铁次卟啉二甲酯仿生催化α-蒎烯分子氧氧化反应

doi:10.3969/j.issn.0253-2417.2016.06.004

林产化学与工业 ›› 2016, Vol. 36 ›› Issue (6): 23-28.doi: 10.3969/j.issn.0253-2417.2016.06.004

铁次卟啉二甲酯仿生催化α-蒎烯分子氧氧化反应

徐士超^1,2, 赵振东^1,2, 毕良武^1,2, 陈玉湘^1,2, 朱守记¹, 卢言菊^1,2, 王婧¹, 古研¹

1. 中国林业科学研究院林产化学工业研究所;生物质化学利用国家工程实验室, 国家林业局林产化学工程重点开放性实验室, 江苏省生物质能源与材料重点实验室, 江苏南京 210042;
2. 中国林业科学研究院林业新技术研究所, 北京 100091

收稿日期:2015-07-03 出版日期:2016-12-25 发布日期:2016-12-23
通讯作者: 赵振东,研究员,博士生导师,主要从事萜类化学、松树病虫害化学、天然产物化学、应用化学等方面的研究与利用工作;E-mail:zdzhao@189.cn E-mail:zdzhao@189.cn
作者简介:徐士超(1985-),男,山东临沂人,助理研究员,博士,主要从事萜类化学加工与利用研究
基金资助:
国家自然科学基金青年科学基金资助（31600466）；江苏省生物质能源与材料重点实验室基本科研业务费项目（JSBEM-S-201605）；中央级公益性科研院所基本科研业务费专项资金（CAFYBB2014QA022）

Biomimetic Catalytic Oxidation of α-Pinene by Molecular Oxygen with Ferric Deuteroporphyrin Dimethyl Ester as Catalyst

XU Shi-chao^1,2, ZHAO Zhen-dong^1,2, BI Liang-wu^1,2, CHEN Yu-xiang^1,2, ZHU Shou-ji¹, LU Yan-ju^1,2, WANG Jing¹, GU Yan¹

1. Institute of Chemical Industry of Forest Products, CAF, National Engineering Lab. for Biomass Chemical Utilization, Key and Open Lab. of Forest Chemical Engineering, SFA, Key Lab. of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, China;
2. Research Institute of Forestry New Technology, CAF, Beijing 100091, China

Received:2015-07-03 Online:2016-12-25 Published:2016-12-23

摘要/Abstract

摘要： 以铁次卟啉二甲酯（FeClDPDME）为模型催化剂，在无任何外加溶剂及助剂的条件下，催化氧气氧化α-蒎烯，探讨了反应温度、反应时间、催化剂质量分数以及氧气流速等工艺条件对反应的影响，并对Fe卟啉催化烃类分子氧反应机理进行初步探讨。研究结果表明：氧化主要发生在α-蒎烯双键和烯丙位碳氢键，当反应温度为80℃、反应时间为6 h、催化剂质量分数为50 mg/kg、氧气流速为60 mL/min时，α-蒎烯转化率及主要氧化产物的选择性更高，分别达到17.9%和86.7%。

关键词: α-蒎烯, 金属卟啉, 仿生催化, 需氧氧化

Abstract: Ferric deuteroporphyrin dimethyl ester (FeClDPDME) was employed as the model catalyst to investigate the catalytic oxidation of α-pinene by molecular oxygen without any solvent and additive. The influences of temperature, time, catalyst mass ratio and molecular oxygen flow rate on this reaction were investigated. The results showed that the oxidation occurred mainly on C=C bond and allylic C-H bonds of α-pinene. The optimal conditions of this reaction were reaction temperature 80℃, reaction time 6 h, catalyst mass ratio 50 mg/kg and molecular oxygen flow rate 60 mL/min, respectively. Under these conditions the conversion rate of α-pinene and the total selectivity of C=C bond and allylic C-H bonds oxidation products reached 17.9% and 86.7%, respectively.

Key words: α-pinene, metalloporphyrin, biomimetic catalysis, aerobic oxidation

中图分类号:

TQ35

徐士超, 赵振东, 毕良武, 陈玉湘, 朱守记, 卢言菊, 王婧, 古研. 铁次卟啉二甲酯仿生催化α-蒎烯分子氧氧化反应[J]. 林产化学与工业, 2016, 36(6): 23-28.

XU Shi-chao, ZHAO Zhen-dong, BI Liang-wu, CHEN Yu-xiang, ZHU Shou-ji, LU Yan-ju, WANG Jing, GU Yan. Biomimetic Catalytic Oxidation of α-Pinene by Molecular Oxygen with Ferric Deuteroporphyrin Dimethyl Ester as Catalyst[J]. Chemistry and Industry of Forest Products, 2016, 36(6): 23-28.

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铁次卟啉二甲酯仿生催化α-蒎烯分子氧氧化反应

Biomimetic Catalytic Oxidation of α-Pinene by Molecular Oxygen with Ferric Deuteroporphyrin Dimethyl Ester as Catalyst

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