Chapter 13 Alcohols - ChemConnectionschemconnections.org/organic/chem226/Solutions/Chapter...
37
Chapter 13 Alcohols Review of Concepts Fill in the blanks below. To verify that your answers are correct, look in your textbook at the end of Chapter 13. Each of the sentences below appears verbatim in the section entitled Review of Concepts and Vocabulary. • When naming an alcohol, the parent is the longest chain containing the __________ group. • The conjugate base of an alcohol is called an ____________ ion. • Several factors determine the relative acidity of alcohols, including ___________, ____________, and _______________________. • The conjugate base of phenol is called a ____________, or _____________ ion. • When preparing an alcohol via a substitution reaction, primary substrates will require S N ___ conditions, while tertiary substrates will require S N ___ conditions. • Alcohols can be formed by treating a carbonyl group (C=O bond) with a ______________ agent. • Grignard reagents are carbon nucleophiles that are capable of attacking a wide range of _________________, including the carbonyl group of ketones or aldehydes, to produce an alcohol. • _______________ groups, such as the trimethylsilyl group, can be used to circumvent the problem of Grignard incompatibility and can be easily removed after the desired Grignard reaction has been performed. • Tertiary alcohols will undergo an S N ___ reaction when treated with a hydrogen halide. • Primary and secondary alcohols will undergo an S N ___ process when treated with either HX, SOCl 2 , PBr 3 , or when the hydroxyl group is converted into a tosylate group followed by nucleophilic attack. • Tertiary alcohols undergo E1 elimination when treated with __________. • Primary alcohols undergo oxidation twice to give a _____________________. • Secondary alcohols are oxidized only once to give a ___________ • PCC is used to convert a primary alcohol into an _____________. • NADH is a biological reducing agent that functions as a ____________ delivery agent (very much like NaBH 4 or LAH), while NAD + is an _____________ agent. • The are two key issues to consider when proposing a synthesis is whether there is: 1. a change in the ___________________. 2. a change in the ____________________.
Transcript of Chapter 13 Alcohols - ChemConnectionschemconnections.org/organic/chem226/Solutions/Chapter...
Chapter 13
Alcohols
Review of Concepts Fill in the blanks below. To verify that your answers are correct, look in your textbook at
the end of Chapter 13. Each of the sentences below appears verbatim in the section
entitled Review of Concepts and Vocabulary.
• When naming an alcohol, the parent is the longest chain containing the
__________ group.
• The conjugate base of an alcohol is called an ____________ ion.
• Several factors determine the relative acidity of alcohols, including ___________,
____________, and _______________________.
• The conjugate base of phenol is called a ____________, or _____________ ion.
• When preparing an alcohol via a substitution reaction, primary substrates will
require SN___ conditions, while tertiary substrates will require SN___ conditions.
• Alcohols can be formed by treating a carbonyl group (C=O bond) with a
______________ agent.
• Grignard reagents are carbon nucleophiles that are capable of attacking a wide
range of _________________, including the carbonyl group of ketones or
aldehydes, to produce an alcohol.
• _______________ groups, such as the trimethylsilyl group, can be used to
circumvent the problem of Grignard incompatibility and can be easily removed
after the desired Grignard reaction has been performed.
• Tertiary alcohols will undergo an SN___ reaction when treated with a hydrogen
halide.
• Primary and secondary alcohols will undergo an SN___ process when treated with
either HX, SOCl2, PBr3, or when the hydroxyl group is converted into a tosylate
group followed by nucleophilic attack.
• Tertiary alcohols undergo E1 elimination when treated with __________.
• Primary alcohols undergo oxidation twice to give a _____________________.
• Secondary alcohols are oxidized only once to give a ___________
• PCC is used to convert a primary alcohol into an _____________.
• NADH is a biological reducing agent that functions as a ____________ delivery
agent (very much like NaBH4 or LAH), while NAD+ is an _____________ agent.
• The are two key issues to consider when proposing a synthesis is whether there is:
1. a change in the ___________________.
2. a change in the ____________________.
CHAPTER 13 275
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 13. The answers appear in the section entitled
SkillBuilder Review.
