• Title/Summary/Keyword: Photoreactions

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Photoreactions of the Skin (피부의 광반응)

  • Bae Sung-Soo;Park Rae-Joon;Kim Jin-Sang;Kwon Hyuk-Cheol
    • The Journal of Korean Physical Therapy
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    • v.4 no.1
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    • pp.13-18
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    • 1992
  • Most of the electromagnetic agents used in physical therapy rely for their effects on tissue heating and photoreaction of the body. Infrared and untraviolet light on the other hand, owns its place in medicine because it produces direct photochemial reaction when it interacts with the body. This study was carried out to investigate and review for photoreaction of the akin. The results were an follows. 1. The effects of the infrared are heat production, increasing metabolism, increasing circulation, vasodilatation and pigmentation. 2. Directed photoreactions are divided into acute reaction and chronic reaction, and the acute reaction makes pigmentation from $290\~320nm$ of ultraviolet ray. 3. Ultraviolet ray formated pigmentations, which are melanoblasts excited from ultraviolet ray and received chemical stimulation, that make melanin granule. 4. If exposured with long duration, at ultraviolet ray, it makes skin thickening and epithelioma. 5. Indirected photoreaction is made by existenced hypersensitivity of photoreaction or lack of photodefence structure. 6. The phototoxic reactions are synthesized by chemical reaction of excitement from ultraviolet ray also this time analysis, synthesis and polymerization from energy of a circumferenced substance. 7. Sunscreen substances are P-amino benzoic acid and oxidate titan.

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Photochemical Reactions of Saccharin-$\alpha$-Silylamine Systems. Desilylmethylation of $\alpha$-Silylamine via Single Electron Transfer Pathway

  • Ung Chan Yoon;Young Sim Koh;Hyun Jin Kim;Dong Yoon Jung;Dong Uk Kim;Sung Ju Cho;Sang Jin Lee
    • Bulletin of the Korean Chemical Society
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    • v.15 no.9
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    • pp.743-748
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    • 1994
  • Photochemical reactions of saccharin with tertiary amines were explored. Saccharin was found to undergo an acid-base reaction with N-trimethylsilylmethyl-N,N-diethyl amine to form N-trimethylsilylmethyl-N,N-diethyl ammonium saccharin salt which is in equilibrium with free saccharin and N-trimethylsilylmethyl-N,N-diethyl amine insolution. Photoreaction of N-trimethylsilylmethyl-N,N-diethyl ammonium saccharin in $CH_3OH\;or\;CH_3CN$ results in the generation of desilylmethylated product, N,N-diethyl ammonium saccharin mainly along with benzamide. Photoreaction of N-methylsaccharin with N-trimethylsilylmethyl-N,N-diethyl amine in $CH_3OH$ leads to the production of o-(N-methylcarbamoyl)-N-ethylbenzenesulfonamid e as the major product along with N-methylbenzamide as the minor product. On the other hand, photoreaction of N,N,N-triethyl ammonium saccharin, generated from saccharin and triethylamine, produces N-methylbenzamide as the exclusive product. These photoreactions are quenched by oxygen indicating that triplets of saccharin and N-methylsaccharin are the reactive excited states. Based on the consideration of the redox potentials of saccharin and N-trimethylsilylmethyl-N,N-diethyl amine, and the nature of photoproducts, pathways involving initial triplet state single electron transfer are proposed for photoreactions of the saccharins with the ${\alpha}$-silylamine.

Exploratory Study of Photocyclization Reactions of N-(Trimethylsilylmethylthioalkyl)phthalimides

  • Ung Chan Yoon;Sang Jin Lee;Kyung Ja Lee;Sung Ju Cho;Chan Woo Lee;Patrick S. Mariano
    • Bulletin of the Korean Chemical Society
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    • v.15 no.2
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    • pp.154-161
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    • 1994
  • Studies have been conducted to explore single electron transfer (SET) induced photocyclization reactions of N-(trimethylsilylmethylthioalkyl)phthalimides (alkyl=ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl). Photocyclizations occur in methanol in modest to high yields to produce cyclized products in which phthalimide carbonyl carbon is bonded to the carbon of side chain in place of the trimethylsilyl group. Mechanism for these photocyclizations involving intramolecular SET from sulfur in the ${\alpha}$-silylmethylthioalkyl groups to the singlet excited state phthalimide moieties followed by desilylation of the intermediate ${\alpha}$ -silylmethylthio cation radicals and cyclization by radical coupling is proposed. In contrast, photoreactions of N-(trimethylsilylmethylthioalkyl)phthalimides in acetone follow different reaction routes to produce another cyclized products in which carbon-carbon bond formation takes place between the phthalimide carbonyl carbon and the carbon ${\alpha}$ to silicon and sulfur atoms via triplet carbonyl hydrogen abstraction pathway. The normal singlet SET pathway dominates this triplet process for photoreactions of these substances in methanol while the triplet process dominates the singlet SET pathway for those in acetone. The efficient and regioselective cyclization reactions observed for photolyses in methanol represent synthetically useful processes for construction of medium and large ring heterocyclic compounds.

