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DMSO arbitrated Oxidative Annulation Followed by Homologated N-Alkylation: Microwave-Assisted Efficient and Greener Approach to Access 3-(3-Oxo-3-arylpropyl) Quinazolinones DMSO仲裁氧化环化后的同质n -烷基化:微波辅助下获得3-(3-氧-3-芳基丙基)喹唑啉酮的高效和绿色方法
IF 2.5 Q2 CHEMISTRY, ORGANIC Pub Date : 2023-05-25 DOI: 10.1055/s-0040-1720079
A. Prasanthi, B. N. Babu
A convenient, time efficient, tandem approach for the synthesis of medicinally privileged 3-(3-oxo-3-arylpropyl) quinazolinones is developed from ubiquitously available acetophenones and anthranilamide via microwave irradiation. This transition-metal-free reaction is initiated by the oxidative annulation of anthranilamide and in situ generation of α,β-unsaturated carbonyl compounds from aryl ketones in the presence of K2S2O8 and dimethyl sulfoxide. The latter acts as a source of two carbons [methine (=CH–) and methylene (–CH2–)] apart from being the solvent. The reaction is carried out under microwave irradiation which has the advantage of homogenous heat distribution, reducing the reaction time drastically compared to the conventional heating reaction.
以苯乙酮和蒽酰胺为原料,通过微波辐照,建立了一种方便、快捷、串联合成3-(3-氧-3-芳基丙基)喹唑啉酮的方法。这个无过渡金属的反应是在K2S2O8和二甲亚砜的存在下,由芳基酮原位生成α,β-不饱和羰基化合物和蒽酰胺的氧化环化引发的。后者除了作为溶剂外,还作为两种碳[甲基(=CH -)和亚甲基(- ch2 -)]的来源。该反应在微波辐射下进行,具有热分布均匀的优点,与传统的加热反应相比,大大缩短了反应时间。
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引用次数: 0
Ziegler–Natta Catalysts: Applications in Modern Polymer Science 齐格勒-纳塔催化剂:在现代聚合物科学中的应用
IF 2.5 Q2 CHEMISTRY, ORGANIC Pub Date : 2023-05-16 DOI: 10.1055/s-0040-1720078
K. Jha, Abhimannu Shome, P. Chawla
Karl Ziegler, a scientist from Germany, discovered that combining TiCl4 and Al(C2H5)3 produced a highly active catalyst that could polymerize ethylene in a stereoregular manner at atmospheric pressure. Later, an Italian chemist named Giulio Natta expanded upon Ziegler’s work by developing methods for using the catalyst with other olefins like propylene. Natta also contributed to our understanding of the mechanism behind the polymerization reaction, which led to the development of various forms of the Ziegler catalyst. Over time, scientists have gained more control over stereospecific polymerization thanks to these discoveries.1–4 The Ziegler–Natta catalyst is comprised of transitionmetal chlorides, including titanium, chromium, vanadium, and zirconium chlorides, that have a distinguished lineage, along with organometallic complexes of triethylaluminium. The crystal structure of the titanium chloride compound contains Ti atoms attached to five chlorine atoms on the surface, with one empty orbital. When the compound reacts with Al(C2H5)3, the latter donates an Et group to Ti, causing one chlorine group to detach from Ti.5–7 This reaction activates the catalyst, as illustrated in Scheme 1, and initiates chain propagation and termination steps, also depicted in the same diagram. These polymers are useful for manufacturing plastics, fibers, and films. Ziegler and Natta’s work on this catalyst earned them the Nobel Prize in Chemistry in 1963.8,9 The Ziegler–Natta catalysts have undergone several advancements, resulting in four distinct generations of catalysts. The first generation utilized diethyl aluminum and titanium chloride as co-catalysts. In the second generation of catalysts, titanium chloride/AlEt2Cl was combined with an internal electron donor, such as ether or ester,10,11 which enhanced the activity and stereospecificity of the catalysts. The third generation of catalysts was introduced in 1968,12 and it utilized a catalytic system made up of TiCl4 complexes supported by MgCl2. This method enabled the production of linear polyethylene and isotactic polypropylene. The fourth generation13,14 of catalysts utilized homogeneous catalysts for conducting olefin polymerizations. Over the years, several noteworthy applications of Ziegler–Natta catalysts have been developed.8 Keshav Taruneshwar Jha is a research Scholar and is pursuing his MPharm (Pharmaceutical Chemistry) from ISF College of Pharmacy, Moga, Punjab and is carrying out research under the supervision of Dr. Pooja A. Chawla.
