5-8 Klein

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2 of 10 12/23/2011 3:12 AM
Review of Concepts
Chapter 5
Stereoisomerism
Fill in the blanks below. To verify that your answers are correct, look in your textbook at
the end of Chapter 5. Each of the sentences below appears verbatim in the section
entitled Review of Concepts and Vocabulary.
___ isomers have the same connectivity of atoms but differ in their spatial
arrangement.
Chiral objects are not superimposable on their . The
most common source of molecular chirality is the presence of a
_______ , a carbon atom bearing ___ different groups.
A compound with one chirality center will have one non-superimposable mirror
image, called its --------
The Cahn-Ingold-Prelog system is used to assign the of a
chirality center.
A polarimeter is a device used to measure the abil ity of chiral organic
compounds to rotate the plane of light. Such
compounds are said to be active.
A solution containing equal amounts of both enantiomers is called a ____ _
mixture. A solution containing a pair of enantiomers in unequal amounts is
described in terms of enantiomeric (ee).
For a compound with multiple chirality centers, a family of stereo.isomers exists.
Each stereoi somer wil l have at most one enantiomer, with the remaining members
of the fami ly being -------
A ___ compound contains multiple chirality centers but is nevertheless
achiral because it possesses reflectional symmetry.
projections are drawings that convey the configuration of chirality
centers, without the use of wedges and dashes.
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 5. The answers appear in the section entitled
SkillBuilder Review.
SkillBuilder 5.1 Identifying tis-trans Stereoisomerism
ASSIGN THE CONFIGURATION
OF THE FOLLOWiNG DOUBLE
BOND AS CIS OR TRANS
SkiliBuilder 5.2 Locating Chirality Centers
CIRCLE THE
CHIRALITY CENTER
IN THE FOLLOWING
COMPOUND
User name: Lean Pirat Book: Organic Chemistry, Student Study Guide and Solutions Manual Page: 79. No part of any book may be reproduced or transmitted by any
3 of 10 12/23/2011 3:12 AM
SkiiLBuilder 5.3 Drawing an Enantiomer
SHOW THREE WAYS TO
DRAW THE ENANTIC>MER I NH2
OF THE FOlLOW/NO
COMPOUND. PLACE
YOUR ANSWERS IN 7HE
BOXES SHOWN.
SkiiiBuilder 5.4 Assignin,:: Configuration
ASSIGN THE CONFIGURATION
OF THE CHIRALITY CENTER W
THE FOLLOW/NO COMPOUND 0
Skill Builder 5.5 Calculating specific rotalion
CALCU&.ATE THE
SPECIFIC ROTATION
GIVEN THE FOLLOWING
INFORMATION:
0.300 grams sucrose
dissolved in 10.0 ml of water
sample cell 1 0.0 em
0
obseoved rotation + 1.99
(l
specific rot ation ; [a] ; c x
1
SkiiiBuilder 5.6 Calculating % ee
% et'
observed I I
CALCULATE T H ~
ENANTIDMERIC EXCESS
GIVEN THE FOLLOWING
INFORMATION:
I of pure cnnntiomer
The specific rot ation of
optically pure adrenaline is
53 . A mixture of (R) and
(S)- adrenaline was found
to have a specific rotation
of 45 . Calculate the %
eeof the mixture
D
D
SkiiJBuilder 5.7 Determining Stereoisomeric Relationship
IDENTIFY THE STeREOISOMERIC
RELATIONSHIP BETWEEN THE
FOLLOWING TWO COMPOUNDS
~ H
..
0
. ''
&
SkillBuilder 5.8 Identifying Meso Compounds
100 %
CHAPTER 5 79
100 %
D
DRAW ALL POSSIBLE STEREOSIOMERS OF 1.2-CYGL.OHEXANEDIOL (SHOWN LEFT), AND THEN LOOK FOR A
PLANE OF SYMMETRY IN ANY OF THE DRAWINGS. THE PRESENCE OF A PLANE OF SYMMETRY INDICATES A
MESO COMPOUND
ENANTIOMERS NESO
4 of 10 12/23/2011 3:12 AM
80 CHAPTER S
SkillBuilder 5.9 Assigning configuration from a Fischer projection
ASSKIN IHE CONFIGURATION
OF THE CHIRALITY CENTER iN
THE FOLLOWING COMPOUND
Solutions
5.1.
5.2.
a) trans
c) trans
e) trans
g) cis
0
b) not stereoisomeric
d) trans
I) not stereoisomeric
Neither double bond exhibits stereoisomerism. so this compound does not have
any stereoisomers.
5.3.
a ) ~
5.4. All chirality centers are highlighted below:
OH
H O ~ o
a) HO OH
HO
b)
e)
5 of 10 12/23/2011 3:12 AM
CHAPTER 5 8 1
f)
5.5.

Br

chirality center
5.6. The phosphorus atom has four different groups attached to it (a methyl group, an
ethyl group. a phenyl group, and a lone pair). This phosphorous atom therefore
represents a chirality center. This compound is not superimposable on its mirror image.
as can be seen clearl y by building and comparing mol ecular models.
5.7.
OH H
:: '

a)
&
I

I
b) OH H
l ../"o ()
N
:'
-........... ....._/ o
c)
Q
Jl .. . Ct
( 'J'N-H
e) VI
H,J )

tl J I
f) N
5.8.
---{Sll

j ,' ,. OH
,,,
H' N . -.,,
0 OH 0
OH H
-= '
N, CH
I 3
d) HO ""'

g) HO
6 of 10 12/23/2011 3:12 AM
82 CHAPTER S
5.9.
OH H
7sN,
a) llJ " I '

1 S i R
b) Cl Br
c)

f) Cl Cl
5.10.
5.11.

v 3
s
a (+1.47)
5.12. specific rotation = [a]= --= = +25.6
ex I (0.0575 g I mL) x ( 1.00 dm)
a (- 2.99)
5.13. specific rotation = [a] = --= = -31.5
cxl (0.09Sg / mL)x( I.OOdm)
a (+0.57)
5.14. specific rotation= [a] = --= = +2.2
ex I (0.260 g I mL) x ( 1.00 dm)
5.15. This compound does not have a chirality center, because two of the groups are
identical:
\ TOH

Accordingly, the compound is achiral and is not optically active.
7 of 10 12/23/2011 3:12 AM
5.16.
5. 17.
5. 18.
5.19.
a
[a]= -
cx l
a = [ a] x ext = (+13.5)(0. 100 g I mL)( I.OO dm) = +1.35
% ee
observed [ aJ
X
100 %
=
I al of pure enantiomer
( . 37 )
(. 39.5)
X 100 %
94 %
% ee
( - 6.0)
(- 6.3)
95 o/o
% ee
92 o/o
observed [a]
X 100 %
I a I of pure enantiomer
X 100 %
observed La ]
X tOO %
I aJ of pure cnantiomcr
X 100 %
CHAPTER 5 83
8 of 10 12/23/2011 3:12 AM
84 CHAPTER 5
a (+0.78)
5.20. Obser ved [o.] = - = = +2.2
ex I (0.350 g I mL) x ( 1.00 dm)
5.21.
% ee =
observed I a I
X 100 %
I al of pure e nantio mer
X 100 %
79%
a) enantiomers
b) diastereomers
c) diastereomers
d) diastereomers
e) diastereomers
f) enantiomers
5.22. There are three chirality centers, and only one of these chirality centers has a
different conf iguration in these two compounds. The other two chirality centers have the
same configurati on in both compounds. Therefore, these compounds are diastereomers.
5.23.
a) yes b) yes c) no d) yes
5.24. 5.23f has three planes of symmetry.
5.25.
Me Cl
a)
~
Me Br
e) yes
r.::Q]
c) b
f) no
5k
d) ~
9 of 10 12/23/2011 3:12 AM
5.26.
HO\_/OH
b) I \
d) Cc
ex
HO .PH
K
CHAPTER 5 85
ex
HQ. OH
K
H O ~ H
5.27. Each of these compounds i s a meso compound and does not have an enantiomer.
5.28 There are only four stereoisomers:
~ -
meso
meso
5.29. a) R b) s c) S
,-- -
j / not s chlrsllty center
OH/ "' (see problem 5.5)
HO,,,NOH
not a chirality center
O H ~ (see problem 5.5)
H O ~ , , , O H
d) s
10 of 10 12/23/2011 3:12 AM
86 CHAPTERS
5.30.

s s
HO H S HO H S H OH R
H OH R HO H S HO H s
a)
CH20H
b)
CH20H
c)
CH20H
5.31.
s
0 OH
R H! OH R
H OH R H OH R HO H s
HO H s H OH R H OH R
a)
CH
2
0H
b)
CH
2
0H
c)
CH
2
0H
5.32.
F
5.33.
5.34.
a) Pacl itaxel has eleven chira.liry centers.
b) The enantiomer of paclitaxel is shown below:
1 of 10 12/23/2011 3:13 AM
5.35.
trans
5.36.
a) enantiomers
b) same compound
c) constitutional isomers
d) constitutional isomers
e) diastereomers
f) same compound
g) enantiomers
h) diastereomers
i) same compound
j) same compound
k) same compound
I) same compound
5.37. a) 8
5.38.
a)
CID::H
Et
d) ''" 6 ''0H
" ~ f
HO H
H OH
g)
CH
3
QH
j ) ~
b) 3
HO
H O ~ O H
not stereoisomeric
c) 16
b)o:
Cl
"' .,,'OH
e)
Me
O":VOH
H+ OH
HO-H
H+ OH
h)
CH20H
QH
~
k)
Cl
CHAPTERS 87
not stereoisomeric
d) 3 e) 3 f) 32
c) ,.0.,,,/
OH OH Cl Cl OH 0
~
i) Me Me
OH
~
l) i
2 of 10 12/23/2011 3:13 AM
88 CHAPTER S
5.39.
~ H
a) s Me
c)
~
H ~
I) 0
,x-x_/
e) T R ~ u
g)
H O ~
Me
H+OH s
HO+H s
h) Me
s s
CJ, _v 0 ~
R l
i ) -
5.40. 96% ee
5.41.
a) diastereomers
b) diastereomers
c) enantiomers
d) same compound
e) enantiomers
f) diastereomers
g) enaotiomers
h) diastereomers
i) enantiomers
j) same compound
k) enantiomer
I) diastereomers
5.42.
% ee
90 %
observed La]
X 100 %
LaJ of pure enantiomer
X 100 %
3 of 10 12/23/2011 3:13 AM
CHAPTER 5 89
5.43.
a) True.
b) False.
c) True.
5.44.
(- 0.47)
___ .;....__....:...._ ___ = -63
r [ J a
spec1 1c rotation = a = --=
ex I (0.0075 g I mL) x ( 1.00 dm)
5.45.
a) (S)-limonene b) (R)-lirnone ne c) (S)-limonene d) (R)-limonene
5.46.

