Design and Analysis of the Solid-State Organic Reactions

我们研究了噻吩基叔醇与DDQ或TCNQ共磨粉末在甲醇蒸气中发生的固相亲核取代反应。结果表明，该反应是通过与甲醇蒸汽接触而进行的，并以正碳阳离子为中间体进行。二醇类化合物分别与TCNQ和四氟TCNQ形成了晶态电荷转移络合物。这些晶体是等结构的，但它们的反应活性不同。四氟TCNQ络合物在研磨后暴露在甲醇蒸汽中发生取代反应，而TCNQ络合物不发生取代反应。当三(苯并噻吩基)衍生物与DDQ共研磨时，得到了一种新型的硫代吲哚化合物。该化合物具有摩擦变色和压电致变色性能。红色和黑色之间的可逆颜色变化归因于研磨引起的固态部分电荷转移相互作用。

We have investigated the solid-state nucleophilic substitution reactions induced in the co-ground powder of thiophene-substituted tert-alcohols and DDQ or TCNQ followed by exposure to methanol vapor. It was revealed that the reaction is propagated by contact with methanol vapor and is proceeded via carbocation as an intermediate. A diol derivative afforded crystalline charge-transfer complexes with TCNQ and tetra-fluoro TCNQ, respectively. These crystals were isostructural, while their reactivities were different. The tetrafluoro TCNQ complexes undergo substitution reactions on grinding followed by exposure to methanol vapor, whereas the TCNQ complexes do not.When a tri(benzothienyl) derivative was co-ground with DDQ, a novel type of thioindigoid compound was obtained. This compound showed tribochromic and piezochromic properties. The reversible change in color between red and black was attributed to occurrence of partial charge-transfer interactions in the solid state induced by grinding.