Trifluoroacetic acid → HCID 86684906, compound

HRID 2402897Notes

Reaction equation

HRID 2402897 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([O:8][C@@H:9]([CH3:14])[C:10]([F:13])([F:12])[F:11])[CH:5]=[CH:4][C:3]=1[S:15]C(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.FC(F)(F)C(O)=O.C([SiH](CC)CC)C>ClCCl>[Cl:1][C:2]1[CH:7]=[C:6]([O:8][C@@H:9]([CH3:14])[C:10]([F:11])([F:12])[F:13])[CH:5]=[CH:4][C:3]=1[SH:15]

Participants

5

Reactant 3

HCID 6422Trifluoroacetic acidHCID 12052TriethylsilaneHCID 86684905HCID 86684905, compound

Product 1

HCID 86684906HCID 86684906, compoundYield 93%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

2-Chloro-4-((S)-2,2,2-trifluoro-1-methyl-ethoxy)-1-tritylsulfanyl-benzene (220 g, 441 mmol) was dissolved in dichloromethane (800 mL) and trifluoroacetic acid (165 mL, 2.15 mol) was added at room temperature, followed by triethylsilane (110 mL, 674 mmol, ice bath cooling necessary). After stirring for 30 min at room temperature, the mixture was concentrated in vacuo. A potassium hydroxide solution (2M in water, 1.1 L) was added to the residue, and the suspension was stirred for 15 min. After filtration, the remaining solid was washed with water. The combined filtrate was acidified to pH<2 by addition of hydrochloric acid (25% in water, 330 mL) and extracted with tert-butyl-methylether (3×500 mL). The combined organic extracts were washed with an aqueous potassium hydrogencarbonate solution (1M, 330 mL), dried over sodium sulfate, and concentrated in vacuo. The turbid oil was treated with heptane (80 mL) and filtered. The remaining solid was further washed with heptane (20 mL). The combined filtrate was concentrated and dried in vacuo to yield the title compound as a colorless liquid (105 g, 93%). 1H NMR (CDCl3, 400 MHz): δ 1.49 (dd, J=6.5 Hz, 0.5 Hz, 3H), 3.75 (s, 1H), 4.55 (qq, J=6.2 Hz, 6.2 Hz, 1H), 6.79 (dd, J=3.0 Hz, 8.9 Hz, 1H), 7.03 (d, J=2.7 Hz, 1H), 7.29 (d, J=8.6 Hz, 1H).

Workup

  1. concentrationthe mixture was concentrated in vacuo
  2. additionA potassium hydroxide solution (2M in water, 1.1 L) was added to the residue
  3. stirringthe suspension was stirred for 15 min
  4. filtrationAfter filtration
  5. washthe remaining solid was washed with water
  6. additionThe combined filtrate was acidified to pH<2 by addition of hydrochloric acid (25% in water, 330 mL)
  7. extractionextracted with tert-butyl-methylether (3×500 mL)
  8. washThe combined organic extracts were washed with an aqueous potassium hydrogencarbonate solution (1M, 330 mL)
  9. dry with materialdried over sodium sulfate
  10. concentrationconcentrated in vacuo
  11. additionThe turbid oil was treated with heptane (80 mL)
  12. filtrationfiltered
  13. washThe remaining solid was further washed with heptane (20 mL)
  14. concentrationThe combined filtrate was concentrated
  15. customdried in vacuo

Sources & evidence

ORD record
ord-e188e4923033472286aee738b8f16f62
Source dataset
uspto-grants-2014_08
Patent number
US08796471B2

Reaction notes

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