• Bulletin of the Korean Chemical Society
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• 제28권8호
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• pp.1299-1304
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• 2007

New sulfur functionalized cyclopentadiene ligands, 1-[2-(thioanisole)]-2,5-dimethylcyclopentadiene (3), 1-[2- (thioanisole)]-2,3,5-trimethylcyclopentadiene (4), and 1-[2-(thioanisole)]-2,3,4,5-tetramethylcyclopentadiene (5), were prepared. In these ligands, the S-donor atom is connected to a cyclopentadiene ring by a rigid phenylene spacer. CpCo(III)-diiodo half-sandwich complexes (6-8) were obtained from reaction the ligands (3- 5) with Co2(CO)8, followed by treatment of I2. Substitution reaction of CpCo(III)-diiodo complexes with MeLi yielded the corresponding CpCo(III)-dimethyl complexes (9-11). Further transformation to the corresponding cationic cobalt complexes (12-14) were achieved by reaction of the CpCo(III)-dimethyl complexes with HB(ArF)4·2Et2O and trapping with CD3CN. The new sulfur functionalized cyclopentadiene ligands having a rigid phenylene spacer and the corresponding cobalt complexes were characterized by 1H, 13C and 19F NMR spectroscopy. The diiodo Complex 6 was also characterized by a single crystal X-ray diffraction method.

• Bulletin of the Korean Chemical Society
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• 제15권6호
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• pp.473-477
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• 1994

Second-order rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of aryl substituted benzenesulfonates $(1,\;X-C_6H_4SO_2-OC_6H_4-Y)$ with aryloxides $(Z-C_6H_4O^{-})$ and ethoxide $(EtO^-)$ in absolute ethanol at $25^{circ}C$. The nucleophilicity of aryloxides increases with increasing electron donating ability of the substituent (Z) on aryloxides, and results in a good Hammett correlation with $\sigma^{-}$ constant. The reactivity of 1 toward aryloxides and ethoxide shows also significant dependence on the electronic nature of the substituent X and Y. Large positive ${\sigma}_{acyl}$ values have been obtained for the reaction of 1 with phenoxide and ethoxide, indicating that the leaving group departure is little advanced at the transition-state of the rate-determining step. This has been further supported from the fact that ${\sigma}^-$ constant gives extremely poor Hammett correlation, while ${\sigma}^0$ does reasonably good correlation for the reaction of 1 with ethoxide. Thus, the present sulfonyl-transfer reaction is proposed to proceed via a ratedetermining attack of nucleophile to the sulfur atom of 1 followed by a fast leaving group departure.

• 한국구조물진단유지관리공학회 논문집
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• 제19권1호
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• pp.139-146
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• 2015

콘크리트의 화학적 침식은 콘크리트 구조물의 내구성 감소로 이어져 문제가 되고 있다. 현재 사용되고 있는 콘크리트 표면보호재의 내구수명이 짧아 유지보수에 많은 비용과 노력이 요구되고 있다. 한편 국내 산업시설에서 유황의 부산량이 늘어나고 있으나, 소비량이 한정되어 있어 잉여유황이 증가하고 있다. 따라서 본 연구에서는 유황폴리머를 콘크리트의 표면보호재로 사용하기 위한 연구로써 채움재의 종류 및 양생조건에 따른 역학적 특성을 평가하였고, 유황폴리머에 대한 유해성을 평가하였다. 압축강도 평가 결과 채움재의 치환비율이 40%까지 증가할수록 압축강도 또한 증가하였으며, 채움재의 종류에 따라 양생온도 $40^{\circ}C$ (SS, FA)와 $60^{\circ}C$ (OPC)에서 높은 압축강도를 나타냈다. 기건양생과 수중양생의 압축강도 차는 미미한 것으로 나타나 양생 시 수분에 의한 영향은 크지 않은 것으로 나타났다. 부착강도 평가 결과 채움재의 종류와 무관하게 기건상태 $40^{\circ}C$에서 가장 높은 부착강도를 나타냈으며, 수중양생시 기건양생에 비하여 부착이 되지 않는 것으로 나타났다. 또한 $60^{\circ}C$에서 양생한 공시체의 경우 온도에 영향을 받아 변색 및 잔갈림 등이 나타냈으며, 채움재의 종류에 따라 치환 비율 20% (SS, FA) 30% (OPC)에서 가장 높은 부착강도를 나타냈다. 유해물질 용출시험 결과, 유해물질이 용출되지 않아 유황폴리머를 활용한 표면보호재의 유해성이 없는 것으로 판단된다. 본 연구범위에서 검토한 결과, 유황폴리머를 표면보호재로 활용하기 위해서는 규사를 20% 정도 치환하여 배합하고 $40^{\circ}C$의 기건상태에서 양생하는 것이 가장 적절한 것으로 판단된다.

• 대한화학회지
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• 제18권3호
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• pp.171-174
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• 1974

Sulfonyl chloride $ RSO_2Cl,\;R=C6H_5-,\;CH3-,\;OCH3-$ 및 $(CH_3)_2N-$에 대하여 EHT계산을 하였으며 바닥상태의 전자구조 특성과 $S_N$반응성을 논의하였다. 특히 $R=OCH_3$의 경우 Buncel이 제안한 Cl에서의 치환가능성을 검토하였다.

