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Problem Set 5

1. Provide valid syntheses for the following compounds starting from either toluene or
benzene:
(a) 2-Bromo-4-nitrobenzoic acid
start with toluene
1. HNO3/H2SO4
2. Br2/FeBr3
3. KMnO4 or chromic acid
(b) 4-chloro-1-nitro-2-propylbenzene
start with benzene
1. CH3CH2COCl/AlCl3
2. Cl2/FeCl3
3. H2/Pd-C
4. HNO3/H2SO4
(c) 2-chloro-4-methylphenol

[cf. McMurray 16.49d]

Start with toluene


(1) SO3/H2SO4
(2) NaOH
(3) Cl2/FeCl2
(d) 4-ethyl-2-nitrotoluene [McMurray 16.50c]
Start with toluene
(1) CH3COCl/AlCl3
(2) HNO3/H2SO4
(3) Zn-Cu/HOAc
(e) 4-bromo-3-nitrobenzoic acid
Start with toluene
(1) Br2/FeBr3
(2) KMnO4
(3) HNO3/H2SO4
(f) 3-Bromo-5-nitrobenzoic acid
COOH

CH3

COOH

KMnO4

HNO3

OH

H2SO4

(g) 1,2-Diphenylethane

COOH
Br2

O2N

FeBr3

O2N

Br

O O

ClCCCl

Zn(Hg)
HCl

AlCl3

(h) 3-Ethylnitrobenzene
O

CH3COCl

HNO3

AlCl3

H2SO4

(i) 3-Bromonitrobenzene
Start with benzene
1. HNO3/H2SO4
2. Br2/FeBr3
(j) 3-Bromo-4-methylaniline
Start with toluene
1. HNO3/H2SO4
2. Br2/FeBr3
3. SnCl2/HCl

Zn(Hg)
HCl

NO2

NO2

2. (a) Provide a mechanism for the following reaction using the curved arrow
formalism.
H3O+

H
O

H3O+
OH

OH

OH

OH2

(b) Provide a mechanism for the following reaction using the curved arrow formalism.
OH
tBu

H3 O+

H3 C
tBu

CH3

CH2 CH2 C(CH3) 2

3. (a) Consider the thiol group as a substituent on benzene.

SH
This group is ____ortho/para___ directing
ortho/para or meta

Benzene thiol
or
Thiophenol

and ____activating___ (2 pts)


activating/deactivating

(b) Explain, using resonance forms. Be sure to indicate why the thiol group is both
ortho/para or meta directing and activating or deactivating.

SH

SH
+

SH

H
E

SH

SH

SH

H
E

ortho
attack

major

esp stable
(PARA ATTACK SIMILAR)

SH

SH

SH

SH

SH
+

meta
attack

minor

The lone pairs on the sulfur atom stabilize the cationic charge in the intermediate leading to ortho and
para isomers. This indicates ortho/para directing ability. Since the intermediates for the favorable
electrophilic aromatic substitution of thiophenol are more stable than those for the EAS of benzene, the
thiol group must be activating.

4. Outline a sequence of reactions that is suitable for the preparation of the indicated
compound below from benzene or toluene and any needed organic or inorganic
reagents containing six carbons or less. Your synthesis will require more than one step.
You must show the structures of intermediate compounds in your synthesis. Do
not provide just a list reagents or you will lose points!
OH
O2N

???

benzene
or
toluene

Br
O

CH3COCl

HNO3

AlCl3

H2SO4

O2N

O
Br2

O2N

OH
NaBH4 O2N

FeBr3

Br

Br

5. Provide a mechanism for the following reaction using the curved arrow
formalism. [McMurray 16.64]
O

O
CH2Cl

H3C

H3C

Cl3Al Cl

O
H3C

CH3

AlCl3

O
H

CH2
H3C

Cl3Al Cl
O
H3C

CH3

CH3

6. Outline a sequence of reactions that is suitable for the preparation of the


indicated compound below from benzene or toluene and any needed organic or
inorganic reagents containing six carbons or less. Your synthesis will require
more than one step. You must show the structures of intermediate
compounds in your synthesis. Do not provide just a list reagents or you
will lose points!
(a) 5-Bromo-2-isobutylnitrobenzene from benzene or toluene
O
O
Cl

H2
Pt-C

AlCl3

Br2
FeBr3

HNO3
H2SO4

Br

Br

NO2

(b) 1-Bromo-3-chlorobenzene from benzene or toluene


NO2

HNO3

HCl

NO2

FeBr3

H2SO4

SnCl2

Br

Br2

Br

NH2

1. NaNO2
2. CuCl/Cl

Br

Cl

7. Outline a sequence of reactions that is suitable for the preparation of each of the
following compounds from the indicated starting material and any organic or
inorganic reagents containing six carbons or less. The syntheses will require more
than one step. Do not just provide reagents; you must provide the nature of the
synthetic intermediates.
(a) 2-Chloro-4-methylphenol from benzene or toluene [McMurray 16.49d]

CH3

CH3

CH3

CH3

SO3

KOH

Cl2

H2SO4

FeCl3

SO3H

Cl

OH

OH

(b) 4-Chloro-2-isobutylnitrobenzene from benzene or toluene [McMurray 16.65b]

O
O

O
Cl

Cl2
FeCl3

AlCl3

NO2
H2

HNO3

Pt-C

H2SO4
Cl

Cl

Cl