Istituto di Struttura della Materia (ISM) Consiglio Nazionale delle Ricerche (CNR), Via Salaria km 29.300, 00015 Monterotondo, Italy.
Molecules. 2021 Mar 21;26(6):1760. doi: 10.3390/molecules26061760.
This work aims to investigate more sustainable reaction conditions for the synthesis of metallophthalocyanines. Anisole, glycerol and their mixtures have been investigated as reaction media for the tetramerization of phthalonitriles. Acetates of three divalent first-transition metal cations, Co(II), Cu(II) and Zn(II), were used and several bases were tested, depending on the chosen substrates and reaction conditions, with a view to making the whole process more sustainable while ensuring its scalability. Unsubstituted phthalocyanines were synthesized to analyze the behavior of the different metal ions in terms of reactivity in the new reaction media, resulting in a general Cu > Co > Zn trend, while the nonpolar tetra--butyl substitution was investigated to evaluate the synthesis of soluble derivatives in the new conditions. Furthermore, the potassium hydroxide (KOH)-aided statistical synthesis of the unsymmetrical 9(10), 16(17), 23(24)-tri--butyl-2-iodophthalocyaninato zinc(II), starting from 4--butylphthalonitrile and 4-iodophthalonitrile in a glycerol/anisole mixture, proceeded with a satisfactory 26% yield. Our results provide insights into the investigation of new reaction environments and the understanding of their strengths and weaknesses, with a view to further increasing the sustainability of the synthesis of metallomacrocycles with high added value while lowering their production cost.
这项工作旨在研究合成金属酞菁更可持续的反应条件。茴香醚、甘油及其混合物已被用作研究腈的四聚反应的反应介质。使用了三种二价第一过渡金属阳离子的醋酸盐，根据所选的底物和反应条件测试了几种碱，以期在确保其可扩展性的同时使整个过程更加可持续。合成了未取代的酞菁，以分析不同金属离子在新反应介质中的反应活性，得出一般的 Cu > Co > Zn 趋势，而非极性四丁基取代则用于评估在新条件下可合成可溶性衍生物。此外，以氢氧化钾（KOH）辅助统计合成了非对称的 9(10)、16(17)、23(24)-三--丁基-2-碘代酞菁酸锌（II），从 4-丁基腈和 4-碘代腈在甘油/茴香醚混合物中，以令人满意的 26%产率进行。我们的研究结果为研究新的反应环境提供了深入的了解，并深入研究了其优缺点，以期进一步提高具有高附加值的金属大环化合物的合成的可持续性，同时降低其生产成本。
