Water → 1-tert-Butoxy-3-fluoropropan-2-ol

HRID 1436919ノート

反応式

HRID 1436919 の反応式
C(O)COCCOCCO.[FH:11].[F-].[K+].[C:14]([O:18][CH2:19][CH:20]1[CH2:22][O:21]1)([CH3:17])([CH3:16])[CH3:15].O>COC(C)(C)C>[C:14]([O:18][CH2:19][CH:20]([OH:21])[CH2:22][F:11])([CH3:17])([CH3:16])[CH3:15]

参加物

6

反応物 4

HCID 962WaterHCID 8172Triethylene GlycolHCID 243142-((1,1-Dimethylethoxy)methyl)oxiraneHCID 11829350Potassium bifluoride

生成物 1

HCID 579396991-tert-Butoxy-3-fluoropropan-2-ol収率 61%

試薬・触媒・溶媒 1

HCID 15413tert-Butyl methyl ether溶媒

反応条件

温度
130 °C

実験手順

A 1.5 L 4-necked sulfonation flask equipped with magnetic stirring bar, reflux condenser, thermometer and an argon in/outlet, was charged with 333.3 mL triethylene glycol, 235.2 g (3.012 mol) finely ground potassium hydrogendifluoride and 200 g (1.536 mol) 2-tert-butoxymethyl-oxirane. The suspension was heated under stirring at an internal temperature of 130° C. for 7.5 h. The mixture was allowed to cool to RT over night, treated with 670 mL water and 350 mL tert-butyl methyl ether, the phases were separated and the aqueous phase was extracted with 350 ml tert-butyl methyl ether. The combined organic phases were washed with 350 mL brine, dried over sodium sulfate, filtered and evaporated. The brown oily residue (286 g) was distilled to provide 141 g (61%) 1-tert-butoxy-3-fluoro-propan-2-ol as colorless liquid, b.p. 80-93° C./70-40 mbar. GC composition: 1.1% 2-tert-butoxymethyl-oxirane, 95.1% 1-tert-butoxy-3-fluoro-propan-2-ol and 3.8% of 3-tert-butoxy-2-fluoro-propan-1-ol. 1H-NMR (CDCl3, 300 MHz): 4.45 (dxm, JH,F=46, —CH2—F); 3.93 (m, br, H—C(2); 3.45 (m, —CH2—O); 2.55 (d, br, J=6, OH); 1.20 (s, C(CH3)3).

後処理

  1. customA 1.5 L 4-necked sulfonation flask equipped with magnetic stirring bar
  2. temperaturereflux condenser
  3. temperatureThe suspension was heated
  4. temperatureto cool to RT over night
  5. customthe phases were separated
  6. extractionthe aqueous phase was extracted with 350 ml tert-butyl methyl ether
  7. washThe combined organic phases were washed with 350 mL brine
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. customevaporated
  11. distillationThe brown oily residue (286 g) was distilled

出典と根拠

ORDレコード
ord-bf32362a6bfa428aa89a7505c140dab8
出典データセット
uspto-grants-2009_11
特許番号
US07619101B2

反応ノート

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