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Name: __________________ Class: Date: _____________
(First Page)Name: __________________ Class: Date: _____________
(Subsequent Pages)1.
IUPAC Naming Instructions: Provide the proper IUPAC name.
Name:
_____________________________________________ 2.
IUPAC Naming Instructions: Provide the proper IUPAC name.
Name:
_____________________________________________ 3.
Exhibit 21-4Consider the information below to answer the following question.
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
Enter the letter of the correct choice in the space provided.
________ 4.
Exhibit 21-4Consider the information below to answer the following question.
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 allelectron flow by using curved arrows, and include all intermediate structures. (use a separate sheet to answer if necessary)
5.
Exhibit 24-4Refer to the reaction below to answer the following question:
Refer to Exhibit 24-4. This reaction is an example of:
a. a Curtius rearrangement.
b. a Hofmann elimination reaction.
c. a Gabriel synthesis.
d. a Hofmann rearrangement.
Enter the letter of the correct choice in the space provided.
________ 6.
Exhibit 24-7Choose the best series of reactions for accomplishing the conversion below.
a.
b.
c.
d.
Enter the letter of the correct choice in the space provided.
________ 7.
Exhibit 24-1Classify the following nitrogen atom in the following compound as primary, secondary, tertiary, or quaternary.
The nitrogen atom in amphetamine is _______________ .8.
Exhibit 24-1Classify the following nitrogen atom in the following compound as primary, secondary, tertiary, or quaternary.
The nitrogen in mepiquat chloride is a _______________ ammonium salt.9.
Exhibit 22-4Consider the reaction sequence below to answer the following question:
Refer to Exhibit 22-4. Compound X, diethyl propanedioate, is more commonly known as:
a. ethyl acetoacetate.
b. acetoacetic ester.
c. oxalic ester.
d. malonic ester.
Enter the letter of the correct choice in the space provided.
________ 10.
Exhibit 22-4Consider the reaction sequence below to answer the following question:
Refer to Exhibit 22-4. Write the complete stepwise mechanism for the conversion of Compound X into Compound Y. Show all electron flow witharrows and draw all intermediate structures. (use a separate sheet to answer if necessary)
11.
Exhibit 24-2Consider the reaction below to answer the following question.
Methamphetamine can be synthesized by reacting phenyl-2-propanone with methylamine in the presence of H2/Ni.
Refer to Exhibit 24-2. Identify the nucleophile in the initial reaction of phenyl-2-propanone to yield intermediate A.
The nucleophile is _______________ .
Exhibit 23-11Give the major organic product(s) for the following reaction or reaction sequence.
This question was omitted on the printed copy. This placeholder question is here to maintain the numbering system integrity between the printedcopy and this testbank.
Please proceed to the next item.13.
Exhibit 22-8How would you prepare the following compound using either an acetoacetic ester synthesis or a malonic ester synthesis? Show all intermediatestructures and all reagents.
(use a separate sheet to answer if necessary)
14.
Drawing Instructions: Draw a structure corresponding to the given name.
Draw: 2-propenamide (use a separate sheet to answer if necessary)
15.
Drawing Instructions: Draw a structure corresponding to the given name.
Draw: (E)-2,4-dimethyl-2-hexenoyl chloride (use a separate sheet to answer if necessary)
16.
Exhibit 21-5Provide structure(s) for the starting material(s), reagent(s) or the major organic product(s) of the following reaction or sequence of reactions.Show all relevant stereochemistry.
(use a separate sheet to answer if necessary)
17.
Exhibit 21-5Provide structure(s) for the starting material(s), reagent(s) or the major organic product(s) of the following reaction or sequence of reactions.Show all relevant stereochemistry.
(use a separate sheet to answer if necessary)
18.
Exhibit 21-5Provide structure(s) for the starting material(s), reagent(s) or the major organic product(s) of the following reaction or sequence of reactions.Show all relevant stereochemistry.
(use a separate sheet to answer if necessary)
19.
Exhibit 23-6Draw the structure of the product you would expect to obtain by Claisen condensation of the following ester. If the ester does not undergoClaisen condensation, explain why it does not.
(use a separate sheet to answer if necessary)
20.
Exhibit 23-9Draw the structures of the precursors to the following Michael reaction product. Label the Michael donor and the Michael acceptor andformulate the reaction.
(use a separate sheet to answer if necessary)
21.
