硅杂六元环化合物的反应

硅杂六元环化合物在有机硅化学中是一类重要的小分子环系化合物,广泛应用于有机化学、高分子化学、金属有机化学以及材料化学等领域。本文综述了环上只含有一个硅原子的硅杂六元环化合物的反应,介绍了硅原子上取代基的反应、立体选择性合成、硅原子α位碳原子上的反应、插入反应、环加成反应、Si—C键的切断反应、硅杂苯衍生物合成以及金属配位反应等,并展望了硅杂六元环化合物反应化学的发展方向。     

金属杂六元环的合成方法研究进展

研究发现许多重要的金属促进的合成反应都是经过金属杂环进行的,因此金属杂环的合成方法学以及反应化学研究受到了学术界及工业界的极大关注.关于金属杂五元环的研究报道数量很多,而金属杂六元环的文献报道非常之少.考虑到金属杂六元环在有机合成化学中潜在的重要用途,结合作者近年的一些研究工作,对目前已经报道的金属杂六元环的合成方法进行回顾与展望.     

硅杂四元环化合物的合成和反应

硅杂四元环化合物在有机硅化学中是一类非常重要的小分子环系化合物, 广泛应用于有机化学、金属有机化学以及材料化学. 环上只含有一个硅原子的硅杂环丁烷可以通过γ-卤代丙基硅烷的Grignard反应、Si＝C键与烯烃的 [2＋2]环加成反应以及硅杂环丙烷的扩环反应合成, 环上只含有一个硅原子的硅杂环丁烯可以通过格氏试剂或锂试剂参与的Si—C键的关环反应、硅杂环丁烷的转化反应、硅卡宾对C—H键的插入反应、Si＝C键与炔烃的[2＋2]环加成反应以及二炔基硅烷的分子内成环反应等途径合成. 硅杂环丁烷和硅杂环丁烯由于存在环张力和具有一定的Lewis酸性, 能够通过扩环反应生成五元和六元含硅杂环化合物, 也能够通过开环反应生成不同结构的有机硅分子和聚合物, 抑或实现有机反应在温和条件下的转化.     

双-杂氮硅三环化合物的合成

杂氮硅三环是一类分子内具有N→Si配位键的化合物，作者曾报道了一系列该类化合物的合成方法和化学结构。对于一个分子内带两个对称的硅三环结构的双一杂氮硅三环化合物的合成，文献报道还很少啪。我们用下     

氮杂硅三环类化合物的质谱研究

本文对二十四个氮杂硅三环类化合物进行了质谱研究.测定了它们的低分辨质谱,收集了大部分化合物的高分辨质谱数据并进行了亚稳跃迁测定。结果表明,分子离子的稳定性、基峰的生成方式以及碎片离子的多少主要取决于取代基R的性质.分子的电子轰击质谱裂解存在三种基本方式:(1)断裂Si～R键,生成高度稳定的(M-R)~ 离子,碎片离子较少;(2)开环,失去碎片C_2H_3O;(3)开环,失去碎片CH_2O或CH_3O.用电荷自由基定域理论解释这类化合物的质谱裂解机理,并对影响分子离子稳定性的有关因素及影响基峰形成的原因进行了讨论.     

具有生物活性的有机硅化合物的研究(Ⅷ)——1-烷酰氧基杂氮硅三环的合成及抗癌活性的研究

报道了用1-溴代Silatrane合成1-烷酰氧基-2,8,9-三氧-5-氮-1-硅杂三环[3,3,3,0~(1.5]十一碳烷的新方法。讨论了反应条件对该类化合物合成的影响,用各种方法确证了产物的结构,对某些化合物进行了抗癌活性实验。     

不饱和的钛杂五元环化合物合成的新方法

报导了钛亲环戊二烯络合物的新合成法, 用双(环戊二烯基)二(苯乙炔基)钛与溴、溴化氢、四溴化碳、四氯化碳和碘甲烷待反应合成了五个不饱和钛亲五元环化合物, 并讨论了反应机理.     

