Synthesis, crystal structure and biological activity of a novel anthranilic diamide insecticide containing allyl ether

In search of environmentally benign insecticides with high activity, low toxicity and low residue, a series of novel anthranilic diamides containing allyl ether were designed and synthesized. All the compounds were characterized by ¹H NMR spectroscopy, HRMS or elemental analysis. The single crystal structure of 18e was determined by X-ray diffraction. The insecticidal activities of the new compounds were evaluated. The results showed that some compounds exhibited excellent insecticidal activities against Lepidoptera pests. Among this series compounds, 18l showed 100 % larvicidal activity against Mythimna separate Walker and Plutella xylostella Linnaeus at the test concentration.     

Synthesis of novel nithiazine analogues containing the 1,4-dihydropyridine structure,and their bioactivity as insecticides

A series of novel nithiazine analogues bearing the 1,4-dihydropyridine structure have been designed and synthesized by reaction of nithiazine, malononitrile or ethyl cyanoacetate, and benzaldehyde. The synthesized compounds were identified by ¹H NMR and IR spectroscopy, and elemental analysis. Preliminary bioassays indicated that most of the compounds had moderate insecticidal activity against Aphis craccivora. The relationship between molecular structure and biological activity is discussed.     

Design,Synthesis, and Biological Screening of Novel Anthranilic Diamides

Three series of new anthranilic diamide derivatives containing sulfide, N‐cyanomethylsulfilimine, and N‐cyanomethylsulfoximine groups were designed and synthesized by combining the active substructures of anthranilic diamides and sulfoxaflor. The structures of all newly synthesized compounds were confirmed by IR and ¹H/¹³C‐NMR, and some of them were confirmed by elemental analysis or HRMS too. The synthesized compounds were screened for their insecticidal and fungicidal activities. Bioasssay results indicated that some of the synthesized compounds possessed certain degrees of insecticidal activity against Mythimna separata. However, some compounds exhibited good fungicidal activity against Sclerotinia sclerotiorum.     

Design,Synthesis, Biological Evaluation and SARs of Novel N‐Substituted Sulfoximines as Potential Ryanodine Receptor Modulators

The sulfoximine group has been evaluated as a pharmacophore. Introducing the sulfoximine structure into medicinal compounds as exciting motifs has brought opportunities in drug discovery. In order to develop new ryanodine receptor (RyR) modulators, a series of phthalamides containing sulfoximine derivatives were designed, synthesized, and evaluated against oriental armyworm and diamondback moth for their insecticidal activities. These studies helped to elucidate the electronic and structural requirements around the sulfoximine motif for insecticidal activity. All new structures were synthesized and characterized by ¹H NMR, ¹³C NMR, HRMS and bioassay and a preliminary structure − activity relationship (SAR) was discussed. The biological assessment indicated that most title compounds showed good to excellent larvicidal activities. Compounds Ia , Ie , and If gave excellent insecticidal activity against oriental armyworm, which showed 100% larvicidal activity at 0.5 mg/L. All compounds showed 100% larvicidal activity at 0.1 mg/L against diamondback moth. In particular, the larvicidal activities of Ie , If , and Ih at 0.0001 mg/L were 50%, 20%, and 40%, respectively, reaching an activity as high as that of the commercial flubendiamide (40%, 0.0001 mg/L). Therefore, Ia , Ie , If and Ih could be considered as new lead structures for the development of new ryanodine receptor (RyR) modulators.     

Novel Heterocyclic Compounds Containing Sulfur: Synthesis and Insecticidal Activity of (2-Chlorothiazol-5-yl)methyl 2-Phenyliminothiazolidines

A series of new (2-chlorothiazol-5-yl)methyl 2-phenyliminothiazolidines were designed and synthesized. All new compounds were characterized by ¹ H NMR and, in some cases, by ¹³ C NMR, IR, and HRMS. They are soluble in most organic solvents, which makes them easier to use. A preliminary bioassay showed that some of the new compounds display insecticidal activity against third-instar larvae of Cx. pipiens pallens at 50 mg/L and moderate insecticidal activity against A. craccivora at 1000 mg/L.     

Synthesis, structure and insecticidal activity of some novel amides containing N-pyridylpyrazole

A novel series of amides containing N-pyridylpyrazole were designed and synthesized. All of the compounds were characterized and confirmed by IR, ¹H NMR, ¹³C NMR, MS and elemental analysis. The single crystal structure of 9d was determined by X-ray diffraction. The bioassay tests showed that the title compounds exhibited good insecticidal activities against Mythimna separata Walker, diamondback moth and Laphygma exigua Hübner.     

