110-59-8Relevant articles and documents
Catalytic Beckmann rearrangement of ketoximes in ionic liquids
Peng, Jiajian,Deng, Youquan
, p. 403 - 405 (2001)
Under mild conditions and without any additional organic solvents, Beckmann rearrangements of several ketoximes were performed in the catalytic media consisting of room temperature ionic liquid based on 1,3-dialkylimidazolium or alkylpyridinium salts and
A convenient procedure for the preparation of alkyl nitriles from alkyl halides. Acetone cyanohydrin as an in situ source of cyanide ion
Dowd,Wilk,Wlostowski
, p. 2323 - 2329 (1993)
A convenient preparation of alkyl nitriles from alkyl halides is described. Acetone cyanohydrin is employed as the source of cyanide ion.
Alkyllithium Compounds Bearing Electrophilic Functional Groups: A Flash Chemistry Approach
Nagaki, Aiichiro,Yamashita, Hiroki,Hirose, Katsuyuki,Tsuchihashi, Yuta,Yoshida, Jun-ichi
, p. 4027 - 4030 (2019)
Flash chemistry based on flow microreactor systems allowed alkyllithiums bearing electrophilic functional groups to be successfully generated and used for subsequent reactions. The series of reactions with high reactivity was achieved by extremely accurate control over residence time in a controlled and selective manner.
Deprotonation-alkylation of alkyl cyanides under sonochemical conditions
Berlan,Delmas,Duee,Luche,Vuiglio
, p. 1253 - 1260 (1994)
Deprotonation-alkylation of n-alkyl cyanides can be readily effected by an alkyl halide in the presence of sodium in a one pot procedure. Yields are generally better than in the usual methods, and the overall reaction conditions have important advantages
Palladium-Catalyzed Isomerization/(Cyclo)carbonylation of Pentenamides: a Mechanistic Study of the Chemo- and Regioselectivity
Limburg, Bart,Gloaguen, Yann,de Bruijn, Hans M.,Drent, Eite,Bouwman, Elisabeth
, p. 2961 - 2971 (2017)
A new isomerizing ring-closing amidocarbonylation reaction is reported using Pd catalysis with bulky diphosphane ligands. From terminal as well as internal pentenamide isomers (PAs), cyclic imides were obtained in good yield (92 %) with cationic Pd catalysts supported by bis-PCg ligands (PCg=6-phospha-2,4,8-trioxa-1,3,5,7-tetramethyladamant-6-yl). An excess of strong acid is required to obtain high selectivity for imide products. From a low-temperature NMR study it was deduced that N coordination of the amide moiety is responsible for a high selectivity to cyclic imide products. In weakly acidic conditions, O coordination of the amide functionality leads to the formation of cyanoacids (i.e., 5-cyanovaleric acid, 2-methyl-4-cyanobutyric acid and 2-ethyl-3-cyanopropionic acid). It is proposed that the formation of these cyanoacids occurs through a novel intramolecular tandem dehydrating hydroxycarbonylation reaction of PAs. This reaction also occurs in intermolecular versions of amidocarbonylation with mixtures of alkene and amide substrates. Experiments with N-alkylated amides have been instrumental in developing mechanistic models. The strong acid co-catalyst ensures double-bond isomerization to occur faster than product formation, resulting in the same product mixture, irrespective of the use of terminal or internal pentenamides. The remaining challenge is to arrive at the desired adipimide by overcoming the undesirable regioselectivity caused by chelation of the amide.
New catalytic properties of iron porphyrins: Model systems for cytochrome P450-catalyzed dehydration of aldoximes
Hart-Davis, Jason,Battioni, Pierrette,Boucher, Jean-Luc,Mansuy, Daniel
, p. 12524 - 12530 (1998)
Various iron porphyrin systems were found to catalyze the dehydration of aldoximes, such as heptanaldoxime or phenylacetaldoxime, into the corresponding nitriles under mild conditions (t = 20 °C, neutral or slightly acidic pH). In all these systems, the presence of both the iron porphyrin catalyst and a reducing agent is required, indicating that the active species is the iron(II) porphyrin. The most efficient systems used either an organosoluble iron porphyrin, such as Fe(OEP), in the presence of a carboxylic acid and zinc amalgam as reducing agent, or a water-soluble heme fragment of cytochrome c (microperoxidase MP-11) in the presence of dithionite. The catalytic activity of the systems was greatly increased when using electron-rich iron porphyrins bearing an electron-donating axial ligand, such as imidazole, and a carboxylic acid cocatalyst in close proximity to the iron center. The activity of the best systems was comparable to that of microsomal cytochromes P450 (between 1 and 10 turnovers per rain). The intermediate (porphyrin)iron-aldoxime complex formed in those dehydration reactions was isolated in the case of Fe(meso-tetra(2,6-dichlorophenyl)-β- octachloroporphyrin) [meso-tetra(2,6-dichlorophenyl)-β-octachloroporphyrin = TDCPCl8P] and characterized by elemental analysis and UV-visible and 1H NMR spectroscopy. Comparison of the 1H NMR spectra of Fe(TDCPCl8P)(CH3- CHNOH)2 and Fe(TDCPCl8P)(pyridine)2 strongly indicates that acetaldoxime is bound to iron(II) via its nitrogen atom in the former. A mechanism for iron porphyrin-catalyzed dehydration of aldoximes based on all these results is proposed. It involves a partial charge transfer from electron-rich Fe(II) to the aldoxime C=NOH moiety, which favors the departure of its OH group assisted by an acid cocatalyst. This illustrates the potential of iron porphyrins as catalysts for new reactions very different from the redox transformations for which they are well-known.
