Alkene Alkyne PDF
Alkene Alkyne PDF
Alkene Alkyne PDF
Session - 2009-10
ORGANIC CHEMISTRY
TOPIC :
Contents : Alkene/Alkyne
Lect.
Lect.
Lect.
(I) Oxidation Reaction
Lect.
(i) Ozonolysis (C = C, C C)
Examples
tetrahalides
(E) Dehydrohalogenation of alkyl halides/
vicinal dihalides
(F) Replacement of the acetylenic hydrogen
Lect.
(ii) Hydroxylation Reactions (Alkenes, Alkynes)
alkynes
(G) Miscellaneous
Examples
Hydrolysis of carbides
Examples
Lect.
Lect.
7. Miscelleneous
6. Chemical Reactions
(D) Alkylation
Examples
Lect.
Discussion
Lect.
(F) Addition of Hydrogen Halides (+ HX) to Alkene
(G) Addition of Hydrogen Halides (+ HX) to Alkyne
Examples
Page # 2
Homologus series
Isomers
1.
Physical state
C1 C3 gases
C4 C20 liquids
> C20 : solids
2.
Dipolemoment ()
3.
Polarity
4.
Melting point
5.
Boiling point
<CC=CC
Polarity increases, boiling point
increases
6.
Solubility
7.
Stability
Practically insoluble
in water but fairly
soluble in nonpolar
solvents like benzene
petroleum ether, etc.
Alkanes
Alkenes
Alkynes
1.
Bond length
1.54 (C C)
1.32 (C = C)
1.20 (C C)
2.
Bond energy(KJmol-1)
415 (C C)
615 (C = C)
835 (C C)
3.
Hybridization
sp3
sp2
sp
4.
% s character
25%
33%
50%
5.
pKa
50
44
25
6.
Electronegativity of C
sp3 (C)
7.
Polarity
R CH2 CH3
R CH = CH2
RCC
8.
Rate of hydrogenation
less
more
9.
Rate of electrophilic
addition reaction
more
less
10.
Heat of combustion
C2H6 ( 373)
11.
Density (g/cm3)
C3H8 (0.50)
C3H6 (0.52)
C3H4 (0.67)
<
sp2 (C)
<
sp (C)
Page # 3
12.
H 121.2 H
C=C
H
H
Structure
1.08
ethene
13.
Shape
Tetrahedral
Planar
Linear
2. Rel at i ve Basi ci t y
(a) CH3 CH2 : H2C CH : HC C :
(b)
OH < OR < C
CR <
NH2 <
CH
3. Stability of Alkenes/Cycloalkenes
Overall relative stabilities of Alkenes
Studies of numerous alkenes reveal pattern of stabilities that related to the number of alkyl groups attached
to the carbon atoms of the double bond. The greater the number of attached alkyl groups (i.e., the highly
substituted the carbon atoms of the double bond), the greater is the alkenes stability. This order of stabilities
can be given in general terms as follows.
Relative stabilities of alkenes
>
>
H
C=C
>
>
R
C=C
>
>
Cycloalkenes
trans-Cycloheptene has been observed spectroscopically, but it is a substance with a very short lifetime and
has not been isolated.
trans-Cyclooctene has been isolated, however. Here the ring is large enough to accommodate the geometry
required by a trans double bond and still be stable at room temperature. Trans-Cyclooctene exists as a pair
of geometrical isomers. You may wish to verify this using hand-held models.
CH2 CH2
CH2
|
CH2
CH
||
CH
CH2 CH2
cis-Cyclooctene
7
6
2
3
8
1
trans-Cyclooctene
The way of measuring the stability of an alkene is the determination of its heat of hydrogenation or the
heats of combustion. Both are exothermic reactions. (H = ve)
Hhyd
1
( ve sign indicates the exothermic nature of reaction)
stability
Page # 4
4.
Methods of preparation
(A)
(i) Lindlars catalyst : Metallic palladium deposited on calcium carbonate conditioned with lead acetate
and quinoline.
H2 ,Pd / CaCO 3
(Lindlar 's catalyst )
quinoline
R C C R
Mechanism of hydrogenation :
(1)
( 2)
Steps : The reactant alkyne molecules and hydrogen molecules get adsorbed at the surface of metal catalyst. It is chemical adsorption (chemisorption).
In this state, the reactants lie very close to each other and so the hydrogen atoms start forming bond with
carbon. Two hydrogen atoms are added to two triply bonded carbon atoms from the
same side of bond and a cis or syn addition product is formed. The product alkene now escapes away
from the surface of the catalyst. Quinoline occupies the metal surface inhibiting further reduction to alkanes.
Quinoline therefore is called catalyst poison and such palladium is called deactivated catalyst or poisoned
catalyst.
Na / Li
Liq. NH3
H
R
C C
H
R
H NH 2
Mechanism :
R C C R
C=C
NaNH2 +
Na+
Note : This process of reduction is not eligible when terminal alkynes are taken.(RCCH) because terminal alkynes
form sodium salt with Na metal.
(B)
BY DEHYDRATION OF ALCOHOLS
Alcohols when heated in presence of following reagents undergo loss of water molecule and form alkenes.
