2-Butene, 1-bromo-3-methyl- → HCID 57941443, compound

HRID 1437971Notes

Reaction equation

HRID 1437971 reaction equation
[C:1]1([N:7]2[C:15](=[O:16])[C:14]3[C@@H:13]4[C:17]([CH3:19])([CH3:18])[C@@:10]([CH3:20])([CH2:11][CH2:12]4)[C:9]=3[NH:8]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Br[CH2:22][CH:23]=[C:24]([CH3:26])[CH3:25]>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.CN(C)C=O>[CH3:20][C@@:10]12[C:17]([CH3:19])([CH3:18])[C@@H:13]([C:14]3[C:15](=[O:16])[N:7]([C:1]4[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=4)[N:8]([CH2:22][CH:23]=[C:24]([CH3:26])[CH3:25])[C:9]=31)[CH2:12][CH2:11]2

Participants

5

Reactant 2

HCID 700922-Butene, 1-bromo-3-methyl-HCID 57941335(4s,7r)-2-Phenyl-7,8,8-trimethyl-1,2,4,5,6,7-hexahydro-4,7-methano-indazol-3-one2×

Product 1

HCID 57941443HCID 57941443, compoundYield 7.2%

Reagents, catalysts & solvents 2

HCID 67553Tetrabutylammonium IodideCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of (4S,7R)-7,8,8-trimethyl-2-phenyl-1,2,4,5,6,7-hexahydro-4,7-methano-indazol-3-one (Intermediate 6; 420 mg, 1.57 mmol), tetrabutylammonium iodide (2.31 g, 6.26 mmol) and 4-bromo-2-methyl-2-butene (720 μL, 6.26 mmol) in dimethylformamide (5 mL) was heated in an oil-bath at 100° C. for 8 h. The solvent was evaporated and the residue was partitioned between dichloromethane and water. The aqueous layer was extracted with dichloromethane (2×100 mL) and the combined organic layers were washed with water (5×100 mL) and aqueous sodium thiosulfate (100 mL). The solvent was evaporated and the residue was purified using an ISCO 40 g column, eluting with 90-100% ethyl acetate/hexanes to give (4S,7R)-7,8,8-trimethyl-1-(3-methyl-but-2-enyl)-2-phenyl-1,2,4,5,6,7-hexahydro-4,7-methano-indazol-3-one (38 mg, 7%) as a viscous yellow oil. APCI(+)-MS (M+H) 337.

Workup

  1. customThe solvent was evaporated
  2. customthe residue was partitioned between dichloromethane and water
  3. extractionThe aqueous layer was extracted with dichloromethane (2×100 mL)
  4. washthe combined organic layers were washed with water (5×100 mL) and aqueous sodium thiosulfate (100 mL)
  5. customThe solvent was evaporated
  6. customthe residue was purified
  7. washeluting with 90-100% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-4866eef03f7243d2affbae0c8c6ab43d
Source dataset
uspto-grants-2009_11
Patent number
US07622492B2

Reaction notes

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