Synthesis,Structure and Biological Activities of Novel 2‐(Trifluoromethyl)‐ 6‐arylimidazo[2,1‐b][1,3,4]‐thiadiazole (bis‐)Mannich Base Derivatives Containing Substitutedpiperazine Moiety

A convenient and practicable method for the synthesis of the novel 2‐(trifluoromethyl)‐6‐arylimidazo[2,1‐b][1,3,4]‐thiadiazole (bis‐)Mannich base derivatives containing various substitutedpiperazine motif has been developed based on the fused‐heterocycle intermediate. The new structures were identified through melting points, ¹H NMR, ¹³C NMR, ¹⁹F NMR, elemental analysis (or HRMS) and X‐ray single‐crystal diffraction. The pesticidal bioassays showed that some of compounds exhibited good fungicidal activities against Cercospora arachidicola, Physalospora piricola and Rhizoctonia cereali at 50 mg/L; some of them displayed favourable insecticidal activities against oriental armyworm (Mythimna separata Walker) at 200 mg/L, particularly, Vk and Vm with mortality rate of 75% and 80% respectively, could be considered as new insecticidal lead compounds for further structural optimization.     

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.     

Synthesis and Insecticidal Activity of New Quinoline Derivatives Containing Perfluoropropanyl Moiety

A series of new quinoline derivatives containing perfluoropropanyl moiety were designed and synthesized. Their structures were confirmed by ¹H‐NMR, MS, and elemental analysis. The bioassay results showed that compound 4e exhibited good insecticidal activity against Plutella xylostella and Mythimna separata at 100 mg/L.     

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.     

Synthesis and Insecticidal Activity of Novel N‐Pyridylpyrazole Carbonyl Thioureas

A series of novel N‐pyridylpyrazole carbonyl thioureas were designed and synthesized. Their structures were characterized by melting points, ¹H NMR, IR and elemental analysis or HRMS. The bioassay tests indicated that some of these compounds exhibited moderate insecticidal activity against Mythimna separata Walker and Culex pipiens pallens. Among 17 compounds, 5n and 5p showed 100% larvicidal activity against Mythimna separata Walker at the test concentration of 100 mg/L.     

新型含N-吡啶基吡唑杂环的邻氨基苯甲酸酯类化合物合成，结构及生物活性研究

设计,合成了8个新的含N-吡啶基吡唑杂环的邻氨基苯甲酸酯类化合物,结构经FTIR, MS, 1H NMR 和元素分析确证,并且采用X-射线衍射分析方法确证了具有较好生物活性的化合物14d的结构。并且对这些化合物进行了杀虫活性测试,结果表明目标化合物在200 µg·mL-1对粘虫 (Mythimna separata Walker)具有一定的杀虫活性,其中14d,14f,14h在1 µg·mL-1对淡色库蚊（Culex pipiens pallens）具有很好的杀幼虫活性。     

Synthesis and Fungicidal Activities of 2,3‐Dimethyl‐4‐(1‐acyloxy)alkoxy‐6‐tert‐butyl‐8‐fluoroquinolines

A series of 2,3‐dimethyl‐4‐(1‐acyloxy)alkoxy‐6‐tert‐butyl‐8‐fluoroquinolines were synthesized by 4‐(tert‐butyl)aniline as the starting material via acylation, substitution, and hydrolysis, and their structures were characterized by ¹H NMR, ¹³C NMR, and HRMS. The fungicidal activity showed that compounds 6c , 6e , and 6f had excellent activity against Sphoaerotheca fuliginea with EC₅₀ values of 38.62, 6.77, and 50.35 mg/L, respectively. The results suggest that this chemotype of compounds warrant further studies as promising fungicide.     

Synthesis and insecticidal activities of O,O-dialkyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carbonyloxy] (aryl) methylphosphonates

A series of novel O,O-Dialkyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carbonyloxy](aryl) methy-lphosphonates I-1–14 were designed and synthesized. The structures of all the title compounds were confirmed by ¹H-NMR, ¹³C-NMR, ³¹P-NMR, IR and elemental analysis. Their insecticidal activities against Mythimna separata and Plutella xylostella were evaluated. The results of bioassays indicated that the title compounds exhibited 20–80% larvicidal activity against Mythimna separata at 1000 mg/L.     

Design,Synthesis, and Insecticidal Activities of Novel Pyranoside Derivatives Targeting at Potential Second Calcium Channel IP3 Receptor

In order to search for potent and environmental friendly insecticides with new modes of action, a series of pyranoside derivatives mimicking D‐myo‐inositol 1,4,5‐trisphosphate (IP₃) were designed and synthesized according to the bioisosteric approach. The biological assay indicated that most of the new compounds showed moderate to good insecticidal activities against oriental armyworm (Mythimna separata) and diamondback moth (Plutella xylostella). Especially, compound 5g displayed 80% larvicidal activity against oriental armyworm at 50 mg/L. Meanwhile, 5a showed 100% and 70% larvicidal activities against diamondback moth at 50 and 25 mg/L, respectively. To further explore the mode of action, calcium imaging technique was applied to study the effects of 5a , 5g , and 5i on the intracellular calcium ion concentration ([Ca²⁺]_i) in central neurons isolated from Spodoptera exigua. The results indicated that the tested compounds released stored calcium ions from endoplasmic reticulum.     

