昆虫信息素结构鉴定和合成的研究 ⅩⅥ.午毒蛾光学活性性信息素及其三个光学异构体的合成

本文报道的一条合成路线是以(+)-甘油醛缩丙酮(2)为原料,各经过9～10步反应可分别合成午毒蛾光学活性性信息素1a及其三个光学异构体1b～d,总得率达20～30％。     

光学活性昆虫性信息素类似物的新合成路线

本文首次报道用丙二酸二乙酯的相转移催化烃化产物经拆分并分别还原,氧化制得的光活性2-甲-戊烯-4-醛与一系列季鏻盐的Wittig反应。通过此反应共合成新的带有两个双键的光活性昆虫性信息素类似物20个,相应的外消旋物10个。该反应原料易得,反应条件温和,产率高,可作为这类化合物的通用方法。     

昆虫信息素结构鉴定与合成 XXI, 淡色库蚊产卵引诱信息素四个光学异构体的立体选择性合成

应用Sharless不对称环氧化反应,合成淡色库蚊产卵引诱信息素的所有四个光学异构体1a～1d, e.e.96～97%. 从炔醇2出发到1a～1d的总得率为15～20%.     

昆虫信息素结构鉴定与合成 ⅩⅩⅠ.淡色库蚊产卵引诱信息素四个光学异构体的立体选择性合成

应用Sharpless不对称环氧化反应,合成淡色库蚊产卵引诱信息索的所有四个光学异构体1a～1d,e.e.96～97％.从炔醇2出发到1a～1d的总得率为15～20％.     

蜂王信息素合成新方法

蜂王信息素;贝克酵母;羟基-(E)-癸烯酸;羰基-(E)-癸烯酸     

小菜蛾性信息素的合成

以十一碳烯醇和碘戊烷为原料,经过苯甲酰基保护、9-硼双环[3.3.1]-壬烷(9-BBN)硼氢化后氧化、氯铬酸吡啶盐(PCC)氧化、Wittig反应、脱苯甲酰基五步反应得到顺-11-十六碳烯-1-醇(Z11-16:OH),五步反应总收率53％.顺-11-十六碳烯-1-醇经PCC氧化或Ac2O乙酰化分别得到顺-11-十六碳烯-1-醛(Z11-16:Ald)、顺-11-十六碳烯-1-醇乙酸酯(Z11-16:Ac),目标化合物及主要中间体结构经NMR,IR和MS确证.合成方法路线短,操作简便,收率较文献中的方法有较大提高.     

蜂王信息素的改进合成

早在50年代,Butler等^[1]发现蜂王的上颚腺能分泌一种影响工蜂活动的物质,并提出了蜂群是靠蜂王分泌的该种化学物质传递各种个体间的信息的论断,Barbier等^[2]测定其结构为9-氧代-2E-癸烯酸1(蜂王物质),并首次进行了人工合成.     

昆虫性信息素的合成

鳞翅目昆虫占农业害虫的一大部分,它们的信息素一般是直链脂肪族单烯醇或多烯醇及其乙酸酯或醛。其合成方法主要有 Wittig 反应,炔化物路线,有机铜锂试剂等。而关键步骤是控制顺反异构比例。曾企图用 Wittig反应高选择性地合成顺式结构的昆虫信息素组分,再经异构化得到反式信息素组分,但收率     

棉红铃虫性信息素的合成

自从1973年Hummel等鉴定了红铃虫性信息素为(Z、Z)及(Z、E)-7,11-十六碳二烯-1-醇醋酸酯(1和2)的两种异构体(1:1)的混合物以来,许多化学工作者相继合成了该性信息素。迄今报道的合成方法已有七种之多,其中Mori的以Grignard偶合反应为关键性一步的合成方法,各步得率均佳,且原料易得。我们为了适应综合防治棉红铃虫的需要,选择了Mori的方法进行合成,并对某些反应在反应条件上作了一定的改进,获得了较好的结果。我们在2-庚炔1-溴(6)和溴丙炔(3)生成1,5-癸二炔(7)及反-2-庚烯-1-溴(11)和溴丙炔(3)生成反-5-烯-1-癸炔(12)的Grignard反应中,先以无水乙醚为溶剂制备丙炔镁     

Studies on the identification and synthesis of insect pheromone: XVI. Synthesis of the optically active sex pheromone of gypsy moth and its three other optical isomers

The sex pheromone of gypsy moth (+)-(7R, 8S)-7,8-epoxy-2-methyl-octadecane (la) and its three other optical isomers lb—d were synthesized stereoselectively from (+)-(R)-glyceraldehyde acetonide (2), obtained from (+)-mannitol, in 9—10 steps in an overall yield of 20—30%.     

