Design,synthesis and insecticidal activities of novel anthranilic diamides containing fluorinated groups as potential ryanodine receptors activitors

In order to search for novel potent and environmentally benign insecticides, a series of anthranilic diamides containing various fluorinated groups were designed and synthesized. Their structures were confirmed by ¹H NMR, ¹³C NMR, ¹⁹F NMR, elemental analysis, HRMS or mass spectra. Their insecticidal activities against oriental armyworm (Mythimna separata) and diamondback moth (Plutella xylostella) were evaluated. The preliminary structure-activity relationship (SAR) was discussed in detail. The biological assay indicated that most of the compounds exhibited moderate to excellent insecticidal activities. Especially, Ia showed high larvicidal activity against oriental armyworm. Meanwhile, Iu had better larvicidal effects against diamondback moth than commercial chlorantraniliprole.     

Design, synthesis and insecticidal activity of novel anthranilic diamides with benzyl sulfide scaffold

A series of novel anthranilic diamides with benzyl sulfide scaffold were synthesized,in which N-pyridylpyrazole moiety generally regarded as key pharmacophore was abandoned.The target compounds were characterized by ¹H NMR,¹³C NMR,¹⁹F NMR and HRMS.The preliminary bioassays indicated that half of the title compounds were endowed with good insecticidal activities against armyworm（Mythimna sepatara） at the concentration of 500 mg/L,Exhilaratingly,the synthesized compound 3a was also active against Tetranychus cinnabarinus at 100 mg/L.The difference in activities between the target compounds was influenced by the substituents,which provided some hints for further investigation on structure modifications.     

Synthesis,insecticidal activities and SAR studies of novel anthranilic diamides containing trifluoroethoxyl substituent and chiral amino acid moieties

Based on the structures of ryanodine receptors (RyRs) activators anthranilic diamide insecticidal agents and FKI- 1033, a series of 18 novel trifluoroethoxyl-containing chiral anthranilic diamides Ia–i and IIa–i were synthesized. Their insecticidal activities were evaluated systematically and the SAR was discussed.     

Design,synthesis and insecticidal activities of novel anthranilic diamides containing polyfluoroalkyl pyrazole moiety

In order to discover new molecules with good insecticidal activities, a series of anthranilic diamides containing polyfluoroalkyl pyrazole were designed and synthesized, and their structures were characterized by ¹H NMR and HRMS. Bioassays demonstrated that some of the title compound exhibited excellent insecticidal activities. The larvicidal activities of compound 8a, 8c, 8g, 8k and 8l against Mythimna separata Walker were 100% at 0.8 mg/L. The insecticidal activities of compound 8a, 8c, 8e, 8g, 8k and 8l against Plutella xylostella Linnaeus were 100% at 0.4 mg/L. Surprisingly compounds 8a and 8c still showed 100% larvicidal activities against Plutella xylostella Linnaeus at 0.08 mg/L comparable to the commercialized Chlorantraniliprole. The LC₅₀ of compound 8a and 8c against M. separata is 0.048 and 0.043 mg/L respectively.     

吲哚基丁烯酮缩氨基硫脲配合物的合成及生物活性

缩氨基硫脲类Schiff碱化合物因具有显著的抗菌和抗肿瘤等活性而受到广泛关注,研究发现很多这类化合物与金属离子形成配合物以后,生物活性明显增强。例如,3-乙氧基-2-氧代丁醛双缩氨基硫脲（H2KTs）单独用于治疗大鼠腹水癌瘤没有效果,而H2KTs与铜的配合物则可明显抑制大鼠腹水癌瘤。由于研究这类化合物有重要意义,考虑到吲哚类化合物往往出具有多种生物活性,我们利用拼合原理设计合成了一种带有吲哚基团的缩氨基硫脲Schiff碱配体,并制备了其铜、镍、锌、钴四种边渡金属的配合物,并对配体和配合物的抗菌、抗种瘤活性进行了测试。     

Bioactive conformation analysis of anthranilic diamide insecticides: DFT-based potential energy surface scanning and 3D-QSAR investigations

Anthranilic diamides are fasting growing class insecticides in modern crop protection for their high activity, low ecotoxicity, and broad insecticidal spectra. However, the bioactive conformations of anthranilic diamides are still unclear until now. In the present study, DFT-based potential energy surface scanning was used to detect the low energy conformations of chlorantraniliprole, then were used respectively in the structure alignment for a series of anthranilic diamide compounds followed by detailed CoMFA and CoMSIA analyses. Finally, the bioactive conformations of anthranilic diamide insecticides were revealed from a series of low energy conformations, which might provide some clues for future insecticide design.     

