10.

2 Conformations of cyclohexane
X-ray and electron diffraction experiments clearly prove that cyclohexane exists
almost exclusively in the chair conformation. An examination of the model
(Dreiding, Fieser,or Prentice-Hall) of the cyclohexane chair shows that it is devoid
of any kind of strain. In an ideal chair, the bond angles are 109°28', i.e., E, = 0:
there is no bond length distortion, i.e., E= 0; all the bonds are staggered
(0=60°), i.e., Eg = 0, and there is no non-bonded interaction. In fact, the chair
form lies at the bottomof a deep energy well and any deviation therefrom is
strongly resisted by internal forces. The structure is rigid and the rigidity can be felt
ven in the model which unlike that of n-butane resists easy rotation around single
bonds.
10.2.1 Characteristics of the chair conformation

The characteristics of the cyclohexane chair are best described under the following
headings:
1. Geometry. The electron diffraction experiments of cyclohexane in the
gaseous phase (Geise et al 1971) show the following geometric parameters:
C-Cbond length=0.1528 nm (152.8 pm)
C-H bond length = 0.1119 nm (111.9 pm)
C-C-Cbond angle = 111°0S (instead of 109°28)
Dihedral angle (as shown in la) = S6° (instead of 60)
The increased CCC bond angle makes the chair conformation slightly
flattened* so that the dihedral angles between adjacent C-C bonds are 56° and
the vertical C-H bonds (axial) are not exactly parallel to the C axis but lean
outwards from it by 7°. The chair form is drawn in three different perspectives
(Figure 10.1). The structure (I) shows the conventional drawing of the chair with
the C, axis vertical and the six carbon atoms distributed in two parallel horizontal
planes, 1-3-5 in one and 2-4-6 in the other separated by a distance of 0.05 nm.
Any consecutive four carbon atoms form a gauche butane unit and since there are
six such units (1-2-3-4, 2-3-4-5, 3-4-5-6etc.), the enthalphy of cyclohexane chair
may be computed as 3.3 X6 or 19.8 kJ mol with respect to a hypothetical
all-anti chair conformationt
In the structure (la), two pairs of n-butane units (2-3-4-5 and 2-1-6-5) are seen
in Newman projection with dihedral angle of 56° in each. The structure (1b) shows

*The flattening brings a balance between angle and torsional strains thus minimising the energy of the
system.
t For various reasons, the calculation may be spurious as well as bypothetical (see Schleyer et al
1970).
 -56°
Ho Ha
H
q6 C2
56
+56°
(56 4
He He 3
Ho
Ho He
Ha 2
-G2
-
() (la) (|b)
D3d
Ha-25|---Ha Ha251--Ha
pm pm
Hel+i°28') Ho

o--249-)
pm/249 pm He 249 pm
Ha Ha H¡
() (lla) (Wb)

Figure 10.1 Geometry of cyclohexane chair

the six carbon atoms alternately up (")and down (o) with signs of torsion angles"
between pairs of adjacent carbon atoms according to Klyne-Prelog convention.
2. Symmetry. The vertical axis passing through the centre of the chair is a C as
well as an Ss axis. In addition, there are three C; axes bisecting pairs of opposite
sides and also a centre of symmetry. Then there are three vertical o planes passing
through diagonal carbon atoms. The cyclohexane chair thus belongs to point group
D3o.
The symmetry number (o) is 6 counted thrice for 120° rotation around C3 and
once each for 180° rotation around the three C axis (see Chapter 2).
3. Equatorial and axial bonds. Two types ofC-H bonds are discernible in the
cyclohexane chair: six are distributed around the periphery of the ing making of the
alternately + 19° 28 and-19°28 angle with the horizontal plane C
vertical axis
molecule and the remaining six are approximately parallel with the structures (Ila)
again alternatively up and down as shown separately in the two
latter axial (a) bonds
and (IIb). The former are called equatorial (e) and the pairs of adjacent
(Barton et al 1953). The approximate distances between different than twice the van der
hydrogens are shown which are within 249-25lpm, greater
Waals radius of hydrogen (120 pm). Thus there isoccurno non-bonded interaction in the
twenty four times in the
cyclohexane chair and since these distances readily understood.
molecule, the stability of the chair conformation is
interaction between le,2e and le,2a substituents is kaown as 1,2-interaction
The 1,3-interaction or synaxial interaction, One
while that between la,3a is known as
interactions is that while the le.2e
significant difference between the two types of
involving four connected atoms have to be
*To designate a torsion angle, three bonds in succession care bonds. Ordinanly, the position of the
a, b. and
considered (Bucourt 1974), e.g., a, b. c where helpful
central bond, i.e., b is indicated. Models will be to understand the diagram (TO).
and le.2a bonds are skewed, the la.3a bonds are parallel. As a result, when H is
substituted by a bulkier group with longer bond length, the 1,2-interaction does
not increase in the same proportion as the I.3-interaction which is thus more
Severe.
4. Cis and trans isomerism. When two substituents are la,2a, they are
typically trans since the dihedral angle between them is 180°. By default.
substituents le.2e are also trans but the dihedral angle between them is approximately
60°. The cis orientation at the adjacent carbon atoms can be only le.2a or la.2e
with dihedral angle of 60° (more precisely 56°). It will be seen later that the trans
isomer exists mostly in the diequatorial conformation (le.2e). Thus in the
cyclohexane chair. there is very little difference between 1.2-cis and 1.2-trans
isomers as far as steric proximity is concerned. Considerable differences are.
however, realised in practice particularly in the ring-forming ability of the two cis
and trans groups which is explained on the basis that an attempt to bring le.2a
substituents (cis) in a plane flattens the ring reducing 1.3-interaction while such an
attempt on le,2e substituents pushes the axial groups inwards increasing 13
interaction considerably. Cis and trans isomerism in other disubstituted cyclohexanes
will be discussed later.

