Synthesis of Heterocyclic Compounds in Water or Alcohol

1.通过与α， β-不饱和化合物的反应的2 H-1-苯并吡烷的合成，这一序列成功地应用于抗生素2，2-二甲基-2 H-1-苯并吡烷-6-羧基、β-结核酸的合成。由于这两种常规和最近的方法都是在吡啶酶失败到转化1到理想的甲基酯的2中，在平等媒体中提供了方便和一罐程序，用于这种化合物的准备;有机合成在一个有机合成中成为当前兴趣的主要主题之一，在一般的限制中限制了自然大气层和非氢条件的约束。基于甲基2，4-二羟基苯并酸盐中的烷基型反应的研究结果（1）与甲基2，4-二羟基苯并酸盐（1）结合使用碱性地球金属试剂作为Ca（OH）的D22的D2， Ba（OH）的D22的D2，CaC-D22的D2/KOH，或BaCl-D22的D2/KOH instead of alkaline metal reagents作为NaOH， KO ... More H、LiCl/KOH或NaCl/KOH，我们在本研究中应用了一种钙催化剂用于苯氧化物与α、β-不饱和的醛或酮的反应。我们发现了含有2，4-二羟基苯基化合物的乙烯基酮的反应，即在HI-D22-O/MeOH中添加了相应的1，4-添加了1，4-添加的反应，并在一个罐子中含有含有丙烯酰胺或甲基丙烯酰胺的3，4-二氢-2 H-苯并烷。在一种戊二烯型醛的情况下，核反应在1，2-添加标记中进行，并为一种新的方法提供了一种新的方法，用于形成一个由2，2-分散的2 H-苯并烷衍生物。C-C键形成在苯并酯1.2的C（3）位置进行了区域性电形成，苯并呋喃与1，2-二碳烯基化合物反应的合成，在77%的yield中处理1和glyoxal与KOH在水中的2，3-二氢-2，3，4-三氢苯并呋喃-6-carboxylate的反应，当反应在一个罐子中排出时，D2 O/MeOH（1/15） gave methyl 2，4-dihydroxy-3-（2-hydroxyacetyl）benzoate。Less（低）

1.Synthesis of 2H-1-Benzopyrans by the Reaction of Phenolic Enolates with α, β-unsaturated CompoundsThis sequence was successfully applied to the synthesis of an antimicrobial 2, 2-dimethyl-2H-1-benzopyran-6-carboxilic acid, β-tubaic acid (2). Because both conventional and recent methods which were performed in pyridine failed to convert 1 into the desired methyl ester of 2, the present method in aqueous media provides a convenient and one-pot procedure for the preparation of this kind of compound.Organic syntheses in aqueous media have become one of the main topics of current interest and in general eliminate the constraints of inert atmosphere and anhydrous conditions. Based on the findings that the aldol-type reaction of phenolic enolate of methyl 2, 4-dihydroxybenzoate (1) with aldehydes in methanol was accomplished using alkaline earth metal reagents such as Ca(OH)ィイD22ィエD2, Ba(OH)ィイD22ィエD2, CaCィイD22ィエD2/KOH, or BaClィイD22ィエD2/KOH instead of alkaline metal reagents such as NaOH, KO … More H, LiCl/KOH or NaCl/KOH, we have applied the calcium reagent for the reaction of phenolic enolates with α, β-unsaturated aldehydes or ketones in this research. We found that the reaction of 2, 4-dihydroxybenzenecarbonyl compounds with vinyl ketones in HィイD22ィエD24-O/MeOH gave the corresponding 1, 4-adducts and that the reaction with acrolein or methacrolein afforded 3, 4-dihydro-2H-benzopyranes in one pot. In the case of an prenyl-type aldehyde, the nucleophilic reaction proceeded in 1, 2-addition manner, and successive dehydrative cyclization provided a new method for the one-pot formation of 2, 2-disubstituted 2H-benzopyran derivatives. The C-C bond formation was regioselectively performed at the C(3) position of benzoate 1.2.Synthesis of Benzofurans by the Reaction of Phenolic Enolates with 1, 2-Dicarbonyl CompoundsThe treatment of 1 and glyoxal with KOH in water afforded methyl 2, 3-dihydro-2, 3, 4-trihydroxybenzofuran-6-carboxilate in 77% yield, while the reaction carried out in HィイD22ィエD2O/MeOH(1/15) gave methyl 2, 4-dihydroxy-3-(2-hydroxyacetyl)benzoate in one pot. Less