• EDISON SW 활용 경진대회 논문집
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• 제6회(2017년)
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• pp.165-171
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• 2017

Diels-Alder 반응은 고리형 탄소화합물을 만드는 유기 합성 과정에서 매우 중요한 반응이다. 이 반응은 중간생성물 없이 오직 1 step으로 진행되는데, diene이나 dienophile에 결합한 치환기의 electron donating 및 electron withdrawing 성질에 따라 반응성이 달라진다고 알려져 있다. 이 때 반응물인 diene과 dienophile의 분자 오비탈 및 전이 상태의 에너지 변화를 계산화학을 통해 분석한다면 Diels-Alder 반응을 보다 심도 있게 이해할 수 있다. 이에 따라 본 연구에서는 DFT 계산을 통하여 치환기에 따른 활성화 에너지의 크기와 diene의 nucleophilicity 및 dienophile의 electrophilicity를 비교하였다. 이를 통해 electron withdrawing group의 경우 분자의 electrophilicity를 증가시키고, electron donating group의 경우 nucleophilicity를 증가시킨다는 것을 확인할 수 있었다. 그 결과, Diels-Alder 반응이 일어날 때 dienophile의 경우 치환된 electron withdrawing group에 의해 electrophilicity가 증가함에 따라 활성화 에너지가 낮아져 반응이 잘 일어나고, 반대로 diene의 경우 electron donating group이 치환되어 있을 때 nucleophilicity의 증가에 따라 반응이 잘 일어난다는 것을 알 수 있었다.

• Journal of Photoscience
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• 제11권1호
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• pp.7-9
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• 2004

The synthesized macrocycle L was found to be a smart fluorescent receptor which distinguishable efficiently from various neutral molecules with the functional groups such as the electron donating (X =$CH_3$, N($CH_3$)$_2$ and O$CH_3$) and electron withdrawing groups (X =F and Cl), respectively. In the case of guest molecules containing electron donating groups, the fluorescence of macrocycle L was enhanced in the presence of the guest molecules. On the contrary, in the case of guest molecules containing electron withdrawing groups, it was almost quenched in the presence of those.

• Macromolecular Research
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• 제15권3호
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• pp.216-220
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• 2007

A new polyfluorene-based copolymer having 2-ethylhexyloxy-5-methoxy-l,4-phenylene as an electron donating group and 2,5-diphenyl-oxadiazole as an electron withdrawing group was synthesized by the Suzuki coupling reaction. The obtained copolymer was characterized by $^1H-NMR,\;^{13}C-NMR$, and IR-spectroscopy. The weight average molecular weight ($M_w$) of the obtained polymer was 18,600 with a polydispersity index of 1.5. The maximum photoluminescence of the solution and film of the polymer was observed at 453 nm and 456 nm, respectively. A double-layer device with the configuration, ITO/PEDOT/copolymer/Al, emitted blue light at 460 nm.

• 대한화학회지
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• 제67권3호
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• pp.175-180
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• 2023

Tetra-aryl substituted A4-type porphyrins (TP, TD, TA) and trans-A2B2 porphyrins (DDP1, AAP1) with electron-donating or withdrawing groups were synthesized. The band gap energy of those porphyrins was calculated from their UV-Vis spectra and CV data. With an electron-withdrawing group, the band gap energy of porphyrin TA increased via the LUMO energy up. Meanwhile, the introduction of an electron-donating group decreased the band gap of porphyrin by HOMO level up as as in the case of porphyrin TD. The band gap (2.19-2.28 eV) of metalloporphyrin PP-Ni was greater than those (1.81-2.06 eV) of non-metalloporphyrins PP due to the LUMO level up.

• Bulletin of the Korean Chemical Society
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• 제16권12호
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• pp.1203-1208
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• 1995

Theoretical studies of the effect of the nonleaving group (RY) on the breakdown mechanism of the tetrahedral anionic intermediate, T-, formed by the addition of a less basic phenoxide nucleophile (X) to phenyl benzoates with a more basic phenoxide leaving group (Z) have been carried out using the PM3 MO method. The identity acyl transfer reactions (X=Z) are facilitated by an electron-withdrawing RY whereas they are inhibited by an electron-donating RY group. The results of non-identity acyl transfer reactions indicate that a more electron-donating RY group leads to a greater lowering of the higher barrier, TS2, with a greater degree of bond cleavage, and a greater negative charge development on the phenoxide oxygen atom, whereas the opposite is true for a more electron-withdrawing RY group, i.e., leads to a greater lowering of the lower barrier, TS1. The results provide theoretical basis for the signs of ρXY(>0) and ρYZ(<0) observations.

• Bulletin of the Korean Chemical Society
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• 제28권8호
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• pp.1363-1370
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• 2007

The geometrical structures of pyridazin-3-one derivatives (4,5-dihalopyridazin-3-one and 4-halo-5- alkoxypyridazin-3-one) with various functional and substituent groups were fully optimized using the ab initio Hartree-Fock (HF) and second order Moller-Plesset perturbation (MP2) methods. At the N2-, C4-, and C5- positions on the pyridazin-3-one rings, the structural and electronic features pertaining to the variations of the functional and substituent groups were analyzed, respectively. The trends in the variation of the bond lengths, atomic charges, and energetics (relative energy, binding energy) of the derivatives induced by changing the electron donating functional groups (X1 = OMe, OEt) to electron withdrawing groups (X1 = Cl, NO2) were examined. The variations of the bond lengths, atomic charges, and binding energies with the electron withdrawing strength of the substituent groups (Y = Me → F) were also investigated.

• Macromolecular Research
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• 제15권6호
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• pp.533-540
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• 2007

We designed and successfully synthesized UV curable, functional acrylate monomers having a polarizing group, i.e., an electron-withdrawing and/or electron-donating group for the optical materials of high refractive index. Optical polymer films made from the functional methacrylate monomers were achieved with photo crosslinking under UV illumination. A monomer having amino and cyano groups (Dimer-CN) exhibited the highest refractive index ($n_{TE}$=1.595 at 850nm) among the studied methacrylate derivatives, due to the large polarizability of the dipolar monomer structures with electron-donating and withdrawing groups. By controlling the compositions of the functional acrylate monomer of copolymers, the refractive indices of the polymers were readily adjusted within a wide range of 1.498-1.595. The copolymers showed a high glass transition temperature $(T_g)$ and good thermal stability, which are desirable for optical applications. $T_g$ and $T_{10%}$ (10%-weight loss occurred) of the copolymers ranged from $120-140^{\circ}C$ and from $329-387^{\circ}C$, respectively.

• 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.