4 June 2022 Chemistry

ALKYL HALIDE
ALKYL HALIDE
(HALOALKANES)
Aliphatic Halogen Derivatives :
Compounds obtained by the replacement of one or more hydrogen atom(s) from
hydrocarbons are known as halogen derivatives. The halogen derivatives of alkanes, alkenes,
alkynes and arenes are known as alkyl halide (haloalkane), alkenyl halide (haloalkenes),
alkynyl halides (haloalkynes) and aryl halides (halobenzenes) respectively.
Alkyl halides : Monohalogen derivatives of alkanes are known as alkyl halides.
Structure of alkyl halides:
C X
Classification of alkyl halides :

(i) Primary halide : The halogen bearing carbon is bonded to one carbon atom or with no
carbon atom.
Example :
CH3 – X, R – CH2 – X
(ii) Secondary halide : If two carbon atoms are bonded to the halogen bearing carbon.
Example :
X Cl
R – CH – R , CH 3 – CH – CH 3
(ii) Tertiary halide : Three other carbon atoms bonded to the halogen bearing carbon
atom.
Example :
R CH3
R– C – X , CH3 – C – Cl
R CH3
Haloalkanes can be classified into following three categories.

(i) Monohaloalkanes (ii) Dihaloalkanes (iii) Polyhaloalkanes
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ALKYL HALIDE
IUPAC nomenclature of alkyl halides

S.N. Compound IUPAC name
CH3
1. CH3 – C – Cl 2 – Chloro-2-methylpropane
CH3
2. CH 3 – CH – CH2 – CH2 3-Bromo-1-chlorobutane

Br Cl
3. CH2 – CH – CH – CH2 2-Bromo-1-chloro-4-fluoro-3-methylbutane

F CH3 Br Cl
4. CH3 – CH – CH2 – CH2 – CH2 5-Chloropentan-2-ol

OH Cl
5. F 5-Fluoropent-1-ene
Cl Cl
6. 2,2-Bis(chloromethyl)-1,3-dichloropropane
Cl Cl
Isomerism in haloalkanes :
S.N. Compound IUPAC name
1. Structural Isomerism
(a) Chain 1. CH3 – CH2 – CH2 – CH2 – Cl 1-Chlorobutane
CH3 – CH – CH2 – Cl 1-Chloro-2-methylpropane

CH3
2. CH3 – CH2 – CH2 – CH 2 – CH2 – Cl 1-Chloropentane

CH3
CH3 – CH – CH 2 – CH2 – Cl 1-Chloro-3-methylbutane
CH3
CH3 – C – CH2 – C l 1-Chloro-2,2-dimethylpropane
CH3

ALKYL HALIDE
(b) Position 1. CH3 – CH2 – CH2 – Cl 1-Chloropropane

Cl
CH3 – CH – CH3 2-Chloropropane
2. CH3 – CH – CH2– Cl 1-Chloro-2-methylpropane

CH3
Cl
CH3 – C – CH3 2-Chloro-2-methylpropane
CH3
2. Stereoisomerism
` (a) Optical isomerism
CH3
H * Cl Plane of
* symmetry
H Cl
CH3
Meso-optically inactive
Mirror Mirror
CH3 CH3 CH3 CH 3
H Cl Cl H H Cl Cl H
Cl H H Cl H Cl Cl H
CH2CH3 CH2CH3 CH 2CH 3 CH2CH3
Enantiomers Enantiomers
2,3-Dichloropentane

ALKYL HALIDE
Bonding in alkyl halide

Table : 1 Carbon halogen bond lengths
Bond Bond length(Å)

CH3 – F 1.39
CH3 – Cl 1.78
CH3 – Br 1.93
CH3 – I 2.14
Physical properties of alkyl halide

Dipole moment of the halogen derivatives:
 = 4.8 ×  × d
Where  is the charge and d is the bond length
These two effects e.g. charge and distance oppose each other, with the larger halogens
having longer bond but lesser value of electronegativity. The overall result is that the bond
dipole moment increase in the order.
C – I < C – Br < C – F < C – Cl
 : 1.29 D 1.48 D 1.51 D 1.56 D
The electronegativities of the halogen increase in the order:
I < Br < Cl < F
Table : 2 Molecular dipole moments of methylhalides

X CH3X CH2X2 CHX3 CX4
F 1.82 D 1.97 D 1.65 D 0
Cl 1.94 D 1.60 D 1.03 D 0
Br 1.79 D 1.45 D 1.02 D 0
I 1.64 D 1.11 D 1.00 D 0
Boiling point :
(a) With respect to the halogen in a group of alkyl halides, the boiling point increases as
one descends in the periodic table. Alkyl fluorides have the lowest boiling points and
alkyl iodides have the highest boiling point. This trend matches the order of increasing
polarizability of the halogens (Polarizability is the ease with which the electrons
distribution around an atom is distorted by a nearby electric field and is a significant
factor in determining the strength of induced-dipole/induced-dipole and dipole/induced-
dipole attractions). Forces that depend on induced dipoles are strongest when the
halogen is a highly polarizable iodine, and weakest when the halogen is a non-polarizable
fluorine.

ALKYL HALIDE
Table : 3 Boiling points of some alkyl halide in °C (1 atm)
Formula X=F X = Cl X = Br X=I

CH3– X – 78 – 24 3 42
CH3– CH2X – 32 12 38 72
CH3– CH2– CH2X –3 47 71 103
CH3– (CH2)3– CH2X 65 108 129 157
CH3– (CH2)4– CH2X 92 134 155 180
Fluorine is unique among the halogens is that increasing the number of fluorines does
not lead to higher and higher boiling point (B.P.).
Density :
Alkyl fluorides and chlorides are less dense and alkyl bromides and iodides more dense
than water.
Table : 5
Because alkyl halides are insoluble in water, mixture of an alkyl halide and water
separates into two layers. When the alkyl halide is a fluoride or chloride, it is on the
upper layer and water is in the lower. The situation is reversed when the alkyl halide is
a bromide or an iodide. In these cases the alkyl halide is in the lower layer.
Polyhalogenation increases the density. The compounds CH2Cl2, CHCl3 and CCl4 for
example, are all more dense than water.
Preparation of alkyl halide :

From alkane :
X2/hv
R–H R – X + HX
From alkenes and alkynes
HX
(a) C C –C–C–
H X
X2
(b) C C –C–C–
X X
(c)
X X
2X2
(d) C C –C–C–
X X

ALKYL HALIDE
From alcohol
HX, PX3,PX5, SOX2
R – OH R–X
From other halides
acetone
R – X + I– R – I + X–
18-crown-6
R – Cl + KF R–F
Finkelstein Reaction
NaI/acetone
1. CH3 – CH2 – Cl CH3 – CH2 – I
Nucleophilicity in polar protic solvent
– F < Cl <Br <I
Polar aprotic solvent
– F> Cl >Br> I
Covalent Nature : NaF < NaCl < NaBr < NaI
Solubility in polar solvent decreases.
CH 3 – C – CH 3 CH3 – S – CH 3
O O
Acetone  Solubility order in acetone
NaF < NaCl < NaBr < NaI
NaBr
2. CH3– CH2– Br Acetone
CH3– CH2– Br
NaCl
3. CH3– CH2– Cl Acetone
CH3– CH2– Cl
NaF
4. CH3– CH2– Cl Acetone
CH3 – CH2 – F
KF
5. CH3–CH2–Cl DMF
CH3–CH2–F
or DMSO
(Swart’s reaction)
Me Me
NaF
6. H Cl DMF F H
Et Et
Me
NaI
Acetone I H
Et
7.
(Racemisation)

ALKYL HALIDE
Chemical reactions of alkyl halide

Nucleophilic substitution reaction:
Those organic compounds in which a sp3 hybridized carbon is bonded to an electronegative
atom or group, can undergo two types of reactions e.g. substitution reaction in which the
electronegative atom or group is replaced by another atom or group. Second is elimination
reaction in which the electronegative atom or group is eliminated along with hydrogen
from an adjacent carbon. The electronegative atom or group which is substituted or
eliminated is known as leaving group.
Because of more electronegativity of halogen atom it has partial negative charge and
partial positive charge develops on carbon atom.
RCH2 – X
X = F, Cl, Br, I
Due to this polar carbon - halogen bonded alkyl halides shows nucleophilic substitution
and elimination reaction.
There are two important mechanisms for the substitution reaction
(1) A nucleophile is attracted to the partially positively charged carbon. As the nucleophile
approaches the carbon, it causes the carbon - halogen bond to break heterolytically
(the halogen keeps both of the bonding electrons.)
(2) The carbon-halogen bond breaks heterolytically without any assistance from the
nucleophile, by the help of polar protic solvent and carbocation is formed (solvolysis).
Formed carbocation then reacts with the nucleophile to form the substitution product.
(A) Bimolecular nucleophilic substitution reaction (SN2)

The mechanism of SN2 reaction
Nu + C–X Nu C X Nu – C + X
Transition state
Characteristic of SN2
(1) It is bimolecular, unistep process.
(2) It is second order reaction because in the rate determining step two species are involved.
(3) Kinetics of the reaction  rate  [alkyl halide] [nucleophile]
rate [alkyl halide] [nucleophile]

ALKYL HALIDE
If the concentration of alkyl halide in the reaction mixture is doubled, the rate of the
nucleophilic substitution reaction is double. If the concentration of nucleophile is
doubled the rate of reaction is also double. If the concentration of both are doubled
then the rate of the reaction becomes four times.
(4) Energetics of the reaction 
Nu C X
transition state +
+
G The difference in free energy between
+ the reactant and the transition state.
Free energy
+
G
Gº The difference in free energy between
Nu + C –X the reactant and product.
Gº
Nu – C +X
Progress of reaction
Figure : A free energy diagrams for a hypothetical SN2 reaction that takes place with a
negative G°
(5) No intermediates are formed in the SN2 reaction, the reaction proceeds through the
formation of an unstable arrangement of atoms or group called transition state.
(6) The stereochemistry of SN2 reaction  As we have seen earlier, in an SN2 mechanism
the nucleophile attacks from the back side, that is from the side directly opposite to
the leaving group. This mode of attack causes an inversion of configuration at the
carbon atom that is the target of nucleophilic attack. This inversion is also known as
walden inversion.
H H
walden
Nu C–l.g. inversion
Nu – C H + l.g.
H H
H
(7) Factors affecting the rate of SN2 reaction  Number of factors affect the relative rate of
SN2 reaction, the most important factors are:
(i) Structure of the substrate
(ii) Concentration and reactivity of the nucleophile
(iii) Effect of the solvent
(iv) Nature of the leaving group
(i) Effect of the structure of the substrate 
Order of reactivity in SN2 reaction : – CH3 > 1º > 2º >> 3º (unreactive)
The important factor behind this order of reactivity is a steric effect. Very large and
bulky groups can often hinder the formation of the required transition state and crowding
raises the energy of the transition state and slows down reaction.

