- A PROCESS FOR THE PREPARATION OF 4-CYANOBENZOYL CHLORIDES
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The present invention relates to a process for the preparation of 4-cyanobenzoyl chlorides of formula I through reaction of compounds of formula II with a chlorinating agent.
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Page/Page column 11-12
(2021/10/22)
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- Room Temperature Hydrolysis of Benzamidines and Benzamidiniums in Weakly Basic Water
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Benzamidinium compounds have found widespread use in both medicinal and supramolecular chemistry. In this work, we show that benzamidiniums hydrolyze at room temperature in aqueous base to give the corresponding primary amide. This reaction has a half-life of 300 days for unsubstituted benzamidinium at pH 9, but is relatively rapid at higher pH's (e.g., t1/2 = 6 days at pH 11 and 15 h at pH 13). Quantum chemistry combined with first-principles kinetic modeling can reproduce these trends and explain them in terms of the dominant pathway being initiated by attack of HO- on benzamidine. Incorporation of the amidinium motif into a hydrogen bonded framework offers a substantial protective effect against hydrolysis.
- Yu, Li-Juan,Cullen, Duncan A.,Morshedi, Mahbod,Coote, Michelle L.,White, Nicholas G.
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supporting information
p. 13762 - 13767
(2021/10/12)
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- Method for preparing terephthalamide from terephthalic acid
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The invention discloses a method for preparing terephthalamide from terephthalic acid, which comprises the following steps: carrying out esterification reaction on terephthalic acid and alcohol, and discharging by-product water generated by the reaction out of the reaction system; introducing ammonia gas into the esterification liquid to be ammonolyzed, and carrying out ammonolysis reaction to obtain a reaction container (marked as a reaction container I) filled with ammonolysis liquid containing high-concentration ammonia gas; connecting the reaction container I with a reaction container (marked as a reaction container II) filled with a next batch of esterification liquid to be ammonolyzed, so as to recover excessive ammonia gas; and cooling the ammonolysis liquid containing the low-concentration ammonia gas in the reaction container I, conducting filtering, and washing and drying a filter cake to obtain terephthalamide. According to the invention, terephthalic acid is subjected to esterification and ammonolysis to produce terephthalamide, the main byproduct in the reaction process is water, and the green production concept is met.
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Paragraph 0046-0112
(2021/06/21)
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- Ru-based complexes as heterogeneous potential catalysts for the amidation of aldehydes and nitriles in neat water
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Five novel heterogeneous mononuclear complex-anchored Ru(III) have been efficiently sono-synthesized and characterized by utilizing several analytical techniques. The assembled complexes could be utilized as effective, robust and recyclable (up to eight consecutive runs) catalysts for one-pot transformation of a vast array of nitriles and aldehydes to primary amides in H2O under aerobic conditions. Moreover, some unreported di- and tetra-amide derivatives were obtained also under the optimal conditions. The results of ICP/OES analysis demonstrated that there is no detected leaching of the recycled catalyst, which suggests the real heterogeneity of the present protocol. The present Ru-complexes exhibited superiority compared to other reported catalysts for amide preparation in terms of low catalyst load, short reaction time, low operating temperature, no hazardous additives required, and high values of TON (990) and TOF (1980 h11).
- Arafa, Wael Abdelgayed Ahmed
-
supporting information
p. 1056 - 1064
(2020/11/09)
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- Half-Sandwich Iridium Complexes for the One-Pot Synthesis of Amides: Preparation, Structure, and Diverse Catalytic Activity
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Several types of air-stable N,O-coordinate half-sandwich iridium complexes containing Schiff base ligands with the general formula [Cp*IrClL] were synthesized in good yields. These stable iridium complexes displayed a good catalytic efficiency in amide synthesis. A variety of amides with different substituents were obtained in a one-pot procedure with excellent yields and high selectivities through the amidation of aldehydes with NH2OHHCl and nitrile hydration under the catalysis of complexes 1-4. The excellent and diverse catalytic activity, mild conditions, broad substance scope, and environmentally friendly solvent make this system potentially applicable in industrial production. Half-sandwich iridium complexes 1-4 were characterized by NMR, elemental analysis, and IR techniques. Molecular structures of complexes 2 and 3 were confirmed by single-crystal X-ray analysis.
