- Efficient nitriding reagent and application thereof
-
The invention discloses an efficient nitriding reagent and application thereof, wherein the nitriding reagent comprises nitrogen oxide, an active agent, a reducing agent and an organic solvent. By applying the nitriding reagent, nitrogen-containing compounds such as amide, nitrile and the like can be produced, and the method is simple in condition, low in waste discharge amount and simple in reaction equipment.
- -
-
Paragraph 0330-0332
(2021/03/31)
-
- Manganese-Pincer-Catalyzed Nitrile Hydration, α-Deuteration, and α-Deuterated Amide Formation via Metal Ligand Cooperation
-
A simple and efficient system for the hydration and α-deuteration of nitriles to form amides, α-deuterated nitriles, and α-deuterated amides catalyzed by a single pincer complex of the earth-abundant manganese capable of metal-ligand cooperation is reported. The reaction is selective and tolerates a wide range of functional groups, giving the corresponding amides in moderate to good yields. Changing the solvent from tert-butanol to toluene and using D2O results in formation of α-deuterated nitriles in high selectivity. Moreover, α-deuterated amides can be obtained in one step directly from nitriles and D2O in THF. Preliminary mechanistic studies suggest the transformations contributing toward activation of the nitriles via a metal-ligand cooperative pathway, generating the manganese ketimido and enamido pincer complexes as the key intermediates for further transformations.
- Ben-David, Yehoshoa,Diskin-Posner, Yael,Kar, Sayan,Milstein, David,Zhou, Quan-Quan,Zou, You-Quan
-
p. 10239 - 10245
(2021/08/24)
-
- Visible light-mediated synthesis of amides from carboxylic acids and amine-boranes
-
Here, a photocatalytic deoxygenative amidation protocol using readily available amine-boranes and carboxylic acids is described. This approach features mild conditions, moderate-to-good yields, easy scale-up, and up to 62 examples of functionalized amides with diverse substituents. The synthetic robustness of this method was also demonstrated by its application in the late-stage functionalization of several pharmaceutical molecules.
- Chen, Xuenian,Kang, Jia-Xin,Ma, Yan-Na,Miao, Yu-Qi
-
supporting information
p. 3595 - 3599
(2021/06/06)
-
- Mechanochemical Synthesis of Primary Amides
-
Ball milling of aromatic, heteroaromatic, vinylic, and aliphatic esters with ethanol and calcium nitride afforded the corresponding primary amides in a transformation that was compatible with a variety of functional groups and maintained the integrity of a stereocenter α to carbonyl. This methodology was applied to α-amino esters and N-BOC dipeptide esters and also to the synthesis of rufinamide, an antiepileptic drug.
- Gómez-Carpintero, Jorge,Sánchez, J. Domingo,González, J. Francisco,Menéndez, J. Carlos
-
p. 14232 - 14237
(2021/10/20)
-
- Supported palladium catalyzed aminocarbonylation of aryl iodides employing bench-stable CO and NH3surrogates
-
A simple, efficient and phosphine free protocol for carbonylative synthesis of primary aromatic amides under polystyrene supported palladium (Pd?PS) nanoparticle (NP) catalyzed conditions has been demonstrated. Herein, instead of using two toxic and difficult to handle gases simultaneously, we have employed the solid, economical, bench stable oxalic acid as the CO source and ammonium carbamate as the NH3source in a single pot reaction. For the first time, we have applied two non-gaseous surrogates simultaneously under heterogeneous catalyst (Pd?PS) conditions for the synthesis of primary amides using an easy to handle double-vial (DV) system. The developed strategy showed a good functional group tolerance towards a wide range of aryl iodides and afforded primary aromatic amides in good yields. The Pd?PS catalyst was easy to separate and can be recycled up to four consecutive runs with small loss in catalytic activity. We have successfully extended the scope of the methodology to the synthesis of isoindole-1,3-diones from 1,2-dihalobenzene, 2-halobenzoates and 2-halobenzoic acid following double and single carbonylative cyclization approaches.
