ChemInform Abstract: Electrosynthesis of Phthalocyanines.

Synthesis of non-substituted phthalocyanines by standard and non-standard techniques. Influence of solvent nature in phthalocyanine preparation at low temperature by UV-treatment of the reaction system

“…Additionally, zeolites and other microporous materials can be also used for obtaining phthalocyanine from phthalonitrile in cavities. [70][71][72] According to the considerations above for optimizing the low-temperature preparation of phthalocyanines, six routes are being developed in our laboratory: (1) UV-irradiation of the reaction system (without use of metals) 45 and use of radicalforming compounds; (2) use of elemental metals 43 in the form of active finely divided pyrophoric metal powders 73 and Rieke metals 69 as ''matrices'' for phthalonitrile cyclization and Pc core formation; (3) direct electrochemical synthesis using sacrificial anodes and even cathodes; 7,8,32,33,36,66,67 (4) use of zeolites and other microporous materials, [70][71][72] (5) use of socalled ''supported metals'' 69 and (6) search of active (or nonstable) complexes or organic bases 68 for the first cyclization reaction step. In this publication, we present the experimental results of the first technique.…”

“…The feasibility of the electrosynthesis of PcM was first reported by C. H. Yang,7 who obtained ''PcM'' of Cu, Ni, Co, Mg, and Pb using metal salts or elemental Fe and Cu as a source for the central atom. Furthermore, Petit's research group 8 studied the electrosynthesis of PcCu by electroreduction of Pc with a copper sheet or an electrodeposited layer of copper on platinum as an anode. Among reported ''non-standard'' techniques for metal phthalocyanine production, microwave irradiation under solvent free conditions has been used for obtaining phthalocyanine derivatives of Ru, Rh, Pt, and Pt, 9 Zn, Mg, Co, and Cu 10 or Si.…”

Phthalocyanine formation using metals in primary alcohols at room temperature

“…Lower-temperature syntheses have been demonstrated [8][9][10][11][12][13][14][15], but unusual substrates, complex approaches and poorer yields have inhibited their widespread use.…”

“…Calcium metal was sufficiently reactive only in ethanol and hence addition of calcium to 5-7 in ethanol at room temperature proceeded slowly to give phthalocyanines 9, 10 and 12 respectively. Magnesium in methanol was sufficiently reactive, so magnesium was added to 5 in methanol to yield 2,9,1 6,23-tetraneopentoxyphthalocyaninato magnesium(Il) (14). Similarly, calcium, magnesium, zinc, iron or copper was added at room temperature to phthalonitrile (8) in ethanol (for calcium) or methanol to give phthalocyanines [15][16][17][18][19] respectively in low yields (Table l, formation at room temperature.…”

“…Tetraneopentoxyphthalocyaninato Magnesium(II) (14) Compound 5 (400mg, l.87mmol) was dissolved in methanol (3 mL). Magnesium powder (53 mg, 2.l8mmol) was added to the reaction mixture.…”