Synthesis and Biological Activity of New Pyrethroid Acid Oxime-esters Containing Pyrazole Ring

A series of compounds containing oxime-ester linkage and pyrazole ring(in place of the ester linkage and the alcohol moiety in pyrethroid ester) was designed and synthesized. The structures of all the compounds prepared were confirmed by 1H NMR and MS spectroscopy as well as elemental analyses. The bioassay data of those compounds against tobacco mosaic virus(TMV), cucumber mosaic virus(CMV), potato virus X(PVX) and potato virus Y(PVY) were presented. Among them compound 6i was found to possess significant plant antiviral activities. But all the compounds showed low insecticidal and acaricidal activities.

NEW POLY(METHACRYLATE)S CONTAINING OXIME ESTERS MOIETIES BASED ON CYCLOHEXANON AND CYCLOPENTANON

The synthesis of two new methacrylates such as 2-[(cyclohexylideneamino)oxy]-2-oxoethyl methylacrylate (CHOEMA)and 2-[(cyclopentylideneamino)oxy]-2-oxoethyl methylacrylate(CPOEMA)are described.The monomers produced from the reaction of corresponding cyclohexanone O-(2-chloroacetyl)oxime and cyclopentanone O-(2- chloroacetyl)oxime with sodium methacrylate was polymerized in 1,4-dioxane solution at 65℃using AIBN as an initiator. The monomers and their polymers were characterized by IR,~1H- and ^(13)C-NMR spec...

Synthesis,Characterization and Antibacterial Activity of New 5-Aryl Pyrazole Oxime Ester Derivatives

Eleven new 1-{5-[4-（benzyloxy）phenyl]-3-methyl-4,5-dihydropyrazol-l-yl} oxime ester dcrivatives were synthesized and characterized by elemental analysis, HRMS, ^1H NMR data. All the compounds were screened for their antibacterial potential in vitro against Bacillus subtilis, Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa. The results indicate that compounds 8c and 8f possess potent activity with the minimum inhibitory concentrations（MIC） of 1.562--3.125 ug/mL against all the four bacteria. Compounds 8c, 8e and 8f show moderate inhibition against the DNA gyrase（IC50=1.9--2.5 ug/mL）. On the basis of the biological activities, structure-activity relationship was discussed.

Stereospecific Assembly of Trisubstituted Alkenes via Photoinduced Nitrogen-Centered Radical-Triggered C—C Bond Cleavage/Functionalization of Oxime Esters

Comprehensive Summary A general and convenient photoredox-catalyzed acylation and alkylcyanation of MBH acetates has been established,enabling the assembly of the C(sp2)–C(sp3)bond by a nitrogen-centered radical strategy for the synthesis of trisubstituted alkenes in moderate to excellent chemical yields(48 examples in total).The reaction of MBH acetates with acyl(indanone)oxime esters afforded trisubstituted alkenes containing 1,4-dicarbonyl groups.Interestingly,the use of Eosin Y as a photocatalyst in the catalytic system resulted in the formation of distal cyano group-anchored trisubstituted alkenes via deconstructive functionalization of cycloketone oxime esters.Notably,these resulting 1,4-dicarbonyl compounds could be applied to late-stage transformations,providing important methods for the synthesis of dihydropyridazin-3(2H)-one.

低迁移咔唑基肟酯光引发剂的合成与性能研究

为降低光引发剂在光固化涂层中的迁移性,以咔唑为生色团,合成了2种以双键封端的可聚合型肟酯类光引发剂。利用紫外-可见光光度计对其紫外吸收、稳态光解和迁移性进行研究,通过傅立叶变换红外光谱仪(FT-IR)研究光致脱羧和光聚合动力学性能,并利用热重分析仪(TGA)对其热稳定性进行研究。结果表明:肟酯类光引发剂的最大吸收波长在338 nm,尾部吸收延至380 nm。在低光强365 nm LED辐照下(1 mW/cm2),咔唑基肟酯可发生光致脱羧反应,释放的活性自由基能有效引发丙烯酸酯单体和巯基-丙烯酸酯体系聚合。且可聚合型咔唑基肟酯类光引发剂在光固化涂层中显示了较低的迁移性。

