Synthesis and bioactivity of some fluorine-containing benzoyl arylureas. Part I: Insecticidal-acaricidal products in which the aryl group bears a trifluoromethyl-substituted alkyl or alkenyl side chain

This paper reports the synthesis and the biological activity of benzoyl arylureas in which the aryl group bears a trifluoromethyl-substitiited alkyl or alkenyl side chain, R. The activity of these compounds has been evaluated on larvae of S. littoralis, A. aegypti, L. decemlineata and on the eggs of T. urticae. In general: (1) the optimum insecticidal activities are achieved when the substituents on the benzoyl moiety, R₁, and R₂, are 2,6-difluoro, the substituents on the aryl moiety, R₃, are 3,5-dichloro and R₁, is 4-(? CH?C(CI)CF₃); (2) the best acaricidal activity is shown when R₁, is 2-CI, R₂, and R₃, are hydrogen atoms and R₁, is 4-(? CH₂CH₂CH(CI)CF₃); (3) the best overall activity is displayed when R₁, is 2-CI, R₂ is hydrogen, R₃ is 3-chloro and R₁ is 4-(? CH₂CH₂CF₃).     

A novel series of O,O-diethyl O-(1,3-disubstituted-1,2,4-triazol-5-yl) phosphorothioates. Part II. Quantitative structure–activity relationships

The in-vivo toxicity data of 33 O,O-diethyl O-(1-alkyl-3-R″-1,2,4-triazol-5-yl) phosphorothioates, reported in Part I of this series, were subjected to multiregression analyses for the following organisms: Leptinotarsa decemlineata (larvae), Macrosiphum euphorbiae (aphids), Culex pipiens (adults), Spodoptera littoralis (larvae) and the rat. The activities were found to depend mainly on the steric parameters of R″, these being best expressed by the values L, B₁ and B₄ of the computer program STERIMOL. It was shown that there were different steric requirements for each species and these are discussed. The predictive values of the best equations were also estimated.     

The vinylogous relationship in some pyrethroids

Attention is drawn to a vinylogous relationship between the structure of certain biologically-active pyrethroids. A series of racemic α-cyano-3-phenoxybenzyl 2-(2,2-dichlorovinyl)-1-phenylcyclopropanecarboxylates, based on this relationship, were synthesised and were found to be only moderately toxic to Musca domestica, Spodoptera littoralis and Leptinotarsa decemlineata.     

Activity of abamectin against larval stages of Spodoptera littoralis boisduval and Heliothis armigera hübner (Lepidoptera: Noctuidae) and possible mechanisms determining differential toxicity

Marked changes in the relative toxicity of topically-applied abamectin were found between larval instars of Spodoptera littoralis, toxicity decreasing up to the fifth instar but increasing over 500-fold (at LD₅₀ level) in the sixth instar. By contrast, the toxicity of abamectin remained constant from fifth to sixth instar Heliothis armigera and there was an increase in the toxicity of two chemically unrelated insecticides, malathion (4-fold) and lambda-cyhalothrin (2.5-fold), from fifth to sixth instar S. littoralis. Prior topical application or injection of the microsomal oxidase inhibitor, piperonyl butoxide (PB) increased the toxicity of abamectin (6–8 and 16-fold respectively) against fifth instar S. littoralis, while topically-applied PB increased the proportion of radioactivity present as abamectin in the ventral nerve cord of this instar following topical application with [³H]abamectin. Topically-applied PB also enhanced the toxicity of abamectin against third (4-fold) and fourth instar (5-fold) S. littoralis but had no significant effect on sixth instar S. littoralis, fifth instar H. armigera, or on the toxicity of malathion and lambda-cyhalothrin against fifth instar S. littoralis. Topical application of the esterase inhibitor, S,S,S-tributyl phosphorothioate (DEF) significantly increased the toxicity of abamectin at the LD₅₀ level (3-fold) against fifth instar S. littoralis. The toxicity of injected abamectin against fifth instar S. littoralis was greater (20-fold) than with topical application but injected abamectin was less toxic (2-fold) against sixth instar S. littoralis and had no significant effect on fifth instar H. armigera. It is suggested that differential toxicity of abamectin is due in part to greater metabolism and reduced penetration in fifth instar S. littoralis than in sixth instar S. littoralis or fifth instar H. armigera.     

