日本拟除虫菊酯研究开发一百年

近年来拟除虫菊酯的研究取得了重大进展,人工合成的拟除虫菊酯已代替天然除虫菊,其应用范围也很快从室内扩大到室外:从防治家庭卫生害虫发展到农、林、牧和建筑物及飞机方面。拟除虫菊酯杀虫剂发展到今天决非一日之功,它是许多先驱者对天然除虫菊的化学组成和性质进行努力研究的结果,在此领域日本研究者的卓越贡献已为世所公认。本文简要综述自除虫菊传入日本一百年来在日本研究拟除虫菊酯的发展史。     

新型拟除虫菊酯Vaporthrin的开发和应用

天然除虫菊素Ⅰ、Ⅱ是除虫菊花萃取物的有效成分,是一种由碳、氢、氧组成的酯类化合物,与其他天然物质相比其化学结构并不太复杂。天然除虫菊素杀虫作用快、对哺乳动物和鸟类毒性低,因此吸引许多人进行化学合成的研究。这里介绍住友公司关于新型拟除虫菊酯Vaporthrin(通用名:empenthrin)的研究和开发工作。     

合成拟除虫菊酯的国内外研究概况

一、天然及合成除虫菊酯的一般介绍拟除虫菊酯(Pyrethroids)是一类在天然除虫菊酯化学结构研究的基础上发展起来的仿生药物。天然除虫菊的特点是击倒力强、杀虫作用快、广谱性、易解降、对高等动物及鸟类毒性低、使用安全、不污染环境。除虫菊的产量有限,有效成份含量低,不耐光和热,残效期极短,长期以来仅用作家庭卫生(蚊香)杀虫剂,而不适用于农业生产。 M.S.Schechter,N.Green等在前人研究     

除虫菊酯类化学的发展与未来

除虫菊酯化学的研究始于1910年,其研究历史大致可分为两个大致相等的阶段。第一阶段致力于对天然除虫菊酯化学结构的探明,它包括一个酸组份和一个由酯链连接的醇组份,并发现了六种活性成份:除虫菊素Ⅰ和Ⅱ、瓜叶菊素Ⅰ和Ⅱ、茉酮菊素Ⅰ和Ⅱ。至1958年,测出了它们醇部分的构型,由此得知了天然除虫菊酯的整个结构。第二个阶段则在上一阶段的基础     

拟除虫菊酯在害虫防治上的前途(上)

一、引言本文的主题是综述一些较稳定的合成拟除虫菊酯,这些化合物是在天然除虫菊素和早期的合成拟除虫菊酯的基础上发展起来的,由于它们在性质和活性上与后者有显著的差别,因而形成了一类新的杀虫剂。 1935年用天然除虫菊素的重石蜡油溶液有效地防治了仓库害虫,从而第一次表明了接触杀虫剂的残留膜在害虫防治上的使用价值;但由于配方中的活性成分——天然除虫菊素     

国内资料文摘(77070～77086)

本文介绍了天然除虫菊素和拟除虫菊素。重点叙述了拟除虫菊素的化学合成及结构变化。以及拟除虫菊素的杀虫机理及其在生物体内的代谢和拟除虫菊素的发展。     

拟除虫菊酯与立体化学

拟除虫菊酯是一类与天然除虫菊素结构类似的化合物,具有立体结构,不同立体结构的生物活性差异很大,如何得到生物活性高的单一异构体,是拟除虫菊酯的研究方向。本文介绍了几种获得单一异构体的方法,并对各种方法进行了评述。     

我国菊酯类杀虫剂的研究与开发——从天然除虫菊到拟除虫菊酯

长期以来,天然除虫菊防治家庭、畜舍、仓贮等害虫,是一种理想的杀虫剂。天然除虫菊素是除虫菊花中的有效成分,除虫菊花的生产受到土地、气候、农田栽培条件和劳力的限制,生产量有限,四十年代后期第一个人工合成的拟除虫菊酯问世,为拟除虫菊酯杀虫剂的     

光学活性拟除虫菊酯的合成

<正> 天然除虫菊素的主要成分之一菊酸,是右旋反式(1R:3R)的立体构型。人工合成的除虫菊酸,若采用重氮乙酸乙酯对烯烃的加成环化反应,则产物是顺反异构体和外消旋体的四个异构体的混合物。用合成的方法获得与天然除虫菊素具有相同构型的菊酸,乃是近年来合成除虫菊研究的一个重要方向。马特塞(Ma-     

