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

2019 ◽  
Vol 14 (4) ◽  
pp. 208-215
Author(s):  
I.S. Kostiv ◽  
R.I. Havryliv

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.

2011 ◽  
Vol 9 (1) ◽  
pp. 192-198 ◽  
Author(s):  
Bożena Bittner ◽  
Ewa Janus ◽  
Eugeniusz Milchert

AbstractA comparative study of the Diels-Alder reactions between cyclopentadiene (1) and dienophiles (2 a–c) in N-hexylpyridinium bis(trifluoromethylsulfonyl)imide in a temperature range of 20–45°C is reported. The reaction rate constants and activation energies were calculated. Moreover, the catalytic systems based on N-hexylpyridinium bis(trifluoromethylsulfonyl)imide and Lewis acids were tested as a reaction media to perform the Diels-Alder reaction. Yb, Y, Mg, Zn triflates and chlorides (0.005 to 0.1 mmol) were used as catalysts. The recycling of catalytic system consisted of YCl3 and ionic liquid was performed.


2004 ◽  
Vol 53 (1) ◽  
pp. 45-50 ◽  
Author(s):  
V. D. Kiselev ◽  
E. A. Kashaeva ◽  
M. S. Shihab ◽  
L. N. Potapova ◽  
G. G. Iskhakova

2020 ◽  
Vol 53 (2) ◽  
pp. 207-212
Author(s):  
Vladimir D. Kiselev ◽  
Anastasia O. Kolesnikova ◽  
Ildar F. Dinikaev ◽  
Alexey A. Shulyatiev ◽  
Alexander E. Klimovitskii ◽  
...  

1989 ◽  
Vol 42 (1-2) ◽  
pp. 15-19 ◽  
Author(s):  
Moustafa Chehna ◽  
Jean Paul Pradere ◽  
Herve Quiniou ◽  
Denis Le Botlan ◽  
Loic Toupet

RSC Advances ◽  
2015 ◽  
Vol 5 (4) ◽  
pp. 2882-2890 ◽  
Author(s):  
Heng Wang ◽  
Na Li ◽  
Zijia Yan ◽  
Jie Zhang ◽  
Xinhua Wan

Soluble and recyclable Cu(ii)–pyridineoxazoline containing polymeric catalyst shows faster reaction rate and higher enantio-selectivity than its low molecular mass counterpart in D–A reaction of 2-alkenoyl pyridine N-oxide and cyclopentadiene.


2016 ◽  
Vol 12 ◽  
pp. 2181-2188 ◽  
Author(s):  
Ángel Cantín ◽  
M Victoria Gomez ◽  
Antonio de la Hoz

Diels–Alder cycloaddition between cyclopentadiene and p-benzoquinone has been studied in the confined space of a pure silica zeolite Beta and the impact on reaction rate due to the concentration effect within the pore and diffusion limitations are discussed. Introduction of Lewis or Brønsted acid sites on the walls of the zeolite strongly increases the reaction rate. However, contrary to what occurs with mesoporous molecular sieves (MCM-41), Beta zeolite does not catalyse the retro-Diels–Alder reaction, resulting in a highly selective catalyst for the cycloaddition reaction.


1976 ◽  
Vol 29 (3) ◽  
pp. 599 ◽  
Author(s):  
JL Garnett ◽  
WD Johnson ◽  
JE Sherwood

At 495� the decomposition of both 1-methylcyclohexene and methylenecyclohexane is homogeneous and first order overall, the rate constants (with 90% confidence limits) being (6.01 � 0.40) x 10-4 and (6.53 � 0.23) x 10-4 s-1 respectively. Pressure is not a good measure of the rate of decomposition of either isomer. Toluene inhibits the decomposition of both olefins, although the effect is more marked for the exo-isomer. The two main reaction pathways for 1-methylcyclohexene are a reverse Diels-Alder reaction, giving 2-methylbuta-1,3-diene and ethene, and a radical chain dehydrogenation to give toluene and benzene. Methylenecyclohexane cannot react through a reverse Diels-Alder reaction and ring fission gives a mixture of C3 and lower hydrocarbons. Dehydrogenation to give benzene and toluene is also important. Isomerization is a much more favoured pathway for methylenecyclohexane as expected from the relative thermodynamic stabilities of the isomers.


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