Steroidal intermediates from the condensation product of dimethyl-3-ketoglutarate and glyoxal

{
  "publication_number": "US4150236A",
  "country": "US",
  "kind": "A",
  "title": "Steroidal intermediates from the condensation product of dimethyl-3-ketoglutarate and glyoxal",
  "abstract": "Tricyclic aromatic compounds of the formula ##STR1## including those wherein: (A) R 1 is H, R 2 is carbomethoxy, and R 3 is methyl; (b) R 1 is acetyl, R 2 is carbomethoxy, and R 3 is methyl; (c) R 1 and R 3 are methyl and R 2 is carbomethoxy; (d) R 1, R 2, and R 3 are hydrogen; and (e) R 1 and R 3 are methyl and R 2 is hydrogen Are intermediates for the total synthesis of steroids.",
  "claims": [
    "1. A method for the synthesis of a tricyclic aromatic compound of the formula ##STR18## wherein R 1 is hydrogen, R 2 is carbomethoxy, and R 3 is methyl comprising the steps of: (a) condensing three moles of a dimethyl 3-ketoglutarate of the formula R 3 OOCCH 2 COCH 2 COOR 3 with two moles of glyoxal to produce a hexacarbomethoxy compound of the formula ##STR19## wherein R 3 is methyl; (b) hydrolyzing the hexacarbomethoxy compound to a dicarbomethoxyaldol of the formula ##STR20## (c) acetylating the dicarbomethoxyaldol to an acetoxy compound of the formula ##STR21## wherein Ac is acetoxy; (d) thermolyzing the acetoxy compound to a tricyclic compound of the formula ##STR22## which spontaneously aldolizes to an intramolecular aldol of the formula ##STR23## and treating the intramolecular aldol with alkali metal methoxide to form the tricyclic aromatic compound of the formula ##STR24## wherein R 3 is as above; or treating said acetoxy compound with the alkali metal methoxide to form said tricyclic aromatic compound.",
    "2. The method of claim 1, including the further step of etherifying the hydroxy of said tricyclic aromatic compound to a dimethoxy compound of the formula ##STR25## wherein R 1 is methyl.",
    "3. The method of claim 1 including the further step of esterifying the hydroxy of said tricyclic aromatic compound to a diacetoxy compound of the formula ##STR26## wherein R 1 is acetyl.",
    "4. The method of claim 1 including the further steps of hydrolyzing said tricyclic aromatic hydrocarbon to a diacid of the formula ##STR27## and decarboxylating to an acid of the formula ##STR28##",
    "5. The method of claim 4 including the further step of etherifying the acid to a dimethoxyacid of the formula ##STR29## wherein R 1 is methyl."
  ],
  "cpc": [
    "C07C 62/38"
  ],
  "assignees": [
    "US HEALTH EDUCATION & WELFARE"
  ],
  "filing_date": "1977-07-19",
  "publication_date": "1979-04-17",
  "grant_date": "1979-04-17",
  "priority_date": "1976-05-26",
  "application_number": "US-81709477-A",
  "family_id": "24772161"
}