100-47-0Relevant articles and documents
Improving Robustness: In Situ Generation of a Pd(0) Catalyst for the Cyanation of Aryl Bromides
Coombs, John R.,Fraunhoffer, Kenneth J.,Simmons, Eric M.,Stevens, Jason M.,Wisniewski, Steven R.,Yu, Miao
, p. 7040 - 7044 (2017)
Conditions have been developed for the palladium-catalyzed cyanation of aryl bromides utilizing the air-stable XantPhos-PdCl2 precatalyst. By employing a trialkylamine as a reducing agent, the active Pd(0) species is generated in situ, alleviating the need to employ the air-sensitive Pd2(dba)3. Twenty-two substituted benzonitriles have been synthesized using this method.
KINETICS OF REACTIONS OF O-(2,4-DINITROPHENYL) BENZALDOXIMES WITH METHYLAMINE, CYCLOHEXYLAMINE AND PIPERIDINE. REACTIVITY AT DIFFERENT ELECTROPHILIC SITES
Bhattacharjee, Gurudas,Singh, Ashok K.,Saikia, Ranjumoni
, p. 4537 - 4540 (1988)
Kinetics of reaction of E-O-(2,4-dinitrophenyl) benzaldoximes have been studied with MeNH2, cyclohexylamine (CHA) and piperdine (PiP) in 1:1 (v/v) ethanol-water at 35+/-0.1 deg C under pseudo first order conditions.The reactions are overall second order, first order with respect to each reactant.Hammett plots are linear with a ρ value of +0.75 for MeNH2, +0.61 for CHA and +1.25 for PiP.MeNH2 and CHA predominantly give the corresponding N-(2,4-dinitrophenyl)amine with attack at the aromatic carbon in sharp contrast to earlier observation with OH-.With piperidine both elimination and substitution products are obtained, the former product predominanting when strong electron-withdrawing substituents are present in the phenyl ring of the oxime.
Efficient synthesis of aromatic nitriles via cyanation of aryl bromides and K4[Fe(CN)6] catalyzed by a palladium(II) complex
Guo, Mengping,Ge, Junying,Zhu, Zhiyong,Wu, Xiaochun
, p. 213 - 215 (2013)
Cyanation of aryl bromides and K4[Fe(CN)6] were carried out in the presence of catalytic amounts of {[(PhCH2O) 2P(CH3)2CHNCH(CH3)2] 2PdCl2} (PdCl2L2) in DMF and a variety of Aromatic nitriles were obtained in good yields under aerobic conditions.
Reaction of Thioamides with Silver Carboxylates in Aprotic Media. A Nucleophilic Approach to the Synthesis of Imides, Amides, and Nitriles.
Avalos, Martin,Babiano, Reyes,Duran, Carlos J.,Jimenez, Jose L.,Palacios, Juan C.
, p. 477 - 480 (1994)
Synthesis of nitriles, imides, and amides by reaction of silver carboxylates with unsubstituted, N-substituted, and N,N-disubstituted thiomaides in aprotic media are described.
Douglas et al.
, p. 1127 (1953)
A base-induced ring-opening process of 2-substituted-1,3,4-oxadiazoles for the generation of nitriles at room temperature
Lu, Guo-Ping,Lin, Ya-Mei
, p. 371 - 374 (2014)
A novel base-catalysed 1,3,4-oxadiazole fragmentation for the synthesis of nitriles at room temperature has been developed. This reaction is performed under transition-metal-free conditions, and provides a new ring cleavage reaction of 1,3,4-oxadiazoles in organic synthesis.
Effect of Zn Substitutions in YBa2Cu3O6+x Phases on Reactivity during the Ammoxidation of Toluene
Otamiri, Jonathan C.,Andersson, Arne,Andersson, S. Lars T.,Crow, Jack E.,Gao, Ye
, p. 1265 - 1271 (1991)
Zn substitution in Y-Ba-Cu-O-phases influences the catalytic ammoxidation of toluene.The activity for formation of both benzonitrile and CO2 at low and high O2 pressures, respectively, decreases strongly with increasing Zn content up to 4percent.Above this substitution level, the activity, however, increases slightly.Characterisations of the surface by XPS and of the bulk by XRD analysis, indicate the presence of overlayers on the catalysts.In these overlayers, irrespective of the Zn content of catalysts, CuI states predominate at low O2 pressure and CuII at high pressure.These states are associated with selective and non-selective properties, respectively.The activity of the catalysts shows a general tendency to increase with surface copper concentrations as found from XPS studies.However, strong deviations from linearity indicate that the activity of the overlayer is greatly influenced by the bulk acting as a support.
