Oxidative Methylation of Toluene with Methane over Basic Zeolite Catalysts Promoted with Alkali Metal Bromides and Alkali Metal Oxides

The catalytic effects for the oxidative methylation of toluene with methane over the basic zeolite catalysts prepared by promoting KY, KX, KM, KZSM-5 or KP with alkali-metal bromides and alkali-metal oxides have been investigated comparatively. The alkali-metal bromides promoted substrates are more effective than the alkali-metal oxides promoted systems. Moreover, the NaBr promoted systems are more active than KBr promoted systems. The most effective catalytic system (8wt%NaBr)/KZSM-5 gave a toluene conversion as high as 76.3% and a total C-8 selectivity of 76.4% (styrene/ethylbenzene=9.76) resulting in a total C-8 yield of 58.3%.

Determination of Standard Molar Enthalpies of Formation of Complexes of Rare Earth Bromides with Glycine

The integral heat of solution of REBr 3·3Gly·3H 2O(RE=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy and Y; Gly is glycine) in water, REBr 3· n H 2O(RE=La, Ce and Pr, n =7; RE=Nd, Sm, Eu, Gd, Tb, Dy and Y, n =6) in aqueous glycine solution and glycine in water have been measured calorimetrically at 298 15±0 15 K. By means of a thermochemical cycle suggested in this paper, the standard molar enthalpies of formation of REBr 3·3Gly·3H 2O have been obtained and their lattice energies have been calculated.

The effect of cations(NH_4^+,Na^+,K^+,and Ca^(2+)) on chemical deactivation of commercial SCR catalyst by bromides

Alkali and alkaline‐earth metals from fly ash have a significant deactivation effect on catalysts used for selective catalytic reduction of NOx by NH3(NH3‐SCR).Bromides are considered effective additives to improve Hg0 oxidation on SCR catalysts.In this work,the effects of different bromides(NH4Br,NaBr,KBr,and CaBr2)on a commercial V2O5‐WO3/TiO2 catalyst were studied.NOx conversion decreased significantly over the KBr‐poisoned catalyst(denoted as L‐KBr),while that over NaBr‐and CaBr2‐poisoned catalysts(denoted as L‐NaBr and L‐CaBr,respectivity)decreased to a lesser extent compared with the fresh sample.Poor N2 selectivity was observed over L‐NaBr,L‐KBr and L‐CaBr catalysts.The decrease in the ratio of chemisorbed oxygen to total surface oxygen(Oα/(Oα+Oβ+Ow)),reducibility and surface acidity might contribute to the poor activity and N2 selectivity over L‐KBr catalyst.The increased Oαratio was conducive to the enhanced reducibility of L‐CaBr.Combined with enhanced surface acidity,this might offset the negative effect of the loss of active sites by CaBr2 covering.The overoxidation of NH3 and poor N2 selectivity in NH3 oxidation should retard the SCR activity at high temperatures over L‐CaBr catalyst.The increased basicity might contribute to increased NOx adsorption on L‐KBr and L‐CaBr catalysts.A correlation between the acid‐basic and redox properties of bromide‐poisoned catalysts and their catalytic properties is established.

Suzuki Reaction of Aryl Bromides Using a Phosphine-Free Magnetic Nanoparticle-Supported Palladium Catalyst

A palladium catalyst immobilized on superparaganetic nanoparticles was prepared with a palladium loading of 0.30 mmol/g. The catalyst was characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, vibrating sample magnetometry, thermogravimetric analysis, Fourier transform infrared, atomic absorption spectrophotometry, and nitrogen adsorption. The immobilized palladium catalyst was an efficient catalyst without added phosphine ligands for the Suzuki cross-coupling reaction of several aryl bromides with phenylboronic acid. The recovery of catalyst was simply by magnetic decantation in the presence of a magnet. The immobilized palladium catalyst can be reused many times without significant degradation in catalytic activity. No leaching of active palladium species into the reaction solution was detected.

Convenient one-pot synthesis of functionalized (E)-2-arylvinyl bromides from (E)-4-(2-bromovinyl)phenyl acetate

A convenient one-pot synthesis of functionalized （E）-2-arylvinyl bromides was achieved by microwave-induced deacetylation and subsequent acylation using dicyclohexyl carbodiimide （DCC） and dimethylamino-pyridine （DMAP） at room temperature from （E）-4-（2-bromovinyl）phenyl acetate.

