LECTURE NOTES

Session - 2009-10

ORGANIC CHEMISTRY
TOPIC :

ALKENE & ALKYNE

Contents : Alkene/Alkyne
Lect.

Lect.

1 Physical properties of Alkenes/Alkyne

2 Relative Besicity
3 Lab test of alkene and alkynes
4 Stability of alkenes/cycloalkenes
5 Method of preparation

(H) Acid-Catalyzed Hydration

(A) By partial reduction of alkynes

(B) Dehydration of alcohol

(i) For Alkene

(a) Oxymercuration-Demercuration
(b) Alkoxymercuration - demercuration
(c) Hydroboration-oxidation (Syn addition)
(ii) Acid-Catalyzed Hydration For Alkyne
Examples

(C) By pyrolysis of esters

Examples

Lect.
(I) Oxidation Reaction

Lect.

(i) Ozonolysis (C = C, C C)

(D) By Dehalogenation of vicinal dihalides/

Examples

tetrahalides
(E) Dehydrohalogenation of alkyl halides/
vicinal dihalides
(F) Replacement of the acetylenic hydrogen

Lect.
(ii) Hydroxylation Reactions (Alkenes, Alkynes)

atom of terminal alkynes to form higher

(iii) Epoxidation of Alkenes

alkynes

(iv) Oxidative cleavage (Alkenes, Alkynes)

(G) Miscellaneous

Examples

Hydrolysis of carbides
Examples

Lect.

Lect.

7. Miscelleneous

6. Chemical Reactions

(B) Addition of NOCl

(A) Electrophilic addition reaction

(C) Halogenation. Allylic substitution

(B) Addition of halogen to alkenes

(D) Alkylation

(C) Addition of halogen to alkynes

Examples

(A) Addition of carbenes to Alkenes

(D) Addition of HOX to Alkene

(E) Addition of HOX to Alkynes
Examples

Lect.
Discussion

Lect.
(F) Addition of Hydrogen Halides (+ HX) to Alkene
(G) Addition of Hydrogen Halides (+ HX) to Alkyne
Examples

Page # 2

Physical properties of alkenes & General method of preparation of alkenes

1. Physical Properties of Alkenes

TABLE : 1
Physical properties

Homologus series

Isomers

1.

Physical state

C1 C3 gases
C4 C20 liquids
> C20 : solids

2.

Dipolemoment ()

3.

Polarity

4.

Melting point

increases with M.W.

trans > cis

(due to more packing capacity)

5.

Boiling point

increases with M.W.

cis > trans

# branching decreases B.P.

cis > trans

cis > trans (for Cab=Cab type of alkenes)

<CC=CC
Polarity increases, boiling point
increases
6.

Solubility

7.

Stability

Practically insoluble
in water but fairly
soluble in nonpolar
solvents like benzene
petroleum ether, etc.

cis > trans

Polarity increases, solubility in polar
solvents increases.

trans > cis

(cis isomers has more VanderWaals
repulsion)

TABLE-2 COMPARATIVE STUDY OF ALKANES, ALKENES, ALKYNES

Properties

Alkanes

Alkenes

Alkynes

1.

Bond length

1.54 (C C)

1.32 (C = C)

1.20 (C C)

2.

Bond energy(KJmol-1)

415 (C C)

615 (C = C)

835 (C C)

3.

Hybridization

sp3

sp2

sp

4.

% s character

25%

33%

50%

5.

pKa

50

44

25

6.

Electronegativity of C

sp3 (C)

7.

Polarity

R CH2 CH3

R CH = CH2

RCC

8.

Rate of hydrogenation

less

more

9.

Rate of electrophilic
addition reaction

more

less

10.

Heat of combustion

C2H6 ( 373)

C2H4 ( 337 kcal)

C2H2 ( 317 kcal)

11.

Density (g/cm3)

C3H8 (0.50)

C3H6 (0.52)

C3H4 (0.67)

<

sp2 (C)

<

sp (C)

Page # 3

12.

H 121.2 H
C=C
H
H

Structure

1.08

ethene

13.

Shape

Tetrahedral

Planar

Linear

2. Rel at i ve Basi ci t y
(a) CH3 CH2 : H2C CH : HC C :
(b)

OH < OR < C

CR <

NH2 <

CH2 < CH2CH 3

CH

3. Stability of Alkenes/Cycloalkenes
Overall relative stabilities of Alkenes
Studies of numerous alkenes reveal pattern of stabilities that related to the number of alkyl groups attached
to the carbon atoms of the double bond. The greater the number of attached alkyl groups (i.e., the highly
substituted the carbon atoms of the double bond), the greater is the alkenes stability. This order of stabilities
can be given in general terms as follows.
Relative stabilities of alkenes
>

>

H
C=C

>

>

R
C=C

>

>

Cycloalkenes
trans-Cycloheptene has been observed spectroscopically, but it is a substance with a very short lifetime and
has not been isolated.
trans-Cyclooctene has been isolated, however. Here the ring is large enough to accommodate the geometry
required by a trans double bond and still be stable at room temperature. Trans-Cyclooctene exists as a pair
of geometrical isomers. You may wish to verify this using hand-held models.

CH2 CH2
CH2
|
CH2

CH
||
CH

CH2 CH2
cis-Cyclooctene

7
6

2
3

8
1

trans-Cyclooctene

The way of measuring the stability of an alkene is the determination of its heat of hydrogenation or the
heats of combustion. Both are exothermic reactions. (H = ve)
Hhyd

1
( ve sign indicates the exothermic nature of reaction)
stability

In general, the order of stability of alkenes is :

R2C = CR2 > R2C = CHR > R2C = CH2 > RCH = CHR (trans > cis) > RCH = CH2 > CH2 = CH2

Page # 4

4.

Methods of preparation

(A)

BY PARTIAL REDUCTION OF ALKYNES

(a) By Catalytic Hydrogenation of Alkenes in presence of poisoned catalyst (A Syn Addition of Hydrogen: Synthesis of cis-Alkenes : This is performed by)

(i) Lindlars catalyst : Metallic palladium deposited on calcium carbonate conditioned with lead acetate
and quinoline.

(ii) P-2 catalyst (Ni2B nickel boride)

General Reaction

H2 ,Pd / CaCO 3
(Lindlar 's catalyst )
quinoline

R C C R

Mechanism of hydrogenation :
(1)

( 2)

Steps : The reactant alkyne molecules and hydrogen molecules get adsorbed at the surface of metal catalyst. It is chemical adsorption (chemisorption).
In this state, the reactants lie very close to each other and so the hydrogen atoms start forming bond with
carbon. Two hydrogen atoms are added to two triply bonded carbon atoms from the
same side of bond and a cis or syn addition product is formed. The product alkene now escapes away
from the surface of the catalyst. Quinoline occupies the metal surface inhibiting further reduction to alkanes.
Quinoline therefore is called catalyst poison and such palladium is called deactivated catalyst or poisoned
catalyst.

