嘧啶联吡唑甲酰胺类化合物的合成及除草活性

设计合成了一系列结构新颖的嘧啶联吡唑甲酰胺类化合物5a~5o,其结构均经过1H NM R和MS分析确证。初步生物活性测试结果表明:在有效成分150 g/hm2剂量下苗后茎叶喷雾处理时,化合物(R)-N-[1-(4-氯苯基)乙基]-3-二氟甲基-1-(4,6-二甲氧基嘧啶-2-基)-1H-吡唑-4-甲酰胺(5c)、N-[1-(4-氯苯基)乙基]-1-(4,6-二甲氧基嘧啶-2-基)-N-甲基-3-三氟甲基-1H-吡唑-4-甲酰胺(5i)和N-[1-(4-氯苯基)乙基]-1-(4,6-二甲氧基嘧啶-2-基)-3-三氟甲基-1H-吡唑-4-甲酰胺(5k)对繁缕Stellaria media的抑制率高达90%以上;而同样剂量下苗前土壤喷雾处理时,化合物N-[1-(4-氯苯基)乙基]-3-二氟甲基-1-(4,6-二甲氧基嘧啶-2-基)-1H-吡唑-4-甲酰胺(5b)和5c对繁缕的抑制率达100%。该类结构化合物有望作为除草先导化合物进行开发。     

7-(1-酰基哌嗪-4-基)甲基喜树碱衍生物的合成及杀虫活性

以(20S)-喜树碱(CPT)为原料,根据类同合成法和亚结构连接法原理,对CPT的7-C位进行修饰,得到了系列新型7-(1-酰基哌嗪-4-基)甲基喜树碱衍生物(4a~4m),所有衍生物的结构均通过核磁共振氢谱(1H NM R)和液-质联用(LC-M S)等方法确证;并初步测定了其对朱砂叶螨Tetranychus cinnabarinus和松材线虫Bursaphelenchu xylophilus的室内杀虫活性。结果表明:与喜树碱相比,各衍生物均表现出不同程度的杀虫活性,其中化合物7-[1-(4-甲氧基苯酰基)哌嗪-4-基]-甲基喜树碱(4g)和7-(1-环戊酰基哌嗪-4-基)-甲基喜树碱(4j)对朱砂叶螨24 h的半数致死浓度(LC50值)分别为8.10和9.05 mg/L,对松材线虫的LC50值分别为6.34和6.68 mg/L。研究结果可为喜树碱衍生物杀虫活性构效关系研究奠定基础。     

嘌呤氧基苯氧丙酸酯的合成及除草活性

以4,6-二氯-5-硝基嘧啶为起始原料,经过还原胺化、取代、醚化等一系列反应,得到11个未见文献报道的嘌呤氧基苯氧丙酸酯类化合物1a~1k,其结构经1H NM R和M S确认。初步生物活性测定表明:在200 mg/L下,所有目标化合物均表现出一定的除草活性,其中化合物1f((R)-2-(4-((9-(4-氯苯)-8-(三氟甲基-9H-嘌呤-6-基)氧)苯氧)丙酸丁酯)和1h((R)-2-(4-((9-(4-氯苯)-8-(三氟甲基-9H-嘌呤-6-基)氧)苯氧)丙酸乙酯)对靶标的抑制率几乎都达到100%。     

Interaction between optical isomerism and plant pharmacological action,change of modes of action and chirality of 1-(α-methylbenzyl)-3-p-tolylurea

The optical isomers, (R)-1(α-methylbenzyl)-3-p-tolylurea ((R)-MBU) and (S)-1-(α-methylbenzyl)-3-p-tolylurea ((S)MBU), which are analogues of daimuron [1-(α,α-dimethylbenzyl)-3-p-tolylurea], a herbicide for Cyperaceae weeds and a safener for paddy rice, exhibited different biological responses. These two physiological properties of daimuron were observed separately in (R)-MBU and (S)-MBU. Only (R)-MBU had herbicidal activity against Cyperaceae weeds, while the (S)-isomer was a more effective safener against bensulfuron-methyl (BSM) injury of rice seedlings than was (R)-MBU. (S)-MBU promoted root growth of rice seedlings, but the (R)-enantiomer inhibited root growth. (S)-MBU was a more potent inhibitor than (R)-MBU on PS II reaction of spinach broken chloroplasts. Furthermore, (S)-MBU and (R)-MBU showed cross intergenus selective phytotoxicity among the Gramineae plants, Oryza sativa L. (rice, cv. Tsukinohikari, japonica), Triticum aestivum L. (wheat, cv. Norin No. 61) and Echinochloa crusgalli var. frumentacea Wight, on root growth inhibition in the dark.     

