Alkenes and alkynes ()

ntroduction: Additions to alkenes

We shall study other examples of additions to
the double bonds of alkenes. We begin with
the additions of hydrogen halides, sulfuric
acid, water (in the presence of an acid
catalyst), and halogens.
C C
+
A-B A C C B
Addition
An Addition reaction
C C
H C C X
Alkene
H X
HOSO
2
OH
H C C OSO
2
OH
H C C OH
HOH
Alkyl halide
Alkyl hydrogen sulfate
Alcohol
X C C X
X - X
Dihaloalkane
. An addition reaction results in
the conversion of one pi -bond
and one sigma-bond into two
sigma bonds
C C
X C C Y
X - Y
6
9
Bonds broken
9

Bonds formed
sp

sp
3
Addition
. The electrons of the pi-bond are exposed.
Because the pi-bond results from overlapping p
orbital, the pi electrons lie above and below the
plane of the double bond:
C C
6
sp

lectrophiles
H

, X

,
Lewis acids; BF
3
and AlCl
3
Metal ions; Ag

, Hg

, Pt

,
Love elctrons
ydrogen halides react with
alkenes
6
H
+
Cl
-
+
H
Cl
-
H Cl
9
Carbocation
Slow fast
C C
C C
H
CI
H
+
Cl
-
H
+
Cl
-
9
9
sp
2
sp
3
slow
fast
Addition Reaction Mechanism
Carbocation
Addition of Hydrogen HaIides
to AIkenes: Markovnikov's
RuIe
What is it Mar's Rule?-----The addition of
to an alkenes, the hydrogen atom adds to the
carbon atom of the double bond that already
has the greater number of hydrogen atoms.

H
+
X
-
CH

CHCH
3
H X
Markovnikov addition product
Carbon atom with the
greater number of
hydrogen atoms
Markovnikov`s Rule

HCl CH
2
C(CH
3
)
2
H CI
(not ClCH
2
CH(CH
3
)
2

tert-Butyl chloride
2-Methylpropene

HCl
CI

H
Methylcyclohexene
-Chloro--Methylcyclohexane
A mechanism for addition of a
hydrogen halide to an alkene
(two steps;)
$tep 1

HX
Slow
H

rate-determining
step
$tep
H

fast
H X
%eoreticaI expIanation of
Markovnikov's RuIe

H-Br CH
3
CHCH
2
H
Br
Markovnikov addition product
(not BrCH
2
CHCH
3
)

H
Methyl push electron
lectronic ffects

HCl CH
2
C(CH
3
)
2
H CI
(not ClCH
2
CH(CH
3
)
2

tert-Butyl chloride
2-Methylpropene
0

CH
3

HCl
CI

H
Methylcyclohexene
-Chloro--Methylcyclohexane
0

. %e StabiIities of carbocation
C
H
CH
2
+
H-Cl
CH
3
CHCH
2
H
Markovnikov addition product
H
3
C
+
b
a
CH
3
CHCH
2
+
Cl
-
CH
3
CHClCH
3
2
o
C
+
Cl
-
CH
3
CH
2
CH
2
Cl
Anti-Mar's Rule

o
C
+
Stable
Unstable
2
o
C
+

o
C
+
a
b
H
%e StabiIities of
carbocation
C
CH
2
+
H-Cl
CH
3
CCH
2
H
Markovnikov addition product
H
3
C
+
b
a
CH
3
CCH
2
+
Cl
-
CH
3
CClCH
3
3
o
C
+
Cl
-
CH
3
CHCH
2
Cl
Anti-Mar's Rule

o
C
+
Stable
Unstable
3
o
C
+

o
C
+
a
b
H
CH
3
CH
3
CH
3
CH
3
CH
3
Mar's Rule help us to predict
the outcome of the addition
reaction

HCl CH
2
C(CH
3
)
2
H CI
(not ClCH
2
CH(CH
3
)
2

tert-Butyl chloride
2-Methylpropene
0

CH
3
Major Product

-Cl
CH
2
C(CH
3
)
2
l
(not ClCH
2
C(CH
3
)
2

2-Chloro--iodo-2-methylpropane
2-Methylpropene
0

CH
3
(Major product)
An exception to Markovnikov's
RuIe
%e addition of HBr to aIkenes, it is OnIy
wen HBr is used in te presence of
peroxides (ROOR), it is an exception to
Mar' RuIe.
CH
3
CHCH
2

HBr
ROOR
CH
3
CH
2
CH
2
Br
Major product
CH
3
CHBrCH
3
Mar's product
onic reaction
Free radical reaction
. Stereochemistry of te
Ionic Addition to an alkene
CH
3
CH
2
CHCH
2
HCl CH
3
CH
2
CHCH
3

CI
( )-2-Chlorobutane
0

e got a racemic form? Do you know why?

