cas 65-45-2, Salicylamide | Articles data

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Copper-mediated α-hydroxylation of N-salicyloyl-glycine. A model for peptidyl-glycine α-amidating monooxygenase (PAM)
Title compound 1 is selectively hydroxytated in α position by three distinct copper- containing oxidant systems, involving dioxygen, peroxide anion or trimethylamine oxide. Trivalent copper is likely the key intermediate in this first reported model for the PHM activity of enzyme PAM.
Capdevielle, Patrice,Maumy, Michel
p. 3831 - 3834
(1991)
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Mg/Al mixed oxides: Heterogeneous basic catalysts for the synthesis of salicylamide from urea and phenol
Several Mg/Al mixed oxides were prepared by thermal decomposition of hydrotalcites and used for the synthesis of salycilamide from urea and phenol. Their physicochemical properties were characterized by ICP, XRD, CO 2-TPD and N2 adso
Wang, Dengfeng,Zhang, Xuelan,Wei, Wei,Sun, Yuhan
p. 159 - 162
(2012)
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Green and efficient Beckmann rearrangement by Cu(II) contained nano-silica triazine based dendrimer in water
In this research, a Cu(II) contained nano-silica triazine based dendrimer was prepared, characterized, and utilized as a retrievable catalytic system (Cu(II)-TrDen@nSiO2) for green formation of primary amides in water at room temperature. The structure of nanoparticles was fully characterized by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), Fourier transform infrared spectroscopy (FT-IR), and thermogravimetry analysis (TGA). The results revealed that the nanoparticles have spherical morphology and an average size of around 40 nm. The analysis also illustrated that the copper nanoparticles had been successfully loaded on the nitrogen-rich dendritic structure with a uniform distribution. The inductively coupled plasma analysis showed that about 0.67 mmol/g of Cu was loaded on the Cu(II)-TrDen@nSiO2 support. Mild reaction conditions, excellent yields, environment-friendly synthesis, and easily prepared starting materials are the key features of the present method. The catalyst is easily removed from the reaction media using a simple filtration and can be re-used at least five times without any considerable loss of its catalytic activity.
Bahreininejad, Mohammad Hasan,Moeinpour, Farid
p. 893 - 901
(2021/01/12)

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.
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Paragraph 0318-0320

(2021/03/31)

Preparation method of aromatic amide compound
The present invention provides a preparation method of an aromatic amide compound. In an organic solvent, under the effect of a catalyst, an aromatic acid compound and an amine source are subjected toa dehydration reaction to obtain the aromatic amide compound, wherein the aromatic acid compound is an aromatic acid, a substituted aromatic acid, a heterocyclic aromatic acid or a substituted heterocyclic aromatic acid; and the substituent group of amide is any substituent group of H, a C1-C8 straight-chain alkyl or branched-chain alkyl group, a benzene ring or an aromatic ring. The aromatic amide compound is an important chemical intermediate, and the synthesis method is mild in reaction condition and high in yield.
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Paragraph 0060-0061

(2020/07/15)

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)

Asymmetric Hydrogenation of Cationic Intermediates for the Synthesis of Chiral N,O-Acetals
For over half a century, transition-metal-catalyzed homogeneous hydrogenation has been mainly focused on neutral and readily prepared unsaturated substrates. Although the addition of molecular hydrogen to C=C, C=N, and C=O bonds represents a well-studied paradigm, the asymmetric hydrogenation of cationic species remains an underdeveloped area. In this study, we were seeking a breakthrough in asymmetric hydrogenation, with cationic intermediates as targets, and thereby anticipating applying this powerful tool to the construction of challenging chiral molecules. Under acidic conditions, both N- or O-acetylsalicylamides underwent cyclization to generate cationic intermediates, which were subsequently reduced by an iridium or rhodium hydride complex. The resulting N,O-acetals were synthesized with remarkably high enantioselectivity. This catalytic strategy exhibited high efficiency (turnover number of up to 4400) and high chemoselectivity. Mechanistic studies supported the hypothesis that a cationic intermediate was formed in situ and hydrogenated afterwards. A catalytic cycle has been proposed with hydride transfer from the iridium complex to the cationic sp2 carbon atom being the rate-determining step. A steric map of the catalyst has been created to illustrate the chiral environment, and a quantitative structure–selectivity relationship analysis showed how enantiomeric induction was achieved in this chemical transformation.
Sun, Yongjie,Zhao, Qingyang,Wang, Heng,Yang, Tilong,Wen, Jialin,Zhang, Xumu
supporting information
p. 11470 - 11477
(2020/08/10)

