吩嗪-1-羧酸双酰肼衍生物的合成、杀菌活性及韧皮部的输导性研究

天然产物吩嗪-1-羧酸（PCA,申嗪霉素）及其衍生物吩嗪-1-甲酰肼具有独特的化学结构和优良的杀菌等生物活性,但均没有韧皮部输导性。本文以具有抑菌活性的吩嗪-1-羧酸和具有韧皮部输导性的马来酰肼为先导化合物,将马来酰肼中的双酰肼结构引入到吩嗪-1-羧酸中,设计、合成了17个新化合物,其结构均经过核磁共振氢谱、高分辨质谱及X-射线单晶衍射分析确证。初步生物活性测试表明:大部分目标化合物在50 mg/L下对水稻纹枯病菌Thanatephorus cucumeris表现出中等偏上的抑制活性,其中化合物6m的抑制率达92%。但输导性研究结果显示,目标化合物没有明显的韧皮部输导性。     

含苯乙酮结构片段的吩嗪-1-羧酸酯类衍生物的合成及生物活性

为了提高吩嗪-1-羧酸 (申嗪霉素) 的生物活性,以吩嗪-1-羧酸和不同取代的苯乙酮为原料,通过溴化反应和亲核取代反应,合成了22个未见文献报道的含苯乙酮结构片段的吩嗪-1-羧酸酯类化合物 3a ～ 3c 和 6a ～ 6s ,其结构均得到核磁共振氢谱(1H NMR)、碳谱(13C NMR)和高分辨质谱确证。分别采用菌丝生长速率法和琼脂保湿浸叶法测定了目标化合物对6种植物病原菌的杀菌活性和对朱砂叶螨雌成螨的杀螨活性。杀菌活性测定结果表明:在0.2 mmol/L下大部分目标化合物对水稻纹枯病菌Rhizoctonia solani具有一定的抑制作用,其中 6b 和 6e 的抑制率分别为56.05%和65.37%,低于对照药剂吩嗪-1-羧酸 (86.83%)。杀螨活性测定结果表明:药后24 h,大部分目标化合物对朱砂叶螨Tetranychus cinnabarinus雌成螨具有良好的杀螨活性,在1 mmol/L下化合物 6k 和 6m 的校正死亡率分别为87.88%和90.82%,进一步测得其相应的LC₅₀值分别为0.25 和0.19 mmol/L。本研究所合成的新化合物不仅具有一定的杀菌活性,还具有较好的杀螨活性,这为吩嗪-1-羧酸的进一步结构改造提供了新思路。     

4-(吩嗪-1-酰氧基)肉桂酸酯和N-吩嗪-1-甲酰基-N'-肉桂酰基乙二胺的合成及生物活性

以不同取代的肉桂酸为原料,通过酯化反应和酰基的亲核取代反应对天然产物吩嗪-1-羧酸(申嗪霉素)进行了结构修饰,合成了2个系列含肉桂酸结构片段的吩嗪-1-羧酸酯类衍生物5a～～5f和吩嗪-1-甲酰胺类衍生物10a～～10r,所有衍生物的结构均得到核磁共振氢谱(1H NMR)、碳谱(13C NMR)和高分辨质谱确证.分别采...     

微生物源农药申嗪霉素的研制与应用

申嗪霉素是中国自主研发的一种新型微生物源农药,具有高效、安全、广谱等特点,其主要成分是甜瓜根际促生菌M18产生的次级代谢产物吩嗪-1-羧酸。文章重点就申嗪霉素产生菌M18的分离及其代谢产物的鉴定、申嗪霉素生物合成及调控机理最新研究进展、申嗪霉素高产工程菌株的构建和产业化、以及申嗪霉素大田防病试验结果及推广应用情况等进行详细综述,并对其抗菌作用机理进行探讨,旨在为申嗪霉素的生物合成机理研究、遗传和代谢改造以及推广应用提供参考。     

(4-亚甲基-5-羰基-3-四氢呋喃基)-苯甲酸甲酯衍生物的合成及其杀菌活性

为了探索天然产物Cedarmycins衍生物的结构与活性关系,以α-亚甲基-β-羟甲基-γ-丁内酯为起始原料,经过与不同取代的羧酸缩合,合成了19个新的(4-亚甲基-5-羰基-3-四氢呋喃基)-苯甲酸甲酯衍生物。杀菌活性测定结果表明,该类衍生物具有广谱的杀菌活性,尤其对水稻纹枯病菌Rhizoctonia solani和辣椒疫霉Phytophthora capsici显示出很强的杀菌活性,其中化合物2e(R=2,4-2Cl)对这2种病菌的EC50值约为1.6 mg/L。     

