- Continuous process for production of CuCF3 via direct cupration of fluoroform
-
The first continuous flow process has been developed for the synthesis of a superior trifluoromethylating reagent, ligandless CuCF3, from fluoroform, by far the best CF3 source in terms of availability, cost, and atom economy. Optimization of the residence time and feed rates for CHF3 (gas), the cuprating reagent (premade from CuCl and t-BuOK in a 1:2 ratio) in DMF, and the stabilizer (Et3N· 3HF) at 23 °C and atmospheric pressure has allowed for the continuous production of CuCF3 in consistently high yields of up to 94%. The thus produced CuCF3 has been shown to be as highly efficient a trifluoromethylating agent as the one from the previously developed batch process.
- Mazloomi, Zahra,Bansode, Atul,Benavente, Pedro,Lishchynskyi, Anton,Urakawa, Atsushi,Grushin, Vladimir V.
-
-
Read Online
- Preparation method of o-trifluoromethylbenzamide
-
The present invention discloses a method for preparing o-trifluoromethyl benzamide. The preparation method comprises the following steps: (1) in an organic solvent, the 2-nitrobenzotrifluoride and fluorinated salts are denitrified as shown below to obtain o-fluorobenzotrifluoride; (2) in an organic solvent, the o-fluortrifluorotoluene and cyanidylation reagent are defluoride cyanidation reaction as shown below to obtain o-trifluoromethylbenzonitrile; (3) in the presence of alkali, the o-trifluoromethylbenzonitrile, hydrogen peroxide hydrolysis reaction as shown below. The preparation method is simple to treat, the product purity is high, the impurities are small, and the yield is high.
- -
-
Paragraph 0052; 0063-0067; 0076-0078
(2022/01/12)
-
- Synthesis method 2 - trifluoromethyl benzamide
-
The invention discloses a synthesis method of 2 -trifluoromethylbenzamide, which comprises the following steps of 2, 3 -dichloro-trifluorotoluene serving as a raw material and fluorinating. The preparation 2 -trifluoro -6 -cyano-trifluorotoluene is prepared by cyano substitution, 2 -fluoro -6 -cyanobenzotrifluoride is subjected to hydrogenation and dehydrochlorination, and 2 -trifluoromethylbenzamide is prepared by first hydrolyzing and dehydrochlorinating and dechlorinating. 2 - Trifluoromethylbenzamide is synthesized by simple reaction, and the method has the characteristics of cheap and easily available raw materials, no participation of the isomer 2 - fluorine -3 - chlorine - trifluorotoluene isomers in subsequent reaction and easy removal. In each reaction step, flammable and explosive, highly toxic or non-volatile agents commonly used in the existing synthetic method are not used, and harm to operating personnel and in the environment is avoided. , The total yield of the product reaches above 67%, and the purity is 97% or more.
- -
-
Paragraph 0028; 0035; 0042-0043; 0055; 0062-0063
(2021/11/27)
-
- Visible light-mediated synthesis of amides from carboxylic acids and amine-boranes
-
Here, a photocatalytic deoxygenative amidation protocol using readily available amine-boranes and carboxylic acids is described. This approach features mild conditions, moderate-to-good yields, easy scale-up, and up to 62 examples of functionalized amides with diverse substituents. The synthetic robustness of this method was also demonstrated by its application in the late-stage functionalization of several pharmaceutical molecules.
- Chen, Xuenian,Kang, Jia-Xin,Ma, Yan-Na,Miao, Yu-Qi
-
supporting information
p. 3595 - 3599
(2021/06/06)
-
- Method for preparing amide compounds by using supported metal oxide catalytic material
-
The invention relates to a catalyst for preparing amide compounds, and aims to provide a method for preparing amide compounds by using a supported metal oxide catalytic material. The method comprisesthe following steps: uniformly mixing a solvent, water, an organic nitrile compound and the catalytic material; performing a reaction at 50-180 DEG C for 0.5-48 h; and hydrating and converting the organic nitrile compound into the corresponding amide compounds through the catalytic hydration effect of the catalyst in the reaction process. Adsorption and activation of the catalytic material to water molecules can be effectively regulated by regulating metal components loaded on the catalytic material and a catalytic material carrier, so that important amide compounds in chemical and agricultural processes are efficiently prepared. The provided method for preparing the amide compounds is effect, and has the advantages of high atom utilization rate in the reaction process, low reaction temperature, no additional reaction assistant in the synthesis process, no generation of toxic or harmful byproducts after the reaction, and green and environment-friendly synthesis process.
