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Synthesis of Aromatic Aldehydes and Carboxylic Acids by the Oxidations of Polyaromatic Hydrocarbons

多环芳烃氧化合成芳香醛和羧酸

基本信息

批准号：
02453090
负责人：
NIKI Etsuo
金额：
$ 3.46万
依托单位：
Research Center for Advanced Science and Technology, The University of Tokyo.
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1990
资助国家：
日本
起止时间：
1990 至 1991
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-02453090/
关键词：
polyaromatic hydrocarbons oxidation aldehyde ketone alcohol エンドペルオキシド

项目摘要

This study has been carried out aiming at the syntheses of oxygenated products such as aldehydes, ketones, alcohols and carboxylic acids by the oxidations of polyaromatic compounds. Specifically, the photooxidation of 2, 6-dialkylnaphthalenes was extensively studied.Photobromination of side-chain methyl groups on arenes with N-bromosuccinimide was carried out in various solvents at ambient temperatures under nitrogen. Visible light irradiation in benzene solvent was extremely effective in increasing the selectivity of the reaction and the efficiency for product purification. The photobromination of 1, 4-, 1.8-, 2, 3- and 2, 6-dimethyinaphthalenes, 4, 4'dimethylbiphenyl, and p-xylens with 2, 2 mol equivalents of N-bromosuccinimide quantitatively afforded the corresponding bis(bromomethyl)arenes, respectively. The(bromomethyl)-methylarenes were also obtained in good yields in the photobromination reactions of the above dimethylarenes with 1.1 mol equivalents of N-bromosuccinimide. The hydrolysis of 2-bromo-6-methylnaphthalene and 2, 6bis(bromomethyl)naphthalene gave 2-hydroxymethyl-6-methylnaphthalene and 2, 6-bis(hydroxy methyl)naphthalene respectively in good yields.2, 6-Dialkylnaphthalenes were partially and selectively hydrogenated to yield corresponding 2, 6dialkyltetrahydronaphthalenes. The oxidations of these compounds by molecular oxygen with cobalt, manganese and bromide as catalysts gave mixtures of products. The oxidation of phenylcyclohexane has been also studied. It gave methylbenzoate as a major product together with dimethyl esters of glutafic acid and succinic acid.

本研究针对多芳香族化合物氧化合成醛、酮、醇、羧酸等含氧产物进行了研究。特别是2,6 -二烷基萘的光氧化反应进行了广泛的研究。在不同溶剂条件下，以氮为溶剂，进行了芳烃侧链甲基与n -溴琥珀酰亚胺的光溴化反应。在苯溶剂中可见光照射对提高反应的选择性和产物的纯化效率非常有效。1,4 -、1.8-、2,3 -和2,6 -二甲基萘、4,4 '二甲基联苯和对二甲苯与2,2 mol当量的n -溴琥珀酰亚胺进行光溴化反应，定量地得到相应的双（溴乙基）芳烃。上述二甲基芳烃与1.1 mol当量的n -溴代琥珀酰亚胺进行光溴化反应，也得到了产率较高的（溴乙基）甲基芳烃。2-溴-6-甲基萘和2,6 -二（溴乙基）萘水解得到2-羟甲基-6-甲基萘和2,6 -二（羟基甲基）萘。2,6 -二烷基萘经部分选择性氢化反应生成相应的2,6二烷基四氢萘。分子氧以钴、锰和溴化物为催化剂氧化这些化合物，得到混合物。还研究了苯基环己烷的氧化反应。它与谷氨酸二甲酯和琥珀酸二甲酯一起生产出主要的苯甲酯。