- Effect of crown ether macrocycle on the methylation of the thioamide derivatives of benzo-15-crown-5 and veratrole
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It was shown that benzo-15-crown-5 ether has an effect on the methylation of the thioamide derivatives. leading to the formation of the nitriles of carboxylic acids.
- Sayfullina,Tashmukhamedova,Shakhidoyatov
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Read Online
- Inductively heated oxides inside microreactors - Facile oxidations under flow conditions
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Inductively heated iron oxides mixed with solid oxidants like CrO 2 and NiO2 efficiently oxidize organic substrates under flow conditions in fixed-bed reactors.
- Wegner, Jens,Ceylan, Sascha,Friese, Carsten,Kirschning, Andreas
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Read Online
- SO2F2-mediated oxidation of primary and tertiary amines with 30% aqueous H2O2 solution
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A highly efficient and selective oxidation of primary and tertiary amines employing SO2F2/H2O2/base system was described. Anilines were converted to the corresponding azoxybenzenes, while primary benzylamines were transformed into nitriles and secondary benzylamines were rearranged to amides. For tertiary amine substrates quinolines, isoquinolines and pyridines, their oxidation products were the corresponding N-oxides. The reaction conditions are very mild and just involve SO2F2, amines, 30% aqueous H2O2 solution, and inorganic base at room temperature. One unique advantage is that this oxidation system is just composed of inexpensive inorganic compounds without the use of any metal and organic compounds.
- Liao, Xudong,Zhou, Yi,Ai, Chengmei,Ye, Cuijiao,Chen, Guanghui,Yan, Zhaohua,Lin, Sen
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supporting information
(2021/11/01)
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- Dehydration of aldoximes to nitriles using trichloroacetonitrile without catalyst
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Trichloroacetonitrile has been found to be an efficient dehydrating agent for a range of aldoximes including aromatic and heterocyclic aldoxime yielding the corresponding nitriles in moderate to good yields. The dehydration reactions can take place in non-acetonitrile media without the aid of a metal catalyst. In addition, it has been confirmed that trichloroacetonitrile was converted into trichloroacetamide in the reaction.
- Ma, Xiaoyun,Liu, Dan,Chen, Zhengjian
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p. 3261 - 3266
(2021/06/30)
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- Cu2O-Catalyzed Conversion of Benzyl Alcohols Into Aromatic Nitriles via the Complete Cleavage of the C≡N Triple Bond in the Cyanide Anion
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Nitrogen transfer from cyanide anion to an aldehyde is emerging as a promising method for the synthesis of aromatic nitriles. However, this method still suffers from a disadvantage that a use of stoichiometric Cu(II) or Cu(I) salts is required to enable the reaction. As we report herein, we overcame this drawback and developed a catalytic method for nitrogen transfer from cyanide anion to an alcohol via the complete cleavage of the C≡N triple bond using phen/Cu2O as the catalyst. The present condition allowed a series of benzyl alcohols to be smoothly converted into aromatic nitriles in moderate to high yields. In addition, the present method could be extended to the conversion of cinnamic alcohol to 3-phenylacrylonitrile.
- Liu, Wenbo,Tang, Peichen,Zheng, Yi,Ren, Yun-Lai,Tian, Xinzhe,An, Wankai,Zheng, Xianfu,Guo, Yinggang,Shen, Zhenpeng
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p. 3509 - 3513
(2021/10/04)
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- Highly Efficient Oxidative Cyanation of Aldehydes to Nitriles over Se,S,N-tri-Doped Hierarchically Porous Carbon Nanosheets
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Oxidative cyanation of aldehydes provides a promising strategy for the cyanide-free synthesis of organic nitriles. Design of robust and cost-effective catalysts is the key for this route. Herein, we designed a series of Se,S,N-tri-doped carbon nanosheets with a hierarchical porous structure (denoted as Se,S,N-CNs-x, x represents the pyrolysis temperature). It was found that the obtained Se,S,N-CNs-1000 was very selective and efficient for oxidative cyanation of various aldehydes including those containing other oxidizable groups into the corresponding nitriles using ammonia as the nitrogen resource below 100 °C. Detailed investigations revealed that the excellent performance of Se,S,N-CNs-1000 originated mainly from the graphitic-N species with lower electron density and synergistic effect between the Se, S, N, and C in the catalyst. Besides, the hierarchically porous structure could also promote the reaction. Notably, the unique feature of this metal-free catalyst is that it tolerated other oxidizable groups, and showed no activity on further reaction of the products, thereby resulting in high selectivity. As far as we know, this is the first work for the synthesis of nitriles via oxidative cyanation of aldehydes over heterogeneous metal-free catalysts.
- Hua, Manli,Song, Jinliang,Huang, Xin,Liu, Huizhen,Fan, Honglei,Wang, Weitao,He, Zhenhong,Liu, Zhaotie,Han, Buxing
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supporting information
p. 21479 - 21485
(2021/08/23)
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- Copper-Catalyzed One-Pot Synthesis of Quinazolinones from 2-Nitrobenzaldehydes with Aldehydes: Application toward the Synthesis of Natural Products
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A novel, efficient, and atom-economical approach for the construction of quinazolinones from 2-nitrobenzaldehydes has been unveiled via copper-catalyzed nitrile formation, hydrolysis, and reduction in one pot for the first time. In this reaction, urea is used as a source of nitrogen for nitrile formation, hydrazine hydrate is used for both the reduction of the nitro group and the hydrolysis of nitrile, and atmospheric oxygen is used as the sole oxidant. The method portrays a wide substrate scope with good functional group tolerances. Moreover, this method was applied for the synthesis of schizocommunin, tryptanthrin, phaitanthrin-A, phaitanthrin-B, and 8H-quinazolino[4,3-b]quinazolin-8-one.