- -
-
Paragraph 0134; 0135
(2020/06/05)
-
- Fluopyram and synthesis method thereof
-
The invention discloses fluopyram and a synthesis method thereof. The fluopyram comprises the following raw materials: trifluoromethylbenzoic acid, thionyl chloride, ammonia water, water, potassium carbonate, paraformaldehyde, formamide, acetic anhydride, 5-trifluoromethyl-2-dimethyl malonate--3-chloropyridine, sodium chloride and hydrochloric acid. The content of fluopyram obtained in the invention is 98% or more, and the total yield of fluopyram is 63% or more. The synthesis method of the invention does not use cyano groups with high activity, and the yield of aminolysis can reach 93%; the raw materials are simple to treat and high in utilization rate; waste gas, waste water and industrial residues are not produced; and the synthesis method is simple in process and easy to operate and implement.
- -
-
Paragraph 0051; 0052; 0065; 0074; 0080; 0083; 0092
(2018/11/27)
-
- Design, synthesis, DFT study and antifungal activity of the derivatives of pyrazolecarboxamide containing thiazole or oxazole ring
-
Pyrazolecarboxamide fungicides are one of the most important classes of agricultural fungicides, which belong to succinodehydrogenase inhibitors (SDHIS). To discover new pyrazolecarboxamide analogues with broad spectrum and high activity, a class of new compounds of pyrazole carboxamide derivatives containing thiazole or oxazole ring were designed by scaffold hopping and bioisosterism, and 36 pyrazole carboxamide derivatives with antifungal activity were synthesized. Those compounds were evaluated against five phytopathogenic fungi, Gibberella zeae, Phytophythora capsici, Sclerotonia sclerotiorum, Erysiphe graminis and Puccinia sorghi. The results indicated that most of the compounds displayed good fungicidal activities, especially against E. graminis. Theoretical calculations were carried out at the B3LYP/6-31G (d, p) level and the full geometry optimization was carried out using the 6-31G (d, p) basis set, and the frontier orbital energy, atomic net charges, molecular docking were discussed, and the structure-activity relationships were also studied.
- Yan, Zhongzhong,Liu, Aiping,Huang, Mingzhi,Liu, Minhua,Pei, Hui,Huang, Lu,Yi, Haibo,Liu, Weidong,Hu, Aixi
-
p. 170 - 181
(2018/03/08)
-
- Aminocarbonylation of Aryl Halides to Produce Primary Amides by Using NH4HCO3 Dually as Ammonia Surrogate and Base
-
An efficient and clean protocol was developed for rapid production of primary aromatic amides by aminocarbonylation with NH4HCO3. Without addition of auxiliary base, the use of solid and cheap NH4HCO3 dually as ammonia surrogate and base not only promoted aminocarbonylation over subsequent dehydration and hydrolysis of amides owing to its weak basicity, and it also made the reaction manipulation clean and simplified without the presence of stinky NH3 or organic amines. The Xantphos ligand with relatively intensive π-acceptor character (1J31P–77Se=758 Hz) and wide natural bite angle (βn=111°) was found to be indispensable for the high efficiency of this reaction.
- Wang, Dong-Liang,Liu, Huan,Yang, Da,Wang, Peng,Lu, Yong,Liu, Ye
-
p. 4206 - 4211
(2017/12/02)
-
- Rh(III)-Catalyzed Redox-Neutral Annulation of Primary Benzamides with Diazo Compounds: Approach to Isoquinolinones
-
Reported herein is a Rh-catalyzed redox-neutral annulation of primary benzamides with diazo compounds, representing an efficient and economic protocol to isoquinolinones. The procedure exhibited good functional group tolerability, scalability, and regioselectivity, obviating the need for oxidants, and only environmentally benign N2 and H2O were released. Further utilization of the method provided an alternative route to functionalized isoquinolines.
- Wu, Youzhi,Sun, Peng,Zhang, Kaifan,Yang, Tie,Yao, Hequan,Lin, Aijun
-
p. 2166 - 2173
(2016/03/15)
-
- PROCESS FOR THE PREPARATION OF 2-(TRIHALOMETHYL) BENZAMIDE
-
The present invention relates to a process for the preparation of 2-(trihalomethyl) benzamide from a 2-(trihalomethyl) benzoyl chloride in the presence of isopropanol or cold water.
- -
-
Page/Page column 7
(2016/05/02)
-
- Synthesis of primary Amides via Copper-Catalyzed Aerobic Decarboxylative ammoxidation of Phenylacetic Acids and α-Hydroxyphenylacetic acids with Ammonia in water
-
A Cu2O-catalyzed aerobic oxidative decarboxylative ammoxidation to primary benzamides from phenylacetic acids and a-hydroxyphenylacetic acids is developed. A variety of primary benzamides could be prepared smoothly, in good to excellent yields, by means of a one-pot domino protocol combining decarboxylation, dioxygen activation, oxidative C-H bond functionalization, and amidation reactions.