Br' '' " "'''Br
H H
a) b) c) d)
5.47.

H H
5.48. The first compound has three chirality centers:

5
three chirality centers two chirality centers
This is apparent if we assign the configuration at Cl and C3 of the cyclohexane ring. In
the first compound, the configuration at C I is different than the configuration at C3. As a
result, there are four different groups attached to the C2 position. That is, Cl and C3
represent two different groups: one with the R configuration and the other with the S
configuration. Tn contrast, consider the configuration at C I and C3 in the second
compound. Both of these positions have the same configuration, and therefore, the C2
position in that compound does not have four different groups. Two of the groups are
identical, so C2 is not a chirality center.
4 of 10 12/23/2011 3:13 AM
90 CHAPTERS
5.49.
a) enantiomers
b) diastereomers
c) enantiomers
d) same compound
e) enantiomers
f) diastereomers
g) same compmtnd
h) constitutional isomers
i) diastereomers
j) diastereomers
k) same compound
I) enantiomers
5.50.
a) -61
b) 90 % ee
c) 95 %of the mi xture is (S)-carvone
5.51.
a) chiral
e) chiral
i) chiral
I) achiral
5.52.
a
[a]= -
cxl
b) chiral
f) achiral
j) achiral
m) crural
c) achiral
g) achiral
k) chiral
n) ach.iral
d) achiral
h) chiral
I) chiraJ
o) achiral
a =[a) xcx l =(+24)(0.0100 g/ mL)(I.00dm)= +0.24
5.53.
a) opticaJiy inactive (meso)
b) optically active
c) optically acli ve
d) optically inactive
e) optically active
f) optically inactive (3-methylpentane bas no chirality centers)
g) optically inactive (meso)
h) optically inactive
5.54.
OH OH
~
OH OH
~
a) OH b) OH
QH QH
~
c)
OH
HG:_,--l'
d) I \
e)
5 of 10 12/23/2011 3:13 AM
CHAJ>TER 5 91
5.55.
OH OH
~
a) OH
b) No. A racemic mixture is not optically active.
c) Yes, because d and e are not enantiomers. They are diastereomers, which are
not expected to exhibit equal and opposite rotations.
5.56.
Ol OH
HO H
H OH
a) CH
2
0H
5.57.
O! OH
HO H
HO H
H OH
b) CH20H
OI OH
HO H
H OH
HO H
c) CH1
2
0H
a) 3-methylpentane and 2-methylpentane are constitutional isomers.
b) rran.s- 1 ,2-dimethylcyclohexane and cis- l ,2-dimethylcyclohexane are diastereomers.
5.58. The following two compounds are enantiomers because they are
nonsuperimposable mirror images. You may find it helpful to construct molecular models
to help visualize the mirror image relationship between these two compounds.
Me
Me''c- c - c'
Hr - - '
H
5.59. This compound wi ll be achiral.
5.60.
a) This compound cannot be completely planar because steric hindrance prevents the two
ring systems from rotating with respect to each other. The compound is locked in a
particular conformation that is chiral.
b) Thi s ring system cannot be planar because of steri c hindrance, and must therefore
adopt a spiral shape (l ike a spiral staircase). l'he spiral can be right handed or left
handed, and the relationship between these two forms is enantiomeric.
5.61. The compound is chiral because it is not superimposable on its mirror image.
O=
CH3
H30 <H
5.62. This compound has a center of inversion, which is a form of reflection symmetry.
As a result, this compound is superimposable on its mirror image and is therefore
optically inactive.
6 of 10 12/23/2011 3:13 AM
Chapter 6
Chemical Reactivity and Mechanisms
Review of Concepts
entitled Review of C(mcepts and Vocabulary.
reactions involve a transfer of energy from the system to the
surroundings, while reactions invol ve a transfer of energy from
the surroundings to the system.
Each type of bond has a unique energy, which is
the amount of energy necessary to accomplish homolytic bond cleavage.
Entr opy is loosely defined .as the of a system.
ln order for a process to be spontaneous, the change in ---------
must be negative.
The study of relative energy levels and equilibrium concentrations is call ed
is the study of reaction rates.
speed up the rate of a reaction by providing an alternate pathway
with a lower energy of' activation.
On an energy diagram, each peak represents a , while each
valley represents -----------
A has an electron-rich atom that is capable of donating a
pair of electrons.
An has an electron-deficient atom that is capable of
accepting a pair of electrons.
For ionic reactions, there are four characteristic arrow-pushing patterns:
I) , 2) ,3) ______ _
and4) ________ _
As a result of hyperconjugation, _____ carbocations are more stable than
secondlary carbocations, which are more stable than _____ carbocations.
7 of 10 12/23/2011 3:13 AM
CHAPTER6 93
Review of Skills
Pill in the empty boxes below. To verify that your answers are correct, look in your
textbook at the end of Chapter 6. The answers appear in the section entitled Skit/Builder
Review.
SkillBu.iJder 6.1 Predicting All" of a Reaction
EXAMPLE STEPS 1 AND2 STEP3
CALCULATE

IDENTIFY THE 8DE OF EACH BOND BROKEN AND FORMED. TAKE THE SUM OF STEPS I
FOR THIS REACTION AND DETERMINE THE APPROPRIATE SIGN FOR EACH VAI..IJE

Cl2
\,H
+ CI- CI
\ P
H- CI
(:81) +
_,..c...._
.....-c...._
+

0 0 0 0
I. }
kJ I mol kJ f mol_;
II. kJ I mol
kJ / mol
.J
0
X
0
:f_
+ H- CI

kJ / mol
kJ / mol
SkillBu.iJder 6.2 Identifying ucleophilic and Electrophilic Centers
CtASSIFY EACH OF THE HIOHtiOHTEO REGIONS BEtOW AS EITHER A NUCtEOI'Hit/C CENTER OR AN EtECTROI'Hit/C CENTER
H
16-
H- C-Li
I f--L
H
H
IM
H- C- CI
1---7
H
__ -J) __ -J) __ __ -J)
SkillBu.iJder 6.3 Identifying an Arrow Pushing Pattern
IOENTIFY EACH OF THE FOUR TYPES OF ARROW PUSHING PATTERNS
( ) (
)
..
..
..
-

YJr:

.. e
+
:sr:
0
..
( ) [
)
.
H3C

,.,- H H' ' H :a

0-.J
)(
A
-
8 of 10 12/23/2011 3:13 AM
94 CHAPTER6
SkiiiBuilder 6.4 Identifying a Sequence of Arrow Pushing Patterns
IDENTIFY EACH OF THE FOLLOWING ARROW PUSHING PATTERN$
) )
SkiiiBuilder 6.5 Drawing Curved Arrows
S TEP 1- IDENTIFY WHICH OF THE FOUR ARROW PUSHING
PATTERNS TO USE IN THE FOLLOWING CASE:
S TEP 2 DRAW THE CURVED ARROW, FOCUSING ON THE
PROPER PLACEMENT OF THE TAIL AND HEAD OF EACH
CURVED ARROW
SkiiiBuilder 6.6 Predicting Carbocation Rearrangements
STEP I CIRCLE THE STEP 2 IDENTIFY S TEP 3 FIND ANY STEP 4 DRAW A CURVED ARROW SHOWING THE C+
CARBON ATOMS
ANY HORCH, GROUPS REARRANGEMENT AND THEN DRAW THE NEW
BELOW THAT ARE
ATTACHED DJRECrL Y
THAT CA.N MIGRATE CARBOCATJON
IMMEDIATELY
TO THESE
TO GENERATE
ADJACENT TO THE C ..
CARBON ATOMS
A MORE STABLE C ..
~
D D
I
I
9 of 10 12/23/2011 3:13 AM
CRAPTER6 95
Solutions
6.1.
a)
Bonds Broken k,)/ mol Bonds Formed k.J/mol
H- CH(CH3h + 397 (CH 3)2CH- Br - 285
Br- Br + 192 H- Br -368
Sum = - 64 k.J/mol.
L-.H
0
for this reaction is negative, which means that the system is losing energy. It
is giving off energy to the environment, so the reaction is exothermic.
b)
Bonds Broken k.J/ mol Bonds Formed k.J/ mol
(CH3)3C-CI + 331 (CH3)JC-OH - 381
H- OH + 498 H-CI - 431
Sum = + 17 kJ/mol.
L-.H
0
for this reaction is positive, which means that the system is gaining energy.
It is receivi ng energy from the environment, so the reaction is endothermic.
c)
Bonds Broken k,)/ mol Bonds Formed k.J/ mol
(CH3)JC-Br + 272 (CH3hC-OH - 381
H- OH + 498 H- Br -368
Sum = + 21 kJ/ mol.
L-.H
0
lt is recei ving energy from the environment, so the reaction is endothermic.
d)
Bonds Broken k.J/ mol Bonds Formed k.J/ mol
(CH3hC-I + 209 (CH3)JC-OH - 381
H-OH +498 H-I - 297
Sum = + 29 kJ/ mol.
l-.H
0
It is receiving energy from the environment, so the reaction is endothermic.
10 of 10 12/23/2011 3:13 AM
96 CHAPTER 6
6.2.
6.3.
6.4.
The C-C bond of CH
3
- CH
3
has a bond dissociation energy of= +368 kJ/mol. l f
a C=C bond has a total bond dissociation ene:rgy of +632 kJ/moL then the pi
component of the double bond can be estimated to be (632 kJ/mol) - (368 kJ/mol)
= 264 kJ/mol. In other words, the pi component of the C=C bond is not as strong
as the sigma component of the C=C bond. ln the reaction shown in this problem,
the pi component of the C=C bond is broken but the sigma component remains
intact. Accordingly, the calculation is as follows:
Bonds Broken k.l/mol
C=C Uust the + 264
pi component)
H-OH + 498
Sum = - 29 kJ/mol.
Bonds Formed k.l/ mol
CH3CH2-0 H - 381

