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Problems 49

■ A covalent bond is formed when two atoms share a pair ■ Atomic orbitals combine to give a bonding MO and a
of electrons. higher energy antibonding MO.
■ A polar covalent bond is a covalent bond between ■ Electrons in a bonding MO assist in bonding. Electrons
atoms with different electronegativities. in an antibonding MO detract from bonding.
■ The greater the difference in electronegativity between ■ There is zero probability of finding an electron at a node.
the atoms forming the bond, the closer the bond is to the ■ Cylindrically symmetrical bonds are called sigma (s)
ionic end of the continuum. bonds; side-to-side overlap of parallel p orbitals forms a
■ A polar covalent bond has a dipole (a positive end and a pi (P) bond.
negative end), measured by a dipole moment. ■ Bond strength is measured by the bond dissociation
■ The dipole moment of a bond is equal to the size of the energy; a s bond is stronger than a p bond.
charge × the distance between the charges. ■ To be able to form four bonds, carbon has to promote an
■ The dipole moment of a molecule depends on the electron from an s orbital to an empty p orbital.
magnitude and direction of all the bond dipole moments. ■ C, N, O, and the halogens form bonds using hybrid
■ Core electrons are electrons in inner shells. Valence orbitals.
electrons are electrons in the outermost shell. ■ The hybridization of C, N, or O depends on the number
Lone-pair electrons are valence electrons that do of p bonds the atom forms: no p bonds = sp3, one
not form bonds. p bond = sp2, and two p bonds = sp. Exceptions are
■ formal charge = # of valence electrons – # of electrons carbocations and carbon radicals, which are sp2.
the atom has to itself (all the lone-pair electrons and ■ All single bonds in organic compounds are s bonds.
one-half the bonding electrons)
■ A double bond consists of one s bond and one p bond;
■ Lewis structures indicate which atoms are bonded a triple bond consists of one s bond and two p bonds.
together and show lone pairs and formal charges.
■ The greater the electron density in the region of orbital
■ When the atom is neutral: C forms 4 bonds, N forms overlap, the shorter and stronger the bond.
3 bonds, O forms 2 bonds, and H or a halogen forms
■ Triple bonds are shorter and stronger than double bonds,
1 bond.
which are shorter and stronger than single bonds. The
■ When the atom is neutral: N has 1 lone pair, O has shorter the bond, the stronger it is.
2 lone pairs, and a halogen has 3 lone pairs.
■ Molecular geometry is determined by hybridization:
■ A carbocation has a positively charged carbon, sp3 is tetrahedral, sp2 is trigonal planar, and sp is linear.
a carbanion has a negatively charged carbon, and a
■ Bonding pairs and lone-pair electrons around an atom
radical has an unpaired electron.
stay as far apart as possible.
■ According to molecular orbital (MO) theory, covalent
■ The more s character in the orbital used to form a
bonds result when atomic orbitals combine to form
bond, the shorter and stronger the bond and the larger
molecular orbitals.
the bond angle.

GLOSSARY

The definitions of the key words used in each chapter can be found at the beginning of each pertinent chapter in the Study
Guide/Solutions Manual. The definitions of all the key words used in this book can be found in the Glossary on page G-1.

PROBLEMS
46. Draw a Lewis structure for each of the following species:
a. H2CO3 b. CO32 - c. CH2O d. CO2
47. a. Which of the following has a nonpolar covalent bond?
b. Which of the following has a bond closest to the ionic end of the bond spectrum?

CH3NH2 CH3CH3 CH3F CH3OH

48. What is the hybridization of all the atoms (other than hydrogen) in each of the following species? What are the bond angles around
each atom?
a. NH3 c. - CH3 e. + NH4 g. HCN i. H3O +
b. BH3 d. . CH3 f. + CH3 h. C(CH3)4 j. H2C “ O
50 CHAPTER 1 Remembering General Chemistry: Electronic Structure and Bonding

49. Draw the condensed structure of a compound that contains only carbon and hydrogen atoms and that has
a. three sp3 hybridized carbons.
b. one sp3 hybridized carbon and two sp2 hybridized carbons.
c. two sp3 hybridized carbons and two sp hybridized carbons.
50. Predict the approximate bond angles: +
a. the C i N i C bond angle in (CH3)2NH2 c. the C i N i H bond angle in (CH3)2NH
b. the C i O i H bond angle in CH3OH d. the C i N i C bond angle in (CH3)2NH
51. Draw the ground-state electronic configuration for the following:
a. Mg b. Ca2 + c. Ar d. Mg2 +
52. Draw a Lewis structure for each of the following species:
a. CH3NH2 b. HNO2 c. N2H4 d. NH2O -
53. What is the hybridization of each of the carbon and oxygen atoms in vitamin C?

