Synthesis,insecticidal and acaricidal properties of some 5-alkoxy-, 5-alkylthio-6-oxo-1-phenyl-1H-pyridazin-4-yl and 6-oxo-5-phenoxy-1-phenyl-1H-pyridazinyl phosphorus esters. II

A series of novel 5-alkoxy-, 5-alkylthio-6-oxo-1-phenyl-1H-pyridazin-4-yl and 6-oxo-5-phenoxy-1-phenyl-1H-pyridazin-4-yl phosphorus esters was prepared from the corresponding alkali pyridazin-4-olates and their insecticidal and acaricidal activities studied. Many of the compounds, especially the diethyl and dimethyl phosphates and OO-diethyl and OO-dimethyl phosphorothioates, showed high insecticidal and acaricidal activity.     

Pénétration, translocation et métabolisme de dinitrophénols

Penetration, transloealion and metabolism of dinitrophenols We had at our disposal DNTBP and DNOC uniformly labelled with ¹⁴C on the benzene ring. Leaf penetration and root uptake were slow with DNTBP as was translocation. After 3 days it was already possible to show degradation compounds far removed from the original herbicides. A catabolite fifty times less active than DNTBP, methyl-2-(hydroxy-2′dinitro-3′5′phenyl)-2-propanol-1, was identified. On the biological plane, DNTBP and DNOC have a disruptive effect on the lipid membranes. Aufnahme, Translokation und Stoffwechsel von Dinitrophenolen     

Organophosphorus poisoning: A comparative study of the toxicity of chlorfenvinphos [2-chloro-1- (2′, 4′, -dichlorophenyl) vinyl diethyl phosphate] to the pigeon,the pheasant and the Japanese Quail

The acute oral toxicity of chlorfenvinphos [2-chloro-1-(2′, 4′-dichlorophenyl)vinyl diethyl phosphate] was measured in pigeon (Columba livia), pheasant (Phasianus colchicus), and quail (Coturnix coturnix japonica) and the compound was shown to be particularly toxic to pigeons. Additionally, all three species were fed chlorfenvinphos at 100 ppm in their diet for two or four weeks and esterase measurements were made by conventional and electrophoretic methods on extracts of liver, kidney and brain. The conventionally measured esterase inhibition correlated well with the acute oral toxicity figures. A more detailed study of the histochemically stained electrophoregams showed some discrepancies compared with conventional methods but offered a possible explanation of the inter-species toxicity difference in that it revealed differential inhibition of some brain iso-esterases in pigeon but not in pheasant or quail.     

Phytotoxic and antiphytopathogenic compounds from Thai Alpinia galanga (L.) Willd. rhizomes

The management of weeds and diseases that are caused by phytopathogenic fungi is important for preventing the loss of agricultural products. The aim of the present study was to identify phytotoxic and antiphytopathogenic agents from the Thai Alpinia galanga rhizome. Extracts of the dried rhizomes of A. galanga (Zingiberaceae) were separated and tested for phytotoxic activity against lettuce (Lactuca sativa L. cv. Great Lakes) and Italian ryegrass (Lolium multiflorum Lam. cv. Wasefudou) and for antiphytopathogenic activity against Alternaria porri, Colletotrichum gloeosporioides, Fusarium oxysporum and Phytophthora nicotianae. 1′‐Acetoxychavicol acetate ( 1 ) was identified as one of the main components, together with trans‐p‐coumaryl acetate ( 3 ) and trans‐p‐acetoxycinnamyl acetate ( 2 ). 1′‐Acetoxychavicol acetate ( 1 ) was solvolyzed with 2% EtOH to yield trans‐p‐coumaryl ethyl ether ( 6 ), trans‐p‐coumaryl acetate ( 3 ) and trans‐p‐coumaryl alcohol ( 5 ). 1′‐Acetoxychavicol acetate ( 1 ) completely inhibited the root growth of the lettuce seedlings at 50 μg mL^–1, but had a weaker inhibitory effect on the growth of Italian ryegrass. 1′‐Acetoxychavicol acetate also inhibited the growth of P. nicotianae and A. porri, with minimum inhibition concentration values of 15.6 and 31.5 μg mL^–1, respectively. The plant growth‐inhibitory activity and fungal growth‐inhibitory activity of trans‐p‐coumaryl acetate ( 3 ), trans‐p‐coumaryl ethyl ether, trans‐p‐coumaryl alcohol ( 5 ) and trans‐p‐acetoxycinnamyl acetate ( 2 ) were lower than those of 1′‐acetoxychavicol acetate. A structure–activity relationship suggested that the strong phytotoxic and antiphytopathogenic activity of 1′‐acetoxychavicol acetate relied on the 1′‐acetoxyl group.     

