Chapter 23: Substitution Reactions of Carbonyl Compounds at The Alpha-Carbon

Chapter 1: Structure and Bonding
44. Which of the following statements about amides is true?

A) Amides react with methyl alcohol in the presence of an acid catalyst to form an
ester.
B) Amides are hydrolyzed in acid or base to form carboxylic acids or carboxylate
anions.
C) Amides react with thionyl chloride to form the acid chloride.
D) Amides do not react under any conditions. They are inert compounds.
45. n-Butanenitrile will undergo all of the following listed reactions except one. Which
reaction listed is not true for n-butanenitrile?
A) n-Butane nitrile will react with ethylmagnesium bromide to form an alcohol.
B) n-Butanenitrile with be reduced to butyl amine in the presence of LiAlH4 with an
aqueous work-up.
C) n-Butanenitrile is hydrolyzed in the presence of acid to form butanoic acid.
D) n-Butanenitrile is reduced with DIBAL-H to form n-butanal.
46. An unknown compound has a sharp, medium peak at 2250 cm-1. The unknown
compound is probably
A) an alkane B) an aldehyde C) an alkene D) a nitrile
47. All of the following contain sp2 hybridized atoms in their functional group except
A) a carboxylic acid B) a nitrile C) an aldehyde D) an anhydride
Chapter 23: Substitution Reactions of Carbonyl Compounds at

the Alpha-Carbon
1. Which is the more stable form of acetophenone?
A) Only I B) Only II C) Only III D) I and II are equally stable
Page 248
2. Which is the most stable form of 1,3-cyclohexanedione?
A) I B) II C) III D) IV
3. Which of the following is an enol form of the following compound?
4. Why is the enolate of acetone less basic than the allyl anion derived from propene?
A) Because there are more atoms in acetone
B) Because there are more resonance structures for the enolate of acetone
C) It isn't; the allyl anion is less basic.
D) One of the resonance structures for the enolate places the negative charge on the
more electronegative oxygen.
5. Which of the following four compounds is the most acidic?
6. Will acetone be completely deprotonated by potassium tert-butoxide?

A) Yes B) No
7. Will acetophenone be completely deprotonated by lithium diisopropylamide (LDA)?

A) Yes B) No
Page 249
8. Which is the kinetic enolate of 2-methylcyclohexanone?
9. If you want to form a thermodynamic enolate, you want to:

A) Keep the reaction as cold as possible. C) Use a protic solvent such as ethanol.
B) Use an aprotic solvent such as THF. D) Use a carboxylic acid.
10. If you want to form a kinetic enolate, you want to:

A) Use a strong, non-nucleophilic base such as LDA.
B) Use a protic solvent.
C) Use a low temperature.
D) Both use a strong, non-nucleophilic base such as LDA and use a low temperature.
11. Which of the following is the intermediate for halogenation of ketones under acidic
conditions?
A) An enolate B) An enol C) A tautomer D) An epimer
12. Why is it difficult to stop the halogenation of ketones under basic conditions at the
mono-halogenated stage?
A) The ketone undergoes a Bayer-Villigar oxidation.
B) The ketone is reduced.
C) The ketone undergoes an Aldol reaction.
D) The bromine helps to stabilize the second enolate, making the product more acidic
than the starting material.
13. Why can't you prepare 2-tert-butylcyclohexanone by the following reaction?
A) Because tert-butyl bromide is too basic.
Page 250
B) Because tert-butyl bromide cannot undergo an SN2 reaction.

C) Because tert-butyl bromide is a nucleophile.
D) Because tert-butyl bromide is not a stable compound.
14. What are the three steps in the malonic ester synthesis?
A) Deprotonation, alkylation, hydrolysis/decarboxylation
B) Hydrogenation, alkylation, deprotonation
C) Alkylation, hydrolysis/decarboxylation. hydrogenation
D) Hydrolysis/decarboxylation, deprotonation, alkylation
15. What is the missing reagent for the following reaction?
A) Br2/HOAc B) Br2/KOH C) Cl2/FeCl3 D) Br2/FeBr3
16. Starting with cyclohexanone, how could you prepare the diketone below?
A) Treat cyclohexanone with a base under thermodynamic conditions.