Synthesis and Herbicidal Activity of Novel 4‐Acyl‐2,5‐disubstituted‐3‐hydroxypyrazoles and 4‐Arylcarbonyl‐3‐substitutedisoxazol‐5‐ones

Two series of novel 4‐acyl‐2,5‐disubstituted‐3‐hydroxypyrazoles 3a , 3b , 3c , 3d , 3e , 3f , 3g , 3h and 4‐arylcarbonyl‐3‐substitutedisoxazol‐5‐ones 7a , 7b , 7c , 7d , 7e , 7f , 7g , 7h , 7i were synthesized by the Scotton–Baumann reaction of 2,5‐disubstituted‐2,4‐dihydro‐pyrazol‐3‐ones 1 or 3‐substituted‐4H‐isoxazol‐5‐ones 6 and various acyl chlorides, followed by the Fries rearrangement in the presence of calcium hydroxide and calcium oxide as the catalyst. Their structures were confirmed by IR, ¹H NMR, mass spectroscopy, and elemental analyses. ¹H NMR indicated that compounds 3 existed in enol forms and compounds 7 in keto configurations. The results of preliminary bioassays showed that some of the title compounds 3 and 7 exhibited moderate to good herbicidal activities against Brassica campestris L. at the concentration of 100 mg/L. Isoxazole compounds 7 showed better herbicidal activity against B. campestris L. than pyrazole compounds 3 did at the concentration of 100 mg/L. Moreover, most of the isoxazole compounds displayed higher herbicidal activity against B. campestris L. than Echinochloa crus‐galli. However, these compounds showed weak herbicidal activities at the concentration of 10 mg/L.     

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.     

Synthesis and Insecticidal Activities of 1,3,5‐Trisubstituted‐1,3,5‐hexahydrotriazine‐2‐N‐nitroimines

A new series of 1,3,5‐trisubstituted‐1,3,5‐hexahydrotriazine‐2‐N‐nitroimines ( 3a – 3j ) were designed and synthesized as novel neonicotinoid analogues, and their structures were characterized by ¹H NMR, IR, elemental analysis and MS. The preliminary bioassay tests showed that most of the target compounds had good insecticidal activities against Nilaparvata lugens as well as Aphis medicaginis at 500 mg/L, while compound 3i had 100% mortality against Nilaparvata lugens at 20 mg/L.     

Synthesis,Crystal Structure,and Biological Activity of Novel Anthranilic Diamide Insecticide Containing Propargyl Ether Group

In search of environmentally benign insecticides with high activity, low toxicity, and low residue, a series of novel anthranilic diamide containing propargyl ether were designed and synthesized. All compounds were characterized by ¹H NMR spectroscopy, high‐resolution mass spectrometry, or elemental analysis. The single crystal structure of 18g was determined by X‐ray diffraction. The insecticidal activities against Lepidoptera pests of the new compounds were evaluated. Their insecticidal activities against oriental armyworm (Mythimna separata) and diamondback moth (Plutella xylostella) indicated that most of the compounds showed moderate to high activities at the tested concentration.     

Synthesis and Biological Activity of O‐Methyl Methyl 1‐(Substituted Phenoxyacetoxy)‐1‐(thien‐2‐yl)methylphosphinates

A series of novel O‐methyl methyl 1‐(substituted phenoxyacetoxy)‐1‐(thien‐2‐yl)methylphosphinates 5a , 5b , 5c , 5d , 5e , 5f , 5g , 5h were synthesized. Their structures were confirmed by IR, ¹H NMR, mass spectroscopy, and elemental analyses. The results of preliminary bioassays show that some of the title compounds exhibit moderate to good herbicidal and fungicidal activities. For example, the title compounds 5c , 5d , and 5g possess 90–100% inhibition against the tested plants at the concentration of 10 mg/L and 100 mg/L, whereas the title compounds 5a , 5b , 5c , and 5h possess 70–94% inhibition against Phyricularia grisea and Sclerotinia sclerotiorum at the concentration of 50 mg/L.     

