JPH072601B2 - Semadara Kogae attractant - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD [0001] The present invention relates to a sex attractant of Coleoptera, Scarabaeidae belonging to the Coleoptera Scarabaeidae, and more specifically, (7Z) -tetradecen-2-one and (7E).
-Tetradecen-2-one as an active ingredient is contained in the sex attractant of Spodoptera litura.

[0002]

[Background Art] Coleoptera (Coleoptera, Scarabaeidae) belonging to the Coleoptera Scarabaeidae (scientific name: Blitopertha orientali
s or Anomala orientalis)
Is an important pest that feeds on leaves and grain of turfgrass, cherry trees, etc., and its larvae feed on the underground parts of plants such as turfgrass.

However, depending on the conventional insecticide,
It is very difficult to prevent or control the damage caused by these scorpions. Therefore, from such a current situation, in order to effectively control this pest, it is strongly desired to develop a predictive means for accurately knowing its occurrence and a new type of control means different from conventional insecticides. It is rare.

Up to now, the chemical structure of the sex pheromone has been clarified for many pests, and depending on the type of the pest, it has become possible to efficiently carry out the investigation of the occurrence of the sex pheromone using a sex pheromone agent. A method for controlling pests by using a sex attractant to capture large numbers of adult males or disturb the mating behavior of males and females is being developed.

Under the circumstances described above, the present inventors have
We conducted research on the sex pheromone of the scorpion beetle, picked up components with attractiveness to males from adult females of sect. It has been found that it exhibits various attractive effects. The present invention has been made based on these findings.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides (7Z) -tetradecene-2.
-On (IUPAC name: (Z) -tetradec-7)
-En-2-one) and (7F) -tetradecene-
2-on (IUPAC name: (E) -tetradec-
7-en-2-one) as an active ingredient. The present invention provides a sex attractant for Scutellaria chafer belonging to the Coleoptera Scarabaeidae characterized by containing 7-en-2-one) as an active ingredient.

(7Z) -tetradecen-2-one and (7E), which are active ingredient substances of the sex attractant according to the present invention.
-Tetradecen-2-one exhibits a strong attracting action and behavioral stimulating action on adult males of the beetle Chafera. This active ingredient can be synthesized organically by using 6-bromohexanoic acid as a starting material, reacting this with triphenylphosphine, and performing a Wittig reaction.

To prepare the sex attractant according to the present invention,
With (7Z) -tetradecen-2-one and (7E) -tetradecen-2-one, it can be carried out by utilizing the formulation technology which is usually applied in the preparation of the sex attractant. For example, (7Z) -tetradecen-2-one and (7E) -tetradecen-2-one are used as they are or as a solution in an organic solvent such as dichloromethane, and this solution is used as a suitable carrier, for example, plastic such as polyethylene or rubber. Or a plastic capsule or a material or device having an appropriate shape depending on the capillarity can be used to obtain a sex attractant in a practical form.

The isolation and identification of the component substance of the sex attractant according to the present invention from adult females, the chemical synthesis, and the confirmation of the sex attractant activity of the chemically synthesized product will be described in detail below.

(1) Identification of Component Substances The component substances were traced by a bioassay method for examining the attractiveness to adult males indoors and a gas chromatography / action observation direct coupling method (GC-BB).

Ten pairs of adult females collected or reared in the field were placed in a glass container having a volume of 1 liter, and while supplying clean air, the air around the females was replaced with porous polymer beads (Tenax, Tenax). The column filled with TA) was run for about 10 hours at night. Immediately thereafter, the extract was obtained by passing hexane through the Tenax column. The activity of causing the action of pushing out the male copulator was observed for the filter paper piece containing this extract. The extract was fractionated by column chromatography using silica gel (Wakogel C-200). That is, hexane, hexane / ether (95: 5, 90:10,
80:20, 50:50) and then ether. Filter the filter paper containing 0.1 of each fraction in a petri dish (9
Most males were attracted to the hexane ether (90:10) fraction as shown in male adults in 0 mm diameter, 60 mm height). However, when the fraction was analyzed by gas chromatography, many components were found.