(b) Birch Reduction : (Anti Addition of Hydrogen: Synthesis of trans-Alkenes)

General Reaction

Na / Li
Liq. NH3

H
R
C C
H
R

Reagents Na(or Li,K) + liq NH3 Na+ + e (solvated electron)

R

H NH 2

Mechanism :

R C C R

C=C

NaNH2 +

Na+

Note : This process of reduction is not eligible when terminal alkynes are taken.(RCCH) because terminal alkynes
form sodium salt with Na metal.

CH3 C CH + Na / NH3 CH3 C C Na+ + H

(B)

BY DEHYDRATION OF ALCOHOLS
Alcohols when heated in presence of following reagents undergo loss of water molecule and form alkenes.
The elimination is elimination.
(i) H2SO4 / 160C
(ii) H3PO4 /
(iii) P2O5 /
(iv) Al2O3 / 350C undergo loss of water molecule and form alkenes

Page # 5

General Reaction

(C)

BY PYROLYSIS OF ESTERS
Thermal cleavage of an ester involves formations of a six membered ring in the transition state leading to the
elimination of an acid leaving behind an alkene.

500C

Remarks:-

(1) When an ester is heated at high temperature, it forms an alkene by elimination of an acid.
(2) It is an intramolecular 1, 2 elimination (-elimination)
(3) It passes through a cyclic T.S. (6 membered).
(4) It is a syn elimination, i.e., both the eliminating groups lie on the same side.
(5) The least crowded -Hydrogen is eliminated to give the major product (Hoffman alkene).

As a direct consequence of cyclic transition state, both the leaving groups namely proton and carboxylate
ion are eliminated from the cis position. This is an example of cis elimination.

Examples :
H2 / Ni2B(P 2 )
or H2 / Pd / CaCO3

1.

CH3CH2C CCH2CH3
( syn addition)

3 Hexyne

2.

Na / NH ( )

CH3 CH2 C C CH2 CH3 3

CH2OH

CH2

3.

CH3

+
(I)
Minor

(II)
Major

CH2OH

4.

If the starting material is labelled with deuterium as indicated, predict how many deuterium will be present in
the major elimination product ?

Page # 6

HO

HO

CD3

HO

(b)

CD3

H2SO4

(a)

+
H2O

CD3

H O

CH3

CH2

CH3

H2SO4

(C D cleavage is about 7 times slower than C H cleavage so the product from C H cleavage should be
formed about 7times as fast)
5.

Write the intermediate species as indicated :

H
3, 3 dimethyl 2 butanol
..................
(A)
oxonium ion

H2 O
Migration

....................
.....................
(B)
(C)
20 carbocation
30 carbocation

-H+

-H+

(E)
Alkene

CH3
Ans.

(A) =

CH3 C

CH3

CH CH3

CH3 OH2
+

CH3
(B) = CH3 C CH
+
CH3

(D)
Alkene

CH3 CH3
(C) = CH3 C
+

CH CH3

CH3

CH3 CH3
(D) =

CH3 C

CH3

(E) =

CH3 C CH CH2
CH3

Major product is (D) Minor product is (E)

6.

CH3 CH2 O C CH2 CH3 ethene + propanoic acid

O

7.

Ph CH2 C O CH2 CH2 CH3 propene + Ph CH2 COOH

O

CH3

8.

O C CH3

Page # 7

O C CH2 CH3

9.

ethene +

+ CH3CH2COOH

COOH

C2H5
O
Et

Et
H

Me

Me
CH3 COOH

H
OH
H

10.

O C CH3

CH3

(D)

+ CH3 COOH

CH3

Dehydrohalogenation of alkyl halides

Dehydrohalogenation is the elimination of a hydrogen and a halogen from an alkyl halide to form an alkene.
Base can be used.
(i) Hot alcoholic solution of KOH EtO / EtOH
(ii) NaNH2
(iii) tBuOK+ in t-BuOH (Hoffmann)
General reaction :

| |
alcohol
C C + KOH

| |
H X

Mechanism

|
|
C C KX H2O

+ BH +

Undergo elimination of hydrogen halide (HX) leading to the formation of alkenes.

(E)

By Dehalogenation of vicinal dihalides

There are two types of dihalides namely gem (or geminal) dihalides in which the two halogen atoms are
attached to the same carbon atom and vicinal dihalides in which the two halogen atoms are attached to the
adjacent carbon atoms.
Dehalogenation of vicinal dihalides can be effected either by NaI in acetone or zinc in presence of acetic acid
or ethanol.
General Reaction

(i)

Br
|
|
CC
| |
Br

NaI
or Zn, CH3COOH

Br
Mech.

ZnBr

C C

Zn

Br
(ii)

C C

+ ZnBr2

Br
Zn dust

CH3 CHBr CH2Br CH3 CH = CH2

CH3 COOH or

C2H5OH as solvent

Mech.
With NaI in acetone :

Page # 8

+ IX

It involves an antielimination of halogen atoms

Remarks
(1)
Both are E2 elimination.
(2)

Both are stereospecific antielimination.

NaI
Acetone

e.g.

CH3 CHBr CHBr CH3 CH3 CH = CH CH3

Method of preparation of alkynes

(A)

Dehalogenation of tetrahaloalkane & Trihaloalkanes

General Reaction

R C C R + 2Zn X2

CHCl3 + 6Ag + Cl3 CH

CH CH + 6 AgCl

(B)

By dehydrohalogenetion of gem and vic dihalide :

Alkynes can be synthesized from alkenes. A vicinal dibromide can be synthesized by addition of bromine to
an alkene. The vic-dibromide can then be subjected to a double dehydrohalogenation reaction with a strong
base to yield an alkyne.
H H
|

General Reaction

2 NaNH

2
R C C R 2NaBr
RCH CHR Br2 R C C R

Br Br
A vic dibromide

The dehydrohalogenations occur in two steps, the first yielding a bromoalkene and the second, the alkyne.
Mechanism :

Bromoalkene

Br

+ HNH +

C
C
Br

Br Br

Amide ion
vic-Dibromide
(The strongly
basic amide ion
brings about an
E2 reaction.)

H
Ammonia

Bromide
ion

R
CC

Step 2

HN + RCCR

H
Step 1

Br

+
R

Bromoalkene
(A second E2 reaction
produces the alkyne)

..
- ..
R C C R + H N H + :Br:
:N H
..
|
|
H
H
Alkyne
Ammonia bromide
Amide ion
ion

From vicinal/Geminal Dihalides (2HX)

Step 1

Step 2

Page # 9

(1) Reactant
(2) Nature of Elimination

E2

(3) Rate of E2

r1
>
(anti elimination)

E2
r2
(anti elimination)

Reagents
(1) NaNH2, or , LiNH2 , or , KNH2
(2) alc. KOH
Depending on the conditions, these two dehydrohalogenations may be carried out as separate reactions, or
they may be carried out consecutively in a single mixture. Sodium amide, a strong base, is capable of
effecting both dehydrohalogenations in a single reaction mixture. (At least two molar equivalents of sodium
amide per mole of the dihalide) must be used. If product is to be a terminal alkyne, then three molar equivalents
must be used because the terminal alkyne is deprotonated by sodium amide as it is formed in the mixture,
consuming the sodium amide otherwise needed for the remaining dehydrohalogenation steps)
Dehydrohalogenations with sodium amide are usually carried out in liquid ammonia or in an inert medium
such as mineral oil.
Geminal dihalides can also be converted to alkynes by dehydrohalogenation. A geminal dihalide (abbreviated
gem-dihalide) has two halogen atoms bonded to the same carbon (from the Latin geminous, twins). Ketones
can be converted to gem-dichlorides through their reaction with phosphorus pentachloride, and these products
can be used to synthesize alkynes. Ketones can be converted to gem-dichloride through their reaction with
phosphorus pentachloride and these products can also be used to synthesize alkynes.