- Pal, Shantanu,Sahoo, Subrata
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p. 18067 - 18080
(2021/12/06)
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- Efficient nitriding reagent and application thereof
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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 0227-0229
(2021/03/31)
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- Novel chalcone/aryl carboximidamide hybrids as potent anti-inflammatory via inhibition of prostaglandin E2 and inducible NO synthase activities: design, synthesis, molecular docking studies and ADMET prediction
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Two series of chalcone/aryl carboximidamide hybrids 4a–f and 6a–f were synthesised and evaluated for their inhibitory activity against iNOS and PGE2. The most potent derivatives were further checked for their in?vivo anti-inflammatory activity utilising carrageenan-induced rat paw oedema model. Compounds 4c, 4d, 6c and 6d were proved to be the most effective inhibitors of PGE2, LPS-induced NO production, iNOS activity. Moreover, 4c, 4d, 6c and 6d showed significant oedema inhibition ranging from 62.21% to 78.51%, compared to indomethacin (56.27 ± 2.14%) and celecoxib (12.32%). Additionally, 4c, 6a and 6e displayed good COX2 inhibitory activity while 4c, 6a and 6c exhibited the highest 5LOX inhibitory activity. Compounds 4c, 4d, 6c and 6d fit nicely into the pocket of iNOS protein (PDB ID: 1r35) via the important amino acid residues. Prediction of physicochemical parameters exhibited that 4c, 4d, 6c and 6d had acceptable physicochemical parameters and drug-likeness. The results indicated that chalcone/aryl carboximidamides 4c, 4d, 6c and 6d, in particular 4d and 6d, could be used as promising lead candidates as potent anti-inflammatory agents.
- Ibrahim, Tarek S.,Moustafa, Amr H.,Almalki, Ahmad J.,Allam, Rasha M.,Althagafi, Abdulhamid,Md, Shadab,Mohamed, Mamdouh F. A.
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p. 1067 - 1078
(2021/05/28)
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- One pot synthesis of aryl nitriles from aromatic aldehydes in a water environment
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In this study, we found a green method to obtain aryl nitriles from aromatic aldehyde in water. This simple process was modified from a conventional method. Compared with those approaches, we used water as the solvent instead of harmful chemical reagents. In this one-pot conversion, we got twenty-five aryl nitriles conveniently with pollution to the environment being minimized. Furthermore, we confirmed the reaction mechanism by capturing the intermediates, aldoximes.
- Chen, Qingqing,Han, Hongwei,Lin, Hongyan,Ma, Xiaopeng,Qi, Jinliang,Wang, Xiaoming,Yang, Yonghua,Zhou, Ziling
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p. 24232 - 24237
(2021/07/29)
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- Nickel-Catalyzed Cyanation of Aryl Thioethers
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A nickel-catalyzed cyanation of aryl thioethers using Zn(CN)2 as a cyanide source has been developed to access functionalized aryl nitriles. The ligand dcype (1,2-bis(dicyclohexylphosphino)ethane) in combination with the base KOAc (potassium acetate) is essential for achieving this transformation efficiently. This reaction involves both a C-S bond activation and a C-C bond formation. The scalability, low catalyst and reagents loadings, and high functional group tolerance have enabled both late-stage derivatization and polymer recycling, demonstrating the reaction's utility across organic chemistry.
- Delcaillau, Tristan,Woenckhaus-Alvarez, Adrian,Morandi, Bill
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supporting information
p. 7018 - 7022
(2021/09/13)
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- Preparation method of apremilast impurity
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The invention discloses a preparation method of an apremilast impurity, and belongs to the technical field of apremilast impurity synthesis, the method comprises the following steps: taking 3-halogenated-2-methyl benzoic acid as a starting raw material to prepare an intermediate M1 through oxidation reaction, and performing dehydration condensation on the intermediate M1 to prepare an intermediate M2; taking 3, 4-dihydroxybenzonitrile as an initial raw material, carrying out an oxygen methylation reaction to prepare an intermediate M3, sequentially carrying out nucleophilic addition, a reduction reaction and alkaline hydrolysis on the intermediate M3 to prepare an intermediate M4, carrying out an amide exchange reaction on the intermediate M2 and the intermediate M4 to prepare an intermediate M5, and carrying out a coupling reaction and acid treatment on the intermediate M5 to obtain a target product. The method has the characteristics of reasonable synthetic route, easily available raw materials, simple and easy operation, high yield and high purity, and the prepared apremilast impurity can be used as a reference substance for qualitative and quantitative research of impurities in apremilast quality research, controls the content of related substances in bulk drugs, and ensures the quality of the bulk drugs.
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Paragraph 0031; 0039-0041
(2021/06/02)
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- Nickel-Catalyzed Reversible Functional Group Metathesis between Aryl Nitriles and Aryl Thioethers
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We describe a new functional group metathesis between aryl nitriles and aryl thioethers. The catalytic system nickel/dcype is essential to achieve this fully reversible transformation in good to excellent yields. Furthermore, the cyanide- and thiol-free reaction shows high functional group tolerance and great efficiency for the late-stage derivatization of commercial molecules. Finally, synthetic applications demonstrate its versatility and utility in multistep synthesis.
