Synthesis of Novel Heterocyclic Compounds Containing Group 15 Heaver Elements, and Their Properties.

本研究旨在合成新的含15族和16族重元素的完全不饱和五元杂环和七元杂环化合物，并对其结构特征、反应活性、热稳定性和手性等化学性质进行研究.用金属试剂（MX_2或M：M=PPh，AsPh，SbPh，BiPh，S，Se和Te）处理由相应的二溴化合物和烷基锂生成的1，4-二硫代丁二烯或1，6-二硫代己三烯体系，使其闭环，得到预期的分别由第15族和第16族重元素组成的杂环化合物或杂环庚烯。理论上可以合成三种噻吩并[2，3-B]、[3，4-B]和[3，2-B]杂环化合物，即3-苯并杂环庚烯、二苯并杂环庚烯和二噻吩并杂环庚烯，其中大部分是一类新的杂环体系。本文所制备的所有杂环庚烯都是热不稳定的杂原子挤出，并逐渐分解为萘 ...更多信息 艾伦通过~ 1H-NMR谱分析估算了它们的热稳定性，结果表明：（a）3-苯并杂环庚烯的热稳定性远低于相应的1-苯并杂环庚烯，（B）16族杂环庚烯的热稳定性按Te>Se>S的顺序降低，但15族杂环庚烯的稳定性没有规律可循，我们还证明了0，b-二硫代苯乙烯与CoI_2（Cp）（PPh_3）反应生成钴茚，后者易于转化为异喹啉，喹啉和二硫代香豆素分别与腈、异氰酸酯和二硫化碳在密封管中加热。这些结果表明，钴茚是一种有用的合成各类杂环化合物的合成子.研究了含15族重元素的1-苯并杂环化合物与改性Sharpless试剂或Davis手性氧氮丙啶试剂（0.5mol eq.）导致对映选择性氧化，得到光学活性氧化物和三价化合物。分离的光学活性的stibindole和bismindole应该是稳定的不对称有机锑（III）和铋（III）化合物的第一个例子。用手性钯配合物作~ 1H-NMR位移试剂测定了它们的光学纯度。少

This study was performed to synthesize new fully unsaturated five- (heteroles) and seven- (heteroepines) membered heterocyclic compounds containing group 15 and 16 heavier elements, and to elucidate their chemical properties such as structural feature, reactivity, thermal stability, and chirality.1. Treatment of 1,4-dilithiobutadiene or 1,6-dilithiohexatriene systems, generated from the corresponding dibromo compounds and alkyllithium, with metal reagents (MX_2 or M : M=PPh, AsPh, SbPh, BiPh, S,Se, and Te) to result in ring closure giving the expected heteroles or heteroepines composed of group 15 and 16 heavier elements respectively. This procedure allowed to prepare theoretically possible three kinds of thieno [2,3-b], [3,4-b], and [3,2-b] heteroles, 3-benzoheteroepines, dibenzo-, and dithieno heteroepines most of which are a new class of heterocyclic ring system. All of the heteroepines prepared here are thermally labile toward heteroatom extrusion and gradually decomposed to naphth … More alene. The thermal stabilities of them were estimated from ^1H-NMR spectral analysis and the results revealed the following : (a) the 3-benzoheteroepines are far less stable than the corresponding 1-benzoheteroepines except for the phosphepine, (b) the thermal stabilities of the group 16 heteroepines decrease in the order Te>Se>S,but there is no pattern to the stabilities of the group 15 heteroepines.We have also demonstrated that 0, b-dilithiostylene react with CoI_2 (Cp) (PPh_3) to give rise to cobaltaindene which can be easily converted to isoquinolines, quinolines, and dithiocoumarin by heating with nitrils, isocyanates and carbon disulfide in sealed tube respectively. These results indicates that the cobaltaindene is a useful synthon of various types of heterocyclic compounds.2. The reaction of 1-benzoheteroles containing group 15 heavier elements with the modified Sharpless reagent or the Davis chiral oxaziridine reagent (0.5mol eq.) resulted in enantio-selective oxidation to afford optically active oxides and trivalent compounds. The isolated optically active stibindole and bismindole should be the first examples of stable unsymmetrical organoantimony (III) and bismuth (III) compounds. The optical purities of them were determined by the use of chiral Pd complex as a shift reagent of ^1H-NMR. Less