Development of insect juvenile hormone active oxime O-ethers and carbamates

Nakayama, Akira; Iwamura, Hajime; Niwa, Atsushi; Nakagawa, Yoshiaki; Fujita, Toshio

doi:10.1021/jf00066a007

Cited by 36 publications

(25 citation statements)

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“…4(b)). Within these conformational restrictions, we investigated the superimposability of JH active diphenylethers onto the optimized structure of methoprene and found that one of the minimum confor- On the other hand, conformational analyses of p-phenoxycinnamaldehyde oximes (12), which are less active than 8, [9] revealed that the side chain lies in the same plane as the attached phenyl ring in the most stable conformation and that it is difficult to adopt the twisted active conformation.…”

Section: Resultsmentioning

confidence: 99%

“…Since the discovery of insect juvenile hormones (JH) [l -41, many compounds have been developed to mimic [ 5 ] 0 * 0 & -H 2 (Nakayama et ai.) [9] 0 U N K 0 4 \ 3 (Nakayama) [lo] ' H ' 0 4 (Nakayama et al) [9] 5 (X=O, CH2) (Karrer et al) [6] Q O M 0 -o A N -H carbamate 6 (Karrer et al) [7] QoDo+carbamate 7 (fenoxycarb) (Fischer et al) [S] 0 0 oxime 0-ether 8 (Nakayama et al) [9] 0 VCH Verlagsgesellschaft mbH, D-6940 Weinheim 0931 -8771/87/0412-0153 $02.50/0 their morphogenetic activity with the aim of insect control. Most of the known JH mimics are classified as terpenoid compounds which are structural mimics of the naturally occurring compounds.…”

Section: Introductionmentioning

confidence: 99%

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A Quantum Chemical Study of Insect Juvenile Hormone Mimics: The Active Conformation and the Electrostatic Similarities

Nakayama

Richards

1987

Quant. Struct.‐Act. Relat.

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The stable conformations and the electrostatic properties of insect juvenile hormone (JH) mimics are studied using semi‐empirical molecular orbital methods. One of the minimum energy conformations of JH active diphenylethers, a new class of JH mimics, is found to be superimposable on the stable extended structure of methoprene which is one of the most highly active JH mimics within the series of terpenoid compounds. As well as the superimposability of the diphenylether and terpenoid structures, JH active functional groups such as esters, carbamates and oxime O‐ethers are also shown to be superimposable. The electrostatic potentials of these functional groups which are commonly found in the diphenylethers and the terpenoid JH mimics are similar to each other in terms of potential contours and the similarity indices of electrostatic potentials. This may account for the bioisosterism of these active functional groups. Here we postulate a model of molecular recognition at the JH receptor in which the electrostatic interaction is important as well as the size and shape of the molecule. The molecular similarities between different classes of JH mimics in terms of steric and electrostatic properties, which are derived from quantum chemical methods, may help to understand the universality of active structures and aid in the design of new active generations.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A Quantum Chemical Study of Insect Juvenile Hormone Mimics: The Active Conformation and the Electrostatic Similarities

Nakayama

Richards

1987

Quant. Struct.‐Act. Relat.

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“…Since the olfactory sensation of the insects requires some degree of lipid solubility (Nakayama et al, 1985), hydrophobicity of the repellents is likely to be an important factor for potent repellent activity.…”

Section: Molecular Similarity Analysis Of Jh-mimic and Deet Compoundsmentioning

confidence: 99%

“…1) are ubiquitous growth regulators in the insect world and serve as a rational source for the design of synthetic insect growth regulators (Judy et al, 1973;Bergot et al, 1980, Nakayama et al, 1985. Structure-activity studies on JH have resulted in the discovery of JH-like compounds (Nakayama et al, 1985;Nakayama and Richards, 1987) which mimic their morphogenetic activity with the aim of controlling insect populations, but to our knowledge no attempt has been made thus far to design insect repellents rationalizing the JH activity. Although considerable efforts have gone into research (Skinner and Johnson, 1980) as to why humans are attractive to insects, especially mosquitoes, and many chemicals have been discovered to have repellent activity, the mode of action of repellents remains poorly understood.…”

Section: Introductionmentioning

confidence: 99%

Molecular similarity analysis between insect juvenile hormone andN, N-diethyl-m-toluamide (DEET) analogs may aid design of novel insect repellents

Bhattacharjee

Gupta

et al. 2000

J. Mol. Recognit.

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Molecular similarity analysis of stereoelectronic properties between natural insect juvenile hormone (JH), a synthetic insect juvenile hormone mimic (JH‐mimic, undecen‐2‐yl carbamate), and N,N‐diethyl‐m‐toluamide (DEET) and its analogs reveals similarities that may aid the design of more efficacious insect repellents and give a better insight into the mechanism of repellent action. The study involves quantum chemical calculations using the AM1 semi‐empirical computational method enabling a conformational search for the lowest and most abundant energy conformers of JH, JH‐mimic, and 15 DEET compounds, followed by complete geometry optimization of the conformers. Similarity analyses of stereoelectronic properties such as structural parameters, atomic charges, dipole moments, molecular electrostatic potentials, and highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies were performed on JH, JH‐mimic and the DEET compounds. The similarity of stereoelectronic attributes of the amide/ester moiety, the negative electrostatic potential regions beyond the van der Waals surface, and the large distribution of hydrophobic regions in the compounds appear to be the three important factors leading to a similar interaction with the JH receptor. The similarity of electrostatic profiles beyond the van der Waals surface is likely to play a crucial role in molecular recognition interaction with the JH receptor from a distance. This also suggests electrostatic bioisosterism of the amide group of the DEET compounds and JH‐mimic and, thus, a model for molecular recognition at the JH receptor. The insect repellent property of the DEET analogs may thus be attributed to a conflict of complementarity for the JH receptor binding sites. Copyright © 2000 John Wiley & Sons, Ltd.

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“…some antimicrobial agents, 1 insecticides, 2 and vasodilators 3 ). Among the most important oxime drugs are compounds that are used as antidotes of nerve agents.…”

Section: Introductionmentioning

confidence: 99%

Mechanochemical and Conformational Study of N-heterocyclic Carbonyl-Oxime Transformations

Primožič¹,

Hrenar²,

Baumann³

et al. 2014

Croat. Chem. Acta

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Abstract. New mechanochemical pathways for the transformation of six N-heterocyclic carbonyl compounds into oximes using hydroxylamine hydrochloride were explored. Reactions were performed first without any base since the heterocyclic moieties (imidazole, benzimidazole, pyridine and quinuclidine) have an intrinsic basic nitrogen atom. This green, solvent free method was suitable for all compounds (up to quantitative yields) except for N-benzyl substituted imidazole and benzimidazole-2-carbaldehyde. For the slower reacting aldehydes, reactions with liquid assisted grinding and addition of sodium hydroxide were performed as well. Conformational analysis and quantum-chemical calculations revealed steric and electronic reasons for the lower reactivity of N-benzyl substituted derivatives.

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Development of insect juvenile hormone active oxime O-ethers and carbamates

Cited by 36 publications

References 5 publications

A Quantum Chemical Study of Insect Juvenile Hormone Mimics: The Active Conformation and the Electrostatic Similarities

A Quantum Chemical Study of Insect Juvenile Hormone Mimics: The Active Conformation and the Electrostatic Similarities

Molecular similarity analysis between insect juvenile hormone andN, N-diethyl-m-toluamide (DEET) analogs may aid design of novel insect repellents

Mechanochemical and Conformational Study of N-heterocyclic Carbonyl-Oxime Transformations

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