13.1 Naming an Alcohol
OH
Cl Cl
PROVIDE A SYSTEMATIC NAME FOR THE FOLLOWING COMPOUND
1) IDENTIFY THE PARENT
2) IDENTIFY AND NAME SUBSTITUENTS
3) ASSIGN LOCANTS TO EACH SUBSTITUENT
4) ALPHABETIZE
5) ASSIGN CONFIGURATION
13.2 Comparing the Acidity of Alcohols
OH OHCl
Cl Cl
OH OH
OHOH
FOR EACH PAIR OF COMPOUNDS BELOW, CIRCLE THE COMPOUND THAT IS MORE ACIDIC:
13.3 Identifying Oxidation and Reduction Reactions
IN THE FOLLOWING REACTION, DETERMINE WHETHER THE STARTING MATERIAL HAS BEEN OXIDIZED, REDUCED, OR NEITHER:
O RO OR
13.4 Drawing a Mechanism, and Predicting the Products of Hydride Reductions
O
H
Al HH
HH
OH
COMPLETE THE MECHANISM BELOW BY DRAWING ALL CURVED ARROWS, INTERMEDIATES AND PRODUCTS.
13.5 Preparing an Alcohol via a Grignard Reaction
Ph Et
O
Ph
O
Me
Et
O
Me
Ph Et
OH
Me
IDENTIFY REAGENTS THAT CAN ACHIEVE EACH OF THE FOLLOWING TRANSFORMATIONS
1)
2)
1)
2)
1)
2)
276 CHAPTER 13
13.6 Proposing Reagents for the Conversion of an Alcohol into an Alkyl Halide
OH Cl
IDENTIFY REAGENTS THAT CAN ACHIEVE EACH OF THE FOLLOWING TRANSFORMATIONS
1)
2)
13.7 Predicting the Products of an Oxidation Reaction
OHCrO3
acetone
H3O+
DRAW THE EXPECTED PRODUCT OF THE FOLLOWING REACTION
13.8 Converting Functional Groups
IDENTIFY REAGENTS THAT CAN ACHIEVE EACH OF THE FOLLOWING FUNCTIONAL GROUP TRANSFORMATIONS
XO OH
CHAPTER 13 277
13.9 Proposing a Synthesis
AS A GUIDE FOR PROPOSING A SYNTHESIS, ASK THE FOLLOWING TWO QUESTIONS:
1) IS THERE A CHANGE IN THE ______________ SKELETON?
2) IS THERE A CHANGE IN THE LOCATION OR IDENTITY OF THE _________________________?
AFTER PROPOSING A SYNTHESIS, USE THE FOLLOWING TWO QUESTIONS TO ANALYZE YOUR ANSWER:
1) IS THE ________________________ OUTCOME OF EACH STEP CORRECT?
2) IS THE ________________________ OUTCOME OF EACH STEP CORRECT?
Review of Reactions Identify the reagents necessary to achieve each of the following transformations. To
verify that your answers are correct, look in your textbook at the end of Chapter 13. The
answers appear in the section entitled Review of Reactions.
Preparation of Alkoxides
ROH RO Na
Preparation of Alcohols via Reduction
R H
O
R H
O
H
H
RR
O
RR
OH
R OH
O
R OH
R OMe
O
R OH + MeOH
Preparation of Alcohols via Grignard Reagents
O OH
R
R
O
OMe R
OH
RR
278 CHAPTER 13
Protection and Deprotection of Alcohols
R OH R O TMS
SN1 Reactions with Alcohols
R
OHRR
R
XRR
+ H2O
SN2 Reactions with Alcohols
OH Br
OH Cl
E1 and E2 Reactions with Alcohols
OH + H2O
OH OTs
Oxidation of Alcohols and Phenols
R
OH
R R
O
R
CHAPTER 13 279
R
OH
R OH
O
OH O
O
R
OH
R H
O
Solutions
13.1. a) 5,5-dibromo-2-methylhexan-2-ol
b) (2S,3R)-2,3,4-trimethylpentan-1-ol
c) 2,2,5,5-tetramethylcyclopentanol
d) 2,6-diethylphenol
e) (S)-2,2,4,4-tetramethylcyclohexanol
13.2.
a)
OH
BrBr
b) OH
c)
OH
13.3. Nonyl mandelate has a longer alkyl chain than octyl mandelate and is therefore
more effective at penetrating cell membranes, rendering it a more potent agent. Nonyl
mandelate has a shorter alkyl chain than decyl mandelate and is therefore more water-
soluble, enabling it to be transported through aqueous media and to reach its target
destination more effectively.
