JPH0899807A - Attractant for bee living in egg of euproctis taiwana - Google Patents

Abstract

PURPOSE: To obtain the subject attractant effective for controlling Euproctis taiwana, having extremely strongly attracting action on bees living in eggs of Euproctis taiwana. CONSTITUTION: This attractant for Euproctis taiwana contains (Z)-16-methyl-9- heptadecenyl isobutylate as an active ingredient. The active ingredient is used as it is or dissolved in an organic solvent such as hexane to give a solution and the solution can be adsorbed on a proper carrier (e.g. plastic or rubber) or sealed in a capsule or a capillary made of a plastic into a sustained release preparation to gradually release the active ingredient substance into air. A parasitism ratio in eggs of Euproctis taiwana is raised and Euproctis taiwana is controlled by attracting bees living in eggs of Euproctis taiwana by using the attractant.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an attractant for the parasitoid wasp of the white-necked moth, which is described in detail in (Z) -16-
TECHNICAL FIELD The present invention relates to an attractant for the parasitoid bee of the white-necked hemlock moth, which contains methyl-9-heptadecenyl isobutyrate as an active ingredient.

[0002]

[Background Art] A white-necked stag beetle (Scientific name: Euproctis taiwana), which belongs to the Lepidoptera family Heteroptera, inhabits regions such as Okinawa and Taiwan, and includes mango, loquat, cha,
In addition to feeding on various crops such as kidney bean or corn, larvae over the second instar have poisoned needles,
This adheres to the cocoons and attaches to the abdomen and tail hair when adults, especially female adults, emerge, and this poisonous needle causes inflammation when sticking to human skin. It is a pest that eats crops and a sanitary pest for humans. In the past, the control of schisandra serrata has been carried out by spraying insecticides, but in order to effectively control squid moths, it is necessary to accurately know the time of its occurrence, and effective insecticide spraying is effective. It is extremely difficult to expect control. On the other hand, with regard to the use of insecticides, the residue is a big social problem. Under these circumstances, in order to effectively control the white-necked stag beetle, an outbreak forecasting method for accurately knowing the outbreak ecology and
It is strongly desired to develop a special control means different from the control method using general insecticides.

[0003] Recently, the existence of parasite bees of many pests has been clarified, and a pest control method using the parasite bees is being developed. As one of the new attempts, it is considered to control the pests by increasing the parasitism rate of the pests on eggs by attracting useful egg parasitoids by using chemical substances released from the pests. An egg parasitoid bee belonging to Hymenoptera (Apidae) belonging to the female adult of the white-necked moth (Telenomus)
sp. cf. euproctis) is known to be present, and it has been considered to control the white stag beetle using this egg parasitoid bee.

In view of such circumstances, the present inventors have conducted diligent research on the egg parasitoid wasps of the giant stag beetle, and as a result, it is a sex pheromone substance of the giant stag beetle (Z).
-16-Methyl-9-heptadecenyl isobutyrate was found, but it was also found that the substance has a very strong attracting action against the egg parasitoid bee of the white stag beetle. The present invention has been completed based on these findings.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides (Z) -16-methyl-9-
It is intended to provide an attractant for an egg-parasitic bee of a white stag beetle containing heptadecenyl isobutyrate as an active ingredient. Of course, other desired components can be blended in the formulation. Hereinafter, the present invention will be described in detail.

[0006] The active ingredient (Z) -16-methyl-9-heptadecenyl isobutyrate of the attractant according to the present invention is a novel substance found by the present inventors. And, it has a strong attracting activity against the parasitoid bee of the white-necked moth. The active ingredient substance is used as it is or is dissolved in an organic solvent such as hexane to give a solution, which is adsorbed on a suitable carrier, for example, a plastic material such as polyethylene or rubber, or
Alternatively, a sustained-release preparation of the type in which the active ingredient substance is gradually released into the air by enclosing it in a plastic capsule or a thin tube can be prepared. The component substance of the attractant according to the present invention and the test for confirming its attracting activity will be described in detail below.

I. Isolation and Identification of Active Substances (a) Isolation of Active Substances Larvae that occurred in a field in the Okinawa Prefectural Agricultural Experiment Station were collected, and adults were obtained from pupae obtained by raising them indoors. Female adult 262
Cut off the sex pheromone secretory glands near the abdominal terminal node of the head,
Extraction was performed by extracting with hexane for 30 minutes. The extract was fractionated by column chromatography packed with Florisil. Also, this extract and 5% -ether /
When the hexane fraction was analyzed using a gas chromatograph equipped with a tactile potential detector (hereinafter abbreviated as GC-EAD), it was found that there were two components that generated a clear potential in the antenna of the male jack squirrel. It was When the 5% -ether / hexane fraction was analyzed using a gas chromatograph directly coupled mass spectrometer (hereinafter abbreviated as GC-MS), the active ingredient was a saturated aliphatic alcohol having 18 carbon atoms and 4 carbon atoms. It is a mixture of a saturated fatty acid ester (hereinafter abbreviated as A component), an aliphatic alcohol having 18 carbon atoms and an unsaturation degree of 1 and a saturated fatty acid ester having 4 carbon atoms (hereinafter abbreviated as B component). found.

