Cyclohexanone 3,3-pentamethylenediaziridine

A. 3,3-Pmtamethylenediaziridine. A solution of 147 g. (1.5 moles) of cyclohexanone in 400 ml. of 15iV aqueous ammonia (6.0 moles) in a 1-1. beaker is stirred mechanically and cooled to 0° with an ice-salt mixture. Maintaining the temperature of the solution between 0° and - -10°, 124 g. (1.0 mole) of 90% hy-droxylamine-O-sulfonic acid (Note 1) is added in portions of about 1 g. The addition requires about 1 hour, and the mixture is stirred for mother hour at 0° and allowed to stand overnight at —15° in a refrigerator. The precipitated crystalline cake is filtered and pressed tight with a glass stopper. The solid is washed with 50-ml. portions of ice-cold ether, toluene, and finally ether. There is obtained 110-115 g. of product which is 70-90% pure (Notes 2 and 3). The product is divided into two portions, each of which is boiled briefly with a 50-ml. portion of toluene the solutions are decanted from small salt residues and cooled to 0° for 2 hours. The precipitates are filtered with suction and washed with 50 ml. of ice-cold petroleum ether. The combined yield of 3,3-pentamethylenediaziridine is 68-78 g. (61-70%), m.p. 104-107°. The purity is 96-100% (Note 4). 

Diazirines are the cyclic isomers of the alphatic diazo compounds. Both the diaziridines and the diazirines are starting materials for the synthesis of alkyl hydrazines. 3,3-Pentamethyl-enediaziridine can be hydrolyzed quantitatively to hydrazine. Methylamine may be substituted for ammonia in the procedure resulting in l-methyl-3,3-pentamethylenediaziridine (m.p. 35-36°, yield 62% of theoretical) and then methyl hydrazine. Use of ethylenediamine leads to ethylene bis-hydrazine via a bifunctional diaziridine (m.p. 143-144°, yield 48% of theoretical). Ammonia can also be replaced by w-propylamine or cydo-hexylamine cyclohexanone by acetone. 

Diaziridines and diazirines. Hydroxylamine-O-sulfonic acid and ammonia react with cyclohexanone to form 3,3-pentamethylenediaziridine, which can be oxidized with silver oxide to 3,3-pentamethylenediazitidine. The product, a liquid, is distilled... 

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