Studies On Reactions Of Halide Organozinc Reagents With Acyl Isothiocyanates

Organometallic chemistry has been not only the sources of new reactions in modern synthesis chemistry, but also one of the most important methods to obtain a high selectivity, high atom economy and warm reaction conditions in organic synthesis. Since organozinc reagent with good chemical selectivity can carry multiple functional groups involved in chemical reactions, it has aroused wide attention from chemists.As a kind of common intermediates in organic synthesis, acyl isothiocyanate, which is applied to composition of heterocyclic compound and all kinds of organic reactions, has been used widely in the organic products, such as pesticide, medicine, dyestuff and so on. However, there is no relevant thesis and papers about reactions of acyl isothiocyanates with organometallic reagents. Hence, in this thesis, researches on additive reactions of halide organozinc reagents and acyl isothiocyanates have been made.This thesis contains two chapters:Chapter one: advances in the research of organozinc reagents in the organic synthesis reactionsIn this chapter, we mainly summarized all kinds of preparation methods of organozinc reagents, the advances in research of its application to various organic synthesis reactions and the latest reports about the relevant research achievement.Chapter two: studies on the reaction of acyl isothiocyanate and halide organozinc reagentsIn this chapter, we mainly do researches on the addition reaction of allyl zinc bromide reagent, propargyl zinc bromide reagent, and aromatic acyl isothiocyanate in the solvent of tetrahydrofuran, as well as the addition reaction of allyl zinc bromide reagent, propargyl zinc bromide reagent and aliphatic acyl isothiocyanate. In these reactions, diallyl alcohol and dipropargyl alcohol compounds have been synthesized, and 20 compounds have been synthesized totally. After optimized some requirements in reaction, such as temperature, reaction time, and materials rate and so on, structures of the product have been testified correctly through tests of 1~H-NMR, (13)~C-NMR, IR, MS, and elemental analysis. This reaction has many characteristics, including easy operation, high production, high regioselectivity and wide application, ec al. In this reaction, acyl isothiocyanates is employed as raw materials in order to achieve coexistence of many functional groups and provide a new synthesis method of diallyl alcohol or dipropargyl alcohol.