B. Organic Chemistry Brown 3e Test Bank
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Test Bank Jeffrey Elbert University of Northern Iowa
INTRODUCTION TO ORGANIC CHEMISTRY Third Edition
William Brown Beloit College
Thomas Poon Claremont McKenna, Pitzer, and Scripps Colleges
John Wiley & Sons, Inc.
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CONTENTS CHAPTER
1. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1
CHAPTER
2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
12
CHAPTER
3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
24
CHAPTER
4. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
36
CHAPTER
5. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
48
CHAPTER
6. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
61
CHAPTER
7. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
75
CHAPTER
8. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
88
CHAPTER
9. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
100
CHAPTER
10. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
116
CHAPTER
11. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
130
CHAPTER
12. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
138
CHAPTER
13. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
148
CHAPTER
14. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
161
CHAPTER
15. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
176
CHAPTER
16. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
191
CHAPTER
17. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
207
CHAPTER
18. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
221
CHAPTER
19. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
235
CHAPTER
20. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
247
CHAPTER
21. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
258
CHAPTER
22. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
271
Chapter 1 Covalent Bonding and Shapes of Molecules Multiple Choice 1. Which is the electronic configuration that describes Mg2+? (Sec. 1.2) a) 1s2, 2s2 b) 1s2, 2s2, 2p6 c) 1s2, 2s2, 2p6, 3s2 d) 1s2, 2s2, 2p6, 3s2, 3p6 2. Which is the electronic configuration that describes C? (Sec. 1.2) a) 1s2, 2s2, 2p5 b) 1s2, 2s2, 2p6, 3s2 c) 1s2, 2s2, 2p2 d) 1s2, 2s2, 2p6 3. Which ion is described by the electronic configuration 1s22s22p63s23p2? (Sec. 1.2) a) Mg+ b) Al+ c) Si+ d) P+ 4. Which atom is described by the electron configuration 1s22s22p63s23p7? (Sec. 1.2) a) S b) Se c) Cl d) Br 5. Which atom is described by the Lewis structure
A ? (Sec. 1.2)
a) C b) P c) Se d) I 6. Which atom is described by the Lewis structure
A ? (Sec. 1.2)
a) C b) P c) Se d) I 7. Which molecules contain both covalent and ionic bonds? (Sec. 1.3) CH3OH I
Na2CO3 II
NH4Cl III
NaCl IV
a) I, II b) II, IV c) I, II, IV d) II, III
1
Chapter 1 Covalent Bonding and Shapes of Molecules
8. Arrange the bonds in increasing order of ionic character (least first). (Sec. 1.3) C-C I
Na-O II
C-N III
O-H IV
C-O V
a) III, I, IV, II, V b) V, III, I, II, IV c) I, III, V, IV, II d) I, III, II, IV, V 9. Which Lewis structure is correct? (Sec. 1.3)
H
H H
a) H C OH
b) H C C H
.. ..
H
c) H O O H
.. ..
d) H
.. :O : .. O C O .. ..
10. Which Lewis structures are correct? (Sec. 1.3)
H O O H
H H
H
H N N H
H N O
I
II a) b) c) d)
H H C
H
H
III
IV
Cl
I, II II, IV III, IV I, III
11. Which molecules are polar? (Sec. 1.5)
NH3
CO2
H2O
I
II
III
a) b) c) d)
I, IV I, III II, III, IV III, IV, V
2
CH4
Br2
IV
V
H
Chapter 1 Covalent Bonding and Shapes of Molecules 12. Which molecules are polar? (Sec. 1.5)
O H2C
CH2 I
H
C
H
II
CH2Cl2
H3C CH3
CH3OH
III
IV
V
a) III, IV, V b) I, IV c) II, III, V d) I, III 13. Which functional groups have correct Lewis structures? (Sec. 1.3)
O C O H
C O
hydroxyl I
carbonyl II
C O H carboxyl III
a) I, II b) II, III c) I, II, III d) I, III 14. Which is the correct Lewis structure for acetic acid (CH3CO2H)? (Sec. 1.3)
H O
H O
H C
C O
H H
H C
H
C O
H C O C
H H
a)
O
O H H
H O C
H
b)
H c)
d)
15. Using the VSEPR model, predict which atoms have bond angles of about 120°. (Sec. 1.4)
O H3C
C
H
I
CH3OH
CH2 CH2 III
II
a) II, IV b) I, IV c) II, III d) I, III
3
C
NH4Cl IV
H
Chapter 1 Covalent Bonding and Shapes of Molecules 16. According to VSEPR model, what is your prediction for the arrangement of electron pairs for CH3-? (Sec. 1.4) a) linear b) tetrahedral c) bent d) trigonal 17. Using the VSEPR model, predict which species have bond angles of about 109°. (Sec. 1.4)
NH3
CO2
H2O
H3O
I
II
III
IV
+
O3 V
a) I, III, IV b) II, III, V c) I, IV d) III, IV, V 18. What is the correct structure for the aldehyde which has the formula C4H8O? (Sec. 1.3)
OH a) CH3
O
CH CH CH2
b) CH3
C CH2
d) H2C
CH CH2
CH3
O c) CH3
CH2
CH2
CH
O CH3
19. Nitrogen has a negative formal charge in which of the following compounds? (Sec. 1.3) a) NaNH2 b) N2 c) NH4Cl d) HCN 20. What is the formal charge of oxygen in H3O+? (Sec. 1.3) a) –1 b) 0 c) +1 d) +2 21. What is the formal charge of indicated carbon in,
NaC CH (Sec. 1.3)
a) –2 b) –1 c) 0 d) +1
4
Chapter 1 Covalent Bonding and Shapes of Molecules 22. The carbon has the correct orbital hybridization in which structures? (Sec. 1.7)
H2C
H2C O
CH2
CH4
sp2 II
sp I
HC N
O C O
sp IV
sp V
sp2 III
a) II, IV, V b) II, III, IV c) I, II, III d) I, IV, V 23. What are the correct orbital hybridizations for carbon in the following species? (Sec. 1.7)
A. CH3
I. sp
B. CH4
II. sp
C. CH 3
III. sp
2
3
a) A and I, B and III b) B and I, C and II c) A and III, C and II d) B and III, C and III 24. Which of the following are pairs of contributing resonance structures? (Sec. 1.6)
I
CH3
II III
H2C
IV
O
CH3
CH3
CH2 OH
H2C O
H2C O
CH CH2
H2C CH CH2
N C O
N C O
a) II, IV b) I, II, III c) III, IV d) II, III, ,IV
5
Chapter 1 Covalent Bonding and Shapes of Molecules 25. Carbon has how many valence electrons? (Sec. 1.2) a) 2 b) 4 c) 6 d) 8 26. Oxygen has how many valence electrons? (Sec. 1.2) a) 4 b) 5 c) 6 d) 7 27. Nitrogen has how many valence electrons? (Sec. 1.2) a) 4 b) 5 c) 6 d) 7 28. Which statement about orbitals is false? (Sec. 1.2) a) Orbitals are regions of space where electrons are found. b) Orbitals may contain up to two electrons. c) Orbitals are filled in order of decreasing energy. d) Orbitals of equivalent energy are half filled before adding two electrons to any one of them. 29. Which statement about resonance structures is false? (Sec. 1.6) a) All contributing resonance structures must have the same number of valence electrons. b) All contributing structures must obey the rules of covalent bonding. c) The position of nuclei may change. d) Third period atoms may have up to 12 electrons around them. 30. Which functional groups are named correctly? (Sec. 1.8)
O H3C
C
O
O H
alcohol I
CH3
OH
aldehyde II
H3C
C
H N CH3 CH3
ketone III
a) III, IV, V b) II, III, IV c) I, III, V d) I, III, IV
6
CH3 amine IV
H3C
C OH
carboxylic acid V
Chapter 1 Covalent Bonding and Shapes of Molecules 31. Which of the following compounds contains a tertiary (3°) alcohol? (Sec. 1.8)
H3C HC
OH
H3C
H3C
C CH3
I
OH
H3C
H3C
II
OH
H3C
C CH3 III
a) I b) II c) III d) IV
7
CH2
H3C
OH
HC
CH
H3C
CH3 IV
Chapter 1 Covalent Bonding and Shapes of Molecules Fill in the Blanks 1. The spins of the electrons must be _______ in an orbital. (Sec. 1.2) 2. Outer shell electrons are called _________ electrons. (Sec. 1.2) 3. ______ is the number of valence electrons for S. (Sec. 1.2) 4. ______ is the number of valence electrons for Br. (Sec. 1.2) 5. The tendency of an element to react such that it achieves a noble gas configuration is called the ______ ______. (Sec. 1.2) 6. The most polar bond in the following molecule is __________. (Sec. 1.3)
H OH H F C C C NH2 H H H 7. A __________ bond is characterized by the unequal sharing of electrons. (Sec. 1.3) 8. The following molecule contains the _________ and __________ functional groups. (Sec. 1.8)
O
OH 9. The following molecule contains the _________ and __________ functional groups. (Sec. 1.8)
NH2
OH O 10. Functional groups undergo the same type of __________ in whatever compound they are found. (Sec. 1.8) 11. ______________ are the basis for compound nomenclature. (Sec. 1.8) True-False 1. Each shell can hold two electrons. (Sec. 1.2) 2. Orbitals make up the majority of the mass of an atom. (Sec. 1.2) 3. The group 7A elements react by losing an electron to achieve a noble gas configuration. (Sec. 1.3) 4. The group 2A elements react by losing two electrons to achieve a noble gas configuration. (Sec. 1.3)
8
Chapter 1 Covalent Bonding and Shapes of Molecules
5. Carbon reacts by gaining 4 electrons to achieve a noble gas configuration. (Sec. 1.3) 6. An atom that gains electrons is called an anion. (Sec. 1.3) 7. Ionic bonds are characterized by the unequal sharing of electrons. (Sec. 1.3) 8. The following molecule is an example of a secondary amine. (Sec. 1.8)
H3C HC
NH2
H3C 9. 10.
CH3CH2CH2CH2CH2OH CH3ONa
is a polar molecule. (Sec. 1.5)
contains only polar covalent bonds. (Sec. 1.3)
9
Chapter 1 Covalent Bonding and Shapes of Molecules
Answers Multiple Choice 1. b 2. c 3. d 4. c 5. c 6. a 7. d 8. c 9. d 10. c 11. b 12. c 13. d 14. d 15. d 16. b 17. a 18. c 19. a 20. c 21. b 22. a 23. c 24. c 25. b 26. c 27. b 28. c 29. c 30. a 31. b Fill in the Blank 1. paired 2. valence 3. 6 4. 7 5. octet rule 6. C-F 7. polar covalent 8. ketone, alcohol 9. 1° amine, carboxylic acid 10. reactions 11. Functional groups True-False 1. F 2. F 3. F 4. T 5. F 6. T
10
Chapter 1 Covalent Bonding and Shapes of Molecules 7. F 8. F 9. T 10. F
11
Chapter 2 Acids and Bases Multiple Choice 1. Identify the Brønsted-Lowry acids in the following reactions. (Sec. 2.3)
CH3OH
+
I
C2H5OH
+
CH3OH2
II
III
NaH
V a) b) c) d)
HCl
Cl
+
IV
C2H5ONa
H2
+
VII
VI
VIII
I, III,VI, VII II, VI I, IV, V, VIII II, III, V, VIII
2. Identify the conjugate bases in the following reactions. (Sec. 2.3)
CH3NH2
+ H3CCO2H
CH3NH3
+
I C2H5OH
+
C2H5ONa
NaH
II +
+
CH3OH2
HCl
V a) b) c) d)
II, III, VI I, IV, V I, III, V II, IV, VI
12
H2 IV
III CH3OH
CH3CO2
+
Cl VI
Chapter 2 Acids and Bases 3. Identify the conjugate acids in the following reactions. (Sec. 2.3)
CH3NH2
+ CH3CO2H
CH3NH3
CH3CO2
+
I CH3OH
+
II
CH3OH2
HCl
Cl
+
IV
III C2H5OH
+
C2H5ONa
NaH
H2
+
VI
V a) b) c) d)
I, IV, VI I, III, VI II, IV, V I, III, V
4. Which are acid-base reactions according to Brønsted-Lowry theory? (Sec. 2.3)
O
O I.
C
II.
III.
IV. a) b) c) d)
C
+
H3CNH3
AlCl3
+
Cl
AlCl4
CH3NH2
+
HCl
CH3NH3Cl
CH3Li
+
H2O
CH3
O
CH3
CH4
I, III I, II, II, IV I, II, III I, III, IV
13
OH
+
CH3NH2
+
LiOH
Chapter 2 Acids and Bases 5. Which are acid-base reactions according to the Brønsted-Lowry theory? (Sec. 2.3)
I.
(CH3)3COH
+
H2SO4
(CH3)3C
+
H2O
II.
Br2
+
FeBr3
FeBr4
+
Br
III.
CH3NH2
+
BF3
CH3NH2BF3
IV.
CH3NH2
+
HCl
CH3NH3Cl
a) b) c) d)
+
I I, III, IV II, III I, IV
6. Which are acid-base reactions according to Lewis theory but not according to the Brønsted-Lowry theory? (Sec. 2.7)
O
O I.
H3C
C
CH3
+
H3C C
CH3
CH3 O
O II.
III.
IV.
H3C
C
OH
NH3
H3C
O
CH3
+
H2O
+
BF3
+
BF3
H3C
C
O
NH3BF3
H3C H3C
a) b) c) d)
CH3
I, II III, IV I, III, IV I, II, III, IV
14
O
BF3
+
H3O
HSO4
Chapter 2 Acids and Bases 7. Which acid has the highest pKa? (Sec. 2.4) a) b) c) d)
CH3COOH H2O NH4+ HCl
8. Arrange the following in order of increasing basicity (weakest to strongest). (Sec. 2.4) I. OH-
II. Cla) b) c) d)
III. H2O
IV. NH3
II, III, IV, I III, I, IV, II IV, I, II, III III, IV, I, II
9. Arrange the following ions in the order of increasing acidity (weakest to strongest). (Sec. 2.4) II. H3O+
I. H2O a) b) c) d)
III. NH4+
II, III, I I, II, III III, II, I I, III, II
10. Which ion is the strongest base? (Sec. 2.4)
O a)
CH3CH2O
b)
CH3
C
O
c) Cl
15
d) CH3CH2
Chapter 2 Acids and Bases 11. Which equilibria lie considerably toward the right? (Sec. 2.5)
O
O
C
I.
+
OH
H3C
NH3
C H3C
O II.
C H3C
NH4
+
O
O O
+
H2O
C H3C
OH
+
OH
III.
NH4
+
OH
NH3
+
H2O
IV.
HCN
+
OH
CN
+
H2O
a) b) c) d)
II, III I, III, IV III, IV I, II, III
12. Which equilibria lie considerably toward the left? (Sec. 2.5)
O
O I.
C
OH
H3C
+
CN
C H3C
O II.
C H3C
O
+
NH4
+
OH
C H3C
a) b) c) d)
C H3C
OH
NH3
O IV.
+
HCN
O
NH4
III.
O
+
NH3
+
H2O
+
CH3OH
O OH +
C
CH3
H3C
II I, IV III, IV I
16
O
Chapter 2 Acids and Bases 13. List the bonds in order of increasing acidity (least to most). (Sec. 2.6)
C
H
O H
I a) b) c) d)
F
II
H
N H
III
IV
II, III, IV, I III, I, II, IV I, IV, II, III IV, III, II, I
14. List the bonds in order of decreasing acidity (most to least). (Sec. 2.6)
F
Br
H I
a) b) c) d)
H II
Cl
H
I
H
III
IV
I, III, II, IV IV, II, III, I II, III, IV, I I, II, III, IV
15. Which substances are Lewis bases? (Sec. 2.7)
H2O
AlCl3
I
II
a) b) c) d)
CH H3C
F CH3
III
IV
I, II I, III III, IV I, IV
16. What is the stronger acid in the following reaction if the equilibrium constant is approximately 108. (Sec. 2.5)
HC
+ NH2
CH a)
b)
HC
C
+
c)
NH3 d)
17. What is the stronger acid in the following reaction if the equilibrium constant is much less than 0.01? (Sec. 2.5)
HNO3 a)
+
H2SO4 b)
H2NO3 + c)
HSO4 d)
17
Chapter 2 Acids and Bases 18. Which is the stronger base if the equilibrium lies considerably to the right? (Sec. 2.5)
O
O C H3C
OH
CN
+
C H3C
a)
b)
+
O
c)
HCN d)
19. What is the role of diethyl ether in the following reaction? (Sec. 2.7)
CH3CH2OCH2CH3 a) b) c) d)
+
BF3
(CH3CH2)2O BF3
Lewis acid Lewis base Brønsted acid Brønsted base
20. What is the role of water in the following reaction? (Sec. 2.3)
NH3 a) b) c) d)
+
H3O
H2O
+
NH4
acid base conjugate acid conjugate base
21. What is the role of methanol in the following reaction? (Sec. 2.7)
CH3
CH3 H3C
C
+ CH3OH
H3C
CH3
CH3 a) b) c) d)
C O
CH3 H
Lewis acid Lewis base Brønsted acid Brønsted base
22. Which statements about acid-base equilibria are true? (Sec. 2.4) I. The pKa is the negative log10 of the acid equilibrium constant. II. A stronger acid has a pKa with a smaller value than a weaker acid. III. A stronger base has a conjugate acid which has a pKa with a smaller value than a weaker base. IV. The Ka = K [HA]. a) b) c) d)
I, III I, II I, II, III II, III, IV
18
Chapter 2 Acids and Bases 23. Which is the order of decreasing acid strength of the following compounds (greatest first)? (Sec. 2.6)
O Cl C H2
C
O OH
Br C H2
C
O F OH
C H2
II
I a) b) c) d)
C
O H
OH
C H2
III
C
OH
IV
II, I, III, IV III, IV, I, II III, I, II, IV IV, II, I, III
24. Which is the order of increasing acid strength of the following compounds (least first)? (Sec. 2.6)
O
O
F OH
O OH
OH
F I a) b) c) d)
O
F
OH
F II
III
I, III, II, IV IV, III, II, I II, I, III, IV IV, III, I, II
19
IV
Chapter 2 Acids and Bases 25. Which is the proper reaction mechanism for the reaction of borontrifluoride and diethyl ether? (Sec. 2.7)
a) :BF3
CH3CH2
b) BF3
CH3CH2
c) :BF3
d)
CH3CH2
BF3
CH3CH2
O
+ BF CH2CH3
CH3CH2
.. O .. CH CH 2 3
O
- BF
CH3CH2
.. O .. CH CH 2 3
3
O + CH2CH3
CH3CH2
CH2CH3
3
O - CH2CH3
BF3 O + CH2CH3
+ BF 3 CH3CH2
O - CH2CH3
Fill in the Blank 1. The weaker the acid, the ________________ the conjugate base. (Sec. 2.5) 2. The higher concentration (reactants or products) at equilibrium will lie on the side of the ___________ acid. (Sec. 2.5) 3. Complete the following reaction. (Sec. 2.3)
O CH3COH
O +
H2O
CH3CO-
+
4. Complete the following reaction. (Sec. 2.3)
O NH4Cl + CH3CONa
NH3 +
5. Complete the following reaction. (Sec. 2.3)
+
H2O
NH3 + H3O+ + Cl-
20
Chapter 2 Acids and Bases
6. Complete the following reaction. (Sec. 2.3)
O
O CH3CONa + NaHCO3
CH3COH +
7. Complete the following reaction scheme with the appropriate equilibrium arrow (indicating the higher concentrations at equilibrium). (Sec. 2.5)
O
O
CH3CONa + HCN
CH3COH + NaCN
8. Complete the following reaction scheme with the appropriate equilibrium arrow (indicating the higher concentrations at equilibrium). (Sec. 2.5)
NaH2PO4 + NaHCO3
Na2PO4 + H2CO3
9. Identify the acid, base, conjugate acid, conjugate base in the following reaction. (Sec. 2.3)
NaCN + NaHSO4
HCN +
Na2SO4
10. Identify the acid, base, conjugate acid, conjugate base in the following reaction. (Sec. 2.3)
NH4Cl + NaHCO3
NH3
+ H2CO3 + NaCl
True-False 1. Brønsted-Lowry acids accept protons when reacting. (Sec. 2.3) 2. Lewis bases donate electrons when reacting. (Sec. 2.7) 3. The stronger acid has the larger (more positive) pKa. (Sec. 2.4) 4. Strong acids have weak conjugate bases. (Sec. 2.4) 5. The equilibrium will lie to the right in the following reaction. (Sec. 2.5)
NH4Cl +
H2O
NH3
+ H3O+
+
6. The equilibrium will lie to the right in the following reaction. (Sec. 2.5)
HCN +
NaH2PO4
H3PO4 + NaCN
21
Cl-
Chapter 2 Acids and Bases
7. Water acts as a base in the following reaction. (Sec. 2.3)
NH3 + H2O
NH4OH
8. Ammonia acts as a Brønsted-Lowry base in the following reaction. (Sec. 2.3)
NH4Cl
+ NaHCO3
NH3 + H2CO3
+
NaCl
9. The strongest acid in the following list is sodium bicarbonate. (Sec. 2.4)
NH4Cl
NaHCO3
H2O
CH3CH2OH
10. The weakest acid in the following list is acetic acid. (Sec. 2.6)
O CH3COH
O ClCH2COH
O
O
FCH2COH
FCH2CH2COH
22
Chapter 2 Acids and Bases Answers Multiple Choice 1. d 2. a 3. b 4. d 5. d 6. b 7. d 8. a 9. d 10. d 11. b 12. a 13. c 14. b 15. d 16. a 17. c 18. b 19. b 20. d 21. b 22. b 23. c 24. b 25. b Fill in the Blank 1. stronger 2. weaker 3. H3O+ 4. CH3COOH + NaCl 5. NH4Cl 6. Na2CO3 7. equilibrium arrow pointed to the left 8. equilibrium arrow pointed to the left 9. base, acid, c.acid, c. base 10. acid, base, c. base, c. acid True-False 1. F 2. T 3. F 4. T 5. F 6. F 7. F 8. T 9. F 10. T
23
Chapter 3 Alkanes and Cycloalkanes
Multiple Choice 1. Which of the following are constitutional isomers of 4-isopropyloctane'? (Sec. 3.3) I. II. Ill. IV.
a) b) c) d)
3-ethyl-2,4,5-trimethyloctane isobutylcyclohexane 4-ethyl-2,2-dimethylheptane 4-ethyl-2-methyloctane
I, IV II, III I, II III, IV
2. Which of the following are constitutional isomers of trans-1,2-dimethylcyclopentane'? (Sec. 3.3)
II
a) b) c) d)
Ill
IV
I, Ill, IV II, IV, V ll,Ill,V III, IV, V
3. Which of the following properties are not identical for constitutional isomers? (Sec. 3.9) I. II. Ill. IV.
a) b) c) d)
molecular formula molecular weight order of attachment of atoms physical properties
I, IV II, III I, II Ill, IV
4. Which of the following molecules are constitutional isomers? (Sec. 3.3)
0
b)
CH3CH20CH3
and
II CH3CH2CH
and
0 II CH3CCH3
and
0 II CH3CCH3
0
c)
II CH3CH2CH
0
d)
CH3CH20H
and
II CH3CH
24
v
Chapter 3 Alkanes and Cycloalkanes
5. Which of the following belong in the group of constitutional isomers for C 1 H 6 0 2? (Sec. 3.3)
a) b) c) d)
II, III II, IV, V I, II, V I
6. Which pairs of molecules are constitutional isomers? (Sec. 3.3)
D
C>-
Ill~ a) b) c) d)
IV
I, IV I, II II, III III, IV
7. Which is the IUPAC name for the following compound? (Sec. 3.4)
H3C
"CH-CH
CH3
/
H2C / I
CH3 a) b) c) d)
"CH2 I CH3
2-ethyl-3-methylpentane 3,4-dimethylhcxane 2,3-diethylbutane 3-methyl-4-ethylpentane
25
6
Chapter 3 Alkanes and Cycloalkanes
8. Which is the IUPAC name for the following cycloalkane'? (Sec. 3.4)
a) b) c) d)
2,4-dimethyl-1-ethylcyclopentane I ,3-dimethyl-5-ethylcyclopentane 1-ethyl-2,4-dimethylcyclopentane 1-ethyl-3,5-dimethylcyclopentane
9. Which is the IUPAC name for the following compound? (Sec. 3.4)
a) b) c) d)
cis-1-ethyl-2-methylcyclohexane trans-1-ethyl-2-methylcyclohexane cis-1-methyl-2-ethylcyclohexane trans-1-methyl-2-ethylcyclohexane
10. Which is the structure for trans-1-ethyl-3-isopropylcyclohexane? (Sec. 3.4 and 3.8)
a)
b)
c)
d)
H
11. How many primary carbons are there in the following molecule? (Sec. 3.4)
a) 1
b) 2 c) 4 d) 6
26
Chapter 3 Alkanes and Cycloalkanes
12. How many secondary hydrogens are there in the following molecule? (Sec. 3.4)
a) 1
b) 2 c) 4 d) 9
13. Which structural formulas represent cis forms of 1,2-dimethylcyclohexane? (Sec. 3.8)
H
H
I.
IV.
III.
II.
a) I, IV b) II, III c) III, IV d) I, II
14. Which cycloalkanes show cis-trans isomerization? (Sec. 3.8)
I.
II.
III.
IV.
V.
a) I, V b) l,ll,V c) ll,III,V d) II, Ill, IV
15. In the most stable conformation of trans- I ,4-dimethylcyclohexane, what positions do the methyl groups occupy? (Sec. 3.7) a) b) c) d)
axiaL axial equatorial, axial equatoriaL equatorial axial, equatorial
27
Chapter 3 Alkanes and Cycloalkanes
16. Which of these diaxial forms has the highest energy? (Sec. 3.7)
a)
b)
d)
c)
17. Which compound has the lowest boiling point? (Sec. 3.9)
CH3
H3C, H3C
/
0
I
H3C-C-CH3
CHCH 2CH3
I
CH3 b)
a)
c)
d)
18. Which compound has the highest boiling point? (Sec. 3.9)
CH2CH3
0
I
H3C-C-CH3 I
CH2CH3 a)
b)
c)
d)
19. Which is a conformer of pentane'? (Sec. 3.7)
H~H
CH3
H~CH 3 H CH3H
H3C H CH3
a)
b)
H~H
H~H
H
H H CHzCH3
H CHzCH3 d)
c)
20. Which conformation of 2-methylbutane is the most stable? (Sec. 3.7)
Hfi~CH, a)
H~H H
CH3 CH 3
CH3
CH3
H3C~CH, H
b) 28
H
H~CH3 CH3
H
H
H
c)
d)
Chapter 3 Alkanes and Cycloalkanes
21. Which conformer of pentane is the least stable? (Sec. 3.7)
3 J)CH
¥(
3
tfl
CH2CH3
H~CH1
CHzCH3
H
M~H
H~H
b)
c)
d)
H
a)
9fzCH3
H
H
H CH3
22. Which fi·action of petroleum distills at the highest temperature? (Sec. 3.11) a) b) c) d)
gasoline gases fuel oil kerosene
23. What is the term for the process of forming ethene (an unsaturated hydrocarbon) from ethane (a saturated hydrocarbon)'! (Sec. 3.11) a) b) c) d)
combustion fractional distillation thermal cracking catalytic reformation
24. Which molecule has the most negative heat of combustion in kcal/mole? (Sec. 3.1 0) a) b) c) d)
methane ethane propane butane
25. Which are the stoichiometric coefficients that complete the following equation? (Sec. 3.10)
a) x = 9 Y,, y = 6, z = 7 b) x=18,y=12,z=14 c) x=1,y=l,z=2 d) X = 6 , y = 6, Z = 4
29
Chapter 3 Alkanes and Cycloalkanes
Fill in the Blank
1. Complete the following reaction by writing the stoichiometric coefficients. (Sec. 3.1 0)
CH3CH2CH2CH3 +
D 02
D
C02
+
D
H20
2. Complete the following reaction by writing the stoichiometric coefficients. (Sec. 3.1 0)
CH3CH3
+
D 02
D
C02
+
D
H20
3. Write the name for the following molecule. (Sec. 3.4)
4. Write the name for the following molecule. (Sec. 3.4)
H
5. Complete the structure by drawing in the cis-1,3-dimethyl groups. (Sec. 3.8)
6. Complete the structure by drawing in the trans-! ,4-dimethyl groups. (Sec. 3.8)
7. What is the configuration of the indicated carbon? (Sec. 3.4)
30
Chapter 3 Alkanes and Cycloalkanes
8. What is the configuration of the indicated carbon? (Sec. 3.4)
j 9. Draw a constitutional isomer ofpropanone. (Sec. 3.3)
10. Complete the Newman projection for the least stable conformation of2-methylbutane. Use the appropriate Newman projection template. (Sec. 3.7)
* *
II. Complete the Newman projection for the most stable conformation of2-methylbutane. Use the appropriate Newman projection template. (Sec. 3.7)
31
Chapter 3 Alkanes and Cycloalkanes
True-False 1. The following structures represent the same molecule. (Sec. 3.3)
cc
~~~a· 11,,
and
2. The following structures represent the same molecule. (Sec. 3.3)
CC
and
3. The indicated carbon is a secondary (2°) carbon. (Sec. 3.4)
4. The molecule shown has 12 primary ( 1°) hydrogens. (Sec. 3.4)
5. Propanal is a primary (1 °) alcohol. (Sec. 3.6) 6. Propanal and propanol are constitutional isomers. (Sec. 3.3) 7. Pentane and cyclopentane are constitutional isomers. (Sec. 3.3) 8. Alkanes all have lower densities than water. (Sec. 3.9)
9. The Newman projection below shows 2,3-dimethylbutane in the most stable conformation. (Sec. 3.7)
32
Chapter 3 Alkanes and Cycloalkanes
10. The Newman projection below shows n-pentane in a gauche conformation. (Sec. 3.7)
33
Chapter 3 Alkanes and Cycloalkanes
Answers Multiple Choice I. d 2. d 3. d 4. c 5. d 6. a
7. b 8. c 9. b lO.a 11. c 12. c 13. a 14.d 15.c 16.c 17.c 18. a 19.d 20. b 21. a 22.c 23.c 24.d 25.a Fill in the Blank I. 6 '/:,, 4, 5 2. 3 '/:,, 2, 3 3. 3,5-diethylheptane 4. 1-ethyl-2,4-dimethylcyclohexane 5.
