Acetic Acid → 19-Hydroxytestosterone

HRID 973213

Reaction equation

HRID 973213 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])[CH2:15][CH2:14][CH2:13]4)[CH2:10][CH2:9][C:8]1=[CH:7][C:6](=[O:21])[CH2:5][CH2:4]2.[BH4-].[K+].O.C(O)(=[O:27])C>C(O)C>[OH:27][C@H:15]1[CH2:14][CH2:13][C@H:12]2[C@H:11]3[C@H:20]([CH2:19][CH2:18][C@:16]12[CH3:17])[C@:3]1([CH2:2][OH:1])[C:8](=[CH:7][C:6](=[O:21])[CH2:5][CH2:4]1)[CH2:9][CH2:10]3

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 962WaterHCID 4192641Potassium borohydride3×HCID 2280225719-Hydroxy-4-androsten-3-one

Product 1

HCID 15096819-Hydroxytestosterone

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 150 g of 19-hydroxyandrost-4-en-3-one in 6 liters of ethanol is cooled in an ice bath. To this cold solution is added 13.5 g of potassium borohydride, and the reaction mixture is stirred for two hours at about 0 ° C after which a second 13.5 g or potassium borohydride is added. Two hours later a third 13.5 g portion of potassium borohydride is added to the reaction mixture which is stirred for an additional 1 hour then poured into 11 liters of water which 70 ml of acetic acid is added. The ethanol is distilled off under reduced pressure and the aqueous residue cooled to 0° C. The solid which separates is filtered off, dried and dissolved in 25 liters of hot chloroform after which the temperature is adjusted to 25° C. To the chloroform solution is added 250 g of manganese dioxide, and the mixture is stirred for 2 hours then filtered and the solvents removed under reduced pressure. The solid residue is recrystallized from acetonitrile to give 17β,19-dihydroxyandrost-4-en-3-one. M.P. 205°-207° C.

Workup

  1. additionis added
  2. additionis added
  3. distillationThe ethanol is distilled off under reduced pressure
  4. filtrationThe solid which separates is filtered off
  5. customdried
  6. dissolutiondissolved in 25 liters of hot chloroform after which the temperature
  7. customis adjusted to 25° C
  8. additionTo the chloroform solution is added 250 g of manganese dioxide
  9. stirringthe mixture is stirred for 2 hours
  10. filtrationthen filtered
  11. customthe solvents removed under reduced pressure
  12. customThe solid residue is recrystallized from acetonitrile

Sources & evidence

ORD record
ord-91bebf9833a54d338a247dfd26941e38
Source dataset
uspto-grants-1977_10
Patent number
US04055641

Linked notes

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