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Biomass chitosan-derived nitrogen-doped carbon modified with iron oxide for the catalytic ammoxidation of aromatic aldehydes to aromatic nitriles
Nitrogen-doped carbon catalysts have attracted increasing research attention due to several advantages for catalytic application. Herein, cost-effective, renewable biomass chitosan was used to prepare a N-doped carbon modified with iron oxide catalyst (Fe2O3@NC) for nitrile synthesis. The iron oxide nanoparticles were uniformly wrapped in the N-doped carbon matrix to prevent their aggregation and leaching. Fe2O3@NC-800, which was subjected to carbonization at 800 °C, exhibited excellent activity, selectivity, and stability in the catalytic ammoxidation of aromatic aldehydes to aromatic nitriles. This study may provide a new method for the fabrication of an efficient and cost-effective catalyst system for synthesizing nitriles.
Wang, Wei David,Wang, Fushan,Chang, Youcai,Dong, Zhengping
(2020/11/24)

Copper-promoted cyanation of aryl iodides with N,N-dimethyl aminomalononitrile
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.
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)

An overview on the progress and development on the palladium catalyzed direct cyanation
Generation of the positive CN ion and the corresponding direct cyanation are both extremely important for cyanation of aromatic compounds. Hereby, we would like to report the simultaneous use of the new Pd nano-catalyst as well as the three types of the N-arylsulfonyl cyanamides (A, B and C) as potent reagents for the in situ generation of the positive CN ion for the direct cyanation of phenylboronic acids in acetonitrile at reflux conditions.
Heydari, Somayyeh,Habibi, Davood,Reza Faraji, Ali,keypour, Hassan,Mahmoudabadi, Masoumeh
(2020/10/02)

METHOD FOR PRODUCING AROMATIC NITRILE COMPOUND AND CATALYST FOR SYNTHESIS OF AROMATIC NITRILE COMPOUND
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
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Paragraph 0053-0065; 0099-0104

(2021/05/07)

Unprecedented Catalysis of Cs+Single Sites Confined in y Zeolite Pores for Selective Csp3-H Bond Ammoxidation: Transformation of Inactive Cs+Ions with a Noble Gas Electronic Structure to Active Cs+Single Sites
We report the transformation of Cs+ ions with an inactive noble gas electronic structure to active Cs+ single sites chemically confined in Y zeolite pores (Cs+/Y), which provides an unprecedented catalysis for oxidative cyanation (ammoxidation) of Csp3-H bonds with O2 and NH3, although in general, alkali and alkaline earth metal ions without a moderate redox property cannot activate Csp3-H bonds. The Cs+/Y catalyst was proved to be highly efficient in the synthesis of aromatic nitriles with yields >90% in the selective ammoxidation of toluene and its derivatives as test reactions. The mechanisms for the genesis of active Cs+ single sites and the ammoxidation pathway of Csp3-H bonds were rationalized by density functional theory (DFT) simulations. The chemical confinement of large-sized Cs+ ions with the pore architecture of a Y zeolite supercage rendered the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap reduction, HOMO component change, and preferable coordination arrangement for the selective reaction promotion, which provides a trimolecular assembly platform to enable the coordination-promoted concerted ammoxidation pathway working closely on each Cs+ single site. The new reaction pathway without involvement of O2-dissociated O atom and lattice oxygen differs from the traditional redox catalysis mechanisms for the selective ammoxidation.
Acharyya, Shankha S.,Ghosh, Shilpi,Iwasawa, Yasuhiro,Kaneko, Takuma,Sasaki, Takehiko,Yoshida, Yusuke
p. 6698 - 6708
(2021/06/25)

NHC-catalyzed silylative dehydration of primary amides to nitriles at room temperature
Herein we report an abnormal N-heterocyclic carbene catalyzed dehydration of primary amides in the presence of a silane. This process bypasses the energy demanding 1,2-siloxane elimination step usually required for metal/silane catalyzed reactions. A detailed mechanistic cycle of this process has been proposed based on experimental evidence along with computational study.
Ahmed, Jasimuddin,Hota, Pradip Kumar,Maji, Subir,Mandal, Swadhin K.,Rajendran, N. M.
supporting information
p. 575 - 578
(2020/01/29)

Method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by Ru coordination compound
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.
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Paragraph 0034-0039; 0124-0129

(2020/09/16)

Acceptorless dehydrogenation of amines to nitriles catalyzed by N-heterocyclic carbene-nitrogen-phosphine chelated bimetallic ruthenium (II) complex
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.
Chen, Hua,Fu, Haiyan,Ji, Li,Li, Ruixiang,Nie, Xufeng,Zheng, Yanling
p. 378 - 385
(2020/10/02)

