100-70-9Relevant articles and documents
One-pot conversion of aromatic bromides and aromatics into aromatic nitriles
Ushijima, Sousuke,Togo, Hideo
, p. 1562 - 1566 (2010)
Various aromatic bromides and iodides were smoothly converted into the corresponding aromatic nitriles in good to moderate yields by the treatment with butyllithium and subsequently DMF, followed by treatment with molecular iodine in aqueous ammonia. The
An improved Balz-Schiemann reaction enabled by ionic liquids and continuous processing
Snead, David R.,Lévesque, Fran?ois,Morris, William J.,Naber, John R.
, p. 4261 - 4265 (2019)
A Balz-Schiemann reaction was developed to convert 2-cyano-5-aminopyridine to 2-cyano-5-fluoropyridine. The use of an ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate, BMIMBF4) as a solvent was found to be critical in achieving high assay yields and high selectivity for the fluorination vs. protonation. A process was developed to recycle and reuse the ionic liquid enabling its cost-effective use as a solvent. Finally, the optimal conditions were demonstrated under as a continuous process to address process safety risks associated with diazonium intermediates and the product was used to access a key intermediate in the synthesis of β-amyloid cleaving enzyme 1 inhibitor, verubecestat.
Mild and efficient copper-catalyzed cyanation of aryl iodides and bromides
Cristau, Henri-Jean,Ouali, Armelle,Spindler, Jean-Francis,Taillefer, Marc
, p. 2483 - 2492 (2005)
An efficient copper-catalyzed cyanation of aryl iodides and bromides is reported. Our system combines catalytic amounts of both copper salts and chelating ligands. The latter, which have potential nitrogen- and/or oxygen-binding sites, have never previously been used in this type of reaction. A protocol has been developed that enables the cyanation of aryl bromides through the copper-catalyzed in situ production of the corresponding aryl iodides using catalytic amounts of potassium iodide. Aryl nitriles are obtained in good yields and excellent selectivities in relatively mild conditions (110°C) compared with the Rose-nmund-von Braun cyanation reaction. Furthermore, the reaction is compatible with a wide range of functional groups including nitro and amino substituents. The protocol reported herein involves two main innovations: the use of catalytic amounts of ligands and the use of acetone cyanohydrin as the cyanating agent in copper-mediated cyanation reactions.
Synthesis, characterization and crystal structure of 2-pyridinecarboxamide
Sun, Kai-Jin,Cai, Zhao-Sheng
, p. 195 - 198 (2020)
2-Pyridinecarboxamide was synthesized from 2-picoline through two-steps reaction. Initially, 2-picoline was converted into 2-cyanopyridine by ammoxidation in a stainless-steel fixed-bed reactor at 370 oC with V2O5 loaded on TiO2 as catalyst. The 2-cyanopyridine was transformed into 2-pyridinecarboxamide through oxidation hydrolysis in basic solution using MnO2 as oxidant at 70 oC. The final product was characterized by FT-IR, NMR and UV-visible analysis, and 2-pyridinecarboxamide in the final product was determined using HPLC. The crystal structure of 2-pyridinecarboxamide was investigated using X-ray diffraction and SHELX 2018/3 (sh) software and the result indicated that 2-pyridinecarboxamide crystallized in the monoclinic system, space group P21/n with a = 5.207(2), b = 7.097(3), c = 16.243(6) ?, V = 595.7 (4) ?3; Z = 4.
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Craig
, p. 231 (1934)
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Biomimetic models of nitric oxide synthase for the oxidation of oximes to carbonyl compounds catalyzed by water-soluble manganese porphyrins in aqueous solution
Ren, Qing-Gang,Zhou, Xian-Tai,Ji, Hong-Bing
, p. 211 - 216 (2011)
A mild green and efficient approach for hydrogen peroxide oxidative converting oximes to the corresponding carbonyl compounds with a water-soluble manganese porphyrin as catalyst in water/acetone mixture has been developed. The water-soluble manganese porphyrin showed an excellent activity for the oxidative deoximation reactions of various oximes under ambient conditions in the absence of any additive. The oxidative deoximation was through the formation of high valent oxo-manganese species, which was confirmed by in situ UV-vis spectroscopy.
