Hydrochloric Acid → (Z)-17beta-hydroxy-2-hydroxymethylene-17alpha-methylandrosta-4,15-dien-3-one

HRID 274313Notes

Reaction equation

HRID 274313 reaction equation
[CH:1](OCC)=[O:2].[OH:6][C@@:7]1([CH3:27])[CH:12]=[CH:11][C@H:10]2[C@H:13]3[C@H:23]([CH2:24][CH2:25][C@:8]12[CH3:9])[C@:21]1([CH3:22])[C:16](=[CH:17][C:18](=[O:26])[CH2:19][CH2:20]1)[CH2:15][CH2:14]3.[H-].[Na+].Cl>O1CCCC1.C1(C)C=CC=CC=1>[OH:6][C@@:7]1([CH3:27])[CH:12]=[CH:11][C@H:10]2[C@H:13]3[C@H:23]([CH2:24][CH2:25][C@:8]12[CH3:9])[C@:21]1([CH3:22])[C:16](=[CH:17][C:18](=[O:26])/[C:19](=[CH:1]\[OH:2])/[CH2:20]1)[CH2:15][CH2:14]3

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 8025Ethyl formateHCID 24758Sodium hydrideHCID 1567913617beta-Hydroxy-17alpha-methylandrosta-4,15-dien-3-one

Product 1

HCID 15679154(Z)-17beta-hydroxy-2-hydroxymethylene-17alpha-methylandrosta-4,15-dien-3-one

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Procedure

At room temperature, 4.6 ml of ethyl formate is added to 4.6 g of 17β-hydroxy-17α-methylandrosta-4,15-dien-3-one in 40 ml of tetrahydrofuran and 70 ml of toluene. Then 3.5 g of sodium hydride (60% paraffin suspension) is added in small portions. After 6 hours, the reaction mixture is gently stirred into ice/water which contains hydrochloric acid, the precipitated product is suctioned off, washed with water, dissolved in methylene chloride, dried, and concentrated under vacuum. After chromatography of the crude product on silica gel with a hexane-ethyl acetate gradient, 2.4 g of (Z)-17β-hydroxy-2-hydroxymethylene-17α-methylandrosta-4,15-dien-3-one is obtained, mp 176° C. (from acetone/hexane).

Workup

  1. washwashed with water
  2. dissolutiondissolved in methylene chloride
  3. customdried
  4. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-1ca2a8c3dd7d4c99b78dc7b6d360a2b1
Source dataset
uspto-grants-1995_02
Patent number
US05389624

Reaction notes

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