• 제목/요약/키워드: Photoreaction

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Photoreaction of 8-Methoxypsoralen with Thymine

  • Shim, Sang-Chul;Kim, Yong-Zu
    • Bulletin of the Korean Chemical Society
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    • 제4권2호
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    • pp.95-99
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    • 1983
  • Photoreaction of 8-methoxypsoralen (8-MOP) with thymine (${\ge}$ 300 nm) was carried out in the dioxane-water frozen state. One major and two minor monoaddition products between 8-MOP and thymine were isolated by various chromatographic methods. Major monoadduct was characterized to be a C4 cycloaddition product formed between 5,6-double bond of thymine and 3,4-double bond of 8-MOP with cis-anti stereochemistry. Two minor adducts were proved to be stereoisomers of this major adduct.

Photocyclodimerization of Maleimide

  • Shim, Sang-Chul;Bong, Pill-Hoon
    • Bulletin of the Korean Chemical Society
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    • 제3권3호
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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.

Chemical Lithography by Surface-Induced Photoreaction of Nitro Compounds

  • Han, Sang-Woo;Lee, In-Hyung;Kim, Kwan
    • ETRI Journal
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    • 제26권1호
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    • pp.38-44
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    • 2004
  • Searching for systems of self-assembled monolayers (SAMs) that can be used as templates for chemical lithography, we found that nitro groups on aromatic SAMs are selectively converted on Ag to amino groups by irradiation with a visible laser. 4-nitrobenzenethiol on Ag was thus converted to 4-aminobenzenethiol by irradiating it with an $Ar^+$ laser. This was evident from surface-enhanced Raman scattering (SERS) as well as from a coupling reaction forming amide bonds. The surface-induced photoreaction allowed us to prepare patterned binary monolayers on Ag that showed different chemical reactivities. Using the binary monolayers as a lithographic template, we induced site-specific chemical reactions, such as the selective growth of biominerals on either the nitro- or amine-terminated regions by adjusting the crystal-growth conditions. We also demonstrated that patterned, amine-terminated monolayers can be fabricated even on gold by using silver nanoparticles as photoreducing catalysts.

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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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    • 제15권9호
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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.

Photoreaction of N-(2-Halophenyl)cyclohexanecarboxamide:Synthesis of 2-Alkylbenzoxazole

  • Park, Yong-Tae;Kim, Moon-Sub;Kwak, Young-Woo;Lee, Jae-Keun;Yoh, Soo-Dong;Kim, Woo-Sik
    • Journal of Photoscience
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    • 제7권4호
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    • pp.135-138
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    • 2000
  • The photochemical behavior of haloarene tethered to alkyl by an amide bone(1,2) was studied. The photoreaction of N-(2-bromophenyl) cyclohexanecarboxamide (1b) in basic medium afforded intramolecular substitute product, 2-cyclohexylbenzoxazole (4) and reduced product, N-phenylcyclohexanecarboxamide (5)in 33 and 26% yield, respectively. The chloro analogue(1a) produced photo-Fries type and photosubstituted products(6,4), whereas the iodo analogue produced extensively photoreduced product 5. N-(2-bromophenyl)-N-methylcyclohexanecarboxamide (2), which can not exist as imidol form, produced a photocyclized product, supporting as imidol form is involved in the intramolecular photosubstitution. since the photoreduction but the photosubstitution reaction is retarded by the presence of oxygen, a trilpet state for the photoreduction and a singlet state for the photosubstitution are involved.

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A Novel Photoreaction of (2-Hydroxyethoxyphenyl)pentamethyldisilane

  • Park, Seung Ki;Seong, Won-Je
    • Bulletin of the Korean Chemical Society
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    • 제30권6호
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    • pp.1331-1336
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    • 2009
  • Photolysis of (2-hydroxyethoxyphenyl)pentamethyldisilane 2 in benzene provides a novel intramolecular cyclization photoproduct 9 which was probably formed from the intramolecular reaction to form a seven-membered ring in silatriene intermediate 7 and then the photochemical disrotatory ring closure of 1,3-butadiene moiety to cyclobutene. Irradiation of 2 in methanol afforded photoproducts 5 and 6 which were formed by the nucleophilic attack of methanol to $\beta$ or $\alpha$ silicon atom in pentamethyldisilanyl group of the photoexcited state of 2. Compounds 10 and 11 were also formed by the same way as in the formation of the photoproducts 5 and 6 in the photolysis of (2-allyloxyethoxyphenyl)pentamethyldisilane 3 in methanol solvent. Photoreaction of (2-acetoxyethoxyphenyl) pentamethyldisilane 4 in methanol gave a photoproduct 12 which was formed via the elimination of dimethylsilylene species in the photoexcited state of 4.