• Bulletin of the Korean Chemical Society
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• 제26권9호
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• pp.1410-1414
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• 2005

Neopentyl arenesulfonates reacted with primary alkylmagnesium halides in the presence of $(PPh_3)_2NiCl_2$ to produce the corresponding alkylarenes. The efficiency of this coupling reaction considerably depends on the nature of catalyst and solvent. Highest yield was obtained by using three equivalents of Grignard reagent to a mixture of $(PPh_3)_2NiCl_2$ and arenesulfonate in refluxing $Et_2O$. This reaction represents a novel method allowing the efficient and creative substitution of sulfur-containing groups in aromatic compounds. It also shows that the alkyloxysulfonyl group might be a suitable alternative to halides and triflate in some circumstances.

• 한국결정학회지
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• 제14권2호
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• pp.110-114
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• 2003

LiAl/sub 0.24/Mn/sub 1.76/O/sub 4-y/S/sub y/ (y=0, 0.02) were synthesized by the sol-gel method. Both structures were refined by Rietveld method, its structure refined as a cubic spinel, space group Fd-3m, a=8.17937(30) Å and 8.18331(19) Å respectively. Though it has been made a charge/discharge experiment above 20 times, there was no change of 3 V/4 V capacity degradation. It was considered that the volume change of MnO/sub 6/ octahedron induced by sulfur substitution plays a key role in keeping the 3 V/4 V capacity. The refined composition of the compound could be confirmed with the ICP analysis.

• Bulletin of the Korean Chemical Society
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• 제31권12호
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• pp.3749-3754
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• 2010

Various terphenyl and quaterphenyl derivatives were prepared by the Ni-NHC catalyzed cross coupling of the corresponding biphenyl- and terphenyl-sulfonates with arylmagnesium bromides. The reactions proceeded rapidly via a nucleophilic aromatic substitution of the alkoxysulfonyl moieties by the aryl nucleophiles to afford high yields within just 1.5 h at room temperature in spite of the low reactivity of the sulfur electrophiles.

• Bulletin of the Korean Chemical Society
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• 제12권1호
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• pp.93-97
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• 1991

Rate constants have been measured spectrophotometrically for the reactions of alkali metal ethoxides with 4-nitrophenyl benzoate, S-4-nitrophenyl thiobenzoate and 4-nitrophenyl thionbenzoate in ethanol at 25$^{\circ}$C. Substitution of S for O in the leaving group has not affected reactivity significantly, while the effect of the similar replacement in the acyl group has led to rate decrease by a factor of 10, although pronounced rate enhancements have been expected for both systems. The replacement of O by a polarizable S has also influenced the reactivity of the esters toward alkali metal ethoxides, i.e. the reactivity decreases as the size of the metal ion decreases. The alkali metal ions have showed inhibition effect instead of catalytic effect which would have been expected for the present system. The effect of replaced sulfur atom on the reactivity for the present system is attributed to the nature of hard and soft acids and bases.

• Transactions on Electrical and Electronic Materials
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• 제4권6호
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• pp.13-16
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• 2003

Mn-doped $ZnGa_{2}O_{4}$:$Mn^{2+}$ (M=S, Se) thin film phosphors have been grown using a pulsed laser deposition technique under various growth conditions. The structural characterization carr~ed out on a series of $ZnGa_{2}O_{4}$:$Mn^{2+}$ (M=S, Se) films grown on MgO(l00) substrates usmg Zn-rich ceramic targets. Oxygen pressure was varied from 50 to 200 mTorr and Zn/Ga ratio was the function of oxygen pressure. XRD patterns showed that the lattice constants of the $ZnGa_{2}O_{4}$:$Mn^{2+}$ (M=S, Se) thin film decrease with the substitution of sulfur and selenium for the oxygen in the $ZnGa_2O_4$. Measurements of photoluminescence (PL) properties of $ZnGa_{2}O_{4}$:$Mn^{2+}$ (M=S, Se) thin films have indicated that MgO(100) is one of the most promised substrates for the growth of high quality $ZnGa_2O_{4-x}M_{x}$:$Mn^{2+}$ (M=S, Se) thin films. In particular, the incorporation of Sulfur or Selenium into $ZnGa_2O_4$ lattice could induce a remarkable increase in the intensity of PL. The increasing of green emission intensity was observed with $ZnGa_2O_{3.925}Se_{0.075}:$Mn^{2+}$ and $ZnGa_2O_{3.925}S_{0.05}$:$Mn^{2+}$ films, whose brightness was increased by a factor of 3.1 and 1.4 in comparison with that of $ZnGa_{2}O_{4}$:$Mn^{2+}$ films, respectively. These phosphors may promise for application to the flat panel displays.

• 환경영향평가
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• 제6권2호
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• pp.93-102
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• 1997

Acid rain below pH 5.6 is responsible for 40% of annual precipitation in Korea and it is more serious especially in major cites. Because of that, it is urgent to make measures to reduce the emission of $SO_2$, one of the major air pollutants causing acid rain. The national total emission of $SO_2$ in 1994 was estimated as 1.6 million tons. The $SO_2$ emission in 2020, is expected to increase up to 3.2 million tons, about 2 times that of 1994 under Business-As-Usual scenario. We could take various $SO_2$ reduction measures such as installing desulfurization facilities, the supply of low-sulfur oil and clean fuel(LNG), energy savings, upgrading of production process. However, it is necessary to check the economic feasibility and the attainability to reduction target with a dynamic optimization mode, "Global 2100 Model". The cost-benefit analyses for the measures using the revised "Global 2100 Model" clearly revealed that the desulfurization facilities should be introduced to reduce the $SO_2$ concentration to 0.01 ppm with fuel substitution. If the introduction of desulfurization facilities is delayed, We can not attain the goal of Ministry of Environment before the year of 2012, even in the case that almost all the fuels would be substituted with LNG.