Synthesis and Herbicidal Activity of 3-Acetyl-4-hydroxy-2,1-benzothiazine Derivatives

In order to develop a novel herbicide containing the 2,1-benzothiazine motif, a series of 3-acetyl-4- hydroxy-2,1-benzothiazine derivatives was synthesized. All the target compounds were confirmed by 1H NMR,13C NMR, and high-resolution mass spectrometry(HRMS).In addition,the crystal structure of compoimd T27 was detemiined by single crystal X-ray diflraction. The bioassay results showed that some of the 3-acetyl-4-hydroxy- 2,1-benzothiazine derivatives(T13, T15, T22, and T24) showed good herbicidal activity at a dosage of 100 pg/mL. Among them,compounds T22 and T24 showed promising post-emergent herbicidal activities against Brassica campestris and Amaranthus retroflexus even at a dosage of 375 g/ha(1ha=104 m^2) in the greeiiliouse test. Studies on the structure-activity relationship demonstrated that the type of acetyl group played an important role in the herbicidal activity, and that the introduction of a phenoxyacetyl group at the 3-position of 2,1-beiizothiazine was beneficial in improving the herbicidal activity. The present study also indicated that 3-phenoxyacetyl-4-hydroxy-2,1-benzothiazine could be a potential lead compound for fiirther development of novel 2,1 -benzothiazine-containing herbicides.     

Synthesis and Biological Evaluation of Novel Saccharin Derivatives Containing 1,2,3-Triazole Moiety

A series of novel saccharin derivatives containing 1,2,3-triazole moiety was synthesized in satisfactory yields. The structures of all the compounds were elucidated and confirmed by Fourier transform infrared(FTIR) spectroscopy, ¹H and ¹³C nuclear magnetic resonance(¹H NMR, ¹³C NMR) spectroscopy, and high resolution mass spectrometry(HRMS). The bioassays indicated that most of the title compounds displayed some extent herbicidal activities at 100 μg/mL.     

含吡唑环的1,2,4-三唑希夫碱类衍生物的合成及生物活性

以自制的4-氨基-4,5-二氢-3-[(3,5-二甲基吡唑-1-基)甲基]-1,2,4-三唑-5-硫酮衍生物为中间体, 与取代苯甲醛反应合成了一系列新型含吡唑环的1,2,4-三唑希夫碱衍生物. 通过红外光谱、 核磁共振波谱、 高分辨质谱、 元素分析及X射线单晶衍射对目标化合物进行了结构表征, 并初步测试了其生物活性. 结果表明, 大部分化合物表现出较好的抑菌活性, 其中化合物G9, G10和G15的抑菌效果优于对照药三唑酮.     

Design,Synthesis and Herbicidal Activity of Novel Sulfonylureas Containing Triazole and Oxadiazole Moieties

Three novel series of 5-substituted sulfonylurea derivatives were designed and synthesized via introducing a triazole or oxadiazole ring at the 5th position of the benzene ring in classical sulfonylurea herbicides. All the target compounds were confirmed by means of ¹H nuclear magnetic resonance(NMR), ¹³C NMR and elemental analysis. The bioassay results show that the target compounds containing an oxadiazole ring at the 5th position display moderate to excellent herbicidal activities against Brassica campestris and Amaranthus retroflexus under soil treatment. Especially, compounds zdk20, zdk21 and zdk22 possess 98.6%, 96.5% and 94.5% inhibition rates, respectively, against Amaranthus retroflexus at a concentration of 75 g/ha(1 ha=1×10⁴ m²) under soil treatment, which approach to those of the commercial herbicide chlorsulfuron.     

Synthesis and Herbicidal Activities of Novel Uracil Derivatives Containing Pyrimidinyl Moiety

In order to find novel protoporphyrinogen oxidase inhibitors with high efficacy, broad-spectrum activity, and safety to crops, nine title compounds（4a-4i） were designed and synthesized by introducing pyrimidine moiety into the uracil skeleton with commercially herbicide butafenacil as the lead compound. Their structures were con- firmed by 1H NMR, IR, mass spectroscopy and elemental analysis. The bioassay results indicate that most of com- pounds 4 tested exhibit good to excellent herbicidal activities against B. campestris, A. retroflexus, E. crusgalli and D. sanguinalis in pre-emergence treatment at a dose of 1.5 kg/ha（1 ha=10^4 m^2）, for example, compound 4i showed 100% inhibition against the four plants tested in pre-emergence treatment at a dose of 1.5 kg/ha. So, this type of skeleton can be used as a valuable lead compound for the further development of a pre-emergent herbicide.     

