Dibromomethane → HCID 22908410, compound

HRID 1079016Notes

Reaction equation

HRID 1079016 reaction equation
BrCBr.[Si:4]([O:11][CH:12]1[CH2:16][C:15](=O)[C:14]([CH:18]([CH3:21])[CH:19]=[CH2:20])=[CH:13]1)([C:7]([CH3:10])([CH3:9])[CH3:8])([CH3:6])[CH3:5].[CH3:22]CCCCC.C(=O)([O-])O.[Na+]>O1CCCC1.ClCCl.O.[Zn].[Ti](Cl)(Cl)(Cl)Cl>[Si:4]([O:11][CH:12]1[CH2:16][C:15](=[CH2:22])[C:14]([CH:18]([CH3:21])[CH:19]=[CH2:20])=[CH:13]1)([C:7]([CH3:10])([CH3:9])[CH3:8])([CH3:6])[CH3:5]

Participants

10

Reactant 4

HCID 3024DibromomethaneHCID 8058HexaneHCID 516892Sodium BicarbonateHCID 22908400HCID 22908400, compound

Product 1

HCID 22908410HCID 22908410, compoundYield 61%

Reagents, catalysts & solvents 5

HCID 23994ZincCatalystHCID 24193Titanium TetrachlorideCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

A suspension prepared by suspending 3.7 g of zinc dust in 30 ml of tetrahydrofuran was mixed with 1.4 ml of dibromomethane in an atmosphere of argon at a temperature of -20° to -10° C. After stirring for fifteen minutes, 12.5 ml of a dichloromethane solution of 1M titanium tetrachloride was added dropwise to the suspension and stirred at the above temperatures for thirty minutes and at 4° C. for three days. A solution prepared by dissolving 3.33 g of (RS)-3-(1-methyl-2-propenyl)-4-oxocyclopent-2-en-1-yl t-butyldimethylsilyl ether in 15 ml of dichloromethane was added dropwise to the reaction solution in an atmosphere of argon at a temperature of -20° to -10° C. After stirring at an ambient temperature for six hours, 30 ml of hexane was further added to the reaction solution. Under stirring, a suspension prepared by suspending 15 g of sodium hydrogencarbonate in 100 ml of water was added gradually to the reaction solution. After stirring at an ambient temperature for two hours, the reaction solution was filtered through celite, extracted with hexane, and dried over anhydrous magnesium sulfate. After removal of the solvent under reduced pressure, the obtained oily substance was subjected to silica gel column chromatography to yield 2.02 g of (RS)-3-(1-methyl-2-propenyl)-4-methylidenecyclopent-2-en-1-yl t-butyldimethylsilyl ether. Yield 61%

Workup

  1. customA suspension prepared
  2. stirringstirred at the above temperatures for thirty minutes and at 4° C. for three days
  3. customA solution prepared
  4. additionwas added dropwise to the reaction solution in an atmosphere of argon at a temperature of -20° to -10° C
  5. stirringAfter stirring at an ambient temperature for six hours
  6. stirringUnder stirring
  7. customa suspension prepared
  8. additionwas added gradually to the reaction solution
  9. stirringAfter stirring at an ambient temperature for two hours
  10. filtrationthe reaction solution was filtered through celite
  11. extractionextracted with hexane
  12. dry with materialdried over anhydrous magnesium sulfate
  13. customAfter removal of the solvent under reduced pressure

Sources & evidence

ORD record
ord-e99e013634a84d44b4ebe23a804428d0
Source dataset
uspto-grants-1996_08
Patent number
US05550258

Reaction notes

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