ALKYL HALIDE
Table : 6 Relative rates of reactions of alkyl halide in SN2 reaction.

Substituent Compound Relative rate
Methyl CH3X 30
1º CH3CH2X 1
2º (CH3)2CHX 0.02
Neopentyl (CH 3)3CCH 2X 0.00001
3º (CH3)3CX ~0
(ii) According to kinetics of SN2 increasing the concentration of the nucleophile increases
the rate of an SN2 reaction. The nature of nucleophile strongly affect the rate of SN2
reaction. A stronger nucleophile is much more effective than a weaker. For example we
know that a negatively charged nucleophile is more reactive than its conjugate acid
e.g. HO > H2O, RO > ROH.
H H H
Inversion
R–O C–I R–O C I R–O–C + I
stronger
nucleophile
H H H
H
H
H
Lower Ea
H H
+ H
R – OH C–I R–O C I R–O–C + I
H H H H H
H
H
H
Higher Ea
Table : 7
Some common nucleophiles listed in decreasing
order of nucleophilicity in hydroxylic solvent
Strong nucleophiles (CH 3CH2)3P Moderate nucleophile : Br
SH NH3
I (CH3)2S
(CH3– CH2) 2NH Cl
– CN AcO
(CH3– CH2) 3N Weak nucleophile F
HO H2O
CH3O CH3OH

ALKYL HALIDE
Steric effects on nucleophilicity

CH3
CH3 C O
CH3 – CH2 – O
CH3

t-Butoxide Ethoxide is weaker base,
Stronger base, yet weaker yet stronger nucleophile
nucleophile cannot approach
the carbon atom so easily.
(iii) The effect of the solvent In polar protic solvent large nucleophiles are good, and the
halide ions show the following order:
I > Br > Cl > F (in polar protic solvent)
This effect is related to the strength of the interaction between nucleophile and solvent
molecules of polar protic solvent forms hydrogen bond to nucleophiles in the following
manner.
Because small nucleophile is solvated more by the polar protic solvent thus its
nucleophilicity decreases and rate of SN2 decreases.
Relative nucleophilicity in polar protic solvent:
SH > CN > I > OH > N3 > Br > AcO > Cl > F > H2O
So, polar protic solvents are not useful for rate of SN2, if nucleophile is anionic. But
polar aprotic solvent does not have any active hydrogen atom so they cannot forms H
bond with nucleophiles. Polar aprotic solvent have crowded positive centre, so they do
not solvate the anion appreciably therefore the rate of SN2 reactions increased when
they are carried out in polar aprotic solvent.
Examples of polar aprotic solvent.
CH3 CH3
H – C – N(CH3)2 CH3 – C – N(CH3)2
S
O O
O (DMA)
(DMF) (DMSO)
In DMSO, the relative order of reactivity of halide ions is
F > Cl > Br > I
(iv) The nature of the leaving group  The best leaving groups are those that become the
most stable ion after they leave, because leaving group generally leave as a negative
ion, so those leaving group are good, which stabilise negative charge most effectively
and weak base do this best, so weaker bases are good leaving groups. A good leaving
group always stabilize the transition state and lowers its free energy of activation and
thereby increases the rate of the reaction.
Order of leaving ability of halide ion
I > Br > Cl > F
Other leaving groups are
O O
O S R O S O–R
O O
Alkane sulphonate ion Alkyl sulphate ion

ALKYL HALIDE
O
O S CH3 CF3SO3
Triflate ion
O
(Best leaving group)
Tosylate ion (OTs)
Strongly basic ions rarely act as leaving group 

Br + R – OH R – X + OH (strong base and bad leaving group)
Nu + CH3 – CH3 CH3 – Nu + CH3 (CH3 is a strong base)

Table : 8 Examples of SN2 reactions of alkyl halide 
SN2
Nu + CH3 – X Nu – R + X (X is not F)
Nucleophile Product Class of Product
R – X +– I
R– I Alkyl halide
R – X +– OH
R – OH Alcohol
–
R – X + OR'
R – OR' Ether
R – X +– SH
R – SH Thiol(mercaptan)
R – X +– SR'
R – SR' Thioether (sulphide)
[R – NH3]+ X– Amine
R – X + NH3
+ +
R – X + – N = N = N– R – N = N = N– Azide
R– C C – R' Alkyne
R – X +– C C – R'
R– C N Nitrile
R – X +– C N
R – X + R' – COO – R – COO – R Ester
[R – PPh3]+X– Phosphonium salt

R – X + P(Ph)3

ALKYL HALIDE
(B) Unimolecular nucleophilic substitution reaction (SN1) :

Acetone
(CH3)3C – Cl + OH H2O (CH3)3C – OH + Cl
Mechanism of SN1 reaction :
Step - 1 Formation of a carbocation (Rate determining step)
R–X R + X
Step - 2 Nucleophilic attack on the carbocation (fast)

R + Nu R – Nu
Characteristics of SN1 reactions :
1. It is unimolecular, two step process and intermediate is formed (intermediate is
carbocation).
2. It is first order reaction.
3. Kinetics of the reaction
Rate  [Alkyl halide]
Rate = k[(CH3)3C–X]
Rate of SN1 reaction is independent of concentration and reactivity of nucleophile.
4. Energetics of the SN1
Intermediate
Ts(1) R – Nu
R–X
Ts(2)
R + Nu + X
Free energy
G1
G2
R – X + Nu
R – Nu + X
Figure : Free energy diagram for the SN1 reaction.
5. Factors affecting the rate of SN1:
(i) The structure of the substrate 
The rate determining step of the SN1 reaction is ionisation step, in this step carbocation
is formed. This ionisation is strongly endothermic process, rate of SN1 reaction depends
strongly on carbocation stability because carbocation is the intermediate of SN1 reaction
which determines the energy of activation of the reaction.
SN1 reactivity : 3º > 2º > 1º > CH3 – X
(ii) Concentration and reactivity of the nucleophile :
The rate of SN1 reactions are unaffected by the concentration and nature of the
nucleophile.

ALKYL HALIDE
(iii) Effect of the solvent the ionizing ability of the solvent:

To solvate cations and anions effectively the use of polar protic solvent will greatly
increase the rate of ionization of an alkyl halide in any SN1 reaction. It does this because
solvation stabilizes the transition state leading to the stabilization of intermediate
carbocation and halide ion more than it does the reactant, thus the energy of activation
is lower.
R–X R + X (Solvolysis)
O
H H
H H
O
H H
O R O H X H H
O
H H O
O H
H H H H
O
Solvated ions
Table : 9 Dielectric constants () and ionization rates of t-Butylchloride in common solvents
Solvent  Relative rate
H2 O 80 8000
CH3OH 33 1000
C2H5OH 24 200
(CH3)2CO 21 1
CH3 CO 2H 6 -
(iv) The nature of the leaving group 
In the SN1 reaction the leaving group begins to acquire a negative charge as the transition
state is reached stabilisation of this developing negative charge at the leaving group
stabilizes the transition state and this lowers the free energy of activation and thereby
increases the rate of reaction.
Leaving ability of halogen is I > Br > Cl >> F
6. Stereochemistry of SN1 reactions   In the SN1 mechanism, the carbocation
intermediate is sp2 hybridized and planar. A nucleophile can attack on the carbocation
from either face, if reactant is chiral than after attack of nucleophile from both faces
gives both enantiomers of the product, which is called racemization.

ALKYL HALIDE
Mechanism of racemization (SN1) 
Comparison of SN1 and SN2 reactions
S N1 S N2
Nucleophile strength is
(i) Effect of the nucleophile Stronger nucleophile is required
not important
(ii) Effect of the substrate 3o > 2o > 1o > CH3X CH3X > 1o >2o
Good ionizing solvent It goes faster in less polar solvent,
(iii) Effect of solvent
required if Nu is present
(iv) Kinetics Rate = k [R-X] Rate = k[R-X] [Nu]
(v) Stereochemistry Racemisation walden inversion
(vi) Rearrangement Common Impossible

ALKYL HALIDE
Some Nucleophilic reaction of R – X :–
RMgX
R–Me
RNa
R–Me (Wurtz Reaction)
R2Zn
R–Me (R2Zn is Frankland Reagent)
R2CuLi
R – Me (R2CuLi is Gilman's Reagent)
R–C CNa
R–C C – Me
NH3
H3N Me–Cl Me–NH2+HCl
MeNH2
Me–NH–Me
Me2NH
Me3N
Me3N
Me—Cl Me3N Me–Cl Me4N Cl
H2S/heat
MeSH + HCl
KCN (K C N)
Me–CN + Me – N C)
(Major product) (Minor product)
AgCN
Me–NC (Methyl isocyanide)
KNO2
(CH3– O – N = O + CH3 – NO2)
(Major product) (Minor product)
AgNO2
Me–NO2
(Ag–O–N=O)
RONa
ROMe (Williamson's ether synthesis)
RSNa
RSMe (Thioether)
Williamson's Ether Synthesis: (SN2)
1. R O Na + R – Cl R – O – R + NaCl
2. EtONa + Me – Cl  EtOMe
3. MeONa + Et – Cl EtOMe
Rate (2) > (3), 2 is better method. (Due to less steric hindrance)
4. PhONa + MeCl PhOMe + NaCl

5. Me3CONa+ MeCl Me3COMe + NaCl
CH3
6. MeONa + Me3C – Cl CH2 = C + MeOH + NaCl
CH3
Major

ALKYL HALIDE
CH3
7. PhONa + Me3C–Cl CH2 = C + PhOH + NaCl
CH3
Reaction of RX with NH3
1.
2.
Me Me
SN2
3. D Br + NH3 H2N D + HCl
H H
4.
(Pyridinium salt)
Some other reactions
Hydrolysis of Ether
18 H3O 18
1. MeOEt Et – OH + MeOH
18
2. MeOEt Et – OH + Me – OH
Me Et Me Et Me Et
H3O H3O
3. H O H H HO H H OH+ HO H
D D D D D D
SNi (Nucleophilic substitution intramolecular)
(Darzen’s process)
Cl
..
R OH + S = O R Cl + SO2 (g) + HCl (g)
Cl
Mechanism
Cl H
.. Cl
R OH + S = O R O O
S O
Cl
Cl
HCl(g)
O
R S=O
Cl
R – Cl + O = S = O  (g)

ALKYL HALIDE
Note : (1) In SNi retention of configuration takes place.