- Song, Qiuling,Feng, Qiang,Yang, Kai
-
supporting information
p. 624 - 627
(2014/04/03)
-
- Trifluoromethylation of aryl and heteroaryl halides with fluoroform-derived CuCF3: Scope, limitations, and mechanistic features
-
Fluoroform-derived CuCF3 recently discovered in our group exhibits remarkably high reactivity toward aryl and heteroaryl halides, performing best in the absence of extra ligands. A broad variety of iodoarenes undergo smooth trifluoromethylation with the ligandless CuCF3 at 23-50 C to give the corresponding benzotrifluorides in nearly quantitative yield. A number of much less reactive aromatic bromides also have been trifluoromethylated, including pyridine, pyrimidine, pyrazine, and thiazole derivatives as well as aryl bromides bearing electron-withdrawing groups and/or ortho substituents. Only the most electrophilic chloroarenes can be trifluoromethylated, e.g., 2-chloronicotinic acid. Exceptionally high chemoselectivity of the reactions (no side-formation of arenes, biaryls, and C2F5 derivatives) has allowed for the isolation of a large number of trifluoromethylated products in high yield on a gram scale (up to 20 mmol). The CuCF3 reagent is destabilized by CuX coproduced in the reaction, the magnitude of the effect paralleling the Lewis acidity of CuX: CuCl > CuBr > CuI. While SNAr and SRN1 mechanisms are not operational, there is a well-pronounced ortho effect, i.e., the enhanced reactivity of ortho-substituted aryl halides 2-RC6H4X toward CuCF3. Intriguingly, this ortho-effect is observed for R = NO2, COOH, CHO, COOEt, COCH3, OCH3, and even CH3, but not for R = CN. The fluoroform-derived CuCF3 reagent and its reactions with haloarenes provide an unmatched combination of reactivity, selectivity, and low cost.
- Lishchynskyi, Anton,Novikov, Maxim A.,Martin, Eddy,Escudero-Adan, Eduardo C.,Novak, Petr,Grushin, Vladimir V.
-
p. 11126 - 11146
(2013/12/04)
-
- Formamide as an ammonia synthon in amination of acid chlorides
-
The use of formamide as a convenient source of ammonia has been explored for the direct transformation of acid chlorides to primary amides. Various aliphatic, alicyclic aromatic, and heterocyclic acid chlorides are converted to the corresponding carboxamides in good yields (75-94%). Copyright Taylor & Francis Group, LLC.
- Srinivasan,Manisankar
-
experimental part
p. 3538 - 3543
(2011/02/22)
-
- Discovering potent small molecule inhibitors of cyclophilin A using de novo drug design approach
-
This work describes an integrated approach of de novo drug design, chemical synthesis, and bioassay for quick identification of a series of novel small molecule cyclophilin A (CypA) inhibitors (1-3). The activities of the two most potent CypA inhibitors (3h and 3i) are 2.59 and 1.52 nM, respectively, which are about 16 and 27 times more potent than that of cyclosporin A. This study clearly demonstrates the power of our de novo drug design strategy and the related program LigBuilder 2.0 in drug discovery.
- Ni, Shuaishuai,Yuan, Yaxia,Huang, Jin,Mao, Xiaona,Lv, Maosheng,Zhu, Jin,Shen, Xu,Pei, Jianfeng,Lai, Luhua,Jiang, Hualiang,Li, Jian
-
supporting information; experimental part
p. 5295 - 5298
(2010/02/28)
-
- Process for the Preparation of a 2-Pyridylethylcarboxamide Derivative
-
Process for the preparation of a N-[2-(2-pyridinyl)ethyl]carbox-amide derivative of general formula (I) or a salt thereof 5 Intermediate of general formula (II) Intermediate of general formula (III).
- -
-
Page/Page column 10
(2008/06/13)
-
- Photolysis of Flutolanil Fungicide and the Effect of Some Photosensitizers
-
Photolysis of the fungicide flutolanil, 3'-isopropoxy-2-(trifluoromethyl)benzanilide, was investigated both in an aqueous solution and on solid surfaces (silica gel and glass) by irradiating with UV light under laboratory conditions.In an ethanolic aqueous solution, irradiation resulted in the formation of a major product and some other products .The latter is considered to have been formed by the reaction with an organic solvent.On the solid surfaces, the main photoproduct was 2'-amino-4'-isopropoxyphenyl 2-(trifluoromethyl)phenyl ketone, a product from the photo-Fries rearrangement reaction.Another photoproduct, 3'-hydroxy-2-(trifluoromethyl)benzanilide was obtained only on the glass surface, this desisopropylated compound not being detected under any other conditions.The photolysis of this fungicide, was accelerated more by carbonyl compounds such as benzophenone, acetophenone, flavone and xanthone than by dye photosensitizers like rose bengal, chlorophyllin and riboflavin.
- Tsao, Rong,Eto, Morifusa
-
p. 763 - 768
(2007/10/02)
-
