Molecular Design of Dinotefuran with Unique Insecticidal Properties

Wakita, Takeo

doi:10.1021/jf1030778

Cited by 42 publications

(25 citation statements)

References 27 publications

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“…The ( S ) ‐ ( + ) ‐ enantiomer of dinotefuran has a higher potency relative to the ( R ) ‐ ( − ) ‐ enantiomer, which could be demonstrated by its binding site interaction with the agonist‐binding pocket of the Aplysia californica acetylcholine‐binding protein (AChBP) . Conversely, the ( S ) ‐ ( + ) ‐ enantiomer and racemic dinotefuran have almost equal affinity at the n AChR target site, as well as in their insecticidal activity …”

Section: Insecticidesmentioning

confidence: 99%

“…The (S)-(+)-enantiomer of dinotefuran has a higher potency relative to the (R)-(−)-enantiomer, which could be demonstrated by its binding site interaction with the agonist-binding pocket of the Aplysia californica acetylcholine-binding protein (AChBP). 80 Conversely, the (S)-(+)-enantiomer and racemic dinotefuran have almost equal affinity at the nAChR target site, as well as in their insecticidal activity. 80 Sulfoxaflor contains two chiral centres (the sulfur atom and the carbon atom attached to position 3 of the trifluoromethyl-pyridine ring) and is comprised of a mixture of four stereoisomers: (1S,2S), (1S,2R), (1R,2R) and (1R,2S) ( Fig.…”

Section: Nicotinic Acetylcholine Receptor Competitive Modulatorsmentioning

confidence: 99%

“…80 Conversely, the (S)-(+)-enantiomer and racemic dinotefuran have almost equal affinity at the nAChR target site, as well as in their insecticidal activity. 80 Sulfoxaflor contains two chiral centres (the sulfur atom and the carbon atom attached to position 3 of the trifluoromethyl-pyridine ring) and is comprised of a mixture of four stereoisomers: (1S,2S), (1S,2R), (1R,2R) and (1R,2S) ( Fig. 8).…”

Section: Nicotinic Acetylcholine Receptor Competitive Modulatorsmentioning

confidence: 99%

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Current status of chirality in agrochemicals

Jeschke

2018

Pest Management Science

153

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The agrochemical industry is searching continuously for new pesticides to develop products that have optimal efficacy, lower application rates in the field, increased selectivity, favourable toxicological and environmental safety, enhanced user friendliness and better economic viability. One strategy by which to achieve these ambitious goals makes use of the unique properties of molecules containing asymmetric centres. In the past, many natural products and their congeners have been a source of inspiration in the design of new active ingredients, and the molecular structures of the resulting compounds have become increasingly complex; some 30% contain fragments with asymmetric centres. However, despite enormous progress in catalytic asymmetric processes over the past decade, few agrochemicals are produced in an enantiomerically pure or enriched form on an industrial scale. Since 2007, ∼ 43% of the 44 products launched (insecticides, acaricides, fungicides, nematicides and herbicides) contain one or more asymmetric centres in the molecule (∼ 47%) and most have been launched as racemic mixtures of enantiomers or diastereomers. This review provides an overview of the current status of chiral agrochemicals launched over the past 10 years and describes the inherently connected challenges of modern agricultural chemistry by managing important aspects resulting from the stereochemistry of these innovative products. © 2018 Society of Chemical Industry.

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Section: Insecticidesmentioning

confidence: 99%

Section: Nicotinic Acetylcholine Receptor Competitive Modulatorsmentioning

confidence: 99%

Section: Nicotinic Acetylcholine Receptor Competitive Modulatorsmentioning

confidence: 99%

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Current status of chirality in agrochemicals

Jeschke

2018

Pest Management Science

153

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“…It is also commercialized in the racemic form. To our best knowledge, many works of dinotefuran up to now have been mostly focused on chemical synthesis [10,12,13], achiral analysis and the residue determinations of its racemate by ELISA [14] or by HPLC [15] or HPLC/MS/MS [16][17][18]. There are also some reports about its toxicity to target and non-target pests [19][20][21][22].…”

Section: Introductionmentioning

confidence: 99%

Enantioselective separation and determination of the dinotefuran enantiomers in rice, tomato and apple by HPLC

