Isopropanol → 3-Hydroxyandrostane-17-carbonitrile

HRID 267626Notes

Reaction equation

HRID 267626 reaction equation
[C:1]([C@H:3]1[CH2:8][CH2:7][C@H:6]2[C@H:9]3[C@H:19]([CH2:20][CH2:21][C@:4]12[CH3:5])[C@:17]1([CH3:18])[C@H:12]([CH2:13][C:14](=[O:22])[CH2:15][CH2:16]1)[CH2:11][CH2:10]3)#[N:2].C(O)(C)C.C(N(CC)CC)C>O>[C:1]([C@H:3]1[CH2:8][CH2:7][C@H:6]2[C@H:9]3[C@H:19]([CH2:20][CH2:21][C@:4]12[CH3:5])[C@:17]1([CH3:18])[C@H:12]([CH2:13][C@H:14]([OH:22])[CH2:15][CH2:16]1)[CH2:11][CH2:10]3)#[N:2]

Participants

5

Reactant 3

HCID 3776IsopropanolHCID 8471TriethylamineHCID 86733140HCID 86733140, compound

Product 1

HCID 1710843-Hydroxyandrostane-17-carbonitrile

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A solution of 17β-cyano-5α-androstan-3-one (1.0 g.) in the minimum volume of isopropanol (ca. 75 ml.) was added to a stock solution of chloroiridic acid/trimethyl phosphite complex (50 ml.) preneutralised to pH4 with triethylamine (4 ml.). This solution, after being refluxed for 20 hours, was poured into water (200 ml.) and extracted with chloroform. The chloroform solution was washed with water, dried (MgSO4), filtered and evaporated to a gum (1.13 g.). This was subjected to preparative t.l.c. eluting successively with ethanol/chloroform (1:49) and ethyl acetate/benzene (1:19). The main band was removed between the eluant change and the final elution was repeated four times before removing the main band. This gave pure title compound (195 mg.) as a white solid; m.p. 156°-159°; [α]D + 56° (c 0.4%).

Workup

  1. temperatureThis solution, after being refluxed for 20 hours
  2. extractionextracted with chloroform
  3. washThe chloroform solution was washed with water
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. customevaporated to a gum (1.13 g.)
  7. washeluting successively with ethanol/chloroform (1:49) and ethyl acetate/benzene (1:19)
  8. customThe main band was removed between the eluant change
  9. washthe final elution
  10. custombefore removing the main band
  11. custom[α]D + 56° (c 0.4%)

Sources & evidence

ORD record
ord-27f4976f2d5c4dda9bd01518dea0c083
Source dataset
uspto-grants-1976_03
Patent number
US03943124

Reaction notes

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