280 CHAPTER 13
13.4.
a)
OHNa
O Na
b)
OH NaH O Na
c)
LiOH O Li
d)
NaH
OH O Na
13.5.
a) OH
F F
The electron-withdrawing effects of the fluorine atoms stabilize the conjugate base.
b) OH
The conjugate base of a primary alcohol will be more easily solvated than the conjugate
base of a tertiary alcohol.
c)
OH
Cl
Cl
Cl
Cl
Cl
The electron-withdrawing effects of the chlorine atoms stabilize the conjugate base.
d) OH
O
The conjugate base is more highly stabilized by resonance, with the negative charge
spread over two oxygen atoms, rather than just one oxygen atom.
CHAPTER 13 281
e)
OH
The conjugate base is stabilized by resonance.
13.6. 2-nitrophenol is expected to be more acidic (lower pKa) because the conjugate
base has a resonance structure in which the negative charge is spread onto an oxygen
atom of the nitro group, shown below. In contrast, 3-nitrophenol does not have such a
resonance structure:
O
NO
O O
NO
O
13.7.
a)
Br OHH2O
b) Br OH
NaOH
c)
OHdilute H2SO4
d) OH
1) BH3 THF
2) H2O2, NaOH
e)
OH
1) Hg(OAc)2, H2O
2) NaBH4
f) HO
1) BH3 THF
2) H2O2, NaOH
282 CHAPTER 13
13.8
a)
OH1) BH3 THF
2) H2O2, NaOH
b)
OH1) Hg(OAc)2, H2O
2) NaBH4
c)
OHdilute H2SO4
13.9. a) (+2) � (+2). The starting material is neither oxidized nor reduced.
b) (+1) � (+3). The starting material is oxidized.
c) (+3) � (-1). The starting material is reduced.
d) (+3) � (+3). The starting material is neither oxidized nor reduced.
e) (0) � (+2). The starting material is oxidized.
f) (+2) � (+3). The starting material is oxidized.
13.10. One carbon atom is reduced from an oxidation state of 0 to an oxidation state of
-1, while the other carbon atom is oxidized from an oxidation state of 0 to an oxidation
state of +1. Overall, the starting material does not undergo a net change in oxidation state
and is, therefore, neither reduced nor oxidized.
13.11. One carbon atom is reduced from an oxidation state of 0 to an oxidation state of
-2, while the other carbon atom is oxidized from an oxidation state of 0 to an oxidation
state of +2. Overall, the starting material does not undergo a net change in oxidation state
and is, therefore, neither reduced nor oxidized.
13.12.
a)
O
H
O
HH
HO
H
O
H
H Al H
H
H
H
H
CHAPTER 13 283
b)
O O
H
HO
H O
H Al H
H
H
H
H
c)
O O
H
HO
MeO
H B H
H
H
H
H
d)
O
H
O
HH
HO
H
O
H
H Al H
H
H
H
H
e)
O
O
O
OH
HO
H
O
H
H Al H
H
H
H
HO
H
H Al H
H
H
O
HH
f)
O
OMe
O H
OMe
OO
HO
Me
H B H
H
H
H
OMe
OHO
284 CHAPTER 13
13.13.
H
O
H
H Al H
H
HO
O
O
O H
H
O
O
H Al H
H
H H
O
O
H
H
O
OH
H
HO
HH
HO
OH
HH
H
13.14.
a)
1) MeMgBr
2) H2O
1) PrMgBr
2) H2O
OHH
O
H
O
b)
1) MeMgBr
2) H2O
1) PrMgBr
2) H2O
OH
O
O
c) OH
1) PrMgBr
2) H2OH H
O
CHAPTER 13 285
d)
1) EtMgBr
2) H2O
1)
2) H2OH
O
H
O
OH
MgBr
e) 1) MeMgBr
2) H2O
1) BuMgBr
2) H2O
OH
O
O
O
1) EtMgBr
2) H2O
f)
O MgBr
1) MeMgBr
2) H2O
1)
2) H2O
OH
O
13.15 Each of the following two compounds can be prepared from the reaction between
a Grignard reagent and an ester, because each of these compounds has two identical
groups connected to the α position:
Me
Me OH OH
The other four compounds from Problem 13.14 do not contain two identical groups
connected to the α position, and cannot be prepared from the reaction between an ester
and a Grignard reagent.
