Chapter 9

alkene ; Iunctional group double bond rxns at double bond

rxns not at double bond
but at other positions
bond is weak, loosely held, exposed reactive
electrophilic addition
Iree radical addition
electron source
a bond is broken
two strong bond are Iormed
a bond is broken
C C
p 319


Hydrogenation

unsaturated
compds
saturated
compds
H

optically inactive
compds
optically active
compds
depends on
catalysts
H

O O
ex)
quantiative
analysis
is possible
Pt, Pd, Ni etc.
on supporter
heterogeneous
catalyst
(two phases)
homogeneous
catalyst
(one phase)
organic
complexes
oI Rh, Ir etc
Iormed ; 2 C-H
broken ; H-H & bond
heat is evolved ; heat oI hydrogenation
~ 30 Kcal/mole
without catalysts, no rxn due to high E
cataysts lower E to provide diIIerent mechanisms (Eig 9-2)
weaken bond
break H-H bond
speed up
dehydrogenation
also lower E oI
the reverse rxn



H

H -28.6
H -27.6
trans is more stable than
cis by about 1Kcal
trans is less crowding
and less van der Waals strain
more stable
R

C CR

C CHR R

C CH

,
RCH CH

C CH

RCH CHR
p327


C C C C
X
CH

CHCH

CH

CH CH

CH

C CH

I
H

C CCH

CH

CH

CH

CHICH

CH

CH

CH

CH CHCH
CH

CH

CH

CHICH

HX
HOAc
( ~1 : 1 )

HI
HI
HI

( not use H

O as a solvent
due to the addition oI H

O )
I
CH

CH

CHCl CH

CHICl
HI


Markovnikov's rule ; H in HX attaches to the carbon having more H.
regioselective
HBr addition ; normal condition (in the presence oI inhibitor )
Markovnikov
addition
hydroquinone
diphenylamine
with peroxide anti-Markovnikov addition
t-butyl peroxide
benzoyl peroxide


ex)
HBr
HBr
peroxide
CH

C CH

Br
CH

CH

CH

CH

Br
CH

C CH

CH

CH

O
CH

CH CH

CH

CH
CH

CH

CH

C CH

OH
H

SO

CH

CH
H

O
CH

CH

CH CH

CH

C CH

CH

CH

C CH

CH

p 331
require more concnd H

SO

OSO

H HO
CH

CH

C C C C
H
H
slow

Z
Z
Z
C C
H
C C
H Z

Iast
(electrophilic addition)
hydration rxn is reversible (p333)
HZ ; H-X, H

SO

, H

O



Evidences Ior the mechanism


1) the rate depends on |alkene| and |HZ|.

2) the rxn requires an acidic reagent.
exception : H

O (requires strong acid)

3) rearrangement is possible

CH

CH CH
CH

CH

CH

CH CHCH

CH

CH

CH CHClCH

CH

CH

CCH

CH

CH

CH

C CH

CH

CH

Cl
HCl



CH

C CH
CH

CH

CH

CH

C CHICH

CH

CH

CH

C CH
CH

I CH

CH

HI



4) consistent with the orientation oI addition
the relative reactivities oI alkenes

C C C C
H
H

Z
Z C C
H Z
+

more electron-releasing groups lower
more alkyl groups lower
explain orientation and reactivity ( Eig 9.4, p338)
ex) is more reactive than CH

CHCl CH

CH

E
E



C C C C
X X
X

; Cl

, Br

ex) p339 & 340

cI) I

Iails to react. (too slow)

vicinal dihalide
electrophilic addition
X

C C
C C C C
Br Br Br
Br
Br
Br
bromonium ion
(halonium ion)
alkene ; base, nucleophile
Br

; acid, electrophile


evidence ?
the eIIect oI the alkene structure on reactivity
the more substituted alkene, the more reactive.
electron-releasing substituents activate an alkene.
electron-withdrawing substituents deactivate.
the eIIect oI the added nucleophiles on the products