CH2OH
HO CH
O O
HC C
C C
HO OH
vitamin C

54. List the bonds in order from most polar to least polar.
a. C i O, C i F, C i N b. C i Cl, C i I, C i Br c. H i O, H i N, H i C d. C i H, C i C, C i N
55. Draw the Lewis structure for each of the following compounds:
a. CH3CHO b. CH3OCH3 c. CH3COOH
56. What is the hybridization of the indicated atom in each of the following molecules?
O
a. CH3CH CH2 b. CH3CCH3 c. CH3CH2OH d. CH3C N e. CH3CH NCH3 f. CH3OCH2CH3

57. Predict the approximate bond angles for the following:


a. the H i C i H bond angle in H2C “ O c. the C i C i N bond angle in CH3C ‚ N
b. the F i B i F bond angle in - BF4 d. the C i C i N bond angle in CH3CH2NH2
58. Show the direction of the dipole moment in each of the following bonds (use the electronegativities given in Table 1.3):
a. H3C i Br b. H3C i Li c. HO i NH2 d. I i Br e. H3C i OH f. (CH3)2 N i H
59. Draw the missing lone-pair electrons and assign the missing formal charges for the following.

H H H H
a. H C O H b. H C O H c. H C O d. H C N H
H H H H H H

60. a. Which of the indicated bonds in each molecule is shorter?


b. Indicate the hybridization of the C, O, and N atoms in each of the molecules.
H CH3
1. CH3CH CHC CH 3. CH3NH CH2CH2N CHCH3 5. C CHC C C H
Solo b H CH3
O H
2. CH3CCH2 OH 4. C CHC C H 6. Br CH2CH2CH2 Cl
H
Problems 51

61. For each of the following molecules, indicate the hybridization of each carbon and give the approximate values of all the bond angles:
a. CH3C ‚ CH b. CH3CH “ CH2 c. CH3CH2CH3 d. CH2 CH CH CH2
62. Draw the Lewis structure for each of the following compounds:
a. (CH3)3COH b. CH3CH(OH)CH2CN c. (CH3)2CHCH(CH3)CH2C(CH3)3
63. Rank the following compounds from highest dipole moment to lowest dipole moment:

CH Cl CH Cl CH Cl CH Cl
HC C HC C HC C HC C
C CH HC C C CH HC CH
Cl CH CH Cl Br CH CH

64. In which orbitals are the lone pairs in nicotine?

H2C CH2
CH CH CH2
HC C N
HC CH CH3
N
nicotine
nicotine increases the concentration of dopamine
in the brain; the release of dopamine makes a
person feel good—the reason why nicotine
is addictive

65. Indicate the formal charge on each carbon that has one. All lone pairs are shown.

H H H
H C H C H C H C H CH2 CH CH2 CH CH2 CH
H H H

66. Do the sp2 carbons and the indicated sp3 carbons lie in the same plane?

CH3
CH3 CH3

67. a. Which of the species have bond angles of 109.5°?


b. Which of the species have bond angles of 120°?

H2O H3O+ +
CH3 BF3 NH3 +
NH4 −
CH3

68. Which compound has a longer C—Cl bond?

CH3CH2Cl CH2 CHCl


at one time it was used as a used as the starting material
refrigerant, an anesthetic, and a for the synthesis of a plastic that
propellant for aerosol sprays is used to make bottles, flooring,
and clear packaging for food

69. Which compound has a larger dipole moment, CHCl3 or CH2Cl2?


70. The following compound has two isomers. One isomer has a dipole moment of 0 D, whereas the other has a dipole moment of
2.95 D. Propose structures for the two isomers that are consistent with these data.
ClCH “ CHCl
52 CHAPTER 1 Remembering General Chemistry: Electronic Structure and Bonding

71. Explain why the following compound is not stable:

H H
H
C
H C C
H C C
C
H
H H

72. Explain why CH3Cl has a greater dipole moment than CH3F even though F is more electronegative than Cl.
73. Draw a Lewis structure for each of the following species:
a. CH3N2+ b. CH2N2 c. N3− d. N2O (arranged NNO)
140 CHAPTER 3 An Introduction to Organic Compounds

PROBLEMS
52. Draw a condensed structure and a skeletal structure for each of the following compounds:
a. sec-butyl tert-butyl ether e. 5-(1,2-dimethylpropyl)nonane i. 3-ethoxy-2-methylhexane
b. isoheptyl alcohol f. triethylamine j. 5-(1,2-dimethylpropyl)nonane
c. sec-butylamine g. 4-(1,1-dimethylethyl)heptane k. 3,4-dimethyloctane
d. isopentyl bromide h. 5,5-dibromo-2-methyloctane l. 4-(1-methylethyl)nonane
53. List the following compounds from highest boiling to lowest boiling:

OH N
N
H O O OH
NH2

54. a. What is each compound’s systematic name?


b. Draw a skeletal structure for each condensed structure given, and draw a condensed structure for each skeletal structure given in
the following list:
Solo b CH3

1. (CH3)3CCH2CH2CH2CH(CH3)2 5. BrCH2CH2CH2CH2CH2NHCH2CH3 9. NCH3

CH2CH3
2. 6. 10.
Br
OH
CH3
3. CH3CHCH2CHCH2CH3 7. CH3CH2CHOCH2CH3 11.
CH3 OH CH2CH2CH2CH3 Br
4. (CH3CH2)4C 8. CH3OCH2CH2CH2OCH3
55. Which of the following represents a cis isomer?
CH3 CH3

CH3 CH3
CH3 CH3

CH3 CH3
A B C D

56. a. How many primary carbons does each of the following compounds have?
b. How many secondary carbons does each one have?
c. How many tertiary carbons does each one have?
1. CH2CH3 2.

