• Bulletin of the Korean Chemical Society
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• v.35 no.3
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• pp.753-757
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• 2014

The nucleophilic substitution reactions of Y-aryl N,N-dimethyl phosphoroamidochloridates with substituted anilines and deuterated anilines are kinetically investigated in acetonitrile at $65.0^{\circ}C$. A stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed based on the positive ${\rho}_{XY}$ value. The deuterium kinetic isotope effects involving deuterated anilines show secondary inverse with all the nucleophiles, rationalized by a dominant backside nucleophilic attack.

• Bulletin of the Korean Chemical Society
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• v.32 no.11
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• pp.4095-4098
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• 2011

• Bulletin of the Korean Chemical Society
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• v.15 no.10
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• pp.901-903
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• 1994

• Bulletin of the Korean Chemical Society
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• v.14 no.4
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• pp.425-427
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• 1993

• Bulletin of the Korean Chemical Society
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• v.14 no.5
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• pp.531-533
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• 1993

• Bulletin of the Korean Chemical Society
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• v.14 no.6
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• pp.654-655
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• 1993

• Bulletin of the Korean Chemical Society
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• v.8 no.4
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• pp.350-351
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• 1987

• Bulletin of the Korean Chemical Society
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• v.18 no.8
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• pp.868-873
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• 1997

Nucleophilic substitution reactions of 1-phenylethyl chlorides (1-PEC; YC6H4CH(CH3)Cl) with phenoxides (XC6H4O-) and thiophenoxides (XC6H4S-) are investigated theoretically using the PM3 method. The Bronsted α and β values are greater for the phenoxides indicating a more advanced reaction in the transition state (TS) than for the thiophenoxides. This is supported by a greater magnitude of ρX (- 6.4 ∼ - 7.4) and ρXY (- 0.76) for the phenoxides than for the thiophenoxides (ρX = - 3.6 ∼ - 4.4 and ρXY = - 0.60). The percentage bond order changes, %Δn≠, suggest that the extents of bond making and breaking are similar for the phenoxides and hence the TS is symmetrical, but bond making is somewhat greater than bond cleavage for the thiophenoxides indicating an unsymmetrical TS. The reactions in the gas phase for both nucleophile series proceed by a SN2 mechanism with a tight TS and negative charge development on the reaction center carbon, Cα. The reactions in water investigated with model systems of benzyl and 1-phenylethyl chlorides using the Cramer-Truhlar solvation model (PM3-SM3) indicate that the reactions of 1-PEC are far more complex due to enhanced stabilization of the carbocation by the methyl substitution for a benzylic hydrogen.

• Proceedings of the Materials Research Society of Korea Conference
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• 2011.05a
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• pp.243.1-243.1
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• 2011

We demonstrate a facile and robust layer-by-layer (LbL) assembly method for the fabrication of nonvolatile resistive switching memory (NRSM) devices based on superparamagnetic nanocomposite multilayers, which allows the highly enhanced magnetic and resistive switching memory properties as well as the dense and homogeneous adsorption of nanoparticles, via nucleophilic substitution reaction (NSR) in nonpolar solvent. Superparamagnetic iron oxide nanoparticles (MP) of about size 12 nm (or 7 nm) synthesized with oleic acid (OA) in nonpolar solvent could be converted into 2-bromo-2-methylpropionic acid (BMPA)-stabilized iron oxide nanoparticles (BMPA-MP) by stabilizer exchange without change of solvent polarity. In addition, bromo groups of BMPA-MP could be connected with highly branched amine groups of poly (amidoamine) dendrimer (PAMA) in ethanol by NSR of between bromo and amine groups. Based on these results, nanocomposite multilayers using LbL assembly could be fabricated in nonpolar solvent by NSR of between BMPA-MP and PAMA without any additional phase transfer of MP for conventional LbL assembly. These resulting superparamagnetic multilayers displayed highly improved magnetic and resistive switching memory properties in comparison with those of multilayers based on water-dispersible MP. Furthermore, NRSM devices, which were fabricated by LbL assembly method under atmospheric conditions, exhibited the outstanding performances such as long-term stability, fast switching speed and high ON/OFF ratio comparable to that of conventional inorganic NRSM devices produced by vacuum deposition.

• Journal of the Korean Chemical Society
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• v.22 no.6
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• pp.396-402
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• 1978

MO theoretical studies on the conformation and the acid-catalyzed nucleophilic substitution of N-acetylpyperidone were carried out by EHT, CNDO/2 and the orbital mixing analytical methods. MO calculations show that the most preferred conformation is the half-chair, cis-trans form and the protonation occurs most readily on the acetyl carbonyl oxygen. These results were interpreted in terms of conjugative, electrostatic and steric effect. From orbital mixing analysis, we found also that the reactivity of protonated carbonyl carbon is greatly enhanced due to increase in positive charge (for charge controlled reaction) of the carbonyl carbon atom. Accordingly, the acetyl cleavage will be preferred in the nucleophilic substitution (acid-catalyzed hydrolysis) to the ring cleavage.