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%。     

Problem of flower shedding caused by thrips,Megalurothrips distalis (Karny), on summer mungbean,Vigna radiata (L.) Wilczek,and its control

Abstract

Flower shedding in summer mungbean, Vigna radiata (L.) Wilczek, is a common feature caused by thrips, Megalurothrips distalis (Karny). Eleven insecticides were tested in field trials for the control of thrips during the period 1982 to 1984. All the treatments were significantly better in controlling the thrips, reducing flower shedding, increasing the pod numbers and grain yield, in comparison with the control. Increases in yield compared with the control during trials ranged from 85 to 89% (1982), 26 to 96% (1983) and 5 to 194% (1984). Dimethoate gave the highest increases in yield and profit followed by monocrotophos and endosulfan.     

新型含苯并咪唑的(S,S)-2,8-二氮杂双环[4.3.0]壬烷类衍生物的合成及生物活性

通过N-烷基化反应合成了一系列新型含苯并咪唑的(S,S)-2,8-二氮杂双环[4.3.0]壬烷类衍生物,中间体化合物通过环化反应和酰化反应合成得到。所有新型化合物的结构均通过熔点测定、核磁共振氢谱和高分辨质谱确认。生物活性测试结果显示,目标化合物拥有中等的抗植物真菌活性,对东方粘虫Mythimna separata Walker和蚊幼虫Culex pipiens pallens具有中等到良好的杀虫活性。其中化合物6e和6f对油菜菌核Sclerotinia sclerotiorum、马铃薯晚疫Phytophthora infestans、小麦赤霉Fusarium graminearum等真菌具有良好的抗菌活性。化合物6e和6k在200mg/L下对东方粘虫的致死率为100%,化合物6h和6k在2mg/L下对蚊幼虫的致死率为75%。     

山蒟中脂肪链酰胺类化合物的分离及杀虫活性

采用提取、萃取及柱层析等方法,从山蒟Piper hancei Maxim甲醇提取物的石油醚和氯仿萃取相中分离到6个脂肪链酰胺类化合物,通过核磁共振、质谱并结合相关文献比对,其结构被分别鉴定为已知化合物chingchengenamide A( C1 )、N-异丁基-反-2-反-4-癸二烯酰胺( C2 )、假荜拨酰胺A( C3 )、荜茇宁( C4 )、N-p-香豆酰酪胺( C5 )和N-反式-阿魏酰酪胺( C6 ),其中 C1 为首次从山蒟中获得。利用幼虫浸液法测试了各化合物对白纹伊蚊Aedes albopictus和致倦库蚊Culex pipiens quinquefasciatus幼虫的12 h杀虫活性。结果表明:在20 mg/L下,化合物 C1 对白纹伊蚊的杀虫活性较高,其校正死亡率为100%,LC₅₀值为5.37 mg/L;化合物 C1 、 C2 、 C3 和 C4 对致倦库蚊的杀虫活性较高,20 mg/L下的校正死亡率分别为100%、88.5%、100%和100%,LC₅₀值分别为1.03、9.68、3.08和2.87 mg/L。     

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。     

Effect of different levels of bruchid,Callosobruchus chinensis (L.) infestation on chickpea,Cicer arietinum L. in India

Abstract

In a study of the effect of initial infestation of chickpea, with one, two, three, four and five sexual pairs of pulse bruchid, up to F₁ (one generation) and F₂ (two generations), a highly positive correlation (r = 0.949) occurred between population in the F₁ and the number of pairs of beetles, but not up to F₂ generation. Significant correlations of r = 0.921 and r = 0.385 between grain damage (%) and final population also occurred for the F₁ and F₂ generations, respectively, also high positive correlations (r = 0.974 for F, and r = 0.959 for F₂) between loss in grain weight and population. The coefficients of determination revealed that 97% and 92% variability in loss in grain weight was due to the number of pairs of beetles initially released, their final population and per cent grain damage, for the F₁ and F₂ generations, respectively.     

