• Bulletin of the Korean Chemical Society
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• v.20 no.8
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• pp.935-938
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• 1999

Reactivity and reaction mechanism for the reactions of 1,1'-(azodicarbonyl) dipiperidine with triphenylphosphines are investigated using kinetic method. The cation radical, Ph3P and the anion radical, -N-N - are produced during the course of the reaction. The cation radical is formed by the transfer of an electron from phosphorus to the nitrogen atom. The anion radical is formed by the addition of the one electron to the azo rad-ical. The rate constants are decreased by electron withdrawing groups while they are increased by electron donating groups present in triphenylphosphine. The electron density increases on nitrogen, while positive charge is developed on phosphorus in the transition state.

• Bulletin of the Korean Chemical Society
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• v.18 no.9
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• pp.945-952
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• 1997

The reactions of diazoindanes and diazoindanones with triphenylphosphine have been studied in acetonitrile. The diazoindanes and diazoindanones react with triphenylphosphazine. The reaction of 1,3-bis(diazo)indan-2-one with a tenfold excess of triphenylphosphine in dry acetonitrile gave the 1,3-bis(phosphazino)indan-2-one, however in acetonitrile containing below of 1% water, the 1,3-bis(hydrazono)indan-2-one was produced by hydrolysis. The phosphazine compound could be easily converted into bishydrazone by recrystallization, due to small amounts of water in the solvent. The reactivity of triphenylphosphine toward diazoindanes and diazoindanones depends on the structrue of the diazo compounds.

• Bulletin of the Korean Chemical Society
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• v.16 no.11
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• pp.1060-1064
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• 1995

The reactivity of superoxide ion (O2-.) with halogenated substrates is investigated by cyclic voltammetry and rotated ring-disk electrode method in aprotic solvents. The more positive the reduction potential of the substituted nitrile, the more facile is nucleophilic displacement by O2-.. The reaction rates of halogenonitriles with O2-. vary according to the leaving-group propensity of halide (Br > Cl > F). The relative reaction rates of other substituted nitriles are in the order of electron-withdrawing propensity of the substituent group (CN > C(O)NH2 > Ph ≒ CH2CN). The reaction of O2-. with dihalocarbons indicates that five-membered rings can be rapidly formed by the cyclization of substrate and O2-., and the relative rates of cyclization depend on the number of methylenic carbons {Br(CH2)nBr, [n=1 < 2 < 3 > 4 > 5]}. Mechanisms are proposed for the reaction of O2-. with halogenated substrates.

• Bulletin of the Korean Chemical Society
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• v.15 no.12
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• pp.1112-1118
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• 1994

Epoxidation of olefins has been studied using iodosylbenzene (PhIO) as the terminal oxidant and binuclear and mononuclear complexes of $Mn^{2+}$, $Co^{2+}$, and $Cu^{2+}$ as catalysts. Epoxides were the predominant products with trace amounts of allylic oxidation products, and the metal complexes were found to be effective catalysts in the epoxidation reactions. The reactivity of binuclear copper complexes was greater than that of the mononuclear copper complexes, whereas the binuclear and mononuclear complexes of $Mn^{2+}$ and $Co^{2+}$ showed similar reactivities. The nature of the ligands bound to copper did not influence the reactivity of the binuclear copper complexes so long as copper ions were held in close proximity. A metal-iodosylbenzene complex, such as suggested previously for Lewis acidic metal complex-catalyzed epoxidation by iodosylbenzene, is proposed as the active epoxidizing species. Some mechanistic aspects are discussed as well.

• Bulletin of the Korean Chemical Society
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• v.16 no.7
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• pp.604-609
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• 1995

The relative dissociation constants of 4-substituted bicyclo[2,2,2]octane-1-carboxylic acids, 4-substituted quinuclidines, and 3-and 4-substituted pyridines were collected from a number of sources. In order to understand the actual substituent effects with a combination of inductive effect (σI) and resonance effect (σR) components. The DSP correlation has been employed statistically for each of the p-and m-series. The inductive effect from the m-position was 1.2 times more effective than that from the p-position and the requirement of σR+ for the best-fit led to the conclusion that pyridine system belongs to the σ+-class reactivity. Also compared with results from Yukawa-Tsuno's LArSR treatment and relevant treatment.