Note : (2) In presence of pyridine above reaction follow the SN2 reaction mechanism.
SNNGP(Neighbouring group participation)
Increase in rate of SN reaction due to attack of internal nucleophile is called as SNNGP is also
known as anchimeric assistance.
For SNNGP :–
1. Internal nucleophile must be present.
2. Internal nucleophile must be anti to leaving group.
Example
Elimination reactions:
In an elimination reaction two atoms or groups (YZ) are removed from the substrate with
formation of pi bond.
Elimination
C C C C
-Y Z
Y Z
Depending on the reagents and conditions involved, an elimination may be a first order
(E1) or second order (E2).
Dehydration of Alcohol (E1)
Conc.H2SO4
CH3–CH2 – OH CH2=CH2
H –H
– H2O
CH3–CH2 – OH2 CH3–CH 2
Characteristics of E1 reaction :
(i) It is unimolecular, two step process.
(ii) It is first order reaction.
(iii) Reaction intermediate is carbocation, so rearrangement is possible.
(iv) In the second step, a base abstracts a proton from the carbon atom adjacent to the
carbocation, and forms alkene.
(v) Kinetics  Rate  [Substrate]
Rate  k[Substrate]

ALKYL HALIDE
Transition state (1)

Transition state (2)
H H
C C C C
Potential energy
H H
H
B
H H
H C C H
H H
B
E2- elimination :
H–CH2 – CH2 – lg CH2 = CH2 + lg
B H B H
H H H H
C C C C
H H
lg lg
H H
Transition state
Transition state
Potential energy
H H
C C
H H
reaction progress
Bimolecular reaction, second order kinetic.

1. Leaving group leads when base is taking proton from adjacent carbon.
2. It is a single step reaction
3. Rate  Leaving group tendency
4. It shows elemental as well as kinetic isotopic effect with leaving group as well as at -
position.
5. Normally saytzeff product is major.
6. Transition state mechanism therefore rearrangement is not possible.
7. The orientation of proton & leaving group should be antiperiplanar for E2.
8. Positional orientation of elimination  In most E1 and E2 eliminations gives two or
more possible elimination products, the product with the most highly substituted double
bond will predominate. This rule is called the saytzeff or zaitsev rule (i.e., most stable
alkene will be the major product)

ALKYL HALIDE
9. E2–elimination is favoured by :
(1) Moderate leaving group.
(2) Strong base (RO, Alc. KOH).
(3) Polar aprotic solvent.
(4) High concentration of base.
(5) High temperature.
Reactivity towards
E2  R – I > R – Br > R – Cl > R – F
Comparison of E1 and E2 elimination:
Promoting factors E1 E2
(i) Base Weak base Strong base required
(ii) Solvent Good ionizing solvent Wide variety of solvent
(iii) Substrate 3º > 2º > 1º 3º > 2º > 1º
(iv) Leaving group Better one required Better one required
Characteristics
(i) Kinetics K[R– X], I order K[R – X] [Base], II order
(ii) Orientation Saytzeff alkene Saytzeff alkene
(iii) Stereochemistry No special geometry transition state
is required must be co-planar
(C) Mechanism of E1CB reaction (Unimolecular conjugate base reaction) :
The E1CB or carbanion mechanism : In the E1CB, H leaves first and then the X. This is a
two step process, the intermediate is a carbanion.
Mechanism:
Step-1 : Consists of the removal of a proton, H by a base generating a carbanion
Step-2 : Carbanion loses a leaving group to form alkene
Condition: For the E1 CB, substrate must be containing acidic hydrogens and poor leaving
groups (i.e., bad l.g.)
Ex.
In case of ethanol, the reaction occurs as follows

CaOCl2 + H2O  Ca(OH)2 + Cl2
Oxidation
CH3CH2OH + Cl2 CH3CHO + 2HCl

ALKYL HALIDE
CH3CHO + 3Cl2 Chlorination CCl3CHO + 3HCl

Chloral
Ca(OH)2 + 2CCl3 CHO Hydrolysis 2CHCl3 + (HCOO)2Ca
Chloroform Calcium formate
1. From carbontetrachloride
Fe/H2O
CCl4 + 2[H] Heat
CHCl3 + HCl (partial reduction)
2. Haloform reaction
(Haloform)
Step 1 : Attack of the Step 2 : Elimination Step 3 : Proton transfer
nucleophile of the leaving group
Dehydrohalogenation (–HX) E2
Aq.KOH
CH3 – CH 2 – Cl CH3 – CH 2 – OH
Alc. KOH
CH2=CH2
OH
H HO H
H H H H
C -----– C C -----– C
H H H H
Cl Cl
Anti elimination
Dehalogenation : – (–X2) E2
+2 –
Zn Zn +2e
CH2 – CH2 CH2 = CH2 + ZnX2

X X
2e
X
H H
C -----– C
H H
X
Anti elimination

ALKYL HALIDE
Ec or Ei (Intramolecular or cyclic elimination mechanism):

(1) Leaving group and Base present in same molecule.
(2) It proceeds by cyclic transition state.
(3) Overall it is syn elimination.
(4) Hoffmann is major product as it is obtained by least hindered site/cyclic transition
state.
(5) No rearrangement.
Example of Ec/Ei
Pyrolysis of Ester :
1.
2.
Chemical properties of chloroform

1. Action of sunlight and air
2 CHCl3 + O2 2COCl2 + 2HCl
Phosgene
As chloroform is used for anaesthetic purposes, we need to maintain a high purity of
chloroform, this reaction can be avoided by storing it in dark bottles, completely filled upto
brim. The use of dark bottles (brown or blue) cuts off active light radiations and filling upto
brim, keeps out air. Apart from this a small amount of ethanol (1%) is usually added to
bottles of chloroform. Addition of a little ethanol fixes the toxic COCl2 as non-poisonous
Diethyl carbonate.
COCl2 + 2C2H5OH O = C(OC2H5)2 + 2HCl
Diethyl carbonate
2. Hydrolysis :
–3KCl +KOH
H – CCl3 + (aq.) 3KOH –H2O H–C–O–H –H2O HCOOK
OOK
O
3. Reduction :
Zn + 2HCl ZnCl2 + 2[H]
CHCl3 + 2[H] CH2Cl2 + HCl
Dichloromethane
(Methylene chloride)
Zn + H2O
CHCl3 CH4 + 3HCl

ALKYL HALIDE
4. Reaction with acetone :
KOH
(CH3)2C = O + CHCl3
Chloretone
Use : Chloretone is used as hypnotic (a sleep inducing) drug.
5. Reaction with nitric acid
2CHCl3 + HONO2 CCl3. NO2 + H2O
(chloropicrin)
Use : Chloropicrin is used as an insecticide and war gas.
6. Reaction with silver powder :
Heat
2CHCl3 + 6 Ag CH  CH + 6 AgCl
(Acetylene)
7. Chlorination :
hv
CHCl3 + Cl2 CCl4 + HCl
8. Reimer-Tiemann reaction:
OH OH
CHO
333-343 K
+ CHCl3 + 3NaOH + 2NaCl + 2H2O
Phenol Salicylaldehyde
(2-Hydroxybenzaldehyde)
Uses of chloroform
1. As solvent in oils and varnishes
2. As preservative for anatomical specimens
3. As laboratory reagent
4. As an anaesthetic

ARYL HALIDE
ARYL HALIDE
(HALOARENES)
Aliphatic Halogen Derivatives :
Compounds obtained by the replacement of one or more hydrogen atom(s) from
hydrocarbons are known as halogen derivatives. The halogen derivatives of alkanes, alkenes,
alkynes and arenes are known as alkyl halide (haloalkane), alkenyl halide (haloalkenes),
alkynyl halides (haloalkynes) and aryl halides (halobenzenes) respectively.
Electrophilic aromatic substitution (EAS) :

Based on its structure and properties, what kind of reaction should benzene undergo ? Are
any of its bond particularly weak does it have electron rich or electron deficient atom.
* Benzene has six p-electron delocalized in six p-orbitals that overlap above and below the
plane of ring.
These loosely held -electron make the benzene ring electron rich, and so it reacts with
electrophile.
* Because benzene six -electron satisfyHuckel’s rule, benzene is especiallystable. Reactions
that keep the aromatic ring intact are therefore, favoured.
* Electron cloud above and below the plane of benzene shields the ring carbon from the
attack of a nucleophile.
As a result, the characteristic reaction of benzene is electrophilic aromatic substitution - a
hydrogen atom is replaced by an electrophile.
Benzene does not undergo addition reaction like other unsaturated hydrocarbons, because
addition would yield a product that is not aromatic . Substitution of a hydrogen on the other
hand, keeps the aromatic ring intact.

ARYL HALIDE
Preparation of haloarene
1. The introduction of halo (–X) group on benzene known as halogenation of benzene
The bromination or chlorination of benzene requires a Lewis acid catalyst such as FeBr3,AlBr3,
FeCl3 or AlCl3.
Sometime Fe orAl is used but real catalyst is not Fe orAl itself but FeX3 orAlX3 is formed
from the reaction between halogen and Fe orAl.
Mechanisms for Bromination
–
Br FeBr3
Mechanisms for Chlorination
–  – 
Bromination and chlorination also occur by HOBr and HOCl , obtained by reaction between
H2O and X2.
H2O + X2  2HOX (X = Cl, Br)
Iodination of benzene requires an acidic oxidizing agent such as nitric acid. Nitric acid is
consumed in the reaction, so it is a reagent rather a catalyst.

