Oxalyl chloride → 17beta-Chlorocarbonyl-5alpha-androstan-3-one

HRID 267642Notes

Reaction equation

HRID 267642 reaction equation
[CH3:1][C@:2]12[CH2:19][CH2:18][C@H:17]3[C@@H:7]([CH2:8][CH2:9][C@@H:10]4[C@:15]3([CH3:16])[CH2:14][CH2:13][C:12](=[O:20])[CH2:11]4)[C@@H:6]1[CH2:5][CH2:4][C@@H:3]2[C:21]([OH:23])=O.CC(=O)[C@@H]1[C@]2(C)[C@H]([C@H]3[C@H](CC2)[C@]2(C)[C@H](CC(=O)CC2)CC3)CC1.C(Cl)(=O)C([Cl:50])=O>C1C=CC=CC=1>[Cl:50][C:21]([C@H:3]1[CH2:4][CH2:5][C@H:6]2[C@H:7]3[C@H:17]([CH2:18][CH2:19][C@:2]12[CH3:1])[C@:15]1([CH3:16])[C@H:10]([CH2:11][C:12](=[O:20])[CH2:13][CH2:14]1)[CH2:9][CH2:8]3)=[O:23]

Participants

5

Reactant 3

HCID 65578Oxalyl chlorideHCID 928105alpha-DihydroprogesteroneHCID 15170639Dutasteride Impurity 54

Product 1

HCID 8673314717beta-Chlorocarbonyl-5alpha-androstan-3-one

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

A solution of 5α-androstan-3-one 17β-carboxylic acid (2.25 g., corrected for the presence of 15% 5α-pregnan-3,20-dione as an impurity) and oxalyl chloride (4.5 ml.) in dry benzene (150 ml.) was refluxed for 1.5 hours, and then evaporated to dryness to afford crude 17β-chlorocarbonyl-5α-androstan-3-one. This acid chloride in benzene (15 ml.) was shaken with 880 ammonia (24 ml.) and water (15 ml.) for 5 minutes. After a further 30 minutes of standing at room temperature the precipitated amide was filtered, washed with water and dried. Recrysyallisation from dichloromethane/petrol afforded title compound (1.18 g.) m.p. 259°-262°. A further recrystallisation from dichloromethane/petrol provided an analytically pure sample; m.p. 276°-277°; [α]D + 51.5°, (c 0.6%).

Workup

  1. temperaturewas refluxed for 1.5 hours
  2. customevaporated to dryness

Sources & evidence

ORD record
ord-f7657679a9cc4aba9aae5d27ca49178c
Source dataset
uspto-grants-1976_03
Patent number
US03943124

Reaction notes

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