• Bulletin of the Korean Chemical Society
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• 제29권1호
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• pp.139-147
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• 2008

New PPV derivatives which contain electron-withdrawing CF3F4phenyl group, poly[2-(2-ethylhexyloxy)-5-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)-1,4-phenylenevinylene] (CF3F4P-PPV), and poly[2-(4-(2-etylhexyloxy)-phenyl)-5-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)-1,4-phenylenevinylene] (P-CF3F4P-PPV), have been synthesized by GILCH polymerization. As the result of the introduction of the electron-withdrawing CF3F4phenyl group to the phenyl backbone, the LUMO and HOMO energy levels of CF3F4P-PPV (3.14, 5.50 eV) and P-CF3F4P-PPV (3.07, 5.60 eV) were reduced. The PL emission spectra in solid thin film are more red-shifted over 50 nm and increased fwhm (full width at half maximum) than solution conditions by raising aggregation among polymer backbone due to electron withdrawing effect of 2,3,5,6-tetrafluoro-4-trifluoromethylphenyl group. The EL emission maxima of CF3F4P-PPV and P-CF3F4P-PPV appear at around 530-543 nm. The current density-voltage-luminescence (J-V-L) characteristics of ITO/PEDOT/polymer/Al devices of CF3F4P-PPV and P-CF3F4P-PPV show that turn-on voltages are around 12.5 and 7.0 V, and the maximum brightness are about 82 and 598 cd/m2, respectively. The maximum EL efficiency of P-CF3F4P-PPV (0.51 cd/A) was higher than that of CF3F4P-PPV (0.025 cd/A).

• 한국섬유공학회:학술대회논문집
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• 한국섬유공학회 2001년도 가을 학술발표회 논문집
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• pp.314-315
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• 2001

전기 전도성 고분자는 폴리 아세틸렌을 적절한 electron withdrawing group이나 electron donating group을 이용하여 도핑하면 전도도의 증가를 가져온다는 보고 이래로 활발하게 연구되어져 왔다. 그 중에서 폴리피롤은 높은 전도도와 산화안정성, 인체에 무해한 특성 때문에 여러 분야에 응용되고 있으며 분자전자장치나 고체 배터리의 전극, 축전기의 고체 전해질, 전자파 차폐 재료, ion센서, 위장막의 제조 등의 용도전개 잠재력이 무궁하다. (중략)

• Bulletin of the Korean Chemical Society
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• 제32권6호
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• pp.1939-1944
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• 2011

The nucleophilic substitution reactions of bis(Y-aryl) chlorophosphates (1) with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at 35.0 $^{\circ}C$. The kinetic results of 1 are compared with those of Y-aryl phenyl chlorophosphates (2). The substrate 1 has one more identical substituent Y compared to substrate 2. The cross-interaction between Y and Y, due to additional substituent Y, is significant enough to result in the change of the sign of cross-interaction constant (CIC) from negative ${\rho}_{XY}$ = -1.31 (2) to positive ${\rho}_{XY}$ = +1.91 (1), indicating the change of reaction mechanism from a concerted $S_N2$ (2) to a stepwise mechanism with a rate-limiting leaving group departure from the intermediate (1). The deuterium kinetic isotope effects (DKIEs) involving deuterated anilines ($XC_6H_4ND_2$) show secondary inverse, $k_H/k_D$ = 0.61-0.87. The DKIEs invariably increase as substituent X changes from electron-donating to electron-withdrawing, while invariably decrease as substituent Y changes from electron-donating to electron-withdrawing. A stepwise mechanism with a rate-limiting bond breaking involving a predominant backside attack is proposed on the basis of positive sign of ${\rho}_{XY}$ and secondary inverse DKIEs.

• Bulletin of the Korean Chemical Society
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• 제34권12호
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• pp.3597-3601
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• 2013

The reactions of bis(Y-aryl) chlorothiophosphates (1) with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at $55.0^{\circ}C$. The Hammett plots for substituent Y variations in the substrates show biphasic concave upwards with a break point at Y = H. The cross-interaction constants (${\rho}_{XY}$) are positive for both electron-donating and electron-withdrawing Y substituents. The kinetic results of 1 are compared with those of Y-aryl phenyl chlorothiophosphates (2). The cross-interaction between Y and Y, due to additional substituent Y, is significant enough to result in the change of the sign of ${\rho}_{XY}$ from negative with 2 to positive with 1. The effect of the cross-interaction between Y and Y on the rate changes from negative role with electron-donating Y substituents to positive role with electron-withdrawing Y substituents, resulting in biphasic concave upward free energy correlation with Y. A stepwise mechanism with a rate-limiting leaving group departure from the intermediate involving a predominant frontside attack hydrogen bonded, four-center-type transition state is proposed based on the positive sign of ${\rho}_{XY}$ and primary normal deuterium kinetic isotope effects.

• 대한화학회지
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• 제34권3호
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• pp.221-226
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• 1990

MeOH-MeCN, $MeOH-Me_2CO의 이성분 혼합용매계에서 치환 페나실토실레이트류의 가용매 분해반응을 55$^{\circ}C$에서 전기 전도도법으로 연구하였다. 기질의 치환기가 전자받개 이거나 전자주개가 모두 페나실토실레이트 보다 반응속도를 증가시켰으며 m-NO_2$의 경우는 80% MeOH-10% MeCN에서 최대 반응속도를 나타내었다. 전이상태 파라미터의 비인 l/m값으로 부터 기질의 치환기가 전자받개에서 전자주개로 변함에 따라 전이상태는 기질과 친핵체의 결합형성이 감소되고, 기질과 이탈기의 결합파괴가 증가되는 dissociative $S_N2$ 반응메카니즘으로 진행됨을 알 수 있었으며 이 결과는 PES모형과 QM해석 방법에 의한 전이상태 구조변화의 논의와도 일치하였다.