(C)

Replacement of the acetylenic hydrogen atom of terminal alkynes to form higher alkynes
(a) General Reaction

(I)
(II)

Ether

R' X
RC = C MgBr
RC C H + CH3MgBr

R C C R

Sodium ethynide and other sodium alkynides can be prepared by treating terminal alkynes with sodium
amide in liquid ammonia :

liq. NH

3
CH3C C H + NaNH2

NH3 +

Na Metal
CH3C C H
+ H2 +

HCCH

(D)

2CH4 + BrMg C C MgBr

CH3 C C CH2 CH3

CH3
|
CH3 C C CH CH3

H5 C2 C C C2 H5

By hydrolysis of carbides
CaC2 + 2HOH C2H2+Ca(OH)2
MgC2 + 2HOH C2H2+Mg(OH)2
Mg2C3 + 4HOH CH3 C CH + 2Mg(OH)2

(E)

BY Kolbe's Electrolysis
Formation of alkene

Page # 10

Formation of alkyne

EXAMPLES :
Identify the product in the following reactions :

CH3

H
Na I / acetone

1.

H3C

Na I / acetone

2.

3.

What are the various product due to loss of HBr from

CH3
CH3
Ans.

,
(minor)

4.

What are the major products of dehydrohalogenation of :

(i) CH3 CH2 CH2 CH2 CH2 Cl

(ii) CH3 CH2 CH2 CH CH3

|
Cl
CH3
|

(iii) CH3 CH2 CH CH2 CH3

|
Cl

(v) CH3 CH CH CH3

|
|
Ans.

|
Cl

Cl
|
(vi) CH3 CH C CH3
|
|
CH3 CH3

Cl CH3
(i) gives CH3CH2CH2CH = CH2, (ii) & (iii) = CH3CH2CH = CHCH3

(iv) & (v) =

5.

(iv) CH3 CH2 C CH3

(vi) =

Identify the major (satytzeff) and minor (Hofmann) product of dehydrochlorination of :

Page # 11

Ans.

NaNH2

CH CH

6.

7.

CH3 CHCl2

NaNH2

CH3 C CH

8.

9.

NaNH2

CH CH

NaNH2
CH3 CH2 CHCl2
CH3 C CH

10.

NaNH2
CH3 CCl2 CH3
CH3 CCl = CH2

11.
12.

NaNH 2
CH3 CH2 CH2 CHCl2
CH3 CH2 C CH
NaNH2
CH3 CH2 C CH

13.

NaNH 2
CH3 CH2 CCl2 CH3
CH3 CH2 C CH
NaNH 2

CH3 CH2 C CH

14.

15.

16.

Give the structure of three isomeric dibromides that could be used as starting materials for the preparation of
3, 3 dimethyl 1 butyne.
CH3

Sol.
17.

CH3 Br

CH3

CH3 C CH2 CHBr2

CH3 C CH
CH3
CH3 Br
(I)
(II)
Show the product in the following reaction
CH3
EtOK
CH CH2
?
EtOH
Br Br

CH2
Br

CH3

CH3

CH3 Br
(III)

Page # 12

CH3
C CH

Sol.
18.

1, 1 dibromopentane on reaction with fused KOH at 470K gives 2 pentyne

Br

Ans.

fused KOH
CH3 CH2 C CCH3
Br CH CH2 CH2 CH 2 CH3
470 K
1, 1 dibromo pentane
2 pentyne
Give the mechanism of this rearrangement.
Mech.
Br H
H
H
-OH
H C C CH2CH2CH3
C C
-OH
Br
CH2CH2CH3
Br H

C C C CH2CH3

C C CH2CH3

-OH

H OH

C C C CH2CH3

H
H

H
C C C CH2CH3
H

H2O
OH

H
H

C C C CH2CH3

C C C CH2CH3

H OH
OH

C C C CH2 CH3
H

2 pentene
19.

Br2
NaNH2
CH3 CH2 C HCH2Br
CH3CH2C CH
CH3 CH2 CH CH2
CCl 4

Br

mineral oil
110 160 C

20.

Page # 13

6. Chemical Reactions :
Due to presence of weak electrons in alkene and alkyne, it well go for electrophilic reaction. Now question
is electrophilic addition or electrophilic substitution ?
In electrophilic substitution reaction, one bond is broken and a new - bond between one of the doubly
bonded carbon atoms and the electrophilic is formed. Since the bond energes of the bond broken and the
new bond formed are not much different therefore electrophilic substitution reaction are not accompnied by
large energy changes.
On the other hand in electrophilic addition reactions one weak -bond (251 KJ mol1) is broken and two
strong bonds (2 347 = 694 KJ mol1) are formed. The overall reaction is accompnied by a release of about
694-251 = 443 KJ mol1 of energy. In other words electrophilic addition reactions are energetically more
favourable than electrophilic substitution reactions Thus the typical reactions of alkenes are electrophilic
addition reaction and not the electrophilic substitution reactions.

(A)

Electrophilic Addition Reaction (Mechanism, Remarks, Reactivity order)

(a) General Reaction of electrophilic addition :

............. Addition product.

(b) Mechanism :

(c) Remarks :
Alkenes, Alkynes and Alkadienes are electron rich species. So they function as
species (due to
loosely bound electrons)
These compounds mainly give electrophilic addition reactions. Due to nucleophilic nature alkenes / alkynes
have affinity for

The reaction is initiated by an attack of

(d) Reactivity of an Alkene:Factors:

(1) Presence of e releasing groups (+m, +I) at C = C increases nucleophilicity and reactivity.

Page # 14

(2) Presence of ERG stabilises the intermediate carbocation.

(3) more stable C , more is reacetivity..
(4) better bridged C
(e) Examples of Reactivity Orders:(i)

(ii)

>

>

>

>

>

>

..

G CH = CH2 >> CH2 = CH2 (reactivity)

( m )

..

NH2 CH = CH2 (enamine)

..
R .O. C = C (vinyl ether)

..