for this renction is predicted to be negative, which means that the system is
losing energy. l t is giving off energy to the e.nvironment, so the reaction is
exothermic.
a) is expected to be negative (a decrease in entropy) because two molecules
are convened into one molecule.
b) is expected to be negati ve (a decrease in entropy) because an acylic
compound is converted into a cyclic compound.
c) is expected to be posi t ive (an increase in entropy) because one molecule
is converted into two molecules.
d) is expected to be positive (an increase in entropy) because one mol ecule
is converted into two ions.
e) is expected to be negative (a decrease in entropy) because two chemical
entities are convened into one.
f) is expected to be positi ve (an increase in entropy) because a cyclic
compound is converted into an. acyclic compound.
a) There is a competition between the two terms contributing to In this case,
the reaction is endothermic, which contributes to a positive value for but the
second term contributes to a negative value for
L'\G = ,"'.H + (-TL'\ S)
@ 8
The sign of will therefore depend on the competition between these two
terms, which is affected by temperature. A h1gh temperature will cause the
second term to dominate, giving rise to a positive value of t.G. A low
1 of 10 12/23/2011 3:14 AM
CHAPTER6 97
temperature will render the second term insignificant, and the first term will
dominme, giving rise to a negative value of 6 0 .
b) In thi s case, both terms contribute to a negative value for 60, so 60 will
definitely be negative (the proces will be spontaneous).
c) ln thi s case, both terms contribute to a positive value for 60, so 60 will
definitely be positi ve (the process will not be spontaneous).
d) There is a competition between the two terms contributing to 6 0 . ln this case,
the reaction is exothermic, which contributes to a negative value for 60, but the
second term contributes ro a posit ive value for 60:
L\G = L\H + (- T L\S)
e e
The sign of 60 will therefore depend on the competition between these two
terms, which is affected by temperature. A high temperature will cause the
second term to dominate, giving rise to a negati ve value of 60. A low
temperature will render the second term insignificant, and the first term will
dominate. giving rise to a positi ve value of 6 0 .
6.5. A system can only achieve a lower energy state by transferring energy to its
surroundings (conservation of energy). This increases the entropy of the
surroundings, whi ch more than offsets the decrease in entropy of the system. As a
result, 6S,"' increases.
6.6.
6.7.
a) A positi ve value of 6 0 favors reactants.
b) A reaction for which Keq < I will favor reactants.
c) 60 = 6 H - T 6S = (33 kJ/mol) - (298 K)(O. I50 kJ/ mol K) = - l I. 7 kJ/mol
A negative value of ~ 0 favors products.
d) Both terms contribute to a negative value of 6 0 , which favors products.
e) Both terms contribute to a positi ve value of ~ 0 , which favors reactants.
a) Process D wi ll occur more rapidly because it has a lower energy of activation
than process A.
b) Process A will more greatly favor products at equilibrium than process B,
because the former is exergonic (the products are lower in energy than the
reactants) whi le the latter is not exergonic.
c) None of these processes exhibits an intermediate, because none of the energy
diagrams has a local minimum (a valley). But all of the processes proceed via
a transition state. because all of the energy diagrams have a local maximum (a
peak).
2 of 10 12/23/2011 3:14 AM
98 CHAPTER 6
6.8.
6.9.
6.10.
6.11.
a)
6.12.
d) In process A, the transition state resembles the reactants more than products
because the transition state is closer in energy to the reactam than the products
(the Hammond postulate).
e) Process A wi ll occur more rapidly because it has a lower energy of activation
than process B.
f) Process D will more greatly favor products at equilibrium than process B,
because the former is exergonic (the products are lower in energy than the
reactants) whi le the latter is not exergonic.
g) In process C, the transition state resembles the products more than reactants
because the transition state is closer in energy to the products than the
reactants (the Hammond postulate).

d) ()
0

0

0

0
0
c) o
Electrophlllc Nucleophilic
center ----. I --- center

0

c)
a) loss of a leaving group
b) proton transfer
c) rearrangement
3 of 10 12/23/2011 3:14 AM
CHAPTER6 99
d) nucleophilic attack
e) proton transfer
f) nucleophilic attack
g) rearrangement
h) loss of a leaving group
i) nucleophilic attack
6.13. The pi bond functions as a nucleophile and attacks the electrophilic carbocation.
This step is therefore a nucleophilic attack.
6.14.
a) proton transfer; nucleophilic attack; proton transfer
b) nucleophilic attack; proton transfer; proton transfer
c) proton transfer; nucleophilic attack; loss of a leaving group
d) proton transfer; loss of a leaving group; nucleophilic attack; proton transfer
e) proton transfer; nucleophilic attack; proton transfer
6.15. Both reactions have the same sequence: l) nucleophilic attack, followed by 2)
Joss of a leaving group. In both cases, a hydroxide ion functions as a nucleophile
and attacks a compound that can accept the negative charge and store it temporari ly.
The charge is then expelled as a chloride ion in both cases.
6.16.
..
+
a)
I
H,(B .
H'
0
'H
b)
H,(1

c)
6.17.
..e

.CI. + '-Br.
a) .. ..
:c1:

-
X(

H,e
X(
H
, I
+
H/ +'H
+
.. e
:Br:

.. e
+ :sr:
User name: Lean Pirat Book: Organic Chemistry, Student Study Guide and Solutions Manual Page: 100. No part of any book may be reproduced or transmitted by
any means without the publisher's prior permission. Use (other than qualified fair use) in violation of the law or Terms of Service is prohibited. Violators will be
prosecuted to the full extent of the law.
4 of 10 12/23/2011 3:14 AM
I 00 CHAPTER 6
:CI:
('fiMe
~ M e
d) H
6.18.
<fh H
a) a-
.. e
:CI:
0
.. e
+ :CI:
b) This carbocation is tertiary and wi ll not rearrange
c) tertiary tertiary allylfc
('((Me
~ +
Me
d) This carbocation is secondary, but it cannot rearrange to form a tertiary
carbocation.
6.19.
e)
0
~
Hv (i)
~
~
()
t)
H
<>
~ u
e
'-"
'-../
g)
h) This carbocation is tertiary and it is resonance stabilized (we will see in
Chapter 7 that this carbocation is cal led a benzylic carbocation). It will not
rearrange.
ct
5 of 10 12/23/2011 3:14 AM
6.20.
6.21.
6.22.
CHAPTER 6 I 0 I
a) a carbon-carbon triple bond is comprised of one sigma bond and two pi bonds.
and is therefore stronger than a carbon-carbon double bond (one sigma and one pi
bond) or a carbon-carbon single bond (onl y one sigma bond).
b) Using tbe data in Table 6.1, the C-F will have the largest bond di ssociation
energy.
a)
Bonds Broken
RCH:r-Br
RCH20 - H
kj/mol
+285
+435
Sum = - 29 kJ/mol.
Bonds Formed
RCH2- 0R
H- Br
k.J/mol
-381
-368
L'.H
0
for this reaction is negative, which means that the system is losing energy. It
is giving off energy to the environment, so the reaction is exothermic.
b) of this reaction is positive because one mole of reactant is convened imo two
moles of producl.
c) Both terms and contribute to a negative value of
d) No.
e) Yes.
a) A reaction for which K<tJ > I will favor products.
b) A reaction for which Keq < I will favor reactants .
c) A positive value of favors reactants.
d) Both terms contribute to a negative value of t.G, which favors products.
e) Both terms contribute to a positive value of which favors reacta nts.
6.23. K,q = I when = 0 kJ/mol (See Table 6.2).
6.24. K.q < l when t.G bas a positive value. The answer is therefore "a" (+I kJ/mol)
6.25.
a) 6Ssys is expected to be negative (a decrease in entropy) because two moles of
reactant are converted into one mole of producl.
b) t.Ssys is expected to be positive (an increase in entropy) because one mole of
reactant is converted into two moles of producl.
6 of 10 12/23/2011 3:14 AM
I 02 CHAPTER 6
6.26.
6.27.
c) 11Ssys is expected to be approximately zero, because two moles of reactant are
converted into two moles of product.
d) 11Ssys is expected to be negative (a decrease in entropy) because an acylic
compound is converted into a cyclic compound.
e) 11Ssys is expected to be approximately zero, because one mole of reactant is
converted into one mole of product, and both the reactant and the product are
acyclic.
Free l J\ Free l ~ Free l M
E n e r g y ~ E n e r g y ~ E n e r g y ~
a)
Reaction
Coordinate
a) Band D
b) A and C
c) C
d) A
e) D
t) D
g) A and B
h) c
b)
Reaction
Coordinate
c)
Reaction
Coordinate
6.28. All local minima (valleys) represent intermediates, while all local maxima (peaks)
represent transition states:
Transition States
Free Energy
Reaction Coordinate
7 of 10 12/23/2011 3:14 AM
6.29.
6.30.
6.31.
6.32.
CHAPTER 6 103
a) Rate= k[nucleophil e][substrate].
b) The rate will be tripled, because the rate is linearly dependent on the
concentration of the nucleophile.
c) The rate will be tripled, because the rate is linearly dependent on the
concentration of the substrate.
d) As a rule of thumb, the rate doubles for every increase of I 0 C. Therefore an
increase of 40
9
C wi ll correspond to .increase in rate of approximately 16-fold (2 x 2
X 2 X 2)
a) loss of a leaving group
b) carbocation rearrangement
c) nucleophilic attack
d) proton transfer
Increasing Stability

e
a) primary secondary tertiary
primary secondary
b)
secondary
resonance-stabilized
LOSS OFA
NUCLEOPHILIC
ATTACK
, LEAVING GROUP
,Jt
/' T .?\'. CI'AI,CI
c
-
- l (:,
e9'
CI- AI - CI
I
Cl
8 of 10 12/23/2011 3:14 AM
104 CHAPTER 6
6.33.
:c> ..e

r(t(H 'o'

-:;:.S.:;:-1.
NUCLEOPHILIC
ATTACK
:o
6
.. II ..
ro- s- o- 7
.. I " PROTON
,0; TRANSFER
[
0 H :o H :o H :o l
II o II e II e
----
V .
0
: eV .O: .. o,.
6.34.
PROTON
TRANSFER
OH
I 9
0 ,OH
0 . ,OH
o-s o
' H 0 S 0 H
[
H S 0 H so
6 (o
A
--./
0
6.35.
0
Br 0
(
Sf@
:9
e
NUCI..EOPHIUC

A TTACK
0
Br 0 HO Br 0
HOlJJ!e' &"41
e
-oe I v
lh --- :::,.._ -
PROTON
TRANSFER
I..OSSOFA
I..EAVING GROUP
HO Br Otttf.i:l HO Br <;?r-'1
' 00 .-. ' 00
&t:r.?
I
h
e
so,
9 of 10 12/23/2011 3:14 AM
CHAPTER 6 105
6.36.
PROTON
TRANSFER H
H- .
:o:/ +'Et

NUCLEOPHILIC
ATTACK
<>; H --:.
:o; n / H- 0 -Et
X - .. -
, OMe
PROTON

.. <> H
:QH
LOSS OFA
LEAVING GROUP
:o:

H- 0 - Et

MeOH ,

Me;g:_H
6.37.
NUCLEOPHILIC
ATTACK
o .......--;.
y. H- Q- H
R Cl:
6.38.
LOSS OFA
LEAVING GROUP
.. e
- :CI:
NUCLEOPHILIC LOSS OF A
ATTACK , .\3 LEAVING GROUP
/ .0.