德国科学家卡尔·齐格勒(Karl Ziegler)发现,将TiCl4和Al(C2H5)3结合可以产生一种高活性催化剂,这种催化剂可以在常压下以立体规则的方式聚合乙烯。后来,一位名叫朱利奥·纳塔(Giulio Natta)的意大利化学家在齐格勒的工作基础上,开发了将这种催化剂与丙烯等其他烯烃一起使用的方法。纳塔也有助于我们理解聚合反应背后的机制,这导致了各种形式的齐格勒催化剂的发展。随着时间的推移,由于这些发现,科学家们对立体特异性聚合有了更多的控制。Ziegler-Natta催化剂由过渡金属氯化物组成,包括钛、铬、钒和锆氯化物,它们具有独特的谱系,以及三乙基铝的有机金属配合物。氯化钛化合物的晶体结构包括钛原子附着在表面的五个氯原子上,有一个空轨道。当化合物与Al(C2H5)3反应时,Al(C2H5)3给Ti一个Et基团,使一个氯基团与Ti分离。5 - 7该反应激活催化剂,如方案1所示,并启动链扩展和终止步骤,也在同一张图中所示。这些聚合物可用于制造塑料、纤维和薄膜。Ziegler和Natta在这种催化剂上的工作为他们赢得了1963年的诺贝尔化学奖。Ziegler - Natta催化剂经历了几次进步,产生了四代不同的催化剂。第一代采用二乙基铝和氯化钛作为共催化剂。在第二代催化剂中,氯化钛/AlEt2Cl与内部电子给体(如醚或酯,10,11)结合,增强了催化剂的活性和立体特异性。第三代催化剂是在1968年推出的,它使用了由MgCl2负载的TiCl4配合物组成的催化体系。这种方法使线性聚乙烯和等规聚丙烯的生产成为可能。第四代催化剂13,14采用均相催化剂进行烯烃聚合。7 .多年来,齐格勒-纳塔催化剂的几个值得注意的应用得到了发展Keshav Taruneshwar Jha是一名研究学者,正在旁遮普省莫加市ISF药学院攻读药物化学硕士学位,并在Pooja a. Chawla博士的指导下进行研究。
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引用次数: 0
Synthetic Utility of N -Acylbenzotriazoles N -酰基苯并三唑的合成及应用
IF 2.5 Q2 CHEMISTRY, ORGANIC Pub Date : 2023-05-14 DOI: 10.1055/a-2157-5782
Mangal S Yadav, Abhishek Gupta, Priyanka Bose, Ashutosh Kumar Singh, P. Mohapatra, V. Tiwari
N-Acylbenzotriazoles are valuable synthons in organic synthesis. They are particularly used as acylating agents and an alternative to acyl chloride. They have been widely explored for a diverse range of applications. This review summarizes the methods for the preparation of N-acylbenzotriazole derivatives and their diverse applications in particular demonstration to serve as alternative acylating agents in organic transformations such as N-, O-, C-, and S-acylating agents for the convenient synthesis of a wide range of biologically important organic compounds. We also emphasize the synthesis of diverse compounds using benzotriazole ring cleavage (BtRC) methodology, including its pharmacophore study and some notable utilities as valuable starting materials, ligands, and intermediates in the field of organic synthesis.
