Effect of Substituents on Benzenesulfonyl Motif of 4-Phenyl-1-arylsulfonylimidazolidinones for Their Cytotoxicity

Lee, Hui-Soon,Park, Kyung-Lae,Choi, Sang-Un,Lee, Chong-Ock,Jung, Sang-Hun The Pharmaceutical Society of Korea 2000 Archives of Pharmacal Research Vol.23 No.6

To explore the effect of substituents' on phenyl motif on sulfonyl function of novel anticancer 4-phenyl-1-benzenesulfonylimidazolidinones (1), electron donating or withdrawing sub-stituents were introduced at 3 or 4-position and the analogs were tested against human lung (A549) and colon (HCT-15) cancer cell lines. Quantitative structure activity relation-ship of the 4-substituted series shows that only STERIMOL L values are well correlated. The increment of substituent's volume enhances the activity against both cell lines. The small substituent at 3-position additionally increases the activity. However naphthyl group in place of phenyl reduces the activity, Therefore the phenyl motif with sterically large substituent at 4-position and small substituent at 3-position may be important for their activity. Integration of these substituents' effects into the structural design led to discover the more potent analog, 4-phenyl-1-(N-acetylindoline-5-sulfonyl) imidazolidinone (1n).

Dual Substituent Effects on Anilinolysis of Bis(aryl) Chlorothiophosphates

Hasi Rani Barai,Hai Whang Lee 대한화학회 2013 Bulletin of the Korean Chemical Society Vol.34 No.12

The reactions of bis(Y-aryl) chlorothiophosphates (1) with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at 55.0 oC. 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 (ρXY) 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 ρXY 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-centertype transition state is proposed based on the positive sign of ρXY and primary normal deuterium kinetic isotope effects.

Dual Substituent Effects on Anilinolysis of Bis(aryl) Chlorothiophosphates

Barai, Hasi Rani,Lee, Hai Whang Korean Chemical Society 2013 Bulletin of the Korean Chemical Society Vol.34 No.12

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.

Influence of Simultaneous Tuning of Molecular Weights and Alkyl Substituents of Poly(thienoisoindigo-<i>alt</i>-naphthalene)s on Morphology and Change Transport Properties

Cho, Hye Jin,Kang, Seok-Ju,Lee, Sang Myeon,Jeong, Mingyu,Kim, Gyoungsik,Noh, Yong-Young,Yang, Changduk American Chemical Society 2017 ACS APPLIED MATERIALS & INTERFACES Vol.9 No.36

<P>To simultaneously assess the impact of molecular weight (M-n) and alkyl substituent variations of polymers on the structural and optoelectronic properties, herein, we conduct a systematic study of a series of poly(thienoisoindigo-alt-naphthalene) (PTIIG-Np)-based polymers containing different alkyl substituents (2-hexyldecyl (HD), 2-octyldodecyl (OD), and 2-decyltetradecyl (DT) chains) and M-n's (low (L) and high (H)). All of the polymers produce almost identical energy levels, whereas their optical spectra, show a clear dependence on M-n's and the alkyl substituents. Interestingly, increasing the alkyl substituent sizes of the polymers steadily increases the lamellar d-spacings (d(100)), ultimately leading to a densely packed lamellar structure for PTIIGHD-Np. In addition, both H-PTIIGOD-Np and H-PTIIGDT-Np exhibit larger pi-stacking crystallites than the corresponding low-M-n polymers, while for PTIIGHD-Np, their size increases in the low-M-n batch. Ultimately, L-PTIIGHD-Np shows the best hole mobility of 1.87 cm(2) V-1 s(-1) in top-gate and bottom-contact organic field-effect transistors (OFETs) with a poly(methyl methacrylate), which is nearly 1 order of magnitude higher than other polymers tested in this study. Our results demonstrate that the simultaneous M-n and alkyl substituent engineering of the polymers can optimize their film morphology to produce high-performance OFETs.</P>

Synthesis and Properties of Salen–Aluminum Complexes as a Novel Class of Color-Tunable Luminophores

Hwang, Kyu Young,Kim, Hyoseok,Lee, Yoon Sup,Lee, Min Hyung,Do, Youngkyu WILEY-VCH Verlag 2009 Chemistry Vol.15 No.26

