- Conversions of aryl carboxylic acids into aryl nitriles using multiple types of Cu-mediated decarboxylative cyanation under aerobic conditions
-
Here, we used malononitrile or AMBN as a cyanating agent to develop efficient and practical protocols for Cu-mediated decarboxylative cyanations, under aerobic conditions, of aryl carboxylic acids bearing nitro and methoxyl substituents at the ortho position as well as of heteroaromatic carboxylic acids. These protocols involved economical methods to synthesize value-added aryl nitriles from simple and inexpensive raw materials. Further diversification of the 2-nitrobenzonitrile product was performed to highlight the practicality of the protocols. This journal is
- Cai, Hu,Cao, Xihan,Fu, Zhengjiang,Guo, Shengmei,Wang, Shuiliang
-
supporting information
p. 8381 - 8385
(2020/11/05)
-
- Method for synthesizing aryl cyanide by taking aryl carboxylic acid as raw material
-
The invention discloses a method for synthesizing aryl cyanide by taking aryl carboxylic acid as a raw material, which is characterized in that aryl cyanide is synthesized by taking aryl carboxylic acid as a raw material, taking a combination of NH4X and N, N-dimethylformamide as a cyanide source and taking silver sulfate and copper acetate as catalysts under the action of acid and oxygen. Compared with a conventional aryl cyanide synthesis method, the method disclosed by the invention has the advantages that reaction raw materials (aryl carboxylic acid, NH4X and N, N-dimethylformamide) are cheap and easy to obtain, and the dosage of a metal catalyst is small; meanwhile, oxygen is used as an oxidizing agent, so that the method has the obvious advantages of small environmental pollution, good tolerance to various functional groups on an aromatic ring, high yield and the like; the method disclosed by the invention can be widely applied to synthesis of medicines, functional materials, natural products and other fields in the industry and academic circles.
- -
-
Paragraph 0068-0070
(2020/08/22)
-
- Ag/Cu-mediated decarboxylative cyanation of aryl carboxylic acids with K4Fe(CN)6 under aerobic conditions
-
A method for facile synthesis of aryl nitriles has been well established via Ag/Cu-mediated decarboxylative cyanation of benzoic acids with K4Fe(CN)6 under aerobic conditions. The approach of using readily accessible aryl carboxylic acids and green K4Fe(CN)6 as starting material provides a feasible alternative to previous cyanation protocols. Control experiments revealed the key role of Cu for the process and excluded the possibility of a radical mechanism for the transformation.
- Fu, Zhengjiang,Jiang, Ligao,Li, Zhaojie,Jiang, Yongqing,Cai, Hu
-
supporting information
p. 917 - 924
(2019/03/17)
-
- Preparation method of 2-nitro-4-trifluoromethyl benzonitrile
-
The invention discloses a preparation method of 2-nitro-4-trifluoromethyl benzonitrile, and belongs to the technical field of synthesis of refined chemical intermediates. The preparation method comprises the following steps: enabling 2-nitro-4-trifluoromethyl benzaldehyde serving as a raw material to be in reaction with hydroxylamine hydrochloride and inorganic alkali in water to obtain 2-nitro-4-trifluoromethyl benzaldehyde oxime, then performing dehydration reaction on the 2-nitro-4-trifluoromethyl benzaldehyde oxime in the presence of a nickel compound catalyst to obtain the 2-nitro-4-trifluoromethyl benzonitrile. The dehydration reaction catalyst used in the preparation method is formed by compounding nickel acetate and Raney nickel, is relatively high in activity, and can improve thereaction selectivity and the product yield; as the cost is low, the production and manufacturing cost is reduced, and economic benefits are increased.
- -
-
Page/Page column 4-6
(2019/04/02)
-
- Synthesis method of p-trifluoromethyl benzonitrile compound
-
The invention relates to a preparation method of a p-trifluoromethyl benzonitrile compound. The structural formula of the p-trifluoromethyl benzonitrile compound is shown as formula (I), wherein X isa group selected from nitro or halogen. The p-trifluoromethyl benzonitrile compound is prepared by reacting a compound shown as formula (II) with cuprous cyanide under the action of sodium bromide or/and potassium bromide. The method provided by the invention adopts a low-cost catalyst, has a reaction conversion rate and selectivity up to 95% or more, also makes inorganic salts and tar easy to separate in the subsequent treatment process, thereby simplifying the post-treatment process and reducing the discharge of three wastes, and the method is suitable for large-scale industrial production.