R
PROTON
TRANSFER
:o: /H=6- H
)l .. H ..
R
H
NUCLEOPHILIC
ATTACK
.. e

:OH
R+ R
R
PROTON
TRANSFER
10 of 10 12/23/2011 3:14 AM
106 CHAITER 6
6.39.
PROTON
TftANSFTR
NUCLEOPHILIC
ATTACK
:o"H
I
R
:OH ,
PROTON
TRANSFER
--...:A

6.40.
PROTON
TRANSFER
\ 0
:
0
. H- A
A
PROTON
TRANSfER
eH
, 0
X
A:
NIJCLEOPHJI.IC
ATTACK
H N R
R
PROTON
TRANSfER
A:
R
NUCLEOPHILIC
ATTACK
PROTON
TRANSFER
:OH , -- :A
L. H

L.OSSOFA
LEAVING
GROUP
- H
2
0
) PROTON
I ,....,.
AD
LOSS OFA
UAVINO
GROUP
, , ' 0 PROTON
H- .A\ TRANSFER
CourseSmart - Print http://www.coursesmart.com/print?xmlid=9780471757399/107&p...
1 of 10 12/23/2011 3:15 AM
6.41.
PROTON
"N \j"
r
... l e
R -
PROTON
TRANSFER
H H
_;z

4
LOSS OFA
LEAVING
GROUP
CHAPTER 6 107
.
X:"J
11Q PROTON
R" MANS""
H
){)__ ""
2 of 10 12/23/2011 3:15 AM
108 CHAPTER 6
6.43.

H- OS03H
H 1., I OH a \
' N., H
CC
> 7
NH2:q.
CCN:(
. . '-"::: "
...-:

3 of 10 12/23/2011 3:15 AM
CHAPTER 6 I 09
6.44.
H :o

,., N
H " H

o H \;!;/
H" ' H H DQ:
_...._______
- N
H" H
6.45.
H
G'\ ----.. o"
H,\;!;//4. H" ' H
o: o

HOUOH
4 of 10 12/23/2011 3:15 AM
1 I 0 CHAPTER 6
6.46 .
.
C))
6.47.
,..... ..... (\ /\
H (8-" 'OH
O +'" ..
A ""''= H
6.48.

a) U

b)u
t:L\..-H 1\
'-"'0 HO: :OH
..
c) This carbocation is secondary, but it cannot rearrange to generate a tertiary
carbocation.
5 of 10 12/23/2011 3:15 AM
6.49.
e)
g) This carbocalion is tertiary and will not rearrange.
a)
.. "'
H-0:/ +H..- "'cL"sr:
. . I
H
b) Nucleophilic attack and loss of a leaving group.
CHAPTER 6 Ill
CH
3
' .. e
H-0- C.._H + :sr:
.. I
H
c) A CH.>CH2-Br is broken, and a CH3CH2-0H is formed. Using the data in
Table 6.1, for this reaction is expected to be approximately (285 kJ/mol)-
(381 kJ/mol). The sign of therefore predicted to be negative, which means
that the reaction should be exothermic.
d) Two chemical entities are convened into rwo chemical entities. Both the
reactants and products are acycl ic. Therefore, L\S for this process is expected to
be approximately zero.
e) L\G has two components: (L\H) and (-TL\S). Based on the answers to the
previous questions, the first term has a negative value and the second term is
insignificant. Therefore. is expected to have a negative value. This is
confirmed by the energy diagram, which shows the products having lower free
energy than the reactants.
f) The position of equilibrium is dependem on tl1e sign and value of L\G. As
mentioned in pan e, L\G is comprised of two terms. The effect of temperature
appears in the second term (-T which is insignificant because L\S is
approximately zero. Therefore, an increase (or decrease) in temperature is not
expected to have a signi ficant impact on the position of equilibrium.
g) This transition state corresponds with the peak of the curve, and has the
following structure:

h) The transition state in this case is closer in energy to the reactants than the
products, and therefore, it is closer in structure to the reactants than the products
(the Hammond postulate).
i) The reaction is second order.
6 of 10 12/23/2011 3:15 AM
112 CHAPTER 6
6.50.
j) According to the rate equation, the rate is linearly dependent on the
concentration of hydroxide. Therefore, the rate will be doubled if the
concentration of hydroxide is doubled.
k) Yes, the rate will increase with increasing temperature.
a) Keq does not affect the rate of the reaction. It only affects the equi librium
concentrations.
b) 6.0 does not affect the rate of the reaction. It only affects the equilibrium
concentrations.
c) Temperature does affect the rate of the reaction, by increasing the number of
collisions that result in a react ion.
d) 6.H does not affect the rate of the reaction. It only affects the equilibrium
concentrations.
e) E, greatly affects the rate of the reaction. Lowering theE, wi ll increase the rate
of reaction.
f) 6.S does not affect the rate of the reaction. It only affects the equilibrium
concentrations.
6.51. In order to determine if reactants or products are favored at high temperature, we
must consider the effect of temperature on the sign of 6.0. Recall that 6.0 has
two components: (6.H) and (-T6.S). The reaction is exothermic, so the first term
(6.H) has a negative value, which contributes to a negative value of 6.0. This
favors products. At low temperature, the second term will be insignificant and the
first term will dominate. Therefore, the process will be thermodynamically
favorable, and the reaction wi ll favor the formation of products. However, at high
temperature, the second term becomes more significant. Tn this case, two moles
of reactants are converted into one mole of product. Therefore, 6.S for this
process is negative, which means that (-T6.S) is positive. At high enough
temperature, the second term (-T 6.S) should dominate over the first term (6.H),
generating a positive value for 6.0. Therefore, the reaction wil l favor reactants at
high temperature.
6.52. Recall that 6.0 has two components: (6.H) and (-T6.S). We must analyze each
term separately. The first term is expected to have a negative value, because three
pi bonds are being converted into one pi bond and two sigma bonds. A sigma
bond is stronger (lower in energy) than the pi component of a double bond (see
problems 6.2 and 6.20). Therefore, reaction is expected to release energy to the
environment, which means the reaction should be exothermic. In other words, the
first term (6.H) has a negati ve value, which contributes to a negative value of 6.0.
This favors products. Now let's consider the second term (-T6.S) contributing to
6.0. In this case, two moles of reactants are converted into one mole of product.
Therefore, 6.S for this process is negative, which means that (-T6.S) is positive.
At low temperature, the second term will be insignificant and the first term wil l
dominate. Therefore, the process wi ll be thermodynamically favorable, and the
reaction wil l favor the formation of products. However, at high temperature, the
7 of 10 12/23/2011 3:15 AM
CHAPTER 6 113
second term becomes more significant. At high enough temperature, Lhe second
term (-Tt.S) should dominate over Lhe frrst term (t.H), generating a positive value
for t.G. Therefore. the reaction will favor reactants at high temperature.
6.53. The nitrogen atom of an ammonium ion is positivel y charged, but Lhat does not
render it electrophilic. In order to be electrophilic, it must have an empty orbital
Lhat can be attacked by a nucleophiJe. The nitrogen atom in Lhis case does not
have an empty orbital. because nitrogen is a second row element and Lherefore
only has four orbitals with which to form bonds. All four orbitals are being used
for bonding, leaving none of the orbitals vacant. As a result, the nitrogen atom is
not electrophilic, despi te the fact that i positi vely charged.
6.54.
In contrast. an iminium ion is resonance stabili zed:
[
H H 1
I
A.@.....,- N,
I @ A - T A
A An Jmlnlum Jon A
The second resonance structure a positive charge on a carbon atom,
which serves as an electrophilic center (a carbocation is an empty p orbital ).
Therefore. an iminium ion is an electrophile and is subj ect to attack by a
nucleophile:
H
A
Nuc . .........____.,.. 'f<ifA
A
Cl (_CI
I I

a
:oH
J2 {>fd

cJ + + CIG
Me
A . ..
:o -
. -
Me
Me''
8 of 10 12/23/2011 3:15 AM
Review of Concepts
Chapter 7
Substitution Reactions
entitled Review of Concepts and Vocabulaty.
Substitution reactions exchange one for another.
Evidence for the concerted mechanism, called SN2. includes the observation of a
_____ -order rate equation. The reaction proceeds with of
configuratjou.
SN2 reactions are said to be because the configuration of the
product is determined by the confi guration of the substrate.
Evidence for the stepwise mechanism, called SNl. incl udes the observation of a
_____ .order rate equation.
The step of an SNI process is the rate-determining step.
An SNl reaction is a stepwise process with a first-order rate equation.
There are four factors that impact the competition between the SN2 mechanism
and SNI: I) the , 2) the , 3) the ___ _
------ and 4) the _____ _
----------solvents favor SN2 .
Review of Skills
Follow the instructions below. To verify that your answers are correct. look in your
textbook at the end of Chapter 7. The answers appear in the secti on entitled Ski// Builder
Review.
SkillBuilder 7.1 Drawing the Curved Arrows of a Substitution Reaction
A CONCER1EDNECHANISM
DRAWCURVEDARIK>WS, SHOWIH(J NUCLEOPHI.IC
A. TrACK ACCOMPANI0 BY SIMUL TMEOUS LOSS()(!
A LEA. VIN(j GROUP
e
Nuc:
)-to ~ u c
A. STEPWISE MECHANISM
DRAW A CURVED ARROW SHOWING THE LOSS OF rHE LEAVINO (JROUP
tO FORMA CARBOCA1fON INrERMEOIAre. FOlLOWED BY ANOTHER
CURVED ARROW SHOWJNO THE NUCLEOPHILIC ATTACK
-j-LG
e
:Nuc \ N
- I uc
SkillBuilder 7.2 Drawing the Product of an SN2 Process
DRAW THE UAJOR PRODUCT OF THE FOUOWJNG REACnON
Br 0
~ + OH
D
+
e
Br
9 of 10 12/23/2011 3:15 AM
Skill Builder 7.3 Drawing the Transition Stale of an SN2 Process
NaSH
../"'sH
[
DRAW THE TRANSITION STATE OF THE FOLLOW'WJ REACTION
TRANSmON STATE
SkiliBuilder 7.4 Drawing the Carbocalion Intermediate of an SNl Process
DRAW THE CARBCCAT/ON THAT WOVI.D BE FOIIWED If' A CHLORIDE ION IS EXPELI.EO
FROM THE FOUOWING COMPOUND

SkillBuilder 7.5 Drawing the Products of an S,.. J Process
PREDICT THE PIIODUCTS OF THE FOLtOWING SNI REACTION
NaCN
I
SklliBuilder 7.6 Drawing the Complete Mechanism of an SNI Process
IDENTIFY THE TWO CORE STEPS AND THREE POSSIBLE ADDfTfOHAL STEPS OF AN SNr PROCESS
CHAPTER 7 I 15
r
/ TWOCORESTEPS
__ l
-------- --------
THREE POSSIBLE ADDITIONAL STEPS
SkillBuilder 7.7 Drawing the Complete Mechanism of an SN2
IDENTIFY THE ONE CORE STEP (CONCERTED} AND TWO POSSJB1E ADDITIONAL STEPS OF AN S,;t PROCESS
CORE STEP
___ H.._ __ H __ _
.""'
/
nvo POSSIBLE ADDITIONAl. STEPS
10 of 10 12/23/2011 3:15 AM
1 16 CHAPTER 7
Skilffiuildcr 7.8 Determining whether a Reaction Proceeds via au SNI Mechanism or an SN2
Mechanism
FII.L tN THE BELOW. SHOWING THE FEATURES
THAT FAVOR S,P OR Sn1 REACTlONS
SN2
SN1
SUBSTRATE
NUC
LO
SOLVENT
Skill Builder 7.9 Identifying the Necessary for a Substitution Reaction
IDENTIFY THE REAGENTS NECESSARY TO ACHIEVE THE FOHOWIHG TRANSFORWo T/ON
OH

2) ['-___ l
Review of Reactions
Follow the instructions below. To verify that your answers are correct, look in your
textbook at the end of Chapter 7. The answers appear in the section entitled Review of
Reactions.
DRAW THE CURVED ARROWS THAT SHOW
THE FLOW OF ELECTRON DENSITY OUR/NO
THE FOLLOW.WG S,;l REACTION
DRAW THE CURVED ARROWS THA T SHOW
THE FLOW OF ELECTRON DENSITY DURING
THE REACTION
H
H-)-LG
H
-1--LG
e
:Nuc
H
Nuc+ H
H
I

e
:Nuc
+
1 of 10 12/23/2011 3:16 AM
Solutions
7.1.
a) 4-chloro-4-ethylheptane
b) 1-bromo- 1-methylc}clohe'ane
c) 4.4-dibromo- 1-chloropenlane
d)
7.2.
a)
b)
7.3.
-
a)
" ..

b)
-
7.4.

