Diazomethane → HCID 12836874, compound

HRID 848780Notes

Reaction equation

HRID 848780 reaction equation
[N+](=[CH2:3])=[N-].[CH3:4][O:5][C@H:6]1[CH2:11][CH2:10][C@H:9]2[C@H:12]3[C@H:22]([CH2:23][CH2:24][C@:7]12[CH3:8])[C@:20]1([CH3:21])[C@H:15]([CH2:16][C:17](=[O:25])[CH:18]=[CH:19]1)[CH2:14][CH2:13]3>C(OCC)C.C([O-])(=O)C.C([O-])(=O)C.[Pd+2]>[CH3:4][O:5][C@H:6]1[CH2:11][CH2:10][C@H:9]2[C@H:12]3[C@H:22]([CH2:23][CH2:24][C@:7]12[CH3:8])[C@:20]1([CH3:21])[C@H:15]([CH2:16][C:17](=[O:25])[C@@H:18]2[CH2:3][C@@H:19]21)[CH2:14][CH2:13]3

Participants

5

Reactant 2

HCID 9550DiazomethaneHCID 12836876HCID 12836876, compound

Product 1

HCID 12836874HCID 12836874, compound

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 3283Diethyl EtherSolvent

Procedure

Ethereal diazomethane (40 ml. generated from 3 g. of N-methyl-N'-nitro-N-nitrosoguinidine) is added to a mixture of 17β-methoxy-5α-androst-1-en-3-one (IV, Example 23, 1.0 g.) and palladium diacetate (10 mg.) in diethyl ether (20 ml.). After a few hours the organic diluents are removed by reduced pressure and the residue is column chromatographed thru silica gel (100 g.) eluting by gradient between ethyl acetate:SSB (5:95, 5 l.) and ethyl acetate:SSB (20:80, 5 l.). The appropriate fractions (TLC) are pooled and concentrated to give the title compound, m.p. 114°-118°; MS (m/e) 316, 301, 269, and 243; NMR (CDCl3) 0.77, 0.97, 3.23 and 3.34 δ; CMR (CDCl3) 9.66 δ.

Workup

  1. customAfter a few hours the organic diluents are removed by reduced pressure
  2. customchromatographed thru silica gel (100 g.)
  3. washeluting by gradient between ethyl acetate
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-2eb83d9020dc472a9c5a97ebbfae12b8
Source dataset
uspto-grants-1981_10
Patent number
US04297350

Reaction notes

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