Hexahydro-1,2-oxazepine

Reaction of the l-aryl-2-phenacylcyclopropanes with chlorosulphonyl isocyanate and subsequent removal of the chlorosulphonyl group with benzenethiol in pyridine affords the 4,5-dihydro-1,3-oxazepines (91) <95SCI939> and in a reaction sequence in which an aziridine is the source of nitrogen, methyl l-benzyloxycarbonylaziridine-2-carboxylate reacts with 2-(N-benzyl-A -/t /7-butoxycarbonyl)aminoethanol to give the derivative (92) which, after removal of the Boc group, is subject to a reductive cyclisation to yield the hexahydro-l,4-oxazepine (93) <95CPBI 137>. 

A low yield of the solid hexahydro-3,3,7,7-tetramethyl-l,2-oxazepin-5-one (38) (m.p. 50°C) can be obtained on reaction of phorone with hydroxylamine in the presence of base. The competing reaction is the formation of the five-membered ring compound, 3-isobutenyl-5,5-dimethyl-4,5-dihydroisoxazole by intramolecular 1,2-addition, rather than by 1,4-addition by nitrogen in the intermediate (37), followed by dehydration. Some of the oxime of (38) is also formed (Scheme 3) <81G279>. 

A further synthesis of the hexahydro-l,3-oxazepine system (28) has been developed by Holmes and co-workers. It is based on the cyclization of the amino alcohol (40 Z = C02CH2Ph) with pyridinium p-toluenesulfonate and phenylselenoacetaldehyde diethylacetal using Dean-Stark con-... 

The compound hexahydro-3-tetradecyl-l,3-oxazepine is useful as a photographic material for magenta dye image stabilization <88JAP6343146>. 

Treatment of l,r-iminobis-2,2-butanols (1) with 70% sulfuric acid gives rise to six-membered cis- and trfl j-2,6-diethylmorpholines (2) and other heterocyclic systems whereas with 50% H2SO4, cis- and tranj-hexahydro-l,4-oxazepines (3) are formed, along with the morpholine derivatives, as the major product (Equation (1)) <83JHC1681>. 

In a similar manner,benzo[6]pyrido[3,2 [l,4]oxazepinones 115 were prepared using a ligand-free, copper-catalyzed process (14RA55640). An intramolecular 1,3-dipolar cycloaddition reaction of 6-azido-4-0-propargyl glucopyranosides generated aryl-substituted hexahydro-4H-pyrano[2,4 [l,2,3]triazolo[5,l-c][l,4]oxazepines 116 (14RA63962). 

An almost complete resolution was attained between unlabeled and di-, tri-, or tetradeuterated drugs active on the central nervous system -l,2,3,4,10,14b-hexahydro-2-methyl- dibenzo [c,/]py-razino[l,2-fl]azepine (mianserin [VII]) and 1,3,4, 10,14b-hexahydro-2,7-dimethy l-2H-dibenzo [c,f -py-razino[l,2fl]oxazepine (Org GC 94 [VIII]). [3,3,-4,4- H4]Org GC 94 was chromatographed on p-Porasil column and n-hexane-2-propanol (90 10, v/v) to which a solution of 4% ethanol and 0.1%... 

Cl7H1UN2O2, 2-Oxo-l-phenyl-1,5-methano-1,2,4,5,6,11-hexahydro-(1,2,3)oxadiazolo[3,2-a]cinnoline, 44B, 344 Cl7H15CIN2O2, 7-Chloro-l,2-dimethyl-2,5-epoxy-5"phenyl-l,2,4,5-tet-rahydro-3H-l,4-benzodiazepin-3-one, 37B, 159 C1 H1gNOg, 7,8-Benzo-3-ethoxycarbonyl-2-methoxycarbonyl-9-methyl-9-aza-5-oxabicyclo[4.3.0]nona-(1(6),2)-dien-4-one, 46B, 275 Cl7H16CIN3O, 2-Chloro-11-(1-piperazinyl)dibenz[b,f](1,4)oxazepine, 43B, 461... 

Kerb, U., H.-D. Berndt, U. Eder, R. Wiechert, P. Buchschacher, A. Furlenmeier, A. Furst, and M. Muller Zur Synthese des Batrachotoxinins Synthese von 3p-Acetoxy-16p,20p-dihydroxy-4 -methyl-18-nor-5p,14p-pregnano-[13,14-f]-hexahydro-r,4 -oxazepin-3 -on-(20a). Experientia 15, 759—761 (1971). 

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