• Bulletin of the Korean Chemical Society
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• v.25 no.9
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• pp.1346-1350
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• 2004

Pseudo-first order rate constants $(k_{obs})$ are reported for the following solvolyses in approximately isodielectric mixtures: 3- and 4-methoxybenzyl chloride, bromo- and chlorodiphenylmethane, and 4-chloro-, 4,4'-dichloro and 4-methyl-chlorodiphenylmethane in 0-80% v/v nitromethane-methanol mixtures; and bromo- and chlorodiphenylmethane and 4-methyl-chlorodiphenylmethane in various acetonitrile-methanol mixtures (in the range 0-50% v/v) at$25^{\circ}C.$ These data, and literature data for t-butyl halides (Cl, Br, and I), and for p-methoxybenzoyl chloride, show rate maxima in solvent compositions of ca. 30% aprotic cosolvent, explained by a stoichiometric solvent effect on electrophilic solvation. Linear relationships are observed between $(k_{obs})/[MeOH]^2$ and [AP]/[MeOH], where [AP] refers to the molar concentration of aprotic cosolvent. The results are consistent with competing third order contributions to $k_{obs}$, $k_{MM}[MeOH]^2$ with hydrogen-bonded methanol as electrophile, and $k_{MAP}[MeOH][AP]$ with hydrogen-bonding disrupted by the aprotic solvent.

• Applied Chemistry for Engineering
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• v.32 no.5
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• pp.532-540
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• 2021

Sodium dodecanoyl-4-oxybenzenesulfonate (DOBS) salt is a substance that exhibits effective bleaching and antimicrobial abilities at low temperatures. A mild and efficient synthesis method of DOBS starting from dodecanoyl chloride and sodium 4-hydroxybenzene sulfonate was investigated under alkaline conditions using a water (W)-polar aprotic solvent system. First, the reaction was carried out using only water as a solvent system with the variables of temperature and time. The yield was found to be as low as about 5% in most cases under the reaction conditions of more than 30 ℃ and 1 h. In order to develop an efficient solvent system, the effect on the yield of DOBS was evaluated in various solvent systems which were prepared by changing the type of polar aprotic solvents while mixing them with the water. A solvent system in which acetone (AC) and water were mixed showed the best yield and about 82 % under mild reaction conditions (30 ℃, 1 h and atmospheric pressure) was obtained. The prepared DOBS showed good bleaching and antimicrobial activities indicating that it could be used an excellent bleach activator.

• Carbon letters
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• v.23
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• pp.55-62
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• 2017

We report on the dispersion state of partially reduced graphene oxide (PRGO) in organic solvents, namely methyl ethyl ketone, ethyl acetate, methylene chloride, toluene, and xylene, by controlling the carbon to oxygen (C/O) atomic ratio of the PRGOs. A two-phase solvent exchange method is also proposed to transfer PRGO from water to an aprotic solvent, such as methyl ethyl ketone. We achieve relatively good dispersion in aprotic and non-polar solvents by controlling the C/O atomic ratio of the PRGOs and applying the two-phase solvent exchange method. There is an increase in the glass transition temperatures with the dispersion of PRGOs into amorphous polymers, in particular a $4.4^{\circ}C$ increase for poly(methyl methacrylate) and $3.0^{\circ}C$ increase for polycarbonate. Good dispersion of PRGO in a nonpolar polymer, such as linear low density polyethylene, is also obtained.

• Archives of Pharmacal Research
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• v.18 no.6
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• pp.454-457
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• 1995

To improve the yield of genuine aglycones from glycosides, the conditions of alkaline hydrolysis were investigated, and a modified method was established. The modified method empolyed pyridine as an aprotic solvent. To complete the hydrolysis and obtain 20(S)-protopanaxadiol (1) and 20(S)-protopanaxatriol(2), which are the genuine aglycones of ginsenosides, total ginsenosides were refluxed with sodium methoxide in pyridine. Addition of methanol, a protic polar solvent to the reaction miuxture, led partial hydrolysis yielding a mixture of the genuine prosapogenols. Of the prosapogenols compound 3 and 6 characteristically possessed D-glucopyranosyl moiety attached at the sterically hindered C-20 hydroxyl group. 3 and 6 were not obtaijned by other hydrolysisw methods except by the soil bacterial hydrolysis.

