JPH0319213B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to a sex attractant for the Peach Moth. The peach moth (Dichocrocispunctiferalis) damages the fruits of a wide range of angiosperms, including 30 species in 15 families, and the damage to chestnuts and peaches is especially severe. is on average 10-20%,
Depending on the variety, the average yearly rate is 30%, sometimes reaching 70%. The larvae of this pest burrow into the fruit pulp and damage it, causing significant economic damage, and it is also extremely difficult to control. In order to effectively control this pest, it is important to accurately know when it appears, but since adults of this species rarely fly to the moth attracting lamp, it is extremely difficult to investigate its occurrence. On the other hand, the chemical structures of the so-called sex pheromones of many pests have recently been clarified, and it has become possible to efficiently investigate the development and development of pests using these attractive sex pheromones. Sex pheromone is a chemical substance that is generally secreted by female adults, and when male adults of the same species sense sex pheromone, they begin to fly towards the female adult, find this female adult, become sexually excited, and mate with her. . For insects that do not have phototaxis (the ability to move toward light), we have discovered the chemical structure of such attractive sex pheromone, chemically synthesized this substance, and used it as a so-called sex attractant. It is possible to efficiently investigate the development and development of the disease. Furthermore, pests can be controlled by using this sex attractant to disrupt the mating behavior of males and females, or by attracting and killing large numbers of adult males. In view of these circumstances, the present inventors conducted research on the sex-attracting substance of the Momonogomadara borer moth, extracted the component with sex-attractive activity from the Prunus moth, determined its chemical structure, and conducted chemical synthesis of the same. succeeded in. The present invention was completed based on these findings. The compounds in the present invention are trans-10-hexadecenal (E) and cis-10-hexadecenal (Z) represented by the chemical formula CH ₃ (CH ₂ ) ₄ CH=CH (CH ₂ ) ₈ CHO; This is the first time a compound has been isolated from an insect as a sex attractant. The above two types of compounds can be synthesized, for example, by the following method. That is, using propargyl alcohol as a raw material, 2-dodecine-1
- Tetrahydropyranyl (THP) ether (1) and then synthesize (1) using Zipper Reaction to synthesize 10-dodecine-
This leads to 1-ol THP ether (2). Next (2)
was coupled with 1-bromopentane using n-butyllithium (BuLi) in tetrahydrofuran (THF)-hexamethylphosphoric triamide (HMPA) to produce 10-hexadecine-1-
Synthesize THP ether (3) of ol. (3) undergoes Birch reduction to give the trans form (4), and catalytic reduction leads to the cis form (5). Finally, the pyranyl protecting groups in (4) and (5) are removed to give an alcohol, and this alcohol is further oxidized, for example, by treatment with pyridinium chlorochromate (PCC) in methylene chloride to obtain the desired aldehyde. When the above-mentioned compound of the present invention is used as an active ingredient in a sex attractant for the Japanese lizard moth, it is desirable to use a mixture of the trans form and the cis form, and the ratio thereof is 97:3 to 8:2, particularly about 9 :1 is the most efficient. The compounds of the present invention can be used as is or
encapsulated in plastic capsules in a suitable organic solvent (e.g. hexane, ether, benzene, toluene, xylene) or in powdered or granular carriers such as rubber, synthetic resin, sand, silica gel, etc. It can be used as a sex attractant by adsorbing the active ingredient on these carriers. Such a solvent, a powder, or an appropriate molded product coated or impregnated with these is applied by an appropriate method, for example, onto a vat containing water or other liquid, or onto an object coated with an appropriate adhesive substance.
Or by installing it near it, the moths are attracted and fall during the vagina or are caught in the sticky substance and die. Isolation of the active substance A bioassay method was used to investigate the sexual behavior of adult males to trace the active substance. Approximately 1000 virgin females were dissected and extracted with methylene chloride to obtain an oil containing the pheromone. When this was fractionated using a column chromatograph packed with Florisil, the activity was eluted in 5% ether/hexane, and this was further purified using a column chromatograph using silver nitrate-impregnated silica gel. Since the activity was eluted in the 3% ether/pentane fraction, this was further purified and fractionated using gas chromatography. On a 5% Dexil 300GC column at 180°C, activity was observed only in a single substance with a relative retention time of 12.16. Hereinafter, this substance will be referred to as Compound A. Structure determination of active substance After examining the mass spectrum of compound A,
The important fragment ions were as follows. m/e (relative intensity), 41 (60), 55 (100), 69
(54), 194(3), 220(10), and 238(5). Since this mass spectrum matched the mass spectrum of the synthetic product trans-10-hexadecenal, it was determined that Compound A was the monoene hexadecenal.
Further, Compound A was subjected to ozonolysis and the resulting product was examined, and 1,10-decanedial was obtained. Compound A is therefore either one or a mixture of the two geometric isomers of 10-hexadecenal. The geometric isomer of Compound A was determined by comparing the thin layer chromatographic behavior of Compound A with the synthesized trans and cis-10-hexadecenals. That is, the above three substances were adsorbed on silica gel impregnated with silver nitrate, and benzene/ethyl acetate (15:
