Testosterone → HCID 11439410, compound

HRID 1022415Notes

Reaction equation

HRID 1022415 reaction equation
[CH3:1][C@@:2]12[C@@H:10]([OH:11])[CH2:9][CH2:8][C@H:7]1[C@@H:6]1[CH2:12][CH2:13][C:14]3[C@@:20]([CH3:21])([C@H:5]1[CH2:4][CH2:3]2)[CH2:19][CH2:18][C:16](=[O:17])[CH:15]=3.Cl[C:23]([O:25][CH3:26])=[O:24]>N1C=CC=CC=1>[CH3:26][O:25][C:23]([O:11][C@H:10]1[CH2:9][CH2:8][C@H:7]2[C@H:6]3[C@H:5]([CH2:4][CH2:3][C@:2]12[CH3:1])[C@:20]1([CH3:21])[C:14](=[CH:15][C:16](=[O:17])[CH2:18][CH2:19]1)[CH2:13][CH2:12]3)=[O:24]

Participants

4

Reactant 2

HCID 6013TestosteroneHCID 6586Methyl chloroformate

Product 1

HCID 11439410HCID 11439410, compoundYield 76%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

Testosterone is treated with methyl chloroformate in pyridine to give 17β-methoxycarbonyloxyandrost-4-en-3-one in 76% yield after recrystallization from methanol. A solution of the 17β-methoxycarbonyloxyandrost-4-en-3-one in toluene is pyrolyzed at 460° C., and the crude product is recrystallized from acetone at room temperature to give androsta-4,16-dien-3-one in 90% yield. The androsta-4,16-dien-3-one is reduced at −55° with lithium tris(1,2-dimethylpropyl)hydridoborate in tetrahydrofuran to give a mixture of androsta-4,16-dien-3β-ol and androsta-4,16-dien-3α-ol; and chromatography on silica gel using dichloromethane/ethyl acetate gives pure androsta-4,16-dien-3β-ol and pure androsta-4,16-dien-3α-ol, each in 48% yield. These may be recrystallized (androsta-4,16-dien-3β-ol from cyclohexane at room temperature and androsta-4,16-dien-3α-ol from petroleum ether at −30° C.).

Sources & evidence

ORD record
ord-c8bcecfb637f4a549e9935bfbdf0610c
Source dataset
uspto-grants-2014_05
Patent number
US08722652B2

Reaction notes

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