Water → HCID 10403204, compound

HRID 2210070Notes

Reaction equation

[N:1]([C:4]1[C:21](=[O:22])[CH:20]=[CH:19][C@@:18]2([CH3:23])[C:5]=1[C:6](=[CH2:25])[CH2:7][C@@H:8]1[C@@H:17]2[CH2:16][CH2:15][C@@:13]2([CH3:14])[C@H:9]1[CH2:10][CH2:11][C:12]2=[O:24])=[N+]=[N-].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.O1CCOCC1.O>O1CCCC1>[NH2:1][C:4]1[C:21](=[O:22])[CH:20]=[CH:19][C@@:18]2([CH3:23])[C:5]=1[C:6](=[CH2:25])[CH2:7][C@@H:8]1[C@@H:17]2[CH2:16][CH2:15][C@@:13]2([CH3:14])[C@H:9]1[CH2:10][CH2:11][C:12]2=[O:24]

Participants

Conditions

Temperature: 35 °C

Procedure

To a stirred solution of 4-azido-6-methylenandrosta-1,4-diene-3,17-dione (3.374 g, 10 mmol) in tetrahydrofuran (25 ml) was added portionwise triphenylphosphine (2.823 g, 10 mmol). During the reaction, which lasted about 2.5 h, the temperature raised to about 35° C. and there was nitrogen evolution. Then dioxane (100 ml) and water (10 ml) was added and the mixture was refluxed for 10 h. Finally the mixture was poured onto water and the raw product extracted with ethyl acetate. The organic phase was extracted 4× with 2N hydrochloric acid, the aqueous phase was separated and the product precipitated by alkalinization with sodium hydroxide solution. Thus almost pure 4-amino-6-methylen-androsta-1,4-diene-3,17dione was obtained in about 30% yield (0.934 g).

Workup

customDuring the reaction, which
temperaturethe mixture was refluxed for 10 h
additionFinally the mixture was poured onto water
extractionthe raw product extracted with ethyl acetate
extractionThe organic phase was extracted 4× with 2N hydrochloric acid
customthe aqueous phase was separated
customthe product precipitated by alkalinization with sodium hydroxide solution

Sources & evidence

ORD record: ord-4cd1f1adbaef4e9f8ace3461c214c5db
Source dataset: uspto-grants-1995_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05457097

Reaction notes

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