Xi:Irritant;
104-85-8Relevant articles and documents
Photochemical equilibration/isomerization of p-, m-, and o-methylbenzonitrile
MacLeod, Paula J.,Pincock, Alexandra L.,Pincock, James A.,Thompson, Kim A.
, p. 6443 - 6450 (1998)
The phototransposition reactions in acetonitrile of p-, m-, and o-methylbenzonitrile have been studied. Any one of the three is converted to the other two by either a 1,2- or 1,3-isomerization in a primary photochemical step. However, the reactivities are quite different with the relative values for para:meta:ortho = 32:4:1. For both the para and meta isomers, extended irradiations approach a calculated steady-state composition of para:meta:ortho = 3:20:77. Quenching of the excited triplet state of the para and meta isomers with 2,4-dimethyl-1,3-butadiene indicates that these reactions are occurring from the excited singlet state. Irradiation of selectively labeled 2,6-dideuterio-4-methylbenzonitrile demonstrates that only the cyano-substituted carbon undergoes migration.
Isomerization of Methylbenzonitriles Catalysed by HZSM-5
Weigert, Frank J.
, p. 2653 - 2655 (1986)
The zeolite HZSM-5 catalyzes methyl migration in toluonitriles and dimethylbenzonitriles by intramolecular 1,2-shifts.Only the three dimethylbenzonitriles with 1,2,4-substituent pattern are small enough to take part in the shape selective reaction.
Cul/1,10-phenanthroline: An efficient catalyst system for the cyanation of aryl halides
Zhu, Yi-Zhong,Cai, Chun
, p. 484 - 485 (2007)
Aryl nitriles have been prepared in good yields from the corresponding aryl halides with potassium hexacyanoferrate(II) using Cul/1,10-phenanthroline as the catalyst system. Furthermore, the reaction is compatible with a wide range of functional groups including nitro and carbonyl substituents.
Simple and efficient one-pot synthesis of nitriles from amides and oximes using in situ-generated burgess-type reagent
Rappai, John P.,Karthikeyan, Jayakumar,Prathapan, Sreedharan,Unnikrishnan, Perupparampil A.
, p. 2601 - 2606 (2011)
The dehydration of aldoximes and amides, and oxidation of benzoin are accomplished in one-pot using in situ-generated Burgess-type reagent. Taylor & Francis Group, LLC.
-
Friedman,Shechter
, p. 2522 (1961)
-
An efficient and convenient KF/Al2O3 mediated synthesis of nitriles from aldehydes
Movassagh, Barahman,Shokri, Salman
, p. 6923 - 6925 (2005)
KF/Al2O3 brings about a facile one-pot and economical conversion of various aryl and alkyl aldehydes into the corresponding nitriles in high yields by reaction with hydroxylamine hydrochloride.
Copper-Catalyzed Oxidation of Amines with Molecular Oxygen
Maeda, Yasunari,Nishimura, Takahiro,Uemura, Sakae
, p. 2399 - 2403 (2003)
An improved system for selective aerobic oxidation of amines to imines or nitriles is presented. It involves commercially available and inexpensive copper(I) or (II) chloride as catalyst, toluene as solvent, and MS3A as dehydrating agent under an atmospheric pressure of oxygen. A variety of amines can be used as substrates for this oxidation system to give the corresponding nitriles from primary amines (up to 97% yield; TON, up to 60) and the imines from secondary amines (up to 90% yield; TON, up to 45).
COUPLING REACTION OF ORGANOMERCURY COMPOUNDS WITH ARYL HALIDES CATALYZED BY PALLADIUM COMPLEXES
Bumagin, N. A.,Kalinovskii, I. O.,Beletskaya, I. P.
