LECTURE NOTES

Session - 2009-10

ORGANIC CHEMISTRY
TOPIC : ALKENE & ALKYNE
 Contents : Alkene/Alkyne

Lect. Lect.
1 Physical properties of Alkenes/Alkyne (H) Acid-Catalyzed Hydration
2 Relative Besicity (i) For Alkene
3 Lab test of alkene and alkynes (a) Oxymercuration-Demercuration
(b) Alkoxymercuration - demercuration
4 Stability of alkenes/cycloalkenes
(c) Hydroboration-oxidation (Syn addition)
5 Method of preparation
(ii) Acid-Catalyzed Hydration For Alkyne
(A) By partial reduction of alkynes
Examples
(B) Dehydration of alcohol
(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
Lect.
(F) Replacement of the acetylenic hydrogen (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.
7. Miscelleneous
Lect. (A) Addition of carbenes to Alkenes
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
(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 () cis > trans
3. Polarity cis > trans (for Cab=Cab 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.

<CC=CC
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 sp3 sp2 sp

4. % s character 25% 33% 50%

5. pKa 50 44 25

6. Electronegativity of C sp3 (C) < sp2 (C) < sp (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)

Page # 3
 H 121.2 H
C=C
12. Structure H H
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 < CH CH2 < CH2CH 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

R H R R
> > C=C > > C=C > >
R H H 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.
CH2 CH2
7
CH2 CH 6
2
| ||
CH2 CH 3
8
1
CH2 CH2 5 4
cis-Cyclooctene 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)
1
Hhyd ( 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 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 (Ni2B nickel boride)
H2 ,Pd / CaCO 3
(Lindlar 's catalyst )
General Reaction R C C R
quinoline

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 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)

Na / Li R H
General Reaction R C C R C C
Liq. NH3 H R

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

R -
H NH 2
C=C

R

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
CH3CH2C CCH2CH3
1. ( syn addition)

3 Hexyne

Na / NH ( )
2. CH3 CH2 C C CH2 CH3 3

CH2OH CH2 CH3

3. +
(I) (II)
Minor
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 CD3 H2O CD3
H
(a) H2SO4

H O
2

HO CH2 CH3
CH3
D D D D
D D

(b) D D D D + D
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 H2 O Migration
.................. .................... .....................
(A) (B) (C)
oxonium ion 20 carbocation 30 carbocation

-H+ -H+

(E) (D)
Alkene Alkene

CH3 CH3
CH3 CH3
CH3 C CH CH3
Ans. (A) = (B) = CH3 C CH+
CH3 (C) = CH3 C CH CH3
CH3 OH2 CH3 +
+
CH3
CH3 CH3
CH3 C CH CH2
(D) = (E) =
CH3 C C CH3
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

O C CH3
8.
O

Page # 7
 O
O C CH2 CH3

9. O ethene + + CH3CH2COOH
C2H5 COOH
O

Et Et
Me H CH3 COOH Me H O
10.

+ CH3 COOH
H OH H H O C CH3
CH3 CH3

(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) NaNH2 (iii) tBuOK+ in t-BuOH (Hoffmann)
General reaction :
| |
| |
alcohol
C C + KOH C C KX H2O
| |
H X

Mechanism + 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

Br
| |
NaI
(i) CC C C
| | or Zn, CH3COOH
Br

Br ZnBr
Zn
Mech. C C
C C C C + ZnBr2
Br Br

Zn dust
(ii) 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
e.g. CH3 CHBr CHBr CH3 CH3 CH = CH CH3
Acetone
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
| |
2 NaNH
General Reaction 2
RCH CHR Br2 R C C R R C C R 2NaBr
| |
Br Br
A vic dibromide

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

Mechanism :
H H H
R
Step 1 +

HN + RCCR
C
C + HNH + Br

H

Br Br

Br R H

Amide ion vic-Dibromide Bromoalkene Ammonia Bromide

(The strongly ion
basic amide ion
brings about an
E2 reaction.)

