Investigation Of Kinetic Regularities For Obtaining Methyl-1,3,4- Trimethylcyclohex-3-Encarboxylate By Reaction Of Diels-Alder

IF 0.7 Q4 CHEMISTRY, ANALYTICAL Methods and Objects of Chemical Analysis Pub Date : 2019-01-01 DOI:10.17721/moca.2019.208-215
I. Kostiv, R. Havryliv
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Abstract

Kinetics of the reaction of the cycloaddition of 2,3-dimethylbuta-1,3-diene (DMB) and methylmethacrylate (MMA) by the Diels-Alder reaction was studied. Reaction rate constants k = 4.4∙10-6 l/(mol∙s) at T = 403 K; k = 10.0∙10-6 l/(mol∙s) at T = 413 K; k = 15.8∙10-6 l/(mol∙s) at T = 423 K; k = 19.4∙10-6 l/(mol∙s) at T = 433 K and the activation parameters of the reaction Eakt = 75.2 kJ/mol, ΔS = -146.8 J/(mol∙K), ΔH = 73.9 kJ/mol were determined. Influence of temperature, molar ratio of reagents on the yield of the target product was investigated. At temperature increase from 403 to 433 K, methyl-1,3,4-trimethylcyclohex-3-encarboxylate (MTMCHC) yield increases from 78 % to 92 %. With further increase in temperature, DMB boils and MMA remains in a liquid state, accordingly it is not expected that the target product yield will materially increase. An increase in the excess of DMB: МMA from 1:1 to 2.5:1 makes it possible to increase yield of MTMCHC from 65 % to 92 %. The production of methyl-1,3,4-trimethylcyclohex-3-encarboxylate at the optimal conditions was established: temperature of 423−433 K and molar ratio of reagents DMB:MMA = 1.5:1, the yield of MTMCHC reaches 89−92 % at productivity of 101−105 g/(l·h). Based on the obtained reaction rate constants and the activation parameters of the [4+2]-cyclic addition of 2,3-dimethylbuta-1,3-diene and methylmethacrylate, it was found that the reaction under study is subject to the kinetic law of the second order.
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Diels-Alder反应制备甲基-1,3,4-三甲基环己基-3-羧化酸酯的动力学规律研究
研究了2,3-二甲基丁酸-1,3-二烯(DMB)与甲基丙烯酸甲酯(MMA)的Diels-Alder环加成反应动力学。T = 403 k时的反应速率常数k = 4.4∙10-6 l/(mol∙s);T = 413 k时k = 10.0∙10-6 l/(mol∙s);T = 423 k时k = 15.8∙10-6 l/(mol∙s);在T = 433 k时k = 19.4∙10-6 l/(mol∙s),确定了反应的活化参数Eakt = 75.2 kJ/mol, ΔS = -146.8 J/(mol∙k), ΔH = 73.9 kJ/mol。考察了温度、试剂的摩尔比对目标产物收率的影响。当温度从403 K提高到433 K时,甲基-1,3,4-三甲基环己基-3-羧化酸酯(MTMCHC)的产率从78%提高到92%。随着温度的进一步升高,DMB沸腾,MMA保持液态,因此预期目标产物收率不会有实质性的提高。将DMB: МMA的过剩量从1:1增加到2.5:1,可以将MTMCHC的收率从65%提高到92%。在温度423 ~ 433 K, DMB:MMA摩尔比为1.5:1的条件下,甲基-1,3,4-三甲基环己基-3-羧酸甲酯的产率为89 ~ 92%,产率为101 ~ 105 g/(l·h)。根据得到的2,3-二甲基丁酸-1,3-二烯与甲基丙烯酸甲酯[4+2]-环加成反应的反应速率常数和活化参数,发现所研究的反应符合二级动力学规律。
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来源期刊
CiteScore
1.00
自引率
14.30%
发文量
12
期刊介绍: The journal "Methods and objects of chemical analysis" is peer-review journal and publishes original articles of theoretical and experimental analysis on topical issues and bio-analytical chemistry, chemical and pharmaceutical analysis, as well as chemical metrology. Submitted works shall cover the results of completed studies and shall make scientific contributions to the relevant area of expertise. The journal publishes review articles, research articles and articles related to latest developments of analytical instrumentations.
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