Substituent effect on exo stereoselectivity in the 1,3-dipolar cycloaddition reaction of tulipalin A with nitrile ylides
Melsa, Petr,Cajan, Michal,Havlas, Zdenek,Mazal, Ctibor
, p. 3032 - 3039 (2008)
(Chemical Equation Presented) 1,3-Dipolar cycloaddition reactions of dihydro-3-methylene-2(3H)-furanone (tulipalin A) with various benzonitrile(p-X-benzylide) ylides prefer formation of exo-cycloadducts in the extent corresponding to an increasing electron donor character of the substituent X in the para-position of the benzylide phenyl ring of the 1,3-dipolar reagent. The substituent effect on diastereoselectivity of the 1,3-DC reaction is rationalized in terms of CH/π interaction between the dipole and the dipolarophile in an exo-transition state. The determining role of such an interaction is demonstrated by the correlation of the observed diastereoselectivities with substituent Hammett σ constants, which shows a small negative ρ value. A certain contribution of CO/π interaction between the lactone carbonyl and the substituted phenyl ring to mediation of the substituent effect is also discussed. The energy profiles of both reaction pathways were analyzed using DFT and RI-MP2 theoretical approaches. Calculated energy and structural differences between located transition states are consistent with reaction diastereoselectivities.
The Dual Reactivity of 5-S/5-O-Phenyl-1,4,2-oxathiazoles: A Fragmentation Pathway That Affords Nitriles in the Presence of Water
Lim, Yi Wee,Hewitt, Russell J.,Burkett, Brendan A.
, p. 4840 - 4842 (2015)
The rearrangement of substituted 1,4,2-oxathiazoles to nitriles in the presence of water is described. Preliminary investigations suggest that the reaction pathway proceeds via a 1,4,2-oxathiazolium intermediate, followed by trapping with water and subsequent decomposition to products. An unprecedented rearrangement of 5-phenyl-1,4,2-oxathiazoles bearing a C5 leaving group to nitriles in the presence of water is described.
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Binkley
, p. 1893 (1969)
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Mukaiyama,T.,Hata,T.
, p. 1712 - 1715 (1960)
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A new method for the generation of nitriles from aldoximes
Jose, Binoy,Sulatha,Madhavan Pillai,Prathapan, Sreedharan
, p. 1509 - 1514 (2000)
A mild and efficient method for the stereoselective dehydration of α-aldoximes to the corresponding nitriles is described which utilises methyl (carboxysulfamoyl)triethylammonium hydroxide inner salt (Burgess reagent) as the dehydrating agent.
The facile fragmentation of trifluoroacetyl groups to nitriles
Kende, Andrew S.
, p. 4035 - 4038 (1995)
Trifluoroacetyl groups attached to a carbon atom devoid of hydrogen undergo facile, high-yield conversion to nitriles by reaction with MeAlClNH2, followed by KOtBu, in a 'one-pot' reaction sequence.
Ultrasound enhanced PTC conversion of benzamide to benzonitrile
Sivakumar,Senthilkumar,Pandit
, p. 2583 - 2587 (2001)
Enhancement of the reaction rate by combining the beneficial effects of PTC and ultrasound has been explored in the present study by taking the transformation of benzamide by dehydration to give benzonitrile as a model system. It was found that there is a
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Cantacuzene et al.
, p. 1365 (1967)
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Microwave assisted, solvent free one pot synthesis of nitriles from aryl aldehydes on melamin formaldehyde as solid support
Rezaei, Ramin,Mohammadi, Mohammad Kazem,Rastin, Nedaa
, p. 993 - 996 (2010)
Various aryl aldehydes underwent prompt one pot conversion into the corresponding nitriles in high yields by reacting with hydroxylamine hydrochloride supported on melamine formaldehyde under microwave irradiation in the presence of ammonium acetate as catalyst.
Electrochemical Behaviour of Diazirines
Elson, Clive M.,Liu, Michael T. H.
, p. 415 - 416 (1982)
The electrochemical reductions of 3-aryl-3-chlorodiazirines and 3-n-butyl-3-phenyldiazirine have been studied by cyclic voltammetry and controlled potential electrolysis in acetonitrile.