High-pressure liquid chromatographic determination of sec-butylamine residues in potatoes

Fluorescamine, 4-phenylspiro[furan-2(3H), 1′(3′H)-isobenzofuran]-3,3′-dione, derivatives of primary aliphatic amines were separated by high-pressure liquid chromatography using a reverse-phase system with fluorescence detection. This technique was applied to the determination of residues of the fungicide sec-butylamine in potato tubers; the limit of detection was 0.36 pmol, equivalent to a residue of 0.1 mg kg^?1 in potato samples. A second amine, phenethylamine, was identified in extracts from artificially rotted potato flesh but this did not interfere with the analysis of sec-butylamine residues.     

The accumulation and distribution of pp′DDT and related compounds in an apple orchard .I. residues in the soil

Soils from an orchard sprayed annually (1953-1969) with technical DDT (77% pp′DDT and 22 % pp′DDT) were analysed for residues from 1964 until 1969. The amount of DDT found after 17 years was 21 %pp′DDTout of 27.1 kg/ha applied, and 7 % of pp′DDT out of 7.6 kg/ha. The vertical distribution of residues (pp′DDT, pp′DDE, pp′TDE and pp′DDT) showed a linear relationship between log amount and depth, with approximately 80% in the top 10 cm of soil. At depths from 50 to 210 cm, residue values were too small to be determined (i.e. < 1 ng/g dry wt). The surface distribution in the orchard showed a systematic pattern of circular areas of residues, with maximum values centred at each trunk (7.5 μg/g) and decreasing rapidly to each alley (1.9 ug/g). The levels of pp′DDT had reached a steady state (3-4 kg/ha) and the half-life time was calculated as 3.0 j′ears. pp′DDE (1.8 kg/ha) was the main metabolite of pp′DDT. Small amounts of pp′TDE were also found, pp′DDT was less persistent than pp′DDT, with a half-life time of 1.5 years.     

Photo-induced fungicidal activity elicited by naturally occurring thiophene derivatives

Photo-induced fungitoxicity was observed in Alternaria alternata, Aspergillus niger, Cladosporium variabile, Colletotrichum sp., Rhizopus nigricans, Pythium aphanidermatum, and Saprolegnia sp., elicited by 5-(but-3-en-l-ynyl)-2,2′-bithienyl, 2,2′: 5′,2″-terthienyl, and 2-chloro-4-[5-(penta-1,3-diynyl)-2-thienyl]but-3-ynyl acetate in the presence of near ultraviolet (u.v.) radiation (320–380 nm). Conidiogenesis in A. niger, and sporangiosporogenesis in R. nigricans were depressed on media treated with 2,2′: 5′,2″-terthienyl and irradiated with near u.v. light. Radial growth of mycelia of all fungi tested was dramatically reduced by all three compounds in the presence of near u.v. light. The viability of conidia of A. niger, and R. nigricans was unaffected by 2,2′: 5′,2″-terthienyl, both in the dark and in near u.v. light. Newly emergent germ-tubes were most sensitive to toxicity mediated by u.v. light. The oomycetous fungi tested were the most sensitive to the photo-activated toxicity generated by the three compounds used. The results indicate that ED₅₀ values are dependent upon the species and the presence or absence of near u.v. light. Dramatically lowered ED₅₀ values were always observed in all systems treated with near u.v. light. The dose of near u.v. light used had no effect on the radial growth of fungi in the absence of the three compounds.     

