Chloride → HCID 22598003, compound

HRID 2184960Notes

Reaction equation

HRID 2184960 reaction equation
[Cl-].Cl[CH2:3][CH2:4][O:5][C:6]1[CH:7]=[C:8]([CH2:16][O:17][Si:18]([CH:25]([CH3:27])[CH3:26])([CH:22]([CH3:24])[CH3:23])[CH:19]([CH3:21])[CH3:20])[CH:9]=[CH:10][C:11]=1[O:12][CH:13]([F:15])[F:14].[OH-].[Na+].N1C(C)=CC=CC=1C.O([Si](C(C)C)(C(C)C)C(C)C)S(C(F)(F)F)(=O)=O.C([O-])(O)=O.[Na+]>[N+](CCCC)(CCCC)(CCCC)CCCC.[O-]S(O)(=O)=O.C1C=CC=CC=1.CCOCC>[CH:4]([O:5][C:6]1[CH:7]=[C:8]([CH2:16][O:17][Si:18]([CH:22]([CH3:24])[CH3:23])([CH:19]([CH3:21])[CH3:20])[CH:25]([CH3:26])[CH3:27])[CH:9]=[CH:10][C:11]=1[O:12][CH:13]([F:14])[F:15])=[CH2:3]

Participants

10

Reactant 6

HCID 312ChlorideHCID 79372,6-LutidineHCID 14798Sodium HydroxideHCID 516892Sodium BicarbonateHCID 2724529Triisopropylsilyl trifluoromethanesulfonateHCID 22598016HCID 22598016, compound

Product 1

HCID 22598003HCID 22598003, compound

Reagents, catalysts & solvents 3

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 241BenzeneSolventHCID 3283Diethyl EtherSolvent

Procedure

A mixture of the chloride, 3-(2-Chloro)ethoxy-4-difluoromethoxy-1-(triisopropylsilyloxy)methylbenzene, from Step 2 (124 g, 303 mmol), 10N NaOH (300 mL, 3.03 mol) and Bu4NHSO4 (102 g, 303 mmol) in benzene (1.3 L) was heated at 65° C. for 4.5 h. The mixture was cooled to room temperature and was partitioned with 25% aq. NH4OAc (500 mL). The aqueous phase was extracted with ether (2×) and the combined organics were washed with brine, dried (Na2SO4) and concentrated. The residual oil was dissolved in dichloromethane (1 L) and 2,6-lutidine (53 mL, 454 mmol) and cooled in an ice bath. Triisopropylsilyl triflate (98 mL, 363 mmol) was slowly added and after addition was complete, the mixture was stirred at room temperature for 3 h. The mixture was cooled to 0° C. and sat. aq. NaHCO3 (50 mL) was added. Ether (1.5L) and 25% aq. NH4OAc (500 mL) were added and the aqueous layer was extracted with ether (2×). The combined organics were washed with brine, dried (Na2SO4) and concentrated. Flash chromatography of the residue (silica gel; hexane/ethyl acetate 98:2 to 95:5) provided 3-Ethenyloxy-4-difluoromethoxy-1-(triisopropylsilyloxy)methylbenzene (67 g).

Workup

  1. customwas partitioned with 25% aq. NH4OAc (500 mL)
  2. extractionThe aqueous phase was extracted with ether (2×)
  3. washthe combined organics were washed with brine
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated
  6. dissolutionThe residual oil was dissolved in dichloromethane (1 L)
  7. additionafter addition
  8. temperatureThe mixture was cooled to 0° C.
  9. extractionthe aqueous layer was extracted with ether (2×)
  10. washThe combined organics were washed with brine
  11. dry with materialdried (Na2SO4)
  12. concentrationconcentrated

Sources & evidence

ORD record
ord-5772db34ec7042bcb6a59d84c22605fc
Source dataset
uspto-grants-2002_06
Patent number
US06399636B2

Reaction notes

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