JPH0571575B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to esters of 7,9-decadien-1-ol and insect attractants containing them as cooperative ingredients.

Recently, the chemical structures of the so-called sex pheromones of many pests have been clarified, and it has become possible to efficiently investigate the occurrence and fate of pests using these attractive sex pheromones. Sex pheromones are chemical substances that are generally secreted by adult females and exhibit a species-specific attracting effect on adult males of the same species. By clarifying the chemical structure of this attractive sex pheromone, chemically synthesizing this substance, and using it as a so-called sex attractant, it becomes possible to efficiently investigate the development and development of sex pheromone. Furthermore, by using this sex attractant to lure and kill a large number of males or disrupt the mating behavior of males and females, it is also possible to control pests targeting the adult stage.

Tetramoera schistaceana , an important pest of sugarcane
Snellen's sex attractant is a compound of formula (): _C2H5CH =CH( _CH2 ) _8O -CO- _CH3 (), i.e. 9-dodecen-1-ol acetate and a compound of formula ( ₎ . : _CH2 =CHCH=CH( _CH2 ) _8O -CO- _CH3
() That is, it is known to be a mixture of 9,11-dodecadien-1-ol acetate.

This pest causes heart wilt in young stems, and causes red rot and breakage in adult stems due to strong winds, leading to a decline in sugarcane yield and quality. It is extremely difficult to control the larvae because they live inside the stems, and it is necessary to control the larvae before they hatch from eggs and feed on the stems, so it is important to know exactly when this pest appears. It is. In addition, it is necessary to devise a control method that targets not only larvae but also adults.

The present inventors synthesized a compound of formula (),
During various researches aimed at determining the probability of an accurate control method for P. chinensis using sex pheromones, it was found that when a synthetic product of formula () was mixed with a compound of formula (), it showed strong attraction. I discovered that. This phenomenon is more likely to be due to the interaction than the attraction when the synthetic products of formula () and formula () are mixed with the respective pure products of the compound of formula (), so when we investigated the cause, we found that Compound of formula (') mixed in the synthesized product of formula (): _CH2 =CHCH=CH( _CH2 ) _6O - _COCH3 (') That is, 7,9-decadien-1-ol
It was found that this was due to the synergistic effect of acetate.

As a result of further exploration around the compound of formula ('), the present inventors found that this cooperative effect is not limited to the compound of formula ('), and that the compound represented by formula (): CH ₂ =CHCH =CH( _CH2 ) _6OH () That is, it was found that this is common to esters of 7,9-decadien-1-ol.

The esters of 7,9-decadien-1-ol of formula () are themselves novel compounds and form part of the present invention.

The essence of the above synergistic action lies in the alcohol of formula (), and there is no characteristic in the acid constituting the ester. Therefore, the acid component constituting the ester is not particularly limited, and includes, for example, saturated or unsaturated fatty acids having _{1 to 18} carbon atoms; phenoxy fatty acids;
Benzoic acid which may have a substituent such as alkyl, halogen or amino; Mono- or di-alkylcarbamic acid; Benzene sulfonic acid which may have a substituent such as alkyl or halogen; Dialkoxyphosphoric acid; Examples include heterocyclic carboxylic acids such as furanic acid, thiophenoic acid, nicotinic acid, isonicotinic acid, and proline. Among these, esters with saturated fatty acids, especially lower alkanoic acids, are preferred, and the most preferred is the acetate of the compound of formula ().

As understood from the structural formula of formula (), the compound of formula () has Z-form and E-form with respect to the double bond at the 7-position, but E-form is preferable in terms of synergy.

The present invention also provides an insect attractant containing esters of the compound of formula () as a cooperating ingredient. Interestingly, the esters of the compound of formula () do not have any attracting effect on insects, especially the insects, but when mixed with the compound of formula () and the compound of formula (), the attraction they have can be increased. Enhances the action.

The insect attractant of the present invention has the formula () and the formula ()
contains a small amount of a compound of formula (), for example, approximately 0.01 part to 1 part, per 100 parts of a mixture of The effect can be enhanced.

Esters of unsaturated alcohols of formula () are:
It can be easily produced by a method known per se. A flowchart of the synthesis method using the compound of formula ('), that is, 7,9-decadien-1-ol acetate of formula () as an example, is as follows.

1 Br− (CH ₂ ) () ₇ −OH+ (CH ₆ H ₅ ) () ₃ P → (CH ₆ H ₅ ) ₃ P (C ₇ H ₁₄ OH) () Br 2 (CH ₆ H ₅ ) ₃ P (C ₇ H ₁₄ OH) () Br + CH ₂ = CHCHO () Wittig reaction, acetylation → CH ₂ = CHCH (') = CH (CH ₂ ) ₆ O-CO-CH ₃ Z form of the compound of formula (1) and E-form can be separated as follows. A mixture of Z-form and E-form is adsorbed onto a silver nitrate-silica gel column. It is eluted with a petroleum ether/diethyl ether solvent system to separate the early eluting E form and the late eluting Z form.