;v ..
:sH
A
+

:o'.

0 ..
.
: c1:

:o e ..
Q + :sr:
CHAPTER 7 117
e ..

Me
+
e ..
:I:
2 of 10 12/23/2011 3:16 AM
I 18 CHAPTER 7
7.5.
7.6.
a) the rate of the reaction is t ripled.
b) the rate of the reaction is doubled.
c) the rate of the reaction will be six times faster.
7.7.
SH
a ) ~
7.8.
~
b) Cl
s
QH
c ) ~
e ..
+
:sr:
The reaction does proceed with inversion of configuration. However, the Cahn-lngold-
Prelog system for assigning a stereodescriptor (R or S) is based on a prioritization
scheme. Specifically, the four groups connected to a chi rality center are ranked (one
through four) . In the reactant (above left), the highes1 priority group is the leaving group
(bromide) which is then replaced by a group that does not receive the highest priority. In
the product, the fluorine atom has been promoted to the highest priority as a result of the
reaction, and as such, the prioritization scheme has changed. In this way, the
stereodescriptor (S) remains unchanged, despite the fact that chirality center undergoes
inversion.
3 of 10 12/23/2011 3:16 AM
CHAPTER 7 119
7.9.
o) [ ~ -------l ------E 1
7.10.
7.11.
Being
formed
Being
broken
b) [5g: __ - k- ---___ r r
*
d)
[ Ht - --- -6--- - - - - - ~ 1
This step is favorable (downhjll in energy) because ring strain is alleviated when the
three-membered ring is opened.
7.12.
H ~ ~
I""' ~ ~ H
h H 3
- H+
N
a) Nicotine
*
4 of 10 12/23/2011 3:16 AM
120 CHAPTER 7
b)
choline
7.13. a) The rate of the reaction will be doubled, because the change in concentration
of sodium chloride will not affect the rate.
b) The rate of the reaction will remain the same, because the change in concentration of
sodium chloride wil l not affect the rate.
7.14. Draw the carbocation intermediate generated by each of the following substrates in
an SN I reaction:
(o) ~ (b) 6
(c)*
(d) _/L
~
7.15.
~ B r
The first compound will generate a tertiary carbocation, while the second compound will
generate a tertiary benzylic carbocation that is resonance stabilized. The second
compound leads to a more stable carbocation, so that compound will lose its leaving
group more rapidly than the first compound.
7.16.
d CI
+ Nal
a)
b ) ~
HS ~
Bre
+
~
+
~
+
~
+
cf3
y
oy
c)
0 0
~
e
+ I
d)
5 of 10 12/23/2011 3:16 AM
CAAPTER 7 121
+
Diastereomers
7. 18.
a) No
7.19.
a) No
g)No
7.20.
a) No
7.21.
a)
b) c) No
b) Ye c) Ye
h) i) No
b) Ye'> c) Yes
'
H- Br:
' \
-" H- Br:
c)
d) e) f)
0
d) Ye
e) f)
0
j) No
1.) Yc' I) No
d) No c) No f) No
H
."6
.. e
+

Br

6 of 10 12/23/2011 3:16 AM
122 CHAPTER 7
d)
X( I
OEt
r;:,i X( q ;-Et EtOH X(

EtOH
- - + ____:__:__.,. -
-
MeXr
g)
-
h)

7 of 10 12/23/2011 3:16 AM
CHAPTER 7 123
7.22.
~
[HUe Attac\ H'
c)
LG
c
Nuc Attack] H'
re.,r.
d)
.w LG INucAttack
H'
e)
.w I.LG
c
(Nuc Attack) H' ,...,.,.
t)
g)
LG Nuc Attack
Nuc Attack
H'
h)
Problem 7.20c and 7.20h exhibit the same pattern. Both problems are characterized by
three mechanistic steps: I ) loss of a leaving group, 2) nucleophil.ic artack, and 3) proton
transfer.
7.23.
~ ~ ' t
-
H ; o ~ ~
~ ;
<>9-H
H
The chirality center at C2 is lost when the leaving group leaves to fonn a carbocation
with trigonal planar geometry. The chirality center at C3 is lost during the hydride shift
in the following step. Once again, the chirality center is converted into a trigonal planar
sp
2
hybridized center (which is no longer a chi ral ity center).
8 of 10 12/23/2011 3:16 AM
124 CHAPTER 7
7.24.
a)

[P
b)
/"""- -""'
I ( EtOH

c)
CI/.::'.
0V
d)

(
..
7.25.
7.26.
a) SNI
e) Both

H- fP-Me
I
H
b) SN2 c) Neither
f) Neither g) Both

9 of 10 12/23/2011 3:16 AM
CHAPTER 7 125
7.27.
a) SNl b) SN2 c) SN2 d) SN2 e) SN2
7.28.
Cl
TsO
OMe
a)
TsO
OMe
b)
7.30.
Acetone i s a pol ar aproti c sol vent and will favor SN2 by rai sing the energy of the
nucleophile, giving a smaller En.
7.31.
.l )
MeOH
6'
SN1
cr8r
c 1
8
crCI
HMPA
SN2
b)
-- o -H
~
H- Br
~
SN1
c)
Racemic
NaCN
SN2
~ O T s
~ C N
d)
DMF
10 of 10 12/23/2011 3:16 AM
126 CHAPTER 7
cr:
SN1
e)
Racemic
NaCN
()CN
SN2
DMSO
7.32.
No. Preparation of this amine via the Gabriel synthesis would require the use of a tertiary
alkyl halide, which will not undergo an SN2 process.
7.33.
(a)
~ ,
NaOH
(b)
0
HBr
6
~ O H
Br
NaSH gH
(d)
~
DMSO
~
~ ,
(c)
~ O H
HI
(e)
0
I eo)(.
~ B r DMSO
OH
~
1) TsCI, pyridine
2) NaBr, OMSO ~
(f)
)!!:
(h) u
(i)
X:,
1) TsCI, pyridine
~
2) NaCN
7.34.
OH
1) TsCI, pyridine
SH
~
2) Nal , DMSO
~
(R)-
3) NaSH, DMSO
(R)-
2-bul anol 2-butanelhlol
1 of 10 12/23/2011 3:17 AM
CHAPTER 7 127
7.35.
0 NH2 <:_"",CI
H -F\ r1
HO
"
melphalan Cl
0 NH2
..
Cl
j
G
Nuc:
0 NH
2
Nuc
H -j=\
HO

0 NH
2
Nuc

HO

Nuc
7.36.
a) Systematic Name= 2-chloropropane
Common Name= isopropyl chloride
b) Systematic Name= 2-bromo-2-melhylpropane
Common Name= tert-butyl bromide
c) Systematic Name= 1-iodopropane
Common Name= propyl iodide
d) Systematic Name= 2-chlorobutane
Common Name= propyl iodide
d) Systematic Name= (R)-2-bromobutane
Common Name= (R)-sec-butyl bromide
e) Systematic Name= 1-chloro-2,2-dimethylpropane
Common Name= neopentyl chloride
f) Systematic Name= cbJorocyclohexane
Common Name= cyclohexyl chloride
2 of 10 12/23/2011 3:17 AM
128 CHAPTER 7
7.37.
Increasing reactivity (SN2)
+-[

I
7.38.
Cl
A_
a) secondary primary
c) secondary tertiary
7.39.

primary
more sterically
b) hindered

d)
primary
less sterically
hindered
better
leaving group
No. Preparation of this compound via the process above would require the use of a
tertiary alkyl halide, which will not undergo an SN2 process.
7.40.
a) NaSH
b) sodium hydroxide
c) methoxide dissolved in DMSO
7.41.
[I

a) tertiary primary
b) primary tertiary
C5
[6J
better
c)
allylic
d)
leaving group
3 of 10 12/23/2011 3:17 AM
7.42. a) The rate of the reaction is doubled.
b) The rate of the reaction is doubled.
7.43. a) The rate of the reaction is doubled
b) The rate of the reaction will remain the same.
7.44. a) aprotic
b) protic
c) aprotic
d) protic
e) protic
7.45.
H Br
~ o ,
a)
b)
R
R
CHAPTER 7 129
c) The reaction is an SN2 process, and it does proceed with inversion of configuration.
However, the prioritization scheme changes when bromide (# I) is replaced with a cyano
group (#2). As a result, the Cahn-lngold-Prelog system assigns the same configuration to
the reactant and the product.
7.46.
[k J: tf
7.47.
Iodide functions as a nucleophile and attacks (S)-2-iodopentane, displacing iodide as a
leaving group. The reaction is an SN2 process, and therefore proceeds via inversion of
configuration. The product is (R)-2-iodopentane. The reaction continues until a racemic
mixture is obtained.
4 of 10 12/23/2011 3:17 AM
130 CHAPTER 7
7.48.

Racemic
The chirality center is lost when the leaving group leaves to form a carbocation with
trigonal planar geometry. The nucleophile can then attack either face of the planar
carbocation, leadi ng to a racemic mixture.
7.49.

.. 8
OH

Racemic
E
Reaction coordinate
7.50.
lncreasin2

e
ct
() ()
7.51.
(f)

secondary tertiary

ct

0

primary secondary
5 of 10 12/23/2011 3:17 AM
7.52.
/\
.. HJ.c1:
7.53.
7.54.
a)

b)

c)
(t
H---;1.:
H
.!f.H

o............,..
0

e

:SH
@
H

-H20
CRAPTER7 13 1
.. e
+ : Br:

c-1 ..

