Journal of Chemical Sciences最新文献

Polythiophene, polypyrrole-NiO ternary hybrid nanocomposites: structural, morphological, dielectric and electrical properties 聚噻吩、聚吡咯-氧化镍三元杂化纳米复合材料：结构、形态、介电和电学特性

IF 1.7 4区化学 Q3 Chemistry

Journal of Chemical Sciences

Pub Date : 2023-12-09 DOI: 10.1007/s12039-023-02236-4

Dharmendra, Srikanta Moharana, Alekha Kumar Sutar, Tungabidya Maharana

Herein, we are reporting the synthesis of polythiophene, polypyrrole, and reinforced nickel oxide (NiO) hybrid nanocomposites by an in-situ chemical oxidative polymerization of thiophene and pyrrole in the presence of NiO nanoparticles. The polymerized nanocomposites were thoroughly characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) studies, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The concentration of polymer-NiO hybrids varied between different ratios of PTh, PPy and NiO contents. A maximum dielectric constant of ≈ 1×10⁶ was observed at a higher ratio of polymer-filler contents. The PTh-PPy-NiO hybrid nanocomposite structure and crystallinity were verified by X-ray diffraction (XRD), and the FTIR approach demonstrated a robust interaction between PTh, PPy, and NiO particles. The surface morphology analysis revealed that NiO particles were successfully integrated with PTh, PPy during the polymerization process by forming a network. The dielectric constant values of the resultant nanocomposites were obtained from capacitance measurements. The dielectric constant for the higher concentration ratio of polymer-NiO hybrids was much higher than that of the pristine PTh, PPy matrix. A significant increase in dielectric loss and AC conductivity was observed for the higher concentration of PTh-PPy-NiO ternary nanocomposites. These PTh-PPy-NiO hybrid nanocomposites can potentially be useful in developing high-performance composite materials in the electronic field.

Graphical abstract

Herein, we are reporting the synthesis of polythiophene, polypyrrole, and reinforced nickel oxide (NiO) hybrid nanocomposites by an in-situ chemical oxidative polymerization of thiophene and pyrrole in the presence of NiO nanoparticles. The concentration of polymer-NiO hybrids varied between different ratios of PTh, PPy, and NiO contents. A maximum dielectric constant of ≈ 1×10⁶ was observed at a higher ratio of polymer-filler contents. The dielectric constant for the higher concentration ratio of polymer-NiO hybrids was much higher than that of the pristine PTh, PPy matrix. A significant increase in dielectric loss and AC conductivity was observed for the higher concentration of PTh-PPy-NiO ternary nanocomposites. These PTh-PPy-NiO hybrid nanocomposites can potentially help develop high-performance composite materials in the electronic field.

在此，我们报告了在氧化镍纳米粒子存在下通过原位化学氧化聚合噻吩和吡咯合成聚噻吩、聚吡咯和增强氧化镍（NiO）杂化纳米复合材料的情况。傅立叶变换红外光谱（FTIR）、X 射线衍射（XRD）研究、扫描电子显微镜（SEM）和热重分析（TGA）对聚合纳米复合材料进行了全面表征。聚合物-氧化镍混合物的浓度在 PTh、PPy 和氧化镍含量的不同比例之间变化。聚合物-填充物含量比例越高，介电常数最大值≈ 1×106。X 射线衍射（XRD）验证了 PTh-PPy-NiO 杂化纳米复合材料的结构和结晶度，傅立叶变换红外（FTIR）方法证明了 PTh、PPy 和 NiO 颗粒之间的强相互作用。表面形貌分析表明，在聚合过程中，NiO 颗粒与 PTh、PPy 成功地结合在一起，形成了一个网络。通过电容测量获得了纳米复合材料的介电常数值。高浓度比的聚合物-NiO 杂化物的介电常数远高于原始 PTh、PPy 基体的介电常数。高浓度的 PTh-PPy-NiO 三元纳米复合材料的介电损耗和交流电导率明显增加。这些 PTh-PPy-NiO 杂化纳米复合材料可用于开发电子领域的高性能复合材料。图解摘要在此，我们报告了在 NiO 纳米粒子存在下，通过原位化学氧化聚合噻吩和吡咯合成聚噻吩、聚吡咯和增强氧化镍（NiO）杂化纳米复合材料的情况。聚合物-NiO 杂化物的浓度随 PTh、PPy 和 NiO 含量的不同比例而变化。聚合物-填料含量比例越高，介电常数最大值≈ 1×106。高浓度比的聚合物-NiO 杂化物的介电常数远高于原始 PTh、PPy 基体的介电常数。高浓度的 PTh-PPy-NiO 三元纳米复合材料的介电损耗和交流电导率明显增加。这些 PTh-PPy-NiO 杂化纳米复合材料可能有助于开发电子领域的高性能复合材料。

