Polysubstituted phthalocyanines by nucleophilic substitution reactions on hexadecafluorophthalocyanines

Abstract

Nucleophilic substitution reactions on hexadecafluorophthalocyaninato zinc(II) with a variety of O, N, C, and S nucleophiles led to narrowly defined mixtures of polysubstituted phthalocyanines, some of which are completely inaccessible by classical phthalonitrile condensation reactions.

Synthesis of substituted phthalocyanines

“…214c, 232 The distribution of the reaction products was monitored by mass spectrometry. Based on these data, it was found that, as expected, aromatic nucleophilic substitution of the fluorine atoms results in a broad distribution of reaction products rather than formation of individual complexes, although in some cases narrowly defined mixtures of polysubstituted products were observed.…”

Synthetic approaches to asymmetric phthalocyanines and their analogues

“…[265][266][267] This research group showed that the C-F bonds in zinc hexadecafluorophthalocyanine 90 could be replaced by a variety of carbon-, oxygen-, sulfur-, and nitrogen-centered nucleophillic reagents to form mixtures of asymmetric phthalocyanines 91 with various degrees of substitution. The reaction product distribution was studied by mass spectrometry.…”

“…If diamines were used as the nucleophiles, the reaction products are mixtures of cyclic substituted phthalocyanines, binuclear and trinuclear (amine bridged) compounds, or mixtures of both of these types depending on the structures of the diamines used. [265][266][267] Scheme 30. Formation of asymmetric phthalocyanines using partial substitution of the peripheral C-F bonds in hexadecafluorophthalocyanine.…”

“…The average number of oxygen-, nitrogen-, sulfur-, and carboncentered nucleophiles present in the reaction product correlates well with their relative nucleophilicity and increases in the order: HNRR′ < RO -< CN -< RS -(Scheme 30). 265,266 The reactivity of 90 was further investigated in aromatic nucleophilic substitution reactions with primary and secondary amines as well as tertiary butyl esters of aminoacids as nucleophiles, using various reaction conditions. [265][266][267] It was found that asymmetric mono-and di-substituted fluorophthalocyanines are formed under mild reaction conditions, while higher degrees of substitution can be achieved with the amines as the reaction solvents.…”

“…265,266 The reactivity of 90 was further investigated in aromatic nucleophilic substitution reactions with primary and secondary amines as well as tertiary butyl esters of aminoacids as nucleophiles, using various reaction conditions. [265][266][267] It was found that asymmetric mono-and di-substituted fluorophthalocyanines are formed under mild reaction conditions, while higher degrees of substitution can be achieved with the amines as the reaction solvents. If diamines were used as the nucleophiles, the reaction products are mixtures of cyclic substituted phthalocyanines, binuclear and trinuclear (amine bridged) compounds, or mixtures of both of these types depending on the structures of the diamines used.…”