• The Korean Journal of Food And Nutrition
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• v.8 no.3
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• pp.172-183
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• 1995

The nucleophilic substitution reactions of p-substituted benzyl bromide with l-substituted N,N-dimethylanilines in methanol and acetonitrile binary solvent mixture which is known to an isodielectric solvent system kinetically and the results are as follows. The positive charge is developed on the reaction center of the substrate and it means that the bond cleavage is preceded more than bond formation in the transition state on the analogy of Hammett px values. The bond form3tlon is not progressed in the case of electron donating substituent of substrate. However, the bond formation is much developed in the case of electron withdrawing substituent of substrate on the analogy of Hammett py values. The nucleophilic attacking ability is shown a highest at 80% (V/V) methanol content and the bond formation is well progressed at the same methanol composition on the result of a cross interaction coefficient, pxy. The result of transition state structure that is applicated to the potential energy surface model is in accord with the result that Is applicated to the reaction susceptibilities. The reaction Is subject to the polarity-polarizability term more than the hydrogen bond donor acidity term by application to the solvatochromic parameter eouation.

• Journal of the Korean Chemical Society
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• v.30 no.3
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• pp.282-288
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• 1986

Kinetic studies were carried out for the substitution of $H-2$O for $Cl^-$ ligand of chloropentaamminecobalt(III) in the presence of $Hg^{2+}$ catalyst by UV spectrophotometer. It has been found that $Hg^{2+}$ ion appears first order dependence and the overall reaction is second order. The reaction system can be believed to occur via $S_N2$ reaction, because the calculated rate equation for our presumed $S_N2$ mechanism is in agreement with the observed one.

• BMB Reports
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• v.41 no.4
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• pp.305-309
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• 2008

Cobalt is an essential microelements in many biological processes involving enzymatic activity. We found that $Zn^{2+}$ and $Mg^{2+}$, which are in the active site of native calf intestine alkaline phosphatase (CIP), can be replaced by $Co^{2+}$ directly in solution. The effect of $Co^{2+}$ concentration on the substitution reaction was examined at ratios of [$Co^{2+}$]/[CIP] from 0:1 to 8:1. The quantity of $Zn^{2+}$ in CIP decreased progressively as the ratio was increased, but the amount of $Mg^{2+}$ changed in irrregular fashion. A series of active site models of the reaction mechanism of CIP are proposed. Low pH was found to promote the replacement of $Mg^{2+}$ by $Co^{2+}$. To understand how the substitution affects the enzyme, we also solved the secondary structure of CIP after reaction with $Co^{2+}$ in different conditions.

• Bulletin of the Korean Chemical Society
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• v.15 no.6
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• pp.473-477
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• 1994

Second-order rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of aryl substituted benzenesulfonates $(1,\;X-C_6H_4SO_2-OC_6H_4-Y)$ with aryloxides $(Z-C_6H_4O^{-})$ and ethoxide $(EtO^-)$ in absolute ethanol at $25^{circ}C$. The nucleophilicity of aryloxides increases with increasing electron donating ability of the substituent (Z) on aryloxides, and results in a good Hammett correlation with $\sigma^{-}$ constant. The reactivity of 1 toward aryloxides and ethoxide shows also significant dependence on the electronic nature of the substituent X and Y. Large positive ${\sigma}_{acyl}$ values have been obtained for the reaction of 1 with phenoxide and ethoxide, indicating that the leaving group departure is little advanced at the transition-state of the rate-determining step. This has been further supported from the fact that ${\sigma}^-$ constant gives extremely poor Hammett correlation, while ${\sigma}^0$ does reasonably good correlation for the reaction of 1 with ethoxide. Thus, the present sulfonyl-transfer reaction is proposed to proceed via a ratedetermining attack of nucleophile to the sulfur atom of 1 followed by a fast leaving group departure.