R H
Step 2 CC - .. .. -
+ :N H R C C R + H N H + :Br:
..
Br R | |
H H
Bromoalkene Alkyne Ammonia bromide
(A second E2 reaction Amide ion ion
produces the alkyne)

From vicinal/Geminal Dihalides (2HX)

Step 1 Step 2

Page # 9
 (1) Reactant

(2) Nature of Elimination E2 E2

(3) Rate of E2 r1 > r2

(anti elimination) (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)
Ether R' X
(II) RC C H + CH3MgBr
RC = C MgBr 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
CH3C C H + NaNH2
3
NH3 + CH3 C C CH2 CH3

CH3
|
Na Metal CH3 C C CH CH3
CH3C C H + H2 +

HCCH 2CH4 + BrMg C C MgBr H5 C2 C C C2 H5

(D) 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 :

H CH3
1. Na I / acetone

H3C H

2. Na I / acetone

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 (iv) CH3 CH2 C CH3
| |
Cl
Cl

Cl
|
(v) CH3 CH CH CH3 (vi) CH3 CH C CH3
| | | |
Cl CH3 CH3 CH3
Ans. (i) gives CH3CH2CH2CH = CH2, (ii) & (iii) = CH3CH2CH = CHCH3

(iv) & (v) = (vi) =

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

Page # 11
Ans.

6. NaNH2
CH CH

7. CH3 CHCl2 NaNH2

CH CH

8. NaNH2
CH3 C CH

9. NaNH2
CH3 CH2 CHCl2 CH3 C CH

10. NaNH2
CH3 CCl2 CH3 CH3 CCl = CH2

11. CH3 CH2 CH2 CHCl2 NaNH 2

CH3 CH2 C CH
12. NaNH2
CH3 CH2 C CH

13. NaNH 2
CH3 CH2 CCl2 CH3 CH3 CH2 C CH

14. NaNH 2
CH3 CH2 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.
CH3 CH3 CH3 Br
CH3 C CH2 CHBr2 CH3 C CH CH2 CH3 C C CH3
Sol.
CH3 CH3 Br Br CH3 Br
(I) (II) (III)
17. Show the product in the following reaction
CH3
CH CH2 EtOK
?
EtOH
Br Br

Page # 12
 CH3
Sol. C CH

18. 1, 1 dibromopentane on reaction with fused KOH at 470K gives 2 pentyne

Br 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.
Ans. Mech.
Br H H
H H -OH
H C C CH2CH2CH3 C C -OH
-OH H C C C CH2CH3
Br CH2CH2CH3
Br H H
H H
H
H C C C CH2CH3 H2O
H C C C CH2CH3 H C C C CH2CH3 H OH
OH
H
H
H C C C CH2CH3 H OH
H C C C CH2CH3 H C C C CH2 CH3
OH
H H H
2 pentene

Br2 NaNH2
19. CH3 CH2 CH CH2 CH3 CH2 C HCH2Br CH3CH2C CH
CCl 4 | mineral oil
Br 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

(enol) O

(iii) ERG CH = CH2 > CH2 = CH2 > EWG CH = CH2

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

(b) CH = CH2 > CH2 = CH2

(c) < CH2 = CH2

CH = CH2 CH = CH2 CH = CH2

(d) > >

ERG EWG

(f) Electrophilic addition in C C

E Nu E Nu
C C

(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
 X
| |
C=C + X2 CC
| |
X
usually anti addition

(b) Mechanism
Step-1 Formation of a halonium ion

.. X .. -
.. + + : .X. :
C=C + : .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 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 )

Br Br Br

Br2 (leq.) Br2 (leq.)

(a) R C C R R C = C R R C C R

(1) r1 Br ( 2) r2 Br Br
(Trans-dihalide) (Tetrahalide)
(b) Rate:- r2 > r1 (Criteria : Stability of carbocation)

Page # 16
 Br

R C C R > R C = C R
+ +

Br Br Br
(Alkyl C + ) (Vinyl 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

OH
| | | |
(a) General Reaction 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.

