368-77-4Relevant academic research and scientific papers
Electron attachment and detachment: Electron affinities of isomers of trifluoromethylbenzonitrile
Miller, Thomas M.,Viggiano,Friedman, Jeffrey F.,Van Doren, Jane M.
, p. 9993 - 9998 (2004)
Rate constants for electron attachment to the three isomers of trifluoromethylbenzonitrile [(CF3)(CN)C6H4, or TFMBN] were measured over the temperature range of 303-463 K in a 133-Pa He buffer gas, using a flowing-afterglow Langmuir-probe apparatus. At 303 K, the measured attachment rate constants are 9.0×10-8 (o-TFMBN), 5.5× 10-8 (m-TFMBN), and 8.9 × 10-8 cm 3 s-1 (p-TFMBN), estimated accurate to ±25%. The attachment process formed only the parent anion in all three cases. Thermal electron detachment was observed for all three anion isomers, and rate constants for this reverse process were also measured. From the attachment and detachment results, the electron affinities of the three isomers of TFMBN were determined to be 0.70(o-TFMBN), 0.67(m-TFMBN), and 0.83 eV (p-TFMBN), all ±0.05 eV. G3(MP2) [Gaussian-3 calculations with reduced Moller-Plesset orders (MP2)] calculations were carried out for the neutrals and anions. Electron affinities derived from these calculations are in good agreement with the experimental values.
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.
Recyclable and Reusable Pd(OAc)2/XPhos–SO3Na/PEG-400/H2O System for Cyanation of Aryl Chlorides with Potassium Ferrocyanide
Cai, Mingzhong,Huang, Bin,Liu, Rong,Xu, Caifeng
, (2021/12/03)
Pd(OAc)2/XPhos–SO3Na in a mixture of poly(ethylene glycol) (PEG-400) and water is shown to be a highly efficient catalyst for the cyanation of aryl chlorides with potassium ferrocyanide. The reaction proceeded smoothly at 100 or 120?oC with K2CO3 or KOAc as base, delivering a variety of aromatic nitriles in good to excellent yields. The isolation of the crude products is facilely performed by extraction with cyclohexane and more importantly, both expensive Pd(OAc)2 and XPhos–SO3Na in PEG-400/H2O system could be easily recycled and reused at least six times without any apparent loss of catalytic efficiency. Graphical Abstract: Palladium-catalyzed cyanation of aryl chlorides with potassium ferrocyanide leading to aryl nitriles by using Pd(OAc)2/XPhos–SO3Na/PEG-400/H2O as a highly efficient and recyclable catalytic system is described.[Figure not available: see fulltext.]
SO2F2-Mediated one-pot cascade process for transformation of aldehydes (RCHO) to cyanamides (RNHCN)
Ding, Chengrong,Ge, Shuting,Wei, Junjie,Zhang, Guofu,Zhao, Yiyong
, p. 17288 - 17292 (2020/05/18)
A simple, mild and practical cascade process for the direct conversion of aldehydes to cyanamides was developed featuring a wide substrate scope and great functional group tolerability. This method allows for transformations of readily available, inexpensive, and abundant aldehydes to highly valuable cyanamides in a pot, atom, and step-economical manner with a green nitrogen source. This protocol will serve as a robust tool for the installation of the cyanamide moiety in various complicated molecules.
Acceptorless dehydrogenation of amines to nitriles catalyzed by N-heterocyclic carbene-nitrogen-phosphine chelated bimetallic ruthenium (II) complex
Chen, Hua,Fu, Haiyan,Ji, Li,Li, Ruixiang,Nie, Xufeng,Zheng, Yanling
, p. 378 - 385 (2020/10/02)
We have developed a clean, atom-economical and environmentally friendly route for acceptorless dehydrogenation of amines to nitriles by combining a new dual N-heterocyclic carbene-nitrogen-phosphine ligand R(CNP)2 (R = o-xylyl) with a ruthenium precursor [RuCl2(η6-C6H6)]2. In this system, the electronic and steric factors of amines had a negligible influence on the reaction and a broad range of functional groups were well tolerated. All of the investigated amines could be converted to nitriles in good yield of up to 99% with excellent selectivity. The unprecedented catalytic performance of this system is attributed to the synergistic effect of two ruthenium centers chelated by R(CNP)2 and a plausible reaction mechanism is proposed according to the active species found via in situ NMR and HRMS.
Method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by Ru coordination compound
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Paragraph 0034-0039; 0136-0141, (2020/09/16)
The invention discloses a method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by a Ru coordination compound. The method comprises: adding a Ru coordination compound, an alkali, a primary amine and an organic solvent into a reaction test tube according to a mol ratio of 1:100:(100-500):1000-3000, and carrying out a stirring reaction under the condition of 80 to120 DEG C; and when gas chromatography monitors that the raw materials completely disappear, stopping the reaction, collecting the reaction solution, centrifuging the reaction solution, taking the supernatant, extracting with dichloromethane, merging the organic phases, drying, filtering, evaporating the organic solvent under reduced pressure to obtain a filtrate, and carrying out column chromatography purification on the filtrate to obtain the target product nitrile. According to the invention, the catalyst is good in activity, single in catalytic system, good in product selectivity, simple in subsequent treatment and good in system universality after the reaction is finished, has a good catalytic effect on various aryl, alkyl and heteroaryl substituted primary amines, and also has a gooddehydrogenation performance on secondary amines.
Metallaphotoredox Perfluoroalkylation of Organobromides
Zhao, Xiangbo,MacMillan, David W. C.
supporting information, p. 19480 - 19486 (2020/12/18)
Ruppert-Prakash type reagents (TMSCF3, TMSC2F5, and TMSC3F7) are readily available, air-stable, and easy-to-handle fluoroalkyl sources. Herein, we describe a mild, copper-catalyzed cross-coupling of these fluoroalkyl nucleophiles with aryl and alkyl bromides to produce a diverse array of trifluoromethyl, pentafluoroethyl, and heptafluoropropyl adducts. This light-mediated transformation proceeds via a silyl-radical-mediated halogen atom abstraction pathway, which enables perfluoroalkylation of a broad range of organobromides of variable steric and electronic demand. The utility of the method is demonstrated through the late-stage functionalization of several drug analogues.
Metal-free dehydrosulfurization of thioamides to nitriles under visible light
Xu, Tianxiao,Cao, Tianpeng,Feng, Qingyuan,Huang, Shenlin,Liao, Saihu
supporting information, p. 5151 - 5153 (2020/05/26)
A visible light-mediated, metal-free dehydrosulfurization reaction of thioamides to nitriles is described. This reaction features high yields, mild reaction conditions, and the use of a cheap organic dye as the photoredox catalyst and air as the oxidant.
A Transition-Metal-Free One-Pot Cascade Process for Transformation of Primary Alcohols (RCH2OH) to Nitriles (RCN) Mediated by SO2F2
Jiang, Ying,Sun, Bing,Fang, Wan-Yin,Qin, Hua-Li
supporting information, p. 3190 - 3194 (2019/05/21)
A new transition-metal-free one-pot cascade process for the direct conversion of alcohols to nitriles was developed without introducing an “additional carbon atom”. This protocol allows transformations of readily available, inexpensive, and abundant alcohols to highly valuable nitriles.
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.
