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CHAPTER 5 |
Aromatic Compounds
5.24 How would you synthesize the following compound starting from benzene?
More than one step is needed.
5.25 The following compound cant be synthesized using the methods discussed
in this chapter. Why not?
Additional Problems
N AMING A ROMATIC
C OMPOUNDS
CH3
CH3
(b)
(c)
CO2H
Br
CHCH2CH2CHCH3
H3C
Br
(d)
(e)
Br
(f)
NH2
NO2
CH2CH2CH3
NO2
Cl
CH3
| Exercises
183
N(CH3)2
(b)
(c)
OCH2CH3
(d)
Cl
(b)
CH3CH2Cl
AlCl3
(c)
CH3CH2COCl
CO2H
AlCl3
(d)
HNO3
H2SO4
N(CH2CH3)2
SO3
H2SO4
184
CHAPTER 5 |
Aromatic Compounds
5.36 Rank the compounds in each group according to their reactivity toward
electrophilic substitution:
(a) Chlorobenzene, o-dichlorobenzene, benzene
(b) p-Bromonitrobenzene, nitrobenzene, phenol
(c) Fluorobenzene, benzaldehyde, o-dimethylbenzene
5.37 The orientation of electrophilic aromatic substitution on a disubstituted
benzene ring is usually controlled by whichever of the two groups already
on the ring is the more powerful activator. Name and draw the structure(s)
of the major product(s) of electrophilic chlorination of the following
substances:
(a) m-Nitrophenol
(b) o-Methylphenol
(c) p-Chloronitrobenzene
5.38 Predict the major product(s) you would expect to obtain from sulfonation of
the following substances (see Problem 5.37):
(a) o-Chlorotoluene
(b) m-Bromophenol
(c) p-Nitrotoluene
5.39 Rank the following aromatic compounds in the expected order of their reactivity toward FriedelCrafts acylation. Which compounds are unreactive?
(a) Bromobenzene
(b) Toluene
(c) Anisole (C6H5OCH3)
(d) Nitrobenzene
(e) p-Bromotoluene
5.40 In some cases, the FriedelCrafts acylation reaction can occur intramolecularly, that is, within the same molecule. Predict the product of the following
reaction:
O
Cl
AlCl3
5.41 What is the structure of the compound with formula C8H9Br that gives
p-bromobenzoic acid on oxidation with KMnO4?
5.42 Draw the three additional resonance structures of anthracene.
Anthracene
M ECHANISMS
5.43 Show the steps involved in the FriedelCrafts reaction of benzene with
CH3Cl.
5.44 Propose a mechanism to explain the fact that deuterium (D, 2H) slowly
replaces hydrogen (1H) in the aromatic ring when benzene is treated with
D2SO4.
| Exercises
185
Biphenyl
5.46 In light of your answer to Problem 5.45, at what position and on which ring
would you expect nitration of 4-bromobiphenyl to occur?
Br
S YNTHESIS
4-Bromobiphenyl
5.47 Starting with benzene, how would you synthesize the following substances?
Assume that you can separate ortho and para isomers if necessary.
(a) m-Bromobenzenesulfonic acid
(b) o-Chlorobenzenesulfonic acid
(c) p-Chlorotoluene
5.48 Starting from any aromatic hydrocarbon of your choice, how would you
synthesize the following substances? Ortho and para isomers can be separated if necessary.
(a) o-Nitrobenzoic acid
(b) p-tert-Butylbenzoic acid
5.49 Explain by drawing resonance structures of the intermediate carbocations
why naphthalene undergoes electrophilic aromatic substitution at C1
rather than at C2.
Br
1
2
G ENERAL P ROBLEMS
Br2
HBr
186
CHAPTER 5 |
Aromatic Compounds
5.52 The following syntheses have flaws in them. What is wrong with each?
(a)
CH3
CO2H
1. Cl2, FeCl3
2. KMnO4
Cl
(b) Cl
Cl
1. (CH3)3CCl, AlCl3
2. KMnO4, H2O
CO2H
5.53 Indole is an aromatic compound that has a benzene ring fused to a pyrrole
ring. Look at the electronic structure of pyrrole in Figure 5.9c, and then
draw an orbital picture of indole.