- Fan, Xiao-Nan,Deng, Wei,Liu, Zhen-Jiang,Yao, Zi-Jian
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p. 16582 - 16590
(2020/11/13)
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- Preparation method of aromatic amide compound
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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 0056-0057
(2020/07/15)
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- Hydration of nitriles using a metal-ligand cooperative ruthenium pincer catalyst
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Nitrile hydration provides access to amides that are important structural elements in organic chemistry. Here we report catalytic nitrile hydration using ruthenium catalysts based on a pincer scaffold with a dearomatized pyridine backbone. These complexes catalyze the nucleophilic addition of H2O to a wide variety of aliphatic and (hetero)aromatic nitriles in tBuOH as solvent. Reactions occur under mild conditions (room temperature) in the absence of additives. A mechanism for nitrile hydration is proposed that is initiated by metal-ligand cooperative binding of the nitrile.
- Guo, Beibei,Otten, Edwin,De Vries, Johannes G.
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p. 10647 - 10652
(2019/12/02)
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- Transfer Hydration of Dinitriles to Dicarboxamides
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We present a robust method for double transfer hydration of dinitriles to afford diamides. The transfer hydration of 1, n -dinitriles (n = 1-6) proceeds smoothly in the presence of a palladium(II) catalyst with acetamide as a water donor, affording the corresponding diamides in moderate to high yields, without involving significant side reactions such as monohydration or cyclization. The equilibrium was shifted in the forward direction by removing coproduced acetonitrile under reduced pressure.
- Naka, Hiroshi,Naraoka, Asuka
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supporting information
p. 1977 - 1980
(2019/10/22)
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- Trash to treasure: Eco-friendly and practical synthesis of amides by nitriles hydrolysis in WepPA
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The hydration of nitriles to amides in a water extract of pomelo peel ash (WEPPA) was realized with moderate to excellent yields without using external transition metals, bases or organic solvents. This reaction features a broad substrate scope, wide functional group tolerance, prominent chemoselectivity, and good reusability. Notably, a magnification experiment in this bio-based solvent at 100 mmol further demonstrated its practicability.
- Sun, Yajun,Jin, Weiwei,Liu, Chenjiang
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supporting information
(2019/11/11)
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- Ionic liquid catalysed aerobic oxidative amidation and thioamidation of benzylic amines under neat conditions
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Tetrabutylammonium hydroxide (TBAOH) was discovered as a highly efficient and green catalyst for aerobic oxidation of the α-methylene carbon of primary amines as well as benzylic groups into the corresponding amides and ketones under neat conditions. We described herein, ionic liquid TBAOH catalysed aerobic oxidation of benzyl amines to benzamides and with elemental sulfur; the corresponding benzylbenzothioamides were obtained under metal-free, oxidant-free and base-free conditions. Applicability at the gram scale for the synthesis of the desired amides/ketones is also demonstrated with the present protocol.
- Joshi, Abhisek,Kumar, Rahul,Semwal, Rashmi,Rawat, Deepa,Adimurthy, Subbarayappa
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supporting information
p. 962 - 967
(2019/03/11)
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- Corresponding amine nitrile and method of manufacturing thereof
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The invention relates to a preparation method of nitrile. Compared with the prior art, the preparation method has the characteristics of obvious reduction of the usage amount of ammonia sources, low environmental pressure, low energy consumption, low production cost, high purity and yields of nitrile products, and the like, and can be used for obtaining nitrile with a more complex structure. The invention also relates to a method for preparing corresponding amine with nitrile.
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Paragraph 0122; 0123; 0127; 0129
(2018/05/24)
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- METHOD OF PREPARING p-PHENYLENEDIAMINE
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Provided is a method for producing paraphenylenediamine. More specifically, the present invention relates to a method for producing paraphenylenediamine, comprising the following steps: carrying out a chlorination reaction using a by-product from a production process of dimethyl terephthalate; preparing terephthalamide through an amidation reaction using the chlorinated product; and carrying out Hofmann rearrangement from the terephthalamide.COPYRIGHT KIPO 2018
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Paragraph 0088-0089; 0101
(2018/07/03)
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- Method for preparing p-benzene diacetamide through amidation of p-diacetylbenzene
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The present invention relates to a method for preparing p-benzene diacetamide through amidation of p-diacetylbenzene. According to the present invention, p-diacetylbenzene is used as a raw material, an aminating agent, a vulcanizing agent and a solvent are added, and a reaction is performed at a reaction temperature of 80-180 DEG C under a reaction pressure of 0.5-2.0 MPa to obtain the product p-benzene diacetamide; and the method has advantages of simple operation, high p-diacetylbenzene conversion rate, high p-benzene diacetamide yield, non-toxic raw material, high reaction safety, high economic benefit, broad industrial application prospect and the like, and can avoid the use of nitrile substances.
