Ammonium Chloride → 3-(Diphenylphosphino)-4-methyl-styrene

HRID 1242822ノート

反応式

HRID 1242822 の反応式
Br[C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][C:9]=1[CH3:10])[CH:5]=[CH2:6].Cl[P:12]([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.[NH4+].[Cl-]>C1COCC1>[C:19]1([P:12]([C:13]2[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=2)[C:2]2[CH:3]=[C:4]([CH:7]=[CH:8][C:9]=2[CH3:10])[CH:5]=[CH2:6])[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1

参加物

5

反応物 3

HCID 25517Ammonium ChlorideHCID 66180ChlorodiphenylphosphineHCID 219403312-Bromo-4-ethenyl-1-methylbenzene

生成物 1

HCID 210631723-(Diphenylphosphino)-4-methyl-styrene収率 40%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

Mg (0.72 g, 30 mmol) was placed in a 50 mL of round-bottom flask. The flask was dried and filled with nitrogen. Anhydrous THF (10 mL) was injected first and followed by injection of a half amount of a solution of 3-bromo-4-methyl-styrene (3.94 g, 20 mmol) in anhydrous THF (10 mL). After an exothermic reaction started, the second half of the solution was added. The resulting Grignard reagent was added to a solution of chlorodiphenylphosphine (5.25 g, 25 mmol) in anhydrous THF (10 mL) at 0° C. After the addition, the reaction mixture was warmed to the room temperature and stirred for another 20 h. Then, it was poured into a saturated NH4Cl aqueous solution (10 mL) at 0° C. and extracted with anhydrous THF (3×20 mL). The organic layer was dried over anhydrous magnesium sulfate and concentrated to a volume of 5 mL. Hexane was added into the resulting oil to precipitate by-products. After filtration and concentration, the residue was purified by a flash column chromatography (hexane/EAC=4/1) to afford 2.42 g of the desired product (39% yield). 1H NMR (300 MHz, CDCl3) δ 2.36 (3H, s), 5.06 (1H, d, J=10.9 Hz), 5.42 (1H, d, J=17.6 Hz), 6.48 (1H, q, J=10.9, 17.6 Hz), 6.79 (1H, q, J=2.1, 5.8 Hz), 7.20–7-34 (11H, m); 13C NMR (75 MHz, CDCl3) δ 20.8, 21.1, 113.0, 126.2, 128.5, 128.6, 128.8, 130.2, 130.3, 130.7, 133.9, 134.1, 135.1, 136.0, 136.3, 136.5, 141.7 ppm; 31P NMR (121 MHz, CDCl3) δ−12.34 ppm; IR (neat) 3057 (m), 3016 (s), 2974 (m), 1957 (w), 1900 (w), 1819 (w), 1629 (m), 1589 (m), 1479 (s), 1435 (s), 1380 (m), 1306 (w), 1262 (m), 1179 (m), 1152 (m), 1093 (m), 1028 (m), 992 (m), 911 (s), 830 (s), 699 (s); MS m/z 302 (M+) 223, 183, 165, 152, 115, 78; HRMS calcd for C21H19P 302.1224, found 302.1227.

後処理

  1. customThe flask was dried
  2. additionfilled with nitrogen
  3. customAfter an exothermic reaction
  4. additionthe second half of the solution was added
  5. additionAfter the addition
  6. extractionextracted with anhydrous THF (3×20 mL)
  7. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  8. concentrationconcentrated to a volume of 5 mL
  9. additionHexane was added into the resulting oil
  10. customto precipitate by-products
  11. filtrationAfter filtration and concentration
  12. customthe residue was purified by a flash column chromatography (hexane/EAC=4/1)

出典と根拠

ORDレコード
ord-63182f4651ff44f49761b0ef92c44e87
出典データセット
uspto-grants-2006_10
特許番号
US07115762B2

反応ノート

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