Efficient Synthesis of Transition-Metal Phthalocyanines in Functional Ionic Liquids

Abstract

The synthesis of transition-metal phthalocyanines by the reaction of substituted and unsubstituted phthalonitriles in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and metal salts in functional imidazolium, pyridinium and ammonium ionic liquids at 100-140 °C, is reported. The best yields of metallated phthalocyanines were achieved in butyl(2-hydroxyethyl)dimethylammonium bromide ionic liquid. Metallation of free-base phthalocyanines with different metal salts in the above ionic liquid has also been achieved in good yields.

phthalocyanines - ionic liquids - 1,8-diazabicyclo[5.4.0]undec-7-ene - DBU - metallations - complexes

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Ionic liquid 7 (1 mmol) was heated in the presence of DBU (1 mmol) in anhyd MeCN (5 mL) at 140 °C for 10 min under a nitrogen atmosphere. Analysis of the ¹H NMR spectrum of the reaction mixture showed a peak at δ = 7.7 ppm, indicating the presence of protonated NH in H⁺-DBU(18) and a downfield shift of 2-3 ppm was observed for all the protons of 18. The reaction mixture was further reacted with butyl bromide (1 mmol) at 60 °C for 24 h under a nitrogen atmosphere, which resulted in the formation of butyl(2-butoxyethyl)dimethylammonium bromide(20) as identified by the presence of a peak (m/z 202), corresponding to [C₁₂H₂₈NO] in ESI-MS spectrum.

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