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【结 构 式】 
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【分子编号】10416 【品名】(3aS,12bS)-2-Methyl-5-nitro-2,3,3a,12b-tetrahydro-1H-dibenzo[2,3:6,7]oxepino[4,5-c]pyrrole 【CA登记号】 |
【 分 子 式 】C17H16N2O3 【 分 子 量 】296.32572 【元素组成】C 68.91% H 5.44% N 9.45% O 16.2% |
合成路线1
该中间体在本合成路线中的序号：(B)The dialkylation of aqueous N,N'-diacetyl-hydrazine by simultaneous addition of diethyl sulfate and potassium hydroxide so as to maintain a pH of 10.5-11.5 affords N,N'-diacetyl-N,N'-diethylhydrazine, which is hydrolyzed to diethylhydrazine (II) by hydrochloric acid. The pH of the acid solution is adjusted to 10, where it is maintained during the addition of epichlorohydrin to give 1,2-diethyl-4-pyrazolidinol (III). The pyrazolidinol is converted to 1,2-diethyl 4-aminopyrazolidine (VIII) by either amination of the corresponding chloro compound (IV) or displacement of the mesyloxy group in compound (V) by the azide ion, followed by reduction.
| 【1】 Munson, H.R. Jr.; Cale, A.D. Jr, Lo, Y.S.; Lunsford, C.D.; Synthetic and pharmacological properties of N-(1,2-dialkyl-4-pyrazolidinyl)benzamides - Selective gastric prokinetic agents. 187th ACS Natl Meet (April 8-13, St. Louis) 1984, 7, 9, 650. |
| 【2】 Cale, A.D.Jr.; Jenkins, H. (A.H. Robins Co. Inc.); Process for the preparation of 4-Pyrazolidinols. DE 2031489; ES 380355; FR 2053022; GB 1309018; US 3660426 . |
| 【3】 Cale, A. Jr.; Dazopride succinate. Drugs Fut 1985, 10, 7, 553. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (B) | 10416 | (3aS,12bS)-2-Methyl-5-nitro-2,3,3a,12b-tetrahydro-1H-dibenzo[2,3:6,7]oxepino[4,5-c]pyrrole | C17H16N2O3 | 详情 | 详情 | |
| (A) | 27379 | N'-acetylacetohydrazide | 3148-73-0 | C4H8N2O2 | 详情 | 详情 |
| (I) | 27380 | N'-acetyl-N,N'-diethylacetohydrazide | C8H16N2O2 | 详情 | 详情 | |
| (II) | 27381 | 1,2-diethylhydrazine | C4H12N2 | 详情 | 详情 | |
| (III) | 27382 | 1,2-diethyl-4-pyrazolidinol | C7H16N2O | 详情 | 详情 | |
| (IV) | 27383 | 4-chloro-1,2-diethylpyrazolidine | C7H15ClN2 | 详情 | 详情 | |
| (V) | 27384 | 1,2-diethyl-4-(methylsulfonyl)pyrazolidine | C8H18N2O2S | 详情 | 详情 | |
| (VIII) | 27385 | 1,2-diethyl-4-pyrazolidinamine | 70180-92-6 | C7H17N3 | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(II)Several radiolabeled forms of Org-5222 and its metabolite Org-30526 have been synthesized: 1) [5-36Cl]-Org-5222: The nitration of trans-2-methyl-2,3,3a,12b-tetrahydro-1H-dibenz[2,3:6,7]oxepino[4,5-c]pyrrole (I) with HNO3/H2SO4 gives the 5-nitro derivative (II), which is reduced with H3PO3 - Pd/C in methanol to the corresponding amino derivative (III). Finally, this compound is deaminated with NaNO2 and [36Cl]-HCl in the presence of powdered Cu.
| 【1】 Wagenaars, G.; Vader, J.; Sperling, E.; Terpstra, A.; Kaspersen, F.; Hilberink, P.; Schlachter, I.; The syntheses of radiolabelled Org 5222 and its main metabolite Org 30526. J Label Compd Radiopharm 1994, 34, 9, 845. |
| 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) | 10415 | (3aS,12bS)-2-Methyl-2,3,3a,12b-tetrahydro-1H-dibenzo[2,3:6,7]oxepino[4,5-c]pyrrole | C17H17NO | 详情 | 详情 | |
| (II) | 10416 | (3aS,12bS)-2-Methyl-5-nitro-2,3,3a,12b-tetrahydro-1H-dibenzo[2,3:6,7]oxepino[4,5-c]pyrrole | C17H16N2O3 | 详情 | 详情 | |
| (III) | 10417 | (3aS,12bS)-2-Methyl-2,3,3a,12b-tetrahydro-1H-dibenzo[2,3:6,7]oxepino[4,5-c]pyrrol-5-ylamine; (3aS,12bS)-2-Methyl-2,3,3a,12b-tetrahydro-1H-dibenzo[2,3:6,7]oxepino[4,5-c]pyrrol-5-amine | C17H18N2O | 详情 | 详情 |