The 5% -ether / hexane fraction was further fractionated by silica gel column chromatography containing silver nitrate. When each fraction was analyzed by GC-MS, the A component was eluted in the 2% -ether / hexane fraction, and the B component was eluted in the 4%-, 5%-and 7% -ether / hexane fractions. The two components could be separated.

(B) Identification of active substance The alcohol component obtained by hydrolyzing the fraction containing the component A was treated with methanesulfonyl chloride to give a chloride, which was subjected to GC-MS. The chloride derived from the component A showed a molecular ion peak at m / z 288 and a peak containing a chlorine atom at m / z 245 and 273 as a characteristic fragment ion. From this result, the carbon number of A component is 18
It was determined that each alcohol had a methyl side chain at the 16th position. Therefore, when separately synthesized 1-chloro-16-methylheptadecane was similarly subjected to GC-MS,
It was confirmed that the retention time and the mass spectrum were the same. Furthermore, separately synthesized 16-methyl-1-heptadecanol isobutyric acid ester (16-methyl-1-heptadecenyl isobutyrate) was used as GC-EAD and GC.
When -MS was used for the analysis, the result was in agreement with the analysis result of the component A derived from the extract (see FIG. 1).

Gas chromatographic retention time and mass spectrum of the product obtained by reducing the component B with diimide, and treatment of the alcohol component obtained by hydrolyzing the diimide reduced product with methanesulfornyl chloride. The chloride mass spectrum was in perfect agreement with the results for component A. Therefore, it was suggested that the chemical structure of the component B has one double bond in the chemical structure of the component A, that is, in the alcohol portion of 16-methylheptadecenyl isobutyrate.

When the fraction containing the component B was subjected to a reductive ozonolysis reaction and the product was immediately analyzed by GC-MS, 8-formyloctyl isobutyrate and an aldehyde having 9 carbon atoms were detected. Therefore, from both the result of this ozonolysis reaction and the result of the analysis of the A component, the B component was estimated to be 16-methyl-9-heptadecenyl isobutyrate.

Then, each geometrical isomer of 16-methyl-9-heptadecenyl isobutyrate was separately synthesized and subjected to gas chromatographic analysis. When compared and analyzed with the analysis result of the B component, the geometrical isomer of the double bond was obtained. Was found to be (Z). Synthesized (Z) -16
-Methyl-9-heptadecenyl isobutyrate by GC
When analyzed using -MS and GC-EAD,
The result was in agreement with the analysis result of the B component derived from the extract (see FIG. 2).

From the above results, the active substance (natural product) that generates a clear electric potential in the antenna of male male stag beetle,
B component which is the main component (amount extracted per female: 22.3
ng) (Z) -16-methyl-9-heptadecenyl isobutyrate, and the minor component A component (extraction amount per female: 7.5 ng) is 16-methylheptadecyl isobutyrate. Was identified.

II. One example of a method for synthesizing an active ingredient (Fig. 3
(See A, FIG. 3B, and FIG. 3C) In the following description, a compound name is sequentially numbered with parentheses and the compound is labeled with the number in accordance with a method commonly used in many chemical literatures. I shall. 2-propyn-1-ol ( 1 )
(25 g) was reacted with 3,4-dihydro-2H-pyran (45 g) in the presence of paratoluenesulfonic acid to give liquid 1- (2-tetrahydropyranyloxy) -2-propyne ( 2 ) (yield 53 g, bp 55 ° C./4 mmHg) was obtained. ( 2 ) (52 g) was dissolved in anhydrous tetrahydrofuran, n-butyllithium was added, and the mixture was stirred for 2 hours. To this reaction system, 1-bromo-3-methylbutane ( 3 ) (70 g) dissolved in hexamethylphosphoric triamide was added, and the mixture was stirred for 8 hours to give liquid 6-methyl-
1- (2-tetrahydropyranyloxy) -2-heptin ( 4 ) (yield 41 g, bp 104 ° C / 2 mmHg)
Got

( 4 ) (41 g) was dissolved in methanol,
By reacting with hydrogen gas in the presence of platinum oxide, 6-methyl-
After being 1- (2-tetrahydropyranyloxy) -heptane ( 5 ), it was filtered, paratoluenesulfonic acid was added, and the mixture was stirred to form liquid 6-methyl-1-heptanol ( 6 ) (crude product 33 g). Got ( 6 ) (33 g of crude product) was refluxed with hydrobromic acid in the presence of sulfuric acid to give liquid 1-bromo-6-methylheptane ( 7 ) (yield 17
g, bp 72 ° C./20 mmHg) was obtained.

