cas 619-24-9, 3-Nitrobenzonitrile | Articles data

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Nitration of deactivated aromatic compounds via mechanochemical reaction
A variety of deactivated arenes were nitrated to their corresponding nitro derivatives in excellent yields under high-speed ball milling condition using Fe(NO3)3·9H2O/P2O5 as nitrating reagent. A radical involved mechanism was proposed for this facial, eco-friendly, safe, and effective nitration reaction.
Wu, Jian-Wei,Zhang, Pu,Guo, Zhi-Xin
supporting information

(2021/05/05)

Photoinduced Iron-Catalyzed ipso-Nitration of Aryl Halides via Single-Electron Transfer
A photoinduced iron-catalyzed ipso-nitration of aryl halides with KNO2 has been developed, in which aryl iodides, bromides, and some of aryl chlorides are feasible. The mechanism investigations show that the in situ formed iron complex by FeSO4, KNO2, and 1,10-phenanthroline acts as the light-harvesting photocatalyst with a longer lifetime of the excited state, and the reaction undergoes a photoinduced single-electron transfer (SET) process. This work represents an example for the photoinduced iron-catalyzed Ullmann-type couplings.
Wu, Cunluo,Bian, Qilong,Ding, Tao,Tang, Mingming,Zhang, Wenkai,Xu, Yuanqing,Liu, Baoying,Xu, Hao,Li, Hai-Bei,Fu, Hua
p. 9561 - 9568
(2021/08/06)

Recyclable and Reusable Pd(OAc)2/XPhos–SO3Na/PEG-400/H2O System for Cyanation of Aryl Chlorides with Potassium Ferrocyanide
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.]
Cai, Mingzhong,Huang, Bin,Liu, Rong,Xu, Caifeng
(2021/12/03)

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)

Dehydration of aldoximes to nitriles using trichloroacetonitrile without catalyst
Trichloroacetonitrile has been found to be an efficient dehydrating agent for a range of aldoximes including aromatic and heterocyclic aldoxime yielding the corresponding nitriles in moderate to good yields. The dehydration reactions can take place in non-acetonitrile media without the aid of a metal catalyst. In addition, it has been confirmed that trichloroacetonitrile was converted into trichloroacetamide in the reaction.
Ma, Xiaoyun,Liu, Dan,Chen, Zhengjian
p. 3261 - 3266
(2021/06/30)

Bis-morpholinophosphorylchloride, a novel reagent for the conversion of primary amides into nitriles
Bis-morpholinophosphorylchloride (Bmpc), in the presence of a base, is an efficient dehydrating agent for both aromatic and aliphatic primary amides, and gives corresponding nitriles under mild conditions in god yields and purity. During the reaction the enantiomeric integrity remains intact.
Rao, P. Purnachandra,Nowshuddin, Shaik,Jha, Anjali,Rao, B. Leela Maheswara,Divi, Murali K.,Rao
supporting information

(2021/01/21)

Facile dehydration of primary amides to nitriles catalyzed by lead salts: The anionic ligand matters
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.
Ruan, Shixiang,Ruan, Jiancheng,Chen, Xinzhi,Zhou, Shaodong
(2020/12/09)

Development and Molecular Understanding of a Pd-Catalyzed Cyanation of Aryl Boronic Acids Enabled by High-Throughput Experimentation and Data Analysis
A synthetic method for the palladium-catalyzed cyanation of aryl boronic acids using bench stable and non-toxic N-cyanosuccinimide has been developed. High-throughput experimentation facilitated the screen of 90 different ligands and the resultant statistical data analysis identified that ligand σ-donation, π-acidity and sterics are key drivers that govern yield. Categorization into three ligand groups – monophosphines, bisphosphines and miscellaneous – was performed before the analysis. For the monophosphines, the yield of the reaction increases for strong σ-donating, weak π-accepting ligands, with flexible pendant substituents. For the bisphosphines, the yield predominantly correlates with ligand lability. The applicability of the designed reaction to a wider substrate scope was investigated, showing good functional group tolerance in particular with boronic acids bearing electron-withdrawing substituents. This work outlines the development of a novel reaction, coupled with a fast and efficient workflow to gain understanding of the optimal ligand properties for the design of improved palladium cross-coupling catalysts.
De Jesus Silva, Jordan,Bartalucci, Niccolò,Jelier, Benson,Grosslight, Samantha,Gensch, Tobias,Schünemann, Claas,Müller, Bernd,Kamer, Paul C. J.,Copéret, Christophe,Sigman, Matthew S.,Togni, Antonio
(2021/11/10)

