Problem Set 4 – Organic Compounds:

Cycloalkanes and Their Stereochemistry

1. Draw 7 constitutional isomers of a cycloalkane with the formula C6 H12

Answer:

2. Name each of the isomers you drew for question 1.

Answer: cyclohexane, methylcyclopentane, 1,2-dimethylcyclobutane, 1,1-dimethylcyclobutane, 1,3-

dimethylcyclobutane, 1,2,3-trimethylcyclopropane, and 1,1,2-trimethylcyclopropane.

3. Provide the IUPAC name for the following compound.

H C(CH3)3

H
CH3CH2

Answer: trans-1-tert-butyl-4-ethylcyclohexane or trans-1-(1,1-dimethylethyl)-4-ethylcyclohexane

Draw the structures corresponding to the following names.

4. cis-1-sec-butyl-2-ethylcyclopentane

CH3
CH2CH3
CHCH2CH3
Answer:
H
H

5. 3-cyclobutylpentane

Answer:
6. 1-chloro-2-isopropylcyclopentane

Answer:

Cl

7. 3,5-dicyclohexylnonane

Answer:

8. Circle all bridgehead carbons in the following structure.

Answer:

9. Draw the two stereoisomers of 1,3-dibromocyclobutane.

Answer:
Br Br

and

Br Br
cis trans
Refer to the structure below to answer the following questions:
e

a d

b c

10. Which of the labeled bonds in the structure are equatorial bonds?

Answer: a and d

11. Which of the labeled bonds are trans to bond b?

Answer: e

12. Which labeled bonds have a 1,3-diaxial interaction with each other?

Answer: b and c

For each substituted cyclohexane below, draw its ring-flip isomer. Circle the most stable conformation.

CH3
13.

CH3
Answer:

CH3

CH3
CH3 CH3
conformations are of equal stability

14. (CH3)3C

CH3
Answer:
(CH3)3C

(CH3)3C

CH3 CH3
15. Cl

Answer:

Cl

Cl

The following questions refer to the structure of camphor shown below.

H3C CH3
CH3
O

camphor

16. Circle all bridgehead carbons in camphor.

Answer:
H3C CH3
CH3
O

camphor

17. Camphor is an example of a:

a. fused bicyclic molecule.

b. bridged bicyclic molecule.
c. fused tricyclic molecule.
d. bridged tricyclic molecule.

Answer: b
18. Below are the two chair conformations of a 1,2,4-trimethylcyclohexane. Estimate the amount of 1,3-
diaxial strain in each conformer and predict which conformer is most stable.
CH3 CH3

H3C CH3
CH3
CH3
A. B.

CH3 CH3
Answer: 1 4
2
H3C 2
CH3
4 1
CH3
CH3
A. B.

Conformer A
C1 − CH 3 2 (H-CH3) = 2 x 3.8 kJ/mol = 7.6 kJ/mol
C2 − CH 3 2 (H-CH3) = 2 x 3.8 kJ/mol = 7.6 kJ/mol
C4 − CH 3 no diaxial interactions = 0 kJ/mol
Strain energy in conformer A 15.2 kJ/mol

Conformer B
C1,C2 − CH 3 one gauche interactions = 3.8 kJ/mol
C4 − CH 3 2 (H-CH3) = 2 x 3.8 kJ/mol = 7.6 kJ/mol
Strain energy in conformer B = 11.4 kJ/mol

Conformer B is more stable than conformer A by 3.8 kJ/mol.

19. The energy difference of 3.8 kJ/mol between gauche and anti butane corresponds to an equilibrium
constant, Keq , of approximately 1.9. Calculate the percentage of each conformer at equilibrium.

Answer: Keq = (anti) (gauche) = 19

.
. (gauche) and (anti) + (gauche) = 100%
(anti) = 19
Substitute 19. (gauche) for (anti) and you have:
. (gauche) + (gauche)
19 = 100%
2.9(gauche) = 100%
(gauche) = 34.4%
(anti) = 19
. (gauche) = 656%
.
20. In general, 5-alkyl substituents in 1,3-dioxane exhibit a smaller equatorial preference than they do in
cyclohexane. To what might you attribute this observation?

CH3 energy difference

7.53 kJ/mol
CH3
methycyclohexane
CH3

O
O 3.35 kJ/mol
O CH3
O
5-methyl-1,3-dioxane

Answer: The 5-alkyl substituted dioxanes do not suffer from 1,3-diaxial interactions since there are no
hydrogens that are axial to the 5-substituent. Hence, the axial conformation is more stable in 5-
substituted 1,3-dioxanes than it is in substituted cyclohexanes.

Label each pair of compounds below as:

a. conformational isomers
b. stereoisomers
c. constitutional isomers
d. identical

Br Br
21. _______ and
CH3 CH3

Answer: b

H H
H CH3 CH3 H
22. ________ and
H H H CH3
CH3 H
Answer: c

OH

OH
23. ________
and
OH

Answer: d OH
 CH3 CH3
24. _________ H Cl H H
and
H H H H
H Cl

Answer: a

CH3 CH3
CH3 H
and
25. ___________ H H
H CH3
Answer: b

For each pair of molecules below, circle the most stable.

26.
H
H

and H

Answer:

H
H

and H

27.
CH3 CH3
H H H CH3

and

H CH3 H CH3

CH3 H

Answer:
 CH3 CH3
H H H CH3

and

H CH3 H CH3

CH3 H

28.

and

Answer:

and

29. (-)-Menthol can be isolated from the peppermint plant and is responsible for the characteristic flavor and
taste of peppermint. The structure of (-)-menthol is:

H3C H

4
HO 1 3
2
H
H CHCH3

CH3

On the chair template provided below, draw the two chair conformations that are in equilibrium for (-)-
menthol.

4
1 2 3
 Answer:
H3C
CHCH3
4 HO CH3
1 2 3 CH3CH
CH3
CH3
OH

30. D-Pinitol is an interesting hexahydroxy cyclohexane, whose structure is shown below.

HO OH
5 6
HO 4 1 OH
3 2

HO OH

On the templates provided, draw the two chair conformations that are in equilibrium for D-pinitol. Circle
the most stable conformation.

5 1
3 6
4 2

Answer:

OH OH OH
OH
HO 5 1
3 6
HO 4 2 OH
HO OH OH
OH OH