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ORGANIC CHEMISTRY

TOPIC : ALKENE & ALKYNE


LECTURE NOTES
Session - 2009-10
Page # 2
Contents : Alkene/Alkyne
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
(A) By partial reduction of alkynes
(B) Dehydration of alcohol
(C) By pyrolysis of esters
Examples
Lect.
(D) By Dehalogenation of vicinal dihalides/
tetrahalides
(E) Dehydrohalogenation of alkyl halides/
vicinal dihalides
(F) Replacement of the acetylenic hydrogen
atom of terminal alkynes to form higher
alkynes
(G) Miscellaneous
Hydrolysis of carbides
Examples
Lect.
6. Chemical Reactions
(A) Electrophilic addition reaction
(B) Addition of halogen to alkenes
(C) Addition of halogen to alkynes
(D) Addition of HOX to Alkene
(E) Addition of HOX to Alkynes
Examples
Lect.
(F) Addition of Hydrogen Halides (+ HX) to Alkene
(G) Addition of Hydrogen Halides (+ HX) to Alkyne
Examples
Lect.
(H) Acid-Catalyzed Hydration
(i) For Alkene
(a) Oxymercuration-Demercuration
(b) Alkoxymercuration - demercuration
(c) Hydroboration-oxidation (Syn addition)
(ii) Acid-Catalyzed Hydration For Alkyne
Examples
Lect.
(I) Oxidation Reaction
(i) Ozonolysis (C = C, C ! C)
Examples
Lect.
(ii) Hydroxylation Reactions (Alkenes, Alkynes)
(iii) Epoxidation of Alkenes
(iv) Oxidative cleavage (Alkenes, Alkynes)
Examples
Lect.
7. Miscelleneous
(A) Addition of carbenes to Alkenes
(B) Addition of NOCl
(C) Halogenation. Allylic substitution
(D) Alkylation
Examples
Lect.
Discussion
Page # 3
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 C
1
C
3
gases
C
4
C
20
liquids
> C
20
: solids
2. Dipolemoment () cis > trans
3. Polarity cis > trans (for C
ab
=C
ab
type of alkenes)
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.
< C C = C C
Polarity increases, boiling point
increases
6. Solubility Practically insoluble cis > trans
in water but fairly Polarity increases, solubility in polar
soluble in nonpolar solvents increases.
solvents like benzene
petroleum ether, etc.
7. Stability 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 sp
3
sp
2
sp
4. % s character 25% 33% 50%
5. pKa 50 44 25
6. Electronegativity of C sp
3
(C) < sp
2
(C) < sp (C)
7. Polarity R CH
2
CH
3
R CH = CH
2
R C C
8. Rate of hydrogenation less more
9. Rate of electrophilic
addition reaction more less
10. Heat of combustion C
2
H
6
( 373) C
2
H
4
( 337 kcal) C
2
H
2
( 317 kcal)
11. Density (g/cm
3
) C
3
H
8
(0.50) C
3
H
6
(0.52) C
3
H
4
(0.67)
Page # 4
12. Structure
C = C
H
H
H H
1.08
ethene
121.2
13. Shape Tetrahedral Planar Linear
2. Rel at i ve Basi ci t y
(a)

2 2 3
: C HC : CH C H : CH CH > = >
O
(b)
OH < OR < C CR < NH <
2
CH CH < CH CH
2 2 3
- - - - - -
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
> >

C = C
R H
R H
> >

C = C
R
H
R
H
> >
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.
CH CH
2 2
CH
2
CH
2
CH
CH
| ||
CH CH
2 2
cis-Cyclooctene
trans-Cyclooctene
1
2
3
4 5
6
7
8
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. (AH = ve)
AH
hyd

stability
1
( ve sign indicates the exothermic nature of reaction)
In general, the order of stability of alkenes is :
R
2
C = CR
2
> R
2
C = CHR > R
2
C = CH
2
> RCH = CHR (trans > cis) > RCH = CH
2
> CH
2
= CH
2
Page # 5
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 Hydro-
gen: 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 (Ni
2
B nickel boride)
General Reaction R C C R
quinoline
) catalyst s ' Lindlar (
CaCO / Pd , H
3 2

Mechanism of hydrogenation :

) 1 (


) 2 (

Steps : The reactant alkyne molecules and hydrogen molecules get adsorbed at the surface of metal cata-
lyst. 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 tri pl y bonded carbon atoms from the
same side of t 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. NH
3
C C R C R C
R
R
H
H
Mechanism : Reagents Na(or Li,K) + liq NH
3
Na
+
+ e (solvated electron)
C = C

-
R
R
H NH
2

NaNH
2
+
Na
+

Note : This process of reduction is not eligible when terminal alkynes are taken.(RCCH) because terminal alkynes
form sodium salt with Na metal.
CH
3
C ! CH + Na / NH
3


CH
3
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) H
2
SO
4
/ 160C
(ii) H
3
PO
4
/ A
(iii) P
2
O
5
/ A
(iv) Al
2
O
3
/ 350C undergo loss of water molecule and form alkenes
Page # 6
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.


C 500


+
# 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 :
1.
Hexyne 3
CH CCH C CH CH
3 2 2 3

) addition syn (
CaCO / Pd / H or
) 2 P ( B Ni / H
3 2
2 2


2. CH
3
CH
2
C C CH
2
CH
3

) ( NH / Na
3
!

3.
CH OH
2

CH
2
( ) I
Minor
+
CH
3
( ) II
Major
CH OH
2

4. If the starting material is labelled with deuterium as indicated, predict how many deuterium will be present in
the major elimination product ?
Page # 7
(a)
CD
3
HO

A
H SO
2 4
CD
3
HO


+
H
CD
3
H O
2
+


O H
2

(b)
CH
3
HO
D
D D
D

A
H SO
2 4

CH
2
D
D
D
D
+
CH
3
D
D
D
(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 :
3, 3 dimethyl 2 butanol

+
H
..................

O H
2 ....................

Migration
.....................
(A) (B) (C)
oxonium ion 2
0
carbocation 3
0
carbocation

-H
+

-H
+
(E) (D)
Alkene Alkene
Ans. (A) =
CH
3
C CH CH
3
CH
3
CH
3
OH
2
+
(B) =
CH
3
C CH CH
3
CH
3
CH
3
+
(C) =
CH
3
C CH CH
3
CH
3
+
CH
3
(D) =
CH
3
C C CH
3
CH
3
CH
3
(E) =
CH
3
C CH CH
2
CH
3
CH
3
Major product is (D) Minor product is (E)
6. CH
3
CH
2
O C
O
CH
2
CH
3

