• 제목/요약/키워드: Substitution reaction

검색결과 580건 처리시간 0.024초

Structural Determination of cis- and trans-5-Hydroxymethyl-5-methyl-2-thiono-r-2-ethoxy-1,3,2-dioxaphosphorinane by NMR and X-ray Crystallography: Model Compounds for the Reaction Mechanism Study of Organophosphorus Pesticides

  • Kim, Jeong Han;Toia, Robert F.;Craig, Donald C.
    • Journal of Applied Biological Chemistry
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    • 제43권1호
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    • pp.37-43
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    • 2000
  • 1,3,2-Dioxaphosphorinanes are suitable compounds for studying the stereochemistry of substitution at phosphorus. Cis- and trans-5-hydroxymethl-5-methyl-2-thiono-2ethoxy-1,3,2-dioxaphosphorinane were prepared, and their structures and stereochemistry unambiguously assigned by NMR and X-ray crystallography with acetoxy and 3,5-dinitrobenzoyloxy derivatives, respectively. Trans isomer gave $^{31}P$ NMR signal at higher field than cis isomer, and the ring proton Spectrum of cis isomer showed characteristic pattern for identifying its geometry. In X-ray crystallography they adopted a chair conformation with the ethoxy groups in the axial positions, and the sulfide groups in the equatorial positions. A flattening of the ring around the phosphorus center was noted, the POC bond angles were about $120^{\circ}$, and the C-O bonds in the ring were significantly longer than the C-O bond for the ethoxy group or the C-O bond for hydroxyl group.

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(Ba1-xCax)(Ti0.85Zr0.12Sn0.03)O3계 세라믹스의 미세구조 및 유전 특성 (Microstructure and Dielectric Properties of (Ba1-xCax)(Ti0.85Zr0.12Sn0.03)O3 Ceramics)

  • 신상훈;류주현;신동찬
    • 한국전기전자재료학회논문지
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    • 제27권12호
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    • pp.797-802
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    • 2014
  • In this study, in order to develop the capacitor composition ceramics with the good dielectric properties, $(Ba_{1-x}Ca_x)(Ti_{0.85}Zr_{0.12}Sn_{0.03})O_3$ (abbreviated as BCTZ) ceramics were prepared by the conventional solid-state reaction method. The effects of Ca substitution on the microstructure and dielectric properties was investigated. The X-ray diffraction patterns demonstrated that all the specimens showed perovskite phase, and secondary phases are indicated in the measurement range of X-ray diffraction. Also, all the specimens indicated an rhombohedron phase structure. It was identified from the X-ray diffraction patterns that the secondary phase formed in grain boundaries and then decreased the dielectric properties. For all the specimens, observed one peak was tetragonal cubic phase transition temperature($T_c$), which is located in the vicinity of room temperature.

Inhibitory Effect of Vitamin C on Mutagenicity of 6-Sulfooxymethylbenzo[a]pyrene

  • Cho, Young-Sik;Hong, Sun-Taek;Chung, An-Sik
    • Toxicological Research
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    • 제12권1호
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    • pp.21-27
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    • 1996
  • Vitamin C has been well known to be a potential chemopreventive agent for several toxic compounds. It reduced the mutation frequencies of 6-sulfooxymethylbenzo[a]pyrene (SMBP) and 6hydroxymethylbenzo[a]pyrene (HMBP) in Salmonella typhimurium TA98 and TA100, indicating that corbic acid affects both frameshift and base-pair substitution mtltations. A similar type of dose-response relationship was shown in the V79 cells, although the inhibitory effect was less dramatic compared with that in S. typhimurium. However, SMBP or HMBP binding to calf thymus DNA was not affected by the presence of vitamin C, suggesting that SMBP seems to be much more reactive to calf thymus DNA than vitamin C. This was supported by migration pattern and fluorescence intensity of SMBP-modified plasmid on the gel. These restilts were not correlated with mutation tests in bacterial and mammalian cell systems. It has been already reported that vitamin C inactivates SMBP through the formation of covalently bound addact. It was found from HPLC analysis that the reaction between vitamin C and SMBP was accomplished within just 5 min and then produced the several products. These findings indicate that the beneficiary of vitamin C is not merely derived from the covalent adducts. On the other hand, the addition of DNA to incubation mixture reduced the amounts of vitamin C adducts while the magnitude of HMBP peak increased, suggesting that DNA accelerates the SMBP hydrolysis to intercept the interaction between SMBP and vitamin C or forms rapidly complex with SMBP.

