Urea, (2,2-diethoxyethyl)- → 21-Chloro-16alpha-(2,2-diethoxyethoxy)-9-fluoro-11beta,17-dihydroxypregna-1,4-diene-3,20-dione

HRID 918374Notes

Reaction equation

HRID 918374 reaction equation
[CH2:1]([O:3][CH:4]([O:8][CH2:9][CH3:10])[CH:5]=[N+]=[N-])[CH3:2].C(OC(OCC)CNC(N)=O)C.[Cl:23][CH2:24][C:25](=[O:50])[C@:26]1([OH:49])[C@:43]2([CH3:44])[C@H:29]([C@H:30]3[C@:40]([F:46])([C@@H:41]([OH:45])[CH2:42]2)[C@:38]2([CH3:39])[C:33](=[CH:34][C:35](=[O:47])[CH:36]=[CH:37]2)[CH2:32][CH2:31]3)[CH2:28][C@H:27]1[OH:48]>CO>[Cl:23][CH2:24][C:25](=[O:50])[C@:26]1([OH:49])[C@:43]2([CH3:44])[C@H:29]([C@H:30]3[C@:40]([F:46])([C@@H:41]([OH:45])[CH2:42]2)[C@:38]2([CH3:39])[C:33](=[CH:34][C:35](=[O:47])[CH:36]=[CH:37]2)[CH2:32][CH2:31]3)[CH2:28][C@H:27]1[O:48][CH2:5][CH:4]([O:8][CH2:9][CH3:10])[O:3][CH2:1][CH3:2]

Participants

5

Reactant 3

HCID 1713901Urea, (2,2-diethoxyethyl)-HCID 21520892Ethane, 2-diazo-1,1-diethoxy-HCID 8673374021-Chloro-9-fluoro-11beta,16alpha,17-trihydroxypregna-1,4-diene-3,20-dione

Product 1

HCID 8673374221-Chloro-16alpha-(2,2-diethoxyethoxy)-9-fluoro-11beta,17-dihydroxypregna-1,4-diene-3,20-dione

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 2,2-diethoxy-1-diazoethane (prepared from 0.0935 mole of N-2,2-diethoxyethyl urea by the method of W. Kirmse and M. Buschhoff, Chem. Ber., 100, 1491 (1967)) in 300 ml of 3:2 ether-pentane is diluted with 100 ml of methanol and cooled to 0°C. A total of 2.5 g of 21-chloro-9-fluoro-11β,16α,17-trihydroxypregna-1,4-diene-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 2.16 g of TLC pure material that is recrystallized from acetone-hexane to give 1.75 g of 21-chloro-16α-(2,2-diethoxyethoxy)-9-fluoro-11β,17-dihydroxypregna-1,4-diene-3,20-dione, melting point 200°-202°C.

Workup

  1. customThe solvent is removed in vacuo
  2. dissolutionthe residue is dissolved in chloroform
  3. customchromatographed on an 80 g
  4. washElution with chloroform
  5. customgives 2.16 g of TLC pure material that
  6. customis recrystallized from acetone-hexane

Sources & evidence

ORD record
ord-060b06ebede347fcb438b48f747a8fea
Source dataset
uspto-grants-1976_07
Patent number
US03971772

Reaction notes

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