2-Methyl-3-diazo-1-propene → 21-Chloro-9-fluoro-11beta,17-dihydroxy-16alpha-((2-methyl-2-propenyl)oxy)pregna-1,4,diene-3,20-dione

HRID 918372Notes

Reaction equation

[CH3:1][C:2]([CH:4]=[N+]=[N-])=[CH2:3].[Cl:7][CH2:8][C:9](=[O:34])[C@:10]1([OH:33])[C@:27]2([CH3:28])[C@H:13]([C@H:14]3[C@:24]([F:30])([C@@H:25]([OH:29])[CH2:26]2)[C@:22]2([CH3:23])[C:17](=[CH:18][C:19](=[O:31])[CH:20]=[CH:21]2)[CH2:16][CH2:15]3)[CH2:12][C@H:11]1[OH:32]>CCOCC.CO>[Cl:7][CH2:8][C:9](=[O:34])[C@:10]1([OH:33])[C@:27]2([CH3:28])[C@H:13]([C@H:14]3[C@:24]([F:30])([C@@H:25]([OH:29])[CH2:26]2)[C@:22]2([CH3:23])[C:17](=[CH:18][C:19](=[O:31])[CH:20]=[CH:21]2)[CH2:16][CH2:15]3)[CH2:12][C@H:11]1[O:32][CH2:3][C:2]([CH3:4])=[CH2:1]

Participants

Conditions

Temperature: 0 °C

Procedure

A solution of 2-methyl-3-diazo-1-propene in 150 ml of ether (prepared from 0.1 mole of N-(2-methyl-2-propenyl)-ethyl carbamate by the method of J. L. Brewbaker and H. Hart, J. Am. Chem., Soc., 91, 711 (1969)) is diluted with 50 ml of methanol and cooled to 0°C. A total of 7 g of 21-chloro-9-fluoro-11β,16α,17-trihydroxypregna-1,4diene-3,20-dione, 16,17-cycloborate is added in portions until nitrogen evolution ceases. The solvent is removed in vacuo and the residue is dissolved in chloroform and chromatographed on an 80 g -silica gel column. Elution with chloroform gives TLC pure material which crystallizes from acetone-hexane to give 5.4 g of 21-chloro-9-fluoro-11β,17 -dihydroxy-16α-[(2-methyl-2-propenyl)oxy]pregna-1,4-diene-3,20-dione, melting point 238°-240°C.

Workup

customThe solvent is removed in vacuo
dissolutionthe residue is dissolved in chloroform
customchromatographed on an 80 g -silica gel column
washElution with chloroform
customgives TLC pure material which
customcrystallizes from acetone-hexane

Sources & evidence

ORD record: ord-6d668e3188bc41deb95a1ddd13988844
Source dataset: uspto-grants-1976_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US03971772

Reaction notes

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