• Bulletin of the Korean Chemical Society
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• v.28 no.12
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• pp.2219-2225
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• 2007

The reaction mechanisms for the cyclizations of N-methyl-2-(2-chloropyridin-3-yloxy)acetamide to 1-methylpyrido[ 3,2-b][1,4]oxazin-2-one and 1-methyl-pyrido[2,3-b][1,4]oxazin-2-one were investigated using ab initio Hartree-Fock, second-order Moller-Plesset perturbation, single point coupled cluster with both single and double substitution, and density functional theory methods. The 5-membered spiro intermediate (2) is optimized from the cyclization of the acyclic reactants through the proton-transfer reaction, and this intermediate proceeds continuously to the 6-membered intermediate through either a stepwise or a concerted reaction. In the stepwise reaction, an N-bridge-type intermediate as a stable structure is optimized, whereas, in the concerted reaction, the O-bridge-type intermediate is not optimized.

• Journal of the Korean Magnetic Resonance Society
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• v.21 no.4
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• pp.135-138
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• 2017

Titanium phenoxide and titanium carboxylate derivatives were prepared by ligand exchange of titanium tetraisopropoxide with the corresponding phenol and carboxylic acids. The substitution reactions were analyzed by NMR focused in the liberation of isopropylalcohol. The chemical shift of secondary proton of isopropyl group shifted to upfield after liberation; from 4.47 ppm at titanium-bound to 4.1~4.3 ppm at free alcohol state in $CDCl_3$. The substitution reaction of titanium tetraisopropoxide with carboxylic acid was applied to form dye-Ti complex for dye-sensitized solar cell.

• 한국정보디스플레이학회:학술대회논문집
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• 2008.10a
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• pp.578-580
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• 2008

Blue-emitting $CaAl_2Si_2O_8:Eu^{2+}(CAS:Eu^{2+})$ phosphor, prepared by solid-state reaction, is described in this paper. We researched the effect of boron ion substitution in the host materials. The phase and luminescent properties were investigated using the powder X-ray diffraction(XRD) and photoluminescence(PL) spectra.

• Bulletin of the Korean Chemical Society
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• v.26 no.2
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• pp.273-277
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• 2005

Dynamic resolution of $\alpha$-bromo tertiary acetamides in asymmetric nucleophilic substitution reaction is described. Intermolecular substitution of $\alpha$-bromo tertiary acetamides with dibenzylamine in the presence of TBAI and $Et_3N$ gave the dipeptide analogues 7-10 with high stereoselectivities up to 90 : 10 dr. Also, cyclic dipeptide analogues 20-29 were produced by the intramolecular nucleophilic cyclization of $\alpha$-bromo tertiary acetamides with low stereoselectivities in 84-42% yields.

• Applied Chemistry for Engineering
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• v.10 no.2
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• pp.275-280
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• 1999

Cellulose has three hydroxyl groups with different reactivity. By substitution reaction, trimethylsiloxyl-, vinyldimethylsiloxyl-, allyldimethylsiloxyl-, phenyldimethylsiloxyl-, 3,3,3-trifluoropropyldimethylsiloxyl- and tris(trimethylsiloxy)siloxylcellulose were synthesized IR, NMR, and elemental analysis were used for confirming their structures, degree of substitution (D.S.) and the reactivity of siloxylation agent, respectively. The D.S. values were 2.5, 2.2, 2.1, 2.2, 2.6, 0.7 for the corresponding siloxylcellulose.

• YAKHAK HOEJI
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• v.58 no.1
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• pp.28-32
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• 2014

A new series of 3-allylthio-6-alkylthiopyridazines (3)~(12) was synthesized from dichloropyridazine (1) for development of candidates to retain anticancer activity of human breast cancer. The process involves allythiolation and alkylthiolation from 3,6-dichloropyridazine. 6-Substituted allylthiopyridazines (3)~(12) were prepared from 3-allylthiopyridazinyl chloride (2) via nucleophilic substitution with alkylthiol anion as nucleophile. 3-Allylthiopyridazinyl chloride (2) could be converted to pyridazines (3)~(11) using 1 equivalent of alkyl mercaptan at reflux temperature in methanol. 3,6-Diallylthiopyridazine (12) was synthesized from 3,6-dichloropyridazine (1) using allyl mercaptan (4 equivalent) and sodium hydroxide in methanol. Synthetic compounds were fully identified using NMR, IR, GC-MS data.