10072-09-0Relevant articles and documents
Supramolecular Catalysis of Acyl Transfer within Zinc Porphyrin-Based Metal-Organic Cages
Li, Lili,Yang, Linlin,Li, Xuezhao,Wang, Jing,Liu, Xin,He, Cheng
supporting information, p. 8802 - 8810 (2021/06/28)
To illustrate the supramolecular catalysis process in molecular containers, two porphyrinatozinc(II)-faced cubic cages with different sizes were synthesized and used to catalyze acyl-transfer reactions between N-acetylimidazole (NAI) and various pyridylcarbinol (PC) regioisomers (2-PC, 3-PC, and 4-PC). A systemic investigation of the supramolecular catalysis occurring within these two hosts was performed, in combination with a host-guest binding study and density functional theory calculations. Compared to the reaction in a bulk solvent, the results that the reaction of 2-PC was found to be highly efficient with high rate enhancements (kcat/kuncat = 283 for Zn-1 and 442 for Zn-2), as well as the different efficiencies of the reactions with various ortho-substituted 2-PC substrates and NAI derivates should be attributed to the cages having preconcentrated and preoriented substrates. The same cage displayed different catalytic activities toward different PC regioisomers, which should be mainly attributed to different binding affinities between the respective reactant and product with the cages. Furthermore, control experiments were carried out to learn the effect of varying reactant concentrations and product inhibition. The results all suggested that, besides the confinement effect caused by the inner microenvironment, substrate transfer, including the encapsulation of the reactant and the release of products, should be considered to be a quite important factor in supramolecular catalysis within a molecular container.
Proton-exchanged montmorillonite-mediated reactions of hetero-benzyl acetates: Application to the synthesis of Zafirlukast
Yang, Lei,Chen, Xuan,Ni, Kaidong,Li, Yuansheng,Wu, Jianhong,Chen, Weilin,Ji, Yin,Feng, Lili,Li, Fei,Chen, Dongyin
supporting information, (2020/06/28)
Proton-exchanged montmorillonite (H-mont) with outstanding surface characteristics can provide abundant acidic sites in the mesopores, and serve as an efficient heterogeneous catalyst for the synthesis of heterocycle-containing diarylmethanes via Friedel-Crafts-like alkylation of (hetero)arenes by heterobenzyl acetates under mild reaction conditions without requiring any additives or an inert atmosphere. Using this strategy, the gram-scale synthesis of indole-containing diarylmethane 13 has been accomplished in good yield for the preparation of Zafirlukast. In addition, H-mont can be applied to the nucleophilic substitution reactions of heterobenzyl acetate 5p with a variety of alcohols and 1,3-dicarbonyl compounds.
A 3 - pyridine formaldehyde synthetic method
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Paragraph 0032; 0034; 0037; 0039; 0042; 0044, (2019/05/28)
The present invention relates to machine the chemical field, in particular to a 3 - pyridine formaldehyde synthetic method, comprises the following steps: 1, to 3 - methyl pyridine as raw materials, under acidic conditions, through the oxidation reaction
Synthesis and characterization of MCM-41@XA@Ni(II) as versatile and heterogeneous catalyst for efficient oxidation of sulfides and acetylation of alcohols under solvent-free conditions
Nazarzadeh, Somayeh,Ghorbani-Choghamarani, Arash,Tahanpesar, Elham
, p. 649 - 659 (2018/01/28)
Herein, Ni(II) immobilized on modified mesoporous silica MCM-41 was designed and synthesized via a facile sequential strategy. The structure of the catalyst was characterized by X-ray diffraction. The thermal property of the as-synthesized materials was studied using thermogravimetric-differential thermal analysis. The average particles size and morphology of MCM-41@XA@Ni(II) were investigated using scanning electron microscopy and transmission electron microscopy. This nanostructure catalyst was effective for the selective oxidation of sulfides and acetylation of alcohols in solvent-free conditions. The easy recyclability of the catalyst and their complete chemoselectivity toward the sulfur group of substrates in the oxidation of sulfides are important “green” attributes of this catalyst.
Synthetic method of 3-pyridylaldehyde
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Paragraph 0032; 0034; 0039; 0044, (2017/11/18)
The invention relates to the field of organic chemistry, in particular to a synthetic method of 3-pyridylaldehyde. The synthetic method comprises the following steps: 1, taking 3-methyl pyridine as a raw material and obtaining 3-pyridine nitrogen oxide through oxidation reaction under an acidic condition; 2, synthesizing the 3-pyridine nitrogen oxide into acetic acid-3-pyridine methyl ester through acetic anhydride rearrangement; 3, hydrolyzing the acetic acid-3-pyridine methyl ester to obtain 3-pyridine methanol; 4, performing oxidation reaction on the 3-pyridine methanol to obtain 3-pyridylaldehyde. After the synthetic method is adopted, the 3-methyl pyridine is used as the raw material, and the 3-pyridine methanol is obtained through N-oxidation, rearrangement and hydrolyzation and is further oxidized to obtain the 3-pyridylaldehyde. The synthetic method provided by the invention is high in total yield, low in raw material price, short in reaction time, mild in condition, and simple in process operation.
