Cyclohexanol and Cyclohexanone
Cyclohexanol and Cyclohexanone
Michael Tuttle Musser, E. I. Du Pont de Nemours & Co., Sabine River Laboratory, Orange, Texas 77631,
United States
1. Introduction . . . . . . . . . . . . . . . . .
2. Physical and Chemical Properties . .
3. Production . . . . . . . . . . . . . . . . . .
3.1. Hydrogenation of Phenol . . . . . . . .
3.2. Liquid-Phase Oxidation of Cyclohex-
ane . . . . . . . . . . . . . . . . . . . . . . .
3.3. Boric Acid Modified Oxidation of Cy-
clohexane . . . . . . . . . . . . . . . . . . .
3.4. Production and Hydration of Cyclo-
hexene . . . . . . . . . . . . . . . . . . . . .
3.5. Dehydrogenation of Cyclohexanol . .
4. Plant Safety . . . . . . . . . . . . . . . . .
5. Quality Specifications and Chemical
Analysis . . . . . . . . . . . . . . . . . . . .
1. Introduction
Cyclohexanol [108-93-0], C6 H11 OH, M r
100.16, is a colorless substance forming hygro-
scopic crystalline needles having a camphor-
like odor. It is very soluble in alcohols, ketones,
ethers, and alicyclic and aromatic hydrocarbons.
In its pure state, it melts near room temperature,
25.15 ◦ C. Cyclohexanone [108-94-1], C6 H10 O,
M r 98.15, is a colorless to pale yellow liquid
having an odor similar to that of acetone. It is
also very soluble in most organic solvents.
Both cyclohexanol and cyclohexanone are
produced on a large commercial scale. The vast
majority of these compounds and their mix-
tures is consumed in the production of capro-
lactam and adipic acid, intermediates in the
manufacture of nylon 6 and nylon 66 (→ Adipic
Acid; → Caprolactam; → 4. Fibers, Synthetic
Organic).
2. Physical and Chemical Properties
Physical Properties. The most important
physical properties of cyclohexanol and cyclo-
hexanone are shown in Table 1.

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
10.1002/14356007.a08 217
1
1 6. Storage and Transportation . . . . . . 7
1 7. Uses and Trade Names . . . . . . . . . . 7
2 8. Derivatives . . . . . . . . . . . . . . . . . . 7
2 8.1. Esters of Cyclohexanol . . . . . . . . . . 7
8.2. Cyclohexanone Oxime . . . . . . . . . . 8
3 8.3. Methylcyclohexanols and Methylcy-
clohexanones . . . . . . . . . . . . . . . . 8
4 8.4. Trimethylcyclohexanols and
Trimethylcyclohexanones . . . . . . . . 8
4 9. Economic Aspects . . . . . . . . . . . . . 10
6 10. Toxicology and Occupational Health . 10
6 11. References . . . . . . . . . . . . . . . . . . 11
7
Chemical Properties. Cyclohexanol under-
goes chemical reactions typical of secondary al-
cohols. It can esterify most organic acids or acyl
halides, whereas halogen acids convert the al-
cohol to the corresponding cyclohexyl halide.
Dehydration with sulfuric acid or vapor-phase
treatment with alumina at 300 – 400 ◦ C leads to
cyclohexene. Mild oxidation or catalytic dehy-
drogenation gives cyclohexanone. Stronger ox-
idizing agents, such as nitric acid, give a good
yield of adipic acid.
Cyclohexanone undergoes most of the reac-
tions expected of aliphatic ketones. At room
temperature, 0.02 % exists in the enol form
[1]. Cyclohexanone reacts with bisulfite to give
the addition product; it also reacts with hydro-
gen cyanide to give the cyanohydrin. It can be
hydrogenated to cyclohexanol and under more
vigorous conditions is further reduced to cyclo-
hexane. Reactions with chlorine or bromine lead
to substitution at either or both of the 2- and
6-positions. It readily undergoes base-catalyzed
Aldol condensation with itself or with other
aldehydes or ketones. The most important com-
mercial reactions of cyclohexanone are with hy-
droxylamine to give cyclohexanone oxime (an
intermediate on the way to caprolactam) and its
oxidation with nitric acid to give adipic acid.
2 Cyclohexanol and Cyclohexanone

