Alkane Stereochemistry

1) For the molecules below:

a) Provide a 3 dimensional structure at the indicated atoms.
b) Draw the Newman projection for your structure indicating the direction of sight with an arrow.
c) Draw the Newman projection for the most stable conformation.
d) Draw the Newman projection for the least stable conformation.
e) If possible, calculate the energy difference between the most and least stable conformations.
(H3C)2HC CH3 (H3C)2HC CH2CH3 H3CH2C CH2OH H3CH2C OH
barrier to rotation =
17kJ/mol (why?)
H3C HH H3C HH H3C HH H3C
O
H3CH H H3CH CH3 HH OH HH H

CH3 CH3 CH3 CH3

H H H H H H : :
Most
Stable
H3C H H3C H H H H H
H CH3 OH H

H3C 6 kJ/mol H3C 11 kJ/mol H3C H3C

H CH3 OH H
Least
Stable
H HH H HH H HH : :H
H3C 4 kJ/mol H3C 4 kJ/mol H 4 kJ/mol H
6 kJ/mol 6 kJ/mol 4 kJ/mol
17 - 4 - 4 = 9 kJ/mol for
each CH3 : OH eclipse

2) a) Draw a chair cyclohexane and put in all the axial bonds.

b) On a second chair cyclohexane, put in all the equatorial bonds.
c) Draw a cyclohexane with a bromine in an equatorial position.
d) Draw a cyclohexane with a bromine in an axial position.
(a) (b) (c) (d)
Br

Br

equatorial bonds
axial bonds

3) Draw both possible conformations for the indicated cyclohexane:

a) trans-1-chloro-2-methylcyclohexane.
b) cis-1-chloro-2-methylcyclohexane.
c) trans-1-chloro-3-methylcyclohexane.
d) cis-1-chloro-3-methylcyclohexane.
a Cl
Cl
e) trans-1-chloro-4-methylcyclohexane.
f) cis-1-chloro-4-methylcyclohexane.
g) a cyclohexane with 2 methyl groups, both axial.
h) a cyclohexane with 2 methyl groups, both equatorial.
b c
Cl
Cl
Cl Cl
 d e f
Cl Cl Cl
Cl Cl
Cl

g h

one possible answer one possible answer

4) Draw the Newman projection for 3 a-d.

(a) H Cl H H (b) H Cl H CH3
H H H Cl H CH3 H Cl
H H H CH3 H H H H
H CH3 H H H H H H

(c) H Cl H H (d) CH3 Cl H H

H H H Cl H H H3C Cl
H3C H H H H H H H
H H CH3 H H H H H

5) For the following pairs:

a) Circle the more stable cyclohexane.
b) Calculate the energy difference between the two structures, if possible. see McMurry Fig. 4.22
c) Indicate whether the structures are conformers (conformational isomers) or stereoisomers.

(a) (b)
*CH * *
t
CH Bu Me
3
3
Cl Me t
Bu
*
CH3
H3C Cl*
conformers, 13.6 kJ/mol
conformers, 23 kJ/mol (see problem 4.44)

(c) (d) CN
NC
Et * conformers CN *
Et
Et
*
CN 8.8 kJ/mol
*Et 8.0 kJ/mol 0.8 kJ/mol
conformers, 7.2 kJ/mol

(e)
* Me H Me
H H
H
(f) Cl *
H H t
Bu
H H t
H CO2H H CO2H Bu Cl Me
H H
*
Me
* *
7.2 kJ/mol 5.8 kJ/mol 9.2 7.2
conformers, 1.8kJ/mol stereoisomers, 2 kJ/mol

6) For every structure above, star the axial substituents and box the equatorial substituents.
7) For every structure below, draw the most stable chair conformation. Where two or more conformations are
equally stable, draw both.

Cl
CH3 Br OH

CH3 OH
CH2CH3 Br
(a) (b) (c) (d)

Br Br OH
HO
Cl Br
(same) Br

F CH3

F H3C
CN CH3
(e) (f) (g)

F CH3
NC F H3C
H3C