Tetrahedron Green Chem最新文献

英文中文

Replacing DMF by Cyrene™ drives the syntheses of pentathiepines towards sustainability, conveniency, and/or higher yields 用昔勒尼™取代DMF推动了五硫代嘌呤的合成走向可持续性、便利性和/或更高的产量

Tetrahedron Green Chem

Pub Date : 2026-01-12 DOI: 10.1016/j.tgchem.2026.100092

Lukas Manuel Jacobsen, Roberto Tallarita, Johannes Fimmen, Siva S.M. Bandaru, Christian Fischer, Carola Schulzke

Building on previous efforts in optimizing the synthesis of 1,2,3,4,5-pentathiepino[6,7-a]indolizines mediated by the molybdenum oxo bistetrasulfido complex, this study advances the respective preparation procedures by introducing an environmentally friendly approach with a concomitant focus on increasing yields and efficiency, and generally improved reaction conditions. Incorporating the sustainable solvent Cyrene™ into the established protocol enables the synthesis of various substituted 1,2,3,4,5-pentathiepino[6,7-a]indolizines in a more environmentally friendly manner, complemented by a new purification approach. Derivatives studied include substituents CF₃, CN, CHO, COOMe, and a urea group at C-9. Realized modifications with a COOMe group at positions C-8, C-10, and C-11 are reported for the first time. Testing three different sets of conditions confirmed that the green Cyrene™ is a valid practical alternative to dimethylformamide (DMF). Although yields and reaction times did not improve in each and every case, the research demonstrates a method utilizing a non-toxic, biodegradable solvent to comprise a significant advancement over traditional, more toxic, and harsh methods for this compound class. Sublimation as a new purification technique was also explored in order to minimize the generation of organic solvent waste. Notably, the CN-substituted compound showed unusual behaviour during synthesis, with no product formation under N₂ conditions, and unexpected tetrasulfide side products could be identified for two COOMe derivatives. To understand the observed differences in reactivity and the chemical/molecular and electronic structures of these compounds, comprehensive analytical characterization was performed on all derivatives supported by computational analysis.

在先前优化由钼氧双四硫配合物介导的1,2,3,4,5-五硫代epino[6,7-a]吲哚啉合成的基础上，本研究通过引入一种环境友好的方法来提高各自的制备工艺，同时注重提高收率和效率，并总体改善反应条件。将可持续溶剂Cyrene™纳入已建立的方案中，可以以更环保的方式合成各种取代的1,2,3,4,5-pentathiepino[6,7-a]吲哚嘧啶，并辅以新的纯化方法。所研究的衍生物包括取代基CF3、CN、CHO、coom和C-9上的脲基。首次报道了在C-8、C-10和C-11位置实现的对COOMe组的修改。测试了三组不同的条件，证实绿色Cyrene™是二甲基甲酰胺（DMF）的有效实用替代品。虽然产率和反应时间在每种情况下都没有提高，但研究表明，一种利用无毒、可生物降解溶剂的方法比传统的、毒性更大、更苛刻的化合物方法有了显著的进步。为了最大限度地减少有机溶剂废物的产生，还探索了升华作为一种新的净化技术。值得注意的是，cn取代的化合物在合成过程中表现出不同寻常的行为，在N2条件下没有生成产物，并且可以在两个COOMe衍生物中鉴定出意外的四硫副产物。为了了解这些化合物在反应性和化学/分子和电子结构上的差异，我们对所有的衍生物进行了全面的分析表征。

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引用次数: 0

Novel Bi2O3/MWCNT@TiO2 nanocomposite for enhanced photocatalytic degradation of Brilliant blue dye under visible light and ozonation 新型Bi2O3/MWCNT@TiO2纳米复合材料在可见光和臭氧氧化下增强光催化降解亮蓝色染料

