Synthesis Of Heteropoly Acids And Electron Transpoting Materials-Diphenoquinone And Its Property

In this paper, five "Keggin" type heteropoly acids(HPA-n):H₅PMo₁₀V₂O₄₀,H₆PMo₉V₃O₄₀,H₇PMo₈V4O₄₀,H₈PMo7V5O₄₀,H₉PMo₆V₆O₄₀ have been prepared by the reaction of Na₂HPO₄·12H₂O,Na₂MoO₄·2H₂O and V₂O₅ through mix-acidifying and reflux-acidifying methods. The yields by reflux-acidifying method are higher than the mix-acidifying method, which can reach 90.1%,74.2%,60.0%,46.2%,24.8% separately. Step method has been also studied, which gives excellent yields in 86.2%,71.1%,58.5%,44.1% and 22.1% separately with simple operation. The structure and composition of HPA-n are confirmed by UV-vis,IR,DSC,XRD and ICP.3,3',5,5'-tetrabutyl-4,4'-diphenoquinone(ET-1),3,3',5,5'-tetramethy-4,4'-diphenoq-uinone(ET-2) and 3,3'-dimethyl-5,5'-dibutyldiphenoquinone(ET-3) have been synthes- ized from 2,6-dibutylphenol, 2,6-dimethylphenol and 2-methy-6-butylphenol catalyz- ed by HPA-n with oxygen as the oxidant. This put forward a green method for the synthesis of diphenoquinone derivatives. The suitable reaction conditions : 3,3',5,5'-tetrabutyl-4,4'-diphenoquinone, solvent is ethanol and water(1:1) , the ratio of reactant and catalyst is 20:1, the reaction temperature is 50℃and the reaction time is 1.5h, in yield 68.8%;3,3',5,5'-tetramethy-4,4'-diphenoquinone, solvent is ethanol and water(1:1) , the ratio of reactant and catalyst is 20:1, reaction temperature is 62℃, the reaction time is 1.5h, with yield 63.1%. Yield of 3,3'-dimethyl-5,5'-dibutyldiphenoqu- inone is 52.8% under the same reaction condition as 3,3',5,5'-tetrabutyl-4,4'-diphenoq- uinone. The compositions and structures of the synthesized diphenoquinones are confirmed by UV-vis,IR,MS and 1HNMR.2-methoxy-6-allylphenol and 2-phenyl-6-allylphenol have been synthesized through Claisen rearrangement method in yield 76.6% and 62.5%. The structure of the phenols are confirmed by UV-vis,IR,MS,and 1HNMR. But the synthesis of ally-substituted diphenoquinone derivatives needs advanced research.2-methyl-6-phenylmethylphenol has been synthesized by Claisen method. The suitable reaction condition:solvent is dimethylbenzene, protected with N2, refluxed 7h, in yield 35.4%.3,3'-dimethyl-5,5'-diphenylmethyl-4,4'-diphenoquinone(ET-4) and 3-methyl-5-phenylmethyl-3',5'-diphenoquinone(ET-5) have been synthesized by the reaction of 2-methyl-6-phenylmethylphenol and 2,6-dibutylphenol separately in yields 33.4% and 8.2%.The structure and composition are confirm by UV-vis,IR,MS,and EA. Positive-charged photoconductive conductors have been prepared using the purified diphenoquinone derivatives and tested. It is proved diphenoquinone derivatives show excellent electron transporting properties, the purification of the diphenoquinones makes great influence on its property.