- Delcaillau, Tristan,Boehm, Philip,Morandi, Bill
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supporting information
p. 3723 - 3728
(2021/04/07)
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- CuO-catalyzed conversion of arylacetic acids into aromatic nitriles with K4Fe(CN)6 as the nitrogen source
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Readily available CuO was demonstrated to be effective as the catalyst for the conversion of arylacetic acids to aromatic nitriles with non-toxic and inexpensive K4Fe(CN)6 as the nitrogen source via the complete cleavage of the C[tbnd]N triple bond. The present method allowed a series of arylacetic acids including phenylacetic acids, naphthaleneacetic acids, 2-thiopheneacetic acid and 2-furanacetic acid to be converted into the targeted products in low to high yields.
- Ren, Yun-Lai,Shen, Zhenpeng,Tian, Xinzhe,Xing, Ai-Ping,Zhao, Zhe
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- Chlorotropylium Promoted Conversions of Oximes to Amides and Nitriles
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Chlorotropylium chloride as a catalyst for the transformations of oximes, ketones, and aldehydes to their corresponding amides and nitriles in excellent yields (up to 99 %) and in short reaction times (mostly 10–15 min). Oximes were electrophilically attacked on the hydroxyl oxygen by chlorotropylium. The produced tropylium oxime ethers were the key intermediates, of which the ketoxime ether led to amide through Beckmann rearrangement, and the aldoxime ether led to nitrile by nitrogen base DBU assisted formal dehydration. This chlorotropylium activation protocol offered general, mild, and efficient avenues bifurcately from oximes to both amides and nitriles by one organocatalyst.
- Xu, Jiaxi,Gao, Yu,Li, Zhenjiang,Liu, Jingjing,Guo, Tianfo,Zhang, Lei,Wang, Haixin,Zhang, Zhihao,Guo, Kai
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p. 311 - 315
(2020/01/25)
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- SO2F2-Mediated one-pot cascade process for transformation of aldehydes (RCHO) to cyanamides (RNHCN)
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A simple, mild and practical cascade process for the direct conversion of aldehydes to cyanamides was developed featuring a wide substrate scope and great functional group tolerability. This method allows for transformations of readily available, inexpensive, and abundant aldehydes to highly valuable cyanamides in a pot, atom, and step-economical manner with a green nitrogen source. This protocol will serve as a robust tool for the installation of the cyanamide moiety in various complicated molecules.
- Ding, Chengrong,Ge, Shuting,Wei, Junjie,Zhang, Guofu,Zhao, Yiyong
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p. 17288 - 17292
(2020/05/18)
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- Atomically Dispersed Ru on Manganese Oxide Catalyst Boosts Oxidative Cyanation
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There is a strong incentive for environmentally benign and sustainable production of organic nitriles to avoid the use of toxic cyanides. Here we report that manganese oxide nanorod-supported single-site Ru catalysts are active, selective, and stable for oxidative cyanation of various alcohols to give the corresponding nitriles with molecular oxygen and ammonia as the reactants. The very low amount of Ru (0.1 wt %) with atomic dispersion boosts the catalytic performance of manganese oxides. Experimental and theoretical results show how the Ru sites enhance the ammonia resistance of the catalyst, bolstering its performance in alcohol dehydrogenation and oxygen activation, the key steps in the oxidative cyanation. This investigation demonstrates the high efficiency of a single-site Ru catalyst for nitrile production.
- Gates, Bruce C.,Guan, Erjia,Meng, Xiangju,Wang, Chengtao,Wang, Hai,Wang, Liang,Wang, Sai,Xiao, Feng-Shou,Xu, Dongyang,Xu, Hua,Yang, Bo,Zhang, Jian
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p. 6299 - 6308
(2020/07/21)
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- Photocatalytic Conversion of Benzyl Alcohols/Methyl Arenes to Aryl Nitriles via H-Abstraction by Azide Radical
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This report presents the visible-light-assisted synthesis of aryl nitriles from easily accessible alcohols or methyl arenes in the presence of O2. Organic photoredox catalyst, 4CzIPN (1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene), induces single electron transfer (SET) from azide N3? and generates azide radical N3?.The photogenerated N3? abstracts H atom from α-C?H bond of benzylic system, which provides aldehyde and hydrazoic acid (HN3) in situ. This reaction subsequently forms azido alcohol intermediate that transforms into nitrile with the assistance of triflic acid (Br?nsted acid). A range of alcohols and methyl arenes successfully underwent cyanation at room temperature with good to excellent yields and showed good functional group tolerance.