- Bains, Rohit,Das, Pralay,Kumar, Ajay,Ram, Shankar,Shaifali,Sheetal
-
supporting information
p. 7193 - 7200
(2020/10/02)
-
- Transamidation for the Synthesis of Primary Amides at Room Temperature
-
Various primary amides have been synthesized using the transamidation of various tertiary amides under metal-free and mild reaction conditions. When (NH4)2CO3 reacts with a tertiary amide bearing an N-electron-withdrawing substituent, such as sulfonyl and diacyl, in DMSO at 25 °C, the desired primary amide product is formed in good yield with good funcctional group tolerance. In addition, N-tosylated lactam derivatives afforded their corresponding N-tosylamido alkyl amide products via a ring opening reaction.
- Chen, Jiajia,Lee, Sunwoo,Xia, Yuanzhi
-
supporting information
(2020/05/05)
-
- Aerobic oxidation of primary benzylic amines to amides and nitriles catalyzed by ruthenium carbonyl clusters carrying N,O-bidentate ligands
-
Four trinuclear ruthenium carbonyl clusters, (6-BrPyCHRO)2Ru3(CO)8 (R = 4-OCH3C6H4, 1a; R = 4-BrC6H4, 1b) and (2-OC6H4-HCN-C6H4R)2Ru3(CO)8 (R = 4-OCH3, 2a; R = 4-Br, 2b), were synthesized from the reactions of Ru3(CO)12 with the corresponding N,O-bidentate ligands (two pyridyl alcohols and two Schiff bases) respectively in a ratio of 1:2. Three new complexes 1b, 2a and 2b have been fully characterized by elemental analysis, FT-IR, NMR and X-ray crystallography. The catalytic activity of these ruthenium complexes for the aerobic oxidation of primary benzylic amines to amides and nitriles in the presence of t-BuOK was investigated, of which the Schiff base complex 2a was found to exhibit the highest activity.
- Dong, Qing,Han, Zhangang,Hao, Zhiqiang,Li, Ying,Lin, Jin,Lu, Guo-Liang,Meng, Lizhen,Yan, Xinlong
-
p. 3480 - 3487
(2020/04/02)
-
- Nitromethane as a nitrogen donor in Schmidt-type formation of amides and nitriles
-
The Schmidt reaction has been an efficient and widely used synthetic approach to amides and nitriles since its discovery in 1923. However, its application often entails the use of volatile, potentially explosive, and highly toxic azide reagents. Here, we report a sequence whereby triflic anhydride and formic and acetic acids activate the bulk chemical nitromethane to serve as a nitrogen donor in place of azides in Schmidt-like reactions. This protocol further expands the substrate scope to alkynes and simple alkyl benzenes for the preparation of amides and nitriles.
- Jiao, Ning,Liu, Jianzhong,Qiu, Xu,Song, Song,Wei, Jialiang,Wen, Xiaojin,Zhang, Cheng,Zhang, Ziyao
-
supporting information
p. 281 - 285
(2020/01/28)
-
- Arene-ruthenium(II)-phosphine complexes: Green catalysts for hydration of nitriles under mild conditions
-
Three new arene-ruthenium(II) complexes were prepared by treating [{RuCl(μ-Cl)(η6-arene)}2] (η6-arene = p-cymene) dimer with tri(2-furyl)phosphine (PFu3) and 1,3,5-triaza-7-phosphaadamantane (PTA), respectively to obtain [RuCl2(η6-arene)PFu3] [Ru]-1, [RuCl(η6-arene)(PFu3)(PTA)]BF4 [Ru]-2 and [RuCl(η6-arene)(PFu3)2]BF4 [Ru]-3. All the complexes were structurally identified using analytical and spectroscopic methods including single-crystal X-ray studies. The effectiveness of resulting complexes as potential homogeneous catalysts for selective hydration of different nitriles into corresponding amides in aqueous medium and air atmosphere was explored. There was a remarkable difference in catalytic activity of the catalysts depending on the nature and number of phosphorus-donor ligands and sites available for catalysis. Experimental studies performed using structural analogues of efficient catalyst concluded a structural-activity relationship for the higher catalytic activity of [Ru]-1, being able to convert huge variety of aromatic, heteroaromatic and aliphatic nitriles. The use of eco-friendly water as a solvent, open atmosphere and avoidance of any organic solvent during the catalytic reactions prove the reported process to be truly green and sustainable.