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Theoretical Studies on the Competitive Sn2 Reactions of O-Imidomethyl Derivatives of Phenols with OH-

  • 김창곤;정동수;김찬경;이본수;정영진;이병준;이익준
    • Bulletin of the Korean Chemical Society
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    • 제22권1호
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    • pp.25-29
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    • 2001
  • Nucleophilic substitution reactions of O-imidomethyl derivatives of phenols with OH- were studied theoretically using the semiempirical AM1 and Solvation Model 2.1 (SM2.1) methods in the gas phase and aqueous solution, respectively. In the gas phase, the two reaction paths, in which the imide (1a) or phenol (1b) is functioning as a leaving group, can occur competitively. In contrast, in aqueous solution, path (1b) becomes more favorable than (1a) because the transition states (TS) of path (1b) are more stabilized by solvent. Differences in solvation energies are caused by the structural differences of TS, i.e., the TS via path (1b) is more dissociative than that via path (1a). Therefore we conclude that the solvent effects play an important role in the hydrolysis of O-imidomethyl derivatives of phenols. However, reactivity is dependent on the acidities of both the imide and the phenol fragments since the ρz values vary progressively from 4.2 (Z' = I) to 2.5 (Z' = IV) as the acidities of imide increase. These are in good agreement with the experimental results.

Syntheses and Reactions of Iridium Complexes Containing Mixed Phosphine-Olefin Ligand: (3-(Diphenylphosphino)propyl)(3-butenyl)phenylphosphine

  • Young-ae W. Park;Devon W. Meek
    • Bulletin of the Korean Chemical Society
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    • 제16권6호
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    • pp.524-528
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    • 1995
  • The reaction of [IrCl(cod)]2 with ppol ligand, Ph2PCH2CH2CH2P(Ph)CH2CH2CH=CH2, in ethanol gives an iridium complex, whose structure is converted from an ionic form, [Ir(cod)(ppol)]Cl·2C2H5OH (1),in polar solvents (ethanol, methanol and acetonitrile), to a molecular form, [IrCl(cod)(ppol)], in non-polar solvents (benzene and toluene). The cationic complexes, [Ir(cod)(ppol)]AsF6·1/2C2H5OH and [Ir(cod)(ppol)]PF6·1/2CH3CN, were prepared to compare with the ionic form by 31P NMR spectroscopy. When carbon monoxide is introduced to 1, cod is replaced by CO to give the 5-coordinated complex, [IrCl(CO)(ppol)]. Hydrogenation of 1-octene was not successful in the presence of 1. In order to verify the reason for 1 not behaving as a good catalyst for hydrogenation, electrophilic reactions with HCl, I2 and HBF4·etherate were performed, which yielded the oxidative addition product, [IrHCl2(ppol)], the substitution product, [IrI(cod)(ppol)], and another cationic product, [Ir(cod)(ppol)]BF4, respectively. Thus, the iridium complex is not sufficiently basic to activate hydrogen atoms or the olefin of the ppol ligand.

Structure Identification of 1,2-Disubstituted Chiral Calix[4]arene : X-Ray and NMR Analysis of 25-(3,5-Dinitrobenzoyloxy)-26-methoxy-27,28-dihydroxycalix[4]arene

  • 박영자;신정미;남계춘;김종민;국승근
    • Bulletin of the Korean Chemical Society
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    • 제17권7호
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    • pp.643-647
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    • 1996
  • 1,2-Disubstituted chiral calix[4]arene "25-(3,5-dinitrobenzoyloxy)-26-methoxy-27,28-dihydroxycalix[4]arene" was synthesized by the reaction of 25-(3,5-dinitrobenzoyloxy)-calix[4]arene with methyl iodide in the presence of K2CO3. Methylation was occurred at the 26-position of calix[4]arene. The partial cone conformation and 1,2-substitution were characterized based on the 1H NMR, 13C NMR and X-ray diffraction analysis. The crystal structure has been determined by X-ray diffraction method. The crystals are orthorhombic, Pbca, a=10.652(1), b=17.687(1), c=32.247(3) Å, Z=8, V=6075.4(9) Å3, Dc=1.38gcm-3. The intensity data were collected on an Enraf-Nonius CAD-4 Diffractometer with a graphite monochromated Cu-Kα radiation. The structure was solved by direct method and refined by full-matrix least-squares methods to a final R value of 0.050 for 2368 observed reflections. The molecule is in the partial cone conformation. It has two strong intramolecular hydrogen bonds of O(1D)-H…O(1C)-H…O(1B).

Enhancement of hydrophilicity and anti-fouling property of polysulfone membrane using amphiphilic nanocellulose as hydrophilic modifier

  • Yang, Xue;Liu, Lifang;Jiang, Shuai
    • Membrane and Water Treatment
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    • 제10권6호
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    • pp.461-469
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    • 2019
  • In the present work, we present a new effective hydrophilicity modifier for polysulfone (PSf) membrane. Firstly, amphiphilic nanocellulose (ANC) with different substitution degrees (SD) was synthesized by esterification reaction with nanocellulose (NC) and dodecyl succinic anhydride (DDSA). The SD and morphology of ANC were characterized by titration method and transmission electron microscopy (TEM). Then, the polysulfone (PSf)/ANC blend membranes were prepared via an immersion phase inversion method. The influence of SD on the morphology, structure and performances of PSf/ANC blend membrane were carefully investigated by Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), mechanical property test, contact angle measuring instrument and filtration experiment. The results showed that the mechanical property, hydrophilicity and anti-fouling property of all the PSf/ANC blend membranes were higher than those of pure PSf membrane and PSf/NC membrane, and the membrane properties were increased with the increasing of SD values. As ANC-4 has the highest SD value, PSf/ANC-4 membrane exhibited the optimal membrane properties. In conclusion, the prepared ANC can be used as an additive to improve the hydrophilicity and anti-fouling properties of polysulfone (PSf) membrane.

