437-81-0Relevant articles and documents
Latent Nucleophilic Carbenes
Marchenko, Anatoliy,Koidan, Georgyi,Hurieva, Anastasiya,Shvydenko, Kostiantyn,Rozhenko, Alexander B.,Rusanov, Eduard B.,Kyrylchuk, Andrii A.,Kostyuk, Aleksandr
, p. 373 - 385 (2021/12/27)
Using DFT and ab initio calculations, we demonstrate that noncyclic formamidines can undergo thermal rearrangement into their isomeric aminocarbenes under rather mild conditions. We synthesized the silylformamidine, for which the lowest activation energy in this process was predicted. Experimental studies proved it to serve as a very reactive nucleophilic carbene. The reactions with acetylenes, benzenes, and trifluoromethane proceeded via insertion into sp, sp2, and spCH bonds. The carbene also reacted with the functional groups, such as CHO, COR, and CN at double or triple bonds, displaying high mobility of the trimethylsilyl group. The obtained silylformamidine can be considered as a latent nucleophilic carbene. It can be prepared in bulk quantities, stored, and used when the need arises. Calculation results predict similar behavior for some other silylated formamidines and related compounds.
Method for efficiently synthesizing fluorine-containing compound
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Paragraph 0071-0073, (2021/06/26)
The invention discloses a method for efficiently synthesizing a fluorine-containing compound, and relates to the field of fluorine-containing compound synthesis. The method is a method for generating a corresponding fluorine atom substituted fluorine-containing compound by reacting aromatic chloride or activated chloride serving as a raw material with potassium fluoride under the action of a novel catalyst. The method disclosed by the invention has the advantages of good product selectivity, high efficiency, mild reaction conditions, simplicity and convenience in operation, convenience in application and the like.
A Magnetically Recyclable Palladium-Catalyzed Formylation of Aryl Iodides with Formic Acid as CO Source: A Practical Access to Aromatic Aldehydes
You, Shengyong,Zhang, Rongli,Cai, Mingzhong
, p. 1962 - 1970 (2021/01/25)
A magnetically recyclable palladium-catalyzed formylation of aryl iodides under CO gas-free conditions has been developed by using a bidentate phosphine ligand-modified magnetic nanoparticles-anchored- palladium(II) complex [2P-Fe 3O 4@SiO 2-Pd(OAc) 2] as catalyst, yielding a wide variety of aromatic aldehydes in moderate to excellent yields. Here, formic acid was employed as both the CO source and the hydrogen donor with iodine and PPh 3as the activators. This immobilized palladium catalyst can be obtained via a simple preparative procedure and can be facilely recovered simply by using an external magnetic field, and reused at least 9 times without any apparent loss of catalytic activity.
Synthesis of 2, 6 - difluoro phenyl -1 - (4, 5 - [...]) -3 - ketone to make a new method
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Paragraph 0040-0044, (2019/04/14)
The invention discloses a method for synthesizing 2, 6 - difluoro phenyl - 1 - (4, 5 - [...]) - 3 - ethyl ketone of the new method. This synthetic route avoids the synthetic intermediate 1, 3 - difluoro - 2 - steps of styrene, overcome prior art intermediate volatile not easy to store, and due to the synthetic process needs to be used sodium hydride synthesis of operation and great danger of defect, so that the synthesis process is more suitable for large-scale production; the synthetic route higher yield, and the final target 2, 6 - difluoro phenyl - 1 - (4, 5 - [...]) - 3 - ethyl ketone through re-crystallization mode is purified, high purity 98%; and this synthetic route uses the raw materials of the commercial production of the raw material, cheap and easy to obtain.
Pd-Catalyzed, ortho C-H Methylation and Fluorination of Benzaldehydes Using Orthanilic Acids as Transient Directing Groups
Chen, Xiao-Yang,Sorensen, Erik J.
supporting information, p. 2789 - 2792 (2018/03/08)
The direct, Pd-catalyzed ortho C-H methylation and fluorination of benzaldehydes have been accomplished using commercially available orthanilic acids as transient directing groups. In these reactions, the 1-fluoro-2,4,6-trimethylpyridinium salts can be either a bystanding F+ oxidant or an electrophilic fluorinating reagent. An X-ray crystal structure of a benzaldehyde ortho C-H palladation intermediate was obtained using triphenylphosphine as the stabilizing ligand.