10.2.2 Ring inversion

The six axial and six equatorial protons form two sets of chemically non
equivalent (diastereotopic) nuclei with different chemical shifts in NMR. the axial
protons appearing at a slightly higher field (ca 0.4--0.5 ppm). However, the NMR
spectrum of cyclohexane at ambient temperature shows a sharp singlet which
means that the two sets of protons exchange sites at a rate faster than the NMR
time scale. The conformational change involved is known as ring inversion, ring
reversal, or flipping of the ring and is accompanied with the interchange of I-3-5
and 2-4-6 carbon planes leading to an inverted chair. No change in the relative
configuration ever occurs during the ring inversion, ie., substituents which are a
remain o and substituents which are B remain B; also cis remains cis and trans
remains trans: similarly. R centres remain R and likewise for S.
1. Conformational itinerary in chair inversion. The most obvious way a chair
can undergo inversion is through aplanar cyclohexane ring. However, this involves
a great deal of energy (> 125 kJ mol ') and is, therefore, very unlikely. According
to Hendrickson (1961. 1967), the most plausible transition sate is one (l11) in
which four carbon atoms lie in a plane with the other twoalternately above and
below the plane (Path A. Figure 10.2). The chair conformer may be suitably

*For simple cyclohexane itself. the ring inversion is a case of degenerate isonerisation since there is no
net change in the che mical structure a null reaction Such homomeric transfornatioas in which
identical ligands are interchanged between distinguisha ble chemical and/or magnetic enviroamens
have been given the general nane of topomerisation (Bnsch et al 197L). The nomenclature nay
urther be extended based on the topc relationship of the exchanging groups. Thus the exchange of
homotopic. enantiotop1c. and diastereotopic groups may be referred to as homo-. enanio-. and
dlaslereotopomerisations respectively. ln cyclohexane. the hydrogen atoms which interchange siles
are diastereolopic and the ring inversion process is a case of diastereolopomensa Uon.
 A
HB He
(la) (la)

HA
Hg HA

(Va)

1 cyclohexane

HA of
Pathway) Pathway)
itinerary

(V) Conformational
(C, (6
A B
Path Path
10.2
Figure

HA
(I) (V)

