• Title/Summary/Keyword: bond cleavage

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Theoretical Studies on the Methanolysis of a Cephalosporin; Mimicking Acylation of the Active Site Serine of D-Ala-D-Ala Transpeptidases

  • Nahm, Kee-Pyung
    • Bulletin of the Korean Chemical Society
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    • v.12 no.6
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    • pp.674-678
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    • 1991
  • Methanolysis of a ${\beta}$-lactam ring of a cephalosporin was simulated with AM1 semiempirical quantum mechanical calculation. The tetrahedral intermediate TD1 from an O-protonated cephalosporin and a methanol transfers the proton intramolecularly to the C-4 carboxylate to generate an oxyanion, i.e., second tetrahedral intermediate TD2, which undergoes the amide bond cleavage without further protonation on the N-5. For this cleavage a low-energy barrier TS2 was located. According to the energy diagram, tetrahedral intermediates easily undergo ring cleavage even without the protonation on the amide nitrogen.

Synthesis of Protoberberine Related Compounds and Their Antifungal Activities (프로토베르베린 관련 화합물합성 및 항균작용)

  • Kim, Sin-Kyu;Kim, Dong-Hyun;Chung, Kyung-Hee;Hwang, Soon-Ho;Kim, Jae-Hyun
    • YAKHAK HOEJI
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    • v.38 no.1
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    • pp.91-96
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    • 1994
  • Irradiation of the berberinephenolbetaine [1] effected valence tautamerization to five 8,14-cycloberbine[21, which was converted to the spirobenzylisoquinolines by regioselective C-N bond cleavage A variety of ring systems such as compounds [4], [5] and [6] were introduced by the structural modification of berberinephenolbetaine.

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Electrochemical Reduction of Triphenylphosphine Phenylimide (Triphenylphosphine Phenylimide의 전기화학적인 환원)

  • Pak Chong Min;Wilson M. Gulick, Jr.
    • Journal of the Korean Chemical Society
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    • v.18 no.5
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    • pp.341-353
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    • 1974
  • The electrochemical reduction of triphenylphosphine penylimide in nonaqueous media has been examined by polarography, cyclic voltammetry, controlled-potential coulometry and electron spin resonance spectroscopy. The reduction of triphenylphosphine phenylimide proceeds by a one-electron transfer to form anion radical which undergoes both protonation and a second one-electron reduction followed by cleavage of the phosphorus-nitrogen double bond. Aniline is a major product. The cleavage of a phosphorus-phenyl bond was also observed after reduction of triphenylphosphine oxide which is one of the major products of the chemical reaction which follow the primary process.

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Photoinduced Electron Transfer Reactions of Aryl Benzyl Sulfides Promoted by 2,4,6-Triphenylpyrilium Tetrafluoroborate (TP+BF4-)

  • Memarian, Hamid Reza;Ira, Mohammadpoor Baltork;Bahrami, Kiumars
    • Bulletin of the Korean Chemical Society
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    • v.27 no.1
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    • pp.106-110
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    • 2006
  • Photocatalytic electron transfer reactions of aryl benzyl sulfides using 2,4,6 triphenylpyrilium tetrafluoroborate ($TP^+BF_4^-$) resulted in the oxidation of these sulfides to the corresponding sulfoxides and also in most cases in the C-S bond cleavage of them along with formation of aromatic aldehydes. In these reactions, the formation of sulfide radical cation has been proposed, which undergoes either oxidation to the corresponding sulfoxide or C-S bond cleavage to the formation of aromatic aldehydes. The further oxidation of sulfoxides to sulfones has not been observed. The influence of substrate structures on the reaction pathways as well as the role of $O_2$ in this respect is discussed.

XPS Studies of CO Adsorption on Polycrystalline Nickel Surface

  • Boo, Jin-Hyo;Ahn, Woon-Sun
    • Bulletin of the Korean Chemical Society
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    • v.9 no.6
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    • pp.388-393
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    • 1988
  • The chemisorption of CO molecules on polycrystalline nickel surface has been studied by investigating the resulting chemisorbed species with the X-ray photoelectron spectroscopy at temperatures between 300K through 433K. It is found that the adsorbed CO molecules are dissociated by the simple C-O bond cleavage as well as by the disproportionation reaction at temperatures above 373K. The former type dissociation is more favored at low coverages and at elevated temperatures. The isotherms of CO chemisorption are obtained from the xps intensities of C 1s peaks, and then the activation energy of the dissociative adsorption is estimated as a function of the CO exposure. These activation energies are extrapolated to zero coverage to obtain the activation energy of chemisorption in which thermal C-O bond cleavage takes place. The value obtained is 38.1 kJ/mol.