ARYL HALIDE
Mechanisms for Iodination
The electrophile required for halogenation reaction is halonium ion (X+)

2. Addition of Halogen
Benzenehexachloride (BHC, C6H6Cl6) is also called Lindane or Gammaxene (-isomer) and

is used insecticide.
3. Direct halogenation :

ARYL HALIDE
Low temperature and the presence of a halogen carrier favour nuclear substitution. The
chlorides or bromides ofAl, Fe, Sb may use used :
Iron is most commonly used being converted to Lewis acid FeCl3 as shown above.
It is again SE reaction and without halogen-carrier (Lewis acid), Cl+ (halonium) is not formed
and hence, reaction is not possible :
A methoxy group is so strongly activating that anisole quickly bromines in water without a
catalyst :

ARYL HALIDE
Direction iodination is not possible since, iodine is least reactive and HI formed makes
reaction reversible.
In presence of oxidising agents like HNO3 or HIO3 , iodination of benzene is possible and HI
formed is converted to I2 :
Iodination probably involves an electrophilic aromatic subtitution with iodonium (I+) acting
as the electrophile. I+ is formed from iodine byoxidation with HNO3.
Diazonium salts are converted to halogen compounds :
Diazonium salts are obtained by diazotisation of amino compounds and this provides a
better route to convert amino compounds into halogen compounds :
Side-Chain Derivatives

ARYL HALIDE
Side-chain halogenation involves free radical mechanisms due to lower bond energyof the
benzyl C–H bond.
Physical Properties
• Less polar, insoluble in water but soluble in organic solvents like ethanol and ether.
• They show physiological activity and are used as insecticides.
Examples are :
Chemical Properties
(a) Wurtz-Fitting Reaction
Only aryl halide is involved, diphenyl is formed (Fitting reaction)

(b) Ullman synthesis
(c) Reaction with Chloral

DDT is formed when chloral reacts with chlorobenzene in presence of concentrated H2SO4.
DDT is causing ecological problems, its use as insecticides is being banned.

ARYL HALIDE
Nitration
Chlorination
Sulphonation
Chlorobenzene sulphonic acid
• Chlorine is not a good donor of electrons by resonance due to its high electronegativity.
Thus, the inductive effect of the Cl atom overcomes the resonance effect, and thus, it
deactivates the benzene ring.
(d) Substitution on benzyl carbon (S) : The greater reactivities of benzylic halides result
from the stabilities of the carbocation intermediates that are formed when they react.
Tertiarycumyl chloride ionises to a carbocation with four important resonance structure :

ARYL HALIDE
Because of the possibilitie of resonance, ortho and para substituent group on the benzene
ring that activate electrophilic aromaticsubstitution further accelerate SN1 reaction at the
benzylic position. Thus p-methoxytert-cumyl chloride (I) undergoes hydrolysisabout 3400
times fasterthan tert-cumyl chloride II.
Benzylic halides undergo SN reactions like aliphatic halides.
This provides a path of converting toluence into so many other compounds benzyl chloride.
Anamalous behaviour of halogen substituent :

– X(F, Cl, Br, I) is o–, p-directing but is deactivating group.
Rate  single step reaction

This deactivating nature is attributed to high electronegativity of the halogen atom due to
which they withdraw electrons; resonance effect explains its electron-donating behaviour.

ALCOHOL
ALCOHOL
Introduction
Physical Properties
(1) Boiling point :
(a) Alcohols show increase in boiling point with increase in molecular weight amongst
homologous series.
(b) Alcohols have higher boiling point than hydrocarbons of the same molecular weight.
The reason for higher boiling point is the intermolecular H-bonding present in alcohols.
H–O H–O H–O
R R R
Intermolecular H bonds in alcohol
(2) Solubility in water :
As molecular weight increases solubility in water decreases. The lower alcohols are
miscible with water. This is due to intermolecular hydrogen bonding between alcohol
and water molecules.
Intermolecular H bond between water & alcohol molecules
Preparation of alcohols
(1) From alkenes
(a) By acid catalyzed hydration of alkenes : Formation of carbocation intermediate
(Markovnikov addition, rearrangement possible).
conc.H SO
General reaction R–CH=CH2  2 4 
Markovnikov 's addition
Boiling H2O
R–CH–CH3   R–CH–CH3
Alkene
OSO3H OH
Alcohol

ALCOHOL
H HSO4 Boiling H2O

e.g. CH–CH=
3 CH2 CH–CH–
3 CH3 CH–CH–
3 CH3
OSO3 H
H2SO4+CH 3–CH–CH3
OH
(b) By Oxymercuration - demercuration process :

(1) Oxymercuration involves an electrophilic attack on the double bond by the positively
charged mercury species. The product is a mercurinium ion, an organometallic cation
containing a three-membered ring.
(2) In the second step, water from the solvent attacks the mercurinium ion to give (after
deprotonation) an organomercurial alcohol.
(3) The third step is demercuration to remove the sodium borohydride (NaBH4, a reducing
agent) replaces the mercuric acetate fragment with hydrogen.
General reaction
H H
H H  O 
  THF
C=C + H2O + Hg   R–C—C–H + CH3COOH
R H  O  C  CH3 2 O
OH Hg–(O–C–CH 3)
H H H H O
R–C— C–H + OH + NaBH4 R–C— C–H + Hg + CH3–C–O

O
OH Hg–(O–C–CH3) OH H
Hg(OAc)2 +OH 
e.g. CH3–CH=CH2   CH 3–CH–CH2   CH3–CH–CH3
THF/H2O NaBH4
Prop-1-ene OH Hg(OAc) OH
Propan-2-ol
(c) By Hydroboration - oxidation process : (Forms anti-markovnikov alcohol, no
rearrangement)
(i) BH , THF
General reaction R–CH=CH2  
3
(ii) H O , NaOH R–CH2–CH2–OH
2 2
CH3H
H3C CH3 (i) BH3 , THF
e.g. C=C   H3C–C—C–CH3
(ii) H O , NaOH
H3C H 2 2
H OH

ALCOHOL
(2) From alkyl halides : By nucleophilic substitution reactions

(a) By SN2 mechanism (second-order substitution) : It is given by primary (and some
secondary) halides
KOH
General reaction : R–CH2–Br 
H2 O R–CH2–OH
KOH
e.g. (CH3)2CHCH2CH2–Br 
H2 O (CH3)2CHCH2CH2– OH
H Br KOH 
 HO H
e.g. C SN2 C
CH3 CH2CH3 CH3 CH2CH3
(S)-2-Bromobutane (R)-2-Butanol
100% inverted configuration
(b) By SN1 mechanism : It is given by tertiary and some secondary halides

R' R'
Acetone / water
General reaction : R–C–R" 
Heat
 R–C–R"
Cl OH
CH3 CH3
Acetone/water /heat
e.g. CH3–C–CH3 
SN1 CH3–C–CH3
Cl OH
Tert-butyl chloride Tert-butyl alcohol
(3) From Grignard reagents

(a) From air
A Grignard reagent may be used to synthesize an alcohol by treating it with dry oxygen
and decomposing the product with acid :
General reaction RMgX  RO2MgX  H3O
 2ROMgX   2ROH
O2 RMgX
e.g. C 2 H 5MgBr  C 2 H 5O 2 MgX  H O

 2C 2H 5 OMgX 2C 2 H 5 OH +
O2 C2H5 MgX

3
MgBr(OH)
(b) From ethylene oxide
Addition of Grignard reagent to ethylene oxide gives a primary alcohol (with two carbon
atoms added)
CH 2
General reaction H3O
RCH2CH2OMgX  RCH2CH2OH + MgX(OH)
O + RMgX
CH 2
CH2
e.g. + C2H5MgBr H3O
C2H5CH2CH2OMgX  C2H5CH2CH2OH + MgBr(OH)
O
CH2
Butyl alchohol

ALCOHOL
MgBr
O CH2CHOH
(1) CH2–CH–CH3
Cyclohexylmagnesium bromide 
CH3
(2) H3O
(c) From carbonyl compounds : Nucleophilic addition to the carbonyl groups by Grignard
reagent
O O MgX OH
General reaction –C– + R – MgX  H3O
ether  –C–  —C— + Mg(OH)X
R R
adduct
(i) Addition of formaldehyde gives a primary alcohol

H H OMgX H O
General reaction Ether
C = O + RMgX  C 
3
RCH2–OH
H H R
(ii) Addition to an aldehyde (other than formaldehyde) gives a secondary alcohol
O
R OMgX R OH
General reaction R–C–H + R'MgX 
Ether C H O C

3
H R' H R'
(sec-Alcohol)
(1) ether solvent

e.g. +  
(2)H3O
(iii) Addition to a ketone gives a tertiary alcohol
(1) ether
General reaction  
(2)H3O
O
(1) ether
e.g. CH3CH2MgCl +  
(2)H3O
Cyclohexanone

ALCOHOL
(iv) Addition to an acid halide or an ester gives a tertiary alcohol

Esters on treatment with Grignard reagent first form ketones which then react with
second molecule of Grignard reagent and form tertiary alcohol.
General reaction
O
OR'
R–C–R+ Mg
X
R H O/H
C=O + R MgX 
2


R
O
R–C–R+ MgX2 OH
RMgX X
R–C–R+ Mg
OH
R'
(4) By reduction of carbonyl compounds
(a) Catalytic hydrogenation of aldehydes and ketones
General reaction
H2 /Ni
R–CHO   R–CH2OH
o
Aldehyde 1 Alcohol
R2C=O H2 /Ni R2CH–OH
 
Ketone o
2 Alcohol
e.g. CH3CHO + 2H 
H 2 / Ni
 CH3CH2OH
Ni
CH2=CHCHO + 4H  
Catalyst CH3CH2CH2OH
(Acrolein)
O H
+ 4H 
Ni OH
(b) Lithium aluminium hydride reduction of aldehydes and ketones

General reaction
(i) R–CHO LiAlH4
  R–CH 2OH
o
Aldehyde 1 Alcohol
LiAlH4
(ii) R2C=O  R2CH–OH
Ketone o
2 Alcohol
LiAlH4
(iii) RCOOH + 4H   RCH2OH + H2O

