Chapter 10

10.1 Give IUPAC names for the following alkyl halides:

(a), CH3CH2CH2CH2I
Solution: 1-iodobutane

CH3
(b), CH3CHCH2CH2Cl

Solution: 1-chloro-3-methylbutane
CH3
BrCH2CH2CH2 CCH2Br
(c), CH3
Solution: 1,5-Dibromo-2,2-dimethylpentane
CH3
CH3CCH2CH2Cl
(d), Cl
Solution: 1,3-Dichloro-3-methylbutane
I CH2CH2I
(e), CH3CHCHCH2CH3
Solution: 3-Ethyl-1,4-diiodopentane
Br

CH3CHCH2CH2CHCH3

(f), Cl
Solution: 2-Bromo-5-chlorohexane

10.2 Draw structures corresponding to the following IUPAC names:

(a), 2-Chloro-3,3-dimethylhexane

Solution: Cl
(b), 3,3-Dichloro-2-methylhexane
Cl Cl

Solution:
(c), 3-Bromo-3-ethylpentane

Br
Solution:
(d), 1,1-Dibromo-4-isopropylcyclohexane
 Br
Solution: Br
(e), 4-sec-Butyl-2-chlorononane

Cl

Solution:

(f), 1,1-Dibromo-4-tert-butylcyclohexane
Br

Solution: Br

10.3 Draw and name all monochloro products you would expect to obtain from radical chlorination of
2-methylpentane. Which, if any, are chiral?
Solution:

hν Cl2

Cl Cl
Cl H
C
+ C + C ＋ Cl
+
H
Cl

1-chloro-2-methylpentane 2-chloro-2-methylpetane 3-chloro-2-methylpentane 2-chloro-4-methylpentane 1-chloro-4-methylpentane

(chiral) (chiral) (chiral)

10.4 Taking the relative reactivities of 1°,2°,3°hydrogen atoms into account, what products
would you expect to obtian from monochlorination of 2-methylbutane? What would the
approximate percentage of each product be?
Solution:
 Cl
Cl
Cl2
hν +

6/26 10/26

Cl

+ +
Cl
7/26 3/26

10.5 Draw three resonance forms for the cyclohexadienyl radical.

Cyclohexadienyl radical

Solution:

10.6 The major product of the reaction of methylenecyclohexane with N-bromosuccinimide is

1-(bromomethyl)cyclohexene. Explain.
CH2 CH2Br

NBS
light, CCl4

Major product
Solution:
 Allylic position Br
More hindered Less hindered

H H
H
CH2
CH2 CH2
NBS
light, CCl4

Br2

CH2Br

Major product

One more reason is the relative stability of alkene.

10.7 What products would you expect from the reaction of the following alkenes with NBS? If
more than one product is formed , show the structures of all.
(a)

CH3

H
CH3 CH3
H CH3

NBS

H
Br
H

CH3 CH3

Br
(b)

CH3

H
H3C C C C C CH3
H H

H
CH3

H
H3C C C C C CH3
H H

H H

A B
CH3 CH3
H H
H3C C C C C CH3 H3C C C C C CH3
H H H H H
H

C D CH3
CH3

H H H
H3C C C C C CH3 H3C C C C C CH3
H H H

H H

From the four radicals above, we can get four products drawn below:

CH3
B CH3
A main
H
H3C C C C C CH3 H
H H H3C C C C C CH3
H H H
Br H
Br
C
CH3 D CH3
H H2 H
H3C C C C C CH3 H3C C C C C CH3
H H H H
Br Br
10.8
How do you prepare the following alkyl halides from the corresponding alcohols?
(a)
Cl

H3C C CH3

CH3

OH Cl

HCl
E
t
h
e
H3C C CH3 r H3C C CH3 + H2O

CH3 CH3

(b)