- Vyas, Komal M.,Mandal, Poulami,Singh, Rinky,Mobin, Shaikh M.,Mukhopadhyay, Suman
-
-
- One-Pot Anodic Conversion of Symmetrical Bisamides of Ethylene Diamine to Unsymmetrical gem-Bisamides of Methylene Diamine
-
Symmetrical bisamides of ethylene diamine of type ArCONHCH2CH2NHCOAr undergo anodic C-C bond cleavage in acetonitrile-LiClO4 under controlled-potential electrolysis. The electrogenerated carbocation intermediates react with the solvent acetonitrile to afford unsymmetrical gem-bisamides of type ArCONHCH2NHCOMe in a one-pot reaction. The yields of the latter products are moderate (up to 60%). Other minor products involve two symmetrical gem-bisamides of type ArCONHCH2NHCOAr and MeCONHCH2NHCOMe and fragmentation products (e.g., ArCONHCHO, ArCONH2, and ArCN).
- Golub, Tatiana,Dou, Gui-Yuan,Zeng, Cheng-Chu,Becker, James Y.
-
supporting information
p. 7961 - 7964
(2019/10/11)
-
- Base promoted peroxide systems for the efficient synthesis of nitroarenes and benzamides
-
A useful and efficient approach for the synthesis of nitroarenes from several aromatic amines (including heterocycles) using peroxide and base has been developed. This oxidative reaction is very easy to handle and afforded the products in good yields. Formation of benzamides from benzylamine was also successfully carried out with this metal-free catalytic system in good to excellent yields.
- Gupta, Sampa,Ansari, Alisha,Sashidhara, Koneni V.
-
supporting information
(2019/09/07)
-
- Ti-superoxide catalyzed oxidative amidation of aldehydes with saccharin as nitrogen source: Synthesis of primary amides
-
A new heterogeneous catalytic system (Ti-superoxide/saccharin/TBHP) has been developed that efficiently catalyzes oxidative amidation of aldehydes to produce various primary amides. The protocol employs saccharin as amine source and was found to tolerate a wide range of substrates with different functional groups. Moderate to excellent yields, catalyst reusability and operational simplicity are the main highlights. A possible mechanism and the role of the catalyst in oxidative amidation have also been discussed.
- Kamble, Rohit B.,Mane, Kishor D.,Rupanawar, Bapurao D.,Korekar, Pranjal,Sudalai,Suryavanshi, Gurunath
-
p. 724 - 728
(2020/01/23)
-
- Method for preparing derivatives of benzamide under microwave condition in aqueous phase
-
The invention discloses a method for preparing derivatives of benzamide under a microwave condition in an aqueous phase. A coupling reaction is carried out between substituted benzoic acid and amine under the microwave condition in the aqueous phase. The method for preparing the derivatives of benzamide is environmentally friendly, easy and convenient to operate, safe, low in cost and efficient. Compared with the prior art, the method can be applicable to a large number of functional groups, is high in yield, produces fewer by-products, and further is easy to operate, safe, low in cost and environmentally friendly. A formula is shown in the description.
- -
-
Paragraph 0018; 0073
(2019/03/28)
-
- 1,3-Dibromo-5,5-dimethylhydantoin mediated oxidative amidation of terminal alkenes in water
-
A variety of terminal alkenes were converted to the corresponding amides in yields of 25 to 86% in water via treatment with 1,3-dibromo-5,5-dimethylhydantoin, followed by reaction with molecular iodine and aq. NH3 (or amine) in one pot. This metal- and organic solvent-free protocol is not only suitable for styrene derivatives, but also, for the first time, works well on terminal aliphatic alkenes.