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
(2019/12/11)

Substrate Profiling of the Cobalt Nitrile Hydratase from Rhodococcus rhodochrous ATCC BAA 870
The aromatic substrate profile of the cobalt nitrile hydratase from Rhodococcus rhodochrous ATCC BAA 870 was evaluated against a wide range of nitrile containing compounds (>60). To determine the substrate limits of this enzyme, compounds ranging in size from small (90 Da) to large (325 Da) were evaluated. Larger compounds included those with a biaryl axis, prepared by the Suzuki coupling reaction, Morita–Baylis–Hillman adducts, heteroatomlinked diarylpyridines prepared by Buchwald–Hartwig crosscoupling reactions and imidazo[1,2a]pyridines prepared by the Groebke–Blackburn–Bienaymé multicomponent reaction. The enzyme active site was moderately accommodating, accepting almost all of the small aromatic nitriles, the diarylpyridines and most of the biaryl compounds and Morita–Baylis–Hillman products but not the Groebke–Blackburn–Bienaymé products. Nitrile conversion was influenced by steric hindrance around the cyano group, the presence of electron donating groups (e.g., methoxy) on the aromatic ring, and the overall size of the compound.
Mashweu, Adelaide R.,Chhiba‐Govindjee, Varsha P.,Bode, Moira L.,Brady, Dean
(2020/01/13)

Application method of antioxidant in salicylamide synthesis process
The invention discloses an application method of an antioxidant in a salicylamide synthesis process, wherein the application method comprises the steps: in the process of synthesizing salicylamide from methyl salicylate, adding the antioxidant, and after reaction is completed, carrying out after-treatment to obtain a finished product white salicylamide. The raw materials of the antioxidant are cheap and easily available; the method has the advantages of simple process, energy conservation, consumption reduction, high production safety and the like; the problem that the color of salicylamide isslightly pink in the existing industrial production is solved; the step of crude product purification is omitted; and the product quality and yield are greatly improved.
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Paragraph 0019-0023

(2020/08/22)

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)

Method for efficient solid-phase synthesis of amide derivative through carboxylic acid and urea
The invention discloses a method for efficient solid-phase synthesis of an amide derivative through carboxylic acid and urea. The method comprises the steps that a carboxylic acid and urea mixture anda catalyst are mixed, a mixture is placed in a sealed pipe of a single-mode microwave device and heated, then through a monitoring reaction endpoint, namely the ratio, being 4:1, of cyclohexane to ethyl acetate in thin-layer chromatography (TLC), reactants are cooled to the room temperature, extraction is conducted through the ethyl acetate, then an extract is sequentially washed by hydrochloricacid, a sodium bicarbonate solution and water, an organic layer is dried by anhydrous magnesium sulfate, a solvent is subjected to decompressed distillation, and thus the amide derivative is obtained.Benzoic acid and the urea are mixed and heated for a long time at 220 DEG C, a chemical reaction can be completed only within 20-80 seconds by applying a microwave assistive technology, and the effect higher than the effect achieved by conventional heating is achieved. By applying a solvent-free solid phase method and utilizing an easy-to-obtain reagent, high-yield amide is prepared through a simple and effective method, and the solvent-free solid phase method has the advantages of high reaction speed, low catalyst cost and the like.
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Paragraph 0022-0030

(2019/11/12)

Photoinduced Hydroxylation of Organic Halides under Mild Conditions
Presented in this paper is photoinduced hydroxylation of organic halides, providing a mild access to a range of functionalized phenols and aliphatic alcohols. These reactions generally proceed under mild reaction conditions with no need for a photocatalyst or a strong base and show a wide substrate scope as well as excellent functional group tolerance. This work highlights the unique role of NaI that allows a challenging transformation to proceed under mild reaction conditions.
Cai, Yue-Ming,Xu, Yu-Ting,Zhang, Xin,Gao, Wen-Xia,Huang, Xiao-Bo,Zhou, Yun-Bing,Liu, Miao-Chang,Wu, Hua-Yue
supporting information
p. 8479 - 8484
(2019/10/16)

