• The Korean Journal of Pesticide Science
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• v.8 no.4
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• pp.258-264
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• 2004

The pyrazole family was discovered as effective insecticides/acaricides, and fenpyroximate and tebufenpyrad were introduced in the market. In this study, new series of pyrazole oxime ethers were designed and synthesized. The pyrazolone 1 was prepared by the condensation of ethyl acetoacetate with methylhydrazine, and then subsequently subjected to the Vilsmeier-Haack chloroformylation yielding 4-formyl-5-chloro-pyrazole 2. The nucleophilic aromatic substitution of 2 generally allowed the introduction of a wide range of heterocycles into the pyrazole ring. The resulting pyrazole aldehydes 3a-i were readily converted to the corresponding pyrazole oxime derivatives 4a-i, and subsequently to 5-substituted pyrazole oxime ether derivatives 6a-i. The screening assay results clearly show that the activities of 6d were comparable to those of fenpyroximate (6a) against BPH, DBM, and TSSM. It indicates that 6d has a potential to be developed as an insecticidal agent.

• Archives of Pharmacal Research
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• v.27 no.6
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• pp.610-614
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• 2004

The in vitro antioxidant properties of some flavone-6(4)-carboxaldehyde oxime ether deriva-tives (Ia-f, lIa-f） were determined by their effects on the rat liver microsomal NADPH-dependent lipid peroxidation (LP） levels by measuring the formation of 2-thiobarbituric acid reactive substances. The free radical scavenging properties of the compounds were also examined in vitro by determining their capacity to scavenge superoxide anions and interact with the stable free radical 2, 2-diphenyl-1-picrylhydrazyl (DPPH). The most active compounds, lib (Flavone-4＇-carboxaldehyde-O-ethyl oxime） and Id (Flavone-6-carboxaldehyde-O-［2-(1-pyrolidino） ethyl］ oxime）, caused 98 and 79％ inhibition of superoxide anion production and DPPH stable free radical at $10^{-3}{\;}M$, respectively.

• Bulletin of the Korean Chemical Society
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• v.24 no.9
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• pp.1368-1370
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• 2003

• Bulletin of the Korean Chemical Society
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• v.15 no.1
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• pp.53-57
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• 1994

A comparison study on asymmetric borane reduction of ketoxime ethers and N-substituted ketimines possesing C = N double bond mediated by the selected chiral oxazaborolidines (1-6) was investigated. Thus, an aromatic ketoxime O-alkyl ether acetophenone oxime O-methyl ether was reduced to the corresponding amine (1-phenylethylamine 8a) with optical yields, such as 58% ee with 1, 86% ee with 2, 3% ee with 3, 99% ee with 4, 60% ee with 5, and 73% ee with 6. However, the reduction of an aliphatic ketoxime derivative 2-heptanone oxime O-methyl ether provided low optical inductions (7-13% ee). For ketoxime O-trimethylsilyl ethers, the reduction of acetophenone O-trimethylsilyl ether afforded 8a with optical yields which were 90% ee with 1, 40% ee with 2, 2% ee with 3, 62% ee with 4, 5% ee with 5, and 60% ee with 6. The reduction of 2-heptanone O-trimethylsilyl ether also gave the product amine with low optical yields (10-40% ee). In the case of N-substituted ketimines, the reduction of acetophenone N-phenylimine afforded the corresponding amine with 79% ee, 78% ee, 9% ee, 73% ee, 78% ee and 67% ee using 1, 2, 3, 4, 5, and 6, respectively, whereas low optical inductions (5-18% ee) for 2-heptanone N-phenylimine were achieved.

• Journal of Pharmaceutical Investigation
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• v.24 no.4
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• pp.273-279
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• 1994

The stability of three oximes, Hl-6 [(4-carbamoyl-2'[(hydroxyimino)-methyl]- 1,1'-oxydimethylenedi-(pyridinium chloride)], Hl-CN [(4 cyano-2'-[(hydroxyimino)-methyl] -1,1'-oxydimethylene-di-(pyridinium chloride)], and 2-PAM [pralidoxime chloride] in aqueous solutions was evaluated by HPLC assay. The rate of degradation is dependent on the pH as well as the temperature at which the solution is stored. The optimum pH for the stability of these oximes was pH 2 to 3. The degradation rate constant for 2-PAM ($k\;at\;70^{\circ}C$, $2.07{\times}10^{-4}/hr;\;E_a\;value$, 27.2 kcal/mol) was smaller than those for bis-pyridiniumoximes, Hl-6 ($k\;at\;70^{\circ}C$, $3.38{\times}10^{-3}/hr$) and Hl-CN ($k\;at\;70^{\circ}C$, $8.66{\times}10^{-3}/hr;\;Ea\;value$, 20.7 kcal/mol). In mechanistic analyses, it was found that Hl-CN was decomposed through not only the hydrolysis of nitrile group but also the cleavage of methylene ether bridge, in contrast to Hl-6 which was degraded mainly through the cleavage of methylene ether bridge.

