• Bulletin of the Korean Chemical Society
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• v.2 no.4
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• pp.125-129
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• 1981

The addition reactions of cysteine without blocking amino and carboxyl groups to substituted and unsubstituted ${\beta}$-nitro-styrene derivatives were investigated. ${\beta}$-Nitrostyrene(1a), p-methyl-${\beta}$-nitrostyrene(1b), 3,4,5-trimethoxy-$[\beta}$ -nitrostyrene(1c), $[\varpi}$-3,4-methylenedioxy-${\beta}$ -nitrostyrene(1d), o-, m- and p-chloro-${\beta}$ -nitrostyrene (1e, 1f, 1g) and o-, m- and p-methoxy-${\beta}$-nitrostyrene (1h, 1i, 1j) easily undergo addition reactions with cysteine to form S-(2-nitro-1-phenylethyl)-L-cysteine(3a), S-[2-nitro-1-(p-methyl)phenyl-ethyl]-L-cysteine(3b), S-[2-nitro-1-(3',4',5'-trimethoxy) phenylethyl]-L-cysteine(3c), S-[2-nitro-1-($[\vatpi}$ -3',4'-methylenedioxy)phenylethyl]-L-cysteine(3d), S-[2-nitro-1-(o-chloro)phenylethyl]-L-cysteine(3e), S-[2-nitro-1-(m-chloro)-phenylethyl]-L-cysteine(3f), S-[2-nitro-1-(p-chloro)phenylethyl]-L-cysteine(3g), S-[2-nitro-1-(o-methoxy)phenylethyl]-L-cysteine(3h), S-[2-nitro-1-(m-methoxy)phenylethyl]-L-cysteine(3i) and S-[2-nitro-1-(p-methoxy)phenylethyl]-L-cysteine(3j), respectively. The structure of adducts were confirmed by means of UV-spectrum, IR-spectrum, molecular weight measurement and elemental analysis. The various factors effecting the yield of cysteine adducts to ${\beta}$-nitrostyrene derivatives were also studied.

• Journal of the Korean Chemical Society
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• v.24 no.2
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• pp.115-120
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• 1980

A kinetic study of the methanolysis of t-butylbromide and benzoylchloride in methanol-acetonitrile mixtures is reported. First order rate constants for the methanolysis of t-butyl bromide show maximum at $X_{MeOH}$=0.75∼0.9 and 25∼$50^{\circ}C$. Apparent second order rate constants for the methanolysis of benzoylchloride also show maximum at $X_{MeOH}$= 0.6∼0.95 and 12∼$26^{\circ}C$. The maximum rate is ascribed to the solvent structure change; the addition of acetonitrile to methanol perturbs the methanol structure increasing the free methanol molecules available to stabilize the transition state for the methanolysis of t-butylbromide and benzoylchloride. It has been shown that methanol acts as nucleophilic and electrophilic catalyst upon methanolysis of t-butylbromide and as electrophilic catalyst upon methanolysis of benzoylchloride.

• Bulletin of the Korean Chemical Society
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• v.24 no.5
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• pp.583-592
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• 2003

The gas phase identity nucleophilic substitution reactions of halide anions (X = F, Cl, Br) with cyclopentadienyl halides (1) are investigated at the B3LYP/6-311+G**, MP2/6-311+G** and G2(+)MP2 levels involving five reaction pathways: σ-attack $S_N2$, β-$S_N$2'-syn, β-$S_N$2'-anti, γ-$S_N$2'-syn and γ-$S_N$2'-anti paths. In addition, the halide exchange reactions at the saturated analogue, cyclopentyl halides (2), and the monohapto circumambulatory halide rearrangements in 1 are also studied at the same three levels of theory. In the σ-attack $S_N2$ transition state for 1 weak positive charge develops in the ring with X = F while negative charge develops with X = Cl and Br leading to a higher energy barrier with X = F but to lower energy barriers with X = Cl and Br than for the corresponding reactions of 2. The π-attack β-$S_N$2' transition states are stabilized by the strong $n_C-{\pi}^{*}_{C=C}$ charge transfer interactions, whereas the π-attack γ-$S_N$2' transition states are stabilized by the strong $n_C-{\sigma}^{*}_{C-X}$ interactions. For all types of reaction paths, the energy barriers are lower with X = F than Cl and Br due to the greater bond energy gain in the partial C-X bond formation with X = F. The β-$S_N$2' paths are favored over the γ-$S_N$2' paths only with X = F and the reverse holds with X = Cl and Br. The σ-attack $S_N2$ reaction provides the lowest energy barrier with X = Cl and Br, but that with X = F is the highest energy barrier path. Activation energies for the circumambulatory rearrangement processes are much higher (by more than 18 kcal $mol^{-1}$) than those for the corresponding $S_N2$ reaction path. Overall the gas-phase halide exchanges are predicted to proceed by the σ-attack $S_N2$ path with X = Cl and Br but by the β-$S_N$2'-anti path with X = F. The barriers to the gas-phase halide exchanges increase in the order X = F < Br < Cl, which is the same as that found for the gas-phase identity methyl transfer reactions.

• Bulletin of the Korean Chemical Society
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• v.35 no.9
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• pp.2673-2678
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• 2014

The detailed mechanisms of the efficient $\small{L}$-proline and pyrrolidine catalyzed transamidation of acetamide with benzylamine have been investigated using density functional theory (DFT) calculations. Our calculated results show: (1) the mechanisms of two catalytic cycle reactions are similar. However, the rate-determining steps of their reactions are different for the whole catalytic process. One is the intramolecular nucleophilic addition reaction of 1-COM, the other is hydrolysis reaction of 2-C. (2) COOH group of $\small{L}$-proline is essential for efficient transamidation. The computational results are in good agreement with the experiment finding and mechanism resported by Rao et al. for $\small{L}$-proline-catalyzed synthesis of amidesin good to excellent yields.

