Article No : a08_217

Cyclohexanol and Cyclohexanone

MICHAEL TUTTLE MUSSER, E. I. Du Pont de Nemours & Co., Sabine River Laboratory,
Orange, Texas 77631, United States

1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . 49 8. Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
2. Physical and Chemical Properties . . . . . . . . . 49 8.1. Esters of Cyclohexanol. . . . . . . . . . . . . . . . . . 55
3. Production . . . . . . . . . . . . . . . . . . . . . . . . . . . 50 8.2. Cyclohexanone Oxime . . . . . . . . . . . . . . . . . . 56
3.1. Hydrogenation of Phenol . . . . . . . . . . . . . . . . 50 8.3. Methylcyclohexanols and
3.2. Liquid-Phase Oxidation of Cyclohexane . . . . 51 Methylcyclohexanones . . . . . . . . . . . . . . . . . 56
3.3. Boric Acid Modified Oxidation of Cyclohexane 51 8.4. Trimethylcyclohexanols and
3.4. Production and Hydration of Cyclohexene . . 52 Trimethylcyclohexanones. . . . . . . . . . . . . . .. 56
3.5. Dehydrogenation of Cyclohexanol . . . . . . . . . 54 9. Economic Aspects . . . . . . . . . . . . . . . . . . . .. 57
4. Plant Safety . . . . . . . . . . . . . . . . . . . . . . . . . . 54 10. Toxicology and Occupational Health . . . . . .. 58
5. Quality Specifications and Chemical Analysis 54 References . . . . . . . . . . . . . . . . . . . . . . . . . .. 58
6. Storage and Transportation. . . . . . . . . . . . . . 55
7. Uses and Trade Names . . . . . . . . . . . . . . . . . 55

1. Introduction Chemical Properties. Cyclohexanol under-

Cyclohexanol [108-93-0], C6H11OH, Mr 100.16,
is a colorless substance forming hygroscopic
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], C6H10O, Mr 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; ! Fibers, 4. Polyamide Fibers).
2. Physical and Chemical Properties
Physical Properties. The most important
physical properties of cyclohexanol and cyclo-
hexanone are shown in Table 1.
goes 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 dehy-
drogenation gives cyclohexanone. Stronger oxi-
dizing 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 hydrogen
cyanide to give the cyanohydrin. It can be hy-
drogenated 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
hydroxylamine to give cyclohexanone oxime

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.a08_217.pub2
50 Cyclohexanol and Cyclohexanone Vol. 11

Table 1. Physical properties of cyclohexanol and cyclohexanone cyclohexene, an intermediate obtained from the
Property Cyclo- Cyclo-
partial hydrogenation of benzene.
hexanol hexanone Cyclohexanone can be prepared by dehydro-
genation of cyclohexanol; the reverse reaction,
mp,
C 25.15 47
bp,
C 161.1 156.4
hydrogenation of cyclohexanone to cyclohexa-
Vapor pressure, kPa 0.15 (20
C) 0.52 (20
C) nol, is also practical although not commercially
0.48 (35
C) practiced. Most large-scale cyclohexanol/cyclo-
d420 0.9493 0.9455 hexanone facilities employ some form of cyclo-
n20
D 1.4656 1.4552
Expansion coefficient 8.25  104 9.14  104
hexane oxidation technology. The only remain-
Dynamic viscosity, mPa  s 41.07 (30
C) 1.803 (30
C) ing large phenol-based plants belong to DSM in
17.20 (45
C) Holland and Allied in the United States. Asahi
Specific heat, J/g 1.747 1.811 has the only commercial cyclohexene-based
Surface tension, mN/m 33.47 (30
C) 33.51 (30
C)
Heat of fusion, kJ/mol 1.791 1.501
plant, and there are reports of planned expansions
Heat of combustion, at that facility in Japan as well as building a new
MJ/mol 3.722 3.521 plant in China.
Heat of vaporization,
kJ/mol 45.51 44.92
Heat of formation, kJ/mol 352 272
Flash point,
C 68 54 3.1. Hydrogenation of Phenol
Autoignition temp.,
C 300 420
Solubility at 20
C, The product of phenol hydrogenation, i.e., cy-
g of compound/100 g
of water 3.6 9.0
clohexanol, cyclohexanone, or a mixture of the
g of water/100 g two, is determined by the metal catalyst. Cyclo-
of compound 12.6 5.7 hexanol can be prepared in high yield by either
Azeotropes vapor- or liquid-phase hydrogenation of phenol.
With water: bp,
C 97.8 96.6
composition,
Vapor-phase hydrogenation can be carried out by
water : compound 80 : 20 56 : 44 using a supported nickel catalyst or a nickel
With phenol: bp,
C 183 catalyst containing copper, cobalt, or manganese.
composition, The support is usually alumina or silicic acid.
phenol : compound 87 : 13
Yields as high as 98 % have been reported [2–5].
A flow diagram of the vapor-phase hydrogena-
tion is shown in Figure 1.
(an intermediate on the way to caprolactam) and
its oxidation with nitric acid to give adipic acid.

