• Bulletin of the Korean Chemical Society
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• 제14권5호
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• pp.636-637
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• 1993

• 대한화학회지
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• 제38권12호
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• pp.915-920
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• 1994

치환(Z)-벤질(X)-아렌 술포네이트류와 치환(Y)-피리딘과의 Menschutkin형 반응을 $35\circC$ 아세토니트릴 용액에서 전기전도도법으로 측정하였다. 이 반응의 2차 반응속도상수로부터 Hammett $\rho$값을 구하였다. 음의 $\rho_Y$값은 전이 상태에서 친핵체로부터 기질의 벤질기에 하전이동이 일어나 친핵체의 질소에 양의 하전을 띤다. 양의 $\rho_X$값은 이탈기인 술포네이트에 음의 하전이 발달되어 있음을 나타내며 음의 $\rho_Z$값은 반응 중심인 벤질 탄소에 양의 하전을 띠고 있음을 각각 나타낸다. 복합 Hammett의 상호작용 항은 │$\rho_YZ$│ > │$\rho_XY$│ > │$\rho_ZX$│의 순으로 나타났으며 이들의 결과로부터 치환 benzyl arenesulfonate류와 치환 pyridine류의 반응은 dissociative $S_N2$으로 진행됨을 알 수 있었다.

• 대한화학회지
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• 제48권4호
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• pp.385-393
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• 2004

Benzofuroxan과 ethyl acetoacetate를 반응시켜 2-ethoxycarbonyl-3-methylquinoxaline 1,4-dioxide (8)를 합성하고, 이것을 hydrazine hydrate 또는 selenium dioxide와 반응시켜 2-hydrazinocarbonyl-3-methylquinoxaline 1,4-dioxide (9) 또는 2-ethoxycarbonyl-3-formylquinoxaline 1,4-dioxide (10)를 합성하였다. 화합물 9를 alkanoyl chloride류, benzoyl chloride류, heteroacyl chloride류 및 benzenesulfonyl chloride류와 반응시켜 3-methyl-2-(substituted hydrazinocarbonyl)quinoxaline 1,4-dioxide류 (11-14)를 합성하였다. 화합물 9를 sodium nitrite와 반응시켜 2-azidocarbonyl- 3-methylquinoxaline 1,4-dioxide (15)를 합성한 다음, 이것을 디옥산/알코올류 용매하에서 환류시켜 Curtius 자리옮김반응에 의한 N-(3-methyl-1,4-dioxoquinoxalin-2-yl)-alkyl carbamate류 (16)를 합성하였다. 그리고 화합물 15를 치환 아닐린류와 반응시켜 2-(3-substituted phenylureido)-3-methylquinoxaline 1,4-dioxide류 (17)를 합성하였다. 한편 화합물 10을 benzoic hydrazide 또는 치환 아닐린류와 반응시켜 quinoxaline 1,4-dioxide류 (18, 19)를 각각 합성하였다. 그리고 합성한 화합물들에 대한 제초력과 살균력도 조사하였다.

• Bulletin of the Korean Chemical Society
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• 제33권10호
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• pp.3253-3257
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• 2012

Second-order rate constants for the reactions of phenyl Y-substituted-phenyl carbonates 5a-g with Z-substituted-phenoxides ($k_{Z-PhO^-}$) have been measured spectrophotometrically in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. 4-Nitrophenyl phenyl carbonate (5e) is up to 235 times more reactive than 4-nitrophenyl benzoate (4e). The Br$\o$nsted-type plot for the reactions of 5e with Z-substituted-phenoxides is linear with ${\beta}_{nuc}=0.54$, which is typical for reactions reported previously to proceed through a concerted mechanism. Hammett plots correlated with ${\sigma}^o$ and ${\sigma}^-$ constants for the reactions of 5a-f with 4-chlorophenoxide exhibit highly scattered points. In contrast, the Yukawa-Tsuno plot results in an excellent linear correlation with ${\rho}_Y=1.51$ and r = 0.52, indicating that the leaving-group departure occurs at the rate-determining step (RDS). A stepwise mechanism, in which leaving-group departure occurs at RDS, has been excluded since the incoming 4-$ClPhO^-$ is more basic and a poorer nucleofuge than the leaving Y-substituted-phenoxides. Thus, the reaction has been concluded to proceed through a concerted mechanism. Our study has shown that the modification of the nonleaving group from benzoyl to phenyloxycarbonyl causes a change in the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway) as well as an increase in the reactivity.

