Synthesis, larvicidal, QSAR and structural studies of some triorganotin 2,2,3,3‐tetramethylcyclopropanecarboxylates

Abstract

A series of triorganotin 2,2,3,3-tetramethylcyclopropanecarboxylates, where R = methyl, ethyl, npropyl, n-butyl, phenyl and cyclohexyl, have been synthesized. Elemental analysis, Mössbauer, infrared and NMR spectroscopies were used to characterize their structures. Based on the spectroscopic results, all the complexes in the solid state with the exception of the tricyclohexyl compound were found to be five-coordinated, while the tricyclohexyltin derivative was determined to be fourcoordinated. Based on the NMR results, all the complexes in solution have a tetrahedral configuration. Larvicidal activities of the complexes were evaluated against the second instar stage of the Aedes aegypti, Anopheles stephensi and Culex pipiens quinquefasciatus mosquitoes. The toxicity results indicated that this series of triorganotins are effective larvicides against all three species of larvae. In addition, quantitative structure-activity relationships (QSARs) were also developed for each species of larvae.

Organotin(IV) carboxylates of cyclopropane carboxylic acid and 3‐cyclohexylpropanoic acid: synthesis, characterization and biological activity. The crystal structure of bis(cyclopropanecarboxylato) tetramethyldistannoxane

“…Although the shift ranges are somewhat dependent on the nature of the substituent at the tin atom, an approximate range between +200 and −60 ppm has been proposed for the four-coordinated alkyltin compounds. [14] On the basis of 119 Sn NMR data (Table 3), it appears reasonable to assume that in all the triorganotin carboxylates the effective coordination number is four in solution, [14 -16] as is consistent with previous literature reports of similar compounds. [14 -16] The 1 H and 13 C NMR spectra of 5, 6 and 11 (Tables 2 and 3, respectively) displayed two sets of R-Sn resonances, as expected for dimeric dicarboxylatotetraorganodistannoxanes, with high-field resonances for exo-cyclic and low-field resonances for the endocyclic R 2 Sn moieties.…”

“…The 2 J( 119 Sn-1 H) coupling constant of 58.80 and 57.00 Hz and 1 J( 119 Sn-13 C) values = 400.00 Hz and 398.60 Hz in 4 and 10, respectively, falls in the range of tetrahedral geometry in solution. [14] The 1 J( 119 Sn-13 C) values of tri-n-butyltin and triphenyltin derivatives confirm the tetrahedral structure in non-coordinating solvents. In addition, the calculated C-Sn-C angles of 111…”

“…As expected, the four hydrogens on the cyclopropane ring were observed as two singlets. [14] In 4 and 10, the Sn-Me protons appear as a sharp singlet at δ 0.52 and δ 0.53 ppm, respectively. The 2 J( 119 Sn-1 H) coupling constant of 58.80 and 57.00 Hz and 1 J( 119 Sn-13 C) values = 400.00 Hz and 398.60 Hz in 4 and 10, respectively, falls in the range of tetrahedral geometry in solution.…”

“…During the preparation of the manuscript we have come across a report on the synthesis and larvicidal activity of a tetramethyl derivative of cyclopropane carboxylic acid incorporating triorganotin moiety. [14] The crystal structures of trimethyltin [15] and tricyclohexyltin [16] derivative of 2,2,3,3-tetramethyl cyclopropane carboxylate have also been reported in literature.…”

Synthesis, structural and larvicidal studies of a series of triorganotin chrysanthemumates

“…Previously, modified fragments of pyrethrin such as a methylbutyrate and/or cyclopropanecarboxylate group have been incorporated into various triorganotins and their activities were evaluated against various mosquito larvae. [10,11] Chrysanthemic acid (2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic acid) is another active fragment in the first synthetic pyrethroid: allethrin. [9] Thus a series of modified triorganotin chrysanthemumates have been synthesized and their efficacies against various species of mosquito larvae are reported herein.…”