含氟2-氧代环己基磺酰胺的合成及杀菌活性

以环己酮为原料,经磺酰化、碱化后得到2-氧代环己基磺酸钾盐,再经生成酰氯后与胺反应得到9个新的标题化合物,其结构经1H NMR、13C NMR和元素分析确证。初步的生物测定结果表明,部分化合物具有一定的杀菌活性,其中 3e 对棉花立枯病菌Rhizoctonia solani和黄瓜灰霉病菌Botrytis cinerea、 3h和3i 对黄瓜灰霉病菌和油菜菌核病菌Sclerotinia sclerotiorum有较好的活性,50 μ g/mL下的抑制率均在90％以上。     

β-Methoxyacrylates; synthesis of new types of strobilurin fungicides with extended side chains

A series of novel oxime ether β-methoxyacrylates have shown good fungicidal activity against a number of fungal pathogens. These were designed by introducing a one- or two-atom spacer group adjacent to the oxime ether group. Best fungicidal activity was obtained when an amino spacer group was used. ©1999 Society of Chemical Industry     

Development of novel pesticides based on phytoalexins: Part 2. Quantitative structure-activity relationships of 2-heteroaryl-4-chromanone derivatives

Phytoalexins are low-molecular-weight chemicals that immune systems of plants produce and accumulate in response to infections, especially those of fungal origin. Although their content is not high in plants, yet they have shown unique fungicidal activity and played an important role in the defence system of plants. In searching for novel environmentally benign fungicides with high activity, the structures of flavanone derivatives, one of the most important phytoalexins groups, have been modified via bioisosteric substitution and a series of 2-heteroaryl-4-chromanones were designed and synthesized. They showed good fungicidal activities against rice blast disease, Pyricularia grisea (Sacc). Their IC50 values were tested in vitro and the relationship between structure and fungicidal activity was analyzed quantitatively using a Hansch-Fujita approach. The results showed that hydrophobicity was very important for fungicidal activity and there is apparently an optimum hydrophobic property for the molecules at a log Pow value of about 2.7. In addition, the results indicated that electronic effects played an important role in binding with the receptor and that the C=O group was probably a electron-accepting site. The quantitative structure-retention correlative equation of the title compounds was also established.     

含苯基吡啶基团的肟醚乙酸酯类化合物的合成与抑菌活性

以3-羟基苯硼酸和取代含溴吡啶为原料,经Suzuki偶联和亲核取代两步反应合成了24个未见报道的含苯基吡啶基团的肟醚乙酸酯类化合物,其结构均通过1H NMR、ESI-MS和IR确证。初步生物活性测定结果表明,大部分目标化合物具有一定的抑菌活性,其中化合物5i、5r、5t在50 mg/L下对黄瓜霜霉病菌的抑制率达到80%。说明此类化合物具有作为杀菌剂先导进行进一步结构优化的潜力。     

The chemistry and biological activity of a new class of azole fungicides: 1-amino-1,2,4-triazoles

The fungicidal activity of a novel class of triazole compounds in which the 1-position of the azole nucleus is bonded to a nitrogen atom was investigated. Such 1-amino-1,2,4-triazoles are amenable to great structural variation which allows the elucidation of the requirements for biological activity. As in most other triazole fungicides, the basic structural requirement for activity is a two-atom bridge connecting the azole nucleus to a hydrophobic group, typically an aromatic ring. The synthesis and optimization of fungicidal activity of this class of triazole fungicide are discussed.     

农用抗生素产生菌Z139菌株的稳定性

从秦蛉山区采集的土样中分离到一株小单孢菌属放线菌菌株Z₁₃₉,其代谢产物对多种农业病原真菌和细菌均有较强的抑制活性。无论是在连续传代过程中,还是在不同温度条件保存中,Z₁₃₉菌株的培养特征和产生抗生素性能均表现稳定。菌株产生的抗菌物质可耐100℃高温,且对酸碱稳定。     

Use of linear free energy related and other parameters in the study of fungicidal selectivity

The modulation of fungicidal activity in a congeneric series of compounds is dependent on several processes taking place in the biological object which may be influenced by the different hydrophobic, electronic and steric properties of the members of the series. These possible influences can be studied in a quantitative way with multiple regression analysis using substituent constants for the properties mentioned. The comparative study of the resulting regression equations for the activity on different fungi or on a fungus and another biological subject may contribute to an understanding of fungicidal selectivity. This is illustrated in studies on the fungitoxicity of isophthalonitriles, 2-chlorobenzonitriles, arylsulphonyl- and arylsulphinyl-alkylthio-cyanates, acetylenic sulphones, methyl benzimidazol-2-ylcarbamates and phosphorus compounds derived from 3-amino-1,2,4-triazole. In these studies new steric parameters were used, which have been introduced recently.     

