• Bulletin of the Korean Chemical Society
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• v.18 no.9
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• pp.1010-1013
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• 1997

Nucleophilic substitution reactions of (Z)-phenylethyl (X)-benzenesulfonates with (Y)-pyridines were investigated in acetonitrile at 60 ℃ under respective pressures. The magnitudes of the Hammett reaction constants, ρX, ρY and ρZ indicate that a stronger nucleophile leads to a greater degree of bond formation of C-N and a better leaving group is accompanied by a less degree of bond breaking. The magnitude of correlation interaction term, ρij can be used to determine the structure of the transition state (TS) for the SN reaction. As the pressure is increased, the Hammett reaction constants, ρX and |ρY|, are decreased, but correlation interaction coefficient, ρXZ and |ρYZ|, are increased. The results indicate that the reaction of (Z)-phenylethyl (X)-benzenesulfonates with (Y)-pyridines probably moves from a dissociative SN2 to early-type concerted SN2 mechanism by increasing pressure. This result shows that the correlation interaction term ρij can be useful tool to determine the structure of TS, and also the sign of the product ρXZ·ρYZ can be predict the movement of the TS.

• Bulletin of the Korean Chemical Society
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• v.21 no.10
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• pp.1044-1046
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• 2000

Catalytic copolymerization of diethyl dipropargylmalonate (DEDPM) and phenylacetylene (PA) by Mo(CO)6 and (toluene) Mo(CO)3/chloranil has resulted in the expected copolymer consiting of a polyene backbone with five-and/or six-membered rings and th e PPA structure. Both complexes exhibited not only varying degree of catalytic activity depending upon the relative mole ratio of two monomers but also characterize the types of coploymers. The former yields the polyene backbone containing only five-membered rings as well as PA while the latter produces the polymers consisting of both five-and six-membered ring structure. Comparative studies show that Mo(CO)6 exhibits reactivity toward DEDPM alone, thus catalyzing initially metathesis cyclopoly-merization of DEDPM followed by copolymerization with PA while the (toluene)Mo(CO)3/chloranil system shows affinity for both PA and DEDPM.

• Bulletin of the Korean Chemical Society
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• v.13 no.4
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• pp.398-404
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• 1992

We have investigated the kinetics of diffusion-influenced bimolecular reactions in which one reactant has an internal mode, called the gating mode, that activates or deactivates its reactivity intermittently. The rate law and an expression for the time-dependent rate coefficient have been obtained from the general formalism based on the hierarchy of kinetic equations involving reactant distribution functions. The analytic expression obtained for the steady-state reaction rate constant coincides with the one obtained by Szabo et al., who derived the expression by employing the conventional concentration-gradient approach. For the time-dependent reaction rate coefficient, we obtained for the first time an exact analytic expression in the Laplace domain which was then inverted numerically to give the time-domain results.

• Bulletin of the Korean Chemical Society
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• v.10 no.5
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• pp.459-462
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• 1989

The transition state (TS) structure for the reactions of phenacyl benzenesulfonates with N,N-dimethylanilines (DMA) is investigated using various selectivity parameters, especially with cross-interaction constants, ${\rho}_{ij}$, ${\beta}_{ij}$ and ${\lambda}_{ij}$. The trends in reactivity were similar to aniline series but the TS was found to be somewhat looser than that for aniline series. It was found that the RSP and BEP principle hold within the DMA series but are violated between two different reaction series with DMA and aniline.

• Bulletin of the Korean Chemical Society
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• v.18 no.5
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• pp.484-488
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• 1997

The angular and planar heterocyclic compounds containing nitrogen, sulfur and oxygen were synthesized by reaction of 6,7-dichloro-5,8-quinoxalinedione with aromatic and aliphatic dinucleophiles. Nucleophilic reactivity was somewhat different between 2,3-dichloro-1,4-naphthoquinone and 6,7-dichloro-5,8-quinolinedione with dinucleophiles. The distribution of electron in heterocycle appeared to contribute to this difference. The intercalation comple of planar heterocyclic compound between GC/GC base pairs showed the optimum intercalation but the intercalation of angular heterocyclic compound was not good. Thus, the planar compound was expected to have antitumor activity.

