Morphanthridines I. 11‐aminoalkylidene‐and ll‐(4‐Piperidylene)‐5,6‐dihydromorphanthridines

Abstract

New methods are described for the preparation of 5,6‐dihydro‐11‐morphanthridone, 5‐substituted 5,6‐dihydro‐11‐morphanthridones and nuclear halogenated derivatives. Basic Grignard reagents convert these ketones to carbinols, which through dehydration affords a convenient route to straight chain and cyclic 11‐aminoalkylidene derivatives.

Novel syntheses of 1,4-benzodiazepines, isoindolo[2,1-d][1,4]benzodiazepines, isoindolo[1,2-a][2]benzazepines, and indolo[2,3-d][2]benzazepines, based on use of the Strecker reaction

“…It is also relevant to note that they did not report any LiAlH4 reductions of their 6-oxo analogs of 4. We find similarly that compounds 35 (Scheme IV) cannot be reduced with LiAlH, to recognizable products.…”

“…Amidoxime 26b.-A solution of hydroxylamine was prepared from 2.73 g of Na in 300 ml of ethanol and 8.2 g of H2NOH-HCl, nitrile 26a (4.2 g) was added, and the whole was refluxed for 6 hr. The filtered solution was evaporated, and a twice filtered and concentrated, dry ether solution of the material was gassed gently with dry HC1 to give 3.5 g (66%) of the hydrochloride as cream-colored crystals: mp 191-193°dec, raised to 195-197°o n recrystallization from ethanol-ether; ir 2.95, 3.05-3.18 (bonded), 5.99-6.03 (doublet), and 6.23 µ; uv 227 nm (e 35,680) and 298 ( 9660) with inflections at 212 (29,760) and 232 (35,110).…”

“…Caled for C18H15C1N203: C, 63.07; , 4.41; N, 8.17. Found: C, 63.26; H, 4.46; N, 8.08. Compound 33a.-Similarly conducted Strecker reaction of 29b (30 g) with intermittent warming on a steam cone for 5 hr gave 35.5 g of viscous, yellow oil which did not crystallize: ir 5.79 and 6.00 µ (no NH band); uv 235 nm (e 18,220) and 362 (1770). Phthalido-3-spiro[3,5']-l-methyl-2-oxo-2,3-dihydro-4,l-benzoxazepine (34a).-Crude 32b (IV = H), from bromoacetylation of 2 g of 29b (IV = H), was treated with 125 ml of saturated ethanolic NH,.…”

Morphanthridines III. 6‐Basic substituted morphanthridines

“…We haye recently reported on the synthesis of 11-aminoalkyl-(1) and ll-aminoalkylidene-5,6-dihydromorphanthridines (2). Although a few 6-alkyland 6arylmorphanthridines had previously been described in the literature ( 3 ) , only after our work on the preparation of 6-basic substituted morphanthridines was completed did references appear describing 6aminoalkylaminomorphanthridines (4).…”