ALCOHOL
LiAlH4
(iv) R–C–Cl + 4H  RCH2OH + HCl
O
(v) R–C–O–R' 
LiAlH4
 R–CH2OH + R’OH
OH
O
O
e.g. CH3–C–O–H 
LiAlH4
 CH3CH2OH
O
C2H5–C–Cl + 4H C2H5CH2OH + HCl

(c) By NaBH4 (sodium borohydride) : It is insoluble in ether and is used in aqueous
ethanolic solution to reduce carbonyl compounds. It does not reduce esters and acids.
O
NaBH
R–C–H 
4
 R–CH2–OH
O
NaBH
e.g. C–H 
4
 CH2OH
Benzaldehyde Benzyl alcohol
NaBH
CH3 CH=CHCHO + 4H  4
 CH3CH=CHCH2OH
(ii) Reduction of a ketone gives a secondary alcohol
O H
NaBH OH

4

Cyclohexanone Cyclohexanol
Mechanism
R–C–OEt Na RC–OEt EtOH

•• Na
RCH–OEt R–CH–OEt
O O• O• O
EtOH Na EtOH •• Na
RCH2OH O RCH2–O RCH2–O• RC–O• RCH=O+OEt
Na
e.g. CH3CHO + 2H   CH CH OH
EtOH 3 2
Na
CH3COOC2H5 + 4H 
EtOH
 2CH CH OH
3 2
CH 3
Na
CH3–C–CH3+2H 
 CH–OH
EtOH
CH3
O
(5) By reaction of nitrous acid on aliphatic primary amines
General reaction
NaNO /HCl
R–NH2+HONO 2
orHONO
 R–OH + N2 + H2O

ALCOHOL
Mechanism
H2O
R–NH2   (R N2 ) 
HNO2

 ROH+ N2+ H
e.g. (i) C2H5NH2 + HNO2 C2H5OH + N2 + H2O
CH3 CH3
NaNO2 /HCl
(ii) CH3–CH2– C–CH3 
 CH3–CH2– C–CH3 + N2+H2O
orHONO
NH2 OH
Mechanism
CH3 CH3 CH 3
HONO H2O
CH3–CH2– C–CH3  CH3–CH2– C–CH3 
 CH3–CH2– C–CH3
NH2 OH
(6) Hydroxylation : Forms vicinal diols (glycols)
Converting an alkene to a glycol requires adding a hydroxy group to each end of the
double bond. This addition is called hydroxylation of the double bond.
(a) Syn hydroxylation, using KMnO4 / NaOH or using OsO4/H2O2
General reaction :
C=C
H CH2CH3
CH2CH3
C KMnO4
  H OH
e.g. cold
C (dilute) H OH
H CH2CH3 CH2CH3
cis-3-Hexene
H
OH
OsO4 /H2O2


OH
Cyclopentene H
cis-Cyclopentane-1, 2-diol
(b) Anti hydroxylation, using per acids

H

OH
RCOOH, H

H2O
Cyclopentene H
OH
trans-Cyclopentane-1, 2-diol

ALCOHOL
Chemical reactions of alcohols

1. Reaction with hydrogen halides
General reaction :
R – OH + HX R – X + H2O (R may rearrange)
Reactivity of HX : Hl > HBr > HCl
Reactivity of ROH : Allyl, benzyl > 3o > 2o > 1o
Mechanism H
R – OH  R–

R X R–X
conc. HBr
e.g. CH3CHCH3 CH3CHCH 3
or NaBr,H2SO4
OH reflux Br
Isopropyl alcohol Isopropyl bromide
HCl, (anhydrous) ZnCl2

Lucas reagent
e.g. CH3CH2CH2CH2CH2OH CH3CH2CH2CH2CH2Cl
heat n-Pentyl chloride
n-Pentyl alcohol
CH3 CH3
conc.HCl
e.g. CH3–C–CH3   CH3–C–CH3
room temp.
OH Cl
tert- Butyl alcohol tert-Butyl chloride
2. Reaction with Phosphorus trihalides

(1) Several phosphorus halides are useful for converting alcohols to alkyl halides. PBr3, PCl3, &
PCl5 work well and are commercially available.
(2) Phosphorus halides produce good yields of most primary and secondary alkyl halides,
but none works well with tertiary alcohols. The two phosphorus halides used most
often are PBr3 and the P4 / I2 combination.
General reaction : (PX 3  PCl3 ,PBr3 ,PI3 )
3R – OH + PX3      3R – X + H3PO3
Mechanism
The mechanism for the reaction involves attach of the alcohol group on the phosphorus
atom, displacing a bromide ion and forming a protonated alkyl dibromophosphite (see
following reaction).


In second step a bromide ion acts as nucleophile to displace HOPBr2, which is a good
leaving group due to the electronegative atoms bonded to the phosphorus.

ALCOHOL

 RCH2X + HOPX2
CH3 CH3
e.g. PBr3
CH3CH2CHCH2OH   CH3CH2CHCH2Br
2–Methyl–1–butanol 2–Methyl–1–bromobutane
P+I
CH 3CH2OH 
2
 CH3CH2I
Ethyl alcohol Ethyl iodide
3. Reaction with thionyl chloride
O
Heat
R–OH+Cl–S–Cl  R–Cl+SO2+HCl
4. Dehydration of alcohols
Acid
– C – C –  – C = C – + H2O (Rearrangement may occur)
H OH
Mechanism
Step 1 :
CH 3 H
Step 2 : CH3– C – ••
O –H

CH3
H CH2
H–C–H H C H

Step 3 : C + O–H CH3 CH3 + H –O – H
••
•• ••
CH3 CH3 2-Methylpropene
Reactivity of ROH : 3° > 2° > 1°

ALCOHOL
5. Ester formation
General reaction
O  O
H
R–C + R'OH R–C + H2O
OH OR'
Acid Alcohol Ester
O O
H 
e.g. CH3CH2O – H + CH3C  CH3C + H2O
OH OC2H5
Acetic acid Ethyl acetate
O H2SO4 O
CH2–CH2–CH2–C + C2H5OH CH2–CH2–CH2–C +H2O
OH reflux OC2H5
-Phenyl butyric acid Ethyl -phenyl butyrate

(1 mole) Ethyl alcohol (85-88% yield)
(8 moles)
6. Oxidation reactions
(a) oxidation of primary alcohols
Oxidation of a primary alcohol initially forms an aldehyde. Obtaining the aldehyde is
often difficult, since most oxidizing agents are strong enough to oxidize the adehydes
formed. CrO3 acid generally oxidizes a primary alcohol all the way upto the carboxylic
acid
(b) oxidation of secondary alcohols
Secondary alcohols are easily oxidized to give excellent yields of ketones. The chromic
acid reagent is often best for laboratory oxidations of secondary alcohols. The active
species in the mixture is probably chromic acid,
H2CrO4, or the acid chromate ion, HCrO 4
(c) Resistance of tertiary alcohols to oxidation

Oxidation of tert-alcohol is not an important reaction in organic chemistry. tert-alcohols
not have hydrogen atoms on the carbinol carbon atom, so oxidation must take place by
breaking C–C bonds. These oxidations require severe conditions and result in mixtures
of products.
Primary

ALCOHOL
R R
K2Cr2O7 or CrO3 /H
Secondary R–CHOH   R–C = O
A ketone
Tertiary KMnO4
R–C–OH   no reaction
R
H
e.g. CH3CH2CH2OH C5H5NHCrO3Cl
 CH3CH2C=O

n-Propyl alcohol Propionaldehyde
(1º)
CH3 CH 3
KMnO4
CH3CH2CHCH2OH  CH3CH2CHCOOH
2-Methyl-1-butanol 2-Methylbutanoic acid
(1º)
CrO /H
CH3CH2CHCH2CH3 
3
 CH3CH2CCH 2CH3
OH O
3-Pentanol 3-Pentanone
(2º)

CARBONYL COMPOUND
CARBONYL COMPOUND
Introduction
These have general formula CnH2nO and contains > C = O group which is present in aldehyde
R R
C = O and C = O ketone. Thus aldehydes and ketones are collectively called ass
H R
carbonyl compounds.
IUPAC Nomenclature of Aldehydes and Ketones

CARBONYL COMPOUND

CARBONYL COMPOUND
Section A
3. General methods of preparation of Aldehyde and Ketones
(I) Hydration of Alkyne :
It is addition of water in the presence of heavy metal ion. Acetylene on hydration gives
aldehyde while any higher alkyne gives ketone.
The preparation of carbonyl compounds from alkyne depends upon R part of alkyne
and also presence of inductive effect group attached to R.
(II) Hydroboration of alkyne :
It is used to get aldehyde from alkyne-1. Here reagents are (i) diborane (B2H6) (ii) H2O2(OH–)
(i) B2H6
R–C C–H R – CH2– CH = O
(ii) H2O2/OH –
In this reaction Borane (BH3) is electrophile.