杀灭菊酯在不同表面防治抗性德国小蠊的效果

合成拟除虫菊酯的出现和发展为虫害防治提供了新型化学杀虫剂,特别是对光稳定性不同于天然除虫菊素,有人提议它可适用于建筑结构害虫和住房害虫的防治。本文拟先对天然和合成拟除虫菊酯的一些最新研究成果作一简介。     

Biobased plastics with insect‐repellent functionality

Natural insecticides/repellents, such as pyrethrum (derived from chrysanthemum plants), and insect repellent N,N‐Diethyl‐meta‐toluamide (DEET) were added to poly(lactic acid) (PLA) fibers through extrusion and spray coating on the PLA fabrics. Contact irritancy assay (CIA) showed that DEET‐treated PLA fabrics caused the lowest relative escape response of mosquitoes with an escape frequency of 33.3% ± 3.3%, indicating that DEET was less effect compared with natural insecticides/repellents. This was followed by the extruded natural pyrethrum‐treated PLA fabric with an escape frequency of 80% ± 6.3%. Finally, the PLA fabrics spray‐coated with natural pyrethrum caused the highest escape frequency of 98.3% ± 1.7%. Thus, it was found that pyrethrum/PLA fabrics functioned as a mosquito repellent better than DEET/PLA fabrics. In addition, TGA and tensile testing results demonstrated that pyrethrum was sufficiently thermally stable to be extrusion compounded with PLA. GPC results showed that DEET promoted de‐polymerization of PLA when co‐extruded. The results demonstrated that pyrethrum can be a viable additive for PLA to produce fibers that function as mosquito repellent to produce temporary garments that are compostable. The potential use of the developed biobased fibers with natural insect repellents is for single use of personal protection equipment (PPE) garments. POLYM. ENG. SCI., 59:E460–E467, 2019. © 2019 Society of Plastics Engineers     

偏氯菊酸对甲氧基苄酯的合成研究

报道了一种新的拟除虫菊酯——偏氯菊酯的合成方法.以贲亭酸甲酯为原料,氯化亚铁作为引发剂在密闭体系中与氯仿加成后得到3,3-二甲基-4,6,6-三氯己酸甲酯,再成环、脱卤化氢,水解酸化后得到2,2-二甲基-3-(乙氯乙烯基)-环丙烷羧酸(偏氯菊酸),偏氯菊酸钠与季铵盐回流得到标题化合物.在合成中得到了3种未见文献报道的新...     

Pyrethrins Protect Pyrethrum Leaves Against Attack by Western Flower Thrips, <Emphasis Type="Italic">Frankliniella occidentalis</Emphasis>

Pyrethrins are active ingredients extracted from pyrethrum flowers (Tanacetum cinerariifolium), and are the most widely used botanical insecticide. However, several thrips species are commonly found on pyrethrum flowers in the field, and are the dominant insects found inside the flowers. Up to 80 % of western flower thrips (WFT, Frankliniella occidentalis) adults died within 3 days of initiating feeding on leaves of pyrethrum, leading us to evaluate the role of pyrethrins in the defense of pyrethrum leaves against WFT. The effects of pyrethrins on WFT survival, feeding behavior, and reproduction were measured both in vitro and in planta (infiltrated leaves). The lethal concentration value (LC50) for pyrethrins against WFT adults was 12.9 mg/ml, and pyrethrins at 0.1 % (w/v) and 1 % (w/v) had significantly negative effects on feeding, embryo development, and oviposition. About 20-70 % of WFT were killed within 2 days when they were fed chrysanthemum leaves containing 0.01-1 % pyrethrins. Chrysanthemum leaves containing 0.1 % or 1 % pyrethrins were significantly deterrent to WFT. In a no-choice assay, the reproduction of WFT was reduced significantly when the insects were fed leaves containing 0.1 % pyrethrins, and no eggs were found in leaves containing 1 % pyrethrins. Our results suggest that the natural concentrations of pyrethrins in the leaves may be responsible for the observed high mortality of WFT on pyrethrum.     