(E) Addition of HOX to Alkynes

X
HOX(leq.) HOX

(a) R C C H R C = CH

(1 eq.)
OH enol

H2O

Page # 17
 R C CH2X R C CHX2
O O
10% (minor) 90% (major)
[-Haloketone] [-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 :
KOH H2 O
R C CHX2
R C CH(OH)2 R C CHO
O O O
(major product)

Examples :

Br / CCl 4
Ex.1 CH3 CH = CH2 2 CH3 CHBr CH2Br

IBr / CCl 4
Ex.2 CH3 CH = CH2

Ex.3 CH3 CH = CH2 BrCl

Ex.4 CH3 CH = CH2 ICl

Br2 H Br
Ex.5
Br H
Me
Br2 Me Br
Ex.6
Br H

Me Me Me Me
X
CH 3 CH3
Br2
Ex.7 C=C (d + mixture)
H H (cis)
cis H H X
H H

Me H X Me H
CH3 H Br2
Ex.8 C=C (meso)
H CH3 (trans)
trans H H X
Me Me

Br
2
Ex.9
Ph CHBr CHBr Ph

(d + ) mix

Br Ph Ph
IBr
Ex.10
H I
H
Page # 18
 HOCl / H
Ex.11 CH2 = CH2 CH2 CH2

Cl OH
HOBr / H
Ex.12 CH3 CH = CH2 CH3 CH CH2

OH Br
Br
Br2 / H2 O |
Ex.13 CH3 CH = CH2 CH3 CH CH2
NaCl, KI
impurities |
G
4 products are formed.
G = OH , Br, I, Cl

Br / H O
Ex.14 2 2 + OH H

Me
Me Br

- 18 18
Cl 18 OH OH
NaO H Me

Me

Me
HOCl / H

Ex.15

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

Cl 2
Ex.16 Ph C C CH3
Excess

Cl2 D / Ni
Ex.17 CH3 C CH (Q ) 2(R )
(leq.) (leq.)

Cl
HOCl (excess)

Ex.18 Ph C C CH3 Ph C C Cl
O CH3
CH3 CH3
HOBr KOH

Ex.19 CH3 C C CH CH3 C C CHO

(Excess)
H H O

Ex. 20

Ex.21

Ex. 22

Page # 19
Ex. 23

Ex. 24 CH
+ Br2 2Cl2

Ex. 25 CH
+ Br2 2Cl2

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
H Br
(MK)

H+ - H + +
(b) Mechanism:- R C C H r [R C CH2 ] Br R C = CH2 R CH CH2 + R C CH3

1
r2
Vinyl C Br Br Br
Vinyl halide Less stable more stable

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
e cloud is
(1) Reactivity order C=C > CC cylindrical
and difficult
to break

+ +
(2) C (Stability) CC > C=C
E E
(alkyl C + ) (vinyl C + )

(3) For H2/Ni (R.O.) C=C < CC

(4) Hhydrogenation (overall) C=C < CC

# Heat of hydrogenation per -bond ?

C=C < CC

(d) Reactivity Order:- R CH CH R > > RC CR

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

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

BrCCl3 / peroxides
n C 6H13 CH CH2
e.g. n C 6H13 CH CH2 CCl3
1 Octene |
Br
3 Bromo 1,1,1 trichlorononane

n C 6H13 CH CH2 HBr / R O

2 2
nC6H13CH2 CH2 Br
1 Octene
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. 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 = CH2 + X R CH CH2 X + HR

R CH = CH2 + F R CH CH2 F exo

R CH = CH2 + Cl R CH CH2 Cl exo

R CH = CH2 + Br R CH CH2 Br exo

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

In step (iv)

R CH CH2 X + H X R CH2 CH2 X + X + HR

R CH CH2 X + H F R CH2 CH2 X + F + endo

R CH CH2 X + H Cl R CH2 CH2 X + Cl + endo

R CH CH2 X + H Br R CH2 CH2 X + Br + exo

R CH CH2 X + H I 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 HBr C

3. CH3 C = CH2 CCC

( dark )
Br
CH3 C

HBr
CH3 C = CH2 C C C # Light can also cleave HBr bond.

