Вы находитесь на странице: 1из 27

Chapter 4A

Reaction of alkenes

Reactions of Alkenes: Addition Reactions


6.1: Hydrogenation of Alkenes addition of H-H (H2) to the
-bond of alkenes to afford an alkane. The reaction must be
catalyzed by metals such as Pd, Pt, Rh, and Ni.
H
C
H

H
+

C-C -bond
= 243 KJ/mol

H-H
= 435 KJ/mol

Pd/C
EtOH

H
C

Hhydrogenation = -136 KJ/mol

C-H
= 2 x -410 KJ/mol

= -142 KJ/mol

The catalysts is not soluble in the reaction media, thus this


process is referred to as a heterogenous catalysis.
The catalyst assists in breaking the -bond of the alkene and
the H-H -bond.
The reaction takes places on the surface of the catalyst. Thus,
the rate of the reaction is proportional to the surface area
of the catalyst.
2

Carbon-carbon -bond of alkenes and alkynes can be reduced


to the corresponding saturated C-C bond. Other -bond bond
such as C=O (carbonyl) and CN are not easily reduced by
catalytic hydrogenation. The C=C bonds of aryl rings are not
easily reduced.
O

O
H2, PtO2
ethanol
O
C5H11

OH

H2, Pd/C

Linoleic Acid (unsaturated fatty acid)

CH3(CH2)16CO2H
Steric Acid (saturated fatty acid)

O
OCH3

H2, Pd/C

OCH3

ethanol

H2, Pd/C
ethanol

6.2: Heats of Hydrogenation -an be used to measure relative stability of isomeric alkenes
H
H3C

H
CH3

cis-2-butene

Hcombustion : -2710 KJ/mol


H
H3C

H2, Pd

CH3

cis-2-butene

Hhydrogenation: -119 KJ/mol

H
H3C

CH3
H

trans-2-butene

trans isomer is ~3 KJ/mol


more stable than the
cis isomer

-2707 KJ/mol
CH3CH2CH2CH3

H2, Pd

H
H3C

CH3
H

trans-2-butene

-115 KJ/mol

trans isomer is ~4 KJ/mol more stable than the cis isomer

The greater release


of heat, the less
stable the reactant.

Table 6.1: Heats of Hydrogenation of Some Alkenes


Alkene
H2C=CH2

monosubstituted

H3C

disubstituted

trisubstituted

tetrasubstituted

136

125 - 126

117 - 119

H3C

CH3

CH3

H3C

H (KJ/mol)

H3C

H3C

H3C

H3C

CH3

H3C

CH3

H3C

CH3

114 - 115

116 - 117

112

110

6.3: Stereochemistry of Alkene Hydrogenation


Mechanism:
H H

H2C CH2

H H H2C CH2

H2C CH2
H2

H
H
C C
H
H

H H
C
H
H
C H

The addition of H2 across the -bond is syn, i.e., from the


same face of the double bond
CH3
CH3

H2, Pd/C

EtOH
H

CH3

CH3
H

CH3

syn addition
of H2

CH3

Not observed

6.4: Electrophilic Addition of Hydrogen Halides to Alkenes


C-C -bond: H= 368 KJ/mol
C-C -bond: H= 243 KJ/mol

-bond of an alkene can


act as a nucleophile!!
Electrophilic addition reaction
H
H

C C

H
+

nucleophile

Br
H-Br

C C

electrophile

Bonds broken
C=C -bond 243 KJ/mol
HBr
366 KJ/mol

Bonds formed
H3C-H2CH -410 KJ/mol
H3C-H2CBr -283 KJ/mol

calc. H = -84 KJ/mol


expt. H= -84 KJ/mol

Reactivity of HX correlates with acidity:


HF << HCl < HBr < HI fastest
6.5: Regioselectivity of Hydrogen Halide Addition:
H
Markovnikov's Rule
H Br
Br H
H-Br
C
H
slowest

C
H

R
C

R
C

C
H

C
R

R C C H
H H

H-Br

H-Br

Br H
R C C H
R H
Br H
R C C R
R H

R C C H
H H
none of this

H Br
R C C H
R H
none of this
H Br
R C C R
R H
none of this

R
C

C
R'

H-Br

Br H
R C C R
H H

H Br
R C C R'
H H

Both products observed

For the electrophilic addition of HX across a C=C bond, the H (of


HX) will add to the carbon of the double bond with the most Hs
(the least substitutent carbon) and the X will add to the carbon of
8
the double bond that has the most alkyl groups.

