(e)
6 •
6
240 UNDERGRADUAE ORGANIC CHEMISTRY

CHzOH
1
(t) CH3-CHO~ HOH~-C-CHzOH
1
CHzOH

o 0
(g) @-~-CH2-CH2-CH2-Br - - @-~-<J

Base I 6
..
o
11 (i) NaOHl6
(c) C6H S-C-CHCI Z )
E9
(ii) HOH/H

(d)
6 + CH
/COOC 2H s
2'COOC 2H s
C 2HsONa
C 2HsOH
,

6
0
e
(e) + CHF'CH-CHO OH
..
0
0

(t)
6 0
+ CH3MgBr HOH/H
@

e
..

0 ..
11 OH/D
(g) C6H s-C-C 6H s +

0 0 $

(h)
11
CH3-C--CHr-C-CH3
11 NaOH/I2
..
I2 /NaOH ..
(i) [>-CHOH-CH3
7. Write an arrow fonnalism mechanism for the conversion of diketone (I) into the important perfurmery


ALDEHYDES AND KETONES 241

ingredient cis-Jasmone-(II). There is another possible cyclopentenone that could be formed from (l).
What is its structure? Write an arrow formalism mechanism for its formation.

8. When p-methylacetophenone is oxidised with an excess of iodine in base, it forms terephthalic acid.
Explain why the methyl group on the benzene ring is oxidised.
9. When 4-hydroxybutanal is dissolved in methanol containing hydrochloric acid the following reaction
occurs:
HO-CH2-CH2-CHrCHO + CH30H

lfi
('0'l<H + HOH
L-.-J OCH3

(a) What type of compound is the product?


(b) Propose a mechanism of this reaction.
10. An acetal can be formed in acidic medium but not in basic, why?
11. 3-Phenyl-2-butanone can form two enols. Write their structures. Which one is the major product?
12. For each of the following pairs of compounds, indicate the member which would be more reactive
towards the indicated reagent. Give the structure of the product formed.
(a) HCHO or CH3CHO towards NaS03H.
(b) Acetophenone or benzophenone towards phenylhydrazine.
(c) Cyclohexanone or 3-hexanone towards semicarbazide.
(d) Benzaldehyde or phenylacetaldehyde towards HCN.
13. Supply the missing reagent/reagents and product/products as required to complete the following
reactions:

Base
(b) C6HSCHO + ? ) C6Hs-CH=CH-COOH

°
11
(c) CH -CH2-C-CH3 HOIHOH)?
e
3

(d) C~s -C
°
11-CHO (i) conc. NaOHl8
E& )
(ii) H30
242 UNDERGRADUAE ORGANIC CHEMISTRY

o
? 11
Ce) C6HSCHO----t C 6HS-CHOH-C-C 6H s
IHN0 3

?
14. Write equations to indicate all organic products, for the reaction of p-bromoacetaldehyde with each
of the following. Indicate the absence of reaction by NR.
(a) dil. NaOH, (b) conc. NaOH
(c) acetaldehyde, dil. NaOH (d) acetone, dil. NaOH
(e) acetophenone, dil. NaOH (t) formaldehyde, conc. NaOH
(g) benzaldehyde, dil. NaOH
15. Starting with acetophenone, and using any other needed reagents suggest synthesi.s for the following:
(a) ethyl phenyl ketone (b) methyl phenyl carbinol
(c) ethylbenzene (d) 2,3-diphenyl-2,3-butanediol
(e) 2,2-diphenylpropionic acid (t) benzoic acid
16. Cyclohexanone reacts with diazomethane to produce A and B. Suggest mechanism.
o

6 + CH,N,

(A) (8)

17. The addition of hydrogen cyanide to carbonyl compound is readily reversible reaction
OH
C=O + HCN ~ c/\
CN
Indicate in each case which of the following would be expected to contain more cyanohydrin at
equilibrium in the above reaction. Indicate your reasoning.
(a) HCHO or CH3CHO
o
Cd) @-CHO or @-~-CH3
18. Suggest reagents for the conversion of 3-pentanone to:
(a) Triethylcarbinol (b) 2,3-Pentandione
Cc) 3,4-Diethyl-3,4-hexanediol (d) Pentane
(e) 3-Pentanol
19. Suggest a method for the conversion of:

Ca) a o
.. r-O-..--COOH
ALDEHYDES AND KETONES 243

o
11
(b) C6Hs-CH=CH-C-CH3 - - 7 C6HS-CH=CH-COOH

(c) 0-
o
1
CHO ----+-~ O-.C-!-fJ
H

o I 11 0
o OH
H
1
(d) C6HSCHO - - 7 C6HS-C-C-C6HS
11 1
o OH
20. Write the structures of the products of the principal reaction, if any, of propanaldehyde with:
(a) Absolute alcohol and dry HCI (b) Phenylhydrazine
(c) Butadiene (d) Lithium aluminium hydride
(e) Tollens' reagent
21. Show how one may accomplish each of the following conversions in a practical manner:
o
11 CH3\ CH3
(a) CH3CH2CtI2-C-CH3 - - 7 /C=C(
CH3 CH2CH2CH3
CH20H
1
(b) CH3-CH2-CH0--7 CH3-C-CH20H
1
CH20H
CH20H
1
(c) CH3-CHO - - 7 HOH2C-C-CH20H
1
CH20H
(d) C6Hs-CHO - - 7 C6HS-CH=CH-CHO
22. Which of the following aldehydes would form the most stable hydrate, the least stable hydrate and
why?
(a) BrCH2-CHO (b) Br2CHCHO (c) Br3CCHO
23. For each of the following pairs of compounds designate a simple chemical test to distinguish one
member of pair from the other. Choose only tests that give visible results. Write equations for the
reactions that occur and indicate what is observed.
(a) Ethylbenzene and acetophenone
(b) Benzaldehyde and acetophenone
(c) C6Hs-C=CH and benzaldehyde
o 0
11 11
(d) CH3-CH=CH-C-H and CH3-CH2-CH2-C-H
24. An alkyl bromide A reacts with magnesium metal in dry ether to form Grignard reagent (B). Treatment
244 UNDERGRADUAE ORGANIC CHEMISTRY

