Sodium Chloride → HCID 86684909, compound

HRID 2402899Notes

Reaction equation

HRID 2402899 reaction equation
CC(C)([O-])C.[K+].[CH2:7]([OH:12])[C:8]([F:11])([F:10])[F:9].F[C:14]1[CH:19]=[CH:18][C:17]([S:20][C:21]([C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)([C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)=[C:16]([C:40]([F:43])([F:42])[F:41])[CH:15]=1.[Cl-].[Na+]>O1CCCC1.CN1CCCC1=O.[Cl-].[Na+].O.O.C(OC)(C)(C)C>[F:9][C:8]([F:11])([F:10])[CH2:7][O:12][C:14]1[CH:19]=[CH:18][C:17]([S:20][C:21]([C:22]2[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=2)([C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)=[C:16]([C:40]([F:43])([F:42])[F:41])[CH:15]=1

Participants

10

Reactant 4

HCID 5234Sodium ChlorideHCID 64092,2,2-TrifluoroethanolHCID 23665647Potassium tert-butoxideHCID 86684907HCID 86684907, compound

Product 1

HCID 86684909HCID 86684909, compoundYield 95.3%

Reagents, catalysts & solvents 5

HCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolvent3×HCID 13387N-methyl-2-pyrrolidoneSolventHCID 15413tert-Butyl methyl etherSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

Potassium tert-butoxide (98% m/m, 39.17 g, 342.1 mmol) was suspended in tetrahydrofuran (190 mL) and a solution of trifluoroethanol (35.65 g, 356.4 mmol) in tetrahydrofuran (28 mL) was added at room temperature (exothermic). The mixture was stirred for 15 min, and a solution of 4-fluoro-2-trifluoromethyl-1-tritylsulfanyl-benzene (125 g, 285 mmol) in 1-methyl-2-pyrrolidon (240 mL) and tetrahydrofuran (290 mL) was added. The resulting brown solution was stirred for 30 min at room temperature, followed by 2 h at 45° C. internal temperature. After that, water (720 mL), brine (125 mL), and tert-butyl-methylether (720 mL) were added and phases were separated. The organic layer was washed with a solution of sodium chloride (59.3 g, 1015 mmol) in water (380 mL) and concentrated in vacuo at 40° C. to a volume of ca. 400 mL. The solution was diluted with ethanol (300 mL), and additional ethanol (480 mL) was continuously added to the distillation, while the overall volume was kept constant at ca. 700 mL (solvent exchange). The resulting suspension was stirred for 14 h at room temperature and 1 h at 0° C. before water (140 mL) was added and the suspension was stirred for further 1.5 h at 0° C. After filtration, the precipitate was washed with cold ethanol/water 5:1 (v/v, 288 mL) and dried in vacuo to yield the title compound as fine yellow crystals (140.9 g, 95%). MS (EI): m/z=243 [CPh3]+. 1H NMR (CDCl3, 600 MHz): δ 4.26 (q, J=8.0 Hz, 2H), 6.61 (dd, J=2.9 Hz, 8.8 Hz, 1H), 7.04 (d, J=8.8 Hz, 1H), 7.07 (d, J=2.9 Hz, 1H), 7.18-7.25 (m, 9H), 7.33-7.37 (m, 6H).

Workup

  1. stirringThe resulting brown solution was stirred for 30 min at room temperature
  2. waitfollowed by 2 h at 45° C.
  3. customphases were separated
  4. concentrationconcentrated in vacuo at 40° C. to a volume of ca. 400 mL
  5. additionThe solution was diluted with ethanol (300 mL), and additional ethanol (480 mL)
  6. additionwas continuously added to the distillation, while the overall volume
  7. stirringThe resulting suspension was stirred for 14 h at room temperature and 1 h at 0° C. before water (140 mL)
  8. additionwas added
  9. stirringthe suspension was stirred for further 1.5 h at 0° C
  10. filtrationAfter filtration
  11. washthe precipitate was washed with cold ethanol/water 5:1 (v/v, 288 mL)
  12. customdried in vacuo

Sources & evidence

ORD record
ord-377679c2359642328d53bb3b94c72bfd
Source dataset
uspto-grants-2014_08
Patent number
US08796471B2

Reaction notes

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