http://rdf.ncbi.nlm.nih.gov/pubchem/patent/GB-754373-A
Outgoing Links
| Predicate | Object |
|---|---|
| assignee | http://rdf.ncbi.nlm.nih.gov/pubchem/patentassignee/MD5_b30d807376962224a66aa244d678104a |
| classificationCPCInventive | http://rdf.ncbi.nlm.nih.gov/pubchem/patentcpc/C07J75-00 http://rdf.ncbi.nlm.nih.gov/pubchem/patentcpc/C07J3-00 |
| classificationIPCInventive | http://rdf.ncbi.nlm.nih.gov/pubchem/patentipc/C07J75-00 http://rdf.ncbi.nlm.nih.gov/pubchem/patentipc/C07J3-00 |
| filingDate | 1954-05-17-04:00^^<http://www.w3.org/2001/XMLSchema#date> |
| publicationDate | 1956-08-08-04:00^^<http://www.w3.org/2001/XMLSchema#date> |
| publicationNumber | GB-754373-A |
| titleOfInvention | 17-formyl audrostadiene derivatives and the preparation thereof |
| abstract | The invention comprises 17-formyl-cyclopent-16 - eno - 10 : 13 - dimethyl - D 4 - dodecahydrophenanthrene - 3 : 11 - diones of the general formula <FORM:0754373/IV(a)/1> and a process for their preparation by treating a 16 : 17 - dihydroxy - cyclohexano - 10 : 13-dimethyl - D 4 - dodecahydrophenanthrene-3 : 11-dione with aqueous periodic acid and cyclodehydrating the resulting dialdehyde with an ammonium or amine salt of a mono-carboxylic acid in the presence of an inert organic solvent. The 16 : 17-dihydroxy compound may be prepared by hydrolysis of a corresponding di-(monocarboxylic acid) ester or unsubstituted cyclic acetal, particularly the diacetate or the acetonide, which in turn is prepared from a diester or cyclic acetal of 16 : 17-dihydroxycyclohexano - 10 : 13 - dimethyl - D 4,9(11)-decahydrophenanthrene-3-one by treatment with a hypohalous acid, then oxidation with a chromium oxide-tertiary amine complex of the 9-halo-11-hydroxy derivative produced to the corresponding 9-halo-11-keto compound, followed by reductive dehalogenation with a metal in an acid medium. The 16 : 17-groups may be derived from the following acids: acetic, propionic, butyric, isobutyric, valeric, caproic, pelargonic, myristic, stearic, phenylacetic, hydrocinnamic, g -phenylbutyric, benzoic or toluic; and the cyclic acetals from symmetrical ketones, e.g. acetone, diethyl ketone, cyclohexanone and p-methyl cyclohexanone. In an example: dl-3-keto-16a : 17a -dihydroxy - D 4,9(11) - D - homoandrostadiene diacetate in aqueous acetone is treated with N-bromosuccinimide to give dl-3-keto-9-bromo-11 : 16a : 17a - trihydroxy - D 4 - D - homoandrostene-16 : 17-diacetate. The 9-chloro-and 9-iodo-analogues are prepared from it by conversion to the 9 : 11-epoxide with potassium acetate in boiling ethanol, followed by treatment with hydrogen halide in chloroform. Subsequent oxidation of the 9-bromo-D-homoandrostene diacetate with chromium trioxide and pyridine yields dl-3 : 11-diketo-9-bromo-16a : 17a - dihydroxy - D 4 - D - homoandrostene diacetate, which on treatment with zinc dust and glacial acetic acid furnishes dl-3 : 11-diketo - 16a : 17a - dihydroxy - D 4 - D - homoandrostene diacetate. The ester is saponified to the 16 : 17-diol, which is cleaved with periodic acid in dioxan and the resulting dialdehyde cyclized in acetic acid-piperidine to dl - 3 : 11 - diketo - 17 - formyl - D 4:16-androstadiene. Other examples illustrate the above process using the corresponding 16b : 17b -, and 16a : 17b -isomers, various individual optical isomers, and also using the dipropionates and acetonides. Specification 749,214 is referred to. |
| priorityDate | 1953-05-15-04:00^^<http://www.w3.org/2001/XMLSchema#date> |
| type | http://data.epo.org/linked-data/def/patent/Publication |
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