The attractant of the present invention can be used in various ways. The compounds of formulas (), (), and () are effective in extremely small amounts and are volatile, so they can be adsorbed onto suitable carriers (such as various synthetic polymers, natural rubber, synthetic rubber, etc.). It is preferable to use these carrier materials in the form of being encapsulated in a molded product.

The content of active ingredients can be determined as appropriate, but when adsorbed onto a carrier or encapsulated in a molded carrier material, the total amount of compounds of formulas (), (), and () in 1 g of carrier is approximately 0.1 to 100 mg. is desirable.

The carrier or carrier material molding containing such an active ingredient is placed on or near a suitable support, for example, on a container containing water or other liquid, or on a substance coated with a suitable adhesive substance. By placing the container in the container, insects, especially the insects, are attracted, and they either fall into the container or become trapped in the sticky material and die.

The present invention will be explained in more detail in the following order.

A synthetic compound having stronger attracting activity than the pure compound of formula () was fractionated by column chromatography using a column packed with Florisil.
The active fraction was eluted with 5% diethyl ether/hexane. The active fraction was then purified by gas chromatography. 3%OV-101
When using a column packed with dodecane-
Relative retention time with 1-ol acetate is 0.85
Appeared in the ~1.22 part. This part is 10% PEG
Further purification was performed using a column packed with -20M. An increase in activity was observed when adding moieties with relative retention times of 0.92 to 1.24 with dodecadien-1-ol acetate.

Next, the following analysis was performed to determine the chemical structure of each component of these peaks.

Analyzed with gas chromatography mass spectrometer,
It turned out to be an acetate ester of an alcohol with 10 carbon atoms and two double bonds. Moreover, since ω-acetoxyheptanal was detected in ozone analysis, the double bond position was estimated to be the 7th position. Therefore, we compared the retention times of substances with conjugated double bonds and capillary column gas chromatography. When using a Silal 10C column
A peak was detected at 7.48 minutes, which is (E)-7,9-
It matched the retention time of decadien-1-ol acetate. From these results, the attractive force increasing component is the E form of the compound represented by formula ('), that is, (E)
It was concluded that it was -7,9-decadien-1-ol acetate.

Test Example 1 (E)-7,9-decadien-1-ol acetate was synthesized and compared in an attraction activity test to confirm attraction increasing activity in an outdoor attraction test. The test was conducted as follows. Traps consisting of rubber caps impregnated with a hexane solution of the compound to be tested and placed on cardboard coated with an adhesive substance were placed in a sugarcane field at a height of approximately 80 cm above the ground at intervals of 6 m. Attractive activity was determined by counting the number of insects caught and killed by the sticky substance. 1 mg of (Z)-9-dodecane-1-ol acetate and (E)-9,11-dodecadiene-1-
A mixture of 10 μg of all acetate and 10 μg of this
We compared the attractive forces of the mixture with and without 10 μg of (E)-7,9-decadien-1-ol acetate, and the results are shown in Table 1.
It was shown to. This result proves that (E)-7,9-decadien-1-ol acetate enhances the attractive effect of formula () and the mixture of formula () by more than 10 times.

Table 1 Field attraction test results to confirm the effect of adding (E)-7,9-decadien-1-ol acetate Attraction source Male adult attraction number (Z)-9-dodecen-1-ol acetate and (E)-9 , 11-dodecadien-1-ol acetate binary mixture 5 3-component mixture of (Z)-9-dodecen-1-ol acetate and (E)-9,11-dodecadien-1-ol acetate 79 Test Example 2 , to find out the ratio of compound (′) and compound (+) showing the maximum attraction, 1.01mg
A rubber cap was impregnated with a mixture of the compound (+) and the compound (') in the range of 0.01 to 10 μg, and the attractive force was compared in a sugarcane field in the same manner as in Test Example 1. 0.1 to 10μ as accounted for in Table 2
It was well attracted by 1 μg of compound ('), and the highest attraction was shown by adding 1 μg of compound ('). These results indicate that a mixture of compounds (+) and () in a ratio of about 100:1 to 0.01 can be suitably used as an attractant for this pest.

Table 2 Field attraction test results comparing the attractivity of different mixed amounts of additional ingredients Amount of additional ingredient (') (μg) Number of male adult attractants 10 140 1 177 0.1 122 0.01 33

Claims (1)

[Claims] 1 Lower alkanoic acid ester of 7,9-decadien-1-ol. 2 7,9-decadien-1-ol acetate. 3 (E)-7,9-decadien-1-ol acetate. 4. An insect attractant containing the compound according to claim 1, 2 or 3 as a cooperating ingredient. 5. The insect attractant according to claim 4, wherein the main component is a mixture of 9-dodecen-1-ol acetate and 9,11-dodecadien-1-ol acetate. 6. The insect attractant according to claim 4 or 5, wherein the insect to be attracted is the insect attractant.