• Bulletin of the Korean Chemical Society
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• 제23권9호
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• pp.1241-1255
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• 2002

Series of m- and p-substituted benzyl derivatives of pyrrole, tetramethyl 1-benzyl-3a,7a-dihydroindole-2,3,3a,4-tetracarboxylate, and trimethyl 1-benzylindole-2,3,4-tricarboxylate were prepared and their 13C NMR spectra were obtained in 0.1 M solutions of chloroform-d. Both single substituent parameter and dual substituent parameter analyses were carried out to correlate the substituent chemical shifts. The ${\beta}$ carbon of the indole series showed the most profound substituent effect dependence as well as the best correlation. The results are explained by the hyperconjugation of the benzyl methylene group.

• Bulletin of the Korean Chemical Society
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• 제25권1호
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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.

• 한국응용과학기술학회지
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• 제21권1호
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• pp.24-30
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• 2004

New electroluminescent materials based on anthracene chromophore with naphthylethenyl substituent, 9,10-bis($\alpha$-naphthylethenyl)anthracene (a-BNA), as well as four kinds of its derivatives were synthesized, and luminescent properties of these materials were investigated. Electrolumineecent(EL) emission band was discussed based on their substituent structure differences. It was found that the emission band strongly depends on the molecular structure of introduced substituent. It can be tuned from 557 nm to 591 nm by changing the substituent structures. On the other hand, the anthracene chromophore with bulky substituent possessed high melting point and they gave stable films through vacuum-sublimation. The double layer EL device of ITO/TPD/emission layer/Mg:Ag was employed, and exhibited efficient orange light originating from emitting materials. EL emission with a maximum luminance was observed in the b-BNA emitting material, : maximum luminance was about 8,060 cd $m^{-2}$ at an applied voltage of 10 V and current density of 680 $mA/cm^2$. In conclusion, the electroluminescent properties also showed good difference with their substituent structure.

• Bulletin of the Korean Chemical Society
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• 제17권4호
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• pp.347-348
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• 1996

A set of substituent constants, σc+, has been widely used comparing the stability of carbocation in super acid condition. Plotting of 13C chemical shifts of cationic carbon (Δδc+) against σc+ constants yields an excellent correlation with a good correlation coefficient (r=0.999) for a cyclopentyl cation system. But these σc+ constants show poor linearity in norbornenyl cations that well known to show homoallylic stabilization in a cationic condition. We calculated the new substituent constant, σc+π, and found that the new substituent constants give an excellent correlation in π- and πσ-participating cation systems.

• Bulletin of the Korean Chemical Society
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• 제3권1호
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• pp.13-18
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• 1982

The new substituent constants $({\sigma}^{\ast})$ are calculated from the acidity constants $(pK^{\ast})$ of phenol derivatives in the excited state ($^1L_b$). These substituent constant are applied to the Hammett equations and found good correlation with $pK^{\ast}$ of 2,6-di-tert-butyl phenol, benzamide, nitroaniline, thiophenol, azobenzene, and benzoic acid derivatives. The correlation was much better than that of ground state substituent constants such as ${\sigma},\;{\sigma}^+$, and ${\sigma}^-$. From these results, the new substituent constants $({\sigma}^{\ast})$are proposed to be used for the linear free energy relationship in the $^1({\pi},{\pi}^{\ast})$ excited states of phenyl compounds.

• Archives of Pharmacal Research
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• 제23권6호
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• pp.579-584
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• 2000

To explore the effect of substituents' on phenyl motif on sulfonyl function of novel anticancer 4-phenyl-1-benzenesulfonylimidazolidinones (1), electron donating or withdrawing sub-stituents were introduced at 3 or 4-position and the analogs were tested against human lung (A549) and colon (HCT-15) cancer cell lines. Quantitative structure activity relation-ship of the 4-substituted series shows that only STERIMOL L values are well correlated. The increment of substituent's volume enhances the activity against both cell lines. The small substituent at 3-position additionally increases the activity. However naphthyl group in place of phenyl reduces the activity, Therefore the phenyl motif with sterically large substituent at 4-position and small substituent at 3-position may be important for their activity. Integration of these substituents' effects into the structural design led to discover the more potent analog, 4-phenyl-1-(N-acetylindoline-5-sulfonyl) imidazolidinone (1n).

