529-19-1Relevant articles and documents
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
Using Data Science To Guide Aryl Bromide Substrate Scope Analysis in a Ni/Photoredox-Catalyzed Cross-Coupling with Acetals as Alcohol-Derived Radical Sources
Doyle, Abigail G.,Gandhi, Shivaani S.,Jiang, Shutian,Kariofillis, Stavros K.,Martinez Alvarado, Jesus I.,?urański, Andrzej M.
supporting information, p. 1045 - 1055 (2022/01/19)
Ni/photoredox catalysis has emerged as a powerful platform for C(sp2)–C(sp3) bond formation. While many of these methods typically employ aryl bromides as the C(sp2) coupling partner, a variety of aliphatic radical sources have been investigated. In principle, these reactions enable access to the same product scaffolds, but it can be hard to discern which method to employ because nonstandardized sets of aryl bromides are used in scope evaluation. Herein, we report a Ni/photoredox-catalyzed (deutero)methylation and alkylation of aryl halides where benzaldehyde di(alkyl) acetals serve as alcohol-derived radical sources. Reaction development, mechanistic studies, and late-stage derivatization of a biologically relevant aryl chloride, fenofibrate, are presented. Then, we describe the integration of data science techniques, including DFT featurization, dimensionality reduction, and hierarchical clustering, to delineate a diverse and succinct collection of aryl bromides that is representative of the chemical space of the substrate class. By superimposing scope examples from published Ni/photoredox methods on this same chemical space, we identify areas of sparse coverage and high versus low average yields, enabling comparisons between prior art and this new method. Additionally, we demonstrate that the systematically selected scope of aryl bromides can be used to quantify population-wide reactivity trends and reveal sources of possible functional group incompatibility with supervised machine learning.
Facile dehydration of primary amides to nitriles catalyzed by lead salts: The anionic ligand matters
Ruan, Shixiang,Ruan, Jiancheng,Chen, Xinzhi,Zhou, Shaodong
, (2020/12/09)
The synthesis of nitrile under mild conditions was achieved via dehydration of primary amide using lead salts as catalyst. The reaction processes were intensified by not only adding surfactant but also continuously removing the only by-product, water from the system. Both aliphatic and aromatic nitriles can be prepared in this manner with moderate to excellent yields. The reaction mechanisms were obtained with high-level quantum chemical calculations, and the crucial role the anionic ligand plays in the transformations were revealed.
Method for dehydrating primary amide into nitriles under catalysis of cobalt
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Paragraph 0048-0050, (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.
H3PO4 catalyzed one-pot synthesis of 1,3-diphenyl-1H-pyrazole-4-carbaldehyde to novel 1,3-diphenyl-1H-pyrazole-4-carbonitrile
Choudhare, Tukaram S,Netankar, Prashant D,Shirsath, Sagar E,Wagare, Devendra S
, (2021/07/10)
Abstract: One-pot condensation of pyrazole-4-aldehydes and hydroxylamine hydrochloride to form the corresponding oxime using formic acid as a medium and further dehydration of oxime using a catalytic amount of orthophosphoric acid to afford novel pyrazole-4-carbonitrile. This protocol serves as an ortho-phosphoric acid-catalyzed one-pot conversion of aldehyde to nitrile. Most remarkable features of this method are metal-free, cost-effective, atom efficiency with excellent yield (98–99%). This process will serve as a robust and scalable tool for the synthesis of valuable and versatile precursor (nitriles). This precursor will pave the way for the synthesis of various medicinally important valuable compounds. Graphic abstract: [Figure not available: see fulltext.].
One pot synthesis of aryl nitriles from aromatic aldehydes in a water environment
Chen, Qingqing,Han, Hongwei,Lin, Hongyan,Ma, Xiaopeng,Qi, Jinliang,Wang, Xiaoming,Yang, Yonghua,Zhou, Ziling
, p. 24232 - 24237 (2021/07/29)
In this study, we found a green method to obtain aryl nitriles from aromatic aldehyde in water. This simple process was modified from a conventional method. Compared with those approaches, we used water as the solvent instead of harmful chemical reagents. In this one-pot conversion, we got twenty-five aryl nitriles conveniently with pollution to the environment being minimized. Furthermore, we confirmed the reaction mechanism by capturing the intermediates, aldoximes.
