86-53-3Relevant academic research and scientific papers
Ligand properties of aromatic azines: C-H activation, metal induced disproportionation and catalytic C-C coupling reactions
D?nnecke, Daniel,Wunderle, Joachim,Imhof, Wolfgang
, p. 585 - 594 (2004)
The reaction of aromatic azines with Fe2(CO)9 yields dinuclear iron carbonyl cluster compounds as the main products. The formation of these compounds may be rationalized by a C-H activation reaction at the aromatic substituent in ortho position with respect to the exocyclic C-N double bond followed by an intramolecular shift of the corresponding hydrogen atom toward the former imine carbon atom. The second imine function of the ligand does not react. Additional products arise from the metal induced disproportionation of the azine into a primary imine and a nitrile. So also one of the imine C-H bonds may be activated during the reaction. Depending on the aromatic substituent of the azine ligands iron carbonyl complexes of the disproportionation products are isolated and characterized by X-ray crystallography. C-C coupling reactions catalyzed by Ru3(CO)12 result in the formation of ortho-substituted azines. In addition, ortho-substituted nitriles are identified as side-products showing that the metal induced disproportionation reaction also takes place under catalytic conditions.
Nitrile Synthesis via Desulfonylative-Smiles Rearrangement
Abe, Masahiro,Nitta, Sayasa,Miura, Erina,Kimachi, Tetsutaro,Inamoto, Kiyofumi
, p. 4460 - 4467 (2022/03/15)
Herein, we designed a simple nitrile synthesis from N-[(2-nitrophenyl)sulfonyl]benzamides via base-promoted intramolecular nucleophilic aromatic substitution. The process features redox-neutral conditions as well as no requirement of toxic cyanide species and transition metals. Our process shows broad scope and various functional group compatibility, affording a variety of (hetero)aromatic nitriles in good to excellent yields.
Highly dispersed Co species in N-doped carbon enhanced the aldehydes ammoxidation reaction activity
Fu, Wenqian,Pan, Liuming,Tang, Tiandi,Wang, Siming,Zhang, Lei
, (2022/01/04)
Developing environmentally friendly catalysts with high activity for the ammoxidation of aromatic aldehydes to aromatic nitriles is greatly important for this industrial transformation. Herein, natural vitamin B12 was used as a carbon source for the preparation of a cobalt- and nitrogen-doped catalyst precursor, which was pyrolyzed at different temperatures to obtain cobalt- and nitrogen-doped carbon (Co@NC-T) (T denotes pyrolysis temperature) catalysts. The Co@NC-800 exhibited excellent activity and selectivity in the ammoxidation of aromatic aldehydes with ammonium carbonate to aromatic nitriles compared to the Co@NC-700, Co@NC-600 and Co@NC-500 catalysts. The high catalytic performance of Co@NC-800 could be due to the presence of the low-density electron cloud of the highly dispersed Co species, which could interact with the benzene ring of benzaldehyde bearing p-π conjugate, thereby promoting the adsorption and activation of benzaldehyde. Consequently, the activated benzaldehyde reacted with amino groups that were decomposed from ammonium carbonate and subsequently underwent a dehydration process to form nitriles.
Cyanide-Free Cyanation of sp2 and sp-Carbon Atoms by an Oxazole-Based Masked CN Source Using Flow Microreactors
Sharma, Brijesh M.,Nikam, Arun V.,Lahore, Santosh,Ahn, Gwang-Noh,Kim, Dong-Pyo
supporting information, (2022/02/25)
This work reports a cyanide-free continuous-flow process for cyanation of sp2 and sp carbons to synthesize aryl, vinyl and acetylenic nitriles from (5-methyl-2-phenyloxazol-4-yl) boronic acid [OxBA] reagent as a sole source of carbon-bound mask
Method for dehydrating primary amide into nitriles under catalysis of cobalt
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Paragraph 0075-0077, (2021/06/21)
The invention provides a method for dehydrating primary amide into nitrile. The method comprises the following steps: mixing primary amide (II), silane, sodium triethylborohydride, aminopyridine imine tridentate nitrogen ligand cobalt complex (I) and a reaction solvent under the protection of inert gas, carrying out reacting at 60-100 DEG C for 6-24 hours, and post-treating reaction liquid to obtain a nitrile compound (III). According to the invention, an effective method for preparing nitrile compounds by cobalt-catalyzed primary amide dehydration reaction by using the novel aminopyridine imine tridentate nitrogen ligand cobalt complex catalyst is provided; and compared with existing methods, the method has the advantages of simple operation, mild reaction conditions, wide application range of reaction substrates, high selectivity, stable catalyst, high efficiency, and relatively high practical application value in synthesis.
