Arenes:

compounds containing both aliphatic and aromatic parts. Alkylbenzenes Alkenylbenzenes Alkynylbenzenes

Etc.

Emphasis on the effect that one part has on the chemistry of the other half. Reactivity & orientation

Example: ethylbenzene
EAS in the aromatic part -CH2CH3 activates and directs ortho- & paraCH3 CH2 Br2, Fe CH3 CH2 Br + Br CH3 CH2

Free radical halogenation in the side chain -C6H5 activates and directs benzyl
Br2, heat CH2 CH3 CH CH3 Br + HBr

Alkylbenzenes, nomenclature: Special names

CH3 CH3 CH3 CH3 CH3 toluene o-xylene m-xylene p-xylene CH3 CH3

others named as alkylbenzenes:

H3C CH3 CH3 H2C CH2

CH

H2 CH3 C CH CH3

isopropylbenzene

n-propylbenzene

isobutylbenzene

CH2 CH3 CH2 CH3

o-diethylbenzene

n-butylbenzene

Use of phenyl

C6H5- = phenyl

CH2CH2

2-methyl-3-phenylheptane

1,2-diphenylethane

do not confuse phenyl (C6H5-) with benzyl (C6H5CH2-)

Alkenylbenzenes, nomenclature:
Special name

CH=CH2 styrene

Rest are named as substituted alkenes

CH2CH=CH2

3-phenylpropene (allylbenzene)

(Z)-1-phenyl-1-butene

Alkynylbenzenes, nomenclature:

C CH

phenylacetylene phenylethyne 5-phenyl-2-hexyne

Alcohols, etc., nomenclature:

H3C CH OH CH2OH 1-phenylethanol

benzyl alcohol

phenylethyl alcohol

CH2CH2-Cl

1-chloro-2-phenylethane

cyclohexylbenzene phenylcyclohexane

-phenylethyl chloride

Alkylbenzenes, syntheses: 1. Friedel-Crafts alkylation

2. Modification of a side chain:

a) addition of hydrogen to an alkene b) reduction of an alkylhalide i) hydrolysis of Grignard reagent ii) active metal and acid c) Corey-House synthesis

Modification of side chain:

H2, Ni

Br + Sn, HCl

ethylbenzene Br + Mg; then H2o

Friedel-Crafts: + R-X, AlCl3 Ar-R + HX

Ar-H

Ar-H

+ R-OH, H+

Ar-R + H2O
Ar-R

Ar-H

+ alkene, H+

CH2=CHCH3,

H+

CH3 CH CH3

isopropylbenzene

+ CH3CH2-OH, H+

CH2 CH3

ethylbenzene

CH3 +

CH3 CH3 H3C C CH3 Br AlCl3 p-tert-butyltoluene H3C C CH3 CH3

H+

cyclohexylbenzene

H3C

CH2Cl AlCl3 CH2 p-benzyltoluene CH3 ortho-

CH2Cl2, AlCl3

CH2 diphenylmethane

Friedel-Crafts limitations:

a) Polyalkylation
b) Possible rearrangement c) R-X cannot be Ar-X

d) NR when the benzene ring is less reactive than bromobenzene

e) NR with -NH2, -NHR, -NR2 groups

polyalkylation

CH3 CH3Br, AlCl3 +

CH3 CH3 + CH3 CH3
+ H3C CH3 CH3

The alkyl group activates the ring making the products more reactive that the reactants leading to polyalkylation. Use of excess aromatic compound minimizes polyalkylation in the lab.

The electrophile in Friedel Crafts alkylation is a carbocation:

R-X + AlX3

R+

R-OH + H+
| | C=C

R+
+ H+ R+

Carbocations can rearrange!

rearrangement
H3C + CH3CH2CH2-Br, AlCl3 CH CH3 isopropylbenzene

CH3 H3C C CH3 + CH3 CH3CHCH2-Br AlCl3 tert-butylbenzene

CH3 CH3CCH2-OH CH3

H+

CH3 CH3CCH2CH3 2-methyl-2-phenylbutane

carbocation rearrangements are possible!

n-alkylbenzenes cannot be made by Friedel-Crafts alkylation due to carbocation rearrangements

R-X cannot be Ar-X

R + R-X, AlCl3

X AlCl3 + NR

The Ar-X bond is strong and does not break like the R-X bond!

