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H2C
CH2
Br2
Br
H2C
Br
CH2
Br
HC
Br
Br
2 Br2
CH
HC
CH
Br
Reactions of
Alkenes and Alkynes
CHAPTER SUMMARY
105
Chapter 5
106
Chapter 5
usually regioselective and the rule for predicting the predominant product
is known as Markovnikov's rule.
5.2 Addition Reactions of Alkynes
A. General Reaction Equation for Addition to Alkynes
Alkynes add hydrogen, hydrogen halides, and halogens (chlorine
and bromine). They can add one mole of reagent to produce a double
bond or two moles to form a single bond.
B. Mechanism of Catalytic Hydrogenation
of Alkenes and Alkynes
Hydrogenation of alkenes and alkynes is accomplished in the
presence of a metal catalyst which attracts both the hydrogen and
hydrocarbon to its surface. As a result of the reactants being adsorbed
onto the same surface, the reaction occurs with cis addition.
C. Electrophilic Addition Mechanism for Alkynes
The mechanism of electrophilic addition to alkynes is the same as
with alkenes. Orientation of addition of unsymmetrical reagents to
unsymmetrical alkynes is determined by the stability of the intermediate
carbocation.
D. Addition of Water to Alkynes
Alkynes add water to form aldehydes and ketones.
5.3 Addition Polymers
A polymer is a giant molecule composed of a repeating structural unit
called a monomer. Addition polymers result from the addition of alkene
molecules to one another. The polymerization occurs by cationic, freeradical, and anionic reaction mechanisms. Examples of addition polymers
include polyethylene, polystyrene, PVC, and Teflon.
107
Chapter 5
108
Chapter 5
Chapter 5
B. Ozonolysis
Ozonolysis cleaves the carbon-carbon double bond of an alkene to
form aldehydes and ketones.
5.8 Acidity of Terminal Alkynes
Terminal alkynes have weakly acidic hydrogens that can be abstracted by
strong bases such as sodium amide.
CONNECTIONS 5.4 The Treatment of Atherosclerosis
SOLUTIONS TO PROBLEMS
5.1 Addition and Elimination Reactions
(a) H2C
Br
H2C
CH 2 + KOH
H2C
H2C
CH 2 + HBr
OH
CH 2
H2SO 4
CH 2
CH 2 + H 2O
H2C
H2C
OH
110
Addition
CH 2
Elimination
+ H 2O
H
H2SO 4
H2C
Elimination
+ KBr + H 2O
Br
(b) H2C
CH 2
CH 2
H
Addition
Chapter 5
CHCH3 + H2
b) CH3CH
CHCH3 + Cl2
Pt
CHCH3
Cl
Cl
c) CH3CH
d) CH3CH
CHCH3 + HBr
CH3CH
CHCH3 + H2O
H2SO 4
CHCH3
Br
H
CH3CH
HO
CHCH3
H
(a)
HCl
Cl
CH 2 + HBr
H
CH 3CH 2CH
Br
CH 2
or
H
CH 2
CH 3CH 2CH
H
Br
CH 3CH 2CH
CH 2
Br -
CH 3CH 2CH
Br
H
CH 3CH 2CH
CH 2
H
CH 2
CH 3CH 2CH
H
CH 2
Br -
CH 3CH 2CH
CH 2
Br
111
Chapter 5
CH 3CH
CH 2
CH 3CH
Cl2
CH 2
Cl
(b)
H3C
Br2
Br
CH 3
Cl
CH 3
H3C
Br
(a) CH 3CH
CH 2
Cl
CH 3CH
CH 2
Cl
CH 3CH
Cl
Cl
(b)
CH 2
Cl
Br
H3C
CH 3
CH 3CH
CHCH 3 + H2O
H2SO 4
CH 3CH
OH
(b) CH 3CH
CHCH 3
H+
CH 3CH
CHCH 3
CHCH 3
H
H2O
H
CH 3CH
OH
H
112
CHCH 3
H
- H+
CH 3CH
OH
CHCH 3
H
Chapter 5
5.8 Carbocations
Arranged most to least stable:
CH 3
CH 3
CH 3CCH 3 > CH 3CHCH 2CH 3 > CH 3CHCH 2 and CH3CH 2CH 2CH 2
3O
2O
1O
1O
most stable
5.9 Orientation of Addition
(a)
CH3
H+
CH3CH 2C
+
Cl
CH3CH 2C
CH3
CH3CH 2C
CH2
CH3
Cl H
predominant
product
more stable
3 carbocation
CH2
CH3
CH3CH 2C
H+
CH2
+
CH2
Cl
CH3
CH3CH 2C
H
CH2
Cl
less stable
1 carbocation
(b)
H+
CH3 H2O
- H+
CH3
OH
CH3
predominant
product
more stable
3 carbocation
CH3
H2O
- H+
CH3
H
OH
less stable
2 carbocation
113
Chapter 5
CCH3 +
1Br2
CH3C
CCH3
Br Br
Br
(b) CH3C
CCH3
2Br2
Br
CH3C
CCH3
Br Br
(c) CH3C
CCH3 +
1Cl2
CH3C
CCH3
Cl Cl
H
(d) CH3C
CCH3
Ni
2H2
CH3C
CCH3
CH3CH 2
CH3
C
Pt
+
H3C
114
CH 3
cis
addition
CCH3
2H 2
Pt
H2
H3C
CH 3
Chapter 5
CH
2HBr
CH3CH 2CH2C
H
CH
Br
Reaction Mechanism
.. _
:Br
.. :
H+
CH3CH 2CH2C
CH3CH2CH2C
CH
HBr adds to
triple bond
and then to
Br
the resulting
double bond.
