Patent GB-1273400-A (GB)
Title: Dibenzocyclopropapentalene compounds, process for their manufacture and compositions containing them
IPC: B01J19/12
Filed: 1969-11-18
Abstract: 1,273,400. Dibenzcyclopropapentalenes. CIBA-GEIGY A.G. 18 Nov., 1969 [26 Nov., 1968; 29 Aug., 1969], No. 56365/69. Heading C2C. Novel Compounds I in which Ph 1  and Ph 2  represent optionally substituted 1,2-phenylene radicals; Am is an amino group which may be substituted, or a hetero cyclic amino group; R 1  is H, etherified or esterified OH, an aliphatic, araliphatic or aromatic radical or 1-4 C alkylene linked with the N of Am; and R 2  and R 3  are H, OH, etherified or esterified OH or aliphatic radicals and acyl, quaternary ammonium, N-oxide and acid addition salt derivatives thereof are prepared (1) by reacting Compounds II in which X is haloalkyl with HAm; (2) by reacting compounds II where X is COAm with LiA1H 4  to give compounds I where -alk-Am is -CH 2 Am; (3) by irradiating compounds III with U.V. light; or (4) by cyclization of Compounds IV. in which Y and Z are halo and if desired a resulting compound is converted to an acyl derivative, N-oxide derivative, or salt thereof or a salt is converted to the free base. Compounds II in which X is haloalkyl, are prepared by reaction of the corresponding hydroxyalkyl derivatives with a halogenating agent. Compounds II in which X is COAm are prepared by reaction of HAm with the corresponding acid halide. Compounds III are prepared by reaction of the appropriate haloalkyl derivative with HAm. Compounds IV are prepared by halogenation of the corresponding dihydroxy derivatives. Further intermediates are isolated in the following reaction schemes. 11-Carboxy-9,10- etheno-9,10-dihydro-anthracene is irradiated with U.V. light to give 8d-carboxy-4b,8b,8c,8dtetrahydro - dienzo[a,f]cyclopropa[c,d]pentalene which on treatment with SOCl 2  gives the corresponding acid chloride. 11 - Carbethoxy - 9,10 - etheno - 9,10-dihydroanthracene is irradiated with U.V. light to give 8d - carbethoxy - 4b,8b,8c,8d - tetrahydro - dibenzo- [a,f]cyclopropa[c,d]pentalene, which is then reduced to the corresponding 8d-hydroxymethyl derivative. Anthracene is reacted with 3-butynol to give 11, - (2 - hydroxyethyl) - 9,10 - etheno - 9,10- dihydro-anthracene which is then reacted with PBr 3  to give the corresponding 11-(2-bromoethyl)- derivative. 8d-Chlorocarbonyl-4b,8b,8c,8d-tetrahydro-dibenzo[a,f]cyclopropa[c,d]pentalene is reacted with diazomethane to give the corresponding 8ddiazomethylcarbonyl derivative which on reaction with silver benzoate and dimethylamine gives 8d - dimethylaminocarbonylmethyl - 4b,8b,8c,8dtetrahydro - dibenzo[a,f]cyclopropa[c,d]pentalene. 2-Chloroanthracene is reacted with ethyl propiolate and the product hydrolysed to give 2- chloro - 9,10 - etheno - 9,10 - dihydro - anthracene- 11-carboxylic acid. The latter is irradiated with U.V. light and the product reacted with SOCl 2  to give 2 -chloro-8d-chlorocarbonyl- 4b,8b, 8c, 8dtetrahydro-dibenzo[a,f]cyclopropa[c,d]pentalene. 9,10 - Dioxo - 4b,9,9a,10 - tetrahydro-indeno- [1,2-a]indene is reacted with HCHO and (CH 3 ) 2 NH to give 9a-dimethylaminomethyl-9,10- dioxo - 4b,9,9a,10 - tetrahydro - indeno[1,2-a]- indene and this is reduced with NaBH 4  to the corresponding 9a-dimethylaminomethyl-9,10- dihydroxy derivative. 2-Methyl-anthracene is reacted with ethyl propiolate and the product hydrolysed to give 2 - methyl - 9,10 - etheno - 9,10 - dihydroanthracene-11-carboxylic acid which is then irradiated with U.V. light to give 2-methyl-4b,8b,8c,8dtetrahydro - dibenzo - [a,f]cyclopropa[c,d]pentalene 8d-carboxylic acid and this is reacted with SOC1 2  to give the acid chloride. 9,10 - Etheno - 9,10 - dihydro - anthracene- 11,12-dicarboxylic acid is irradiated with U.V. light to give 4b,8b,8c,8d-tetrahydro-dibenzo[a,f]- cyclopropa[c,d]pentalene- 8b,8d - dicarboxylic acid which is then converted to its anhydride. The latter is reacted with methylamine to give the mono .N-methylamide of the diacid which on cyclization gives the corresponding N-methylimide. The N-ethyl imide is similarly prepared. Pharmaceutical compositions having antidepressant and amphetamine-potentiating effects comprise a compound I together with a suitable excipient for oral or parenteral administration.