• Journal of the Korean Chemical Society
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• v.20 no.3
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• pp.212-220
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• 1976

The photocyclization of 1,1'-dicycloalkenyls (1,1'-dicyclohexenyl, 1,1'-dicyclopentenyl, 1,1'-dicycloheptenyl and 1,1'-dicyclooctenyl) is studied. Irradiation at liquid nitrogen temperature does not show trans double bond band in IR spectra. Even though naphthalene and pyrene fluorescence are quenched very efficiently by 1, 1'-dicycloalkenyls, no or trace amount of cyclobutenes are accompanied. When acetophenone or benzophenone is used, cyclobutene is obtained only from 1,1'-dicyclohexenyls, 1,1'-dicycloheptenyl giving some adducts. Naphthalene and pyrene sensitizes adduct formation but not cyclization. From above observations, it is concluded that photocyclization occurs from the planar s-cis triplet state rather than twisted triplet, singlet excited state or vibrationally excited ground state in sensitized photocyclization of 1,1'-dicycloalkenyls.

• Journal of Photoscience
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• v.10 no.1
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• pp.1-7
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• 2003

The results of recent work on the dye-sensitized photooxygenation of sulfides is discussed. In the case of dialkyl sulfides, the weakly bonded adduct initially formed with singlet oxygen (the persulfoxide) decays unproductively unless protonation by an acid (an alcohol or a carboxylic acid) facilitates its conversion to the sulfoxide. The effect is proportional to the strength of the acid (eg., less than 0.1 % chloroacetic acid in benzene is sufficient for maximal efficiency) and corresponds to general acid catalysis, suggesting that protonation of the persulfoxide occurs. On the other hand, with sulfides possessing an activated hydrogen in ${\alpha}$ position (eg., benzyl and allyl sulfides), hydrogen transfer becomes an efficient process in aprotic media and yields a S-hydroperoxysulfoniumm ylide, possibly arising from a conformation of the persulfoxide that is different from the one protonated in the presence of acids. Calculations on some substituted sulfides support this hypothesis. This process, which leads to C-S bond fragmentation with formation of an aldehyde, may be viewed as a general method for the preparation of aryl and heteroaryl aldehydes. In this effort, mechanistic studies offered new hints on the structure of the intermediate persulfoxide.

• Proceedings of the PSK Conference
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• 2001.04a
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• pp.100.2-101
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• 2001

• BMB Reports
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• v.28 no.1
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• pp.1-5
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• 1995

The effect of 6-sulfooxymethyl benzo(a)pyrene (SMBP) on conformational changes of calf thymus DNA was investigated. As SMBP is a strong electrophile, the covalent binding of SMBP to DNA should distort three dimensional conformation of DNA at the binding sites. A formaldehyde-unwinding methods were used to determine the rate of DNA denaturation. The increase in absorbance at 251nm was detected by addition of formaldehyde following treatment with SMBP. SMBP changed supercoiled DNA to relaxed and linear DNA as determined by electrophoresis, which was similar to the change in DNA due to in vitro treatment with benzo(a) pyrene diol epoxide. Treatment with SMBP completely denatured DNA under alkaline conditions. However, DNA was nicked or partially denatured under neutral condition. The absorption band of DNA was increased by the treatment with SMBP in V79 cells, which may be explained by the formation of stabilized SMBP-DNA adduct.

• Journal of Photoscience
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• v.1 no.2
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• pp.89-94
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• 1994

The reaction of decaborane with trimethylsilyldiazomethane gives 1, 2-bis (trimethylsilyl)-1, 2-carba-closo-dodecaborane(12). This compound is similar to the icosahedral cage structure of o-carborane. This formation of the first adduct proceeds through deprotonation of the acidic center of B(9) and B(6) by intermolecular attack by the lone electron pair of the carbene, : CHSiMe$_3$. The yield of product is influenced by irradiation and thermal conditions.

• Proceedings of the Korean Society of Toxicology Conference
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• 2001.10a
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• pp.41-42
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• 2001

The chemopreventive effect of tea against 2-amino-l-methyl-6-phenylimidazo［4, 5-b ］pyridine (PhIP)-DNA adduct formation and its mechanism were studied. Rats were exposed to freshly prepared aqueous extracts of green tea (3% w/v) as the sole source of drinking water for 10 days prior to administration with a single dose of PhIP (10 mg/kg body wt) by oral gavage. PhIP-DNA adducts in the liver, colon, heart, and lung were measured using the $^{32}$ P-postlabelling technique.(omitted)

• Bulletin of the Korean Chemical Society
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• v.8 no.6
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• pp.444-449
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• 1987

Solvent effects on gas phase reactions of methoxide ion with substituted ethylenes, $CH_2$ = CHR where R = CN, CHO and $NO_2$, are investigated theoretically using the AM1 method. Results show that the methoxide approaches in-plane in all reactions, but subsequently rotate out-of-plane to form tetrahedral complexes in additon reactions. All reactions of a bare methoxide are found to be exothermic, the exothermicity being the greatest in the ${\beta}$-addition, in which the excess energy is forced to be contained within the ${\beta}$-adduct rendering extreme instability. However a part of the excess energy can be removed by a solvate molecule giving a stable complex prior to the product formation. The hydride transfer processes were found to be unfavorable due to the high activation barriers. The ${\alpha}-H^+$ abstraction process from acrylonitrile becomes endothermic as a result of monosolvation of the methoxide, in agreement with experimental results.

