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Essential Organic Chemistry (Bruice)

Chapter 5

Essential Organic Chemistry (Bruice)


Chapter 5
Reactions of Alkenes and Alkynes: An Introduction to Multistep Synthesis
1)
What is the role of the bond of an alkene in an electrophilic addition reaction?
Answer:

The relatively loosely held electrons of the carbon-carbon double bond attack an electrophile to begin the reaction.
Section: 5.0

2)
Complete the following reaction and provide a detailed, step-by-step mechanism for the process.

Answer:

Section: 5.1

3)
What is the product in the following reactions?

Answer:

Essential Organic Chemistry (Bruice)


Chapter 5

Section: 5.1 and 5.3

Essential Organic Chemistry (Bruice)


Chapter 5

4)
Which of the following is the most stable carbocation?

A)
I

II

III

IV

B)

C)

D)

E)

Answer:

D
Section: 5.2

Essential Organic Chemistry (Bruice)


Chapter 5

5)
Which of the following alkenes reacts with HCl at the slowest rate?
A)

B)

C)

D)

E)

Answer:

A
Section: 5.2

6)
Which of the following compounds will react most rapidly with HCl?
A)

Essential Organic Chemistry (Bruice)


Chapter 5

5-methyl-1-hexene
B)
4-methyl-1-hexene
C)
(E)-5-methyl-2-hexene
D)
(E)-2-methyl-3-hexene
E)
2-methyl-2-hexene
Answer:

E
Section: 5.2

7)
Draw the major organic product generated in the reaction below.

Answer:

Section: 5.3

8)
Draw the major organic product generated in the reaction below.

Answer:

Essential Organic Chemistry (Bruice)


Chapter 5

Section: 5.3

9)
Draw the major organic product generated in the reaction below.

Answer:

Section: 5.3

10)
Draw the major organic product generated in the reaction below.

Answer:

Section: 5.3

11)
Draw the major organic product generated in the reaction below.

Essential Organic Chemistry (Bruice)


Chapter 5

Answer:

Section: 5.3

Essential Organic Chemistry (Bruice)


Chapter 5

12)
Draw the major organic product generated in the reaction below.

Answer:

Section: 5.3

13)
Draw the structures of the two alkenes that react with HBr to yield 1-bromo-1-methylcyclohexane as the major organic
product.
Answer:

Section: 5.3

Essential Organic Chemistry (Bruice)


Chapter 5

14)
What is the major product of the following reaction?

A)
I

B)

II

C)

III

D)

IV

E)

Answer:

C
Section: 5.4

15)
Draw the major organic product generated in the reaction below.

Essential Organic Chemistry (Bruice)


Chapter 5

Answer:

Section: 5.4

16)
Draw the major organic product generated in the reaction below.

Answer:

Section: 5.4

Essential Organic Chemistry (Bruice)


Chapter 5

17)
Complete the following reaction and provide a detailed, step-by-step mechanism for the process.

Answer:

Section: 5.4

18)
What is the major product from the acid-catalyzed hydration of 2-methyl-2-pentene?
A)
2-methylpentane
B)
2-methyl-1-pentanol
C)
2-methyl-2-pentanol
D)
2-methyl-3-pentanol
E)
1-methoxypentane
Answer:

Section: 5.4

19)
Provide the structure of the major organic product of the following reaction.

Essential Organic Chemistry (Bruice)


Chapter 5

Answer:

Section: 5.4

20)
Provide the structure of the major organic product of the following reaction.

Answer:

Section: 5.5

Essential Organic Chemistry (Bruice)


Chapter 5

21)
What is/are the product(s) of the following reaction?

Answer:

Section: 5.5

22)
How many electrons are involved in a carbon-carbon triple bond?
A)
1

B)

C)

D)

E)

Answer:

Section: 5.6

Essential Organic Chemistry (Bruice)


Chapter 5

23)
What is the IUPAC name for the following alkyne?

