Electrosynthesis in systems of two immiscible liquids and a phase transfer catalyst

Ellis, Steven Richard (1982) Electrosynthesis in systems of two immiscible liquids and a phase transfer catalyst. University of Southampton, Doctoral Thesis.

Abstract

This thesis examines the effect upon yield of the electrolysis parameters for anodic aromatic substitution in two phase systems using phase transfer catalysis. The mechanism of such roactiona was also studied. Product yields from acotoxylation of 1,4-dimethoxybenzene are shown to be dependent upon (i) ratio of nucleophilo to substrate (in the organic phase) (ii) current density (iii) charge passed. The optimum conditions are 1,4-dimethoxybenzene (4 mmoles) in CH2C12 (40 cm3), AcOH (0.18 moles), NaOAc (0.18 moles) and BuiNHSOi (4 mmoles) in sat. Na2S04 (sq. 40 cm3) i - 32.5 mA cm-2 Q - 2F/mole organic yield 87%, current yield 61%. Other acyloxylations of 1,4-dimethoxybenzene and acetoxylotions of other aromatic substrates are also reported. The yield of cyanonaphthalene is shown to be dependent upon (1) and (ii) above. However, (iii) is less important. The optimum conditions are C1SHS (0.02 moles) in CH2C12 (100 cm3), NaCN (0.06 moles) and BusN+Na+SO42- (0.03 moles) in sat. Na2SO4 (sq. 100 cm 3), 1 - 20 mA Cm 2 Q -1.5 F/Mol 100% organic yield 67% current yield. The yield of chloronaphthalene is shown to be dependent upon (i), (ii) and (iii) above. Complexation of the chloride with ZnC12 improves organic yields from 56% to 92%. The optimum conditions are C1SHs (0.01 moles) in CHZC12 (100 cm3), ZnC12 (0.15 moles), NaCl (0.3 moles) and Bu4NH80i (0.01 moles) in sat. Na2S04 (sq. 100 cm3) 1 = 48.7 mA cm Q - 1F/mol organic yield 74% current yield 56%.

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