286 CHAPTER 13
13.16 Each of the following three compounds can be prepared from the reaction
between a hydride reducing agent (NaBH4 or LAH) and a ketone or aldehyde, because
each of these compounds has a hydrogen atom connected to the α position:
OH
OH
OH
The other three compounds from Problem 13.14 do not contain a hydrogen atom
connected to the α position and, therefore, cannot be prepared from the reaction between
a hydride reducing agent (NaBH4 or LAH) and a ketone or aldehyde.
13.17.
OO
C
H
H
H
MgBrO
O
CH3O
O
CH3
OCH3
OCH3
C
H
H
H
MgBr
HO
H
H
OCH3
OHCH3
HO
H
H
OHCH3
OHCH3
In this case, H3O
+ must be used as a proton source because water is not sufficiently acidic
to protonate a phenolate ion (see Section 13.2, Acidity of Alcohols and Phenols).
13.18.
a)
BrHO
HO
OH
TMSCl, Et3N 1) Mg
2)O
3) H2OTBAF
BrTMSO TMSO
OH
CHAPTER 13 287
b)
TMSO
OH
OTMS
BrHO
BrTMSO
OMe
O
TMSCl, Et3N 1) Mg
2)
3) H2O
TBAF
(0.5 equivalents)
HO
OH
OH
13.19.
a)
OH Br1) TsCl, py
2) NaBr
PBr3
b)
OH Br
HBr
c)
OH Cl
1) TsCl, py
2) NaCl
SOCl2
py
288 CHAPTER 13
d)
OH Br
1) TsCl, py
2) NaBr
PBr3
e)
OH Cl
1) TsCl, py
2) NaCl
SOCl2
py
f)
OH Br
1) TsCl, py
2) NaBr
PBr3
HBr
13.20.
OH I
1) TsCl, py
2) NaI
NaClCl
13.21.
a) H2SO4
heat
OH
+
major minor
b) 1) TsCl, py
2) NaOEtOH
CHAPTER 13 289
13.22.
a)
PCC
CH2Cl2H
OHO
H
OO
H
b)
Na2Cr2O7
H2SO4 , H2O
OH OHO
c)
OHxs CrO3H
Oacetone
H3O+OH
HO
O
O
c)
PCC
CH2Cl2
OH OH
e)
OHPCC
CH2Cl2O
f)
OHNa2Cr2O7
H2SO4 , H2OO
13.23.
a)
Br
O
H1) NaOH
2) PCC, CH2Cl2
b)
H
O1) BH3 THF
2) H2O2, NaOH
3) PCC, CH2Cl2
290 CHAPTER 13
c)
O2) Na2Cr2O7, H2SO4 , H2O
1) dilute H2SO4
1) Br2
2) xs NaNH2
3) H2O
4) H2SO4, H2O, HgSO4
d)
O3) Na2Cr2O7, H2SO4 , H2O
1) Hg(OAc)2, H2O
1) Br2
2) xs NaNH2
3) H2O
4) H2SO4, H2O, HgSO4
2) NaBH4
13.24.
a)
OH
2) BH3 THF
1) H2, Lindlar's Catalyst
1) 9-BBN
2) H2O2, NaOH
3) LAH
4) H2O
3) H2O2, NaOH
b)
OH
H2SO4, heat
1) TsCl, py
2) t-BuOK
1) Br2
2) xs NaNH2
3) H2O
CHAPTER 13 291
d)
H
O1) BH3 THF
3) PCC, CH2Cl2
2) H2O2, NaOH
e)
OH
1) H2SO4, heat
1) TsCl, py
2) NaOEt
2) H2, Pt
3) H2, Pt
f)
O
H
OH1) LAH
2) H2O
H2SO4, heat
1) TsCl, py
2) t-BuOK
g)
O1) LAH
2) H2O
OH
H2SO4, heat
1) TsCl, py
2) NaOEt
13.25.
