100-48-1Relevant articles and documents
An efficient new procedure for the one-pot conversion of aldehydes into the corresponding nitriles
Zhu, Jia-Liang,Lee, Fa-Yen,Wu, Jen-Dar,Kuo, Chun-Wei,Shia, Kak-Shan
, p. 1317 - 1319 (2007)
A new and efficient procedure for the one-pot conversion of various aldehydes into the corresponding nitriles under mild reaction conditions has been developed. The ethyl dichlorophosphate/DBU-mediated dehydration of aldoxime intermediates was utilized as a key operation to effect the transformation. Georg Thieme Verlag Stuttgart.
Eine effiziente Synthese von 4-Cyanopyridin
Schantl, Joachim,Gstach, Hubert
, p. 694 - 695 (1980)
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An efficient one-pot synthesis of nitriles from carboxylic acids without solvent under microwave irradiation
Juncai, Feng,Bin, Liu,Yang, Lhi,Changchuan, Li
, p. 4545 - 4548 (1996)
Nitriles were prepared from alkyl and aryl carboxylic acids in dry media conditions, under microwave irradiation. Heating of the carboxylic acid, urea and amidosulfonic acid adsorbed on alumina support in a microwave oven affords nitriles in 20-93% yields.
A mild deoxygenation of heteroaromatic N-oxides by formamidinesulfinic acid
Balicki, Roman,Chmielowiec, Urszula
, p. 1105 - 1107 (2000)
Various heteroaromatic N-oxides were efficiently deoxygenated to the corresponding bases under mild conditions using formamidinesulfinic acid (thiourea S,S-dioxide).
Efficient and chemoselective deoxygenation of amine N-oxides using polymethylhydrosiloxane
Chandrasekhar,Reddy, Ch. Raji,Rao, R. Jagadeeshwar,Rao, J. Madhusudana
, p. 349 - 351 (2002)
Deoxygenation of aromatic and aliphatic amine N-oxides to the corresponding amines is achieved under mild conditions. The reagent combination employed for this transformation is polymethylhydrosiloxane (PMHS) in the presence of either tetrakis (triphenylphosphine) palladium (0) [Pd(PPh3)4], titanium (IV) isopropoxide [Ti(i-PrO)4] or palladium on carbon (Pd/C).
Boryl Radicals-Triggered Selective C-H Functionalization for the Synthesis of Diverse Phenanthridine Derivatives
Guo, Ao,Han, Jia-Bin,Tang, Xiang-Ying
, p. 2351 - 2355 (2018)
A boryl radical-triggered C-H functionalization of aliphatic ethers/amines or DMF with isocyanides is developed to deliver diverse phenanthridine derivatives in good to excellent yields. The substrate scope is broad, and a wide range of functional groups
A Novel and Efficient Deoxygenation of Hetero Cyclic N-Oxides Using ZrCl4/NaBH4
Chary, K. Purushothama,Mohan, G. Hari,Iyengar, D. S.
, p. 1339 - 1340 (1999)
A practical and novel reagent system ZrCl4/NaBH4 is used for the deoxygenation of N-Oxides to amines is described.
Highly efficient gold nanoparticle catalyzed deoxygenation of amides, sulfoxides, and pyridine N-oxides
Mikami, Yusuke,Noujima, Akifumi,Mitsudome, Takato,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
, p. 1768 - 1772 (2011)
Selective deoxygenation is one of the most important reactions in the areas of total synthesis, biological chemistry, and transformation of renewable biomass resources.To date, many useful methods for the selective deoxygenation of oxygen-containing organic molecules, such as amides, nitro compounds, epoxides, sulfoxides, and those with Noxide groups, have been developed. However, these methods often include stoichiometric reactions. Some successful catalysts have been reported,but most of them are homogeneous systems and still suffer from low activities and selectivities, harsh reaction conditions, and tedious workup procedures. Therefore, further development of highly efficient heterogeneous catalysts for selective deoxygenations is highly desired.
Efficient catalytic conversion of pyridine N-oxides to pyridine with an oxorhenium(V) catalyst
Wang, Ying,Espenson, James H.