Revisiting the synthesis of aryl nitriles: a pivotal role of CAN
Facilitated by the dual role of Ceric Ammonium Nitrate (CAN), herein we report a cost-effective approach for the cyanation of aryl iodides/bromides with CAN-DMF as an addition to the existing pool of combined cyanation sources. In addition to being an oxidant, CAN acts as a source of nitrogen in our protocol. The reaction is catalyzed by a readily available Cu(ii) salt and the ability of CAN to generate ammonia in the reaction medium is utilized to eliminate the additional requirement of a nitrogen source, ligand, additive or toxic reagents. The mechanistic study suggests an evolution of CN?leading to the synthesis of a variety of aryl nitriles in moderate to good yields. The proposed mechanism is supported by a series of control reactions and labeling experiments.
Saikia, Rakhee,Park, Kwihwan,Masuda, Hayato,Itoh, Miki,Yamada, Tsuyoshi,Sajiki, Hironao,Mahanta, Sanjeev P.,Thakur, Ashim J.
p. 1344 - 1351
(2021/02/27)

Pd@CeO2-catalyzed cyanation of aryl iodides with K4Fe(CN)6·3H2O under visible light irradiation
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.
Wang, Shengyu,Wang, Jianqiang,Pan, Junyi,Liu, Cheng,Gong, Xubin,Guo, Cheng
(2021/01/12)

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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(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)

Pd/CoFe2O4/chitosan: A highly effective and easily recoverable hybrid nanocatalyst for synthesis of benzonitriles and reduction of 2-nitroaniline
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.
Baran, Talat,Nasrollahzadeh, Mahmoud
(2020/10/02)

An easily fabricated palladium nanocatalyst on magnetic biochar for Suzuki-Miyaura and aryl halide cyanation reactions
Biochar is a carbon-rich solid, the surface of which is covered with a high density of functional carbonyl, hydroxyl and carboxylic acid groups. In this work, palladium nanoparticles were embedded on magnetic biochar and a new reusable and environmentally-friendly catalyst was developed and applied for the promotion of Suzuki-Miyaura C-C coupling and cyanation reactions. The high-carbon (77%), low-ash content (5.8%) and the relatively high surface area (266 m2g?1) of pine tree biochar (PTB) suggested that it might be highly suitable as a catalyst substrate. The Fe3O4-Pd-biochar nanocomposite was successfully characterized using SEM, TEM, EDX, FT-IR, BET and XRD. Its catalytic role was initially evaluated usingp-NO2C6H4I as a model reactant (for both types of reactions) and later for the production of biaryls and benzonitriles from a wide range of aryl halides under mild reaction conditions. Biaryls and benzonitriles were characterized using GC-MS. In the case of the Suzuki-Miyaura reaction, the optimum yield of 98% was obtained with a catalyst concentration of 0.04 mol%, microwave irradiation of 400 W, and a residence time of 5 min, using K2CO3as the base. With respect to the cyanation reaction, dimethylformamide, Na2CO3and 6 h were the optimum solvent, base and reaction duration, respectively. Subsequently, the nanocatalyst showed excellent catalytic activity in both reactions, achieving >88% yields in most cases, regardless of the aryl iodide or bromide used and the type of substitution.
Akay, Sema,Baran, Talat,Kalderis, Dimitrios,Kayan, Berkant,Tsubota, Toshiki,Turun?, Ersan
p. 12519 - 12527
(2021/07/25)

