Action of juvenoids on the metamorphosis of cyclorrhaphous Diptera

Administrations of high doses of juvenoids to the last instar larvae of cyclorrhaphous flies cause occasionally lethal defects in puparium formation but mostly affect only the pupal-adult transformation. In pupae, juvenoids impede proliferation and differentiation of the imaginal disks and of abdominal histoblasts: at low doses they cause incomplete rotation of male genitalia and deformations of the ovipositor, at higher doses their effects gradually spread from the tip of abdomen towards the middle of the body. The highest amounts influence the entire abdomen, size and pigmentation of the eyes, and development of hairs and sclerotization of the integument on the head and thorax. Various species slightly differ in the pattern of morphological effects produced, in the ability of affected insects to leave the puparium, and in the sensitivity to juvenoids of different types. A uniform scale for classification of morphological effects in the species examined is described in this paper. The most potent juvenoids are effective at doses around one nanogramme per specimen. Out of 29 selected compounds tested, isopropyl 11-methoxy-3,7,11-trimethyl-2,4-dodecadienoate is the most active juvenoid for Drosophila, Musca, and Sarcophaga; methyl 10,11-epoxy-3,7,11-trimethyl-2,6-tridecadienoate is the most active juvenoid for Ceratilis; and isopropyl 11-chloro-3,7,11-trimethyl-2-dodecenoate possesses the highest activity for Calliphora.     

Synthesis of the Thiirane Analogs of Juvenile Hormone III and Other Juvenile Hormone Mimics

Methyl (2E,6E)-10,11-epithio-3,7,11-trimethyl-2,6-dodecadienoate (the thiirane analog of JH III), 6,7-epithiogeranyl 4-methylphenyl ether and 6,7-epithiogeranyl 3,4-methylenedioxyphenyl ether were synthesized. An infrared absorption band at ~1090 cm^?1 was attributable to the thiirane group. The biological activity of these three sulfur-containing JH mimics was tested on Culex pipiens, Aedes aegypti and Spodoptera litura to reveal weak or no JH-like activity.     

Development of superfluous soldiers induced by juvenile hormone analogues in the termite,Reticulitermes lucifugus santonensis

Summary The synthetic juvenile hormone (JH): 17% alltrans+83%trans, trans, cis-methyl 10-epoxy-3,7,11-trimethyl-2,6 tridecadienoate and juvenile hormone analogues (JHA): methyl 10-chloro-3,7,11-trimethyl-2 dodecenoate and ethyl 10-epoxy-3,7,11-trimethyl-2,6-dodecadienoate administered on filter paper to small groups of the European subterranean termiteReticulitermes lucifugus santonensis Feyt. caused differentiation of larvae and pseudergates into pre-soldiers and/or pseudergate-soldier intercastes. In contrast to the proportion of one soldier to 100–300 other individuals in normal colonies, the effect of the compounds tested that showed JH activity was to induce the development of a large number of superfluous soldiers in quantities that even exceeded the number of other kinds of individuals. Such a disturbance in the caste ratio leads to increased mortality.

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Zusammenfassung Das synthetische Juvenilhormon (JH): 17% alltrans+83%trans, trans, cis-Methyl 10-epoxy-3,7,11-trimethyl-2,6 tridecadienoate und die Juvenilhormonanaloge (JHA): Methyl 10-chloro-3,7,11-trimethyl-2 dodecenoate und Ethyl 10-epoxy-3,7,11-trimethyl-2,6-dodecadienoate, die auf Filterpapier kleinen Termitengruppen der europäischen ErdtermitenartReticulitermes lucifugus santonensis Feyt. zugeführt wurden, verursachten eine Differenzierung von Larven und Pseudergaten in Vorsoldaten und/oder Interkasten Pseudergate-Soldat. Zum Unterschied vom Verhältnis ein Soldat zu 100 bis 300 anderen Individuen in normalen Kolonien erscheint unter der Einwirkung der getesteten juvenilhormonwirksamen Stoffe eine grosse Menge überzähliger Soldaten, deren Anzahl jene der übrigen Individuen sogar übersteigen kann. Die Gleichgewichtstörung zwischen den Kasten hat eine höhere Absterberate der Termiten zur Folge.

