Chapter 10 PDF
Chapter 10 PDF
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
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
(CH3)3COCl
+ +
400 C Cl
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.
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
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:
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%.
Cl2
CH3
light
Answer:
16. Label the chirality centers in the monochlorination products of methylcyclopentane with an asterisk.
Answer:
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.
Answer:
* *
CH3CH CHCH2CH2CH3
A
19. Draw the resonance forms of the allylic radical intermediate that accounts for the formation of B and C.
Answer:
Answer: Products D and E are formed from the other allylic radical, whose resonance forms are shown
below.
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.
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
24.
Answer:
25.
Cl
SOCl2
pyridine
Answer:
OH Cl
SOCl2
pyridine
26.
NBS
+
CCl4
Answer:
NBS
Br +
CCl4
Br
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
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
Answer:
CH3 CH3 CH3
PBr3
CH3CHCH2CH2OH CH3CHCH2CH2Br KOH CH3CHCH CH2
ether ethanol
Answer:
Br
a b
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
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