CH
MH
H
etc.
6.
HCr+cH H
3
3
H etc. 7. quaternary (4°) 8. secondary (2°)
34
Chapter 3 Alkanes and Cycloalkanes
, enol is also a possibility
True-False l.T 2. T 3. F 4. T 5. F 6. F 7. r
8. T 9. F 10. F
35
Chapter 4 Alkenes and Alkynes Multiple Choice 1. Which are the approximate carbon-carbon bond angles at positions I and II in the following compound? (Sec. 4.2)
CH3
I II a) b) c) d)
109°, 109° 120°, 180° 120°, 109° 109°, 120°
2. Which is the best description for the indicated bond in the following compound? (Sec. 4.2)
CH3 a) b) c) d)
sp3-sp3 sp3-sp3 and 2p-2p sp2-sp2 and 2p-2p sp-sp and sp-sp
3. Which is the IUPAC name for the following structure? (Sec. 4.3)
CH3 H3C
C
CH CH2
CH2 CH3 a) b) c) d)
3,3-dimethyl-4-pentene 3-methyl-3-ethyl-1-butene isopropylpentene 3,3-dimethyl-1-pentene
4. Which is the correct structure for vinylcyclobutane? (Sec. 4.3)
CH2 a)
b)
CH2 c)
CH CH2 d)
36
Chapter 4 Alkenes and Alkynes 5. Which is the correct name for the following compound? (Sec. 4.3)
CH3 H3C
C
C CH2
H a) b) c) d)
H C
C
CH3
H
2E, 5E-5-methyl-2,5-heptadiene 2E, 5E-3-methyl-2,5-heptadiene 2Z, 5E-3-methyl-2,5-heptadiene 2E, 5Z-5-methyl-2,5-heptadiene
6. Which is the correct name for the following compound? (Sec. 4.3)
CH3
CH3 a) b) c) d)
1,3-dimethylcyclohexene 2,4-dimethylcyclohexene 3,5-dimethylcyclohexene 2,4-dimethyl-1-cyclohexene
7. Which is the correct name for the following compound? (Sec. 4.3)
H3C
CH3 C
H a) b) c) d)
C CH2CH3
E-2-ethyl-2-butene Z-3-methyl-3-pentene E-3-methyl-2-pentene Z-3-ethyl-2-butene
8. Which is the IUPAC name for the following compound? (Sec. 4.3)
H3C C C CH3 a) b) c) d)
dimethyl acetylene 3-butyne 3-butene 2-butyne
37
Chapter 4 Alkenes and Alkynes
9. Which is the IUPAC name for the following compound? (Sec. 4.3)
H3C H3C CH2CH3 a) b) c) d)
1,1-dimethyl-4-ethyl-2,5-cyclohexadiene 1-ethyl-4,4-dimethyl-2,5-cyclohexadiene 3-ethyl-6,6-dimethyl-1,4-cyclohexadiene 6-ethyl-3,3-dimethyl-1,4-cyclohexadiene
10. Which of the following alkenes do not show cis-trans isomerization? (Sec. 4.3) I) 2-methyl-2-hexene II) 1-chloro-1-butene III) 1-methylcyclohexene IV) 2-methyl-3-hexene a) b) c) d)
I, II III, IV II, III, IV I, III
11. Which of the following alkenes show cis-trans isomerization? (Sec. 4.3) I) 1-chloropropene II) 3-methylcyclohexene III) 2,6-dimethyl-2,5-octadiene IV) 3-ethyl-3-methyl-1-pentene a) b) c) d)
I, II II, III III, IV I, III
12. How many trans isomers are there for an alkene with the formula, C4H7Cl? (Sec. 4.3) a) b) c) d)
2 3 6 8
13. How many cycloalkanes of molecular formula C5H10 show cis-trans isomerism? (Sec. 4.3) a) b) c) d)
1 2 3 4
38
Chapter 4 Alkenes and Alkynes
14. How many cycloalkanes of molecular formula C6H12 do not show cis-trans isomerization? (Sec. 4.3) a) b) c) d)
2 3 4 5
15. Arrange the following groups in the order of increasing priority (lowest first). (Sec. 4.3)
CH2CH3
CH2NH2
I a) b) c) d)
CH2Br
II
CH2OH
III
IV
I, II, IV, III III, IV, II, I I, IV, II, III IV, II, III, I
16. Arrange the following groups in the order of increasing priority (lowest first). (Sec. 4.3)
CH CH2
C CH II
I a) b) c) d)
C N
C O CH3 IV
III
IV, III, II, I I, II, III, IV III, IV, I, II III, I, IV, II
17. Arrange the following groups in the order of increasing priority (lowest first). (Sec. 4.3)
O
O
O
O
C OCH3
C OH
C CH3
C NH2
I
II
III
IV
a) b) c) d)
II, I, IV, III II, III, I, IV I, II, IV, III III, IV, II, I
39
Chapter 4 Alkenes and Alkynes
18. Which structure is Z-2-bromo-3-methyl-2-pentene? (Sec. 4.3)
CH3 H3C
CH2CH3 C
H
C
Br
C CH3
CH CH2CH3
C
H
CH3 C
Br
a)
H3C C
Br
C CH2CH3
b)
Br
H3C C
H3C
CH2CH3
c)
d)
19. Which alkenes have E configurations? (Sec. 4.3)
O
O
HO C
Cl Cl
C OH C
C
H
C H
H2C
C
H
I a) b) c) d)
CH2Cl
F C
CH3
H3C
II
C Cl
III
Cl
Br C H3C
C I
IV
I, II II, III III, IV II, IV
20. How many cis-trans isomers are possible for geraniol? (Sec. 4.3 and 4.5)
CH3 H2C H2C
C CH
C H
CH2OH
C H3C a) b) c) d)
CH3
2 3 4 6
21. How many distinct terpene structure types can be made from the assembly of 2-isoprene units? (Sec. 4.5) a) b) c) d)
1 2 3 4
40
Chapter 4 Alkenes and Alkynes
22. How many isoprene units are there in vitamin A? (Sec. 4.5)
CH2OH
a) b) c) d)
2 3 4 8
23. Cleavage of which of the indicated bonds in limonene leads to a head to tail terpene? (Sec. 4.5)
c) d)
b) a)
24. Arrange the following compounds in decreasing order of boiling point (highest first). (Sec. 4.4)
H3C
C
C CH2CH2CH3 I
a) b) c) d)
CH3 H3C C C CH CH3 II
CH3 H3C
C
C CH3
III
HC
C C IV
I, II, IV, III II, IV, III, I III, IV, II, I IV, II, III, I
25. Arrange the following molecules in order of increasing boiling point (lowest first). (Sec. 4.4)
I a) b) c) d)
II
III
I, II, IV, III IV, II, III, I III, IV, II, I I, II, III, IV
41
IV
CH3
CH3
Chapter 4 Alkenes and Alkynes Fill in the Blank 1. The IUPAC name of the following molecule is ____________________________________________________. (Sec. 4.3)
2. The IUPAC name of the following molecule is ____________________________________________________. (Sec. 4.3)
3. The structure of (3E, 6Z) 2,9-dimethyl-3,6-decadiene is
(Sec. 4.3) 4. The structure of 3,7-diethyl-4,8-dimethyl-1,5-cyclooctadiene is
(Sec. 4.3) 5. The IUPAC name of the following molecule is ____________________________________________________. (Sec. 4.3)
42
Chapter 4 Alkenes and Alkynes 6. The structure of 2-cyclobutyl-6,6-dimethyl-4-octyne is
(Sec. 4.3) 7. The approximate bond angles of the indicated carbons are 1) ______, 2) _______, 3) _______, 4) ______. (Sec. 4.2)
1
2
3 4
8. The number of isoprene units in menthol is ___________. (Sec. 4.5)
OH
9. The number of isoprene units in grandisol is ____________. (Sec. 4.5)
OH
H 10. The priority order of the groups –CH2CH3, -CH3, -OCH3, -CH=CH2 is;
>
>
> (Sec. 4.3)
43
Chapter 4 Alkenes and Alkynes True-False 1. The structure of 4-isopropyl-1-methylcyclohexene is
(Sec. 4.3) 2. The name of the following structure is (3E, 5E) 2-ethyl-3,5-octadiene. (Sec. 4.3)
3. The following compounds are listed in order of increasing boiling point (lowest first). (Sec. 4.4)
<
<
<
4. The following groups are listed in order of decreasing priority (highest first). (Sec. 4.3)
CH3 C CH >
CH
>
CH3
C CH2 > H
CH3
5. The following groups are listed in order of increasing priority (lowest first). (Sec. 4.3)
O
O H
<
Cl
<
OCH2CH3
<
Cl
6. The following structures represent identical compounds. (Sec. 4.3)
7. The following structures represent isomers. (Sec. 4.3)
8. 2,2-Dimethylcyclohexene occurs as E and Z isomers. (Sec. 4.3)
44
Chapter 4 Alkenes and Alkynes 9. 2,3-dimethyl-3-hexene occurs as E and Z isomers. (Sec. 4.3) 10. There are 4 possible E,Z isomers of 1,3-pentadiene. (Sec. 4.3)
45
Chapter 4 Alkenes and Alkynes Answers Multiple Choice 1. c 2. c 3. d 4. d 5. b 6. c 7. c 8. d 9. d 10. d 11. d 12. b, two alkenes and a cycloalkane 13. a 14. d 15. a 16. b 17. d 18. c 19. c 20. a 21. c 22. c 23. a 24. a 25. c Fill in the Blank 1. (Z) 7-methyl-3-nonene 2. 6,6-dimethyl-1,4-cycloheptadiene 3.
4.
5. 2,8,9-trimethyl-3-decyne
46
Chapter 4 Alkenes and Alkynes 6.
7. 1) 120, 2) 109, 3) 120, 4) 180 8. 2 9. 2 10.
OCH3
>
C CH2 > H
CH2CH3 >
True-False 1. F 2. F 3. F 4. F 5. T 6. T 7. F 8. F 9. T 10. F
47
CH3
Chapter 5 Reactions of Alkenes Multiple Choice 1. The reaction of propene with which of the following reagents are oxidation reactions? (Sec. 5.3 - 5.5) HBr/CH2Cl2 I a) b) c) d)
OsO4 II
H2/Pt III
H+/H2O V
Br2 IV
II III I and V II and IV
2. Which point on the potential energy diagram represents the intermediate? (Sec. 5.2)
B C
E
D A
reaction coordinate 3. Which diagram represents the slowest reaction? (Sec. 5.2)
E
E
reaction coordinate A
reaction coordinate B
E
E
reaction coordinate C
reaction coordinate D
48
Chapter 5 Reactions of Alkenes
4. Which compound has the highest heat (most negative) of hydrogenation? (Sec. 5.5)
A
C
B
D
5. Which statement does not describe a transition state? (Sec. 5.2) a) b) c) d)
Possesses a definite geometry Maximum on the potential energy diagram Structure can be determined experimentally Can not be isolated
6. Using Markovnikov’s rule, predict the position of the Cl atom in the major product from the reaction of 1methylcyclohexene with HCl. (Sec. 5.3)
A
C
B
D
7. Which species are electrophiles? (Sec. 5.3)
I a) b) c) d)
OH
NH3
H
II
III
IV
II, III II, IV I, IV I, III
8. Arrange these carbocations in order of increasing stability (least to most). (Sec. 5.3)
H3C I a) b) c) d)
II
III
I, II, III, IV III, I, II, IV II, IV, I, III I, III, IV, II
49
IV
Chapter 5 Reactions of Alkenes 9. Arrange these carbocations in order of increasing stability (least to most). (Sec. 5.3)
II
I a) b) c) d)
III
I, II, III I, III, II II, I, III III, II, I
10. Which reagents react with an alkene by syn addition? (Sec. 5.3 - 5.5) I. Cl2 a) b) c) d)
II. Br2
III. H2/Pt
IV. OsO4/ROOH
I, II III, IV II, III I, IV
11. Which reagents react with an alkene by anti addition? (Sec. 5.3 - 5.5) I. Cl2 II. Br2 III. H2/Pt IV. OsO4/ROOH a) b) c) d)
I, II III, IV II, III I, IV
12. Which reagents react with an alkene in a Markovnikov orientation? (Sec. 5.3) I. HBr II. H2O/H2SO4 III. Br2 IV. OsO4/ROOH a) b) c) d)
I, II III, IV II, IV II, III, IV
13. Which is the major product from the reaction of propene with OsO4/ROOH? (Sec. 5.4) a) b) c) d)
1-propanol 2-propanol 1,2-propanediol 1,3-propandiol
14. Which reagents react with an alkene by an electrophilic mechanism? (Sec. 5.3) I. H2O/H2SO4 a) b) c) d)
II. Br2/CCl4
III. HBr
I, II, III I, II, IV II, IV III, IV
50
IV. H2/Pt
Chapter 5 Reactions of Alkenes
15. Which is the product of the reaction of 1-methylcyclohexene with H2O/H2SO4? (Sec. 5.3)
CH3
CH3 OH OH
H
OH
H
CH3
H
H
OH
OH
a)
c)
b)
d)
16. Which is the major product from acid catalyzed hydration of 2-methyl-2-pentene? (Sec. 5.3) a) b) c) d)
2-methyl-3-pentanol 2-methyl-2-pentanol 4-methyl-2-pentanol 3-methyl-3-pentanol
17. Which is the intermediate formed in the reaction of propene with HBr? (Sec. 5.3)
Br Br a)
c)
b)
d)
18. Which is the major product from the reaction of cyclopentene with Br2/CCl4? (Sec. 5.3)
Br
H
H
Br a)
Br H
H
H
Br
Br
b)
c)
Br Br d)
19. Compound A has a molecular formula C8H14 and reacts with H2/Pt to give compound B, C8H16. Which is compound A? (Sec. 5.5)
a)
b)
c)
51
d)
CH3
Chapter 5 Reactions of Alkenes 20. Which is the major product from the reaction of 1,2-dimethylcyclohexene with D2/Pt? (Sec. 5.5) CH3
D
D
CH3 D
CH3 CH3
D CH3
CH3
b)
CH3
d)
c)
21. Which alkene has the highest rate of reaction with HBr? (Sec. 5.3)
a)
c)
b)
d)
22. Which potential energy diagram represents the reaction of HBr with 2-butene? (Sec. 5.2)
E
E
reaction coordinate A
reaction coordinate B
E
E
reaction coordinate C
reaction coordinate D
23. Which compound does not give two isomers when reacted with Cl2/CCl4? (Sec. 5.3)
a)
b)
D
D
D
a)
D
c) 52
d)
CH3
Chapter 5 Reactions of Alkenes
24. Which compound has the lowest (least negative) heat of hydrogenation? (Sec. 5.5)
b)
a)
c)
d)
25. Which point on the potential energy diagram represents the activation energy? (Sec. 5.2)
B C
E
D A
reaction coordinate
53
Chapter 5 Reactions of Alkenes Fill in the Blank 1. The stereoselective reagents from the following list are _________________________________. (Sec. 5.3-5.5) H+/H2O
HCl
Br2
OsO4
H2
2. Complete the following reaction by providing the major product. (Sec. 5.4)
OsO4 CH3COOH 3. Complete the following reaction by providing the major product. (Sec. 5.3)
HBr CH2Cl2 4. Complete the following reaction by providing the major product. (Sec. 5.5)
H2 Pt
5. Complete the following reaction by providing the necessary reagents. (Sec. 5.3)
Br Br 6. Complete the following reaction by providing the necessary reagents. (Sec. 5.3)
OH
54
Chapter 5 Reactions of Alkenes
7. Complete the following reaction by providing the starting material and reagents. (Sec. 5.3)
Cl Cl
8. Complete the following reaction by providing the starting materials. (Sec. 5.5)
H2
or
Pt
9. Draw the intermediate of the following reaction. (Sec. 5.3)
+ HCl
10. Draw the intermediate of the following reaction. (Sec. 5.3)
+ Br2
11. Draw the reaction arrows (curved arrows) for the following reaction. (Sec. 5.3)
H
Cl +
H Cl
C
55
+
Cl
Chapter 5 Reactions of Alkenes
True-False
E C
B
D A
E
reaction coordinate 1. The reaction represented by the above reaction energy diagram is endothermic. (Sec. 5.2) 2. The rate determining step of the reaction represented by the above reaction energy diagram is the first step. (Sec. 5.2) 3. The activation energies of the reaction represented by the above reaction energy diagram are noted as A and B. (Sec. 5.2) 4. The following carbocations are listed in increasing order of stability (least first). (Sec. 5.3)
H +
H
CH3
C
< HC 3
C
+
C
+
CH3
<
H
5. The following alkenes are listed in decreasing order of heat of hydrogenation (highest first). (Sec. 5.5)
>
>
>
6. The product of the reaction of cyclohexene and bromine is cis-1,2-dibromocycloheane. (Sec. 5.3) 7. The major product of the reaction of catalytic hydrogenation of 1,2-dimethylcyclohexene is cis-1,2dimethylcyclohexane. (Sec. 5.5)
56
Chapter 5 Reactions of Alkenes
8. Bromination, catalytic hydrogenation, and hydroxylation via osmium tetroxide are cis stereoselective reactions. (Sec. 5.3-5.5) 9. Hydrohalogenation, hydration, and bromination reactions proceed through an open carbocation intermediate. (Sec. 5.3) 10. The reaction arrows (curved arrows) are accurately drawn for the following reaction. (Sec. 5.3)
H
H
Br
H Br
+
Br-
57
Chapter 5 Reactions of Alkenes Answers Multiple Choice 1. d 2. c 3. a 4. b 5. c 6. c 7. c 8. b 9. d 10. b 11. a 12. a 13. c 14. a 15. b 16. b 17. d 18. a 19. a 20. b 21. d 22. c 23. a 24. d 25. d Fill in the Blank 1. Br2, OsO4, H2 2.
OH OH 3.
Br
4.
H
H
58
Chapter 5 Reactions of Alkenes 5.
Br2 CH2Cl2 6.
H+ H2O 7.
Cl2 CH2Cl2 8.
or 9.
+ 10.
Br
+
11.
H
Cl +
H Cl
C
59
+
Cl
Chapter 5 Reactions of Alkenes True-False 1. F 2. F 3. T 4. F 5. F 6. F 7. T 8. F 9. F 10. F
60
Chapter 6 Chirality Multiple Choice 1. Which compounds contain stereocenters? (Sec. 6.3) I) 1-chloropentane II) 2-chloropentane III) 3-chloropentane IV) 1,2-dichloropentane a) b) c) d)
I, II III, IV I, III II, IV
2. Which compounds contain stereocenters? (Sec. 6.3) I) 2-methylpentane II) chlorocyclohexane III) 3-methyl-2-butanol IV) 2-hydroxypropanoic acid a) b) c) d)
I, II III, IV I, III II, IV
3. Which compounds contain stereocenters? (Sec. 6.3)
OH OH I.
HO
OH O
III.
CH3CCH2CH3
CH CH2
II.
IV.
H3C H3C
a) b) c) d)
I, II III, IV I, III II, IV
61
OH CHCHCH3
Chapter 6 Chirality
4. Which compounds have multiple stereocenters? (Sec. 6.3, 6.5)
HO CH3 I. CH3CHCHCH3
HO OH O II. CH3CHCH COH O
Cl OH III. CH3CHCHCH3
CH2COH
IV.
HO C
COH
CH2O COH O a) b) c) d)
I, II III, IV II, III I, III
5. How many stereoisomers are possible for 1,2-dichlorocyclopentane? (Sec. 6.3) a) b) c) d)
1 2 3 4
6. How many stereoisomers are possible for 2,3-butanediol? (Sec. 6.3) a) b) c) d)
1 2 3 4
7. How many stereoisomers are possible for the following structure? (Sec. 6.2-6.3)
OH
O
CH3CHCHCOH NH2 a) b) c) d)
1 2 3 4
62
Chapter 6 Chirality
8. Which structures are chiral? (Sec. 6.3)
H Cl
H C
Cl H2C
C
H
H2C C
C
CH2CH2CH3
CH2CH2CH3
I.
II.
CHCH2CH3 Cl III. H
H H2C
H2C C
C CH2CHCH3 IV.
a) b) c) d)
CH2CH2CH2
Cl
V.
I, II, V I, II II, II, IV III, IV
9. Which pair of structures are enantiomers? (Sec. 6.3)
CH3 H HOC
I.
OH
H O HO H3C
O Cl Br
II.
Br
H3C CH3 CH2CH3 H3CH2C
a) b) c) d)
I
OH
Cl
CH3
H III.
COH
CH3
I
H
OH
I, II II, III I, III I, II, III
63
Cl
Chapter 6 Chirality
10. What is the relationship between these two structures? (Sec. 6.3, 6.5)
NH2 H
CH3
H3C
NH2
H
NH2
H2N
CH3
CH3 a) b) c) d)
H
H
Identical structures Enantiomers Diastereomers Constitutional isomers
11. What is the relationship between these two structures? (Sec. 6.3, 6.5)
a) b) c) d)
H
H
H
Cl
Br
Cl
Br
H
identical structures enantiomers diastereomers constitutional isomers
64
Chapter 6 Chirality
12. Which are meso compounds? (Sec. 6.5) O CH2OCH3
CH
H
OH
H
OH
H
OH
H
OH
CH2OH
CH O
I.
II. CH2OH
a) b) c) d)
CH2OH
H
OCH3
H3CO
H
OCH3
H
CH2OH
III.
IV.
13. How many stereoisomers are possible for Prilosec? (Sec. 6.7)
H N
N
CH3 O a) b) c) d)
OCH3
CH2OH
I, II I, III II, III III, IV
O
H
.HCl
CH3
OH
4 8 16 32
65
Chapter 6 Chirality
14. How many pairs of enantiomers are possible for cortisone acetate? (Sec. 6.7)
OH O
CH3
O
O
CH3
O
O a) b) c) d)
32 64 128 256
15. Which forms of lactic acid are R forms? (Sec. 6.4)
O
O COH HO H3C
H
CH3 H HOC
CH3
COH HO
OH
H CH3 HO
H
O I.
a) b) c) d)
II.
III.
COH O
IV.
I, II III, IV I, III II, IV
16. What is the R,S configuration for the following structure of isocitric acid? (Sec. 6.4)
O
O HOCCH2 HO
COH H C #1 C H
a) b) c) d)
COH O
2-R, 3-R 2-R, 3-S 2-S, 3-R 2-S, 3-S
66
Chapter 6 Chirality 17. The specific rotation of dextrorotatory tartaric acid is +12.7 degrees. A mixture of dextrorotatory and levorotatory tartaric acid has a specific rotation of +6.35 degrees. What is the optical purity of the mixture? (Sec. 6.9) a) b) c) d)
25% 33 1/3% 50% 75%
18. Rank the following substituents in order of increasing priority. (Sec. 6.4)
OH
Cl
I. a) b) c) d)
CH3
II.
H
III.
IV.
I, III, II, IV II, I, III, IV III, I, II, IV IV, III, I, II
19. Rank the following substituents in order of increasing priority. (Sec. 6.4)
H C
C
H I. a) b) c) d)
OH
OCH3
II.
III.
H
C O H
IV.
III, II, IV, I I, IV, II, III IV, I, III, II I, II, III, IV
20. Rank the following substituents in order of decreasing priority (highest first). (Sec. 6.4)
OCH3 I. a) b) c) d)
O
O
COH
CH
OCH2CH3
II.
III.
IV.
II, III, IV, I III, IV, I, II IV, III, II, I IV, I, II, III
67
Chapter 6 Chirality
21. Rank the following substituents in order of increasing priority. (Sec. 6.4)
H C
C H
H I.
CH3
CH3
C
C H
CH3
CH3
CH3
II.
III.
H C
C H
H3C IV.
a) III, II, IV, I b) IV, I, II, III c) I, III, II, IV d) IV, II, I, III 22. Which structures represent R-3-methylhexane? (Sec. 6.4)
H3C
H
H
I. a) b) c) d)
CH3
CH3
H
II.
H III.
CH3
IV.
II, III I, III I, II III, IV
23. Which structure is correctly named 3R,4S-3,4-dimethylhexane (Sec. 6.4)
H3C
H
H
H3C
H
I. a) b) c) d)
CH3
H3C H
H CH3
H3C
II.
H
H3C H
III.
IV.
II I, III III III, IV
24. Which statement about enantiomers is false? (Sec. 6.8) a) b) c) d)
enantiomers have the same boiling and melting points. enantiomers have the same chemical properties. enantiomers have the same atom connectivity. enantiomers have the same three dimensional orientation.
68
H CH3
Chapter 6 Chirality 25. Which statements about stereoisomers are true? (Sec. 6.8, 6.9) I) enantiomers and diastereomers have the same physical properties. II) 50/50 mixtures of R and S enantiomers are called racemic mixtures. III) meso isomers rotate the plane of plane polarized light. IV) dextrorotatory compounds rotate plane polarized light to the right. a) b) c) d)
I, II II, III II, IV III, IV
Fill in the Blank 1. The following structure contains ___________ stereocenters. (Sec. 6.7)
OH OH O
Nadolol (beta-blocker)
OH N
2. The following structure contains __________ stereocenters. (Sec. 6.7)
CH3 N morphine O
OH
3. The priority order for the following groups are (highest = 1),
CH3 C CH3 CH3
H
CH3 C C
CH3 C C H
H
C H CH3
(Sec. 6.4)
69
Chapter 6 Chirality
4. The priority order for the following groups is (highest = 1),
Br
Cl
C H CH3
C Cl CH3
Cl
OH
C OH CH3
C H CH3
(Sec. 6.4) 5. The following structure is the _____________ configuration. (Sec. 6.4)
OH
OH 6. The following structure is the _____________ configuration. (Sec. 6.4)
NH2 OH Br 7. The structure of the R,R enantiomer of 2,3-butanediol is,
(Sec. 6.4) 8. The structure of the S,R enantiomer of 3-bromo-4-chlorohexane is,
(Sec. 6.4)
70
Chapter 6 Chirality
9. The following structures are __________________ (what type of stereoisomer). (Sec. 6.3, 6.5)
NH2
OH
NH2
OH
10. The following structures are ________________ (what type of stereoisomer). (Sec. 6.3, 6.5)
True-False 1. The following structures are enantiomers. (Sec. 6.3)
Cl
H Cl HO
CH3
H HO
CH3
2. The following structures are diastereomers. (Sec. 6.5)
Cl
Br
Cl
Br
3. The name of the following structure is 2S,3S-2,3-dibromobutane. (Sec. 6.4)
Br
Br 4. The diastereomer of 2R,3R-dichlorobutane is achiral. (Sec. 6.5) 5. The following groups are listed in decreasing order of priority. (Sec. 6.4)
O
O OH >
OCH3 >
> CH3
OH
71
Chapter 6 Chirality
6. The following groups are listed in decreasing order of priority. (Sec. 6.4)
OH >
NH2
>
Br
>
CH3
7. Enantiomers have the same physical properties (m.p., b.p., index of refraction, density). (Sec. 6.8) 8. Meso compounds rotate plane polarized light the same magnitude as enantiomers, but in opposite directions. (Sec. 6.5) 9. Diastereomers are achiral. (Sec. 6.5) 10. Enantiomers and meso compounds are diastereomers. (Sec. 6.5)
72
Chapter 6 Chirality Answers Multiple Choice 1. d 2. b 3. d 4. c 5. c 6. c 7. d 8. d 9. a 10. a 11. c 12. c 13. b 14. a 15. a 16. b 17. c 18. d 19. b 20. d 21. d 22. c 23. c 24. d 25. c Fill in the Blank 1. 2. 3. 4. 5. 6. 7.