The highly efficient air oxidation of aryl and alkyl boronic acids by a microwave-assisted protocol under transition metal-free conditions
Molecular oxygen is the most important green-oxidant due to its excellent properties. However, the effective utilization of molecular oxygen remains a major challenge in modern chemistry. Herein, we report the development a rapid, green and efficient microwave-assisted protocol for the air oxidation of boronic acids to phenols and alcohols under transition metal-free conditions. In the presence of KOH and DMSO, high yields of the expected phenols and alcohol were obtained with microwave-assistance, and a variety of functional groups were tolerated in this procedure. Notably, this transition metal-free method represents a breakthrough in both organic synthesis and green chemistry for the oxidative hydroxylation of boronic acids to phenols and alcohols.
Yin, Weiyan,Pan, Xizhi,Leng, Wenxi,Chen, Jian,He, Haifeng
supporting information
p. 4614 - 4618
(2019/09/09)

Technology for synthesizing 5-acetylsalicylamide
The invention discloses a technology for synthesizing 5-acetylsalicylamide. Methyl salicylate, methyl alcohol, acetylchloride, a self-made modified nano-scale solid acid catalyst and the like are subjected to recrystallization, magnetic stirring, acid treatment and other operation means to prepare the 5-acetylsalicylamide.
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Paragraph 0009-0034

(2019/08/20)

(Ar-tpy)RuII(ACN)3: A Water-Soluble Catalyst for Aldehyde Amidation, Olefin Oxo-Scissoring, and Alkyne Oxygenation
The synthetic chemists always look for developing new catalysts, sustainable catalysis, and their applications in various organic transformations. Herein, we report a new class of water-soluble complexes, (Ar-tpy)RuII(ACN)3, utilizing designed terpyridines possessing electron-donating and -withdrawing aromatic residues for tuning the catalytic activity of the Ru(II) complex. These complexes displayed excellent catalytic activity for several oxidative organic transformations including late-stage C-H functionalization of aldehydes with NH2OR to valuable primary amides in nonconventional aqueous media with excellent yield. Its diverse catalytic power was established for direct oxo-scissoring of a wide range of alkenes to furnish aldehydes and/or ketones in high yield using a low catalyst loading in the water. Its smart catalytic activity under mild conditions was validated for dioxygenation of alkynes to highly demanding labile synthons, 1,2-diketones, and/or acids. This general and sustainable catalysis was successfully employed on sugar-based substrates to obtain the chiral amides, aldehydes, and labile 1,2-diketones. The catalyst is recovered and reused with a moderate turnover. The proposed mechanistic pathway is supported by isolation of the intermediates and their characterization. This multifaceted sustainable catalysis is a unique tool, especially for late-stage functionalization, to furnish the targeted compounds through frequently used amidation and oxygenation processes in the academia and industry.
Joarder, Dripta De,Gayen, Subrata,Sarkar, Rajarshi,Bhattacharya, Rajarshi,Roy, Sima,Maiti, Dilip K.
p. 8468 - 8480
(2019/07/03)

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.
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Paragraph 0018; 0069

(2019/03/28)

Base-promoted nucleophilic fluoroarenes substitution of C–F bonds
With the use of KOH/DMSO as the superbase medium, the nucleophilic fluoroarene substitution for C–F bonds is presented. The transformation proceeds smoothly with the use of fluoroarenes bearing not only electron-withdrawing group, but also electron-donating group and a variety of nucleophiles such as alcohols, phenols, amines, amides and nitrogen-heterocyclic compounds. The double nucleophilic substitution using ortho-difluoroarenes and nucleophiles bearing ortho-dinucleophilic groups results in the formation of 2,3-dihydro-1,4-benzodioxins, dibenzo[b,e][1,4]dioxins and 10H-phenoxazines in moderate to good yields.
Su, Ji,Chen, Qian,Lu, Le,Ma, Yuan,Auyoung, George Hong Lok,Hua, Ruimao
supporting information
p. 303 - 307
(2017/12/11)

Novel design of recyclable copper(II) complex supported on magnetic nanoparticles as active catalyst for Beckmann rearrangement in poly(ethylene glycol)
Copper complex-functionalized magnetic core–shell nanoparticles (Fe3O4@SiO2-Lig-Cu) were prepared and characterized using various techniques. The activity of the new catalyst was tested for the Beckmann rearrangement. The reaction conditions allow for the conversion of a wide variety of aldoximes, including aromatic and heterocyclic ones, to amides in good to excellent yields. High efficiency, mild reaction conditions, easy work-up, use of poly(ethylene glycol) as a green medium and simple purification of products are important advantages of this system. Moreover, the eco-friendly heterogeneous nanocatalyst could be easily recovered from the reaction mixture using an external magnet and reused several times.
Keyhaniyan, Mahdi,Shiri, Ali,Eshghi, Hossein,Khojastehnezhad, Amir
(2018/05/23)