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Paragraph 0024-0047
(2018/05/01)
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- Modulation of Nitrile Hydratase Regioselectivity towards Dinitriles by Tailoring the Substrate Binding Pocket Residues
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The regioselective hydration of dinitriles is one of the most attractive approaches to prepare ω-cyanocarboxamides or diamides and such regioselectivity is often beyond the capability of chemical catalysts. The use of nitrile hydratase to biotransform dinitriles selectively would be highly desirable. Molecular docking of two aliphatic dinitriles and two aromatic dinitriles into the active site of a nitrile hydratase (NHase) from Rhodococcus rhodochrous J1 allowed the identification of proximal NHase substrate binding pocket residues. Four residues (βLeu48, βPhe51, βTyr68, and βTrp72) were selected for single- and double-point mutations to modulate the NHase regioselectivity towards dinitriles. Several NHase mutants with an altered regioselectivity were obtained, and the best one was Y68T/W72Y. Docking experiments further indicated that the poor binding affinity of aliphatic and aromatic ω-cyanocarboxamides to the NHase variants resulted in distinct regioselectivity between wild-type and mutated NHases.
- Cheng, Zhongyi,Cui, Wenjing,Xia, Yuanyuan,Peplowski, Lukasz,Kobayashi, Michihiko,Zhou, Zhemin
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p. 449 - 458
(2017/12/15)
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- Corresponding amine nitrile and method of manufacturing thereof
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The present invention relates to a nitrile manufacturing method, which has characteristics of significantly-reduced ammonia source consumption, low environmental pressure, low energy consumption, low production cost, high nitrile purity, high nitrile yield and the like compared with the method in the prior art, wherein nitrile having a complicated structure can be obtained through the method. The present invention further relates to a method for producing a corresponding amine from the nitrile.
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-
Paragraph 0125; 0126; 0131; 0132
(2018/05/24)
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- Efficient Bimetallic Catalysis of Nitrile Hydration to Amides with a Simple Pd(OAc)2/Lewis Acid Catalyst at Ambient Temperature
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Transition-metal-catalyzed nitrile hydration is an atom-economic method for the synthesis of various amides. This work demonstrates for the first time that the addition of non-redox metal ions like Sc3+ dramatically accelerate the hydration of various nitriles to amides at ambient temperature with the simple Pd(OAc)2 salt as catalyst, whereas the reactions with Pd(OAc)2 alone were very sluggish. The formation of a heterobimetallic PdII/ScIII species has been proposed as the key species for the hydration that demonstrates a bimetallic synergistic effect in this process.
- Zhang, Sicheng,Xu, Haosheng,Lou, Chenlin,Senan, Ahmed M.,Chen, Zhuqi,Yin, Guochuan
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p. 1870 - 1875
(2017/04/21)
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- Corresponding amine nitrile and method of manufacturing thereof (by machine translation)
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The invention relates to a method of manufacturing one kind of nitrile, compared with the prior art, has significantly reduced the amount of ammonia, the environmental pressure of the small, low energy consumption, low production cost, nitrile product purity and yield and the like, and can obtain more complex structure of the nitriles. The invention also relates to the corresponding amine by the nitrile manufacture method. (by machine translation)
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-
Paragraph 0123-0124; 0129-0130
(2017/10/22)
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- Chemoselective hydration of nitriles to amides using hydrated ionic liquid (IL) tetrabutylammonium hydroxide (TBAH) as a green catalyst
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A transition metal-free process, catalyzed by tetrabutylammonium hydroxide (TBAH), has been developed for the convenient and selective hydration of nitriles to the corresponding amides. The present process converts aromatic, aliphatic, and heteroaromatic nitriles with a wide variety of functional groups into amides. The regioselective hydration of one nitrile moiety in the presence of another nitrile group gives the present protocol high impact.
