222 Organic Chemistry

van der Waals

repulsions

H,C CH HC H
EXPLORE MORE S
... through solved
problem41
H H
H
CH
cis (Less stable) trans (More stable)

6.3.2 Electrophilic Addition Reactions

The carbon-carbon double bond in alkenes consists of a strong bond (by overlap of
hybridized orbital on each carbon) and a weak bond (by the overlap of pure p orbital on ea
carbon). Because of this unsaturation, alkenes undergo addition reactions, which involves breakine
of a weak r bond and formation of two new a bonds. During addition reactions, the doublebon
provides the loosely held r electrons (thus, behaving as an electron rich centre) and is readiy
attacked by electron deficient species (electrophiles).
For this reason the reactions are termed electrophilic addition reactions. In the additi
reactions of alkenes the electrophilic and nucleophilic part of reagent may add across the doubie
bond from opposite sides and in such case the addition is known as anti or trans addition. The
addition of reagent may occur from the same side of the double bond and in such case the aditin
in known as
syn or cis addition.

NOTABILIA 7
TERMINOLOGY
TERMS WE COME ACROSS FREQUENTLY
Regioselective reaction [Latin; regionem meaning direction] Reactions in which more
site
than
only,
one site of attack is possible but through preferential
occur a attack at one of the
to produce predominantly, of the isomeric
one product (constitutional isomer
Stereospecific reaction: Reactionsin which a particular stereoisomer of the nu
the
the formation of a specific stereoisomeric
reactant results in product. In other words.
stereochemistry of initial reactant governs the stereochemistry of the product.
Stereoselective reaction: The reactions which only stereoisomer or
product

is formed
in one t than one
preferentially, although there is a
possibility of formation of
Ion o
more

stereoisomer.
of
Syn- addition and Anti- addition: These terms are used to indicate
whether
addition

a
group has occurred to the same the opposit
syn-) o r to
side of the double bond (syn o r trans
of the double bond (anti-). At times, these terms are also referred to as co-
(for anti-) addition.

A-B B c=c A-B

B AB
anti- addition Syn-addition

(cis- addition)
(trans-addition)
 Alkenes 223

Addition of halogens-formation of vicinal dihaloal kanes

Alkenes react readily with chlorine or bromine, in dark, in a solvent such as CCl, to produce
vicinal-dihaloalkanes as the addition products. Iodine, generally, does not react with alkenes.

CH,-CH, + Br CCla CH,CH,Br

Br
Ethene 1,2-dibromoethane

CH,CH- CH, + Cl CCla

dark CH,CHCH,
CI
Propene 1,2-dichloropropane
Br

CH,CH,CH=CH, + Br CCla EXPLORE MORE

dark CH,CH,CHCH, SETAI
.. through solved
Br problem 42

But-1-ene 1,2-dibromobutane

The general mechanism for the electrophilic addition of bromine to alkene is as follows:
Step 1. Addition of bromine to alkene (Formation of carbocation)
The bromine molecule is non polar in nature. However, as the t electrons of alkene approach
the bromine molecule, the bromine becomes polarized. The addition of Br* to alkene occurs in the
first step that results in the formation of carbocation. The carbocation exists in the form of a cyclic
intermediate and is known as bromonium ion.

+ Br-Br
-Br
Alkene Br
(7T electron rich) Carbocation Bromonium ion
Electrophile
Step 2. Attack of bromide ion on carbocation (formation of 1,2-dibromoalkane)
The addition of bromide ion to the cyclic carbocation takes place from the opposite side. Thus,
ne
addition of bromine occurs in an trans- (or anti-) manner as follows:

Br
Br
Br
Proof for electrophilic addition mechanism:
Ve
mechanism is further supported by the fact that the reaction of bromine with ethene in
 224 Organic Chemistry
as 1,2-dibrome
products identified as 1,2-dibromoethane
the formation of two
presence of sodium chloride results in
and 1-bromo-2-chloroethane.

Br2 1,2-Dibromoethane

CH,=CH Br. NaCl 1-Bromo-2-chloroethane + 1,2-dibromoethane

(Br*) attacks fins

the electrophile
The formation of
1-bromo-2-chloroethane is possible only when
negatively
with the charged species (Br from
to form a carbocation intermediate
which further reacts
to form 1,2-dibromoethane
and 1-bromo-2-chloroethane
bromine and CI from sodium chloride)

respectively.
Br

CH,=CH, + Br-Br
-Br
H,C-CH
Bromonium ion

Br
Br
CH-CH
Br Br
1,2-dibromoethane
H.C-CH EXPLORE MORE
S
Br . through solved

CI CH-CH,
problem 45
(from NaC)

Cl
1-bromo-2-chloroethane

What if it would have been a nucleophilic addition reaction? )wouldhave

In a nucleophilic mechanism, the nucleophilic part of the reagent (Br from bromine) wmine
attacked first to form a carbanion intermediate followed by the attack of electrophile (Br roNaCl
N of
Only one product would have been obtained, i.e. 1,2-dibromopropane even in the presci

