3,4-Dichlorotoluene Ammoxidation to 3,4-Dichlorobenzonitrile over VPO/SiO_2 Catalyst

Ammoxidation of 3,4\|dichlorotoluene(DCT) to prepare 3,4\|dichlorobenzonitrile (DCBN) over silica supported vanadium phosphorus oxide catalysts has been studied. On the VPO/SiO 2 catalyst, the influence of the reaction temperature, the molar ratio of air/DCT, the molar ratio of NH 3 /DCT in the feed gas and the space velocity ( v s) on the conversion, yield and selectivity was observed. The most appropriate reaction condition is: reaction T =673 K, n (DCT)∶ n (NH 3 )∶ n (air)=1∶7∶30 and v s=250 h -1 . At this optimum reaction condition, the conversion of DCT is 97.8%; the molar yield of DCBN is 67.4%. It was found that the addition of element phosphorus can improve the yield of DCBN compared with VO/SiO 2 catalyst.

Ammoxidation of Substituted Toluenes on Silica-Supported VPO Catalysts

The ammoxidation of substituted toluenes to their corresponding nitriles over silica-supported vanadium phosphorus oxide (VPO/SiO2) catalysts has been studied. the effects of carrier silica, the addition of phosphorus, the substituents and the loadings have been discussed. Compared with unsupported VPO, the VPO/SiO2 catalysts have higher catalytic activity for ammoxidation of substituted toluenes and much lower reaction temperature. XRD shows that vanadium phosphorus oxides exist as amorphous phase and disperse to a high degree on the silica surface in 10%loading catalyst. When the loadings are over 10%, the crystalline α-VOPO4 would emerge, which would decrease the yield and selectivity. Additional phosphorus can form composite oxides with vanadia and play concerted catalytic function, which increase the selectivity of nitriles remarkably. Different substituents or same substituents on different positions have different influences because of the variant electronic stability of intermediates, the hindered accessibility of methyl group or the chemisorption state of the substrate molecule on the electrophilic catalyst surface.

Synthesis of 4-Phenylphthalonitrile by Vapor-Phase Catalytic Ammoxidation of Intermediate 4-Phenyl-<i>o</i>-Tolunitrile: Reaction Kinetics

Kinetic regularities of 4-phenyl-o-tolunitrile ammoxidation on V-Sb-Bi-Zr/γ-Al2O3 oxide catalyst in the temperature interval 633 - 673 K have been studied. It has been established that rates of conversion of 4-phenyl-o-tolu- nitrile into the aimed 4-phenylphthalonitrile and CO2 are described by half-order equation on concentration of substratum and to be independent of the oxygen and ammonia partial pressures. It has been revealed that formation of 4-phenylphthalimide from byproducts is due to hydrolysis of 4-phenylphthalonitrile;carbon dioxide is produced by oxidation of 4-phenyl-o-tolunitrile and decarboxylation of 4-phenylphthalimide, and 4-phenylben- zonitrile is produced from 4-phenyl-o-tolunitrile and 4-phenylphthalimide.

Research on Preparation of 2,4-Dichlorobenzonitrile by Ammoxidation of 2,4-Dichlorotoluene

A process for ammoxidation of 2, 4-dichlorotoluene to prepare 2, 4-dichlorobenzonitrile which is a key intermediate of organic synthesis was studied. Having appraised and screened catalysts on an apparatus of umicroreactor-chromatograghy', the further experiments confirming the catalyst and find-ing the optimum technological conditions were carried out by using a fixed-bed reactor made of quartz (30mm inside diameter). The influence of temperature, the ratio of ammonia, the ratio of air and the space velocity of catalyst upon the conversion, molar yield and selectivity of the reaction were observed, respec-tively. Using catalyst of DC124, on the suitable conditions, the highest conversion is 98. 1 %, molar yield is 89. 5%. The 2, 4-dichlorobenzonitrile obtained is white sheet or needle crystal with the purity hlgher than 99%. The effect of two chlorine atoms at 2, 6 or 2,4 position on the reaction is discussed based on the research of the ammoxidation of 2, 6-dichlorotoluene and 2,4-dichlorotoluene.

Influence of V/P Ratio on the Catalytic Performance of VPO/SiO_2 Catalysts for Ammoxidation of Chloro-Substituted Toluenes

A series of vanadium phosphate oxide(VPO) catalysts supported on silica(VPO/Si O2) with various mole ratios of V/P(nV:nP=1:0.8-1:3) were prepared through impregnation method. The catalytic activity was evaluated by ammoxidation reactions of several kinds of chloro-substituted toluenes(CT) in a fixed-bed reactor. The catalyst presented the best performance when nV:nP is 1:1.6. The prepared catalysts were characterized by N2 adsorption, hydrogen temperature programmed reduction(TPR) and ammonia temperature programmed desorption(TPD) and etc. The results reveal that P can decrease the bonding energy of V=O and increase the mobility of lattice oxygen which was beneficial for the improvement of the catalysts, while too much P can greatly decrease the average oxidation number of V which leads to deactivation of the catalysts. The surface acidity of the VPO/Si O2 catalysts is affected by nV:nP and the catalyst had the highest surface acidity when nV:nP is 1:1.6. The selectivity of catalysts is proportional to the surface acidity when nV:nP is lower than 1:3.0.

A New Synthetic Route for Preparation of 2-Chloro-6-fluoro- benzonitrile and 2-Chloro-6-fluorobenzoic Acid

An effective synthetic route for preparation of 2-chloro-6-fluorobenzonitrile, 2-chloro-6-fluorobenzamide and 2-chloro-6-fluorobenzoic acid has been described. It includes diazotization, fluorination, ammoxidation and hydrolysis reactions.

Synthesis of 2, 4-Dibromo-5-Fluorobenzonitrile

2,4-Dibromo-5-fluorobenzonitrile has been synthesized for the first time (81.5% yield). It may be used in synthesizing 2,4-dibromo-5-fluorobenzoic acid, the intermediates of fluoroquinolones. The ammoxidation procedure for preparation of the nitrile has been described in detail.

A New Synthetic Route for 2,4-Dibromo-5-fluorobenzoic Acid

A convenient and practical synthetic route for 2,4-dibromo-5-fluorobenzoic acid is described. Two intermediates, 2,4-dibromo-5-fluorobenzonitrile and 2,4-dibromo-5-fluorobenzamide, have not been reported before. This route can be easily industrialized.

Catalytic Amidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxamide over Alkali Manganese Oxides

2,5-Furandicarboxamide was firstly synthesized in yield of 85% via catalytic oxidative amidation of 5-hydroxy- methylfurfural with aqueous NH3 over alkali manganese oxides of a-MnO2/NaxMnO〉 The intermediates of 5-hydroxymethyl-furonitrile, 2,5-dicyanofuran, and 5-cyano-2-furancarboxamide were verified and their reactivities were further examined. The kinetic analysis results showed that the transformation of intermediate product of 5-cyano-2-furancarboxamide to 2,5-furan-dicarboxamide is a slower step, which is closely relative to the reaction temperature and basicity of catalyst.