• Title/Summary/Keyword: Isonicotinate

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Kinetic Study on Nucleophilic Substitution Reaction of 5-Nitro-8-quinolyl Benzoate, Picolinate, Nicotinate and Isonicotinate with Alkali Metal Ethoxide: Effect of Nonleaving Group on Reactivity and Transition State Structure

  • Lee, Jieun;Kim, Min-Young;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.6
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    • pp.1789-1793
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    • 2014
  • Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the reactions of 5-nitro-8-quinolyl nicotinate (4) and 5-nitro-8-quinolyl isonicotinate (5) with alkali metal ethoxides (EtOM; M = K, Na and Li) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [EtOM] curve slightly upward for the reactions with EtOK and EtONa but are linear for the reactions with EtOLi and for those with EtOK in the presence of 18-crown-6-ether. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the reactivity increases in the order $EtO^-{\approx}EtOLi$ < EtOK < EtONa for the reactions of 4 and EtOLi < $EtO^-$ < EtOK < EtONa for the reactions of 5. Comparison of the kinetic results for the reactions of 4 and 5 with those reported previously for the corresponding reactions of 5-nitro-8-quinolyl benzoate (2) and picolinate (3) has revealed that the esters possessing a pyridine ring (i.e., 3-5) are significantly more reactive than the benzoate ester 2 due to the presence of the electronegative N atom (e.g., 2 << 3 < 4 < 5). It has been concluded that $M^+$ ion catalyzes the reactions of 3-5 by increasing the electrophilicity of the reaction center through a five-membered cyclic transition state (TS) for the reaction of 3 and via a four-membered cyclic TS for the reactions of 4 and 5.

Catalytic Effects of Co(Ⅲ) Complexes on the Hydrolysis of p-Nitrophenyl Picolinate (p-Nitrophenyl Picolinate의 가수분해에 대한 코발트(Ⅲ) 착물의 촉매효과)

  • Noh, Jae Geun;Kim, Chang Suk;Hong, Soon Yung
    • Journal of the Korean Chemical Society
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    • v.40 no.4
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    • pp.254-263
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    • 1996
  • Five cobalt(Ⅲ) complexes were synthesized from bi- or tridentate nitrogen ligands. Catalytic actions of these complexes for hydrolyses of p-nitrophenyl picolinate, p-nitrophenyl nicotinate, and p-nitrophenyl isonicotinate were investigated by a spectrophotometric method. p-Nitrophenyl picolinate showed the most senstive reaction among three substrates by these catalysts. Aquohydroxo Co(Ⅲ) complexes raised as much as 21∼40 times the rate of hydrolysis of p-nitrophenyl picolinate at pH 6.5. Activities of complexes were in the order: Co(ibpn)(OH)2(OH2) > Co(aepn)(OH)2(OH2) > Co(tn)2(OH)(OH2) > Co (bpy)2(OH)(OH2) > Co(dien)(OH)2(OH2). Catalytic hydrolysis was postulated to proceed through a intramolecular general base catalysis path which is mixed by a partial intramolecular nucleophilic catalysis.

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Ring-Conformations via the Competition of Electrostatic Interaction and Argentophilic Interaction. Cyclodimeric Structures of Silver Trifluoromethanesulfonate Containing Isonicotinate Ester Ligands

  • Kim, Chi-Won;Kim, Cho-Rong;Noh, Tae-Hwan;Jung, Ok-Sang
    • Bulletin of the Korean Chemical Society
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    • v.30 no.10
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    • pp.2341-2344
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    • 2009
  • Metallacyclodimers, [Ag(OTf)($L1)]_2$ and [Ag($L2)]_2(OTf)_2$ (L1 = 1,3-dibromo-2,2-bis[(isonicotinoyloxy)methyl] propane; L2 = 2,5-dimethyl-2,5-bis(isonicotinoyloxy)hexane) were constructed and characterized. The crystal structure of [Ag(OTf)($L1)]_2$ reveals a 32-membered cyclodimer, whereas that of [Ag($L2)]_2(OTf)_2$ shows a linked 34-membered cyclodimer chain via intercyclic argentophilic (Ag…Ag) interactions. [Ag(OTf)($(L1)]_2$ affords “intramolecular $\pi-\pi$ interaction cyclodimer” whereas [Ag($L2)]_2(OTf)_2$ produces a racemic mixture of “twisted cyclodimer”. Ring-conformation of the cyclodimers was affected via the competition of electrostatic interaction and argentophilic interaction.

Push-pull Strategy for Control of Sweet-potato Whitefly, Bemisia tabaci (Hemiptera: Aleyrodidae) in a Tomato Greenhouse (Push-pull 전략을 이용한 시설 토마토 담배가루이 방제효과)

  • Lee, Young Su;Lee, Hee A;Lee, Hyun Ju;Choi, Jong Yoon;Lee, Sang-Woo;Hong, Soon Sung;Jang, Myoung Jun
    • Korean journal of applied entomology
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    • v.58 no.3
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    • pp.209-218
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    • 2019
  • This study was conducted to develop a technology for environmentally friendly control of sweet-potato whitefly, Bemisia tabaci, by controlling their behavior using a push-pull strategy in a tomato greenhouse. B. tabaci was attracted the most by yellow color, light source of 520 nm, whereas it avoided the complex light treatment of 450 + 660 nm. The two natural enemies of B. tabaci, Cyrtopeltis tenuis and Orius laevigatus, were attracted the most by 520 nm light source. B. tabaci was repelled by the volatile organic compounds ocimene and carvacrol and was the most attracted by methyl isonicotinate. When buckwheat was added into the tomato greenhouse, the density of C. tenuis was maintained at about 16 times higher than when untreated for 15 days. As a result of the combined treatment of push-pull strategy, the density per trap of B. tabaci was three times lower than when no treatment was applied, and the control of this pest increased with time and reached up to 68.7%.