- Shee, Maniklal,Shah, Sk. Sheriff,Singh, N. D. Pradeep
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supporting information
p. 14070 - 14074
(2020/10/12)
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- Method for converting aromatic aldehyde into aromatic nitrile by using sulfur powder promoted inorganic ammonium as nitrogen source (by machine translation)
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The invention discloses a method for converting aromatic aldehyde into aromatic nitrile. The method is conversion of high yield of aromatic aldehyde one-pot reaction of sulfur powder promoted inorganic ammonium as a nitrogen source into aromatic nitrile. The method has the advantages of no need of metal participation, no need of strong oxide, compatibility of reaction to air, easiness in amplification to a gram scale and the like, and overcomes the problems of harsh reaction conditions, complex operation, low functional group compatibility and the like in the prior art. (by machine translation)
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Paragraph 0044; 0045
(2020/09/12)
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- Nitromethane as a nitrogen donor in Schmidt-type formation of amides and nitriles
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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
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supporting information
p. 281 - 285
(2020/01/28)
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- Nickel-Catalyzed Transformation of Alkene-Tethered Oxime Ethers to Nitriles by a Traceless Directing Group Strategy
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Nickel-catalyzed transformation of alkene-tethered oxime ethers to nitriles using a traceless directing group strategy has been developed. A series of alkene-tethered oxime ethers derived from benzaldehyde and cinnamyl aldehyde derivatives were converted into the corresponding benzonitriles and cinnamonitriles in 46-98% yields using the nickel catalyst system. Control experiments showed that the alkene group tethered to an oxygen atom on the oximes via one methylene unit plays a key role as a traceless directing group during the catalysis.
- Takahashi, Yoshiyuki,Tsuji, Hiroaki,Kawatsura, Motoi
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p. 2654 - 2665
(2020/02/04)
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- Preparation method of 3, 4-dimethoxybenzonitrile
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The invention provides a preparation method of 3, 4-dimethoxybenzonitrile, which comprises the following steps of adding 3, 4-dimethoxyphenyl acetone and nitrogen oxide into an organic solvent, and carrying out catalytic reaction by an iron catalyst under the protection of inert gas to obtain the 3, 4-dimethoxybenzonitrile. According to the method, 3, 4-dimethoxyphenyl acetone is used as a raw material, so that high yield can be realized at a relatively mild reaction temperature.
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Paragraph 0018-0020
(2020/07/13)
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- Organophotoredox assisted cyanation of bromoarenes: via silyl-radical-mediated bromine abstraction
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The insertion of a nitrile (-CN) group into arenes through the direct functionalization of the C(sp2)-Br bond is a challenging reaction. Herein, we report an organophotoredox method for the cyanation of aryl bromides using the organic photoredox catalyst 4CzIPN and tosyl cyanide (TsCN) as the nitrile source. A photogenerated silyl radical, via a single electron transfer (SET) mechanism, was employed to abstract bromine from aryl bromide to provide an aryl radical, which was concomitantly intercepted by TsCN to afford the aromatic nitrile. A range of substrates containing electron-donating and -withdrawing groups was demonstrated to undergo cyanation at room temperature in good yields.
- Shah, Sk. Sheriff,Shee, Maniklal,Singh, N. D. Pradeep
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supporting information
p. 4240 - 4243
(2020/04/22)
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- Iron-Promoted Decarboxylation of Arylacetic Acids for the Synthesis of Aromatic Nitriles with Sodium Nitrite as the Nitrogen Source
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A new and effective method was developed for the synthesis of aromatic nitriles from arylacetic acids by using NaNO 2as the nitrogen source and Fe(OTf) 3as the promoter at 50 °C. A series of arylacetic acids underwent this transformation to give the targeted products in yields of 51-90%. Because of the mild conditions, the reaction is compatible with a broad range of functional groups, including ester, carboxy, hydroxy, acetamido, halo, nitro, cyano, methoxy, and even highly reactive formyl groups.
- Shen, Zhenpeng,Liu, Wenbo,Tian, Xinzhe,Zhao, Zhe,Ren, Yun-Lai
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supporting information
p. 1805 - 1808
(2020/11/02)
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- Preparation method of 3, 4-dimethoxybenzonitrile
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A preparation method of 3,4-dimethoxybenzonitrile is characterized in that 3,4-dimethoxyphenylacetic acid and sodium nitrite are used as raw materials, and ferric trichloride is used as a catalyst. The preparation method which is different from previous synthesis methods has the following characteristics: the used raw materials are cheap and easily available phenylacetic acid compounds, and the sodium nitrite is used as a nitrogen source, so the toxicity of the raw materials is low, and the price is low. The problem of high comprehensive cost of materials such as reaction reagents used in theexisting method is solved. The preparation method of the 3,4-dimethoxybenzonitrile has the advantages of low toxicity, simple process, mild conditions and high finished product yield.
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Paragraph 0018-0025
(2020/01/25)
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- Ionic-Liquid Controlled Nitration of Double Bond: Highly Selective Synthesis of Nitrostyrenes and Benzonitriles
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Unprecedented in literature, the conversion of aryl alkenes into β-nitrostyrenes (2) or benzonitriles (3) with sodium nitrite can be governed by an appropriate choice of ionic liquid (IL) medium. A general trend was found for the selectivity of these processes, which depends on the nature of IL, with imidazolium-based ILs, such as [Bmim]Cl, that favor the C–H nitration leading to β-nitrostyrenes, while tetraalkylammonium-based ILs, such as TBAA, privilege the C=C bond cleavage affording benzonitriles. Besides a substrate scope, mechanistic hypotheses were provided on the origin of the different selectivity in the two kinds of ILs, based on their own tunable properties such as polarity, viscosity, and solvent cage effects.
- Casiello, Michele,Caputo, Daniela,Fusco, Caterina,Cotugno, Pietro,Rizzi, Vito,Dell'Anna, Maria Michela,D'Accolti, Lucia,Nacci, Angelo
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supporting information
p. 6012 - 6018
(2020/08/24)
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- Thiocyanate radical mediated dehydration of aldoximes with visible light and air
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We developed a new means of activating aldoximes by an in situ generated thiocyanate radical from ammonium thiocyanate and molecular oxygen at room temperature. With a catalytic amount of organic dye aizenuranine as the photocatalyst, the dehydration of aldoximes proceeds smoothly under visible light irradiation, providing a simple to handle, excellent functional group tolerance, and metal-free protocol for a wide range of nitriles.