Photochemical Radical Cascade 6-endo Cyclization of Dienes withα-Carbonyl Bromides for the Synthesis of Six-Membered Benzo-Fused Lactams

Comprehensive Summary A novel visible-light-induced radical cascade 6-endo cyclization of dienes(N-(2-vinylphenyl)acryl amides)is developed utilizingα-carbonyl bromides as alkyl reagents.This approach affords an efficient way for synthesizing six-membered benzo-fused lactam derivatives with chemo-and regio-selectivity and good functional group tolerance.Primary,secondary,and tertiary bromides are well-compatible with this cascade cyclization reaction.

Lead-promoted Barbier-type reaction of aldehydes with propargyl bromides in aqueous media

This paper reports that the reaction of the propargyl bromides with aldehydes promoted by powdered lead in aqueous media. The selectivity and possible mechanism of these reactions are discussed. The yields of products for reaction of propargyl bromide are 31 similar to 71%. The ratios of allenyl alcohol and homopropargyl alcohol are 1:1.5 to 1:3. The product for reaction of phenyl propargyl bromide is allenyl alcohol and the yields are 52 similar to 84%.

Palladium-Catalyzed Desulfitative Cross-Coupling of Sodium Arylsulfinates with Aryl Bromides and Chlorides： An Alternative Convenient Synthesis of Biaryls

An alternative method for synthesis of biaryls has been developed through the Pd catalyzed desulfitative coupling reaction of sodium arylsulfinates with aryl bromides and chlorides. The procedure tolerates a variety of functional groups, such as cyano, formyl, acetyl, chloro, methoxy, trifluoromethyl and heteroaromatic unit. The desired products were obtained in moderate to excellent yields under relatively mild reaction conditions without additives, base or co-catalyst.

Palladium-phosphinous acid complexes catalyzed Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid in water/alcoholic solvents

Highly active, air-stable and water-soluble palladium-phosphinous acid complexes have been applied to Suzuki cross-coupling reaction of heteroaryl bromides under mild conditions in water/alcoholic solvents. Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid occurred efficiently using palladium phosphinous acid complexes （POPd） and phase transfer catalyst （tetrabutylammonium bromide and polyethylene glycol） in water/ethanol mixture, water/propanol mixture and neat water respectively, the corresponding yields of cross-coupling heteroaryl-aryls were satisfied. The tert-butyl substituted ligand di-tert-butylphosphino in combination with POPd was found to be more active than the same family derived catalysts dipalladium complexes POPdl and POPd2, and other two kinds of Pd-catalysts Pd（PPh3）4 and Pd2（dba）3. The mechanism of Suzuki cross-coupling reaction between heteroaryl bromides and phenylboronic acid in water was proposed with respect to the key role of phase transfer catalyst on the transmetallation step. Compared with other solid phase transfer catalysts, TBAB was tested as the ideal one. The alkalinity of base and the molar proportion between POPd and TBAB were investigated in water and alcoholic solvents. Notably, in the presence of TBAB adding alcoholic solvents into water enhanced the yields of target products. However in terms of the liquid phase transfer catalyst of PEGs, mixing water into PEGs could slightly decrease the yields with respect to the water free PEGs bulk phase, which was probably due to the homogenous liquid conditions in pure PEGs and weak interactions between PEGs and heteroaryl bromide molecules in water depending on their molecular chain lengths.

In-situ defect passivation assisted three-step printing of efficient and stable formamidine-lead bromide solar cells

Perovskite solar cells(PSCs)emerge as the most promising photovoltaics(PV)for their high performance and potential convenient cost-effective production routes comparing to the sophomore PV technologies.The printed PSCs with simplified device architecture and fabrication procedures could further enhance the competitive strength of PSC technology.In this work,we present an in-situ defect passivation(ISDP)assisted full-printing of high performance formamidine-lead bromide(FAPbBr_(3))PSCs.Only three rapid printing steps are involved for electron transporting layer(ETL),perovskite and carbon to form a complete solar cell on the low-cost fluorine-doped tin oxide(FTO)substrate.Long-chain polymer monomethyl ether polyethylene glycol is particularly utilized as the ISDP passivator,leading to conformal coating on the rough FTO and defect passivation for both ETL and perovskite during printing.A high efficiency of 10.85%(certified 10.14%)and a high V_(oc)up to 1.57 V are achieved for the printed device.The unencapsulated PSCs maintain above 90%of the initial efficiency after continuously heating at 85℃for 1000 h and over 80%of the efficiency after the maximum power point tracking for 3500 h.The fully printed semitransparent PSCs with carbon grids(CGs)show average visible light transmittance over 33%and an efficiency of 8.81%.

