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With sodium hydride; In tetrahydrofuran; at 0 - 20℃; for 13h;Heating / reflux; |
[0312] l-(5'-Fluoro-2'-methoxyphenyl)-4-ethylenedioxy-l-butene (7): To a suspension of 2-(l,3-dioxolan-2-yl)ethyltriphenylphosphonium bromide (5.0 g, 11.3 mmol) in THF (30 niL) under Ar was added NaH (60% in mineral oil, 0.48 g, 11.3 mmol). The reaction was heated to reflux for 1 h. The resulting orange colored suspension was cooled to 0C and 5- fluoro-2-methoxybenzaldehyde (1.54 g, 10.0 mmol) was added and the reaction was stirred for 12 h at room temperature. The mixture was poured to a separatory funnel containing ammonium chloride aqueous solution (sat. NH4C1/H2O = 1:1, v:v, 30 mL). The organics were extracted with EtOAc (3 x 80 mL) and the combined organic layers were washed with brine (60 mL) and dried over Na2SO4. The solvent was removed in vacuo and product was purified by flash column chromatography (Rf = 0.15, EtOAc/Hexane, 7:93, v:v) to result in the product (2.63 g, 66%) as a mixture of CM and trans (cis:trans = 4: 1): 1H NMR (the major isomer): (CDCl3, 500 MHz): delta 7.08 (dd, J= 3.1, 8.7 Hz, 1 H), 6.93 (dt, J= 3.1, 8.7 Hz, 1 H), 6.78 (dd, J= 4.3, 8.7 Hz, 1 H), 6.63 (d, J= 11.9 Hz, 1 H), 5.83 (td, J= 7.3 Hz, 11.9 Hz, 1 H), 4.99 (t, J= 4.6 Hz, 1 H), 4.02-3.99 (m, 2 H), 3.90-3.87 (m, 2 H), 3.80 (s, 3 H), 2.64-2.62 (m, 2 H).; [0470] l-(5'~Fluoro-2'-methoxyphenyl)-4-ethylenedioxy-l-butene (5): To a suspension of 2-(l,3-dioxolan-2-yl)ethyltrirhohenylrhohosrhohonium bromide (5.0 g, 11.3 mmol) in THF (30 mL) under an atmosphere of Ar was added NaH (60% in mineral oil, 0.48 g, 11.3 mmol) and the mixture obtained was heated to reflux for 1 h. The orange suspension obtained was cooled to 0 C and <strong>[19415-51-1]5-fluoro-2-methoxybenzaldehyde</strong> (1.54 g, 10.0 mmol) was added and the reaction was warmed to room temperature and continued with stirring for 12 h. The reaction mixture was poured to a separatory funnel containing ammonium chloride aqueous solution (sat. NH4C1/H2O 50:50, v:v, 50 mL). The organics were extracted with EtOAc (3 x 80 mL) and the combined organic layers were washed with brine (60 mL) and dried over sodium sulfate. The solvent was then removed in vacuo and the crude product obtained was purified by flash column chromatography (EtOAc/hexane, 7:93, v:v, Rf = 0.15) to give the product (2.63 g, 66%) as a 4:1 mixture of cis and trans diastereomers: 1H NMR (major isomer): (CDCl3, 500 MHz): delta 7.08 (dd, J= 3.1, 8.7 Hz, 1 H), 6.93 (dt, J= 3.1, 8.7 Hz, 1 H), 6.78 (dd, J= 4.3, 8.7 Hz, 1 H), 6.63 (d, J= 11.9 Hz, 1 H), 5.83 (td, J= 7.3 Hz, 11.9 Hz, 1 H), 4.99 (t, J= 4.6 Hz, 1 H), 4.02-3.99 (m, 2 H), 3.9-3.87 (m, 2 H), 3.8 (s, 3 H), 2.64-2.62 (m, 2 H). |
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