685-87-0Relevant academic research and scientific papers
Orienting effect of the cage addends: The case of nucleophilic cyclopropanation of C2-C70(CF3)8
Apenova, Marina G.,Semivrazhskaya, Olesya O.,Borkovskaya, Eugenia V.,Belov, Nikita M.,Ioffe, Ilya N.,Markov, Vitaliy Yu.,Troyanov, Sergey I.,Lukonina, Natalia S.,Sidorov, Lev N.,Goryunkov, Alexey A.
, p. 1370 - 1378 (2015)
C2-C70(CF3)8 was found to be a very promising substrate in the Bingel and the Bingel-Hirsch reactions combining perfect regioselectivity with much higher reactivity compared to its analogs. The reactions with diethyl malonate yield a single isomer of the monoadduct C70(CF3)8[C(CO2Et)2] and a single C2-symmetrical bisadduct C70(CF3)8[C(CO2Et)2]2. The Bingel-Hirsch variation is particularly interesting in that it additionally affords, in a similar regioselective manner, the unexpected alkylated derivatives C70(CF3)8[CH(CO2Et)2]H and C70(CF3)8[C(CO2Et)2][CH(CO2Et)2]H. The novel compounds have been isolated and structurally characterized by means of 1H and 19F NMR spectroscopy as well as single-crystal X-ray diffraction. The mechanistic and regiochemical aspects of the reaction are explained with the aid of DFT calculations. Conventional vs. unconventional: Acceptor-derivatized fullerene substrates can exhibit an enhanced reactivity and regioselectivity in important organic reactions. Bingel and Bingel-Hirsch functionalization of C2-C70(CF3)8 are reported, which affords rapid and LUMO-directed regioselective formation of both conventional cyclopropanated and unusual alkylated products. The mechanistic and regiochemical aspects of the reaction are explained with the aid of the DFT calculations.
2-methoxyphenoxy pyrimidine antitumor compound as well as preparation method and application thereof
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Paragraph 0045-0047, (2021/05/12)
The invention belongs to the technical field of medicines, relates to a compound with anti-tumor activity and a specific chemical structure, and particularly relates to a 2-methoxyphenoxy pyrimidine compound as well as a preparation method and application thereof. The structural general formula of the 2-methoxyphenoxy pyrimidine compound is shown in the specification, wherein an R group is a hydrogen atom, or a 2-position monosubstituted fluorine atom, or 3-position and 4-position monosubstituted methyl, methoxy, fluorine atom, chlorine atom, bromine atom and iodine atom. Experimental research shows that the prepared 2-methoxyphenoxy pyrimidine compound shows a good result in an in-vitro anti-tumor activity test, has certain inhibitory activity on human malignant melanoma A375 cells, can be used for preparing anti-tumor drugs, and opens up a new way for developing new anti-tumor drugs. The preparation method provided by the invention is simple and feasible, relatively high in yield and easy for large-scale production.
Phenyl pyrimidinamine anti-tumor compound as well as preparation method and application thereof
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Paragraph 0045-0047, (2021/06/06)
The invention belongs to the technical field of medicines, relates to a compound with anti-tumor activity and a specific chemical structure, and particularly relates to a phenyl pyrimidinamine compound as well as a preparation method and application thereof. The structural general formula of the phenyl pyrimidinamine compound is shown in the specification, wherein an R group is a hydrogen atom, a 2-position monosubstituted fluorine atom, or 3-position and 4-position monosubstituted methyl, a fluorine atom, a chlorine atom and a bromine atom. Experimental research shows that the prepared phenyl pyrimidinamine compound shows a good result in an in-vitro anti-tumor activity test, can be used for preparing anti-tumor drugs, and opens up a new way for developing the anti-tumor drugs with an endothelin receptor as a new target. The preparation method provided by the invention is simple and feasible, higher in yield and easy for large-scale production.
NBS/DBU-Promoted One-Pot Three-Component Cycloaddition of Malonic Acid Derivatives, Nitrosoarenes, and Alkenes: Synthesis of Isoxazolidines
Li, Xing,Zheng, Leijie,Gong, Xiaolei,Chang, Honghong,Gao, Wenchao,Wei, Wenlong
, p. 1096 - 1107 (2021/01/14)
A general DBU-mediated one-pot three-component cycloaddition reaction of easily accessible malonic acid derivatives, nitrosoarenes, and alkenes has been successfully established with the aid of NBS to provide direct access to highly functionalized isoxazolidine derivatives with generally good to excellent yields, broad functional group tolerance, and excellent regio- and diastereo-selectivities under mild conditions. The mechanism study shows that the NBS-mediated formation of bromomalonic acid derivatives from malonic acid derivatives and DBU-promoted synthesis of nitrone intermediates via the reaction of bromomalonic acid derivatives with nitrosoarenes are key steps.
