Short Syntheses of some ‘Decalin‐1,8‐diones’ and their Derivatives: Breaking the Pretended Symmetry

A cheap synthesis of the so‐called ‘decalin‐1,8‐diones’ started with the conjugate (1,4‐) addition of cyclohex‐2‐en‐1‐one derivatives to the γ‐position of the dilithium derivative (buta‐1,3‐diene‐1,1‐bis(olate)) of crotonic acid. Hydrogenation of these ‘1,4‐γ’ adducts and final cyclization afforded the enol tautomers of decalin‐1,8‐diones. Nucleophilic substitutions at these 3‐oxoenols by NH₃ or primary amines created only monoamino products (namely, 3‐oxoenamines) whose reactions with OPCl₃ yielded dihydro(1,3,2)oxazaphosphinin‐2‐one derivatives. The two regioisomers of a trimethyl‐3‐oxoenamine served as models for the constitutional assignments of the two rapidly interconverting (hence, individually NMR‐invisible), tautomeric trimethyl‐3‐oxoenols. Such methyl substitutions served to break the ‘pretended’ symmetry of ‘decalin‐1,8‐dione’. Hydrazine and 3‐oxoenols furnished oxygen‐free indazole derivatives whose N?H bonds exchanged with t_1/2=ca. 0.00035 s at ca. ?58(9) °C.     

Interaction of 1-acylamino-2,2-dichloroethenyl(triphenyl)phosphonium chlorides with alkanolamines

Abstract

It is shown that the interaction of 1-acylamino-2,2-dichloroethenyl(triphenyl)-phosphonium chlorides with alkanolamines having a primary amino group results in the formation of 4-oxazolylphosphonium salts containing hydroxyalkylamine substituents at position 5 of the oxazole cycle. Under similar conditions the reaction of N-substituted alkanolamines with 1-acylamino-2,2-dichloroethenyl-(triphenyl)phosphonium chlorides leads to the formation of 1,3-oxazolidin-2-ylidene derivatives, in which the triphenylphosphonium group is located in the side chain. The structure of the new synthesized compounds has been reliably proven by elemental analysis, IR, ¹Н, ¹³С, ³¹Р NMR spectroscopy, mass spectrometry and single crystal X-ray diffraction.     

Synthesis of 2-amino-3,6-di(het)arylpyridines from 5-cyano-3,6-di(het)aryl-1,2,4-triazines and arylhydrazines via the SNipso/aza-Diels–Alder reaction sequence

Reaction between 5-cyano-3,6-di(het)aryl-1,2,4-triazines and arylhydrazines with the following aza-Diels–Alder autoclave reaction affords hardly available 2-amino-3,6-di(het)aryl-pyridines in up to 67% yield after two steps and in 75% yield for the one-pot way. The compounds obtained can be promising for medicinal chemistry.     

基于激光雷达的垂直能见度反演算法及其误差评估

针对大气垂直方向上消光系数分布不均匀难以用传统方法直接测量垂直能见度的问题,提出了一种基于激光雷达探测垂直能见度的计算方法。根据大气辐射传输基本原理,借助于辐射传输方程,推导出了垂直能见度的计算公式;然后利用激光雷达原理方程和Klett算法反演出大气垂直方向上的消光系数分布,基于此提出了垂直能见度的迭代算法。最后,利用灰色模型GM(1,1)和批统计算法,对激光雷达反演得到的后向散射系数进行了评估,给出了误差置信区间为(0.760±0.339)×10^-4(srad·km)^-1。结果表明,该方法是一种特别有效的计算垂直能见度的方法,符合探测的基本需求,且误差小精度高。     

Green synthesis of Fe3O4/ZnO magnetic core-shell nanoparticles by Petasites hybridus rhizome water extract and their application for the synthesis of pyran derivatives: Investigation of antioxidant and antimicrobial activity

In this research, Fe₃O₄/ZnO magnetic core-shell nanoparticles (Fe₃O₄/ZnO MCNPs) were synthesized through a green method using Petasites hybridus rhizome water extract as a reducing and stabilizing agent. The morphology and size of the Fe₃O₄/ZnO MCNPs was identified by X-ray diffraction, scanning electron microscopy, and Energy-dispersive X-ray spectroscopy (EDX) analysis. The catalytic activity of the Fe₃O₄/ZnO MCNPs was evaluated in the efficient and green preparation of pyran derivatives in excellent yield using three-component reactions of dimedone, aldehydes, and malononitrile in ethanol at room temperature. The ability of some synthesized compounds to scavenge the 2,2-diphenyl-1-picrylhydrazyl radical was measured and the results proved this observation. Moreover, the antimicrobial activity of some synthesized compounds was proved by employing the disk diffusion test on Gram-positive and Gram-negative bacteria. The results for the disk diffusion test showed that compounds ( 4c, 4d, 4f and 4g ) prevented bacterial growth.     

