119-67-5Relevant articles and documents
Prevention of manganese precipitation during the continuous selective partial oxidation of methyl aromatics with molecular oxygen in supercritical water
Fraga-Dubreuil, Joan,Garcia-Verdugo, Eduardo,Hamley, Paul A.,Perez, Eduardo,Pearson, Ian,Thomas, W. Barry,Housley, Duncan,Partenheimer, Walt,Poliakoff, Martyn
, p. 1866 - 1876 (2009)
Presented here is an investigation of the activity and recovery of the homogeneous manganese/bromide catalyst during the continuous flow oxidation of o-xylene, as model substrate, with molecular oxygen (O2) in supercritical water (scH2O). Two strategies are discussed for preventing catalyst precipitation, mainly in the form of oxides such as manganese(IV) oxide, The first strategy involves varying the manganese:bromide ratio using either manganese(II) acetate or manganese (II) bromide in the presence of hydrobromic and other acids. The results show that the effect of acidity and bromide concentration plays an important role in preventing the manganese/bromide catalyst from precipitating. The second strategy uses aromatic carboxylic acids in combination with the manganese/bromide catalyst, particularly benzoic acid, which improves the catalyst recovery dramatically over a certain range of acid concentrations. Our studies show how the presence of an organic acid and/or its precursors is important in stabilising the catalyst. Our results are rationalised on the basis of a tentative reaction mechanism.
Selectivity in catalytic diol electrooxidation using a polypyridine ru(iv) complex
Navarro, Marcelo,De Giovani, Wagner F.,Romero, Jose R.
, p. 851 - 857 (1991)
1,2-, 1,3-, and 1,4-Butanediols and phthatic alcohol were oxidized electrocatalytically using the polypyridine [(bpy)(trpy)RuO]2+ complex (1) as oxidant under different conditions: concentration of 1, pH, and temperature. By controlling the number of coulombs passed through the electrolytic cell, it was possible to obtain selective reactions. 1-Hydroxy-2-butanone,1-hydroxy-3-butanone, γ-butyrolactone, phthalide, phtalic aldehyde, and phthalic acid were the products obtained by controlled potential electrolysis from these substrates, with yields ranging from 41 to 89%.
Facile construction of pyrrolo[1,2-: B] isoquinolin-10(5 H)-ones via a redox-amination-aromatization-Friedel-Crafts acylation cascade reaction and discovery of novel topoisomerase inhibitors
Wu, Shanchao,Liu, Na,Dong, Guoqiang,Ma, Lin,Wang, Shengzheng,Shi, Wencai,Fang, Kun,Chen, Shuqiang,Li, Jian,Zhang, Wannian,Sheng, Chunquan,Wang, Wei
, p. 9593 - 9596 (2016)
An efficient redox-amination-aromatization-Friedel-Crafts acylation cascade process from trans-4-hydroxyproline and 2-formylbenzoic acids has been developed for the synthesis of pyrrolo[1,2-b]isoquinolin-10(5H)-ones. Compound 3h was identified as a new potent dual topoisomerase I/II inhibitor.
Oxidation of benzyl alcohol by pyridinium dichromate in acetonitrile. Using the paralmeta ratio of substituent effects for mechanism elucidation
Kabilan,Girija,Reis, Joao Carlos R.,Segurado, Manuel A.P.,De Oliveira, Jaime D. Gomes
, p. 1151 - 1157 (2002)
Rate constants were measured for the oxidation reaction of benzyl alcohol and twenty-five ortho-, recta- and para-monosubstituted derivatives in the temperature range 293-323 K at intervals of 10 K. The kinetics were followed spectrophotometrically in dry acetonitrile acidified with trichloroacetic acid (TCA) using pyridinium dichromate (PDC) as oxidising agent under pseudo-first-order conditions with respect to PDC. Benzaldehyde is the only oxidation product and no reaction takes place without TCA. From good linear Eyring plots activation enthalpies Δ?H° and entropies Δ?S° are calculated. For ortho-substituted benzyl alcohols high Δ?H° values and small negative Δ?S° values point to an ortho effect on the rate-determining step. Using the tetralinear approach to substituent effects, the average value λ = 1.09 ± 0.05 for the para/meta ratio of inductive or Electra effects is obtained and negative Hammett reaction constants decreasing in magnitude with increasing temperature are found. A mechanism implicating the prior acid-catalysed formation of neutral benzyl hydrogen dichromate ester followed by intramolecular proton transfer is proposed. Modelling of parameter λ in terms of the electrostatic theory showed its experimental value to be consistent with the ratio of electric potentials generated in the immediate vicinity of the nearest chromium atom by dipolar substituents introduced in the aromatic ring on para and meta positions. At a molecular level the oxidative, rate-determining step is suggested to be triggered by the retraction or shrinkage of electron pairs from sigma bonds in Cr2VI species to non-bonding orbitals in unstable CrIV-O-CrVI species. In contrast with past interpretations, an electrochemical approach is used to explain negative values for the Hammett reaction constant.
