HCID 20593839, compound → HCID 12135235, compound

HRID 1369372Notes

Reaction equation

HRID 1369372 reaction equation
[CH3:1]C(C)([O-])C.[K+].[CH3:7][C@@H:8]1[CH2:25][C:24]2[CH2:23][C:22](=O)[CH2:21][CH2:20][C:19]=2[C@@H:18]2[C@@H:9]1[C@H:10]1[C@@:14]([CH2:16][CH2:17]2)([CH3:15])[C:13](=[CH2:27])[CH2:12][CH2:11]1>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[CH3:7][C@@H:8]1[CH2:25][C:24]2[CH2:23][C:22](=[CH2:1])[CH2:21][CH2:20][C:19]=2[C@@H:18]2[C@@H:9]1[C@H:10]1[C@@:14]([CH2:16][CH2:17]2)([CH3:15])[C:13](=[CH2:27])[CH2:12][CH2:11]1

Participants

5

Reactant 2

HCID 20593839HCID 20593839, compoundHCID 23665647Potassium tert-butoxide

Product 1

HCID 12135235HCID 12135235, compoundYield 80.2%

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

Methyltriphenylphosphonium bromide (2.2 g, 6 mmol) was added to a stirred solution of potassium t-butoxide (680 mg, 6 mmol) in 25 ml dry THF under a nitrogen atmosphere. The yellow suspension was stirred for 30 minutes at room temperature. A solution of (7α)-7-methyl-3-keto-17-methyleneestr-5(10)ene (850 mg, 3 mmol) in 25 ml dry THF was added rapidly (approx. 30 seconds) to the suspension, resulting in a slightly exothermic reaction. The reaction mixture was stirred for 30 minutes at room temperature, poured on ice-water (100 ml) and extracted with ethyl acetate (100 ml). The organic layer was washed with water (50 ml), dried (Na2SO4) and evaporated to dryness to give (7α)-7-methyl-3,17-dimethyleneestr-5(10)ene (680 mg, 80%) as a colorless oil. [α]D +115° (c 0.185 in ethanol).

Workup

  1. customresulting in a slightly exothermic reaction
  2. stirringThe reaction mixture was stirred for 30 minutes at room temperature
  3. additionpoured on ice-water (100 ml)
  4. extractionextracted with ethyl acetate (100 ml)
  5. washThe organic layer was washed with water (50 ml)
  6. dry with materialdried (Na2SO4)
  7. customevaporated to dryness

Sources & evidence

ORD record
ord-54828b2abe6146348f5ddc38246356a5
Source dataset
uspto-grants-2003_06
Patent number
US06579864B1

Reaction notes

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