The elimination is elimination.
(i) H2SO4 / 160C
(ii) H3PO4 /
(iii) P2O5 /
(iv) Al2O3 / 350C undergo loss of water molecule and form alkenes
Page # 5
General Reaction
(C)
BY PYROLYSIS OF ESTERS
Thermal cleavage of an ester involves formations of a six membered ring in the transition state leading to the
elimination of an acid leaving behind an alkene.
500C
Remarks:-
(1) When an ester is heated at high temperature, it forms an alkene by elimination of an acid.
(2) It is an intramolecular 1, 2 elimination (-elimination)
(3) It passes through a cyclic T.S. (6 membered).
(4) It is a syn elimination, i.e., both the eliminating groups lie on the same side.
(5) The least crowded -Hydrogen is eliminated to give the major product (Hoffman alkene).
As a direct consequence of cyclic transition state, both the leaving groups namely proton and carboxylate
ion are eliminated from the cis position. This is an example of cis elimination.
Examples :
H2 / Ni2B(P 2 )
or H2 / Pd / CaCO3
1.
CH3CH2C CCH2CH3
( syn addition)
3 Hexyne
2.
Na / NH ( )
CH2OH
CH2
3.
CH3
+
(I)
Minor
(II)
Major
CH2OH
4.
If the starting material is labelled with deuterium as indicated, predict how many deuterium will be present in
the major elimination product ?
Page # 6
HO
HO
CD3
HO
(b)
CD3
H2SO4
(a)
+
H2O
CD3
H O
CH3
CH2
CH3
H2SO4
(C D cleavage is about 7 times slower than C H cleavage so the product from C H cleavage should be
formed about 7times as fast)
5.
H
3, 3 dimethyl 2 butanol
..................
(A)
oxonium ion
H2 O
Migration
....................
.....................
(B)
(C)
20 carbocation
30 carbocation
-H+
-H+
(E)
Alkene
CH3
Ans.
(A) =
CH3 C
CH3
CH CH3
CH3 OH2
+
CH3
(B) = CH3 C CH
+
CH3
(D)
Alkene
CH3 CH3
(C) = CH3 C
+
CH CH3
CH3
CH3 CH3
(D) =
CH3 C
CH3
(E) =
CH3 C CH CH2
CH3
7.
CH3
8.
O C CH3
Page # 7
O C CH2 CH3
9.
ethene +
+ CH3CH2COOH
COOH
C2H5
O
Et
Et
H
Me
Me
CH3 COOH
H
OH
H
10.
O C CH3
CH3
(D)
+ CH3 COOH
CH3
| |
alcohol
C C + KOH
| |
H X
Mechanism
|
|
C C KX H2O
+ BH +
(E)
(i)
Br
|
|
CC
| |
Br
NaI
or Zn, CH3COOH
Br
Mech.
ZnBr
C C
Zn
Br
(ii)
C C
+ ZnBr2
Br
Zn dust
C2H5OH as solvent
Mech.
With NaI in acetone :
Page # 8
+ IX
e.g.
(A)
R C C R + 2Zn X2
(B)
General Reaction
2 NaNH
2
R C C R 2NaBr
RCH CHR Br2 R C C R
Br Br
A vic dibromide
The dehydrohalogenations occur in two steps, the first yielding a bromoalkene and the second, the alkyne.
Mechanism :
Bromoalkene
Br
+ HNH +
C
C
Br
Br Br
Amide ion
vic-Dibromide
(The strongly
basic amide ion
brings about an
E2 reaction.)
H
Ammonia
Bromide
ion
R
CC
Step 2
HN + RCCR
H
Step 1
Br
+
R
Bromoalkene
(A second E2 reaction
produces the alkyne)
..
- ..
R C C R + H N H + :Br:
:N H
..
|
|
H
H
Alkyne
Ammonia bromide
Amide ion
ion
Step 2
Page # 9
(1) Reactant
(2) Nature of Elimination
E2
(3) Rate of E2
r1
>
(anti elimination)
E2
r2
(anti elimination)
Reagents
(1) NaNH2, or , LiNH2 , or , KNH2
(2) alc. KOH
Depending on the conditions, these two dehydrohalogenations may be carried out as separate reactions, or
they may be carried out consecutively in a single mixture. Sodium amide, a strong base, is capable of
effecting both dehydrohalogenations in a single reaction mixture. (At least two molar equivalents of sodium
amide per mole of the dihalide) must be used. If product is to be a terminal alkyne, then three molar equivalents
must be used because the terminal alkyne is deprotonated by sodium amide as it is formed in the mixture,
consuming the sodium amide otherwise needed for the remaining dehydrohalogenation steps)
Dehydrohalogenations with sodium amide are usually carried out in liquid ammonia or in an inert medium
such as mineral oil.
Geminal dihalides can also be converted to alkynes by dehydrohalogenation. A geminal dihalide (abbreviated
gem-dihalide) has two halogen atoms bonded to the same carbon (from the Latin geminous, twins). Ketones
can be converted to gem-dichlorides through their reaction with phosphorus pentachloride, and these products
can be used to synthesize alkynes. Ketones can be converted to gem-dichloride through their reaction with
phosphorus pentachloride and these products can also be used to synthesize alkynes.
