• Title/Summary/Keyword: Radical addition

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Radical Additions of Arenethiols to Ynamides for the Selective Synthesis of N-[(Z)-2-(Arylsulfanyl)-1-alkenyl]amides

  • Sato, Akinori;Yorimitsu, Hideki;Oshima, Koichiro
    • Bulletin of the Korean Chemical Society
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    • v.31 no.3
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    • pp.570-576
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    • 2010
  • A variety of ynamides undergo highly regio- and stereoselective radical addition of arenethiols with the aid of triethylborane as a radical initiator. The products, N-[(Z)-2-arylsulfanyl-1-alkenyl]amides, can be reduced with triethylsilane in trifluoroacetic acid to yield N-[2-(arylsulfanyl)alkyl]amides.

Determination of Reactivity by MO Theory (XXII). MO Studies of Substituent Effects of Rates of Phenylthiyl Radical Additions to ${\alpha}$-Methylstyrene (分子軌道論에 의한 反應性 決定 (제22보). ${\alpha}$-Methylstyrene 에 대한 Phenylthiyl Radical 부가반응에서의 치환기 효과에 관한 分子軌道論的 연구)

  • Ikchoon Lee;Young Gu Cheun
    • Journal of the Korean Chemical Society
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    • v.26 no.1
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    • pp.1-6
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    • 1982
  • The addition of thiophenol to ${\alpha}$-methylstyrene has been studied MO theoretically using CNDO/2 method. Although overall reaction proceeds in two steps i.e., (1) decomposition of thiophenol to give phenylthiyl radical and (2) addition of the radical to ${\alpha}$-methylstyrene to give a new monomer radical, theoretical results suggested that the phenylthiyl radical formation step, (1), was the dominant process in determining the rate of addition; this was the rationale behind the negative ${\rho}$ value obtained experimentally from the Hammett plots for substituents on the thiyl radicals. The departure from a linear Hammett plot for addition of ${\rho}$-chlorophenylthiyl and m-trifluoromethyl phenylthiyl to ${\rho}$-methoxy-${\alpha}$-methylstyrene could be explained as a result of an increased contribution of the addition step, (2) to the overall reaction rate.

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Radical Addition Reaction of Phosphorous based Flame Retardant with End Groups of PET (2) - Reaction of Resorcinol bis(diphenyl phosphate) - (PET 말단에 대한 인계난연제의 라디칼계 부가반응 (2) - 리소시놀비스다이페닐포스페이트의 반응 -)

  • Kim, Min-Kwan;Sohn, Kwang-Ho;Ghim, Han-Do
    • Textile Coloration and Finishing
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    • v.24 no.1
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    • pp.39-44
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    • 2012
  • To improve flame retardation of poly(ethylene terephthalate) (PET) against burning, resorcinol bis(diphenyl phosphate) (RDP), phosphorous containing flame retardant, was incorporated into PET backbone by radical reaction pathway. Radical endcapping of PET with RDP was confirmed by spectroscopic and thermal analysis. From 400 MHz $^{31}P$ solid state FT-NMR spectrum of PET with RDP (PET-RDP), phosphorus spectra peak in RDP was found at ca. -10 ppm. Furthermore, P-C bond stretching vibration peaks were found ca. $530cm^{-1}$ in FT-IR spectrums of PET-RDP. These results indicated that RDP can be chemically bound at the ends of PET by radical addition method. Thermal characteristics of pure PET (pPET) and PET-RDP were measured and evaluated by TGA thermal analysis. There was not significant changes in thermal characteristics of PET-RDP compared to that of pPET.

The estimation of Hydroxyl radical generation rate in Ozonation (오존산화공정에서 수산화라디칼(OH.)의 생성속도 측정)

  • 권충일;공성호;배성렬
    • Journal of Soil and Groundwater Environment
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    • v.6 no.1
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    • pp.3-12
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    • 2001
  • During ozonation process, the hydroxyl radical generation rates were measured under different experimental conditions (ozone feed rate, nitrobenzene concentration, hydroxyl radical scavenger, pH, HO$_2$O$_2$/O$_3$ etc.) Nitrobenzene could be decomposed by hydroxyl radical rather than ozone only and nitrobenzene decomposition rate was expressed with functions of ozone and nitrobenzene concentration. The rate was decreased as the hydroxyl radical scavenger concentration was increased, and all results were followed pseudo first-order reaction. Using a competitive method, hydroxyl radical generation rate was measured with probe compound and scavenger. It was proportional to ozone concentration, and 0.24mo1 of hydroxyl radical was produced with 1mol of ozone. Under different pH conditions, hydroxyl radical generation rates were measured (pH 10.2 (0.91Ms$^{-1}$ ) > pH 7.3 (0.72Ms$^{-1}$ ) > pH 5.6 (0.67Ms$^{-1}$ ) > pH 3.4 (0.63Ms$^{-1}$ )) showing higher generation rate at high pH values. Addition of hydrogen peroxide promoted the generation rate of hydroxyl radical. Considering the results of pH experiments and addition of hydrogen peroxide experiments, the hydroxyl radical generation rate was 1.6 times higher in hydrogen peroxide solution than in high pH solution, indicating addition of hydrogen peroxide is better promoter to produce the hydroxyl radical in ozonation. These results could be applied to AOPs to remediate the contaminated wastewater and groundwater.

