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

HRID 267904Notes

Reaction equation

HRID 267904 reaction equation
[CH3:1][C:2]([CH:4]=[N+]=[N-])=[CH2:3].[F:7][C@:8]12[C@@H:28]([OH:29])[CH2:27][C@@:26]3([CH3:30])[C@@H:18]([CH2:19][C@@H:20]([OH:32])[C@:21]3([OH:31])[C:22](=[O:25])[CH2:23][OH:24])[C@@H:17]1[CH2:16][CH2:15][C:14]1[C@:9]2([CH3:34])[CH2:10][CH2:11][C:12](=[O:33])[CH:13]=1>CCOCC.CO>[F:7][C@:8]12[C@@H:28]([OH:29])[CH2:27][C@@:26]3([CH3:30])[C@@H:18]([CH2:19][C@@H:20]([O:32][CH2:3][C:2]([CH3:4])=[CH2:1])[C@:21]3([OH:31])[C:22](=[O:25])[CH2:23][OH:24])[C@@H:17]1[CH2:16][CH2:15][C:14]1[C@:9]2([CH3:34])[CH2:10][CH2:11][C:12](=[O:33])[CH:13]=1

Participants

5

Reactant 2

HCID 2287859-Fluoro-11beta,16alpha,17,21-tetrahydroxypregn-4-ene-3,20-dioneHCID 215208452-Methyl-3-diazo-1-propene

Product 1

HCID 681289879-Fluoro-11beta,17,21-trihydroxy-16alpha-[(2-methyl-2-propenyl)oxy]pregn-4-ene-3,20-dione

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 2-methyl-3-diazo-1-propene in 250 ml of ether (prepared from 0.2 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 300 ml of methanol and cooled to 0°C. A total of 6.5 g of 9-fluoro-11β ,16α ,17,21-tetrahydroxypregn-4-ene-3,20-dione, 16,17-cycloborate is added in portions until the initial red color fades and nitrogen evolution ceases. The solvent is evaporated in vacuo and the residue dissolved in chloroform and chromatographed on a 100 g - silica gel column. Elution with chloroform and chloroform-ethyl acetate gives TLC homogeneous material which crystallizes from acetone-hexane to give 3.73 g of 9-fluoro-11β ,17,21-trihydroxy-16α-[(2-methyl-2-propenyl)oxy]pregn-4-ene-3,20-dione, melting point 213°-215°C, softening at 198°-200°C.

Workup

  1. customThe solvent is evaporated in vacuo
  2. dissolutionthe residue dissolved in chloroform
  3. customchromatographed on a 100 g - silica gel column
  4. washElution with chloroform and chloroform-ethyl acetate
  5. customgives TLC homogeneous material which
  6. customcrystallizes from acetone-hexane

Sources & evidence

ORD record
ord-d58c3c4242c249b687e424e89d6a3cd0
Source dataset
uspto-grants-1976_03
Patent number
US03945997

Reaction notes

Loading…