【结 构 式】 |
【分子编号】32192 【品名】4-amino-5-hexynoic acid 【CA登记号】 |
【 分 子 式 】C6H9NO2 【 分 子 量 】127.143 【元素组成】C 56.68% H 7.13% N 11.02% O 25.17% |
合成路线1
该中间体在本合成路线中的序号:(VIII)This compound can be prepared in two different ways: 1) The reaction of 1,4-dichloro-2-butene (I) with diethyl malonate (II) by means of sodium ethoxide in refluxing ethanol gives 1,1-bis(ethoxycarbonyl)-2-vinylcyclopropane (III), which by reaction with ammonia gas in DMF at 120 C is converted into 3-carboxamido-5-vinyl-2-pyrrolidone (IV). Finally, this compound is treated with concentrated HCl in refluxing acetic acid. 2) The treatment of (IV) with sodium ethoxide in refluxing ethanol gives 3-carboxy-5-vinyl-2-pyrrolidone (V), which is decarboxylated by treatment with refluxing acetic acid to afford 5-vinyl-2-pyrrolidone (VI). The bromination of (VI) with Br2 in CCl4 yields 5-(1,2-dibromoethyl)-2-pyrrolidone (VII), which by treatment with Na in liquid NH3 in a pressure vessel at 25 C is converted into 4-aminohex-5-inoic acid (VIII). Finally, this compound is partially reduced with H2 over a suitable catalyst.
【1】 Gittos, M.W.; Leterre, G.J.; Process for making 4-aminohex-5-enoic acid. FR 2415630; GB 2013205; JP 54112860; US 4178463 . |
【2】 Metcalf, B.W.; Jung, M.; Olefinic derivatives of amino acids. US 4039549 . |
【3】 Metcalf, B.W.; Jung, M.; Olefinic derivatives of amino acids. CA 1077487; FR 2304329; GB 1472525; JP 76125320; US 3960927 . |
【4】 Blancafort, P.; Paton, D.M.; Serradell, M.N.; Castaner, J.; RMI-71,754. Drugs Fut 1981, 6, 6, 363. |
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) | 32186 | (E)-1,4-dichloro-2-butene | 110-57-6 | C4H6Cl2 | 详情 | 详情 |
(II) | 16829 | Diethyl malonate | 105-53-3 | C7H12O4 | 详情 | 详情 |
(III) | 32187 | Diethyl 2-vinyl-1,1-cyclopropanedicarboxylate | C11H16O4 | 详情 | 详情 | |
(IV) | 32188 | 2-Oxo-5-vinyl-3-pyrrolidinecarboxamide; 3-Carboxamido-5-vinyl-2-pyrrolidone | 71107-19-2 | C7H10N2O2 | 详情 | 详情 |
(V) | 32189 | 2-oxo-5-vinyl-3-pyrrolidinecarboxylic acid | C7H9NO3 | 详情 | 详情 | |
(VI) | 32190 | 5-Vinyl-2-pyrrolidinone | C6H9NO | 详情 | 详情 | |
(VII) | 32191 | 5-(1,2-dibromoethyl)-2-pyrrolidinone | C6H9Br2NO | 详情 | 详情 | |
(VIII) | 32192 | 4-amino-5-hexynoic acid | C6H9NO2 | 详情 | 详情 |