• Title/Summary/Keyword: Photochemical Reactions

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Dipole-Forming Photochemical Group Transfer Reactions of Phthalimides and ${\alpha}-Ketoamides$

  • Yoon, Ung-Chan;Mariano Patrick S.
    • Journal of Photoscience
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    • v.12 no.3
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    • pp.155-162
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    • 2005
  • Results of studies of SET-promoted dipole-forming photochemical group transfer reactions of phthalimide and ${\alpha}-ketoamide$ derivatives are discussed. Azomethine ylide forming photochemical reactions, which are initiated by intramolecular SET from tethered silylmethyl-, carboxymethyl-, and ${\beta}-hydroxyethyl$ containing electron donors to excited states of phthalimides, related maleimides, and conjugated imides, are presented first. Following this, investigations of regioselective 1,4-dipole forming photochemical reactions of N-trialkylsilylmethyl- and N-trialkylstannyl-${\alpha}$-ketoamides are described.

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Thermal and Photochemical Reactions of Benzosilacyclobutenes with Alcohols. Intermediacy of o-Silaquinone Methide in the Photochemical Reactions

  • Kang, Kyung-Tae;Yoon, Ung-Chan;Seo, Hee-Chan;Kim, Kwang-Nam;Song Hwan Young;Lee, Jae-Chul
    • Bulletin of the Korean Chemical Society
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    • v.12 no.1
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    • pp.57-60
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    • 1991
  • Benzosilacyclobutenes were prepared from the reactions of 1,1-dichlorobenzosilacyclobutene with Grignard reagents or t-butyllithium. In the thermal reactions with alcohols, benzosilacyclobutenes underwent both benzyl-silicon and aryl-silicon bond rupture to yield (dialkyl)alkoxy-o-tolylsilanes and (dialkyl)alkoxybenzylsilanes, respectively. The photochemical reactions, however, produced only the former products via o-silaquinone methides.

EFFECT OF PHOTOCHEMICAL REACTIONS ON LUMINESCENCE OF CRYSTALLINE RDX

  • Kim, Hack-Jin;Kang, Tai-Jong
    • Journal of Photoscience
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    • v.2 no.2
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    • pp.83-87
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    • 1995
  • Luminscence spectra and decay of crystalline hexahydro-1,3,5-trinitro-1,3,5-s-tetrazine (RDX) are observed at 90 K and the effects of photochemical reaction on the luminescence of RDX are investigated. The uv light from high power Hg lamp is used for the photochemical reaction of RDX. While no significant changes are observed in the luminescence spectra after the photochemical reaction, the intensity profile of the spectra changes with the progress of chemical reactions. The biexponential decay of luminescence is modified by chemical reactions. Features of the electronic states of crystalline RDX are discussed in relation to the luminescence.

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Daytime and Nighttime Photochemical Reactions of the Pure Oxygen System (순수 산소계의 주간 및 야간 광화학반응)

  • Kwnag Sik Yun
    • Journal of the Korean Chemical Society
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    • v.13 no.4
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    • pp.249-261
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    • 1969
  • Studies of photochemical reactions of the pure oxygen atmosphere are made using reaction rate constants and atmospheric data available in the latest literature. The daytime and nighttime variations in atomic oxygen and ozone are computed, based on three different conditions: 1) photochemical equilibrium, 2) direct integrations of the rate equations with modifications and approximation to the equations, and 3) by numerical integrations. The departure from the photochemical equilibrium concentrations during day and nighttime are discussed by comparing the results obtaind from the three conditions.

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Synchrotron Radiation Induced Photochemical Reactions for Semiconductor Processes

  • Rhee, Shi-Woo
    • Journal of the Korean Vacuum Society
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    • v.3 no.2
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    • pp.147-157
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    • 1994
  • Valence or core electron excitations induced by Synchrotron radiation (SR) irradiation and ensuing chemical reactions can be applied for semiconductor processes i, e, deposition etching and modifications of thin film materials. Unique selectivity can be achieved by this photochemical reactions in deposition and etching. Some materials can be ecvaporated by SR irradiation which can be utilized for low temperature surface cleaning of thin films. Also SR irradiation significantly lowers the reaction temperature and photon activated surface reactions can be utilized for direct writing or projection lithography of electronic materials. This technique is especially effective in making nanoscale feature size with abrupt and well defined interfaces for next generation electronic devices.