3 5 2, 3, 1, 4 2, 1, 3, 4 2R, 3R 1S, 2S
OH
OH 8.
Cl
Br 9. enantiomers 10. diastereomers
73
Chapter 6 Chirality True-False 1. T 2. T 3. F 4. T 5. F 6. F 7. T 8. F 9. F 10. T
74
Chapter 7 Haloalkanes Multiple Choice 1. Which of the following structures have the correct IUPAC name? (Sec. 7.2)
Cl H
C CH CH CH 2 2 3 CH3
CH3 F
R-2-chloropentane I
R-4-fluoro-4-methylcyclohexene II
H3CO Br
H
CH3 Cl
Br H
S-2-chloro-2-fluorobutane IV
I, II III, IV I, III II, IV
2. Which of the following structures have correct common names? (Sec. 7.2)
H3C H2C
CHCH2F
CHCH2Br H3C
allyl fluoride I
isobutyl bromide II I
HCCl3 methylene chloride III a) b) c) d)
F
CH2CH3
OCH3
meso-1,2-dibromo-1,2-dimethoxyethane III a) b) c) d)
C
H3C
CH CH2CH3
isopropyl iodide IV
I, II III, IV I, III II, IV
75
Chapter 7 Haloalkanes
3. Which of the following compounds are secondary halides? (Sec. 7.6) I) Isobutyl bromide a) b) c) d)
II) 2-iodobutane
III) isopropyl fluoride
IV) neopentyl chloride
I, II III, IV II, III I, IV
4. Which compounds are primary halides? (Sec. 7.6)
H H3C
C
C
CH3
CH3 H3C
CH3
I
Cl
H3C
CH2 CBr3
FH2C
CH3
II
III
IV
I, II III, IV II, III I, IV
5. Which of the following halides is prepared from the following reactions? (Sec. 7.1, 5.3)
HBr
Br Br
Br Br
Br a)
b)
c)
d)
6. Which is the best reaction condition for preparing 2-iodohexane from 1-hexene? (Sec. 7.1, 5.3) a) b) c) d)
CH2 CH
CH3
I a) b) c) d)
C
CH3
I2 / CCl4 HI NaI HIO4
76
Chapter 7 Haloalkanes
7. Arrange the nucleophiles in order of increasing reactivity (least first). (Sec. 7.6)
NH3
H2O
OH
I
II
III
a) b) c) d)
CH3O IV
I, IV, II, III IV, II, I, III II, I, III, IV IV, III, I, II
8. Arrange the nucleophiles in order of increasing reactivity (least first). (Sec. 7.6)
O H3CCO
H3CO
Br
H2O
II
III
IV
I a) b) c) d)
III, II, I, IV IV, I, II, III I, III, II, IV III, I, IV, II
9. Arrange the leaving groups in order of increasing leaving group ability (least first). (Sec. 7.6)
O H3CCO I a) b) c) d)
H3CO
Br
HO
II
III
IV
I, III, II, IV III, I, IV, II VI, II, I, III IV, III, II, I
10. Arrange the leaving groups in order of increasing leaving group ability (least first). (Sec. 7.6)
a) b) c) d)
Cl
I
Br
F
I
II
III
IV
IV, I, III, II III, I, IV, II II, IV, I, III II, III, I, IV
77
Chapter 7 Haloalkanes 11. Arrange the alkyl halides in order of increasing reactivity in an SN2 reaction with KI in acetone (least first). (Sec. 7.6-7.7)
Cl CH2CH2Br
Cl
Br
CCH3 CH3
I a) b) c) d)
II
III
I, IV, III, II IV, I, III, II II, III, I, IV III, II, IV, I
12. Which are optimum conditions for an SN2 reaction? (Sec. 7.6-7.7)
I.
II.
acetone
CH2Cl
+
NaSH
Cl
+
CH3OH
+
CH3S Na
+
NaI
CH3 III.
IV.
a) b) c) d)
Cl
CH2Br
I, II II, III III, IV I, IV
78
H2O
DMSO
DMSO
IV
Chapter 7 Haloalkanes
13. Which nucleophilic substitution reactions will proceed? (Sec. 7.6-7.7)
I. NaCl + CH3CH2OH
II. NH3
+
acetone
Br
ethanol
III. CH3CH2O + CH3CH2CH2Cl ethanol IV. LiCl + CH4 a) b) c) d)
acetone
I, II II, III III, IV I, IV
14. Which reactions will proceed with inversion of configuration? (Sec. 7.6-7.7)
OCH2CH3 R-2-bromohexane CH3CH2OH
S-2-iodobutane
OH R-3-bromo-3-methylhexane CH3CH2OH III.
R-2-bromohexane IV.
I, II III, IV II, III I, IV
15. Which solvents are polar aprotic? (Sec. 7.6) I) DMSO II) H2O III) Acetone IV) Formic acid a) b) c) d)
acetone
II.
I.
a) b) c) d)
NaSCH3
II, III III, IV I, III II, IV
79
CH3OH heat
Chapter 7 Haloalkanes 16. Arrange the alkyl halides in order of increasing rate of solvolysis (slowest first)? (Sec. 7.6)
CH3 H3C
H3CH2C
CCl
CHCl
H3CH2C
CH3 I a) b) c) d)
H3C
CHCl
H3C III
II
IV, III, II, I I, II, III, IV III, II, I, IV II, III, I, IV
17. Which conditions are optimum for an SN1 reaction? (Sec. 7.6-7.7)
a)
CH3CH2Cl
+
NaCN
CHCl
+
CH3OH
CH3CH2CH2Br
+
NaSH
+
NaCN
acetone
H3C b)
H2O
H3C c)
DMSO
CH3 d)
H3C
CCl
DMSO
CH3 18. Which solvents are polar protic? (Sec. 7.6) I) ethanol II) hexane III) DMSO IV) water a) b) c) d)
III, IV II, III I, IV I, III
80
CH3CH2CH2Cl
IV
Chapter 7 Haloalkanes
19. Which statements apply to an SN1 reaction? (Sec. 7.6) I) The rate limiting step of the reaction involves the alkyl halide and the nucleophile. II) The order of reactivity is methyl > 1°>2°>3°. III) The rate limiting step of the reaction involves only the alkyl halide. IV) There is an intermediate carbocation. a) b) c) d)
I, II III, IV I, IV III
20. Which statements apply to an SN2 reaction? (Sec. 7.6) I) The rate limiting step of the reaction involves the alkyl halide and the nucleophile. II) The order of reactivity is methyl > 1°>2°>3°. III) The rate limiting step of the reaction involves only the alkyl halide. IV) There is an intermediate carbocation. a) b) c) d)
I, II III, IV I, IV II, IV
21. Which conditions are optimum for an E2 reaction? (Sec. 7.8-7.9)
a)
CH3I
+
CH3 b) CH3CHCl
CH3 +
CH3CO K
+
CH3OH
+
CH3O
CH3 d) CH3CHCH2Br
DMSO
CH3
CH3 c) CH3CHCH2Cl
DMSO
F
H2O
H2O
22. What is the major product from an elimination reaction starting with 2-bromopentane? (Sec. 7.8-7.9) a) b) c) d)
1-pentene cis-2-pentene trans-2-pentene a mixture of cis and trans-2-pentene
81
Chapter 7 Haloalkanes
23. Which alkyl halide leads to the product shown, in an E2 reaction? (Sec. 7.8-7.9)
CH2
Cl
CH2Cl
CH3 CH3
a)
b)
CH3 c)
d)
Cl
Cl
24. Which statements are true for an E1 reaction? (Sec. 7.9) I) The rate limiting step of the reaction involves only the alkyl halide. II) The rate limiting step of the reaction involves the alkyl halide and the base. III) There is an intermediate carbocation. IV) The order of reactivity is 1°>2°>3°. a) b) c) d)
I, III II I, III, IV II, IV
25. Which conditions are best for preparing isopropyl methyl ether? (Sec. 7.10)
H3C a)
b)
Na OCH3
Na OCH
d)
CHBr
H3C
CH3 CH3
c)
+
CH3OH
CH3OH
+
CH3Br H3C
+
+
CHBr
heat
CHOH
acid catalysis
H3C H3C H3C
82
Chapter 7 Haloalkanes Fill in the Blank 1. The major product of the following reaction is,
KSCH3 Cl
H
DMSO (Sec. 7.6)
2. The major product of the following reaction is,
KOH Br
H2O
H
(Sec. 7.6)
3. The major product of the following reaction is,
NH3 H
I
(Sec. 7.6)
4. The major product of the following reaction is,
I
NaOCH2CH3 CH3CH2OH
(Sec. 7.9)
5. The major product of the following reaction is,
H2O H Br
(Sec. 7.6)
6. The reagent needed to complete the following reaction is,
Cl (Sec. 7.9)
83
Chapter 7 Haloalkanes
7. The reagent needed to complete the following reaction is,
H
Br
H
OH
(racemic) (Sec. 7.6) 8. The reagent needed to complete the following reaction is,
Br
H
H3CO
H
H
OCH3
+ (Sec. 7.6) 9. The starting material needed to complete the following reaction is,
KI I CH3CH2OH (Sec. 7.6) 10. The starting material needed to complete the following reaction is,
HS
H
NaSH acetone
(Sec. 7.6)
True-False 1. Polar aprotic solvents favor SN1 reactions. (Sec. 7.6) 2. The order of SN1 reactivity of the following alkyl halides are listed in decreasing order. (Sec. 7.6)
Cl > H3C Cl
>
Cl
>
Cl
3. The order of SN2 reactivity of the following alkyl halides are listed in decreasing order. (Sec. 7.6)
Br >
I
>
F >
Cl
84
Chapter 7 Haloalkanes
4. The following nucleophiles are listed in decreasing order of reactivity in an SN2 reaction. (Sec. 7.6)
I- > Br- > Cl-
> F-
5. The following nucleophiles are listed in decreasing order of reactivity in an SN2 reaction. (Sec. 7.6)
F- > HO- > H2N6. The name of the following compound is cis- (1R,2S)-1-chloro-2-bromocyclohexane. (Sec. 7.2)
Cl Br
7. The name of the following compound is R, E - 4-bromo-2-pentene. (Sec. 7.2)
Br
8. The major product of the reaction of R-2-bromobutane with sodium iodide in acetone is S-2-iodobutane. (Sec. 7.6) 9. The major product of the reaction of R-2-bromobutane with water is a racemic alcohol. (Sec. 7.6) 10. The major product of the reaction of bromocyclohexane and potassium t-butoxide in water is an ether. (Sec. 7.6)
85
Chapter 7 Haloalkanes Answers Multiple Choice 1. c 2. a 3. c 4. b 5. a 6. b 7. c 8. b 9. c 10. a 11. d 12. d 13. b 14. a 15. c 16. a 17. b 18. c 19. b 20. a 21. b 22. c 23. c 24. a 25. b Fill in the Blank 1.
H SCH3 2.
H OH 3.
H2N
H
86
Chapter 7 Haloalkanes
4.
5.
+ HO H
H OH
6. base 7. H2O 8. HOCH3 9.
Br or
Cl
10.
H
Cl
(or –Br, -I) True-False 1. F 2. F 3. F 4. T 5. F 6. F 7. T 8. T 9. T 10. F
87
Chapter 8 Alcohols, Ethers, and Thiols Multiple Choice 1. Which is the IUPAC name for the following structure? (Sec. 8.2)
OH a) b) c) d)
cyclohexenol 3-cyclohexen-1-ol 1-cyclohexen-4-ol 4-cyclohexenol
2. Which structures have the correct IUPAC name? (Sec. 8.2)
CH2OH
O
C OCH H 3 H3C
O CH2
cis-1,2-dimethoxycyclohexane I
R-2-methoxy-1-propanol II
OH
H3C HC OCH3 H3C
OH
2-methoxypropane III
a) b) c) d)
trans-1,3-cyclohexanediol IV
I, II III, IV II, III I, IV
3. Arrange the compounds in the order of increasing solubility in water (least first). (Sec. 8.4)
CH3CH2CH2CH2OCH3 I CH3OCH2CH2OCH3 III a) b) c) d)
CH3OCH3 II CH3CH2CH2CH2CH2OH IV
I, III, II, IV III, I, IV, II I, IV, II, III IV, I, III, II
88
Chapter 8 Alcohols, Ethers, and Thiols
4. Which are secondary alcohols? (Sec. 8.2)
CH3
CH3 H3C
OH I a) b) c) d)
H3C
H
H C C
C OH
H
CH3
CHCH3 OH
II
III
IV
I, III II, III III, IV I, IV
5. Arrange the compounds in the order of increasing acidity (least first). (Sec. 8.3)
CH3 CH3CH2OH I a) b) c) d)
CH3COH CH3 II
OH CH3CHCH3
H2O
III
IV
III, I, II, IV I, III, IV, II II, III, I, IV II, I, III, IV
6. Arrange the compounds in the order of increasing acidity (least first). (Sec. 8.6)
H3C CHOH
CH3CH2SH
H2S
H2O
II
III
IV
H3C I
a) b) c) d)
OH
II, I, III, IV I, IV, II, III III, II, I, IV II, I, IV, III
89
Chapter 8 Alcohols, Ethers, and Thiols
7. Arrange the compounds in the order of increasing boiling point (lowest first). (Sec. 8.3, 8.4, 8.6)
H3C
O
CH3
I a) b) c) d)
H2O
CH3CH2OH
CH3CH2SH
II
III
IV
II, I, III, IV I, IV, II, III IV, I, III, II I, IV, III, II
8. Arrange the compounds in the order of increasing solubility in water (lowest first). (Sec. 8.2)
CH3OH
CH3CH2CH2CH2CH2OH
I
II
CH3CH2CH2CH2OH
HOCH2CH2CH2CH2CH2OH
III
IV
a) b) c) d)
IV, III, II, I II, III, IV, I III, IV, II, I II, IV, III, I
9. Which alcohol will form the most stable carbocation? (Sec. 8.3)
CH3 a)
CH3CHCH2OH CH3
b)
CH3
COH CH3
c)
d)
OH
CH3OH
90
Chapter 8 Alcohols, Ethers, and Thiols
10. How many isomers, including stereoisomers, can be formed from the hydroxylation of 4methylcyclohexene using osmium tetroxide? (Sec. 8.3, 8.4) a) b) c) d)
2 4 6 8
11. Arrange the following in order of increasing ability to hydrogen bond (lowest first). (Sec. 8.3, 8.4, 8.6)
I. III. a) b) c) d)
CH3
II.
H
CH3O H
CH3S
H
IV. HO H
I, II, III, IV III, I, IV, II II, IV, I, III I, IV, II, III
12. Which reagents do not effect the following conversion? (Sec. 8.3)
HO
a) b) c) d)
CH3
Cl
CH3
HCl
Cl2
SOCl2
NaCl
I.
II.
III.
IV.
I, II II, III II, IV I, III
13. Which is the major product from the acid catalyzed hydrolysis of cyclohexene oxide? (Sec. 8.5)
a)
b)
H H
OH H H OH
HO OH
O c)
d)
91
Chapter 8 Alcohols, Ethers, and Thiols
14. Which is the major product of the following reaction? (Sec. 8.5)
H
2
H
H
C
C H
O
H2NCH2CH2NH2
+
a) HOCH2CH2NH2
b) O
N
c) HOCH2CH2NHCH2CH2OH
d) HOCH2CH2NHCH2CH2NHCH2CH2OH
15. Which is the best method for making the following conversion? (Sec. 8.3)
OH CH3CH2CH2OH
a)
H3PO4 heat
CH3CHCH3
dilute H2SO4
Pt / H2
b)
dilute H2SO4 O
c)
PCC
d)
COO H
H3PO4 heat
16. Which is the product of the following reaction? (Sec. 8.3, 8.5)
OH H3PO4 heat
OsO4 / ROOH
OH a)
O b)
OH
OH H
O c)
O
d)
H
92
Chapter 8 Alcohols, Ethers, and Thiols 17. Which is the product of the following reaction? (Sec. 8.3)
CH2OH
PCC
O O
O
H
b)
a)
O O
C
c) H3CCCH2CH2CH2CH
d)
18. Treatment of cyclopentene with dilute sulfuric acid, followed by reaction with chromic acid gives which of the following compounds as the major product? (Sec. 8.3)
O
OH O a)
b)
OH
c)
O
d)
O
19. Which is the major product of the following reaction? (Sec. 8.3, 8.5)
CH3
Pt / H2
H3PO4
CH3CHCH2OH
heat
CH3
CH3
a) CH3CHCH
b) CH3CHCOH
O
O
CH3 c) CH3CHCH3
d) CH3CH2CH2CH3
20. Which are the best conditions for the preparation of 1-chloro-2-methylpropane starting from 2-methyl1-propanol? (Sec. 8.3)
a)
c)
H3PO4
HCl
heat K
Cl2
b)
d)
SOCl2
NaCl
93
OH
Chapter 8 Alcohols, Ethers, and Thiols
21. Which is the major product of the following reaction? (Sec. 8.5)
H3C
O COOH
CH2Cl2 HO CH3 OH H3C O a)
b)
HO CH2
H3C O
c)
d)
22. Which is the major product of the following reaction? (Sec. 8.3, 8.5)
O C C H
H
H+ / H2O
H
O O a)
C
CrO3 H2SO4
O O
COH
b)
C CH
OH O
O c)
C CH2OH
d)
23. Arrange the following in order of increasing rate of reactivity with HBr (least first). (Sec. 8.3)
OH
OH
CH2OH
CH3 I a) b) c) d)
CH3OH
II
III
I, II, IV, III II, I, III, IV IV, III, I, II III, II, IV, I
24. Classify the following reaction. (Sec. 8.6)
CH3CH2S a) b) c) d)
SCH2CH3
2 CH3CH2SH
oxidation reduction neither both
94
IV
CH COH
Chapter 8 Alcohols, Ethers, and Thiols
25. Which is the major product of the following reaction? (Sec. 8.5)
O H+ / H2O C CH CH2CH3
H3C H3C a) b) c) d)
3-pentanol 2-pentanol 2-methyl-2,3-pentanediol 4-methyl-3,4-pentanediol
Fill in the Blank 1. The major product of the following reaction is,
OH
H2SO4 heat (Sec. 8.3)
2. The major product of the following reaction is,
H2CrO4 OH
acetone H2O
(Sec. 8.3)
3. The major product of the following reaction is,
OH
Na (Sec. 8.3)
4. The major product of the following reaction is,
H2NCH3
O
(Sec. 8.5) 5. The reagent needed to complete the following reaction is,
O
OH
95
(Sec. 8.3)
Chapter 8 Alcohols, Ethers, and Thiols 6. The reagent needed to complete the following reaction is,
Cl
OH
(Sec. 8.3)
7. The reagent needed to complete the following reaction is,
O (Sec. 8.5) 8. The starting material needed to complete the following reaction is,
H3PO4 heat
(Sec. 8.3)
9. The starting material needed to complete the following reaction is,
SOCl2
Cl
(Sec. 8.3)
10. The reaction arrows (curved arrows) required to complete the following reaction mechanisms are, H +
OH
H SO4H
O H
H
+
H
-
(Sec. 8.3)
96
SO4H
C H
H
Chapter 8 Alcohols, Ethers, and Thiols True-False 1. The strongest acid in the following list is water. (Sec. 8.3, 8.4, 8.6)
H 3C
O
S
H 3C
CH3
CH3
O
H
H
H3C
O
S
H H3C
H
2. The major product of the reaction of 1-propanol with PCC is propanoic acid. (Sec. 8.3) 3. The product of the reaction of methanol with sodium metal is sodium methoxide. (Sec. 8.3) 4. The major product of the reaction of 3-methyl-2-butanol with hot, concentrated sulfuric acid is 3methyl-1-butene. (Sec. 8.3) 5. The following compound is named 1-chloro-2,2-dimethyl-4-pentanol. (Sec. 8.2)
Cl OH 6. The following compound is named 2,6-dimethyl-1,4-cyclohexanediol. (Sec. 8.2)
OH
OH 7. The following compounds are listed in decreasing boiling point order (highest first). (Sec. 8.2)
H3C
O
O
H > CH CH 3 2
H > CH3CH2CH2
O
H > CH3CH2CH2CH2
O
H
8. The following compounds are listed in decreasing boiling point order (highest first). (Sec. 8.2, 8.4)
H3C
O
CH3 > H3C
O
H >
H
O
H
9. The following compounds are listed in decreasing order of solubility in water (highest first). (Sec. 8.2)
CH3CH2CH2CH2
O
H > CH3CH2CH2
O
H > CH3CH2
O
H > H 3C
10. The following compounds are listed in increasing order of solubility in water (lowest first). (Sec. 8.2, 8.4)
<
OH
<
97
O
O
H
Chapter 8 Alcohols, Ethers, and Thiols Answers Multiple Choice 1. b 2. b 3. c 4. c 5. c 6. b 7. d 8. b 9. b 10. a 11. a 12. c 13. b 14. d 15. a 16. a 17. b 18. c 19. c 20. b 21. d 22. a 23. c 24. b 25. c Fill in the Blank 1.
2.
OH O 3.
O
Na+
4.
OH NHCH3 5. PCC
98
Chapter 8 Alcohols, Ethers, and Thiols 6. SOCl2 7. a peracid 8.
OH
9.
OH 10. H +
OH
H
+
H
SO4H
O H
H
-
True-False 1. F 2. F 3. T 4. F 5. F 6. T 7. F 8. F 9. F 10. F
99
SO4H
C
H
H
Chapter 9 Benzene and Its Derivatives Multiple Choice 1. Which structures have the correct IUPAC names? (Sec. 9.4)
CH3
CH3
Cl
Br
Br I. 2-bromotoluene II. para methyl, meta chloro bromobenzene OCH3
NO2
Cl III. meta chloroaniline a) b) c) d)
CH2CH3 IV. para ethylanisole
I, II III, IV I, IV II, III
100
Chapter 9 Benzene and Its Derivatives
2. Which of the named compounds have correct structures? (Sec. 9.4)
OH
O CH3
Cl
CH2CH2Br
I. meta chlorotoluene
Br
II. bromomethyltoluene
III. para bromophenol NH2
OCH3
Cl
Cl
NO2
Cl IV. ortho nitroanisole a) b) c) d)
V. 2,4,6-trichloroaniline
I, II, IV I, III, IV I, IV, V II, III, V
3. How many Kekule structures are possible for naphthalene? (Sec. 9.2, 9.3)
a) b) c) d)
3 4 5 6
4. How many π-orbital electrons are in the following molecule? (Sec. 9.3)
N N H a) b) c) d)
4 6 8 10 101
Chapter 9 Benzene and Its Derivatives
5. Which structures are aromatic? (Sec. 9.3)
O O
N
O
III
IV
CH2 I a) b) c) d)
II
II, III III, IV I, III II, IV
6. Arrange the compounds in order of increasing acidity (least first). (Sec. 9.9)
OH
OH
OH
OH NO2
I a) b) c) d)
Cl
NO2
NO2
II
III
IV
I, II, III, IV III, II, IV, I I, IV, III, II II, III, IV, I
7. Arrange the compounds in order of increasing acidity (least first). (Sec. 9.9)
OH
OH
I
II a) b) c) d)
OH
O
OCH3
IV
III
I, II, III, IV III, I, II, IV IV, II, I, III IV, II, III, I
102
Chapter 9 Benzene and Its Derivatives 8. Arrange the compounds in order of increasing acidity (least first).
OH
(Sec. 9.9, 2.4)
OH O
II
I a) b) c) d)
H2CO3
CH3COH
III
IV
I, II, III, IV III, IV, II, I I, II, IV, III II, I, III, IV
9. How can phenol be distinguished from cyclohexanol? (Sec. 9.9, 8.3) a) b) c) d)
solubility in water solubility in hydrochloric acid solution solubility in sodium bicarbonate solution solubility in sodium hydroxide solution
10. How many mono-bromoanthracenes are possible? (Sec. 9.2, 9.3) a) b) c) d)
1 2 3 4
11. Which contributing resonance structure is the most important for the bromination of anisole? (Sec. 9.8)
OCH3 a)
OCH3 b)
H
Br
OCH3 c)
H
Br
OCH3 d)
H
Br
12. Which is the electrophile in the nitration of benzene? (Sec. 9.7)
a) HNO3
b) NO2
c) NO3
d) NO
103
H
Br
Chapter 9 Benzene and Its Derivatives 13. Which compound reacts most readily in the nitration reaction? (Sec. 9.7)
CH3
CH3 a)
b)
CH3 c)
OCH3
HNCCH3
CH3 d)
COH
SO3H
O
O
14. Arrange the compounds in order of increasing reactivity toward electrophilic aromatic substitution (lowest first). (Sec. 9.7)
O
O
CNHCH3
NH2
NO2
I
II
III
a) b) c) d)
HNCCH3
IV
II, I, IV, III I, III, IV, II III, I, IV, II IV, III, II, I
15. Arrange the compounds in order of increasing reactivity toward electrophilic aromatic substitution (lowest first). (Sec. 9.7)
CH3
Cl
OH
I
II
III
O
IV
a) III, II, I, IV b) IV, II, I, III c) III, I, II, IV d) I, II, III, IV
104
Chapter 9 Benzene and Its Derivatives 16. Which is the major product of the following reaction? (Sec. 9.6)
OCH3
O
NO2
H3CCCl AlCl3 O OCH3
OCH3
NO2
NO2 a)
OCH3
b)
OCH2CCH3 NO2
c)
d) CCH3
H3CC O
O
CCH3
O
17. Which is the major product of the following reaction? (Sec. 9.6, 9.8)
O HC Br2
CH2
FeBr3
O
O
HC
HC CH2
a)
CH2
b)
Br
Br O
O
HC c)
HC CH2
Br
d)
CH2 Br
105
NO2
Chapter 9 Benzene and Its Derivatives 18. Which is the major product of the following series of reactions? (Sec. 9.5, 9.8)
CH3 AlCl3
K2Cr2O7
H3CCCl
H2SO4
O
O COH a)
O
O
CCH3
CCH3
b)
c)
OCH3 d)
COH
COH
CCH3
COH
O
O
O
O
19. Which is the best reaction sequence for preparing the following compound from benzene? (Sec. 9.6, 9.8)
O COH NO2
a)
AlCl3 CH3Cl
K2Cr2O7 H2SO4
b)
HNO3 H2SO4
AlCl3 CH3Cl
c)
AlCl3 H3CCl
HNO3 H2SO4
d)
O AlCl3 CH3Cl
HNO3 H2SO4
HNO3 H2SO4 K2Cr2O7 H2SO4
K2Cr2O7 H2SO4
106
Chapter 9 Benzene and Its Derivatives
20. Which is the major product of the following reaction? (Sec. 9.6, 9.8)
O
O
CCH2 CH2 CCl
AlCl3
O a)
b) O
O
c)
d) O
21. Which is the electrophile in the final reaction step for the following reaction? (Sec. 9.7)
O OH +
H3CCCH3
CH3
H3PO4
HO
C
OH
CH3
CH3 a) HO
CCH3
b) HO
O c) HO
C
C OH
d)
CH3
H3CCCH3
22. Which is the major product of the following reaction? (Sec. 9.6, 9.8)
HNO3 H2SO4 a) b) c) d)
Cl2 FeCl3
1-chloro-4-nitrobenzene 1-chloro-3-nitrobenzene 1-chloro-2-nitrobenzene a mixture of 1-chloro-4-nitrobenzene and 1-chloro-2-nitrobenzene
107
OH
Chapter 9 Benzene and Its Derivatives
23. Which is the major product of the following reactions? (Sec. 9.6, 9.8)
HNO3 H2SO4
CH2 Br
Br2 FeBr3 Br
NO2
a)
CH2
CH2
b)
NO2 NO2
c)
Br
CH2
NO2
d)
Br
24. Which is the major product of the following reactions? (Sec. 9.5, 9.6, 9.8)
CH3Cl FeCl3
Cl2 FeCl3 a) b) c) d)
K2Cr2O7 H2SO4
para chlorobenzoic acid meta chlorobenzoic acid a mixture of para and meta chlorobenzoic acid a mixture of ortho and para chlorobenzoic acid
25. Which is the electrophile in the following reaction? (Sec. 9.7)
H3PO4
+
a)
b)
c) HPO3
108
d)
CH2
Chapter 9 Benzene and Its Derivatives
Fill in the Blank 1. The major product of the following reaction is,
OH H3PO4 (Sec. 9.6, 9.8) 2. The major product of the following reaction is,
K2Cr2O7 H2SO4 (Sec. 9.5) 3. The major product of the following reaction is,
O
Br
Cl AlCl3
(Sec. 9.6, 9.8)
4. The major products of the following reaction are,
OH
OH +
NaOH H2O (Sec. 9.9)
109
Chapter 9 Benzene and Its Derivatives 5. The major products of the following reaction are,
O
OH
OH +
NaHCO3 H2O (Sec. 9.9)
6. The reagent that completes the following reaction is,
CH3
CH3
NO2
(Sec. 9.6, 9.8)
7. The reagents that complete the following reactions are,
SO3H 8. The starting material and reagent that complete the following reaction are,
SO3H
Cl
110
(Sec. 9.6, 9.8)
(Sec. 9.6, 9.8)
Chapter 9 Benzene and Its Derivatives 9. The reagents and mid-reaction product that complete the following scheme are,
Cl
O (Sec. 9.6, 9.8) 10. The reaction arrows (curved arrows) required to complete the following reaction mechanisms are,
Br
+
H +
C
Br
Br
H (Sec. 9.7) True-False 1. The name of the following structure is 2,4-diethylnitrobenzene. (Sec. 9.4)
NO2
2. The name of the following structure is 3,5-dibromobenzoic acid. (Sec. 9.4)
O
Br
OH
Br
3. The product of the reaction of toluene with concentrated nitric and sulfuric acid is m-nitrotoluene. (Sec. 9.6, 9.8) 4. The product of the reaction of isopropylbenzene with chromic acid is methylphenyl ketone. (Sec. 9.5) 5. The product of the reaction of benzoic acid and chlorine/AlCl3 is m-chlorobenzoic acid. (Sec. 9.6, 9.8)
111
Chapter 9 Benzene and Its Derivatives
6. The following compound is aromatic. (Sec. 9.3)
7. The following reaction scheme will synthesize the product shown. (Sec. 9.5, 9.6, 9.8)
OH
O CH3CH2Cl AlCl3
K2Cr2O7
Br2
H2SO4
FeBr3 Br
8. The following reaction scheme will synthesize the product shown. (Sec. 9.6, 9.8)
SO3H SO3
CH3CH2Cl
H2SO4
AlCl3
9. The following compounds are listed in decreasing order of reactivity toward electrophilic aromatic substitution. (Sec. 9.7)
OH
CH3 >
SO3H >
>
10. The following compounds are listed in decreasing order of reactivity toward electrophilic aromatic substitution. (Sec. 9.7)
Cl
O
NO2 >
>
>
112
Chapter 9 Benzene and Its Derivatives
Answers Multiple Choice 1. c 2. c 3. a 4. b 5. c 6. a 7. c 8. a 9. d 10. c 11. d 12. b 13. b 14. c 15. b 16. b 17. c 18. b 19. d 20. d 21. a 22. b 23. c 24. d 25. b Fill in the Blank 1.