A 2, 6 - difluoro toluene of continuous oxidation to prepare 2, 6 - difluorobenzaldehyde method (by machine translation)
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Paragraph 0026; 0028; 0030; 0032; 0034; 0036; 0038; 0040, (2017/08/29)
The invention relates to a 2, 6 - difluoro toluene of continuous oxidation to prepare 2, 6 - difluorobenzaldehyde method, which belongs to the technical field of organic synthesis process. The method is to 2, 6 - difluoro toluene compound as a raw materia
Barbier Continuous Flow Preparation and Reactions of Carbamoyllithiums for Nucleophilic Amidation
Ganiek, Maximilian A.,Becker, Matthias R.,Berionni, Guillaume,Zipse, Hendrik,Knochel, Paul
supporting information, p. 10280 - 10284 (2017/08/07)
An ambient temperature continuous flow method for nucleophilic amidation and thioamidation is described. Deprotonation of formamides by lithium diisopropylamine (LDA) affords carbamoyllithium intermediates that are quenched in situ with various electrophi
DIRECT DYES AND COMPOSITION COMPRISING THE DYES
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Page/Page column 32, (2016/07/27)
The present invention relates to novel direct dyes and compositions comprising them for dyeing keratin fibers especially human hair. The novel dyes of the present invention have benzothiophene structure providing intensive and homogeneous dyeing on kerati
Polyoxometalate-Intercalated Layered Double Hydroxides as Efficient and Recyclable Bifunctional Catalysts for Cascade Reactions
Liu, Kai,Xu, Yanqi,Yao, Zhixiao,Miras, Haralampos N.,Song, Yu-Fei
, p. 929 - 937 (2016/03/15)
The polyoxometalate (POM) intercalated layered double hydroxides (LDHs) have been widely used as heterogeneous catalysts. However, the application of POM-LDHs as bifunctional catalysts for cascade reaction has seldom been studied compared to the noble-metal-based catalysts. Herein, a series of POM-LDHs catalysts of Tris-LDH-X4(PW9)2 (X=Mn, Fe, Co, Ni, Cu, and Zn; Tris=Tris(hydroxymethtyl)aminomethane) have been prepared. The efficacy of Tris-LDH-Zn4(PW9)2 as efficient bifunctional catalyst has been demonstrated for cascade reactions involving oxidation of benzyl alcohol to benzaldehyde followed by Knoevenagel condensation with ethyl cyanoacetate to produce benzylidene ethyl cyanoacetate. The combination of POM's redox/acidic sites and LDHs's basic sites led to a composite catalyst with excellent activity (99 %) and selectivity (≥99 %) under mild and soluble-base-free conditions. This work offers a new design strategy for the fabrication of efficient bifunctional catalysts for the promotion of one-pot cascade reactions.
Green and Efficient: Iron-Catalyzed Selective Oxidation of Olefins to Carbonyls with O2
Gonzalez-De-Castro, Angela,Xiao, Jianliang
supporting information, p. 8206 - 8218 (2015/07/15)
A mild and operationally simple iron-catalyzed protocol for the selective aerobic oxidation of aromatic olefins to carbonyl compounds is described. Catalyzed by a Fe(III) species bearing a pyridine bisimidazoline ligand at 1 atm of O2, α- and β-substituted styrenes were cleaved to afford benzaldehydes and aromatic ketones generally in high yields with excellent chemoselectivity and very good functional group tolerance, including those containing radical-sensitive groups. With α-halo-substituted styrenes, the oxidation took place with concomitant halide migration to afford α-halo acetophenones. Various observations have been made, pointing to a mechanism in which both molecular oxygen and the olefinic substrate coordinate to the iron center, leading to the formation of a dioxetane intermediate, which collapses to give the carbonyl product. (Chemical Equation).