Actions of pyrethroid insecticides on insect axonal sodium channels

The actions of pyrethroid insecticides were tested on isolated giant axons of the cockroach Periplaneta americana, using oil-gap, single-fibre recording techniques. Current-clamp and voltage-clamp experiments were used to determine the actions of pyrethroids on axonal membrane potentials and ionic currents. Treatment with deltamethrin at micromolar concentrations caused gradual depolarisation of the axon accompanied by a reduction in amplitude of the action potential. This depolarisation was enhanced by an increase in stimulation frequency. Other synthetic pyrethroids: 3,4,5,6-tetrahydrophthalimidomethyl (1RS)-cis-3-[(RS)-2,2-dimethylcyclopropyl]-2,2-dimethylcyclopropanecarboxylate, biopermethrin and its (1S)-enantiomer, (1R)-tetramethrin, S-bioallethrin, bioresmethrin and its (1S)-enantiomer, cismethrin, and 5-benzyl-3-furylmethyl (E)-(1R)-cis-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate (RU-15525, ‘Kadethrin’) were investigated. The (1S)-enantiomers were inactive, but all the other pyrethroids tested, apart from deltamethrin, induced prolonged negative (depolarising) after-potentials. All the treatments with the active pyrethroids resulted in the appearance of a voltage and time-dependent ‘maintained’ sodium conductance. The duration of this ‘slow’ conductance varied considerably depending on the pyrethroid under test. Clearly, the effectiveness of pyrethroids on whole insects is not determined only by the degree to which they directly modify the properties of sodium channels. Nevertheless, voltage-clamp experiments on isolated axons readily permit direct comparison of the actions of different pyrethroids on the sodium channels of insect neurones.     

Phosphorous acid treatments control Phytophthora diseases in Australia1

Treatments with a partially neutralized formulation of phosphorous acid containing potassium phosphite were assessed for control of Phytophthora diseases in subtropical and temperate crops in Australia. In Queensland, trunk injections of phosphite (10% solution) controlled severe root rot (Phytophthora cinnamomi) of avocado trees and resulted in the recovery of trees. Single pre-harvest sprays (2.5 kg ha^-1) of phosphite controlled root and heart rot (P. cinnamomi) of pineapples. Foliar sprays of phosphite (64 g per tree) controlled root rot (P. nicotianae var. parasitica) and trunk canker (P. citrophthora) of mandarin trees. In Victoria, a foliar spray of phosphite (300 g ha^-1) reduced root rot (P. clandestina) of subterranean clover and increased dry matter by 1.96 to 5.11 t ha^-1. Trunk injections of phosphite (10% solution) controlled trunk rot (P. cactorum) of peach trees and foliar sprays (10 kg ha^-1) reduced severity of root rot (P. nicotianae var. nicotianae) of tomatoes.     

Independent and joint biological activity of isomeric forms of synthetic pyrethroids

Various isomeric mixtures of pyrethroids were examined in topical application tests against houseflies, Musca domestica. On the basis of the activities of the separate isomers of 5-benzyl-3-furylmethyl (±)-cis,trans-chrysanthemate, it was shown that when combined in pairs to give the (±)-trans or (±)-cis or (+)-cis,trans mixtures the observed mortalities did not differ from those expected by simple additive action calculated by the harmonic mean. In contrast the (±)-cis,trans mixture showed considerable antagonism with a mortality only 60% of that expected. Similar evaluations using the separate and combined isomers of bioallethrin [(R,S)-3-allyl-2-methyl-4-oxocyclopent-2-enyl (allethronyl) ( + )-trans-[(1R,3R)-chrysanthemate] and the corresponding (+)-cis-(1R,3S)-chrysanthemate indicate antagonism calculated to be correlated with the content of the (R)-isomer of the alcoholic moiety. Hence the activity of the most active isomer of the “allethrin” series, (S)-3-allyl-2-methyl-4-oxocyclopent-2-enyl ( + )-trans-(1R,3R)-chrysanthemate, (S)-bioallethrin, is not fully realised unless it is present in pure form and a substantial part of the value of bioresmethrin (5-benzyl-3-furylmethyl ( + )-trans-chrysanthemate] as a killing agent is lost when the racemic form is used. In racemic mixtures there is mutual antagonism between pairs of isomers so that considerable masking of activity occurs.     

