P-82 重合度を制御した直鎖及び環状ポリグリセロールの合成(ポスター発表の部)

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概要

• 論文の詳細を見る

• Polyglycerols (PG) are oligmers of a glycerol (Gly). Although PGs are readily available in bulk quantities by industrial manufacture, the reaction requires drastic conditions, including high temperature and alkaline media. Therefore, commercially available PGs are very complicated oligomeric mixtures and undefined molecular composition with difficult characterization. We therefore focused our attention on the synthesis of single and fine structure of highly linear and cyclic PGs ad an authentic standard. In this presentation, we reported a synthesis of the linear decaglycerol (Gly_<10>) controlled the polymerization degree and an efficient synthesis of the cyclic PGs with the intramolecular macrocyclization. Further more, we tried a new functionality of the synthetic linear and cyclic PG derivatives. 1. Synthesis of linear decaglycerol controlled the polymerization degree First, we examined a synthesis of Gly_<10> controlled the polymerization degree. Our concept is consisted that a step-by-step coupling among the two variety of diglycerol (DG) units protected all of the hydroxy groups except for the reaction point. According to our concept, we prepared two type of DG units from solketal. The coupling of the two type DG unit was given tetraglycerol (Gly_4) derivatives without other oligomeric isomers. The Gly_4 derivatives was coupled with a DG unit to give hexaglycerol (Gly_6). Unfortunately, we could synthesize Gly_<10> by repeating this protocol. GPC analysis of the synthesized Gly_<10> was shown a single oligomeric isomer. 2. Synthesis of cyclic PGs Next, we tried to the development of an efficient synthetic route. First, we tried to an intermolecular cyclization of the ditosylate of PGs and diol of PGs, but the desired product was given in low yield. So, we tried to an intramolecular cyclization of monotosylate of PGs. When the monotosylates of tri-, tetra-, penta-, and hexaglycerol was treated with NaH in DMF at 80 ℃ for 2 days to give desired cyclic TG, Gly_4, Gly_5, and Gly_6 in 38%, 38%, 54%, 70% yields, respectively. To increase the yield of cTG, we modified the experimental procedure, that is, a solution of monotosylate of TG in THF was added dropwise to a mixture of NaH in refluxed THF over 3 hours, and then the mixture was refluxed 19 hours to give cTG in 60% yield. The debenzylation of cTG was smoothly proceeded to give a free cTG in 98% yield. The given cTG derivatives was used as a phase transfer catalyst for an epoxidation of trans-chalcone. In the result, these compounds were shown a promoting effect of this reaction, although the ability for PTC was not shown.

• 天然有機化合物討論会の論文
• 2007-08-24

著者

• 中島 範行

  富山県大工

• 中島 範行

  富山県立大学工学部生物工学科

• 吉川 公夫

  富山県立大学工学部生物工学科

• 濱田 昌弘

  富山県立大学工学部生物工学科

• 濱田 昌弘

  富山県大工

• 吉川 公夫

  富山県大工

• 川岸 貴博

  富山県大工

• 藤原 亮

  富山県大工

• 清登 達朗

  富山県大工

• 岸本 崇生

  富山県大工

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