Sodium cyclohexoxide

C. Diazomethane. Sodium cyclohexoxide method (Note 10). A solution of sodium cyclohexoxide is prepared from 4 g. of sodium and 100 ml. of cyclohexanol (Note 11) in a 2-1. flask the cyclohexanol is heated to boiling under reflux to speed up the formation of the alkoxide. As soon as the sodium has disappeared, heating is discontinued and the condenser is removed. When solid begins to separate from the solution, the mixture is stirred with a stout rod to prevent the formation of a hard cake. The flask is surrounded by an ice bath, and, when the temperature of the mixture has dropped to 10°, 300 ml. of dry ether and a solution of 49 g. (0.33 mole) of N-nitroso-j8-methylaminoiso-butyl methyl ketone dissolved in 600 ml. of dry ether are added. The flask is connected to a 25-cm. fractionating column and an efficient water-cooled condenser (Note 12). The delivery end of the condenser should be connected to an adapter which dips below the surface of 50 ml. of ether contained in a 1-1. Erlenmeyer... 

Treatment of methyl N-nitroso- -alkylaminoisobutyl ketones with sodium isopropoxide or sodium cyclohexoxide furnishes a third method (equation 3)- The preparation of the starting materials involves simply the addition of an amine to mesityl oxide with subsequent nitrosation. In this case the starting material (equation 3, R=H) for diazomethane is more stable than nitrosomethylurea and does not have an irritating action like methyinitrosourethane. ... 

McManus er at, J. Org. Chem. 33, 4272 (1968) from KOH and nitrOsomethylurea Dessaux, Durand, Bull. Soc. Chim. Prance 1963, 41. These methods yield gaseous diazo-methane The following procedures yield ether solns of diazomethane. From N-nitroso-d-meihylaminoisobutyl methyl ketone in ether and isopropanol by reaction with sodium isopropoxide or from the same ketone in ether by reaction with sodium cyclohexoxide Redemann et at, Org. Syn. 25, 28 (1945). By KOH saponification of nitrOsomethylurea in ether Arndt, Org. Syn. coll. vol. II, 165 (1943), Or of nitro-somethylurethan in ether von Pechmann. Ber. 27, 1888... 

One mole of alkoxide was present in each preparation together with 1.5 mole of sodium chloride and around 0.34 to 0.43 mole of allylsodium, as recorded in the second column. The abbreviations refer, respectively, to isopropoxide, butoxide, pentoxide, cyclopentoxide, and cyclohexoxide. 

Certain non-reactive chlorides can be dehydrochlorinated with sodium l-butyl-2-cyclohexoxide without the use of an autoclave . A simple and selective demethylation of o-methoxyphenols has been found... 

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