Chlorotrimethylsilane → HCID 67905434, compound

HRID 1885905Notes

Reaction equation

HRID 1885905 reaction equation
BrCCBr.C[Si](C)(C)Cl.Br[CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[C:18](=[CH:23][O:24][CH3:25])[C:19]([O:21][CH3:22])=[O:20].[Cu](C#N)C#N.[Cl-].[Li+].[Cl:33][C:34]1[CH:42]=[CH:41][CH:40]=[CH:39][C:35]=1[C:36](Cl)=[O:37]>O1CCCC1.[Zn]>[Cl:33][C:34]1[CH:42]=[CH:41][CH:40]=[CH:39][C:35]=1[C:36]([CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[C:18](=[CH:23][O:24][CH3:25])[C:19]([O:21][CH3:22])=[O:20])=[O:37]

Participants

9

Reactant 6

HCID 6397ChlorotrimethylsilaneHCID 78391,2-DibromoethaneHCID 691102-Chlorobenzoyl chlorideHCID 433294Lithium ChlorideHCID 53395349Methyl 2-[2-(bromomethyl)phenyl]-3-methoxyprop-2-enoateHCID 178418260HCID 178418260, compound

Product 1

HCID 67905434HCID 67905434, compoundYield 35%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 8028TetrahydrofuranSolvent4×

Conditions

Temperature
-78 °C

Procedure

700 mg of 1,2-dibromoethane are added to 2.3 g of zinc powder in 20 ml of THF (tetrahydrofuran). Refluxing is carried out until evolution of gas has ended, the mixture is allowed to cool to room temperature (20° C.) and 0.2 ml of trimethylchlorosilane is added. A solution of 10 g (35 mmol) of methyl α-(2-bromomethylphenyl)-β-methoxyacrylate in 40 ml of THF is added dropwise to this solution at 0° C. and stirring is continued for 3 hours at 5° C. Thereafter, the mixture is cooled to -78° C. and a solution of 3.2 g of copper cyanide and 3 g of lithium chloride in 40 ml of THF is added. The mixture is allowed to thaw for 5 minutes at -20° C. and is again cooled to -78° C., and a solution of 6.1 g of 2-chlorobenzoyl chloride in 20 ml of THF is added dropwise. Stirring is carried out overnight at room temperature. The reaction mixture is poured onto water and extracted with ethyl acetate, and the organic phase is dried and evaporated down. Chromatography over silica gel using hexane/ethyl acetate gives 4.1 g of compound No. 5 (Table 2) as a colorless solid of melting point 70°-75° C. Yield: 35%.

Workup

  1. temperatureRefluxing
  2. additionis added
  3. customthaw for 5 minutes
  4. customat -20° C.
  5. temperatureis again cooled to -78° C.
  6. stirringStirring
  7. waitis carried out overnight at room temperature
  8. additionThe reaction mixture is poured onto water
  9. extractionextracted with ethyl acetate
  10. customthe organic phase is dried
  11. customevaporated down

Sources & evidence

ORD record
ord-1e4609d694eb4e6fa0616afe2b127619
Source dataset
uspto-grants-1992_09
Patent number
US05147892

Reaction notes

Loading…