Synthesis,structure and antiproliferative activity of organometallic iridium(III) complexes containing thiosemicarbazone ligands

A series of half‐sandwich iridium complexes ( 1 – 4 ) with thiosemicarbazone ligands in two types of coordination modes were synthesized and characterized. The molecular structures of compounds 1 , 2 and 3 were determined using single‐crystal X‐ray diffraction analysis. The nature of the complexes was studied using density functional theory calculations. The stability of the complexes was investigated using UV–visible absorption spectroscopy. The compounds were further evaluated for their in vitro antiproliferative activities against HeLa, HepG2, CNE‐2, SGC‐7901, KB and HEK‐293 T cell lines. Compound 2 displays the highest antiproliferative activity among the other analogues and cisplatin.     

Synthesis,bioactivity, action mode and 3D-QSAR of novel anthranilic diamide derivatives

Several newly synthesized anthranilic diamide derivatives were found to exhibit excellent bioactivity. The action mode test and 3D-QSAR analysis provided valuable information for evaluation and future design of anthranilic diamide insecticides.     

Preparation and properties of triorganostannylmethyl 2,3:5,6-di-O-isopropylidene-α-D-mannofuranosides; pesticidal and fungicidal activities of triphenylstannyl-carbohydrate derivates

The synthesis of trioganostannylmethyl 2,3:5,6-di-O-isopropylidene-α-D-mannofuranoside (compound 3, R*OCH₂SnR₂R′:R?R′?Me or Ph) from D-mannose is reported. The compound 3 (R?R′?Ph) is transmetallated by PhLi to compound 5, R*OCH₂Li, Which can be trapped by HgCl₂ [as (R*OCH₂)₂Hg] and by ketones, R³COMe [as compound 7, R*OCH₂CR³MeOH]. Two stereoisomers of this compound (7a, R³?Ph) were formed in a ratio of 40:60, indicating some asymmetric induction, arising from the chiral R* moiety. Reactions of compound 3, (R?R′?Ph), with I₂, HO₂CCF₃ and Cl₂PtCOD result in Ph–Sn bond cleavage and formation of compound 3 with R?Ph; R′?I, OCOCF₃ and Cl respectively. Reactions of compound 3 (R?R′?Me) with electrophiles can lead to cleavage of either of both types of C–Sn bonds present (e.g. by I₂, Br₂, Cl₂PtCOD or SnCl₄) or to attack at the C₅–C₆ protecting group with release of acetone (e.g. by CF₃CO₂H, SO₂ or CH₃COCl). Pesticidal and fungicidal activities of compound 3(R?R′?Ph) as well as of 1,2:5,6-di-O-isopropylidene-3-O(triphenylstannylmethyl)-α-D-glucofuranose (compound 2, R?Ph) and methyl 4, 6-O-benzylidene-2-deoxy-2-triphenylstannyl-α-D-altropyranoside (compound 1, R?Ph) are reported.     

两个基于多金属氧酸盐和水杨醛缩氨基硫脲的有机-无机杂化配合物的合成与晶体结构

采用自然蒸发法,合成了2个新颖的有机-无机杂化配合物[C_8H_6N_3S]_2[H_2Mo_2O_7](1)和[CoⅡ(C_8H_8N_3OS)_2]_2[H_3PW_(12)O_(40)]·4DMF(2),并对其进行了元素分析、IR、TG和单晶X-射线衍射表征.结果表明:化合物1是由1个双核多阴离子[H2Mo2O7]2-与2个有机组分[C_8H_6N_3S]+通过共价键形成的一维链状结构;化合物2是由水杨醛缩氨基合钴与DMF分子及多酸阴离子通过氢键作用形成的三维网状结构,其中水杨醛缩氨基硫脲合钴呈风车型.     

水杨醛缩氨基硫脲合钴(Ⅱ)的晶体结构及其荧光性质

在甲醇和DMF溶剂里,以Schiff碱水杨醛缩氨基硫脲(简写为HL)和六水二氯化钴合成了配合物[CoHL2].H2O.DMF.在配合物[CoHL2]中,钴(Ⅱ)原子具有扭曲的N2O2S2八面体配位构型,晶体通过分子间氢键作用形成二维的无限网状结构.红外光谱表明,配体在形成配合物后,νS=O,νC=O和νC=N红移.荧光光谱表明,配合物金属对配体n-π*激发引起的荧光发射峰有较大的影响.     

