Synthesis and insecticidal evaluation of imidacloprid analogs

Boëlle, Jérôme; Schneider, Raphaël; Gérardin, Philippe; Loubinoux, B.; Maienfisch, Peter; Rindlisbacher, Alfred

doi:10.1002/(sici)1096-9063(1998110)54:3<304::aid-ps832>3.3.co;2-q

Cited by 8 publications

(7 citation statements)

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“…The reported binding strengths (k i ) of compounds 18, 19, and 20 to the Drosophila nAChR are 1.2 ( 0.3, 180 ( 15, and 36000 ( 2750 nM (45), respectively. The calculated charge for XII-XV (Table 2) is actually highly related with the reported binding strength order as well as the nil insecticidal activity of 21 (46). As above, we could grasp the parallel relationship between the neuroblocking activity and the nitro oxygen charge.…”

Section: Resultsmentioning

confidence: 55%

“…To certify the relationship of the charge to the activity, we took up compounds 18-21 for referral ( Figure 5). Table 2) is actually highly related with the reported binding strength order as well as the nil insecticidal activity of 21 (46). As above, we could grasp the parallel relationship between the neuroblocking activity and the nitro oxygen charge.…”

Section: Resultsmentioning

confidence: 99%

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Insecticidal and Neuroblocking Potencies of Variants of the Imidazolidine Moiety of Imidacloprid-Related Neonicotinoids and the Relationship to Partition Coefficient and Charge Density on the Pharmacophore

Kagabu

Ishihara

Hieda

et al. 2007

J. Agric. Food Chem.

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The pharmacophore of the neonicotinoid insecticide imidacloprid, nitroiminoimidazolidine, was modified to heterocycles such as thiazolidine, pyrrolidine, dihydroimidazole, dihydrothiazole, and pyridone conjugated to nitroimine (=NNO2) or nitromethylene (=CHNO2). Their 6-chloro-3-pyridylmethyl or 5-chloro-3-thiazolylmethyl derivatives were examined for insecticidal activity against the American cockroach by injection and for neuroblocking activity using the cockroach ganglion. Most of the compounds having the neonicotinoidal pharmacophore exhibited insecticidal activity at the nanomolar level, which was enhanced in the presence of synergists, and high neuroblocking activity at the micromolar level. Quantitative analysis for the compounds showed that the neuroblocking potency is proportional both to the Mulliken charge on the nitro oxygen atom and to the partition coefficient log P value. The equation for the insecticidal versus neuroblocking potencies indicated that both potencies are related proportionally with each other when the other factors are the same.

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Section: Resultsmentioning

confidence: 55%

Section: Resultsmentioning

confidence: 99%

Insecticidal and Neuroblocking Potencies of Variants of the Imidazolidine Moiety of Imidacloprid-Related Neonicotinoids and the Relationship to Partition Coefficient and Charge Density on the Pharmacophore

Kagabu

Ishihara

Hieda

et al. 2007

J. Agric. Food Chem.

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“…This differs from the sp 3 nature of the ammonium or pyrrolidinyl nitrogen of nicotine. Interestingly, N1 can be replaced with a carbon atom with retention of significant insecticidal activity (41). Thus, N1 of neonicotinoids may only play a complementary role in the binding interaction and/or selectivity.…”

Section: Discussionmentioning

confidence: 99%

The Neonicotinoid Electronegative Pharmacophore Plays the Crucial Role in the High Affinity and Selectivity for theDrosophilaNicotinic Receptor: An Anomaly for the Nicotinoid Cation−π Interaction Model

