Benzenesulfenyl chloride → 4,9,14-Estratriene-3,17-dione

HRID 746159Notes

Reaction equation

HRID 746159 reaction equation
C([C@H:5]1[C@H:10]2[C@H:11]3[C:20]([CH2:21][CH2:22][C@:8]2([CH3:9])[C:7](=[O:24])[CH2:6]1)=[C:19]1[C:14](=[CH:15][C:16](=[O:23])[CH2:17][CH2:18]1)[CH2:13][CH2:12]3)CCC.C1(SCl)C=CC=CC=1>C(Cl)Cl.C(N(CC)CC)C>[CH3:9][C@:8]12[CH2:22][CH2:21][C:20]3[C@@H:11]([CH2:12][CH2:13][C:14]4[C:19]=3[CH2:18][CH2:17][C:16](=[O:23])[CH:15]=4)[C:10]1=[CH:5][CH2:6][C:7]2=[O:24]

Participants

5

Reactant 2

HCID 11008040Benzenesulfenyl chlorideHCID 1342361815beta-n-Butyl-4,9-estradiene-3,17-dione

Product 1

HCID 134236164,9,14-Estratriene-3,17-dioneYield 100.6%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent3×HCID 8471TriethylamineSolvent

Procedure

A solution of 1.5 g of 15 α-hydroxy-4,9-estradiene-3,17-dione in 20 ml of methylene chloride and 1.2 ml of triethylamine is mixed with a solution of 0.83 g of phenylsulfenyl chloride in 5 ml of methylene chloride drop by drop at -20° C. After addition, stirring is performed for 10 minutes at -20° C., the reaction solution is then diluted with 100 ml of methylene chloride, washed, one after the other, with saturated sodium hydrogen carbonate solution and saturated ammonium chloride solution, dried with sodium sulfate and concentrated. Crystallization of the crude product from ethyl acetate/diisopropyl ether yields 1.24 g (88.2% of theory) of 4,9,14-estratriene-3,17-dione with a melting point of 143° to 144° C.

Workup

  1. additionAfter addition
  2. washwashed
  3. dry with materialone after the other, with saturated sodium hydrogen carbonate solution and saturated ammonium chloride solution, dried with sodium sulfate
  4. concentrationconcentrated
  5. customCrystallization of the crude product from ethyl acetate/diisopropyl ether

Sources & evidence

ORD record
ord-29f0114715f54cddaa3489d6be618cdc
Source dataset
uspto-grants-1986_07
Patent number
US04603013

Reaction notes

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