• Title/Summary/Keyword: Nitromethane

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Equilibria between Low-spin State ($D_{4h}$) and High-spin State ($O_h$) of the Ni(II)-$N_4$ Complex Ion ($N_4$ : 2,12-dimethyl-3,7,11,17-tetraazabicyclo-11,3,1-heptadeca-1(17),2,11,13,15-pentaene) (Ni(II)-$N_4$ 착이온의 낮은 스핀상태 ($D_{4h}$)와 높은 스핀상태 ($O_h$)간의 평형 ($N_4$ : 2,12-dimethyl-3,7,11,17-tetraazabicyclo-11,3,1-heptadeca-1(17),2,11,13,15-pentaene))

  • Yu-Chul Park;Jong-Chul Byun;Mahn-Su Yu
    • Journal of the Korean Chemical Society
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    • v.33 no.6
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    • pp.607-613
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    • 1989
  • The chemical equilibria of Ni(II)-tetraamine (tetraamine = 2,12-dimethyl-3,7,11,17-tetraazabicyclo-11,3,1-heptadeca-1(17),2,11,13,15-pentaene) complex ion in water, acetonitrile, acetone and nitromethane were investigated using spectrophotometric method, respectively. The equilibria between low-spin ($D_{4h}$) and high-spin ($O_h$) structures of Ni-tetraamine complex ion were presented in water, acetonitrile and acetone, but not in nitromethane. The eqilibrium constants, the reaction enthalpies and the reaction entropies were determined from analysis of the temperature dependence of the electronic spectra. The formation of the triplet species ($O_h$) was found to be exothermic. The solvent and electrolyte effects on the equilibrium constants could be explained by the dielectric constants of solvents and the reaction entropies.

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Solvation in Mixed Solvents (VII). Solvolysis of t-Butyl Halide in Isodielectric Solvents (혼합용매에서의 용매화 (제 7 보). 등유전상수 용매에서 t-Butyl Halide 의 가용매분해반응)

  • Lee, Ick-Choon;Lee, Hai-Whang;Uhm, Tae-Seop;Sung, Dae-Dong;Ryu, Zoon-Ha
    • Journal of the Korean Chemical Society
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    • v.32 no.2
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    • pp.85-93
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    • 1988
  • Solvolyses of t-butylhalides (X = Cl, Br, I) in quasi isodielectric solvent system, MeOH-nitromethane, MeOH-nitrobenzene and MeOH-ethyleneglycol have been studied kinetically. Methanolyses for t-butylhalides in MeOH-NM and MeOH-NB show rate maxima at 40~100 % (v/v) MeOH. The rate maxima observed have been interpreted as a result of cooperative enhancement of polarity-polarizability and hydrogen bonddonor ability of solvents. The influences of polarity-polarizability and hydrogen bonddonor ability on reactivities of substrates have been discussed in terms of Y value changes. The solvolysis rates for t-butylhalides in E.G. are more than 20 fold faster than those in MeOH and this was attributed to the solvent structure of E.G.

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An Improved Procedure for 2-amino-5-nitro-4,6-diarylcyclohex-1-ene-1,3,3-tricar Bonitriles; Carbonate on Polymer Support as Mild and Reusable Catalyst

  • Prasanna, T.S.R.;Raju, K. Mohana
    • Journal of the Korean Chemical Society
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    • v.55 no.5
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    • pp.808-811
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    • 2011
  • A new catalytic system has been developed in the synthesis of 2-amino-5-nitro-4,6-diarylcyclohex-1-ene-1,3,3-tricarbonitriles using carbonate on polymer support (Amberlyst A-26 $NaCO_3{^-}$). Short reaction time, simplicity of isolation, safe catalyst and high yields of product are the features.