A)
5-Bromo-2-heptyne
B)
3-Bromo-5-heptyne
C)
2-Bromo-2-methyl-4-hexyne
D)
5-Bromo-5,5-dimethylhexyne
E)
5-Bromo-5-methyl-2-hexyne
Answer:

E
Section: 5.7

24)
Write structures and give IUPAC names for all alkynes with molecular formula C5H8.
Answer:

Section: 5.7

25)

Essential Organic Chemistry (Bruice)


Chapter 5

Give the IUPAC name for


Answer:

2,5,5-trimethyl-3-heptyne
Section: 5.7

26)

Give the IUPAC name for


Answer:

1-pentyne
Section: 5.7

27)

Give the IUPAC name for


Answer:

1-bromo-3-hexyne
Section: 5.7

28)
Draw an acceptable structure for acetylene.
Answer:

HCCH

Section: 5.7

29)
Draw an acceptable structure for 3-sec-butyl-1-heptyne.
Answer:

Essential Organic Chemistry (Bruice)


Chapter 5

Section: 5.7

30)
Draw an acceptable structure for 2-hexyne.
Answer:

Section: 5.7

31)
How many distinct terminal alkynes exist with a molecular formula of C5H8?
A)

B)

C)

D)

E)

Answer:

B
Section: 5.7

32)

Essential Organic Chemistry (Bruice)


Chapter 5

How many distinct internal alkynes exist with a molecular formula of C6H10?
A)

B)

C)

D)

E)

Answer:

Section: 5.7

33)
What is the common name for the following alkyne?

A)
Neohexyne

B)

Trimethylpropyne
C)
Trimethylacetylene
D)
tert-Butylacetylene
E)
Isopropylacetylene

Essential Organic Chemistry (Bruice)


Chapter 5

Answer:

D
Section: 5.7

34)
Give the systematic name for the alkyne

Answer:

6,6,6-trichloro-2-hexyne
Section: 5.7

35)
Which of the following is a correct statement about the carbon-carbon triple bond in an alkyne?
A)
composed of one sigma bond and one pi bond
B)
composed of two sigma bonds and one pi bond
C)
composed of one sigma bond and two pi bonds
D)
composed of two sigma bond and two pi bond
E)
composed of one sigma bond, one pi bond and one delta bond
Answer:

C
Section: 5.8

Essential Organic Chemistry (Bruice)


Chapter 5

36)
What is the hybridization of the carbon atoms numbered 1 and 2 respectively in the following structure?

A)
sp3, sp2

sp2, sp2

B)

C)

sp, sp
D)
sp2, sp

E)

sp, sp2
Answer:

D
Section: 5.8

37)
Which of the following statements is not true about propyne, HCCCH3?
A)

It contains six sigma bonds.


B)
It contains three pi bonds.
C)
The HCH bond angle is about 109.5.
D)
The CCC bond angle is 180.
E)
The pi bond is weaker than the sigma bond.

Essential Organic Chemistry (Bruice)


Chapter 5

Answer:

B
Section: 5.8

38)
What two atomic orbitals or hybrid atomic orbitals overlap to form the carbon-carbon bond in ethyne?
A)
sp3sp3
B)
pp

C)

sp2sp2
D)
ss
E)
spsp
Answer:

Section: 5.8

39)
What are the hybridizations of the carbon atoms numbered 1 and 2 in the structure below?
1 2
H3C-CHCH-CC-H
A)

sp3, sp2

sp2, sp2

sp2, sp

B)

C)

D)

Essential Organic Chemistry (Bruice)


Chapter 5

sp, sp
Answer:

D
Section: 5.8

40)
Which of the following improperly describes the physical properties of an alkyne?
A)
relatively nonpolar
B)
nearly insoluble in water
C)
less dense than water
D)
insoluble in most organic solvents
Answer:

Section: 5.9

41)
Which of the following are correct statements concerning unsaturated hydrocarbons?
A)
All hydrocarbons are insoluble in water.
B)
All hydrocarbons are soluble in nonpolar solvents.
C)
All hydrocarbons are more dense than water.
D)
A and B

A, B, and C

E)

Essential Organic Chemistry (Bruice)


Chapter 5

Answer:

D
Section: 5.9

42)
Although you might expect 1-propyne to be more reactive than 1-propene in electrophilic addition reactions, the reverse
is true. Explain this using your knowledge of the mechanism of electrophilic additions to both alkynes and alkenes.
Answer:

When HCl is added to an alkene, a secondary carbocation intermediate is formed,

When HCl is added to an

alkyne, a vinylic carbocation is formed as an intermediate,


Alkynes are less stable than alkenes but vinylic
carbocations are less stable than secondary carbocations. Thus, alkenes are more reactive than alkynes since the difference
in stabilities between the carbocations is greater than the difference in stabilities between the alkene and alkyne.
Section: 5.10

43)
Which of the following statements correctly describes the general reactivity of alkynes?
A)
An alkyne is an electron-rich molecule and therefore reacts as a nucleophile.
B)
The bonds of alkynes are higher in energy than the bonds and are thus more
reactive.
C)
Unlike alkenes, alkynes fail to undergo electrophilic addition reactions.
D)
Alkynes are generally more reactive than alkenes.
E)
none of the above
Answer:

A
Section: 5.10

Essential Organic Chemistry (Bruice)


Chapter 5

44)
Describe the role of the alkyne in the reaction between an alkyne and a hydrogen halide.
Answer:

An alkyne is an electron-rich molecule because of its two bonds and thus an alkyne is a nucleophile. electrons from the
alkyne triple bond attack the electrophilic hydrogen of the hydrogen halide during the first step of the reaction between
an alkyne and a hydrogen halide.
Section: 5.10

Essential Organic Chemistry (Bruice)


Chapter 5

45)
What is the major product of the following reaction?
HCl
CH3CCH
A)

B)

C)
CH3CHCHCl
D)

E)

Answer:

B
Section: 5.10

46)
Provide the structure of the major organic product(s) in the reaction below.

Essential Organic Chemistry (Bruice)


Chapter 5

Answer:

Section: 5.10

47)
In the addition of hydrogen bromide to alkynes, which of the following species is believed to be an intermediate?
A)
vinyl anion

vinyl cation

B)

C)

vinyl radical
D)
carbene

E)

none of the above


Answer:

Section: 5.10

48)
Which of the following compounds is the major product when 1-hexyne is treated with excess HBr?
A)
1,1-dibromohexane
B)
1,1-dibromohexene

Essential Organic Chemistry (Bruice)


Chapter 5

C)
1,2-dibromohexene
D)
1,2-dibromohexane
E)
2,2-dibromohexane
Answer:

E
Section: 5.10

49)
Provide the structure of the major organic product of the following reaction.

Answer:

Section: 5.10

50)
Provide the structure of the major organic product of the following reaction.

Answer:

Essential Organic Chemistry (Bruice)


Chapter 5

Section: 5.10

Essential Organic Chemistry (Bruice)


Chapter 5

51)
Which of the following are enol forms of 2-butanone?

A)

B)

C)

D)

E)

Answer:

E
Section: 5.11

Essential Organic Chemistry (Bruice)


Chapter 5

52)
Which of the following is the final and major product of this reaction?

A)
I

B)

II

C)

III

D)

IV

E)

Answer:

Section: 5.11

53)
Provide the structure of the major organic product(s) in the reaction below.

Essential Organic Chemistry (Bruice)


Chapter 5

Answer:

Section: 5.11

54)
Which of the alkyne addition reactions below involves an enol intermediate?
A)
hydroboration/oxidation
B)
treatment with HgSO4 in dilute H2SO4
C)

hydrogenation
D)
both A and B
E)
none of the above
Answer:

Section: 5.11

Essential Organic Chemistry (Bruice)


Chapter 5

55)
Provide the structure of the major organic product of the following reaction.

