• Title/Summary/Keyword: Pyridyl-urea

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Smile Rearrangement of Herbicidal Flazasulfuron (제초성 Flazasulfuron의 Smile 자리옮김 반응)

  • Lee, Gwnag-Jae;Kim, Yong-Jip;Kim, Dae-Whang;Sung, Nack-Do
    • Applied Biological Chemistry
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    • v.39 no.1
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    • pp.70-76
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    • 1996
  • A series of the herbicidal pyridylsulfonyl areas, none substitutent, 1-(4,6-dimethoxypyrimidine-2-yl)-3-(2-pyridylsulfonyl) urea, 3 and 3-trifluoromethyl substitutent, 1-(4,6-dimethoxypyrimidine-2-yl)-3-(3-trifluoromethyl-2-pyridylsulfonyl) urea, 5(Flazasulfuron) were synthesizied and the rate of hydrolysis of their has been studied in 25%(v/v) aqueous dioxane at $45^{\circ}C$. From the results of solvent effect($m{\ll}1,\;n{\ll}3\;&\;{\mid}m{\mid}{\ll}{\mid}{\ell}{\mid}$), thermodynamic parameter (${\Delta}S^{\neq}=0.54{\sim}\;-2.19\;e.u.\;&\;{\Delta}H^{\neq}=0.025\;Kcal.mol.^{-1}$), hydrolysis product analysis, $pK_a$ constant(3: 4.9 & 5: lit.4.6) and the rate equation, a marked difference in the kinetics of the reaction of 3 and 5(Flazasulfuron) was observed. It may be concluded that the hydrolysis of 5 proceeds through the $A-S_N2Ar$ reaction via conjugate acid$(5H^+)$ below pH 7.0, whereas, above pH 9.0, the hydrolysis proceeds through irreversibly $(E_1)_{anion}$ and reversibly $(E_1CB)_R$ mechanism via conjugate base(CB), respectively. But in case of 5, $A-S_N2Ar,\;(E_1)anion\;and\;(E_1CB)_R$ mechanism involved Smile rearrangement. The mate of rearrangement of 5 to a 3-trifluoromethyl-2-pyridylpyrimidinyl urea(PPU) in acid and 3-trifluoromethyl-2-pyridyl-4.6-dimethoxypyridinyl amine (PPA) in base was increased about 3.5 times by the introduction of trifluoromethyl group in the 3-position on the 2-pyridyl ring. From the basis of these findings, a possible mechanism for the hydrolysis of 5 was proposed and discussed.

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Simultaneous Determination of Isocyanates by High Performance Liquid Chromatography (고속액체크로마토그래피를 이용한 이소시아네이트의 동시 정량)

  • Lee, Seon Joo;Lee, Kwang Mook;Roh, Young Man
    • Journal of Korean Society of Occupational and Environmental Hygiene
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    • v.4 no.2
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    • pp.137-147
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    • 1994
  • This study was designed to identify and quantitate airborne isocyanate simultaneously by HPLC. These samples were collected using 1-(2-pyridyl)piperazine(1-2PP) coated glass fiber filter from polyurethane painting works at 8 wood furniture factories in Kimpo and Inchun. The results obtained were as follows : 1. The most suitable mobile phase condition of simultaneously analyzing isocyanates was 0.01 M ammonium acetate buffer ACN(70/30) adjusted to pH 6.2 from the beginning of the analysis to 20 min and 0.01 M ammonium acetate buffer/ACN(50/50) adjusted to pH 6.2 from 21 min to 40 min using the gradient mode. The peaks of isocyanates were able to obtain within 30 min. 2. The recovery efficiencies for 2,6-TDI, 2,4-TDI, HDI and MDI urea derivates spiked at the target concentration on coated glass fiber tillers were 91.00, 93.42, 91.31 and 94.21 %, respectively. 3. The qualitative analysis of the isocyanates samples from polyurethane spray painting works in wood furnture factories identified Ihree isocyanates, 2,6-TDI, 2,4-TDI and MOI. And their concentration ranges were 0-312.6, 0-56.3 and $0-62.1{\mu}g/m^3$, respectively. A disadvantage of using the colorimetric method for isocyanate analysis is its inability of separating isocyanates. This study identified such three isocyanates as 2,6-TDI, 2,4-TDI and MDI from polyurethane spray painting works in wood furniture factories. These isocyanates were successfully quantitated by HPLC by modifying the mobile phase condition and switching to gradient mode.

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Effect of PGRs and various co-packing materials on storage quality in 'Shine Muscat' grapes

  • Kim, Sung-Joo;Kim, Yu-Rim;Choi, Cheol;Ahn, Young-Jik;Choi, Hyun-Jin;Chun, Jong-Pil
    • Korean Journal of Agricultural Science
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    • v.48 no.2
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    • pp.241-250
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    • 2021
  • This investigation assessed the berry quality after two months of low-temperature storage (3 ± 1℃) of 'Shine Muscat' grapes, which were treated with CPPU (N-[2-chloro-4-pyridyl]-N'-phenylurea) or TDZ (1-phenyl-3-[1,2,3-thiadiazol-5-yl] urea) in combination with gibbrellic acid (GA3). The berry shatter rate was the lowest (1%) in 4 cm + CPPU treatment, while it was the highest (2.4%) in 3 cm floral length treated with CPPU. On the other hand, the 4 cm + TDZ treatment resulted in a shatter rate of 2.0%, which was twice as high as that observed after 4 cm + CPPU treatment. The 4 cm + TDZ treatment resulted in a 5.5% berry decay rate, which was the highest among all treatments. Alternatives to using a sulfur dioxide (SD) pad to maintain the quality of 'Shine Muscat' grapes, namely, using ethylene scrubbers (ESs, 3 g × 2 sachet) and alcohol releasers (ARs, 2 g × 2 sachet) in a 2 kg carton package for export, were explored in this study. The berry shatter rate with ES treatment (1.0%) was found to be comparable to that with SD treatment (0.6%) during three months of cold storage. Regarding the berry decay rate, that of the untreated control surged to 36.0% in the three months of storage, followed by 19.9% and 15.5% in samples subjected to AR and ES treatments respectively. Compared with the untreated control, the samples subjected to SD treatment showed a decay rate of 2.2%, which was the most effective in reducing berry decay by 95%. These results demonstrated that SD pad treatment of 'Shine Muscat' grapes was the most effective method of maintaining berry quality, and ES treatment partially reduced the berry shatter and berry decay rates.