Cyclohexanol and Cyclohexanone

Cyclohexanol and Cyclohexanone

Michael Tuttle Musser, E. I. Du Pont de Nemours & Co., Sabine River Laboratory, Orange, Texas 77631,
United States

Introduction . . . . . . . . . . . . . . . . .
Physical and Chemical Properties . .
Production . . . . . . . . . . . . . . . . . .
Hydrogenation of Phenol . . . . . . . .
Liquid-Phase Oxidation of Cyclohexane . . . . . . . . . . . . . . . . . . . . . . .
3.3. Boric Acid Modied Oxidation of Cyclohexane . . . . . . . . . . . . . . . . . . .
3.4. Production and Hydration of Cyclohexene . . . . . . . . . . . . . . . . . . . . .
3.5. Dehydrogenation of Cyclohexanol . .
4.
Plant Safety . . . . . . . . . . . . . . . . .
5.
Quality Specications and Chemical
Analysis . . . . . . . . . . . . . . . . . . . .
1.
2.
3.
3.1.
3.2.

1
1
2
2
3
4
4
6
6

Storage and Transportation . . . . . .

Uses and Trade Names . . . . . . . . . .
Derivatives . . . . . . . . . . . . . . . . . .
Esters of Cyclohexanol . . . . . . . . . .
Cyclohexanone Oxime . . . . . . . . . .
Methylcyclohexanols and Methylcyclohexanones . . . . . . . . . . . . . . . .
8.4. Trimethylcyclohexanols and
Trimethylcyclohexanones . . . . . . . .
9.
Economic Aspects . . . . . . . . . . . . .
10. Toxicology and Occupational Health .
11. References . . . . . . . . . . . . . . . . . .

6.
7.
8.
8.1.
8.2.
8.3.

7
7
7
7
8
8
8
10
10
11

1. Introduction
Cyclohexanol [108-93-0], C6 H11 OH, M r
100.16, is a colorless substance forming hygroscopic crystalline needles having a camphorlike 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 mixtures is consumed in the production of caprolactam 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 cyclohexanone are shown in Table 1.

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a08 217

Chemical Properties. Cyclohexanol undergoes chemical reactions typical of secondary alcohols. It can esterify most organic acids or acyl
halides, whereas halogen acids convert the alcohol 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 dehydrogenation gives cyclohexanone. Stronger oxidizing agents, such as nitric acid, give a good
yield of adipic acid.
Cyclohexanone undergoes most of the reactions expected of aliphatic ketones. At room
temperature, 0.02 % exists in the enol form
[1]. Cyclohexanone reacts with bisulte to give
the addition product; it also reacts with hydrogen cyanide to give the cyanohydrin. It can be
hydrogenated to cyclohexanol and under more
vigorous conditions is further reduced to cyclohexane. 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 commercial reactions of cyclohexanone are with hydroxylamine to give cyclohexanone oxime (an
intermediate on the way to caprolactam) and its
oxidation with nitric acid to give adipic acid.

Cyclohexanol and Cyclohexanone

3. Production
Cyclohexanol and cyclohexanone were rst produced on an industrial scale by the hydrogenation of phenol. This was followed in the 1940s
by transition metal-catalyzed liquid-phase air
oxidation of cyclohexane, which gave a mixture
of cyclohexanol and cyclohexanone, the ratio of
which could be partially controlled by the choice
of metal catalyst. In the 1950s, Scientic Design
developed a boric acid modied liquid-phase air
oxidation of cyclohexane. This process, in which
the intermediate cyclohexyl hydroperoxide was
trapped as the peroxoborate ester, led to a higher
yield and a higher ratio of cyclohexanol to cyclohexanone. Around 1990, Asahi commercialized the production of cyclohexanol from cyclohexene, an intermediate obtained from the
partial hydrogenation of benzene.
Table 1. Physical properties of cyclohexanol and cyclohexanone
Property

Cyclohexanol

Cyclohexanone

mp, C
bp, C
Vapor pressure, kPa

25.15
161.1
0.15 (20 C)
0.48 (35 C)
0.9493
1.4656
8.25 104
41.07 (30 C)
17.20 (45 C)
1.747
33.47 (30 C)
1.791

47
156.4
0.52 (20 C)

