Synthesis Of Benzo-1,4,2-cyclohexyl Phosphorus And Nitrogen Oxide Heterocyclic Derivatives

The chemistry of organophosphorus heterocycles has received considerable attention owing to their unique structural features and diverse potential biological properties. Mann, F.G, one of the founders of the phosphorus heterocyclic chemistry, reported a review about phosphorus in1950, and since then the research of the phosphorus heterocyclic has developed rapidly. The types of the phosphorus heterocyclic are countless at present.This paper mainly introduced the research progress of1,3,2-oxazaphosphinanes,1,4,2-oxazaphosphinanes and other heterocyclic compounds containing phosphorus.1,3,2-oxazaphosphinanes have a wide range of biological and physiological activities such as weeding, insecticidal, sterilization, anti-tumor, anti-virus and so on, and many of their derivatives have been developed into pesticides and medicines. The typical examples are cyclophosphamide and ifosfamide.1,4,2-oxazaphosphinanes, which is the cyclic derivatives of α-aminophosphates, has some special activities as the heterocyclic compounds, and also has anti-tumor, antioxidant, enzyme inhibition activity and many other properties of α-aminophosphates; at the same time, because there is a C who can has series substituents introduced into the a position of the P atom, they have some important optical activities as well. Because of the chiral characteristics of the phosphorus atom feature, other heterocyclic compounds containing phosphorus occupy an important position as chiral ligands in the transition metal catalysis.α-aminophosphonates might be considered as phosphorus analogue of natural α-amino acid ester (bioisosterism) and have played more and more important role in medicine and pesticide because of their plant virus resistance, antitumoral, weeding, antiseptic, antioxidantal, radiation-proof and other pronounced biological activities. So, they have received much attention of chemists for long times. Cyclic α-amino phosphonates, as a kind of α-aminophosphonates, has some special biological activities. Accordingly a number of similar compounds have been studied in order to acquire more information on the mode of action of these agents and to reveal certain structure-activity relationships. But only few papers in relation to3-phenoxyl-1,4,2-beneoxaphosphole2-oxides, to the best of our knowledges, have been reported. Therefore it’s of vital significance to carry out the research of synthetic methodology of this kind of compounds.o-aminophenol as the substrate, we synthesized a new type of1,4,2-beneoxazaphosphole2-oxides by reacting with carbonyl compounds and H-phosphinates. A series of cyclic products were finally efficiently obtained using the optimized conditions. The experiment was further expanded to use chrysin to synthesize the corresponding heterocycles. In summary, the article provides a practical and efficient method to afford the related novel heterocyclic compounds under mild conditions, and lays a good foundation for its characterization and application development.The main contents are as follows:(1) Nineteen2-phenoxy-1,4,2-beneoxazaphosphole2-oxides were effectively synthesized besides two non-cyclic a-aminophosphonats, using o-aminophenol, carbonyl compounds, and various hydrogen phosphites as reactants. The structures of the compounds were confirmed by IR, ESI-MS, NMR and X-Ray. The influencing factors of the reaction were investigated, and the structure of this kind of compound was analyzed in detail.(2)8-amino-chrysin were employed to synthesize the corresponding2-phenoxy-1,4,2-beneoxazaphosphole2-oxides under the reaction conditions. The structures of three related products were confirmed byIR, ESI-MS, NMR and X-Ray.