Chloromethyl Methyl Ether → ethyl 3-tert-butyl-1-{4-[(methoxymethoxy)methyl]benzyl}-1H-pyrazole-5-carboxylate

HRID 2110864Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2110864
[C:1]([C:5]1[CH:9]=[C:8]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[NH:7][N:6]=1)([CH3:4])([CH3:3])[CH3:2].Cl[CH2:16][C:17]1[CH:22]=[CH:21][C:20]([CH2:23][OH:24])=[CH:19][CH:18]=1.C(=O)([O-])[O-].[K+].[K+].C(N(C(C)C)C(C)C)C.[CH3:40][O:41][CH2:42]Cl>O1CCCC1.O.CN(C)C=O>[C:1]([C:5]1[CH:9]=[C:8]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[N:7]([CH2:16][C:17]2[CH:22]=[CH:21][C:20]([CH2:23][O:24][CH2:40][O:41][CH3:42])=[CH:19][CH:18]=2)[N:6]=1)([CH3:4])([CH3:2])[CH3:3]

Komponenten

9

Edukt 5

HCID 7864Chloromethyl Methyl EtherHCID 11430Potassium CarbonateHCID 81531DiisopropylethylamineHCID 2743509Ethyl 3-tert-butyl-1H-pyrazole-5-carboxylateHCID 5107660[4-(Chloromethyl)phenyl]methanol

Produkt 1

HCID 23157202ethyl 3-tert-butyl-1-{4-[(methoxymethoxy)methyl]benzyl}-1H-pyrazole-5-carboxylateAusbeute 35,4 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 962WaterLösungsmittelHCID 6228DimethylformamideLösungsmittelHCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

A mixed solution of ethyl 3-tert-butyl-1H-pyrazole-5-carboxylate (3.00 g, 15.3 mmol), [4-(chloromethyl)phenyl]methanol (2.50 g, 16.0 mmol), potassium carbonate (2.11 g, 15.3 mmol) and N,N-dimethylformamide (40 mL) was stirred at 70° C. for 3 hr. Water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The extract washed with aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. To a mixture of the obtained oil, N-ethyldiisopropylamine (8.00 mL, 45.9 mmol) and tetrahydrofuran (50 mL) was added dropwise a solution of chloromethyl methyl ether (4.40 mL, 46.3 mmol) in tetrahydrofuran (10 mL) at 0° C. The reaction mixture was stirred overnight at room temperature, and concentrated, and the obtained residue was subjected to silica gel chromatography (ethyl acetate:hexane=1:3) to give the title compound (1.95 g, yield 35%) as a colorless oil. 1H NMR (CDCl3) δ: 1.31 (1H, t, J=7.1 Hz), 1.32 (9H, s), 3.39 (3H, s), 4.26 (2H, q, J=7.1 Hz), 4.54 (2H, s), 4.68 (2H, s), 5.70 (2H, s), 6.71 (1H, s), 7.15-7.33 (4H, m).

Aufarbeitung

  1. extractionthe mixture was extracted with ethyl acetate
  2. washThe extract washed with aqueous sodium chloride solution
  3. dry with materialdried over anhydrous magnesium sulfate
  4. concentrationconcentrated under reduced pressure
  5. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-d6fc6efcfd7a4890b85ef08a5dc0001f
Quelldatensatz
uspto-grants-2009_04
Patentnummer
US07517910B2

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