Chal!..

ter7 - Alkenes: Reactions and Svnthesis

To answer the questions below consider the following reaction:

When cyclohexene reacts with chlorine in carbon tetrachloride the trans-dihalide is fonned.
CI

1.
0 ~CC4
(X ". Cl

Write the complete stepwise mechanism for this reaction. Be sure to show all intennediate structures and
all electron flow using arrows.

Answer:
H

O ALt .
-- C?~Cj~ (X "'CI
CI

2. Since the two chlorine atoms add to opposite faces of the cyclohexene double bond, we say that the
reaction occurs with:

a. syn stereochemistry
b. cis stereochemistry
c. anti stereochemistry
d. retention of stereochemistry

Answer: c

3. The observed stereochemistry of addition of chlorine to cyclohexene is explained by the intennediacy of a:

a. cyclonium ion
b. carbocation
c. carbene
d. chloronium ion

Answer: d

4. Provide the IUPAC name for the product of the reaction of cyclohexene with chlorine.

Answer: trans-l ,2-dichlorocyclohex~e

5. Draw both chair confonnations of trans-l ,2-dichlorocyclohexane on the templates provided below. Circle
the least stable confonnation.

-
c:::;J - ~
48 Chapter 7: Alkenes: Reactions and Synthesis
 Answer:

-
~

~a CI

Consider the reaction sequence below to answer the following questions:

OH

(J' Hg(OAch, H20/TH~

~ ?"

~
I

6. Write the complete reaction mechanism for the first step of this reaction sequence.
with arrows and show all intermediate structures.
HgOAc

+ HOAc
NaB~.
cf+ Hg
Show all electron flow

Answer:

~f\ ?AC ~HgOAC

() ~
I
" \Hg-OAC
U (). + HOAc

I
H r'lHf'e
~ @/OAc 4-""'"6: OAc
'"
~ (H +
e
OAc .
~HgOAC

() r H2O:

7. The intermediate in the first step of this reaction sequence is called a:

a. carbocation b. cyclonium ion c. mercurinium ion d. mercapto species.

Answer: c

8. In the second step of this reaction sequence, the organomercury compound is treated with sodium
borohydride, NaBH4, to yield the alcohol product. This replacement of a carbon-mercury bond with a
carbon-hydrogen bond is termed:

a. an oxidation b. a reduction c. a hydroxylation d. a cycloaddition

Answer: b

Test Items for McMurry's Organic Chemistry, Seventh Edition 49

Consider the reaction below to answer the following questions.

Alkenes may be hydrated by the hydroborationloxidation procedure shown.

~ OH

0-CH3
1. BH~, THF
2. H202, NaOH, H2O
. &:'
9. The intermediate formed in the first step of this reaction is:

H
H ~, BH2
\ ~-
;:<
a.
0
~,
'H
". CH3

OH
b.
V'CH3

H2~
,~H

OH
;:< ,~H
c.
0< ".
BH2
CH3
, d.
V'CH3

Answer: b

10. Hydroboration ofalkenes is an example of:

a. a rearrangement reaction.
b. a substitution reaction.
c. an elimination reaction.
d. an addition reaction.

Answer: d

11. Hydroborationloxidation of alkenes occurs with:

a. anti stereochemistry.
b. trans stereochemistry.
c. syn stereochemistry.
d. unpredictable stereochemistry.

Answer: c

12. The regiochemistry of hydroborationloxidation of alkenes is:

a. Markovnikov.
b. non-Markovnikov
c. subject to solvent effects.
d. unrelated to alkene structure.

Answer: b

50 Chapter 7: Alkenes: Reactions and Synthesis

Consider the reaction below to answer the following questions.

When dichlorocarbene is generated in the presence of an alkene, a dichlorocyclopropane is fonned.

CI, Cl
H3C CH3
\ /
C=C + CHCl3 KOH~
/ \ H]c---A--- ill]
H H
H H
13. Write the complete stepwisemechanismfor the fonnation of dichlorocarbene,:CCh. Show all intennediate
structuresand show all electron flow with arrows.

Answer:

Cl Cl
I ~. t. fl- + \
Cl-C.. \ H + K :OH
..
~ Cl-C: K + H2O ~ C: + KCl
I~ I
Cl C/
Cl

14. Draw the complete Lewis electron dot structure for dichlorocarbene,:CCh.

Answer:
..
:Cl: C:Cl:- '
15. In the reaction of an alkene with dichlorocarbene, the dichlorocarbene is the:

a. electrophile. b. Lewis base. c. nucleophile. d. both band c.

Answer: a

16. The reaction of an alkep.ewith dichlorocarbene is:

a. regiospecific. b. Markovnikov. c. stereospecific. d. non-Markovnikov.

Answer: c

The sequence of (1) alkene hydroxyl ation followed by (2) diol cleavage is often an excellent alternative to
direct alkene cleavage with ozone. For this sequence below, answer the following questions.
CH3

(Jill] 1. OS04, pyridine

~ A
B
~
2. NaHS03, H2O

H
17. Draw the structure of A.
OH

Answer:
(t: H

18. Give the fonnula for reagent B.

Answer: HI04

Test Items for McMurry's Organic Chemistry, Seventh Edition 51

Predict the products of each reaction below. Indicate regiochemistry and stereochemistry when relevant.