Chen

Dong

Liu

et al. 2012

J of Separation Science

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An effective chiral analytical method was developed for the resolution and determination of dinotefuran enantiomers in rice, tomato and apple samples. Dinotefuran enantiomers were baseline-separated and determined on a novel chiral column, ChromegaChiral CCA, with n-hexane-ethanol-methanol (85:5:10, v/v/v) as the mobile phase at a flow rate of 1.0 mL/min with UV detection at 270 nm. The resolution of dinotefuran enantiomers was about 1.8. The first eluted enantiomer was (+)-dinotefuran and the second eluted one was (-)-dinotefuran. The effects of mobile-phase composition and column temperature on the enantioseparation were evaluated. The method was validated for linearity, repeatability, accuracy, LOD and LOQ. LOD was 0.15 mg/kg in rice and tomato, 0.05 mg/kg in apple, with an LOQ of 0.5 mg/kg in rice and tomato, 0.2 mg/kg in apple. The average recoveries of the pesticide from all matrices ranged from 75.8 to 92.9% for all fortification levels The precision values associated with the analytical method, expressed as RSD values, were <16.5% for the pesticide in all matrices. The methodology was successfully applied for the enantioselective analysis of dinotefuran enantiomers in real samples, indicating its efficiency in investigating the environmental stereochemistry of dinotefuran in food matrix.

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“…[1][2][3][4][5][6][7][8][9][10] A prodrug is a substance that has to be transformed in order to show or enhance activity or to lessen unfavorable properties of the original ingredient. 11) Drabek and Neumann 12) introduced the term proinsecticide for an insecticide by referring to the pharmaceutical term.…”

mentioning

confidence: 99%

Proneonicotinoid

Kagabu

2011

J. Pestic. Sci.

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Since the discovery of imidacloprid in 1986, various structural modifications have been attempted to devise molecules with favorable biological properties different from those of the first product. [1][2][3][4][5][6][7][8][9][10] A prodrug is a substance that has to be transformed in order to show or enhance activity or to lessen unfavorable properties of the original ingredient. 11) Drabek and Neumann 12) introduced the term proinsecticide for an insecticide by referring to the pharmaceutical term. This article addresses nine prodrug types of the neonicotinoid, using the term proneonicotinoid in this context. Oxadiazine and Related Cyclic AzinesAcetal, thioacetal and aminal have been frequently used as a protective group for aldehyde or ketone in synthetic chemistry. 13) The assembled framework regenerates the carbonyl group by hydrolysis after the task, leaving the individual protecting fragments (Eq. 1, Fig. 1). Oxadiazine (XϭO), thiadiazine (XϭS) or triazine (XϭNMe) structure (1), constructed by linking both the amine ends of original insecticidal molecule (2) with formaldehyde through the corresponding hetero fragment, can be viewed as a similar assembly. 14-16) The cleavage of thiamethoxam (3) into clothianidin (5) in insects and plant tissues has been reported. 17,18) Hydrolysis comparison of the three cyclic azines (1) to the corresponding diaminonitroimines (2) in a physiological salt solution showed that the half-lives of the oxadiazines were notably longer than the corresponding thiadiazines and triazines. We have attributed the stability of the oxadiazine framework to the relatively strong -NCH 2 -O-CH 2 N-linkage by comparing the bond energy for C-O of 85-91 kcal/mol with 61 kcal/mol for C-S and 69-75 kcal/mol for C-N. 19) Thus, the devised thiamethoxam displays several favorable profiles in field practice, 16) and its present sales volume worldwide ranks second in the neonicotinoid class. This prodrug development practice clearly shows that a small structural variant (only one atom in this case) leads to large differences in the success. Mannich BasesThe Mannich reaction is the condensation of a labile C-H bond with an aldehyde and a primary or secondary amine to form a so-called Mannich base. 20) This well-established synthetic protocol was applied to a proneonicotinoid construction (Eqs. 2-4, Fig. 2). 21,22) The Mannich bases (7a, b) derived from b ,b -diamino nitroethylene molecules (6a, b) can regenerate the parent component in an acidic milieu. The concentrations of Mannich bases (7a, b) to cause spontaneous neuroblocking in the excised central nerve cord of American cockroaches (Periplaneta americana L.) were 100-140 mM at the level of 140 mM of 3N-Me (6c) derivative, and far higher than the 1.6-1.9 mM of the starting molecules (6a, b). However, 24 hr after the injection the minimum lethal doses were ProneonicotinoidShinzo KAGABU* Department of Chemistry, Faculty of Education, Gifu University, Gifu 501-1193, Japan (Received January 5, 2011 Accepted February 18, 2011) Prodrug is a biologi...

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Molecular Design of Dinotefuran with Unique Insecticidal Properties

Cited by 42 publications

References 27 publications

Current status of chirality in agrochemicals

Current status of chirality in agrochemicals

Enantioselective separation and determination of the dinotefuran enantiomers in rice, tomato and apple by HPLC

Proneonicotinoid

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