Novel Allosteric Inhibitors of Deoxyhypusine Synthase against Malignant Melanoma: Design, Synthesis, and Biological Evaluation
Li, Shuai,Li, Xin-Yang,Li, Yu-Heng,Lin, Qi-Qi,Liu, Kai-Li,Meng, Fan-Hao,Qian, Xin-Hua,Wang, De-Pu,Xue, Wen-Han
, p. 13356 - 13372 (2021/09/20)
Based on the novel allosteric site of deoxyhypusine synthase (DHPS), two series of 30 novel 5-(2-methoxyphenoxy)-2-phenylpyrimidin-4-amine derivatives as DHPS inhibitors were designed and synthesized. Among them, compound8m, with the best DHPS inhibitory potency (IC50= 0.014 μM), exhibited excellent inhibition against melanoma cells, which was superior to that of GC7. Besides, molecular docking and molecular dynamics (MD) simulations further proved that compound8mwas tightly bound to the allosteric site of DHPS. Flow cytometric analysis and enzyme-linked immunosorbent assay (ELISA) showed that compound8mcould inhibit the intracellular reactive oxygen species (ROS) level. Furthermore, by western blot analysis, compound8meffectively activated caspase 3 and decreased the expressions of GP-100, tyrosinase, eIF5A2, MMP2, and MMP9. Moreover, both Transwell analysis and wound healing analysis showed that compound8mcould inhibit the invasion and migration of melanoma cells. In thein vivostudy, the tumor xenograft model showed that compound8meffectively inhibited melanoma development with low toxicity.
Acridine Orange Hemi(Zinc Chloride) Salt as a Lewis Acid-Photoredox Hybrid Catalyst for the Generation of α-Carbonyl Radicals
Das, Sanju,De Sarkar, Suman,Mandal, Tanumoy
supporting information, (2021/12/10)
A readily accessible organic-inorganic hybrid catalyst is reported for the reductive fragmentation of α-halocarbonyl compounds. The robust hybrid catalyst is a self-stabilizing combination of ZnCl2 Lewis acid and acridine orange as the photoactive organic dye. Mechanistic specifics of this hybrid catalyst have been studied in detail using both photophysical and electrochemical experiments. A systematic study enabled the discovery of the appropriate Lewis acid for the effective LUMO stabilization of α-halocarbonyl compounds and thereby lowering of reduction potential within the range of a standard organic dye. This strategy resolves the issues like dehalogenative hydrogenation or homo-coupling of alkyl radicals by guiding the photoredox cycle through an oxidative quenching pathway. The cooperativity between the photoactive organic dye and the Lewis acid counterparts empowers functionalization with a wide range of coupling partners through efficient and controlled generation of alkyl radicals and serves as an appropriate alternative to the expensive late transition metal-based photocatalysts. To demonstrate the application potential of this cooperative catalytic system, four different synthetic transformations of α-carbonyl bromides were explored with broad substrate scopes.
Alkyl Halides via Visible Light Mediated Dehalogenation
Rathnayake, Manjula D.,Weaver, Jimmie D.
supporting information, p. 9681 - 9687 (2019/11/28)
Net selective bromination and chlorination of activated C-H bonds can be effected in generally high yield via a simple perhalogenation/dehalogenation sequence. The photochemical reductions require no photocatalyst, relying instead on the formation of an electron donor-acceptor complex of the substrate and reductant, or alternatively autophotocatalysis. Some reactions proceed despite any apparent photon absorption, serving as a cautionary tale for other photochemical reactions involving amines. Mechanistic experiments provide an explanation for this observation.
Synthetic routes for a variety of halogenated (chiral) acetic acids from diethyl malonate
Mazenauer, Manuel R.,Manov, Stole,Galati, Vanessa M.,Kappeler, Philipp,Stohner, Jürgen
, p. 55434 - 55440 (2018/04/05)
Chiral halomethane is the smallest stable molecule with a single asymmetric C-atom and halogenated acetic acids often serve as precursors. We focus on a synthetic route to synthesise chiral halogenated acetic acids with F, Cl, Br, and H/D isotopic substitution at the α-C-atom starting from diethyl malonate. This reactant is easily available, cheap and allows the obtainment of target acids in a few reaction steps with great versatility. Among all of the possible fully halogenated acetic acids (more than one hundred, which are, in principle, accessible by this route), there are only a small number of chiral halogenated acetic acids, which have been synthesized following the devised synthetic route.
Enantioselective cyclopropanation of (Z)-3-substituted-2-(4-pyridyl)-acrylonitriles catalyzed by Cinchona ammonium salts
Del Fiandra, Claudia,Moccia, Maria,Adamo, Mauro F. A.
supporting information, p. 3105 - 3111 (2016/03/19)
Cyclopropane esters holding two quaternary centres were prepared in high yields, complete diastereoselection and up to 83% ee. The reaction described herein entailed reacting (Z)-3-substituted-2-(4-pyridyl)-acrylonitrile, a reactive class of Michael acceptor, with 2-bromomalonate esters in the presence of Cinchona derived phase-transfer catalysts. The reaction allowed multi-gram preparation of the desired products.
Preparation method for 2-halogenated-1,3-dicarbonyl derivative
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Paragraph 0048, (2017/02/28)
The invention discloses a preparation method for a 2-halogenated-1,3-dicarbonyl derivative. The preparation method is suitable for wide 1,3-dicarbonyl derivatives. The raw materials are easy to obtain, and multiple varieties are achieved. The product obtained through the method is diversified in type, and can be directly used and used for other further reactions. According to the method, reaction conditions are gentle, the reaction operation and after-treatment process is simple, reaction time is short, the yield is high, pollution is low, and the preparation method is suitable for industrial production.
