Catalyst-free synthesis of imidazo [1,2-a] pyridines via Groebke multicomponent reaction

Deep eutectic solvents are becoming more popular nowadays since they are green, safe and often save raw materials and energy compared to organic solvent. Due to the importance of environmentally compatible solvent in multicomponent reactions, herein we report an efficient and sustainable catalyst-free synthesis of imidazo [1,2-a] pyridines via Groebke multicomponent reaction in choline chloride-based deep eutectic solvent. One-pot, three-component reaction of 2-amino pyridine, aromatic aldehydes and cyclohexyl isocyanide in six different choline chloride-based deep eutectic solvents in the absence of catalyst were examined. Urea–choline chloride was selected as an efficient solvent for this isocyanide-based multicomponent reaction and afforded the imidazo [1,2-a] pyridines in good yields of 57–87 % and reaction times of 2–6 h. The method has several advantages such as environmentally benign and biodegradable solvent, easy purification processes by a simple filtration and methodological simplicity.     

Fast 62–92 % yield preparation of amino acid dithiocarbamates in green solvent at room temperature

Dithiocarbamate and their derivatives are of importance in medicinal chemistry due to their biological activities, in agriculture as fungicides and in organic synthesis as versatile synthetic intermediates. Green solvents such as deep eutectic solvents and polyethylene glycol are new emerging alternatives to conventional harmful organic solvents. Here, we report the synthesis of amino acid–based dithiocarbamates by one-pot three-component reaction of the electrophilic reagent, carbon disulfide and α-amino acids in deep eutectic solvent and polyethylene glycol as a catalyst and reaction media. In situ preparation of dithiocarbamates by the reaction of different amino acids and carbon disulfide, followed by addition reaction with epoxides, alkyl halides and α, β-unsaturated enones at room temperature, gave the corresponding products in 62–92 % yield with a short reaction time without any tedious workup procedures. The deep eutectic solvents and polyethylene glycol were recycled without activity or yield decrease. Therefore, the synthesis of amino acid–based dithiocarbamates in green solvents is a promising alternative to previously used procedures.     

Greener coumarin synthesis by Knoevenagel condensation using biodegradable choline chloride

Aqueous catalysis is an innovative task for the sustainable chemical industry. The use of biodegradable catalysts from natural sources may lead to greener reactions. Here, we report the synthesis of coumarin by Knoevenagel condensation using choline chloride as catalyst. Results show that even 10% of choline chloride can catalyze Knoevenagel condensation to yield coumarin in good yields. Almost all reactions proceeded faster, cleaner and in higher yields in aqueous media. Reaction mechanisms are proposed. The choline chloride catalyst was recycled five times without activity or yield decrease. Therefore, the synthesis of coumarin by Knoevenagel condensation using choline chloride as catalyst is a promising alternative to previously used procedures.     

芳烃混合物溶解规律的研究

本文利用双波长紫外分光光度法测定了多种组成的芳烃混合物在水相的溶解度,发现有机相中共存物质的组成及相互作用对它们各自的水溶解度具有重要影响。实验表明:液-液混合物表现出接近理想溶液的溶解行为;固-固混合物的溶解行为比较复杂,结构相近的固-固混合物的溶解行为接近理想溶液,而结构不相近的固-固混合物中各组份的溶解度与纯物质的溶解度接近;完全相溶的液-固混合物经固/液逸度比校正后,表现出接近理想溶液的溶解行为,本文还利用UNIFAC官能团法估算了芳烃混合物的溶解度,理论预测和实验值吻合很好。     

Glycerol as a green solvent for high product yields and selectivities

Organic synthesis is usually performed in solution to dissolve both reactants and catalysts and to deliver heat. Here, we show that glycerol, which is a non-toxic, biodegradable, and recyclable liquid manufactured from renewable sources, has a high potential to serve as alternative green solvent for organic reactions. Several catalytic and non-catalytic reactions were successfully performed in glycerol. High products yields and selectivities were achieved. Besides solubility of the reactants and the catalysts and easy separation of the product, glycerol offers several other benefits such as catalyst recycling, microwave assisting reaction, and biphasic and emulsion modes.     

