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41.
Oxidation of cyclohexene and styrene with sodium periodate and tetra‐n‐butylammonium periodate (TBAP) catalyzed by MnT(3‐MePy)P(OAc), MnT(4‐SO3)PP(OAc) and MnTPP(OAc) has been studied in water, methanol, acetonitrile and dichloromethane as solvents. The results show significant dependence of the product distribution on the type of solvent and the electronic nature of the aryl substituents introduced at the porphyrin periphery. While the oxidation of cyclohexene and styrene in the presence of MnT(3‐MePy)P(OAc) and MnTPP(OAc) in water (also in methanol) gave the corresponding epoxides as nearly the sole product, performing the reactions in the presence of MnT(4‐SO3)PP(OAc) yielded the products of allylic oxidation, cyclohexene‐2‐ol and cyclohexene‐2‐one and acetophenone as the major products. In the case of styrene, performing the reaction in the presence of MnT(4‐SO3)PP(OAc), MnT(3‐MePy)P(OAc) and MnTPP(OAc) in acetonitrile gave a mixture of styrene oxide and acetophenone as the products. Under the same conditions, the oxidation of cyclohexene afforded cyclohexene oxide as approximately the exclusive product. Furthermore, the oxidation of olefins in dichloromethane gave the corresponding epoxide as the exclusive products. The product distributions observed in the protic and aprotic solvents were used to provide indirect evidence on the relative contribution and reactivity of high valent manganese oxo and periodato Mn(III) porphyrin species to the oxidation reactions. 相似文献
42.
Saeed Bahadorikhalili Samira Ansari Haleh Hamedifar Leila Ma'mani Mohsen Babaei Rahim Eqra Mohammad Mahdavi 《应用有机金属化学》2019,33(4)
In this paper, a novel catalyst is introduced based on the immobilization of palladium on modified magnetic graphene oxide nanoparticles. The catalyst is characterized by several methods, including transmission electron microscopy, scanning electron microscopy, X‐ray fluorescence, vibrating‐sample magnetometer, Fourier transform‐infrared and dynamic light scattering (DLS) analysis. The activity of the catalyst was investigated in the synthesis of 4(3H)‐quinazolinones via Pd‐catalyzed carbonylation‐cyclization of N‐(2‐bromoaryl) benzimidamides by Mo (CO)6. The Mo (CO)6 is used as a carbon monoxide source for performing the reaction under mild conditions. The catalyst showed good reusability, and no change in activity was observed after 10 cycles of recovery. 相似文献
43.
Poul Erik Hansen Bahjat A. Saeed Rita S. Rutu Teobald Kupka 《Magnetic resonance in chemistry : MRC》2020,58(8):750-762
1J(15N,H) coupling constants for enaminones and NH-forms of intramolecularly hydrogen-bonded Schiff bases as model compounds for sp2-hybridized nitrogen atoms are evaluated using density functional theory (DFT) to find the optimal functionals and basis sets. Ammonia is used as a test molecule and its one-bond coupling constant is compared with experiment. A methylamine Schiff base of a truncated molecule of gossypol is used for checking the performance of selected B3LYP, O3LYP, PBE, BHandH, and APFD density functionals and standard, modified, and dedicated basis sets for coupling constants. Both in vacuum and in chloroform, modeled by the simple continuum model of solvent, the modified basis sets predict significantly better the 1J(15N,H) value in ammonia and in the methylamine Schiff base of a truncated molecule of gossypol than the standard basis sets. This procure is then used on a broad set of intramolecularly hydrogen-bonded molecules, and a good correlation between calculated and experimental one-bond NH coupling constants is obtained. The 1J(15N,H) couplings are slightly overestimated. The calculated data show for hydrogen-bonded NH interatomic distances that the calculated values depend on the NH bond lengths. The shorter the bond lengths, the larger the 1J(15N,H). A useful correlation between 1J(15N,H) and NH bond length is derived that enables realistic predictions of one-bond NH coupling constants. The calculations reproduce experimentally observed trends for the studied molecules. 相似文献
44.
45.
Majid Abdellahi Aliakbar Najfinezhad Saeed Saber-Samanadari Amirsalar Khandan Hamid Ghayour 《Chinese Journal of Physics (Taipei)》2018,56(1):331-339
In the present study, hard ferromagnetic (M-type strontium hexaferrite) SrFe12O19 was co-doped by Zn and Zr for magnetic hyperthermia applications. As a result of the high concentration of single domain SrFe12O19 nanoparticles (suspended in the ferrofluid), they found a large hydrodynamic diameter, which caused a long-time Brownian relaxation under the AC magnetic field. On the other hand, increasing the Zn-Zr content (low concentration of SrFe12O19) led to a drop in anisotropy, which coincided with a short-time N´eel relaxation. All of the substituted samples with a multi-disperse state in ferrofluid exhibited an almost equal amount of the N´eel and Brownian effects. Consequently, the magnetic saturation (Ms) was considered as the dominant factor in the specific absorption rate (SAR) of the substituted samples. Transformation to the mono-disperse state was followed by the decrease of the Brownian relaxation time and hence the increase of the SAR. The interesting point in mono-disperse state was the heat generation of pure SrFe12O19 under the AC magnetic field as a result of the decrement of the Brownian relaxation time. 相似文献
46.