, p. 3525 - 3526 (2000)
(Equation Presented) The compound CH3Re(O)(SR)2PPh3, where (SR)2 represents the dianion of 2-(mercaptomethyl)thiophenol, catalyzes the rapid and efficient transfer of an oxygen atom from a wide range of ring-substituted pyridine N-oxides to triphenylphosphine, yielding the pyridines in high yield.
Efficient Deoxygenation of Heteroaromatic N-Oxides with Ammonium Formate as a Catalytic Hydrogen Transfer Agent
Balicki, Roman
, p. 645 - 646 (1989)
Ammonium formate catalytic transfer hydrogenation in the presence of 10percent palladium on carbon has shown utility for mild and excellent deoxygenation of heteroaromatic N-oxides in neutral medium.
Masuda, Yoshio,Susuki, Toshio,Yamada, Tomoko,Sawada, Kiyoshi
, p. 225 - 236 (1988)
Reaction of N-aminopyridinium salt with cyanide ion.
Okamoto,Hirobe,Tamai
, p. 1089 - 1090 (1963)
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Reactivity of Heterocyclic Nitrogen Donors in Systems containing the Tetrachloroaurate(III) Anion
Canovese, Luciano,Cattalini, Lucio,Tomaselli, Michele,Tobe, Martin L.
, p. 307 - 314 (1991)
A series of gold(III) complexes of the type has been prepared and characterized (L = oxazole, benzoxazole, thiazole, their benzo and methyl-substituted derivatives, or 2-methylbenzoselenazole).The five-membered N.O-, N,S- and N,Se-heterocyclic bases are all bound to Au(III) through nitrogen.The kinetics of the displacement of L by chloride to give (1-) has been studied in methanol-water (95:5. v/v) at 25.0 deg C and I = 0.20 mol dm-3 (LiClO4).The equilibrium constants for the reversible processes have also been determined.The reactions of the corresponding pyridine, 4-chloro-, 4-cyano- and 2,6-bis(chloromethyl)-pyridine complexes have also been reexamined under the same conditions.The equlibrium constants, K2, depend upon the basicity of the nitrogen in the ligands and points for all ligands, irrespective of ring size and composition, lie roughly on the same log K2 versus pKa curve.There is no significant systematic steric effect on the equilibrium constants of the sort found for the more basic methyl pyridines.The complexes of the five-membered heterocyclic ligands are approximately ten times less reactive than those of the six-membered N-heterocycles of comparable basicity and exhibit steric retardation from ortho-methyl substituents.The nucleophilicities of these ligands have been calculated and five-membered N,O- and N,S-heterocycles are considerably less reactive than six-membered N-heterocycles of similar basicity.
Formation and Reaction of Trichloro Complexes of Bivalent Transition Metals in 1,2-Dichloroethane
Satoh, Keiichi,Suzuki, Toshio,Sawada, Kiyoshi
, p. 591 - 594 (1988)
Trichloro complexes of some bivalent transition metals (M2+) have been prepared in tetra-n-butylammonium chloride-1,2-dichloroethane solution saturated with the metal chlorides.Their chemical forms and reactions, and the effect of water, have been investigated by means of spectrophotometry and vapour-pressure osmometry at 25.0 deg C.Copper(II) and cadmium(II) form monomeric tetrahedral trichloro complexes containing onoe water molecule, NBu4, whilst cobalt(II) forms a dimeric tetrahedral trichloro complex 2.Zinc(II) exists as a mixture of monomeric and dimeric forms.Manganese(II) and nickel(II) do not form trichloro complexes.Copper(II) forms a monomeric tetrachloro complex.Cobalt(II) forms a monomeric tetrachloro complex and a trichloromono(pyridine base) complex by reaction with NBu4Cl and with pyridine base respectively.The formation constants of the copper(II) and cobalt(II) complexes have been evaluated by means of spectrophotometry.The effect of water on the equilibria of the trichloro complexes of coppoer(II) and cobalt(II) is discussed.
An Efficient Deoxgenation of Heteroaromatic N-Oxides Using Zinc Dust/Ammonium Formate Reagent System
Balicki, Roman,Cybulski, Marcin,Maciejewski, Grzegorz
, p. 4137 - 4141 (2003)
Heteroaromatic N-oxides were readily and selectively deoxygenated to the corresponding bases with zinc/ammonium formate reagent system.