HA

() ()
twisted in the directions shown by the arrows to get the transition state (III), There
occurs extensive bond angle deformation accompanied by increased torsional
strain and the energy of the transition state is computed as 46.0 kJ mol which
agrees fairly wellwith that (42-43 kJ mol ) found experimentally (see later). The
transition state conformation (1I) has a C axis but no o plane and belongs to
point group C (chiral). Further change along the direction of the arrows leads to
the twist-boat' conformation (IV) which does not have any angle strain but suffers
from some residual torsional strain. Lying in a high energy valley, it corresponds to
an energy minimum (23 kJ mol with respect to the chair) and is actually a
conformer. Three such indistinguishable twist-boats are possible; they are inter
converted intoone another by pseudorotation. The conformer (IV) can either go
back to the original chair through the transition state (III) or be converted into the
inverted chair (a topomer of the original) equally well through the enantioneric
transition state (III'). This is shown in the energy diagram (A) in Figure 10.3 and
is called the C; path way, since the C axis of the ground state chair form is
retained along this pathway.
An alternative pathway (B in figure 10.2) is also possible in which the chair is
twisted to an envelope-like transition state (V) with five of the carbon atoms in a
plane and the sixth one either above or below it. According to calculation, its
energy is only slightly higher (ca 47.3 kJ mol') than the transition state (III) (ca
46.0 kJ mol ') and so this pathway cannot be entirely ruled out. Conformation
(V) has a o plane and so is achiral and leads directly to an energy minimum
conformation (VI) which is the clasical boat. The latter has a slightly higher
energy (by ca 3.7 kJ mol)more than the twist-boat and exists in three
interconvertible homomeric forms. The boat intermediate in its turn can go back to
the original chair or its topomer--through two equivalent transition states () and
(Va) respectively --with equal facility. Pathway Bmay be called a o pathway.
since both Vand VI retain the symmetry plane of the chair ground state. The
energy diagram is shown in Figure 10.3 by the dotted lines.

kJ mo+!
43 kJ 43kJ

A
3.7kJ
23kJ

Inversion coordinate

Flgure 10.3 Energy profile of ring inversion

 In principle, the two pathways (A and B) are mutually exclusive, i.e., the ring
inversion takes place either through a twist-boat or through a true boat. However,
once a twist-boat or a true boat is formed, they undergo interconversion through
Dseudorotation* before they are converted back into the chair forms. The entire
range of conformations between a true boat and a twist-boat are called flexible
forms and depending on the nature of substituents, one or the other may be
stabilised. The boat form is of slightly higher energy and may be regarded as the
transition state of the pseudorotation process. The twist-boat is of lowest energy
and the term flexible form generally refers to it (in contrast, the chair forms are
rigid conformers of cyclohexane not interconvertible' by pseudorotation). The
transition state in path A, ie., III is a half-chair while that in path B, iLe., Vis a
half-boat which also suggests that path A is energetically preferred.
2. The flexible conformers. The boat (B) and the twist-boat (TB) are the two
extremes of the flexible forms of cyclohexane. The boat conformation is shown in
three different perspectives in Figure 10.4. The conventional boat (VI) with a Ca
axis and two o planes (point group Czv)t shows the following types of bonds:
normalequatorial and axial at C-1 and C-4, designated linear (lin) and perpendi
cular (perp) respectively (one of the perp bonds is also designated flagpole,
abbreviated as fp and the other bowsprit abbreviated as bs), four boat-equatorial
(perp) (perp)
bs fp (e') -54°
H H(e)
lin

(')beq 2|beqle')
lin H +54°
b3 s
bax(a') bax(a') HH HH -54°
(a') (a')
(VI) C2v (Vla) (VIb)

tax tax iso t65 -3/°

iso. teq teg iso teq
-iso
iso iso
teq -teq
tax -31° t65
tax tax

(vI),D2 (Vla) (VIIb)

