Reactions of phenol

Alcohol can react with sodium to give off hydrogen,

but it is not acidic enough to neutralize NaOH.
2CH3O-H + 2Na  2CH3O-Na+ + H2
Alkyl groups in alcohols push electrons toward the –OH
group, so that the oxygen does not attract the electrons in
the –O-H bond
CH3O-H CH3O- + H+ Ka = 10-17 mol dm-3
The negative charge on the CH3O- is localized by
the electron-releasing effect from the CH3- group,
so that stabilization by charge delocalisation is not
possible.
 Acidity of phenols
Phenol is acidic enough to react with both sodium
and sodium hydroxide. Phenol easily loses a
proton to form the phenoxide ion, which is
stabilized by resonance. (mesomeric effect)
OH O - O O
O
+
+ H
- -

OH ONa Ka=0.1 mol dm-3

+ NaOH + H2O
 Acidity of phenols
 Phenol is acidic due to two reasons:
 Non bonded electrons on the oxygen atom become
partially incorporated in the delocalized system of the
benzene ring. This electron withdrawal from the O-atom
makes it slightly electron deficient, thus facilitating the
loss of a proton by weakening the O-H bond.
 The phenoxide ion is stabilized relative to phenol by
delocalization of the negative charge throughout the
benzene ring. The presence of electron-withdrawing
-NO2 group further stabilizes the phenoxide ion, making
nitrophenol a very acidic compound
 Phenol is, however, not acidic enough to neutralize
NaHCO3 to give carbonic acid (CO2 + H2O).
OH ONa
+ NaHCO3 + CO2 + H2O
 Separate acid-phenol mixture
Phenols dissolve in aqueous sodium hydroxide by
neutralization whereas alcohols do not. This helps to
distinguish & separate between phenols & alcohols
Due to its weaker acidity, phenol does not react with
NaHCO3 solution, whereas carboxylic acids react to
liberate carbon dioxide. NaHCO3(aq) offers a method
for distinguishing & separating most phenols from
carboxylic acids.
R-COOH + HCO3- R-COO- + H2O + CO2
 Separate an organic mixture
e th e re a l m ix tu re o f
A c id -p h e n o l-a lc o h o l
+ N aH C O 3

e th e re a l la y er a q u e o u s la y e r
+ N aO H + HCl

e th e re a l la y er a q u e o u s la y e r R -C O O H to b e
+ HCl e x tra c te d w ith e th er

d istil o ff e th er p h e n o l filte red d istil o ff e th er

to g e t a lc o h o l out to g e t R -C O O H
 Characteristic reactions of phenols
The delocalization of electrons has strengthened the
C-O bond, the partial double bond character between
the carbon and oxygen is confirmed by its bond length
being shorter than that of normal C-O bonds.
As a result of this strengthening of C-O bond,
Displacement of the OH group is difficult
Oxidation does not give such breakdown products as acid,
alkanal, but form complex polymers
Formation of alkenes by dehydration is not possible
Delocalization of the lone pair in the oxygen atom with the
benzene ring makes the oxygen less readily available to
attack the electropositive carbon of the –COOH group of
carboxylic acids; esterification is slower than with alcohols
Prior change to the more reactive phenoxide ion will
help phenol esterify with the reactive acid derivatives
 Phenol Reactions
Aqueous solubility < 1 g cm-3, pH of solution = 4
Dissolves readily in NaOH(aq) but not in NaHCO3(aq)
Melts easily in hot water (m.p.=42oC)
Na shows vigorous effervescence with phenol to give H2
Adding Na2CO3, drop by drop, to neutralize FeCl3(aq)
until a trace of the brown precipitate just remains after
shaking; Violet coloration appears when a few drops of the
neutralized FeCl3 solution is added to a phenol solution.
Through delocalization of the non-bonded electrons, the –
OH group activates the benzene ring toward electrophilic
substitution. Phenol rapidly decolorizes bromine water as
2,4,6-tribromophenol is formed from bromination at RT.
 Esterification of phenol
ethanoyl chloride