H2SO4, heat
1) TsCl, py
2) NaOEt
OH
13.26.
OH
OH
H2SO4, heat
1) TsCl, py
2) NaOEt
1) BH3 THF
2) H2O2, NaOH
292 CHAPTER 13
13.27.
a)
O
H
O
1) EtMgBr
3) Na2Cr2O7 ,
H2SO4 , H2O
2) H2O
b)
O
H
O1) MeMgBr
3) Na2Cr2O7 ,
H2SO4 , H2O
2) H2O
13.28.
a)
H
O
OHPCC
CH2Cl2
O
1) MeMgBr
2) H2O
1) Br2
2) xs NaNH2
3) H2O
1) BH3 THF
2) H2O2, NaOH
1) 9-BBN
2) H2O2, NaOH
3) Na2Cr2O7,
H2SO4, H2O
b)
O
1) NaNH2
2) I
1) 9-BBN
2) H2O2, NaOH
O
H
1) EtMgBr
2) H2O
3) Na2Cr2O7 ,
H2SO4 , H2O
c)
O O1) EtMgBr
2) H2O
3) Na2Cr2O7 ,
H2SO4 , H2O
H
CHAPTER 13 293
d)
O
OH1) TsCl, py
2) t-BuOK
1) BH3 THF
2) H2O2, NaOH
OH
PCC, CH2Cl2
O
H1) MeMgBr
2) H2O
3) Na2Cr2O7 ,
H2SO4 , H2O
e)
O
1) 9-BBN
2) H2O2, NaOH
1) MeMgBr
2) H2O
3) Na2Cr2O7 ,
H2SO4 , H2O
H
O
f)
OH OH
2) MeMgBr
3) H2O
1) Na2Cr2O7 ,
H2SO4 , H2O
13.29.
a) OH
H
O 1) MeMgBr
2) H2O
b)
Br
C CH Na
H
OH2SO4, H2O
HgSO4
H2
O
OH
dilute H2SO4
1) LAH
2) H2O
Lindlar'sCatalyst
1) Mg
2)
3) H2O
294 CHAPTER 13
c)
Br
C CH Na
H2
H
O
OH
1) HBr, ROOR
2) NaOH
1) 9-BBN
2) H2O2, NaOH
1) LAH
2) H2O
Lindlar'sCatalyst
d)
Br
C CH Na
HgSO4
H2SO4, H2O
H
O
O
OH1) 9-BBN
2) H2O2, NaOH
1) EtMgBr
2) H2O
1) NaNH2
2) EtBr
1) LAH
2) H2O
13.30. a) 2-propyl-1-pentanol
b) (R)-4-methyl-2-pentanol
c) 2-bromo-4-methylphenol
d) (1R,2R)-2-methylcyclohexanol
13.31.
a) OH
OH
b) OH
c) OH
NO2O2N
NO2
CHAPTER 13 295
d)
OH
e) OHHO
f) HO
13.32.
HO
OH OH
OH
1-butanol 2-butanol 2-methyl-2-propanol 2-methyl-1-propanol
13.33.
a)
Cl Cl
OH
ClClCl
Cl
Cl
OH
ClCl
OH
Increasing acidity
b)
OH OH OH
Increasing acidity
c)
OH OH OH
NO2
Increasing acidity
296 CHAPTER 13
13.34. a)
O O O O O
b)
O O
c)
O O O
13.35. a) 1-bromobutane b) 1-chlorobutane c) 1-chlorobutane d) trans-2-butene
e)
O
H f)
O
OH g) O Li
h) O Na
i) OTMS j) OTs k) O Na
l) O K
13.36.