Answer:

Section: 5.11

56)
Which of the following reagents gives the reaction shown below?
CH3CH=CH2 + ? CH3CH2CH3
A)

H2/HCl

B)

H2/H2SO4

H2/Ni

H2O/Ni

C)

D)

E)

H2O/H2SO4
Answer:

Section: 5.12

Essential Organic Chemistry (Bruice)


Chapter 5

57)
Upon hydrogenation, which of the following alkenes releases the least heat per mole?
A)
3,4-dimethyl-1-hexene
B)
(Z)-3,4-dimethyl-2-hexene
C)
(E)-3,4-dimethyl-2-hexene
D)
(Z)-3,4-dimethyl-3-hexene
E)
(E)-3,4-dimethyl-3-hexene
Answer:

E
Section: 5.12

58)
The reagent needed to convert 2-butyne to cis-2-butene is:
A)
H2/Pt

B)

H2/Lindlar's catalyst
C)
Li/NH3

Na/NH3

D)

E)

H+/Zinc dust
Answer:

Essential Organic Chemistry (Bruice)


Chapter 5

Section: 5.12

Essential Organic Chemistry (Bruice)


Chapter 5

59)
A mixture of 1-heptyne, 2-heptyne, and 3-heptyne was hydrogenated in the presence of a platinum catalyst until
hydrogen uptake ceased. If one assumes that the hydrogenation went to completion, how many distinct seven-carbon
hydrocarbons were produced?
A)
1

B)

C)

D)

E)

Answer:

A
Section: 5.12

60)
Provide the structure of the major organic product(s) in the reaction below.

Answer:

Section: 5.12

61)
Provide the structure of the major organic product of the following reaction.

Essential Organic Chemistry (Bruice)


Chapter 5

Answer:

Section: 5.12

62)
Provide the structure of the major organic product of the following reaction.

Answer:

Section: 5.12

63)
Which is the correct order of decreasing acidity in the following compounds?
H2O
A

CH3CH3
B
A)

A>E>C>D>B
B)
A>E>D>B>C

NH3
C

CH2CH2
D

HCCH
E

Essential Organic Chemistry (Bruice)


Chapter 5

C)
E>A>C>B>D
D)
A>C>E>D>B
E)
E>D>B>A>C
Answer:

A
Section: 5.13

64)
Explain why HCN is a stronger acid than HCCH.
Answer:

Because nitrogen is more electronegative than carbon.


Section: 5.13

65)
Which hydrogens are more acidic, those of benzene or those of cyclohexane? Why?

Answer:

Benzene. The carbon hybridization of benzene is sp2 while that of cyclohexane is sp3. The more s character in benzene
causes its hydrogens to be more acidic than those of cyclohexane.
Section: 5.13

66)
Why are terminal alkynes more acidic than other hydrocarbons?
Answer:

The carbanion which results upon deprotonation of a terminal alkyne has the lone pair of electrons in an sp hybridized

Essential Organic Chemistry (Bruice)


Chapter 5

orbital. The greater % s character of this orbital gives the orbital a significantly lower energy.
Section: 5.13

67)
Which of the species below is less basic than acetylide,
A)
CH3Li

CH3ONa

NaOH

B)

C)

D)

both B and C
E)
all of the above
Answer:

D
Section: 5.13

68)
Among the compounds water, 1-butyne, 2-butyne, and ethane, which are stronger acids than ammonia?
A)
1-butyne and ethane
B)
water and 1-butyne
C)
water and ethane
D)
1-butyne and 2-butyne
Answer:

Essential Organic Chemistry (Bruice)


Chapter 5

B
Section: 5.13

69)
What type of organic product results when 1-butyne is treated with 6M aqueous NaOH?
A)
a sodium acetylide
B)
an enol

C)

an alcohol

D)

an aldehyde

E)

Not much reaction; most of the alkyne remains unchanged.


