6574-99-8Relevant academic research and scientific papers
Method for catalyzing oxidation of amines to generate nitrile by using nonmetal mesoporous nitrogen-doped carbon material
-
Paragraph 0019; 0034, (2021/05/08)
The invention discloses a method for preparing nitrile by catalyzing amine oxidation with a non-metal mesoporous nitrogen-doped carbon material catalyst, which is applied to the field of synthesis, the material is prepared by using a nitrogen-containing organic ligand as a precursor and silica sol as a template agent, calcining in the atmosphere of inert gases such as N2 or Ar and then removing the template agent; oxygen or air is used as an oxygen source, the reaction is performed at 80-130 DEG C under the action of ammonia water in the presence of a solvent, the effect is good, and the product still keeps higher activity after being recycled for more than 8 times, and has a wide industrial application prospect. The invention provides a heterogeneous non-metal catalytic system for catalyzing amine oxidation to prepare nitrile for the first time, and compared with a reported metal catalyst, the heterogeneous non-metal catalytic system does not bring metal pollution to a product to influence the effect of cyano drugs.
Investigation of BiVO4 structure variations on the dichlorotoluene ammoxidation performance
Li, Xiongjian,Huang, Chi
, p. 866 - 870 (2020/12/30)
In this study, BiVO4 synthesized by hydrothermal and calcination methods were explored as catalysts in the ammoxidation of dichlorotoluenes to shed light on the structure-reactivity correlations. The BiVO4 samples were characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), Brunauer–Emmett–Teller (BET), and UV–Vis spectrophotometry. The results showed that the catalytic activity of BiVO4 greatly relied on the structure variations. The hydrothermal prepared BiVO4 exhibited better catalytic activities as a consequence of its greater structure deformation, with maximum yields of 73.1, 72.2, and 70.8% for 3,4-, 2,4- and 2,6- dichlorobenzonitrles, respectively.
Hydrothermal synthesis of V-doped hexagonal WO3 microspheres comprising of nanoblocks for catalytic ammoxidation of dichlorotoluene
Li, Xiongjian,Huang, Chi
, (2020/12/17)
V-doped hexagonal WO3 microspheres comprising of nanoblocks were successfully prepared via a facile hydrothermal approach. Several techniques such as XRD, SEM, TEM, FTIR, EDS, TPR, BET and Raman have been performed and the characterization results reveal that V replaced W atoms into the hexagonal lattice-structure. The microspheres possess diameter of about 4.4 μm and the nanoblocks have thicknesses of 40–100 nm and widths of about 150 nm. In addition, the catalytic performance of the obtained V-doped WO3 nanomaterial was investigated in the ammoxidation of dichlorotoluene. The catalytic results indicate that the as-prepared nanostructures show significantly improved selective performance with the selectivities of 3,4-DCBN and 2,6-DCBN reaching up to 89.8% and 86.2%, respectively.
Cu2O-Catalyzed Conversion of Benzyl Alcohols Into Aromatic Nitriles via the Complete Cleavage of the C≡N Triple Bond in the Cyanide Anion
Liu, Wenbo,Tang, Peichen,Zheng, Yi,Ren, Yun-Lai,Tian, Xinzhe,An, Wankai,Zheng, Xianfu,Guo, Yinggang,Shen, Zhenpeng
, p. 3509 - 3513 (2021/10/04)
Nitrogen transfer from cyanide anion to an aldehyde is emerging as a promising method for the synthesis of aromatic nitriles. However, this method still suffers from a disadvantage that a use of stoichiometric Cu(II) or Cu(I) salts is required to enable the reaction. As we report herein, we overcame this drawback and developed a catalytic method for nitrogen transfer from cyanide anion to an alcohol via the complete cleavage of the C≡N triple bond using phen/Cu2O as the catalyst. The present condition allowed a series of benzyl alcohols to be smoothly converted into aromatic nitriles in moderate to high yields. In addition, the present method could be extended to the conversion of cinnamic alcohol to 3-phenylacrylonitrile.
Cascade Process for Direct Transformation of Aldehydes (RCHO) to Nitriles (RCN) Using Inorganic Reagents NH2OH/Na2CO3/SO2F2 in DMSO
Fang, Wan-Yin,Qin, Hua-Li
, p. 5803 - 5812 (2019/05/14)
A simple, mild, and practical process for direct conversion of aldehydes to nitriles was developed feathering a wide substrate scope and great functional group tolerability (52 examples, over 90% yield in most cases) using inorganic reagents (NH2OH/Na2CO3/SO2F2) in DMSO. This method allows for transformations of readily available, inexpensive, and abundant aldehydes to highly valuable nitriles in a pot, atom, and step-economical manner without transition metals. This protocol will serve as a robust tool for the installation of cyano-moieties to complicated molecules.