菌株NDBJJ-BFG的鉴定及其对马铃薯甲虫不同虫态的毒力测定

为筛选出对马铃薯甲虫Leptinotarsa decemlineata(Say)具有防治潜力的菌株,本研究从马铃薯甲虫僵虫虫体上分离菌株NDBJJ-BFG,通过形态学特征和分子生物学方法明确其分类地位,采用喷雾法和覆土法测定了不同浓度下该菌株对马铃薯甲虫室内毒力的致死中浓度LC50及半致死时间LT50。结果表明,经形态特征与r DNA ITS序列分析最终确定菌株NDBJJ-BFG为球孢白僵菌Beauveria bassiana(Bals.)Vuill。该菌株对1、2、3和4龄马铃薯甲虫幼虫的LC50分别为0.91×10~6、1.51×10~6、5.09×10~6和6.84×10~6个/m L;采用喷雾法和覆土法处理蛹的LC50分别为1.43×10~7个/m L和8.15×10~6个/m L,成虫的LC50分别为5.08×10~7个/m L和2.97×10~7个/m L。在孢子悬浮液浓度相同时LT50随虫龄的增大而延长,其中成虫的LT50最长,其次是蛹;在相同龄期下LT50随着孢子悬浮液浓度的增大而缩短。表明菌株NDBJJ-BFG对马铃薯甲虫1龄和2龄幼虫具有高毒力,其在马铃薯甲虫的生物防治中将具有较大的应用潜力。     

Uncoupling activity of some N-phenylcarbamates

In the N-phenylcarbamate family several compounds inhibit cell division and some others prevent the light-driven electron transfer in thylakoids. In this family (general formula R₁-NH-COO-R₂ where R₁ is a phenyl), 18 compounds were investigated for their possible uncoupling activity. Potent uncouplers, able to uncouple fully the oxidative phosphorylation or the photophosphorylation between 1 and 10 μM, were obtained when R₂ was 4-NO₂C₆H₄, CH₂CHCl₂ or CH₂CF₃ and R₁ was a 3,4-Cl₂C₆H₃. The -NH-group of the carbamate function is probably involved in the proton transfer through the two types of biological membranes studied here (mitochondria and thylakoids).     

Synthesis and insecticidal activity of 3-(haloalkyl-1,3-dienyl)-2,2-dimethylcyclopropanecarboxylates

New 2,2-dimethylcyclopropanecarboxylic acids bearing halogenated 1,3-alkadienyl substituents at position 3 of the cyclopropane ring were synthesised and the insecticidial activities of their 3-phenoxybenzyl and α-cyano-3-phenoxybenzyl esters against housefly (Musca domestica), Colorado potato beetle (Leptinotarsa decemlineata) and Egyptian cotton leafworm (Spodoptera littoralis) were determined. The activity of these compounds varied according to the relative position of the halogen substituents on the diene chain. The observed changes of activity with the structure of the side chain are discussed in terms of the coplanarity of the conjugated double bonds.     

滴灌施肥量对棉花生长、养分吸收及产量的影响

2012年以新陆早33号棉花为供试作物,利用田间小区试验研究了大田膜下滴灌施肥条件下,不同滴灌施肥量对棉花植株氮、磷、钾养分的吸收、干物质积累及籽棉产量的影响。设置了5个N-P2O5-K2O施肥水平150-60-30、200-80-40、250-100-50、300-120-60 kg·hm-2和350-140-70 kg·hm-2(分别记为F1、F2、F3、F4和F5),灌水量为100%ETc(作物蒸发蒸腾量)。结果表明:在新疆膜下滴灌条件下,棉花干物质积累与氮、磷、钾养分吸收和吸收速率均随着滴灌施肥量的增加呈增大的趋势,施肥量达到F4时,棉花的干物质累积和氮、磷、钾的吸收和吸收速率最大;随着施肥量的增加,棉花产量有增加的趋势,但当施肥量大于F3,棉花产量随施肥量的增加(F3,F4,F5)无显著性差异;F3施肥水平下的氮肥农学效率、磷肥农学效率、钾肥农学效率和肥料偏生产力显著大于F4与F5施肥水平。从节肥和生态可持续发展角度来看,F3施肥水平,即250-100-50 kg·hm-2(NP2O5-K2O)为最佳滴灌施肥量。     

小麦白粉病反应型和产孢量的关系

利用小麦的6个品种及小麦白粉菌的3个小种研究了小麦苗期白粉病反应型与产孢量之间的关系。分别用累积单斑产孢量(LBSY)、累积单位面积产孢量(LASY)与反应型组建了反应型-产孢量关系模型:Y_1=exp(1.7178×lnX 0.0256X-2.484)(LBSY法);Y_2=exp(1.5168×lnX 0.052X-2.309)(LASY法)(X为反应型,Y为产孢系数)。通过LBSY方法获得反应型0,1,2,3~-,3,3~ ,4~-,4所对应的产孢系数分别为0,0.09,0.29,0.49,0.60,0.71,0.96,1。     