Figure 10.4 Geometry of flexible forms

Ihe term pseudorot ation was originally adopted by Pitzer to describe the rotation of the out-of-plane
dsplacements in a puckered cyclopentane ring. It is now used to describe a variety of conformational
Changes in cyclic systems which are low-energy processes and do not involve bond angle variations
but only changes intorsional strain and other non-bonded interactions, as in transformations of the
exible forms of cyclohexanes (but not the chair-chair interconversion) and interconversions of
mobile forms of higher cycloalkanes. The rotation is limited to an oscillation of dihedral angles
within certain limits without ever making a complete turn (180°).
Tmay be noted that symmetry has been reduced relative to the chair both in the boat and in the
twist boat.
(beg, or -e, or e') on C-2, C-3, C-5, and C-6 which are eclipsed in
boat -axial (bax,or -a, or a) on the same four carbon pairs,and four
atoms
The boat consists of four gauche butane and two eclipsed alsoeclipsed inpairs
butane units and the
strain may be computed as 4x3.3+2x18.0=F49.2 kJ mol
(minimum) or
4x3.3+2x26.0=65.2 kJ mol'(maximum). The difference in enthalpies between the
chair and boat forms is thus 29,4 kJ mol (minimum) or 45.4 kJ
mol
(maximum), the enthalpy of the chair being 19.8 kJ mol..In addition, the two
perpendicular H's at C-1 and C-4 is only 183 pm away giving rise to a non
bonded interaction, known as flagpole-bowsprit interaction. Structure Vla
the two eclipsed butane units in Newman projection and structure VIb shows
torsion angles according to Klyne-Prelog convention. shows the
If the fp and bs H's are pulled a little apart, the twist-boat results in
which the
fp-bs interaction is minimised and the conformation becomes more stable. It
belongs to point group D(3 XC) and is chiral. The different bonds are shown in
the structure (VII) in which tax, teg, and iso stand for twist-axial,
and isoclinal (the two geminal bonds are equivalent) respectively. twist-equatorial,
The
(VIla) shows one butane unit in Newman projection and the structurestructure (VIlb)
shows the torsion angles according to Klyne-Prelog convention. Although the
boats and twist-boats (flexible forms) are of high energy, they have favourable
entropy due to more degrees of freedom than the chair and the population of the
flexible form is approximately 1in 1000 at ambient temperature quite insufficient
for detection by physical methods.
3. Determination of barrier energy. The axial and equatorial protons of cyclo
hexane form two broad and complex (due to spin-spin coupling) bands in NMR at
- 100°C and below separated approximately by 0.45 ppm which
coalesce to a
broad singlet at -66.7°C (at 60 MHz). The free energy of activation (AG)as
determined by the coalescence temperature (Chapter 9) is found to be 42.2 +0.4
kJ mol (Jensen et al 1962). In order to avoid complexity due to spin-spin
coupling, cyclohexane-d11 (C%HD) has been used for variable temperature NMR
with deuterium-decoupling so that two sharp signals one due to the axial and the
other due to the equatorial proton are obtained (Figure 10.5a) at low temperature
(Anet et al 1967). The coalescence temperature is found to be-61.4C (at 60 MHz)
Corresponding to the free energy of activation of 43.2 kJ mol". A complete line
shape analysis (which requires measurements of line-widths at different temper
atures) gives the values of AH! and AST as 45.1 kJ mo' and 11.7 JK mol'
respectively. The large entropy of activation arises from the fact that the transition
state (as n) can adopt as many as six (three for simple cyclohexane) conformations
giving considerable amount of entropy of mixing. Substituents in the ring do not
Substantially raise the barrier energy and the usual range of barrier height is 42
50 kJ mol.
Anet et al (1975) heated cyclohexane to 800°C when
boat form rose to 25% and then suddenly cooled the the population of twist
iodide plate so that all the conformers were frozen*.sample to -253°C on a cesium
twist-boat-chair interconversion by IR, the free energyFrom the study of kinetics ol
of activation is found to be
*The procedure is known as matrix
separation ( see butadie ne ).
 ot-61.4'c/Tc
Ho
D
D D
D
D Hezi.7
D D
D D
D
D H)
60 MHz

Figure 10.5a Ring inversion of cyclohexane-d1

H

H H H H

(VI) (1X)

Figure 10.5b Energy of chair and boat forms

22 kJ mol which marks the position of the twist-boat conformer almost half-way
up the energy path to the transition state of chair-chair tonversion. The entropy of
activation is 16 JK mol'. The difference in enthalpies between a chair and twist
boat form of cyclohexane has also been determined (Margrave et al 1963) from
the heats of combustion of trans-syn-trans (VIII) (all-chair) and trans-anti-trans
(IX) (with the central ring as twist-boat) isomers of perhydroanthracenes (Figure
10.5b). By taking due consideration of the heat of vaporisation of each isomer
and the destabilising efect (ca 2.5 kJ mol') of the two terminal rings on the
flexible form, AH came up to a value of 20.1 kJ mol. The difference in free
energies of the twist-boat and the true boat has been computed by Hendrickson to
be around 3.7 kJ mol. All these values are shown in the energy profile diagram
(Figure 10.3).
10.2.3 Stabilisation of the flexible conformers

It is evident from the previous discussion that the chair form of cyclohexane is
ordinarily the most stable conformer. It may be understood, however, that to under
certain conditions the boat or the twist-boat can be stabilised in preference chair the
chair. In some molecules, the configurational requirement such is such that the
form is not possible, as in IX and X. Other factors as formation of
intramolecular H-bond (as in XI) or electronic effects (as in XII) also favour the
molecules
formation of the flexible conformers. Finally, structural features of someconformers.
torce them to exist exclusively in one or the other of the cyclohexane
fixation of boat form in
Examples are fixation of chair form in adamantane (XII), (Figure 10.6).
pentaasterane (XIV),and fixation of twist form in twistane (XV)
 H

CH3

(X) (X1) (X)

H

(X) (XIV) (XV)

Figure 10.6 Rigid molecules from cyclohexane conformers