• 콘크리트학회지
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• 제9권3호
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• pp.149-156
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• 1997

시멘트 모르타르의 압축강도 향상을 휘하여 분말혼화제를 제조하였으며,분말혼화재 사용에 따르는 유동성 감소를 억제하고자 고유동화제를 사용하였다. 분말혼화재(FAS)는 불산부생 II형 무수석고와 플라이애쉬 및 실리카흄을 혼합제조하여 시멘트 대신 각각10,20 wt% 씩 치환하였다. 물/고형분비(W/S)=0.40에서 FAS 로 치환된 시멘트 페이스트의 유동성은 저하되었고, 유동성 저하의 억제를 위한 고유동화제는 NSF와 NT-2가 효과적이었다. 시멘트 모르타르의 유동성은 II형 무수석고의 분말도가 미세할수록 증가하였고, 유동성저하는 FAS를 10 wt% 치환하였을 때 작게 나타났다. 압축강도는 10 wt%치환한 공시체가 20 wt%치환한 것보다 높게 나타났고 특히 $\gamma$ 를 10 wt%치환한 공시체( CI )에서 가장 높은 압축강도값을 나타내었다.

• Bulletin of the Korean Chemical Society
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• 제30권10호
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• pp.2403-2407
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• 2009

Second-order rate constants have been measured for two series of nucleophilic displacement reactions, i.e., reactions of 4-nitrophenyl benzoate with Z-substituted phenoxides and those of Y-substituted phenyl benzoates (1a-h) with 4-chlorophenoxide (4-ClPhO–) in 80 mol% $H_2O$/20 mol% DMSO at 25.0 ${\pm}\;0.1\;{^{\circ}C}$. The Br$\phi$nsted-type plot for reactions of 4-nitrophenyl benzoate with Z-substituted phenoxides exhibits an excellent linear correlation with ${\beta}_{nuc}$ = 0.72. Reactions of 1a-h with 4-chlorophenoxide result in also a linear Br$\phi$nsted-type plot with ${\beta}_{lg}$ = –0.62, a typical ${\beta}_{lg}$ value for a concerted mechanism. The Hammett plots correlated with ${\sigma}^o\;and\;{\sigma}^-$ constants show many scattered points for reactions of 1a-h with 4-chlorophenoxide. In contrast, the corresponding Yukawa-Tsuno plot exhibits an excellent linear correlation with $\rho_Y$ = 2.26 and r = 0.53, indicating that expulsion of the leaving group occurs at the rate-determining step (RDS) either in a concerted mechanism or in a stepwise pathway. However, a stepwise mechanism with leaving group departure being the RDS is excluded since the leaving Y-substituted phenoxide is less basic and a better nucleofuge than the incoming 4-ClPh$O^-$. Thus, the reactions have been concluded to proceed through a concerted mechanism, in which bond formation between the nucleophile and electrophilic center is more advanced than expulsion of the leaving group in the transition state on the basis of the magnitude of ${\beta}_{nuc}\;and\;{\beta}_{lg}$ values.

• Archives of Pharmacal Research
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• 제19권3호
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• pp.235-239
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• 1996

Six, heretofore undescribed, $5^I-Methyl-5^I-(5-Substituted uracil-1-ylmethyl)-2^I-oxo-3^I-methylenetetrahydrofurans(F, Cl, Br, l, CH_3, H)(6a-f)$were synthesized and evaluated against three cell lines (FM-3A, P-388 and U-937). For the preparation of .alpha.-methylene-.gamma.-butyrolactone bearing 5-substituted uracils (6a-f), the effcient Reformatsky type reaction was employed which involves the treatment of ethyl .alpha.(bromomethyl) acrylate and zinc with the respective 5-substituted uracil-1-ylacetones (5a-f). The acetone derivatives (5a-f) were directly obtained by the respective alkylation reaction of 5-substituted uracils with chloroacetone in the presence of $K_{2}$$CO_{3}$(or NaH). These lactone compounds 6a-f exhibited moderate to significant activity in all of the three cell lines, and 6b, 6c and 6e showed significant antitumor activities (inhibitory concentrations ($IC_{50}$) ranged from 1.3-3.8 .mu.g/ml.

