有機イオウ化合物に関する研究(第15報)脱硫閉環反応におけるプロトンならびに重金属イオンの役割

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概要

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• A role of proton and heavy metallic ions in the desulfurization ring-closure reaction of 4-(o-aminophenyl)-3-thioallophanic acid ester (Ib) is discussed from the concept of charge and frontier controlled reactions based on a quantum chemical perturbation theory. It is assumed that the protonation to Ib may occur at the position of O-12,S-13,and N-14 atoms but heavy metallic ions, which are known as soft acids, make the selective coordination at the position of S-13,which has the largest highest-occupied density. The energy change in the π-conjugated intramolecular ring-closure reaction is estimated from the perturbation term by the HMO approximation on the assumption that the increase of Coulomb integrals h_<O12>, h_<S13>, and h_<x14> may be caused by the protonation. The increase of h_<S13> and/or the decrease of h_<x14> makes the partial bond orders P^<HO>_<8,13> negative and P^<HO>_<8,14> positive resulting in the decrease of P_<8,13> and the increase of P_<8,14> Namely, the protonation to S-13 (the increasing electronegativity of S-13) suggests the tendency of the formation of a new bond between C-8 and N-14,and the weakening of the bond between C-8 and S-13. However, the protonation to O-12 or N-14 (the increasing electronegativity of O-12 or N-14) suggests the opposite tendency. It is understandable that the presence of heavy metallic ions which may cause the selective addition to S-13 accelerates the ring-closure reaction of Ib.

• 公益社団法人日本薬学会の論文
• 1974-05-25

著者

• 木下 武

  三共株式会社 分析代謝研究所

• 長野 光男

  Central Research Laboratories, Sankyo Co., Ltd.

• 木下 武

  三共株式会社中央研究所

• 松井 孝司

  三共株式会社農業研究所

• 長野 光男

  三共株式会社中央研究所

• 長野 光男

  Central Research Laboratories Sankyo Co. Ltd.

• 松井 孝司

  Agricultural Chemicals Research Laboratories

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