(a) How many electrons does indole have?
(b) What is the electronic relationship of indole to naphthalene?
Indole
N
H
5.55 Starting with toluene, how would you synthesize the three nitrobenzoic
acids?
5.56 Carbocations generated by reaction of an alkene with a strong acid catalyst can react with aromatic rings in a FriedelCrafts reaction. Propose a
mechanism to account for the industrial synthesis of the food preservative
BHT from p-cresol and 2-methylpropene:
OH
H3C
H3C
CH2
H3PO4
H3C
CH3
OH
H3C
CH3
p-Cresol
CH3
BHT
CH3
CH3
C
CH3
| Exercises
187
5.57 You know the mechanism of HBr addition to alkenes, and you know the
effects of various substituent groups on aromatic substitution. Use this
knowledge to predict which of the following two alkenes reacts faster with
HBr. Explain your answer by drawing resonance structures of the carbocation intermediates.
CH
CH
CH2
CH2
and
CH3O
O2N
5.58 Identify the reagents represented by the letters a through d in the following scheme:
CH2CH3
a
CH2CH3
b
Br
CO2H
HO3S
CO2H
Br
Br
IN
THE
M EDICINE
C ABINET
5.60 Ribavirin, an antiviral agent used against hepatitis C and viral pneumonia, contains a 1,2,4-triazole ring. Look at the electronic structure of imidazole in Figure 5.9d, and then explain why the ring is aromatic.
1,2,4-Triazole
ring
O
C
N
HOCH2
N
O
OH
OH
NH2
N
Ribavirin
188
CHAPTER 5 |
IN
THE
Aromatic Compounds
F IELD
5.61 The herbicide metolachlor is broadly used in the United States to control
weeds but is being phased out in Europe because of possible environmental
risks. Usually marketed under the name Dual, approximately 50 million
pounds of metolachlor are applied on crops each year in the United States.
The preparation of metolachlor begins with the conversion of acetanilide to
2-ethyl-6-methylacetanilide. How would you accomplish this conversion?
O
H
C
N
H
CH3
C
N
CH3
C
CH3
H3C
Acetanilide
O
ClCH2
CH2CH3
2-Ethyl-6-methylacetanilide
CHCH2OCH3
H3C
CH2CH3
Metolachlor
OH
OCH2CO2H
Cl
Cl2
Cl
1. ClCH2CO2H,
NaOH
2. H O+
3
Cl
Phenol
Cl
2,4-D
216
CHAPTER 6 |
Additional Problems
I DENTIFYING C HIRALITY
C ENTERS
H3C CH3
(b) H C
3
(c)
CH3CH2CHCCH2CH3
H3C
CH3
(e)
(d)
CH3
H
(f)
H
O
H3C
H
H
H3C
BrCH2CHCHCH2Br
CH3
6.30 There are eight alcohols with the formula C5H12O. Draw them, and tell
which are chiral.
6.31 Propose structures for compounds that meet the following descriptions:
(a) A chiral alcohol with four carbons
(b) A chiral carboxylic acid
(c) A compound with two chirality centers
6.32 Erythronolide B, the biological precursor of the broad-spectrum antibiotic
erythromycin, has ten chirality centers. Identify them with asterisks.
O
H3C
CH3
OH
H3C
CH3
OH
H3C
Erythronolide B
H3C
O
OH
OH
O
CH3
| Exercises
O PTICAL A CTIVITY
217
6.33 Cholic acid, the major steroid found in bile, was found to have a rotation
of 2.22 when a 3.00 g sample was dissolved in 5.00 mL of alcohol in a
sample tube with a 1.00 cm pathlength. Calculate []D for cholic acid.
6.34 Polarimeters are so sensitive that they can measure rotations to the thousandth of a degree, an important advantage when only small amounts of
a sample are available. For example, when 7.00 mg of ecdysone, an insect
hormone that controls molting in the silkworm moth, was dissolved in
1.00 mL of chloroform in a cell with a 2.00 cm pathlength, an observed rotation of 0.087 was found. Calculate []D for ecdysone.
