Synthesis of Crowned Triazolephthalocyanines

Abstract

The synthesis of triazolephthalocyanines bearing crown ether and aza‐crown ether substituents is described. Different substituents have been introduced on the nitrogen atom of the aza‐crown moiety to improve the solubility and the intrinsic amphiphilic character of these macrocycles. The crowned triazolephthalocyanines described have been prepared by a statistical procedure, and also by different variations of a stepwise method. Preliminary studies of the aggregation properties of one representative of this new family of compounds have also been carried out. An exhaustive study of the synthesis of the corresponding dicyano derivative precursors of the triazolephthalocyanines is displayed. Two different approaches have been used for this goal: The first one inserts the cyano groups prior to the synthesis of the crown ether moiety, while the second one builds the crown ether part of the molecule in advance of the cyanation process. The incompatibility of the Rosemund‐von‐Braun cyanation conditions and the presence of nitrogen atoms in the molecule is the main difficulty of the synthesis of these precursors.

Synthesis of branched alkoxy side chains containing phthalocyanine derivates and their application in mass sensitive QCM sensors

“…9-Tosyloxy-7,11-dioxa-heptadecane (1) was synthesized according to the literature [29]. 1,2-dicyano-4,5-dihydroxybenzene (2) was prepared as previously reported [30]. Elemental analyses were obtained with a Thermo Finnigan Flash 1112 instrument.…”

Synthesis of branched alkoxy side chains containing phthalocyanine derivates and their application in mass sensitive QCM sensors

“…9-Tosyloxy-7,11-dioxa-heptadecane (1) was synthesized according to the literature [29]. 1,2-dicyano-4,5-dihydroxybenzene (2) was prepared as previously reported [30]. Elemental analyses were obtained with a Thermo Finnigan Flash 1112 instrument.…”

Modern Synthetic Approaches to Phthalonitriles with Special Emphasis on Transition-Metal Catalyzed Cyanation Reactions

“…For example, attempt of alkylation of dicyanocatechol with chloroethoxyethanol by Torres et al, failed to produce workable amount of 1b because of the strong electron-withdrawing effect of the cyano-groups. [19] We also previously took an attempt to prepare 1b by cyanation of 4,5-dibromo-4,5-bis[2'-(2''-benzyloxyethoxy)-ethoxy]benzene 2a and subsequent debenzylation (H 2 , Pd/C) of resulting dinitrile 2b. [16] It was demonstrated that phthalonitrile unit, which is present in 2b, poisons Pd/C catalyst and precludes deprotection of benzyl groups.…”

“…In these cases, the introduction of protective groups is required, [15][16][17][18] but even these precautions sometimes do not guarantee high yields of Rosenmund-Braun cyanation of certain substrates. [19] In course of reaction, the resulting phthalonitrile forms complexes with Cu I ions, which should be decomposed to release target compound. For this purpose, oxidative cleavage is applied, by prolonged treatment of reaction mixture with conc.…”

Synthesis and Copper(I)‐Driven Disaggregation of a Zinc‐Complexed Phthalocyanine Bearing Four Lateral Coordinating Rings

“…Implementation of this strategy required preparation of a phthalonitrile bearing two diethylene glycol (DEG) chains (4 in Scheme 1). Previous attempts to prepare 4 either by alkylation of 4,5-dicyanocatechol with chloroethoxyethanol [27] or by Pd/C-catalysed hydrogenolysis of bis{2Ј-[2ЈЈ-(benzyloxy)ethoxy]ethoxy}phthalonitrile [28] were unsuccessful. So, we decided to study the cyanation of the odibromide, which already contains the required DEG chains.…”

Synthesis of branched alkoxy side chains containing phthalocyanine derivates and their application in mass sensitive QCM sensors

“…9-Tosyloxy-7,11-dioxa-heptadecane (1) was synthesized according to the literature [29]. 1,2-dicyano-4,5-dihydroxybenzene (2) was prepared as previously reported [30]. Elemental analyses were obtained with a Thermo Finnigan Flash 1112 instrument.…”

