含1,3,4-噻二唑的吡啶联吡唑乙酰胺类化合物的合成及除草活性

以乙酰丙酮、溴乙酸乙酯和2,6-二氯吡啶为起始原料,经取代、肼基化、环合、水解、酸化及缩合等反应,得到9个未见文献报道的吡啶联吡唑乙酰基类化合物 B1~B9 。其结构均经核磁共振氢谱和质谱表征。初步生物活性测定表明:在150 g/hm2的处理剂量下,大部分目标化合物表现出一定的除草活性,其中化合物 B2、B3、B6 和 B8 对苘麻Abutilon theophrasti Medicus、反枝苋Amaranthus retroflexus和凹头苋Amaranthus lividus L.生长的抑制率接近100%。     

Novel 1,3,5-triazine derivatives with herbicidal activity

New fluoroalkyl-substituted 1,3,5-triazine derivatives were synthesized and screened for herbicidal activity using a greenhouse pot test. Surprisingly, a series of 2-alkyl-4-fluoroalkyl-6-aralkylamino-1,3,5-triazines e.g. 6-(4-bromobenzylamino)-2-methyl-4-trifluoromethyl-1,3,5-triazine was found to possess strong pre- and post-emergence herbicidal activities, although the conventional herbicidal 1,3,5-triazines generally should have a 2-substituted-4,6-diamino-1,3,5-triazine structure for herbicidal activity. Our compounds show strong Photosynthetic Electron Transport inhibitory activity (PI₅₀ c 7). Although their herbicidal effect is considered to be caused by a process similar to that for the conventional 1,3,5-triazine herbicide atrazine, they can control atrazine-resistant Chenopodium album effectively, and will thus form promising trial compounds for new triazine herbicide design.     

1-取代苯胺基- 4,4-二甲基-2-(1H-1,2,4-三唑-1-基)-1-戊烯-3-酮的合成及其生物活性

为寻找高活性的烯基三唑类杀菌剂,利用1-二甲氨基-4,4-二甲基-2-(1H-1,2,4-三唑-1-基)-1-戊烯-3-酮与取代苯胺进行亲核取代反应,合成了一系列新型1-取代苯胺基-4,4-二甲基-2-(1H-1,2,4-三唑-1-基)-1-戊烯-3-酮化合物,其结构经元素分析、核磁共振氢谱确认。由1H NMR分析结果推测该类化合物E式构型为优势产物。初步生物活性测试结果表明,化合物 1n (取代基R=3-OCH3)在50 μg/mL浓度下对葡萄白腐菌Coniothyrium diplodiella、黄瓜黑星菌Cladosporium cucumerinum等的抑制率均达到100%;在10 μg/mL浓度下对促进黄瓜子叶生根的活性达到155.2%。     

2-(5,7-二甲基-1,2,4-三唑[1,5-a]嘧啶-2-硫代)乙酰胺类化合物的合成及除草活性

以芳胺或取代稠杂环胺、氯乙酰氯和2-巯基-5,7-二甲基-1,2,4-三唑 嘧啶为原料,合成了8个含稠杂环及芳环的三唑并嘧啶类新化合物,结构经1H NMR, MS 和IR确证,初步测定了该类化合物在室温下对稗草等3种禾本科杂草和反枝苋等3种阔叶杂草芽前芽后的抑制率,结果表明:有6个化合物在有效剂量75 g/hm2下的抑制率超过80%。     

3-芳氧基-6-氯(或氟)哒嗪类化合物的合成及除草活性研究

从3,6-二氯哒嗪( Ⅰ) 出发,通过氟代得到3,6-二氟哒嗪( Ⅱ )。将 Ⅰ,Ⅱ 分别与取代苯酚缩合,得到了18个3-芳氧基-6-氯哒嗪( Ⅲ )和12个3-芳氧基-6-氟哒嗪( Ⅳ )。所有目标化合物( Ⅲ,Ⅳ )的结构都经过 1H NMR和元素分析确证,部分化合物经IR确证。初步的生物测定结果表明,目标化合物具有不同程度的除草活性,其中化合物 Ⅲ3、Ⅲ8和Ⅳ2 在100 μg/mL的浓度下对稗草Echinochtoa crus-galli的抑制率分别达到95.7%、96.1%和91.2%。     

