385-00-2Relevant academic research and scientific papers
Nanosheet-assembled microflower-like coordination polymers by surfactant-assisted assembly with enhanced catalytic activity
Han, Suzhen,Hu, Mingjun,Huang, Chao,Lu, Guizhen,Mi, Liwei,Qin, Na,Zhang, Ying-Ying,Zhu, Kaifang
, p. 7858 - 7863 (2020/12/04)
Tuning the morphology and size of coordination polymers (CPs) is an effective strategy to enable crystalline materials for desired applications. Herein, two CPs, named [Cd2(DBTP)(H2O)2]n (1) and {[Zn2(DBTP)(H2O)]·2.5H2O}n (2), were prepared by employing a rigid V-shaped and multidentate N-heterocyclic ligand 2,6-di(1H,2′H-[3,3′-bi(1,2,4-triazol)]-5′-yl)pyridine (H4DBTP) under solvothermal conditions. Their crystal morphologies and sizes were controlled by varying the type and the amount of surfactants. The morphology can be changed from bulk blocks to microflower-like hierarchical spheres assembled by nanosheets and the mean size of the microflowers is approximately 2 μm. Nanoscale 1a and 2a were further evaluated as heterogeneous catalysts for the conversion reactions of nitromethylbenzenes into benzoic acids. The results showed that nanoscale 2a is a more efficient catalyst than nanoscale 1a and their corresponding bulk counterparts.
Surfactant-assisted assembly of nanoscale zinc coordination compounds to enhance tandem conversion reactions in water
Huang, Chao,Zhu, Kaifang,Zhang, Yingying,Lu, Guizhen,Shao, Zhichao,Gao, Kuan,Mi, Liwei,Hou, Hongwei
supporting information, p. 16008 - 16016 (2019/11/13)
Precise control over the morphology and size of coordination polymers (CPs) is crucial for extending these inorganic-organic materials to many advanced applications, in particular for heterogeneous catalysis. In this work, two Zn-based CPs, {[Zn3(idbt)2(4,4′-dmbpy)2]·H2O}n (1) and {[Zn3(idbt)2(H2O)3]·H2O}n (2) (H3idbt = 5,5′-(1H-imidazole-4,5-diyl)-bis-(2H-tetrazole), 4,4′-dmbpy = 4,4′′-dimethyl-2,2′-bipyridine), were synthesized through solvothermal reactions. The morphologies and particle sizes of 1 and 2 could be controlled from large scale to nanoscale by regulating the amount of poly(vinyl alcohol) (PVA). Furthermore, for the conversion reactions of nitromethylbenzenes into benzoic acids, the catalytic properties of nanoscale 1 and 2 were much more efficient than those of large size of 1 and 2, because of the benefit of readily accessible active sites in the nanoscale sized particles, which provide a tunable and functionalizable platform for the conversion reaction by minimizing the diffusion distance but do little for the selectivity.
A biocatalytic method for the chemoselective aerobic oxidation of aldehydes to carboxylic acids
Knaus, Tanja,Tseliou, Vasilis,Humphreys, Luke D.,Scrutton, Nigel S.,Mutti, Francesco G.
supporting information, p. 3931 - 3943 (2018/09/11)
Herein, we present a study on the oxidation of aldehydes to carboxylic acids using three recombinant aldehyde dehydrogenases (ALDHs). The ALDHs were used in purified form with a nicotinamide oxidase (NOx), which recycles the catalytic NAD+ at the expense of dioxygen (air at atmospheric pressure). The reaction was studied also with lyophilised whole cell as well as resting cell biocatalysts for more convenient practical application. The optimised biocatalytic oxidation runs in phosphate buffer at pH 8.5 and at 40 °C. From a set of sixty-one aliphatic, aryl-Aliphatic, benzylic, hetero-Aromatic and bicyclic aldehydes, fifty were converted with elevated yield (up to >99%). The exceptions were a few ortho-substituted benzaldehydes, bicyclic heteroaromatic aldehydes and 2-phenylpropanal. In all cases, the expected carboxylic acid was shown to be the only product (>99% chemoselectivity). Other oxidisable functionalities within the same molecule (e.g. hydroxyl, alkene, and heteroaromatic nitrogen or sulphur atoms) remained untouched. The reaction was scaled for the oxidation of 5-(hydroxymethyl)furfural (2 g), a bio-based starting material, to afford 5-(hydroxymethyl)furoic acid in 61% isolated yield. The new biocatalytic method avoids the use of toxic or unsafe oxidants, strong acids or bases, or undesired solvents. It shows applicability across a wide range of substrates, and retains perfect chemoselectivity. Alternative oxidisable groups were not converted, and other classical side-reactions (e.g. halogenation of unsaturated functionalities, Dakin-Type oxidation) did not occur. In comparison to other established enzymatic methods such as the use of oxidases (where the concomitant oxidation of alcohols and aldehydes is common), ALDHs offer greatly improved selectivity.
