Die Nitril‐Carboxamid‐Umlagerung

The Nitrile Carboxamide Rearrangement By reaction of cyclohexanone-2-carboxamide (4) with cyan amide 1-cyano-cyclohex-1-en-2-yl-urea (6) is formed via nitrile carboxamide rearrangement. Whilst compound 6 with 1,2-diaminobenzene hydrochloride forms 11-amino-1 H-2,3,4,5-tetrahydrodibenzo[b,e][1,4]diazepin hydrochloride (8 and 8a), compound 6 and 1,2-diaminobenzene form hexahydro-benzimidazo[1,2-c]-quinazolin-6-one (12). Compound 8 with sodium hydroxide yields 11-amino-1 H-2,3,4,11a-tetrahydrodibenzo[b,e]-[1,4]diazepin (9). Compound 6 reacts with cyclohexylamine to form N-(1-cyanocyclohex-1-en-2-yl)-N′-cyclohexyl urea (10). Compound 10 with 1,4- or 1,2-diaminobenzene hydrochloride yields compound 7 and 8. In alkaline solution 10 cyclises to 4-amino-3-cyclohexyl-2,3,5,6,7,8-hexahydroquinazolin-2-one (11). Compound 4 and malonitrile form either 3-amino-4-cyano-1,2,5,6,7,8-hexahydro-isoquinol-1-one (13) or 1-amino-4-cyano-2,3,5,6,7,8-hexahydro-isoquinol-3-one (14). Compound 13 and alkaline formaldehyde react to cyanooctahydroisoquinoline-[2,3-c] [1,3,5]oxdiazin-6-one (17). 2-Cyanoethyl-cyclohexan-one-2-carboxamide (22), prepared by Michael-reaction from 4 and acrylonitrile, forms via nitrile carboxamide rearrangement 10-cyano-1,2,3,4,5,6,7,10-octahydroquinolin-2-one (24) and 2-(1′-cyano-cyclohexyl-2′-one)-propionic acid (25). Nucleophilic attack of the NH2-group at the cyanogroup of compound 22 forms 5-(spirocyclohexan-2′-one)-hexahydropyridin-2,6-dione (27).