A convenient synthesis of phenols
Anilines are rapidly, often within 60 minutes, converted into the corresponding phenols in up to 87% isolated yield. The presented experimentally simple protocol display broad compatibility with a variety of functional groups, and in particular, well suited for the preparation of methyl-substituted phenols. Such phenols are not easily available by other synthetic approaches. The formation of phenolic radical coupling products was not observed even for activated anilines using this open flask method.
Kristianslund, Renate,Vik, Anders,Hansen, Trond V.
supporting information
p. 2809 - 2814
(2018/12/04)

Photocatalytic benzene and benzene derivative direct hydroxylation or amination method
The invention discloses a photocatalytic benzene and benzene derivative direct hydroxylation or amination method. The method is characterized by comprising the following steps: (1) adding a photo-sensitizer and a cobalt catalyst into a solvent to obtain a solution (A); (2) adding benzene (or benzene derivatives), water, ammonia gas, and amide derivatives (or sulfonamide derivatives) into the solution (A) to obtain a solution (B); and (3) in a N2 (or Ar) environment, radiating the solution (B) by a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, or an LED lamp to obtain phenols or amines and H2. For the first time, a photo-sensitizer and a cobalt catalyst are combined and applied to photocatalytic hydroxylation and amination of benzene. The conditions of the method are mild, light is taken as the driving energy, no oxidant is added, the only byproduct is H2, and the whole process is green, concise, and efficient. High selective benzene one-step hydroxylation to generate phenol or high selective phenol/benzene one-step amination to generate aniline is realized, and the method can be applied to the production of phenol and aniline.
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Paragraph 0118-0119

(2017/11/29)

A Brevibacterium process for synthesizing amide
The invention discloses a method for synthesizing amide through nitrile hydrolysis. The method comprises the following steps: adding nitrile, acetaldoxime, water, a water-soluble rhodium complex to a reaction vessel, and cooling to room temperature after reaction of a reaction mixture for several hours at the temperature of 50-80 DEG C; and adding ethyl acetate for extraction so as to obtain an organic layer, and carrying out rotary evaporation to remove a solvent, thus obtaining a target product. Compared with a method for synthesizing amide through nitrile hydrolysis by using oxime as a water source in a transition metal catalysis process, the method has the advantages that a used catalyst is low in loading and does not contain a phosphine ligand seriously polluting environments, synthesis can be performed in air, and nitrogen protection is not needed; and therefore, the method meets the green chemistry requirements and has a wide development prospect.
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Paragraph 0052; 0053; 0054; 0055

(2017/04/29)

A selective hydration of nitriles catalysed by a Pd(OAc)2-based system in water
In situ formation of a [Pd(OAc)2bipy] (bipy = 2,2′-bipyridyl) complex in water selectively catalyses the hydration of a wide range of organonitriles at 70 °C. Catalyst loadings of 5 mol% afford primary amide products in excellent yields in the absence of hydration-promoting additives such as oximes and hydroxylamines.
Sanz Sharley, Daniel D.,Williams, Jonathan M.J.
supporting information
p. 4090 - 4093
(2017/09/27)

Preparation method of salicylamide
The invention provides a preparation method of salicylamide and belongs to the field of fine chemicals. The preparation method is characterized by comprising the following steps that under normal pressure, methyl salicylate and a buffer solution are added into a reaction bottle according to the weight ratio being 1:2-4, the temperature is increased to 30-60 DEG C, ammonia gas is introduced continuously to conduct an amidation reaction, the reaction temperature is controlled to be 40-60 DEG C, the ammonia gas is stopped being introduced after the reaction is conducted for 1 hour, the temperature is decreased to 20-25 DEG C through cooling, centrifugation and drying are conducted, and the salicylamide is obtained. By the adoption of the preparation method, the hydrolysis side reaction of methyl salicylate is effectively reduced, the prepared salicylamide is high in yield, easy to separate, high in purity and free of mixed color in appearance, and the preparation method is low in cost and environmentally friendly.
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Paragraph 0017-0018

(2017/09/02)

