• Bulletin of the Korean Chemical Society
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• 제34권8호
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• pp.2325-2329
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• 2013

Second-order rate constants $k_N$ have been measured for reactions of benzyl 2-pyridyl thionocarbonate (4b) and t-butyl 2-pyridyl thionocarbonate (5b) with a series of cyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. The $k_N$ values for the reactions of 4b and 5b have been compared with those reported previously for the corresponding reactions of benzyl 2-pyridyl carbonate (4a) and t-butyl 2-pyridyl carbonate (5a) to investigate the effect of changing the electrophilic center from C=O to C=S on reactivity and reaction mechanism. The thiono compound 4b is more reactive than its oxygen analogue 4a. The Br${\o}$nsted-type plots for the reactions of 4a and 4b are linear with ${\beta}_{nuc}=0.57$ and 0.37, respectively. The reactions of 4a were previously reported to proceed through a concerted mechanism, while those of 4b in this study have been concluded to proceed through a stepwise mechanism with formation of an intermediate being the rate-determining step on the basis of the ${\beta}_{nuc}$ value of 0.37. Enhanced polarizability upon changing the C=O in 4a by C=S has been suggested to be responsible for the reactivity order and the contrasting reaction mechanisms. In contrast, the reactivity of 5a and 5b is similar, but they are much less reactive than 4a and 4b. Furthermore, the reactions of 5a and 5b have been concluded to proceed through the same mechanism (i.e., a concerted mechanism) on the basis of linear Bronsted-type plots with ${\beta}_{nuc}=0.45$ or 0.47. It has been concluded that the strong steric hindrance exerted by the t-Bu in 5a and 5b causes a decrease in their reactivity and forces the reactions to proceed through a concerted mechanism.

• 분석과학
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• 제5권3호
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• pp.239-247
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• 1992

메틸기가 한 개 또는 두 개 치환된 10가지 메틸아닐리늄 이온과 18-크라운-6와의 착물 형성 및 선택성을 메탄올에서 적하수은 전극에 의해 조사하였다. 메틸아닐리늄 이온과 18-크라운-6와의 착물의 안정도 상수는 메틸기의 위치와 개수에 따른 입체장애 효과에 의해 큰 차이를 나타내었다. 또한 반파전위의 차가 매우 작아 일반적인 방법으로는 분석이 불가능한 메틸아닐리늄 이성질체 혼합물 등에 보조 착화제로 18-크라운-6를 첨가하여 입체장애에 의한 착물반응의 선택성을 이용하여 분석을 시도하였다. 그 결과 18-크라운-6와 두 게스트 이온의 안정도 상수의 차, ${\Delta}log\;K$가 대략 0.7~1.3인 경우 이성분 혼합물의 확인이 정성적으로 가능하였으며, 1.6 이상인 경우에는 정량적인 개별분석도 가능하였다. 이는 18-크라운-6가 아닐리늄의 메틸치환기의 위치에 따라 입체장애의 정도를 선별적으로 인식하여 큰 착물형성 선택성을 나타낸 결과로 각 환원파의 음전위 이동 정도가 크게 달라지기 때문이다.

• Bulletin of the Korean Chemical Society
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• 제29권8호
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• pp.1459-1463
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• 2008

Second-order rate constants (kN) have been measured spectrophotometrically for reactions of 3,4-dinitrophenyl 2-thiophenecarboxylate (2) with a series of alicyclic secondary amines in 80 mol % $H_2O$/20 mol % dimethyl sulfoxide at 25.0 ${^{\circ}C}$. The Brønsted-type plot exhibits a downward curvature for the aminolysis of 2. The curved Brønsted-type plot is similar to that reported for the corresponding reactions of 2,4-dinitrophenyl 2- thiophenecarboxylate (1). The reactions of 1 and 2 have been suggested to proceed through the same mechanism, i.e., through a zwitterionic tetrahedral intermediate ($T^{\pm}$) with a change in the rate-determining step. Substrate 2 is less reactive than 1 toward weakly basic amines (e.g., $pK_a$ < 10.4) but becomes more reactive as the basicity of amines increases further. Dissection of kN into the microscopic rate constants has revealed that the reaction of 2 results in a smaller $k_2/k_{-1}$ ratio but larger $k_1$ than the corresponding reaction of 1. Steric hindrance exerted by the ortho-nitro group has been suggested to be responsible for the smaller $k_1$ value found for the reactions of 1.

