2314-36-5Relevant academic research and scientific papers
Activator free, expeditious and eco-friendly chlorination of activated arenes by N-chloro-N-(phenylsulfonyl)benzene sulfonamide (NCBSI)
Misal, Balu,Palav, Amey,Ganwir, Prerna,Chaturbhuj, Ganesh
supporting information, (2021/01/04)
N-Chloro-N-(phenylsulfonyl)benzene sulfonamide (NCBSI) has been explored for the first time as a chlorinating reagent for direct chlorination of various activated arenes and heterocycles without any activator. A comparative in-silico study was performed to determine the electrophilic character for NCBSI and commercially available N-chloro reagents to reveal the reactivity on a theoretical viewpoint. The reagent was prepared by an improved method avoiding the use of hazardous t-butyl hypochlorite. This reagent was proved to be very reactive compared to other N-chloro reagents. The precursor of the reagent N-(phenylsulfonyl)benzene sulfonamide was recovered from aqueous spent, which can be recycled to synthesize NCBSI. The eco-friendly protocol was equally applicable for the synthesis of industrially important chloroxylenol as an antibacterial agent.
Ceria-promoted Co@NC catalyst for biofuel upgrade: synergy between ceria and cobalt species
Wang, Bowei,Gao, Ruixiao,Zhang, Dan,Zeng, Yuyao,Zhang, Fangying,Yan, Xilong,Li, Yang,Chen, Ligong
supporting information, p. 8541 - 8553 (2021/04/12)
Ceria-promoted Co@NC (NC, N doped carbon) catalysts are prepared by pyrolysis of biomass materials. Characterization results indicate that ceria and Co species facilitate the distribution of each other due to the formation of a Ce-O-Co solid solution. The specific surface area of the catalyst increased from 378.77 to 537.7 m2g?1viathe introduction of ceria. The electron transfer from Co to Ce further enhanced their interaction, and Co species facilitate the formation of more defective oxygen vacancies on ceria, which are beneficial to the activities of catalytic hydrogenation and catalytic transfer hydrogenation (CTH), respectively. Thus, Co/Ce@NC (0.99% Co loading) pyrolyzed at 850 °C exhibits excellent performance in the hydrodeoxygenation (HDO) of vanillin with high metal utilization. Catalytic hydrogenation and CTH coexisted in the presence of H2and ethanol, and >99% yield of creosol can be obtained in each of them. The reaction processes are monitored. No intermediate is found in aqueous media, while ethoxymethyl-4-methoxy-2-phenol is detected in ethanol. Moreover, Co/Ce@NC presents outstanding stability and general applicability. This work provides new insights into the construction of M@NC (M, metal) catalysts and the HDO process of biofuel upgrade.
Encapsulated Ni-Co alloy nanoparticles as efficient catalyst for hydrodeoxygenation of biomass derivatives in water
Chen, Chun,Gong, Wanbing,Han, Miaomiao,Wang, Dongdong,Wang, Guozhong,Zhang, Haimin,Zhang, Jifang,Zhang, Yunxia,Zhao, Huijun
, p. 2027 - 2037 (2021/09/02)
Catalytic hydrodeoxygenation (HDO) is one of the most promising strategies to transform oxygen-rich biomass derivatives into high value-added chemicals and fuels, but highly challenging due to the lack of highly efficient nonprecious metal catalysts. Herein, we report for the first time of a facile synthetic approach to controllably fabricate well-defined Ni-Co alloy NPs confined on the tip of N-CNTs as HDO catalyst. The resultant Ni-Co alloy catalyst possesses outstanding HDO performance towards biomass-derived vanillin into 2-methoxy-4-methylphenol in water with 100% conversion efficiency and selectivity under mild reaction conditions, surpassing the reported high performance nonprecious HDO catalysts. Impressively, our experimental results also unveil that the Ni-Co alloy catalyst can be generically applied to catalyze HDO of vanillin derivatives and other aromatic aldehydes in water with 100% conversion efficiency and over 90% selectivity. Importantly, our DFT calculations and experimental results confirm that the achieved outstanding HDO catalytic performance is due to the greatly promoted selective adsorption and activation of C=O, and desorption of the activated hydrogen species by the synergism of the alloyed Ni-Co NPs. The findings of this work affords a new strategy to design and develop efficient transition metal-based catalysts for HDO reactions in water.