2.
O
OH
113
Chapter 9 Benzene and Its Derivatives
3.
Br
O 4.
O
OH +
5.
O
O
OH +
6. HNO3, H2SO4 7.
Cl
SO3, H2SO4
AlCl3 8.
Cl SO3 , H2SO4
114
Chapter 9 Benzene and Its Derivatives
9.
O Cl
O Cl2 , FeCl3
AlCl3
10.
Br
+
H +
C
Br
Br
H
True-False 1. T 2. T 3. F 4. F 5. T 6. F 7. F 8. T 9. T 10. F
115
Chapter 10 Amines Multiple Choice 1. Which is the correct structure for diphenylamine? (Sec. 10.3)
NH2 H a)
N
b)
CH2 c)
NH2
d) NH2
2. Which is the IUPAC name for the following structure? (Sec. 10.3)
CH3 H H3C C
N CH3
CH3 a) b) c) d)
N-methyl-tert-butylamine N-methyl-1,1-dimethylethylamine N-methyl-2-methyl-2-propanamine tert-butyl methyl amine
3. Which is the structure for N,N-dimethyl-3-hexanamine? (Sec. 10.3)
CH3
NHCH3
a) CH3NCH2CH2CH2CH3
b) CH3CH2CH2CCH2CH3 NHCH3 CH3
CH3 c) CH3CH2CCH2CH2CH2NH2
N CH3 d) CH3CH2CHCH2CH2CH3
CH3
116
Chapter 10 Amines
4. Which pairs of names and structures match correctly? (Sec. 10.3)
I. piperidine
A.
II. pyrrolidine
B.
III. pyrrole
C.
IV. pyridine
D.
V. cyclohexylamine
NH
NH NH2 NH
E. N
a) b) c) d)
I and D, II and B III and A, IV and E V and C, III and B III and D, IV and E
5. Which structures are secondary amines? (Sec. 10.2)
CH3
NCH3
CH3CHCH2NH2
H
I
II
NH
NH2 III a) b) c) d)
IV
I, II II, III III, IV II, IV
117
Chapter 10 Amines
6. Which is the classification of the following amine? (Sec. 10.2)
CH3 H3CCH2CH2CH2
a) b) c) d)
N CH3 Cl
1° 2° 3° 4°
7. Which is the name for the following compound? (Sec. 10.3)
NH3 Cl
a) b) c) d)
phenylammonium chloride phenyltrihydrogenammonium chloride aniline chloride benzylammonium chloride
8. Which is the name for the following compound? (Sec. 10.3)
O H2N a) b) c) d)
COH
4-carboxy aniline 1-amino-4-carboxybenzene benzylamine carboxylic acid 4-aminobenzoic acid
9. Which compound is the strongest base? (Sec. 10.5)
CH3 a) CH3NH2
b) CH3NH
CH3 c) CH3NCH3
118
d) CH3NH3 OH
Chapter 10 Amines 10. Which compound is the strongest base? (Sec. 10.5)
NH2 a)
NH2
NH2
b)
c) Br
NH2 d)
NO2
CH3
11. Which reactions will proceed predominately to products as written? (Sec. 10.6)
I. CH3NH2
+
H2O
CH3NH3 + OH O
O II. CH3NH2 +
CH3NH3 + CH3CO
CH3COH CH3
III. CH3NH2 +
CH3
CH3NCH3
CH3NH + CH3NCH3 H
IV. CH3NH2 +
a) b) c) d)
CH3NH3 +
NH3
NH2
I, II III, IV II, IV I, III
12. When the following compounds are dissolved in water at the same concentrations, which one will have the lowest pH (i.e., most acidic)? (Sec. 10.5)
CH3
CH3 a)
CH2NCH3
CH2NCH3 OH
b)
CH3 CH3
CH3 c)
CH2NCH3 Cl d)
CH2NCH3 Cl CH3
H
119
Chapter 10 Amines 13. Arrange the amines in order of increasing basicity (weakest first). (Sec. 10.5)
NH2
NH2
NH2
H N
CH3 I
a) b) c) d)
II
IV
III
IV, II, III, I II, I, III, IV I, II, III, IV II, I, IV, III
14. At pH 5.0, the ratio of morpholine and morpholinium ion is 1:1622. Which is the pKb of morpholine? (Sec. 10.5) a) b) c) d)
3.21 5.79 8.21 9.25
15. Guanidine has a pKb value of 0.4. Which is the ratio of guanidine to its conjugate acid at blood pH of 7.4? (Sec. 10.5) a) b) c) d)
10-6.2:1 10+6.2:1 1:1 2.5:1
16. Which are the correct positions for the site of protonation of the bases, guanidine and imidazole? (Sec. 10.6)
NH
I H2N
C
N
NH2
III
N II a) b) c) d)
IV
H
I, III II, IV I, IV II, III
120
Chapter 10 Amines 17. Arrange the amines in order of increasing boiling point (lowest first). (Sec. 10.4)
CH2CH3 N
CH3CH2
CH2CH3
CH2CH3
CH3CH2NH2
I a) b) c) d)
CH3CH2NH
II
CH3CH2NH3 Cl
III
IV
II, III, I, IV III, I, IV, II IV, II, III, I IV, III, I, II
18. Arrange the amines in order of increasing boiling point (lowest first). (Sec. 10.4) methylamine I a) b) c) d)
ethylamine II
propylamine III
cyclohexylamine IV
IV, III, II, I I, II, III, IV III, II, I, IV II, I, IV, III
19. Arrange the amines in order of increasing solubility in water (least first). (Sec. 10.4)
CH2CH3 CH3CH2
N
CH2CH3
I a) b) c) d)
CH2CH3 CH3CH2NH2 II
CH3CH2NH
CH3CH2NH3 Cl
III
II, III, I, IV IV, II, III, I IV, III, II, I I, III, II, IV
20. Arrange the amines in order of increasing solubility in water (least first). (Sec. 10.4) ethylamine I a) b) c) d)
methylamine II
propylamine III
II, I, III, IV IV, II, III, I IV, III, I, II I, III, II, IV
121
cyclohexylamine IV
IV
Chapter 10 Amines 21. Arrange the following in order of increasing strength of the hydrogen bonds (weakest first). (Sec. 10.4)
I. H2NH III. H2O a) b) c) d)
OH2
II. H3N
HNH2
HOH
IV. H3N
HOH
I, II, III, IV II, I, IV, III II, IV, I, III I, IV, II, III
22. Which is the product of the following reaction? (Sec. 10.7)
NO2 Fe, HCl H3C
CH3
ethanol/water
NO2
NH3Cl
a)
b)
HOOC
COOH
H 3C
CH3
NO2 Cl c)
Cl
d) H 3C
CH3
H 3C
122
CH3
Chapter 10 Amines 23. Which is the product of the following reaction? (Sec. 10.8)
NH2 NaNO2 HCl, 0° C CH3 N +
N Cl-
NH2 a)
b) CH3
NH2
NO2
O2N
c)
d)
CH3
O2N
CH3
CH3
24. Which is the product of the following reaction? (Sec. 10.8)
NH2 H3PO2
NaNO2 HCl, 0° C CH3 NH3Cl a)
NH2
NH2 c)
b) O2 P CH3
d)
PO2 CH3
CH3
123
NO2
Chapter 10 Amines
25. The following mixture was extracted with 1 M HCl, followed by 1 M NaOH, followed by ether. Which compound is recovered from the acid solution? (Sec. 10.6)
H3C
N
CH3
H3C
II
I a) b) c) d)
OH
CH
CH3
III
I II III None of the above
Fill in the Blank 1. The name of the following compound is _______________________________. (Sec. 10.3)
N H
CH3
CH3 2. The name of the following compound is ______________________________. (Sec. 10.3)
Br N H 3. The name of the following compound is _________________________________. (Sec. 10.3)
N +
N Cl-
CH3
124
Chapter 10 Amines
4. The starting material needed to complete the following reaction is,
NH2 Fe, HCl Br
Br (Sec. 10.7
5. The starting material needed to complete the following reaction is,
H3PO2
CH3
H 3C
CH3 6. The reactants needed to complete the following reaction are,
NH2
OH
(Sec. 10.8) 7. The major product of the following reaction is,
NH2 1) NaNO2, HCl, H2O, 0° C O
2) warm solution OH
(Sec. 10.8)
125
(Sec. 10.8)
Chapter 10 Amines
8. The order of decreasing basicity of the following amines is (1 is the most basic),
CH3 O2N
NH2
N
H3 C
N
CH3
H3C NH2
(Sec. 10.5) 9. The order of increasing basicity of the following compounds is (1 is the least basic),
CH3
OH
O
NH2
OH
(Sec. 10.5) 10. The order of increasing boiling point of the following compounds is (1 is lowest boiling),
CH3
OH
O
NH2
OH
(Sec. 10.5)
True-False 1. The name of the following compound is N-cyclopentylethanamine. (Sec. 10.3)
H
N
CH2CH3
126
Chapter 10 Amines
2. The name of the following compound is 3,5-dimethylpiperidine. (Sec. 10.3)
H N H3C
CH3
3. The strongest base in the following group is aniline. (Sec. 10.5)
NH2
NH2 N
4. The strongest base in the following group is methylthiocyclohexane. (Sec. 10.5)
HN
CH3
O
CH3
S
CH3
5. Cyclohexanamine is a 2º amine. (Sec. 10.2) 6. tert-butyl methyl amine is a 3º amine. (Sec. 10.2) 7. The pKa for ethyl ammonium ion is 10.8 (ethyl amine pKb is 3.2). (Sec. 10.5) 8. Tertiary amines are generally stronger bases than secondary amines. (Sec. 10.5) 9. The equilibrium for the reaction of p-nitroaniline and acetic acid lies to the right. (Sec. 10.6) 10. The reaction of aniline with nitrous acid after warming yields phenol. (Sec. 10.8)
127
Chapter 10 Amines Answers Multiple Choice 1. b 2. c 3. d 4. d 5. d 6. d 7. a 8. d 9. b 10. d 11. c 12. c 13. c 14. b 15. a 16. c 17. a 18. b 19. d 20. c 21. b 22. b 23. c 24. c 25. a Fill in the Blank 1. N-methyl 2-methylcyclohexanamine 2. 3-bromopiperidine 3. 3-methylbenzene diazonium chloride 4.
NO2
Br
Br
128
Chapter 10 Amines 5.
N +
N Cl-
6.
1) NaNO2, H2O, HCl, O° 2) warm 7.
OH
HO O 8. 4, 3, 2, 1 9. 1, 3, 4, 2 10. 1, 3, 2, 4 True-False 1. F 2. T 3. F 4. F 5. F 6. F 7. T 8. F 9. F 10. T
129
Chapter 11 Infrared Spectroscopy Multiple Choice 1. Which is the approximate energy range for absorptions in the infrared region of the electromagnetic spectrum? (Sec. 11.4) a) b) c) d)
50 to 100 kcal/mol 10 to 50 kcal/mol 1 to 10 kcal/mol 0.01 to 0.1 kcal/mol
2. Which is the wave number for an infrared band at 5 microns (µm)? (Sec. 11.2) a) b) c) d)
500 cm-1 2000 cm-1 5000 cm-1 10,000 cm-1
3. Which is the wavelength (µm) of an infrared absorption band at 500 cm-1? (Sec. 11.2) a) b) c) d)
0.2 2.0 20 25
4. Which is the order of increasing bond stretching frequency (lowest first)? (Sec. 11.4) I) C=N II) C=O III) C=C IV) C=S a) b) c) d)
II, I, IV, III I, II, IV, III III, I, II, IV IV, III, I, II
5. Which is the order of increasing bond stretching frequency (lowest first)? (Sec. 11.4) I) C-H II) N-H III) O-H IV) F-H a) b) c) d)
I, II, III, IV I, III, II, IV IV, III, II, I III, II, I, IV
6. The broadening of the stretching vibration peak for alcohols is mainly due to which of the following? (Sec. 11.5) a) b) c) d)
water contamination a strong dipole moment hydrogen bonding coupling peaks
130
Chapter 11 Infrared Spectroscopy
7. A compound has the molecular formula C5H10O, and strong absorptions at 1100 and 3350 cm-1. Which is the most likely structure for the compound? (Sec. 11.5)
O
O a)
b) CH3CH2CCH2CH3 CH2OCH3
H c)
OH
d)
C C H3C
H
8. Which compound has a sharp IR absorption at 1710 cm-1 and a broad band at 3300 cm-1? (Sec. 11.5)
O
O
a) CH3COH b) CH3CH2OH c) CH3CCH3 d) CH3OCH3 9. Which compound has an IR absorption at 3300 cm-1 but no band at 1710 cm-1? (Sec. 11.5)
O
O
a) CH3COH b) CH3CH2OH c) CH3CCH3 d) CH3OCH3 10. Which is the most likely structure for a compound with molecular formula C5H8O, and an IR spectrum with a peak at 1710 cm-1 but no peak at 1650 cm-1? (Sec. 11.5)
a)
O
b)
c)
O
d)
OH H3C
H C
H
C CH2CH O
131
Chapter 11 Infrared Spectroscopy
11. Which compound has characteristic IR peaks at 3100 cm-1, 1600 cm-1, and 1480 cm-1? (Sec. 11.5)
H3C
H C
a) H
C CH CH3
CH3
b)
CH3
CH3 d) H3C
c) CH3CH2CH2OCH2CH3
CCH2CH3 CH3
12. Which compound has characteristic IR peaks at 3100 cm-1 and 1650 cm-1, but not 1480 cm-1? (Sec. 11.5)
H3C
H C
a)
C
H
CH CH3
CH3
b)
CH3
CH3
c) CH3CH2CH2OCH2CH3
d) H3C
CCH2CH3 CH3
13. Which compound has a characteristic IR peak at 2900 cm-1? (Sec. 11.5)
H3C
H C
I. H
C CH CH3
CH3
II.
CH3 III. CH3CH2CH2OCH2CH3
CH3 IV. H3C CCH2CH3 CH3
a) b) c) d)
I, II, III I, II, III, IV III, IV I, III, IV
132
Chapter 11 Infrared Spectroscopy
14. Which compounds will have a particularly weak characteristic IR stretching frequency? (Sec. 11.5)
H3C
CH3 C
H3C
C
H3CC
CCH3
CH3
I
II CH3
H2C
C
CH3CH2C
CH2
CH3 III a) b) c) d)
IV
I, II III, IV I, III II, IV
15. A compound has a molecular formula, C5H10O and no peaks in the IR spectrum at 3300 cm-1or 1680-1750 cm-1. Which could be this compound? (Sec. 11.5)
OCH3 OH
CH3CHC
CH2
CH3CCH2CH2CH3 O
H II
I a) b) c) d)
O
IV
III
I, II III, IV II, III II, IV
16. A compound has a molecular formula C7H14O2 and a broad signal in the region of 2850-3000 cm-1 and a signal in the region of 1710-1780 cm-1 in the IR spectrum. Which could be the compound? (Sec. 11.5)
O a) CH3CH2CH2COCH
CH3
b)
CH3
O O
OCH2CH3 O
c) CH3CH2CH2CH2CH2CH2COH d)
133
COH
Chapter 11 Infrared Spectroscopy
17. A compound has a molecular formula of C5H9N and the IR spectrum has no peaks in the region of 3000-3500 cm-1. Which could be the compound? (Sec. 11.5)
CH3 a) CH3CCH2NH2
CH2CH3 b) H3C N
CH3
c)
NH
CH2CH3 CH3 d) H2C
C
N CH3 H
18. Which region in the IR spectrum could be used to distinguish between butanoic acid and 2-butanone? (Sec. 11.5) a) b) c) d)
3200-3600 cm-1 1600 cm-1 1680-1750 cm-1 2500-3300 cm-1
19. Which region in the IR spectrum could be used to distinguish between benzyl amine and benzamide? (Sec. 11.5) a) b) c) d)
1475 cm-1 and 1600 cm-1 3030 cm-1 3100-3500 cm-1 1630-1690 cm-1
20. Which region in the IR spectrum could be used to distinguish between benzene and cyclohexane? (Sec. 11.5) a) b) c) d)
3000 cm-1 1600 cm-1 1680-1750 cm-1 3200-3600 cm-1
21. Very prominate peaks in the IR spectrum are sufficient to distinguish between which compounds? (Sec. 11.5) I) butane and cyclobutane II) toluene and methylcyclohexane III) 2-pentanone and 3-pentanone IV) pentanal and 1-pentene a) b) c) d)
I, III II, III II, IV III, IV
134
Chapter 11 Infrared Spectroscopy
22. Very prominate peaks in the IR spectrum are sufficient to distinguish between which compounds? (Sec. 11.5) I) diethyl ether and diethylamine II) cyclohexanone and cyclopentanone III) pentanal and pentanol IV) 2-hexene and 3-hexene a) b) c) d)
I, III II, III II, IV III, IV
23. Very prominate peaks in the IR spectrum are sufficient to distinguish between which compounds? (Sec. 11.5) I) butanoic acid and methyl butanoate II) dimethylamine and N,N-dimethylformamide III) triethylamine and dimethylpropanamine IV) 2-pentanol and 3-pentanol a) b) c) d)
I, II II, III I, IV III, IV
24. Which is the index of hydrogen deficiency for a compound having molecular formula C7H5Cl2NO? (Sec. 11.5) a) b) c) d)
4 5 6 7
25. Which is the index of hydrogen deficiency for a compound having molecular formula C12H13Br2NO2? (Sec. 11.5) a) b) c) d)
5 6 7 8
Fill in the Blank 1. The energy in kcal/mol of 606.06 µm light is ___________________. (Sec. 11.2) 2. The energy in kcal/mol of 3350 cm-1 light is ___________________. (Sec. 11.2) 3. The _______________ cm-1 region would best distinguish between the following structures. (Sec. 11.5)
O
O OH
135
Chapter 11 Infrared Spectroscopy
4. The ______________ cm-1 region would best distinguish between the following structures. (Sec. 11.5)
O
5. The ___________________functional group has a characteristic absorption in the 3200-3500 cm-1. (Sec. 11.5) 6. The ___________________functional group has a characteristic absorption in the 1630-1800 cm-1. (Sec. 11.5) 7. The index of hydrogen deficiency for the compound of formula C11H15NO is ______________. (Sec. 11.5) 8. The index of hydrogen deficiency for the compound of formula C8H10Br2O2 is ______________. (Sec. 11.5) 9. The _______________ cm-1 region is characteristic of the alkane stretch. (Sec. 11.5) 10. The _______________ cm-1 region is characteristic of the alkene stretch. (Sec. 11.5) True-False 1. The following molecule is not IR active. (Sec. 11.5)
H
2. The following molecule is not IR active. (Sec. 11.5)
3. 3-Hexanone has an IR absorption in the 3200-3500 cm-1 region. (Sec. 11.5) 4. 2-Pentenal has an IR absorption in the 1630-1800 and 1600-1680 cm-1 region. (Sec. 11.5) 5. The 3200-3500 cm-1 region can be used to distinguish between alcohols and amines by frequency alone. (Sec. 11.5) 6. The 1630-1800 cm-1 region can be used to distinguish between alcohols and carboxylic acids. (Sec. 11.5) 7. The strength of absorption signal in the 3200-3500 cm-1 region is greater for alcohols than amines. (Sec. 11.5) 8. The strength of absorption signal in the 1630-1680 cm-1 region is greater for carbonyl groups than alkene groups. (Sec. 11.5) 9. The index of hydrogen deficiency for C7H6Br4O2 is 3. (Sec. 11.5) 10. The index of hydrogen deficiency for C9H12N2O is 4. (Sec. 11.5)
136
Chapter 11 Infrared Spectroscopy Answers Multiple Choice 1. c 2. b 3. c 4. d 5. a 6. c 7. c 8. a 9. b 10. a 11. b 12. a 13. b 14. a 15. d 16. a 17. d 18. d 19. d 20. b 21. c 22. a 23. a 24. b 25. b Fill in the Blank 1. 4.722 kcal/mol 2. 9.572 kcal/mol 3. 2400-3300 cm-1 4. 1630-1800 cm-1 5. alcohol 6. carbonyl 7. 5 8. 3 9. 2800-3000 cm-1 10. 1600-1680 cm-1 True-False 1. F 2. T 3. F 4. T 5. F 6. T 7. T 8. T 9. T 10. F
137
Chapter 12 Nuclear Magnetic Resonance Spectroscopy Multiple Choice 1. How many sets of equivalent hydrogen atoms are there for 2-propanol? (Sec. 12.6) a) b) c) d)
2 3 4 8
2. How many sets of equivalent hydrogen atoms are there for the following compound? (Sec. 12.6)
CH3
a) b) c) d)
3 4 5 6
3. How many sets of signals are there in the 1H-NMR spectrum for 1,1-dichlorocyclohexane? (Sec. 12.6) a) b) c) d)
2 3 4 6
4. How many sets of signals are there in the 1H-NMR spectrum for diisopropyl ether? (Sec. 12.6) a) b) c) d)
1 2 3 6
5. How many sets of equivalent carbon atoms are there for the following compound? (Sec. 12.10)
CH3
OH a) b) c) d)
3 4 5 6
6. How many sets of equivalent carbon atoms are there for 1-bromo-3-chlorocyclohexane? (Sec. 12.10) a) b) c) d)
3 4 5 6 138
Chapter 12 Nuclear Magnetic Resonance Spectroscopy
7. A compound gave two sets of signals in the 1H-NMR spectrum with an integration ratio of 60 to 10. Which is the most likely structure for the compound? (Sec. 12.6, 12.7)
O a) CH3CH2CH2CCH2CH2CH3
b) H3C
CH3 d)
c) O
H3C
OH O
CHCCH
H3C
CH3 CH3
CH3 8. Which are the relative areas of integration in the 1H-NMR spectrum for 2-chloro-3-methylbutane? (Sec. 12.7) a) b) c) d)
9:1:1 3:3:3:1:1 6:3:2 6:3:1:1
9. Which is the order of increasing δ values downfield from TMS for the methyl groups shown (lowest first)? (Sec. 12.8)
CH3 Br CH3 I CH3 OH CH3 F I a) b) c) d)
II
III
IV
I, III, IV, II II, I, III, IV IV, II, III, I III, IV, II, I
10. Which is the order in increasing chemical shift values in the 1H-NMR spectrum for the indicated hydrogen atoms (lowest first)? (Sec. 12.8)
O CH3 CH CH CH2 COH I
a) b) c) d)
II
III
IV
IV, II, III, I I, III, II, IV III, I, IV, II II, IV, I, III
139
Chapter 12 Nuclear Magnetic Resonance Spectroscopy
11. Which is the splitting pattern for the indicated hydrogen atom? (Sec. 12.9)
O
CH3
CH3COCH CH3 a) b) c) d)
septet quartet doublet singlet
12. Which is the splitting pattern for the hydrogen atoms in 2,2-dibromopropane? (Sec. 12.9) a) b) c) d)
septet quartet doublet singlet
13. The splitting pattern for a compound with molecular formula C3H5OCl gave a quartet and a triplet. Which is the most likely structure for this compound? (Sec. 12.9)
O a) CH3CCH2Cl
b) O
Cl
O
O
c) CH3CH2CCl
d) ClCH2CH2CH
14. Which compounds show signal splitting in the 1H-NMR spectrum? (Sec. 12.9)
CH3 O
O CH3 CH3COC
CH3
CH3
CH3
C
CH3
COCH2CH3
CH3O C
CH3
I
CH3 III
II
a) b) c) d)
CH3
OCH3 IV
I, II III, IV I, III II, IV
15. Which compound has a singlet in the 1H-NMR at approximately 2.0 ppm and integrates to 3 hydrogens? (Sec. 12.8, 12.9)
O
O
a) CH3CHOCH CH3
b) CH3COCH2CH3 O
c) CH3CH2CH2OCH
O d) CH3OCCH2CH3 140
Chapter 12 Nuclear Magnetic Resonance Spectroscopy 16. Which compound has four sets of signals in the 1H-NMR spectrum? (Sec. 12.6)
O
O
a) CH3CHOCH CH3
b) CH3COCH2CH3 O
c) CH3CH2CH2OCH
O d) CH3OCCH2CH3
17. Which compounds have 3 signals in the 13C NMR spectrum? (Sec. 12.10)
HO
OH
OH
OH
OH
OH OH I
II a) b) c) d)
IV
III
I, II I, II, III I, III I, II, III, IV
18. Which is the order of increasing δ values in the 13C NMR spectra for the following carbon atoms? (Sec. 12.8) CH4 I a) b) c) d)
CH3F II
CH3Br III
CH3OH IV
CH3Cl V
III, V, II, IV, I I, IV, II, V, III V, IV, II, III, I I, III, V, IV, II
19. A compound has a single signal in the 13C NMR spectrum and a single signal in the 1H-NMR spectrum. Which is most likely the compound? (Sec. 12.6, 12.10) a) b) c) d)
dimethyl ether diethyl ether 2,2-dimethylpropane methyl ethanoate
20. A compound has two signals in the 13C NMR spectrum and a single signal in the 1H-NMR spectrum. Which is most likely the compound? (Sec. 12.6, 12.10) a) b) c) d)
dimethyl ether diethyl ether 2,2-dimethylpropane methyl ethanoate
141
Chapter 12 Nuclear Magnetic Resonance Spectroscopy 21. A compound has three signals in the 13C NMR spectrum and two signals in the 1H-NMR spectrum. Which is most likely the compound? (Sec. 12.6, 12.10) a) bromobenzene b) para dibromobenzene c) ortho dibromobenzene d) meta dibromobenzene 22. Which are the characteristic shift ranges for the indicated hydrogen atoms? (Sec. 12.8)
O H3C
CCH2CH2CH3 H
I
III
