Synthesis Of 4-chloro Phthalic Anhydride And The Utility Of "green" Fluorous Solvent Hexafluoropropene Dimers

4-Chlorophthalic anhydride was synthesized by chloridization of phthalic anhydride in the presence of base. The technical influences on the conversion of phthalic anhydride and selectivity of 4-Chlorophthalic anhydride were investigated, and then optimum synthesis technics was given :50℃,pH4.5～5.5, reacting 200 min, n(phthalic anhydride ): n(base):n(Cl₂) = 1:2.59:1, n(H₂O): n(phthalic anhydride) = 20 : 1. It was studied to dewater 4-Chlorophthalic acid and to purify 4-Chlorophthalic anhydride .Perfluorous hexenen(PFH) was first used as "green solvent ". Appropriate fluorous biphase system have been selected by measuring the solubilities of PFH in general solvents. Toluene was nitrated effectively with nitro-sulfuric acid in PFH. Effects of reaction temperature, the ratio of V(PFH) to V(organic solvent) and reaction time on the nitration were investigated. It was observed optimum conditions for fluorous phase nitration of toluene that was reaction temperature 50℃, n(toluene): n(HNO₃) = 1:1.05, n(HNO₃): n(H₂SO₄) = 1:1.2, V(PFH): V(organic solvent) =1:1, reacting 4h. Conversion of toluene was 99.5%. The product contained mononitrotoluene more than 98.3%. By simple separation, fluorous solvent and sulfuric acid have been recovered easily and reused for a number of times.Esterification was studied by reacting equimolar alcohol and hydrocarbon acid in the presence of sulfuric acid in PFH. It was observed that the conversion of the acid was increased significantly. Especially amyl acetate synthesized, the conversion of acid was increased to 94.72%. By simple separation, fluorous solvent was recovered and reused for a number of times. Byproducts decreased.