Synthesis and insecticidal activity of anthranilic diamides with hydrazone substructure

A series of anthranilic diamides with a hydrazone substructure was synthesised and characterised using ¹HNMR, ¹³C NMR, IR and elemental analyses. The in vitro insecticidal activity of all the compounds was tested against Plutella xylostella. The results showed the synthesised compounds to possess good insecticidal activity. The LC₅₀ values of compounds VIIg, VIIl, VIIm, VIIn exhibited excellent insecticidal activities, with the LC₅₀ affording 7.92 mg L^?1, 12.01 mg L^?1, 0.62 mg L^?1 and 10.71 mg L^?1, respectively. These may prove to be useful as potential insecticidal agents.     

Synthesis and Insecticidal Evaluation of Novel N‐Pyridylpyrazolecarboxamides Containing Different Substituents in the ortho‐Position

In order to look for novel insecticides containing N‐pyridylpyrazole, ten novel pyrazolecarboxamides containing different ortho‐substituents in the aniline part were synthesized, and their structures were characterized by ¹H NMR, ¹³C NMR and HRMS. The single crystal structure of 10b was determined by X‐ray diffraction. Their evaluated insecticidal activity against oriental armyworm (Mythimna separata) indicated that all the compounds exhibited moderate insecticidal activities.     

The Synthesis and Biological Activities of N-(3-pyridylmethyl) N ′-(trans-2-thio-4-substitutedphenyl- 5,5-dimethyl-1,3,2-dioxaphosphinane-2-yl)thioureas

A series of novel title compounds were synthesized by the addition reaction of trans 2-isothiocyano-4-substitutedphenyl-5, 5-dimethyl-1,3,2-dioxaphosphinane 2-sulfide to 3-aminomethylpyridine or 2-chloro-5-amino methylpyridine. Their structures were confirmed by ¹H NMR, ³¹P NMR, IR, MS, and elemental analyses. Results of preliminary bioassay showed that all new compounds possess good fungicidal activity and insecticidal activity to some extent.     

Synthesis of 1,3-dithiolane-containing nitromethene compounds and their biological activity as insecticides

1,3-Dithiolane-containing nitromethylene derivatives, as candidates for screening as neonicotinoid insecticides, were synthesized by reaction of compound (4) with 1,2-ethanedithiol. Compounds 7a–g were obtained via Mannich reaction of (E)-1-((1,3-dithiolan-2-yl)methyl)-2-(nitromethylene)imidazolidine (6), primary amines and formaldehyde. The synthesized compounds were identified by ¹H NMR, IR spectroscopy and elemental analysis. Preliminary bioassays indicated that most of the compounds had moderate insecticidal activity against Aphis craccivora. The relationship between molecular structure and biological activity is discussed.     

Design,Synthesis and Biological Activities of Novel Anthranilic Diamide Insecticide Containing Trifluoroethyl Ether

Two series of novel anthranilic diamide insecticide containing trifluoroethyl ether were designed and synthesized, and their structures were characterized by ¹H NMR spectroscopy, elemental analysis and single crystal X‐ray diffraction analysis. The insecticidal activities of the new compounds were evaluated. The results of bioassays indicated that some of these title compounds exhibited excellent insecticidal activities. The insecticidal activities of compounds 19a , 19b , 19d , 19g , 19k and 19m against oriental armyworm at 2.5 mg·kg^?1 were 100%. The larvicidal activities of 19a , 19b , 19c , 19d , 19e , 19g and 19n against diamond‐back moth were 100% at 0.1 mg·kg^?1. Surprisingly, most of them still exhibited perfect insecticidal activity against diamond‐back moth when the concentration was reduced to 0.05 mg·kg^?1, which was higher than the commercialized Chlorantraniliprole.     