IV
II a) b) c) d)
I = 0.8-1.0, II = 6.5-8.5, III = 2.2-2.5, IV = 2.1-2.3 I = 0.8-1.0, II = 2.2-2.5, III = 6.5-8.5, IV = 2.1-2.3 I = 2.2-2.5, II = 6.5-8.5, III = 0.8-1.0, IV = 2.1-2.3 I = 2.2-2.5, II = 6.5-8.5, III = 2.1-2.3, IV = 0.8-1.0
23. The compounds shown below can be distinguished by which 1H-NMR characteristics? (Sec. 12.11)
O O
I) number of signals II) splitting III) integration IV) chemical shift a) b) c) d)
I, II, IV I, IV II IV
142
Chapter 12 Nuclear Magnetic Resonance Spectroscopy 24. The compounds shown below can be distinguished by which 1H-NMR characteristics? (Sec. 12.11)
Cl
Cl Cl
Cl I) number of signals II) splitting III) integration IV) chemical shift a) b) c) d)
I, II I, IV I, II IV
25. The compounds shown below can be distinguished by which 1H-NMR characteristics? (Sec. 12.11)
O
O O
I) number of signals II) splitting III) integration IV) chemical shift a) b) c) d)
I, II, III I, III, IV I, II IV
Fill in the Blank 1. The number of 1H signals for the following molecule is _____________. (Sec. 12.6)
O O
143
Chapter 12 Nuclear Magnetic Resonance Spectroscopy
2. The number of 1H signals for the following molecule is _____________. (Sec. 12.6)
CH3
CH3 3. The number of 1H signals for isopropyl ethyl ether is _____________. (Sec. 12.6) 4. The splitting of the three 1H signals of methyl propanoate are (left to right as drawn) _____, ______, ______. (Sec. 12.9)
O O 5. The splitting of the three 1H signals of tetrahydropyran are (top to bottom as drawn) _____, ______, ______. (Sec. 12.9)
O
6. The integration of the 1H signal at 2.2 ppm for 3-pentanone is _________. (Sec. 12.7)
O 7. The integration of the 1H signal at 3.8 ppm for dipropyl ether is _________. (Sec. 12.7, 12.8) 8. The number of 13C signals for meta dimethoxybenzene is ________. (Sec. 12.10) 9. The expected chemical shift range (in ppm) for the indicated carbon of ethyl benzoate is ___________. (Sec. 12.10)
O O
144
Chapter 12 Nuclear Magnetic Resonance Spectroscopy 10. The expected chemical shift range (in ppm) for the indicated protons of E-2-pentene is ___________. (Sec. 12.8)
H
H
True-False 1. The number of 1H-NMR signals for propyl propanoate is 3. (Sec. 12.6)
O O 2. The number of 1H-NMR signals for para methoxytoluene is 4. (Sec. 12.6) 3. The splitting of the signal for the indicated protons of 3-methylcyclohexanone is a quartet. (Sec. 12.9)
O
H CH3 4. The splitting of the signal for the indicated protons of isopropyl formate is a septet. (Sec. 12.9)
CH3
O H
O
H
CH3
5. The integration of the signal that includes the indicated protons of isopropyl formate is 3. (Sec. 12.7)
CH3
O H
O
H
CH3
145
Chapter 12 Nuclear Magnetic Resonance Spectroscopy 6. The integration of the signal that includes the indicated protons of meta hydroxybenzene is 2. (Sec. 12.7)
OH
OH H 7. Ethyl 3-oxopentanoate has 5 proton signals and 5 carbon signals in the NMR spectra. (Sec. 12.6, 12.10)
O
O O
8. 1,4-Cyclohexanedione has 2 proton signals and 4 carbon signals in the NMR spectra. (Sec. 12.6, 12.10)
O
O 9. A 1H-NMR shows a single signal and a 13C-NMR shows two signals. A possible structure for this compound is,
O (Sec. 12.6, 12.10) 10. A 1H-NMR shows a single signal and a 13C-NMR shows two signals. A possible structure for this compound is,
O
(Sec. 12.6, 12.10)
146
Chapter 12 Nuclear Magnetic Resonance Spectroscopy Answers Multiple Choice 1. b 2. d 3. b 4. b 5. c 6. d 7. d 8. d 9. b 10. b 11. a 12. d 13. c 14. d 15. b 16. c 17. d 18. d 19. a 20. c 21. c 22. d 23. d 24. b 25. b Fill in the Blank 1. 4 2. 4 3. 4 4. t, q, s 5. t, q(5), q(5) 6. 4 7. 4 8. 5 9. 165-200 ppm 10. 5-5.7 ppm True-False 1. F 2. T 3. F 4. T 5. F 6. T 7. F 8. F 9. T 10. T
147
Chapter 13 Aldehydes and Ketones Multiple Choice 1. Which compounds are named correctly? (Sec. 13.3)
OH
CH3
O
O CH
CH
HO O CH3CHCOH
o-hydroxybenzaldehyde I
2-hydroxypropanoic acid III
2-methylbenzaldehyde II
H O
O
O
C O
benzophenone V
cinnamaldehyde VI
I, II, III IV, V, VI II, IV, V III, IV, VI
2. Which is the correct structure for 2-hydroxybenzophenone? (Sec. 13.3)
OH a)
O
CH3CH
O
CH
b)
C OH O
O c)
C
CH3
CH
d) OH
OH
3. How many chiral ketones are there that have the molecular formula C6H12O? (Sec. 13.2) a) b) c) d)
C CH3
1,3-butanedione IV
a) b) c) d)
C
CCH3
CH3CCH2CH
H
1 2 3 4 148
Chapter 13 Aldehydes and Ketones 4. Which compounds are acetals? (Sec. 13.7)
CH3
O
O
O
II
I
O
O
a) b) c) d)
OH
OCH3
III CH3
O
CH3
CH3
O
O
O
IV
V
VI
CH3
I, II, III IV, V, VI III, IV, VI II, IV, V
5. Which is the product of the following reaction? (Sec. 13.7)
O
O
H3O H2O
O a) CH3CH2CH + O
O b) HOCH2CH2CH2OH + HCH
CH3OH
O
O
c) CH3CCH2CH2CH2CH
O
d) HCCH2CH + CH3OH
6. Which compound reacts with aqueous acid to give an aldehyde? (Sec. 13.7)
O
HO
H3C a)
O
b)
OCH3
CH3 O
c)
O
d)
CH3 OCH3
149
Chapter 13 Aldehydes and Ketones
7. A Grignard reagent is prepared by reacting cyclopentanol with first thionyl chloride and then magnesium in ether. The Grignard reagent is then reacted with acetaldehyde (ethanal) and the reaction mixture acidified. What is the major final product of this series of reactions? (Sec. 13.6)
OH
OH
CHCH3
a)
b)
CH2CH2OH
c)
d)
CH2CH3 8. Which is the major product of the reaction of ethyl Grignard and propiophenone (ethyl phenyl ketone)? (Sec. 13.6)
CH2CH3 a)
CH2CH3 b)
CCH2CH3
CCH3
OH
OH
CH3
CH3
c)
CCH2CH3
CCH3
d)
OH
OH
9. Which is the major product of the following reaction? (Sec. 13.11)
O O
NaBH4 H2O
Mg ether
HCl
OH
OH b)
a)
HO
OH c)
d)
10. Which reaction does not lead to 3-methyl-3-hexanol? (Sec. 13.6) a) b) c) d)
2-butanone + propylmagnesium bromide 3-hexanone + methyl magnesium bromide 2-pentanone + ethylmagnesium bromide 3-pentanone + ethylmagnesium bromide
150
CH2OCH3
Chapter 13 Aldehydes and Ketones
11. Which is the major product of the following reaction? (Sec. 13.6)
MgBr +
a)
D
CH3CH2ND2
b)
H
ether
c)
ND2
d)
NDCH2CH3
12. Which is the major product of the following reaction? (Sec. 13.6)
O ether
CCH3 + CH3MgBr
OH a)
CCH3
H3O
OH b)
CH2CHCH3
CH3 OH c)
CHCH2OH d)
CHCH2CH3
CH3 13. Which is the major product of the reaction of cyclopentylamine and benzaldehyde followed by nickel and hydrogen? (Sec. 13.8)
a)
CH2NH
b)
NH
c)
NHCH2
d)
CH2NHCH2
151
Chapter 13 Aldehydes and Ketones
14. The following product can be made from the reductive amination of which combination of compounds? (Sec. 13.8)
NH2 CH
a) b) c) d)
benzaldehyde and benzylamine benzaldehyde and aniline benzophenone and ammonia acetophenone and ammonia
15. Which is the major product of the following reaction? (Sec. 13.11)
O CH
NaBH4 H2O
O a)
COH
b)
CH2OH
d)
CH2OH
O c)
CH
16. 1-Hexene was treated with dilute sulfuric acid. The product of that reaction was reacted with potassium dichromate in sulfuric acid. This product was then treated with methanol in hydrochloric acid. What is the major product of this series of reactions? (Sec. 13.7, 13.10)
OCH3 a) CH3CH2CH2CH2CH2CH
OCH3 b) CH3CH2CH2CH2CCH3
OCH3
OCH3
O
O
c) CH3CH2CH2CH2CH2COCH3 d) CH3CH2CH2CH2CH2CCH3
152
Chapter 13 Aldehydes and Ketones
17. Which oxidation conditions are used in the industrial transformation of cyclohexanone to adipic acid? (Sec. 13.10)
a) K2Cr2O7 / H2SO4 b) KMnO4 c) HNO3 d) AgNO3 / NH3 18. Which is the best procedure for the following preparation? (Sec. 13.6, 13.10, 13.11)
O
O
CH2CH
CH
a)
CH3MgBr H2SO4
K2Cr2O7 H2SO4
b)
Ag(NH3)2 NH3/H2O
CH3MgBr H2SO4
c)
NaBH4 H2O
HCl
d)
LiAlH4 H2O
HBr
NaBH4 H2O Mg ether
Mg ether
H2CO
PCC
CO2 H3O+
19. Which is the best procedure for the following preparation? (Sec. 13.8)
O
N
HN a)
HN
NaBH4 H2O
HN
HN c)
Ni / H2
NaBH4 H2O
b)
d)
Ni / H2
153
Chapter 13 Aldehydes and Ketones
20. Which compound is a Schiff base? (Sec. 13.8)
NH2
a)
b) H2N N
c) CH3CH2NH3 CH3
d)
NH
21. Arrange the compounds in order of increasing solubility in water (least first). (Sec. 13.4)
O CH
O O
I a) b) c) d)
CH3CH2CH
II
O
H3C
CHCH2CH2CH2CH2CCH3 H3C
III
IV
I, II, III, IV IV, I, II, III IV, III, II, I II, II, I, IV
22. Arrange the compounds in order of increasing solubility in water (least first). (Sec. 13.4)
O
OH
CH3CH2CH2CH
CH3CH2CH2CH2
CH3CH2CH2CH2CH3
I
II
III
a) b) c) d)
O CH3CH2
CH2CH3 IV
II, I, IV, III I, II, IV, III III, IV, I, II II, I, IV, III
23. Arrange the compounds in order of increasing boiling point (lowest first). (Sec. 13.4)
O
OH
CH3CH2CH2CH
CH3CH2CH2CH2
CH3CH2CH2CH2CH3
I
II
III
a) b) c) d)
II, I, IV, III I, II, IV, III III, IV, I, II II, I, IV, III
154
O CH3CH2
CH2CH3 IV
Chapter 13 Aldehydes and Ketones
24. Arrange the compounds in order of increasing boiling point (lowest first). (Sec. 13.4)
O CH O I a) b) c) d)
CH3CH2CH
II
O
H3C
O
CHCH2CH2CH2CH2CCH3 H3C
III
IV
III, II, I, IV IV, I, II, III IV, III, II, I II, II, I, IV
25. Which structure is the major tautomer of 2-pentanone in aqueous acid? (Sec. 13.9)
OH
OH
a)
OH
b)
c)
OH d)
Fill in the Blank 1. The IUPAC name of the following structure is ___________________________. (Sec. 13.3)
O
O
Br 2. The IUPAC name of the following structure is ___________________________. (Sec. 13.3)
O
O
3. The major product that completes the following reaction is,
O
1)
MgBr , ether
H 2) H+, H2O (Sec. 13.6)
155
Chapter 13 Aldehydes and Ketones
4. The starting material that completes the following reaction is,
1)
MgBr
, ether
HO
2) H+, H2O (Sec. 13.6) 5. The starting material that completes the following reaction is,
OH
HO
O H+
O
(Sec. 13.7)
6. The reagents that complete the following reaction are,
O
N
(Sec. 13.8) 7. The starting material that completes the following reaction is,
NH3
NH2
H2, Ni (Sec. 13.8) 8. The reagents that complete the following reaction are,
O
O H
OH (Sec. 13.10)
156
Chapter 13 Aldehydes and Ketones
9. The major product that completes the following reaction is,
1) LiAlH4, ether O
2) H2O (Sec. 13.11)
10. The reagents that complete the following reaction are,
O
OH H (Sec. 13.11)
True-False 1. The name of the following molecule is 1,5-cyclohexanecarbaldehyde. (Sec. 13.3)
O H
2. The name of the following compound is 3-cyclohexenone. (Sec. 13.3)
O
3. The order of boiling points for the following functional groups, of similar molecular weights, is, ether > aldehyde > alcohol > carboxylic acid
(Sec. 13.4)
4. The enol form of cyclohexanone is,
OH
(Sec. 13.9)
157
Chapter 13 Aldehydes and Ketones
5. The product of the reaction of acetone (propanone) with bromine and acetic acid is 1-bromo-2propanone. (Sec. 13.9) 6. The product of the reaction of 2-hydroxybutanal with phenyl magnesium bromide is 1-phenyl-1,2butanediol. (Sec. 13.6) 7. The product of the reaction of benzaldehyde with silver ammonium nitrate (Tollen’s reagent) is benzoic acid. (Sec. 13.10) 8. The product of the reaction of 3-pentanone with ammonia, hydrogen, and nickel is 3-pentanamine. (Sec. 13.8) 9. The mechanism for the formation of the enol form of propanal under basic conditions (NaOH) is,
O
O H
H
Na+ H
+ H2O
H -OH
(Sec. 13.9)
10. Two ways to drive the acetal reaction to completion are to use excess alcohol and remove water produced. (Sec. 13.7)
158
Chapter 13 Aldehydes and Ketones Answers Multiple Choice 1. a 2. b 3. b 4. c 5. b 6. c 7. a 8. a 9. a 10. d 11. a 12. a 13. c 14. c 15. b 16. b 17. c 18. c 19. c 20. d 21. b 22. c 23. c 24. a 25. c Fill in the Blank 1. R – 4-bromo-5-oxohexanal 2. E – 4-nonene-2,8-dione 3.
OH H
4.
O
159
Chapter 13 Aldehydes and Ketones 5.
O H 6.
H2N Ni, H2 7.
O H 8. H2CrO4 or Ag+ conditions 9.
OH 10. 1) NaBH4, ethanol 2) H2O True-False 1. F 2. T 3. F 4. F 5. T 6. F 7. T 8. T 9. F 10. T
160
Chapter 14 Carboxylic Acids Multiple Choice 1. Which is the IUPAC name for the following compound? (Sec. 14.3)
O C
H3C a) b) c) d)
O CH2 CH2 CH2 C OH
2-oxohexanoic acid 5-oxohexanoic acid methyl butyroxo ketone 4-ketopentanoic acid
2. Which is the correct structure for Z-3-hexenedioic acid? (Sec. 14.3)
O
O
CH2COH a)
H C
H
H b)
CH2COH
HOCH2C
C C
CH2COH H
O
O O
O H c) H
C CH2COH C
COH H
d)
CH2COH
H
O
COH O
3. Which is the IUPAC name for the following compound? (Sec. 14.3)
H C H
C COH O
a) b) c) d)
E-3-phenylpropenoic acid Z-3-carboxy-1-phenylethene E-1-phenylpropenoic acid Z-benzylacrylic acid
161
Chapter 14 Carboxylic Acids
4. Which is the structure for potassium hydrogen oxalate? (Sec. 14.3)
a)
O
O
CO K
CO K
CH2
b)
CH2 4
COH
COH
O
O
c)
CO K COH O
5. Which structures are correctly named (common name)? (Sec. 14.3)
O
O CH3COH I formic acid O COH CH2 COH O III malonic acid a) b) c) d)
H2C
O
O
CHCOH II
acrylic acid O COH COH O IV succinic acid
I, II II, III III, IV II, IV
162
CO K d) COH O
Chapter 14 Carboxylic Acids
6. Arrange the compounds in order of increasing solubility in water (least soluble first). (Sec. 14.4)
O
O
HOC
CH2 CH2 CH3
K OC CH2 CH2 CH3
I
II
O HOC
O CH3
HOC
III a) b) c) d)
IV
II, III, I, IV IV, I, III, II I, IV, II, III II, III, I, IV
7. Arrange the compounds in order of increasing order of solubility in water (least soluble first). (Sec. 14.4)
O
O
O
COH
CO K
COH
8.
C C
CO K
CO K
COH
O
O
O
I a) b) c) d)
O
II
III
O
O
IV
IV, III, I, II I, III, II, IV IV, II, III, I I, II, III, IV
Which compounds are soluble in water? (Sec. 14.4)
O
O HOC
CH2 CH3 I
a) b) c) d)
HOCH2CH2CH3 II
H3C
C III
I, II, IV I, III, IV I, II, III II, III, IV
163
CH3
CH3CH2CH3 IV
Chapter 14 Carboxylic Acids
9. Arrange the compounds in order of increasing boiling point (lowest first). (Sec. 14.4)
O CH3
O
O
C OH
COH
CO Na
C
CH3
H II
I a) b) c) d)
III
IV
II, I, III, IV I, II, III, IV III, I, II, IV IV, I, II, III
10. Arrange the compounds in order of increasing boiling point (lowest first). (Sec. 14.4)
O
O
O
HOCCH2CH2COH
O
HOCCH2CH2CH3
I
HOCCH2CH2CH2CH2CH3
II a) b) c) d)
O
HOCCH2CH2CH2CH2COH IV
III
I, II, III, IV IV, II, II, I II, III, I, IV I, II, IV, III
11. Arrange the compounds in order of increasing acidity (lowest first). (Sec. 14.5)
Cl CH3
C
Cl COH
Cl
CH2CH2COH
H O I a) b) c) d)
CH3
O
C
O COH
CH3CH2COH
Cl O
II
III
IV, I, II, III III, II, IV, I IV, II, I, III II, I, III, IV
164
O
IV
Chapter 14 Carboxylic Acids
12. Arrange the compounds in order of increasing acidity (lowest first). (Sec. 14.5)
OH O COH
H 3C C H I a) b) c) d)
CH3CH2
O
O
COH
C OH
O Cl
IV
III
II III, II, I, IV I, II, IV, III II, III, I, IV II, I, III, IV
13. Arrange the compounds in order of increasing acidity (lowest first). (Sec. 14.5)
O
O
O
O
COH
COH
COH
COH
CH3
NO2
III
IV
Cl I a) b) c) d)
II
IV, I, III, II III, II, I, IV II, III, I, IV III, II, IV, I
165
CH2
COH
Chapter 14 Carboxylic Acids
14. Which reactions proceed nearly to completion as written? (Sec. 14.5)
O I.
O
CH3COH +
NaOH
CH3CO Na
O II.
CH3COH +
Na2CO3
CH3CO Na
CH3COH +
NaHSO4
CH3CO Na O
H2CO3
+
H2SO4
CH3CO Na
I, II III, IV I, III II, IV
15. Which mixtures can be separated by treatment with aqueous NaOH? (Sec. 14.5)
O OH
CH2OH
COH
CH2COH and
I
II O
COH
a) b) c) d)
O
and
O CH2OH
O
O
CO Na
CH3COH + a) b) c) d)
+
O
O IV.
H2O
O
O III.
+
COH
OH
and
and
III
IV
I, II III, IV II, IV I, III
166
+
COH
Chapter 14 Carboxylic Acids
16. Which reactions yield the same carboxylic acid? (Sec. 13.10)
O I.
CH2CH
II.
CH2CH2Br
III.
CH2CH3
IV. a) b) c) d)
CH2OH
K2Cr2O7 H2SO4
+ Mg
KMnO4
ether
CO2
H3O
OH K2Cr2O7 H2SO4
I, II III, IV II, IV I, III
17. Which compounds undergo thermal decarboxylation? (Sec. 14.9)
O O
COH I.
COH
II.
COH
COH
O
O O
O
O COH III.
C
C CH3
CH2COH IV.
CH3 a) b) c) d)
O
I, II II, III III, IV II, IV
167
H3O
Chapter 14 Carboxylic Acids
18. Which conditions are best for the transformation? (Sec. 14.6)
O
O O
a) b) c) d)
HO
COH
COH
LiAlH4 NaBH4 Ag(NH3)2OH / NH4OH Pyridine . Cr3O4
19. Which conditions are best for making the following compound? (Sec. 14.7)
O CH3
C
OCH2CH2CH3 O
a)
CH3OH
+
CH3CH2COH
O b) CH3COH
+
HCl
O +
CH3CH2COH
+ HCl
O c)
CH3COH
+ CH3CH2CH2OH + HCl O
d) CH3CH2CH2O Na + CH3COH 20. The following compound is prepared by Fischer esterification of which combination of reagents? (Sec. 14.7)
O COCH3 COCH3 O a) b) c) d)
1,2-dihydroxybenzene and methanol salicylic acid and methanol phthalic acid and methanol benzoic acid and methanol
168
Chapter 14 Carboxylic Acids
21. Which compound is prepared by reaction of benzoic acid with ammonia and water? (Sec. 14.5)
O C
O C
NH2
O CO
O NH4
CH2NH2
NH3 a)
b)
c)
d)
22. Which conditions will convert pentanoic acid to pentanoyl chloride? (Sec. 14.8) a) b) c) d)
HCl NaCl SOCl2 LiAlH4 followed by HCl
23. Acetophenone (methyl phenyl ketone) is the product from thermal degradation of which compound? (Sec. 14.7)
O
O COH CH2 C H
O
O
COH
CCH2COH
O
C CCH3
CH2CCH2COH
H O
COH O a)
b)
d)
c)
24. A mixture of the following compounds was extracted in the order 1) 1 M HCl, 2) 1 M NaOH, 3) ether. Which compound is extracted into the basic layer? (Sec. 14.5)
O NH2
COH
O C
I a) b) c) d)
II
III
I II III All of the above 169
O
CH3
Chapter 14 Carboxylic Acids
25. A mixture of the following compounds was extracted in the order 1) 1 M HCl, 2) 1 M NaOH, 3) ether. Which compound is extracted into the ether layer? (Sec. 14.5)
O COH
NH2
O C
I a) b) c) d)
II
CH3
III
I II III All of the above
Fill in the Blank The IUPAC name of the following structure is ___________________________. (Sec. 14.3)
O OH 2. The IUPAC name of the following structure is ___________________________. (Sec. 14.3)
O
O OH
3. The major product that completes the following reaction is,
O
1) LiAlH4, ether OH 2)H2O (Sec. 14.6)
170
Chapter 14 Carboxylic Acids 4. The reagents that complete the following reaction are,
O
O
OH
O
OH
OH (Sec. 14.6)
5. The major product that completes the following reaction is,
O
OH
OH H+ (Sec. 14.7) 6. The reagents that complete the following reaction are,
O
O
Cl
OH
(Sec. 14.8) 7. The major product that completes the following reaction is,
O
O
heat OH
(Sec. 14.9) 8. The reagents that complete the following reaction are,
O
O OH
O (Sec. 14.7)
171
Chapter 14 Carboxylic Acids
9. The reagents that complete the following reaction are,
O
O OH
OH (Sec. 14.6)
10. Complete the following reaction mechanism for the Fisher esterification of acetic acid. (Sec. 14.7)
O
+O H
H+ OH
OH OH + OCH3 H
OH HOCH3
OH
+O H
O OCH3
H+
+ OH2 OCH3
OCH3
True-False 1. The order of acidity of the following carboxylic acids is,
O
O OH
>
Cl OH
O
>
O OH
Cl
>
Cl OH
(Sec. 14.5) 2. The order of acidity of the following carboxylic acids is,
Cl
Cl
O
O OH >
Cl
Cl
O
O OH
>
Cl
Cl
(Sec. 14.5)
172
OH
>
OH
Chapter 14 Carboxylic Acids
3. The order of acidity of the following carboxylic acids is,
O Cl
>
OH
F
O
O
O
> OH
OH
> Br
OH
(Sec. 14.5) 4. The name of the following compound is 2,2-dibromopropanedioic acid. (Sec. 14.3)
O
O
Br
Br
HO
OH
5. The order of boiling points for the following compounds is,
O OH
>
O
OH >
>
O
(Sec. 14.4) 6. The structure of Z-2-butendioic acid is,
O OH
HO O
(Sec. 14.3)
7. The product of heating 4-oxopentanoic acid is butanone and carbon dioxide. (Sec. 14.9) 8. The product of the reaction of hexanoic acid and chromic acid is hexanol. (Sec. 13.10) 9. The product of the reaction of benzoic acid and sodium hydroxide is sodium benzoate. (Sec. 14.5) 10. The product of the reaction of acetic acid and thionyl chloride is acetyl chloride. (Sec. 14.8)
173
Chapter 14 Carboxylic Acids
Answers Multiple Choice 1. b 2. c 3. a 4. c 5. b 6. b 7. a 8. c 9. d 10. c 11. c 12. c 13. b 14. a 15. d 16. b 17. b 18. b 19. c 20. c 21. b 22. c 23. b 24. b 25. c Fill in the Blank 1. 2,4-cyclopentadiene carboxylic acid 2. 2,2-dimethyl-3-oxobutanoic acid 3.
OH 4. 1) NaBH4, ethanol, 2) H2O 5.
O O 6. SOCl2 7.
O CH3 8. phenol, H+ 174
Chapter 14 Carboxylic Acids 9. Pt, H2 10.