寡肽手性膦酸酯硫脲的合成及其抗烟草花叶病毒活性

为了寻找新型具有抗烟草花叶病毒 (TMV) 作用的化合物,在前期研究工作基础上,以取代苄胺、氨基酸及亚膦酸二烷基酯等为原料,按照由C端向N端依次接肽的合成策略,采用缩合剂O-苯并三氮唑-四甲基脲六氟膦酸酯 (HBTU) 合成酰胺的方法,获得了18个新型寡肽手性膦酸酯硫脲,其结构均经红外光谱、(1H、13C、31P、19F) NMR及元素分析确证和表征,并首次研究了该类化合物抗TMV活性。结果表明:部分目标物对TMV具有较高治疗作用,其中化合物 5i 、 5j 和 5p 在500 μg/mL时对TMV侵染的活体治疗作用效果分别为52.6%、55.7%和56.1%,接近对照药剂宁南霉素 (55.4%)。值得进一步结构改造和构型优化,并在此基础上进行作用机制研究。     

International Symposium on Diseases of Tropical Food Crops,Louvain-La-Neuve. September 1978

Abstract

Covering maize cobs by wrapping maize leaves around them reduced damage by rose‐ringed parakeets (Psittacula krameri) by 97% in the field and 82% in aviary experiments. Being hidden and camouflaged, the wrapped cobs may have escaped detection by birds and thus were not damaged. The wrapping treatment also provided some protection to uncovered cobs within the treated plot, possibly by reducing the density of visible cobs in this plot compared with the control. There was no adverse effect of the wrapping treatment on grain yield.     

Possible Methods for Controlling Ischaemum afrum (J. F. Gamel) Dandy,in Fallow

Abstract

Different mechanical cultivations and herbicide treatments were compared for controlling Ischaemum afrum in a heavily infested fallow area. Of the mechanical cultivations, disc ploughing to a depth of more than 15 cm, following removal of tufts and watering, was found very effective (83% reduction). Incorporated pre-emergence triluralin (1.90 kg a.i./ha) alone or in tank mixtures with oxadiazon (0.95 + 0.95 kg a.i./ha) was also found promising (79 and 76% reduction respectively). Three applications of dalapon (8.09 kg a.i./ha), as post-emergence, at two weekly intervals or two applications followed by another application at 4.05 kg a.i./ha gave almost complete eradication of Ischaemum afrum seedlings for about 12 weeks (99% reduction).     

异香豆素噁二唑类化合物的合成及除草活性

为了寻找具有较高除草活性的异香豆素类化合物,设计合成了16个新型异香豆素噁二唑类化合物4a～4p,其结构均经核磁共振氢谱、碳谱及高分辨质谱确证。初步除草活性测定结果表明,部分目标化合物在500 mg/L下对马唐Digitaria sanguinalis L.和反枝苋Amaranthusretroflexus L.具有一定的除草活性,其中化合物4j（4-[5-（4-氯-苯基）-[1,2,4]二唑-3-基]-3-己基-6,7-二甲氧基异香豆素）的活性最好,对马唐和反枝苋的致死率分别为64%和62%。     

N-(2-三氟甲基-4-氯苯基)-2-吡唑酰氨基环己烷基磺酰胺类化合物的合成与杀菌活性

吡唑酰胺类杀菌剂是近年新农药开发的热点。本研究采用EDCI/HOBt酰胺化法合成了14个结构新颖的N-(2-三氟甲基-4-氯苯基)-2-吡唑酰氨基环己烷基磺酰胺类化合物 ( 3a ~ 3n ),其结构均经1H NMR、13C NMR、质谱和元素分析确认,并用X-射线衍射法确定了化合物 3g 的单晶结构和立体构型。菌丝生长速率法试验结果表明,化合物 3a 、 3e 和 3j 对番茄灰霉病菌Botrytis cinerea KZ-9的EC₅₀值分别为4.28、10.08和11.31 mg/L,抑菌活性不及对照药剂啶酰菌胺和腐霉利;但在孢子萌发试验中,目标化合物表现出与对照药剂相近的抑菌活性,在10 mg/L下有7个化合物对灰霉病菌孢子萌发的抑制率超过了85%;在番茄活体盆栽试验中,化合物 3e 在200 mg/L下对番茄叶片及其花上灰霉病菌的防治效果分别为77.5%和65.2%,高于对照药剂啶酰菌胺 (防效分别为59.8%和30.3%),有进一步研究的价值。     

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。     

Leafminers in vegetables,ornamental plants and weeds in Indonesia: Surveys of host crops,species composition and parasitoids