N-酰基苯并三唑是有机合成中有价值的合成子。它们特别用作酰化剂和酰氯的替代品。它们已被广泛探索用于各种各样的应用。本文综述了N-酰基苯并三唑衍生物的制备方法及其各种应用,特别是证明了在有机转化中作为替代酰化剂,如N-、O-、C-和S-酰化剂可以方便地合成各种具有重要生物意义的有机化合物。我们还强调了使用苯并三唑环切割(BtRC)方法合成各种化合物,包括其药效团研究以及在有机合成领域作为有价值的起始材料、配体和中间体的一些显著用途。
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引用次数: 0
Copper Sulfate (CuSO 4 ): An Efficient Reagent in Organic Synthesis 硫酸铜(CuSO4):一种高效的有机合成试剂
IF 2.5 Q2 CHEMISTRY, ORGANIC Pub Date : 2023-05-11 DOI: 10.1055/a-2134-9007
Housemberg D. S. Ferrreira, E. Barbosa, A. K. Jordão
Copper sulfate (CuSO4) is a simple, inexpensive, and commercially available salt synthesized by the treatment of cupric oxide with sulfuric acid. Copper sulfate enables a variety of diverse reactions and functionalization, that include: triazole formation, reduction of alkenes and alkynes, complexes formation, among others. In organic synhesis, this compound is normally used as a catalyst for reactions, due to its low cost, possibility of use at low temperatures and ecological advantages.
硫酸铜(CuSO4)是一种简单、廉价且可商购的盐,通过用硫酸处理氧化铜而合成。硫酸铜能够进行各种不同的反应和功能化,包括:三唑的形成、烯烃和炔烃的还原、络合物的形成等。在有机合成中,由于其低成本、在低温下使用的可能性和生态优势,该化合物通常用作反应的催化剂。
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引用次数: 0
Synthesis of the Key Saccharide Fragments of the Glucuronic Acid-Containing Repeat Unit of Pentosan Polysulfate, a Heparin Sulfate Mimetic 硫酸肝素模拟物戊聚糖多硫酸酯葡萄糖醛酸重复单元关键糖片段的合成
IF 2.5 Q2 CHEMISTRY, ORGANIC Pub Date : 2023-05-08 DOI: 10.1055/a-2126-0346
M. Banwell, Sarah Marshall, J. Ward, B. Schwartz
Suitably protected mono- and di-saccharide residues associated with the glucuronic acid-containing repeat unit (1) related to pentosan polysulfate have been prepared. The stereo-controlled coupling, using trichloroacetimidate chemistry, of certain of these is also described and the
已经制备了与戊聚糖聚硫酸酯相关的含葡萄糖醛酸重复单元(1)相关的适当保护的单糖和双糖残基。本文还描述了利用三氯乙酸酯化学对其中某些化合物的立体控制偶联
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引用次数: 0
Temperature-Controlled Diastereoselective Doebner/Ugi Tandem Reaction 温度控制的双立体选择性Doebner/Ugi串联反应
IF 2.5 Q2 CHEMISTRY, ORGANIC Pub Date : 2023-04-19 DOI: 10.1055/a-2091-7934
Yana I Sakhno, Oleksandr V Radchenko, V. Saraev, Yuliia V. Shliapkina, Mariia B. Kaidash, Mariia O Shyshkina, S. Shishkina, V. Musatov, S. Desenko, V. Chebanov
Novel peptidomimetics containing a pyrrolone fragment were synthesized by a tandem combination of Doebner and Ugi-type multicomponent reactions with controlled diastereoselectivity. This approach represents a convenient synthesis in the temperature range from 25 °C to 45 °C. In most cases, the new method allowed each diastereomer to be isolated separately.
