The history of extensive structural modifications of pyrethroids

Abstract

The structural modification of natural pyrethrins has led to a number of synthetic pyrethroid insecticides, and each compound has its own characteristics. At present, pyrethroid insecticides are applied not only for household use, the original use for pyrethrins, but also for a wide range of uses such as crop protection, pharmaceuticals, and veterinary applications. Quoting primary sources, this review describes the historical view of structural modifications of pyrethroids, with a focus on structural similarities, and their use.

Nematicidal activity of menthol and its dithiophosphoric derivatives

“…Pyrethroids are known to be derivatives of pyrethrins -substances found in Dalmatian chamomile Pyrethrum cinerariaefolium, cinerarii folium tansy Tanacetum cinerariifolium and some other plants of the Compositae family. For several decades, a large number of substances with a wider spectrum of insecticidal activity and higher toxicity than pyrethrins have been synthesized [30].…”

Pyrethroid insecticides Chapter IVb. Selected transformations of chrysanthemic acid and its lower esters to Pyrethroid. Use of the Wittig and related reactions

“…Variations on the structure of pyrethrin I (1aA) and to a lower extend on that of Pyrethin II (1bMeA) have affected [1][2][3][4][5] (i) the alkoxy part exemplified by allethrin (1aB) (LaForge; 1949) or prallethrin (1aC) (Katsuda; 1967) in which the structural variations are minimal (Figure 1, entry a) to resmethrin (1aD) (Elliot 1966), phenothrin (1aE) (Itaya, 1973) and cyphenothrin (1aF) (Itaya, 1976) that possess an alkoxy part dramatically different from the original one (Figure 1, entry b) [1][2][3][4][5][6][7] (ii) those in which slight changes appear on the vinyl cyclopropane moiety [1][2][3][4][5] such as "nor-allethrin" (1cB) (Elliot, Ohno; or metofluthrin (1cG) (Matsuo; 1998) 2,11 (iii) those in which important changes are present on the vinyl cyclopropane moiety such as "dichloro-allethrin" (1dB) (Farkas;1958), or (iv) on both the vinyl cyclopropane and the alkoxy moieties [1][2][3][4][5][6][7] such as fluorethrin 1eD , chlorethrin (1dD), bromethrin (1fD) (Brown, Elliott;1973) or permethrin (1dE) and cypermethrin (1dF) 1973) or deltamethrin (1fF) .…”

“…Cypermethrin (1dF) is sold as the mixture of stereoisomers, whereas deltamethrin (1fF) is sold as the enantiopure (S,1R,3S)-cis-enantiomer and is the most active insecticide of the series. 1,2,3,4,5 The transformations of chrysanthemic acid to analogues has been carried out in different companies and research centres especially in France, UK, Japan and Germany, among others. Comparative results that are reported below speak for themselves [Relative toxicity against Spodoptera littoralis: [deltamethrin/cypermethrin/parathion/monocrotophos/DDT: 1/10/1.300/7.700/32.000].…”

Structural Aspects of Potential Endocrine-Disrupting Activity of Stereoisomers for a Common Pesticide Permethrin against Androgen Receptor

“…The majority of the pyrethroid compounds contain a cyclopropane ring in their structure as most of them are derivatives of 2, 2-dimethylcyclopropanecarboxylic acid [ 25 ]. However, these compounds show chirality due to the presence of two chiral centers in their cyclopropane ring, hence generating stereoisomers.…”