Synthesis of 1,128-Octacosahectanediol and Its Sharp Thermoresponse in Solution with Concomitant Structural Change
Synthesis of 1,128-Octacosahectanediol and Its Sharp Thermoresponse in Solution with Concomitant Structural Change
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1,128-八十六烷二醇的合成及其在溶液中的急剧热响应以及伴随的结构变化
DOI：
10.1002/slct.201701356
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发表时间：
2017
期刊：
影响因子：
2.1
通讯作者：
Shinozaki Yasuhiro、Shigeno Masanori、Mushiake Kumiko、Yamaguchi Masahiko
中科院分区：
文献类型：
--
作者：
Saito Nozomi;Shinozaki Yasuhiro、Shigeno Masanori、Mushiake Kumiko、Yamaguchi Masahiko
合成了具有极长聚亚甲基链的1，128-二十八碳十六烷。通过Wittig反应和缩醛脱保护的顺序，以双向方式合成了两端甲硅烷基化的七烯C128中间体。通过在甲苯回流下的均相氢化将不饱和化合物转化为饱和二甲硅烷基醚，随后在THF/甲苯/12 M HCl水溶液条件下脱甲硅烷基，得到C128二醇。 采用高温条件溶解底物，冷却释放产物，通过过滤分离产物。1，128-十八碳十六烷在有机溶剂中的溶解度随着温度变化10 K而急剧增加，沿着伴有热滞后，这归因于伴随的结构变化。 固态下的扩展结构在溶液中转变为球状结构，这涉及较大的焓损失和熵增益。
1,128‐Octacosahectanediol, which has an extremely long polymethylene chain, was synthesized. The heptaene C128intermediate with both ends silylated was synthesized by the sequence of the Wittig reaction and acetal deprotection in a two‐directional manner. The unsaturated compound was converted to a saturated disilyl ether by homogeneous hydrogenation under toluene reflux, and was subsequently desilylated under THF/toluene/12 M HCl refluxing conditions to yield a C128diol. High‐temperature conditions were employed to dissolve the substrates, and cooling liberated the products, which were isolated by filtration. 1,128‐Octacosahectanediol showed a sharp increase in solubility in organic solvents with temperature changes of 10 K along with thermal hysteresis, which was ascribed to the concomitant structural change. The extended structure in the solid state was converted to a globular structure in solution, which involved large enthalpic loss and entropic gain.