Oxidation/ MCR domino protocol for direct transformation of methyl benzene, alcohol, and nitro compounds to the corresponding tetrazole using a three-functional redox catalytic system bearing TEMPO/Co(III)-porphyrin/ Ni(II) complex
A redox catalytic system for oxidation-reduction reactions and the domino preparation of tetrazole compounds from nitro and alcohol precursors was designed, prepared and characterized by UV–vis, GPC, TGA, XRD, EDX, XPS, VSM, FE-SEM, TEM, DLS, BET, NMR, and ICP analyses. The catalyst was prepared via several successive steps by demetalation of chlorophyll b, copolymerization with acrylated TEMPO monomers, complexation with Ni and Co metals (In two different steps), then immobilized on magnetic nanoparticles. The presence of three functional groups including TEMPO, coordinated cobalt, and coordinated nickel in the catalyst, allowed the oxidation of various types of alcohols, alkyl benzenes as well as the reduction of nitro compounds by a single catalyst. All reactions yielded up to 97 % selectivity for oxidation and reduction reactions. Next, the ability of the catalyst to successfully convert alcohol, methyl benzenes and nitro to their corresponding tetrazoles was studied.
Mahmoudi, Boshra,Rostami, Amin,Kazemnejadi, Milad,Hamah-Ameen, Baram Ahmed
(2020/12/21)

NITRATION
The present invention relates to a process for preparing a nitrated compound, comprising the step of reacting a compound (A) comprising at least one substituted or unsubstituted aromatic or heteroaromatic ring, wherein said heteroaromatic ring comprises at least one heteroatom selected from the group consisting of oxygen, sulfur, phosphor, selenium and nitrogen, with a compound of formula (I) wherein Y is selected from the group consisting of hydrogen and nitro.
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(2020/05/28)

A convenient reagent for the conversion of aldoximes into nitriles and isonitriles
For the dehydroxylation of aldoximes with 4-nitro-1-((trifluoromethyl)sulfonyl)-imidazole (NTSI), slight modifications of reaction conditions resulted in significantly different reaction paths to provide either nitriles or isonitriles. The challenging conversion of aldoximes into isonitriles was achieved under mild conditions.
Zhang, Wei,Lin, Jin-Hong,Zhang, Pengfei,Xiao, Ji-Chang
supporting information
p. 6221 - 6224
(2020/06/29)

An Efficient Synthesis of Nitriles from Aldoximes in the Presence of Trifluoromethanesulfonic Anhydride in Mild Conditions
Abstract: A new and convenient protocol has been proposed for the transformation of aldoximes to nitriles using trifluoromethanesulfonic anhydride and triethylamine. The proposed method allows a range of aldoximes, including aromatic, heterocyclic, aliphatic, and cycloaliphatic aldoximes, to be converted to the corresponding nitriles in good to excellent yields.
Uludag, N.
p. 1640 - 1645
(2020/10/22)

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)

Photocatalytic Conversion of Benzyl Alcohols/Methyl Arenes to Aryl Nitriles via H-Abstraction by Azide Radical
This report presents the visible-light-assisted synthesis of aryl nitriles from easily accessible alcohols or methyl arenes in the presence of O2. Organic photoredox catalyst, 4CzIPN (1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene), induces single electron transfer (SET) from azide N3? and generates azide radical N3?.The photogenerated N3? abstracts H atom from α-C?H bond of benzylic system, which provides aldehyde and hydrazoic acid (HN3) in situ. This reaction subsequently forms azido alcohol intermediate that transforms into nitrile with the assistance of triflic acid (Br?nsted acid). A range of alcohols and methyl arenes successfully underwent cyanation at room temperature with good to excellent yields and showed good functional group tolerance.
Shee, Maniklal,Shah, Sk. Sheriff,Singh, N. D. Pradeep
supporting information
p. 14070 - 14074
(2020/10/12)