Primary amides to amines or nitriles: A dual role by a single catalyst
We report a manganese-catalyzed hydrosilylative reduction of various primary amides to amines (25 examples). On simple modification of the reaction conditions such as in the presence of a catalytic amount of secondary amide, the same catalyst can transform the primary amides into intermediate nitrile compounds (16 examples) in excellent yields. This is the first example where such a controlled catalytic transformation of primary amides to amines or nitriles with a single catalyst has been demonstrated.
Das, Hari S.,Das, Shyamal,Dey, Kartick,Singh, Bhagat,Haridasan, Rahul,Das, Arpan,Ahmed, Jasimuddin,Mandal, Swadhin K.
supporting information
p. 11868 - 11871
(2019/10/11)

Method for directly synthesizing M-chlorobenzonitrile from M-chlorobenzoic acid and urea
The invention provides a method for directly synthesizing m-chlorobenzonitrile from m-chlorobenzoic acid and urea, belonging to the technical field of organic chemistry and the technical field of organic fine chemicals. The method for synthesizing m-chlorobenzonitrile comprises the following steps: reacting m-chlorobenzoic acid with urea to generate an intermediate reaction mixture containing m-chlorobenzamide, and carrying out dehydration reaction on the intermediate reaction mixture containing m-chlorobenzamide to generate a mixture containing m-chlorobenzonitrile; and subjecting the mixturecontaining m-chlorobenzonitrile to underpressure distillation to obtain crude nitrile, and subjecting the crude nitrile to washing with water, filtering, drying, and underpressure distillation successively to obtain the finished m-chlorobenzonitrile. The synthetic method of the invention is short in route, simple to operate, easily controllable in reaction conditions, low in production cost and small in environmental pollution; and the synthesized m-chlorobenzonitrile is stable in quality. The intermediate reaction mixture containing m-chlorobenzamide is subjected to ultrasonic or microwave catalytic dehydration, so the yield and the purity of m-chlorobenzonitrile can be remarkably improved.
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Paragraph 0017-0027

(2019/11/29)

Synthesis, characterization and catalytic performance of Pd(II) complex immobilized on Fe3O4@SiO2 nanoparticles for the ligand-free cyanation of aryl halides using K4Fe(CN)6
This work shows the preparation of a novel magnetic catalyst via immobilization of Pd(II)-N-benzyl-N-(4-bromophenyl)-5-amino-1H-tetrazole complex on the Fe3O4@SiO2 nanoparticles (NPs). The application of Fe3O4@SiO2 NPs supported Pd(II)-N-benzyl-N-(4-bromophenyl)-5-amino-1H-tetrazole complex [Fe3O4@SiO2-BAT-Pd(II)] nanocatalyst is described for the cyanation of aryl iodides and bromides to the corresponding aryl nitriles using potassium hexacyanoferrate(II) [K4Fe(CN)6] as a non-toxic and economic cyanating agent under ligand- and additive-free conditions. Some aryl nitriles were efficiently synthesized from the corresponding aryl bromides and iodides in the presence of Fe3O4@SiO2-BAT-Pd(II) nanocomplex. The core-shell nanocomplex demonstrated the superior catalytic performance for the synthesis of synthetically valuable aryl nitriles within good to excellent yields. This process eliminates the need to handle highly toxic metal cyanides, and it can be easily recovered and reused for six consecutive runs with no decreasing of its catalytic capability. Highlights: Preparation of Pd(II) complex immobilized on Fe3O4@SiO2 nanoparticles [Fe3O4@SiO2-BAT-Pd(II) nanocomplex]. Characterization of Fe3O4@SiO2-BAT-Pd(II) nanocomplex using XRD, FT-IR, EDS, VSM, TEM and FESEM analyses. Catalytic cyanation of the various aryl halides with K4Fe(CN)6 under ligand-free conditions. The nanocomplex can be recovered and isolated six times with no significant loss of its catalytic ability.
Nasrollahzadeh, Mahmoud,Maryami, Mahboobe,Sajjadi, Mohaddeseh,Mehdipour, Ebrahim
(2019/03/11)

Catalytic oxidative conversion of aldehydes into nitriles using NH3·H2O/FeCl2/NaI/Na2S2O8: A practical approach to febuxostat
A novel approach to convert aldehydes into nitriles using NH3·H2O/FeCl2/NaI/Na2S2O8 has been developed. Both alkyl and aryl nitriles were obtained in good to excellent yields. Electron-withdrawing and electron-donating groups, such as fluoro, chloro, bromo, nitro, ester, cyano, trifluoromethyl and alkoxy were tolerated. Notably, febuxostat and its intermediate, ethyl 2-[3-cyano-4-(2-methylpropoxy)phenyl]-4-methyl-5-thiazolecarboxylate, were obtained in excellent yields.
Chen, Han,Sun, Sijia,Xi, Haoying,Hu, Kaifang,Zhang, Ning,Qu, Jingping,Zhou, Yuhan
supporting information
p. 1434 - 1436
(2019/05/01)