<P>Showing their true colors? Full emission color tuning in the visible region can be achieved with salen–aluminum complexes that are electronically modulated at C5 of the phenoxide ring in the salen moiety. Emission spectra for various substituents R<SUP>5</SUP> are shown (EWG: electron-withdrawing group, EDG: electron-donating group). <img src='wiley_img/09476539-2009-15-26-CHEM200900137-content.gif' alt='wiley_img/09476539-2009-15-26-CHEM200900137-content'> </P><P>A series of salen–aluminum complexes, [{(R<SUP>5</SUP>)<SUB>2</SUB>-salen(3-tBu)<SUB>2</SUB>}Al(OC<SUB>6</SUB>H<SUB>4</SUB>-p-C<SUB>6</SUB>H<SUB>5</SUB>)] (salen=N,N′-bis(salicylidene)ethylenediamine; R<SUP>5</SUP>=H (1), tBu (2), Br (3), Ph (4), OMe (5), NMe<SUB>2</SUB> (6)) and [{5,5′-(NMe<SUB>3</SUB>)<SUB>2</SUB>-salen(3-tBu)<SUB>2</SUB>}Al(OC<SUB>6</SUB>H<SUB>4</SUB>-p-C<SUB>6</SUB>H<SUB>5</SUB>)][OTf]<SUB>2</SUB> (7; OTf=CF<SUB>3</SUB>SO<SUB>3</SUB>) that are electronically modulated directly at C5 of the phenoxide ring in the salen moiety has been prepared. The crystal structures of 1, 4, 6, and 7 determined by X-ray diffraction reveal distorted square-pyramidal geometries around the Al atoms. Complexes 1–7 are all air-stable in both the solid and solution states and have high thermal stability (decomp 313–338 °C). Differential scanning calorimetric analyses show that they can form amorphous glasses with glass transition temperatures of 95–132 °C depending on the C5 substituent. UV/Vis absorption spectra of the complexes exhibit major bands at λ=338–413 nm assignable to salen-centered π–π* transitions with a gradual red shift of the absorption maximum wavelengths as the substituent is varied from an electron-withdrawing (NMe<SUB>3</SUB>) to an electron-donating group (NMe<SUB>2</SUB>). The maxima in the emission spectra of 1–7 occur over the entire visible region, ranging from λ=438 nm for 7 to λ=599 nm for 6, with high fluorescence quantum efficiencies of up to Φ=0.40 for 4 in solution. DFT calculations suggest that the low-energy electronic transitions in 1–7 are characterized by HOMO<SUB>−i</SUB>–LUMO<SUB>+1</SUB> (i=1 for 1–6 or i=4 for 7) transitions localized on the salen moiety, with much involvement of the C5 position in the HOMO<SUB>−i</SUB>. Thus, the electronic alteration at the C5 position of the phenoxide ring, which mainly affects the HOMO<SUB>−i</SUB> energy levels of salen–Al luminophores, is responsible for the observed emission color-tuning properties over the entire visible region.</P> <B>Graphic Abstract</B> <P>Showing their true colors? Full emission color tuning in the visible region can be achieved with salen–aluminum complexes that are electronically modulated at C5 of the phenoxide ring in the salen moiety. Emission spectra for various substituents R<SUP>5</SUP> are shown (EWG: electron-withdrawing group, EDG: electron-donating group). <img src='wiley_img/09476539-2009-15-26-CHEM200900137-content.gif' alt='wiley_img/09476539-2009-15-26-CHEM200900137-content'> </P>

Tailoring the Excited-State Intramolecular Proton Transfer (ESIPT) Fluorescence of 2-(2'-Hydroxyphenyl)benzoxazole Derivatives

Seo, Jang-Won,Kim, Se-Hoon,Park, Sang-Hyuk,Park, Soo-Young Korean Chemical Society 2005 Bulletin of the Korean Chemical Society Vol.26 No.11

The excited-state intramolecular proton transfer (ESIPT) fluorescence in the 2-(2'-hydroxyphenyl)benzoxazole (HBO) derivatives with different electron donor and acceptor substituents was studied by spectroscopic and theoretical methods. Changes in the electronic transition, energy levels, and orbital diagrams of HBO analogues were investigated by the semi-empirical molecular orbital calculation and were correlated with the experimental spectral position of ESIPT keto emission. It was found that the presence of substituents, regardless of their nature, resulted in the red-shifted absorption relative to HBO. However, the spectral change of the ESIPT fluorescence was differently affected by the nature of substituent: hypsochromic shift with electron donor and bathochromic shift with electron acceptor.

Tailoring the Excited-State Intramolecular Proton Transfer (ESIPT) Fluorescence of 2-(2'-Hydroxyphenyl)benzoxazole Derivatives

박수영,Sehoon Kim,박상혁,Jangwon Seo 대한화학회 2005 Bulletin of the Korean Chemical Society Vol.26 No.11

The excited-state intramolecular proton transfer (ESIPT) fluorescence in the 2-(2'-hydroxyphenyl)benzoxazole (HBO) derivatives with different electron donor and acceptor substituents was studied by spectroscopic and theoretical methods. Changes in the electronic transition, energy levels, and orbital diagrams of HBO analogues were investigated by the semi-empirical molecular orbital calculation and were correlated with the experimental spectral position of ESIPT keto emission. It was found that the presence of substituents, regardless of their nature, resulted in the red-shifted absorption relative to HBO. However, the spectral change of the ESIPT fluorescence was differently affected by the nature of substituent: hypsochromic shift with electron donor and bathochromic shift with electron acceptor.

