含吡啶环拟除虫菊酯的合成及其杀虫杀螨活性

在新农药的创制中 ,吡啶作为苯环的生物等排体常被用作分子设计的有效基团 [1,2 ] ,近年来若干含有吡啶环的高效农药如吡虫啉 (Imidacloprid) [3 ] 、盖草能 (Haloxyfop) [4 ] 、啶氧菌酯 (Picoxystrobin) [5]等已被开发应用 .为合成筛选高生物活性化合物 ,我们在前期研究[6 ,7] 的基础上 ,将吡啶环引入拟除虫菊酯的酸部分 ,合成了与戊菊酯 (S- 5 4 3 9) [8] 和氰戊菊酯 (Fenvalerate) [8] 结构相近的新化合物 (5 ,6 ) ,并分离得到化合物 6的两对对映异构体 (α-和β-体 ) .生物活性测试表明 ,这些新化合物具有较高的杀虫或杀螨活性 .目标…     

Synthesis and Biological Activity of Novel Anthranilic Diamides Containing N-Substituted Arylmethylene Moieties

A series of novel anthranilic diamides containing N-substituted arylmethyl moieties was designed and synthesized, in which the bond distance and conjugation pattern between pyrazole and pyridine rings contained in Chlorantraniliprole were changed. Their structures were confirmed by JH NMR, IR, elemental analysis or high resolution mass spectromentry{HRMS）, and the conformation of compound 4d was confirmed by X-ray diffraction. The preliminary bioassay results indicate that all the target compounds exhibited moderate insecticidal activity against oriental armyworm at 200 mg/L and some of them presented favorable antitumor activities against human lung cancer cells（A549）, liver cancer cells（BelT402） and colon cancer celIs（HCT-8） in vitro by microculture tetrazolium（MTT） method, among which compound 6j afforded the best anti-proliferative activity at 5μg/mL.     

Syntheses and Biological Activities of Novel 3-Bromo-1-（3-chloropy- ridin-2-yl）-N-hydroxy-N-aryl- 1H-pyrazole-5-carboxamides

A series of novel 3-bromo-1-（3-chloropyridin-2-yl）-N-hydroxy-N-aryl-lH-pyrazole-5-carboxamides was synthesized by the reaction of pyrazole carbonyl chloride with each of substituted phenylhydroxyamines. The latter ones were prepared in good yields by reducing substituted nitrobenzene compounds with Zn/NH4CI reductant system in alcohol. Structures of the title compounds were determined by IR, 1H NMR, and HRMS. Their insecticidal and fungicidal activities were evaluated by larvicidal test against oriental armyworm and the mycelium growth rate method, respectively.     

Synthesis of novel N-pyridylpyrazole derivatives containing 1,2,4-oxadiazole moiety via 1,3-dipolar cycloaddition and their structures and biological activities

A series of novel 1,2,4-oxadiazole-containing N-pyridylpyrazole derivatives 12a−h were efficiently synthesized with pivaldehyde, pyridylpyrazole carboxylic acid and arylamine as raw materials via 1,3-dipolar cycloaddition. Their structures were identified by melting points, ¹H NMR, ¹³C NMR and elemental analysis or HRMS. The exploration on the single-crystal structures of 12c and 12g revealed the stereochemical and substituent oriental characteristics, and the relevance of the structure and the reaction activity of this type of compounds. The preliminary bioassays indicated that several compounds had good insecticidal activities, among which 12c showed a lethality rate of 80% towards Mythimna separata Walker at 200 μg/mL; some of the compounds exhibited favorable fungicidal activities at 50 μg/mL against Physalospora piricola, Rhizoctonia cereal, Sclerotinia sclerotiorum, etc. Among which, 12a, 12b, 12c and 12h could be considered as new fungicidal leading compounds for further structural optimization. These discoveries along with the structure-activity relationship analysis in this paper will provide useful guidance for the innovative studies on new pyridylpyrazole derivatives and their applications in agrochemical area.     

