Drawing and calculating Keq for cycloalkane conformers

Cycloalkane conformers, while looking at first difficult to draw, are really quite simple. Let’s use
chair cyclohexane as an example:

A B C D
Start by drawing two parallel, but offset lines (A). Put a nose on it (B), followed by
a tail (C). Finally, add in the axial and equitorial bonds (D). When transcribing groups e a
from a cyclohexyl structure to the chair conformation, remember the relationship of a a e
e
axial and equitorial groups (and don’t mix this up with cis and trans!!). Practice will e a
e a
make perfect! a e

Let’s now examine how to calculate equlibrium concentrations of cyclohexane

conformers. Before beginning it must be clear that the A values (in Kcal!) are related to the equlibrium
constant in the following manner:
A = -DGox = RT lnK eq ; and Keq is is the equlibrium constant of a group going from axial to
equitorial (a favored shift). Thus a positive A value indicates that a group would much rather be
equitorial than axial; as a result, the A values you are given have been DEFINED as values for an
AXIAL group going to an EQUITORIAL orientation. Let’s begin with methylcyclohexane:
CH3

CH3 H

I H
II
To calculate the relative percentages or ratios of I to II:
• Find the A values for the groups involved. Here only methyl need be considered and it has
an A value of +1.7 kcals.
• Determine the sign of the A value for the equlibrium you are examining. For the example
above, the sign of the A value has to be negative (since AMe=+1.7 and the reaction as shown
above is going from eq to ax).
• Calculate the Keq using the equation above at 23°C (R= 1.986x10-3 Kcal/°K and T is in
[II] [II]
Kelvin [°K=273 + °C]). So, A = RT ln or -1.7= (1.986x10-3)(300)ln . Multiplication
[I] [I]
[II]
and division gives ln =-2.85; solving for the ratio (i.e. taking the antilog) gives
[I]
[II]
=0.058. This says that there is about 17 times more of conformer I than II at any given
[I]
time (or there is only about 6% of II in the equlibrium at any given time). This result should
make sense based on the A values.
Thats all! It really is simple (unless your math skills are poor) as long as you remember the
correct sign of the A value. What about multiple groups? They are handled in the same
manner:
Cl
CH3
H
CH3 H
Cl

I H
II
H
Cl has an A value of 0.43 and CH 3 has an A value of 1.7. A values are additive so:
Atotal=ACl+(-AMe)=0.43+(-1.7)=-1.27.
[II]
Substituting this into the equation (and using 23°C) gives a ratio of =0.119. This says that
[I]
there is about 8.3 times more of conformer I than II at any given time (or there is only about
12% of II in the equlibrium at any given time). Notice how the addition of another group
changes things? On your own, calculate equlibrium constants and relative ratios for the
equlibrium conformation concentrations one would expect for the following:
1-t-butylcyclohexane; cis 1,3-dimethylcyclohexane; trans 1,4-dihydroxycyclohexane; and
NH2
CH3

H H
Cl

H
 Standard A Values (kJ)

A value ( kJ) = - DGoX = RT ln Keq

X
Keq
H X

H
R = 8.314 x 10-3 kJ/°K
Note: A is defined as a positive value when going from axial to equitorial

X A Value X A Value X A Value

F 0.63 -CN 0.71 CH3 7.11
Cl 1.80 -NC 0.88 CF3 8.79
Br 1.59 -NCO 2.13 CH2CH3 7.32
I 1.80 -NCS 1.17 CH=CH2 5.65
OH 3.64 -N=C=N-R 4.18 C H 1.72
OCH3 2.51 NH2 6.69 CH2C(CH3)3 8.37
OCD3 2.34 NHCH3 4.18 CH2OTs 7.32
OC2H5 3.77 N(CH3)2 8.79 CH(CH3)2 9.00
OAc 2.51 -NH3+ 7.95 c-C6H11 9.00
OC(O)CF3 2.85 -NO2 4.60 C(CH3)3 >16.74
OCHO 1.13 PH2 6.69 C6H5 12.55
OTs 2.09 P(CH3)2 6.28 CO2H 5.65
-ONO2 2.47 PCl2 7.95 CO2- 8.03
SH 3.77 P(OCH3)2 6.28 CO2CH3 5.31
SCN 5.15 P+(CH3)3 >12.55 CO2C2H5 5.02
SCH3 2.93 P(S)(CH3)2 >12.55 CO2CH(CH3) 4.02
2
SC6H5 3.35 HgBr -1.26 COCl 5.23
-S- 5.44 HgCl 1.26 COCH3 4.90
SOC6H5 7.95 Si(CH3)3 ------
SOCH3 5.02 Ge(CH3)3 8.79
SO2C6H5 10.46 Sn(CH3)3 4.60
SO2CH3 10.46 Pb(CH3)3 2.93
 Standard A Values

A value (kcal) = -DGoX = RT ln Keq

X
Keq
H X

H
R = 1.986 x 10-3 kcal/°K
Note: A is defined as a positive value when going from axial to equitorial

X A Value X A Value X A Value

F 0.15 -CN 0.17 CH3 1.70
Cl 0.43 -NC 0.21 CF3 2.1
Br 0.38 -NCO 0.51 CH2CH3 1.75
I 0.43 -NCS 0.28 CH=CH2 1.35
OH 0.87 -N=C=N-R 1.0 C H 0.41
OCH3 0.60 NH2 1.60 CH2C(CH3)3 2.0
OCD3 0.56 NHCH3 1.0 CH2OTs 1.75
OC2H5 0.9 N(CH3)2 2.1 CH(CH3)2 2.15
OAc 0.6 -NH3+ 1.9 c-C6H11 2.15
OC(O)CF3 0.68 -NO2 1.1 C(CH3)3 >4
OCHO 0.27 PH2 1.6 C6H5 3.0
OTs 0.50 P(CH3)2 1.5 CO2H 1.35
-ONO2 0.59 PCl2 1.9 CO2- 1.92
SH 0.9 P(OCH3)2 1.5 CO2CH3 1.27
SCN 1.23 P+(CH3)3 >3.0 CO2C2H5 1.20
SCH3 0.7 P(S)(CH3)2 >3.0 CO2CH(CH3) 0.96
2
SC6H5 0.8 HgBr -0.3 COCl 1.25
-S- 1.3 HgCl 0.3 COCH3 1.17
SOC6H5 1.9 Si(CH3)3 ---
SOCH3 1.2 Ge(CH3)3 2.1
SO2C6H5 2.5 Sn(CH3)3 1.1
SO2CH3 2.5 Pb(CH3)3 0.7