BH HO
3R–CC–H 3
(R–CH= CH)3B 2 2 R – CH = CH – OH R – CH2 – CH = O
Higher alkyne except alkyne-1 will give ketone during hydroboration
(i) BH3, THF

CH3 – CH2 – C  C – CH2 – CH3 –
CH3 – CH2 – –CH2 – CH2 – CH3
(ii) H2O2(OH )
(III) Ozonolysis of alkene :
It is used to get carbonyl compounds from alkene. The reaction is
Ex.
O
CH3
CH–CH C CH 3
O3 3
CH3 Zn–H2O
CH3 – CH = C – CH 3 CH 3– CH = O + C = O + ZnO
O O CH 3
CH3
(CH3)2 S CH3
CH3 – CH = O + C = O + (CH3)2 S = O
CH 3
H2O CH3
CH3 – CH = O + C = O + H2O2
CH 3
H2O2
CH3COOH

CARBONYL COMPOUND
Note :
(I) During the cleavage of ozonide Zn is used to prevent further oxidation of aldehyde into
acid.
(II) By this method we can locate double bond in olefin or exact structure of hydrocarbon
can be determined by knowing ozonolysis product i.e. by placing double bond at the
place of two carbonyl oxygen of two carbonyl compounds.
(IV)Dehydrogenation of Alcohol :
Dehydrogenation means removal of hydrogen and the reagent used is heated copper.
Cu/300ºC
1º alcohol (RCH2OH) Aldehyde (R–CH = O)
–H2O
Cu/300ºC
2º alcohol (R2CHOH) Ketone (R2C = O)
–H2O
Cu/300ºC
3º alcohol Alkene
–H2O
(V) Dry distillation of Calcium salt of acid :

O
(RCOO)2Ca R – C – R + CaCO3
Ketone
(VI) On aqueous alkali hydrolysis of gem-dihalides :
Terminal gemdihalides will give aldehyde while non-terminal will give ketones as follows,
aq. KOH OH
R – CHCl2 R – CH R – CH = O
OH –H2O
Aldehyde
Cl
aq. KOH
R – C – R' R – C – R' R – C – R'
–H2O
OH OH O Ketone
Cl
(VII) Wacker Process :
Alkenes can directly be oxidised to corresponding aldehydes or ketone by treating them
with a solution of PdCl2 containing a catalytic amount of CuCl2 in presence of air or O2.
Except ethene any higher alkene will give ketone.
CuCl2
CH2 = CH2 + H2O + PdCl2 CH3 – CH = O + Pd + 2HCl
air or O2
O
CuCl2
R – CH = CH2 + H2O + PdCl2 R – C – CH3 + Pd + 2HCl
air or O2
Note : During the reaction PdCl2 is reduced to Pd and CuCl2 is reduced to Cu(I)

CARBONYL COMPOUND
(VIII) Preparation of Carbonyl compounds using Grignard’s Reagent :

(a) Hydrogen cyanide on treating with Grignard reagent followed by double decomposition
with water gives aldehyde via imine.
Alkylcyanide by using above process gives ketone via ketimine
(b) Alkyl formate with Grignard reagent gives 2° alcohol via aldehyde, while alkyl alkanoate
under similar condition gives 3° alcohol via ketone
(A) Methods used for the preparation of Aldehydes only.

(i) Rosenmund’s reaction :
Here acid chlorides are reduced to aldehyde with H2 in boiling xylene using palladium
as a catalyst supported on barium sulphate.
O
Pd-BaSO4 O
R – C – Cl + H2 R–C + HCl
Boiling Xylene H
(ii) Stephen’s reduction :
(iii) Oxo-process :
It is also called as formylation, here alkene reacts with water gas at high temperature
and pressure in the presence of cobalt carbonyl catalyst to give aldehyde.

CARBONYL COMPOUND
(iv) Reimer-Tiemann Reaction :

By this method phenolic aldehyde is prepared
(B) Methods used for the preparation of Ketones only.

(i) Using alkanoyl chloride and dialkyl cadmium
O O
R – C – Cl + R'Cd
2 R – C – R' + R' – Cd – Cl
Alkyl cadmium
chloride
O O
2R – C – Cl + R'Cd
2 2R – C – R' + CdCl2
Cadmium
chloride
(ii) By acylation or benzoylation of aromatic hydrocarbon (Friedel-Craft Reaction)
Dry
C6H6 + CH3COCl C6H5COCH3 + HCl
AlCl3
Acetophenone
(iii) By acid hydrolysis followed by heating of -Ketoester.
– Keto acid
Note :
(i) It is -ketoacid which decarboxylate more readily as it proceeds via six membered
cyclic transition state

CARBONYL COMPOUND
Note :
(ii) If two ester units are same then it is intermolecular Claisen ester condensation
Q. Predict the unknown (s) for the following :
Sol.
O
O O O O
C2H5O CH 3–CH 2–C–OC 2H 5
CH3–CH2–C–OC2H5 CH3–CH–C–OC2H5 CH3–CH2–C–CH–C–OC2H5
–C2H5OH
–OC2H5
(A) CH3
H2O/H
H
O O O
CH3–CH2–C–CH2–CH3 + CO2 C C=O
CH 3–CH2 C
(C)
(B) CH3
Note :
(iii) If two ester units are different then it is crossed Claisen ester condensation
O
C2H5ONa
(a) C5H5COOC2H5 + CH3COOC2H5 C5H5 – C – CH2 – COOC2H5
–C2H5OH
O O
C2H5ONa
(b) CH3 – CH2 – COOC2H5 + CH3COOC2H5
–C 2H5OH
CH3 – CH2 – C – CH2 – C – OC2H5
Note :
(iv) If two ester units are present with in the same molecule then we get cyclic  -
ketoester and the reaction is intramolecular Claisen ester condensation.
COOC2H5 O
C2H5ONa
(CH2)4
COOC2 H5 –C2H5OH COOC2H5
Note : Active methylene group hydrogen is too acidic that it can be replaced by alkyl or aryl
halide in the presence of base like sodium ethoxide.
(C) Pinacol-Pinacolone rearrangement :
Pinacol is obtained when 2 moles of acetone are heated with divalent active metal
magnesium followed by treating with water.
O O CH3CH3 CH3 CH3
H2 O
CH3–C–CH3 + CH3–C–CH3 CH3—C—C—CH3 CH3—C—C—CH 3
O O OH OH
Mg Pinacol

CARBONYL COMPOUND
Pinacol undergoes rearrangement in acidic media to give pinacolone

CH3 O
+
H
(CH 3)2C C(CH 3)2 CH3–C C–CH3
–H2O
OH OH CH3
Pinacol Pinacolone
Section B
4. Chemical Reactions of Carbonyl Compounds :
Carbonyl compounds undergo nucleophilic addition reaction and reactivity order will
be :
(I) Nucleophilic Addition Reaction :
H R R
C=O > C=O > C = O (reactivity order)
H H R
(i) Reaction with alcohol :
Carbonyl compounds react with alcohols in the presence of dry HCl gas to give acetal
(if aldehyde) and ketal (if ketone) via formation of unstable hemiacetal and hemiketal
respectively.
R H R R
R'OH
C=O + R'OH C – OH C – OR' + H2O
H dry HCl H
H
OR' OR'
Hemiacetal acetal
Note :
(i) Acetal is formed to protect aldehyde for a long time.
(ii) Acetal has ether as the functional group.
(iii) Acetal formed can be decomposed to original aldehyde by dilute acids.
(iv) On treating with ethylene glycol we get cyclic acetal or ketal (1, 3-dioxolane)
CH2–OH O – CH2
C=O + | C
Para toluene O – CH2
CH2–OH
sulphonic acid (PTS)
Mechanism :
HO – CH2 O – CH2
C=O+ C
–H2O O – CH2
HO – CH2
(v) Acetal formation is found to be more favourable than ketal formation if both the carbonyl
groups are present within the molecule.

CARBONYL COMPOUND
(ii) Addition of HCN :

Base catalysed addition
(iii) Addition of sodium bisulphite (NaHSO3):

This addition is used to isolate carbonyl compounds from the mixture as we get salt.
C = O + NaHSO3 C – ONa C – OH
SO3H SO3Na
(salt)
Salt on acidification gives carbonyl compounds again.
H2O
C – OH C – OH C=O
–H2O
SO3Na OH
(II) Addition elimination reactions :
Certain compounds related to ammonia add to the carbonyl group to form derivatives
that are important chiefly for the characterization and identification of aldehydes and
ketones, the product contain a carbon nitrogen double bond resulting from elimination
of a molecule of water from the initial addition products.
C + :NH2OH H+ –C – NHOH C = NOH + H2 O

+
O OH2 Oxime
C + :NH2NHC6 H5 H+ –C – NHNHC6H6 C = NNHC6H6 + H2O

+
O OH2 Phenylhydrazone
+
C + :NH2NHCONH2 H –C – NHNHCONH2 C = NNHCONH2 + H2O
+
O OH 2 Semicarbazone

CARBONYL COMPOUND
:
(i) Reaction with ammonia derivatives (H2N–Z) :
This reaction is nucleophilic followed by water elimination :
C = O +H2 N–Z C = N–Z

–H2O
:
C = O + H2N–Z C–O C – OH C = N–Z

– –H2O
H–N–H N–H
Z Z
This reaction is carried out in slightly acidic media which will generate a nucleophilic
centre for weak base ammonia derivatives.
:
C = O: + H C=O–H C – OH
On using strong acidic media lone pair of electrons present at N-atom of ammonia
derivatives will accept protonforming protonated ammonia derivatives which cannot
act as nucleophile for carbonyl carbon.
C = O + H2N – Z >C = N – Z
Z
–OH Hydroxylamine Oxime
–NH2 Hydrazine Hydrazone
–NH – C6H6 Phenylhydrazine Phenylhydrazone
–NH NO2 2,4-Dinitrophenylhydrazine 2,4-Dinitrophenylhydrazone

(Brady's reagent) or 2,4-DNP (Solid orange precipitate)
NO2
O
–NH – C – NH2 Semicarbazide Semicarbazone
(III) Beckmann Rearrangement in Oxime :

R' O O
H+ or
C = N – OH R–C–NHR' + R'–C–NHR
dry HCl (if R' is bulkier than R)
R (E + Z)

CARBONYL COMPOUND
Mechanism :
H H
R' R' O OH
:
H H2O: –H
: :
C = N – OH C = N – OH2 R–C=N–R' R–C=N–R' R–C=NR'
–H2O
R R
Tautomerism
O
R – C – NHR'
Note :
(i) Brady’s reagent is used to distinguish carbonyl compounds from the mixture.
(ii) Oxime undergoes Beckmann rearrangement to give its isomer amide.
(iii) In this reaction the group which is anti to –OH group migrates.
C6H5 O
Rearrangement
C = N – OH CH3 – C – NH – C6H5
CH 3
C6H5 O
OH Rearrangement
C=N C6H 5 – C – NH – CH3
CH3
(–CH3 is anti to –OH)
C6H5 O
Rearrangement
C=N CH3 – C – NH – C6H5
OH
CH3
(–C6H5 is anti –OH)
Section C
(IV)Aldol Condensation :
It is condensation between two moles of carbonyl compounds among which at least
one must have two -hydrogen atoms in dilute basic media to get -unsaturated
aldehyde / ketone via the formation of -hydroxy aldehyde / ketone.
Ex. CH3

CARBONYL COMPOUND
Mechanism : CH3 – CH = O 'B' CH2 – CH = O + BH
From -hydroxy aldehyde / ketone, water is eliminated on using either acidic or basic media
as –
:
B (basic media)
CH3–CH–CH2–CH=O CH3–CH–CH–CH=O
–BH
:OH OH
:
(Acidic
media) H –OH
CH3–CH–CH2–CH=O CH3–CH–CH–CH=O CH3–CH=CH–CH=O

