• Bulletin of the Korean Chemical Society
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• 제28권12호
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• pp.2153-2161
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• 2007

The transition metal-induced in situ generation of carbene complexes from alkynes having a carbonyl or imino group as a nucleophilic functionality has been investigated. These reactive carbenoid species are generated with high atom efficiency through a 6-endo-dig cyclization mode based on the electrocyclization of vinylidene complexes or a 5-exo-dig cyclization mode in π-alkyne complexes, and have been found to serve as versatile intermediates in catalytic carbene transfer reactions. Highlighted and reviewed in this account are the generation and preparation of pyranylidene, furylcarbene, pyrrolylcarbene, and vinylcarbene complexes and their application to [3,3]sigmatropic rearrangement of acylcyclopropylvinylidenes, catalytic cyclopropanation reactions, [2,3]sigmatropic rearrangement or condensation reactions via ylides, ring-opening and substitution reactions with heteroaromatic compounds, and catalytic isomerization of oligoynes.

• 한국세라믹학회지
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• 제49권3호
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• pp.266-271
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• 2012

The effect of $Bi(Mg_{1/2}Sn_{1/2})O_3$ (BMS) modification on the crystal structure, ferroelectric and piezoelectric properties of $Bi_{1/2}(Na_{0.8}K_{0.2})_{1/2}TiO_3$ (BNKT) ceramics has been investigated. The BMS-substitution induced a transition from a ferroelectric (FE) tetragonal to a nonpolar pseudocubic phase, leading to degradations in the remnant polarization, coercive field, and piezoelectric coefficient $d_{33}$. However, the electric-field-induced strain was significantly enhanced by the BMS substitution-induced phase transition and reached a highest value of $S_{max}/E_{max}$ = 633 pm/V under an applied electric field of 6 kV/mm when the BMS content reached 6 mol%. The abnormal enhancement in strain was attributed to the field-induced transition of the pseudocubic symmetry to other asymmetrical structure, which was not clarified in this work.

• Bulletin of the Korean Chemical Society
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• 제35권5호
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• pp.1506-1510
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• 2014

A kinetic study on nucleophilic substitution reaction of 5-nitro-8-quinolyl picolinate (6) with alkali-metal ethoxides (EtOM; M = K, Na, and Li) in anhydrous ethanol is reported. The plot of $k_{obsd}$ vs. [EtOM] curves upward in the absence of crown ethers but is linear with significantly decreased reactivity in the presence of crown ethers. Dissection of $k_{obsd}$ into $k_{EtO}$- and $k_{EtOM}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the ion-paired EtOM is significantly more reactive than the dissociated $EtO^-$ (e.g., $k_{EtOM}/k_{EtO^-}$ = 33.4-141). This indicates that the reaction of 6 is catalyzed by $M^+$ ions in the order $Na^+$ > $Li^+$ > $K^+$ and the catalytic effect disappears in the presence of a proper crown ether. Picolinate ester 6 is much more reactive and is more strongly catalyzed by $M^+$ ions than 5-nitro-8-quinolyl benzoate (5). It has been concluded that $M^+$ ions catalyze the reaction of 6 by increasing electrophilicity of the reaction center through a cyclic transition state, which is structurally not possible for the reaction of 5.

• Bulletin of the Korean Chemical Society
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• 제32권6호
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• pp.1951-1956
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• 2011

A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl nicotinate 5 and isonicotinate 6 with alkali metal ethoxide EtOM (M = K, Na, and Li) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. Plots of pseudo-first-order rate constant $k_{obsd}$ vs. EtOM concentration exhibit upward curvature for the reactions of 5 and 6 with EtOK and EtONa but are almost linear for those with EtOLi. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constant for the reaction with dissociated $EtO^-$ and ion-paired EtOM, respectively) has shown that $k_{EtOK}$ ${\geq}$ $k_{EtONa}$ > $k_{EtO^-}$ but $k_{EtOLi}$ < $k_{EtO^-}$. It has been concluded that $K^+$ and $Na^+$ ions catalyze the reactions by increasing the electrophilicity of the carbonyl carbon atom through formation of a 4-membered cyclic transition state $TS_3$ or $TS_4$. However, $M^+$ ion catalysis has been found to be much less significant for the reactions of 5 and 6 than for the corresponding reactions of 4-nitrophenyl picolinate 4, which was reported to proceed through a 5-membered cyclic transition state $TS_2$. Although 5 and 6 are significantly more reactive than 4-nitrophenyl benzoate 3, the reactions of 5 and 6 result in smaller $k_{EtOK}/k_{EtO^-}$ ratios than those of 3. The electron-withdrawing ability of the nitrogen atom in the acyl moiety of 5 and 6 has been suggested to be responsible for the increase in reactivity and the decrease in the $k_{EtOK}/k_{EtO^-}$ ratio.

