Simultaneous effect of microemulsions and phase-transfer agents on aminolysis reactions.
The catalytic effect of triethylene glycol dimethyl ether (glyme) on the butylaminolysis of 4-nitrophenylcaprate (NPC) in water/AOT/chlorobenzene microemulsions has been studied. Experimental results show the existence of four simultaneous reaction pathways. One of them takes place at the microemulsion interphase where the rate-determining step of butylaminolysis is the formation of the addition intermediate, T+/-. The locus of the other three pathways is the continuous medium of the microemulsion. These three pathways consist of the decomposition of the addition intermediate catalyzed by butylamine, by glyme, and by both of them. The kinetic model allows us to obtain the value of every rate and distribution constant involved in the overall reaction mechanism. We must emphasize that the reactions located in the continuous medium exhibit a kinetic behavior similar to the corresponding one found in pure chlorobenzene. On the basis of the pseudophase model, the percentage of reaction in each of the microdomains of the microemulsion has been calculated. Likewise, changes in the loci of reaction from the interphase to the continuous medium as a function of catalyst concentration have been proved.
García-Río
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Departamento de Química Física, Facultade de Química, Universidade de Santiago, 15782 Santiago, Spain. qflgr3cn@usc.es
Mejuto
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JC
Pérez-Lorenzo
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