- Acceptorless dehydrogenation of amines to nitriles catalyzed by N-heterocyclic carbene-nitrogen-phosphine chelated bimetallic ruthenium (II) complex
-
We have developed a clean, atom-economical and environmentally friendly route for acceptorless dehydrogenation of amines to nitriles by combining a new dual N-heterocyclic carbene-nitrogen-phosphine ligand R(CNP)2 (R = o-xylyl) with a ruthenium precursor [RuCl2(η6-C6H6)]2. In this system, the electronic and steric factors of amines had a negligible influence on the reaction and a broad range of functional groups were well tolerated. All of the investigated amines could be converted to nitriles in good yield of up to 99% with excellent selectivity. The unprecedented catalytic performance of this system is attributed to the synergistic effect of two ruthenium centers chelated by R(CNP)2 and a plausible reaction mechanism is proposed according to the active species found via in situ NMR and HRMS.
- Chen, Hua,Fu, Haiyan,Ji, Li,Li, Ruixiang,Nie, Xufeng,Zheng, Yanling
-
p. 378 - 385
(2020/10/02)
-
- Method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by Ru coordination compound
-
The invention discloses a method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by a Ru coordination compound. The method comprises: adding a Ru coordination compound, an alkali, a primary amine and an organic solvent into a reaction test tube according to a mol ratio of 1:100:(100-500):1000-3000, and carrying out a stirring reaction under the condition of 80 to120 DEG C; and when gas chromatography monitors that the raw materials completely disappear, stopping the reaction, collecting the reaction solution, centrifuging the reaction solution, taking the supernatant, extracting with dichloromethane, merging the organic phases, drying, filtering, evaporating the organic solvent under reduced pressure to obtain a filtrate, and carrying out column chromatography purification on the filtrate to obtain the target product nitrile. According to the invention, the catalyst is good in activity, single in catalytic system, good in product selectivity, simple in subsequent treatment and good in system universality after the reaction is finished, has a good catalytic effect on various aryl, alkyl and heteroaryl substituted primary amines, and also has a gooddehydrogenation performance on secondary amines.
- -
-
Paragraph 0034-0039; 0196-0201
(2020/09/16)
-
- Transformation of aromatic bromides into aromatic nitriles with n-BuLi, pivalonitrile, and iodine under metal cyanide-free conditions
-
Various aromatic nitriles could be obtained in good yields by the treatment of aryl bromides with n-butyllithium and then pivalonitrile, followed by the treatment with molecular iodine at 70 °C, without metal cyanides under transition-metal-free conditions. The present reaction proceeds through the radical β-elimination of imino-nitrogen-centered radicals formed from the reactions of imines and N-iodoimines under warming conditions.
- Uchida, Ko,Togo, Hideo
-
-
- Iron and Phenol Co-Catalysis for Rapid Synthesis of Nitriles under Mild Conditions
-
A mild, scalable, high yielding, and rapid route to access diverse nitriles from aldehyde oxime esters enabled by iron(III) and phenol co-catalysis has been developed. The reaction was performed at room temperature to give nitriles in excellent yield within minutes. Mechanistic studies show that the reaction may proceed through a radical process in which benzoyl aldehyde oxime is not only a substrate, but also an ancillary ligand to support iron salt in the promotion of the transformation.
- Meng, Hong,Gao, Sen,Luo, Meiming,Zeng, Xiaoming
-
p. 4617 - 4623
(2019/07/15)
-
- Access to nitriles from aldehydes mediated by an oxoammonium salt
-
A scalable, high yielding, rapid route to access an array of nitriles from aldehydes mediated by an oxoammonium salt (4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate) and hexamethyldisilazane (HMDS) as an ammonia surrogate has been developed. The reaction likely involves two distinct chemical transformations: reversible silyl-imine formation between HMDS and an aldehyde, followed by oxidation mediated by the oxoammonium salt and desilylation to furnish a nitrile. The spent oxidant can be easily recovered and used to regenerate the oxoammonium salt oxidant.
- Kelly, Christopher B.,Lambert, Kyle M.,Mercadante, Michael A.,Ovian, John M.,Bailey, William F.,Leadbeater, Nicholas E.
-
supporting information
p. 4241 - 4245
(2015/04/14)
-
- Two ways of preparing benzonitriles using BrCCl3-PPh3 as the reagent
-
Benzamides were converted into benzonitriles with BrCCl3- PPh3-Et3N in CH2Cl2 in an Appel-type reaction. Benzaldoximes could be transformed to benzonitriles under identical conditions. It was found that the reaction system BrCCl3-(2 equiv.)PPh3 was also suitable for these transformations with PPh 3 replacing Et3N.