- -
-
Paragraph 0047-0051; 0054-0067
(2019/10/02)
-
- 2 - Nitro - 4 - trifluoromethyl-benzonitrile preparation method
-
The invention discloses a preparation method of 2-nitro-4-trifluoromethylbenzonitrile which is prepared by enabling 3-nitro-4-chlorobenzotrifluoride to react with cyanide with existence of organic solvent, bromide and tetraphenylphosphonium bromide. The organic solvent is N,N-dimethyl formamide, N,N-dimethyl acetamide, N-methyl pyrrolidone, sulfolane and cyanophenyl, bromide is lithium bromide, potassium bromide and cuprous bromide, cyanide is cuprous cyanide, potassium cyanide and sodium cyanide, reaction temperature is 100-200 DEG C, and reaction time is 2-5h. A catalyst system composed of tetraphenylphosphonium bromide and bromide is adopted in the preparation method, so that reaction yield identical with that when nickel bromide is used can be acquired, and cost of the catalyst system is smaller than half that when nickel bromide is used.
- -
-
Paragraph 0019-0022; 0026
(2018/02/21)
-
- Method for preparing 2-nitro-4-trifluoromethylbenzonitrile
-
The invention discloses a method for preparing 2-nitro-4-trifluoromethylbenzonitrile. The method includes the steps that cuprous cyanide is dissolved in N-methyl-2-pyrrolidone, then a catalyst is added, a thermal reaction is conducted for 8-14 h at 150-160 DEG C after addition, and GC detection is conducted till reaction of 2-nitro-4-(trifluoromethyl)halogenobenzene is finished; the product is cooled to room temperature, the solution is poured into a 40-50% ethyl acetate aqueous solution with the molar weight being 4.0-8.0 times that of a 2-nitro-4-trifluoromethylbenzonitrile crude product under the stirring condition, copper salt is filtered out, a filter cake is washed and extracted by means of ethyl acetate with the molar weight being 2-4 times that of 2-nitro-4-trifluoromethylbenzonitrile, oil layers are mixed and then washed with water, finally the product is dried with anhydrous magnesium sulfate and then subjected to vacuum rectification, and a 2-nitro-4-trifluoromethylbenzonitrile fine product is obtained. Use of virulent cyaniding reagents like sodium cyanide and potassium cyanide is avoided, the catalyst is used, reaction selectivity is improved, the yield is increased, the process is mild, and the yield reaches 90-93%.
- -
-
Paragraph 0014; 0015; 0016
(2017/04/25)
-
- Preparation method of 2-nitryl-4-trifluoromethyl benzonitrile
-
The invention relates to the technical field of organic synthesis, in particular to a preparation method of 2-nitryl-4-trifluoromethyl benzonitrile. According to the method, 3-nitryl-4-chlorobenzotrifluoride and cyaniding reagents, as raw materials, react with each other under the action of metal bromides and cuprous cyanide to obtain the 2-nitryl-4-trifluoromethyl benzonitrile. The cyaniding reagents are selected from at least one type of ferrous cyanides. The preparation method has the advantages that the metal bromides, which are low in price and easy to get, serve as activating agents, the cuprous cyanide serves as a catalyst, catalysis yield same as nickel bromide can be achieved, and production cost of enterprises can be reduced remarkably; non-toxicity of reaction reagents can be realized through cyanation based on the almost poisonless ferrous cyanides, environment protection requirements can be met, and industrialization can be realized.
- -
-
Paragraph 0028-0031
(2017/08/29)
-
- A 2-nitro-4-trifluoromethyl-benzonitrile method for the preparation of (by machine translation)
-
The invention provides a preparation method for 2-nitro-4-trifluoromethyl cyanobenzene. Under the catalysis of a metal catalyst, heating 3-nitro-4-halogen benzotrifluoride shown in the structural formula (2) and an organic cyanogen source in a solvent for reaction to obtain the 2-nitro-4-trifluoromethyl cyanobenzene shown in the structural formula (1), and the structural formula (2) and the structural formula (1) of 3-nitro-4-halogen benzotrifluoride and 2-nitro-4-trifluoromethyl cyanobenzene refer to the Specification. According to the invention, cheap copper salt or cuprous salt is used as the catalyst, and the method has the advantages of high conversion rate, relative low toxicity of a cyanation reagent, the capability of reaction under the atmosphere, and the like.
