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ky888银虫 (正式写手)
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[求助]
帮忙翻译下 吧 谢谢啦
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According to retro-synthetic analyses and the literature, 2,6 both methyl 2-oxo-2-arylacetate and methyl 2- hydroxyimino-2-arylacetate 2 are the key intermediates of the analogues of strobilurins. Our initial goal was to develop a new method for synthesis of methyl 2- oxo-2-arylacetate in which the commercially available and cheap arylamines and glyoxylic acid were used as starting material based on previous literature.10,11 In our work, we first found that the coupling reaction between aryldiazonium salt derived from 2-methylaniline and methyl 2-(hydroxyimino)-acetate gave stereoselectively oxime 2 in 44% yield.12 The E/Z ratio determined in the crude mixture by 1H NMR spectroscopy was ca. 14:1. After further column chromatography purification, the purity of E-2 could exceed 99% in41% yield. The compound E-2 was methylated by sodium hydride-dimethyl sulfate in 91% yield and successively brominated with NBS to afford oxime ether 4 in 81% yield. |
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6楼2011-08-05 19:10:08
【答案】应助回帖
★ ★ ★
sltmac(金币+1): 鼓励交流~ 2011-08-05 18:55:54
8814402(金币+2): 努力应助,自然会有回报 2011-08-05 23:20:48
ky888(金币+10, 翻译EPI+1): 10 2011-08-07 00:43:39
sltmac(金币+1): 鼓励交流~ 2011-08-05 18:55:54
8814402(金币+2): 努力应助,自然会有回报 2011-08-05 23:20:48
ky888(金币+10, 翻译EPI+1): 10 2011-08-07 00:43:39
| 根据逆向合成分析以及文献[2,6],methyl 2-oxo-2-arylacetate和methyl 2-hydroxyimino-2-arylacetate[2]都是strobilurins类似物的中间体。我们原先的目标是希望利用可以通过商业途径获得的廉价的芳基胺和水合乙醛酸为起始原料开发一种新的合成methyl 2-oxo-2-arylacetate的合成方法,参考的文献为10,11.在我们的试验中,我们一开始就发现由2-methylaniline衍生得到的aryldiazonium盐与methyl 2-(hydroxyimino)-acetate之间的耦合反应可以得到具有立体异构选择性的肟【产物2】,产率为44%[12].利用1H NMR表征混合产物的E/Z比大约为14:1. 利用柱色谱进一步纯化之后,产物E-2的纯度达到99%,产率为41%。 产物E-2利用sodium hydride-dimethyl sulfate进行甲基化化反应之后产率为91%,然后继续使用NBS进行溴代反应之后得到oxime ether【产物 4】,产率为81%。 |
2楼2011-08-05 11:18:51
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sltmac(金币+1): 谢谢交流~ 2011-08-05 18:56:04
sltmac(金币+1): 谢谢交流~ 2011-08-05 18:56:04
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