H .O. C = C tauto. C C
O

(enol)

(iii)

ERG CH = CH2 > CH2 = CH2 > EWG CH = CH2

(a) CH3 O CH CH2 > CH2 = CH2 > CH2 CH CN
(acrylonitr ile )
( vinyl ether )
(b)

CH = CH2 > CH2 = CH2

(c)

< CH2 = CH2

CH = CH2

>

>

(d)

CH = CH2

CH = CH2

ERG

EWG

(f) Electrophilic addition in C C

E Nu

C C

E Nu

(i) + X2
(ii) + HOX
(iii) + HX
(iv) + H2O/H+

(B) Additon of halogen to alkenes (Halogenation)

X2
(a) General Reaction:- R CH = CH R
R CHX CHX R
Page # 15

C=C

X
|
|
CC
|
|
X
usually anti addition

+ X2

(b) Mechanism
Step-1
Formation of a halonium ion
..
+ : .X.

.. + : .X. :

: .X.
..

C=C

Halonium ion

Step-2

Opening of the halonium ion.

X attacks from the back side of halonium ion.

The nucleophile attacks the electrophilic nucleus of one halogen atom, and the other halogen serves as the
leaving group, departing as halide ion. Many reactions fit this general pattern.
(c) Reagents:- Br2 > Cl2 (F2, I2 not used)
Solvents:- CCl4 , CHCl3 (H2O, MeOH, EtOH, CH3COOH)
best
(d)Remarks :
(i) F2 is not added because F+ is never generated. Morever reaction is explosive giving CO2 & H2O
(ii) I2 is not added because reaction is reversible with equilibrium in backward direction.
(iii) Reaction with bromine is basis for test of alkenes.
(iv) Halogen addition is stereospecific anti addition.
(v) Halogens can also be added in presence of sun light and give free radical addition.
(Reactivity of halogen addition in sunlight is F2 (explosive) > Cl2 > Br2 > I2)
(e) Stereospecific Nature:- With longer E (longer than H ion) the reaction is highly stereospecific.
If a bridged C is formed, then it is anti-addition or trans addition of two species at C = C.
i.e., one stereoisomer of alkene (cis/trans) will give only one stereoisomer of product.
(either d/ or meso)
Alkene
Cis
Cis
Trans
Trans

Product
meso type
d type
d type
meso type

Addition of halogen to alkynes ( C C )

Br Br
Br
Br2 (leq.)
Br2 (leq.)
(a) R C C R R C = C R R C C R
(1) r1
( 2) r2
Br Br
Br
(Tetrahalide)
(Trans-dihalide)

(C)

Addition
Syn.
Anti
Syn.
Anti

(b) Rate:- r2 > r1 (Criteria : Stability of carbocation)

Page # 16

Br
R C C R > R C = C R
+
+
Br
Br Br
(Vinyl C+ )
(Alkyl C + )
(c) Nature of Addition:- Anti in both step

X (leq.)
D
R C C R 2 2
(1) Anti
( 2) Syn.

D / Pd / CaCO 3
R C C R 2

(1) Syn.
[lindlar , catalyst ]

(D)

Addition of HOX to Alkene

(a) General Reaction

OH
| |
| |
C C + HOX C C
| |
X

(b) Reagents
(i) X2 + H2O HOX + HX
(ii) HOX
Remarks :

Anti adition
No rearrangement
No carbocation
Bridged Carbocation

As H2O attacks the bromonium ion, positive charge develops on the carbon from which the bromine departs.
The transition state has some of the character of a carbocation. More substituted carbocation are more
stable than less substituted ones; therefore, when the bromonium ion ring opens, it does so by breaking the
bond between bromine and the more substituted carbon.

Addition of HOX to Alkynes

X
HOX
HOX(leq.)

R C = CH
R C C H
(1 eq.)
OH enol

(a)

(E)

H2O

Page # 17

R C CH2X

R C CHX2

O
10% (minor)
[-Haloketone]

O
90% (major)
[-Dihaloketone]

(b) Remakrs :
# Two molecules of HOX can be added, the end product is -Dihaloketone.
# The intermediate product is an enol which gives a minor product -haloketone.
Extention :
H2 O
KOH
R C CH(OH)2
R C CHO
R C CHX2
O
(major product)

Examples :
Ex.1

Br / CCl 4
CH3 CHBr CH2Br
CH3 CH = CH2 2

Ex.2

IBr / CCl 4

CH3 CH = CH2

Ex.3

CH3 CH = CH2

BrCl

Ex.4

CH3 CH = CH2

Br2

Ex.5

Me
Ex.6

ICl

H
Br

Br2

Br
H
Br
H

Me

Br

Me Me
CH 3

Ex.7

CH3
C=C

cis

Ex.9

(d + mixture)

(cis)

H
C=C
trans

CH3

Me Me

Br2

X
H

Me H

CH3
Ex.8

Me H

Br2

(meso)

(trans)
Me

X
Me

Br

Ph CHBr CHBr Ph

(d + ) mix

Br
Ex.10

Ph Ph

IBr

I
H
Page # 18

Ex.12

HOBr / H
CH3 CH CH2
CH3 CH = CH2
OH Br

Ex.13

HOCl / H
CH2 CH2
CH2 = CH2
Cl
OH

Ex.11

Br
|
Br2 / H2 O
CH3 CH = CH2 CH3 CH CH2
NaCl, KI
|
impurities
G
4 products are formed.
G = OH , Br, I, Cl

Br / H O
2 2

Ex.14

OH H

Me

Me Br

Ex.17

Ex.16

Ex.15

- 18
18
OH
18
OH
Cl
NaO
H
Me
Me

Me

HOCl / H

CH CH3

Ph CH CH3 50 60 C Ph CH CH3 Ph
O
OH
OH

Cl 2
Ph C C CH3
Excess

Cl2
D / Ni
(Q ) 2(R )
CH3 C CH
(leq.)
(leq.)

Cl
HOCl (excess)
Ph C C CH3 Ph C C Cl
O CH3

Ex.19

CH3
CH3
HOBr
KOH
CH3 C C CHO
CH3 C C CH
(Excess)
H
H O

Ex.18

Ex. 20

Ex.21

Ex. 22

Page # 19

Ex. 23

Ex. 24

CH
2Cl2
+ Br2

Ex. 25

CH
2Cl2
+ Br2

Stereo Chemistry of addition to Alkene :

Since Cis & Trans isomers form differnet products which are stereoisomers the reaction is stereospecific
as well as stereoselective.

(F)

Addition of Hydrogen Halides (+ HX) to Alkene

(a) General Reaction

+ H X

Page # 20

Markovnikovs Rule :
When reagent (like: HX, H2O) adds to asymmetrical alkene eg, propene isobutene etc. the addition occurs
such that the nucleophilic attaches itself to the carbon atom of the alkene bearing the least number of
hydrogen and electrophilic adds to the sp2 carbon that is bonded ot the greater number of hydrogen.
(b) Remarks :
(i) Non stereoselective
(ii) Markovnikob additon
(iii) Rearrangement

A. Reaction in which two or more constitutional isomers could be formed but one of them predominates is
called a regioselective reaction.
Regioselective reaction can be 1.

Moderately Regioselective :-

eg.

2.

Highly Regioselective : -

CH3 CH = CH CH2 CH3 + HCl

Not Regioselective because intermediate
is only sec. carbocation.