1.811
33.51 (30 C)
1.501

3.722

3.521

45.51
352
68
300

44.92
272
54
420

3.6

9.0

12.6

5.7

97.8

96.6

80 : 20
183

56 : 44

d 20
4
n20
D
Expansion coefcient
Dynamic viscosity, mPa s
Specic heat, J/g
Surface tension, mN/m
Heat of fusion, kJ/mol
Heat of combustion,
MJ/mol
Heat of vaporization,
kJ/mol
Heat of formation, kJ/mol
Flash point, C
Autoignition temp., C
Solubility at 20 C,
g of compound/100 g
of water
g of water/100 g
of compound
Azeotropes
With water: bp, C
composition,
water : compound
With phenol: bp, C
composition,
phenol : compound

hexanone facilities employ some form of cyclohexane oxidation technology. The only remaining large phenol-based plants belong to
DSM in Holland and Allied in the United States.
Asahi has the only commercial cyclohexenebased plant, and there are reports of planned
expansions at that facility in Japan as well as
building a new plant in China.

3.1. Hydrogenation of Phenol

The product of phenol hydrogenation, i.e., cyclohexanol, cyclohexanone, or a mixture of the
two, is determined by the metal catalyst. Cyclohexanol can be prepared in high yield by
either vapor- or liquid-phase hydrogenation of
phenol. Vapor-phase hydrogenation can be carried out by using a supported nickel catalyst or
a nickel catalyst containing copper, cobalt, or
manganese. The support is usually alumina or
silicic acid. Yields as high as 98 % have been reported [25]. A ow diagram of the vapor-phase
hydrogenation is shown in Figure 1.

0.9455
1.4552
9.14 104
1.803 (30 C)

87 : 13

Cyclohexanone can be prepared by dehydrogenation of cyclohexanol; the reverse reaction,

hydrogenation of cyclohexanone to cyclohexanol, is also practical although not commercially
practiced. Most large-scale cyclohexanol/cyclo-

Figure 1. Vapor-phase phenol hydrogenation process

a) Phenol evaporator; b) Hydrogenation reactor; c) Condenser; d) Low-boiler removal column; e) Cyclohexanol/cyclohexanone recovery column

Hydrogenation of phenol to cyclohexanone

can be carried out in the vapor phase with a
large variety of supported noble metal catalysts,
including palladium, platinum, iridium, ruthenium, rubidium, and osmium. The hydrogenation is normally carried out at 140 170 C and
atmospheric pressure. Yields as high as 95 % at
100 % conversion can be obtained [6], [7].

Cyclohexanol and Cyclohexanone

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 adjusting the operating conditions and changing to
a Raney nickel catalyst, 99.9 % selectivity for cyclohexanol can be achieved [9]. Hydrogenation
conditions can be adjusted to produce the mixture 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, although 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 cyclohexyl hydroperoxide [766-07-4](Eq. 1) is converted in the oxidizers to cyclohexanol, cyclohexanone, 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 exiting 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 cyclohexanone ratio of about 3.5. If chromium(III)
is added to the air oxidizer, it appears to promote dehydration of cyclohexyl hydroperoxide to cyclohexanone and water, as opposed to
the free-radical decomposition mechanism of
cobalt, leading to a lower cyclohexanol to cyclohexanone ratio [1214].
Because the intermediate cyclohexyl hydroperoxide 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 conversion, the total yield of alcohol, ketone, and

hydroperoxide varies from 70 to 90 %. Byproducts 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 cyclohexane leaving the oxidizers as cyclohexyl
hydroperoxide. To maximize the amount of cyclohexyl hydroperoxide leaving the air oxidizers, the oxidation can be carried out uncatalyzed
or with a modied catalyst that minimizes hydroperoxide decomposition in the oxidizer [15
20]. This permits cyclohexyl hydroperoxide to
be decomposed into cyclohexanol and/or cyclohexanone 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 cyclohexanol and cyclohexanone with a homogeneous or heterogeneous metal catalyst [2135].
Another method of decomposing the hydroperoxide is to contact it with an aqueous caustic phase containing a few parts per million of
cobalt, which decomposes the hydroperoxide in
high yield to the ketone and alcohol [3641].
This caustic decomposition process can result
in a lower alcohol to ketone ratio in the nal
product. A ow diagram of this caustic process
is shown in Figure 2.
Table 2. Ratio of cyclohexanol to cyclohexanone produced from
cyclohexyl hydroperoxide
Solution
Modication

Catalyst

Temperature, C

Ratio

A
A
A
A
A
A
B
A hydrogenation of 1
A separate caustic
aqueous phase

none
Cr
Ni
V
Co
Mn
Co
Pd

155
155
155
155
155
155
160
150

0.8
0.4
1.4
1.4
3.0
3.3
2.5
5 10

Co

120

0.2

A = cyclohexyl hydroperoxide (1) in cyclohexane; B = 1 in air

oxidizer tails.
Cyclohexanol : cyclohexanone.

