Phosphonate Applied Research, To Build A New Heavy Key Compounds

Compounds containing C-P bond with special bioactivity are applied in agrochemical and pharmaceutical fields. Because of their characteristic structure, they play very important roles in organic synthesis, especially in synthesis of double bond compounds. In order to pursue novel compounds containing C-P bond and explore their application in organic synthesis, we focused the study on olefination methodologies based on elimination of p-toluenesulfon- amide. We also studied the consecutive reactions of functionalized vinylphosphonates and their application in synthesis of double bond compounds. This thesis mainly includes three parts as below:1.Synthesis of diethyl (E)- a -methoxycarbonyl- ~ -aryl-vinylphosphonates.Treatment of diethyl methoxycarbonylmethylphosphate with catalytic amount of base gave the corresponding phosphoryl-stabilized carbanion, which added to the carbon-nitrogen double bond of N-tosyl imines. The newly generated nitrogen anion occurred intramolecule [1,3] electron shift, eliminated p-toluenesulfonyl amine nitrogen anion to diethyl (E)- a -methoxycarbonyl- ~ -aryl-vinylphosphonates. The p-toluenesulfonyl amine nitrogen anion, as base, can also react with diethyl methoxycarbonylmethylphosphate to finish the recycled reaction.The characteristic features of this reation are:1> This novel olefinjc reaction is different from the traditional HWE reaction. The olefinic reaction forms carbon-carbon double bond after eliminating p-tolunensulfonamide, while traditional HWE reaction eliminates phosphonic acidanion. Thus, the phosphonate moiety is remained in the products and this methodology can be used in the synthesis of substituted viny] phosphonates.2>The base used in this reaction is catalytic amount while in HWE reaction is stoichiometric amount.3>Besides the reaction is fast, the reaction condition is mild.4>The reaction with high stereoselectivity produces only the E-isomer.2.Research on consecutive reactions of tetraethyl methylene- 1,1 -bisphosphonate and diethyt benzenesulfinyl methylenephosphonate.1)Synthesis of diethyl (E)- a -(3-propionitrile)- P -arylvinylphosphonatesTreatment of tetraethyl methylene- 1.1 -bisphosphonate with base gave the corresponding bisphosphoryl-stabilized carbanion, which added to vinyl cyanide, followed by intramolecule [1,3] electron shift, a more stable carbonion was formed. Then this carbonion was treated with aldehyde to give diethyl (E)- a -(3- propionitrile)- P -arylvinylphosphonate.2)Synthesis of (E) ?梐ryl-4梑enzenesulfinylpentaene-4 -cyanideTreatment of diethyl benzenesulfinylmethylenephosphonate with base gave the corresponding sulfonyl and phosphoryl-stabilized carbanion, which added to vinyl cyanide, followed by intramolecule [1,3] electon shift, a more stable carbanion was formed. Then the treatment of this carbanion with aIdehyde produced (E) ??aryl-4 ?benzenesulfinylpentaene-4 �'yanide.3.Research on application of diethyl a -ethoxycarbonylvinylphosphonate in the synthsesis of allyI oxime ethers.3-hydroxy-5-methyl-zso-oxazole and diethyl a -ethoxycarbonylvinylphosphonate were prepared successfully. And their Michael-HWE consecutive reaction was on-going research.