Diphenylphosphine → 1-(Diphenylphosphinomethyl)pyrazole

HRID 1169021노트

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HRID 1169021 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.Cl.Cl[CH2:21][N:22]1[CH:26]=[CH:25][CH:24]=[N:23]1>O1CCCC1>[C:8]1([P:7]([CH2:21][N:22]2[CH:26]=[CH:25][CH:24]=[N:23]2)[C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=1

참가 물질

5

반응물 3

HCID 70017DiphenylphosphineHCID 122483031-(chloromethyl)-1H-pyrazole hydrochlorideHCID 178418339Butyllithium

생성물 1

HCID 98350751-(Diphenylphosphinomethyl)pyrazole수율 47%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

반응 조건

온도
-78 °C

실험 절차

Diphenylphosphine (2.642 g, 14.2 mmol) is placed into a Schlenk flask with degassed tetrahydrofuran (50 ml). The solution is cooled to −78° C. and n-butyllithium (8.4 ml, 1.6 M in hexanes, 15.0 mmol) is added dropwise. The red solution is stirred at −78° C. for an additional 1 hour then the cooling bath is removed and the solution is stirred for 3 hours. The red solution is cooled to 0° C. and 1-(chloromethyl)pyrazole hydrochloride (0.698 g, 4.56 mmol) is added at once. The ice bath is removed and the reaction is stirred for 11 hours before adding degassed methanol (25 ml) and water (20 ml). The organic phase is separated and the aqueous phase is extracted with diethyl ether (3×10 ml). The organic phase is dried over magnesium sulfate, filtered and concentrated. The crude material is purified by chromatography (SiO2, 10% ethyl acetate/petroleum ether) to give 1-(diphenylphosphinomethyl)pyrazole as a white solid in 47% yield (0.574 g, 2.16 mmol). This material is characterized as follows: 1H NMR (CDCl3, 500 MHz) δ7.49 (dd, J=2.0, 0.5 Hz, 1H), 7.45-7.40 (m, 4H), 7.40-7.35 (m, 6H), 7.25 (dd, J=2.5, 0.5 Hz, 1H), 6.19 (dd, J=2.5, 2.0 Hz, 1H), 4.91 (d, J=4.5 Hz, 2H); 13C{1H} NMR (CDCl3, 125 MHz) δ139.50, 136.04 (d, J=13.4 Hz), 133.18 (d, J=19.3 Hz), 129.34, 129.49, 128.95 (d, J=6.4 Hz), 106.11, 53.01 (d, J=16.0 Hz); 13P{1H} NMR (CDCl3, 80 MHz) δ−14.98.

후처리

  1. customthe cooling bath is removed
  2. stirringthe solution is stirred for 3 hours
  3. temperatureThe red solution is cooled to 0° C.
  4. customThe ice bath is removed
  5. stirringthe reaction is stirred for 11 hours
  6. additionbefore adding
  7. customdegassed methanol (25 ml) and water (20 ml)
  8. customThe organic phase is separated
  9. extractionthe aqueous phase is extracted with diethyl ether (3×10 ml)
  10. dry with materialThe organic phase is dried over magnesium sulfate
  11. filtrationfiltered
  12. concentrationconcentrated
  13. customThe crude material is purified by chromatography (SiO2, 10% ethyl acetate/petroleum ether)

출처 및 근거

ORD 기록
ord-19251bc6f53049388e4c1ea56cdfa169
출처 데이터셋
uspto-grants-2003_09
특허 번호
US06627758B2

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