931-17-9Relevant academic research and scientific papers
Ammonium Fluoroperoxomonophosphate Dihydrate, 2*2H2O. First Chemical Synthesis of a Fluorinated Peroxophosphate
Bhattacharjee, Manish,Chaudhuri, Mihir K.
, p. 2005 - 2006 (1988)
The salt 2*2H2O has been synthesised from the reaction of with 48 percent HF and 30 percent H2O2 at pH 10 - 11, maintained by the addition of aqueous ammonia, at an ice-bath temperature.The compound has been characterised by chemical analysis, i.r., and laser-Raman spectroscopic studies.Some properties of the compound are also reported.
Enhanced catalytic (ep)oxidation of olefins by VO(II), ZrO(II) and Zn(II)-imine complexes; extensive characterization supported by DFT studies
Adam, Mohamed Shaker S.,Abdel-Rahman, Laila H.,Ahmed, Hanan El-Sayed,Makhlouf,Alhasani, Mona,El-Metwaly, Nashwa M.
, (2021)
Three mononuclear di-valent VO2+, ZrO2+ and Zn2+-complexes (VOL, ZrOL and ZnL, respectively) were prepared from asymmetrical di-basic tetradentate di-imine ligand (6,6′-((1E,1′E)-((4-chloro-1,2-phenylene)bis(azaneylylidene))bis(methaneylylidene))bis(2-ethoxy phenol, H2L). To confirm the M-complexes compositions, various spectral tools (FT-IR, EI/M and UV-Vis. spectra), molar conductance, thermal, elemental analysis and pXRD analyses were accomplished. Distorted octahedral geometry was confirmed for ZnL and square pyramidal geometry was elucidated for VOL and ZrOL. Their catalytic efficiency was investigated in the epoxidation of 1,2-cyclohexene by H2O2. They exhibited moderate to excellent catalytic control. The effect of temperature, time, solvent, type of oxidant and amount of catalysts were studied in order to determine the optimal catalytic atmosphere. The catalysts screening for epoxidation of alternative cyclic and acyclic olefins at optimization was reported. The variation of central metal ions from high to low valents (Zr4+, V4+and Zn2+ ions) and their capability for oxidation control their catalytic potential are the most effective aspects in the epoxidation reaction. The catalytic oxidation of 2-aminothiophene within VOL, ZrOL and ZnL, as a first trial, by H2O2 was examined. Also, QSAR parameters and DFT studies were performed to predict the catalytic properties of VOL, ZrOL and ZnL, to assert on chosen application. Effective surface properties of VO(II) complex were promoted for progressing its catalytic activity, which already happened. The catalytic mechanism was supported by the sequenced stability difference between proposed intermediates based on the difference in their recorded formation energy from the DFT study.
Two routes to 1,2-cyclohexanediol catalyzed by zeolites under solvent-free condition
Lei, Wenkang,Wu, Zaikun,Ma, Jie,Yu, Ping,Luo, Yunbai
, p. 6893 - 6905 (2016)
Two routes to 1,2-cyclohexanediol were studied. Specifically: (a) the hydrolysis of cyclohexene oxide and (b) the direct dihydroxylation of cyclohexene with aqueous hydrogen peroxide. Both reactions were carried out with zeolites as catalysts under solvent-free conditions, aiming to establish green routes for the synthesis of 1,2-cyclohexanediol. In the first route, H-Beta and H-ZSM-5 zeolites were used as catalysts, respectively. According to the results, H-ZSM-5 was a suitable catalyst for the hydrolysis of cyclohexene oxide. A 88.6?% yield of 1,2-cyclohexanediol could be obtained at a 96.2?% conversion of cyclohexene oxide under mild conditions, and the catalyst could be reused for three times. Compared with H-ZSM-5, H-Beta gave a much lower selectivity (63?%), although it was more active. In the second route, Ti-Beta zeolites with three different Ti loadings prepared via a simple two-step strategy were characterized and used. The results indicated that it was the framework Ti species which was responsible for the catalytic activity. The resultant Ti-Beta-3?% could give a 90.2?% cyclohexene conversion at a 66.2?% selectivity of 1,2-cyclohexanediol.
