Water → 5-Amino-3-cyano-4-(cyclohept-2-enyl)-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole

HRID 1421501Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1421501
[NH2:1][C:2]1[N:6]([C:7]2[C:12]([Cl:13])=[CH:11][C:10]([C:14]([F:17])([F:16])[F:15])=[CH:9][C:8]=2[Cl:18])[N:5]=[C:4]([C:19]#[N:20])[C:3]=1I.[CH:22]1[CH2:28][CH2:27][CH2:26][CH2:25][CH2:24][CH:23]=1.C(N(CC)CC)C.O>CN(C=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[NH2:1][C:2]1[N:6]([C:7]2[C:12]([Cl:13])=[CH:11][C:10]([C:14]([F:17])([F:16])[F:15])=[CH:9][C:8]=2[Cl:18])[N:5]=[C:4]([C:19]#[N:20])[C:3]=1[CH:28]1[CH2:27][CH2:26][CH2:25][CH2:24][CH:23]=[CH:22]1

Komponenten

7

Edukt 4

HCID 962WaterHCID 8471TriethylamineHCID 12363Cycloheptene2×HCID 154620775-Amino-3-cyano-4-iodo-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]pyrazole

Produkt 1

HCID 98665095-Amino-3-cyano-4-(cyclohept-2-enyl)-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418476HCID 178418476, VerbindungKatalysatorHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
65 °C

Versuchsvorschrift

To 5-amino-3-cyano-4-iodo-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole (2.23 g, 5 mmol, WO97/07102) and cycloheptene (3 ml) in dry DMF (25 ml), under a nitrogen atmosphere, was added bis(triphenylphosphine)palladium dichloride (100 mg, 0.13 mmol), cuprous iodide (100 mg) and triethylamine (2 ml). The mixture was heated at 65° C. for 18 h. A further 3 ml of cycloheptene was added and the mixture heated at 70° C. for 82 h. The cooled mixture was poured into water (500 ml) and extracted with DCM (2×100 ml). The organic phase was dried (MgSO4), filtered and the solvent removed in vacuo to leave a brown oil. This was purified by silica chromatography (eluting with hexane/diethyl ether 1/1 v/v). The resulting cream solid was further purified by silica chromatography (eluting with hexane, hexane/diethyl ether 19/1, hexane/diethyl ether 9/1 and finally hexane/diethyl ether 3/1) to yield 564 mg of the title compound as a cream solid.

Aufarbeitung

  1. temperaturethe mixture heated at 70° C. for 82 h
  2. extractionextracted with DCM (2×100 ml)
  3. dry with materialThe organic phase was dried (MgSO4)
  4. filtrationfiltered
  5. customthe solvent removed in vacuo
  6. customto leave a brown oil
  7. customThis was purified by silica chromatography (eluting with hexane/diethyl ether 1/1 v/v)
  8. customThe resulting cream solid was further purified by silica chromatography (
  9. washeluting with hexane, hexane/diethyl ether 19/1, hexane/diethyl ether 9/1 and finally hexane/diethyl ether 3/1)

Quellen und Nachweise

ORD-Eintrag
ord-fa95e32891d64cdb9afc8fc868d0269d
Quelldatensatz
uspto-grants-2000_06
Patentnummer
US06077859

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