Tetrahedron Green Chem

Pub Date : 2025-12-24 DOI: 10.1016/j.tgchem.2025.100091

Pushpavati Pilla , Alice Rinky Robert , Himavathi Ganja , Suresh Maddila

This study aimed to develop an efficient photocatalyst for the degradation of Brilliant Blue G (BBG) dye in aqueous solutions under visible light and ozonation. The research focused on synthesising and characterising a novel Bi₂O₃/MWCNT@TiO₂ nanocomposite (BMT) to enhance photocatalytic performance through synergistic effects. The Bi₂O₃/MWCNT@TiO₂ nanocomposite was prepared using a wet impregnation method. Techniques such as PXRD, UV–visible DRS, BET surface area analysis, SEM-EDX, and TEM were employed to evaluate structural and morphological properties. Variants, BMT-1 to BMT-5, were synthesised with varying compositions and extensively characterised. The results revealed that BMT-1 and BMT-5 exhibited particle sizes in the range of 20–45 nm and band gaps of 2.76 eV and 3.0 eV, respectively, indicating their suitability for visible-light-driven photocatalysis. The nanocomposites demonstrated exceptional efficiency in degrading BBG dye under solar irradiation and ozonation. At an optimal catalyst dose of 0.025 g/L and an initial dye concentration of 20 ppm, a maximum degradation efficiency of 98.3 % was achieved. The influence of pH was investigated at acidic (pH 3), natural, and alkaline (pH 11) conditions. BMT-5 exhibited superior performance at the dye's natural pH, while BMT-1 showed high degradation of 97 % and 93 % at pH 3 and 11, respectively. Additionally, the catalysts displayed excellent reusability, confirming their stability and potential application for practical wastewater treatment applications. This work highlights the usefulness of Bi₂O₃/MWCNT@TiO₂ as a robust photocatalyst for pollutant degradation under environmentally relevant conditions.

本研究旨在开发一种高效的光催化剂，在可见光和臭氧氧化下降解水溶液中的亮蓝G （BBG）染料。研究重点是合成和表征一种新型Bi2O3/MWCNT@TiO2纳米复合材料（BMT），通过协同效应提高光催化性能。采用湿浸渍法制备了Bi2O3/MWCNT@TiO2纳米复合材料。采用PXRD， uv -可见DRS， BET表面积分析，SEM-EDX和TEM等技术评价其结构和形态特性。变体，BMT-1到BMT-5，用不同的成分合成并广泛表征。结果表明，BMT-1和BMT-5的粒径在20 ~ 45 nm之间，带隙分别为2.76 eV和3.0 eV，适合用于可见光驱动光催化。该纳米复合材料在太阳辐照和臭氧化作用下对BBG染料具有优异的降解效率。催化剂的最佳用量为0.025 g/L，初始染料浓度为20 ppm时，降解效率可达98.3%。考察了pH在酸性（pH 3）、自然和碱性（pH 11）条件下的影响。BMT-5在染料的自然pH下表现出优异的降解性能，而BMT-1在pH为3和11时的降解率分别为97%和93%。此外，催化剂表现出良好的可重复使用性，证实了其稳定性和在实际废水处理中的潜在应用。这项工作强调了Bi2O3/MWCNT@TiO2在环境相关条件下作为污染物降解的强大光催化剂的实用性。

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引用次数: 0

Selective oxidative cleavage of lignin through tailored reactive oxygen species 通过定制活性氧选择性氧化裂解木质素

Tetrahedron Green Chem

Pub Date : 2025-12-17 DOI: 10.1016/j.tgchem.2025.100090

Ying He, Rongji Li, Mingyang Hu, Yun Liu

Transforming lignin into valuable aromatic compounds is a critical objective for sustainable biorefining. While oxidative depolymerization has been proven effective in breaks down lignin's macromolecule, its practical application has been limited by low selectivity. This review presents a paradigm shift in the field, moving from broad, non-selective oxidative degradation methods to highly targeted catalytic processes driven by controlled reactive oxygen species (ROS). It offers a comprehensive analysis of how various catalytic systems—utilizing O₂, H₂O₂, metals oxides, electricity, light, and organic oxidants—generate distinct ROS profiles, ranging from non-specific hydroxyl radicals to more selective superoxide anions or high-valent metal-oxo complexes. These ROS serve as "molecular scissors", directly influencing the efficiency of C–O and C–C bond cleavage, thereby determining the yields of key products such as aldehydes, ketones, and acids. This review also explores emerging strategies, including single-atom catalysis and external field activation, which provide unparalleled precision in managing these reactive intermediates. Finally, it addresses ongoing challenges related to catalyst stability and the heterogeneity of lignin, while outlining promising future research directions focused on tandem processes and real-time mechanistic studies, to further unlock lignin's potential as a renewable source of aromatic feedstocks.