Green synthesis of palladium nanocatalyst derived from the β-cyclodextrin used as effective heterogeneous catalyst for cyanation of aryl halides
In this study, preparation of highly stable palladium nanoparticles (Pd NPs) on Schiff base modified β-cyclodextrin (β-CD-Sch) in the absence of reducing agents has been successfully carried out. Pd NPs&at;β-CD-Sch has then been applied as nanocatalyst in the synthesis of benzonitriles via cyanation reaction using K4Fe(CN)6, which is a low cost, commercially available and non-toxic cyanide source. A series of benzonitriles containing different substrates were successfully fabricated with 77–98percent yields using Pd NPs&at;β-CD-Sch. Moreover, Pd NPs&at;β-CD-Sch catalyst was quantitatively recovered and reutilized several times, showing good reaction yields. This work revealed that i) prepared β-CD-Sch is an effective stabilizer for the fabrication of Pd NPs and ii) Pd NPs&at;β-CD-Sch catalyst play an important role in the fabrication of benzonitriles.
Baran, Talat,Nasrollahzadeh, Mahmoud
(2020/07/31)

Difluorocarbene-Based Cyanation of Aryl Iodides
A large number of efficient cyanation methods have been developed because of the wide range of applications of nitriles, but conventional methods usually suffer from the need for a toxic cyanation reagent. Although difluorocarbene chemistry has received increasing attention, the use of difluorocarbene as a sources of the nitrile carbon for nitrile groups remains largely unexplored. We describe a difluorocarbene-based cyanation of aryl iodides promoted by a cheap copper source, Cu(NO 3) 2 ·2.5H 2 O, under an air atmosphere. Ph 3 P + CF 2 CO 2-, an easily available and shelf-stable difluorocarbene reagent, and NaNH 2 are used as the carbon source and the nitrogen source for the nitrile group, respectively. The cyanation protocol is attractive because no toxic reagent is used and performing the reactions under an air atmosphere is operationally convenient.
Cao, Yu-Cai,Du, Ruo-Bing,Fu, Zhi-Hong,Guo, Yu,Lin, Jin-Hong,Xiao, Ji-Chang,Xiao, Xuan,Yao, Xu,Zhang, Yin-Xiang,Zheng, Xing
supporting information
p. 713 - 717
(2020/04/08)

Organophotoredox assisted cyanation of bromoarenes: via silyl-radical-mediated bromine abstraction
The insertion of a nitrile (-CN) group into arenes through the direct functionalization of the C(sp2)-Br bond is a challenging reaction. Herein, we report an organophotoredox method for the cyanation of aryl bromides using the organic photoredox catalyst 4CzIPN and tosyl cyanide (TsCN) as the nitrile source. A photogenerated silyl radical, via a single electron transfer (SET) mechanism, was employed to abstract bromine from aryl bromide to provide an aryl radical, which was concomitantly intercepted by TsCN to afford the aromatic nitrile. A range of substrates containing electron-donating and -withdrawing groups was demonstrated to undergo cyanation at room temperature in good yields.
Shah, Sk. Sheriff,Shee, Maniklal,Singh, N. D. Pradeep
supporting information
p. 4240 - 4243
(2020/04/22)

Pd NPs?Fe3O4/chitosan/pumice hybrid beads: A highly active, magnetically retrievable, and reusable nanocatalyst for cyanation of aryl halides
In this study, Fe3O4/chitosan/pumice hybrid beads were developed as a new stabilizer agent, and palladium nanoparticles (Pd NPs) were successfully decorated on the designed stabilizer without adding any toxic reducing resource. Then, the potential use of Pd NPs?Fe3O4/chitosan/pumice hybrid beads as a heterogeneous catalyst against different aryl halide cyanations was investigated with K4[Fe(CN)6]. In these reactions, Pd NPs? Fe3O4/chitosan /pumice hybrid beads showed high catalytic activity by converting aryl halides to the desired benzonitriles with high product yields (80 %–98 %). Due to the magnetically separable nature of Pd NPs?Fe3O4/chitosan/pumice hybrid beads, they were reused several times, and 86 % yield was obtained even after six successive runs. This paper reveals that Pd NPs?Fe3O4/chitosan/pumice hybrid beads have a high potential to synthesis a broad range of nitriles due to their excellent catalytic and retrievable capability.
Baran, Talat
(2020/03/17)

