Macroheterocycles

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.