Synthesis, spectral, and thermal properties of some phosphorus-containing 9,10-anthraquininoid, thermally stable dyes

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Abstract

The multi-component, one-step reaction of dialkyl acetylenedicarboxylates with 1-amino-9,10-anthraquinone in the presence of triphenyl phosphite or trialkyl phosphites, produces 9,10-anthraquinone derivatives containing dialkyl(aryl) phosphoryl groups as novel, thermally stable dyes in fairly good yields. The structural characterization and some physical properties of these dyes are reported.

Introduction

Aminoanthraquinones are the basic structural units of disperse dyes [1], [2], [3], [4], [5], [6], which are an important class of dye, characterized by good fastness properties and brightness on hydrophobic fibres, such as poly(ethylene terephthalate), on which they provide mostly bright red to blue hues; also are included acylamino-anthraquinones which furnish mainly yellow and orange dyes. In addition, anthraquinones have become recently very important due to their application in high technology electronics. Some aminoanthraquinone derivatives are used in transfer printing toners and others are used in thermal printing [7], [8]. The Pdouble bondO group has often been incorporated into the compounds to enhance their thermal/oxidative stability and ignition resistance [9].

In a continuation of our current interest in the development of new routes to 9,10-anthraquinones [10], [11], herein we report a simple, one-pot synthesis of some thermally stable anthraquinone derivatives containing dialkyl(aryl) phosphoryl moieties.

Section snippets

Structural characterization of dyes

The reaction of dialkyl acetylenedicarboxylates (2) with 1-aminoanthraquinone (3) in the presence of trialkyl(aryl) phosphites (1) in toluene, under reflux, leads to dialkyl 2-{bis[alkyl(aryl)oxy]-phosphoryl}-3-[(9,10-dioxo-9,10-dihydro-1-anthracenyl)amino]-butanedioates (4) in 70–90% yield (Scheme 1).

The structures of 4a4f were deduced from their elemental analyses and high-field 1H, 13C, and 31P NMR spectra, IR spectra and UV–vis absorption spectral data. The mass spectra of these compounds

Conclusions

The reaction of 1-aminoanthraquinone with dialkyl acetylenedicarboxylates in the presence of trialkyl(aryl) phosphites leads to the efficient synthesis of thermally stable anthraquinone derivatives containing dialkyl(aryl) phosphoryl moieties. All of the pigments were fully characterized by 1H NMR, 13C NMR, 31P NMR, IR, and UV–vis absorption spectra, mass spectra and TGA–DSC measurements. Some structural characterization and physical properties of the dyes are reported.

General

Compounds 13 were obtained from Fluka and were used without further purification. M.p.: Electrothermal-9100 apparatus; uncorrected. IR spectra: Shimadzu IR-460 spectrometer. 1H, 13C, and 31P NMR spectra: Bruker DRX-500 Avance instrument; in CDCl3 at 500.1, 125.8, and 202.4 MHz, respectively; δ in parts per million, J in hertz. EI-MS (70 eV): Finnigan-MAT-8430 mass spectrometer, in m/z. Elemental analyses (C, H, N) were performed with a Heraeus CHN–O-Rapid analyzer. UV spectra were taken on a

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