- Ma, Chunhua,Fan, Guojie,Wu, Ping,Li, Zhi,Zhou, Yang,Ding, Qingjie,Zhang, Wei
-
p. 9889 - 9894
(2017/12/12)
-
- Highly efficient synthesis of primary amides: Via aldoximes rearrangement in water under air atmosphere catalyzed by an ionic ruthenium pincer complex
-
The transformation of aldoximes to primary amides has been evaluated using pincer ruthenium complexes a-c, among which the ionic Ru catalyst a proved to be the most efficient in water under air atmosphere. A variety of (hetero)arene aldoximes proceeded smoothly to afford amides in high yields with good functional group compatibilities. Furthermore, a direct synthetic route of amides from aldehydes, hydroxylamine hydrochloride and sodium carbonate was also described with broad substrates including conjugated and aliphatic aldehydes. This protocol is operationally simple and proceeds with a low catalyst loading (0.5 mol%).
- Yang, Fa-Liu,Zhu, Xinju,Rao, Dun-Kang,Cao, Xiao-Niu,Li, Ke,Xu, Yan,Hao, Xin-Qi,Song, Mao-Ping
-
p. 37093 - 37098
(2016/05/24)
-
- Supported Gold Nanoparticles-Catalyzed Microwave-Assisted Hydration of Nitriles to Amides under Base-Free Conditions
-
Polystyrene-supported gold (Au@PS) nanoparticles were synthesized by the reduction deposition approach and well characterized by UV-visible, XRD, TEM, SAED, EDX, and XPS studies. The Au@PS was applied as catalyst for the hydration of nitriles to amides in water under microwave irradiation. Several functionalized aromatic, heterocyclic and aliphatic nitriles were found to be active for synthesis of the corresponding amides where no activation of water by base, ligand and support is needed. Easy recovery, negligible leaching and recyclability for up to eight runs are added advantages of the catalyst under water-mediated reaction conditions. (Figure presented.).
- Kumar, Sandeep,Sharma, Saurabh,Das, Pralay
-
supporting information
p. 2889 - 2894
(2016/09/16)
-
- Design, synthesis and fungicidal activity of N-substituted benzoyl-1,2,3,4-tetrahydroquinolyl-1-carboxamide
-
To find a new lead compound with high biological activity, a series of N-substituted benzoyl-1,2,3,4-tetrahydroquinolyl-1-carboxamide were designed using linking active substructures method. The target compounds were synthesized from substituted benzoic acid by four steps and their structures were confirmed by 1H NMR, IR spectrum and elemental analysis. The in vitro bioassay results indicated that some target compounds exhibited excellent fungicidal activities, and the position of the substituents played an important role in fungicidal activities. Especially, compound 5n, exhibited better fungicidal activities than the commercial fungicide flutolanil against two tested fungi Valsa Mali and Sclerotinia sclerotiorum, with EC50 values of 3.44 and 2.63 mg/L, respectively. And it also displayed good in vivo fungicidal activity against S. sclerotiorum with the EC50 value of 29.52 mg/L.
- Lei, Peng,Xu, Yan,Du, Juan,Yang, Xin-Ling,Yuan, Hui-Zhu,Xu, Gao-Fei,Ling, Yun
-
p. 2544 - 2546
(2016/07/07)
-
- Pd/C-catalyzed facile synthesis of primary aromatic amides by aminocarbonylation of aryl iodides using ammonia surrogates
-
Use of Pd/C as an efficient, phosphine free, heterogeneous and recyclable catalyst for one pot carbonylative synthesis of primary aromatic amides has been demonstrated. The developed protocol is simple to perform and employs ammonium carbamate as an in situ solid ammonia source which is feasible and more convenient than direct use of ammonia gas. The applicability of the developed protocol was studied for various aryl iodide substrates and it was found that it provides good to excellent yields of the desired amides. The catalyst is easily separable and shows significant recyclability for up to four consecutive cycles without loss of catalytic activity.
- Mane, Rajendra S.,Bhanage, Bhalchandra M.
-
p. 76122 - 76127
(2015/09/22)
-
- Palladium on manganese ferrite: An efficient catalyst for one pot synthesis of primary amides from iodobenzene
-
Amidation of aryl iodide in one pot is reported using Pd-MnFe2O4 as a catalyst. The catalyst was characterized by various techniques such as XRD, FEG-SEM, EDS, TEM, BET surface area and ICP AES. K4[Fe(CN)6]is used as a non toxic cyanation reagent for in situ generation of benzonitrile and hydrolyzed as soon as it formed. The catalyst was found to be efficient and can be used for several cycles without loss in activity. Good to excellent yields of primary amides were obtained.
