• Title/Summary/Keyword: electron donating group

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Structure activity relationships on the herbicidal activities of 5-(2,3-dihydro-2,2-dimethylbenzothiophene-7-yl)-2-(1-(alkoxyimino)butyl)-3-hydroxy-2-cyclohexene-1-one derivatives (5-(2,3-dihydro-2,2-dimethylbenzothiophene-7-yl)-2-(1-(alkoxyimino)butyl)-3-hydroxy-2-cyclohexene-1-one 유도체의 구조와 살초활성 관계)

  • Sung, Nack-Do;Song, Jong-Whan
    • The Korean Journal of Pesticide Science
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    • v.4 no.2
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    • pp.69-71
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    • 2000
  • The herbicidal activities ($pI_{50}$) with alkoxy (RO-) groups on the azomethine nitrogen atom in 5-(2,3-dihydro-2,2-dimethylbenzothiophene-7-yl)-2-(1-(alkoxyimino)butyl)-3-hydroxy-2-cyclohexene-1-one derivatives against various weeds were measured in the flooded and in the paddy conditions. Particularly, i-propoxy subsutuent, 5 of them showed excellent herbicidal activity at a rate of 4kg/ha with pre-emergence against barnyard grass (Echinochloa crus-galli) with good selectivity on rice plant (Oryza sativa). The results of the structure-activity relationships (SAR) analyses are shown that the alkyl subsituents with higher hydrophobicity (logp>0) and electron donating (${\sigma}^*<0$) group as a new substrate rather than alkoxy substituents seems to be contribute to the herbicidal activity with pre-emergence.

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Kinetics and Mechanism of the Hydrolysis of N-(p-Nitrophenyl)-benzohydrazonyl Azide Derivatives (N-(p-니트로페닐)-벤조히드라조닐아지드 유도체의 가수분해 반응메카니즘과 그의 반응속도론적 연구)

  • Nack-Do Sung;Ki-Sung Kwon;Tae-Rin Kim
    • Journal of the Korean Chemical Society
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    • v.22 no.3
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    • pp.150-157
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    • 1978
  • The rate constants for the hydrolysis of the derivatives of N-(p-nitrophenyl)-benzohydrazonyl azide (p-$CH_3,\;p-CH_3O,\;p-NO_2$, p-Cl, p-Br) have been determined by UV spectrophotometry in 50% dioxane-water at $25^{\cicr}C$ and a rate equation which can be applied over wide pH range was obtained. Below pH 5, the rate of hydrolysis of hydrazonyl azides is accelerated by electron-donating group ($\rho$ = -0.47), whereas at the pH values greater than 7, the $\rho$-value is 0.68. The effect of salt, solvent, substituent and azide ion on the rate of hydrolysis are rationalized in terms of $S_N1$ and $S_N2$ mechanism; below pH 5, the hydrolysis proceed through $S_N1$, however, above pH 7, the hydrolysis is started by the attack of hydroxide ion and in the range of pH 5∼7, these two reactions occur competitively.

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Kinetic Study on Aminolysis of 4-Chloro-2-Nitrophenyl X-Substituted-Benzoates in Acetonitrile and in 80 mol % H2O/20 mol % DMSO: Effect of Medium on Reactivity and Reaction Mechanism

  • Kim, Ha-Ram;Um, Tae-Il;Kim, Min-Young;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.4
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    • pp.1128-1132
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    • 2014
  • A kinetic study on aminolysis of 4-chloro-2-nitrophenyl X-substituted-benzoates (6a-i) in MeCN is reported. The Hammett plot for the reactions of 6a-i with piperidine consists of two intersecting straight lines, while the Yukawa-Tsuno plot exhibits an excellent linear correlation with ${\rho}_X$ = 1.03 and r = 0.78. The nonlinear Hammett plot is not due to a change in rate-determining step (RDS) but is caused by the resonance stabilization of substrates possessing an electron-donating group in the benzoyl moiety. The Br${\phi}$nsted-type plot for the reactions of 4-chloro-2-nitrophenyl benzoate (6e) with a series of cyclic secondary amines is linear with ${\beta}_{nuc}$ = 0.69, an upper limit for reactions reported to proceed through a concerted mechanism. The aminolysis of 6e in aqueous medium has previously been reported to proceed through a stepwise mechanism with a change in RDS on the basis of a curved Br${\phi}$nsted-type plot. It has been concluded that instability of the zwitterionic tetrahedral intermediate ($T^{\pm}$) in MeCN forces the reaction to proceed through a concerted mechanism. This is further supported by the kinetic result that the amines used in this study are less reactive in MeCN than in $H_2O$, although they are more basic in MeCN over 7 $pK_a$ units.

