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Problem set for chapters 19-22 from McMurry’s test bank

Ketons and aldehydes

1.

2.

3.

4.

5. Show the synthetic path of the following reaction:

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6. The nucleophile in this reaction is:

6b. Write the complete stepwise mechanism for the reaction above. Show all electron flow with arrows
and show all intermediate structures.

Carboxylic acids and Nitriles


1. Give the major product of the following reactions:

2. Design a synthetic path for the following transformation using inorganic compounds only, your “lab”
also does not contain any cyanide, but it does contain ether and benzene.

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3. Carboxylic acids are synthesized from alkyl halides via Grignard reagent carboxylation or nitrile
hydrolysis. Choose the best method for effecting each of the following conversions. Explain each of your
choices. If neither method is appropriate, explain.

A.

B.

C.

Derivatives of Carboxylic acids


1. Write the complete stepwise mechanism for this reaction. Show intermediate structures and all electron
flow with arrows.

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.

3. 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.

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The nucleophile in this reaction is _____.

Compound C functions as _____ in this reaction.


a. a base scavenger
b. a solvent
c. a catalyst
d. a neutralizer

Fischer esterification is an example of:


a. nucleophilic acyl addition
b. nucleophilic acyl substitution
c. nucleophilic acyl elimination
d. nucleophilic acyl rearrangement

Write the stepwise mechanism for the Fischer esterification reaction of benzoic acid and methanol given
above. Show all electron flow by using curved arrows, include all intermediate structures.

4. 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.

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Carbonyl Alpha-Substitution Reactions
1. Indicate all the acidic hydrogens in Compounds I through IV. Draw the structures for all enols of
Compound I.

2. Write the complete stepwise mechanism for the conversion of Compound X into Compound Y. Show
all electron flow with arrows and draw all intermediate structures. Et is ethane, EtOH is ethanol.

Below are the structures and electron flow for the conversion of Compound Y into Compound Z. Draw
the structure of Compound Z. (Hint: Compound Z is an alcohol.)

3. Write the complete stepwise mechanism for the reaction of cyclopentanone with bromine in acetic acid
to give 2-bromocyclopentanone. Show all intermediate structures and all electron flow with arrows.

4. Give the major organic product(s) of each of the following reactions or sequences of reactions. Show
all relevant stereochemistry.

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Answers:
Ketons and aldehydes

1.

2.

3. C
4. B
5.

6. B

6b.

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Carboxylic acids and Nitriles

1.

2.

3.

A.

ANSWER: Since SN2 displacements do not occur at tertiary alkyl halides the Grignard reagent
carboxylation is the best method for carrying out this conversion.

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B.

ANSWER: Either method would be appropriate for this conversion.

C.

ANSWER: Neither method of acid synthesis yields the desired product. Any Grignard reagent formed
will react with the carbonyl function group present in the starting material. Reaction with
cyanide occurs at the carbonyl functional group as well as at the halogen. However, if the
aldehyde is first protected by forming an acetal, either method can be used to synthesize a
carboxylic acid.

Derivatives of Carboxylic acids


1.

2.

3.
B
c
b

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4.

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Carbonyl Alpha-Substitution Reactions
1.

2.

Compound Z =

3.

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4.

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