(C)
Replacement of the acetylenic hydrogen atom of terminal alkynes to form higher alkynes
(a) General Reaction
(I)
(II)
Ether
R' X
RC = C MgBr
RC C H + CH3MgBr
R C C R
Sodium ethynide and other sodium alkynides can be prepared by treating terminal alkynes with sodium
amide in liquid ammonia :
liq. NH
3
CH3C C H + NaNH2
NH3 +
Na Metal
CH3C C H
+ H2 +
HCCH
(D)
H5 C2 C C C2 H5
By hydrolysis of carbides
CaC2 + 2HOH C2H2+Ca(OH)2
MgC2 + 2HOH C2H2+Mg(OH)2
Mg2C3 + 4HOH CH3 C CH + 2Mg(OH)2
(E)
BY Kolbe's Electrolysis
Formation of alkene
Page # 10
Formation of alkyne
EXAMPLES :
Identify the product in the following reactions :
CH3
H
Na I / acetone
1.
H3C
Na I / acetone
2.
3.
CH3
CH3
Ans.
,
(minor)
4.
|
Cl
Cl
|
(vi) CH3 CH C CH3
|
|
CH3 CH3
Cl CH3
(i) gives CH3CH2CH2CH = CH2, (ii) & (iii) = CH3CH2CH = CHCH3
(vi) =
Page # 11
Ans.
NaNH2
CH CH
6.
7.
CH3 CHCl2
NaNH2
CH3 C CH
8.
9.
NaNH2
CH CH
NaNH2
CH3 CH2 CHCl2
CH3 C CH
10.
NaNH2
CH3 CCl2 CH3
CH3 CCl = CH2
11.
12.
NaNH 2
CH3 CH2 CH2 CHCl2
CH3 CH2 C CH
NaNH2
CH3 CH2 C CH
13.
NaNH 2
CH3 CH2 CCl2 CH3
CH3 CH2 C CH
NaNH 2
CH3 CH2 C CH
14.
15.
16.
Give the structure of three isomeric dibromides that could be used as starting materials for the preparation of
3, 3 dimethyl 1 butyne.
CH3
Sol.
17.
CH3 Br
CH3
CH2
Br
CH3
CH3
CH3 Br
(III)
Page # 12
CH3
C CH
Sol.
18.
Br
Ans.
fused KOH
CH3 CH2 C CCH3
Br CH CH2 CH2 CH 2 CH3
470 K
1, 1 dibromo pentane
2 pentyne
Give the mechanism of this rearrangement.
Mech.
Br H
H
H
-OH
H C C CH2CH2CH3
C C
-OH
Br
CH2CH2CH3
Br H
C C C CH2CH3
C C CH2CH3
-OH
H OH
C C C CH2CH3
H
H
H
C C C CH2CH3
H
H2O
OH
H
H
C C C CH2CH3
C C C CH2CH3
H OH
OH
C C C CH2 CH3
H
2 pentene
19.
Br2
NaNH2
CH3 CH2 C HCH2Br
CH3CH2C CH
CH3 CH2 CH CH2
CCl 4
Br
mineral oil
110 160 C
20.
Page # 13
6. Chemical Reactions :
Due to presence of weak electrons in alkene and alkyne, it well go for electrophilic reaction. Now question
is electrophilic addition or electrophilic substitution ?
In electrophilic substitution reaction, one bond is broken and a new - bond between one of the doubly
bonded carbon atoms and the electrophilic is formed. Since the bond energes of the bond broken and the
new bond formed are not much different therefore electrophilic substitution reaction are not accompnied by
large energy changes.
On the other hand in electrophilic addition reactions one weak -bond (251 KJ mol1) is broken and two
strong bonds (2 347 = 694 KJ mol1) are formed. The overall reaction is accompnied by a release of about
694-251 = 443 KJ mol1 of energy. In other words electrophilic addition reactions are energetically more
favourable than electrophilic substitution reactions Thus the typical reactions of alkenes are electrophilic
addition reaction and not the electrophilic substitution reactions.
(A)
(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
Page # 14
(ii)
>
>
>
>
>
>
..
..
..
H .O. C = C tauto. C C
O
(enol)
(iii)
(c)
CH = CH2
>
>
(d)
CH = CH2
CH = CH2
ERG
EWG
E Nu
C C
E Nu
(i) + X2
(ii) + HOX
(iii) + HX
(iv) + H2O/H+
C=C
X
|
|
CC
|
|
X
usually anti addition
+ X2
(b) Mechanism
Step-1
Formation of a halonium ion
..
+ : .X.
.. + : .X. :
: .X.
..
C=C
Halonium ion
Step-2
Product
meso type
d type
d type
meso type
Br Br
Br
Br2 (leq.)
Br2 (leq.)
(a) R C C R R C = C R R C C R
(1) r1
( 2) r2
Br Br
Br
(Tetrahalide)
(Trans-dihalide)
(C)
Addition
Syn.
Anti
Syn.