Heterocyclic Insecticides Acting at the GABA-Gated Chloride Channel: 5-Alkyl-2-arylpyrimidines and -1,3-thiazines

5-tert-Butyl-2-(4-ethynylphenyl)pyrimidine and the corresponding 2,5-disubstituted-4H-1,3-thiazine block the GABA-gated chloride channel at c.20and c.200 nm , respectively, measured as 50% inhibition of the binding of 1-(4-ethynylphenyl)-4-[³H]propyl-2,6,7-trioxabicyclo[2.2.2]octane (4′-ethynyl-4-n-[³H]propylbicycloorthobenzoate; [³H]EBOB) in house fly and mouse brain membranes, and they are also toxic to topically-treated flies with LD₅₀ values of 6–27 μg g⁻¹ alone and 2–6 μg g⁻¹ with piperonyl butoxide (PB) as synergist. In the pyrimidine series, the general pattern of effectiveness of substituents in the 5-position is tert-butyl>isopropyl≈cyclohexyl≈cyclopropyl>methyl, phenyl and 3- and 4-fluorophenyl, and in the 2-position is 4-ethynylphenyl≪4-bromophenyl. These planar pyrimidines and nearly-planar 4H-1,3-thiazines with 2-ethynylphenyl or 2-bromophenyl and 5-tert-butyl or 5-isopropyl substituents are more effective than the corresponding 6H-1,3-thiazine, 6-oxo-1,3-thiazines and 4,6-dioxo-1,3-thiazine examined, but they are less active than the analogous conformationally flexible trans-1,3-dioxanes and -1,3-dithianes. The heterocyclic moiety confers a region of high electron density and positions the 2- and 5-substituents in a linear or parallel relationship for optimal affinity at the receptor. Two observations indicate that the new pyrimidines and thiazines probably act as chloride channel blockers. First, the poisoning signs are identical to those of EBOB in both mice and house flies. Second, each of the pyrimidines, thiazines and dioxanes falls on the same correlation line for inhibition of [³H]EBOB binding and toxicity to house flies (with PB) as that obtained earlier for EBOB analogs, dithianes and polychlorocycloalkanes, suggesting that they all act at the same or closely coupled binding sites in the GABA-gated chloride channel.     

Screening of chemical attractants for second-stage juveniles of Meloidogyne species on agar plates

The attractiveness of 60 aromatic compounds, mainly carboxylic acids, alcohols, aldehydes, and phenols, to second-stage juveniles (J2) of four Meloidogyne species (M. hapla, M. incognita, M. javanica, and M. marylandi) was evaluated based on the relative density of J2 attracted to a test compound on an agar plate in an 8.5-cm Petri dish. Three types of nematode responses were observed in the single-compound assays: attraction, in which J2 were attracted to test compounds; concentration-dependent attraction, in which J2 were attracted to the zone located 1–2 cm from test compounds; and no response. None of the test compounds effectively attracted M. incognita or repelled J2 of any species. Thirty-five compounds attracted J2 of at least one of the other three nematode species. Highly effective attractants were trans-cinnamic acid, salicylic acid, 4′-hydroxy-3′-methoxyacetophenone, o-vanillin, carvacrol, 3-methoxybenzyl alcohol, 2-methoxycinnamaldehyde, trans-p-methoxycinnamaldehyde, 4-methoxy-3-methylbenzaldehyde, 2-methoxy-4-propenylphenol, and thymol. Salicylic acid dissolved in the agar reduced the attraction of M. marylandi J2 to salicylic acid and to o-vanillin. Two- and three-compound assays revealed differences in attractiveness to M. marylandi J2 between or among structural isomers of the attractants. o-Vanillin and salicylic acid were much more attractive to M. marylandi than vanillin and the two isomers of salicylic acid, respectively. It is not clear whether nematodes utilize the attractants found in the study for locating hosts in nature, but the attractants may have potential for use in nematode control.     

N-[2-(4,6-二甲氧基嘧啶-2-氧基)苯亚甲基]取代胺类衍生物的合成及除草活性

以水杨醛为原料,经取代、加成和消除反应合成了6个标题化合物(3a~3f),其中4个(3a~3d)为新化合物,其结构经核磁共振氢谱、质谱和元素分析确认。初步的除草活性测试结果表明,在有效成分150 g/hm2的剂量下,除化合物3f对稗草Echinochloa crus-galli的抑制率为55%外,其余5个化合物对供试杂草的抑制率均在80%以上,部分化合物对稗草、早熟禾Poa annua、反枝苋Amaranthus retroflexus或小藜Chenopodium album的抑制率达100%。     

Accumulation and distribution of pp′-DDT and related compounds in an apple orchard. II. Residues in trees and herbage