A
ethene + propanoic acid
7. Ph CH
2
C
O
O CH
2
CH
2
CH
3

A
propene + Ph CH
2
COOH
8.
O
CH
3

O C CH
3

A
Page # 8
9.
O
O
O C CH CH
2 3

O
C H
2 5

A
ethene +
COOH
+ CH
3
CH
2
COOH
10.
Et
H
OH
Me
H
CH
3


H
COOH CH
3

A
Et
H
O C CH
3
Me
O
H
CH
3

A
+ CH
3
COOH
(D) 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) NaNH
2
(iii) tBuOK
+
in

t-BuOH (Hoffmann)
General reaction :
X H
| |
C C
| |

+ KOH

alcohol

O H KX C C
| |
2
+ + =
Mechanism

+ B H +
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
| |
C C
| |
Br


NaI
or Zn, CH COOH
3
C C
Mech.
C C
Br
Br


Zn
C C
Br
ZnBr


C C + ZnBr
2
(ii) CH
3
CHBr CH
2
Br
|
|
.
|

\
|

solvent as OH H C
or COOH CH
dust Zn
5 2
3
CH
3
CH = CH
2
Mech.
With NaI in acetone :
Page # 9


+ IX
It involves an antielimination of halogen atoms
Remarks
(1) Both are E2 elimination.
(2) Both are stereospecific antielimination.
e.g. CH
3
CHBr CHBr CH
3

Acetone
Na

I
CH
3
CH = CH CH
3
Method of preparation of alkynes
(A) Dehalogenation of tetrahaloalkane & Trihaloalkanes
General Reaction R C C R' + 2Zn X
2
CHCl
3
+ 6Ag + Cl
3
CH

A
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.
General Reaction
dibromide vic A
Br Br
NaBr 2 R C C R R C C R Br CHR RCH
H H
2
NaNH 2
|
|
|
|
2

+ + =
The dehydrohalogenations occur in two steps, the first yielding a bromoalkene and the second, the alkyne.
Mechanism :
Step 1
HN + RCCR

Br Br
Br
H
H
H
+
H
C C
R
R
H
+ HNH + Br

Amide ion
(The strongly
basic amide ion
brings about an
E2 reaction.)
Bromoalkene Ammonia Bromide
ion
vic-Dibromide
Step 2

Br
C C
R
R
H
Bromoalkene
(A second E2 reaction
produces the alkyne)
:N H
-
+
|
H
..
Amide ion



-
R C C R + H N H + :Br:
..
|
H
..
Alkyne
Ammonia
bromide
ion
From vicinal/Geminal Dihalides (2HX)
Step 1 Step 2
Page # 10
(1) Reactant
(2) Nature of Elimination E2 E2
(3) Rate of E2 r
1
> r
2
(anti elimination) (anti elimination)
Reagents
(1) NaNH
2
, or , LiNH
2
, or , KNH
2
(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) RC C H + CH
3
MgBr
Ether
RC = C MgBr

X ' R
R C C R
Sodium ethynide and other sodium alkynides can be prepared by treating terminal alkynes with sodium
amide in liquid ammonia :
CH
3
C C H + NaNH
2

3
NH . liq
NH
3
+ CH
3
C C CH
2
CH
3
CH
3
C C H
Metal Na
+ H
2
+
3 3
3
CH CH C C CH
|
CH

H C C H 2CH
4
+ BrMg C C MgBr H
5
C
2
C C C
2
H
5
(D) By hydrolysis of carbides
CaC
2
+ 2HOH C
2
H
2
+Ca(OH)
2
MgC
2
+ 2HOH C
2
H
2
+Mg(OH)
2
Mg
2
C
3
+ 4HOH CH
3
C CH + 2Mg(OH)
2
(E) BY Kolbe's Electrolysis
Formation of alkene
Page # 11
Formation of alkyne
EXAMPLES :
Identify the product in the following reactions :
1.

acetone / NaI
H
H
CH
3
H C
3
2.

acetone / NaI
3. What are the various product due to loss of HBr from
Ans. ,
CH
3
CH
3
(minor)
,
4. What are the major products of dehydrohalogenation of :
(i) CH
3
CH
2
CH
2
CH
2
CH
2
Cl (ii)
Cl
|
CH CH CH CH CH
3 2 2 3

(iii)
Cl
|
CH CH CH CH CH
3 2 2 3
(iv)
Cl
|
CH C CH CH
|
CH
3 2 3
3

(v)
3
3 3
CH Cl
| |
CH CH CH CH
(vi)
3 3
3 3
CH CH
| |
CH C CH CH
|
Cl

Ans. (i) gives CH
3
CH
2
CH
2
CH = CH
2
, (ii) & (iii) = CH
3
CH
2
CH = CHCH
3
(iv) & (v) = (vi) =
5. Identify the major (satytzeff) and minor (Hofmann) product of dehydrochlorination of :
Page # 12
Ans.
6.

2
NaNH
CH CH
7. CH
3
CHCl
2


2
NaNH
CH CH
8.

2
NaNH
CH
3
C CH
9. CH
3
CH
2
CHCl
2


2
NaNH
CH
3
C CH
10. CH
3
CCl
2
CH
3


2
NaNH
CH
3
CCl = CH
2

11. CH
3
CH
2
CH
2
CHCl
2


2
NaNH
CH
3
CH
2
C CH
12.

2
NaNH
CH
3
CH
2
C CH
13. CH
3
CH
2
CCl
2
CH
3

2
NaNH
CH
3
CH
2
C CH
14.

2
NaNH
CH
3
CH
2
C CH
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.
Sol.
CH
3
C CH
2
CHBr
2
CH
3
CH
3
( ) I
CH
3
C CH CH
2
CH
3
CH
3
( ) II
Br Br
CH
3
C C CH
3
CH
3
CH
3
( ) III
Br
Br
17. Show the product in the following reaction
CH
CH
3
CH
2
Br Br
EtOK
EtOH
?
Page # 13
Sol.
C CH
CH
3
18. 1, 1 dibromopentane on reaction with fused KOH at 470K gives 2 pentyne
CH CH CH CH CH
2 2 2 3
Br
Br
fused KOH
470 K
3 2 3
CCH C CH CH

1, 1 dibromo pentane 2 pentyne
Give the mechanism of this rearrangement.
Ans. Mech.
H C C CH
2
CH CH
2 3
Br
Br H
H
-OH
C C
H H
Br
CH
2
CH CH
2 3
-OH
H C C CH
2
CH
3
H
H
-OH
C
H C C CH
2
CH
3
H
C

H C C CH
2
CH
3
H
H
C
OH
H C C CH
2
CH
3
H
C
H

H O
2
OH
H C C CH
2
CH
3
H
C
H C C CH
2
CH
3
H
C

H OH
OH
H C C CH
2
H
C
H
CH
3
2 pentene
19.
Br
Br HCH C CH CH CH CH CH CH
C 160 110
oil eral min
NaNH
2
|
2 3
CCl
Br
2 2 3
2
4
2

=
CH
3
CH
2
C CH
20.
Page # 14
6. Chemical Reactions :
Due to presence of weak t electrons in alkene and alkyne, it well go for electrophilic reaction. Now question
is electrophilic addition or electrophilic substitution ?
In electrophilic substitution reaction, one o bond is broken and a new o- bond between one of the doubly
bonded carbon atoms and the electrophilic is formed. Since the bond energes of the o bond broken and the
new o 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 t-bond (251 KJ mol
1
) is broken and two
strong o bonds (2 347 = 694 KJ mol
1
) are formed. The overall reaction is accompnied by a release of about
694-251 = 443 KJ mol
1
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 t 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 # 15
(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)
) m (
G
+
. .
CH = CH
2
>> CH
2
= CH
2
(reactivity)
!
2
NH
. .
CH = CH
2
(enamine)
!R O C = C
. .
. .
(vinyl ether)
"H O C = C