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Résumé L'hormone juvénile synthétique: 17% alltrans+83%trans, trans, cis-méthyle 10-epoxy-3,7,11-triméthyle-2,6 tridecadienoate et l'analogue de l'hormone juvénile: méthyle 10-chloro-3,7,11-triméthyle-2 dodecenoate et éthyle 10-epoxy-3,7,11-triméthyle-2,6-dodecadienoate, qui ont été administrés amenés sur papier filtre à de petits groupes de termitesReticulitermes lucifugus santonensis Feyt., ont causé une différenciation de larves et de pseudergates en présoldats et/ou intermédiaires pseudergate-soldat. A la différence du rapport de 1 soldat à 100–300 autres individus dans des colonies normales, on assiste sous l'effet de la substance testée avec effet d'hormone juvénile à l'apparition d'un grand nombre de soldats en surplus, dont le nombre peut même dépasser celui des autres individus. Le trouble de l'équilibre entre les castes conduit à un taux de mortalité supérieur des termites.

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Dedicated to Prof.K. Gösswald at the occasion of his 65th birthday.     

Effects of insect growth regulators on the tobacco cutworm, Spodoptera litura: Rectal prolapse

Prolapse of the rectum was observed when ZR-515 (isopropyl 11-methoxy-3,7,11-trimethyl-2,4-dodecadienoate) was applied to the 6th instar larva of the tobacco cutworm, Spodoptera litura. It was induced by an administration of ZR-515 in the middle of the 6th instar larval stage, and either by a dose higher than required for the induction of larval-pupal intermediates or by a dose lower than the dose that produces extra larvae. Larvae with a rectal prolapse appeared only on the 3rd day after treatment. These larvae did not survive for more than 1 to 2 days because the prolapsed rectum ruptured, leading to haemorrhage.Rectal prolapse was also induced by other two IGRs, ZR-512 (ethyl 3,7,11-trimethyl-2,4-dodecadienoate) and ZR-619 (ethyl 11-methoxy-3,7,11-trimethyl-2,4-dodecadienethiolate).     

The identification and biosynthesis of two juvenile hormones from the tobacco budworm moth (Heliothis virescens)

Brain-corpora cardiaca-corpora allata complexes from the tobacco budworm $\text{Heliothis virescens}$ produce both radiolabelled methyl (2E, 6E, 10Z)-10,11-epoxy-3, 11-dimethyl-7-ethyl-2, 6-tridecadienoate (JH I) and methyl (2E, 6E, 10Z)-10, 11-epoxy-3, 7, 11-trimethyl-2, 6-tridecadienoate (JH II) when cultured in medium containing L-[$\text{methyl}$−¹⁴C] methionine or sodium [1−¹⁴C] propionate. Degradative studies of the hormones derived from propionate show the specific incorporation of the latter into the homo-isoprenoid portions of these compounds.     

Isoprenoid enzyme systems of silkworm. II. Formation of the juvenile hormone skeletons by farnesyl pyrophosphate synthetase II

