Chloroacetonitrile → 17beta-Cyanomethoxycarbonyl-3alpha-hydroxy-5alpha-androstan-11-one

HRID 267620Notes

Reaction equation

HRID 267620 reaction equation
C([N:3]([CH2:6][CH3:7])CC)C.[OH:8][C@@H:9]1[CH2:26][CH2:25][C@@:24]2([CH3:27])[C@@H:11]([CH2:12][CH2:13][C@@H:14]3[C@@H:23]2[C:22](=[O:28])[CH2:21][C@@:19]2([CH3:20])[C@H:15]3[CH2:16][CH2:17][C@@H:18]2[C:29]([OH:31])=[O:30])[CH2:10]1.ClCC#N>CC(C)=O>[C:6]([CH2:7][O:31][C:29]([C@H:18]1[CH2:17][CH2:16][C@H:15]2[C@H:14]3[C@H:23]([C:22](=[O:28])[CH2:21][C@:19]12[CH3:20])[C@:24]1([CH3:27])[C@H:11]([CH2:10][C@H:9]([OH:8])[CH2:26][CH2:25]1)[CH2:12][CH2:13]3)=[O:30])#[N:3]

Participants

5

Reactant 3

HCID 7856Chloroacetonitrile2×HCID 8471TriethylamineHCID 227882653alpha-Hydroxy-5alpha-androstan-11-one 17beta-carboxylic acid

Product 1

HCID 13171009217beta-Cyanomethoxycarbonyl-3alpha-hydroxy-5alpha-androstan-11-one

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

Triethylamine (4.5 mmole) was added to a solution of 3α-hydroxy-5α-androstan-11-one 17β-carboxylic acid (1.025g.) in warm acetone (50 ml.) followed by chloroacetonitrile (6 mmole). After refluxing this mixture for 3 hr. further chloroacetonitrile (6 mmole) was added and refluxing continued for 4 hr. Removal of the solvent afforded a residue which was partitioned between ether and water. The ethereal solution was washed with water, dried (MgSO4) and evaporated, to give a foam (1.187g.) which was purified by preparative t.l.c. to afford the pure title compound; m.p. 142°-146°; [α]D + 74°,.

Workup

  1. temperatureAfter refluxing this mixture for 3 hr
  2. temperaturerefluxing
  3. customRemoval of the solvent
  4. customafforded a residue which
  5. customwas partitioned between ether and water
  6. washThe ethereal solution was washed with water
  7. dry with materialdried (MgSO4)
  8. customevaporated
  9. customto give a foam (1.187g.) which
  10. customwas purified by preparative t.l.c

Sources & evidence

ORD record
ord-6f6388ad62094fc4995c14036fe5f63c
Source dataset
uspto-grants-1976_03
Patent number
US03943124

Reaction notes

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