(G)

Addition of Hydrogen Halides (+ HX) to Alkyne

Br
Br
HBr (dark )
HBr
(a) General Reaction R C C H R C = C H r R C CH 3
r1
2
Br
H
(MK)

+
+
H
R C = CH2 R CH CH2 + R C CH3
r2
Br
Br
Br
Vinyl halide
Less stable
more stable

H+
(b) Mechanism:- R C C H r [R C CH2 ] Br
1
Vinyl C

Br -

(c) Remarks:Page # 21

(1) MK Addition in both steps.

(2) r2 > r1 criteria : carbocation stability I < II.
(3) If two moles of HX one added the final product is Gemdihalide.
(4) Electrophilic addition to terminal alkyne is regioselective.
C=C

VS

CC

addition

(1) Reactivity order

C=C

>

CC

(2) C (Stability)

+
CC

>

+
C=C

E
(alkyl C + )

e cloud is
cylindrical
and difficult
to break

E
(vinyl C + )

(3) For H2/Ni (R.O.)

C=C

<

CC

(4) Hhydrogenation (overall)

C=C

<

CC

<

CC

# Heat of hydrogenation per -bond ?

C=C
(d) Reactivity Order:-

R CH CH R >

> RC CR

Free Radical Addition of HBr:- Kharasch Effect or Peroxide Effect

General Reaction

e.g.

HBr / R O 2 / h
R CH2 CH2 Br
R CH = CH2 2

BrCCl3 / peroxides
n C 6H13 CH CH2

n C 6H13 CH CH2 CCl3

1 Octene
|
Br
3 Bromo 1,1,1 trichlorononane

n C 6H13 CH CH2
1 Octene

HBr / R O

2 2

nC6H13CH2 CH2 Br

Mechanism : Steps:-

Remarks:(1) When HBr is added to an unsymmetrical alkene in presence of sunlight and peroxide. Then an
Anti MK Addition Product is obtained.
(2) It is a free radical chain reaction.
(3) In presence of peroxide and sunlight Br is formed in chain initiation step.
(4) Br forms more stable alkyl radical by homolysis of C = C bond.
(5) In the last step alkyl radical abstracts H from HBr and AMK product is obtained.

Page # 22

Examples :
1.
Ans.

Why do we get AMK product ?

In the chain propagation Step (3), more stable alkyl radical (3 > 2 > 1) is formed which gives the major
product.

2.

If HF, HCl, HI are used even in sunlight electrophilic addition takes place. Why only HBr give free radical
addition ?
In chain propagation (iii) steps:
R CH = CH2 + X
R CH CH2 X + HR

Ans.

R CH = CH2 + F

R CH = CH2 + Cl

R CH = CH2 + Br
R CH = CH2 + I
B.E.:- CF > CCl > CBr > CI

R CH CH2 F

R CH CH2 Cl

R CH CH2 Br

R CH CH2 I

In step (iv)

R CH CH2 X + H X

R CH CH2 X + H F

R CH CH2 X + H Cl

R CH CH2 X + H Br

R CH CH2 X + H I

exo
exo
exo
endo

R CH2 CH2 X + X + HR
R CH2 CH2 X + F + endo
R CH2 CH2 X + Cl + endo
R CH2 CH2 X + Br + exo
R CH2 CH2 X + I + exo

B.E.:- HF > HCl > HBr > HI

Chain propagration steps indicate that addition of I is endo. is step 3 and is unfavourable.
Addition of F, Cl is endothermic, unfavourable in step 4.
Addition of HBr is energetically favourable [in both chain propagation steps-3 & 4]

CH3
C
HBr

CH3 C = CH2
CCC
( dark )
Br

CH3
C
HBr
CH3 C = CH2 C C C
(light )
Br

CH3
C
HBr
CH3 C CH = CH2 C C C C
(R 2 O 2 )
Br
C
CH3

4.

# Light can also cleave HBr bond.

# R2O2 accelerates cleavage of HBr bond.

3.

HBr

(light )
HBr

( dark )

Br

HBr (R O )
Ph CH = CH2 22 Ph CH2 CH2
Br

6.

Br

5.

CH3
C
HBr

CH3 C CH = CH2
CCCC
( dark )
CH3
Br C

Page # 23

HBr
Ph CH = CH2 Ph C C
Br

7.

CH3
CH3
HBr

CH3 C CH = CH2
CH3 C CH CH3
CH3
Br CH3
HBr

8.

Br

9.

10.

HCl

Cl

11.

HBr

Me

Br

CH3
CH3 O CH2 CH = CH CH CH3

HCl (dry)

CH3
..
CH3 O CH CH2 CH2 CH CH3

12.

Cl

If water is taken, ether will be hydrolysed. Dry HCl is used.

13.

14.

+ HCl

Give the reactants (alkene) of the following products.

or

The planar carbocation (x) is responsible for nonstereoselectivity. The bromide nucleophile can attack from
the top or bottom, leading to a mixture of stereoisomers. The addition is therefore a mixture of syn and anti
addition.

Page # 24

17.

HCl(leq.)
CH2 = CH CH2 C CH CH3 CH CH2 C CH
Cl
HCl(leq.)
CH2 = CH C CH CH2 = CH C = CH2 Conjugated product
Cl
Conjugated System
Neoprene

16.

Cl
HCl(leq.)
H C = CH 2 H C CH3
Cl
Cl
gem dihalide
Vinyl Chloride

15.

HCl(leq.)
H C C H

more stable product

(H)

Acid-Catalyzed Hydration

(i)

For Alkene
Alkenes add water in the presence of an acid catalyst to yield alcohols. The addition takes place with
Markovnikov regioselectivity. The reaction is reversible, and the mechanism for the acid-catalyzed hydration
of an alkene is simply the reverse of that for the dehydration of an alcohol.
The carbocation intermediate may rearrange if a more stable carbocation is possible by hydride or alkanide
migration. Thus, a mixture of isomeric alcohol products may result.
General Reaction

Mech.
Step 1 :

+ H2 O

Protonation of the double bond forms a carbocation

Step 2 :

Nucleophilic attack by water

Step 3 :

Deprotonation to the alcohol

(a) Oxymercuration-Demercuration (ANTI ADDITION)

Alkenes react with mercuric acetate in a mixture of water and tetrahydrofuran (THF) to produce (hydroxyalkyl)
mercury compounds. These can be reduced to alcohols with sodium borohydride and water.
Oxymercuration

Page # 25

O
OH
O

||
|

|
||
THF
+ H2O + Hg OCCH C C
+ CH3 COH
O
3 2

|
|
||
Hg OCCH3

General Reaction

OH
|
|
CC
O
+
|
|
||
Hg OCCH3

| |
+ NaBH4 C C + Hg +
| |
HO H

(Demercuration)

In the oxymercuration step, water and mercuric acetate add to the double bond ; in the demercuration step,
sodium borohydride reduces the acetoxymercury group and replaces in with hydrogen. The net addition of H
and OH takes place with Markovikov regioselectivity and generally takes place without the complication
of rearrangements.

