Chlorotrimethylsilane → ethyl P-(3-cyano-1,1,1-trifluoro-prop-2-yl)-P-methyl-phosphinate

HRID 865854ノート

反応式

HRID 865854 の反応式
[CH2:1]([O:3][P:4]([CH3:6])[OH:5])[CH3:2].C(N(CC)CC)C.C[Si](Cl)(C)C.[F:19][C:20]([F:26])([F:25])/[CH:21]=[CH:22]/[C:23]#[N:24]>O1CCCC1>[C:23]([CH2:22][CH:21]([P:4]([CH3:6])(=[O:5])[O:3][CH2:1][CH3:2])[C:20]([F:26])([F:25])[F:19])#[N:24]

参加物

6

反応物 4

HCID 6397ChlorotrimethylsilaneHCID 8471TriethylamineHCID 57087824,4,4-trifluorocrotononitrileHCID 13145048O-ethyl-P-methyl-phosphonous acid

生成物 1

HCID 10421332ethyl P-(3-cyano-1,1,1-trifluoro-prop-2-yl)-P-methyl-phosphinate

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

A solution of 2.16 g (20 mmol) of O-ethyl-P-methyl-phosphonous acid and 4.05 g (40 mmol) of triethylamine in 100 ml of dry tetrahydrofuran is stirred under an atmosphere of argon at 25°. To this solution are added at 25° 4.35 g (40 mmol) of trimethylsilyl chloride over a period of 10 minutes. A white precipitate is formed. The reaction mixture is stirred at 25° for additional 16 hours. Then, 2.42 g (20 mmol) of 4,4,4-trifluorocrotononitrile, dissolved in 20 ml of dry tetrahydrofuran, are added at 25° over a period of 10 minutes. The reaction mixture is refluxed for 40 hours, cooled to 25°, poured into ice-water and extracted with dichloromethane. The extracts are combined, washed with water, dried over anhydrous sodium sulphate and evaporated under reduced pressure to dryness. The crude product is chromatographed on 200 g of silica gel with trichloromethane as eluent. The product-containing fractions are combined and evaporated to give ethyl P-(3-cyano-1,1,1-trifluoro-prop-2-yl)-P-methyl-phosphinate as an oil.

後処理

  1. customA white precipitate is formed
  2. additionare added at 25° over a period of 10 minutes
  3. temperatureThe reaction mixture is refluxed for 40 hours
  4. temperaturecooled to 25°
  5. extractionextracted with dichloromethane
  6. washwashed with water
  7. dry with materialdried over anhydrous sodium sulphate
  8. customevaporated under reduced pressure to dryness
  9. customThe crude product is chromatographed on 200 g of silica gel with trichloromethane as eluent
  10. customevaporated

出典と根拠

ORDレコード
ord-cd7bde9d2dbe43b2a7dc90fbf7aa06f7
出典データセット
uspto-grants-1996_10
特許番号
US05567840

反応ノート

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