• Title/Summary/Keyword: Substituent

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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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Substituent Effects on the Binding Energies of Benzyl Alcohol-H2O Clusters: Ab initio Study

  • Ahn, Doo-Sik;Lee, Sung-Yul
    • Bulletin of the Korean Chemical Society
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    • v.23 no.2
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    • pp.262-266
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    • 2002
  • Computations are presented for the ortho- and para-substituted benzyl alcohol-$H_2O$ clusters. A variety of conformers are predicted, and their relative energies are compared. Binding energies of the clusters are computed, and detailed analysis is presented on the effects of substitution on the strength of the hydrogen bond in the clusters. F- and $NH_2-$ substituted clusters are studied to analyze the effects of electron-withdrawing and electron-pushing groups. In para-substituted clusters, the inductive effects are dominant, affecting the binding energies in opposite way depending on whether the hydroxyl group is proton-donating or -accepting. For ortho-substituted clusters, more direct involvement of the substituting group and the resulting geometry change of the hydrogen bond should be invoked to elucidate complicated pattern of the binding energy of the clusters.

Investigation of the Annealing Time Effects on the Properties of Sputtered ZnO:Al Thin Films

  • Kim, Deok Kyu;Kim, Hong Bae
    • Applied Science and Convergence Technology
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    • v.23 no.6
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    • pp.366-370
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    • 2014
  • ZnO:Al transparent conductive films were deposited on glass substrates by RF magnetron sputtering technique and annealed by rapid thermal annealing system. The influence of annealing time on the structural, electrical, and optical properties of ZnO:Al thin films was investigated by atomic force microscopy, X-ray diffraction, Hall method and optical transmission spectroscopy. As the annealing time increases from 0 to 5 min, the crystallinity is improved, the root main square surface roughness is decreased and the sheet resistance is decreased. The lowest sheet resistance of ZnO:Al thin film is 90 ohm/sq. The reduction of sheet resistance is caused by increasing carrier concentration due to substituent Al ion. All films are transparent up to 80% in the visible wavelength range and the adsorption edge is a blue-shift due to Burstein-Moss effect with increasing annealing time.

Synthesis of Red Disperse Dyes with Various Diazo Components and Coloration of Unmodified Pure Polypropylene Fibers

  • Kim, Tae-Kyeong;Jang, Kyung-Jin;Jeon, Seon-Hee
    • Textile Coloration and Finishing
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    • v.22 no.1
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    • pp.1-7
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    • 2010
  • The five new red disperse dyes for unmodified pure polypropylene fibers were synthesized. As a coupling component, a di-n-hexyl substituent was used in common, while various substituents were used for the diazo component. The dye having electron donating group at diazo component showed hypsochromic shift compared to the unsubstituted dye, while the dyes having electron withdrawing groups showed bathochromic shift. Owing to their extreme hydrophobicity caused by the di-n-hexyl substituent, all dyes exhibited very high affinity toward pure polypropylene fibers. Fastness to washing was very good for all dyes and fastness to light was good except two purplish red dyes.

Synthesis of Novel Morpholine Appended Crystal violet lactone Derivatives and an Investigation of Their Thermochromic Behavior

  • Kim, Myeong Jin;Muthukumar, Palanisamy;Angupillai, Satheshkumar;Son, Young-A
    • Textile Coloration and Finishing
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    • v.30 no.1
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    • pp.1-8
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    • 2018
  • In the present study, three morpholine substituted crystal violet lactone (CVL) have been synthesized to monitor the thermochromic property. This work is explaining the role of substituent on the lactone ring. The methyl substituents induced greater chromic effects than the chloro substituents. Furthermore, the three-component mixtures that contained CVL, bisphenol-A, and methyl stearate were used to analyse the thermochromic effect of the CVLs as bulk samples with various temperature. The thermochromic properties of the CVLs were evaluated using solid-state UV-Vis and FT-IR spectroscopic techniques. Finally, one of the synthesized CVL has been successfully converted into the form of a test paper similar to pH paper for use as thermal indicators.

The Fluorescent Effects on the N-Substituents of Polyarylenevinylenes Having 1,2-Diphenylmaleimide Moieties

  • Lee, Jun-Kyu;Yang, Nam-Choul;Park, Ho-Wook;Suh, Dong-Hack
    • Macromolecular Research
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    • v.11 no.2
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    • pp.92-97
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    • 2003
  • Model compounds and polymers having N-substituted 1,2-diphenylmaleimide moieties were synthesized and characterized by NMR, IR, UV, and fluorescence spectroscopy. The fluorescence intensity could be controlled by N-substituents of model compounds and polymers. As the structure of an N-substituent of them was bulkier, or the electron density of an N-substituent was denser, the photoluminescence intensity was increased. All the compounds showed greenish yellow photoluminescence with the maximum intensity between 510 and 537 nm. From quantum efficiency data of the model compounds and the polymers, the fluorescence intensity of the polymer 11 was higher than that of the model compound 4.

