Unlocking PEG-400: A Sustainable Reaction Medium for Phthalocyanine Synthesis and Pd-Catalyzed C–C Bond Formation
4 affiliations
- 1Istituto di Struttura della Materia (CNR-ISM), Strada provinciale 35d/9, Montelibretti, Italy, 00010
- 2Department of Chemistry, Sapienza University of Rome, P.le Aldo Moro 5, Rome, Italy, 00185
- 3Istituto di Struttura della Materia (CNR-ISM), Via del Fosso del Cavaliere 100, Rome, Italy, 00133
- 4Department of Chemistry and Technology of Drugs, Sapienza University of Rome, P.le Aldo Moro 5, Rome, Italy, 00185
Abstract
In this work, we demonstrate that poly(ethylene glycol)-400 (PEG-400) can efficiently replace conventional and hazardous solvents such as N,N-dimethylaminoethanol (DMAE) and N,N-dimethylformamide (DMF) in the synthesis of phthalocyanines, a class of functional molecular materials widely investigated for optoelectronic and energy-related applications. Used at a loading as low as 1.0 equivalent relative to the phthalonitrile precursor, PEG-400 enables cyclotetramerization reactions under operationally simple and comparatively safer conditions, providing isolated yields of 50-83% across a range of metalated and metal-free derivatives and substitution patterns. The robustness of the protocol was further demonstrated at the multigram scale, affording cobalt phthalocyanine in 79% yield, with 88% of the PEG-400 recovered from the reaction mixture. Remarkably, PEG-400 proved compatible with sequential cyclotetramerization followed by Sonogashira or Suzuki coupling without isolation of the macrocyclic intermediate, affording functionalized products in up to 75% yield and enabling pot-economical access to more complex derivatives. E-factor and Process Mass Intensity (PMI) analyses quantitatively support the improved material-efficiency profile of the method when compared to representative literature procedures. Overall, these results establish PEG-400 as a versatile and sustainable medium for the resource-efficient synthesis and functionalization of phthalocyanine derivatives.
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BibTeX
@misc{palmeri2026unlocking,
title = {{Unlocking PEG-400: A Sustainable Reaction Medium for Phthalocyanine Synthesis and Pd-Catalyzed C–C Bond Formation}},
author = {Federica Palmeri and Venanzio Raglione and Chiara Salvitti and Anna Troiani and Gloria Zanotti},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15007374/v2},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15007374/v2},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Unlocking PEG-400: A Sustainable Reaction Medium for Phthalocyanine Synthesis and Pd-Catalyzed C–C Bond Formation
AU - Federica Palmeri
AU - Venanzio Raglione
AU - Chiara Salvitti
AU - Anna Troiani
AU - Gloria Zanotti
PY - 2026
DA - 2026/09/16
PB - ChemRxiv
DO - 10.26434/chemrxiv.15007374/v2
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15007374/v2
AB - In this work, we demonstrate that poly(ethylene glycol)-400 (PEG-400) can efficiently replace conventional and hazardous solvents such as N,N-dimethylaminoethanol (DMAE) and N,N-dimethylformamide (DMF) in the synthesis of phthalocyanines, a class of functional molecular materials widely investigated for optoelectronic and energy-related applications. Used at a loading as low as 1.0 equivalent relative to the phthalonitrile precursor, PEG-400 enables cyclotetramerization reactions under operationally simple and comparatively safer conditions, providing isolated yields of 50-83% across a range of metalated and metal-free derivatives and substitution patterns. The robustness of the protocol was further demonstrated at the multigram scale, affording cobalt phthalocyanine in 79% yield, with 88% of the PEG-400 recovered from the reaction mixture. Remarkably, PEG-400 proved compatible with sequential cyclotetramerization followed by Sonogashira or Suzuki coupling without isolation of the macrocyclic intermediate, affording functionalized products in up to 75% yield and enabling pot-economical access to more complex derivatives. E-factor and Process Mass Intensity (PMI) analyses quantitatively support the improved material-efficiency profile of the method when compared to representative literature procedures. Overall, these results establish PEG-400 as a versatile and sustainable medium for the resource-efficient synthesis and functionalization of phthalocyanine derivatives.
ER -