Phthalocyanine formation using metals in primary alcohols at room temperature

✍ Scribed by Clifford C. Leznoff; Anna M. D’Ascanio; S. Zeki Yildiz

• Publisher: John Wiley and Sons
• Year: 2000
• Tongue: English
• Weight: 95 KB
• Volume: 04
• Category: Article
• ISSN: 1088-4246
• DOI: 10.1002/(sici)1099-1409(200001/02)4:1<103::aid-jpp209>3.0.co;2-e

✦ Synopsis

Lithium metal added to a solution of 4-neopentoxyphthalonitrile in 1-octanol or other long-chain primary alcohols at room temperature resulted in phthalocyanine formation at a reasonable rate in good yield, while preformed lithium 1-octanolate under the same conditions gave 2,9,16,23-tetraneopentoxyphthalocyanine, but in lower yield at a slower rate. The use of lower-molecular-weight alcohols slowly gave a phthalocyanine in lower yields. Reverse micelle formation when using long-chain alcohols is proposed as a possibility for enhanced phthalocyanine formation at room temperature. 2,9,16,23-Tetrasubstituted phthalocyanines and metallated phthalocyanines were prepared at room temperature from 4-neopentoxyphthalonitrile, 4-bis(4-methoxyphenyl)methoxyphthalonitrile, 4-[1-(4-ethoxy-3-methoxyphenyl)-1-phenyl]methoxyphthalonitrile and phthalonitrile using lithium 1-octanolate in 1-octanol or by the addition, to a solution of the phthalonitrile in ethanol, of calcium turnings or, to a solution of the phthalonitrile in methanol, of magnesium, zinc, iron or copper powder. The tetrasubstituted phthalocyanines produced exhibited a non-statistical distribution of regioisomers, indicating that electronic effects become important in room-temperature cyclotetramerization of phthalonitriles to phthalocyanines.