Stereoselectivity and Environmental
Behaviour of Pyrethroids
Cláudio Ernesto Taveira Parente, Olaf Malm,
and Francisco Radler de Aquino Neto
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
2 Pyrethroid Structure Configuration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
3 Metabolic Pathways and Toxicity in Nontarget Organisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
3.1 Soil Organisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
3.2 Aquatic Environments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
3.3 Mammals: In Vivo and In Vitro Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
3.4 Abiotic and Laboratory-Based Epimerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
4 Stereoisomeric Profile and Environmental Dynamics of Chiral Pollutants . . . . . . . . . . . . . . . . 164
4.1 Pyrethroid Stereoisomerism on Environmental Samples . . . . . . . . .. . . . . . . . . . . . . .. . . . . . 165
5 Conclusions and Trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
Abstract Pyrethroids are chiral insecticides due to the occurrence of up to three
asymmetric carbons. Each stereogenic centre generates two possible spatial configurations (R- or S-enantiomers), which are non-superimposable mirrored forms. Two
chiral carbons on the cyclopropane ring generate four enantiomers on Type I
pyrethroids, while a third chiral centre on Type II pyrethroids generates eight
enantiomers. The chiral nature of enzymatic sites favours specific insecticidal
activity only for some enantiomers in commercial formulations. On the other
hand, there is an overabundance of enantiomers with no desired activity or even
undesired side effects. In this sense, in addition to the previously described toxicity
of insecticide enantiomers to nontarget organisms, adverse effects, such as endocrine
C. E. T. Parente (*) and O. Malm
Laboratório de Radioisótopos Eduardo Penna Franca, Instituto de Biofísica Carlos Chagas
Filho, Universidade Federal do Rio de Janeiro, Rio de Janeiro, Brazil
e-mail: cparente@biof.ufrj.br; claudioetparente@gmail.com
F. R. de Aquino Neto
Laboratório de Apoio ao Desenvolvimento Tecnológico – LADETEC, Instituto de Química,
Universidade Federal do Rio de Janeiro, Rio de Janeiro, Brazil
Ethel Eljarrat (ed.), Pyrethroid Insecticides,
Hdb Env Chem (2020) 92: 149–176, DOI 10.1007/698_2019_426,
© Springer Nature Switzerland AG 2020, Published online: 4 January 2020
149
Behaviour of Pyrethroids
Cláudio Ernesto Taveira Parente, Olaf Malm,
and Francisco Radler de Aquino Neto
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
2 Pyrethroid Structure Configuration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
3 Metabolic Pathways and Toxicity in Nontarget Organisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
3.1 Soil Organisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
3.2 Aquatic Environments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
3.3 Mammals: In Vivo and In Vitro Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
3.4 Abiotic and Laboratory-Based Epimerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
4 Stereoisomeric Profile and Environmental Dynamics of Chiral Pollutants . . . . . . . . . . . . . . . . 164
4.1 Pyrethroid Stereoisomerism on Environmental Samples . . . . . . . . .. . . . . . . . . . . . . .. . . . . . 165
5 Conclusions and Trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
Abstract Pyrethroids are chiral insecticides due to the occurrence of up to three
asymmetric carbons. Each stereogenic centre generates two possible spatial configurations (R- or S-enantiomers), which are non-superimposable mirrored forms. Two
chiral carbons on the cyclopropane ring generate four enantiomers on Type I
pyrethroids, while a third chiral centre on Type II pyrethroids generates eight
enantiomers. The chiral nature of enzymatic sites favours specific insecticidal
activity only for some enantiomers in commercial formulations. On the other
hand, there is an overabundance of enantiomers with no desired activity or even
undesired side effects. In this sense, in addition to the previously described toxicity
of insecticide enantiomers to nontarget organisms, adverse effects, such as endocrine
C. E. T. Parente (*) and O. Malm
Laboratório de Radioisótopos Eduardo Penna Franca, Instituto de Biofísica Carlos Chagas
Filho, Universidade Federal do Rio de Janeiro, Rio de Janeiro, Brazil
e-mail: cparente@biof.ufrj.br; claudioetparente@gmail.com
F. R. de Aquino Neto
Laboratório de Apoio ao Desenvolvimento Tecnológico – LADETEC, Instituto de Química,
Universidade Federal do Rio de Janeiro, Rio de Janeiro, Brazil
Ethel Eljarrat (ed.), Pyrethroid Insecticides,
Hdb Env Chem (2020) 92: 149–176, DOI 10.1007/698_2019_426,
© Springer Nature Switzerland AG 2020, Published online: 4 January 2020
149