rac-Me₂Si(2-p-tolylindenyl)₂ZrCl₂ 촉매를 이용한 에틸렌/1-옥텐의 공중합 특성

안성현,박융호,Ahn, Sung-Hyun,Park, Yeung-Ho 한국공업화학회 2007 공업화학 Vol.18 No.5

새롭게 합성된 $rac-Me_2Si(2-p-tolylindenyl)_2ZrCl_2$ 촉매와 인디닐 리간드에 치환체가 붙어 있지 않는 상용촉매인 $rac-Me_2Si(Ind)_2ZrCl_2$ 촉매들을 조촉매인 methylaluminoxane (MMAO)를 사용하여 에틸렌/1-옥텐 공중합을 실시하였고, 반응물 내 1-옥텐의 농도를 변화시키며 얻어진 공중합체의 특성을 조사하였다. 촉매활성에 있어서 $rac-Me_2Si(2-p-tolylindenyl)_2ZrCl_2$ 촉매를 이용하여 공중합을 실시한 경우 다리구조를 가진 다른 촉매들과 달리 촉매활성이 감소하여 comonomer의 첨가에 따라 활성이 증가하는 comonomer effect는 발견되지 않았다. $^{13}C$ NMR 분석에서 공중합체에 삽입된 1-옥텐의 양은 촉매 리간드에 붙은 치환체에 의존함을 보였으며, 2-p-tolyl 치환체가 붙은 촉매로 얻어진 공중합체에서 1-옥텐 삽입량이 더 높음을 보였다. DSC, GPC 분석에서 반응물 내 1-옥텐의 농도가 증가함에 따라 공중합체의 녹는점, 결정성, 분자량이 모두 감소하였으며 $rac-Me_2Si(Ind)_2ZrCl_2$ 촉매보다 $rac-Me_2Si(2-p-tolylindenyl)_2ZrCl_2$ 촉매의 경우 녹는점, 결정성 및 분자량의 감소폭이 더 크게 나타났다. The copolymerization characteristics of a newly-synthesized catalyst, $rac-Me_2Si(2-p-tolylindenyl)_2ZrCl_2$, and its analogue, $rac-Me_2Si(Ind)_2ZrCl_2$, were examined in the ethylene/1-octene copolymerization while varying the concentration of 1-octene in the reaction mixture. The activity of $rac-Me_2Si(2-p-tolylindenyl)_2ZrCl_2$ catalyst was decreased with increase of comonomer concentration, which is different from the usual comonomer effect of the metallocene catalysts with a bridge structure. The contents of 1-octene in the copolymer from the catalyst with 2-p-tolyl substituent were higher than those from the catalyst without that substituent. The melting point, crystallinity, and molecular weight decreased with comonomer content which was more apparent for $rac-Me_2Si(2-p-tolylindenyl)_2ZrCl_2$ catalyst.

Substituent-Dyeing Properties Relationship of Disperse Dyes on Polyester in Low Pressure Waterless Dyeing System

Shunjie Yu,Hongjuan Zhang,Liujun Pei,Shuaitong Liang,Aixue Dong,Jiping Wang 한국섬유공학회 2022 Fibers and polymers Vol.23 No.2

Decamethylcyclopentasiloxane (D5) has attracted an increasing attention because it can realize waterless dyeing ofchemical fibers. In this paper, two azo disperse dyes with different substituents were synthesized, and compared with C.I. Disperse Red 73 to study the relationship between structure and dyeing properties systematically in D5 media. The resultsshowed that the dyeing uptake of dyes increased from 85.5 % to 98.0 % with the substituent changing from N-ethyl to Nacetoxyethylgroup. This was because the solubility of dyes in D5 media showed an evident reduction. Although the dyescontaining N-cyanoethyl group had the lowest solubility, the dyeing uptake became 93.4 %, which was slight lower than thatof dyes with N-acetoxyethyl group. This was because an introduction of N-cyanoethyl group increased dye molecularaggregation in D5 media, making it difficult to diffuse. Additionally, the dyes with N-ethyl or N-acetoxyethyl groups showedbetter washing fastness and rubbing fastness than that of dye containing N-cyanoethyl group. These results provide apotential theoretical guidance for improving exhaustion of disperse dyes in waterless dyeing system. This study will promotetextile industry sustainable development.

Significant Substituent Effects on Pyridinolysis of Aryl Ethyl Chlorophosphates in Acetonitrile

어디까리,이해황 대한화학회 2014 Bulletin of the Korean Chemical Society Vol.35 No.5

The substituent effects on the pyridinolysis (XC5H4N) of Y-aryl ethyl chlorophosphates are investigated in acetonitrile at 35.0 oC. The two strong π-acceptor substituents, X = 4-Ac and 4-CN in the X-pyridines, exhibit large positive deviations from the Hammett plots but little positive deviations from the Brönsted plots. The substituent Y effects on the rates are really significant and the Hammett plots for substituent Y variations in the substrates invariably change from biphasic concave downwards via isokinetic at X = H to biphasic concave upwards with a break point at Y = 3-Me as the pyridine becomes less basic. These are interpreted to indicate a mechanistic change at the break point from a stepwise mechanism with a rate-limiting bond formation (ρXY = –6.26) for Y = (4-MeO, 4-Me, 3-Me) to with a rate-limiting leaving group expulsion from the intermediate (ρXY = +5.47) for Y = (4-Me, H, 3-MeO). The exceptionally large magnitudes of ρXY values imply frontside nucleophilic attack transition state.