有机硅试剂在昆虫性信息素合成中的应用: 桃小食心虫性息素-顺-7-二十烯酮-11和顺-7-十九烯酮-11的全合成

本文报导应用有机硅试剂合成顺式烯烃-桃小食心虫性信息素的结果, 这条合成路线原料易得, 产率高和具有较好的立体选择性。     

有机硅试剂在昆虫性信息素合成中的应用——桃小食心虫性信息素-顺-7-二十烯酮-11和顺-7-十九烯酮-11的全合成

桃小食心虫性信息素是由Tamaki等人分离并经鉴定为顺-7-二十烯酮-11(7a)和顺-7-十九烯酮-11(7b)比例为20:1的混合物。最近,陈德恒等人提出了一条利用有机硅试剂合成顺式烯烃的方法,其立体选择性在95％以上。本文报道应用该法合成桃小食心虫性信息素的结果(见图示1)。这条合成路线具有原料比较易得,产率高和具有较好的立体选择性的优点。首先,三甲基烯丙基硅烷(1)在Schlosser’s碱(n-BuLi/t-BoOK)作用下生成的负离子与溴代缩醛2发生具有立体专一性和区域选择性的烷基化反应,产生优势量的γ-烷基化产物3和少量的α-烷基化产物。因为α-产物能够在催化量的氢碘酸存在下很容易地脱去硅基,这样我们就能除去少量的α-产物而得到纯的γ-产物3。通过具有立体选择性的碘代反应可把3转化为碘代顺式烯烃4.4在Pd(PPh_3)_4催化下与有机锌试剂偶合得到的烯烃缩醛,再在酸性的硅胶柱上水解得到醛5.5     

桃小食心虫性信息素——顺-7-二十碳烯酮-11和顺-7-十九碳烯酮-11的合成

桃小食心虫(Carposina niponensis Walsingham)是远东地区重要蛀果害虫之一,在我国北方水果产区危害亦十分严重,有的果园虫果率高达50%。此虫危害苹果、梨、枣等。由于桃小食心虫发生规律不易掌握,用黑光灯及糖醋水诱捕均无效。目前用查幼虫、查果实上虫卵的测报方法,既费工费时、又不太准确。因此,迫切需要建立一种简便有效的测报方法,应用昆虫性信息素进行测报,方法简单、也便于推广使用。1977年日本Tamaki等人从桃小食心虫雌蛾中分离并鉴定其性信息素的化学结构为顺-7-二十碳烯酮-11和顺-7-十九碳烯酮-11。本间健平等在田间试验中发现,当这两种成分以20:1混和使用时,诱蛾活性为最高。     

红铃虫性信息素 顺、顺-及顺、反-7、11-十六碳双烯-1-醇乙酸酯的合成

红铃虫[Pectinophora gossypiella(Saund.)]^**是世界上许多地区棉花的主要害虫。在我国南方产棉区棉花因受红铃虫的危害,产量和质量每年损失较大。由于害虫对一般化学农药产生抗药性,以及农药在杀灭害虫的同时又伤害了天敌和其它益虫,对环境造成严重污染,因此人们正在寻找防治害虫的新方法。应用昆虫性信息素防治害虫即是其中的一个方法^[1,2]。我们开展了红铃虫性信息素合成的研究。     

棉铃虫性信息素顺-11-十六碳烯-1-醛及其反式几何异构体的合成

顺-11-十六碳烯-1醛(1)是世界上许多地区棉花害虫——棉铃虫(Heliothis armigera)——的性信息素。也是某些其它害虫如二化螟(chilo suppresslis)等的性信息素或其组份。棉铃虫在我国北方棉区危害颇为严重,为了棉铃虫的测报和防治试验需要,我们合成了化合物(1)及其反式几何异构体(8)。关于化合物(1)的合成,Nesbittt和Sekul等虽曾简单地叙述过相同的示意合成路线,但未见具     

昆虫性信息素的研究 Ⅱ.顺-11-十六碳烯醛的合成

顺-11-十六碳烯醛(10)是鳞翅目昆虫信息素的主要组份之一,它的合成在文献上已有一些报道。本文则报道从顺-5-癸烯醇-1(3)     

