Sustainable Approaches to the Synthesis of Metallophthalocyanines in Solution
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),...
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| Format: | Article |
| Language: | English |
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MDPI AG
2021-03-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/26/6/1760 |
| _version_ | 1797540592774807552 |
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| author | Gloria Zanotti Patrizia Imperatori Anna Maria Paoletti Giovanna Pennesi |
| author_facet | Gloria Zanotti Patrizia Imperatori Anna Maria Paoletti Giovanna Pennesi |
| author_sort | Gloria Zanotti |
| collection | DOAJ |
| description | 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-<i>tert</i>-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-<i>tert</i>-butyl-2-iodophthalocyaninato zinc(II), starting from 4-<i>tert</i>-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. |
| first_indexed | 2024-03-10T13:03:24Z |
| format | Article |
| id | doaj.art-ee042fc6223c49ff8ae94d5465ce3c04 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T13:03:24Z |
| publishDate | 2021-03-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-ee042fc6223c49ff8ae94d5465ce3c042023-11-21T11:23:24ZengMDPI AGMolecules1420-30492021-03-01266176010.3390/molecules26061760Sustainable Approaches to the Synthesis of Metallophthalocyanines in SolutionGloria Zanotti0Patrizia Imperatori1Anna Maria Paoletti2Giovanna Pennesi3Istituto di Struttura della Materia (ISM) Consiglio Nazionale delle Ricerche (CNR), Via Salaria km 29.300, 00015 Monterotondo, ItalyIstituto di Struttura della Materia (ISM) Consiglio Nazionale delle Ricerche (CNR), Via Salaria km 29.300, 00015 Monterotondo, ItalyIstituto di Struttura della Materia (ISM) Consiglio Nazionale delle Ricerche (CNR), Via Salaria km 29.300, 00015 Monterotondo, ItalyIstituto di Struttura della Materia (ISM) Consiglio Nazionale delle Ricerche (CNR), Via Salaria km 29.300, 00015 Monterotondo, ItalyThis 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-<i>tert</i>-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-<i>tert</i>-butyl-2-iodophthalocyaninato zinc(II), starting from 4-<i>tert</i>-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.https://www.mdpi.com/1420-3049/26/6/1760sustainabilityalternative solventsmetallomacrocycles |
| spellingShingle | Gloria Zanotti Patrizia Imperatori Anna Maria Paoletti Giovanna Pennesi Sustainable Approaches to the Synthesis of Metallophthalocyanines in Solution Molecules sustainability alternative solvents metallomacrocycles |
| title | Sustainable Approaches to the Synthesis of Metallophthalocyanines in Solution |
| title_full | Sustainable Approaches to the Synthesis of Metallophthalocyanines in Solution |
| title_fullStr | Sustainable Approaches to the Synthesis of Metallophthalocyanines in Solution |
| title_full_unstemmed | Sustainable Approaches to the Synthesis of Metallophthalocyanines in Solution |
| title_short | Sustainable Approaches to the Synthesis of Metallophthalocyanines in Solution |
| title_sort | sustainable approaches to the synthesis of metallophthalocyanines in solution |
| topic | sustainability alternative solvents metallomacrocycles |
| url | https://www.mdpi.com/1420-3049/26/6/1760 |
| work_keys_str_mv | AT gloriazanotti sustainableapproachestothesynthesisofmetallophthalocyaninesinsolution AT patriziaimperatori sustainableapproachestothesynthesisofmetallophthalocyaninesinsolution AT annamariapaoletti sustainableapproachestothesynthesisofmetallophthalocyaninesinsolution AT giovannapennesi sustainableapproachestothesynthesisofmetallophthalocyaninesinsolution |