- Cooperative Co(III)/Cu(II)-Catalyzed C-N/N-N Coupling of Imidates with Anthranils: Access to 1H-Indazoles via C-H Activation
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Cooperative cobalt- and copper-catalyzed C-H activation of imidate esters and oxidative coupling with anthranils allowed efficient synthesis of 1H-indazoles in the absence of metal oxidants. The anthranil acts as a convenient aminating reagent as well as an organic oxidant in this transformation. The copper catalyst likely functions at the stage of N-N formation.
- Li, Lei,Wang, He,Yu, Songjie,Yang, Xifa,Li, Xingwei
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Read Online
- Metal-Free Synthesis of Anthranils by PhIO Mediated Heterocyclization of ortho-Carbonyl Anilines
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Here, we report a metal-free synthesis of anthranils from ortho-carbonyl anilines using PhIO as a sole additive under ambient conditions. This methodology did not require any external additives and delivered anthranils in excellent yields with broad substrate scope. The mechanistic studies suggest that the reaction proceeds via in-situ generation of iminoiodane leading to nitrene and a subsequent nucleophilic attack from oxygen of ortho-carbonyl aniline on nitrene results in heterocyclization.
- Garia, Alankrita,Grover, Jatin,Jain, Nidhi
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p. 4125 - 4131
(2021/08/24)
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- Rh(iii)-Catalyzed tandem indole C4-arylamination/annulation with anthranils: Access to indoloquinolines and their application in photophysical studies
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An efficient Rh(iii)-catalyzed straightforward strategy was developed for the tandem C4 arylamination/annulation of indole derivatives with anthranil to provide indoloquinoline moieties. This method is simple and regioselective with a wide scope and functional group tolerance. Mechanistic studies revealed the important role of the newly installed azacycle in the conversion of O-protected aldoximes to their cyano derivatives. Studies were carried out to explore the promising photophysical properties of the obtained indoloquinoline derivatives.
- Biswas, Aniruddha,Bera, Satabdi,Poddar, Puja,Dhara, Dibakar,Samanta, Rajarshi
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supporting information
p. 1440 - 1443
(2020/02/11)
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- Practical Synthesis of Benzimidazo[1,2- A[quinolines via Rh(III)-Catalyzed C-H Activation Cascade Reaction from Imidamides and Anthranils
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We report a novel and practical one-pot Rh(III)-catalyzed strategy to construct benzimidazo[1,2-a]quinolines from readily available imidamides and anthranils. The cascade reaction proceeds via a C-H amination-cyclization-cyclization process in ionic liquid without any additives and possesses simple operation, moderate-to-high yield, and broad substrate scope features, which will provide the reference for the construction of biologically active fused benzimidazoles.
- Hu, Yao,Wang, Ting,Liu, Yanzhao,Nie, Ruifang,Yang, Ninghong,Wang, Qiantao,Li, Guo-Bo,Wu, Yong
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supporting information
p. 501 - 504
(2020/01/31)
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- RhIII-Catalyzed Straightforward Synthesis of Benzophenanthroline and Benzophenanthrolinone Derivatives using Anthranils
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An efficient pot-economic and step-economic RhIII-catalyzed site-selective direct amination/annulation strategy was developed for the synthesis of benzophenanthroline derivatives using quinoline N-oxides and anthranils. The method was further extended to the synthesis of nitrogen-containing extended π-conjugated benzophenanthrolinone derivatives. Late-stage functionalizations of cinchonidine and cinchophen derivatives and synthesis of a bioactive quinolino-indole were achieved.
- Biswas, Aniruddha,Sarkar, Souradip,Samanta, Rajarshi
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supporting information
p. 3000 - 3004
(2019/02/13)
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- Gold(III)-catalyzed chemoselective annulations of anthranils with N-allylynamides for the synthesis of 3-azabicyclo[3.1.0]hexan-2-imines
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We herein report the gold(iii)-catalyzed selective annulation of anthranils with N-allylynamides under mild conditions. By trapping the in situ-generated α-imino gold carbenes, 3-azabicyclo[3.1.0]hexan-2-imines were obtained in high synthetic efficiency. The reaction, which can be conducted in the gram scale, tolerates electron-rich and electron-deficient anthranils as well as a diverse set of functionalized ynamides (aryl- and alkyl-substituted terminal).
- Song, Lina,Tian, Xianhai,Rudolph, Matthias,Rominger, Frank,Hashmi, A. Stephen K.