Several patents report that cyclohexyl hydroperoxide in the oxidizer efuent can be hydrogenated in high yield to cyclohexanol [42
47].

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) Cyclohexane recovery column; g) Cyclohexanol/cyclohexanone recovery column

Table 2 shows the cyclohexanol to cyclohexanone ratio that can be obtained by using a range
of conditions and a variety of hydroperoxide
decomposition methods.

3.3. Boric Acid Modied Oxidation of

Cyclohexane
In the 1950s, Scientic Design (now Halcon International) developed a process in which anhydrous metaboric acid [13460-50-9]was added as
a slurry to the rst of several staged air oxidation
vessels (see Figure 3) [48], [49]. The cyclohexyl
hydroperoxide formed is trapped as the cyclohexyl perborate ester (Eq. 3). The perborate ester then reacts with additional cyclohexane in
the air oxidizer to yield the borate ester and additional cyclohexanol (Eq. 4). This borate ester
is relatively stable in the air oxidizer and is protected from over oxidation to ring-opened products. The ester is subsequently hydrolyzed to cyclohexanol 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 attack. 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 cyclohexanone (up to 88 %) and an alcohol to ketone ratio as high as 10 : 1. The technology was
further developed by Institut Francais du Petrole
[50], [51]. The Halcon process has been licensed
to several companies around the world. The major producers using this technology today are
Solutia, DuPont (UK), Bayer, and Mitsubishi.
The original plant at Rhone-Poulenc, based on
this technology, was now shut down.

3.4. Production and Hydration of

Cyclohexene
In 1972 the rst patent covering the selective hydrogenation of benzene [71-43-2] to cyclohexene [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

Figure 3. Boric acid modied oxidation of cyclohexane

a) Air oxidizers; b) Ester hydrolysis vessel; c) Decanter; d) Extraction column; e) Cyclohexane recovery column; f) Rening
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 purication; 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 cyclohexene; g) Recycle of unconverted cyclohexene; h) Purication of cyclohexanol

plant in Japan. The process involves three primary steps: the selective hydrogenation of benzene; the separation of the cyclohexene from
the unconverted benzene and the over-hydrogenation product cyclohexane; and the hydration of
the cyclohexene (Fig. 4).
The hydrogenation is carried out with a specially 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 % unconverted benzene. The selectivity is very sensitive to impurities such as sulfur and iron. For

this reason the benzene must be specially puried and the hydrogenation vessel lined with an
inert material [5558].
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 [5962].
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 performed with a heterogeneous catalyst in a slurry

Cyclohexanol and Cyclohexanone

reactor. The extent of hydration is limited by the

equilibrium constant, which would restrict conversion to about 14 %. The use of several additives to increase the conversion of cyclohexene
to cyclohexanol has also been patented [6368].
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 signicantly higher
than that of a conventional cyclohexane oxidation plant. The fact that the product is cyclohexanol, not cyclohexanone, could make it unattractive as the basis for a caprolactam plant.

3.5. Dehydrogenation of Cyclohexanol

Cyclohexanol can be dehydrogenated to cyclohexanone (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 hydrogen separated, and the cyclohexanone, which
contains cyclohexene and water, is puried in
a distillation column. The purity of the resulting
cyclohexanone is 98 99 % [6972].
The catalytic dehydrogenation, which is generally 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 sulde, and zinc iron catalyst [7779],
cobalt carbonate [80], and other metals [81].

4. Plant Safety
The major industrial hazard associated with producing cyclohexanol and cyclohexanone is oxidation 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 incident occurred in which the air sparger, entering
the oxidizer, was observed to be  glowing red,
indicating a re inside the sparger. An incident
of a re 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 process line or a break in the air oxidation vessel itself) 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 occurred at a Nipro plant in Flixborough, England.
A section of 50-cm pipe connecting two air oxidation vessels ruptured, resulting in the release
of a large cloud of cyclohexane vapor. About
30 s after the break occurred, the vapor cloud ignited, and the resulting explosion destroyed the
plant. A total of 28 lives were lost.