O OH
H
HH O
H
HO
HHO
HH
13.37. a)
OH PCC
CH2Cl2
O
H
CHAPTER 13 297
b) O
OH
OH Na2Cr2O7
H2SO4 , H2O
c) OHOH
1) PCC, CH2Cl2
2) EtMgBr
3) H2O
d)
OHOH
1) PCC, CH2Cl22) EtMgBr
3) H2O
4) Na2Cr2O7, H2SO4 , H2O
5) MeMgBr
6) H2O
e)
OOH1) PCC, CH2Cl22) PrMgBr
3) H2O
4) Na2Cr2O7, H2SO4 , H2O
13.38. a)
OH
1)
2) H2OH H
OMgBr
b) O
O
OMgBr
OH
1) MeMgBr
2) H2O
1)
2) H2O
1) PrMgBr
2) H2O
298 CHAPTER 13
c)
1) EtMgBr
2) H2O
1) PrMgBr
2) H2O
OH
H
O
H
O
d) 1) MeMgBr
2) H2O
1) PrMgBr
2) H2O
OH
O
O
O
1) EtMgBr
2) H2O
13.39.
a)
O
H
b)
O
c)
O
d)
O
13.40. a)
O
H
O1) EtMgBr
2) H2O
3) Na2Cr2O7 ,
H2SO4 , H2O
CHAPTER 13 299
b)
O
H OH
1) LAH
2) H2O
NaBH4
MeOH
13.41.
OBr
OH H
OBr
Br-
13.42. The major product is 1-methylcyclohexanol (resulting from Markvonikov
addition), which is a tertiary alcohol. Tertiary alcohols do not generally undergo
oxidation. The minor product (2-methylcyclohexanol) is a secondary alcohol and can
undergo oxidation to yield a ketone.
13.43.
Mg
O
H2SO4
Compound A Compound B Compound C
1)
2) H2O heat
Br MgBrOH
300 CHAPTER 13
13.44.
PBr3
OH
Br
O
OH
H H
O
O
H
O
H
OH
OH
CH2Cl2
PCC
1) MeMgBr
2) H2O
Na2Cr2O7
1) PhMgBr
2) H2O
1) TsCl, py
2) t-BuOK
H2SO4, H2O
1) BH3 THF
2) H2O2, NaOH
1) Mg
2)
3) H2O
13.45.
O OH1) PrMgBr
2) H2O
OH Na2Cr2O7
H2SO4, H2O
1) TsCl
2) NaOEt
1) HBr, ROOR
2) Mg
CHAPTER 13 301
13.46.
a)
O O
HH
OH
O
H Al H
H
H
H
H
b)
O HO
HO
H
H Al H
H
H
HHO
c)
O HO
HO
Me
H B H
H
H
HHO
13.47. a)
SOCl2
Cl
SCl
O
OSH
Cl
Cl
OO
SH
Cl
O
N
OS
Cl
O
Cl
+ SO2 +py Cl
OH Cl
302 CHAPTER 13
b)
OH BrP Br
Br
Br
OPH
Br
Br
+ Br + PBr2OHSN2
c)
O
O
O
OH
HO
HO
H
H Al H
H
H
H
HO
H
H Al H
H
H
O
HH
13.48.
a)
OH
H2SO4, H2O
ONa2Cr2O7
b)
OHPCC
CH2Cl2
O
c)
OH
O
PCC
CH2Cl2
H
d)
OH O
OHH2SO4, H2O
Na2Cr2O7
e)
OHO
H
1) LAH
2) H2O f)
OHO 1) LAH
2) H2O
13.49
a) 1) O3
2) DMS
3) Excess LAH
4) H2O
OHHO
CHAPTER 13 303
b) 1) O3
2) DMS
3) Excess LAH
4) H2O
OHHO
c) 1) O3
2) DMS
3) Excess LAH
4) H2O
OHHO
d)
1) EtMgBr
3) Na2Cr2O7 , H2SO4 , H2O
4) EtMgBrH
O 2) H2O
5) H2O
OH
e)
O
H
OTs
1) LAH
2) H2O
3) TsCl , pyridine
f)
PhOH
1) H3O+
2) Na2Cr2O7 , H2SO4 , H2O
3) PhMgBr
4) H2O
13.50. a)
O OHH3CC
H
H
H
MgBr OH3C
HO
H
304 CHAPTER 13
b)
O
O C
H
H
H
MgBr
O
O CH3
CH3
HO
OH
CH3
H
O
O
HO
H
C
H
H
H
CH3
O
OH
CH3
MgBr
CH3
O
O
CH3
H
O
H
13.51.
