Deck 21: Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions

Question 1

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.
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.

Answer 1

Question 2

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.

Answer 2

Question 3

Draw: (E)-2,4-dimethyl-2-hexenoyl chloride

Answer 3

Question 4

Draw: N,N-dimethylformamide

Question 5

Exhibit 21-3
Consider the reaction below to answer the following question(s):
Refer to Exhibit 21-3.The purpose of the base catalyst in this reaction is:

A)to polarize the carbonyl group to make it more electrophilic
B)to convert the ester to an intermediate carboxylic acid
C)to convert the alcohol group to an alkoxide anion,which is a better nucleophile
D)all of the above

Question 6

Draw: acetic formic anhydride

Question 7

Name:

Question 8

Draw: 2-propenamide

Question 9

Draw: methyl cis-3-ethylcyclobutanecarboxylate

Question 10

Name:

Question 11

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Question 12

Name:

Question 13

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.

Question 14

Exhibit 21-3
Consider the reaction below to answer the following question(s):
Refer to Exhibit 21-3.Write the complete stepwise mechanism for this reaction.Show intermediate structures and all electron flow with arrows.

Question 15

Draw: 3,4,5-trimethoxybenzoyl chloride

Question 16

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.
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.

Question 17

Exhibit 21-3
Consider the reaction below to answer the following question(s):
Refer to Exhibit 21-3.This reaction is an example of:

A)an intermolecular nucleophilic acyl substitution reaction
B)an intramolecular nucleophilic acyl substitution reaction
C)an intermolecular S_N2 reaction
D)an intramolecular S_N2 reaction

Question 18

Name:

Question 19

Exhibit 21-3
Consider the reaction below to answer the following question(s):
Refer to Exhibit 21-3.The product of this reaction is:

A)a lactone
B)an anhydride
C)a lactam
D)an ether

Question 20

What is the correct structure for phenylbenzoate?

A)
B)
C)
D)

Question 21

Name the following substance.Atoms other than carbon and hydrogen are labeled.

Question 22

Which line in the following spectrum would indicate the presence of a carbonyl group?

A)1
B)2
C)3
D)4
E)5

Question 23

Ethyl phenylacetate is a pleasant smelling compound used in perfumery.Draw structures for each of the intermediates in the synthesis of ethyl phenylacetate below.

Question 24

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.
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.

Question 25

Consider the following molecular model.Atoms other than carbon and hydrogen are labeled. Which of the following reactants could be used to produce this compound?

A)2-chloropropanoic acid and ethanol
B)propanoic acid and chloroethanol
C)propanoic acid and ethanol

Question 26

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.

Question 27

Aklomide,2-chloro-4-nitrobenzamide,is an ingredient in veterinary antibacterial preparations.Propose a synthesis of aklomide starting with toluene.Show all reagents and all intermediate structures.

Question 28

Based on the following spectrum the sample used would probably be classified as a(n):

A)aldehyde.
B)ketone.
C)ester.
D)The spectrum is not specific enough to classify the substance.

Question 29

Which of the following will take place via nucleophilic acyl substitution?

A)thioester producing an acid chloride
B)ester producing a thioester
C)ester producing an amide
D)acid anhydride producing an acid chloride

Question 30

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

Question 31

Name the following substance.Atoms other than carbon and hydrogen are labeled.

Question 32

The following is an excerpt from a spectrum taken on an unknown sample. To which of the following functional groups might the unknown belong?

A)amide
B)acid chloride
C)carboxylic acid
D)ester
E)None of these can be eliminated.

Question 33

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.
Refer to Exhibit 21-4.Fischer esterification is an example of:

A)nucleophilic acyl addition
B)nucleophilic acyl substitution
C)nucleophilic acyl elimination
D)nucleophilic acyl rearrangement

Question 34

Poly(ethylene terephthalate),PET,is the polymeric material of Mylar and Dacron .What are the monomers from which PET is prepared?

Question 35

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-cyclohexanedimethanol.Fabric made from Kodel has good crease resistance.
Refer to Exhibit 21-9.Draw the structure of the Kodel polymer.

Question 36

Consider the structure given below which might be found in a protein. Which of the following is not applicable to this structure?

A)contains three monomers
B)contains amide bonds
C)formed from a diacid and diamine
D)contains three types of monomers
E)All of these apply to this structure.

Question 37

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.
Refer to Exhibit 21-4.Compound C functions as _____ in this reaction.

A)a base scavenger
B)a solvent
C)a catalyst
D)a neutralizer

Question 38

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.

Question 39

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-cyclohexanedimethanol.Fabric made from Kodel has good crease resistance.
Refer to Exhibit 21-9.Kodel is an example of:

A)a polyurethane
B)a polyester
C)a polyamide
D)a polycarbonate

Question 40

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.
Refer to Exhibit 21-4.The nucleophile in this reaction is _____.

Question 41

Draw the mechanism of acid-catalyzed hydrolysis of propyl ethanoate to yield propanoic acid.​

Question 42

​Draw the mechanism of base-induced hydrolysis of ethyl propanoate.

Question 43

Which of the following describes nucleophilic acyl substitution?

A)Nucleophile adds to the electrophilic carbon of the carbonyl bond.
B)Electrophile replaces a group on the carbon alpha to the carbonyl.
C)Nucleophile replaces a group adjacent to the carbon of carbonyl.
D)Two carbonyl groups react with each other.

Question 44

​Draw the mechanism of the Fischer esterification of butanoic acid,in the presence of ethanol and hydrochloric acid,which is the catalyst.