- Veisi, Hojat,Maleki, Behrooz,Hamelian, Mona,Ashrafi, Samaneh Sedigh
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p. 6365 - 6371
(2015/02/19)
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- Selective NaOH-catalysed hydration of aromatic nitriles to amides
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The selective synthesis of aromatic and heteroaromatic amides through base-catalysed hydration of nitriles was achieved using inexpensive and commercially available NaOH as the only catalyst. A wide range of nitriles was selectively converted to their corresponding amides. Kinetic studies show that the double hydration of nitriles towards undesirable carboxylic acids is negligible under our reaction conditions.
- Schmid, Thibault E.,Gómez-Herrera, Alberto,Songis, Olivier,Sneddon, Deborah,Révolte, Antoine,Nahra, Fady,Cazin, Catherine S. J.
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p. 2865 - 2868
(2015/05/27)
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- Transition-metal-free hydration of nitriles using potassium tert -butoxide under anhydrous conditions
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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)
-
- Efficient and selective hydration of nitriles to amides in aqueous systems with Ru(II)-phosphaurotropine catalysts
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A simple and efficient synthesis of amides by selective hydration of aromatic and aliphatic nitriles is described. The catalysts are prepared in situ from easily available Ru-precursors and ligands using water as the solvent. The most active catalyst, is obtained from [RuCl2(dmso)4] and benzylated 1,3,5-triaza-7-phosphaadamantane. Of the 16 substrates examined, 92-99% conversions of 14 nitriles were achieved in one hour at reflux temperature.
- Bolyog-Nagy, Evelin,Udvardy, Antal,Joó, Ferenc,Kathó, ágnes
-
supporting information
p. 3615 - 3617
(2014/06/23)
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- N3 as an efficient reagent for the Schmidt reactions of ketones, arylaldehydes and aromatic carboxylic acids
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Schmidt reaction of arylaldehydes, ketones and aromatic carboxylic acids using task-specific ionic liquid, [bmim]N3 in the presence of AcOH/H2SO4 proceeds at 50-60 °C within 2-4 h to give the corresponding products. Benzaldehydes containing electron releasing groups afforded to the related benzamide derivatives. Benzonitrile derivatives were formed from the reaction of benzaldehydes containing electron withdrawing groups under these conditions. High yields of the related amides and anilines were obtained from the reaction of a variety of ketones and aromatic carboxylic acids, respectively, utilizing this procedure.
- Valizadeh, Hassan,Gholipour, Hamid,Ahmadi, Mina,Vaghefi, Sevil
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p. 1287 - 1294
(2014/11/07)
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- Ruthenium on chitosan: A recyclable heterogeneous catalyst for aqueous hydration of nitriles to amides
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Ruthenium has been immobilized over chitosan by simply stirring an aqueous suspension of chitosan in water with ruthenium chloride, and has been utilized for the oxidation of nitriles to amides; the hydration of nitriles occurs in high yield and excellent selectivity, which proceeds exclusively in aqueous medium under neutral conditions. the Partner Organisations 2014.
- Baig, R. B. Nasir,Nadagouda, Mallikarjuna N.,Varma, Rajender S.
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p. 2122 - 2127
(2014/04/17)
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- Ruthenium-catalyzed one-pot synthesis of primary amides from aldehydes in water
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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
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p. 5889 - 5894
(2013/05/09)
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- Transition metal-free 1,3-dimethylimidazolium hydrogen carbonate catalyzed hydration of organonitriles to amides
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An efficient hydration of organonitriles to the corresponding amides was accomplished using 1,3-dimethylimidazolium hydrogen carbonate as an organocatalyst. The developed catalytic method was also applicable for the synthesis of metal phthalocyanines.
- Verma, Praveen Kumar,Sharma, Upendra,Bala, Manju,Kumar, Neeraj,Singh, Bikram
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p. 895 - 899
(2013/04/23)
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- Solid-supported ruthenium(0): An efficient heterogeneous catalyst for hydration of nitriles to amides under microwave irradiation
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Solid-supported ruthenium(0) was synthesized by the reduction deposition method and used as a heterogeneous catalyst for the hydration of nitriles to amides under microwave irradiation. A wide range of aromatic, α,β-unsaturated and aliphatic nitriles were efficiently converted to their corresponding primary amides under milder conditions. The catalyst was found to be very stable under moisture and microwave irradiation, easily separable from the reaction mixture, to cause negligible metal contamination of the product and was recyclable up to ten times without significant loss of catalytic activity.