Kinetic role of tert-amines in the osmium tetroxide catalyzed trimethylamine N-oxide dihydroxylation of cyclohexene
Erdik, Ender,Kahya, Didem
, p. 359 - 366 (1997)
Effect of some tert-amines on the catalytic osmium tetroxide dihydroxylation of cyclohexene in aqueous tert-butyl alcohol has been investigated. All amines have been found to retard the catalysis greatly and beyond a definite concentration of amine, the rate reaches a minimal and remains constant. The oxidation of cyclohexene is inhibited by pyridine, 2,2′-bipyridyl, and DABCO with an inverse first-order dependence whereas inhibition by triphenylamine, N,N-diethylaniline, picoline, pyrazine, hexamethylenetetraamine, and TMEDA shows an inverse partial order dependence. The involvement of dioxomonoglycolatoosmium(VI) esters and their monoamine adducts in the rate determining oxidation step was established by the linear plots of 1/Δk2 vs. 1/[L] where Δk2 is the decrease in the second-order rate constant in the presence of [L] concentration of tert-amine. The ligand-accelerated or ligand-decelerated catalysis of tert-amines in the catalytic osmium tetraoxide dihydroxylation of alkenes may vary depending on the secondary oxidant, on the alkene, and on the structure and concentration of the tert-amine.
PROCESS FOR THE PREPARATION OF HYDROPEROXY ALCOHOLS USING A HETEROGENOUS CATALYST
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Page/Page column 23, (2021/07/02)
The present invention relates to a process for preparing hydroperoxy alcohols using hydrogen peroxide as an oxidant in a solvent selected from water-soluble carboxylic acids, in the presence of a metallic mixed oxide heterogeneous catalyst. It also pertains to the use of this catalyst in the synthesis of hydroperoxy alcohols.
Oxidative cleavage of cycloalkenes using hydrogen peroxide and a tungsten-based catalyst: Towards a complete mechanistic investigation
Cousin, Tony,Chatel, Gregory,Andrioletti, Bruno,Draye, Micheline
, p. 235 - 242 (2021/01/11)
The identification of the intermediates and by-products produced during the oxidative cleavage of cycloalkenes in the presence of H2O2 and a tungsten-based catalyst for the production of dicarboxylic acids has been carried out under various experimental conditions. On the basis of this mechanistic investigation and previous studies from the literature, a complete reaction scheme for the formation of the reaction products and by-products is proposed. In this hypothetical mechanism, the production of a hydroperoxyalcohol intermediate accounts for the two pathways proposed by Noyori and Venturello for the formation of the targeted dicarboxylic acid. In addition, Baeyer-Villiger oxidation of the mono-aldehyde intermediate allows explaining the formation of short chain diacids observed as by-products during the reaction. Hence, the proposed mechanism constitutes a real tool for scientists looking for a better understanding and those heading to set up environmentally friendly conditions for the oxidative cleavage of cycloalkenes.
Tandem Lewis acid catalysis for the conversion of alkenes to 1,2-diols in the confined space of bifunctional TiSn-Beta zeolite
Lei, Qifeng,Wang, Chang,Dai, Weili,Wu, Guangjun,Guan, Naijia,Hunger, Michael,Li, Landong
, p. 1176 - 1184 (2021/02/16)
The generation of multifunctional isolated active sites in zeolite supports is an attractive method for integrating multistep sequential reactions into a single-pass tandem catalytic reaction. In this study, bifunctional TiSn-Beta zeolite was prepared by a simple and scalable post-synthesis approach, and it was utilized as an efficient heterogeneous catalyst for the tandem conversion of alkenes to 1,2-diols. The isolated Ti and Sn Lewis acid sites within the TiSn-Beta zeolite can efficiently integrate alkene epoxidation and epoxide hydration in tandem in a zeolite microreactor to achieve one-step conversion of alkenes to 1,2-diols with a high selectivity of >90%. Zeolite confinement effects result in high tandem rates of alkene epoxidation and epoxide hydration as well as high selectivity toward the desired product. Further, the novel method demonstrated herein can be employed to other tandem catalytic reactions for sustainable chemical production.
