Novel and Mild Route to Phthalocyanines and 3-Iminoisoindolin-1-ones via N,N-Diethylhydroxylamine-Promoted Conversion of Phthalonitriles and a Dramatic Solvent-Dependence of the Reaction
✍ Scribed by Konstantin V. Luzyanin; Vadim Yu. Kukushkin; Maximilian N. Kopylovich; Alexey A. Nazarov; Markus Galanski; Armando J. L. Pombeiro
- Publisher
- John Wiley and Sons
- Year
- 2008
- Tongue
- English
- Weight
- 247 KB
- Volume
- 350
- Category
- Article
- ISSN
- 1615-4150
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✦ Synopsis
Abstract
Refluxing a mixture of phthalonitrile C~6~R^1^R^2^R^3^R^4^(CN)~2~ 1 (R^1^–R^4^=H), or its substituted derivatives 2 (R^1^, R^3^, R^4^=H, R^2^=Me), or 3 (R^1^, R^4^=H, R^2^, R^3^=Cl) (1 equiv.) and N,N‐diethylhydroxylamine, Et~2~NOH, (4 equivs.) in methanol for 4 h results (Route A) in precipitation of the symmetrical (6 and 8) and an isomeric mixture of unsymmetrical (7) phthalocyanines, isolated in good (55–65 %) yields. The reaction of phthalonitriles 1, 2, or 4 (R^1^, R^3^, R^4^=H, R^2^=NO~2~) (4 equivs.) with Et~2~NOH (8 equivs.) in the presence of a metal salt MCl~2~ (M=Zn, Cd, Co, Ni) (1 equiv.) in __n‐__BuOH or without solvent results in the formation of metallated phthalocyanine species (9–17). Upon refluxing in freshly distilled dry chloroform, phthalonitrile 1 or its substituted analogues 2, 3 or 5 (R^1^–R^4^=F) (1 equiv.) react with N,N‐diethylhydroxylamine (2 equivs.) affording 3‐iminoisoindolin‐1‐ones 18–21 (Route B) isolated in good yields (55–80 %). All the prepared compounds were characterized with C, H, and N elemental analyses, ESI‐MS, IR, and compounds 18–21 also by 1D (^1^H, ^13^C{^1^H}), and 2D (^1^H,^15^N‐HMBC and ^1^H,^13^C‐HMQC, ^1^H,^13^C‐HMBC) NMR spectroscopy.