Anti
Page # 16
Br
R C C R > R C = C R
+
+
Br
Br Br
(Vinyl C+ )
(Alkyl C + )
(c) Nature of Addition:- Anti in both step
X (leq.)
D
R C C R 2 2
(1) Anti
( 2) Syn.
D / Pd / CaCO 3
R C C R 2
(1) Syn.
[lindlar , catalyst ]
(D)
OH
| |
| |
C C + HOX C C
| |
X
(b) Reagents
(i) X2 + H2O HOX + HX
(ii) HOX
Remarks :
Anti adition
No rearrangement
No carbocation
Bridged Carbocation
As H2O attacks the bromonium ion, positive charge develops on the carbon from which the bromine departs.
The transition state has some of the character of a carbocation. More substituted carbocation are more
stable than less substituted ones; therefore, when the bromonium ion ring opens, it does so by breaking the
bond between bromine and the more substituted carbon.
X
HOX
HOX(leq.)
R C = CH
R C C H
(1 eq.)
OH enol
(a)
(E)
H2O
Page # 17
R C CH2X
R C CHX2
O
10% (minor)
[-Haloketone]
O
90% (major)
[-Dihaloketone]
(b) Remakrs :
# Two molecules of HOX can be added, the end product is -Dihaloketone.
# The intermediate product is an enol which gives a minor product -haloketone.
Extention :
H2 O
KOH
R C CH(OH)2
R C CHO
R C CHX2
O
(major product)
Examples :
Ex.1
Br / CCl 4
CH3 CHBr CH2Br
CH3 CH = CH2 2
Ex.2
IBr / CCl 4
CH3 CH = CH2
Ex.3
CH3 CH = CH2
BrCl
Ex.4
CH3 CH = CH2
Br2
Ex.5
Me
Ex.6
ICl
H
Br
Br2
Br
H
Br
H
Me
Br
Me Me
CH 3
Ex.7
CH3
C=C
cis
Ex.9
(d + mixture)
(cis)
H
C=C
trans
CH3
Me Me
Br2
X
H
Me H
CH3
Ex.8
Me H
Br2
(meso)
(trans)
Me
X
Me
Br
Ph CHBr CHBr Ph
(d + ) mix
Br
Ex.10
Ph Ph
IBr
I
H
Page # 18
Ex.12
HOBr / H
CH3 CH CH2
CH3 CH = CH2
OH Br
Ex.13
HOCl / H
CH2 CH2
CH2 = CH2
Cl
OH
Ex.11
Br
|
Br2 / H2 O
CH3 CH = CH2 CH3 CH CH2
NaCl, KI
|
impurities
G
4 products are formed.
G = OH , Br, I, Cl
Br / H O
2 2
Ex.14
OH H
Me
Me Br
Ex.17
Ex.16
Ex.15
- 18
18
OH
18
OH
Cl
NaO
H
Me
Me
Me
HOCl / H
CH CH3
Ph CH CH3 50 60 C Ph CH CH3 Ph
O
OH
OH
Cl 2
Ph C C CH3
Excess
Cl2
D / Ni
(Q ) 2(R )
CH3 C CH
(leq.)
(leq.)
Cl
HOCl (excess)
Ph C C CH3 Ph C C Cl
O CH3
Ex.19
CH3
CH3
HOBr
KOH
CH3 C C CHO
CH3 C C CH
(Excess)
H
H O
Ex.18
Ex. 20
Ex.21
Ex. 22
Page # 19
Ex. 23
Ex. 24
CH
2Cl2
+ Br2
Ex. 25
CH
2Cl2
+ Br2
(F)
+ 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 : -
(G)
Br
Br
HBr (dark )
HBr
(a) General Reaction R C C H R C = C H r R C CH 3
r1
2
Br
H
(MK)
+
+
H
R C = CH2 R CH CH2 + R C CH3
r2
Br
Br
Br
Vinyl halide
Less stable
more stable
H+
(b) Mechanism:- R C C H r [R C CH2 ] Br
1
Vinyl C
Br -
(c) Remarks:Page # 21
VS
CC
addition
C=C
>
CC
(2) C (Stability)
+
CC
>
+
C=C
E
(alkyl C + )
e cloud is
cylindrical
and difficult
to break
E
(vinyl C + )
C=C
<
CC
C=C
<
CC
<
CC
C=C
(d) Reactivity Order:-
R CH CH R >
> RC CR
e.g.
HBr / R O 2 / h
R CH2 CH2 Br
R CH = CH2 2
BrCCl3 / peroxides
n C 6H13 CH CH2
n C 6H13 CH CH2
1 Octene
HBr / R O
2 2
nC6H13CH2 CH2 Br
Mechanism : Steps:-
Remarks:(1) When HBr is added to an unsymmetrical alkene in presence of sunlight and peroxide. Then an
Anti MK Addition Product is obtained.
(2) It is a free radical chain reaction.
(3) In presence of peroxide and sunlight Br is formed in chain initiation step.
(4) Br forms more stable alkyl radical by homolysis of C = C bond.
(5) In the last step alkyl radical abstracts H from HBr and AMK product is obtained.