of (B) with D20 gives a monodeuterated compound (C). When (C) is brominated a new alkyl bromide
(D) is formed, which still contains deuterium, (A) and (D) are isomer. Treatment of (B) with water
gives 2-methylpropane. On the basis of this information, draw structures for (A) to (D).
25. A neutral compound (A) CIOH2202, is optically active. (A) does not react with Br2 in CCI4 or
2-4-dinitrophenylhydrazine or sodium metal. (A) is unaffected by heating it in the presence of
aqueous base. When heated with aque0us acid. however. (A) is converted into two new compounds,
(B) and (C); it is found that 1 mole of (A) yields 1 mole of (B). C6H I20, and 2 moles of (C),
C2H60. (B) is optically active, and it reacts with NH20H to give an oxime but does not give a silver
mirror when treated with Ag(NH3)1. (B), when treated first with I2 and NaOH (aqueous) and then
neutralized with acid gives (D), CSHI002 and iodoform. Draw the structures of compounds (A) to
(D). Indicate briefly the reasoning you use in reaching these answers.
26. An optically active compound (A), C lO H20, gives optically active compound (B), ClO H 220 2 on
treatment with dilute protassium permangnate. (B) reacts with periodic acid HI04, to yield 'two
products (C) and (D). These same compounds can be obtained by treating (A) first with ozone and
then with water and zinc metal. Compound (C), CSHlOO is still optically active and it gives a positive
Tollens' test. Compound (D), CsHlOO is optically inactive and gives a positive iodoform test but a
negative Tollens' test, it does react readily with 2-4-dinitrophenylhydrazine to form a yellow-orange
precipitate. Clemmensen reduction of compounds (C) and (D) gives the same hydrocarbon (E),
CsHI2' Deduce the structures of compounds (A) to (E), and write equations for the reactions that
occur.
27. Compound (A), C I4H20 is an optically active aromatic compound, which decolourizes bromine in
carbon tetrachloride. Ozonolysis of (A) gives two compounds (B) and (C), compound (B), C9H IOO,
is optically active and contains an aromatic ring. (B) gives silver mirror with Tollens' reagent.
Compound (C), CSHlOO is optically inactive and is unaffected by Tollens' reagent. On reduction with
lithium aluminium hydride (C) gives compound (D), CsHI20, which, when heated with concentrated
H2S04, gives a single compound (E), CSHlO' Ozonolysis of (E) gives equimolar amounts of
acetaldehyde and propionaldehyde. On the basis of these data, deduce the structures of compounds
. (A) to (E).
28. An aqueous NaOH solution is added to a mixture of acetone and formaldehyde.
(a) What is the structure of organic anion formed?
(b) Would this anion undergo reaction at a faster rate with acetone or with formal-dehyde?
(c) Show each step in the mechanism for the predominant adol condensation that would occur.
29. Predict the major organic product:

° .
vJ
e e
HO (1) HO IH 20
(b) -...:..(i'-i)-H-$I-L\--=--....,.~

°
ALDEHYDES AND KETONES 245

ANSWERS TO VERY SHORT ANSWER QUESTIONS


1. Due to electron-withdrawing nature of C=O group and resonance stabilisation of the resultant
carbanion.
2. CH3CHO (only aliphatic aldehydes give positive Fehling's solution test).
3. Crossed aldol addition occurs:
NaOH
CH3COCH3 + HCHO~ CH3CHOCH2CH20H
4. Perbenzoic acid (Baeyer- Viii iger oxidation).
5. Phosphorus ylide is called a Wittig reagent. it is prepared by treating on alkyltriphenyl phosphonium
halide with a strong base such as n-butyllithium.
o
~ I ~ e
(C6HshP4-H + R'-Li ~ (C6HshP-i-R + R 'H

R R

o
11
6. (a) (CH3hCHCHO (b) CH3CH2CCH3 (c) CH2=CH-CHOH-CH3
7. (a) Ethanal (b) Ethanol
8. Aldehydes are more readily oxidised than ketones due to the presence of a hydrogen atom on the
carbonyl group which can be converted into OH group without involving the cleavage of any other
bond.
~ e
9. Pyridinium chlorochromate (PCC) CSHSNHCr0 3Ci. For the oxidation of primary alcohols upto the
aldehyde stage only.
10. (a) C6HsCH2CH2CH20H (b) CH2=CH-CHOHCH3
11. (i) ~ (iii), (ii) ~ (iv), (iii) ~ (i), (iv) ~ (v), (v) ~ (ii)
12. The +R effect of the benzene ring increases the electron density in the carbonyl group of
benzaldehyde. This, in turn, increases the electron density in the C-H bond of the aldehyde group.
Thus, the C-H bond becomes stronger and is oxidised by only stronger oxidising agents like Tollens'
reagent from C-H to C-OH but weaker oxidising agents like Fehling's solution fail to oxidise
benzaldehyde to benzoic acid. On the other hand, both the reagents oxidise aliphatic aldehydes to
carboxylic acids.
OH 0
1 11
13. (a) C~54-C-OCH3
H Chloral hydrate
Methyl mandelate

14.
(I H® (I n-BuLi (I DOD (I Hi+/Hp 11 (I
C6HsCHO + HS SH - Sx S n-BuH" S'{LS\.@-LiOD"SX S ---=~..~ C6HS-C-D + HS SH
1.3-Propanedithiol Hs C6 H H5C[6 HSC6 D Deuterated
benzaldehyde
1,3-Dithiane
246 UNDERGRADUAE ORGANIC CHEMISTRY

OH 0 CH20H
15. (a) O-1H-~-O
o 0
(b) @:
0
COOH

1. Both the steric and electrical effects have profound influence on the rate (or reactivity) on nucleophilic
additions.
The carbonyl carbon atom is in sp2 hybridised state and the bond angles are 1200 approximately;
while in the adduct this carbon becomes sp3 hybridised and the bond angle on it are around 109.so.
The transition state of such an addition reaction being more similar to the adduct than to the
substrate,
E>
o 0
11 e 1
+Nu----7 /C,
C'.....
R/ 'R R 1 'R
Substrare Nu
Adduct
it suffers from the steric strain and this strain increases with the increasing bulk of the group already
present on the carbonyl carbon. The steric strain in its turn will slow down the reaction and ketones
being very bulky hydrocarbon groups practically do not undergo addition reactions with bulky
nucleophiles. Thus the rate of the reaction will go on decreasing as the size of Rand nucIeophile
increases.
Since the nucleophilic attack occurs on the electron-deficient, i.e., partially positively charged
carbonyl carbon atom, any thing that decreases the same will decrease the rate of the reaction. Since
alkyl groups have +1 effect, their presence slows the reaction. Since ketones have two alkyl groups
whereas aldehydes have only one, ketones are less reactive than aldehydes.
2. Electron-withdrawing effect on the carbonyl carbon, due to either -I effect or resonance effect,
increases the reactivity of the carbonyl group towards nucleophilic reagents. The greater the
electron-withdrawing effect, the greater is the reactivity. On the other hand, the greater the
delocalisation or neutralisation of the partial positive charge on the carbonyl carbon by +1 effect or
+R effect, the less is the reactivity of the carbonyl group. On the basis of the discussions above, the
reactivity order of the given compounds is as follows:
o
11
(a) CH3-CH=CH-CHO < CH3-C-CH3 < CH3-CHO < CF3-CHO
The -I effect of three F atoms in CF3-CHO makes it highly reactive towards nucleophilic addition,
whereas resonance effect in CH3-CH=CH-CHO and +1 effect in CH3COCH3 decreases their
reactivity. The resonance effect being stronger than the +1 effect the order of reactivity is as shown.
o
11
CH3-CH=CH-C-H
1 0 0 0
Et) 11 11 F\. 11
CH3-CH-CH=«-H < CH3-C-CH3 < CH3-C-H < F?C--C-H
i F
g
ALDEHYDES AND KETONES 247

o 0 0 0
11 11 11 11
(b) Ar-C-Ar < Ar-C-R < R-C-R < Ar-CH2-C-R
An aryl group directly linked to a carbonyl group delocalises its positive charge.
An alkyi group directly linked to a carbonyl group neutralises th" positive charge by +1 effect; and
Ar-CH2 group has low order of +1 effect owing to the -I effect of an aryl group.
3. The CHO group of benzaldehyde is less reactive towards nucleophilic attack by semicarbazide than
the CO group of cyclohexanone since resonance effect neutralises the 8+ charge on CHO more than
the +1 effect on CO. For these reasons, cyclohexanone reacts faster than benzaldehyde and the
kinetically controlled cyclohexanone semicarbazone is obtained. On standing, exchange of
H2NNHCONH2 group occurs between cyclohexanone semicarbazone and benzaldehyde for the
following reasons.
The semicarbazone formation reaction is reversible and the semicarbazone of benzaldehyde is more
stable than the semicarbazone of cyclohexanone because the former gets stability through resonance
and hence it is being thermodynamically stable, it forms slowly on standing.
o
00 <}-~-H +

