Abstract :
New highly organosoluble metallophthalocyanines (M = Zn, Co, Ni and Cu) bearing four [4-(3,3,6,6-tetramethyl-1,8-dioxo-2,3,4,5,6,7,8,9-octahydro-1H-xanthen-9-yl)phenoxy] substituents at peripheral positions have been prepared by tetramerization of 4-[4-(3,3,6,6-tetramethyl-1,8-dioxo-dodecahydro-1H-xanthen-9-yl)phenoxy]phthalonitrile in 2-(dimethylamino)ethanol using microwave irradiation or conventional heating. Ni(II), Co(II), and Cu(I) chloride were employed in order to synthesize the corresponding metal phthalocyanines and Zn(OAc)2 was used for the preparation of the zinc phthalocyanines. 4-[4-(3,3,6,6-Tetramethyl-1,8-dioxo-2,3,4,5,6,7,8,9-octahydro-1H-xanthen-9-yl)phenoxy]phthalonitrile was obtained by nucleophilic displacement of the nitro group in 4-nitrophthalonitrile with 9-(4-hydroxyphenyl)-3,3,6,6-tetramethyl-3,4,6,7-tetrahydro-2H-xanthene-1,8(5H,9H)-dione. 9-(4-Hydroxyphenyl)-3,3,6,6-tetramethyl-3,4,6,7-tetrahydro-2H-xanthene-1,8(5H,9H)-dione was synthesized efficiently from dimedone and 4-hydroxybenzaldehyde. All the phthalocyanines are soluble in DMSO, DMF, CHCl3, THF, CH2Cl2, and CH3CN. The new compounds were characterized by IR, NMR, and UV–vis spectroscopy, elemental analysis, and thermogravimetric analysis.