When developed in step 1), compound A was separated into two different substances, which corresponded to trans-10-hexadecenal (Rf: 0.45) and cis-10-hexadecenal (Rf: 0.35), respectively. As a result, Compound A was found to be a mixture of trans-10-hexadecenal and cis-10-hexadecenal. Note that the abundance ratio of trans isomer and cis isomer was approximately 9:1. While trans-10-hexadecenal itself showed attracting activity, no activity was observed in the cis form. However, the activity was increased by mixing both compounds at a ratio of 9:1, so a mixture of both compounds is necessary as a sex attractant for the green leafhopper moth, with the trans isomer being the main component and the cis isomer being a minor component. Conceivable. Example 1 (Synthesis of active compound) (1) Add 0.2 mol of 2,3-dihydropyran and 200 mg of para-toluenesulfonic acid to 30 ml of anhydrous ether solution of 0.12 mol of propargyl alcohol,
Stir for 3 hours. The reaction solution was then washed with saturated potassium carbonate, and the ether layer was dehydrated with Na ₂ SO ₄ and then distilled under reduced pressure. bp.50~51℃/0.4mmHg Yield 14g
(85%), m/e85 (base), (2) Anhydrous THF 30ml and anhydrous HMPA 30ml under nitrogen flow
Add 0.1 mol of 1-bromooctane to a mixed solution of
() Gradually add 0.1 mol dropwise. Then n-
When 0.1 mol of BuLi is added dropwise over 10 minutes, the solution turns black, so this is stirred for 6 hours under a nitrogen stream. The reaction solution was poured into ice-cold 6NHCl and extracted with ether. After washing the ether layer with deuterated water, Na ₂ SO ₄
to remove ether. Yield 19.0g (80%), m/e85 (base) (3) Make 0.075 mol of () into 60 ml of methanol solution, add 1 g of para-toluenesulfonic acid,
Stir for 2 hours. Add water and extract with hexane,
After washing the hexane layer with saturated potassium carbonate, the crude product is purified by distillation. bp246~254℃
(0.3mmHg), yield 11.8g (95%), m/e168 (M ⁺ ),
125 (base). (4) CH ₃ (CH ₂ ) ₇ C≡C・CH ₂ OH → CH≡C・(CH ₂ ) ₉ OH () 1,3-diaminopropane is added to 0.2 mol of potassium hydride (KH) under a nitrogen stream. 100ml
To this mixture, gradually add 0.07mol ()
Add dropwise and stir overnight. A yellow paste-like precipitate is formed, so add 300 ml of ice-cold 2NHCl to dissolve the precipitate, and after cooling, extract with hexane. The hexane layer is dehydrated with Na ₂ SO ₄ , and the hexane is distilled off to obtain a crude solution. The product is purified by distillation. bp95℃/1.0mmHg, yield 10.2g (86%), m/
e168 (M ⁺ ), 155 (base). (Five) In 30 ml of an anhydrous ether solution of 0.06 mol (),
Add 0.08 mol of 2,3-dihydropyran and 200 mg of para-toluenesulfonic acid and stir for 3 hours.
The brown-black reaction solution is then washed with saturated potassium carbonate, the ether layer is dried over Na ₂ SO ₄ , the ether is distilled off and the crude product is purified by distillation. bp125℃/1.0mmHg, yield 13g (85%), m/e85
(Base), 251, 252, 253. (6) Under nitrogen flow, anhydrous THF 30ml and anhydrous HMPA30
0.07 mol of 1-bromopentane and 0.05 mol of () are gradually added dropwise to ml of the mixed solution. Then n-
When 30 mol of BuLi was added dropwise over 10 minutes, the solution turned black, so this was stirred for 6 hours under a nitrogen stream. The reaction solution was poured into ice-cold 6NHCl and extracted with ether. After washing the ether layer with heavy sodium water,
Dry with Na ₂ SO ₄ and evaporate the ether. Yield 13.2g (80%). m/e85 (base). (7) Remove the pyranyl protecting group according to method 3,
Produces alcohol. Yield 9.3g (95%), m/
e238(M ⁺ ), (8) Under nitrogen flow, 1g of Li (lithium) is added to 30ml of
EtNH ₂ (ethylamine) plus dry ice
Stir in acetone under low temperature. After a short time,
As the lithium dissolves and the solution turns deep blue,
Gradually add 0.01 mol of () dropwise to this and stir for 5 minutes. Next, 5 g of ammonium chloride was added to decompose unreacted lithium, and the reaction solution was extracted with hexane. The hexane layer was washed with 2NHCl and sodium chloride water, and after dehydration with Na ₂ SO ₄ , the hexane was distilled off and trans. -10-hexadecenol () was obtained. Yield 1g (40%), m/e82 (base), 220 (M ⁺ -18)
6 ml of 95% ethanol solution of 161 mg of Ni (OAC) ₂ ,
Add 25 mg of NaBH ₄ to 0.5 ml of 95% ethanol solution, add 117 mg of ethylenediamine and 1.3 g of ()
Add. Then, the gas phase in the flask was replaced with hydrogen gas, and the mixture was stirred using a magnetic stirrer for 1 hour. 10 ml of 2NHCl was added to the reaction solution to decompose Ni(oAc) ₂ , and then extracted with hexane. The hexane layer was washed with hydrogenated sodium chloride water, dehydrated with Na ₂ SO ₄ , and the hexane was distilled off to give cis- 10-hexadecenol ()
I got it. Yield 0.6g (46%), m/e82 (base),
220 (M ⁺ −18). (9) CH ₃ (CH ₂ ) ₄ CH=CH(CH ₂ ) ₉ OH → CH ₃ (CH ₂ ) ₄ CH=CH(CH ₂ ) ₈ CHO Compounds () and () were each dissolved in methylene chloride solution (20 ml ) and PCC (pyridinium chlorochromate,
Add 1.5g of pyridiniumchlorochromate) and
Stir for 30 minutes. Add 50ml of anhydrous ether to the reaction solution.
is added, and the organic layer is purified using a Florisil column.
In this way, the desired trans-10-hexadecenal and cis-10-hexadecenal were synthesized. Yield 100%. Example 2 (Attractive activity of synthetic compounds under field conditions) Trans-10-hexadecenal and cis-
10-hexadecenal, 100:0, 97:3,
Mixed compound of 90:10, 80:20 per rubber cap
An attraction effect test was conducted using an attraction source with 0.3 mg adsorbed. The adhesive trap used for the attraction test was
Adhesive substance (polybdenum 20
The bottom plate (25 x 30 cm) is made of cardboard coated with 100 g/paper), and this is attached to a plastic roof plate. A trap containing one rubber cap as an attraction source was installed outdoors (in a chestnut garden) at a height of 1.5 m above the ground.
The attracted male adults were attracted and captured. The effect of the sex attractant was shown by the number of captured animals. The results are shown in Table 1.

