14704-41-7Relevant academic research and scientific papers
Preparation method of dinotefuran
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Paragraph 0013; 0063-0068, (2021/08/07)
The invention provides a preparation method of dinotefuran, and belongs to the field of organic synthesis. The invention provides a preparation method of dinotefuran, which is characterized by comprising the following steps: step 1, adding a compound I, a compound II and a solvent into a reaction container, heating to 50 DEG C which is the reflux temperature of the solvent, reacting for 1-24 hours, then adding tetrahydrofuran-3-methylamine, and continuously reacting for 1-24 hours to obtain a reaction solution; and 2, cooling the reaction solution to 0-20 DEG C, standing, filtering, separating the solid and filtrate, and purifying the solid to obtain dinotefuran, wherein the structural formula of the compound I is shown in the specification, the structural formula of the compound II is shown in the specification, and R1 and R2 are independently selected from any one of H, C1-C5 alkyl and C1-C5 alkyl substituted by at least one halogen atom. According to the invention, a brand new dinotefuran synthesis route is developed, the synthesis route is greatly shortened, and the production efficiency is improved.
[3+2] Cycloaddition reactions of 1-substituted 3,3,3-trifluoropropenes with diazo compounds and nitrilimines – synthesis of pyrazolines and pyrazoles
Маrkitanov, Yuriy N.,Тimoshenko, Vadim М.,Мykhaylychenko, Sergiy S.,Rusanov, Eduard B.,Khyzhan, Alexandr I.,Shermolovich, Yuriy G.
, p. 1107 - 1115 (2022/01/12)
[Figure not available: see fulltext.] 1,3-Dipolar cycloaddition reactions of 3,3,3-trifluoropropene derivatives containing a sulfonyl, sulfamide, or sulfoximine substituent in position 1 with diazomethane proceed with the formation of 3-substituted 4-(trifluoromethyl)-4,5-dihydro-1H-pyrazoles and 3-(trifluoromethyl)-1H-pyrazole, whereas reactions with ethyl diazoacetate and 2,2,2-trifluorodiazoethane lead to the formation of isomeric 5(3)-substituted 4-trifluoromethyl-3,4(4,5)-dihydro-2(1)H-pyrazoles and 4-substituted 5-(trifluoromethyl)-4,5-dihydro-1Hpyrazoles, the stability of which depends on the nature of the heteroatomic substituent. The cycloaddition of 1-sulfonyl- and 1-sulfamoylsubstituted derivatives of 3,3,3-trifluoropropene to C-carbethoxy-N-phenylnitrilimine gives rise to 4-substituted ethyl 1-phenyl-5-(trifluoromethyl)-4,5-dihydro-1H-pyrazole-3-carboxylates and ethyl 1-phenyl-4-(trifluoromethyl)-1H-pyrazole-3-carboxylate.
Trifluoromethylated 3-(Pyrazol-1-yl)propanamide (PPA) Ligands
Liebing, Phil,Edelmann, Frank T.
, (2020/09/09)
The new PPA ligands 3-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]propanamide (CF3MePPA; 3) and 3-[3,5-bis(trifluoromethyl)-1H-pyrazol-1-yl]propanamide ((CF3)2PPA; 4) were synthesized by Aza-Michael addition of the specific pyrazole derivatives to acrylamide. Both products were characterized by elemental analyses, IR and NMR spectroscopy, and mass spectrometry. X-Ray structure determination of 3 revealed the presence of a one-dimensional hydrogen-bonded structure in the solid state. The ligating ability of the new ligands towards PdCl2 was studied, showing that 3 behaves similar to Me2PPA and reacts cleanly with PdCl2 to afford the sparingly soluble complex PdCl2(CF3MePPA-κN)2. By contrast, the donor ability of pyrazolyl group in 4 was found to be considerably reduced, thus resulting in the formation of the unusual complex PdCl2{(CF3)2PPA-κN}{(CF3)2PPA-κO}.
Tris(pyrazolyl)borate Cobalt-Catalyzed Hydrogenation of C=O, C=C, and C=N Bonds: An Assistant Role of a Lewis Base
Lin, Yang,Zhu, De-Ping,Du, Yi-Ran,Zhang, Rui,Zhang, Suo-Jiang,Xu, Bao-Hua
supporting information, p. 2693 - 2698 (2019/04/25)
The combination of tris(pyrazolyl)borate cobalt complexes and Lewis base is developed as an efficient catalyst precursor in the homogeneous hydrogenation. A broad substrate scope including carbonyls, alkenes, enamines, and imines is reduced with 60 atm of H2 at 60 °C. Mechanistic studies support the hydrogenation operates through a frustrated Lewis pair (FLP)-like reduction process. These results highlight the development of novel non-noble metal catalytic processes, when combined with the diverse small molecule activation chemistry associated with FLPs.
Method for breaking C-N bond through biomimetic catalysis in aryl nitrogen-containing compound
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Paragraph 0027; 0028, (2018/09/21)
The invention discloses a method for breaking a C-N bond through biomimetic catalysis in an aryl nitrogen-containing compound. A reaction system for breaking the C-N bond in the aryl nitrogen-containing compound through metalloporphyrin mimic enzyme biomimetic catalysis is used, and the preparation of the catalyst and the optimization of the reaction system are involved. Iron porphyrin, manganeseporphyrin and cobalt porphyrin are adopted as mimetic enzymes and H2O2 is used as an oxidant to respectively break the C-N bonds of arylpyrazole derivatives with different structures through catalyst,the yield of a nitrogen heterocyclic product can reach 15.2% to the largest content, and the yield is 4 times of that of bio-enzyme catalysis, and is close to the yield (20%) of cerium ammonium nitrate oxidation. The method has the advantages of simplicity, mildness, economy, and greenness compared with conventional oxidants or transition metal catalyst systems.