Volatile organic compounds (VOCs) from cereal plants infested with crown rot: their identity and their capacity for inducing production of VOCs in uninfested plants

When infested with Fusarium sp., the cereals Triticum aestivum L. emend. Fiori et Paol. cv. ‘Bombona’, Avena sativa L. cv. ‘Deresz’, and Hordeum vulgare L. cv. ‘Rastik’ can emit volatile organic compounds (VOCs). The VOCs differ both qualitatively and quantitatively from those emitted by non-infested wheat, oat, and barley plants. We detected increased amounts of VOCs released by green leaves (green leaf volatiles – GLVs): (Z)-3-hexenal, (E)-2-hexenal, (Z)-3-hexen-1-ol, (E)-2-hexen-1-ol, (Z)-3-hexen-1-yl acetate, 1-hexyl acetate as well as the other VOCs like (Z)-ocimen, linalol, linaloloxide, benzyl acetate, indole, and β-caryophyllene. The lipoxygenase pathway resulted in the highest release of GLVs in comparison to the other biochemical pathways of volatile production. As a result of Fusarium infestation, the amounts of VOCs varied between tested cereals. We also subjected uninfested wheat, barley, and oat plants to infested wheat plants, and found that these cereals released larger amounts of VOCs compared to control plants. Emitted amounts of VOCs were significantly higher the shorter the distance between uninfested and infested plants.     

The uptake of metabolites of permethrin by plants grown in soil treated with [14C]permethrin

Sugar beet, wheat, lettuce and cotton were grown in soil treated with [¹⁴C]permethrin, the crops being sown at intervals of 30, 60 and 120 days after treatment of the soil. The uptake of radioactive residues into these crops was measured. Low radioactive residues (up to 0.86 μg g^?1) were detected in the mature plants sown 30 days after soil treatment, and this uptake declined significantly as the interval between soil treatment and sowing increased. Metabolites derived from the acid moiety of the permethrin molecule were shown to constitute the greater part of the residue transferring from the soil to the crops. (1RS)-cis- and (1RS)-trans-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropanecarboxylic acid and 3-(2,2-dichlorovinyl)-1-methylcyclopropane-1,2-dicarboxylic acid were identified as the major acidic metabolites. The latter compound is a metabolite of permethrin which has not previously been identified in soil or plants.     

稻水蝇危害水稻产量损失研究

采用相关分析和通径分析法研究了稻水蝇危害与水稻产量损失的关系。结果表明:水稻产量(y,kg/hm²)与田间虫口密度(x,头 /m²)、穗损失率 (x₅,% )间0.01水平显著时的关系符合方程:y^=9433.965-6.6637x₁-402.7469x₅;产量损失(Y,kg/hm²)与田间虫口密度(x,头/m²)间关系符合下列方程 :Y^=-13.4989+6.0043x(r=0.9647^**)。通径分析显示 ,穗损失率和虫口密度对产量建成直接效应最大 ,分别为-0.9218和-0.1422     

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.     

新型含吡唑杂环邻氨基苯甲酰胺类化合物的合成与杀螨活性

以氯虫苯甲酰胺和氟虫腈的结构为基础,通过活性亚结构拼接的方法,设计合成了24个新型含吡唑杂环邻氨基苯甲酰胺类化合物,其结构经1H NM R、IR及APCI-M S表征。初步生物活性测试结果表明:化合物5-溴-N-[4-氯-2-甲基-6-(甲氨基甲酰基)苯基]-1-1-[2,6-二氯-4-(三氟甲基)苯基]-4-三氟甲基亚磺酰基-1H-吡唑-3-甲酰胺(5k)和5-溴-N-[4-溴-2-甲基-6-(甲氨基甲酰基)苯基]-1-[2,6-二氯-4-(三氟甲基)苯基]-4-三氟甲基亚磺酰基-1H-吡唑-3-甲酰胺(5l)在500 mg/L下对朱砂叶螨Tetranychus cinnabarinus的致死率为100%,但在100 mg/L下其致死率则分别降至30%和50%。所得结果可为邻氨基苯甲酰胺类化合物构效关系研究提供参考。     

The activity of some pyrethroids against Periplaneta americana and Blattella germanica

The knockdown and contact killing actions of various pyrethroids were compared using Blattella germanica and Periplaneta americana. A wide range of knockdown activity was found; 5-benzyl-3-furylmethyl (1R)-cis-3-(dihydro-2-oxo-3-thienylidenemethyl)-2,2-dimethylcyclopropanecarboxylate (RU 15525) acted fastest, more rapidly than pyrethrins, against B. germanica as well as having a low LD₅₀ value. Topical application and direct spray tests showed that (S)-α-cyano-3-phenoxybenzyl (1R)-cir-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate (NRDC 161) was more active as a killing agent, by an order of magnitude, than cismethrin, the next most active compound, and also had considerable knockdown activity. Piperonyl butoxide generally had little synergist effect. Female P. americana were over three times more tolerant than males to a range of insecticides applied topically. Residual knockdown action in the WHO resistance test was observed to provide baseline data. There was little overlap in speed of action between pyrethroids and other insecticides among the compounds tested.     