Comparative substrate specificities of farnesyl pyrophosphate synthetases I and II purified from larvae of silkworm, Bombyx mori, were studied by use of the possible biosynthetic intermediates of juvenile hormones in the insect. In the presence of Mn2+ ions farnesyl pyrophosphate synthetase II showed higher activity than synthetase I and the corresponding enzyme from pig liver with the following substrate homologues: (Z)-3-methyl-2-pentenyl-, 3-ethyl-3-butenyl-, (2E,6Z)-3,7-dimethyl-2,6-nonadienyl-, and (2E,6Z)-3-ethyl-7-methyl-2,6-nonadienyl pyrophosphate. When (Z)-3-methyl-2-pentenyl-, 3-ethyl-3-butenyl-, and isopentenyl pyrophosphate were mixed and incubated with farnesyl pyrophosphate synthetase II, (2E,6E,10Z)-3,11-dimethyl-7-ethyl-2,6,10-tridecatrienyl-, (2E,6E,10Z)-3,7,11-trimethyl-2,6,10-tridecatrienyl, and a trace amount of (2E,6E,10Z)-3,7-diethyl-11-methyl-2,6,10-tridecatrienyl pyrophosphate, whose carbon skeletons were the same as those of juvenile hormone I, II, and O, respectively, were formed. (Z)-3-Methyl-2-pentenyl pyrophosphate was produced from 3-ethyl-3-butenyl pyrophosphate as a single product by the action of silkworm isopentenyl pyrophosphate isomerase, though the enzyme activity was much lower with this substrate than with the usual substrate, isopentenyl pyrophosphate.     

Critical Sensitivity of the Ovary of <Emphasis Type="Italic">Aedes aegypti</Emphasis> Adults to Sterilization by Juvenile Hormone Mimics

STERILIZATION of adult insects with juvenile hormone mimics has been reported several times^1–5, but only once for adult mosquitoes and no details were given². I report here on the sterilizing effect of three juvenile hormone mimics on female Aedes aegypti. They were (i) mixed geometric isomers of methyl 10,11-epoxy-3,7,11-trimethyl-2,6-tridecadienoate (CJH2), one of two substances with high juvenile hormone activity isolated from Cecropia oil⁶; (ii) mixed geometric isomers of farnesyl methyl ether (FME) and (iii) 2 cis/trans, 6 trans farnesenic acid ethyl ester (FAE). All three compounds were first tested on fifth instar Rhodnius prolixus using Wiggles-worth's method⁷. The doses to give a score of ten were as follows: CJH2 1.3µg; FME 1.4 µg; FAE 31.7 µg.     

Juvenile hormone production by corpora allta of Tenebrio molitor in vitro

$\text{In vitro}$ organ cultures of corpora allata or corpora cardiaca-corpora allata complexes from $\text{Tenebrio molitor}$ were found to produce methyl-(2E, 6E)-(10R)-10, 11- epoxy-3, 7, 11 trimethyl-2, 6-dodecadienoate (JH III). No detectable JH I or II was produced. The hormone was identified by derivation, chromatography and mass spectral analysis. A ¹⁴C radiolabel was incorporated into the methyl carbon of the ester function from precursor L-[$\text{methyl}$-¹⁴C]-methionine added to the culture medium.     

Structure,haemolymph titre,and regulatory effects of juvenile homone during ovarian maturation in Leucophaea maderae

Juvenile hormone (JH) synthesized and secreted in vitro by the corpora allata of mated adult Leucophaea maderae females was determined to be JH III (methyl-10,11-epoxy-3,7,11-trimethyl-2,6-dodecadienoate).The haemolymph titre of JH was determined during maturation of the terminal oöcytes in the first reproductive cycle of L. maderae. In virgin females, JH is not detectable in the haemolymph during the first eight days following adult emergence; however, by 10 days after emergence, trace quantities of JH are apparent. Mating stimuli induce a dramatic increase in the concentration of haemolymph JH, with a peak occurring approximately 12 days after mating; thereafter, the JH concentration declines until it has reached an undetectable level 19 days after mating, at the time of chorion deposition.During ovarian maturation, changes in the rates of synthesis of vitellogenin by the fat body and DNA by the ovary correlate closely with the haemolymph titre of JH. However, no such correlation exists between the JH titre and the extensive ovarian protein synthesis that occurs in L. maderae coincident with chorion formation.The effects of JH I and JH III on both vitellogenin synthesis and ovarain DNA synthesis are statistically similar.     