An aerobic and green C-H cyanation of terminal alkynes
This study describes a benign C-H cyanation of terminal alkynes with α-cyanoesters serving as a nontoxic cyanide source. In situ generation of the key copper cyanide intermediate is proposed by a sequence of α-C-H oxidation and copper-mediated β-carbon elimination of α-cyanoesters, releasing the α-ketoester byproduct observed experimentally. The ensuing reaction of copper cyanide with terminal alkynes delivers preferentially cyanoalkynes and surpasses the possible Glaser type dimerization of terminal alkynes or the undesired accumulation of HCN under protic conditions. The presence of the co-oxidant K2S2O8 is crucial to this selectivity, probably by promoting oxidative transmetalation and the resulting formation of the Cu(iii)(acetylide)(CN) intermediate. All the reagents and salts used are commercially available, cheap and nontoxic, avoiding the use of highly toxic cyanide salts typically required in cyanation studies. The scope of this reaction is demonstrated with a set of alkynes and α-cyanoesters. The application of this method to late-stage functionalization of the terminal alkyne group in an estrone derivative is also feasible, showing its practical value for drug design.
Si, Yi-Xin,Zhang, Song-Lin,Zhu, Peng-Fei
supporting information
p. 9216 - 9220
(2020/12/03)

Dibenzonitrile derivative of o-carborane, modified compound thereof, and synthetic methods thereof
The invention provides a dibenzonitrile derivative of o-carborane. Besides, in order to further improve the affinity with tumor cells and the high-boron aggregation effect in the tumor cells so as toenable the derivative to have a potential anti-tumor application performance, structural modification is performed on the derivative, and a modified compound of the derivative is provided. Meanwhile,the invention also provides a synthesis method of the compounds. An in-vitro experiment is adopted to screen the structure of the dibenzonitrile derivative of the novel o-carborane; an m-amino benzonitrile structure is introduced through chemical synthesis; the purpose of increasing the lipophilicity of the compound and the affinity of tumor cells is achieved, the technical effect of targeted ultra-high concentration enrichment of boron ions in the tumor cells is achieved through the novel structure, and then the bottleneck problem that the concentration of p-borane phenylalanine (BPA) in thetumor cells cannot reach a high level is solved.
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(2020/06/16)

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)

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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(2019/06/13)

Sulfuryl Fluoride Mediated Conversion of Aldehydes to Nitriles
Aliphatic, aromatic, and heteroaromatic aldehydes were readily converted to corresponding nitriles in a one-pot reaction sequence with hydroxylamine and sulfuryl fluoride. The reaction proceeds at room temperature, does not require metal catalysts and special precautions, and produces nitriles in excellent yields. It is compatible with a variety of functional groups, can be performed in aqueous and organic solvents, and is readily scalable to multigram quantities. Mild conditions and high selectivity of the reaction enabled the construction of polyfunctional probes containing nitrile, alkyne, azide, and fluorosulfate groups for further orthogonal derivatization.
Gurjar, Jitendra,Bater, Jorick,Fokin, Valery V.
supporting information
p. 1906 - 1909
(2019/01/24)