(Z)-/(E)-胡椒酮基吡唑-肟酯化合物的合成及其抑菌活性研究

以胡椒酮为原料,将羰基肟化后再与取代吡唑发生O-酰化反应,合成了42个新型(Z)-/(E)-胡椒酮基吡唑-肟酯化合物(6a~6u,包括21对Z/E异构体),采用核磁共振氢谱(^(1)H NMR)、核磁共振碳谱(^(13)C NMR)、傅里叶变换红外光谱(FT-IR)和高分辨质谱(HRMS)对目标产物的结构进行了表征,并通过单晶X射线衍射(SC-XRD)分析了其Z/E构型。离体生物活性测试结果表明:当质量浓度为50 mg/L时,(Z)-/(E)-胡椒酮基吡唑-肟酯化合物对黄瓜枯萎病菌、花生褐斑病菌、苹果轮纹病菌、番茄早疫病菌、小麦赤霉病菌、水稻纹枯病菌、玉米小斑病菌和西瓜炭疽病菌这8种植物病原菌,均表现出一定的抑菌活性且受其Z/E构型影响显著,尤其对番茄早疫病菌的抑制活性最好,其中化合物(Z)-胡椒酮基(3′,5′-二三氟甲基)苯基吡唑-肟酯((Z)-6o)、(Z)-胡椒酮基(p-三氟甲基)苯基吡唑-肟酯((Z)-6u)、(Z)-胡椒酮基(p-硝基)苯基吡唑-肟酯((Z)-6p)、(E)-胡椒酮基(p-硝基)苯基吡唑-肟酯((E)-6p)、(Z)-胡椒酮基(p-三氟甲氧基)苯基吡唑-肟酯((Z)-6g)和(E)-胡椒酮基(o-氟)苯基吡唑-肟酯((E)-6i)对番茄早疫病菌的抑制率分别为83.8%、78.7%、76.3%、76.3%、74.8%和74.3%,而化合物(Z)-6u对苹果轮纹病菌的抑制率达82.5%,均优于阳性对照百菌清。采用比较分子场分析(CoMFA)方法对目标化合物Z构型对番茄早疫病菌抑制活性的三维定量构效关系(3D-QSAR)进行了初步探讨,建立了合理有效的3D-QSAR模型(r^(2)=0.928,q^(2)=0.732)。

含肟酯/醚结构的枯茗醛衍生物合成及抑菌活性

以孜然精油的主要成分枯茗醛为原料,设计合成了系列含肟酯/醚结构的枯茗醛衍生物18个,并通过^(1)H NMR、^(13)C NMR和HRMS进行了结构表征;以地毯草黄单胞柑橘致病变种和水稻黄单胞菌为对象,采用浑浊度法对目标化合物的抑菌活性进行了评估。抑菌活性测试结果表明:化合物(Z)-4-异丙基苯甲醛-O-(3-甲氧基苯甲酰基)肟(4i)在质量浓度50μg·mL^(-1)下对地毯草黄单胞柑橘致病变种的抑制率为3280%,优于对照药剂叶枯唑(1688%);目标化合物(Z)-4-异丙基苯甲醛-O-(苯甲酰基)肟(4d)、(Z)-4-异丙基苯甲醛-O-(4-三氟甲基苯甲酰基)肟(4h)和(Z)-4-异丙基苯甲醛-O-(3-甲氧基苯甲酰基)肟(4i)在质量浓度100μg·mL-1下对地毯草黄单胞柑橘致病变种的抑制率分别为60.3%、31.37%和33.30%,优于对照药剂叶枯唑的抑制率(45.82%)。

Studies on the esterifications of 9-(hydroxyimino)-4-methyl-8,9-dihydrofuro[2,3-h]chromen-2-one with acid chlorides under different conditions