Br CH3
H2
H3C C C C CH3
H H

OH CH3 Br CH3

H2 PBr3 H2
E
t
h
e
r

H3C C C C CH3 H3C C C C CH3

H H H H

(c)
CH3
H2 H2 H2 H2
Br C C C C C CH3
H

CH3 CH3
H2 H2 H2 H2 PBr3 H2 H2 H2 H2
E
t
h
e
r

HO C C C C C CH3 Br C C C C C CH3
H H

(d)
 CH3 Cl
H2 H2
H3C C C C C CH3
H

CH3

CH3 OH CH3 Cl
H2 H2 HCl H2 H2

E
t
h
e
r
H3C C C C C CH3 H3C C C C C CH3
H H
CH3 CH3

10.9
Just how strong a base would you expect a Grignard reagents to be? Look at Table 8.1, and the
predict whether the following reactions will occur as written. (The pKa of NH3 is 35)
CH4 + H C C MgBr
(a) CH3MgBr + H C C H

(b) CH3MgBr + NH3 CH4 + H2N MgBr

Solution: The Grignard reagent can be thought of as the magnesium salt of a hydrocarbon acid.
Because hydrocarbons are very weak (pKa’s in the range 44 to 60), it is very strong base.
All the two reactions can occur.
10.10
How might you replace a halogen substituent by a deuterium atom if you wanted to prepare a
deuterated compound?
Br D
?
CH3CHCH2CH3 CH3 CHCH2CH3
Solution: Br MgBr D

Mg D2O
CH3CHCH2CH3 CH3CHCH2CH3 CH3CHCH2CH3
Ether

10.11
How would you carry out the following transformations using an organocopper coupling reaction ?
More than one step is required in each case.
?

(a) CH3
Solution:
 NBS
CCl4
Br

Ether
(CH 3)2CuLi

Br CH3
?

(b) H3CH2CH2CH2C Br CH3CH2CH2CH2CH2CH2CH2CH3

Solution:

2Li
H3CH2CH2CH2C Br Pentane H3CH2CH2CH2C Li LiBr

Ether
2 H3CH2CH2CH2C Li CuI (H3CH2CH2CH2C)2 Cu+Li-

H3CH2CH2CH2C Br 2(H2CH2CH2CH3C)2 Cu+Li-

Ether
CH3CH2CH2CH2CH2CH2CH2CH3
LiBr (H3CH2CH2CH2C) Cu
(c)
?
H3CH2CH2CHC CH2

CH3CH2CH2CH2CH2CH2CH2CH2CH2CH3
Solution:
 1 BH 3,THF
H3CH2CH2CHC CH2 H3CH2CH2CH2CH2C OH
2 H 2O2,OH

PB3
H3CH2CH2CH2CH2C OH H3CH2CH2CH2CH2C Br

2Li
H3CH2CH2CH2CH2C Br H3CH2CH2CH2CH2C Li+ LiBr
Pentane

Ether
2 H3CH2CH2CH2CH2C Li+ CuI

(CH2CH2CH2CH2CH3)2Cu+Li- LiI

H3CH2CH2CH2CH2C Br (CH3CH2CH2CH2CH2)2Cu+Li-

Ether
CH3CH2CH2CH2CH2CH2CH2CH2CH2CH3

10.12
Rank each of the following series of compounds in order of increasing oxidation level:
(a)

O Cl

O Cl

Oxidation level order: < = <

(b) CH3CN CH3CH2NH2 NH2 CH2CH2NH2

Oxidation level order:

CH3CH2NH2 < NH2 CH2CH2NH2 < CH3CN
10.13
Tell whether each of the following reaction is an oxidation, a reduction, or neither.
Explain your answer.
 O
NaBH4
(a) CH3CH2CH CH3CH2CH2OH
H2O

OH

(b) 1. BH3
2. NaOH, H2 O2

Solution: (a) Because of breaking one C-O, so it is reduction.

(b) Because of forming one C-O and forming one C-H, so it is neither reduction
nor oxidation.

10.14
Give an IUPAC name for each of the following alkyl halides (yellow-green=Cl):
(a)

cis-1-Chloro-3-methyl-cyclohexane
(b)

4-chloro-2-methyl-2-heptene
10.17
Name the following alkyl halides according to IUPAC rules:
CH3 Br Br CH3
H2
H3 C C C C C C CH3
(a) H H H H

Solution: 3,4-dibromo-2,6-dimethyl-heptane
I

(b) H3CHC CHCH2CHCH3

Solution: 5-iodo-2-hexene
Br Cl CH3
H2
H3 C C C C C CH3
H H

(c) CH3
Solution: 2-bromo-4-Chloro-2,5-dimethyl-hexane
CH2Br

H3CH2C C CH2CH2CH3
(d) H

Solution: 3-bromomethylhexane
(e) ClH2CH2CH2CC CCH2Br
Solution: 1-bromo-6-chloro-2-hexyne