Exhibit 23-9Draw the structures of the precursors to the following Michael reaction product. Label the Michael donor and the Michael acceptor andformulate the reaction.
(use a separate sheet to answer if necessary)
22.
Exhibit 23-9Draw the structures of the precursors to the following Michael reaction product. Label the Michael donor and the Michael acceptor andformulate the reaction.
(use a separate sheet to answer if necessary)
23.
Exhibit 24-6Show how the following transformation might be best accomplished. More than one step may be required. Show all reagents and all intermediatestructures.
(use a separate sheet to answer if necessary)
24.
Exhibit 24-6Show how the following transformation might be best accomplished. More than one step may be required. Show all reagents and all intermediatestructures.
(use a separate sheet to answer if necessary)
25.
Exhibit 22-9Show how you would accomplish the following transformation. More than one step may be required. Show all reagents and all intermediatestructures.
(use a separate sheet to answer if necessary)
26.
Exhibit 24-5Give the major organic product(s) of the following reaction or sequence of reactions. Show all relevant stereochemistry.
(use a separate sheet to answer if necessary)
27.
Exhibit 24-5Give the major organic product(s) of the following reaction or sequence of reactions. Show all relevant stereochemistry.
(use a separate sheet to answer if necessary)
28.
Exhibit 24-5Give the major organic product(s) of the following reaction or sequence of reactions. Show all relevant stereochemistry.
(use a separate sheet to answer if necessary)
29.
Exhibit 24-5Give the major organic product(s) of the following reaction or sequence of reactions. Show all relevant stereochemistry.
(use a separate sheet to answer if necessary)
30.
Exhibit 24-5Give the major organic product(s) of the following reaction or sequence of reactions. Show all relevant stereochemistry.
(use a separate sheet to answer if necessary)
31.
Exhibit 24-5Give the major organic product(s) of the following reaction or sequence of reactions. Show all relevant stereochemistry.
(use a separate sheet to answer if necessary)
32.
Exhibit 22-7Give the major organic product(s) of the following reaction or sequence of reactions. Show all relevant stereochemistry.
(use a separate sheet to answer if necessary)
33.
Exhibit 22-7Give the major organic product(s) of the following reaction or sequence of reactions. Show all relevant stereochemistry.
(use a separate sheet to answer if necessary)
34.
Exhibit 22-6Consider the reaction below to answer the following question:
Refer to Exhibit 22-6. Explain the product ratio in this reaction. (use a separate sheet to answer if necessary)
35.
Exhibit 21-3Consider the reaction below to answer the following question:
Refer to Exhibit 21-3. Write the complete stepwise mechanism for this reaction. Show intermediate structures and all electron flow witharrows. (use a separate sheet to answer if necessary)
36.
Exhibit 23-3Consider the data below to answer the following question:
The Friedlander Quinoline Synthesis, first reported in 1882, is the base-catalyzed condensation of 2-aminobenzaldehydes with ketones to formquinoline derivatives.
Refer to Exhibit 23-3. The second step of the Friedlander Quinoline Synthesis is a nucleophilic addition of a primary amine to a ketone yielding animine. Write the complete stepwise mechanism for this imine forming reaction. Show all electron flow with arrows and show all intermediatestructures.
(use a separate sheet to answer if necessary)
37.
Exhibit 21-2Consider the reaction below to answer the following question:
Acid halides react with diazomethane to yield diazoketones. Excess diazomethane is used to prevent the HCl produced in the reaction fromreacting 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.
(use a separate sheet to answer ifnecessary)
38.
Exhibit 24-8Refer to the data below to answer the following question:
Triclocarban is a disinfectant prepared from 3,4-dichloroaniline and 4-chlorophenylisocyanate.
Refer to Exhibit 24-8. Prepare 4-chlorophenylisocyanate from toluene.
(use a separate sheet to answer if necessary)
39.
Exhibit 23-1Draw the structure of the aldol self-condensation product for the following compound. If the compound does not undergo aldolself-condensation, explain why it does not.
(use a separate sheet to answer if necessary)
40.
Exhibit 21-7Show how you would accomplish the following transformation. More than one step may be required. Show all reagents and all intermediatestructures.
(use a separate sheet to answer if necessary)
41.