Study on A Laser-induced Photoredox Reaction for the Extraction of Precious Elements from Aqueous Solutions

  • Kyuseok Song;Hyungki Cha;Lee, Jongmin;Park, Jongsoo;Lee, Yong-Ill
    • Nuclear Engineering and Technology
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    • 제32권6호
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    • pp.531-536
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    • 2000
  • The extraction of precious metals from aqueous solutions is performed by using a photoredox reaction with a Q-switched Nd:YAG laser. The metallic silver was efficiently precipitated and extracted from the silver nitrate solution by laser photolysis. An optimum reaction condition for silver extraction was determined by adjusting various experimental factors such as type of reducing agent, type of acids and reaction time. The composition of the reaction product was analyzed and it was identified as metallic silver, not other molecular types. The photoreaction of chromium(III) chloride in an acidic aqueous solution was also investigated. The 355 nm laser light was better suited for the reaction of silver nitrate as well as chromium(III) chloride in an acidic solution compared to the 532 nm light.

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3차원 광기록용 포토폴리머 (Photopolymers for 3D optical recording)

  • 이효진;김정훈;김은경
    • 한국광학회:학술대회논문집
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    • 한국광학회 2006년도 하계학술발표회 논문집
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    • pp.411-412
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    • 2006
  • Photopolymers have been of considerable due to their easy of processing and high sensitivity. Exposure of photopolymers to optical source produce recroding mark where the light initiates a photoreaction that occurs preferentially in regions of high illumination. The photoreaction typically involves polymerization of an acrylic or epoxy monomer dispersed together with a photoinitiators in a polymeric binder. A number of photopolymerizable materials have been developed to apply them in 3D optical recording such as holographic or 3-dimensional data storage. In this presentation, photopolymers derived from sol-gel matrix and transparent polymer binder are summarized. The effect of monomer composition and plasticizers on optical recording will be discussed based on the monomer transport during the photopolymerization.

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Photochemistry of Conjugated Polyacetylenes. Photoreaction of 1,4-Diphenylbutadiyne with a Mixture of Olefins

  • Chang Beom Chung;Geon-Soo Kim;Jang Hyuk Kwon;Shim Sang Chul
    • Bulletin of the Korean Chemical Society
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    • 제14권4호
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    • pp.506-510
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    • 1993
  • Irradiation of 1,4-diphenylbutadiyne (DPB) with a mixture of electron-deficient and electron-rich olefins in deaerated tetrahydrofuran yields a 1 : 1 primary photoadduct between DPB and electron-deficient olefins. Irradiation of the primary photoadduct of DPB and dimethyl fumarate (DMFu) with various olefins such as DMFu, acrylonitrile (AN), and 2,3-dimethyl-2-butene (DMB) in deaerated tetrahydrofuran yields regiospecific 1 : 1 photoadducts. The electron-deficient olefins are more reactive than electron-rich olefins in the photoreaction which proceeds through excited triplet state.

The Photochemical Reactivities of Benzenes Tethered to Haloarene

  • 박용태;김영희;황철균;성대동
    • Bulletin of the Korean Chemical Society
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    • 제17권6호
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    • pp.506-510
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    • 1996
  • The syntheses and photoreactions of haloarenes, in which the aryl and haloaryl moieties are tethered by a simple alkyl group, were studied. For 2-benzyl-1-halobenzene, in which two aryl moieties were connected by methylene group, photoreduced product, diphenylmethane, was obtained along with the minor formation of the photocyclized product, fluorene, in acetonitrile solvent. For 1-halo-2-phenethylbenzene, in which two aryl moieties were connected by ethylene group, photocyclized products, 9,10-dihydrophenanthrene and phenanthrene, were obtained along with the minor formation of photoreduced product, bibenzyl, in acetonitrile solvent. The photoreaction selectivities in several solvent systems were studied: In cyclohexane, 2-benzyl-1-chlorobenzene was photoreduced more effective than 2-benzyl-1-bromobenzene; In the presence of NaOH, 1-halo-2-phenethylbenzenes gave 9,10-dihydrophenanthrene and, in the presence of toluene, they gave phenanthrene. A radical reaction mechanism is proposed for the explanation of the reactions. This study shows that the photoreaction of haloarene, in which haloaryl and aryl moieties are tethered by ethylene group, can be used for ring formation of 9,10-dihydrophenanthrene otherwise difficultly accessible.