Carbon tetrabromide → 7alpha-(5-Bromopentyl)-11beta-fluoro-estr-4-ene-3,17-dione

HRID 1838890Notes

Reaction equation

HRID 1838890 reaction equation
[F:1][C@H:2]1[CH2:19][C@@:17]2([CH3:18])[C@@H:13]([CH2:14][CH2:15][C:16]2=[O:20])[C@H:12]2[C@H:3]1[C@@H:4]1[C:9]([CH2:10][C@H:11]2[CH2:21][CH2:22][CH2:23][CH2:24][CH2:25]O)=[CH:8][C:7](=[O:27])[CH2:6][CH2:5]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(Br)(Br)(Br)[Br:48]>ClCCl>[Br:48][CH2:25][CH2:24][CH2:23][CH2:22][CH2:21][C@@H:11]1[CH2:10][C:9]2[C@H:4]([CH2:5][CH2:6][C:7](=[O:27])[CH:8]=2)[C@@H:3]2[C@@H:12]1[C@H:13]1[C@@:17]([CH2:19][C@@H:2]2[F:1])([CH3:18])[C:16](=[O:20])[CH2:15][CH2:14]1

Participants

5

Reactant 3

HCID 11205Carbon tetrabromideHCID 11776TriphenylphosphineHCID 1587066111beta-Fluoro-7alpha-(5-hydroxypentyl)-estr4-ene-3,17-dione

Product 1

HCID 158706627alpha-(5-Bromopentyl)-11beta-fluoro-estr-4-ene-3,17-dioneYield 74%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of 33 g of 11β-fluoro-7α-(5-hydroxypentyl)oestr-4-ene-3,17-dione in 330 ml of dichloromethane is treated with 28.9 g of triphenylphosphine and 36.7 g of carbon tetrabromide at −5° C. and stirred for 0.5 hours. Dichloromethane is then added and the mixture is washed with water, saturated sodium hydrogencarbonate solution and sodium chloride solution. The organic phase is dried over sodium sulphate and concentrated in vacuo. The crude product is then chromatographed on silica gel using a hexane-ethyl acetate gradient. 28.5 g of 7α-(5-bromopentyl)-11β-fluorooestr-4-ene-3,17-dione of melting point 75-76° C. are obtained.

Workup

  1. washthe mixture is washed with water, saturated sodium hydrogencarbonate solution and sodium chloride solution
  2. dry with materialThe organic phase is dried over sodium sulphate
  3. concentrationconcentrated in vacuo
  4. customThe crude product is then chromatographed on silica gel using a hexane-ethyl acetate gradient

Sources & evidence

ORD record
ord-7c2f4baf7e9f49a8a3851ef5994ab8d2
Source dataset
uspto-grants-2004_01
Patent number
US06677324B1

Reaction notes

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