一种双铁氢化酶配合物(μ-dmedt)Fe_(2)(CO)_(5)[Tricyclohexyl phosphine]的制备及其羟基化苯酚的性能的探究  

Preparation of a Diferric Hydrogenase Complex(μ-dmedt)Fe_(2)(CO)_(5)[Tricyclohexyl Phosphine]and Study on Its Hydroxylated Phenol Properties

作　　者：尹龙 张夏[2] Yin Long;Zhang Xia(Jinan Hebeier Health Products Co.,Ltd.,Jinan 250022,China;Advanced Research Institute for Multidisciplinary Science,Qilu University of Technology,Jinan 250022,China)

机构地区：[1]济南荷贝尔保健制品有限公司,山东济南250022 [2]齐鲁工业大学前沿交叉学科研究院,山东济南250022

出　　处：《山东化工》2023年第8期1-4,9,共5页Shandong Chemical Industry

基　　金：齐鲁工业大学博士科启动经费项目(81110361);生物基材料与绿色造纸国家重点实验室开放基金(ZZ20200129);山东省自然科学基金(ZR2020QB042)。

摘　　要：以五羰基铁、三环己基膦以及丁二硫醇类化合物为原料,制备了一种双铁氢化酶活性中心模拟化合物,并对其基本结构进行了研究;除此之外,还考察了以过氧化氢为氧化剂时其催化苯酚羟基化反应,对苯二酚和邻苯二酚产生过程中的反应温度、反应物用量、催化剂用量以及反应时间对反应收率的影响进行研究。发现:以[(μ-dmedt)Fe_(2)(CO)_(5)]_(2)(Tricyclohexyl phosphine)为催化剂,水做溶剂,反应温度40℃,苯酚与过氧化氢物质的量比为1∶0.8,催化剂添加量5 mg,苯酚的转化率为42.9%,对苯二酚和邻苯二酚的选择性分别为34%和60%。其中苯二酚总选择性94%、总产率40.3%,总反应数TON=59.2,总反应频数TOF=14.8 h^(-1)。A kind of diferric hydrogenase active site mimics were prepared from pentacarbonyliron,cyclohexane and butanedithiol compounds,and their basic structures were studied In addition,when hydrogen peroxide was used as oxidant,the effects of reaction temperature,amount of reactants,amount of catalyst and reaction time on the yield of hydroquinone and hydroquinone in the process of catalytic hydroxylation of phenol with 1,2-Dihydroxybenzene.With[(μ-dmedt)Fe_(2)(CO)_(5)]_(2)(Tricyclohexyl phosphine)as catalyst,the conversion of phenol was 42.9%at 40℃,the molar ratio of phenol to hydrogen peroxide was 1∶0.8,the amount of catalyst was 5 mg,the selectivity of hydroquinone and 1,2-Dihydroxybenzene was 34%and 60%,respectively.The total selectivity of hydroquinone was 94%,the total yield was 40.3%,the total reaction number was TON=59.2,the total reaction frequency was TOF=14.8 h-1.

关 键 词：氢化酶 苯酚 羟基化 化学模拟 双铁氢化酶 

分 类 号：O643[理学—物理化学] O646[理学—化学]