JPS5862103A - Sexual attractant for dichocrocis punctiferalis - Google Patents

Abstract

NEW MATERIAL:10-Hexadecenal expressed by formulaI. USE:A sexual attractant for Dichocrocis punctiferalis, preferably in a mixture of the trans-and the cis-isomers at a ratio of (97:3)-(8:2), particularly most efficiently at a ratio of (9:1). PROCESS:Propargyl alcohol as a raw material is converted into a tetrahydropyranyl (THP) ether of 2-dodecyn-1-ol, which is then converted into THP ether of 10-dodecyn-1-ol. The resultant compound is then reacted with 1-bromooctane in the presence of n-butyl lithium to give THP ether of 10-hexadecyn-1-ol expressed by formula II, which is then reduced by the Birch method to afford the trans- isomer or catalytically reduced to give the cis-isomer. The protecting groups of the pyranyl groups are then removed to give an alcohol, which is oxidized with pyridinium chlorochromate (PCC) in methylene chloride, etc. to afford the compound of the trans- and the cis-isomers expressed by formulaI.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a sexual attractant for the Lamina chinensis, a method for producing the same, and an attractant for the Lamina lanternaria moth containing the attractant.

Dichocrocispu
nctiferalis) damages the fruits of a wide range of angiosperms belonging to 15 families and 80 species, and the damage to chestnuts and peaches is especially severe.In recent years, damage to chestnuts has been particularly severe nationwide, with an average damage multiplier of 10. ~20s, depending on the variety, the average year is 80%, 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 the adults in this column rarely fly to moth attracting lamps, it is extremely difficult to investigate their occurrence.

On the other hand, the chemical structures of so-called sex pheromones have recently been clarified for many pest insects, and it has become possible to efficiently investigate the occurrence and development of pests using these attractive sex pheromones. Sex pheromones are chemical substances that are generally secreted by female adults, and when male adults of the same species sense sex pheromones, 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 towards light), we have discovered the chemical structure of these attractive sex pheromones, chemically synthesized these substances, and used them as so-called sex attractants. It is possible to efficiently investigate orders. Furthermore, this sex attractant can be used to control pests by disrupting 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 of the present invention are the first time that two chemical compounds have been isolated from insects as sex attractants.

The above two types of compounds can be synthesized, for example, by the following method. That is, the production of tetrahydropyranyl (TI-IP) of 2-dobcin-1-ol (1) using prono, elugyl alcohol as a raw material,
Combine (2) and (5), then combine (1) with zipper reaction (Zip
-per Reaction) to lead to the T HP ether (2) of 1o-dobsin-1-ol.

(2) was then coupled with 1-bromopentane using n-methyllithium (BuLi) in tetrahydrofuran (THF)-hexamethylphosphoric triamide (HMPA) to generate 1o-hexadecin-1-ol. Synthesize THP ether (8). (8) is birch (
Birch) reduction leads to the trans form (4), and catalytic reduction leads to the cis form (5). Finally, the bilacyl protecting groups in (4) and (5) are removed to make the alcohol, and the alcohol of the saranico is oxidized, for example, by treatment with pyridinium chlorochromate (FCC) 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 sexual attractant for the Japanese lizard moth, it is desirable to use a mixture of the trans form and the cis form, and the ratio is 97=3 to 8:2, especially about 9 :1 is the most efficient.

The compound of the present invention may be encapsulated in a plastic capsule as it is or dissolved in a suitable organic solvent (e.g., hexane, ether, benzene, toluene, xylene), or in a plastic capsule such as rubber, synthetic resin, sand, etc. It can be used as a sex attractant by mixing it with powdered or granular carriers such as silica gel, sono, etc., and having the active ingredient adsorbed onto 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, on a vat containing water or other liquid, or on an object coated with an appropriate adhesive substance, By placing the pad near the pad, the moths are attracted and fall into the pad or become trapped 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 pheromones.

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 8% ether/pentane fraction, this was further purified and fractionated using gas chromatography. 5
% Dexil (Dexil) 3 Q□oc column 18
Under conditions of 0°C, activity was observed for only a single substance with a relative retention time of 12.16. Hereafter, this substance will be referred to as compound A.
It is called.

