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【结 构 式】 
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【分子编号】32775 【品名】2-[(E)-(dimethylamino)methylidene]-1-(3-methoxy-2-nitrophenyl)-1,3-hexanedione 【CA登记号】 |
【 分 子 式 】C16H20N2O5 【 分 子 量 】320.34528 【元素组成】C 59.99% H 6.29% N 8.74% O 24.97% |
合成路线1
该中间体在本合成路线中的序号：(IV)The reaction of 3-methoxy-2-nitrobenzoic acid methyl ester (I) with 2-pentanone (II) by means of LDA gives 1-(3-methoxy-2-nitrophenyl)hexane-1,3-dione (III), which is condensed with dimethylformamide dimethyl acetal (DMFA) yielding the enamine (IV). The cyclization of (IV) by hydrogenation with H2 over Pd/C affords quinolone (V), which is treated with refluxing POCl3 to give 1-(4-chloro-8-methoxyquinolin-3-yl)-1-butanone (VI). Finally, this compound is condensed with o-toluidine in refluxing dioxane. The intermediate, the quinolone (V) has also been obtained as follows: The reaction of 1-chloro-1-hexen-3-one (VIII) with NaOH in methanol gives 3-oxohexanal (IX) (enol form), which is condensed with 2-amino-3-methoxybenzoic acid methyl ester (X) yielding the enamine (XI). Finally, this compound is cyclized by means of sodium methoxide to afford the desired quinolone (V).
| 【1】 Atkins, R.J.; et al.; Synthetic routes to quinoline derivatives: Novel syntheses of 3-butyryl-8-methoxy-4-[(2-methylphenyl)amini]quinoline and 3-butyryl-8-(2-hydroxyethoxy)-4-[(2-methylphenyl)amino]quin. Org Process Res Dev 1997, 1, 3, 185. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (I) | 32773 | methyl 3-methoxy-2-nitrobenzoate | 5307-17-5 | C9H9NO5 | 详情 | 详情 |
| (II) | 15048 | 2-pentanone | 107-87-9 | C5H10O | 详情 | 详情 |
| (III) | 32774 | 1-(3-methoxy-2-nitrophenyl)-1,3-hexanedione | C13H15NO5 | 详情 | 详情 | |
| (IV) | 32775 | 2-[(E)-(dimethylamino)methylidene]-1-(3-methoxy-2-nitrophenyl)-1,3-hexanedione | C16H20N2O5 | 详情 | 详情 | |
| (V) | 12519 | 3-Butyryl-8-methoxy-4(1H)-quinolinone | C14H15NO3 | 详情 | 详情 | |
| (VI) | 12520 | 1-(4-Chloro-8-methoxy-3-quinolinyl)-1-butanone | C14H14ClNO2 | 详情 | 详情 | |
| (VII) | 15511 | o-toluidine; 2-methylphenylamine;2-Methylaniline；2-Aminotoluene;1-Amino-2-methylbenzene;1-Methyl-2-aminobenzene; ortho-Toluidine | 95-53-4 | C7H9N | 详情 | 详情 |
| (VIII) | 32776 | (Z)-1-chloro-1-hexen-3-one | C6H9ClO | 详情 | 详情 | |
| (IX) | 32777 | (Z)-1-hydroxy-1-hexen-3-one | C6H10O2 | 详情 | 详情 | |
| (X) | 32778 | methyl 2-amino-3-methoxybenzoate | C9H11NO3 | 详情 | 详情 | |
| (XI) | 32779 | methyl 3-methoxy-2-[[(Z)-3-oxo-1-hexenyl]amino]benzoate | C15H19NO4 | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(XVI)The intermediate quinolone (V) has also been obtained by two other ways: a) The reaction of 3-methoxy-2-nitrobenzoic acid methyl ester (XIII) with 2-pentanone (XIV) by means of LDA gives 1-(3-methoxy-2-nitrophenyl)hexane-1,3-dione (XV), which is condensed with dimethylformamide dimethyl acetal (DMFA) yielding the enamine (XVI). Finally, this compound is cyclized by hydrogenation with H2 over Pd/C to afford the desired quinolone (V). b) The reaction of 1-chloro-1-hexen-3-one (XVII) with NaOH in methanol gives 3-oxohexanal (XVIII) (enol form), which is condensed with 2-amino-3-methoxybenzoic acid methyl ester (XIX) yielding the enamine (XX). Finally, this compound is cyclized by means of sodium methoxide to afford the desired quinolone (V).
| 【1】 Atkins, R.J.; et al.; Synthetic routes to quinoline derivatives: Novel syntheses of 3-butyryl-8-methoxy-4-[(2-methylphenyl)amini]quinoline and 3-butyryl-8-(2-hydroxyethoxy)-4-[(2-methylphenyl)amino]quin. Org Process Res Dev 1997, 1, 3, 185. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (V) | 12519 | 3-Butyryl-8-methoxy-4(1H)-quinolinone | C14H15NO3 | 详情 | 详情 | |
| (XIII) | 32773 | methyl 3-methoxy-2-nitrobenzoate | 5307-17-5 | C9H9NO5 | 详情 | 详情 |
| (XIV) | 15048 | 2-pentanone | 107-87-9 | C5H10O | 详情 | 详情 |
| (XV) | 32774 | 1-(3-methoxy-2-nitrophenyl)-1,3-hexanedione | C13H15NO5 | 详情 | 详情 | |
| (XVI) | 32775 | 2-[(E)-(dimethylamino)methylidene]-1-(3-methoxy-2-nitrophenyl)-1,3-hexanedione | C16H20N2O5 | 详情 | 详情 | |
| (XVII) | 32776 | (Z)-1-chloro-1-hexen-3-one | C6H9ClO | 详情 | 详情 | |
| (XVIII) | 32777 | (Z)-1-hydroxy-1-hexen-3-one | C6H10O2 | 详情 | 详情 | |
| (XIX) | 32778 | methyl 2-amino-3-methoxybenzoate | C9H11NO3 | 详情 | 详情 | |
| (XX) | 32779 | methyl 3-methoxy-2-[[(Z)-3-oxo-1-hexenyl]amino]benzoate | C15H19NO4 | 详情 | 详情 |