Page # 22
Examples :
1.
Ans.
2.
If HF, HCl, HI are used even in sunlight electrophilic addition takes place. Why only HBr give free radical
addition ?
In chain propagation (iii) steps:
R CH = CH2 + X
R CH CH2 X + HR
Ans.
R CH = CH2 + F
R CH = CH2 + Cl
R CH = CH2 + Br
R CH = CH2 + I
B.E.:- CF > CCl > CBr > CI
R CH CH2 F
R CH CH2 Cl
R CH CH2 Br
R CH CH2 I
In step (iv)
R CH CH2 X + H X
R CH CH2 X + H F
R CH CH2 X + H Cl
R CH CH2 X + H Br
R CH CH2 X + H I
exo
exo
exo
endo
R CH2 CH2 X + X + HR
R CH2 CH2 X + F + endo
R CH2 CH2 X + Cl + endo
R CH2 CH2 X + Br + exo
R CH2 CH2 X + I + exo
CH3
C
HBr
CH3 C = CH2
CCC
( dark )
Br
CH3
C
HBr
CH3 C = CH2 C C C
(light )
Br
CH3
C
HBr
CH3 C CH = CH2 C C C C
(R 2 O 2 )
Br
C
CH3
4.
3.
HBr
(light )
HBr
( dark )
Br
HBr (R O )
Ph CH = CH2 22 Ph CH2 CH2
Br
6.
Br
5.
CH3
C
HBr
CH3 C CH = CH2
CCCC
( dark )
CH3
Br C
Page # 23
HBr
Ph CH = CH2 Ph C C
Br
7.
CH3
CH3
HBr
CH3 C CH = CH2
CH3 C CH CH3
CH3
Br CH3
HBr
8.
Br
9.
10.
HCl
Cl
11.
HBr
Me
Br
CH3
CH3 O CH2 CH = CH CH CH3
HCl (dry)
CH3
..
CH3 O CH CH2 CH2 CH CH3
12.
Cl
13.
14.
+ HCl
or
The planar carbocation (x) is responsible for nonstereoselectivity. The bromide nucleophile can attack from
the top or bottom, leading to a mixture of stereoisomers. The addition is therefore a mixture of syn and anti
addition.
Page # 24
17.
HCl(leq.)
CH2 = CH CH2 C CH CH3 CH CH2 C CH
Cl
HCl(leq.)
CH2 = CH C CH CH2 = CH C = CH2 Conjugated product
Cl
Conjugated System
Neoprene
16.
Cl
HCl(leq.)
H C = CH 2 H C CH3
Cl
Cl
gem dihalide
Vinyl Chloride
15.
HCl(leq.)
H C C H
(H)
Acid-Catalyzed Hydration
(i)
For Alkene
Alkenes add water in the presence of an acid catalyst to yield alcohols. The addition takes place with
Markovnikov regioselectivity. The reaction is reversible, and the mechanism for the acid-catalyzed hydration
of an alkene is simply the reverse of that for the dehydration of an alcohol.
The carbocation intermediate may rearrange if a more stable carbocation is possible by hydride or alkanide
migration. Thus, a mixture of isomeric alcohol products may result.
General Reaction
Mech.
Step 1 :
+ H2 O
Step 2 :
Step 3 :
Page # 25
O
OH
O
||
|
|
||
THF
+ H2O + Hg OCCH C C
+ CH3 COH
O
3 2
|
|
||
Hg OCCH3
General Reaction
OH
|
|
CC
O
+
|
|
||
Hg OCCH3
| |
+ NaBH4 C C + Hg +
| |
HO H
(Demercuration)
In the oxymercuration step, water and mercuric acetate add to the double bond ; in the demercuration step,
sodium borohydride reduces the acetoxymercury group and replaces in with hydrogen. The net addition of H
and OH takes place with Markovikov regioselectivity and generally takes place without the complication
of rearrangements.
Advantage over acidic hydrolysis (1) no requrement of acidic condition, which are harmful to many organic molecules.
(2) No rearrangement occur.
Mechanuism
Step (A) : -
Step (B)
NaBH4
OH
NaBH4 converts the carbon mercury bond into a carbon- Hydrogen bond. Because the reaction result in the
loss of mercury , it is called demercuration.
If solvent taken is alcohol product will be ether & process is called alkoxymercuration
demercuration.
(b)
Alkoxymercuration - demercuration
General reaction
RO
OR
|
|
| |
NaBH4
ROH
+ Hg(OAc)2
CC
C C
|
|
| |
H
HgOAc
(Markovnikov
orientation)
Page # 26
(c)
| |
ROH
+ BH3.THF
C C
| |
H B H
|
H
An alkene reacts with BH3 ; THF or diborane to produce an alkylborane. Oxiation and hydrolysis of the
alkyborane with hydrogen peroxide and base yields an alcohol.
(1) HBO leads to hydrogen of an alkene, however H2O is not a reactant.
(2) During process of addition H comes from BH3 & OH comes from H2O2
(3) Net result is addition of H2O by anti markov. rule without rearrangement because no inermediate is
formed.
