Diisopropylamine → 4-(3,3-dimethyl-3,4-dihydro-2H-benzo[b][1,4]dioxepin-7-ylethynyl)-benzoic acid ethyl ester

HRID 2373441

Reaktionsgleichung

[C:1]([C:3]1[CH:15]=[CH:14][C:6]2[O:7][CH2:8][C:9]([CH3:13])([CH3:12])[CH2:10][O:11][C:5]=2[CH:4]=1)#[CH:2].[CH2:16]([O:18][C:19](=[O:27])[C:20]1[CH:25]=[CH:24][C:23](Br)=[CH:22][CH:21]=1)[CH3:17].C(NC(C)C)(C)C.O=[Si]=O>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.[Cu]I.CCOC(C)=O.C1COCC1>[CH2:16]([O:18][C:19](=[O:27])[C:20]1[CH:25]=[CH:24][C:23]([C:2]#[C:1][C:3]2[CH:15]=[CH:14][C:6]3[O:7][CH2:8][C:9]([CH3:12])([CH3:13])[CH2:10][O:11][C:5]=3[CH:4]=2)=[CH:22][CH:21]=1)[CH3:17]

Komponenten

Reaktionsbedingungen

Temperatur: 57 °C

Versuchsvorschrift

To a mixture under Ar of 7-ethynyl-3,3-dimethyl-3,4-dihydro-2H-benzo[b][1,4]dioxepine (6) (1.0 g), ethyl-4-bromobenzoate (1.13 g), [PdCl2(PPh3)2] (174 mg) and copper(I) iodide (94 mg) is added a degassed solution of diisopropylamine (20 ml) and THF (20 ml). The reaction mixture is stirred over night at 57° C. After addition of AcOEt (100 ml) and filtration over dicalite, the solution is washed with 1 N aq. HCl sol. (3×50 ml) and H2O (3×50 ml). The organic layer is dried over MgSO4 and the solvent is evaporated. The crude product is purified by flash chromatography (silica gel, heptane/AcOEt 9:1) followed by preparative HPLC. 756 mg of 4-(3,3-dimethyl-3,4-dihydro-2H-benzo[b][1,4]dioxepin-7-ylethynyl)-benzoic acid ethyl ester are obtained as a white solid, MS (ESI) 350.2 (M•)+.

Aufarbeitung

washthe solution is washed with 1 N aq. HCl sol. (3×50 ml) and H2O (3×50 ml)
dry with materialThe organic layer is dried over MgSO4
customthe solvent is evaporated
customThe crude product is purified by flash chromatography (silica gel, heptane/AcOEt 9:1)

Quellen und Nachweise

ORD-Eintrag: ord-fc58c7b853b34f8b96ad9dbca0ebf450
Quelldatensatz: uspto-grants-2008_12
DOI: 10.6084/m9.figshare.5104873.v1
Patentnummer: US07459480B2

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