Chapter 8 - Alkynes: An Introduction to Organic Synthesis

Draw structures corresponding to each of the following names.

1.

ethynylcyclopropane
Answer:

2.

3,10-dimethyl-6-sec-butylcyclodecyne

Answer:

3.

4-bromo-3,3-dimethyl-1-hexen-5-yne
CH3 Br

Answer: H2C

CH

CH

CH3

4.

acetylene
Answer:

Provide names for each compound below.

5.

CH3
CH3C

Answer:

CCHCH2CH2CH3

4-methyl-2-heptyne

CH3

6.

Answer:

CH

1-ethynyl-2-methylcyclopentane

Test Items for McMurrys Organic Chemistry, Seventh Edition

59

The compound below has been isolated from the safflower plant. Consider its structure to answer the following
questions.
H

H
C
H3C

C
C

7.

What is the molecular formula for this natural product?

Answer:

8.

C13H10

What is the degree of unsaturation for this compound?

Answer:

We can arrive at the degree of unsaturation for a structure in two ways. Since we know that the
degree of unsaturation is the number of rings and/or multiple bonds in a compound, we can
simply count them. There are three double bonds (3 degrees) and three triple bonds (six
degrees), so the degree of unsaturation is 9.
We can verify this by using the molecular formula, C13H10, to calculate a degree of unsaturation.
The saturated 13-carbon compound should have the base formula C13H28, so (28 - 10) 2 = 18
2 = 9.

9.

Assign E or Z configuration to each of the double bonds in the compound.

Answer:
H

H
E C
H3C C

H
C E
C C
H

10. Provide the name for this unusual natural product.

Answer:

(3E, 11E)-1,3,11-tridecatrien-5,7,9-triyne or (3E,11E)-trideca-1,3,11-trien-5,7,9-triyne

To answer the following questions, consider the information below:

The heat of hydrogenation of 1,4-pentadiene is 254.4 kJ/mol. The heat of hydrogenation of 1-pentyne is
approximately 292.9 kJ/mol.
11. Which structure is more stable, 1,4-pentadiene or 1-pentyne?
Answer:

60

1,4-pentadiene

Chapter 8: Alkynes: An Introduction to Organic Synthesis

12. Show the energy differences between the hydrogenation of 1,4-pentadiene and 1-pentyne on a reaction
energy diagram.
Answer:

A = 1-pentyne
B = 1,4-pendatiene
C = 1-pentene
D = pentane

A
Energy
B

C
292.9 kJ/mol

254.4 kJ/mol
D

Reaction Progress

Consider an unknown with the molecular formula C4 H 6 .

13. How many degrees of unsaturation are present?
Answer:

A saturated four carbon compound has the formula C4 H10 . Therefore this compound has
(10 6) 2 = 2 degrees of unsaturation.

14. Draw six of the nine possible structures with this formula.
Answer:
H
H2C

CCH2CH3
C

CH3C

CCH3

H2C

CHCH

CH2

CHCH3
CH3

CH3

CH2

Predict the product of each reaction below. Be sure to indicate stereochemistry when appropriate.
Br

15.

2 KOH
ethanol
Br

Test Items for McMurrys Organic Chemistry, Seventh Edition

61

Answer:
Br
2 KOH
ethanol
Br

16.

CH3CH2

D2

CH3

Lindlar catalyst

Answer:
CH3CH2

D2

CH3

CH3CH2

CH3
C

Lindlar catalyst

17.

1. BH3, THF
2. H2O2, NaOH, H2O

C
D

Answer:
O

18.

1. BH3, THF
2. H2O2, NaOH, H2O

1. NaNH2, NH3
2. CH3CH2I

1. NaNH2, NH3
2. CH3CH2I

CH2

Answer:
C

CH2CH3

KMnO4

19.

H3O+

Answer:
KMnO4
+

H3O
62

COOH
COOH
Chapter 8: Alkynes: An Introduction to Organic Synthesis

20.

CH3CH2C

CH

HgSO4, H2SO4
H2O

Answer:
O
CH3CH2C

CH

HgSO4, H2SO4
H2O

CH3CH2CCH3

CH

CH

CH

CH

excess H2
Pd/C

21.