Green synthesis of benzonitrile using ionic liquid with multiple roles as the recycling agent
Preparation of benzonitrile from benzaldehyde and hydroxylamine hydrochloride is one of the most advantageous approaches. Nevertheless, it suffers from various constraints such as longer reaction time, corrosion and recovery of hydrochloric acid, the use of metal salt catalysts and their separation. For these reasons, a novel green benzonitrile synthetic route was proposed with ionic liquid as the recycling agent in this study. The results indicated that hydroxylamine 1-sulfobutyl pyridine hydrosulfate salt ((NH2OH)2·[HSO3-b-Py]·HSO4) was an expert alternative to hydroxylamine hydrochloride. Meanwhile, the ionic liquid [HSO3-b-Py]·HSO4 exhibited the multiple roles of co-solvent, catalysis and phase separation, thus the use of metal salt catalyst was eliminated, and no additional catalyst was needed. Hence, the separation process was greatly simplified. When the molar ratio of benzaldehyde to (NH2OH)2·[HSO3-b-Py]·HSO4 was 1:1.5, the volume ratio of paraxylene to [HSO3-b-Py]·HSO4 was 2:1, the benzaldehyde conversion and benzonitrile yield were both 100% at 120 °C in 2 h. Even better, the ionic liquid could be recovered easily by phase separation, and recycled directly after reaction. Additionally, this novel route is applicable to the green synthesis of a variety of aromatic, heteroaromatic and aliphatic nitriles with excellent yields.
Li, Zhihui,Wang, Tingting,Qi, Xudong,Yang, Qiusheng,Gao, Liya,Zhang, Dongsheng,Zhao, Xinqiang,Wang, Yanji
p. 17631 - 17638
(2019/06/24)

Method for preparing nitrile
The invention provides a method for preparing nitrile. Aldoxime carboxylic ester is used as a reactant to prepare a nitrile compound. The aldoxime carboxylic ester can be completely converted into corresponding nitrile under common catalysis of ferric salt and phenol within a few minutes. The method for preparing the nitrile has the advantages of gentle reaction conditions, simple and easy-to-getused reagents, cheap and environment-friendly catalyst, wide substrate application range, simple operation, rapid reaction and the like.
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Paragraph 0015

(2019/06/13)

Iron and Phenol Co-Catalysis for Rapid Synthesis of Nitriles under Mild Conditions
A mild, scalable, high yielding, and rapid route to access diverse nitriles from aldehyde oxime esters enabled by iron(III) and phenol co-catalysis has been developed. The reaction was performed at room temperature to give nitriles in excellent yield within minutes. Mechanistic studies show that the reaction may proceed through a radical process in which benzoyl aldehyde oxime is not only a substrate, but also an ancillary ligand to support iron salt in the promotion of the transformation.
Meng, Hong,Gao, Sen,Luo, Meiming,Zeng, Xiaoming
p. 4617 - 4623
(2019/07/15)

2,2-Diazido-1,2-diarylethanones: Synthesis and Reactivity with Primary Amines
We describe the synthesis and reactivity of a new class of diazidated compounds: the 2,2-diazido-1,2-diarylethanones. The diazides are easily accessible from 1,2-diarylethanones through a mild and simple protocol for the direct oxidative diazidation, using iodine and sodium azide in DMSO at room temperature. In studies towards their reactivity with amine nucleophiles under basic conditions, the diazides are shown to undergo a controlled fragmentation reaction that provides a straightforward access to the corresponding amides. In stark contrast to our previous results on the amine-triggered fragmentation of diazidated compounds, aromatic nitriles are found to be by-products of synthetic value. The net reaction consisting of diazidation and subsequent fragmentation, thus, provides a simple way to convert 1,2-diarylethanones into both aromatic amides and nitriles.
Holzschneider, Kristina,H?ring, Andreas P.,Kirsch, Stefan F.
p. 2824 - 2831
(2019/04/30)

Dual Ligand-Enabled Nondirected C-H Cyanation of Arenes
Aromatic nitriles are key structural units in organic chemistry and, therefore, highly attractive targets for C-H activation. Herein, the development of an arene-limited, nondirected C-H cyanation based on the use of two cooperatively acting commercially available ligands is reported. The reaction enables the cyanation of arenes by C-H activation in the absence of directing groups and is therefore complementary to established approaches.
Chen, Hao,Mondal, Arup,Wedi, Philipp,Van Gemmeren, Manuel
p. 1979 - 1984
(2019/02/19)

Palladium-Catalyzed Late-Stage Direct Arene Cyanation
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.
Zhao, Da,Xu, Peng,Ritter, Tobias
supporting information
p. 97 - 107
(2019/01/21)