, p. 1469 - 1473 (1983)
-
A general and convenient catalytic synthesis of nitriles from amides and silanes
Zhou, Shaolin,Junge, Kathrin,Addis, Daniele,Das, Shoubhik,Beller, Matthias
, p. 2461 - 2464 (2009)
A new and convenient protocol for the catalytic dehydration of aromatic and aliphatic amides using silanes in the presence of catalytic amounts of fluoride is presented. The synthesis of aliphatic and aromatic nitriles proceeds with high selectivity under mild conditions. Notably, a wide substrate range is converted in good to excellent yields.
Potassium, fluoride doped on alumina: An efficient catalyst for conversion of aldoximes into nitriles
Movassagh, Barahman,Shokri, Salman
, p. 887 - 890 (2005)
Potassium fluoride loaded on alumina catalyzed the dehydration of alkyl and aryl aldoximes into nitriles in good to high yields.
Nitrosation of Cyanamide: Preparation and Properties of the Elusive E- and Z-N'-Cyanodiazohydroxides
Guethner, Thomas,Huber, Evi,Sans, Juergen,Thalhammer, Franz
, (2020)
Nitrosation of cyanamide leads to unstable E/Z-cyanodiazohydroxides that easily deprotonate to E/Z-cyanodiazotates. Pursuing observations of E. Drechsel 145 years ago, the structure and reactivity of those products was determined, mainly in aqueous solution. Depending on the pH, three different thermal decomposition pathways give either N2O + HCN or N2 + HNCO. They were evaluated experimentally and by quantum mechanical calculations.
The palladium-catalyzed desulfitative cyanation of arenesulfonyl chlorides and sodium sulfinates
Chen, Jianbin,Sun, Yang,Liu, Bin,Liu, Dongfang,Cheng, Jiang
, p. 449 - 451 (2012)
A palladium-catalyzed desulfitative cyanation of arenesulfonyl chlorides and sodium sulfinates has been developed, providing aryl nitriles in moderate to excellent yields. It represents a facile procedure to access aryl nitriles.
Stable palladium nanoparticles catalyzed synthesis of benzonitriles using K4[Fe(CN)6]
Ganapathy, Dhandapani,Kotha, Surya Srinivas,Sekar, Govindasamy
, p. 175 - 178 (2015)
A stable palladium nanocatalyst is used in the synthesis of benzonitriles by cyanation of aryl iodides. A nontoxic and economic potassium hexacyanoferrate was used as a safe cyanide source. A variety of benzonitriles are efficiently synthesized using the stable nanocatalyst. The catalyst was quantitatively recovered and reused without any apparent loss in the catalytic activity.
Phosphinoferrocene ureas: Synthesis, structural characterization, and catalytic use in palladium-catalyzed cyanation of aryl bromides
?koch, Karel,Císa?ová, Ivana,?těpni?ka, Petr
, p. 1942 - 1956 (2015)
Phosphinoferrocene ureas Ph2PfcCH2NHCONR2, where NR2 = NH2 (1a), NHMe (1b), NMe2 (1c), NHCy (1d), and NHPh (1e); the analogous thiourea Ph2PfcCH2NHCSNHPh (1f); and the acetamido derivative Ph2PfcCH2NHCOMe (1g) (Cy = cyclohexyl, fc = ferrocene-1,1′-diyl) were prepared via three different approaches starting from Ph2PfcCH2NH2·HCl (3·HCl) or Ph2PfcCHO (4). The reactions of the representative ligand 1e with [PdCl2(cod)] (cod = cycloocta-1,5-diene) afforded [PdCl(μ-Cl)(1e-κP)2]2 or [PdCl2(1e-κP)2]2 depending on the metal-to-ligand stoichiometry, whereas those with [PdCl(η3-C3H5)]2 and [PdCl(LNC)]2 produced the respective bridge cleavage products, [PdCl(η3-C3H5)(1e-κP)] and [PdCl(LNC)(1e-κP)] (LNC = [(2-dimethylamino-κN)methyl]phenyl-κC1). Attempts to involve the polar pendant in coordination to the Pd(II) center were unsuccessful, indicating that the phosphinoferrocene ureas 1 bind Pd(II) preferentially as modified phosphines rather than bifunctional donors. When combined with palladium(II) acetate, the ligands give rise to active catalysts for Pd-catalyzed cyanation of aryl bromides with potassium hexacyanoferrate(II). Optimization experiments revealed that the best results are obtained in 50% aqueous dioxane with a catalyst generated from 1 mol % of palladium(II) acetate and 2 mol % of 1e in the presence of 1 equiv of Na2CO3 as the base and half molar equivalent of K4[Fe(CN)6]·3H2O. Under such optimized conditions, bromobenzenes bearing electron-donating substituents are cyanated cleanly and rapidly, affording the nitriles in very good to excellent yields. In the case of substrates bearing electron-withdrawing groups, however, the cyanation is complicated by the hydrolysis of the formed nitriles to the respective amides, which reduces the yield of the desired primary product. Amine- and nitro-substituted substrates are cyanated only to a negligible extent, the former due to their metal-scavenging ability.