(light ) Br
CH3 C

HBr
4. CH3 C CH = CH2 C C C C # R2O2 accelerates cleavage of HBr bond.

CH3 (R 2 O 2 ) C Br

CH3 HBr C

CH3 C CH = CH2 CCCC

( dark )

CH3 Br C

HBr
5. Br
(light )

HBr

Br
( dark )
HBr (R O )
6. Ph CH = CH2 22 Ph CH2 CH2

Br

Page # 23
 HBr
Ph CH = CH2 Ph C C

Br
CH3 CH3
HBr

7. CH3 C CH = CH2 CH3 C CH CH3

CH3 Br CH3

HBr
8.

Br

H
9.

HCl
10.

Cl

HBr
11.

Me
Br
CH3

12. CH3 O CH2 CH = CH CH CH3

CH3
HCl (dry) ..

CH3 O CH CH2 CH2 CH CH3
Cl

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 # 24
 Cl
HCl(leq.) HCl(leq.)

15. H C C H H C = CH 2 H C CH3

Cl Cl
Vinyl Chloride gem dihalide
HCl(leq.)
16. CH2 = CH CH2 C CH CH3 CH CH2 C CH

Cl
HCl(leq.)
17. CH2 = CH C CH CH2 = CH C = CH2 Conjugated product

Conjugated System Cl
Neoprene

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 + H2 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 # 25
 OH O
O
| | ||
|| THF
General Reaction + H2O + Hg OCCH C C O + CH3 COH
3 2 | | ||
Hg OCCH3

OH
| | | |
CC O + + NaBH4 C C + Hg + (Demercuration)
| | ||
| |
Hg OCCH3
HO H
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.

NaBH4
Step (B)

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

OR RO
| | | |
ROH NaBH4
General reaction + Hg(OAc)2 C C
CC
| | | |
HgOAc H
(Markovnikov
orientation)

Page # 26
(c) Hydroboration-oxidation (SYN ADDITION)
| |
ROH
General Reaction + 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
OH 3

Mechanism
HOOH + HO HOO + H2O

Re peat the two

Pr eceding steps two time

Re peat the three

Pr eceding steps
3 ROH + BO33 ROH +

two times

(ii) Acid-Catalyzed Hydration For Alkynes

H SO / HgSO 4
G.R. R C C H 2 4 R C CH3
O
OH OH
Hg 2 H SO 4

Mechanism:- R C C H R C = C H R C = C H 2
R C = CH2
:

H2O:

+ Hg
Hg + HgSO4
O
tauto.
R C CH3
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) CH3 (CH2)3 CH = CH2 < CH3 (CH2)2 CH = CH CH3 < H3 C (CH2 )2 C CH2
|
CH3

H H H3C H
(b) C=C < C=C < H3 C C CH2
H3C CH3 H CH3 |
trans-2-butene CH3
cis-2-butene

(c) CH2 CH = CH 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 H O, H
2
CH3 CHCH3
Pr opene
|
OH
Isopropyl alcohol

CH3 CH3 H
| | |
2. CH3 C CH CH2 50 % H SO 4
2 CH3 C C CH3
| | |
CH3 OH CH3
3,3 dim ethyl 1 butene
2, 3-dimethyl-2-butanol
(major product)

CH3 CH3 H

3. D O/ D
CH3 C C CH3 2 CH3 C C CH3
H OD D

CH2 CH3 CH3

0
83 C
4. CH3 C + H2SO4 CH3 C OSO3H CH3 C OH .
H2O
CH3 CH3 CH3
t Butyl hydrogen sulphate t butyl alcohol, bp 830C

CH3 H CH3
| dil. aqueous H SO | |
5. H3 C C CH CH2 2
4
H3 C C C CH3 + H3 C C C CH3
| | | | |
CH3 CH3 OH CH3 CH3
3,3 dim ethyl 1 butene 2, 3 dim ethyl 2 bu tanol 2, 3 dim ethyl 2 butene
(major ) (min or )

OH
NaBH4 |
6. H2 C CHCH2 CH3 CH3 CHCH2CH3
1 butene 2 butanol

CH2 CH CH2 CH3

7. 1 butene

8. + 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.