Efficient preparation method of salicylamide
The invention relates to an efficient preparation method of salicylamide. The preparation method comprises the following steps: (1) weighing raw materials, wherein the raw materials comprise the following components in parts by weight: 35-50 parts of salicylic acid, 10-20 parts of liquid ammonia, 100-200 parts of ionized water and 5-10 parts of catalyst; (2) uniformly mixing the 35-50 parts of salicylic acid, the 10-20 parts of liquid ammonia and 10-20 parts of ionized water, and heating at the temperature of 85-110 DEG C to obtain an ammonization solution; (3) adding the 12-22 parts of catalyst into the ammonization solution, and performing dehydration treatment for 2-4 hours to obtain a primary product; (4) uniformly mixing the residual ionized water and the primary product by stirring to obtain a secondary product, adding the secondary product into a centrifugal machine to perform centrifuging, removing supernate, and drying precipitate to obtain the salicylamide. The method for preparing the salicylamide has the advantages of low cost and prevention of pollution.
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Paragraph 0009

(2016/12/16)

Photocatalytic Hydrogen-Evolution Cross-Couplings: Benzene C-H Amination and Hydroxylation
We present a blueprint for aromatic C-H functionalization via a combination of photocatalysis and cobalt catalysis and describe the utility of this strategy for benzene amination and hydroxylation. Without any sacrificial oxidant, we could use the dual catalyst system to produce aniline directly from benzene and ammonia, and phenol from benzene and water, both with evolution of hydrogen gas under unusually mild conditions in excellent yields and selectivities.
Zheng, Yi-Wen,Chen, Bin,Ye, Pan,Feng, Ke,Wang, Wenguang,Meng, Qing-Yuan,Wu, Li-Zhu,Tung, Chen-Ho
supporting information
p. 10080 - 10083
(2016/09/04)

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)

A mild hydration of nitriles catalysed by copper(ii) acetate
A simple, mild and general procedure for the hydration of nitriles to amides using copper as catalyst and promoted by N,N-diethylhydroxylamine is described. The reaction can be conducted in water at low temperature in short reaction times. This new procedure allows amides to be obtained from a wide range of substrates in excellent yields.
Marcé, Patricia,Lynch, James,Blacker, A. John,Williams, Jonathan M. J.
supporting information
p. 1436 - 1438
(2016/01/25)

METHOD TO PREPARE PHENOLICS FROM BIOMASS
The present invention is directed to a method for preparing a final phenolic product from biomass comprising the steps of providing a furanic compound obtainable from biomass; reacting the furanic compound with a dienophile to obtain a phenolic compound; reacting the phenolic compound further to obtain the final phenolic product.
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Page/Page column 36

(2016/08/10)

Acid Catalyzed Direct-Amidation-Dehydrocyclization of 2-Hydroxy-acetophenones to Benzoxazoles by a One-Pot Sustainable Synthesis
A series of 2-methyl-benzoxazoles have been synthesized starting from 2-hydroxy-acetophenones via a one-pot three steps reaction. Hydroxylamonium salt has been used as amidation agent. The reaction occurs with different anions, but the best results is achieved with hydroxylamonium hydrchloride. Despite the number of consecutive stages, the reaction is highly selective. Mild reaction conditions and various solvents can be used, but trifluoroacetic acid is the preferred. Almost, complete recovery of the trifluoroacetic acid can be achieved by vacuum distillation. The role of trifluoroacetic acid, as well as, of the hydroxylamonium salt suggests a cooperative effect leading to high selective formation of 2-methyl-benzoxazoles. Graphical Abstract: One-pot TFA catalyzed synthesis of benzoxazoles starting from 2-hydroxyacetophenones. (Chemical Equation Presented).
Rancan, Elia,Aric, Fabio,Quartarone, Giuseppe,Ronchin, Lucio,Vavasori, Andrea
p. 939 - 946
(2015/08/06)