One-step conversion of aldehydes into nitriles in dry media under microwave irradiation
Feng, Jun-Cai,Liu, Bin,Dai, Li,Bian, Ning-Sheng
, p. 3765 - 3768 (1998)
Aldehydes undergo rapid reaction with hydroxylammonium chloride using HCOOH/SiO2 as solid support catalyst, under microwave irradiation without solvent to affords nitriles in 60-90% yields.
Synthesis of aryl dihydrothiazol acyl shikonin ester derivatives as anticancer agents through microtubule stabilization
Lin, Hong-Yan,Li, Zi-Kang,Bai, Li-Fei,Baloch, Shahla Karim,Wang, Fang,Qiu, Han-Yue,Wang, Xue,Qi, Jin-Liang,Yang, Raong-Wu,Wang, Xiao-Ming,Yang, Yong-Hua
, p. 93 - 106 (2015)
The high incidence of cancer and the side effects of traditional anticancer drugs motivate the search for new and more effective anticancer drugs. In this study, we synthesized 17 kinds of aryl dihydrothiazol acyl shikonin ester derivatives and evaluated their anticancer activity through MTT assay. Among them, C13 showed better antiproliferation activity with IC50 = 3.14 ± 0.21 μM against HeLa cells than shikonin (IC50 = 5.75 ± 0.47 μM). We then performed PI staining assay, cell cycle distribution, and cell apoptosis analysis for C13 and found that it can cause cell arrest in G2/M phase, which leads to cell apoptosis. This derivative can also reduce the adhesive ability of HeLa cells. Docking simulation and confocal microscopy assay results further indicated that C13 could bind well to the tubulin at paclitaxel binding site, leading to tubulin polymerization and mitotic disruption.
Pd/C-catalyzed cyanation of aryl halides in aqueous PEG
Chen, Gong,Weng, Jiang,Zheng, Zhanchao,Zhu, Xinhai,Cai, Yaoyao,Cai, Jiwen,Wan, Yiqian
, p. 3524 - 3528 (2008)
An environmentally friendly Pd/C-PEG-H2O system was developed for the cyanation of aryl halides under microwave irradiation. A wide range of aryl bromides, iodides, and some activated chlorides were demonstrated to be cyanated smoothly by using nontoxic K4[Fe(CN)6] ·3H2O as the cyanide source. There is no phosphorus- or nitrogen-containing ligand or solvent involved. Moreover, this reaction can be carried out without the protection of inert atmosphere. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
Highly Efficient Oxidative Cyanation of Aldehydes to Nitriles over Se,S,N-tri-Doped Hierarchically Porous Carbon Nanosheets
Hua, Manli,Song, Jinliang,Huang, Xin,Liu, Huizhen,Fan, Honglei,Wang, Weitao,He, Zhenhong,Liu, Zhaotie,Han, Buxing
, p. 21479 - 21485 (2021)
Oxidative cyanation of aldehydes provides a promising strategy for the cyanide-free synthesis of organic nitriles. Design of robust and cost-effective catalysts is the key for this route. Herein, we designed a series of Se,S,N-tri-doped carbon nanosheets with a hierarchical porous structure (denoted as Se,S,N-CNs-x, x represents the pyrolysis temperature). It was found that the obtained Se,S,N-CNs-1000 was very selective and efficient for oxidative cyanation of various aldehydes including those containing other oxidizable groups into the corresponding nitriles using ammonia as the nitrogen resource below 100 °C. Detailed investigations revealed that the excellent performance of Se,S,N-CNs-1000 originated mainly from the graphitic-N species with lower electron density and synergistic effect between the Se, S, N, and C in the catalyst. Besides, the hierarchically porous structure could also promote the reaction. Notably, the unique feature of this metal-free catalyst is that it tolerated other oxidizable groups, and showed no activity on further reaction of the products, thereby resulting in high selectivity. As far as we know, this is the first work for the synthesis of nitriles via oxidative cyanation of aldehydes over heterogeneous metal-free catalysts.
