Aromatic Cross-Conjugated Hydrazones as Inhibitors of the Radical Chain Oxidation of Styrene

IF 1.3 4区 化学 Q4 CHEMISTRY, PHYSICAL Kinetics and Catalysis Pub Date : 2024-11-04 DOI:10.1134/S0023158424601852
S. A. Grabovskii, I. S. Odin, A. A. Golovanov, A. V. Antipin, R. L. Safiullin
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Abstract

The bond dissociation enthalpy of the N–H bond was calculated for the following compounds: 1-((E)-1,5-diphenylpent-1-en-4-yn-3-ylidene)-2-(o-tolyl)hydrazine, 1-((E)-1-(4-methoxyphenyl)-5-phenylpent-1-en-4-yn-3-ylidene)-2-phenylhydrazine, 1-((E)-1-phenylpent-1-en-4-yn-3-ylidene)-2-(p-tolyl)hydrazine, 1-((E)-1-(4-methoxyphenyl)-5-trimethylsilyl-1-en-4-yn-3-ylidene)-2-phenylhydrazine, and 1-((E)-1-(toiphenyl-2)-5-phenylpent-1-en-4-yn-3-ylidene)-2-phenylhydrazine. The calculations were performed by the M06-2X/6-311+G(2df,2pd)//B3LYP/6-31G(d) method using the homodesmotic approach. The bond dissociation enthalpy is lower than 77 kcal/mol for all the cross-conjugated hydrazone derivatives under study. The experimental rate constants for the reactions of the derivatives with peroxyl radicals in chlorobenzene during the initiated styrene oxidation are comparable to those of aromatic amines and are in the range (1.1–2.5) × 105 M−1 s−1. The stoichiometric inhibition coefficient depends on the structure of the derivatives and varies from 0.7 to 1.9. The inhibition is discussed within the framework of the radical mechanism.

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作为苯乙烯自由基链氧化抑制剂的芳香族交叉共轭肼酮
计算了下列化合物 N-H 键的键解离焓:1-((E)-1,5-二苯基戊-1-烯-4-炔-3-亚基)-2-(邻甲苯基)肼、1-((E)-1-(4-甲氧基苯基)-5-苯基戊-1-烯-4-炔-3-亚基)-2-苯肼、1-((E)-1-苯基戊-1-烯-4-炔-3-亚基)-2-(对甲苯基)肼、1-((E)-1-(4-甲氧基苯基)-5-三甲基硅基-1-烯-4-炔-3-亚基)-2-苯肼,以及 1-((E)-1-(甲苯-2)-5-苯基戊-1-烯-4-炔-3-亚基)-2-苯肼。计算采用 M06-2X/6-311+G(2df,2pd)//B3LYP/6-31G(d)方法,使用同调方法。所研究的所有交叉共轭腙衍生物的键解离焓均低于 77 kcal/mol。在启动苯乙烯氧化过程中,这些衍生物与氯苯中的过氧自由基发生反应的实验速率常数与芳香胺的速率常数相当,范围在 (1.1-2.5) × 105 M-1 s-1 之间。化学计量抑制系数取决于衍生物的结构,范围在 0.7 到 1.9 之间。我们在自由基机理的框架内讨论了这种抑制作用。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Kinetics and Catalysis
Kinetics and Catalysis 化学-物理化学
CiteScore
2.10
自引率
27.30%
发文量
64
审稿时长
6-12 weeks
期刊介绍: Kinetics and Catalysis Russian is a periodical that publishes theoretical and experimental works on homogeneous and heterogeneous kinetics and catalysis. Other topics include the mechanism and kinetics of noncatalytic processes in gaseous, liquid, and solid phases, quantum chemical calculations in kinetics and catalysis, methods of studying catalytic processes and catalysts, the chemistry of catalysts and adsorbent surfaces, the structure and physicochemical properties of catalysts, preparation and poisoning of catalysts, macrokinetics, and computer simulations in catalysis. The journal also publishes review articles on contemporary problems in kinetics and catalysis. The journal welcomes manuscripts from all countries in the English or Russian language.
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