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Chapter 10 - Organohalides

Give the name for each of the following alkyl halides.

1.

Cl

Cl

Cl

Answer:
2.

triiodomethane

Cl

Br

Answer:
4.

1,1,2-trichloroethane

CHI3
Answer:

3.

H , Halothane

2-bromo-2-chloro-1,1,1-trifluoroethane

CH2Cl2
Answer:

dichloromethane

Draw structures corresponding to these names.


5.

3-iodopropene
Answer:
I

6.

trans-1-chloro-3-sec-butylcyclohexane
Answer:
Cl

7.

1,2-dichloro-1,1,2,2-tetrafluoroethane (Cryofluorane)
Answer:
F

80

Cl

Cl

F
Chapter 10: Organohalides

8.

(S)-2-bromobutane
Answer:
H

Br

To answer the following questions consider the reaction below:


Cl
(CH3)3COCl
400 C

Cl

+
65%

9.

+
Cl
25%

10%

When propylbenzene reacts with tert-butylhypochlorite three monochlorinated products are formed in the
ratios indicated. Calculate a reactivity order for each type of hydrogen atom in propylbenzene.
Answer:

Ar CH 2 = 65% 2 = 32.5% product 33


. = 9.85

CH 2 = 25% 2 = 12.5% product 33


. = 38
.
CH 3 = 10% 3 = 33%
.
product 33
. =1
: . :9.85 .
Therefore the Relative Reactivity for CH 3:CH 2:ArCH 2 is 138

10. The reaction of propylbenzene with tert-butylhypochlorite proceeds by a radical substitution pathway.
Draw the structure of the radical intermediate leading to each product.
Answer:
Cl

+ (CH3)3COCl

Cl
Cl

Test Items for McMurrys Organic Chemistry, Seventh Edition

81

11. Based on your answers to the two questions above explain why (1-chloropropyl)benzene is the major
product of this reaction.
Answer:

In question 9 we calculated that the hydrogens next to the aryl group, the benzylic hydrogens,
are about 2.5 times more reactive than the methylene hydrogens and about 10 times more
reactive than the methyl hydrogens. This means that the benzylic radical is more stable than a 2
or 1 radical. The reason the benzylic radical is more stable is because it is resonance
stabilized. The resonance forms for the benzylic radical are:

The 2 or 1 radicals have no other resonance forms.


12. Are any of the products of this reaction chiral? If so draw them and label the chirality center with an
asterisk.
Answer:

Yes!
Cl

*
and

Cl

13. Will the product mixture of this reaction display optical activity?
Answer:

No, the radical intermediates for the chiral products are symmetrical and the transition states
leading to chiral products are of equal energy so racemic mixtures are formed.

14. In the discussion on relative reactivity of alkane hydrogens towards radical chlorination, we showed that
the relative rate of 2 to 1 hydrogen atom abstratction is 3.5 : 1 for butane. Calculate the relative amounts
of 1-chloropropane and 2-chloropropane obtained the radical chlorination of propane, using this relative
rate of reactivity.
Cl
CH3CH2CH3

Answer:

82

Cl2
light

CH3CH2CH2

Cl

CH3CHCH3

Propane has six 1 hydrogrens, so 6 x 1 = 6; and two 2 hydrogens, so 2 x 3.5 = 7. The


percentage of 1-chloropropane is therefore 6/13 or 46% and the percentage of 2-chloropropane
is 7/13 or 54%.

Chapter 10: Organohalides

Consider the reaction below to answer the following questions.


Cl2

CH3

light

15. Draw all the monochlorination products of methylcyclopentane (ignore stereoisomers).


Answer:
CH3 +

CH2Cl +

CH3 +

Cl

CH3

Cl
Cl

16. Label the chirality centers in the monochlorination products of methylcyclopentane with an asterisk.
Answer:
CH3 +

CH2Cl +
Cl

CH3 +

CH3

Cl
Cl
17. Tell whether radical chlorination of methylcyclopentane is an oxidation or a reduction process.

Answer:

In the radical chlorination of methylcyclopentane a C-H bond is broken and a C-Cl bond is
formed, so the process is an organic oxidation.

Consider the reaction below to answer the following questions.