- Jadhav, Vilas Gangadhar,Bhojane, Jeevan Manohar,Nagarkar, Jayashree Milind
-
p. 6636 - 6641
(2015/02/19)
-
- Direct conversion of aromatic aldehydes into benzamides via oxidation with potassium permanganate in liquid ammonia
-
Oxidation of aromatic aldehydes by KMnO4 in liquid ammonia gives amides directly. The reaction proceeds satisfactorily when the aldehydes are activated by electron-withdrawing substituents on the ring.
- Antoniak, Damian,Sakowicz, Arkadiusz,Loska, Rafa?,Makosza, Mieczys?aw
-
supporting information
p. 84 - 86
(2015/02/05)
-
- Transition-metal-free hydration of nitriles using potassium tert -butoxide under anhydrous conditions
-
Potassium tert-butoxide acts as a nucleophilic oxygen source during the hydration of nitriles to give the corresponding amides under anhydrous conditions. The reaction proceeds smoothly for a broad range of substrates under mild conditions, providing an efficient and economically affordable synthetic route to the amides in excellent yields. This protocol does not need any transition-metal catalyst or any special experimental setup and is easily scalable to bulk scale synthesis. A single-electron-transfer radical mechanism as well as an ionic mechanism have been proposed for the hydration process.
- Midya, Ganesh Chandra,Kapat, Ajoy,Maiti, Subhadip,Dash, Jyotirmayee
-
supporting information
p. 4148 - 4151
(2015/05/05)
-
- Direct oxidative esterification of alcohols and hydration of nitriles catalyzed by a reusable silver nanoparticle grafted onto mesoporous polymelamine formaldehyde (AgNPs@mPMF)
-
A nitrogen-rich mesoporous organic polymer was synthesized as a novel support. A silver nanoparticle was synthesized and grafted onto it. The prepared catalyst (AgNPs@mPMF) was characterized by powder X-ray diffraction (XRD), scanning electron microscopy(SEM) and energy dispersive X-ray spectrometry (EDS), thermogravimetric analysis (TGA), high-resolution transmission electron microscopy (HRTEM), UV-vis diffuse reflectance spectroscopy (DRS), N2 adsorption, Raman spectroscopy and EPR study. The catalytic activity was evaluated for the oxidative esterification reaction of alcohols and hydration of nitriles. The oxidative esterification reaction was carried out for various activated alcohols giving excellent yields of the corresponding ester products. The catalyst was also efficient in the hydration of nitriles. Both reactions were optimized by varying the bases, temperatures and solvents. The catalyst can be facilely recovered and reused six times without a significant decrease in its activity and selectivity.
- Ghosh, Kajari,Iqubal, Md. Asif,Molla, Rostam Ali,Mishra, Ashutosh,Kamaluddin,Islam, Sk Manirul
-
p. 1606 - 1622
(2015/04/27)
-
- A phosphine-free approach to primary amides by palladium-catalyzed aminocarbonylation of aryl and heteroaryl iodides using methoxylamine hydrochloride as an ammonia equivalent
-
The palladium-catalyzed synthesis of primary amides by aminocarbonylation of aryl and heteroaryl iodides under phosphine-free conditions is reported for the first time. Methoxylamine hydrochloride, acting as an ammonia equivalent, undergoes sequential carbonylation and demethoxylation under mild reaction conditions. The procedure does not require a phosphine ligand and takes place in short reaction times at low temperatures to provide the products in excellent yields. Georg Thieme Verlag Stuttgart · New York.
- Gadge, Sandip T.,Bhanage, Bhalchandra M.
-
-
- Direct conversion of aromatic aldehydes into benzamides via oxidation with potassium permanganate in liquid ammonia
-
Oxidation of aromatic aldehydes by KMnO4 in liquid ammonia gives amides directly. The reaction proceeds satisfactorily when the aldehydes are activated by electron-withdrawing substituents on the ring.