Synthesis of novel 1,3,4-oxadiazole derivatives containing diamides as promising antibacterial and antiviral agents

In this paper, a variety of novel 1,3,4-oxadiazole derivatives possessing diamides were synthesized and tested for their antibacterial and antiviral activity. Preliminary antibacterial assays indicated that some intermediates and title compounds displayed excellent inhibition effects against plant pathogens Xanthomonas oryzae pv. oryzae (Xoo) and Xanthomonas axonopodis pv. citri (Xac). Further studies revealed that compound H15 exhibited the strongest activities against Xoo and Xac with minimal EC₅₀ values of 0.7 and 5.9 μg/mL, respectively. Antiviral bioassays suggested that some of these structures displayed appreciable curative activities and moderate protective effects against tobacco mosaic virus (TMV) in vivo. Among them, compound H8 exerted the best chemotherapeutic effect against TMV with the curative rate of 60.0% at 500 µg/mL, which was comparable with those of commercial agricultural antiviral agent ningnanmycin (54.2%). Given their significant biological activities, this kind of compound could serve as new leading compounds in the study of antibacterial and antiviral chemotherapy.     

含1,2,3-噻二唑的邻甲酰胺基苯甲酰胺类化合物的合成、晶体结构与生物活性

以取代邻氨基苯甲酸为起始原料, 设计并合成了一系列未见文献报道的含1,2,3-噻二唑的邻甲酰胺基苯甲酰胺类化合物. 所有化合物的结构均经元素分析和1H NMR确证, 并且采用X射线单晶衍射分析方法测定了化合物7g的结构. 初步的生物活性试验结果表明, 部分化合物具有一定的杀菌活性.     

N-[4-氯-2-取代氨基甲酰基-6-甲基苯基]-1-芳基-5-氯-3-三氟甲基-1H-吡唑-4-甲酰胺的合成及生物活性

通过改变传统氯虫酰胺中吡唑环上氨基甲酰基与吡啶环之间的相对位置, 或以其它芳环取代原分子中的吡啶环, 设计合成了24个结构新颖的N-[4-氯-2-取代氨基甲酰基-6-甲基苯基]-1-芳基-5-氯-3-三氟甲基-1H-吡唑-4-甲酰胺类化合物. 所有目标化合物的结构均通过¹H NMR谱、 元素分析或高分辨质谱表征确定. 初步的生物活性测试结果表明, 部分化合物对东方粘虫具有较好的杀虫活性, 其中化合物6m在浓度为50 mg/L时具有80%的杀虫活性. 同时, 在浓度为50 mg/L时目标化合物对5种常见病菌具有明显的抑制作用, 其中化合物6n和6x对苹果轮纹菌的抑菌率达62.1%.     

Synthesis,characterization and antitumor activities of some novel thiazinones and thiosemicarbazones derivatives

Abstract

Two series of thiazinone and thiosemicarbazone derivatives (1-12) were synthesized using 2,4-diaryl-3-azabicyclo[3.3.1]nonan-9-ones (ABNs) and 3–alkyl–2,6–diarylpiperidin–4–ones as the starting materials. The structures of newly synthesized compounds were established on the basis of FT–IR, NMR spectroscopy and mass spectrometry. From the spectroscopic data, we identified that the cyclization reaction of thioamide with dialkyl acetylenedicarboxylate selectively gives six membered methyl 2-(2-(2,4-disubstituted-3-azabicyclo[3.3.1]nonan-9-ylidene)hydrazinyl)-4-oxo-4H-1,3-thiazine-6-carboxylates (1-6). In order to investigate the antitumor activities of the synthesized compounds, in vitro cytotoxicity studies were carried out using human prostate cancer cell lines. Tested compounds showed good/moderate activities against cancer cell lines and further investigation carried out by live/dead assay.     

Synthesis and Insecticidal Evaluation of Novel Anthranilic Diamides Derivatives Containing 4‐Chlorine Substituted N‐Pyridylpyrazole

To search for potent insecticides targeting at ryanodine receptors (RyRs), a series of novel anthranilic diamides analogs containing 4‐chlorine N‐pyridylpyrazole were designed and synthesized. Their insecticidal activities were evaluated and the preliminary structure‐activity relationships (SARs) were discussed. The insecticidal results showed that some of the compounds (8a—8h, 8m, 8n) exhibited good larvicidal activities against oriental armyworm at 2.5 mg·L^–1, and compound 8m possessed 60% insecticidal activity at 0.5 mg·L^–1. For diamondback moth, 8m exhibited better activity than Chlorantraniliprole at a hundred fold preference. The calcium imaging technique experiment results suggested that compound 8m could increase the intracellular [Ca²⁺]_i. With the neurons preincubated experiment, the results confirmed that the target of this series of compounds could be RyRs in the central larvae neurons of oriental armyworm. The results indicated that compound 8m could respond as a potential modulator of the insect ryanodine receptor.     