CH3CH

NBS
hv

CHCH2CH2CH3

CH3CH

CHCHCH2CH3

CH3CHCH

Br
A

CHCH2CH3

Br
C

18. Place asterisks(*) at all allylic positions in compound A.


Answer:
*
CH3CH

*
CHCH2CH2CH3
A

19. Draw the resonance forms of the allylic radical intermediate that accounts for the formation of B and C.
Answer:
CH3CH

CH

CHCH2CH3

Test Items for McMurrys Organic Chemistry, Seventh Edition

CH3CH

CH

CHCH2CH3

83

20. D and E, below, are minor products in this reaction. Explain why.

BrCH2CH

CHCH2CH2CH3

CH2

CHCHCH2CH2CH3
Br

Answer: Products D and E are formed from the other allylic radical, whose resonance forms are shown
below.
CH2CH

CHCH2CH2CH3

CH2

CHCHCH2CH2CH3
2o allylic

1o allylic

This allylic radical forms more slowly than the radical for products A and B because is has some
1 character, and thus, is less stable. The allylic radical intermediate for products A and B is 2
allylic.
Choose the best reagent or sequence of reagents from the list provided below for carrying out the following
transformations. Place the letter of your response to the left of the reaction.
a.
b.
c.

PBr3
HCl (gas), ether
1. Mg, ether
2. D2O

d. SOCl2, pyridine
e. HBr (gas), ether
f. 1. Mg, ether
2. NBS

CH3

CH3

21. _____

H3C

OH

84

CH3

CH3

Br

OH

23. _____

Answer:

Br

22. _____

Answer:

C
CH3

CH3

Answer:

H3C

Cl

Chapter 10: Organohalides

Provide structures for the reactants, intermediates, or products, as indicated, in the following reactions. Draw
the structures in the boxes provided.
24.

CH3CH2I

CH3I

1. Li, pentane
2. CuI

Answer:

CH3CH2I

1. Li, pentane
2. CuI

(CH3CH2)2CuLi

CH3I

CH3CH2CH3

25.
Cl

SOCl2
pyridine

Answer:
OH

Cl

SOCl2
pyridine

26.
NBS
CCl4

NBS
CCl4

Br +

Answer:

Test Items for McMurrys Organic Chemistry, Seventh Edition

Br

85

27.
Cl
HCl
ether

Answer:
Cl

OH

HCl
ether

28.
Br
+ (CH3CH2)2CuLi

ether

Answer:
Br
+ (CH3CH2)2CuLi

CH2CH3
ether

29.
1. NBS, CCl4
2. KOH, ethanol

Answer:
1. NBS, CCl4
2. KOH, ethanol

86

Chapter 10: Organohalides

30.

Mg
ether

Br

Answer:
Mg
ether

Br

MgBr

31.
Br

PBr3
ether

Answer:
OH

Br

PBr3
ether

Propose a synthesis of each of the following compounds from the given starting material and any inorganic
reagents necessary.
32.
CH3
CH3CHCH

CH3
CH2

from

CH3CHCH2CH2OH

Answer:
CH3
CH3CHCH2CH2OH

PBr3
ether

CH3
CH3CHCH2CH2Br

Test Items for McMurrys Organic Chemistry, Seventh Edition

CH3
KOH
ethanol

CH3CHCH

CH2

87

33.
H3C

H3C

CH3

Br

from
H3C

(only source of carbon)

H3C

CH3

Answer:

H3C
Br

H3C

4 Li
pentane

H3C
Li

H3C

CuI
ether

H3C
CuLi
H3C

(CH3)2CHBr
ether

H3C

CH3

H3C

CH3

34. Identify the reagents a and b in the following scheme.


Br

Answer:

a = NBS, hv

b = KOH, ethanol

Label each transformation below as:


a.
b.
c.

an oxidation
a reduction
neither an oxidation nor a reduction

Place the letter corresponding to the correct answer in the blank to the left of the transformation.
OH

OH

NH2
OH

35. _____
O

Answer:

OH

36. _____

Answer:

88

Chapter 10: Organohalides

OH

37. _____

Answer:

b
CH3

38. _____

CH3

CH3CHCH3

CH3CCH3
Br

Answer:

39. Rank the following compounds in order of increasing oxidation level. Place the number rank (1 = lowest;
4 = highest) in the blank below the structure.
O
CH3C

O
OH

CH3CH3

CH3C

H2C

CH2

Answer:
O

CH3C

OH
4

CH3CH3

CH3C

Test Items for McMurrys Organic Chemistry, Seventh Edition

H2C

CH2
2

89

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