TLC 이용한 젖산 분리와 정량분석 개발을 위한 연구

  • Jo, Gap-Su;Choe, Mi-Hwa;Ryu, Hwa-Won;Kim, Geun-A;Yu, Seon-Gyun;Kim, Do-Man
    • 한국생물공학회:학술대회논문집
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    • 2002.04a
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    • pp.165-168
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    • 2002
  • TLC(Thin Layer Chromatography) 는 제약산업이나 생화학 연구 그리고 여러 산업 현장에서 널리 이용되는 화학 분석 방법이다 . 본 연구에서는 적은 비용으로도 많은 양의 시료를 신속하게 분리할 수 있는 TLC를 이용하여 유기산인 젖산 (Lactic acid) 을 분리는 전개방법을 개발하였다 . 전개용매는 2 가지 용매 (1) nitroethane nitromethane : ethanol: water: I-propanol = 1 : 2 : 3 : 4 : 5 (v/v/v/v/v), (2) diisopropyl ether. formic acid. water = 90 : 7 : 3 (v/v/v) 를 사용하였다 . 발색시약은 A : bromocresol purple reagent I, B . bromocresol purple reagent II, C : bromocresol green-bromophenol blue-potassium permanganate reagent 를 사용하여 분석하는 방법을 개발하였다 $^6)$. 젖산의 분리는 silica gel TLC plate를 이용하는 경우 , 용매 (1) 에 발색시약 B를 사용했을 때 , 분리 확인이 가장 좋았다.

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Efficient Fluorescence Quenching of tert-butyl substituted Phthalocyanines with Picric Acid

  • Gupta, Ankush;Kim, Meena;Park, Jong S.
    • Textile Coloration and Finishing
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    • v.26 no.4
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    • pp.277-282
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    • 2014
  • Two tert-butyl substituted phthalocyanines(Pcs), in metal-free and metallated forms, were synthesized and the fluorescence responses toward various nitro derivatives, including picric acid(PA), 2,4-dinitrotoluene(DNT), 1,4-dinitrobenzene(DNB), 4-nitrotoluene(NT), nitrobenzene(NB), 1,4-benzoquinone(BQ), and nitromethane(NM) were investigated. Among the various nitro derivatives, current Pc derivatives exhibited efficient and exclusive fluorescence quenching in the presence of picric acid, which was readily observed by a naked eye. Quenching efficiency was estimated by the Stern-Volmer relationship, in which quenching constant, KSV, was calculated to be in the range of $10^4M^{-1}$. It was also found out that the aggregational behaviors of these Pcs are heavily dependent on the nature of solvent systems, subsequently affecting the quenching efficiency.

A Functionalised Macrobicycle Complex Available for Surface Immobilisation and Protein Grafting

  • Bernhardt, Paul V.;Harrowfield, Jack M.;Kim, Yang;Lee, Young-Hoon;Park, Yu-Cheol;Sujandi, Sujandi
    • Bulletin of the Korean Chemical Society
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    • v.28 no.4
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    • pp.589-595
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    • 2007
  • The conversion of both the racemic and resolved forms of the Co(III) complex of an hydroxymethyl-substituted tripodal hexamine to macrobicycles via reaction with formaldehyde and nitromethane (and subsequent reduction of the product) has been conducted. The prospect is that it will provide cage complexes in which the hydroxyl substituent is sufficiently remote from the metal ion centre for its nucelophilicity to be largely unaffected. X-ray structure determinations have been used to characterise these new cage species as well as some complexes of the precursor hexamine and its mono-aminal. The electrochemistry and optical activity of the complexes have also been studied in detail.

The First Report on Chemoselective Biguanide-Catalyzed Henry Reaction under Neat Conditions

  • Alizadeh, Abdolhamid;Khodaei, Mohammad M.;Abdi, Gisya;Kordestani, Davood
    • Bulletin of the Korean Chemical Society
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    • v.33 no.11
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    • pp.3640-3644
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    • 2012
  • An efficient synthetic method for direct Henry reaction catalyzed by a biguanide; namely metformin, as an organosuper-base, between a variety of aromatic and aliphatic aldehydes and nitromethane under neat conditions has been developed. Convenient procedure for removal of the catalyst, chemoselective acquiring of ${\beta}$-nitroalcohols as predominant products, as far as possible short reaction time with excellent conversions are advantages of the developed protocol.

