Ammonium Chloride → 4-Bromo-1-isopropoxy-2-vinylbenzene

HRID 448832ノート

反応式

HRID 448832 の反応式
[CH2:1]([Li])CCC.[Br:6][C:7]1[CH:8]=[CH:9][C:10]([O:15][CH:16]([CH3:18])[CH3:17])=[C:11]([CH:14]=1)[CH:12]=O.[Cl-].[NH4+]>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1.COC(C)(C)C.CCCCCC>[Br:6][C:7]1[CH:8]=[CH:9][C:10]([O:15][CH:16]([CH3:18])[CH3:17])=[C:11]([CH:12]=[CH2:1])[CH:14]=1

参加物

7

反応物 3

HCID 25517Ammonium ChlorideHCID 8199735-Bromo-2-isopropoxybenzaldehydeHCID 178418339Butyllithium

生成物 1

HCID 125424254-Bromo-1-isopropoxy-2-vinylbenzene収率 95%

試薬・触媒・溶媒 3

HCID 74505Methyltriphenyliphosphonium bromide触媒HCID 8028Tetrahydrofuran溶媒2 回HCID 21982663Methyl t-butylether hexane溶媒

反応条件

温度
0 °C

実験手順

To a suspension of methyltriphenylphosphonium bromide (41.1 g, 115 mmol) in anhydrous THF (1.2 L) was added n-butyllithium (123 mmol, 2.5 M in hexanes) at −70° C. The mixture was stirred for a further 10 min, and then allowed to warm up to 0° C. and stirred at this temperature for 10 min. The reaction mixture is then cooled again at −50° C., and 5-bromo-2-isopropoxybenzaldehyde (20.0 g, 82.2 mmol) in solution in anhydrous THF (5 mL) was added. The mixture was stirred for 10 min, and then allowed to warm up to room temperature. An ammonium chloride solution was added and the reaction mixture was diluted with a mixture methyl t-butylether/hexane, filtered through celite, and then dried over magnesium sulfate. The solvent was removed in vacuo to afford compound AY (18.9 g) as a pale yellow oil in 95% yield. 1H NMR (CDCl3, 400 MHz): δ (ppm) 1.34 (d, J=6.0 Hz, 6H), 4.50 (sept., J=6.0 Hz, 1H), 5.27 (dd, J=11.0 and 1.1 Hz, 1H), 5.71 (dd, J=17.9 and 1.2 Hz, 1H), 6.75 (d, J=8.7 Hz, 1H), 6.97 (dd, J=17.7 and 11.2 Hz, 1H), 7.28 (dd, J=8.7 and 2.5 Hz, 1H), 7.57 (d, J=2.5 Hz, 1H).

後処理

  1. stirringstirred at this temperature for 10 min
  2. temperatureThe reaction mixture is then cooled again at −50° C.
  3. stirringThe mixture was stirred for 10 min
  4. temperatureto warm up to room temperature
  5. filtrationfiltered through celite
  6. dry with materialdried over magnesium sulfate
  7. customThe solvent was removed in vacuo
  8. customto afford compound AY (18.9 g) as a pale yellow oil in 95% yield

出典と根拠

ORDレコード
ord-e2f59932a7be44319363ce357e130ed6
出典データセット
uspto-grants-2013_07
特許番号
US08481748B2

反応ノート

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