Aluminum isopropoxide → (5alpha)-17-(3-Pyridinyl)androst-16-en-3-one

HRID 53186Notes

Reaction equation

HRID 53186 reaction equation
[N:1]1[CH:6]=[CH:5][CH:4]=[C:3]([C:7]2[C@:8]3([CH2:25][CH2:24][C@H:23]4[C@@H:13]([CH2:14][CH2:15][C@@H:16]5[C@:21]4([CH3:22])[CH2:20][CH2:19][C@@H:18]([OH:26])[CH2:17]5)[C@@H:10]3[CH2:11][CH:12]=2)[CH3:9])[CH:2]=1.CC(C)[O-].[Al+3].CC(C)[O-].CC(C)[O-]>C1(C)C=CC=CC=1.C1(=O)CCCCC1.C(OCC)C>[N:1]1[CH:6]=[CH:5][CH:4]=[C:3]([C:7]2[C@:8]3([CH2:25][CH2:24][C@H:23]4[C@@H:13]([CH2:14][CH2:15][C@@H:16]5[C@:21]4([CH3:22])[CH2:20][CH2:19][C:18](=[O:26])[CH2:17]5)[C@@H:10]3[CH2:11][CH:12]=2)[CH3:9])[CH:2]=1

Participants

6

Reactant 2

HCID 11143Aluminum isopropoxideHCID 10089316(3alpha,5alpha)-17-(3-Pyridinyl)androst-16-en-3-ol

Product 1

HCID 11725391(5alpha)-17-(3-Pyridinyl)androst-16-en-3-oneYield 86%

Reagents, catalysts & solvents 3

HCID 1140TolueneSolventHCID 3283Diethyl EtherSolventHCID 7967CyclohexanoneSolvent

Conditions

Temperature
90 °C

Procedure

From a solution of 17-(3-Pyridyl)-5α-androst-16-en-3α-ol (1.05g, 3.0 mmol) in dry toluene (60 ml) and cyclohexanone (10 ml) was distilled off part of the solvent (20 ml) to eliminate moisture. After allowing to cool to 90° C., aluminium isopropoxide (1.02 g, 5.0 mmol) was added and the mixture heated under reflux for 90 min. then allowed to cool. The mixture was diluted with diethyl ether (250 ml), washed with aqueous trisodium citrate (15% w/v; 2×30 ml), dried (Na2CO3), and concentrated. Chromatography, on elution with toluene-methanol (40:1), afforded the title compound (0.90 g, 86%) which crystallised from toluene, m.p. 190°-192° C. IR νmax 1713 cm- ; 1H-NMR (CDCl3) inter alia δ 1.04 (3H,s,19-CH3), 1.07 (3H,s, 18-CH3), 5.98 (1M,16-H), 7.22 (1H,m,Py 5-H), 7.64 (1H,m,Py 4-H), 8.46 (1 H,m,Py 6-H), 8.61 (1H,m,Py 2-H); MS m/z 349 (M+). Anal. Calcd: C,82.47; H,8.94; N,4.01. Found: C.82.00; H,8.94; N,3.84%

Workup

  1. temperaturethe mixture heated
  2. temperatureunder reflux for 90 min.
  3. temperatureto cool
  4. washwashed with aqueous trisodium citrate (15% w/v; 2×30 ml)
  5. dry with materialdried (Na2CO3)
  6. concentrationconcentrated
  7. washChromatography, on elution with toluene-methanol (40:1)

Sources & evidence

ORD record
ord-6b55b59762fe4b1c8815b77deea8ad97
Source dataset
uspto-grants-1997_04
Patent number
US05618807

Reaction notes

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