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问题:翻译一段话
类型:求助 (悬赏分:3分)
提问:quick208
等级:
版块:有机化学问题(jimuwei,fpcwin1211,netpanda,yjgzfl,Ftian,)
信誉:95%
回复:3
阅读:893
时间:2008-06-29 09:48:53  编辑    加入/取消收藏    订制/取消短消息    举报该贴    

In this research, the reductive amination was attempted first
with magnesium in methanol, ethanol or an alcohol-acetic acid
mixture, where no reduction occurred, except for hydrogen
evolution. Then, various buffering systems were examined,
including potassium acetate-acetic acid, sodium hydrogen
carbonate (with tetrabutylammonium chloride), potassium
hydrogen carbonate/ 18-crown-6 or sodium dihydrogen phos-
phate, without success. However, when triethylammonium
acetate was used (prepared in situ from triethylamine and acetic
acid), reductive amination proceeded smoothly. Best results
were obtained with 3 equiv. of triethylammonium acetate, with
additional acetic acid added portionwise to the reaction
mixture, as indicated in Scheme 1. The reaction is completed
in 12-24 h at room temperature, compared to 4-6 h in boiling
methanol. Interestingly, when trimethylammonium acetate was
used, poor yields were observed, regardless of the temperature,
probably because of the high volatility of trimethylamine. The
pH of the reaction mixture is of crucial importance. If the pH is
< ca. 7, hydrogen evolution becomes predominant, while at a
pH >9-10, the reduction does not proceed. This may be
explained in terms of the reaction mechanism. Since the species
which actually undergo reduction is the protonated imine
(immonium ion), its concentration must be considerable in the
reaction medium, which is the case at pH 7-9.
谢谢,英语不学不行啊!
回复人:cpujacs, (我爱我老婆) 时间:2008-06-29 16:02:51   编辑 1楼
在这方面的研究,首先尝试镁在甲醇,乙醇或酒精-乙酸混合物中还原胺,没有发生还原反应,只有氢气放出。随后研究各种缓冲系统下的情况, 包括醋酸钾-乙酸,碳酸氢钠(四丁基氯化铵),碳酸氢钾/18-冠-6或磷酸二氢钠,均没有成功。然而,当使用三乙胺的醋酸盐时(准备由三乙胺和醋酸酸) ,还原胺化进行的很温和。获得最好的结果是3当量的三乙胺的醋酸盐。额外的乙酸加入反应溶液中,如Scheme 1中显示。室温反应12-24小时完成。有趣的是,当使用三乙基醋酸盐时发现收率较低, 可能是温度过高三乙胺挥发的缘故。同时pH值对反应是至关重要的。如果pH值<7时,产生氢气成为主导,而在pH> 9-10时,还原反应不进行。这可以解释反应的机理。由于发生还原反应的物质实际上是质子化的亚胺(亚胺离子),pH值7-9时,其浓度在反应介质很大。


回复人:quick208, (以父之名) 时间:2008-06-29 16:09:18   编辑 2楼
已经打分了!


回复人:david_zhan,★★ () 时间:2008-06-29 16:36:24   编辑 3楼
在本研究中,最初尝试以镁的甲醇、乙醇以及醇和醋酸的混合物还原胺,除了生成氢气外,反应并没有发生。后来,试验了几种不同的缓冲体系,包括醋酸钾/醋酸,碳酸氢钠(加有四丁基氯化铵), 碳酸氢钾/18-冠-6,磷酸二氢钾等体系也没有取得成功。但是当使用三乙胺醋酸盐时(以三乙胺和醋酸反应制得), 亚胺还原顺利进行。 采用3倍当量的三乙胺醋酸盐、醋酸溶液滴加到反应混合物中,得到了最佳的结果,正如例1中中演示。反应在室温下进行12-24小时结束,相比较在沸腾的甲醇中反应4-6小时结束。有意思的是,使用三乙胺醋酸盐时,不管温度如何,收率都比较低,可能是由于三乙胺较易挥发造成的。反应混合物的PH值也是至关重要的,当 pH <7时,氢气生成占据主要地位,当pH >9-10时, 还原不会发生。这可以通过反应机理进行解释:因为真正发生反应的是质子化的亚胺(亚胺离子),在反应介质中的浓度必须得到考虑,在本例中在pH 7-9时为最佳浓度.


得分人:cpujacs :3,


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