(4) There are two steps(a) Hydroboration: - Addition of borane on alkenes. In this reaction, the addition of electrophilic Borane &
the nucleophilic H take place in one steps i.e. it is concerted reaction.
- No intermediate is formed.
In this way one BH3 react with three molecules o alkene successively to form trialkyl borane.
There are two reasons for the borane, alkylborane and dialkylborane to add to the sp2 carbon that is bonded
to the most hydrogen .
(A) To achieve most stable carbocation like T.S.
(B) There is moree room at this carbon for the bulky group to attach itself i.e stearic factor.
Page # 27
(b)
HOO + H2O
3 ROH + BO33
(ii)
G.R.
H SO / HgSO 4
R C CH3
R C C H 2 4
O
OH
OH
H SO 4
R C = CH2
R C = C H 2
Hg
+ HgSO4
Hg 2
R C = C H
Mechanism:- R C C H
H2O:
+
Hg
O
R C CH3
tauto.
Remarks:-
(b)
CH3 (CH2)3 CH = CH2 < CH3 (CH2)2 CH = CH CH3 < H3 C (CH2 )2 C CH2
|
CH3
H
C=C
CH3
H3C
cis-2-butene
(c)
<
H3C
H
C=C
H
CH3
trans-2-butene
< H3 C C CH2
|
CH3
Page # 28
EXAMPLES
1.
CH3 CH CH2
Pr opene
H O, H
2
CH3 CHCH3
|
OH
Isopropyl alcohol
2.
CH3
|
CH3 C CH CH2
|
CH3
3,3 dim ethyl 1 butene
CH3 H
|
|
50 % H SO 4
2
CH3 C C CH3
|
|
OH CH3
2, 3-dimethyl-2-butanol
(major product)
CH3 H
CH3
3.
D O/ D
C CH3 2 CH3 C
CH3 C
C CH3
OD D
CH2
CH3
CH3
4.
CH3 C
+ H2SO4
CH3
5.
CH3
|
H3 C C CH CH2
|
CH3
8.
dil. aqueous H SO
4
2
H2 C CHCH2 CH3
1 butene
7.
CH3 C OSO3H
CH3
t Butyl hydrogen sulphate
6.
83 C
H2O
CH3 C OH .
CH3
t butyl alcohol, bp 830C
H
|
H3 C C
|
CH3
CH3
|
C CH3
|
OH
+ H3 C C C CH3
NaBH4
|
|
CH3 CH3
2, 3 dim ethyl 2 butene
(min or )
OH
|
CH3 CHCH2CH3
2 butanol
+ enantiomer
Page # 29
In the first step, boron and hydrogen undergo syn addition to the alkene in the second step, treatment with
hydrogen peroxide and base replaces the boron with OH with retention of configuration. The net addition of
H and OH occurs with anti Markovnikov regioselectivity and syn stereoselectivity. Hydroboration-oxidation
therefore, serves as a useful regiochemical complement to oxymercuration demercuration.
9.
C3H7CH = CH2
Hg(OAC)2
THF / H2O
NaBH 4 / NaOH
C3H7CH(OH)CH2 HgOAC C3H7CH(OH)CH3
Hg(OAC)2
10.
NaBH
CH3OH
OCH3
OH
11.
12.
Hg( OAC )
NaBH4
NaOH
CH3
CH3
|
|
NaBH4
Hg(OAc )2 , H2O
CH3 C CH CH2
CH3 C CH CH3
|
|
|
CH3
CH3 OH
3,3 Dimethyl 1 butene
3, 3 Dimethyl 2 bu tan ol
(No rearrangement )
13.
14.
CH3
CH3
CH3
+
|
|
|
H (dil. H2SO4)
+
+
CH3 shift
CH3 C CH CH3
CH3 C CH = CH2
CH3 C
CH CH3
|
|
|
3carbocation
CH3
CH3
CH3
2carbocation
( H+ ) H2O
CH3
OH CH3
|
Hydroboration
|
|
CH3 C CH2 CH2OH
oxidation
|
CH3 C CH CH3
|
CH3
CH3 OH
CH3
Hg(OAc)2
|
|
CH3 C CH CH3
NaBH4
|
CH3
Page # 30
15.
H
16.
BH / THF
H2O2 / OHO
Me
BH2
Me
HBr
Br
OH
H
trans 2 cyclopentanol
1 methylcyclopentene
17.
Me
BH3/THF
H SO
OH 24
OH
H2O2/OH-
HBr
Br
18.
Hg2 / H2 SO 4
RCCH
( A ) (dil.)
BH3 THF
R CH2 CHO
(B) H O / OH
2 2
19.
( A ) /( B )
H C C H
CH3 CHO
20.
Ph C C CH2 CH3
(1) Hg 2
D 2 SO 4
(2) D 2O 2 / OD
(1) BD 3 THF
(2) D 2 O 2 / OD
Common Sense :
OD OD Present in D2O
21.
Hg / H 3 O
Ph C CH
Acetophenone
(Reactant)
OH
|
Ph C = CH2 Retrosynthesis
Ph C CH
Page # 31
Hg 2 / H SO
2
4
22.
23.
