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

HRID 1985972ノート

反応式

HRID 1985972 の反応式
[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

参加物

6

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 76524Titanium tetraethoxide触媒

反応条件

温度
0 °C

実験手順

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 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 Spectrum (−ESI): 344 (M−H)−.

後処理

  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 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

出典と根拠

ORDレコード
ord-0c3f740dfb154dabad96a3eaf402a336
出典データセット
uspto-grants-2009_06
特許番号
US07547725B2

反応ノート

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