3 Steps

2Steps
C :=e

3 Steps
6 of 10 12/23/2011 3:17 AM
132 CHAPTER 7
d)

4 Steps
7.55.

EtOH

a)
NaBr
b)

OH
HCI
c) y

NaCN
DMSO
7.56.
(o)
0
7.57.

e ..
/1 :o- H
j("Br
Although the substrate is primary. it is still sterically hindered. As a result, SN2 reactions
at neopentyl hal ides do not occur at an appreciable rate.
7 of 10 12/23/2011 3:17 AM
7.58.
a)
CHAPTER 7 133

b) The substrate i s primary, and therefore, the reaction must proceed via an SN2 process.
SN2 reactio-ns are highly sensitive 10 the strength or the nucleophile, amlthe nucleophi le
(water) i s a weak nucleophil e. As a result, the reaction occurs slowly.

( /1 :o- H

c)

.. e
+ : Br:
Hydroxide i s a strong nucleophi le, which favors the SN2 process.
7.59.
a)

b)

Cl

Br

NaOH
1) TsCI, py
2) NaCN
HBr
NaSH
0
NaO)l___

SH

0
OA_

8 of 10 12/23/2011 3:17 AM
134 CHAPTER 7
7.60.
a ) ~ l + 8 0H
d)0 .,, ,
e) X
f) s
7.61.
SH
a ) ~
7.62.
+
8
sH
+ H
2
0
+ H
2
S
CN
c ) ~
The second method is more efficient because the alkyl halide (methyl iodjde) is not
sterically hindered. The first method is not efficient because it employs a tertiary alkyl
halide, and SN2 reactions do not occur at tertiary substrates.
7.63.
D OH
1) TsCI, pyridine
0
sr
2) NaBr
a)
-j--oH
HCI
-j--c1
b)
c) _............._CI
NaOH
_............._OH
9 of 10 12/23/2011 3:17 AM
7.64.

e ..
..e
:S-H
a) --"---l
+ :er:
b) Rate = k I ] [ NaSH ]
c) The rate would be slower.
E
d)
React ion coordinate
:j:
e)
[ -------;rt- -----t l
7.65.
a) SN I (tertiary substrate)
b)
\If.!

\;!;.> I
H
CHAPTER 7 135
d) No. The rate is not dependent on the concentration or strength of the nucleophile.
E
e)
Reaction coordinate
10 of 10 12/23/2011 3:17 AM
136 CIIAI>TER 7
Br 8
/
:eN

v
gN <::? .
~ + .Br .
b)
Rate- k j
c)
d) Ye . The reaction rate would double.
E
e)
Reaction coordinate
7.67.
[
tr - 'd'
0
~
} ) : ~
0
. tr H
H' ' H
:::,...1 - :::,... 1
1 of 10 12/23/2011 3:18 AM
CHAPTER 7 137
7.68.
/--- .. e
0 (\ /

+
a)
b) This reaction occurs via an SN2 process. As such, the rate of the reaction is highly
sensitive to the nature of t11e substrate. The reaction will be faster in this case, because
the methyl ester is less sterically hindered than the ethyl ester.
7.69.
cf) 8
ex

Br
7.70.

( /1 ::i.:

7.71.
.e
o:
C$.

When the leaving group leaves, the carbocation formed is resonance stabilized:
Resonance stabilized
7.72.
Iodide is a very good nucleophile (because it is polarizable), and it is also a very good
leaving group (because it can stabilize the negative charge by spreading the charge over a
large volume of space). As such, iodide will function as a nucleophile to displace the
chloride ion. Once installed, the iodide group is a better leaving group than chloride,
thereby increasing the rate of the reaction.
2 of 10 12/23/2011 3:18 AM
138 CHAPTER 7
7.73.
H
'l>(j)
H' ' H
6 ]
6
0H
6
~ 0 H
~ I
~
3 of 10 12/23/2011 3:18 AM
Chapter 8
Alkenes: Structure and
Preparation via Elimination Reactions
Review of Concepts
the end of Chapter 8. Each of the sentences below appears in the section entitled Review
of Concepts and Vocabulary.
Alkene stabi.lity increases with increasing degree of _______ _
E2 reactions are said to be regioselective, because the more substituted alkene.
called the product, is generally the major product.
When both the substrate and the base are steri cally hindered. the less substituted
alkene, called the product, is the major producr.
E2 reactions are ster eospecific because they generally occur via the
---------conformation.
Substituted cyclohexane only undergo E2 reactions from the chair conformation
in which the leaving group and the proton both occupy positions.
El reactions exhibit a regiochemical preference for the _____ product.
El reactions are not stereospecific. but they are stereo. _____ _
Strong nucleophiles are compounds that contain a and/or are
Strong bases are compounds whose conjugate acids are --------
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 8. The answers appear in the section enlitled
Ski/IBuilder Review.
8.1 Assembling t he S)stematic Name of an Alkene
PROVIDE A SYSTE .. ATIC NAME FOR THE FOtLOWINQ COMP<JUND
1/ tDEIITIFY THE PARENT
2} IDENTIFY AND NAME SUBSTITUENTS
3) ASSJGN LOCANTS fO EACH SUBSTmJENT
4) ALPHABETIZE
8.2 Assigning the Configuration of a double bond
ASSIGN Tl-iE CONFIGURATION
OF THE DOUBLE BONO IN THE
FOLLOWING COMPOOND
HOX o
)
4 of 10 12/23/2011 3:18 AM
140 CHAPTER 8
8.3 Comparing the Stability of Isomeric Alkenes
CiRCLE THf MOST STABL.EALI<6NE BELOW
8.4 Drawing the Curved Arrows of an Elimination Reaction
A CONCERTED IIECHANJSII A STEPWISE llECHANISJI
DRAW THREE CURVED ARROWS. SHOWING A
PROTON TRANSFER ACCOiAPANIEO BV
SJIIUH ANEOtJS LOSS OF A LEAVING GROUP
DRAW A CURVED ARROW SHOWING THE LOSS OF THE LEAVING GROUP
TO FORM A CARBOCATiON INTERMEDIATE, FOl.LOWEO BY ANOtHER
TWO CURVED ARROWS SllWING A PROTON TRANSFER
-
- LGG
e
Base: -\LG
8.5 Predicting the RegiochemiClll Outcome or an E2 Reaction
: Base
-
DRAW THE ELAIINATION PRODUCTS OBTAINED WHEN THE COMPOUND SHOW IS TREATED WITH A STRONG BASE.
Strong Base
D
+
D
ZAITSEV HOFfAAHH
8.6 Predicting the Stereochemical Outcome of an E2 Reaction
PREDICT THE STEREOCHE .. ICAL OUTOOAAE OF THE FOLLOWING REACTION ANO OIIAW THE PRODUCT.
~
Ct
Strong Base
I
8.7 Drawing the Products of an E2 Reaction
PREDICT TilE w.JOR AND .. /NOR PRODUCTS OF THE FOLLOWING REACTION
Br
~
NaOEt
IIAJOR II IN OR
8.8 Predicting tbe Regiochemical Outcome of an El Reaction
PREDICT THE AAAJOR AND UINOR PRODUCTS OF THE FOLLOWING REACTION.
heat
ltiAJOii
MINOii
5 of 10 12/23/2011 3:18 AM
8.9 Drawing the Complete Mechanism of on El Reaction
iDENTIFY THE TWO CORE STEPS AND TWO POSSIBLE ADDITIONAL. STEPS OF AN El PROCESS
TWO CORE STEPS
/ ~
._....JH,-------H.----.,H..______,Jl
~ /
TWO POSSIBLE ADDITIONAL STEPS
8.10 Determining the Function of a Reagent
IDENTIFY REAGENTS fflAT FALL INTO EACH OF THE FOUR CATEGORIES BELOW:
NUCLEOPHILE (ONLY) BASE
(ONLY)
- -
8.11 Identifying the Expected Mechanism(s)
JDENTIFY THE MECHANISM(S) THAT
OPERATE IN EACH OF THE CASES BELOW:
STRONG/ STRONG
NUC BASE
0
ONLY
8.12 Predicting the Products of Substitution and Elimination Reactions
FlU. tN THE BLMKS BEL. OW.
STEP 1 STEP 2 STEPS
CHAPTER 8 141
WEAK/ WEAK
NUC BASE
DETERMINE THE FUNCTION ANALYZE THE CONSIDER ANY RELEVANT REGIOCHEMJC.AL AND
OF THE AND DETERMINE THE EXPECTED REQUIREMENTS
WECHANISJA(S).
6 of 10 12/23/2011 3:18 AM
142 CHAPTER 8
Review of Synthetically Useful Elimination Reactions
Identify reagents that wil l achieve each of the transformations below. To veri fy that your
answers are correct, look in your textbook at the end of Chapter 8. The answers appear in
the section entitled Review of Synthetically Useful Elimination Reactions .
..
Solutions
8.1.
a) 2,3,5-trimethyl-2-heptene
b) 3-ethyl-2-rnethyl-2-heptene
c) 3-isopropyl-2,4-dimethyl-1-pentene
d) 4-tert-butyl-l-heptene
8.2.
a) ycr
b) Y'(' c) o(
8.3. 2,3-dimethylbicyclo[2.2.1 )hept-2-ene
8.4.
- -
((
u ~ t h i s substituent counts twice
a)
trlsubstltuted b) dtsubstltuted c) trlsubstltuted
y
+
d)
trlsubstltuted e) monosubstituted
7 of 10 12/23/2011 3:18 AM
CHAPTER 8 143
8.5 .
. )r b ) ~ o )
~
d) z z
8.6. When using cis-trans terminology, we look for two identical groups. In this case,
there are two ethyl groups that are in the trans configuration:
Cl
~
trans
However, when using E-Z terminology, we look for the highest priority at each vinylic
position. Chlorine recei ves a higher priori ty than ethyl, so in this case, the highest
priority groups are on the same side of the pi bond:
Cl
~
z
Below are two other examples of alkenes that have the trans configuration, but
nevertheless have the Z configuration:
r BrF
8.7.
a)
Increasing stability
& & &
df trl tetra
substituted substituted substituted
b)
Increasing stability
~
~
~
mono- dl- trl-
substituted substituted substituted
8 of 10 12/23/2011 3:18 AM
144 CHAPTER 8
8.8. In the first compound, all of the carbon atoms of the ring ares,} hybridized and
tetrahedral. As a result, they are supposed to have bond angles of approximately 1 09.5'',
but their bond angles are compressed due to the ring (and are almost 90). In other
words, the compound exhibits angle strain characteristic of small rings. In the second
compound, two of the carbon atoms are sp
2
hybridized and trigonal planar. As a result,
they are supposed to have bond angles of approximately 120, but their bond angles are
compressed due to the ring (and are almost 90). The resulting angle strain (120 ~ 90)
is greater than the angle strain in the first compound (l09.5 ~ 90). Therefore, the
second compound is higher in energy, despite the fact that it has a more highl y
substituted double bond.
8.9.
8.10.
a)
: - - - ~
CJO
.. r e ..
.. s : ~ E t
b)
c)
a) d i:;i:
..e
- :CI:
~
b)
c r ~ ~ :
.. e
- : sr:
k r:
c) ..
.. G
- : I :
-
0
9 of 10 12/23/2011 3:18 AM
8.11. This mechanism is concerted:
8.12.
8.13.
.. Q ( OTs

