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Apart from the areas mentioned in the forgoing pages there are special reviews and even journals devoted to developments in organic synthesis (72-85). The authors are presenting the latest developments using ILs in the following named reactions of organic chemistry, which has never been done by previous reviewers exclusively. This paper also includes the authors’ own work in the area of green chemistry . Aldol reaction . Knoevenagel reaction . Michael reaction Aldol reaction Among carbon-carbon bond forming reactions in organic chemistry, the Aldol reaction (Scheme 1) is the most popular for this process; it was discovered by Charles-Adolphe Wurtz and A. P. Borodin independently in 1872 and thus have a long history (8688). Aldol, when dehydrates, yields ab-unsaturated ketones called chalcones and is known as the ClaisenSchmidt reaction. In both these reactions the present authors, while looking for greener procedures/processes, have developed the use of Al(III) and Bi(III) (89). However, the use of ILs in this reaction is of latest interest and is discussed below. Knoevenagel reaction This reaction represents an efficient way of producing carbon-carbon double bonds and was discovered back in 1894 by Knoevenagel (101103). The conventional Knoevenagel reaction (Scheme 2) has been reported in several reviews and monographs; however, the use of ILs in this reaction is recent. In the pursuit of developing green chemistry we did make considerable efforts for solvent free and also milder Lewis acids catalysts developments such as LiBr, CdI2, BiCl3, KI, Alum (104108), and so on. Evidently, these were milder processes than the earlier reported ones employing strong Lewis acids or strong organic bases. No doubt that ILs are of current interest for use in this reaction and developments are given below. Michael reaction The discovery of this reaction dates back to 1883; it was generalized by and named after Arthur Michael (143145). The reaction is very similar to the Knoevenagel reaction and in conventional chemistry, in both the reactions, similar solvents and catalysts have been employed and volumous research work reported and both seem complementary to each other. Precisely, Knoevenagel is 1-2 and Michael is 1-4 conjugate addition (Scheme 5) on to carbonyl and electron deficient alkenes, respectively. In pursuit of green chemistry, here also the authors made considerable contributions in developing some environmentally benign protocols using non-polluting catalysts and replacing volatile organic solvents (VOCs) under solvent-free conditions. Already reported by the authors are catalysts like BiCl3, Cu(II), alumina, and so on (146151), efforts to obtain solvent-free mild catalyst are much reported by the authors. ILs being solvents of the present, their recent progress is given here. |
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jiangguofeng
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xiaotian113: 金幣+200, 翻譯EPI+1, ★★★★★最佳答案, 很好！ 2014-03-12 13:12:08
xiaotian113: 金幣+200, 翻譯EPI+1, ★★★★★最佳答案, 很好！ 2014-03-12 13:12:08
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除了上述幾頁(yè)提及的以外，還有幾篇專述乃至期刊文章論及有機(jī)合成的進(jìn)展(72-85)。本作者們介紹了在下文列舉的有機(jī)化學(xué)反應(yīng)中使用離子液體的最新進(jìn)展，先前的評(píng)論者從未涉及過(guò)這些內(nèi)容。本文還包括了作者們?cè)诰G色化學(xué)領(lǐng)域內(nèi)自己的研究成果. 醛醇縮合反應(yīng). 諾文葛耳反應(yīng) . 邁克爾加成反應(yīng) 醛醇縮合反應(yīng) 對(duì)于這種方法，在產(chǎn)生有機(jī)化學(xué)反應(yīng)的碳-碳鍵中間，醛醇縮合反應(yīng)（圖1）是最受歡迎的；這是由Charles - Adolphe Wurtz和A. P. Borodin于 1872年各自獨(dú)立地發(fā)現(xiàn)的，因而具有悠久的歷史(86-88)。 醛醇經(jīng)脫水得到叫做查耳酮的α，β-不飽和酮，這被稱為克來(lái)森施密特反應(yīng)。在這兩個(gè)反應(yīng)中，本作者們?cè)趯ふ腋h(huán)保的方法／工藝過(guò)程中開(kāi)發(fā)了Al(III)和Bi(III)的應(yīng)用。然而，離子液體在這種反應(yīng)中的應(yīng)用卻是最新的熱點(diǎn)，以下予以論述。 諾文葛耳反應(yīng)這種反應(yīng)代表了碳-碳雙鍵生產(chǎn)的一種有效方法，是1894年后由諾文葛耳（101-103）發(fā)現(xiàn)的。這種普通的諾文葛耳反應(yīng)（圖２）已在幾篇綜述文章和專題論文中有過(guò)報(bào)道，然而離子液體在這種反應(yīng)中的應(yīng)用卻是近來(lái)才提到的。 在綠色化學(xué)方法的研究中，我們?yōu)殚_(kāi)發(fā)無(wú)溶劑的以及LiBr、CdI2 BiCl3 KI、Alum等溫和的路易氏酸催化劑做出很大努力（104-108）。很明顯，與先前報(bào)導(dǎo)的使用強(qiáng)路易斯酸或強(qiáng)有機(jī)堿的方法相比，這些是更溫和的方法。 毫無(wú)疑問(wèn)，離子液體在這些反應(yīng)中的應(yīng)用具有現(xiàn)時(shí)意義，以下詳述研究進(jìn)展。 邁克爾加成反應(yīng)這種反應(yīng)發(fā)現(xiàn)于1883年，統(tǒng)一以Arthur Michael命名（143-145）。 這種反應(yīng)在普通化學(xué)中與諾文葛耳反應(yīng)非常相似，在這兩種反應(yīng)中，使用同樣的溶劑和催化劑，報(bào)導(dǎo)過(guò)大量的研究工作，兩者似乎具有互補(bǔ)性。 確切地說(shuō)諾文葛耳是1-2位，邁克爾是1-４位的共軛加成（圖5）至羰基上，并且分別都是缺電子的鏈烯。為了尋求綠色化學(xué)方法,在此，作者們還在無(wú)溶劑條件下對(duì)使用無(wú)污染催化劑并取代揮發(fā)性有機(jī)溶劑(VOC)的環(huán)保方案的提出做出了很大貢獻(xiàn)。 本作者們已報(bào)導(dǎo)過(guò)諸如BiCl3、Cu ( II)、氧化鋁等催化劑（146-151），而且更多地報(bào)導(dǎo)了為得到無(wú)溶劑的溫和的催化劑所作的努力。 本文在此介紹離子液體作為本方法的溶劑應(yīng)用以及它們的最新進(jìn)展。 |
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