- Jasem, Yosef Al,Barkhad, Mohamed,Khazali, Mona Al,Butt, Hifsa Pervez,El-Khwass, Noha Ashraf,Azani, Mariam Al,Hindawi, Bassam Al,Thiemann, Thies
-
-
- Schmidt reaction in ionic liquids: Highly efficient and selective conversion of aromatic and heteroaromatic aldehydes to nitriles with [BMIM(SO3H)][OTf] as catalyst and [BMIM][PF6] as solvent
-
A mild and selective method is presented for the conversion of aromatic and heteroaromatic aldehydes to nitriles via the Schmidt reaction with TMSN 3 by using [BMIM(SO3H)][OTf] as catalyst and [BMIM][PF6] as solvent. The method offers high yields and simple product isolation, and avoids the use of liquid superacids or corrosive Lewis acids commonly employed for this transformation. It also offers some potential for recycling/reuse of the IL solvent.
- Nandi, Ganesh C.,Laali, Kenneth K.
-
p. 2177 - 2179
(2013/04/24)
-
- Practical one-pot transformation of electron-rich aromatics into aromatic nitriles with molecular iodine and aq NH3 using Vilsmeier-Haack reaction
-
Various electron-rich aromatics could be efficiently transformed into the corresponding aromatic nitriles in good to moderate yields by treatment with DMF and POCl3, followed by the reaction with molecular iodine or 1,3-diiodo-5,5-dimethylhydantoin (DIH) in aq NH3. Some of less reactive aromatics, such as anisole, 1,2-dimethoxybenzene, 1,4-dimethoxybenzene, and mesityrene, could be also transformed into the corresponding aromatic nitriles in good to moderate yields using N-methylformanilide and O(POCl 2)2, followed by the reaction with molecular iodine in aq NH3. Moreover, propiophenone derivatives could be successfully transformed into the corresponding β-chlorocinnamonitriles by the reaction with DMF and POCl3, followed by the reaction with molecular iodine and aq NH3. These reactions are novel metal-free one-pot methods for the preparation of aromatic nitriles from electron-rich aromatics and β-chlorocinnamonitriles from propiophenones.
- Ushijima, Sousuke,Moriyama, Katsuhiko,Togo, Hideo
-
experimental part
p. 4588 - 4595
(2012/07/27)
-
- One-pot conversion of aromatic bromides and aromatics into aromatic nitriles via aryllithiums and their DMF adduct
-
Various aromatic bromides and iodides were smoothly converted into the corresponding aromatic nitriles in good to moderate yields by the treatment with n-butyllithium and subsequently DMF, followed by treatment with molecular iodine in aq NH3. The same treatment of typical aromatics and heteroaromatics with n-butyllithium and subsequently DMF, followed by treatment with molecular iodine in aq NH3 also provided the corresponding aromatic nitriles in good yields. Moreover, the same treatment of aromatic bromides and aromatics with half amount of DIH (1,3-diiodo-5,5- dimethylhydantoin) instead of molecular iodine worked effectively to give the corresponding aromatic nitriles, respectively, in good yields. These reactions are novel and environmentally benign one-pot methods for the preparation of aromatic nitriles from aromatic bromides and aromatics, respectively, through the formation of aryllithiums and their DMF adducts.
- Ushijima, Sousuke,Moriyama, Katsuhiko,Togo, Hideo
-
experimental part
p. 958 - 964
(2011/03/19)
-
- One-pot conversion of aromatic bromides and aromatics into aromatic nitriles
-
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
- Ushijima, Sousuke,Togo, Hideo
-
experimental part
p. 1562 - 1566
(2010/09/05)
-
- Controlled conversion of phenylacetic acids to phenylacetonitriles or benzonitriles using bis(2-methoxyethyl)aminosulfur trifluoride
-
A mild, efficient, and practical method for the one-step synthesis of benzonitriles from phenylacetic acids using bis(2-methoxyethyl)aminosulfur trifluoride is described. The reaction was easily extended to the synthesis of the corresponding phenylacetonitriles by inclusion of triethylphosphine.
- Kangani, Cyrous O.,Day, Billy W.,Kelley, David E.
-
p. 914 - 918
(2008/09/17)
-
- Palladium-catalyzed, copper(I)-mediated coupling of boronic acids and benzylthiocyanate. A cyanide-free cyanation of boronic acids
-
(Equation Presented) A new method for the synthesis of nitriles is described. As a complement to the classic cyanation of aryl halides using cyanide sources and a transition metal catalyst, the palladium-catalyzed cross-coupling of thiocyanates with boronic acids in the presence of copper(I) thiophene-2-carboxylate (CuTC) affords nitriles in good to excellent yields.