• 폴리머
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• 제26권3호
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• pp.344-352
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• 2002

본 연구에서는 두 가지 열잠재성 양이온 촉매인 triphenyl benzyl phosphoinium hexa-fluoroantimonate (TBPH)와 benzyl 2-methylpyrazinium hexafluoroantimonate (BMPH)를 새로이 합성하였다. 그리핀 TBPH 혹은 BMPH 1 phr에 의해 개시되어진 이관능성 에폭시 수지(diglycidylether of bisphenol A, DGEBA)의 열 및 기계적 특성들을 연구하였다. 그 실험적인 결과들로서, 에폭시/TBPH 시스템은 에폭시/BMPH 시스템 보다 더 높은 경화 온도와 임계응력 세기인자 ($K_{IC}$) 값을 보였다. 이것은 TBPH에서 4개의 페닐기의 느린 열확산 속도와 벌크 구조 때문으로 사료된다. 그러나, Coats-Redfern 방법에 의하여 결정된 분해 활성화 에너지는 TBPH의 경우가 더 낮게 나타났다. 이러한 결과는 TBPH의 입체장애에 의해서 끊어진 짧은 사슬 구조가 발달되었기 때문인 것으로 사료된다.

• Archives of Pharmacal Research
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• 제21권5호
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• pp.595-598
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• 1998

The rate of the GSH conjugate formation, the inhibition of DNA topoisomerase-I and the cytotoxic activity against L1210 cells of the naphthoquinones showed the same order; 5,8-dimethoxy-1,4-naphthoquinone (DMNQ)>6-(1-hydroxyethyl)-DMNQ>2-(1-hydroxyethyl)-DMNQ; the steric hindrance of the substituents, particularly 2-substutuent, in reacting with cellular nucleophiles must be the main cause for lowering the bioactivities. Acetylation of 2-(1-hydroxyethyl)-DMNQ producing 2-(acetyloxyethyl)-DMNQ potentiated the bioactivities; 2-(-hydroxyethyl)-DMNQ did not react with GSH and the enzyme, and showed $ED_{50}$ of 0.146 mg/ml for the cytotoxcity. Furthermore, the acetylation 2-(1-hydroxyethyl)-DMNQ(T/C, 119%) enhanced the T/C values for the mice bearing S-180 tumor {T/C of 2-(1-acetyloxyethyl)-DMNQ, 276%]. It was assumed that the difference in bioactivities ensued by acetylation was based on the mechanism of the so-called bioreductive alkylation.

• Bulletin of the Korean Chemical Society
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• 제29권4호
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• pp.772-776
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• 2008

Second-order rate constants ($k_N$) have been measured spectrophotometrically for reactions of 3,4-dintrophenyl 2-furoate (2) with a series of secondary alicyclic amines in 80 mol % $H_2O$/20 mol % dimethyl sulfoxide (DMSO) at 25.0 ${^{\circ}C}$. The Bronsted-type plot exhibits a downward curvature for the aminolysis of 2, which is similar to that reported for the corresponding reactions of 2,4-dintrophenyl 2-furoate (1). Substrate 2 is less reactive than 1 toward all the amines studied but the reactivity difference becomes smaller as the amine basicity increases. Dissection of the second-order rate constants into the microscopic rate constants has revealed that the reaction of 2 results in a smaller $k_2/k_{-1}$ ratio but slightly larger $k_1$ value than that of 1. Steric hindrance has been suggested to be responsible for the smaller $k_1$ value found for the reactions of 1, since the ortho-substituent of 1 would inhibit the attack of amines (i.e., the $k_1$ process).