Synthesis and bioactivity of novel 3-(1-hydroxyethylidene)-5-substituted-pyrrolidine-2,4-dione derivatives

Ten novel 5-substituted derivatives of 3-(l-hydroxyethylidene)pyrrolidine-2,4-dione were synthesized.The compounds were confirmed by IR,:H NMR,MS and elemental analysis.The bioassay indicated that these compounds showed noticeable herbicidal activities,and compounds 6f and 6j exhibited excellent inhibitory activities against the stalk of Echinochloa crusgalli,with EC50 values of 94.4 and 72.7 mg/L,respectively.     

Synthesis and biological activity of novel N-(3-furan-2-yl-1-phenyl-1H-pyrazol-5-yl) amides derivatives

A series of novel N-(3-furan-2-yl-1-phenyl-1H-pyrazol-5-yl) amides derivatives were designed and synthesized. Their structures were confirmed by ¹H NMR, ¹³C NMR and HRMS. All title compounds were evaluated for their herbicidal and antifungal activities. Preliminary bioassay results indicated that the title compounds showed good to moderate herbicidal activity at 1000 mg/L. Compound 6q presented the best activity against Digitaria sanguinalis (L) Scop., Amaranthus retroflexus L. and Arabidopsis thaliana with an inhibition degree of five. Compound 6d also showed an inhibition degree of five against D. sanguinalis. In addition, at 50 mg/L, most compounds exhibited good in vitro antifungal activity against Sclerotinia sclerotiorum, with compound 6c showing over 90% antifungal activity against S. sclerotiorum and Pellicularia sasakii.     

Design,Synthesis and Herbicidal Activity of Novel Sulfonylureas Containing Tetrahydrophthalimide Substructure

To develop novel sulfonylurea herbicides, a series of chlorsulfuron derivatives was designed and synthesized through introducing tetrahydrophthalimide substructure taken from protoporphyrinogen IX oxidase(PPO) inhibitors onto the critical 5-position of the classical benzene ring. The structures of title compounds were confirmed by infrared spectroscopy, ultraviolet spectroscopy, ¹H and ¹³C NMR spectrometry, mass spectrometry and elemental analysis. In addition, the crystal structure of compound II-5 was further determined by X-ray diffraction analysis. Bioassay results showed that individual compounds exhibited good herbicidal activities, especially compound II-8, which displayed 100% inhibition rate against Echinochloa crusgalli at 150 g/ha(1 ha=10⁴ m²) with the method of foliage spray in the pot experiment.     

Design,Syntheses and Biological Activities of Novel Sulfonylureas Containing an Oxime Ether Moiety

Since sulfonylurea is one of the most potent acetohydroxyacid synthase(AHAS) inhibitors, a series of novel sulfonylureas containing an oxime ether moiety was designed and synthesized and their chemical structures were determined by means of ¹H nuclear magnetic resonance(NMR), ¹³C NMR and high-resolution mass spectrometry(HRMS). In the herbicidal bioassay, several compounds showed moderate to good herbicidal activities against dicotyledons, but their activities against monocotyledons decreased. The in vitro antifungal activity was tested at a dosage of 50 mg/L. And the results show that compounds 7l, 7m and 7n exhibit promising antifungal activities against six common plant pathogenic fungi. Further investigations on molecular modification are in progress.     

Improved Antiproliferative Activities of a New Series of 1,3,4-Thiadiazole Derivatives Against Human Leukemia and Breast Cancer Cell Lines

Twenty-two novel 1,3,4-thiadiazole derivatives were synthesized using different aromatic acids as starting materials, followed by cyclization, coupling and deprotection reaction. The structures of all the target compounds were identified by means of ¹H nuclear magnetic resonance(NMR), ¹³C NMR and high resolution mass spectrometer(HRMS). Further biological evaluations were performed for chronic myelogenous leukemia cell and breast cancer cell. The results suggest that most of the target compounds exhibit potent anti-proliferative activities. Especially, compound 5b shows better antiproliferative activities against MDA-MB-231 and K562 cell lines compared with gossypol.     

