Chapter 16

aliphatic aromatic arene

ex)
ethylbenzene
the reactivity and the
orientation oI each portion
in the molecule are determined
by the other portion
more reactive
than benzene
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
NO
2
NO
2 HNO
3
H
2
SO
4
CH
2
CH
3
CHCH
3
Br
Br
2
h

more reactive
than ethane
CH
2
CH
3
nomenclature : p551
CH
3
CH
3
CH CH
2
CH
2
C OH
xylene styrene phenyl benzyl
carbinol
Ar X Ar R X
aryl halide aralkyl halide ( the chemistry is similar to that oI alkyl halide)
arene : low polarity
soluble in non-polar solvents
higher m.p.
less soluble in a given solvent
less dense than H
2
O
more symmetric
(Table 16-1)
(stronger intermolecular
Iorce)

Alkylbenzene
Irom Eriedel-CraIts alkylation
R
RX
(R may rearrange)
Lewis acid

C
O
R CH
2
R
Zn(Hg), HCl,
or N
2
H
4
, base
Clemmensen reduction
WolII-Kishner reduction
Eriedel-CraIts alkylation

CH
3
Cl
AlCl
3
CH
3
HCl
(RX)
alcohol and
alkene may
be used
BE
3
HE
H
2
SO
4
more reactive than
reactant
do the rxn with a large
excess oI reactant to
prevent polyalkylation
C
6
H
6
ClCH
2
CH
2
Cl PhCH
2
CH
2
Ph
AlCl
3

C
6
H
6

CCl
4
Ph
3
CCl

CH CHR
CH
2
CH
2
R
H
2
Ni
PhCH
2
Cl is usable
ArX is not usable
AlCl
3

R H

R

R
H

AlCl
4
R
HCl
AlCl
3
RCl AlCl
3
AlCl
4 R

RX BE
3
R XBE
3

RX EeCl
3
R XEeCl
3

RX HE R X HE
involved carbocation
ROH H

ROH
2
R H
2
O
C C

H

C C
H
PhC(CH
3
)
3
PhC(CH
3
)
3
H
2
SO
4
H
2
SO
4
PhH (CH
3
)
3
COH
(CH
3
)
2
CCH
2

PhH CH
3
CH
2
CH
2
Cl
AlCl
3
PhCH
2
CH
2
CH
3
PhCH
CH
3
CH
3

( 1 : 2)
CH
3
CH
2
CH
2
CH
2
Cl
AlCl
3
PhCH
2
CH
2
CH
2
CH
3
PhCH
CH
3
CH
2
CH
3

( 1 : 2)
0
o
CH
3
CHCH
2
Cl
AlCl
3
PhC(CH
3
)
3

CH
3
BE
3
PhCCH
2
CH
3

CH
3
CCH
2
OH
CH
3
CH
3
beIore rearrangement
it reacts with PhH.
primary carbocation is
unstable, so it is highly
reactive
not via carbocation?
hard to answer

CH
3
CH
3

another possible
mechanism ;
Al Cl
Cl
Cl
Cl R
H
R

ClAlCl
3
H
R

AlCl
4
( especially Ior 1
o
X and CH
3
X )
limitation oI Eriedel-CraIts alkylation
1) polyalkylation 2) rearrangement
3) ArX is not usable as alkylating reagent.
4) no rxn with less reactive aromatic compds than ArX
5) no rxn with Ar-NH
2
, ArNHR, ArNR
2
CH
2
CH
3
CH
2
CH
3
H
2
Ni, Pt or Pd
CH
2
CH
2
CH
2
CH
3
COOH
hot KMnO
4
CO
2

cI) benzene & alkane are very resistant

to the usual oxidizing reagents.
CH
3
CH
3
KMnO
4
COOH
COOH
CH
3
NO
2
Cr
2
O
7
COOH
NO
2
H

useIul Ior identiIication

R
Cl
2
or Br
2
rxn at the side chain
rxn at the ring
Iree radical rxn (Cl , Br )
electrophilic substitution rxn
( Cl , Br )
CH
3

