Formaldehyde → HCID 54145314, compound

HRID 2398002Notes

Reaction equation

HRID 2398002 reaction equation
[OH:1][CH2:2][C@@:3]12[C@@H:20]3[C@H:11]([C@H:12]4[C@@:16]([CH2:18][CH2:19]3)([CH3:17])[C:15](=[O:21])[CH2:14][CH2:13]4)[CH2:10][CH2:9][C:8]1=[CH:7][C:6](=[O:22])[CH2:5][CH2:4]2.[C:23]1([SH:29])[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.[CH2:30]=O.[OH-].[Na+]>CCOCC.C(O)C.C(N(CC)CC)C>[OH:1][CH2:2][C@@:3]12[C@@H:20]3[C@H:11]([C@H:12]4[C@@:16]([CH2:18][CH2:19]3)([CH3:17])[C:15](=[O:21])[CH2:14][CH2:13]4)[CH2:10][CH2:9][C:8]1=[C:7]([CH2:30][S:29][C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)[C:6](=[O:22])[CH2:5][CH2:4]2

Participants

8

Reactant 4

HCID 712FormaldehydeHCID 7969ThiophenolHCID 14798Sodium HydroxideHCID 25237919-Hydroxyandrostenedione

Product 1

HCID 54145314HCID 54145314, compound

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 3283Diethyl EtherSolventHCID 8471TriethylamineSolvent

Procedure

A mixture of 19-hydroxy-4-androstene-3,17-dione, thiophenol, 40% aqueous formaldehyde, triethylamine and ethanol are heated at the reflux temperature for about 48 hours. The cooled solution is poured into an aqueous sodium hydroxide solution and the product isolated by ether extraction. The ether extract is washed with water, dried over magnesium sulfate and the solvent removed under reduced pressure. The residue is triturated with hot hexane to remove the condensation products derived from the thiophenol and formaldehyde. The 19-hydroxy-4-phenylthiomethyl-4-androsten-3,17-dione so obtained is desulfurized by dissolving in acetone and adding to a suspension of Raney Nickel in refluxing acetone. The mixture is heated at its reflux temperature while stirring for about 5 hours. The hot solution is filtered and the nickel washed with boiling ethanol and water. The combined filtrates are concentrated under vacuum whereupon the product separates as a solid. Recrystallization from an acetone-hexane solution yields 19-hydroxy-4-methyl-4-androstene-3,17-dione.

Workup

  1. temperatureare heated at the reflux temperature for about 48 hours
  2. extractionThe ether extract
  3. washis washed with water
  4. dry with materialdried over magnesium sulfate
  5. customthe solvent removed under reduced pressure
  6. customThe residue is triturated with hot hexane
  7. customto remove the condensation products

Sources & evidence

ORD record
ord-c19d717b619c49ebb8a24b9cd7ab19de
Source dataset
uspto-grants-1977_05
Patent number
US04022769

Reaction notes

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