Highly Efficient Microwave-assisted One-Pot Synthesis of Aromatic Nitriles from Aromatic Aldehydes
A highly efficient and environmentally benign protocol is described for the microwave-assisted one-pot synthesis of aromatic nitriles from aromatic aldehydes by the reaction with hydroxylamine hydrochloride in DMSO, which involves the intermediate formation of aldoximes and subsequent dehydration. The developed synthetic methodology can be readily accomplished with various aldehydes containing both electron-donor and electron-acceptor groups, providing excellent yields of the target products in shorter reaction times (1–2 min) compared to previously reported methodologies.
Pujari,Thorat,Mahipal,Bhondwe
p. 702 - 706
(2019/07/17)

Continuous-flow synthesis of nitriles from aldehydes via Schmidt reaction
A continuous-flow synthesis of nitriles by Schmidt reaction has been developed. Using this procedure, a variety of aldehydes could be smoothly transformed into the desired nitriles in good to excellent yields. The mild reaction conditions and the flowing reaction system greatly improved the safety and make the reaction easy to scale up.
Zhan, Wei,Tong, Meng,Ji, Ling,Zhang, Han,Ge, Zemei,Wang, Xin,Li, Runtao
p. 973 - 976
(2019/01/29)

Visible-light-driven catalytic oxidation of aldehydes and alcohols to nitriles by 4-acetamido-tempo using ammonium carbamate as a nitrogen source
A mild and efficient route to prepare nitriles from aldehydes by combining photoredox catalysis with oxoammonium cations is reported. The reaction is performed using ammonium carbamate as the nitrogen source. The practicality of the method is increased by the extension of the dual catalytic system to one-pot two-step conversion of alcohols to nitriles.
Nandi, Jyoti,Leadbeater, Nicholas E.
supporting information
p. 9182 - 9186
(2019/11/05)

Cascade Process for Direct Transformation of Aldehydes (RCHO) to Nitriles (RCN) Using Inorganic Reagents NH2OH/Na2CO3/SO2F2 in DMSO
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.
Fang, Wan-Yin,Qin, Hua-Li
p. 5803 - 5812
(2019/05/14)

A Transition-Metal-Free One-Pot Cascade Process for Transformation of Primary Alcohols (RCH2OH) to Nitriles (RCN) Mediated by SO2F2
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.
Jiang, Ying,Sun, Bing,Fang, Wan-Yin,Qin, Hua-Li
p. 3190 - 3194
(2019/05/21)

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)

SO 2 F 2 -Promoted Dehydration of Aldoximes: A Rapid and Simple Access to Nitriles
A rapid, simple and mild process for the dehydration of aldoximes to give the corresponding nitriles, which utilizes SO 2 F 2 as an efficient reagent, has been developed. A variety of (hetero)arene, alkene, alkyne and aliphatic aldoximes proceeded with high efficiency to afford nitriles in excellent to quantitative yields with great functional group compatibilities in acetonitrile under ambient conditions. Furthermore, an eco-friendly synthetic protocol to access nitriles from aldehydes with ortho -, meta - and para -nitrile groups was also described in aqueous methanol by using inorganic base Na 2 CO 3, and a one-pot synthetic strategy to generate nitriles from aldehydes was proved to be feasible.
Ding, Chengrong,Mei, Guangyao,Wang, Haibo,Zhang, Guofu,Zhao, Yiyong
p. 1484 - 1488
(2019/07/15)

An Insight into Nitromethane as an Organic Nitrile Alternative Source towards the Synthesis of Aryl Nitriles
Directed by an unusual in situ reduction of CuII, our protocol is a simple CuI-mediated synthesis of aryl nitriles, with inexpensive and readily available nitromethane as the cyanating source, in moderate to good yields. Exhibiting a wide substrate scope, the method involves simple reaction conditions, is additive free with low catalyst loading. The plausible mechanism of cyanation of aryl halides is elucidated by a congregation of three cycles, namely the in situ reduction of CuII species by nitromethane, generation of HCN species from nitromethane and a regular organometallic pathway which releases the nitrile derivative. The detail of the mechanism of generation of CN– from nitromethane is computationally validated. Our protocol holds the distinction of involving a rarely encountered CuI catalytic species as well as facile in situ generation of nucleophilic CN– to yield synthetically useful aromatic nitriles.
Saikia, Rakhee,Dey Baruah, Satyajit,Deka, Ramesh C.,Thakur, Ashim J.,Bora, Utpal
p. 6211 - 6216
(2019/11/05)

