• 제목/요약/키워드: 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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    • 제31권3호
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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.

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 (Determination of Reactivity by MO Theory (XXII). MO Studies of Substituent Effects of Rates of Phenylthiyl Radical Additions to ${\alpha}$-Methylstyrene)

  • 이익춘;전용구
    • 대한화학회지
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    • 제26권1호
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    • pp.1-6
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    • 1982
  • Thiophenol이 ${\alpha}$-methylstyrene에 부과되는 반응에 대하여 CNDO/2 방법을 써서 분자궤도론적으로 고찰하였다. 전체 부가반응은 두 단계, 즉 (1)티오페놀이 분해하여 Phenylthiyl 라디칼이 되는 단계와 (2)이 라디칼이 ${\alpha}$-methylstyrene에 부가되어 새로운 단위체 라디칼이 되는 단계로 되어 있으나 부가반응속도를 결정하는데 지배적인 과정은 첫째 (1)과정임을 계산결과로 알 수 있었다. 이것이 바로 thiyl라디칼의 치환기에 대한 Hammertt관게에서 陰의 ${\rho}$값이 실험적으로 얻어진 이유이다. ${\rho}$-chlorophenylthiyl 및 m-trifluoromethyl phenylthiyl 라디칼이 ${\rho}$-methoxy-${\alpha}$-methylstyrene에 부가될 때 Hammett 직선관계로 부터 벗어나는 이유는 전체 반응속도에 미치는 부가반응단계 (2)의 기여가 증가하였기 때문이라고 설명 할 수가 있었다.

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

  • 김민관;손광호;김한도
    • 한국염색가공학회지
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    • 제24권1호
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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.

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

  • 권충일;공성호;배성렬
    • 한국지하수토양환경학회지:지하수토양환경
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    • 제6권1호
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    • pp.3-12
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    • 2001
  • 오존산화공정에서 수산화라디칼(OH.)의 생성속도가 다양한 실험조건(오존의 주입농도, 니트로벤젠의 농도, scavenger, pH, 과산화수소)에서 측정되었다. 니트로벤젠은 오존과의 직접적인 반응보다는 수산화라디칼에 의해 분해되었으며 분해속도는 오존과 니트로벤젠의 농도의 함수로 표현되었다. 또한 수산화라디칼 scavenger의 농도가 증가할수록 반응속도는 감소하였다. 실험상에서 얻은 모든 결과는 일차반응속도식을 따랐다. Probe compound와 scavenger를 이용한 경쟁적 방법을 사용하여 수산화라디칼을 측정하였는데, 그 결과 수산화라디칼의 생성속도는 오존의 농도에 선형적으로 비례하였으며, 오존 1몰당 수산화라디칼은 0.24몰이 생성되었다. 동일 오존농도에서 pH의 변화에 따른 수산화라디칼의 생성속도가 측정되었으며, (pH 10.2 ($0.91Ms^{-1}$) > pH 7.3($0.72Ms^{-1}$) > pH 5.6($0.67Ms^{-1}$) > pH 3.4($0.63Ms^{-1}$)) 중성이하의 pH에서보다 알칼리성 pH에서 수산화라디칼은 많이 발생됨을 알 수 있다. 또한 과산화수소의 첨가도 수산화라디칼의 생성속도를 증진시키는 결과를 낳았다. pH의 조절과 과산화수소의 첨가시 발생속도를 비교해보면 과산화수소를 첨가했을 때 수산화라디칼의 발생속도는 1.6배정도 더 크게 측정되었는데 이는 수산화라디칼을 발생시키는 데 있어서 과산화수소의 첨가가 pH의 조절보다는 더 좋은 증진제로써 작용할 수 있다는 것을 설명해준다. 이러한 결과들은 오염된 토양이나 지하수를 처리하기 위한 오존을 이용한 고급산화공정에 충분히 적용될 수 있을 것이라 판단된다.

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

  • 이원남;송영훈;차민석
    • 한국연소학회:학술대회논문집
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    • 한국연소학회 1997년도 제15회 KOSCO SYMPOSIUM 논문집
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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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    • 제29권2호
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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.

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

  • 박형숙
    • Environmental Analysis Health and Toxicology
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    • 제11권1_2호
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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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개암 첨가가 청국장의 품질과 항산화 활성에 미치는 영향 (Changes in the Quality Characteristics and Antioxidative Activities of Cheonggukjang prepared Using Hazelnut)

  • 최원석;이난희;최웅규
    • 한국식품영양학회지
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    • 제30권6호
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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.

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

  • 이기용;신성수
    • 한국연소학회:학술대회논문집
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    • 대한연소학회 2003년도 제27회 KOSCO SYMPOSIUM 논문집
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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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