The gas-phase dissociation reactions of chlorantraniliprole (Rynaxypyr) and cyantraniliprole (Cyazypyr) have been studied in triple-quadrupole, ion trap, and orbitrap mass spectrometers equipped with electrospray and desorption electrospray ion sources, revealing the formation of odd-electron fragment ions, the structures of which were elucidated. The odd-electron fragments were unusually abundant, and their formation is proposed to occur via a tricyclic intermediate. The applicability of the QuEChERS multiresidue method for the quantitation of chlorantraniliprole and cyantraniliprole was also assessed in this study. Four matrices representative of oily, watery, acidic, and dry crop groups were tested, with a targeted limit of quantitation (LOQ) of 0.01 mg/kg. Average recoveries ranged between 87 and 107%, with relative standard deviations (RSD) of ≤ 8%. Linear calibration functions with correlation coefficients r > 0.99 were obtained. The study provides an expansion of the QuEChERS method to include anthranilic diamides and a mass spectrometric assessment for these two novel agrochemical active ingredients.

The quick, easy, cheap, effective, rugged, and safe (QuEChERS) and the U.S. Food and Drug Administration pesticide multiresidue methods were systematically tested for the analysis of aminocyclopyrachlor, a new synthetic auxin herbicide. Results revealed that these procedures are not suitable, highlighting the need for a publicly available residue method for this new active ingredient. Such a method has been developed and is reported herein for aminocyclopyrachlor residue analysis in vegetation, including white pine, Norway spruce, grass forage, and grass hay. Aminocyclopyrachlor residues were purified from plant tissue extracts by filtration through SPE cartridges with strong anion exchange stationary phases and analyzed using LC/MS/MS. This method was validated at five laboratories across the United States; their results were compared to evaluate reproducibility and ruggedness. The method LOQ was 0.01 mg/kg (ppm) and the LOD 0.003 mg/kg (ppm) for the matrixes tested. A qualitative procedure to confirm the molecular identity of residues based on retention time measurements and ion transition peak area ratios (m/z 214 --> 681m/z 214 --> 101) is also presented.