f ..
..e
:sr:
CHAPTER 8 145
a) 3x fasrer b) 2x faster c) 6x fasrer
8.14.
8.15.
a)
primary
substrate
b)
Increasing reactivity towards E2
secondary
substrate
Increasing reacti vity towards E2
Cl

primary secondary
substrate substrate
-15
8
EtO
t)
major
a)
(more substituted)
cfBr
tertiary
substrate

tertiary
substrate
+
t
minor
(less substituted)
10 of 10 12/23/2011 3:18 AM
146 CHAPTERS
A
-1 oe
A A
+
major minor
b)
(less substituted) (more substituted)
~
NaOH
~
+
~
major minor
c)
(more substituted) (less substituted)
~
-}-oe
~
+
~
major minor
d)
(less substituted) (more substituted)
Br
NaOH
~
+
e)
only product
Br
-}-oe
~
+
f)
only product
8.16.
a) The more substituted alkene is desired, so hydroxide should be used.
b) The less substituted alkene is desired, so tert-butoxide s hould be used.
8.17.
a)
~ B r
1 of 10 12/23/2011 3:19 AM
b)
8.18.
~
a)
major
~
~
c)
the only E2 product
f) the only E2 product
~
h)
major
8.19.
crY
+
+
L
()
Qf
minor
~
d)
the only E2 product
~
g)
major
minor
Strong Base
CHAPTER 8 147
Qf ,&
b) the only E2 product
~
,&
e)
the only E2 product
+
minor
2 of 10 12/23/2011 3:19 AM
148 CHAPTER 8
8.20. The leaving group in menthyl chloride can only achieve antiperiplanarity with one
beta proton, so only one elimination product is observed. In contrast, the leaving group
in neomenthyl chloride can achieve antiperiplanarity with two beta protons, giving rise to
two possible products:
" ' ~ .. d'
H
menthyl chloride
"0::
H
neomenthyl chloride
8.21. Because of the bulky tert-butyl group, the first compound is essentially locked in a
chair conformation in which the chlorine occupies an equatorial position. This
conformation cannot undergo an E2 reaction because the leaving group is not
antiperiplanar to a proton. However, the second compound is locked in a chair
conformation in which the chlorine occupies an axial position. This conformation rapidly
undergoes an E2 reaction. Therefore, the second compound is expected to be more
reactive towards an E2 process than the first compound.
8.22.
"-..../
y
"-..../
()(
NaOEt
Vi v
+
~
a)
major minor
Br
cY
NaOEt
~ CY
+
b)
major minor
).if NaOEt
).d'
c)
only E2 product
3 of 10 12/23/2011 3:19 AM
CHAPTERS 149
cfl
NaOEt
u
()
+
d)
major minor
Br
-1-oe
()
cr+
v
e)
major minor
Br
-1-oe
6'' o'
.'
0
only E2 product
8.23.
X
RA R
strong base
RYYR
R R R R
all R groups are identical
8.24.
~ rongba"
8.25.
X
~
strong base
+
8.26.
a) Only the concentration of tert-butyl iodide affects the rate, so the rate will double.
b) Only the concentration of tert-butyl iodide affects the rate, so the rate will remain
the same.
8.27.
~
a ) u=
~
b) 0
' ~ /
c) l(t)J
d ) ~
4 of 10 12/23/2011 3:19 AM
150 CHAPTER 8
8.28.
a ) ~
~
b) v
8.29.
~
H2S04
heat
a)
EIOH
~ r
heat
b)
OH
~
H2S04
heat
c)
dY
"'<:::
EtOH
heat ..--;;.
d)
' l /
c) rwr
~
+
~
major minor
-'Y
+
~
major minor
d ) ~
u VI
+
..--;;.
maj or minor
dv
+
dY
major minor
8.30. Both alcohols below can be used to form the product. The tertiary alcohol below
will react more rapidly because the rate determini ng step involves formation of a tertiary
carbocation rather than a secondary carbocation.
CXH
H2S04
5 of 10 12/23/2011 3:19 AM
8.31.
8.32.
8.33.
~
H
2
S0
4
heat
a)
b)xzx
H
2
S0
4
heat
a) No. the leaving group is not OH
b) Yes, the leaving group is OH
c) No. the leaving group is not OH
d) Yes, the leaving group is OH
c) No. the leaving group is not OH
f) No. the leaving group is not OH
CHAPTER 8 151
a) No. Loss of the leaving group forms a tertiary carbocation, which will not
rearrange.
b) Yes. Loss of the leaving group forms a secondary carbocation, which can
undergo a methyl shift to form a more stable tertiary carbocation.
c) Yes. Loss of the leaving group forms a secondary carbocation, which can
undergo a hydride shift to form a more stable tertiary carbocation.
d) No. Loss of the leaving group forms a secondary carbocation, which cannot
rearrange in this case to form a tertiary carbocation.
e) No. Loss of the leaving group fom1s a rertiary carbocation, which will not
rearrange.
f) No. Loss of the leaving group forms a secondary carbocation, which cannot
rearrange in this case ro form a tertiary carbocation.
6 of 10 12/23/2011 3:19 AM
152 CHAPTER 8
8.34.
a)

\(\
u H- 0 - S- 0 - H

6
b)
&
e
- Br
c)

'-'::::
.,.,:;
d)
4 10
!(\"
-cf>
H- O- S- 0 - H
II
0

&
..

oA
..
.,.,:;
7 of 10 12/23/2011 3:19 AM
CHAPTER 8 153
8.35. Problem 8.34b and 8.34c exhibit the same pattern because both have leaving
groups that can leave without being protonated, and both do not exhibit a carbocation
rearrangement. As a result both mechanisms involve only two steps: I ) loss of a leaving
group and 2) proton transfer.
+ H+
a)
- LG
b)
-LG
c)
d)
-LG
-LG
C+
rearr.
8.36. The first method is more efficient because it employs a strong base to promote an
E2 process for a secondary substrate bearing a good leaving group. The second method
rel ies on an E I process occurring at a secondary s ubstrate, which will be slow and will
involve a carbocation rearrangement to produce a different product.
8.37.
a)
8.38
Cl Cl _ ~ N H 2
~ ~ / -
H H
R- - - R
8 of 10 12/23/2011 3:19 AM
I 54 CHAPTER 8
8.39.
a) weak nucleophile, weak base
b) strong nucleophile, weak base
c) strong nucleophile, strong base
d) strong nucleophile, weak base
e) strong nucleophile, strong base
t) weak nucleophile, weak base
g) strong nucleophile, strong base
h) weak nucleophile, strong base
8.40. Aluminum is a larger atom and is polarizable. Therefore, the entire complex can
function as a strong nucleophile, and can serve as a delivery agent of a hydride
ion. In contrast, the hydride ion by itself is not polarizable and does not function
as a nucleophile.
8.41.
8.42.
8.43.
a) NaOH is a strong nucleophile and strong base. The substrate in this case is
primary. Therefore, we expect SN2 (giving the major product) and E2 (giving the
minor product).
b) NaSH is a strong nucleophile and weak base. The substrate in this case is
primary. Therefore, we expect only SN2.
c) When a primary alkyl halide is treated with t-BuOK, the predominant pathway
is expected to be E2.
d) DBN is a weak nucleophile and a strong base. Therefore, we expect only E2.
e) NaOMe is a strong nucleophile and strong base. The substrate in this case is
primary. Therefore, we expect SN2 (giving the major product) and E2 (giving the
minor product).
a) NaOEt is a strong nucleophile and strong base. The substrate in this case is
secondary. Therefore, we expect E2 (giving the major product) and SN2 (giving
the minor product).
b) Nal is a strong nucleophile and weak base. DMSO is a polar aprotic solvent.
The substrate is secondary. Under these conditions, only SN2 can occur.
c) DBU is a weak nucleophile and a strong base. Therefore, we expect only E2.
d) NaOH is a strong nucleophile and strong base. The substrate in this case is
secondary. Therefore, we expect E2 (giving the major product) and SN2 (giving
the minor product).
e) t-BuOK is a strong, sterically hindered base. Therefore, we expect only E2.
a) EtOH is a weak nucleophile and weak base. The substrate in thi s case is
tertiary. Therefore, we expect both SN I and El.
9 of 10 12/23/2011 3:19 AM
8.44.
CHAPTER 8 155
b) 1-BuOK is a strong, stericall y hiJ1dered base. Therefore. we expect only E2.
c) Nal is a strong nucl eophile and weak base. The substrate in this case is tertiary.
Therefore, we expect onl y SN I.
d) NaOEt is a strong nucleophile and strong base. The substrate in this case is
tertiary. Therefore, we expect onJy E2.
e) NaOH is a strong nucleophile and strong base. The substrate in this case is
tertiary. Therefore, we expect only E2.
a) An E2 reaction does not readily occur because the base is weak.
b) An El react ion does not readily occur because the substrate is primary.
c) Replacing the weak base (EtOH) with a strong base (such as NaOEt) would
greatly enhance tJ1e rate of an E2 process.
d) Replacing the primary substrate with a tertiary substrate (such as 1-chloro-1 ,l -
dimethylbutane) would greatly enhance the rate of an El process.
8.45. The substrate is tertiary, so SN2 cannot occur at a reasonable rate. There are no
beta protons, so E2 also cannot occur.
8.46.
a)
OTs
NaCI
Cl
~
i
DMSO
~
b)
~
NaOH
~
~
+
major minor
c)
if
.:r-oe K0
oA ci'
+
major minor
d)
if
crl
DBN
I
:::,.-.
c)
~ I
IBuOK
~
10 of 10 12/23/2011 3:19 AM
156 CHAPTERS
f)
NaSH
~ I ~ S H
g)
U Br
NaOH
U OH
~
+
major minor
h)
()Br
NaOEt
()OEI
()
+
major minor
i)
~
EtOH
~
~ E t
heat
+ ~ +
major minor minor
j )
u+
~
major minor
OlBr
NaOH
CJ:OH
()n
+
minor minor
k)
OlBr
NaOMe
major minor
+
CJ:OMe
minor minor
1 of 10 12/23/2011 3:20 AM
CHAPTERS 157
I)
c/1"'
NaOMe
en
~
c00M
+ +
major minor
minor
m)
o:Br
NaOH
0 .. ,,
o::,QH
+
'It
.,,
n)
major minor
C(r
NaOH
Q
Q
o:H
+ +
major minor minor
8.47. There are only two constitutional isomers with molecularformula C
3
H
7
CI:
Cl
/"-./CI A
a primary a secondary
alkyl halide alkyl halide
Sodium methoxide is both a strong nucleophile and a strong base. When compound A is
treated with sodium methoxide, a substitution reaction predominates. Therefore,
compound A must be the primary alkyl chloride above. When compound B is treated
with sodium methoxide, an elimination reaction predominates. Therefore, compound B
must be the secondary alkyl chloride:
Cl
/"-./CI
A
Compound A CompoundS
2 of 10 12/23/2011 3:20 AM
158 CHAI>TER 8
8.48.
a)
C l ~
X
Cl
NaOMa
~ ~
~ C I
- X
~
X
b)
C l ~
- X
Cl
X
>=
~
..
~
NaOMa
~
NaOMa
8.49.
Cl >--<
NaOEt
>=<
8.50.
a) trl//M-3.4,5.5-tetramelhyl-3-hcptene
b) 1-cthylcyclohexene
c) 2-mcthylbicyclo[2.2.2]oct-2-cne
3 of 10 12/23/2011 3:20 AM
CHAPTER 8 159
8.51.
8.52. Because of the bulky tert-butyl group, the trans isomer is locked in a
chair conformation in whi ch the chlorine occupies an equatorial position. Thi
conformation cannot readily tmdergo an E2 react ion because the leaving group is not
anti peri planar to a proton. However, the cis isomer is locked in a chair conformation in
which the chlorine occupies an axial position. This conformation rapidly undergoes an
E2 reaction.
8.53.
8.54.
8.55.
8.56.
a)
(this comound Is
too unstable to form
because of Bredt's rule)
rn
/'-.../CI
tertiary primary
Cl