. .
. .
(enol)
tauto. C C

O
(iii) ERG CH = CH
2
> CH
2
= CH
2
> EWG CH = CH
2
(a)
) ether vinyl (
CH CH O CH
2 3
= > CH
2
= CH
2
>
) ile acrylonitr (
CN CH CH
2
=
(b) CH = CH
2
CH = CH
2
CH = CH
2
CH = CH
2
CH = CH
2
CH = CH
2
CH = CH
2
CH = CH
2
CH = CH
2
CH = CH
2
CH = CH
2
CH = CH
2
CH = CH
2
CH = CH
2
CH = CH
2
> CH
2
= CH
2
(c) < CH
2
= CH
2
(d)

CH = CH
2
ERG

CH = CH
2
ERG

CH = CH
2
ERG

CH = CH
2
ERG

CH = CH
2
ERG

CH = CH
2
ERG

CH = CH
2
ERG

CH = CH
2
ERG

CH = CH
2
ERG

CH = CH
2
ERG

CH = CH
2
ERG

CH = CH
2
ERG

CH = CH
2
ERG

CH = CH
2
ERG

CH = CH
2
ERG
>

CH = CH
2

CH = CH
2

CH = CH
2

CH = CH
2

CH = CH
2

CH = CH
2

CH = CH
2

CH = CH
2

CH = CH
2

CH = CH
2

CH = CH
2

CH = CH
2

CH = CH
2

CH = CH
2

CH = CH
2
>

CH = CH
2
EWG

CH = CH
2
EWG

CH = CH
2
EWG

CH = CH
2
EWG

CH = CH
2
EWG

CH = CH
2
EWG

CH = CH
2
EWG

CH = CH
2
EWG

CH = CH
2
EWG

CH = CH
2
EWG

CH = CH
2
EWG

CH = CH
2
EWG

CH = CH
2
EWG

CH = CH
2
EWG

CH = CH
2
EWG
(f) Electrophilic addition in C ! C
C ! C

O
u N E


O
u N E

(i) + X
2
(ii) + HOX
(iii) + HX
(iv) + H
2
O/H
+
(B) Additon of halogen to alkenes (Halogenation)
(a) General Reaction:- R CH = CH R

2
X
R CHX CHX R
Page # 16
C = C + X
2

addition anti usually
X
| |
C C
| |
X

(b) Mechanism
Step-1 Formation of a halonium ion
C = C : X +
. .
. .
: X
. .
. .
C C
Halonium ion
X
+
+ : X :
. .
. .
-
Step-2 Opening of the halonium ion.
O
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:- Br
2
> Cl
2
(F
2
, I
2
not used)
Solvents:- CCl
4
best
CCl
4
CCl
4
CCl
4
CCl
4
CCl
4
CCl
4
CCl
4
CCl
4
CCl
4
CCl
4
CCl
4
CCl
4
CCl
4
CCl
4
, CHCl
3
(H
2
O, MeOH, EtOH, CH
3
COOH)
(d)Remarks :
(i) F
2
is not added because F
+
is never generated. Morever reaction is explosive giving CO
2
& H
2
O
(ii) I
2
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 F
2
(explosive) > Cl
2
> Br
2
> I
2
)
(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 Addition Product
Cis Syn. meso type
Cis Anti d ! type
Trans Syn. d ! type
Trans Anti meso type
(C) Addition of halogen to alkynes ( C ! C )
(a) R C C R
1
2
r ) 1 (
.) leq ( Br

Br
Br
R C = C R
(Trans-dihalide)

Br
Br
R C = C R
(Trans-dihalide)

Br
Br
R C = C R
(Trans-dihalide)

Br
Br
R C = C R
(Trans-dihalide)

Br
Br
R C = C R
(Trans-dihalide)

Br
Br
R C = C R
(Trans-dihalide)

Br
Br
R C = C R
(Trans-dihalide)

Br
Br
R C = C R
(Trans-dihalide)

Br
Br
R C = C R
(Trans-dihalide)

Br
Br
R C = C R
(Trans-dihalide)

Br
Br
R C = C R
(Trans-dihalide)

Br
Br
R C = C R
(Trans-dihalide)

Br
Br
R C = C R
(Trans-dihalide)

Br
Br
R C = C R
(Trans-dihalide)

Br
Br
R C = C R
(Trans-dihalide)

2
2
r ) 2 (
.) leq ( Br

Br

Br

Br
Br
R C C R
(Tetrahalide)

Br
Br
R C C R
(Tetrahalide)

Br
Br
R C C R
(Tetrahalide)

Br
Br
R C C R
(Tetrahalide)

Br
Br
R C C R
(Tetrahalide)

Br
Br
R C C R
(Tetrahalide)

Br
Br
R C C R
(Tetrahalide)

Br
Br
R C C R
(Tetrahalide)

Br
Br
R C C R
(Tetrahalide)

Br
Br
R C C R
(Tetrahalide)

Br
Br
R C C R
(Tetrahalide)

Br
Br
R C C R
(Tetrahalide)

Br
Br
R C C R
(Tetrahalide)

Br
Br
R C C R
(Tetrahalide)

Br
Br
R C C R
(Tetrahalide)

(b) Rate:- r
2
> r
1
(Criteria : Stability of carbocation)
Page # 17
Br
Br
R C C R
+
+

Br
(Alkyl C )
Br
Br
R C C R
+
+

Br
(Alkyl C )
Br
Br
R C C R
+
+

Br
(Alkyl C )
Br
Br
R C C R
+
+

Br
(Alkyl C )
Br
Br
R C C R
+
+

Br
(Alkyl C )
Br
Br
R C C R
+
+

Br
(Alkyl C )
Br
Br
R C C R
+
+

Br
(Alkyl C )
Br
Br
R C C R
+
+

Br
(Alkyl C )
Br
Br
R C C R
+
+

Br
(Alkyl C )
Br
Br
R C C R
+
+

Br
(Alkyl C )
Br
Br
R C C R
+
+

Br
(Alkyl C )
Br
Br
R C C R
+
+

Br
(Alkyl C )
Br
Br
R C C R
+
+

Br
(Alkyl C )
Br
Br
R C C R
+
+

Br
(Alkyl C )
Br
Br
R C C R
+
+

Br
(Alkyl C )
> R C = C R
+
+
Br
(Vinyl C )
R C = C R
+
+
Br
(Vinyl C )
R C = C R
+
+
Br
(Vinyl C )
R C = C R
+
+
Br
(Vinyl C )
R C = C R
+
+
Br
(Vinyl C )
R C = C R
+
+
Br
(Vinyl C )
R C = C R
+
+
Br
(Vinyl C )
R C = C R
+
+
Br
(Vinyl C )
R C = C R
+
+
Br
(Vinyl C )
R C = C R
+
+
Br
(Vinyl C )
R C = C R
+
+
Br
(Vinyl C )
R C = C R
+
+
Br
(Vinyl C )
R C = C R
+
+
Br
(Vinyl C )
R C = C R
+
+
Br
(Vinyl C )
R C = C R
+
+
Br
(Vinyl C )
(c) Nature of Addition:- Anti in both step
R C C R
Anti ) 1 (
.) leq ( X
2