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Katritzky,Sammes
, p. 247 (1975)
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Ceria-catalyzed conversion of carbon dioxide into dimethyl carbonate with 2-cyanopyridine
Honda, Masayoshi,Tamura, Masazumi,Nakagawa, Yoshinao,Sonehara, Satoru,Suzuki, Kimihito,Fujimoto, Ken-Ichiro,Tomishige, Keiichi
, p. 1341 - 1344 (2013)
DMC run: Carbon dioxide can be converted into dimethyl carbonate in a reaction system involving 2-cyanopyridine as a dehydration agent, catalyzed by CeO2. Regeneration of the coproduct 2-picolinamide can be achieved over a Na2O/SiO2 catalyst. As a whole, the system servest to react carbon dioxide with methanol to produce dimethyl carbonate. Copyright
Facile dehydration of primary amides to nitriles catalyzed by lead salts: The anionic ligand matters
Ruan, Shixiang,Ruan, Jiancheng,Chen, Xinzhi,Zhou, Shaodong
, (2021)
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.
Importance of Acidity on an Energetically Unfavorable Electron-Transfer Reaction-An Extension of the Rehm-Weller Equation. Photoreaction of Triplet 2,4-Pyridinedicarbonitrile with 2-Propanol
Caronna, Tullio,Morrocchi, Sergio,Vittimberga, Bruno M.
, p. 2205 - 2208 (1986)
An electron spin resonance study of the radical formed when 2,4-pyridinedicarbonitrile (1) is irradiated in the cavity of an ESR spectrometer has been done and the values of the ?-spin populations on the ring atoms were determined from the measured proton and nitrogen couplings.Radicals were generated by in situ photolysis of deaerated solutions of 1.The rate of radical formation was measured in acetonitrile at 33 deg C with varying amounts of 2-propanol, water, and hydrochloric acid.Quenching and photosensitization studies show the triplet state of 1 to be the photoreactive state. ΔGet values calculated by the Rehm-Weller equation were found to be endoergic when either the T1 or the T2 state of 1 is involved.Evidence is presented which supports a mechanism in which N-H bond formation is coupled to the electron-transfer step, resulting in an exoergic process.N-H bond formation becomes the driving force for the reaction.
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Hamana,Matsumoto
, (1971)
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One-pot conversion of aromatic bromides and aromatics into aromatic nitriles via aryllithiums and their DMF adduct
Ushijima, Sousuke,Moriyama, Katsuhiko,Togo, Hideo
, p. 958 - 964 (2011)
Various aromatic bromides and iodides were smoothly converted into the corresponding aromatic nitriles in good to moderate yields by the treatment with n-butyllithium and subsequently DMF, followed by treatment with molecular iodine in aq NH3. The same treatment of typical aromatics and heteroaromatics with n-butyllithium and subsequently DMF, followed by treatment with molecular iodine in aq NH3 also provided the corresponding aromatic nitriles in good yields. Moreover, the same treatment of aromatic bromides and aromatics with half amount of DIH (1,3-diiodo-5,5- dimethylhydantoin) instead of molecular iodine worked effectively to give the corresponding aromatic nitriles, respectively, in good yields. These reactions are novel and environmentally benign one-pot methods for the preparation of aromatic nitriles from aromatic bromides and aromatics, respectively, through the formation of aryllithiums and their DMF adducts.
Nitrile Synthesis via Desulfonylative-Smiles Rearrangement
Abe, Masahiro,Nitta, Sayasa,Miura, Erina,Kimachi, Tetsutaro,Inamoto, Kiyofumi
, p. 4460 - 4467 (2022/03/15)
Herein, we designed a simple nitrile synthesis from N-[(2-nitrophenyl)sulfonyl]benzamides via base-promoted intramolecular nucleophilic aromatic substitution. The process features redox-neutral conditions as well as no requirement of toxic cyanide species and transition metals. Our process shows broad scope and various functional group compatibility, affording a variety of (hetero)aromatic nitriles in good to excellent yields.
A new reagent for efficient synthesis of nitriles from aldoximes using methoxymethyl bromide
ULUDAG, Nesimi,GIDEN, Ozge NUR
, p. 993 - 998 (2021/02/05)
This study outlines an efficient, high-yielding, and rapid method by which to access diverse nitriles from aldoximes with methoxymethyl bromide (MOM-Br) in THF. It represents the first application of MOM-Br as a deoximation reagent to synthesize nitriles. The reaction was performed at reflux to ensure excellent yield (79-96%) of the nitriles within 20-45 minutes. Furthermore, this method has been successfully applied to the synthesis of the synthesis precursor of aromatic, heteroaromatic, cyclic, and acyclic aliphatic.