含稠杂环结构的螺环丁烯内酯类化合物的合成及杀菌活性

为了发现更高杀菌活性的螺环丁烯内酯类化合物并分析该类化合物的构效关系，设计并合成了一系列未见文献报道的含咪唑并噻唑、咪唑并噻嗪和咪唑并噻嗪酮等稠杂环结构的螺环丁烯内酯类化合物，其结构通过核磁共振氢谱 (1H NMR)、碳谱 (13C NMR)及高分辨质谱 (HRMS)确证。离体杀菌活性测试结果表明，化合物 5f 和 6f 对油菜菌核病菌的EC₅₀值分别为33.2和29.8 mg/L，优于对照药剂咪唑菌酮(46.8 mg/L)，化合物 7b 和 7e 对辣椒疫霉的EC₅₀值分别为45.8和43.5 mg/L，优于咪唑菌酮(50.7 mg/L)，与先导化合物相比，其杀菌活性高于2-甲硫基衍生物，低于2-芳氨基衍生物，表明稠杂环的引入可以提高化合物的杀菌活性，而结构中的NH片段对杀菌活性具有关键作用。     

Rationally Designed Guanidine and Amidine Fungicides

A previous investigation established that compounds containing a guanidinium or amidinium grouping are effective inhibitors of sterol Δ⁸–Δ⁷ isomerase and/or Δ¹⁴ reductase activity in plant pathogenic fungi. A binding model for known fungicidal inhibitors of this enzyme has now been used to rationally design further guanidinium or amidinium inhibitors. Three novel classes of chemistry were investigated. The results of biochemical testing against ergosterol biosynthesis in Ustilago maydis (DC) Corda and of in-vivo testing for fungicidal activity against Erysiphe graminis DC f. sp. hordei Marchal (powdery mildew of barley), do much to support the binding model, and compounds with significant fungicidal activity have been found. © 1997 SCI.     

2-(溴代吡咯腈-1-基)乙酸衍生物的设计、合成及生物活性

为了发现具有生物活性的新化合物,以溴代吡咯腈为先导化合物,通过亲核取代等反应合成了一系列新型2-(溴代吡咯腈-1-基)乙酸衍生物(5a～5m, 6a～6o),其结构均经核磁共振氢谱(¹H NMR)、碳谱(¹³C NMR)和高分辨质谱(HRMS)确证。杀菌活性测定结果显示：化合物2、3和5m对水稻稻瘟病菌Magnaporthe oryzae均表现出良好的杀菌活性,其EC₅₀值分别为0.0532、0.0470和0.0174 mmol/L,优于对照药剂咯菌腈(0.0914 mmol/L),但不及对照药剂嘧菌酯(0.0001 mmol/L);化合物5m表现出一定的杀菌广谱性,其对水稻纹枯病菌Rhizoctonia solani和小麦根腐病菌Bipolaris sorokiniana的EC₅₀值分别为0.0218和0.0420 mmol/L,但均不及对照药剂咯菌腈(EC₅₀值分别为0.0002和0.0010 mmol/L)。杀虫、杀螨活性测定结果显示,在0.2 mmol/L浓度下,目标化...     

Triazolines VII. Results of screening l,5-diaryl-Δ2-l,2,3-triazolines for pesticidal properties

Twenty-one l,5-diaryl-δ2-l,2,3-triazolines were screened for the first time for pesticidal properties—insecticidal, fungicidal, bactericidal and virucidal. Five of the compounds showed some fungicidal activity, and 13 exhibited low level insecticidal activity, mostly toward the Mexican bean beetle.     

Diastereoisomers and enantiomers of paclobutrazol: Their preparation and biological activity

Paclobutrazol is a highly active plant growth regulator with very good fungicidal activity. Aspects of the synthesis of paclobutrazol and its diastereoisomer are discussed, the resolution of paclobutrazol into its two enantiomers is described. It has been shown for the first time that it is possible to separate the plant growth regulatory activity from the fungicidal activity by resolution. Computer graphic studies are also included.     

Synthesis and fungicidal activity of 1,4-dithiino[2,3-b]quinoxaline-2,3-dicarbonitriles

A series of eleven 1,4-dithiino[2,3-b]quinoxaline-2,3-dicarbonitriles was prepared by reaction of 2,3-dichloroquinoxalines with disodium (2)-2,3-dimercapto-2-butenedinitrile in N,N-dimethylformamide. These products were tested for in-vitro fungicidal activity by a Minimum Inhibitory Concentration (MIC) method. Several of these compounds showed broad-spectrum fungicidal activity. The activity exhibited by these compounds was greatly dependent upon the substituents of the quinoxaline ring, with the nitro-substituted derivatives showing the highest levels of antifungal activity. None of the compounds prepared, however, showed fungicidal activity comparable to that of the commercial fungicides screened.     