Cyanation of aryl chlorides using a microwave-assisted, copper-catalyzed concurrent tandem catalysis methodology
Coughlin, Mary M.,Kelly, Colin K.,Lin, Shirley,Macarthur, Amy H. Roy
, p. 3537 - 3543 (2013)
A microwave-assisted, copper-catalyzed concurrent tandem catalytic (CTC) methodology has been developed for the cyanation of aryl chlorides, where the aryl chloride is first converted to an aryl iodide via halogen exchange and the aryl iodide is subsequently transformed to the aryl nitrile. A variety of aryl chlorides were converted to aryl nitriles in 44-97% yield using 20 mol % of CuI, 40 mol % of N,N'-cyclohexane-1,2-diamine, and 1.2 equiv of KCN in acetonitrile at 200 C after 1-2 h. The same copper/ligand system served as a multifunctional catalyst for both steps of the concurrent catalytic process. Unlike our previously reported CTC hydrodehalogenation of aryl chlorides, CTC cyanation was catalytic in iodide. Kinetic simulations of the proposed CTC mechanism were consistent with experimental results and stipulate the relative reaction rates of the two catalytic cycles necessary to achieve reasonable yields of product. This article not subject to U.S. Copyright. Published 2013 by the American Chemical Society.
Deciphering a 20-Year-Old Conundrum: The Mechanisms of Reduction by the Water/Amine/SmI2 Mixture
Maity, Sandeepan,Hoz, Shmaryahu
, p. 18394 - 18400 (2015)
The reaction of SmI2 with the substrates 3-methyl-2-butanone, benzyl chloride, p-cyanobenzyl chloride, and anthracene were studied in the presence of water and an amine. In all cases, the water content versus rate profile shows a maximum at around 0.2 M H2O. The rate versus amine content profile shows in all cases, except for benzyl chloride, saturation behavior, which is typical of a change in the identity of the rate-determining step. The mechanism that is in agreement with the observed data is that electron transfer occurs in the first step. With substrates that are not very electrophilic, the intermediate radical anions lose the added electron back to samarium(III) relatively quickly and the reaction cannot progress efficiently. However, in a mixture of water/amine, the amine deprotonates a molecule of water coordinated to samarium(III). The negatively charged hydroxide, which is coordinated to samarium(III), reduces its electrophilicity, and therefore, lowers the rate of back electron transfer, which allows the reaction to progress. In the case of benzyl chloride, in which electron transfer is rate determining, deprotonation by the amine is coupled to the electron-transfer step.
