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PHOTOCATALYTIC SYNTHESIS OF L-PIPECOLINIC ACID FROM $N_{varepsilon}$-CARBAMYL-L-LYSINE BY AQUEOUS SUSPENSION OF PLATINIZED TITANIUM(IV) OXIDE
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  • PHOTOCATALYTIC SYNTHESIS OF L-PIPECOLINIC ACID FROM $N_{varepsilon}$-CARBAMYL-L-LYSINE BY AQUEOUS SUSPENSION OF PLATINIZED TITANIUM(IV) OXIDE
  • PHOTOCATALYTIC SYNTHESIS OF L-PIPECOLINIC ACID FROM $N_{varepsilon}$-CARBAMYL-L-LYSINE BY AQUEOUS SUSPENSION OF PLATINIZED TITANIUM(IV) OXIDE
저자명
Ohtani. Bunsho,Aoki. Eishiro,Iwai. Kunihiro,Nishimoto. Sei-Ichi
간행물명
Journal of photoscience: an international journal officail organ of the Korean Society of Photoscience
권/호정보
1994년|1권 1호|pp.31-37 (7 pages)
발행정보
한국광과학회
파일정보
정기간행물|ENG|
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이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
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기타언어초록

Photoirradiation at > 300 nm onto a suspension of platinized TiO$_2$ (TiO$_2$-Pt) particles in an aqueous solution. of N$_{varepsilon}$-carbamyI-L-lysine (Lys(CONH)$_2$) induced the selective N-cyclization of Lys(CONH$_2$) into almost optically pure L-pipecolinic acid (PCA) under argon atmosphere at ambient temperature. Among various TiO$_2$-Pt catalysts, a P-25 (Degussa) powder platinized via impregnation from chloroplatinic acid followed by hydrogen reduction at 753 K exhibited the highest photocatalytic activity for Lys(CONH$_2$) consumption and L-PCA production. GC-MS analyses of L-PCA obtained photocatalytically from $^{15}$N$alpha$-Lys(CONH$_2$) revealed the selective formation $^{15}$N-substituted L-PCA. This implies that the mechanism for L-PCA production contains selective cleavage of C$_{varepsilon}$-N bond and intramolecular alkylation at $alpha$-amino group. Effect of pH on the rate of this photocatalytic reaction was investigated in detail and compared with the pH-dependent charge distribution in Lys(CONH$_2$) molecule. It is clarified that protonation-deprotonation of $alpha$-amino group gives marked influence on the rate and selectivity of the photocatalytic reaction. On the basis of these results, it is concluded that the selective production of optically pure L-PCA, especially in an acidic suspension of TiO$_2$-Pt, was attributed to the enhanced protonation of $alpha$-amino group to prevent undesirable oxidation by photogenerated positive holes and blocking of $varepsilon$-amino group to yield racemic Schiff base intermediate.