CH2CHCH3
CH3

57. Which of the following conformers of isobutyl chloride is the most stable?

CH3 CH3 Cl
H H H Cl H3C CH3
H CH3 H CH3 H H
Cl H H
A B C
Problems 141

58. Draw the structural formula for an alkane that has


a. six carbons, all secondary.
b. eight carbons and only primary hydrogens.
c. seven carbons with two isopropyl groups.
59. What is each compound’s systematic name?
a. CH3CH2CHCH3 e. CH3CHCH2CH2CH3 h. CH3CHCH2CH2CH2OH
NH2 CH3 CH3
b. CH3CH2CHCH3 f. CH3CHNH2 i.
Cl CH3 Br
CH3
c. CH3CH2CHNHCH2CH3 g. CH3C Br j. OH

CH3 CH2CH3
d. CH3CH2CH2OCH2CH3
60. Which has
a. the higher boiling point: 1-bromopentane or 1-bromohexane?
b. the higher boiling point: pentyl chloride or isopentyl chloride?
c. the greater solubility in water: 1-butanol or 1-pentanol?
d. the higher boiling point: 1-hexanol or 1-methoxypentane?
e. the higher melting point: hexane or isohexane?
f. the higher boiling point: 1-chloropentane or 1-pentanol?
g. the higher boiling point: 1-bromopentane or 1-chloropentane?
h. the higher boiling point: diethyl ether or butyl alcohol?
i. the greater density: heptane or octane?
j. the higher boiling point: isopentyl alcohol or isopentylamine?
k. the higher boiling point: hexylamine or dipropylamine?
61. a. Draw Newman projections of the two conformers of cis-1,3-dimethylcyclohexane.
b. Which of the conformers would predominate at equilibrium?
c. Draw Newman projections of the two conformers of the trans isomer.
d. Which of the conformers would predominate at equilibrium?
62. Ansaid and Motrin belong to the group of drugs known as nonsteroidal anti-inflammatory drugs (NSAIDs). Both are only slightly
soluble in water, but one is a little more soluble than the other. Which of the drugs has the greater solubility in water?

F CH3 CH3 CH3

CHCOOH CH3CHCH2 CHCOOH

Ansaid® Motrin®

63. Draw a picture of the hydrogen bonding in methanol.


64. A student was given the structural formulas of several compounds and was asked to give them systematic names. How many did the
student name correctly? Correct those that are misnamed.
a. 4-bromo-3-pentanol e. 5-(2,2-dimethylethyl)nonane i. 1-bromo-4-pentanol
b. 2,2-dimethyl-4-ethylheptane f. isopentyl bromide j. 3-isopropyloctane
c. 5-methylcyclohexanol g. 3,3-dichlorooctane k. 2-methyl-2-isopropylheptane
d. 1,1-dimethyl-2-cyclohexanol h. 5-ethyl-2-methylhexane l. 2-methyl-N,N-dimethyl-4-hexanamine
65. Which of the following conformers has the highest energy (is the least stable)?

CH3 CH3

Cl Cl CH3 Cl
A B C
142 CHAPTER 3 An Introduction to Organic Compounds

66. Give the systematic names for all alkanes with molecular formula C7H16 that do not have any secondary hydrogens.
67. Draw skeletal structures for the following:
a. 5-ethyl-2-methyloctane c. 2,3,3,4-tetramethylheptane e. 2-methyl-4-(1-methylethyl)octane
b. 1,3-dimethylcyclohexane d. propylcyclopentane f. 2,6-dimethyl-4-(2-methylpropyl)decane
68. For rotation about the C@3 i C@4 bond of 2-methylhexane, do the following:
a. Draw the Newman projection of the most stable conformer.
b. Draw the Newman projection of the least stable conformer.
c. About which other carbon–carbon bonds may rotation occur?
d. How many of the carbon–carbon bonds in the compound have staggered conformers that are all equally stable?
69. Draw all the isomers that have molecular formula C5H11Br. (Hint: There are eight.)
a. Give the systematic name for each of the isomers.
b. Give a common name for each isomer that has a common name.
c. How many of the isomers are primary alkyl halides?
d. How many of the isomers are secondary alkyl halides? solo c-e
e. How many of the isomers are tertiary alkyl halides?
70. What is each compound’s systematic name?

a. e. i.
NH2

b. OH f. j.
Cl
O

c. g.

