Study On The Synthesis Of Polysubstituted 3-esteryl Furans,2-esteryl Pyrrolidones And 2-phosphono-3-hydroxybenzothiophenes

Furan,pyrrole,thiophene compounds are the most basic five-membered heterocyclic compounds.Polysubstituted furans,pyrrolidones,benzothiophenes and their derivatives are widely present in natural products and synthetic drugs with good biological activities such as insecticide,herbicide,bacteriostasis,antiviral,anti-HIV,antitumor,etc.In addition,furan,pyrrolidone,benzothiophene and their derivatives also have a wide range of applications in the fields of organic synthesis,dyes,fragrances and new polymer optoelectronic materials.Therefore,the synthesis of polysubstituted furans,pyrrolidones,benzothiophenes and their derivatives has always been one of the most enthusiastic research topics to chemical researchers.In recent years,methods for synthesizing polysubstituted furans,pyrrolidones,benzothiophenes and their derivatives still have problems such as expensive raw materials,expensive metal catalysts(Triphenylphosphine gold(1)complex catalyst,Platinum chloride catalyst,etc.),Harsh reaction conditions(high temperature,high pressure,strong alkali,etc.).Therefore,the development of new,green,concise and efficient synthetic methods for the synthesis of polysubstituted furans,pyrrolidones,benzothiophenes and their derivatives is a crucial scientific research subject in the field of organic synthesis.The main research work of this paper is divided into the following three parts:Part 1:First,tricarbonyl compounds were used as a starting material to synthesize aldol condensed compounds through diazotization reaction,oxidation reaction,and aldol reaction.Then,the polysubstituted 3-ester furans was synthesized by using the aldol condensation compound as the substrate and nucleophile under acid catalysis.After screening a series of acid catalysts,the best reaction was obtained:boron trifluoride ether was used as the catalyst,and the reaction was heated at 90? for 24 hours.In this chapter,10 aldol condensed compounds and 14 new polysubstituted 3-ester furans were synthesized.The data of the synthesized compounds were characterized by NMR,HR-MS,properties,melting point and so on.A possible reaction mechanism was proposed through research literature.Part 2:First,tricarbonyl compounds were used as starting materials to synthesize chiral aldol condensation compounds via diazotization reaction,oxidation reaction,and aldol reaction.Then,synthesize of chiral polysubstituted 2-ester pyrrolidones via an intermolecular cyclization reaction of chiral aldol condensation compounds and amines under trifluoroacetic acid.Finally,quaternary ammonium salt ionic liquids was synthesized from polysubstituted 2-ester pyrrolidones and methyl triflate under mild conditions.In this chapter,6 pairs of aldol condensed compounds which are non-corresponding isomers,12 chiral polysubstituted 2-ester pyrrolidones and corresponding 4 quaternary ammonium ionic liquids were synthesized.The data of the synthesized compounds were characterized by NMR,HR-MS and so on.Part 3:First,(iodomethyl)diarylphosphine oxides were synthesized by using diarylphosphine oxides as raw material.Then,synthesize of 2-phosphono-3-hydroxybenzothiophenes via an intermolecular cyclization reaction of(iodomethyl)diarylphosphine oxide and methyl thiosalicylate under potassium t-butoxide.In this chapter,10(iodomethyl)diarylphosphine oxides and corresponding 82-phosphono-3-hydroxybenzothiophenes were synthesized.The data of the synthesized compounds were characterized by NMR and so on.