1NH'-NH-~-NH'
/L
"----I:N-NH-C-NH2
o
11

(Kinetically Controlled Product)


+ 0-\\'I
-
'\
0
11
C-H

1l o
< }-CH=N-NH-~-NH2
(Thermodynamically controlled product)

4. The hydrated carbon atom of the chloralhydrate bears a greater steric strain than the similar carbon
atom of acetaldeyde hydrate. Therefore, it seems that chloral hydrate will be less stable than the
acetaldehyde hydrate. However, both the hydrates may give back the parent aldehyde since the
hydration reaction is essentially a reversible reaction and the equilibrium lies to the left usually.
8-
OH 0
Cl--..... 1 -HOH C~ 0+ 11
CI-C-C-H ~ CI-C-C-H
Cl/ 1 .iliQH CV 2 1
OH
8-
OH 0
1 -HOH 11
CH3-C-H ~ H3C- C- H
1 +HOH 0+
OH
248 UNDERGRADUAE ORGANIC CHEMISTRY

In chloral, the -I effect of the three chlorine atoms develops a <i+ charge on C-2 and -I effect of
o atom develops the same on Cl' These partial positive charges repel each other and bring instability
to chloral; in the chloral hydrate this effect is minimum owing to the absence of carbonyl group. So
the chloral hydrate is more stable than chloral. Since hydrated acetaldehyde experiences steric strain
and since acetaldehyde does not have any steric strain, acetaldehyde is more stable than acetaldehyde
hydrate: and consequently acetaldehyde hydrate decomposes and gives acetaldehyde. So chloral
hydrate is more stable than acetaldehyde hydrate.
5. (a) Monohalo acetone makes the hydrogen atoms of -CH2X more acidic than those of -CH3
because of the -I effect of X and C=O groups. For this reason halogenation occurs further.
(b) The acid-catalysed halogenation takes place through enolisation. The enol froms of
R-CH-.-C-CH3 are:
~ 11 -
o
Etl
o OH
11 11
R-CH2-C-CH3 + ff9~ R-CH2-C-CH3

OH Jr OH
1 1
R-CH=C-CH3 + R-CH2-C=CH2
(I) (IJ)

(I) is more stable than (II) due to the hyperconjugative effect. So halonium ion adds to (I) and not
to (II) which leads to the formation of R-CHX-CO-CH3'

C?-H o
!I
-----.~
R-~.J-CH3 R - CI-IX - C - CH3

6. The reacting species of the aldol condensation reaction is the carbanion. Carbanions formed by the
abstraction of alpha hydrogens being more stable than other,~ and that is why they take part in the
reaction.
e
o
R- CH2 - C -
11
H .......
~H ~-:J ~.)
:::,. R-CH-C-H ~ R-CH=C-H
?
(Carbanion) (enolate ion)

7. The sorbic aldehyde is


CH3-CH=CH-CH=CH-CHO
The y-atoms of crotonaldehyde (i.e., a, /3-unsaturated aldehyde) are more acidic than the a-carbon
atoms of acetaldehyde because of the greater resonance stabilisation of ihe conjugate base of the
crotonaldehyde than that of the acetaldehyde as shown below:
e
o El 0 0
11 OH e 11 I
CH3-CH=CH-C-H ~ CHz-CH=CH-C-H~ CH2=CH-CH=C-H
ALDEHYDES AND KETONES 249

So the carbanion of the croton aldehyde makes nucleophile attack on the electron-deficient carbonyl
carbon of acetaldehyde.

cjre
CH 3-C + CH2- CH =CH-C-H
?i
h
e
I
°, ooH' OH
CH3-CH-CH2-CH=CH-CHO- CH3-CH-CH2-CH=CH-CHO
JI-HOH
CH3-CH=CH-CH=CH-CHO
8. When aldehydes with alpha hydrogen atoms are treated with a strong base. they form the
corresponding resonance stabilised carbanion which then combines with another molecule of the
aldehyde to give aldol condensation product. the aldol. The rate of the aldol condensation being much
faster than the rate of the Cannizzaro reaction. aldehydes with a-hydrogen atom do not undergo the
Cannizzaro reaction.
9. A carbon-carbon multipule bond is an electron-rich moiety where electrophilic attack occurs. A
hydride ion is an electron rich species and thus behaves as a strong nucleophile. So, a hydride ion
experiences a repulsion when it comes closer to a carbon-carbon multiple bond and thus fails to react
with it. On the other hand. the electron-withdrawing effect of an aromatic ring on one side and that
of the carbonyl group on the other side make the carbon-carbon multiple bond less electron rich and
enable the hydride ion to attack the C-C moiety. For this reason such a C-C muitipule bond gets
reduced by LiAIH4'
10. (a) Acetylacetone contains an active methylene group. The hydrogens atoms of the active methylene
group are more acidic than the -CH3 group because of the -I effects of two CO groups. So at first
CH3COCI2COCH3 is obtained which through decomposition and further reaction gives iodoform as
shown below:
e
°
11
CH3-C-CH2-C-CH3
°
11 gH
r= 1I e" ° 1 °'I
CH3-C-CH-C-CH3 ~ CH3-C=CH-C-CH3
° °
112
qOI I1 011 (i) e OH 0" 0"
CH3 - C- C- C- CH3 ( CH3-C-CHI-C-CH3
I (ii) [2
( e I
OH

°
11 e °
11
CH3-C-0 + CHI2-C-CH3
(A) (8)
250 UNDERGRADUAE ORGANIC CHEMISTRY

o
1
CHI2-C-CH3
(8)

So the overall reaction is

o o
11 11
(b) R-C-CHr-C-R

o
l
e
OH

0
e
0 0 0 0
11 e 11 1 11 12 11 11
R-C-CH-C-R ~ R-C=CH-C-R -R-C-CHI-C-R
e
(i) OH
j (H) 12

C~
In
0
11
R-C-CI2-C-R ~
CO
1
R-C-CI2-C-R
0
1

6H ~e
o! 0 OH

1 e 1
R- C-OH + CI2-C-R

o
1l o
1 e 11
R-C-O + I 2HC-C-R
(A) CB)