CI
(from NaC)
No product
(as Cl attack carbanion)
CH,=CH
cannot
CH,CH
Br-Br Br Br
CH,CHCH,Br
(from bromine)
Carbanion
Br
possibie
(Onily dibromo product
i o n u

An aqueous solution can formon add

of sodium chloride is inert towards ethene. Sodiun
bond but it form (from NaC) can
cannot covalent bond with carbon. A chloride ion (from a a n o l e f i n i ccarte

to a
positively charged species like a carbocation but
cannot react directly wi
CH,=CH, + NaCl No reaction
 Alkenes 225

trans- addition of reagent

Prooffor
the stereochemical aspects of addition in alkenes]
Evidence for
open chain alkenes the intermediate carbocation is said to existin cyclic form (as cyclic
n i u of
In
case
m jon). The rigidity of cyclic structure prevents the attack of nucleophilic part of reagent
of the electrophile.
side as that
from the same for the trans- addition (stereochemical aspects) to the alkenes in the
The direct proof
ctronhilic addition
reactions can be easily studied by the addition reactions in cycloalkenes. For
ddition
example, the addi bromine to cyclopentene results in the formation
of
only. This indicates that addition of
of
trans-1,2-dibromocyclopentane EXPLORE MORE
occur in one step from the side of alkene. In fact, the
same
hromine does not of the reagent adds
addition occurs in two steps, first the electrophilic part .. through solved
followed by the attack of problems 43,44
(as cyclic intermediate)
togive a carbocation sidee to give trans- addition product.
nucleophilicpart from
the opposite

Br
Br
H H trans addition
H

H BrB Br Br
Back side attack trans-1,2-Dibromocyclopentane
Br (nucleophile) of nucleophile
can not attack Br
from the same Br
side due to steric H
hindrance cis addition

H
cis-1,2-Dibromocyclopentane

Addition of hydrogen halides

Regioselectivity and Markovnikov' Rule]
Cl, Br, D results in the formation
he reaction alkenes with hydrogen halides (HX, where X
=
of
a solvent such acetic acid or by
O Coresponding haloalkanes. The reaction is carried out in
as

passing dry gaseous HX directly over an al kene.

dry
-C=c + HX

H
Alkene X= CI, Br, I Haloalkane

As an example,

CH,=CH, + HCI CH,CH,C

Ethene Chloroethane
226 Organic Chemistry

In case of unsymmetrical alkene like propene, reaction with i I may

an result in the
formation
two products, namely 1-chloropropane or 2-chloropropane. However, it is
2-chloropropane
is produced selectively hich
Markovnikov's rule: The addition of polar reagents like HX to
unsymmetrical alkenes foll
Markovnikov's rule, which states that the negative part of the addendum (polar reagent) add
that carbon of double bond which has minimum number to
of hydrogen(s).

CH,CH=CH, +HCI CH,CH,CH,CI or

CH,CHCH
CI EXPLORE MORE
SET D
1-Chloropropane 2-Chloropropane .. through solved
(minor) (major) problems 46-51
The addition of HX to an
unsymmetrical alkene is a
regioselective reaction.
Explanation to Markovnikov's rule: A modern approach
Consider the mechanism of addition of
HCI to
of the olefinic carbons propene. The attack of the electrophile H
may result in the formation of 1° or a on either
of a
electrophile H is always favoured in a direction which 2 carbocation. In general, the attack
carbocation. In propene, results in the formation of
stable 20 carbocation. 2-chloropropane forms predominantly
more stable
through the formation of a more

ACI CH,CHCH CL CHCHCH, Reaction ot

2° carbocation alkenes with
CH,H=CH, +H (more stable) CI HBr in
Favoured) presence of a
peroxide
results in Anti
AtC Markovnikovw's
CH,CH.CH, C CH,CHCH addition. This
is discussed later
1 carbocation in this chapter
(less stable)
CI I n sec. 6.3.3.
(Not favoured)

Redefining the
In the addition reactions of Markovnikov's Rule
that carbon of the unsymmetrical alkenes, the attack of electrophile on
double bond which occus
carbocation. results in the fomation of a more Stable

This redefined version of

explains a number of Markovnikov's rule, based on the stabiliry of cu ocation,
electrophilic addition reactions
which was not
possible with the earlier definition. in unsymmetrical aalkenes
et The carbocation fornmed
during electrophilic addition may be hrough

Wagner-Meerwein rearrangement stabilized rut in the

involving 1.2-hvdride or 1,2-methyl sh
carbocation. Besides, the nature of substituent also affecis
the stability ot ca
 Alkenes 227

in alkenes based the of carbocations is discussed as follows:

The electrophilic addition on stability
Case StudyI (Stability of carbocation involving 1,2-hydride shift)
3-methylbut-1-ene with HCI
Reaction of
the major product obtained is 2-chloro-2-methylbutane rather than the expected
In this reaction,
2-chloro-3-methylbutane.

