TiSiW_(12)O_(40)/TiO_2催化合成环己酮1,2-丙二醇缩酮

以固载杂多酸盐TiSiW1 2 O4 0 /TiO2 为多相催化剂 ,通过环己酮和 1 ,2 丙二醇反应合成了环己酮 1 ,2 丙二醇缩酮 ,探讨TiSiW1 2 O4 0 /TiO2 对缩酮反应的催化活性 ,较系统地研究了酮醇量比 ,催化剂用量 ,反应时间诸因素对产品收率的影响。实验表明 :TiSiW1 2 O4 0 /TiO2 是合成环己酮 1 ,2 丙二醇缩酮的良好催化剂 ,在n(酮 )∶n(醇 ) =1 0∶1 5 ,催化剂用量为反应物料总质量的 0 6 % ,环己烷为带水剂 ,反应时间 40min的优化条件下 ,环己酮 1 ,2 丙二醇缩酮的收率可达 92 2 %。     

Supported TiO2/silica gel as an efficient and inexpensive catalyst for nonsolvent liquid-phase oxidation of cyclohexylamine to cyclohexanone oxime

A benign approach is proposed for the highly efficient synthesis of cyclohexanone oxime through nonsolvent liquid-phase oxidation of cyclohexylamine with dioxygen over supported TiO₂/silica gel. The as-prepared catalyst was characterized by Brunauer–Emmett–Teller (BET), Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), and X-ray powder diffraction (XRD) analyses. The results indicate that titanium active sites could be grafted on silica gel supports as catalytic centres. Various parameters such as reaction time and reaction temperature were systematically optimized; the results showed that supported 20%TiO₂/silica gel exhibited the best catalytic effect with 63.2% of amine conversion and 86.3% of selectivity to CHO. A possible pathway is proposed for cyclohexylamine oxidation over supported TiO₂/silica gel. The method developed in this study using dioxygen as the oxidant and inexpensive TiO₂/silica gel as an efficient catalyst has incredible industrial application potential for green synthesis of cyclohexanone oxime.     

Crosslinked Aggregates of Fusion Enzymes in Microaqueous Organic Media

Baeyer-Villiger monooxygenases (BVMOs) are attractive for selectively oxidizing various ketones using oxygen into valuable esters and lactones. However, the application of BVMOs is restrained by cofactor dependency and enzyme instability combined with water-related downsides such as low substrate loading, low oxygen capacity, and water-induced side reactions. Herein, we described a redox-neutral linear cascade with in-situ cofactor regeneration catalyzed by fused alcohol dehydrogenase and cyclohexanone monooxygenase in aqueous and microaqueous organic media. The cascade conditions have been optimized regarding substrate concentrations as well as the amounts of enzymes and cofactors with the Design of Experiments (DoE). The carrier-free immobilization technique, crosslinked enzyme aggregates (CLEAs), was applied to fusion enzymes. The resultant fusion CLEAs were proven to function in microaqueous organic systems, in which the enzyme ratios, water contents (0.5–5 vol. %), and stability have been systematically studied. The fusion CLEAs showed promising operational (up to 5 cycles) and storage stability.