Advantage over acidic hydrolysis (1) no requrement of acidic condition, which are harmful to many organic molecules.
(2) No rearrangement occur.
Mechanuism

There are two step

Step (A) : -

Step A is called oxymercuration i.e. addition of H2O & Hg(CH3COO)2.

Step (B)

NaBH4

OH

NaBH4 converts the carbon mercury bond into a carbon- Hydrogen bond. Because the reaction result in the
loss of mercury , it is called demercuration.

If solvent taken is alcohol product will be ether & process is called alkoxymercuration
demercuration.

(b)

Alkoxymercuration - demercuration

General reaction

RO
OR
|
|
| |
NaBH4
ROH
+ Hg(OAc)2

CC

C C
|
|
| |
H
HgOAc
(Markovnikov
orientation)

Page # 26

(c)

Hydroboration-oxidation (SYN ADDITION)

General Reaction

| |
ROH
+ BH3.THF

C C
| |
H B H
|
H

An alkene reacts with BH3 ; THF or diborane to produce an alkylborane. Oxiation and hydrolysis of the
alkyborane with hydrogen peroxide and base yields an alcohol.
(1) HBO leads to hydrogen of an alkene, however H2O is not a reactant.
(2) During process of addition H comes from BH3 & OH comes from H2O2
(3) Net result is addition of H2O by anti markov. rule without rearrangement because no inermediate is
formed.
(4) There are two steps(a) Hydroboration: - Addition of borane on alkenes. In this reaction, the addition of electrophilic Borane &
the nucleophilic H take place in one steps i.e. it is concerted reaction.
- No intermediate is formed.

In this way one BH3 react with three molecules o alkene successively to form trialkyl borane.

There are two reasons for the borane, alkylborane and dialkylborane to add to the sp2 carbon that is bonded
to the most hydrogen .
(A) To achieve most stable carbocation like T.S.
(B) There is moree room at this carbon for the bulky group to attach itself i.e stearic factor.

Page # 27

(b)

Oxidation :- Replacement of B from OH ap.

H2O
2
3ROH + BO 3
(CH3CH2CH2)3 B OR R3B
3
OH
Mechanism
HOOH + HO

HOO + H2O

Re peat the two

Pr eceding steps two time

3 ROH + BO33

Re peat the three

Pr eceding steps

ROH +
two times

(ii)

Acid-Catalyzed Hydration For Alkynes

G.R.

H SO / HgSO 4
R C CH3
R C C H 2 4
O

OH
OH
H SO 4
R C = CH2
R C = C H 2
Hg
+ HgSO4

Hg 2
R C = C H
Mechanism:- R C C H
H2O:
+
Hg

O
R C CH3

tauto.

Remarks:-

(1) Alkynes add one molecule of water.

(2) The product enol tautomerises to a carbonyl compound (aldehyde or ketone) and further addition
does not take place.
(3) The reaction is catalysed by Hg+2 ions.
(4) The product is M.K. Addition of water.
(5) If HBO oxidation method is used, then AMK addition of water takes place.
Important:- The product does not appears to be addition product.
Arrange the following alkenes in order of their reactivity towards acid catalysed hydration
(a)

(b)

CH3 (CH2)3 CH = CH2 < CH3 (CH2)2 CH = CH CH3 < H3 C (CH2 )2 C CH2
|
CH3

H
C=C

CH3
H3C
cis-2-butene

(c)

<

H3C

H
C=C

H
CH3
trans-2-butene

CH2 CH = CH CH3 <

< H3 C C CH2
|
CH3

CH = CH CH2 CH3 < H3C C = CH CH3

Page # 28

(Greater the stability of carbocation (intermediate), greater the hydration.)

EXAMPLES
1.

CH3 CH CH2
Pr opene

H O, H

2
CH3 CHCH3
|
OH
Isopropyl alcohol

2.

CH3
|
CH3 C CH CH2
|
CH3
3,3 dim ethyl 1 butene

CH3 H
|
|
50 % H SO 4
2
CH3 C C CH3
|
|
OH CH3
2, 3-dimethyl-2-butanol
(major product)

CH3 H

CH3
3.

D O/ D
C CH3 2 CH3 C

CH3 C

C CH3

OD D

CH2

CH3

CH3

4.

CH3 C

+ H2SO4

CH3

5.

CH3
|
H3 C C CH CH2
|
CH3

8.

dil. aqueous H SO

4
2

H2 C CHCH2 CH3
1 butene

7.

CH3 C OSO3H
CH3
t Butyl hydrogen sulphate

3,3 dim ethyl 1 butene

6.

83 C
H2O

CH3 C OH .
CH3
t butyl alcohol, bp 830C

H
|
H3 C C
|
CH3

CH3
|
C CH3
|
OH

+ H3 C C C CH3

2, 3 dim ethyl 2 bu tanol

(major )

NaBH4

|
|
CH3 CH3
2, 3 dim ethyl 2 butene
(min or )

OH
|
CH3 CHCH2CH3
2 butanol

CH2 CH CH2 CH3

1 butene

+ enantiomer + dialkyl-and trialkylborane

+ enantiomer

Page # 29

In the first step, boron and hydrogen undergo syn addition to the alkene in the second step, treatment with
hydrogen peroxide and base replaces the boron with OH with retention of configuration. The net addition of
H and OH occurs with anti Markovnikov regioselectivity and syn stereoselectivity. Hydroboration-oxidation
therefore, serves as a useful regiochemical complement to oxymercuration demercuration.

9.

C3H7CH = CH2

Hg(OAC)2
THF / H2O

NaBH 4 / NaOH
C3H7CH(OH)CH2 HgOAC C3H7CH(OH)CH3

(An organomercurial alcohol)

Hg(OAC)2

10.

NaBH

CH3OH

OCH3
OH

11.

12.

Hg( OAC )

NaBH4

NaOH

CH3
CH3
|
|
NaBH4
Hg(OAc )2 , H2O
CH3 C CH CH2


CH3 C CH CH3
|
|
|
CH3
CH3 OH
3,3 Dimethyl 1 butene
3, 3 Dimethyl 2 bu tan ol
(No rearrangement )

13.

14.

CH3
CH3
CH3
+
|
|
|
H (dil. H2SO4)
+
+
CH3 shift
CH3 C CH CH3
CH3 C CH = CH2
CH3 C
CH CH3
|
|
|
3carbocation
CH3
CH3
CH3
2carbocation
( H+ ) H2O
CH3
OH CH3
|
Hydroboration
|
|
CH3 C CH2 CH2OH
oxidation
|
CH3 C CH CH3
|
CH3
CH3 OH
CH3
Hg(OAc)2
|
|
CH3 C CH CH3
NaBH4
|
CH3

(i) Hydration with dil. H2SO4 proceeds via carbocation rearrangement

(ii) Hydration with Hg(OAc)2, H2O, followed by NaBH4 proceeds via Markonikovs rule.
(iii) Hydration with (BH3)2 followed by H2O2 / OH proceeds via Anti Markonikovs rule.

Page # 30

15.

H
16.

