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The phthalic acid (1mmol) dissolved in 20 ml of acid in the aqueous solution, the stirring 1.5 hours later, into the chlorine gas, reaction 3 hours, all the solvent is pumped, by adding ethyl acetate 50 ml, the resulting solution with saturated salt water washing 3 times, the organic phase after separation, the aqueous phase is extracted with twice ethyl acetate (50 ml). The combined organic phase, drying agent, filtration of the drying agent, the solvent evaporation to dryness, to obtain the corresponding ortho and meta-substituted phthalic acid chloride (yield 100percent, GC purity (two isomers) 99percent). The phthalic acid chloride (1mmol) dissolved in 20 ml of methanol, add alkaline solution, stirring 1.5 hours, all the solvent is pumped, by adding ethyl acetate 50 ml, the resulting solution with saturated salt water washing 3 times, the organic phase after separation, the aqueous phase is extracted with twice ethyl acetate (50 ml). The combined organic phase, drying agent, filtration of the drying agent, the solvent evaporation to dryness, to obtain the corresponding ortho and meta-substituted phthalic acid methyl ester mixture (the yield is 100percent, GC purity (two isomers) 99percent). The respectively 50mLDMF, 10mmol the above-mentioned phthalic acid methyl ester mixture, 10mmol metal nickel powder and 10mL1mol/L dilute hydrochloric acid solution is added with a condensation device 250 ml stirring at room temperature in three-necked flask 0.5h to the 60 °C to continue stirring 5h, tracking detection reaction by TLC, until the reaction is stopped when the substrate is no longer reduce the reaction, the reaction cooling, filtering to remove the metallic catalyst, solvent evaporation to dryness. Adding ethyl acetate 50 ml, the resulting solution with saturated salt water washing 3 times, the organic phase after separation, the aqueous phase is extracted with twice ethyl acetate (50 ml). The combined organic phase, drying agent, filtration of the drying agent, to evaporate the solvent, to the corresponding of the biphenyl tetracarboxylic acid ester mixture (yield 90percent, GC purity (three isomers) 95percent). The biphenyltetracarboxylic acid methyl ester mixture (1mmol) dissolved in 20 ml of aqueous solution of alkali, stirring 1.5 hours, neutralizing solution instillment acid, instillment to PH value is less than 2 is stopped when the dropping, stirring 3 hours, all the solvent is pumped, by adding ethyl acetate 50 ml, the resulting solution with saturated salt water washing 3 times, the organic phase after separation, the aqueous phase is extracted with twice ethyl acetate (50 ml). The combined organic phase, drying agent, filtration of the drying agent, to evaporate the solvent, to the corresponding ortho and meta substituted neighbouring benzene two bitter wine mixture (yield 90percent, GC purity (three isomers) 90percent). |