|
【结 构 式】 
|
【分子编号】39081 【品名】butanal oxime 【CA登记号】110-69-0 |
【 分 子 式 】C4H9NO 【 分 子 量 】87.1216 【元素组成】C 55.15% H 10.41% N 16.08% O 18.36% |
合成路线1
该中间体在本合成路线中的序号：(V)1) The condensation of 1,3-dibromopropane (II) with diethyl phosphonate (III) gives diethyl 3-bromopropylphosphonate (IV), which by reaction with butyraldehyde oxime (V) by means of sodium ethoxide in ethanol is converted to diethyl 3-(butylideneamino)propylphosphonate-N-oxide (VI). Finally, this compound is hydrolyzed with HCl in refluxing acetic acid to obtain compound (I). 2) The condensation of (IV) with N-(p-methoxybenzyloxy)-p-toluenesulfonamide (VII) by means of sodium ethoxide in ethanol gives diethyl 3-[N-methoxybenzyloxy)-N-tosylamino]propyl phosphonate (VIII), which is hydrolyzed with HCl in acetic acid to obtain compound (I). 3) The condensation of (IV) with methyl N-(benzyloxy)carbamate (IX) by means of sodium ethoxide in ethanol yields diethyl 3-(N-benzyloxy-N-methoxycarbonylamino)propylphosphonate (X), which is hydrolyzed with HCl in acetic acid to obtain compound (I). 4) The condensation of (IV) with hydroxylamine by means of NaOH in MeOH-H2O gives diethyl 3-(N-hydroxylamino)propylphosphonate (XI), which is hydrolyzed with HCl in acetic acid to obtain compound (I).
| 【1】 Kuroda, Y.; et al.; US 4143135 . |
| 【2】 Prous, J.R.; Castaner, J.; FR-31564. Drugs Fut 1980, 5, 5, 239. |
| 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) | 39088 | 3-(hydroxyamino)propylphosphonic acid | C3H10NO4P | 详情 | 详情 | |
| (II) | 12581 | 1,3-Dibromopropane | 109-64-8 | C3H6Br2 | 详情 | 详情 |
| (III) | 12714 | diethyl phosphonate; diethyl phosphite | 762-04-9 | C4H11O3P | 详情 | 详情 |
| (IV) | 39080 | diethyl 3-bromopropylphosphonate | C7H16BrO3P | 详情 | 详情 | |
| (V) | 39081 | butanal oxime | 110-69-0 | C4H9NO | 详情 | 详情 |
| (VI) | 39084 | (Z)butylidene[3-(diethoxyphosphoryl)propyl]ammoniumolate | C11H24NO4P | 详情 | 详情 | |
| (VII) | 39083 | N-[(4-methoxybenzyl)oxy]-4-methylbenzenesulfonamide | C15H17NO4S | 详情 | 详情 | |
| (VIII) | 39087 | diethyl 3-[[(4-methoxybenzyl)oxy][(4-methylphenyl)sulfonyl]amino]propylphosphonate | C22H32NO7PS | 详情 | 详情 | |
| (IX) | 39082 | methyl benzyloxycarbamate | C9H11NO3 | 详情 | 详情 | |
| (X) | 39086 | diethyl 3-[(benzyloxy)(methoxycarbonyl)amino]propylphosphonate | C16H26NO6P | 详情 | 详情 | |
| (XI) | 39085 | diethyl 3-(hydroxyamino)propylphosphonate | C7H18NO4P | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(XIX)Butyraldehyde oxime (XIX) was alkylated with bromopropyl phosphonate (V) to give the imine N-oxide (XX), which was then hydrolyzed under acidic conditions. A closely related procedure used octanaldehyde oxime instead of (XIX).
| 【1】 Takeno, H.; Hemmi, K.; Hashimoto, M.; Kamiya, T. (Fujisawa Pharmaceutical Co., Ltd.); Hydroxyaminohydrocarbonphosphonic acids. DE 2733658; US 4182758; US 4206156 . |