Chlorotrimethylsilane → HCID 86721103, compound

HRID 1396325Notes

Reaction equation

HRID 1396325 reaction equation
Cl[Si](C)(C)C.Br[CH2:7][C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9].[F:15][C:16]1[C:23]([CH3:24])=[CH:22][CH:21]=[C:20]([F:25])[C:17]=1[CH:18]=[O:19]>O1CCCC1.[Zn]>[F:15][C:16]1[C:23]([CH3:24])=[CH:22][CH:21]=[C:20]([F:25])[C:17]=1[CH:18]([OH:19])[CH2:7][C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9]

Participants

6

Reactant 3

HCID 6397ChlorotrimethylsilaneHCID 79177tert-Butyl bromoacetateHCID 27741372,6-Difluoro-3-methylbenzaldehyde

Product 1

HCID 86721103HCID 86721103, compoundYield 56%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

To a suspension of zinc (1.256 g, 19.21 mmol) in dry tetrahydrofuran (18 mL) was added chlorotrimethylsilane (1.228 mL, 9.61 mmol). After 20 min, tert-butyl 2-bromoacetate (1.420 mL, 9.61 mmol) was added. The reaction was stirred at rt for 10 min, then heated at 40° C. for 20 min. The reaction mixture was cooled to 0° C. under Ar, and 2,6-difluoro-3-methylbenzaldehyde (1.5 g, 9.61 mmol) in 3 mL of dry THF was added. The reaction was allowed to warm to rt and stirred overnight. The reaction mixture was quenched with 5% aqueous NaHCO3, filtered, and rinsed with EtOAc. The filtrate was washed with water and brine, dried over MgSO4, filtered, concentrated and purified by silica gel chromatography to yield the desired product (1.46 g, 56%). MS (ESI) m/z: 295.1 (M+Na)+.

Workup

  1. temperatureheated at 40° C. for 20 min
  2. additionwas added
  3. temperatureto warm to rt
  4. stirringstirred overnight
  5. customThe reaction mixture was quenched with 5% aqueous NaHCO3
  6. filtrationfiltered
  7. washrinsed with EtOAc
  8. washThe filtrate was washed with water and brine
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated
  12. custompurified by silica gel chromatography

Sources & evidence

ORD record
ord-8d5655e1546d467da3904b84a7004baa
Source dataset
uspto-grants-2014_12
Patent number
US08901115B2

Reaction notes

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