Nonlinear Absorption and Low-threshold Two-photon Pumped Amplified Stimulated Emission from FAPbBr_(3) Nanocrystals

Formamidinium lead bromide(FAPbBr_(3))nanocrystals(NCs)have been considered to be a good optoelectronic material due to their pure green emission,excellent stability and superior carrier transport characteristics.However,two-photon pumped amplified spontaneous emission(ASE)and the corresponding nonlinear optical properties of FAPbBr_(3) NCs are scarcely revealed.Herein,we synthesized colloidal FAPbBr_(3) NCs with different sizes by changing the molar ratio of FABr/PbBr_(2) in the precursor solution,using ligand assisted precipitation(LARP)technology at room temperature.Photoluminescence(PL)and time resolved photoluminescence(TRPL)spectroscopy were measured to characterize their ASE properties.And their nonlinear optical properties were studied through the Zscan technique and the two-photon excited fluorescence method.The stimulated emission properties including oneand two-photon pumped ASE have been realized from FAPbBr_(3) NCs.With large two-photon absorption coefficient(0.27 cm/GW)and high non-linear absorption cross-section(7.52×10^(5) GM),ASE with threshold as low as 9.8μJ/cm^(2) and 487μJ/cm^(2) have been obtained from colloidal FAPbBr_(3) NCs using one-and two-photon excitations.These results indicate that as a new possible green-emitting frequency-upconversion material with low thresholds,FAPbBr_(3) NCs hold great potential in the development of high-performance two-photon pump lasers.

Copper-Catalyzed Cyanations of Aromatic Bromides with Benzoyl Cyanide

Aromatic nitriles were synthesized through copper-catalyzed cyanations of aromatic bromides using benzoyl cyanide as the cyanide source.A series of functional groups were tolerated under the reaction conditions to provide the products in good yields.Moreover,this protocol avoids using of highly toxic alkali cyanides and expensive palladium catalysts.

Nickel-Catalyzed Cross-Electrophile Coupling of Aryl Bromides with Pyrimidin-2-yl Tosylates

A new protocol for the NiC12-catalyzed cross-electrophile coupling of aryl bromides with pyrimidin-2-yl tosyl- ates to give the corresponding C2-arylation pyrimidine derivatives has been developed. This study provides an improvement over previous methods by using pyrimidin-2-yl tosylates instead of halides as coupling partners that are stable and easily available.

Copper（I）-Catalyzed Intramolecular Direct C-Arylation of Azoles with Aryl Bromides

A concise route to access 5H-imidazo[2,1-a]isoindole heterofused compounds by copper（I）-catalyzed intra- molecular coupling of non-activated aryl bromides with azoles is reported. With CuI as catalyst, 1,10-phenanth- roline as ligand, and K3PO4 as base, the reactions of 1-（2-bromobenzyl）-IH-imidazoles in DMF/o-xylene （I ： 1, V ： V） at 145 ℃ afford the corresponding substituted 5H-imidazo[2,1-a]isoindoles in high yields via intramolecu- lar C-arylation.

A New Synthetic Method of （Z）-4-Aryl-but-2-en-l-ols via Suzuki-Miyaura Cross-Coupling Reaction of 4-Substituted 1,2-Oxaborol-2（5H）-ols with Benzyl Bromides

Z and E configuration 4-aryl-but-2-en-1-ols were isolated from several terrestrial plants, and （Z）-4-aryl-but-2- en-l-ols were found to have choleretic activity. Strategies have been reported to synthesize （E）-4-aryl-but-2-en-l- ols with high selectivity. However, there is no method to obtain （Z）-4-aryl-but-2-en-1-ols with high selectivity now. We developed a Suzuki-Miyaura cross-coupling reaction of 1,2-oxaborol-2（5H）-ols with benzyl bromides to synthesize （Z）-4-aryl-but-2-en-1-ols, the products were obtained in up to 94% isolated yield.