- Zhang, Zhihui,Liebeskind, Lanny S.
-
p. 4331 - 4333
(2007/10/03)
-
- S,S-dimethyl dithiocarbonate: A useful reagent for efficient conversion of aldoximes to nitriles
-
Dimethyl dithiocarbonate (DMDTC) has been shown to be an efficient dehydrating agent for a range of oximes derived from aliphatic, aromatic and heteroaromatic aldehydes yielding the corresponding nitriles in high yields.
- Khan, Taukeer Ahmad,Peruncheralathan, Saravanan,Ila, Hiriyakkanavar,Junjappa, Hiriyakkanavar
-
p. 2019 - 2021
(2007/10/03)
-
- Direct release of nitriles from solid phase
-
Cleavage conditions are described which allow resin bound secondary amides to be liberated from Sieber or Rink resin as nitriles. The method has been applied to the synthesis of a series of cyanobiaryls. Published by 2001 Elsevier Science Ltd.
- Hone, Neal D.,Payne, Lloyd J.,Tice, Colin M.
-
p. 1115 - 1118
(2007/10/03)
-
- Tetrabutylammonium peroxydisulfate in organic synthesis. Part 8. An efficient and convenient nickel-catalyzed oxidation of primary amines to nitriles with tetrabutylammonium peroxydisulfate
-
A series of primary amines are oxidized to corresponding nitriles in excellent yields with tetrabutylammonium peroxydisulfate catalyzed by nickel copper formate under basic aqueous conditions.
- Chen, Fen-Er,Peng, Zuo-Zhong,Fu, Han,Liu, Ji-Dong,Shao, Lan-Ying
-
p. 726 - 727
(2007/10/03)
-
- Selective preparation of 4-(bromo or iodo)-2,5-dimethoxybenzonitrile and 2-(bromo or iodo)-3,6-dimethoxybenzonitrile from 2,5-dimethoxybenzaldehyde
-
By use of appropriate reactions and sequence of steps, 2,5- dimethoxybenzaldehyde can be converted either to 4-(bromo or iodo)-2,5- dimethoxybenzonitrile or 2-(bromo or iodo)-3,6-dimethoxybenzonitrile.
- Hathaway, Bruce A.,Taylor, Brian E.,Wittenborn, Jeremy S.
-
p. 4629 - 4637
(2007/10/03)
-
- Cyanation anodique de substrats aromatiques en milieux micellaires cationique, anionique et non ionique
-
Anodic cyanation of 1,2- 1,3 and 1,4 dimethoxybenzenes (o, m and pDMB) is studied in cationic (CTAB or CTAS), anionic (SDS) and non ionic (Brij 35) micellar solutions and in a cationic microemulsion (oDMB only).Analytical measures (current-potentiel curves on PtRDE and LSV) mainly performed with pDMB are consistent with a single electron transfer which is quasi reversible in anionic and non ionic micellar media but becomes progressively irreversible in cationic micelles (Tabl. 2).The increase of irreversibility with the CTAB concentration is probably connected with the adsorption of this surfactant.With cyanide, these adsorption (mainly of CTACN) leads to a more extensive CN- oxidation (curve 2, Fig. 5a) than in pure water (curve 1) whereas SDS and Brij 35 have no influence (curve 1, Fig. 5a) (this indicates a weaker adsorption or a highly porous film).The decrease of the limiting currents on RDE (Fig. 1) arises from important neutral substrates-micelles associations.The half-wave potentials are constant in the whole range of SDS and Brij 35 concentrations whereas they shift quickly to positive values with CTAB beyond the CMC (Tabl. and Fig. 1).These results suggest equal interactions of the anodicaly formed cation radical and the neutral parent with the anionic and non ionic micelles (Sch. 1).The strong E1/2 shift observed with the cationic micelles results mainly from the CTAB adsorption.Anionic and non ionic micellar inhibition of cyanation leads to lower yields than in homogeneous organic solutions (Tabl. 4).In consequence of the local concentrations, anodic cyanation occurs in the aqueous pseudophase and therefore is limited by the exit of the radical cation and (or) the neutral parent compound from the anionic and non ionic micelles.Moreover, in aqueous solution and in anionic micellar medium, the CN- addition on pDMB+. competes with the homogeneous electron transfer (reaction 3, Sch. 3) as shown by the kinetic currents observed in water with and without SDS (Tabl. 3, Fig. 2 and 3).The indirect CN- oxidation (Sch. 2) is negligible in CH3CN (Fig. 4) and in non ionic micelles (which behave like an organic medium).It probably does not occur with cationic micelles (CTAS) as a consequence of the increase of the direct oxidation (reaction 2, Sch. 3) due to the increase of the anodic potential.The higher yields of cyanated products in cationic micelles (Tabl. 4) can be explained by the classical concept (increase of CN- concentrations near the cationic micelles and the film of surfactant adsorbed on the anode).The change in cyanation selectivity between the cationic micellar solution and the other media (organic solutions, anionic and non ionic micelles) (Tabl. 5) can be interpreted in two ways: 1.In cationic micellar medium the strong CN- oxidation (curves 1, Fig. 5b,c; curves 1 and 1' Fig. 6) would give CN. radicals in the vicinity of DMB+..The coupling between these species (reaction 4, Sch. 3, and Sch. 4) would then be governed by the spin density repartition in the radical catio...
