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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
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
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:
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
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:
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
CH3
light
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.
CH3CH
NBS
hv
CHCH2CH2CH3
CH3CH
CHCHCH2CH3
CH3CHCH
Br
A
CHCH2CH3
Br
C
*
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
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
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:
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
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
CH3
KOH
ethanol
CH3CHCH
CH2
87
33.
H3C
H3C
CH3
Br
from
H3C
H3C
CH3
Answer:
H3C
Br
H3C
4 Li
pentane
H3C
Li
H3C
CuI
ether
H3C
CuLi
H3C
(CH3)2CHBr
ether
H3C
CH3
H3C
CH3
Answer:
a = NBS, hv
b = KOH, ethanol
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
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
H2C
CH2
2
89