• Bulletin of the Korean Chemical Society
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• v.4 no.1
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• pp.55-57
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• 1983

• Journal of the Korean Chemical Society
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• v.31 no.3
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• pp.250-257
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• 1987

The electrical conductances for the thorium (IV) complexes with crown ethers have been measured in DMSO, and water solvents, and the oxidation-reduction reaction mechanisms, electron number and diffusion coefficients in the reversible reduction process have been examined by polarography and cyclic voltammography. The dissociation mole ratio of $Th^{4+}$ and nitrate ion are 1:1 and in aprotic solvent, and 1:4 in protic solvent like as water. The limiting molar conductances of all complexes in aprotic solvent have been found to be in the range of $92.2{\times}159$ $ohm^{-1}cm^2mol^{-1}$. In aprotic solvent, DMSO, the reduction of each complex is reversible by one electron reduction of one step, and the range of diffusion coefficients is obserbed to be $5.83\;10^{-6}{\sim}6.90{\times}10^{-6}$. The complexes which have reduction step were hydrolyzed above at 1.8volt with reference saturated calomel electrode, generating the hydrogen gas. The reaction mechanisms of thorium (IV)-crown ether complexes appear as follows. ${Th_m(IV)L_n(H_2O)_x(NO_3)_{4y}}_=^{DMSO} {\overline{{Th_m(IV)L_n(H_2O)_x(NO_3)_{4y-1}}}^+ + NO_3-$

• Journal of the Korean Chemical Society
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• v.27 no.1
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• pp.1-8
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• 1983

Solvent effects on nucleophilic substitution reaction of naphthalene sulfonyl chlorides with pyridine in protic and aprotic solvent have been studied by means of conductometry. Results showed that the rate constants increased with dielectric constants for protic solvents, while they decreased with dielectric constants for aprotic solvents, except for acetonitrile which has a higher dielectric constant but had also greater rate constant. The rate constants were shown to be more susceptible to polarity-polarizability parameter, , than to hydrogen bond donor acidity parameter, ${\alpha}$, indicating that the pulling effect of hydrogen bonding solvent.

• Elastomers and Composites
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• v.55 no.3
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• pp.205-214
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• 2020

A series of wholly aromatic polyhyroxyamide (PHA) copolymers were prepared by direct polycondensation reaction of isophthalic acid and diacids containing bulky units with 3,3'-dihydroxybenzidine. The inherent viscosities of the PHAs measured at 35℃ in DMAc solution were in the range of 0.31-0.56 dL/g. The solubility study revealed that the PHAs were readily soluble in aprotic solvents such as, dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), and N-methyl-2-pyrrolidone (NMP) at room temperature and in less polar solvent such as pyridine. However, the polybenzoxazole (PBO) copoymers were quite insoluble in all organic solvents except partially soluble in concentrated sulfuric acid and partially soluble in NMP containing LiCl. The PBO copolymers showed maximum weight loss temperature in the range of 593-632℃ and high char yields in the range of 65.0-71.2% at 900℃ in a nitrogen atmosphere.

• Bulletin of the Korean Chemical Society
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• v.15 no.5
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• pp.329-330
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• 1994

• Bulletin of the Korean Chemical Society
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• v.31 no.5
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• pp.1199-1203
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• 2010

Second-order rate constants ($k_N$) have been measured spectrophotometrically for Michael-type reactions of 1-(X-substituted phenyl)-2-propyn-1-ones (2a-f) with a series of alicyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. The $k_N$ value increases as the incoming amine becomes more basic and the substituent X changes form an electron-donating group (EDG) to an electron-withdrawing group (EWG). The Br${\o}$nsted-type plots are linear with ${\beta}_{nuc}$ = 0.48 - 0.51. The Hammett plots for the reactions of 2a-f exhibit poor correlations but the corresponding Yukawa-Tsuno plots result in much better linear correlations with ${\rho}$ = 1.57 and r = 0.46 for the reactions with piperidine while ${\rho}$ = 1.72 and r = 0.39 for those with morpholine. The amines employed in this study are less reactive in MeCN than in water for reactions with substrates possessing an EDG, although they are ca. 8 pKa units more basic in the aprotic solvent. This indicates that the transition state (TS) is significantly more destabilized than the ground state (GS) in the aprotic solvent. It has been concluded that the reactions proceed through a stepwise mechanism with a partially charged TS, since such TS would be destabilized in the aprotic solvent due to the electronic repulsion between the negative-dipole end of MeCN and the negative charge of the TS. The fact that primary deuterium kinetic effect is absent supports a stepwise mechanism in which proton transfer occurs after the rate-determining step.