Mechanistic Change-Over in Nucleophilic Solvent Assisted Reactions

  • Sung, Dae Dong;Kim Yang Hee;Park Yoo-Mee;Ryu Zoon Ha;Lee Ickchoon
    • Bulletin of the Korean Chemical Society
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    • v.13 no.6
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    • pp.599-605
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    • 1992
  • Rate constants of methanolyses of para-Z-substituted benzenesulfonyl chlorides have been determined in various isodielectric solvent mixtures. A third-order kinetic behavior has been observed in the methanolysis of p-nitrobenzenesulfonyl chloride in methanol-nitromethane mixture from the correlation figure of logarithms of rate constants were plotted against Y-values based on solvolyses of 1-adamantyl tosylate. $S_N1$-$S_N2$ mixing mechanisms are favored by neutral or weak electron-donating and weak electron-withdrawing substituents of p-Z-substituted benzenesulfonyl chlorides in methanol-nitrobenzene mixture. While the methanolyses of para-Z-substituted benzenesulfonyl chlorides in methanol-ethylene glycol solvent mixture are appropriate for $S_N2$ mechanism from the mechanistic criterion by means of m-values.

Degradation and Metabolism of Phorate in Soil (토양중(토양중) Phorate의 분해(분해)와 대사(대사))

  • Lee, Hae-Keun;Hong, Jong-Uck
    • Applied Biological Chemistry
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    • v.26 no.2
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    • pp.97-103
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    • 1983
  • To get further information on the behavior of phorate(0,0-diethyl S-ethylthiomethyl phosphorodithioate) in soil under the subtropical conditions, a field experiment has been conducted. Phorate granule (10%) was applied to silt loam soil at the rate of 40kg a.i./ha and incorporated to 10cm soil depth. Residues of phorate and its metabolites in soil were determined with GLC and confirmed qualitatively with TLC. Phorate was rapidly oxidized to its sulfoxide and sulfone. Therefore, main metabolic pathway of phorate in soil was the oxidation of phorate to phorate sulfoxide and sulfone. Phorate sulfoxide and sulfone were relatively more persistent than phorate itself. Phoratoxon was detected at low level only up to 30 days after treatment and its sulfoxide and sulfone were not detected during the whole experimental period. Toluene-acetonitrile-nitromethane(40 : 30 : 30, v/v/v) solvent system separated satisfactorily phorate and its five metabolites. Most of the residues was found in the initial incorporation depth $(0{\sim}10cm)$. Consequently, insecticides showed a little downward movement.

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Enzyme-Catalyzed Henry Reaction in Choline Chloride-Based Deep Eutectic Solvents

  • Tian, Xuemei;Zhang, Suoqin;Zheng, Liangyu
    • Journal of Microbiology and Biotechnology
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    • v.26 no.1
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    • pp.80-88
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    • 2016
  • The enzyme-catalyzed Henry reaction was realized using deep eutectic solvents (DESs) as a reaction medium. The lipase from Aspergillus niger (lipase AS) showed excellent catalytic activity toward the substrates aromatic aldehydes and nitromethane in choline chloride:glycerol at a molar ratio of 1:2. Addition of 30 vol% water to DES further improved the lipase activity and inhibited DES-catalyzed transformation. A final yield of 92.2% for the lipase AS-catalyzed Henry reaction was achieved under optimized reaction conditions in only 4 h. In addition, the lipase AS activity was improved by approximately 3-fold in a DES-water mixture compared with that in pure water, which produced a final yield of only 33.4%. Structural studies with fluorescence spectroscopy showed that the established strong hydrogen bonds between DES and water may be the main driving force that affects the spatial conformation of the enzyme, leading to a change in lipase activity. The methodology was also extended to the aza-Henry reaction, which easily occurred in contrast to that in pure water. The enantioselectivity of both Henry and aza-Henry reactions was not found. However, the results are still remarkable, as we report the first use of DES as a reaction medium in a lipase-catalyzed Henry reaction.