6.35 Naturally occurring (S)-serine has []D 6.83. What specic rotation do
you expect for (R)-serine?
TO
A SSIGNING R,S
C ONFIGURATION
C HIRALITY C ENTERS
CH3
CH3
CH2CCH3
CH2CH2CH2CH2CH3
CH2CHCH2CH3
CH3
(b)
SH
NH2
SO3H
OCH2CH2OH
6.38 One enantiomer of lactic acid is shown below. Is it R or S? Draw its mirror
image in the standard tetrahedral representation.
CO2H
H
OH
CH3
Serine
NH2
H
NC
C
CH3
(b)
OH
OCH2CH3
C
H
Cl
CH3
(c)
OH
C
H3C
H
CH2OH
218
CHAPTER 6 |
OH
Cl
(b)
(c)
OCH3
HOCH2
CO2H
6.42 Assign R or S conguration to each chirality center in the following biological molecules:
(a)
(b)
OH
H
CH3
(c) HO
H3C
CH3CH2
OH
CH3
Cl
H
S TEREOCHEMICAL
R ELATIONSHIPS
6.43 What is the relationship between the specic rotations of (2R,3R)-pentane2,3-diol and (2S,3S)-pentane-2,3-diol? Between (2R,3S)-pentane-2,3-diol
and (2R,3R)-pentane-2,3-diol?
6.44 What is the stereochemical conguration of the enantiomer of
(2S,4R)-dibromooctane?
6.45 What are the stereochemical congurations of the two diastereomers of
(2S,4R)-dibromooctane?
6.46 Draw examples of the following:
(a) A meso compound with the formula C8H18
(b) A compound with two chirality centers, one R and the other S
6.47 Tell whether the following Newman projection of 2-chlorobutane is R or S.
(You might want to review Section 2.5.)
Cl
CH3
H3C
H
6.48 Draw a Newman projection that is enantiomeric with the one shown in
Problem 6.47.
6.49 Draw a Newman projection of meso-tartaric acid.
6.50 Draw Newman projections of (2R,3R)- and (2S,3S)-tartaric acid, and compare them to the projection you drew in Problem 6.49 for the meso form.
G ENERAL P ROBLEMS
6.51 -Glucose has the following structure. Identify the chirality centers in
-glucose, and tell how many stereoisomers of glucose are possible.
HO
HO
CH2OH
O
OH
OH
-Glucose
| Exercises
219
OH
OH
(b)
(c) H3C
CH3
OH
CH3CHCH2CH2CHCH3
H3C
CH3
HO
OH
CH2OH
Ascorbic acid
O H
O
6.56 We saw in Section 4.6 that alkenes undergo reaction with peroxycarboxylic
acids to give epoxides. For example, cis-but-2-ene gives 2,3-epoxybutane:
CH3
H3C
C
H
RCO3H
O
CH3CH CHCH3
2,3-Epoxybutane
Assuming that both C O bonds form from the same side of the double
bond (syn stereochemistry; Section 4.5), show the stereochemistry of the
product. Is the epoxide chiral? Is it optically active?
6.57 Ribose, an essential part of ribonucleic acid (RNA), has the following
structure:
H H
H OH
CHO
HO
Ribose
HO H HO H
How many chirality centers does ribose have? Identify them with asterisks. How many stereoisomers of ribose are there?
6.58 Draw the structure of the enantiomer of ribose (Problem 6.57).
6.59 Draw the structure of a diastereomer of ribose (Problem 6.57).
220
CHAPTER 6 |
H OH
CH2OH
HO
Ribitol
HO H HO H
CH
CH
CH
CH
CH
CH
CH2CO2H
Mycomycin
HO H
C
H3C
C
C
C
SACP
H3C
Ha Hb
THE
M EDICINE C ABINET
C
C
SACP
H2O
(R)-3-Hydroxybutyryl ACP
IN
trans-Crotonyl ACP
CO2H
NHCOCH3
CH3CO2
A
HO
CO2H
H
HO
NH2
Dopa
| Exercises
221
THE
F IELD
CH3
C
ClCH2
H3C
CHCH2OCH3
CH2CH3
Metolachlor