3. Production hexanone facilities employ some form of cy-

clohexane oxidation technology. The only re-
Cyclohexanol and cyclohexanone were first pro- maining large phenol-based plants belong to
duced on an industrial scale by the hydrogen- DSM in Holland and Allied in the United States.
ation of phenol. This was followed in the 1940s Asahi has the only commercial cyclohexene-
by transition metal-catalyzed liquid-phase air based plant, and there are reports of planned
oxidation of cyclohexane, which gave a mixture expansions at that facility in Japan as well as
of cyclohexanol and cyclohexanone, the ratio of building a new plant in China.
which could be partially controlled by the choice
of metal catalyst. In the 1950s, Scientific Design
developed a boric acid modified liquid-phase air 3.1. Hydrogenation of Phenol
oxidation of cyclohexane. This process, in which
The product of phenol hydrogenation, i.e., cy-
the intermediate cyclohexyl hydroperoxide was
clohexanol, cyclohexanone, or a mixture of the
trapped as the peroxoborate ester, led to a higher
two, is determined by the metal catalyst. Cy-
yield and a higher ratio of cyclohexanol to cy-
clohexanol can be prepared in high yield by
clohexanone. Around 1990, Asahi commercial-
either vapor- or liquid-phase hydrogenation of
ized the production of cyclohexanol from cy-
phenol. Vapor-phase hydrogenation can be car-
clohexene, an intermediate obtained from the
ried out by using a supported nickel catalyst or
partial hydrogenation of benzene.
a nickel catalyst containing copper, cobalt, or
Table 1. Physical properties of cyclohexanol and cyclohexanone manganese. The support is usually alumina or
silicic acid. Yields as high as 98 % have been re-
Property Cyclo- Cyclo-
hexanol hexanone ported [2–5]. A flow diagram of the vapor-phase
hydrogenation is shown in Figure 1.
mp, ◦ C 25.15 −47
bp, ◦ C 161.1 156.4
Vapor pressure, kPa 0.15 (20 ◦ C) 0.52 (20 ◦ C)
0.48 (35 ◦ C)
d 20
4 0.9493 0.9455
n20
D 1.4656 1.4552
Expansion coefficient 8.25 × 10−4 9.14 × 10−4
Dynamic viscosity, mPa · s 41.07 (30 ◦ C) 1.803 (30 ◦ C)
17.20 (45 ◦ C)
Specific heat, J/g 1.747 1.811
Surface tension, mN/m 33.47 (30 ◦ C) 33.51 (30 ◦ C)
Heat of fusion, kJ/mol 1.791 1.501
Heat of combustion,
MJ/mol −3.722 −3.521
Heat of vaporization,
kJ/mol 45.51 44.92
Heat of formation, kJ/mol −352 −272
Flash point, ◦ C 68 54
Autoignition temp., ◦ C 300 420
Solubility at 20 ◦ C,
g of compound/100 g
of water 3.6 9.0
g of water/100 g
of compound 12.6 5.7
Figure 1. Vapor-phase phenol hydrogenation process
Azeotropes
With water: bp, ◦ C 97.8 96.6 a) Phenol evaporator; b) Hydrogenation reactor; c) Con-
composition, denser; d) Low-boiler removal column; e) Cyclohexanol/cy-
water : compound 80 : 20 56 : 44 clohexanone recovery column
With phenol: bp, ◦ C 183
composition, Hydrogenation of phenol to cyclohexanone
phenol : compound 87 : 13
can be carried out in the vapor phase with a
large variety of supported noble metal catalysts,
Cyclohexanone can be prepared by dehydro- including palladium, platinum, iridium, ruthe-
genation of cyclohexanol; the reverse reaction, nium, rubidium, and osmium. The hydrogen-
hydrogenation of cyclohexanone to cyclohex- ation is normally carried out at 140 – 170 ◦ C and
anol, is also practical although not commercially atmospheric pressure. Yields as high as 95 % at
practiced. Most large-scale cyclohexanol/cyclo- 100 % conversion can be obtained [6], [7].

Commercial liquid-phase hydrogenation of
phenol under mild conditions with a palladium
on carbon catalyst gives greater than 99 % yield
of cyclohexanone at 90 % conversion [8]. By ad-
justing the operating conditions and changing to
a Raney nickel catalyst, 99.9 % selectivity for cy-
clohexanol can be achieved [9]. Hydrogenation
conditions can be adjusted to produce the mix-
ture of cyclohexanol and cyclohexanone that is
preferred by adipic acid producers.
3.2. Liquid-Phase Oxidation of
Cyclohexane
The liquid-phase air oxidation of cyclohexane
[110-82-7] to cyclohexanol and cyclohexanone
was developed in the 1940s. The oxidation is
usually carried out, either uncatalyzed or with
a soluble cobalt catalyst, in a series of agitated
reactors at 140 – 180 ◦ C and at 0.8 – 2 MPa, al-
though a single tower oxidizer can be used [10],
[11]. The total residence time in the oxidizers is
15 – 60 min. Some of the initially formed cyclo-
hexyl hydroperoxide [766-07-4](Eq. 1) is con-
verted in the oxidizers to cyclohexanol, cyclo-
hexanone, and byproducts (Eq. 2).
C6 H12 + O2 −→ C6 H11 OOH (1)
3 C6 H11 OOH −→ 2 C6 H11 OH + C6 H10 O + H2 O + O2
+ byproducts (2)
The cyclohexanol to cyclohexanone ratio ex-
iting the air oxidizers can be altered by the
choice of catalyst used in the air oxidizer.
The normal cobalt-catalyzed air oxidation and