B) Hydrogenate cyclohexanone with Raney nickel.
C) Convert cyclohexanone into the -bromoketone and then react this with the enolate
of cyclohexanone.
D) Convert cyclohexanone into an enamine with diethylamine and then react this with
more cyclohexanone.
Page 251
17. What is the product of the following reaction?
18. What is the product of the following reaction?
19. What is (are) the product(s) of the following reaction?
A) Only I B) Only II C) Only III D) Only I and III
20. What is the missing reagent in the reaction below?
A) Br2/AcOH B) I2/KOH C) I2 D) KOH
Page 252
21. What is the starting material in the following reaction?
22. What is the starting material for the following reaction?
23. Which of the following compounds is an enol of compound X drawn below?
A) Only I B) Only II C) Only III D) Only I and II
Page 253
24. Which of the following are enol forms of ethyl acetoacetate drawn below?
A) Only I B) Only II C) Only III D) I, II, and III
25. For most compounds with a single keto group in the molecule, equilibrium favors the
keto form over the enol form of the compound. This is due largely to what?
A) The C=O bond is much stronger than the C=C bond.
B) The C=C bond is much stronger than the C=O bond.
C) The keto form can undergo intramolecular hydrogen bonding.
D) The enol form can undergo intramolecular hydrogen bonding.
26. It has been found that -dicarbonyl compounds have a greater concentration of the enol
form over the keto form. This can be explained by:
A) The C=C of the enol is conjugated with the carbonyl group.
B) The -OH of the enol can hydrogen bond to the oxygen of the nearby carbonyl
group.
C) Both A and B above are true.
D) None of the choices are true.
27. The reaction below is a direct enolate alkylation. It has been found that this reaction
only works well with unhindered methyl and 1° alkyl halides. Pick the statement that
best explains this observation.
A) The nucleophilic enolate requires a reaction center that has a positive charge.
B) Hindered alkyl halides do not undergo SN1 reactions.
C) Hindered alkyl halides do not undergo SN2 reactions.
D) Methyl and 1° alkyl halides can form carbocations that can readily react with the
nucleophilic enolate.
Page 254
28. The following molecule is called:
A) a 1,3-diketopentanoate. C) an ethyl acetoacetate.

B) a diethyl malonate. D) a -keto ester.
29. A simple chemical test to distinguish between acetone and 3-pentanone would be the
reaction of the compounds with
A) bromine with acetic acid.
B) bromine and aqueous hydroxide ion.
C) THF, LDA at -78 °C followed by reaction with bromine.
D) base and methyl bromide.
30. Which is the thermodynamic enolate of 2-methylcyclohexanone?
31. Which of the following compounds is the most acidic?

A) Ethyl acetoacetate B) 2-Butanone C) 1-Butanol D) 3-Pentanone
32. Which is the most acidic proton in the following compound?
Page 255
33. Which is the most acidic proton in the following compound?
34. Which of the following bases will completely convert 1,4-cyclohexandione into an
enolate?
A) Sodium hydroxide C) Sodium tert-butoxide
B) Sodium methoxide D) Sodium hydride
35. Which of the following compounds would undergo racemization in the presence of a
base?
36. Which of the following ketones will give a positive iodoform test?
A) 3-Heptanone B) 2-Pentanone C) 3-Hexanone D) Cyclohexanone
37. What is the major product of the following reaction?
Page 256
38. Treatment of 2-hexanone with NaOCH2CH3 followed by CH3Br affords compound X

(C7H14O) as the major product. X shows a strong absorption in the IR spectrum at 1713
cm-1, and its 1H NMR data is given below. What is the structure of X?
39. The malonic ester synthesis can be adapted to synthesize -amino acids by using diethyl
acetamidomalonate as the starting material. Select the structure of the amino acid
produced by the following synthesis.
Page 257
40. Select the appropriate sequence of reactions to accomplish the following synthesis.
A) [1] Br2, CH3CO2H; [2] Li2CO3, LiBr, DMF; [3] CH3CH2CH2CH2Br