–H2O
H –H
OH2
Now try to get carbonyl compounds from -unsaturated carbonyl compounds as –

Keep ‘H’ at -position and –OH at -position of  unsaturated carbonyl compounds to get
-hydroxy carbonyl compounds.
O O
C=C–C–R C–C–C–R
OH H
Now break  and  carbon as shown below to get carbonyl compound.
These two carbonyl compounds can be obtained on ozonolysis of hydrocarbon C = C — CH2

R
if it is asked.
Intramolecular aldol condensation :
O
O O O O O
B– C
:
–OH H –H2O
OH CH
3

CARBONYL COMPOUND
(V) Cannizzaro reaction :

Carbonyl compounds having no -hydrogen atom undergo disproportionation or redox
reaction in strong basic media.
H O
NaOH
(i) 2 H – C = O H – C – ONa + CH3 – OH
(ii) 2 C6H5CH=O NaOH C6H5CO ONa + C6H5CH2OH

Sodium benzoate Benzyl alcohol
(iii)
These reaction are intermolecular cannizzaro reaction :

Mechanism :
Hydration in base deprotonation of
O
(Hydroxide as O O– hydrate –O O–
HO– nucleophile) H
(Hydroxide as base)
R H HO– H H
aldehyde R R
Hydrate anion Hydrate dianion
By this mechanism it is clear that acid is corresponding to that carbonyl compound over
which OH is going easily as nucleophile.
Note : It is observed that hydride ion transfer from (I) to Carbonyl compound (B) is rate
determining step.
Crossed Cannizzaro reaction :
On using two types of carbonyl compounds having no -hydrogen atom, acid will be
corresponding to that aldehyde over which OH will approach without any hindrance.
Example
H
O
OH
(i) H – C = O + C6H5 – CH = O H–C + C6H5CH2OH
O–
(A) (B)
H
O
OH
(ii) (CH2OH)3C – CH = O + H – C = O excess (CH2OH)3C – CH2OH + H – C
(B) O
(A) –
In case (i) OH will easily go to (A) and in case (ii) it will go to (B) hence acid will be formate
ion in both the cases.
(VI)Perkin reaction :
When aromatic aldehyde like benzaldehyde is treated with anhydride in the presence of
sodium salt of acid from which anhydride is derived, we get -unsaturated acid.

CARBONYL COMPOUND
CH = O CH = CH – COOH
e.g. (CH3CO)2O/CH3COONa
Acetic Sodium acetate
anhydride (Act as base)
Benzaldehyde Cinnamic acid
:
Mechanism : CH3COOCOCH3 B
CH2COOCOCH3
–BH
O– O– compare
O O O– OH H
R H + B–
R H R O– R H R H H H O
H H H
Hydride is least bad
Carboxylate anion alcohol R H
leaving group H
(VII) Reformatsky reaction :
When carbonyl compound and -halogenated ester are heated with zinc followed by treating
with water we get -hydroxyester.
This reaction can be represented as –
Br – CH – COOC2H5 Br – Zn – CH – COOC2H5
R R
(VIII) Wittig reaction :

It is used to get alkene from carbonyl compound using phosphorus ylide via the formation
of cyclic structure betaine.
C = O + C – P(Ph)3 C–O C=C + O = P(Ph)3
C – P(Ph) 3 Alkene
Betaine
Note : Phosphorus ylides are prepared from alkyl halide and triphenylphosphine in the
presence of base like sodium ethoxide as –
Base
:
R – CH2 – Br + (C6H5)3P R – CH2 – P(C6H5)3 R –CH–P(Ph)3 or R–CH = P(Ph)3

–Br –BH Phosphorus ylide

CARBONYL COMPOUND
(IX)Baeyer-Villiger oxidation : It is the preparation of ester from ketone using peracid.

R
R"COOOH
C=O R’–C–OR + R"COOH
peracid
R'
O
Mechanism :
(X) Haloform reaction :

Acetaldehyde and methylalkyl ketones react rapidly with halogen (Cl2, Br2 or I2) in the
presence of alkali to give haloform and acid salt.
O O
Br2 /NaOH
R – C – CH3 R – C – ONa + CHBr3 (Bromoform)
O
In this reaction –CH3 of CH3 –C– group is converted into haloform as it contains acidic
hydrogen atom and rest-part of alkyl methyl ketone give acid salt having one less carbon
atom corresponding to alkyl ketone.
(a) Halogenation
(b) Alkaline hydrolysis
O O
Br2
R – C – CH3 R – C – CBr3 (Halogenation)
O O
NaOH
R – C – CBr3 CHBr3 + R – C – ONa (Alkali hydrolysis)
O
Note : This reaction is used to distinguish the presence of CH3 –C– group.

CARBONYL COMPOUND
Section D
(XI)Clemmensen reduction :
Used to get alkane from carbonyl compounds.
Zn – Hg/HCl
C=O CH2
sp2 sp3
Zn Zn
2+
H + 2e 2H
C=O C = O –H C – OH C – OH
2
sp
H Zn Zn2+ + 2e
CH2 CH CH CH – OH2
–H2O
3
sp
(XII) Wolff-Kishner reduction :

(Used to get alkane from carbonyl compounds
NH2 –NH2/KOH
C=O CH2
Using high boiling
solvent (ethylene glycol) 3
sp
2
sp
:
–H2O B
C = O + H 2 N – NH 2 C = N – NH2 C = N – NH C – N = NH
–BH (A)
sp
2
:
BH B BH
CH2 CH CH – N = N CH – N = NH
–N2
:
–B
:
–BH –B
sp
3
(XIII) Addition of Grignard reagent over Carbonyl compound :

It gives alcohol
H2O /H
C=O + R – MgBr C – OMgBr C – OH + MgBr – OH
R R
(XIV) Reduction of Carbonyl Compounds :
(i) Reduction to alcohols

CARBONYL COMPOUND
OH
O O H
C
C Ni/H2 C Ni/H2 H
H H H
e.g. H (Raney nickel) H
(90%)
O OH
(1) NaBH4
CH3CH2CH2CCH3 CH3CH2CH2CHCH3
(2) H, H2O
(ii) Reduction to pinacols
CH3 CH3 CH3 CH3
(i) Mg
CH3 – C + C – CH3 CH3 – C C – CH3
(ii) H2O
O O OH OH
(XV) Reaction with PCl5 :
Carbonyl compounds give geminal dihalides
Cl
>C = O + PCl5 C + POCl3
Cl
(i) CH3CH=O+PCl5 CH3 – CHCl2 + POCl3
(ii)
Other reaction :
NH 3
Hexamethylene
tetraamine(urotropine)
Evaporated
(1) CH2 = O –CH2OCH2OCH2O–
to dryness Paraformaldehyde
(Formaldehyde)
O
Kept at room CH 2 CH 2
tempt. for a
longtime O O
CH2
Trioxane
(metaformaldehyde)
(2)

CARBONYL COMPOUND
(3)
(4)

CARBONYL COMPOUND
(5)
O
C6H5 – C – C6H5
(Benzophenone)
(6) C6H5COCl /AlCl3 COCl2 /AlCl3
excess
Section E
Some important reagents used for identification of aldehyde.
(i) Tollen’s reagent :
It is an ammonical silver nitrate solution, prepared by adding ammonium hydroxide to
AgNO3 solution. During reaction, first Ag2O is formed which is dissolved in ammonium
hydroxide to give Tollen’s reagent.
2AgNO3 + 2NH4OH Ag2O + NH4NO3 + H2O
Ag2O + 4NH4OH 2[Ag(NH3)2]OH + 3H2O
Tollen’s reagent
Tollen’s reagent is a weak oxidising agent, it gives Ag mirror test with aldehyde.
R – CH = O + 2Ag(NH3)2 + 3OH RCOO + 2Ag + 2NH3 + 2H2O
(ii) Fehling’s solution :
It is an alkaline solution of cupric ion complexed with sodium potassium tartrate. Two
solutions are kept by naming Fehling solution (I) (CuSO4 solution) and Fehling solution (II)
(Alkaline solution of sodium potassium tartrate). When these two solutions are mixed we
get deep blue coloured solution.
CuSO4 + 2NaOH Cu(OH)2 + Na2SO4

CARBONYL COMPOUND
Equal volume of both the solution are heated with aldehyde to give red brown precipitate
of cuprous oxide (Cu2O) which confirms the presence of aldehyde.
R – CHO + 2CuO RCOOH + Cu2O (Red precipitate)
Blue
RCHO + 2Cu2+ + 3OH
(iii) Benedict solution :

It is a solution of CuSO4, sodium citrate and sodium carbonate. It also consists of two
solution. Solution (I) is alkaline solution of sodium citrate and solution (II) is CuSO4 solution.
CuSO4 + 2NaOH Cu(OH)2 + Na2SO4
CH2COONa CH2COONa
Cu(OH)2 + HO – C – COONa HO – Cu – O – C – COONa
CH2 – COONa CH2COONa

(Blue colour)
Aldehyde gives positive test with Benedict solution.

(iv) Schiff’s reagent :
It is a dilute solution of rosaniline hydrochloride whose red colour has been discharged by
passing SO2. Aldehyde restores red colour when treated with schiff’s reagent (Magenta
solution in H2SO4).