Stability studies of bis(pyridiniumaldoxime) reactivators of organophosphate-inhibited acetylcholinesterase
Lin,Klayman
, p. 797 - 799 (1986)
Relative stability studies of three organophosphate-inhibited acetylcholinesterase reactivators, 1-(2-hydroximinomethyl-1-pyridinium)-3-(4-carbamoyl-1-pyridi nium)-2-oxapropane dichloride (HI-6), 1,1'-methylenebis(4-hydroximinomethylpyridinium) dichloride (MMB-4), and 1,1'-trimethylenebis(4-hydroximinomethylpyridinium) dibromide (TMB-4) were carried out by semiquantitative TLC and NMR methods. TMB-4 appears to be the most, and HI-6 the least stable of the three compounds. The extent of hydrolysis of HI-6, MMB-4, and TMB-4 in 0.05 M, pH 7 phosphate buffer was ~50, 25, and 2O and of the protons at the 2- and 6-positions of the pyridinium ring of TMB-4 in NaOD/D2 were observed.
Selective and efficient deoxygenation of amine-n-oxides with CeCl 3 7H2O/zinc system
Yoo, Byung Woo,Jung, Ha Il,Kim, Se Heon,Ahn, Young Sun,Choi, Ji Yong
, p. 359 - 360 (2013)
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Efficient Chemoselective Reduction of N-Oxides and Sulfoxides Using a Carbon-Supported Molybdenum-Dioxo Catalyst and Alcohol
Li, Jiaqi,Liu, Shengsi,Lohr, Tracy L.,Marks, Tobin J.
, p. 4139 - 4146 (2019)
The chemoselective reduction of a wide range of N-oxides and sulfoxides with alcohols is achieved using a carbon-supported dioxo-molybdenum (Mo@C) catalyst. Of the 10 alcohols screened, benzyl alcohol exhibits the highest reduction efficiency. A variety of N-oxide and both aromatic and aliphatic sulfoxide substrates bearing halogens as well as additional reducible functionalities are efficiently and chemoselectively reduced with benzyl alcohol. Chemoselective N-oxide reduction is effected even in the presence of potentially competing sulfoxide moieties. In addition, the Mo@C catalyst is air- and moisture-stable, and is easily separated from the reaction mixture and then re-subjected to reaction conditions over multiple cycles without significant reactivity or selectivity degradation. The high stability and recyclability of the catalyst, paired with its low toxicity and use of earth-abundant elements makes it an environmentally friendly catalytic system.
Mild and efficient method for the synthesis of nitriles
Coskun, Necdet
, p. 1625 - 1630 (2004)
The treatment of aldoximes with a mixture of DMAD and triethylamine serve as an efficient and mild method for the synthesis of aromatic and α,β-unsaturated nitriles in high yields at room temperature.
Cyclic Hydroxamic Acid Analogues of Bacterial Siderophores as Iron-Complexing Agents prepared through the Castagnoli–Cushman Reaction of Unprotected Oximes
Bakulina, Olga,Bannykh, Anton,Dar'in, Dmitry,Krasavin, Mikhail
, p. 17667 - 17673 (2017)
The first application of multicomponent chemistry (the Castagnoli–Cushman reaction) toward the convenient one-step preparation of cyclic hydroxamic acids is described. Cyclic hydroxamic acids are close analogues of bacterial siderophores (iron-binding com
Electrochemical Deoxygenation of N-Heteroaromatic N -Oxides
Xu, H.-C.,Xu, P.
, p. 1219 - 1221 (2019)
An electrochemical method for the deoxygenation of N-heteroaromatic N -oxide to give the corresponding N-heteroaromatics has been developed. Several classes of N-heterocycles such as pyridine, quinoline, isoquinoline, and phenanthridine are tolerated. The electrochemical reactions proceed efficiently in aqueous solution without the need for transition-metal catalysts and waste-generating reducing reagents.
