Acetate → Pregna-4,20-dien-3,6-dione

HRID 1953483Notes

Reaction equation

HRID 1953483 reaction equation
[CH3:1][C@@:2]12[C@@H:10](O)[CH2:9][CH2:8][C@H:7]1[C@@H:6]1[CH2:12][CH2:13][C:14]3[C@@H:20]([C@H:5]1CC2)[CH2:19][CH2:18][C:16](=O)[CH:15]=3.[C:21]([O-:24])(=O)[CH3:22].CC(O[C:29]([CH3:31])=[O:30])=O.N#N.[C:34]1(C)C=CC=CC=1>C(Cl)Cl.N1C=CC=CC=1>[CH2:12]=[CH:13][C@@H:14]1[C@:20]2([CH3:19])[C@H:18]([C@H:8]3[C@H:7]([CH2:6][CH2:5]2)[C@:2]2([CH3:10])[C:31](=[CH:34][C:21](=[O:24])[CH2:22][CH2:1]2)[C:29](=[O:30])[CH2:9]3)[CH2:16][CH2:15]1

Participants

8

Reactant 5

HCID 175Acetate2×HCID 947NitrogenHCID 1140TolueneHCID 7918Acetic AnhydrideHCID 9904Nandrolone

Product 1

HCID 15429665Pregna-4,20-dien-3,6-dioneYield 28%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 6344DichloromethaneSolvent

Procedure

This synthesis is depicted in FIG. 153. 19-Nor-testosterone (XIX) is commercially available, e.g., from Chemical Dynamics Corp. It provides the starting material for 19-Nor-16-androstene derivatives. 19-Nor-testosterone (XIX) was converted into the acetate (Hartman, J. A. et al., J. Am. Chem. Soc. (1956) 78:5662) with acetanhydride and pyridine. (a) A solution of this acetate (4.8 g, 15.17 mmol) in toluene (10 ml) was pyrolyzed (b) at 540° (200 Torr, slow N2-stream) in a glass tube packed with quartz pieces. Chromatography of the crude pyrolysate (3.1 g) on silica gel (150 g) with CH2Cl2 gave 1.1 g (28%) of the homogenous oily ketone 9; +57.9° (C 1) ((27]: m.p. 71-73°). -IR. (CHCl3): 1660s, 1615m, 1585w, -1H-NMR. (90 MHz): 0.84 (s, 3H); 5.82 (m, 2H); 5.87 (br. s, 1H).

Workup

  1. customat 540°

Sources & evidence

ORD record
ord-6a16ddd848204c4e8b895825d74f945a
Source dataset
uspto-grants-2000_09
Patent number
US06117860

Reaction notes

Loading…