Acetic Acid → benzyl (2R)-2-[4-[4-(2,2,3,3-tetrafluoropropoxy)phenyl]-4,5-dihydro-5-oxo-1H-1,2,4-triazol-1-yl]propionate

HRID 1489415ノート

反応式

HRID 1489415 の反応式
[F:1][C:2]([F:20])([CH:17]([F:19])[F:18])[CH2:3][O:4][C:5]1[CH:10]=[CH:9][C:8]([N:11]2[CH:15]=[N:14][NH:13][C:12]2=[O:16])=[CH:7][CH:6]=1.FC(F)(F)S(O[C@@H:27]([CH3:38])[C:28]([O:30][CH2:31][C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)=[O:29])(=O)=O.C(O)(=O)C>CN(C)C=O.[H-].[Na+].O1CCCC1.C(OCC)(=O)C.C(OC(C)C)(C)C>[F:20][C:2]([F:1])([CH:17]([F:19])[F:18])[CH2:3][O:4][C:5]1[CH:10]=[CH:9][C:8]([N:11]2[C:12](=[O:16])[N:13]([C@H:27]([CH3:38])[C:28]([O:30][CH2:31][C:32]3[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=3)=[O:29])[N:14]=[CH:15]2)=[CH:7][CH:6]=1

参加物

9

反応物 3

HCID 176Acetic AcidHCID 10779907HCID 10779907、化合物HCID 10881508Phenylmethyl (2S)-2-[[(trifluoromethyl)sulfonyl]oxy]propanoate

生成物 1

HCID 10694967benzyl (2R)-2-[4-[4-(2,2,3,3-tetrafluoropropoxy)phenyl]-4,5-dihydro-5-oxo-1H-1,2,4-triazol-1-yl]propionate収率 85.6%

試薬・触媒・溶媒 5

HCID 6228Dimethylformamide溶媒HCID 7914Diisopropyl Ether溶媒HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒HCID 24758Sodium hydride溶媒

実験手順

4-[4-(2,2,3,3-Tetrafluoropropoxy)phenyl]-3(2H,4H)-1,2,4-triazolone (18 g) was dissolved in 180 ml of dimethylformamide, to which 60% sodium hydride in oil (2.52 g) was added. The mixture was vigorously stirred at room temperature for 40 minutes. The reaction solution was added to a solution of 20 g of benzyl (2S)-2-trifluoromethanesulfonyloxypropionate prepared in Example 3 in 240 ml of tetrahydrofuran under nitrogen atmosphere at -40° to -30° C. over the period of ca. 40 minutes. The mixture was stirred at -40° to -20° C. for 40 minutes, to which 10 ml of acetic acid was added. Then, the reaction solution was diluted with a mixture of 100 ml of ethyl acetate and 500 ml of diisopropyl ether, washed with 250 ml of water, 2N-hydrochloric acid (250 ml×2) and 250 ml of an aqueous solution of sodium chloride successively. After dring over magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (silica gel: 250 g, eluent; hexane:ethyl acetate=2:1) to give 24 g of benzyl (2R)-2-[4-[4-(2,2,3,3-tetrafluoropropoxy)phenyl]-4,5-dihydro-5-oxo-1H-1,2,4-triazol-1-yl]propionate (yield: 82%) as a colorless oil.

後処理

  1. additionwas added
  2. additionwas added
  3. washwashed with 250 ml of water, 2N-hydrochloric acid (250 ml×2) and 250 ml of an aqueous solution of sodium chloride successively
  4. distillationthe solvent was distilled off under reduced pressure
  5. customThe residue was purified by silica gel chromatography (silica gel: 250 g, eluent; hexane:ethyl acetate=2:1)

出典と根拠

ORDレコード
ord-0e9491efff11447b8873c584ef7f8c42
出典データセット
uspto-grants-1997_10
特許番号
US05677464

反応ノート

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