Water → 4-Androstene-3,17-dione, 1alpha-methyl-

HRID 1415723Notes

Reaction equation

[CH3:1][C@:2]12[CH2:19][CH2:18][C@H:17]3[C@@H:7]([CH2:8][CH2:9][C:10]4[C@:15]3([CH3:16])[CH:14]=[CH:13][C:12](=[O:20])[CH:11]=4)[C@@H:6]1[CH2:5][CH2:4][C:3]2=[O:21].[CH3:22][Al](C)C.O>O1CCOCC1.C1(C)C=CC=CC=1.[Cu]Br>[CH3:22][C@@H:14]1[C@@:15]2([CH3:16])[C:10]([CH2:9][CH2:8][C@@H:7]3[C@@H:17]2[CH2:18][CH2:19][C@@:2]2([CH3:1])[C@H:6]3[CH2:5][CH2:4][C:3]2=[O:21])=[CH:11][C:12](=[O:20])[CH2:13]1

Participants

Conditions

Temperature: 25 °C

Procedure

14.2 g (50 mmol) of androsta-1,4-diene-3,17-dione is dissolved under nitrogen atmosphere in 100 ml of anhydrous dioxane. 716 mg (5 mmol) of copper(I) bromide is added and the solution is heated to 25° C. Then, 47 ml (55 mmol) of a 10% trimethylaluminum solution in toluene is added to the reaction, so that the temperature does not rise above 35° C. Then, it is stirred for 1.5 more hours at 35° C. For hydrolysis, 2.5 ml of water mixed with 10 ml of dioxane is added to the reaction and the solution is stirred for 15 more minutes. The inorganic solid is suctioned off and rewashed with 30 ml of dioxane. After concentration by evaporation of the dioxane solution, 17 g of crude product is obtained, which is chromatographed as eluent on silica gel with hexane/ethyl acetate mixtures. After concentration by evaporation of the fractions and recrystallization from diisopropyl ether, 11.66 g of 1α-methylandrost-4-ene-3,17-dione (77% of theory) of melting point 154° C. is obtained.

Workup

customdoes not rise above 35° C
additionis added to the reaction
stirringthe solution is stirred for 15 more minutes
concentrationAfter concentration
customby evaporation of the dioxane solution

Sources & evidence

ORD record: ord-b91d3dffe4a94fad90f49f0ab97b3fa6
Source dataset: uspto-grants-1999_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05908945

Reaction notes

Loading…