Sodium Hydroxide → 3alpha-Hydroxy-16alpha-methyl-5alpha-androstan-11-one 17beta-carboxylic acid

HRID 267635Notes

Reaction equation

HRID 267635 reaction equation
[OH-].[Na+].BrBr.Br[O-].[Na+].[OH:8][C@@H:9]1[CH2:28][CH2:27][C@@:26]2([CH3:29])[C@@H:11]([CH2:12][CH2:13][C@@H:14]3[C@@H:25]2[C:24](=[O:30])[CH2:23][C@@:22]2([CH3:31])[C@H:15]3[CH2:16][C@@H:17]([CH3:32])[C@@H:18]2[C:19](=[O:21])C)[CH2:10]1.Br[O-].O.O.O.O.O.O.O.S([O-])([O-])=[O:43].[Na+].[Na+]>O.O1CCOCC1>[OH:8][C@@H:9]1[CH2:28][CH2:27][C@@:26]2([CH3:29])[C@@H:11]([CH2:12][CH2:13][C@@H:14]3[C@@H:25]2[C:24](=[O:30])[CH2:23][C@@:22]2([CH3:31])[C@H:15]3[CH2:16][C@@H:17]([CH3:32])[C@@H:18]2[C:19]([OH:21])=[O:43])[CH2:10]1

Participants

9

Reactant 6

HCID 14798Sodium HydroxideHCID 24408BromineHCID 160916Sodium sulfite heptahydrateHCID 5460626HypobromiteHCID 23673712Sodium hypobromiteHCID 705839113alpha-Hydroxy-16alpha-methyl-5alpha-pregnane-11,20-dione

Product 1

HCID 227882583alpha-Hydroxy-16alpha-methyl-5alpha-androstan-11-one 17beta-carboxylic acidYield 99.5%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent3×HCID 312751,4-DioxaneSolvent2×

Procedure

A solution of sodium hydroxide (7.35g.) in water, (55 ml.) was stirred at -5° and bromine added slowly maintaining the temperature between -5° and 0°. Cold dioxan (45 ml.) was added and the pale yellow sodium hypobromite solution stirred at 0° until required. 3α-Hydroxy-16α-methyl-5α-pregnane-11, 20-dione (5.0g.) was dissolved in dioxan (200 ml.) and water (55 ml.). The hypobromite solution was added over 5 min. and the resulting mixture kept between 5° and 10° with stirring for 3 hr. Sodium sulphite heptahydrate (2.8g.) in water (15 ml.) was added and the solution refluxed for 15 min. The mixture was acidified and concentrated to incipient crystallisation before pouring into water (1 1.). Filtration afforded the title compound (3.85g.); m.p. 265°-268°.

Workup

  1. temperaturemaintaining the temperature between -5° and 0°
  2. customkept between 5° and 10°
  3. temperaturethe solution refluxed for 15 min
  4. concentrationconcentrated to incipient crystallisation
  5. additionbefore pouring into water (1 1.)
  6. filtrationFiltration

Sources & evidence

ORD record
ord-ccc9c6197c7e4ac380bc095a5da15d80
Source dataset
uspto-grants-1976_03
Patent number
US03943124

Reaction notes

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