Ligand-Promoted Non-Directed C?H Cyanation of Arenes
This article reports the first example of a 2-pyridone accelerated non-directed C?H cyanation with an arene as the limiting reagent. This protocol is compatible with a broad scope of arenes, including advanced intermediates, drug molecules, and natural products. A kinetic isotope experiment (kH/kD=4.40) indicates that the C?H bond cleavage is the rate-limiting step. Also, the reaction is readily scalable, further showcasing the synthetic utility of this method.
Liu, Luo-Yan,Yeung, Kap-Sun,Yu, Jin-Quan
supporting information
p. 2199 - 2202
(2019/01/24)

Biosynthesis of Pd/MnO2 nanocomposite using Solanum melongena plant extract and its application for the one-pot synthesis of 5-substituted 1H-tetrazoles from aryl halides
In this work, for the first time, Solanum melongena plant extract was used for the green synthesis of Pd/MnO2 nanocomposite via reduction osf Pd(II) ions to Pd(0) and their immobilization on the surface of manganese dioxide (MnO2) nanoparticles (NPs) as an effective support. The synthesized nanocomposite were characterized by various analytical techniques such as Fourier transform infrared (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS) and UV–Vis spectroscopy. The catalytic activity of Pd/MnO2 nanocomposite was used as a heterogeneous catalyst for the one-pot synthesis of 5-substituted 1H-tetrazoles from aryl halides containing various electron-donating or electron-withdrawing groups in the presence of K4[Fe (CN)6] as non-toxic cyanide source and sodium azide. The products were obtained in good yields via a simple methodology and easy work-up. The nanocatalyst can be recycled and reused several times with no remarkable loss of activity.
Nasrollahzadeh, Mahmoud,Ghorbannezhad, Fatemeh,Sajadi, S. Mohammad
(2018/12/14)

Mechanistic Insight Facilitates Discovery of a Mild and Efficient Copper-Catalyzed Dehydration of Primary Amides to Nitriles Using Hydrosilanes
Metal-catalyzed silylative dehydration of primary amides is an economical approach to the synthesis of nitriles. We report a copper-hydride(CuH)-catalyzed process that avoids a typically challenging 1,2-siloxane elimination step, thereby dramatically increasing the rate of the overall transformation relative to alternative metal-catalyzed systems. This new reaction proceeds at ambient temperature, tolerates a variety of metal-, acid-, or base-sensitive functional groups, and can be performed using a simple ligand, inexpensive siloxanes, and low catalyst loading.
Liu, Richard Y.,Bae, Minwoo,Buchwald, Stephen L.
supporting information
p. 1627 - 1631
(2018/02/17)

A Magnetically Recoverable and Reusable Catalyst for Synthesis of 5-Substituted 1H-Tetrazoles
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Elhampour, Ali,Nemati, Firouzeh
p. 493 - 501
(2019/01/09)

Copper-Catalyzed Unstrained C-C Single Bond Cleavage of Acyclic Oxime Acetates Using Air: An Internal Oxidant-Triggered Strategy toward Nitriles and Ketones
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.
Zhu, Chuanle,Chen, Fulin,Liu, Chi,Zeng, Hao,Yang, Zhiyi,Wu, Wanqing,Jiang, Huanfeng
p. 14713 - 14722
(2018/12/14)

Catalytic Promiscuity of Galactose Oxidase: A Mild Synthesis of Nitriles from Alcohols, Air, and Ammonia
We report an unprecedented catalytically promiscuous activity of the copper-dependent enzyme galactose oxidase. The enzyme catalyses the one-pot conversion of alcohols into the related nitriles under mild reaction conditions in ammonium buffer, consuming ammonia as the source of nitrogen and dioxygen (from air at atmospheric pressure) as the only oxidant. Thus, this green method does not require either cyanide salts, toxic metals, or undesired oxidants in stoichiometric amounts. The substrate scope of the reaction includes benzyl and cinnamyl alcohols as well as 4- and 3-pyridylmethanol, giving access to valuable chemical compounds. The oxidation proceeds through oxidation from alcohol to aldehyde, in situ imine formation, and final direct oxidation to nitrile.
Vilím, Jan,Knaus, Tanja,Mutti, Francesco G.
supporting information
p. 14240 - 14244
(2018/10/15)

Cyaniding method for preparing nitrile compound
The invention provides a cyaniding method for preparing a nitrile compound. Organic halide or pseudohalide, CO2 and NH3 which are low in price and are easily obtained and a reducing agent react, a selective cyaniding reaction is conducted in the presence of a transition metal catalyst, and the target product namely organic the nitrile compound is obtained. According to the cyaniding method for preparing the nitrile compound, a new reaction route is used, through a CO2 and NH3 reaction of metal catalysis, dehalogenation cyaniding or quasi halide cyaniding of halide or pseudohalide is directly achieved through a one-pot method, the problem is solved that a traditional cyanation reaction needs equivalent toxic cyanide, a new direct and convenient method for preparing isotope-labeled nitrile compounds is provided at the same time, and the method can be applied to medicine, tracing, biology and medicine research and development.
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Paragraph 0086-0088

