ORG CHEM IIProblem Set Chapter 16

ANSWER KEY

1. Show the major product for the monoiodination of the following compounds usingCuCl2 and I2.

C O

O

O2N CH3

C O

O

O2N CH3I

I

2. Show the major product for for each of the following reactions or series of reactions.

H2SO4

SO3 Br2

FeBr3

H+/H2O

H2SO4

SO3NaOH∆

Cl

AlCl3

CH3CH2C–Cl

O

AlCl3

Rh/CH2

H2

Pd/CHNO3

H2SO4

CH3Cl

AlCl3

Br2FeBr3

HNO3H2SO4

NO REACTION

CH3

CH3

SO3H

Br

Br

NO2

Br

NO2

+

NO2

No Reaction on 2nd step

OH

CCHCH3

O

3. Show a possible synthesis scheme for the following conversions. Show the majorproduct for each reaction used, but do not show any mechanism.

CH CH2

O2N

CH2CH3

CH3CH2ClAlCl3

HNO3

H2SO4

CH2CH3

O2N

NBSPeroxides

CHCH3

O2N

Br

KOH

CH2CH2CH3

CH3CH2C Cl

O

AlCl3

CCH2CH3

O

2 H2, Pt/Cor1) NaBH4

2) H3O+

4. Rank the following compounds in their expected order of reactivity toward theFriedel-Crafts reaction with ethyl chloride in the presence of aluminum chloride.(Rank #1 is most reactive; #4 is least reactive)

a. Nitrobenzene 4b. Bromobenzene 3e. Phenol 1d. Toluene 2

5. Show the major products for each of the following reactions. If no reaction willoccur, write ‘NR’ in place of a product.

AlCl30°

OH

+ CH3CH2CH2Cl

OH

CH(CH3)2

+ some ortho

0°AlCl3

NH 2

CH3CH2CH2Cl+

No ReactionThe nitrogen of aniline complexeswith the AlCl3, thereby destroying thecatalyst

FeBr3NO2

CH3

Br2+

CH3

NO2

Br

The o,p activatortakes priority over themeta in directing theincomming electrophile

peroxides

NBSNO2

CH3

Br2+

CH2Br

NO2

6. Show the reactions necessary to synthesize the following compounds from benzene.

a. m-Bromonitrobenzene

HNO3

H2SO4

NO2Br2

FeBr3

NO2

Br

b. CH CH2Cl

CH2CH3

CH3CH2ClAlCl3

CH2CH3

Br

NBSPeroxides

CHCH3

Br

Br

KOH

Br2

FeBr3

HC

Br

CH2

7. Name the following compounds using IUPAC nomenclature.

CH3

CH3

CO2H

Cl

NO2

m -xylene of m-methyltoluene 2-chloro-6-nitrobenzoic acid

8. Show the major product expected from the folowing reactions. If no reaction willoccur with the given conditions, write ‘NR’ for the product.

NH2

Cl

AlCl3 0°

CH3ClNo Reaction

AlCl3 0°

CH3Cl

CH3

Cl

CH3

Cl

CH3

SO3

H2SO4

NO2

CH3

NO2

CH3

SO3H

CH3C–Cl

O

AlCl3 0°

OH

Br

OH

Br

COCH3

O CCH3

OHNO3

H2SO4O CCH3O2N

O

9. Show a synthesis scheme for the following conversions. You may use anycombination of reactions and reagents you need. Show the major product and neededconditions for each reaction used.

CH2CH2CH3

Br

2 H2, Pt/Cor1) NaBH4

2) H3O+CCH2CH3

O

CH3CH2C Cl

O

AlCl3

Br2

FeBr3

CCH2CH3

OBr

NH2

Br

NO2 Br2, FeBr3 NO2Br

HNO3, H2SO4 Sn, HCl

10. Show the major product for each of the following reactions. If no reaction willoccur, write no reaction.

a. OH

CN

heat

SO3/H2SO4

CN

OHSO3H

b.

NH2

CH3

AlCl3

CH3CH2CH2CH2Br NO REACTIONNitrogen of aniline reactswith the catalyst

c.

CH3

SO3H

HNO3/H2SO4

CH3NO2

SO3H

d.

NO2Cl

Cl

Br2/FeNO REACTIONAromatic ring isTOO DEACTIVATED

e.

NaNH2/heatBr

CH3

NH2

CH3

via Benzyne

11. Show the complete synthesis of the following compounds from benzene. Show themajor products from each step but do not show any mechanisms. You may use anyadditional reagents needed

a.

CH2CH3 CH2CH3

O2N

CHCH3

O2N

Br

CH3CH2ClAlCl3

HNO3H2SO4

NBS

peroxides

b.

CH2CH3 CH2CH3

Cl

CHCH3

Cl

Br

CH3CH2ClAlCl3

NBS

peroxides

Cl2

AlCl3

KOHCH=CH2

Cl

HBr

peroxides

CH2CH3

Cl

Br

12. Show the major product from each of the following reactions.

CH3CH2CHCH3

CH3Cl

AlCl3, 0°

H2SO4

NHO3

Br2/Fe

Sn/HCl

SO3

H2SO4

CH3CH2C–Cl

OAlCl3, 0°

Sn/HCl

CH3

NO2

CH3

NH2

CH3

C CH3

CH3

CH3

CH3

COCH2CH3CH3

CH2CH2CH3

CH3

Br2

CH3

SO3H

13. Show the major product for each of the following reactions.

CH3 CCH3

OSO3

H2SO4CH3

HO3S

CCH3

O

H2N NO2CH3CH2Cl

AlCl3, 0°NO REACTION!

14. Rank each set of compounds, below, in their decreasing order of reactivity towardsaromatic nucleophilic substitution.

CO2H NO2 CH(CH3)2 Cl

4 32 1

C N OCH3 CH3

C

O

H

1 234