CH
3
CH
2
CHCH
2
+ HCl CH
3
CH
2
CHCH
3
`
CI
( )-2-Chlorobutane
0

H
+
CH
2
H
C
+
H
CH
2
CH
3
Cl
-
H
3
C
CI
H
3
CH
2
C
H
Cl
-
CH
3
CI
H
CH
2
CH
3
Achiral, trigonal
Planar carbocation
( S )-2-Chlorobutane
(50)
( R )-2-Chlorobutane
(50)
nantiomers
A recemic form (
.4 Addition of sulfuric acid to
alkenes
HO S O
O
O

Step , The alkene accepts a proton (H

+
)
from sulfuric acid to form a carbocation
Carbocation
Sulfuric acid
Slow
Alkene

-
O S O
O
O

OSO

O
Carbocation
Hydrogen Sulfate ion
Alkyl hydrogen sulfate
fast
Step
2
, The carbocation reacts with a hrdrogen sulfate ion
to form an alkyl hydrogen sulfate
The addition of sulfuric acid is
also regioselective
HO
S OH
O
O
CH
3
CHCH
2
+
CH
3
CHCH
2
+
CH
3
CH
2
CH
2
+
HOSO
2
O-
CH
3
CHCH
3
OSO
2
OH
HOSO
2
O-
CH
3
CH
2
CH
2
OSO
3
H
Sulfuric acid
Propene
Mar's addition
Anti Mar's addition
More Stable
carbocation
Less Stable
carbocation
sopropyl hydrogen
sulfate
Propyl hydrogen
sulfate
.4A AIcooI from aIkyI
ydrogen suIfates
AIkyI ydrogen suIfates can be easiIy
ydroIyzed to aIcooIs by eating tem wit
water
HO
S OH
O
O
CH
3
CHCH
2
+
CH
3
CHCH
2
+
HOSO
2
O-
CH
3
CHCH
3
OSO
2
OH
H
2
O
CH
3
CHCH
3
OH
Sulfuric acid
Propene
Mar's addition
More Stable
carbocation
sopropyl hydrogen
sulfate
Heat
H
2
SO
4
sopropanol
.5 Addition of water to
alkenes: Acid-catalyzed
hydration
%e acid-cataIyzed addition of water to te
doubIe bond of an aIkene is a metod for
te preparation of Iow moIecuIar weigt
aIcooIs
C C
+
C C
OH
H
HOH
H+
Alkene
ater
Alcohol
Hydration
This reaction is followed Markovnikov's addition Rule
An exampIe is te ydration
of 2-metyIpropene
C C
2-Methylpropene
(sobutylene)
+
ater
H
3
C C
CH
3
C
H
OH
H
H
tert-Butyl alcohol
H
3
C H
H H
3
C
HOH
H
+
Hydration (
This reaction is also followed Markovnikov's addition Rule
0

Mechanism for the hydration of

-methylpropene
C C
H
3
C H
H H
3
C
+
H
3
C C
CH
3
C
H
H
H
+
HOH
H+
H
2-Methylpropene
(sobutylene)
Hydration
0

Step
+ H
2
O
Carbocation
Slow
Step 2 H
3
C C
CH
3
C
H
H
H
+
+ H
2
O:
Carbocation
H
3
C C
CH
3
C
H
H
H
O
+
H
H
fast
H
3
C C
CH
3
C
H
H
H
O

$tep 3.
H
2
O:
1,8t
H
3
C C
CH
3
CH
3
O
+ H
3
O
+
tert-Butyl alcohol
AIkenes ydration is foIIowed te
occurrence of rearrangements
H
C CH
2
C
CH
3
CH
3
H
3
C
+
H
3
C C
CH
3
CH
CH
3
CH
3
+
HOH
+ H
2
SO
4
H
3,3-Dimthyl-2-butene
Hydration
0