将木质素转化为有价值的芳香族化合物是可持续生物精炼的关键目标。虽然氧化解聚在木质素大分子的分解中被证明是有效的，但它的实际应用受到低选择性的限制。本文综述了该领域的范式转变，从广泛的非选择性氧化降解方法转向由受控活性氧（ROS）驱动的高度靶向催化过程。它提供了一个全面的分析如何各种催化系统-利用O2， H2O2，金属氧化物，电，光和有机氧化剂-产生不同的活性氧谱，从非特异性羟基自由基到更选择性的超氧阴离子或高价金属-氧配合物。这些ROS就像“分子剪刀”，直接影响C-O和C-C键的裂解效率，从而决定醛、酮、酸等关键产物的产率。这篇综述还探讨了新兴的策略，包括单原子催化和外场激活，它们在管理这些反应性中间体方面提供了无与伦比的精度。最后，它解决了与木质素催化剂稳定性和异质性相关的持续挑战，同时概述了未来有希望的研究方向，重点是串联过程和实时机制研究，以进一步释放木质素作为芳香原料可再生来源的潜力。

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引用次数: 0

Natural acids as catalysts for the continuous flow production of the green solvent 2,2,5,5-tetramethyltetrahydrofuran 天然酸催化绿色溶剂2,2,5,5-四甲基四氢呋喃的连续流生产

Tetrahedron Green Chem

Pub Date : 2025-12-03 DOI: 10.1016/j.tgchem.2025.100089

Bernice M. Currie , Estefan van Vuuren , Jaimee Jugmohan , Jenny-Lee Panayides , Darren L. Riley

As the demand for chemists to adhere to green chemistry principles increases, so does the demand for green solvents. Unfortunately, many green solvents, such as 2,2,5,5-tetramethyltetrahydrofuran (TMTHF), are costly and difficult to source. Traditional synthesis of TMTHF from 2,5-dimethyl-2,5-hexanediol has been reported to be catalysed by acids such as phosphoric and sulfuric acid, or, more recently, by H-beta zeolite. Although H-beta zeolite catalysts are high-yielding and selective, the energy required for their regeneration is high, and their production has questionable environmental impacts. A new approach was developed using flow technologies and naturally occurring acids as catalysts for TMTHF synthesis. Flow technologies are scalable, safe, efficient, and reproducible for daily chemical reactions, aligning with principles of green chemistry. This study observed several key improvements, including i) the use of a natural acid as a catalyst, ii) the use of water as a solvent, and iii) a continuous process for multigram-scale synthesis of TMTHF using citric acid monohydrate, with a yield of 72 %, resulting in a throughput of 8.24 g h⁻¹ (9.43 kg L ⁻¹ h⁻¹ space-time yield).

随着对化学家坚持绿色化学原则的要求的增加，对绿色溶剂的需求也在增加。不幸的是，许多绿色溶剂，如2,2,5,5-四甲基四氢呋喃（TMTHF），价格昂贵且难以获得。传统的由2,5-二甲基-2,5-己二醇合成TMTHF的方法有报道是由磷酸和硫酸等酸催化的，或者最近用h - β沸石催化。虽然h- β沸石催化剂具有高产率和选择性，但其再生所需的能量很高，并且其生产对环境的影响值得怀疑。开发了一种利用流动技术和天然酸作为催化剂合成TMTHF的新方法。Flow技术在日常化学反应中具有可扩展性、安全性、高效性和可重复性，符合绿色化学的原则。本研究发现了几个关键的改进，包括i)使用天然酸作为催化剂，ii)使用水作为溶剂，以及iii)使用一水合物柠檬酸进行多克尺度连续合成TMTHF，收率为72%，吞吐量为8.24 gh−1 （9.43 kg L−1 h−1时空收率）。

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引用次数: 0

Amphiphilic bile acid-amino acid conjugates as sustainable organocatalysts for aqueous asymmetric aldol reactions: From molecular design to aggregation-controlled selectivity 两亲性胆汁酸-氨基酸偶联物作为水不对称醛醇反应的可持续有机催化剂：从分子设计到聚集控制选择性