Synthesis of novel angular diazaphenoxazinone derivatives via palladium catalyzed Buchwald-Hartwig amidation protocols
The synthesis of new amido derivatives of angular diazaphenoxazinone via tandem amidation protocol is reported. This was achieved by the condensation of 4,5-diamino-6-hydroxypyrimidine (7) with 2,3-dichloro-1,4-naphthoquinone (8) in anhydrous basic medium to furnish the key intermediate, 11-amino-6-chloro-8,10-diazabenzo[a]phenoxazin-5-one (9). Palladium catalyzed amidation reaction of 11-amino-6-chloro-8,10-diazabenzo[a]phenoxazin-5-one (9) with different amides (12a-c) (benzamide, acetamide, salicylamide and 4-nitrobenzamide) in the presence of palladium(II) acetate, triphenyl phosphine (PPh3), water and tertiary butanol at 110°C for 3 h gave the new amido derivatives 13a-c. Structures of the new compounds were established by elemental analysis, UV, FTIR, 1H NMR and 13C NMR.
Odaa,Okoro,Ugwu
p. 3069 - 3073
(2016/08/24)

AIEE active perylene bisimide supported mercury nanoparticles for synthesis of amides via aldoximes/ketoximes rearrangement
Aggregates of perylene bisimide (PBI) derivative 3 serve as reactors and stabilizers for the preparation of mercury nanoparticles (HgNPs) which exhibit excellent catalytic efficiency in the conversion of aldoximes/ketoximes into primary/secondary amides via Beckmann rearrangement. This journal is
Kaur, Sandeep,Kumar, Manoj,Bhalla, Vandana
supporting information
p. 4085 - 4088
(2015/03/18)

Hydration of nitriles to amides by a chitin-supported ruthenium catalyst
Chitin-supported ruthenium (Ru/chitin) promotes the hydration of nitriles to carboxamides under aqueous conditions. The nitrile hydration can be performed on a gram-scale and is compatible with the presence of various functional groups including olefins, aldehydes, carboxylic esters and nitro and benzyloxycarbonyl groups. The Ru/chitin catalyst is easily prepared from commercially available chitin, ruthenium(III) chloride and sodium borohydride. Analysis of Ru/chitin by high-resolution transmission electron microscopy indicates the presence of ruthenium nanoparticles on the chitin support.
Matsuoka, Aki,Isogawa, Takahiro,Morioka, Yuna,Knappett, Benjamin R.,Wheatley, Andrew E. H.,Saito, Susumu,Naka, Hiroshi
p. 12152 - 12160
(2015/02/19)

A simple synthesis of salicylamide and 2,5-diphenylpyrazine
The compound I (C7H7NO2, salicylamide) and the compound II (C16H12N2, 2,5-diphenylpyrazine) were both obtained as the by-product of the onepot synthesis of oxazolinyl zinc complexes from the reaction of 2-hydroxybenzonitrile and 3-(N-ethyl-N-phenyl)-propanenitrile with D-phenylalaninol, which was catalyzed by 235 and 83.1 mol% zinc dichloride. Their structures were determined by X-ray diffraction, IR ,and elemental analysis.
Mei, Luo,Bing, Yan
p. 3491 - 3496
(2015/06/08)

Oxidation with air by ascorbate-driven quinone redox cycling
Transition metal-free oxidation with air at room temperature has been achieved by simply using ascorbate (vitamin C) and catalytic amounts of menadione (vitamin K3). A combination of the mentioned vitamins transforms atmospheric oxygen into hydrogen peroxide, which is able to oxidize arylboronic acids and other chemical moieties. This journal is
Silveira-Dorta, Gastón,Monzón, Diego M.,Crisóstomo, Fernando P.,Martín, Tomás,Martín, Víctor S.,Carrillo, Romen
supporting information
p. 7027 - 7030
(2015/04/22)

Palladium catalyzed Csp2-H activation for direct aryl hydroxylation: The unprecedented role of 1,4-dioxane as a source of hydroxyl radicals
A novel strategy for direct aryl hydroxylation via Pd-catalysed Csp2-H activation through an unprecedented hydroxyl radical transfer from 1,4-dioxane, used as a solvent, is reported with bio relevant and sterically hindered heterocycles and various acyclic functionalities as versatile directing groups.
Seth, Kapileswar,Nautiyal, Manesh,Purohit, Priyank,Parikh, Naisargee,Chakraborti, Asit K.
supporting information
p. 191 - 194
(2015/01/09)

