讨论了含硫大杂环化合物的合成方法、结构和光谱特征。以α,_-二卤代烷与碱α,_-烷二硫醇反应,合成了含2-6个硫原子的12-42元大杂环。通过芳香族1,2-二硫醇或2-巯基酚与脂肪族α-二卤代衍生物的反应,制备了含硫和氧原子的氧杂硫大环烷烃。硫大环烷烃的合成包括二甲醚或α,_烷二羧酸二氯化物与α,_烷二胺的反应,然后用LiAlh4或B2H6还原大杂环二胺。以二羧酸二氯化物与α,_-恶烷二胺反应,以及氯磺酰-β-内酰胺与乙二醇反应制备了氧杂氮杂大环烷,双(溴甲基)取代芳烃与双(巯基甲基)苯的反应是合成低聚噻环烷的一般途径。以2,6-双(溴甲基)吡啶与α,_-烷烃二硫醇反应制备了含硫环吡啶衍生物。对于含有一个、两个或多个噻吩环的大环化合物的合成,基于-噻吩烷羧酸氯化物的分子内和分子间酰化、2,5-双(碳烷氧基烷基)噻吩的酰偶姻缩合和-卤代烷基取代的噻吩β-酮酯的分子内烷基化的一些步骤。研究了含二硫化物和多硫化物的大杂环化合物的合成路线。合成过程中,均三甲苯或1,3-二甲氧基苯与二硫二氯化物或二硫二氯化物硫化,并氧化二硫醇,以1,3,5-三(巯基烷基)苯与三(溴代烷基)-甲烷或L,3,5-三[4-(巯基甲基)苯基]-苯的反应为基础,合成了双和三丙烯基环化合物。以1,3,5-三-[4-(溴甲基)苯基]苯为原料,研究了含硅、碲或铁的含硫大杂环化合物的合成方法,并用X射线衍射、核磁共振、红外光谱、紫外光谱等分析结果,讨论了含硫大杂环化合物的结构及其导电性和磁性。
Synthetic methods for, and structural and spectroscopic characteristics of sulfur-containing macroheterocycles are discussed. The synthesis of oligothiamacrocycloalkanes is based on the reaction of α, ò-dihaloalkanes with alkali α,ò-alkanedithiolates to form 12-42-membered macroheterocycles with 2-6 sulfur atoms in the ring. Oxathiamacrocycloalkanes containing sulfur and oxygen atoms in the ring have been prepared by reaction of aromatic 1,2-dithiols or 2-mercaptophenols with aliphatic α-ò-dihalo derivatives. The synthesis of thiamacrocycloalkanes involves the reaction of dimethyl ethers or α,ò-alkanedicarboxylic acid dichlorides with α,ò-alkanediamines followed by reduction of the macroheterocyclic diamides with LiAlH4 or B2H6. Oxathiaazamacrocycloalkanes have been prepared in a similar way by reaction of dicarboxylic acid dichlorides with α,ò-oxaalkanediamines as well as by reaction of chlorosulfonyl-β-lactams with glycols.A general synthetic route to oligothiacyclophanes is the reaction of bis-(bromomethyl) substituted arenes with bis-(mercaptomethyl)benzenes. Analogously, sulfur-containing cyclopyridinophanes have been prepared by reaction of 2,6-bis(bromomethyl)pyridine with α,ò-alkanedithiols. For the synthesis of macrocyclic compounds containing one, two, or several thiophene rings, some procedures based on intra-and intermolecular acylation of ò-thienylalkanecarboxylic acid chlorides, acyloin condensation of 2,5-bis(carbalkoxyalkyl)thiophenes, and intramolecular alkylation of ò-haloalkyl substituted β-keto esters of the thiophene series have been developed.Synthetic routes to macroheterocycles containing di-and polysulfide groups are discussed. The synthesis involves sulfurization of mesitylene or 1,3-dimethoxybenzene with disulfur dichloride or sulfur dichloride as well as the oxidation of dithiols.The synthesis of bi-and trimacrocyclic compounds is based on the reaction of 1,3,5-tris(mercaptoalkyl)benzenes with tris(bromoalkyl)-methanes or l,3,5-tris[4-(mercaptomethyl)phenyl]-benzene with 1,3,5-tris-[4-(bromomethyl)phenyl] benzene.Some methods for the synthesis of sulfur-containing macroheterocycles containing silicon, tellurium, or iron are considered.The structures of the sulfur-containing macroheterocycles are discussed using the results of X-ray diffraction, H NMR, IR, and UV spectroscopy as well as their electroconductive and magnetic properties.
大类学科 | 分区 | 小类学科 | 分区 | Top期刊 | 综述期刊 |
化学 | 4区 | CHEMISTRY, MULTIDISCIPLINARY 化学综合 | 4区 | 否 | 否 |
JCR分区等级 | JCR所属学科 | 分区 | 影响因子 |
Q4 | CHEMISTRY, MULTIDISCIPLINARY | Q4 | 1.418 |
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