CHEM 14D/Garg

Spring 2015

Problem Set #6

1. Provide reaction conditions for each of the following transformations.

a.
Br

Br2
FeBr3

b.
SO3H

SO3
H2SO4

c.
NO2

HNO3
H2SO4

d.
O
Cl

O
Me

Me

AlCl3

2. Predict the major product(s) for each of the following reactions.

a.
Cl

Cl

HNO3
H2SO4

Cl

O2N

NO2

major

minor

b.
CF3

CF3

MeCOCl
AlCl3
Me

c.
CO2Et

CO2Et

HNO3
H2SO4
NO2

d.
O

Cl
AlCl3

CHEM 14D/Garg

Spring 2015

Problem Set #6

e.
NMe2

NMe2

SO3
H2SO4

NMe2
SO3H

HO3S
major

minor

f.
Me

Me

Br
AlBr3

MeO

Note: As with all Friedel-Crafts alkylations,

overalkylation is also possible

MeO

g.
Me

Me
NO2

HNO3
H2SO4
NO2

NO2

h.
Me

Me

O
Me

MeCOCl
AlCl3

CHEM 14D/Garg

Spring 2015

Problem Set #6

3. Predict the major product and draw detailed arrow-pushing mechanisms for each of the
following transformations.
a.
Br

Br2
FeBr3

Br

FeBr3

Br

Br Br

FeBr3

H
Br Br

Br

FeBr3

Br

FeBr3

Br
FeBr3

HBr

b.
O
Et

O
Cl

Et

AlCl3

MeO

MeO

O
AlCl3

Et

Cl

Et
Et

Et

C O

Cl AlCl3
and
Cl

AlCl3
MeO
H O

O
Et
MeO

Et
MeO

C O

CHEM 14D/Garg

Spring 2015

Problem Set #6

c.
HNO3
H2SO4

F3C

F3C

O
O

O
O

O S O

OH

OH

O N O
OH2

+
H2O

O H
N
O

CF3
O N O

CF3

O
O S O
OH

O
O

CF3

O
H O S O
OH

4. Indicate with an asterisk (*) the most reactive site toward electrophilic aromatic substitution in
each of the following molecules.
a.
NO2

NO2
NH2

NH2

NO2

NO2

b.

*
Me

Me

Me

Me

c.
Me
CF3

Me

CF3

d.
Me
Me
EtO
EtO

*
4

CHEM 14D/Garg

Spring 2015

Problem Set #6

e.
Br

Br
NO2

NO2

Me
NH2

Me
NH2

5. Rank the following substrates 14 in terms of reactivity (1 being the most reactive) for
electrophilic aromatic substitution reactions.
a.
O

OMe

b.
Me
Me

NO2

O2N

Cl

6. Some of the ortho/para directors you have learned can be converted to meta directors and vice
versa. Show the reagents necessary to complete the desired transformations.
a.
O
F3C

ortho/para
director

OOH

NH2

NO2

meta
director

Zn(Hg), HCl

CHEM 14D/Garg

Spring 2015

Problem Set #6

b.
Zn(Hg), HCl

O
R

meta
director

ortho/para
director

CrO3, H2SO4, H2O

7. Propose syntheses for each of the compounds shown below. You may use fragments of 2carbons or less (these fragments may contain atoms other than just carbon, including hydrogen,
oxygen, MgBr, and Li), and any of the compounds shown in the Chem 14D Toolbox. Please be
sure to include key reagents and solvents in your solutions, consistent with what you have
learned in this course through exams, problem sets, lectures, and practice tests. It is not necessary
to show mechanisms or retrosynthetic analyses in your solutions
CHEM 14D Toolbox
O

Cl

Cl
CF3

a.
MgBr

Br2

Br

FeBr3

MgBr

Mg
Et2O

b.
NH2

HNO3
H2SO4

NO2

NH2

Zn(Hg)
HCl

CHEM 14D/Garg

Spring 2015

Problem Set #6

c.
NH2

Br

NO2

NH2

NO2
Br2

Zn(Hg)
HCl

FeBr3

Br

Br

(see part b)
d.
O
I

Me

O
Me

Cl

O
Me

AlCl3

I2
FeI3

Me

e.
HO3S

Cl

SO3
H2SO4

HO3S

HO3S

Cl2
FeCl3

Cl

CHEM 14D/Garg

Spring 2015

Problem Set #6

f.

Br
O

OH

Cl
AlCl3

Br2

NaBH4

FeBr3

EtOH
Br

Br
TsOH
benzene, heat

Br

g.
Br
O
Cl

Br2
FeBr3

Br

OH

O
NaBH4

AlCl3

EtOH

Br

Br
TsOH
benzene, heat

Br

CHEM 14D/Garg

Spring 2015

Problem Set #6

Bonus Synthesis Problems - These are a little more difficult. Use the same instructions as for
question #7.
a.
HO

Me

Br

NO2
H

Cl
AlCl3

Zn(Hg)

HNO3

HCl

H2SO4
NO2
Br2
FeBr3

Me

HO
Br

MeMgBr

Br

Br

CrO3

Et2O

H2O, H2SO4
NO2

NO2

NO2

b.
NO2

H2, Pd/C

HNO3

EtOH

H2SO4

(heat not necessary for

benzyne Diels-Alder)

NO2

CHEM 14D/Garg

Spring 2015

Problem Set #6

c.

CF3

Br2

Br

Mg
Et2O

FeBr3
CF3

BrMg

CF3

CF3

Cl
AlCl3

Et2O
Me

HO
Me

CF3
TsOH
benzene, heat

heat

CF3

CF3

10