Oxidative ammonolysis of 2,4,6-collidine at vanadium-titanium oxide catalyst
Kagarlitsky,Krichevsky
, p. 315 - 317 (2003)
4-Cyanopyridine was synthesized from the readily obtainable 2,4,6-collidine by oxidative ammonolysis in the presence of vanadium-titanium oxide catalyst. Conditions under which the yield of the product amounted to 73% on the amount of the trimethylpyridin
Photocatalytic deoxygenation of N-O bonds with rhenium complexes: From the reduction of nitrous oxide to pyridineN-oxides
Anthore-Dalion, Lucile,Cantat, Thibault,Kjellberg, Marianne,Nicolas, Emmanuel,Ohleier, Alexia,Thuéry, Pierre
, p. 10266 - 10272 (2021)
The accumulation of nitrogen oxides in the environment calls for new pathways to interconvert the various oxidation states of nitrogen, and especially their reduction. However, the large spectrum of reduction potentials covered by nitrogen oxides makes it difficult to find general systems capable of efficiently reducing variousN-oxides. Here, photocatalysis unlocks high energy species able both to circumvent the inherent low reactivity of the greenhouse gas and oxidant N2O (E0(N2O/N2) = +1.77 Vvs.SHE), and to reduce pyridineN-oxides (E1/2(pyridineN-oxide/pyridine) = ?1.04 Vvs.SHE). The rhenium complex [Re(4,4′-tBu-bpy)(CO)3Cl] proved to be efficient in performing both reactions under ambient conditions, enabling the deoxygenation of N2O as well as synthetically relevant and functionalized pyridineN-oxides.
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Prijs et al.
, p. 571,574 (1948)
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Oxidative ammonolysis of 3(4)-methyl- and 3,4-dimethylpyridines using vanadium oxide catalysts
Vorobyev,Serebryanskaya
, p. 1987 - 1993 (2012)
Oxidative ammonolysis of 3(4)-methyl- and 3,4-dimethylpyridines using vanadium oxide catalyst doped with Cr2O3, SnO2, and ZrO2 was studied. The yields of nitriles and conversion of the starting compounds were found to depend on the CH-acidity of the latter in the gas phase. The possible mechanisms of the formation of pyridine-3,4-dicarboxylic acid imide at the oxidative ammonolysis of 3,4-dimethylpyridine was discussed. The relation between the activity of the modified catalysts and the proton affinity of the vanadyl oxygen calculated by the extended Hueckel method was established.
Metal-Free Deoxygenation of Amine N-Oxides: Synthetic and Mechanistic Studies
Lecroq, William,Schleinitz, Jules,Billoue, Mallaury,Perfetto, Anna,Gaumont, Annie-Claude,Lalevée, Jacques,Ciofini, Ilaria,Grimaud, Laurence,Lakhdar, Sami
, p. 1237 - 1242 (2021/06/01)
We report herein an unprecedented combination of light and P(III)/P(V) redox cycling for the efficient deoxygenation of aromatic amine N-oxides. Moreover, we discovered that a large variety of aliphatic amine N-oxides can easily be deoxygenated by using only phenylsilane. These practically simple approaches proceed well under metal-free conditions, tolerate many functionalities and are highly chemoselective. Combined experimental and computational studies enabled a deep understanding of factors controlling the reactivity of both aromatic and aliphatic amine N-oxides.
Lewis Acidic Boranes, Lewis Bases, and Equilibrium Constants: A Reliable Scaffold for a Quantitative Lewis Acidity/Basicity Scale
Mayer, Robert J.,Hampel, Nathalie,Ofial, Armin R.
supporting information, p. 4070 - 4080 (2021/01/29)
A quantitative Lewis acidity/basicity scale toward boron-centered Lewis acids has been developed based on a set of 90 experimental equilibrium constants for the reactions of triarylboranes with various O-, N-, S-, and P-centered Lewis bases in dichloromethane at 20 °C. Analysis with the linear free energy relationship log KB=LAB+LBB allows equilibrium constants, KB, to be calculated for any type of borane/Lewis base combination through the sum of two descriptors, one for Lewis acidity (LAB) and one for Lewis basicity (LBB). The resulting Lewis acidity/basicity scale is independent of fixed reference acids/bases and valid for various types of trivalent boron-centered Lewis acids. It is demonstrated that the newly developed Lewis acidity/basicity scale is easily extendable through linear relationships with quantum-chemically calculated or common physical–organic descriptors and known thermodynamic data (ΔH (Formula presented.)). Furthermore, this experimental platform can be utilized for the rational development of borane-catalyzed reactions.