Chitosan supported ionic liquid: A recyclable wet and dry catalyst for the direct conversion of aldehydes into nitriles and amides under mild conditions
A green and highly efficient chitosan supported magnetic ionic liquid (CSMIL) was synthesized with chitosan (the most abundant biopolymer in nature and a cheap industrial waste product), methyl imidazole and anhydrous/hydrous FeCl3. The heterogeneous catalyst thus obtained was used for the direct conversion of aldehydes to the corresponding nitriles in the presence of NH2OH·HCl/dry-CSMIL/MeSO2Cl and amides with NH 2OH·HCl/wet-CSMIL/MeSO2Cl. A highlight of our approach is the easy separation of the catalyst from the reaction medium and thus the recyclability of the catalyst. This simple method can be applied to obtain a wide range of aromatic, heterocyclic, and aliphatic nitriles and amides.
Khalafi-Nezhad, Ali,Mohammadi, Somayeh
p. 13782 - 13787
(2014/04/17)

High-temperature synthesis of amides from alcohols or aldehydes by using flow chemistry
An efficient conversion of aliphatic and aromatic alcohols or aldehydes into the corresponding primary amides was successfully achieved by using flow chemistry. Excellent yields were obtained in very short reaction times, and thus this method offers an efficient alternative to traditional methods for amide formation.
Ambreen, Nida,Wirth, Thomas
p. 7590 - 7593
(2015/04/22)

Stannous chloride dihydrate-mediated efficient access to secondary and primary amides from oximes
Highly selective, efficient and expeditious Beckmann rearrangement of a wide range of ketoximes to secondary amides (20 examples) has been accomplished using stoichiometric amount of stannous chloride dihydrate in the presence of nucleophilic additive, tetra-n-butylammonium iodide (TBAI) (10 moI%) and 4 ? MS in dry acetonitrile at reflux temperature. Aldoximes delivered primary amides through intermediacy of nitriles upon heating with an equimolar amount of SnCl2·2H2O and DBU in dry toluene at reflux in good to acceptable yields (12 examples). Utilization of mild Lewis acid, inexpensive rack reagents and procedural simplicity including easy isolation of products are key advantageous features of the protocol.
Ganguly, Nemai C.,Nayek, Subhasis,Chandra, Sumanta
p. 1695 - 1702
(2014/01/17)

Silica chloride-catalyzed microwave-assisted efficient and selective one-pot synthesis of amides from aldehydes
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Datta, Bandita,Pasha
experimental part
p. 2129 - 2130
(2012/08/28)

Quinazolinone-directed C-H activation: A novel strategy for the acetoxylation-methoxylation of the arenes
2-Aryl-4-quinazolinones undergo smooth acetoxylation in the presence of 5 mol% Pd(OAc)and a stoichiometric amount of PhI(OAc)via C-H activation to produce the corresponding acetoxy-substituted 4(3H)-quinazolinone derivatives in good yields with high regioselectivity. Georg Thieme Verlag Stuttgart · New York.
Reddy, B.V. Subba,Narasimhulu,Umadevi,Yadav
experimental part
p. 1364 - 1370
(2012/07/27)

Chemistry by nanocatalysis: First example of a solid-supported RAPTA complex for organic reactions in aqueous medium
A ruthenium-arene-PTA (RAPTA) complex has been supported for the first time on an inorganic solid, that is, silica-coated ferrite nanoparticles. The resulting magnetic material proved to be a general, very efficient and easily reusable catalyst for three synthetically useful organic transformations; selective nitrile hydration, redox isomerization of allylic alcohols, and heteroannulation of (Z)-enynols. The use of low metal concentration, environmentally friendly water as a reaction medium, with no use at all of organic solvent during or after the reactions, and microwaves as an alternative energy source renders the synthetic processes reported herein "truly" green and sustainable. RAPTA's delight: A nano-RAPTA complex supported on silica-coated ferrite nanoparticles proved to be a general, very efficient and easily reusable catalyst for three synthetically useful organic transformations; selective nitrile hydration, redox isomerization of allylic alcohols, and heteroannulation of (Z)-enynols. The use of low metal concentrations, water as a reaction medium, and microwaves as an energy source renders these processes green and sustainable.
García-Garrido, Sergio E.,Francos, Javier,Cadierno, Victorio,Basset, Jean-Marie,Polshettiwar, Vivek
experimental part
p. 104 - 111
(2012/01/06)

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)

A heterogeneous catalytic method for the conversion of nitriles into amides using molecular sieves modified with copper(II)
A heterogenous catalytic method is developed for the hydration of nitriles into amides with acetaldoxime. Copper(II) supported on 4 molecular sieves is an efficient catalyst for this reaction.
Kiss, árpád,Hell, Zoltán
experimental part
p. 6021 - 6023
(2011/11/28)