Exhibit 22-1Refer to the compounds below to answer the following question:
Refer to Exhibit 22-1. Indicate all the acidic hydrogens in Compounds I through IV. (use a separate sheet to answer if necessary)
42. Write the complete stepwise mechanism for the basic hydrolysis of acetamide, shown below. Show all electron flow with arrows and draw allintermediate structures.
(use a separate sheet to answer if necessary)
43. Methyl butanoate has been isolated from pineapple oil and can be prepared by the Fischer esterification reaction shown below. Write the completestepwise mechanism for this reaction. Show all electron flow with arrows and include all intermediate structures.
(use a separate sheet to answer ifnecessary)
44. Write the complete stepwise mechanism for the acid-catalyzed hydrolysis of the following amide to yield mandelic acid. Show all electron flowwith arrows and draw the structures of all intermediate species.
(use a separate sheet to answer if necessary)
45. 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.
Enter the letter of the correct choice in the space provided.
________ 46. Ethyl phenylacetate is a pleasant smelling compound used in perfumery. Draw structures for each of the intermediates in the synthesis of ethylphenylacetate below.
(use a separate sheet to answer if necessary)
47. Write the complete stepwise mechanism for the reaction of cyclopentanone with bromine in acetic acid to give 2-bromocyclopentanone. Show allintermediate structures and all electron flow with arrows. (use a separate sheet to answer if necessary)
48. In the alkylation of cyclohexanone, better yields are obtained by first reacting cyclohexanone with an equivalent of lithium diisopropylamide inTHF and then adding the alkyl halide, rather than mixing cyclohexanone, alkyl halide, and a catalytic amount of sodium ethoxide in ethanol.Explain this observation by pointing out what the problems with the second reaction conditions might be and how the first set of reactionconditions help alleviate the problems. (use a separate sheet to answer if necessary)
49. Oxaloacetic acid is an important intermediate in the biosynthesis of citric acid. Synthesize oxaloacetic acid using a mixed Claisen condensation as akey carbon-carbon bond forming reaction.
(use a separate sheet to answer if necessary)
50. Rank the following compounds in order of increasing basicity. Label the least basic compound "1" and the most basic compound "4". Place thenumber corresponding to the compound's rank in the blank below the compound.
(use a separate sheet to answer if necessary)
51. When a THF solution of phenyl-2-propanone and bromobutane is treated with 50% aqueous NaOH, poor yields of 3-phenyl-2-heptanone result.However, when a small amount of benzyltriethylammonium chloride is added to the reaction mixture, the yield of 3-phenyl-2-heptanone increasesto 90%. Explain these results.
(use a separate sheet to answer ifnecessary)
PAGE 1 (First Page)
PAGE 1 (Subsequent Pages)
ANSWER KEY
21-24
1 m-chloro-N,N-dimethylaniline2 p-nitroaniline3 c
4 5 d6 c7 primary8 quaternary
9 d
10 11 methylamine
13
14
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23
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33 34 Lithium diisoproylamide is a sterically hindered base, so abstraction of a proton is more favorable at the less sterically crowded side of theketone. Hence, the substitution occurs primarily at position 6 rather than position 2.
35
36
37
38
39
40 41 Acidic hydrogens are underlined.
42
43
44 45 b
46
47 48 When cyclohexanone is placed in a solution of sodium ethoxide in ethanol, the enolate is generated in small amounts in the presence of largeamounts of ketone-ideal conditions for an aldol self-condensation. Consequently, aldol self-condensation competes with alkylation of the enolate,and product mixtures result.
Conversely, when cyclohexanone is treated first with an equivalent of LDA, the enolate is rapidly generated and no ketone remains. Addition ofalkyl halide then yields the desired alkylated product.
49
50 51 The reaction that is occurring is a carbonyl -substitution reaction. Hydroxide ion abstracts a proton from C-l on phenyl-2-propanone togenerate an enolate ion, which then undergoes SN2 attack at the primary carbon of bromobutane. However, since the organic layer and waterlayer are immiscible, the hydroxide is unable to come into contact with the ketone in the organic phase, so there is little or no reaction.
When the quaternary ammonium salt is added, it dissolves in both the aqueous and organic layers. When it moves into the organic layer, it takeshydroxide ion with it, to preserve the charge neutrality. Once in the organic layer, hydroxide ion reacts with the ketone to generate the enolate,which then undergoes SN2 displacement of bromide to give the carbonyl -substitution product.
ANSWER KEY - Page 1