BH / THF
CH3 C C CH3
HOO
I / OH
+ CHI3
I / OH
NaOH / CaO ( s )
CH3 CH2 COOH Yellow ppt.
CH3 CH3
Alkadines (conjugated) :
E+ addn :
Mechanism :
Page # 32
Ex.
HBr
(1)
H2C = CH CH = CH2
(r , t )
Page # 33
HCl (1eq)
(2)
(r , t )
(3)
HCl
H3C CH = CH CH = CH2
HOX
(4)
6.
Miscellaneous
(A)
1eq
Methylene is the simplest of the carbenes : uncharged, reactive intermediates that have a carbon atom with
two bonds and two nonbonding electrons. Like borane (BH3), methylene is a potent electrophile because it
has an unfilled octet. It adds to the electrons rich pi-bond of an alkene to form a cyclopropane.
General Reactions
Heating or photolysis of diazomethane (CH2N2) gives nitrogen gas and methylene.
..
. .
: N N CH2 : N N C H2
diazometha ne
N2 + :C
H
Methylene
There are two difficulties with using CH2N2 to cyclopropanate double bonds. First, it is extremely toxic and
explosive. A safer reagent would be more convenient for routine use. Second, methylene generated from
CH2N2 is so reactive that it inserts into C H bonds as well as C = C bonds.
Structure :
Page # 34
(a)
H2C
H2 C
(b)
(c)
(d)
(e)
Singlet
sp2/120/bent
Diamagnetic
6e /e deficient (electrophilic)
triplet
paramagnetic
(electrophilic)
2 2
ex.
CH CHCO /
CH3CH=CH2
(B)
Addition of NOCl
NaCl
CH3 CH = CH2
(C)
General Reaction
X2 = Cl2, Br2
NBS = N-Bromosccinimide
(D)
NCS = N-Chlorosuccinimide
Alkylation :
General Reaction
| |
|
|
acid
C C + R H C C
|
|
H R
Examples :
1.
..
C H2 N N: sh
Page # 35
Propene
+
2.
Cl2 , 600C
CH3 CH CH2
Cl CH2 CH CH2
Pr opylene
(Pr opene )
3.
4.
Allyl chloride
(3 Chloro 1 propene )
CH3
CH3
CH3
CH3
|
|
|
|
H SO 4
CH3 C CH2 + CH3 C H
2
CH3 C CH2 C CH3
Isobutylene
|
|
|
CH3
H
CH3
Isobu tane
2, 2, 4 Trimethylpen tan e
(a)
CH3 CH CHCH3 +
2 Butene
light
Diazometha ne
NaOH / H2O
+ CHBr3
(b)
5.
CH 2N2
Show how the insertion of methylene into a bond of cyclohexene can produce the following.
CH3
(a)
(b)
(c) norcarane,
CH3
6.
Ans.
Br
7.
+ NBS
Cyclohexene
1.
3-Bromocyclohexene
Br / r.t.
2
(1)
Page # 36
Br / 400 500 C
(2)
NBS / R O
2
2
(3)
X2 = Br2/Cl2
#
X2
[H CH=CH ] + HX
2C
2
(2)
(500 C)
X2
(NBS)
(i)
ROOR 2 RO
(ii)
RO + HBr ROH + Br
(iii)
(rds )
H2CCH=CH2 H2CCH=CH2CH + HBr
Br
(iv)
(v)
+ HBr
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.
X2
Page # 37
+ HOR
18
H3 O
Mechanism
H3CCH=O18
ex.
An alkene X (C5H10O) on hydrolysis with dil H2SO4 produces Y and Z. Both give iodoform test (+ve) X is 1015
times more reactive than ethene toward E
(I) (X)
(Y)
(Z)
(II) (X)
(Y)
(Z)
(I)
Oxidation Reaction
(1)
[O]
Terminal CH
CO2 + H2O
[O]
Non Terminal alkene = CHR RCOOH
[O]
[O]
C R RCOOH
(2)
Ozonolysis :
Like permanganate ozone cleaves double bonds to give Ketones and aldehydes. However, ozonolysis is
milder, and both Ketones and aldehydes can be recovered without further oxidation.
O
R'
C
+ O3
R'
C
R
O
Ozonide
(CH3)2S
R
C
O+ O
R'
C
H
R
Ketone
(1) O 3
( 2 ) H2 O
+ R'COOH
(Oxidative ozonolysis)
(1) O 3
(2 ) Zn / H2 O or
CH3 COOH or
Me 2 S / H2 O
(1) O3
(2) LiAlH4/NaBH4
(reductive ozonolysis)
+ R'CH2OH
(reductive ozonolysis)
(b) Mechanism
O+
C
O
O+
Ozonide
Page # 39
R'
C
R
O
CH3 - S - CH3
dimethyl sulfide
C
H
R'
O+ O
+ CH3 S
CH3
dimethyl sulyoxide
(DMSO)
(3)
Ozonolysis of alkyne : Alkynes gives acid by ozonolysis ozonolysis of alkyne required neither oxidative nor reductive work up - it is
followed only by hydrolysis. carbon dioxide is obtained from the CH gp. of a terminal alkyne.