一种新的有机污染物C18 EmporeTM膜/水分配系数测定方法的探讨

本文采用C18Empore^TM膜替代正辛醇模拟生物体，建立了一套新的C18Empore^TM膜／水分配系数的测定方法，并从理论和实验两方面分析了C18Empore^TM膜／水分配 系数与正辛醇／水分配系数的异同点。实验结果表明，此法测定混合有机化合物的C18Empore^TM膜／水分配系数，可以取得较为满意的结果，这种新的有机污染物C18Empore^TM膜／水分配系数测定方法的建立，可为受污染可流中混合有机物生物富集因子（BCF）的预测和水环境纳污容量的评价提供技术支持，也为多经且分有机化合物定量结果－活性相关（QSARs）的研究和实际应用开辟广阔前景。     

Direct synthesis of 2,4,5-trisubstituted imidazoles from alcohols and α-hydroxyketones by microwave

This article reports a fast, simple and efficient method to synthesize highly substituted imidazoles. Green organic synthesis is needed to face current environmental pollution. For instance the replacement of hazardous organic compounds by safe alternatives is particularly relevant. Ionic liquids are an environmentally friendly alternative to conventional organic solvents due to their unique physicochemical properties. Substituted imidazoles have been widely used to prepare pharmaceuticals. Many synthetic approaches have been developed to produce substituted imidazoles. However, despite considerable efforts only a few green methods are reported for the synthesis of highly substituted imidazoles. Here a straightforward and atom-economic approach is reported to synthesize a series 2,4,5-trisubstituted imidazoles directly from α-hydroxyketones and alcohols employing 1-methyl-3-H-imidazolium nitrate as a promoter and medium under microwave irradiation. The protocol has several advantages such as high yields of 77–91 %, short reaction times of 6–8 min, easy purification processes, and methodological simplicity due to the formation of carbon–carbon and carbon–heteroatom bonds in a single step. The methodology has been further extended towards the facile synthesis of Trifenagrel in good yield. This method provides new opportunities for the rapid screening of a wide range of compounds, either for the development of new drugs or total synthesis of natural products.     

中心复合设计射线法考察离子液体C16H31ClN2与乐果的毒性相互作用

离子液体(ILs)是一种用于替代传统易挥发有机溶剂的新型"绿色"溶剂.由于不挥发、不会对大气产生污染而得到广泛应用.但是某些ILs易溶于水,其自身毒性能够对生态环境造成潜在影响,这已引起诸多学者对ILs毒性的研究兴趣.然而ILs与其它污染物的毒性相互作用目前研究很少.论文选取咪唑类离子液体C16H31ClN(2DMI)与有机磷杀虫剂乐果(DIM)作为目标化合物,以青海弧菌Q67为检测生物,采用微板毒性分析法测定了目标化合物及其混合物的毒性.为全面考察不同浓度范围DMI与DIM的毒性相互作用,将中心复合设计与固定浓度比射线法有机结合起来构建5个不同浓度比的混合物射线,通过浓度加和与独立作用模型对混合物射线进行比较评估.结果表明在DMI浓度较大且DIM浓度较低时,DMI与DIM之间存在明显拮抗作用,而在其它浓度范围内两者之间为加和作用.     

Halogenated organic compounds (volatile and non volatile) as parameters for the evaluation of drinking water quality)†

Trihalomethanes are a well known parameter of water quality, but the determinations of the other volatile organochlorine compounds and of total organic halogen can give us more complete informations. Results are given about their use for ground waters and for treated surface waters. Ground waters may be polluted by halogenated solvents. The choice of an oxidizing agent has a great influence upon the quality of treated river water.     

Optimized porous clay heterostructure for removal of acetaldehyde and toluene from indoor air

Adsorption is the most widely used technology for the removal of indoor volatile organic compounds (VOCs). However, existing adsorbent-based technologies are inadequate to meet the regulatory requirement, due to their limited adsorption capacity and efficiency, especially under high relative humidity (RH) conditions. In this study, a series of new porous clay heterostructure (PCH) adsorbents with various ratios of micropores to mesopores were synthesized, characterized and tested for the adsorption of acetaldehyde and toluene. Two of them, PCH25 and PCH50, exhibited markedly improved adsorption capability, especially for hydrophilic acetaldehyde. The improved adsorption was attributed to their large micropore areas and high micropore-to-mesopore volume ratios. The amount of acetaldehyde adsorbed onto PCH25 at equilibrium reached 62.7 mg·g⁻¹, eight times as much as the amount adsorbed onto conventional activated carbon (AC). Even at a high RH of 80%, PCH25 removed seven and four times more of the acetaldehyde than AC and the unmodified raw PCHs did, respectively. This new PCH optimized for their high adsorption and resistance to humidity has promising applications as a cost-effective adsorbent for indoor air purification.     

Monitoring of total volatile organic compound emissions from plastic runway surfaces

Abstract

Simulated with small environmental chambers, the emission characteristics of total volatile organic compounds from plastic runway surfaces were investigated by thermal desorption–gas chromatography–mass spectrometry. This quantitative approach was validated using a dynamic recovery experiment, and the variation of emission factors from mixed-type plastic surfaces was determined. Also, the photodegradation of volatile organic compounds in chambers was introduced to decrease the background interference.     