Mechanism of electrophilic addition of HX to alkenes

6.6: Mechanistic Basis for Markovnikov's Rule:


Markovnikovs rule can be explained by comparing the
stability of the intermediate carbocations

For the electrophilic addition of HX to an unsymmetrically


substituted alkene:
The more highly substituted carbocation intermediate is
formed.
More highly substituted carbocations are more stable than
less substituted carbocations. (hyperconjugation)
The more highly substituted carbocation is formed faster
than the less substituted carbocation. Once formed, the
more highly substituted carbocation goes on to the final
product more rapidly as well.

10

6.7: Carbocation Rearrangements in Hydrogen Halide


Addition to Alkenes - In reactions involving carbocation
intermediates, the carbocation may sometimes rearrange if a
more stable carbocation can be formed by the rearrangement.
These involve hydride and methyl shifts.
H
H3C
H3 C

H-Cl

H3C
H3C

Cl
C

H
C
H

H3C
H3 C

~ 50%
expected product
H
H3C
H3C

C
CH3

C
H

H-Cl

H3C
H3C

C
CH3

C
H

H
H

C
H

Cl

H
H

~ 50%

Cl

H3C
H3C
H3C

C
Cl

H
C

C
H

H
H

Note that the shifting atom or group moves with its electron pair.
A MORE STABLE CARBOCATION IS FORMED. 11

6.8: Free-radical Addition of HBr to Alkenes


H3CH2C

H3CH2C

H
C

H
C

H
C

R
C

R
C

R
C

C
H

C
H

C
H

C
H

C
R

C
R'

H-Br

Br H
H3CH2C C C H
H H

H-Br

Br H
H3CH2C C C H
H H

peroxides
(RO-OR)

H-Br

ROOR
(peroxides)
H-Br

ROOR

H-Br

ROOR
H

H-Br

ROOR

H Br
H3CH2C C C H
H H
none of this
H Br
H3CH2C C C H
H H

Polar mechanism
(Markovnikov addition)
Radical mechanism
(Anti-Markovnikov addition)

none of this

Br H
R C C H
H H
none of this
Br H
R C C H
R H
none of this
Br H
R C C R
R H
none of this
Br H
R C C R
H H

H Br
R C C H
H H
H Br
R C C H
R H

H Br
R C C R
R H

H Br
R C C R'
H H

Both products observed

The regiochemistry of
HBr addition is reversed
in the presence of
peroxides.
Peroxides are radical
initiators - change in
mechanism
12

The regiochemistry of free radical addition of H-Br to alkenes


reflects the stability of the radical intermediate.
H

R C
H
Primary (1)

R C

<

R
Secondary (2)

R C

<

R
Tertiary (3)

13

6.9: Addition of Sulfuric Acid to Alkenes


Reaction type: Electrophilic Addition
When treated with aq. acid, most commonly H2SO4, alkenes form alcohols.
Electrophile : H+
Regioselectivity predicted by Markovnikov's rule
Reaction proceeds via protonation to give the more stable
carbocation intermediate.
Not stereoselective since reactions proceeds via a planar carbocation.

14

6.10: Acid-Catalyzed Hydration of Alkenes - addition of water


(H-OH) across the -bond of an alkene to give an alcohol;
opposite of dehydration

H3C
C
H3C

CH2

H2SO4, H2O

H3C
H3C
H3C

OH

This addition reaction follows Markovnikovs rule The more


highly substituted alcohol is the product and is derived from
The most stable carbocation intermediate.
Reactions works best for the preparation of 3 alcohols

15

6.11: Thermodynamics of Addition-Elimination Equlibria


H3C

H2SO4

CH2

+H2O

H3C

Bonds broken
C=C -bond 243 KJ/mol
HOH
497 KJ/mol

H3C

C
H3C
H3C

OH

Bonds formed
H3C-H2CH -410 KJ/mol
(H3C)3COH -380 KJ/mol

calc. H = -50 KJ/mol


G = -5.4 KJ/mol

H = -52.7 KJ/mol

S = -0.16 KJ/mol

How is the position of the equilibrium controlled?