菲并吲哚里西啶生物碱及其盐衍生物 的生物活性研究

分别采用菌丝生长速率法和盆栽法,测定了一系列菲并吲哚里西啶生物碱及其盐衍生物的杀菌及除草活性。结果表明:该类生物碱及其盐衍生物表现出了很好的杀菌活性,尤其是生物碱安托芬 ± )-antofine]( 2 )和脱氧娃儿藤宁碱 ± )-deoxytylophorinine]( 3 )在50 μ g/mL下,对番茄早疫Alternaria solani、花生褐斑Cercospora arachidicola、苹果轮纹Physalospora piricola 和黄瓜枯萎Cladosporium cucumerium 4种菌体的抑制率达70%~100%;但未表现出明显的除草活性。     

含取代吡啶基的不对称硫代磷(膦)酸酯的合成及杀菌活性研究

从二硫代磷酸二乙酯钠盐或O,O-二乙基硫代磷酰氯出发 ,经酯化、去烷基化反应得到相应的硫代或二硫代铵盐 ,分别与 2 -氯 - 5 -氯甲基吡啶反应得产物 2 a～ 2 c。从 O-乙基硫代磷酰二氯或苯基硫代膦酰二氯出发 ,先与取代苯酚或甲胺反应 ,然后与 2 -氯 - 5 -羟甲基吡啶反应得到产物 2 d～ 2 k和 2 m～ 2 u。O-乙基 - S-丙基二硫代磷酰氯、O-乙基硫代磷酰二氯和苯基硫代膦酰二氯与 2 -氯 - 5 -羟甲基吡啶反应分别得产物 2 l、2 v和 2 w。所合成的 2 3个新化合物对9种植物病菌的离体及活体杀菌活性测试表明 ,其中一些化合物对水稻稻瘟病和水稻纹枯病有一定活性 ,个别化合物活性很好 ,但对其它病菌的活性均较低     

Mode of action and pesticidal activity of the natural product dunnione and of some analogues

This paper reports the investigation of the insecticidal and fungicidal activity of dunnione, a natural product obtained inadvertently as a by-product of a synthesis programme. Dunnione exhibits no insecticidal activity but has an unusually broad spectrum of antifungal activity. In vitro and in vivo (preventative) activities were comparable to those of several long-established fungicides (eg carbendazim). However, in whole-plant assays, its eradicant activity was unexpectedly low, probably due to poor dose-transfer from leaf surface to fungus. The level of residual activity appears to be influenced by the formulation. Finally, its potential as a lead structure was assessed, and several analogues synthesised which exhibited high activity in the in vitro assays. Mode-of-action studies revealed that dunnione exerts its action primarily through initiation of redox cycling. This contrasts to the activity of BTG 505, the biochemical/chemical precursor, which does not initiate redox cycling but instead exhibits both insecticidal and fungicidal activity by inhibiting mitochondrial Complex III.     

N-(芳基磺酰氨基乙基)-1,6-己内酰胺的合成及杀菌活性

以环己酮为原料,合成了9个结构新颖的N-(芳基磺酰氨基乙基)-1,6-己内酰胺( 3 ),其结构均经IR、1H NMR、13C NMR和元素分析确证。初步的生物活性测定结果表明,部分化合物对供试的6种病原真菌具有一定的杀菌活性,其中 3a、3b、3d和3g 对番茄叶霉病菌的抑制活性与对照药剂百菌清相当,抑制率大于90％。     

不对称S-烷基(烯丙基)O-取代苯基二硫代磷酸酯的合成及其杀菌活性研究

从二硫代磷酸二酯钠盐出发 ,经烷基化得二硫代磷酸三酯 ,用二甲胺为去烷基化试剂 ,得二硫代磷酸铵盐 ,再用五氯化磷或三氯氧磷氯化 ,并进一步与取代苯酚反应得到目标化合物 O-烷基 S-烷基 (烯丙基 ) O-取代苯基二硫代磷酸酯 ,共 2 8个新化合物。它们分别与 8种植物病菌的离体实验表明 ,这些化合物对其中 7种病菌只有很低的抑菌活性 ,而对稻瘟病菌却有明显的活性。     

N-取代苯基-1-(2,4-二氟苯基)-2-(1H-1,2,4-三唑-1-基)乙基氨基甲酸酯的合成及生物活性

为了寻找高活性的三唑类苯基氨基甲酸酯衍生物,以 1,2,4-三氮唑、2-氯-2,4-二氟苯乙酮为原料,采用活性亚结构拼接的策略,设计并合成了18个未见文献报道的N-取代苯基-1-(2,4-二氟苯基)-2-(1H-1,2,4-三唑-1-基)乙基氨基甲酸酯衍生物 6a ~ 6r 。其结构均通过 1H NMR、13C NMR和高分辨质谱（HRMS）的确证。抑菌活性测定结果显示:在100 μmol/L下,化合物 6m 对6种供试真菌具有良好的抑制作用,抑制率均达到50%以上。化合物 6p 对油菜菌核病菌Sclerotinia sclerotiorum的EC₅₀值为7.1 μmol/L,抑菌活性高于对照药剂烯唑醇（EC₅₀值9.1 μmol/L）。杀螨活性测定结果显示,在150 μmol/L时,化合物 6h 、 6k 和 6o 在48 h时对朱砂叶螨Tetranychus cinnabarinus的致死率分别为67.7%、74.9%和57.5%,杀螨活性低于对照药剂阿维菌素B1a(致死率100%)。本研究所合成的化合物 6o 兼具一定杀菌和杀螨活性,可为新型三唑类杀菌杀螨化合物的设计与研究提供参考。     

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。