deperoxidation gives a cyclohexanol to cyclo-
hexanone ratio of about 3.5. If chromium(III)
is added to the air oxidizer, it appears to pro-
mote dehydration of cyclohexyl hydroperox-
ide to cyclohexanone and water, as opposed to
the free-radical decomposition mechanism of
cobalt, leading to a lower cyclohexanol to cy-
clohexanone ratio [12–14].
Because the intermediate cyclohexyl hy-
droperoxide and the products, cyclohexanol and
cyclohexanone, are more readily oxidized than
cyclohexane, the conversion of cyclohexane in
the air oxidizers must be kept low (usually under
6 %) to maximize yield. Depending on the con-
version, the total yield of alcohol, ketone, and
Cyclohexanol and Cyclohexanone 3
hydroperoxide varies from 70 to 90 %. Byprod-
ucts of the oxidation include a wide range of
mono- and dicarboxylic acids, esters, aldehydes,
and other oxygenated materials.
To maximize overall yield of cyclohexane to
the alcohol and ketone, most companies try to
maintain a high percentage of the oxidized cy-
clohexane leaving the oxidizers as cyclohexyl
hydroperoxide. To maximize the amount of cy-
clohexyl hydroperoxide leaving the air oxidiz-
ers, the oxidation can be carried out uncatalyzed
or with a modified catalyst that minimizes hy-
droperoxide decomposition in the oxidizer [15–
20]. This permits cyclohexyl hydroperoxide to
be decomposed into cyclohexanol and/or cyclo-
hexanone under milder conditions and in higher
yields than if it had occurred in the air oxidizer.
For example, the air oxidation product may
or may not be washed with water followed by
conversion of cyclohexyl hydroperoxide to cy-
clohexanol and cyclohexanone with a homoge-
neous or heterogeneous metal catalyst [21–35].
Another method of decomposing the hydroper-
oxide is to contact it with an aqueous caus-
tic phase containing a few parts per million of
cobalt, which decomposes the hydroperoxide in
high yield to the ketone and alcohol [36–41].
This caustic decomposition process can result
in a lower alcohol to ketone ratio in the final
product. A flow diagram of this caustic process
is shown in Figure 2.
Table 2. Ratio of cyclohexanol to cyclohexanone produced from
cyclohexyl hydroperoxide
Solution ∗ – Catalyst Tempera- Ratio ∗∗
Modification ture, ◦ C
A none 155 0.8
A Cr 155 0.4
A Ni 155 1.4
A V 155 1.4
A Co 155 3.0
A Mn 155 3.3
B Co 160 2.5
A – hydrogenation of 1 Pd 150 5 – 10
A – separate caustic
aqueous phase Co 120 0.2
∗ A = cyclohexyl hydroperoxide (1) in cyclohexane; B = 1 in air
oxidizer tails.
∗∗ Cyclohexanol : cyclohexanone.
Several patents report that cyclohexyl hy-
droperoxide in the oxidizer effluent can be hy-
drogenated in high yield to cyclohexanol [42–
47].
4 Cyclohexanol and Cyclohexanone
Figure 2. Cyclohexane oxidation/caustic decomposition process
a) Air oxidizers; b) Water wash decanter; c) Decantation; d) Caustic decomposition reactor; e) Caustic decantating; f) Cyclo-
hexane recovery column; g) Cyclohexanol/cyclohexanone recovery column
Table 2 shows the cyclohexanol to cyclohex-
anone ratio that can be obtained by using a range
of conditions and a variety of hydroperoxide
decomposition methods.
3.3. Boric Acid Modified Oxidation of
Cyclohexane
In the 1950s, Scientific Design (now Halcon In-
ternational) developed a process in which anhy-
drous metaboric acid [13460-50-9]was added as
a slurry to the first of several staged air oxidation
vessels (see Figure 3) [48], [49]. The cyclohexyl
hydroperoxide formed is trapped as the cyclo-
hexyl perborate ester (Eq. 3). The perborate es-
ter then reacts with additional cyclohexane in
the air oxidizer to yield the borate ester and ad-
ditional cyclohexanol (Eq. 4). This borate ester
is relatively stable in the air oxidizer and is pro-
tected from over oxidation to ring-opened prod-
ucts. The ester is subsequently hydrolyzed to cy-
clohexanol and boric acid [10043-35-3](Eq. 5).
The boric acid is dehydrated to metaboric acid
and is recycled to the air oxidizer (Eq. 6).
18 C6 H12 + 9 O2 + 2 H3 B3 O6 −→ 6 B(OOC6 H11 )3
+ 12 H2 O (3)
B(OOC6 H11 )3 + 3 C6 H12 −→ B(OC6 H11 )3
+ 3 C6 H11 OH (4)
B(OC6 H11 )3 + 3 H2 O −→ 3 C6 H11 OH + H3 BO3 (5)
3 H3 BO3 −→ H3 B3 O6 + 3 H2 O (6)
The chemistry of this process is very similar
to the metal-catalyzed oxidation except that the
cyclohexyl rings are protected from further at-
tack. Compared to other commercial processes,
the boric acid process is characterized not only
by a higher investment and a higher operating
cost (to recover and recycle the boric acid), but
also by a higher yield of cyclohexanol and cy-
clohexanone (up to 88 %) and an alcohol to ke-
tone ratio as high as 10 : 1. The technology was
further developed by Institut Français du Pétrole
[50], [51]. The Halcon process has been licensed
to several companies around the world. The ma-
jor producers using this technology today are
Solutia, DuPont (UK), Bayer, and Mitsubishi.
The original plant at Rhône-Poulenc, based on
this technology, was now shut down.
3.4. Production and Hydration of
Cyclohexene
In 1972 the first patent covering the selec-
tive hydrogenation of benzene [71-43-2] to cy-
clohexene [110-83-8] appeared [52]. Shortly
thereafter, two patents described the hydration
of cyclohexene to cyclohexanol by using various
catalysts [53], [54]. Since then, a large number
of patents have appeared worldwide. In 1990,
Asahi commercialized this process with a 100 t/a
 Cyclohexanol and Cyclohexanone 5

Figure 3. Boric acid modified oxidation of cyclohexane

a) Air oxidizers; b) Ester hydrolysis vessel; c) Decanter; d) Extraction column; e) Cyclohexane recovery column; f) Refining
column; g) Stripping column; h) Vaccuum crystallizer; i) Boric acid centrifuge; j) Boric acid slurry tank; k) Dehydrator

Figure 4. Partial hydrogenation of benzene to cyclohexene, followed by hydration to cyclohexanol

a) Benzene purification; b) Partial hydrogenation; c) Separation of unconverted benzene from cyclohexene and cyclohexane;
d) Separation of cyclohexene from cyclohexane; e) Separation of cyclohexene from extractive solvent; f) Hydration of cy-
clohexene; g) Recycle of unconverted cyclohexene; h) Purification of cyclohexanol