Synthesis,spectral properties and insecticidal,acaricidal and ovicidal activities of some O-(1,5-disubstituted- 6-oxo-12H-pyridazin-4-yl) phosphorothioates

A synthesis of O,O-dialkyl, O-alkyl O-2-chloroethyl (or O-2-ethoxyethyl) O-(1,5-disubstituted-6-oxo-1H-pyridazin-4-yl) phosphorothioates is described. Infrared, Raman and ultraviolet spectra of the compounds prepared are interpreted. The wave-numbers of the v(C? C) bands were correlated with substituent constants. Good linear correlations of v(C? O) with σ, σ^F, σ_I and σ_R were observed for compounds containing various substituents in the neighbourhood of the keto group of the pyridazinone ring. The insecticidal, acaricidal and ovicidal activities of O-(ethyl or isopropyl), O-(alkyl, 2-chloroethyl, or 2-ethoxyethyl) O-(5-methoxy-1-methyl-6-oxo-1H- pyridazin-4-yl) phosphorothioates, O-ethyl O-isopropyl O-(5-methoxy-1-substituted-6-oxo-1H-pyridazin-4-yl) phosphorothioates and O-ethyl O-isopropyl O-(1-methyl-5-substitutedd-oxo-1H-pyridazin-4-yl) phosphorothioates are reported together with the toxicity of some of these compounds to rats.     

Field strains of Stemphylium vesicarium with a resistance to dicarboximide fungicides correlated with changes in a two-component histidine kinase

In Stemphylium vesicarium, four phenotypes were recognized according to their in vitro responses to dicarboximide fungicides: S (sensitive), S₊ (low resistant to iprodione and procymidone but moderately resistant to vinclozolin), R₁ (moderately resistant to iprodione and vinclozolin but highly resistant to procymidone), R₂ (highly resistant to all dicarboximides). Cross-resistance was observed between dicarboximides and aromatic hydrocarbon fungicides in all cases while cross-resistance to phenylpyrroles was only detected in R₂ phenotype. Moreover, no changes were noted in sensitivity to oxidative and osmotic stress inducers. An osmosensing histidine kinase gene, homologous to OS1 from Neurospora crassa, was sequenced from several field isolates of Stemphylium vesicarium. This gene is predicted to encode a 1,329 amino acid protein, comprising a conserved histidine-kinase domain in the C-terminal region and six tandem repeats of about 90 amino acids at the N-terminal end. In S₊ and R₁ phenotype isolates, a single amino acid substitution was observed in the first amino acid repeat; F267L and L290S respectively. For the R₂ isolates, the exchanges T765R or Q777R were located within the histidine-kinase domain.     

Comparative toxicity of two ecdysteroid agonists,RH-2485 and RH-5992, on susceptible and pyrethroid-resistant strains of the Egyptian cotton leafworm,Spodoptera littoralis

The comparative toxicity of two non-steroidal ecdysteroid agonists, RH-2485 and RH-5992 (tebufenozide), on development stages, fecundity and egg viability of a susceptible laboratory strain and a pyrethroid-resistant field strain ofSpodoptera littoralis (Boisduval) was evaluated. Taking the LC₅₀s as the criterion, RH-2485 was 3–7-fold more potent than RH-5992 against the susceptible and 7–14-fold more against the field strain. The LC₅₀ of RH-2485 in the 1st and 6th instars of the susceptible strain was 0.32 and 0.57 mg a.i./l, respectively. The field strain showed a mild cross-resistance of about threefold to both compounds in 1st instars and to a lesser extent in 6th instars. A considerable increase in fecundity (~3-fold) and no effect on egg viability was observed when 6th instars were fed on cotton leaves treated with 0.25 mg a.i./l RH-2485 (~LC₄₀). Our results indicate that both compounds are potentially potent insecticides for controllingS. littoralis larvae, being 10-60-fold more potent than a previous ecdysteroid agonist, RH-5849.     