. Syn ) 2 (
D
2

R C C R
] catalyst , lindlar [
. Syn ) 1 (
CaCO / Pd / D
3 2

(D) Addition of HOX to Alkene
(a) General Reaction = C C
| |
+ HOX
X
| |
C C
| |
OH

(b) Reagents
(i) X
2
+ H
2
O HOX + HX
(ii) HOX
Remarks : Anti adition
No rearrangement
No carbocation
Bridged Carbocation
As H
2
O 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.
(E) Addition of HOX to Alkynes
(a) R C C H

.) leq ( HOX

X
R C = CH
OH enol
.) eq 1 (
HOX



H O
2
Page # 18
R C
O
CH
2
X R C
O
CHX
2
10% (minor) 90% (major)
[o-Haloketone] [o, o-Dihaloketone]
(b) Remakrs :
# Two molecules of HOX can be added, the end product is o, o-Dihaloketone.
# The intermediate product is an enol which gives a minor product o-haloketone.
Extention :
R C
O
CHX
2

KOH
R C
O
CH(OH)
2

O H
2
R C CHO
O
(major product)
Examples :
Ex.1 CH
3
CH = CH
2

4 2
CCl / Br
CH
3
CHBr CH
2
Br
Ex.2 CH
3
CH = CH
2


4
CCl / Br I

Ex.3 CH
3
CH = CH
2


BrCl

Ex.4 CH
3
CH = CH
2


Cl I

Ex.5

2
Br Br
Br
H
H
Ex.6
Me

2
Br Br
Br
Me
H
Ex.7
H H
CH
3
cis
C = C
CH
3
cis
C = C
CH
3
cis
C = C
CH
3
cis
C = C
CH
3
cis
C = C
CH
3
cis
C = C
CH
3
cis
C = C
CH
3
cis
C = C
CH
3
cis
C = C
CH
3
cis
C = C
CH
3
cis
C = C
CH
3
cis
C = C
CH
3
cis
C = C
CH
3
cis
C = C
CH
3
cis
C = C
CH
3

2
Br

Me
Me
(cis)
H
H
Me
Me
X
X
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
(d + ! mixture)
Ex.8
H
H
CH
3
trans
C = C
CH
3
trans
C = C
CH
3
trans
C = C
CH
3
trans
C = C
CH
3
trans
C = C
CH
3
trans
C = C
CH
3
trans
C = C
CH
3
trans
C = C
CH
3
trans
C = C
CH
3
trans
C = C
CH
3
trans
C = C
CH
3
trans
C = C
CH
3
trans
C = C
CH
3
trans
C = C
CH
3
trans
C = C
CH
3

2
Br
Me
Me
(trans)
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
Me
Me
X
X
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
(meso)
Ex.9

2
Br
Ph CHBr CHBr Ph
(d + !) mix
Ex.10

Br I

H
H
Ph
Ph
I
Br
H
H
Ph
Ph
I
Br
H
H
Ph
Ph
I
Br
H
H
Ph
Ph
I
Br
H
H
Ph
Ph
I
Br
H
H
Ph
Ph
I
Br
H
H
Ph
Ph
I
Br
H
H
Ph
Ph
I
Br
H
H
Ph
Ph
I
Br
H
H
Ph
Ph
I
Br
H
H
Ph
Ph
I
Br
H
H
Ph
Ph
I
Br
H
H
Ph
Ph
I
Br
H
H
Ph
Ph
I
Br
H
H
Ph
Ph
I
Br

Page # 19
Ex.11 CH
2
= CH
2


H / HOCl

OH

Cl
CH CH
2 2
CH CH
2 2
CH CH
2 2
CH CH
2 2
CH CH
2 2
CH CH
2 2
CH CH
2 2
CH CH
2 2
CH CH
2 2
CH CH
2 2
CH CH
2 2
CH CH
2 2
CH CH
2 2
CH CH
2 2
CH CH
2 2
Ex.12 CH
3
CH = CH
2

+
H / HOBr
CH
3

OH

Br
CH CH
2
CH CH
2
CH CH
2
CH CH
2
CH CH
2
CH CH
2
CH CH
2
CH CH
2
CH CH
2
CH CH
2
CH CH
2
CH CH
2
CH CH
2
CH CH
2
CH CH
2
Ex.13 CH
3
CH = CH
2
impurities
K NaCl,
O H / Br
2 2
I


G
|
CH CH CH
|
Br
2 3

4 products are formed.
G = OH

, Br

, I

, Cl

Ex.14

Me

O H / Br
2 2
+ H OH
Me Br
Ex.15


H / HOCl
Cl
CH CH
3
OH
Ph
Me

C 60 50
H NaO
18

OH
CH CH
3
O
Ph
Me

18
---------------

A
OH
CH CH
3
OH
Ph
Me

18
Ex.16 Ph C C CH
3

Excess
Cl
2

Ex.17 CH
3
C CH ) R (
.) leq (
Ni / D
) Q (
.) leq (
Cl
2 2

Ex.18 Ph C C CH
3

) excess (
HOCl
Ph C
O
C Cl

Cl
CH
3
Ex.19 CH
3
C

H
CH
3
C CH

KOH
) Excess (
HOBr
CH
3
C

H
CH
3
C
O
CHO
Ex. 20
Ex.21
Ex. 22
Page # 20
Ex. 23
Ex. 24 + Br
2


2 2
Cl CH

Ex. 25 + Br
2


2 2
Cl CH
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 # 21
Markovnikovs Rule :
When reagent (like: HX, H
2
O) 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 sp
2
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 : -
-
CH
3
CH = CH CH
2
CH
3
+ HCl

Not Regioselective because intermediate
is only sec. carbocation.
(G) Addition of Hydrogen Halides (+ HX) to Alkyne
(a) General Reaction R C C H
1
r
) dark ( HBr

H
Br
R C = C H
(MK)
R C = C H
(MK)
R C = C H
(MK)
R C = C H
(MK)
R C = C H
(MK)
R C = C H
(MK)
R C = C H
(MK)
R C = C H
(MK)
R C = C H
(MK)
R C = C H
(MK)
R C = C H
(MK)
R C = C H
(MK)
R C = C H
(MK)
R C = C H
(MK)
R C = C H
(MK)
2
r
HBr