t-BuOK
HBr, ROOR
NaOH
PBr3
H
O
OH
Br
NaOH
CH2Cl2
PCC 1) LAH
2) H2O
1) 9-BBN
2) H2O2 , NaOH
1) BH3 THF
2) H2O2 ,
H2 , Lindlar's Catalyst
1) Br22) xs NaNH2
3) H2O
1) TsCl
2) NaOEt
CHAPTER 13 305
13.52.
a)
H
O O1) MeMgBr
3) Na2Cr2O7 , H2SO4 , H2O
2) H2O
b)
H
O 1) LAH
2) H2O
3) TsCl, py
4) NaOEt
c)
H
O
O1) LAH
2) H2O
3) TsCl, py
4) NaOEt
5) O3
6) DMS
d)
H
O1) MeMgBr
3) TsCl, py
2) H2O
4) t-BuOK
e)
Cl H
O1) NaOH
2) PCC, CH2Cl2
f)
Cl
O1) NaOH
2) PCC, CH2Cl2
3) MeMgBr
5) Na2Cr2O7 , H2SO4 , H2O
4) H2O
306 CHAPTER 13
g) O
2) Na2Cr2O7 , H2SO4 , H2O
1) dilute H2SO4
h)
OH2) Na2Cr2O7 , H2SO4 , H2O
1) dilute H2SO4
3) MeMgBr
4) H2O
i)
2) Na2Cr2O7 , H2SO4 , H2O
1) dilute H2SO4
3) MeMgBr
4) conc. H2SO4, heat
j) OH
1) HgSO4, H2SO4, H2O
2) MeMgBr
3) H2O
k)
OH
1) dilute H2SO4
2) Na2Cr2O7, H2SO4, H2O
3) MeMgBr
4) H2O
l) OH
H
O 1) EtMgBr
2) H2O
m) O
1) LAH
2) conc. H2SO4
CHAPTER 13 307
n)
O1) LAH
2) H2O
3) TsCl, Et3N
4) t-BuOK
o)
O
HO
1) LAH
2) H2O
3) TsCl, Et3N
4) t-BuOK
5) BH3 THF
6) H2O2, NaOH
p)
O1) MeMgBr
2) H2O
3) conc. H2SO4, heat
q) OHO 1) EtMgBr
2) H2O
r)
H Br
O1) LAH
2) H2O
3) PBr3
s) OH1) BH3 THF
2) H2O2, NaOH
3) PCC, CH2Cl2
4) MeMgBr
5) H2O
308 CHAPTER 13
13.53. HO
13.54. OH
13.55.
OH OH
13.56. OH
13.57
O
O
O
O
H Al H
H
H
O
H
H
O
O
O
HO
O
O
O H
O
H Al H
H
H
OH H
O
H
O H
O
H
O
O
O
OH
HO
O
OH
H Al H
H
H
H Al H
H
H
O
H
O
O
H
O
O
H
O
O
H
O
H
2
CHAPTER 13 309
13.58
O
O
O
O
C
H
H
H
MgBr
O
O
O CH3
O
O
CH3
O
O
O
C
H
H
H
MgBr
O
CH3
O CH3
O
OH3C
O
O CH3
CH3
O
H
H
O
HO CH3
CH3
OH H OH
HO CH3
CH3
C
H
H
H
MgBr
C
H
H
H
MgBr
O
CH3
O
O
CH3
O
O
CH3
O
O
CH3
O
H3C
2
13.59
O1) Br2, hv
2) NaOMe
1) BH3 THF
2) H2O2, NaOH
3) Na2Cr2O7, H2SO4, H2O
1) MeMgBr
2) H2O
OHconc. H2SO4
heat
H2
Pt
310 CHAPTER 13
13.60.
CH3O
H H
O
O
O
HH
H Al H
H
H
H Al H
H
H
O
O
H
CH3O
H HH
OHO
H
O
O
OH
H
O
HH
H
H Al H
H
H
O
O
O
-
-
13.61.
HO OHH O S O
O
O
H
HO
HO
HO O
H
H
OH
HO
HO
- H2O
methylshift
13.62. One carbon atom is oxidized from an oxidation state of +1 to an oxidation state
of +2, while the other carbon atom is reduced from an oxidation state of +1 to an
oxidation state of 0. Overall, the starting material does not undergo a net change in
oxidation state and is, therefore, neither reduced nor oxidized.
