Mechanism of The Ullmann Condensation Reaction. II. Effects of the Medium, the Additives and the Substituents

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The effects of the medium, the additives, and the oxidation state of the copper catalyst on the rate of the Ullmann condensation reaction of sodium 1-amino-4-bromoanthraquinone-2-sulfonate and aniline in an aqueous buffered solution were investigated. The reaction rate was not affected by the ionic strength but depended very largely on the hydrogen-ion concentration. It was also established that the reaction was retarded by the addition of anions which can coordinate to copper; the retarding effect was in the order: F−<<Cl−<Br−<I−<CN−. The inhibiting effects of copper-chelating agents and oxygen were also observed. No marked difference, except a slight increase in initial rate, was observed when cuprous chloride was used as the catalyst instead of cupric sulfate. The effect of the substituents of aniline on the reaction rate can be expressed by Yukuwa-Tsuno's equation, in which the parameters, ρ and r, were −2.20 and 0.50 respectively. The experimental results are discussed.
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