Generation of new carbon–carbon and carbon–heteroatom bonds mediated by agro-waste extracts: a review

Agro-waste extracts are considered green solvents since they are easy to handle, readily accessible from natural waste feedstock, biodegradable and recyclable. Therefore, the employment of these extracts in reaction media has emerged as the most useful and eco-friendly alternative in modern organic chemistry. Here, we review recent developments for the generation of new carbon–carbon and carbon–heteroatom bonds mediated by agro-waste extracts. We show that these aqueous extracts have great applicability in several transformations, including condensations, oxidations, multicomponent and coupling reactions. The challenges and advantages on the use of water of agro-waste extracts in synthetic methodologies is also detail.

     

Direct production of hydroxymethylfurfural from raw grape berry biomass using ionic liquids and metal chlorides

We report for the first time the direct conversion of raw grape berry biomass to hydroxymethylfurfural (HMF) using ionic liquid solvents with metal chloride catalysts. Exploiting raw plant biomass as a biorefinery feedstock is innovative for sustainable chemical industry. The use of the raw biomass to synthesize compounds can indeed lead to less energy consumption and less CO₂ emissions. Using raw plant biomass skips pretreatment steps that are required to produce biomaterials such as carbohydrates or cellulosic biomass. Here, grape berry biomass was used as a raw chemical feedstock for the production of hydroxymethylfurfural, a key platform intermediate for syntheses of future renewable biofuels. We examined 3 ionic liquid solvents, 3 reaction temperatures, 5 chloride catalysts, and 5 concentrations of HCl. We found an increasing HMF yields depending on reaction conditions. 1-octyl-3-methylimidazolium chloride was most effective for HMF synthesis. Addition of HCl or metal chlorides alone showed little improvement. The highest HMF yield of about 100 mg HMF per mL of grape biomass extract was obtained using 0.3 M HCl, [OMIM]Cl, and CrCl₂ at 100°C for 3 h. Our study provides a model system of sustainable production of valuable compounds from raw plant biomass.     

离子液体与有机磷农药间的毒性相互作用

"绿色"溶剂离子液体(ILs)与其他污染物之间的毒性相互作用已有报道,但相关数据仍较为缺乏。以7种具有不同阴阳离子组成的ILs:溴化丁基吡啶(IL1)、氯化丁基-2,3-二甲基咪唑(IL2)、丁基-3-甲基咪唑翁磷酸盐(IL3)、丁基-3-甲基咪唑正辛基硫酸(IL4)、丁基-2,3-二甲基咪唑二乙二醇单甲醚硫酸盐(IL5)、辛基-3-甲基咪唑二乙基醚单甲磺硫酸(IL6)和氯化己基-3-甲基咪唑(IL7),与5种有机磷农药(OPs):敌敌畏(DIC)、乐果(DIM)、草甘膦(GLY)、久效磷(MON)和磷胺(PHO),作为混合物组分,以等效应浓度比射线法设计7种ILs分别与5种OPs等EC_(50)配比的35组二元混合物,应用微板毒性分析法(MTA)测定这些混合物对青海弧菌Q67的毒性,以浓度加和(CA)和独立作用(IA)为参考模型分析毒性相互作用。结果表明,不同的IL-OP混合物呈现的作用类型不同:如IL1-DIM、IL2-DIM、IL3-DIM、IL6-DIM、IL2-MON和IL7-DIM的混合物呈明显的拮抗作用;IL3-DIC和IL2-GLY的混合物呈明显的协同作用;IL5-DIM和IL4-MON的混合物在较高浓度区呈拮抗作用;而IL3-GLY和IL6-DIC的混合物在较高浓度区呈协同作用;其余的混合物则为加和作用。     

The determination of partition coefficients of organic compounds in technical products and waste waters for the estimation of their bioaccumulation potential using reversed phase thin layer chromatography

Reversed phase thin layer chromatography (RPTLC) has been investigated for the estimation of octanol/water partition coefficients (P), an important parameter for the prediction of the environmental behaviour of organic chemicals. A strong correlation between P derived from the traditional octanol/water system and RPTLC has been established over five orders of magnitude. RPTLC data are likewise correlated to results obtained by high performance chromatography (HPLC). Due to the low costs, simplicity and separation power RPTLC is especially suited for the investigation and screening of mixtures of compounds before more complicated tests are involved.

Results from a round robin test on the determination of partition coefficients by HPLC, RPTLC and the batch method indicate the simplicity and accuracy of the RPTLC technique. Applications of the RPTLC‐technique on technical products and industrial waste waters are described.     