The esterifications of 9-（hydroxyimino）-4-methyl-8,9-dihydrofuro[2,3-h]chromen-2-one （4） with acid chlorides afforded normal oxime-esters 3a-e in 35-78% yields in presence of excessive 4-dimethylaminopyridine as the acid scavenger, whereas the reactions gave unexpected 8-substituted products N-（8-chloro-4-methyl-2-oxo-2H-furo-[2,3-h]chromen-9-yl）amides （5a-c） and 4-methyl-2,9-dioxo-8,9-dihydro-2H-furo[2,3-h]chromen-8-ylcarboxyloates （6d-e） by using excessive acid chlorides. The structures of 10 new compounds were determined by 1H NMR, 13C NMR, MS and HRMS, and the possible mechanism for the formation of unexpected products 5a--c and 6d-e was also proposed.

5-甲基异噁唑-4-甲酸肟酯衍生物的合成及抑菌活性

异噁唑是具有较好活性的五元杂环,本文设计并合成了15个5-甲基异噁唑-4-甲酸肟酯类新化合物,利用核磁氢谱、核磁碳谱和高分辨质谱对其结构进行确证,并测试了其对番茄灰霉病菌Botrytis cinerea、水稻纹枯病菌Rhizoctonia solani、苹果树腐烂病菌Valsa mali和小麦全蚀病菌Gaeumannomyces graminis的离体抑菌活性。结果表明,在50μg/mL下,目标化合物对供试病原菌均有一定的抑菌活性,其中化合物5g对番茄灰霉病菌的抑制活性优于先导化合物L1和肟菌酯,EC50值为1.95μg/mL。

光可裂解型LED敏感的光引发剂的研究进展

目前LED光聚合体系所用的光引发剂大多是多组分光引发体系,只有少数是单组分光可裂解型光引发剂体系。光可裂解型光引发剂具有机理简单、引发速率快、应用便利等众多优势。但多数工业上常用的可裂解光引发剂在LED光源下光吸收效率较差,必须红移它们的吸收波长达到与LED适配的效果。因此,研发新型的光可裂解LED敏感的光引发剂是光聚合领域迫切的需求。其中,鎓盐类和肟酯类光引发剂,由于其优异的光化学物理性质成为了研究的热点,本文综述了这两类光引发剂的研究进展,以期为更优异的光引发剂的设计提供有价值的启示。

欧芹酚甲醚肟酯类化合物的制备及其抗乙酰胆碱酯酶活性研究

为研发具有AChE双位点抑制的新型乙酰胆碱酯酶抑制剂,本论文以香豆素类化合物欧芹酚甲醚为先导化合物,通过氧化、还原、酯化等反应设计合成了14个欧芹酚甲醚肟酯衍生物,并经核磁共振波谱(NMR)和质谱(MS)进行结构确证。采用Ellman法测定了目标化合物在1μmol·mL^(-1)下对乙酰胆碱酯酶的抑制活性,结果显示目标化合物4i和4n对乙酰胆碱酯酶的抑制率分别达到61.6%和51.2%,且与化合物浓度呈正相关。分子对接分析表明化合物4i可以和AChE的催化位点和外周阴离子位点结合。

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 Anticancer Activity of 2,3,4-Trimethoxyacetophenoxime Ester Containing Benzothiazole Moiety

A series of 2,3,4-trimethoxyacetophenoxime esters containing benzothiazole moiety were synthesized by the reaction of oxime with acyl chloride in alkaline medium. Their structures were established by elemental analysis, IR, and ^1H NMR spectra. The bioassay tests showed that these title compounds exhibit moderate anticancer activity in vitro by MTT method and compounds 6c and 6d could inhibit ERK phosphorylation in NIH 3T3 cell induced by PDGF.

Iron-catalyzed cyanoalkylation of difluoroenol silyl ethers with cyclobutanone oxime esters

An iron-catalyzed coupling reaction of difluoroenol silyl ethers and cyclobutanone oxime esters is described. This protocol provides a convenient access to various previously unknown and potentially useful gem-difluoromethylenated ketonitriles inmoderate to good yields. The transformations of resulting products to other fluorinecontaining products is also documented.