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Comparative Study on Photochemical Reactions of Aromatic Hydrocarbons in Indoor and Outdoor Smog Chambers (실내/외 스모그 챔버에서의 방향족계 탄화수소의 광화학 반응 비교 연구)

  • Dong Jong-In;Ahn Heung-Soon
    • Journal of Environmental Science International
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    • v.14 no.2
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    • pp.231-240
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    • 2005
  • The number of cases exceeding environmental standards of atmospheric ozone in the major cities in Korea has steadily increased during the past decades. In order to understand and analyze the atmospheric reactions in the atmosphere, especially the secondary photochemical reactions, smog chambers studies have been performed very actively by many research groups worldwide. However, these studies have focused on the mechanism of photochemical reactions in high concentration conditions, not at the ambient levels. Therefore, in-depth studies in these conditions are essentially needed to realize exact mechanism in the atmosphere near the earth surface, especially at Korean atmospheric conditions. In this experiment, the mechanism of photochemical smog was examined through a comparative experiment of smog chambers under sun light and black light conditions. The results of our study indicated that concentrations of ozone, aldehyde, and PAN increased as the radiation of light source increases. Photochemical reaction patterns can be considered quite similar for both black light and sun light experiments. Based on our experiments using toluene as a reactant which is present at significant high levels in ambient air relative to other VOCs, it was found that toluene could contribute notably to oxidize NO to $NO_2$, this reaction can eventually generate some other photochemical oxidants such as ozone, aldehyde, and PAN. The results of simulation and experiments generally showed a good agreement quite well except for the case of $O_3$. The restriction of oxidization of NO to $NO_2$ seems to cause this difference, which is mainly from the reaction of peroxy radical itself and other reactants in the real gas.

The Link Between Stereoselectivity and Spin Selectivity in Intermolecular and Intramolecular Photochemical Reactions

  • Griesbeck, Axel G.
    • Journal of Photoscience
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    • v.10 no.1
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    • pp.49-60
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    • 2003
  • How stereo selectivity in singlet and triplet photocycloaddition and photocyclization reactions, respectively, is linked to spin selectivity and how this link affects our understanding of photochemical reaction mechanisms, is described in this review. As illustrative examples, the Paterno-Buchi reaction and the Norrish-Yang cyclization are described with emphasis on triplet biradical structure and dynamics.

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EXPLORATORY PHOTOCHEMICAL STUDY ON THE o-NITROBENZYLSULFONYL DERIVATIVES

  • Chang, Sun-Ki
    • Journal of Photoscience
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    • v.1 no.1
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    • pp.67-68
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    • 1994
  • INTRODUCTION : The photochemistry of nitro chromophore has been the subject of intense study only in recent years. Unlike the carbonyl functional group, of which the photochemistry has been quite extensively studied and fairly well understood, as a result of excellent work done by numerous physical and organic photochemists alike, the nature of photochemistry of nitro group has only recently been systematically explored. The photochemistry of nitro group exhibits general features of the photochemistry of the carbonyl groups such as hydrogen abstraction by the diradical species generated from the n-$\pi$$^*$ excited state of the nitro group. Other photochemical pathways common to the carbonyl group such as the biradical intermidiate formation, photocycloelimination, and cydoaddition reactions are also open for the nitro group. Of all the photochemical reactions of the nitro group mentioned above, hydrogen abstraction by the n-$\pi$$^*$ excited state of the nitro group has drawn much attention by synthetic organic chemists and polymer chemists. In the field of organic synthesis, above mintioned photochemical reaction has been utilized in the photoprotection-deprotection chemistry.

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The Mechanisms for Thermal and Photochemical Isomerizations of N-Substituted 2-Halopyrroles: Syntheses of N-Substituted 3-Halopyrroles

  • Park, Sung-Hyun;Ha, Hong-Joo;Lim, Chul-Taek;Lim, Dong-Kwon;Lee, Kwang-Hee;Park, Yong-Tae
    • Bulletin of the Korean Chemical Society
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    • v.26 no.8
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    • pp.1190-1196
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    • 2005
  • Halopyrroles, N-substituted 2-halopyrroles were prepared by halogenation of N-substituted pyrroles with NBS, NCS, or surfuryl chloride. N-Substituted 3-halopyrroles were synthesized by acid-catalyzed thermal and photochemical isomerization reactions of N-substituted 2-halopyrroles. Both the thermal and photochemical reactions were acid-catalyzed. For the acid-catalyzed isomerization, a mechanism of [1,3] bromine shift followed by deprotonation is operated. For the acid-catalyzed photoisomerization, an excited triplet state of 2-protonated N-benzyl-2-halopyrrole produces an intermediate N-substituted pyrrole complex with halonium ion which is equilibrated with N-substituted pyrrole plus halonium ion, and then the halonium ion newly adds to 3-position of N-substituted pyrrole followed by deprotonation to afford N-benzyl-3-halopyrrole.

Photochemical Reaction of Nalidixic Acid in Methanol

  • Park, Hyoung-Ryun;Park, Ok-Hyun;Lee, Hong-Yune;Seo Jung-Ja;Bark, Ki-Min
    • Bulletin of the Korean Chemical Society
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    • v.24 no.11
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    • pp.1618-1622
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    • 2003
  • The photochemical reactions of methanolic nalidixic acid (NAL) solution in the absence and in the presence of air have been investigated using 300 nm UV light. From the reactions, 1-ethyl-7-methyl-4-oxo-4-hydro-1,8-naphthyridine (EMDN),formic acid, and formaldehyde are produced. In the presence of air, hydrogen peroxide is also detected along with the products listed above. The presence of oxygen during the irradiation of methanolic NAL solution effects on the product yield. The initial quantum yields of the products and of the NAL decomposition are determined. Possible reaction pathways for the photochemical reaction are suggested on the basis of the products analysis.