Effects of Halogen Introduction at the C5 Position of the Imidacloprid Pyridine Ring upon Insecticidal Activity

Kagabu, Shinzo; Ito, Nakako; Imai, Rie; Hieta, Yosuke; Nishimura, Keiichiro

doi:10.1584/jpestics.30.409

Cited by 13 publications

(22 citation statements)

References 18 publications

(25 reference statements)

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“…We have thus far observed the activity enhancement of neonicotinoid compounds by the presence of PB and NIA. 1,8,14,16,17,[21][22][23]30,31) Also, in the present case, the potency improvement was observed in all compounds. The high synergistic effect for compound 23 was noticeable; the potency was enhanced by factor 2.…”

Section: )supporting

confidence: 75%

“…Yield (propargyl propyl benzenephosphonate; NIA) was the same sample used in our previous studies. 8,[14][15][16][17] NIA was originally an inhibitor of the hydrolytic metabolism of pyrethroids, 18) and was found to be a synergist for neonicotinoids in insecticidal tests. 14) Recently, Nishiwaki et al evidenced the interference of the enzymatic hydroxylation at the imidazolidine ring of imidacloprid by NIA.…”

Section: -(2-chloropyridin-5-ylmethyl)-2-(cyanoimino)-oxazolidinementioning

confidence: 99%

“…8,[14][15][16][17] Various volumes (1-10 ml) of each compound dissolved in methanol containing some amount of dimethyl sulfoxide (DMSO) were injected into the abdomen of a cockroach. Organic solvents alone in this range did not have a toxic effect.…”

Section: Insecticidal Test Against American Cockroachesmentioning

confidence: 99%

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Insecticidal and neuroblocking potencies of variants of the thiazolidine moiety of thiacloprid and quantitative relationship study for the key neonicotinoid pharmacophore

Kagabu

Nishimura

Naruse

et al. 2008

Journal of Pesticide Science

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The pharmacophore of the neonicotinoid insecticide thiacloprid, cyanoiminothiazolidine, was modified to heterocycles such as imidazolidine, pyrrolidine and oxazolidine (the central ring hereafter). Their 6-chloro-3-pyridylmethyl or 5-chloro-3-thiazolylmethyl derivatives were examined for insecticidal activity against the American cockroach by injection and neuroblocking activity using the cockroach ganglion. The derivatives showed strong insecticidal activity with the minimum lethal dose (MLD) of about 10 nmol, which were however mostly weaker than the corresponding nitromethylene or nitroimine compounds. The activity was enhanced in the presence of synergists. The neuroblocking effect of cyanoimino compounds was at the micromolar level. Quantitative analysis for 23 variants of the key pharmacophore, constructed with the central ring conjugated to an NCN, CHNO 2 , or NNO 2 , showed that the neuroblocking potency is proportional to the Mulliken charge on the nitro oxygen atom or cyano nitrogen atom. The optimum log P value was evaluated as 1.19. The equation for the insecticidal-vs. the neuroblocking-potencies indicated that both potencies are related proportionally with each other when the other factors are the same.

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Section: )supporting

confidence: 75%

Section: -(2-chloropyridin-5-ylmethyl)-2-(cyanoimino)-oxazolidinementioning

confidence: 99%

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Insecticidal and neuroblocking potencies of variants of the thiazolidine moiety of thiacloprid and quantitative relationship study for the key neonicotinoid pharmacophore

Kagabu

Nishimura

Naruse

et al. 2008

Journal of Pesticide Science

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“…[2][3][4][5] Imidacloprid (1), the first neonicotinoid insecticide acting on a nAChR, has been widely used to control not only various plant pests, but also fleas on cats and dogs, and termites. [6][7][8] Following imidacloprid, thiamethoxam (2), thiacloprid (3), acyclic neonicotinoid insecticides, dinotefuran (4), acetamiprid (5), nitenpyram (6), and clothianidin (7) have been registered as agricultural insecticides. [9][10][11][12][13][14] These six products were developed by replacing the pyridine ring with a thiazole ring or a saturated heterocyclic ring, changing the nitroimino group to an isoelectronic nitromethylene or cyanoimine group, or reconstructing the imidazolidine ring with bioisosteric cyclic or acyclic moieties.…”

Section: Introductionmentioning

confidence: 99%

Design, synthesis, and insecticidal activity of novel neonicotinoid derivatives containing N-oxalyl groups