Br
Br
R C CH
3
R C CH
3
R C CH
3
R C CH
3
R C CH
3
R C CH
3
R C CH
3
R C CH
3
R C CH
3
R C CH
3
R C CH
3
R C CH
3
R C CH
3
R C CH
3
R C CH
3
(b) Mechanism:- R C C H
H
r
+
1
R C C H
H
r
+
1
R C C H
H
r
+
1
R C C H
H
r
+
1
R C C H
H
r
+
1
R C C H
H
r
+
1
R C C H
H
r
+
1
R C C H
H
r
+
1
R C C H
H
r
+
1
R C C H
H
r
+
1
R C C H
H
r
+
1
R C C H
H
r
+
1
R C C H
H
r
+
1
R C C H
H
r
+
1
R C C H
H
r
+
1

C Vinyl
] CH C R [
2
-
Br
-
Br
-
Br
-
Br
-
Br
-
Br
-
Br
-
Br
-
Br
-
Br
-
Br
-
Br
-
Br
-
Br
-
Br

Br
R C = CH
2
Vinyl halide
2
r
H

Br
R CH CH
2
Less stable
+
R CH CH
2
Less stable
+
R CH CH
2
Less stable
+
R CH CH
2
Less stable
+
R CH CH
2
Less stable
+
R CH CH
2
Less stable
+
R CH CH
2
Less stable
+
R CH CH
2
Less stable
+
R CH CH
2
Less stable
+
R CH CH
2
Less stable
+
R CH CH
2
Less stable
+
R CH CH
2
Less stable
+
R CH CH
2
Less stable
+
R CH CH
2
Less stable
+
R CH CH
2
Less stable
+
+

Br
R C CH
3
more stable
+
R C CH
3
more stable
+
R C CH
3
more stable
+
R C CH
3
more stable
+
R C CH
3
more stable
+
R C CH
3
more stable
+
R C CH
3
more stable
+
R C CH
3
more stable
+
R C CH
3
more stable
+
R C CH
3
more stable
+
R C CH
3
more stable
+
R C CH
3
more stable
+
R C CH
3
more stable
+
R C CH
3
more stable
+
R C CH
3
more stable
+
Br
---------------
(c) Remarks:-
Page # 22
(1) MK Addition in both steps.
(2) r
2
> r
1
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 C ! C addition
(1) Reactivity order C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C > C C
e cloud is
cylindrical
and difficult
to break

(2)

C (Stability)
(alkyl C )
C C
+
+
E
C C
+
+
E
C C
+
+
E
C C
+
+
E
C C
+
+
E
C C
+
+
E
C C
+
+
E
C C
+
+
E
C C
+
+
E
C C
+
+
E
C C
+
+
E
C C
+
+
E
C C
+
+
E
C C
+
+
E
C C
+
+
E
>
(vinyl C )
C = C
+
+
E
C = C
+
+
E
C = C
+
+
E
C = C
+
+
E
C = C
+
+
E
C = C
+
+
E
C = C
+
+
E
C = C
+
+
E
C = C
+
+
E
C = C
+
+
E
C = C
+
+
E
C = C
+
+
E
C = C
+
+
E
C = C
+
+
E
C = C
+
+
E
(3) For H
2
/Ni (R.O.) C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C < C C
(4) AH
hydrogenation
(overall) C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C < C C
# Heat of hydrogenation per t-bond ?
C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C C = C < C C
(d) Reactivity Order:- R CH CH R = > > R C C R
Free Radical Addition of HBr:- Kharasch Effect or Peroxide Effect
General Reaction R CH = CH
2

v h / O R / HBr
2 2
R CH
2
CH
2
Br
e.g.
Octene 1
2 13 6
CH CH H C n

=


peroxides BrCCl /
3

onane trichloron 1 , 1 , 1 Bromo 3
Br
|
CCl CH CH H C n
3 2 13 6


Octene 1
2 13 6
CH CH H C n

=

2 2
O R / HBr
nC
6
H
13
CH
2
CH
2
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 t bond.
(5) In the last step alkyl radical abstracts H from HBr and AMK product is obtained.
Page # 23
Examples :
1. Why do we get AMK product ?
Ans. 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 ?
Ans. In chain propagation (iii) steps:-
R CH = CH
2
+
-
X R CH
-
CH
2
X + AH
R
R CH = CH
2
+
-
F R CH
-
CH
2
F exo
R CH = CH
2
+
-
Cl
R CH
-
CH
2
Cl exo
R CH = CH
2
+
-
Br R CH
-
CH
2
Br exo
R CH = CH
2
+
-
I R CH
-
CH
2
I endo
B.E.:- CF > CCl > CBr > CI
In step (iv)
R CH
-
CH
2
X + H X R CH
2
CH
2
X +
-
X + AH
R
R CH
-
CH
2
X + H F R CH
2
CH
2
X +
-
F + endo
R CH
-
CH
2
X + H Cl R CH
2
CH
2
X +
-
Cl + endo
R CH
-
CH
2
X + H Br R CH
2
CH
2
X +
-
Br + exo
R CH
-
CH
2
X + H I R CH
2
CH
2
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]
3. CH C = CH
3 2

CH
3

) dark (
HBr

C
C C C
Br
CH C = CH
3 2

CH
3

) light (
HBr

C
C C C
Br
# Light can also cleave HBr bond.
4. CH C CH = CH
3 2

CH
3
CH
3

) O R (
HBr
2 2

C
C C C C
Br

C
# R
2
O
2
accelerates cleavage of HBr bond.
CH C CH = CH
3 2

CH
3
CH
3

) dark (
HBr

C
C C C C
Br

C
5.
) light (
HBr

Br

) dark (
HBr


Br

6. Ph CH = CH
2

) O R ( HBr
2 2
Ph CH
2

CH
2
Br
Page # 24
Ph CH = CH
2

HBr

Ph C C
Br
7. CH C CH = CH
3 2
CH
3
CH
3


HBr
CH C CH CH
3 3
CH
3
CH
3

Br

8.

HBr
Br
9.

I H

I
10.

HCl
Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl
11.

Me

Me

Me

Me

Me

Me

Me

Me

Me

Me

Me

Me

Me

Me

Me

HBr
Br Br Br Br Br Br Br Br Br Br Br Br Br Br Br
12. CH
3
O CH
2
CH = CH
CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH CH
3
HCl (dry) HCl (dry) HCl (dry) HCl (dry) HCl (dry) HCl (dry) HCl (dry) HCl (dry) HCl (dry) HCl (dry) HCl (dry) HCl (dry) HCl (dry) HCl (dry) HCl (dry)
CH
3

Cl
O CH
. .
Cl
O CH
. .
Cl
O CH
. .
Cl
O CH
. .
Cl
O CH
. .
Cl
O CH
. .
Cl
O CH
. .
Cl
O CH
. .
Cl
O CH
. .
Cl
O CH
. .
Cl
O CH
. .
Cl
O CH
. .
Cl
O CH
. .
Cl
O CH
. .
Cl
O CH
. .
CH
2
CH
2

CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH
CH
3

CH CH
3
If water is taken, ether will be hydrolysed. Dry HCl is used.
13. + HCl


14. 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 # 25
15. H C C H

.) leq ( HCl
Cl

H C = CH
2
Vinyl Chloride

.) leq ( HCl
Cl
Cl

H C CH
3
gem dihalide
16. CH
2
= CH CH
2
C CH

.) leq ( HCl
CH
3

Cl
CH

CH
2
C CH
17. CH = CH C CH
Conjugated System
2

more stable product

.) leq ( HCl
Cl
CH = CH C = CH
2 2
Neoprene

Conjugated 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 + H
2
O
Mech.
Step 1 : 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 # 26
General Reaction + H
2
O + Hg
2
3
OCCH
||
O
|
|
|
.
|

