Facile synthesis of phthalocyanine at low temperature with diisopropylamide anion as nucleophile

Zheng, Wei; Wan, Chunru; Zhang, Jingxuan; Li, Chenghui; You, Xiao‐Zeng

doi:10.1016/j.tetlet.2015.05.086

Cited by 13 publications

(10 citation statements)

References 25 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Nevertheless, it still often requires an organic base, commonly 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU), to catalyze the reagent tetramerization and reaction media such as alkyl alcohols (pentanol, hexanol), dimethylaminoethanol (DMAE) nitrobenzene, chlorobenzene, quinoline and α-chloronaphthalene [ 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 ], most of which are non-environmentally friendly. Given their extreme technological importance, many unconventional synthetic approaches have been studied and developed in parallel with their applications to increase their yields and sustainability while reducing their production cost, such as (i) microwave-assisted [ 22 ] and UV-assisted [ 23 , 24 ] processes, which are usually much faster and cleaner than their “standard” counterparts but requiring specific instrumentation and lacking scalability, and (ii) room-temperature reactions promoted by strong organic bases such as lithium diisopropylamide (LDA) [ 25 ] and pre-formed lithium alcoholate solutions [ 26 ]. With a view to increase the sustainability of the phthalocyanine synthesis on the lab scale, we systematically studied the effect of solvent and base replacement on the yield and cost of the macrocyclization reaction of phthalonitrile and 4- tert -butylphthalonitile templated by three first-transition metal ions: Co(II), Cu(II) and Zn(II).…”

Section: Introductionmentioning

confidence: 99%

Sustainable Approaches to the Synthesis of Metallophthalocyanines in Solution

et al. 2021

View full text Add to dashboard Cite

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-tert-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-tert-butyl-2-iodophthalocyaninato zinc(II), starting from 4-tert-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.

show abstract

Section: Introductionmentioning

confidence: 99%

Sustainable Approaches to the Synthesis of Metallophthalocyanines in Solution

et al. 2021

View full text Add to dashboard Cite

show abstract

“…Furthermore, deamination of Im‐2 , which has the core structure of Pr, proceeds with a high activation energy (61.6 kcal mol −1 ) to form Pr‐1 . Therefore, these reactions are impractical at low temperatures and can only be performed under solvent‐free high temperature (230 °C) conditions . We have performed the reactions in various solvents with different boiling points (dichloromethane, tetrahydrofuran, ethanol, dimethylformamide, etc.)…”

Section: Methodsmentioning

confidence: 99%

Phthalorubines: Fused‐Ring Compounds Synthesized from Phthalonitrile

et al. 2018

Self Cite

View full text Add to dashboard Cite

A series of dibenzo[a,f][1,3,5]triazino[2,1,6‐cd] pyrrolizine compounds have been synthesized from phthalonitriles by a facile intramolecular cyclization process using “half‐phthalocyanine” precursors, and they were characterized by X‐ray crystallography, 1H NMR spectroscopy, UV/Vis, and theoretical calculations. These compounds have spectroscopic profiles similar to phthalocyanines and porphyrins, although their inner‐core structures and coordination types are totally different. They can be regarded as a new class of aromatic fused‐ring compounds. The low‐energy absorption of these new fused‐ring compounds are located at around 600 nm. Such a low‐energy π–π* transition is scarce in aromatic compounds having a similar molecular size. According to the nomenclature of phthalocyanines, these types of compounds have been named phthalorubines (Prs).

show abstract

“…One aspect, which has been of particular interest to us in this context, is the fabrication of self‐assembled monolayers (SAMs) of such macrocyclic species on gold by chemisorption from solution as a form of nanotechnology , . We have been pursuing a strategy, which is based on metal complexes of phthalocyanine derivatives with eight peripheral β‐positioned alkylthio substituents RS (Figure ), which are conveniently accessible by cyclotetramerisation of the corresponding 4,5‐bis(alkylthio)phthalodinitriles …”

Section: Introductionmentioning

confidence: 99%

Phthalocyanine Derivatives with Eight Peripheral Long‐Chain n‐Alkylseleno Substituents

et al. 2016

View full text Add to dashboard Cite

4,5-Bis(n-octylseleno)phthalodinitrile and 4,5-bis(ndodecylseleno)phthalodinitrile were efficiently synthesised from 4,5-dichlorophthalodinitrile and the corresponding selenolate RSeMgBr (prepared in situ from elemental selenium and RMgBr; R = n-octyl, n-dodecyl). Lithium chloride was essential for achieving the substitution of both chloro substituents. The crystal structures of the monosubstitution product 4-chloro-5n-octylselenophthalodinitrile and both disubstitution products were determined by single-crystal X-ray diffraction, with that of 4,5-bis(n-dodecylseleno)phthalodinitrile exhibiting inter- [a] 5610 molecular C-H···Se contacts compatible with hydrogen bonds. Cyclotetramerisation of these 4,5-bis(n-alkylseleno)phthalodinitriles under Tomoda conditions afforded the corresponding 2,3,9,10,16,17,23,24-octakis(n-alkylseleno)phthalocyanines Pc SeR H 2 (R = n-octyl, n-dodecyl). The phthalocyaninatomanganese(III) complexes [MnCl(Pc SeR )] were obtained from the cyclotetramerisation in the presence of manganese(II) chloride after aerobic workup. The use of terbium(III) chloride as metal salt in the cyclotetramerisation furnished the "double-decker" complexes [Tb(Pc SeR ) 2 ].

show abstract

Facile synthesis of phthalocyanine at low temperature with diisopropylamide anion as nucleophile

Cited by 13 publications

References 25 publications

Sustainable Approaches to the Synthesis of Metallophthalocyanines in Solution

Sustainable Approaches to the Synthesis of Metallophthalocyanines in Solution

Phthalorubines: Fused‐Ring Compounds Synthesized from Phthalonitrile

Phthalocyanine Derivatives with Eight Peripheral Long‐Chain n‐Alkylseleno Substituents

Contact Info

Product

Resources

About