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Chapter 12
Synthesis
Review of Concepts
Fill in the blanks below. To verify that your answers are correct, look in your textbook at
the end of Chapter 12. Each of the sentences below appears verbatim in the section
entitled Review of Concepts and Vocabulary.
• The position of a halogen can be moved by performing __________ followed by
______________.
Review of Skills
Fill in the blanks and empty boxes below. To verify that your answers are correct, look
in your textbook at the end of Chapter 12. The answers appear in the section entitled
SkillBuilder Review.
12.1 Changing the Identity or Position of a Functional Group
IDENTIFY THE TWO PROCESSES THAT ARE REQUIRED TO CHANGE THE POSITION OF A HALOGEN:
Br Br
254
CHAPTER 12
12.2 Changing the Carbon Skeleton
C
H
H
C C
H
H
HC C
H
H
C C
H
H
HCC
H
H
C C
H
H
H
H
H
+
IDENTIFY THE REAGENT NECESSARY TO ACHIEVE THE FOLLOWING C-C BOND FORMING REACTION:
12.3 Approaching a Synthesis Problem by Asking Two Questions
IDENTIFY THE TWO QUESTIONS TO ASK WHEN APPROACHING A SYNTHESIS PROBLEM:
1) __________________________________________________________________________________________________?
2) __________________________________________________________________________________________________?
12.4 Retrosynthetic Analysis
PRODUCT STARTING
MATERIAL
COMPLETE THE FOLLOWING RETROSYNTHETIC ANALYSIS BY DRAWING THE APPROPRIATE STRUCTURES IN THE BOXES PROVIDED:
CHAPTER 12
255
Solutions
12.1.
OH
OH
O
O
H
Br
HBr
ROOR
HBr
NMO
Br
+ En
1) O
3
2) DMS
OsO
4
256
CHAPTER 12
12.2.
Br
Br
Br
CH
3
O
O
H
H
2
SO
4
, H
2
O
HgSO
4
H
2
2) H
2
O
2
, NaOH
1) 9-BBN Lindlar's
Catalyst
HBr
HBr
1) xs NaNH
2
2) H
2
O
12.3.
a)
Br
2
1) xs NaNH
2
2) H
2
O
Br
Br
d)
Br
2,
hv
Br
NaOMe
CHAPTER 12
257
e)
OH
OH
conc. H
2
SO
4
1) TsCl, py
2) NaOEt
heat dilute H
2
SO
4
h)
OH
1) TsCl, py
2) NaOEt
OH
1) HBr, ROOR
1) BH
3
THF
2) H
2
O
2
, NaOH
2) NaOH (S
N
2)
258
CHAPTER 12
12.6.
a)
Br
Br
2
, hv
d)
Br
NaOMe 1) HBr, ROOR
Br
2
, hv
2) t-BuOK + En
12.7.
a)
1) NaNH
2
2) EtI
1) NaNH
2
2) MeI
CHAPTER 12
259
12.8.
a)
Br
C C HH NaNH
2
C CH Na H
2
Lindlar's
catalyst
12.9. The alkyl halide is a tertiary substrate and does not readily undergo S
N
2. Under
these conditions, the acetylide ion functions as a base, rather than a nucleophile, giving
an E2 reaction, instead of S
N
2:
12.10.
a)
2) I
260
CHAPTER 12
b)
Na
H
2
NH
3
(l)
HBr, ROOR
Br
C C HH NaNH
2
C CH Na
Lindlar's
Catalyst
d)
C C HH
3
CNaNH
2
e)
1) HBr, ROOR
2) t-BuOK
C C HH NaNH
2
C CH Na
ROOR
HBr Br
CHAPTER 12
261
12.11.
Na
NaNH
2
C C HH
C CH
Br
HO
HBr
ROOR
1) TsCl, py
2) t-BuOK
12.12.
C C HH
262
CHAPTER 12
12.13.
a)
H
2
Lindlar's
b)
Br
C CH
C C HH
NaNH
2
Na
H
2
O
MCPBA
Lindlar's
Catalyst
e)
Br
2
Br
t-BuOK
hv
1) BH
3
THF
2) H
2
O
2
, NaOH
OH
CHAPTER 12
263
f)
OH
Br Br O
1) xs NaNH
2
2) H
2
O
1) O
3
2) H
2
O
h)
Br
2
NaOEt
hv
Br
1) HBr, ROOR
2) t-BuOK
264
CHAPTER 12
12.14.
C CH Na
Br
C C HH
H
2
Lindlar's
Catalyst
HBr, ROOR
CHAPTER 12
265
12.15.
Br
C CH
C C HH
NaNH
2
Na
1) H
2
, Lindlar's Catalyst
2) HBr
HBr, ROOR
Br
C CH Na
266
CHAPTER 12
12.16.
Br
C CH
C C HH
NaNH
2
Na
H
2
1) H
2
, Lindlar's Catalyst
2) HBr
12.17.
Br
OH
Br
H
2
Pt
t-BuOK
H
3
O
+
HBr
ROOR
Br
2
hv
CHAPTER 12
267
12.18.
Br
CH
3
O
O
H
Br
HBr
HBr
H
2
SO
4
, H
2
O
HgSO
4
1) 9-BBN
2) H
2
O
2
, NaOH
268
CHAPTER 12
12.19.
C C HH
NaNH
2
12.20.
C C HH
NaNH
2
12.21.
a)
O
H
OH
1) TsCl, py
2)
t
-BuOK
1) BH
3
THF
2) H
2
O
2
, NaOH
CHAPTER 12
269
12.22.
12.23.
a)
OH
O
1) Br
2
2) xs NaNH
2
3) H
2
O
1) O
3
2) H
2
O
Catalyst
d)
1) NaOMe
2) HBr, ROOR
Br
2
hv
Br
Br
HC CNa
H
2
Lindlar's
Catalyst
270
CHAPTER 12
12.24.
1) NaNH
2
2) EtI
1) NaNH
2
2) MeI
12.25.
1) NaNH
2
2) EtI
1) NaNH
2
2) MeI
12.26.
a)
O
Br
H
2
SO
4
, H
2
O
HgSO
4
HBr
ROOR
HC CNa
CHAPTER 12
271
b)
HBr
Br
HC CNa
2) H
2
O
2
, NaOH
ROOR
1) 9-BBN
H
O
e)
Br
2
Br
NaOMe 1) O
3
O
H
O
hv 2) DMS
12.27.
H
2
HBr
Br
Lindlar's
Catalyst
272
CHAPTER 12
12.28.
H
2
1) O
3
O
H H
Lindlar's
Catalyst
2) DMS
12.29.
HO
H
2
HO
OH
Lindlar's
Catalyst
12.30.
a)
HgSO
4
H
O
H
2
SO
4
, H
2
O
CHAPTER 12
273
c)
C C HH
H
d)
Br
C CH
C C HH
NaNH
2
Na
1) H
2
, Lindlar's Cat.
2) HBr
12.31.
1) MCPBA
2) H
3
O
+
OH
HO xs NaH
