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.

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.

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-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.

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.

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.

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.

Rapid Synthesis of Glycosyl Bromides by Ultrasound Irradiation

A convenient and environmentally friendly reactor for the synthesis of glycosyl bromides via ultrasound irradiation was designed. Peracetylated glycosyl bromides were synthesized from free saccharides by means of a one-pot method. Benzoylated and 6-subsituted glycosyl bromides were prepared from protected saccharides. The glycosyl bromides were obtained in isolated yields of 83% to 96%.

Homocoupling of Aryl Bromides Catalyzed by Nickel Chloride in Pyridine

Pyridine was used as a solvent for homocoupling of aryl bromides catalyzed by nickel chloride/triarylphosphine in the presence of zinc and recycled easily. Triphenylphosphine was the best ligand for nickel in this coupling reaction.

Stereoselective synthesis of D-α-glucopyranosides,di-and tri-saccharides via 6-O-acetyl-glucopyranosyl bromides

Acetyl bromide cleaved 2,3,4-tri-O-benzyl-l,6-anhydro-B-D-glucopyranose (la) or 2,3,4-tri-O-benzyl-1,6-anhydro-B-Z)-galactopyranose (1a') to give the corresponding a-D-pyranosyl bromides (2). Reaction of 2 with ROH/diisopropylethylamine gave the corresponding a-glucopyra-nosides, di- and tri-saccharides with good yield. It was available to use 13C NMR to monitor the glycosidation reaction.

A Sustainable Synthesis of 2-Benzoxazyl and 2-Benzothiazyl Ketones from Alkynyl Bromides and 2-Amino（thio）phenols Promoted by a Recyclable Catalytic System

An environmentally and economically sustainable synthesis of 2-benzoxazyl ketones and 2-benzothiazyl ke- tones through FeC13·6H2O catalyzed tandem reactions of alkynyl bromides with 2-amino（thio）phenols in [bmim]BF4 has been developed. Remarkable advantages of this new synthetic strategy include high efficiency, readily available starting materials, and recyclable catalyst and reaction medium.

Azoximer bromide and hydroxyapatite:promising immune adjuvants in cancer

Immune adjuvants are immune modulators that have been developed in the context of infectious vaccinations.There is currently a growing interest in immune adjuvants due to the development of immunotherapy against cancers.Immune adjuvant mechanisms of action are focused on the initiation and amplification of the inflammatory response leading to the innate immune response,followed by the adaptive immune response.The main activity lies in the support of antigen presentation and the maturation and functions of dendritic cells.Most immune adjuvants are associated with a vaccine or incorporated into the new generation of m RNA vaccines.Few immune adjuvants are used as drugs.Hydroxyapatite(HA)ceramics and azoximer bromide(AZB)are overlooked molecules that were used in early clinical trials,which demonstrated clinical efficacy and excellent tolerance profiles.HA combined in an autologous vaccine was previously developed in the veterinary field for use in canine spontaneous lymphomas.AZB,an original immune modulator derived from a class of heterochain aliphatic polyamines that is licensed in Russia,the Commonwealth of Independent States,and Slovakia for infectious and inflammatory diseases,is and now being developed for use in cancer with promising results.These two immune adjuvants can be combined in various immunotherapy strategies.

Preparation of Spherical Tungsten Particles Assisted by Hydrothermal Method

We presented a strategy to prepare spherical tungsten powder by the combination of hydrothermal method and H2reduction process.In hydrothermal process,the micelle of tetraethylammonium bromide(TEAB)act as spherical templates for the deposition of tungsten oxide,whereas the excessive TEAB inhibit the formation of spherical tungsten oxide due to the dense molecular layer of TEAB on the tungsten oxide particles.Citric acid(CA)can control the formation rate and structure of the tungsten oxide when its concentration is more than 0.2 mol/L,because of its ability to coordinate with tungsten atoms.The synergistic effect of TEAB and CA facilitates the formation of spherical tungsten oxide with nanorod crown.After being treated by H_(2)at 600 and 650℃,the tungsten oxide particles are reduced to tungsten particles,which maintain the spherical structure of tungsten oxide and have porous structure.