OH O CH3COCl O COCH3
RT
NaOH(aq)
+ Cl

O COCH3
CH3CO-OCOCH3 + CH3CO2-
ethanoic acid anhydride
phenyl ethanoate (an ester)

Phenols contain an active hydrogen, which can be replaced

by an acetyl group in a reaction called acetylation.
The acetylating agent is CH3COCl or CH3CO2-COCH3 ,
which can react with the compounds containing active
hydrogen such as phenol or amine (primary, secondary)
NHCH3 NCH3
+ Cl COCH3 COCH3 + HCl
 Carbonyl Compounds
Aldehydes & ketones contain the carbonyl group.
R-C-H and R-C-R are the general structure of an
O O aldehyde and a ketone respectively
R= H or an alkyl R= alkyl or Both classes of compounds show reactions
or aryl group aryl group characteristic of the carbonyl group
The carbonyl carbon is sp2 hybridized, with its 3 attached
atoms lying in the same plane. The bond angles between
the three attached atoms are about 120o.(trigonal planar)
Within the carbonyl group, the electrons in the  and  bonds
are drawn toward the more electronegative oxygen atom.
The carbonyl oxygen thus bears a substantial partial negative
charge, whereas the carbonyl carbon bears a substantial
positive charge. + -
C O
 Naming alkanalsCHO
and alkanones
HO
CH3CH=CH-CH- CHO
CH3
Br CHO
2-methylpent-3-enal 2-bromobenzaldehyde 4-hydroxybenzaldehyde
O
O
CH3COCH2CH=CHCH3 CH3

CH3
hex-4-en-2-one
phenylethanone 2-methylcyclohexanone

The reactions of aldehydes and ketones include:

Nucleophilic addition reactions
 Addition-elimination (condensation) reactions
 Oxidation and reduction
 Triiodomethane reaction
Nucleophilic Addition Reactions
The carbonyl group is strongly polarized, with the el
ectrons in the  and  bonds shifted toward the
more electronegative oxygen atom. The carbonyl
carbon is thus electron-deficient or electrophilic,
whereas the oxygen is electron-rich or nucleophilic.
The carbonyl carbon is readily attacked by an
electron-rich nucleophile, and addition reactions of
nucleophiles at the carbonyl carbon dominate the r
eactivity of carbonyl compounds.
Neutral/anionic nucleophiles offer the extra pair of e
lectrons for co-ordinating with the carbonyl carbon
Once a new bond is formed from the nucleophile to
the carbonyl carbon, the carbonyl oxygen gains an
unshared electron pair. This electron rich oxygen c
an transfer its electron pair to a proton, completing t
he overall addition of Nu-H to the carbonyl group.
The Carbonyl Group: Structure and Mechanism
- Nu: +
Nu H Nu
O O H
O
+ -
Due to the higher electronegativity of the oxygen atom
, there exists an electropositive carbon in the carbonyl
group where an electron-rich nucleophile initiate an att
ack on it. Despite the high electron density of the carb
onyl group, a nucleophile-induced addition occurs
HNu adds across the C=O double bond in such a
way that the electron-rich nucleophile attacks th
e electropositive carbon to form a Nu-C bond, a
nd a H+ then attacks the intermediate anion to fo
rm the O-H bond.
Nucleophlic and Electrophilic Addition
The carbonyl carbon in the highly polarized C=O b
ond can act as an electron-deficient site to attract e
lectron-rich species (nucleophiles). Addtion to the
C=O bond is a nucleophilic addition, with the initial
attack from an nucleophiles, e.g.
CN- +H-CN-
O O OH
CN CN
The CN- serves as the attacking nucleophile for the electron-deficient carbonyl carbon
The C=C ond is non-polar and acts as an electron-
rich centre instigating an initial attack onto the elect
ron-deficient species, e.g.
HO-
OH
+
Br--OH
Br Br