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supporting information
p. 9007 - 9010
(2019/08/01)
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- Catalyst-free cyclization of anthranils and cyclic amines: One-step synthesis of rutaecarpine
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An efficient synthesis of a variety of quinazolinone derivatives via a direct cyclization reaction between commercially available anthranils and cyclic amines is described. The developed transformation proceeds with the merits of high step- and atom-efficiency, a broad substrate scope, and good to excellent yields, without additional catalysts, and offers a practical way for the preparation of rutaecarpine and its derivatives with structural diversity.
- Li, Jian,Wang, Zheng-Bing,Xu, Yue,Lu, Xue-Chen,Zhu, Shang-Rong,Liu, Li
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supporting information
p. 12072 - 12075
(2019/10/14)
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- Gold(III)-Catalyzed Site-Selective and Divergent Synthesis of 2-Aminopyrroles and Quinoline-Based Polyazaheterocycles
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A facile, site-selective, and divergent approach to construct 2-aminopyrroles and quinoline-fused polyazaheterocycles enabled by a simple gold(III) catalyst from ynamides and anthranils under mild reaction conditions is described. This one-pot strategy uses readily available starting materials, proceeds in a highly step- and atom-economical manner, with broad substrate scope and scale-up potential. The key element for success in this tandem reaction is a catalyst-directed preferred quenching of the in situ generated gold carbene intermediates by a nucleophilic benzyl/2-furylmethyl moiety on the ynamides as an alternative to the known C?H annulation leading to indoles.
- Zeng, Zhongyi,Jin, Hongming,Rudolph, Matthias,Rominger, Frank,Hashmi, A. Stephen K.
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supporting information
p. 16549 - 16553
(2018/11/23)
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- Preparation method of alprazolam intermediate
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The invention discloses a preparation method of an alprazolam intermediate. The method comprises the following steps: sequentially adding methanol and p-nitrochlorobenzene in a sodium hydroxide watersolution, dropwise adding phenylacetonitrile under stirring, reacting at 40 +/-5 DEG C after the dropwise addition is finished, and carrying out post-treatment to obtain an intermediate (II) ; and dissolving the intermediate (II) in ethanol, adding iron powder, refluxing, dropwise adding sulfuric acid, refluxing for 1 hour, and carrying out post-treatment to obtain an intermediate(III). Accordingto the method disclosed by the invention, the sodium hydroxide water solution is used in the synthesis of the intermediate (II) to replace a dangerous mode of refluxing and dissolving solid sodium hydroxide by using ethanol, a small amount of methanol is added into the reaction system, and the problem of two-phase reaction is successfully solved. The sulfuric acid is used for replacing volatile hydrochloric acid during the synthesis of the intermediate (III), the reaction time is effectively shortened, and the reaction efficiency is improved. The method disclosed by the invention is safer to operate, short in reaction time and more suitable for industrial production.
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Paragraph 0030; 0032; 0033; 0036; 0040
(2018/07/30)
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- Preparation method of 2-amino-5- chlorobenzophenone
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The invention discloses a preparation method of 2-amino-5- chlorobenzophenone. The preparation method comprises the following steps: (1) mixing ethanol with the mass concentration of 95%, sodium hydroxide, parachloronitrobenzene and benzyl cyanide, mixing the mixture and performing ultrasonic oscillation on the mixture at the temperature of 25-35 DEG C for 1h; (2) performing microwave heating on aproduct obtained in step (1) for 10min, adding water in a system, filtering, washing filter residues with methanol three times and drying the filter residues, so as to obtain 5-chlorine-3-phenyl-2, 1-benzisoxazole; (3) mixing methanol, the 5-chlorine-3-phenyl-2, 1-benzisoxazole, a palladium carbon catalyst and ammonium formate, heating and refluxing for 2h, cooling to room temperature, filteringand performing vacuum drying on the filter residues. The method provided by the invention is high in product yield, short in reaction time and less in waste discharge and is environmentally friendly.
