372-09-8Relevant articles and documents
Electrocarboxylation of chloroacetonitrile mediated by electrogenerated cobalt(I) phenanthroline
Fabre,Reynes
, p. 1360 - 1362 (2010)
The electrocarboxylation of chloroacetonitrile mediated by [Co(II)(phen)3]2+ has been investigated. Cyclic voltammetry studies of [Co(II)(phen)3]2+ have shown that [Co(I)(phen)3]+, an 18 electron complex, activates chloroacetonitrile by an oxidative addition through the loss of a phenanthroline ligand to give [RCo(III)(phen)2Cl]+. The unstable one-electron-reduced complex underwent Co-C bond cleavage. In carbon dioxide saturated solution, CO2 insertion proceeds after reduction of the alkylcobalt complex. A catalytic current is observed which corresponds to the electrocarboxylation of chloroacetonitrile into cyanoacetic acid. Electrolyses confirmed the process and gave faradic yield of 62% in cyanoacetic acid at potentials that are about 0.3 V less cathodic than the one required for Ni(salen).
Hydrogen peroxide oxidation of 2-cyanoethanol catalyzed by metal complexes
Veghini,Shul'pina,Strelkova,Shul'pin
, p. 167 - 170 (2006)
Oxidation of 2-cyanoethanol, a relatively inert primary alcohol, with several systems (both homogeneous and heterogenized) based on transition metal complexes was studied. The oxidation was performed under homogeneous conditions with 35% hydrogen peroxide upon catalysis by the chlorides FeCl3 or OsCl3. The best result was obtained upon the oxidation catalyzed by OsCl3 at 70°C for 3 h in the absence of solvent: the total yield of the corresponding aldehyde and cyanoacetic acid reached 90%, and the turnover number was 1500. The systems [LMnIV(O)3Mn IVL]n(X)m-oxalic acid (where L = 1,4,7-trimethyl-1,4,7-triazacyclononane) also catalyze oxidation of 2-cyanoethanol with yields of 50-70% either under homogeneous conditions (X = PF- 6, n = 1, and m = 2) or with the use of the catalyst in the heterogenized form (as insoluble heteropoly acid salt), where X = W 12SiO4- 40, n = 2, and m = 1. Nauka/Interperiodica 2006.
5-Oxyacetic Acid Modification Destabilizes Double Helical Stem Structures and Favors Anionic Watson–Crick like cmo5U-G Base Pairs
Strebitzer, Elisabeth,Rangadurai, Atul,Plangger, Raphael,Kremser, Johannes,Juen, Michael Andreas,Tollinger, Martin,Al-Hashimi, Hashim M.,Kreutz, Christoph
, p. 18903 - 18906 (2018)
Watson–Crick like G-U mismatches with tautomeric Genol or Uenol bases can evade fidelity checkpoints and thereby contribute to translational errors. The 5-oxyacetic acid uridine (cmo5U) modification is a base modification at the wobble position on tRNAs and is presumed to expand the decoding capability of tRNA at this position by forming Watson–Crick like cmo5Uenol-G mismatches. A detailed investigation on the influence of the cmo5U modification on structural and dynamic features of RNA was carried out by using solution NMR spectroscopy and UV melting curve analysis. The introduction of a stable isotope labeled variant of the cmo5U modifier allowed the application of relaxation dispersion NMR to probe the potentially formed Watson–Crick like cmo5Uenol-G base pair. Surprisingly, we find that at neutral pH, the modification promotes transient formation of anionic Watson–Crick like cmo5U?-G, and not enolic base pairs. Our results suggest that recoding is mediated by an anionic Watson–Crick like species, as well as bring an interesting aspect of naturally occurring RNA modifications into focus—the fine tuning of nucleobase properties leading to modulation of the RNA structural landscape by adoption of alternative base pairing patterns.
Kinetics of the Deamination of Amides by Nitrous Acid
Al-Mallah, Khawla,Stedman, Geoffrey
, p. 670 - 671 (1998)
The kinetic profile of the rate constant for the nitrous acid-amide reaction in sulfuric acid as a function of acidity for a range of aliphatic and aromatic primary amides has been interpreted in terms of the HNO2/NO+ and the amide/ amide · H+ equilibria.