(1) O
CH COOH + CH CH COOH
CH3 C CCH2 CH2 (
3
3
2
2) H2O
(1) O 3
CH3CH2 CH2 C CH CH3CH2CH2COOH + CO2
(2) H2O
Comparison of permanganate cleavage and ozonolysis : Both permanganate and ozonolysis break the carboncarbon double bond and replace it with carbonyl C =0
groups. In the permanganate cleavage, any aldehyde products are further oxidized to carboxylic acids. In the
ozonolysis-reduction procedure, the aldehyde products are generated in the dimethyl sulfide reduction step,
and they are not oxidized.
Examples :
CH3
CH3
CH3
Conc. KMnO4
- OH
1.
H
(not isolated)
CH3
CH3
2.
H
(i) O3
(ii) (CH3)2 S
O
H
3.
O3
KMnO4/OH -
+ R'COOH
KMnO / H
4
+ R'COOH
K Cr2O 7 / H /
2
or, CrO3 / H /
+ R'COOH
dil.KMnO 4
cold
HIO 4
Page # 40
O
O
Lemienx Reagent
(KMnO4 + NaO4)
4.
OH
OH
H
H
HO4
H
HIO 4
no reaction
OH
OH
H O
(1) TFPAA
2
5.
7.
H
H
( 2) OsO 4
H O
2
6.
OH HIO 4
OH
O
O
O + AgIO ppt.
3
O
OH HIO 4 / AgNO3
OH
cis
H
OH
OH
H
HIO / AgNO3
4
No reaction
trans
(i) O3
(ii) (CH3)2 S
8.
3 - nonene
H
(i) O3
(ii) (CH3)2 S
9.
C
H
CHO
CHO
H
O +
C
H
(i) O3
(ii) (CH3)2 S
10.
CHO
CHO
(ii)
Page # 41
2H 2O
+ H3MnO 4
( 5 )
(colorless )
R CH = CH R
R CH CH R
O
Os
Os
(Cyclic
osmate
ester)
+ H2OsO 4
( 6)
(48)
2H 2O
(3) Epoxidation/Hydrolysis:-
R CH = CH R
..
O
18
(iii)
Epoxidation of Alkenes :
An alkene is converted to an epoxide by a peroxyacid, a carboxylic acid that has an extra oxygen atom in a
O O (peroxy) linkage.
C=C
O
||
+R C O
O
||
+ R C O H (acid)
The epoxidation of an alkene is clearly an oxidation, since an oxidation, since an oxygen atom is added.
Peroxyacids are highly selective oxidizing agents. Some simple peroxyacids (sometimes called peracids)
Page # 42
(b) Mechanism
(iv)
C
O
C
O
H
transition state
R'
C
General Reaction
KMnO4
Warm
conc.
Glycol
R'
O
R'
O O
OH
Aldehye
(Oxidizable)
Ketone
(Stable)
The same reagents that oxidize alkenes also oxodoze alkynes. Alkynes are oxidized to diketone by a basic solution of KMnO4 at room temp.
KMnO 4 dil
CH3 C CCH2CH3
OH
Examples
1.
2.
OsO 4
H2 O / NaHSO 3
3.
Me
OH
H
H
Me H
OH OH
Me
4.
OH
(1) PBA
18
(2) H 2O /OH -
Page # 43
R (1) OsO 4
(2) H2O
H
R CHOH CHOH R
(d / mix )
C=C
C=C
R
5.
R
H
H(meso isomer)
OH OH
H Bayer ' s
C = C (d / mix )
H
R (1) Re agent
6.
H Ag / O 2 /
C = C (meso isomer)
H
( 2) H 2 O
R
7.
What is the main utility of this reaction and why is it superior to KMnO4 cleavage for this purpose ?
Sol.
It locates the position of C = C's in molecules. KMnO4 cleavage is more vigorous and can oxidize other
groups, i.e. OH.
8.
KMnO 4
(aq. bassic )
(ii)
or
Cis-1, 2-Cyclopentanediol
OsO 4 in
H2 O 2
KMnO (aq.)
4 mesoor
OsO 4 in H2O 2
(iii)
KMnO (aq.)
4 rac-CH3CHOHCHOHCH3
or
OsO 4 in H2O 2
9.
(i)
(ii)
10.
(a)
(b)
hot KMnO 4
(or K 2 Cr2 O 7 )
hot KMnO 4
(or K 2 Cr2 O 7 )
not KMnO 4
(or K 2 Cr2 O 7 )
not KMnO 4
HOOCCH2CH2COOH
(or K 2 Cr2 O 7 )
Page # 44
KMnO4
Warm
cond.
11.
13.
KMnO4
Warm
cond.
12.
OH
COOH
CO2
COOH
Epoxycyclohexane
14.
Predict the products, including stereochemistry where appropriate, for the m-chloroperoxy-benzoic acid
epoxidations of the following alkenes.
(a)
H
CH3
H
C=C
CH2CH2CH3
(c) Cis-cyclodecene
(b)
CH3
CH2CH2CH3
C=C
H
(d) Trans-cyclodecene
Page # 45