3,5-Dimethylpyrazole → 1-(3-Methoxyphenyl)-3,5-dimethyl-1H-pyrazole

HRID 1509644Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1509644
I[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([O:8][CH3:9])[CH:3]=1.[CH3:10][C:11]1[CH:15]=[C:14]([CH3:16])[NH:13][N:12]=1.C([O-])([O-])=O.[K+].[K+].[C@@H]1(N)CCCC[C@H]1N>O1CCOCC1.[Cu]I>[CH3:9][O:8][C:4]1[CH:3]=[C:2]([N:12]2[C:11]([CH3:10])=[CH:15][C:14]([CH3:16])=[N:13]2)[CH:7]=[CH:6][CH:5]=1

Komponenten

7

Edukt 4

HCID 62103,5-DimethylpyrazoleHCID 11430Potassium CarbonateHCID 438061,2-Diaminocyclohexane, trans-HCID 69839Benzene, 1-iodo-3-methoxy-

Produkt 1

HCID 392404991-(3-Methoxyphenyl)-3,5-dimethyl-1H-pyrazole

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
110 °C

Versuchsvorschrift

A mixture of 1-iodo-3-methoxybenzene (7.15 mL, 60 mmol, 1.0 eq), 3,5-dimethyl-1H-pyrazole (6.92 g, 72 mmol, 1.2 eq), CuI (0.46 g, 2.4 mmol, 0.04 eq), K2CO3 (17.41 g, 126 mmol, 2.1 eq), trans-1,2-cyclohexanediamine (1.37 g, 12 mmol, 0.2 eq) in dioxane (45 mL) was stirred at a temperature of 110° C. for 3.5 days under a nitrogen atmosphere and then cooled to ambient temperature. The solid was filtered off and washed with ethyl acetate. The filtrate was concentrated under reduced pressure and the residue was purified through column chromatography on silica gel using hexane and ethyl acetate (10:1-3:1) as an eluent to obtain the desired product, 1-(3-methoxyphenyl)-3,5-dimethyl-1H-pyrazole 1, as a brown liquid (7.12 g in 59% yield). 1H NMR (DMSO-d6, 400 MHz): δ 2.18 (s, 3H), 2.30 (s, 3H), 3.80 (s, 3H), 6.06 (s, 1H), 6.95 (dd, J=8.0, 2.4 Hz, 1H), 7.02-7.06 (m, 2H), 7.39 (t, J=8.0 Hz, 1H).

Aufarbeitung

  1. temperaturecooled to ambient temperature
  2. filtrationThe solid was filtered off
  3. washwashed with ethyl acetate
  4. concentrationThe filtrate was concentrated under reduced pressure
  5. customthe residue was purified through column chromatography on silica gel

Quellen und Nachweise

ORD-Eintrag
ord-92c650b15e8945a19bc63890d306cb3e
Quelldatensatz
uspto-grants-2015_12
Patentnummer
US09224963B2

Notizen zur Reaktion

Wird geladen…