plant in Japan. The process involves three pri-
mary steps: the selective hydrogenation of ben-
zene; the separation of the cyclohexene from
the unconverted benzene and the over-hydrogen-
ation product cyclohexane; and the hydration of
the cyclohexene (Fig. 4).
The hydrogenation is carried out with a spe-
cially prepared heterogeneous nickel catalyst.
The reaction is run to about 50 % conversion, at
which point the product consists of about 35 %
cyclohexene, 15 % cyclohexane, and 50 % un-
converted benzene. The selectivity is very sen-
sitive to impurities such as sulfur and iron. For
this reason the benzene must be specially puri-
fied and the hydrogenation vessel lined with an
inert material [55–58].
The mixture of cyclohexane, cyclohexene,
and benzene can not be distilled but must go
through two successive extractive distillations.
The best solvent to use in these distillations has
been the subject of numerous patents [59–62].
The recovered cyclohexane could be converted
back to benzene, but is probably sold to other
caprolactam and adipic acid manufacturers.
The hydration of cyclohexene is also per-
formed with a heterogeneous catalyst in a slurry
6 Cyclohexanol and Cyclohexanone
reactor. The extent of hydration is limited by the
equilibrium constant, which would restrict con-
version to about 14 %. The use of several addi-
tives to increase the conversion of cyclohexene
to cyclohexanol has also been patented [63–68].
The yield of this process from benzene
to cyclohexanol is extremely high, probably
greater than 95 %. Although byproducts are not
a concern, the investment is significantly higher
than that of a conventional cyclohexane oxida-
tion plant. The fact that the product is cyclohex-
anol, not cyclohexanone, could make it unattrac-
tive as the basis for a caprolactam plant.
3.5. Dehydrogenation of Cyclohexanol
Cyclohexanol can be dehydrogenated to cyclo-
hexanone (the desired starting material for
caprolactam manufacture) without catalyst by
passing the vapors through a tube furnace at
400 – 450 ◦ C. The vapors are cooled, the hydro-
gen separated, and the cyclohexanone, which
contains cyclohexene and water, is purified in
a distillation column. The purity of the resulting
cyclohexanone is 98 – 99 % [69–72].
The catalytic dehydrogenation, which is gen-
erally practiced, can be carried out under milder
conditions and in better yield over a variety
of catalysts, including chromium oxide – copper
[73], copper chromate [74], nickel [75], [76],
zinc sulfide, and zinc – iron catalyst [77–79],
cobalt carbonate [80], and other metals [81].
4. Plant Safety
The major industrial hazard associated with pro-
ducing cyclohexanol and cyclohexanone is ox-
idation of cyclohexane at elevated temperature
and pressure. Inside the air oxidation unit, the
vapor is usually too rich in fuel (cyclohexane) to
be explosive. However, in the air inlet piping, an
explosive mixture can result if hot cyclohexane
backs up into this system. Some of the solids
formed in the oxidation, usually called  coffee
grounds, can be pyrophoric. At least one inci-
dent occurred in which the air sparger, entering
the oxidizer, was observed to be  glowing red,
indicating a fire inside the sparger. An incident
of a fire inside an oxidizer at the sparger nozzles
has been reported by ICI.
A sudden release of the hot cyclohexane to
the atmosphere, (e.g., from the rupture of a pro-
cess line or a break in the air oxidation vessel it-
self) results in an extremely hazardous situation.
An incident of this type occurred at a Monsanto
plant at Pensacola, Florida in 1971. Fortunately,
the resulting vapor cloud was dispersed by the
prevailing winds before it could ignite.
In 1974, a much more serious incident oc-
curred at a Nipro plant in Flixborough, England.
A section of 50-cm pipe connecting two air ox-
idation vessels ruptured, resulting in the release
of a large cloud of cyclohexane vapor. About
30 s after the break occurred, the vapor cloud ig-
nited, and the resulting explosion destroyed the
plant. A total of 28 lives were lost.
5. Quality Specifications and
Chemical Analysis
High-grade commercial cyclohexanol, usually
obtained from hydrogenation of phenol, has the
following specifications:
mp 19 – 23 ◦ C
bp 159 – 162 ◦ C
Water content 0.1 %
Phenol content 0.0001 %
The best analytical method for cyclohex-
anol is gas chromatography with Carbowax
20M on Chromosorb. Common impurities, such
as cyclohexane, cyclohexanone, phenol, pen-
tanol, and benzene, do not interfere. Cyclohex-
anol can be characterized as the 4-nitrobenzoyl
derivative, mp 52 ◦ C. It can be determined
colorimetrically by using a solution of 4-
hydroxybenzaldehyde in sulfuric acid [82]. The
preferred acylating agent for microscale quanti-
ties is acetic anhydride [83].
Commercial cyclohexanone is available in
several grades. A typical material is colorless to
pale yellow, contains 98 – 99 % cyclohexanone
and 0.2 % water, and has a boiling range of
151 – 157 ◦ C.
Cyclohexanone, like cyclohexanol, is best
analyzed by using a Carbowax 20M on Chro-
mosorb gas chromatography column. Cyclohex-
anone can be characterized as the oxime (mp
90.5 ◦ C), the semicarbazone (mp 167 ◦ C), or the
nitrophenylhydrazone (mp 146 ◦ C). It can be

