新型银锭夜蛾性信息素类似物的合成及初步活性

昆虫性信息素具有微量、高效、绿色等优点，利用性信息素防治害虫具有良好的应用前景。但随着对性信息素的研究不断深入，性信息素田间释放速率较快、易分解等问题日益凸显。为提高性信息素对银锭夜蛾的防治效果，以银锭夜蛾性信息素主要成分顺-7-十二碳烯乙酸酯（Z7-12:Ac）为母体结构，通过醇与酰氯或酸酐的反应，合成结构稳定且新颖的6种性信息素类似物，包括顺-7-十二碳烯-2,2-二氟代乙酸酯（Y₁），顺-7-十二碳烯-2,2,2-三氟乙酸酯（Y₂），顺-7-十二碳烯-2,2,3,3,3-五氟丙酸酯（Y₃），顺-7-十二碳烯-2,2,2-三氟甲磺酸酯（Y₄），顺-7-十二碳烯-2-溴丙酸酯（Y₅），顺-7-十二碳烯-3-甲硫基丙酸酯（Y₆），其结构经核磁共振（NMR）和高分辨质谱（HR-MS）表征。室内生物活性研究表明：所有的性信息素类似物在触角电生理试验（EAG）中均表现出一定的生物活性，其中Y₁具有较好的剂量-效应关系，在浓度10 μg时EAG直接刺激响应值为2.07 mV。     

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.     

马尾松毛虫性信息素的立体选择性合成新法

马尾松毛虫(Dendrolimus punctatus Walker)是一种毁灭性的森林害虫,在我国分布较广[1].利用昆虫信息素进行农林病虫害防治在保护环境和生态平衡等方面有突出的优点.马尾松毛虫性信息素的主要成份是(5Z,7E)-5,7-十二碳二烯-1-醇(Ⅲ)及其乙酸酯、丙酸酯[2,3].     

昆虫信息素结构和合成的研究——ⅩⅦ.桑毛虫性信息素的结构鉴定

我们采用昆虫性信息素腺体漂洗结合色-质谱分析方法,从桑毛虫性信息素腺体中鉴定出四个戊酸十八碳烯酯.它们是异戊酸顺-7-十八碳烯酯(1a)(92％),异戊酸6-十八碳烯酯(1.4％),异戊酸9-十八碳烯酯(5％)和正戊酸6-十八碳烯酯(16％).大田诱蛾生测和触角电位试验证明1a有很强的生理活性,可用于桑毛虫的测报和防治试验.1a是新的性信息素结构,在毒蛾科中性信息素是异戊酸酯尚属首次发现.     

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)     

昆虫信息素结构鉴定和合成的研究ⅩⅩⅤ.用三乙胺作烯铜锂试剂配位体合成棉铃虫和午毒蛾性信息素

烯铜锂试剂对合成含有顺式双键的昆虫信息素极为有效,可以缩短合成步骤,产率高,而且顺式产物纯度非常高。我们曾用这种试剂合成了棉铃虫性信息素,因为烯铜锂试剂配位体亚膦酸三乙酯的毒性较大,且气味难闻,操作不方便。本文报道以三乙胺代替亚膦酸三乙酯,合成了棉铃虫性信息素顺-7-十六碳烯醛(1)和顺-11-十六碳烯醛(2)以及消旋的午毒蛾性信息素顺-7,8-环氧-2-甲基十八烷(3)。     

立体定向合成粘虫性信息素

粘虫是一种多食性害虫,分布极广。它的危害对象包括麦类、水稻、玉米等十多种粮食和经济作物。1979年Takahashi等首先确定粘虫雄蛾(Mythimna Separata male)的性信息素,这是由8:1比例混合的(Z)-11-十六碳烯-1-醇乙酸酯3和(Z)-11-十六碳烯-1-醇4组     

