Study On New Synthesis Of9,9-Bis(Methoxymethyl)Fluorene As Diether Electron Donor

This article successfully explores a new synthesis of9,9-bis(methoxymethyl)fluoren e, in which9,9-bis(methoxymethyl)fluorene was synthesized from fluroene, normal buty1lithium and chloromethyl methyl ether. this method included synthesis of fluorene dil ithium by reaction of fluorene with normal butyl lithium and successive methylation o f fluorene dilithium with chloromethyl methyl ether.Studied the synthesis of9,9-bis(methoxymethyl)fluorene by normal butyl lithium a s alkali with one feeding time. The optimization process conditions is researched, and the yield of9,9-bis(methoxymethyl)fluorene is up to78.4%. The optimal reaction co ndition was found as follows:(1) synthesis of fluorene dilithium, THF was used as s olvent, n(normal butyl lithium):n(fluorine)=2.5:1.0, the reaction temperature was from78℃to12℃, the reaction time was2.5h.(2) methylation reaction, n(fluoene):n(chl oromethyl methyl ether)=1.0:4.0, the reation temperature was23℃, the reaction time was2h. It was easy to control the reaction, and could perform high yield. According to the feature of the synthesis of9,9-bis(methoxymethyl)fluorene with one-feeding tim e of normal butyl lithium as alkali and referring to the synthesis of alkyl fluorene. a twice feeding method is designed to synthesize9,9-bis(methoxymethyl)fluorene.9-Flu orene lithium is prepared through fluorene reaction with an equimolar amount of norm al butyl lithium in proper condition. Nucleophilic substitution between9-(methoxymeth yl) fluorene and an equimolar amount of normal butyl lithium produces9-(methoxymet hyl)fluorene lithium salt. which reacted with chloromethyl methyl by alkylation and th en produce9,9-bis(methoxymethyl)fluorene.Studied the synthesis of9,9-bis(methoxymethyl)fluorene by LDA as alkali with on e feeding time. The alkalinity value of LDA is close to that of normal butyl lithium, but there was more by-product during the process with a lower yield using LDA. The optimization process conditions is researched, and the yield of9,9-bis(methoxymethyl) fluorene is up to41.0%.Alkali metal and florene can form carbon anion by removing H proton. Carbon a nion compound is a reactive intermediate, thus it can seize the protons as a nucleophi lic reagent. Using the properties of active metal, this paper designed synthesis of9,9-bis(methoxymethyl)fluorene from fluroene, alkali metal and chloromethyl methyl etherIn this article, we tested the melting point, IR and NMR of the purified product, analysized the corresponding results and confirmed that the compound synthesized wa s9,9-bis (methoxymethyl) fluorene...