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【结 构 式】 
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【分子编号】37460 【品名】ethyl 4-(4-chlorophenyl)-4-oxobutanoate 【CA登记号】 |
【 分 子 式 】C12H13ClO3 【 分 子 量 】240.68612 【元素组成】C 59.88% H 5.44% Cl 14.73% O 19.94% |
合成路线1
该中间体在本合成路线中的序号：(II)The reaction of p-chlorobenzaldehyde (I) sodium cyanide and ethyl acetate gives ethyl 4-(p-chlorophenyl)-4-oxobutyrate (II), which is hydrolyzed with KOH to the corresponding free acid (III). The reduction of (III) with Zn and aqueous HCl affords 4-(p-chlorophenyl)butyric acid (IV), which is condensed with heptylamine (B) by means of oxalyl chloride (A) in refluxing benzene to yield N-heptyl-4-(p-chlorophenyl)butyramide (V), which is reduced with diborane in refluxing THF to afford N-heptyl-4-(p-chlorophenyl)butylamine (VI). The acetylation of (VI) with acetyl chloride (C) by means of Na2CO3 in acetone gives N-acetyl-N-heptyl-4-(p-chlorophenyl)butylamine (VII), which is reduced with diborane as before to yield N-ethyl-N-heptyl-4-(p-chlorophenyl)butylamine (VIII). The quaternization of (VIII) with refluxing ethyl bromide (D) gives N,N-diethyl-N-heptyl-4-(p-chlorophenyl)butylammonium bromide (IX), which by elution through a column with Dowex 1-X8, hydroxide form, resin is converted into N,N-diethyl-N-heptyl-4-(p-chlorophenyl)butyl ammonium hydroxide (X). Finally, this compound is salified with diluted aqueous phosphoric acid.
| 【1】 Molloy, B.B.; Steinberg, M.I.; EP 0002604 . |
| 【2】 Hillier, K.; Castaner, J.; Clofilium Phosphate. Drugs Fut 1981, 6, 12, 764. |
| 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) | 23252 | 1-heptanamine; heptylamine | 111-68-2 | C7H17N | 详情 | 详情 |
| (A) | 29841 | Oxalyl chloride; 2-Chloro-2-oxoacetyl chloride | 79-37-8 | C2Cl2O2 | 详情 | 详情 |
| (D) | 30344 | 1-bromoethane；ethyl bromide | 74-96-4 | C2H5Br | 详情 | 详情 |
| (I) | 29029 | 4-chlorobenzaldehyde | 104-88-1 | C7H5ClO | 详情 | 详情 |
| (II) | 37460 | ethyl 4-(4-chlorophenyl)-4-oxobutanoate | C12H13ClO3 | 详情 | 详情 | |
| (III) | 37461 | 4-(4-chlorophenyl)-4-oxobutyric acid | 3984-34-7 | C10H9ClO3 | 详情 | 详情 |
| (IV) | 37462 | 4-(4-chlorophenyl)butyric acid | C10H11ClO2 | 详情 | 详情 | |
| (V) | 37463 | 4-(4-chlorophenyl)-N-heptylbutanamide | C17H26ClNO | 详情 | 详情 | |
| (VI) | 37464 | N-[4-(4-chlorophenyl)butyl]-1-heptanamine; N-[4-(4-chlorophenyl)butyl]-N-heptylamine | C17H28ClN | 详情 | 详情 | |
| (VII) | 37465 | N-[4-(4-chlorophenyl)butyl]-N-heptylacetamide | C19H30ClNO | 详情 | 详情 | |
| (VIII) | 37466 | N-[4-(4-chlorophenyl)butyl]-N-ethyl-N-heptylamine; N-[4-(4-chlorophenyl)butyl]-N-ethyl-1-heptanamine | C19H32ClN | 详情 | 详情 | |
| (IX) | 37467 | N-[4-(4-chlorophenyl)butyl]-N,N-diethyl-1-heptanaminium bromide | C21H37BrClN | 详情 | 详情 | |
| (X) | 37468 | N-[4-(4-chlorophenyl)butyl]-N,N-diethyl-1-heptanaminium hydroxide | C21H38ClNO | 详情 | 详情 | |
| (C) | 19273 | acetyl chloride | 75-36-5 | C2H3ClO | 详情 | 详情 |