• Bulletin of the Korean Chemical Society
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• 제35권5호
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• pp.1460-1464
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• 2014

The substituent effects on the pyridinolysis (XC5H4N) of Y-aryl ethyl chlorophosphates are investigated in acetonitrile at $35.0^{\circ}C$. The two strong ${\pi}$-acceptor substituents, X = 4-Ac and 4-CN in the X-pyridines, exhibit large positive deviations from the Hammett plots but little positive deviations from the Br$\ddot{o}$nsted plots. The substituent Y effects on the rates are really significant and the Hammett plots for substituent Y variations in the substrates invariably change from biphasic concave downwards via isokinetic at X = H to biphasic concave upwards with a break point at Y = 3-Me as the pyridine becomes less basic. These are interpreted to indicate a mechanistic change at the break point from a stepwise mechanism with a rate-limiting bond formation (${\rho}_{XY}$ = -6.26) for Y = (4-MeO, 4-Me, 3-Me) to with a rate-limiting leaving group expulsion from the intermediate (${\rho}_{XY}$ = +5.47) for Y = (4-Me, H, 3-MeO). The exceptionally large magnitudes of ${\rho}_{XY}$ values imply frontside nucleophilic attack transition state.

• Bulletin of the Korean Chemical Society
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• 제28권6호
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• pp.1031-1034
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• 2007

The R- and Z-substituent effects for the gas-phase thermal decompositions of carbamates, R2NC(=O)- OCH2CH2Z, have been investigated theoretically at B3LYP level with 6-31G(d) and 6-31++G(d,p) basis sets. Both the Z- and R-substituent effects on reactivity (ΔH≠) were well consistent with experimental results, although the R-substituent effect was underestimated theoretically. No correlations were found between activation enthalpies and reaction enthalpies. The substituent effects on reactivity seemed to be complicated at a glance, but were understandable by concurrent electronic and steric factors. Variations of bond lengths at TS structures were well correlated with the Taft's σ* values and the TS structures became tighter as the Zsubstituent became a stronger electron-acceptor (δσ* > 0). However the effects of R-substituents on the TS structures were much smaller when compared to those of Z-substituents.

• 대한화학회지
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• 제19권2호
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• pp.116-122
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• 1975

Benzyl arenesulfonate와 피리딘과의 아세톤 용매중에서의 反應速度를 測定하였다. Benzyl arenesulfonate의 離脫基의 치환기효과는 p-MeO基 및 $p-NO_2$기를 除外하고는 Hammett 式에 잘 적용되었으며, 전자끄는기는 반응속도를 증가시켰다. 離脫基의 치환효과는 벤질炭素에 아민이 親核的으로 공격하여 전이상태에서 치환기의 電子끄는 능력이 C-N 結合의 形成과 C-O結合의 쪼개짐에 변화를 주고 있다는 사실로서도 설명이 되어진다. 치환기효과는 benzyl p-bromobenzeneslfonate가 benzyl p-nitrobenzenesulfonate보다 N-C結合이 tight 한 전이상태의 구조를 가지고 있음을 말해주며 이는 結合의 형성과 쪼개짐에 있어 Thornton의 $S_N2$전이상태 구조의 예상과도 잘 符合된다.

• Bulletin of the Korean Chemical Society
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• 제2권1호
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• pp.12-16
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• 1981

Alkyl and alkenyl substituent effects on nonbonded interactions of hexatriene were examined using CNDO/2 method. The results showed that: (1) rapid rate of thermal electrocyclization of 3-vinyl hexa-1, 3, 5-triene is due to increased overlap population between atom pair reacting resulting from strong electron repelling interaction of vinly group on the triene moiety; (2) stability of a conformer is determined by additive effect of composite ${\pi}$ structures; (3) a substituent on positions 2 and 3 increases the HOMO AO coefficient of sites 1 and 4 considerably and activates interactions with these sites.