9-Fluoro-11beta,16alpha,17,21-tetrahydroxypregn-4-ene-3,20-dione → 9-Fluoro-11beta,17,21-trihydroxy-16alpha-[(2-phenyl-2-propenyl)oxy]pregn-4-ene-3,20-dione

HRID 918371Notes

Reaction equation

[C:1]1([C:7]([CH:9]=[N+]=[N-])=[CH2:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[F:12][C@:13]12[C@@H:33]([OH:34])[CH2:32][C@@:31]3([CH3:35])[C@@H:23]([CH2:24][C@@H:25]([OH:37])[C@:26]3([OH:36])[C:27](=[O:30])[CH2:28][OH:29])[C@@H:22]1[CH2:21][CH2:20][C:19]1[C@:14]2([CH3:39])[CH2:15][CH2:16][C:17](=[O:38])[CH:18]=1>CO>[F:12][C@:13]12[C@@H:33]([OH:34])[CH2:32][C@@:31]3([CH3:35])[C@@H:23]([CH2:24][C@@H:25]([O:37][CH2:9][C:7]([C:1]4[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=4)=[CH2:8])[C@:26]3([OH:36])[C:27](=[O:30])[CH2:28][OH:29])[C@@H:22]1[CH2:21][CH2:20][C:19]1[C@:14]2([CH3:39])[CH2:15][CH2:16][C:17](=[O:38])[CH:18]=1

Participants

Conditions

Temperature: 0 °C

Procedure

The solution of 2-phenyl-3-diazo-1-propene prepared as described above is diluted with 150 ml of cold methanol and stirred well at 0°C as 13 g of 9-fluoro-11β,16α,17,21-tetrahydroxypregn-4-ene-3,20-dione, 16,17-cycloborate is added in portions. The slurry is stirred for 1 hour at 0°C and filtered to give 9.6 g of the title compound. The filtrate is stirred at room temperature for 1 hour with 4 g of the cycloborate and the resulting solution is cooled to 0°C and filtered to give 4.2 g of the title compound. The filtrate is evaporated in vacuo and the residue is dissolved in 400 ml of 3:1 ether-methanol and cooled to -10°C to give a further 3.0 g of material. A small sample recrystallized from acetone-hexane has a melting point of 161°-163.5°C.

Workup

addition16,17-cycloborate is added in portions
filtrationfiltered

Sources & evidence

ORD record: ord-87c0d49479ad4f6caab9ec9b630faa66
Source dataset: uspto-grants-1976_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US03971772

Reaction notes

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