Abstract
The objective of the present work is to reduce the temperature of preparation
of metal-free phthalocyanine and metal phthalocyaninates from “standard” 80-
200oC to relatively low temperatures (0-60oC) starting from phthalonitrile as a
precursor. To accomplish this, three routes are being developed, among others:
1) use of elemental metals, finely divided metal powders, “supported” and
Rieke metals as “matrices” for phthalonitrile cyclization; 2) UV-irradiation of the
reaction system (without use of metals); 3) use of microporous materials, 4)
direct electrochemical synthesis using sacrificial metal anodes.
Use of elemental metals. The following metals in the form of powder,
granules or sheet were used: Fe, Sn, Zn, Ni, Cu, Mg, Al, and the alloy Pb-Ca-Sn.
Ethyleneglycol, methanol, ethanol, i-propanol, 1-buthanol, i-butanol, t-butanol,
1-octanol, 2-ethoxyethanol were used as solvents. All reactions were performed
using ultrasonic treatment of the reaction system during 3-25 hrs. at 0-50oC.
Quantitative yields were obtained for the systems: Zn-1-octanol, Ni-methanol,
Mg-methanol, Ni-butanol, and Zn-methanol at 50oC. At lower temperatures, the
yields were smaller. Nickel was used in three different forms: sheet, Raney nickel,
and pyrophoric nickel under a water layer. In general, the nickel activity with
respect to the Pc formation decreases in this order: pyrophoric nickel > nickel
sheet > Raney nickel. Use of zeolites. Use of zeolites and other microporous

materials showed positive results at r.t. in some low molecular weight alcohols.
Conclusions
According to the preliminary results, the PcH2 or PcM are formed at 0-
50oC in alcohol solutions in the presence of elemental metals or microporous
materials using phthalonitrile as a precursor. Metals in their activated form are
much stronger with respect of phthalonitrile cyclization in comparison with nonactivated
metals. A high number of defects and imperfections on the activated
metal surface can be related to their major reactivity and may serve as matrices
for phthalocyanine formation. The results show that the nature of the solvent is
the most important factor in the phthalocyanine synthesis at low temperatures.
Acknowledgement. The authors are very grateful to CONACyT-Mexico
(project 39,558-Q) and Paicyt-UANL for financial support.
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