et al. 2003

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Cation-pi interaction, a prominent feature in agonist recognition by neurotransmitter-gated ion channels, does not apply to the anomalous action of neonicotinoids at the insect nicotinic acetylcholine receptor (nAChR). Insect-selective neonicotinoids have an electronegative pharmacophore (tip) in place of the ammonium or iminium cation of the vertebrate-selective nicotinoids, suggesting topological divergence of the agonist-binding sites in insect and vertebrate nAChRs. This study defines the molecular and electronic basis for the potent and selective interaction of the neonicotinoid electronegative pharmacophore with a unique subsite of the Drosophila but not of the vertebrate alpha4beta2 nAChR. Target site potency and selectivity are retained when the usual neonicotinoid N-nitroimine (=NNO(2)) electronegative tip is replaced with N-nitrosoimine (=NNO) or N-(trifluoroacetyl)imine (=NCOCF(3)) in combination with an imidazolidine, imidazoline, thiazolidine, or thiazoline heterocycle. X-ray crystallography establishes coplanarity between the heterocyclic and imine planes, including the electronegative substituent in the trans configuration. The functional tip is the coplanar oxygen atom of the N-nitrosoimine or the equivalent oxygen of the N-nitroimine. Quantum mechanics in the gas and aqueous phases fully support the conserved coplanarity and projection of the strongly electronegative tip. Further, a bicyclic analogue with a nitro tip in the cis configuration but retaining coplanarity has a high potency, whereas the N-trifluoromethanesulfonylimine (=NSO(2)CF(3)) moiety lacking coplanarity confers very low activity. The coplanar system between the electronegative tip and guanidine-amidine moiety extends the conjugation and facilitates negative charge (delta(-)) flow toward the tip, thereby enhancing interaction with the proposed cationic subsite such as lysine or arginine in the Drosophila nAChR.

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“…After the discovery of imidacloprid, research on molecules with a similar structure containing the 6‐chloro‐3‐pyridylmethyl moiety led to acetamiprid, nitenpyram and thiacloprid 15–17. Additionally, the substitution of the chloropyridinyl moiety by a chlorothiazolyl group resulted in a second subgroup of neonicotinoid insecticides 18. Compounds in this group are clothianidin and thiamethoxam 19.…”

Section: Introductionmentioning

confidence: 99%

Resistance and cross‐resistance to neonicotinoid insecticides and spinosad in the Colorado potato beetle, Leptinotarsa decemlineata (Say) (Coleoptera: Chrysomelidae)

Mota-Sánchez

Hollingworth

Grafius

et al. 2005

Pest Management Science

236

182

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The Colorado potato beetle, Leptinotarsa decemlineata (Say), has developed resistance to many insecticides used for its control, recently including imidacloprid, a neonicotinoid compound. Other neonicotinoids are now being deployed to control this pest. A key point in the strategies of resistance management is the monitoring of resistance and cross-resistance. In the summer of 2003, imidacloprid-resistant adult Colorado potato beetles collected from Long Island, New York, USA were bioassayed using topical applications of imidacloprid and nine other neonicotinoids. Compared to a standard susceptible strain, the Long Island beetles showed 309-fold resistance to imidacloprid, and lower levels of cross-resistance to all other neonicotinoids, despite these never having been used in the field, i.e., 59-fold to dinotefuran, 33-fold to clothianidin, 29-fold to acetamiprid, 28-fold to N-methylimidacloprid, 25-fold to thiacloprid, 15-fold to thiamethoxam, 10-fold to nitenpyram, but less than 2-fold to nicotine. In injection bioassays, high resistance to imidacloprid was also found (116-fold). Piperonyl butoxide partially suppressed resistance to imidacloprid, but the resistance level was still over 100-fold, indicating that other mechanisms were primarily responsible for resistance. Low levels of resistance (8- to 10-fold) were found to the nicotinic activator, spinosad, in an imidacloprid-resistant strain collected from the same field in 2004. The cross-resistance seen with all the neonicotinoids tested suggests that the rotation of imidacloprid with other neonicotinoids may not be an effective long-term resistance management strategy. Rotation with spinosad also carries some risk, but it is unlikely that spinosad resistance in this case is mechanistically related to that for the neonicotinoids.

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Synthesis and insecticidal evaluation of imidacloprid analogs

Cited by 8 publications

References 0 publications

Insecticidal and Neuroblocking Potencies of Variants of the Imidazolidine Moiety of Imidacloprid-Related Neonicotinoids and the Relationship to Partition Coefficient and Charge Density on the Pharmacophore

Insecticidal and Neuroblocking Potencies of Variants of the Imidazolidine Moiety of Imidacloprid-Related Neonicotinoids and the Relationship to Partition Coefficient and Charge Density on the Pharmacophore

The Neonicotinoid Electronegative Pharmacophore Plays the Crucial Role in the High Affinity and Selectivity for theDrosophilaNicotinic Receptor: An Anomaly for the Nicotinoid Cation−π Interaction Model

Resistance and cross‐resistance to neonicotinoid insecticides and spinosad in the Colorado potato beetle, Leptinotarsa decemlineata (Say) (Coleoptera: Chrysomelidae)

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