Study of hydrolysis processes of 2,6-dicyanopyridine

Евстратова, М. И.; Прокопов, А. А.; Ivanova, I. L.; Markova, I. G.; Tubina, I. S.; Анисимова, О. С.; Skwirskaya, N. V.; Kan, I. I.; Suvorov, B. V.; Yakhontov, L. N.

doi:10.1007/bf00771778

Cited by 5 publications

(6 citation statements)

References 2 publications

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“…The solid was dissolved in dioxane (30 mL), and aqueous ammonia (75 mL) was added. After 30 min, the white precipitate was collected by filtration, washed with water (1 × 10 mL), and dried in vacuo to give 18i (1.46 g, 74%) as a white solid: mp 311–313 °C (lit . mp 305–306 °C); 1 H NMR (500 MHz, DMSO- d 6 ) δ 8.89 (s, 2 H), 8.13–8.20 (m, 3 H), 7.71 (s, 2 H); 13 C NMR (126 MHz, DMSO- d 6 ) δ 165.8, 149.5, 139.6, 124.6; HRMS-ESI ( m / z ) [M + Na] + calcd for C 7 H 7 N 3 O 2 Na 188.04305, found 188.04291.…”

Section: Methodsmentioning

confidence: 99%

“…After 30 min, the white precipitate was collected by filtration, washed with water (1 × 10 mL), and dried in vacuo to give 18i (1.46 g, 74%) as a white solid: mp 311−313 °C (lit. 63 Pyridine-2,6-dicarbonitrile 62 (18j). Pyridine-2,6-dicarboxamide (18i) (1.45 g, 8.8 mmol) was dissolved in dry N,N-dimethylformamide (92 mL).…”

Section: -(Ethylcarbamoyl)-1-methylpyrazinium Trifluoromethanesulfona...mentioning

confidence: 99%

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Electron-Deficient Heteroarenium Salts: An Organocatalytic Tool for Activation of Hydrogen Peroxide in Oxidations

et al. 2015

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A series of monosubstituted pyrimidinium and pyrazinium triflates and 3,5-disubstituted pyridinium triflates were prepared and tested as simple catalysts of oxidations with hydrogen peroxide, using sulfoxidation as a model reaction. Their catalytic efficiency strongly depends on the type of substituent and is remarkable for derivatives with an electron-withdrawing group, showing reactivity comparable to that of flavinium salts which are the prominent organocatalysts for oxygenations. Because of their high stability and good accessibility, 4-(trifluoromethyl)pyrimidinium and 3,5-dinitropyridinium triflates are the catalysts of choice and were shown to catalyze oxidation of aliphatic and aromatic sulfides to sulfoxides, giving quantitative conversions, high preparative yields and excellent chemoselectivity. The high efficiency of electron-poor heteroarenium salts is rationalized by their ability to readily form adducts with nucleophiles, as documented by low pKR+ values (pKR+ < 5) and less negative reduction potentials (Ered > -0.5 V). Hydrogen peroxide adducts formed in situ during catalytic oxidation act as substrate oxidizing agents. The Gibbs free energies of oxygen transfer from these heterocyclic hydroperoxides to thioanisole, obtained by calculations at the B3LYP/6-311++g(d,p) level, showed that they are much stronger oxidizing agents than alkyl hydroperoxides and in some cases are almost comparable to derivatives of flavin hydroperoxide acting as oxidizing agents in monooxygenases.

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Section: Methodsmentioning

confidence: 99%

Section: -(Ethylcarbamoyl)-1-methylpyrazinium Trifluoromethanesulfona...mentioning

confidence: 99%

Electron-Deficient Heteroarenium Salts: An Organocatalytic Tool for Activation of Hydrogen Peroxide in Oxidations

et al. 2015

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“…In other studies modeling kerogen reactivity, decyl decanoate was readily hydrolyzed in water at 250 °C in an ionic reaction that was further catalyzed by brine (10% NaCl) and calcium montmorillonite. Evstratova et al hydrated 2,6-dicyanopyridine stepwise to the diamide in boiling water in a reaction that is acid- and base-catalyzed. Norton described a hydrolytic process for making aromatic carboxylic acids from nitriles at 200−300 °C in a process where no catalyst is added directly, but the aqueous solution from earlier hydrolyses is used in order to take advantage of autocatalysis by ammonia formed during the hydrolysis of the amide intermediate.…”

Section: Cleavage/hydrolysis Reactionsmentioning

confidence: 99%

Aquathermolysis: Reactions of Organic Compounds with Superheated Water

1996

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I. Preliminaries1. Introduction. In this Account, we will emphasize that organic molecules undergo a wide range of chemistry in neutral superheated water. Counter to what is traditionally taught in organic chemistry courses, no acids, bases, or catalysts need to be added. In this chemistry, water participates as a catalyst, reactant, and solvent. For example, polyethylene terephthalate (plastic soda bottles), polyurethanes, and other polymers are cleaved to their starting materials at 300 °C. Diaryl ethers cleave rapidly, Diels-Alder reaction selectivities are dramatically enhanced, and several types of deuteration reactions are effected in pure superheated deuterium oxide. Such reactions, and many others, are facilitated by changes in the chemical and physical properties of water as temperature increases. These changes make the solvent properties of water (density, dielectric constant) at high temperature similar to those of polar organic solvents at room temperature, thus facilitating reactions with organic compounds in an environmentally friendly medium. An increase in the dissociation constant by 3 orders of magnitude allows water at

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“…Nitrile hydrolysis to amides occurs only under extreme pH conditions or very high temperature. 11 Consequently, DCP is a non-toxic, water-stable and thus biocompatible stapling reagent.…”

Section: Introductionmentioning

confidence: 99%