• Title/Summary/Keyword: Substituent

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Synthesis and mesomorphic properties of biphenly thioester series in ferroelectric liguke crystal (Biphenyl thioester 계열 강유전성액정의 합성 및 물성에 관한 연구)

  • Jeon, Yeong-Jae
    • Korean Journal of Materials Research
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    • v.3 no.1
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    • pp.72-83
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    • 1993
  • Abstract A new and versatile method for the preparation of biphenyl thioester series was studied in ferroelectric liquid crystal. Many of the resulting liquid crystal showed a ferroelectric chiral smectic C phase in addition to the chiral nematic and smectic A phase. We obtained a large spontaneous polarization exceeding $10^{-8}$C/c$m^2$ in new biphenyl thioester series. It was found that the size and polarity of the substituent in chiral carbon influenced the magnitude of spontaneous polarization. The series allow us to determine the influence of substituent size in the chiral carbon the existence and the stability of the Sc* phase.

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Tailoring the Excited-State Intramolecular Proton Transfer (ESIPT) Fluorescence of 2-(2'-Hydroxyphenyl)benzoxazole Derivatives

  • Seo, Jang-Won;Kim, Se-Hoon;Park, Sang-Hyuk;Park, Soo-Young
    • Bulletin of the Korean Chemical Society
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    • v.26 no.11
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    • pp.1706-1710
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    • 2005
  • The excited-state intramolecular proton transfer (ESIPT) fluorescence in the 2-(2'-hydroxyphenyl)benzoxazole (HBO) derivatives with different electron donor and acceptor substituents was studied by spectroscopic and theoretical methods. Changes in the electronic transition, energy levels, and orbital diagrams of HBO analogues were investigated by the semi-empirical molecular orbital calculation and were correlated with the experimental spectral position of ESIPT keto emission. It was found that the presence of substituents, regardless of their nature, resulted in the red-shifted absorption relative to HBO. However, the spectral change of the ESIPT fluorescence was differently affected by the nature of substituent: hypsochromic shift with electron donor and bathochromic shift with electron acceptor.

Substituent Effects on Conformational Changes in (+)-CSA Doped Polyaniline Derivatives

  • Lee, Eung;Kim, Eunok
    • Bulletin of the Korean Chemical Society
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    • v.34 no.7
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    • pp.2111-2116
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    • 2013
  • This paper reports substituent effects on the conformational changes in polyaniline (PAni) derivatives. PAni, poly-o-toluidine (POT), and poly-o-anisidine (POA) were formed by potentiodynamic electropolymerization in aqueous solution containing (+)-camphorsulfonic acid (CSA) as a dopant. UV-Vis spectroscopy and cyclic voltammetry measurements revealed that the methyl group showed a greater steric hindrance than the methoxy group. Further, the doping level decreased with increasing steric hindrance. The sign pattern of the circular dichroism (CD) bands for POA was opposite to that for PAni. However, no CD bands were observed in POT. The steric hindrance caused helical inversion, but at a high level of steric hindrance, the helical conformation could not be adopted, because of the reduced doping level. The reduced crystallinity was greatly affected by the decreased doping level. The steric effect influenced the polymer conformation and the doping level, thus determining the optical activity, morphology, and crystallinity of the PAni derivatives.

Theoretical Study on the Pyrolysis of Sulphonyl Oximes in the Gas Phase

  • Xue, Ying;Lee, Kyung-A;Kim, Chan-Kyung
    • Bulletin of the Korean Chemical Society
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    • v.24 no.6
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    • pp.853-858
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    • 2003
  • The reaction mechanism of the pyrolysis of sulphonyl oximes ($CH_3-C_6H_4-S(O)_2O-N=C(H)-C_6H_4Y$), in the gas phase is studied theoretically at HF/3-21G, ONIOM (B3LYP/6-31G**:HF/3-21G) and ONIOM (MP2/6- 31G**:HF/3-21G) levels. All the calculations show that the thermal decomposition of sulphonyl oximes is a concerted asynchronous process via a six-membered cyclic transition state. The activation energies (Ea) predicted by ONIOM (B3LYP/6-31G**: HF/3-21G) method are in good agreement with the experimental results for a series of tosyl arenecarboxaldoximes. Five para substituents, Y = $OCH_3$, $CH_3$, H, Cl, and $NO_2$, are employed to investigate the substituent effect on the elimination reaction. Linear Hammett correlations are obtained in all calculations in contrast to the experimental finding.

Mn(III)-, Fe(III)-porphyrin Catalyzed Oxidation of cycloolefins (Mn(III)-, Fe(III)-porphyrin 유도체를 촉매제로 한 시클로올레핀 화합물의 산화반응)

  • Na, Hun-Gil;Park, Yu-Chul
    • Journal of the Korean Applied Science and Technology
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    • v.15 no.2
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    • pp.41-48
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    • 1998
  • The catalytic oxidations of several cycloolefins in $CH_2Cl_2$ were been investigated using Mn(III)-, Fe(III)-porphyrin complexes as a catalyst and sodium hypochlorite as a terminal oxidant. Porphyrins were $(p-CH_3O)TTP,\;(p-CH_3)TTP,$ TPP, (p-F)TPP, (p-Cl)TPP and $(F_{20})TPP$ (TPP = tetraphenylporphyrin), and olefins were cyclopentene, cyclohexene and cycloheptene. The substrate conversion yield was discussed according to the substituent effects of metalloporphyrin. The conversion yield of substrate by changing the substituent of TPP increased in the order of $p-CH_3O$ < $p-CH_3$ < H < p-F < p-Cl, which was consistent with the sequence of $4{\sigma}$ values of TPP. The conversion of cycloalkene followed the order of $C_5\;<\;C_6\;<\;C_7$.