The Br- acts as the electrophile attacked by the electron rich C=C bond
Stereochemical aspect of nucleophilic addition
In the nucleophilic addition across the C=O bond, nu
cleophilic attack can come from above or below the p
lanar carbonyl group, in order to minimize steric hindr
ance. Since addition can occur at both sides of the pl
ane at equal rates, both enantiomers are formed in e
xactly the same amount, resulting in a racemic mixtur
e of products.
Nu Nu from R
R Nu from OH
O R and R'
OH top R' áre different
R R' bottom Nu
R' Propanone does not form a racemic mixture in its reaction with cyanide

Aldehydes have fewer bulky groups than ketones

 Relative reactivities of carbonyl compounds
The relative reactivities of aldehydes & ketones toward
nucleophilic addition reactions depend on 2 factors:
Electronic influence of the groups attached to the carbonyl
carbon - The higher the number of electron-releasing group
s, the less electron-deficient is the carbonyl carbon, an the l
ess reactive it is toward nucleophiles.
Steric hindrance of the groups.
Alkyl groups are electron-releasing relative to hydrogen
and are also much more bulky. Hence, for both electronic
and steric reasons, ketones with the carbonyl group fl
anked by two alkyl or aryl groups, are generally less
reactive than aldehydes. Least
O reactive
R R O O
H
O O O H R
H H R
Delocalization of electrons from the ring reduces the electron deficiency of
the carbonyl carbon and makes it much less reactive.
 Addition of hydrogen cyanide (KCN)
Hydrogen cyanide adds to the carbonyl groups of ald
ehydes and most ketones to form 2-hydroxynitriles
O R'
OH
+ H CN CN
R R' R
R’ = H or alkyl group
HCN is never used for addition across the C=O bond
HCN is a dangerously toxic gas at RT
HCN itself is a poor nucleophile and a weak acid
CN-, being a stronger nucleophile than HCN, is able t
o attack the carbonyl carbon very rapidly. As a weak
acid, it adds slowly. The reaction is base catalysed as
the base can increase the [CN-]
 Nucleophilic addition with KCN(aq)
It‘s safer to replace HCN & OH- by CN- and acid. This can
be done by mixing the aldehyde or ketone with aqueous N
aCN and then slowly adding sulphuric acid to the mixture.
Even with this procedure, great care must be taken the re
action must be done in fume cupboard.
Hydroxynitriles are useful intermediates in organic sy
ntheses, especially for preparing -hydroxyacids or
,-unsaturated acids: the CN- group being readily hy
drolysed to -COOH by refluxing with 70% sulphuric ac
id or dilute alkaline solutions.
Formation of cyanohydrins offers a useful way of mak
ing molecules with 2 functional groups and with a lon
ger carbon chain than the original reactant.
 Hydroxyacids and unsaturated acids
OH OH
HCN HCl
CH3CH2COCH3 CH3CH2C-CN CH3CH2C-CO2H
H2O, heat
CH3 CH3
Dehydration,
Hydrolysis of CN group conc. H2SO4 , heat
CH3CH=C-CO2H
CH3
When reacted with HCN, ketone/aldehyde gives hy
droxynitriles, which hydrolyzes to form -hydroxy
acids. Then dehydration of the acid with conc. H2S
O4 gives ,-unsaturated acids.
Upon nucleophilic addition, all aldehydes and uns
ymmetrical ketones give a racemic mixture of ena
ntiomers, which cannot be separated by careful di
stillation. HCN adds preferentially to the carbonyl
group, leaving other unsaturated carbon centre
s intact.
 Reactivity of carbonyl compounds
Nucleophilic addition of carbonyl compounds is affected by
electronic and steric factors.
The presence of electron-withdrawing groups at the -
carbon of aldehyde/ketone makes the carbonyl carbon
more electron-deficient, thus increasing the reactivity of
the carbonyl compound. CH3COCHCl2 is more reactive
than propanone toward nucleophilic addition by HCN. T
he increased steric hindrance of Cl is less important in
affecting reactivity in this case.
Addition of HSO3- is more prone to steric factors. With
more bulky groups attached to the carbonyl carbon, ket
ones are less reactive than aldehydes.
 Addition of Sodium bisulphite NaHSO3
3,3-diethylpentan-2-one is unreactive toward h
ydroxynitrile formation because
there are bulky substituents around the carbonyl group,
the 3 ethyl groups produce positive inductive effect, redu
cing the electrophilic nature of the carbonyl carbon
On shaking the aldehyde/ketone with excess 40% aq
ueous sodium hydrogen sulphite at RT, colorless cryst
als called bisulphite adducts are formed:
CH3 O OH
O -:SO3H H3C SO3H H3C SO3-
H H H