- Kumar, Sandeep,Das, Pralay
-
supporting information
p. 2987 - 2990
(2013/10/01)
-
- Homogeneous and stereoselective copper(II)-catalyzed monohydration of methylenemalononitriles to 2-cyanoacrylamides
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A facile and efficient route for the homogeneous and highly stereoselective monohydration of substituted methylenemalononitriles to (E)-2-cyanoacrylamides catalyzed by copper(II) acetate monohydrate in acetic acid containing 2% water is described, and a mechanism is proposed. The protocol has proved to be suitable for the monohydration of dicyanobenzenes and 2-substituted malononitriles.
- Xin, Xiaoqing,Xiang, Dexuan,Yang, Jiming,Zhang, Qian,Zhou, Fenguo,Dong, Dewen
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p. 11956 - 11961
(2014/01/06)
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- A facile one-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica: Aqueous hydration of nitriles to amides
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One-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica is described which involves the in situ generation of magnetic silica (Fe 3O4@SiO2) and ruthenium hydroxide immobilization; the hydration of nitriles occurs in high yield and excellent selectivity using this catalyst which proceeds exclusively in aqueous medium under neutral conditions. The Royal Society of Chemistry 2012.
- Baig, R. B. Nasir,Varma, Rajender S.
-
supporting information; experimental part
p. 6220 - 6222
(2012/07/03)
-
- Efficient and practical transition metal-free catalytic hydration of organonitriles to amides
-
K2CO3 can act as an efficient catalyst for the hydration of organonitriles in aqueous conditions assisted by microwave irradiation, which represents an inexpensive, practical, atom-economical, and straightforward transition metal-free protocol to various amides.
- Tu, Tao,Wang, Zhixun,Liu, Zelong,Feng, Xike,Wang, Qingyi
-
supporting information; experimental part
p. 921 - 924
(2012/06/01)
-
- Metal-free one-pot oxidative conversion of benzylic alcohols and benzylic halides into aromatic amides with molecular iodine in aq ammonia, and hydrogen peroxide
-
Various primary alcohols, particularly benzylic alcohols, could be converted into the corresponding aromatic amides in good yields in a one-pot manner by treatment with molecular iodine in aq. NH3, followed by reaction with ~30% aq H2O2. Similarly, various benzylic halides could be also converted into the corresponding aromatic amides in good yields in a one-pot manner by treatment with molecular iodine in aq NH3, followed by reaction with ~30% aq H2O 2. The present reactions involve the metal-free one-pot oxidative conversion of benzylic alcohols and benzylic halides into the corresponding aromatic amides, respectively.
- Ohmura, Ryosuke,Takahata, Misato,Togo, Hideo
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experimental part
p. 4378 - 4381
(2010/09/12)
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- Gold Activation of Nitriles: Catalytic Hydration to Amides
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A gold-based catalytic system that efficiently mediates the hydration of a broad spectrum of nitriles, including aromatic, heteroaromatic and aliphatic examples and efficiently catalyze the hydration of a range of organonitriles has been reported. Nitriles are considered inert in the context gold catalysis and have only been used as reaction solvent or as throw-away ligands in well-defined cationic gold catalysis. The obtained product was purified by flash chromatography using a gradient of pentane/ethyl acetate and compound 1 was isolated as a colorless solid. Aromatic substrates bearing two nitrile groups as in rn-benzenedinitrile and p-benzenedinitrile underwent double nitrile hydration and afforded excellent yields in the corresponding diamides. There is high relevance for the use of cationic gold complexes bearing such ligands and should have important implications in catalysis.
- Ramon, Ruben S.,Marion, Nicolas,Nolan, Steven P.
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supporting information; experimental part
p. 8695 - 8697
(2010/03/24)
-
- Facile and highly selective conversion of nitriles to amides via indirect acid-catalyzed hydration using TFA or AcOH-H2SO4
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(Chemical Equation Presented) Both aliphatic and aromatic nitriles are conveniently and selectively converted in a single step, via an indirect acid-catalyzed hydration, into the corresponding amides in 1-8 h using a TFA-H2SO4 mixture as a reagent system. Although the same reagent did not work for the sterically hindered nitriles such as mesitonitrile, the transformation could be accomplished by changing TFA to AcOH at higher temperatures (>90°C).
- Moorthy, Jarugu Narasimha,Singhal, Nidhi
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p. 1926 - 1929
(2007/10/03)
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- Method for the synthesis of amides and related products from esters or ester-like compounds
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A versatile, eco-friendly, and efficient method for the convenient conversion of esters and ester-like compounds into amides, peptides, carbamates, ureas, oxamides, oxamates, hydrazides, oxazolidinones, pyrazolones, oxazolidinediones, barbituric acids, and other molecules containing one or more OCN moieties in the presence of a diol or polyol is disclosed.