OH
d. h.

71. Draw the two chair conformers for each of the following, and indicate which conformer is more stable:
a. cis-1-ethyl-3-methylcyclohexane d. cis-1,2-diethylcyclohexane
b. trans-1-ethyl-2-isopropylcyclohexane e. cis-1-ethyl-3-isopropylcyclohexane
c. trans-1-ethyl-2-methylcyclohexane f. cis-1-ethyl-4-isopropylcyclohexane
72. Why are lower molecular weight alcohols more soluble in water than higher molecular weight alcohols?
73. a. Draw a potential energy diagram for rotation about the C i C bond of 1,2-dichloroethane through 360⬚, starting with the least
stable conformer. The anti conformer is 1.2 kcal/mol more stable than a gauche conformer. A gauche conformer has two energy
barriers, 5.2 kcal/mol and 9.3 kcal/mole.
b. Draw the conformer that would be present in greatest concentration.
c. How much more stable is the most stable staggered conformer than the most stable eclipsed conformer?
d. How much more stable is the most stable staggered conformer than the least stable eclipsed conformer?
74. For each of the following compounds, is the cis isomer or the trans isomer more stable?

a. b. c.

75. How many ethers have molecular formula C5H12O? Draw their structures and give each a systematic name. What are their
common names?
Problems 143

76. Draw the most stable conformer of the following molecule. (A solid wedge points out of the plane of the paper toward the viewer.
A hatched wedge points back from the plane of the paper away from the viewer.)
CH3

H3C CH3

77. What is each compound’s systematic name?


CH2CH3
a. CH3CH2CHCH2CH2CHCH3 c. CH3CHCHCH2Cl e.
NHCH3 CH3 Cl
CH3
b. CH3CH2CHCH2CHCH2CH3 d. CH3CH2CHCH3 f.
CH3CHCH3 CH3CHCH3

78. Calculate the energy difference between the two chair conformers of trans-1,2-dimethylcyclohexane.
79. The most stable form of glucose (blood sugar) is a six-membered ring in a chair conformation with its five substituents all in equatorial
positions. Draw the most stable conformer of glucose by putting the OH groups on the appropriate bonds in the structure on the right.

CH2OH
HO CH2OH
O O
HO OH
OH
glucose

80. What is each compound’s systematic name?

a. CH3CHCH2CHCH2CH3 d. CH3CHCH2CH2CHCH2CH2CH3 g. HO
CH3 OH CH3 Br
Br
OH
b. e. h. Br
OH
CH3
OH
c. CH3CHCHCH2CH3 f.
Br
OH

81. Explain the following:


a. 1-Hexanol has a higher boiling point than 3-hexanol.
b. Diethyl ether has very limited solubility in water, but tetrahydrofuran is completely soluble.

O
tetrahydrofuran

82. One of the chair conformers of cis-1,3-dimethylcyclohexane is 5.4 kcal/mol (23 kJ/mol) less stable than the other. How much steric
strain does a 1,3-diaxial interaction between two methyl groups introduce into the conformer?
Problems 181

SOME IMPORTANT THINGS TO REMEMBER

■ Stereochemistry is the field of chemistry that deals with ■ A racemic mixture is a mixture of equal amounts of
the structures of molecules in three dimensions. two enantiomers.
■ Isomers are compounds with the same molecular ■ The letters R and S indicate the configuration about an
formula but different structures. asymmetric center.
■ Constitutional isomers differ in the way their atoms are ■ If one member of a pair of stereoisomers has the
connected. R configuration and the other has the S configuration,
■ Stereoisomers differ in the way their atoms are arranged they are enantiomers; if they both have the R
in space. configuration or both have the S configuration, they
are identical.
■ There are two kinds of stereoisomers: cis–trans isomers
and isomers that contain asymmetric centers. ■ Chiral compounds are optically active; achiral
compounds are optically inactive.
■ Because rotation about the bonds in a cyclic compound
is restricted, disubstituted cyclic compounds exist as ■ If one enantiomer rotates the plane of polarization
cis-trans isomers. The cis isomer has the substituents clockwise ( + ), its mirror image will rotate it the same
on the same side of the ring; the trans isomer has the amount counterclockwise ( - ).
substituents on opposite sides of the ring. ■ Each optically active compound has a characteristic
■ Because rotation about a double bond is restricted, an specific rotation.
alkene can exist as cis–trans isomers. The cis isomer ■ A racemic mixture, indicated by ( { ), is optically
has its hydrogens on the same side of the double bond; inactive.
the trans isomer has its hydrogens on opposite sides of ■ In the case of compounds with two asymmetric
the double bond. centers, enantiomers have the opposite configuration
■ A chiral molecule has a nonsuperimposable mirror at both asymmetric centers; diastereomers have
image; an achiral molecule has a superimposable the same configuration at one asymmetric center
mirror image. and the opposite configuration at the other
■ An asymmetric center is an atom bonded to four asymmetric center.
different atoms or groups. ■ A meso compound has two or more asymmetric centers
■ Enantiomers are nonsuperimposable mirror images. and a plane of symmetry; it is optically inactive.
■ Diastereomers are stereoisomers that are not ■ A compound with the same four groups bonded to
enantiomers. two different asymmetric centers will have three
stereoisomers—namely, a meso compound and a pair of
■ Enantiomers have identical physical and chemical
enantiomers.
properties; diastereomers have different physical and
chemical properties. ■ Atoms other than carbons (such as N and P) can be
asymmetric centers if they are bonded to four different
■ An achiral reagent reacts identically with both
atoms or groups.
enantiomers; a chiral reagent reacts differently with
each enantiomer.

