Chirality recognition in solvent-free solid-state crystallization: chiral adduct formation by bis-beta-naphthol derivatives and benzoquinone crystals.
Chirality recognition in solvent-free solid-state crystallization: chiral adduct formation by bis-beta-naphthol derivatives and benzoquinone crystals.
复制标题
无溶剂固态结晶中的手性识别：双-β-萘酚衍生物和苯醌晶体形成手性加合物。
作者：
R. Kuroda;Y. Imai;T. Sato
在无溶剂条件下，通过简单地混合/研磨双-β-萘酚（BN）衍生物与苯醌（BQ）的组分晶体获得新的加合物晶体。手性识别被发现在此过程中操作，并且BN衍生物的外消旋或手性晶体通过固态结晶与BQ产生加合物晶体。手性偏好根据BN衍生物的分子结构而微妙地变化。即使在没有形成加合物的情况下，向研磨混合物中加入第三组分如萘的晶体也产生加合物晶体。值得注意的是，发现这些加合物晶体随时间自发分解，并通过从晶格中失去BQ分子而恢复为BN衍生物的起始晶体。发现由研磨压力引起的晶体的局部熔融不太可能是加合物形成的机制。总之，这些结果表明，在固态分子可以改变它们的相对位置和氢键合作伙伴，从而发挥手性歧视。
New adduct crystals were obtained by simply mixing/grinding component crystals of bis-beta-naphthol (BN) derivatives with benzoquinone (BQ) under solvent-free conditions. Chiral recognition was found to operate during this process and either a racemic or a chiral crystal of a BN derivative produced an adduct crystal with BQ by solid-state crystallization. The chirality preference changed subtly according to the molecular structure of the BN derivative. Even in circumstances in which no adduct was formed, addition of a third component, such as crystals of naphthalene, to the grinding mixture yielded an adduct crystal. Remarkably, these adduct crystals were found to decompose spontaneously with time and revert to the starting crystal of the BN derivative by losing BQ molecules from the crystal lattice. Local melting of crystals by the grinding pressure was found unlikely to be the mechanism of adduct formation. Overall, these results demonstrate that molecules in the solid state could change their relative location and hydrogen bonding partners, thereby exerting chiral discrimination.