Ammonia → HCID 86748619, compound

HRID 1455907Notes

Reaction equation

HRID 1455907 reaction equation
N.[Li].[CH2:3]1[CH2:16][O:15][C:10]23[O:11][CH2:12][CH2:13][O:14][C:5]2([C@:6]2([CH2:28][C:27]([C:29]4[CH:34]=[CH:33][C:32]([O:35][CH3:36])=[CH:31][CH:30]=4)=[C:26]4[C@@H:17]([CH2:18][CH:19]=[C:20]5[C@@H:25]4[CH2:24][CH2:23][CH2:22][CH2:21]5)[C@@H:8]2[CH2:9]3)[CH3:7])[O:4]1.O>O1CCCC1>[CH2:13]1[CH2:12][O:11][C:10]23[O:15][CH2:16][CH2:3][O:4][C:5]2([C@:6]2([CH2:28][C@H:27]([C:29]4[CH:34]=[CH:33][C:32]([O:35][CH3:36])=[CH:31][CH:30]=4)[C@H:26]4[C@@H:17]([CH2:18][CH:19]=[C:20]5[C@@H:25]4[CH2:24][CH2:23][CH2:22][CH2:21]5)[C@@H:8]2[CH2:9]3)[CH3:7])[O:14]1

Participants

6

Reactant 4

HCID 222AmmoniaHCID 962WaterHCID 3028194Lithium2×HCID 67788990HCID 67788990, compound

Product 1

HCID 86748619HCID 86748619, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

800 ml of ammonia are condensed at -70° C. and 1.39 g of lithium are added. After the characteristic blue colouring appears, 18.6 g (40 mmol) of 3,3;17,17-bis-(ethylenedioxy)-11-(4-methoxyphenyl)-5,9(11)-oestradiene dissolved in 400 ml of tetrahydrofuran are added dropwise. After stirring the mixture for 20 minutes, the excess lithium is decomposed by the addition of water, and the ammonia is evaporated off. The reaction mixture is poured onto saturated ammonium chloride solution and the aqueous phase is extracted with ethyl acetate. The combined organic phases are washed with saturated sodium chloride solution, dried over sodium sulphate and concentrated in vacuo. After chromatography of the crude product on silica gel with a mixture of ethyl acetate/hexane, 15.2 g of 3,3;17,17-bis-(ethylenedioxy)-11β-(4-methoxyphenyl)-5-oestrene and 1.4 g of 17,17-bis-(ethylenedioxy)-11-(4-hydroxyphenyl)-5, 9(11)-oestradiene, m.p. 168°-170° C. (ethyl acetate), [α]D20 =-11° (CHCl3 ; c=0.505), are isolated in the form of white foams.

Workup

  1. customcondensed at -70° C.
  2. additionare added dropwise
  3. customthe ammonia is evaporated off
  4. additionThe reaction mixture is poured onto saturated ammonium chloride solution
  5. extractionthe aqueous phase is extracted with ethyl acetate
  6. washThe combined organic phases are washed with saturated sodium chloride solution
  7. dry with materialdried over sodium sulphate
  8. concentrationconcentrated in vacuo
  9. additionAfter chromatography of the crude product on silica gel with a mixture of ethyl acetate/hexane, 15.2 g of 3,3

Sources & evidence

ORD record
ord-5e98cd9cd53d4655b41accc2514bb409
Source dataset
uspto-grants-1998_12
Patent number
US05843931

Reaction notes

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