Nickel-Catalyzed Enantioselective Desymmetrizing Aza-Heck Cyclization of Oxime Esters

Densely functionalized chiral nitrogen-containing heterocycles are ubiquitous in bioactive synthetic compounds and natural products.Herein,we report a nickel(Ni)-catalyzed enantioselective desymmetrizing aza-Heck cyclization of oxime esters with a commercially available chiral pyridinebis(oxazoline)(pybox)ligand.This reaction proceeds under mild reaction conditions,tolerates various functional groups,and leads to chiral 2-substituted-3,7a-dihydro-3aH-indoles.

肟类衍生物的合成与农药生物活性的研究进展

肟类化合物具有优良的杀虫、杀菌及除草活性,不少品种还具有低毒、低残留等优点.目前该类化合物的分子设计和合成及生物活性研究是农药创制的热点之一.按照不同的生物活性和结构进行分类,对近年来肟类化合物在农业中应用作了综述,着重从分子合成和生物活性进行讨论,并对它的发展趋势、应用前景作了进一步展望.

新型1,5-二苯基-1,4-戊二烯-3-酮肟酯类化合物的合成及其抑菌活性研究

以1,5-二苯基-1,4-戊二烯-3-酮肟和酰氯为原料,合成了15个新型的1,5-二苯基-1,4-戊二烯-3-酮肟酯类化合物,通过元素分析,IR,1HNMR,13CNMR等对其结构进行了表征.初步生物活性试验结果表明,在50mg?L-1浓度下,化合物3i和3o对小麦赤霉病菌抑制率分别为51.1%和53.4%,与对照药剂恶霉灵抑制活性相当.

姜黄素双肟酯衍生物的合成与生物活性研究

采用生物活性因子拼接的方法将活性基团肟酯引入植物源活性化合物姜黄素中对其结构进行修饰,通过肟化、酰化、最后酯化合成目标化合物姜黄素二苯甲肟酯和姜黄素二对氯苯甲肟酯,其结构经IR和^1H NMR确证.初步生物活性测试结果表明：姜黄素和目标化合物在浓度为500mg/L条件下对6种植物病原菌的抑菌活性都较小,分别在1.6%-11.1%和-0.5%-15.2%之间;在浓度为1250mg/L时,目标化合物对朱砂叶螨的触杀效果较姜黄素显著提高.药剂处理后48h时,姜黄素对朱砂叶螨的校正死亡率为12.5%,目标化合物的校正死亡率在48.5%-82.6%之间;72h时,姜黄素对朱砂叶螨的校正死亡率上升为19.3%,而目标化合物的校正死亡率则高达92.4%-97.0%.

新型5-芳基-N-吡唑肟酯化合物的合成与杀菌活性

以水杨醛和丙酮缩合形成α,β不饱和酮,与水合肼和冰乙酸关环形成5-(2-羟基苯基)吡唑酮骨架,合成了10种未见报道的1-(5-(2-(苯氧基)苯基)-3-甲基)-4,5-二氢-N-吡唑肟酯类衍生物。通过元素分析、红外光谱及核磁共振氢谱测试技术对其结构进行了表征,初步测定了化合物的杀菌活性。结果表明,化合物对小麦赤霉病菌有较好的杀灭活性(其中化合物5f杀灭活性达到81.3%);化合物5g和5i对水稻纹枯病菌有中等杀灭活性,对稻瘟病菌的杀灭活性差。

含肟酯类姜黄素衍生物的合成及其抑菌活性研究

将肟酯引入单羰基姜黄素衍生物1,5-二取代芳基-1,4-戊二烯-3-酮化合物中,通过醚化、肟化、酰化,最后酯化合成11个不对称1,5-二取代-1,4-戊二烯-3-酮肟酯类姜黄素衍生物,其结构经IR、1HNMR、13CNMR和元素分析确证。初步生物活性测试结果表明,部分化合物具有一定的抑菌活性。