Hg(OAC)2 NaBH 4 / NaOH

9. C3H7CH = CH2 C3H7CH(OH)CH2 HgOAC C3H7CH(OH)CH3
THF / H2O
(An organomercurial alcohol)

Hg(OAC)2 NaBH
4
10.
CH3OH
OCH3

OH
Hg( OAC )
2 NaBH4 O
11.

NaOH

CH3 CH3
| |
12. Hg(OAc )2 , H2O NaBH4
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.

CH3 CH3 CH3

| +
H (dil. H2SO4) | + CH3 shift + |
14. CH3 C CH = CH2 CH3 C CH CH3 CH3 C CH CH3
| | | 3carbocation
CH3 CH3 CH3
2carbocation ( H+ ) H2O
CH3
Hydroboration | OH CH3
CH3 C CH2 CH2OH | |
oxidation | CH3 C CH CH3
CH3 |
CH3 OH CH3
Hg(OAc)2 | |
NaBH4 CH3 C CH CH3
|
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 H
H
16. BH / THF
3 Me H2O2 / OHO

Me


BH2 OH
Me
H H
1 methylcyclopentene trans 2 cyclopentanol

HBr H SO BH3/THF
17. Br OH 24 OH
H2O2/OH-

HBr
Br

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

BH3 THF
(B) H O / OH R CH2 CHO
2 2

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

(1) Hg 2
20. Ph C C CH2 CH3
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

2
21. Ph C CH Acetophenone
Hg / H 3 O

(Reactant)
OH
|
Ph C = CH2 Retrosynthesis

Ph C CH

Page # 31
 Hg 2 / H SO
2 4 2 I / OH
22.
+ CHI3

BH / THF
3
23. CH3 C C CH3

2

I / OH

HOO

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)

1eq

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 (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.

. . .. Heat or ultraviole t light H

: N N CH2 : N N C H2 N2 + :C

H
diazometha ne 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) Singlet triplet
(c) sp2/120/bent
(d) Diamagnetic paramagnetic
(e) 6e /e deficient (electrophilic) (electrophilic)

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

CH N /
2 2
ex.

3 CH CHCO /
CH3CH=CH2

(B) Addition of NOCl

NaCl
CH3 CH = CH2

(C) Halogenation. Allylic substitution

General Reaction X2 = Cl2, Br2

NBS = N-Bromosccinimide NCS = N-Chlorosuccinimide

(D) Alkylation :
| | | |
acid
General Reaction 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 Allyl chloride
(Pr opene ) (3 Chloro 1 propene )

CH3 CH3 CH3 CH3

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

light
4. (a) CH3 CH CHCH3 + CH 2N2
2 Butene Diazometha ne

(b) NaOH / H2O

+ CHBr3

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

(a) (b) (c) norcarane,

CH3

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

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

Br

+ NBS
7.
Cyclohexene
3-Bromocyclohexene

1. F.R Allylic substitution :

Br / r.t.
H2CCH=CH2 2 ........... Eaddition (or F.R. addition)
(1)

Page # 36
 Br / 400 500 C
2 .......... Allylic substitution
(2)

NBS / R O
2
2

(3)

X2 = Br2/Cl2

X2
[H CH=CH ] + HX
# (2)
2C 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

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

(iv) + HBr + Br2 (low conc.)

