The structure and properties of O-ethyl O-isopropyl O-(5-methoxy-1-methyl-6-oxo-1H-pyridazin-4-yl) phosphorothioate and by-products in the technical product

The structure and some chemical and physical properties of a new insecticide O-ethyl O-isopropyl O-(5-methoxy-1-methyl-6-oxo-1H-pyridazin-4-yl) phosphorothioate ( I ) and by-products present in the technical product are described. The structures of I and the by-products were proved by infrared, ultraviolet, ¹H-n.m.r., Raman and mass spectrometry.     

Synthesis and insecticidal and acaricidal properties of some 5-methoxy-1-methyl-6-oxo-1H-pyridazin-4-yl phosphorus esters. III

A series of new 5-methoxy-1-methyl-6-oxo-1H-pyridazin-4-yl phosphorus esters, which was prepared by phosphoroylation of 5-methoxy-1-methyl-6-oxo-1H-pyri-dazin-4-ol, is described. Many of the compounds showed high insecticidal and acaricidal activity.     

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.     

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.     

N-取代苯基-4-(1-甲基-1H-吡唑-5-基)噻吩-2-甲酰胺的合成、杀菌活性及分子对接

为了寻找结构新颖的琥珀酸脱氢酶(SDH)类衍生物,在前期发现吡唑联苯甲酰胺基础上,采用骨架跃迁的策略,设计并合成了18个N-取代苯基-4-(1-甲基-1H-吡唑-5-基)噻吩-2-甲酰胺类衍生物(3a～3n,4a～4d),其中17个为新化合物.通过1H NMR、13C NMR和高分辨质谱(HRMS)确证了化合物的结构....     

Residues of the carbamate acaricide, 3-methyl-5-isopropylphenyl-N(n-butanoyl)-N-methylcarbamate (promacyl) and two metabolites in the tissues and milk of cattle

In order to assess some of the residue characteristics of the experimental carbamate acaricide, 3-methyl-5-isopropylphenyl-N-(n-butanoyl-)-N-methylcarbamate (promacyl) a 0.2 % aqueous emulsion was applied to cattle in a series of five trials and in a sixth, the technical product was added to the feed of stalled cattle. A method of analysis involving the formation of a derivative suitable for gas chromatographic analysis on electron capture detection mode was developed. Separate estimations of levels of the parent compound and the metabolites, 3-methyl-5-isopropylphenyl -N-methylcarbamate and 3-methyl-5- isopropylphenol, were carried out on fatty tissues and butterfat but for non-fatty tissues “total” levels, which were a combined estimate of 3-methyl-5-isopropylphenol itself and all substances hydrolysable to it, were estimated and quoted as Promacyl. The highest group average level of the parent compound was 0.9 part/million in fatty tissues 24 h after the last of 8 applications at 3 day intervals. In a single spray trial the maximum group average of 0.7 part/million in fatty tissues 24 h after treatment fell to 0.2 part/million after 5 days. Residues in butterfat, 7 h after a single dermal application showed a maximum level of 1.2 parts/million and this declined to 0.1 part/million on the seventh day after treatment. “Total” residues in non-fatty tissues were of the order of 1/10 those found in fatty tissues.     

Synthesis and herbicidal activity of new 3-(3-bromothiophen-2-yl)-5-(2,6-difluorobenzyl)oxymethyl-5-methyl-4,5-dihydroisoxazole as a paddy field herbicide

A new compound 3-(3-bromothiophen-2-yl)-5-(2,6-difluorobenzyl)oxymethyl-5-methyl-4,5-dihydroisoxazole was synthesized and the herbicidal activity was assessed under glasshouse and flooded paddy field conditions. This compound demonstrated good rice selectivity and potent herbicidal activity against annual weeds at 125 g ai ha⁻¹ under greenhouse conditions. Soil application of this compound showed the complete control of barnyardgrass to the 4th leaf stage at 250 g ai ha⁻¹. Field trials indicated that this compound, combined with pyrazosulfuron-ethyl, controlled annual and perennial weeds rapidly with good tolerance by transplanted rice seedlings from postemergence and soil application. This compound showed a low mammalian and environmental toxicity in various toxicological tests.     