Answer:

Section: 5.13

70)
Provide the structure of the major organic product of the following reaction.

Answer:

Section: 5.13

Essential Organic Chemistry (Bruice)


Chapter 5

71)
Provide the structure of the major organic product(s) in the reaction below.
CH3CH2CH
2. PhCH2Br
Answer:

CH3CH2CCCH2Ph
Section: 5.14

72)
Provide the structure of the major organic product of the following reaction.

Answer:

Section: 5.14

73)
Suggest a plausible scheme for the following synthesis

Answer:

Essential Organic Chemistry (Bruice)


Chapter 5

Section: 5.15

74)
Describe a sequence of reactions by which 3-heptyne can be straightforwardly prepared from acetylene.
Answer:

1)
2)
3)
4)

NaNH2

CH3CH2Br
NaNH2

CH3CH2CH2Br
Section: 5.15

75)

Describe a sequence of reactions by which


butyne.
Answer:

can be straightforwardly prepared from 1-

1) NaNH2
2) CH3CH2Br

3) HgSO4, H2O, H2SO4


Section: 5.15

76)
Describe a sequence of reactions by which cis-2-pentene could be prepared from acetylene.
Answer:

Essential Organic Chemistry (Bruice)


Chapter 5

1)
2)
3)
4)
5)

NaNH2

CH3CH2Br
NaNH2

CH3Br
H2, Lindlar's catalyst
Section: 5.15

Essential Organic Chemistry (Bruice)


Chapter 5

77)
What is/are the major organic product(s) of the following reaction?
A)
CH2CH2 + HCCH
B)
CH3CH2CCH
C)
HCCBr
D)
HCCCH2CH2Br
E)
CH3CCCH3
Answer:

B
Section: 5.15

78)
What is the structure of the monomer from which the following polymer is made?

A)
CH3CH3

CH2CH2

B)

C)

CH3CHCH2
D)
CH2CHCHCH2

Essential Organic Chemistry (Bruice)


Chapter 5

E)
CH3CHCHCH3
Answer:

Section: 5.16

Essential Organic Chemistry (Bruice)


Chapter 5

79)
What is the structure of the monomer from which the following polymer is made?

A)
I

B)

II

C)

III

D)

IV

E)

Answer:

Section: 5.16

80)
Which of the following addition polymers results from the reaction below?
nCF2CF2

A)

Essential Organic Chemistry (Bruice)


Chapter 5

[CF-CF]n
B)
[CF3-CF3]n

C)

[-CF2-CHCHCF2-]n
D)

[-CF2-CF2-]n

E)

[-CF2CF2-]n

Answer:

Section: 5.16

81)
Which of the following species can best serve as a radical initiator for radical polymerization?
A)
ROH

ROR

ROOR

RCOOR

RCOOH

B)

C)

D)

E)

Answer:

C
Section: 5.16

Essential Organic Chemistry (Bruice)


Chapter 5

82)
Which of the following is the first chain propagating step in the radical polymerization of ethylene using a peroxide
initiator?
A)
ROOR + CH2CH2 ROCH2CH2OR
B)

RO + CH2CH2 ROCH2CH2
C)
RO + CH2CH2 ROCHCH2 + H
D)

ROOR + CH2CH2 2 ROH + CHCH


E)

2RO + CH2CH2 2 ROH + CHCH
Answer:

B
Section: 5.16

83)
List the three phases in the mechanism of chain-growth polymerization.
Answer:

1.
2.
3.

Initiation
Propagation
Termination
Section: 1.2

Essential Organic Chemistry (Bruice)


Chapter 5

84)
Show the mechanism for the formation of a segment of polystyrene containing two molecules of styrene and initiated by
hydrogen peroxide.
Answer:

Section: 5.16

85)
Provide a mechanism to show how H2CC(CH3)2 is polymerized using BF3 as the initiatior.
Answer:

Section: 5.16

Essential Organic Chemistry (Bruice)


Chapter 5