Feasibility of Tiotropium Bromide Treatment in Patients with Asthma-COPD Overlap Syndrome and its Effect on Lung Function

Objective:To explore the feasibility of tiotropium bromide therapy and its effect on the lung function of patients with asthma-COPD overlap syndrome(ACOS).Method:The 58 subjects selected in this study were all ACOS patients admitted to our hospital(Hohhot First Hospital)from October 2020 to October 2022.They were grouped according to the random number table method and divided into a control group(29 cases)and an observation group(29 cases).The control group received routine treatment plus salmeterol-fluticasone powder inhalation treatment,and the observation group received tiotropium bromide treatment.The relevant indicators of the two groups were compared.Results:The total clinical effective rate of the observation group was significantly higher than that of the control group.Besides,the forced vital capacity(FVC),forced expiratory volume in 1 second(FEV1)levels,and ACT scores of the two groups increased after treatment,with the observation group having better results than the control group.The residual volume-total lung capacity ratio(RV/TLC),acute exacerbation frequency,and CAT scores all decreased,with the observation group showing smaller values than the control group.The difference between the results of both groups were significant(P<0.05)Conclusion:Tiotropium bromide has a significant clinical effect in the treatment of ACOS patients and can effectively improve the lung function of patients.

Tiotropium Bromide/Olodaterol Related Acute Cognitive Impairments

Background: The use of anticholinergics has been on the rise. With the increase in population longevity, more medication-related cognitive impairments (ACIs) have been reported. These impairments result in significant morbidities. We present a case that stresses on the importance of being vigilant when prescribing anticholinergic medications, especially in the elderlies. Case Report: A case of ACIs related to the use of tiotropium bromide/olodaterol (Stiolto Respimat) is being reported in a 71-year-old white man with COPD. Treatment with budesonide 180 mcg/actuation, and tiotropium bromide/olodaterol (Stiolto Respimat) inhalers was initiated. Two days after initiating treatment, the patient developed ACIs which manifested by gait imbalance, short-term memory dysfunction, inability to remember his family members, or to take his medications. Tiotropium bromide/olodaterol (Stiolto Respimat) was discontinued. After three days, a full recovery of ACIs was reported. A month later, due to worsening dyspnea, the patient self-resumed the medicine. Similar ACIs were reported within two days of resuming treatment. Tiotropium bromide/olodaterol (Stiolto Respimat) was discontinued indefinitely. Full recovery of ACIs was reported. Conclusion: ACIs should be noted as a significant side effect of tiotropium bromide/olodaterol. Clinicians should be vigilant, when prescribing anticholinergic medications to elderlies.

Effects of Combined Inhalation of Budesonide,Formoterol,and Tiotropium Bromide on Arterial Blood Gas and Pulmonary Function Indexes in Patients with Chronic Obstructive Pulmonary Disease

Objective:To analyze the effect of combined inhalation of budesonide formoterol and tiotropium bromide on arterial blood gas and pulmonary function indexes in patients with chronic obstructive pulmonary disease(COPD).Methods:100 patients with COPD treated from January to December 2022 were selected as observation objects,and were divided into a control group(n=50,in which budesonide and formoterol were administered)and an experimental group(n=50,the treatment drug was budesonide formoterol combined with tiotropium bromide)according to the computer grouping method,and compared the treatment results.Results:(i)Before treatment,there was no difference in the partial pressure of carbon dioxide and partial pressure of oxygen between the control group and the experimental group(P>0.05);after treatment,the partial pressure of carbon dioxide and partial pressure of oxygen in the experimental group were higher than those in the control group,with significant differences(P<0.05).(ii)Before treatment,there was no difference in forced vital capacity(FVC),forced expiratory volume in one second(FEV1),FEV1/FVC between the control group and the experimental group(P>0.05);after treatment,the FVC,FEV1,and FEV1/FVC in the experimental group were significantly higher than those in the control group(P<0.05).(iii)There was no difference in the levels of CRP,IL-6,and TNF-αbetween the control group and the experimental group(P>0.05);after treatment,the levels of CRP,IL-6,and TNF-αin the experimental group were lower than those in the control group,with significant differences(P<0.05).(iv)Compared to the total incidence of adverse reactions in the control group(28.00%),the incidence of total adverse reactions in the experimental group was lower at 10.00%,and the difference was significant(P<0.05).Conclusion:The combined inhalation of budesonide and formoterol with tiotropium bromide has demonstrated a clear therapeutic efficacy and safety in treating chronic obstructive pulmonary disease.This treatment approach effectively enhances arterial blood gas levels and lung function,showing promising potential for widespread application.