Toluene → HCID 86738379, compound

HRID 1065703Notes

Reaction equation

HRID 1065703 reaction equation
[C:1]([O:4][C@@H:5]1[CH2:10][C@H:9]2[C@H:11]3[C@H:21]([CH2:22][CH2:23][C@:7]2([CH3:8])[C@H:6]1[N:25]([CH3:32])[C:26](=[O:31])[C:27]([F:30])([F:29])[F:28])[C@:19]1([CH3:20])[C:14](=[CH:15][C:16](=[O:24])[CH2:17][CH2:18]1)[CH2:13][CH2:12]3)(=[O:3])[CH3:2].C1(C)C=CC=CC=1>ClC1C=CC=CC=1>[C:1]([O:4][C@@H:5]1[CH2:10][C@H:9]2[C@H:11]3[C@H:21]([CH2:22][CH2:23][C@:7]2([CH3:8])[C@H:6]1[N:25]([CH3:32])[C:26](=[O:31])[C:27]([F:29])([F:28])[F:30])[C@:19]1([CH3:20])[C:14](=[CH:15][C:16](=[O:24])[CH:17]=[CH:18]1)[CH2:13][CH2:12]3)(=[O:3])[CH3:2]

Participants

4

Reactant 2

HCID 1140TolueneHCID 12962060HCID 12962060, compound

Product 1

HCID 86738379HCID 86738379, compoundYield 81.2%

Reagents, catalysts & solvents 1

HCID 7964ChlorobenzeneSolvent

Procedure

A solution of 16α-acetyloxy-17β-(N-trifluoroacetyl-methylamino)-androst-4-en-3-one (1.88 g) and diphenylselenic anhydride (1.7 g) in chlorobenzene (39 ml) was heated under reflux for 1 h. The solution was cooled, toluene was added and the solution was filtered through a column (7.5 cm×2.5 cm) of silica gel (0.063-0.2 mm). Elution with toluene removed diphenylselenide. Elution with ether yielded a fraction which was evaporated to dryness to give 16α-acetyloxy-17β-(N-trifluoroacetyl-methylamino)-androsta-1,4-dien-3-one as a yellow gum (1.52 g). A solution of the product in ethanol (40 ml) and aqueous sodium hydroxide solution (3 ml; 4 N) was heated under reflux for 1.5 h.; the solution was concentrated and cooled, then water was added to precipitate an off-white solid, which was filtered off, washed with water and dried in vacuo to give 16α-hydroxy-17β-methylamino-androsta-1,4-dien-3-one (1 g). The product was dissolved in ethanol (20 ml), a solution of maleic acid (0.37 g) in ethanol (10 ml) was added and the resulting solution was treated with charcoal, filtered and evaporated to give a pale yellow gum (1.44 g). Crystallisation from acetone gave 16α-hydroxy-17β-methylamino-androsta-1,4-dien-3-one (Z)-2-butenedioate (1:1) (salt) as colourless prisms (0.88 g), m.p. 184°-191° C. (decomp.), [α]D +14.2° (c 0.88 in ETOH).

Workup

  1. temperatureunder reflux for 1 h
  2. temperatureThe solution was cooled
  3. filtrationthe solution was filtered through a column (7.5 cm×2.5 cm) of silica gel (0.063-0.2 mm)
  4. washElution with toluene
  5. customremoved diphenylselenide
  6. washElution with ether
  7. customyielded a fraction which
  8. customwas evaporated to dryness

Sources & evidence

ORD record
ord-8160dd4c1e714959988431108b40eaff
Source dataset
uspto-grants-1982_05
Patent number
US04330539

Reaction notes

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