- Antoniak, Damian,Sakowicz, Arkadiusz,Loska, Rafa?,Makosza, Mieczys?aw
-
supporting information
(2015/01/08)
-
- Synthesis of primary Amides via Copper-Catalyzed Aerobic Decarboxylative ammoxidation of Phenylacetic Acids and α-Hydroxyphenylacetic acids with Ammonia in water
-
A Cu2O-catalyzed aerobic oxidative decarboxylative ammoxidation to primary benzamides from phenylacetic acids and a-hydroxyphenylacetic acids is developed. A variety of primary benzamides could be prepared smoothly, in good to excellent yields, by means of a one-pot domino protocol combining decarboxylation, dioxygen activation, oxidative C-H bond functionalization, and amidation reactions.
- Song, Qiuling,Feng, Qiang,Yang, Kai
-
supporting information
p. 624 - 627
(2014/04/03)
-
- Polymer-anchored Ru(II) complex as an efficient catalyst for the synthesis of primary amides from nitriles and of secondary amides from alcohols and amines
-
A polymer-anchored ruthenium(II) catalyst was synthesized and characterized. Its catalytic activity was evaluated for the preparation of primary amides from aqueous hydration of nitriles in neutral condition. A range of nitriles were successfully converted to their corresponding amides in good to excellent yields. The catalyst was also effective in the preparation of secondary amides from the coupling of alcohols and amines. The catalyst can be facilely recovered and reused six times without a significant decrease in its activity.
- Islam, Sk Manirul,Ghosh, Kajari,Roy, Anupam Singha,Molla, Rostam Ali
-
p. 900 - 907
(2015/02/19)
-
- Agonists for the adenosine A1 receptor with tunable residence time. a case for nonribose 4-amino-6-aryl-5-cyano-2-thiopyrimidines
-
We report the synthesis and evaluation of previously unreported 4-amino-6-aryl-5-cyano-2-thiopyrimidines as selective human adenosine A 1 receptor (hA1AR) agonists with tunable binding kinetics, this without affecting their nanomolar affinity for the target receptor. They show a very diverse range of kinetic profiles (from 1 min (compound 52) to 1 h (compound 43)), and their structure-affinity relationships (SAR) and structure-kinetics relationships (SKR) were established. When put in perspective with the increasing importance of binding kinetics in drug discovery, these results bring new evidence of the consequences of affinity-only driven selection of drug candidates, that is, the potential elimination of slightly less active compounds that may display preferable binding kinetics.
- Louvel, Julien,Guo, Dong,Agliardi, Marta,Mocking, Tamara A. M.,Kars, Roland,Pham, Tan Phát,Xia, Lizi,De Vries, Henk,Brussee, Johannes,Heitman, Laura H.,Ijzerman, Adriaan P.
-
p. 3213 - 3222
(2014/05/20)
-
- Palladium(III)-catalyzed fluorination of arylboronic acid derivatives
-
A practical, palladium-catalyzed synthesis of aryl fluorides from arylboronic acid derivatives is presented. The reaction is operationally simple and amenable to multigram-scale synthesis. Evaluation of the reaction mechanism suggests a single-electron-transfer pathway, involving a Pd(III) intermediate that has been isolated and characterized.
- Mazzotti, Anthony R.,Campbell, Michael G.,Tang, Pingping,Murphy, Jennifer M.,Ritter, Tobias
-
supporting information
p. 14012 - 14015
(2013/10/21)
-
- A general and practical oxidation of alcohols to primary amides under metal-free conditions
-
A general procedure for oxidation of both benzyl alcohols and alkyl alcohols to primary amides under catalyst free conditions has been developed. 34 examples of primary amides were produced from their corresponding alcohols in moderate to excellent yields. This is a practical procedure for primary amides synthesis; water and tert-butanol are the only by-products. A commercial drug, Piracetam, was prepared in one step with 73% yield as well.