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Paragraph 0014; 0015; 0016; 0017
(2018/03/26)
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- Preparation method of 2-amino-5-chlorobenzophenone
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The invention discloses a preparation method of 2-amino-5-chlorobenzophenone. The preparation method of 2-amino-5-chlorobenzophenone comprises the following steps: (1) mixing ethanol and sodium hydroxide, performing heating reflux, adding parachloronitrobenzene, stirring for 30 to 60 minutes, cooling to 28 DEG C, adding benzyl cyanide, reacting at 25 to 35 DEG C for 3 hours and naturally cooling to room temperature; (2) performing microwave heating, adding water, filtering, washing the filter residue with methanol and drying to obtain 5-chlorine-3-phenyl-2,1 benzisoxazole; and (3) performing heating reflux on 5-chlorine-3-phenyl-2,1 benzisoxazole, iron powder and ethanol, dropwise adding a hydrochloric acid ethanol solution into a system, refluxing at 35 DEG C for 2 hours, adjusting the pHof the system to be 7 to 8, adding activated carbon into the system, continuously refluxing, filtering and vacuum-drying the filter residue to obtain 2-amino-5-chlorobenzophenone. By the method, theyield of products is high and can reach to 94 percent, the reaction time is short, emission of waste is reduced, and the production method is environment-friendly.
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Paragraph 0014; 0015; 0016
(2018/03/26)
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- Synthesis method of 2-amino-5-chlorobenzophenone
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The invention discloses a synthesis method of 2-amino-5-chlorobenzophenone. The method comprises the following steps: (1) mixing ethanol having a mass concentration of 95% with sodium hydroxide, parachloronitrobenzene and phenylacetonitrile, stirring, and carrying out ultrasonic oscillating at the temperature of 25-35 DEG C; (2) carrying out microwave heating, adding water into a system, filtering, washing filter residue with methanol, and then drying to obtain 5-chloro-3-phenyl-2,1-benzisoxazole; (3) mixing tetrahydrofuran with triethylamine, then adding the 5-chloro-3-phenyl-2,1-benzisoxazole and a palladium carbon catalyst and mixing, introducing nitrogen, carrying out air replacement, then introducing nitrogen until the pressure is 0.1MPa, and carrying out magnetic stirring; then, filtering, and carrying out vacuum drying on the obtained filter residue so as to obtain the 2-amino-5-chlorobenzophenone. The method provided by the invention has the advantages that product yield is high, and can reach 95%; the reaction time is short, waste emission is reduced, and the production method is environmentally-friendly.
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Paragraph 0014; 0015; 0016
(2018/07/30)
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- A nerve of surgical medicine temazepam intermediate synthetic method of the compound (by machine translation)
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The invention provides a nerve of surgical medicine temazepam intermediate compound of the formula (III) compound synthetic method, the synthetic method is as follows: in the catalyst, ligand, in the presence of alkali and accelerator, the following formula (I) compounds of the formula (II) compound in the organic solvent in the reaction, after-treatment after the reaction, so as to obtain states the type (III) compounds, the synthesis method through the unique reaction system, but can yield to obtain the target product. The invention also provides the above-mentioned compound recrystallization purification method, through the unique the re-crystallization method, can significantly improve the purity of the product, for the compound to provide new method for the purification of, and has good application prospect and potential. (by machine translation)
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Paragraph 0047; 0048; 0049; 0050; 0061; 0062; 0063-0100
(2017/08/29)
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- Synthesis of 3-Substituted 2,1-Benzisoxazoles by the Oxidative Cyclization of 2-Aminoacylbenzenes with Oxone
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An efficient approach to the synthesis of 2,1-benzisoxazoles through direct construction of the N-O bond by the chemoselective oxidation of 2-aminoacylbenzenes with Oxone is described. This alternative methodology is characterized by its simple and transition-metal-free conditions and good functional group compatibility utilizing Oxone as a green oxidant instead of hypervalent iodine compounds. Moreover, this new procedure simplifies the number of steps compared to the previously reported procedure by circumventing the use of 2-azido-substituted aryl ketones.
- Chiarini, Marco,Del Vecchio, Luana,Marinelli, Fabio,Rossi, Leucio,Arcadi, Antonio
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p. 3017 - 3030
(2016/10/12)
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- Mechanism of formation of 2,1-benzisoxazoles in reactions of nitroarenes with arylacetonitriles
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Main regularities in reactions of arylacetonitriles with nitroarenes were discussed. The reaction mechanism has been suggested proceeding from the experimental data and the quantum chemical modeling of the limiting stage, the formation of the 2,1-benzisoxazole ring.