CH CH CH
CH,CHCH=CH,+ HCI CH,CCHCH,+CH,CHCHCH,
CI CI
2-Chloro-3-methylbutane
2-Chloro-2-methylbutane
(minor)
(major)
carbocation formed
be the basis of carbocation rearrangement. The 2°
explained on
This reaction can
carbocation. This 3
1,2-hydride shift to give a more stable 3°
as an
intermediate undergoes a 2-chlorO-2-
as an intermediate.on reaction with Cl
results in the formation of
formed
carbocation
methylbutane as the major product.

CH3 CH CH
CH
1,2-hydride shift CH,CCHCH, CH,CCH,CH
CH,CCH=CH, CH,C-CHCH,
H Cl
H H
3° carbocation
2° carbocation
(more stable)

are known as Wagner-Meerwein

The reactions proceeding through carbocation rearrangement
rearrangement reactions (p. 216).
carbocation involving 1,2-methyl shift)
Case Study II (Stability of
HCI
Reaction of 3,3-dimethylbut-1-ene with
of 2-chloro-2,3-dimethylbutane as the major product
The reaction involves the formation
Instead of expected 3-chloro-2,2-dimethylbutane.

CH CH3 CH
CH,CCH=CH, HCI CH,CCHCH CH,C-CHCH
CI CH CH, CI
CH 2-Chloro-2,3-dimethylbutane 3-Chloro-2,2-dimethylbutane
3,3-Dimethylbut-1-ene (major) (minor)

formed which rearranges through 1,2-methyl shift to give m o r e

In this reaction, 2° carbocation is
stable 3 carbocation. Thus, 2-chloro-2,3-dimethylbutane
is
obtained as a result of addition of
Cto a more stable 3° carbocation.

CH CH CH
CH 1,2-methyl shift
CH,CCH=CH,H CH,-CHCH CH,C-CHCH CH,C-CHCH,
CH CH CH, CI CH
3 carbocation (more stable)
2 carbocation 3-Chloro-2,3-dimethy lbutane
(major)
 228 Organic Chemistry
Case Study Ill (Effect of electron-withdrawing group on stability of carbocation)

Reaction of propenenitrile with HC

2-chloropropanenitrile the product obtained is
In this reaction, instead of expected
3-chloropropanenitrile. C-ve)
v e

twe
haue
fo
C-CH,CH,CN
iechar CH,=CH>CN+ HCI
3-Chloropropanenitrile

CH-CH-CN
CI
2-Chloropropanenitrile

formation of a 1° or 2° carbocation. However,

The addition of electrophile (H) may result in the
carbocation. This is due to the presence
o
than 1°
the 2° carbocation is unexpectedly less stable carbon bearing
electron withdrawing (H effect)-CN group. The CN group directly attached to
of 2° carbocation) destablizes it
charge. Thus,
by intensifying the positive
positive charge (in case
attack of C occurs at relatively stable 1° carbocation.

CH-CH-CN Noreaction
2 carbocation
electron withdrawing
CH=CH-CN+H -CN group destabilizes the carbocation

CH-CH-CN CH-CH,-CN
1 carbocation dCl

Addition of sulfuric acid of

The alkene, when passed through cold, concentrated sulphuric acid results in the forma
elective

The addition is regiose

alkylhydrogensulfate (ester of sulfuric acid) as the addition product. ter,

and follows Markovnikov's rule. The alkylhydrogensulphate, on hydrolysis (heating wiu

forms alcohol as the final product.

H,O/A CH,CH,OH
H,C=CH+H,SO CH,CH,OSO0,H
Ethanol
Ethene Ethylhydrogensulfate

CH,CH,CHCH, H,O/A CH,CH,CHCH

CH,CHCH=CH, + H,SO,
But-f-ene OH
OSO,H Butan-2-ol
Butyl-2-hydrogensulfate
 L i n jt abio
Alkenes 229

cannot be used for the preparation of alcohols, except in case of reaction with
This method
ethanol. Further, during the reaction the carbocation rearrangement may occur
ethene, which yields
shift and 1,2-methyl shift.
through 1,2-hydride

Addition of water (Formation of alcohol)

addition
of water with alkenes results in the formation of alcohol. The
The acid catalyzed reaction
follows Markovnikov's rule.

General reaction

10% H,SO4 RCH-CH3

RCH=CH, + H,O

OH

Mechanism

HOH RCH-CH RCH-CH

RCH-CH, HRCH-CH OH
Carbocation
Alkene Alcohol

For example,

CH,CH,CH=CH, + H,O H CH,CH,CHCH,

OH
Butan-2-ol

CH
CH
CH,C=CH, + H,O CH,CCH
OH
2-Methylpropan-2-ol
2-Methylpropene
carbocation
this method. Further,
ethanol) cannot be prepared by where
nary alcohols (except for preparation of lower alcohols
method is used industrially
the ent may occur. This
ere is no possibility of cabocation rearrangement.