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Page/Page column 8
(2008/06/13)
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- Rh-catalyzed one-pot and practical transformation of aldoximes to amides
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Wilkinson's complex has been found to catalyze the one-pot transformation of aldoximes to the corresponding amides with high selectivity and efficiency under essentially neutral conditions.
- Park, Soyoung,Choi, Yoon-aa,Han, Hoon,Yang, Soon Ha,Chang, Sukbok
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p. 1936 - 1937
(2007/10/03)
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- Direct conversion of aldehydes to amides, tetrazoles, and triazines in aqueous media by one-pot tandem reactions
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A variety of aldehydes reacted with iodine in ammonia water at room temperature to give the nitrile intermediates, which were trapped by addition of hydrogen peroxide, sodium azide, or dicyandiamide to produce their corresponding amides, tetrazoles, and 1,3,5-triazines in modest to high yields. The one-pot tandem reactions were conducted in water media, and the products were obtained simply by extraction or filtration.
- Shie, Jiun-Jie,Fang, Jim-Min
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p. 1158 - 1160
(2007/10/03)
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- Preparation of indoIizine-3-carboxamides and indolizine-3-carbonitriles by 1, 3-dipolar cycloaddition of 7V-(cyanomethyl)pyridiniuni ylides to alkenes in the presence of tetrakispyridinecobalt(n) dichromate or manganese(iv) oxide
-
Two selective procedures for the synthesis of potentially important agrochemicals, indoIizine-3-carboxamides (6) and indolizine-3-carbonitriles (7), were developed. In the presence of tetrakispyridinecobalt(n) dichromate (TPCD), compounds 6 are readily synthesized by a one-pot reaction sequence which consists of a 1, 3-dipolar cycloaddition of pyridinium N-ylides to alkenes, followed by an aromatization and a regiospecific hydration reaction. When MnO2 instead of TPCD was used in the 1, 3-dipolar addition reaction, the nitrite group of the indolizine product was not hydrated and compounds 7 were obtained as final products. Both procedures utilize convenient conditions and inexpensive reagents, and give products in good to high yields.
- Wang, Bingxiang,Zhang, Xucchun,Li, Jun,Jiang, Xin,Hu, Yuefei,Hua, Hongwen
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p. 1571 - 1579
(2007/10/03)
-
- Process for converting pet scrap to diamine monomers
-
Scrap poly(ethyleneterephthalate) is converted to useful amine and diamine monomers such as para-xylylenediamine, 1,4-bis(aminomethyl)cyclohexane and 4-aminomethyl benzoic acid for the production of various polyamides. The conversion of poly(ethyleneterephthalate) to diamine monomers is achieved by a three step process involving (a) ammonolysis of the poly(ethyleneterephthalate) to produce terephthalamide and ethylene glycol; (b) pyrolytic dehydration of the terephthalamide to produce terephthalonitrile; and (c) hydrogenation of the terephthalonitrile to produce the para-xylylene diamine and/or 1,4-bis(aminomethyl)cyclohexane. The conversion of poly(ethyleneterephthalate) to 4-aminomethyl benzoic acid involves the steps of (a) ammonolysis of the poly(ethyleneterephthalate) to produce terephthalamide; (b) partial pyrolytic dehydration of said terephthalamide to produce 4-cyanobenzoic acid; and (c) hydrogenation of said 4-cyanobenzoic acid to produce 4-aminomethylbenzoic acid. The process of the present invention permits the conversion of low value PET scrap such as beverage bottles, fibers and film to relatively high value and relatively pure diamine monomers and ethylene glycol.
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-
- FURTHER FUNCTIONAL GROUP OXIDATIONS USING SODIUM PERBORATE
-
Sodium perborate in acetic acid is an effective reagent for the oxidation of aromatic aldehydes to carboxylic acids, iodoarenes to (diacetoxyiodo)arenes, azines to N-oxides, and various types of sulfur heterocycles to S,S-dioxides.Nitriles are unaffected by the reagent in acetic acid, but undergo smooth hydration to amides when aqueous methanol is employed as solvent.
- McKillop, Alexander,Kemp, Duncan
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p. 3299 - 3306
(2007/10/02)
-