从月桂烯合成梨圆蚧性信息素

梨圆蚧是对果林危害较大的害虫。该虫的性信息素包括三个组分:3-亚甲基-7-甲基-7-辛烯-1-醇丙酸酯(1)、(2Z)-3,7-二甲基-2,7-辛二烯-1-醇丙酸酯(2)和(2E)-3,7-二甲基-2,7-辛二烯-1-醇丙酸酯(3)。本文介绍了通过对月桂烯进行结构改造来合成梨圆蚧性信息素,从月桂烯到1,总产率为19%。工业上从月桂烯制龋萑花醇和香叶醇,再将橙花醇和香叶醇转变为相应的氯烯醇后再还原、丙酰化即得2和3,其总产率分别为30%和28%。(以橙花醇和香叶醇计)。月桂烯可从β-蒎烯裂解而得。我国有丰富的蒎烯资源,所以开辟从月桂烯合成梨圆蚧性信息素的新途径具有重要的意义。     

聚合物试剂的研究——Ⅱ.应用聚合物试剂合成桃柱螟性信息素——反-10-十六碳烯-1-醛

以二甲亚砜钠盐和四氢呋喃作为碱和溶剂,应用聚合物 Wittig 试剂合成顺-10-十六碳烯-1-醇5,产率31%,选择性可达90%。5经异构化得反式-10-十六碳烯-1-醇6,6的异构体比例达到生物活性要求。6氧化后得到桃柱螟性信息素——反-10-十六碳烯-1-醛7。产物结构均经 IR、NMR、MS 和元素分析等得到证实。     

高纯度的棉铃虫性信息素主要组份的合成

棉铃虫(Heliothis amigora)是世界性棉花害虫,在我国产棉区的危害也甚为严重.棉铃虫性信息素主要组份为顺-9-十六碳烯醛-1(1)和顺-11-十六碳烯醛-1(2)等烯醛类化合物.1和2的合成报道是以 Wittig 反应为主或炔锂和卤代烷缩合,这种合成路线所得的1和2.其顺式双键的纯度均仅95～98％,总产率约35％.因为昆虫对信息素的几何异构体组成非常敏感.所以几何异构体的纯度在合成昆虫信息素中特别重要.为此我们选择了用顺-二(烯基)铜锂的烷基化反应合成1和2(图式1A).得到了>99.5％顺式构型的产物.用此法不仅合成步骤短,而且总产率高达80％.此外用本法还可通过变换图式1中的 m 或 n 数得到一系列双键位置不同的长链脂肪醛、醇及其乙酸酯的昆虫性信息素化合物.溴化物3和锂反应生成的锂试剂与碘化亚铜,乙炔及碘代烷通过一步反应即生成顺式烯化合物4,产率90％.然后除去4的保护基团和再经 PCO 氧化,得1和2,总产率分别为79.5％     

Convenient syntheses of dibenzo[c,p]chrysene and its possible proximate and ultimate carcinogens: in vitro metabolism and DNA adduction studies