(halohydrins))
ddition of halogen and water (Formation of
haloalcohols
of
in the formation
an alkene with bromine or chlorine
dissolved in water results
brome addition of hypohalous acid
The actual mechanism does not involve the electrOpiie
y itoteoroalcohols. water where
an

1s reaction
the of halogen followed by that of In all,
t
1s
(Br or C+
and nucleophilic part (HO) is provided by water
the additi provided by halogen as HO X".
The electropu

addition c O elements of hypohalous acid, though separately,

addition follows
Markovnikov's rule.
232 Organic Chemistry

Hydroboration-Oxidation (Formation of alcohol)

results in the formation of alkylborane that on oxidat
The hydroboration of alkenes using borane Borane (B,H) is a dimer of bo
idation
medium produces alcohol. Doron
with hydrogen peroxide in alkaline
as boronyhydride. In boronhvdrid
however in reactions we represent the reagent ide,
hydride (BH;), and nucleophilic part 15 hydrogen (as hydride
deficient)
the electrophilic part is boron (electron and thus hydroboration is
from the same side of the alkenes
H). The addition of borane occurs
the reagent BH, furnished three hydride ions, reacts with
it
syn-addition (or cis-addition). Since, For example,
three molecules of alkene to form trialkylborane.

Hydroboration:

BH3 CH,CH-CH CH,CH,CH,-BH,

CH,CH=CH
CH,CH=CH,
HBH
Four membered transition
state depicting addition of
reagent from the same
side
of alkene (syn- or cis-addition)

(CH,CH,CH,),BH CHCHC, (CH,CH,CH,),B o oe

Tripropylborane

Oxidation:
H,O, OH
3CH,CH,CH,OH + H,BO,
(CH,CH,CH,),B
Propan-1-ol

Similarly,

(1) BH3
(2) H,O. OH
3CH,CHCH=CH, 3CH,CH,CH,CH,OH
But-1-ene Butan-1-olomammen s n
Hydroboration
(1) BH3 is regioselecetive

(2) H,O, OH (addition tollows

3CH,CH=CHCH, 3CH,CH,CHCH, Markovnikov's

OH 0 nule). The boron

attacks at the
Butan-2-ol least hindered

olefinic carbon

1) BH3
(2) H,O, OH
3CH,CH-C=CH 3CH,CH,-CHCH,OH
CH CH
2-Methylbut-1-ene 2-Methylbutan-1-ol
o ft h ep r o d u c t

The hydroboration-oxidation reaction is carried out readily and results in high yields of u
 Alkenes 233

fobixogs to nolfemo) bios poog to nolibbA

as
The overall hydroboration-oxidation reaction can be depicted
occurs in an ant
hydration of alkene where addition of water to alkene
Markovnikov's manner to yield alcohol as the product. The hydroboration-oxidationusual
cannot be prepared by
of alkene is thus used in the preparation of alcohols that
alkenes where addition of water occurs in accordance with
hydration of
Markovnikov's rule.

Methods
Alcohol from Alkene: A Comparison of Preparative
formation of alcohol.
The of water to an alkene results in the
addition alcohol from
used for the preparation of
REVISITING The different methods, which are
THE KEY
POINTS alkene, are as follows:
acidic medium:
1. Hydration of alkene in
in presence of acid and
The addition of water to alkene
occurs

formation of alcohol in accordance with

results in the
Markovnikov's rule.
formation of alkyl carbocation
. The reaction proeedes through the
rearrangement.
involves carbocation
intermediate and

Yield of the product

formed is poor
2. Oxymecuration-demercuration process:
with
the addition of water in accordance
It also involves
Markovnikov's rule.
mercurinium ion intermediate and
The reaction proceeds through
carbocation rearrangement.
does not involve
occurs readily and good yields of alcohols are

The reaction
r auoelon owlanoibe
snols to
obtained. Td dt olduol
3. Hydroboration-oxidation process:

cis-addition (addition from same side) of borane as

It involves the
per Markovnikov's rule.
through a four membered transition state
The reaction proceeds
involve carbocation rearrangement.
and does not
oft hydration of alkene depicts the addition of
The overall process
s manner to give alcohol.
water in anti-markovnikov
reaction gives very good yields of alcohol
The
 Reaction
6.3.3 Free Radical Addition
(Peroxide Effect)
Addition of hydrogen bromide
results in the formation of
in the presence of peroxide,
The reaction of HBr with an alkene
anti to Markovnikov's rule. For example,
reaction of
occurs
of HBr
bromoalkane where addition an anti-Markovnikov' s addition product, in the presence
HBr with propene gives 1-bromopropane,
of peroxides.
leoibs
(oldae oond
238 Organic Chemistry