- Orlov,Kotov,Tsivov,Rusakov
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p. 245 - 252
(2015/04/14)
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- Intramolecular Fe(II)-Catalyzed N-O or N-N bond formation from aryl azides
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(Figure presented) Iron(II) bromide catalyzes the transformation of aryl and vinyl azides with ketone or methyl oxime substituents into 2,1-benzisoxazoles, indazoles, or pyrazoles through the formation of an N-O or N-N bond. This transformation tolerates a variety of different functional groups to facilitate access to a range of benzisoxazoles or indazoles. The unreactivity of the Z-methyloxime indicates that N-heterocycle formation occurs through a nucleophilic attack of the ketone or oxime onto an activated planar iron azide complex.
- Stokes, Benjamin J.,Vogel, Carl V.,Urnezis, Linda K.,Pan, Minjie,Driver, Tom G.
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supporting information; experimental part
p. 2884 - 2887
(2010/08/21)
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- Nucleophilic replacement of hydrogen in para-substituted nitrobenzenes by phenylacetonitrile carbanion
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The kinetic relations holding in nucleophilic replacement of hydrogen in para-substituted nitrobenzenes by phenylacetonitrile carbanion suggest a complex reaction mechanism involving two alternative pathways. The direction of the process is determined by the structure of intermediate σ-complex.
- Orlov,Sokovikov,Kotov
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p. 100 - 103
(2007/10/03)
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- Nucleophilic substitution of hydrogen in activated nitroarenes by phenylacetonitrile carbanion
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General relations holding in nucleophilic substitution of hydrogen in para-substituted nitroarenes by phenylacetonitrile carbanion were analyzed in terms of the Klopman reactivity indices. Requirements to the substrate structure were determined, which restrict the scope of application of this method to synthesis of 2,1-benzisoxazole derivatives.
- Orlov,Sokovikov,Kotov,Starikov
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p. 1735 - 1738
(2007/10/03)
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- Synthesis of 2,1-benzisoxazole derivatives from nitroarenes and CH acids in aprotic media
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DBU/MgCl2 mediated reaction between nitroarenes and some CH acids bearing leaving group lead to 2,1-benzisoxazole derivatives under aprotic conditions. Ortho-directing effect was observed.
- Wrobel
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p. 2384 - 2388
(2007/10/03)
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- Substituent Effect on the Reaction Rate of para-Substituted Nitrobenzenes with Phenylacetonitrile
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The substituent effect on the reaction rate of para-substituted nitrobenzenes with the phenylacetonitrile was evaluated using the model of orbital interactions. The limiting step of the reaction was presumed to have associative character.
- Orlov,Kotov,Rusakov,Bystryakova,Kopeikin,Mironov
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p. 538 - 540
(2007/10/03)
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- FUNCTIONALIZATION OF AROMATIC COMPOUNDS BY NUCLEOPHILIC SUBSTITUTION OF A HYDROGEN ATOM BY THE PHENYLACETONITRILE CARBANION
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Aromatic nitro compounds containing a substituent at the para react with phenylacetonitrile in an alcohol solution of alkali with the formation of 2,1-benzisoxazoles.The CH3, NH2, OH, and certain other substituents prevent the reaction.In the reaction of benzonitrile and phthalonitrile with phenylacetonitrile in the sodium hydroxide-DMSO system substitution of a hydrogen atom at the ortho position to the nitrile group is observed; the products from substitution of a hydrogen atom were not obtained in the reaction of phenylacetonitrile with aromatic nitriles containing other substituents.
- Orlov, V. Yu.,Kotov, A. D.,Bystryakova, E. B.,Kopeikin, V. V.,Mironov, G. S.
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p. 1481 - 1484
(2007/10/02)
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- Pyrolysis of Aryl Azides. VIII. Hammett Correlations of Rates of Pyrolysis of Substituted 2-Azidobenzophenones
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Eight 2-azidobenzophenones with 4- or 5-substituents have been pyrolysed in decalin solution to yield 3-phenyl-2,1-benzisoxazoles.Rate values at 100 deg are correlated with the Hammett substituent constants, with respect to both the azido (A) and benzoyl (B) reaction centres, and yield the eqation log k = -4.38 + 2.08?-A -1.52?B.There is a similar equation for rates measured at 120 deg.Although nitro and benzoyl differ considerably in their neighbouring group abilitites in azide pyrolyses, it is concluded that they exert their effects through the same mechanism.The results are consistent with both published variants of an electrocyclic mechanism (Dyall; Smith, Budde and Chou).
- Dyall, Leonard K.,Karpa, Gary J.
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p. 1231 - 1241
(2007/10/02)
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