Dibenzo[c,p]chrysene (DB[c,p]C) is the only hexacyclic polycyclic aromatic hydrocarbon having two fjord regions, both in different chemical environments. Its environmental presence and relative tumorigenic potency are not known due to the lack of synthetic standards. We report here the synthesis of dibenzo[c,p]chrysene (1), its proximate carcinogens, i.e., trans-1,2-dihydroxy-1,2-dihydro-DB[c,p]C (2) and trans-11,12-dihydroxy-11,12-dihydro-DB[c,p]C (3), and possible ultimate carcinogens, i.e., anti-trans-1,2-dihydroxy-3,4-epoxy-1,2,3,4-tetrahydro-DB[c,p]C (4) and anti-trans-11,12-dihydroxy-13,14-epoxy-11,12,13,14-tetrahydro-DB[c,p]C (5). The syntheses of 1 and the appropriately methoxy-substituted DB[c,p]C (12 and 27), key intermediates for the synthesis of its proximate and ultimate metabolites, were tried first using a Suzuki cross-coupling reaction. However, the cyclization of olefins (10 and 11) gave poor yields of the desired products. An alternate method was thus developed employing a photochemical approach. The in vitro metabolism of DB[c,p]C was established with the S9 fraction of liver homogenate from phenobarbital/beta-naphthoflavone-induced Sprague-Dawley rats. The major dihydrodiol formed was identified as the fjord region 11,12-dihydroxy-11,12-dihydro-DB[c,p]C, while the major and minor phenols were identified as 11-hydroxy-DB[c,p]C and 12-hydroxy-DB[c,p]C, respectively. Further, the DNA adduction studies with the calf thymus DNA led to a mixture of dA and dG adducts for both fjord region diol epoxides (4 and 5). Interestingly, the dA to dG ratio for 1,2-dihydroxy-3,4-epoxide was much higher (3.2) compared to that of 11,12-dihydroxy-13,14-epoxide (0.5).     

Analysis of insect pheromones by quadrupole mass fragmentography and high-resolution gas chromatography.

A sensitive technique is described for the analysis of insect pheromones. Insect extracts are separated into fractions by column chromatography and are analyzed directly by quadrupole mass fragmentography on high-resolution glass capillary columns and by mass spectrometry. Applications are illustrated with two important pests. In the codling moth, trans-8, trans-10-dodecadien-1-ol was found to be present at a level of 3.5 ng per female, and in the European grapevine moth trans-7, cis-9-dodecadienyl acetate at a level of 1.6 ng. Both compounds appear to be present in high isomeric purity in the female insect and are absent in the corresponding males.     

A Highly Abbreviated Synthesis of Dibenzo[def,p]chrysene and Its 12-Methoxy Derivative, a Key Precursor for the Synthesis of the Proximate and Ultimate Carcinogens of Dibenzo[def,p]chrysene

Dibenzo[def,p]chrysene (DBC) (1), is by far the most mutagenic and toxic polycyclic aromatic hydrocarbon identified. Its metabolic activation leads to trans-11,12-dihydroxy-11,12-dihydro-DBC (2), which is further metabolized to the ultimate metabolite, anti-trans-11,12-dihydroxy-13,14-epoxy-11,12,13,14-tetrahydro-DBC (3), that binds to DNA causing mutations and ultimately tumor induction. We report a facile route for the syntheses of DBC (1) and its 12-methoxy derivative (12-methoxy-DBC) (13), a key intermediate for the synthesis of 2 and 3, using a Suzuki cross-coupling approach.     

由有机硼烷立体选择合成(Z)、(E)链烯-1-醇乙酸酯类昆虫性信息素

等摩尔的甲硼烷甲硫醚(H₃B·SMe₂)与四溴化碳在60℃下反应20h,定量得到一溴硼烷甲硫醚。从链端烯烃、一卤硼烷甲硫醚和2-[7-辛炔-1-氧基]四氢吡喃及其8-溴代衍生物出发,经硼氢化反应和Zweifel的顺-,反-烯烃合成法,立体选择地合成了鳞翅目昆虫性信息素:(Z)-7-十四烯-1-醇乙酸酯9a、(Z)-7-十六烯-1-醇乙酸酯9b、(E)-7-十四烯-1-醇乙酸酯12及其相应的醇13。产物经GC分析和MS、¹H及¹³C NMR数据证实了它们的纯度和几何构型。     

Resolution studies on two regioisomeric chiral stationary phases: effects from reversed orientation of an amide group

Two new polymeric chiral stationary phases, incorporating the selectors trans-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboxylic acid bis-allylamide, 1 (DEABA) and trans-11,12-diamino-9,10-dihydro-9,10-ethanoanthracene bis-butenoylamide, 2 (DDEBB), respectively, have been evaluated by chromatographic resolution of a series of structurally different racemates. For some groups of compounds, where large separation factors were obtained, more detailed studies were performed by the use of different retention modifiers. As an effect from the reversed orientation of the amide group in the two selectors, the enantiomers of the racemates investigated are separated in opposite order of elution on the two columns.     