2-(5,7-二甲基-1,2,4-三唑[1,5-a]嘧啶-2-硫代)乙酰胺类化合物的合成及除草活性

以芳胺或取代稠杂环胺、氯乙酰氯和2-巯基-5,7-二甲基-1,2,4-三唑[1,5a-]嘧啶为原料,合成了8个含稠杂环及芳环的三唑并嘧啶类新化合物,结构经1H NMR,M S和IR确证,初步测定了该类化合物在室温下对稗草等3种禾本科杂草和反枝苋等3种阔叶杂草芽前芽后的抑制率,结果表明:有6个化合物在有效剂量75g/hm2下的抑制率超过80%。     

Binding activity of substituted benzyl derivatives of chloronicotinyl insecticides to housefly‐head membranes,and its relationship to insecticidal activity against the housefly Musca domestica

Variously substituted benzyl derivatives of chloronicotinyl insecticides were synthesized with a wide range of substituents including halogens, NO₂, CN, CF₃ and small alkyl and alkoxy groups at the ortho, meta and para positions, as well as multiple‐substituted benzyl analogues. Their binding activity to the α‐bungarotoxin binding site in housefly (Musca domestica) head membrane preparations was measured. Among the compounds tested, the activity of the meta‐CN derivative was the highest, being 20–100 times higher than those of imidacloprid, acetamiprid and nitenpyram. The synergized insecticidal activity against houseflies was also measured for selected compounds with the metabolic inhibitor, NIA16388 (propargyl propyl phenylphosphonate). For the nitromethylene analogues, including both benzyl and pyridylmethyl analogues, higher binding activity usually resulted in higher insecticidal activity. © 2000 Society of Chemical Industry     

2-[4-(对氟苯基)噻唑-2-基]-3-羟基-3-烃氧基丙烯腈的合成及杀菌活性

为了寻找生物活性良好的噻唑基丙烯腈类化合物,利用2-氰甲基-4-(对氟苯基)噻唑( 3 )与取代氯甲酸酯( 4 )在碱存在下反应,合成了15个未见文献报道的2- -3-羟基-3-烃氧基丙烯腈化合物( 5 ),其结构经核磁共振氢谱、质谱和元素分析表征。初步杀菌活性测试结果表明:所有化合物在试验浓度下均具有一定的抑菌活性,尤其对炭疽病菌Colletotrichum gossypii表现出较好的抑制活性,在质量浓度25 mg/L下,所有化合物的抑制率均在50%以上,其中化合物 5a、5e、5g、5k、5n和5o 的抑制率在80%以上。     

1-(3-氯吡啶-2-基)-5-二氟甲基-1H-4-吡唑酰胺类化合物的合成及杀菌活性

以2,3-二氯吡啶(1)为起始原料,经肼基化、环合、水解和酰氯化反应,生成1-(3-氯-2-吡啶)-5-二氟甲基-1H-吡唑-4-甲酰氯(6),(6)与取代基苯胺(7) 反应,制得13个未见文献报道的1-吡啶基吡唑酰胺类目标化合物。利用核磁共振氢谱、质谱(LC-MS)和元素分析对目标化合物的结构进行了表征。初步杀菌活性测定结果表明,在 50 mg/L下,大部分目标化合物对瓜类炭疽病菌Gibberella zeae、瓜类灰霉病菌Botrytis cinerea和水稻纹枯病菌Rhizoctonia solani的抑制活性均不高,仅ZJ-10对瓜类灰霉病菌的抑制率达76.03%。     