• Bulletin of the Korean Chemical Society
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• v.19 no.10
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• pp.1084-1090
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• 1998

The oxidation of triphenylphosphine by [(tpy)(phen)RuⅣ(O)]2+ and [(bpy)(p-tert-butylpy)RuⅣ(0)]2+ (tpy is 2,2': 6',2"-terpyridine, phen is 1,10-phenanthroline, bpy is 2,2'-bipyridine, and p-tert-butylpy is para-tertbutylpyridine) in CH3CN has been studied. Experiments using 18O-labeled complex show the oxyl group transfer from [RuⅣ=O]2+ to triphenylphosphine occured quantitatively within experimental error. Kinetic data were fit to a second-order for [RuⅣ=O]2+ and [PPh3]. The initial product, [RuⅡ-OPPh3]2+, was formed as an observable intermediate and then underwent slow solvolysis. The reaction proceeded as endothermic in activation enthalpy and a decrease in activation entropy. The oxidative reactivity of four representative ruthenium mono-oxo oxidants against triphenylphosphine was compared. These systems have been utilized as electrochemical oxidative catalysts.

• Bulletin of the Korean Chemical Society
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• v.15 no.12
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• pp.1118-1121
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• 1994

Reactions of alkaline metal carbonates with sulfur are investigated in detail. The evolution of CO and a trace of $SO_2$ were observed in the course of reaction with major component of polysulfides. Some evidences that the reaction proceeds with breaking of terminal sulfur-sulfur bond in the sulfur polymer, and forming CO, $SO_2$ and polysulfide are presented. Polysulfides have the role of keeping free sulfur and allow it to react with other chemicals to rather high temperatures.plexes, whereas the binuclear and mononuclear complexes of Mn$^{2+}$ and Co$^{2+}$

• Bulletin of the Korean Chemical Society
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• v.22 no.12
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• pp.1380-1384
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• 2001

The chemoselective reactions of 1,n-dicarbonyl compounds with allyl halides using indium metal were investigated. $\alpha-Ketoesters$ such as ethyl pyruvate, ethyl 3-methyl-2-oxobutyrate and ethyl benzoylformate reacted with a variety of allyl halides i n the presence of indium to afford hydroxy unsaturated carbonyl compounds in good to excellent yields in MeOH/HCl at $25^{\circ}C.$ For the allyl bromide, the presence of various substituents at the $\alpha$ or $\gamma$ position exhibited little effects on both the reaction rates and yields. Ethyl acetoacetate or ethyl levulinate was treated with allylindium reagent to give hydroxy unsaturated carbonyl compounds in good yield. These results mean that both reactivity and selectivity are independent of the distance between carbonyl groups. 2,3-Butanedione or 1-phenyl-1,2-propanedione reacted with allylindium to produce monoallylation product as major compound.

• Bulletin of the Korean Chemical Society
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• v.20 no.12
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• pp.1418-1420
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• 1999

Kinetics and mechanism of the aminolysis of Z-thiophenyl acetates with X-benzylamines are investigated in acetonitrile at 45.0 ℃. The magnitudes of Bronsted coefficients β$_x$ (=1.3~-1.6) and β$_z$ (= -2.1~-2.4) are all large and cross-interaction constant ρxz is relatively large and positive (0.90). These trends are consistent with the rate-limiting breakdown of a tetrahedral intermediate, $T^±$. The proposed mechanism is also supported by adherence of the rate data to the reactivity-selectivity principle (RSP). The kinetic isotope effects, $k_H/k_D$, are greater than unity (1.3-1.4) suggesting a possibility of hydrogen-bonded four-centered transition state. The activation parameters, ΔH$^≠$ and ΔS$^≠$, are consistent with this transition-state structure.

• Bulletin of the Korean Chemical Society
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• v.12 no.5
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• pp.537-540
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• 1991

Electrophilic methylation reactions of five-membered heteroaromatic compounds, furan, pyrrole and thiophene, with the dimethylfluoronium ion, ${CH_3}{FCH_3}(+), have been investigated theoretically by the MNDO method. The site selectivity of ${\alpha}, {\beta}$ and heteroatom (X) is related to charge density of the site, indicating that the site selectivity is dictated by electrosatic interaction between two reaction centers. The reactivity order between the three heteroaromatics can not be determined decisively since the order differs depending on which site is compared, with relatively low activation enthalpies, ${\Delta}{H^\neq}$= 20-30 kcal/mol, in all cases. These site and substrate selectivity behaviors are consistent with the gas-phase experimental results.