10.18
Draw structures corresponding to the following IUPAC names:
(a) 2,3-Dichloro-4-methylhexane
Cl CH3

Solution: Cl
(b) 4-Bromo-4-ethyl-2-methylhexane
Br

Solution:
(c) 3-Iodo-2,2,4,4-tetramethylpentane
Solution: I
(d) cis-1-bromo-2-ethylcyclopentane
Br CH2CH3

Solution: H H

10.19:
Draw and name the monochlorination products you might obtain by radical chlorination of
2-methylbutane. Which of the products are chiral? Are any of the products optically active?

Solution: As there are four kinds of hydrogen atoms, so there should be four kinds of products, witch
are (a):1-chloro-2-methylbutane, (b):2-chloro-2-methylbutane, (c):3-chloro-2-methylbutane and
(d):4-chloro-2-methylbutane.
The products (a) and (c) are chiral. And the products (a) and (c) are optically active.

10.20:
A chemist requires a large amount of 1-bromo-2-pentene as starting material for a synthesis and
decides to carry out an NBS allylic bromination reaction:
NBS
Br
CCl4
What is wrong with this synthesis plan? What side products would form in addition to the desired
product?
Solution:
Br
NBS
Br +
CCl4
Mixture will be obtained.

10.21
What product(s) would you expect from the reaction of 1-methylcyclohexene with NBS? Would you
use this reaction as part of a synthesis?
CH3
NBS ?
CCl4
 CH3 Br
CH3

Solution: The products will be Br and

As a part of synthesis I will not use this reaction. Because from this reaction I will get two
mixed products. But usually in synthesis we only need one single product.

10.22
How would you prepare the following compounds, starting with cyclopentene and any other reagents
needed?
(a) Chlorocyclopentane (b) Methylcyclopentane
(c) 3- Bromocyclopentene (d) Cyclopentanol
(e) Cyclopentylcyclopentane (f) 1,3-Cyclopentadiene

HCl Cl
Solution: (a)

HI I (CH3)2CuLi CH3

(b)
Br
NBS

(c)

1.BH3,THF OH
(d) 2.H2O2,OH

(e)

HI I

I 2Li Li CuI Cu Li
Pentane Ether

Br
NBS Base

(f)

10.23
Predict the product(s) of the following reactions:
 H3C OH
HBr
? SOCl2
(a) Ether (b) OH ?
OH
NBS PBr3
? ?
(c) CCl4 (d) Ether

Mg H2O
A? B?
Ether
(e) Br
Li CuI
Br A? B?
(f) Pentane
Ether
(CH3)2CuLi ?
(g) Br +
H3C OH H3 C Br
HBr
+ H2O
Ether
Solution: (a)
SOCl2
+ HCl
(b) OH Cl + SO2
Br
O
NBS
CCl4 + N H

(c) O
OH Br
PBr3
3 3 + H3PO3
(d) Ether

Mg H2O
+ Mg(OH)Br
Ether
Br MgBr
(e)
(f)
2Li CuI
Br + LiBr (CH3CH2CH2CH2)2 CuLi + LiI
Pentane Li

Ether
(CH3)2CuLi + CH3Cu + LiBr
(g) Br +

10.24
(S)-3-Methylhexane undergoes radical bromination to yield optically inactive 3-bromo-3-methylhexane
as the major product. Is the product chiral? What conclusions can you draw about the radical
intermediate?
CH2CH3

C
Br
H3C CH2CH2CH3

Solution: Two stereoisomers of the product are formed. (R)-3-bromo-3-methylhexane and

 CH2CH3

C
H3C
Br CH2CH2CH3

(S)-3-bromo-3-methylhexane. They are all chiral and form in a ratio of 1:1.

CH2CH3

C
H3C
Conclusions: The radical intermediate is CH2CH2CH3. It’s planar
and the two sides have equal chance to be attacked.