quantitatively determined by reaction with hy-
droxylamine hydrochloride, followed by basic
titration of the hydrogen chloride that is liber-
ated [84], [85].
6. Storage and Transportation
Cyclohexanol and cyclohexanone are not corro-
sive to iron or steel and can be stored or trans-
ported in drums, tank trucks, or tank cars. An
inert gas (nitrogen) blanket is not required. The
U.S. DOT classifies both cyclohexanol and cy-
clohexanone, or mixtures thereof, as hazardous
flammable liquids. For transportation, they must
be labeled flammable and marked Hazard Level
III [86]
7. Uses and Trade Names
Cyclohexanol has numerous industrial ap-
plications, the major two being as an interme-
diate in the production of adipic acid (for use
in nylon 66) and cyclohexanone, which is then
converted to caprolactam (the monomer for ny-
lon 6). The U.S. market for refined cyclohex-
anol, other than as a nylon intermediate was
10 × 103 t in 1992 [87]. The major uses are:
1) As a solvent for lacquers, varnishes, oils,
alkyd resins, gums, shellacs, ethyl cellulose,
acid dyes, and natural resins
2) In the preparation of esters for plasticizers,
e.g., dicyclohexyl phthalate
3) In the laundry industry and in soaps and syn-
thetic detergents as a homogenizer and sta-
bilizer
4) In paint and varnish removers
5) In the insecticide, fragrance, polish, and rub-
ber cement industries
Trade names: Cyclohexyl Alcohol,
Hexahydrophenol, Hydrophenol, Hexalin, and
A.
Cyclohexanone. Over 97 % of all cyclohex-
anone produced is oxidized to adipic acid or con-
verted to cyclohexanone oxime, which is then
rearranged with sulfuric acid to caprolactam.
Other uses for cyclohexanone include thinner or
solvent for synthetic resins, polymers, and lac-
quers. It is also used as a starting material in the
Cyclohexanol and Cyclohexanone 7
synthesis of many insecticides, herbicides, and
pharmaceuticals, as well as being a good solvent
for many insecticides.
Trade names: Hexanon, Hydrol-O, Sextone,
Pimelic Ketone, Ketohexamethylene, and K.
8. Derivatives
8.1. Esters of Cyclohexanol
Numerous esters of cyclohexanol are of com-
mercial significance, the more important be-
ing dicyclohexyl phthalate, dicyclohexyl adi-
pate, and cyclohexyl acrylate.
Dicyclohexyl phthalate [84-61-7], C20 H26
O4 , M r 330.45, mp 65 ◦ C, bp 218 ◦ C (0.6 kPa),
d 20 1.148. This diester is normally prepared
from the reaction of phthalic anhydride with cy-
clohexanol in an inert solvent like toluene at ca.
130 ◦ C.
Dicyclohexyl phthalate is used as a plasticizer
to modify the properties of synthetic resins, in
alkyd resins and cellulose nitrate to increase their
stability to light and weathering, and to improve
the chemical and physical properties of plastics
by preventing creep. It is very stable to heat and
light and imparts a glossy finish to extruded ma-
terials. It is also used in paper finishes and makes
printers ink water-resistant.
Dicyclohexyl adipate [849-99-0], C18 H30
O4 , M r 294.50, mp 35.5 ◦ C, bp 324 ◦ C, d 20
1.037, n20 1.4720.
This diester can be prepared by esterification
of adipic acid, transesterification of dimethyl
adipate, or direct reaction of adipic acid with cy-
clohexene [65]. It is used as a plasticizer in vinyl
copolymers, polystyrene, and paints. A patent
indicates that it can be oxidized in high yield to
adipic acid [88].
8.2. Cyclohexanone Oxime
Cyclohexanone oxime [100-64-1], C6 H10 NOH,
Mr 113.16 , mp 90.5 ◦ C, bp 204 ◦ C, sublimes at
room temperature (0.6 kPa); it is a white crys-
talline solid that can be crystallized as prisms
from hydrocarbon solvents. This compound is
8 Cyclohexanol and Cyclohexanone
the most important commercial derivative of cy-
clohexanone. It can be prepared by warming
cyclohexanone with an aqueous mixture of hy-
droxylamine hydrochloride and sodium bicar-
bonate. The oxime undergoes a Beckmann re-
arrangement in the presence of sulfuric acid to
give caprolactam.
Large commercial quantities of cyclohex-
anone oxime are used in the preparation of
caprolactam, the intermediate for the prepara-
tion of nylon 6. The cyclohexanone oxime can
also be reduced to a mixture of cyclohexylamine
and dicyclohexylamine or it can hydrolyzed to
cyclohexanone.
8.3. Methylcyclohexanols and
Methylcyclohexanones
Methylcyclohexanol, CH3 C6 H10 OH, M r
114.19, is usually available as a mixture of the
cis and trans isomers of 2-, 3-, and 4-methylcy-
clohexanol. These derivatives are prepared by
hydrogenation of individual or mixed cresols.
Table 3 gives the physical properties of the indi-
vidual isomers and of a commercial mixture.
The commercial mixture is a colorless liq-
uid and is used as a solvent for resins, oils, and
waxes, as a blending agent in soaps, and as an
antioxidant in lubricants [89], [90].
Methylcyclohexanone is normally sold as a
mixture of three isomers (2-, 3-, and 4-methylcy-
clohexanone). The individual isomers can be
isolated; their physical properties, along with
those of a commercial mixture, are listed in Ta-
ble 3.
Methylcyclohexanones can be prepared by
mild oxidation of the corresponding alcohols or
by direct hydrogenation of cresol in a process
similar to the hydrogenation of phenol to cyclo-
hexanone.
The technical-grade commercial mixture
contains all three isomers. At 20 ◦ C its solubil-
ity in water is 1.5 %, and 3 % water is soluble
in the methylcyclohexanones. Methylcyclohex-
anones are used as solvents in the dye and resin
industries.
8.4. Trimethylcyclohexanols and
Trimethylcyclohexanones
3,3,5-Trimethylcyclohexanol (2), C6 H18 O,
Mr 142.23, is a colorless, crystalline material,
which is commercially produced as a mixture
of the cis and trans isomers. The individual iso-
mers can be separated by careful distillation or
crystallization.
The physical properties of the two isomers
are: cis isomer [933-48-2], mp 37.3 ◦ C, n60
1.4390, d 60 0.860, vapor pressure 1.3 kPa (at
86 ◦ C), flash point 88 ◦ C, solubility in water
0.19 % (at 60 ◦ C), water solubility in alcohol
4.0 % (at 60 ◦ C); trans isomer [767-54-4], mp
57.3 ◦ C, n60 1.4390, d 60 0.862, vapor pressure
1.3 kPa (at 76 ◦ C), flash point 76 ◦ C, solubility
in water 0.17 % (at 60 ◦ C), water solubility in
alcohol 2.6 % (at 60 ◦ C).
Trimethylcyclohexanol (2) is miscible in
all proportions with most organic solvents. It
is a cyclic alcohol with similar properties to
cyclohexanol. Oxidation of trimethylcyclohex-
anol with nitric acid gives a mixture of 2,2,4-
trimethyladipic acid and 2,4,4-trimethyladipic
acid. Trimethylcyclohexanol is prepared by
hydrogenating 3,5,5-trimethyl-2-cyclohexen-1-
one [78-59-1] (1), isophorone (a condensation-
product of acetone).
The best catalyst for the hydrogenation is nickel
or a mixture of nickel and copper on either silica
gel or alumina. The hydrogenation is carried out
in high yield at 120 – 200 ◦ C and 1 – 2 MPa. The
byproducts of the reaction are small amounts of
 Cyclohexanol and Cyclohexanone 9
Table 3. Physical properties of methylcyclohexanols and methylcyclohexanones

Isomer CAS registry mp, ◦ C bp, ◦ C d 20 n Flash

number point, ◦ C

Methylcyclohexanols
dl-cis-2-Methylcyclohexanol [7443-70-1] 7 165.2 0.934
dl-trans-2-Methylcyclohexanol [7443-52-9] −4 166.5 0.924
d-cis-3-Methylcyclohexanol [5454-79-5] −4.7 174.0 0.917
l-trans-3-Methylcyclohexanol [7443-55-2] −1 175.0 0.915
cis-4-Methylcyclohexanol [7731-28-4] −9.2 174.0 0.912
trans-4-Methylcyclohexanol [7731-29-5] 173.0 0.916
Commercial mixture [25639-42-3] −50 173 – 175 0.913 154
Methylcyclohexanones
dl-2-Methylcyclohexanone [583-60-8] −13.9 165.1 0.925 1.4440 48
(25 ◦ C)
dl-3-Methylcyclohexanone [591-24-2] −73.5 170.0 0.920 1.4449 48
(20 ◦ C)
4-Methylcyclohexanone [589-92-4] −40.6 171.3 0.916 1.4451 48
(20 ◦ C)
Commercial mixture [1331-22-2] 165 – 171 0.918 – 0.925

trimethylcyclohexanone, trimethylcyclohexane, water 0.3 %, water in ketone 1.4 %. It is miscible