• Bulletin of the Korean Chemical Society
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• 제10권2호
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• pp.151-154
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• 1989

4-Methoxy-4-methylcyclohexa-2,5-dienone 1 in aqueous sulfuric acid underwent the normal dienone-phenol rearrangement with methyl group migration. The fact that methyl is migrating group and methoxy is remaining group can be rationalized by the stabilization of positive charge at C-4 during the transition state. Methoxy methyl dienone 1 $((H_0)_{1/2} = - 4.6)$ is less basic than 4,4-dimethylcyclohexa-2,5-dienone whose half protonation acidity is reported as - 3.15 or - 3.66. This basicity difference comes from the unstabilization of the protonated methoxy methyl dienone 1 due to the electron withdrawing inductive effect of a methoxy group.

• 한국응용과학기술학회지
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• 제14권1호
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• pp.95-102
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• 1997

The synthetic method of pyrazole was performed by 1,3-dipolar cycloaddition with dipolarophile instead of the reaction between diazomethane and acetylene. The cycloaddition mechanism and reactivity of 3-phenyloxadiazole derivatives with dipolarophiles was investigated. In order to investigate the mechanism and reactivity of this cycloaddition, the effect of substituents having various kinds of electron withdrawing or releasing groups were examinated. Considering the effect of substituents, an electron withdrawing group attached at the 4-carbon position in 3-phenyloxadiazole derivatives decrease the reaction rate because of the lack of electron density in oxadiazole ring. The reaction rate of 3-phenyloxadiazole derivatives with dipolarophiles were more conveniently measured using UV than using a volumetric analysis which was used before. From the result of this study, it was that the cycloaddition was found to be a first-order reaction depending upon the concentration of 3-phenyloxadiazole only.

• 한국응용과학기술학회지
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• 제14권3호
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• pp.39-46
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• 1997

Ultraviolet spectrophotometric investigation has been carried out on the rate constants for 1,3-dipolar cycloaddition of 4-substituted-3-phenyloxadiazole derivatives with dipolarophiles such as phenyl acetylene, propiolic acid methyl ester and dimethylacetylene dicarboxylate. From there, the rate constants for 1,3-dipolar cycloaddition were determined at 80, 100 and $120^{\circ}C$, and the reaction rates were increased with increasing temperature. From these rate constants, the values of the thermodynamic activation parameters were obtained. Some thermodynamic activation parameters such as $E_{\alpha}$, ${\Delta}H^{\ast}$, ${\Delta}S^{\ast}$ and ${\Delta}G^{\ast}$ from Arrhenius equation were also calculated for the electrophilic 1,3-dipolar cycloaddition of 3-phenyloxadiazole derivatives with dipolarophiles. In order to the proposal the mechanism and reactivity of 1,3-dipolar cycloaddition reaction, the effect of substituents having various kinds of electron withdrawing or releasing groups were examinated. Considering the effect of substituents, an electron withdrawing group attached at the 4-carbon position in 3-phenyloxadiazole derivatives decreases the reaction rate because of the lack of electron density in 3-phenyloxadiazole ring.

• Bulletin of the Korean Chemical Society
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• 제8권3호
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• pp.168-170
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• 1987

The reaction between 1-benzyl-3-carbamoyl-1,4-dihydropyridine (BNAH) 1 and various 1-arylpyridinium salts 2, and the reaction between 1-(4-methylphenyl)-1,4-dihydropyridine 4b and 1-aryl-3-carbamoylpyridinium (1-arylnicotinamide) salts 5 were carried out. The extents of reaction in equilibrium were estimated by nmr integration data. The equilibrium constants for the reactions, K, and the standard Gibbs free energy changes for the reduction of the pyridinium salts to the corresponding 1,4-dihydropyridines ${\Delta}G^{\circ}'$ were evaluated. The Hammett plot of log K for the reaction between 1 and 2, and ${\Delta}G^{\circ}'$ against ${\sigma}_p$ of the substituents in 1-aryl moiety shows linear correlation with the reaction constant ${\rho}$ of 9.4 (for log K vs ${\sigma}_p$) and -54.5 KJ/mole (for ${\Delta}G^{\circ}'$ vs ${\sigma}_p$). It was found that 1-aryl-1,4-dihydropyridines have much higher reducing power than the corresponding 1-aryl-1,4-dihydronicotinamides, and the power is affected greatly by the electron-withdrawing ability of the substituents in aryl group. The reactions were utilized for preparation of 1,4-dihydropyridines bearing highly electron-withdrawing groups such as 4-nitrophenyl and 2,4-dinitrophenyl, which could not be obtained by conventional dithionite reduction of the corresponding pyridinium salts due to the base-labile nature of the salts.

• 대한화학회지
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• 제32권6호
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• pp.581-587
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• 1988

EtOH-$H_2O, Acetone-H_2O$의 이성분 혼합용매계에서 치환 브롬화벤질류의 가용매분해반응을 $25^{\circ}C$ 와 $45^{\circ}C$에서 전기전도도법으로 연구하였다. 반응속도상수는 벤젠고리에 전자주게 치환기가 도입되거나, 물함량이 증가할수록 컸으며 전자받게 치환기로 바뀜에 따라 용매의 이온화능, Y에 대한 치환 브롬화벤젠류의 가용매분해반응의 감도, m은 연속적으로 감소하였고, 반면에 친핵도에 대한 감도는 증가하였다. 이 결과로 부터 전자주게에서 전자받게로 치환기가 변함에 따라 전이상태는 loose한 결합상태에서 tight한 상태로 변함을 알 수 있었다. 이 결과는 PES 모형과 양자역학적 해석 방법에 의한 전이상태 구조변화의 논의와도 일치하였다.