(i) ~H
ALDEHYDES AND KETONES 251

o 10
11 e e 11
CHI3+R-C-O CI3+R-C-OH
o
CH~

I
NaOI Hydrolysis 11
(C) CH3-CH-NH2--~) /C=NOH • CH3-C-CH3
[0]

C~
1
~ e
0000
(ii) 12

o
11 e
CHI3 + CH3-C-O
11. If a base abstracts the aldehydic hydrogen as shown below, the carbanion formed will be highly
unstable since the negative charge has no scope for delocalisation; but the a-carbon with a negative
charge gets stability through resonance. For this reason, a base abstracts an a-hydrogen instead of
the hydrogen of the carbonyl carbon.
o 0
11 e 11
(i) R-C-H + OH~ R-C + HOH
e
Highly unstable

e
0 0 0
11 e 11 e 1
(ii) R-C-CH2-H + OH ~ R-C-CH2 + HOH - - R-C=CH2
(Stable)
12. Formaldehyde is always oxidised in cross Cannizzaro reaction because of the following three reasons:
(i) Formaldehyde is the most reactive aldehyde.
(ii) Formaldehyde exists in aqueous basic medium as the conjugate base of its hydrate. This
conjugate base is the reacting species of the Cannizzaro reaction.
e
o OH o
11 1 1
Step I. H-C-H+HOH H-C-H H-C-OH
1 1
OH H
Conjugate base of the hydrate of formaldehyde
Step-II
o
11.
H-C-OH
I
H

(Hi) Formaldehyde is the only aldehyde which has two hydrogens on the carbonyl carbon. Thus there
is statistical factor because formaldehyde has two hydrogens available for transfer in step 11, the
anions of other aldehyde hydrates have only one hydrogen available for transfer.
000
o
II
Carboxylic acids are structurally characterized by the presence of a carboxylic group, -C-OH,
which is sometimes also represented as -COOH or -C02H. The properties of the carboxyl group
remain almost the same whether it is attached to an aliphatic, aromatic, saturated, unsaturated, or
alicyclic moiety. The carbon atom in a carboxylic acid is present in its highest oxidation state which
makes it stable towards further oxidation. For this reason, they are stable and occur abundantly in
nature as oils, fats and amino acids, etc.

6.1 Nomenclature

Carboxylic acids can be classified as mono-, di-, tri- and polycarboxylic acids depending on the
number of carboxylic groups present in them. The common names of carboxylic acids are still
widely used. These names are derived from a plant or animal source in \" 'hich they are abundant. For
example:
Formic acid (Latm: fonnica = ant): acetic acid (Latin: acetum = vinegar); butyric acid (Latin:
butyrum = butter): valeric acid occurs in the strong smelling medicinal plant valerian (Latin:
valere = to be strong); and caproic, caprylic and capric acids (Latin: caper = goat) are responsible for
unsociable odour of goats. Many of the carboxylic acids were jirst isolated from fats, hence they are
known as fatty acids.
In IUPAC naming system, carboxylic acids are named as the derivatives of the hydrocarbon
corresponding to the longest continuous carbon chain containing the carboxyl group. The suffix -e of
parent hydrocaron is replaced by -oic acid.
For example, IUPAC names of some carboxylic acids are given below, their common names are
given 111 parentheses:
o
H-C-OH
"
Methanoic acid Ethanoic acid Propanoic acid
(Fonnic acid) (Propionic acid)
(Acetic acid)

o o o
1/
CH3CH2CH2-C-OH CH3(CH2hC-OH CH3(CH2)4C-OH
"
Butanoic acid
(Butyric acid)
"
Pentanoic acid
(Valeric acid)
Hexanoic acid
(Caproic acid)
CARBOXYLIC ACIDS 253

o o
11 11
CH3(CH2)6-C-OH CH3(CH2)S-C-OH
Octanoic acid Decanoic acid
(Capry lic acid) (Capric aCId)

The substituted and branched chain acids are referred to as derivatives of the main chain
indicating the position of attachment of Greek letters, U-, B-, Y-, etc. in the common naming system,
and by numbers in the IUPAC naming system as illustrated below:

~-C-~~-COOH
S 4 3 2 I
C-C-C-C-COOH
CH3CH2CHCOOH
I
Cl
a-Chlorobutyric acid (common name)
2-Chlorobutanoic acid (IUPAC name)

C6HsCH2CH2COOH
~-Phenylpropionic
acid
(Common name)

tl-Bromo-y-methylbutyric acid 3-Phenylpropanoic acid


(Common name) (IUPAC name)
3-Bromo-4-methylbutanoic acid
(lUPAC name)
Aromatic acids are usually referred to as the derivative of benzoic acid, for example:

c$fCl ~OH ~NO'


o -Chlorobenzoic acid N0
(2---<:hlorobenzoic acid) 2
p-Nitrobenzoic acid 2, 4-Dinitrobenzoic acid
(4-Nitrobenzoic acid)

COOH
COOH

Cl
©lCH)
m-Methylbenzoic acid
©r: COOH
Phthalic acid
(m-Toluic acid or (I, 2-Benzenedicarboxylic acid)
2, 4, 6--Trichlorobenzoic acid 3-Methylbenzoic acid)
The common names of most of the aromatic compounds are accepted as their IUPAC names.
When a carboxyl group appears as a substituent on a parent structure, it is referred to by the prefix
carboxy. Alternatively, the name of the parent hydrocarbon may be used followed by the term
carboxylic acid. For example:
COOH

0
COOH

2-Carbox}l::yclohexanone cyclohexanecarboxylic acid


~
Cyclopropanecarboxylic acid
254 UNDERGRADUATE ORGANIC CHEMISTRY

6.2 Aliphatic Carboxylic Acids

A asliphatic carboxylic acids are carboxyl derivatives of aliphatic hydrocarbons. These are represented
R-COOH, where R is an alkyl, alkenyl, or alkynyl group.
6.2.1 Methods of preparation
(i) From primary alcohols and aldehydes: Primary alcohols or aldehydes undergo oxidation
with oxidising agents to form carboxylic acids. The alcohol is first oxidised to an aldehyde and then
to a carboxylic acid.
[0] [0]
RCH20H --~) RCHO --~) RCOOH

K 2Cr20 7 K 2Cr20 7
CH3CH2CH20H H so ) CH3CH2CHO ) CH3CH2COOH
2 4 H2S0 4 Propanoic acid

Acetic acid is the most important carboxylic acid. It is widely used both as a reagent and solvent
in various industrial processes. It is prepared by air oxidation of acetaldehyde which is readily
available from dehydrogenation of ethyl alcohol or the hydration of acetylene.

