Water → (NZ)-4-methyl-N-[4,4,4-trifluoro-2-(2,2,2-trifluoroethyl)butylidene]benzenesulfinamide

HRID 1594320Notes

Reaction equation

HRID 1594320 reaction equation
[F:1][C:2]([F:13])([F:12])[CH2:3][CH:4]([CH2:7][C:8]([F:11])([F:10])[F:9])[CH:5]=O.[C:14]1(C)[C:15]([S@@:20]([NH2:22])=[O:21])=[CH:16][CH:17]=[CH:18][CH:19]=1.O.[CH3:25]COCC>[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC>[CH3:25][C:18]1[CH:19]=[CH:14][C:15]([S:20](/[N:22]=[CH:5]\[CH:4]([CH2:7][C:8]([F:11])([F:10])[F:9])[CH2:3][C:2]([F:13])([F:12])[F:1])=[O:21])=[CH:16][CH:17]=1

Participants

6

Reactant 4

HCID 962WaterHCID 3283Diethyl EtherHCID 252317334,4,4-Trifluoro-2-(2,2,2-trifluoroethyl)butanalHCID 68430204(s)-(+)-Toluene sulfinamide

Product 1

HCID 87452018(NZ)-4-methyl-N-[4,4,4-trifluoro-2-(2,2,2-trifluoroethyl)butylidene]benzenesulfinamideYield 41.2%

Reagents, catalysts & solvents 1

HCID 76524Titanium tetraethoxideCatalyst

Conditions

Temperature
0 °C

Procedure

To the crude organic extract of 4,4,4-trifluoro-2-(2,2,2-trifluoroethyl)butyraldehyde (prepared as in Example 26, part F, 0.6 g, 2.88 mmol) in ether (5 mL) was added titanium (IV) ethoxide (2.63 g, 11.54 mmol) followed by (S)-(+)-toluene sulfinamide (0.537 g, 3.46 mmol) and the solution was heated to reflux for 5 h. The mixture was then cooled to 0° C. and water (35 mL) was added to precipitate titanium salts. The suspension was filtered through a pad of the Celite® reagent and the filter cake was washed with CH2Cl2. The layers of the filtrate were separated and the aqueous layer was extracted with CH2Cl2. The combined organic extracts were dried over MgSO4, filtered, and concentrated to obtain a crude yellow oil (1.05 g). The crude product was purified by the Biotage Flash™ 40 chromatography system, eluent: 1:9 EtOAc-hexanes, to afford 4-methyl-N-[(1Z)-4,4,4-trifluoro-2-(2,2,2-trifluoroethyl)butylidene]benzenesulfinamide as a yellow oil (0.41 g, 41.2%). Mass

Workup

  1. temperaturethe solution was heated
  2. temperatureto reflux for 5 h
  3. customto precipitate titanium salts
  4. filtrationThe suspension was filtered through a pad of the Celite® reagent
  5. washthe filter cake was washed with CH2Cl2
  6. customThe layers of the filtrate were separated
  7. extractionthe aqueous layer was extracted with CH2Cl2
  8. dry with materialThe combined organic extracts were dried over MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customto obtain a crude yellow oil (1.05 g)
  12. customThe crude product was purified by the Biotage Flash™ 40 chromatography system, eluent

Sources & evidence

ORD record
ord-db59e2a2a0084bb8ac8cb57836b01438
Source dataset
uspto-grants-2007_11
Patent number
US07300951B2

Reaction notes

Loading…