通过具有可控非对映选择性的Doebner和Ugi型多组分反应的串联组合,合成了含有吡咯酮片段的新型拟肽。这种方法代表了在25°C至45°C的温度范围内进行方便的合成。在大多数情况下,新方法允许单独分离每个非对映异构体。
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引用次数: 0
Recent Applications of Hexamethyldisilathiane (TMS 2 S) in Organic Synthesis 六甲基二硫代烷(tms2s)在有机合成中的最新应用
IF 2.5 Q2 CHEMISTRY, ORGANIC Pub Date : 2023-04-14 DOI: 10.1055/s-0040-1720071
D. Hazelard, P. Compain
Hexamethyldisilathiane (TMS2S), also named bis(trimethylsilyl) sulfide, (CAS: 3385-94-2), was reported for the first time in the early 1950’s.1 This liquid compound (bp 160 °C) was prepared by the reaction between iodotrimethylsilane and silver sulfide. Alternatively, bis(trimethylsilyl) sulfide has been also prepared by the addition of disodium sulfide on chlorotrimethylsilane.1,2 TMS2S is nowadays commercially available (ca. 28 €/g).3 This reagent can be viewed as a S1 source of sulfide that is less toxic, less flammable, and easier to handle than gaseous hydrogen sulfide (H2S). On contact with water, TMS2S releases H2S and should be stored in a cold and dry place in an oxygen-free atmosphere. TMS2S is used as a sulfur transfer agent for the synthesis of alkyl sulfides, thioaldehydes, or thioketones but also as a reducing agent.4 TMS2S is also employed in the synthesis of inorganic–organic hybrid clusters5 or phosphinidene sulfide compounds.6 It is noteworthy that the number of publications describing the use of TMS2S has steadily increased since the 1950’s to reach an average of 65 publications per year from 2015 to 2022.7 This Spotlight article highlights the versatility of TMS2S as a S1 source of sulfides and its recent applications in organic synthesis. In 1999, Hu and Fox reported a trimethylsilylthioxy dehalogenation reaction for the synthesis of functionalized thiols (Table 1, A).8 In this process, tetrabutylammonium trimethylsilylthiolate (Me3SiSBu4N), generated in situ Dr Damien Hazelard (right) obtained his PhD in 2005 under the supervision of Dr A. Fadel (Paris-Sud University). In 2006, he performed a postdoctoral training in the field of organocatalysis in the group of Prof. Y. Hayashi at the Tokyo University of Science. Then he joined the group of Prof. F. Colobert to work on total synthesis at the University of Strasbourg. He was appointed in 2010 as assistant professor at the same university in the group of Prof. P. Compain. In July 2019, he defended his habilitation (‘Habilitation à Diriger des Recherches’). His main research interests are the development of new synthetic methodologies for the synthesis of glycomimetics.
六甲基二硅氧烷(TMS2S),又称双(三甲基硅氧烷)硫化物(CAS: 3385-94-2),于20世纪50年代初首次报道该液体化合物由碘三甲基硅烷与硫化银反应制备,温度160℃。或者,也可以通过在氯三甲基硅烷上加成硫化二钠来制备双(三甲基硅基)硫化物。1,2 TMS2S现在是市售的(约28欧元/克)该试剂可被视为硫化物的S1源,毒性较小,不易燃,并且比气态硫化氢(H2S)更容易处理。TMS2S遇水会释放出H2S,应保存在无氧环境下,阴凉干燥处。TMS2S用作合成烷基硫化物、硫代醛或硫酮的硫转移剂,也用作还原剂TMS2S也被用于合成无机-有机杂化簇5或膦烯硫化物化合物值得注意的是,自20世纪50年代以来,描述TMS2S使用的出版物数量稳步增加,从2015年到2022.7年平均每年达到65篇。本文重点介绍了TMS2S作为硫化物S1来源的多功能性及其在有机合成中的最新应用。1999年,Hu和Fox报道了一个合成功能化硫醇的三甲基硅基硫氧基脱卤反应(表1,a) 8Damien Hazelard博士(右)在A. Fadel博士(巴黎南部大学)的指导下于2005年获得博士学位。2006年,他在东京科学大学Hayashi教授的指导下进行了有机催化领域的博士后培训。随后,他加入了F. Colobert教授的团队,在斯特拉斯堡大学从事全合成研究。他于2010年被任命为同一所大学P. Compain教授小组的助理教授。2019年7月,他为自己的康复辩护(“康复 Diriger des reches”)。他的主要研究兴趣是糖仿制品合成新合成方法的发展。
