• 제목/요약/키워드: Substitution reaction

검색결과 580건 처리시간 0.02초

미셀용액에서 Cyanocobalt(II) 착물의 리간드치환 반응에 대한 속도론적 연구 (Kinetic Studies on the Ligand Substitution Reactions of Cyanocobalt(II) Complexes in Micellar Solutions)

  • 안범수
    • 한국응용과학기술학회지
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    • 제26권3호
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    • pp.370-378
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    • 2009
  • Kinetic studies on the ligand substitution reactions of cyanocomplexes were performed in several micellar solutions. It showed the observed rate constants was found to be independent of the entering ligand concentration at high concentration of cyanopyridine and pyrazinecarboxylate. We could see also that in nonionic and anionic micellar solutions no influence of changes in the surfactant concentration on the observed rate constants was found. Taking into account the hydrophilic nature of the cobalt complex, the cobalt complex molecule was expected to be located in the aqueous phase of the micellar systems, where the reaction would take place. In cationic micellar solutions, a small increase in the observed rate constant was found when the cationic surfactant concentration increased. After reaching a maximum, the rate constant decreased on increasing surfactant concentration and subsequently it reached a plateau, where the observed rate constant was independent of changes in the surfactant concentration.

Synthesis, Characterization and Biological Evaluation of a Series of Levofloxacin Carboxamide Analogues

  • Sultana, Najma;Arayne, Muhammad Saeed;Rizvi, Syeda Bushra Shakeb;Mesaik, Muhammad Ahmed
    • Bulletin of the Korean Chemical Society
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    • 제30권10호
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    • pp.2294-2298
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    • 2009
  • In present work an attempt was made to synthesize various analogues of levofloxacin by introducing new functionality at carboxylic group position via nucleophilic substitution reaction. For this purpose the carboxylic group at C-6 was esterified and later subjected to nucleophilic attack at the carbonyl carbon by various aromatic amines. Structure of the analogues was confirmed by different techniques i.e. IR, $^1H$ NMR and mass spectrometry. The antibacterial activity of the derivatives was also assessed and compared with the parent against a series of Gram-positive and Gramnegative bacteria. A synergistic as well as antagonistic behavior was observed in these derivatives. Additionally unlike levofloxacin, the derivatives were also found to modulate oxidative burst response of phagocytes exhibiting moderate to significant inhibitory activity.

Synthesis and Antiviral Evaluation of Novel Methyl Branched Cyclopropyl Phosphonic Acid Nucleosides

  • Kim, Jin-Woo;Ko, Ok-Hyun;Hong, Joon-Hee
    • Archives of Pharmacal Research
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    • 제28권7호
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    • pp.745-749
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    • 2005
  • A simple synthetic route for the synthesis of novel methyl branched cyclopropyl phosphonic acid nucleosides is described. The characteristic cyclopropyl moiety 8 was constructed by employing Simmons-Smith reaction as a key step. The condensation of mesylate 11 with natural nucleosidic bases (A,C,T,U) under standard nucleophilic substitution conditions ($K_2CO_3$, 18-Crown-6, DMF) and after subsequent hydrolysis resulted in the formation of target nucleosides, 16, 17, 18, and 19. In addition, the antiviral evaluations of the synthesized nucleotides against various viruses were also performed.

The Effect of Solvation and Polarizability on the $\alpha$-Effect: Nucleophilic Substitution Reactions of p-Nitrophenyl Benzoate with Various Anionic Nucleophiles

  • 엄익환
    • Bulletin of the Korean Chemical Society
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    • 제13권6호
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    • pp.632-636
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    • 1992
  • Second-order rate constants have been determined spectrophotometrically for nucleophilic substitution reactions of p-nitrophenyl benzoate with various anionic nucleophiles including 6 ${\alpha}$ -effect nucleophiles. The logarithmic second-order rate constants for the aryloxides give a good Bronsted correlation with the respective basicity while the ones for p-chlorothiophenoxide and hydroxide exhibit significantly positive and negative deviations, respectivity, from the Bronsted linear line. The deviations are attributed to a solvation effect rather than a change in the reaction mechanism. The ${\alpha}$-effect nucleophiles except highly basic ones demonstrate significantly higher nucleophilicity (the ${\alpha}$ -effect) than would be predicted from the respective basicity. The effect of solvation and polarizability appears to be important for the ${\alpha}$-effect as well as for the reaction rate.

The Effect of Alkali Metal Ions on Nucleophilic Substitution Reactions of Aryl 2-Furoates with Alkali Metal Ethoxides in Ethanol

  • Dong-Sook Kwon;Jung-Hyun Nahm;Ik-Hwan Um
    • Bulletin of the Korean Chemical Society
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    • 제15권8호
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    • pp.654-658
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    • 1994
  • Rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of p-and m-nitrophenyl 2-furoates (4 and 5, respectively) with alkali metal ethoxides ($EtO^-M^+$) in absolute ethanol at 25$^{\circ}$C. The reactivity of $EtO^-M^+$ toward 4 is in the order $EtO^-K^+$ > $EtO^-Na^+$> $EtO^-Li^+$ > $EtO^-K^+$+ 18-crown-6 ether. This is further confirmed by an ion pairing treatment method. The present result indicates that (1) ion paired $EtO^-M^+$ is more reactive than dissociated $EtO^-$ ; (2) the alkali metal ions ($K^+,\;Na^+,\;Li^+$) behave as a catalyst; (3) the catalytic effect increases with increasing the size of the metal ion. A similar result has been obtained for the reaction of 5, however, the catalytic effects shown by the metal ions are more significant in the reaction of 5 than in that of 4.

Nucleophilic Substitution Reactions of 1- and 2-Naphthylethyl Arenesulfonates with Anilines and Benzylamines

  • 오혁근;송세정;조인호;이익춘
    • Bulletin of the Korean Chemical Society
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    • 제17권3호
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    • pp.254-257
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    • 1996
  • Nucleophilic substitution reactions of 1- and 2-naphthylethyl arenesulfonates, 2 and 3, with anilines and benzylamines in methanol at 65.0 ℃ are investigated. The rates are slower than those for the corresponding derivatives of 2-phenylethyl arenesulfonates, 1, which can be attributed to a greater degree of positive charge stabilization at Cα in the transition state (TS) by a greater electron supply from a phenyl ring compared to a naphthyl ring. The mechanism for the two naphthylethyl systems are similar to that for the 2-phenylethyl derivatives, except that the transition state is formed at somewhat an earlier position along the reaction coordinate. The secondary kinetic isotope effects involving deuterated nucleophilies indicate that naphthylethyl series are sterically more crowded in the TS than 2-phenylethyl system. The data in this work can not elucidate the possible participation of the aryl-assisted pathway in the reaction.