Method for preparing 3,4-dichlorobenzonitrile
-
Paragraph 0006; 0017-0019, (2019/10/22)
The invention discloses a method for preparing 3,4-dichlorobenzonitrile. 3,4-Dichlorotoluene is taken as a raw material, benzoyl peroxide is added at 80-110 DEG C, chlorine gas is introduced for a reaction, when the content of the 3,4-dichlorotoluene is less than or equal to 0.03%, the reaction is stopped, 3,4-dichlorobenzotrichloride is prepared, then in the presence of a catalyst, the 3,4-dichlorobenzotrichloride and ammonium chloride react at 170-230 DEG C, when the content of the 3,4-dichlorobenzotrichloride is less than 0.05%, the reaction is stopped, the product is subjected to reduced pressure distillation, and the pure 3,4-dichlorobenzonitrile product is obtained. The method has the advantages that the reaction conditions are mild, the control is easy, the yield is high, no side reaction exists, environmental friendliness is achieved, the cost of reaction raw materials is low, hydrogen chloride gas produced by the reaction can be collected as a by-product hydrochloric acid, andeconomic benefits are increased.
Palladium-Catalyzed Late-Stage Direct Arene Cyanation
Zhao, Da,Xu, Peng,Ritter, Tobias
supporting information, p. 97 - 107 (2019/01/21)
Methods for direct benzonitrile synthesis are sparse, despite the versatility of cyano groups in organic synthesis and the importance of benzonitriles for the dye, agrochemical, and pharmaceutical industries. We report the first general late-stage aryl C–H cyanation with broad substrate scope and functional-group tolerance. The reaction is enabled by a dual-ligand combination of quinoxaline and an amino acid-derived ligand. The method is applicable to direct cyanation of several marketed small-molecule drugs, common pharmacophores, and organic dyes. Benzonitriles are some of the most versatile building blocks for organic synthesis, in particular in the pharmaceutical industry, but general methods to make them by direct C–H functionalization are unknown. In this issue of Chem, Ritter and coworkers describe a late-stage aryl C–H cyanation with broad substrate scope and functional-group tolerance, enabled by a palladium-dual-ligand catalyst system. The reaction may serve for the late-stage modification of drug candidates. Aryl nitriles constitute an important class of organic compounds that are widely found in natural products, pharmaceuticals, agricultural chemicals, dyes, and materials. Moreover, nitriles are versatile building blocks to access numerous other important molecular structure groups. However, no general method for direct aromatic C–H cyanation is known. All approaches to date require either an appropriate directing group or reactive electron-rich substrates, such as indoles, which limit their synthetic applications. Here we describe an undirected, palladium-catalyzed late-stage aryl C–H cyanation reaction for the synthesis of complex aryl nitriles that would otherwise be more challenging to produce. The wide substrate scope and good functional-group tolerance of this reaction provide direct and quick access to structural diversity for pharmaceutical and agrochemical development.
Copper-Catalyzed Unstrained C-C Single Bond Cleavage of Acyclic Oxime Acetates Using Air: An Internal Oxidant-Triggered Strategy toward Nitriles and Ketones
Zhu, Chuanle,Chen, Fulin,Liu, Chi,Zeng, Hao,Yang, Zhiyi,Wu, Wanqing,Jiang, Huanfeng
, p. 14713 - 14722 (2018/12/14)
A copper-catalyzed aerobic oxidative C-C single bond cleavage of acyclic unstrained oxime acetates is reported, providing various aryl nitriles and ketones in good yields. Mechanistic studies indicate a radical procedure is involved in this transformation, and the oxygen atom in the ketone products is originated from O2 in the air. Oxime acetates as an internal oxidant have been proved to be an initiator, which may promote the discovery of novel protocol for C-C bond cleavage and dioxygen activation.
Synthesis method of 3,4-dichlorobenzonitrile
-
Paragraph 0032-0036; 0037-0041; 0042-0046; 0047-0056, (2018/05/01)
The invention discloses a synthesis method of 3,4-dichlorobenzonitrile. The synthesis method comprises the following steps of (1) adopting 1,2-dichlorobenzene as a raw material, adding a catalyst A, rising the temperature, then dropwise adding bromine, carrying out heat insulating reaction after the dropwise adding is finished, and carrying out aftertreatment to obtain 3,4-dichlorobromobenzene; (2) after mixing cuprous cyanide, a catalyst B and a solvent, dropwise adding 3,4-dichlorobromobenzene diluent after rising the temperature, carrying out heat insulating reaction after the dropwise adding is finished, and carrying out aftertreatment to obtain the 3,4-dichlorobenzonitrile. The synthesis method disclosed by the invention has the beneficial effects that the 1,2-dichlorobenzene is adopted as the raw material, and after two-step reaction of bromination and cyaniding, the 3,4-dichlorobenzonitrile is obtained, the molar yield can reach 85% or above and the purity is greater than or equal to 98%. The synthesis method disclosed by the invention is low in raw-material cost so as to be suitable for industrial production.
Practical CuCl/DABCO/4-HO-TEMPO-catalyzed oxidative synthesis of nitriles from alcohols with air as oxidant
Hu, Yongke,Chen, Lei,Li, Bindong
supporting information, p. 464 - 466 (2017/11/13)
A mild and efficient methodology for the direct oxidative synthesis of nitriles from easily available alcohols and aqueous ammonia by employing CuCl/DABCO/4-HO-TEMPO as the catalysts is described. This protocol uses the air as a green oxidant and aqueous ammonia as the nitrogen source at room temperature. A variety of aryl, heterocyclic and allylic alcohols are smoothly converted into the corresponding nitriles in good to excellent yields.