新型含2(1H)-喹啉酮的甲氧基丙烯酸酯类

以(E)-2-[2'-(bromo-methyl)phenyl]3-甲氧基丙烯酸甲酯和2(1H)-喹啉酮类化合物为原料,通过醚化等反应,合成了11个新型含2(1H)-喹啉酮结构的甲氧基丙烯酸酯类化合物,其结构经红外、电喷雾串联质谱(ESI-MS)和核磁共振氢谱确证。初步生物活性测试结果表明:在100 mg/L质量浓度下,部分目标化合物对烟草赤星病菌Alternaria alternata等6种病原菌具有一定的抑菌活性,其中5a对水稻稻瘟病菌Pyricularia grisea的抑菌率达100%。     

Rhizome-induction activity of chiral 2-α-methylbenzylamino-4-alkylamino-6-chloro-1, 3, 5-triazines in Cyperus serotinus Rottb.

A cytokinin-like effect of chiral 2-α-methylbenzylamino-4-alkylamino-6-chloro-1,3,5-triazines was found using a rhizome-inducing assay with Cyperus serotinus Rottb. tubers. C. serotinus tubers germinated in distilled water yielded plantlets with roots and leaves. Secondary rhizomes were normally not observed within the regular 14-day incubation time in water culture, whereas after increasing incubation periods a very short rhizome appeared (controls). 6-Benzylaminopurine (BA) significantly stimulated rhizome induction, while other plant hormones were inactive. The (R)-isomers of the 1, 3, 5-triazine compounds also stimulated induction of the rhizomes, whereas the (S)-isomers did not. The described rhizome induction system seems to be suitable as a cytokinin bioassay. The (R)-1, 3, 5-triazine compounds showing rhizome-inducing activity (RI activity) inhibited root formation and plant growth at high concentrations with symptoms which were very similar to those of BA. Therefore, the (R)-isomers appear to act as cytokinins in the rhizome induction assay.     

(Z)-3-hexenyl acetate and 1-undecanol increase male attraction to sex pheromone trap in Grapholita molesta (Busck) (Lepidoptera: Tortricidae)

The effects of host-plant volatiles (HPVs) on male oriental fruit moth, Grapholita molesta (Busck) (Lepidoptera: Tortricidae), and response to sex pheromone trap were studied in a pear orchard. Two HPVs compounds, (Z)-3-hexenyl acetate and 1-undecanol, combined with sex pheromone of G. molesta in traps were tested. The results showed that most of the male moths were captured in the traps baited with the sex pheromone combined with these two HPVs compounds than by the pheromone alone. Also, more males were captured by the trap containing pheromone plus (Z)-3-hexenyl acetate than by the one containing 1-undecanol. It appeared that these HPVs act as sex pheromone synergists to enhance the attraction of male G. molestato pheromone traps, since males were not captured in the traps baited only with (Z)-3-hexenyl acetate and/or 1-undecanol.     

Synthetic pyrethroids containing a C–C triple bond

The three commercial synthetic pyrethroids containing a carbon–carbon triple bond, α-ethynyl-2-methylpent-2-enyl (1R)-trans-chrysanthemate, (S)-2-methyl-4-oxo-3-(2-propynyl)cyclopent-2-enyl (1R)-trans,cis-chrysanthemate and [2,5-dioxo-3-(2-propynyl)-1-imidazolidinyl]methyl (1R)-trans-chrysanthemate are reviewed with emphasis on their inventive histories. Their chemistry and efficacy are described briefly. The relationship between stereochemistry and the biological activity is also discussed. © 1998 SCI.     

Further studies on the role of monoterpenes in pine host selection and oviposition ofThaumetopoea pityocampa

In a young mixed pine plantation (Pinus nigra andP. pinea) in central Italy, the influence of the pine needle monoterpenes (R)-(+)-limonene, (S)-(−)-limonene and (1S)-(−)-β-pinene on the oviposition activity of the pine processionary moth,Thaumetopoea pityocampa (Denis et Schiffermüller), was assessed. Two application methods were compared: spraying the trees with the substances emulsified with water, and setting up polyethylene dispensers from which the monoterpenes evaporated. During the moth’s flight period weekly treatments (at 500 mg of monoterpene /l water) were carried out and the evaporation from the polyethylene dispensers (each with 5 g of a single monoterpene) was checked on each occasion by weighing the dispensers. The GLM analysis did not uncover any difference between the methods of application or between the pine species.T. pityocampa laid a significantly (P=0.01) lower number of egg masses on the trees treated with (1S)-(−)-β-pinene than on those treated with the other substances and on the control trees. A ∼45% reduction in egg mass number was obtained on the pines treated with (1S)-(−)-β-pinene, independent of the level of infestation, method of application or pine species. (R)-(+)-limonene and (S)-(−)-limonene were not effective. http://www.phytoparasitica.org posting July 29, 2008.     

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%。