Ammonium Chloride → (S)-1-(2-fluorophenyl)-2-((1,1,1-trifluorobut-3-en-2-yl)oxy)ethanone

HRID 1429608ノート

反応式

HRID 1429608 の反応式
C([Li])CCC.Br[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1[F:13].CON(C)[C:17](=[O:27])[CH2:18][O:19][C@@H:20]([CH:25]=[CH2:26])[C:21]([F:24])([F:23])[F:22].[NH4+].[Cl-]>CCCCCC.C1COCC1.[Cl-].[Na+].O>[F:13][C:8]1[CH:9]=[CH:10][CH:11]=[CH:12][C:7]=1[C:17](=[O:27])[CH2:18][O:19][C@@H:20]([CH:25]=[CH2:26])[C:21]([F:23])([F:22])[F:24]

参加物

8

反応物 4

HCID 25517Ammonium ChlorideHCID 612591-Bromo-2-fluorobenzeneHCID 86668361(S)-N-Methoxy-N-methyl-2-((1,1,1-trifluorobut-3-en-2-yl)oxy)acetamideHCID 178418339Butyllithium

生成物 1

HCID 69936486(S)-1-(2-fluorophenyl)-2-((1,1,1-trifluorobut-3-en-2-yl)oxy)ethanone収率 72.8%

試薬・触媒・溶媒 3

HCID 8028Tetrahydrofuran溶媒2 回HCID 8058Hexane溶媒HCID 57417360Sodium chloride; water溶媒

反応条件

温度
-60 °C

実験手順

A solution of n-butyllithium in hexane (2.50 M; 90 mL) was added dropwise over 25 mins to a solution of 2-bromofluorobenzene (40.35 g) in THF (250 mL) under a N2 atmosphere at −78° C. The reaction solution was allowed to warm to −60° C. and stir for 60 min. (S)—N-Methoxy-N-methyl-2-((1,1,1-trifluorobut-3-en-2-yl)oxy)acetamide (40 g) in THF (25 mL) was added dropwise to the reaction solution, and after stirring at −60° C. for 2 h, aqueous NH4Cl (100 mL) was added to the reaction solution, followed by warming to RT. Brine (200 mL) was added to the reaction solution, and the mixture was extracted with EtOAc (3×400 mL). The combined organic portions were dried over MgSO4, evaporated, and the residue was purified by silica gel column chromatography (1% to 10% EtOAc in hexanes) to obtain the title compound (33.59 g). 1H-NMR (400 MHz, CDCl3) δ (ppm): 4.40 (pentet, J 6.3 Hz, 1 H) 4.81-4.87 (m, 2 H), 5.54-5.69 (m, 2 H), 5.86 (ddd, J 17.4, 10.4, 7.3 Hz, 1 H) 7.12-7.22 (m, 1 H) 7.24-7.34 (m, 1 H) 7.54-7.63 (m, 1 H) 7.94-8.02 (m, 1 H).

後処理

  1. additionwas added dropwise to the reaction solution
  2. temperatureby warming to RT
  3. extractionthe mixture was extracted with EtOAc (3×400 mL)
  4. dry with materialThe combined organic portions were dried over MgSO4
  5. customevaporated
  6. customthe residue was purified by silica gel column chromatography (1% to 10% EtOAc in hexanes)

出典と根拠

ORDレコード
ord-11744bb704334363b21871067f7d1f53
出典データセット
uspto-grants-2015_01
特許番号
US08940734B2

反応ノート

読み込み中…