Clinical Efficacy Analysis of Tiotropium Bromide Combined with Budesonide and Formoterol Inhalation in Treating COPD

Objective:To analyze the clinical efficacy of tiotropium bromide(TB)combined with budesonide formoterol(BUD/FM)inhalation in treating chronic obstructive pulmonary disease(COPD).Methods:62 COPD patients admitted to the hospital between June 2020 and December 2022 were selected as samples for this study.The patients were divided into a combination group and a conventional group using the random number table method,with 31 cases in each group.The patients in the combination group were treated with TB combined with BUD/FM inhalation,whereas the patients in the conventional group were treated with BUD/FM inhalation only.The treatment efficacy and changes in lung function indicators of both groups were compared.Results:The total efficacy of treatment in the combined group was higher than that in the conventional group,and the difference was statistically significant(P<0.05).Before treatment,there was no difference in pulmonary function indicators between the two groups(P>0.05).After three months of treatment,all lung function indicators of the combined group were higher than those of the conventional group,and the difference was statistically significant(P<0.05).Conclusion:Combining TB with BUD/FM inhalation therapy increases the efficacy of treatment for patients with COPD.Besides,it also improves lung function and leads to a better prognosis.

Studies on sulfinatodehalogenation——ⅪⅩ.The reaction of perfluoroalkyl iodides and perfluoroalkane-sulfonyl bromides with conjugated dienes

The reaction of TbCl_3 with K[2,4-(CH_2)_2C_5H_5] at 0℃ in THF followed by crystalliza- tion at -90℃ led to a pale yellow hexagonal prismatic crystalline product [2,4-[CH_3)_2-η~5-C_5H_5]_(2-) Tb·1/2THF, which is highly sensitive to air and water and rapidly efflorescent at ambient temper- ature. The single Crystal X-ray diffraction data of the compound have been collected at low tem- perature (-60℃) and the crystal structure has been solved by heavy atom method. It belongs to triclinic system, space group Pl with lattice parameters a=8.477 (?),b=12.583 (?),c=12.858 (?), a=118.08°,β=91.38°,γ=108.75°,V=1120.36 (?)~ 3 and Z=2. Least-squares refinement converged to a final value R=0.043. The compound possesses an idealized G_(2h) symmetry、with three 2,4- dimethylpentadienyl ligands bound to the central terbium atom in a pentahapto mode (η~5). Each unit cell contains two molecules of[2,4-(CH_3)_2-η~5-C_5H_5]_3Tb and one molecule of solvent THF, of which the role in the lattice has been discussed in detail.

Direct C-H Bond Activation of Benzoxazole and Benzothiazole with Aryl Bromides Catalyzed by Palladium（Ⅱ）-N-heterocyclic Carbene Complexes

Herein, we report that a series of novel palladium（II）-NHC complexes （NHC=N-heterocyclic carbene） were synthesized. The structures of all novel complexes were characterized by ^1H NMR, ^13C NMR, FT-IR spectroscopy and elemental analysis techniques. These palladium（ll）-NHC complexes were tested as efficient catalysts in the direct C-H bond activation of benzoxazole and benzothiazole with aryl bromides in the presence of 1 mol% catalyst loading at 150 ℃ for 4 h. Under the given conditions, various aryl bromides were successfully applied as the arylating reagents to achieve the 2-arylbenzoxazoles and 2-arylbenzothiazoles in acceptable to high yields.

An Easy Access to Oxime Ethers by Pd-Catalyzed C—O Cross-Coupling of Activated Aryl Bromides with Ketoximes and Chalcone Oximes

An efficient Pd-catalyzed method for C—O cross-coupling of ketoximes and chalcone oximes with activated aryl bromides and bromo-chalcones has been developed.All oxime ethers were obtained in good to excellent yields by[(π-allyl)PdCl]2/tBuXPhos(L7)catalyst system.TrixiePhos(L11)was also found to be effective for the oxime coupling.This method offers an easy and smooth coupling of chalcone oximes with activated aryl bromides and bromo-chalcones,which has not been previously explored.