Methyl iodide → HCID 12135245, compound

HRID 1369373Notes

Reaction equation

HRID 1369373 reaction equation
[CH3:1][O:2][C:3]1([O:23][CH3:24])[CH2:20][CH2:19][C:18]2[C@@H:17]3[C@H:8]([C@H:9]4[C@@:13]([CH2:15][CH2:16]3)([CH3:14])[C:12](=[O:21])[CH2:11][CH2:10]4)[C@H:7]([CH3:22])[CH2:6][C:5]=2[CH2:4]1.[CH3:25]N1CCCN(C)C1=O.C[Si]([N-][Si](C)(C)C)(C)C.[Li+].IC.[Cl-].[NH4+]>O.C1COCC1>[CH3:24][O:23][C:3]1([O:2][CH3:1])[CH2:20][CH2:19][C:18]2[C@@H:17]3[C@H:8]([C@H:9]4[C@@:13]([CH2:15][CH2:16]3)([CH3:14])[C:12](=[O:21])[C@H:11]([CH3:25])[CH2:10]4)[C@H:7]([CH3:22])[CH2:6][C:5]=2[CH2:4]1

Participants

8

Reactant 5

HCID 6328Methyl iodideHCID 25517Ammonium ChlorideHCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-HCID 2733832Lithium HexamethyldisilazideHCID 15380148(7R,8R,9S,13S,14S)-3,3-dimethoxy-7,13-dimethyl-1,2,4,6,7,8,9,11,12,14,15,16-dodecahydrocyclopenta[a]phenanthren-17-one

Product 1

HCID 12135245HCID 12135245, compoundYield 65%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-40 °C

Procedure

A solution of (7α)-3,3-dimethoxy-7-methylestr-5(10)-en-17-one (1.5 g, 4.5 mmol) and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU, 1.2 mL, 9.9 mmol) in 30 mL dist. THF was added in approx. 8 minutes to a stirred solution of lithium bis(trimethylsilyl)amide (LiHMDS, 4.96 mL, 1M in THF) in 15 mL distillated THF at −40° C. under a nitrogen atmosphere. The reaction mixture was stirred for 45 minutes at −40° C. A solution of iodomethane (730 μL, 11.7 mmol) in 1 mL dist. THF was added and stirred for 1 hour and the temperature was allowed to warm up to 0° C. Water and sat. ammonium chloride solution were added and extracted with ethyl acetate. The organic layer was washed with brine, dried (Na2SO4) and evaporated to dryness. Column Chromatography using heptane/ethyl acetate 95/5 (v/v %) as eluent gave (7α,16α)-3,3-dimethoxy-7,16-dimethylestr-5(10)-en-17-one (990 mg, yield 65%).

Workup

  1. customat −40° C.
  2. stirringstirred for 1 hour
  3. temperatureto warm up to 0° C
  4. extractionextracted with ethyl acetate
  5. washThe organic layer was washed with brine
  6. dry with materialdried (Na2SO4)
  7. customevaporated to dryness

Sources & evidence

ORD record
ord-cabb9193c38042369ba599240284176c
Source dataset
uspto-grants-2003_06
Patent number
US06579864B1

Reaction notes

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