\
|

THF

Hg OCCH
3
| ||
C C
O
| |
OH
|
+ COH CH
||
O
3

Hg OCCH
3
| ||
C C
O
| |
OH
|
+ + NaBH
4


H HO
| |
C C
| |

+ Hg + (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 H
2
O & Hg(CH
3
COO)
2
.
Step (B)

4
OH
NaBH


NaBH
4
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 + Hg(OAc)
2


ROH

HgOAc
| |
C C
| |
OR


4
NaBH

| |
C C
| |
H
(Markovnikov
orientation)
RO
Page # 27
(c) Hydroboration-oxidation (SYN ADDITION)
General Reaction + BH
3
.THF
ROH

H
|
H B H
| |
C C
| |


An alkene reacts with BH
3
; 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 H
2
O is not a reactant.
(2) During process of addition H comes from BH
3
& OH comes from H
2
O
2
(3) Net result is addition of H
2
O 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 BH
3
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 sp
2
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 # 28
(b) Oxidation :- Replacement of B from OH ap.
(CH
3
CH
2
CH
2
)
3
B OR R
3
B

2 2
OH
O H

3ROH + BO
3
3
Mechanism
HOOH + HO

HOO

+ H
2
O





time two steps eceding Pr
two the peat Re



3 ROH + BO
3
3
times two
steps eceding Pr
three the peat Re


ROH +



.
( i i ) Acid-Catalyzed Hydration For Alkynes
G.R. R C C H

4 4 2
HgSO / SO H
R C
O
CH
3
Mechanism:- R C C H

+2
Hg
Hg
R C = C H
+
H O
2
:
:

OH
R C = C H

Hg

4 2
SO H
OH
R C = CH
+ HgSO
2
4
R
O
C CH
3
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) CH
3
(CH
2
)
3
CH = CH
2
< CH
3
(CH
2
)
2
CH = CH CH
3


<
3
2 2 2 3
CH
|
CH C ) CH ( C H =
(b)

C = C
H
H
H C
3
CH
3
cis-2-butene
<

C = C
H
H H C
3
CH
3
trans-2-butene
<
3
2 3
CH
|
CH C C H =
(c) CH CH = CH CH
2 3
< CH = CH CH CH
2 3
< H C = CH CH
3 3
C
Page # 29
(Greater the stability of carbocation (intermediate), greater the hydration.)
EXAMPLES
1.
opene Pr
2 3
CH CH CH =


+
H , O H
2

alcohol Isopropyl
OH
|
CHCH CH
3 3
2.
butene 1 ethyl dim 3 , 3
3
2 3
3
CH
|
CH CH C CH
|
CH

=

4 2
SO H % 50

CH
| |
CH C C CH
| |
OH CH
3
3 3
3
2, 3-dimethyl-2-butanol
(major product)
H
3.
CH
3
C
H
C CH
3
CH
3



D / O D
2

CH
3
C
D
C CH
3
CH
3
OD
H
4.
CH
3
C
CH
2
CH
3
+ H
2
SO
4
CH
3
C
CH
3
CH
3
OSO H
3
83 C
0
A H O
2
CH
3
C
CH
3
CH
3
OH.
t Butyl hydrogen sulphate t butyl alcohol, bp 83
0
C
5.
butene 1 ethyl dim 3 , 3
3
2 3
3
CH
|
CH CH C C H
|
CH

=

4 2
SO H aqueous . dil

) major (
ol tan bu 2 ethyl dim 3 , 2
OH CH
| |
CH C C C H
| |
CH H
3
3 3
3

+
) or (min
butene 2 ethyl dim 3 , 2
3 3
3 3
CH CH
| |
CH C C C H

=
6.
butene 1
3 2 2
CH CHCH C H

=

4
NaBH

ol tan bu 2
CH CHCH CH
|
OH
3 2 3

7.
butene 1
3 2 2
CH CH CH CH

=

8. + enantiomer + dialkyl-and trialkylborane
+ enantiomer
Page # 30
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. C
3
H
7
CH = CH
2

THF / H O
2
Hg(OAC)
2
C
3
H
7
CH(OH)CH
2
HgOAC

NaOH /
4
NaBH
C
3
H
7
CH(OH)CH
3
(An organomercurial alcohol)
10.
CH OH
3
Hg(OAC)
2


4
NaBH
OCH
3
11.
OH


2
) OAC ( Hg

NaOH
NaBH
4 O
12.
butene 1 Dimethyl 3 , 3
CH
|
CH CH C CH
|
CH
3
2 3
3

=
O H , ) OAc ( Hg
2 2


4
NaBH
) ent rearrangem No (
ol tan bu 2 Dimethyl 3 , 3
OH CH
| |
CH CH C CH
|
CH
3
3 3
3


13.
14.
CH
|
CH C CH = CH
3
3 2
CH
|
CH C CH CH
3
3 3
CH
|
CH C CH CH OH
3
3 2 2
CH
|
CH C CH CH
3
3 3
|
|
|
|
CH
3
CH
3
CH
3
CH
3
H (dil. H SO )
+
2 4 + +
+
CH shift
3
CH C CH CH
3 3
|
|
CH
3
CH
3
OH CH
| |
CH C CH CH
3
3 3
|
CH
3
|
OH
H O
2
Hydroboration
Hg(OAc)
2
NaBH
4
( H )
oxidation
2carbocation
3carbocation
(i) Hydration with dil. H
2
SO
4
proceeds via carbocation rearrangement
(ii) Hydration with Hg(OAc)
2
, H
2
O, followed by NaBH
4
proceeds via Markonikovs rule.
(iii) Hydration with (BH
3
)
2
followed by H
2
O
2
/ OH proceeds via Anti Markonikovs rule.
Page # 31
15.
16.
H
Me

THF / BH
3

H
BH
2
H
Me


O
OH / O H
2 2

H
OH
H
Me
1 methylcyclopentene trans 2 cyclopentanol
17. Br
HBr
OH

4 2
SO H BH /THF
3
H O /OH
2 2
-

OH

HBr
Br
18. R C ! C H
.) dil ( ) A (
SO H / Hg
4 2
2 +
$%
O
OH / O H ) B (
THF BH
2 2
3
$% R CH
2
CHO
19. H C ! C H

) B /( ) A (
CH
3
CHO
20. Ph C ! C CH
2
CH
3

4 2
2
SO D
Hg ) 1 (

+
$%

O

OD / O D ) 2 (
THF BH ) 1 (
2 2
3
$%

O

OD / O D ) 2 (
THF BD ) 1 (
2 2
3
$%
Common Sense : D
2
SO
4
D
2
SO
4
Present in D
2
O
O O
OD OD
Present in D
2
O
21. Ph C CH

+
O H / Hg
3
2
Acetophenone $%
(Reactant) |
OH
|
Ph C = CH
2
Retrosynthesis
|
Ph C CH
Page # 32
22.