C C C C C C
Br Y
Br
Br
Y

how about open carbocation? (p342)

cyclic Iorm Irom stereochemistry


























CH

CH

CH

CH

Br OH
Br

O
bromohydrin, chlorohydrin ; halohydrin
X

C C
X
H

O
C
X
C
OH

anti-addition
H
CH

CH CH

CH

CH CH

Cl
H

O Cl

C CH

CH

OH

H
Cl
+
+
CH

CH

CH

Cl
OH

H
CH

CH

CH

Cl
OH
more stable
transition state
CH

C
CH

CH

SO

CH

C CH

CH

or H

PO
CH

C
CH

CH

CH

C CH

CH

CH

C
CH

CH

CH

C CH
CH

CH

C
CH

CH

CH

C CH

CH

CH

C
CH

CH

H
more addition
dimers oI isobutylene
80

CH

C
CH

CH

CH

C CH

CH

H
CH

C CH

CH

CH

C
CH

CH

CH

C CH

CH

CH

C
CH

CH

C
CH

CH

H
CH

C CH

CH

CH

C
CH

CH

CH

C CH

CH

SO

or HE
0

~ 10

intermolecular
hydride shiIt
H
CH

Carbocation

1) combine with Nu
2) rearrange to a more stable carbocation
3) eliminate a H to Iorm an alkene
4) add to an alkene
5) abstract a hydride Irom an alkane
CH

C CH
CH

CH

CH

Hg(OAc)

O / THE
CH

C CH
CH

C
CH

OH Hg(OAc)
NaBH

CH

C CH
CH

C
CH

OH




NaBH

tBuCHCH
tBuCH CH

Hg
not open carbocation due to no
rearrngement and anti-addition
oI H

O
H

O
like halonium ion,
orientation is
controlled by
polar eIIect, not
steric hindrance
tBu CH CH

OH

HgOAc

tBu CH CH

OH HgOAc
tBu CH CH

OH
the result corresponds
to Markovnikov's rule




borane (BH

) exists as dimer
diborane (B

)
B
H
H
H
H
B
H
H
O
(THE)
B
H
H
H
O (complex)

(BH

Et

O
THE
or diglyme
( diethylene glycol methyl ether )
CH

CH

BH

(CH

CH

BH (CH

CH

B
H

OH
CH

CH

OH


CH

CHCH

CH

CH CH

H BH

H BH

+

CH

CH

CH

BH

no rearrangement (not via carbocation)

corresponds to anti-Markovnikov's addition


Me Me
H OH
(syn-addition)
B

OH



CH

CHCH

HBr
peroxide
or h
CH

CH

CH

Br

via Iree-radical rxn

Peroxide rad
O O O
rad HBr rad H Br
CH

CHCH

Br CH

CH CH

Br
CH

CH

CH

Br
CH

CH CH

Br HBr
Br
propagation
initiation


evidence ; a small amount oI peroxide or h
a small amount oI inhibitor
ESR
CHCH

Br CH

CH CH

Br
CH
( not CH

CHBrCH

)


1) radical stability
Br
CH

CH CH

Br

more stable
transition state
CH

CHCH

CH

Br
CH

CH

2) polar eIIect
CH

CHCH

Br
CH

Br
CH

CH

CH

CH CH

Br
+

carry a partial
carbocation character



3) steric eIIect
the addition to C-1 is less hindered than the addition to C-2
less crowed transtion state
which are is more important?
it depends on the rxn
ex) conjugated system
styrene
radical stability
How about Ior HBr?
three Iactors may work
similarly.
CBr

steric eIIect
CE

polar eIIect


carbocation mechanism ;
Iree radical mechanism ;
orientation is
reversed
peroxides
Br
RCHCH

CCl

RCH CH

CCl

Cl

is added Iirst (eletrophilic)

is added Iirst



rad Peroxide
rad ClCCl

Cl rad CCl

RCHCH

CCl

RCH CH

CCl

RCH CH

CCl

ClCCl

RCHCl CH

CCl

CCl

G
CH

CH
peroxides
CH

CH CH

G
CH
G
monomer polymer



rad Peroxide
rad CH

CHG
CH

CH rad
G
CH

CH
G
initiation
propagation
CH

CH
G
rad
CH

CH rad
G
CH

CHG



C C
C
HO
C
OH
cold alkaline
KMnO

1) HCO

OH
2) H

1,2-diol or glycol

C C
C C
O
O
O
O
C
O
C
O
C O
Zn or H

S
KMnO

(cat)
NaIO

ozonide
C
HO
C
OH
C O
C O
O

ketone
aldehyde RCOOH
CH

O HCOOH CO

Simple tests Ior alkenes
C C

Br

/CCl

colorless soln ; alkyne is possible

MnO

brown ppt (Baeyer test) ; alkyne or

aldehyde is possible
MnO

soluble in conc
alcohol is also
1

- or 2

-OH
CrO

in aq H

SO

carboxylic acid or ketone Cr

(blue-green)
Jone's reagent (orange color)
soluble in conc
H

SO

SO