(2018/05/30)

[1+1+3] Annulation of Diazoenals and Vinyl Azides: Direct Synthesis of Functionalized 1-Pyrrolines through Olefination
A dirhodium carboxylate catalyzed [1+1+3] annulation reaction of diazoenals and vinyl azides that gives synthetically important enal-functionalized 1-pyrroline derivatives was developed. The reaction involves a novel rhodium-catalyzed olefination of diazoenals with vinyl azides via electrophilic enal carbenoids, resulting in a new class of enal acrylates. The annulation reaction was used for the direct synthesis of valuable deuterated 1-pyrrolines. Structural diversification of the enal-functionalized 1-pyrrolines resulted in the biologically important pyrrolidine-fused oxaziridine, amino acid derivatives, and a 6-azabicyclo[3.2.1]octane motif present in polycyclic alkaloids.
Kanchupalli, Vinaykumar,Katukojvala, Sreenivas
p. 5433 - 5437
(2018/04/09)

Pd-Catalyzed Cyanation of (Hetero)Aryl Halides by Using Biphosphine Ligands
Tetraadamantylbiphosphine (TABP; L1), which showed superior activity in the palladium-catalyzed cyanation of 4-chloroanisole compared to standard phosphines, was synthesized as a new ligand. The generality of the new catalytic system was shown by the cyanation reaction of approximately 30 (hetero)aryl halides including hindered, electron-rich, and electron-poor aryl chlorides. These reactions constitute the first examples of using biphosphine ligands in Pd-catalyzed coupling reactions.
Zhang, Shaoke,Neumann, Helfried,Beller, Matthias
supporting information
p. 67 - 70
(2017/11/27)

Method for synthesizing aromaticnitrile by using metalloporphyrin to catalyze aromatic olefin
The invention discloses a method for synthesizing aromaticnitrile by using metalloporphyrin to catalyze aromatic olefin. The method is characterized in that an aromatic alkene compound or an aromaticheterocyclic alkene compound and nitrite are reacted to generate an aromaticnitrile compound or an aromatic heterocyclic nitrile compound under the catalyzing function of the metalloporphyrin by a one-step method in air atmosphere and an acid solution system. The method has the advantages that (1) the reaction conditions are moderate, the operation is simple, the control is easy, and the yield rate is higher; (2) the high-efficiency metalloporphyrin catalyst is used, but the poisonous CN (carbon-nitrogen) negative ion reagent is not used, so that the pollution to the environment is decreased;(3) the prices of raw materials, nitrogen sources, acid reagents and the like are low, the obtaining is easy, the production cost is obviously reduced, and the method can be popularized and applied toindustrialized production.
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Paragraph 0097-0101

(2018/03/01)

Pd/Mn Bimetallic Relay Catalysis for Aerobic Aldoxime Dehydration to Nitriles
A Pd/Mn bimetal system was found to be an effective catalyst for dehydration of aldoximes to the useful nitriles under mild aerobic conditions. Different to the known metal-catalyzed aldoxime dehydration reactions, this reaction very possibly proceeded via an alternative mechanism of Pd/Mn bimetal relay catalysis involving a Mn-catalyzed aerobic oxidation of aldoximes to nitrile oxides by air and a Pd-catalyzed oxygen transfer from the nitrile oxides to the solvent acetonitrile. This method tolerates a variety of substrates including sterically bulky ones and also the natural product derivative. (Figure presented.).
Zhang, Dongliang,Huang, Yaping,Zhang, Erlei,Yi, Rong,Chen, Chao,Yu, Lei,Xu, Qing
supporting information
p. 784 - 790
(2018/01/04)

Selective aerobic oxidation of benzylic amines to aryl nitriles catalyzed by CuBr2/N-methyl imidazole
A convenient and efficient copper-catalyzed aerobic oxidation of primary amines to aryl nitriles was described. Various benzylic and allylic amines were selectively oxidized to the corresponding nitriles in high yields using CuBr2/NMI as the catalyst and O2 as the oxidant. The oxidation reaction profiles monitored by 1H NMR disclosed the scenario of the reaction path as well as the role of the additives. The addition of NMI increased the rate of reaction and suppressed the hydrolysis and the deamination.
Shen, Yifan,Zhou, Yu,Jiang, Lili,Ding, Guangni,Luo, Luo,Zhang, Zhaoguo,Xie, Xiaomin
p. 4266 - 4271
(2018/07/06)