3-苄基-5-(1-(2-氧代-1-氧杂螺[4,5]癸-3-烯-3-基)亚乙基)-2-氨基咪唑啉-4-酮类化合物的合成及杀菌活性

为寻找高活性的杀菌化合物,在前期合成5-(1-(4-甲基-2-氧代-1-氧杂螺[4,5]癸-3-烯-3-基) 亚乙基)-2-氨基咪唑啉-4-酮类化合物的基础上进行结构修饰,在咪唑啉-4-酮的3-位引入苄基,设计并合成了一系列未见文献报道的化合物,其结构经过核磁共振氢谱 (1H NMR)、碳谱 (13C NMR) 及高分辨质谱 (HR-ESI-MS) 确证。经高效液相色谱 (HPLC) 分析显示,Z-构型中间体化合物 6 在酸性条件下会发生氮质子化开环再环化,转化为E-构型化合物 7 。离体杀菌活性测定结果表明,3-位苄基的引入改善了该类化合物的杀菌活性,其中化合物 (E)-3-苄基-5-(1-(4-甲基-2-氧代-1-氧杂螺[4,5]癸-3-烯-3-基) 亚乙基)-2-(4-甲氧基苯基) 氨基-咪唑啉-4-酮 ( 9c ) 和 (E)-3-苄基-5-(1-(4-甲基-2-氧代-1-氧杂螺[4,5]癸-3-烯-3-基) 亚乙基)-2-(4-氟苯基) 氨基-咪唑啉-4-酮 ( 9h ) 对油菜菌核病菌的EC₅₀ 值分别为14.3和21.1 mg/L。活体杀菌活性测试结果显示,在400 mg/L下化合物 9c 对于黄瓜霜霉病和小麦白粉病的防治效果分别为 80%和85%。     

Effects of a Chenopodium-based botanical insecticide/acaricide on Orius insidiosus (Hemiptera: Anthocoridae) and Aphidius colemani (Hymenoptera: Braconidae)

UDA-245 is a Chenopodium-based natural insecticide. Forty-eight hours after treatment with this compound, Orius insidiosus (Say) and Aphidius colemani Viereck showed slight contact toxicity at 5 g AI liter(-1). There was no residual toxicity to A colemani. These two beneficials are currently used in commercial flower and vegetable greenhouses for the management of thrips, spider mites, aphids and small caterpillars. In contrast, abamectin and insecticidal soap were toxic by contact to both species. UDA-245 did not reduce the number of eggs laid by treated O insidiosus. The eclosion of these eggs was also not adversely affected by UDA-245. The other two insecticides, abamectin and insecticidal soap had no effect on the emergence of A colemani from treated aphid mummies. However, abamectin decreased the percentage of aphid parasitism by A colemani following a residual treatment. The LC50 for UDA-245 for the two beneficials is slightly over twice the recommended field dose.     

4-甲基-2-(1H-吡唑-1-基)-噻唑-5-甲酰胺类化合物的合成及杀菌活性

以4-甲基-2-(1H-吡唑-1-基)-噻唑-5-甲酰氯为原料,与取代胺作用制得10个结构新颖的4-甲基-2-吡唑基-噻唑甲酰胺类化合物,利用1H NMR和MS对其结构进行了表征。盆栽法试验结果表明,在500 mg/L质量浓度下,部分化合物对黄瓜霜霉病和黄瓜白粉病的相对防效达100%,对黄瓜灰霉病的防效达85%。     

N-[4-叔丁基-6-芳基-5-(1,2,4-三唑-1-基)-1,3-噻嗪-2-基]酰胺类化合物的合成及抑菌活性

以α-三唑基频那酮为起始原料,经缩合、环化和酰胺化反应合成了15个未见文献报道的化合物,其结构均经核磁共振氢谱、红外光谱和质谱确认。初步抑菌活性测试结果表明,在50 mg/L下,目标化合物对供试植物病原菌均有不同程度的抑制作用,其中化合物3a-3、3a-4、3a-5、3b-2和3b-3对番茄灰霉病菌Botrytis cinerea的抑制率达80%以上,3a-4和3a-5对棉花枯萎病菌Fusarium oxysporum vasinfectum的抑制率分别达78.6%和82.4%。     

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%。     

Effect of 4-amino-6-methyl-3-phenylamino-l,2,4-triazin-5(4H)-one on the lignification process catalysed by peroxidase from lupin (lupinus albus)