Tetrahedron Green Chem

Pub Date : 2025-08-27 DOI: 10.1016/j.tgchem.2025.100086

Venanzio Raglione , Federica Palmeri , Fabrizio Vetica , Andrea D'Annibale

The amine-catalyzed aldol reaction has become a stable of organic synthesis with numerous applications affording predominantly the anti aldol product. Using our synthesized and characterized bile acid-amino acid conjugates with l-proline and l-phenylalanine, and bile acids amino derivatives we successfully performed regioselective aldol reactions in aqueous media controllably giving either the anti or syn diastereomer. These novel derivatives exhibited high catalytic activity, with the l-proline-based organocatalyst showing the highest efficiency, achieving yields up to 99 %, high diastereoselectivity for the anti product and moderate enantioselectivity. The l-phenylalanine-based one demonstrated good catalytic performance, achieving yields up to 99 % and good diastereoselectivity for the syn product. The environmental sustainability of these catalytic systems was further enhanced in the use of bio-based surfactants-amino acids conjugates utilizing water as the reaction medium, without the addition of any cosolvent, while aligning with the modern ethics of environmentally friendly practices. These findings reveal the potential application of natural bile acids scaffolds as versatile and eco-friendly conjugates to afford highly efficiency in sustainable organocatalysis for successfully achieving organic transformations in aqueous environments.

胺催化的醛醇反应已成为一种稳定的有机合成方法，具有广泛的应用，主要提供抗醛醇产物。利用我们合成和表征的胆汁酸-氨基酸与l-脯氨酸和l-苯丙氨酸的偶联物，以及胆汁酸氨基酸衍生物，我们成功地在水介质中进行了区域选择性醛醇反应，可控制地产生抗或顺非对映体。这些新型衍生物具有较高的催化活性，其中以l-脯氨酸为基础的有机催化剂表现出最高的效率，产率高达99%，抗产物具有较高的非对映选择性和中等的对映选择性。以l-苯丙氨酸为基础的催化产物表现出良好的催化性能，产率高达99%，对合成产物具有良好的非对映选择性。这些催化系统的环境可持续性在使用生物基表面活性剂-氨基酸缀合物时得到进一步增强，利用水作为反应介质，不添加任何助溶剂，同时符合现代环境友好实践的伦理。这些发现揭示了天然胆汁酸支架作为多功能和生态友好的缀合物的潜在应用，为在水环境中成功实现有机转化提供了高效的可持续有机催化。

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引用次数: 0

Reusable copper iron oxide for heterogeneously oxidative cyclization of (hetero)aryl methyl ketones and 2-phenylglycines 可重复使用的铜氧化铁用于（杂）芳基甲基酮和2-苯基甘氨酸的异质氧化环化

Tetrahedron Green Chem

Pub Date : 2025-08-23 DOI: 10.1016/j.tgchem.2025.100087

Hao T. Tran , Duyen K. Nguyen , Phuong T. Dinh , Ngoc D.Q. Chau , Tung T. Nguyen

Annulation of methyl C–H bonds in acetophenone derivatives with 2-phenylglycines to furnish 2,5-diphenyloxazoles under the assistance of heterogeneous catalyst is firstly reported. Successes are attributed to the use of commercially available copper iron oxide, in combination with molecular iodine, p-toluenesulfonic acid, and DMSO. The efficiency of our method is somewhat proven as 19 examples were isolated with yields varied from 32 % to 84 %. The copper iron oxide could be recovered and reused up to 4 times with nearly identical catalytic activity.

