3.3- Pentamethylenediaziridine

For the analysis an ethanolic solution of the 3,3-pentamethylenediaziridine is treated with a solution of potassium iodide in 2N sulfuric acid. It liberates two equivalents of iodine instantaneously. 

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 96a and 96b react with diethyl acetylenedicarboxylate to yield oily products, presumed to be 97a and 97b. These have been characterized by hydrolyzing them to the known pyrazolinones 98a and 98b, respectively [Eq. (17)]. A similar observation has been made in the reaction of l-methyl-3,3-pentamethylenediaziridine (96b) with ethyl propiolate. The reaction of 3,3-pentamethylenediaziridine with ethyl propiolate, on the other hand, yields a simple 1 1 Michael adduct. ... 

An interesting anionic aziridination of a,p-unsaturated amides was reported this past year <99TL5207> utilizing Uthiated 3,3-pentamethylenediaziridine (134) as the nitrogen atom donor. Formation of ds-aziridines was generally observed, regardless of e stereoc emistry o e... 

Besides being precursors to diazirines (and by extension, carbenes), diaziridines have found application as aziridinat-ing agents <2002HCA4272, 1999TL5207>. 3,3-Pentamethylenediaziridine 87 was found to aziridinate a,/3-unsatu-rated amides in good yield, and with high diastereoselectivity. This diastereoselectivity was found to be independent of the substrate geometry (Scheme 29). 

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... 

In the reaction of 3,3-pentamethylenediaziridine 116 with diphenyl-cyclopropenone the C—N—N moiety can add either to the carbonyl group, to give 123, or to the ring-opened cyclopropenone to give 124. ... 

An ethereal soln. of 3,3-pentamethylenediazirine added with ice-cooling to a Grignard soln. prepared from cyclohexyl bromide and Mg in ether, then allowed to stand 1 hr. without cooling l-cyclohexyl-3,3-pentamethylenediaziridine. Y F. e. s. E. Schmitz and R. Ohme, B. 94, 2166 (1961). 

---