Noperoxide CH,CHCH3 [Markovnikov's

addition]
Br
2-Bromopropane
CH,CH=CHHBr

Peroxide CH,CH,CH, [Anti-Markovnikov's

ICH,COO addition]
Br
1-Bromopropane

of peroxide is also known as Peroxide Effect or

The anti-Markovnikov's addition in the presence
Kharasch Effect.
radical addition whereas in absence
Note: The addition of HBr in the presence of peroxide is a free
the usual electrophilic addition of
HBr takes place.
of peroxide,
Free radical addition mechanism single bond
Peroxides are very good free radical generators.
In peroxides, the oxygen-oxygen

radicals. Thus, above mentioned reaction proceeds

undergoes homolytic cleavage
to produce
through the following steps:
Step 1. Generation of free radicals.

cHC-0-¢-CH, 2CH,C-ó -2C0 2cHs

2H,
O Phenyl radical
Benzoylperoxide
H from
abstracts
The CHs
Step 2. of bromine free radical.
Generation HBr to form CH, as this is an

is thus
to form CH6. This results
in reaction and
The CHs abstracts H' from HBr
exothermic
energetically favoured.
radical (Br from
the generation of bromine abstraction
of Br
The
the CHs
to tom
HBr by e n e r g e t i c a l l y

CH, + Br is
H, +HBr CH,Br
unfavourable (endothermie).

olefinic carbon.
Step 3. Addition of bromine radical to

CH,CHCH
Br
s f nobibb 1 radical
no
ol l
CH,CH=CH, +Br poTby
lo

o9) obimond
CH,HCH
Br
2 radical
(more stable)
 stable fre
r e stable
Here, a more free radical (2°) is Alkenes 239
1-Bromopropane. preferentially formed which further
reacts with
HBr to form
CH,CHCH, + HBr
Br
CH,CH,CH, +Br
Br

ThePeroxide Effect is Observed

HCI, or HI. Why? Only in Case of HBr and Not with
The order of HE
bond
HF and HCI have strength of halogen acids is HF > HCI> HBr>HI.
high bond strength and
not occur
easily. In HBr and HI, polarity, so homolytic cleavage does
bromine and iodine free radicals. homolytic cleavage occurs readily to
However, iodine radical undergoes produce
with another iodine coupling reaction
radical to produce iodine.

As a result iodine
radicals are not available for addition on alkene.
Can
provide bromine free radical which is formed Thus, only HBr
to olefinic carbon. easily and is for available addition
 17.3.2 Nucleophilic Addition Reactions
The carbonyl compounds undergo addition of carbon, oxygen, sulfur, and nitrogen nucleophiles.
In general, the reaction follows two types of mechanisms.
Mechanism 1. Addition of strong nucleophiles
The addition of strong nucleophiles (like CN) occurs in neutral or alkaline medium. The general
mechanism of this reaction is depicted here.

General mechanism

Nu
-o C=OHI
bong nhbdor Nu lobyd Nu
sp2 od

the
n general reactionof carbon nucleophiles with carbonyl compounds follow this mechanism. For
ekample, reaction of HCN, witting reaction, Reformatsky reaction and reaction of organometallic
compounds.
Mechanism 2. Addition of weak
nucleophiles
ourong acids catalyze the addition of weak nucleophiles to carbonyl compounds. In presence of acid,
protonation of carbonyl oxygen occurs which increases the electrophilicity of carbonyl carbon.
nCrefore, addition of weak nucleophile occurs readily at carbonyl carbon as shown
general mechanism that through the
follows:
582 Organic Chemistry

General mechanism:

Nu
C=o c=oH -OH OH
Nu
mechanism is followed in reaction of water, alcohol, thiols, percarboxvlic
In general this
acid.
ammonia derivatives with carbonyl compounds. and

With carbon nucleophiles

)Reaction with HCN. The carbonyl compounds react with
hydrogen cyanide to
cyanohydrin, an addition product. form

CN
CH--H HCN CH-C-H
OH
Ethanal
2-Hydroxypropanenitrile
CN
CH,CCH +HCN CH,CCH,0oionM

O OH
Propanone
Mechanism. The carbon nucleophile (CN), which is a strong nucleophile, first attacks the
carbonyl carbon followed by addition of proton to form
cyanohydrin.
CN CN
CH,-C=O CN CH-C-0 CH-C-OH
H H H
ne advantage of this method is that hydrolysis of cyanohydrin produces carboxyne aacid. This
reaction is
frequently used in the synthesis of a-hydroxycarboxylic acids.

woll H,O
o ot CH,CHCN CH,CHCOOH
OH OH
2-Hydroxypropanoic acid
(Lactic acid)

on of
Wittig reaction. The Wittig reaction is used for the synthesis of alkenes tion of
compounds with ylides. Phosphorous ylide is prepared
pnosphorous
pcnyiphosphine with haloalkane (methyl, 1° or 2°). This reaction resu
 Aliphatic Carbonyl Compounds (Alkanals and Alkanones)583

onitum salt which on treatment with strong base (such as PhLi, BuLi, NaOC,Hs) undergoes
pnnation to form the phosphorous ylide. The reaction of phosphorous ylide with carbonyl
deprotona
rmation of betaine, which undergoes elimination to produce an alkene. The
form
results in the
this reaction involves the following steps:
hesis of alkene (for example, propene) through
group

Preparation of phosphorous ylide

Sep 1.