Growth regulator inhibition of tobacco callus growth

The activity of two groups of growth regulators, substituted dinitroanilines and nitrophenylhydrazines, were evaluated in a tobacco (Nicotiana tabacum L. “X-73”) callus tissue bioassay. Molar concentrations required to inhibit fresh weight gain by 50% (I₅₀) was determined by using linear regression analysis on data obtained by testing a range of five concentrations of each chemical. All chemicals tested were inhibitory to callus tissue grown in the dark. Cell division seemed to be the primary activity inhibited. The most active of the dinitroaniline series was α,α,α-trifluoro-2,6-dinitro-N-ethyl-N-2′,6′-dichlorobenzyl-p-toluidine (I) (I₅₀ = 1.5 × 10^?10M). I and two other N-(o-halobenzyl) dinitroanilines were more active than α,α,α-trifluoro-2,6-dinitro-N-ethyl-N-2′-chloro-6′-fluorobenzyl-p-toluidine (IV), which is being developed commercially for suppression of axillary buds in tobacco. The two most active nitrophenylhydrazines tested were 1,1-dimethyl-2-(2′,6′-dinitro-3′-n-propylamino-α,α,α-trifluoro-p-tolyl)hydrazine (XVIII) and 3′,5′-dinitro-p-(2,2-diethylhydrazino)-N-methoxy-N-methylbenzamide (XIX) (I₅₀ values of 7.9 × 10^?9 and 9.3 × 10^?9M, respectively). Factors such as electronic distribution, steric hindrance, and lipid solubility were considered to influence the biological activity of the compounds tested.     

Synthesis of 2-amino-6-oxocyclohexenylsulfonamides and their activity against Botrytis cinerea

BACKGROUND: With the objective of exploring the fungicidal activity of 2‐oxocyclohexylsulfonamides (2), a series of novel 2‐amino‐6‐oxocyclohexenylsulfonamides (6 to 23) were synthesised, and their fungicidal activities against Botrytis cinerea Pers. were evaluated in vitro and in vivo. RESULTS: The compounds were characterised by IR, ¹H NMR and elemental analysis. Bioassay results of mycelial growth showed that compounds 6 to 23 had a moderate antifungal activity against B. cinerea. N‐(2‐methylphenyl)‐2‐(2‐methylphenylamino)‐4,4‐dimethyl‐6‐oxocyclohexenylsulfonamide (13) and N‐(2‐chlorophenyl)‐2‐(2‐chlorophenylamino)‐6‐oxocyclohexenylsulfonamide (21) showed best antifungal activities, with EC₅₀ values of 8.05 and 10.56 µg mL^?1 respectively. Commercial fungicide procymidone provided an EC₅₀ value of 0.63 µg mL^?1. The conidial germination assay showed that most of compounds 6 to 23 possessed excellent inhibition of spore germination and germ‐tube elongation of conidia of B. cinerea. For in vivo control of B. cinerea colonising cucumber leaves, the compound N‐cyclohexyl‐2‐(cyclohexylamino)‐4,4‐dimethyl‐6‐oxocyclohexenylsulfonamide (19) showed a better control effect than the commercial fungicide procymidone. CONCLUSION: The present work demonstrated that 2‐amino‐6‐oxocyclohexenylsulfonamides can be used as possible new lead compounds for further developing novel fungicides against B. cinerea. Copyright © 2011 Society of Chemical Industry     

2-硝基-1-芳乙烯类化合物的设计合成及其对稻瘟病菌的抑制活性

为了筛选得到对稻瘟病菌Magnaporthe grisea具有较高抑菌活性的新型化合物,根据稻瘟病菌中1,3,8-三羟基萘酚还原酶（3HNR）的结构信息,设计合成了系列2-硝基-1-芳乙烯（2a~2e）和2-溴-2-硝基-1-芳乙烯（3a,3b）目标化合物,并测试了其对3HNR和稻瘟病菌的抑制活性,同时运用分子对接方法对目标化合物与3HNR可能的结合模式进行了分析。结果表明:大部分目标化合物对3HNR都有很好的抑制作用（IC503的抑制活性最好,IC50值为0.53 μmol/L。在50 μg/mL下,目标化合物对稻瘟病菌的生长具有不同程度的抑制作用,其中2e、3a和3b的抑制率高于96%;3a和3b的EC50值分别为16.4和11.6 μg/mL。分子对接方法分析结果表明,硝基苯乙烯骨架结构与稻瘟病菌的3HNR活性空腔的氨基酸残基有较好的相互作用,其中化合物3中的溴原子可与3HNR中Tyr223和Tyr178的羟基形成氢键,从而解释了化合物3对3HNR有较好抑制作用的原因。     

