La ciclohexanona

Cyclohexanol and Cyclohexanone

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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 Modified Oxidation of Cyclohexane . . . . . . . . . . . . . . . . . . . 3.4. Production and Hydration of Cyclohexene . . . . . . . . . . . . . . . . . . . . . 3.5. Dehydrogenation of Cyclohexanol . . 4. Plant Safety . . . . . . . . . . . . . . . . . 5. Quality Specifications and Chemical Analysis . . . . . . . . . . . . . . . . . . . . 1.2. 3. 3.1. 3.2.

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

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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 andtheir 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.

Chemical Properties. Cyclohexanolundergoes 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 nitricacid, 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 bisulfite 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 tocyclohexane. 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 nitricacid to give adipic acid.

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a08 217

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Cyclohexanol and Cyclohexanone 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...