関与物質
| 役割 | 名称 | HCID | 仕込み量 |
|---|
| 反応物 | Picolinic acid | HCID 1018 | — |
| 反応物 | Diethyl Malonate | HCID 7761 | — |
| 反応物 | Cesium carbonate | HCID 10796 | — |
| 反応物 | 5-Bromo-2-iodopyridine | HCID 593690 | — |
| 触媒 | Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI) | HCID 24350 | — |
| 溶媒 | 1,4-Dioxane | HCID 31275 | — |
| 生成物 | Diethyl 2-(5-bromopyridin-2-yl)malonate | HCID 59238270 | 50% |
反応手順
A mixture of 5-bromo-2-iodo-pyridine (56.8 g, 0.2 mol), malonic acid diethyl ester (64 g, 0.4 mol), CuI (3.8 g, 0.02 mol), Cs2CO3 (195.5 g, 0.6 mol) and pyridine-2-carboxylic acid (2.46 g, 0.04 mol) in 1,4-dioxane (400 mL) was stirred at 70 degrees Celsius under N2 for 24 hours. After cooling to room temperature, the solid was filtered and the solvent was evaporated. The residue was dissolved in ethyl acetate (400 mL) and washed with water, brine, dried over Na2SO4, filtered, concentrated in vacuo, the crude product was purified by flash chromatography (Petroleum Ether:EtOAc=20:1) to obtain an oil (31.6 g, 50%). MS: calc'd 316 (MH+), exp 316 (MH+). 1H NMR (d6-DMSO, 400 MHz), 8.68 (d, 1H, J=2.4 Hz), 8.11 (dd, 1H, J=2.4, 8.4 Hz), 7.45 (d, 1H, J=8.4 Hz), 5.16 (s, 1H), 4.20-4.07 (m, 4H), 1.18 (t, J=8.4 Hz, 6H).
情報源と証拠
| DOI | 10.6084/m9.figshare.5104873.v1 |
|---|
| 特許番号 | US08202866B2 |
|---|
| 出典データセット | uspto-grants-2012_06 |
|---|
| ORD ID | ord-a0f0e68cae3740dab0a1c7d2c66551dc |
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| 出典メモ | uspto-grants-2012_06 |
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