- Ban, Yong-Liang,Dai, Jian-Ling,Jin, Xiao-Ling,Zhang, Qing-Bao,Liu, Qiang
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supporting information
p. 9701 - 9704
(2019/08/15)
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- Iron and Phenol Co-Catalysis for Rapid Synthesis of Nitriles under Mild Conditions
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A mild, scalable, high yielding, and rapid route to access diverse nitriles from aldehyde oxime esters enabled by iron(III) and phenol co-catalysis has been developed. The reaction was performed at room temperature to give nitriles in excellent yield within minutes. Mechanistic studies show that the reaction may proceed through a radical process in which benzoyl aldehyde oxime is not only a substrate, but also an ancillary ligand to support iron salt in the promotion of the transformation.
- Meng, Hong,Gao, Sen,Luo, Meiming,Zeng, Xiaoming
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p. 4617 - 4623
(2019/07/15)
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- Enhanced catalytic activity of cobalt nanoparticles encapsulated with an N-doped porous carbon shell derived from hollow ZIF-8 for efficient synthesis of nitriles from primary alcohols in water
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A cobalt catalyst derived from a unique core-shell structure based on hollow ZIF-8 and ZIF-67 (ZIF-67@ZIF-8) is prepared, which exhibits excellent catalytic efficiency for the synthesis of nitriles from alcohols in water under mild conditions (1 atm O2, 50 °C) owing to its large BET surface area, high pore volume, high basicity and hydrophilicity.
- Sun, Kang-Kang,Sun, Jia-Lin,Lu, Guo-Ping,Cai, Chun
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supporting information
p. 4334 - 4340
(2019/08/21)
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- Method for preparing nitrile
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The invention provides a method for preparing nitrile. Aldoxime carboxylic ester is used as a reactant to prepare a nitrile compound. The aldoxime carboxylic ester can be completely converted into corresponding nitrile under common catalysis of ferric salt and phenol within a few minutes. The method for preparing the nitrile has the advantages of gentle reaction conditions, simple and easy-to-getused reagents, cheap and environment-friendly catalyst, wide substrate application range, simple operation, rapid reaction and the like.
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Paragraph 0015
(2019/06/13)
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- A carboxamide is the cyanogen source of aromatic nitrile to the preparation method of the (by machine translation)
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The invention discloses a method for preparing aromatic nitrile, is under the action of the nickel catalyst, in order to carboxamide is the cyanogen source, and with various substituents haloarene coupled reactions, preparing aromatic nitrile. The reaction temperature is 100 - 160 °C, the reaction time is 6 - 24 hours. It overcomes the traditional aromatic nitrile of the synthesis method operation of complex steps, requires the use of a toxic, more expensive, functionalization of the cyanogen source as the reaction raw material and the like. Compared with the traditional method, this method is simple to use cheap, green non-toxic of the formamide is cyano sources; without the need of external dehydrating agent, formamide in the nickel catalyst of the catalytic dehydration at the same time, with a nickel catalyst in coordination with the halogenated aromatic hydrocyanation, more economic, high-efficiency, environmental protection; at the same time the method exhibits good substrate universality, to air, moisture, light are not sensitive, high yield, product separation and purification is simple, with wide application. (by machine translation)
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Paragraph 0015; 0016; 0017; 0018-0024; 0116; 0117-0120
(2019/05/08)
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- Sulfuryl Fluoride Mediated Conversion of Aldehydes to Nitriles
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Aliphatic, aromatic, and heteroaromatic aldehydes were readily converted to corresponding nitriles in a one-pot reaction sequence with hydroxylamine and sulfuryl fluoride. The reaction proceeds at room temperature, does not require metal catalysts and special precautions, and produces nitriles in excellent yields. It is compatible with a variety of functional groups, can be performed in aqueous and organic solvents, and is readily scalable to multigram quantities. Mild conditions and high selectivity of the reaction enabled the construction of polyfunctional probes containing nitrile, alkyne, azide, and fluorosulfate groups for further orthogonal derivatization.
- Gurjar, Jitendra,Bater, Jorick,Fokin, Valery V.
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supporting information
p. 1906 - 1909
(2019/01/24)
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- Method for converting lignin into isoxazole and aromatic nitrile
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The present invention relates to a method for obtaining isoxazole and aromatic nitrile from a lignin model and pre-oxidized birch lignin. The method is characterized in that hydroxylamine hydrochloride and a beta-O-4 model compound containing ketone in the benzyl position, which are used as reaction substrates, undergo oximation condensation Cbeta-O bond fracture under the action of magnesium andother additives to prepare the isoxazole compound, and undergo oximation rearrangement Calpha-Cbeta bond fracture the action of magnesium and other additives to prepare the fragrant nitrile compound.The method can be applied to the conversion of pre-oxidized lignin into the isoxazole and aromatic nitrile. The preparation method comprises the following steps: mixing the beta-O-4 model compound orpre-oxidized birch lignin, hydroxylamine hydrochloride and the additives in an alcohol solvent, adding the obtained mixture into a pressure-resistant container, replacing air in the container with nitrogen, sealing the container, and stirring the mixture at 120 DEG C for 8-12 h to obtain the products isoxazole and aromatic nitrile. The method realizes the obtaining of nitrogen-containing compoundssuch as isoxazole and aromatic nitrile from lignin for the first time, and the reaction process is simple and controllable, and is easy to operate.
