Chlorination of cyclohexylamine with

Chlorination of cyclohexylamine with i-butyl hypochlorite, 45,16 Chlorine, reaction with 2-butyne, 46, 34... 

Although complete replacement of chlorine atoms can be accomplished with most kinds of amines, this becomes difficult in the reactions with sterically hindered amines. Thus in the reactions of N3P3C16 with cyclohexylamine (71) and adamantyl amine (72), the yields of fully substituted products are low. In the reactions of N3P3C16 with further sterically encumbered amines such as... 

When cyclohexyl chloride is the desired product for use in the preparation of cyclohexylamine or for condensations according to the Friedel and Crafts reaction, it appears advantageous to chlorinate in the presence of light and to use at least a 10 1 molar ratio of cyclohexane to chlorine in a cyclic process. The products of reaction are continuously withdrawn from the reaction chamber to a still (Fig. 6-6) where the unconverted cyclohexane is distilled off, condensed, and returned to the chlorinator which is provided with an encased battery of electric lights. The chlorinator, which is maintained at 65-65°C, is preferably made of lead, nickel, or Monel metaJ in order to provide better resistance against the corrosive action of the reaction products. A 5deld of about 94 per cent cyclohexyl chloride is thus obtained in batch operations when about half of the chlorine theoretically required to convert all the cyclohexane to cyclohexyl chloride has been reacted. 

Analysis of Reagent Purity mp, NMR, combustion analysis. Preparative Methods )V-cyclohexylbenzenesulfonamide can be prepared by addition of benzenesulfonyl chloride to a solution of cyclohexylamine in pyridine and purified by recrystallization from ethanol. TV-Chlorination is accomplished by treating a solution of TV-cyclohexylbenzenesulfonamide in dichloromethane with NaOCl solution at 0°C followed by dropwise addition of glacial acetic acid. Alternatively, a suspension of W cyclohexylbenzenesulfonamide in acetic... 

Scheme 9.103. The Hofmann rearrangement, which results in the loss of carbon dioxide (CO2) and the production of an amine from oxidation of an amide with bromine (Br ) or chlorine (CI2).The oxidation produces the A -halo-compound, which, on treatment with base, undergoes rearrangement to generate the N-alkylisocyanate (cyclohexylisocyanate in this case). Treatment of the Af-alkyhsocyanate with water, produces the transient carbamic acid. The carbamic acid undergoes spontaneous decarboxylation in water to carbon dioxide (CO2) and cyclohexylamine (Chapter 10). Details of the Hofinann rearrangement will be discussed subsequently. But see Hofmann, A. W. Chem. Ber., 1881,7 /, 2725.

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