New Psychotropic Agents.^1a IV. Derivatives of Dibenzo[a,d][1,4]cycloöctadiene

Abstract

The residue was treated with 50 nil. of * hydrochloric acid and the aqueous solution was extracted with ether. The ether layer was discarded. The aqueous layer was made alkaline by the addition of 15 ml. of 5 X sodium hydroxide and the organic base was extracted into ether. The ether layer was washed with water, dried over magnesium sulfate and distilled. A low-boiling forerun -was discarded and (-)V was collected at 144-148°(0.08 mm.). The yield was 4.6 g. (57%), zz25d 1.562, [a]25u -18.8°.

.beta.-Iodo Ketones by Prevost Reaction Of Vinyl Carbinols

“…6-(Iodomethyl)-5,6.11>12-tetrahydrodibenzo[o,e]cycloocten-5-one (10). Yield of crude product (oil): 99%.…”

Synthesis of 5-oxo-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-10-carboxylic acids corresponding nitriles, and related bridged lactones, hemiketals, lactams, amines, amidoximines, and amidines (5,10-epoxymethano and 5,10-iminomethano compounds)

“…Found: C, 81.20; H, 6.42. 10-Cyano-5.ff-dibenzo[a,d]cyclohepten-5-one (6). A. Bromination.-A solution of 12.7 g of keto nitrile 5a and 12 g of bromine in 300 ml of benzene was let stand 2 days (room temperature). The ether-diluted, washed (NaHCOs solution, water) and dried solution on evaporation gave 18 g of crude bromo keto nitrile, a slightly fuming, viscous, yellow oil which did not crystallize.…”

“…Similar hydrogenolysis of keto acid 8a gave acid 12. Amide 11a was also obtained from acid 12 as shown.…”

Synthesis of 6-substituted 5,6,7,12-tetrahydrodibenzo[a,d]cyclooctenes

“…Thus it was necessary to have available a series of mono-and di-6-substituted 5,6,7,12-tetrahydrodibenzo [a, d]cyclooctenes 1 and this paper describes the synthesis of these compounds. The only other carbocyclic compounds reported in the literature having the skeleton of 1 are those with substitution at C-12 (3). These were prepared according to Scheme 1 where R, = R2 = EI.…”

“…Also, Winthrop et ul. (3) found that the cyclization step was very sensitive to structural change in the reactants, and in some cases the desired cyclization product was not obtained. ' The reaction sequence chosen by us is shown in Scheme 2.…”