CH3-CH20H 200-~~OOC) CH3CHO] ---+) CH3COOH 02

HgS041H2S04 Acetic acid


CH=CH+H20 ) CH3CHO
Large amounts of acetic acid are also produced by oxidation of ethanol in the presence of
acetobacter enzyme.
Mild oxidisng agents, such as Tollens' reagent, are sufficient to oxidise an aldehyde to an acid.
By this method an unsaturated aldehyde can also be oxidised to an unsaturated carboxylic acid.
R-CH=CH-CHO + 2Ag(NH3hOH-~) R-CH=CH-COONH4 + 2Ag + 3NH3 + H20
(ii) Hydrolysis of Nitriles: Alkyl cyanides on hydrolysis by boiling with acid or alkali give
carboxylic acids.
If>
R-C==N + H20 --~) RCOOH + NH3
NaOH ee
R-C==N + H20 --~) RCOONa + NH3
lHe
RCOOH
(ill) From Grignard reagents: By the action of C02 on Grignard reagent the carboxylic acid
can be prepared. Dry ice is employed as the source of C02. The resulting complex is hydrolysed to
give an acid.
o
~ I)-lit- 11 ®
o=c::bb + RMgX ----. R-C-oMgX HOHlH.. ReOOH
~
(iv) From 1,3-dicarboxylic acids: Dicarboxylic acids in which two carboxylic groups are
attached to the same carbon, dicarboxylate on heating to give monocarboxylic acids.
CARBOXYLIC ACIDS 255

/COOH /).
CH2\. ) CH3COOH + C02
"COOH
Malonic acid
(v) Arndt-Eistert synthesis: This is a means of converting an acid RCOOH (aliphatic,
aromatic, alicyclic, or heterocyclic) into the next higher homologue, RCH2COOH. The acid is first
converted into its acid chloride which is then treated with diazomethane (CH2N2) to give diazoketone
(RCOCHN2)' The diazoketone loses nitrogen to form a ketene by Wolff rearrangement when warmed
in the presence of silver oxide as catalyst.
o 0
11 CH2 N2 11 Ag20
RCOOH + SOCl2 ----7 R-C-CI----7 R-C-CHN2 ----7 R-CH=C=O
/).
Ketene
When the rearrangement is carried out in the presence of water, a carboxylic acid is formed.
RCH=C=O + H20 ----7 RCH 2COOH
(vi) Baeyer-Villiger oxidation: Carboxylic acids can be obtained by oxidation of ketones to
esters by means of peracids (Baeyer-Villiger oxidation) followed by hydrolysis.
o 0
11 11
R-C-R' + C6H5COOOH ----7 R-C-OR' + C6H5COOH
1 Hydrolysis

o
11
R-C-OH + R'OH
6.2.2 Structure of carboxyl group
The carboxylic acid group is resonance hybrid of the following two Lewis structures:

..~]
[ -c~Q
..
.........OH
(I)
••
~
~
_c'/:O.
~ ..
G:>OH
(11)
= ~O
-C:' 0+
"""'OH
(Ill )

There is separation of charge in structure 11, hence it is less stable than I and makes minor
&-

contribution to the resonance hybrid. The structure III provides an average of structures I and H, and
gives an instant picture of the electron distribution in the carboxyl group. Measurements of bond
distances is a convenient way to demonstrate the existence of resonance hybrid. The carbon-oxygen
bond length in the carbonyl group of a ketone is 1.22 A, while this distance is 1.39 A in an alcohol.
However, these distances are 1.25 A and 1.31 A, respectively in acetic acid. These differences can
reasonably be explained on the basis of resonance.
o
R-ef-longer than expected (partial single bond character)
"'\.(5H" shorter than expected (partial double bond character)

Similar to that of carbonyl group, 1t bond in carboxylic group is formed by parallel to axes
overlapping of p orbitals on carbon and oxygen. In carboxylic acid, the shape of C=O 1t bond allows
further orbital overlap. In this case, a p orbital of the hydroxyl oxygen interacts with the 1t electrons
of the carbonyl group to form 1t molecular orbitals that extend over three atoms. (Fig. 6.1).
256 UNDERGRADUATE ORGNIIC CHEMISTRY

6.2.3 Physical properties


Carboxylic acids are capable of forming hydrogen bond and they have
higher boiling points and water solubility than compounds of corresponding
molecular weight which are incapable of forming hydrogen bond. Carboxylic
acids have higher boiling points than aIcohols of the same molecular weight
because of the greater polarity of the O-H bond due to the adjacent
electron-attracting carbonyl group and because carboxylic acids can hydrogen
bond in two places. p-p ovedapping
Fig 6 ~ Orbital
().-H-O formulatioi I of carboxyl
R-C~ "C-R group
"v-H-'()~
Aciddimer

The first three members are colourless pungent smelling liquids. The acids from C4 to C9 are
oily liquids with goat's butter like smell, while the higher members are odourless waxy solids. Aqueous
solutions of carboxylic acids are acidic and turn blue litmus red.
6.2.4 Acidity of carboxylic Acids
Among the principal classes of organic compounds, only phenols and carboxylic acids are acidic.
This acidity can be detected by salt formation with a base. Even though alcohols have a polar hydroxyl
group, they do not react with sodium hydroxide, whereas both phenols and carboxylic acids do.
e $
R-OH + NaOH ~ ) RONa + H20

@-oH+NaOH ~
- - - - l.. <0r e $
3a + H 20

RCOOH + NaOH -~) R-COONa + H20


. Phenols, although definitely acidic compared with aIcohols, are considerably weaker acids than
carboxylic acids. Experimentally this is shown by the fact that carboxylic acids are neutralised by the
weak base NaHC03 but phenols are not.
e Et>
R-OH + NaHC03 ~ ) RONa + H20 + C02

@ - o H + NaHC03 IS!.. <0r e Et>


3a + H 20 + CO2

R-COOH + NaHC03 ) RCOONa + H20 + C02


Even though carboxylic acids are very acidic compared WIth most organic substances, they are
very weak acids in comparison with inorganic acids like HCI, H2S04, HN03, etc.
Strengths of carboxylic acids
The strength of an acid i.e., acidity is measured by the extent to which it can lose protons in a
solvent medium which acts as a base. Water is the common solvent used for this purpose. Other
nonaqueous solvents can also be used if required. Thus we get the following eqUilibrium for the
acid-solvent system:
CARBOXYLIC ACIDS 257

o o
11 11 e.
R-C-O-H+HOH~R~-O +
Acid Base Acid anion (Conjugate acid of the base)
(Conjugate base of acid)
The equilibrium constant for the above reaction is written as:
e Ea
[RCOO][H30]
Keq = [RCOOH][HOH]
For dilution solution, in which the concentration of water is large and atmost constant, another
expression, the acidity constant, Ka, is used.

