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

HRID 1509644ノート

反応式

HRID 1509644 の反応式
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

参加物

7

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 312751,4-Dioxane溶媒

反応条件

温度
110 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-92c650b15e8945a19bc63890d306cb3e
出典データセット
uspto-grants-2015_12
特許番号
US09224963B2

反応ノート

読み込み中…