Design, synthesis and insecticidal activities of novel pyrazole amides containing hydrazone substructures

BACKGROUND: Pyrazole and hydrazone derivatives possess good insecticidal activities; their substructural units are widely used in pesticide design. In an effort to discover new molecules with good insecticidal activities, a series of pyrazole amide derivatives containing hydrazone substructures were synthesised and bioassayed. RESULTS: Bioassays demonstrated that some of the title compounds exhibited notable control of Plutella xylostella (Linnaeus), Helicoverpa armigera (Hübner), Culex pipiens pallens, Laphygma exigua (Hübner), Spodoptera litura (Fabricius), Nilaparvata lugens (Stål) and Rhopalosiphum maidis (Fitch) at 5, 10, 0.25, 200, 20, 100 and 500 mg L^?1 respectively. Comparative molecular field analysis (CoMFA) based on the bioactivities for P. xylostella was studied; the values of q² and r² for the CoMFA model were 0.701 and 0.964 respectively. CONCLUSION: Some of the title compounds displayed good and broad‐spectrum insecticidal activities against different insect species; the CoMFA model revealed that a bulky and negatively charged group at the 4‐position of benzene could enhance insecticidal activity. These results could provide useful information for the design of novel insecticide containing substructural units of pyrazole amide and hydrazone. Copyright © 2011 Society of Chemical Industry     

1-酰基苯并咪唑酮酰胺衍生物的合成及其抗菌活性

以邻苯二胺和乙酰乙酸乙酯为起始原料制得异丙烯基苯并咪唑酮(Ⅲ),再经N-酰化反应得到13个苯并咪唑酮酰胺衍生物(Ⅳ-01～Ⅳ-13)以及由Ⅳ-02脱异丙烯基的产物Ⅳ-02a,其中9个为未见文献报道的新化合物。通过核磁共振氢谱和碳谱、质谱以及元素分析对其结构进行了表征。抑菌活性测定结果表明,化合物Ⅳ-01～Ⅳ-03、Ⅳ-11及Ⅳ-02a对供试病原细菌和真菌均表现出明显的抑菌活性,其中化合物Ⅳ-02和Ⅳ-02a尤为突出,且二者活性相近,其中Ⅳ-02对蜡状芽孢杆菌Bacillus cereus(1.184 6)、枯草芽孢杆菌Bacillus subtilis(1.88)、金黄色葡萄球菌Staphylococcus aureus(1.89)和大肠杆菌Escherichia coil(1.157 4)的MIC(抑制生长的最低浓度)值分别为0.78、12.5、1.56和1.56 μg/mL,对番茄灰霉病菌Botrytis cinerea的有效抑制中浓度(EC50)为7.02 μg/mL。     

含苯并咪唑环的1,3,4-噻二唑酰胺衍生物的合成与抑菌活性

为寻找新型活性杂环化合物,通过活性亚结构拼接,以取代苯酚和氯乙酸为起始原料,经醚化、缩合、烃基化和氨解反应,设计并采用微波辅助合成了6种未见文献报道的含苯并咪唑环的1,3,4-噻二唑酰胺衍生物,其结构经红外和核磁共振氢谱确证。初步抑菌活性测试结果表明,所有目标化合物对5种供试病原菌都表现出一定的抑菌活性,其中,化合物7c、7d、7e和7f在50 mg/L下对5种供试病原菌的抑制率均达到80%以上。     

对猪血品质影响的研究

通过近年多次试验，对猪血短期贮存的护色效果进行了研究．结果表明，在猪血中加入抗氧化剂──抗坏血酸钠2g／L和发色助剂──烟酰胺0．5g／L，在0—5℃环境中贮存2～4d效果最佳．并研究证实亚硝酸钠不能作为猪血发色剂使用．     

山东省主要土壤对不同形态氮素吸持能力的研究

通过对１７个土壤样品的吸附试验和２个土壤样品的淋失试验,研究了山东省主要土壤对铵态氮、硝态氮和酰胺态氮（尿素）的吸持能力。结果表明,供试土壤对铵态氮的吸附符合Ｌａｎｇｍｕｉｒ、Ｆｒｅｕｎｄｌｉｃｈ、Ｔｅｍｋｉｎ方程,最大吸附量为４２９７４～１７５４３９μｇ／ｇ土,其中褐土＞棕壤＞潮土;吸附量主要受粘粒含量的影响;供试土壤对硝态氮基本不吸附。在试验范围内,氮素在土壤中主要以硝态氮流失,酰胺态氮也有一定程度流失,其数量受土壤质地和施肥量的影响,铵态氮几乎无流失现象。     

羧酸制备伯胺的方法综述

系统综述了羧酸制备伯胺的各种常用方法,包括羧酸通过酰胺化制备伯胺和羧酸还原为醇、酮或醛后再经氨解反应得到伯胺,以及羧酸直接转化为伯胺的方法,并指出了各种方法的优点以及存在的问题.最后,对羧酸制备伯胺的方法进行了展望.     

