Triethylamine → Ethyl (3R)-N-[(allyloxy)carbonyl]-4,4,4-trifluorovalinate

HRID 626424ノート

反応式

HRID 626424 の反応式
C(N(CC)CC)C.C1(=O)NC(=O)CC1.Cl[C:16]([O:18][CH2:19][CH:20]=[CH2:21])=[O:17].[F:22][C:23]([F:34])([F:33])[C@H:24]([CH3:32])[C@@H:25]([C:27]([O:29][CH2:30][CH3:31])=[O:28])[NH2:26]>C(OCC)(=O)C.C1COCC1>[CH2:19]([O:18][C:16]([NH:26][C@H:25]([C:27]([O:29][CH2:30][CH3:31])=[O:28])[C@H:24]([C:23]([F:34])([F:33])[F:22])[CH3:32])=[O:17])[CH:20]=[CH2:21]

参加物

7

反応物 4

HCID 8471TriethylamineHCID 11439SuccinimideHCID 18052Allyl chloroformateHCID 124507558Ethyl (3R)-4,4,4-trifluorovalinate

生成物 1

HCID 131735216Ethyl (3R)-N-[(allyloxy)carbonyl]-4,4,4-trifluorovalinate

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
0 °C

実験手順

9.7 ml (69.3 mmol) of triethylamine were added dropwise to a solution of 6.38 g (55.4 mmol) of succinimide in 90 ml of abs. THF. The resulting suspension was cooled to 0° C., and a solution of 6.68 g (55.4 mmol) of allyl chloroformate in 10 ml of abs. THF was added dropwise. The mixture was stirred at 0° C. for 1 h, and three portions of in total 9.2 g (about 46 mmol) of ethyl (3R)-4,4,4-trifluorovalinate (diastereomer mixture, crude product) were added. The reaction mixture was warmed to RT overnight, then diluted with ethyl acetate, washed with sat. sodium bicarbonate solution and sat. sodium chloride solution, dried over sodium sulphate and concentrated under reduced pressure. The crude product was purified by chromatography on silica gel (mobile phase cyclohexane/ethyl acetate 10:1→4:1). This gave 6.50 g of the target product (about 50% of theory, diastereomer ratio about 2:1).

後処理

  1. temperatureThe reaction mixture was warmed to RT overnight
  2. washwashed with sat. sodium bicarbonate solution and sat. sodium chloride solution
  3. dry with materialdried over sodium sulphate
  4. concentrationconcentrated under reduced pressure
  5. customThe crude product was purified by chromatography on silica gel (mobile phase cyclohexane/ethyl acetate 10:1→4:1)

出典と根拠

ORDレコード
ord-3fe86a5cfd3b4932aa9e84601ab655f1
出典データセット
uspto-grants-2016_04
特許番号
US09309198B2

反応ノート

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