The molecular action of herbicides with a triazine structure, such as atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) and metribuzin (4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5(4H)-one), has been related to their inhibition of the electron carrier system between chloroplastic photosystems II and I. This report provides evidence that 4-amino-6-methyl-3-phenylamino-1,2,4-triazin-5(4H)-one, a recently synthesised triazine, structurally analogous to metribuzin, causes a powerful inhibition of the cell-wall lignification catalysed by peroxidase from lupin. The two reactions involved in this lignification process are: oxidative polymerisation of coniferyl alcohol and the generation of hydrogen peroxide at the expense of NADH oxidation.     

A novel series of O,O-diethyl O-(1,3-disubstituted-1,2,4-triazol-5-yl) phosphorothioates. Part I. Synthesis and laboratory evaluation

A novel series of O,O-diethyl O-(1-R′-3-R″-1,2,4-triazol-5-yl) phosphorothioates, in in which R″ was an alkyl group and R″ was a radical characterised by the presence of a conjugated multiple bond, generally of a vinyl nature, has been synthesised and tested in the search for new insecticides. Several of the compounds showed a broad spectrum of activity, covering important species of Orthoptera, Hemiptera, Lepidoptera, Coleoptera, Diptera and mites. At the same time they were characterised by a relatively low oral toxicity to rats.     

Synthesis and bioactivity of some new N-aryl/alkyl/cyclohexyl-N'-(2,3-dihydro-2-oxo-4H-benz[e][1,3,2]oxazaphosphorin-2-yl) ureas

Several new substituted oxazaphosphorinyl urea derivatives of the type RR'P(O)NHC(O)NHR' were synthesized from alpha-(3-chloro-4-fluoroanilino)-o-cresol by reaction with chlorides of aryl/alkyl/cyclohexyl carbamidophosphoric acids in the presence of triethylamine at 0-50 degrees C. Their significant insecticidal and antimicrobial activity and promotion of Rhizobium bacteria growth in the soil without effect on the host tissue suggests their possible commercial application as ecofriendly pesticides and antimicrobial agents.     

Effect of 4-amino-6-methyl-3-phenylamino-1,2,4-triazin-5(4H)-one on the integrity of chloroplasts from barley leaves

4-Amino-6-methyl-3-phenylamino-1,2,4-triazin-5(4H)-one alters the integrity of chloroplasts in barley (Hordeum vulgare L. var. Hassan) leaves as judged by their sedimentation profiles in linear gradients of sucrose. This effect may be related to the inhibition caused by 4-amino-6-methyl-3-phenylamino-1,2,4-triazine-5(4H)-one of both ascorbate peroxidase and superoxide dismutase activities, and could thus be explained by an accumulation of toxic reduced-oxygen species in illuminated chloroplasts.     

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%。     

N-(7-氟-3-氧-3,4-二氢-苯并[b][1,4]口恶嗪-6-基-)乙酰胺类化合物的合成及除草活性

为了寻找高效、安全的具有除草活性的新化合物,利用2-取代乙酰氯和2H苯并[b][1,4]口恶嗪-3-酮反应合成了9个N-(7-氟-3-氧-3,4-二氢苯并[b][1,4]口恶嗪-6-基-)乙酰胺类化合物,其结构经元素分析、IR1、H NMR确证。初步除草活性测试表明:在有效剂量75g/hm2下,化合物5d芽后茎叶处理对刺苋Amaranthus spinosus等4种杂草显示出90%以上的抑制率。     

(4-亚甲基-5-羰基-3-四氢呋喃基)-苯甲酸甲酯衍生物的合成及其杀菌活性

为了探索天然产物Cedarmycins衍生物的结构与活性关系,以α-亚甲基-β-羟甲基-γ-丁内酯为起始原料,经过与不同取代的羧酸缩合,合成了19个新的(4-亚甲基-5-羰基-3-四氢呋喃基)-苯甲酸甲酯衍生物。杀菌活性测定结果表明,该类衍生物具有广谱的杀菌活性,尤其对水稻纹枯病菌Rhizoctonia solani和辣椒疫霉Phytophthora capsici显示出很强的杀菌活性,其中化合物2e(R=2,4-2Cl)对这2种病菌的EC50值约为1.6 mg/L。