Reductive dehalogenation and formation of sulfonated quinones in the aqueous reactions between various chloro-1,4-benzoquinones and sulfur(IV)

IF 2.1 3区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Journal of Sulfur Chemistry Pub Date : 2023-05-24 DOI:10.1080/17415993.2023.2214267
V. Kiss, Á. Kecskeméti, Bence Marcell Hülvely, Péter Tarczali Sarudi, Luca Judit Csépes-Ruzicska, Fruzsina Mercs, Ágnes Tóth, I. Fábián, Katalin Ősz
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Abstract

In this paper, the kinetic study of the reaction between substituted 1,4-benzoquinones (RBQs) and Na2SO3 (S(IV)) is presented in aqueous solutions at different pH values and reagent concentrations. The stoichiometry of the reaction is 1:2 RBQs:S(IV) and one equivalent of chloride ion was also detected as a product when using mono- (2-CBQ) or dichloro-benzoquinones (2,5-DCBQ; 2,6-DCBQ) as reactants. This shows that reductive dehalogenation occurs instead of simple reduction to the corresponding substituted 1,4-hydroquinones (RBQHs) and quinone bisulfites are formed, analogously to the addition of bisulfite ion to carbonyl compounds. Various sulfonated quinones have been identified as products by electrospray mass spectrometry. Kinetic traces at different wavelengths were obtained by the stopped-flow technique with spectrophotometric detection, a kinetic fitting program (ZiTa) was used to fit a multi-step model to the data. A detailed mathematical evaluation of the reaction scheme was carried out under non-pseudo-first order conditions showing that our model can be fitted with a double exponential function even when none of the reagents are in large excess. GRAPHICAL ABSTRACT
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在各种氯-1,4-苯并醌与硫的水反应中还原脱卤和磺化醌的形成(IV)
本文研究了取代的1,4-苯并醌(RBQ)与Na2SO3(S(IV))在不同pH值和试剂浓度的水溶液中的反应动力学。反应的化学计量为1:2 RBQ:S(IV),当使用单-(2-CBQ)或二氯-苯并醌(2,5-DCBQ;2,6-DCBQ)作为反应物时,也检测到一当量的氯离子作为产物。这表明还原脱卤发生,而不是简单还原为相应的取代的1,4-氢醌(RBQHs),并形成醌亚硫酸氢盐,类似于将亚硫酸氢离子添加到羰基化合物中。电喷雾质谱法已鉴定出各种磺化醌类化合物。通过停流技术和分光光度法检测获得了不同波长的动力学痕迹,并使用动力学拟合程序(ZiTa)将多步模型拟合到数据中。在非伪一阶条件下对反应方案进行了详细的数学评估,表明即使没有任何试剂过量,我们的模型也可以用双指数函数拟合。图形摘要
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来源期刊
Journal of Sulfur Chemistry
Journal of Sulfur Chemistry CHEMISTRY, MULTIDISCIPLINARY-
CiteScore
4.10
自引率
9.10%
发文量
38
审稿时长
6-12 weeks
期刊介绍: The Journal of Sulfur Chemistry is an international journal for the dissemination of scientific results in the rapidly expanding realm of sulfur chemistry. The journal publishes high quality reviews, full papers and communications in the following areas: organic and inorganic chemistry, industrial chemistry, materials and polymer chemistry, biological chemistry and interdisciplinary studies directly related to sulfur science. Papers outlining theoretical, physical, mechanistic or synthetic studies pertaining to sulfur chemistry are welcome. Hence the target audience is made up of academic and industrial chemists with peripheral or focused interests in sulfur chemistry. Manuscripts that truly define the aims of the journal include, but are not limited to, those that offer: a) innovative use of sulfur reagents; b) new synthetic approaches to sulfur-containing biomolecules, materials or organic and organometallic compounds; c) theoretical and physical studies that facilitate the understanding of sulfur structure, bonding or reactivity; d) catalytic, selective, synthetically useful or noteworthy transformations of sulfur containing molecules; e) industrial applications of sulfur chemistry; f) unique sulfur atom or molecule involvement in interfacial phenomena; g) descriptions of solid phase or combinatorial methods involving sulfur containing substrates. Submissions pertaining to related atoms such as selenium and tellurium are also welcome. Articles offering routine heterocycle formation through established reactions of sulfur containing substrates are outside the scope of the journal.
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