- Wu, Xiao-Feng,Sharif, Muhammad,Feng, Jian-Bo,Neumann, Helfried,Pews-Davtyan, Anahit,Langer, Peter,Beller, Matthias
-
p. 1956 - 1961
(2013/09/24)
-
- Ruthenium-catalyzed one-pot synthesis of primary amides from aldehydes in water
-
The readily available arene-ruthenium(ii) complex [RuCl2(η 6-C6Me6){P(NMe2)3}] (5 mol%) proved to be an efficient catalyst for the direct synthesis of primary amides from aldehydes and hydroxylamine hydrochloride (NH2OH· HCl) in water at 100 °C. The process, which requires the presence of NaHCO3 to catch the HCl released during the formation of the key aldoxime intermediates, was operative with both aromatic, heteroaromatic, α,β-unsaturated and aliphatic aldehydes, and tolerated several functional groups. A greener approach using commercially available NH 2OH solution (50 wt.% in water) is also presented.
- Garcia-Alvarez, Rocio,Diaz-Alvarez, Alba E.,Crochet, Pascale,Cadierno, Victorio
-
p. 5889 - 5894
(2013/05/09)
-
- Thiazolyl-phosphine hydrochloride salts: Effective auxiliary ligands for ruthenium-catalyzed nitrile hydration reactions and related amide bond forming processes in water
-
A series of water-soluble N-protonated thiazolyl-phosphine hydrochloride salts have been synthesized and coordinated to the ruthenium(ii) fragment [RuCl2(η6-p-cymene)]. The resulting complexes were evaluated as potential catalysts for the selective hydration of nitriles to primary amides in environmentally friendly aqueous medium. The best results in terms of activity were achieved when tris(5-(2-aminothiazolyl))phosphine trihydrochloride was used as ligand. Using the Ru(ii) complex 9 derived from this salt (3 mol%), the catalytic reactions proceeded cleanly in pure water at 100 °C without the assistance of any additive, affording the desired amides in high yields (>78%) after short reaction periods (0.5-7 h). The process was operative with both aromatic, heteroaromatic, α,β-unsaturated and aliphatic nitriles, and tolerated several functional groups. The utility of 9 in promoting the formation of primary amides in water by catalytic rearrangement of aldoximes and direct coupling of aldehydes with NH2OH·HCl has also been demonstrated.
- Garcia-Alvarez, Rocio,Zablocka, Maria,Crochet, Pascale,Duhayon, Carine,Majoral, Jean-Pierre,Cadierno, Victorio
-
p. 2447 - 2456
(2013/09/12)
-
- Arene-ruthenium(II) complexes containing inexpensive tris(dimethylamino) phosphine: Highly efficient catalysts for the selective hydration of nitriles into amides
-
The catalytic hydration of nitriles into amides, in water under neutral conditions, has been studied using a series of arene-ruthenium(II) derivatives containing the commercially available and inexpensive ligand tris(dimethylamino)phosphine. Among them, best results were obtained with the complex [RuCl2(η6-C6Me6) {P(NMe2)3}], which selectively provided the desired amides in excellent yields and short times (TOF values up to 11 400 h-1). The process was operative with both aromatic, heteroaromatic, aliphatic, and α,β-unsaturated organonitriles and showed a high functional group tolerance. The stability of [RuCl2(η6-C 6Me6){P(NMe2)3}] in water was evaluated, observing its progressive decomposition into the less-active dimethylamine-ruthenium(II) complex [RuCl2(η6-C 6Me6)(NHMe2)] by hydrolysis of the coordinated P(NMe2)3 ligand. The X-ray crystal structure determination of the toluene complex [RuCl2(η6-C6H 5Me){P(NMe2)3}] is also included.
- Garcia-Alvarez, Rocio,Diez, Josefina,Crochet, Pascale,Cadierno, Victorio
-
experimental part
p. 5442 - 5451
(2011/12/13)
-
- One-pot synthesis of symmetrical 1,3-diarylureas or substituted benzamides directly from benzylic primary alcohols and effective oxidation of secondary alcohols to ketones using phenyliodine diacetate in combination with sodium azide
-
Benzylic primary alcohols can be directly converted into symmetrical 1,3-diarylureas or substituted benzamides via an one-pot oxidative reaction using the combined reagent of phenyliodine diacetate and sodium azide. This new reaction constitutes a step-economical way to prepare symmetric 1,3-diarylureas or substituted benzamides depending upon the substituents on the phenyl rings of starting alcohols. The sodium acetate generated in situ from the ligand exchange between phenyliodine diacetate and sodium azide plays the pivotal role in the formation of 1,3-diarylureas. In addition, it is also found that various secondary alcohols can be readily oxidized to their corresponding ketones in excellent yields using the same reagent system of phenyliodine diacetate and sodium azide. Generally, secondary alcohols are preferentially oxidized to the corresponding ketones in the presence of primary ones with the limited amounts of phenyliodine diacetate and sodium azide.
