• Title/Summary/Keyword: Sulfur substitution

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Preparation and Characterization of Half-Sandwich Cobalt(III) Complexes of Cp Ligands with a Rigid Thioanisole Side-Chain

  • S, Sujith;Lee, Bun-Yeoul;Han, Jin-Wook
    • Bulletin of the Korean Chemical Society
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    • v.28 no.8
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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.

A Mechanistic Study on Nucleophilic Substitution Reactions of Aryl Substituted Benzenesulfonates with Anionic Nucleophiles

  • Um Ik-Hwan;Lee Seok-Joo;Kim Jung-Joo;Kwon Dong-Sook
    • Bulletin of the Korean Chemical Society
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    • v.15 no.6
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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.

Strength Development of Sulfur-Polymer-Based Concrete Surface Protecting Agents Depending on Curing Condition and Hazard Assessment of Sulfur Polymers (유황폴리머를 활용한 콘크리트 표면보호재의 양생조건에 따른 강도 평가 및 유황폴리머의 유해성 평가)

  • Lee, Byung-Jae;Lee, Eue-Sung;Kim, Seung-Gu;Kim, Yun-Yong
    • Journal of the Korea institute for structural maintenance and inspection
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    • v.19 no.1
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    • pp.139-146
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    • 2015
  • The amount of by-product from sulphur increases in domestic industrial facilities. However, the amount of its consumption is limited so that the amount of unused sulphur continues to increase. Therefore, in this study, the use sulfur polymer as the concrete surface protecting material was conducted. The compressive strength showed that as the substitution ratio of filler increased up to 40%, the compressive strength also increased. A high compressive strength was shown at the curing temperature of $40^{\circ}C$ (SS, FA) and $60^{\circ}C$ (OPC) according to the type of filler. The difference of compressive strength between air dry curing and water curing was insignificant so that there was no significant influence of moisture during curing process. The evaluation result of bond strength showed that the highest bond strength was shown at the air-dry condition of $40^{\circ}C$ regardless of type of filler. Bonding didn't occur properly during water curing in comparison to air dry curing. Also, in case of the specimen cured at $60^{\circ}C$, discoloration and hair cracks appeared due to the influence of temperature, and the highest bond strength was shown at the substitution ratio of 20% (SS, FA) and 30% (OPC) according to the type of filler. The releasing test result of harmful substance showed that no harmful substance was released, so there is no harmfulness in the surface protecting material using sulfur polymer. As a conclusion drawn in this study, it is most appropriate to substitute silica by approximately 20%, mix and cure at the air-dry condition of $40^{\circ}C$ in order to use sulfur polymer as the surface protecting material.

Nucleophilic Displacement at Sulfur Center (V). EHT Calculations on Sulfonyl Chlorides (황의 친핵치환 반응 (제5보). 각종 Sulfonyl Chloride에 대한 EHT 계산)

  • Lee Ikchoon;Kim, Ui Rak;Bae, Seon Ho
    • Journal of the Korean Chemical Society
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    • v.18 no.3
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    • pp.171-174
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    • 1974
  • The extended Huckel calculations have been conducted on sulfonyl chlorides $ RSO_2Cl,\;R=C6H_5-,\;CH3-,\;OCH3-$. Results are discussed using ground state electronic structures. $S_N$ reactivity has been discussed using calculated reactivity indices. Particularly, which the substitution of chlorine is take placed or not on $ROSO_2Cl$ in which is suggested by Buncel et al., is discussed by means of some basis on the MO theoretical ground.

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Nickel-Catalyzed Coupling of Arenesulfonates with Primary Alkylmagnesium Halides

  • Cho, Chul-Hee;Sun, Myung-Chul;Park, Kwang-Yong
    • Bulletin of the Korean Chemical Society
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    • v.26 no.9
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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.

Rietveld Refinement of Oxysulfide $LiAl_{0.24}Mn_{1.76}O_{4-y}S_y (y=0, 0.02)$ Spinel Materials

  • Park, Hyun-Min;Y.K Cho;Sun, Yang-Kook
    • Korean Journal of Crystallography
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    • v.14 no.2
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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.

Synthesis of Terphenyls and Quaterphenyls via the Nickel N-Heterocyclic Carbene-Catalyzed Cross-Coupling of Neopentyl Arenesulfonates with Aryl Grignard Reagents

  • Jo, Hyun-Jong;Kim, Chul-Bae;Ryoo, Tae-Yong;Ahn, Bo-Kyoung;Park, Kwang-Yong
    • Bulletin of the Korean Chemical Society
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    • v.31 no.12
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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.

The Effect of the Changing of C-O-C to C-S-C and C=O to C=S on Reactivity of 4-Nitrophenyl Benzoate with Alkali Metal Ethoxides in Ethanol

  • Kwon, Dong-Sook;Park, Hee-Sun;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.12 no.1
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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.

Photoluminescence of ZnGa2O4-xMx:Mn2+ (M=S, Se) Thin Films

  • Yi, Soung-Soo
    • Transactions on Electrical and Electronic Materials
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    • v.4 no.6
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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.

Development and Evaluation on a Model for Reducing SO2: Case Study on Global 2100 Model (산성비 원인물질인 이산화황 저감모형 구축과 평가에 관한 연구: Global 2100 모형을 중심으로)

  • Lee, Dong-Kun
    • Journal of Environmental Impact Assessment
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    • v.6 no.2
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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.

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