PROBLEMS

53. Disregarding stereoisomers, draw the structures of all compounds with molecular formula C5H10. Which ones can exist as stereoisomers?
54. Draw all possible stereoisomers for each of the following. Indicate if no stereoisomers are possible.
a. 1-bromo-2-chlorocyclohexane f. 1,2-dimethylcyclopropane
b. 2-bromo-4-methylpentane g. 4-bromo-2-pentene
c. 1,2-dichlorocyclohexane h. 3,3-dimethylpentane
d. 2-bromo-4-chloropentane i. 1-bromo-2-chlorocyclobutane
e. 1-bromo-4-chlorocyclohexane j. 1-bromo-3-chlorocyclobutane
55. Which of the following has an asymmetric center?
CHBr2Cl BHFCl CH3CHCl2 CHFBrCl BeHCl
182 CHAPTER 4 Isomers: The Arrangement of Atoms in Space

56. Name the following compounds using R,S designations:


CH3 CH2OH CH3CH2 Br
a. HO H b. HO CH3 c. C C CH3
H Cl H
CH2CH2CH2OH HO CH2Br
CH2CH3

57. Mevacor is used clinically to lower serum cholesterol levels. How many asymmetric centers does Mevacor have?
HO O

O
O
O
CH3

Mevacor®

58. Are the following pairs identical, enantiomers, diastereomers, or constitutional isomers?
CH3CH2 Br CH3CH2 CH3
a. and e.
Br Br Br Br C C CH3 and C C CH(CH3)2
H HO
HO CH(CH3)2 H Br
Cl Cl
b. and f. and
Br Br Br Br Cl Cl
H CH3 H Br
CH3 and
c. g. C C and C C
CH3 CH3 CH3
CH3 Br CH3 CH3
CH3 CH3
CH3 CH3 Br CH3 H CH3
d. and
h. C C and C C
CH3 CH3 H CH3 Br CH3

59. Which of the following are optically active?

CH3 CH3

CH3
Br Br Br CH3
Br

60. For many centuries, the Chinese have used extracts from a group of herbs known as ephedra to treat asthma. A compound named
ephedrine has been isolated from these herbs and found to be a potent dilator of air passages in the lungs.
a. How many stereoisomers does ephedrine have?
b. The stereoisomer shown here is the one that is pharmacologically active. What is the configuration of each of the asymmetric centers?

CH3
H
CHCHNHCH3
C C NHCH3
OH HO
ephedrine H CH3

61. Name each of the following:

a. b.
Cl OH Br
Problems 183

62. Which of the following has an achiral stereoisomer?


a. 2,3-dichlorobutane f. 2,4-dibromopentane
b. 2,3-dichloropentane g. 2,3-dibromopentane
c. 2,3-dichloro-2,3-dimethylbutane h. 1,4-dimethylcyclohexane
d. 1,3-dichlorocyclopentane i. 1,2-dimethylcyclopentane
e. 1,3-dibromocyclobutane j. 1,2-dimethylcyclobutane
63. Are the following pairs identical, enantiomers, diastereomers, or constitutional isomers?
a. Cl Cl c. Cl CH3
and and
CH3 CH3 CH3 Cl

b. Cl Cl Cl
and
d. Cl
CH3 CH3 and
CH3 CH3

64. Citrate synthase, one of the enzymes in the series of enzyme-catalyzed reactions known as the citric acid cycle (Section 25.10),
catalyzes the synthesis of citric acid from oxaloacetic acid and acetyl-CoA. If the synthesis is carried out with acetyl-CoA that
contains radioactive carbon (14C) in the indicated position (Section 1.1), the isomer shown here is obtained. (If two isotopes—atoms
with the same atomic number, but different mass numbers—are being compared, the one with the greater mass number has the
higher priority.)