杂氮硅三环成环反应的研究

本文报导了与硅原子直接相连的有机基团(R)对杂氮硅三环成环速率的影响。利用气相色谱检测成环反应的产物之一——乙醇的生成速率和数量,并同与硅相连的R基团对成环反应速率的影响作比较。实验结果表明五种杂氮硅三环成环速度顺序为Cl_2CH—>ClCH_2—>ClCH_2CH_2CH_2—>CH_2=CH—>CH_3—,这与理论推断相符。     

1-杂环芳酰氧基-2,8,9-三氧杂-5-氮杂-1-硅杂三环[3.3.3.0~(1,5)]十一碳烷的研究

本文合成了六个1-杂环芳酰氧基杂氮硅三环和三个1-杂环芳酰氧甲基杂氮硅三环,这些化合物均未见文献报道。通过1~H NMR、IR 和 X 射线衍射的方法,确证上述化台物为五配位结构,分子内的 N→Si 配键强度较大。这是一类低毒或中毒化合物。     

1-卤代杂氮硅三环的合成

作者曾对具不同环骨架和不同R取代基的杂氮硅三环(silatrane,简称硅三环)进行过研究.其中硅与R间均为Si—C键.标题化合物中高电负性的卤素与硅直接成键,因而是一组考察硅三环各种性质的典型化合物.     

Microwave-Assisted Synthesis of Six-Membered S-Heterocycles

The development of new strategies for synthesis of six-membered S-heterocycles has remained a highly attractive but challenging proposition. An overview of the application of microwave irradiation in sulfur-containing six-membered heterocyclic compounds synthesis is presented, focusing on the developments in the past 5–10 years. This contribution covers the literature concerning the total synthesis of six-membered S-heterocycles.     

Microwave-Assisted Synthesis of Six-Membered O-Heterocycles

The development of new strategies for synthesis of six-membered O-heterocycles has remained a highly attractive but challenging proposition. An overview of the application of microwave irradiation in oxygen-containing six-membered heterocyclic compounds synthesis is presented, focusing on the developments in the past 5–10 years. This contribution covers the literature concerning the total synthesis of six membered O-heterocycles.     

Polycyclic Six-Membered N-Heterocycles: Microwave-Assisted Synthesis

The development of new strategies for synthesis of polycyclic heterocycles has remained a highly attractive but challenging proposition. An overview of the application of microwave irradiation in nitrogen-containing six-membered polycyclic heterocyclic compounds synthesis is presented, focusing on the developments in the past 5–10 years. This contribution covers the literature concerning the total synthesis of N-heterocycles.     

Microwave-Assisted Synthesis of Six-Membered O,O-Heterocycles

The development of new strategies for synthesis of six-membered O,O-heterocycles has remained a highly attractive but challenging proposition. An overview of the application of microwave irradiation in two oxygen atoms containing six-membered heterocyclic compounds synthesis is presented, focusing on the developments in the past 5–10 years. This contribution covers the literature concerning the total synthesis of six-membered O,O-heterocycles.     

Nitrogen-Containing Six-Membered Heterocycles: Solid-Phase Synthesis

Solid-phase organic synthesis is a rapidly expanding area of synthetic chemistry that is being widely exploited in the search for new medicinally important compounds using combinatorial techniques. In recent decades, a large number of reports related to solid-phase synthesis of heterocycles have appeared because of the wide variety of their biological activity. In this review, we report the important role of solid-phase synthesis in the synthesis of nitrogen containing six-membered ring heterocycles.     

Microwave-Assisted Synthesis of Fused Polycyclic Six-Membered N-Heterocycles

The development of new strategies for synthesis of fused polycyclic heterocycles has remained a highly attractive but challenging proposition. An overview of the application of microwave irradiation in nitrogen-containing six-membered fused polycyclic heterocyclic compounds synthesis is presented, focusing on the developments in the past 5 to 10 years. This contribution covers the literature concerning the total synthesis of fused polycyclic N-heterocycles.     

Review of Microwave-Assisted Synthesis of Benzo-Fused Six-Membered N,N-Heterocycles

The development of new strategies for synthesis of fused heterocycles has remained a highly attractive but challenging proposition. An overview of the application of microwave irradiation in nitrogen-containing benzo-fused six-membered heterocyclic compounds synthesis is presented, focusing on the developments in the past 5–10 years. This contribution covers the literature concerning the total synthesis of benzo-fused N,N-heterocycles.