Ph,P-CH,Br BULPhP-CH, + BuHLiBr

PhP:+CH,Br

Ph,P-CH Ph,P=CH
[Resonance stabilization of ylide]

positive and
is a resonance hybrid of two structures and the structure with
Phosphorous ylide structure.
negative charge on adjacent atoms is the major contributing

Step 2. Reaction of phosphorous ylide with carbonyl compounds

H noitmo faH
CHC-CH, Fast CH,C-CH,
CH,C CH,PPh
0 PPh3 0PPh
Betaine Oxaphosphetane

Ph,P=0
CH,CH=CH Triphenylphosphine oxide
Propene
in the position of double
ne Tormation of alkene is regiospecific, that is, there is no ambiguity
be prepared using suitable
ond. In a similar manner, a number of phosphorous ylides may
result in the formation
dalkane. The phosphorous ylides on reaction with carbonyl compounds,
of different alkenes. For example,

CH,CH,C0 + Ph,P-CH, CH,CH,CH=CH, +Ph,P=O

But-1-ene

Propanal
CH,CH=CHCH, Ph,P=0
CH,C-O+ Ph,P-CHCH,
But-2-ene
H
abooiEthanal CH,C=CHCH,+Ph,P=O
CH,C=O + Ph,P-CHCH,
CH o CH,
2-Methylbut-2-ene
Propanone
ECHCH,CH, +Ph,P=0
F0+Ph,P-CHCHCH,
Cyclohexanone Propenylcyclohexane

CHCH.C=0+Ph,P-CHCHCH,
+P CH,CH,C=CHCH=CH, + Ph,P=0

CH CH,
Butanone 4-Methylhexa-1,3-diene
 Aliphatic Carbonyl Compounds (Alkanals and Alkanones)

G Reaction with ammonia derivatives. Derivatives of ammonia react with carbonyl compounds
in acidic medium to give addition products, which undergo elimination of water molecule give
to

as imine derivatives:
the final product
General reaction

c-0H,N-Z H c=N-Z+ H,O

For various
ammonia derivatives HO

Z= alkyl,-OH, NH,-NHCONH,,-NH- O. NH- -NO

NO
General mechanism:
HN-Z -Z
c=o OH
OH H

H C-N-ZHO
-H,o
=N
OH
Addition product

The reaction of carbonyl compounds with

general form crystalline solid products,
ammonia derivatives in

which have sharp melting points and are used for identification of
aldehydes and ketones. A few
with ammonia derivatives are as follows:
1lustrative examples showing reactions of carbonyl compounds
the addition
Amines are good nucleophiles and
(a) With 1° amines (formation of Schiff"'s base). elimination
with amines, further undergoes
product formed by the reaction of carbonyl compounds The reaction is catalyzed
imines also known as Schif's bases.
o water in acidic medium to produce this reaction with carbonyl compounds
does
y mild acidic conditions. In highly acidic medium,
not occur due to protonation of amine (RNH, + H" RNH3).

CH.C=O + HNCH,CH, H CH,CH-NCH,CH, + H,O

Imine
H (a schiff base)

CH,C=O + H,NCH CH,C=NCH,+ H,0

CH
CH Imine
(a schift base)

CH,C=O+H,N- CH,CH=N-O) HO
Imine
(a schiff base)

NCH, NCH, + H
F0+HN-CH,
Imine
(a schiff base)
590 Organic Chemistry

(b) With hydroxylamine (formation of oxime)

H
CH,C=OH,NOH -H,O CH,CH=NOH
Hydroxylamine Aldoxime
H

CH,C=0 + H,NOH H
-H,O CH,C=NOH
CH CH
Ketoxime
F0 + HÑOH H =NOH
H,O
Ketoxime

Oximes have planar structure (C=N) and they exhibit geometrical isomerism.
One of the important reactions of oxime is Beckmann rearrangement which is disCncced
cussed n
Chapter 18.

