Production of cycloaliphatic nitrates

Abstract

Abstract Cycloaliphatic nitrates are produced by dissolving cycloaliphatic alcohols in an indifferent solvent and then treating them in this solution with nitrating acid. A suitable temperature range for the reaction is between +20 DEG and -40 DEG C., preferably between -5 DEG and -10 DEG C. Suitable cycloaliphatic alcohols are cyclopentanol, cyclohexanol, cyclo-octanol, cyclodecanol, decahydronaphthol, the isomers of methyl cyclohexanol and dimethylcyclohexanol and mixtures of such alcohols. Examples of indifferent solvents are aliphatic halogenated hydrocarbons, such as chloroform, carbon tetrachloride and ethylene chloride, or aliphatic hydrocarbons, such as petroleum ether, hexane, or heptane, or cyclic hydrocarbons, such as methylcyclopentane, cyclohexane, methylcyclohexane, dimethyl cyclohexane or mixtures thereof. The alcohol is dissolved in the solvent in a ratio of 1 part alcohol to 1, 2, 3 or more parts of solvent. The nitrating acid is a mixture of 1 part of concentrated nitric acid to 1, 2, 3 or more parts of concentrated sulphuric acid. The nitration may be carried out continuously by leading the reactants through a tubular coil at the desired temperature. In examples: (1) cyclohexanol dissolved in carbon tetrachloride is introduced rapidly with stirring into a nitrating acid mixture cooled to -5 DEG to -10 DEG C., and the organic layer is washed with water and soda solution and fractionally distilled to obtain cyclohexanol nitrate; methylcyclohexanol nitrate and dimethylcyclohexanol nitrate are similarly obtained; (2) cyclopentanol dissolved in chloroform is nitrated as in (1) and poured on to crushed ice, the organic layer is washed with sodium bisulphite to remove cyclopentanone, then with water and soda and then is fractionally distilled to obtain cyclopentanol nitrate; cyclo-octanol nitrate is similarly obtained; (3) decahydronaphthol nitrate is obtained by the process of (1). The products are valuable fuel additives.

Inventors

• 👤 Schickh Otto Von

Bibliographic Details