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Homework Chapter 21-Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions - Mandatory Problems Are Highlighted (Up To Page 16)
Homework Chapter 21-Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions - Mandatory Problems Are Highlighted (Up To Page 16)
SHORT ANSWER
1. Name:
ANS:
Ethyl p-aminobenzoate
2. Name:
ANS:
bis(2-methylpropanoic) anhydride
3. Name:
ANS:
methyl phenylacetate
4. Name:
1
Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions
ANS:
trans-2-butenoyl chloride
5. Name:
ANS:
N-cyclopentyl-3-methylbutanamide
6. Draw: 2-propenamide
ANS:
ANS:
ANS:
2
Chapter 21
9. Draw: N,N-dimethylformamide
ANS:
ANS:
ANS:
3
Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions
a. b.
c. d.
ANS:
a
Exhibit 21-1
What is the order of decreasing reactivity towards nucleophilic acyl substitution for the carboxylic
acid derivatives? (most reactive first)
13.
a. I, II, III, IV
b. I, III, IV, II
c. II, IV, III, I
d. II, I, III, IV
ANS:
b
14.
a. I, III, II, IV
b. II, III, I, IV
c. III, II, I, IV
d. IV, I, III, II
ANS:
d
4
Chapter 21
15. The ester ethyl p-nitrobenzoate is more reactive towards nucleophilic acyl substitution than
ethyl p-methyoxybenzoate. Explain this reactivity difference using both words and
structures.
ANS:
In general, any factor that makes the carbonyl carbon more polarized will increase the reactivity of
the carboxylic acid derivative. In these particular examples, both are aromatic ethyl esters. It is the
substituent on the aromatic ring that is affecting the reactivity difference. The electron-
withdrawing nitro group increases the polarization of the carbonyl by withdrawing electrons from
it through the aromatic ring. The electron donating methoxy group decreases the polarization of
the carbonyl by donating electrons to it through the aromatic ring.
16. Write the complete stepwise mechanism for the basic hydrolysis of acetamide, shown below.
Show all electron flow with arrows and draw all intermediate structures.
ANS:
5
Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions
Exhibit 21-2
Consider the reaction below to answer the following question(s):
Acid halides react with diazomethane to yield diazoketones. Excess diazomethane is used to
prevent the HCl produced in the reaction from reacting with the diazoketone.
17. Refer to Exhibit 21-2. Diazomethane is an example of a dipolar molecule; a molecule which
is neutral overall but has charges on individual atoms. One resonance form of diazomethane
is drawn below. Draw the Lewis structure of the other resonance form of diazomethane. Be
sure to include all formal charges.
ANS:
18. Refer to Exhibit 21-2. The intermediate structures for the mechanism for the reaction of
propanyl chloride with diazomethane are provide below. Show all electron flow with arrows
on these structures.
6
Chapter 21
ANS:
Exhibit 21-3
Consider the reaction below to answer the following question(s):
19. Refer to Exhibit 21-3. Write the complete stepwise mechanism for this reaction. Show
intermediate structures and all electron flow with arrows.
ANS:
7
Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions
ANS:
b
21. Refer to Exhibit 21-3. The purpose of the base catalyst in this reaction is:
ANS:
c
a. a lactone
b. an anhydride
c. a lactam
d. an ether
ANS:
a
23. Methyl butanoate has been isolated from pineapple oil and can be prepared by the Fischer
esterification reaction shown below. Write the complete stepwise mechanism for this
reaction. Show all electron flow with arrows and include all intermediate structures.
8
Chapter 21
ANS:
24. Write the complete stepwise mechanism for the acid-catalyzed hydrolysis of the following
amide to yield mandelic acid. Show all electron flow with arrows and draw the structures of
all intermediate species.
ANS:
9
Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions
25. The purpose of the acid catalyst in the hydrolysis of an amide is:
a. to enhance the nucleophilicity of the water molecule
b. to enhance the electrophilicity of the amide carbonyl carbon
c. to enhance the electrophilicity of the water molecule
d. to shift the equilibrium of the reaction
ANS:
b
Exhibit 21-4
Consider the information below to answer the following question(s).
The reaction of a carboxylic acid with an alcohol in the presence of acid is termed Fischer
esterification.
ANS:
B
ANS:
c
ANS:
b
10
Chapter 21
29. Refer to Exhibit 21-4. Write the stepwise mechanism for the Fischer esterification reaction
of benzoic acid and methanol given above. Show all electron flow by using curved arrows,
and include all intermediate structures.
ANS:
Exhibit 21-5
Provide structure(s) for the starting material(s), reagent(s) or the major organic product(s) of each
of the following reactions or sequences of reactions. Show all relevant stereochemistry.
30.
ANS:
11
Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions
31.
ANS:
32.
ANS:
33.
ANS:
12
Chapter 21
34.
ANS:
35.
ANS:
36.
ANS:
13
Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions
37.
ANS:
38.
ANS:
39.
ANS:
14
Chapter 21
40.
ANS:
41.
ANS:
42.
