RESEARCH IN NITROMONOMERS AND THEIR APPLICATION TO SOLID SMOKELESS PROPELLANTS.
Annual progress rept. no. 26, 15 Sep 63-14 Sep 64,
PURDUE UNIV LAFAYETTE IND
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The mono-nitration of cyclic ketones with alkyl nitrates in the presence of potassium t-butoxide affords two products, alpha-mononitroketones and omega-nitro carboxylic esters. The infrared, NMR and ultraviolet spectra of cyclic alpha-nitroketones and of their potassium salts are reported. The reaction of alpha-nitroketones in acidic media was investigated. The major product with the five membered cyclic ketone, 2-nitro-3,5,5trimethylcyclopentanone is a six membered cyclic N-hydroxyimide, 2,6-dioxo-3,3,5-trimethyl-l-hydroxy-laza-cyclohexane. A study of the ring opening reaction of salts of cyclic alpha, alpha-dinitroketones to alpha, omega-dinitroalkanes was continued. In the case of alpha, alpha-dinitrocyclopentanone, dipotassium 2-keto1,3-cyclopentanedinitronate and potassium 2-keto-3nitrocyclopentanenitronate are converted to 1,4dinitrobutane in yields of 71 and 84, respectively, on treatment with formic acid at pH4. In the case of alpha, alpha-dinitrocyclohexanone, ring cleavage of dipotassium 2-keto-1,3-cyclohexanedinitronate I already occurs with carbon dioxide at about pH6 to give 1,5dinitropentane II in 82 yield with aqueous acetic acid at pH5 the yield of V amounts to 88. 2,6-Dinitrocyclohexanone, a surprisingly stable compund is obtained when pure compound I is treated with hydrogen chloride in anhydrous ether 93.5 yield or in anhydrous methanol 76 yield.