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引用次数: 0

Peripheral (anti)aromaticity in the singlet and triplet states of cyclopenta[fg]acenaphthylene, pyrrolo[2,1,5-cd]indolizine and 2a1 boracyclopenta[cd]indene: NICS scan approach 环戊并[fg]苊烯、吡咯并[2,1,5-cd]吲嗪和 2a1 硼并环戊并[cd]茚的单重态和三重态的外围（反）芳香性：NICS 扫描方法

IF 1.7 4区化学 Q3 Chemistry

Journal of Chemical Sciences

Pub Date : 2023-12-09 DOI: 10.1007/s12039-023-02230-w

Bijan K Paul

The π-electron count of cyclopenta[fg]acenaphthylene (1), pyrrolo[2,1,5-cd]indolizine (2) and 2a¹-boracyclopenta[cd]indene (3) reveals antiaromaticity of 1, and aromaticity of 2 and 3 in the ground electronic singlet state in accordance with the Hückel’s rule of aromaticity. This conjecture is well-corroborated from the Nucleus-Independent Chemical Shift (NICS) scan results. However, a systematic NICS scan study shows that in 1, the overall antiaromaticity in the S₀-state is predominantly due to contributions of the 5-membered ring, while the 6-membered ring reflects weak aromaticity even in the singlet-state. For 2 and 3, the aromatic character of the molecules is comprised of contributions from both the rings. On the contrary, the aromaticity of 1 and antiaromaticity of 2 and 3 in the triplet-state (according to Baird’s rule) are found to be due to contributions from both the (5- and 6-membered) rings of the molecules. In all the cases, the isotropic chemical shifts of the probe (Bq) atom have been separated into the in-plane and out-of-plane contributions to extract quantitative evaluation of the individual components. Further, the net paratropic (antiaromatic) or diatropic (aromatic) ring currents in a given ring have been analyzed from the separation of the individual components (in-plane and out-of-plane) into the paramagnetic and diamagnetic contributions. A quantitative comparison of the NICS values of 2 with those of 3 reveals greater aromaticity in the S₀-state and antiaromaticity in the T₁-state of 2.

Graphical abstract

Synopsis: Author, please provide a 50-word synopsis of the article.

环戊并[fg]苊烯（1）、吡咯并[2,1,5-cd]吲嗪（2）和 2a1-boracyclopenta[cd]indene （3）的 π 电子计数显示，根据 Hückel 的芳香性规则，1 具有反芳香性，而 2 和 3 在地面电子单子态具有芳香性。核独立化学位移（NICS）扫描结果充分证实了这一猜想。然而，系统的核不依赖化学位移扫描研究表明，在 1 中，S0 状态下的整体反芳香性主要是由于 5 元环的贡献，而 6 元环即使在单态也反映出微弱的芳香性。对于 2 和 3，分子的芳香特性由两个环的贡献组成。相反，1 的芳香性以及 2 和 3 在三重态下的反芳香性（根据贝尔德规则）是由分子的两个（5 元环和 6 元环）贡献的。在所有情况下，探针（Bq）原子的各向同性化学位移都被分离成平面内和平面外的贡献，以便对各个部分进行定量评估。此外，通过将单个成分（面内和面外）分离成顺磁性和二磁性贡献，分析了给定环中的各向异性（反芳香）或各向异性（芳香）环电流净值。对 2 和 3 的 NICS 值进行定量比较后发现，2 在 S0 状态下具有更大的芳香性，而在 T1 状态下具有更大的反芳香性：作者，请提供 50 个字的文章概要。

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引用次数: 0

High-resolution rovibrational cavity ring-down spectroscopy of (1200←0200) vibrational band of β-site-specific N2O isotopologue near 7.8 µm region 对 7.8 µm 波段附近的 β-位特异性 N2O 同素异形体的 (1200←0200) 振荡波段进行高分辨率滚振腔环向下光谱分析