Insecticidal properties of benzofuran-2-carboxylic acid derivatives

A series of amides and esters of substituted benzo[b]furan-2-carboxylic acids have been synthesised, and their activity against adult sweet potato weevils, Cylas formicarius elegantulus (Summer) studied. The topical insecticidal potency of these compounds was compared in acetone solution and in a mixture of piperonyl butoxide (PB) and acetone (0·05+99·95 by volume). The compounds were much more active when administered in the acetone/PB mixture, and exhibited 48-h LD₅₀ values ranging from 1·7 to 26·6 μg per insect. The most active compound, 2-(3,5-dimethylpyrazol-1-ylcarbonyl)-6-methoxy-3-methylbenzofuran, was equiactive with technical grade dimethoate (in acetone/PB) on a weight basis. © 1998 SCI     

Dimethoxypyrimidines as Novel Herbicides. Part 2. Synthesis and Herbicidal Activity of O-Pyrimidinylsalicylates and Analogues

A new series of the O-pyrimidinylsalicylates was synthesized and their herbicidal activity was examined. Some of these compounds showed very strong herbicidal activity under pre- and post-emergent treatment conditions against various kinds of grass and broadleaf weeds. Among these compounds, O-(4, 6-dimethoxypyrimidin-2-yl) salicylic acid and its methyl ester were found to exhibit the highest activity. The herbicidal symptoms observed after the treatments included early cessation of plant growth followed by chlorosis, necrosis and plant death. The symptoms were similar to those caused by sulfonylureas and imidazolinones, which inhibit branched-chain amino acid biosynthesis.     

Synthesis and insecticidal activity of lipophilic amides. Part 7. Alternative aromatic groups for phenyl in 6-phenylhexa-2,4-dienamides

Synthesis of a wide range of analogues of the lead compound, N-2-methylpropyl-6-phenylhexa-2,4-dienamide, in which phenyl was replaced by other aromatic systems is reported. In cases where rearrangement rendered the N-2-methylpropyl compound less accessible, N-2,2-dimethylpropyl substitution was used, because rearrangement was then suppressed. Several of the groups examined, for instance 2-naphthyl, enhanced insecticidal activity, and when appropriately substituted, particularly with halogen, led to the most active compounds discovered in this series.     

乙酰胆碱酯酶抑制剂Territrem B类似物的合成新方法

设计了一条新的2-烯- 1 -酮-类伊比林-20-基-取代苯甲酸酯( 6 )土震素(Territrem)B类似化合物的合成方法。以甲磺化伊比林醛( 2 )为原料,经脱甲磺酸生成2-烯类伊比林-13-醛( 3 ),化合物 3 经溴代丁二酰亚胺(NBS)光照溴化一步法生成中间产物 4,4 不经分离直接与酚反应生成化合物 5,5 再经一步法水解氧化制得目标产物 6 。该方法不仅提高了 6 的收率(提高5%~30%),还合成了5个新化合物 3和5b~5e 。生物活性测试表明,在10-4 mol/L条件下,只有化合物 6a 对乙酰胆碱酯酶(AChE)显示出17%的抑制活性。     

Response of susceptible and resistant peach-potato aphids Myzus persicae (Sulz.) to insecticides in leaf-dip bioassays