2
o
Carbocation
Slow
H
3
C C
CH
3

3
o
Carbocation
CH
3

H
3
C C
CH
3
CH
3

H
2
O:
O

H
3
C C
CH
3
CH
3

O
2,3-Dimethyl-2-butanol
(Major product)
-CH
3
immagration
.6 Addition of bromine and
chlorine to alkenes
. AIkanes react wit bromine
R H
+
Br
2
Room temp
in the dark, CCl
4
No appreciable reaction
Alkane
R
H
+
Br
2
Room temp
sunlight, CCl
4
Alkane
R Br
+
HBr
Alkyl halide
Hydrogen bromide
(detected by moist
blue litmus)
(red brown)
(Colorless)
2. Addition of bromine and
cIorine to aIkenes
+
Br
2
Br Br
Room temp
in the dark, CCl
4
Alkene
(red brown)
Vic-Dibromide
(colorless)
Because of rapid decolorization of Br
2
/CCl
4
,
it is a useful test for carbon-carbon multiple bonds
istinguis aIkanes wit AIkenes
+
Br
2
Room temp
in the dark, CCl
4
Alkene
(red brown)
CH
2
CH
2
CH
2
BrCH
2
Br
,2-Dibromoethane
(Colorless)
CH
3
CH
3
Br
2
Room temp
in the dark, CCl
4
(red brown)

No reaction
Alkane
istinguis cycIoaIkanes wit
cycIoaIkenes
+
Br
2
in the dark, CCl
4
cyclohexene (red brown)
Br
2
Room temp
in the dark, CCl
4
(red brown)
No reaction
trans-,2-Dibromocyclohexane
cyclohexane
(Colorless)
Br
Br
H
H
. Addition reaction of chlorine to
alkenes
+
Cl
2
2-butene
2,3-Dichlorobutane
(Colorless)
CH
3
CHCHCH
3
CH
3
CHClCHClCH
3
-9
o
C
CH
3
CH
2
CHCH
2
+ Cl
2
-9
o
C
,2-Dichloropentane
(Colorless)
CH
3
CH
2
CHClCH
2
Cl
-Pentene
.6A Mechanism of halogen
addition
Br
Br
Br

lectrophiles

0
Bromonium ion
Br
-
Br
+
Br
Br
Br
Br
+
trans-Dibromide
trans-Dibromide
.7 Stereochemistry of the
addition of halogens to alkenes
It is anti addition
Br
2
CCl
4
Br
H
H
Br
cyclopentene trans-,2-Dibromocyclopentane
()-,2-Dibromocyclopentane
%is anti addition of bromine
to cycIopentene can be
expIained by a mecanism
Br
2
CCl
4
cyclopentene
Br

Bromonium ion
Br
H
Br
H
H
Br
H
Br
+
nantiomer
trans-,2-Dibromocyclopentane
()-,2-Dibromocyclopentane
Cyclohexene
Br
2
Br
+
Br
-
inversion
at C-
Br
Br
+
Br
Br
Br
Br
Br
Br
Most stable
conformation
.7A Stereospecific reactions
trans-2-Butene
Bromonium ion
H
H
3
C H
CH
3
+ Br
2
H
3
C
H
CH
3
H
Br
+
Br
-
a
b
(chiral CC
Br
Br
H
3
C
H
H
CH
3
Br
Br
H
H
3
C CH
3
H
a
b
(2R, 3S) (meso
(2R, 3S) (meso
trans-2-Butene reacts with bromine
is--Butene reacts with
bromine
H
3
C
H H
CH
3
+ Br
2
H
H
3
C
CH
3
H
Br
+
Br-
cis-2-Butene
Bromonium ion
a
b
achiral
Br
Br
H
H
3
C
H
CH
3
a
b
(2R, 3R) chiral
Br
Br
H
3
C
H CH
3
H
nantiomer
(2S, 3S) chiral
.8 HaIoydrin formation
f the halogenation of an alkene is carried out
in aqueous solution (rather than in carbon
tetrachloride), the major product of the
overall reaction is not a vic-diaIide, but
rather it is a halo alcohol caIIed a
aIoydrin.
+ X
2
+
H
2
O
C
X
C
OH
+
C
X
C
X
Halohydrin
vic-Dihalide
Major product Minor product
alohydrin formation can be
explained by the following
mechanism:
+
X
H
2
O
X
0

