【结 构 式】 |
【分子编号】39562 【品名】7-bromo-1,3-benzodioxole-5-carbaldehyde 【CA登记号】 |
【 分 子 式 】C8H5BrO3 【 分 子 量 】229.0299 【元素组成】C 41.95% H 2.2% Br 34.89% O 20.96% |
合成路线1
该中间体在本合成路线中的序号:(XI)The starting phenylethylamine (I) is prepared by condensation of N-formyl-5-bromo-3,4-methylenedioxyphenylethylamine (VIII) with N-carbobenzoxy-3-methoxy-4-hydroxyphenylethylamine (IX) through an Ullman condensation catalysed by CuO, followed by elimination of the formyl group with HCl in methanol. Compound (VIII) is prepared as follows: 3,4-dihydroxy-5-bromobenzaldehyde (X) is methylenated with methylene bromide (A) and CuO in DMF giving 3,4-methylenedioxy-5-bromobenzaldehyde (XI), which is condensed with nitromethane (B) in acetic acid containing ammonium acetate affording 3,4-methylenedioxy-5-bromo-beta-nitrostyrene (XII). The reduction of (XII) under Clemensen conditions yields 3,4-methylenedioxy-5-bromophenylethylamine (XIII), which is finally formylated with formic acid in decalin. Compound (IX) is prepared as follows: 3-methoxy-4-hydroxy-beta-nitrostyrene (XIV) is treated with ethyl chloroformate (C) in pyridine yielding the corresponding ethoxycarbonyl derivative (XV), which is reduced under Clemensen conditions to 3-methoxy-4-ethoxycarbonyloxyphenylethylamine (XVI). Finally, this compound is treated first with benzyloxycarbonyl chloride and then with aqueous NaHCO3.
【1】 Tomita, M.; et al.; Synthesis of di-cepharanthine. Tetrahedron Lett 1967, 1201-06. |
【2】 Serradell, M.N.; Blancafort, P.; Mealy, N.; Castañer, J.; Cepharanthine. Drugs Fut 1979, 4, 7, 481. |
【3】 Kondo, H.; et al.; US 2206407 . |
中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
---|---|---|---|---|---|---|
(A) | 10252 | 1,2-Dibromoethane; Ethylene dibromide | 106-93-4 | C2H4Br2 | 详情 | 详情 |
(B) | 39563 | nitromethane | 75-52-5 | CH3NO2 | 详情 | 详情 |
(I) | 39554 | benzyl 4-[[6-(2-aminoethyl)-1,3-benzodioxol-4-yl]oxy]-3-methoxyphenethylcarbamate | C26H28N2O6 | 详情 | 详情 | |
(VIII) | 39566 | 2-(7-bromo-1,3-benzodioxol-5-yl)ethylformamide | C10H10BrNO3 | 详情 | 详情 | |
(IX) | 39570 | benzyl 3-hydroxy-4-methoxyphenethylcarbamate | C17H19NO4 | 详情 | 详情 | |
(X) | 39561 | 3-bromo-4,5-dihydroxybenzaldehyde | 16414-34-9 | C7H5BrO3 | 详情 | 详情 |
(XI) | 39562 | 7-bromo-1,3-benzodioxole-5-carbaldehyde | C8H5BrO3 | 详情 | 详情 | |
(XII) | 39564 | 4-bromo-6-[(E)-2-nitroethenyl]-1,3-benzodioxole | C9H6BrNO4 | 详情 | 详情 | |
(XIII) | 39565 | 2-(7-bromo-1,3-benzodioxol-5-yl)ethylamine; 2-(7-bromo-1,3-benzodioxol-5-yl)-1-ethanamine | C9H10BrNO2 | 详情 | 详情 | |
(XIV) | 39567 | 2-methoxy-5-[(E)-2-nitroethenyl]phenol | C9H9NO4 | 详情 | 详情 | |
(XV) | 39568 | ethyl 2-methoxy-5-[(E)-2-nitroethenyl]phenyl carbonate | C12H13NO6 | 详情 | 详情 | |
(XVI) | 39569 | 5-(2-aminoethyl)-2-methoxyphenyl ethyl carbonate | C12H17NO4 | 详情 | 详情 | |
(C) | 11229 | 1-[(Chlorocarbonyl)oxy]ethane;ethyl carbonochloridate; Carbonchloridic acid ethyl ester;Ethyl chloroformate;Ethyl chlorocarbonate | 541-41-3 | C3H5ClO2 | 详情 | 详情 |