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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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除了上述几页提及的以外，还有几篇专述乃至期刊文章论及有机合成的进展(72-85)。本作者们介绍了在下文列举的有机化学反应中使用离子液体的最新进展，先前的评论者从未涉及过这些内容。本文还包括了作者们在绿色化学领域内自己的研究成果. 醛醇缩合反应. 诺文葛耳反应 . 迈克尔加成反应 醛醇缩合反应 对于这种方法，在产生有机化学反应的碳-碳键中间，醛醇缩合反应（图1）是最受欢迎的；这是由Charles - Adolphe Wurtz和A. P. Borodin于 1872年各自独立地发现的，因而具有悠久的历史(86-88)。 醛醇经脱水得到叫做查耳酮的α，β-不饱和酮，这被称为克来森施密特反应。在这两个反应中，本作者们在寻找更环保的方法／工艺过程中开发了Al(III)和Bi(III)的应用。然而，离子液体在这种反应中的应用却是最新的热点，以下予以论述。 诺文葛耳反应这种反应代表了碳-碳双键生产的一种有效方法，是1894年后由诺文葛耳（101-103）发现的。这种普通的诺文葛耳反应（图２）已在几篇综述文章和专题论文中有过报道，然而离子液体在这种反应中的应用却是近来才提到的。 在绿色化学方法的研究中，我们为开发无溶剂的以及LiBr、CdI2 BiCl3 KI、Alum等温和的路易氏酸催化剂做出很大努力（104-108）。很明显，与先前报导的使用强路易斯酸或强有机碱的方法相比，这些是更温和的方法。 毫无疑问，离子液体在这些反应中的应用具有现时意义，以下详述研究进展。 迈克尔加成反应这种反应发现于1883年，统一以Arthur Michael命名（143-145）。 这种反应在普通化学中与诺文葛耳反应非常相似，在这两种反应中，使用同样的溶剂和催化剂，报导过大量的研究工作，两者似乎具有互补性。 确切地说诺文葛耳是1-2位，迈克尔是1-４位的共轭加成（图5）至羰基上，并且分别都是缺电子的链烯。为了寻求绿色化学方法,在此，作者们还在无溶剂条件下对使用无污染催化剂并取代挥发性有机溶剂(VOC)的环保方案的提出做出了很大贡献。 本作者们已报导过诸如BiCl3、Cu ( II)、氧化铝等催化剂（146-151），而且更多地报导了为得到无溶剂的温和的催化剂所作的努力。 本文在此介绍离子液体作为本方法的溶剂应用以及它们的最新进展。 |
2楼2014-03-12 12:39:14
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