萃取天然除虫菊 化学成分的GC-MS分析

采用GC-MS法对超临界CO₂萃取天然除虫菊的化学成分进行了分析,用归一化法测定了各组分的相对百分含量。结果共分离出53个组分,鉴定了31个成分,已鉴定的化合物组分占总馏出组分的58.5%。结果表明超临界CO₂萃取的天然除虫菊的主要成分为除虫菊酯类以及烷烃类、烯醇、烯酸、甾醇、脂肪酸,其中除虫菊酯的相对含量为50.70%。     

Effect of nitrification inhibitors on herb and essential oil yield of Japanese mint on sandy soil

Pyrethrum (Chrysanthemum cinerariefolium) flowers have been observed to have insecticidal properties and could be used as an indigenous nitrification inhibitor for increasing N-use efficiency. A field experiment was conducted at the Central Institute of Medicinal and Aromatic Plants, Lucknow, India during 1988 and 1989 to evaluate the relative performance of pyrethrum flower waste and Dicyandiamide (DCD) as nitrification inhibitors applied with prilled urea (PU) to Japanese mint (Mentha arvensis L.). The results revealed that application of the nitrification inhibitors with prilled urea significantly increased the herb and essential oil yield of the crop compared to that of prilled urea alone. Addition of Dicyandiamide and pyrethrum flower waste gave 30 and 23% more herb yield than prilled urea alone, the corresponding increase in oil yield being 27 and 22%, respectively. Application of nitrogen at 200 kg ha^–1 in dicayndiamide or pyrethrum flower waste treated soil significantly enhanced the herb and essential oil yields and N-uptake by the crop to more than that for 300 kg N ha^–1 with prilled urea. Both the materials improved the N use efficiency by one and half time as compared to that with PU at 100 kg N ha^–1. The results indicate pyrethrum flower dust can be effectively used as a potential nitrification inhibitor.     

Recent research on sesamin,sesamolin, and related compounds

This review covers the literature on sesamin, sesamolin and related compounds published since 1951. The topics reviewed include structural con-siderations, natural occurrence, influence of oil processing, analytical methods, isolation proce-dures and commercial preparations, various bio-logical effects and stability questions. Recent developments in pyrethrum synergists are discussed at length, since they owe so much to the discovery of the synergistic activities of sesamin and sesamolin. Contribution from the National and University Institute of Agricul-ture, Rehovot, 1963, Series No. 566-E.     

7''''-O-菊酰基井冈羟胺A的合成

将拟除虫菊酸酰化后,与井冈霉素A的水解产物井冈羟胺A反应,合成了3个未见报道的7'-O-菊酰基井冈羟胺A(4a￣4c),其结构经1HNMR、IR和MS确认。初步的生物活性测试显示,其中4a和4b均表现出一定的杀蚜虫活性,4b对纹枯病菌也表现出一定的抑制作用。     

毛细管气相色谱法测定天然除虫菊酯

研究了毛细管气相色谱法定量分析天然除虫菊提取液中6种酯的方法,FID检测,邻苯二甲酸二丁酯作为内标物。方法的线性范围为:0.1～1.0g/L:线性相关系数为0.9958～0.9964,平均回收率为99.50%(RSD=1.10%,n=5)。     

Extraction of Organic Solutes from Vegetable Materials. Extraction of Pyrethrins from Chrysanthemum cinerariae folium

Abstract

In order to elucidate the extraction kinetics of valuable organic substances from dried vegetable materials, extraction of pyrethrins from ground pyrethrum blossoms was taken as an example and studied at various conditions. It was shown that the apparent diffusivity is a nonmonotonous function of the solute content in the solid phase. Due to the superposition of several phenomena, its value passes through a maximum and may change a hundred or even more times. Simple laboratory batch experiments and numerical solution of the appropriate extraction models are necessary prerequisites for successful design of large-scale extraction processes of vegetable raw materials.     

The insecticidal properties of some fatty acid derivatives

Summary The insecticidal properties of a number of fatty acid derivatives have been investigated, and it was found that certain primary and secondary amines were highly lethal to the common house fly, Musca domestica. Of the primary amines examined, octyl and decyl amine possessed the highest insecticidal activity; however, they were considered to be somewhat irritating for general use. Dioctyl amine was found to be the most active of the secondary amines examined. In view of its exceptionally high paralyzing and killing power for insects and its comparatively non-irritating properties to humans, together with its absence of toxicity to domestic animals, it can be considered as a possible substitute for pyrethrum.