Nickel-Catalyzed Amination of Aryl Nitriles for Accessing Diarylamines through C?CN Bond Activation
Wu, Ke,Rong, Qiang,Sun, Nan,Hu, Baoxiang,Shen, Zhenlu,Jin, Liqun,Hu, Xinquan
supporting information, p. 4708 - 4713 (2021/08/27)
A nickel-catalyzed amination to access diarylamines has been developed through C?CN bond activation of aryl nitriles with anilines. In this developed catalytic protocol, various aromatic and heteroaromatic nitriles could be utilized as the electrophiles to couple with substituted anilines. A diversity of diarylamines were obtained in 15–95% yields. (Figure presented.).
Nickel-Catalyzed Reversible Functional Group Metathesis between Aryl Nitriles and Aryl Thioethers
Delcaillau, Tristan,Boehm, Philip,Morandi, Bill
supporting information, p. 3723 - 3728 (2021/04/07)
We describe a new functional group metathesis between aryl nitriles and aryl thioethers. The catalytic system nickel/dcype is essential to achieve this fully reversible transformation in good to excellent yields. Furthermore, the cyanide- and thiol-free reaction shows high functional group tolerance and great efficiency for the late-stage derivatization of commercial molecules. Finally, synthetic applications demonstrate its versatility and utility in multistep synthesis.
Copper-promoted cyanation of aryl iodides with N,N-dimethyl aminomalononitrile
Liu, Si-Zhan,Li, Jing,Xue, Cao-Gen,Xu, Xue-Tao,Lei, Lin-Sheng,Huo, Chen-Yu,Wang, Zhen,Wang, Shao-Hua
supporting information, (2021/02/01)
A copper-promoted cyanation of aryl iodides has been successfully developed by using N,N-dimethyl aminomalononitrile as the cyanide source with moderate toxicity and better stability. This reaction features broad substrate scope, excellent reaction yields, readily available catalyst, and simple reaction conditions.
Decarbonylative Synthesis of Aryl Nitriles from Aromatic Esters and Organocyanides by a Nickel Catalyst
Iizumi, Keiichiro,Kurosawa, Miki B.,Isshiki, Ryota,Muto, Kei,Yamaguchi, Junichiro
supporting information, p. 1555 - 1559 (2020/11/10)
A decarbonylative cyanation of aromatic esters with aminoacetonitriles in the presence of a nickel catalyst was developed. The key to this reaction was the use of a thiophene-based diphosphine ligand, dcypt, permitting the synthesis of aryl nitrile without the generation of stoichiometric metal- or halogen-containing chemical wastes. A wide range of aromatic esters, including hetarenes and pharmaceutical molecules, can be converted into aryl nitriles.
CuO-catalyzed conversion of arylacetic acids into aromatic nitriles with K4Fe(CN)6 as the nitrogen source
Ren, Yun-Lai,Shen, Zhenpeng,Tian, Xinzhe,Xing, Ai-Ping,Zhao, Zhe
, (2020/10/26)
Readily available CuO was demonstrated to be effective as the catalyst for the conversion of arylacetic acids to aromatic nitriles with non-toxic and inexpensive K4Fe(CN)6 as the nitrogen source via the complete cleavage of the C[tbnd]N triple bond. The present method allowed a series of arylacetic acids including phenylacetic acids, naphthaleneacetic acids, 2-thiopheneacetic acid and 2-furanacetic acid to be converted into the targeted products in low to high yields.
