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

HRID 1242822노트

반응식

HRID 1242822 반응식
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

참가 물질

5

반응물 3

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

생성물 1

HCID 210631723-(Diphenylphosphino)-4-methyl-styrene수율 40%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

실험 절차

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.

후처리

  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)

출처 및 근거

ORD 기록
ord-63182f4651ff44f49761b0ef92c44e87
출처 데이터셋
uspto-grants-2006_10
특허 번호
US07115762B2

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