本文首次报道了在非均相催化剂作用下，苯乙酮衍生物与2-苯基甘氨酸的甲基C-H键环化生成2,5-二苯氯唑。成功的原因是使用了市售的氧化铜铁，与分子碘、对甲苯磺酸和二甲基亚砜结合使用。结果表明，该方法的效率在一定程度上得到了验证，共分离出19个样品，产率从32%到84%不等。氧化铜铁可回收再利用4次，且催化活性基本相同。

引用次数: 0

Green chemistry methods: Synthesis of bioactive molecules-based quinazoline, quinoline, quinoxaline, benzimidazole and imidazole 绿色化学方法：合成基于生物活性分子的喹唑啉、喹啉、喹诺啉、苯并咪唑和咪唑

Tetrahedron Green Chem

Pub Date : 2025-08-09 DOI: 10.1016/j.tgchem.2025.100085

Ibrahim A. Bala , Abdullah M. Asiri , Maha M. Alotaibi , Reda M. El-Shishtawy

The destruction of the ecosystem caused by chemicals such as pesticides, fertilizers, plastics, and greenhouse gases has provoked the conscience of the public and regulators to control the use of chemicals. There is a growing concern and awareness about preserving the environment against the danger of toxic substances. Sustainable industrial development as a means of cutting pollution from industry and developing renewable raw materials for industry has been a challenge in the twenty-first century. This review outlines the basics and ideas of green chemistry with examples and emphasis on the synthesis of bioactive molecules—based quinazoline, quinoline, quinoxaline, benzimidazole and imidazole from 2012 to 2025 to illustrate different fronts for developmental improvement in achieving sustainable procedures.

农药、化肥、塑料和温室气体等化学物质对生态系统造成的破坏，引发了公众和监管机构控制化学品使用的良知。保护环境免受有毒物质危害的关注和意识日益增强。可持续工业发展作为减少工业污染和为工业开发可再生原料的手段，已成为二十一世纪的一项挑战。本文概述了绿色化学的基本原理和思想，并举例介绍了2012年至2025年以生物活性分子为基础的喹唑啉、喹啉、喹诺啉、苯并咪唑和咪唑的合成，以说明在实现可持续过程中发展改进的不同领域。

引用次数: 0

Engineering TiO2 photocatalysts for enhanced visible-light activity in wastewater treatment applications 工程TiO2光催化剂在废水处理应用中增强可见光活性

Tetrahedron Green Chem

Pub Date : 2025-07-30 DOI: 10.1016/j.tgchem.2025.100084

Mariam El Mchaouri , Safiya Mallah , Dikra Abouhajjoub , Wafaa Boumya , Rachid Elmoubarki , Abdelhafid Essadki , Noureddine Barka , Alaâeddine Elhalil

Wastewater treatment is an environmental imperative due to increasing water stress and ecological crises particularly in view of the inherent limitations of conventional treatment methods, which frequently demonstrate suboptimal efficiency and tend to produce undesirable secondary by-products. In this context, advanced oxidation processes (AOPs), especially heterogeneous photocatalysis, have demonstrated significant potential as ecologically and economically viable solutions for the complete degradation of pollutants into CO₂ and H₂O under ambient conditions. Titanium dioxide (TiO₂) is the most widely used photocatalyst owing to its non-toxicity, photochemical stability, and high reactivity. However, its practical application is hindered by several limitations, including activation restricted to UV light (due to a wide bandgap), rapid recombination of photogenerated electron–hole pairs, and relatively low surface area. To overcome these challenges, this review discusses recent strategies for modifying the properties and structure of TiO₂ to enhance its photocatalytic performance under visible light. These strategies include metal or non-metal doping, the formation of heterostructures, and dye sensitization, all aimed at extending light absorption into the visible range and improving charge separation and transport. Furthermore, the integration of TiO₂ with bismuth-based photocatalysts, such as BiVO₄, Bi₂WO₆, and Bi₂MoO₆, is explored. These materials exhibit efficient visible-light absorption and favorable electronic properties, significantly boosting the photocatalytic activity of TiO₂. By implementing these modifications, TiO₂-based photocatalysts are expected to play a key role in environmental remediation and contribute to the development of sustainable water treatment technologies.