Sidra Jabeen Zhe Zeng Mohammednoor Altarawneh Xiangpeng Gao Anam Saeed Bogdan Z. Dlugogorski 《国际化学动力学杂志》2019,51(9):696-710
This contribution investigates thermal decomposition of leucine, as a representative model compound for amino acids in algal biomass. We map out potential energy surface for a wide array of unimolecular and self-condensation reactions operating in the decomposition of leucine. Decarboxylation and dehydration of leucine ensues by eliminating CO2 and –OH, respectively, from the –COOH group attached to the α-carbon. The molecular channel for deamination involves cleavage of NH2 from α-carbon of leucine. The activation energies for direct elimination of CO2, NH3, and H2O from a leucine molecule lie within 20.7 kJ/mol of each other. Activation energies for these decomposition pathways reside below the bond dissociation enthalpy of H–C(α) of 323.1 kJ/mol. The decarboxylation, deamination, and dehydration pathways, via radical-prompted pathways, systematically require lower energy barriers, in reference to closed-shell reaction corridors. Detailed computations at the CBS-QB3 level provide the Arrhenius rate parameters for the unimolecular and bimolecular reactions, and standard enthalpies of formation, standard entropies, and heat capacities for all the products and intermediates. A kinetic analysis of gas-phase reactions, within the context of a plug-flow reactor model, accounts qualitatively for the formation of major products observed experimentally in the thermal degradation of the condensed-phase leucine. Among notable N-containing species, the model predicts the prevailing of NH3 over HCN and HNCO, in addition to corresponding appreciable concentrations of amines, imines, and nitriles. Our detailed kinetic investigation illustrates a negligible contribution of the self-condensation reactions of leucine in the gas phase. 相似文献
47.
Mitra Talaee Bahareh Lorestani Majid Ramezani Mehrdad Cheraghi Saeed Jamehbozorgi 《Journal of separation science》2019,42(14):2418-2425
A simple and fast method named microfunnel‐filter‐based emulsification microextraction is introduced for an efficient determination of some organophosphorus pesticides including diazinon, malathion, and chlorpyrifos in the environmental samples including the river, sea, and well water. This method is based upon the dispersion of a low‐toxicity organic solvent (dihexyl ether), as the extractant, in a high volume of an aqueous sample solution (45 mL). It is implemented without a centrifugation step, and using a syringe filter and a micro‐funnel, the phase separation and transfer of the enriched analytes to the gas chromatograph are simply achieved. By filtration of the extractant phase, a suitable sample clean‐up is obtained, and the total extraction time is just a few minutes. The factors influencing the extraction efficiency are optimized, and under the optimal conditions, the proposed method provides a good linearity (in the range of 15–1500 ng/mL (R2 > 0.996). A high enrichment factor is obtained (in the range of 306–342), and the method provides low limits of detection and quantification (in the ranges of 4–8 and 15–25 ng/mL, respectively). 相似文献
48.
Asif Nisar Muhammad Saeed Muhammad Usman Majid Muneer Muhammad Adeel Iltaf Khan Javaid Akhtar 《国际化学动力学杂志》2020,52(10):645-654
Photodegradation of organic pollutants strongly depends on design of metal oxide semiconductor photocatalysts. Graphene, if composited with ZnO, can effectively enhance its photocatalytic performance for the eradication of pollutants from aqueous medium. Here in, ZnO-rGO is reported as highly active catalyst for degradation of methylene blue. A 200-mg/L solution of methylene blue dye was completely degraded within 1 h in comparison to 74% and 56% degradation over ZnO and rGO, respectively. The commonly used mechanisms of heterogeneous catalytic reactions, the Langmuir-Hinshelwood mechanism, and the Eley-Rideal mechanisms, were used to describe the reaction kinetics. The Langmuir-Hinshelwood mechanism was found as more favorable in this study. Apparent activation energy, Eap, true activation energy, ET, entropy, ΔS, and enthalpy, ΔH were calculated as 36.2 kJ/mol, 13.1 kJ/mol, 197.5 J/mol, and 23.1 kJ/mol, respectively. 相似文献
49.
50.
Synthesis,characterization and application of 3‐methyl‐1‐sulfonic acid imidazolium tetrachloroferrate as nanostructured catalyst for the tandem reaction of β‐naphthol with aromatic aldehydes and amide derivatives 下载免费PDF全文
Ardeshir Khazaei Ahmad Reza Moosavi‐Zare Saeed Firoozmand Mohammad Reza Khodadadian 《应用有机金属化学》2018,32(2)
3‐methyl‐1‐sulfonic acid imidazolium tetrachloroferrate {[Msim]FeCl4} was prepared and fully characterized by fourier transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD), thermal gravimetric analysis (TGA), differential thermal gravimetric (DTG), field emission scanning electron microscopy (FESEM), energy dispersive X‐ray analysis (EDX) and vibrating sample magnetometer (VSM) and used, as an efficient catalyst, for the tandem reaction of β‐naphthol with aromatic aldehydes and benzamide at 110 °C under solvent‐free conditions to give 1‐amidoalkyl‐2‐naphthols in high yields and very short reaction times. 相似文献