DDT residues in or on the roots and leaves of the herbage and the roots, bark, leaves and fruit of the trees are given for an apple orchard sprayed annually (1953–1969). The distribution of DDT in both the grass and the grass roots was in circular areas of residues, with maximum values at each trunk and decreasing radially to each alley. Of the spray applied at the green cluster stage 80% was deposited on the grass sward and very little, if any, directly on the soil surface. The pp′-DDT content of the grass fell rapidly with successive mowings (from which the cuttings remained in situ) from 400 μg/g at spraying to 2 μg/g after nine months. 33 g/ha pp′-DDT was found in the herbage roots (0.87% of the total residues in the soil). The residues in the bark (87.5 g/ha) were much lower than expected after 13 years spray application. There were increased amounts of pp′-DDE, pp′-TDE and pp′-TDEE relative to pp′-DDT, indicating some breakdown on the bark, but the chief losses were attributed to volatilisation and to removal by wind and rain. The residue content of root bark varied from 3 μg/g near the emerging trunk to 0.05 μg/g at a depth of 90 cm. The pp′-DDT content of leaves at leaf fall rose from <1 ng/g after a single spring spray to 8.33 μg/g following an additional spray in late June. There was a large loss of DDT from the canopy between the June spray and leaf fall (440–480 g/ha down to 25 g/ha), attributed to volatilisation. The amount of pp′-DDT on the fruit, after a single spray, was 3 ng/g fresh weight (80.9 mg/ha out of a total of 1.0–1.5 kg/ha used).     

Distribution and breakdown of DDT in orchard soil

Amounts of DDT and its breakdown products were determined in soil in an apple orchard in Herefordshire. Samples were taken for a number of years (1972–79) after use of the insecticide in the orchard had ceased in 1969. The results were compared with those obtained in an investigation of the same orchard in 1968. From 1968 to 1979, soil residues of pp′-DDT, p′--DDT and pp′--TDE decreased gradually whereas those of pp′--DDE increased, and there were linear relationships between log (concentration) and time. The calculated time for 50% decrease in concentration (Dt₅₀) was 11.7 years for pp′--DDT, 3.3 years for pp′--TDE and 7.1 years for op′--DDT; the time for doubling the concentration for pp′--DDE was 9.1 years. Regression analysis on the two major components (pp′--DDT+pp′--DDE) indicated that the total amount (2.7 mg kg^?1) was not decreasing with time. It was concluded that during a post-spray era, the breakdown of pp′--DDT to pp′--DDE was a significant feature of the persistence of DDT, and that, in contrast to the findings of other workers who sampled when DDT was being used, there were no losses by volatilisation. There was an exponential decrease in the amount of DDT residues with increasing soil depth and approximately 90% was found in the top 10 cm of the undisturbed soil profile.     

Japanese star anise ringspot-associated virus is a distinct emaravirus transmitted by the eriophyid mite (the family Diptilomiopidae)

Japanese star anise (Illicium anisatum L., JSA) is seriously damaged by a ringspot disease in Japan. Herein, to determine the causal agent using high-throughput sequencing, we discovered viral RNAs associated with JSA ringspot disease. We then determined the complete or near-complete nucleotide sequences of these RNAs using Sanger sequencing and RACE. The complementary strand of viral RNAs 1, 2, 3, 4, and 5 encoded a single protein, which shared sequence identity with P1 (RNA-dependent RNA polymerase), P2 (glycoprotein precursor), P3 (nucleocapsid protein), P4 (movement protein), and a protein with unknown function of emaraviruses (genus Emaravirus), respectively; however, the highest amino acid sequence identity for the P1–P5 proteins between JSARaV and known emaraviruses was 41.9%, 30.0%, 30.1%, 52.2%, and 38.0%, respectively, all of which were lower than the species demarcation criterion. Furthermore, RNA segments harbored conserved 12-nt terminal sequences at the 5′- and 3′-termini, and a high complementarity of approximately 20 nt in 5′- and 3′-terminal sequences. Transmission electron microscopy confirmed the presence of virus-like particles. JSA ringspot disease was found to be transmitted by an eriophyid mite (subclass Acari, superfamily Eriophyoidea) that belongs to the family Diptilomiopidae. Taken together, these results identified the virus responsible for the ringspot disease of JSA as a new member of the genus, Emaravirus, which we named as the Japanese star anise ringspot-associated virus (JSARaV). Moreover, this is the first report noting that eriophyid mites of the family Diptilomiopidae are capable of transmitting emaravirus.

