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

関与物質

役割	名称	HCID	仕込み量
反応物	Diisopropylamine	HCID 7912	—
反応物	Ethyl 4-bromobenzoate	HCID 22043	—
反応物	Silica	HCID 24261	—
反応物	7-Ethynyl-3,3-dimethyl-3,4-dihydro-2H-benzo[b][1,4]dioxepine	HCID 59852695	—
触媒	Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)	HCID 24350	—
触媒	HCID 178418476	HCID 178418476	—
溶媒	Tetrahydrofuran	HCID 8028	—
溶媒	Ethyl Acetate	HCID 8857	—
生成物	4-(3,3-dimethyl-3,4-dihydro-2H-benzo[b][1,4]dioxepin-7-ylethynyl)-benzoic acid ethyl ester	HCID 11291038	43.7%

反応条件

温度	57 °C

反応手順

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•)+.

情報源と証拠

DOI	10.6084/m9.figshare.5104873.v1
特許番号	US07459480B2
出典データセット	uspto-grants-2008_12
ORD ID	ord-fc58c7b853b34f8b96ad9dbca0ebf450
出典メモ	uspto-grants-2008_12