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【结 构 式】 
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【分子编号】11371 【品名】(2-methyl-1,3-dioxolan-2-yl)methyl (Z)-2-acetyl-3-(2-nitrophenyl)-2-propenoate 【CA登记号】 |
【 分 子 式 】C16H17NO7 【 分 子 量 】335.31352 【元素组成】C 57.31% H 5.11% N 4.18% O 33.4% |
合成路线1
该中间体在本合成路线中的序号：(V)This compound can be prepared in two related ways: 1) The condensation of diketene (I) with 2,2-(ethylenedioxy)propanol (II) by means of NaH in refluxing benzene gives 2,2-(ethylenedioxy)propyl acetylacetate (III), which is condensed with 2-nitrobenzaldehyde (IV) by means of piperidine and acetic acid in benzene, yielding 2,2-(ethylenedioxy)propyl 2-(2-nitrobenzylidene)acetoacetate (V). The cyclization of (V) with methyl 3-aminocrotonate (VI) in refluxing ethanol affords the protected dihydropyridine (VII), which is finally hydrolyzed with acetic acid in hot water. 2) The reaction of the acetoacetate (III), obtained as before, with ammonia in methanol gives the 3-aminocrotonate (VIII), which is cyclized with methyl 2-(2-nitrobenzylidene)acetoacetate (IX) in refluxing ethanol to afford the dihydropyridine (VII), already obtained.
| 【1】 Ohno, S.; Mizukoshi, K.; Komatsu, O.; Ichiara, K.; Morishima, T. (Maruko Seiyaku); Novel 1,4-dihydropyridines, especially useful as hypotensives. FR 2514761 . |
| 【2】 Castaner, J.; Prous, J.; MPC-1304. Drugs Fut 1991, 16, 1, 25. |
| 【3】 Sumita, T.; Nakamura, Y.; Ichihara, K.; Mizukoshi, K.; Komatsu, O.; Morishima, T.; Ohno, S.; Synthesis of asymmetric 4-aryl-1,4-dihydro-2,6-dimethyl-3,5-pyridinedicarboxylates with vasodilating and antihypertensive activities. Chem Pharm Bull 1986, 34, 4, 1589-606. |
| 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) | 11367 | 4-Methylene-2-oxetanone; Acetyl ketene | 674-82-8 | C4H4O2 | 详情 | 详情 |
| (II) | 11368 | (2-Methyl-1,3-dioxolan-2-yl)methanol | C5H10O3 | 详情 | 详情 | |
| (III) | 11369 | (2-methyl-1,3-dioxolan-2-yl)methyl 3-oxobutanoate | C9H14O5 | 详情 | 详情 | |
| (IV) | 11370 | 2-Nitrobenzaldehyde | 552-89-6 | C7H5NO3 | 详情 | 详情 |
| (V) | 11371 | (2-methyl-1,3-dioxolan-2-yl)methyl (Z)-2-acetyl-3-(2-nitrophenyl)-2-propenoate | C16H17NO7 | 详情 | 详情 | |
| (VI) | 11372 | Methyl (E)-3-amino-2-butenoate; Methyl 3-aminocrotonate | C5H9NO2 | 详情 | 详情 | |
| (VII) | 11373 | 3-methyl 5-[(2-methyl-1,3-dioxolan-2-yl)methyl] 2,6-dimethyl-4-(2-nitrophenyl)-1,4-dihydro-3,5-pyridinedicarboxylate | C21H24N2O8 | 详情 | 详情 | |
| (VIII) | 11374 | (2-methyl-1,3-dioxolan-2-yl)methyl (E)-3-amino-2-butenoate | C9H15NO4 | 详情 | 详情 | |
| (IX) | 11375 | Methyl-2-(2-nitrobenzylidene)acetoacetate; methyl (Z)-2-acetyl-3-(2-nitrophenyl)-2-propenoate | 39562-27-1 | C12H11NO5 | 详情 | 详情 |