Cydohexanol

In a 1500 ml. round-bottomed flask, carrying a reflux condenser, place 100 g. of pure cydohexanol, 250 ml. of concentrated hydrochloric acid and 80 g. of anhydrous calcium chloride heat the mixture on a boiling water bath for 10 hours with occasional shaking (1). Some hydrogen chloride is evolved, consequently the preparation should be conducted in the fume cupboard. Separate the upper layer from the cold reaction product, wash it successively with saturated salt solution, saturated sodium bicarbonate solution, saturated salt solution, and dry the crude cycZohexyl chloride with excess of anhydrous calcium chloride for at least 24 hours. Distil from a 150 ml. Claisen flask with fractionating side arm, and collect the pure product at 141-5-142-5°. The yield is 90 g. 

Geminale Chlor-nitroso-Verbindungen werden durch Lithiumalanat in Diathylather (40-70% d.Th.) oder besser mit Natriumboranat in waBrigem Athanol (50-80% d.Th.) zu Oximen reduziert. Als Nebenprodukte konnen gelegentlich Hydroxylamine isoliert werden. So erhalt man z.B. aus 1-Chlor-l-nitroso-cyclohexan mit Natriumboranat neben 61 % d.Th. Cyclohexanon-oxim 11 % d.Th.V-Cyclohexyl-hydroxylamin5. Dagegen werden bei der Reduktion von 1-Nitroso-l-acetoxy-cyclohexan Cydohexanol (8% d.Th.) und N-Cyclohexyl-acetamid (34% d.Th.) erhalten6. 

Reactions. w-Hydroxybenzoic acid affords a variety of products, depending on the catalyst and conditions employed. Catalytic reduction over platinum black or platinum oxide in alkaline solution gives 3-hydroxycyclohexanecarboxylic acid [22267-35-2]. Reduction of a warm aqueous solution over platinum oxide or over colloidal platinum yields cyclohexanecarboxylic acid. w-Hydroxybenzaldehyde can be prepared by reducing ///-hydroxybenzoic acid with sodium amalgam. Finally, reduction over Raney nickel gives cydohexanol. 

Commerdal absolute ethanol is used without additional drying. The submitters state that the use of absolute ethanol may be avoided by employment of the alternative condensation procedure of Wood and Cadorin3 using 5 mole per cent of sodium hydroxide in aqueous methanol at 15-20° for 6 hours, but the yield of l-(nitromethyl)cydohexanol is appreciably lower... 

When camphene reacts with guaiacol (2-methoxyphenol), a mixture of terpenyl phenols is formed. Hydrogenation of the mixture results in hydrogenolysis of the methoxy group and gives a complex mixture of terpenyl cydohexanols (eg, 3-(2-isocamphyl) cyclohexanol [70955-714] (45)), which after fractional distillation produces a useful sandalwood fragrance product (85). A similar process has also been developed using catechol and camphene (86). 

Hydrocarbon Oxidation. The oxidation of hydrocarbons (qv) and hydrocarbon derivatives can be significantly altered by boron compounds. Several large-scale commercial processes, such as the oxidation of cyclohexane to a cydohexanol—cyclohexanone mixture in nylon manufacture, are based on boron compounds (see Cylcohexanol and cyclohexanone Fibers, polyamide). A number of patents have been issued on the use of borate esters and boroxines in hydrocarbon oxidation reactions, but commercial processes apparently use boric acid as the preferred boron source. The literature in this field has been covered through 1967 (47). Since that time the literature consists of foreign patents, but no significant applications have been reported for borate esters. 

BASF. In the Badische process, cyclohexanone is produced by liquid-phase catalytic air oxidation of cyclohexane to KA oil, which is a mixture of cyclohexanone and cydohexanol, and is followed by vapor-phase catalytic dehydrogenation of the cydohexanol in the mixture. Overall yidds range from 75% at 10% cydohexane conversion to 80% at 5% cydohexane conversion. 

Dutch State Mines (Stamicarbon). Vapor-phase, catalytic hydrogenation of phenol to cyclohexanone over palladium on alumina, licensed by Stamicarbon, the engineering subsidiary of DSM, gives a 95% yield at high conversion plus an additional 3% by dehydrogenation of coproduct cydohexanol over a copper catalyst. Cyclohexane oxidation, an alternative route to cyclohexanone, is used in the United States and in Asia by DSM. A cyclohexane vapor-cloud explosion occurred in 1975 at a co-owned DSM plant in Flixborough, UK (12) the plant was rebuilt but later closed. In addition to the conventional Raschig process for hydroxylamine, DSM has developed a hydroxylamine phosphate—oxime (HPO) process for cyclohexanone oxime no by-product ammonium sulfate is produced. Catalytic ammonia oxidation is followed by absorption of NOx in a buffered aqueous phosphoric acid... 

A recent paper by Kwiatek and co-workers1891 discloses the use of a homogeneous catalysis system for the hydrogenation of epoxides. Reduction of cyclohexene oxide to cydohexanol, and of styrene oxide to 2-phenylethanol, was carried at atmospherio pressure, using Ks[Co(CN) ] to catalyze the reaction. 

The alkene mixture obtained on dehydration of 2,2-dimethyl-cydohexanol contains appreciable amounts of 1,2-dimethylcydohexene. Give a mechanistic explanation for the formation of this product. 

Jan F. VanPeppen, Allied Signal Inc.. Petersberg. )A. hup //www. alliedsignal.com/. Cydohexanol-Cyclohexanone... 

Cydohexanol or Hexahydrophenol (called Cyclo-hexanol or Hexahydrophenol in Ger),... 

A typical loss maximum of this type was observed for poly(methyl methacrylate) containing caprolactam or derivatives of cyclohexane12,13. It is noteworthy70 that in the latter case the relaxation induced by the cyclohexyl group present in the incorporated plasticizer and the secondary relaxation of poly(cyclohexyl methacrylate) or poly(cyclohexyl acrylate) are characterized by an identical temperature position, 190 K (1 Hz), and activation energy, 47.9 kJ/mol (AU = 47.7 kJ/mol is reported for the chair-chair transition of cydohexanol). Hence, it can be seen that the cyclohexyl ring inversion, which represents a specific molecular motion, is remarkably insensitive to the surrounding molecules. 

In a 500-cc. modified Claisen flask (Org. Syn. 1, 40) are placed 400 g. of cydohexanol (Note 1) and 12 cc. of concentrated sulfuric acid, and the flask is connected to a condenser and receiver. It is then placed in an oil bath which is heated to a temperature of 130-140°. The distillation is continued until only a small residue remains and the odor of sulfur dioxide is apparent. Toward the end of the distillation the temperature of the bath may be raised to 150°. The receiver is surrounded with an ice bath (Note 2) during the entire distillation which requires from five to six hours. 

Dihydroxy compounds and quinones were detected in trace amounts, whereas hydrogenated compounds such as cyclohexane, cydohexanol and cyclohexanone... 

A similar retardation effect of cosolvent was reported previously for benzene oxidation [90, 91]. The solvent may compete with reactant for diffusion in the channels and adsorption at the active sites of TS-1 catalyst. The activity Ti-beta for 1-hexene and cydohexanol oxidations is highest in acetonitrile, which is a polar, nonprotic solvent [92]. This is in contrast with the observed enhancement of the activity of TS-1 by methanol and protic solvents [68]. These differences have been... 

---