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Paragraph 0055; 0056; 0064
(2019/07/04)
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- Ni-Mediated Generation of "cN" Unit from Formamide and Its Catalysis in the Cyanation Reactions
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The in situ generation of a "cyano" unit from readily available organic precursors is of high interest in synthetic chemistry. Herein, we report the first example of Ni-mediated dehydration of formamide to form "CN" and its subsequent catalytic applications in the hydrocyanation of alkynes and cyanation of aryl halides. Formamide can serve as a convenient source for the nitrile unit, in that it releases water as the only byproduct.
- Yang, Luo,Liu, Yu-Ting,Park, Yoonsu,Park, Sung-Woo,Chang, Sukbok
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p. 3360 - 3365
(2019/03/26)
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- Direct Synthesis of Nitriles from Carboxylic Acids Using Indium-Catalyzed Transnitrilation: Mechanistic and Kinetic Study
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Aliphatic and aromatic carboxylic acids can be quantitatively converted to the corresponding nitriles in the presence of catalysts using acetonitrile both as a solvent and reactant at 200 °C. This transformation is based on the acid-nitrile exchange (i.e., transnitrilation) and uses a nontoxic and water resistant catalyst, indium trichloride (InCl3). The mechanism of the transnitrilation was investigated both experimentally and computationally and compared to the previously proposed mechanism. In contrast to the usually assumed formation of amide as an intermediate, transnitrilation is an equilibrium reaction and proceeds via an equilibrated Mumm reaction with the formation of an imide as an intermediate. A simple and reversible mechanism was proposed for this reaction, which was validated by kinetics measurement and by density functional theory calculations of the reaction intermediates and reaction mechanisms.
- Vanoye, Laurent,Hammoud, Ahmad,Gérard, Hélène,Barnes, Alexandra,Philippe, Régis,Fongarland, Pascal,De Bellefon, Claude,Favre-Réguillon, Alain
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p. 9705 - 9714
(2019/10/14)
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- Easy Ruthenium-Catalysed Oxidation of Primary Amines to Nitriles under Oxidant-Free Conditions
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A dehydrogenation of primary amine to give the corresponding nitrile under oxidant- and base-free conditions catalysed by simple [Ru(p-cym)Cl2]2 with no extra ligand is reported. The system is highly selective for alkyl amines, whereas benzylamine derivatives gave the nitrile product together with the imine in a ratio ranging from 14:1 to 4:1 depending on the substrate. Preliminary mechanistic investigations have been performed to identify the key factors that govern the selectivity.
- Achard, Thierry,Egly, Julien,Sigrist, Michel,Maisse-Fran?ois, Aline,Bellemin-Laponnaz, Stéphane
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supporting information
p. 13271 - 13274
(2019/10/21)
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- Development and Utilization of a Palladium-Catalyzed Dehydration of Primary Amides to Form Nitriles
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A palladium(II) catalyst, in the presence of Selectfluor, enables the efficient and chemoselective transformation of primary amides into nitriles. The amides can be attached to aromatic rings, heteroaromatic rings, or aliphatic side chains, and the reactions tolerate steric bulk and electronic modification. Dehydration of a peptaibol containing three glutamine groups afforded structure-activity relationships for each glutamine residue. Thus, this dehydration can act similarly to an alanine scan for glutamines via synthetic mutation.
- Al-Huniti, Mohammed H.,Rivera-Chávez, José,Colón, Katsuya L.,Stanley, Jarrod L.,Burdette, Joanna E.,Pearce, Cedric J.,Oberlies, Nicholas H.,Croatt, Mitchell P.
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supporting information
p. 6046 - 6050
(2018/09/27)
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- Cu(OAc)2/malononitrile/water: A simple reaction system for synthesis of aromatic nitriles from aldoximes
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A simple method for the preparation of nitriles in moderate to good yield has been achieved by treatment of aromatic and heterocyclic aldoximes with malononitrile in water at reflux in the presence of copper acetate as catalyst. Arylaldoximes with an electron-donating group showed the highest reactivity, their conversion being achievable at room temperature.
- Ma, Xiaoyun,He, Daqin,Chen, Zhengjian
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p. 595 - 597
(2018/12/13)
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- Pd/Mn Bimetallic Relay Catalysis for Aerobic Aldoxime Dehydration to Nitriles
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A Pd/Mn bimetal system was found to be an effective catalyst for dehydration of aldoximes to the useful nitriles under mild aerobic conditions. Different to the known metal-catalyzed aldoxime dehydration reactions, this reaction very possibly proceeded via an alternative mechanism of Pd/Mn bimetal relay catalysis involving a Mn-catalyzed aerobic oxidation of aldoximes to nitrile oxides by air and a Pd-catalyzed oxygen transfer from the nitrile oxides to the solvent acetonitrile. This method tolerates a variety of substrates including sterically bulky ones and also the natural product derivative. (Figure presented.).