The response of susceptible (S), moderately resistant (R₁) and strongly resistant (R₂) peach-potato aphids, Myzus persicae (Sulz.) to organophosphorus, carbamate and pyrethroid insecticides was tested by a leaf-dip bioassay. The aphids were placed on potato leaves (dipped in insecticide solutions 1–2 or 24 h before infestation) and their mortality examined 48 h later. R₁ aphids were virtually susceptible to most of the carbamates, demephion and acephate, but were slightly to moderately resistant (2.1–9.4 times) to permethrin, cypermethrin and (S)-α-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate (I), (NRDC 161), to 5,6,7,8-tetrahydro-2-methylquinolin-4-yl dimethylcarbamate (II), (Hoechst 25 682) and demeton-S-methyl. R₂ aphids resisted more strongly or very strongly (between 65 and 1280 times) the pyrethroids, demeton-S-methyl (×94), II (×83) and demephion (×9), and were slightly to moderately (2–5 times) resistant to acephate, pirimicarb, ethiofencarb and 2-(dimethylcarbamoyloxyimino)-3-methoxyimino-N,N- dimethylbutyramide (III), (DPX 3853). Both resistant strains were susceptible to nitrilacarb [4,4-dimethyl-5-(methylcarbamoyloxyimino)pentanenitrile] complex (1:1) with zinc chloride (IV), (AC 85 258). The implications of these results in terms of practical aphid control are discussed.     

取代苯甲醛缩氨基硫脲(脲、硝基胍)类化合物的合成及其对小菜蛾酪氨酸酶的抑制活性

酪氨酸酶是昆虫生长发育过程中的一个关键性酶,控制酪氨酸酶的活性即可调节昆虫的生长行为。以苯甲醛缩氨基硫脲为母体化合物,通过变换硫脲结构片段,设计了18个结构类似的苯甲醛缩氨基硫脲(脲、硝基胍)类化合物,以取代苯甲醛、氨基硫脲、水合肼等为原料经1~2步反应合成了目标化合物,其结构通过红外、核磁共振氢谱、质谱(ESI)表征。生物活性测试结果表明,硫脲类化合物对小菜蛾酪氨酸酶的抑制活性明显高于脲(硝基胍)类化合物,说明硫脲结构的存在对化合物的活性有利。     

Pyrethroid insecticides derived from 2,2-dimethyl-3-(3-phenoxybenzyloxy)propanal

Fourteen oxime ethers and eleven other unsaturated compounds derived from 2,2-dimethyl-3-(3-phenoxybenzyloxy)propanal were synthesised and their insecticidal activity against Musca domestica, Locusta migratoria, Dysdercus cingulatus, Aedes aegypti, Plutella xylostella, Drosophila melanogaster, Tetranychus urticae and Spodoptera littoralis tested. Structural variations including chain length, branching and unsaturation of the oxime ether O-alkyl group and substituent exchange at the carbon-carbon double bond of the unsaturated compounds were made in order to examine the structure-activity relationship. All biological activities were compared with the activity of the ether pyrethroid MTI-500.     

Synthesis and Structure–Activity Relationships of Miticidal 4,5-Dihydropyrazole-5-thiones

A series of novel 4,5-dihydropyrazole-5-thiones (DHPs) was synthesised by treating the corresponding dihydropyrazolones with ‘Lawesson’s reagent and evaluated for miticidal activity against two-spotted spider mites (Tetranychus urticae Koch). Of these, 3-(4-chlorophenyl)-4,4-dimethyl-1-phenyl-4,5-dihydropyrazole-5-thione, 3-(4-chlorophenyl)-4-ethyl-4-methyl-1-phenyl-4,5-dihydropyrazole-5-thione, 3-(4-chlorophenyl)-1-phenyl-4,5-dihydropyrazole-5-thione-4-spirocyclopentane and 4,4-dimethyl-1-phenyl-3-(4-trifluoromethyl-phenyl)-4,5-dihydropyrazole-5-thione were highly active (pEC₅₀>4·0) and were more effective than the miticide dicofol (pEC₅₀=3·879), which has traditionally been used for the control of phytophagous mites. Structure–activity relationship (SAR) studies were performed on each position of the pyrazole ring of DHPs. The results indicated that the unsubstituted phenyl, 4-substituted phenyl and thioxo groups on the 1-, 3- and 5-positions of DHPs respectively were required for activity. Quantitative SAR studies using physicochemical parameters of substituents and the capacity factor k′ as a hydrophobicity index suggested that: (a) the activities of all types of DHPs examined were mainly dominated by hydrophobicity, (b) the bulkiness of 4-substituents of the 3-phenyl ring favoured the activity and (c) the log k′ optimum for all DHPs was 1·675, equivalent to a log P_ow value of c. 5·0.