• Title/Summary/Keyword: photochemistry

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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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Substituent Effect in Photochemistry of Carbonyl Compounds: α-Halovalerophenones

  • Cho, Sung-Su;Park, Bong-Ser
    • Bulletin of the Korean Chemical Society
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    • v.25 no.1
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    • pp.42-44
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    • 2004
  • Valerophenones containing a substituent at alpha position to the carbonyl group show the remarkable substituent effects on their photochemical reactions. ${\alpha}$-Bromovalerophenone gives only the C-Br bond cleavage products, but the ${\alpha}$-chlorovalerophenone follows the classical Norrish/Yang reaction pathway predominantly.

The Synthetic Potential of SET Photochemistry of Silicon-Substituted Polydonor-Linked Phthalimides

  • Yoon, Ung Chan;Mariano, Patrick S.
    • Bulletin of the Korean Chemical Society
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    • v.27 no.8
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    • pp.1099-1114
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    • 2006
  • Our studies in the area of single electron transfer (SET) photochemistry have led to the discovery of efficient processes, in which regioselective formation of carbon-centered radicals takes place by nucleophile assisted desilylation of $\alpha$-trialkylsilyl substituted ether, thioether, amine and amide centered cation radicals. The rates of bimolecular desilylation of the intermediate cation radicals exceed those of other cation radical $\alpha$-fragmentation processes (e.g.,-deprotonation). This sereves as the basis for the design of highly regioselective, SET-induced photomacrocyclization reactions of polyether, polythioether, polyamide, and polypeptide linked phthalimides. Photocyclization reactions of trimethylsilyl-terminated substrates in these families are unique in that they produce polyfunctionalized macrocyclic substances in a highly efficient and regioselective manner. In addition, our studies in this area have led to important information about the factors that govern chemical and quantum efficiencies that should be applicable to a wide variety of redox processes promoted by SET from substrates containing more than one electron donor site.

Solvent Effects on the Electronic Spectra of Some Heterocyclic Azo Dyes

  • Behera, Pradipta Kumar;Xess, Anita;Sahu, Sachita
    • Bulletin of the Korean Chemical Society
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    • v.35 no.2
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    • pp.610-616
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    • 2014
  • The influence of solvent polarity on the absorption spectra of some synthesized azo dye with heterocyclic moieties and ${\beta}$-naphthol (1-3) have been investigated using a UV-Visible spectrophotometer. The spectral characteristics of the azo dyes (1-3) in different solvents at room temperature were analyzed. The solvatochromic empirical variables like ${\pi}^*$, ${\alpha}$, and ${\beta}$ have been used to discuss the solvatochromic behaviour of the dyes and to evaluate their contributions to the solute-solvent interactions. A multi-parameter regression model for quantitative assessment of the solute/solvent interaction and the absorption has been used to explain the solvent effect on azo dyes (1-3).

Photochemistry of o-Nitrobenzyl System Coupled with a Benzylsulfonyl Chromophore (벤질술포닐 흡광단에 결합된 2-니트로벤질계의 광화학에 관한 연구)

  • Kim, Hee Jong;Chang, Sun Ki;Choo, Dong Joon
    • Applied Chemistry for Engineering
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    • v.10 no.1
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    • pp.124-128
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    • 1999
  • The photochemistry of the derivatives of o-nitrobenzylcarboxyl esters or benzylsulfonyl derivatives has been well studied separately. But little attempt has been made to combine the fruits these two studies. Being photochemically active, benzylsulphonyl and intro groups should influence the reactivity of each other's, especially when the excited states are fully mixed due to the proximity of their location. The questions which should be clearly answered are; what kind of effect will be excerted to the other group, and whether these two functional groups are coupled in the course of the reaction. To answer the questions raised above, wer have synthesized two sulfonyl esters and four amides from the newly available starting material, 2-nitro-${\alpha}$-toluenesulfonyl chloride. The products identified from the exploratory solution photochemistry were cyclohexanol, phenol, cyclohexylamine, and sulfur dioxide. The results are not much different from the products originally anticipated. It has been temporarily concluded that there is little interaction between the benzyl sulfonyl group and ortho-nitro chromophore. The fact that a base (an amine) has been photochemically generated in solution photochemistry was further confirmed by and utilized in the solid phase quantitative photochemistry done on the film, so as to carry out the photochemical epoxide cure.

