Insecticide synergists are key components to increase the control efficacy and reduce active ingredient use. Here, we describe a novel insecticide synergist with activity specific for insecticidal neonicotinoids. The synergist IPPA08, a cis configuration neonicotinoid compound with a unique oxabridged substructure, could increase the toxicity of most neonicotinoid insecticides belonging to the Insecticide Resistance Action Committee (IRAC) 4A subgroup against a range of insect species, although IPPA08 itself was almost inactive to insects at synergistic concentrations. Unfortunately, similar effects were observed on the honey bee (Apis mellifera) and the brown planthopper (Nilaparvata lugens), resistant to imidacloprid. IPPA08 did not show any effects on toxicity of insecticides with different targets, which made us define it as a neonicotinoid-specific synergist. Unlike most insecticide synergists, by inhibition of activities of detoxification enzymes, IPPA08 showed no effects on enzyme activities. The results revealed that IPPA08 worked as a synergist through a distinct way. Although the modulating insect nicotinic acetylcholine receptors (nAChRs, targets of neonicotinoid insecticides) were supposed as a possible mode of action for IPPA08 as a neonicotinoid-specific synergist, direct evidence is needed in further studies. In insect pest control, IPPA08 acts as a target synergist to increase neonicotinoid toxicity and reduce the amount of neonicotinoid used. Combinations of IPPA08 and insecticidal neonicotinoids may be developed into new insecticide formulations. In summary, combining an active ingredient with a "custom" synergist appears to be a very promising approach for the development of effective new insecticide products.

A series of novel 1,2,3-benzotriazin-4-one derivatives were synthesized by the reaction of 3-bromoalkyl-1,2,3-benzotriazin-4-ones with potassium salt of 2-cyanoimino-4-oxothiazolidine in the presence of potassium iodide. Nematicidal assays in vivo showed that some of them exhibited good control efficacy against the cucumber root-knot nematode disease caused by Meloidogyne incognita, up to 100% at the concentration of 10.0 mg L(-1), which indicated that 1,2,3-benzotriazin-4-one derivatives might be potential for novel promising nematicides. The nematicidal activity was influenced by the combination of substituent type, substituted position, and linker length in the molecule. The inhibition rate data at the concentrations of 5.0 and 1.0 mg L(-1) for the compounds with high inhibitory activities were also provided. When tested in vitro, none of them showed direct inhibition against M. incognita. The investigation of a significant difference between in vivo and in vitro data is in progress.

Cycloxaprid (CYC) is a new cis-configuration neonicotinoid insecticide, which is currently under development in China for agricultural pest control. Considering the photodegradation of CYC is important for the application of CYC in the future, the photochemical behavior of CYC in aqueous solution was herein investigated in a "merry-go-round" reactor under a 300 W high-pressure mercury lamp. Twenty-five photodegradation products were identified via UPLC-TOF-ESI-MS/MS. The results suggested that NTN32692, the precursor of CYC was the predominant photodegradation product. CYC photodegrades via a more complex mechanism than imidacloprid and four potential photodegradation pathways were proposed.

Table of Contents Materials and Methods S2 General Procedure for the Synthesis of Dihydropyrrolo[1,2-a]imidazol-one 1 S2 Characterization data of Dihydropyrrolo[1,2-a]imidazol-one 1 S2 General Procedure for the Synthesis of N-Substituted imidazol-6-ones 1b-1p S3 Characterization data of imidazol-6-ones 1b-1p S3-S6 General Procedure for the Synthesis of N-phenyl imidazol-6-one 1r S7 Characterization data of N-phenyl imidazol-6-one 1r S7 General Procedure for the Preparation of Tetrahydropyrrolotriazepin-8-ones 5a-5q S7 Characterization data of Tetrahydropyrrolotriazepin-8-ones 5a-5q S8-S13 S2 Materials and Methods: Melting points (mp) were recorded on a Büchi B540 apparatus (Büchi Labortechnik AG, Flawil, Switzerland) and are uncorrected. Nuclear Magnetic Resonance (NMR) spectra were recorded on a Bruker AM-400 ( 1 H at 400MHz, 19 F at 376 MHz and 13 C at 100MHz) spectrometer with DMSO-d 6 as the solvent and TMS as the internal standard. Chemical shifts are reported in δ (parts per million) values. Coupling constants n J were reported in Hz. High-resolution mass spectra were recorded under electron impact (70 eV) condition using a MicroMass GCT CA 055 instrument. Analytical thin-layer chromatography (TLC) was carried out on precoated plates (silica gel 60 F 254 ), and spots were visualized with ultraviolet (UV) light. X-ray diffraction was performed with a Bruker Smart 1000 instrument. The following abbreviations were used to explain the multiplicities: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet. Unless otherwise indicated, all common reagents and solvents were used as obtained from commercial suppliers without further purification.General Procedure for the Synthesis of Dihydropyrrolo[1,2-a]imidazol-one 1 2-(nitromethylene)imidazolidine (12.9 g, 100 mmol), prepared using the previously reported method, was dissolved in dichloromethane (150 ml), and then methylglyoxal (120 mmol) was added. The mixture was stirred at room temperature for 1 h. The precipitate formed was filtered and washed with acetone to provide tetrahydro-1H-pyrrolo[1,2-a]imidazole-5,6-diol as a white solid (15.0 g, 75%). Then AlCl 3 (7.5 mmol) was added to a solution of tetrahydro-1H-pyrrolo[1,2-a]imidazole-5,6-diol (75 mmol) in acetone (150 ml) and the progress of the reaction was monitored by TLC. After completion, the solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography (DCM :MeOH = 15:1) to give the pure product 1. Characterization data of Dihydropyrrolo[1,2-a]imidazol-one 15-Methyl-7-nitro-2,3-dihydro-1H-pyrrolo[1,2-a]imidazol-6(5H)-one (1).

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