+
Step
C C
X
+
Halonium ion
Step2 C C
X
+
Halonium ion
H
2
O X
-
Anti-addition
C
X
C
OH
+
C
X
C
X
Halohydrin
vic-Dihalide
Major product Minor product
sobutene reacts with bromine
in water
C CH
2
H
3
C
H
3
C
0

Br
2
CH
3
C H
3
C CH
2
Br
+
0

:OH
2
H
3
C
CH
3
+OH
2
CH
2
Br
- H
+
H
3
C
CH
3
OH
CH
2
Br
(73)
. Radical addition to alkenes:
The anti-Markovnikov addition
of hydrogen bromide
R
O O R
R
O O H
An organic peroxide
An organic hydroperoxide
HC CH
2
H
3
C
HBr
H
3
C CHCH
3
Br
0
0

No peroxide
Markovnikov addition
HC CH
2
H
3
C
HBr
H
3
C CH
2
CH
2
Br
R
O O R
0
0

organic peroxide
Anti-Markovnikov addition
Do you know why?
ree Radical reaction
R
O O R
2 R
O
An organic peroxide
Step
heat
Chain nitiation
Step 2
R
O

HBr
ROOH + Br
HC CH
2
Br
H
3
C
Chain Propagation
CH
3
CHCH
2
Br
Step 3
H
3
C CHCH
2
Br H
CH
3
CHCH
2
Br H Br
Anti-Markovnikov addition
Step 4
HC CH
2
H
3
C
HBr
H
3
C CH
2
CH
2
Br
R
O O R
0
0

organic peroxide
Anti-Markovnikov addition
Do you know why?
t i8 , 17ee 7,/ic,l 7e,ction
HC CH
2
H
3
C
HBr
H
3
C CHCH
3
Br
0
0

No peroxide
Markovnikov addition
t i8 ,n ionic 7e,ction
.A Other radical additions to
alkenes
%etrabromometane (CBr
4
) reacts wit -
octene to yieId ,,,3-tetrabromononane
CH
3
(CH
2
)
5
CHCH
2
CBr
3
Br
Br
ROOR
CH
3
(CH
2
)
5
CHCH
2
+ CBr
3
,,,3-tetrabromononane
Radical additions
The mechanism for this
reaction is as follows:
Chain nition
Step RO OR 2RO
RO +
Br CBr
3
ROBr + CBr
3
Step 2
CH
3
(CH
2
)
5
CHCH
2
CBr
3
Br
CH
3
(CH
2
)
5
CHCH
2
CBr
3
CH
3
(CH
2
)
5
CHCH
2
CBr
3
CH
3
(CH
2
)
5
CHCH
2
CBr
3
Br
CBr
3
+
+
,,,3-tetrabromononane
Chain Propagation
Step 3
Step 4
Other examples of radical
additions to alkenes are the
following:
CH
3
(CH
2
)
3
CHCH
2
+ HCCl
3
ROOR
peroxide
CH
3
CH
2
CH
2
CH
2
CH
2
CCl
3
,,-Trichlorohexane
-Hexene
(CH
3
)
2
CCH
2
CH
3
CH
2
SH
ROOR
peroxide
(CH
3
)
2
CHCH
2
SCH
2
CH
3
sobutene
CH
3
CH
2
CCH
2
CH
3
+
CCl
4
CH
3
CH
2
CCH
2
CCl
3
CH
3
CI
,,,3-Tetrachloro-3-methylpentane
peroxide
ROOR
sopentene
RadicaI poIymerization of :Addition
poIymers
ROOR
* CH
2
CH
2
* m CH
2
CH
2
thylene Monomer
Polymerization
n
Polyethylene polymer
Dm and n are large numbers)
ROOR
* CH
2
CH * m CH
2
CH
Styrene Monomer
Polymerization
n
Polystyrene polymer
Dm and n are large numbers)
Oter common addition
poIymers
ROOR
* CH
2
CH *
CI CI
m CH
2
CH
Chloroethene
Polymerization
n
Poly(vinyl chloride)
ROOR
* CH
2
CH *
CN CN
m CH
2
CH
Acrylonitrile
Polymerization
n
Polyacrylonitrile Orlon
ROOR
* CF
2
CF
2
* m CF
2
CF
2
Tetrafluoroethene
Polymerization
n
Polytetrafluoroethene (Teflon)
ROOR
* CH
2
C
CH
3
COOCH
3
*
CH
3
m CH
2
CCOOCH
3
Methyl methacrylate
Polymerization
n
Poly(methyl methacrylate)
Oxidations of aIkenes : Syn ydroxyIation
AIkenes undergo a number of reactions in wic
te carbon-carbon doubIe bond is oxidized.
Potassium permanganate (KMnO
4
) or osmiun
tetroxide OsO4), for exampIe, can be used to
oxidize aIkenes to ,2-dioIs caIIed gIycoIs.
C C
cold 5 KMnO
4
or OsO
4
, Na
2
SO
3
OH OH
Syn-,2-diols
C C

