Synthesis and Properties of an Unsymmetrical Triazole‐Functionalized (Phthalocyaninato)zinc Complex

Abstract

The synthesis of 5,6-dicyano-1H-1,2,3-benzotriazole (2) was significantly simplified and its overall yield was increased. This opens up the possibility for an extended use of 2 as a precursor for triazole-functionalized phthalocyanines. One of them, the unsymmetrical {9, 10,16,17,23,24-hexakis(3,5-ditert-butylphenoxy) [1,2,3]triazolo [4,5-b]phthalocyaninato}-zinc (5) was prepared in a statistical condensation of 2 and 4,5-bis(3,5-di-tert-butylphenoxy)phthalonitrile (3) with subsequent separation by column chromatography. The triazolefunctionalized (phthalocyanine)zinc complex 5 shows inter-

New Unsymmetrical Zinc‐Phthalocyanine Conjugated with One Azo‐Dye Moiety: Synthesis via Opening the Fused Triazole Ring and Spectral Properties

“…These unsymmetrical Pc synthons have been used for the preparation of ethynyl‐substituted phthalocyanines, ethynyl‐ and diethynylethene‐bridged bis(phthalocyanines), binuclear and trinuclear phthalocyanine‐containing phosphonium salts, as well as for the synthesis of other important Pc synthons containing vinyl or aldehyde functionalities 3. Recently, we reported the preparation of a new unsymmetrical, soluble zinc‐phthalocyanine with one fused 1,2,3‐triazole ring in the periphery (compound 1 in Scheme ) 4. First investigations on the properties of 1 have shown that it is another useful synthon for various unsymmetrical modifications of phthalocyanines.…”

Reactivity of Dehydrometallophthalocyanines and ‐porphyrazines

“…[9] Investigation of its spectral properties (UV/Vis, 1 H and 13 C NMR) revealed many similarities between 5 and 7.…”

“…UV/Vis spectroscopy: Shimadzu UV-365. 1 (1), [2] bis(4-tert-butylphenyl)fumaronitrile (A), [15] 5,6-dicyano-1H-benzotriazole (B), [9] and 1-aminobenzotriazole (15) [6] were prepared as described earlier. Other chemicals and solvents were purchased from commercial sources and were used without additional purification, unless mentioned.…”

[1,2,3]Triazolo[4,5‐b]porphyrins: New Building Blocks for Porphyrinic Materials

“…However, a completely different synthetic approach was used: 5,6-dicyano-1H-benzotriazole was prepared first, and then it was used to synthesize tetra- [39] and monotriazolophthalocyanines. [40] 1N-Amination of the latter compound and oxidation of the resulting amino derivative resulted in the generation of a dehydrophthalocyanine, which could be trapped in situ with several dienes to afford the corresponding Diels-Alder adducts. [41] The N-alkylation and N-arylation of triazoloporphyrins 2 are convenient routes to other porphyrinic derivatives.…”