Quantifying cropping practices in relation to inoculum levels of Fusarium graminearum on crop stubble

This study was conducted in 58 producer‐field locations in Manitoba from 2003 to 2006 to understand how cropping practices influence Fusarium graminearum inoculum levels on stubble of various crops, including wheat, collected from the soil surface. Colonies per m² (CN) were determined and converted to base‐10 logarithm values (log₁₀CN). Mean log₁₀CN of the sampled field for various crops and groups of crops grown in the 3 years prior to sampling were tested to find significant differences. Average log₁₀CN values were also used to determine significant differences between tillage systems and the effect of number of years. Average log₁₀CN values for zero and minimum tillage systems were not different but were significantly higher than values for conventional tillage. A series of three crop rotation scenarios were tested using weighted log₁₀CN values for crop, tillage, their interaction and their squared terms in step‐wise regression models to identify which model was the best predictor of log₁₀CN. This was selected as the cropping practice index (CPI) model and was expressed as: CPI = 1·98423 + 0·55975 (C₂ × C₁ × T)² + 0·4390 (C₂ × T)², where C₁, C₂ and T represent the weighted log₁₀CN values for crops grown 1 and 2 years previously and tillage system, respectively. R² value for this model was 0·933 (P < 0·0001). The reliability of the CPI model was tested using jack‐knife full cross‐validation regression. The resulting R² was 0·899. The CPI model was tested using data collected from seven wheat fields in 2006 (R² = 0·567). The relationship between CPI and FHB index (R² = 0·715) was significant.     

Synthesis and fungitoxic activity of 5‐aryl‐1‐formyl‐4,5‐dihydro‐3‐(2‐hydroxyphenyl)‐1H‐pyrazoles and their complexes

Cyclization of 3‐aryl‐1‐(2‐hydroxyphenyl)prop‐2‐en‐1‐ones with hydrazine hydrate in refluxing formic acid afforded the title ligands, 5‐aryl‐1‐formyl‐4,5‐dihydro‐3‐(2‐hydroxyphenyl)‐1H‐pyrazoles (HL¹–HL⁴, Ar = Ph, 4‐CH₃O‐C₆H₄‐, 2‐furyl, 2‐thienyl). Reaction of HL¹–HL⁴ with the divalent metal ions, Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, and Zn²⁺, afforded novel complexes of the type [ML₂] (M = metal ion; L = deprotonated ligand) which were characterized by elemental analyses, molecular weight determinations, molar conductances, magnetic moments and electronic and infrared spectral data. The ligands behaved as tridentate, coordinating through the phenolic oxygen after deprotonation, N‐2 of the pyrazole ring and oxygen of the 1‐formyl group. The ligands and their complexes were evaluated for growth‐inhibiting activity against four phytopathogenic fungi. Macrophomina phaseoli was generally most sensitive followed by Alternaria alternata and Colletotrichum falcatum while Fusarium oxysporum was least sensitive to the tested compounds. The ligand HL¹ and its complexes showed the best activity against the fungi tested. © 2000 Society of Chemical Industry     

Synthesis and Structure–Activity Relationships for the Fungicidal Activity of O,O-bisaryl sec-butylphosphonates

Sixteen O,O-bisaryl sec-butylphosphonates have been synthesised by condensing sec-butylphosphonyl dichloride with substituted phenols. The compounds were tested against two phytopathogenic fungi, Rhizoctonia bataticola and Helminthosporium oryzae. The most active compound against R. bataticola is O,O-bis(3-methylphenyl) sec-butylphosphonate (ED₅₀ 29·56 mg litre^-1) and against H. oryzae, O,O-bis(2-chlorophenyl) sec-butylphosphonate and its para-chloro analogue (ED₅₀ 0·14 and 0·13 mg litre^-1 respectively). Quantitative structure–activity relationships on the fungicidal activity have been analysed by means of multiple regression analysis using physicochemical substituent parameters. Electronic parameters viz., σ and F have expressed significant variability in fungitoxicity against both the fungi, viz. R. bataticola and H. oryzae. Hydrophobic and steric parameters are also found to be important in the correlation studies. © 1997 SCI.     

Differential responses to phosphorus availability in the halophytes Aeluropus Littoralis,Catapodium rigidum,and Hordeum maritimum

The objective of this experiment was to explore the variability of response to phosphorus (P) availability in three fodder Poaceae species native of saline biotopes, Aeluropus littoralis, Catapodium rigidum, and Hordeum maritimum. The behavior of these wild species has been compared to that of a cultivated one, Hordeum vulgare. Plants were grown in plastic pots filled with inert sand. The experiment was carried out in a greenhouse with six P levels: 0, 5, 15, 60, 180, and 360?µM P concentration supplied as KH₂PO₄. Results showed that the growth of the four species is strongly affected by the low phosphorus availability in the medium. Furthermore, to reach 80% of their maximum yield expressed as shoot dry weight (DW), a soil phosphorus concentration of approximately 40?µM P concentration is sufficient for Hordeum maritimum, whereas approximately 66, 120, and 132?µM P concentration are needed for C. rigidum, A. littoralis, and Hordeum vulgare plants, respectively. Thus, our results showed that spontaneous species are more tolerant to P deficiency than cultivated barley. The relative performance of the three wild Poaceae species is likely related to their capacity to maintain higher P acquisition efficiency (PAE) under low P concentration conditions. These native Poaceae species may therefore represent genetic resources for the improvement of barley.     