吩嗪类化合物对梨火疫病菌的抗菌活性研究

由解淀粉欧文氏菌Erwinia amylovora引起的梨火疫病是危害梨、苹果等蔷薇科果树的一种重要细菌病害,在世界范围内造成严重损失,是果树上重要的防控对象。药剂防治是控制梨火疫病传播蔓延的一种重要手段。吩嗪类化合物是绿针假单胞菌Pseudomonas chlororaphis和抗生素溶杆菌Lysobacter antibioticus等生防细菌产生的抗菌活性物质,在农药、医药等领域有广阔的应用前景。为明确吩嗪类化合物对梨火疫病菌的抗菌活性,本研究通过测定含不同浓度药剂的菌悬液OD₆₀₀的方法,评价了本课题组分离的5个吩嗪类化合物以及常见的抗细菌药剂对梨火疫病菌的室内抗菌活性。结果表明,堆囊粘菌素(myxin)和吩嗪-1-羧酸(PCA)活性较好,EC₅₀分别为7.20μg/mL和46.41μg/mL。中生菌素、噻霉酮、春雷霉素等药剂EC₅₀为7.21～50.74μg/mL。进一步对活性较好的药剂进行了复配筛选,结果显示,吩嗪-1-羧酸∶中生菌素=9∶1复配组合的EC₅₀为27.15μg/mL,增效...     

新型N-芳基-2-((5-((4,6-二甲基嘧啶-2-基)硫甲基)-1,3,4-噻二唑-2-基)硫)乙酰胺类化合物的合成及杀菌活性

为寻找新型杂环活性化合物,通过活性亚结构拼接,以硫脲和乙酰丙酮为起始原料合成4,6-二甲基嘧啶-2-硫醇,随后经酯化、肼化、环化和缩合反应,设计并采用微波辅助合成了10个新型N-芳基-2-（（5-（（4,6-二甲基嘧啶-2-基）硫甲基）-1,3,4-噻二唑-2-基）硫）乙酰胺类化合物,其结构通过核磁共振氢谱和碳谱、红外光谱、质谱及元素分析确认。初步生物活性测试结果表明,在50 mg/L下,大部分目标化合物对植物病原真菌具有一定的抑制活性,其中化合物8h对黄瓜炭疽病菌Colletotrichum orbiculare的抑制率达77.3%。     

生防细菌PA2101和PG3402抑菌和促生特性的研究

以本实验室分离的在烟草生产上具有较大生防潜力的铜绿假单胞杆菌PA2101和格拉纳达假单胞杆菌PG3402为对象,测定了这2株细菌的抑菌活性及促生特性。试验结果表明,菌株PA2101和PG3402对烟草根腐病、烟草赤星病、小麦纹枯病、芝麻茎点枯病和地黄轮纹病等多种作物常见病害的病原菌具有较强的拮抗作用;2株菌株的无菌发酵滤液能使烟草疫霉和根串珠霉菌丝生长畸形、抑制根串珠霉分生孢子的萌发。菌株PA2101和PG3402产生对2种病原菌有抑制作用的挥发性物质。抑菌特性检测结果表明,菌株PA2101和PG3402均能产生蛋白酶、纤维素酶和β-1,3-葡聚糖酶等胞外酶,PA2101还能分泌几丁质酶。另外,2株菌株能合成抑菌活性物质氢氰酸（HCN）。抗生素合成基因检测结果发现,菌株PA2101和PG3402均包含吩嗪-1-羧酸（Phenazine-1-carboxylic acid,PCA）合成基因,PG3402还含有2,4-二乙酰基间苯三酚（2,4-diacetylphloroglucinal,DAPG）合成基因。促生物质的检测结果表明,菌株PA2101和PG3402均可产生嗜铁素和生长素（IAA）,且具备溶磷特性。综上所述,菌株PA2101和PG3402抑菌谱较广,产生多种抑菌和促生物质,含有合成PCA和DAPG的基因,可用于烟草病害的防控。     

含硝基亚氨基1,3,4-噻二唑啉类化合物的合成及生物活性

1,3,4-噻二唑环在医药上已被广泛研究 ,但目前在农药中的应用相对较少。许多 1 ,3,4-噻二唑衍生物具有杀虫、除草等各种生物活性 [1 ] ,而硝基亚氨基是吡虫啉类杀虫剂中具有特殊作用的活性基团 ,我们把硝基亚氨基引入 1 ,3,4-噻二唑啉环 ,合成了系列化合物 ,期望能发现新的具有较好生物活性的化合物。选择羧酸为起始原料 ,与氨基硫脲 在脱水剂浓硫酸作用下反应关环生成 5 -烷基 - 2 -氨基 - 1 ,3,4-噻二唑 , 与发烟硝酸于 0℃左右反应 ,得到 5 -烷基 - 2 -硝基氨基 - 1 ,3,4-噻二唑 , 与硫酸酯或卤代烷反应生成目标化合物 。其合成路线…     

