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