Carbon skeletons for amide synthesis during ammonium nutrition in tomato and wheat roots

Heavy application of ammonium nitrogen to plant roots results in the conversion of ammonium nitrogen to the nitrogen of amides, glutamine, and asparagine, which are stored in roots or translocated to shoot. Since the net synthesis of such amides requires the supply of corresponding carbon skeletons, the carbon metabolism in amide synthesis in response to ammonium supply was investigated in tomato and wheat roots. The content of major primary amino acids was determined in tomato and wheat roots during a 4-d period of ammonium nutrition after 1-d culture in nitrogen-free nutrient solution. Ammonium supply led to a continuous increase in the asparagine content in wheat roots, whereas in tomato roots, the glutamine content increased 1 d after ammonium supply and thereafter the glutamine content was higher than the asparagine content. The amounts of amino acids synthesized from glucose-¹⁴C increased while the amounts of organic acids decreased in tomato roots by the supply of ammonium nitrogen for 1 d, compared to the roots that did not receive nitrogen. In tomato roots, the proportion of labeled glutamine was higher than that of labeled asparagine and the C5 amino acids were more strongly labeled than the C4 amino acids. These findings were different from the previous ones in wheat roots where the proportion of asparagine was found to be extremely high (Koga and Ikeda 2000: J. Fac. Agr. Kyushu Univ45, 7–13). To examine the in vivo asparagine synthesis, aspartate-'4C was fed to the roots. The labeling of asparagine, which was the most strongly labeled amino acid among the free amino acids, was remarkably strong in wheat roots whereas the labeling of glutamine was also pronounced in tomato roots. These results indicate that the ability to replenish carbon skeletons for amide synthesis in ammonium nutrition is different between tomato and wheat roots.     

杂环酰胺类化合物的杀菌活性研究进展

酰胺化合物因具有广谱的生物活性而引起广泛关注,将酰胺基团引入到各种不同的杂环结构中,通过结构修饰能产生一系列具有广谱生物活性的化合物,使得它在新型超高效农药创制中发挥出越来越重要的作用。本文综述了杂环酰胺类化合物的杀菌活性,重点介绍了五元杂环、六元杂环、苯并杂环酰胺类化合物的生物活性研究,展望了该类化合物的发展趋势和应用前景。     

Development of a multiplex allele‐specific primer PCR assay for simultaneous detection of QoI and CAA fungicide resistance alleles in Plasmopara viticola populations

BACKGROUND: DNA‐based diagnosis has become a common tool for the evaluation of fungicide resistance in obligate phytopathogenic fungus Plasmopara viticola. RESULTS: A multiplex allele‐specific primer PCR assay has been developed for the rapid detection of fungicide resistance in P. viticola populations. With this assay, a glycine‐to‐alanine substitution at codon 143 of the P. viticola cytochrome b gene, which conferred QoI fungicide resistance, and a glycine‐to‐serine substitution at codon 1105 of the P. viticola cellulose synthase gene PvCesA3, which conferred CAA fungicide resistance, were detected simultaneously. CONCLUSION: It is suggested that the present assay is a reliable tool for the rapid and simultaneous detection of QoI and CAA fungicide resistance alleles in P. viticola populations. The assay required only 2 h from the sampling of symptoms to the detection of resistance alleles to both fungicides. Copyright © 2012 Society of Chemical Industry     

Insulin‐independent actions of glucagon‐like peptide‐1 in wethers

Insulin‐independent actions of glucagon‐like peptide‐1 (GLP‐1) are not yet clear in ruminants. Four Suffolk mature wethers (60.0 ± 6.7 kg body weight (BW)) were intravenously infused with insulin (0.5 mU/kg BW/min; from 0 to 90 min) and GLP‐1 (0.5 μg/kg BW/min; from 60 to 150 min) with both hormones co‐administered from 60 to 90 min, in a repeated‐measure design under euglycemic clamp for 150 min, to investigate whether GLP‐1 has insulin‐independent actions. Jugular blood samples were taken at 15‐min intervals for plasma hormones and metabolites analysis. Compared to baseline concentrations (at 0 min), insulin infusion decreased (P < 0.05) plasma concentrations of glucagon, non‐esterified fatty acids (NEFA), lactate, nonessential amino acids (NEAA), branched‐chain amino acids (BCAA), total amino acids (TAA) and urea nitrogen (UN). Insulin plus GLP‐1 infusion induced a greater increase (P < 0.05) in plasma concentrations of insulin and triglyceride (TG), but decreased (P < 0.05) glucagon, total cholesterol (T‐Cho), NEAA and UN plasma concentrations. GLP‐1 infusion increased (P < 0.05) NEFA, β‐hydroxybutyrate and TG, but decreased (P < 0.05) glucagon, T‐Cho, NEAA, BCAA and UN plasma concentrations. In conclusion, GLP‐1 exerts extrapancreatic roles in ruminants not only insulin‐independent but probably, in contrast to non‐ruminants, antagonistic to insulin effects.