Epichlorohydrin → 2-[1-oxiranylmethyl-3-(4-trifluoromethyl-phenyl)-1H-pyrazol-4-yl]-pyrazine

HRID 1371008Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1371008
[F:1][C:2]([F:21])([F:20])[C:3]1[CH:8]=[CH:7][C:6]([C:9]2[C:13]([C:14]3[CH:19]=[N:18][CH:17]=[CH:16][N:15]=3)=[CH:12][NH:11][N:10]=2)=[CH:5][CH:4]=1.[CH2:22]([CH:24]1[O:26][CH2:25]1)Cl.C(=O)([O-])[O-].[Cs+].[Cs+]>CN(C=O)C.CCOC(C)=O>[O:26]1[CH2:25][CH:24]1[CH2:22][N:11]1[CH:12]=[C:13]([C:14]2[CH:19]=[N:18][CH:17]=[CH:16][N:15]=2)[C:9]([C:6]2[CH:7]=[CH:8][C:3]([C:2]([F:20])([F:1])[F:21])=[CH:4][CH:5]=2)=[N:10]1

Komponenten

6

Edukt 3

HCID 7835EpichlorohydrinHCID 10796Cesium carbonateHCID 178506123HCID 178506123, Verbindung

Produkt 1

HCID 222936232-[1-oxiranylmethyl-3-(4-trifluoromethyl-phenyl)-1H-pyrazol-4-yl]-pyrazineAusbeute 59 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6228DimethylformamideLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

To a solution of 2-[3-(4-trifluoromethyl-phenyl)-1H-pyrazol-4-yl]-pyrazine (200 mg, 0.69 mmol) and epichlorohydrin (0.540 mL, 6.9 mmol) in DMF (2 mL) was added cesium carbonate (450 mg, 1.38 mmol). The reaction mixture was allowed to stir for 24 h, diluted with EtOAc, and washed with saturated NaHCO3, water, and brine. The organic layer was dried over Na2SO4, concentrated and purified by column chromatography (silica, 5% acetone/CH2Cl2) to afford 2-[1-oxiranylmethyl-3-(4-trifluoromethyl-phenyl)-1H-pyrazol-4-yl]-pyrazine (141 mg, 59%). TLC (silica, 20% acetone/CH2Cl2): Rf=0.38. MS (electrospray) m/z 347.1 (347.1, calculated for C17H13F3N4O, M++H). 1H NMR (400 MHz, CDCl3): 8.51 (dd, J=2.8,1.8 Hz, 1H), 8.45 (d, J=1.5 Hz, 1H), 8.38 (d, J=12.8 Hz, 1H), 8.01 (s, 1H), 7.66 (d, J=8.6 Hz, 1H), 7.62 (d, J=8.6 Hz, 1H), 4.57 (dd, J=14.7, 3.1 Hz, 1H), 4.21 (dd, J=14.7, 6.1 Hz, 1H), 3.44 (m, 1H), 2.91 (t, J=4.5 Hz, 1H), 2.62 (dd, J=4.0, 2.5 Hz, 1H).

Aufarbeitung

  1. washwashed with saturated NaHCO3, water, and brine
  2. dry with materialThe organic layer was dried over Na2SO4
  3. concentrationconcentrated
  4. custompurified by column chromatography (silica, 5% acetone/CH2Cl2)

Quellen und Nachweise

ORD-Eintrag
ord-835728fe8ad14f7ab5be3646305d08b8
Quelldatensatz
uspto-grants-2003_06
Patentnummer
US06583155B2

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