No abstract

No abstract

The treatment of alkylcyclohexanone oximes with sodium azide and chlorosulfonic acid has been shown to lead through ring expansion and a second cyclization to alkylpentamethylenetetrazoles (1). When this reaction was applied to unsymmetrically substituted cyclohexanone oximes (I), structurally isomeric pentamethylenetetrazoles (II and III) could result depending upon the extent of 1-2 or 1-6 bond rupture occurring in the cyclohexanone oxime ring. When the reaction was applied to 3,5-dialkylcyclohexanone oximes, pure dialkylpentamethylenetetrazoles were isolated, but no attempt was made to determine the position of the substituents in the products (1). It has been the purpose of this investigation to determine the position of the substituents in such dialkylpentamethylenetetrazoles.The initial stage of tetrazole formation from the cyclohexanone oximes was assumed to be similar to the Beckmann rearrangement; at some point after ring expansion but before completion of the rearrangement by amide formation, the addition of the azide group caused tetrazole formation (1). Although amides do not react directly with hydrazoic acid or sodium azide to form tetrazoles, this conversion may be accomplished indirectly if the amide is first allowed to react with phosphorus pentachloride. The imide chloride so formed reacts readily with hydrazoic acid to form a tetrazole (2-4). It appeared feasible to accomplish stepwise conversion of cyclohexanone oximes to pentamethylenetetrazoles by first rearranging the oxime and determining the structure of the cyclic amides (IV and V) formed, and second, converting the cyclic amides into pentamethylenetetrazoles by way of their imide chlorides. This procedure has now been employed to establish the position of the substituents in 7-methyl-9-ethylpentamethylenetetrazole (II)3 and its isomer, 7-ethyl-9-methylpentamethylenetetrazole (III) and to establish the identity of the methylethylpentamethylenetetrazole described by Harvill, et al. (1).Since the structures of the pentamethylenetetrazoles would depend on knowledge of the structures of the lactams, a satisfactory method of converting the lactams into saturated aliphatic acids or other easily identifiable compounds was essential. The conversion of the parent e-caprolactam into n-caproic acid was reinvestigated for this purpose. Attempts to reduce e-caprolactam or e-amino-1 Based on a thesis submitted to the School of Graduate Studies at Michigan State College in 1952 by Richard L. Burke in partial fulfillment of the requirements for the degree of Doctor of Philosophy.

No abstract

No abstract