15
Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions
ANS:
43.
ANS:
44.
ANS:
16
Chapter 21
Exhibit 21-6
Choose the best reagent(s) from the list provided below for carrying out the following
transformations. Place the letter corresponding to the best choice in the blank to the left of the
transformation.
45. _____
ANS:
h
46. _____
ANS:
a
47. _____
ANS:
d
17
Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions
48. _____
ANS:
f
49. _____
ANS:
d
Exhibit 21-7
Show how you would accomplish each of the following transformations. More than one step may
be required. Show all reagents and all intermediate structures.
50.
ANS:
51.
18
Chapter 21
ANS:
52.
ANS:
53.
ANS:
19
Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions
ANS:
55. Ethyl phenylacetate is a pleasant smelling compound used in perfumery. Draw structures for
each of the intermediates in the synthesis of ethyl phenylacetate below.
20
Chapter 21
ANS:
Exhibit 21-8
For each pair of compounds below, tell which spectroscopic technique you would use to
distinguish between the two members of the pair. Tell what differences you would expect to see.
56.
ANS:
IR 2250 cm 1 (nitrile)
−
1730−1760 cm 1 −
(four-membered lactam)
Although you would not be expected to know the absorption of a four-membered lactam, you
should be able to predict that IR spectroscopy would differentiate these two compounds based
solely on the nitrile absorption in the first compound and the fact that the lactam would have a
carbonyl absorption somewhere in the region of 1660−1750 cm 1. −
57.
21
Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions
ANS:
IR 1735 cm 1−
1720 cm 1 −
58.
ANS:
IR 1820, 1760 cm 1 −
2500−3300 cm 1 (acid−OH)
−
1715 cm 1 (ketone)
−
1
H NMR one triplet three overlapping triplets
one quartet one quartet
one singlet
Exhibit 21-9
Refer to the data below to answer the following question(s):
Kodel is a staple and filament fiber prepared from dimethyl terephthalate and 1,4-
®
59. Refer to Exhibit 21-9. Draw the structure of the Kodel polymer.
®
ANS:
22
Chapter 21
a. a polyurethane
b. a polyester
c. a polyamide
d. a polycarbonate
ANS:
b
61. Poly(ethylene terephthalate), PET, is the polymeric material of Mylar and Dacron . What
® ®
ANS:
2. Name the following substance. Atoms other than carbon and hydrogen are labeled.
ANS:
4-methylpentanoyl chloride
23
Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions
63. Name the following substance. Atoms other than carbon and hydrogen are labeled.
ANS:
ethyl 1-chloropropanoate
MULTIPLE CHOICE
1. Which of the following will take place via nucleophilic acyl substitution?
a. thioester producing and acid chloride
b. ester producing a thioester
c. ester producing an amide
d. acid anhydride producing an acid chloride
ANS: C
2. The following reaction could be classified as which type of nucleophilic acyl substitution?
More than one step might be needed.
a. amoniolysis
b. alcoholysis.
c. reduction.
d. hydrolysis.
e. Grignard reaction.
f. c or e depending on reaction conditions.
g. The reaction will not occur via nucleophilic acyl substitution.
ANS: D
24
Chapter 21
3. The following reaction could be classified as which type of nucleophilic acyl substitution?
More than one step might be needed.
a. amoniolysis
b. alcoholysis.
c. reduction.
d. hydrolysis.
e. Grignard reaction.
f. c or e depending on reaction conditions.
g. The reaction will not occur via nucleophilic acyl substitution.
ANS: B
4. The following reaction could be classified as which type of nucleophilic acyl substitution?
More than one step might be needed.
a. amoniolysis
b. alcoholysis.
c. reduction.
d. hydrolysis.
e. Grignard reaction.
f. c or e depending on the reaction conditions.
g. The reaction will not occur via nucleophilic acyl substitution.
ANS: C
5. The following reaction could be classified as which type of nucleophilic acyl substitution?
25
Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions
a. amoniolysis
b. alcoholysis.
c. reduction.
d. hydrolysis.
e. Grignard reaction.
f. c or e depending on reaction conditions.
g. The reaction will not occur via nucleophilic acyl substitution.
ANS: G
6. What is the product when the following substance reacts with trimethylamine ((CH3)3N)?
Atoms other than carbon and hydrogen are labeled.
a.
b.
c.
d.
No reaction occurs.
ANS: D
26
Chapter 21
7. What is the name of the product when the following substance reacts with NaCH3COO?
Atoms other than carbon and hydrogen are labeled.
a. 4-methylbutanoic acid
b. acetic 4-methylbutanoic anhydride
c. 4-methylbutyl acetate
d. acetyl 4-methylbutanoate
e. No reaction occurs.
ANS: B
8. Which line in the following spectrum would indicate the presence of a carbonyl group?
a. 1
b. 2
c. 3
d. 4
e. 5
ANS: E
27
Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions
28
Chapter 21
11. Consider the following molecular model. Atoms other than carbon and hydrogen are
labeled.
12. Consider the structure given below which might be found in a protein.
29