Highly Soluble and Green Indigo Dyes: 4,4′,7,7′-Tetraalkoxy-5,5′-diaminoindigotins

✍ Scribed by Gundula Voss; Michael Gradzielski; Jürgen Heinze; Helmut Reinke; Carlo Unverzagt

• Publisher: John Wiley and Sons
• Year: 2003
• Tongue: German
• Weight: 400 KB
• Volume: 86
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.200390156

✦ Synopsis

Abstract

Two new types of 4,4′,7,7′‐tetraalkoxyindigotins, 1a–f and 2a–f along with the new N‐substituted indigotins 4e–f, were synthesized from dinitrobenzaldehydes 5a–f, which were prepared from 2‐hydroxy‐5‐methoxybenzaldehyde (7) via dialkoxybenzaldehydes 6a–f (Scheme). The new dialkoxyindigotin 3g was obtained from dialkoxybenzaldehyde 6g via nitrobenzaldehyde 8g. The 1,4‐dialkoxy‐2,3‐dinitrobenzenes 9 were isolated as by‐products. The 4,4′,7,7′‐tetraalkoxy‐5,5′‐diaminoindigotins 1 are soluble in organic solvents, and their solutions are green, which is highly uncommon for indigotins and is primarily caused by electronic effects of substituents, steric effects playing a minor role. The indigotins 1 produce a strong red shift of the longest‐wavelength absorption and negative solvatochromism indicating the predominance of polar resonance structures in the ground state. Tautomeric structures were excluded. These indigotins are valuable compounds for technical applications, for synthetic purposes, and for analytical studies. SANS (Small‐angle neutron scattering) experiments showed that certain 4,4′,7,7′‐tetraalkoxy‐5,5′‐diaminoindigotins 1 form rod‐like aggregates in solution. The similarly substituted 4,4′,7,7′‐tetraalkoxy‐5,5′‐dinitroindigotins 2 are far less soluble. They produce red monoanions (preferably dimers) and bluish‐purple dianions in organic solvents.