Novel Synthesis of Phthalocyanines from Phthalonitriles under Mild Conditions

Abstract

A convenient preparation of phthalocyanines from phthalonitriles was accomplished by treatment with metal salts and hexamethyldisilazane (HMDS) in DMF at 100 °C. This reaction provides a new preparative method under mild conditions for phthalocyanines having a variety of metals and substituted phthalocyanines as well as Zn-naphthalocyanine.

Key words

phthalocyanine - naphthalocyanine - phthalonitrile - hexamethyldisilazane - dye

References

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AISIN COSMOS R&D Co., Ltd.

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Representative Procedure: A mixture of phthalonitrile (107 mg, 0.84 mmol), HMDS (0.35 mL, 1.66 mmol), ZnBr₂ (50 mg, 0.22 mmol), and DMF (0.21 mL) was heated at 100 °C under Ar atmosphere. The mixture was separated into two phases. After heating for 10 h, the reaction mixture was subjected to evaporation under reduced pressure. The resultant solid was washed successively with MeOH (50 mL) and with water (50 mL). The obtained crude product was further purified by extraction with chloroform (50 mL) using Soxhlet’s extractor, and dried under reduced pressure, affording Zn-phthalocyanine 7a (91 mg) in 78% yield. Anal. Found: C, 66.21; H, 2.88; N, 19.59. Calcd: C, 66.50; H, 2.79; N, 19.39. IR (KBr):1608, 1486, 1456, 1412, 1331, 1285, 1167, 1118, 1090, 1061, 887, 778, 752, 727 cm^-1. TOF MS (MALDI): 576.2 (M⁺). All the compounds obtained are known and in agreement with the spectral and analytical data.