- Zhang, Dongliang,Huang, Yaping,Zhang, Erlei,Yi, Rong,Chen, Chao,Yu, Lei,Xu, Qing
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supporting information
p. 784 - 790
(2018/01/04)
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- Catalytic Promiscuity of Galactose Oxidase: A Mild Synthesis of Nitriles from Alcohols, Air, and Ammonia
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We report an unprecedented catalytically promiscuous activity of the copper-dependent enzyme galactose oxidase. The enzyme catalyses the one-pot conversion of alcohols into the related nitriles under mild reaction conditions in ammonium buffer, consuming ammonia as the source of nitrogen and dioxygen (from air at atmospheric pressure) as the only oxidant. Thus, this green method does not require either cyanide salts, toxic metals, or undesired oxidants in stoichiometric amounts. The substrate scope of the reaction includes benzyl and cinnamyl alcohols as well as 4- and 3-pyridylmethanol, giving access to valuable chemical compounds. The oxidation proceeds through oxidation from alcohol to aldehyde, in situ imine formation, and final direct oxidation to nitrile.
- Vilím, Jan,Knaus, Tanja,Mutti, Francesco G.
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supporting information
p. 14240 - 14244
(2018/10/15)
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- Copper-Catalyzed Unstrained C-C Single Bond Cleavage of Acyclic Oxime Acetates Using Air: An Internal Oxidant-Triggered Strategy toward Nitriles and Ketones
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A copper-catalyzed aerobic oxidative C-C single bond cleavage of acyclic unstrained oxime acetates is reported, providing various aryl nitriles and ketones in good yields. Mechanistic studies indicate a radical procedure is involved in this transformation, and the oxygen atom in the ketone products is originated from O2 in the air. Oxime acetates as an internal oxidant have been proved to be an initiator, which may promote the discovery of novel protocol for C-C bond cleavage and dioxygen activation.
- Zhu, Chuanle,Chen, Fulin,Liu, Chi,Zeng, Hao,Yang, Zhiyi,Wu, Wanqing,Jiang, Huanfeng
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p. 14713 - 14722
(2018/12/14)
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- Transformation of lignin model compounds to: N -substituted aromatics via Beckmann rearrangement
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Here we present the highly effective cleavage of C-C bonds in lignin model compounds for the production of N-substituted aromatics in up to 96% total yield, including benzonitriles and amides, via oxime formation followed by Beckmann rearrangement (BR). The amides could be further hydrolyzed to anilines (>92% yield) and carboxylic acids (>90% yield), respectively. In addition, the employment of a substrate with a γ-OH group will lead to the formation of C-2 monosubstituted oxazole. A one-pot process involving the BR reaction and hydrolysis has also been developed to directly afford an up to 96% total yield of benzonitriles, benzamides, and anilines. This strategy enabled us to successfully apply the BR reaction to the degradation of lignin model compounds to N-functionalized aromatic products under mild conditions.
- Wang, Yinling,Du, Yiman,He, Jianghua,Zhang, Yuetao
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supporting information
p. 3318 - 3326
(2018/07/29)
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- Nickel-catalyzed cyanation of phenol derivatives activated by 2,4,6-trichloro-1,3,5-triazine
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A nickel-catalyzed cyanation of phenol derivatives activated by 2,4,6-trichloro-1,3,5-triazine (TCT) using aminoacetonitrile as the cyanating agent is described. This catalytic system delivered the desired products in moderate to good yields with good substrate compatibility. The readily available starting materials, cost-effective nickel catalyst and metal-free cyanating agent are the major features of the present method.
- Wang, Liang,Wang, Yaoyao,Shen, Jun,Chen, Qun,He, Ming-Yang
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supporting information
p. 4816 - 4820
(2018/07/13)
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- [1+1+3] Annulation of Diazoenals and Vinyl Azides: Direct Synthesis of Functionalized 1-Pyrrolines through Olefination
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A dirhodium carboxylate catalyzed [1+1+3] annulation reaction of diazoenals and vinyl azides that gives synthetically important enal-functionalized 1-pyrroline derivatives was developed. The reaction involves a novel rhodium-catalyzed olefination of diazoenals with vinyl azides via electrophilic enal carbenoids, resulting in a new class of enal acrylates. The annulation reaction was used for the direct synthesis of valuable deuterated 1-pyrrolines. Structural diversification of the enal-functionalized 1-pyrrolines resulted in the biologically important pyrrolidine-fused oxaziridine, amino acid derivatives, and a 6-azabicyclo[3.2.1]octane motif present in polycyclic alkaloids.
- Kanchupalli, Vinaykumar,Katukojvala, Sreenivas
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p. 5433 - 5437
(2018/04/09)
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- Itopride preparation method
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The invention discloses an itopride preparation method, the method comprises the steps of 1, 2-(dimethylamino) chloroethane hydrochloride and hydroxybenzaldehyde synthesizing into 4-(2- dimethylamino ethoxy) benzaldehyde, then synthesizing into 4-(2- dimethylamino ethoxy) benzyl alcohol in alcohol solvent by revivification; 2, in alcohol solvent 3, 4-dimethoxy benzaldehyde and hydroxylamine hydrochloride creating reaction, then in nonpolar solvent synthesizing into 3, 4- dimethoxybenzonitrile by dehydration using the dehydrant; 3, the 4-(2-dimethylamino ethoxy) benzyl alcohol and the 3, 4- dimethoxybenzonitrile synthesizing into itopride in one step; 4, obtaining hydrochloric acid itopride by dissolving itopride in hydrogen chloride alcohol solution and salifying. The adopted raw material in the method is wide in sourcing scope, simple in preparation processing, and is suitable for large scale industrialization production; the preparation process involves no danger process, the production equipment is simple, the synthesized circuit is shorter than the existed circuits, the preparation time is short and the use effect is good.