由于日益增加的水资源压力和生态危机，特别是考虑到传统处理方法的固有局限性，废水处理是一项环境势在必行的任务，这些方法经常表现出次优的效率，并倾向于产生不良的二次副产品。在这种情况下，高级氧化工艺（AOPs），特别是多相光催化，已经证明了在环境条件下将污染物完全降解为CO2和H2O的生态和经济可行的解决方案的巨大潜力。二氧化钛（TiO2）具有无毒、光化学稳定性好、反应活性高等优点，是目前应用最广泛的光催化剂。然而，它的实际应用受到几个限制的阻碍，包括仅限于紫外光的激活（由于宽的带隙），光产生的电子-空穴对的快速重组，以及相对较低的表面积。为了克服这些挑战，本文综述了近年来对TiO2的性质和结构进行修饰以提高其在可见光下的光催化性能的策略。这些策略包括金属或非金属掺杂、异质结构的形成和染料敏化，所有这些策略都旨在将光吸收扩展到可见光范围，并改善电荷的分离和传输。此外，还探讨了TiO2与铋基光催化剂BiVO4、Bi2WO6和Bi2MoO6的集成。这些材料具有高效的可见光吸收和良好的电子性能，显著提高了TiO2的光催化活性。通过这些修饰，二氧化钛基光催化剂有望在环境修复中发挥关键作用，并为可持续水处理技术的发展做出贡献。

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引用次数: 0

A green method for the direct precipitation of 3-methylpyrido[2,3-b]pyrazin-2(1H)-one and 2-methylpyrido[3,4-b]pyrazin-3(4H)-one from ethyl lactate solutions 从乳酸乙酯溶液中直接沉淀3-甲基吡啶多[2,3-b]吡嗪-2(1H)- 1和2-甲基吡啶多[3,4-b]吡嗪-3(4H)- 1的绿色方法

Tetrahedron Green Chem

Pub Date : 2025-07-17 DOI: 10.1016/j.tgchem.2025.100083

Nicolas Elia, Eric D. Helms

Green methods for synthesizing pyridopyrazinones were developed due to their usefulness as scaffolds in the design of therapeutic compounds. Reaction conditions using aqueous ethyl lactate solutions were optimized to maximize yields through direct product precipitation. Two key scaffolds, 3-methylpyrido[2,3-b]pyrazin-2(1H)-one and 2-methylpyrido[3,4-b]pyrazin-3(4H)-one, were obtained in yields of 88 % and 85 %, respectively. The highest yields were achieved using 92:8 and 99:1 ethyl lactate:water mixtures, with the latter including 1.5 mol% lactic acid at 35 °C. These results are comparable to traditional syntheses using anhydrous chloroform but offer a more sustainable alternative by avoiding hazardous solvents.

绿色合成吡啶吡嗪酮的方法是由于它们在设计治疗性化合物中作为支架的用途而发展起来的。优化了乳酸乙酯水溶液的反应条件，通过直接沉淀法使收率最大化。2-甲基吡啶多[2,3-b]吡嗪-2(1H)- 1和2-甲基吡啶多[3,4-b]吡嗪-3(4H)- 1两个关键支架的产率分别为88%和85%。使用92:8和99:1乳酸乙酯：水的混合物，后者在35°C下含有1.5 mol%乳酸，获得了最高的收率。这些结果与使用无水氯仿的传统合成相当，但提供了一种更可持续的替代方法，避免了有害溶剂。

引用次数: 0

Deep eutectic solvent mediated synthesis of β-carbolines and related natural products via Pictet–Spengler reaction and aerobic oxidation 深共晶溶剂介导的Pictet-Spengler反应及有氧氧化合成β-碳啉及其相关天然产物

Tetrahedron Green Chem

Pub Date : 2025-07-10 DOI: 10.1016/j.tgchem.2025.100082

Bhuvana Narasimman

An eco-friendly, one-pot synthesis of β-carboline derivatives using deep eutectic solvent is reported. This protocol utilizes commercially available aldehydes and tryptamine, involving Pictet–Spengler cyclization followed by aerobic oxidation. This environmentally friendly methodology offers access to various β-carboline alkaloids Nitramarine, Nitraridine, Eudistomin U, Norharmane, Harmane, and their analogues in a single step with 30–68% yields.

报道了一种利用深共晶溶剂一锅法合成β-羰基衍生物的方法。该方案利用市售醛和色胺，包括Pictet-Spengler环化，然后进行有氧氧化。这种环境友好的方法可以在一个步骤中获得各种β-碳碱生物碱Nitramarine， Nitraridine, Eudistomin U, Norharmane， Harmane及其类似物，收率为30-68%。

引用次数: 0

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