Alkene Reaction

CARBON
CHEMISTRY 2
Alkene
Reaction and Mechanisms
6 Characteristic Reactions
Hydrochlorination (hydrohalogenation)
C C + HCl C C
H Cl
Hydration
C C + H2 O C C
H OH
6-2
Copyright © 2000 by John Wiley & Sons, Inc. All rights reserved.
Bromination (halogenation)
C C + B r2 C C
Br Br
Hydroxylation (oxidation)
C C + OsO 4 C C
HO OH
6-3
Hydrogenation (reduction)
C C + H2 C C
H H
Polymerization
initiator
n C C C C
n
6-4
6 PE Diagrams
transition
state
Potential energy
Ea
A+B ΔH
C+D
Reaction Coordinate
6-5
6 Addition of HX
• Addition is regioselective
CH 3 CH = CH 2 + H C l
Propene
Cl H H Cl
CH 3 C H-CH 2 + C H3 C H- CH 2
2-Chloropropane 1-Chloropropane
(not observed)
• Markovnikov’s rule:
rule in the addition of HX or H2O
to an alkene, H adds to the carbon of the double
bond that has the greater number of hydrogens
bonded to it
6-6
6 HCl + 2-Butene
• A two-step mechanism
Step 1: formation of sec-butyl cation, a 2° carbocation
•
intermediate
slow, rate-
δ+ δ-
C H3 C H= C HCH 3 + H -C l limiting step
H
+ -
C H3 C H -C H CH 3 + Cl
sec-Butyl cation
6-7
6 HCl + 2-Butene
• Step 2: reaction of the sec-butyl cation with chloride
ion
Cl
- + fast
Cl + C H3 CH C H 2CH 3 C H3 C HC H 2C H3
Chloride ion sec-Butyl cation
(a Lewis base) (a Lewis acid)
6-8
6 Carbocations
• Carbocation:
Carbocation a species containing a positively
charged carbon
• Carbocations are
• classified as 1°, 2°, or 3° depending on the number of
carbons bonded to the carbon bearing the positive
charge
• electrophiles; that is, they are “electron-lovers”
6-9
6 Carbocation Structure
• Bond angles about the + R
positively charged carbon are R C
R
120°
• Carbon uses sp2 hybrid orbitals
to form sigma bonds to the
three attached groups
• The unhybridized 2p orbital lies
perpendicular to the sigma
bond framework and contains
no electrons
6-10
6 Carbocation Stability
• Relative stability
H H C H3 C H3
H C+ C H3 C + C H3 C + C H3 C +
H H H C H3
Methyl Ethyl Isopropyl tert-Butyl
cation cation cation cation
(methyl) (1°) (2°) (3°)
Increasing carbocation stability
6-11
6 Carbocation Stability
• Carbocations are stabilized by the electron-
withdrawing inductive effect of the positively-
charged carbon
• according to molecular orbital calculations:
+0.06 +0.13 C H3
H
H C H3 C C
H +0.83 C H3 +0.60
6-12
6 Addition of H2O
• Addition of water is called hydration
• Acid-catalyzed hydration of an alkene is
regioselective - hydrogen adds to the less
substituted carbon of the double bond
OH H
H 2 SO 4
CH 3 CH = C H 2 + H 2 O C H3 C H - C H2
Propene 2-Propanol
6-13
6 Addition of H2O
• Step 1: proton transfer from solvent to the alkene
slow, rate- +
CH 3 CH = C H 2 + H O H limiting step
H +
C H3 C H CH 3 + O H
A 2o carbocation H
intermediate
6-14
6 Addition of H2O
• Step 2: reaction of the carbocation intermediate with
H2O to form an oxonium ion
+
CH 3 C H CH 3 + fast
O-H CH 3 C HCH 3
H O+
H H
An oxonium ion
• Step 3: proton transfer to solvent
fast C H 3 C HC H 3 + +
C H3 C H CH 3 H O H
O
+ OH
H H
H H
O
H 6-15
6 Addition of Cl2 and Br2
• Carried out with either the pure reagents or in an
inert solvent such as CCl4 or CH2Cl2
Br Br
C H3 C H = C HCH 3 + B r 2 CH 3 CH -C HC H3
C C l4
2-Butene 2,3-Dibromobutane
6-16
• Addition is stereoselective
Br
+ Br 2
CCl 4
Br
Cyclohexene trans-1,2-Dibromo-
cyclohexane
• Stereoselective reaction:
reaction a reaction in which
one stereoisomer is formed or destroyed in
preference to all others than might be formed
or destroyed 6-17
• Addition involves a two-step mechanism
• Step 1: formation of a bridged bromonium ion
intermediate
Br
Br
Br
+ Br -
C C C C
A bridged bromonium
ion intermediate
6-18
• Step 2: Attack of halide ion from the opposite side of
the three-membered ring
+
Br Br
C C C C
- Br
Br
Anti addition
6-19
• For a cyclohexene, anti coplanar addition
corresponds to trans-diaxial addition
Br
B r2 Br
Br
trans-Diaxial trans-Diequatorial
(less stable) B r (more stable)
6-20
6 Oxidation with OsO4
• Oxidation by OsO4 converts an alkene to a
glycol, a compound with -OH groups on two
adjacent carbons
• oxidation is syn stereoselective
+ O sO 4 ROOH H H
HO OH
Cyclopentene cis-Cyclopentanediol
(a cis glycol)
6-21
6 Oxidation with OsO4
• Intermediate is a cyclic osmic ester containing a
five-membered ring
H H H H
O O HO OH
O O
Os
Os
O O
O O
A cyclic osmic ester
6-22
6 Reduction of Alkenes
• Most alkenes react with H2 in the presence of a
transition metal catalyst to give alkanes
• commonly used catalysts are Pt, Pd, Ru, and Ni
Pt
+ H2
Cyclohexene Cyclohexane
• The process is called catalytic reduction or,

alternatively, catalytic hydrogenation
6-23
6 Reduction of Alkenes
• the most common pattern is syn stereoselectivity
C H3 C H3 C H3
H2 / P t +
C H3 C H3 C H3
1,2-Dimethyl- 70% to 85% 30% to 15%
cyclohexene cis-1,2-Dimethyl- trans-1,2-Dimethyl-
cyclohexane cyclohexane
6-24
6 Reaction Stereochemistry
• how many stereoisomers are formed in the addition of
bromine to cis-2-butene?
H H Br 2
C C
H 3C CH 3
cis--2-Butene
Br H H Br
C H3 H3 C
C C + C C
H H
H3 C Br Br CH 3
A pair of enantiomers
(a racemic mixture)
6-25
• Consider the oxidation of 2-butene by OsO4
OH OH
OsO 4
CH 3 C H = C H2 C H3 CH 3 C H -C HCH 3
2-Butene 2,3-Butanediol
• three stereoisomers are possible for 2,3-butanediol;

one pair of enantiomers and one meso compound
• which are formed in this oxidation?
6-26
• syn hydroxylation of cis-2-butene produces only the
meso compound
H H
H 3C 2 3 C H3
C C
HO OH identical;
(2S,3R)-2,3-Butanediol
a meso
compound
HO OH
2 3
C C
H
H C H3
H3 C
(2R,3S)-2,3-Butanediol
6-27
• Enantiomerically pure products can never be
formed from achiral starting materials and achiral
reagents
• An enantiomerically pure product can be
generated in a reaction if at least one of the
reactants is enantiomerically pure, or if the
reaction is carried out in an achiral environment
6-28

Alkene Reaction

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CARBON

• The process is called catalytic reduction or,

• three stereoisomers are possible for 2,3-butanediol;

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