It’s a nucleophilic addition with the attack initiated by the -SO3H nucleophile
This reaction is very sensitive to steric hindrance and is limited to aliphatic
aldehydes and sterically unhindered ketones (methyl ketones) only.
The reaction with NaHSO3 helps distinguish aldehydes/ketones from others
Purification & separation of aldehydes/methyl ketones
Bisulphite reaction is used for the separation and puri
fication of aldehydes and methyl ketones from other
compounds because these compounds can be regen
erated by treating the bisulphite adducts with aqueou
s alkali or dilute acids, which reverse the bisulphite e
quilibria to the left
A few derivatives of ammonia (amine/hydroxylamine/
hydrazine/2,4-dinitrophenylhydrazine) serve as an ac
tive nucleophile, initiating nucleophilic addition on the
carbonyl carbon of aldehydes/ketones. The adduct fo
rmed is easily dehydrated to form a product containin
g a -C=N group.
 Addition-Elimination (Condensation)
 The lone pair on the nitrogen atom of a derivative of
ammonia attacks the carbonyl carbon, forming an un
stable intermediate. This adduct then rapidly loses a
water molecule to form a condensation product.
R' R'
R"-NH2 O R"-N=C + H2O
R R
R' H OH R'
R'
R"-NH2 O R"-N--C R"-N=C + H2O
R R R

Aldehydes and ketones react with hydroxylamine to form

oximes, known as aldoximes and ketoximes respectively.
Due to the high solubility of aliphatic oximes, careful
crystallization is required to get the crystalline oxime solid.
 Condensation with ammonia derivatives
R' H HO R'
HO R'
N: O N HO-N==C + H2O
H R HO R R
H
 Aldehydes & ketones react with 2,4-dinitrophenylhydrazine
to form 2,4-dinitrophenylhydrazones. The condensation
products have sharp characteristic melting points and
is useful for identification of the original compounds.
R' R'
O N-NH NO2 + OH2
O2N NO2 R
R
O2N
2,4-dinitrophenylhydrazone (an orange precipitate)
NH-NH2