O
H+ OH
+O H
OH OH + OCH3 H
OH HOCH3
OH
+O H
O OCH3
H+
+ OH2 OCH3
OCH3
True-False 1. F 2. T 3. F 4. T 5. F 6. F 7. F 8. F 9. F 10. T
175
Chapter 15 Functional Derivatives of Carboxylic Acids Multiple Choice 1. Which is the correct structure for phenyl benzoate? (Sec. 15.2)
O
O
CO
a)
b)
OCCH2 O
O c)
CH2OCCH2
d)
CH2OC
2. Which compounds are named correctly? (Sec. 15.2)
O
O
O
O
O O CH3CH2COCH3
succinic anhydride I O
O
O
γ-butyrolactone IV a) b) c) d)
ethyl acetate III
cyclohexyl anhydride II
HCN
CH3
CH3 N,N-dimethylformamide V
I, II, III II, III, IV I, IV, V III, IV, V
3. Which is the common name for the following compound? (Sec. 15.2)
O CNH2 OH a) b) c) d)
aspirin cyclosporin succinamide salicylamide
176
Chapter 15 Functional Derivatives of Carboxylic Acids
4. Which functional groups are correctly named? (Sec. 15.2)
O
O
O
HCN
CH3
O CH3CH2COCH3
CH3 anhydride I
amide II
ester III
O O
O
CH3CH2COCCH2CH3
acyl chloride V
lactone IV a) b) c) d)
CH3CCl
II, III, IV III, IV, V II, III, V I, II, IV
5. What is the order of decreasing reactivity toward nucleophilic acyl substitution for these carboxylic acid derivatives (most reactive first)? (Sec. 15.3)
O
O
O
O O
CH3COCH3
CH3CCl
CH3CNH2
CH3COCCH3
I
II
III
IV
a) b) c) d)
II, IV, I, III III, IV, I, II IV, I, II, III I, II, III, IV
6. Carboxylic acids and amides have in general higher boiling points than esters and anhydrides because of which property? (Sec. 15.2, 14.4) a) b) c) d)
dispersion forces resonance stabilization conjugated functional groups hydrogen bonding
177
Chapter 15 Functional Derivatives of Carboxylic Acids
7. Which is the order of increasing boiling point of the following compounds (lowest first)? (Sec. 15.2, 14.4)
O CH3COCH3 I a) b) c) d)
O
O
CH3CNH2 III
CH3COH IV
O CH3CCl II
IV, I, III, II I, III, IV, II II, I, III, IV IV, III, II, I
8. Which is the order of increasing solubility in water of the following compounds (least first)? (Sec. 15.2, 14.4)
O
O
CH3CH2COCH3
CH3CH2CCl
I
II
O
O
CH3CH2CNH2
CH3CH2COH IV
III a) b) c) d)
I, III, II, IV III, I, IV, II I, IV, II, III II, I, III, IV
9. Which reactions proceed at room temperature as written? (Sec. 15.4, 15.6, 15.7)
O
O
I CH3CH2CCl + H2O O
CH3CH2COH + HCl O
II CH3CH2CNH2 + H2O O O
CH3CH2COH + NH3
III CH3COCCH3 +2 NH3
CH3CNH2 + CH3CO NH4
O
O
O
IV HCOCH2CH3 + NH3 a) b) c) d)
O
HCNH2 + CH3CH2OH
I, II I, III II, III II, IV 178
Chapter 15 Functional Derivatives of Carboxylic Acids
10. The following reaction is fastest when Z is which group? (Sec. 15.3)
O
O Z + OH
C
CO
+ HZ
O O
CH3
a)
CH3O
b)
CH3CO
c)
d)
11. Which is the major product when 1,2-diaminoethane is heated with dimethyl oxalate? (Sec. 15.6)
O
O
b) O
O
O
O
a) CH3CN CH2CH2 NCCH3 H
H O
O O
c) HN
NH
H
d) CH3CN C
O NCCH3
H CH3 H 12. Which are the best conditions for the following preparation? (Sec. 15.6)
O
O
COH
CN
CH3 CH3
CH3
CH3 a) b) c) d)
SOCl2 NaOH NH3
(CH3)2NH (CH3)2NH CH3CH2Br
(CH3)2NH room temp 179
Chapter 15 Functional Derivatives of Carboxylic Acids 13. Which compounds will yield benzoic acid when hydrolyzed? (Sec. 15.4) I) benzyl ethanoate II) benzamide III) phenyl ethanoate IV) methyl benzoate a) b) c) d)
I, II III, IV I, III II, IV
14. Which is the product from the following reaction? (Sec. 15.6, 15.9)
O O
NH3
1) LiAlH4 2) H2O
H
H
N
CH2CH2OH
N
a)
b)
OH
c)
OH d) CH2CH2NH2
NH2 15. Which of the following compounds does not yield nicotinamide when reacted with ammonia at room temperature? (Sec. 15.6)
O
O
OH
Cl N
N
I a) b) c) d)
O
O O N
I, II II, IV II, III III, IV
180
CH3
OCH3 N
III
II
O
IV
Chapter 15 Functional Derivatives of Carboxylic Acids 16. Which is the product of the reaction of 4-aminophenol with 1 equivalent of acetic anhydride? (Sec. 15.5)
O NH2
O
HNCCH3
NH2
O
HNCCH3
CCH3 a)
b) OCCH3
c)
d)
OH
OH
OCCH3
O
O
17. Which is the product of the reaction of phthalic anhydride with 1 equivalent of methanol? (Sec. 15.5)
O
O
O
O O
COH
COCH3
CCH3
COCCH3
a)
b)
c)
d)
COCH3
COCH3
COH
COH
O
O
O
O
18. Which reactions can be used to prepare an ester? (Sec. 15.5)
OH
O
SOCl2
COH
I
O CO Na
II
O COH
III
+
O IV a) b) c) d)
OH
+
CNH2 +
OH
OH
II, IV I, III I, II III, IV
181
H3O
heat
Chapter 15 Functional Derivatives of Carboxylic Acids 19. Which is the final product of a series of reactions starting with ethyl benzoate and reacting with 1) aqueous sulfuric acid and heat, 2) thionyl chloride, and 3) ethylamine? (Sec. 15.4, 15.6)
O a)
NCH2CH3
b)
CNCH2CH3
H
H
O c)
NCCH3
OH d)
CHNCH2CH3
H
H
20. Which is the product from the reaction of sodium benzoate and acetyl chloride? (Sec. 15.5, 15.6)
O a)
c)
O
COCH3 b)
OCCH3
O
O O
CCH3 d)
COCCH3
182
Chapter 15 Functional Derivatives of Carboxylic Acids 21. Partial hydrolysis of phenobarbitol gives which compound? (Sec. 15.4)
O NH
C6H5
O
CH3CH2
NH O O COH O
O I
H2NCNH2
II
C
COH
CH2CH3 O COH
OO III H2NCCOH
IV
CNH2 CH2CH3
a) b) c) d)
I, II II, III III, IV I, III
22. Which is the product of the reaction of ethyl benzoate with 2 equivalents of methyl grignard followed by aqueous acid? (Sec. 15.8)
a)
O
CH3
O
CCH3
COH
COCH3
b)
CH3
c)
183
CH2CH2CH3 d)
Chapter 15 Functional Derivatives of Carboxylic Acids 23. Which is the major product of the following reaction? (Sec. 15.8)
O O
1)
CH3CH2MgBr
2)
H3O+
HO
a)
CH3CH2
c)
OH CH2CH3
HO CH3CH2
b)
O
OH CH2CH3
d)
CH3 CH3CH2
CH2CH3
OH CH2CH3
24. Which are the best conditions for the following reaction? (Sec. 15.9)
O CH3CH2CH2COCH2CH3
a)
1) NaBH4 / ether 2) H2O
b)
1) LiAlH4 / ether 2) H2O
c) d)
CH3CH2CH2CH2OH
1) CH3CH2MgBr / ether 2) H3O+ 1) NH3 2) H3O+
184
Chapter 15 Functional Derivatives of Carboxylic Acids 25. Which are the best conditions for the following reaction? (Sec. 15.9)
O
O
CH3CCH2COCH2CH3
a)
1) NaBH4 / ether 2) H2O
b)
1) LiAlH4 / ether 2) H2O
c) d)
OH
O
CH3CHCH2COCH2CH3
1) CH3CH2MgBr / ether 2) H3O+ 1) NH3 2) H3O+
Fill in the Blank 1. The IUPAC name of the following compound is ______________________________. (Sec. 15.2)
O O 2. The IUPAC name of the following compound is ______________________________. (Sec. 15.2)
O N
3. The reagents that complete the following reaction are,
O
O
OH
O
(Sec. 15.4)
185
Chapter 15 Functional Derivatives of Carboxylic Acids
4. The starting material that completes the following reaction is,
O
HN
N
(Sec. 15.6) 5. The reagents that complete the following reaction are,
O
O Cl
O (Sec. 15.5)
6. The major product that completes the following reaction is, MgBr
O
1) O 2) H+, H2O
(Sec. 15.8) 7. The reagents that complete the following reaction are,
O N
N (Sec. 15.9)
8. The reagents that complete the following reaction are,
O
O N H
OH
186
(Sec. 15.4)
Chapter 15 Functional Derivatives of Carboxylic Acids 9. The major product that completes the following reaction is,
OH
Cl O
(Sec. 15.5) 10. The major product that completes the following reaction is,
O
O
H2O
O
(Sec. 15.4)
True-False 1. The order of reactivity of the carboxylic acid derivatives with water is,
O
O
O Cl
> O
O >
O OCH2CH3
> NH2
(Sec. 15.3)
2. The order of reactivity of the carboxylic acid derivatives with ammonia is,
O
O
> NH2
> OCH2CH3
O
O O
>
O Cl (Sec. 15.3)
3. The name of the following compound is 3-methylbutanoyl 2-methylbutanoate. (Sec. 15.2)
O
O O
187
Chapter 15 Functional Derivatives of Carboxylic Acids 4. The structure for cyclohexanecarboxylic 2,2-dimethylpropanoic anhydride is,
O
O O (Sec. 15.2)
5. The product of the reaction of 5-pentanolactam with aqueous acid and heat is 5-aminopentanoic acid. (Sec. 15.4) 6. The product of the reaction of 4-butanolactone with ethanol and acid is butanoic acid and diethylether. (Sec. 15.5) 7. The product of the reaction of propanamide with ethanol is ethyl propanoate. (Sec. 15.5) 8. Sodium borohydride reduces propanamide to propanamine. (Sec. 15.9) 9. Lithium aluminum hydride reduces 3-oxobutanoic acid to 4-hydroxy-2-butanone. (Sec. 15.9) 10. The proper mechanism for the reaction of acetyl chloride and water is shown below. (Sec. 15.3)
O
O Cl
O
Cl O H + H
Cl OH
H2O
188
O + ClOH
Chapter 15 Functional Derivatives of Carboxylic Acids Answers Multiple Choice 1. a 2. c 3. d 4. c 5. a 6. d 7. c 8. d 9. b 10. d 11. c 12. a 13. d 14. d 15. b 16. b 17. a 18. b 19. b 20. d 21. a 22. b 23. a 24. b 25. a Fill in the Blank 1. 2. 3. 4.
E – 1-methylethyl 2-pentenoate or E – isopropyl 2-pentenoate N,N-dimethyl cyclohexane carboxamide H2O, H+ As written,
O
O
O Cl or
O
if heat is assumed,
O
OR may also be correct
189
Chapter 15 Functional Derivatives of Carboxylic Acids 5.
HO
6.
OH
7. 1) LiAlH4, ether 2) H2O 8. H2O, H+, heat 9.
O O 10.
O 2
OH
True-False 1. T 2. F 3. F 4. T 5. T 6. F 7. F 8. F 9. F 10. T
190
Chapter 16 Enolate Anions Multiple Choice 1. What is the order of increasing acidity for these compounds (least acidic first)? (Sec. 16.2)
O
O
O
CH3CH2OH
CH3CCH3
CH3COCH3
CH3COH
I
II
III
IV
a) b) c) d)
IV, III, II, I IV, II, III, I II, III, I, IV III, II, I, IV
2. What is the order of decreasing acidity for the indicated protons (most acidic first)? (Sec. 16.2)
O
O
CH3COCH2CH3 I
a) b) c) d)
CH3CCH3
O
O
CH3CCH2COCH2CH3
II
CH3CH2OH
III
IV
I, II, III, IV III, IV, II, I II, I, III, IV IV, III, II, I
3. Which compound undergoes the fastest exchange of hydrogen for deuterium when treated with D2O and a trace of OD-? (Sec. 16.2)
H3C O a)
CH3 O
O
O
b)
c) O
191
O d)
O
O
Chapter 16 Enolate Anions 4. Which are contributing resonance structures of the enolate formed by the treatment of butanone with base? (Sec. 16.2)
O H2C
C I
O CH2CH3
H3C
O
C II
CH2CH3 H3C
CH3
O
C
CH2CH2
H2C
IV a) b) c) d)
C
III H
O H3C
C
C V
CH2CH3
II, IV, V I, III, V II, IV, V I, III, IV
5. Which are the most important contributing structures for the enolate formed by the treatment of 2,4-pentanedione with base? (Sec. 16.2)
O
O
I a) b) c) d)
O
O
O
II
O
III
I, II II, III III, IV I, IV
192
O
O
IV
Chapter 16 Enolate Anions 6. Which are the reactants for the aldol product shown? (Sec. 16.3)
O
CH3 CHCHCH2CH3 OH
CH3
CH3
a) CH3CH2CHCH +
O
b) CH3CHCH2CH +
O
O
O O O
O
CH3
7. Which is the product of the series of reactions? (Sec. 16.3)
O
OH
CH3CH2CH
H3O heat
Rh H2 O
O CH3CH2CHCCH3 CH3
CH3CH2
CH C
C CH3
H
a)
b) CH3
CH3CH2CH2CHCH c)
O
d) CH3CH2CH2CH +
CH
c) CH3CH2CCH3 +
O
CH3 CH3CH2CH2CHCH2OH d)
193
Chapter 16 Enolate Anions
8. Which is the major product of the following reaction? (Sec. 16.3)
O
O
HCCH2CH2CH2CH2CCH3 +
Na OCH2CH3 O
CH3
O
O
O
CCH3
CH
a)
b)
c)
CH3
d)
9. Which of the following compounds can be used in an aldol self reaction to make a product with 5 or more carbon atoms? (Sec. 16.3) I) ethanal II) propanone (acetone) III) benzaldehyde IV) acetophenone a) b) c) d)
I, II III, IV I, III II, IV
10. Which is the major product from the reaction of 1,6-cyclodecanedione with hot aqueous NaOH? (Sec. 16.3)
OH
a)
OH b)
c)
O d)
11. How many possible compounds are formed when acetone and ethanal are mixed in the presence of base? (Sec. 16.3) a) b) c) d)
1 2 3 4
194
Chapter 16 Enolate Anions
12. How would you characterize this reaction forming fructose 1,6-bisphosphate? (Sec. 16.5)
CH2OPO32C O
CH2OPO32-
CH2OPO 32-
C O
HC OH
+
CH2OH
HO C
HC O
H
H C OH H C OH 2-
CH2OPO3 a) b) c) d)
aldol reaction substitution Claisen condensation Dieckmann Condensation
13. How many possible compounds are formed when ethyl propanoate and ethyl methanoate are mixed with sodium ethoxide? (Sec. 16.4) a) b) c) d)
1 2 3 4
14. Which pair of esters is most likely to provide a useful Claisen synthesis (Sec. 16.4) a) b) c) d)
ethyl propanoate and ethyl ethanoate ethyl benzoate and ethyl methanoate ethyl ethanoate and ethyl oxalate ethyl nicotinate and diethyl phthalate
15. Which is the major product formed in the following reaction? (Sec. 16.4)
O
O
CH3CH2OCCH2CH2CH2CH2CH2COCH2CH3 O
O
O
COCH2CH3
COCH2CH3 a)
O
b) O O
c)
NaOCH2CH3
CCH3
O d)
O
195
H3O
Chapter 16 Enolate Anions
16. What is the major product of the following reaction? (Sec. 16.4)
O
O
COCH2CH3 +
CH2COCH2CH3
1) NaOCH2CH3 2) H3O+
O COCH2CH3 C
a)
C
O b)
H
CCH2
O
O c)
CCH2C
d)
CCH COCH2CH3 O
17. What is the major product of the following reaction? (Sec. 16.4)
O CH2COCH2CH3
NaOCH2CH3
H3O
CH2COCH2CH3 O
O
O
CCH3
COCH2CH3
O
a)
b)
O
O
O
O COCH2CH3
c)
d) O
196
O
Chapter 16 Enolate Anions
18. Which compounds will undergo decarboxylation upon heating? (Sec. 16.4)
O
O
O
CH3CH2OCCH2COCH2CH3 I O
CH3CH2CCH2COCH2CH3 II
O
O
CH3CH2OCCH2COH
O
HOCCH2COH IV
III a) b) c) d)
O
I, II II, III III, IV II, IV
19. Which is the major product of the following series of reactions? (Sec. 16.6)
O
O
O
NaOH, H2O
+
O
CH3CH2OH
O
O
a)
O
O
O
b)
O
c)
CH3CH2ONa
O
O
O O
d)
O
O
197
HCl, H2O
heat
Chapter 16 Enolate Anions
20. Which is the product of the following series of reactions? (Sec. 16.4)
O CH3CH2COCH2CH3 1) NaOH, heat
1) NaOCH2CH3
+
2) H3O +
2) H3O
O O
heat
CH3CH2OC COCH2CH3 O
O
a) CH3CH2CCH2COH
O O b) CH3CH2C
O c) CH3CH2CCH3
COH
O d) CH3CHCH COH O
21. Which ester is likely to undergo a Claisen condensation to give this product? (Sec. 16.4)
O
O
CH3CH2CH2CCHCOCH2CH3 CH2CH3 a) b) c) d)
ethyl 2-methylpropanoate ethyl butanoate butyl ethanoate 2-methylpropyl ethanoate
198
Chapter 16 Enolate Anions 22. Which is the product of the reaction of ethyl 3-phenylpropanoate with 1) sodium ethoxide, 2) aqueous sodium hydroxide, 3) aqueous hydrochloric acid, and 4) heat? (Sec. 16.4)
O CH2CCH2CH2
a)
O CH2CH2CCH
b)
CH3 O c)
CH2CCH2 O
d)
CH2CH2CCH2CH2
23. The following synthesis will proceed by which reaction? (Sec. 16.5)
O
enzyme CH3CSCoA + CH3CSCoA catalysis a) b) c) d)
O
O
O
CH3CCH2CSCoA + CoASH
Claisen condensation Dieckmann condensation Aldol addition Aldol condensation reaction
24. Which is the major product of the following series of reactions? (Sec. 16.4)
O
SOCl2 CH3CH2OH
CH3COH
O
O
a) CH3CCH2COCH2CH3
NaOCH2CH3 1) NaOH, heat ethanol 2) H3O+
O
O
b)
heat
O
O
c) CH3CCH3 d) CH3CH2OCCH2COCH2CH3 O
199
Chapter 16 Enolate Anions
25. Which is the major product of the following series of reactions? (Sec. 16.4)
O
O
HOCCH2CH2CH2CH2CH2CCH3 OH
NaOCH2CH3 ethanol, heat CH3
CH3
CH3
a)
SOCl2 CH3CH2OH
C
b) COCH2CH3
O
O
CH3 C
O
c)
COCH2CH3
H3O
d) O
OH
Fill in the Blank 1. The major product of the following reaction is,
NaOH, H2O
O 2
(Sec. 16.3) 2. The starting material that completes the following reaction is,
O H
O
NaOH, H2O
+
H
(Sec. 16.3) 3. The starting material that completes the following reaction is,
O NaOH, H2O
H (Sec. 16.3)
200
O
Chapter 16 Enolate Anions
4. The major product of the following reaction is,
O
O
NaOH, H2O
+
O (Sec. 16.4)
5. The major product of the following reaction is,
O
NaOH, H2O
O
O O (Sec. 16.4)
6. The major product of the following reaction is,
O
O +
O
NaOH, H2O O
(Sec. 16.4) 7. The starting material that completes the following reaction is,
O
O
O
O
O
NaOH, H2O
+
O
O
O
H (Sec. 16.6) 8. The major product of the following reaction is,
O + CH3NH2 O (Sec. 16.6) 201
O
Chapter 16 Enolate Anions 9. The major product of the following reaction is,
O
O +
O
1) NaOCH2CH3, ethanol O
2) NaOH, H2O 3) HCl, H2O 4) heat
(Sec. 16.4) 10. The starting material that completes the following reaction is,
O
O
O
1) NaOCH2CH3, ethanol +
O
2) NaOH, H2O 3) HCl, H2O 4) heat
(Sec. 16.4, 16.6) True-False 1. The major enolate form of 2-pentanone is,
O (Sec. 16.2) 2. The major enolate form of ethyl 3-oxobutanoate is,
O
O O
(Sec. 16.2)
3. The position of the most acidic hydrogen of the following compound is indicated by the arrow.
O
O O
(Sec. 16.2)
202
O
O
Chapter 16 Enolate Anions 4. The position of the most acidic hydrogen of the following compound is indicated by the arrow.
O
O OH
(Sec. 16.2) 5. The major product of the reaction of two moles of ethyl benzoate with sodium ethoxide is,
O
O O
(Sec. 16.4) 6. The major product of the reaction of 2,4-pentanedione and 3-buten-2-one with ethoxide followed by hydroxide, acid, and heat sequentially, is,
O
O (Sec. 16.3)
7. 1-Cyclohexenecarbaldehyde can be produced from the following starting material and base.
O
H
H O
(Sec. 16.3)
8. The Michael addition of dimethylamine and 3-buten-2-one produces the following product,
O
N (Sec. 16.6) 9. The condensation of acetoacetyl-CoA with acetyl-CoA is an Aldol reaction. (Sec. 16.5) 10. The self condensation of Acetyl-CoA to Acetoacetyl-CoA is a Claisen reaction. (Sec. 16.5)
203
Chapter 16 Enolate Anions Answers Multiple Choice 1. d 2. b 3. d 4. b 5. b 6. a 7. c 8. b 9. d 10. d 11. d 12. a 13. b 14. c 15. a 16. c 17. b 18. c 19. a 20. b 21. b 22. d 23. a 24. c 25. c Fill in the Blank 1.
O
O
HO
or
2.
O H 3.
O
H
O H
204
Chapter 16 Enolate Anions 4.
O
O
5.
O
O O
6.
O
O O
7.
O H 8.
O O N H 9.
O
10.
O O
True-False 1. F 2. F 205
Chapter 16 Enolate Anions 3. T 4. F 5. F 6. F 7. F 8. T 9. T 10. T
206
Chapter 17 Organic Polymer Chemistry Multiple Choice 1. Which of the following are polymer architectures? (Sec. 17.2) I) linear II) tetrahedral III) star IV) ladder V) forked a) b) c) d)
II, III, IV III, IV, V I, III, IV I, II, IV
2. Which terms are correctly matched to their definitions? (Sec. 17.2) I) Plastic – a long chain molecule synthesized by linking together many single parts. II) Polymer – can be molded when hot and retains its shape when cooled. III) Thermoplastic - can be molded when hot and retains its shape when cooled. IV) Thermosetting plastic – can be molded when first prepared, but hardens irreversibly when cooled. a) b) c) d)
III, IV II, III I, II I, IV
3. Determine the repeat unit for the following polymer. (Sec. 17.1, 17.5, 17.6)
CH3
CH3
CH3
CH2CH O CH2CH O CH2CH O
CH3 a)
CH3
CH2CH O
b)
n
c)
CH O
CH2CH O CH2CH O CH3
CH3 d) n
CH3
CH2CH
207
n
n
Chapter 17 Organic Polymer Chemistry
4. Determine the repeat unit for the following polymer. (Sec. 17.1, 17.5, 17.6) CH2CH2
O
a)
c)
O CH2CH2 O
O CH2CH2 O
O
O CH2CH2 O
b)
n
O CH2CH2 O
O
n
O
O CH2CH2 O
d)
CH2CH2
O
CH2CH2
n O CH2CH2
5. Which characteristics are found in polymers with high degrees of crystallinity? (Sec. 17.4) I) regular, compact structures II) high Tm III) weak intermolecular forces IV) elasticity a) b) c) d)
I, III I, II III, IV II, IV
6. Which characteristics are found in polymers with low degrees of crystallinity? (Sec. 17.4) I) large molecular side groups II) high Tm III) strong intermolecular forces IV) elasticity a) b) c) d)
I, III II, III III, IV I, IV
7. Which terms are matched correctly with their definitions? (Sec. 17.4) I) Crystalline domain – order regions in the solid state of a polymer. II) Amorphous domain – disordered regions in the solid state of a polymer. III) Melt transition temperature – temperature at which a polymer undergoes the transition from hard to rubbery state. IV) Glass transition temperature – temperature at which glass polymers melt. a) b) c) d)
II, III III, IV I, IV I, II
208
n
Chapter 17 Organic Polymer Chemistry
8. Which polymers are correctly classified? (Sec. 17.5)
O I
O
CCH2CH2CH2CH2CNCH2CH2CH2CH2CH2CH2N H polyamide
H O
O II
NCH2CH2CH2CH2CH2C H
O
III
n
C
n
CH3 O
C CH3 polyurethane
polycarbonate
IV
O
O
C
COCH2CH2O
n
polyester a) b) c) d)
II, III III, IV I, IV I, II
9. Which polymers are correctly classified? (Sec. 17.5)
O I
NCH2CH2CH2CH2CH2C H
n
II
O
CCH2CH2CH2CH2COCH2CH2O polyether
polycarbonyl
O III
O
CH3
CN H
O
O NCOCH2CH2CH2O H
n
IV
polyurethane a) b) c) d)
n
O
C
O
CH2
polycarbonate
I, III II, III III, IV II, IV
209
n
Chapter 17 Organic Polymer Chemistry 10. Which pair of compounds would react to form the polymer shown? (Sec. 17.5)
O
O
CCH2CH2CH2CH2CNCH2CH2CH2CH2CH2CH2N H
H
O a)
O
HOCCH2CH2CH2CH2COH + HOCH2CH2OH O
b)
H2NCH2CH2CH2CH2CH2CH2NH2 O
c)
+
Cl
C
Cl
O
HOCCH2CH2CH2CH2COH + H2NCH2CH2CH2CH2CH2CH2NH2 CH3
d)
Na O
O
C
O Na + H2C
CH3
C H + H2NCH2CH2NH2 CH2Cl
11. Which pair of compounds would react to form the polymer shown? (Sec. 17.5)
O O
C
CH3 O
C CH3
O a) HO C
O C OH + HOCH2CH2OH CH3
b)
Na O
O
C
O Na
CH3 O c)
+
Cl
Cl
O
HOCCH2CH2CH2CH2COH + H2NCH2CH2CH2CH2CH2CH2NH2 CH3
d)
C
Na O
O
C
O Na + H2C
CH3 210
C H + H2NCH2CH2NH2 CH2Cl
Chapter 17 Organic Polymer Chemistry
12. Which pair of compounds would react to form the polymer shown? (Sec. 17.5)
OH
OH
CH3 O
H
O
C
N
N
CH3
O
H
O
a) HO C
C OH + HOCH2CH2OH CH3
b)
O
C
Na O
O Na
CH3 O c)
+
Cl
Cl
HOCCH2CH2CH2CH2COH + H2NCH2CH2CH2CH2CH2CH2NH2
Na O
O
C
O Na + H2C
CH3 13.
C
O
CH3 d)
n
C H + H2NCH2CH2NH2 CH2Cl
Which compound would react to form the polymer shown? (Sec. 17.6)
n
a)
b)
c) Cl
OH
d)
14. Which is not a step in the mechanism of a chain growth polymerization? (Sec. 17.6) a) b) c) d)
initiation propagation proliferation termination
15. Which classification best describes the mechanism of step growth polymerization? (Sec. 17.5) a) b) c) d)
nucleophilic acyl addition nucleophilic acyl substitution electrophilic addition radical substitution 211
O
Chapter 17 Organic Polymer Chemistry
16. Which statements are true describing the Ziegler-Natta process? (Sec. 17.6) I) the process yields low density polyethylene II) the process involves radicals III) the process uses an alkytitanium catalyst IV) the process yields polyethylene 3 to 10 times stronger than other methods a) b) c) d)
I, II II, IV II, III III, IV
17. Which polymers will be brittle at 0° C? (Sec. 17.4) I) PVC, Tg = 83° C II) PVA, Tg = 200° C III) teflon, Tg = -80° C IV) polypropylene, Tg = -100° C a) b) c) d)
III, IV II, III I, II II, IV
18. Which polymers will be elastic at 0° C? (Sec. 17.4) I) PVC, Tg = 83° C II) PVA, Tg = 200° C III) teflon, Tg = -80° C IV) polypropylene, Tg = -100° C a) b) c) d)
III, IV II, III I, II II, IV
19. Which polymers will be strongest? (Sec. 17.4) a) b) c) d)
PET 0% crystallinity PET 20% crystallinity PET 35% crystallinity PET 55% crystallinity
20. Which polymers will be the most elastic? (Sec. 17.4) a) b) c) d)
PET 0% crystallinity PET 20% crystallinity PET 35% crystallinity PET 55% crystallinity
212
Chapter 17 Organic Polymer Chemistry 21. Which polymers are step-growth polymers? (Sec. 17.5) I) nylon II) HDPE III) Teflon IV) PET a) b) c) d)
I, II II, III I, IV III, IV
22. Which polymers are chain-growth polymers? (Sec. 17.6) I) nylon II) HDPE III) Teflon IV) PET a) b) c) d)
I, II II, III I, IV III, IV
23. Which polymers are step-growth polymers? (Sec. 17.5) I) Kevlar II) Mylar III) PVC IV) Lucite a) b) c) d)
I, II II, III I, IV III, IV
24. Which polymers are chain-growth polymers? (Sec. 17.6) I) Kevlar II) Mylar III) PVC IV) Lucite a) b) c) d)
I, II II, III I, IV III, IV
213
Chapter 17 Organic Polymer Chemistry 25. Which polymers are correctly matched to their primary use? (Sec. 17.5, 17.6) I) Kevlar and containers II) Polymethylmethacrylate and Plexiglas III) Polytetrafluoroethylene and nonstick coatings IV) PET and bulletproof vests a) b) c) d)
I, III II, III II, IV III, IV
Fill in the Blank 1. The repeat unit of polyacrylonitrile is,
H CH2 C
H CH2 C
CN
H H CH2 C CH2 C
CN
CN
n
CN
2. The repeat unit of polymethylacrylate is,
H H H H CH2 C CH2 C CH2 C CH2 C O
O
O
n
O
OCH3 OCH3 OCH3 OCH3
(Sec. 17.6)
214
(Sec. 17.6)
Chapter 17 Organic Polymer Chemistry
3. The polymer (Nylon 612) synthesized from the following monomers is,
H 2N
CH2
CH2 CH2
CH2
CH2 CH2
NH2
and
O HO
C
CH2 CH2
CH2
CH2 CH2
CH2
CH2
CH2 CH2
CH2
C O
OH (Sec. 17.5)
4. The polymer (PEN) synthesized from the following monomer is
O
O
CH3O C
C OCH3 and
HO
CH2 CH2 OH
5. The monomers used to synthesize Nomex are,
O
O N H
N H
n
(Sec. 17.5)
and
215
(Sec. 17.5)
Chapter 17 Organic Polymer Chemistry
6. The monomers used to synthesize the following polyurethane are,
O
O CH2
N H
O CH2 CH2 O
N H
n
(Sec. 17.5)
and
7. Complete the mechanism for radical chain propagation begun below. (Sec. 17.6)
.
. In
Cl Cl
Cl
In
Cl
8. The label of the following step of radical chain polymerization is __________________________.
. Cl Cl Cl R
Cl
. Cl Cl Cl Cl
R (Sec. 17.6)
9. A carbonate, which forms the backbone of polycarbonates, has the following structure,
(Sec. 17.5)
216
Chapter 17 Organic Polymer Chemistry
10. A diepoxide, which forms the backbone of epoxy resins, has the following structure,
(Sec. 17.5) True-False 1. The glass transition temperature (Tg) must be low for an elastomer to maintain its properties. (Sec. 17.4) 2. The opaquety of a crystalline polymer correlates to the Tm. (Sec. 17.4) 3. The polymer synthesized from the following monomer is,
Cl
Cl
Cl
Cl
Cl
Cl n
Cl
Cl
Cl
Cl
Cl
Cl
(Sec. 17.6)
4. A polymer synthesized from the following monomers could have the form,
H2C CH2
and
H2C CH CH2 CH2 HC CH3 H 3C
(Sec. 17.6)
n
217
Chapter 17 Organic Polymer Chemistry
5. A polymer synthesized from the following monomers could have the form,
H H 2C C
and CN
CH3
H 2C
O O
CH3
(Sec. 17.6)
H H H H CH2 C CH2 C CH2 C CH2 C CN
O OCH3
CN
n
O OCH3
6. Radical chain growth polymers tend to form head to head bonds between carbon one of one monomer and carbon one of another monomer. (Sec. 17.6) 7. Branching of polyethylene, due to a chain transfer reaction, produces low density polyethylene (LDPE). (Sec. 17.6) 8. The Zeigler-Natta process yields low density polyethylene (LDPE). (Sec. 17.6) 9. A polymer with a melt transition temperature (Tm) of 200° C is stronger than a polymer with a Tm of 150° C. (Sec. 17.4) 10. An elastomer with a glass transition temperature (Tg) of 25° C will lose its elasticity below 25° C. (Sec. 17.4)
218
Chapter 17 Organic Polymer Chemistry Answers Multiple Choice 1. c 2. a 3. a 4. b 5. b 6. d 7. d 8. c 9. c 10. c 11. b 12. d 13. a 14. c 15. b 16. d 17. c 18. a 19. d 20. a 21. c 22. b 23. a 24. d 25. b Fill in the Blank 1.