Triphenylbismuth Dichloride-Mediated Conversion of Thioamides to Nitriles
Thioamides were efficiently converted to nitriles using the pentavalent triphenylbismuth dichloride in combination with triethylamine. The reaction involved the dehydrosulfurization of primary thioamides to afford substituted aromatic or aliphatic nitriles in good to excellent yields. The process was also successfully extended to the synthesis of cyanamides starting from the corresponding thioureas and of thiocyanates from dithiocarbamates.
Gopi, Elumalai,Gravel, Edmond,Doris, Eric
supporting information
p. 4043 - 4045
(2019/06/24)

TiCl3 catalyzed one-pot protocol for the conversion of aldehydes into 5-substituted 1H-tetrazole
An efficient protocol has been explored for the one-pot synthesis of tetrazole derivatives with wide functional group compatibility in moderate to very high yields starting from aliphatic and aromatic substituted aldehydes. The reaction proceeds via non-isolated oxime and nitrile intermediates. The structures of the products were confirmed by IR and NMR spectroscopy. A plausible reaction mechanism is also provided.
Ranjan Chakraborty, Rakesh,Ghosh, Pranab
p. 3616 - 3619
(2018/09/11)

Combining Oxoammonium Cation Mediated Oxidation and Photoredox Catalysis for the Conversion of Aldehydes into Nitriles
A method to oxidize aromatic aldehydes to nitriles has been developed. It involves a dual catalytic system of 4-acetamido-TEMPO and visible-light photoredox catalysis. The reaction is performed using ammonium persulfate as both the terminal oxidant and nitrogen source.
Nandi, Jyoti,Witko, Mason L.,Leadbeater, Nicholas E.
supporting information
p. 2185 - 2190
(2018/09/29)

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)

A practical oxidative conversion of aldehydes into N-chloroaldimines
A novel method for the preparation of N-chloroaldimines from commonly available aromatic aldehydes has been developed. The reaction proceeded effectively by two steps: aldehydes were initially transformed into imines and then chloro-substitution with NaClO2 gave the N-chloroaldimines. This simple protocol allows for the preparation of a variety of aromatic N-chloroaldimines in moderate to excellent yields without the isolation of the imine intermediate. We also found that 3-nitrobenzaldehyde and 4-cyanobenzaldehyde were converted into the related benzonitrile directly under the standard conditions.
Jin, Can,Wang, Feng,Sun, Bin,Zhuang, Xiaohui
p. 547 - 551
(2018/11/27)

Oxidative cyanide-free cyanation on arylboronic acid derivatives using aryl/heteroaryl thiocyanate using novel IL-PdCl4 catalyst under mild condition
An efficient and simple method is reported for the cyanation on arylboronic acid using various simple/indole thiocyanates using a new IL-PdCl4 catalyst. The cascade process involves a coupling reaction without any additive to give a wide range of cyanide derivatives. Cyanation on various arylboronic acids underwent smoothly affording the corresponding arylnitriles in good to high yields.
Vaghasiya, Beena K.,Satasia, Shailesh P.,Thummar, Rahul P.,Kamani, Ronak D.,Avalani, Jemin R.,Sapariya, Nirav H.,Raval, Dipak K.
p. 507 - 515
(2018/05/15)

[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)