     

梨和苹果腐烂病菌不同培养表型菌株的致病性分析

The pathogenicity of three strains (F-SD-8, F-BJ-2c-2 and F-HN-2a-1) of Valsa mali var. pyri causing pear canker and one strain (F-SX-A6) of V. mali var. mali causing apple canker in China were comparatively tested by wound inoculation on in vitro twigs of pear, apple and some other woody plants, and in vivo twigs of pear. Significant pathogenicity differentiation was detected in V. mali var. pyri. Generally strains F-SD-8 and F-BJ-2c-2 were highly pathogenic on pear although their culturing characteristics differed greatly. The strain F-SX-A6 was more aggressive on apple than on pear, and the strain F-HN-2a-1 showed significant lower pathogenicity on ten pear cultivars and other seven species of woody plants. Our results confirmed that two variants of V. mali had host preference and were also aggressive to crabapple, apricot, and peach besides apple and pear. Meanwhile, strains F-SD-8 and F-BJ-2c-2 could induce the formation of pycnidia on in vivo twigs of pear, which was not observed on in vivo twigs inoculated with F-HN-2a-1 and F-SX-A6.     

Design,synthesis and structure–activity relationships of novel ALS inhibitors

The paper describes the biophore models of sulfonylurea, imidazolinone, triazolopyrimidinesulfonamide and 5‐pyrimidyltriazolo‐3‐sulfonamides established by the Apex‐3D method. A series of N‐phenylsulfonyl‐N ′‐(thiadiazol‐2‐yl)oxamides and three types of triazolopyrimidinesulfonamide were synthesised and their herbicidal activities determined to assess the validity of the model. In general, the model gave useful leads to activity, although the actual level was not always predicted accurately. In only a few cases did compounds predicted as being active prove to be inactive in the bioassay, and compounds with little or no activity were clearly indicated. As a result of this work, the compound N,N ′‐[1‐(5,7‐dimethyl‐1,2,4‐triazolo[1,5‐a]pyrimidin‐2‐yl‐thio)butane‐2,3‐di‐imino]bis(2‐chlorobenzenesulfonamide) was selected as showing good activity against a range of species, and will be used as a lead for further development. © 2000 Society of Chemical Industry     

N-取代苯基-2-(苯并异噻唑啉-3-酮-2-基)甲酰胺的合成及抑菌活性

通过取代苯异氰酸酯与1,2-苯并异噻唑啉-2(3H)-酮(BIT)反应,制备了13个2-(苯并异噻唑啉-3-酮-2-基)甲酰胺类化合物,其中9个未见文献报道。所有化合物的结构均经IR、1H NMR和元素分析确认。初步的抑菌活性测定结果表明,部分目标化合物对供试病原菌具有很好的抑菌活性,尤其对于枯草芽孢杆菌Bacillus subtilis和芒果蒂腐病菌Botryodiplodia theobromae,大部分化合物在50 mg/L下的抑制率在80%~100%之间。     

2-氧代-2-苯基乙磺酰胺化合物组合合成与杀菌活性研究

为了快速获得具有高效杀菌活性的先导化合物,利用组合化学与传统合成方法相结合的方案,研究了N-取代-2-氧代-2-苯基乙磺酰胺类化合物对灰霉病菌的杀菌活性。首先以苯乙酮为原料,经过磺化、氯化反应,制备得到2-氧代-2-苯基乙磺酰氯,再分别与苯胺、苄胺和烷基胺组合库反应,制备了33个组合库,其中包含105个化合物,收率在60%~90%之间,纯度在70%~95%之间。筛选其中的10个活性库进行平行合成,得到29个化合物,又对其中10个活性化合物进行了纯化与结构鉴定。最后用灰霉病菌Botrytis cinerea对所有组合库与化合物进行离体与活体双重筛选,快速确定了高活性先导化合物,为进一步的结构优化奠定了基础。     

Characterization of ISPsy2 and ISPsy3, Newly Identified Insertion Sequences in Pseudomonas syringae pv. eriobotryae