. .. (1)

The Ka is the measure of the acidity of the acid. Higher the value of Ka, stronger will be the
acid.
The acidity constant for different acids has magnitude ranging from 10 14 to 10-5 °. Such large
-~ Ea
and such small numbers are most convenientently expressed as logarithms. Just as pH is -log[H30],
so pKa is defined as -log Ka.
In water medium at 25°C Ka of acetic acid is 1.75 x 10-5. Therefore, pKa =4.76. The pKa of
benzoic acid is 4.20. Thus, smaller the value of pKa stronger is the acid and vice-versa. In fact, if
two acids differ in their pKa value by one unit, the acidity of one acid will be ten times that of the
other acid. Therefore, benzoic acid is (4.76 - 4.20) x 10 or 5.6 times stronger than acetic acid.
Relative Strengths of Acids and Structural Effects
Relative strengths of acids in a given series may be assessed with the help of the following
considerations: .
(1) Conjugate acid-base pairs of given species are to be ascertained.
(2) Polarity of the O-H bond of an acid.
(3) Relative stabilities of the conjugate bases (i.e., acid anions) are to be determined.
The most stable conjugate base (or acid anion) in the series of the conjugate bases has least
tendency to accept proton, i.e., donate electrons. Hence it will be the weakest base of the series. Again,
if the conjugate base (i.e., acid anion) is weak, the acid will be strong and vice-versa. Therefore, the
acid which corresponds to the weakest base will be the strongest acid in the series. In other words,
acidity of an acid depends on the stability of acid anion of that acid. More is the stability of an acid
anion, more will be acidity of the corresponding acid.
Relative stabilities of acid anion can be assessed by considering the following main structural
effects:
(i) Resonance effect
(ii) Inductive effect
(iii) Intramolecular hydrogen bonding, and
(iv) Solvation effect
Thus any factor that can increase the polarity of O-H bond will increase acidity. Similarly, the
factor which can increase stability of acid anion will increase acidity.
(i) Resonance effect: Stability of species is determined by the number and nature of
contributing structures in a resonance hybrid of a series.
258 UNDERGRADUATE ORGANIC CHEMISTRY

More the number of contributing structures in a resonance hybrid of a neutral or negatively
charged species, more is the stability of the hybrid and greater is the delocalisation of electrons. Thus
delocalisation increases stability of acid anion and thus increases acidity of acid.
Let us compare the acidity of alcohols and carboxylic acids. For this let us examine the stabiliese
of reactants and products (equations 1 and 2) in order to fully explain the acidity of carboxylic acid.
ROH ~ROe + HEt) ... (1)
(I) (ll)

. '.' RCOOH ~ RCOOe + HEt) ... (2)

R-C~o
'O--H
( ) R-C/Oe~
~
~
~
[0'a
R-C.?'
e
( ) R-C/ oe] + He
~O
(Ill) (IV) H (V). (VI)
. alent resonance strucures
Non-equlv t Equivalent resonance structures

Alcohol and alkoxide ion can be represented by single localised structure (I and I1, respectively).
Both the carboxylic acid and carboxylate anion are resonance-stabilised (Ill, IV and V, VI). By the
principle one knows that resonance is much more important between the equivalent structures (V and
VI) than between the non-equivalent structures (HI and IV). As a result, although both acid and
carboxylate anion are stabilised by resonance, stabilisation is far greater for the carboxylate anion than
for the acid (Fig. 6.2).

e Extent of resonance stablisation


o
J
E of carboxylate anion as
compared to a1koxide ion.

I AE'

Extent of
resonance stablisation RCOOH
of carboxylic acid
as compared to
alcohol.
Reaction coordinate
Fig. 6.2

Thus carboxylate anion is more stable than the alkoxide ion. The stability of carboxylate anion
can also be explained on the basis of its molecular orbital structure. The carbon atom of carboxylate
anion is sp2 hybridis~. It is bonded to each oxygen atom by a (J bond. The unhybridised p orbital of
carbon overlaps with p orbitals of both oxygen atoms to form stable delocalised molecular orbital
(Fig. 6.1). This delocalisation of 1t electrons is responsible for the extra stability of the carboxylate
anion (Fig. 6.2).
(ii) Inductive effect: In general, electron-withdrawing substitutents increase acidity, whereas
electron-releasing groups decrease acidity. The following are the two priciples used for comparing
acidity of organic species:
CARBOXYLIC ACIDS 259,

(i) +1 effect: +1 groups increase magnitude of negative charge in acid anion, hence decrease
stability of the acid anion. Therefore, +1 groups decrease acidity. Thus:
ACl·d·ltyoc
1
+1 power of the group
(ii) -I effect: -I groups decrease magnitude of negative charge in acid anion, hence increase
stability of the acid anion. Therefore, -I groups increase acidity. Thus:
Acidity oc -I power of the group
(a) Electron-releasing groups:
0 0 0
11 11 11
H-C-OH CH3-C-OH CH3-CH2-C-OH
Ka 17.7 x 10-5 1.76 x 10-5 1.34 x 10-5
Alkyl groups, decrease O-H polarity and intensify the negative character of the carbox~'\ate
ion, through the +1 effect.
(b) Electron-withdrawing groups:
o o o o
11 11 11
CH3-C-OH HO-CHr-C-OH Br-CH2-C-OH CNCHr-C-OH
Ka 1.76 x 10-5 14.8 x 10-5 125 x 10-5" 365 x 10-5
-OH, -Br and -CN are the electron-withdrawing groups through -I effect and thus increase
O-H polarity and disperse the negative charge on the carboxylate ion.
As the number of electron-withdrawing substitutents increases so does acidity.
o 0 0 0
11 11 11 Cl 11
CH3-C-OH CI-CH2-C-OH g~>CH-C-OH CI~/-C-OH
Cl
Ka 1.76 x 10-5 136 x 10-5 5630 X 10-5 23,200 x 10-5
The proximity of the electron-withdrawing group is also important in considering acidity. The
nearer the group to the carboxyl, the greater the effect.
o o
11 11
CH3-CH2-CH-C-OH CH3-CH-CHr -C-OH
1 1
Cl Cl
Ka 139 X 10-5 8.9 X 10-5

CI-CH2--CH2CH2COOH
Ka 3.0x 10-5
(ill) Intramolecular hydrogen bonding: Intramolecular hydrogen bonding stabilises a
species. If the species is an acid, certainly this will diminish the dissociation of the proton therein.
Thus, intramolecular hydrogen bonding decreases acidity.
OH

6-
Ka = 600 x
N02

H)--IO
260 UNDERGRADUATE ORGANIC CHEMISTRY

If an acid anion is stabilised by intramolecular hydrogen bonding, the acidity of parent acid is
increased. For example, the ionisation constant of salicylic acid is 105 x 10-5 and that of its p-isomer
is 2.9 x 10-5. For the same reason, the ionisation constant of o-hydroxybenzoic acid (salicylic acid)
is 17 times higher than benzoic acid, and 2,6-dihydroxybenzoic acid is 800 times more acidic than
benzoic acid.

o
@(O 'H
C-OH
-H®
o ?I-oe
@(O'-H \
11
0 0
Ko = 105 x I(}-s stabilised by intramolecular
hydrogen bonding

COOH COoe

$ OH
·-H®

$ OH
Intramolecular hydrogen bonding
Ko = 2.9 x 10-s
is not possible

. e .

-@-
COOH . O':C;'O" .

