取代苯甲醛肟羧酸酯的合成及生物活性研究Ⅵ.4-二甲氨基苯甲醛肟酯的合成及生物活性

苯甲醛肟酯;取代苯甲醛肟羧酸酯的合成及生物活性研究Ⅵ.4-二甲氨基苯甲醛肟酯的合成及生物活性     

N-酰基吡唑衍生物的合成与生物活性

N-酰基吡唑衍生物的合成与生物活性;拟除虫菊酯;1H吡唑衍生物;合成;生物活性     

鱼藤酮肟羧酸酯的合成和生物活性

以鱼藤酮为原料,经肟化、酯化反应合成了9种鱼藤酮肟羧酸酯新化合物,化合物经1H NMR、红外、元素分析等确证结构.生物活性试验结果表明:3a,3b和3c对家蝇(0.30 mg/mL)死亡率分别为80.0%,90.0%和95.0%,对甜菜夜蛾(0.10 mg/mL)的致死率分别为57.1%,60.0%和73.3%;3b对粘虫(1.00mg/mL)的致死率为86.4%,对叶蝉(0.50 mg/mL)的致死率为71.8%;3c对粘虫(1.00mg/mL)的致死率为100%;3a对叶蝉(0.50 mg/mL)的致死率为54.2%.     

1，3，5－取代吡唑－4－亚甲基环丙烷羧酸酯的合成及生物活性

１，３，５－取代吡唑－４－亚甲基环丙烷羧酸酯的合成及生物活性黄润秋，宋健，冯磊（南开大学元素有机化学研究所，元素有机化学国家重点实验室，天津，３０００７１）关键词吡唑，环丙烷羧酸酯，杀虫剂，杀病毒剂吡唑类杂环化合物有广泛的生物活性，并有若干高效的杀虫...     

1-苯基-3-甲基-5-芳氧基-1H-吡唑-4-甲醛-O-[(2-氯吡啶-5-基)甲基]肟的合成与生物活性

利用1-苯基-3-甲基-5-芳氧基吡唑4-甲醛肟与2-氯-5-氯甲基吡啶发生缩合反应,合成了14个新型含吡啶环的吡唑肟醚衍生物.通过1H NMR,13C NMR和元素分析对所合成的化合物进行了结构表征.初步生物活性测试结果表明,在试验浓度下部分化合物具有一定的杀菌和植物生长调节活性.     

新型含噻唑环的吡唑肟醚类衍生物的合成及其生物活性

为了寻找活性较好的杂环农药,将噻唑基团引入到吡唑分子结构中,设计合成了一系列新型含噻唑环的吡唑肟醚衍生物.通过1H NMR、13C NMR和元素分析测试对标题化合物的结构进行了表征.对合成的目标化合物进行了初步的生物活性测试,部分化合物显示出一定的的杀菌、杀虫或植物生长调节活性.     

含取代噁唑结构的新型吡唑肟衍生物的合成与生物活性

为了发现具有良好生物活性的吡唑肟化合物,以唑螨酯为先导化合物,在吡唑肟中引入取代噁唑结构,设计并制备了20个未见文献报道的新型吡唑肟衍生物,利用1H NMR,13C NMR和元素分析确证了目标产物的结构.生物活性测试结果显示,部分目标化合物在500和100μg/mL浓度下对粘虫或蚜虫表现出优良的杀虫活性,其中5-(3-氟苯氧基)-1,3-二甲基-1H-吡唑-4-甲酰基-O-{[5-(4-氯苯基)噁唑-2-基]甲基}肟(9j)、5-(4-氟苯氧基)-1,3-二甲基-1H-吡唑-4-甲酰基-O-{[5-(4-氯苯基)噁唑-2-基]甲基}肟(9k)、5-(4-叔丁基苯氧基)-1,3-二甲基-1H-吡唑-4-甲酰基-O-{[5-(4-氯苯基)噁唑-2-基]甲基}肟(9r)和5-(4-甲氧基苯氧基)-1,3-二甲基-1H-吡唑-4-甲酰基-O-{[5-(4-氯苯基)噁唑-2-基]甲基}肟(9s)在浓度为100μg/mL时对粘虫的防治效果均达100%,5-(4-溴苯氧基)-1,3-二甲基-1H-吡唑-4-甲酰基-O-{[5-(4-氟苯基)噁唑-2-基]甲基}肟(9g)和9s在浓度为100μg/mL时对蚜虫的杀灭活性均为100%.此外,化合物9s在500μg/mL时对朱砂叶螨的防治效果为70%.     

