• Proceeding of EDISON Challenge
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• 2014.03a
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• pp.371-383
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• 2014

이 연구에서는 팔라듐 착물 $Pd(PPh_3)_2$을 사용한 bromotoluene과 morpholine간의 coupling reaction (Buchwald-Hartwig amination) 반응 메커니즘을 계산화학적 방법을 이용하여 연구하였다. 용매화 자유에너지를 고려한 중간체 에너지를 비교하였으며, 반응물질이 o-bromotoluene 일 때와 p-bromotoluene 일 때, 반응 중간체로 monophosphine 착물이 형성되는 경우와 bisphosphine 착물이 형성되는 경우를 비교하였으며, 반응 중간체로 bisphosphine 착물이 형성되는 경우 cis 이성질체가 중간체인 경우와 trans 이성질체가 중간체인 경우를 비교하였다. 그 결과, 반응물로 p-bromotoluene을 사용할 때 o-bromotoluene을 사용할 때보다 중간체가 상대적으로 더 안정하여 더 좋은 수득률을 얻을 수 있을 것으로 예상되었다. 또한 $Pd(PPh_3)_n(o-tolyl)(N(CH_2CH_2)_2O)$ (n=1 또는 2) 중간체를 제외하고는 모든 경우에서 bisphosphine 중간체가 형성되는 반응경로가 더 안정한 것으로 밝혀졌다. 그리고 $Pd(PPh_3)_2ArBr$의 경우 trans 이성질체가 cis 이성질체보다 안정하지만 $Pd(PPh_3)_2Ar(N(CH_2CH_2)_2O)$의 경우 반대로 cis 이성질체가 trans 이성질체보다 안정한 것으로 나타났다.

• Bulletin of the Korean Chemical Society
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• v.30 no.1
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• pp.83-91
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• 2009

To develop new anticancer agents, 3-allylthio-6-aminopyridazine derivatives were synthesized from maleic anhydrides or phthalic anhydrides by formation of a pyridazine nucleus, dichlorination, allylthiolation and amination. The pyridazine nuclei were obtained by condensing a hydrazine monohydrate with maleic anhydride. An allylthio group as a pharmacologically active group was introduced into one side of a pyridazine ring. Arylalkylamines with benzene or pyridine moieties or heterocycloalkylamines with heterocycle moieties such as morpholine, piperidine, or pyrrolidine were also introduced into the para-position of allylthio pyridazine. These new compounds showed antiproliferative activities against SK-Hep-1 human liver cancer cells in MTT assays. These compounds are thus promising candidates for chemotherapy of hepatocellular carcinomas. Two compounds, 20c and 22a, showed higher potencies for inhibiting growth of hepatocellular carcinoma cells than did K6 ($ID_50$=1.08 mM). This suggests the potential anticancer activity of these two compounds.

• The Korean Journal of Rheology
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• v.10 no.1
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• pp.44-49
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• 1998

셀룰로오스/N-methyl morpholine N-oxide(NMMO)용액에 있어서 셀룰로오스의 분 자량 및 농도, 그리고 NMMO의 수화도가 유변학적 특성에 미치는 영향을 고찰하였다. 12wt%의 경우 NMMO의 수화도가 감소할수록 더 높은 온도에서 lower Newtonian 흐름영 역이 사라졌다. 15wt%에서는 측정된 전단영역에서 lower Newtonian 유동영역의 관찰되지 않았다. 동일한 농도에서 NMMO의 수화도가 감소할수록 점도가 증가하였으나 중량평균중 합도가 940인셀룰로오스/NMMO 용액의 경우 9$0^{\circ}C$에서 점도가 오히려 낮아졌다. 뿐만아니 라 이온도에서 power-law의 급작스런 감소도 나타낫다. NMMO의 수화도가 클수록 제1법 선응력차나 연신점도에 대한 온도의 영향이 증가하였다.

• YAKHAK HOEJI
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• v.33 no.5
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• pp.273-279
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• 1989

2,3-Dichloro-1,4-naphthoquinone was reacted with o-fluoroaniline, p-sulfadiazine, p-acetoanline, N,N-dimethyl-1,4-phenylenediamine as a nucleophilic substitution to form 2-chloro-3-(N-arylamino)-1,4-naphthoquinones (1.-6.) in good yield. 2,3-Dibromo-1,4-naphthoquinone was also reacted with o-fluoroaniline, m-aminobenzoic acid, m-chloroaniline, morpholine, p-acetoaniline, N,N-dimethyl-1,4-phenylenediamine as a nucleophilic substitution to give 2-bromo-3-(N-arylamino)-1,4-naphthoquinones (7.-12.). These new compounds are expected to have a biological activities such as anticoagulant, cytotoxic.

• Applied Chemistry for Engineering
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• v.30 no.1
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• pp.81-87
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• 2019

In this study, synthetic methods and physical properties for a new class of glycidyl azide polymer (GAP) were investigated for energetic thermoplastic elastomers (ETPE). Four kinds of GAP copolymer polyols were synthesized by introducing nucleophiles such as azide, alkoxide and alkyl amine into poly(epichlorohydrin) (PECH). The GAP copolymer synthetic reaction can be evaluated as an environmental benign and efficient synthetic method due to the simultaneous one-step reaction using two kinds of nucleophiles and the complete consumption of sodium azide. The relative stoichiometric substitution ratio analysis and the progress of reaction were checked and monitored by inverse gated decoupled $^{13}C$ NMR and Fourier transform infrared (FT-IR) spectroscopy. The glass transition temperature and molecular weight were measured by differential scanning calorimetry (DSC) and gel permeation chromatography (GPC) analysis. The synthesized poly($GA_{0.8}-butoxide_{0.2}$), poly($GA_{0.7}-n-butylamine_{0.3}$), poly($GA_{0.7}-dipropylamine_{0.3}$) and poly($GA_{0.7}-morpholine_{0.3}$) had a glass transition temperature ranged from -39 to $-26^{\circ}C$.

