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【结 构 式】 
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【分子编号】30445 【品名】1-chloro-7-methoxy-9H-thioxanthen-9-one 【CA登记号】 |
【 分 子 式 】C14H9ClO2S 【 分 子 量 】276.74296 【元素组成】C 60.76% H 3.28% Cl 12.81% O 11.56% S 11.59% |
合成路线1
该中间体在本合成路线中的序号：(V)The bromination of 3-methoxybenzoic acid (I) with Br2 in refluxing acetic acid gives 2-bromo-5-methoxybenzoic acid (II), which is condensed with 3-chlorothiophenol (III) by means of cupric acetate in DMF at 150 C yielding the sulfide (IV). The cyclization of (IV) in sulfuric acid affords the thioxanthenone (V), which is condensed with 2-(diethylamino)ethylamine (VI) in pyridine at 115 C giving the corresponding 2-(diethylamino)ethylamino derivative (VII). The hydroxymethylation of (VII) with formaldehyde in hot 5N acetic acid yields the hydroxymethyl derivative (VIII), which is oxidized with MnO2 in hot toluene affording the corresponding aldehyde (IX). Finally, this compound is treated with formamide and formic acid at 170 C.
| 【1】 Perni, R.B.; Wentland, M.P.; Huang, J.I.; Powles, R.G.; Aldous, S.; Klingbeil, K.M.; Peverly, A.D.; Robinson, R.G.; Corbett, T.H.; Jones, J.L.; Mattes, K.C.; Rake, J.B.; Coughlin, S.A.; Synthesis and antitumor activity of 4-aminomethylthioxanthenone and 5-aminomethylbenzothiopyranoindazole derivatives. J Med Chem 1998, 41, 19, 3645. |
| 【2】 Miller, T.C.; Collins, J.C.; Wentland, M.P.; Perni, R.B.; Corbett, T.H.; Mattes, K.C. (Sanofi-Synthelabo); Thioxanthenone antitumor agents. EP 0518414; EP 0619315; EP 0882723; JP 1993178853; JP 1994340655; US 5346917 . |
| 【3】 Wentland, M.P.; et al.; Anti-solid tumor efficacy and preparation of N-[[1-[[2-(diethylamino)ethyl]amino]-9-oxo-9H-thioxanthen-4-yl]methyl]methanesulfonamide (WIN 33377) and related derivatives. Bioorg Med Chem Lett 1994, 4, 4, 609. |
| 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) | 28559 | m-Anisic acid; 3-Methoxybenzoic acid | 586-38-9 | C8H8O3 | 详情 | 详情 |
| (II) | 17819 | 2-bromo-5-methoxybenzoic acid | 22921-68-2 | C8H7BrO3 | 详情 | 详情 |
| (III) | 30443 | 3-chlorophenylhydrosulfide; 3-chlorobenzenethiol | 2037-31-2 | C6H5ClS | 详情 | 详情 |
| (IV) | 30444 | 2-[(3-chlorophenyl)sulfanyl]-5-methoxybenzoic acid | C14H11ClO3S | 详情 | 详情 | |
| (V) | 30445 | 1-chloro-7-methoxy-9H-thioxanthen-9-one | C14H9ClO2S | 详情 | 详情 | |
| (VI) | 12420 | N-(2-Aminoethyl)-N,N-diethylamine; N,N-Diethylethylene-diamine; N(1),N(1)-Diethyl-1,2-ethanediamine | 100-36-7 | C6H16N2 | 详情 | 详情 |
| (VII) | 30446 | 1-[[2-(diethylamino)ethyl]amino]-7-methoxy-9H-thioxanthen-9-one | C20H24N2O2S | 详情 | 详情 | |
| (VIII) | 30447 | 1-[[2-(diethylamino)ethyl]amino]-4-(hydroxymethyl)-7-methoxy-9H-thioxanthen-9-one | C21H26N2O3S | 详情 | 详情 | |
| (IX) | 30448 | 1-[[2-(diethylamino)ethyl]amino]-7-methoxy-9-oxo-9H-thioxanthene-4-carbaldehyde | C21H24N2O3S | 详情 | 详情 |