cold 5 KMnO
4
or OsO
4
, Na
2
SO
3

OH OH
,2-thanediol
(ethylene glycol)
thene
C C
H
H
H
H
3
C
H
H
H
H
OH OH
cold
5
KMnO
4
or OsO
4
, Na
2
SO
3
,2-Propanediol
(propylene glycol)
Propene
.A Syn hydroxylation of
alkenes----Mechanism
C C
cold 5 KMnO
4
O O
Mn
O O
-
NaOH, H
2
O
Mn
O
O O
O
-
Syn-,2-diols
OH OH
OH
-
H
2
O
C C
OsO
4
, Na
2
SO
3
O O
Syn-,2-diols
OH OH
Os
O O
-
OH
-
H
2
O
Os
O
O O
O
+ MnO
4
-
O
Mn
O
O O
-
H H
H
2
O
OH
-
OH OH
H
H
cis-,2-Cyclopentanediol
(a meso compound)
Cold
+ OsO
4
O
Os
O
O O
H H
NaHSO
3
OH OH
H
H
cis-,2-Cyclopentanediol
(a meso compound)
However, osmium tetroxide is highly toxic and is very expensive
Oxidative cleavage of alkenes
Alkenes are oxidatively cleaved to salts of
carboxylic acids by hot permanganate
solutions.
KMnO
4
H
3
CHC CHCH
3
Acetic acid
OH
-
, heat
2
CH
3
COOH
KMnO
4
H
3
CC
CHCH
3
CH
3
CH
3
CCH
3
O

Acetic acid
OH
-
, heat
2
CH
3
COOH
acetone
CH
3
CH
2
C CH
2
CH
3
KMnO
4
Carbon dioxide
OH
-
, heat
CH
3
CH
2
CCH
3
O

Butanone
OCO + H
2
O
An unknown aIkene wit te
formuIa C
7
H
2
undergoes oxidation
by ot basic KMnO
4
to yieId, after
acidification, onIy one product:
KMnO
4
,
OH
-
, heat ,
2, H
+
C
7
H
2
CH
3
CCH
2
CH
2
CH
2
CH
2
COOH
O
Unknown alkene
C)
CH
3
-Methylcyclohexene
OzonoIysis of aIkenes
-O
O
O
O
O
O
nitial ozonide
M
Second ozonide
M
O
O O
n, H
2
O
O O +
Aldehydes or ketones
(
reduction
The overall process of ozonolysis
followed by reduction with zinc and
water amounts to a disconnection
of the carbon-carbon double bond
in the following fashion.
( 2 ) n, H
2
O reduction
R
R
R''
H
( ) O
3
, CH
2
Cl
2
, -78
o
C
R
R
O
O
R''
H
+
Aldehydes
()
ketones
(
( 2 ) n, H
2
O reduction
H
3
C
H
3
C
CH
3
H
( ) O
3
, CH
2
Cl
2
, -78
o
C
( 2 ) n, H
2
O reduction
CH
H
H
H
( ) O
3
, CH
2
Cl
2
, -78
o
C
H
3
C
CH
3
H
3
C
H
3
C
O
O
CH
3
H
+
Acetaldehyde
()
Acetone
(
CH
H
O O
H
H
+
Formaldehyde
()
sobutylaldehyde
(
CH
3
H
3
C
.4 Addition of bromine and
cIorine to aIkynes
Br
2
, CCl
4
C C C C
Br
Br
Dibromoalkene
Br
2
, CCl
4
C C
Br
Br
Br
Br
Tetrabromoalkane
Cl
2
, CCl
4
C C C C
CI
CI
Dichloroalkene
Cl
2
, CCl
4
C C
CI
CI
CI
CI
Tetrachloroalkane
t is usually possible to prepare
a dihaloalkene by simply adding
one molar equivalent of the
halogen
Br
2
, ( mol)
C C