取代苯甲醛肟羧酸酯的合成及生物活性研究 (Ⅲ)──取代苯甲醛肟四甲基环丙烷羧酸酯的合成及生物活性

肟醚(酯)类化合物具有优良的杀虫、杀螨、杀菌、除草及昆虫生长调节活性^[1].我们在前文^[2,3]基础上,合成一系列取代苯甲醛肟四甲基环丙烷羧酸酯,芳香醛肟对位为二甲氨基或二乙氨基取代的化合物(5m,5n)呈现较好的杀菌或杀虫活性.     

新型含吡啶环取代的吡唑肟醚类化合物的合成及生物活性研究

为了寻找新型高效低毒的农药先导化合物,通过N-吡啶基吡唑肟与2-氯-5-氯甲基吡啶的缩合反应,合成了一系列含吡啶环取代的吡唑肟醚类化合物.目标化合物的结构均经1H NMR,13C NMR和元素分析确证.初步生物活性试验结果表明,部分化合物具有一定的杀菌、杀虫和植物生长调节活性.如化合物5e在浓度为50 μtg/mL时对番茄早疫的抑制率为61.4％;化合物5j在浓度为50 μg/mL时对花生褐斑的抑制率为60.2％;化合物5i在浓度为500 μg/mL时对蚜虫表现出50.3％的杀死率;化合物5f在浓度为10 μg/mL时对黄瓜子叶生根表现出71.0％的促进生长作用.     

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.     

α－酰氨基环十二酮的合成及其结构表征

以易得的环十二酮为原料,制得中间体α-硝基环十二酮后,选择性还原为α-氨基环十二酮(Ⅱ),再经氨基的酰化,共合成12种目标化合物(Ⅲ).它们的结构用IR,MS,¹H NMR和元素分析进行了表征。初步的生物测定表明,它们中的一些对稗草和油菜显示出良好的除草活性。在合成Ⅱ的过程中,分离到一种结晶化合物,经波谱测定和元素分析确定其结构为双[邻-1,10-亚癸基]吡嗪(Ⅳ),并得到合成的验证。     

Rapid screening for synthetic antidiabetic drug adulteration in herbal dietary supplements using direct analysis in real time mass spectrometry

Adulteration of herbal supplements with synthetic drugs is illegal. A rapid and reliable method which utilizes direct analysis in real time mass spectrometry (DART-MS) was developed for the identification of seven synthetic antidiabetic drugs used as adulterants in herbal dietary supplements. The supplement sample was simply extracted with methanol/water by manually shaking several times and directly analyzed using DART-MS. The presence of synthetic drug adulterants was confirmed through the accurate m/z values and MS/MS data obtained via quadruple time of flight mass spectrometry (QTOF MS). Parameters for the DART source were systematically optimized, and the limits of detection (LODs) in herbal supplement matrices were measured. This method was successfully applied to examine five commercial herbal dietary supplements, and two of them proved to be adulterated with metformin without labeling.     

Identification of caffeic acid derivatives in Actea racemosa (Cimicifuga racemosa,black cohosh) by liquid chromatography/tandem mass spectrometry

Caffeic acid derivatives occurring in black cohosh [Cimicifuga racemosa (L.) Nutt., Actaea racemosa (Ranunculaceae)], some of which may have pharmacological activity, were analyzed using high-performance liquid chromatography (HPLC) electrospray ionization tandem mass spectrometry (ESI-MS/MS) with the aim of developing a methodology for their rapid identification in a complex plant matrix. Based on these studies, structurally characteristic product ions and neutral molecule losses were identified, which were then used during LC/MS/MS with product ion scanning, precursor scanning and constant neutral loss scanning to detect caffeic acid derivatives in a crude extract of black cohosh. Several caffeic acid derivatives were detected, and the identification of six of them were confirmed by comparison with authentic standards including caffeic acid, ferulic acid, isoferulic acid, fukinolic acid, cimicifugic acid A, and cimicifugic acid B. Four other compounds were detected that appeared to be caffeic acid derivatives based on LC/MS/MS retention times, molecular weights, and fragmentation patterns during MS/MS. Since standards were unavailable for these four compounds, they were tentatively identified using LC/MS/MS as cimicifugic acid E, cimicifugic acid F, dehydrocimicifugic acid A, and dehydrocimicifugic acid B. Dehydrocimicifugic acid A and dehydrocimicifugic acid B have not been reported previously to be constituents of black cohosh.     