A novel ligand for cloud point extraction to determine gold content in ore samples

Gold is a valuable metal occurring usually at very low concentrations in complex natural samples. Gold analysis thus needs preconcentration methods. Classical liquid–liquid extraction involves hazardous organic solvents. Alternatively, cloud point extraction involves non-toxic and nonvolatile surfactants. Here, we analyzed ore samples. The complex of Au(III) with sulphapyridylazo resorcin was extracted by the cloud point method. Concentrations were measured by flame atomic absorption spectrometry. We tested the effects of pH, reagent concentration, Triton X-100 surfactant concentration, equilibration temperature and time. Results show that the best detection limit of the method was 0.48 µg L^?1 for Au with a preconcentration factor of 31 times. Calibration is linear in range of 6.4–2,000 µg L^?1, and relative standard deviations are lower than 5 %. Quantum chemical computations reveal the plausible structure of the gold–ligand complex. This report represents the first determination of gold using sulphapyridylazo resorcin as a ligand.     

Design and prediction for highly efficient SO2 capture from flue gas by imidazolium ionic liquids

An efficient method for prediction in the capture of SO2 from flue gas by imidazolium ionic liquids was reported, where the concentration of SO2 is 2000 ppm. On the basis of quantitative calculations through a combination of Langmuir simulation, theoretical calculation and quantum chemical method, SO2 absorption and desorption performance from flue gas by twelve kinds of imidazolium ionic liquids with different anions were designed and predicted. Then, among them, five kinds of imidazolium ionic liquids were chosen and prepared to investigate their behavior of SO2 absorption capacity, desorption residue, and available absorption capacity. The results indicated that the experimental values were in good agreement with the predicted values. Thus, an ideal ionic liquid [Emim][Tetz] was obtained through the predictive method for the capture of SO2 of 2000 ppm, which showed high available absorption capacity of 0.24 g SO2 per g ionic liquid and excellent reversibility.     

Extraction,isolation, and identification of various environment friendly components from cock's comb (Celosia argentea) leaves for allelopathic potential

In this study, the aqueous extract of leaves of the plant cock's comb (Celosia argentea) was fractioned into five batches using n-hexane, dichloromethane, ethyl acetate, and n-butanol, respectively. High performance liquid chromatography analysis of the methanol re-dissolved residues of 3 polar fractions, including dichloromethane, ethyl acetate, and n-butanol separately which exhibited altogether 12 compounds identified as 4-hydroxycinnamic acid (p-coumaric acid), 4-hydroxybenzoic acid, protocatechuic acid, caffeic acid, m-coumaric acid, gallic acid, 4-hydroxybenzaldehyde, m-hydroxybenzaldehyde, 2,4-dihydroxybenzoic acid, pyrogallol, 3,5-dihydroxybenzoic acid, and genetic acid was categorized by retention time using known compounds. Similarly, the mass confirmation of most of the identified compounds was achieved by injecting 20 µl of composite sample of these three polar fractions into liquid chromatography–mass spectrometry. Similarly, the physiochemical analysis of C. argentea aqueous extract showed the presence of various constituents such as phenols, flavonoids, tannins, and glycosides. All four organic fractions were examined for phytotoxicity against Lepidium sativum. Analysis of variance showed significant differences among these fractions against germination and growth of L. sativum. Further allelopathic effects appeared to be concentration dependent. Thus, C. argentea may prove effective as a substitute of herbicides to control the weeds like L. sativum from attacking crops and to protect the environment from the health hazard effects of herbicides.     

香港河流沉积物中有机碳对铜的吸附特性

采用厌氧序列分批滴定装置（ＡＳＢＴ）研究了香港青山湾避风塘和屯门河、城门河、林村河感潮河段沉积物中有机碳对铜的吸附特性。结果表明，在ｐＨ１６和ｐＨ７的条件下，沉积物中有机碳对铜的吸附特性可用Ｌａｎｇｍｕｉｒ等温式描述，铜在不同河流沉积物有机碳中的分配系数差别较大，吸附容量差别较小，Ｈ＾＋可以结合沉积物有机碳的重金属结合位点，导致吸附容量和分配系数随ｐＨ增大而增大。     

城市垃圾二次性好氧堆肥化工艺的若干设计方程

二次性好氧堆肥化工艺是基于将堆肥化过程中高温微生物和中温微生物在分开的、各自适宜的环境中 进行不同基质降解和稳定化的一种较新工艺．通过实验，由物料平衡式结合微生物反应动力学 建立了 城市垃圾二次性好氧堆肥工艺的若干基本设计方程式：一次发酵阶段的生物降解方程， Ｋ Ａｖ 值高的易降解物具有一级反应的性质，试验求出的比率常数 Ｋｄ 为０１１９ ｄ － １ ；一次 发酵阶段的堆肥减量二元线性方程，减量主要与挥发性固体降解率和水份蒸发量有关；一次 发酵动态反应器容积和二次发酵构筑物有效面积的计算式，计算式主要考虑了减量、容重变化及堆肥返料量的影响；一次发酵阶段所需理论通风量的计算式，通风量主要由微生 物需氧量和水份蒸发量所需的空气量组成，后者需气量往往大于前者，有时高达２ ～６ 倍．