10.25
Assume that you have carried out a radical chlorination reaction on (R)-2-chloropentane and have
isolated (in low yield) 2,4-dichloropentane. How many stereoisomers of the product are formed and in
what ratio? Are any of the isomers optically active? (See Problem 10.24)
Cl
Cl

Cl2
+ Cl + HCl Cl +

(R)-2-chloropentane

Cl Cl Cl Cl

(S) (R) + (R) (R)

2,4-Dichloro-pentane 2,4-Dichloro-pentane
Α Β
Solution:
Two stereoisomers of the product are formedin 1 : 1 ratio. The first one (A) is a meso compound,
so it is optically inactive. The second one (B) is optically active.

10.26
Calculate ΔH for the reactions of Cl and Br with CH4 , and then draw a reaction energy
diagram showing both processes. Which reaction is likely to be faster?
Solution:
Product bonds formed Reactant bonds broken
C-Cl D=351kJ/mol C-H D=438kJ/mol
H-Cl D=432kJ/mol Cl-Cl D=243kJ/mol
Total D=783kJ/mol Total D=681kJ/mol
ΔH＝681－783＝－102kJ/mol
Product bonds formed Reactant bonds broken
 C-Br D=293kJ/mol C-H D=438kJ/mol
H-Br D=366kJ/mol Br-Br D=193kJ/mol
Total D=659kJ/mol Total D=631kJ/mol
ΔH＝631-659＝－28kJ/mol
The reaction energy diagram:

Reaction energy diagram of Reaction energy diagram of

Cholomethane Bromomethane
900
800 900
700 800
600 700
600
Energy

500

Energy
400 500
400
300
200 300
100 200
100
0
0
0 2 4 6
0 2 4 6
Reaction process
Reaction process

The reaction between Cholorine radical and methane is much faster.

10.27
Use the bond dissociation energies listed in Table 5.3 on page 154 to calculate △H0 for the reactions
of Cl. and Br. with a secondary hydrogen atom of propane. Which reaction would you expect to
be more selective?
For Cl. △H0=401-339=62kj/mol
For Br. △H0=401-274=127kj/mol
It is clear that Cl. has higher reactivity while Br. has lower reactivity; thus according to
“lower reactivity higher selectivity”, the reaction of Br. with a secondary hydrogen atom
of propane is more selective.

10.28
What product(s) would you expect from the reaction of 1, 4-hexdiene with NBS? What is the structure
of the most stable radical intermediate?
Solution: The reaction will be following:
 Br major

Br
NBS

Br

Br

Br

Br

That’s because of relative stability of conjugated diene.

10.29
Alkyl benzenes such as toluence (methylbenzene) react with NBS to give products in which bromine
substitution has occurred at the position next to the aromatic ring (the benzylic position). Explain,
based on the bond dissociation energies in Table 5.3
The reason is show bellow:

Br
NBS

CCl 4

H CH2 368kJ/mol
H
nearly 464kJ/mol
H

The carbon hydrogen bond of the methyl has the lowest bond dissociation energy, so this bond is
most likely to be broken and yields the most stable radical.

10.30:
Draw resonance structures for the benzyl radical, C6H5CH2 , the intermediate produced in the NBS
bromination reaction of toluene (Problem 10.29)
Solution:
CH2
CH2 CH2
CH2
10.32
Draw resonance structure for the following species:

CH3C N O
(a) CH3CH CHCH CHCH CHCH2 (b) (c)
Solution:
(a).

(b).

(c).

N O N O

10.33
Rank the compounds in each of the following series in order of increasing oxidation level:
O O

(a) OH
 NH2 Br
Cl Br Cl

(b) O

Solution:
O O

a) = < < OH

Cl
NH2 Br
b) = <Br Cl < O

10.34.
Which of the following compounds have the same oxidation level and which have different levels?
O
O
OH

1 2 3

4 5
Solution: compound 1, 2, 4 have the same oxidation level and compound 3， 5 has different
oxidation level.