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OH Radical Distribution and Sooting Characteristics in Co-Flow Diffusion Flames (동축류 확산화염의 OH 라다칼 분포 및 매연 특성)

  • Lee, Won-Nam;Song, Young-Hoon;Cha, Min-Suk
    • 한국연소학회:학술대회논문집
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    • 1997.06a
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    • pp.1-11
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    • 1997
  • The soot and OH radical distributions have been experimentally studied in ethylene and propane laminar diffusion flames. The integrated soot volume fraction was measured along the centerline of a flame using a laser light extinction method. Planar laser light scattering and PLIF techniques are employed for the soot and OH radical distribution measurements utilizing Nd:YAG laser and OPO, FDO system. The concentration of OH radical is rapidly decreased at the edge of sooting region, which implies the importance of OH radical species on the soot oxidation process. For ethylene flames, the addition of air in fuel moves the OH radical distribution towards the center line of a flame at the soot oxidation region, while the concentration of OH radical remains relatively high at the soot formation region. The interaction between soot particles and OH radicals becomes more active with fuel-air at the soot oxidation region. For propane flames, however, any indication of the increased interaction between soot particles and OH radicals with fuel-air was not noticed.

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Aromatic Formation from Vinyl Radical and Acetylene. A Mechanistic Study

  • Natalia, Debby;Indarto, Antonius
    • Bulletin of the Korean Chemical Society
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    • v.29 no.2
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    • pp.319-322
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    • 2008
  • The viability of acetylene addition in each step of aromatic formation initiated by vinyl radical and acetylene also with its competition with structure rearrangement is investigated by determining optimal geometries and barrier and reaction energies using quantum mechanical methods. In principle, the addition reaction has more difficult in term of free energy and enthalpy compared to geometry arrangement. Under combustion conditions, i.e. T = 1200 K, acetylene addition is unfavorable mechanism as the barrier energy values rise much higher than that of geometry arrangement. However, in longer chain hydrocarbon case, e.g. n-CxHx+1 where x ³ 8, C-C bond rotation is rather difficult and requires high energy to form a ring structure, elongation chain is preferable.

Formation of Reactive Oxygen Species and Cr(V) Entities in Chromium(VI) Exposed A549 Cells (크롬 6가 투여 후 A549 세포에서의 Reactive Oxygen Species와 크롬 5가의 발생)

  • 박형숙
    • Environmental Analysis Health and Toxicology
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    • v.11 no.1_2
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    • pp.49-57
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    • 1996
  • The production of reactive oxygen species on addition of hexavalent chromium (potassium dichromate, $K_2Cr_2O_7$ ) to lung cells in culture was studied using flow cytometer analysis. A Coulter Epics Profile flow cytometer was used to detect the formation of reactive oxygen species after $K_2Cr_2O_7$ was added to A549 cells grown to confluence. The cells were loaded with the dye, 2',7'-dichlorofluorescein diacetate, after which cellular esterases removed the acetate groups and the dye was trapped intracellularly. Reactive oxygen species oxidized the dye, with resultant fluorescence. Increased doses of Cr(VI) caused increasing fluorescence (10-fold higher than background at 200 gM). Addition of Cr(III) compounds, as the picolinate or chloride, caused no increased fluorescence. Electron paramagnetic resonance (EPR) spectroscopic studies indicated that three (as yet unidentified) spectral "signals" of the free radical type were formed on addition of 20, 50, 100 and 200 gM Cr(VI) to the A549 cells in suspension. Two other EPR 'signals" with the characteristics of Cr(V) entities were seen at field values lower than the standard free radical value. radical value.

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Changes in the Quality Characteristics and Antioxidative Activities of Cheonggukjang prepared Using Hazelnut (개암 첨가가 청국장의 품질과 항산화 활성에 미치는 영향)

  • Choi, Won-Seok;Lee, Nan-Hee;Choi, Ung-Kyu
    • The Korean Journal of Food And Nutrition
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    • v.30 no.6
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    • pp.1229-1234
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    • 2017
  • This study was carried out to investigate the changes in the antioxidant activity of Cheonggukjang with the addition of hazelnut. The number of Bacillus subtilis and the content of crude fat were increased with the addition of hazelnut. The addition of hazelnut made the color of Cheonggukjang lighter. The flavonoid and polyphenol content were sharply increased in proportion to the addition of hazelnut. The DPPH radical scavenging activity of Cheonggukjang was also increased with the addition of hazelnut. Taken together, it was found that the addition of hazelnut had a positive influence on Cheonggukjang by increasing the antioxidant activity.

The Function of Halogen Additive in $CH_4/O_2/N_2$ Flames ($CH_4/O_2/N_2$ 화염에서 할로겐 첨가제의 역할)

  • Lee, Ki-Yong;Shin, Sung-Su
    • 한국연소학회:학술대회논문집
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    • 2003.12a
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    • pp.209-214
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    • 2003
  • Numerical simulations are performed at atmospheric pressure in order to understand the effect of additives on flame speed, flame temperature, the radical concentration, the NOx formation in freely propagating $CH_4/O_2/N_2$ flames. The additives used are carbon dioxide and hydrogen chloride which have a combination of physical and chemical behavior on hydrocarbon flame. In the flame established with the same mole of methane and additive, $CO_2$ addition significantly contributes toward the reduction of flame speed and flame temperature by the physical effect, whereas addition of HCl mainly does by the chemical effect. The impact of HCl addition on the decrease of the radical concentration is about 1.6-1.8 times as large as $CO_2$ addition. Hydrogen chloride addition is higher on the reduction of EINO than $CO_2$ addition because of the chemical effect of HCl.

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