• Bulletin of the Korean Chemical Society
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• v.3 no.4
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• pp.157-162
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• 1982

9-Methylenethioxanthene(6) was synthesized and for the first time good mp and spectral data were taken. Reaction of (6) with thioxanthylium ion (1) in acetonitrile led to a carbenium addition adduct (8) which then was either attacked by a variety of nucleophiles subsequently added or underwent deprotonation reaction to give an olefin (13). From these reactions, was obtained bis-9,9'-thioxanthenylmethane (2). These results indicate clearly that (2) can be formed via (8) by accepting hydride. Isolation of (2) and (6) from the reaction of (1) with 9-methylthioxanthylium ion (18) also supports the involvement of (8) in the reaction of (1) with dimethylmercury. However, addition of thioxanthene radical (4) to (6) has not been ruled out.

• Bulletin of the Korean Chemical Society
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• v.32 no.8
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• pp.2711-2716
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• 2011

para-Substituted phenoxide derivatives of Pd(II) having an NCN pincer, Pd(NCN)($OC_6H_4$-p-X) (NCN = 2,6-$(CH_2NMe_2)_2C_6H_3$; X = $NO_2$ (1), Me (2)) were prepared by the reaction of Pd(NCN)($OSO_2CF_3$) with equi-molar amount of $NaOC_6H_4$-p-X. Treatment of Pd(NCN)($OSO_2CF_3$) with an excess amount of $NaOC_6H_4$-p-Me affords the hydrogen-bonding adduct complex 3 ($2{\cdot}HOC_6H_4$-p-Me). Complex 3 can also be obtained from benzene solution of 2 in the presence of free $HOC_6H_4$-p-Me. Complex 1 does not undergo adduct formation with $HOC_6H_4-p-NO_2$ neither from metathesis reaction of Pd(NCN)($OSO_2CF_3$) with an excess amount of $NaOC_6H_4-p-NO_2$ nor from treatment of 1 with free $HOC_6H_4-p-NO_2$. Complex 3 undergoes fast exchange of the coordinated p-cresolate with the hydrogen-bonding p-cresol. Complex 2 undergoes ${\sigma}$-ligand exchange reaction with $HOC_6H_4-p-NO_2$ to give 1. The exchange reaction, however, is irreversible as readily anticipated from their respective $pK_a$ values of the phenol derivatives. Reaction of 2 with diphenyliodium chloride quantitatively produced Pd(NCN)Cl and PhI along with liberation of O-phenylated product $PhOC_6H_4$-p-Me which was identified by GC/MS spectroscopy.

• Bulletin of the Korean Chemical Society
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• v.27 no.5
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• pp.718-724
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• 2006

The heterogeneous association behaviour of various concentration binary mixtures of mono alkyl ethers of ethylene glycol with ethyl alcohol were investigated by dielectric measurement in benzene solutions over the entire concentration range at 25 ${^{\circ}C}$. The values of static dielectric constant $\epsilon_0$ of the mixtures were measured at 1 MHz using a four terminal dielectric liquid test fixture and precision LCR meter. The high frequency limiting dielectric constant $\epsilon_\infty$ values were determined by measurement of refractive index $n_D$ ($\epsilon_\infty\;=\;n_D\;^2$). The measured values of $\epsilon_0$ and $\epsilon_\infty$ were used to evaluate the values of excess dielectric constant $\epsilon^E$, effective Kirkwood correlation factor $g^{eff}$ and corrective correlation factor $g_f$ of the binary polar mixtures to obtain qualitative and quantitative information about the H-bond complex formation. The non-linear behaviour of the observed $\epsilon_0$ values of the polar molecules and their mixtures in benzene solvent confirms the variation in the associated structures with change in polar mixture constituents concentration and also by dilution in non-polar solvents. Appearance of the maximum in $\epsilon^E$ values at different concentration of the polar mixtures suggest the formation of stable adduct complex, which depends on the molecular size of the mono alkyl ethers of ethylene glycol. Further, the observed $\epsilon^E$ < 0 also confirms the heterogeneous H-bond complex formation reduces the effective number of dipoles in these polar binary mixtures. In benzene solutions these polar molecules shows the maximum reduce in effective number of dipoles at 50 percent dilutions. But ethyl alcohol rich binary polar mixtures in benzene solvent show the maximum reduce in effective number of dipoles in benzene rich solutions.