Synthesis and Properties of Novel pi-Electronic Hydrocarbons Having sigma-pi Interaction

具有σ-π相互作用的新型π电子烃的合成与性能

• 批准号: 07454165
• 负责人: KOMATSU Koichi
• 金额: $ 4.03万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07454165/
• 关键词: sigma-pi conjugation; C-C hyperconjugation; bicyclo [2.2.2] octene; silole; germole; cation radical; benzyne; anthracene; σ-π共役; ビシクロオクテン; デヒドロアヌレン; カップリング 反応; サイクリック ボルタメトリー; σ-π相互作用; π共役素; 酸化還元; バンザイン

1.Synthesis of the Cyclopentadienylpi-System Annelated with Bicyclooctene Frameworks.Bicyclo [2.2.2] octene (abbreviated as BCO) was used as the structural unit for the synthesis of pi-systems having novel properties. Thus, a series of substituted cyclopentadienyl derivatives annelated with two BCO units have been synthesized and their redox behaviors investigated in detail.2.Synthesis of Sila-and Germacyclopentadienes Annelated with BCO Units.The above silole and germole derivatives have been newly synthesized and their spectral properties fully characterized. The presence of sigma-pi interaction has been investigated based on the results of UV data and MO calculations.3.Generation of the Benzyne Annelated with Two BCO Units.The generation of the above mentioned benzyne has been confirmed by trapping experiment. This benzyne has also been converted to the biphenylene derivative and its unique redox behaviors were clarified.4.Synthesis and Properties of the Anthracene Annelated with Four BCO Units.The above mentioned anthracene derivative has been newly synthesized by the use of double Diels- Alder reaction of the BCO dimer with p-benzoquinone as a dienophile. The notable increase in HOMO level owing to the sigma-pi interaction has been demonstrated by the use of electrochemical and organochemical redox reactions. The stable cation radical and dication have successfully been generated from this anthracene derivative.

1.双环辛烯骨架连接的环戊二烯基π体系的合成。以双环[2.2.2]辛烯（缩写为BCO）为结构单元，合成了具有新颖性质的π体系。由此，合成了一系列两个BCO单元稠合的取代环戊二烯基衍生物，并详细研究了它们的氧化还原行为。2.BCO单元稠合的Sila-和Germacyclopentadiene的合成。新合成了上述噻咯和germa环戊二烯衍生物，并对其光谱进行了研究。特性得到充分表征。根据UV数据和MO计算结果，研究了sigma-pi相互作用的存在。3.两个BCO单元退火的苯炔的生成。上述苯炔的生成已通过捕获实验得到证实。该苯炔也被转化为亚联苯衍生物，并阐明了其独特的氧化还原行为。 4.四个BCO单元退火的蒽的合成及性能。上述蒽衍生物是利用双Diels-Alder反应新合成的BCO 二聚体与对苯醌作为亲二烯体。电化学和有机化学氧化还原反应的使用已经证明了由于 sigma-pi 相互作用而导致 HOMO 水平显着增加。该蒽衍生物已成功生成稳定的阳离子自由基和双阳离子。

项目成果

T.Nishinaga: "sigma-pi conjugation, C-C Hyperconjugation" J Synth.Org.Chem.Jpn.vol.54, No.10. 879-879 (1996)

T.Nishinaga：“sigma-pi 共轭，C-C 超共轭”J Synth.Org.Chem.Jpn.vol.54，No.10。

T.Nishinaga: "Synthesis and Properties of Dehydroannulenes Annelated with Bicyclo [2.2.2] octene Frameworks" J.Org.Chem.(submitted for publication).

T.Nishinaga：“双环[2.2.2]辛烯骨架退火的脱氢环烯的合成和性质”J.Org.Chem.（已提交出版）。

K.Komatsu: Houben-Weyl, Methods of Organic Chemistry, Cyclopropenylium Salts. Georg Thieme Verlag, stuttgart., 3079-3193 (1996)

K.Komatsu：Houben-Weyl，有机化学方法，环丙烯盐。

A.Matsuura: "Synthesis and Properties of Novel Anthracene Tetra-annelated with Bicyclo [2.2.2] octene Frameworks" Tetrahedron Lett.(in press).

A.Matsuura：“双环[2.2.2]辛烯框架的新型蒽四退火的合成和性能”Tetrahedron Lett.（出版中）。

A.Matsumura,K.Komatsu et al.: "Synthesis and propertis of Novel Anthracene Tetra-annelated with Bicyclo[2.2.2]octene Framewroks" Tetrahedron Letters. (発表予定).

A.Matsumura、K.Komatsu 等人：“新型蒽四退火与双环[2.2.2]辛烯框架的合成和性能”四面体快报（待出版）。