含芳氧乙酰基和间-三氟甲基苯基的双酰胺化合物的合成及其除草活性

通过组合不同除草作用机制的活性基团,采用芳氧乙酸为酸组分的Ugi四组分反应合成了一系列芳氧乙酰基和间三氟甲基苯基片段的双酰胺化合物3a~3v,采用IR、¹H NMR、EI-MS和元素分析等技术手段对其结构进行了表征。 温室盆栽测试结果表明,部分目标化合物对油菜、反枝苋、稗草和马唐表现出中等至良好的除草活性,如化合物3r在温室盆栽时,在1.5 kg/ha剂量下,在苗前处理时对反枝苋和马唐显示出100%的抑制活性;在苗后处理时对马唐显示出100%的抑制活性。 初步探讨了目标化合物的构效关系。     

Synthesis and biological activities of novel 2-amino-1,3-thiazole-4-carboxylic acid derivatives

A series of novel 2-amino-1, 3-thiazole-4-carboxylic acid derivatives were designed and synthesized. Their structures were confirmed by melting points, IR, ¹H NMR, ¹³C NMR, and HRMS or elemental analysis. Biological activities of all title compounds including fungicidal activity and antivirus activity were evaluated systematically. Preliminary bioassays indicated that these compounds exhibited good fungicidal activity at 50 μg/mL, compounds 4b and 4i exhibited over 50% activity against six fungi tested. Most compounds showed good activity against TMV with different models in vivo at 100 μg/mL. Compounds 4c and 4e stood out with high effects against TMV in vivo in all models tested, including protective, inactivative, curative, and inductive activities. These data demonstrate a new strategy for fungi and virus control.     

三唑酰胺1,4-戊二烯-3-酮衍生物的合成及生物活性

以丙酮和水杨醛为起始原料,设计合成了9个新型含氟1,2,4-三唑酰胺姜黄素类化合物,通过¹H NMR、¹⁹F NMR、IR及元素分析等技术手段对目标化合物进行了结构表征。 采用Airbrush喷雾法进行生物活性测试,结果表明部分化合物具有不同程度的杀虫活性。     

Synthesis and Antifungal Activities of Novel Strobilurin Derivatives Containing Quinolin-2(1H)-one Moiety

To discover novel lead compounds with better antifungal activities, a series of novel strobilurin derivatives containing quinolin-2(1H)-one moiety was designed and synthesized via intermediate derivatization method. Their structures were characterized by means of ¹H nuclear magnetic resonance(¹H NMR), ¹³C NMR and high resolution mass spectrometry(HRMS). The biological assay results indicate that most target compounds exhibit good to excellent fungicidal activities against 10 plant pathogens. Compounds 4d, 5b and 5c possess 94.1%, 83.8% and 80.9% in vitro inhibition respectively against Rhizotonia cereals at the concentration of 50 μg/mL, which are better than that of the control agents. Especially, the inhibition activities of compound 4d against all of the tested fungi approach or exceed those of the controls. The structure-activity relationship was also discussed.     

Synthesis and Bioactivity Evaluation of Novel N-Pyridylpyrazolemethanamine Derivatives

To further explore the structure-activity relationship(SAR) of amide bridge moeity of anthranilic diamides derivatives, a series of N-pyridylpyrazole derivatives was designed, synthesized and their biological activities were evaluated. The chemical structures of novel target compounds were confirmed by ¹H nuclear magnetic resonance (NMR), ¹³C NMR and elemental analyses(EA). Bioassay results of insecticidal activity demonstrated that the target compound 6h displayed 70% lethality rate against oriental armyworms at 200 mg/L. Moreover, most compounds displayed moderate to excellent antifungicidal activities against Fusarium oxysporum f. sp. cucumerinum, Cercospora arachidicola Hori, Botryosphaeria dothidea, Alternaria solani, Gibberella zeae and Phytophthora capsici at 50 mg/L. In particular, compound 6e showed 61.5% and 92.3% inhibition rate against Cercospora arachidicola Hori and Botryosphaeria dothidea, which was superior to the commercial positive control Chlorothalonil. These results will provide a potential clue for exploring novel high-effective agrochemicals.     