Studies on the identification and syntheses of insect pheromones XXI stereoselective synthesis of all the possible optical isomers of the mosquito oviposition attractant pheromone

All the four optical isomers of the oviposition attractant pheromone of the mosquito $\text{Gulex pipiens fatigans}$ were synthesized via Sharpless asymmetric epoxidation.     

Synthesis of syn-4,6-dimethyldodecanal, the male sex pheromone and trail-following pheromone of two species of the termite Zootermopsis

Recently, we reported that syn-4,6-dimethyldodecanal is the male sex pheromone and the trail-following pheromone of the Termopsidae Zootermopsis nevadensis and Zootermopsis angusticollis. In this article, we describe the syntheses of the mixture of the four stereoisomers of 4,6-dimethyldodecanal using a synthetic pathway where the key step is a Wittig reaction between methyl 4-methyl-5-oxo-pentanoate and 1-methylheptyl-triphenylphosphonium iodide, and of (±)-syn-4,6-dimethyldodecanal starting from 3,5-dimethyl-2-cyclohexen-1-one. Direct GC-MS comparison of these synthetic samples with the natural pheromone allowed its unambiguous identification.     

A study of the sex pheromone ofTortrix viridana

cis-Tetradec-ll-en-l-ol acetate has been isolated from an extract of the sex pheromone of the green oak tortrixTortrix viridana L., and has proved to be attractive under sexual conditions for the males of this species.     

Stereoselective synthesis of the Paulownia bagworm sex pheromone

According to our retrosynthesis, the main chain of the target molecule could be constructed using a C5 + C7 + C5 strategy. The key induction reaction afforded chiral methyl group moieties using different Evans templates with different configurations. Li_2 Cu Cl_4was effectively employed in the Csp~3 Csp~3 coupling protocol. The target molecular was obtained in a 12.6% overall yield with nine steps in the longest linear route.     

Mass-spectrometric study of the pheromone of the cotton bollworm and its precursors

The structures of the products of intermediate stages of the synthesis of the sex pheromone hexadec-11Z-enal that are labile to electron impact have been studied with the aid of low-resolution mass spectrometry and metastable ions.V. I. Lenin Tashkent State University. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 255–260, March–April, 1990.     

Trail pheromone of Kalotermes flavicollis

The trail pheromone of the termiteKalotermes flavicollis Fabr. has been isolated with the aid of column, liquid, and gas chromatography. Four of its components have been identified by PMR and chromato-mass spectrometry: nonan-l-ol, decan-l-ol, undecan-l-ol, and dodecan-l-ol, which are present in the natural trail pheromone in a ratio of 1:2:4:4. This has been confirmed by comparison with standard substances by means of gas chromatography and biotesting.Institute of the Physiology of Active Substances, Academy of Sciences of the USSR, Chernogolovka. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 129–132, January–February, 1989.     

On-site airborne pheromone sensing

Pheromones and other semiochemicals play an important role in the natural world by influencing the behavior of plants, mammals, and insects. In the latter case, species-dependent pheromone communication has numerous applications, including the detection, trapping, monitoring and guiding of insects, as well as pest management in agriculture. On-site sensors are desirable when volatile organic compounds (VOCs) are used as semiochemicals. Insects have evolved highly selective sensors for such compounds, so biosensors comprising complete insects, isolated organs or individual proteins can be highly effective. However, isolated insect organs have a limited lifetime as biosensor, so biomimetic approaches are needed for prolonged monitoring, novel applications, or measurements in challenging environments. We discuss the development of on-site biosensors and biomimetic approaches for airborne-pheromone sensing, together with biomimetic VOC sensor systems. Furthermore, the infochemical effect describing the anthropogenic contamination of the ecosystem through semiochemicals, will be considered in the context of novel on-site pheromone sensing-systems.     

Identification of the sex pheromone of the tortricid mothCacocimorpha pronubana

Four components have been isolated from an extract of the sex pheromone ofC. pronubana by gas-liquid chromatography, electroantennography, and chromato-mass spectrometry: cis-tetradec-11-en-1-ol and its acetate and the acetates of transtetradec-11-en-l-ol and of cis-tetradec-9-en-l-ol.All-Union Scientific-Research Institute of Biological Methods of Plant Protection, Kishinev. State Nikitskii Botanical Garden, Academy of Sciences of the USSR, Yalta. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 110–112, January–February, 1985.