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Substituent Effect on Diastereoselectivity in Photochemistry of Valerophenone

  • Park, Bong-Ser;Cho, Sung-Su;Chong, Sang-Hyuk
    • Bulletin of the Korean Chemical Society
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    • v.28 no.7
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    • pp.1156-1158
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    • 2007
  • Valerophenone shows a dramatic shift of photoreactivity by a cyclopropyl group at alpha position to the carbonyl group. By the minor change of structure, the diastereoselectivity of the Yang photocyclization is reversed and the ratio of cyclization to elimination products increases significantly.

A One-Step Synthesis and Antimicrobial Activities of New Substituted Dihydro-1,3,4-Thiadiazoles

  • Mahran, Asma M.;Hassan, Nasser A.
    • Archives of Pharmacal Research
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    • v.29 no.1
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    • pp.46-49
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    • 2006
  • In this study, 2-N-arylimino-2,3-dihydro-1,3,4-thiadiazoles derivatives (6a-h) were synthetized. The mechanism of the studied reactions was discussed. The chemical structures of the compounds were elucidated by their IR, $^1H-NMR,\;^{13}C-NMR$, and Mass spectral data and elemental analyses. The compounds were tested for antimicrobial activity using diffusion agar technique.

Effect of an Extra Chloro Substituent on Photochemistry of o-Alkylphenacyl Chloride

  • Park, Bong-Ser;Jeong, Seong-Jin
    • Bulletin of the Korean Chemical Society
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    • v.30 no.12
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    • pp.3053-3056
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    • 2009
  • The title compound, ${\alpha},{\alpha}$-dichloro-o-methylacetophenone, was prepared and its photochemical behavior was investigated. Addition of an extra chlorine at alpha position to the carbonyl showed many different features from photochemical reactivities of mono chloro analogue, 2,5-dimethylphenacyl chloride. In benzene, a rearrangement product with a formal 1,5-Cl shift and a reduction product were formed beside indanone. In methanol, solvolysis and cyclization of a common dienol intermediate occurred at comparable reaction rates.

New Photochemistry of UV-Absorbing Chemicals in Phase-Controlled Polymer Microspheres (상구조가 조절된 고분자 미립구에서 자외선 흡수제의 거동에 대한 연구)

  • Lee Jong-Suk;Kim Jin-Woong;Kim Junoh;Han Sang-Hoon;Chang Ih-Seop
    • Journal of the Society of Cosmetic Scientists of Korea
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    • v.30 no.3 s.47
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    • pp.361-367
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    • 2004
  • In this study, a different UV (ultra-violet) ray absorption system is presented in which butyl methoxydiben-zoylmethane (BMDM, a model UV-A absorbent, 320$\~$400 nm) is stabilized in phase-controlled poly(methyl methacrylate) (PMMA) microspheres. The photochemistry of BMDM in the microspheres was investigated considering its phase characteristics therein. The analysis of a differential scanning calorimeter and X-ray diffractometer showed that the BMDM in the microspheres was present with a non-crystalline state. The phase control of BMDM in the polymer microsphere has an excellent ability to protect UV-A with maintaining its photo- and thermal stability. The results obtained in this study illustrate well that the phase control of the UV absorbents in the polymer microspheres is another key factor that de-termines its photochemistry and photostability in the final formulations.

Facile Synthesis of Porous TiO2 Nanopearl and Nanorice toward Visible-Light Photocatalysts

  • Lee, Jooran;Bae, Eunju;Yoon, Minjoong
    • Rapid Communication in Photoscience
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    • v.1 no.1
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    • pp.13-15
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    • 2012
  • New porous $TiO_2$ nanostructures with shapes of pearl and rice were synthesized by hydrothermal treatment of $TiO_2$-liposome nanocomposites in acid and base solutions, respectively, as identified by scanning electron microscopy (SEM), transmission electron microscopy (TEM) images and large Brunauer-Emmett-Teller (BET) surface areas. The x-ray diffraction (XRD) patterns and selected area electron diffraction proved them to be well-defined anatase crystals. Their UV-visible reflectance absorption spectra were observed to have low band gap energy (3.03 and 3.07 eV, respectively), exhibiting surface absorption band in the visible range from 400 to 600 nm. The degradation of methylene blue (MB) over the $TiO_2$ nanostructures was observed upon visible-light irradiation, which was found to be very efficient as compared with any other conventional visible-light responsive $TiO_2$ nanostructures.