NR with rings less reactive than bromobenzene

Br + CH3CH2-Br, AlCl3 CH2CH3 COOH + CH3-Br, AlCl3 NR Br + Br CH2CH3

-CHO, -COR
-SO3H -COOH, -COOR

NO2 + CH3CH2-OH, H+ NR

-CN -NR3+ -NO2

NR with NH2, -NHR, -NR2

NH2 + CH3CH2-Cl, AlCl3 NR

NH2 + AlCl3

NH2 AlCl3

Lewis base

Lewis acid

deactivated to EAS

Friedel-Crafts limitations: a) Polyalkylation b) Possible rearrangement c) R-X cannot be Ar-X d) NR when the benzene ring is less reactive than bromobenzene e) NR with -NH2, -NHR, -NR2 groups

In syntheses it is often best to do Friedel-Crafts alkylation in the first step!

Alkylbenzenes, reactions:
1. Reduction 2. Oxidation

3. EAS
a) nitration b) sulfonation c) halogenation d) Friedel-Crafts alkylation

4. Side chain
free radical halogenation

Alkylbenezenes, reduction:
H2 C CH3

CH3CH3

H2, Ni

NR

NR

NR
H2 C

H2, Ni 300oC, 100 atm.

NR

CH3

Alkylbenezenes, oxidation:
H2 C CH3

CH3CH3

KMnO4

NR

NR

NR
COOH

KMnO4 heat

NR

NR

COOH + KMnO4, heat COOH

COOH + KMnO4, heat + 2 CO2

Oxidation of alkylbenzenes.
1) Syn
H2C CH3 bp 136oC COOH mp 122oC

2) identification

C8H10:
CH3 CH3 bp 144oC COOH COOH mp 231oC

CH3 bp 139oC CH3 CH3

COOH mp 348oC COOH

COOH bp CH3 COOH 138oC mp 300oC

Alkylbenzenes, EAS
CH2CH3 HNO3, H2SO4 CH2CH3 NO2 CH2CH3 + NO2 CH2CH3 + SO3H CH2CH3 Br CH2CH3 +

-R is electron releasing. Activates to EAS and directs ortho/para

H2SO4, SO3

CH2CH3 SO3H

Br2, Fe

Br CH2CH3 +

CH3Cl, AlCl3

CH2CH3 CH3

CH3

Alkylbenzenes, free radical halogenation in side chain: benzyl free radical

CH2CH3

Cl2, heat

CHCH3 Cl 91%

CH2CH2-Cl

9%

CH2CH3

Br2, heat

CHCH3 Br only

X2

2X

. .
CHCH . 3

CH2CH3 + X

. .
CHCH3 CHCH3

CHCH3

benzyl free radical > 3o > 2o > 1o > CH3

Alkenylbenzenes, syntheses: 1. Modification of side chain:

a) dehydrohalogenation of alkyl halide

b) dehydration of alcohol c) dehalogenation of vicinal dihalide d) reduction of alkyne (2. Friedel-Crafts alkylation)

Alkenylbenzenes, synthesis modification of side chain

KOH(alc) CHCH3 Br CH=CH2 heat styrene

H+, CHCH3 OH

Zn CHCH2 Cl Cl

H2, Pd-C C CH

Alkenylbenzenes, synthesis Friedel-Crafts alkylation not normally used for alkenylbenzenes.

+ CH2=CH-Br, AlCl3 NR

an exception:
+ CH2=CHCH2-Br, AlCl3 CH2CH=CH2 allylbenzene

KOH(alc) Br conjugated with the ring

KOH, heat

Alkenylbenzenes, reactions:

1.
2. 3. 4.

