Design and Analysis of the Solid-State Organic Reactions

固态有机反应的设计与分析

• 批准号: 11640526
• 负责人: KOBAYASHI Keiji
• 金额: $ 2.05万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11640526/
• 关键词: Solid-State Reactions; Charge-Transfer; Clathrate Crystals; Tribochromism; Piezochromism; Ion Radical; 固相ラセミ化; 固相求核置換反応; カルボカチオン塩; 固相酸触媒; 転位反応; 混晶; 立体選択性; カルボカチオン; 分子内転位

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.

我们研究了噻吩取代叔醇与DDQ或TCNQ共研磨粉末在甲醇蒸汽中引发的固态亲核取代反应。结果表明，该反应是通过与甲醇蒸气接触来进行的，并通过碳正离子作为中间体来进行。二醇衍生物分别与TCNQ和四氟TCNQ形成电荷转移络合物。这些晶体是同构的，但它们的反应性不同。四氟TCNQ配合物在研磨后暴露于甲醇蒸气中发生取代反应，而TCNQ配合物则不发生取代反应.当三（苯并噻吩）衍生物与DDQ共研磨时，得到一种新型的硫靛类化合物.该化合物表现出摩擦变色和压致变色特性。在红色和黑色之间的可逆颜色变化归因于部分电荷转移相互作用的发生在固态诱导研磨。

项目成果

M.Tanaka: "Solid State Solvolysis of Thiophene-Substituted Trityl-Type Alcohols : Nucleophilic Substitution"J. Orgl. Chem. 66. 803-808 (2001)

M.Tanaka：“噻吩取代的三苯甲基醇的固态溶剂分解：亲核取代”J。

N.Tanifuji: "Pseudo-Polymorphs Arising from Weak and Strong -OH- N≡C- Hydrogen Bonding in Inclusion Crystals"Cryst En Comm.. 3. (2001)

N.Tanifuji：“包合物晶体中弱和强-OH-N≡C-氢键产生的伪多晶型”Cryst En Comm.. 3. (2001)

M.Tanaka: "Solid State Solvolysis of Thiophene-Substituted Trityl-Type Alcohols : Nucleophilic Substitution"J. Org. Chem.. 66. 803-808 (2001)

M.Tanaka：“噻吩取代的三苯甲基醇的固态溶剂分解：亲核取代”J。

Y. Pontillon: "Experimental and Theoretical Spin Density in a Ferromagnetic Molecular Complex"Molecular Cryst. Liq. Cryst.. 334. 211-220 (1999)

Y. Pontillon：“铁磁分子复合物中的实验和理论自旋密度”分子晶体。

K. Takahashi: "Preparation and Redox Properties of Longitudinally Twinned TCNQ:"Tetrahedron Letters. 40. 5349-5352 (1999)

K. Takahashi：“纵向孪生 TCNQ 的制备和氧化还原性质：”四面体字母。