Darstellung von (s) -2,5-dimethyl-2-isopropyl-2,3-dihydrofuran,einem der beiden enantiomeren des sexuallockstoffs des werftkäfers hylecoetus dermestoides L.

The optical pure title compound II is synthesized by conversion of the branched chain sugar methyl-2-C-acetyl-4,6-O-benzylidene-3-deoxy-α-d-ribo-hexopyranose (I) which is available from d-glucose. 2,5-Di-methyl-2-isopropyl-2,3-dihydrofuran is found for the first time as a natural product and represents a new type of insect pheromones.     

INCORPORATION OF 11,12-DIHYDRORETINAL INTO THE RETINAE OF VITAMIN A DEPRIVED RATS

Abstract— The incorporation of 11,12-[15–³H]-dihydroretinal, a retinal in which the crucial 11-ene is saturated, into the retinae of vitamin A deficient rats as a result of intraperitoneal injection of the corresponding alcohol was shown by the presence of the tritium label in the rod outer segments and by identification of the extracted retinals using high pressure liquid chromatography. The amplitude of the electroretinogram (ERG) b-wave, diminished as the result of vitamin A deprivation, was not affected by administration of the analogue, although similar treatment of deprived litter mates with trans retinal restored the ERG b-wave amplitude to a normal level.
The evidence that the analogue is bound to opsin forming 11,12-dihydrorhodopsin is as follows: (1) when incubated with 11- cis retinal, extracts from vitamin A deficient rats regenerate 1.4 nmol rhodopsin while extracts from rats deficient in vitamin A and supplemented with 11,12-dihydroretinal regenerate 0.6 nmol rhodopsin indicating binding of the dihydroretinal blocks rhodopsin regeneration. (2) 11,12-dihydroretinal is shown to remain unchanged in hexane-washed retinae after extraction with methylene chloride and (3) injection of retinal into animals previously injected with 11,12-dihydroretinal also fails to restore visual sensitivity as measured by the ERG b-wave. Our results indicate that the dihydro-chromophore occupies the same binding site as the natural 11- cis retinal and that occupation of the chromophore binding site of opsin is not sufficient to restore the visual sensitivity in a vitamin-A-deprived animal.     

昆虫信息素缓释技术的研究进展

昆虫信息素是一类由昆虫个体释放于体外来调节或诱发同种其它个体行为与反应的化学物质。 近年来,应用昆虫信息素防治虫害是当前有机农业绿色防控的新技术之一。 与传统农药防治虫害相比,信息素具有高效、无毒、不产生抗药性以及对天敌无害的特点。 此外,昆虫信息素通常易降解且挥发性高。 因此,基于信息素的缓释技术引起了科研工作者的广泛关注,是涵盖化学、材料与农业的新兴交叉学科。 通过某种特定的方法或技术使昆虫信息素缓慢控制释放,既能有效防治虫害,减少农药使用,提升环境生态水平,同时也能促进区域环境化学品总量与农业成本的降低。 本文详细综述了昆虫信息素缓释技术的最新研究进展并对发展前景进行了展望。     

Stereocontrolled synthesis of all of the possible stereoisomers of 3,11-dimethylnonacosan-2-one and 29-hydroxy-3,11-dimethylnonacosan-2-one : The female sex pheromone of the german cockroach

All of the possible stereoisomers of 3, 11 - dimethylnonacosan - 2 - one 1 and 29 - hydroxy - 3, 11 -dimethylnonacosan - 2 - one 2 were synthesized from (R)-(+)- citronellic acid as the chiral source. The natural pheromones were shown to be (3S,11S)-1 and (3S, 11S)-2 by direct comparisons.