Selective upgrading of biomass-derived benzylic ketones by (formic acid)–Pd/HPC–NH2 system with high efficiency under ambient conditions
Chen, Yuzhuo,Chen, Zhirong,Gong, Yutong,Mao, Shanjun,Ning, Honghui,Wang, Yong,Wang, Zhenzhen
, p. 3069 - 3084 (2021/11/16)
Upgrading biomass-derived phenolic compounds provides a valuable approach for the production of higher-value-added fuels and chemicals. However, most established catalytic systems display low hydrodeoxygenation (HDO) activities even under harsh reaction conditions. Here, we found that Pd supported on –NH2-modified hierarchically porous carbon (Pd/HPC–NH2) with formic acid (FA) as hydrogen source exhibits unprecedented performance for the selective HDO of benzylic ketones from crude lignin-derived oxygenates. Designed experiments and theoretical calculations reveal that the H+/H? species generated from FA decomposition accelerates nucleophilic attack on carbonyl carbon in benzylic ketones and the formate species formed via the esterification of intermediate alcohol with FA expedites the cleavage of C–O bonds, achieving a TOF of 152.5 h?1 at 30°C for vanillin upgrading, 15 times higher than that in traditional HDO processes (～10 h?1, 100°C–300°C). This work provides an intriguing green route to produce transportation fuels or valuable chemicals from only biomass under mild conditions.
Recyclable Pd/C catalyzed one-step reduction of carbonyls to hydrocarbons under simple conditions without extra base
Zhou, Xiao-Yu,Chen, Xia
supporting information, (2019/12/06)
The reductions of carbonyls for the synthesis of hydrocarbons were developed with hydrazine hydrate, hydrogen gas and ammonium formate respectively. The simple, mild and efficient conditions were provided by employing recyclable Pd/C as catalyst in normal solvents at 100 °C and the reactions proceeded smoothly to produce the corresponding products with good to excellent yields. And gram-scale reactions and recycling of the catalyst were also demonstrated. Furtherly, the mechanism has been proposed.
A process for preparing a broad pH fluorescent probe of the organic compound and use thereof (by machine translation)
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Paragraph 0134; 0135, (2018/04/03)
The present invention discloses a process for the preparation of a wide range of fluorescent probe in the pH of the organic compound, the organic compound can be produced according to the actual need to carry out any proportion of combination, and can be fixed in the hydrophilic high polymer further preparing and detecting water environment acidity and alkalinity of the product. The product can be realized to the pH value of the continuous measuring, thereby greatly improving the efficiency, sensitivity and repeatability. (by machine translation)
Method for reducing carbonyl into methylene at normal temperature and normal pressure
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Paragraph 0044; 0045; 0046; 0047; 0048, (2017/04/29)
The invention discloses a method for reducing carbonyl into methylene at normal temperature and normal pressure. The method includes the following steps that a carbonyl compound, a nitrogen doped carbon material loaded palladium catalyst and a solvent are added into a reaction container, the ratio of the carbonyl compound to the nitrogen doped carbon material loaded palladium catalyst is (1-5) mol:(10-40) g, hydrogen is introduced, reacting is carried out for 0.5-20 h at normal temperature and normal pressure, and carbonyl can be reduced into methylene through catalytic hydrogenation. The reaction formula of the reaction is shown in the specification. The method is simple, easy to operate, mild in condition, high in conversion rate, good in selectivity, low in cost and free of pollution to the environment.
