Hexane → 17beta-Acetoxy-l-methyl-androsta-1,4-dien-3-one

HRID 259891Notes

Reaction equation

HRID 259891 reaction equation
C[Al](C)C.[CH3:5]CCCCC.C(C1C=C(C)C=C(C(C)(C)C)C=1O)(C)(C)C.[C:27]([O:30][C@H:31]1[CH2:36][CH2:35][C@H:34]2[C@H:37]3[C@H:47]([CH2:48][CH2:49][C@:32]12[CH3:33])[C@:45]1([CH3:46])[C:40](=[CH:41][C:42](=[O:50])[CH:43]=[CH:44]1)[CH2:39][CH2:38]3)(=[O:29])[CH3:28]>C(OCC)(=O)C.[Ni+2].C/C(/[O-])=C/C(C)=O.O>[C:27]([O:30][C@H:31]1[CH2:36][CH2:35][C@H:34]2[C@H:37]3[C@H:47]([CH2:48][CH2:49][C@:32]12[CH3:33])[C@:45]1([CH3:46])[C:40](=[CH:41][C:42](=[O:50])[CH:43]=[C:44]1[CH3:5])[CH2:39][CH2:38]3)(=[O:29])[CH3:28]

Participants

8

Reactant 4

HCID 8058HexaneHCID 314042,6-Di-tert-butyl-4-methylphenolHCID 102247Boldenone acetateHCID 16682925Trimethylaluminum

Product 1

HCID 1042750517beta-Acetoxy-l-methyl-androsta-1,4-dien-3-oneYield 20%

Reagents, catalysts & solvents 3

HCID 131719428nickel(2+);(Z)-4-oxopent-2-en-2-olateCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
60 °C

Procedure

12 ml of trimethylaluminum of a 10% solution in hexane (12 mmol) is introduced at room temperature under nitrogen atmosphere. With stirring, 2.64 g of 2,6-di-tert-butyl-4-methylphenol is added in portions. The solution is stirred for 30 more minutes and 3.27 g (10 mmol) of 17β-acetoxy-androsta-l,4-dien-3-one in 20 ml of ethyl acetate is added at 25° C. The solution is heated to 60° C. and 143 mg of nickel(II)-acetylacetonate is added at 60° C. The solution is stirred for another 2.5 hours at this temperature. After cooling, 1.1 ml water is added for hydrolysis and stirred for 15 minutes. The solid is filtered off, rewashed twice-with 50 ml of ethyl, acetate. After concentration by evaporation of the ethyl acetate phases, a crude product is obtained, which is chromatographed on silica gel with hexane/ethyl acetate as eluent with increasing ethyl acetate portion. 1.55 g of initial material is recovered. 0.68 g of 17β-acetoxy-l-methyl-androsta-1,4-dien-3-one of melting point 144.1° C. is obtained. The yield is 20% of theory or 38% taking into consideration the initial material recovered.

Workup

  1. additionis added at 25° C
  2. stirringThe solution is stirred for another 2.5 hours at this temperature
  3. temperatureAfter cooling
  4. stirringstirred for 15 minutes
  5. filtrationThe solid is filtered off
  6. concentrationAfter concentration
  7. customby evaporation of the ethyl acetate phases
  8. customa crude product is obtained
  9. customwhich is chromatographed on silica gel with hexane/ethyl acetate as eluent with increasing ethyl acetate portion
  10. custom1.55 g of initial material is recovered

Sources & evidence

ORD record
ord-2d2a04f0cfae4c46a518e861bbdb55fd
Source dataset
uspto-grants-1996_06
Patent number
US05523428

Reaction notes

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