Cydohexyl chloride

In a 1500 ml. round-bottomed flask, carrying a reflux condenser, place 100 g. of pure cycZohexanol, 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 cydohexyl 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 6-142 5°. The yield is 90 g. 

Replacing cydohexyl bromide with cydohexyl chloride. 

Determine the percentage of unreacted cydohexyl bromide in the sample mixture from the chromatogram for parameters 1,2, and 3. Determine the percentage of cydohexyl chloride and iodide in parameters 4 and 5, respectively. 

Cydohexyl-NENA or N-(2-Nitroxyethyl)-cydo-hexylnitramine, CgH,. N(N02).CH2.CH2.ON02 mw 233.22, N 18.02% col crysts (from acet ligroin), mp 37.8-38.4° can be prepd from cyclohexanol amine, 98% HNOa acetic anhydride in the presence of a chloride catalyst. This compd was prepd as a possible NC plasticizer for use in double-base proplnts... 

The effect of the leaving group was briefly examined but cinnamyl bromide gave a substantially lower ee (38%). Cinnamyl dimethyl phosphonate or acetate gave very poor results. The cydohexyl-substituted allylic acetate 21 on the other hand afforded a completdy y-selective reaction but the product turned out to be racemic. Changing the Grignard reagent halide from bromide to either chloride or iodide resulted in very low ees. 

The Calculations Using an Internal Standard. The calculations allow us to compare the amount (%) of cydohexyl bromide (or chloride or iodide) reacted at the 30-min time point for each of the different reaction parameters. 

Cydohexyl isocyanate Cyclohexylisopropylamine Cydohexyl isothiocyanate Cyclohexylmagnesium chloride Cyclohexyl methacrylate Cyclohexylmelhylamine... 

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