A Mechanochemical-Assisted Oxidation of Amines to Carbonyl Compounds and Nitriles
A mild, efficient, metal- and solvent-free oxidation of primary amines to aldehydes, ketones, and nitriles under ball-milling conditions is presented. This method has proved to be compatible with various functional groups and only requires easily accessible starting materials. Simple purification of the reaction mixtures by short-column chromatography afforded pure aldehydes, ketones, and nitriles as products.
Gaspa, Silvia,Porcheddu, Andrea,Valentoni, Antonio,Garroni, Sebastiano,Enzo, Stefano,De Luca, Lidia
supporting information
p. 5519 - 5526
(2017/09/06)

PROCESS FOR THE PREPARATION OF ORGANIC HALIDES
The present invention provides a halo-de-carboxylation process for the preparation of organic chlorides, organic bromides and mixtures thereof, from their corresponding carboxylic acids, using a chlorinating agent selected from trichloroisocyanuric acid (TCCA), dichloroisocyanuric acid (DCCA), or combination thereof, and a brominating agent.
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Paragraph 00146

(2017/08/01)

O-BENZENESULFONYL-ACETOHYDROXAMIC ACID ESTER DERIVATIVE AND MANUFACTURING METHOD OF NITRYL COMPOUND
PROBLEM TO BE SOLVED: To provide a novel synthetic agent for manufacturing a nitryl compound without using a hydroxylamine derivative which has problems in storage property or handleability. SOLUTION: There is related O-benzene sulfonyl-acetohydroxamic acid ester derivative represented by the following chemical formula, where R1 is H, CF3 or CH3, R2 is CH3, C2H5 or C3H7. There is related a nitryl compound synthesizing agent for synthesizing a nitryl compound from an aldehyde compound containing the O-benzene sulfonyl-acetohydroxamic acid ester derivative and further a manufacturing method of a nitryl compound including a process for transferring the aldehyde compound to oxime in the presence of the synthesizing agent, an organic solvent and an acid catalyst. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0033; 0035-0037

(2017/10/26)

AEROBIC OXIDATIVE CONVERSION OF PRIMARY ALCOHOLS TO NITRILES USING A NITROXYL/NOx CATALYST SYSTEM
The present invention refers to a primary alcohol (Aromatic primary alcohol) (Nitrile) aerobic oxidation conversion to aromatic 1 knight reel (Aerobic oxidative conversion) method relates to a, preferably oxygen plasma under conditions provided NO and 31gx Non-metallic catalyst system consisting of aromatic aldehyde alcohol after conversion into aromatic 1 difference, won - under such conditions by adding aromatic aldehydes into ammonia source port (One-a pot) manner by switching knight reel, to replace the existing transition metal catalyst to selectively can be obtained for various substrate for high yield knight reel and intermediates can be isolated without synthesizing simple manner to positive number can be calculated even interlayer dielectric green [khey [khey] america, night-lock chambers/NOx Catalyst system using oxidative cycle difference alcohol to aerobic knight reel 1, and applied to the optimization of the reaction conditions are disclosed. (by machine translation)
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Paragraph 0088-0103; 0133

(2017/11/14)

A practical iodine-catalyzed oxidative conversion of aldehydes to nitriles
A simple and efficient method for the direct synthesis of nitriles from aldehydes using ammonium acetate as the nitrogen source has been developed. The reactions were performed with iodine as the catalyst and tert-butyl hydroperoxide (TBHP) as the oxidant under mild conditions. A variety of aromatic, heteroaromatic, aliphatic and allylic aldehydes could be converted into their corresponding nitriles in good to excellent yields.
Fang, Chaojie,Li, Meichao,Hu, Xinquan,Mo, Weimin,Hu, Baoxiang,Sun, Nan,Jin, Liqun,Shen, Zhenlu
p. 1484 - 1489
(2017/01/21)

Catalytic and oxidizing synthetic method of nitriles compound
The invention discloses a catalytic and oxidizing synthetic method of a nitriles compound. The catalytic and oxidizing synthetic method comprises the following steps: adding reaction substrate aldehyde, NH4OAc, alkaline additives, I2 and TBHP (tert-butyl hydroperoxide) into an ethanol solvent, facilitating the reaction for 3 to 17 h at 40 to 60 DEG C, adding a sodium thiosulfate solution into a reaction solution, stirring, extracting with diethyl ether, separating to obtain an organic layer, decompressing and steaming to remove the solvent, performing the column chromatography isolation, adopting a mixed solution of ethyl acetate/petroleum ether in a volume ratio of 1: 100 as an eluent, collecting an elution solution containing a target compound, and steaming to remove the solvent, thus obtaining the product nitriles, wherein a weight ratio of the reaction substrate aldehyde to the alkaline additives to NH4OAc to I2 to TBHP is 100: (100 to 120): (120 to 160): (2 to 3): (100 to 120). The synthetic method has the beneficial effects that the operation is simple and safe, and the reaction condition is relatively moderate; and the reaction substrate is wide in application range.
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Paragraph 0035