3. Production
Cyclohexanol and cyclohexanone were first pro-
duced on an industrial scale by the hydrogenation
of phenol. This was followed in the 1940s by
transition metal-catalyzed liquid-phase air oxi-
dation 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, Scientific Design
developed a boric acid modified liquid-phase air
oxidation of cyclohexane. This process, in which
the intermediate cyclohexyl hydroperoxide was
trapped as the peroxoborate ester, led to a higher
Figure 1. Vapor-phase phenol hydrogenation process
yield and a higher ratio of cyclohexanol to cy- a) Phenol evaporator; b) Hydrogenation reactor; c) Conden-
clohexanone. Around 1990, Asahi commercial- ser; d) Low-boiler removal column; e) Cyclohexanol/cyclo-
ized the production of cyclohexanol from hexanone recovery column
Vol. 11
Hydrogenation of phenol to cyclohexanone
can be carried out in the vapor phase with a large
variety of supported noble metal catalysts, in-
cluding palladium, platinum, iridium, ruthenium,
rubidium, and osmium. The hydrogenation is
normally carried out at 140 – 170
C and atmo-
spheric pressure. Yields as high as 95 % at 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
adjusting the operating conditions and changing
to a Raney nickel catalyst, 99.9 % selectivity for
cyclohexanol can be achieved [9]. Hydrogena-
tion 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 þO2 ! C6 H11 OOH ð1Þ
3 C6 H11 OOH ! 2 C6 H11 OHþC6 H10 OþH2 O
ð2Þ
þO2 þbyproducts
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 ‘‘deperoxida-
tion’’ gives a cyclohexanol to cyclohexanone
ratio of about 3.5. If chromium(III) is added to
the air oxidizer, it appears to promote dehydra-
tion of cyclohexyl hydroperoxide to cyclohexa-
none and water, as opposed to the free-radical
decomposition mechanism of cobalt, leading to a
lower cyclohexanol to cyclohexanone ratio
[12–14].
Cyclohexanol and Cyclohexanone 51
Because the intermediate cyclohexyl hydro-
peroxide 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
hydroperoxide varies from 70 to 90 %. Bypro-
ducts 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 oxidizers,
the oxidation can be carried out uncatalyzed or
with a modified catalyst that minimizes hydro-
peroxide decomposition in the oxidizer [15–20].
This permits cyclohexyl hydroperoxide to be
decomposed into cyclohexanol and/or cyclohex-
anone 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 caustic
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.
Several patents report that cyclohexyl hydro-
peroxide in the oxidizer effluent can be hydroge-
nated in high yield to cyclohexanol [42–47].
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
International) developed a process in which
52 Cyclohexanol and Cyclohexanone Vol. 11