5. Quality Specications and

Chemical Analysis
High-grade commercial cyclohexanol, usually
obtained from hydrogenation of phenol, has the
following specications:
mp
bp
Water content
Phenol content

19 23 C
159 162 C
0.1 %
0.0001 %

The best analytical method for cyclohexanol is gas chromatography with Carbowax
20M on Chromosorb. Common impurities, such
as cyclohexane, cyclohexanone, phenol, pentanol, and benzene, do not interfere. Cyclohexanol can be characterized as the 4-nitrobenzoyl
derivative, mp 52 C. It can be determined
colorimetrically by using a solution of 4hydroxybenzaldehyde in sulfuric acid [82]. The
preferred acylating agent for microscale quantities 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 Chromosorb gas chromatography column. Cyclohexanone can be characterized as the oxime (mp
90.5 C), the semicarbazone (mp 167 C), or the
nitrophenylhydrazone (mp 146 C). It can be

Cyclohexanol and Cyclohexanone

quantitatively determined by reaction with hydroxylamine hydrochloride, followed by basic
titration of the hydrogen chloride that is liberated [84], [85].

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.

6. Storage and Transportation

Cyclohexanol and cyclohexanone are not corrosive to iron or steel and can be stored or transported in drums, tank trucks, or tank cars. An
inert gas (nitrogen) blanket is not required. The
U.S. DOT classies both cyclohexanol and cyclohexanone, or mixtures thereof, as hazardous
ammable liquids. For transportation, they must
be labeled ammable and marked Hazard Level
III [86]

7. Uses and Trade Names

Cyclohexanol has numerous industrial applications, the major two being as an intermediate in the production of adipic acid (for use
in nylon 66) and cyclohexanone, which is then
converted to caprolactam (the monomer for nylon 6). The U.S. market for rened cyclohexanol, 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 synthetic detergents as a homogenizer and stabilizer
4) In paint and varnish removers
5) In the insecticide, fragrance, polish, and rubber cement industries
Trade
names:
Cyclohexyl
Alcohol,
Hexahydrophenol, Hydrophenol, Hexalin, and
A.
Cyclohexanone. Over 97 % of all cyclohexanone produced is oxidized to adipic acid or converted 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 lacquers. It is also used as a starting material in the

8. Derivatives
8.1. Esters of Cyclohexanol
Numerous esters of cyclohexanol are of commercial signicance, the more important being dicyclohexyl phthalate, dicyclohexyl adipate, 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 cyclohexanol 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 nish to extruded materials. It is also used in paper nishes 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 esterication
of adipic acid, transesterication of dimethyl
adipate, or direct reaction of adipic acid with cyclohexene [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 crystalline solid that can be crystallized as prisms
from hydrocarbon solvents. This compound is

Cyclohexanol and Cyclohexanone

the most important commercial derivative of cyclohexanone. It can be prepared by warming

cyclohexanone with an aqueous mixture of hydroxylamine hydrochloride and sodium bicarbonate. The oxime undergoes a Beckmann rearrangement in the presence of sulfuric acid to
give caprolactam.
Large commercial quantities of cyclohexanone oxime are used in the preparation of
caprolactam, the intermediate for the preparation 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-methylcyclohexanol. These derivatives are prepared by
hydrogenation of individual or mixed cresols.
Table 3 gives the physical properties of the individual isomers and of a commercial mixture.
The commercial mixture is a colorless liquid 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-methylcyclohexanone). The individual isomers can be
isolated; their physical properties, along with
those of a commercial mixture, are listed in Table 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 cyclohexanone.
The technical-grade commercial mixture
contains all three isomers. At 20 C its solubility in water is 1.5 %, and 3 % water is soluble
in the methylcyclohexanones. Methylcyclohexanones 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 isomers 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), ash 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), ash 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 trimethylcyclohexanol with nitric acid gives a mixture of 2,2,4trimethyladipic acid and 2,4,4-trimethyladipic
acid. Trimethylcyclohexanol is prepared by
hydrogenating 3,5,5-trimethyl-2-cyclohexen-1one [78-59-1] (1), isophorone (a condensationproduct 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