Answer:
CH2CH2CH2CH3

excess H2
Pd/C

To answer the following questions consider this reaction:

Br
CH3CH2CH2CH2

HBr
CH3COOH

CH3CH2CH2CH2

CH2

22. On the structures provided, draw arrows showing the electron flow for the reaction mechanism for the
electrophilic addition of hydrogen bromide to 1-hexyne
CH3CH2CH2CH2

Br

+
C

CH3CH2CH2CH2

CH2

Br

Br
CH3CH2CH2CH2

CH2

Answer:
CH3CH2CH2CH2

Br

CH3CH2CH2CH2

+
C

CH2

Br

Br
CH3CH2CH2CH2

Test Items for McMurrys Organic Chemistry, Seventh Edition

CH2

63

23. The key intermediate in the electrophilic addition reaction shown above is called:
a.
b.
c.
d.

an acetylenic carbocation
a vinylic bromide
a secondary carbocation
a vinylic carbocation

Answer:

Select the best reagent or sequence of reagents from the list provided which would best accomplish each
transformation below. Place the letter corresponding to the reagent(s) in the blank to the left of each reaction.
Each transformation requires only one answer.
a.
b.
c.

H2SO4, H2O, HgSO4

H2, Lindlar
1. BH3, THF
2. H2O2
1. NaNH2, NH3
2. CH3CH2I

d.

e. 1. Br2, CCl4
2. 2 NaNH2, NH3
f. 1. HCl
2. NaNH2, NH3
g. Li/NH3
h. 1. NaNH2, NH3
2. CH3CH2CH2I
H3C

24.

CH3C

CCH3
H

Answer:

H
C
CH3

g
O
CH2

25.

Answer:
26.

Answer:

64

CH2

CH

CH3

a
C

CH3 CH2 CH2 C

CH

27.
Answer:

CH

Chapter 8: Alkynes: An Introduction to Organic Synthesis

Show all reagents and intermediates necessary to carry out the following conversions.
H

28.

(CH3)2CHCH2C

CH

CH2CH3
C

C
H

(CH3)2CHCH2

Answer:
(CH3)2CHCH2C

CH

1. NaNH2, NH3
2. CH3CH2Br
(CH3)2CHCH2C

CCH2CH3

Li/NH3

CH2CH3
C

(CH3)2CHCH2

OH

29.

CH3CH2C

CH3CH2CHCH2CH2CH3

Answer:
CH3CH2C

1. NaNH2, NH3
2. CH3CH2Br

CH3CH2C

CCH2CH3

H2, Pd/C
or
Li/NH3

CH3CH2CH

CHCH2CH3

1. Hg(OAc)2, H2O,/THF
2. NaBH4
or

1. BH3, THF
2. H2O2, NaOH, H2O

OH
CH3CH2CHCH2CH2CH3

Test Items for McMurrys Organic Chemistry, Seventh Edition

65

Using acetylene and any alkyl halides as starting materials, synthesize the following compounds. More than
one step may be required. Show all reagents and all intermediate compounds in your synthetic scheme.
O
CH3CCH2CH2CH2CH2CH3

30.

2-heptanone
(responsible for the odor of cheddar cheese)

Answer:
HC

1. NaNH2, NH3

CH

2. CH3CH2CH2CH2CH2I

HC

CCH2CH2CH2CH2CH3
HgSO4, H2SO4
H2O
O

CH3CCH2CH2CH2CH2CH3

31.

Answer:
HC

1. NaNH2, NH3
2. C6H5CH2I

CH

CH2C

Cl

32.

Cl

CCH2

CH2C

1. NaNH2, NH3
2. C6H5CH2I

CH

Li/NH3

1,2-dichloropropane
(a degreasing solvent used in dry cleaning)

Answer:

HC

CH

1. NaNH2, NH3
2. CH3I

HC

CCH3

H2/Lindlar
or
Li/NH3

H2C

CHCH3
Cl2
CCl4
Cl

Cl
66

Chapter 8: Alkynes: An Introduction to Organic Synthesis

33.

O
H3C

OH

acetic acid
(raw material for the vinyl acetate
polymer used in paints and adhesives)

Answer:
HC

CH

1. NaNH2, NH3
2. CH3I

CH3C

CH

1. NaNH2, NH3
2. CH3I

CH3C

CCH3
KMnO4
H3O+

O
2

H3C

OH

Br

34.

CH3CHCH2CH2CH3

Answer:
HC

CH

1. NaNH2, NH3
2. CH3CH2CH2I

HC

CCH2CH2CH3

H2
Lindlar catalyst

H2C

CHCH2CH2CH3
HBr
ether
Br

CH3CHCH2CH2CH3

Test Items for McMurrys Organic Chemistry, Seventh Edition

67