Problems 991

Meanwhile, there is mounting concern about polybro- toxicity to humans and other animals. As with PCBs, poly-
modiphenyl ethers (PBDEs). Although use of PBDEs could brominated biphenyls and polybrominated diphenyl ethers
potentially save lives and property in their roles as flame retar- persist in the environment and accumulate in fatty biological
dants, these compounds are now widespread in the environ- tissues. PBDEs have been found in birds, fish, and breast milk.
ment, and studies have led to significant concern about their They are now banned in a number of areas.

Key Terms and Concepts

The key terms and concepts that are highlighted in bold, blue text within the chapter are
defined in the glossary (at the back of the book) and have hyperlinked definitions in the
accompanying WileyPLUS course (www.wileyplus.com).

Problems
Note to Instructors: Many of the homework problems are available for assignment via WileyPLUS, an online
teaching and learning solution.

PHYSICAL PROPERTIES
21.13 Rank the following in order of increasing acidity.
O O O O O O O

OCH3 NO2 CF3

CF3

21.14 Without consulting tables, select the stronger acid from each of the following pairs:
(a) 4-Methylphenol and 4-fluorophenol (d) 4-Methylphenol and benzyl alcohol
(b) 4-Methylphenol and 4-nitrophenol (e) 4-Fluorophenol and 4-bromophenol
(c) 4-Nitrophenol and 3-nitrophenol
21.15 What products would be obtained from each of the following acid–base reactions?
(a) Sodium ethoxide in ethanol 1 phenol S
(b) Phenol 1 aqueous sodium hydroxide S
(c) Sodium phenoxide 1 aqueous hydrochloric acid S
(d) Sodium phenoxide 1 H2O 1 CO2 S
21.16 Describe a simple chemical test that could be used to distinguish between members of each of the following pairs
of compounds:
(a) 4-Chlorophenol and 4-chloro-1-methylbenzene (c) 4-Methylphenol and 2,4,6-trinitrophenol
(b) 4-Methylphenol and 4-methylbenzoic acid (d) Ethyl phenyl ether and 4-ethylphenol

GENERAL REACTIONS
21.17 Complete the following equations:
(a) Phenol 1 Br2 99999:
58C, CS
(b) Phenol 1 concd H2SO4 99:
258C
(c) Phenol 1 concd H2SO4 999:
1008C
2

(d) CH3 OH 1 p-toluenesulfonyl chloride OH2

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992 Chapter 21 
   


(
 Phenol 1 Br2 99:

H2O O
(i) Phenol 1
b;<=
O C6H5 >O
(f) Phenol 1 O
(j) Phenol 1 NaH 9:
O
(k) Product of (j) 1 CH3OSO2OCH3 9:
(g) p-Cresol 1 Br2 9H9:
O2
(l) Product of (j) 1 CH 3 I 9:
O
(m) Product of (j) 1 C 6H 5CH 2Cl 9:
(h) Phenol 1
C6H5 Cl base

2 Predict the product of the following reactions.

(a) O (f) 3C 78
0B4 *excess) *+, -.0:
(2) heat
OH
(b) O (g)
*+, -.0 0-/3, H2SO4
(2) 78

O
(c) O O (h) 56
O
1
-.-02, NH3
OCH3
CH3
(d) (i)
OH
B42 (excess) *+, -./0
H2O
O
(2)
1
3C

(e)
O O O

)
e%&e''

OH

MM  

2 A synthesis of the b-receptor blocker called toliprolol begins with a reaction between 3-methylphenol and epichloro-
hydrin. The synthesis is outlined below. Give the structures of the intermediates and of toliprolol.

3 !"#ylphenol 1 C$ C10H13O2Cl
OH2
O
Epichlorohydrin

(CH3)2CHNH2
C10H12O2 toliprolol, C13H21NO2