(c)With hydrazine (formation of hydrazone)

CH,CH.C=0 + HNNH, H
H.O CH,CHC=NNH,
-H,O
H
Propanal Hydrazine Hydrazone derivative

CH,C=0 + H,NNH, H
-H,0
-H,O CH,C=NNH,
CH CH
Propanone Hydrazine Hydrazone derivative

d) With phenylhydrazine (formation of phenylhydrazone)

CH,CHC=0 + H,NNH- H CH,CH,CH=NNH

H,O
H
Propanal
Phenylhydrazine Phenylhydrazone of propanal

CH,CHC=0 H,NNHO) H,0 CH,CH,C=NNHu-

H
CH, CH
Butanone Phenylhydrazone of butanone
 Aliphatic Carbonyl Compounds (Alkanals and Alkanones) 591

semicarba (formationo semicarbazone)

With
(e)

CH,C=O + H,NNH NH, CH,C=NNHCNH,

H H
Semicarbazide Semicarbazone derivative

CH,C=O + HNNH NH, CH,C=NNHCNH,

CH3 CH
Semicarbazone derivative

With 2,4-dinitrophenylhydrazine (formation of 2,4-dinitrophenylhydrazone)

NO NO,

CH,C=O+H,NNHKONo, CH,C=NNH- -NO

H H
2,4- Dinitrophenylhydrazine 2,4- Dinitrophenylhydrazone
Ethanal (2,4-DNP reagent) (2,4-DNP derivative)

NO NO
CH,C=O + H,NNH NO CH,C=NNH NO
CH CH3
Acetone 2,4-DNP derivative

NO, NO,

F0H,NNH-O-No, NNH O>No,

Cyclohexanone 24-DNP derivative

Reaction of carbonyl compounds with 2,4-Dinitrophenylhydrazine

ns reaction is of special interest and is used for the qualitative analysis of carbonyl
pounds since the product 2,4-dinitrophenylhydrazone has an intense yellow or
tnge colour. Therefore if addition of 2,4-dinitrophenylhydrazine (commonuy
r e d to as DNP reagent) to an organic compound gives deep yellow or orange
Od,the compound is said to be a carbonyl compournd.
 I nese are discussed as follolows:
Aldol c o n d e n s a t i o n

molecules of
aldehyde containing a-hydrogen
to nroduce p-hydroxy aldehyde known as aldol andundergo condensation in the presence
the reaction is known as Aldol
of a base

acetaldehyde (ethanal) molecules condense in reaction. The

the presence of base like sodium hydroxide to
a
Pnroduce 3-hydroxybutanal (p-hydroxybutanal). Other bases such as barium
hydroxide may also be used. hydroxide or calcium

CHCH + CH,CHH NaOH

CH,CHCH,CH
O OH O
Ethanal
3-Hydroxybutanal
HO (an aldol)

osl CH3
o CH,CHCH + CH,CH,CH NaOH CH,CH,CHCHÇH
O OH O
unoPropanal 3-Hydroxy-2-methylpentanal
(aldol)
Mechanism
Step 1. Abstraction of o-hydrogen of aldehyde by base (formation of enolate ion):
The a-hydrogen, being acidic, is abstracted by base to produce carbanion.

O
OH CH,CH o
CH,CH
H
Step 2. Nucleophilic attack of carbanion on the second molecule of aldehyde:
The carbonyl carbon is electrophilic in nature and is attacked by a nucleophilic carbanion.

H H

CH C CH,H CH,C-CH,CH
600 Onganic Chemistry

Step 3. Protonation (formation of aldol):

HOH
CH,C-CH,CH CH,CHCH,CH
OH
aldol

Heating causes elimination of water from aldol to produce an a,ß-unsaturated

as Aldol condensation.
aldehyde, The.
reaction is known Dehydration can also be affected by using minera overall
HO O
CH CH-HH A
-H,O CH,CH=CHCH
But-2-enal (Crotonaldehyde)
OH Ob mesenban a. 5-unsaturated aldehyde]

The ketones containing

a-hydrogen also undergo similar reactions to produce
that is, ketols. Propanone (acetone) in the
presence of a base undergoes condensation
B-hydroxyketones
to form
4-hydroxy-4-methylpentan-2-one.

CH3
CH,CCH + CH,CCH NaOH
CH,C-CH,CCH
O OH
(a ketol)

Ketols under acidic conditions or heating undergo dehydration to produce a.B-unsaturated ketones.

CH, H CH
CHCCHCCH, A
-H,O CH,C=CHCCH,
OH Mesityl oxide
O

an a, B-unsaturated ketone]

The mesityl oxide may be condensed with another molecule of acetone to form phoronc

CH CH3 CH3 CH
CH,C=CHCCH, + NaOH
O=CCH CH,C=CHCCH=CCH,
O
Mesityl oxide Phorone
o-hydrogen abstracted
from this carbon to form
HO
carbanion
 Aliphatic Carbonyl Compounds (Alkanals and Alkanones) 601

Mixed aldol c o n d e n s a t i o n

lehydes
wo different aldeh (both having a-hydrogen) may undergo condensation in presence of base
two different
ive a mixture of different B-hydroxy aldehydes. The condensation reaction of
to
is commonly termed as mixed aldol condensation. For example,
ethanal and propanal,
hvdes
aldehy
in presence of base, undergo condensation to form a mixture of four products.

3-hydroxybutanal () formed by self condensation of ethanal.