Industrial synthesis method of o-aldehyde phenyl fatty acid
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Paragraph 0074; 0076; 0077; 0083; 0085; 0086; 0088; 0090, (2020/01/08)
The invention provides an industrial synthesis method of o-aldehyde phenyl fatty acid, which comprises the following steps: by using aromatic lactone or o-methylphenyl fatty acid as a raw material, carrying out halogenation reaction and hydrolysis to obtain the o-aldehyde phenyl fatty acid. In the method, halogen is used in the production process; however, if haloid acid or haloid salt formed byhydrolysis is directly discharged to the environment, the cost of a halogen source accounts for most of the cost of the whole process, and severe environmental pollution is caused; by means of the method, an activated halogen source can be obtained in real time by adding a specific oxidant in the reaction process, so that the closed cycle of halogen elements is realized by means of the subsequenthydrolysis process; therefore, a large amount of raw material cost is saved on the whole, environmental pollution is reduced, the product yield is high, and large-scale production is facilitated.
Synthesis method of O-formyl benzoic acid
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Paragraph 0009 0011-0012, (2019/12/25)
The invention discloses a synthesis method of o-formyl benzoic acid. The synthesis method includes the following steps that (1) 20 mL of o-dimethyl benzene is taken and placed in a reactor, the reactor is heated to 130 to 135 DEG C, and DMF, a catalyst and a cocatalyst are added in turn; (2) reaction liquid is cooled to the room temperature, and an obtained clear colorless crystal is o-methyl benzonitrile; and (3) the o-methyl benzonitrile is placed in the reactor, and heated to 110 to 115 DEG C, the DMF, the catalyst and the cocatalyst are added, oxygen intake is controlled to be 900 mL/min,hydrogen intake is controlled to be 100 mL/min, reaction is conducted for 2 to 3 h, and the o-formyl benzoic acid can be obtained through hydrolysis of obtained white crystalline powder under the acidic condition. The o-methyl benzonitrile is synthesized by a one-step method of liquid phase ammoxidation of o-xylene under normal pressure, then the o-formyl benzoic acid is synthesized by further oxidation of the o-methyl benzonitrile, the yield is high, the purity of product is high, and the requirements on equipment are low.
Synthesis of chiral isoindolinones via asymmetric propargylation/lactamization cascade
Meng, Jiao-Long,Jiao, Tang-Qian,Chen, Ya-Heng,Fu, Rui,Zhang, Shu-Sheng,Zhao, Qian,Feng, Chen-Guo,Lin, Guo-Qiang
supporting information, p. 1564 - 1567 (2018/03/23)
A Zn-mediated propargylation/lactamization cascade reaction with chiral 2-formylbenzoate derived N-tert-butanesulfinyl imines was realized, which provided a practical and efficient method for the synthesis of chiral isoindolinones. High diastereoselectivities (up to 97:3 dr) and good reaction yields were observed for most examined cases.
Cu/Fe Catalyzed Intermolecular Oxidative Amination of Benzylic C-H Bonds
Liu, Cong,Zhang, Qi,Li, Hongbo,Guo, Shuangxi,Xiao, Bin,Deng, Wei,Liu, Lei,He, Wei
supporting information, p. 6208 - 6212 (2016/05/09)
We report a Cu/Fe co-catalyzed Ritter-type C-H activation/amination reaction that allows efficient and selective intermolecular functionalization of benzylic C-H bonds. This new reaction is featured by simple reaction conditions, readily available reagents and general substrate scope, allowing facile synthesis of biologically interesting nitrogen containing heterocycles. The Cu and Fe salts were found to play distinct roles in this cooperative catalysis. With a little help: A Ritter-type intermolecular amination of benzylic C-H bonds with acetonitrile, co-catalyzed by CuII/FeIII is reported. A wide array of biologically interesting nitrogen containing heterocycles was prepared from 2-alkyl benzoic acids and heteroaromatic carboxylic acids under operationally simple conditions. The Cu and Fe salts were found to play distinct roles in this cooperative catalysis.
Structure-based design of potent human dihydroorotate dehydrogenase inhibitors as anticancer agents
Song, Wenlin,Li, Shiliang,Tong, Yi,Wang, Jiawei,Quan, Lina,Chen, Zhuo,Zhao, Zhenjiang,Xu, Yufang,Zhu, Lili,Qian, Xuhong,Li, Honglin
supporting information, p. 1441 - 1448 (2016/07/21)
It has been proven that inhibiting human dihydroorotate dehydrogenase (hDHODH) restricts the growth of rapidly proliferating cells, thus hDHODH can be developed as a promising target for the treatment of immunological disease and cancer. Here, a succession of substituted hydrazino-thiazole derivatives were designed, synthesized, and biologically evaluated through structure-based optimization, of which compound 22 was the most potent inhibitor of hDHODH with an IC50 value of 1.8 nM. Furthermore, 22 exhibited much better antiproliferative activity than brequinar, both in HCT-116 and BxPC-3 cancer cell lines. Flow cytometry analysis revealed that 22 induced S phase cell cycle arrest and promoted induction of apoptosis. All results established a proof that blocking the pyrimidine de novo synthesis pathway by inhibiting the rate-limiting enzyme hDHODH is an attractive therapy for cancer.
Enantioselective addition of arylboronic acids to methyl 2-formylbenzoates by using a ruthenium/Me-BIPAM catalyst for synthesis of chiral 3-aryl-isobenzofuranones
Yohda, Masaaki,Yamamoto, Yasunori
, p. 10874 - 10880 (2015/11/17)
Ruthenium/Me-BIPAM-catalyzed asymmetric addition of arylboronic acids to methyl 2-formylbenzoates afforded chiral 3-aryl-isobenzofuranones. [RuCl2(p-cymene)]2/Me-BIPAM and RuCl2(PPh3)3/Me-BIPAM catalyst systems tolerate a variety of functional groups and give high yields with high enantioselectivities.