Immobilization of an Aminobisphosphine–PdII Complex over Graphene Oxide: An Efficient and Reusable Catalyst for Suzuki–Miyaura, Ullmann Coupling and Cyanation Reactions
The grafting of an aminobis(phosphine)–PdII complex (PNP–PdII) [PdCl2{(Ph2P)2N(CH2)3Si(OMe)3}] (2) on graphene oxide (GO) has been carried out by a condensation reaction between methoxysilane groups of 2 and hydroxyl groups of GO. The composite material was characterized by FTIR spectroscopy, solid-state 31P NMR spectroscopy, SEM, TEM, XPS and ICP-AES techniques. All these tools support the clean immobilization of compound 2 on GO. The composite material showed high catalytic activity in Suzuki–Miyaura, Ullmann coupling and cyanation reactions. The heterogeneity of the composite was confirmed by a hot filtration test. The immobilized PNP–PdII shows comparable activity to its homogeneous analogue 2. The recycling ability of the catalyst was examined for five consecutive runs, which showed little or no reduction in its catalytic efficiency.
Sengupta, Debasish,Pandey, Madhusudan K.,Mondal, Dipanjan,Radhakrishna, Latchupatula,Balakrishna, Maravanji S.
p. 3374 - 3383
(2018/05/08)

Practical CuCl/DABCO/4-HO-TEMPO-catalyzed oxidative synthesis of nitriles from alcohols with air as oxidant
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.
Hu, Yongke,Chen, Lei,Li, Bindong
supporting information
p. 464 - 466
(2017/11/13)

Aromatic nitriles synthetic method of the compound (by machine translation)
The invention relates to an aromatic nitrile compound synthetic methods, is to benzaldehyde or a benzene ring substituted benzaldehyde derivatives as raw materials, in the catalysis of hydrazine hydrate, with ammonia reaction under normal temperature, adding sodium thiosulfate for removing excess iodine, adding pure water, for extractant, product and then with anhydrous sodium sulfate as the drying agent, using a rotary evaporation instrument rotary drying solvent, to obtain the product. The method of mild reaction conditions, without using a metal catalyst, operation is simple and easy, and the adaptability of the wide range of the substrate and the like, can be used for preparing different substituents on the benzene ring of the aromatic nitrile compounds. (by machine translation)
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Paragraph 0018

(2018/03/13)

p-TsOH mediated solvent and metal catalyst free synthesis of nitriles from aldehydes via Schmidt reaction
A new and efficient protocol for the conversion of aldehyde into nitriles by modified Schmidt reaction. The reaction is carried out under solvent free condition using sodium azide as a source of nitrogen and catalysed by p-toluene sulphonic acid in presence of silica surface with no side product. This transformation gives good to excellent yield for numerous aromatic, aliphatic and heterocyclic nitriles using very simple reagent. This method has avoided the use of transition metal catalyst, toxic cyanide, hazardous solvent and offers a greener, simple and environment friendly procedure.
Mitra, Bijeta,Pariyar, Gyan Chandra,Singha, Rabindranath,Ghosh, Pranab
supporting information
p. 2298 - 2301
(2017/05/19)

Poly(ethylene glycol)–bound sulfonyl chloride as an efficient catalyst for transformation of aldoximes to nitriles
An operationally simple, efficient, and environmentally benign preparation of nitriles in good to excellent yields from various aldoximes in the presence of recyclable poly(ethylene glycol)–bound sulfonyl chloride is described.
Zhang, Xiao-Lan,Liu, Xiao-Ling,Sang, Xiao-Yan,Sheng, Shou-Ri
p. 232 - 237
(2017/01/22)

Polyethylene glycol supported phosphorus chloride: An efficient and recyclable catalyst for the preparation of nitriles from aldoximes
Polyethylene glycol (PEG) supported phosphorus chloride has been developed and used as an efficient and recyclable catalyst for dehydration of various aldoximes into the corresponding nitriles. This protocol has many advantages such as high conversion, high selectivity, short reaction time, mild reaction conditions, and simple experimental procedure.
Zhang, Xiao-Lan,Sheng, Shou-Ri,Wei, Mei-Hong,Liu, Xiao-Ling
p. 513 - 517
(2017/05/01)