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

含15族重元素的新型杂环化合物的合成及其性质。

• 批准号: 07672298
• 负责人: KURITA Jyoji
• 金额: $ 1.02万
• 依托单位: Hokuriku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 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-07672298/
• 关键词: organometallic chemistry; group 15 and 16 heavier elements; heterol; heteroepine; thermal stability; cobaltaindene; enantio-selective oxidation; optical resolution; ヒ素; アンチモン; ビスマス; 複素環; 渡環相互作用; 置換反応; 重元素; 1-ベンゾヘテロール; 1-ベンゾヘテロピン; 3-ベンゾヘテロ

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

本研究合成了含第15和16族较重元素的新型全不饱和五元杂环和七元杂环化合物，并对它们的结构特征、反应活性、热稳定性和手性进行了研究。用金属试剂(MX_2或M：M=PPh、AsPh、SbPh、BiPh、S、Se和Te)与相应的二溴化合物和烷基锂生成的1，4-二硫代丁二烯或1，6-二锂硫代己三烯体系进行环合反应，得到预期的第15族和第16族较重元素组成的杂环化合物或杂环化合物。该方法可以合成理论上可能的三种硫代[2，3-b]、[3，4-b]和[3，2-b]杂环化合物，即3-苯并杂环、二苯并杂环和二硫杂环，其中大部分是一类新的杂环体系。所有制备的杂环己烷都是热不稳定的，不利于杂原子挤出，并逐渐分解为环状…。再来点清新的。结果表明：(A)除膦以外，3-苯并异构体的热稳定性远不如相应的1-苯并异构体，(B)第16族杂环化合物的热稳定性按Te&Gt、Se&Gt、Se&Gt的顺序递减；我们还证明了0，b-二锂硫代苯乙烯与CoI_2(Cp)(PPh_3)反应生成钴烯，在密封管中分别与丁腈、异氰酸酯和二硫化碳加热，可以很容易地转化为异喹啉、喹啉和二硫香豆素。这些结果表明钴是一种有用的各种杂环化合物的合成子。研究了含有第15族较重元素的1-苯并杂环化合物与改进的夏普莱斯试剂或Davis手性恶氮杂环试剂(0.5moleq.)导致对映体选择性氧化，得到光学活性氧化物和三价化合物。分离的光学活性的二苯二酚和双心酮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。用手性钯配合物作为~1H-核磁共振的位移试剂测定了它们的光学纯度。较少

项目成果

Naoki Kakusawa: "Reaction of 1,2,4-Triazine 1-Oxide with Benzyne : Formation of 1,3-Benzoxepine and 1,3,5,6-Benzotriazonine Derivatives." Heterocycles. 43. 2091-2094 (1996)

Naoki Kakusawa：“1,2,4-三嗪 1-氧化物与苯炔的反应：形成 1,3-苯并氧杂环庚烷和 1,3,5,6-苯并三嗪衍生物。”

Shuji Yasuike, Jyoji Kurita and Takashi Tsuchiya: "Synthesis of novel group 15 and 16 thieno [2,3-b] -, thieno [3,4-b]-and thieno [3,2-b] -heteroles" Heterocycles. 45. 1891-1894 (1997)

Shuji Yasuike、Jyoji Kurita 和 Takashi Tsuchiya：“新型第 15 组和 16 噻吩并[2,3-b]-、噻吩并[3,4-b]-和噻吩并[3,2-b]-杂环的合成”杂环。

Shuji Yasuike: "Syntheses of the Group 15 1-Benzoheteroepines, Dibenzo〔b, d〕heteraepines and Dibenzo〔b,f〕heteraepines involving the First Isolated Examoles of Arsepines and Bismepimes" J. Chem. Socy Chem. Communy. 1817-1819 (1993)

Shuji Yasuike：“第 15 族 1-苯并杂庚烷、二苯并[b，d]杂庚烷和二苯并[b，f]杂庚烷的合成，涉及第一个分离的胂化合物和双甲肟”J. Chem Socy Community。 (1993)

Jyoji Kurita: "A Virsatile Synthetic Route to 1-Benzometalloles involving First Examples of Several C-Unsubstituted Benzometalloles" J. Chem. Socy Chem. Communy. 1309-1310 (1993)

Jyoji Kurita：“一种通用的 1-苯并金属醇合成路线，涉及几种 C-未取代的苯并金属醇的第一个例子”J. Chem。

Shuji Yasuike, Fumio Nakajima, Jyoji Kurita and Takashi Tsuchiya,: "Synthesis of novel dithieno[2,3-b,3',2'-f]-and dithieno[3,4-b,3',4'-f]heteroepines containing group 14,15 and 16 heavier elements" Heterocycles. 45. 1899-1903 (1997)

Shuji Yasuike、Fumio Nakajima、Jyoji Kurita 和 Takashi Tsuchiya，：“新型 dithieno[2,3-b,3,2-f]- 和 dithieno[3,4-b,3,4-f 的合成”