Therefore, active components were examined by gas chromatography / behavior observation direct coupling method (GC-BB). This method examines the activity of each component separated by gas chromatography by behavioral observation.
That is, by splitting the gas chromatograph's capillary column into two directions and passing it through a hydrogen flame ion detector (FID) and a plastic box containing male adults, FID recording and behavior observation can be performed simultaneously. Is possible.

Hexane ether (90:10) above
The active fraction of DB-wax (30 mx
0.254 mm; 0.25 μm), hold at 50 ° C. for 1 minute, then raise the temperature to 180 ° C. at a rate of 4 ° C./min, hold at that temperature for 1 minute, and then 230 at a rate of 10 ° C./min. When the temperature was raised to 0 ° C. and the temperature was maintained for 10 minutes, the activity was recognized at 29.1 min. In addition, a non-polar column HP-1 (12 m × 0.2 mm; 0.33 μ)
m), and under the same conditions, activity was observed at 31.5 min after sample injection. Using both columns under the same conditions,
When the extract obtained from the virgin female worms by the air collection method was analyzed, the activity was observed at the same retention time, and the FID peak was also detected.

This component is the same as DB-Wax and HP-1.
When injected into a gas chromatograph directly coupled mass spectrometer (GC-MS analysis) under the above conditions using a column for analysis, a molecular ion peak m / z 210 and a base ion peak m / z 43 were observed. Other characteristic ion peaks are m / z 55 (34%), 58 (16),
67 (35), 69 (24), 71 (54), 79 (2
4), 81 (33), 96 (24), 97 (27), 1
11 (22), 125 (23), 128 (7), 152
(8), 192 (6) and 195 (1) were recognized. After catalytic reduction of the active ingredient, analysis by GC-MS revealed a base ion peak m / z 58.
Other peaks are 43 (73%) and 71 (4
5), 85 (16), 96 (9), 111 (4), 12
7 (4), 141 (1), 154 (4), 169
(2), 183 (1), 197 (3) and 212 (6) were observed. Therefore, the original component is tetradecene-2-
I could conclude that it was on.

In order to examine the position of the double bond, the active ingredient was reacted with dimethyl disulfide (DMDS) and analyzed by GC-MS. As a result, m / z 145 and m / z
A peak of 159 was obtained. The double bond of the original active ingredient was confirmed by the interpretation of this pattern to be in the 6 or 7 position. The two types of tetradecene-2-
When the on was synthesized and compared with the active ingredient, it was confirmed that the position of the double bond was 7. 7-tetradecene-2
The -one was in agreement with the active ingredient data, but the 6-tetradecen-2-one differed not only in retention time but also in MS data. For example, when 6-tetradecen-2-one was subjected to GC-MS analysis, the base ion peak m / z
43 and 54 (43%), 58 (12), 67 (57),
71 (17), 82 (55), 96 (42), 110
(27), 124 (33), 152 (25), 192
(3), 195 (1) and 210 (4) were obtained.

Regarding the geometrical isomerism of the double bond, two kinds of 7
-Tetradecen-2-one, i.e. (7Z) -tetradecen-2-one and (7E) -tetradecene-2
-Verified by on-synthesis. The isomers could be separated under non-polar column HP-1 under the above conditions. (7
Z) -tetradecen-2-one and (7E) -tetradecen-2-one were 31.53 min and 31.6, respectively.
It was detected at 7 min. 31.53 for active ingredients
Since it was detected in min, the structure of the substance is (7Z)-
It was identified to be tetradecen-2-one. However, the active ingredient contained (7F) -tetradecen-2-one as a trace component (12%). That is, the release rate of adult females is (7Z) -tetradecen-2-one (8
8%) and (7E) -tetradecen-2-one (12%)
Became clear.