BH / THF

H2O2 / OHO

Me

BH2

Me

HBr
Br

OH

H
trans 2 cyclopentanol

1 methylcyclopentene

17.

Me

BH3/THF

H SO
OH 24

OH

H2O2/OH-

HBr

Br

18.

Hg2 / H2 SO 4
RCCH
( A ) (dil.)

BH3 THF

R CH2 CHO

(B) H O / OH
2 2
19.

( A ) /( B )
H C C H
CH3 CHO

20.

Ph C C CH2 CH3

(1) Hg 2

D 2 SO 4

(1) BH3 THF

(2) D 2O 2 / OD

(1) BD 3 THF


(2) D 2 O 2 / OD

Common Sense :

D2SO4 D2SO4 Present in D2O

OD OD Present in D2O
21.

Hg / H 3 O
Ph C CH
Acetophenone
(Reactant)

OH
|
Ph C = CH2 Retrosynthesis

Ph C CH
Page # 31

Hg 2 / H SO

2
4

22.

23.

BH / THF

CH3 C C CH3

HOO

I / OH

+ CHI3

I / OH

NaOH / CaO ( s )
CH3 CH2 COOH Yellow ppt.
CH3 CH3

Alkadines (conjugated) :
E+ addn :

Mechanism :

Page # 32

With a non-classical C+, the product is always a trans-alkene (anti-addition).

Ex.
HBr

(1)

H2C = CH CH = CH2
(r , t )

(trans) > (cis) .........classical.

Page # 33

HCl (1eq)

(2)

(r , t )

(1,2) (1, 6) > (1, 4) > (1, 2).

(3)

HCl
H3C CH = CH CH = CH2

Alkenes = (I/I) ~ II > II. ...........on the basis of alkene stability.

HOX

(4)

6.

Miscellaneous

(A)

Addition of carbenes to Alkenes :

1eq

Methylene is the simplest of the carbenes : uncharged, reactive intermediates that have a carbon atom with
two bonds and two nonbonding electrons. Like borane (BH3), methylene is a potent electrophile because it
has an unfilled octet. It adds to the electrons rich pi-bond of an alkene to form a cyclopropane.

General Reactions
Heating or photolysis of diazomethane (CH2N2) gives nitrogen gas and methylene.
..

. .

: N N CH2 : N N C H2

diazometha ne

Heat or ultraviole t light

N2 + :C

H
Methylene

There are two difficulties with using CH2N2 to cyclopropanate double bonds. First, it is extremely toxic and
explosive. A safer reagent would be more convenient for routine use. Second, methylene generated from
CH2N2 is so reactive that it inserts into C H bonds as well as C = C bonds.

Structure :

Page # 34

(a)

H2C

H2 C

(b)
(c)
(d)
(e)

Singlet
sp2/120/bent
Diamagnetic
6e /e deficient (electrophilic)

triplet
paramagnetic
(electrophilic)

Carbene is an E species. So it gives E addition reactions with alkenes/ alkynes

CH N /

2 2

ex.

CH CHCO /

CH3CH=CH2

(B)

Addition of NOCl
NaCl

CH3 CH = CH2

(C)

Halogenation. Allylic substitution

General Reaction

X2 = Cl2, Br2

NBS = N-Bromosccinimide

(D)

NCS = N-Chlorosuccinimide

Alkylation :
General Reaction

| |
|
|
acid
C C + R H C C
|
|
H R

Examples :
1.

..

C H2 N N: sh

Page # 35

Propene
+

2.

Cl2 , 600C
CH3 CH CH2

Cl CH2 CH CH2
Pr opylene
(Pr opene )

3.

4.

Allyl chloride
(3 Chloro 1 propene )

CH3
CH3
CH3
CH3
|
|
|
|
H SO 4
CH3 C CH2 + CH3 C H
2
CH3 C CH2 C CH3
Isobutylene
|
|
|
CH3
H
CH3
Isobu tane
2, 2, 4 Trimethylpen tan e

(a)

CH3 CH CHCH3 +
2 Butene

light

Diazometha ne

NaOH / H2O
+ CHBr3

(b)

5.

CH 2N2

Show how the insertion of methylene into a bond of cyclohexene can produce the following.
CH3

(a)

(b)

(c) norcarane,
CH3

6.
Ans.

Assertion (A):- Propene (CH3CH = CH2) undergoes allylic substitution.

Reason (R) : CH2 = CHCH2 (allylic) free radical is stabilised by resonance.
(A)

Br
7.

+ NBS
Cyclohexene

1.

3-Bromocyclohexene

F.R Allylic substitution :

H2CCH=CH2

Br / r.t.

2
(1)

........... Eaddition (or F.R. addition)

Page # 36

Br / 400 500 C

.......... Allylic substitution

(2)

NBS / R O

2
2

(3)

X2 = Br2/Cl2
#

X2
[H CH=CH ] + HX

2C
2

(2)

(500 C)
X2

............... (Chain reaction continues)

At high temperature, an allyl free radical can be formed

NCS/NBS ...... N- Bromosuccinimide

(NBS)

(i)

ROOR 2 RO

(ii)

RO + HBr ROH + Br

(iii)

(rds )
H2CCH=CH2 H2CCH=CH2CH + HBr
Br

(iv)

(v)

+ HBr

+ Br2 (low conc.)

H2 C CH=CH2 + Br2

+ Br

NBS is used to provide very slow but steady supply of Br2 . If Br2 is used in excess then addition reaction
takes place but if NBS is used then in one step only 1 molecule of Br2 is formed which is insufficient to give
addtion product so the substitution product is the major product.

Addition always takes place when Br2 is in excess.

Halolactonisation : [unsaturated acid + X2 + basic med.]
NaHCO

H2C = CH CH2 CH2 CH2 COOH

X2

Page # 37

Hydrolysis of vinyl ethers :

Vinyl ethers = Alkoxy alkenes
= Highly reactive alkene (Eaddition)

+ HOR

18

H3 O

Mechanism

H3CCH=O18
ex.

An alkene X (C5H10O) on hydrolysis with dil H2SO4 produces Y and Z. Both give iodoform test (+ve) X is 1015
times more reactive than ethene toward E

(I) (X)

(Y)

(Z)

(II) (X)

(Y)

(Z)

(I)

Oxidation Reaction

(1)

Oxidation of alkene & alkyne by acidic KMnO4

When alkene & alkyne heated with KMnO4 in acidic or in alkaline medium ; following changes takes place.
[O]
Terminal = CH2 CO2 + H2O
Page # 38

[O]
Terminal CH
CO2 + H2O
[O]
Non Terminal alkene = CHR RCOOH
[O]

[O]
C R RCOOH

(2)

Ozonolysis :
Like permanganate ozone cleaves double bonds to give Ketones and aldehydes. However, ozonolysis is
milder, and both Ketones and aldehydes can be recovered without further oxidation.
O

R'
C

(a) General Reaction

+ O3

R'
C

R
O

Ozonide
(CH3)2S

R
C

O+ O

R'
C
H

R
Ketone
(1) O 3

( 2 ) H2 O

+ R'COOH
(Oxidative ozonolysis)

(1) O 3


(2 ) Zn / H2 O or
CH3 COOH or
Me 2 S / H2 O

(1) O3
(2) LiAlH4/NaBH4

(reductive ozonolysis)

+ R'CH2OH
(reductive ozonolysis)

(b) Mechanism

O+

C
O

Molozonide (Primary ozonide)

C

O+

Ozonide

Page # 39

R'
C

R
O

CH3 - S - CH3
dimethyl sulfide

C
H

R'

O+ O

+ CH3 S

CH3

dimethyl sulyoxide
(DMSO)

(3)

Ozonolysis of alkyne : Alkynes gives acid by ozonolysis ozonolysis of alkyne required neither oxidative nor reductive work up - it is
followed only by hydrolysis. carbon dioxide is obtained from the CH gp. of a terminal alkyne.