Study on the Characteristic of Elastomer Composite Containing Tungsten Powder

  • Chung, Kyungho
    • Elastomers and Composites
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    • 제56권1호
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    • pp.6-11
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    • 2021
  • In order to develop an ultra-high-density elastomeric material for substitution of steel dynamic dampers, a new curing system and technique for high-loading of the filler were examined in this study. Mechanochemical modification of chloroprene rubber (MAH-g-CR) using an internal mixer was carried out with maleic anhydride (MAH) as a reactive monomer. The optimum amount of MAH was 10 phr and the efficient grafting of MAH on CR could be achieved at a mixing temperature of 100℃. After preparing MAH-g-CR, 50 mol% epoxidized natural rubber (ENR 50) was blended with MAH-g-CR to develop a "self-curable rubber blend system" via reaction between the functional groups of the elastomeric matrices without the curing agent and additives. The content of ENR 50 was fixed at 30 wt.% throughout evaluation of the curing behavior of the MAH-g-CR/ENR blend. Tungsten powder was added to the MAH-g-CR/ENR matrix up to 60 vol.% to obtain ultra-high-density, and the maximum density obtained was 7.57 g/㎤. Stable ts2 (scorch time) and t90 (90% cure time) could be obtained even when tungsten powder was incorporated up to 60 vol.%. In addition, the tensile strength and damping properties of MAH-g-CR/ENR containing 60 vol.% of tungsten were better than those of CR containing 60 vol.% of tungsten.

광경화형 사이클로포스파젠 유도체를 이용한 양모섬유의 친환경 내구성 방염가공 (Eco-friendly Durable Flame-Retardant Finish of Wool Fabrics Using a UV-curable Cyclophosphazene Derivative)

  • 백지윤;장진호
    • 한국염색가공학회지
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    • 제33권4호
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    • pp.230-237
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    • 2021
  • The flame-retardant (FR) treatments of wool fibers using Hexafluorozirconate/titanate salts and tetrabromophthalic anhydride can cause skin irritation and gas toxicity due to Zr and Br compounds respectively. A water-soluble polyfunctional cyclophosphazene derivative, synthesized through substitution reaction of Hexachloro cyclophosphazene and N-[3-(Dimethylamino)propyl] metacrylamide, was applied as a durable flame-retardant for wool fabrics. Also, a crosslinked structure was introduced to improve washing durability of the FR-wool, up to 10 laundering cycles, using Acrylamide(AAm) and Triacryloylhexahydrotriazine (TAHT) as a comonomer and a crosslinker respectively. The mole ratios of the TAHT and AAm concentrations compared to the Dichloro tetrakis{N-[3-(Dimethylamino)propyl]methacrylamido} cyclcophosphazene (DCTDCP) were optimized to 1.33 and 7.5 respectively. In addition, the pyrolysis and combustion properties of the FR wool were assessed using LOI, TGA and microcalorimetry suggesting a solid-phase FR mechanism.

건설폐기물을 활용한 이산화탄소 반응경화 시멘트 제조에 관한 연구 (Manufacturing of Calcium Silicate Cement Using Construction Waste)

  • 이향선;손배근;송훈
    • 한국건축시공학회:학술대회논문집
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    • 한국건축시공학회 2023년도 봄 학술논문 발표대회
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    • pp.47-48
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    • 2023
  • In the domestic industrial sector, greenhouse gases emitted from the cement industry account for about 10%, with most of them generated during the cement clinker calcination process. During the calcination process, 57% of carbon dioxide is emitted from the decarbonation reaction of limestone, 30% from fuel consumption, and 13% from electricity usage. In response to these issues, the cement industry is making efforts to reduce carbon dioxide emissions by developing technologies for raw material substitution and conversion, improving process efficiency by utilizing low-carbon alternative heat sources, developing CO2 capture and utilization technologies, and recycling waste materials. In addition, due to the limitations in purchasing and storing industrial byproducts generated from industrial facilities, many studies are underway regarding the recycling of construction waste. Therefore, this study analyzes the manufacture of calcium silicate cement (CSC), which can store carbon dioxide as carbonate minerals in industrial facilities, and aims to contribute to the development of environmentally friendly regenerated cement using construction waste.

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