METHOD FOR PRODUCING AROMATIC NITRILE COMPOUND AND CATALYST FOR SYNTHESIS OF AROMATIC NITRILE COMPOUND
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Paragraph 0053-0065; 0093-0098, (2021/05/07)
PROBLEM TO BE SOLVED: To efficiently produce an aromatic nitrile compound by oxidizing a methyl group directly bonded to an aromatic ring into a cyano group by ammoxidation. SOLUTION: The present invention relates to a method for producing an aromatic nitrile compound wherein a zeolite carrying at least one selected from the group consisting of an alkali metal and an alkaline earth metal is used to, in the presence of ammonia, oxidize an aromatic compound having a methyl group bound to a carbon atom of an aromatic ring with oxygen. SELECTED DRAWING: Figure 2 COPYRIGHT: (C)2021,JPOandINPIT
Pd@CeO2-catalyzed cyanation of aryl iodides with K4Fe(CN)6·3H2O under visible light irradiation
Wang, Shengyu,Wang, Jianqiang,Pan, Junyi,Liu, Cheng,Gong, Xubin,Guo, Cheng
, (2021/01/12)
Cyanation of aryl iodides is still challenging work for chemical researchers because of harsh reaction conditions and toxic cyanide sources. Herein, we have developed a new protocol based on the combination of the catalyst Pd@CeO2, nontoxic cyanide source K4[Fe (CN)6]·3H2O, and driving force visible light irradiation. The reaction is operated at relatively moderate temperature (55°C) and exhibits good catalytic efficiency of product aryl nitriles (yields of 89.4%). Moreover, the catalyst Pd@CeO2 possesses good reusability with a slight loss of photocatalytic activity after five consecutive runs. The reaction system based on the above combination shows a wide range of functional group tolerance under the same conditions. Reaction conditions such as temperature, time, the component of catalyst, and solutions are optimized by studying cyanation of 1-iodo-4-nitrobenzene as model reaction. According to these results, the possible mechanism of Pd@CeO2-catalyzed cyanation of aryl iodides under visible light irradiation is proposed based on the influence of visible light on the catalyst and reactant compounds. In all, we provided an environmental and economic method for preparation of aryl nitriles from cyanation of aryl iodides based on the goal of green chemistry for sustainable development.
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.
Pd/CoFe2O4/chitosan: A highly effective and easily recoverable hybrid nanocatalyst for synthesis of benzonitriles and reduction of 2-nitroaniline
Baran, Talat,Nasrollahzadeh, Mahmoud
, (2020/10/02)
In this study, a novel catalyst system with high activity and easy recoverability was successfully prepared through the deposition of Pd nanoparticles (NPs) onto designed sustainable hybrid beads containing magnetic cobalt ferrite and chitosan (Pd/CoFe2O4/chitosan). The catalytic potential of Pd/CoFe2O4/chitosan hybrid nanocatalyst was then assessed in i) preparation of benzonitriles via aryl halides cyanation and ii) reduction of 2-nitroaniline (2-NA). Various aryl iodides and bromides were successfully cyanated by Pd/CoFe2O4/chitosan hybrid nanocatalyst with excellent reaction yields within 3 h. In addition to the production of benzonitriles, the hybrid nanocatalyst showed excellent activity by reducing 2-NA in 65 s. It was proved that the Pd/CoFe2O4/chitosan hybrid nanocatalyst outperformed many catalysts used in the cyanation of aryl halides and catalytic reduction of 2-NA previously reported in the literature. Moreover, it was found that the designed Pd/CoFe2O4/chitosan hybrid nanocatalyst was easily and effectively separated from the reaction mixture using an external magnet and reused several times in catalytic reactions without considerable loss of catalytic activity.