顺,顺,顺-3,6,9-二十碳三烯及顺,顺,顺-3,6-9-二十一碳三烯的合成

由于昆虫信息素研究的需要,我们曾于1979年合成了顺、顺、顺-3,6,9-二十碳三烯(1)和顺、顺、顺-3,6,9-二十一碳三烯(2),最近Conner等报道,1和2为鳞翅目昆虫信息素组分,并发表了以亚麻油酸及亚麻油醇为原料的合成路线。本文报道我们的合成路线,以丙炔醇为原料,经2-戊炔醇-[1](3),1-溴-2-戊炔     

昆虫性信息素的研究 II:顺-11-十六碳烯醛的合成

顺-11-十六碳烯醛是鳞翅目昆虫信息素的主要组份, 本文研究了它的合成从顺-5-癸烯醇-1得相应的对甲苯磺酸酯, 再与格氏试剂反应在Li2CuCl4催化下进行偶联反应得到关键中间体2-(Z-11-十六碳烯氧基)四氢呋喃.     

(+)-菊花烯酮的Baeyer-Villiger反应

Baeyer-Villiger反应是酮在过氧酸氧化下形成酯的反应,是有机反应中合成酯的主要方法,这一反应可应用在环酮扩环形成含氧杂环内酯的反应上．由于反应是立体控制的,已广泛应用于天然产物,例如：抗生素、类固醇和信息素中间体的合成,某些用其它方法难以合成的羟基酸可由内酯水解得到。     

2-烷基环戊-2-烯酮的简便合成新方法

2-位取代的环戊-2-烯酮是一类重要的有机合成中间体,它们的合成方法虽然已有不少文献报道,但大都路线较长,原料难得,条件苛刻且收率较低.本文报道一个以环戊二烯为原料,仅两步反应合成2-烷基环戊-2-烯酮的简便新方法. 以聚乙二醇(PEG)作为相转移催化剂,环戊二烯在氢氧化钾作用下与卤代烷在固-液相条件下反应,可方便地得到相应的烷基取代环戊二烯,主要为1-位和2-位烷基取代异构体的混合物.通过该方法制备烷基环戊二烯较之采用钠氨于液氨中反应的通常制备方法更可取.烷基环戊二烯进一步于甲醇中经溴代及酸性水解后,即可得到2-烷基环     

New synthesis of (Z)-5- and (Z)-7-monoene components of insect sex pheromones of the Lepidoptera order

A new procedure was developed for the synthesis of (Z)-5- and (Z)-7-monoene components of sex pheromones of Lepidoptera insects based on cometathesis of readily accessible cycloocta-1,5-diene and ethylene. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1304–1307, July, 2000.     

(Z,Z)-6,9-nonadecadien-3-one and (Z,Z,Z)-3,6,9-nonadecatriene: identification and synthesis of sex pheromone components of peribatodes rhomboidaria.

(Z,Z)-6,9-Nonadecadien-3-one and (Z,Z,Z)-3,6,9-nonadecatriene were identified by GC-EAD and GC-MS in ovipositor extracts of $\text{P}$. $\text{rhomboidaria}$; the synthetic mixture is attractive to males of the species in the field.     

Synthesis of aliphatic insect pheromones from alicyclic starting materials: (Z)-6-heneicosen-11-one and (z)-8-dodecenyl acetate

Both (Z)-6-heneicosen-11-one, the pheromone of Douglas fir tussock moth, and (Z)-8-dodecenyl acetate, the pheromone of oriental fruit moth, have been synthesized from cyclohexane-1,3-dione.     

A stereocontrolled synthesis of (R,Z)- and (R,E)-14-methyl-8-hexadecenals (trogodermal), the sex pheromones of trogoderma species

A stereocontrolled synthesis of (R,Z)- and (R,E)-14-methyl-8-hexadecenals with high stereochemical purity in both absolute and geometrical configurations was achieved by the use of the S_N2 type ring-opening reaction of (S)-β-methyl-β-propiolactone for the construction of the (R)-configurations, adn the cis-addition of diorganocuprate to acetylene adn the S_N2′ type ring-opening reaction of δ-vinyl-δ-valerolactone for the introduction of (Z)- and (E)-double bonds, respectively.     

