Diphenylphosphine → Nmdpp

HRID 1604751

반응식

HRID 1604751 반응식
[C:1]1([PH:7][C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C([Li])CCC.[CH:19]1([CH3:29])[CH2:24][CH2:23][CH:22]([CH:25]([CH3:27])[CH3:26])[CH:21](Cl)[CH2:20]1>O1CCCC1>[CH3:29][C@@H:19]1[CH2:20][C@@H:21]([P:7]([C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=2)[C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[C@@H:22]([CH:25]([CH3:27])[CH3:26])[CH2:23][CH2:24]1

참가 물질

5

반응물 3

HCID 70017DiphenylphosphineHCID 859512-Chloro-4-methyl-1-(1-methylethyl)cyclohexaneHCID 178418339Butyllithium

생성물 1

HCID 12665338Nmdpp수율 54.1%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

반응 조건

온도
-20 °C

실험 절차

Diphenylphosphine (140 g, 0.75 mol) was charged into a 2-L, 3-neck, round-bottom flask in a glove box under a nitrogen atmosphere. The reactor was connected to a nitrogen manifold. Freshly distilled tetrahydrofuran (400 mL) was added to the mixture and the mixture was cooled to -20° C. Normal butyllithium (1.6 M in hexanes, 468 mL, 0.75 mol) was added over a 2 hour period. The cold bath was removed and the orange solution was warmed to room temperature. After stirring at room temperature for 0.5 hour, (-)-menthyl chloride (129 g, 0.74 mol) was added. The mixture was stirred at room temperature for 21 hours and then heated at reflux for 40 hours. The reaction mixture was cooled to room temperature and quenched with H2O (125 mL). After stirring for 2 hours, the organic layer was separated, washed with H2O (125 mL) and concentrated to an oil. The resulting material was distilled under vacuum until crystal formation was observed in the distillation condenser to give about 130 g of crude NMDPP in the pot.

후처리

  1. customThe cold bath was removed
  2. temperaturethe orange solution was warmed to room temperature
  3. stirringThe mixture was stirred at room temperature for 21 hours
  4. temperatureheated
  5. temperatureat reflux for 40 hours
  6. temperatureThe reaction mixture was cooled to room temperature
  7. customquenched with H2O (125 mL)
  8. stirringAfter stirring for 2 hours
  9. customthe organic layer was separated
  10. washwashed with H2O (125 mL)
  11. concentrationconcentrated to an oil
  12. distillationThe resulting material was distilled under vacuum until crystal formation

출처 및 근거

ORD 기록
ord-2f82544475b74aa2b8f9bca6bec8bd1a
출처 데이터셋
uspto-grants-1999_11
특허 번호
US05994587

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