• 제목/요약/키워드: Decarboxylation

검색결과 89건 처리시간 0.027초

Efficient Biomimetic Oxidative Decarboxylation of Some Carboxylic Acids Catalyzed by a Manganese (III) Schiff Base Complex

  • Nasr-Esfahani, Masoud;Montazerozohori, Morteza;Akhlaghi, Parisa
    • Bulletin of the Korean Chemical Society
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    • 제30권7호
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    • pp.1583-1587
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    • 2009
  • The four dentate $N_2O_2$ Schiff base ligand of bis(2-hydroxyacetophenone)-1,2-propanediimine (BHAPN) and its manganese (III) complex were synthesized and identified by microanalysis, spectral data ($^1H$ NMR, MS, FT-IR and UV-Visible) and molar conductivity measurement. The mild and efficient homogeneous oxidative decarboxylation of some carboxylic acids by catalytic amount of this manganese (III) complex, using tetrabutylamonium periodate as a mild oxidant in chloroform at room temperature is reported. The catalyst used in this study showed good activity for the decarboxylation of the titled compounds.

2,3,4,5-Tetrafluorobenzoic Acid의 합성 (Preparation of 2,3,4,5-Tetrafluorobenzoic Acid)

  • Li, Hua;Wang, Hongkai;Zhao, Ruiju;Liu, Juan;Zhao, Zhengui;Hu, Guoqin;Liang, Zhengyong
    • 대한화학회지
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    • 제54권6호
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    • pp.744-748
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    • 2010
  • Fluoroquinolone 항생제의 중요한 중간체인 2,3,4,5-tetrafluorobenzoic acid를 tetrachloride phthalic anhydride에서 출발 하여 imidation, fluorination, hydrolysis과 decarboxylation단계를 거쳐서 합성하였다. Imdation 단계에서는 상전이 촉매를 이용하여 98.2%의 수율로 합성하였으며, fluorination 단계에서는 81.3%, 가수분해 단계에서는 88.6%, 마지막으로 decarboxylation단계에서는 81.6%의 수율로 합성하였다.

Peroxy Acid Oxidations: A Kinetic and Mechanistic Study of Oxidative Decarboxylation of $\alpha$-Keto Acids by Peroxomonophosphoric Acid

  • Radhasyam Panda
    • Bulletin of the Korean Chemical Society
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    • 제22권8호
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    • pp.909-913
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    • 2001
  • The kinetics of oxidative decarboxylation of pyruvic acid and benzoylformic acid by peroxomonophosphoric acid (PMPA) in aqueous medium have been investigated. The reaction follows second order-first order each in PMPA and substrate concentration a t constant pH. The reactivity of different peroxo species in the oxidation has been determined. Activation energy and thermodynamic parameters have been computed. A plausible mechanism consistent with the observed results is proposed.

Theoretical Analysis and Prediction of Catalysts for Oxidative Decarboxylation of Melanin-Concentrating Hormone

  • Kim, Min-Gyum;Kim, Myoung-Soon;Park, Hwang-Seo;Lee, Sang-Youb;Suh, Jung-Hun
    • Bulletin of the Korean Chemical Society
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    • 제28권7호
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    • pp.1151-1155
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    • 2007
  • In a previous study, a catalyst (A) was discovered for oxidative decarboxylation of melanin-concentrating hormone (MCH). To explain the catalytic action and to predict the structure of a new catalyst with improved activity, docking simulations were carried out for the complex formed between A and MCH. The simulations suggested that the three terminal groups of A form a hydrophobic pocket and that van der Waals interactions between the hydrophobic pocket and MCH play a role in stabilizing the MCH-A complex. Consequently, a new catalyst (B) was designed and synthesized in expectation of improved catalytic activity resulting from enhanced van der Waals interactions. The new catalyst, however, showed slightly lower catalytic activity. Lack of the accurate solution structure of MCH may be one of the factors associated with difficulties in prediction of improvement in catalytic activity by purely theoretical means. The results, however, revealed that variation of the acyl portion of the hydroxyproline portion may lead to improved catalysts.

Spectral and Mechanistic Investigation of Oxidative Decarboxylation of Phenylsulfinylacetic Acid by Cr(VI)

  • Subramaniam, Perumal;Selvi, Natesan Thamil;Devi, Soundarapandian Sugirtha
    • 대한화학회지
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    • 제58권1호
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    • pp.17-24
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    • 2014
  • The oxidative decarboxylation of phenylsulfinylacetic acid (PSAA) by Cr(VI) in 20% acetonitrile -80% water (v/v) medium follows overall second order kinetics, first order each with respect to [PSAA] and [Cr(VI)] at constant [$H^+$] and ionic strength. The reaction is acid catalysed, the order with respect to [$H^+$] is unity and the active oxidizing species is found to be $HCrO_3^+$. The reaction mechanism involves the rate determining nucleophilic attack of sulfur atom of PSAA on chromium of $HCrO_3^+$ forming a sulfonium ion intermediate. The intermediate then undergoes ${\alpha}$,${\beta}$-cleavage leading to the liberation of $CO_2$. The product of the reaction is found to be methyl phenyl sulfone. The operation of substituent effect shows that PSAA containing electron-releasing groups in the meta- and para-positions accelerate the reaction rate while electron withdrawing groups retard the rate. An excellent correlation is found to exist between log $k_2$ and Hammett ${\sigma}$ constants with a negative value of reaction constant. The ${\rho}$ value decreases with increase in temperature evidencing the high reactivity and low selectivity in the case of substituted PSAAs.