No abstract

The diaziridine -Gy-dihydrospiroicyclohexane-bVClffl-diazirinotl^-cKS.lJbenzodiazocmeJ-S'.lO'-dione (7) isomerizes in refluxing benzene into 3-(cyclohexylideneamino)-lR-3-benzazepine-2,4(3if,5H)-dione ( 8) and rearranges in refluxing benzene containing triethylamine hydrochloride into 3-(1 -cyclohex-1 -yl) -1,3,4,6-tetrahydro-3,4-benzodiazocine-2,5-dione (9). l-p-Nitrobenzoyl-2,3,3-trialkyldiaziridines isomerize in chloroform or acetonitrile at ambient temperatures into labile 2-aryl-4,5,5-trialkyl-A2-l,3,4-oxadiazolines (lla-c). The latter compounds react with both electrophiles and nucleophiles such as aromatic aldehydes and ynamines to give 2,5-diaryl-4-alkyl-A2-l,3,4-oxadiazolines and pyrazoline derivatives, respectively.

A new method for preparing mono-and bis(hexahydro-3,3,5,5,7-pentaalkyl-2H-l,4-diazepin-2-ones) is reported (Schemes I and ). The key step of this synthesis is the final one in which a 1,3-diamine is reacted with a ketone in the presence of sodium hydroxide, chloroform, and a phase-transfer catalyst (PTC). Bis(hexahydro-3,3,5,5,7-pentaalkyl-2H-l,4-diazepin-2-ones) are isolated as a mixture of diastereomers. Of these bis compounds, diastereomers of l,l'-(l,2-ethanediyl)bis(hexahydro-3,3,5,5,7-pentamethyl-2H-l,4-diazepin-2-one) (5a) can be readily separated by a fractional recrystallization, or their diastereomeric distributions can be measured by 13C NMR.

Metalation of 2‐Methylpyridine Derivatives: Ethyl 6‐Methylpyridine‐2‐Acetate reactant: 32.1 g. (0.300 mole) of 2,6‐lutidine product: ethyl 6‐methylpyridine‐2‐acetate

Das durch Umsetzung von o‐Phenylendiacetylchlorid (I) mit überschüssigem 3,3‐Pentamethylendiaziridin (II) erhältliche Diaziridin (III) isomerisiert in siedendem Benzol quantitativ zum Benzoazepindion (IV), in Gegenwart von Triäthylaminhydrochlorid unter den gleichen Bedingungen zum Tetrahydrobenzodiazocindion (V).