(v) 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.]
3 NaHCO
H2C = CH CH2 CH2 CH2 COOH
X2

Page # 37


# Hydrolysis of vinyl ethers :

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

H + HOR

18
H3 O

Mechanism

H H

H3CCH=O18 H

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.
R O
R'
R R' C C
(a) General Reaction C C + O3 R H
R H
O O
Ozonide

(CH3)2S

R R'
C O+ O C
R H
Ketone
(1) O 3
+ R'COOH
( 2 ) H2 O
(Oxidative ozonolysis)

(1) O 3
+ (reductive ozonolysis)
(2 ) Zn / H2 O or
CH3 COOH or
Me 2 S / H2 O

(1) O3
(2) LiAlH4/NaBH4 + R'CH2OH

(reductive ozonolysis)

(b) Mechanism

O
-
C
C O
O+ O
C
O O
O

Molozonide (Primary ozonide)

C
C
O O O O -

C O C O+

Ozonide

Page # 39
 R O
R' R O
C C CH3 - S - CH3 R'
H C O+ O C + CH3 S CH3
R dimethyl sulfide
R H
O 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.

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

(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 O O
Conc. KMnO4
1. O O
- OH
H H O

(not isolated)

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

O3
3. +

KMnO4/OH - + R'COOH

KMnO / H + R'COOH
4

K Cr2O 7 / H /
2 + R'COOH
or, CrO3 / H /

dil.KMnO 4
HIO 4 +
cold

Page # 40
4. Lemienx Reagent O
(KMnO4 + NaO4) O

OH H HO4
OH H

5. (1) TFPAA H O OH H HIO 4

2
no reaction
H OH

6. ( 2) OsO 4 H O H OH HIO 4 O
2

H OH O

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

H OH HIO 4 / AgNO3 O + AgIO ppt.
3
H OH O
cis

H OH HIO / AgNO3
4 No reaction
OH H
trans

(i) O3
8. CH3CH2CHO + CH3(CH2)4CHO (65%)
(ii) (CH3)2 S
3 - nonene

H CHO
H H
H
(i) O3 C
9. O +
(ii) (CH3)2 S C
H H
H O
H CHO

(i) O3
10. CHO
(ii) (CH3)2 S CHO
O
(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:-

2H 2O
R CH = CH R R CH CH R + H2OsO 4
O O O O (Cyclic ( 6)
osmate
Os Os ester)
O (48) O O O

(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)

R CH = CH R ........... E addition + R'COOH

..
O
18 O
H
C
R
O

(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.

O O
|| ||
(a) General Reaction C=C +R C O H + 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

C O R
C
O
C
O +
H
transition state

(iv) 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' R' R R'

KMnO4
General Reaction C C O C + C O O C
R H Warm H
conc. R OH
Glycol Aldehye Ketone
(Oxidizable) (Stable)

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

Examples

1. +

Bayer ' s Re agent OH H

2.
OH H

OsO 4
3.
H2 O / NaHSO 3 Me H

Me
OH OH

Me

(1) PBA
4.
(2) H 2O /OH -
18

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 R R

5. C=C R CHOH CHOH R

H H (d / mix )

R R (1) OsO 4 R R

C=C H H(meso isomer)
(2) H2O
H H OH OH
R H Bayer ' s
6. C = C (d / mix )

H R (1) Re agent

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

H R ( 2) H 2 O

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:-

or
(i) + KMnO 4 Cis-1, 2-Cyclopentanediol
OsO 4 in
(aq. bassic )
H2 O 2

KMnO (aq.)
(ii) 4 meso-
or
OsO 4 in H2O 2

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

hot KMnO 4
9. (i)
(or K 2 Cr2 O 7 )

hot KMnO 4
(ii)
(or K 2 Cr2 O 7 )

not KMnO 4
10. (a)
(or K 2 Cr2 O 7 )

not KMnO 4
(b) HOOCCH2CH2COOH
(or K 2 Cr2 O 7 )
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 KMnO4 O OH
11. Warm + C
cond. O

KMnO4
12. Warm COOH + CO2
COOH
cond.

13. + O +

Epoxycyclohexane

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

H H CH2CH2CH3
H C=C
(a) C=C (b)
CH3 H
CH3 CH2CH2CH3

(c) Cis-cyclodecene (d) Trans-cyclodecene

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