Emergence ofKeiferia lycopersicella [Lepidoptera: Gelechiidae], andApanteles sp. [Hymenoptera: Braconidae] from pupae and soil treated with insect growth regulators

Two insect growth regulators (IGR's), ZR-619 (ethylin-methoxy-3,7,11-trimethyl-(2E, 4E)-2,4-dodecadienethiolate), and ZR-777 (Prop-2 ynyl 3,7,11-trimethyl-(2E, 4E)-dodecadienoate) were tested for potential use against the tomato pinworm,Keiferia lycopersicella (Walsh.) The IGR's were applied to cocoons and to soil where cocoons were formed. Both IGR's, alone and in combination, suppressed pinworn adult emergence from 23 to 7% when applied direct but were ineffective when applied to the soil. All treatments of IGR's in both methods of application reduced emergence of the parasitoApanteles sp. to 0% from levels as high as 61%. Use of the IGR's in this situation resulted in greater harm to potential biological control agents than in benefit to pest control.

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Résumé Deux régulateurs de croissance des insectes: le ZR-619 (éthyl n-méthoxy-3, 7, 11-triméthyl-(2E, 4E)-2, 4-dodecadienethiolate) et le ZR 777 (Prop-2 ynyl-3, 7, 11-triméthyl-(2E, 4E)-dodecadienoate) ont été expérimentés pour lutter contre le ver de la tomateKeiferia lycopersicella (Walsh.). Le traitement a été réalisé dans le sol où s'effectue la nymphose de ce ravageur. Les deux produits, isolément ou en mélange, ont réduit la sortie des adultes de 23 à 7% lorsqu'its, sont appliqués directement sur les nymphes, ils sont inefficaces quand ils sont introduits dans le sol. Les deux méthodes d'emploi ont supprimé les sorties d'Apanteles sp. jusqu'à 0%, à partir d'un taux de parasitisme allant jusqu'à 61%. L'utilisation de ces régulateurs de croissance dans de telles conditions est donc plus dommageable aux antagonistes naturels qu'elle n'est profitable contre le ravageur.

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Florida Agricultural Experiment Stations Journal Series No. 5093.     

Analysis of insecticidal Azadirachta indica A. Juss. fractions

As a result of chemical investigation on the ethanolic extract of fresh fruit coatings of Azadirachta indica A. Juss. (neem), twenty-seven compounds were identified in non-polar to less polar fractions which showed pesticidal activity determined by WHO method against Anopheles stephensi Liston. These identifications were basically made through GC-EIMS and were further supported by other spectroscopic techniques, including 13C NMR, UV and FTIR as well as retention indices. Thus sixteen n-alkanes, 1-16; three aromatics 2,6-bis-(1,1-dimethylethyl)-4-methyl phenol (17), 2-(phenylmethylene)-octanal (20), 1,2,4-trimethoxy-5-(1Z-propenyl)-benzene (27); three benzopyranoids 3,4-dihydro-4,4,5,8-tetramethylcoumarin (18), 3,4-dihydro-4,4,7,8-tetramethylcoumarin-6-ol (19), 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta[g]-2-benzopyran (22); one sesquiterpene methyl-3,7,11-trimethyl-2E,6E,10-dodecatrienoate (21); three esters of fatty acids methyl 14-methyl-pentadecanoate (23), ethyl hexadecanoate (24), ethyl 9Z-octadecenoate (25) and one monoterpene 3,7-dimethyl-1-octen-7-ol (26) were identified. Except 6, 8, 24 and 25 all these compounds were identified for the first time from the pericarp and fifteen of these, 1-3, 7, 9, 10, 17-23, 26, 27, are hitherto unreported previously from any part of the tree. Although this tree is a rich source of various natural products, it is the first report of identification of mono- and sesquiterpenes 26 and 21 and a potent antioxidant, 17.     

Ethyl (E)-3,5-ethano-7,11-dimethyl-2,4-dodecadienoate,A new insect growth regulator with potent juvenile hormone activity

A number of analogs of ethyl (2E,4E)-3,7,11-trimethyl-2,4-dodecadienoate were prepared and bioassayed for juvenile hormone activity on the yellow-fever mosquito (Aedes aegypti), the greater wax moth (Galleria mellonella), the yellow mealworm (Tenebrio molitor), the house fly (Musca domestica), and the tobacco budworm (Heliothis virescens). The analog ethyl (E)-3,5-ethanol-7,11-dimethyl-2,4-dodecadienoate (VI), containing a cyclopentene ring, showed remarkable potency on the above insect species. Since this compound possesses a fixed 3-s-trans-diene conformation it may provide some insight into the active conformation of bound 2,4-dienoate analogs.     

