Functionalization of Methylaromatic Hydrocarbons

甲基芳烃的官能化

• 批准号: 03650668
• 负责人: FUTAMURA Shigeru
• 金额: $ 1.02万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03650668/
• 关键词: Dimethylaromatic hydrocarbons; Photobromination; Bis(bromomethyl)aromatics; Hydrolysis; Bis(hydroxymethyl)aromatics; Tetrabutylammonium periodate; Oxidation; Aromatic dialdehydes; メチル芳香族炭化水素; 照射光の波長の影響; 溶媒効果; (ブロモメチル)メチル芳香族化合物

Functionalization of dimethylaromatic hydrocarbons such as 1,4-, 1,8-, 2,3- and 2,6-dimethylnaphtalenes, 4,4' -dimethylbiphenyl and p-xylene was investigated in order to aim at highly selective and convenient syntheses of1) bis(bromomethyl)aromatics, 2) bis(hydroxymethyl)aromatics and 3) aromatic dialdehydes.In the synthesis of bis(bromomethyl)aromatics from dimethylaromatic hydrocarbons, visible light irradiation in benzene with N-bromosuccinimide as brominating agent was greatly effective in increasing selectivities of the bis(bromomethyl)aromatics and efficiency of product purification.Bis(hydroxymethyl)aromatics were produced in good yields by refluxing the bis(bromomethyl)aromatics in strongly basic water in the presence of a phase transfer catalyst like triethylbenzylammonium bromide, whose chemical affinity with the bis(bromomethyl)aromatics could be expected to be high.Aromatic dialdehydes were produced in good yields in the tetrabutylammonium periodate oxidation of the bis(bromomethyl)aromatics in dioxane. In order to achieve high selectivities of the dialdehydes, it was necessary to add 2.2 mol equivalents of tetrabutylammonium periodate and a bromine trap like anthracene.The synthetic methods described above are of significance since bis(hydroxymethyl)aromatics and aromatic dialdehydes cannot be synthesized by direct oxidation of dimethylaromatic hydrocarbons.

本文研究了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等二甲基芳烃的功能化反应，旨在高选择性和方便地合成1）双（溴甲基）芳烃，2）双（羟甲基）芳族化合物和3）芳族二醛。在双（羟甲基）芳族化合物的合成中，来自二甲基芳族烃的（溴甲基）芳族化合物，以N-溴代丁二酰亚胺为溴化剂，在可见光照射下，（溴甲基）芳族化合物和产品纯化效率的影响。双羟甲基芳烃的收率较高，（溴甲基）芳族化合物在强碱性水中在相转移催化剂如三乙基苄基溴化铵的存在下，其与双（溴甲基）芳香族化合物的化学亲合性很高，在二氧六环中，高碘酸四丁基铵氧化双（溴甲基）芳香族化合物以良好的产率生成芳香二醛。为了获得高的二醛选择性，需要加入2.2mol当量的四丁基高碘酸铵和类似蒽的溴捕集剂，上述合成方法具有重要意义，因为二甲基芳烃不能直接氧化合成双（羟甲基）芳烃和芳香二醛。

项目成果

Shigeru FUTAMURA and Zhi-Min zong: "Photobromination of Side-chain Methyl Groups on Arenes with N-Bromosuccininide" Bull.Chlm.Soc.Jpn.65. 345-348 (1992)

Shigeru FUTAMURA 和zhi-min zong：“用 N-溴代琥珀酰亚胺对芳烃上的侧链甲基进行光溴化”Bull.Chlm.Soc.Jpn.65。

Shigeru Futamura and ZhiーMin Zong: "Photobromination of SideーChain Methyl Groups on Arenes with NーBromosuccinimide" Bull.Chem.Soc.Jpn.65. 345-348 (1992)

Shigeru Futamura 和zhi-min zong：“用 N-溴代琥珀酰亚胺对芳烃上的侧链甲基进行光溴化”Bull.Chem.Soc.Jpn.65 (1992)。

Shigeru Futamura,and Zhi-Min Zong: "Photobromination of Side-Chain Methyl Groups on Arenes with N-Bromosucainimide" Bull.Chem.Soc.Jpn.65. 345-348 (1992)

Shigeru Futamura 和zhi-min zong：“用 N-溴代琥珀酰亚胺对芳烃上的侧链甲基进行光溴化”Bull.Chem.Soc.Jpn.65。

Shigeru Futamura: "Selective Synthesis of Aromatic Dialdehydes from Bis(bromomethyl) aueues with Tetrabutyl ammonium Periodate Oxidation." Bull.Chem.Soc.Jpn.

Shigeru Futamura：“用四丁基高碘酸铵氧化从双（溴甲基）水选择性合成芳香族二醛。”

Shigeru Futamura and Zhi-Min Zong: "Photobromination of Side-Chain Methyl Groups with N-Bromosuccinimide" Bull. Chem. Soc. Jpn.65-2. 345-348 (1992)

Shigeru Futamura 和zhi-min zong：“用 N-溴代琥珀酰亚胺对侧链甲基进行光溴化”公报。