When examining the mass spectrum of Compound A, important fragment ions were as follows. rrVe(
relative strength), 41 (60), 55 (100), 69 (5
4), 194(8), 22o(10), and 238(5
). Since this mass spectrum matched the mass spectrum of the synthesized product, trans-10-hexadecenal, it was determined that Compound A was hexadecenal, a monoene.

Further, Compound A was subjected to ozonolysis and the product was examined to obtain 1.10-decanedial. Therefore, compound A is either one of the two geometric isomers of 10-hexadecenal or a mixture thereof.

Geometric isomers of compound A are synthesized trans and cis-
It was determined by comparing the behavior of 10-hexadecenal and the compound on a thin layer romatograph. That is, when the above three substances are adsorbed on silica gel impregnated with silver nitrate and developed with benzene/ethyl acetate (15:1), compound A is obtained.
Separated into two different substances, each containing trans-1
0-hexadecenal (Rf: 0.45), cis-10
-Hexadecenal (Rf: 0.85).

As a result, Compound A was found to be a mixture of trans-10-hexadecenal and cis-10-hexadecenal. In addition, the abundance ratio of the trans isomer and the cis isomer was approximately 9:1. While trans-10-hexadecenal itself showed attracting activity, no activity was observed in the cis form. However, since the activity was increased by mixing both compounds at a ratio of 9:1, a mixture of both compounds is necessary as a sex attractant for the Streptococcus japonica moth, and the trans isomer is considered to be the main component and the cis isomer is considered to be the minor component. Otsu.

0.12 mol of propargyl alcohol in anhydrous ether: 11 om1, 0.2 mol(7)2,
8-dihydropyran and para-toluenesulfonic acid 200
mg and stir for 3 hours. The reaction solution was then reduced to a saturated carbonate yield of 14 g (85%), rrVe 85 (base).

Under nitrogen flow, 80 ml of anhydrous THF and anhydrous HMPAa Q
ml7) Add 1-bromoocta:/O, 1m to the mixed solution.
ol and 0.1 mol of (I) were gradually added dropwise. Then, when 1 mol of n-BuLiQ 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-cooled 6NHO1 and extracted with ether. After washing the ether layer with heavy sodium chloride water, Na, 8
04 to remove ether.

1-→CH, (Cut), O=C, (m, OHQ[)
0.075 m01 of (IN) was made into 60 m1 of methanol solution, 1 g of para-toluenesulfonic acid was added to this, and 2
Stir for an hour. After adding water and extracting with hexane and washing the hexane layer with saturated potassium carbonate, the crude product is purified by distillation. b, p, 246-254℃ (0,8rr
rrHg), yield t1.8g (95%), r+yb1
68 (M), 125 (base).

(4) CHsCα(,), 0=C-OH,OH-1-→CH=C-(OH,), α■(lv) under nitrogen stream,
0.2 mol of potassium hydride (KH),
100 ml of t,a-diaminopropane is gradually added, and 97 mol of Q (2) is added dropwise to this mixture, followed by stirring overnight. A yellow paste-like precipitate was formed, so 1800 ml of ice-cooled 2NHO was added to dissolve the precipitate, and after cooling, extraction was performed with hexane, and the hexane layer was diluted with Na, 80.
The hexane is distilled off and the crude product is purified by distillation.

'P, 9 f/1. OmmHg, yield 10.2g (
86%).

rn/P31'68 (M), 155 (base).

Q, Q (i mol of anhydrous ether solution of (5) 3
8 mol of 2,8-dihydrobyran and 209 mg of para-toluenesulfonic acid are added to Qml, and the mixture is stirred for 8 hours.

Then, the brown-black reaction solution was washed with saturated potassium carbonate, and the ether 1 was washed with Na, 80. The ether is distilled off and the crude product is purified by distillation.

b, p, 125℃/1.0 mmHg, yield 18g
(85%), rr)/e 85 (base), 25
1,252.2 (9) Under nitrogen flow, 3 Qml of anhydrous THF and 3 ml of anhydrous HMPA
0.07 m of 1-bromopencune in a mixed solution of Qml
01 and (V) 0.05 mol were gradually added dropwise. Next, 3Qmol of n-BuLi was added dropwise over 10 minutes, and since the sult solution turned black, it was stirred for 6 hours under a nitrogen stream. The reaction solution was poured into ice-cooled 6NHO1 and extracted with ether. After washing the ether layer with deuterated water, Na, 8
04 to remove ether.