Synthesis,antifungal and insecticidal activity of novel [1,2,4]triazolo[4,3-<Emphasis Type="Italic">a</Emphasis>]pyridine derivatives containing a sulfide substructure

A series of [1,2,4]triazolo[4,3-a]pyridine derivatives bearing a sulfide substructure was designed, synthesized and characterized via ¹H·NMR, ¹³C·NMR, IR and elemental analyses. Bioassay Results indicated some of the derivatives displayed good fungicidal activity on Rhizoctonia cerealis, moderated insecticidal activity against Plutella xylostella and good insecticidal activity on Helicoverpa armigera. The inhibitory effects of compounds 4g and 4u against Rhizotonia cerealis were 70.9% at 50 μg mL^?1; the IC₅₀ values of compounds 4d and 4s against Plutella xylostella were 43.87 and 50.75 μg mL^?1, respectively. And the IC₅₀ values of compounds 4d, 4q, and 4s on Helicoverpa armigera were 58.3, 77.14 and 65.31 μg mL^?1, respectively, which were better than that of commercial chlorpyrifos (103.77 μg mL^?1).     

2-氧代-2-[(2-氯-5-吡啶甲氨基)(芳基)甲基]-4-芳基-5,5-二甲基-1,3,2-二氧膦杂环己烷的合成及其生物活性研究

通过类Mannich 反应“一锅法”合成了10个未见文献报道的含吡啶基的环状α-氨基膦酸酯, 其结构经¹H NMR, ³¹P NMR, IR, MS和元素分析确证. 测定了该系列化合物的杀虫、杀菌和除草活性, 结果表明, 所测化合物的杀虫活性不太好, 但所有化合物在药液浓度为1.0×10^－4 g/mL 时都具有较好的除草活性, 部分化合物在5.0×10^－5 g/mL时显示出良好的杀菌活性.     

Synthesis and Insecticidal Evaluation of Novel Phthalic Diamides Containing 1,2,3‐Triazoles via Click Reaction

A series of novel phthalic diamide derivatives containing 1,2,3‐triazole moiety were synthesized using one‐pot click chemistry approach and characterized by ¹H NMR and HRMS. The insecticidal activity against armyworm (Mythimna separata), Tetranychu scinnabarinus and cowpea aphid (Aphis craccivora) was evaluated. Compounds 4II‐a and 4II‐i showed 50% insecticidal activity against armyworm (Mythimna separata) at the concentration of 4 mg/L and one‐third of the compounds had moderate activity against Tetranychus cinnabarinus at 500 mg/L.     

Quinoline and 2-nitroimino-1, 3-diazacycloalkane hybrids: Design,synthesis and insecticidal activity

A library of new hybrid molecules comprising quinoline, 2-nitroimino-1, 3-diazacycloalkane motifs were designed and synthesized as plausible neonicotinoid analogues. These compounds were synthesized from 2-chloro/aryloxy-3-formyl quinolines and guanidine nitrate with the coupling of 2-chloro/aryloxy-3-(chloromethyl)quinolines, 2-nitroimino-1, 3-diazacycloalkanes under phase transfer catalysis (PTC) as crucial step. All the compounds were obtained in excellent yields (80–90%) and were characterized by ¹H, ¹³C NMR and mass spectrometry. The newly generated compounds were screened for insecticidal activity against aphids in safflower field and some of them displayed moderate activity.     

Design,Synthesis and Biological Evaluation of Novel Thienylpyridyl- and Thioether-Containing Acetamides and Their Derivatives as Pesticidal Agents

Referring to the structural information of the “hit” compound A from the reported pharmacophore-based virtual screening, a series of novel thienylpyridyl- and thioether/sulfoxide/sulfone-containing acetamide derivatives have been designed and synthesized. The structures of new compounds were confirmed by ¹H NMR, ¹³C NMR and HRMS. The single-crystal structure of A was firstly reported. All the new synthesized compounds were evaluated for insecticidal activities on Mythimna separata Walker and Plutella xylostella L. Through a step-by-step structural optimization, the high insecticidal agents, especially towards Plutella xylostella L., have been found, and thienylpyridyl- and sulfone/thioether-containing acetamides Iq, Io, Ib and A, which are comparable with the control insecticides cartap, triflumuron and chlorantraniliprole in the present study, can be used as novel lead structures for new insecticides innovation research. In addition, some of the compounds, e.g., A, Ih, Id, Io and Iq, also exhibited favourable fungicidal activities against Physalospora piricola, Rhizoctonia cerealis and Sclerotinia sclerotiorum and would provide useful guidance for the design and development of new fungicides.     