Facile dehydration of primary amides to nitriles catalyzed by lead salts: The anionic ligand matters
Ruan, Shixiang,Ruan, Jiancheng,Chen, Xinzhi,Zhou, Shaodong
, (2020/12/09)
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.
Surface active ionic liquid assisted metal-free electrocatalytic-carboxylation in aqueous phase: A sustainable approach for CO2utilization paired with electro-detoxification of halocarbons
Bhat, Khursheed Ahmad,Bhat, Mohsin Ahmad,Bhat, Sajad Ahmad,Ingole, Pravin P.,Manzoor Bhat, Zahid,Pandit, Sarwar Ahmad,Rather, Mudasir Ahmad,Rehman, Shakeel U.,Sofi, Feroz Ahmad,Thotiyl, Musthafa Ottakam
, p. 9992 - 10005 (2021/12/24)
Electrocarboxylation of halocarbons is a promising green synthetic strategy for capture, fixation and utilization of CO2 for the synthesis of high-added-value industrial compounds. However, the unparalleled kinetic/thermodynamic stability and solubility concerns of CO2 and halocarbons warrant the use of appropriate (often precious metal based) electrocatalytic electrodes and environmentally non-green solvent systems to drive this otherwise kinetically slow electrochemical process. Herein we demonstrate that owing to their unique solubility and excellent electrocatalytic properties, the aqueous micellar solutions of imidazolium-based surface active ionic liquids (SAILs) can be used for the efficient and selective electrocatalytic-carboxylation of halocarbons to produce carboxylic acids. Specifically, we present results from our detailed electrochemical investigations regarding the electroreductive cleavage of the C-X bond and electrocarboxylation of 9-bromoanthracene (9-BAN) and chloroacetonitrile (CAN) in buffered (pH 7, phosphate buffer) micellar solutions of 1-dodecyl-3-methyl-imidazolium chloride ([DDMIM][Cl]). We demonstrate that the unique ability of [DDMIM][Cl] micelles to stabilize the electrogenerated reactive intermediates facilitates a novel reaction pathway that ensures selective and efficient electrocatalytic-reductive carboxylation of 9-BAN and CAN. The presented results clearly establish that besides allowing for the electrocarboxylation of halocarbons in aqueous green electrolytes, the use of SAILs ensures electrochemical fixation of CO2 at practically low cost current and potential conditions imposed over metal free, economically viable and electrochemically robust carbon electrodes. The use of SAILs is reported to improve the faradaic efficiency (～95%) and reduce the chances of undesired side product reactions which continue to be a major concern in the state of art electro-carboxylation processes. The presented approach we opine offers a promising avenue toward design of eco-green pathways in the direction of CO2 fixation and electro-organic synthesis of a diverse range of value-added products from water insoluble halocarbons (toxic pollutants) in aqueous media.
Synthesis of α-aminonitriles using aliphatic nitriles, α-amino acids, and hexacyanoferrate as universally applicable non-toxic cyanide sources
Nauth, Alexander M.,Konrad, Tim,Papadopulu, Zaneta,Vierengel, Nina,Lipp, Benjamin,Opatz, Till
supporting information, p. 4217 - 4223 (2018/09/29)
In cyanation reactions, the cyanide source is often directly added to the reaction mixture, which restricts the choice of conditions. The spatial separation of cyanide release and consumption offers higher flexibility instead. Such a setting was used for the cyanation of iminium ions with a variety of different easy-to-handle HCN sources such as hexacyanoferrate, acetonitrile or α-amino acids. The latter substrates were first converted to their corresponding nitriles through oxidative decarboxylation. While glycine directly furnishes HCN in the oxidation step, the aliphatic nitriles derived from α-substituted amino acids can be further converted into the corresponding cyanohydrins in an oxidative C-H functionalization. Mn(OAc)2 was found to catalyze the efficient release of HCN from these cyanohydrins or from acetone cyanohydrin under acidic conditions and, in combination with the two previous transformations, permits the use of protein biomass as a non-toxic source of HCN.