Naphthochromenones: Organic Bimodal Photocatalysts Engaging in Both Oxidative and Reductive Quenching Processes
Mateos, Javier,Rigodanza, Francesco,Vega-Pe?aloza, Alberto,Sartorel, Andrea,Natali, Mirco,Bortolato, Tommaso,Pelosi, Giorgio,Companyó, Xavier,Bonchio, Marcella,Dell'Amico, Luca
, p. 1302 - 1312 (2020)
Twelve naphthochromenone photocatalysts (PCs) were synthesized on gram scale. They absorb across the UV/Vis range and feature an extremely wide redox window (up to 3.22 eV) that is accessible using simple visible light irradiation sources (CFL or LED). Their excited-state redox potentials, PC*/PC.? (up to 1.65 V) and PC.+/PC* (up to ?1.77 V vs. SCE), are such that these novel PCs can engage in both oxidative and reductive quenching mechanisms with strong thermodynamic requirements. The potential of these bimodal PCs was benchmarked in synthetically relevant photocatalytic processes with extreme thermodynamic requirements. Their ability to efficiently catalyze mechanistically opposite oxidative/reductive photoreactions is a unique feature of these organic photocatalysts, thus representing a decisive advance towards generality, sustainability, and cost efficiency in photocatalysis.
Cu2O-mediated room temperature cyanation of aryl boronic acids/esters and TMSCN
Ye, Yong,Wang, Yanhua,Liu, Pengtang,Han, Fushe
, p. 27 - 30 (2013)
A method for the efficient and reliable synthesis of aryl nitriles via the Cu2O-catalyed cross-coupling of aryl boronic acids or esters and TMSCN is presented. A broad range of substrates decorated by electron-rich and deficient, sterically very congested, and labile functionalities were tolerated. Moreover, the reaction can proceed under mild conditions at room temperature. These advantages paired with the use of cheap, readily available, and halogen-free Cu2O as catalysts make the protocol an appealing option for aryl cyanations. A method for the efficient and reliable synthesis of aryl nitriles via the Cu2O-catalyed cross-coupling of aryl boronic acids or esters and TMSCN is presented. The room temperature operation paired with the use of cheap, readily available, and halogen-free Cu2O as catalysts makes the protocol an appealing option for aryl cyanations. Copyright
Cu(NO3)2·3H2O-mediated cyanation of aryl iodides and bromides using DMF as a single surrogate of cyanide
Zhang, Lianpeng,Lu, Ping,Wang, Yanguang
, p. 2840 - 2843 (2015)
Aryl nitriles were prepared through Cu(NO3)2·3H2O-mediated cyanation of aryl iodides and bromides using DMF as a single surrogate of cyanide. Moreover, this protocol could be scalable and practiced with benign operation.
Pyrolysis and Photolysis of 1-Aroylamino-4,5-diaryl-1,2,3-triazoles: Generation and Thermal Transformations of 4,5-Diaryl-1,2,3-triazolyl Radicals
Hadjiantoniou-Maroulis,Charalambopoulos,Maroulis
, p. 891 - 894 (1998)
The pyrolysis of 1-aroylamino-4,5-diphenyl-1,2,3-triazoles 1 yields, pressumably via the 4,5-diphenyl-1,2,3-triazolyl radical (2a), 2,3-diphenyl-2H-azirine (11a) and 2-aryl-4,5-diphenylimidazoles 14 as the major products. Upon irradiation 1-benzoylamino-4,5-diphenyl-1,2,3-triazole (1a) gives 4,5-diphenyl-1(2)H-1,2,3-triazole (4a) via the 1,2,3-triazolyI radical 2a, together with benzamide (5a) and 1,2-bisbenzoylhydrazine (6a). Products 5a and 6a result from the benzoylamino radical 3a by hydrogen atom abstraction and dimerization respectively.