Cavity-promotion by pillar[5]arenes expedites organic photoredox-catalysed reductive dehalogenations
Esser, Birgit,Schmidt, Maximilian
supporting information, p. 9582 - 9585 (2021/09/28)
The efficiency of the photo-induced electron transfer in photoredox catalysis is limited by the diffusional collision of the excited catalyst and the substrate. We herein present cavity-bound photoredox catalysts, which preassociate the substrates, leading to significantly shortened reaction times. A pillar[5]arene serves as the cavity and phenothiazine as a catalyst in the reductive dehalogenation of aliphatic bromides as a proof of concept reaction.
Zinc Oxide/Graphene Oxide as a Robust Active Catalyst for Direct Oxidative Synthesis of Nitriles from Alcohols in Water
Sarvi, Iraj,Zahedi, Ehsan
, (2021/08/30)
In this work, without using any linker or chemical modification of graphene oxide, a zinc oxide immobilized graphene oxide-based catalyst was used for the direct aerobic oxidative conversion of alcohols to the nitriles in water. In the first step, graphene oxide was prepared and then zinc ions were electrostatically adsorbed onto the surface of graphene oxide. In the following step, zinc oxide nanoparticles were generated via in-situ growth in presence of NaOH. It was illustrated that graphene oxide layers can control the size of in-situ generated zinc oxide nanoparticles. Various aromatic/aliphatic/heteroaromatic primary alcohols converted to the nitriles in high yields under O2 balloon with ZnO/GO catalyst. This catalyst can be used for 7 successful consecutive runs without significant loss of activity. Graphic Abstract: [Figure not available: see fulltext.]
Conversion of Dinitrogen into Nitrile: Cross-Metathesis of N2-Derived Molybdenum Nitride with Alkynes
Hong, Xin,Jin, Li,Liao, Qian,Mézailles, Nicolas,Song, Jinyi
supporting information, p. 12242 - 12247 (2021/04/05)
The direct synthesis of nitrile from N2 under mild conditions is of great importance and has attracted much interest. Herein, we report a direct conversion of N2 into nitrile via a nitrile–alkyne cross-metathesis (NACM) process involving a N2-derived Mo nitride. Treatment of the Mo nitride with alkyne in the presence of KOTf afforded an alkyne-coordinated nitride, which was then transformed into MoV carbyne and the corresponding nitrile upon 1 e? oxidation. Both aryl- and alkyl-substituted alkynes underwent this process smoothly. Experiments and DFT calculations have proved that the oxidation state of the Mo center plays a crucial role. This method does not rely on the nucleophilicity of the N2-derived metal nitride, offering a novel strategy for N2 fixation chemistry.
Method for preparing valeronitrile through hydrogenation of pentenenitrile
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Paragraph 0032-0036, (2021/07/21)
The invention relates to a method for preparing valeronitrile through hydrogenation of pentenenitrile, and belongs to the technical field of chemical engineering. The method comprises the following steps: adding pentenenitrile, ethanol, a novel catalyst and an amorphous Fe-Mo-Ni-Al catalyst into a hydrogenation reaction kettle, starting stirring, carrying out nitrogen replacement for 3 times, then carrying out hydrogen replacement for 3 times, controlling the hydrogen pressure to be 0.2 Mpa, heating the reactants to 60 DEG C, and performing a reaction for 2 hours or determining that the hydrogen is not absorbed any more, continuously maintaining the hydrogen pressure, carrying out stirring reaction for half an hour, and then ending the reaction. The novel catalyst is a high-molecular palladium complex prepared from poly-gamma-(m-diphenylphosphinophenyl) propyl siloxane palladium with silicon dioxide as a carrier and sodium chloropalladite tetrahydrate through the interaction thereof.