IF 1.7 4区化学 Q3 Chemistry

Journal of Chemical Sciences

Pub Date : 2023-12-09 DOI: 10.1007/s12039-023-02232-8

Soumyadipta Chakraborty, Ardhendu Pal, Biswajit Panda, Indrayani Patra, Manik Pradhan

An external-cavity quantum cascade laser (EC-QCL) coupled cavity ring-down spectroscopy was employed at 7.8 µm to investigate high-resolution rovibrational spectral features associated with the P- and R-branches of the 12⁰0←02⁰0 vibrational hot band transition of the β-site-specific isotopologue of nitrous oxide, i.e., ¹⁵N¹⁴N¹⁶O molecule. The air-broadening phenomena of several probed rotational transitions of β-N₂O were examined by calculating the pressure-broadening coefficients. We calculated significant spectroscopic parameters such as the band centre, rotational constant, and centrifugal distortion constant for this selected vibrational band. Subsequently, we elucidated the dependence of rovibrational Einstein A coefficients on the rotational quantum number (J) and estimated the vibrational contribution of the Einstein A coefficients. We also determined the Herman Wallis coefficients corresponding to this 12⁰0←02⁰0 vibrational band. Finally, we investigated the line-oscillator strengths of the experimentally probed rovibrational transitions to gain deeper insights into the fundamental aspects of high-resolution spectroscopy of site-specific β-N₂O molecules. These new high-resolution spectroscopic features of the β-N₂O isotopologue will significantly enhance our understanding of the fundamental rovibrational spectroscopy of linear polyatomic molecules.

Graphical Abstract

This work shows the high-resolution fundamental rovibrational spectroscopy of the 12⁰0←02⁰0 vibrational hot band of site-specific ¹⁵N¹⁴N¹⁶O isotopologue of nitrous oxide using quantum cascade laser (QCL) coupled cavity ring-down spectroscopy at 7.8 µm region.

利用波长为 7.8 µm 的外腔量子级联激光器（EC-QCL）耦合腔环向下光谱技术，研究了与一氧化二氮的 β 位特异同素异形体（即 15N14N16O 分子）的 1200←0200 振动热带跃迁的 P 支和 R 支相关的高分辨率旋转振动光谱特征。通过计算压力展宽系数，研究了 β-N2O 的几个探究旋转转变的空气展宽现象。我们计算了这一选定振带的带中心、旋转常数和离心变形常数等重要光谱参数。随后，我们阐明了旋转振动爱因斯坦 A 系数与旋转量子数 (J) 的关系，并估算了爱因斯坦 A 系数的振动贡献。我们还确定了与这一 1200←0200 振带相对应的赫尔曼-沃利斯系数。最后，我们研究了实验探测到的摇振跃迁的线振子强度，从而更深入地了解了特定位点 β-N2O 分子高分辨率光谱学的基本方面。这些新的 β-N2O 同素异形体高分辨率光谱特征将极大地增强我们对线性多原子分子基本振动光谱的理解。图文并茂的摘要这项工作利用量子级联激光（QCL）耦合腔环向下光谱技术在 7.8 µm 波段显示了一氧化二氮的特定位点 15N14N16O 同素异形体的 1200←0200 振动热带的高分辨率基本振动光谱。

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引用次数: 0

Catalysis via bimetallic Pd-Sn nanoparticles: green oxidation of secondary benzyl alcohol in water in the absence of base 双金属钯锡纳米颗粒催化:水中无碱条件下仲苯甲醇的绿色氧化

IF 1.7 4区化学 Q3 Chemistry

Journal of Chemical Sciences

Pub Date : 2023-11-23 DOI: 10.1007/s12039-023-02229-3

Priyabrata Mukhi, Mukesh Kumar Nayak, Anuradha Mohanty, Sujit Roy

Novel Pd-Sn bimetallic nanoparticles have been synthesized using the wet chemical technique. The nanoparticles show excellent catalytic activity in oxidizing secondary benzyl alcohol to the corresponding carbonyl in water as the solvent without any additive. It also withstood multiple cycles without loss of activity. Preliminary kinetic studies indicate a β-hydride elimination mechanism.

Graphical abstract

A bench-friendly wet-chemical method is designed to synthesize Pd-Sn bimetallic nanoalloys characterized by PXRD, FESEM, HRTEM, UV-Vis, FT-IR, EDAX, and ICP-OES. The nanoalloy is highly dispersible in water and catalyzes the oxidation of secondary alcohols in water with high TOF.

