• Bulletin of the Korean Chemical Society
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• v.25 no.10
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• pp.1559-1563
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• 2004

The topoisomerase II poisoning effect of certain protoberberine alkaloids is associated with anti-cancer activity. Structure-activity relationships of protoberberine analogues substituted on the ring protons reveal that substitution at the C19 position is an important determinant of biological activity. In this study, the effects of substituent modification at the C19 position on the interaction of protoberberines with DNA are determined using UV and NMR spectroscopy. The line broadening effect on aliphatic resonances, chemical shift changes of the imino protons of HP14 upon berberine and berberrubine binding to HP14, and the rate of the exchange process between protoberberine analogs bound indicate that berberrubine binds HP14 more specifically than berberine. In addition, the free HP14 is altered by the substituent at the 19-position. UV spectra of berberrubine have shown a hypochromic effect together with a slight red shift, which are usually regarded as characteristics of DNA intercalation. These results are consistent with our previous report that the berberrubine is partially intercalated with HP14 with molar ratio 1 : 1, whereas a non-specific interaction is predominant between the berberine and HP14.

• Journal of the Korean Applied Science and Technology
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• v.8 no.2
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• pp.175-181
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• 1991

The kinetics of the addition of 1-benzylindole-3-(p-substituted) acetophenone derivatives was investigated by ultraviolet spectrophotometery in 30% dioxane -$H_2O\;at\;25^{\circ}C$. A rate equation which can be applied over wide pH range was obtained. The Substituent effects on 1-benzylindole-3-(p-substituted) acetophenone derivatives were studied, and addition were facilitated by electron attracting groups. On the base of the rate equation, substituent effect, and general base effect the plausible addition mechanism was proposed : Below pH 3.0, only neutral thiourea molecule was added to the carbon-carbon double bond, and in the range of pH 0.0${\sim}$14.0, netural thiourea molecule and thiourea anion competitively attacted the double bond. By contrast, above pH 10.0, the reaction was dependent upon only the addition of thiourea anion.

• Archives of Pharmacal Research
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• v.12 no.2
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• pp.63-67
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• 1989

The various esters of 20R and 20S-dihydroprednisolonic acid were prepared and evaluated for their local and topical anti-inflammatory activities in rats, including systemic effects. It was demonstrated that the size of the substituent at C-21 and configurational arrangement at C-20 have significant effects on local and topical activity. It was also found that all the derivatives did not show systemic effects as accessed by thymus weight and adrenal weight at the dose level used, while prednisolone showed profound effects on thymus weight.

• Journal of Photoscience
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• v.11 no.32
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• pp.75-76
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• 2004

${\alpha}$,${\alpha}$-Dibromovalerophenone and ${\alpha}$,${\alpha}$-dichlorovalerophenone were prepared and their photochemical behaviors were investigated. The former gives C-Br cleavage products and the latter gives mainly the Yang photocyclization products upon irradiation. The reactivity of the chlorine substituted ketone turned out to be quite different from that of ${\alpha}$,${\alpha}$-difluorovalerophenone which gives both the cyclization and elimination products from the 1,4-biradical intermediate.

• Journal of the Korean Chemical Society
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• v.8 no.1
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• pp.15-19
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• 1964

Basicities of nine dimethylanilines have been determined in 50, 70, and 90 volume % ethanol, at $25^{\circ},\;30^{\circ},\;35^{\circ},\;and\;40^{\circ}C$. Temperature coefficients were found to be independent of solvent composition, while they showed a linear correlation with basicities of the compounds. Thermodynamic parameters obtained have been used in the discussion of substituent and solvent effects in conjunction with the general equation derived in the preceding papers.

• Bulletin of the Korean Chemical Society
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• v.28 no.5
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• pp.851-854
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• 2007

• Bulletin of the Korean Chemical Society
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• v.10 no.1
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• pp.47-50
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• 1989

The methanolysis reactions of phenylacetyl chlorides have been investigated in methanol-acetonitrile mixtures at temperatures ranging - $15.0-0.0^{\circ}C.$ Substituent and solvent effects on the rate supported an associative $S_N2$ mechanism for the solvolysis. Activation parameters indicated that the reaction is entropy controlled, while the a/s ratios of the Taft's solvactochromic correlation proved to be remarkably constant with a typical value of 0.50 that is consistent for the reactions proceeding by a typical $S_N2$ path.

• Bulletin of the Korean Chemical Society
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• v.5 no.6
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• pp.226-230
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• 1984

LIS's of cis and trans-methyl-2-phenylcyclopropanecarboxylate, cis and trans-t-butyl-2-phenylcyclopropanecarboxylate, cis and trans-N,N-dimethylcyclopropanecarboxamide, trans-2-phenylcyclopropyl methyl ketone and trans-2-phenylcyclopropyl t-butyl ketone have been studied. The LIS's hold the McConnell-Robertson relation and are mainly influenced by the steric effect. LIS's of trans isomers are larger than those of cis isomers. In trans isomers, the LIS's decrease in the following order: methyl ketone > methyl ester > N,N-dimethyl amide > t-butyl ketone${\sim}$t-butyl ester.

• Bulletin of the Korean Chemical Society
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• v.9 no.5
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• pp.311-317
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• 1988

The surface-enhanced Raman scattering(SERS) of methoxybenzonitrile in a silver sol was investigated. All of ortho-, meta-, and para-substituted benzonitriles were found to adsorb on the silver surface via the nitrogen lone pair electrons. The benzene ring of meta derivative seemed likely to stand perpendicular to the silver surface, while the benzene rings of both otho and para derivatives assumed tilted stances with respect to the surface. The SERS technique appeared to be a useful means to study the substituent electronic effects.

• Bulletin of the Korean Chemical Society
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• v.32 no.11
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• pp.3880-3886
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• 2011

The nucleophilic substitution reactions of diisopropyl thiophophinic chloride (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $65.0^{\circ}C$. The anilinolysis rate of 3 is rather slow to be rationalized by the conventional stereoelectronic effects. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D$ = 0.80-0.96). The anilinolyses of ten P=S systems in MeCN are reviewed on the basis of DKIEs and selectivity parameters to obtain systematic information on the DKIEs and mechanism for thiophosphoryl transfer reactions. The steric effects of the two ligands on reactivity, DKIEs, mechanism, and substituent effects of the nucleophile (X) on the DKIEs are discussed.