Extensive surveys of vegetable, ornamental and weedy plant species were conducted in highland and lowland vegetable production areas in Indonesia with the aim of recording leafminer species present and their associated natural enemies. The most common dipterous species reared from samples was the pea leafminer, Liriomyza huidobrensis (Blanchard) (Diptera: Agromyzidae). This introduced pest was particularly serious in highland vegetables in Java, Sumatra and South Sulawesi, causing yield losses as high as 60-70%. Another alien species, the vegetable leafminer, Liriomyza sativae Blanchard, contributed to problems in lowland areas on the north coast of West Java, where cucumbers were heavily damaged. An Asian leafminer species, Chromatomyia horticola Goureau, was more common in snow peas (Pisum sp.). Intensive sampling of leafminer-infested leaves from surveyed host plants yielded 11 species of hymenopteran parasitoids: 10 eulophids (Asecodes sp., Chrysocharis sp., Cirrospilus ambiguus (Hansson and LaSalle), Closterocerus sp., Hemiptarsenus varicornis (Girault), Neochrysocharis formosa (Westwood), Neochrysocharis sp., Pnigalio sp., Quadrastichus sp., Zagrammosoma sp.) and 1 eucoilid (Gronotoma sp.). The most abundant parasitoid species was H. varicornis. Levels of parasitism varied among crops and growing seasons, but were usually low, especially on potato (< 3%). Surveys revealed that most farmers (63%) attempted to control leafminers by applying insecticides twice weekly although these applications were neither effective nor economical according to responses of about 72% of the farmers. An integrated pest management approach is suggested that emphasizes IPM training for vegetable farmers and includes reductionor elimination of broad spectrum chemicals that would adversely affect parasitoids that may already be present as well as those that may be introduced. The initiation of a classical biological control programme is recommended to enhance the limited parasitoid complex present in Indonesia and increase levels of biological control.     

O-酰基化丝氨酸的合成及其对樱桃番茄乙烯合成量和果实硬度的影响

通过L-丝氨酸与不同的酰氯在室温下反应,合成了8个未见文献报道的乙烯合成抑制剂O-酰基化丝氨酸（2a~2h）,其结构通过核磁共振氢谱、碳谱及高分辨质谱确证。以氨乙氧乙烯基甘氨酸（aminoethoxyvinylglycine,AVG）为阳性对照,测定了目标化合物对樱桃番茄Lycopersivon esculentum Mill.乙烯合成量和果实硬度的影响,同时运用分子对接的方法分析了目标化合物与番茄1-氨基环丙烷羧酸（1-aminocyclopropane-1-carboxylic acid, ACC）合成酶（ACS, 1IAY）可能的结合模式。结果显示:大部分目标化合物具有延缓樱桃番茄果实软化和抑制乙烯合成的作用,其中化合物2c和2h效果较为突出。用2c和2h处理番茄后第5天,与空白对照相比,果实硬度分别提高27.62%和40.04%,均与AVG处理无显著性差异;2c和2h对乙烯合成量的抑制率分别达71.89%和53.28%,其中2c处理的抑制效果显著优于AVG处理。分子对接方法分析结果表明:化合物2c与番茄ACS酶活性空腔的氨基酸残基有较好的相互作用,2c的羧基可与Ala54和Arg412的氨基形成氢键,从而占据ACS酶的活性空腔。O-酰基化丝氨酸类化合物结构简单,容易获取,对乙烯合成抑制剂的开发具有推动作用。     

Fourth International Congress of Pesticide Chemistry,Zurich, July 1978

Soybean Rust. By Kenneth R. Bromfield. American Phytopathological Society, Monograph no. 11, 1984, pp. 65. ISBN 0–89054–062–4. Price $10.50 (A.P.S. members $ 8.00).

Plant‐Microbe Interactions. Volume 1. Molecular and Genetic Perspectives. Edited by Tsune Kosuge and Eugene W. Nester. New York: Macmillan, 1984., ISBN 0–02–949470–2. Price $38.00.

Coffee Rust in the Americas. Edited by R. A. Fulton. American Phytopathological Society, Symposium Book No. 2, 1984, pp. 120. ISBN 0–89054–064–0. Price $18.00 (APS members $14).

Acarology VI, Volume 2. Edited by D. A. Griffiths and C. E. Bowman. Proceedings of the VI International Congress of Acarology held at Edinburgh University, Scotland, 5–11 September 1982, pp. 647–1296. Chichester: Ellis Horwood Limited. ISBN 0–85312–604–6. Price £49.50. (Distributed by John Wiley &; Sons Ltd.)

Index Phytosanitaire 1985: France, Afrique Méditer‐ranéenne et Tropicale. Association de Coordination Technique Agricole. Price 98 f (in France), 91 f (overseas, without tax).     

