Derivatisation of 4-nonylphenol and bisphenol A with halogenated anhydrides

• Published in: Water science and technology 2004-01, Vol.50 (5), p.115-118
• Main Authors: Stehmann, A, Schröder, H Fr
• Format: Article
• Language: English
• Subjects: Acetic Anhydrides; Acetonitrile; Anhydrides; Anhydrides - chemical synthesis; Benzhydryl Compounds; Bisphenol A; Chemical synthesis; Derivatives; Diethyl ether; Endocrine disruptors; Endocrine System - drug effects; Fluoroacetates; Fourier transforms; Gas chromatography; Gas Chromatography-Mass Spectrometry; Halogenated compounds; Halogenation; Halogens - chemistry; Infrared detectors; Infrared spectroscopy; Magnetic Resonance Spectroscopy; Molecular Structure; NMR; Nuclear magnetic resonance; Phenols; Phenols - analysis; Phenols - chemistry; Phenols - pharmacology; Separation; Spectrometry; Spectroscopy, Fourier Transform Infrared; Spectrum analysis; Triethylamine; Trifluoroacetic Acid - chemistry
• ISSN: 0273-1223; 1996-9732
• DOI: 10.2166/wst.2004.0317

The aim of this work is to synthesize and characterise the halogenated derivatives of the endocrine disrupting compounds (EDCs) 4-nonylphenol (4-NP) and bisphenol A (BPA). Characterisation was performed after gas chromatographic (GC) separation on-line coupled to mass spectrometric (MS) detector and a Fourier Transform Infrared (FTIR) spectroscopic detector. Further structure elucidation was done applying Nuclear Magnetic Resonance spectroscopy (NMR). Two different approaches for the preparation of derivatives were evaluated. At first trifluoroacetyl derivatives were synthesized by the reaction of trifluoroacetic acid (TFA) anhydride and the EDCs in acetonitrile at a temperature of 50 degrees C for 30 minutes. In a second step the 4-NP was derivatised using trichloroacetic acid anhydride and triethylamine in diethyl ether at 20 degrees C for 30 minutes. After synthesis the halogenated NP and BPA derivatives were characterised applying GC/MS, GC/FTIR and NMR. Three indices for a successful derivatisation were observed: El-GC/MS proved a complete derivatisation presenting a characteristic fragmentation pattern for each derivative. The IR spectra obtained by GC/FTIR after derivatisation and separation confirmed the loss of the phenolic O-H stretching vibration at 3,600 cm(-1) while typical absorptions for halogenated compounds now were observed. The NMR-spectra contained the predicted resonance signals.