β-异佛尔酮氧化反应网络及反应机理

Oxidation reaction network of β-isophorone and reaction mechanism

以乙酰丙酮铁为催化剂、吡啶为溶剂对β-IP(异佛尔酮)氧化反应网络及反应机理进行系统研究.通过GCMS和NMR等方法分析产物组成并鉴定产物结构,确定反应体系中6种二聚体副产物的结构.单因素实验研究表明:当氧分压高、氧气流量大、催化剂用量较少、温度较低时,反应主产物选择性高,副产物含量相对较低;当含氧不足、催化剂用量较多、温度较高时,反应主产物选择性较低,二聚体反应为主要副反应.由于α-IP(α-异佛尔酮)或KIP(氧代异佛尔酮)在乙酰丙酮铁存在下通入氧气时不反应,结合反应体系各组分浓度变化关系提出β-IP的氧化反应网络和主副反应机理,为选择生产工艺条件以提高目标产物选择性及反应动力学的深入研究提供基础.

The reaction network and mechanism of β-IP （β- isophorone） oxidation catalyzed by iron （III） acetylacetonate were systematically studied. A variety of analytic methods such as GC-MS and NMR were used to determine the products’ structures and the structures of six dimer byproducts were determined. The single factor experiments’ results show that when the oxygen pressure is high, the flow rate of oxygen is big, the concentration of catalyst is small and the temperature is low, the selectivity of main product is high and meanwhile the concentration of byproducts is rather small; when there is not enough oxygen, the concentration of catalyst is large and the temperature is high, the yield of main product is relatively small and dimerization becomes the main side reaction. Since neither crIP nor KIP would further react under the reaction condition, referring to changes of components’ concentration, the oxidation reaction network of β- IP , main reaction mechnism and side reaction mechnism were proposed, which could provide foundation for selecting the manufacturing conditions, improving the selectivity and further kinetics study.