(1) O

CH COOH + CH CH COOH
CH3 C CCH2 CH2 (
3
3
2
2) H2O

(1) O 3
CH3CH2 CH2 C CH CH3CH2CH2COOH + CO2
(2) H2O

Comparison of permanganate cleavage and ozonolysis : Both permanganate and ozonolysis break the carboncarbon double bond and replace it with carbonyl C =0
groups. In the permanganate cleavage, any aldehyde products are further oxidized to carboxylic acids. In the
ozonolysis-reduction procedure, the aldehyde products are generated in the dimethyl sulfide reduction step,
and they are not oxidized.

Examples :
CH3

CH3

CH3

Conc. KMnO4
- OH

1.
H

(not isolated)
CH3
CH3

2.
H

(i) O3
(ii) (CH3)2 S

O
H

3.

O3

KMnO4/OH -

+ R'COOH

KMnO / H
4

+ R'COOH

K Cr2O 7 / H /
2

or, CrO3 / H /

+ R'COOH

dil.KMnO 4

cold

HIO 4

Page # 40

O
O

Lemienx Reagent
(KMnO4 + NaO4)

4.

OH
OH

H
H

HO4

H
HIO 4

no reaction
OH

OH
H O
(1) TFPAA
2

5.

7.

H
H

( 2) OsO 4
H O

2

6.

OH HIO 4

OH

O
O

How will you distingnish cis, trans cyclohexane-1, 2-diol.

H
H

O + AgIO ppt.
3
O

OH HIO 4 / AgNO3

OH

cis
H
OH

OH
H

HIO / AgNO3
4
No reaction

trans
(i) O3
(ii) (CH3)2 S

8.

CH3CH2CHO + CH3(CH2)4CHO (65%)

3 - nonene

H
(i) O3
(ii) (CH3)2 S

9.

C
H

CHO

CHO

H
O +

C
H

(i) O3
(ii) (CH3)2 S

10.

CHO

CHO

(ii)

Hydroxylation Reactions of alkenes

(a) General Reaction

(b) Mechanism:(1) With Bayer's Reagent:-

Page # 41

2H 2O

+ H3MnO 4
( 5 )
(colorless )

(2) With OsO4/H2O/NaHSO3:-

R CH = CH R

R CH CH R

O
Os

Os

(Cyclic
osmate
ester)

+ H2OsO 4
( 6)

(48)

2H 2O

(3) Epoxidation/Hydrolysis:-

RCO3H = Peroxy acid

HCO3H = PFA (Performic acid)
CH3CO3H = PAA (Peracetic acid)
Ph CO3H = PBA
CO H
3

= MCPBA (Metachloro perbenzoic acid)

Cl
CF3CO3H = TFPAA (Trifluoro peracetic acid)

........... E addition + R'COOH

R CH = CH R
..
O
18

(iii)

Epoxidation of Alkenes :
An alkene is converted to an epoxide by a peroxyacid, a carboxylic acid that has an extra oxygen atom in a
O O (peroxy) linkage.

(a) General Reaction

C=C

O
||
+R C O

O
||
+ R C O H (acid)

The epoxidation of an alkene is clearly an oxidation, since an oxidation, since an oxygen atom is added.
Peroxyacids are highly selective oxidizing agents. Some simple peroxyacids (sometimes called peracids)
Page # 42

and their corresponding carboxylic acids are shown below :-

(b) Mechanism

(iv)

C
O
C

O
H
transition state

Oxidative cleavage of Alkenes

(a) Cleavage by permanganate
In a KMnO4 hydroxylation, if the solution is warm or acidic or too concentrated, oxidative cleavage of the
glycol may occur. Mixtures of Ketones and carboxylic acids are formed, depending on whether there are any
oxidizable aldehydes in the initial fragments. A terminal = CH2 group is oxidized to CO2 and water.
R

R'
C

General Reaction

KMnO4
Warm
conc.
Glycol

R'
O

R'

O O

OH

Aldehye
(Oxidizable)

Ketone
(Stable)

The same reagents that oxidize alkenes also oxodoze alkynes. Alkynes are oxidized to diketone by a basic solution of KMnO4 at room temp.
KMnO 4 dil
CH3 C CCH2CH3
OH

Examples

1.

Bayer ' s Re agent

2.

OsO 4

H2 O / NaHSO 3

3.

Me

OH

H
H

Me H
OH OH

Me

4.

OH

(1) PBA
18
(2) H 2O /OH -

Page # 43

R (1) OsO 4
(2) H2O
H

R CHOH CHOH R
(d / mix )

C=C

C=C

R
5.

R
H

H(meso isomer)
OH OH

H Bayer ' s
C = C (d / mix )

H
R (1) Re agent

6.

H Ag / O 2 /
C = C (meso isomer)
H
( 2) H 2 O
R

7.

What is the main utility of this reaction and why is it superior to KMnO4 cleavage for this purpose ?

Sol.

It locates the position of C = C's in molecules. KMnO4 cleavage is more vigorous and can oxidize other
groups, i.e. OH.

8.

Give the products of the following reactions:(i)

KMnO 4
(aq. bassic )

(ii)

or
Cis-1, 2-Cyclopentanediol
OsO 4 in
H2 O 2

KMnO (aq.)
4 mesoor
OsO 4 in H2O 2

(iii)

KMnO (aq.)
4 rac-CH3CHOHCHOHCH3
or
OsO 4 in H2O 2

9.

(i)

(ii)

10.

(a)

(b)

hot KMnO 4

(or K 2 Cr2 O 7 )

hot KMnO 4

(or K 2 Cr2 O 7 )

not KMnO 4

(or K 2 Cr2 O 7 )

not KMnO 4

HOOCCH2CH2COOH
(or K 2 Cr2 O 7 )
Page # 44

KMnO4
Warm
cond.

11.

13.

KMnO4
Warm
cond.

12.

OH

COOH

CO2

COOH

Epoxycyclohexane
14.

Predict the products, including stereochemistry where appropriate, for the m-chloroperoxy-benzoic acid
epoxidations of the following alkenes.
(a)

H
CH3

H
C=C
CH2CH2CH3

(c) Cis-cyclodecene

(b)

CH3

CH2CH2CH3
C=C
H

(d) Trans-cyclodecene

Page # 45