• 약학회지
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• 제54권5호
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• pp.328-333
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• 2010

Comparative molecular field analyses (CoMFA) on the antiproliferative activity of N-substituted (R) 2-amino-5-(2,4-dihydroxyphenyl)-1,3,4-thiadiazole analogues (ADTs: 1-17) against bladder cancer (HCV29T) and rectal cancer (SW707) cells were studied quantitatively. The statistical predictability and fitness of CoMFA A1 model for bladder cancer cells were better than those of CoMFA F1 model for rectal cancer cells and the antiproliferative activity of ADTs depends on steric field (HCV29T: 93.1% & SW707: 83.8%). Also, from the contour maps of optimized CoMFA models, the activity for bladder cancer cells had predicted to increase when sterically favored groups were substituted on meta- and para-position, and sterically disfavored groups were substituted on one ortho-position of phenyl ring. The activity for rectal cancer cells had predicted to increase when sterically favored groups were substituted on para-position, and sterically disfavored groups were substituted on two ortho-position of phenyl ring as R-group.

• 한국식품과학회지
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• 제34권4호
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• pp.642-646
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• 2002

본 연구에서는 기능성 쌀을 이용한 쿠키를 개발하여 이화학적 관능적 품질 특성을 조사하였다. 반죽의 pH는 기능성 쌀가루를 10% 대체한 반죽이 대조군 보다 유의적으로 높은 pH를 나타내었다. 쿠키의 퍼짐성에서는 20%와 30% 대체한 시료군이 대조군 보다 유의적으로 높은 퍼짐성을 보였다. 시료군의 L값은 대조군이 69.31으로 가장 높았으며, b값은 20%대조 시료군이 35.60의 값으로 가장 높았다. 기능성 쌀가루를 다양한 수준으로 대체한 쿠키의 관능검사를 실시한 결과 기능성 쌀가루를 10% 대체한 시료군이 고소한 냄새, 고소한 맛, 경도, 색의 갈색정도에서 유의적으로 특성이 강하게 평가되었다. 쿠키의 기호도 검사 결과 쿠키의 전반적인 기호도에서 기능성 쌀가루를 20%와 30% 대체한 시료가 대조군과 함께 유의적으로 높은 기호도를 나타내었다. 따라서 기능성 쌀가루로 대체된 쿠키는 모든 대체비에서 대조구와 비교하였을 때 유의적인 차이가 없거나 유의적으로 높은 기호도를 나타내어 기능성 쌀쿠키 개발의 가능성을 보여주었다.

• 한국표면공학회지
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• 제54권4호
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• pp.178-183
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• 2021

The temperature and frequency dependence of the dielectric constant of the BaTiO₃ substituted with two types of donor dopants, Nb⁵⁺ and Ta⁵⁺, respectively, were compared and analyzed. Dielectric specimens of four specific compositions, Ba_0.95Nb_0.05TiO₃, Ba_0.90Nb_0.10TiO₃, Ba_0.95Ta_0.05TiO₃, and Ba_0.90Ta_0.010TiO₃ were prepared by calcining at 1100 ℃ and sintering at 1300 ℃ to have a perovskite structure to measure capacitance. XRD and SEM analysis were used to observe the structure, with particular focus on the integration into the Nb⁵⁺ and Ta⁵⁺ substituted BaTiO₃ crystal lattice. X-ray diffraction peaks in the (200) and (002) planes were observed between 45.10° and 45.45° of the BaTiO₃ solid solution substituted with different fractions of Nb⁵⁺ and Ta⁵⁺. The dielectric properties were analyzed and the relationship between the properties and structure of the substituted BaTiO₃ was established. The fine particles and high density of the substituted BaTiO₃ were maintained like pure BaTiO₃, and in particular, a shift toward the low temperature side of the phase transition temperature range was clearly found, unlike pure BaTiO₃. In addition, the phase transition at a temperature higher than the Curie temperature relatively satisfies the modified Curie-Weiss law.