Use of an accurate-mass database for the systematic identification of transformation products of organic contaminants in wastewater effluents

In this article, a systematic approach is proposed to assist and simplify the identification of transformation products (TPs) of organic contaminants. This approach is based on the use of characteristic fragmentation undergone by organic contaminants during MS/MS fragmentation events, and the relationship and consistency with the transformations experimented by these chemicals in the environment or during water treatment processes. With this in mind, a database containing accurate-mass information of 147 compounds and their main fragments generated by CID MS/MS fragmentation experiments was created using an LC-QTOF-MS/MS system. The developed database was applied to the identification of tentative TPs and related unexpected compounds in eight wastewater effluent samples. The approach comprises basically three stages: (a) automatic screening, (b) identification of possible TPs and (c) confirmation by MS/MS analysis. Parameters related to the search of compounds in the database have been optimized and their dependence with the exhaustiveness of the study evaluated. Eight degradation products, from the pharmaceuticals acetaminophen, amoxicillin, carbamazepine, erythromycin and azithromycin and from the pesticide diazinon, were identified with a high grade of accuracy. Three of them were confirmed by analysis of the corresponding analytical standards.     

Marker peptide selection for the determination of hazelnut by LC–MS/MS and occurrence in other nuts

The aim of this work was identifying and selecting hazelnut marker peptides and subsequently developing a complementary method of common immunoassay for the detection of hazelnut. For this purpose, at first, an in silico digestion of three major hazelnut allergens (Cor a 8, Cor a 9 and Cor a 11) was performed to get information about expected peptides. After extraction and trypsin digestion of hazelnut proteins, the samples were measured with tandem mass spectrometry (MS/MS) by direct infusion, which led to identification of 14 peptides. Eight of them with the highest MS signal were synthesized and used as standards for developing a liquid chromatography (LC)–MS/MS method in selected reaction monitoring (SRM) mode. Since almost all food allergens derived from nuts belong to the seed storage protein family and have homologue structure, a Basic Local Alignment Search Tool (BLAST) search was performed to identify the hazelnut specificity of the developed method. According to BLAST, only one peptide occurs in three other nuts, and the remaining seven selected peptides are hazelnut specific. Additionally to hazelnut, the eight other listed nuts in Directive 2003/89/EC as allergen were extracted, digested and measured with the developed method to prove the BLAST results. The analytical data confirmed that six peptides are hazelnut specific, on the contrary to anti-hazelnut antibodies, which showed cross-reactivities to all other nut extracts. Comparing these results, it could be shown that with this LC–MS/MS method in SRM mode, the specific detection of hazelnut is possible.     

Accurate mass and nuclear magnetic resonance identification of bisphenolic can coating migrants and their interference with liquid chromatography/tandem mass spectrometric analysis of bisphenol A

Two unknown compounds were previously determined to be potential interferences in liquid chromatography/tandem mass spectrometry (LC/MS/MS) analysis of bisphenol A (BPA) in canned infant formula. Both yielded two identical MS/MS transitions to BPA. The identities of the unknowns were investigated using accurate mass LC/MS, LC/MS/MS, and elemental formula and structures proposed. Exact identities were confirmed through purification or synthesis followed by (1)H and (13)C nuclear magnetic resonance (NMR) experiments, as well as comparisons of one unknown with commercial standards. Comparisons of negative ion electrospray ionization (ESI) MS/MS and accurate mass spectra suggested both unknowns to be structurally identical (to BPA and each other). Positive ion ESI spectra confirmed both were larger molecules, suggesting that in the negative mode they likely fragmented to the deprotonated BPA ion in the source [corrected]. Elemental composition of positive ion accurate mass spectra and NMR analysis concluded the unknowns were oxidized forms of the known epoxy can coating monomer, bisphenol A diglycidyl ether (BADGE). One of the unknowns, 2,2-[bis-4-(2,3-dihydroxypropoxy)phenyl]propane, commonly known as BADGE*2H(2)O, is widely reported as an epoxy-phenolic can coating migrant, but has not been suggested to interfere with the MS/MS analysis of BPA. The other unknown, 2-[4-(2,3-dihydroxypropoxy)phenyl]-2-[4'-hydroxyphenyl]propane, or the oxidized form of bisphenol A monoglycidyl ether (BAMGE*H(2)O), has not been previously reported in food or packaging.     