Iodine catalyzed oxidation of alcohols and aldehydes to carboxylic acids in water: A metal-free route to the synthesis of furandicarboxylic acid and terephthalic acid
Hazra, Susanta,Deb, Mayukh,Elias, Anil J.
supporting information, p. 5548 - 5552 (2017/12/06)
A metal-free iodine/NaOH-catalyzed oxidation of alcohols and aldehydes has been developed for the practical synthesis of a wide range of carboxylic acids using water as the solvent. This transformation involves dehydrogenation of an alcohol, followed by a fast attack of water on an aldehyde. This method is mostly free from chromatographic purification, which makes it suitable for large-scale synthesis. The iodine species formed during the reaction as the active oxidation catalyst has been deduced as IO2- by control experiments. We also demonstrate a 10 gram scale synthesis of furandicarboxylic acid (FDCA) from HMF in good yield using our method.
A fluorine-containing tetrazine pyridine compound and its use
-
Paragraph 0013-0014; 0033; 0034, (2017/08/25)
The invention provides fluorine-containing tetrazine pyridine compounds disclosed as Formula I. The compounds have ultrahigh inhibiting and killing actions on harmful acarids and acarid ova, and can be used as an acaricide for controlling acarid harm in agriculture and forestry.
A fluorine-containing tetrazine pyrazoles acaricide
-
Paragraph 0036; 0037; 0038, (2017/08/25)
The invention provides fluorine-containing tetrazine pyrazol acaricide. The structure is shown as the formula I (please find the formula I in the specification). The compound has the super efficient restraining and killing effects on harmful mites and mite eggs and can be used as the acaricide for preventing and treating mite diseases in agriculture and forestry.
Synthesis method of 6-fluorosalicylic acid
-
Paragraph 0013; 0014; 0015, (2017/05/12)
The invention discloses a synthesis method of 6-fluorosalicylic acid, and belongs to the field of preparation of fine chemical compounds. The method includes the steps of mixing 2,6-difluorobenzonitrile, sodium hydroxide and water for reaction under the pressure of 0.25 MPa at the temperature of 150 DEG C, cooling and then adjusting the pH value of reaction liquid through acid liquor, taking out separated solid, washing and drying the solid, dissolving the solid in solvent for recrystallization, and obtaining 6-fluorosalicylic acid. The method is characterized in that the mixing molar ratio of 2,6-difluorobenzonitrile to sodium hydroxide to water is 1:3:10; the acid liquor for adjusting the pH value of the reaction liquid is a sulfuric acid aqueous solution and is used for adjusting the pH value to be 1; the solvent for recrystallization is an ethyl alcohol and water mixed solution. The method is low in production cost and high in yield.
Conversion of nitroalkanes into carboxylic acids via iodide catalysis in water
Marcé, Patricia,Lynch, James,Blacker, A. John,Williams, Jonathan M. J.
supporting information, p. 1013 - 1016 (2016/01/16)
We report a new method for the conversion of nitroalkanes into carboxylic acids that achieves this transformation under very mild conditions. Catalytic amounts of iodide in combination with a simple zinc catalyst are needed to give good conversions into the corresponding carboxylic acids.
A facile and rapid preparation of hydroxamic acids by hydroxylaminolysis using DBU as base
Beillard, Audrey,Bhurruth-Alcor, Yushma,Bouix-Peter, Claire,Bouquet, Karinne,Chambon, Sandrine,Clary, Laurence,Harris, Craig S.,Millois, Corinne,Mouis, Grégoire,Ouvry, Gilles,Pierre, Romain,Reitz, Arnaud,Tomas, Loic
supporting information, p. 2165 - 2170 (2016/05/02)
While there are many protocols for the preparation of hydroxamic acids from their corresponding carboxylic acid or carboxylic ester precursors, most use strong mineral bases that can lead to carboxylic acid impurities that can be difficult to remove using standard chromatographic techniques. This problem is exacerbated when the carbonyl group is hindered. Herein, we communicate a robust hydroxylaminolysis protocol for the preparation of hydroxamic acids in high yield and purity.
Potassium-alkyl magnesiates: Synthesis, structures and Mg-H exchange applications of aromatic and heterocyclic substrates
Baillie, Sharon E.,Bluemke, Tobias D.,Clegg, William,Kennedy, Alan R.,Klett, Jan,Russo, Luca,De Tullio, Marco,Hevia, Eva
supporting information, p. 12859 - 12862 (2014/12/11)
Using structurally well-defined dipotassium-tetra(alkyl)magnesiates, a new straightforward methodology to promote regioselective Mg-H exchange reactions of a wide range of aromatic and heteroaromatic substrates is disclosed. Contacted ion pair intermediates are likely to be involved, with K being the key to facilitate the magnesiation processes. This journal is