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Paragraph 0009
(2017/04/29)
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- Preparation method of medicine of itopride hydrochloride for promoting gastrointestinal motility
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The invention discloses a preparation method of medicine of itopride hydrochloride for promoting gastrointestinal motility. The method comprises the following steps that p-hydroxy methylbenzene is used as a raw material to take a reaction with dimethylaminoethyl chloride hydrochloride; then, 4-(2-dimethylamino oxethyl) benzyl bromide is synthesized through bromination; next, the 4-(2-dimethylamino oxethyl) benzyl bromide and 3,4-dimethoxybenzonitrile take a reaction to obtain a product of itopride under the solvent-free condition through copper trifluoromethanesulfonate catalysis. The preparation method has the advantages a bran-new synthesis route is provided; the itopride is synthesized through Ritter reaction under the solvent-free condition; the advantage of green and environment-friendly effects is realized; meanwhile, the used raw material resources are wide and sufficient; the price is low; the reaction conditions are mild.
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Paragraph 0040; 0061; 0062
(2017/07/19)
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- An efficient synthesis of nitrile, tetrazole and urea from carbonyl compounds
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An efficient conversion of carbonyl compounds (aldehydes and ketones) to nitrile, tetrazole, and urea was developed with the use of a POCl3 and sodium azide mixture using a convergent and microwave method. This is the first report on the direct conversion of ketone to urea. The synthesized compounds were characterized by 1H NMR, 13C NMR, mass and IR spectroscopies and were found to be in agreement with reported compounds.
- Sribalan, Rajendran,Sangili, Arumugam,Banuppriya, Govindharasu,Padmini, Vediappen
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p. 3414 - 3421
(2017/07/13)
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- A practical iodine-catalyzed oxidative conversion of aldehydes to nitriles
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A simple and efficient method for the direct synthesis of nitriles from aldehydes using ammonium acetate as the nitrogen source has been developed. The reactions were performed with iodine as the catalyst and tert-butyl hydroperoxide (TBHP) as the oxidant under mild conditions. A variety of aromatic, heteroaromatic, aliphatic and allylic aldehydes could be converted into their corresponding nitriles in good to excellent yields.
- Fang, Chaojie,Li, Meichao,Hu, Xinquan,Mo, Weimin,Hu, Baoxiang,Sun, Nan,Jin, Liqun,Shen, Zhenlu
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p. 1484 - 1489
(2017/01/21)
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- Diisopropylethylammonium acetate (DIPEAc): An efficient and recyclable catalyst for the rapid synthesis of 5-substituted-1H-tetrazoles
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A simple and efficient protocol developed for the synthesis of 5-substituted 1H-tetrazole derivatives through [2+3] cycloaddition reaction between benzonitriles and sodium azide using diisopropylethylammonium acetate as a recyclable reaction medium is described. The reactions proceed well at 80 °C and provide the corresponding tetrazoles in good to excellent yields (up to 94% yield). Developed method has notable advantages, such as simple and mild conditions, easy workup, reusability with consistent catalytic activity, and safer alternative to hazardous, corrosive conventional Lewis acid catalysts.
- Bhosle, Manisha R.,Shaikh, Dastgir S.,Khillare, Lalit D.,Deshmukh, Amarsinh R.,Mane, Ramrao A.
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p. 695 - 703
(2017/03/27)
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- Ligand controlled switchable selectivity in ruthenium catalyzed aerobic oxidation of primary amines
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A ligand controlled catalytic system for the aerobic oxidation of 1° amines to nitriles and imines has been developed where the varying π-acidic feature of BIAN versus phen in the frameworks of ruthenium catalysts facilitates switchable selectivity.
- Ray, Ritwika,Chandra, Shubhadeep,Yadav, Vishal,Mondal, Prasenjit,Maiti, Debabrata,Lahiri, Goutam Kumar
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supporting information
p. 4006 - 4009
(2017/04/11)
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- An efficient one-pot protocol for the conversion of benzaldehydes into tetrazole analogs
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An efficient protocol has been developed for the one-pot synthesis of tetrazole derivatives in moderate to good yields starting from substituted benzaldehydes and proceeding via non-isolated oxime and nitrile intermediates. The structures of the desired products were confirmed by IR, and NMR spectroscopy as well as mass spectrometry. A plausible reaction mechanism is also discussed.
- Khan, Khalid Mohammed,Fatima, Itrat,Saad, Syed Muhammad,Taha, Muhammad,Voelter, Wolfgang
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p. 523 - 524
(2016/01/20)
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- Method for preparing nitrile by alcohol oxidation
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The invention provides a method for preparing nitrile by alcohol oxidation. The method comprises the following steps: mixing substrate alcohol which is shown as formula (I), a catalyst, a cocatalyst TEMPO, a ligand, an alkaline matter, 25 weight percent to 28 weight percent of ammonium hydroxide and a solvent; reacting for 2 to 24 hours with stirring in an oxygen atmosphere at 25 to 100 DEG C, and performing aftertreatment on reaction liquid to obtain a product nitrile which is shown in a formula (II). The method provided by the invention is environment friendly, wide in substrate application range, high in yield and mild in reaction conditions, has the preparation scale from grams to over hundreds of grams, and also has relatively high practical application value.
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Paragraph 0043; 0066; 0067
(2017/01/23)
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