6
secondary secondary
b)
allyllc
a) NaOH, because hydroxide bears a negati ve charge.
b) sodium ethoxide, because ethoxide bears a negative charge.
c) trimethylamine, because of Lhe electron donatjng effectll of the alkyl groups.
Q':_
.... ..
... ,
V(
Me

Ph
strong base
4 of 10 12/23/2011 3:20 AM
160 CHAPTER 8
8.57.
8.58.
8.59.
a) The rate of an E2 process is dependent on the concentrations of the substrate
and the base. Therefore, the rate will be doubled if the concentration of tert-
butyl bromide is doubled.
b) The rate of an E2 process is dependent on the concentrations of the substrate
and the base. Therefore, the rate will be doubled if the concentration of
sodium ethoxjde is doubled.
a) The rare of an E I process is dependent only on the concentration of the
substrate (not the base). Therefore, the rate wi ll be doubled if the
concentration of tert-butyl bromide is doubled.
b) The rate of an El process is dependent only on the concentration of the
substrate (not the base). Therefore, the rate will remain the same if the
concentration of ethanol is doubled.
major product
8.60. There are only two beta protons to abstract: one at C2 and the other at C4.
Abstraction of either proton leads to rhe same product.
+A
Br
NaOH
~ ~
8.61.
NaOH
~
~
a)
Br
major
~
NaOH
~
b)
Br
major
~
KOC(CH3)s
~
c)
Br
major
5 of 10 12/23/2011 3:20 AM
CHAPTER S 161
y
~
d)n
KOC(CH3)3
8.62.
H
2
0
~
heat
~ '' Br
a)
~
H
2
S0
4
~
heat
major
b)
OH
8.63.
~
NaOH
~
a)
Br
major
~
NaOH
~
-
b)
major
8.64. The reagent is a strong nucleophile and a strong base, so we expect a bimolecular
reaction. The substrate is tertiary so only E2 can operate (SN2 is too sterically hindered to
occur). There is only one possible regiochemical outcome for the E2 process, because
the other beta positions lack protons.
NaOEt
8.65.
> ~
b ) ~ c ) ~
6 of 10 12/23/2011 3:20 AM
162 CHAPTER S
8.66.
a) one
b) three
c) two
d) two
e) fi ve
8.67.
a)
d.'
E2
ci'
b)
x{j-
E2
cf
c)
cC
E2
;:-
d)
CJx
E2
8.68.
a)
~ ~ 0
~ ~ I I
H- 0- S- 0 - H
II
0
~ H
H20
G9@
H
b) This is an El process, so the rate is dependent only on the substrate:
Rate= k[substrate]
7 of 10 12/23/2011 3:20 AM
c)
Free
Energy
CHAPTER 8 163
Loss of
LG
Reaction Coordinate
8.69. The primary substrate wiU not undergo an E I reaction because primary
carbocations are too high in energy to form readil y.
a) secondary b) tertiary
8.70.
r
3-
H ,r
I H
HO---- -H-- --Q-
\ &-
H c ..:CBr
3 I
CH3
J
~
G)
c) primary d) secondary
8.71. The first compound produces a trisubstituted alkene, while the second compound
produces a monos ubstituted alkene. As such, the transition state for the reaction
of the first compound will be lower in energy than the transition state for the
reaction of the second compound.
8.72. The first reaction is very slow, because the tert-butyl group effectively locks the
ring in a chair conformation in which the leaving group (Br) occupies an
equatorial position. In this conformation, the leaving group cannot be
8 of 10 12/23/2011 3:20 AM
164 CHAPTER 8
antiperipl anar to a beta proton. So the reaction can only occur from the other
chair conformation, which the compound does not readil y adopt. The second
reaction is very rapid, because the tert-butyl group effectively locks the ring in a
chair conformation in which the leaving group (Br) occupies an axial position. In
this conformation, the leaving group is antiperiplanar to a beta proton. The third
reaction does not occur at all because there are no beta protons that are
antiperiplanar to the leaving group (on a cyclohexane ring, there must be at least
one beta proton that is trans to the leaving group in order to be able to adopt an
antiperiplanar conformation).
8.73. Pi bonds cannot be formed at the bridgehead of a bicyclic compound, unless one of
the rings is large (at least eight carbon atoms). This rule is known as Bredt's rule.
8.74.
8.75.
a) The first compound will react more rapidly because it is tertiary
b) The second compound will react more rapidly in an E2 reaction because the
first compound does not have any beta protons (and therefore cannot undergo E2
at all).
a) The Zaitsev product is desired, so sodium hydroxide should be used.
b) The Hofmann product is desired, so potassium tert-butoxide should be used.
c) The Zaitsev product is desired, so sodium hydroxide should be used.
d) The Hofmann product is desired, so potassium tert-butoxide should be used.
8.76. There is only one beta proton that can be abstracted so as to form the Zaitsev
product. This proton is cis to the leaving group, and therefore, it cannot be
8.77.
a)
anti peri planar to the leaving group (not in either chair conformation). As a result,
only the Hofmann product can be formed.
c f
~
.. \A ~
H-0-S-0-H
~ 0
9 of 10 12/23/2011 3:20 AM
CHAJ>TER 8 165
b)
~
\
~
H- 0 - S- 0 - H
II
0
c)
-
d)
~ :
- IG
-
e)
8.78.
Cl
~
t-BuOK
a)
major minor minor
10 of 10 12/23/2011 3:20 AM
166 CHAPTER 8
NaOH

+

b)
major minor
OH
H
2
S0
4

heat

+

+

c)
major minor minor
d)
NaCI
DMSO
Br
NaOEt
QEt
_)"-v/

+
F\
+

e)
major minor minor minor

NaOEt

+
f)
major minor

+
Br .0

NaOEI
major minor
EtOH
QEt
+

g)
r
Br
QEt

NaOEI
Ol:
+
-
EtOH
-
h)
major minor
Br OEt
(il
NaOEt
vY' VI
+
EtOH -&
i)
major minor
1 of 10 12/23/2011 3:21 AM
CHAPTER 8 167
"' Br KOC(CH3l3
~
~
~
+
j)
major minor
~
NaOMe
~ ~
+
g)
major minor
Cl
NaOH
QH
~ ~ +
F\
+
~
+ /'-..../
h)
major minor minor minor
R.79.
b) For an E2 process, the rate is dependent on the concentrations of the substrate
and the nucleophile: Rate= k[substrate][base]
c) If the concentration of base is doubled, the rate will be doubled.
d)
Free
Energy
8
+ EtO
Reaction Coordinate
+
2 of 10 12/23/2011 3:21 AM
J 68 CHAPTER 8
e)
Br 1-
H
'
8.80.
Cl
NaSH
!H
a)
A./
b)
~ O T s
DBN
~
NaOH
0
c)
H20
H
2
0
0
heat
d )
u OTs
-1-oe Ke
()
e)
I
-j-oe KA
if u
f)
QTs
NaOH
()
g)
H20
3 of 10 12/23/2011 3:21 AM
OTs
0''
NaOH
~
h) '
H
2
0
~
NaOMe
~
i)
MeOH
XX
.:;-oe KG)
)(A
j )
8.81.
B r ~
8.82.
~ H
J
/a'
~ {) II
H-0- S- 0-H
II
0
Increasing reactivity towards E2
Br
~ B r
~
[Cl&
1
~
CHAPTERS 169
4 of 10 12/23/2011 3:21 AM
170 CHAPTER 8
8.83.
8.84.
a)
v._
observer _ Br
....
Ph
H ~ B r
HY H
Ph
j NaOEI
rotate C-C bond
r
H
H ~ B r
HA.}APh
Ph
j NaOEt
dO
trans-stilbene cis-stilbene
(major product)
b) There are still two beta protons t hat can be abstracted in a beta el imination, and
both products are still possible. The reaction wi ll sti ll proceed via the
conformation with the least sreric hinderance. That conformation will lead to the
formation of trans-stilbene.
do
carbocatl on rearrangement
(ring expansion)
00
1
H, _,H
. Q .
. "\
/
5 of 10 12/23/2011 3:21 AM
8.85.
CQ
<oTs
CQ
<:oTs
CHAPTER 8 171
MH f)--\ f)--\
0-::< ..
<>o._H oEt
Et' \)
J . r,J"
oorqH
8.86. The stereoisomer shown below does not readily undergo E2 elimination because
none of the chlorine atoms can be anti peri planar to a beta proton in a chair conformation.
Recall that for substituted cyclohexanes, the leaving group must be Jrans to a beta proton
in order to achieve antiperiplanarity. In the isomer below, none of the chlorine atoms are
trans to a beta proton.
Cl
CI, .. A.'CI

ct
8.87. The first compound is a tertiary substrate. The second compound is a tertiary
aUylic substrate. The latter will undergo El more rapidly because a tertiary allylic
carbocation is more highly stabilized than a tertiary carbocation. The rate-determining
step (loss of the leaving group) will therefore occur more rapidly for the second
compound.

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r;:,i X( q ;-Et EtOH X(

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