Metal Ion Catalysis in Nucleophilic Displacement Reactions of 2-Pyridyl X-Substituted Benzoates with Potassium Ethoxide in Anhydrous Ethanol

  • Lee, Jae-In;Kang, Ji-Sun;Im, Li-Ra;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.31 no.12
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    • pp.3543-3548
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    • 2010
  • A kinetic study on nucleophilic displacement reactions of 2-pyridyl X-substituted benzoates 1a-e with potassium ethoxide (EtOK) in anhydrous ethanol is reported. Plots of pseudo-first-order rate constants ($k_{obsd}$) vs. $[EtOK]_o$ exhibit upward curvature. The $k_{obsd}$ value at a fixed $[EtOK]_o$ decreases steeply upon addition of 18-crown-6-ether (18C6) to the reaction mixture up to [18C6]/$[EtOK]_o$ = 1 and then remains nearly constant thereafter. In contrast, $k_{obsd}$ increases sharply upon addition of LiSCN or KSCN. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ has revealed that ion-paired EtOK is more reactive than dissociated $EtO^-$, indicating that $K^+$ ion acts as a Lewis acid catalyst. Hammett plots for the reactions of 1a-e with dissociated $EtO^-$ and ion-paired EtOK result in excellent linear correlation with $\rho$ values of 3.01 and 2.67, respectively. The $k_{EtOK}/k_{EtO^-}$ ratio increases as the substituent X in the benzoyl moiety becomes a stronger electron-donating group. $K^+$ ion has been concluded to catalyze the current reaction by stabilizing the transition state through formation of a 6-membered cyclic complex.

Synthesis and Characterization of a Near-Infrared Optical Materials for Shielding Infrared Rays

  • Park Su-Yeol;Sin Seung-Rim;Sin Jong-Il;O Se-Hwa;Jeon Geun
    • Proceedings of the Korean Society of Dyers and Finishers Conference
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    • 2005.05a
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    • pp.213-215
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    • 2005
  • The metal complexes can be influenced not only by the central metal atoms and the substituent groups, but also by the native of the chelating atoms. For example, near-infrared absorbing chromophores were synthesized by the reaction of phenylenediamine derivatives with a solution of pottassium hydroxide followed by the addition of nickel(II) chloride. These dyes provide absorbing infrared light over 780-840 nm with an extinction coefficient of $2.5-6.0{\times}10^4$. By introduction of alkyl, alkoxyl, cyano, and other functional group into the parent dye, these dyes greatly improved the solubility in organic solvent. New near-infrared absorbing donor-acceptor chromophores have been investigated by varying the electron donating and accepting strength of the two halves of the molecule. The cyanine chromophores permit the simplest way of obtaining systems that absorb well into the near-infrared region of the spectrum. Cyanine dyes possess high extinction coefficients that initially increase with Increasing chain length. These chromophores could be useful in near-infrared optical materials.