B) [1] Br2, CH3CO2H; [2] Mg, Et2O; [3] CH3CH2CH2CH2Br
C) [1] LDA; [2] BrCH2CH2CH2CH2Br; [3] NaOEt
D) [1] NaOEt; [2] BrCH2CH2CH2CH2Br; [3] LDA
41. What is the starting material required to accomplish the following transformation?
Chapter 24: Carbonyl Condensation Reactions
1. What is the general name for the reaction product formed in an aldol addition reaction?
A) -hydroxy carbonyl compound. C) -hydroxy carbonyl compound.
B) -hydroxy carbonyl compound. D) ,-hydroxy carbonyl compound.
2. In the correct order, what are the three steps in the mechanism of an Aldol reaction?
A) Protonation, enolate formation, nucleophilic addition.
B) Enolate formation, protonation, nucleophilic addition.
C) Enolate formation, nucleophilic addition, protonation.
Page 258
C) acetone
D) All of these compounds contain -hydrogens
43. Complete this statement: A major difference between the Aldol condensation and the
Claisen condensation reactions is that
A) the Aldol reaction involves substitution while the Claisen reaction involves
addition.
B) the Aldol reaction is acid catalyzed while the Claisen reaction is base-catalyzed.
C) the Aldol reaction is base catalyzed while the Claisen reaction requires a full
equivalent of base.
D) the Aldol reaction is base catalyzed while the Claisen reaction is acid-catalyzed.
44. If a Claisen condensation reaction is run using methyl propanoate as the reactant,
NaOCH3 is the ideal base. Why is it important to use NaOCH3 and not NaOCH2CH3?
A) NaOCH3 is a stronger base than NaOCH2CH3, and this reaction requires a stronger
base.
B) NaOCH3 is a weaker base than NaOCH2CH3, and this reaction requires a weaker
base.
C) Transesterfication can occur when esters react, and this transesterfication would
result in a mixture of products.
D) NaOCH3 is more soluble than NaOCH2CH3 in organic solvents, and this reaction
requires a full equivalent of base to proceed. A full equivalent of NaOCH2CH3
would not dissolve, so the reaction would not proceed.
45. There are several variations of the Aldol reaction. Which of the following types of
reactants leads to only one possible product with the Aldol condensation reaction?
A) Two different aldehydes with -hydrogens are able to form a single aldol
condensation product.
B) Two different ketones with -hydrogens are able to form a single aldol
condensation product.
C) Any aldehyde and ketone mixed together can react to form a single condensation
product.
D) Any pair of aldehyde or ketone reactants where one of the reactants has no -
hydrogens will lead to a single aldol product.
Chapter 25: Amines
Page 268
1. Which of the following amines are classified as primary (1°) amines?
A) I B) II C) III D) I and II
2. Which of the following amines are classified as secondary (2°) amines?
A) I B) II C) III D) I and II
3. Which of the following amines are classified as tertiary (3°) amines?
4. What is the approximate bond angle of the substituents around a nitrogen atom in
amines?
A) 90° B) 109.5° C) 120° D) 180°
5. Although an amine nitrogen atom containing an electron pair and bonded to three
different groups is technically a stereogenic center, the chirality of the amine nitrogen is
often ignored. Why is that?
A) Because four bonds are needed to define a stereogenic center.
B) Because chirality only exists with the tetrahedral carbon atoms.
C) Because there is usually slow interconversion between the two isomeric forms at
room temperature.
D) Because there is usually rapid interconversion between the two isomeric forms at
room temperature.
6. Why should the chirality of an ammonium salt with four different groups on the
nitrogen atom not be ignored?
A) Because there is rapid interconversion between the two isomeric forms at room
temperature.
Page 269
B) Because interconversion cannot occur between the two isomeric forms at room
temperature.
C) Because the compound would be a meso compound.
D) Because the compound would be a racemic mixture.
7. What is the common name of the following compound?
A) isopropylamine C) 2-methyl-1-propanamine
B) sec-butylamine D) isobutylamine
A) isopropylamine
B) sec-butylamine
C) isobutylamine
D) tert-butylamine
A) isopropylamine C) tert-butylamine
B) 2-methyl-2-propanamine D) isobutylamine
A) diisopropylamine
B) dipropylamine
C) diisopropanamine
D) dibutylamine
Page 270
A) dimethylisobutylamine C) N,N-dimethylbutanamine
B) butyldimethylamine D) sec-butyldimethylamine
12. What is the IUPAC name of the following compound?
A) N-propylhexanamine C) N-ethylcyclohexylamine
B) N-propylaniline D) N-propylcyclohexanamine
A) N-ethyl-N-methylpentylamine C) N-methyl-3-octanamine
B) N-ethyl-N-methyl-1-pentanamine D) N-ethyl-2-heptanamine
A) 3-methyl-1-hexanamine C) 4-methyl-1-hexanamine
B) 4-methyl-1-hexylamine D) 3-methyl-6-hexylamine
A) N-ethyl-N-methylcyclopentanamine C) N-methyl-N-ethylcyclopentylamine
B) N-cyclopentyl-N-methylethanamine D) N-ethyl-N-methylpentanamine
Page 271
A) 1-methyl-N-propyl-1-propanamine C) 2-propyl-3-hexanamine
B) 4-methyl-4-heptanamine D) N-propyl-2-pentanamine
A) (S)-methyl-4-hexanamine C) (R)-2-methyl-4-hexanamine
B) (S)-5-methyl-3-hexanamine D) (R)-5-methyl-3-hexanamine
A) (Z)-4-hexen-1-amine C) (E)-2-hexen-6-amine
B) (E)-4-hexen-1-amine D) (Z)-2-hexen-6-amine
19. What is the correct assignment of the names of the following aromatic amines?
A) I = pyrrolidine; II = pyrimidine; III = aniline.