• Journal of the Korean Chemical Society
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• v.28 no.2
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• pp.135-142
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• 1984

New type dioxygen bridged complexes of palladium were prepared by using $KO_2$ as a source of superoxide ion $(O_2^-)$. The method is completely different from the traditional one which has adopted the oxidative addition of molecular oxygen to transition metal complexes in low valency. It was suggested that the reaction to prepare the dioxygen complexes proceeded via nucleophilic displacement followed by electron transfer reaction. Five new type dioxygen complexes having ${\pi}$-allyl ligand were prepared and characterized by the application of the reaction of $O_2^-$.

• Journal of the Korean Applied Science and Technology
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• v.15 no.2
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• pp.49-57
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• 1998

This study is to develop a new synthetic method for the nitroarenes via non-electrophilic substitution. Direct nitration at the C-1 position of isoquinoline has never been reported and substitution in isoquinoline under the normal nitration condition occurs at C-5 and C-8. We have demonstrated a facile one-step sythetic method for the nitration of isoquinolines at the C-1 position, which involves the electrophilic attack of a $DMSO-Ac_2O$ complex, followed by nucleophilic addition of nitrate ion to this intermediate. Since the reaction is simple and mild, this method has preparative merit since 1-nitroisoquinolines are not readily accessible by other methods. Application to the synthesis of poly nitroarenes from the corresponding anilines was also described.

• Applied Chemistry for Engineering
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• v.3 no.1
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• pp.64-71
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• 1992

New type dioxygen bridged complexes of palladium were prepared by using $KO_2$ as a source of superoxide ion($O_2{^-}$). The method is completely different from the traditional one which has adopted the oxidative addition of molecular oxygen to prepare the dioxygen complexes. This reaction proceeds via nucleophilic displacement followed by electron transfer reaction. Three new type dioxygen complexes of palladium having amine ligands were prepared and characterized by the application of the reaction of $O_2{^-}$.

• 한국정보디스플레이학회:학술대회논문집
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• 2002.08a
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• pp.724-727
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• 2002

2,7-dibromo-9, 9-dialkyl-substituted-fluorene derivatives were prepared by the alkylation of 2,7-dibromofluorene with various alkyl groups under two-phase phase transfer catalysis (PTC) conditions, as monomers for synthesizing poly(dialkylfluorene)s. Tetra-nbutylammonium hydrogen sulfate (TBAHS) was used as a phase transfer catalyst to enhance nucleophilic substitution. In addition, NaOH in water (25M) was used as a base to generate anions. Compared to conventional alkylation using butyllithium(BuLi), the reaction using the PTC technique attained high selectivity and substantial conversion of reactants, due to the enhanced reaction rate, while the reaction was carried out under moderate conditions. An approximately 90% yield was obtained from the reaction and the reaction time was remarkably reduced. 2,7-dibromo-9,9-dihexyl-fluorene, 2,7-dibromo-9,9-dioctyl-fluorene, and 2,7-dibromo-9,9-di(2-ethylhexyl)-fluorene were effectively synthesized by phase transfer catalytic reaction.

• Natural Product Sciences
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• v.12 no.2
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• pp.94-100
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• 2006

The essential oil (EC-oil) obtained from the buds of Eugenia caryophyllata (Myrtaceae) was examined for its free radical-scavenging activity, cytotoxicity, and in vivo toxicity. To find the xenobiotic properties of EC-oil, serum thiobarbituric acid reactive substances (TBARS) level and hepatic drug-metabolizing enzyme activities were measured. It was found that EC-oil displayed xenobiotic properties like bromobenzene. The cytotoxicities of eugenol and of the EC-oil were greatly attenuated by the sulfhydryl-containing N-acetyl-L-cysteine (NAC), suggesting that eugenol was susceptible to nucleophilic sulfhydryl. In addition, eugenol also showed potent free radical-scavenging activity in the 1,1-diphenyl-2-picrylhydrazyl (DPPH) assay. Moreover, methyleugenol considerably exhibited less cytotoxicity and less potent free radical-scavenging activity than eugenol, and the cell viability of the methyleugenol was more increased with NAC treatment than the eugenol. These results indicate that the phenolic OH in eugenol may play a crucial role in both cytotoxicity and free radical-scavenging activity. The fashion on oxidative stress and hepatic drug-metabolizing enzyme activities of eugenol resembled those of bromobenznene.

• Bulletin of the Korean Chemical Society
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• v.29 no.5
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• pp.1018-1024
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• 2008

Photolysis of 2-(pentamethyldisilanyloxy)phenylpentamethyldisilane 1 in methanol provides five photoproducts 3, 4, 5, 6, and 7. Compounds 3 and 4 were probably formed from the methanol addition reactions of silene intermediate 2 and the formation of 5, 6, and 7 can best be explained by the nucleophilic attack of methanol to silicon atom in pentamethyldisilanyloxy or pentamethyldisilanyl group of the photoexcited state of 1. Irradiation of 1 in n-hexane gives a photoproduct 6 via silyl radical intermediate 8 and a novel intramolecular cyclization photoproduct 11 via silene 9 and silyl radical intermediate 10. Irradiation of 1 in deaerated methylene chloride in the presence of acetone affords a novel photoproduct 11 and phenol 7 but the expected photoproducts from the reaction of the silene intermediate with acetone were not obtained.