A thiophosphoryl chloride assisted transformation of arylaldoximes to thioamides
Pandey, Lokesh Kumar,Pathak, Uma,Mathur, Sweta,Suryanarayana
, p. 377 - 379 (2012)
Primary benzothioamides were accessed from benzaldoximes (benzaldehyde oximes) via benzonitriles in a sequential tandem approach utilizing thiophosphoryl chloride as a dehydrating and thionating agent. Georg Thieme Verlag Stuttgart New York.
Quantum Dots in Visible-Light Photoredox Catalysis: Reductive Dehalogenations and C-H Arylation Reactions Using Aryl Bromides
Pal, Anuushka,Ghosh, Indrajit,Sapra, Sameer,K?nig, Burkhard
, p. 5225 - 5231 (2017)
In the recent past, visible-light-mediated photoredox catalysis has made a huge impact on the development of new synthetic methods under very mild and ecologically benign conditions. Although semiconductor nanocrystals or quantum dots (QDs) possess suitable optoelectronic and redox properties for photoredox catalytic applications, surprisingly, their use for the activation of challenging chemical bonds in the synthesis of organic molecules is little explored. We report here the application of ZnSe/CdS core/shell QDs for the synthetically important photoredox catalytic activation of carbon-halogen bonds in dehalogenation and C-H arylation reactions using (hetero)aryl halides as bench-stable inexpensive bulk starting materials, under very mild reaction conditions. The outstanding catalytic activity of ZnSe/CdS core/shell QDs is a direct consequence of the high specific surface area and homogeneity of QDs in solution and their high photostability toward oxidation.
Catalytic oxidative conversion of alcohols, aldehydes and amines into nitriles using KI/I2-TBHP system
Rajender Reddy,Uma Maheswari,Venkateshwar,Prashanthi,Lakshmi Kantam
, p. 2050 - 2053 (2009)
The oxidative conversion of alcohols, aldehydes and amines to give corresponding nitriles in excellent yields was easily achieved by the catalytic amount of KI or I2 in combination with TBHP as an external oxidant. This non-transition metal catalyst is cost effective and provides easy work-up and separation of the product.
OsO4-mediated conversion of primary amines to nitriles
Gao,Herzig,Wang
, p. 544 - 546 (2001)
Nitriles are very important intermediates in synthetic organic chemistry. Herein, we report our observation that certain primary amines can be converted to nitriles by trimethylamine N-oxide (TMO) under mild conditions in the presence of a catalytic amount of OsO4. Such a reaction could be used for synthetic purposes as well as for the analysis of functional group compatibility in designing reactions involving OsO4.
CN-Dimeric ortho-palladated complex catalyzed cyanation of aryl halides under microwave irradiation
Hajipour, Abdol Reza,Rafiee, Fatemeh
, p. 1391 - 1395 (2014)
The catalytic activity of dimeric [Pd{C6H2(CH 2CH2NH2)-(OMe)2,2,3}(m-Br)] 2 complex was investigated in the synthesis of benzonitriles under microwave irradiation conditions. The substituted benzonitriles were produced from various aryl halides in excellent yields and short reaction times using a catalytic amount of this complex as efficient, stable and air- and moisture-tolerant catalyst, and K4[Fe(CN)6] as a green cyanide source in DMF at 130 °C.
