Asymmetric Chloronicotinyl Insecticide, 1-[1-(6-Chloro-3-pyridyl)ethyl]- 2-nitroiminoimidazolidine: Preparation, Resolution and Biological Activities toward Insects and Their Nerve Preparations

Kagabu, Shinzo; Kiriyama, Kazuhisa; Nishiwaki, Hisashi; Kumamoto, Yuko; Tada, Toshiji; Nishimura, Keiichiro

doi:10.1271/bbb.67.980

Cited by 11 publications

(12 citation statements)

References 22 publications

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“…With compound 2, the frequency decreased to zero around 13 min after the start of treatment at 1:3 Â 10 À6 M. With compound 18, however, some discharges were still counted even 20 min after the start of treatment at 5:7 Â 10 À4 M, this being the highest concentration tested. By estimating in a similar manner to that for the previous electrophysiological experiments, 21,22,[32][33][34] the blocking concentration for compounds 18, 26 and 27 was almost the same in a range of 0.6-1.0 mM. The much larger values than for prototype 2 of 4.5 mM are due to the evidently weak neuroblocking activity of these acetals.…”

Section: Resultssupporting

confidence: 63%

Prodrug-Oriented Molecular Design of Neonicotinoids: Preparation of Imidacloprid-Related 5,5-Dimethoxy-1,3-diazacyclohexane Derivatives and Their Insecticidal Activity

Kagabu

Hibi

Nishimura

2005

Bioscience, Biotechnology, and Biochemistry

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Prodrug-oriented molecular design was attempted for the potent acyclic neonicotinoid insecticide, clothianidin (1-(2-chloro-5-thiazolylmethyl)-3-methyl-2-nitroguanidine). Molecules bearing a CH 2 COCH 2 bridge linking the 1,3-NH ends of clothianidin or their acetals would possibly be hydrolyzed, regenerating the mother compounds. This strategy was used to prepare seven acetals of clothianidin-based molecules that combined 2-chloro-5-thiazolylmethyl, 6-chloro-3-pyridylmethyl or 3-tetrahydrofurfuryl with a nitroimine, cyanoimine or nitromethylene group. The key intermediate, 1,3-diamino-2,2-dimethoxypropane, was prepared from the dihydroxyacetone dimer in four steps. A selected acetal showed a characteristic nerve-impulse pattern for neonicotinoids on an excised American cockroach ganglion, although the neuroblocking activity was fairly low. Some acetals were highly insecticidal against the pea aphid at 0.8-20 ppm 7 days after a spray treatment, this being in a contrast to their far weaker activity by injection into American cockroaches. The biological results suggest that the intrinsic insecticidal activities of the acetals are weak, but would exhibit enhanced activity if hydrolyzed in an external environment.

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Section: Resultssupporting

confidence: 63%

Prodrug-Oriented Molecular Design of Neonicotinoids: Preparation of Imidacloprid-Related 5,5-Dimethoxy-1,3-diazacyclohexane Derivatives and Their Insecticidal Activity

Kagabu

Hibi

Nishimura

2005

Bioscience, Biotechnology, and Biochemistry

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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: 74%

“…8,17,[21][22][23][24][25] In brief, a nerve preparation containing the abdominal fifth and sixth ganglia of a male adult American cockroach was excised and placed in a saline solution. One of two bundles of the nerve cord was taken up 60 S. Kagabu et al Journal of Pesticide Science Alone Ratio…”

Section: Neurophysiological Assaymentioning

confidence: 99%

“…According to the preliminary calculations performed only with PM3 Hamiltonian using MNDO optimized structures, the Mulliken charge magnitudes on the nitro oxygen atoms of imidacloprid (1) are (negatively) larger than on the cyano nitrogen atom of thiacloprid (23). 42) In the present paper, calculations were performed at the B3LYP/6-31G(d) level, which includes the electronic factors, to evaluate the charges of a series of the analogue compounds (i.e.…”

Section: Quantitative Analysis Of the Neuroblocking Potenciesmentioning

confidence: 99%

“…Commercial products thiacloprid (23) 2,3) and acyclic acetamiprid 4) are sharing this moiety, and compounds with this pharmacophore have been a target for insecticidal, physiological or biochemical study. [5][6][7][8][9][10] In this paper we report the insecticidal and neuroblocking activities of five cyanoimine variants, the measured log P values, and the calculated quantum chemical factors following the previous method.…”

Section: Introductionmentioning

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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Enzymatic Dynamic Kinetic Resolution in Stereoselective Synthesis

Rebolledo

González‐Sabín

Gotor

2013

Stereoselective Synthesis of Drugs and Natural Products

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The chemoenzymatic dynamic kinetic resolution (DKR) protocol combines the enzyme‐catalyzed resolution of a racemic substrate with the in situ racemization of the less reactive enantiomer, thus, producing optically active products in up to quantitative yield. This is of great interest for the pharmaceutical industry because by using this methodology, some of the serious drawbacks associated with drug production can be solved. Enzymatic DKRs are environmentally friendly processes that could help reduce cost and waste. The first and principal section of this chapter addresses the usefulness of hydrolases (particularly lipases) for the DKR of alcohols, diols, amines, and esters. In the following sections, DKRs with other enzymes such as haloalcohol dehalogenase, dehydrogenases, transaminases, and Baeyer‐Villiger monooxygenases are considered.

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Asymmetric Chloronicotinyl Insecticide, 1-[1-(6-Chloro-3-pyridyl)ethyl]- 2-nitroiminoimidazolidine: Preparation, Resolution and Biological Activities toward Insects and Their Nerve Preparations

Cited by 11 publications

References 22 publications

Prodrug-Oriented Molecular Design of Neonicotinoids: Preparation of Imidacloprid-Related 5,5-Dimethoxy-1,3-diazacyclohexane Derivatives and Their Insecticidal Activity

Prodrug-Oriented Molecular Design of Neonicotinoids: Preparation of Imidacloprid-Related 5,5-Dimethoxy-1,3-diazacyclohexane Derivatives and Their Insecticidal Activity

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

Enzymatic Dynamic Kinetic Resolution in Stereoselective Synthesis

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