Novel Synthesis of Metal-Free Phthalocyanines from Phthalimides and Phthalic Anhydrides with Hexamethyldisilazane

Hitoshi Uchida; Hideyuki Yoshiyama; Paidi Yella Reddy; Shuichi Nakamura; Takeshi Toru

doi:10.1055/s-2003-41484

LETTER

Novel Synthesis of Metal-Free Phthalocyanines from Phthalimides and Phthalic Anhydrides with Hexamethyldisilazane

Hitoshi Uchida, Hideyuki Yoshiyama, Paidi Yella Reddy, Shuichi Nakamura, Takeshi Toru*
Department of Applied Chemistry, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555, Japan
Fax: +81(52)7355217; e-Mail: toru@ach.nitech.ac.jp;

Abstract

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Abstract

Metal-free phthalocyanines and their peripherally substituted derivatives have been synthesized from unsubstituted and substituted phthalimides, phthalic anhydrides, and naphthalimide on heating with hexamethyldisilazane under mild conditions.

Key words

phthalocyanine - naphthalocyanine - phthalimide - phthalic anhydride - hexamethyldisilazane

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References

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Typical Procedure for the Preparation of 3a. A glass tube was charged with phthalimide (100 mg, 0.68 mmol), p-TsOH·H₂O (13 mg, 0.07 mmol), HMDS (560 µL, 438 mg, 2.7 mmol) and DMF (50 µL, 0.68 mmol) under argon atmosphere. Then the tube was sealed. The mixture was heated at 150 °C, when a dark purple solid immediately appeared. After heating for 10 h, the mixture was cooled and filtered. The solid was washed with MeOH, and then dissolved in conc. H₂SO₄ (5.0 mL). The resulting solution was poured into H₂O (100 mL) and the blue precipitates were filtered and washed with H₂O. The solid was further purified by extraction by soxhlet extractor with methanol to give 62 mg (58%) of 3a as a blue solid.

Metal-free phthalocyanines are not formed in the absence of either p-TsOH or DMF. p-TsOH probably plays a role to activate HMDS as a silylating agent as well as phthalimides and DMF is requisite for dissolving substrates, although the role of these reagents is not clear enough.

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We also found that metal-free phthalocyanines were obtainable from phthalonitriles by the action of HMDS. The results will be reported in due course.