- Rauniyar, G.,Thomalla, M.
-
p. 156 - 167
(2007/10/02)
-
- Simple and Efficient Copper-Catalyzed One-Pot Conversion of Aldehydes into Nitriles
-
Aromatic, heterocyclic, and tertiary aliphatic nitriles are prepared from the corresponding aldehydes by the ammonium chloride/copper powder/oxygen system in pyridine.This new one-flask procedure affords very high to quantitative yields of pure nitriles.
- Capdevielle, Patrice,Lavigne, Andre,Maumy, Michel
-
p. 451 - 452
(2007/10/02)
-
- Direct Synthesis of 5-Methyl-3-aryl-1,2,4-oxadiazoles from Aryl Aldehydes, Nitroethane, and Ammonium Acetate
-
The condensation of 2,5-dimethoxybenzaldehyde (1b) with nitroethane and ammonium acetate in glacial acetic acid has been found to give three diffrent products, depending on reactant ratio and reaction time.At an aldehyde:nitroethane:ammonium acetate ratio of 1:1.5:0.8 a normal Knoevenagel condensation occured, yielding 1-(2,5-dimethoxyphenyl)-2-nitropropene.At a reactant ratio of 1:3:2 (same reactant sequence), the primary product was 2,5-dimethoxybenzonitrile, and at a reactant ratio of 1:40:8, with extended reflux time, the major product was 3-(2,5-dimethoxyphenyl)-5-methyl-1,2,4-oxadiazole (8b).This last reaction served as a prototype for a new oxadiazole synthesis which was then extended to include six additional 5-methyl-3-aryl-1,2,4-oxadiazoles (8a,c-g; where aryl = Ph, 2,5-dimethoxyphenyl, 2,4-dichlorophenyl, m-chlorophenyl, p-tolyl, 3,5-dimethoxyphenyl, and p-carboxyphenyl), whose structures were assigned on the basis of 13C NMR characteristics of known reference compounds.Benzonitrile also reacted with excess nitroethane and ammonium acetate to yield 5-methyl-3-phenyl-1,2,4-oxadiazole (8a).The overall mechanism of oxadiazole formation is shown to be dependent on a preliminary reaction wherein the nitroalkane, in the presence of ammonium acetate and acetic acid, is first transformed into the corresponding alkanoic acid and hydroxylamine.Hydroxylamine then converts the aromatic aldehyde, via the intermediary nitrile, to the oxadiazoles following reactions of established precedent.
- Young, Thomas E.,Beidler, William Thomas
-
p. 1182 - 1186
(2007/10/02)
-
- Synthesis of Substituted Phenazines from Benzofurazanoxid and Hydroquinones
-
The sterical course of the formation of substituted phenazines from benzofurazanoxid and hydroquinone derivatives was investigated.The additional functional group of the hydroquinone determines the substitution pattern and the product ratio of the phenazines formed. - Key words: Phenazine, Synthese, Hydrochinone
- Roemer, A.,Sammet, M.
-
p. 866 - 872
(2007/10/02)
-
- THE HYDROCYANATION OF FREE AND POLYMER-BOUND BENZOQUINONE
-
The polimer-bound quinone 2 has been prepared and used in column form with organic solvents for the convenient preparation of other quinones.In contrast to the solution reaction hydrocyanation of this quinone by the Thiele-Meisenheimer reaction did not yield a useful proportion of polymer-bound dicyanohydroquinone but instead gave a mixture of products including much monocyanohydroquinone.Helferich and Bodenbender's 2,3-dicyanocyclohexan-1,4-dione is in fact wholly the di-enol and is a likely intermediate in the hydrocyanation of benzoquinone, being oxidised by the latter to 2,3-dicyanocyclohex-2-ene-1,4-dione which tautomerises to the observed product, 2,3-dicyanohydroquinone.A lower accessibility to polymer-bound reactants as compared with those in solution is implied by these results.
- Perry, Gregory J.,Sutherland, Maurice D.
-
p. 1471 - 1476
(2007/10/02)
-