-m-→OH, (OH,) 4.佽C, (Ca,)〆…
(To) Remove the pyranyl protecting group according to method 3 to generate alcohol. Yield: 9 Jg (95%).

%’6288 (M).

(B) (1, (OH,)4.0=C・(OH,)'
, 80 m10 of Li (lithium) Ig under an OH nitrogen stream
In addition to EtNf (, (ethylamine)), dry ice-
Stir in acetone under low temperature. After a while, the lithium dissolves and the solution turns deep blue.
1 0.01 mol was gradually added dropwise and stirred 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 2N HOI and sodium chloride water. After dehydration, hexane was distilled off to obtain a trans-10-hexadecenol end. Yield tIg (40%'), rQ/e8
2 (Base), 220 (M”-”)” (OA
C) t, 161 mg of 95% ethanol solution in 5 m
1 of NaB horse, 25 mg of 95% ethanol solution.
5 ml, and 117 mg of ethylenediamine and 1.8 g of ethylenediamine were added thereto. Then, the gas phase in the flask was replaced with hydrogen gas, and the mixture was stirred using a magnetic stirrer for 1 hour. Add 2NH011Qml to the reaction solution to
c) was decomposed and then extracted with hexane, and the hexane layer was washed with hydrogenated sodium chloride water, dehydrated with Na at 80°, and the hexane was distilled off to obtain cis-10-hexadecenol (5). Yield 0.6g (46%).

T'rVf382 (base), 220 (M→18).

(9) 0H1(OH,), (l-OK(CH,),
OH+(l, (OH,), 0) LOH(CH,), (l
ffi.

v-'-to, piiidiniumchloroch
Add ISg and stir for 1 hour and 30 minutes. Add 50 ml of anhydrous ether to the reaction solution, and purify the organic layer 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, 100:0,97:8.90:1
0.80:20 mixed compound per rubber cap
An attraction effect test was conducted using an attraction source that adsorbed mg. The adhesive trap used in the attraction test consisted of a bottom plate (25 x 80 cm) and a thick gong coated with an adhesive substance (20 g of polybdenum/paper) and attached to a plastic roof plate in order to capture attracted males. .

A trap containing one rubber cap as an attraction source is placed outdoors (
The plant was installed at a height of 1.5 m above the ground in a chestnut garden, and male adults were attracted and captured. The effectiveness of the sex attractant was determined by the number of captured animals. The results are shown in Table 1.

100: O6 97: 8 490:10
2880:20
17 controls (no attraction source)
0II, E results (Table 1) show that trans-10-hexadecenal alone does not have sufficient effects as a sex attractant for the white borer moth, and that a small amount of cis-10-hexadecenal was added to it. It can be said that it is preferable. Moreover, the mixing ratio of Homare is preferably 9:1, and increasing the number of cis-forms more than this can be said to be undesirable as it will lead to a decrease in the number of attractants.

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 100:0.97:8.90:10
, 10 mixed compounds (Nanogun 4) of 80:20
An attraction effect test was conducted using an attraction source in which a hexane solution was allowed to adhere to P paper and the solvent was evaporated. A simple trap containing one attraction source is installed indoors.
cm x 45 Cm ), 100 male adults were released, and the attracted male adults were captured for 80 minutes.

The effectiveness of the sex attractant was determined by the number of captured animals.

The results are shown in the table below.

Number of kills in 30 minutes (average value of 4 repetitions) ■ / (average 100: 0 26.097:
8 a2.090:10
49.880:20 85.
0 control (no attraction source) 10

Claims (1)

[Claims] (1) 10-hexadecenal. (2) A method for producing 10-hexadecenal, which comprises oxidizing 10-hexadecenol. (8) A sexual attractant for the Lamina borer moth containing 10-hexadecenal.