N-[5-（1-邻氯苯氧乙基）-1,3,4-噻二唑-2-基]-N′-芳氧乙酰基硫脲的合成与生物活性

为了寻找新的高生物活性农药,通过2-氨基-5-（1-邻氯苯氧乙基）-1,3,4-噻二唑与芳氧乙酰基异硫氰酸酯反应,合成了9个新的芳氧乙酰基硫脲,初步的生物活性测定结果表明,部分目标化合物具有良好的植物生长调节活性,其中2c、2d具有较好的生长素活性,其生长促进率分别为26.9%和27.2%.     

高效液相色谱法检测申嗪霉素在人参及其土壤中的残留

通过田间植株直接施药、定期采样后,采用高效液相色谱法检测人参及其土壤中申嗪霉素的残留量,研究了其在人参及田间土壤中的消解动态和最终残留量,并在室内模拟环境条件下,初步探讨了土壤类型及含水量、微生物、温度因素对其在土壤中降解的影响。结果表明:1%申嗪霉素悬浮剂在人参叶片及其田间土壤中的消解动态均符合一级动力学方程,消解半衰期分别为3.4和3.0d;以推荐高剂量有效成分用量18g/hm2(制剂用量为1.8kg/hm2)和推荐高剂量的1.5倍有效成分用量27g/hm2(制剂用量为2.7kg/hm2)2个施药剂量喷雾施药,距最后一次施药后7、14和21d采收的人参鲜根和干根中申嗪霉素的最终残留量均低于检测限(0.002mg/kg);室内模拟环境条件下,微生物作用增强、有机质含量高、温度升高和含水量增加,均可有效促进土壤中申嗪霉素的降解。     

1-甲基-3-二氟甲基吡唑酰胺类化合物的合成及抑菌活性

以1-甲基-3-二氟甲基吡唑-4-甲酸为原料,经过1-甲基-3-二氟甲基吡唑-4-甲酰氯与相应的氨基苯并杂环类、芳胺类化合物反应,得到了14个未见文献报道的吡唑-4-甲酰胺类化合物(6a~6g、7a~7g),其结构均通过1H NMR、MS和IR表征。抑菌活性测试结果表明,在100 mg/L下,目标化合物对供试植物病原菌均有不同程度的抑制作用,其中7a~7g的抑菌活性较高,部分对苹果炭疽病菌的抑制率在90%以上。     

Phytotoxic activity of norbornane and nortricyclene lactones

A series of bromo-, hydroxy- and keto-derivatives of norbornane-6-hydroxy-2-carboxylic acid, y-lactone and some related compounds have been prepared and examined for phytotoxic activity. The 3-exo-propionyl, and 3-exo-5-exo-dibromo substituted compounds have been found to have the greatest activity.     

Studies on the mechanism of selectivity of the auxin herbicide quinmerac

Investigations were conducted to elucidate the mechanism of selectivity of the auxin herbicide, quinmerac, in cleavers (Galium aparine) and the tolerant crops sugarbeet (Beta vulgaris), oilseed rape (Brassica napus) and wheat (Triticum aestivum). After root treatment with the herbicide, the selectivity has been quantified as approximately 400-fold between oilseed rape and Galium and 1000-fold between sugarbeet or wheat and the weed species. When 1 and 10 μM [¹⁴C]quinmerac were applied for 4 h, no significant differences between root absorption and translocation of ¹⁴C by Galium and the crop species were found. After 16 h, metabolism of [¹⁴C]quinmerac to the biologically inactive hydroxymethyl and dicarboxylic acid derivatives was more rapid in wheat and sugarbeet than in Galium. In oilseed rape, a lower rate of herbicide metabolism was observed. In Galium, accumulations of abscisic acid (ABA), triggered by quinmerac-stimulated ethylene biosynthesis, were found to cause the herbicidal growth inhibition which develops during 24 h of application. Within 1 h of treatment, quinmerac stimulated 1-aminocyclopropane-1-carboxylic acid (ACC) synthase activity and ACC concentration specifically in Galium shoot tissue. During the next 4 h, ACC synthase activity was increased up to 50-fold, relative to the control. Within 3 h of exposure to quinmerac, increased ethylene formation followed by higher ABA levels was detected. In sugarbeet, oilseed rape and wheat, quinmerac did not stimulate ACC synthase activity and ACC and ABA levels. It is suggested that (i) the selectivity of quinmerac is primarily based upon the lower sensitivity to the herbicide of the tissue/target in the crop species, (ii) the induction process of the ACC synthase activity in the shoot tissue is the primary target of herbicidal interference. In wheat and sugarbeet, tolerance to quinmerac is additionally increased by a more rapid metabolism. © 1998 SCI.     