Purification of the condensation products is done by recrystallization from

ethanol. Its melting point is then determined after washing and drying the
crystals. The m.p. values can be compared with that from data book for
the purpose of identification of the original aldehyde or ketone.
 Identification of a carbonyl compound
2,4-dinitrophenylhydrazine, dissolved in ethanol, is mixed with a little
concentrated sulphuric acid to give an orange reagent commonly used in the
identification of aldehydes and ketones.
When it reacts with an aldehyde or ketone, the reagent gives an orange-
yellow solid of 2,4-dinitrophenylhydrazone. These hydrazones can be
isolated in relatively pure forms, which have characteristic melting points.
2,4-dinitrophenylhydrazine is preferred to hydroxylamine for the formation of
derivatives because 2,4-dinitrophenylhydrazones have higher melting points and are
less soluble.
The hydrazone solid is often much more soluble in ethanol near its boiling point
than at room temperature. Boiling ethanol is thus added to an impure hydrazone
until just enough has been added to dissolve it all. Any insoluble impurities can
be removed by filtering with suction
The hot filtrate (hydrazone) collected is cooled slowly in an ice-water mixture
until crystals reappear. Since the solid derivative is much less soluble at RT, it
will precipitate out from the filtrate and can be removed by further filtration. Any
soluble impurities (such as unreacted aldehydes or ketones, minerals), will remain
dissolved in the solvent.
Identification of a carbonyl compound (2)
The hydrazone is said to be purified by recrystallization. The
effectiveness of this method depends very much on the selection of a
suitable solvent in which the hydrazone is much more soluble at high
temperature than low temperature, thus regenerating purer product
crystals in good yield.
After recrystallization the derivative is further washed under suction with a few
drops of ethanol and then dried by drawing air through them. The crystals are
spread on a dry watch glass & left overnight for drying.
Proper recrystallization is vital because any impurities left will depress the m.p.
of the hydrazone, thus leading to a false identification.
A dilute solution of 2,4-dinitrophenylhydrazine is used because solid
2,4-dinitrophenylhydrazine easily precipitates out and the solid might
be mistaken as the hydrazone.
Ethanol in this case is chosen largely out of trial and error, careful tests
being made on small product samples with different solvents.
By comparing the measured m.p. with those in a data book, the particular
aldehyde or ketone can be identified. Further chemical tests (Tollen’s test),
may be necessary to distinguish the aldehyde from the ketone if there are
two 2,4-dinitrophenylhydrazones with the same m.ps.
 Triiodomethane Reaction
 Ethanal and methyl ketones contain the CH3CO- group,
which would react with iodine in aqueous NaOH to give
yellow crystals of triiodomethane.
 A small sample of ethanal or methyl ketone can be warmed
with NaOH(aq) and a large amount of iodine (2 drops of
propanone require ~1 g of iodine). Pale yellow crystalline
precipitates of triiodomethane appear on cooling.
 CH3CH2OH reacts with I2/NaOH to give ethanal and
thus ethanol also shows positive triiodomethane test.
O O
H
R H + 3NaOH + 3 I2 + 3NaI + 3H2O
R CI3
H
A secondary alcohol
O O
with the -OH group
+ -OH + CHI3 at C-2 also shows
R CI3 R O postive iodoform test
 Structural Determination
Result Structural information
Positive 2,4-dinitrophenylhydrazine test An aldehyde or a ketone
Positive Triiodomethane CHCl3 test A methyl ketone
Ozonolysis gives ethanal R-CR’==CHCH3
Deduction R’ = CH3C=O
R = H if the formula is C5H8O
The equations involved in the deduction:
O R
N NH
H2N-NH
R R' R'
O2N NO2
O2N NO2
O O Yellow precipitate
H
R H + 4OH- + 3 I2 + CHI3 + 3I- + 3H2O
R O
H
H The possible structures for C5H8O are:
R O3 R O O
O + CH3CHO H CH3
CH3 R' CH3 CH3
R' CH3 H H
H
 Oxidation and Reduction
 Aldehydes are oxidized to carboxylic acids redily by a nu
mber of oxidants such as acidified KMnO 4, K2Cr2O7 or eve
n mild oxidant such as ammoniacal silver nitrate and Fehli
ng‘s solution.
O O
[O]
R OH
R H acidified KMnO4 or
acidified K2Cr2O7
 Unlike aliphatic aldehydes, aromatic counterparts do not
undergo oxidation readily. (Benaldehyde does not change
easily to benzoic acid)
 Ketones do not undergo oxidation readily. It requires mor
e drastic conditions to bring about the cleavage of the car
bon-carbon single bond, forming 2 acids.
The Silver Mirror Test (Tollen‘s reagent)
Mixing aqueous silver nitrate with aqueous ammonia fo
rms a solution known as Tollen‘s reagent, a weak oxida
nt but when heated gently in water it can oxidize aldehy
des to carboxylate ions, itself being reduced to metallic
silver which deposits on the wall of the test tube as silv
er mirror.
The Tollen‘s reagent is prepared by adding excess aqueous
ammonia solution to a clean test tube of silver nitrate solutio
drop until the precipitate is just dissolved. 2Ag+
n, drop by drop,
+ 2OH- Ag2O(s) + H2O Ag2O
+ 4NH3 + H2O 2Ag(NH3)2OH
A few drops of aldehyde are then added to the reagent
and the tube placed in a beaker of warm water:
O O
2 Ag(NH3)2OH + R R + 2Ag + H2O + 3NH3
O NH4+
H
 Fehling‘s Test