采用湿化学技术合成了新型的Pd-Sn双金属纳米颗粒。纳米颗粒在不添加任何添加剂的情况下，以水为溶剂将仲苯甲醇氧化为相应的羰基，表现出优异的催化活性。它也经受住了多次循环而没有失去活性。初步动力学研究表明β-氢化物的消除机制。设计了一种适合实验台的湿化学方法来合成Pd-Sn双金属纳米合金，并通过PXRD、FESEM、HRTEM、UV-Vis、FT-IR、EDAX和ICP-OES进行了表征。该纳米合金在水中具有良好的分散性，可催化高TOF水中仲醇的氧化。

引用次数: 0

Rh-catalyzed asymmetric hydroformylation of olefins using phosphorus ligands 磷配体催化烯烃不对称氢甲酰化反应

IF 1.7 4区化学 Q3 Chemistry

Journal of Chemical Sciences

Pub Date : 2023-11-20 DOI: 10.1007/s12039-023-02227-5

Rohit Kumar, Anirban Sen, Samir H Chikkali

Easily accessible BINOL-based monodentate phosphite ligand L1 and hybrid ligand L2 have been synthesized in good yield by following a one-pot, two-step protocol. A single ³¹P resonance at 146.6 ppm confirmed the formation of L1. Subsequent 1-2D NMR and mass spectrometric analysis authenticated the existence of L1. These ligands afforded excellent activity and regio-selectivity in the Rh-catalyzed AHF of styrenic substrates. L1 showed excellent regioselectivity but did not discriminate between the two enantiomers, while L2 displayed an enantiomeric excess (ee) of up to 20%. In our attempts to understand the reasons for low ee, the coordination behavior of L2 was investigated. The coordination study revealed that L2 coordinates with the Rh as a monodentate ligand, although there are two P-sites. It was found that only the phosphine arm was coordinated to the Rh and the phosphite arm stayed away from the Rh core at the ambient temperature, leading to moderate ee.

Graphical abstract

One-step synthesis of a phosphite (L1) and a phosphine-phosphite (L2) ligand and their implication in the asymmetric hydroformylation of olefins with excellent regioselectivity (>95%) and moderate enantioselectivity (up to 20%) is reported.

二酚基单齿亚磷酸酯配体L1和杂化配体L2通过一锅两步法合成，收率高。在146.6 ppm的单次31P共振证实了L1的形成。随后的1-2D NMR和质谱分析证实了L1的存在。这些配体在铑催化苯乙烯底物的AHF中具有良好的活性和区域选择性。L1表现出优异的区域选择性，但不区分两种对映体，而L2表现出高达20%的对映体过剩(ee)。为了了解低ee的原因，我们研究了L2的配位行为。配位研究表明L2与Rh作为单齿配体配位，尽管有两个p位。结果发现，在环境温度下，只有膦臂与Rh协调，而亚磷酸盐臂远离Rh核心，导致中等ee。摘要:本文报道了亚磷酸酯(L1)和亚磷酸酯-亚磷酸酯(L2)配体的一步合成及其在烯烃不对称氢甲酰化反应中的应用，该配体具有优异的区域选择性(95%)和中等的对映选择性(高达20%)。

{"title":"Rh-catalyzed asymmetric hydroformylation of olefins using phosphorus ligands","authors":"Rohit Kumar, Anirban Sen, Samir H Chikkali","doi":"10.1007/s12039-023-02227-5","DOIUrl":"10.1007/s12039-023-02227-5","url":null,"abstract":"<div><p>Easily accessible BINOL-based monodentate phosphite ligand L1 and hybrid ligand L2 have been synthesized in good yield by following a one-pot, two-step protocol. A single <sup>31</sup>P resonance at 146.6 ppm confirmed the formation of L1. Subsequent 1-2D NMR and mass spectrometric analysis authenticated the existence of L1. These ligands afforded excellent activity and regio-selectivity in the Rh-catalyzed AHF of styrenic substrates. L1 showed excellent regioselectivity but did not discriminate between the two enantiomers, while L2 displayed an enantiomeric excess (ee) of up to 20%. In our attempts to understand the reasons for low ee, the coordination behavior of L2 was investigated. The coordination study revealed that L2 coordinates with the Rh as a monodentate ligand, although there are two P-sites. It was found that only the phosphine arm was coordinated to the Rh and the phosphite arm stayed away from the Rh core at the ambient temperature, leading to moderate ee.</p><h3>Graphical abstract</h3><p>One-step synthesis of a phosphite (L1) and a phosphine-phosphite (L2) ligand and their implication in the asymmetric hydroformylation of olefins with excellent regioselectivity (>95%) and moderate enantioselectivity (up to 20%) is reported.\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":50242,"journal":{"name":"Journal of Chemical Sciences","volume":"135 4","pages":""},"PeriodicalIF":1.7,"publicationDate":"2023-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138138618","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Synthesis and Photoelectric Properties of D-A Conjugated Polymers of Benzothiadiazoles with Different Molecular Weights 不同分子量苯并噻唑类D-A共轭聚合物的合成及光电性能

