|
【结 构 式】 
|
【分子编号】69142 【品名】1-methyl-1H-pyrazole-4,5-diamine 【CA登记号】 |
【 分 子 式 】C4H8N4 【 分 子 量 】112.134 【元素组成】C 42.84% H 7.19% N 49.96% |
合成路线1
该中间体在本合成路线中的序号：(VIII)The pyrazolyl urea intermediate (IV) is prepared as follows. Treatment of 5-amino-1-methylpyrazole (VI) with NaNO2/HCl in water at 5 oC gives the 4-nitrosopyrazole derivative (VII), which is reduced to the diaminopyrazole (VIII) by catalytic hydrogenation over Pd/C in the presence of H2SO4. Selective acylation of the 4-amino group of compound (VIII) with phenyl chloroformate in the presence of NaOH in H2O/dioxane at 10 oC then yields the phenyl carbamate (IX). After protection of the free amine group of carbamate (IX) with chlorotriphenylmethane in the presence of Et3N in THF, the resulting N-trityl derivative (X) is coupled with N-Boc-ethylenediamine (XI) in the presence of Et3N in DMF to afford pyrazolyl urea (IV) .
| 【1】 Ohki, H., Yamanaka, T., Toda, A. et al. (Astellas Pharma, Inc.; Wakunaga Pharmaceutical Co., Ltd.). Cephem compounds. EP 1556389, JP 2006506459, US 7129232, US 2007037786, WO 2004039814. |
| 【2】 Toda, A., Ohki, H., Yamanaka, T. et al. Synthesis and SAR of novel parenteral anti-pseudomonal cephalosporins: Discovery of FR264205. Bioorg Med Chem Lett 2008, 18(17): 4849-52. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (IV) | 69139 | 4-[(N-Boc-aminoethyl)carbamoylamino]-1-methyl-5-tritylaminopyrazole;tert-butyl (2-(3-(1-methyl-5-(tritylamino)-1H-pyrazol-4-yl)ureido)ethyl)carbamate | C31H36N6O3 | 详情 | 详情 | |
| (VI) | 69140 | 1-methyl-1H-pyrazol-5-amine；1-Methyl-1H-pyrazol-5-ylamine | 1192-21-8 | C4H7N3 | 详情 | 详情 |
| (VII) | 69141 | 1-methyl-4-nitro-1H-pyrazol-5-amine；5-Amino-1-methyl-4-nitropyrazole | 19868-85-0 | C4H6N4O2 | 详情 | 详情 |
| (VIII) | 69142 | 1-methyl-1H-pyrazole-4,5-diamine | C4H8N4 | 详情 | 详情 | |
| (IX) | 69143 | phenyl (5-amino-1-methyl-1H-pyrazol-4-yl)carbamate | C11H12N4O2 | 详情 | 详情 | |
| (X) | 69144 | phenyl (1-methyl-5-(tritylamino)-1H-pyrazol-4-yl)carbamate | C30H26N4O2 | 详情 | 详情 | |
| (XI) | 13241 | N-Boc-ethylenediamine;tert-butyl (2-aminoethyl)carbamate；tert-butyl 2-aminoethylcarbamate; tert-Butyl n-(2-aminoethyl)carbamate | 57260-73-8 | C7H16N2O2 | 详情 | 详情 |