Studies On The Synthesis Of Carboranylthioether And Carboranylboron Compounds

In recent decades, boron cluster chemistry has expanded rapidly and developed into aninteresting field that includes boranes, carboranes, metallaboranes and metallacarboranes,main group heteroboranes and their metal derivatives. These compounds have provided a lotof potential applications in medicine chemistry, boron neutron capture therapy （BNCT） oftumors, nonlinear optics, catalysis, etc. Therefore it is of interest to continue studying thesyntheses and structures of new borane derivatives.This thesis mainly describes the research on the reactions of the dithiolato-o-carboranesalt （Et₃NH）₂[1,2-S₂C₂B₁₀H₁₀] with allyl bormide,1-bromo-3-chloropropane, benzyl chlorideand ethyl bromoacetate, respectively. Some of the products were isolated and characterized byvarious techniques.The five sections of this thesis are as follows:In chapter1, a general review is given to introduce the synthesis and reactivity ofo-carborane and their derivatives, and of trialkylboranes and borole derivatives.In chapter2, the reactions of the dithiolato-o-carborane salt （Et3NH）2[1,2-S2C2B10H10]with allyl bromide,1-bromo-3-chloropropane, benzyl chloride and ethyl bromoacetate, etc,respectively, are described. The isolated products:1,2-（CH₂CHCH₂S）₂C₂B₁₀H₁₀,1,2-（ClCH₂CH₂CH₂S）₂C₂B₁₀H₁₀,1,2-（PhCH₂S）₂C₂B₁₀H₁₀,1,2-（CH₃CH₂COOCH₂S）₂-C2B10H10, etc, were characterized by IR, NMR, MS and single-crystal X-ray analysis(1,2-（PhCH₂S）₂C₂B₁₀H₁₀). The reactions of some of the products with metal ions werestudied.In chapter3, the attempted synthesis of a triarylborane bearing an o-carborane cage isreported. The reaction of dilithio-o-carborane with dimesitylboron fluoride affordsMes2BOBMes2and Mes2BOH, while the expected product was not formed. The preliminaryresults of the reaction of1-lithio-o-carborane with dimesitylboron fluoride showed that a newcarborane derivative was formed. The fluoride binding ability of Mes2BOBMes2is alsoreported.In chapter4, the attempted synthesis of borole intermediate1,4-dihalo-1,3-dienes isreported. The palladium-catalyzed dimerization of phenylacetylene save new product. We also tried the reaction of phenylacetylene and diphenylacetylene, with boron tribromiderespectively, and after the reaction mixture was oxidized, no1,4-dibromo-1,3-diene wasformed.In chapter5, the results of this thesis are summarized and the conclusions are given.