CH3CH2CH2C
In each case
the more stable
Br
carbocation is formed.
H
.. _
:Br
.. :
CH3CH2CH2C
CH
CH
Br H
CH3CH 2CH2C
CH
H+
CH
Br H
CH 3C
CH +
H2O
H2SO 4
CH 3C
HgSO 4
CH 2
CH 3CCH 3
OH
enol
ketone
CH2
.. CH
H .. CH2
CH3
H .. CH2
CH
CH3
CH2
CH+
CH2
.. CH
CH3
CH+ etc. etc.
CH3
.. A -
CH3
H
CH2
CH
CH3
115
Chapter 5
ROOR
Cl
RO.
CH 2
.. C
RO..CH 2
Cl
RO.. CH2
Cl
CH 2
Cl
Cl
Cl
C. CH2
C.
Cl
Cl
Cl
.. C
Cl
Cl
etc. etc.
RO
CH2
OR
Cl
(a)
CH
CH 2
Br
H
1,2 addition
CH 2 CH
CH
CH 2
+ 1HBr
CH 2 CH
CH
CH 2
H
Br
1,4 addition
(b)
Br
+ Br2
Br
Br
+
Br
1,2 addition
116
1,4 addition
Chapter 5
Reaction Mechanism
STEP 1: Electrophile, H+
is attracted to pi-cloud and uses
two pi-electrons to bond. More
stable allylic carbocation results.
CH 2 CH
CH 2 CH
CH 2
H+
CH
+
CH 2
CH 2 CH
+
CH 2
H
Br-
CH
CH 2
Br
CH 2 CH
CH
Br
1,2 addition
(b)
CH
Resonance Forms
CH 2 CH
CH
CH 2
H
1,4 addition
Reaction Mechanism
Br+
Br
Br
Resonance Forms
Br-
Br
+
Br
Br
Br
1,2 addition
1,4 addition
117
Chapter 5
CH 3CH
CHCH 2
CH 3CH
CH
CH 3CHCH
CH 2
+
CH 3CH
(b)
CH 3CH
CHCH 2
CH 3CH
CH
CH
CH 3CHCH
CH 2
CH 2
CH 2
CH 3CH
(c)
CH 2
CH 3CH
CHCH 2
CH 3CH
CH
CH
CH 3CHCH
CH 2
CH 2
CH 2
CH 3CH
CH
CH 2
(d)
CH 3
CH 3
CH 3
5.20 Terpenes
(a) monocyclic monoterpene
118
CH 3
Chapter 5
CH 3CH
KMnO 4
CH 2
CH 3CH
H2O
OH
KMnO 4
(b)
CH 2
OH
H CH
3
H2O
HO
CH 3
OH
5.22 Ozonolysis
Each double bond is cleaved; the carbons become carbon-oxygen double
bonds.
CH3
(a) CH3C=CHCH2CH 3
O3
H2O
O
+
CH 3CCH3
CH 3CH 2CH
Zn
CH 3
CH 3
O3
H2O
O CH 3
O
+
HCH
HC
Zn
O
O
+
HCCH 2CH
c)
O3
H2O
Zn
CH 3CCH 3
5.23 Ozonolysis
Whereever you see a carbon-oxygen double bond, there was originally a
carbon-carbon double bond. Since there are only two carbon-oxygen double
bonds, they must have been involved in the carbon-carbon double bond.
CH 3 CH=CHCH2 CH 3
5.24 Acidity of Terminal Alkynes
CH3CH 2C CH + NaNH 2
CH3CH 2C
CNa + NH3
119
Chapter 5
CH 3
CH 2
(b)
CH 3
CH 3
(e)
CH 3C
Cl
Cl
Br
Br
CH 3CH 2CCH 3
(g) CH 2
(c)
CH 2CH 3
CH 3
CH
CH
CH 2
Cl
Cl
Cl
OH
CH 2CH 3
(h)
OH
CH
Cl
b) CH3CH 2C
CCH3
c) CH3CH 2CH2CH2CH
CH2
Br Br
Cl
Br
(e)
CH 3CH 2CH 2C
CH 2
Br
Br
Br
(a) CH 3CH
CH 2
CH 3CH
CH 2
CH 3CH
Br
The carbocation in this case is actually a bromonium ion.