Two new active insertion sequences, ISPsy2 and ISPsy3, were isolated from Pseudomonas syringae pv. eriobotryae, the causal agent of stem cankers of loquat trees. ISPsy2 is 1194-bp long, has 16-bp imperfect terminal inverted repeats, and generates a 4-bp target site duplication upon insertion into the selective cartridge of the entrap vector pSHI1063. The nucleotide sequence of ISPsy2 is completely identical with that of the previously identified IS-like element located adjacent to the virulence gene psvA of Pseudomonas syringae pv. eriobotryae NAE6. The single open reading frame of ISPsy2 encodes a 323-amino-acid protein that has similarity to the transposase of the IS5 subgroup of the IS5 family. The ISPsy3 belonging to the IS91 family is 1507 bp in length, does not duplicate its target sequence, GAAC, and presents an 81% sequence homology with IS801 in P. s. pv. phaseolicola. The transposase of ISPsy3 possesses the conserved amino acid motifs found in the rolling-circle replication protein. Southern blot analysis indicated that multiple copies of ISPsy2 and ISPsy3 are present in the genomes of P. s. pv. eriobotryae and some of the other P. s. pathovars tested. Received 16 August 2001/ Accepted in revised form 19 October 2001     

Development of a robust,VdNEP gene-based molecular marker to differentiate between pathotypes of Verticillium dahliae

Verticillium dahliae is a soilborne fungus that causes Verticillium wilt disease in a plethora of crops. Based on symptoms that develop on cotton, olive and okra, V. dahliae isolates are categorized into two pathotypes, namely defoliating and nondefoliating, with the former showing increased virulence and causing severe defoliation. Reliable differentiation between V. dahliae pathotypes is crucial for the management of Verticillium wilt in cotton and olive. In the present study, a polymorphism was detected among isolates of defoliating and nondefoliating pathotypes in Southern blots using the VdNEP gene as a probe. The regions flanking this gene were isolated by inverse PCR and sequence differences in the 3′ untranslated region (3′-UTR) of the VdNEP gene were detected between the two pathotypes. Based on these sequences, primers were designed and assessed to develop a multiplex PCR detection assay. Using this assay, a collection of cotton and olive V. dahliae isolates from Greece and Cyprus was screened, revealing that the defoliating pathotype is present in several regional units of Greece. Thus, this work presents a new, sensitive molecular marker for the differentiation between V. dahliae pathotypes based on the VdNEP gene. Because the 3′-UTR is involved in the phenotypes displayed by the pathotypes, an expression experiment was conducted under conditions simulating the xylem of a host plant. Expression of the VdNEP gene was elevated at all time points in the defoliating compared to the nondefoliating strain, suggesting a possible involvement of VdNEP expression in the defoliation process.     

Occurrence and genetic diversity of Blackcurrant reversion virus found on various cultivated and wild Ribes in Latvia

A large‐scale survey was carried out to assess the occurrence, natural host range and genetic diversity of Blackcurrant reversion virus (BRV) in cultivated and wild Ribes in Latvia using RT‐PCR and sequence analyses of 3′ NTR of BRV RNA2. The virus was detected in all surveyed habitats in most of the studied Ribes, except gooseberries, Ribes sanguineum, Ribes laxiflorum and crossbreeds between blackcurrants and gooseberries. The overall occurrence of BRV was 27%, although it varied significantly among the surveyed Ribes habitats, exceeding 40% in home gardens and germplasm collections. Among cultivated Ribes, blackcurrants were the most infected and BRV was detected in all commonly grown cultivars. The virus was detected for the first time in Ribes aureum, Ribes fragrans, Ribes nigrum var. pauciflorum and Ribes fasciculatum var. chinense. The sequence identities of the studied fragments of RNA2 3′ NTR varied from 92.8% to 99.7% among 26 BRV isolates from various cultivated, ornamental and wild hosts from Latvia and from 91.1% to 97.1% when they were compared with 27 corresponding sequences from GenBank. Phylogenetic analyses revealed that the major clustering of isolates was not related to host, origin or symptoms. Grouping of BRV isolates based on host or location was identified within the phylogenetic subclusters. Several well‐supported clades were formed within the subclusters, including a group of BRV isolates from redcurrants that had unique nucleotide substitutions. Five putative recombinants were identified for the first time among BRV isolates from Latvia, Finland, Scotland and the Czech Republic.