Structure-Based Bioisosterism Design,Synthesis, Biological Activity and Toxicity of 1,2,4-Oxadiazole Substituted Benzamides Analogues Containing Pyrazole Rings

In order to discover pesticidal lead compounds with high activity and low toxicity, a series of novel benzamides substituted with pyrazole-linked 1,2,4-oxadiazole were designed via bioisosterism. The chemical structures of the target compounds were confirmed via ¹H NMR, ¹³C NMR and HRMS analysis. The preliminary bioassay showed that most compounds exhibited good lethal activities against Mythimna separate, Helicoverpa armigera, Ostrinia nubilalis and Spodoptera frugiperda at 500 mg/L. Particularly in the case of Mythimna separate, compound 14q (70%) exhibited obvious insecticidal activity. In addition, compound 14h demonstrated good fungicidal activity against Pyricularia oryae with an inhibition rate of 77.8%, and compounds 14e, 14k, 14n and 14r also showed certain antifungal activities (55.6–66.7%). The zebrafish toxicity test showed that the LC₅₀ of compound 14h was 14.01 mg/L, which indicated that it may be used as a potential leading compound for further structural optimization.     

Synthesis,insecticidal activities,and SAR studies of novel piperazine-containing heterocyclic mono-/di-/tri-amide derivatives

Diamide compounds such as chlorantraniliprole, a famous anthranilic diamide insecticide targeting the insect ryanodine receptor (RyR), have received continuous attention in pesticide research during the past 15 years owing to their excellent insecticidal potentials. With the aim of discovering new heterocyclic pesticides used for crop protection, based on the structural information of compound M from the reported pharmacophore-based virtual screening for RyR insecticides and diamide compound, a series of new heterocyclic mono-, di-, and tri-amide derivatives containing piperazine moiety have been synthesized in this paper. The new compounds were identified and confirmed by melting point, ¹H NMR, ¹³C NMR and HRMS. Compound M was firstly validated for insecticidal activities, and the new synthesized compounds were all made comprehensive insecticidal evaluations against diamondback moth and oriental armyworm. The bioassay results showed that some of the compounds exhibit favorable insecticidal potentials, particularly some novel piperazine-containing heterocyclic mono-/di-/tri-amide derivatives such as 8g, 14a, 15a, 15g, 15i, 15j, 15k, 15l, and 15m could be used as new insecticidal leading structures for further study (e.g., towards diamondback moth, 15i-15m LC₅₀: 0.0022−0.0081 mg/L). The structure-activity relationships of the compounds discussed in detail provide useful guidance for further design and development of new insecticides.     

Design,Synthesis, and Insecticidal Activity of 1,5‐Diphenyl‐1‐pentanone Analogues

Three series of novel 1,5‐diphenyl‐1‐pentanone derivatives were designed and synthesized. Their structures were characterized by IR, ¹H NMR techniques, and elemental analysis. The insecticidal activities of the new compounds were preliminarily evaluated. The bioassay results indicated that the compounds X11 – X30 displayed better aphicidal activity against Aphis gossypii than compounds X1 – X10 and the lead compound (E)‐1,5‐diphenyl‐1‐penten‐1‐one ( A ). The inhibitory rates of compounds X6 and X29 were 100% against Plutella xylostella (L.) at 600 mg·L^?1. Compounds X12 , X13, X19 , X24, X25 , X26 and X27 showed higher insecticidal activity against Tetranychus cinnabarinus (Boisduval) at 600 mg·L^?1 than the lead compound ( A ).     

Design,Synthesis, and Bioassay of Novel Compounds of Isolongifolenone Oxime Derivatives

A succession of new isolongifolenone oxime derivatives have been designed and synthesized. The structures of these compounds were identified by IR, ¹H‐NMR, ¹³C‐NMR, mass spectra, and elemental analysis. The bioassays of antibacterial, antifungal, and insecticidal activity were carried out. The in vitro antibacterial and antifungal activities were evaluated by the disk diffusion method, and the minimum inhibitory concentration was determined by the microdilution method, while the insecticidal activity was tested by the spraying method or the straw impregnation method. The results of bioassays showed that compound 3f was more active in resisting all the tested bacterial and fungal organisms when compared to the standard drug amoxicillin at the lowest concentration of 31.3 μg/ml. Compound 4 , synthesized by Beckmann rearrangement reaction of isolongifone oxime, exerted moderate insecticidal activity against soybean aphid. Furthermore, compound 3m exhibited more activity in killing armyworms than the standard drug flucycloxuron at the concentration of 0.5 mg/l.