O
C C
H
3
CH
2
CH
2
C
Br
Br
CH
2
OH
( 80)
CH
3
CH
2
CH
2
CCl
4
HOOCC CCOOH
Br
2
, (mol)
C C
HOOC
Br
Br
COOH
( 70)
CCl
4
Acetylenedicarboxylic acid
(E
trans or ()-2,3-Dibromobutenedicarboxylic acid
(23-aE
Addition of ydrogen aIides
to aIkynes
C C
C C
H
CI
chloroalkene
HCl
HCl
follow Mar's Rule
C C
H
H
CI
CI
gem-Dichloride
C C
C C
H
Br
bromoalkene
HBr
HBr
follow Mar's Rule
C C
H
H
Br
Br
gem-Dibromide
C CH H
3
C
C CH
2
CI
H
3
C
2-Chloropropene
HCl
HCl
follow Mar's Rule
H
3
C C C H
CI
CI
H
H
2,2-Dichloropropane
. Simple chemical tests for
alkanes, alkenes, alkynes, alkyl
halides, and alcohols
.A CemicaI tests
.B Concentrated suIfuric acid
(H
2
SO
4
)
Alkenes
alkynes
alcohols
H
2
SO
4
Alkanes
Alkyl halides
cold
Soluble in H
2
SO
4
insoluble in H
2
SO
4
. Bromine in carbon
tetracIoride ) (Br
2
/CCI
4
)
Alkenes
alkynes
Br
2
/ CCl
4
Alkanes
Alkyl halides
alcohols
Decolorization of bromine
do not react with bromine
in the absence of light
. CoId diIute potassium
permanganate (KMnO
4
)
Alkenes
alkynes
cold KMnO
4
Alkanes
Alkyl halides
alcohols
The deep-purple color
of KMnO
4
disappear
to form MnO
2
do not react with KMnO
4
. AIcooIic siIver
nitrate (AgNO
3
/ ROH)
Alkenes
Alkynes
Alcohols
AgNO
3
Alkanes
ROH
Alkyl halides
No reaction
AgX
.F SiIver Nitrate in
ammonia (AgNO
3
/ NH
3
)
Alkenes
Alcohols
Ag(NH
3
)
2
+
Alkanes
OH
-
Alkyl halides
Alkynes
R
No reaction
RC CAg
(terminal alkynes)
Special Topic -----ivalent carbon
compounds: Carbenes
Neutral divalent carbon compounds are
called carbenes (CH
2
: MetyIene
Most carbenes are highly unstable
compounds.
The reactions show a stereospecificity
The reactions of carbenes are also of great
synthetic use
. Structure of methylene
(carbenes)
. The preparation of carbenes
:CH
2
N N:
+
:CH
2 :N N:
Heat
Light
+
Diazomethane
Methylene
or carbene
Nitrogen

H
3
C
CH
3
CH
3
OK HCCl
3
(CH
3
)
3
COH :CCl
3

-
2
:CCl
2
+ Cl-
+ K
+
Dichlorocarbene
potassium
tert--butoxide
. Reactions of Methylene
MetyIene reacts wit aIkenes by
adding to te doubIe bond to form
cycIopropanes
:CH
2
Methylene
or carbene
+
Dichlorocarbene
]
R
H
H
R
+
R
H
H
R
:CCl
2
CI CI
trans-
trans-
:CCl
2

CHCl
3
+ (CH
3
)
3
COK
l
l
7,7-Dichlorobicyclo40]heptane
1

3
4
5
6
7
Cyclohexene
Cyclohexene

CH
2

2
n, Cu
2
Cl
2
Bicyclo40]heptane
(92)