B) I = pyrrole; II = pyrimidine; III = anisole.
C) I = pyrrolidine; II = pyridine; III =aniline.
D) I = pyrrole; II = pyridine; III = aniline.
Page 272
20. Arrange the following compounds in order of decreasing boiling point, putting the
compound with the highest boiling point first.
A) I > II > III B) I > III > II C) III > I > II D) III > II > I
21. Arrange the following compounds in order of increasing boiling point, putting the
compound with the least boiling point first.
A) I < II < III B) II < I < III C) I < III < II D) II < III < I
22. Arrange the following amines in order of decreasing water solubility, putting the most
soluble amine first.
A) I > II > III B) II > I > III C) III > I > II D) II > III > I
23. The mass spectrum of an amine shows a parent peak with an odd mass for the molecular
ion. What does this tell you about the amine?
A) The amine is a primary amine.
B) The amine is a secondary amine.
C) The amine contains an even number of N atoms.
D) The amine contains an odd number of N atoms.
24. What is a typical characteristic absorption in the IR spectrum of a primary amine?

A) Two N-H absorptions at 2500-2600 cm-1
B) One N-H absorption at 2500-2600 cm-1
C) Two N-H absorptions at 3300-3500 cm-1
D) One N-H absorption at 3300-3500 cm-1
Page 273
25. A compound with molecular formula C6H15N exhibits a singlet at  0.9 (1H), a triplet at
 1.10 (3H), a singlet at  1.15 (9H), and a quartet at  2.6 (2H) in its 1HNMR spectrum.
Its IR spectrum shows one medium absorption band near 3400 cm-1. What is the
structure of this compound?
26. What is the name given to naturally occurring amines derived from plant sources?
A) Enamines B) Imines C) Alkaloids D) Alkamines
27. Why is direct nucleophilic substitution of an alkyl halide with NH3 not a very useful
method for preparing primary amines?
A) NH3 is not a nucleophile.
B) Elimination will occur.
C) NH3 is too bulky to act as a nucleophile.
D) Polyalkylation of the amine will result in multiple products.
28. In the preparation of primary amines, how can direct nucleophilic substitution between
NH3 and alkyl halide be made more practical than reacting NH3 and the alkyl halide in a
1:1 ratio?
A) Use a large excess of NH3.
B) Use a large excess of alkyl halide.
C) Use a limited amount of NH3.
D) Make the alkyl halide sterically hindered.
29. Why is the N-H bond of an imide especially acidic?