CH 3
(b)
CH 3C
CHCH 3
H+
CH 3
CH 3C
CHCH 3
H
120
Cl
CH 2
Br
Br
CH 3
CH 3C
CHCH 3
Cl H
CH 3
(c)
Chapter 5
+ CH 3
Br
CH 3
Br
CH 3
(d)
CH 3C
CH 2
CH 3
H+
CH 3C
CH 3
H2O
CH 2
CH 3C
CH 2
+ OH
-H
CH 3
CH 3C
CH 2
OH H
CH 3C
CCH 3
H+
Cl
CH 3C
CCH 3
CH 3C
H
Cl
CH 3C
Cl
CCH 3
Cl
Cl
+
CH 3C
CCH 3
H
CCH 3
Cl
H
H+
CH3CHC
CCH3
(b)
+
CH3
CH3
1H2
1H2
Pd
CH3
CH3CH
C
H
Pd
H
CH3
CH3
H
121
Chapter 5
OH OH
KMnO 4/H2O
H3C
H3C
(a) CH3CH 2C
H2SO 4
H2O HgSO
4
CH 3CH 2CCH3
O
(b) CH3C
CCH3
H2SO 4
H2O HgSO
4
CH 3CH 2CCH3
CH 2
CH
CH 2
H+
CH 3
CH 3
H2C
CH
H2C
CH 2
CH
CH 2
resonance forms
H2 O
- H+
CH 3
H2C
H
CH
OH
1,2 addition
122
CH 3
CH 2
H2C
CH
H
1,4 addition
CH 2
OH
Chapter 5
Cl +
(b)
Cl
Cl
+
resonance forms
The electrophile
attacks one of the
double bonds to
form an allylic
carbocation that
is described by
two resonance
forms. Neutralization forms two
products.
Cl
Cl
Cl
Cl
+
Cl
1,2 addition
1,4 addition
(a) CH3CH
CH CH
. 2
Resonance hybrid
CH3CH CH
(c)
CH 2
..
_
CH
..
O:
..
CH 2
H
CH3
CH2
CH 2
H
CH3
CH3CH
.. _
:O:
..
O:
(b)
CH2
C
H
CH3
CH3
+
+
(d)
O
123
Chapter 5
-. ..
. .O.
.. .
O.
C
... ..O.
. ..O
.. ..O
.O..
2-
O
O
-. ..
.. .O. ..-
.. ..O..C
...
..O. -
CH2
CF2
b)
CH2
CH
Br
KMnO4
CH 3CHCH2
OHOH
(b)
KMnO4
OHOH
5.38 Ozonolysis: Section 5.7B
Each place there is a carbon-carbon double bond it cleaves and each carbon
becomes a carbon-oxygen double bond.
124
a) CH 3CCH3
O
c) CH3C
HCCH2CH2C
CCH2CHCH2CH
Chapter 5
CH3
C
2 HCH
CH
O
O
CH3
b)
CH3
HCH
CH2CH
O
CCH3
O
CH 3CH 2C
(b)
CCH 2CH 3
CH 3 CH 3
CCH 3
CH 3
CH 3
(c)
CH 3C
CH 3
(d)
CH 3
CH 3
NH3
CHCH3
CH3
OH
OH
CH3
d) D = CH3CHCH
c) C = CH 3CHCH2CHCH3
CH2
e) E =
F=
125
Chapter 5
H = CH3CH
CH2
X = Cl, Br, I
X
g) I = CH 3CH
CHCH 3
K =CH 3CH
CHCH 3
J = CH 3CH 2CHCH 3
Br
..
:OH
CH3
CH3
CH2
CH3
+ :..
OH
CH3
..+
-H
OH
CH3
:O :
CH3CH 2C CCH3
1H2
Pt
CH3CH 2
CH3
C C
H
CH3
(b)
1H2
Pt
CH3
CH3CH 2CH
H
CH3
C C
2HBr
126
CH3
Chapter 5
Cl
2HCl
2Cl2
CH 3CH 2CCH2CH 3
Cl
Cl Cl
CH3CH 2C CCH3
Cl Cl
C8H10
4H2
C8H18
hydrogenation product
127
Chapter 5
resonance forms
products
CH 3CH=CH-CH=CH-CHCH2CH 3
CH 3CH=CH-CH=CH-CHCH2CH 3
Br
CH 3CH=CH-CH-CH=CHCH2CH 3
Br CH 3CH=CH-CH-CH=CHCH2CH 3
Br
CH 3CH-CH=CH-CH=CHCH2CH 3
CH 3CH-CH=CH-CH=CHCH2CH 3
Br
+ Br 2
2Br2
128
Chapter 5
HBr
HBr
major
product
3. Make a model of 2-butyne and the product of cis addition of hydrogen.
H2
Pt
129
Chapter 5
Br2
130