棉籽带枯萎病菌检验方法的研究

棉籽带菌是远距离传病的主要途径。病棉株种子带菌率0.01—46.8%。带菌部位以种壳为主,但子叶、胚均带菌。棉籽上除带枯萎病菌外,还带有半棵、串珠、茄病、木贼等几种镰刀菌及其他杂菌,干扰检验。文中介绍一种选择性培养基,其成分为:甲基纤维素1克、KH_2PO_4克、蛋白胨5克、MgSO_4·7H_2O0.5克、K_2S_20.2克、KCl 0.6克,NH_4NO_30.3克、五氯硝基苯0.1克、蔗糖20克、链霉素0.1克、琼脂20克、蒸馏水1000毫升。应用其进行分离培养棉籽,可根据菌落形态特征及颜色反应,较容易地检验出棉花枯萎病菌。     

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.     

Comparative studies on acylurea insect growth regulators and neuroactive insecticides for the control of the armyworm Spodoptera exempta walk

Leaf-dip bioassays with commercial pesticide formulations were used throughout this study. Third-instar larvae of Spodoptera littoralis were bioassayed for comparative purposes. The end-point mortality against the third-instar larvae (L3) of two Spodoptera exempta populations (Bangor and Gent) and a S. littoralis population (NRI) was found to occur at 72 h and 120 h for neuroactive compounds (carbamate, organophosphate and pyrethroid insecticides) and acylureas respectively. Overall, the acylureas were found to be more toxic (up to 240-fold at the LC₅₀ level) than the most active of the neuroactive compounds tested, the pyrethroids. This difference was greatest against S. littoralis, which was markedly less sensitive to the latter compounds. The Gent population of S. exempta was also found to be significantly less sensitive (7-folt at LC₅₀) to the pyrethroid, lambda-cyhalothrin, than the Bangor strain. Two of the most toxic neuroactive and non-neuroactive compounds, the pyrethroid, cypermethrin and the acylurea, teflubenzuron were chosen for further studies with S. exempta (Gent) and S. littoralis. Relatively little difference in the toxicity of teflubenzuron was observed against different larval instars (L2, L3 and L4) of S. exempta when compared with cypermethrin. Choice-chamber-experiments on feeding behaviour showed that when L3 larvae of either species were exposed to both treated and untreated leaves. teflubenzuron had no significant effect on larval distribution, the percentage of each leaf disc consumed or larval weight gain when compared with untreated controls. In contrast, a marked dose-dependent repellent response to cypermethrin-treated leaves was shown by S. littralis after 6 h. together with corresponding reductions in the percentage of the treated leaf consumed and in larval weight gain. Similarly, when L3 S. exempta were exposed only to pesticidetreated leaves, cypermethrin significantly reduced premoult larval weight gain, whereas tefiubenzuron had no premoult effect. However, following exposure of L3 S. exempta and S. littoralis to teflubenzuron for 48 h prior to moulting, L4 which survived the moult showed reduced weight gain compared with controls, the reduction being more pronounced on maize than on artificial diet. This antifeedant effect increased in proportion to the concentration of teflubenzuron originally administered. The effect of exposure time to teflubenzuron was examined by placing L3 S. exempta and S. littoralis on leaves treated with the approximate LC₅₀ or LC₉₅ dose for 6–48 h. The exposure time required to produce appreciable mortality (relative to LC values) within the treated population was found to be 24 h.     

水稻抗稻瘿蚊品种筛选鉴定研究初报

1978～1979年在广州郊区进行水稻抗稻瘿蚊品种筛选鉴定,经多次重复鉴定,国外引进的品种中,无标葱的有W_(1263)、R_(7-2757)、R_(35-2750)、RD_9、BKNBR_(1030-76-2)、ARC_(6650)等13个;标葱率1～5%的有R_(35-2739)、IET_(6013)、BG_(404-1)等12个;标葱率在15%以下的有CR_(180-4)等12个。初步鉴定本国品种资源,无标葱的有鸡咀占,标葱率在5%以下的有大科占、晚金风6号等17个。鉴定方法先行苗期初筛和复筛,将标葱率15%以下的在本田期再行重复鉴定,这样能比较准确、快速地进行筛选鉴定,以明确其抗性,找到抗源。