Reduction
Oxidation EAS Side chain a) addn of H2 b) addn of X2 c) addn of HX d) addn of H2SO4 e) addn of H2O f) addn of X2 & H2O g) dimerization h) alkylation i) dimerization j) oxymercuration k) hydroboration l) addition of free rad. m) addn of carbenes n) epoxidation o) hydroxylation p) allylic halogenation q) ozonolysis r) vigorous oxidation

Alkenylbenzenes, reactions: reduction

CH=CH2

H2, Ni

CH2CH3

CH=CH2 +

H2, Ni, 250 C, 1,500 psi

CH2CH3 H

Alkenylbenzenes, reactions oxidation

CH=CH2

KMnO4

CHCH2 OHOH

KMnO4 CH=CH2 COOH heat + CO2

1. O3 CH=CH2 2. Zn, H2O

CH=O

O=CH2

Alkenylbenzenes, reactions EAS?

electrophilic addition

CH=CH2

electrophilic aromatic substitution

alkenes are more reactive with electrophiles than aromatic rings!

CH=CH2

Br2, Fe

CHCH2 Br Br

In syntheses of alkenylbenzenes, the carbon-carbon double bond must be synthesized after any EAS reactions CH2CH3 CH2=CH2 HF Cl Cl2, hv Cl CHCH3 KOH(alc) Cl2, Fe + ortho CH2CH3

CH=CH2

CH2CH2-Cl

Cl p-chlorostyrene

Cl

Cl

Alkenylbenzenes, reactions side chain:

H2, Ni CH=CHCH3 CH2CH2CH3

Br2, CCl4

Br CHCHCH3 Br

HBr CHCH2CH3 Br

H2SO4 CHCH2CH3 OSO3H

Benzyl carbocation
CH=CHCH3 + H+ CHCH2CH3

CHCH2CH3

CHCH2CH3

CHCH2CH3

resonance stabilization of benzyl carbocation > 3o > 2o > 1o

CH=CHCH3

H2O, H+ CHCH2CH3 OH

Br2, H2O

Br CHCHCH3 OH

1. H2O, Hg(OAc)2 2. NaBH4 CHCH2CH3 OH

1. (BH3)2 2. H2O2, NaOH CH2CHCH3 OH

HBr, perox. CH=CHCH3 CH2CHCH3 Br

polymer. CH=CH2 CHCH2 n polystyrene

CH2N2, hv CH=CHCH3

PBA CH=CHCH3 O

CH=CHCH3

Br2, heat

CH=CHCH2-Br

H C C H CH3

KMnO4

CH3 H OH HO H

CH3 HO H H OH

(E)-1-phenylpropene

100 syn-oxidation; make a model!

Alkynylbenzenes, syntheses: Dehydrohalogenation of vicinal dihalides

Br2 CH=CH2

Br CHCH2 Br

1. KOH C CH 2. NaNH2

KOH(alc) H C CH3 Br H2 C CH3 CH2=CH2 HF

Alkynylbenzenes, reactions: 1. Reduction 2. Oxidation 3. EAS 4. Side chain

a) reduction
b) addn of X2 c) addn of HX

e) as acids
f) with Ag+ g) oxidation

d) addn of H2O, H+

Alkynylbenzenes, reactions: reduction

C C CH3 + 2 H2, Ni CH2CH2CH3

(xs) H2, Ni heat & pressure

C C CH3

Li, NH3

anti-

H2, Pd-C

syn-

Alkynylbenzenes, reactions: oxidation

O3; then Zn, H2O

KMnO4 C C CH3 COOH + HOOCCH3

KMnO4, heat

Alkynylbenzenes, reactions EAS?

electrophilic addition

C CH

electrophilic aromatic substitution

alkynes are more reactive with electrophiles than aromatic rings!

C CH

Br2, Fe

Br C=CH Br

Alkynylbenzenes, reactions: side chain:

Br2 C C H Br C=CH Br

2 Br2

Br Br C C H Br Br

HBr C=CH2 Br Br CCH3 Br

2 HBr

H2O, H+ C CH

O CCH3

Na C CH C C-Na+

Ag+ C CH C C-Ag+

Ag+ C CCH3 NR, not terminal

Arenes:

alkylbenzenes

alkenylbenzenes

alkynylbenzenes

As expected, but remember that you cannot do EAS on alkenyl- or alkynylbenzenes.