کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
8954825 | 1646047 | 2018 | 54 صفحه PDF | دانلود رایگان |
عنوان انگلیسی مقاله ISI
Experimental and DFT studies for the kinetics and mechanism of the pyrolysis of 2-(4-substituted-phenoxy)tetrahydro-2H-pyranes in the gas-phase
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کلمات کلیدی
موضوعات مرتبط
مهندسی و علوم پایه
شیمی
شیمی آنالیزی یا شیمی تجزیه
پیش نمایش صفحه اول مقاله
چکیده انگلیسی
DFT theoretical calculations were performed to 2-(4-substituted-phenoxy) tetrahydro-2H-pyranes with groups H, OCH3, C(CH3)3, CN and Br. The calculated values for thermodynamic parameters using the WB97XD/6-311â¯+â¯+G(d,p) level have a good agreement with the experimental values except for the cyano compound. Experimental and theoretical data suggest a mechanism with four-membered cyclic transition state (TS). The results indicate a small increment of rate constants values with raising electron donating ability groups in the phenoxy ring, and a slight decrease effect with electron withdrawing substituents. The effect of resonance structures giving by the phenyl ring seems to be the main factor in the TS stabilization. The assistance of the oxygen atom belonging to the phenoxy group in the pyranyl hydrogen abstraction exerts influence on the rate constants, but the polarization of Cδ+â¯Î´âOPh bond is proposed as the rate determining process.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Analytical and Applied Pyrolysis - Volume 134, September 2018, Pages 52-60
Journal: Journal of Analytical and Applied Pyrolysis - Volume 134, September 2018, Pages 52-60
نویسندگان
Alvaro Alvarez-Aular, Loriett Cartaya, Alexis Maldonado, Yeljair Monascal, David Santiago Coll, Gabriel Chuchani,