Dienic sex pheromones : Stereoselective syntheses of (7E,9Z)-7,9-dodecadien-1-yl acetate, (E)-9,11-dodecadien-1-yl acetate,and of (9Z), 11E)-9,11- tetradecadien-1-yl acetate by palladium-catalyzed reactions

Pure (7E,9Z-7, 9-dodecadien-1-yl acetate (1), the sex pheromone of Lobesiabotrana, has been prepared in 21.6% overall yield by a reaction scheme involving; (i) the cross-coupling of (E) - 8 - (2 - tetrahydropyranyloxy) -1 - octenyldisiamylborane with 1 - bromo - 1 - butyne, in the presence of a Pd (O) catalyst and base; (ii) the acetylation of the crude product of this reaction; (iii) the (Z)-stereoselective reduction of the obtained conjugated (E)-enyn-1-yl acetate. (E)-9,11-Dodecadien-1-yl acetate (2), a sex pheromone component of Diparopsiscastanea, has been analogously obtained (in 54.3% overall yield) by cross-coupling of (E) - 10 - (2 - tetrahydropyranyloxy) - 1 - decenyl borane with vinyl bromide, in the presence of a Pd (O) catalyst and base, followed by acetylation of the crude product. Compound 2, which was 87.7% chemically pure, was purified by column chromatography over SiO₂-AgNO₃. Chemically pure (9Z, 11E) - 9,11 - tetradecadien - 1 - yl acetate (3), a sex pheromone component of Spodopteralittoralis, has been prepared (in 30.2% overall yield) by reaction of 10 - (2 - tetrahydropyranyloxy) - 1 - decynylamagnesium bromide with (E)-1-iodo-1-butene, in the presence of a Pd (O) catalyst, followed by acetylation of the crude product and by (Z)-stereoselective reduction of the obtained (E)-enyn-1-yl acetate.The stereoisomeric purity of 1, 2 and 3 has been evaluated by glc analysis on glass capillary columns or by reverse phase hplc analysis.     

Synthetic investigations in the field of attractive substances (sex attractants) of insects XI. Convenient synthesis of nonadec-cis-7-en-11-one and eicos-cis-7-en-11-one — Components of the sex pheromone of Carposina niponensis

A simple synthesis of the nonadec-cis-7-en-11-one and eicos-cis-7-en-11-one, components of the sex pheromone of the peach moth, has been performed from homopropargyl alcohols.All-Union Scientific-Research Institute of Biological Methods of Plant Protection, Kishinev. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 123–126, January–February, 1988.     

Synthesis of (7Z,9Z)-dodecadienyi acetate,a component of sex pheromones of the leafrollersEpinotia andEucosma,using conjugated diynols

Two analogous routes to the title pheromones were elaborated based on organocuprate cross-coupling ofZ,Z-dienic electrophiles, (2Z,4Z)-1-acetoxy-2,4-heptadiene (6) and (3Z,5Z)-1-bromoctadiene (8), with -tert-butoxy-1-chloropentane and -butane, respectively. Optimal conditions for the reduction of 2,4-heptadiyn-1-ol and 3,5-octadiyn-1-ol to the respectiveZ,Z-alkadienols as precursors for the electrophiles were found. Treatment of diynols with activated zinc in aqueous alcohol provided high geometrical purity of the product (94 %). In both cases, copper-catalyzed cross-coupling afforded 1-tert-butoxy-7,9-dodecadiene (four stereoisomers), acetolysis of which gave the target pheromone contaminated by stereoisomers. In the case of allylic electrophile6, the reaction occurred with the loss of the initial configurational purity, whereas the use of homoallylic bromide8 ensured almost complete retention of the configuration of the double bonds and obtaining the target pheromone of 87 % configurational purity.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1656–1660, September, 1993.     

Syntheses of (4E,6E, 11Z)-4,6,11-hexadecatrienyl acetate and (4E, 6E, 11Z)-4,6,11-hexadecatrienal, female sex pheromones of eri-silkworm, Samia cynthia ricini (Lepidoptera: Saturniidae)

Syntheses of (4E,6E,11Z)-4,6,11-hexadecatrienyl acetate (1) and (4E,6E, 11Z)-4, 6,11-hexadecatrienal (2), female sex pheromones of eri-silkworm,Samia cynthia ricini have been achieved through Claisen ortho ester rearrangement of (6).