Hydrochloric Acid → HCID 22788011, compound
Reaction equation
[OH:1][CH:2]1[CH2:6][O:5][C:4]2([CH2:11][CH2:10][C@H:9]3[C@H:12]4[C@H:21]([CH2:22][CH2:23][C@:7]23[CH3:8])[C@@H:20]2[C:15](=[CH:16][C:17](=[O:24])[CH2:18][CH2:19]2)[CH2:14][CH2:13]4)[CH2:3]1.Cl.CC(C)=O.OS(O)(=O)=O.O=[Cr](=O)=O>CO.CC(C)=O>[O:5]1[CH2:6][C:2](=[O:1])[CH2:3][C:4]21[CH2:11][CH2:10][C@H:9]1[C@H:12]3[C@H:21]([CH2:22][CH2:23][C@:7]21[CH3:8])[C@@H:20]1[C:15](=[CH:16][C:17](=[O:24])[CH2:18][CH2:19]1)[CH2:14][CH2:13]3Participants
Reactant 3
Product 1
Reagents, catalysts & solvents 2
Procedure
The compound of this invention defined by the introductory formula when R therein represents hydrogen can be prepared as follows: 21-(Hydroxymethyl)-3-methoxy-17α-pregna-1,3,5(10), 20-tetraen-17-ol, upon prolonged contact with p-toluenesulfonyl chloride in pyridine, affords 3-methoxyspiro[estra-1,3,5(10)-triene-17,2'(5'H)-furan]. Consecutively contacting the latter intermediate in cold tetrahydrofuran under nitrogen with borane and sodium peroxide (formed in situ) affords 4',5'-dihydro-3-methoxyspiro[estra-1,3,5(10)-triene-17,2'(3'H)-furan]-4'-ol, from which, upon consecutively contacting in tetrahydrofuran and 1,1-dimethylethanol with liquid ammonia and lithium, 4',5'-dihydro-3-methoxyspiro[estra-2,5(10)-diene-17,2'(3'H)-furan[-4'-ol is obtained. Conversion of this enol ether to the corresponding 5(10)-en-3-one occurs upon contact with 90% acetic acid, and from the 4',5'-dihydro-4'-hydroxyspiro[estr-5(10)-ene-17,2'(3'H)-furan]-3-one thus obtained, 4',5'-dihydro-4'-hydroxyspiro[estr- 4-ene-17,2'(3'H)-furan]-3-one eventuates on contact with hydrochloric acid in methanol. Finally, the hydroxyl therein is oxidized with Jones' reagent in acetone, affording 4',5'-dihydrospiro[estr-4-ene- 17,2'(3'H)-furan]-3,4'-dione.
Sources & evidence
- ORD record
- ord-3ed6ad9d39e94f4a830990a39bb82596
- Source dataset
- uspto-grants-1976_02
- Patent number
- US03939155
Reaction notes
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