Tollen‘s reagent gives a negative result with all k

etones and thus can serve as a specific test for
distinguishing aldehydes from ketones.
A Fehling‘s reagent is an alkaline solution of cop
per(II) tartrate (clear royal blue in color).
Aliphatic aldehydes reduce the copper(II) ion in
Fehling‘s reagent to the reddish-brown copper(I)
oxideO precipitate. O
R + 2Cu2+ + R + 3H2O + Cu2O(s)
H 5 OH- O red precipitate
Ketones and aromatic aldehydes give negative result to the Fehling‘s
test, so the reagent acts to distinguish alehydes & ketones.
Fehling’s reagent is a solution mixture of CuSO 4 & sodium potassium tartrate in excess NaOH
 Reduction
 Aldehydes & ketones are reduced to primary & secondary
alkanols respectively by the two reductants:
 Lithium tetrahydridoaluminate (LiAlH4) in ethoxyethane solution
followed by addition of water, or
 Sodium tetrahydridoborate (NaBH 4) in aqueous solution/ethanol
 These reductants generate the nucleophile H-, the hydride
ion, which is attracted to the electropositive carbonyl carbon
The nucleophilic attack by the hydride ions gives alcohols as
the reduction product. The alcohol is released upon hydrolysis
of the addition intermediate.
 A ketone gives a secondary alcohol
 An aldehyde gives a primary alcohol
R
H R H H+ R H
O
from solvent
R' O R' OH
R'
 NaBH4 is used to reduce aldehydes (to minimize hazard).
However, LiALH4 is a more versatile 用途廣的 reductant.
 Reduction (2)
NaBH4 H
O H
suspended in

aqueous ethanol OH
OH
O
LiAlH4/ethoxyethane H H
HO HO
O then H3O+
O H OH
 LiAlH4 can reduce carboxylic acid, acid anhydride, ester and
acid chloride to alcohols whereas NaBH4 cannot.
 LiAlH4 and NaBH4 produce H- ion for their reducing action,
both of them cannot reduce carbon-carbon double, triple
bonds and aromatic rings to full saturation. The H- ions are
simply repelled by the non-polar and electron-rich  bonds
in the carbon-carbon double bond.
 Reduction (3)
H HO
O O LiAlH4/ethoxyethane

then H3O+ H H
CH3O H
HO H
H H
LiAlH4 /ethoxyethane
CHO CH2OH
then H3O+ double bond
H H

H LiAlH4 /ethoxyethane
O LiAlH4 /ethoxyethane CH3CHO CH3CH2OH
OH then H3O+
then H3O+

 LiAlH4 must be used in dry ether because it reacts violently

with water to give hydrogen and an alkaline solution.
 IR Spectra of the carbonyl compounds
The >C=O group shows a prominent dip at around 1700 cm-1
as a result of C=O bond vibration. The dip is often strong &
sharp. In aldehydes it is at between 1720 and 1740 cm-1. In
ketones it is between 1705 and 1725 cm-1.