and trimethylcyclohexene. in all proportions with most organic solvents.
The most important use for the alcohol Trimethylcyclohexanone (3) is also prepared
is as a feedstock for trimethyladipic acid by hydrogenating trimethylcyclohexenone (2).
[93–97]. This mixture of 2,2,4-trimethyladipic However, the olefin hydrogenation can be car-
acid [3586-39-8]and 2,4,4-trimethyladipic acid ried out without hydrogenating the ketone
[3937-59-5], is used in the manufacture of plas- by using a palladium-supported catalyst at
ticizers and lubricants, and can be converted to 110 – 170 ◦ C and 0.2 – 6 MPa [98]. The com-
dinitriles, diamines, or glycols. Other uses for bination of catalyst, reaction conditions, and
trimethylcyclohexanol are as replacement for amount of hydrogen determines whether the ke-
cyclohexanol in polishes and waxes. Because of tone or alcohol is produced.
its lower vapor pressure and unique structure, Trimethylcyclohexanone is a good solvent
trimethylcyclohexanol is better than cyclohex- for low molecular mass poly(vinyl chloride)-
anol in varnishes and shellacs. type alkyd resins and for nitrocellulose. It can
The trimethylcyclohexanol that is sold com- be used in place of methylcyclohexanone, where
mercially is a mixture of the cis and trans iso- its higher boiling point results in superior per-
mers. Analysis of a typical commercial prod- formance in some applications.
uct indicates 98 % trimethylcyclohexanols, 1 %
trimethylcyclohexanone, 0.4 % trimethylcyclo-
hexane, 0.3 % trimethylcyclohexene, 0.1 % 9. Economic Aspects
isophorone, and 0.2 % water.
Trimethylcyclohexanol can be stored and The quoted price for technical-grade cyclohex-
transported in iron or steel drums, containers, anol in February 1999 was $ 1.83/kg [99] as
tank cars, or tank trucks. It is stable indefinitely
compared to $ 1.32/kg in 1986 [100]. U.S. sales
and does not need to be blanketed with an inert of cyclohexanol in 1992 were about 10 × 103 t
gas. [87], up from 4.3 × 103 t in 1971 [101]. The re-
maining Western world sales were believed to
3,3,5-Trimethylcyclohexanone (3) [873-94-9], be about half of the U.S. sales.
C6 H16 O, Mr 140.24, is a colorless liquid hav- In 1992, U.S. non-adipic acid, non-capro-
ing properties similar to those of cyclohexanone. lactam sales of cyclohexanone were about
It has the following physical properties: mp – 20 × 103 t, up from 15 × 103 t in 1970 [101].
◦ ◦ 20 20
10 C, bp 188.8 C, d 0.888, n 1.4455, flash The early 1999 cost of technical-grade cyclo-
point 72 ◦ C, solubility (at 20 ◦ C) of ketone in hexanone was $ 1.61/kg [99], whereas the quote
10 Cyclohexanol and Cyclohexanone
for the same material in November 1986 was
$ 1.25/kg [100].
This sales volume for either chemical does
not represent capacity, as the vast majority of
both are consumed within the manufacturing
companies to make adipic acid or caprolactam.
In 1992, the worldwide capacity for cyclo-
hexanol-cyclohexanone manufacture was about
3.2 × 106 t. Of that total, about 58 % was used
for caprolactam manufacture, 40 % for adipic
acid manufacture, and the remainder was sold
for other uses.
10. Toxicology and Occupational
Health
Cyclohexanol and cyclohexanone are mod-
erately toxic [102], but have no apparent car-
cinogenicity. For cyclohexanol the OSHA TLV
for exposure to vapor for 8 h is 50 ppm [103].
The ACGIH has established TLV-TWA values
for exposure to cyclohexanol vapor of 50 ppm,
200 mg/m3 [104]. The TLV-TWA for cyclohex-
anone is 25 ppm, 100 mg/m3 . The MAKs for
both compounds are 50 ppm, 200 mg/m3 .
Excessive exposure to vapor of either chem-
ical results in irritation to the eyes, nose, and
throat. Exposure of animals to a high concentra-
tion of cyclohexanol vapor resulted in irritation,
lacrimation, salivation, lethargy, incoordination,
narcosis, mild convulsions, and, in some cases,
death. Degenerative changes were noted in the
brain, kidney, and liver of rabbits exposed re-
peatedly to high vapor concentrations of cyclo-
hexanol [102].
Exposure of animals to high concentrations
of cyclohexanone vapor also resulted in irri-
tation, lacrimation, and salivation. Decreased
heart rate and depression of the CNS were also
noted [105]. Degenerative changes were noted
in the kidney and liver of monkeys and rabbits
exposed repeatedly to high vapor concentrations
of cyclohexanone.
For single dosages of cyclohexanol, the oral
LD50 for rats is 2.06 g/kg [106] and the min-
imum lethal dose for rabbits is 2.4 g/kg [92].
With cyclohexanone, the oral LD50 for rats is
1.62 g/kg [107] and the minimum lethal dose for
rabbits is 1.6 – 1.9 g/kg [92].
Cyclohexanol and cyclohexanone are moder-
ately irritating to the eye and can cause corneal
injury [107], [108]. Cyclohexanol can be ab-
sorbed through the skin in toxic amounts, and
extensive exposure can cause tremors, narcosis,
hypothermia, and death [92]. Cyclohexanone is
only moderately irritating to the skin. Defatting
and dermatitis of the skin occurred when animals
were exposed for long periods of time [109].
Derivatives. Commercial methylcyclohex-
anol is low in toxicity, and the ACGIH has
set TLVs of 75 ppm, 350 mg/m3 (STEL) and
50 ppm, 235 mg/m3 (8-h TWA). The MAK value
