• Journal of the Korean Chemical Society
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• v.32 no.6
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• pp.567-574
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• 1988

Kinetic studies on the vanadium(IV)-catalyzed oxidation of dimethylsulfoxide by hydrogen peroxide in water and aqueous methanol and ethanol show that the reaction is the first order in the concentration of dimethylsulfoxide and hydrogen peroxide, respectively. Activation parameters are also measured for the oxidation of dimethylsulfoxide. It is suggested that the rate determining step is a process involving oxidation of dimethylsulfoxide as the result of nucleophilic attack by the sulfur on the O-O bond of vanadium(V)-peroxide complex.

• Journal of the Korean Chemical Society
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• v.37 no.8
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• pp.753-756
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• 1993

Studies on the molecular interactions of dimethylsulfoxide (DMSO) with water and/or some alkanols were carried out by vapor pressure osmometry at 40$^{\circ}C$. Negative deviation from Raoult's law was observed for the DMSO-water, methanol, ethanol, 1-propanol, 2-propanol, and 2-methyl-1-propanol systems, whereas positive deviation from Raoult's law was observed for the DMSO-1-butanol and 1-pentanol systems. The results were interpreted in terms of molecular interactions between unlike molecules, and of self-association of DMSO molecules, respectively. Measured chemical shift of hydroxyl proton of the solvents also supported the results.

• Journal of the Korean Chemical Society
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• v.33 no.2
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• pp.247-256
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• 1989

4-Acetyl-5,6-dihydro-2-methyl-1,4-thiazine carboxylic acid derivatives 24 were prepared by ring expansion of corresponding thiazolidine sulfoxides. Oxidation of 2-methyl-1,3-thiazolidine-2-acetic acid derivatives 12 gave a mixture of cis and trans sulfoxides, 14 and 15. Assignments of the cis and trans sulfoxides were based on the $^1HNMR$ and IR spectroscopy and regioselectivity of deuterium exchange reaction. With PTSA as acid catalyst both the cis and trans sulfoxide, 14 and 15 were transformed via sulfenic acid 18 to dihydro-1,4-thiazine 24. However, under the neutral conditions (in DMF at $100^{\circ}C$) the trans sulfoxides 15 rearranged via sulfenic acid 21 to isomeric dihydrothiazines 27. The mechanism of formations of 24 and 27 is also discussed.

• Composites Research
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• v.32 no.1
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• pp.71-77
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• 2019

In this study, the structural and rheological characterizations of polyacrylonitrile(PAN)/dimethyl sulfoxide(DMSO) solutions for PAN fiber were investigated according to the change of storage times and temperatures. As a result, PAN/DMSO solutions exhibited a very characteristic rheological behavior with variation of temperature. The solutions showed an increase of complex viscosity and a decrease of loss tangent($tan{\delta}$) as temperature was increased over the temperature range of 40 and $70^{\circ}C$ and it could be seen that the viscosity rapidly increased at low frequency. These results indicated that the gel polymer and denser gel structure were formed due to the intermolecular hydrogen bonding of water in the polymer solution depending on the storage time.

• Journal of the Korean Chemical Society
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• v.26 no.2
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• pp.114-115
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• 1982

• Journal of the Korean Chemical Society
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• v.37 no.1
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• pp.119-130
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• 1993

The stereochemistry of 1,3-thiazolidine sulfoxides 1 in which 3 chiral centres are present in a molecule was elucidated by deuterium exchange and trapping reactions. 3-Acetoxy-1,3-thiazolidines 5 was oxidized to 6 and 8, corresponding $\alpha$-cis 10, $\alpha$-trans 11, $\beta$ -cis 12, and $\beta$ -trans 13 isomers were separated from their diasteromeric mixtures. Sulfoxide 10 was isomerized to more thermodynamically stable isomer 13 under neutral conditions in refluxing benzene or toluene. The methyl hydrogens of 2-methyl group in the sulfoxide 13 and those of the sulfoxide 11 were deuterated by the deuterium incorporation reactions. The intermediate sulfenic acids 25 and 26 derived from the sulfoxides 10 and 12 via sigmatropic rearrangement were trapped by 2-mercaptobenzothiazole (2-MBT) to give disufides 27 and 28 respectively. However, the sulfoxides 11 and 13 were transformed to ring expansion product dihydro-1,4-thiazine 29 under the same reaction conditions. In the presence of acid catalyst, the sulfoxides 10, 11, and 12 were converted to dihydro-1,4-thiazine 29 through the sulfoxide 13 quantitatively. The mechanisms of isomerization of sulfoxides and the formation of 29 were also discussed.

