摘要:在分子中酮酸这种化合物能够同时含有羧基和酮基两种基团。酮酸的品种可以 分为三种分别为α β γ-酮酸,其辨别依据为分子中羧基和酮基的相对位置。α β这两类酮酸是人体内蛋白质代谢、糖类和脂肪的中间产物。同时酮酸也是一类在 人体和动物体内起着无足轻重的有机酸,在氨基酸推陈出新和维持氧化还原状态的 行程中起着一个中心的感化。β-酮酸是高能量的(不稳定的)代谢物,它可以失 去羧基同时释放能量促进其它反应进行(脱羧)。β-酮酸的两个羧基之间还隔着 一个碳原子。β-酮酸非常不稳定,它会自愿脱掉羧基,在细胞中这个过程通过 Lewis 酸催化剂的作用发生的,比如在糖异生过程中草酰乙酸的脱羧。最重要的是β-酮 酸可以作为有吸引力的酮的比较优秀的替代物。从化学性质上看 :酮酸分子中含有 羧基和酮基两种官能团,因此它既有羧酸的性质,如成盐和成酯等;又有酮的典型 反应,如与羟胺反应和加氢还原等。此外,鉴于两种官能团的相互影响,酮酸还有 一些特殊性质,如β-酮酸很容易脱羧等。β-酮酸的分解有两种形式:一种是酮 式分解,乙酰乙酸乙酯(又叫β-丁酮酸乙酯,简称三乙),及其取代衍生物与稀碱 作用,水解生成β-羰基酸,受热后脱羧生成甲基酮。故称为酮式分解。另一种是 酸式分解,乙酰乙酸乙酯及其取代衍生物在浓碱作用下,主要发生乙酰基的断裂, 生成乙酸或取代乙酸,故称为酸式分解。在本文中报道了β-酮酸与一系列底物之 间的加成反应研究,其中包括环状亚胺,对甲基苯醌类,香豆素衍生物等底物的合 成与表征,各种亲核试剂,Lewis 酸催化剂,三氟甲磺酸镱催化剂以及反应条件的摸 索与筛选,加成产物的合成与表征;β-酮酸,一系列底物及其加成产物的结构都 经过 1H NMR,MS 进行了表征。
关键词:β-酮酸;亲核试剂;Lewis 酸催化剂;三氟甲磺酸镱;脱羧反应;加成 反应
Abstract:The compounds in the molecule can contain both carboxyl and ketone groups at the same time. The varieties of keto acids can be pided into three kinds of α β γ -keto acids, which are based on the relative position of carboxyl and ketone groups in the molecule. Α β These two types of keto is the body of protein metabolism, sugar and fat intermediates. At the same time keto acid is also a class in the human body and animal body plays an important organic acid, in the amino acid and maintain the redox state of the trip plays a central role. Β-keto acid is a high-energy (unstable) metabolite that can lose the carboxyl group while releasing energy to promote other reactions (decarboxylation). The two carboxyl groups of β - keto acid are also separated by a carbon atom. β-keto acid is very unstable, it will voluntarily take off the carboxyl, in the cell this process through the role of Lewis acid catalyst occurs, such as sugar in the process of glucoacetic acid decarboxylation. The most important is that β- ketoacetic acid can be used as an attractive substitute for attractive ketones. From the chemical point of view: keto acid molecules contain both carboxyl and ketone functional groups, so it has both the nature of carboxylic acids, such as salt and ester, etc and ketone typical reaction, such as reaction with hydroxylamine and hydrogenation Restore and so on. In addition, due to the interaction of the two functional groups, keto acid has some special properties, such as β-keto acid is easy to decarboxylation and so on. There are two forms of β - keto acid decomposition: one is ketone decomposition, ethyl acetoacetate (also known as ethyl β - butyrate, referred to as tri-B), and its substituted derivatives with dilute alkali, hydrolysis Β- carbonyl acid, hedecarboxylation to produce methyl ketone. It is called ketone decomposition. The other is acid decomposition, ethyl acetoacetate and its substituted derivatives in the role of concentrated alkali, the main occurrence of acetylation of the broken, the formation of acetic acid or acetic acid, it is called acid decomposition. In this paper, we report the addition reaction between β - keto acid and a series of substrates, including the synthesis and characterization of cyclic imines, p - methylbenzoquinones and coumarin derivatives. The synthesis and characterization of the addition products of β - keto acid, a series of substrates and their addition products have been carried out. The structure and characterization of β-keto acid, a series of substrates and their addition products have been studied. 1H NMR, MS were