IF 1.7 4区化学 Q3 Chemistry

Journal of Chemical Sciences

Pub Date : 2023-11-20 DOI: 10.1007/s12039-023-02226-6

Wenming Yang, Pengfei Li, Qunxiang Fang, Weihong Huang, Wanzhen Xu

In this work, we have synthesized and characterized a series of Donor−Acceptor (D–A) conjugated polymers (PffBT4T-2DT) with different molecular weights, introduced a microwave method into the synthesis process, shortened the experimental cycle time by over 5 days and increased the molecular weight of the polymers. The conditions affecting the molecular weight of the polymers were investigated. It is shown that the prepared conjugated polymers have excellent thermal stability and solubility, higher molecular weight polymers have broader absorption spectra and stronger inter-chain aggregation, and the strong aggregation ability of polymer chains is dependent on molecular weight and solution temperature, with lower polymer molecular weight and higher solution temperature both causing weaker polymer chain aggregation. The polymer films of the three molecular weights have a uniform surface with a roughness of about 0.83 and good crystallinity. Transistor test results show that the higher molecular weight polymers perform better when applied to field effect transistors, with mobilities as high as 0.124 cm² V⁻¹ s⁻¹ and threshold voltages as low as 2 V.

Graphical Abstract

A series of donor-acceptor conjugated polymers (PffBT4T-2DT) with different molecular weights were synthesized by introducing the microwave method. The thermodynamic, optical, electrochemical and photovoltaic properties of the polymers were characterized, and the effect of molecular weight on the performance of organic field effect transistors (OFETs) was investigated.

在这项工作中，我们合成了一系列不同分子量的供体-受体(D-A)共轭聚合物(PffBT4T-2DT)，并对其进行了表征，在合成过程中引入了微波方法，将实验周期缩短了5天以上，提高了聚合物的分子量。研究了影响聚合物分子量的条件。结果表明，所制备的共轭聚合物具有优异的热稳定性和溶解度，高分子量的聚合物具有更宽的吸收光谱和更强的链间聚集，聚合物链的强聚集能力与分子量和溶液温度有关，聚合物分子量越低，溶液温度越高，聚合物链的聚集能力越弱。三种分子量的聚合物薄膜表面均匀，粗糙度约为0.83，结晶度好。晶体管测试结果表明，高分子量聚合物应用于场效应晶体管时表现更好，迁移率高达0.124 cm2 V−1 s−1，阈值电压低至2 V。摘要采用微波法合成了一系列不同分子量的给受体共轭聚合物(PffBT4T-2DT)。表征了聚合物的热力学、光学、电化学和光电性能，并研究了分子量对有机场效应晶体管性能的影响。

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引用次数: 0

Synthesis of highly efficient nitrogen enrich graphene eosin-Y coupled photocatalyst that uses solar energy in trifluoromethylation of benzaldehydes 利用太阳能合成苯甲醛三氟甲基化高效富氮石墨烯-伊红- y偶联光催化剂

IF 1.7 4区化学 Q3 Chemistry

Journal of Chemical Sciences

Pub Date : 2023-11-20 DOI: 10.1007/s12039-023-02223-9

Swati Srivastava, Rajesh K Yadav, Satyam Singh, Rehana Shahin, Atul P Singh, Navneet K Gupta, Tae Wu Kim, Jin-Ook Baeg

The production of trifluoromethyl groups on organic compounds by graphene-based photocatalysts is an emerging research area in the 21^st century. However, the pricey and poisonous nature of metal-based photocatalysts poses a significant barrier to the insertion of trifluoromethyl groups. Therefore, the trifluoromethylation of organic compounds and conversion into sustainable, greener chemicals via solar light irradiation is a hot and challenging topic. So, herein we developed a solar light-harvesting nitrogen enrich Eosin-Y functionalized graphene-based (NDGFE-Y) photocatalytic system with appropriate band gap and supported by UV-Visible, FTIR, XRD, and FE-SEM, Raman spectra and TGA curve. This prepared photocatalyst is a yardstick example for the photoinduced oxide CF₃SO₂Na to produce the CF₃ as an electrophilic radical, effectively making the trifluoromethylation of benzaldehyde and their derivatives.