Zhao¹,

Li²,

Wang³

et al. 2009

Arkivoc

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Two series of novel neonicotinoid derivatives containing N-oxalyl groups were designed and synthesized, and their structures were characterized by 1 H NMR spectroscopy, high-resolution mass spectroscopy, elemental analysis and single crystal X-ray diffraction analysis. The insecticidal activities of the new compounds were evaluated. The results of bioassays indicated that some of these title compounds exhibited excellent insecticidal activities. The insecticidal activities of compounds 13c, 13d, 13g, 13h, and 13i against bean aphids at 12.5 mg kg -1 were 100%; the insecticidal activities against bean aphids of the derivative 13 c, 13d, 13g, 13h, and 14h were comparable to imidacloprid at 6.25 mg kg -1 . Surprisingly, the results indicated that the activity of ethyl 2-(3-((6-chloropyridin-3-yl)methyl)-2-(nitroimino)imidazolidin-1-yl)-2-oxoacetate (13b) against bean aphids at 6.25 mg kg -1 was 96%, which was higher than the commercialized imidacloprid.

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“…12,13) Here, we report their substituent effects obtained by means of the quantitative analysis of neuroblocking activity. This work is also connected with a recent finding of the extraordinary binding affinity of 5-azidoimidacloprid (21, XϭN 3 , Fig.…”

Section: Introductionmentioning

confidence: 99%

Quantitative structure-activity relationships of imidacloprid and its analogs with substituents at the C5 position on the pyridine ring in the neuroblocking activity

2006

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IntroductionImidacloprid (1, XϭH in Fig. 1) began the era of a structurally as well as a physiologically new type of insecticides having highly effective and widely used chemicals for crop protection and veterinary pest control. 1) Starting from this compound, variously modified neonicotinoids were developed as highly effective insecticides.2) Early modification researches focused overwhelmingly on the imidazolidine moiety of imidacloprid and cyclic and acyclic isosters were contrived. Recently, a non-aromatic neonicotinoids bearing a saturated heterocyclic ring in place of the pyridine ring, dinotefuran, was developed. 3,4) For further evolution of the structure to give a new class of neonicotinoids, quantitative analyses of the structure-activity relationship of neonicotinoids and analogous compounds are one of the most important tools, and have been widely performed for this class of compounds by means of conformational, 5) three-dimensional 6-8) as well as substituent-effect analyses.9,10) The conformational analysis, however, was conducted only for limited structures related to dinotefuran, so that the results obtained cannot be generalized. The other analyses were mostly carried out for the imidazolidine moiety of imidacloprid and the corresponding parts of the series compounds. Although a number of variously substituted benzyl analogs of imidacloprid were prepared, 11) their substituent effects have not been quantitatively analyzed.To conduct more detail quantitative analysis of the aromatic-ring part, we prepared a set of compounds with various substituents at the 5-position on the pyridine ring of imidacloprid and measured their insecticidal activity.12,13) Here, we report their substituent effects obtained by means of the quantitative analysis of neuroblocking activity. This work is also connected with a recent finding of the extraordinary binding affinity of 5-azidoimidacloprid (21, XϭN 3 , Fig. 1) to insect nAChR.14,15) We will be able to view the new information about the azido group in light of the quantitative analysis of a set of substituents at this position.Quantitative structure-activity relationships of imidacloprid and its analogs with substituents at the C5 position on the pyridine ring in the neuroblocking activity Two nerve activities of imidacloprid analogs with various substituents at the 5-position of the pyridine ring were measured: the conduction blockage in the excised central nerve cord of the American cockroach, and the binding inhibition of a radioligand, [ 3 H]imidacloprid, to the membrane preparation of housefly-head homogenates. Neuroblocking activity was quantitatively analyzed using physicochemical substituent parameters. The greater the electron-releasing resonance effect, the higher the activity. The introduction of sizable and alkoxy substituents was unfavorable. The nerve-binding activity of the tested compounds was linearly related to the neuroblocking activity with one exception. The higher the binding activity, the higher the blocking activity. © Pesticide Science Soc...

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Effects of Halogen Introduction at the C5 Position of the Imidacloprid Pyridine Ring upon Insecticidal Activity

Cited by 13 publications

References 18 publications

Insecticidal and neuroblocking potencies of variants of the thiazolidine moiety of thiacloprid and quantitative relationship study for the key neonicotinoid pharmacophore

Insecticidal and neuroblocking potencies of variants of the thiazolidine moiety of thiacloprid and quantitative relationship study for the key neonicotinoid pharmacophore

Design, synthesis, and insecticidal activity of novel neonicotinoid derivatives containing N-oxalyl groups

Quantitative structure-activity relationships of imidacloprid and its analogs with substituents at the C5 position on the pyridine ring in the neuroblocking activity

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