PHOTOCHEMICAL REACTIONS OF PSEUDOSACCHARIN 3-ALLYL ETHER (PROBENAZOLE) AND ITS ALKYL ETHER

  • Yoon, Ung-Chan
    • Journal of Photoscience
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    • v.2 no.2
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    • pp.77-81
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    • 1995
  • Photoreactions of pseudosaccharin ethers have been investigated. Pseudosaccharin 3-allyl ether undergoes a facile photoreaction via reaction pathways involving homolysis of bond between pseudosaccharyl oxygen and 3-allyl carbon, and excited nucleophilic substitution of allyloxy group by solvent which are not quenched by oxygen present in the reaction. Product yield demonstrates that the homolysis pathway predominates over the nucleophilic substitution in ca. 7:1 ratio. In contrast, pseudosaccharin alkyl ethers follow different reaction routes to produce two products, solvent-substituted pseudosaccharin alkyl ethers and reduction products, 3-alkoxy-1, 2-benzisothiazoles. The formations of reduction products, 3-alkoxy-1, 2-benzisothiazoles are completely quenched by oxygen.

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Silyl-Tranfer Photoreactions of Trimethylsilylmethyl Substituted Acyclic N-Sulfonylbenzamides

  • Oh, Sun-Wha
    • Journal of Photoscience
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    • v.12 no.2
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    • pp.63-66
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    • 2005
  • The azomethine ylide forming photoreaction has been explored by probing the excited state chemistry of several N-trimethylsilylmethyl substituted cyclic and acyclic imides and amide analogs. N-[(Trimethylsilyl)methyl]-N-mesylbenzamide (5) undergoes the excited state C to O silyl migration reaction to produce azomethine ylide intermediate 13. This ylide undergoes electrocyclization to form transient aziridine intermediate 14 which react further by ring opening to generate N-phenacylamine product 10. On the other hand, photolysis of N-[N-mesyl-N-(trimethylsilyl)methyl]aminoethyl-N-mesylbenzamide (8) brings about desilylation resulting in the production of dimer 17.

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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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Medium effects on the H-Atom Abstraction and Silyl-Transfer Photoreactions of Silylalkyl Ketones

  • Oh, Sun-Wha
    • Journal of Photoscience
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    • v.12 no.1
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    • pp.47-50
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    • 2005
  • Mediumeffects have been explored on the competitive H-atom abstraction and SET-promoted, silyl-transfer reactions of excited states of silylalkyl-substituted phenyl ketones. The chemical selectivities of photochemical reactions of silylalkyl phenyl ketones appear to depend on medium polarity, medium silophilicity, added metal cation and alkyl length. Irradiations of silylalkylketones in aqueous solvent system and in presence of metal cation such as $Li^+$ and $Mg^{+2} $lead to formation of acetophenone predominantly by the sequential SET-silyl transfer route.

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Photocyclodimerization of Maleimide

  • Shim, Sang-Chul;Bong, Pill-Hoon
    • Bulletin of the Korean Chemical Society
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    • v.3 no.3
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    • pp.115-119
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    • 1982
  • The photoreaction of maleimide, one of the best model compounds of DNA molecules for psoralen-DNA photoreactions, is studied in order to investigate the photoreactivity and the mechanism of the maleimide-psoralen photoreaction. The (2+2) photocyclodimer of maleimide was obtained in solution state by direct or sensitized irradiation. The rate constant of dimerization is determined by quenching studies and found to be of the order of $10^9 M^{-1}sec^{-1}$. The direct dimerization of maleimide is found to undergo through the triplet excited state. The quantum yields of dimerization are dependent on the maleimide concentration.

Photo-Crosslinking of Poly(glycidyl methacrylate) Initiated by N-Hydroxyphthalimide Sulfonates

  • Kyu Ho Chae;Ik Ju Park;Min Ho Choi
    • Bulletin of the Korean Chemical Society
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    • v.14 no.5
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    • pp.614-618
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    • 1993
  • The photoacid generation efficiency of four N-hydroxyphthalimide sulfonate derivatives was studied by photo-crosslinking reaction of poly(glycidyl methacrylate) in solid film state. The relative photoacid generation efficiency was increased in the order of N-hydroxyphthalimide methanesulfonate > -toluenesulfonate > -nitrobenzenesulfonate > -dinitrobenzensulfonate, and the reaction was efficiently sensitized by benzophenone suggesting that this photoreactions is likely to proceed through its triplet excited state.

Photochemistry of Some Vinylcyclopropanes (비닐시클로프로판의 光化學反應에 관한 硏究)

  • Shim Sang Chul;Suh Shi Woo
    • Journal of the Korean Chemical Society
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    • v.23 no.2
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    • pp.115-118
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    • 1979
  • The photochemical reactions and spectral properties of 1,1-diphenyl-2-vinylcyclopropane were studied. Upon direct irradiation of the compound at 253.7nm, 1,1-diphenylethylene was formed as a major product along with a small amount of 4,4-diphenylcyclopentene. Sensitized photoreactions showed quite a different phenomena from those of conjugated dienes supporting the spectral results that the cyclopropane ring does not transmit the conjugation in the compound.

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