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

anhydrous metaboric acid [13460-50-9]was BðOOC6 H11 Þ3 þ3 C6 H12 ! BðOC6 H11 Þ3 þ3 C6 H11 OH ð4Þ
added as a slurry to the first of several staged
air oxidation vessels (see Figure 3) [48, 49]. The BðOC6 H11 Þ3 þ3 H2 O ! 3 C6 H11 OHþH3 BO3 ð5Þ
cyclohexyl hydroperoxide formed is trapped as
the cyclohexyl perborate ester (Eq. 3). The per- 3 H3 BO3 ! H3 B3 O6 þ3 H2 O ð6Þ
borate ester then reacts with additional cyclohex-
ane in the air oxidizer to yield the borate ester and
additional cyclohexanol (Eq. 4). This borate es- The chemistry of this process is very similar to
ter is relatively stable in the air oxidizer and is the metal-catalyzed oxidation except that the
protected from over oxidation to ring-opened cyclohexyl rings are protected from further at-
products. The ester is subsequently hydrolyzed tack. Compared to other commercial processes,
to cyclohexanol and boric acid [10043-35-3] the boric acid process is characterized not only by
(Eq. 5). The boric acid is dehydrated to meta- a higher investment and a higher operating cost
boric acid and is recycled to the air oxidizer (to recover and recycle the boric acid), but also by
(Eq. 6). a higher yield of cyclohexanol and cyclohexa-
none (up to 88 %) and an alcohol to ketone ratio
18 C6 H12 þ9 O2 þ2 H3 B3 O6 ! 6 BðOOC6 H11 Þ3 þ12 H2 O as high as 10 : 1. The technology was further
ð3Þ developed by Institut Français du Petrole [50,
51]. The Halcon process has been licensed to
Table 2. Ratio of cyclohexanol to cyclohexanone produced from several companies around the world. The major
cyclohexyl hydroperoxide producers using this technology today are Solu-
Solution*– Catalyst Tempera- Ratio** tia, DuPont (UK), Bayer, and Mitsubishi. The
Modification ture,
C original plant at Rhône-Poulenc, based on this
A none 155 0.8
technology, was now shut down.
A Cr 155 0.4
A Ni 155 1.4
A V 155 1.4
A Co 155 3.0
3.4. Production and Hydration of
A Mn 155 3.3 Cyclohexene
B Co 160 2.5
A – hydrogenation of 1 Pd 150 5 – 10 In 1972 the first patent covering the selective
A – separate caustic
aqueous phase Co 120 0.2 hydrogenation of benzene [71-43-2] to cyclohex-
ene [110-83-8] appeared [52]. Shortly there-
*
A ¼ cyclohexyl hydroperoxide (1) in cyclohexane; B ¼ 1 in air
oxidizer tails. after, two patents described the hydration of
**
Cyclohexanol : cyclohexanone. cyclohexene to cyclohexanol by using various
Vol. 11 Cyclohexanol and Cyclohexanone 53

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

catalysts [53, 54]. Since then, a large number of
patents have appeared worldwide. In 1990, Asahi
commercialized this process with a 100 t/a plant
in Japan. The process involves three primary
steps: the selective hydrogenation of benzene;
the separation of the cyclohexene from the un-
converted benzene and the over-hydrogenation
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 sensi-
tive to impurities such as sulfur and iron. For this
reason the benzene must be specially purified 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].

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
cyclohexene; g) Recycle of unconverted cyclohexene; h) Purification of cyclohexanol
54 Cyclohexanol and Cyclohexanone
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
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 cyclo-
hexene 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
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 cyclo-
hexanone (the desired starting material for cap-
rolactam manufacture) without catalyst by pass-
ing the vapors through a tube furnace at 400 –
450
C. The vapors are cooled, the hydrogen
separated, and the cyclohexanone, which con-
tains 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], opper 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 oxi-
dation 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
Vol. 11
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
process line or a break in the air oxidation vessel
itself) results in an extremely hazardous situa-
tion. An incident of this type occurred at a
Monsanto plant at Pensacola, Florida in 1971.
Fortunately, the resulting vapor cloud was dis-
persed 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
oxidation vessels ruptured, resulting in the re-
lease 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 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 cyclohexanol
is gas chromatography with Carbowax 20M on
Chromosorb. Common impurities, such as cyclo-
hexane, 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 4-hydroxybenzaldehyde
in sulfuric acid [82]. The preferred acylating
agent for microscale quantities is acetic anhy-
dride [83].
Vol. 11
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 Chromo-
sorb gas chromatography column. Cyclohexa-
none 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 liberated
[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 intermedi-
ate 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 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 rub-
ber cement industries
Cyclohexanol and Cyclohexanone 55
Trade names: Cyclohexyl Alcohol, Hexahy-
drophenol, Hydrophenol, Hexalin, and A.
Cyclohexanone. Over 97 % of all cyclohex-
anone 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 lac-
quers. It is also used as a starting material in the
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 being
dicyclohexyl phthalate, dicyclohexyl adipate,
and cyclohexyl acrylate.
Dicyclohexyl Phthalate
[84-61-7], C20H26O4, Mr 330.45, mp 65
C, bp
218
C (0.6 kPa), d20 1.148. This diester is nor-
mally 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 finish to extruded
materials. It is also used in paper finishes and
makes printers ink water-resistant.
DicyclohexylAdipate [849-99-0], C18H30O4,
Mr 294.50, mp 35.5
C, bp 324
C, d20 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
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].
56 Cyclohexanol and Cyclohexanone Vol. 11