Activity enhancement in cyanation of aryl halides through confinement of ionic liquid in the nanospaces of SBA-15 -supported Pd complex
Karimi, Babak,Zamani, Asghar,Mansouri, Fariborz
, p. 57639 - 57645 (2014)
A novel and practical ionic-liquid mediated route for the synthesis of various aromatic nitriles has been developed via the cyanation of aryl halides with K4[Fe(CN)6] as a low cost, non-toxic and easily handled cyanating reagent in the presence of SBA-15 functionalized palladium complex partially confined with ionic liquids (IL@SBA-15-Pd) as the catalyst. Among the various ionic liquids tested in the cyanation reaction, 1-butyl-3-methylimidazolium hexafluorophosphate was found to provide the best medium for Pd-catalyzed cyanation of aryl halides. A variety of electron-rich and electron-poor aryl iodides and bromides gave the corresponding benzonitrile derivatives in good yield. Moreover, the catalyst was reused in four consecutive cycles with consistent catalytic activity. It was found that the presence of ionic liquid in the mesochannels of the mesoporous support not only provides a means of stabilizing Pd nanoparticles during the reaction but also the salient phase transfer feature of the imidazolium moieties may also serve as handles for faster penetration of Fe(CN)63- into the system pores to achieve highly concentrated reaction sites in close proximity to the catalytic (Pd NPs) centers, which resulted in an enhancement of the catalyst activity performance. This journal is
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Wislicenus,Goldschmidt
, p. 1471 (1900)
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Highly selective aerobic oxidation of primary amines to nitriles by ruthenium hydroxide
Zhang, Yuan,Xu, Kunling,Chen, Xiaorong,Hu, Tongjie,Yu, Yanpeng,Zhang, Junli,Huang, Jun
, p. 951 - 954 (2010)
A highly selective ruthenium catalyzed aerobic oxidation of primary amines to corresponding nitriles was developed in water and organic solvents. The catalyst system was highly efficient and widely applicable, and several functional groups were tolerated under the reaction conditions employed.
Highly dispersed Co species in N-doped carbon enhanced the aldehydes ammoxidation reaction activity
Fu, Wenqian,Pan, Liuming,Tang, Tiandi,Wang, Siming,Zhang, Lei
, (2022/01/04)
Developing environmentally friendly catalysts with high activity for the ammoxidation of aromatic aldehydes to aromatic nitriles is greatly important for this industrial transformation. Herein, natural vitamin B12 was used as a carbon source for the preparation of a cobalt- and nitrogen-doped catalyst precursor, which was pyrolyzed at different temperatures to obtain cobalt- and nitrogen-doped carbon (Co@NC-T) (T denotes pyrolysis temperature) catalysts. The Co@NC-800 exhibited excellent activity and selectivity in the ammoxidation of aromatic aldehydes with ammonium carbonate to aromatic nitriles compared to the Co@NC-700, Co@NC-600 and Co@NC-500 catalysts. The high catalytic performance of Co@NC-800 could be due to the presence of the low-density electron cloud of the highly dispersed Co species, which could interact with the benzene ring of benzaldehyde bearing p-π conjugate, thereby promoting the adsorption and activation of benzaldehyde. Consequently, the activated benzaldehyde reacted with amino groups that were decomposed from ammonium carbonate and subsequently underwent a dehydration process to form nitriles.
Wavelength-Specific Product Desorption as a Key to Raising Nitrile Yield of Primary Alcohol Ammoxidation over Illuminated Pd Nanoparticles
Han, Pengfei,Tang, Cheng,Sarina, Sarina,Waclawik, Eric R.,Du, Aijun,Bottle, Steven E.,Fang, Yanfen,Huang, Yingping,Li, Kun,Zhu, Huai-Yong
, p. 2280 - 2289 (2022/02/14)
Research on visible-light photocatalysts of metal nanoparticles (NPs) has focused on increasing the reactant conversion by light-excited charges (electrons and positively charged holes). However, light irradiation can accelerate catalysis by other mechanisms. Here, we report that 650 nm wavelength irradiation of 0.75 W·cm-2 significantly increases nitrile yield of ammoxidation of primary aromatic alcohols with an ammonium salt over supported Pd NPs at 80 °C in air. We found that the desorption of the nitrile product from the catalyst is the rate-determining step; the irradiation promotes not only alcohol oxidation and subsequent aldehyde cyanation over the Pd NPs but also the nitrile desorption selectively via resonance energy transfer to achieve a high nitrile yield. This new mechanism provides a knob for the exquisite control of catalytic reaction pathways for ecofriendly synthesis.
Tandem Fe/Zn or Fe/In Catalysis for the Selective Synthesis of Primary and Secondary Amines?via Selective Reduction of Primary Amides
Darcel, Christophe,Wu, Jiajun
, (2022/03/18)
Tandem iron/zinc or iron/indium-catalysed reductions of various primary amides to amines under hydrosilylation conditions are reported under visible light activation. By a simple modification of the nature of the co-catalyst (Zn(OTf)2 vs In(OTf)3), Fe(CO)4(IMes) can promote the highly chemoselective reduction of primary amides into primary amines (21 examples, up to 93 % isolated yields) and secondary amines (8 examples, up to 51 % isolated yields), respectively. Notably, both benzamide and alkanamide derivatives can be reduced.