• Macromolecular Research
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• 제17권11호
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• pp.870-873
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• 2009

In this study, 2-diglycidylether of benzotrifluoride (2-DGEBTF) and 4-diglycidylether of benzotrifluoride (4-DGEBTF) epoxy resins, which contained fluorine groups in the main chain, were synthesized. The resins were characterized by FTIR, $^1H$ NMR, $^{13}C$ NMR and $^{19}F$ NMR spectroscopy. The 2-DGEBTF and 4-DGEBTF epoxy resins were cured with triethylene tetramine (TETA), and the effect of the fluorine group on the synthesized epoxy resin on the cure behavior, thermal, and mechanical properties was investigated. The 2-DGEBTF/TETA system was more reactive than the 4-DGEBTF/TETA system, whereas the thermal stability factor i.e., the decomposition activation energy ($E_d$), of 4-DGEBTF/TETA was higher than that of 2-DGEBTF/TETA. These results can be explained by the decrease in cross-linking density and decomposition of the short side chains, resulting in the $CF_3$ group at the para position. However, the $K_{IC}$ value of 4-DGEBTF/TETA was higher than that of 2-DGEBTF/TETA. This was attributed to the increase in flexibility in the epoxy backbone, resulting in a difference in steric hindrance and polarlizability.

• Korean Chemical Engineering Research
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• 제50권1호
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• pp.135-140
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• 2012

반응열량계를 사용하여 1, 2, 3차 아민 수용액과 이산화탄소의 반응열을 각각 측정하였다. 이를 통해 MEA(monoethanolamine, 1차 아민), EAE(2-(ethylamino) ethanol, 2차 아민), MDEA (N-methyldiethanolamine, 3차 아민) 30 wt% 수용액이 $40^{\circ}C$에서 이산화탄소와 반응시 발생하는 반응열을 측정하고 이를 $CO_2$의 loading ratio에 따라 어떻게 변화하는지 평가하였다. 또한, 입체장애 구조를 가지는 AMP(2-amino-2-methyl-1-propanol, 1차 아민), DEA(diethanolamine, 2차 아민), TEA(triethanolamine, 3차 아민) 30 wt% 수용액의 반응열을 각각 측정하여 입체장애 구조가 반응열에 미치는 영향을 살펴보았다. 그 결과, 흡수제의 입체장애 유무와 관계없이 1차 > 2차 > 3차 아민 순으로 반응열이 증가함을 확인하였다. 그리고 입체장애 아민이 동일 차수의 비 입체장애 아민보다 상대적으로 반응열이 낮지만 그 차이는 크지 않음을 확인하였다.

• Bulletin of the Korean Chemical Society
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• 제18권8호
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• pp.865-868
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• 1997

Second-order rate constants have been measured spectrophotometrically for the reactions of p-nitrophenyl phenylacetate (1) and benzoate (2) with a series of alicyclic amines in H2O containing 20 mole % DMSO at 25.0 ℃. 1 appears to be more reactive than 2 toward all the amines studied, although phenylacetic acid is a weaker acid than benzoic acid. The higher reactivity of 1 can be attributed to resonance and/or steric effect, since the ground state of 2 can be stabilized by resonance and 1 would experience less steric hindrance due to the presence of CH2 group between phenyl and C=O group. The reactivity of the amines increases with increasing their basicity. The Bronsted-type plots for aminolysis of 1 and 2 show good linearity with βnuc values of 0.81 and 0.85, respectively, indicating that the TS structures of the aminolyses of 1 and 2 are similar. Besides, the linear Bronsted plots obtained in the present system clearly suggest that there is no mechanism change for the given series of the amines and the reactions of 1 and 2 proceed in a same mechanism.

• Bulletin of the Korean Chemical Society
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• 제19권11호
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• pp.1233-1238
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• 1998

Transglycosylation reactions among methyl 2,3,4,6-tetra-O-methyl-D-glycopyranosides and isomeric butyl alcohols or cyclohexanol took place in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf) in dichloromethane. The extent of the reaction after 1 h and 24 h from mixing was determined by gas chromatography (GC). Anomerization of the substrate took place during the course of transglycosylation, which favors α anomer regardless of the anomeric configurations of the starting glycosides. Transglycosylation also favors the a anomer regardless of the steric bulkiness of the alcohol. tert-Butyl alcohol did not give any transglycosylation, suggesting the steric hindrance of approaching the bulky alcohol to the oxonium intermediate. A mechanism for the transglycosylation have been proposed.