14
O O CH2COOH
14 citrate synthase
HOOCCH2CCOOH + CH3CSCoA C
HO COOH
oxaloacetic acid acetyl-CoA
CH2COOH
citric acid

a. Which stereoisomer of citric acid is synthesized, R or S?


b. Why is the other stereoisomer not obtained?
c. If the acetyl-CoA used in the synthesis contains 12C instead of 14C, will the product of the reaction be chiral or achiral?
65. Are the following pairs identical, enantiomers, diastereomers, or constitutional isomers?
HC CH2 CH2CH3 CH2CH3

a. C and C e. and
CH3CH2 CH3 H CH3 CH3
H HC CH2
CH2OH CH2CH3
b. H CH3 and CH3 H f. and
CH2CH3 CH2OH
Cl Cl Cl Cl
CH3 CH3
c. HO H and H OH g. and
H Cl Cl H
Cl
CH3 CH3
Cl Cl Cl
CH3 CH2CH3
d. HO H and HO H h. and
H Cl H Cl
CH2CH3 CH3
Cl Cl Cl Cl
66. The specific rotation of (R)-( + )-glyceraldehyde is +8.7. If the observed specific rotation of a mixture of (R)-glyceraldehyde and
(S)-glyceraldehyde is +1.4, what percent of glyceraldehyde is present as the R enantiomer?
184 CHAPTER 4 Isomers: The Arrangement of Atoms in Space

67. Indicate whether each of the following structures is (R)-2-chlorobutane or (S)-2-chlorobutane.


Cl Cl
Cl H 3 C H
a. C c. e.
CH3CH2 CH 3 H CH3
H
H
CH3
CH3
Cl H H
b. H Cl d. f.
H Cl
CH2CH3
CH3

68. A solution of an unknown compound (3.0 g of the compound in 20 mL of solution), when placed in a polarimeter tube 2.0 dm long, was
found to rotate the plane of polarized light 1.8⬚ in a counterclockwise direction. What is the specific rotation of the compound?
69. Butaclamol is a potent antipsychotic that has been used clinically in the treatment of schizophrenia. How many asymmetric centers
does it have?

OH
C(CH3)3
N
H H

butaclamol

70. Explain how R and S are related to ( + ) and ( - ).


71. Are the following pairs identical, enantiomers, diastereomers, or constitutional isomers?
OH CH3 CH3 CH2CH3
H H H CH3 H Br H Cl
a. and b. and
H CH3 H OH H CH2CH3 H CH3
CH3 H Cl Br
72. a. Draw all possible stereoisomers of the following compound:
HOCH2CH CH CHCH2OH
OH OH OH

b. Which stereoisomers are optically inactive?


73. What is the configuration of the asymmetric centers in the following structures?
CH2CH2Br BrCH2 OH H3C CH2CH3
a. C b. C C H c. C C H
Br H H Br
CH2CH2CH3 Br CH O H Br

74. a. Draw all the isomers with molecular formula C6H12 that contain a cyclobutane ring. (Hint: There are seven.)
b. Name the compounds without specifying the configuration of any asymmetric centers.
c. Identify:
1. constitutional isomers 5. achiral compounds
solo 2. stereoisomers 6. meso compounds
3. cis–trans isomers 7. enantiomers
a y c 4. chiral compounds 8. diastereomers
75. A compound has a specific rotation of -39.0. A solution of the compound (0.187 g/mL) has an observed rotation of -6.52⬚ when
placed in a polarimeter tube 10 cm long. What is the percent of each enantiomer in the solution?
Problems 185

76. Are the following pairs identical, enantiomers, diastereomers, or constitutional isomers?

a. c.
and and

b. d.
and and

77. Draw structures for each of the following:


a. (S)-1-bromo-1-chlorobutane
b. (2R,3R)-2,3-dichloropentane
c. an achiral isomer of 1,2-dimethylcyclohexane
d. a chiral isomer of 1,2-dibromocyclobutane
e. two achiral isomers of 3,4,5-trimethylheptane
78. Explain why the enantiomers of 1,2-dimethylaziridine can be separated, even though one of the “groups” attached to nitrogen is a
lone pair.

H 3C CH3

N N
CH3 H3C
enantiomers of 1,2-dimethylaziridine

79. A sample of (S)-( + )-lactic acid was found to have an enantiomeric excess of 72%. How much R isomer is present in the sample?
80. Indicate whether each of the structures in the second row is an enantiomer of, a diastereomer of, or is identical to the structure in the
top row.

CH3
H Br
H CH3
CH2CH3

CH3 CH3 CH3


Br
Br H Br H Br H
H CH3 CH3 CH2CH3 CH3CH2 H
Br
CH2CH3 H CH3
A B C D E

81. a. Using the wedge-and-dash notation, draw the nine stereoisomers of 1,2,3,4,5,6-hexachlorocyclohexane.
b. From the nine stereoisomers, identify one pair of enantiomers.
c. Draw the most stable conformation of the most stable stereoisomer.
82. Tamiflu is used for the prevention and treatment of flu. What is the configuration of each of its asymmetric centers? (How Tamiflu
Works is explained on page 1124.)