8.2. Cyclohexanone Oxime The commercial mixture is a colorless liquid

Cyclohexanone oxime [100-64-1], C6H10NOH,
Mr 113.16 , mp 90.5
C, bp 204
C, sublimes at
room temperature (0.6 kPa); it is a white crystal-
line solid that can be crystallized as prisms from
hydrocarbon solvents. This compound is the
most important commercial derivative of cyclo-
hexanone. It can be prepared by warming cyclo-
hexanone with an aqueous mixture of hydroxyl-
amine hydrochloride and sodium bicarbonate.
The oxime undergoes a Beckmann rearrange-
ment in the presence of sulfuric acid to give
caprolactam.
Large commercial quantities of cyclohexa-
none oxime are used in the preparation of capro-
lactam, 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.
and is used as a solvent for resins, oils, and waxes,
as a blending agent in soaps, and as an antioxi-
dant in lubricants [89, 90].
Methylcyclohexanone is normally sold as a
mixture of three isomers (2-, 3-, and 4-methyl-
cyclohexanone). 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 con-
tains 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.

8.3. Methylcyclohexanols and

Methylcyclohexanones
Methylcyclohexanol, CH3C6H10OH, Mr
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
individual isomers and of a commercial mixture.
8.4. Trimethylcyclohexanols and
Trimethylcyclohexanones
3,3,5-Trimethylcyclohexanol (2), C6H18O,
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.

