A novel route to 4-chloro-5-alkyl-phthalonitrile and phthalocyanines derived from it

Dincer H., Gul A., KOÇAK M.

JOURNAL OF PORPHYRINS AND PHTHALOCYANINES, cilt.8, sa.10, ss.1204-1208, 2004 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 8 Sayı: 10
  • Basım Tarihi: 2004
  • Doi Numarası: 10.1142/s1088424604000544
  • Dergi Adı: JOURNAL OF PORPHYRINS AND PHTHALOCYANINES
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.1204-1208
  • İstanbul Teknik Üniversitesi Adresli: Evet

Özet

A new route to the synthesis of 4-chloro-5-alkyl-phthalonitrile derivatives was shown by the displacement reaction of 4,5-dichloro-phthalonitrile and diethylmalonate, a CH-acidic precursor, in the presence of K2CO3. Cyclotetramerization of 1-chloro-3,4-dicyano-6-(1,1-dicarbethoxymethyl)benzene and the metal salt without any solvent gave the corresponding metallophthalocyanines (M = Co, Cu or Pd). Transesterification occurred when the reaction was carried out in hexanol in the presence of DBU to obtain the metal-free derivative. Treatment of 1-chloro-3,4-dicyano-6-(1,1-dicarbethoxy-methyl)benzene with sodium ethoxide at ambient temperature and further acidification resulted in 2,9,16,23-tetra(carboxymethyl)-3,10,17,24-tetrachloro-phthalocyaninatopalladium(II) with partial decarboxylation. Its electronic spectrum in aqueous solution indicated no appreciable change over a pH range from 7 to 12. Copyright (c) 2004 Society of Porphyrins & Phthalocyanines.