+
4 2
2
SO H / Hg



OH /
2
I
+ CHI
3

23. CH
3
C ! C CH
3
O

HOO
THF / BH
3


O
OH / I
2
CH
3
CH
2
COOH . ppt Yellow +
3 3
) s ( CaO / NaOH
CH CH
Alkadines (conjugated) :
E
+
add
n
:
Mechanism :
Page # 33
With a non-classical C
+
, the product is always a trans-alkene (anti-addition).
Ex.
(1) H
2
C = CH CH = CH
2

) t , r (
HBr

(trans) > (cis) .........classical.
Page # 34
(2)
) t , r (
) eq 1 ( HCl

+ + +
(1,2) (1, 6) > (1, 4) > (1, 2)'.
(3) H
3
C CH = CH CH = CH
2


HCl
Alkenes = (I/I') ~ II' > II. ...........on the basis of alkene stability.
(4)
eq 1
HOX


6. Miscellaneous
(A) Addition of carbenes to Alkenes :
Methylene is the simplest of the carbenes : uncharged, reactive intermediates that have a carbon atom with
two bonds and two nonbonding electrons. Like borane (BH
3
), 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 (CH
2
N
2
) gives nitrogen gas and methylene.
ne diazometha
H C N N : CH N N :
2
. .
2
. .
(

= =
O

O


light t ultraviole or Heat

N + :C
2
H
H
Methylene
There are two difficulties with using CH
2
N
2
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
CH
2
N
2
is so reactive that it inserts into C H bonds as well as C = C bonds.
Structure :
Page # 35

(a) H
2
C | +
|
|
C H
2
(b) Singlet triplet
(c) sp
2
/120/bent
(d) Diamagnetic paramagnetic
(e) 6e

/e

deficient (electrophilic) (electrophilic)
Carbene is an E

species. So it gives E

addition reactions with alkenes/ alkynes
ex.

A / N CH
2 2

CH
3
CH=CH
2


A = = / O C CH CH
3

(B) Addition of NOCl
CH
3
CH = CH
2

NaCl

(C) Halogenation. Allylic substitution
General Reaction X
2
= Cl
2
, Br
2
NBS = N-Bromosccinimide NCS = N-Chlorosuccinimide
(D) Alkylation :
General Reaction = C C
| |
+ R H
acid

R H
| |
C C
| |

Examples :
1.

v

O
sh : N N H
. .
C
2
Page # 36
Propene
+ +
+
2.
) opene (Pr
opylene Pr
2 3
CH CH CH =


C 600 Cl ,
2
) propene 1 Chloro 3 (
chloride Allyl
2 2
CH CH CH Cl

=
3.
e Isobutylen
2 3
3
CH C CH
|
CH
= +
e tan Isobu
CH
|
H C CH
|
CH
3
3
3



4 2
SO H

e tan en Trimethylp 4 , 2 , 2
3
3 2 3
3 3
CH H
| |
CH C CH C CH
| |
CH CH


4. (a)
Butene 2
3 3
CHCH CH CH

= +
ne Diazometha
2 2
N CH
light

(b) + CHBr
3


O H / NaOH
2
5. Show how the insertion of methylene into a bond of cyclohexene can produce the following.
(a)
CH
3
(b)
CH
3
(c) norcarane,
6. Assertion (A):- Propene (CH
3
CH = CH
2
) undergoes allylic substitution.
Reason (R) : CH
2
= CHCH
2
(allylic) free radical is stabilised by resonance.
Ans. (A)
7.
Cyclohexene
+ NBS

3-Bromocyclohexene
Br
1. F.R Allylic substitution :
H
2
CCH=CH
2
) 1 (
. t . r / Br
2

........... E

addition (or F.R. addition)
Page # 37
) 2 (
C 500 400 / Br
2

.......... Allylic substitution
) 3 (
O R / NBS
2 2


X
2
= Br
2
/Cl
2
# (2)
2
X
) C 500 (

A


[H
2
-
C
CH=CH
2
] + HX

2
X
............... (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) H
2
CCH=CH
2

Br
) rds (

H
2
CCH=CH
2
CH + HBr
(iv) + HBr

+ Br
2
(low conc.)
(v) H
2
-
C
CH=CH
2
+ Br
2


+ Br
NBS is used to provide very slow but steady supply of Br
2
. If Br
2
is used in excess then addition reaction
takes place but if NBS is used then in one step only 1 molecule of Br
2
is formed which is insufficient to give
addtion product so the substitution product is the major product.
Addition always takes place when Br
2
is in excess.
# Halolactonisation : [unsaturated acid + X
2
+ basic med.]
H
2
C = CH CH
2
CH
2
CH
2
COOH
2
3
X
NaHCO

Page # 38

# Hydrolysis of vinyl ethers :
Vinyl ethers = Alkoxy alkenes
= Highly reactive alkene (E

addition)



H
+ HOR


18
3
O H
Mechanism



H



H

H
3
CCH=O
18


H

ex. An alkene X (C
5
H
10
O) on hydrolysis with dil H
2
SO
4
produces Y and Z. Both give iodoform test (+ve) X is 10
15
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 KMnO
4
When alkene & alkyne heated with KMnO
4
in acidic or in alkaline medium ; following changes takes place.
Terminal = CH
2

] O [
CO
2
+ H
2
O
Page # 39
Terminal CH

] O [
CO
2
+ H
2
O
Non Terminal alkene = CHR
] O [
RCOOH
=
] O [

C R
] O [
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.
(a) General Reaction
C C
R
R'
H
R
+ O
3

O O
O
C C
R
R
R'
H
Ozonide

(CH ) S
3 2
C O
R
R
+
O C
R'
H
Ketone
O H ) 2 (
O ) 1 (
2
3

+ R'COOH
(Oxidative ozonolysis)

O H / S Me
or COOH CH
or O H / Zn ) 2 (
O ) 1 (
2 2
3
2
3

+ (reductive ozonolysis)
(1) O
(2) LiAlH /NaBH
3
4 4
+ R'CH
2
OH
(reductive ozonolysis)
(b) Mechanism
C
O
O
O
O
+
-

O
O
O
C
C
Molozonide (Primary ozonide)
O
O
O
C
C

C
O
O
O
C
+
-
Ozonide
Page # 40
O O
O
C C
R
R
R'
H
CH - S - CH
3 3
dimethyl sulfide

C O
R
R
+
O C
R'
H
+CH
3
S CH
3
O
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.
CH
3
C CCH
2
CH
2

O H ) 2 (
O ) 1 (
2
3

CH
3
COOH + CH
3
CH
2
COOH
CH
3
CH
2
CH
2
C CH
O H ) 2 (
O ) 1 (
2
3

CH
3
CH
2
CH
2
COOH + CO
2
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 :
1.
CH
3
H
Conc. KMnO
4
- OH
O
O
H
CH
3
O
O
O
CH
3
(not isolated)
2.
CH
3
H
(i) O
3
(ii) (CH ) S
3 2

O
O
H
CH
3
3.