Modern Synthetic Approaches to Phthalonitriles with Special Emphasis on Transition-Metal Catalyzed Cyanation Reactions

“…For example, attempt of alkylation of dicyanocatechol with chloroethoxyethanol by Torres et al, failed to produce workable amount of 1b because of the strong electron-withdrawing effect of the cyano-groups. [19] We also previously took an attempt to prepare 1b by cyanation of 4,5-dibromo-4,5-bis[2'-(2''-benzyloxyethoxy)-ethoxy]benzene 2a and subsequent debenzylation (H 2 , Pd/C) of resulting dinitrile 2b. [16] It was demonstrated that phthalonitrile unit, which is present in 2b, poisons Pd/C catalyst and precludes deprotection of benzyl groups.…”

“…In these cases, the introduction of protective groups is required, [15][16][17][18] but even these precautions sometimes do not guarantee high yields of Rosenmund-Braun cyanation of certain substrates. [19] In course of reaction, the resulting phthalonitrile forms complexes with Cu I ions, which should be decomposed to release target compound. For this purpose, oxidative cleavage is applied, by prolonged treatment of reaction mixture with conc.…”

Synthesis and Copper(I)‐Driven Disaggregation of a Zinc‐Complexed Phthalocyanine Bearing Four Lateral Coordinating Rings

“…Implementation of this strategy required preparation of a phthalonitrile bearing two diethylene glycol (DEG) chains (4 in Scheme 1). Previous attempts to prepare 4 either by alkylation of 4,5-dicyanocatechol with chloroethoxyethanol [27] or by Pd/C-catalysed hydrogenolysis of bis{2Ј-[2ЈЈ-(benzyloxy)ethoxy]ethoxy}phthalonitrile [28] were unsuccessful. So, we decided to study the cyanation of the odibromide, which already contains the required DEG chains.…”

Synthesis of branched alkoxy side chains containing phthalocyanine derivates and their application in mass sensitive QCM sensors

“…9-Tosyloxy-7,11-dioxa-heptadecane (1) was synthesized according to the literature [29]. 1,2-dicyano-4,5-dihydroxybenzene (2) was prepared as previously reported [30]. Elemental analyses were obtained with a Thermo Finnigan Flash 1112 instrument.…”

Modern Synthetic Approaches to Phthalonitriles with Special Emphasis on Transition-Metal Catalyzed Cyanation Reactions

“…For example, attempt of alkylation of dicyanocatechol with chloroethoxyethanol by Torres et al, failed to produce workable amount of 1b because of the strong electron-withdrawing effect of the cyano-groups. [19] We also previously took an attempt to prepare 1b by cyanation of 4,5-dibromo-4,5-bis[2'-(2''-benzyloxyethoxy)-ethoxy]benzene 2a and subsequent debenzylation (H 2 , Pd/C) of resulting dinitrile 2b. [16] It was demonstrated that phthalonitrile unit, which is present in 2b, poisons Pd/C catalyst and precludes deprotection of benzyl groups.…”

“…In these cases, the introduction of protective groups is required, [15][16][17][18] but even these precautions sometimes do not guarantee high yields of Rosenmund-Braun cyanation of certain substrates. [19] In course of reaction, the resulting phthalonitrile forms complexes with Cu I ions, which should be decomposed to release target compound. For this purpose, oxidative cleavage is applied, by prolonged treatment of reaction mixture with conc.…”

Synthesis and Copper(I)‐Driven Disaggregation of a Zinc‐Complexed Phthalocyanine Bearing Four Lateral Coordinating Rings

“…Implementation of this strategy required preparation of a phthalonitrile bearing two diethylene glycol (DEG) chains (4 in Scheme 1). Previous attempts to prepare 4 either by alkylation of 4,5-dicyanocatechol with chloroethoxyethanol [27] or by Pd/C-catalysed hydrogenolysis of bis{2Ј-[2ЈЈ-(benzyloxy)ethoxy]ethoxy}phthalonitrile [28] were unsuccessful. So, we decided to study the cyanation of the odibromide, which already contains the required DEG chains.…”