Chiral Mesophase Derived from Achiral Polymers with Banana-Shaped Mesogens and Their Model Compounds

  • Choi, E-Joon;Kim, Eun-Chul;Kwon, Myung-Hun;Zin, Wang-Cheol;Kim, Young-Chul;Paek, Sang-Hyon
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.242-243
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    • 2006
  • In this work, we report the synthesis and characterization of azomethineester polymers that consist of banana-shaped mesogen in their backbone. Two parts of the key structure of five-ring bent-core mesogen were modified by connecting different angle of central unit (Ar), and introducing lateral substituent into the outer ring (X). The synthetic details includes (1) placing the dioxydodecamethylene unit as a flexible spacer, (2) possessing 2,3- or 2,7-naphthylene, or 1,2-phenylene connection on the central unit, and (3) introducing fluorine or chlorine substituent (X = F or Cl) into the outer phenylene unit.

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Synthesis and Mesomorphism of Polymers with Banana-Shaped Mesogens in the Main Chain

  • Choi, E-Joon;Zin, Wang-Cheol;Kim, Young-Chul;Paek, Sang-Hyon;Chien, Liang-Chy;Samulski, Edward T.
    • 한국정보디스플레이학회:학술대회논문집
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    • 2006.08a
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    • pp.171-174
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    • 2006
  • In this work, we report the synthesis and characterization of azomethine-ester polymers that consist of banana-shaped mesogen in their backbone. Two parts of the key structure of five-ring bent-core mesogen were modified by connecting different angle of central unit (Ar), and introducing lateral substituent into the outer ring (X). The synthetic details includes (1) placing the dioxydodecamethylene unit as a flexible spacer, (2) possessing 2,3- or 2,7-naphthylene, or 1,2-phenylene connection on the central unit, and (3) introducing fluorine or chlorine substituent (X = F or Cl) into the outer phenylene unit.

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SUBSTITUENT EFFECT ON THE INHIBITION OF CHLOROPHYLL FORMATION BY N-PHENYL OXADIAZOLIDINEDIONE DERIVATIVES IN CUCUMBER AND SPECULATION ON THE HERBICIDAL ACTION

  • Hwang, Kwang-Jin;Kim, Hyung-Jin;Kim, Jin-Seog
    • Journal of Photoscience
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    • v.3 no.3
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    • pp.137-140
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    • 1996
  • The inhibition of chlorophyll formation in cucumber cotyledons by N-phenyl oxadiazolidinedione derivatives Ia-u showed similar trend as their herbicidal activities. In case of oxadiazolidinedione Iq, with a propargyloxy substituent, both the highest herbicidal activity and inhibitory action(pI$_{50}$ = 6.37) were observed. The accumulation of protoporphyrin IX and cellular electrolyte leakage by oxadiazolidinedione Ia, Ik and Iq were well correlated with their inhibition of chlorophyll biosynthesis. These results suggest that the herbicidal activity of oxadiazolidine Ia-u is originated from the inhibition of chlorophyll biosynthesis.

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Kinetics and Mechanism of the Reaction of Benzyl Bromide with Thiobenzamides (벤질브로미드와 티오벤즈아미드의 반응에 있어서의 반응속도와 반응메카니즘)

  • Hong Soon-Yung;Yoh Soo-Dong
    • Journal of the Korean Chemical Society
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    • v.16 no.5
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    • pp.284-289
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    • 1972
  • Rates of the reactions of m-and p-ring-substituted thiobenzamides with benzyl bromide in acetone have been determined by an electric conductivity method. The Hammett rule has been adopted for these reactions. It has been observed that an electron-attracting substituent accelerates the reaction while an electron-donating substituent retards the reaction, and a mechanism which accounts for the observed kinetics has been postulated. The activation energies and entropies of activation for these reactions have also been calculated.

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The Wallach Rearrangement The Behaviour of Monosubstituted Azoxybenzenes in Strongly Acidic Solution (强酸溶液中에서의 Azoxybenzene 系化合物들의 轉移反應. Wallach 轉移反應)

  • Hahn, Chi-Sun
    • Journal of the Korean Chemical Society
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    • v.6 no.2
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    • pp.162-170
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    • 1962
  • The rearrangement reaction of azoxybenzenes into hydroxyazobenzenes in strongly acidic solution has been studied by an U. V. spectrophotometric method and by isolation of the rearranged compound. In all cases under investigation, it appeared that the oxygen atom in the azoxy group migrated to the unsubstituted ring, depending neither on the substituent already present in the other ring, nor on the distance between the oxygen atom and the eligible position; whereas, the position in the open ring, ortho or para, to which the oxygen migrates depends on the substituent already present in the other ring. In all compounds besides ${\alpha}$-and ${\beta}$-4-methyl azoxybenzene, the oxygen atom migrates to the para position. In the case of ${\alpha}$ and ${\beta}$-4-methylazoxybenzene, the oxygen atom migrates to the ortho position of the unsubstituted ring.

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