- -
-
Paragraph 0059; 0060
(2016/10/07)
-
- Decarboxylative Halogenation and Cyanation of Electron-Deficient Aryl Carboxylic Acids via Cu Mediator as Well as Electron-Rich Ones through Pd Catalyst under Aerobic Conditions
-
Simple strategies for decarboxylative functionalizations of electron-deficient benzoic acids via using Cu(I) as promoter and electron-rich ones by employing Pd(II) as catalyst under aerobic conditions have been established, which lead to smooth synthesis of aryl halides (-I, Br, and Cl) through the decarboxylative functionalization of benzoic acids with readily available halogen sources CuX (X = I, Br, Cl), and easy preparation of benzonitriles from decarboxylative cyanation of aryl carboxylic acids with nontoxic and low-cost K4Fe(CN)6 under an oxygen atmosphere for the first time.
- Fu, Zhengjiang,Li, Zhaojie,Song, Yuanyuan,Yang, Ruchun,Liu, Yanzhu,Cai, Hu
-
p. 2794 - 2803
(2016/04/26)
-
- A practical and cost-efficient, one-pot conversion of aldehydes into nitriles mediated by 'activated DMSO'
-
Participation of activated DMSO in the one-pot transformation of aldehydes to nitriles has been described by reacting aldehydes with NHHHCl in DMSO in the absence of any added base or catalyst. The method is applicable to access a wide range of aromatic, heterocyclic, and aliphatic nitriles, in which only water is a byproduct. A straightforward and practical procedure is demonstrated on a multigram scale. Georg Thieme Verlag Stuttgart - New York.
- Augustine, John Kallikat,Bombrun, Agnes,Atta, Rajendra Nath
-
scheme or table
p. 2223 - 2227
(2011/10/31)
-
- INHIBITORS OF BETA-SECRETASE
-
The present invention relates to compounds represented by Structural Formula (I) or a pharmaceutically acceptable salt thereof. Definitions for the variables are provided herein.
- -
-
Page/Page column 74
(2011/09/30)
-
- CAPSAICIN RECEPTOR AGONISTS
-
Capsaicin receptor agonists are provided. Such compounds are ligands that may be used to modulate VRl activity in vivo or in vitro, and are particularly useful in the treatment of conditions responsive to capsaicin receptor activation in humans, domesticated companion animals and livestock animals. Pharmaceutical compositions and methods for using them to treat such disorders are provided, as are methods for using such ligands for receptor localization studies.
- -
-
Page/Page column 45
(2010/02/11)
-
- Chemical processes
-
The invention relates to a process for the preparation of a compound of formula (I) wherein: R1represents C1-4haloalkyl, fluorine, chlorine or bromine; and R2represents hydrogen or C1-4alkoxy; which process comprises the reaction of the corresponding ortho-nitrohalobenzene of formula (II): wherein R1and R2are as hereinbefore defined and X represents a fluorine or bromine atom, with, when X represents a fluorine atom: (a) an alkali metal cyanide, in a non aqueous solvent, optionally in the presence of a catalyst; or when X represents a bromine atom: (b) cuprous cyanide, in a non aqueous solvent, optionally in the presence of a catalyst selected from an alkali metal bromide or an alkaline earth metal bromide; or (c) an alkali metal cyanide, in a non aqueous solvent, in the presence of a catalytic amount of cuprous cyanide and a phase transfer catalyst.
- -
-
Page/Page column 6-7
(2008/06/13)
-
- Nucleophilic aromatic substitution for heteroatoms: An oxidative electrochemical approach
-
The nucleophilic aromatic substitution for heteroatom through electrochemical oxidation of the intermediate σ-complexes (Meisenheimer complexes) in simple nitroaromatic compounds is reported for the first time (NASX process). The studies have been carried out with hydride, cyanide, fluoride, methoxy, and ethanethiolate anions and n-butylamine as a nucleophile, at the cyclic voltammetry (CV) and preparative electrolysis level. The cyclic voltammetry experiments allow for detection and characterization of the σ-complexes and they have led us to a proposal for the mechanism of the oxidation step. Furthermore, the power of the CV technique in the analysis of the reaction mixture throughout the whole chemical and electrochemical process is described.
