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Development of One-Step Synthetic Process of Phenol form Benzene

苯酚一步合成工艺的开发

基本信息

批准号：
04555208
负责人：
FUJIWARA Yuzo
金额：
$ 2.5万
依托单位：
HIROSHIMA UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Developmental Scientific Research (B)
财政年份：
1992
资助国家：
日本
起止时间：
1992 至 1993
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-04555208/
关键词：
One-step Phenol Synthesis Oxidation of Benzene Pd(OAc)_2 phen CO Catalysts Phenanthroline C-H Bond Activation Homogeneous Catalyst Phenol from Benzene Carbon Monoxide パラジウム触媒フェナントロリン CO O_2混合ガス O_2 CO系によるベンゼンの酸化酢酸パラジウム

项目摘要

Our research on this project has developed the high possibility of industrialization of our new phenol synthetic process.1. Palladium CatalystsThe Pd(OAc)_2/phen/O_2/CO system gives phenol in 1270% yield based on Pd with 91% selectivity. Pd(acac)_2, Pd-black, Pd-carbon are also good catalysts. Without CO, the phenol yield reaches to 50000% but the selectivity decreases to 56%.2. MechanismBy ^<18>O isotope experiments, it has been confirmed that the O atom of phenol comes from O_2, and that the another O atom of O_2 is accepted by CO to give CO_2.3. Substitution of CO with Other ReductantsAlthough CO increases the phenol selectivity, four equivalents of CO_2 are formed per one mole of phenol. Thus, other reductants rather than CO were tested to find that addition of n-methylmorphorine to the Pd(OAc)_2/phen/O_2 system gives phenol in 4060% yield with 91% selectivity, and that the Pd(OAc)_2/O_2/hexafluoroacetylacetone or bipyrizylmethane systems give phenol selectively in 830 and 950% yields, respectively.In summary, the Pd/phen/CO/O_2, Pd/phen/n-methylmorphorine/O_2 and Pd/O_2/hexafluoroacetylacetone or bipyrizylmethane systems are newly developed for direct phenol synthesis from benzene, which have high possibility of industrialization in near future.

本项目的研究表明我们的苯酚合成新工艺具有较高的工业化可能性。 1．钯催化剂Pd(OAc)_2/phen/O_2/CO体系以Pd为基础，苯酚收率为1270%，选择性为91%。 Pd(acac)_2、Pd-black、Pd-carbon也是很好的催化剂。没有CO时，苯酚收率可达50000%，但选择性下降至56%。2．机理通过^<18>O同位素实验，证实苯酚的O原子来自于O_2，并且O_2的另一个O原子被CO接受，得到CO_2.3。用其他还原剂取代CO虽然CO提高了苯酚选择性，但每摩尔苯酚会形成4当量的CO_2。因此，测试了除CO之外的其他还原剂，发现将n-甲基吗啉添加到Pd(OAc)_2/phen/O_2体系中以4060%的产率和91%的选择性产生苯酚，并且Pd(OAc)_2/O_2/六氟乙酰丙酮或联吡啶甲烷体系以830%和950%的产率选择性地产生苯酚，综上所述，Pd/phen/CO/O_2、Pd/phen/n-甲基吗啉/O_2和Pd/O_2/六氟乙酰丙酮或联吡啶甲烷体系是新开发的用于苯直接合成苯酚的体系，在不久的将来具有很高的工业化可能性。