CN 2.
O CH3O 3.
O
H N
* O 4.
O *
O O
O
n
*
219
N H
n
*
Chapter 17 Organic Polymer Chemistry 5.
O
O
HO
OH
NH2
H2N and
6.
O C N
CH2
N C O
and
7.
. In
Cl Cl
Cl
In
Cl
8. Termination 9.
O OR
RO 10.
O
O R
True-False 1. T 2. T 3. F 4. T 5. F 6. F 7. T 8. F 9. T 10. T
220
HO
OH
Chapter 18 Carbohydrates Multiple Choice 1. Which sugars and classifications are correctly matched? (Sec. 18.2)
CH2OH O HO
H
H
OH
HO
H CH2OH
aldohexose I
a) b) c) d)
CHO
CHO H
OH
H
H
OH
HO
H
OH
H
CH2OH
HO
OH H
H
OH
OH
HO
H
H CH2OH
CH2OH
aldotetrose II
aldohexose III
ketotetrose IV
III, V II, III, IV I, III III, IV, V
I) D-Glucose and aldohexose II) D-Galactose and aldopentose III) D-Ribose and ketopentose IV) D-Fructose and ketohexose V) D-Mannose and ketohexose I, III, V I, IV III, IV, V II, III
3. Which is the correct structure for D-glyceraldehyde? (Sec. 18.2)
CHO H C
H
CHO HO C
H
CH2OH
CHO
H C OH
H C OH
CH2OH
CH2OH
CH2OH
CH2OH
a)
b)
c)
d)
221
O H
OH
H
OH CH2OH
2. Which sugars and classifications are correctly matched? (Sec. 18.2)
a) b) c) d)
CH2OH
CHO
ketopentose V
Chapter 18 Carbohydrates 4. Which monosaccharides have the D configuration? (Sec. 18.2)
CH2OH H
OH
HO
H
H
CHO HO H
OH
HO
CHO
CHO
CHO
H
H
OH
H
OH
HO
OH
H
OH
H
OH
H
H
OH
H
HO
CH2OH
H
H
OH
H
OH
H
OH
H
OH HO
H
CHO
CH2OH
CH2OH
CH2OH
CH2OH
CHO
I
II
III
IV
V
VI
a) b) c) d)
I, IV, V II, III, VI IV, V IV, VI
5. What is the relationship between the following compounds? (Sec. 18.2)
CHO
CHO
H
OH
H
OH
H
OH
H
OH
H
H
OH
HO
CH2OH a) b) c) d)
CH2OH
enantiomers anomers meso compounds diastereomers
6. What is the relationship between the following compounds? (Sec. 18.2)
CHO HO
H
H
OH
HO
H
H
OH
CH2OH a) b) c) d)
CHO
CH2OH
anomers diastereomers enantiomers identical structures
222
Chapter 18 Carbohydrates
7. What is the relationship between the following compounds? (Sec. 18.2, 18.3)
CH2OH O OH H H OH H H OH H OH a) b) c) d)
CH2OH O H H H OH H OH OH H OH
anomers meso compounds enantiomers identical structures
8. The Fischer projection for L-idose corresponds to which Haworth projection? (Sec. 18.3)
CHO H
OH H
HO H
OH
HO
H CH2OH
H
O H CH2OH a) OH H OH H OH H OH
c)
CH2OH O OH H H OH H H OH H OH
CH2OH O H H b) OH H OH H OH H OH
H d)
OH H
H
O H
OH
OH
H
CH2OH
OH
223
Chapter 18 Carbohydrates
9. Which is the correct structure for α-D-glucopyranose? (Sec. 18.2, 18.3)
CHO CH2OH HO HO
H O
OH
HO OH
OH
H
H
OH
H
OH
OH
CH2OH O OH OH
C3H7O3 H C OH OH
CH2OH
CH2OH a)
c)
b)
10. How many stereocenters are there in a 2-ketohexose? (Sec. 18.2) a) b) c) d)
2 3 8 16
11. Which of the labeled bonds is a glycosidic bond? (Sec. 18.4)
a) OH
CH2OH O OH
OCH3 d)
OH b)
c)
12. Which of the labeled atoms is the anomeric carbon? (Sec. 18.3)
d)
a)
OH
CH2OH O OH b)
OH
OCH3 c)
224
d)
Chapter 18 Carbohydrates
13. Which reagents could be used to convert galactose to galactitol? (Sec. 18.4) I) NaBH4 / H2O II) Tollen’s solution III) Benedict’s solution IV) Ni / H2 a) b) c) d)
I, II II, III III, IV I, IV
14. Which reagents could be used to convert galactose to galacturonic acid? (Sec. 18.4) I) NaBH4 / H2O II) Tollen’s solution III) Benedict’s solution IV) Ni / H2 a) b) c) d)
I, II II, III III, IV I, IV
15. Which compounds and functional types are correctly matched? (Sec. 18.4)
O CH2OH
COH CH2OH HO HO
H O OH
HO OCH3
OH H
H
OH
H
OH
OH
CH2OH O OH
H OH
NH2
CH2OH alditol I
a) b) c) d)
aldonic acid II
I, IV I, II III, IV II, III
225
amino sugar III
HO
OH H
H
OH
H
OH CH2OH glycoside IV
Chapter 18 Carbohydrates
16. Which are reducing sugars? (Sec. 18.4) I) lactose II) sucrose III) glucose IV) fructose V) galactose a) b) c) d)
I, II, III I, III, IV, V II, III, IV, V III, IV, V
17. Which are disaccharides? (Sec. 18.7) I) sucrose II) glucose III) maltose IV) lactose V) galactose a) b) c) d)
II, IV, V I, II, III III, IV, V I, III, IV
18. Which will reduction of D-fructose with NaBH4 yield? (Sec. 18.4)
CH2OH O HO
H
H
OH
H
OH CH2OH
a) b) c) d)
a single chiral alditol a pair of enantiomeric alditols a meso compound two diastereomers
226
Chapter 18 Carbohydrates
19. Two sugars give identical products when treated with NaBH4. Which of the following are possible structures for the sugars? (Sec. 18.4)
CHO
CHO
a) b) c) d)
CHO
CHO
H
OH
HO
H HO
H
H
OH
HO
H
OH HO
H
H
OH H
CH2OH
CH2OH
CH2OH
CH2OH
I
II
III
IV
I, II I, III III, IV II, IV
20. Which sugars are monosaccharides? (Sec. 18.2) I) mannose II) maltose III) ribose IV) lactose V) glucose a) b) c) d)
I, II, III II, III, IV II, IV, V I, III, V
21. Cellulose, starch, and glycogen are polysaccharides that contain which sugar? (Sec. 18.8) a) b) c) d)
sucrose glucose fructose lactose
22. Which sugars are reducing sugars? (Sec. 18.4) I) sucrose II) maltose III) lactose IV) fructose a) b) c) d)
I, II, III II, III, IV I, III, IV I, II, IV
227
Chapter 18 Carbohydrates
23. Which of the statements about sucrose is false? (Sec. 18.7) a) b) c) d)
The linkage between anomeric carbon atoms is 1,4’. It is the most abundant disaccharide. It cannot reduce Tollens’ reagent. It is a disaccharide composed of glucose and fructose.
24. Which statements about the following sugar are true? (Sec. 18.7)
CH2OH
HO HO
O OH O HO
O OH
CH2OH OH
I) It is a reducing sugar. II) It will undergo mutarotation. III) The linkage is 1,1’. IV) It is composed of two units of D-glucose. a) b) c) d)
I, II II, III III, IV I, IV
25. Which statements about L-ascorbic acid are true? (Sec. 18.6) I) L-ascorbic acid is synthesized from D-glucose. II) Humans enzymatically synthesize L-ascorbic acid. III) L-ascorbic acid is easily oxidized to the diketone, L-dehydroascorbic acid. IV) L-dehydroascorbic acid is not physiologically active. a) b) c) d)
I, II II, IV I, III III, IV
228
Chapter 18 Carbohydrates Fill in the Blank 1. Complete the following reaction by providing the product of the reaction. (Sec. 18.4)
CHO H
OH
HO
H
HO
H
H
enzyme catalyzed oxidation
OH CH2OH
2. Complete the following reaction by providing the product of the reaction. (Sec. 18.4)
CHO HO
H
HO
H
H
OH
H
OH
Tollen's Reagent
CH2OH 3. Complete the following reaction by providing the reagent needed. (Sec. 18.4)
CHO H HO
CH2OH
OH
H
H
HO
OH H
H
OH
H
OH
H
OH
H
OH
CH2OH
CH2OH
4. Complete the following reaction by providing the reagent needed. (Sec. 18.4)
H
CH2OH O OH OH H
H OH H OH
CH2OH O OCH3 OH H H OH H OH H
229
Chapter 18 Carbohydrates 5. Complete the following reaction by providing the product of the reaction. (Sec. 18.4) NH2 N
CH2OH H O
H
H
H OH
OH
OH
O
N H
6. The β-pyranose form of D-Galactose is,
CHO H
OH
HO
H
HO
H
H
OH CH2OH
(Sec. 18.3)
7. The α-furanose form of D-Fructose is,
CH2OH O HO
H
H
OH
H
OH CH2OH
(Sec. 18.3)
8. Complete the following reaction by providing the products of the reaction. (Sec. 18.3)
HO
OH
OH
O
aqueous solution +
OH OH
9. The structure of cellulose is a(n) _________________ polymer of glucose. (Sec. 18.8) 10. The structure of amylopectin is a(n) __________________ polymer of glucose. (Sec. 18.8)
230
Chapter 18 Carbohydrates True-False 1. The structure of α-D-Mannose is,
CH2OH O OH H H OH OH OH H H H (Sec. 18.3) 2. The structure of β-D-Galacuronic acid is,
COOH O OH OH H OH H H H H OH (Sec. 18.4) 3. The structure of D-Gluconic acid is,
COOH H HO
OH H
H
OH
H
OH CH2OH
(Sec. 18.4)
4. The structure of D-Mannitol is,
COOH HO
H
HO
H
H
OH
H
OH COOH (Sec. 18.4)
5. D-Glucosamine, D-Mannosamine, and D-Galactosamine are C-2 stereoisomers of each other. (Sec. 18.4) 6. Glycogen is a branched component of starch. (Sec. 18.8) 7. Amylose and amylopectin are unbranched components of starch. (Sec. 18.8)
231
Chapter 18 Carbohydrates 8. Glucose, Galactose, and Fructose are aldohexoses. (Sec. 18.2) 9. α-D-glucopyranose is a hemi-acetal. (Sec. 18.3) 10. Sucrose is an acetal. (Sec. 18.7)
232
Chapter 18 Carbohydrates Answers Multiple Choice 1. a 2. b 3. d 4. c 5. d 6. c 7. a 8. c 9. c 10. c 11. d 12. c 13. d 14. b 15. d 16. b 17. d 18. d 19. a 20. d 21. b 22. b 23. a 24. c 25. c Fill in the Blank 1.
CHO H
OH
HO
H
HO
H
H
OH COOH
2.
COOH HO
H
HO
H
H
OH
H
OH CH2OH
3. NaBH4/H2O or H2 and metal catalyst 233
Chapter 18 Carbohydrates
4. CH3OH / H+ 5.
NH2 N CH2OH O N H O H H
H OH
OH
6.
CH OH OH 2 OH O OH OH 7.
CH2OH O
OH
CH2OH OH
OH 8.
OH HO
OH
OH +
O
HO
OH
OH OH
O OH
OH
9. linear 10. branched True-False 1. F 2. T 3. T 4. F 5. F 6. F 7. F 8. F 9. T 10. T
234
Chapter 19 Amino Acids and Proteins Multiple Choice 1. Which amino acid has a nonpolar side chain? (Sec. 19.2)
O
O
O
a) H2NCCH2CH2CHCO
b) CH3SCH2CH2CHCO
NH3 N
NH3 OH
O
c)
CH2CHCO
N
d)
NH3
H
O CH2CHCO NH3
2. Which amino acid has an acidic side chain? (Sec. 19.2)
O
OH a)
b) CH3SCH2CH2CHCO NH3 O CH2CHCO NH3 O
O
c) H2NCCH2CH2CHCO NH3
N d)
O N H
235
CH2CHCO NH3
Chapter 19 Amino Acids and Proteins
3. Which amino acid has a basic side chain? (Sec. 19.2)
O
O
a) HSCH2CHCO
b) CH3SCH2CH2CHCO
NH3
NH3
O
NH2
O
c) H2NCCH2CH2CHCO
O
d) H2NCNHCH2CH2CH2CHCO NH3
NH3 4. Which molecules are zwitterions? (Sec. 19.2)
O
NH2
HSCH2CHCOH
O
H2NCNHCH2CH2CH2CHCO
NH3
NH3
I
II
O
O
O
H2NCCH2CH2CHCO NH3 III a) b) c) d)
CO
N H
H IV
I, III II, III III, IV I, IV
5. Which describes the isoelectric point of an amino acid? (Sec. 19.3) a) b) c) d)
The degree of ionization of the amino acid at pH 7. The pH at which there is no net charge for the amino acid. The pH at which the ionized form predominates. The pH at which the amino acid is present as the dipolar ion.
236
Chapter 19 Amino Acids and Proteins
6. Which is the order of increasing acidity for the indicated carboxyl groups (least first)? (Sec. 19.3)
O
O CH3COH
O
O
H3NCH2COH CH3CNCH2COH H
I a) b) c) d)
II
III
I, II, III II, III, I III, II, I I, III, II
7. Which is the order of increasing basicity for the indicated amino groups (least first)? (Sec. 19.3)
HN C
NH2
O
NHCH2CH2CH2CHCOH I
CH3CH2NH2
NH2 III II
a) b) c) d)
I, II, III II, III, I III, II, I I, III, II
8. Tyrosine has an isoelectric point of 5.63. What charge does tyrosine have at pH 7 and which electrode does it migrate to during electrophoresis? (Sec. 19.3) a) b) c) d)
negative, anode positive, cathode negative, cathode positive, anode
9. Lysine has an isoelectric point of 9.74. What charge does tyrosine have at pH 7 and which electrode does it migrate to during electrophoresis? (Sec. 19.3) a) b) c) d)
negative, anode positive, cathode negative, cathode positive, anode
237
Chapter 19 Amino Acids and Proteins
10. Aspartic acid has an isoelectric point of 2.98. At which pH would the predominate form of aspartic acid in solution migrate toward the negative electrode during electrophoresis? (Sec. 19.3) a) b) c) d)
1 2.98 4 7
11. Arginine has an isoelectric point of 10.76. At which pH would the predominate form of arginine in solution migrate toward the positive terminal during electrophoresis? (Sec. 19.3) a) b) c) d)
5 7 10.76 12
12. Isoleucine has pka values of 2.32 (-COOH) and 9.76 (-NH3+). Which is isoleucine’s isoelectric point? (Sec. 19.3) a) b) c) d)
3.08 7.64 6.04 9.74
13. Glutamic acid has an isoelectric point of 3.08. At which pH is the cationic form in greatest concentration? (Sec. 19.3) a) b) c) d)
2 3.2 5.6 9.7
14. Which is the order of increasing mobility of the molecule toward the cathode (least first)? (Sec. 19.3)
NH2
O
H2NCNHCH2CH2CH2CHCO I NH2
O
H2NCCH2CH2CHCO
NH3 O
H2NCNHCH2CH2CH2CHCOH
O
II O
O
H2NCCH2CH2CHCO
NH3
NH2
III a) b) c) d)
NH3
IV
III, I, II, IV I, III, II, IV IV, II, I, III III, IV, I, II
238
Chapter 19 Amino Acids and Proteins
15. Which is the predominate form of lysine in blood plasma at pH 7.4? (Sec. 19.3)
O
O
a) H3NCH2CH2CH2CH2CHCOH b) H2NCH2CH2CH2CH2CHCO NH3
NH2
O
O
c) H3NCH2CH2CH2CH2CHCO
d) H3NCH2CH2CH2CH2CHCO
NH2
NH3
16. Which is the charge on lysine at pH 11? (Sec. 19.3) a) b) c) d)
0 +1 –1 +2
17. Which is the charge of lysine at pH 2? (Sec. 19.3) a) b) c) d)
0 +1 –1 +2
18. Which is the structure of the pentapeptide that gave lys-leu-phe on reaction with cyanogen bromide, and gave fragments met-lys, leu-phe, and arg on reaction with trypsin. (Sec. 19.5) a) b) c) d)
arg-met-phen-leu-lys lys-leu-phe-arg-met arg-met-lys-leu-phe met-arg-lys-leu-phe
19. A polypeptide gave the following proportions of amino acids upon hydrolysis: ala (1), gly (1), ile (2), phe (2), ser (1), tyr (2). Edman degradation yields tyrosine phenylthiohydantoin. Partial hydrolysis of the peptide gave a mixture of smaller peptides including: ala-gly, gly-tyr, ile-ile, phe-ile, ser-phe, tyr-ser, tyr-phe, ile-ala. Which is the C-terminal amino acid in the original peptide? (Sec. 19.5) a) b) c) d)
tyr ser phe ile
239
Chapter 19 Amino Acids and Proteins
20. A penta-peptide has the following proportions of amino acids: gly (1), leu (1), val (1), phe (2). Treatment of the pentapeptide with chymotrypsin gave the following fragments: gly-val, leu, phe. Which is the structure of the penta-peptide? (Sec. 19.5) a) b) c) d)
phe-phe-gly-val-leu gly-val-phe-leu-phe leu-gly-val-phe-phe phe-leu-gly-val-phe
21. Which is the chemical structure of the tripeptide glutathione (glu-cys-gly)? (Sec. 19.5)
O
O
O
O
O
CH2SH
CO
CH2SH
O O
O
O
O
O
O
d) H3NCHCNHCHCNHCH2CO
c) H3NCH2CNHCHCNHCHCH2CH2CO
CH2SH CH2CH2CO
CH2SH CO
O
O 22. Which characteristics are correct for a peptide bond in a polypeptide? (Sec. 19.4) I) planar II) cis III) trans IV) tetrahedral a) b) c) d)
I, II I, III II, IV III, IV
23. Which are true describing the secondary structure of a protein that is an α-helix? (Sec. 19.6) I) The helix is coiled counterclockwise. II) The N-H bond and the C=O bond point outward. III) Hydrogen bonding is between groups 4 amino acid units apart. IV) The coil has 3.6 amino acids per turn. a) b) c) d)
O
b) H3NCHCH2CH2CNHCHCNHCH2CO
a) OCCH2CH2CHCNHCHCNHCH2CO NH3
O
I, II I, III II, IV III, IV
240
Chapter 19 Amino Acids and Proteins
24. The secondary structure of proteins depends primarily on which property of amino acids? (Sec. 19.6) a) b) c) d)
disulfide bonds hydrogen bonds amide bonds polar side chains
25. The tertiary structure of proteins depends primarily on which property of amino acids? (Sec. 19.6) I) disulfide bonds II) hydrogen bonds III) amide bonds VI) polar side chains a) b) c) d)
III, IV I, VI II, III I, II
Fill in the Blank 1. The isoelectric point of proline is ______________. (Sec. 19.3) pKa (COOH) = 2.00, pKa (NH3+) = 10.60 2. The isoelectric point of cysteine is ______________. (Sec. 19.3) pKa (COOH) = 2.05, pKa (NH3+) = 10.25, pKa (SH) = 8.00 3. The structure of a common amino acid with a polar side chain is
(Sec. 19.2) 4. The structure of a common amino acid with an acidic side chain is
(Sec. 19.2)
241
Chapter 19 Amino Acids and Proteins 5. The structure of a common amino acid with a basic side chain is
(Sec. 19.2)
6. The structure of the tripeptide Met-Ile-Pro is
(Sec. 19.5) 7. The structure of the tripeptide Glu-Gly-Phe is
(Sec. 19.5) 8. The result of the reaction of Asp-Val-Met-Leu-His with cyanogens bromide is _______________________. (Sec. 19.5) 9. The result of the reaction of the hydrolysis of Ala-Phe-Leu-Tyr-Leu-Pro with chymotrypsin is __________________________. (Sec. 19.5) 10. The result of the reaction of the hydrolysis of Leu-Ile-Lys-Cys-Val-Asn-Gln-Tyr with trypsin is __________________________. (Sec. 19.5) True-False 1. The isoelectric point of Glycine is 6.06 (pKa (COOH) = 2.35, pKa (NH3+) = 9.78). (Sec. 19.3) 2. At pH 7.05 lysine (pI = 9.74) will migrate toward the positive electrode during electrophoresis. (Sec. 19.3) 3. Asparagine is an amino acid with an acidic side chain. (Sec. 19.2) 4. Arginine is an amino acid with a basic side chain. (Sec. 19.2)
242
Chapter 19 Amino Acids and Proteins 5. The sequence of an octa-peptide can be deduced from the following experimental results as Cys-Asn-Met-TyrVal-Phe-Lys-Pro. (Sec. 19.5) Edman degradation Hydrolysis catalyzed by Trypsin Hydrolysis catalyzed by Chymotrypsin Treatment with Cyanogen Bromide
Cys Cys, Asn, Met, Tyr, Val, Phe, Lys Pro Cys, Asn, Met, Tyr Val, Phe Lys, Pro Cys, Asn, Met Tyr, Val, Phe, Lys, Pro
6. The sequence of a hepta-peptide can be deduced from the following experimental results as Thr-Tyr-Cys-GlnArg-Trp-His (Sec. 19.5) Edman degradation Hydrolysis catalyzed by Trypsin Hydrolysis catalyzed by Chymotrypsin
Thr Thr, Tyr, Cys, Gln, Arg Trp, His Thr, Tyr Cys, Gln, Arg, Trp His
7. The sequence of a deca-peptide can be deduced from the following experimental results as Leu-Met-Ser-Thr-TrpHis-Phe-Asp-Lys-Glu. (Sec. 19.5) Edman degradation Hydrolysis catalyzed by Trypsin Hydrolysis catalyzed by Chymotrypsin Treatment with Cyanogen Bromide
Leu Leu, Met, Ser, Thr, Trp, His, Phe, Asp, Lys Glu Leu, Met, Ser, Thr, Trp His, Phe Asp, Lys, Glu Leu, Met Ser, Thr, Trp, His, Phe, Asp, Lys, Glu
8. α-Helix and β-sheet are examples of protein secondary structure. (Sec. 19.6) 9. A major stabilizing factor of protein tertiary structure is disulfide linkages. (Sec. 19.6) 10. The major stabilizing factor of the quaternary protein structure is hydrogen bonding. (Sec. 19.6)
243
Chapter 19 Amino Acids and Proteins Answers Multiple Choice 1. b 2. a 3. d 4. c 5. b 6. d 7. b 8. a 9. b 10. a 11. d 12. c 13. a 14. c 15. d 16. c 17. d 18. c 19. c 20. b 21. a 22. b 23. d 24. b 25. d Fill in the Blank 1. 6.30 2. 5.02 3.
OH
O
O HO
O
O NH3 +
NH3 +
O
O
O
O O H2N
NH3 +
H2N
O NH3 +
244
Chapter 19 Amino Acids and Proteins 4.
O
O HS
O
O NH3 +
NH3 +
HO
O
O
O
O O O
O
O
NH3 +
NH3 +
5.
O
+ NH 2 O
N NH
H2N
NH3 +
H3N
O
N H
O NH3 +
O
+
O NH3 +
6.
O + NH3
H N
O
O N
O
SCH3
245
Chapter 19 Amino Acids and Proteins 7.