Biomimetic Cleavage of Aryl–Nitrogen Bonds in N-Arylazoles Catalyzed by Metalloporphyrins
Yu, Zongjiang,Zhai, Guoqing,Xian, Mo,Lu, Ming,Wang, Pengcheng,Jiang, Tao,Xu, Chao,Sun, Weizhi
, p. 2636 - 2642 (2018/06/20)
The cleavage of C–N single bonds of N-containing compounds provides either an excellent nitrogen source or an excellent carbon source. In this study, an efficient metalloporphyrins/H2O2 cleavage of C–N bonds of arylpyrazoles was investigated. The effects of different factors, including different catalysts, catalyst dosages, H2O2 dosages, reaction temperature and reaction time were studied. The experimental results showed that the optimal catalyst was FeTPPCl, and the yield of pyrazole derivatives could reach up to 12.3%, which was fourfold higher than hemin catalyzed reaction and closed to ceric ammonium nitrate catalyzed reaction, respectively. Compared with transition-metal-catalyzed and strong-oxidization cleavage of C–N bonds, this protocol is characterized by environmentally-friendly, stable, mild reaction conditions and simplified operation procedures. Graphical Abstract: [Figure not available: see fulltext.].
New efficient synthetic routes to trifluoromethyl substituted pyrazoles and corresponding β-diketones
Grünebaum, Mariano,Buchheit, Annika,Günther, Christina,Wiemh?fer, Hans-D.
supporting information, p. 1555 - 1559 (2018/03/29)
An improved and more efficient synthesis procedure for trifluoromethyl substituted pyrazoles, namely 3,5-bis(trifluoromethyl)-1H-pyrazole (1a), 5-(pentafluoroethyl)-3-(trifluoromethyl)-1H-pyrazole (1b), 5-(heptafluoropropyl)-3-(trifluoromethyl)-1H-pyrazol
Filling the gap: Chemistry of 3,5-bis(trifluoromethyl)-1H-pyrazoles
Maspero, Angelo,Giovenzana, Giovanni B.,Monticelli, Damiano,Tagliapietra, Silvia,Palmisano, Giovanni,Penoni, Andrea
experimental part, p. 53 - 57 (2012/06/30)
Pyrazoles represent important building blocks for the preparation of bioactive compounds and a large variety of materials, due to their rich coordination chemistry. Unusual and interesting properties may be imparted to molecules embodying highly fluorinated pyrazoles, but to date only few examples of polyfluorinated pyrazoles have been described. In this work we report an improved preparation of 3,5-bis(trifluoromethyl)-1H-pyrazole, the subsequent transformation into hitherto unknown 4-functionalized (F, Cl, Br, I, NO 2, NH2) derivatives and the evaluation of selected chemical and physical properties of these compounds.
"Reported, but still unknown." A closer look into 3,4-bis- and 3,4,5-tris(trifluoromethyl)pyrazoles
Gerus, Igor I.,Mironets, Roman V.,Kondratov, Ivan S.,Bezdudny, Andrei V.,Dmytriv, Yurii V.,Shishkin, Oleg V.,Starova, Viktoriia S.,Zaporozhets, Olga A.,Tolmachev, Andrey A.,Mykhailiuk, Pavel K.
experimental part, p. 47 - 56 (2012/03/10)
Straightforward practical synthetic approaches to 3,4-bis- and 3,4,5-tris(trifluoromethyl)pyrazoles have been developed. The key step of the both syntheses is a transformation of the carboxylic group in a pyrazole core into the trifluoromethyl group by sulfur tetrafluoride. The elaborated synthetic protocols allow gram-scale preparation of the target products. The obtained compounds are comprehensively characterized by means of crystallographic analysis, determination of pKa values and fluorescence measurements.
High-Yield Synthesis of Sodium, Potassium, and Thallium Hydrotrisborates and the X-Ray Crystal Structure of borato>thallium(I)
Renn, Oliver,Venanzi, Luigi M.,Marteletti, Arianna,Gramlich, Volker
, p. 993 - 1000 (2007/10/02)
An improved synthesis of 3,5-bis(trifluoromethyl)pyrazole (1) is described.This compound was used for the high-yield syntheses of the tris(pyrazolyl)borates Na (2a) and the corresponding potassium salt, 2b, starting from 1 and NaBH4 and KBH4, respectively.A convenient route to the corresponding thallium(I) salt, 2c, using thallium(I) acetate and either 2a or 2b in CHCl3, is also described.The sodium (3a), potasium (3b), and thallium (3c) salts of bis(pyrazolyl)borate were also prepared.The above pyrazolylborates were characterized by 1H-, 13C-, 19F-, and 11B-NMR spectroscopy.The X-ray crystal structure of the thallium derivate 2c was determined.The compound crystallizes in the monoclinic space group P21/m with a = 8.248(9) Angstroem, b = 15.034(12) Angstroem, c = 9.243(8) Angstroem, β = 100.10(7) deg, Z = 2.The T1-atom adopts a pyramidal geometry with respect to the three N-atoms.However, two T1-N distances (2.725(7) Angstroem) are longer than the third (2.675(10) Angstroem).
