| 摘要 |
1,263,044. Substituted pyrido- and tetrahydropyrido-thioxanthenes. MERCK PATENT G.m.b.H. 1 July, 1970 [22 Aug., 1969], No. 31992/70. Heading C2C. Novel 1,2,3,11b-tetrahydropyrido[3,4,5 - m,n]- thioxanthenes of the general formula wherein R represents hydrogen or C 1-4 alkyl, and X and Y both represent hydrogen, chlorine or C 1-4 alkyl and acid addition salts thereof, are prepared by cyclizing a compound of formula wherein Z represents -CHO or -CH 2 Q (Q is OH or a reactively esterified OH group); by reacting a compound of formula with sulphur, sulphur dichloride, sulphur dibromide or a reactant which splits off sulphur under the reaction conditions to form a thioether bridge; and by reducing a compound corresponding to the first formula above except that it has one or more reducible groups in the nitrogen-containing ring for example, one or more double bonds in the 2,3- and/or 1,11b- or 1,2-positions or a carbonyl group in the 1- and/or 3-positions. Pyrido[3,4,5 : m,n]-thioxanthene is obtained as a by-product from the reaction of 10-formylaminomethylthioxanthene (obtainable by boiling 10-aminomethylthioxanthene and formic acid) with phosphorus pentoxide and phosphoric acid to form 1,2,3,11b-tetrahydropyrido[3,4,5 : m,n]- thioxanthene and may be converted to the corresponding 2-methoiodide. Other by-products obtained are 4-chloro-, 10-chloro-, 4-methyl- and 10-methyl-pyrido[3,4,5 : m,n]-thioxanthene. 2-Chloro-10-formylaminomethylthioxanthene is prepared by the reaction of 5-chloro-2-mercaptobenzoic and sulphuric acid, reduction of the resulting 2-chlorothioxanthone to form 2-chlorothioxanthene, stepwise treatment with lithium butyl, carbon dioxide (2-chlorothioxanthene-10- carboxylic acid), thionyl chloride, ammonia (2- chlorothioxanthene - 10 - carboxylic acid amide), LiAlH 4 /AlCl 3 , hydrobromic acid (2-chloro-10- aminomethylthioxanthene hydrobromide) and boiling with formic acid in toluene. 2-Methyl-10- formylaminomethylthioxanthene is prepared by a similar method. 2 - Methyl - 4 - phenyltetrahhdroisoquinoline hydrobromide is prepared by the cyclization of N - formyl - 2,2 - diphenyl - 1 - aminoethane with polyphosphoric acid, hydrogenation in presence of Raney nickel and methylation with formaldehyde and formic acid. Pharmaceutical compositions for parenteral, enteral or topical application which have a tranquillizing and/or hypnotic and/or antidepressant and/or narcosis-potentiating action and also have a slight muscle-relaxant action contain the 1,2,3,11b-tetrahydropyrido-[3,4,5 : m,n]-thioxanthenes of the first formula above as the active ingredient. |