O + NH3
H N
O H N
H H O
O O
O
8. Asp-Val-Met, Leu-His 9. Ala-Phe, Leu-Tyr, Leu-Pro 10. Leu-Ile-Lys, Cys-Val-Asn-Glu-Tyr True-False 1. T 2. F 3. F 4. T 5. T 6. F 7. F 8. T 9. T 10. F
246
Chapter 20 Nucleic Acids Multiple Choice 1. Which structures are named correctly? (Sec. 20.2)
O
O
O
a) b) c) d)
CH3
HN
HN O
N
O
NH2 N
N
N
N
N
N
HN N
NH2
H
H
H
H
guanine I
thymine II
N
adenine III
uracil IV
I, II II, III III, IV I, III
2. Which structure is a nucleoside? (Sec. 20.2)
O NH2 N
N
a)
b) N
HOH2C O
N
N O
H O O
O CH3
HN c)
HOH2C O
N
HOH2C
OH O
d) O
O O
OH
CH3
HN
OH
P O O
247
OH
P O O
Chapter 20 Nucleic Acids
3. Which structures are named correctly? (Sec. 20.2)
O
NH2 CH3
HN HOH2C O
N
O
HOH2C O
O
O
CH3
N
OH
N O
O
P O
O
O
OH
P O O
O
P O O
thymidine 5'-monophosphate I
cytidine 3'-diphosphate II
O
O
N
HN
O
P OH2C H2N O O OH
NH2
N
N H
O
O
O
P O
P OH2C
O
O
OH
a) b) c) d)
N O OH
adenosine 5'-monophosphate III
N
N
N H
OH
adenosine 5'-diphosphate IV
I, II II, III I, IV II, IV
248
Chapter 20 Nucleic Acids
4. Which nucleotides are named correctly? (Sec. 20.2)
O HN
O O
P OH2C O O
O
O
P OH2C H2N O O
OH
OH
O 5'-TMP I
CH3
HN
HOH2C O
O OH
P O P O
H OH
3'-GMP II
NH2
O
O
O
P O
P OH2C
O
O
N
N N O
3'-TDP III I, III II, III III, IV II, IV
249
N H
OH
5'-GDP IV
O
a) b) c) d)
N
OH
O O
N
N
O O
N
HN
O
N
OH
O
CH3
Chapter 20 Nucleic Acids
5. What is the correct name for this structure? (Sec. 20.2)
O CH3
HN HOH2C O
N O
O O
P O O
a) b) c) d)
5’-dAMP 5’-TMP 3’-AMP 3’-dTMP
6. How do DNA and RNA differ? (Sec. 20.3, 20.4) I) the position of attachment of phosphate groups II) the position of attachment of base groups III) the sugar structure at C-2’ IV) structure of bases a) b) c) d)
I, II II, III III, IV II, IV
7. Which are the correct pairings of bases in the structure of DNA? (Sec. 20.3) I) A-C II) G-T III) A-G IV) G-C V) A-T VI) C-T a) b) c) d)
I, II III, V III, IV IV, V
250
Chapter 20 Nucleic Acids
8. In both RNA and DNA structures, the phosphate groups are attached to the sugar structure at which positions? (Sec. 20.3, 20.4) a) b) c) d)
5’, 5’ 3’, 3’ 3’, 5’ 5’, 3’
9. What is the charge on adenosine phosphate at blood serum pH of 7.4? (Sec. 20.3) a) b) c) d)
0 –1 –2 –3
10. Which is the complementary tetranucleotide for 5’-AGCT-3’? (Sec. 20.3) a) b) c) d)
5’-TCGA-3’ 5’-CTAG-3’ 5’-AGCT-3’ 5’-GATC-3’
11. How many nucleotides direct a specific amino acid into a polypeptide sequence? (Sec. 20.5) a) b) c) d)
1 2 3 4
12. Which is the DNA complement for 5’-ACCGTTAAT-3’? (Sec. 20.3) a) b) c) d)
5’-ATTAACGGT-3’ 5’-GTTACCGGC-3’ 5’-TGGCAATTA-3’ 5’-CAATGGCCG-3’
251
Chapter 20 Nucleic Acids
13. Hydrogen bonding is strongest between which two bases? (Sec. 20.3)
NH2
O
N N
O
a) b) c) d)
CH3
HN O
N
H
H
I
II
O
NH2 N
N
N
N
N
HN NH2
N
H
H III
N
IV
I, II I, IV II, III II, IV
14. Where does protein synthesis occur? (Sec. 20.4) a) b) c) d)
chromatin ribosome codon histones
15. Which is the complementary sequence in RNA for the DNA sequence 5’-AATCAGTT-3’? (Sec. 20.4) a) b) c) d)
5’-AAUCAGUU-3’ 5’-AACUGAUU-3’ 5’-UUAGUCAA-3’ 5’-CCAUCGAA-3’
16. A complete turn of the DNA helix occurs at which distance? (Sec. 20.3) a) b) c) d)
34 Å 10 Å 20 Å 4Å
17. Which statement about the base mole-percent composition of DNA is true? (Sec. 20.3) a) b) c) d)
A=G=C=T (A+G)=(C+T) (A+T)=(G+C) There is no relationship
18. The backbone of DNA is best described as: (Sec. 20.3) a) b) c) d)
pairs of complementary bases poly(1,3-diol-phosphate esters) pyrophosphates sugar glycosides
252
Chapter 20 Nucleic Acids 19. Which statements about differences between DNA and RNA are true? (Sec. 20.3, 20.4) I) The sugar unit is β-D-ribose in RNA and β-2-deoxyribose in DNA. II) The pyrimidine bases are uracil and thymine in RNA and cytosine and thymine in DNA. III) RNA is single stranded, DNA double stranded. IV) The phosphodiester groups join the 3’ to 5’ ends of sugars in RNA, and join the 5’ to 3’ ends in DNA. a) b) c) d)
I, II I, III II, III III, IV
20. Which are types of RNA? (Sec. 20.4) I) ribosomal II) histonal III) helix IV) transfer a) b) c) d)
I, II I, III II, IV I, IV
21. Which is the order of increasing percentage in cells of messenger RNA, transfer RNA, ribosomal RNA (least first)? (Sec. 20.4) a) b) c) d)
mRNA, tRNA, rRNA tRNA, rRNA, mRNA rRNA, tRNA, mRNA mRNA, rRNA, tRNA
22. Which statements about mRNA codons are correct? (Sec. 20.4) I) Each amino acid is coded by only one codon. II) Codons code for several amino acids. III) UAA, UAG, UGA are stop codons. IV) Several amino acids are coded by more than one codon. a) b) c) d)
I, II III, IV I, III II, IV
23. Which is the key to the chain termination method of DNA sequencing? (Sec. 20.6) a) b) c) d)
polyacrylamide gels restriction endonucleases primer 2’,3’-dideoxynucleoside triphosphate
253
Chapter 20 Nucleic Acids
24. Which is the key to in vitro DNA replication? (Sec. 20.6) a) b) c) d)
polyacrylamide gels restriction endonucleases primer 2’,3’-dideoxynucleoside triphosphate
25. Which statements about restriction endonucleases are true? (Sec. 20.6) I) Each cleave DNA at the same site, but leave different fragment lengths. II) Each recognizes 4 to 8 nucleotides, and cleaves at all sites containing the sequence. III) Approximately 1000 restriction endonucleases have been isolated and characterized. IV) Each cleaves the DNA strand by reducing the base off at the sugar 1’ position. a) b) c) d)
I, IV II, IV II, III III, IV
Fill in the Blank 1. The name of the following base is ____________________________. (Sec. 20.2)
O HN N H
O
2. The name of the following nucleoside is _____________________________________. (Sec. 20.2)
O N
HN H2N
N
N
CH2OH O OH
OH
254
Chapter 20 Nucleic Acids 3. The name of the following nucleotide is _____________________________________. (Sec. 20.2)
NH2 N O
O O
P O CH2 O
N
O
OH
OH
4. The complementary DNA single strand of 5’-AGTGTTCCAGT-3’ is 5’-____________________________-3’. (Sec. 20.3) 5. The complementary RNA strand to the DNA single strand 5’-GGACTTGACTA-3’ is 5’-____________________________-3’. (Sec. 20.4) 6. The first four amino acids of the protein coded for by AUUAUCCAUAAUGGUGGAAAACGA are __________________________________________________________. (Sec. 20.5) 7. The first four amino acids of the protein coded for by GCUGCCGAUGACGGACGGUGGUGU are __________________________________________________________. (Sec. 20.5) 8. An mRNA strand that codes for the pentapeptide Ile-Thr-Pro-Lys-Arg could have __________ codons in the first position. (Sec. 20.5) 9. An mRNA strand that codes for the pentapeptide Met-Ser-Tyr-Met-Cys could have __________ codons in the first position. (Sec. 20.5) 10. The original DNA strand that results in the following fragments after the Dideoxy method is 5’-_____________________________-3’. (Sec. 20.6) Primer = AGCT Fragments AAGCT, GAAGCT, AGAAGCT, AAGAAGCT, CAAGAAGCT, TCAAGAAGCT True-False 1. The following nucleoside is named Cytidine. (Sec. 20.2)
NH2 N O
O O
P O CH2 O OH
N
O OH 255
Chapter 20 Nucleic Acids
2. The following nucleotide is named 5’-Guanisine diphosphate. (Sec. 20.2)
O N
HN
P O
H2N H2 P O C
O
O
O O
O
N
OH
N
O OH
3. The mole % of purine bases must be equal in human DNA. (Sec. 20.3) 4. The tertiary structure of DNA involves supercoiling. (Sec. 20.3) 5. t-RNA is the lowest molecular weight and most abundant of the RNAs. (Sec. 20.4) 6. mRNA is the shortest lived of the RNAs and the least abundant. (Sec. 20.4) 7. The complementary strand of mRNA to the DNA sequence TAGAAGTAG is ATCTTCATC. (Sec. 20.4) 8. tRNA with the codon UGA codes for Cys. (Sec. 20.5) 9. If the smallest fragment produced during the Dideoxy method and separated by PAGE includes the primer and the base T, the original DNA template begins with T after the primer sequence. (Sec. 20.6) 10. The Chain Termination method uses dideoxy nucleosides to stop DNA synthesis. (Sec. 20.6)
256
Chapter 20 Nucleic Acids Answers Multiple Choice 1. b 2. c 3. d 4. a 5. d 6. c 7. d 8. c 9. c 10. c 11. c 12. a 13. b 14. b 15. b 16. a 17. b 18. b 19. b 20. d 21. a 22. b 23. d 24. c 25. c Fill in the Blank 1. Thymine 2. Guanisine 3. 5’-cytidine monophosphate 4. 5’-ACTGGAACACT-3’ 5. 5’-UAGUCAAGUCC-3’ 6. Ile-Ile-His-Asn 7. Ala-Ala-Asp-Asp 8. 3 9. 1 10. 5’-AGTTCT-3’ True-False 1. F 2. T 3. F 4. T 5. F 6. T 7. F 8. F 9. F 10. T
257
Chapter 21 Lipids Multiple Choice 1. Which saturated fatty acids have the correct name? (Sec. 21.2) I) CH3(CH2)10COOH – stearic acid II) CH3(CH2)14COOH – palmitic acid III) CH3(CH2)16COOH – lauric acid IV) CH3(CH2)18COOH – arachidic acid a) b) c) d)
I, II III, IV I, III II, IV
2. Which properties are characteristic of the most abundant fatty acids found in plants and animals? (Sec. 21.2) I) They contain an even number of carbon atoms, in the range 10-20. II) The cis isomer predominates. III) The unsaturated fatty acids have higher melting points than the corresponding saturated acids. IV) The most abundant fatty acids are lauric, myristic and linolenic. a) b) c) d)
I, II III, IV I, III II, IV
3. Which physical property of triacylglycerols rich in saturated fatty acids is responsible for the higher melting point than the corresponding unsaturated compounds? (Sec. 21.2) a) b) c) d)
Dispersion forces Hydrophilic interactions Cis-carbon-carbon double bond steric interactions Hydrogen bonding
4. Which physical property of triacylglycerols rich in unsaturated fatty acids is responsible for the lower melting point than the corresponding saturated compounds? (Sec. 21.2) a) b) c) d)
Van der Waals attractions Hydrophilic interactions Cis-carbon-carbon double bond steric interactions Hydrogen bonding
5. Deposits and films are a problem with soaps but not detergents because of which property? (Sec. 21.3) a) b) c) d)
Soaps form soluble calcium salts. Detergents form more stable micelles. Detergents do not form insoluble calcium salts. Soap micelles are unstable in acid.
6. How many triglycerides, including stereoisomers, are possible if two fatty acids are present in the triglyceride? (Sec. 21.2) a) b) c) d)
3 4 5 6 258
Chapter 21 Lipids 7. Which natural products have structures derived from cholesterol? (Sec. 21.5, 21.7) I) vitamin A II) vitamin D III) cholic acid IV) cortisone V) squalene a) b) c) d)
I, II, III II, III, IV III, IV, V I, III, V
8. Which is not a characteristic group in phospholipids? (Sec. 21.4) a) b) c) d)
phosphate esters fatty acid esters glycerides polyamides
9. Which property of phospholipids accounts for their ability to form micelles? (Sec. 21.4) a) b) c) d)
nonpolarity unsaturation hydrophilicity and lipophilicity lipophilicity
10. Which property of phospholipids accounts for their ability to form fluid membranes? (Sec. 21.4) a) b) c) d)
nonpolarity unsaturation hydrophilicity and lipophilicity lipophilicity
259
Chapter 21 Lipids 11. Which is the structure of a phosphatidyl choline? (Sec. 21.4)
O H 2C O O O a)
H2NCH2CH2
O
(CH2)16CH3
O
(CH2)14CH3
HC O
P O CH2
H 2C O O
O HC O + COO c) NH3 CH CH2 O P O CH2
O
(CH2)16CH3 (CH2)14CH3
O O H 2C O O + b) (CH3)3NCH2CH2
O O
P
HC O
(CH2)16CH3 (CH2)14CH3
O
O CH2
O
H2C O O
OH HO d)
O
HO
HO
O OH
P
HC O
(CH2)16CH3 (CH2)14CH3
O CH2
O
12. The fluid-mosaic model of the lipid bilayer states; (Sec. 21.4) a) lipids coexist side by side as discreet units and proteins float in the bilayer, able to move along the plane of the membrane. b) the lipids form new covalent bonds between chains and lock the proteins into position, much like a mosaic tile. c) the lipids form a fluid-like membrane that metabolic components (the mosaic) can freely cross. d) the lipid bilayer forms a rigid structure with channels that allow fluid to pass. 13. Which are the most common fatty acids found in phospholipids? (Sec. 21.4) a) b) c) d)
palmioleic, stearic, lauric lauric, myristic, palmitic palmitic, stearic, oleic stearic arachidic, oleic
260
Chapter 21 Lipids 14. Which is the number of stereocenters in methandrostenolone? (Sec. 21.5)
OH CH3 CH3 H
CH3
H
O a) b) c) d)
4 6 8 10
15. Which reagents could be used to harden an oil to a fat? (Sec. 21.3) a) b) c) d)
NaBH4 / H2O Ni / H2 Ag(NH3)2+ / H2O Cu2+ / buffer
16. Which common structural feature of vitamin E and vitamin K1 best accounts for the greater solubility of these molecules in organic solvent than water? (Sec. 21.7)
O CH3
O CH3
vitamin K1
HO H3C
O CH3
a) b) c) d)
CH3 vitamin E
aromatic rings oxygen atoms 4 isoprene units a quinone / hydroquinone units
261
Chapter 21 Lipids 17. Which is a prostaglandin? (Sec. 21.6)
CH3
CH3
CH3 CH2OH
a)
HO COOH
b)
CH3 CH3
HO
HO
H
O CCH2OH CH3 OH
HO CH3 c)
H
H
H
d)
O
HO
18. Which structure is vitamin A? (Sec. 21.7)
CH3
CH3
CH3 CH2OH
a)
COOH
b)
CH3 CH3
HO O CCH2OH CH3 OH
HO CH3 c)
HO
H
H H
d)
O
HO
262
HO
H
Chapter 21 Lipids
19. Which structure is a cortisone? (Sec. 21.5)
CH3
CH3
CH3 CH2OH
a)
HO COOH
b)
CH3 CH3
HO
HO
H
O CCH2OH CH3 OH
HO CH3 c)
H
H
H
d)
O
HO
20. Fats, oils, phospholipids, prostaglandins and steroids have which properties in common? (Sec. 21.1) I) oxygen functionality II) nonpolar groups III) rings IV) unsaturation a) b) c) d)
I, II III, IV I, III II, IV
263
Chapter 21 Lipids
21. Which is the best description of the first step (A) of the biosynthesis of prostaglandin? (Sec. 21.6)
COOH
A O COOH O OOH a) b) c) d)
hydration reduction oxidation Claisen condensation
22. Which is the best description of the second step (B) of the biosynthesis of prostaglandins? (Sec. 21.6)
O COOH O OOH B O COOH O OH
a) b) c) d)
hydration reduction oxidation Claisen condensation
264
Chapter 21 Lipids
23. Which statements about steroids are false? (Sec. 21.5) I) The fusion of all rings is cis. II) Sex hormones, adrenocorticoid hormones, bile acids and vitamin D are derived from cholesterol. III) The biosynthesis of cholesterol produces several isomers. IV) Steroids are tetracyclic ring systems a) b) c) d)
I, III II, IV I, II III, IV
24. Which statements about vitamins are true? (Sec. 21.7) I) Vitamins A, D, E and K are fat soluble. II) Vitamins A, D, E and K are derived from cholesterol. III) Vitamins A, D, E and K each contain 4 isoprene units. IV) Vitamins A, D, E and K have distinct physiological activities. a) b) c) d)
II, III III, IV I, III I, IV
25. The key step in the preparation of soap, saponification, is best described by which mechanism? (Sec. 21.3) a) b) c) d)
base catalyzed acyl addition electrophilic addition acid catalyzed acyl substitution base catalyzed acyl substitution
Fill in the Blank 1. The melting point order of the following fatty acids is (lowest to highest), lauric (12:0) _______
palmitic (16:0) _______
palmitoleic (16:1) _______
oleic (18:1) ______
(Sec. 21.2)
2. The lower melting point of unsaturated fatty acids compared to saturated fatty acids is due to ______________________________ differences. (Sec. 21.2)
265
Chapter 21 Lipids 3. Complete the reaction below by providing the missing products. (Sec. 21.3)
O H2C O O
(CH2)7 C C H H
HC O H 2C
(CH2)14CH3
O
(CH2)7CH3
3NaOH, H2O
H2C OH HC OH H2C
(CH2)16CH3
+
OH
O
4. Complete the structure of the alkylbenzene sulfonate detergent below. (Sec. 21.3)
CH3(CH2)12CH2
5. Complete the structure of the phospholipid below. (Sec. 21.4)
O H 2C O O O P
HC O
(CH2)16CH3 (CH2)14CH3
O CH2
O 6. The forces which drive bilayer formation by phospholipids are __________________ and ________________. (Sec. 21.4) 7. Androsterone has ________ stereocenters and ____________ possible stereoisomers. (Sec. 21.5)
CH3 O CH3 H
H H
HO 8. Vitamin A precursor β-carotene belongs to the _____________ class of compounds and contains ________ isoprene units. (Sec. 21.7) 9. Prostaglandin is a member of the _________________ class of compounds, which are synthesized from ____________________. (Sec. 21.6) 10. Vitamins A, D, E, and K are included in the lipid class because they are _______ soluble. (Sec. 21.7)
266
Chapter 21 Lipids
True-False 1. Stearic acid is an unsaturated fatty acid. (Sec. 21.2) 2. Human fat has more unsaturated fatty acids than plant fats. (Sec. 21.2) 3. Soaps and detergents form micelles when added to water. (Sec. 21.3) 4. Soap micelles form in water by aggregating the negatively charged carboxylate groups toward the inside and the lipophilic carbon chains toward the outside of the micelle. (Sec. 21.3) 5. The forces that drive micelle and lipid bilayer formation are the same. (Sec. 21.4) 6. There are several stereoisomers of cholesterol found in living systems. (Sec. 21.5) 7. Aldosterone is an androgen. (Sec. 21.5) 8. Vitamin D precursors have the cholesterol ring system. (Sec. 21.7) 9. Vitamin E is required for blood clotting. (Sec. 21.7) 10. Prostaglandins are involved with the inflammatory response. (Sec. 21.6)
267
Chapter 21 Lipids Answers Multiple Choice 1. d 2. a 3. a 4. c 5. c 6. d 7. b 8. d 9. c 10. c 11. b 12. a 13. c 14. b 15. b 16. c 17. b 18. a 19. c 20. a 21. c 22. b 23. a 24. d 25. d Fill in the Blank 1. 3, 4, 1, 2 2. Conformational 3.
O -O
(CH2)14CH3 O
-O
(CH2)7 C C H H
-O
(CH2)16CH3
(CH2)7CH3
O 4.
CH3(CH2)12CH2
_ SO3
268
Chapter 21 Lipids 5.
O (CH2)16CH3
H 2C O O O H2NCH2CH2O
(CH2)14CH3
HC O
P
O CH2
O O or
H 2C O O O
(CH3)3NCH2CH2O
P
(CH2)16CH3 (CH2)14CH3
HC O O CH2
O O or _
H 2C O O O
OOC
(CH2)16CH3 (CH2)14CH3
HC O
C C O P O CH2 + NH3 H H2 O O or HO HO
H 2C O O OH
OH O OH
O P
(CH2)14CH3
HC O O CH2
O
6. hydrophobic and electrostatic 7. 7, 128 8. terpene, 8 9. eicosanoid, arachidonic acid 10. fat or low polarity organic True-False 1. 2. 3. 4.
(CH2)16CH3
F F T F 269
Chapter 21 Lipids 5. T 6. F 7. F 8. T 9. F 10. T
270
Chapter 22 The Organic Chemistry of Metabolism Multiple Choice 1. Which are oxidation / reduction reagents in the metabolism of fatty acids? (Sec. 22.2, 22.6) I) ATP II) ADP III) NAD+ / NADH IV) FAD / FADH2 a) b) c) d)
I, II III, IV I, III II, IV
2. Which are agents for energy storage and transport? (Sec. 22.2) I) ATP II) ADP III) NAD+ / NADH IV) FAD / FADH2 a) b) c) d)
I, II III, IV I, III II, IV
3. Which is the oxidizing agent for the following reaction? (Sec. 22.6)
O O CH2CH2CH2CSCoA
CSCoA
H C H3C
a) b) c) d)
C H
FAD FADH2 NAD+ NADH
271
Chapter 22 The Organic Chemistry of Metabolism
4. Which is the oxidizing agent for the following reaction? (Sec. 22.6)
OH
O
O
CH3CHCH2CSCoA a) b) c) d)
O
CH3CCH2CSCoA
FAD FADH2 NAD+ NADH
5. Which is reagent X and product Y in this reaction? (Sec. 22.6)
O
O
X
CH3CH2CCH2CSCoA a) b) c) d)
O CH3CH2CSCoA
+ Y
X= acetyl CoA, Y= coenzyme A X=coenzyme A, Y= acetyl CoA X= FAD, Y= FADH2 X= NAD+, Y= NADH
6. The following are key steps in fatty acid metabolism. What is the best description for the first step (A)? (Sec. 22.6)
O RCH CHCSCoA
A
OH
O
RCH CH2CSCoA
O
B
O
RC CH2CSCoA C O
O
RCSCoA + CH3CSCoA a) b) c) d)
oxidation hydration reverse-Claisen condensation selective reduction
272
Chapter 22 The Organic Chemistry of Metabolism 7. The following are key steps in fatty acid metabolism. What is the best description for the first step (B)? (Sec. 22.6)
O RCH CHCSCoA
A
OH
O
RCH CH2CSCoA
O
B
O
RC CH2CSCoA C O
O
RCSCoA + CH3CSCoA a) b) c) d)
oxidation hydration reverse-Claisen condensation selective reduction
8. The following are key steps in fatty acid metabolism. What is the best description for the first step (C)? (Sec. 22.6)
O RCH CHCSCoA
A
OH
O
RCH CH2CSCoA
O
B
O
RC CH2CSCoA C O
O
RCSCoA + CH3CSCoA a) b) c) d)
oxidation hydration reverse-Claisen condensation selective reduction
9. The biosynthesis of butanoic acid proceeds via a Claisen reaction of Acetyl-CoA. If the starting material is labeled at the methyl carbon atom, which atoms will be labeled in the product? (Sec. 22.6)
O CH3CSCoA O CH3CH2CH2COH I a) b) c) d)
II
III IV
I, II I, III II, III II, IV
273
Chapter 22 The Organic Chemistry of Metabolism
10. Which best describes this reaction? (Sec. 22.6)
O
O
CH3CH2CCH2CSCoA a) b) c) d)
X
O CH3CH2CSCoA
+ Y
reverse aldol reaction aldol reaction reverse-Claisen condensation Claisen condensation
11. Unsaturated fatty acids require an additional enzyme in the metabolic pathway. Which process involves this enzyme? (Sec. 22.6) a) b) c) d)
oxidation reduction enol / keto isomerization cis / trans isomerization
12. Which agent initially activates fatty acids for further reaction? (Sec. 22.6) a) b) c) d)
NAD+ FAD Coenzyme A + ATP ADP
13. Which statements describing β-oxidation of fatty acid are true? (Sec. 22.6) I) More energy is released in the oxidation of fatty acids than sugars. II) Only NAD+ / NADH are involved in the reactions. III) The series of four reactions is repeated until the entire fatty acid chain is degraded to acetylCoA. IV) The activated fatty acid is a carboxylic-diphosphoric mixed anhydride. a) b) c) d)
II, IV I, III II, III I, IV
14. Which statement is true concerning the balanced half reaction for the oxidation of glucose to pyruvate? (Sec. 22.3, 22.4) a) b) c) d)
The reaction produces two moles of oxygen. The reaction is a four-electron oxidation. The reaction uses two moles of NAD+. The reaction uses two moles of FAD
274
Chapter 22 The Organic Chemistry of Metabolism
15. Which reactions are involved in the conversion of pyruvate to ethanol? (Sec. 22.5) I) oxidation II) reduction III) decarboxylation IV) keto-enol tautomerization a) b) c) d)
I, III II, IV II, III III, IV
16. If carbon atom 3 of glucose is labeled with 13C, which carbon atom is labeled after oxidation to pyruvate? (Sec. 22.5) a) b) c) d)
carbon atom 1 carbon atom 2 carbon atom 3 carbon atoms 1 and 2
17. Which describes Step 4 of glycolysis, the cleavage of fructose 1,6-bisphosphate to two trioses? (Sec. 22.4) a) b) c) d)
Claisen condensation aldol addition reaction reverse-Claisen condensation reverse-Aldol reaction
18. How many moles of ethanol and CO2 are produced in the glycolysis and fermentation of sucrose? (Sec. 22.5) a) b) c) d)
2 moles ethanol, 2 moles CO2 2 moles ethanol, 4 moles CO2 4 moles ethanol, 4 moles CO2 4 moles ethanol, 4 moles CO2
19. If carbon 2 of glucose is labeled with 13C, which carbon is labeled in the alcohol fermentation products? (Sec. 22.5) a) b) c) d)
CO2 ethanol carbon 1 ethanol carbon 2 ethanol carbon 1 and carbon 2
20. Which describes the effect of lactate fermentation of glucose on blood pH and CO2 concentration? (Sec. 22.5) a) b) c) d)
pH increases, CO2 concentration increases pH decreases, CO2 concentration is unchanged pH is unchanged, CO2 concentration decreases pH decreases, CO2 concentration decreases
275
Chapter 22 The Organic Chemistry of Metabolism 21. If deuterium is substituted for hydrogen in NADH, where will the deuterium be in the final product of the metabolic reduction of pyruvate to lactate? (Sec. 22.5)
I H3C
II
OH C
CO
H O III a) b) c) d)
I II III II, III
22. If palmitic acid is labeled at carbon 2 with 13C, which carbon will be labeled in acetyl-CoA after β-oxidation? (Sec. 22.6) a) b) c) d)
the methyl carbon the carbonyl carbon both carbons neither carbon
23. Which reagents are necessary in the glycolysis of glucose to pyruvate? (Sec. 22.4) I) NAD+ II) ADP III) HPO42IV) FAD V) ATP a) b) c) d)
I, II, III, V II, III, IV, V I, III, V III, IV, V
24. How many steps are there in the glycolysis pathway? (Sec. 22.4) a) b) c) d)
4 6 8 10
25. How many steps are there in the fatty acid β-oxidation pathway? (Sec. 22.6) a) b) c) d)
4 6 8 10
276
Chapter 22 The Organic Chemistry of Metabolism 26. Which is the key intermediate in the enzyme catalyzed reverse-aldol reaction of fructose 1,6-bisphosphate to two trioses? (Sec. 22.6) a) b) c) d)
an amine an aldehyde an imine an amide
27. Which statements about carbohydrate digestion and absorption are true? (Sec. 22.3, 22.4) I) The main function of carbohydrates is as a carbon source. II) Hydrolysis begins in the mouth with α-amylase in saliva. III) Starch is hydrolyzed directly to glucose. IV) Hydrolysis is completed in the small intestine. a) b) c) d)
I, III II, IV I, IV II, III
Fill in the Blank 1. Complete the structure of Nicotinamide adenine dinucleotide (NAD). (Sec. 22.2)
O O
P O CH2 O O
OH
NH2
OH N
O
P
O CH2
O OH
N O
N N
OH
277
Chapter 22 The Organic Chemistry of Metabolism 2. Complete the following reaction mechanism by providing the correct mechanism arrows. (Sec. 22.2)
-:Base-Enzyme
H-Base-Enzyme
H
O
O
C
C
H H
O
H H NH2
O NH2
+
N
N
Ad
Ad
3. Provide the product of the following reaction. (Sec. 22.2)
H H HOOC
R
H
+ FAD
+ FADH2
H
4. Provide the product of the following reaction. (Sec. 22.4)
HOCH2 HO
O + ATP
HO
OH
hexokinase + ADP
Mg2+ OH
5. Provide the products of the following reaction. (Sec. 22.4)
2-
CH2OPO3 O HO
H
H
OH
H
OH
aldolase
+
2CH2OPO3 278
Chapter 22 The Organic Chemistry of Metabolism
6. Provide the product of the following reaction. (Sec. 22.4)
2-
CH2OPO3 O HO
H
H
OH
H
OH
+ H3N-Enzyme-Base: 2-
CH2OPO3
7. Provide the product of the following reaction. (Sec. 22.5)
O H 3C C
COO
-
lactate + NADH + H3O+
+ NAD+ + H3O+
dehydrogenase
8. Provide the product of the following reaction. (Sec. 22.6)
O
O
R C CH2 C
O SCoA
+
thiolase-S-
R C
S-Enzyme
+
9. Provide the product of the following reaction. (Sec. 22.6)
-OOC
O
-
O
CH2 C COO + H3C C
citrate
SCoA + H2O
+ CoA-SH
synthase
10. Provide the product of the following reaction. (Sec. 22.7)
COO COO-
H2C COO H C O
C
+ H+
+ CO2
279
Chapter 22 The Organic Chemistry of Metabolism True-False 1. The citric acid cycle is the main metabolic pathway under anaerobic conditions. (Sec. 22.7) 2. The following structure is ADP. (Sec. 22.2)
O N
HN
P O
H2N H2 P O C
O
O
O O
O
N
N O
OH
OH
3. The following reaction is a reduction of the alcohol, oxidation of NAD=. (Sec. 22.2)
OH
O
C
+ NAD+
C
H
4. The following structure is FAD. (Sec. 22.2)
O N
NH N
N H
H
H
OH
H
OH
H
OH
NH2
O
P O
O
N
N
CH2 O
O
O
H 2N
P
O CH2
N
O OH
N
O OH
280
+ NADH + H+
Chapter 22 The Organic Chemistry of Metabolism 5. FAD is reduced in the following reaction. (Sec. 22.2)
CH2 CH2
+ FAD
CH CH
+ FADH2
6. Acetyl-CoA is derived from the degradation of foodstuffs. (Sec. 22.6) 7. The cleavage of fructose-1,6-bisphosphate to two triose phosphates (reaction 4 of the glycolysis sequence) is an example of an aldol reaction. (Sec. 22.6) 8. Pyruvate is the conjugate base of a β-keto carboxylic acid. (Sec. 22.5)
O H3C C COO
-
9. Cleavage of the β-ketoacyl-CoA in reaction 4 of the β-oxidation of fatty acids is an example of a retro-Claisen condensation. (Sec. 22.6) 10. The citric acid cycle oxidizes acetyl-CoA to CO2, producing NADH and FADH2. (Sec. 22.7)
281
Chapter 22 The Organic Chemistry of Metabolism Answers Multiple Choice 1. b 2. a 3. a 4. c 5. b 6. b 7. a 8. c 9. b 10. c 11. d 12. c 13. b 14. b 15. c 16. a 17. d 18. d 19. c 20. b 21. c 22. a 23. a 24. d 25. a 26. c 27. b Fill in the Blank 1.
O NH2
O O
P
O CH2
N
O O
OH
NH2
OH N
O
P
O CH2
O OH
N O
N N
OH
282
Chapter 22 The Organic Chemistry of Metabolism 2.
-:Base-Enzyme
H-Base-Enzyme
H
O
O
C
C
H H
O
H H NH2
NH2
+
N
N
Ad
Ad
3.
H
R
HOOC
H
4.
2- O POH C 3 2
O
HO HO
OH OH
5.
2CH2OPO3 O
+
H
O
H
OH
CH2OH
2-
CH2OPO3
6.
2CH2OPO3
N-Enzyme-Base: -
HO
H
H
OH
H
OH
O
2CH2OPO3 283
Chapter 22 The Organic Chemistry of Metabolism 7.
OH H3C C COO
-
H 8.
O H3C C SCoA 9.
H 2C HO C H 2C
COO COOCOO
10.
H2C COO
-
CH2
O
C COO-
True-False 1. F 2. F 3. F 4. T 5. T 6. T 7. F 8. F 9. T 10. T
284
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