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Cinnamic Acid Derivatives V. the Kinetics and Mechanism of the Hydrolysis of Cinnamenylisophorone Derivatives (신남산 유도체 V. Cinnamenylisophorone 유도체의 가수분해 반응에 대한 메카니즘과 그 반응속도론적 연구)

  • Lee, Ki-Chang;Yun, Cheol-Hun;Ryu, Jung-Wook;Lee, Seok-Woo;Jung, Duk-Chal
    • Journal of the Korean Applied Science and Technology
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    • v.8 no.2
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    • pp.161-167
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    • 1991
  • The kinetics of hydrolysis of cinnamenylisophorone derivatives (${rho}-H,\;{rho}-Br,\;P-Cl,\;{rho}-OCH_3$) was investigated using ultraviolet spectrophotometry in 20%(v/v) dicxane-$H_2O$ at 25$^{\circ}C$. A rate equation which can be applied over wide pH range (pH $1.0{\sim}13.0$) was obtained. In order to investigate the substituent effects on cinnarnenylisophorone derivatives, Hammett constant was plotted. As the result, the rate of hydrolysis of cinnamenylisophorone derivatives was facilitated by electron donating group. Final products of the hydrolysis were benzaldehyde and isophorone, From the measurement of reaction rate constant according to pH changes, substituent effect, and final products, it was found that the hydrolysis of cinnarnenylisophorone derivatives was initiated by the neutral $H_2O$ molecule which does not dissociated at below pH 9.0, and in the range of pH $9.0{\sim}11.0$ this reaction occurs by $H_2O$ or hydroxide ion competitively, but proceeded by the hydroxide ion above pH 11.0. On the basis of this kinetic study, the reaction mechanism of the hydrolysis of cinnamenylisophorone derivatives was proposed.

Effects of the Fermentation Periods on the Qualities and Functionalities of the Fermentation Broth of Wild Vegetables (발효기간이 산야채 발효액의 품질과 기능성에 미치는 영향)

  • Kim, Na-Mi;Lee, Jong-Won;Do, Jae-Ho;Yang, Jae-Won
    • Korean Journal of Food Science and Technology
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    • v.35 no.2
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    • pp.272-279
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    • 2003
  • To determine optimal fermentation period of wild vegetables mixed with black sugar without microorganisms during plant extract fermentation food processing, changes in chemical components, quality characteristics of the fermented broth, and physiological functionality during fermentation period were investigated. pH and $^{\circ}Bx$ of fermented broths decreased gradually during fermentation period. Except persimmon leaf, viscosity of fermented broths of wild vegetables decreased after 3 months fermentation period. Amylase activity increased to $167{\sim}800%$ of its initial level after 6 months fermentation period, and invertase activity decreased by $60{\sim}170$ units after 1 month fermentation. No significant level of cellulase activity was observed. In the sensory evaluation test, inherent flavors and tastes of the wild vegetable decreased during the fermentation period, while those of others gradually increased. Overall acceptability was the highest after 3 months fermentation. Content of total phenolic compounds and electron-donating ability were highest after 3 to 4 months fermentation period, and decreased thereafter. Except Mugwort, tyrosinase inhibitory activity was found in all fermented broths. SOD-like activities were $23.0{\sim}25.1$ and $27.0{\sim}29.2%$ in fermentation broths of acacia flower and persimmon leaf, respectively, and were maintained throughout the fermentation period. Based on these results, fermentation period of 3 to 4 months was determined to be appropriate for plant extract fermentation food processing.

Screening of Antioxidant Activity in Dansam(Salvia miltiorrhiza) and Additional Effect on the Shelf-Life and the Characteristics of Yakgwa (단삼추출물의 항산화능 검색 및 약과에의 첨가효과)

  • 김윤화;한영실;백재은;송태희
    • Korean journal of food and cookery science
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    • v.19 no.4
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    • pp.463-469
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    • 2003
  • This study was carried out to investigate the antioxidant activities of Dansam (S. miltiorrhiza). The Dansam (S. miltiorrhiza) was extracted with ethanol and methanol, and the extracts were fractionated with hexane, chloroform, ethyl acetate and butanol and water, in that order. The antioxidant activities of Dansam (S. miltiorrhiza) were determined by measuring the radical scavenging effects, using the 1, l-diphenyl-2-picryl-hydrazyl (DPPH) method. The electron donating ability was shown to be about 50% (IC50) at concentration of L-ascorbic acid, Dansam that reflected eliminatory effect by 50% were 9.48$\mu\textrm{g}$/$m\ell$, 8.28$\mu\textrm{g}$/$m\ell$, and l2.59$\mu\textrm{g}$/$m\ell$ respectively. According to the results of the above anti oxidation experiments, those for the group with the added Dansam showed a decreased oxidation, but the antioxidation increased with time. With a storage temperature of 60 C for 5 days, the acid value for the relative antioxidant activities were higher than in the Control group. The peroxide values for the relative antioxidant activities were also higher than in the Control group. The TBA values for the relative antioxidant activities were higher than in the Control group.