19.
oeCH3 Hz
~Pd
CH3
Answer:
,CH3

oeCH3
Ct:3
Hz
~Pd
CH3
H

H3C H
\c=d CHCI3~
20.
/ \ KOH
H CH3

Answer:

CI CI
H3C H
\C= d\ CHCl3
~
/ KOH H3c--A--H
H CH3
H CH3

21.

a
~Answer:
CH= CH2
Clz
HzO

OH
I
aCH=CH2 Clz aCH-CH2a
HzO

52 Chapter 7: Alkenes: Reactions and Synthesis

22. H H
\ /
1. OsO
4'
pyridine
.
cSc=cb 2. NaHS03' H2O

Answer:

H H HO OH
\ /
\ /
1. OsO pyridine
.
cSC=Cb
4'
2. NaHS03' H2O
ac-c'Q

23. C(°H .
HlO4
,

H2O
OH
Answer:

C(oH .
HlO4 H~H
H2O
OH 0 0

24. ()CH3 Clz

CC4
.
Answer:

a:
.CH3
()CH3
I
\ .
Clz
CCl4
CI

Test Itemsfor McMurry's Organic Chemistry, Seventh Edition 53

 H H
25. \
C=C
/ CH2I2
Zn(Cu), ether
.
/ \
H3C CH3

Answer:

H H
\
C=C
/ CH2I2
Zn(Cu), ether
. II---~-'II
/ \
H3C CH3 H3C CH3

03, CH2C1~
26. ~1.
2. Zn, HOAc

Answer:
0 0

1. 03, CH2C1~ ~+ H~
~'
2. Zn, HOAc

27.
Hg(OACh,
~1.
2.NaBH4
H2O
.

Answer:

Hg(OACh,
~1.
2.NaBH4
H2O
~.

(yCH3
28.0
KMn04
H30+
.

Answer:

(JCII3 KMn04
. IIO~
H30+
0

Chapter 7: Alkenes: Reactions and Synthesis

54
 ROOR
heat .
29.
HzC= CHCI
(polymer segment)

Answer:
CI CI CI
I I I
heat.
ROOR
HzC= CHCI ~ CHz- CH- CHz- CH- CHz- CH+

Choose the best reagent from the list below for carrying out each transformation. Place the letter of the reagent
in the blank to the left of the reaction.

a. I. 03 e. I. OS04
2. Zn, H3O+ 2. NaHS03, H2O

b. 1. BH3, THF f. KMn04, acid

2. H202, NaOH, H2O

c. CHCh, KOH g. CH2I2,Zn(Cu)

d. H2O, H2SO4,heat h. 1. Hg(OAc)2, H2O

2. NaBH4

30. -
(JCH1. . ex:J
Answer: b

31.
-
(JCHJ . H~CHJ
0
Answer: a

32. - (JCHJ . eyCHJ

H
Answer:g
.CH3
33. (JCHJ . ()OH
Answer:h
Test Items for McMurry's Organic Chemistry, Seventh Edition 55
For each reaction below suggest structures for alkenes that give the indicated reaction products. There may be
more than one answer in some cases.

H2
.
34.
Pd
I
Answer:

~ or
lor~

OH

.
35. 1. BH3, THF
2. H202, NaOH, H2O
~
Answer:

~
36.
HBr
ether
. ~
Answer:

~ or ~
56 Chapter 7: Alkenes: Reactions and Synthesis
37.
ROOR
heat
.. + aIzaIaIzaIaIzaI*
I I I
C6Hs C6Hs C6Hs

Answer:

aIz= aIC6Hs

To answer the questions below consider the following information:

In an abandoned laboratory has been found a flammable liquid, A, in a bottle bearing only the label "Compound
A: C7H12'" Government agents have offered you a considerable sum to determine the structure of this
compound. After verifying the molecular formula by elemental analysis, you find that Compound A reacts with
I mol equiv of hydrogen; and, after treatment with acidic KMn04, Compound A gives the dicarboxylic acid C
(see below). Another bottle from the same laboratory is labeled "Compound B (isomer of A)." Compound B
also reacts with 1 mol equiv of hydrogen, but yields cyclohexanone after treatment with acidic KMn04'

°
°
II '
HO- C- aIaIzaIzaIz-
I
aI3

Compound C
°
II
C- OH
6
cyclohexanone

38. How many degrees ofunsaturation does Compound A possess?

Answer: A saturated seven carbon compound should have the formula C7H16so compound A has
(16-12)+2 = 2 degrees ofunsaturation.

39. Suggest structures for A and B.

Answer:

c5 c5
Compound A Compound B

40. What was the other product formedin the KMn04 oxidation ofB?

Answer: CO2

Test Items for McMurry's Organic Chemistry, Seventh Edition 57

 l

41. Lyapolate Sodium, whose structure is shown below, is used as an anticoagulant. Identify the monomer
unit(s) in lyapolate sodium.

+ CH2- CH-
I
CH2- CH+: n
I
S03Na S03Na

Answer:
H2C= CH- S03Na

42. Povidone is produced commercially as a series of products having mean molecular weights ranging from
about 10,000 to 700,000. Complexed with iodine, povidone yields an iodophor, marketed under the
tradename Betadine, which is used as a topical anti-infective.

CAo
I
CAo
I
t +CH-CH2-CH-CH2-t:- n
Identify the monomer unit(s) in povidone.

Answer:

CAo
I
CH= CH2

58 Chapter 7: Alkenes: Reactions and Synthesis