Hydroxyamine hydrochloride → (E)-but-2-enedioic acid;(3R,6E,8R,9S,10R,13S,14S)-6-hydroxyimino-10,13-dimethyl-3-pyrrolidin-3-ylsulfanyl-2,3,4,5,7,8,9,11,12,14,15,16-dodecahydro-1H-cyclopenta[a]phenanthren-17-one

HRID 42076Notes

Reaction equation

HRID 42076 reaction equation
[C:1]([OH:8])(=[O:7])/[CH:2]=[CH:3]/[C:4]([OH:6])=[O:5].[NH:9]1[CH2:13][CH2:12][CH:11]([S:14][C@@H:15]2[CH2:32][CH2:31][C@@:30]3([CH3:33])[CH:17]([C:18](=O)[CH2:19][C@@H:20]4[C@@H:29]3[CH2:28][CH2:27][C@@:25]3([CH3:26])[C@H:21]4[CH2:22][CH2:23][C:24]3=[O:34])[CH2:16]2)[CH2:10]1.Cl.[NH2:37][OH:38]>>[C:1]([OH:8])(=[O:7])/[CH:2]=[CH:3]/[C:4]([OH:6])=[O:5].[NH:9]1[CH2:13][CH2:12][CH:11]([S:14][C@@H:15]2[CH2:32][CH2:31][C@@:30]3([CH3:33])[CH:17](/[C:18](=[N:37]/[OH:38])/[CH2:19][C@@H:20]4[C@@H:29]3[CH2:28][CH2:27][C@@:25]3([CH3:26])[C@H:21]4[CH2:22][CH2:23][C:24]3=[O:34])[CH2:16]2)[CH2:10]1

Participants

3

Reactant 2

HCID 443297Hydroxyamine hydrochlorideHCID 69007676HCID 69007676, compound

Product 1

HCID 87653434(E)-but-2-enedioic acid;(3R,6E,8R,9S,10R,13S,14S)-6-hydroxyimino-10,13-dimethyl-3-pyrrolidin-3-ylsulfanyl-2,3,4,5,7,8,9,11,12,14,15,16-dodecahydro-1H-cyclopenta[a]phenanthren-17-one

Procedure

The title compound was prepared following the procedure described in Example 1 and starting from 3α-[3-(RS)-pyrrolidinylthio]androstane-6,17-dione fumarate (I-dc, Example 81, 115 mg) and hydroxylamine hydrochloride (20 mg). The crude product was purified by flash chromatography (SiO2, CH2Cl2/MeOH/NH3 9/1/0.1). To the concentrated fractions the stoichiometric amount of fumaric acid in MeOH was added. After addition of EtOAc, the precipitate was filtered to give the title compound I-dd as a white solid in 65% yield. 1H-NMR (300 MHz, DMSO-d6, ppm from TMS): δ 10.72 (1H, bs), 6.42 (1H, m), 4.69 (1H, m), 3.57 (1H, m), 3.30-3.10 (6H, m), 2.40-0.95 (20H, m), 0.76 (3H, s), 0.63 (3H, s).

Workup

  1. customThe title compound was prepared
  2. customThe crude product was purified by flash chromatography (SiO2, CH2Cl2/MeOH/NH3 9/1/0.1)
  3. additionTo the concentrated fractions the stoichiometric amount of fumaric acid in MeOH was added
  4. additionAfter addition of EtOAc
  5. filtrationthe precipitate was filtered

Sources & evidence

ORD record
ord-7127e0140cd24d569a64493ba359a420
Source dataset
uspto-grants-2013_09
Patent number
US08536160B2

Reaction notes

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