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【结 构 式】 
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【分子编号】41194 【品名】dimethyl 4,5-bis[(trimethylsilyl)oxy]-1,4-cyclohexadiene-1,2-dicarboxylate 【CA登记号】 |
【 分 子 式 】C16H28O6Si2 【 分 子 量 】372.56572 【元素组成】C 51.58% H 7.58% O 25.77% Si 15.08% |
合成路线1
该中间体在本合成路线中的序号：(IV)The silylation of butane-2,3-dione(I) with TMSCl and TEA in hot DMF gives the silylated enol (II), which is cyclized with dimethyl acetylenedicarboxylate (III) in refluxing toluene to yield 4,5-bis(trimethylsilyloxy)-3,6-dihydrophthalic acid dimethyl ester (IV). The condensation of (IV) with aniline (V), with simultaneous aromatization in refluxing acetic acid affords 4,5-bis(phenylamino)phthalic acid dimethyl ester (VI), which is hydrolyzed with LiOH in methanol and anhydrized with acetic anhydride in toluene giving the corresponding phthalic anhydride (VII). Finally this compound is treated with ammonium formate at 140-50 C to furnish the target phthalimide.
| 【1】 Traxler, P.; Lydon, N.; Recent advances in protein tyrosine kinase inhibitors. Drugs Fut 1995, 20, 12, 1261. |
| 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) | 37053 | biacetyl | 431-03-8 | C4H6O2 | 详情 | 详情 |
| (II) | 41193 | 2,2,7,7-tetramethyl-4,5-dimethylene-3,6-dioxa-2,7-disilaoctane; 1-methylene-2-[(trimethylsilyl)oxy]-2-propenyl trimethylsilyl ether | C10H22O2Si2 | 详情 | 详情 | |
| (III) | 24551 | Dimethyl acetylenedicarboxylate; Dimethyl 2-butynedioate;Acetylenedicarboxylic acid dimethyl ester | 762-42-5 | C6H6O4 | 详情 | 详情 |
| (IV) | 41194 | dimethyl 4,5-bis[(trimethylsilyl)oxy]-1,4-cyclohexadiene-1,2-dicarboxylate | C16H28O6Si2 | 详情 | 详情 | |
| (V) | 12294 | Aniline; Phenylamine | 62-53-3 | C6H7N | 详情 | 详情 |
| (VI) | 41195 | dimethyl 4,5-dianilinophthalate | C22H20N2O4 | 详情 | 详情 | |
| (VII) | 41196 | 5,6-dianilino-2-benzofuran-1,3-dione | C20H14N2O3 | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(IV)The silylation of butane-2,3-dione(I) with TMSCl and TEA in hot DMF gives the silylated enol (II), which is cyclized with dimethyl acetylenedicarboxylate (III) in refluxing toluene to yield 4,5-bis(trimethylsilyloxy)-3,6-dihydrophthalic acid dimethyl ester (IV). The condensation of (IV) with 4-fluoroaniline (V), with simultaneous aromatization in refluxing acetic acid affords 4,5-bis(4-fluorophenylamino)phthalic acid dimethyl ester (VI), which is hydrolyzed with LiOH in methanol and anhydrized with acetic anhydride in toluene giving the corresponding phthalic anhydride (VII). Finally this compound is treated with ammonium formate at 140-50 C to furnish the target phthalimide.
| 【1】 Traxler, P.; Lydon, N.; Recent advances in protein tyrosine kinase inhibitors. Drugs Fut 1995, 20, 12, 1261. |
| 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) | 37053 | biacetyl | 431-03-8 | C4H6O2 | 详情 | 详情 |
| (II) | 41193 | 2,2,7,7-tetramethyl-4,5-dimethylene-3,6-dioxa-2,7-disilaoctane; 1-methylene-2-[(trimethylsilyl)oxy]-2-propenyl trimethylsilyl ether | C10H22O2Si2 | 详情 | 详情 | |
| (III) | 24551 | Dimethyl acetylenedicarboxylate; Dimethyl 2-butynedioate;Acetylenedicarboxylic acid dimethyl ester | 762-42-5 | C6H6O4 | 详情 | 详情 |
| (IV) | 41194 | dimethyl 4,5-bis[(trimethylsilyl)oxy]-1,4-cyclohexadiene-1,2-dicarboxylate | C16H28O6Si2 | 详情 | 详情 | |
| (V) | 37690 | 4-fluorophenylamine; 4-fluoroaniline | 371-40-4 | C6H6FN | 详情 | 详情 |
| (VI) | 41197 | dimethyl 4,5-bis(4-fluoroanilino)phthalate | C22H18F2N2O4 | 详情 | 详情 | |
| (VII) | 41198 | 5,6-bis(4-fluoroanilino)-2-benzofuran-1,3-dione | C20H12F2N2O3 | 详情 | 详情 |