An Elastic Monolithic Catalyst: A Microporous Metalloporphyrin-Containing Framework-Wrapped Melamine Foam for Process-Intensified Acyl Transfer
Wu, Keyi,Guo, Jia,Wang, Changchun
supporting information, p. 6013 - 6017 (2016/05/19)
The advent of conjugated microporous polymers (CMPs) has had significant impact in catalysis. However, the presence of only micropores in these polymers often imposes diffusion limitations, which has resulted in the low utilization of CMPs in catalytic reactions. Herein, the preparation of a foam-supporting CMP composite with interconnective micropores and macropores and elastic properties is reported. Metalloporphyrin-based CMP organogels are synthesized within the melamine foam by a room-temperature oxidative homocoupling reaction of terminal alkynes. Upon drying, the CMP-based xerogels tightly wrap the framework skeletons of the foam, while the foam cells are still open to allow for the preservation of elasticity and macroporosity. Such a hierarchical structure is efficient for acyl transfer, facilitates substrate diffusion within interpenetrative macropores and micropores, and could be used to intensify catalytic processes.
Pyridinium saccharinate salts as efficient recyclable acylation catalyst: A new bridge between heterogeneous and homogeneous catalysis
Lu, Norman,Chang, Wei-Hsuan,Wei, Rong-Jyun,Fang, Yung-Cheng,Han, Tu-Wen,Wang, Guo-Quan,Chang, Jia-Yaw,Wen, Yuh-Sheng,Liu, Ling-Kang
, p. 3468 - 3476 (2016/06/06)
It is important to find a way for separation of concerned chemicals from product mixture after reaction, in order to avoid spreading harmful chemicals to society. The homogeneous nature of DMAP-catalyzed acylation still suffers from the problems of catalyst separation and/or residual DMAP contamination. DMAP causes acute dermal toxicity, whereas the corresponding DMAP salt exhibits only slight irritation to the skin. Very recently, we found that the DMAP saccharinate salt is also great recyclable catalyst, whose acylation of alcohols has been successfully and effectively carried out 10 times without loss in activity. This report covers our comprehensive studies on using the pyridinium saccharinate salts as efficient recyclable acylation catalysts including 4-N,N-dimethylaminopyridinium saccharinate (A), 4-(1-pyrrolidinyl) pyridinium saccharinate (B), 2-N,N-dimethylaminopyridinium saccharinate (C), and pyridinium saccharinate (D). Their structure and reactivity have been studied. The salts A, C, and D contain very interesting seven-membered synthon showing multiple H-bonding interactions for pair of pyridinium cation and saccharinate anion in the solid state. The salt B exhibits H-bonding interaction of N(sac) ... H-N(py) in the solid state, instead of seven-membered synthon. The catalytic reactivity studies show that salts A and B are both very effective, with salt B even better in reactivity, and are both recyclable in the esterification of a variety of alcohols, under solvent-free and base-free conditions at room temperature.
An approach to heterodiarylmethanes via sp2-sp3 Suzuki-Miyaura cross-coupling
Stewart, Gavin W.,Maligres, Peter E.,Baxter, Carl A.,Junker, Ellyn M.,Krska, Shane W.,Scott, Jeremy P.
, p. 3701 - 3706 (2016/06/06)
The synthesis of a range of structurally diverse diarylmethanes via the Suzuki-Miyaura cross-coupling of aryl methane acetates and arylboronic acids is reported, including several challenging examples containing nitrogen, oxygen and sulfur heteroatoms in one or both coupling partners. A single set of optimized conditions was used to generate the diarylmethanes in 52-91% yield.
A basic germanodecatungstate with a - 7 charge: Efficient chemoselective acylation of primary alcohols
Sugahara, Kosei,Satake, Naoto,Kamata, Keigo,Nakajima, Takahito,Mizuno, Noritaka
supporting information, p. 13248 - 13252 (2015/01/09)
The synthesis of highly negatively charged polyoxometalates with electrically and structurally controlled uniform basic sites can lead to the unique base catalysis. In this work, a γ-Keggin germanodecatungstate, [γ-HGeW10O36]7- (A), having a -7 charge was, for the first time, successfully synthesized by the reaction of [γ-H2GeW10O36]6- with one equivalent of [(n-C4H9)4N]OH under non-aqueous conditions. The activities of germanodecatungstates for base-catalyzed reactions dramatically increased with increase in the number negative charges from -6 to -7. In the presence of A, various combinations of acylating agents and primary alcohols including those with acid-sensitive functional groups chemoselectively gave the desired acylated products in high yields even under the stoichiometric conditions.
Tribromo melamine as novel and versatile catalyst for the formylation and acetylation of alcohols
Hajjami, Maryam,Ghorbani-Choghamarani, Arash,Karamshahi, Zahra,Norouzi, Masoomeh
, p. 260 - 263 (2014/03/21)
Tribromo melamine has been found to be an efficient and green organocatalyst for the acetylation and formylation reactions of alcohols with acetic anhydride and ethyl formate at room temperature and under mild reaction conditions.
