Phthalocyanines, synthesis

The first commercial copper phthalocyanine synthesis, a baking process, involved melting phthalic anhydride with urea at 150°C in the presence of boric acid. Cop-per(II)chloride was then added and the temperature increased to approximately 200°C until the copper phthalocyanine production was completed. The reaction mixture was cooled and the crude product milled. After being washed, first with dilute sodium hydroxide solution and then with dilute sulfuric acid, the material was filtered off and dried. The crude copper phthalocyanine obtained was then... 

The general phthalocyanine synthesis takes an abnormal course when uranium oxychloride is employed as the template (Scheme 108).201 The product showed a broadened and bathochromically shifted optical spectrum compared to those of phthalocyanines, and turned out to be the pentameric compound (45a) as elucidated by X-ray analysis. 

Several syntheses of tetrabenzoporphyrin complexes make use of similar template strategies to those used in phthalocyanine synthesis, so they will be discussed here. An isoindole has been found to undergo a very complex series of reactions promoted by a range of metal ions in refluxing 1,2,4-trichlorobenzene to produce tetrabenzoporphyrin complexes (Scheme 55).240 In contrast, an extremely simple synthesis of tetrabenzoporphyrin can be achieved from 2-acetylbenzoic acid, using zinc as templating metal (equation 44).241... 

The formation of the macrocyclic complex (98) is a template reaction reminiscent of phthalocyanine synthesis, and aza linkages are formed (Scheme 56).242 The resulting complex (98) can be transformed into a complex with a fully conjugated macrocyclic ligand. The dibromocobaIt(III) complex related to (98) can also be prepared and can function to some extent as a model for vitamin... 

Classic Chemical and Electrochemical Methods of Metal Phthalocyanine Synthesis... 

Figure 5.1 Divided electrochemical cell for phthalocyanine synthesis (a reference electrode could be added). (From Ref. 10, with permission.)...

Phthalimide 930 has also been used for phthalocyanine synthesis (Example 25). In case of Mg [2], only the metal itself can be utilized. The process requires a much more careful control of temperature than that utilizing o-cyanobenzamide and gave only 20% of PcMg under optimum conditions. 

Chen Y, Hanack M, Blau WJ, Dini D, Liu Y, Lin Y, Bai J (2006) Soluble axially substituted phthalocyanines synthesis and nonlinear optical response. J Mater Sci 41(8) 2169—2185... 

Eberhardt W, Hanack M (1997) Synthesis of hexadecaalkoxy-substituted nickel and iron phthalocyanines. Synthesis 1 95-100... 

Yarasir MN, Kandaz M, Koca A, Salih B (2006) Functional alcohol-soluble double-decker phthalocyanines synthesis, characterization, electrochemistry and peripheral metal ion binding. J Porphyrins Phthalocyanines 10(8) 1022-1033... 

Fukuda F, Homma S, Kobayashi N (2005) Deformed phthalocyanines synthesis and characterization of zinc phthalocyanines bearing phenyl substituents at the 1,4,8,11,15,18,22, and/or 25-positions. Chem Euro J 11(18) 5205-5216... 

Kadish, K. M., Moninot, G., Hu, Y., Dubois, D., Ibnlfassi, A., Barbe, J.-M., Guilard, R. (1993). Double-decker actinide porphyrins and phthalocyanines. Synthesis and spectroscopic characterization of neutral, oxidized, and reduced homo- and het-eroleptic complexes, J. Am. Chem. Soc., 115 8153. 

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