- Gallardo, Iluminada,Guirado, Gonzalo,Marquet, Jordi
-
p. 2548 - 2555
(2007/10/03)
-
- Nucleophilic aromatic substitution of hydrogen: A novel electrochemical approach to the cyanation of nitroarenes
-
The nucleophilic aromatic substitution of hydrogen through electrochemical oxidation of the intermediate σ complexes (Meisenheimer complexes) in simple nitroaromatic compounds is reported for the first time. The studies have been carried out with hydride and cyanide anions as the nucleophiles using cyclic voltammetry (CV) and preparative electrolysis. The cyclic voltammetry experiments allow for the detection and characterization of the σ complexes and led us to a proposal for the mechanism of the oxidation step. Furthermore, the power of the CV technique in the analysis of the reaction mixture throughout the whole chemical and electrochemical process is described.
- Gallardo, Iluminada
-
p. 1759 - 1765
(2007/10/03)
-
- Synthesis of dialkyl cyanoboronates and their application in palladium-catalyzed cyanation of aryl halides
-
A new type of cyanoboronate 4 was prepared and used as a new cyano group source in palladium-catalyzed cyanations of aryl and heteroaryl halides to afford the corresponding aryl and heteroaryl nitriles.
- Jiang, Biao,Kan, Ying,Zhang, Ao
-
p. 1581 - 1584
(2007/10/03)
-
- Arthropodicidal pyrazolines, pyrazolidines and hydrazines
-
Arthropodicidal pyrazoline, pyrazolidine and hydrazine compounds, including all their geometric and stereoisomers, agriculturally suitable salts thereof and compositions containing them; and a method for controlling arthropods employing said compounds which are: STR1 wherein Q, X, X1, Y and G are as defined in the text.
- -
-
-
- Process for the production of ortho-nitrobenzonitriles
-
Ortho-nitrobenzonitriles are produced from the corresponding ortho-nitrochlorobenzenes by reaction with cuprous cyanide and an alkali metal bromide, an alkaline earth metal bromide, or zinc bromide or with a combination of lithium cyanide and cuprous bromide, optionally in the presence of a solvent.
- -
-
-
- Potential Antimalarials. IX Di-Mannich Bases of 4-(7'-Trifluoromethylquinazolin-4'-ylamino)phenol and 4-(7'-Trifluoromethylquinolin-4'-ylamino)phenol
-
Syntheses are reported for a series of di-Mannich bases of 4-(7'-trifluoromethylquinazolin-4'-ylamino)phenol derived from 4-chloro-7-trifluoromethylquinazoline with the di-Mannich bases of 4-aminophenol.Some analogous quinolines were prepared similarly.When tested for antimalarial activity against Plasmodium falciparum in vitro, the quinazolines were rather less active than the corresponding quinolines.
- Barlin, Gordon B.,Jiravinyu, Chuenjit
-
p. 311 - 319
(2007/10/02)
-
- Arthropodicidal tetrahydrobenzopyranopyrazoles
-
This invention concerns substituted tetrahydro-benzopyranopyrazoles of the formula wherein R1 to R5 are substituents, or R1, R2 and R5 may independently be hydrogen; intermediates thereto, agricultural compositions containing the tetrahydro-benzopyranopyrazoles and a method for using them to control arthropods in agronomic and nonagronomic environments. Also disclosed is a process for preparing the tetrahydrobenzopyranopyrazoles by cyclization of phosphorus-containing starting reactants in the presence of a halogenating agent and base.
- -
-
-
- Process for the production of ortho-nitrobenzonitriles
-
Ortho-nitrobenzonitriles are produced from the corresponding ortho-nitrochlorobenzenes by reaction with cuprous cyanide and an alkali metal bromide, an alkaline earth metal bromide, or zinc bromide or with a combination of lithium cyanide and cuprous bromide, optionally in the presence of a solvent.
- -
-
-
- 3-Aminoindazole derivatives
-
.Iadd.Pharmaceutical compositions having muscle relaxant and analgesic activity containing 3-aminoindazoles..Iaddend.
- -
-
-