New Chalcidoidea (Hymenoptera) parasitoids of Dasineura saliciperda (Dufour) (Diptera, Cecidomyiidae) in Bulgaria

Abstract The parasitoid complex of Dasineura saliciperda (Dufour) (Diptera, Cecidomyiidae) on Salix fragilis L. was studied in 1997 and 2002 in two localities in Bulgaria. As a result, 5 species from 3 families of Chalcidoidea (Hymenoptera) were reared from pest galls: Eurytoma afra Boheman, Eurytoma salicis Walker (Eurytomidae), Torymus microcerus (Walker) (Torymidae), Gastrancistrus sp. and Mesopolobus sp. (Pteromalidae). E. afra and T. microcerus are new species for the fauna of Bulgaria, and E. salicis – a new parasitoid of the host. Total parasitism of D. saliciperda in the studied years ranged between 44.1 and 53.5 %. E. afra was the most important, destroying 21.9-53.5 % of the pest.     

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%。     

Evolution and status of Oecophylla smaragdina (Fabricius) as a pest control agent in citrus in the Mekong Delta,Vietnam

Citrus farmers in the Mekong Delta have a long tradition of managing the weaver ant Oecophylla smaragdina (Fabricius). From 1994 to 1998, insecticide use increased significantly (P< 0.01) from 66% to 84% in orchards where O. smaragdina occurred. In 1998, ca 75% of the sweet orange (Citrus sinensis) and 25% of the Tieu mandarin (C. reticulata) orchards had large O. smaragdina populations, due to lower pesticide pressure in the first crop. In orchards with O. smaragdina, farmers sprayed less frequently and used fewer highly hazardous insecticides. Major insecticides used in sweet orange were monocrotophos and alpha-cypermethrin, and those used in Tieu mandarin were methidathion, imidacloprid and fenpropathrin. Expenditure on pesticides was reduced by half when O. smaragdina was abundant, without affecting either the yield or the farmers' income. Therefore, O. smaragdina husbandry is a good example of a traditional practice which should be further promoted as an important component of sustainable citrus production. The experience of those farmers who use no or few pesticides should be drawn upon in developing farmer training programmes or mass media tools to promote IPM in citrus. Farmers practicing ant husbandry were significantly older than those not doing so.     

Suppression of Meloidogyne hapla by arbuscular mycorrhiza fungi (AMF) on pyrethrum in Kenya

Two arbuscular mycorrhiza fungi (AMF) isolated from a pyrethrum-growing region in Kenya were screened for efficacy against a nematode, Meloidogyne hapla, in greenhouses. The fungi were identified at INVAM (International Culture Collection of Vesicular Arbuscular Mycorrhizal Fungi) as Glomus etunicatum (Isolate KS18) and Glomus sp. (Isolate KS14). Isolate KS14 (Glomus sp.) significantly suppressed nematode population, growth and development by up to 54%, egg production by up to 75% and disease severity by up to 71%. Glomus etunicatum (Isolate KS18) suppressed nematode growth and development by up to 50%, egg production by up to 75% and disease severity by up to 57%. In addition, G. etunicatum and Isolate KS14, significantly improved top dry biomass of pyrethrum by up to 33% and 47%, respectively. Glomus etunicatum and M. hapla were mutually inhibitory as root colonization by G. etunicatum was significantly reduced (up to 24%) by the presence of the nematode. The presence of the nematodes, on the other hand, did not significantly affect root colonization by Isolate KS14.     

香豆素类化合物对朱砂叶螨的触杀活性及定量构效关系研究

采用玻片浸渍法,测定并筛选了25种具有代表性的香豆素类化合物对朱砂叶螨Tetranychus cinnabarinus雌成螨的触杀活性,并构建了一个预测能力较强的定量构效关系(QSAR)模型。结果表明:所有供试化合物对朱砂叶螨均具有触杀活性,且随着处理时间的延长活性升高。处理48 h后,LC50值低于1000 mg/L的化合物有8个,分别是3-(2-苯并咪唑)-7-(二乙氨基)香豆素(1)、3-(2-苯并噻唑)-7-(二乙氨基)香豆素(2)、3-氨基香豆素(3)、3-乙酰基香豆素(4)、4-甲氧基香豆素(5)、6-硝基香豆素(8)、6,7-二甲氧基香豆素(13)和7,8-二羟基香豆素(21),其中化合物1、2、3、5和13的杀螨活性优于药剂对照螺螨酯或与其活性相当;活性最好的化合物为13,处理48 h和72 h后LC50值分别为284.8和122.2 mg/L,其毒力约为螺螨酯的2倍。通过计算得到25种香豆素类化合物的34种物化参数,以此为描述子,经过SPSS相关性剔除、逐步回归分析和校正,得到一个以扭转力、取向力、总能量和分子半径为自变量的QSAR模型,该模型复相关系数R达到0.987,复判定系数R2也达到0.967,通过F检验证明上述模型具有较高的预测能力。