[Table] The above results (Table 1) show that trans-10-hexadecenal alone does not have a sufficient effect as a sex attractant for the white borer moth, and it is preferable to add a small amount of cis-10-hexadecenal to it. It can be said. The mixing ratio is 9:1
is preferable, and increasing the number of cis isomers is
This can be said to be undesirable as it leads to a decrease in the number of attractions. Furthermore, as is clear from Table 1, its attracting and killing effect is higher than that of conventional moth-attracting lamps, and synthetic compounds can be used to investigate the occurrence of moths. Example 3 (Indoor Attractive Activity) Trans-10-hexadecenal and cis-
10-hexadecenal 100:0,97:3,90:
An attraction effect test was conducted using an attraction source in which 10 ng (nanograms) of a 10:80:20 mixed compound was applied to paper and the solvent was evaporated.
A simple trap containing one attractant was placed in an indoor cage (60 cm x 60 cm x 45 cm), 100 male adults were released, and the attracted male adults were captured for 30 minutes. The effect of the sex attractant was shown by the number of captured animals. The results are shown in the table below.

[Table] Experimental example 1 It is a component of the sex pheromone of the diamondback moth, and is highly effective against the diamondback moth.
The following experiment was conducted to examine whether (Z)-11-hexadecenal, which exhibits EAG activity, exhibits an attracting effect on the fruit tree pest Prunus elegans moth. Materials and Methods: (Z) was applied to 25 male moths housed in a plastic screen cage (L.60 x W.30 x H.40 cm) in a thermostatic chamber at a temperature of 23 ± 1°C.
-11-hexadecenal or (E)-10- of the present invention
Hexadecenal was exposed to examine the attractivity of these compounds. The compound exposure method involves adding a certain amount of the compound to a piece of paper 2 cm wide x 3 cm long, and hanging it from a metal clip set on the ceiling inside the cage.
The frequency of localization of individuals flying to this piece of paper within 3 minutes was recorded. 3 for each compound, each dose
Repeat the experiment twice and find the average value, average value / 25
×100 was taken as the activity value. The interval between each experiment was 15 minutes or more. As shown in Figure 1, we conducted an experiment in five stages with a drug dose ranging from 1 to 150 ng, and found that (E)-
10-hexadecenal showed attracting activity starting from 10 ng, and particularly showed clear attracting activity at 30 and 150 ng. However, no activity was observed for (Z)-11-hexadecenal. As shown in the above data, (Z)-11-hexadecenal, which has an attractive effect on diamondback moths,
It had no effect at all against the Momonogomadarano borer moth.

[Brief explanation of the drawing]

Figure 1 is a graph showing the results of the attractive activity test of (Z)-11-hexadecenal and (E)-10-hexadecenal against the male moth Momonogomadara in Experimental Example 1. , ● represents (E)-10-hexadecenal.

Claims (1)

[Scope of Claims] 1. A sexual attractant for the Lamina chinensis moth containing 10-hexadecenal. 2. The sexual attractant for the Lamina borer moth according to claim 1, wherein the 10-hexadecenal is a mixture of trans-10-hexadecenal and cis-10-hexadecenal in a ratio of 9:1 to 8:2.