Table 3. Physical properties of methylcyclohexanols and methylcyclohexanones

CAS registry Flash

Isomer number mp,
C bp,
C d20 n 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
Vol. 11
The physical properties of the two isomers
are: cis isomer [933-48-2], mp 37.3
C, n60
1.4390, d600.860, 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, d600.862, 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 cyclo-
hexanol. Oxidation of trimethylcyclohexanol
with nitric acid gives a mixture of 2,2,4-trimethy-
ladipic acid and 2,4,4-trimethyladipic acid.
Trimethylcyclohexanol is prepared by hydroge-
nating 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 car-
ried out in high yield at 120 – 200
C and 1 –
2 MPa. The byproducts of the reaction are small
amounts of trimethylcyclohexanone, trimethyl-
cyclohexane, and trimethylcyclohexene.
The most important use for the alcohol is as a
feedstock for trimethyladipic acid [93–97]. 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 trimethylcy-
Cyclohexanol and Cyclohexanone 57
clohexanol are as replacement for cyclohexanol
in polishes and waxes. Because of its lower vapor
pressure and unique structure, trimethylcyclo-
hexanol is better than cyclohexanol in varnishes
and shellacs.
The trimethylcyclohexanol that is sold com-
mercially is a mixture of the cis and trans iso-
mers. Analysis of a typical commercial product
indicates 98 % trimethylcyclohexanols, 1 % tri-
methylcyclohexanone, 0.4 % trimethylcyclohex-
ane, 0.3 % trimethylcyclohexene, 0.1 % isophor-
one, and 0.2 % water.
Trimethylcyclohexanol can be stored and
transported in iron or steel drums, containers,
tank cars, or tank trucks. It is stable indefinitely
and does not need to be blanketed with an inert
gas.
3,3,5-Trimethylcyclohexanone (3) [873-
94-9], C6H16O, Mr 140.24, is a colorless liquid
having properties similar to those of cyclohexa-
none. It has the following physical properties: mp
–10
C, bp 188.8
C, d20 0.888, n201.4455, flash
point 72
C, solubility (at 20
C) of ketone in
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 olefin 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 cata-
lyst, reaction conditions, and amount of hydro-
gen 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 high-
er boiling point results in superior performance in
some applications.
9. Economic Aspects
Cyclohexanol and cyclohexanone are primarily
captively consumed-either isolated or as a mix-
ture-in the production of adipic acid and capro-
lactam less than 5% is used in other markets [99].
Important producers are Invista (USA), Honey-
coell (USA), Solutia (USA), BASF (Germany),
and DSM (Netherlands).
58 Cyclohexanol and Cyclohexanone
10. Toxicology and Occupational
Health
Cyclohexanol and Cyclohexanone are
moderately toxic [100], but have no apparent
carcinogenicity. For cyclohexanol the OSHA
TLV for exposure to vapor for 8 h is 50 ppm
[101]. The ACGIH has established TLV-TWA
values for exposure to cyclohexanol vapor of
50 ppm, 200 mg/m3 [102]. 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 chemi-
cal 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 [100].
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 [103].
Degenerative changes were noted in the kidney
and liver of monkeys and rabbits exposed repea-
tedly to high vapor concentrations of cyclo-
hexanone.
For single dosages of cyclohexanol, the oral
LD50 for rats is 2.06 g/kg [104] 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 [105] 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 [105, 106]. Cyclohexanol can be absorbed
through the skin in toxic amounts, and extensive
exposure can cause tremors, narcosis, hypother-
mia, 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 [107].
Derivatives. Commercial methylcyclohexa-
nol 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
Vol. 11
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-Methyl-
cyclohexanone 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.
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).
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).
Vol. 11
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. Vvos-
kuil, 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).
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 Petrole, FR 1 556 979, 1969 (J.
Alagy, A. Zuech, B. Cha).
51 Institut Français du Petrole, FR 1 573 834, 1969 (J.
Alagy, L. Asselineau, C. Busson, B. Cha).
52 Du Pont, BE 782 721, 1972 (W. C. Drinkard).
Cyclohexanol and Cyclohexanone 59
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.
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, Inter-
science, 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 Regula-
tions’’, 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 Plas-
ticizers, 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, Germany
1986.
60 Cyclohexanol and Cyclohexanone
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 http://www.sriconsulting.com (accessed 3 September
2010).
100 G. D. Clayton, F. E. Clayton (eds.): Patty’s Industrial
Hygiene and Toxicology, 3rd ed., Wiley-Interscience,
New York 1982, pp. 4643 – 4649.
101 U.S. Government, CFR 29, Washington, D.C., Jul. 1,
1978, Section 1910.1000.
102 ACGIH (ed.): Threshold Limit Values (TLV) and Bio-
logical Exposure Indices, ACGIH, Cincinnati, Ohio,
1986/1987.
103 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 Bul-
letin, no. 176, Division of Industrial Hygiene, 1940,
pp. 1 – 66.
104 F. Bar, F. Griepentrog, Med. Ernaehr. 8 (1967) 244.
105 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.
Vol. 11
106 J. Pohl, Zentralbl. Gewerbehyg. Unfallverhuet. 12
(1925) 91.
107 P. K. Gupta, W. H. Lawrence, J. E. Turner, J. Autian:
‘‘Toxicological Aspects of Cyclohexanone,’’ Toxicol.
Appl. Pharmacol. 49 (1979) 525 – 533.
Further Reading
G. C. Bond: Metal-catalysed Reactions of Hydrocarbons,
Springer, New York, NY 2005.
G. Centi, F. Trifiró, S. Perathoner, F. Cavani: Sustainable
Industrial Processes, Wiley-VCH, Weinheim 2009.
G. P. Chiusoli, P. M. Maitlis (eds.): Metal-Catalysis in
Industrial Organic Processes, Royal Society of Chemis-
try, Cambridge, UK 2006.
B. L. Deopura, R. Alagirusamy, M. Joshi, B. Gupta (eds.):
Polyesters and Polyamides, CRC Press/Woodhead Publ.,
Cambridge, UK 2008.
A. C. Dimian, C. S. Bildea: Chemical Process Design, Wiley-
VCH, Weinheim 2008.
W. B. Fisher, J. F. Van Peppen: ‘‘Cyclohexanol and Cyclo-
hexanone’’, Kirk Othmer Encyclopedia of Chemical Tech-
nology, 5th edition, John Wiley & Sons, Hoboken, NJ,
online DOI: 10.1002/0471238961.0325031206091908.
a01.
W. B. Gratzer: Giant Molecules: From Nylon to Nanotubes,
Oxford University Press, Oxford, UK 2009.
K. C. Seavey, Y. A. Liu: Step-growth Polymerization Process
Modeling and Product Design, Wiley, Hoboken, NJ 2008.