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【结 构 式】 
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【分子编号】13535 【品名】2-(1H-Imidazol-1-yl)acetonitrile 【CA登记号】 |
【 分 子 式 】C5H5N3 【 分 子 量 】107.11492 【元素组成】C 56.07% H 4.7% N 39.23% |
合成路线1
该中间体在本合成路线中的序号：(I)The reaction of 2-(1-imidazolyl)acetonitrile (I) with CS2 and KOH in DMF gives the dithiolate (II), which is then cyclized with 1-(2-chlorophenyl)-1,2-di(methanesulfonyloxy)ethane (III). A column chromatography over silicagel allows the separation of the (E)- and (Z)-isomers.
| 【1】 Seo, A.; Kanno, H.; Hasegawa, N.; Miyagi, Y.; Nishimura, A.; Konaka, S.; Ohmi, T.; Munechika, Y.; Uchida, M.; Ikeda, K. (Nihon Nohyaku Co., Ltd.); A novel ketene S,S-acetal deriv., a process for manufacturing thereof and a method for curing mycosis by administering it. EP 0218736 . |
| 【2】 Seo, A.; Sugano, H.; Hasegawa, C.; Ikeda, K.; Munechica, Y.; Konoe, T.; Konaka, M. (Nihon Nohyaku Co., Ltd.); Antifungal agent. JP 1987093227 . |
| 【3】 Seo, A.; Sugano, H.; Hasegawa, C.; Ikeda, K.; Nishimura, A.; Miyashiro, Y. (Nihon Nohyaku Co., Ltd.); Non-medicinal bactericidal agents and method for their preparation. JP 1987093204 . |
| 【4】 Seo, A.; Kanno, H.; Hasegawa, N.; Miyagi, Y.; Nishimura, A.; Konaka, S.; Ohmi, T.; Munechika, Y.; Uchida, M.; Ikeda, K. (Nihon Nohyaku Co., Ltd.); Antimycotic agent and fungicidal agent. US 4738976 . |
| 【5】 Seo, A.; Sugano, H.; Hasegawa, C.; Miyashiro, Y.; Nishimura, A.; Ikeda, K. (Nihon Nohyaku Co., Ltd.); Ketene S,S-acetals. JP 1985218387 . |
| 【6】 Castaner, J.; Prous, J.; Lanoconazole. Drugs Fut 1993, 18, 3, 222. |
合成路线2
该中间体在本合成路线中的序号：(IV)This compound has been obtained by two similar ways: The enantiocontrolled reduction of 2,4-dichlorophenacyl bromide (I) with BH3/THF and a chiral oxazaborole catalyst gives 1(S)-(2,4-dichlorophenyl)-2-bromoethanol (II), which is treated with Ms-Cl and TEA in dichloromethane to yield the corresponding mesylate (III). Finally, this compound is cyclized with 2-(1-imidazolyl)-3,3-disulfanylacrylonitrile (VI) by means of KOH in DMSO. Alternatively, 1(S)-(2,4-dichlorophenyl)ethane-1,2-diol (VII) is treated with Ms-Cl and TEA in dichloromethane to give the corresponding dimesylate (VIII), which is condensed with the acrylonitrile (VI) with KOH as before. The intermediate acrylonitrile (VI) has been obtained by condensation of 2-(1-imidazolyl)acetonitrile (IV) with CS2 (V) by means of KOH in DMSO.
| 【1】 Kodama, H.; Niwano, Y.; Kanai, K.; Yoshida, M. (Nihon Nohyaku Co., Ltd.); Antifungal agent, cpd. therefor, process for producing the same. JP 1997100279; JP 1998158168; US 5900488; WO 9702821 . |
| 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) | 36408 | 2-bromo-1-(2,4-dichlorophenyl)-1-ethanone | C8H5BrCl2O | 详情 | 详情 | |
| (II) | 53962 | (1S)-2-bromo-1-(2,4-dichlorophenyl)-1-ethanol | n/a | C8H7BrCl2O | 详情 | 详情 |
| (III) | 53963 | (1S)-2-bromo-1-(2,4-dichlorophenyl)ethyl methanesulfonate | n/a | C9H9BrCl2O3S | 详情 | 详情 |
| (IV) | 13535 | 2-(1H-Imidazol-1-yl)acetonitrile | C5H5N3 | 详情 | 详情 | |
| (V) | 53967 | Alcohol of sulfur; Carbon bisulfuret; Carbon disulfide; Carbon sulfide; Dithiocarbonic anhydride; Methyl disulfide; Sulfocarbonic anhydride | 75-15-0 | CS2 | 详情 | 详情 |
| (VI) | 53964 | 2-(1H-imidazol-1-yl)-3,3-disulfanylacrylonitrile | n/a | C6H5N3S2 | 详情 | 详情 |
| (VII) | 53965 | (1S)-1-(2,4-dichlorophenyl)-1,2-ethanediol | n/a | C8H8Cl2O2 | 详情 | 详情 |
| (VIII) | 53966 | (1S)-1-(2,4-dichlorophenyl)-2-[(methylsulfonyl)oxy]ethyl methanesulfonate | n/a | C10H12Cl2O6S2 | 详情 | 详情 |