• YAKHAK HOEJI
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• v.41 no.3
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• pp.283-293
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• 1997

Some analogs and their Mannich bases of Antineoplaston A10 (A10) were synthesized. Chemical yield for the 2-(or 3-)thienyl, benzol, and phenylpropionyl analogs were high but 1-naphthyl analog was synthesized in low yield. The Mannich bases formation of these analogs with morpholine went verywell compared to other bases. 1-Naphthyl, 4-nitrobenzoyl, and phenylpropionyl analogs of A10 showed weak in vitro activity but the other A10 analogs showed weaker or no activity at 10-1000mcg/ml. But their Mannich bases containing A10analogs showed good in vitro activity compared to simple A10 analogs.

• Bulletin of the Korean Chemical Society
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• v.35 no.7
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• pp.2130-2134
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• 2014

A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl isonicotinate (7) with a series of cyclic secondary amines in MeCN. The plots of $k_{obsd}$ vs. [amine] curve upward for the reactions with weakly basic amines (e.g., morpholine, 1-(2-hydroxyethyl)piperazine, and piperazine) but are linear for those with strongly basic amines (e.g., piperidine and 3-methylpiperidine). The curved plots for the reactions with the weakly basic amines are typical for reactions reported previously to proceed through uncatalyzed and catalyzed routes with two intermediates (e.g., a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$). In contrast, the linear plots for the reactions with the strongly basic amines indicate that the catalytic route (i.e., the deprotonation process to yield $T^-$ from $T^{\pm}$ by a second amine molecule) is absent. The Br${\o}$nsted-type plots for $Kk_2$ and $Kk_3$ (i.e., the rate constants for the uncatalyzed and catalyzed routes, respectively) exhibit excellent linear correlations with ${\beta}_{nuc}$ = 0.99 and 0.69, respectively. The effect of amine basicity on the reaction mechanism is discussed in detail.

• Journal of the Korean Applied Science and Technology
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• v.27 no.2
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• pp.168-174
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• 2010

In this research, an effective method for reducing the fibrillation of lyocell fibers, which are spun from a solution of cellulose in N-methyl morpholine-N-oxide(NMMO), through consecutive chemical treatments. Undried solution-spun cellulosic fiber was firstly treated with 10 to 30 wt% of multifunctional crosslinking agents, such as ethylene glycol poly(3-chloro-2-hydroxypropyl) ether, and then dipped into alkaline solution to introduce epoxy functions. Finally steam condition was applied to occur a chemical crosslinking in order to reduce the fibrillation on the surface of fibers. Fibrillation was also reduced significantly by adding extra $Na_2SO_4$ in NaOH solution. In addition, Antifibrilllated lyocell fibers show the slightly higher dyeability(4 %) to Cibacron Blue without serious reduction of mechanical properties.

• Bulletin of the Korean Chemical Society
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• v.29 no.4
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• pp.767-771
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• 2008

Second-order rate constants have been measured spectrophotometrically for the Michael-type reaction of 1-(Xsubstituted phenyl)-2-propyn-1-ones (2a-f) with amines in $H_2O$ at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. A linear Brønsted-type plot is obtained with ${\beta}_{nuc}$ = 0.25 ${\pm}$ 0.02, a typical $\beta_{nuc}$ value for reactions which proceed through a stepwise mechanism with attack of amine on the electrophilic center being the rate-determining step. Secondary alicyclic amines are found to be more reactive than isobasic primary amines. The Hammett plot for the reactions of 2a-f with morpholine is not linear, i.e., the substrate with a strong electron-donating group (e.g., 4-MeO) exhibits a negative deviation from the Hammett plot. However, the Yukawa-Tsuno plot for the same reactions exhibits an excellent linear correlation with ρ = 0.62 and r = 0.82. Thus, it has been proposed that the nonlinear Hammett plot is not due to a change in the ra te-determining step but due to ground-state stabilization through resonance interactions.

• Journal of the Korean Chemical Society
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• v.57 no.2
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• pp.234-240
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• 2013

The synthesis of title compounds were accomplished by synthetic sequence shown in Scheme 1. Chalcones on cyclocondensation with thiourea in ethanol and potassium hydroxide under reflux yielded the respective dihydropyramidin-2(1H)-thiones. Each of the dihydropyrimidin thiones was, then subjected to the Mannich condensation in alkaline medium using three different secondary amines, viz., dimethylamine, diethylamine and morpholine to obtain a new series of S-Mannich bases. All the synthesised compounds ($C_1-C_{15}$) were evaluated for their antiulcer and antibacterial activities. Compounds $C_4$, $C_5$, $C_6$, $C_{14}$ and $C_{15}$ exhibited relatively more potent antiulcer activity but not comparable to the standard; Omeprazole, while $C_1$, $C_2$, $C_3$ and $C_{13}$ were moderate in activity at 100 mg/kg p.o. All the compounds ($C_1-C_{15}$) showed mild to moderate activity against both Gram-positive (S.aureus, L.delbrueckii) and Gram-negative (P.vulgaris, E.coli) bacteria. Amongst the compounds tested, only $C_6$, $C_9$, $C_{12}$ and $C_{15}$ were found to be potent.