OH~OH _HEll
H' 0 0 0/
H

(iv) Solvation effect: Structural features are not the only factors that affect acidity. The same
compound can have its acidity changed when the conditions are changed. For example, the solvent
can exert considerable influence on acid strength by differential solvation. If the acid anion is more
solavted than the parent acid, its stability is increased. Thus the acidity of the acid is also increased.
For example, acetic acid is stronger acid than propionic acid in aqueous solution because the anion,
S e
CH3COO is more solvated than CH3CH2COO due to its smaller size. It should be noted that the
propionic acid is a stronger acid in the gas phase where solvation is not possible.
6.2.5 Chemical Properties
(i) Salt formation: Acids combine with strong electropositive metals, metal oxides,
carbonates, alkalies, ammonia, amines, etc. and fonn salts.
Jlo
e EB
RCOOH + NaOH ----7 RCOONa + H20
Sodium carboxylate
e EB
RCOOH + NH3 ----7 RCOON14
e EB
RCOOH + Na2C03 ----7 RCOONa + C02 + H20

e
2RCOOH + Zn ----+) (RCOOhZn 2+ + H2
CARBOXYLIC ACIDS 261

The salts of carboxylic acids of low molecular weight are water-soluble and are insoluble in
organic solvents. The carboxylic acids can be regenerated by treating these salts with mineral acids.
RC009 NaEr> + HCl ) RCOOH + NaCl
The saIts of carboxylic acids are important for the synthesis of following class of compounds:
(a) Hydrocarbon:

RCOO~aEr> + NaOH + CaO _il---+> RH + Na2C03


(b) Amides:

RCOO~r-il---+) RCONH2 + H20


(c) Alkyl Nitriles:

(d) Ketones:
o
il 11
(RCOO)zCa ----+) R-C-R + CaC03
(e) Alkyl halides: Hunsdiecker reaction
e Er> il
RCOOAg + X2 ----+) RX + AgX + CO2
(ii) Ester fonnation; Carboxylic acids react with aIcohols in the presence of a strong mineral
acid, like H2S04, to form esters.
o 0
11 He 11
R-C-OH + H-O-R' ~ R-C-O-R' + H20
This ia a reversible reaction but the equilibrium can be pushed towards the right by using an
exc~ss of alcohol.
(ill) Formation of Acid halides: Acids react with phosphorus haIides or thionyl chloride to
form acid halides.
3RCOOH + PCl3 ----+) 3RCOCl + H3P03
RCOOH + PCIs ) RCOCl + POCl3 + HCl
RCOOH + SOCl2 ) RCOCl + S02 + HCI
(iv) Formation of Acid anhydrides: When carboxylic acids are treated with dehydrating
agents, acid anhydrides are formed:
o 0
11 11
R-C,,,- OH P20S R-C"
----+) /0 + H20
R-C/ OH il R-C
. 11 11
o 0
Acid anhydrides can also be obtained by treating sodium salt of carboxyli~ acid with an acid
chloride. .
262 UNDERGRADUATE ORGANIC CHEMISTRY

o
11
R-C\
RCOO~aE9 + R'COCl-~) /0 + NaCI
R-C
11
o
(v) Reduction
(a) Reduction to Hydrocarbons: Acids are resistant to reduction but on prolonged heating
with HI and red phosphorus, they are reduced to hydrocarbons. Hydrocarbons are also obtained when
acids are reduced with hydrogen at high temperature in the presence of Ni as catalyst.
HIIP(red)
R-COOH ) R-CH3 + 2H20

(b) Reduction to alcohols: Carboxylic acids also undergo reduction with lithium aluminium
hydride or diborane in THF to give primary alcohols.
RCOOH + LiAI14 ) RCH20H
RCOOH + B2H6 ) RCH20H
(vi) Formation of Ketones: Carboxylic acids react with alkyllithium to give lithium salts.
These salts further react with second molecule of akyllithium to give diIithium salt. This diIithium salt
on treatment with mineral acids gives a ketone.
o
11
(i) RCOOH + R'Li --~) R'H + R-C-OLi
o OLi 0
11 1 He 11
(ii) R-C-OLi + R'Li ) R-C-R'--~) R-C-R' + 2LiE9 + H20
1
OLi
(vii) a-Halogenation: Hell-Volhard-Zelinsky reaction: When a carboxylic acid contaning
a-hydrogens is treated with halogen in the presence of red phosphorus, the a-hydrogen atoms are
replaced by halogen. This reaction, known as Hell-Volhard-Zelinsky reaction, has wide synthetic
utility. Thus acids are convenient starting materials for preparing other a-substituted acids.
Br

R-CH2-COOH + Br2
RadP I
) R-CH-COOH
a-Bromo acid
OH
NaOH 1
r---~R-CH-COOH
a-Hydroxy acid
Br CN
1
R-CH-COOH---I NaCN 1
I---~ R-CH-COOH
a-Cyano acid
NH2

L...-NH_3~ R-CH-COOH
1

a-Amino acid
CARBOXYLIC ACIDS 263

In this reaction, first of all phosphorus reacts with halogen to form phosphorus pentahalide
which, in turn, converts the acid into the corresponding acyl halide. The acyl hali4e having a little
enol content undergoes halogenation at ex-position via enolic form giving rise to ex~halogenated acid
halide.
2P + 5Br2 ~ 2PBrs

o
11
R-CH2-COOH + P Brs - R-CH 2-C -Br + POBr3 + HBr
o OH Br (:R-H
11 I Br I ~I
R-CH 2-C-Br ~ R-CH=C-Br~ R-CH-C-Br
C~r
I e
fBr

Br 0 Br elOH
I 11 -H@ I 11
R-CH -C-Br"- R-CH-C-Br

This ex-bromoacyl bromide reacts with acid to give ex-bromo acid by an interchange reaction.
~ 0 fu 0 0
1 11 I 11 11
R-CH-C-Br + RCH2COOH ~ R-CH-C-OH + RCH2-C-Br
All the a.-hydrogen atoms can successively be replaced using an excess of halogen. The reaction
can, however, be stopped at mono-, di- or tri-substituted stage using appropriate amount of halogen.

Monobromoacetic acid

isr2/P
CBr3COOH CHBr:z-COOH
Tribromoacetic acid Dibromoacetic acid

(vUi) Formation of Primary amines: Carboxylic acids yield primary amines by the action of
hydrazoic acid. A vigorous reaction starts with the evolution of nitrogen and when the resulting
solution is warmed with water primary amine is formed with the evolution of carbon dioxide. This
reaction is known as Schmidt rearrangement.
RCOOH + N3H ) RNH2 + N2 + C02
6.3 Substituted Acids

Sinubstituted acids are the polyfunctional compounds containing at least one more functional group
addition to a carboxylic group. The functional group may be halogen atom, a hydroxyl group,
a carbonyl group, a multiple bond or another carboxylic group. For example:
X OH
1 1
R-CH-COOH R-CH-COOH R-CH=CH-COOH
Halo acid Hydroxy acid Unsaturated acid
264 UNDERGRADUATE ORGANIC CHEMISTRY

o
11
R-CH-COOH R-C-COOH
1 Keto acid
COOH
Dicarboxylic acid

6.4 Halo acids (ali~hatic)

Thethe halogen substituted carboxylic acids are compounds in which one or more hydrogen atoms of
hydrocarhJil chain have been replaced by halogen atoms. Halogen acids are usually named by
common system of nomenclature. The position of the halogen atoms is indicated by Greek letters.
o
11
CI-CH2-C-OH Br-CH2-CH2-COOH
Chloroacetic acid I3-Bromopropionic acid