Action of ecdysoids,juvenoids, and non-hormonal agents on termination of pupal diapause in the flesh fly

Pupal diapause in Sarcophaga crassipalpis can be immediately terminated with high doses of ecdysterone or 5,β-hydroxyecdysterone. Within a range of lower doses diapause is not immediately terminated, but the duration of diapause is shortened. Injection of small doses at 3-day intervals is more effective than a single application of the same total amount. 5,β-hydroxy-ecdysterone is more effective than ecdysterone. The juvenoid isopropyl (2E,4E)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoate does not cause immediate termination of diapause but diapause is shortened. Simultaneous application of ecdysterone and the juvenoid synergistically produce a shorter duration of diapause than either hormone applied separately. Topical application of acetone and several other organic compounds can cause an immediate break of diapause. Neckligated pupae, however, do not respond to acetone treatment. Temperature shocks caused by brief exposure to high or low temperatures are ineffective.Although high doses of ecdysoids cause immediate termination of diapause, subsequent adult morphogenesis is protracted in direct proportion to the dose of ecdysoid. With the highest doses many flies fail to complete adult morphogenesis. Flies receiving high doses of ecdysoid are characterized by developmental abnormalities such as underdeveloped antennae, compound eyes, and mouthparts. By contrast, adultoids produced with juvenoids are characterized by abdominal abnormalities.     

Morphological effects of insect growth regulating compounds on Aedes aegypti (Diptera: Culicidae) larvae.

Cuticular development of $\text{Aedes aegypti}$ larvae was examined by electron microscopy and comparisons were made between larvae exposed to methoprene, isopropyl (E, E)-11-methoxy-3, 7, 11-trimethyl-2, 4-dodecadienoate, those treated with the fluorescent insect growth regulator, 5-[[[5-(dimethylamino)-1-naphthalenyl]-sulfonyl]amino]-1, 3-benzodioxole (DNSAB), and untreated larvae. Larvae of all three groups were routinely fixed at 24, 48, and 72 hr posttreatment. Thin sections of the sixth-abdominal segment, anal papillae, midgut tissue, and Malpighian tubules were examined for morphological variations from controls.     

Production of insect juvenile hormone III and its precursors in cell suspension cultures of the sedge, Cyperus iria L.

 Juvenile hormones (JHs) are sesquiterpenoids that regulate metamorphosis and reproduction in most insect species. There has been one report of an insect JH in plants: JH III, methyl-10R,11-epoxy-3,7,11-trimethyl 2E, 6E-dodecadienoate, has been identified in two sedge species, Cyperus iria L. and C. aromaticus (Ridley) Mattf and Kük. This is the first report of callus and cell suspension cultures derived from C. iria. Farnesol and methyl farnesoate, two biosynthetic intermediates of JH III in insects, as well as JH III have been identified in suspension culture cell extracts by gas chromatography-mass spectroscopy. These cultures thus provide a useful in vitro model to investigate the biosynthesis of JH III in the sedge, C. iria. Received: 30 October 1998 / Revision received: 11 February 1999 / Accepted: 3 March 1999     

雌性中缅树鼩繁殖期尿液的挥发性成分分析

正动物化学通讯包含信号发出者、化学信号、信号接收者三要素。尿液、粪便及特化腺分泌物是哺乳动物的主要气味源,由醇、烷烃、酸、酯、肽、蛋白质等组成,且其化学成分较为复杂(Novotny et al.,1999;Zhao and Wang,2010;Zhang and Zhang,2011)。尿液中化学信号发挥着极为重要作用,可以编码多种信息,如编码身体质量     

