Production of Chloro-5-hydroxy-2-nitrobenzoic Acid through Chlorination of 3-Methyl-4-nitrophenol, a Typical Hydrolysate of Fenitrothion

Abstract

Fenitrothion [O, O-dimethyl O-(3-methyl-4-nitrophenyl)phosphorothioate], a typical organophosphorus pesticide, is widely used as an insecticide in Japan. In this study, 3-methyl-4-nitrophenol (3M4NP), which is a typical hydrolysate of fenitrothion, was focused as a possible mutagen precursor because it is reported as a common contaminant in raw water for water works, and is capable of forming mutagens when it is chlorinated in water works. In order to examine molecular formulae of mutagens produced from 3M4NP, a chlorinated 3M4NP sample was analyzed with a high-resolution LC/MS. Several peaks were found in a base peak chromatogram. A peak of m/z 215.971 was focused to be analyzed, suggesting a formation of C 7 H 4 O 5 NCl (mass error = 0.397 mmu or 1.837 ppm). To examine the chemical structure of the found substance, MS 2 experiments were conducted with a collision induced disassociation technique. Four product ions: m/z 198.9679, 187.9757, 170.9731 and 136.0043 which can be attributed to losses of OH, CO, COOH and Cl functional groups were observed. From these fragment ions and the structure of 3M4NP, the substance was extrapolated to be chloro-5-hydroxy-2-nitrobenzoic acid (C5H2NB). The mutagen formation potential (MFP) of 5-hydroxy-2-nitrobenzoic acid, which is considered to be a precursor of C5H2NB, was tested and the MFP of 3,400 net rev./µmol was observed.

The Status Quo of Causal Substance Exploration for Fishy Odor in Raw Water for Taps

“…Bade et al utilized LC-HRMS to screen pharmaceuticals and illicit drugs in wastewater and surface water, identifying many compounds including irbesartan, valsartan, benzoylecgonine, caffeine, and so on [82]. Takanashi et al focused on 3-methyl-4-nitrophenol (3M4NP), a typical hydrolysate of fenitrothion, and proposed that chloro-5-hydroxy-2-nitrobenzoic acid was possibly generated as a chlorination product of 3M4NP [83]. Kondo et al monitored pesticides and their transformation products in water environments utilizing LC-MS/MS [84].…”

National trends in pesticides in drinking water and water sources in Japan

“…Fipronil yields its sulfone or additional forms in chlorine treatment (Teerlink et al, 2017). Fenitrothion is transformed into its oxon form and other fragments by chlorine treatment (Takanashi et al, 2012). Chlorine treatment also decomposes bensulfuron methyl (Hu et al, 2015) and halosulfuron methyl (Wang et al, 2015).…”

Identification of mutagenic transformation products generated during oxidation of 3-methyl-4-nitrophenol solutions by orbitrap tandem mass spectrometry and quantitative structure–activity relationship analyses

“…C5H2NBA is thought to be a major contributor to the mutagenicity observed after chlorination of 3M4NP solutions (i.e., it is thought to be a mutagenic CTP) (Takanashi et al 2012). In the present study, we focused Effect of UV irradiation time on mutagenicity intensity (MI 500 ) of 3-methyl-4-nitrophenol solutions before and after chlorination: AOP (white circles) and AOP/Cl (black circles), without (−S9mix) and with (+S9mix) metabolic activation in the Ames assay.…”

“…In fact, Kishida et al (2010) reported that a 3M4NP solution became mutagenic after the addition of free chlorine, indicating that 3M4NP is transformed into a mutagenic compound or compounds during chlorination. Takanashi et al (2012) reported that chloro-5-hydroxy-2-nitrobenzoic acid (C5H2NBA) is largely responsible for the mutagenicity induced by chlorination of 3M4NP solutions. Moreover, Kishida et al (2010) reported that the mutagenicity of a chlorinated 3M4NP solution is much higher than that of a chlorinated fenitrothion solution at the same molar concentration.…”