Study on the degradation mechanism and pathway of benzene dye intermediate 4-methoxy-2-nitroaniline: Via multiple methods in Fenton oxidation process
Guo, Ying,Xue, Qiang,Cui, Kangping,Zhang, Jia,Wang, Hui,Zhang, Huanzhen,Yuan, Fang,Chen, Honghan
, p. 10764 - 10775 (2018/03/26)
Benzene dye intermediate (BDI) 4-methoxy-2-nitroaniline (4M2NA) wastewater has caused significant environmental concern due to its strong toxicity and potential carcinogenic effects. Reports concerning the degradation of 4M2NA by advanced oxidation process are limited. In this study, 4M2NA degradation by Fenton oxidation has been studied to obtain more insights into the reaction mechanism involved in the oxidation of 4M2NA. Results showed that when the 4M2NA (100 mg L-1) was completely decomposed, the TOC removal efficiency was only 30.70-31.54%, suggesting that some by-products highly recalcitrant to the Fenton oxidation were produced. UV-Vis spectra analysis based on Gauss peak fitting, HPLC analysis combined with two-dimensional correlation spectroscopy and GC-MS detection were carried out to clarify the degradation mechanism and pathway of 4M2NA. A total of nineteen reaction intermediates were identified and two possible degradation pathways were illustrated. Theoretical TOC calculated based on the concentration of oxalic acid, acetic acid, formic acid, and 4M2NA in the degradation process was nearly 94.41-97.11% of the measured TOC, indicating that the oxalic acid, acetic acid and formic acid were the main products. Finally, the predominant degradation pathway was proposed. These results could provide significant information to better understand the degradation mechanism of 4M2NA.
Unusual differences in the reactivity of glutamic and aspartic acid in oxidative decarboxylation reactions
But, Andrada,Van Der Wijst, Evie,Le N?tre, Jér?me,Wever, Ron,Sanders, Johan P. M.,Bitter, Johannes H.,Scott, Elinor L.
supporting information, p. 5178 - 5186 (2017/11/09)
Amino acids are potential substrates to replace fossil feedstocks for the synthesis of nitriles via oxidative decarboxylation using vanadium chloroperoxidase (VCPO), H2O2 and bromide. Here the conversion of glutamic acid (Glu) and aspartic acid (Asp) was investigated. It was observed that these two chemically similar amino acids have strikingly different reactivity. In the presence of catalytic amounts of NaBr (0.1 equiv.), Glu was converted with high selectivity to 3-cyanopropanoic acid. In contrast, under the same reaction conditions Asp showed low conversion and selectivity towards the nitrile, 2-cyanoacetic acid (AspCN). It was shown that only by increasing the amount of NaBr present in the reaction mixture (from 0.1 to 2 equiv.), could the conversion of Asp be increased from 15% to 100% and its selectivity towards AspCN from 45% to 80%. This contradicts the theoretical hypothesis that bromide is recycled during the reaction. NaBr concentration was found to have a major influence on reactivity, independent of ionic strength of the solution. NaBr is involved not only in the formation of the reactive Br+ species by VCPO, but also results in the formation of potential intermediates which influences reactivity. It was concluded that the difference in reactivity between Asp and Glu must be due to subtle differences in inter- and intramolecular interactions between the functionalities of the amino acids.
Preparation method for cyanoacetic acid and derivatives thereof
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Paragraph 0022; 0023; 0024; 0025; 0026; 0027; 0028-0045, (2016/12/01)
The invention discloses a preparation method for cyanoacetic acid and derivatives thereof. According to the invention, a mixed solution of cyanoacetic acid and sodium chloride is subjected to continuous chromatographic separation so as to obtain a cyanoacetic acid solution and sodium chloride; so the cyanoacetic acid solution with low chloride ion content or high-content solid cyanoacetic acid products and derivatives thereof are obtained, and the disadvantages of considerable decomposition and low yield of cyanoacetic acid in traditional distillation, concentration and separation are overcome. The preparation method is simple to operate, low in production cost, high in product yield and low in the amounts of waste gas, waste water and industrial residues, is an environment-friendly clean production method and can prepare the cyanoacetic acid solution with low chloride ion content or high-content solid cyanoacetic acid products and derivatives thereof.