3
O
+
-
KMnO /OH
4 + R'COOH


H / KMnO
4 + R'COOH
A

A

/ H / CrO , or
/ H / O Cr K
3
7 2 2
+ R'COOH
cold
KMnO . dil
4


4
O HI
+
Page # 41
4.
H
O
OH
H OH
O
Lemienx Reagent
(KMnO + Na O )
4 4
I
H O I
4
5.

TFPAA ) 1 (

O H
2
H OH
H OH

4
HIO
no reaction
6.

4
OsO ) 2 (

O H
2
H OH
H OH

4
HIO
O
O
7. How will you distingnish cis, trans cyclohexane-1, 2-diol.
H OH
H OH
cis

3 4
AgNO / HIO
O
O
+ AgIO
3
+ . ppt
H OH
H OH
trans

3 4
AgNO / HIO
No reaction
8.
(i) O
3
(ii) (CH ) S
3 2
CH
3
CH
2
CHO + CH
3
(CH
2
)
4
CHO (65%)
3 - nonene
9.
H
H
(i) O
3
(ii) (CH ) S
3 2

C
H
H
C
O
H
O
H
+
H
CHO
H
CHO
10.
(i) O
3
(ii) (CH ) S
3 2
CHO
CHO
O
(ii) Hydroxylation Reactions of alkenes
(a) General Reaction
(b) Mechanism:-
(1) With Bayer's Reagent:-
Page # 42

O H 2
2
+
) colorless (
) 5 (
MnO H
4 3
+
(2) With OsO
4
/H
2
O/NaHSO
3
:-
Os
(48)
O
O
OO
R CH = CH R
O
O
OO
R CH = CH R
O
O
OO
R CH = CH R
O
O
OO
R CH = CH R
O
O
OO
R CH = CH R
O
O
OO
R CH = CH R
O
O
OO
R CH = CH R
O
O
OO
R CH = CH R
O
O
OO
R CH = CH R
O
O
OO
R CH = CH R
O
O
OO
R CH = CH R
O
O
OO
R CH = CH R
O
O
OO
R CH = CH R
O
O
OO
R CH = CH R
O
O
OO
Os
(Cyclic
osmate
ester)
OO
OO
R CH CH R
OO
OO
R CH CH R
OO
OO
R CH CH R
OO
OO
R CH CH R
OO
OO
R CH CH R
OO
OO
R CH CH R
OO
OO
R CH CH R
OO
OO
R CH CH R
OO
OO
R CH CH R
OO
OO
R CH CH R
OO
OO
R CH CH R
OO
OO
R CH CH R
OO
OO
R CH CH R
OO
OO
R CH CH R
OO
OO
R CH CH R

O H 2
2
+
) 6 (
OsO H
4 2
+
(3) Epoxidation/Hydrolysis:-
RCO
3
H = Peroxy acid
HCO
3
H = PFA (Performic acid)
CH
3
CO
3
H = PAA (Peracetic acid)
Ph CO
3
H = PBA

CO H
3

Cl

CO H
3

Cl

CO H
3

Cl

CO H
3

Cl

CO H
3

Cl

CO H
3

Cl

CO H
3

Cl

CO H
3

Cl

CO H
3

Cl

CO H
3

Cl

CO H
3

Cl

CO H
3

Cl

CO H
3

Cl

CO H
3

Cl

CO H
3

Cl
= MCPBA (Metachloro perbenzoic acid)
CF
3
CO
3
H = TFPAA (Trifluoro peracetic acid)
H
C
R
18
O
O
O
. .
R CH = CH R
O
O
O
. .
R CH = CH R
O
O
O
. .
R CH = CH R
O
O
O
. .
R CH = CH R
O
O
O
. .
R CH = CH R
O
O
O
. .
R CH = CH R
O
O
O
. .
R CH = CH R
O
O
O
. .
R CH = CH R
O
O
O
. .
R CH = CH R
O
O
O
. .
R CH = CH R
O
O
O
. .
R CH = CH R
O
O
O
. .
R CH = CH R
O
O
O
. .
R CH = CH R
O
O
O
. .
R CH = CH R
O
O
O
. .
R CH = CH R ...........

E addition + R'COOH
(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 + R
C
||
O
O H + R
C
||
O
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 # 43
and their corresponding carboxylic acids are shown below :-
(b) Mechanism

transition state
O
O
H
O
C
R
(
(
(

(
C
C
+
(iv) Oxidative cleavage of Alkenes
(a) Cleavage by permanganate
In a KMnO
4
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 = CH
2
group is oxidized to CO
2
and water.
General Reaction
C C
R
R'
H
R
KMnO
4
Warm
conc.
Glycol
O C
R'
H
Aldehye
(Oxidizable)
+
C O
R
R
Ketone
(Stable)

OH
C O
R'
* The same reagents that oxidize alkenes also oxodoze alkynes. Alkynes are oxi-
dized to diketone by a basic solution of KMnO
4
at room temp.
CH
3
C CCH
2
CH
3

4
OH
dil KMnO


Examples
1. +



2.

agent Re s ' Bayer H OH
H OH
3.
Me

3 2
4
NaHSO / O H
OsO


H Me
OH OH
4.
Me

-
(1) PBA
(2) H O /OH
2
18
Page # 44
5. C = C

R
H
R
H
) mix / d (
R CHOH CHOH R
!
C = C

R
H
R
H
(1) OsO
(2) H O
4
2

R
H
R
OH OH
H (meso isomer)
6. C = C

R
H R
H agent Re ) 1 (
s ' Bayer

) mix / d ( !
C = C

R
H R
H O H ) 2 (
/ O / Ag
2
2

A
(meso isomer)
7. What is the main utility of this reaction and why is it superior to KMnO
4
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) +
) bassic . aq (
KMnO
4

2 2
4
O H
in OsO
or
Cis-1, 2-Cyclopentanediol
(ii)
2 2 4
4
O H in OsO
or
.) aq ( KMnO
meso-
(iii)
2 2 4
4
O H in OsO
or
.) aq ( KMnO
rac-CH
3
CHOHCHOHCH
3
9. (i)
) O Cr K or (
KMnO hot
7 2 2
4

(ii)
) O Cr K or (
KMnO hot
7 2 2
4

10. (a)
) O Cr K or (
KMnO not
7 2 2
4

(b)
) O Cr K or (
KMnO not
7 2 2
4
HOOCCH
2
CH
2
COOH
Page # 45
11.
KMnO
4
Warm
cond.
O
+
C
O
OH
12.
KMnO
4
Warm
cond.
COOH
COOH
+ CO
2
13. +
O
Epoxycyclohexane
+
14. Predict the products, including stereochemistry where appropriate, for the m-chloroperoxy-benzoic acid
epoxidations of the following alkenes.
(a)

C = C
H
H
CH
3
CH CH
2 3
CH
2

(b)

C = C
H
H
CH
3
CH CH
2 3
CH
2


(c) Cis-cyclodecene

(d) Trans-cyclodecene