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
Relative reactivity of anti- and syn-oximino carbonates and carbamates of 2-pyridylacetic acid esters
Kim, Ha Young,Lantrip, Douglas A.,Fuchs, Philip L.
, p. 2137 - 2140 (2001)
(Matrix presented) anti-Oximes of 2-pyridylacetic acid esters are rapidly transformed to pyridine-2-carbonitrile under a variety of conditions while syn-oximes bearing tert-butyl esters can be conveniently deprotected to the corresponding carboxylic acid with subsequent fragmentation to the nitrile.
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.
General and Mild Nickel-Catalyzed Cyanation of Aryl/Heteroaryl Chlorides with Zn(CN)2: Key Roles of DMAP
Zhang, Xingjie,Xia, Aiyou,Chen, Haoyi,Liu, Yuanhong
, p. 2118 - 2121 (2017)
A new and general nickel-catalyzed cyanation of hetero(aryl) chlorides using less toxic Zn(CN)2 as the cyanide source has been developed. The reaction relies on the use of inexpensive NiCl2·6H2O/dppf/Zn as the catalytic system and DMAP as the additive, allowing the cyanation to occur under mild reaction conditions (50-80 °C) with wide functional group tolerance. DMAP was found to be crucial for successful transformation, and the reaction likely proceeds via a Ni(0)/Ni(II) catalysis based on mechanistic studies. The method was also successfully extended to aryl bromides and aryl iodides.
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.
Silica supported potassium oxide catalyst for dehydration of 2-picolinamide to form 2-cyanopyridine
Li, Yamei,Zhao, Yujun,Wang, Shengping,Ma, Xinbin
, p. 494 - 498 (2019)
The dehydration of 2-picolinamide to produce 2-cyanopyridine was investigated thoroughly using silica supported potassium oxide as a heterogeneous catalyst. Both large specific surface area and pore size of SiO2 (B) contributed to the favorable catalytic performance for the synthesis of 2-CP. In addition, the yield of 2-CP showed the linear relationship with the amounts of medium basicity of the catalysts, demonstrating that medium basic sites were the active sites of silica supported potassium oxide catalysts. The catalysts were further characterized by XRD and FT-IR to clarify the active species. The results indicated the Si–O–K group produced by the reaction of K2CO3 with Si–OH was the active species, which was further evidenced by the adjustment of the amount of Si–OH by silylation and hydroxylation procedure.
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.
A Mild Method for Electrochemical Reduction of Heterocyclic N-Oxides
Fukazawa, Yasuaki,Rubtsov, Aleksandr E.,Malkov, Andrei V.
, p. 3317 - 3319 (2020)
Deoxygenation of heteroaromatic N-oxides is commonly accomplished using chemical or enzymatic methods. In this work, we report on an expedient protocol for electrochemical reduction of pyridine N-oxide derivatives under mild conditions. A diverse range of mono- and bis N-oxides were converted into the corresponding nitrogen bases in good yields. Importantly, the method is highly selective towards N-oxides and tolerates challenging halo and nitro substituents in the heteroaromatic ring.
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.
Tandem oxidation processes: The direct conversion of activated alcohols into nitriles
McAllister, Graeme D.,Wilfred, Cecilia D.,Taylor, Richard J. K.
, p. 1291 - 1292 (2002)
The direct conversion of primary alcohols into nitriles is reported (RCH2OH into RCN) using manganese dioxide and ammonia in 2-propanol - THF, containing magnesium sulfate at room temperature. This transformation, which proceeds via an in situ