Graphical abstract

The graphical abstract represents the highly selective NDGFE-Y photocatalyst for trifluoromethylation of Benzaldehyde under solar light irradiation. The NDGFE-Y photocatalyst has effective photocatalytic properties due to the functionalization of Eosin -Y dye.

石墨烯基光催化剂在有机化合物上生成三氟甲基是21世纪新兴的研究领域。然而，金属基光催化剂的昂贵和有毒性质对三氟甲基的插入构成了重大障碍。因此，有机化合物的三氟甲基化并通过太阳光照射转化为可持续的、更环保的化学品是一个热门和具有挑战性的课题。因此，我们开发了一种具有合适带隙的太阳能光收集富氮伊红- y功能化石墨烯(NDGFE-Y)光催化体系，并得到了uv -可见、FTIR、XRD、FE-SEM、拉曼光谱和TGA曲线的支持。所制备的光催化剂是光诱导氧化物CF3SO2Na产生CF3为亲电自由基，有效地使苯甲醛及其衍生物三氟甲基化的标尺实例。图摘要为太阳光照下苯甲醛三氟甲基化的高选择性NDGFE-Y光催化剂。NDGFE-Y光催化剂由于伊红-Y染料的功能化而具有良好的光催化性能。

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引用次数: 0

Transmission of substituent effect through π-conjugation by cyclobutane ring 环丁烷环π共轭传递取代基效应

IF 1.7 4区化学 Q3 Chemistry

Journal of Chemical Sciences

Pub Date : 2023-11-14 DOI: 10.1007/s12039-023-02220-y

Sanjeev Rachuru, Jagannadham Vandanapu

A simple mathematical approach is provided in this article about the sp² character of the carbons of cyclobutane and its ability to transmit substituent effect through π-conjugation comparing the Hammett reaction constants (ρ) of the dissociation equilibriums of cinnamic acids, 2-(3 or 4-X-phenyl)cyclobutane-1-carboxylic acids and 3-phenylpropionic acids.

Graphical abstract

The substituent (X) effect on dissociation equilibriums of 2-(3 or 4-X-phenyl)-cyclobutane-1-carboxylic acids through π-conjugation by cyclobutane ring is demonstrated comparing its Hammett reaction constant (ρ) with those of 3-X-phenylpropionic acids and cinnamic acids. The substituent effect in 2-(3 or 4-X-phenyl)-cyclobutane-1-carboxylic acids is 18% as effective as cinnamic acids.

本文对肉桂酸、2-(3或4-苯基)环丁烷-1羧酸和3-苯基丙酸的解离平衡的Hammett反应常数ρ进行了比较，提出了一种简单的数学方法来研究环丁烷碳的sp2性质及其通过π共轭传递取代效应的能力。摘要通过环丁烷环的π共轭，证明了取代基(X)对2-(3或4-X-苯基)-环丁烷-1-羧酸解离平衡的影响，并与3-X-苯基丙酸和肉桂酸的Hammett反应常数(ρ)进行了比较。2-(3或4- x -苯基)-环丁烷-1-羧酸的取代效应是肉桂酸的18%。

引用次数: 0

Synthesis, type II diabetes inhibitory activity and docking studies of novel thiazole molecules 新型噻唑类分子的合成、II型糖尿病抑制活性及对接研究