• Journal of the Korean Chemical Society
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• v.30 no.1
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• pp.51-56
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• 1986

Polarographic behavior of cadmium(II) and copper (II) complexes of 1,5-diphenylcarbohydrazide in dimethylsulfoxide have been investigated by the DC polarography. The reduction processes are estimated as follows; Cd(II)${\cdot}$DPH Complex$\frac{e^-}{(E_{\frac{1}{2}}=-0.12V)}$${\to}$Cd(I)${\cdot}$DPH Complex. Cd(I)${\cdot}$DPH Complex$\frac{e^-}{(E_{\frac{1}{2}}=-0.74V)}$${\to}$Cd(Hg) + nDPH. Cu(II)${\cdot}$DPH Complex$\frac{e^-}{(E_{\frac{1}{2}}=-0.44V)}$${\to}$Cu(I)${\cdot}$DPH Complex. Cu(I)${\cdot}$DPH Complex$\frac{e^-}{(E_{\frac{1}{2}}=-0.84V)}$${\to}$Cu(Hg) + nDPH. The limiting currents of all reduction wave are irreversible. The number of ligand and the dissociation constant for Cu(I)${\cdot}$1.5-diphenylcarbohydrazide complex were found to be 2 and 5.12 ${\times}10^{-8}$, respectively. All reduction waves of complexes are irreversible. Based on the experimental results, the polarographic reductions of complexes in dimethylsulfoxide solution occurred in two one-electron steps.

• The Korean Journal of Rheology
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• v.11 no.1
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• pp.28-33
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• 1999

Introducing boric acid to the polyviny alcohol(PVA) solutions has a profound effect on the rheological properties through crosslinking between hydroxyl groups of PVA. This study investigates the effect of boric acid on the rheological properties of polyvinyl alcohol(PVA)/dimethyl sulfoxide(DMSO)/water systems in the absence of cations. The viscosity of PVA/ DMSO/water systems containing 1 wt.% boric acid was decreased with increasing water content. PVA/DMSO systems containing 1 wt.% boric acid exhibited rheological properties similar to elastic gels by forming crosslinked structures. On the other hand, PVA/water systems containing 1 wt.% boric acid exhibited rheological properties typical of viscous materials. In-corporation of boric acid into PVA/DMSO system caused a notable change in the viscosity of the system, whereas boric acid had little effect on the viscosity of PVA/water system. PVA/DMSO/boric acid system gave the greatest storage modulus among the PVA solution systems. Increasing water level in the mixed solvent of DMSO and water diminished the storage modulus of the systems.

• Journal of the Korean Chemical Society
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• v.33 no.2
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• pp.238-246
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• 1989

1,3-Oxathiolane sulfoxide 4 in which the sulfoxide oxygen and the 2-methyl group are on the same face of the oxathiolane ring undergoes a sigmatropic rearrangement to produce a ring expansion product. The structure of this product would be dihydro-1,4-oxathiin 6 or isomeric exo compound 7. This paper describes physical and chemical methods to determine the correct structure of the two alternatives. Thus, $^1HNMR$, UV spectroscopies, and mass spectrometry showed that the product actually obtained had the structure 6. It was also found that from deuteration reactions of the product the compound 7 was initaly formed and then tautomerized to endo compound 6.

• Analytical Science and Technology
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• v.12 no.1
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• pp.1-6
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• 1999

Copper(II) complex of piperidine dithiocarbamate (Pipdtc) was synthesized from the reaction of Cu(II) and piperidine dithiocarbamate. The possible structure of the complex was proposed on the basis of elemental analysis, molar conductivity, infrared spectroscopy, electronic absorption spectroscopy, and $^{13}C-NMR$ studies. The extraction of copper(II)-Pipdtc complex by carbon tetrachloride can be achieved in the pH range of 6.0~10. The solution of copper(II) with piperidine dithiocarbamate was bey Beer's law in the concentration up to ${\sim}8.0{\times}10^{-5}M$ at pH 9.0.