6.4.1 a-Halo acids


Methods of formation
(i) Hell-Volhard-Zelinky Reaction: As we know, this is the usual method of preparing a-halo
acids. The acids contaiQing a-hydrogen atoms are treated with halogen in the presence of red
phosphorus to give an cl-halo acid.
X
RedP 1
R-CH2-COOH + X2 ) R-CH-COOH
Br
P 1
CH3-CH2-COOH +Br2-~) CH 3-CH-COOH
a-Bromopropionic acid
(ii) From Acid chloride: Acid chlorides when treated with N-bromosuccinimide (NBS) in the
presence of acid catalyst, give a-bromo acids.
Br Br
1 H$1H20· 1
R-CH2COCl + NBS -----4) R-CH-COCI ) R-CH-COOH
The possible reaction pathway is shown below:
Br 0 Br
o ~ OH sill Hp$ 1
R-CHz-C ~ ) R-CH=C/ NB) R-CH-C-Cl - R-CH-COOH
\Cl \ Cl (Br®)
(iii) From Alkyl malonic Acid: Alkyl malonic acid on treatment with halogen gives halo alkyl
malonic acid. This, on decarboxylation, gives a-halo aci~.
Br Br
/COOH 1 /COOH ~ 1
R-CH, + Br2 -~) R-C\ -C0 ) R-CH-COOH
2
COOH COOH
6.4.2 ~-Halo acids
Methods of formation
(i) From unsaturated aldehydes: Addition of a halogen acid to an a, ~ unsaturated aldehyde
CARBOXYLIC ACIDS 265

results in the formation of a ~-haloaldehyde. This is an example of anti-Markovnikov addition. This.


on subsequent oxidation, produces the ~-halo acid.
X X
1 [0] 1
R-CH=CH-CHO + HX ) R-CH-CHz-CHO - R-CH-CH2-COOH
~-Halo acid
(ii) From a, ~ unsaturated acids: ~-Halo acids are formed by the addition of hydrogen
halides to a, ~ unsaturated acids.
x
R-CH=CH-COOH + HX-~) R-CH-CH2-COOH
I
6.4.3 Properties of halo acids: Halo acids exhibit the properties of an alkyl halide as well as
an acid. Due to the presence of electron-withdrawing carboxyl group, the halogen atom (specially
halogen of a-halo acids) is far more reactive than that in alkyl halide. The halogen atom of halo acids
can be readily replaced by -H, -OH, -N02, -NH2' -CN, etc. The following scheme depicts the
important chemical reactions of the a-halo acids.
N02 Br OH
1 AgN02 I gH I
R-CH-COOH ( R-CH-COOH ) R-CH-COOH
9
NH2
I
R-CH-COON14
e
7 EB
R-CH-COOH
J
C;N
I
~~
.__
R-CH-COOH
I1

The behaviour of h~lo acids with an alkali is of particular interest and it depends on the position
of the halogen atom in the molecule.
(i) a-Haloacids when treated with alkali, form a-hydroxy acids.
e
OH
R-CH-COOH-~)R-CH-COOH
I I
Br OH
(ii) ~-Haloacids are first converted to ~-hydroxy acid which eliminates a molecule of water
giving a, ~-unsaturated acid.

R-CH-CH2-COOH -~) R-CH-CH2-COOH -


3H gH R-CH=CH-COOH + H20
I I Cl, ~-unsaturated acid
Br OH
In some cases the ~-halo acids form internal esters (lactones). For example, the sodium salt of
a ~-halo acid on shaking with chloroform gives the ~-lactone.

,/?G
R-CH-CH-C=O --.... R-CH-O

et bH3 CH3-lH-l=O
Lactone

(iii) y-Halo acids are converted into y-lactones.


266 UNDERGRADUATE ORGANIC CHEMISTRY

y-lactone
6.5 Hydroxy Acids (Aliphatic)
ydroxy carboxylic acids contain at least one -OH group attached to the hydrocarbon chain.
HVarious hydroxy acids occur naturally, for instance, tartaric acid (in grapes) citric acid (in citrus
fruits), malic acid (in fruit juice), glycollic acid (in sugar-cane) and lactic acid (in milk). Hydroxy
acids are often given the trivial names and the position of hydroxy group is denoted by Greek letters.
In IUPAC system, the position is designated by using numbers.
Some of the important hydroxy acids are given below:
Hydroxy Acid Common name IUPAC name
HOH 2CCOOH Glycollic acid or Ethanoic acid
Hydroxyacetic acid
OH
I
CH3-CH-COOH
a-Hydroxypropionic acid 2-Hydroxypropanoic acid
HO-CH-COOH
I
HO--CH-COOH
Tartaric acid 2,3-dihydroxybutanedioic acid

yOOH

1H2
COOH4-0H Citric acid 2-Hydroxy-l,2,3-popane-
tricarboxylic acid
CH2COOH

6.S.1 a-hydroxy acids


Methods of formation
(i) From aldehydes and ketones: A widely used method for the synthesis of a-hydroxy acids
involves the conversion of an aldehyde or a ketone to the corresponding cyanohydrin followed by
acid catalysed hydrolysis of the cyano group.
OH OH
0 e
OH I H$/H 0 I
R-C< +HCN )R-C-CN 2 ) R-CH-COOH
H
H
I
0 OH OH
11
e
OH I ~/HO R" I
R-C-R'+HCN )R-C-CN 2 ) /C-COOH
I
R'
R'
CARBOXYLIC ACIDS 267

(U) From ketones: Lithium derivative of N, N-di-isopropylformamide reacts with ketones to


give a-hydroxy acids.
o 0 . OLiEt) OH
11 11 /Pr 1 NaOH 1
R-C-R'+Li-C-N, .-~)R-C-R' • R-C-R'
Pr 1 /Pri 1
CO-N\. . COOH
Pr a-Hydroxy acid

(ill) From a-halo acids: Dilute alkali, moist silver oxide or even water converts a-haloacids
into corresponding a-hydroxy acids.
X OH
1 1 ~H
R-CH-COOH--~)R-CH-COOH

6.5.2 (3-hydroxy acids


Methods of formation
(i) Reformatsky Reaction: The best known and, in large number of cases, the most efficient
method of production of f3-hydroxy acid ester is the Reformatsky reaction. This method involves the
conversion of an a-bromo ester into an organo-zinc derivative in situ followed by the reaction of this
with an aldehyde or a ketone.
Br ZoBr
1 1
R-CH-COOC2HS + Zn --~) R-CH-COOC2HS
Organozinc compound
o ZnBr OZnBr OH
11 1 1 H30 $ 1
R'-C-R" + R-CH-COOC2Hs --~) R'-C-CH-COOC2HS- R'-C-CH-COOH
1 1 1 1
R" R R" R
~-Hydroxy acid
(U) From Ketones: In the presence of titanium tetra-alkoxide ketenes react with ketones to
give (3-hydroxy ester.
o ~ 0
11 1 11
3 CH2=C=O + 3 R'-C-R" + Ti(OR)4-~)RO-Ti -O-C-CH:z-C-O-R
1
R"
IHe /H20
R' ~1H20 R'
')C-CH2COOR----4) )C-CH:z-COOH