(2017/07/23)

Electrocatalytic synthesis of nitriles from aldehydes with ammonium acetate as the nitrogen source
A simple synthesis method of nitriles from corresponding aldehydes by electrochemical oxidation was developed with ammonium acetate as the nitrogen source and 4-acetamido- 2,2,6,6-tetramethylpiperidinyl-l-oxy (4-AcNH-TEMPO) as the catalyst. Cyclic voltammetry was performed to investigate the electrocatalytic activity of 4-AcNH-TEMPO for the conversion of benzaldehyde to benzonitrile. On the basis of in situ FTIR data and cyclic voltammetry experiments, a reaction mechanism, involving the redox of 4-AcNH-TEMPO and the generation of intermediate imine during the reaction, was proposed. This electrocatalytic reaction system provided an efficient protocol for synthesis of aromatic nitriles at room temperature with moderate to high yields.
Yang, Xianjing,Fan, Zhongquan,Shen, Zhenlu,Li, Meichao
p. 53 - 59
(2017/01/09)

Diisopropylethylammonium acetate (DIPEAc): An efficient and recyclable catalyst for the rapid synthesis of 5-substituted-1H-tetrazoles
A simple and efficient protocol developed for the synthesis of 5-substituted 1H-tetrazole derivatives through [2+3] cycloaddition reaction between benzonitriles and sodium azide using diisopropylethylammonium acetate as a recyclable reaction medium is described. The reactions proceed well at 80 °C and provide the corresponding tetrazoles in good to excellent yields (up to 94% yield). Developed method has notable advantages, such as simple and mild conditions, easy workup, reusability with consistent catalytic activity, and safer alternative to hazardous, corrosive conventional Lewis acid catalysts.
Bhosle, Manisha R.,Shaikh, Dastgir S.,Khillare, Lalit D.,Deshmukh, Amarsinh R.,Mane, Ramrao A.
p. 695 - 703
(2017/03/27)

A highly efficient heterogeneous copper-catalyzed chlorodeboronation of arylboronic acids leading to chlorinated arenes
A highly efficient heterogeneous copper-catalyzed chlorodeboronation of arylboronic acids with inexpensive N-chlorosuccinimide (NCS) was achieved in MeCN in the presence of 10 mol% of l-proline-functionalized MCM-41-immobilized copper(i) complex [MCM-41-l-proline-CuCl] under mild conditions, yielding a variety of aryl chlorides in excellent yields. This method proved to be tolerant of a broad range of functional groups and particularly useful for the conversion of electron-deficient arylboronic acids to aryl chlorides, a transformation that is inefficient without copper catalysis. This heterogeneous copper catalyst can be recovered by a simple filtration of the reaction solution and recycled for at least 10 times without any decreases in activity.
He, Wen,Zhang, Rongli,Cai, Mingzhong
p. 764 - 770
(2017/01/13)

Synthesis of nitriles from aerobic oxidation of amines catalyzed by ruthenium supported on activated carbon
Nitriles were synthesized from the aerobic oxidation of amines over commercially available catalysts, which were activated carbon-supported ruthenium catalysts (Ru/AC). The 5%Ru/AC catalyst can tolerate a wide range of substrates, such as aromatic, aliphatic, and heterocyclic amines, and afford the target nitriles in good-to-excellent yields. The 5%Ru/AC catalyst was easily recovered and no ruthenium leaking took place in the catalytic run.
Niu, Baoqiang,Lu, Fei,Zhang, Hong-Yu,Zhang, Yuecheng,Zhao, Jiquan
supporting information
p. 330 - 333
(2017/02/23)

Direct synthesis of nitriles by Cu/DMEDA/TEMPO-catalyzed aerobic oxidation of primary amines with air
By screening the copper catalysts, ligands, and the reaction conditions, a simple CuCl/DMEDA/TEMPO catalyst system readily available from commercial sources is developed for a direct and selective synthesis of the useful nitriles by an aerobic oxidation reaction of primary amines using air as an advantageous oxidant under mild conditions.
Ma, Xian-Tao,Xu, Hao,Xiao, Ying-Lin,Su, Chen-Liang,Liu, Jian-Ping,Xu, Qing
p. 1336 - 1339
(2017/06/21)

Ligand controlled switchable selectivity in ruthenium catalyzed aerobic oxidation of primary amines
A ligand controlled catalytic system for the aerobic oxidation of 1° amines to nitriles and imines has been developed where the varying π-acidic feature of BIAN versus phen in the frameworks of ruthenium catalysts facilitates switchable selectivity.
Ray, Ritwika,Chandra, Shubhadeep,Yadav, Vishal,Mondal, Prasenjit,Maiti, Debabrata,Lahiri, Goutam Kumar
supporting information
p. 4006 - 4009
(2017/04/11)