Cl
2
Ee or EeCl
3
CH
3
Cl
CH
3

Cl
Cl
2
or h
CH
2
Cl CHCl CCl
3
benzyl chloride
benzal chloride benzotrichloride
CH
2
CH
3
CHCH
3
CH
2
CH
2
Br
only
none
(benzylic hydrogen)
Br
2
or h

allylic 3
o
2
o
1
o
Br
CH
3
vinylic
more stable (by bond dissociation energy)
easier to be Iormed
(by rxns)
CH
2
CH
3
Cl
2
or h
CHCH
3
CH
2
CH
2
Cl
91
9

Cl
less selective
Cl is more reactive than Br
less Iree-radical character
early transition state
the Iactors stabilizing the benzyl radical have less eIIect on the transition state.
benzylic

CH
4
PhCH
3
CH
3
H
H 104 kcal
H 85 kcal PhCH
2
H

CH
3
CH
3
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
these resonance structures are responsible
Ior the extra stabilization.
benzyl & allyl Iree radical are more stable than alkyl Iree radical, but extremely
reactive and unstable.
C Cl

Zn
C C
Ph
Ph
Ph C Ph
Ph
Ph
I
O
2
X
2
Ph
3
COO
Ph
3
CX
C
Ph
3
C
H
Ph
Ph
II
Why is II Iormed rather than I ? I : sterically much crowded.
II : sacriIice some aromaticity.
sterically less crowded than I.
steric eIIect wins over
electronic eIIect.
CPh
3

Why does II dissociate easily

to triphenylmethyl radical ?
II : sterically crowded.
triphenylmethyl radical : get more aromaticity.
relieve steric strain.
CC single bond 80 ~ 90 kcal
~
~
radical can be detected
by paramagnetic resonance
absorption (esr)
CC in II 11 kcal
~
~
PhCH
2
X PhCH
2
X
p22
3
o benzyl
allyl
CH
3
more stable
( X halide, OH )

1
o
2
o
due to the contribution oI
a phenyl group stabilizes
the cation more by 61 kcal
PhCH
2
Cl
CH
3
Cl
PhCH
2
Cl

CH
3
Cl

H 166
H 227
CH
2
CH
2
CH
2
benzyl substrates
S
N
1 : as Iast as 2
o
substrates
S
N
2 : as Iast as 1
o
substrates ( similar steric eIIect )
PhCH
2
X Ph
2
CHX Ph
3
CX
S
N
1
S
N
2

alc KOH
substituents on the ring ( para & meta ; ortho exerts steric hindrance )
aIIect the rate oI solvolysis greatly.
ex)
CH
2
Cl
OMe
CH
2
Cl
CH
3
CH
2
Cl
NO
2

CH
2
CH
2
H
3
PO
4
CH
2
CH
3
CHCH
2
Cr
2
O
3
Al
2
O
3
600
o
alc KOH
acid
CH CH
3
Cl
CHCH
2
CH CH
3
OH
CHCH
2
CH
2
CH CH
3
Cl
CH
2
CH CH
3
OH
CHCH
2
CH
3
CH
2
CHCH
2

KOH or H
(none)
more stable alkene
conjugated double bond
acid
alkenylbenzene ; substitution in the ring
addition in the side chain
the double bond in the side chain
is more reactive
CH CH
2
CH
2
CH
3
CH
2
CH
3
H
2
, 2~3 atm
Ni, 20
o
75 min
H
2
, 110 atm
Ni, 125
o
100 min

CHCH
2
H
2
O
2
HCOOH
CH CH
2
OH OH
COOH
KMnO
4
CH
2
CH
3
Cl
2
EeCl
3
CH
2
CH
3
Cl
Cl
2
CH CH
3
Cl
Cl
KOH
CHCH
2
Cl CHCH
2
PhCHCHCH
3
HBr
PhCH CH
2
CH
3
PhCH CH
2
CH
3
Br
Br
PhCH CHCH
3
Br
PhCH
2
CH CH
3
Br
HBr
without peroxide
with peroxide
PhCHCH
2
CH
3
PhCHCHBrCH
3
PhCH
2
CHCH
3
PhCHBrCHCH
3
more stable
conjugated alkenylbenzene is more stable than simple alkene.
does addition to a conjugated alkenylbenzene occur Iaster than
addition to a simple alkene?
depends on E ( depends on which is more stabilized, either
reactant or transition state )
generally conjugated alkenylbenzene is more reactive than
simple alkene toward both ionic and Iree-radical addition.
Ph
2
CCPh
2
Br
2
CCl
4
( not always true, no rxn )
alkynylbenzene
identiIication