• Bulletin of the Korean Chemical Society
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• 제30권12호
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• pp.2913-2917
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• 2009

Second-order rate constants (k$_{Nu–}$) have been measured for nucleophilic substitution reactions of Y-substituted phenyl benzoates (1a-i) with butane-2,3-dione monoximate ($Ox^-\;an\;\alpha$-nucleophile) and Z-substituted phenoxides in 80 mol% H$_2$O/20 mol% DMSO at 25.0${\pm}$0.1$^{\circ}C$. Hammett plots correlated with ${\sigma}^o$ and ${\sigma}^-$ constants for reactions of 1a-h with Ox$^–$ exhibit many scattered points. In contrast, the Yukawa-Tsuno plot results in a good linear correlation with ${\rho}_Y$ = 2.20 and r = 0.45, indicating that expulsion of the leaving group occurs in the rate-determining step (RDS). A stepwise mechanism with expulsion of the leaving-group being the RDS has been excluded, since Y-substituted phenoxides are less basic and better nucleofuges than Ox$^–$. Thus, the reactions have been concluded to proceed through a concerted mechanism. Ox$^–$ is over 10$^2$ times more reactive than its reference nucleophile, 4-chlorophenoxide (4-ClPhO$^–$). One might suggest that stabilization of the transition-state (TS) through intramolecular general acid/base catalysis is responsible for the ${\alpha}$-effect since such general acid/base catalysis is not possible for the corresponding reactions with 4-ClPhO$^–$. However, destabilization of the ground-state (GS) of Ox$^–$ has been concluded to be mainly responsible for the ${\alpha}$-effect found in this study on the basis of the fact that the magnitude of the ${\alpha}$-effect is independent of the nature of the substituent Y.

• Journal of Magnetics
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• 제18권1호
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• pp.34-38
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• 2013

This paper studies the effects of the Mn-site substitution by nickel on the magnetic properties and the magnetocaloric properties of $La_{0.7}Ca_{0.3}Mn_{1-x}Ni_xO_3$ (x = 0, 0.05 and 0.1). The orthorhombic crystal structures of the samples are confirmed by the room temperature X-ray diffraction. The dependence of the Curie temperature ($T_C$) and the magnetic entropy change (${\Delta}S_M$) on the Ni doping content was investigated. The samples with x = 0 had the first order phase transition, while the samples with x = 0.05 and 0.1 had the second order phase transition. As the concentration of Ni increased, the maximum entropy change (${\mid}{\Delta}S_M{\mid}_{max}$) decreased gradually, from 2.78 $J{\cdot}kg^{-1}{\cdot}K^{-1}$ (x = 0) to 1.02 $J{\cdot}kg^{-1}{\cdot}K^{-1}$ (x = 0.1), in a magnetic field change of 15 kOe. The measured value of $T_C$ was 185 K, 150 K and 145 K for x = 0, 0.05 and 0.1, respectively. The phase transition temperatures became wider as x increased. It indicates that the Mn-site substitution by Ni may be used to tailor the Curie temperature in $La_{0.7}Ca_{0.3}Mn_{1-x}Ni_xO_3$.

• 대한전기학회논문지
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• 제45권2호
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• pp.235-241
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• 1996

In this paper dielectric and electrostrictive strain properties of (1-y-x)Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_{3}$-PbTiO$_{3}$$-yPbTiO_{3}-xSrTiO_{3}[(1-y-x)PMN-yPT-xST]$ ceramics fabricated by using columbite precursor method have been investigated with the substitution of SrTiO$_{3}$(ST). Dielectric constant of the specimens increased with the increase of ST content up to 5[m/o] and decreased with further substitution of ST. And the pyrochlore phase decreased with the increase of ST content up to 5[m/o] in XRD analysis. The elimination of the pyrochlore phase improved dielectric constants. The electrostrictive strains generated by AC electric field have the highest value at 5[m/o] SrTiO$_{3}$ addition and the hysteresis of strain ranged from 12 to 20[%]. The electrostrictive strain at various temperature investigated in the temperature range of $-50[^{\circ}C]~74[^{\circ}C].$ In higher temperature than phase transition region, it showed paraelectric property which shows very small hystersis.

• Bulletin of the Korean Chemical Society
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• 제18권8호
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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.

• 대한화학회지
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• 제29권5호
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• pp.478-481
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• 1985

염화 알칸술포닐과 파라 치환된 아닐린간의 친핵성 치환반응을 메탄올-아세토니트릴 혼합용매하에서 연구하였다. 기질의 반응성, 친핵체의 치환기효과 및 용매효과로 부터 반응 메카니즘이 $S_N2$임을 알았다. i-PSC의 경우 메탄올 조성이 커짐에 따라 전이상태가 더 loose해 짐을 알았다.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2011년도 춘계학술발표대회
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• pp.29.2-29.2
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• 2011

B-site substitution with isovalent and donor impurities was compared in terms of the piezoelectric properties of Bi-based ABO3 perovskite ceramics. X-ray diffraction study revealed that both impurities bring about degradation in their ferroelectric properties as well as piezoelectric characteristics. However, there existed a difference between the isovalent and heterovalent impurities that influence a phase transformation of ferroelectric anisotropic-to-electrostrictive pseudocubic symmetry. Based upon analyses including the crystal, microstructure, dielectric, ferroelectric properties, we believed that A-site vacancies in the ABO3 ceramic significantly contribute to a ferroelectric-nonpolar phase transition, which give rise to lead to a giant strains. The present paper will discuss the origin of giant strains in Bi-based perovskite ceramics.