Co embedded within biomass-derived mesoporous N-doped carbon as an acid-resistant and chemoselective catalyst for transfer hydrodeoxygenation of biomass with formic acid
Yang, Huanhuan,Nie, Renfeng,Xia, Wang,Yu, Xiaolong,Jin, Dingfeng,Lu, Xinhuan,Zhou, Dan,Xia, Qinghua
, p. 5714 - 5722 (2017/12/06)
An N-doped Co@C catalyst (Co@NC) is synthesized by a one-pot carbonization of biomass-derived glucose and harmless melamine with CoCl2 as the catalyst, where C and N resources could be transformed into highly graphitic N-doped carbon, while the coordinated Co2+ ions are reduced to uniform Co nanoparticles (NPs), which are embedded in N-doped graphitic structures. Under base-free conditions with formic acid (FA) as a hydrogen donor, the optimized Co@NC-700 (pyrolyzed at 700 °C) shows a highly efficient H2 generation from FA and the best activity for vanillin hydrodeoxygenation (HDO) with FA. For example, Co@NC-700 exhibits 15.4 times higher activity in comparison with uncovered Co on AC (Co/AC), and affords >95% vanillin conversion with 2-methoxy-4-methylphenol (MMP) as the sole product at 180 °C for 4 h. Compared with molecular hydrogen, Co@NC-700 gives a much higher activity and MMP selectivity for vanillin HDO with FA. The Co@NC-700 demonstrates enhanced acid resistance in acidic medium and adsorption of vanillin, and is recyclable and versatile for hydrogenating various unsaturated compounds. The superior performance of Co@NC-700 could be ascribed to N-derived defective sites on Co@NC, which could play multiple roles as base additives in FA dehydrogenation and as a metal-like active center in vanillin HDO.
2-THIOXOTHIAZOLIDIN-4-ONE DERIVATIVES ACTIVE AS TRANSTHYRETIN LIGANDS AND USES THEREOF
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Paragraph 00307; 00308; 00309, (2016/06/15)
Compounds of formula (II) are provided for stabilizing protein transthyretin (TTR) and inhibiting amyloid fibril formation, for example, transthyretin-mediated amyloid fibril formation, and for treating, preventing, or ameliorating one or more symptoms of amyloid diseases, for example, transthyretin-related amyloidosis (ATTR).
Scope and Mechanistic Analysis for Chemoselective Hydrogenolysis of Carbonyl Compounds Catalyzed by a Cationic Ruthenium Hydride Complex with a Tunable Phenol Ligand
Kalutharage, Nishantha,Yi, Chae S.
supporting information, p. 11105 - 11114 (2015/09/15)
A cationic ruthenium hydride complex, [(C6H6)(PCy3)(CO)RuH]+BF4- (1), with a phenol ligand was found to exhibit high catalytic activity for the hydrogenolysis of carbonyl compounds to yield the corresponding aliphatic products. The catalytic method showed exceptionally high chemoselectivity toward the carbonyl reduction over alkene hydrogenation. Kinetic and spectroscopic studies revealed a strong electronic influence of the phenol ligand on the catalyst activity. The Hammett plot of the hydrogenolysis of 4-methoxyacetophenone displayed two opposite linear slopes for the catalytic system 1/p-X-C6H4OH (ρ = -3.3 for X = OMe, t-Bu, Et, and Me; ρ = +1.5 for X = F, Cl, and CF3). A normal deuterium isotope effect was observed for the hydrogenolysis reaction catalyzed by 1/p-X-C6H4OH with an electron-releasing group (kH/kD = 1.7-2.5; X = OMe, Et), whereas an inverse isotope effect was measured for 1/p-X-C6H4OH with an electron-withdrawing group (kH/kD = 0.6-0.7; X = Cl, CF3). The empirical rate law was determined from the hydrogenolysis of 4-methoxyacetophenone: rate = kobsd[Ru][ketone][H2]-1 for the reaction catalyzed by 1/p-OMe-C6H4OH, and rate = kobsd[Ru][ketone][H2]0 for the reaction catalyzed by 1/p-CF3-C6H4OH. Catalytically relevant dinuclear ruthenium hydride and hydroxo complexes were synthesized, and their structures were established by X-ray crystallography. Two distinct mechanistic pathways are presented for the hydrogenolysis reaction on the basis of these kinetic and spectroscopic data. (Chemical Equation Presented).