(2) Synthesis of (7Z) -tetradecen-2-one and (7E) -tetradecen-2-one Triphenylphosphine (32.75 g) and 6-bro
After heating and refluxing mohexanoic acid (25 g) in acetonitrile (80 ml) overnight, decompressing and concentrating, washing with ether 3 times, and then 5-carboxy
pentyltriphenylphosphoniu
A crystal of mbromide (I) was obtained (yield 94
%). I (20 g) was added to anhydrous THF (50 ml), the mixture was cooled to -15 ° C, and an ether solution of methyllithium (1.5 M, 100 ml) was added dropwise thereto with stirring, and the mixture was stirred for 30 minutes. Thereafter, heptyl aldehyde (5.1 g) dissolved in anhydrous ether was added dropwise with stirring little by little, then, the temperature was raised to room temperature, and then the mixture was stirred for 30 minutes. After the reaction solution was poured into water and extracted with ether, the ether layer was washed with brine, dried over anhydrous sodium sulfate. After the ether solution was concentrated under reduced pressure, a mixture of (7Z) -tetradecen-2-one and (7F) -tetradecen-2-one (yield 65%) was isolated.
Also, using silica gel containing silver nitrate (10%),
The isomers were isolated by flushing with hexane ether (98: 2).

The thus chemically synthesized (7Z) -tetradecen-2-one and (7F) -tetradecene-
The non-polar column HP-
1 was used and analyzed under the above conditions. The retention times of (7Z) -tetradecen-2-one and (7E) -tetradecen-2-one are 31.53 min and 31.67 mi, respectively.
It became n. On the other hand, when the active ingredient previously isolated from the adult female of the scorpion beetle was analyzed under the same conditions, two peaks were detected at a ratio of 7: 1.

From the above results, the substance (natural product) having an extremely high attracting action to the adult male of the beetle, Coleoptera, Scarabaeidae, is (7Z) -tetradecen-2-one and (7E) -tetradecene- It was determined to be 2-on.

(3) Confirmation test of sex attracting activity of chemically synthesized substance (7Z) -tetradecene-2-obtained by chemical synthesis
When on and (7E) -tetradecen-2-one were subjected to a bioassay by gas chromatography / behavioral observation direct coupling method, extremely high sex-attracting activity was observed in the investigated range (1-1000 ng).

Further, an evaluation test of attracting activity was conducted in the field as follows. The basin trap (A) and wing trap (B) were used to compare sexual attraction for traps with synthetic pheromones, traps with 4 new virgin females daily in cages and untreated traps. This synthetic pheromone was prepared by mixing the active ingredients in the same proportions as the adult female release. That is, (7Z)-
It is a mixture of tetradecen-2-one (88%) and (7E) -tetradecen-2-one (12%). The trap to which 5 mg of this mixture was attached and the other traps were placed 10 m apart on the ground. To investigate the effect of height, one trap (B) was buried in the ground. The results of the 12-day survey are shown in Table 1. As shown in Table 1, three and one Scorpionidae were captured in the untreated traps of the trap (A) and the trap (B), respectively. On the other hand, a total of 64 animals were attracted to the trap with the synthetic pheromone. At that time, the peak of the scorpion beetle had passed, but it was confirmed that 32 traps were attracted per trap. Under the same conditions, 3 male adults were attracted to the trap containing 4 virgin females. That is, this test shows that the attractiveness of synthetic pheromones is 10 times higher than that of 4 virgin females. The number of trap insects embedded in the ground was higher than that on the ground.

Thus, a substance having an extremely high sex-inducing activity against males of the Coleoptera chafer belonging to the Coleoptera Scarabaeidae was isolated, and its chemical structure was determined by comparison with chemically synthesized substances. This makes it possible to provide the sex attractant of Spodoptera litura of the present invention containing (7Z) -tetradecen-2-one and (7E) -tetradecen-2-one as active ingredients. Conventionally, it has been difficult to prevent damage caused by the scorpion beetle using ordinary insecticides, but the sex-inducing agent according to the present invention enables effective control of the scorpion beetle.

[0023]

[Table 1]

Claims (1)

[Claims] 1. A sex attractant for Spodoptera litura, which contains (7Z) -tetradecen-2-one and (7E) -tetradecen-2-one as active ingredients.