2,2,2-Trifluoro-1,1-ethanediol → Ethyl 2-methyl-4,4,4-trifluorocrotonate

HRID 1975440ノート

反応式

HRID 1975440 の反応式
[C:1]([CH2:6][CH:7]=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([O:3][CH2:4][CH3:5])=[O:2].[CH:27](O)(O)[C:28]([F:31])([F:30])[F:29]>O1CCCC1>[CH3:7]/[C:6](=[CH:27]\[C:28]([F:31])([F:30])[F:29])/[C:1]([O:3][CH2:4][CH3:5])=[O:2]

参加物

4

反応物 2

HCID 679012,2,2-Trifluoro-1,1-ethanediolHCID 12607919Ethyl 3-(triphenyl-lambda~5~-phosphanylidene)propanoate

生成物 1

HCID 5702867Ethyl 2-methyl-4,4,4-trifluorocrotonate

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

A suspension of (carbethoxyethylidene)triphenylphosphorane (400 g, 1.10 mole) in tetrahydrofuran (600 mL) was treated with aqueous fluoral hydrate (71.5% w/w, 180 g, 1.10 mole) over a period of 4 hours. During the addition the reaction temperature rose to 45° C. and all of the solid dissolved to give a clear brown solution. The mixture was allowed to stand for 15 hours and was then heated under reflux for 3.5 hours. The solution was distilled at 2,700 Pa until the temperature in the distillation flask reached 140° C., giving ethyl (E)-2-methyl-4,4,4-trifluorobut-2-enoate as a solution in tetrahydrofuran (Solution A, 0.75 L, containing a maximum of 201 g of alkene); NMR (270 MHz, CDCl3): 1.3 (t, 3H, J=7Hz), 2.1 (br, s, 3H), 4.3 (q, 2H, J=7Hz) and 6.7 (m, 1H), (plus signals due to tetrahydrofuran).

後処理

  1. additionDuring the addition the reaction temperature
  2. customrose to 45° C.
  3. dissolutionall of the solid dissolved
  4. customto give a clear brown solution
  5. temperaturewas then heated
  6. temperatureunder reflux for 3.5 hours
  7. distillationThe solution was distilled at 2,700 Pa until the temperature in the distillation flask
  8. customreached 140° C.

出典と根拠

ORDレコード
ord-1755f01e8908469a8f896ec9b340c575
出典データセット
uspto-grants-1994_02
特許番号
US05286740

反応ノート

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