• Bulletin of the Korean Chemical Society
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• v.16 no.3
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• pp.277-281
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• 1995

The relationship between the signs of ${\rho}i(0)$, ${\rho}j(0)$ and ${\rho}ij$ and validity of the reactivity-selectivity principle (RSP) has been derived: RSP is valid when W = ${\rho}i(0){\cdot}{\rho}j(0)/{\rho}ij$ is negative. The analysis of 100 reaction series indicated that for normal SN2 reactions involving variations of substituents in the nucleophile (X) and in the substrate (Y) RSP is valid only for a dissociative type for which ${\rho}Y(0)$ is negative, whereas for the acyl transfer reactions with rate-limiting breakdown of the tetrahedral intermediate RSP is valid in general for all substituent changes, X, Y and/or Z (substituent on the leaving group). The trends in the validity of RSP for certain types of reaction can be useful in supplementing the mechanistic criteria based on the signs of ${\rho}i(0)$, ${\rho}j(0)$ and ${\rho}ij$.

• Bulletin of the Korean Chemical Society
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• v.8 no.4
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• pp.313-318
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• 1987

The approximate rate and stoichiometry of the reaction of excess Thexylbromoborane-methyl sulfide, $ThxBHBr{\cdot}SMe_2,$ with selected organic compounds containing representative functional groups under standardized conditions (methylene chloride, $0^{\circ}C)$ were studied in order to characterize the reducing characteristics of the reagent for selective reductions. The selectivity of the reagent was also compared to the selectivity of thexylchloroborane-methyl sulfide. Thexylbromoborane appears to be a much milder and hence more selective reducing agent than thexylchloroborane. The reagent tolerates many organic functionalities. Thus, the reagent shows very little reactivity or no reactivity toward acid chlorides, esters, epoxides, amides, nitro compounds including simple olefins. However, this reagent can reduce aldehydes, ketones, carboxylic acids, nitriles, and sulfoxides. Especially the reagent reduces carboxylic acids including ${\alpha},{\beta}$ -unsaturated ones and nitriles to the corresponding aldehydes. In addition to that, thexylbromoborane shows good stereoselectivity toward cyclic ketones, much better than the chloro-derivative.

• Bulletin of the Korean Chemical Society
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• v.7 no.4
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• pp.289-293
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• 1986

The photocycloaddition reactivity of 5,7-dimethoxycoumarin (DMC) to thymidine is much higher than that of cis-syn 8-methoxypsoralen $<\array{4^{\prime},5\\5^{\prime},6}>$ thymidine monoadducts, due to the steric effect. The different rate is also due to the relative reactivity of the singlet rather than the triplet excited state of the compounds. The biadducts of 8-methoxypsoralen and thymidine are first splitted into 4',5'-monoadducts and thymidine, not into 3,4'-monoadducts and thymidine by 254 nm light.

• Bulletin of the Korean Chemical Society
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• v.29 no.11
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• pp.2183-2188
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• 2008

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.18 no.4
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• pp.481-496
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• 2020

After nuclear power plants are permanently shut down and decommissioned, the remaining irradiated metal components such as stainless steel, carbon steel, and Inconel can be used as neutron absorber. This study investigates the possibility of reusing these metal components as neutron absorber materials, that is burnable poison. The absorption cross section of the irradiated metals did not lose their chemical properties and performance even if they were irradiated over 40-50 years in the NPPs. To examine the absorption capability of the waste metals, the lattice calculations of WH 17×17 fuel assembly were analyzed. From the results, Inconel-718 significantly hold-down fuel assembly excess reactivity compared to stainless steel 304 and carbon steel because Inconel-718 contains a small amount of boron nuclide. From the results, a 20wt% impurity of boron in irradiated Inconel-718 enhances the excess reactivity suppression. The application of irradiated Inconel-718 as a burnable absorber for SMR core was investigated. The irradiated Inconel-718 impurity with 20wt% of boron content can maintain and suppress the whole core reactivity. We emphasize that the irradiated metal components can be used as burnable absorber materials to control the reactivity of commercial reactor power and small modular reactors.