O
O O
HN
O
H2N
Tamiflu®
186 CHAPTER 4 Isomers: The Arrangement of Atoms in Space

83. A student decided that the configuration of the asymmetric centers in a sugar such as d-glucose could be determined rapidly
by simply assigning the R configuration to an asymmetric center with an OH group on the right and the S configuration to an
asymmetric center with an OH group on the left. Is he correct? (We will see in Chapter 21 that the “d” in d-glucose means the
OH group on the bottommost asymmetric center is on the right.)

HC O
H OH
HO H
H OH
H OH
CH2OH
D-glucose

84. What the configuration of each of the asymmetric centers in the following compounds?
O CH3 OH
a. CH2CH3 b. c.
CH3
O
Br
85. a. Draw the two chair conformers for each of the stereoisomers of trans-1-tert-butyl-3-methylcyclohexane.
b. For each pair, indicate which conformer is more stable.
86. a. Do the following compounds have any asymmetric centers?
1. CH2 “ C “ CH2
2. CH3CH “ C “ CHCH3
b. Are the compounds chiral? (Hint: Make models.)
87. Is the following compound optically active?

Cl Br

Br Cl
Problems 79

■ Approximate pKa values are as follows: protonated and the closer it is to the acidic hydrogen, the stronger
alcohols, protonated carboxylic acids, protonated is the acid.
water  6 0; carboxylic acids ~5; protonated amines ~10; ■ Delocalized electrons (electrons that are shared by
alcohols and water ~15. more than two atoms) stabilize a compound.
■ The pH of a solution indicates the concentration of ■ A resonance hybrid is a composite of the resonance
protons in the solution; the smaller the pH, the more contributors, structures that differ only in the location
acidic the solution. of their p electrons and lone-pair electrons.
■ In acid–base reactions, the equilibrium favors ■ The Henderson–Hasselbalch equation gives the
formation of the weaker acid. relationship between pKa and pH: a compound exists
■ Curved arrows indicate the bonds that are broken and primarily in its acidic form (with its proton) in solutions
formed as reactants are converted into products. more acidic than its pKa value and primarily in its basic
■ The strength of an acid is determined by the stability of form (without its proton) in solutions more basic than
its conjugate base: the more stable (weaker) the base, the its pKa value.
stronger its conjugate acid. ■ A buffer solution contains both a weak acid and its
■ When atoms are similar in size, the strongest acid conjugate base.
will have its hydrogen attached to the more electro- ■ In this text, the term acid is used to mean a proton-
negative atom. donating acid, the term Lewis acid is used to refer to
■ When atoms are very different in size, the strongest acid non-proton-donating acids such as AlCl3 or BF3, and
will have its hydrogen attached to the larger atom. the term electrophile refers to both proton-donating
and non-proton-donating acids.
■ Hybridization affects acidity because an sp hybridized
atom is more electronegative than an sp2 hybridized ■ In this text, the term base is used to mean a compound
atom, which is more electronegative than an sp3 that shares its lone pair with a proton, and the term
hybridized atom. nucleophile is used for a compound that shares its lone
pair with an atom other than a proton.
■ Inductive electron withdrawal increases acidity: the
more electronegative the electron-withdrawing group

PROBLEMS
47. a. List the following alcohols in order from strongest acid to weakest acid:
CCl3CH2OH CH2ClCH2OH CHCl2CH2OH
Ka = 5.75 × 10−13 Ka = 1.29 × 10−13 Ka = 4.90 × 10−13

b. Explain the relative acidities.


48. Which is a stronger base?
a. HS− or HO− c. CH3OH or CH3O− e. CH3COO− or CF3COO−

b. CH3O− or CH3NH d. Cl− or Br− f. CH3CHClCOO - or CH3CHBrCOO -

49. Draw curved arrows to show where the electrons start from and where they end up in the following reactions:
+
O OH
+ − −
a. NH3 + H Cl NH4 + Cl c. C + H Cl C + Cl
H OH H OH

b. H2O + FeBr3 H2O+ FeBr3

50. a. List the following carboxylic acids in order from strongest acid to weakest acid:

CH3CH2CH2COOH CH3CH2CHCOOH ClCH2CH2CH2COOH CH3CHCH2COOH


Ka = 1.52 × 10−5 Ka = 2.96 × 10−5
Cl Cl
Ka = 1.39 × 10−3 Ka = 8.9 × 10−5

b. How does the presence of an electronegative substituent such as Cl affect the acidity of a carboxylic acid?
c. How does the location of the substituent affect the acidity of the carboxylic acid?
80 CHAPTER 2 Acids and Bases: Central to Understanding Organic Chemistry

51. Draw the products of the following reactions:

a. CH3OCH3 + BF3 b. CH3OCH3 + H Cl c. CH3NH2 + AlCl3


52. For the following compound,
a. draw its conjugate acid. b. draw its conjugate base.
HOCH2CH2CH2NH2
53. List the following compounds in order from strongest acid to weakest acid:
CH3CH2OH CH3CH2NH2 CH3CH2SH CH3CH2CH3
54. For each of the following compounds, draw the form in +which it will predominate at pH = 3, pH = 6, pH = 10, and pH = 14:
a. CH3COOH b. CH3CH2NH3 c. CF3CH2OH
pKa ⴝ 4.8 pKa ⴝ 11.0 pKa ⴝ 12.4

55. Give the products of the following acid–base reactions, and indicate whether reactants or products are favored at equilibrium
(use the pKa values that are given in Section 2.3):
O O
a. CH3COH + CH3O − c. CH3COH + CH3NH2


b. CH3CH2OH + NH2 d. CH3CH2OH + HCl
56. a. List the following alcohols in order from strongest acid to weakest acid.
b. Explain the relative acidities.