10.35
Tell whether each of the following reactions is an oxidation or reduction:
O
CrO3
a. CH3CH2 OH CH3CH

Oxidation
O O

b. H2C CHCCH3 + NH3 NH2CH2CH2 CCH3

Neither
1.Mg
CH3CH2CHCH3 CH3CH2CH2CH3
2.H2O
c. Br
 Reduction

10.36
How would you carry out the following syntheses?
(a) Butylcyclohexane from cyclohexene
(b) Butylcyclohexane from cyclohexanol
(c) Butylcyclohexane from cyclohexane
Br
HBr (CH3CH2CH2CH2)2CuLi
In ether

+ CH3CH2CH2CH2Cu + LiBr

OH Br

PBr3 (CH3CH2CH2CH2)2CuLi
Ether In ether

+ CH3CH2CH2CH2Cu + LiBr

Br

Br2 (CH3CH2CH2CH2)2CuLi
Heat/hv In ether

+ CH3CH2 CH2 CH2Cu + LiBr

10.37
The syntheses shown here are unlikely to occur as written. What is wrong with each?
(a)
F
1. Mg
2.OH3
(b)
Br

CH2 CH2
NBS
CCL4
CH3 CH3
(c)
F CH3

(CH3)2CuLi
Ether

Solution:
(a) Organofluorides rarely react with magnesium. So there is no alkyl magnesium fluorides.
(b) The reaction reacts as follow:
CH2
CH2 CH2 CH2Br
NBS
CCL4
CH3
CH3 CH3 CH3

Br

CH2Br CH2

CH3 is more stable than CH3 because of Zaitsev’s rule.

(c)
Gilman reagents couldn’t react with fluorides because of high density of electron on fluorine atom.
So this reaction could not occur.

10.38
Why do you suppose it’s not possible to prepare a Gringard reagent from a bromo alcohol such as
4-bromo-1-pentanol?

Br MgBr

OH Mg OH
 Give another example of a molecule that is unlikely to form a Grignard reagent.

Solution: If 4-bromo-1-pentanol can form a Gringard reagent, it will nucleophilic attack the active
atom H in –OH, so it’s not possible to prepare a Gringard reagent.
O

C
Such as Br OH which has active H is unlikely to
form a Grignard reagent.

10.39
Addition of HBr to a double bond with an ether substiutent occurs regiospecifically to give a
product in which the Br and OR are bonded to the same carbon:
OCH3 OCH3

H Br
Br

Draw two possible carbocation intermediates in this electrophilic addition reaction, and
explain using resonance why the observed product is formed.

Answer:
OCH3 OCH3 OCH3

H Br

OCH3

more stable form

10.40
Phenols, compounds that have an –OH group bonded to a benzene ring, are relatively acidic because
their anions are stabilized by resonance. Draw resonance structures for the phenoxide ion.

phenoxide ion

Solution:
 O O O

O O

10.41
Alkyl halides can be reduced to alkanes by a radical reaction with tributyltin hydride, (C4H9)3SnH ,
in the presence of light (hv):

R X + (C4H9 )3SnH R H + (C4 H9 )3SnX

solution:
Initiation step:

(C4H9)3Sn H (C4H9)3Sn + H
Propagation steps:
H R X
(C4H9 )3SnH

X R H

Termination steps:
(C4H9 )3Sn + (C4H9)3Sn (C4 H9)3 Sn Sn(C4H9)3

(C4H9)3 Sn + X (C4H9)3Sn X

R + H R H
R H
R + X R X

R + R R R
H + H
H H

X + X X X

(C4H9)3Sn + H (C4H9)3Sn H

(C4H9)3Sn + R (C4H9)3 Sn R
X + H H X

10.42 Identify the reagents a-c in the following scheme:

 OH Br CH3

a b c

Solution: a, 1) BH3, 2) OH-, H2O2; b, PBr3; c, 1) Li, 2) CuI, 3) CH3I

10.43
Tertiary alkyl halides, R3CX, undergo spontaneous dissociation to yield a carboncation,
R3C+.Which do you think reacts faster,(CH3)3CBr,or H2C=CHC(CH3)2Br? Explain

Solutions: H2C=CHC(CH3)2Br .Because of double bond’s conjugate effect. So the carboncation is

more stable .And the △G is smaller .And as a result the reaction is faster.

10.44
Carboxylic acids (RCO2H; pKa≈5) are approximately 1011 times more acidic than alcohols (ROH;
pKa≈16). In other words, a carboxylate ion (RCO2-) is more stable than an alkoxide ion(RO-).
Explain, using resonance.
Solution:
O O

C H C
R O R O

O O

C C
R O R O

The carboxylate ion has two resonance forms, which is rather than the alkoxide
ion,only one
Form. Thus the RCO2-is much stable than RO- .