Effect of Substituents on the Formation of 2-Substituted Phenyl-5-phenyltetrazole (2-Substituted Phenyl-5-phenyltetrazole 生成에 있어서의 置換基의 影響에 關하여)

  • Hong, Soon-Yong
    • Journal of the Korean Chemical Society
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    • v.11 no.4
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    • pp.170-172
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    • 1967
  • 2-Phenyl-5-substituted phenyltetrazole and 2-substituted phenyl-5-phenyltetrazole were prepared from the corresponding hydrazone and phenyl azide with 2-methoxyethanol and metallic sodium as reaction medium at 110~115 $^{\circ}C$. At this reaction condition, however, the preparation of 2-substituted phenyl-5-phenyltetrazoles with substituents of relatively high Hammett substituent constant was unsuccessful. Surprisingly it was found that the solvent molecule was exchanged with substituent during the reaction when tried to obtain 2-m-fluorophenyl-5-phenyltetrazole using benzaldehyde m-fluorophenylhydrazone as starting material. Also disscussed the effect of electronic nature of substituents on the formation of 2,5-diphenyltetrazole derivatives.

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Kinetic and Theoretical Consideration of 3,4- and 3,5-Dimethoxybenzoyl Chlorides Solvolyses

  • Park, Kyoung-Ho;Kevill, Dennis N.
    • Bulletin of the Korean Chemical Society
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    • v.34 no.10
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    • pp.2989-2994
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    • 2013
  • The solvolysis rate constants of 3,4- (1) and 3,5-dimethoxybenzoyl (2) chlorides were measured in various pure and binary solvents at $25.0^{\circ}C$, and studied by application of the extended Grunwald-Winstein (G-W) equation, kinetic solvent isotope effect in methanolysis and activation parameters. The solvolysis of 1 was interpreted as the unimolecular pathway due to a predominant resonance effect from para-methoxy substituent like 4-methoxybenzoyl chloride (3), while that of 2 was evaluated as the dual mechanism, with unimolecular or bimolecular reaction pathway according to the character of solvent systems (high electrophilic/nucleophilic) chosen, caused by the inductive effect by two meta-methoxy substituents, no resonance one. In the solvolyses of 1 and 2 with two $-OCH_3$ groups, the resonance effect of para-methoxy substituent is more important to decide the mechanism than the inductive effect with other corresponding evidences.

Solvolysis of Benzyl Arenesulfonates in Acetone-Water Mixture (IV) (아세톤 용매에서의 Benzyl Arenesulfonate 의 가용매 분해 (제4보))

  • Lee, Woo Bung;Yoh, Soo Dong
    • Journal of the Korean Chemical Society
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    • v.20 no.5
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    • pp.391-397
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    • 1976
  • Substituent effects of leaving group in benzylarenesulfonates solvolysis have been carried out in 10∼50% water-acetone mixtures by electric conductivity method. Results of solvent effects, substituent effects and variable rate difference of water contents, show that $S_N1$ character almost predominates through the substituents, though p-MeO favors more or less $S_N2$ character in low water contents.

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Selective Reduction of Organic Compounds with Al-Trifluoromethanesulfonyldiisobutylalane. Comparison of Its Reactivity with Al-Methanesulfonyldiisobutylalane

  • Cha, Jin-Soon
    • Bulletin of the Korean Chemical Society
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    • v.32 no.1
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    • pp.219-224
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    • 2011
  • The new MPV type reagent, Al-trifluoromethanesulfonyldiisobutylalane ($DIBAO_3SCF_3$), has been prepared and its reducing characteristics in the reduction of selected organic compounds containing representative functional groups have been examined, and compared its reactivity with that of Al-methanesulfonyldiisobutylalane ($DIBAO_3SCH_3$) in order to understand the fluorine-substituent effect on its reactivity. In general, the reactivity of $DIBAO_3SCF_3$ appears to be much higher than that of $DIBAO_3SCH_3$, apparently due to the acidity increase by the electron-withdrawing fluorine-substituent. The reagent reduced aldehydes and ketones readily, but showed a perfect selectivity in the reduction of $\alpha,\beta$-unsaturated aldehydes and ketones to produce the corresponding allylic alcohols in an absolutely 100% purity. In addition, the reagent achieved the regioselective cleavage of phenyl- or/and alkyl-substituted epoxides to the less substituted alcohols in a perfect regioselectivity. Moreover, the reagent also showed an high stereoselectivity in the reduction of substituted cycloalkanones to produce the thermodynamically more stable alcohol epimers exclusively.