Sterically controlling 2-carboxylated imidazolium salts for one-step efficient hydration of epoxides into 1,2-diols
Cheng, Weiguo,Dong, Li,Fu, Mengqian,Su, Qian,Tan, Xin,Yao, Xiaoqian,Ying, Ting,Zhang, Suojiang
, p. 2992 - 3000 (2021/05/07)
In order to overcome the disadvantages of excessive water and many byproducts in the conventional process of epoxide hydration into 1,2-diols, 2-carboxylated imidazolium salts were first adopted as efficient catalysts for one-step hydration of epoxides into 1,2-diols. By regulating the cation chain lengths, different steric structures of 2-carboxylated imidazolium salts with chain lengths from C1 to C4 were prepared. The salt with the shortest substituent chain (DMIC) exhibited better thermal stability and catalytic performance for hydration, achieving nearly 100% ethylene oxide (EO) conversion and 100% ethylene glycol (EG) selectivity at 120 °C, 0.5 h with just 5 times molar ratio of H2O to EO. Such a tendency is further confirmed and explained by both XPS analysis and DFT calculations. Compared with other salts with longer chains, DMIC has stronger interaction of CO2?anions and imidazolium cations, exhibiting a lower tendency to release CO2?and form HO-CO2?, which can nucleophilically attack and synergistically activate ring-opening of epoxides with imidazolium cations. The strong huge sterically dynamic structure ring-opening transition state slows down the side reaction, and both cations and anions stabilized the transition state imidazolium-EG-HO-CO2?, both of which could avoid excessive hydration into byproducts, explaining the high 1,2-diol yield. Based on this, the cation-anion synergistic mechanism is then proposed.
Selective Oxidation of Cyclohexene with H2O2 Catalyzed by Resin Supported Peroxo Phosphotungstic Acid Under Mild Conditions
Liu, Jia,Yang, Guoqiang,Liu, Ying,Zhou, Zheng,Zhang, Zhibing,Hu, Xingbang
, p. 147 - 152 (2020/06/20)
Abstract: A series of modified chloromethyl polystyrene resins loaded with peroxo phosphotungstic acid catalysts were synthesized for the selective oxidation of cyclohexene. The surface of resin was enriched with high concentration quaternary ammonium salt, and grafted with a large amount of peroxo PW-anion through ion exchange. The novel resin catalyst showed excellent cyclohexene conversion and epoxide selectivity using 30% H2O2 as oxidant at ambient temperature. Furthermore, the resin catalyst exhibited excellent recycling stability, which can be reused by a simple filtration and the peroxo phosphotungstic acid did not leach into the solvent after reaction. Graphic Abstract: [Figure not available: see fulltext.]
Catalytic Performance of Zr-Based Metal–Organic Frameworks Zr-abtc and MIP-200 in Selective Oxidations with H2O2
Maksimchuk, Nataliya V.,Ivanchikova, Irina D.,Cho, Kyung Ho,Zalomaeva, Olga V.,Evtushok, Vasiliy Yu.,Larionov, Kirill P.,Glazneva, Tatiana S.,Chang, Jong-San,Kholdeeva, Oxana A.
supporting information, p. 6985 - 6992 (2021/03/17)
The catalytic performance of Zr-abtc and MIP-200 metal–organic frameworks consisting of 8-connected Zr6 clusters and tetratopic linkers was investigated in H2O2-based selective oxidations and compared with that of 12-coordinated UiO-66 and UiO-67. Zr-abtc demonstrated advantages in both substrate conversion and product selectivity for epoxidation of electron-deficient C=C bonds in α,β-unsaturated ketones. The significant predominance of 1,2-epoxide in carvone epoxidation, coupled with high sulfone selectivity in thioether oxidation, points to a nucleophilic oxidation mechanism over Zr-abtc. The superior catalytic performance in the epoxidation of unsaturated ketones correlates with a larger amount of weak basic sites in Zr-abtc. Electrophilic activation of H2O2 can also be realized, as evidenced by the high activity of Zr-abtc in epoxidation of the electron-rich C=C bond in caryophyllene. XRD and FTIR studies confirmed the retention of the Zr-abtc structure after the catalysis. The low activity of MIP-200 in H2O2-based oxidations is most likely related to its specific hydrophilicity, which disfavors adsorption of organic substrates and H2O2.
