Chapter 10 - Organohalides

Give the name for each of the following alkyl halides.

Cl Cl
1. H C C H

Cl H

Answer: 1,1,2-trichloroethane

2. CHI3

Answer: triiodomethane

F Cl
3. F C C H , Halothane

F Br

Answer: 2-bromo-2-chloro-1,1,1-trifluoroethane

4. 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:
Cl Cl

F C C F

80
F F Chapter 10: Organohalides
8. (S)-2-bromobutane

Answer:
H Br

To answer the following questions consider the reaction below:

Cl Cl

(CH3)3COCl
+ +
400 C Cl

65% 25% 10%

9. 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
Therefore the Relative Reactivity for CH 3:CH 2:ArCH 2 is 138
: . :9.85 .

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 McMurry’s 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
Cl2
CH3CH2CH3 CH3CH2CH2 Cl + CH3CHCH3
light

Answer: 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%.

82 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:

CH2Cl + CH3 + CH3 + CH3

Cl
Cl
Cl

16. Label the chirality centers in the monochlorination products of methylcyclopentane with an asterisk.

Answer:

CH2Cl + CH3 + * CH3 + * CH3

* *
Cl
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 CHCH2CH2CH3 NBS CH3CH CHCHCH2CH3 + CH3CHCH CHCH2CH3

hv
Br Br
A B 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 CH3CH CH CHCH2CH3

Test Items for McMurry’s Organic Chemistry, Seventh Edition 83

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

BrCH2CH CHCH2CH2CH3 + CH2 CHCHCH2CH2CH3

Br
D E

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

CH2CH CHCH2CH2CH3 CH2 CHCHCH2CH2CH3

1o allylic 2o 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. PBr3 d. SOCl2, pyridine

b. HCl (gas), ether e. HBr (gas), ether
c. 1. Mg, ether f. 1. Mg, ether
2. D2O 2. NBS

CH3 CH3
21. _____ H3C C OH H3C C Br

CH3 CH3

Answer: e

CH3 CH3
22. _____
Br D

Answer: c

OH Cl
23. _____

Answer: d

84 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.

1. Li, pentane CH3I

CH3CH2I
2. CuI

Answer:

1. Li, pentane CH3I

CH3CH2I (CH3CH2)2CuLi CH3CH2CH3
2. CuI

25.

Cl
SOCl2
pyridine

Answer:

OH Cl
SOCl2
pyridine

26.

NBS
+
CCl4

Answer:

NBS
Br +
CCl4
Br

Test Items for McMurry’s Organic Chemistry, Seventh Edition 85

27.
Cl
HCl
ether

Answer:
Cl
OH
HCl
ether

28.
Br
ether
+ (CH3CH2)2CuLi

Answer:

Br CH2CH3
ether
+ (CH3CH2)2CuLi

29.

1. NBS, CCl4
2. KOH, ethanol

Answer:

1. NBS, CCl4
2. KOH, ethanol

86 Chapter 10: Organohalides

30.
Mg
Br ether

Answer:

Mg
Br ether 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 CH3

CH3CHCH CH2 from CH3CHCH2CH2OH

Answer:
CH3 CH3 CH3
PBr3
CH3CHCH2CH2OH CH3CHCH2CH2Br KOH CH3CHCH CH2
ether ethanol

Test Items for McMurry’s Organic Chemistry, Seventh Edition 87

33.

H3C CH3 H3C

from Br (only source of carbon)

H3C CH3 H3C

Answer:

H3C H3C H3C H3C CH3

4 Li CuI (CH3)2CHBr
2 Br 2 Li CuLi
H3C pentane ether ether
H3C H3C H3C CH3

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

Br

a b

Answer: a = NBS, hv b = KOH, ethanol

Label each transformation below as:

a. an oxidation
b. a reduction
c. 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

35. _____ OH

O
Answer: a
OH

36. _____

Answer: c

88 Chapter 10: Organohalides

 O OH
37. _____

Answer: b

CH3 CH3

CH3CHCH3 CH3CCH3
38. _____
Br

Answer: a

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 O
CH3C OH CH3CH3 CH3C H H2C CH2

Answer:
O O
CH3C OH CH3CH3 CH3C H H2C CH2
4 1 3 2

Test Items for McMurry’s Organic Chemistry, Seventh Edition 89