GB1274263A - Dibenzocycloheptene derivatives - Google Patents

Abstract

1,274,263. Dibenzocycloheptene derivatives. F. HOFFMANN-LA ROCHE & CO. A.G. 1 May, 1969 [3 May, 1968], No. 28706/71. Divided out of 1,274,261. Heading C2C. Novel compounds of Formula I wherein the dotted bonds can be hydrogenated, R<SP>1</SP> represents a methyl or ketalized acetyl (as hereinafter defined) group and X represents a chlorine atom or a lower alkylsulphonyloxy group, a (lower - alkyl) - phenylsulphonyloxy group or a phenyl-(lower alkyl)-sulphonyloxy group or, when an exocyclic double-bond is present in the 5-position, a group of the formula -N<SP>+</SP>(CH 3 ) 3 A<SP>-</SP> in which A represents an anion of an acid; (the term " ketalized acetyl " group is used herein to mean an acetyl group ketalized with an alkanol or alkylene glycol containing up to 7 carbon atoms), are prepared as follows: (a) Those which contain an exocyclic double-bond in the 5-position and in which X represents a chlorine atom or a substituted sulfonyloxy group can be prepared, for example, by reacting a corresponding 5H-dibenzo[a,b]cyclohepten-5- one or 10,11 - dihydro - 5H - dibenzo[a,d] cyclohepten - 5 - one with a 3 - methoxypropyl magnesium halide and subsequently hydrolysing the reaction product. After dehydration of the resulting carbinol and treatment of the resulting product with a chlorinating agent or, after hydrolysis in a manner known per se, with a sulphonylating agent, there is obtained the desired dibenzocycloheptene derivative of Formula I. (b) Those which contain an exocyclic single-bond in the 5-position can be prepared, for example, by reacting a halide of the formula wherein R<SP>1</SP> and the broken line have the significance given earlier and W represents a halogen atom, with a 3-methoxypropyl magnesium halide. The resulting 5-(3-methoxypropyl) compound is subsequently converted by treatment with a chlorinating agent or, after hydrolysis in a manner known per se, with a sulphonylating agent in both cases where deketalization at the 1-position occurs during the foregoing reactions, the deketalized dibenzocycloheptene derivatives obtained can be ketalized in accordance with usual known methods and (c). The dibenzocycloheptene derivatives of Formula I hereinbefore in which X represents a grouping of the formula -N<SP>+</SP>(CH 3 ) 3 A<SP>-</SP> can be prepared by quaternizing a corresponding amino, monomethylamino or dimethylamino compound with a methylating agent such as methyl chloride, methyl bromide, methyl iodide or dimethyl sulfate. Intermediates of Formula I above wherein X is a methoxy group are prepared by dehydration of the corresponding 5-hydroxy compound which is obtained by reaction of the 5-keto compound with the Grignard reagent derived from 1-chloro-3-methoxypropane.