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引用次数: 0
SynOpen is Fast, Fair, and Flexible SynOpen是快速,公平和灵活的
IF 2.5 Q2 CHEMISTRY, ORGANIC Pub Date : 2023-04-01 DOI: 10.1055/s-0040-1720063
Thierry Ollevier
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引用次数: 0
Multi-step Flow Synthesis of the Anthelmintic Drug Praziquantel 驱虫药吡喹酮的多步流合成
IF 2.5 Q2 CHEMISTRY, ORGANIC Pub Date : 2023-04-01 DOI: 10.1055/s-0042-1751479
M. S. Phull, S. S. Jadav, Chander Singh Bohara, R. Gundla, P. Mainkar
Praziquantel (PZQ; Brand name: Biltricide) is categorized as an anthelminthic drug, and it is used for the treatment of Schistosomiasis and other parasitic infections. The World Health Organization (WHO) has classified it as one of the essential and emergency medicines needed across the globe. The price of PZQ formulated product depends on the associated method of preparation, along with cost of raw materials. A precise and reliable method for the preparation of PZQ using a flow-chemistry approach is described in this study using phenylethylamine as the starting material. The main objective of the present study is to identify a new economical route for the synthesis of PZQ that could decrease the production time drastically from days to minutes and be transferred to large-scale production. Simultaneously, the purity of the obtained intermediates in essential steps, as single or continuous process, determined by HPLC analysis were more than 90% pure. The continuous preparation process of PZQ in the current study was achieved in less time (ca. 3–4 h) than using conventional methods (ca. 3–4 days). Moreover, the required quantity of key intermediate dimethoxyethanamine is 40–50% less than in existing methods.
吡喹酮(PZQ;品牌名称:Biltricide)被归类为驱虫药物,用于治疗血吸虫病和其他寄生虫感染。世界卫生组织(WHO)已将其列为全球所需的基本和紧急药物之一。PZQ配方产品的价格取决于相关的制备方法,以及原材料的成本。本文介绍了以苯乙胺为原料,采用流动化学方法制备PZQ的一种精确、可靠的方法。本研究的主要目的是确定一种新的合成PZQ的经济路线,可以将生产时间从几天大幅减少到几分钟,并转移到大规模生产。同时,通过HPLC分析,所得中间体的纯度均在90%以上。在本研究中,PZQ的连续制备过程比使用常规方法(约3-4天)在更短的时间内(约3-4小时)实现。关键中间体二甲氧基乙胺的需要量比现有方法减少40 ~ 50%。
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引用次数: 0
Electrochemical/I – Dual-Catalyzed Access to Sulfonated Pyrazoles under External Oxidant-Free Conditions 在无外部氧化剂条件下电化学/I-双催化获得磺化吡唑
IF 2.5 Q2 CHEMISTRY, ORGANIC Pub Date : 2023-03-28 DOI: 10.1055/a-2089-0485
Jing Ma, Jianjing Yang, Kelu Yan, Boju Luo, Kexin Huang, Ziling Wu, Yumeng Zhou, Shuyun Zhu, Xian-En Zhao, Jiangwei Wen
An electrochemical/I− dual-catalyzed access to sulfonated pyrazoles from pyrazolones and sodium sulfites under external oxidant-free conditions has been developed. This established electrochemical reaction works smoothly under external oxidant-free conditions, and has the advantages of good functional group tolerance, easy to gram-scale synthesis, delivering up to 95% yield for 35 examples.
研究了在无氧化条件下,由吡唑酮和亚硫酸钠在电化学/I−双催化下获得磺化吡唑的方法。所建立的电化学反应在无外界氧化剂的条件下顺利进行,具有良好的官能团耐受性,易于克级合成,35个样品的产率高达95%。
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引用次数: 1
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SynOpen
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