is the same as the TLV/TWA value [91]. Exces-
sive exposure causes headaches and eye and
nose irritation.
Methylcyclohexanones are moderately toxic
to laboratory animals and cause eye, nose,
and throat irritation; they have produced
corneal damage to the eyes of rabbits. The
single-dose oral LD50 for rats is ca. 2 g/kg
[92]. 2-Methylcyclohexanone may be absorbed
through the skin. Its TLV/TWA and MAK are
50 ppm, 230 mg/m3 ; the TLV/STEL is 75 ppm,
345 mg/m3. .
Trimethylcyclohexanol has the same toxico-
logical properties as methylcyclohexanol, but
because of its lower vapor pressure, it presents
fewer hazards. Neither TLV nor MAK values
have been adopted.
The toxicity of trimethylcyclohexanone is
similar to that of methylcyclohexanone, but its
lower vapor pressure makes it less dangerous to
handle.
11. References
1. G. Schwarzenbach, E. Felder, Helv. Chim.
Acta 27 (1944) 1044. G. Schwarzenbach, C.
Witwer, Helv. Chim. Acta 30 (1947) 659, 669.
2. BASF, DE 352 439, 1913.
3. Tetralin Ges., DE 299 012, 1916.
4. Chem. Tech. (Leipzig) 18 (1966) no. 10,
608 – 613.
5. Stamicarbon, US 3 305 586, 1967 (P. Bernard).
6. Stamicarbon, GB 890 095, 1960.
7. G. D. Lyubarskii, G. K. Kervalishvili, Khim.
Promst. (Moscow) 7 (1972) 491.
8. Allied Chemical Corp., US 4 092 360, 1978
(J. F. van Peppen, W. B. Fisher).
9. Allied Chemical Corporation, US 5 015 787,
1991 (J. F. van Peppen).
 Cyclohexanol and Cyclohexanone
10. Du Pont, US 3 530 185, 1970 (K. Pugi).
11. Du Pont, US 3 957 876, 1976 (M. Rapoport,
J. O. White).
12. Union Carbide, US 3 404 185, 1968 (T.
Adams).
13. Celanese, US 3 598 869, 1971 (P. J. Volpe,
W. J. Humphrey).
14. Du Pont, US 3 987 100, 1976 (W. J. Barnett,
D. L. Schmitt, J. O. White).
15. Rhône-Poulenc, US 3 510 526, 1970 (J. P. M.
Bonnart, Y. Bonnet, P. P. M. Rey).
16. Arco, US 3 949 004, 1976 (H. A. Sorgenti,
S. N. Rudnick).
17. Rhône-Poulenc, BE 731 125, 1969.
18. Arco, GB 1 335 296, 1973 (H. A. Sorgenti,
S. N. Rudnick).
19. Du Pont, US 4 675 450, 1987 (J. B. Lyon, G. T.
Stowe).
20. Monsanto, US 3 260 742, 1966.
21. Du Pont, US 2 851 496, 1958 (H. L. Cates,
R. W. Wheatcroft, A. B. Stiles, J. O.
Punderson).
22. Rhône-Poulenc, US 3 925 316, 1975 (J-C.
Brunie, N. Crenne, F. Maurel).
23. Rhône-Poulenc, US 3 923 895, 1975 (M.
Constantini, N. Crenne, M. Jouffret, J.
Nouvel).
24. Rhône-Poulenc, US 3 928 452, 1975 (J-C.
Nouvel, M. Costantini, N. Crenne, M.
Jouffret).
25. Rhône-Poulenc, US 3 927 105, 1975 (J-C.
Brunie, N. Crenne).
26. Stamicarbon (DSM), US 3 941 845, 1976 (W.
Vvoskuil, J. J. M. van der Donck).
27. Stamicarbon (DSM), US 3 987 101, 1976 (J.
Wolters, J. L. J. P. Hennekens).
28. Stamicarbon (DSM), US 4 042 630, 1977 (J.
Wolters, J. L. J. P. Hennekens).
29. Du Pont, GB 777 087, 1957.
30. Rhône-Poulenc, BE 715 662, 1968.
31. Rhône-Poulenc, GB 1 229 734, 1971 (J-C.
Brunie, N. Crenne).
32. Rhône-Poulenc, US 3 923 895, 1975 (M.
Constantini, N. Crenne, M. Jouffret, J.
Nouvel).
33. Du Pont, US 4 326 084, 1981 (J. D. Druliner,
P. J. Krusic, S. D. Ittel, C. Tolman).
34. Du Pont, US 4 503 257, 1985 (J. D. Druliner,
J. Hermolin).
35. DSM, US 5 298 665, 1992 (H. A. C. Baur,
Hoogendoorn, Janssen, Ragten).
36. Phillips, US 2 931 834, 1960 (W. W. Crouch,
J. C. Hillyer).
37. BASF, GB 1 382 849, 1975 (O. A. Grosskinsky,
G. Herrmann, R. Kaiser, A. Kuessner).
11
38. Stamicarbon (DSM), US 4 238 415, 1980
(W. O. Bryan).
39. Stamicarbon (DSM), EP 0 004 105, 1979
(W. O. Bryan).
40. DSM, CA 1 244 475, 1983 (Housmans,
Vannispen, Plantema).
41. DSM, EP 659 776, 1995 (H. A. C. Baur, U. F.
Kragten).
42. Rhône-Poulenc, US 3 557 215, 1971 (J. P. M.
Bonnart, Y. Bonnet, P. P. M. Rey).
43. Rhône-Poulenc, US 3 694 511, 1972 (J.
Nouvel).
44. Stamicarbon (DSM), US 3 927 108, 1975
(C. G. M. van der Moesdijk, A. M. J. Thomas).
45. Stamicarbon (DSM), US 3 937 735, 1976
(P. L. M. Dois).
46. Rhône-Poulenc, GB 1 221 629, 1971 (J.
Nouvel).
47. DuPont, US 4 720 592, 1988 (U. N. Besmar, J.
B. Lyon, F. J. Miller, M. T. Musser).
48. Halcon, US 3 317 614, 1967 (W. C. Long).
49. Halcon, US 3 665 028, 1972 (J. L. Russell).
50. Institut Français du Pétrole, FR 1 556 979,
1969 (J. Alagy, A. Zuech, B. Cha).
51. Institut Français du Pétrole, FR 1 573 834,
1969 (J. Alagy, L. Asselineau, C. Busson, B.
Cha).
52. Du Pont, BE 782 721, 1972 (W. C. Drinkard).
53. BASF, DE 2 124 590, 1972 (R. Platz, W.
Fuchs, C. Dudeck).
54. Ube Industries, JP 7 809 746, 1978 (T.
Kawahito, M. Tamure).
55. Asahi, JP 60 255 738, 1985 (H. Nagahara, Y.
Fukuoka).
56. Asahi, JP 90 016 736B, 1990.
57. Bayer, DE 4 414 328, 1995 (H. Fiege, H.
Haerle, A. Klausener).
58. Sumitomo, US 4 665 274, 1987.
59. Asahi, JP 61 221 134, 1985 (Y. Fukuoka, O.
Mitsui).
60. DSM, US 4 927 974, 1989 (van den Brink, van
Geem).
61. Sumitomo, JP 62 126 139, 1987.
62. Sumitomo, JP 62 123 136, 1987.
63. Asahi, EP 162 475, 1985 (M. Tojo, O. Mitsui).
64. Asahi, JP 63 154 636, 1988 (O. Mitsui, H.
Goto).
65. Du Pont, US 5 321 155, 1994 (W. C. Drinkard,
G. C. Grunewald).
66. Sumitomo, US 4 691 064, 1987.
67. Sumitomo, US 4 716 253, 1987 (T. Shirafuji,
K. Sakai, K. Hirose).
68. Sumitomo, US 4 670 612, 1986.
69. F. Andreas, Chem. Tech. (Leipzig) 18 (1966)
no. 10, 608.
12 Cyclohexanol and Cyclohexanone