90

50

30
C-H bond C=O bond
stretch stretch Wavenumber
3400 3000 1700 1330 cm-1
 Carboxylic acids
The carboxyl group –CO2H is a combination of the carbonyl
group and the hydroxyl group. These two groups modify the
behavior of each other, so that the chemistry of the acids
differs from that of aldehydes, ketones and alcohols.
2-chlorobutanoic acid 3-hydroxy-5-methylhexanoic acid
O
Benzoic acid
O
CO2H CH3 OH
OH
Cl
OH
Propanedioic acid Benzene-1,2-dicarboxylic acid
H O Hex-4-enoic acid (cis, trans) CO H 2
CH3 O
OH
H OH
H H
CO2H
Aldehydes & ketones can be changed to -hydroxynitriles,
which hydrolyze to -hydroxycarboxylic acids.
 R
Carboxylic acids (2) R OH
OH H3O+
O + H CN
CN R COOH
heat
R' /H R/H R/H
Nitriles, precursors of carboxylic acids, can also be made
from haloalkanes by nucleophilic substitution with NaCN.
Only primary haloalkanes are useful in making the nitriles
useful for conversion into carboxylic acids. As CN- ion is a
relatively strong base, the use of secondary or tertiary
haloalkanes leads to elimination rather than substitution
H H H
CN- SN2 H3O+
X H3C H H3C H + NH4+
H3C heat
H CN COOH
Alkaline hydrolysis of nitriles produces H
OH-/H2O
the acid salt and ammonia. Prolonged
heat H + NH3
reflux in acid solution produces the H3C CO2-
carboxylic acid and ammonium salt.
Br Br
NC HO2C
CN CO2H
NaCN H3O+
hexanedinitrile hexanedioic acid
Oxidation of primary alcohols, aldehydes & alkylbenzenes
Strong oxidants such as K2Cr2O7 or KMnO4 oxidizes primary
alcohols to give carboxylic acids in fairly good yield. Since
aldehydes are formed as an intermediate in the course of
such oxidation, most aldehydes undergo oxidation to acids
under even milder conditions. RCHO + [O]  RCOOH Dil KMnO 4

RCH2OH + 2[O]  RCOOH + H2O Alkaline KMnO4, H3O+

The side chains of alkylbenzenes are always susceptible to

oxidation by strong oxidants such as hot alkaline KMnO 4:
CO2H
CH3 (1) KMnO4/OH- , heat

(2) H3O+

Alkylbenzenes with alkyl groups larger than methyl are also degraded to
benzoic acids. Since oxidation of side chain occurs at the phenylmethyl
Carbon, 2-methyl-2-phenylpropane is resistant to side chain oxidation.
 Oxidation of methyl ketones and some alcohols
Methyl ketones, with the group –COCH3 or alcohols with the
group –CH(OH)-CH3 are liable to undergo iodoform reaction to
form CHI3 as well as a carbon skeleton with a carboxylate group
O O

CH3 + 3I2 + 4OH- + CHI3 + 3I- + 3H2O

O

The group to which the -COCH3 or -CH(OH)CH3 function is attached

can be aromatic, alkyl or hydrogen. The resulting carboxylate has
one carbon less than the original carbon skeleton.
By utilizing different oxidants, CH3-C6H4-COCH3 can form different products
OH
I2/OH-
H3C
CH3 H3 O +
H3C O
O
MnO4-/OH- OH
H3O+ HO2C
O
 Acidity of Carboxylic acids
Ethanoic acid, CH3COOH, is the key ingredient in vinegar.
It is the –COOH group in the molecule that is responsible
for its acidity. In water the molecule dissociates into ions:
H
O O +
O H
:O -- + H
O H H O H

The ethanoate ion is stabilized by the spreading of the

negative charges over a carbon and two oxygen atoms.
Being a weak acid, the acid dissociation constant is small.
The smaller the pKa value, the greater is the acid strength
Compound HCOOH CH3COOH Cl2CHCOOH Cl3CCOOH