Iodine-catalyzed, efficient, one-pot protocol for the conversion of araldehydes into 5-aryl-1H-tetrazoles
Reddy, M.B.Madhusudana,Pasha
, p. 2081 - 2085 (2011)
An easy access to various 5-aryl-1H-tetrazoles by a one-pot direct conversion of aldehydes to tetrazoles without the isolation of the intermediate nitriles using commercially available iodine as a catalyst is described. The protocol offers advantages in terms of good yields, mild reaction conditions, short reaction times, and use of readily available environmentally compatible catalyst. Copyright
Aldoxime- and hydroxy-functionalized chalcones as highly potent and selective monoamine oxidase-B inhibitors
Oh, Jong Min,Rangarajan,Chaudhary, Reeta,Gambacorta, Nicola,Nicolotti, Orazio,Kumar, Sunil,Mathew, Bijo,Kim, Hoon
, (2021/11/16)
A panel of 30 chalcone derivatives, including 19 aldoxime-chalcone ethers (ACE), and 11 hydroxyl?chalcones (HC), previously synthesized using a Pd-catalyzed C–O cross-coupling method were evaluated for their inhibitory activities against monoamine oxidases (MAOs), cholinesterases (ChEs), and β-secretase (BACE-1). HC6 was the most potent inhibitor of MAO-B with an IC50 value of 0.0046 μM and a selectivity index (SI) of 1,113. HC3 also potently inhibited MAO-B (IC50 = 0.0067 μM) and had the highest SI (1,455). ACE7 and ACE15 were also potent MAO-B inhibitors (IC50 = 0.012 and 0.018 μM, respectively), with SIs of 260 and 1,161, respectively. HC3 and HC6 were reversible competitive inhibitors of MAO-B, with Ki values of 0.0036 and 0.0013 μM, respectively. A structure–activity relationship revealed that methyl and fluorine substituents contributed to increasing both inhibition and selectivity. ACE7 was the most effective inhibitor of MAO-A (IC50 = 1.49 μM), followed by ACE3 (IC50 = 3.75 μM). No compounds effectively inhibited AChE, BChE, or BACE-1. A docking simulation showed that the ligand efficiency and docking scores of HC3 and HC6 toward MAO-B were consistent with the experimental IC50 values. These results suggest that HC3 and HC6 can be considered promising candidates for the treatment of neurological disorders.
Construction of N-Acyliminophosphoranes via Iron(II)-Catalyzed Imidization of Phosphines with N-Acyloxyamides
Lin, Sen,Lin, Bo,Zhang, Zongtao,Chen, Jianhui,Luo, Yanshu,Xia, Yuanzhi
, p. 3302 - 3306 (2022/05/05)
Employing FeCl2as a cheap and readily available catalyst, a facile imidization of phosphines with N-acyloxyamides is described, affording synthetically useful N-acyliminophosphoranes with high functional group tolerance. The transformation is easily performed under an air atmosphere at room temperature and could be scaled up to gram scale with a catalyst loading of 1 mol %. The iminophosphoranyl moiety in the product was further utilized as an effective directing group for controllable ortho C(sp2)-H bond amidations under Rh(III) catalysis.
Product selectivity controlled by manganese oxide crystals in catalytic ammoxidation
Hui, Yu,Luo, Qingsong,Qin, Yucai,Song, Lijuan,Wang, Hai,Wang, Liang,Xiao, Feng-Shou
, p. 2164 - 2172 (2021/09/20)
The performances of heterogeneous catalysts can be effectively tuned by changing the catalyst structures. Here we report a controllable nitrile synthesis from alcohol ammoxidation, where the nitrile hydration side reaction could be efficiently prevented by changing the manganese oxide catalysts. α-Mn2O3 based catalysts are highly selective for nitrile synthesis, but MnO2-based catalysts including α, β, γ, and δ phases favour the amide production from tandem ammoxidation and hydration steps. Multiple structural, kinetic, and spectroscopic investigations reveal that water decomposition is hindered on α-Mn2O3, thus to switch off the nitrile hydration. In addition, the selectivity-control feature of manganese oxide catalysts is mainly related to their crystalline nature rather than oxide morphology, although the morphological issue is usually regarded as a crucial factor in many reactions.