- Li, Xiao-Qiang,Wang, Wei-Kun,Han, Yi-Xin,Zhang, Chi
-
experimental part
p. 2588 - 2598
(2010/12/25)
-
- AMINOALYL-IMIDAZOTETRAZINES FOR TREATMENT OF CANCER
-
The present invention relates to imidazotetrazines of Formula (I) and their use in the treatment of cancer.
- -
-
-
- Selective ruthenium-catalyzed hydration of nitriles to amides in pure aqueous medium under neutral conditions
-
A study was conducted to demonstrate that water-soluble ruthenium(II) complexes can be used as catalysts for the hydration of nitriles in pure aqueous media and under neutral conditions. The hydration of benzonitrile was investigated as a model reaction and the ruthenium precursor was added to a 0.33M aqueous solution of benzonitrile at 100°C, while the reaction was monitored by gas chromatography. All the complexes checked, were found to be active and selective catalysts in the hydration process, providing benzamide as a specific reaction product. The most relevant results were obtained by using ruthenium complexes, bearing a nitrogen-containing ligand, which led to appropriate production of benzamide. The most effective ruthenium complex was found to be an efficient catalyst for the selective hydration of a large number of other nitriles.
- Cadierno, Victorio,Francos, Javier,Gimeno, Jose
-
scheme or table
p. 6601 - 6605
(2009/07/10)
-
- Efficient tandem process for the catalytic deprotection of N-allyl amides and lactams in aqueous media: A novel application of the bis(allyl)- ruthenium(IV) catalysts [Ru(η3:η2: η3-C12H18)Cl2] and [Ru(η3:η3-C10H16)-(μ-Cl) Cl}2]
-
An operationally simple and highly efficient methodology for the removal of the allyl protecting group in amides and lactams has been developed by using the commercially available bis(allyl)-ruthenium(IV) catalysts [Ru(η3:η2:η3-C12H 18)Cl2] (C12H18 = dodeca-2,6,10-triene-1,12-diyl) and [(Ru(η3:η3- C10H16)(μ-Cl)Cl}2] (C10H 16 = 2,7-dimethylocta-2,6-diene-1,8-diyl). The tandem process, which takes place in aqueous media and proceeds in a one-pot manner, involves the initial isomerization of the C=C bond of the allyl unit and subsequent oxidative cleavage of the resulting enamide.
- Cadierno, Victorio,Gimeno, Jose,Nebra, Noel
-
p. 6590 - 6594
(2008/03/13)
-
- The use of an electrophile carrier to determine the number of intermediates in the chlorination of 1-methylpyrrole
-
A kinetic and product study of the dichloroacetic acid catalyzed chlorination of 1-methylpyrrole with 3- and 4-substituted N-chlorobenzamides was carried out. Protonated N-chlorobenzamides served as carriers of CI+. A Hammett correlation was obtained with ρ=-0.68 (r=0.98, n=8). General acid catalysis was observed with α=0.48 (r=0.99 and n=7). The yields of 2-chlorination (84±0.7%) and 3-chlorination (2.6±0.4%) were essentially constant (constant intramolecular selectivity) as the substituent on the N-chlorobenzamide was varied. Observation of constant intramolecular selectivity indicated that two intermediates were formed during the acid catalyzed chlorination of 1-methylpyrrole with N-chlorobenzamides. The carrier method is applicable to all types of aromatic systems and limited only by the availability of suitable carrier molecules.
- De Rosa, Michael,Marquez, Manuel
-
p. 2125 - 2129
(2007/10/03)
-