Lithium acetylide ethylenediamine complex is dissolved in anhydrous dimethylsulfoxide, and ( 7 ) (17)
g) was added and the mixture was stirred for 24 hours to give a liquid 8-
Methyl-1-nonine ( 8 ) (yield 5 g, bp 62 ° C. /
18 mmHg) was obtained. 8-Bromo-1-octanol ( 9 ) (10 g) was added in the presence of paratoluenesulfonic acid.
Reacting with 3,4-dihydro-2H-pyran (5 g), liquid 8-bromo-1- (2-tetrahydropyranyloxy) -octane ( 10 ) (yield 10 g, bp 1
41 ° C./2 mmHg) was obtained.

( 8 ) (5 g) was dissolved in anhydrous tetrahydrofuran, n-butyllithium was added, and the mixture was stirred for 2 hours.
To this reaction system, ( 10 ) (10 g) dissolved in hexamethylphosphoric triamide was added, and the mixture was stirred for 8 hours to give liquid 16-methyl-1- (2-tetrahydropyranyloxy) -9-heptadecine. ( 11 ) (crude product yield 17 g) was obtained. ( 11 ) (Crude product yield 17
g) was dissolved in methanol, paratoluenesulfonic acid was added, and the mixture was stirred to obtain liquid 16-methyl-9-heptadecin-1-ol ( 12 ) (crude product 14 g).

( 12 ) (14 g of crude product) was dissolved in methanol and reacted with hydrogen gas in the presence of a Lindlar catalyst to give liquid 16-methyl-9-heptadecen-1-ol ( 13 ) (yield 2. 2g, bp 137 ° C / 1mm
Hg) was obtained. ( 13 ) (yield 2.2 g) was dissolved in pyridine and stirred with isobutyric anhydride (2.5 g) for 8 hours to obtain liquid 16-methyl-9-heptadecenyl isobutyrate ( 14 ) (crude product yield 2.9g)
Got

( 14 ) (2.2 g of the crude product) was subjected to silica gel column chromatography containing silver nitrate to give (Z) -16-methyl-9-heptadecenyl isobutyrate ( 14- Z) (yield 2.0 g). And (E)
Purified by -16-methyl-9-heptadecenyl isobutyrate ( 14- E) (yield 0.1 g) and each geometric isomer. ( 14 ) (0.2 g of crude product) was dissolved in methanol and reacted with hydrogen gas in the presence of platinum oxide to obtain liquid 16-methylheptadecyl isobutyrate ( 15 ), which was purified by silica gel column chromatography. Chromatography (yield 0.1 g).

III. Confirmation test of attracting activity of component substances (Z) -16-methyl-9-heptadecenyl isobutyrate (component B) and 16-methylheptadecyl isobutyrate (component A), which are identified as sex pheromones from adult females of the white-necked moth. ) Was used to examine the attracting activity against the egg parasitoid bee alone or in combination. The B component alone or a mixture of these components contained in a filter paper was used as an attracting source, and the component mounted in the trap was set outdoors. We attracted the attracted parasitoid wasps of the white-necked stag beetle, and compared the attracting activity of the compounds by the number of trapped eggs. In addition, the trap used here is a sticker plate coated with sticky substance, and a metal basket containing an attracting source or an uncopulated female of the white stag beetle is hung on it to prevent rain and dew. The structure was covered with the same type of roof. The results of this attracting activity test are shown in Tables 1 and 2.

[0021]

[Table 1]

As a result of this test, (Z) -16-methyl-
9-heptadecenyl isobutyrate (component B) and 16-methylheptadecyl isobutyrate (component A)
It was found that the mixture with and had a remarkable attracting activity against egg parasitoids. In addition, it was confirmed that their attracting activity exceeded the attracting activity of three virgin females of the white-necked moth.

[0023]

[Table 2]

As a result of the above-mentioned test, it was confirmed that (Z) -16-methyl-9-heptadecenyl isobutyrate (component B) alone has an activity of attracting parasitoid bees exceeding the attractiveness of three virgin females of the giant staghorn beetle. Was done.

[Brief description of drawings]

FIG. 1 Mass spectrum of component A (EI 70 eV)
Is.

FIG. 2 Mass spectrum of B component (EI 70 eV)
Is.

FIG. 3A is a synthetic route for B and A components.

FIG. 3B is a continuation of FIG. 3A. It is a synthetic route of B and A components.

FIG. 3C is a continuation of FIG. 3B. It is a synthetic route of B and A components.

Claims (1)

[Claims] 1. An attractant for a parasitoid bee of an Eurasian beetle stag beetle, which contains (Z) -16-methyl-9-heptadecenyl isobutyrate as an active ingredient.