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【结 构 式】 
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【分子编号】32358 【品名】methyl 5-[(E)-2-(2,5-dimethoxyphenyl)ethenyl]-2-hydroxybenzoate 【CA登记号】 |
【 分 子 式 】C18H18O5 【 分 子 量 】314.33792 【元素组成】C 68.78% H 5.77% O 25.45% |
合成路线1
该中间体在本合成路线中的序号：(VIII)The formylation of 1,4-dimethoxybenzene (I) with C6H11-Li, TMEDA and DMF gives 2,5-dimethoxybenzaldehyde (II), which is reduced with NaBH4 to the corresponding alcohol (III). The treatment of (III) with HBr affords the benzyl bromide (IV), which by reaction with PPh3 in hot toluene is converted into the phosphonium salt (V). The condensation of (V) with 5-formyl-2-hydroxybenzoic acid methyl ester (VI)(obtained by esterification of the corresponding acid (VII) with methanol and H2SO4) by means of LDA in THF affords the stilbene (VIII). Finally, this compound is reduced with H2 over Pd/C in ethyl acetate.
| 【1】 Kucerovy, A.; et al.; An efficient large-scale synthesis of methyl 5-[2-82,5-dimethoxyphenyl)ethyl]-2-hydroxybenzoate. Org Process Res Dev 1997, 1, 4, 287. |
| 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) | 21946 | 1,4-dimethoxybenzene; 4-methoxyphenyl methyl ether | 150-78-7 | C8H10O2 | 详情 | 详情 |
| (II) | 10174 | 2,5-Dimethoxybenzaldehyde | 93-02-7 | C9H10O3 | 详情 | 详情 |
| (III) | 32353 | (2,5-dimethoxyphenyl)methanol | 33524-31-1 | C9H12O3 | 详情 | 详情 |
| (IV) | 32354 | 2-(bromomethyl)-4-methoxyphenyl methyl ether; 2-(bromomethyl)-1,4-dimethoxybenzene | C9H11BrO2 | 详情 | 详情 | |
| (V) | 32355 | (2,5-dimethoxybenzyl)(triphenyl)phosphonium bromide | C27H26BrO2P | 详情 | 详情 | |
| (VI) | 32356 | methyl 5-formyl-2-hydroxybenzoate | C9H8O4 | 详情 | 详情 | |
| (VII) | 32357 | 5-Formylsalicylic acid; 5-formyl-2-hydroxybenzoic acid | 616-76-2 | C8H6O4 | 详情 | 详情 |
| (VIII) | 32358 | methyl 5-[(E)-2-(2,5-dimethoxyphenyl)ethenyl]-2-hydroxybenzoate | C18H18O5 | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(VIII)Improved large scale synthesis: The formylation of 1,4-dimethoxybenzene (I) with C6H11-Li, TMEDA and DMF gives 2,5-dimethoxybenzaldehyde (II), which is reduced with NaBH4 in toluene/methanol to the corresponding alcohol (III). The treatment of (III) with PBr3 in ethyl acetate affords the benzyl bromide (IV), which by reaction with dimethyl phosphite (IX) and NaH in toluene is converted into the phosphonate (X). The condensation of (X) with 5-formyl-2-hydroxybenzoic acid methyl ester (VI)(obtained by esterification of the corresponding acid (VII) with methanol and H2SO4) by means of LiHMDS in THF affords the stilbene (VIII). Finally, this compound is reduced with H2 over Pd/C in ethyl acetate.
| 【1】 Kucerovy, A.; et al.; An efficient large-scale synthesis of methyl 5-[2-82,5-dimethoxyphenyl)ethyl]-2-hydroxybenzoate. Org Process Res Dev 1997, 1, 4, 287. |
| 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) | 21946 | 1,4-dimethoxybenzene; 4-methoxyphenyl methyl ether | 150-78-7 | C8H10O2 | 详情 | 详情 |
| (II) | 10174 | 2,5-Dimethoxybenzaldehyde | 93-02-7 | C9H10O3 | 详情 | 详情 |
| (III) | 32353 | (2,5-dimethoxyphenyl)methanol | 33524-31-1 | C9H12O3 | 详情 | 详情 |
| (IV) | 32354 | 2-(bromomethyl)-4-methoxyphenyl methyl ether; 2-(bromomethyl)-1,4-dimethoxybenzene | C9H11BrO2 | 详情 | 详情 | |
| (VI) | 32356 | methyl 5-formyl-2-hydroxybenzoate | C9H8O4 | 详情 | 详情 | |
| (VII) | 32357 | 5-Formylsalicylic acid; 5-formyl-2-hydroxybenzoic acid | 616-76-2 | C8H6O4 | 详情 | 详情 |
| (VIII) | 32358 | methyl 5-[(E)-2-(2,5-dimethoxyphenyl)ethenyl]-2-hydroxybenzoate | C18H18O5 | 详情 | 详情 | |
| (IX) | 32359 | dimethyl phosphonate | 868-85-9 | C2H7O3P | 详情 | 详情 |
| (X) | 32360 | dimethyl 2,5-dimethoxybenzylphosphonate | C11H17O5P | 详情 | 详情 |