Ammonium Chloride → 3-Benzyloxy-7alpha-(5-hydroxypentyl)-15beta-methyl-estra-1,3,5(10)-trien-17-one

HRID 1603335Notes

Reaction equation

[CH3:1][Mg]Br.[CH2:4]([O:11][C:12]1[CH:29]=[CH:28][C:27]2[C@@H:26]3[C@H:17]([C@H:18]4[C@@:22]([CH2:24][CH2:25]3)([CH3:23])[C:21](=[O:30])[CH:20]=[CH:19]4)[C@H:16]([CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][OH:36])[CH2:15][C:14]=2[CH:13]=1)[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1.[Cl-].[NH4+]>O1CCCC1.C(OCC)(=O)C.[Cu]I>[CH2:4]([O:11][C:12]1[CH:29]=[CH:28][C:27]2[C@@H:26]3[C@H:17]([C@H:18]4[C@@:22]([CH2:24][CH2:25]3)([CH3:23])[C:21](=[O:30])[CH2:20][C@H:19]4[CH3:1])[C@H:16]([CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][OH:36])[CH2:15][C:14]=2[CH:13]=1)[C:5]1[CH:6]=[CH:7][CH:8]=[CH:9][CH:10]=1

Participants

Conditions

Temperature: 0 °C

Procedure

5.35 g of copper(I) iodide is added to an ice-cooled solution of 11.9 ml of a 3-molar methylmagnesium bromide solution in 68 ml of tetrahydrofuran under a nitrogen stream. Then, a solution of 4.26 g of 3-benzyloxy-7α-(5-hydroxypentyl)-estra-1,3,5(10),15-tetraen-17-one (see Example 6b) in 50 ml of tetrahydrofuran is added in drops and stirred for 30 minutes at a bath temperature of 0° C. Then, the excess reagent is decomposed with saturated ammonium chloride solution, diluted with ethyl acetate, washed with ammonium chloride solution and water, dried on sodium sulfate, concentrated by evaporation in a vacuum and chromatographed on silica gel with hexane/acetone. 3.6 g of 3-benzyloxy-7α-(5-hydroxypentyl)-15β-methyl-estra-1,3,5(10)-trien-17-one is obtained as oil. [α]D22 =+66.4° (c=0.515% in chloroform).

Workup

washwashed with ammonium chloride solution and water
customdried on sodium sulfate
concentrationconcentrated by evaporation in a vacuum
customchromatographed on silica gel with hexane/acetone

Sources & evidence

ORD record: ord-d48f28ddafea40588af7567902d55385
Source dataset: uspto-grants-1999_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05986115

Reaction notes

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