Changes in Glucosinolate Content of Dolsan Leaf Mustard Kimchi during Fermentation and Correlation with Antioxidant, Antihypertensive, and Antidiabetic Activities (발효기간에 따른 돌산갓김치의 glucosinolates 함량변화와 항산화, 항고혈압 및 항당뇨활성과의 상관관계)

  • Oh, Sun-Kyung;Kim, Ki-Woong;Choi, Myeong-Rak
    • Journal of Life Science
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    • v.28 no.11
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    • pp.1290-1300
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    • 2018
  • The glucosinolate content, antioxidant activity, and antihypertensive and antidiabetic activities were measured in a crude extract of Dolsan leaf mustard kimchi (DLMK). The glucosinolate content was low at 6.41 and 7.92 mg/g in leaves and stems of DLMK after 21 days of fermentation. The total polyphenol and total flavonoid contents were more than 2 times higher in the leaves (211.7 mg GAE/g, 158.8 mg QE/g) than in the stem (53.7 mg GAE/g, 85.2 mg QE/g) during the fermentation period. The 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) radical scavenging activity and electron donating ability (EDA) were similar to those of the control group after 14 days of fermentation, while the ferric reducing antioxidant power (FRAP) was higher in the leaves after 14 days of fermentation when compared to the control group. The angiotensin converting enzyme (ACE) inhibitory activity showed similar or higher inhibitory activity in the leaves when compared to the control group (0.01% captopril), and the ${\alpha}$-glucosidase inhibitory activity was higher in the leaves and stems when compared to the control group (0.05% acarbose). The glucosinolate content and the ABTS, ACE, and ${\alpha}$-glucosidase inhibitory activity were correlated, as determined by the observed straight line plot with a positive grade. During the fermentation period, the detected glucosinolates were sinigrin, glucobrasicin, glucotropeolin, and progoitrin. The DLMK extract is therefore expected to be valuable as a functional food because of its effective antioxidant, antihypertensive, and antidiabetic activities.

Improving the efficacy of Lespedeza cuneata ethanol extract on ultraviolet-induced photoaging (야관문 에탄올 추출물의 자외선 노출에 의한 피부 광노화 개선 효과)

  • Jung, Hee Kyoung;Choi, Mi Ok;Kim, Bae Jin;Jo, Seung Kyeung;Jeong, Yoo Seok
    • Food Science and Preservation
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    • v.21 no.2
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    • pp.264-275
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    • 2014
  • This study evaluated the improving efficacy of Lespedeza cuneata ethanol extract on skin photoaging induced by ultraviolet (UV) irradiation. The total polyphenol and flavonoid contents of the extract were respectively $134.98{\pm}1.70$ and $16.20{\pm}0.05$ mg/g, respectively. The superoxide anion radical scavenging activity and electron-donating ability of the extract were shown to be dependent on concentration, and the antioxidant ability was shown to be more effective in superoxide anion radical scavenging activity than in electron-donating ability under the same concentration conditions. In the in vivo test conducted using hairless mouse with skin photoaging induced by UVB irradiation, the skin erythema of the groups treated with the extract (AS) reduced to 28% of the control, and the skin moisture content increased to 131%.. The extract treatment of the UV-damaged skin improved the morphological and histopathological state of the skin. Furthermore, the SOD, GST and CAT activities in the skin tissue of the AS group increased, and the XO activity and TBARS generation decreased. With regard to the genes related to the photoaging skin, the expression of PAK, p38, c-Fos, c-Jun, TNF-${\alpha}$ and MMP-3 in the skin of the AS group were found to have decreased. It was therefore concluded that Lespedeza cuneata ethanol extract can reduce wrinkle formation in the skin due to the regulation of the gene expression caused by the exposure to UVB light.