Synthesis and biological activities of some fluorine-and piperazine-containing 1,2,4-triazole thione derivatives

A series of fluorine-and piperazine-containing 1,2,4-triazole thione derivatives were synthesized by the Mannich reaction of triazole intermediates with various substituted piperazines and formaldehyde in high yields. Structures of title compounds were confirmed by melting points, IR, ¹H NMR, ¹³C NMR and elemental analysis. The preliminary bioassays for 17 novel title compounds showed that several compounds have significant fungicidal activity against Cercospora arachidicola, Physalospora piricola and Rhizoctonia cerealis at 50μg/mL.     

Design and synthesis of novel triazole derivatives containing γ-lactam as potential antifungal agents

A series of novel triazole derivatives containing γ-lactam were designed and synthesized, and their structures were confirmed by ~1H NMR,~(13)CNMR and HRMS. The in vitro antifungal activities of the target compounds were evaluated. The results showed that all of the compounds exhibited stronger activity against the six clinically important fungi tested than fluconazole. 3D and 3E showed comparative activity against the fungi tested except for Candida glabrata and Aspergillus fumigatus as voriconazole. In addition,the docking model for 2A and CYP51 was investigated.     

Synthesis and insecticidal evaluation of tetrahydroimidazo[1,2-a]pyridin-5(1H)-one derivatives

A series of novel tetrahydroimidazo[1,2-a]pyridine-5(1H)-one derivatives containing a electronegative pharmacophore(=CNO₂) were synthesized via practical aza-ene reaction and characterized by ¹H NMR, ¹³C NMR, ¹⁹F NMR and HRMS. Preliminary bioassays showed that some of the target compounds exhibited good insecticidal activity against brown planthopper(Nilaparvata lugens) and cowpea aphids(Aphis craccivora) at 500 mg L^-1. Among them, compound 11h was active against brown planthopper at 100 mg L^-1. The insecticidal activities varied significantly depending on the types and patterns of the substituents, which provided guidance for further investigation on structure modifications.     

新型2-(芳氨基乙基氨基)苯甲醇的合成及其杀菌活性

2-氨基苯甲醇及其衍生物是一类很重要的具有双官能团的化合物,在有机化学和药物合成中具有广泛的用途。本文主要提供了一种简单、有效合成2-(芳氨基乙基氨基)苯甲醇类化合物的方法,同时测定了目标化合物的杀菌活性。溴乙酰芳胺与2-氨基苯甲醇经N-烷基化反应生成2-[(2-羟甲基苯基)氨基]乙酰芳胺类化合物3,然后经LiAlH4还原生成了一系列结构新颖的2-(芳氨基乙基氨基)苯甲醇类化合物5a~5i,产率为76%~95%。用IR、~1H NMR、~(13)C NMR和元素分析等对产物结构进行了表征。目标化合物的杀菌活性结果表明,在测试浓度下,大部分显示中等至良好的活性,化合物5e对辣椒疫霉病菌的抑制活性达73.0%。     

Synthesis of Aminoalkyl-substituted Polymethoxychalcone Derivatives and Their Antiproliferative Activities Against Three Human Cancer Cell Lines

Two novel series of sixteen aminoalkyl-substituted polymethoxychalcone derivatives 2a-2h and 3a-3h were synthesized from 2'-hydroxy-3,4,5,4',6'-pentamethoxy chalcone(1) through extending alkoxy side chain at the 2'-position, and introducing amine hydrogen bond receptor at the end of the side chain. The structures of all the synthesized compounds were confirmed by ¹H NMR, ¹³C NMR and MS techniques. Furthermore, all the compounds were tested for antiproliferative activities in vitro against a panel of three human cell lines(HeLa, HCC1954 and SK-OV-3) via CCK-8 assay. The results show that all the target compounds exhibit antiproliferative activities against the three human cancer cells with IC₅₀ values of 4.62-48.21 μmol/L, except compound 2h against SK-OV-3 cells. Most of these compounds were more active when compared to the positive control cis-Platin.