CARBOXYLIC ACID & IT’S DERIVATIVES
CARBOXYLIC ACID & IT’S

DERIVATIVES
Carboxylic Acid Derivatives
Closely related to the carboxylic acids and to each other are a number of chemical families
known as functional derivatives of carboxylic acids : acid chloride, anhydrides, amide, and
esters. These derivatives are compounds in which the -OH of a carboxyl group has been
replaced by–Cl, –OOCR, –NH2 or –OR
O
O R—C
O
R—C
Cl R—C
O
Acid chloride Anhydride
O O
R—C R—C
NH2 OR
Amide Ester
O
They all contain the acyl group , R—C
Acid Halides
Methods of preparations of Acyl halides
(i) RCOOH + PCl5  RCOCl + POCl3 + HCl
(ii) 3RCOOH + PCl3  3RCOCl + H3PO3
(iii) RCOOH + SOCl2 Pyridine
  RCOCl + SO2 + HCl
Ex. 3CH3COONa+PCl3 
Distillation
 3CH3COCl+ Na3PO3
Acetyl chloride
Distillation
Ex. 2C 6H 5COONa + POCl 3   2C6H5COCl + NaCl + NaPO3
Sodium. benzoate Benzoyl chloride
Chemical reaction
Reaction with carboxylic acids :

Reaction with alcohols :

Acyl chlorides react with alcohols to form esters. The reaction is typically carried out in the
presence of pyridine.
O O
Py
RCCl + R'OH RCOR' + HCl
Acyl Alcohol Ester Hydrogen
chloride chloride
O O
–
RCCl + R2'NH + HO RCNR2' + H2O + Cl–
O O
NaOH
C6H5CCl + HN C6H 5C—N
H2O
Hydrolysis :
O O
RCCl + H2O RCOH + HCl
O O
C6H 5CH2CCl + H2O C6H 5CH2COH + HCl
Reaction of acid halide with organometallic reagent :

(a) With Grignard reagent
O O O
–
OH
|| || R'—MgX H2O
R–C–Cl + R MgX R–C–R R—C—R' R—C—R'
R' R'
(b) Reaction with Gilman reagent
O O
R—C—Cl + R2'CuLi R—C—R'
Reduction of acid halide
(a) Reduction with LiAlH4
O
R—C—Cl + LiAlH 4 R—CH2—OH

(b) Reduction with H2/Pd/BaSO4 (Rosenmund reduction)
O O
H2/Pd/BaSO4
R—C—Cl R—C—H

H2O RCOOH + HCl (Hydrolysis)

R'OH RCOOR' + HCl (Alcoholysis)
2NH3
RCONH2 + NH4Cl (Ammonolysis)
2R'NH2 + –
RCONHR' + R'NH 3 Cl
RCOOH/Pyridine
(RCO)2O + HCl
O RCOONa
(RCO)2O + NaCl
C6H 6/Anhyd. AlCl3
R—C—Cl C6H5COR + HCl (Friedel-Crafts reaction)
Acid chloride H2/Pd-BaSO4 RCHO + HCl (Rosenmund's reduction)
+S or quinoline
R2' Cd/Ether
2RCOR'+CdCl2
LiAlH4 / Ether
RCH2OH
KCN H+/H2O
R—CO—CN R—CO—COOH+NH3
Acid Amides
Methods of preparation of acid amides
1. By reaction of esters with ammonia and amines :
Ammonia is more nucleophilic than water, making it possible to carry out this reaction
using aqueous ammonia.
Ex.
2. From acid halides :

RCOCl + 2NH3  RCONH2 + NH4Cl
3. From anhydride :
(RCO)2O + 2NH3  RCONH2 + RCOONH4
4. From ammonium salt of carboxylic acid :
RCOONH4  
 RCONH2 + H2O
CH3COONH4   CH3CONH2

5. From cyanides :
 
R – C  N + H2O or   R – CONH
Conc. HCl
H O  NaOH
2 2 2
CH3C  N + H2O Conc

  CH3 - CONH2
. H 2SO 4
6.

Chemical reactions
Hoffmann rearrangement
General reaction :
O
R—C—NH2 + NaOH + Br2
hydrolysis
R—N=C=O R – NH 2
Hydrolysis of amides :
+
In acid, however, the amine is protonated, giving an ammonium ion, R2NH2
Summary of reaction of amide:
+
H /H2O +
RCOOH + NH4
NaOH
RCOONa + NH3
Conc. HCl
RCONH2HCl
2Na
O
RCONHNa + ½ H2
R – C – NH2 2 5
3RC N +2H3PO4
Acid amide
SOCl2
RC N + SO2 + HCl
HONO
RCOOH + N2+ H2O
Br2+ 4KOH
RNH2 + K2CO3 + 2KBr + 2H2O (Hoffmann
LiAlH4 /dry ether bromamide reaction)
RCH2NH2
1º Amine
Esters
Methods of Preparation
(i) CH3COOH + C2H5OH  CH3COOC2H5 + H2O

H
Acetic acid

C6H5COOH+CH3OH 
H
C6H5COOCH3 + H2O

(ii) CH3COCl+C2H5OH Pyridine

  CH3COOC2H5+ HCl
Alcohols react with acyl chlorides by nucleophilic acyl substitution to yield esters. These
reactions are typically performed in the presence of a weak base such as pyridine.
o o
RCCl + R'OH + RCOR' + Cl–
+
N N
H H
SUMMARY OF REACTION OF ESTERS

H /H2O
+
RCOOH+R'OH(Hydrolysis)
NaOH/H2O
RCOONa + R'OH(Saponification)
NH 3
RCONH2 + R'OH(Ammonolysis)
O
R''NH2
RCONHR'' + R'OH
R —C—OR'
R''OH/H or R'' ONa
+
Ester RCOOR" + R'OH(Trans-esterification)
H2/Copper chromite
RCH2OH + R'OH
or LiAlH 4
Na/alcohol
RCH2OH + R'OH(Bouveault-Blanc reduction)
R"
(1) 2R''MgX
R—C—OH (In case of esters of formic acid.
(ii) H /H2O
+
2° alcohols are obtained)
R"
3° alcohol
Acid anhydrides
Methods of preparation of acid anhydrides
1. From carboxylic acids :
Ex. CH3COOH + HOOCCH3 P  CH3COOCOCH3 + H2O
2O5 ,
Acetic acid Acetic anhydride

O
C
CH2—COOH CH2
O
Ex. CH2—COOH —H2O CH2
C
O
O
CH2—COOH
O
Ex. CH2 —H2O
CH2—COOH
O

2. From acid and acid halide :

Ex. CH3COOH+CH3COCl Pyridine
  CH3COOCOCH3 + HCl
Ex. CH3COCl + CH3COONa 
 CH3CO.O.COCH3 + NaCl
Chemical reactions
1. Reaction with aromatic compounds (Friedel crafts acylation)
2. Reaction with alcohols :

O O O O
Ex. RCOR' + RCOH
RCOCR + R'OH
3. Reaction with ammonia and amines :
4. Hydrolysis :
Acid anhydrides react with water to yield two carboxylic acids. Cycylic anhydrides yield
dicarboxylic acids.
O O O O
RCOCR' + H2O RCOH + R'—C—O—H
O
O
COH
O + H 2O
COH
O
O
5. Heating Effects :
(a) Heating effect on monocarboxylic acid
O O
2R—COOH R—C—O—C—R
—H2O
(b) Heating effect on dicarboxylic acid

COOH
—CO2
CH2 CH3—COOH
COOH

(c) Heating effect on Hydroxy acids

O
O
O
1.   Hydroxy acid CH 2—CH2—CH2—CH 2—C—OH
—H2O
OH
O
O
O
CH2—CH2—CH2—C—OH
2.   Hydroxy acid —H2O
OH
O O
3.   Hydroxy acid CH2—CH 2—C—OH CH2=CH—C—OH

—H2O
OH
Since 4 or 8 membered rings are less stable therefore -Hydroxy acids on heating
produce ,  unsaturated carboxylic acid.
O O
O
OH
HO OH –2H2O
4. -Hydroxy acid HO O
O
O
 Heating effect on esters
O
R—C—O—CH2—CH2—R R'—COOH to R' — CH = CH 2
O R
CH2 C
Mechanism : R'—CH=CH2+R—COOH
CH O
R' H
This reaction follows syn elimination & Hoffmann product is formed.

4 June 2022 Chemistry

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ALKYL HALIDE

Classification of alkyl halides :

Haloalkanes can be classified into following three categories.

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IUPAC nomenclature of alkyl halides

2. CH 3 – CH – CH2 – CH2 3-Bromo-1-chlorobutane

3. CH2 – CH – CH – CH2 2-Bromo-1-chloro-4-fluoro-3-methylbutane

4. CH3 – CH – CH2 – CH2 – CH2 5-Chloropentan-2-ol

CH3 – CH – CH2 – Cl 1-Chloro-2-methylpropane

2. CH3 – CH2 – CH2 – CH 2 – CH2 – Cl 1-Chloropentane

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(b) Position 1. CH3 – CH2 – CH2 – Cl 1-Chloropropane

2. CH3 – CH – CH2– Cl 1-Chloro-2-methylpropane

` (a) Optical isomerism

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Bonding in alkyl halide

Bond Bond length(Å)

Physical properties of alkyl halide

Table : 2 Molecular dipole moments of methylhalides

Cl 1.94 D 1.60 D 1.03 D 0

Br 1.79 D 1.45 D 1.02 D 0

I 1.64 D 1.11 D 1.00 D 0

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Table : 3 Boiling points of some alkyl halide in °C (1 atm)

Formula X=F X = Cl X = Br X=I

CH3– CH2– CH2X –3 47 71 103

CH3– (CH2)3– CH2X 65 108 129 157

CH3– (CH2)4– CH2X 92 134 155 180

Preparation of alkyl halide :

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Chemical reactions of alkyl halide

(A) Bimolecular nucleophilic substitution reaction (SN2)

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Table : 6 Relative rates of reactions of alkyl halide in SN2 reaction.

Neopentyl (CH 3)3CCH 2X 0.00001

Strong nucleophiles (CH 3CH2)3P Moderate nucleophile : Br

(CH3– CH2) 2NH Cl

(CH3– CH2) 3N Weak nucleophile F

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Steric effects on nucleophilicity

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Strongly basic ions rarely act as leaving group 

Nu + CH3 – CH3 CH3 – Nu + CH3 (CH3 is a strong base)

R – X + R' – COO – R – COO – R Ester

[R – PPh3]+X– Phosphonium salt

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(B) Unimolecular nucleophilic substitution reaction (SN1) :

Step - 2 Nucleophilic attack on the carbocation (fast)

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(iii) Effect of the solvent the ionizing ability of the solvent:

Solvent  Relative rate

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Mechanism of racemization (SN1) 

Comparison of SN1 and SN2 reactions

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Some Nucleophilic reaction of R – X :–

Williamson's Ether Synthesis: (SN2)

4. PhONa + MeCl PhOMe + NaCl

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Note : (1) In SNi retention of configuration takes place.