A method for preparing of the benzonitrile derivatives
The invention discloses a preparation method of a cyanobenzene derivative. The cyanobenzene derivative is prepared by taking phenylacetic acid or the derivative thereof as well as urea as raw materials, copper salt as a catalyst and oxygen as an oxidizing agent. According to the preparation method disclosed by the invention, by adopting copper salt as the catalyst and oxygen as the oxidizing agent without an extra cocatalyst, the raw materials phenylacetic acid or the derivative thereof are easy to purchase in the market, low in cost and various in type, and urea as the source of cyanogen is low in toxicity, low in price, mild in reaction condition and environmentally friendly, and has a good functional group compatibility.
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Paragraph 0021; 0022; 0023; 0054; 0055; 0056; 0057

(2016/10/17)

Synthesis of nitriles from aldehydes with trimethylphenylammonium tribromide and ammonium acetate
Various aromatic and heterocyclic aldehydes were easily converted to respective nitriles with the combination of trimethylphenylammonium tribromide and ammonium acetate in good yields at room temperature.
Sayama, Shinsei
p. 1796 - 1802
(2016/11/06)

A Mild TEMPO-Catalyzed Aerobic Oxidative Conversion of Aldehydes into Nitriles
An efficient method to prepare nitriles from aldehydes using hexamethyldisilazane (HMDS) as the nitrogen source has been developed. The reactions were performed with 2,2,6,6-tetramethylpiperidine l-oxyl (TEMPO) as the catalyst, NaNO2 or TBN as the co-catalyst, and molecular oxygen as the terminal oxidant under mild conditions. A variety of aromatic, heteroaromatic, aliphatic and allylic aldehydes could be converted into their corresponding nitriles in good to excellent yields.
Fang, Chaojie,Li, Meichao,Hu, Xinquan,Mo, Weimin,Hu, Baoxiang,Sun, Nan,Jin, Liqun,Shen, Zhenlu
p. 1157 - 1163
(2016/04/19)

Direct synthesis of nitriles from aldehydes with hydroxylamine-O-sulfonic acid in acidic water
Herein is reported the selective transformation of aldehydes to nitriles in the presence of hydroxylamine-O-sulfonic acid (NH2OSO3H) as a source of the N atom and acidic water. The reaction works with high yields for a large array of aromatic and aliphatic aldehydes, as well as hindered aldehydes and conjugated aldehydes without purification. The reaction conditions are very mild and tolerate a wide array of functional groups. In principle, the reaction can be completed in vinegar.
Quinn, Dylan J.,Haun, Graham J.,Moura-Letts, Gustavo
supporting information
p. 3844 - 3847
(2016/08/02)

Electrochemical synthesis of nitriles from aldehydes using TEMPO as a mediator
A novel electrochemical route to generate nitriles from aldehydes under mild conditions using a catalytic amount of TEMPO (2,2,6,6-tetramethylpiperidinyl-l-oxy) as the mediator and hexamethyldisilazane as the nitrogen source in the presence of acetic acid has been developed. A variety of aromatic, heteroaromatic and aliphatic aldehydes have been converted to their corresponding nitriles in good to excellent yields. A plausible reaction mechanism is proposed based on the cyclic voltammetry, in situ FTIR and the identification of intermediates.
Chen, Qiguo,Fang, Chaojie,Shen, Zhenlu,Li, Meichao
p. 51 - 55
(2016/02/18)

Nitrilation of carboxylic acids with acetonitrile catalyzed by molybdenum and vanadium complexes
Various carbonitriles were synthesized by reaction of the corresponding carboxylic acids with acetonitrile in carbon tetrachloride in the presence of VO(acac)2and Mo(CO)6in 6 h at 150–170°C.
Khusnutdinov,Shchadneva,Bayguzina,Mayakova, Yu. Yu.
p. 1282 - 1286
(2016/10/26)

An aerobic Cu-mediated practical approach to aromatic nitriles using cyanide anions as the nitrogen source
A Cu-mediated cyanation of aryl methyl ketones using cyanide anions as the nitrogen source was achieved to provide aromatic nitriles in moderate to good yields. The reaction tolerates a variety of synthetically important functional groups.
Gu, Lijun,Jin, Cheng,Zhang, Hongtao,Liu, Jiyan,Li, Ganpeng,Yang, Zhi
p. 6687 - 6690
(2016/07/23)

Cleavage of the Carbon–Carbon Triple Bonds of Arylacetylenes for the Synthesis of Arylnitriles without a Metal Catalyst
Cleavage of the carbon–carbon triple bonds of alkynes was achieved, which led to the synthesis of arylnitriles under transition-metal-free conditions. A vast range of terminal alkyne substrates underwent this reaction to provide the corresponding nitriles in moderate to good yields with good functional group tolerance.
Lin, Yuanguang,Song, Qiuling
p. 3056 - 3059
(2016/07/12)