pKa 3.8 4.8 1.29 0.80

Electron
Electronreleasing
releasinggroups
groupssuch
suchas as-CH
-CH3 3reduce
reducethe
theacid
acidstrength.
strength.
HCOOH
HCOOHisisslightly
slightlymore
moreacidic
acidicthan
thanCH
CH3CO CO2HHas
asitithas
hasno
no-CH
-CH3. .
3 2 3
 Acidity of carboxylic acids (2)
There are 3 factors affecting the acidity of organic acids:
the strength of the H-A bond
the electronegativity of A (electronic factor)
factors stabilizing its conjugate anion A- with respect to HA
Since the O-atom is considerably more electronegative th
an carbon, the O-H bond in methanol breaks more readily
than the C-H bond in methane. Also the resulting conjuga
te anion, CH3O- is more stable than CH3-.
The
ThepKpKa aofofmethanoic
methanoicacid acidisis4.4.The
Theelectron-withdrawing
electron-withdrawing>C=O >C=Ogroup,group,
which
whichenhances
enhancesthe theelectron
electronaffinity
affinityofofthe
theoxygen
oxygenatomatomtotowhich
whichthe the
incipient
incipientproton
protonisisattached
attachedand andweakens
weakensthe theO-H
O-Hbond.
bond.Factor
Factor33isisthe the
most
mostimportant
important factor:
factor: the
thestabilization
stabilization ofofthe
the resulting
resulting conjugate
conjugate anion
anion
HCO
HCO2 2-when
-
whencompared
comparedwith withthethemethanoic
methanoicacid acidmolecule
moleculeitself.
itself.InInthe
the
anion,
anion,negative
negativecharge
chargeisisspread
spreadoverover33atoms
atomsandandisisthus
thusstabilized.
stabilized.
 Influence of substituents on acidity
 Electron-withdrawing groups weakens the O-H bond and
helps spread out the negative charge on the resulting
carboxylate ion, thus raising the acidity of carboxylic acid.
 The acidity of a carboxylic acid is greatly increased when
the number of electron-withdrawing chlorine attached to the
-carbon increases. The electron-withdrawing groups can
increase acid strength as the O-H bond is weakened and
the acid anion is stabilized. Inductive effects are additive;
the more numerous the electron-withdrawing groups on
the -carbon, the stronger will then be the acid. The more
electronegative the -substituent, the stronger is the acid.
 The Inductive effect on acidity decreases rapidly when the
substitutents are placed farther away from the -CO2H group
 Influence of substituents on acidity
 The presence of electron-releasing group in the acid will re
sult in reduction of the acid strength for 2 reasons:
 The electron-donating group pushes electrons toward the electron
deficient carbonyl carbon atom, thus reducing its charge. The hydr
oyl oxygen will then have a better chance of attracting more than it
s fair share of electrons in the C-O bond, thus strengthening the
O-H bond and consequently it will not break easily.
 When dissociation has occurred, the electron-donating substituent
will push electrons toward the electron-rich -CO2- group, thus inten
sifying the negative charge and consequently destabilizes the res
ulting anion.
Carboxylic
Carboxylicacidsacidsare
aremore
moreacidic
acidicthan
thanphenols
phenolsand
andthey
theydisplace
displaceCO
CO2 2from.
from.
HCO
HCO3 3.-.Carboxylic
-
Carboxylicacids
acidsreact
reactwith
withammonia
ammoniatotogive
giveammonium
ammoniumsalts,
salts,which
which
can
canbe
bedehydrated
dehydratedby bystrong
strongheating
heatingtotoOgive
giveamides
amides
O
O strong CH3
CH3 + NH3 H3C
heat NH2
+ H2O
OH O NH4+
ethamide
 Acidity of organic compounds
 In the case of alcohols there is no delocalization of charge
stabilizing the alkoxide anion, RO-, with respect to alcohol
molecule itself. Alcohols are neutral.
 In the case of phenol, there is also the stabilization of the
conjugate ion by the delocalization of its negative charge
through interaction with the p orbitals of the benzene ring
The negative charge spreads over the electropositive C-
atoms and the stability of the phenoxide ion is less stable
than the carboxylate as the negative charge in it is spread
over two highly electronegative oxygen atoms.
 The order of stability follows the order of stability of their
conjugate anions: O OH

R >> >> R OH
OH
 IR Spectra of the carbonyl compounds
 The >C=O group shows a prominent dip at around 1700 cm-1
as a result of C=O bond vibration. The dip is often strong &
sharp. In aldehydes it is at between 1720 and 1740 cm-1. In
ketones it is between 1705 and 1725 cm-1.

90

50

30
C-H bond C=O bond
stretch stretch Wavenumber
3400 3000 1700 1330 cm-1
 L
 L
 L
 L