Synthesis of Heterocyclic Compounds in Water or Alcohol

水或醇中杂环化合物的合成

• 批准号: 10650851
• 负责人: SAIMOTO Hiroyuki
• 金额: $ 1.28万
• 依托单位: Tottori University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10650851/
• 关键词: Water; Alcohol; Phenol; Metal salt; Metal hydroxide; Glyoxal; Benzopyran; Addition-cyclization reaction

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

1.酚烯醇酯与α， β-不饱和化合物反应合成2h -1-苯并吡喃。该序列成功应用于抗菌物质2,2 -二甲基- 2h -1-苯并吡喃-6-羧酸，β-管酸的合成(2)。由于在吡啶中进行的传统方法和最近的方法都不能将1转化为所需的2的甲酯，因此本方法在水介质中为这种化合物的制备提供了一种方便的一锅方法。在水介质中有机合成已成为当前关注的主要问题之一，并且通常消除了惰性气氛和无水条件的限制。基于发现的aldol-type反应的甲基酚烯醇化物2,4-dihydroxybenzoate与醛类(1)甲醇完成使用碱土金属试剂如Ca (OH)ィイD22摊位ィエD2, Ba (OH)ィイD22摊位ィエD2, CaCィイD22摊位ィエD2 / KOH,或BaClィイD22摊位ィエD2 / KOH代替碱性金属试剂如氢氧化钠、KO ... 更多的H、氯化锂/ KOH或生理盐水/ KOH,我们应用钙试剂与α酚烯醇化物的反应,β-不饱和醛或酮类化合物。我们发现2的反应,4-dihydroxybenzenecarbonyl与乙烯基酮化合物HィイD22摊位ィエD24-O /甲醇给相应的1,4-adducts和丙烯醛的反应或methacrolein提供3 4-dihydro-2H-benzopyranes在一个锅里。在一个prenyl-type醛,1的亲核反应进行加法的方式和连续dehydrative环合锅2的形成提供了一种新的方法,2-disubstituted 2 h-benzopyran衍生品。C-C键的形成是在苯甲酸酯的C(3)位置进行区域选择性的。苯酚烯醇酯与1,2 -二羰基化合物反应合成苯并呋喃1和乙二醛在水中用KOH反应得到2,3 -二氢- 2,3,4 -三羟基苯并呋喃-6-羧酸甲酯，产率为77%，而在H / 2o /MeOH（1/15）反应得到2,4 -二羟基-3-（2-羟基乙酰）苯甲酸甲酯，产率较低

项目成果

H. Saimoto: "Synthesis of Enantiomerically Enriched 2,5-Dihydrofuran Derivatives from Easily Available Enantiomerically 2-Butyne-1,4-diols by Stereospecific Transformation"Bull. Chem. Soc. Jpn.. 72・2. 279-284 (1999)

H. Saimoto：“通过立体定向转化从容易获得的对映体 2,5-二氢呋喃衍生物合成”，Soc. 279-284。 ）

H.Saimoto: "Synthesis of Enantiomerically Enriched 2,5-Dihydrofuran Derivatives from Easily Avairable Enantiomerically Enriched 2-Butyne-1,4-diols by Stereospecific Transformation"Bull.Chem.Soc.Jpn.. 72・2. 279-284 (1999)

H.Saimoto：“通过立体定向转化从容易获得的对映体富集的 2-丁炔-1,4-二醇合成对映体富集的 2,5-二氢呋喃衍生物”Bull.Chem.Soc.Jpn.. 72・2. 1999）

H.Saimoto: "Synthesis of Enantiomerically Enriched 2, 5-Dihydrofuran Derivatives from Easily Available Enantiomerically Enriched 2-Butyn-1, 4-diols by Stereospecific Transformation"Bull. Chem. Soc. Jpn.. 72-2. 279-284 (1999)

H.Saimoto：“通过立体特异性转化从容易获得的对映体富集的 2-Butyn-1, 4-二醇合成对映体富集的 2, 5-二氢呋喃衍生物”Bull。

H.Saimoto: "Synthesis of Enantiomerically Enriched 2,5-Dihydrofuran Derivatives from Easily Avairable Enantiomerically Enriched 2-Butyne-1,4-diols by Stereospecific Transformation" Bull.Chem.Soc.Jpn.72・2. 279-284 (1999)

H. Saimoto：“通过立体定向转化从容易获得的对映体富集的 2-丁炔-1,4-二醇合成对映体富集的 2,5-二氢呋喃衍生物”Bull.Chem.Soc.Jpn.72・2. ）