Chemoenzymatic Kinetic resolution of (R)-malathion in aqueous media

Chemistry Central Journal

Carlos A. Enríquez-Núñez¹  Alejandro A. Camacho-Dávila¹  Víctor H. Ramos-Sánchez¹  Gerardo Zaragoza-Galán¹  Lourdes Ballinas-Casarrubias¹  David Chávez-Flores¹ 

[1] Facultad de Ciencias Químicas, Universidad Autónoma de Chihuahua, Circuito No.1 Campus Universitario, Chihuahua, Arboledas 31125, Chihuahua, México

关键词: Malathion;    Resolution;    Enzymatic;    Enantiomer;   

Others  :  1225400
DOI  :  10.1186/s13065-015-0119-y

 received in 2015-01-03, accepted in 2015-07-10,  发布年份 2015

【 摘 要 】

Background

Malathion (R,S)-diethyl-2-[(dimethoxyphosphorothioyl)sulfanyl]butanedioate is a chiral organophosphorus compound used widely as pesticide for suppression of harmful insects such as mosquitoes. It is well known that in biological systems (R)-malathion is the active enantiomer, therefore a sustainable approach could be the use of only the biologically active enantiomer. The resolution of the commercial racemic mixture to obtain the pure active enantiomer combined with a recycling of the undesired enantiomer through a racemization process could be an attractive alternative to reduce the environmental impact of this pesticide. Thus, this work evaluates the use of four commercially available lipases for enantioselective hydrolysis and separation of malathion enantiomers from the commercial racemic mixture.

Results

Several lipases were methodologically assessed, considering parameters such as enzyme concentration, temperature and reaction rates. Among them, Candida rugosa lipase exhibited the best performance, in terms of enantioselectivity, E = 185 (selective to the (S)-enantiomer). In this way, the desired unreacted (R)-enantiomer was recovered in a 49.42 % yield with an enantiomeric excess of 87 %. The monohydrolized (S)-enantiomer was recovered and racemized in basic media, followed by esterification to obtain the racemic malathion, which was recycled. In this way, an enantioenriched mixture of (R)-malathion was obtained with a conversion of 65.80 % considering the recycled (S)-enantiomer.

Conclusion

This work demonstrated the feasibility of exploiting Candida rugosa lipase to kinetically resolve racemic malathion through an environmentally friendly recycling of the undesired (S)-enantiomer.

【 授权许可】

   
2015 Enríquez-Núñez et al.

【 图 表 】

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