Juvenile hormone and its assay in virgin adult Blattella germanica females

The physiological bases for the gonadotrophic assay as presented by Kunkel were confirmed, and the assay method was found to be reproducible. However, the assay method was not found to be as useful as presented, due to the departure from linearity of the ovarian growth response above a hormone level of 5 μg/μl. Juvenile hormone (JH) titre higher than this level results in a depression of terminal oöcyte growth. Therefore, a valid assay of activity cannot be based on a single concentration.By injection, JH and FMC 23509 (10,11-epoxy-N-ethyl-3,7,11-trimethyl-2,6-dodecadienamide) were approximately equal in gonadotrophic activity. Topical application of FMC 23509 resulted in terminal oöcyte length of 2.45 mm in comparison to a length of 1.28 mm after injection of the same amount. This agrees with previous observations that such compounds are more active topically than by injection.     

New syntheses of the rice moth and stink bug pheromones by employing (2R, 6S)-7-acetoxy-2,6-dimethyl-1-heptanol as a building block

(2R, 6R, 10R)-6,10,14-Trimethyl-2-pentadecanol, the female pheromone of the rice moth (Corcyra cephalonica), methyl (2R, 6R, 10R)-2,6,10-trimethyltridecanoate, the male pheromone of the stink bug (Euschistus heros) were synthesized by employing (2R, 6S)-7-acetoxy-2,6-dimethyl-1-heptanol as the common chiral building block.     

苏铁的化学成分研究

对苏铁(Cycas revoluta)的化学成分进行研究,采用多种色谱技术(硅胶、氧化铝和Sephadex LH-20等)从苏铁茎的乙酸乙酯部位分离得到16个化合物,其结构由HR-ESI-MS、1H和13CNMR等波谱学方法鉴定为5,6-去氢柳杉酚(1)、cunningine A (2)、6-羟基-5,6-去氢柳杉酚(3)、6α-羟基-7-氧代弥罗松酚(4)、ligballinol (5)、xanthoxyol (6)、callislignan A (7)、(2R,3R)-bis[(4-hydroxy-3-methoxyphenyl) methyl]-1,4-diacetate (8)、开环异落叶松脂醇(9)、二氢山柰酚(10)、4'-甲基木犀草素(11)、5-methoxypinosylvin (12)、N-benzoylphenyl alaninol(13)、(E,4R)-4-hydroxy-4,5,5-trimethyl-3-(3-oxobut-1-enyl) cyclohex-2-enone (14)、3-hydroxy-5α,6α-epoxy-β-io-none (15)和acuminantin (16)。以上化合物均为首次从苏铁属植物中分离得到,其中化合物13和16为首次以天然产物报道。本研究还首次发现了苏铁属植物中含有松香烷型二萜类(1～4)和芪类(12)化合物。化合物11具有中等的体外α-葡萄糖苷酶抑制活性。     

Susceptibility of malathion-resistant strains of Tribolium castaneum and T. confusum to the insect growth regulators methoprene and hydroprene

A comparison was made of the effects of methoprene (isopropyl 11-methoxy-3, 7, 11-trimethyl-2, 4-dodecadienoate) and hydroprene (ethyl 3, 7, 11-trimethyl dodeca-2, 4 dienoate) on the developmental survival of three malathion-resistant strains of Tribolium castaneum (Herbst) and one of T. confusum J. du Val, with a malathion-susceptible strain of each species. No cross-resistance to either IGR in any of the malathion-resistant strains was detected.

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Résumé On a fait une comparaison des effets de methoprene (isopropyl 11-methoxy-3, 7, 11-trimethyl-2, 4-dodecadienoate) et hydroprene (ethyl 3, 7, 11-trimethyldodeca-2, 4 dienoate) sur le développement de trois races de Tribolium castaneum résistantes au malathion, et une race de T. confusum résistante au malathion, avec une race de chaque espèce prédisposée au malathion. Aucune résistance croisée a l'un ou l'autre IGR ne fut découverte dans les races résistantes au malathion.