70. J. W. Bruce, Ind. Chem. 1963, no. 3, 121.
71. Scientific Design, BE 598 094, 1960.
72. Monsanto, US 2 970 172, 1959 (D. R. Cova).
73. Wingfoot Corp., US 2 218 457, 1937 (C. F.
Winans).
74. Du Pont, US 2 163 284, 1937 (W. A. Lazier).
75. Monsanto, US 2 970 172, 1959 (D. R. Cova).
76. L. K. Filippenko, K. N. Belonogov, V. P.
Gostikin, Izv. Vyssh. Uchebn. Zaved. Khim.
Tekhnol. 13 (1970) 3.
77. F. Laucht, US 2 338 445, 1939.
78. I. G. Farben, DE 743 004, 1940 (F. Laucht, O.
Klopfer).
79. K. Smeykal, H.-J. Naumann, Chem. Tech.
(Leipzig) 13 (1961) no. 3, 132.
80. Allied Signal Corporation, US 3 974 221, 1976
(J. Duggan).
81. BASF, US 3 149 166, 1964 (G. Poehler, A.
Wegerich, H. Giehne, O. Goerhre).
82. S. D. Nogare, J. Mitchell, Jr., Anal. Chem. 25
(1953) 1376.
83. N. A. Cheronics, T. S. Ma: Organic Functional
Group Analysis by Micro and Semimicro
Methods, Interscience, New York 1964,
pp. 493 – 496.
84. J. Mitchell, Jr., D. M. Smith, W. M. D. Bryant,
J. Am. Chem. Soc. 63 (1941) 573.
85. W. M. D. Bryant, D. M. Smith, J. Am. Chem.
Soc. 57 (1935) 57.
86. United States Government, “Code of Federal
Regulations”, 49CFR172.101, Oct. 1, 1998.
87. Kirk-Othmer, 4th ed., 49 (1993) 885.
88. Toray, GB 1 402 480, 1975.
89. A. K. Doolittle: The Technology of Solvents
and Plasticizers, J. Wiley & Sons, New York
1954.
90. I. Mellon: Industrial Solvents, Reinhold Publ.,
New York, 1950, pp. 521 – 522.
91. DFG (ed.): Maximum Concentrations at the
Workplace (MAK), VCH Verlagsgesellschaft,
Weinheim 1986.
92. J. F. Treon, W. E. Crutchfield, Jr., K. V.
Kitzmiller, J. Ind. Hyg. Toxicol. 25 (1943) 199.
93. VEBA, DE 1 111 163, 1959.
94. VEBA, DE 1 229 510, 1963 (K. Schmitt, H.
Heumann, W. Pollack).
95. VEBA, DE 1 418 067, 1959.
96. VEBA, DE 1 418 074, 1959 (E. Rindtorff, K.
Schmitt, H. Heumann).
97. VEBA, DE 1 468 693, 1963 (K. Schmitt, H.
Neumann).
98. VEBA, US 3 361 822, 1968 (K. Schmitt, J.
Disteldorf, H. Schnurbusch, W. Hilt).
99. Chemical Market Reporter, 1999 (Feb.15),
Schnell Publishing Co., New York.
100. Chemical Market Reporter, 1986 (Nov.10),
Schnell Publishing Co., New York.
101. C. S. Hughes (compiler): Chemical Economics
Handbook, SRI International, Menlo Park,
CA., Apr. 1983, 638.7020-A.
102. G. D. Clayton, F. E. Clayton (eds.): Patty’s
Industrial Hygiene and Toxicology, 3rd ed.,
Wiley-Interscience, New York 1982,
pp. 4643 – 4649.
103. U.S. Government, CFR 29, Washington, D.C.,
Jul. 1, 1978, Section 1910.1000.
104. ACGIH (ed.): Threshold Limit Values (TLV)
and Biological Exposure Indices, ACGIH,
Cincinnati, Ohio, 1986/1987.
105. H. Specht, J. W. Miller, P. J. Valaer, R. R.
Sayers: “Acute Response of Guinea Pigs to the
Inhalation of Ketone Vapors,” U.S. Public
Health Service, NIH Bulletin, no. 176,
Division of Industrial Hygiene, 1940,
pp. 1 – 66.
106. F. Bar, F. Griepentrog, Med. Ernaehr. 8 (1967)
244.
107. H. F. Smyth, Jr., C. P. Carpenter, C. S. Weil,
U. C. Pozzani et al.: “Range Finding Toxicity
Data VII,” Am. Ind. Hyg. Assoc. J. 30 (1969)
470 – 476.
108. J. Pohl, Zentralbl. Gewerbehyg. Unfallverhuet.
12 (1925) 91.
109. P. K. Gupta, W. H. Lawrence, J. E. Turner, J.
Autian: “Toxicological Aspects of
Cyclohexanone,” Toxicol. Appl. Pharmacol.
49 (1979) 525 – 533.

Cyclooctadiene → Cyclododecatriene and Cyclooctadiene