Synthesis and Herbicidal Activities of N''-(substituted pyrimidin-2-yl)-N-Substituted Phenoxyacetyl Thiourea Derivatives

Acylthiourea derivatives are well known for a wide range of biological activities likebactericidal, fungicidal, herbicidal, insecticidal action and regulating activity for plantgroWth"'. In recent years, substituted phenoxyacetic acid derivatives have beenreported as highly efficient herbicides4. In this paper. a series of substitutedphenoxyacetyl thiourea containing substituted pyrimidine ring sa~so were synthesizedand tested for their biological activities. All of them are new compounds and…     

Liquid chromatography/triple quadrupole tandem mass spectrometry with multiple reaction monitoring for optimal selection of transitions to evaluate nutraceuticals from olive-tree materials

Optimal transitions have been selected for the identification and quantitation of the most interesting hydrophilic biophenols in extracts from olive-tree materials, which are of interest because of their nutraceutical properties. The tested materials were extra virgin olive oil, waste from oil production (known as alperujo), and olive-tree materials such as leaves, small branches and fruit stones. The identification and determination steps of the target biophenols are based on liquid chromatography/tandem mass spectrometry (LC/MS/MS) with a triple quadrupole (QQQ) mass detector. The interface between the chromatograph and the QQQ was an electrospray ionization source operated in the negative ion mode. Highly selective identification of the biophenols was confirmed by multiple reaction monitoring (MRM) using the most representative transitions from the precursor ion to the different product ions. Quantitative MS/MS analysis was carried out by optimization and selection of the most sensitive transition for each analyte, which resulted in estimated detection limits of 5.10 to 11.65 ng/mL for the extracts. The biophenols were extracted from the tested samples by different methods: liquid-liquid extraction for virgin olive oil, microwave-assisted leaching for olive leaves, branches and stones, and pressurized liquid leaching for alperujo. This study provides valuable information about the most suitable source for the isolation of each nutraceutical biophenol and enables us to obtain a complete profile of them in Olea Europaea.     

新型吡唑甲酰脲类化合物的合成及其生物活性

５－氯－１，３－二甲基吡唑－４－甲酰基异氰酸酯同胺类化合物反应，合成了２３个新型吡唑甲酰脲类化合物，其化学结构经ＩＲ、１ＨＮＭＲ、ＭＳ和元素分析确证。所有化合物均具有一定的杀菌活性，部分化合物具有较好的杀虫活性。     

Rapid screening for bisbibenzyls in bryophyte crude extracts using liquid chromatography/tandem mass spectrometry

A simple and rapid qualitative liquid chromatography-diode-array detection/tandem mass spectrometry (LC-DAD/MS/MS) method was developed and validated for screening bisbibenzyl compounds in bryophyte crude extracts at sub-ppm levels. After simple extraction with ethanol and analyte concentration with diethyl ether, the extracts were subjected to LC-DAD/MS/MS analysis. The overall instrument turnaround time was 50 min to obtain baseline separation of bisbibenzyl isomers in bryophytes. MS full scan, MS/MS precursor ion scan and MS/MS product ion scan modes were used for the screening. The bisbibenzyl standards studied gave limits of detection (LODs) at or below 10 ng/mL. The results also indicated that the method had acceptable precision to be used on a day-to-day basis for qualitative identification. The bisbibenzyl types, i.e. one biphenyl ether bond (A-type), two biphenyl ether bonds (B-type), one biphenyl ether and one biphenyl bond (C-type), or other biphenyl types can be differentiated by their ESI-MS/MS product profiles, and the number of alkoxyl substituents can also be identified. The linkage sites of biphenyl and biphenyl ether bonds cannot be identified for an unknown bisbibenzyl solely from its mass spectra. This system was used to support three screening assays of bryophytes including Marchantia polymorpha L., Ptagiochasm intermedium L. and Asterella angusta, which were collected from different places in China. From them, 7/12, 8/5 and 8/9 confirmed/unconfirmed bisbibenzyls were identified, respectively, based on their MS/MS data, UV spectra and the retention behavior. The screening method considerably reduced the time and the cost for the qualitative analyses, and the structure-fragmentation-UV relationships will facilitate the high-throughput screening (HTS) of bisbibenzyl compounds in bryophytes. It is also intended as a simple and convenient way for the determination of other structural families of natural products.