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Studies on Synthetic Organic Reactions Using Iodobenzene Dicarboxylate

碘苯二甲酸合成有机反应的研究

基本信息

批准号：
59870070
负责人：
TAMURA Yasumitsu
金额：
$ 1.86万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Developmental Scientific Research
财政年份：
1984
资助国家：
日本
起止时间：
1984 至 1985
项目状态：
已结题

项目摘要

Thallium(III), mercury(II) and lead(IV) salts are very useful reagents in organic syntheses. However, the reactions using these metalic salts are unsuitable for industrial production because of high toxicity of these reagents. We have found that the following reactions(1-4) can be carried out using iodobenzene dicarboxylate (PhI(OCOR)2' 1) in place of the above reagents.1) The 1,2-aryl migration of 3-aroylpropionic acid to 2-arylsuccinate was effected by using iodobenzene diacetate(la). The migration was successfully applied to the preparation of 2-arylsuccinic acid which is important synthetic intermediate for indan-1-carboxylic acid possessing antiinflammatory activity.2) The short and efficient conversion of ethynylcarbinol groups into dihydroxyacetone groups was achieved by using iodobenzene ditrifluoroacetate (lb). The conversion was successfully applied to the syntheses of dihydroxyacetone side chains of adriamycin(antitumor agent) and cortico steroid(antiinflammatory agent).3) Treatment of <alpha> -acylsulfides with the reagent lb gave the same products as obtained by the Pummerer reaction of <alpha> -acylsulfoxides. The reaction was successfully applied to the carbon-carbon bond forming reactions such as Friedel-Crafts type cyclization and olefin cyclization.4) The reaction of <beta> -substituted <alpha> , <beta> -unsaturated carbonyl compound with the reagent la under basic reaction conditions gave <alpha> '-hydroxy- <alpha> , <beta> -unsaturated carbonyl compound. The same reaction of <beta> -nonsubstituted <alpha> , <beta> -unsaturated carbonyl compound afforded <alpha> -hydroxy- <beta> -methoxydimethylacetal compound.5) In the above reactions(1-4), the reagent 1 was recovered as iodobenzene, which was successfully converted into the reagent 1 through iodobenzene dichloride. Consequently, the reagent 1 can be recycled.

铊（III）、汞（II）和铅（IV）盐在有机合成中是非常有用的试剂。然而，使用这些金属盐的反应由于这些试剂的高毒性而不适合于工业生产。我们已经发现，使用二羧酸碘苯（PhI（OCOR）2 ′ 1）代替上述试剂可以进行下列反应（1-4）. 1）通过使用二乙酸碘苯（1a）实现3-芳酰基丙酸向2-芳基琥珀酸酯的1，2-芳基迁移.该迁移反应成功地应用于2-芳基丁二酸的制备，该丁二酸是合成茚满-1-羧酸的重要中间体，具有良好的催化活性。2）以二（三氟乙酸）碘苯（Ib）为催化剂，实现了乙炔基甲醇向二羟基丙酮的快速高效转化。该转化成功地应用于抗肿瘤药物阿霉素和抗肿瘤药物皮质类固醇的二羟基丙酮侧链的合成。3）<alpha>用试剂lb处理-酰基硫醚得到与-酰基亚砜的Pummerer反应相同的产物<alpha>。该反应成功地应用于Friedel-Crafts型环化反应和烯烃环化反应等碳-碳键形成反应。4）α<beta>-取代，<alpha>β<beta>-不饱和羰基化合物与试剂Ia在碱性条件下反应，得到<alpha>β-羟基-<alpha>，β<beta>-不饱和羰基化合物。5<beta><alpha><beta><alpha><beta>）在上述反应（1-4）中，试剂1以碘苯的形式回收，碘苯通过二氯化碘苯成功地转化为试剂1。因此，试剂1可以再循环。