CH2 CHCH2OH CH3CH2CH2OH HC CCH2OH

57. For each compound, indicate the atom that is most apt to be protonated.
CH3 CH3
a. CH3 CH CH2NH2 b. CH3 C OH c. CH3 C CH2OH
OH NH2 NH2
58. a. Given the Ka values, estimate the pKa value of each of the following acids without using a calculator (that is, is it between 3 and
4, between 9 and 10, and so on?):
1. nitrous acid (HNO2), Ka = 4.0 * 10 - 4 3. bicarbonate 1HCO3- 2 , Ka = 6.3 * 10 - 11
2. nitric acid (HNO3), Ka = 22 4. hydrogen cyanide (HCN), Ka = 7.9 * 10 - 10
5. formic acid (HCOOH), Ka = 2.0 * 10 - 4
b. Determine the exact pKa values, using a calculator.
c. Which is the strongest acid?

59. A single bond between two carbons with different hybridizations has a small dipole. What is the direction of the dipole in the indi-
cated bonds?

a. CH3 CH CH2 b. CH3 C CH


60. Tenormin, a member of the group of drugs known as beta-blockers, is used to treat high blood pressure and improve survival
after a heart attack. It works by slowing down the heart in order to reduce its workload. Which hydrogen in Tenormin is the
most acidic?

O OCH2CHCH2NHCH(CH3)2

C OH
H2N CH2
Tenormin®
atenolol

61. From which acids can HO- remove a proton in a reaction that favors product formation?

+
CH3COOH CH3CH2NH2 CH3CH2NH3 CH3C CH
A B C D
Problems 81

62. a. For each of the following pairs of reactions, indicate which one has the more favorable equilibrium constant (that is, which one
most favors products): + +
1. CH3CH2OH + NH3 L CH3CH2O - + NH4 2. CH3CH2OH + NH3 L CH3CH2O - + NH4
or +
or +
CH3OH + NH3 L CH3O - + NH4 CH3CH2OH + CH3NH2 L CH3CH2O - + CH3NH3
b. Which of the four reactions has the most favorable equilibrium constant?
63. You are planning to carry out a reaction that produces protons. The reaction will be buffered at pH = 10.5. Would it be better to use a
protonated methylamine/methylamine buffer or a protonated ethylamine/ethylamine buffer? (pKa of protonated methylamine = 10.7;
pKa of protonated ethylamine = 11.0)
64. Which is a stronger acid?
a. CH2 CHCOOH or CH3CH2COOH c. CH2 CHCOOH or HC CCOOH

O
b. d.
+ or + + or +
N N N N
H H H H H H H
65. Citrus fruits are rich in citric acid, a compound with three COOH groups. Explain the following:
a. The first pKa (for the COOH group in the center of the molecule) is lower than the pKa of acetic acid.
b. The third pKa is greater than the pKa of acetic acid.

O OH O
C C C
pKa = 4.5 HO CH2 CH2 OH pKa = 5.8
C
O OH
pKa = 3.1

66. Given that pH + pOH = 14 and that the concentration of water in a solution of water is 55.5 M, show that the pKa of water is 15.7.
(Hint: pOH = -log 3 HO - 4 )
67. How could you separate a mixture of the following compounds? The reagents available to you are water, ether, 1.0 M HCl, and
1.0 M NaOH. (Hint: See Problem 42.)
+ +
COOH NH3Cl− OH Cl NH3Cl−

pKa = 4.17 pKa = 4.60 pKa = 9.95 pKa = 10.66

68. Carbonic acid has a pKa of 6.1 at physiological temperature. Is the carbonic acid/bicarbonate buffer system that maintains the pH of
the blood at 7.4 better at neutralizing excess acid or excess base?
69. a. If an acid with a pKa of 5.3 is in an aqueous solution of pH 5.7, what percentage of the acid is present in its acidic form?
b. At what pH will 80% of the acid exist in its acidic form?
70. Calculate the pH values of the following solutions. (Hint: See Special Topic I in the Study Guide and Solutions Manual.)
a. a 1.0 M solution of acetic acid (pKa = 4.76)
b. a 0.1 M solution of protonated methylamine (pKa = 10.7)
c. a solution containing 0.3 M HCOOH and 0.1 M HCOO - (pKa of HCOOH = 3.76)