Methanol → 17-Hydroxy-16-methylidenepregn-4-ene-3,20-dione

HRID 1285323Notes

Reaction equation

HRID 1285323 reaction equation
C1(S([CH2:9][C:10]2[CH2:29][C@@H:28]3[C@:15]([CH3:32])([CH2:16][CH2:17][C@H:18]4[C@H:27]3[CH2:26][CH2:25][C:24]3[C@:19]4([CH3:31])[CH2:20][CH2:21][C:22](=[O:30])[CH:23]=3)[C:11]=2[C:12](=[O:14])[CH3:13])=O)C=CC=CC=1.CO.C(N(CC)CC)C.C[O:43]P(OC)OC>C1(C)C=CC=CC=1.C1(C)C=CC=CC=1.CCCCCCC>[OH:43][C@:11]1([C@:15]2([CH3:32])[C@H:28]([C@H:27]3[C@H:18]([CH2:17][CH2:16]2)[C@:19]2([CH3:31])[C:24](=[CH:23][C:22](=[O:30])[CH2:21][CH2:20]2)[CH2:25][CH2:26]3)[CH2:29][C:10]1=[CH2:9])[C:12](=[O:14])[CH3:13]

Participants

7

Reactant 4

HCID 887MethanolHCID 8471TriethylamineHCID 8472Trimethyl phosphite2×HCID 57250872HCID 57250872, compound

Product 1

HCID 19279117-Hydroxy-16-methylidenepregn-4-ene-3,20-dione

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 22263336Toluene heptaneSolvent

Procedure

The crude 16-(phenylsulfinylmethyl)pregna-4,16-diene-3,20-dione (VIA, Example 38) is slurried in toluene (300 ml) under a nitrogen atmosphere. Methanol (2 mmole), triethylamine (0.13 mmole) and then trimethylphosphite (0.79 mmole) are added. The reaction mixture is sealed and heated under pressure at 90° for 4 hours, then cooled to 20°-25°. The reaction mixture is subjected to acid hydrolysis of the access trimethylphosphite, base and buffer washes and finally crystallization from toluene/heptane to give the title compound. NMR (CDCl3) 0.82, 1.20, 1.30, 3.5, 5.04, 5.21 and 5.68 δ

Workup

  1. customThe reaction mixture is sealed
  2. temperatureheated under pressure at 90° for 4 hours
  3. temperaturecooled to 20°-25°

Sources & evidence

ORD record
ord-b1b2120da7bf4af0b7a16098d6132898
Source dataset
uspto-grants-1986_01
Patent number
US04567001

Reaction notes

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