Bis(allyl)ruthenium(rV) complexes containing water-soluble phosphane ligands: Synthesis, structure, and application as catalysts in the Selective hydration of organonitriles into amides
The novel mononuclear ruthenium(IV) complexes [RuCl2(η 3: η3-C10H16)(L)] [L = (meta-sulfonatophenyl)diphenylphosphane sodium salt (TPPMS) (2a), 1,3,5-triaza-7-phosphatricyclo[3.3.1.13,7]decane (PTA) (2b), 1-benzyl-3,5-diaza-1-azonia-7-phosphatricyclo[3.3.1.13,7]decane chloride (PTABn) (2c), 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA) (2d), and 2,4,10-trimethyl-1,2,4,5,7,10-hexaaza-3-phosphatricyclo[3.3.1. 13,7]decane (THPA) (2e)] have been synthesized by treatment of the dimeric precursor [{RuCl(μ-Cl)((η3: η3-C 10H16)}2] (C10H16 = 2,7-dimethylocta-2,6-diene-1,8-diyl) (1) with two equivalents of the corresponding water-soluble phosphane. Reaction of 1 with one equivalent of the cage-type diphosphane ligand 2,3,5,6,7,8-hexamethyl-2,3,5,6,7,8-hexaaza-1,4- diphosphabicyclo[2.2.2]octane (THDP) allowed also the high-yield preparation of the dinuclear derivative [[RuCl2(η3: η3-C10H16)}2(μ-THDP)] (2f). All these new complexes have been analytically and spectroscopically (IR and multinuclear NMR) characterized. In addition, the structure of 2b, 2c, 2d, and 2 f was unequivocally confirmed by X-ray diffraction methods. Complexes 2a-f are active catalysts for the selective hydration of nitriles to amides in pure aqueous medium under neutral conditions. The wide scope of this catalytic transformation has been evaluated by using the most active catalysts [RuCl 2(η3: η3-C10H 16)(THPA)] (2e) and [{RuCl2(η3: η3-C10H16)}2(μ-THDP)] (2f). Advantages of using MW versus conventional thermal heating are also discussed.
Cadierno, Victorio,Diez, Josefina,Francos, Javier,Gimeno, Jose
experimental part
p. 9808 - 9817
(2010/10/21)

Mild, efficient and rapid O-debenzylation of ortho-substituted phenols with trifluoroacetic acid
The mild and efficient deblocking of aryl benzyl ethers with TFA is reported. Cleavage was fastest with ortho-electron-withdrawing groups on the phenolic ring, which we have attributed to a proton chelation effect, furnishing the deprotected phenols in excellent yields. The corresponding para-methoxybenzyl, allyl and iso-propyl ethers were also cleanly removed under these conditions. In addition, the selective aryl benzyl ether debenzylation in the presence of benzyl ester, Cbz carbamate and Boc carbamate functionalities was also observed. Crown Copyright
Fletcher, Steven,Gunning, Patrick T.
p. 4817 - 4819
(2008/09/21)

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)

Highly efficient ruthenium-catalyzed oxime to amide rearrangement
A wide range of aldoximes has been converted into the corresponding amides using the ruthenium-based catalyst Ru(PPh3)3(CO)H 2/dppe/ TsOH. The amides are generated in high yield and selectivity, with catalyst loading as low as 0.04 mol %.
Owston, Nathan A.,Parker, Alexandra J.,Williams, Jonathan M. J.
p. 3599 - 3601
(2008/02/12)

CeCl3·7H2O-NaI/SiO2 promoted Beckmann rearrangement (under solvent-free and microwave irradiation)
CeCl3·7H2O-NaI/SiO2 system promoted Beckmann rearrangement of a variety of aldoximes and ketoximes was efficiently conducted under solvent-free and microwave irradiation conditions. This protocol afforded an alternative method for the preparation of amides by Beckmann rearrangement with advantages of short reaction time, high yield, no pollution, simple operation and easy work-up.
Li, Zheng,Lu, Zhong,Ding, Runbo,Yang, Jingya
p. 668 - 670
(2007/10/03)

Synthesis of amides from carboxylic acids and urea in the presence of pyridine under microwave irradiation
A very simple and efficient procedure for the synthesis of primary amides from carboxylic acids and urea in presence of pyridine under microwave irradiation is described. Various amides were prepared within 20-30 s and in excellent yields.
Pasha, M. Afzal,Jayashankara
p. 675 - 676
(2007/10/03)