Synthesis of 4＂-benzyloxyimino-4＂-deoxyavermectin B 1 a derivatives

Six new 4＂-benzyloxyimino-4＂-deoxyavermectin B la derivatives were synthesized from avermectin Bla by the selective protection of C-5-hydroxy group, oxidation of C-4＂-hydroxy group, and deprotection followed by reaction with O-substituted hydroxylamine hydrochlorides. Their structures were confirmed by IR, 1H NMR, 13C NMR and MS. Insecticidal activities of the derivatives against Phopalosiphum pseudobrassicae, Spodoptera exigua and Pluteua xylosteua were evaluated.     

Design,Synthesis and Insecticidal Activity of Novel Anthranilic Diamides Containing Oxime Ester and Diacylhydrazine Moieties

Two series of novel anthranilic diamides containing oxime ester and diacylhydrazine moieties were designed and synthesized.Their structures were characterized by melting points,1H NMR,13C NMR and high resolution mass spectrometry（HRMS）.The single crystal structure of compound 7e was determined by X-ray diffraction and their evaluated insecticidal activity against oriental armyworm（Mythimna separata） indicates that some of the compounds exhibited moderate insecticidal activities.Among the 20 compounds,6a and 6b show 100％ larvicidal activity against Mythimna separate Walker at the test concentration of 100 mg/L.     

Synthesis and Biological Activities of Novel Methyl Xanthine Derivatives

Caffeine is one of methyl xanthine compounds,which has the similar mode of action as ryanodine receptor insecticide.In order to find novel and efficient insecticide,structural modification of certain methyl xanthine compounds was made by introducing some common pesticidal active moieties into the structure of caffeine.Eleven novel methyl xanthine compounds were synthesized and characterized by 1H nuclear magnetic resonance（1H NMR）,elemental analylsis or high-resolution mass spectrometry（HRMS）.According to the biological activity results,it was found that these new compounds show moderate activity towards Mythimna separata Walker and Culex pipiens pallens.For example,compound 2d shows a lethality rate of 40％ at 200 mg/L towards Mythimna separata Walker,compounds 2i and 2f show 56.7％ and 53.3％ lethality rates at 2 mg/L towards Culex pipiens pallens,which are all better than caffeine.In addition,some compounds of them show moderate antifungal activity to some plant pathogenous fungi.     

4-(7-甲氧基-2,2-二甲基-2,3-二氢苯并呋喃-5-基)-2-芳氨基噻唑的合成、晶体结构与杀虫活性

以2-(2-甲基烯丙氧基)苯酚为原料, 经Claisen重排、呋喃环化、醚化、Friedel-Crafts乙酰化、α-溴代和噻唑环化等反应合成了22种4-(7-甲氧基-2,2-二甲基-2,3-二氢苯并呋喃-5-基)-2-芳氨基噻唑化合物. 化合物的结构经质谱、1H NMR和元素分析等确证. 采用单晶X射线衍射仪测定了化合物7j的晶体结构, 该晶体属于单斜晶系, 空间群为C2/c, 晶胞参数a=2.21140(12) nm, b=0.87602(5) nm, c=2.13911(12) nm, β=115.5380(10)°; V=3.7391(4) nm3, Z=8, Dc=1.375 g/cm3, F(000)=1616, S=1.046, μ=0.333 mm-1, 最终偏差因子R1=0.0390, wR2=0.1079. 杀虫活性实验结果表明, 化合物7a, 7b, 7h和7t在浓度为500 mg/L时对蚕豆蚜死亡率分别为95.12%, 62.60%, 57.53%和59.06%.     

Synthesis and insecticidal bioactivities of 2,3-dihydroimidazo[1,2-a]pyridin-5(1H)-one derivatives

A novel synthesis of 2,3-dihydroimidazo[1,2-a]pyridin-5(1H)-one, and insecticidal derivatives were described.     

Syntheses and insecticidal activities of novel 2,5-disubstituted 1,3,4-oxadiazoles

Nine novel symmetrical and asymmetrical 2,5-disubstituted 1,3,4-oxadiazoles have been synthesized by a facile and mild method with high yield. Meantime, it was found that the fluorine was easy substituted by hydrazine in polyhalogen-substituted aroyl hydrazine. The preliminary bioassay tests show that two of the compounds (D5 and D6) exhibited a significant insecticidal activity (LC₅₀=116.02 and 70.93 mg l⁻¹) on armyworm, Leucania separata Walker. Using the Drug Discovery Workbench (DDW) (Cerius²), structure-activities relationship was studied.