Design,synthesis, and pesticidal activities of novel pyrimidin-4-amine derivatives containing trifluoroethyl sulfide moiety

In order to overcome the problem of pesticide resistance, it is necessary to discover novel pesticides with new mechanisms of action. Herein, a series of novel pyrimidin-4-amine derivatives containing trifluoroethyl sulfide moiety were designed and synthesized. Bioassays indicated that the title compounds synthesized possessed excellent acaricidal activity against Tetranychus urticae and fungicidal activity against Erysiphe graminis and Puccinia sorghi. Especially, the acaricidal activity of 5-chloro-6-(difluoromethyl)-N-(2-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenoxy)ethyl)pyrimidin-4-amine (compound T4 , LC₅₀ = 0.19 mg/L) against T. urticae was close to commercial acaricide cyenopyrafen, and the fungicidal activity of 5-chloro-6-(difluoromethyl)-2-methyl-N-(2-(3-((2,2,2-trifluoroethyl)thio)phenoxy)ethyl)pyrimidin-4-amine (compound T15 , EC₅₀ = 1.32 mg/L) against P. sorghi. was superior to commercial fungicide tebuconazole. The synthesis and characterization of these compounds were given and the structure–activity relationships were discussed.     

Synthesis, characterization and optical band gap of NiO nanoparticles derived from anthranilic acid precursors via a thermal decomposition route

This study focuses on the preparation and characterization of single phase NiO nano particles. Four nickel anthranilic acid complexes were synthesized by the semi-solid phase reaction method as precursors for the preparation of NiO nanoparticles via a solid-state decomposition procedure at 700 °C. Thermogravimetric analysis (TGA) was applied to determine the thermal behavior of the precursors and the temperature at which the precursors decompose leaving the oxide. The crystalline structures of the products were investigated by X-ray diffraction (XRD), the morphology of particles by SEM and TEM. The particles size was determined by STM, and the average particle size was found to be 8 nm. Electronic spectra were used to clarify qualitatively the change in absorption band positions on changing the particle size of NiO. The optical band gap of the NiO nanoparticles was calculated and indicated a direct transition. The values of the optical band gap of NiO nanoparticles increase as the particle size decreases.     

哌嗪含磷双取代衍生物的合成及结构表征

以无水哌嗪为原料,合成了9个1,4-位分别带有磷酰化氨基酸和缩氨基硫脲取代基团的哌嗪衍生物,通过1 H NMR、13C NMR、31 P NMR、IR、MS对其结构进行表征.并通过ESI-MS研究目标化合物与细胞色素的弱相互作用,初步评价了他们的生物活性.     

Synthesis under Micromave Irradition and Crystal Structure of 4''-Acetylbenzo-15 -crown-5thiosemicarbazone

The title compound is a bifunctional receptors including a thiourea group and a crown ether ring. Due to many possible potentials as a new class of reagents for membrane transports,ion-selective electrodes as well as reaction catalysts, the design and synthesis of bifunctional receptors for simultaneous binding of cations and anions is of ongoning interest in srprarnolecular chemistry1-5. In bifunctional receptors, the binding sites for anions and cations are covalently linked so as to exhibit allosteric or cooperative complexation where the binding affinity for anions(cations)is modified as a result of the cation(anion) complexation.Literature[6] reported that the ability of the thiourea group to bind anions is significantly enhanced when Na+ is bound to the crown moiety. To date, however only a few receptors of this class have been reported.6-8In this paper, we report an improved procedure under microwave irradiation that gives higher yields of title compound and needs fewer reaction times than traditional method.The structure of this compound was determined by IR ,element analysis and X-ray analysis.Scheme 1 The reaction equationThe crystal belongs to triclinic crystal system, P-1 space group, a=0.9547(0)nm, b=1.3637(3)nm,c=1.6029(3)nm, α =75.33(3) , β =83.62(3) , γ =70.99(3) ,Z=4,Dc=1.335g/cm3,F(000)=816,R1= 0.0557 ,wR2=0.1281. It is assembled into a three-dimensionalsupramolecule by intermolecular hydrogen bonds.