Le Chateliers Principle - an equilibrium will adjusts to any stress
The hydration-dehydration equilibria is pushed toward hydration
(alcohol) by adding water and toward alkene (dehydration) by
17
removing water

The acid catalyzed hydration is not a good or general method for


the hydration of an alkene.
Oxymercuration: a general (2-step) method for the Markovnokov
hydration of alkenes
H
C4H9

H
C

1) Hg(OAc)2, H2O

O
H3C

C
H H

Ac= acetate =

C4H9

OH

Hg(OAc)

2) NaBH4
C4H9

OH
C

H H

NaBH4 reduces the C-Hg


bond to a C-H bond

18

6.12: Hydroboration-Oxidation of Alkenes - Anti-Markovnikov


addition of H-OH; syn addition of H-OH
CH3

1) B2H6, THF
2) H2O2, NaOH, H2O

HO

CH3
H

6.13: Stereochemistry of Hydroboration-Oxidation


6.14: Mechanism of Hydroboration-Oxidation Step 1: syn addition of the H2BH bond to the same face of the
-bond in an anti-Markovnikov sense; step 2: oxidation of the
BC bond by basic H2O2 to a COH bond, with retention of
stereochemistry

19

6.15: Addition of Halogens to Alkenes


X2 = Cl2 and Br2
X2

C C

C C

alkene

1,2-dihalide

(vicinal dihalide)

6.16: Stereochemistry of Halogen Addition - 1,2-dibromide


has the anti stereochemistry
Br

Br
+

Br2

Br

Br

not observed

CH3

Br2

Br

CH3
Br
20

6.17: Mechanism of Halogen Addition to Alkenes:


Halonium Ions - Bromonium ion intermediate explains the
stereochemistry of Br2 addition

21

6.18: Conversion of Alkenes to Vicinal Halohydrins


"X-OH"

OH

C C

C C

alkene

halohydrin

X2, H2O

+ HX

OH
anti
stereochemistry

Mechanism involves a halonium ion intermediate

22

For unsymmterical alkenes, halohydrin formation is


Markovnikov-like in that the orientation of the addition of
X-OH can be predicted by considering carbocation stability

CH3
Br

more + charge on the


more substituted carbon

H2O adds in the second step and adds to the


carbon that has the most + charge and ends
up on the more substituted end of the double bond
CH3

Br2, H2O

HO

CH3
+ HBr

Br

Br adds to the double bond first (formation of


bromonium ion) and is on the least substituted
end of the double bond
23

Organic molecules are sparingly soluble in water as solvent. The


reaction is often done in a mix of organic solvent and water using
N-bromosuccinimide (NBS) as he electrophilic bromine source.
O
N Br

OH
Br

DMSO, H2O

N H

Note that the aryl ring does not react!!!


6.19: Epoxidation of Alkenes - Epoxide (oxirane): threemembered ring, cyclic ethers.
O

Reaction of an alkene with a peroxyacid:


peroxyacetic acid
O
H3 C

H
O

H3C

H3C

peroxyacetic
acid

OH

HO OH

acetic
acid

peroxide

OH
H 3C

O
24

Stereochemistry of the epoxidation of alkenes: syn addition of


oxygen. The geometry of the alkene is preserved in the product
Groups that are trans on the alkene will end up trans on the
epoxide product. Groups that are cis on the alkene will end
up cis on the epoxide product.
H

H3CCO3H

trans-alkene

R
R
cis-epoxide

cis-alkene
H

H3CCO3H

H
R
trans-epoxide

6.20: Ozonolysis of Alkenes - oxidative cleavage of an alkene


to carbonyl compounds (aldehydes and ketones). The - and
-bonds of the alkene are broken and replaced with C=O
double bonds.
C=C of aryl rings, CN and C=O do not react with ozone,
CC react very slowly with ozone

25

3 O2

Ozone (O3):

electrical
discharge

2 O3

+
O

mechanism
R1
R2

R3
R4

O3, CH2Cl2
-78 C

O
R1

R2

R1

R3

R2

R4

O O

Zn
-or(H3C)2S

R3
R4

O
ozonide

molozonide

1) O3
2) Zn

R2

R3

R4
+ ZnO or (H3C)SO

1) O3
2) Zn

H
O

1) O3
2) Zn

R1

H
O C

O
H
O

26

27

28