IF 1.7 4区化学 Q3 Chemistry

Journal of Chemical Sciences

Pub Date : 2023-11-14 DOI: 10.1007/s12039-023-02225-7

Jaysinh I Jadeja, Mahesh M Savant

A series of novel ethyl (E)-2-cyano-3-((4-methyl-5-(arylcarbamoyl)thiazol-2-yl)amino)-3-(methylthio)acrylate have been synthesized starting from various 2-amino-N-aryl-4-methylthiazole-5-carboxamide. The reaction of 3-oxo-N-arylbutanamide 2a-i with N-bromosuccinimide and cyclization with thiourea under reflux conditions yielded derivatives of 2-amino-N-aryl-4-methylthiazole-5-carboxamide 3a-i. Further reaction of thiazoles 3a-i with ethyl 2-cyano-3,3-bis(methylthio)acrylate in DMF and K₂CO₃ as a base under room temperature gave new thiazole molecule 4a-i with excellent yields. The significant features of this reaction procedure are novel, modest, and short time. The spectral characterization of molecules was confirmed by ¹H NMR, ¹³C NMR, FTIR, and MS. Synthesized molecules were evaluated in vitro for their α-amylase inhibitory activity and displayed moderate to excellent inhibition with IC₅₀ values varying from 12.55 μg/mL to 69.47 μg/mL using acarbose (IC₅₀=23.62 μg/mL) as control. Moreover, a molecular docking study was carried out for synthesized molecules 4a-i against human pancreatic α-amylase (2QV4) via utilizing the Autodock technique. The docking outcomes of molecules 4g and 4h showed good cytotoxic activity.

Graphical abstract

An efficient procedure for synthesizing highly functionalized thiazole molecules, type II diabetes inhibitory activity with molecular docking studies.

以各种2-氨基- n -芳基-4-甲基噻唑-5-羧酰胺为原料，合成了一系列新型的(E)-2-氰基-3-((4-甲基-5-(芳基氨基)噻唑-2-基)氨基)-3-(甲基硫)丙烯酸酯。3-氧- n -芳基丁酰胺2a-i与n -溴琥珀酰亚胺反应，并在回流条件下与硫脲环化，得到2-氨基- n -芳基-4-甲基噻唑-5-羧酰胺3a-i衍生物。噻唑3a-i与2-氰基-3,3-双(甲基硫)丙烯酸乙酯在DMF中以K2CO3为碱，在室温下进一步反应，得到了收率优异的新噻唑分子4a-i。该反应程序的显著特点是新颖、温和、时间短。通过1H NMR、13C NMR、FTIR和ms对合成的分子进行了光谱表征，体外评价了合成的分子对α-淀粉酶的抑制活性，以阿卡波糖(IC50=23.62 μg/mL)为对照，IC50值为12.55 ~ 69.47 μg/mL。此外，利用Autodock技术对合成的抗人胰腺α-淀粉酶(2QV4)分子4a-i进行分子对接研究。分子4g和4h的对接结果显示出良好的细胞毒活性。高效合成高功能化噻唑分子，与分子对接研究二型糖尿病抑制活性。

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引用次数: 0

A facile, metal-free synthesis of aryl bromides using molecular bromine-an alternative to the Sandmeyer reaction 一种简单、无金属的芳基溴合成方法，使用分子溴——一种替代桑德梅尔反应的方法

IF 1.7 4区化学 Q3 Chemistry

Journal of Chemical Sciences

Pub Date : 2023-11-07 DOI: 10.1007/s12039-023-02228-4

Satish Wakchaure, Kiran Nathe, Sharayu Deshmukh

An efficient metal-free synthesis of aryl bromides from aniline derivatives using molecular bromine is described. This one-pot reaction affords aryl bromides from corresponding electron-rich anilines in moderate to excellent yields without isolation of diazonium salts. The transformation has short reaction times, an ambient temperature, a simple workup, and insensitivity to moisture and air. This synthetic strategy represents an alternative approach to the classic Sandmeyer reaction.

Graphical abstract

A Metal-free Sandmeyer reaction strategy has been used to synthesize various aryl bromides. An aryl amines have diazotized by using sodium nitrite and 48% HBr in water and subsequently reaction mass treated with liquid bromine to offord variety of aryl bromides. Around 12 different aryl amines have been studied. Excellent yield has been obtained from electron rich aryl amine.

介绍了一种利用分子溴从苯胺衍生物合成芳基溴的高效无金属方法。此一锅反应可从相应的富电子苯胺中获得芳基溴，产率中等至优异，无需分离重氮盐。该转化反应时间短，环境温度低，操作简单，对水分和空气不敏感。这种综合策略代表了经典桑德梅尔反应的另一种方法。无金属的Sandmeyer反应策略已被用于合成各种芳基溴。用亚硝酸钠和48% HBr水溶液重氮化芳基胺，然后用液态溴处理反应质量，得到多种芳基溴。研究了大约12种不同的芳基胺。富电子芳胺得到了很好的收率。

引用次数: 0