Benz indole, 1,3,4,5-tetrahydro

Some other ring expansions involving the intramolecular amino Claisen rearrangement of vinylarylaziridine [ 123], the Diels-Alder reaction of indoles with acetylene derivative [124-127] and the dibromocarbene insertion into quinoline enol ethers [ 128] have been used to prepare 1-benzazepines. On the other hand, treatment of 3-chloro-3-phenyl-l,2,3,4,5,6-hexahydro-l-benz-azocin-2-ones with piperidine causes a ring contraction to give 2-phenyl-2-(l-piperidinylcarbonyl)-2,3,4,5-tetrahydro-l//-l-bcnzazepines in an excellent yield [23]. 

Fig. 5 l-p-toluenesulfonyl-6,7,8,9-tetrahydro-N,Al-di- -propyl-lH-benz [g]indol-7-amine (TPBIA) [112]... 

Ennis, M.D., Stjernldf, P, Hoffman, R.L., Ghazal, N.B., Smith, M.W., Svensson, K., Wikstrdm, H., Haadsma-Svensson, S.R., and Lin, C.-H., Structure-activity relationships in the 8-amino-6,7,8,9-tetrahydro-377-benz[e]indole ring system. Part 2. Effects of 8-amino nitrogen substitution on serotonin receptor binding and pharmacology, J. Med. Chem., 38, 2217, 1995. 

Chloro-l,4-dihydro-9-methylnaphthalen-l,4-imine is converted into isomeric dihydrocyclo-but[(j]indoles by direct photolysis, which are in turn converted into 6- and 9-chloro-1-methyl-1//-benz[/)]azepines upon heating in toluene. The azepines are converted back into the dihydrocyclo-but[/)]indoles by light, from which it has been postulated that the azepines may be the primary products in the reaction <85TL2827>. The isomerization of a number of l,4-dimethyl-9-halogeno-l,2,3,4-tetrahydro-l,4-iminonaphthalenes to 2,3,4,5-tetrahydro-l//-benz[/>]azepines by AgBp4 in benzene/methanol mixtures has been reported <86TL407i>. Under similar conditions, the 1,4-dihydro-derivatives are converted into quinolines. 

Various 4-substituted indoles were prepared and a synthetic method for 4-nitro-l,3,4,5-tetrahydrobenz[cd]-indole derivatives was carried out [46] and also for 4,5-disubstituted lH-l,3,4,5-tetrahydrobenz[cd]indole derivatives [47] using intramolecular Michael addition. Furthermore, a method [48] was published describing the successful syntheses of 4-nitro-l,3,4,5-tetrahydro-benz[cd] indole and its 1-hydroxy derivative. 

Substituted 7,12-dihydroindolo[3,2-c(][l]benzazepin-6(5/0ones 2a and 2b were first reported in 1958 by MacPhillamy et al. [33] as the last intermediate in an 11-step synthesis of 4-ethyl-5,6,7,12-tetrahydro-2-methylindolo[3,2-t/][l]benzazepine. In 1992, Kunick reported the preparation of six indolo[3,2-d][l]benzazepin-6(5/f)ones [34] in a three-step procedure. The crucial step was the decarboxylation reaction of 2,3-dihydro-5-hydroxy-2-oxo-l/7-benz[(t]azepin-4-carboxylic acid ethyl ester into 3,4-dihydro-lH-benz[ ]azepin-2,5-dione, which made possible the subsequent Fischer indole synthesis, with formation of the desired 7,12-dihydroindolo[3,2-fiT [l]benzazepin-6(5/f)ones. 

C14H16N2O3 0.5 H2O, 2,3a,4,5-Tetrahydro-7,8-dimethoxy-3a-methyl-3H-benz[g]indazol-3-one hemihydrate, 46B, 272 Cl4H16N2O4, 2,3-Hydroxy-2,3-dimethyl-4a,9a-diaza-1,2,3,4,4a,9,9a,10-octahydroanthracene-9,10-dione, 44B, 256 Cl4H16N2O5 f 1,2/3-Dimethoxycarbonyl-3aa-hydroxy-2a,3,3,8,8aa-penta-hydropyrrolo[2,3-b]indole, 44B, 256 C14H1yBrjN, trans-6,8-Dibromo-1,2,3,4,4a,9a-hexahydro-4a,9-dimethyl-carbazole, 37B, 146... 

Isopropylmagnesium chloride in tetrahydrofuran added slowly during 10 min. via a syringe to 2-N-methylamino-3,4-dihydronaphthalene and dry tetrahydrofuran at a rate to maintain gentle reflux, then bromodiloroethane added in the same manner followed by additional Grignard reagent 3-methyl-l,2,4,5-tetrahydro-3H-benz[e]indole. Y ca. 100%. F. method s. D. A. Evans, C. A. Bryan, and G. M. Wahl, J. Org. Chem. 55, 4122 (1970). 

A sealed stainless-steel bomb containing spiro[cyclopropane-l,l -(l, 2, 3, 4 -tetra-hydro-2 -oxonaphthalene)], methylamine, CaO, and benzene rocked and heated 7 days at 100-120 3-methyl-l,2,4,5-tetrahydro-3H-benz[e]indole. Y 72.5%. F. e. s. S. L. Keely, Jr., A. J. Martinez, and F. C. Tahk, Tetrahedron 26, 4729 (1970). 

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