A) The conjugate base is stabilized by electron-donating inductive effect.
B) The conjugate base is stabilized by resonance.
C) The conjugate acid is stabilized by resonance.
D) The conjugate base is stabilized by intramolecular hydrogen bonding.
Page 274
30. Which of the following alkyl halides cannot be used to prepare primary amines by the
Gabriel synthesis?
A) 2-bromo-2-methylbutane C) 2-bromo-3-methylbutane
B) 1-bromo-2-methylbutane D) 1-bromo-3-methylbutane
31. Predict the product(s) of the following reaction.
A) I B) II C) III D) None of the choices
32. What is the major organic product obtained in the following reaction?
Page 275
36. Why are 1°, 2°, and 3° alkylamines more basic than ammonia (NH3)?
A) Because of the electron-withdrawing inductive effect of the alkyl groups.
B) Because of the steric hindrance of the alkyl groups.
C) Because of the resonance delocalization of the alkyl groups.
D) Because of electron-donating inductive effect of the alkyl groups.
37. Why are alkylamines more basic than arylamines?

A) The lone pair electrons are localized in alkylamines and delocalized in arylamines.
B) The lone pair electrons are delocalized in alkylamines and localized in arylamines.
C) The lone pair electrons are less readily available in alkylamines.
D) The lone pair electrons are more readily available in arylamines.
Page 276
38. Rank the following compounds in order of increasing basicity, putting the least basic
compound first.
A) III < II < IV < I C) I < IV < II < III

B) II < III < IV < I D) III < I < II < IV
39. Rank the following compounds in order of decreasing basicity, putting the most basic
compound first.
A) II > I > III > IV C) I > III > II > IV

B) I > II > III > IV D) IV > II > III > I
40. Rank the following compounds in order of increasing basicity, putting the least basic
first.
A) II < III < IV < I C) IV < III < II < I

B) I < II < III < IV D) II < I < III < IV
41. Rank the following compounds in order of decreasing basicity, putting the most basic
first.
A) I > II > III > IV C) IV > III > I > II
Page 277
B) I > III > II > IV D) II > I > III > IV
42. Why is pyrrole much less basic than pyridine?

A) The lone pair of electrons in pyrrole is located on an sp2 orbital.
B) The lone pair of electrons in pyrrole is part of the aromatic  system.
C) The lone pair of electrons in pyrrole is not part of the aromatic  system.
D) The pKa of the conjugate acid of pyrrole is much greater than the conjugate acid of
pyridine.
43. Why is piperidine a stronger base than pyridine?

A) The lone pair of electrons in pyridine is part of the delocalized  system.
B) Aromatic compounds are always less basic than non-aromatic compounds.
C) The lone pair of electrons in piperidine is in an sp3 hybrid orbital; the lone pair of
electrons in pyridine is in an sp hybrid orbital.
D) The lone pair of electrons in piperidine is in an sp3 hybrid orbital; the lone pair of
electrons in pyridine is in an sp2 hybrid orbital.
44. Rank the following compounds in increasing order of basicity, putting the least basic
first.
A) II < I < IV < III C) IV < II < III < I

B) I < III < II < IV D) I < II < III < IV
45. Rank the nitrogen atoms in chloroquine, shown below, in order of decreasing basicity,
putting the most basic nitrogen atom first.
A) N1 > N2 > N3 B) N2 > N1 > N3 C) N3 > N2 > N1 D) N3 > N1 > N2
Page 278
46. Histamine, a vasodilator, is responsible for a wide variety of physiological effects. Rank
the three nitrogen atoms in histamine in increasing order of basicity, putting least basic
nitrogen atom first.
A) N2 < N1 < N3 B) N1 < N2 < N3 C) N3 < N1 < N2 D) N3 < N2 < N1
47. Predict the major organic product of the following reaction.
Page 279
51. Predict the major product of the following reaction.
Page 280
53. Select the reagent(s) required for the following transformation.
A) NaI B) (1) NaNO2, HCl; (2) NaI C) (1) NaNO2, HCl; (2) I2 D) I2
A) NaF B) (1) NaNO2, HCl; (2) F2 C) (1) NaNO2, HCl; (2) HBF4 D) F2
A) (1) NaNO2, HCl; (2) H2 C) (1) NaNO2, HCl; (2) H3PO4