A Convenient Synthesis and Biological Research of Novel 5,6,7,8‐Tetrahydro‐1,6‐naphthyridin‐2(1H)‐one Derivatives Hydrochloride as Cytotoxic Agents

A series of 5,6,7,8‐tetrahydro‐1,6‐naphthyridin‐2(1H)‐one derivatives hydrochloride were obtained using a convenient and mild method from 4‐piperidone monohydrate hydrochloride. The newly synthesized compounds and their derivatives were characterized by ¹H NMR, ¹³C NMR, and high‐resolution mass spectrometry. Furthermore, cytotoxicity in vitro of the synthesized compounds were screened using MTT or CCK8 assay. The results showed that some of the compounds showed potential antitumor activity. Among of them, compound 10a had effects against tumor cells (MOLM‐13), and the half maximal inhibitory concentration value was 76 μmol/L.     

Design,Synthesis and Biological Activities of Novel Benzoyl Hydrazines Containing Pyrazole

In search of environmentally benign compounds with high biological activity, low toxicity and low resistance, 8 novel benzoyl hydrazines containing pyrazole were designed and synthesized. All compounds were characterized by ¹H NMR spectra and HRMS. The preliminary results of biological activity assessment indicated that most of title compounds exhibited certain insecticidal activities against Mythimna separata Walker at 200 mg·L^?1 but excellent fungicidal activities against six fungus at 50 mg·L^?1, which were better than the control.     

Synthesis and Bioactivities Evaluation of Novel Anthranilic Diamides Containing N‐(tert‐Butyl)benzohydrazide Moiety as Potent Ryanodine Receptor Activator

Anthranilic diamides have been proven to be a class of efficacious and safe insecticides targeting ryanodine receptors (RyRs) during the last decade. In order to develop innovative scaffolds with high insecticidal activity, two series of N‐pyridylpyrazole derivatives containing N‐(tert‐butyl)benzohydrazide substructures were designed and synthesized. Their insecticidal activities against oriental armyworm (Mythimna separata) and diamondback moth (Plutella xylostella) were evaluated. Preliminary bioassay results revealed that some of the new compounds exhibited good insecticidal activity against the oriental armyworm and diamondback moth. The mode of action of these compounds were verified using calcium‐imaging technique and the results showed that some new compounds could effectively modulate the insect cytosolic Ca²⁺ level, and break the cellular calcium homeostasis, indicating some of these compounds were potent activators of the RyRs.     

Utility of Benzoxazin‐4‐one and 3‐Aminoquinazolin‐4‐one Derivatives as Precursors for Construction of Potent Insecticidal Heterocycles

In demanding to develop new insecticidal agents, both of 2‐pentylbenzoxazin‐4‐one 1 and 3‐amino‐2‐pentylquinazolin‐4‐one 6 derivatives were subjected to react with different nucleophilic agents, for example, ammonia, o‐phenylenediamine, hydrazine hydrate, and hydroxylamine hydrochloride, and sulfur nucleophile, for example, phosphorous pentasulfide, to construct different heterocyclic systems. The structural elucidations of the synthesized compounds were ascertained from the elemental analyses and the spectral data. Assessment of the biological potency for some of the synthesized compounds as insecticidal agents was evaluated against two different insects named Mythimna separata and Nilaparvata lugens.     

Design,Synthesis, Structure‐Activity Relationship and Insecticidal Activities of Trifluoromethyl‐Containing Sulfiliminyl and Sulfoximinyl Phthalic Acid Diamide Structure

Due to a novel mode action, low toxicity to mammals and low residue characteristics, phthalic acid diamides have aroused considerable interests in agricultural chemistry. With introduction of N‐cyano, N‐trifluoroacetyl, N‐carbamoylsulfiliminyl and sulfoximinyl substituents into phthalamides, 12 novel derivatives containing trifluoromethyl moiety were designed and synthesized. All title compounds were characterized by ¹H NMR and high‐resolution mass spectrometry. The preliminary results of biological activity assessment indicated that some title compounds exhibited moderate to good insecticidal activities against oriental armyworm (Pseudaletia separata Walker). In particular, Va gave higher activity against oriental armyworm and diamondback moth. The present work reported that the new trifluoromethylated diamides incorporating N‐trifluoroacetylsulfoximinyl moieties are potential lead compounds for further structure optimization, providing some insight into the relating structure‐activity relationship.     

Synthesis and Herbicidal Activities of 3‐Trifluoromethyl‐5‐[3‐(trifluoromethyl)phenoxy]‐1,2,4‐Triazol‐4‐Schiff Bases

In order to find novel bleaching herbicide lead compounds, a series of novel 3‐(trifluoromethyl)‐4‐(arylimino)‐5‐[3‐(trifluoromethyl)phenoxy]‐1,2,4‐triazoles were designed and synthesized by the multi‐step reactions. Their structures were confirmed by IR, ¹H NMR, EI‐MS and elemental analyses. The preliminary bioassay indicated that compounds 4b , 4f , and 4h possessed 69.4%, 72.6%, and 88.5% inhibition against Brassica campestris L at the concentration of 100 mg/L. Generally speaking, this type of compounds exhibited weak herbicidal activity and might be not suitable as herbicide lead compound for further optimization.