Rearomatization of trifluoromethyl sulfonyl dihydropyridines: Thermolysis vs photolysis

被引:3
作者
Firpo, Guadalupe [1 ]
Cooke, Maria V. [1 ]
Pelaez, Walter J. [1 ]
Chans, Guillermo M. [2 ]
Arguello, Gustavo A. [1 ]
Gomez, Elizabeth [3 ]
Alvarez-Toledano, Cecilio [3 ]
机构
[1] Univ Nacl Cordoba, INFIQC, Dept Fis Quim, Fac Ciencias Quim, Ciudad Univ,X5000HUA, Cordoba, Argentina
[2] Univ Anahuac Mexico Norte, Fac Ingn, Huixquilucan, Argentina
[3] Univ Nacl Autonoma Mexico, Inst Quim, Mexico City, DF, Mexico
关键词
gas-phase and microwave-induced pyrolysis; rearomatization reactions; TD-DFT calculations; trifluoromethyl sulfonyl dihydropyridines; 1,1-BIS(TRIMETHYLSILYLOXY)KETENE ACETALS; DELTA-LACTONES; GAMMA-LACTONES; ACTIVATION; ANHYDRIDE; ADDITIONS; SALTS;
D O I
10.1002/poc.3789
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
In this article, we describe the static gas-phase pyrolysis, microwave-induced pyrolysis, and photolysis reactions of trifluoromethyl sulfonyl dihydropyridines. The goal of this work was to find a methodology that allows obtaining of substituted pyridines-which are known to be difficult to synthesize-to be reused in a new substitution reaction. We demonstrated that it is possible to achieve the rearomatization process by the elimination of the trifluoromethyl sulfonyl moiety through the 3 processes, with the static pyrolysis being the best method to obtain the substituted pyridines. In addition, we propose the 1,4-elimination (CF3SO2 + H) as the first step, since it is the less energetic process, as has also been corroborated by calculations. A competitive reaction (CO2 extrusion) also occurs, yielding undesired products.
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页数:12
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