CARBOXYLIC ACID DERIVATIVES SOLUTIONS
Don’t forget that the final exam is comprehensive. These problems are only for the last unit on
carboxylic acid derivatives. You will also need to review the other units for the final.
1. Draw structures of the following compounds.
f) acetic benzoic anhydride
a) -naphthoyl chloride
O
O
O
O
Cl
g) -ethyl--valerolactone
b) benzamide
O
O
CH3CH2
NH2
O
CH3
c) p-nitrobenzonitrile
h) N-bromocyclopentanecarboxamide
O
O2N
C
Br
N
N
H
d) ethyl 3-methylbenzoate
i)
-chloro--caprolactam
O
O
H3C
NH
CH2CH3
Cl
e) cyclohexyl propionate
j)
propanenitrile
O
CH3CH2C
N
O
2. Name the following compounds. Give IUPAC (I), and where possible, or common (c).
O
a)
d)
O
F
C
Cl
CH3CH2
(c) -ethyl--butyrolactone
(I) 2-ethyl-4-hydroxybutanoic acid lactone
m-fluorobenzoyl chloride
O
b)
C
e)
OCH2CH3
(I) isopropyl methanoate
(c) isopropyl formate
ethyl 3-chlorocyclopentanecarboxylate
O
O
CH3C O C H
(c) acetic formic anhydride
(I) ethanoic methanoic anhydride
O
(CH3)2CHOCH
Cl
c)
O
f)
H3C
C
N
3-methylcyclopentanecarbonitrile
PAGE 1
CARBOXYLIC ACID DERIVATIVES SOLUTIONS
3. Draw structures of the following compounds
a) N-bromoacetamide
O
e) phthalic anhydride
O
Br
O
N
H
O
f) -fluorocaproyl chloride
b) N-methyl-3-hydroxybutanamide
OH
O
O
F
CH3
N
CH3CH2CH2CHCH2C
H
Cl
g) -caprolactam
c) cyclobutanecarbonitrile
O
C
N
NH
h) -propiolactone
d) t-butyl acetate
O
O
O
O
4. Draw complete mechanisms for the following reactions. You must show all intermediates
formed and all reagents and products. Use arrows to push electrons. There is one mark for
each arrow. Also name the product.
a) reaction of the amide shown below with NaOH upon refluxing.
2
1
: O:
..

2
NH2
+
: O:
: O:
NH2-
..
O
..
-
Na OH
..
..:
Na+NH2-
O
H
+
Na+
NH3
acid/base
1
sodium benzoate
nucleophilic
addition
b) Hydride reduction of the acid chloride shown below using excess LiAlH4 , and followed
by excess H3O+.
1
H3C
2
:O :
C
1
:O :
-
Cl
2
..
.. :
LiAlH4
H3C
1
ethanoyl chloride
:H
LiAlH4
H
-
1
ethanal
:H
-
H
O+
:O :
C
Cl
..
..
H
:O :
H
H
H3C
C
H
H
ethoxide
H3C
acid/base
H2O
C
H
H
ethanol
PAGE 2
CARBOXYLIC ACID DERIVATIVES SOLUTIONS
c) Fischer esterification of the acid shown below with methanol using dry HCl as catalyst.
H
: O: ..
O
C ..
..
Cl :
..
H
: O: ..
O
C ..
+
H
nucleophilic
addition
H
..
O
..
CH3
H
H
: O: ..
O
C ..
: O: ..
+O
..
H
..
: Cl..:
C
H
H
H2O
H
C
+
OCH3
H proton
transfer
H3C
O
+
: O:
..
O
..
CH3
HCl
methyl cyclobutanecarboxylate
5. Draw structures of the major products of the following reactions. No mechanisms required.
a)
O
Gilman
1 (CH3)2CuLi
+
2 H3O
O
O
CH3
C Cl
-
C
C CH3
O
O
C O
C
+
O Na
CH3
+
NaCl
O
C NHCH3
2 NH2CH3
+
HCl
b)
acid/base
CH3MgBr
O
C O-
O
H3O+
C OH
acid/base
O
SOCl2
C OH
O
C Cl
NH3
O
C O- NH4+
acid/base
c)
CH3MgBr
O
C
O
OH
CH3MgBr
C CH3 1
+
2 H3O
C CH3
CH3
OCH3
O
DIBAH; H3O+
C H
PAGE 3
CARBOXYLIC ACID DERIVATIVES SOLUTIONS
O
NH2-
d)
C
NaOH 
1 LiAlH4
2 H2O
O
C
O
acid/base
OH
O- Na+ + NH3
C
CH2NH2
NH2
O
O
CH3MgBr
C
acid/base
H3O+
NH-
C
NH2
acid/base
SOCl2
C
N
O
O
CH2C
H3O+ 
e)
1 LiAlH4
+
2 H3O
CH2C
H3O+ 
CH2C
NH2
OH
CH2CH2NH2
O
N
1 C6H5MgBr
+
2 H3O
CH2C
O
1 DIBAH
+
2 H3O
CH2C
H
6. Outline a synthesis for each of the following products from the starting material shown.
More than one step may be necessary. List all reagents; show all reagents used and the
product formed after each step. There are no marks for showing mechanisms
a)
OH
other routes are possible
CH2OH
C
oxidation
Cr+6, H+
acid/base
NaOH
O
2 equiv.
COH
SOCl2
O
CO- Na+
O
C
CH3Br
SN2
1
Cl
MgBr
2 H O+
3
O
COCH3
PAGE 4
CARBOXYLIC ACID DERIVATIVES SOLUTIONS
b)
O
Br
C
CH2CH3
Cr+6, H+
oxidation
NaCN
Mg, ether
O
OH
CN
2°
1 HCCH2CH3
MgBr
H3O+

1 CO2
+
2 H3O
O
C OH
CHCH2CH3
H3O+
2
1 (CH3CH2)2CuLi
O
C Cl
+
2 H3O
SOCl2
c)
O
CH3
C
CH3
N
C
H3O+
2 N(CH3)2H
O
CH3
N(CH3)2
O
C
OH
SOCl2
CH3
C Cl
O
d)
Br
C
H
Mg, ether
MgBr
O
O
1 CO2
+
2 H3O
C
1 DIBAH
+
2 H3O
OH
SOCl2
C
Cl
PAGE 5
CARBOXYLIC ACID DERIVATIVES SOLUTIONS
e)
O
CH2CH2CH3
CH3C OH
Zn[Hg}, HCl or
N2H4, KOH
reduction
O
SOCl2
O
CH2
1
CH3C
Cl
H3O+
2
CuLi
2
CH2CCH3
Gilman
f)
CH3CH CH2
oxidation
cleavage
O
CH3C
SOCl2
dehydration
or
POCl3
O
KMnO4
O
SOCl2
CH3
+
C
N
OH
CH3
C
NH3
Cl
CH3
C
NH2
CO2
7. Draw the structures of all the carboxylic acid derivatives as well as carboxylic acid,
aldehyde, and ketone in order of decreasing carbonyl group reactivity. Place the most
electrophilic group on the left and the least on the right.
acid
chloride
O
R
C
Cl
R
most reactive
electrophile
ester
O
aldehyde
amide
O
O
R
acid
anhydride
O
O
C
O
C
R
C
C
OR
H
O
R
R
C R
ketone
R
O
R
C
OH
carboxylic
acid
C
carboxylate
O
NH2
R
C
O-
nitrile
R C N
least reactive
electrophile
decreasing electrophilic reactivity
PAGE 6