Analysis of polar metabolites of organophosphorus insecticides on an anion-exchange chromatographic column

A simple and rapid procedure is described for the qualitative and quantitative analysis of metabolites of malathion and other insecticides. The omission of an extraction at low pH, and mild conditions of anion-exchange chromatography on QAE-Sephadex prevent the degradation of a malathion metabolite, S-(1-carboxy-2-ethoxycarbonyl)-ethyl O,O-dimethyl phosphorothioate (malaoxon α-carboxylic acid), which takes place under strongly acid conditions. Disadvantages of the commonly used fractionation of malathion and malaoxon metabolites based on partitioning are discussed.     

四种杀菌剂对两种赤眼蜂的毒性分析及敏感性比较

采用药膜法分别测定了95%三唑酮、99.5%肟菌酯、96.2%咪鲜胺和95%申嗪霉素4种杀菌剂对玉米螟赤眼蜂Trichogramma ostriniae和松毛虫赤眼蜂Trichogramma dendrolimi Matsumura的急性毒性。结果表明,4种供试杀菌剂对玉米螟赤眼蜂的直接接触毒性LC50值分别为0.822 0、48.70、12.94和24.25 mg/L, 对松毛虫赤眼蜂的LC50值分别为10.55、180.3、218.1和240.3 mg/L。 即4种杀菌剂对两种赤眼蜂的风险性存在差异,供试药剂对松毛虫赤眼蜂相对较为安全。由于玉米螟赤眼蜂比松毛虫赤眼蜂对供试杀菌剂更为敏感,因此以玉米螟赤眼蜂作为评价农药对赤眼蜂风险的供试生物更为适宜。     

The antifungal activity of some sulphonyl derivatives of isoxazole,pyrazole, thiazole and thiophene

Fifty-three heterocyclic sulphonyl derivatives including eight sulphonamides, three sulphonyl azides, nine sulphonohydrazides and twenty sulphonohydrazones of substituted thiophenes, and a smaller range of analogous isoxazoles pryazoles and thiazoles, were tested as potential fungicides in a simple screening procedure against Mucor mucedo, Septoria nodorum, Trichoderma viride, Chaetomium globosum and Aspergillus niger. Several thiophene-2-sulphonyl based compounds exhibited a high level of antifungal activity at 100 mg litre^?1 against the five test species, especially the mono-halogen-substituted sulphonamides and sulphonohydrazines, in which a single chlorine or bromine atom was substituted in the para position of an attached phenyl ring. The most active compound, against all five species of fungus was N-(4-chlorophenyl)-N-(trichloromethylthio) thiophene-2-sulphonamide which had average MIC₅₀ and MIC₁₀₀ values of 86 and 180 μmol respectively. (MIC₅₀ and MIC₁₀₀ values are, respectively, the concentrations required to inhibit fungal growth by 50% and to inhibit it totally.) In general, the isoxazole analogues of the thiophene-2-sulphonyl compounds exhibited a much lower fungitoxic activity, whilst the pyrazole and thiazole based compounds had little or no activity. Compared with the other results, the considerable activity shown by 4-[2′-(3,4-dichlorobenzylidene)hydrazinosulphonyl]thiophene-2-carboxylic acid was unexpected.     

Cell surfaces in plant micro-organism interactions. VIII. Increased proteinase inhibitor activity in melon plants in response to infection by Colletotrichum lagenarium or to treatment with an elicitor fraction from this fungus

Proteinase inhibitor activity had increased sharply in melon seedlings infected by Colletotrichum lagenarium 3 days after inoculation. The activity was associated with heat stable proteins and was effective against the protease produced by the fungus as well as against trypsin. Treatment of healthy melon leaves with an elicitor of ethylene isolated from the pathogen, resulted in a three-fold increase in proteinase inhibitor activity after 24 h. Ethylene production increased early in elicitor-treated leaves and may be involved in the elicitation of proteinase inhibitor activity. In the presence of aminoethoxyvinylglycine, an inhibitor of ethylene biosynthesis, both elicitor-induced ethylene and, to a lesser extent, elicitor-induced proteinase inhibitor activity were inhibited. In contrast, 1-aminocyclopropane-1-carboxylic acid, the direct precursor of ethylene, triggers proteinase inhibitor activity. It is concluded that ethylene is involved in the elicitation of proteinase inhibitor activity, but its exact role remains to be defined.