• Bulletin of the Korean Chemical Society
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• v.35 no.4
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• pp.1073-1076
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• 2014

In attempt to lead compounds exhibiting both insecticidal and fungicidal activities, a series of O-benzyl oximeether derivatives were designed and synthesized by introducing ${\beta}$-methoxyacrylate pharmacophore into a scaffold. The insecticidal activity against Aphis fabae and the fungicidal activity against Erysiphe graminis were screened. The title compounds exhibited remarkable insecticidal and fungicidal activities. The most potent compound 6d was identified. Its insecticidal $LC_{50}$ against A. fabae is 6.4 mg/L, which is lower than that of chlorfenapyr (19.4 mg/L) and even close to the level of imidacloprid (4.8 mg/L). Its fungicidal $EC_{90}$ in preventive and curative treatment against E. graminis are 2.2 and 4.8 mg/L, respectively, which are lower than azoxystrobin (7.0 and 5.9 mg/L). These results indicate that compound 6d can be considered as a lead for further developing new O-benzyl oxime-ether typed candidates with both fungicidal and insecticidal activities.

• YAKHAK HOEJI
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• v.46 no.5
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• pp.320-323
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• 2002

A method for the determination of acidic drug, mefenamic acid and ibuprofen with ion-selective electrode(ISE) using Fe(II)-di-2-pyridyl ketone oxime complex as a counter ion were developed. Benzyl-2-nitrophenyl ether(BNPE) plasticized membrane was more selective and sensitive than the other tested membranes. The acidic drug selective electrode exhibits a linear response for 10$^{-2}$ M 510$^{-5}$ M of acidic drugs, mefenamic acid and ibuprofen with a slope of -55.9 and -56.3 mV/dec. in borate buffer solution (pH 8.9). Potentiometric selectivity measurements revealed negligible interferences from aromatic and aliphatic carboxylic acid salts. The electrodes were found to be useful for the direct determination of mefenamic acid and ibuprofen in pharmaceutical preparations.

• Bulletin of the Korean Chemical Society
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• v.31 no.9
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• pp.2467-2472
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• 2010

Twenty novel tetramic acid derivatives (E)-3-(1-(alkyloxyamino)ethylidene)-1-alkylpyrrolidine-2,4-diones were synthesized by the reaction of 3-(1-hydroxyethylidene)pyrrolidine-2,4-diones with O-alkyl hydroxylamines. The title compounds were confirmed by IR, $^1H$ NMR, MS and elemental analysis. The structure of compound 6r was further verified by X-ray diffraction crystallography. The bioassays showed that most of the title compounds exhibited noticeable herbicidal and fungicidal activities.

• Bulletin of the Korean Chemical Society
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• v.16 no.5
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• pp.416-421
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• 1995

The approximate rates and stoichiometry of the reaction of excess lithium gallium hydride with selected organic compounds containing representative functional groups were examined under the standard conditions (diethyl ether, 0 $^{\circ}C)$ in order to compare its reducing characteristics with lithium aluminum hydride and lithium borohydride previously reported, and enlarge the scope of its applicability as a reducing agent. Alcohols, phenol, and amines evolve hydrogen rapidly and quantitatively. However lithium gallium hydride reacts with only one active hydrogen of primary amine. Aldehydes and ketones of diverse structure are rapidly reduced to the corresponding alcohols. Conjugated aldehyde and ketone such as cinnamaldehyde and methyl vinyl ketone are rapidly reduced to the corresponding saturated alcohols. p-Benzoquinone is mainly reduces to hydroquinone. Caproic acid and benzoic acid liberate hydrogen rapidly and quantitatively, but reduction proceeds slowly. The acid chlorides and esters tested are all rapidly reduced to the corresponding alcohols. Alkyl halides and epoxides are reduced rapidly with an uptake of 1 equiv of hydride. Styrene oxide is reduced to give 1-phenylethanol quantitatively. Primary amides are reduced slowly. Benzonitrile consumes 2.0 equiv of hydride rapidly, whereas capronitrile is reduced slowly. Nitro compounds consumed 2.9 equiv of hydride, of which 1.9 equiv is for reduction, whereas azobenzene, and azoxybenzene are inert toward this reagent. Cyclohexanone oxime is reduced consuming 2.0 equiv of hydride for reduction at a moderate rate. Pyridine is inert toward this reagent. Disulfides and sulfoxides are reduced slowly, whereas sulfide, sulfone, and sulfonate are inert under these reaction conditions. Sulfonic acid evolves 1 equiv of hydrogen instantly, but reduction is not proceeded.