B) (1) NaNO2, HCl; (2) H2O D) (1) NaNO2, HCl; (2) H3PO2
Page 281
58. What starting materials are required to synthesize the following azo compound?
Page 282

Chapter 23: Substitution Reactions of Carbonyl Compounds at The Alpha-Carbon

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Chapter 23: Substitution Reactions of Carbonyl Compounds at The Alpha-Carbon

Uploaded by

Copyright:

Available Formats

Chapter 1: Structure and Bonding

44. Which of the following statements about amides is true?

Chapter 23: Substitution Reactions of Carbonyl Compounds at

1. Which is the more stable form of acetophenone?

A) Only I B) Only II C) Only III D) I and II are equally stable

2. Which is the most stable form of 1,3-cyclohexanedione?

3. Which of the following is an enol form of the following compound?

5. Which of the following four compounds is the most acidic?

6. Will acetone be completely deprotonated by potassium tert-butoxide?

7. Will acetophenone be completely deprotonated by lithium diisopropylamide (LDA)?

8. Which is the kinetic enolate of 2-methylcyclohexanone?

9. If you want to form a thermodynamic enolate, you want to:

10. If you want to form a kinetic enolate, you want to:

13. Why can't you prepare 2-tert-butylcyclohexanone by the following reaction?

A) Because tert-butyl bromide is too basic.

B) Because tert-butyl bromide cannot undergo an SN2 reaction.

15. What is the missing reagent for the following reaction?

A) Br2/HOAc B) Br2/KOH C) Cl2/FeCl3 D) Br2/FeBr3

A) Treat cyclohexanone with a base under thermodynamic conditions.

17. What is the product of the following reaction?

18. What is the product of the following reaction?

19. What is (are) the product(s) of the following reaction?

A) Only I B) Only II C) Only III D) Only I and III

20. What is the missing reagent in the reaction below?

A) Br2/AcOH B) I2/KOH C) I2 D) KOH

21. What is the starting material in the following reaction?

22. What is the starting material for the following reaction?

23. Which of the following compounds is an enol of compound X drawn below?

A) Only I B) Only II C) Only III D) Only I and II

A) Only I B) Only II C) Only III D) I, II, and III

28. The following molecule is called:

A) a 1,3-diketopentanoate. C) an ethyl acetoacetate.

30. Which is the thermodynamic enolate of 2-methylcyclohexanone?

31. Which of the following compounds is the most acidic?

32. Which is the most acidic proton in the following compound?

33. Which is the most acidic proton in the following compound?

37. What is the major product of the following reaction?

38. Treatment of 2-hexanone with NaOCH2CH3 followed by CH3Br affords compound X

A) [1] Br2, CH3CO2H; [2] Li2CO3, LiBr, DMF; [3] CH3CH2CH2CH2Br

Chapter 24: Carbonyl Condensation Reactions

Chapter 25: Amines

1. Which of the following amines are classified as primary (1°) amines?

2. Which of the following amines are classified as secondary (2°) amines?

3. Which of the following amines are classified as tertiary (3°) amines?

7. What is the common name of the following compound?

8. What is the common name of the following compound?

9. What is the common name of the following compound?

10. What is the common name of the following compound?

11. What is the common name of the following compound?

12. What is the IUPAC name of the following compound?

13. What is the IUPAC name of the following compound?

14. What is the IUPAC name of the following compound?

15. What is the IUPAC name of the following compound?

16. What is the IUPAC name of the following compound?

17. What is the IUPAC name of the following compound?

18. What is the IUPAC name of the following compound?

A) I = pyrrolidine; II = pyrimidine; III = aniline.

24. What is a typical characteristic absorption in the IR spectrum of a primary amine?

29. Why is the N-H bond of an imide especially acidic?

31. Predict the product(s) of the following reaction.

A) I B) II C) III D) None of the choices

37. Why are alkylamines more basic than arylamines?