3-hydroxy-2-methylpentanal (1) formed by self condensation of propanal.
3-hydroxy-2-methylbutanal (II) by condensation of carbanion from propanal
(CH-CH-CHO) with ethanal.
with
3-hydroxypentanal (IV) by condensation of carbanion from ethanal (CH,CHO)
propanal.

CH Self
condensation
CH,CHCH,CH+ CHCH,CHCHCH product
OH O OH O
CH CH + CH CH,CH
NaOH motaibo[I]
HO CH, O Mixed
condensation
CH,CHCHCH+ CH,CH,CHCH,CH
product
c-hydrogen a-hydrogen
OH OH
IV

Crossed aldol condensation l o s a ) id obrbed viovn

is carried
To avoid formation of a mixture of products, the aldol reaction with different aldehydes
out in such a way that one aldehyde contains -hydrogen and the other does not have any
For
-hydrogen. During reaction, the carbanion is formed from the a-hydrogen containing aldehyde.
example,

NaOH CHCH,CH
CH CH,CH EXPLORE MORE
SH
O O OH .. through solved
Benzaldehyde
No a-hydrogen thus
Ethanal
problem 102
no carbanion formed
Carbanion formed at this carbon 3-Hydroxy-3-phenylpropanal
(a-hydrogen containing aldehyde)

Claisen-Schmidt reaction
The reaction may occur between an aldehyde and a ketone In a ossed aldol condensation
of the
ne component is ketone having a-hydrogen and the other is an aldehyde with no
-ydrogen, the reaction is called Claisen-Schmidt reaction.ou
ilb
602 Organic Chemistry

CH
CH,CCH
NaOH
CH-CH.CCH,
OH
o o1 no 41ydroxy-4-phenylbutan

compared to the
the
In general, the reactivity
of aldehydic
carbonyl group 1s more
carbonyl
carbon of aldehyde.
carbonyl group of
carbaniono c c u r s on

ketone. Thus, attack of

' s reaction r a
a r m a l a
 Aromatic Aldehydes and Ketones 629

18.3
18.3 CHEMICAL PROPERTIES OF AROMATIC ALDEHYDES AND
KETONES
of chemical reactions which include
Thearomatic carbonyl compounds undergo various types
the nucleophilic addition reactions,
a reaction involving carbonyl (C=0) groups, namely
axidation reactions, and reduction reactions, (ii) reactions involving a-carbon of carbonyl
mpounds,
comp
(ii) some typical reactions of aromatic aldehydes, and (iv) electrophilic substitution
The varous reactions are discussed as follows:
reactions.

18.3.1 Reactivity of Carbonyl Group: A General Discussion

of oxygen makes the carbon-oxygen double bond polar in nature, which
The high elctronegativity
reactions. The reactions are similar to their
makes them undergo characteristic nucleophilic addition
are more reactive compared to
aliphatic counterparts (refer Section 17.3.1). The aromatic aldehydes
is less compared to
aromatic ketones, however, the reactivity of aromatic carbonyl compounds
carbonyl compounds due to steric factor. The order of reactivity may be generalized
as:
aliphatic

- CR
RCH RCR CH>

Benzaldehyde and benzophenone do not undergo the reactions involving reactivity at a-carbon
which
of the carbonyl compounds due to absence of a-hydrogen. However, there are some reactions,
are typical of aromatic aldehydes and are not exhibited by aliphatic carbonyl compounds. The
substitution reactions. Since carbonyl group is
aromatic carbonyl compounds undergo electrophilic
an electron withdrawing group (-R effect and -I effect), the aromatic aldehydes and ketones
deactivate the aromatic ring towards electrophilic substitution and behave as meta-directors.

bw aloilool
o
Co R O
R

R =H,
--
alkyl or aryl

18.3.2 Nucleophilic Addition Reactions

reactions similar to their aliphatic
e aromatic
Counter
carbonyl compounds undergo nucleophilic addition
parts. The reactions occur with carbon, oxygen, nitrogen, and sulfur nucleophiles. The

mechanism of nucleophilic addition reactions is simitar to that discussed for aliphatic

cheral
carbonyl compounds (for details, refer section 17.3.2).

Keaction with carbon nucleophiles

) With HCN. The The aromatic carbonyl compounds react with hydrogen cyanide to form

cyanohydrin.
 630 Organic Chemistry

-CH
AOITAMORA 0 2am
+HCN OHO
CH OT
o1sbu abruor CN
n o Benzaldehyde oun d O (0Cyanohydrin nou
O oitosor o r pota OHH
-CCH, + HCN

Aetophenone
CCHone
CN
O o0 A :quuo10 ynodhe OH

O)
Benzophenone
+HCN
obbs igos
CN
The hydrolysis of cyanohydrin is often used as a method for
synthesizing hydroxy acids,
OH OH
H,0
CH CH O
CN COOH
odp-oMitvioeun rvlovpt enotosor sib 2-Hydroxy-2-phenylethanoic acid ban sbedeblo
(Mandelic acid)
ub 2bEO