Table 3. Physical properties of methylcyclohexanols and methylcyclohexanones

CAS registry
number

mp, C

bp, C

d 20

[7443-70-1]
[7443-52-9]
[5454-79-5]
[7443-55-2]
[7731-28-4]
[7731-29-5]
[25639-42-3]

7
4
4.7
1
9.2
50

165.2
166.5
174.0
175.0
174.0
173.0
173 175

0.934
0.924
0.917
0.915
0.912
0.916
0.913

[583-60-8]

13.9

165.1

0.925

dl-3-Methylcyclohexanone

[591-24-2]

73.5

170.0

0.920

4-Methylcyclohexanone

[589-92-4]

40.6

171.3

0.916

Commercial mixture

[1331-22-2]

165 171

0.918 0.925

Isomer

Methylcyclohexanols
dl-cis-2-Methylcyclohexanol
dl-trans-2-Methylcyclohexanol
d-cis-3-Methylcyclohexanol
l-trans-3-Methylcyclohexanol
cis-4-Methylcyclohexanol
trans-4-Methylcyclohexanol
Commercial mixture
Methylcyclohexanones
dl-2-Methylcyclohexanone

trimethylcyclohexanone, trimethylcyclohexane,
and trimethylcyclohexene.
The most important use for the alcohol
is as a feedstock for trimethyladipic acid
[9397]. This mixture of 2,2,4-trimethyladipic
acid [3586-39-8]and 2,4,4-trimethyladipic acid
[3937-59-5], is used in the manufacture of plasticizers and lubricants, and can be converted to
dinitriles, diamines, or glycols. Other uses for
trimethylcyclohexanol are as replacement for
cyclohexanol in polishes and waxes. Because of
its lower vapor pressure and unique structure,
trimethylcyclohexanol is better than cyclohexanol in varnishes and shellacs.
The trimethylcyclohexanol that is sold commercially is a mixture of the cis and trans isomers. Analysis of a typical commercial product indicates 98 % trimethylcyclohexanols, 1 %
trimethylcyclohexanone, 0.4 % trimethylcyclohexane, 0.3 % trimethylcyclohexene, 0.1 %
isophorone, and 0.2 % water.
Trimethylcyclohexanol can be stored and
transported in iron or steel drums, containers,
tank cars, or tank trucks. It is stable indenitely
and does not need to be blanketed with an inert
gas.

Flash
point, C

154
1.4440
(25 C)
1.4449
(20 C)
1.4451
(20 C)

48
48
48

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

in all proportions with most organic solvents.
Trimethylcyclohexanone (3) is also prepared
by hydrogenating trimethylcyclohexenone (2).
However, the olen hydrogenation can be carried out without hydrogenating the ketone
by using a palladium-supported catalyst at
110 170 C and 0.2 6 MPa [98]. The combination of catalyst, reaction conditions, and
amount of hydrogen determines whether the ketone or alcohol is produced.
Trimethylcyclohexanone is a good solvent
for low molecular mass poly(vinyl chloride)type alkyd resins and for nitrocellulose. It can
be used in place of methylcyclohexanone, where
its higher boiling point results in superior performance in some applications.

9. Economic Aspects

The quoted price for technical-grade cyclohexanol in February 1999 was $ 1.83/kg [99] as
compared to $ 1.32/kg in 1986 [100]. U.S. sales
of cyclohexanol in 1992 were about 10 103 t
[87], up from 4.3 103 t in 1971 [101]. The remaining 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 havIn 1992, U.S. non-adipic acid, non-caproing 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, ash
The early 1999 cost of technical-grade cyclopoint 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 cyclohexanol-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 moderately toxic [102], but have no apparent carcinogenicity. 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 cyclohexanone is 25 ppm, 100 mg/m3 . The MAKs for
both compounds are 50 ppm, 200 mg/m3 .
Excessive exposure to vapor of either chemical results in irritation to the eyes, nose, and
throat. Exposure of animals to a high concentration 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 repeatedly to high vapor concentrations of cyclohexanol [102].
Exposure of animals to high concentrations
of cyclohexanone vapor also resulted in irritation, 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 minimum 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 moderately irritating to the eye and can cause corneal

injury [107], [108]. Cyclohexanol can be absorbed 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 methylcyclohexanol 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]. Excessive 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 toxicological 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.

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Cyclohexanol and Cyclohexanone

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11

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Cyclohexanol and Cyclohexanone

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Cyclooctadiene

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Cyclododecatriene and Cyclooctadiene