Metabolomics techniques applied in the investigation of phenolic acids from the agro-industrial by-product of Carapa guianensis Aubl

Processing of Carapa guianensis seeds to obtain oil on an industrial scale generates a significant amount of by-product, approximately 66% w/w, which is called cake and is a potential source of biomolecules, including simple phenolic structures. For this reason, studies were carried out on the chemical profiles of hydrolyzed extract from this agro-industrial by-product through High Performance Thin-Layer Chromatography (HPTLC) and Gas Chromatography coupled to Mass Spectrometry (GC–MS). These techniques were used to detect metabolic classes and/or groups, and to identify, for the first time, thirteen simple phenolic acids in this by-product. The sample antioxidant capacity was determined by methods of 2,2-diphenyl-1-picrylhydrazyl (DPPH)and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS⁺) radicals direct sequestration. The hydrolyzed fraction showed a total of 63.47% in the relative abundance of the total of compounds, standing out: p-hydroxybenzoic acid (39.19%) and protocatechuic acid (3,4-dihydroxybenzoic acid) (5.62%), both from hydroxybenzoic acids and 3-(3,4-dihydroxyphenyl)lactic acid, (7.76%) hydroxycinnamic acids derivatives. In these results, the fraction rich in simple phenolic acids was obtained, attributing the prominent behavior of this matrix antioxidant activity, expressed by (IC₅₀: of 16.42 µg/mL and 6.52 µg/mL for DPPH and ABTS⁺ radicals, respectively). The research demonstrated an alternative to applicability that involves sustainability from agro-industrial. These techniques were used to detect metabolic classes and/or groups, and to identify, for the first time, thirteen simple phenolic acids in this by-product, generating a process capable of converting biomass into a bioproduct, consisting of bioactive compounds, in addition to adding value to the industrial chain.     

19F-detected dual-optimized inverted 1JCC 1,n-ADEQUATE

Modification of the recently reported ¹⁹F-detected 1,1-ADEQUATE experiment that incorporates dual-optimization to selectively invert a wide range of ¹J_CC correlations in a 1,n-ADEQUATE experiment is reported. Parameters for the dual-optimization segment of the pulse sequence were modified to accommodate the increased size of ¹J_CC homonuclear coupling constants of poly- and perfluorinated molecules relative to protonated molecules to allow broadband inversion of the ¹J_CC correlations. The observation and utility of isotope shifts are reported for the first time for 1,1- and 1,n-ADEQUATE correlations.     

含硫柔性二苯甲酸及氮杂环配体的Zn(Ⅱ)和Mn(Ⅱ)配合物的合成及晶体结构

以2,2′-二硫代二苯甲酸、2,2′-联吡啶、咪唑、硝酸锌和硝酸锰为原料,使用水热方法合成了配合物[Zn(EBLA)(2,2′-bipy)(H2O)](EBLA=2,2′-二苯甲酸硫醚)(2,2′-bipy=2,2′-联吡啶)(1),自然挥发法制备了配合物[Mn(EBSA)(im)2(H2O)]n(EBSA=2,2′-二硫代二苯甲酸)(im=咪唑)(2)。利用元素分析、红外和热重分析对其进行了表征。利用X-射线单晶衍射对结构进行了测定,并研究了配合物1的荧光性质。配合物1中,2,2′-二苯甲酸硫醚是通过水热方法由2,2′-二硫代二苯甲酸发生原位反应制备,Zn2+离子是五配位的四角锥双核结构;配合物2中,Mn2+离子是六配位的变形八面体一维链状结构。配合物中存在氢键和π-π堆积等弱的分子间作用力。     

2,2-二甲基-1-[5-二茂铁基-3-(三氟甲基)-1H-吡唑-1-基]丙-1-酮的合成及其电化学性质

以乙酰基二茂铁为原料,经3步反应合成了一个新型的二茂铁衍生物——2,2-二甲基-1-[5-二茂铁基-3-(三氟甲基)-1H-吡唑-1-基]丙-1-酮(4),其结构经1H NMR,ESI-MS,元素分析和X-射线单晶衍射表征。4属单斜晶系,P2(1)/c空间群,晶胞参数a=7.805 6(4),b=20.906 1(11),c=11.124 6(6),β=93.820(2)°,V=1 811.33(17)3,Z=4,Dc=1.482 g·cm-3,μ=0.872 mm-1,R1=0.034 8,wR2=0.089 2。采用循环伏安法研究了4的电化学性质。结果表明:4有一对可逆的氧化还原峰,Epa=0.640 V,Epc=0.482 V,ΔE=153 m V。     

纳米二氧化钛-氧化锌/硅溶胶/导电胶复合材料固定联吡啶钌制备磷酸可待因电化学发光传感器

利用硅溶胶的成膜性、纳米二氧化钛-氧化锌大的比表面积及导电胶的粘结性,制备了纳米二氧化钛-氧化锌/硅溶胶/导电胶复合材料,基于此复合材料将联吡啶钌固定到金电极表面,制备了磷酸可待因电化学发光(ECL)传感器.在优化的实验条件(800 V负高压、扫描速度100 mV/s,磷酸盐缓冲体系(pH 6.5))下,可待因浓度在1.0×10-7～1.0×10-4 mol/L范围内与电化学发光强度呈良好的线性关系(r2=0.9973),检出限为2.56×10-8 mol/L (S/N=3).传感器表现出良好的重现性与稳定性,连续平行测定1.28×10-5 mol/L可待因溶液10次,发光强度的相对标准偏差(RSD)为2.7％;室温下保存10天后,发光强度为初始值的92％以上.测定可待因药物实际样品的加标回收率在99.3％ ～ 102.5％之间.