Patent GB-777682-A (GB)
Title: Polyhydrophenanthrene compounds
IPC: C07D317/72
Filed: 1953-09-17
Abstract: The invention comprises compounds having the formula: <FORM:0777682/IV(b)/1> in which the 7-position is occupied either by a bivalent group convertible to keto by acid hydrolysis or by a pair of univalent groups together convertible to a single keto group by acid hydrolysis; and compounds having the formula: <FORM:0777682/IV(b)/2> in which the 7-position is occupied by a univalent group which is convertible to keto by acid hydrolysis, and in each formula R0 represents a (1) carboalkoxymethylene, (2) carboalkoxymethyl, (3) carboxymethylene or (4) carboxymethyl group, and their preparation as follows: 1 - alkoxyethinyl - 1 - hydroxy - 2 - methallyl - 2,4b - dimethyl - 4 - keto - 7 - ethylenedioxy - 1,2,3,4,4a,4b,5,6,7,8,10,10a - dodecahydrophenanthrene is reacted with dilute mineral acid to produce 1-carboalkoxymethylene - 2 - methallyl - 2,4b - dimethyl - 4 - keto- 7 - ethylenedioxy - 1,2,3,4,4a,4b,5,6,7,8,10,10a-dodecahydrophenanthrene (compound 2); compound 2 is saponified to produce 1-carboxymethylene - 2 - methallyl - 2,4b - dimethyl - 4-keto - 7 - ethylenedioxy - 1,2,3,4,4a,4b,5,6,7,8,10,10a - dodecahydrophenanthrene (compound 3) which is reduced e.g. with alkali metal in a lower alkanol or in liquid ammonia to produce 1 - carboxymethyl - 2 - methallyl - 2,4b - dimethyl - 4 - hydroxy - 7 - ethylenedioxy - 1,2,3,4,4a,4b,5,6,7,8,10a-dodecahydrophenanthrene (compound 4); compound 4 is converted to a 1-carboalkoxymethyl - 2 - methallyl - 2,4b - dimethyl - 4 - hydroxy - 7 - ethylenedioxy - 1,2,3,4,4a,4b,5,6,7,8,10,10a-dodecahydrophenanthrene (compound 6) which may be oxidized to 1 - carboalkoxymethyl - 2 - methallyl - 2,4b-dimethyl - 4 - ket - 7 - ethylenedioxy - 1,2,3,4,4a,4b,5,6,7,8,10,10a - dodecahydrophenanthrene (compound 7). Alternatively compound 4 can be reacted with an oxidizing agent to produce 1-carboxymethyl - 2 - methallyl- 2,4b - dimethyl- 4 - keto - 7 - ethylenedioxy - 1,2,3,4,4a,4b,5,6,7,8,10,10a - dodecahydrophenanthrene (compound 8) which is then esterified to form compound 7.  Examples disclose the production of 1-carboethoxymethylene - 2 - methallyl - 2,4b - dimethyl - 4 - keto - 7 - ethylenedioxy - 1,2,3,4,4a,4b,5,6,7,8,10,10a - dodecahydrophenanthrene, 1-carboethoxymethylene - 2 - methallyl - 2,4b-dimethyl - 4,7 - diketo - 1,2,3,4,4a,4b,5,6,7,8,10,10a - dodecahydrophenanthrene, 1 - carboxymethylene - 2 - methallyl - 2,4b - dimethyl - 4,7-diketo - 1,2,3,4,4a,4b,5,6,7,8,10,10a - dodecahydrophenanthrene, 1 - carboxymethyl - 2-methallyl - 2,4b - dimethyl - 4 - keto - 7 - ethylenedioxy - 1,2,3,4,4a,4b,5,6,7,8,10,10a - dodecahydrophenenthrene, 1 - carboxymethyl - 2-methallyl - 2,4b - dimethyl - 4 - keto - 7 - ethylenedioxy - 1,2,3,4,4a,4b,5,6,7,8,10,10a - dodecahydrophenenthrene, 1 - carboxymethyl - 2-methallyl - 2,4b - dimethyl - 4,7 - diketo - 1,2,3,4,4a,4b,5,6,7,8,10,10a-dodecahydrophenanthrene, 1 - carbomethoxymethyl - 2 - methallyl-2,4b - dimethyl - 4 - keto - 7 - ethylenedioxy - 1, - 1,2,3,4,4a,4b,5,6,7,8,10,10a-dodecahydrophenanthrene, 1 - carbomethoxymethyl - 2 - methallyl - 2,4b - 4,7 - diketo - 1,2,3,4,4a,4b,5,6,7,8,10,10a - dodecahydrophenanthrene and their stereoisomers.  Specifications 763,208, 777,681, 777,684 and 777,685 are referred to.