JPH0253753A - Insect attractant containing 9,11-dodecadienylbutylate and 9,11-dodecadienylhexanoate as ingredient - Google Patents

Abstract

NEW MATERIAL:9,11-Dodecadiene-1-ol butylate expressed by formula I and 9,11-dodecadiene-1-ol hexanoate expressed by formula II. USE:An insect attractant (sex pheromone) effective against Melanotus sakishimensis. PREPARATION:A compound expressed by formula III is reacted with triphenylphosphine to give a compound expressed by formula IV, which is then subjected to Wittig reaction with a compound expressed by formula V to afford a compound expressed by formula VI. Then the compound expressed by VI is reacted with formula VII-formula VIII to provide the compound expressed by formula Iformula II. Furthermore, the compound expressed by formula I exhibits sex pheromone independently, but the compound expressed by formula II does not independently exhibit sex pheromone. However, when the compound expressed by formula II is blended with the compound expressed by formula I, the blend exhibits action stronger than a single compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel diene compound and an insect attractant containing the same.

Recently, the chemical structures of so-called sex pheromones have been clarified for many pest insects, 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 generally secreted by adult female insects that exhibits a species-specific attracting effect on adult insects of the same species. By clarifying the chemical structure of such an 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.

Melanotus
sakishimensis) is an important pest of sugarcane. These larvae prefer to feed on sugarcane buds, root zones, and stems underground, resulting in missing plants in sugarcane seedlings, heart withering or severely stunted growth in growing stems, and damage caused by feeding damage on harvested stems. Red rot causes a decline in yield and quality.

In addition, zero seeds are one of the causes of sugarcane cultivation problems in Okinawa Prefecture, such as failure to sprout. For control, chemical treatment has sometimes been used during planting, but since eggs are laid by adult insects that appear in early spring, no fundamental control method has been established. Since it is a soil pest, it is difficult to predict the density of occurrence, and it is important to know the amount of occurrence. In addition, it is necessary to devise a control method that targets not only the larval stage but also adults.

In view of these circumstances, the present inventors conducted research on the sex attractant of P. chinensis, extracted a component from the virgin female adult of P. chinensis and determined its chemical structure. did. Furthermore, by mixing chemically synthesized compounds,
I learned that this has an effective attracting effect on the Sakinmakan-shakushikmetsuki. The present invention was completed based on these findings.

By the method described below, the sex fumon isolated from a virgin female adult of P. chinensis contains 9,11-dodecadien-1-ol butyrate represented by formula (I) and 9,11-dodecadien-1-ol butyrate represented by formula (II). 9,11-dodecadiene-1
- all hexanoate.

CHz = CHCH= CH(CI□), 0CO(C
HI2) 2C) Iffi (1) CIlt = C
HCH= C)I (CIlt), OCO(C11
□), cll, (IT) Both of the above two compounds are new compounds that have not been described in any literature, and each constitutes a part of the present invention by itself.

As shown in the test examples below, the compound of formula (1) exhibits sex pheromone action by itself. On the other hand, 2(I)
The compound I) alone does not exhibit sex pheromone activity, at least in its naturally occurring proportion, i.e., in a minor proportion of approximately 3 parts per 100 parts of the compound of formula (+), as described below. does not indicate. However, 2 (
When the compound of formula II) is mixed with the compound of formula (+), the compound of formula (
It shows a stronger effect than the effect of compound 1) alone.

The compound of Ni(+) and formula ([1) exists in Z form and E form with respect to the double bond at the 9-position, but as shown in the test example below, any combination of them has sex pheromone action. Therefore, both the Z-form and E-form of both compounds, as well as mixtures thereof, are included in the present invention.

Compound 2 (1) can be synthesized, for example, by the following method.

1) Br (Cllz)q 0H(In) triphenylphosphine = ((C&l1s)zP(C1tl+eOH))
Br(rV) 2) ((Ci, Its)-P(C911+*011
) ) Br +Cl1z=CIICIIO(TV)
(V) Wittig reaction → c++z = CIICII = C1l (C1l
□), 0■ (Vl) 3) CI□=CHCl1=CII (CHz)toll
+ C11i(Cllz)zcOcl(■)
(■) →C1+□=C11C11=C11(CHI)30CO
(CH2C1h (1) The compound (II) can be synthesized, for example, by the following method.

1) CHx=CHCH=CH(Clh)sOtl
+ C11i (Cl+□), C0C1 (■)
(■) →CL=CHCH=CI(C1lz)eOco(CL)
ictlt (■) (1) and (The Z-form and E-form of the old compound can be separated as follows. Compound (Vr), which is a mixture of the Z-form and E-form, was impregnated with silver nitrate. It is adsorbed on a silver nitrate-silica gel column. It is eluted with a petroleum ether/ether solvent system to separate the E form that elutes earlier and the Z form that elutes later. These are each reacted with compound (■) (1 The Z-form and E-form of CHI) are also reacted with compound (■) to obtain two compounds of CHI) and the E-form.

When using the compounds of the invention as attractants, various forms of use are possible. Since these compounds are effective in extremely small amounts and are volatile, they can be adsorbed onto appropriate carriers (various synthetic polymers, natural rubber, synthetic rubber, etc.) or molded into these carrier materials. It is preferable to use it in the form of being encapsulated in a product.

The content of active ingredients can be determined as appropriate, but 78
When adsorbed to the body or encapsulated in a molded carrier material,
Approximately 1 to 10 Qmg per gram of carrier is desirable.

The compound of formula (1) of the present invention can be used alone as a sex pheromone agent as described above, but the compound of formula (U)
The mixing ratio is preferably close to the natural abundance ratio, that is, about fool, for example, 100:1 to 100.
: Can be used at a ratio of 10.

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 an object coated with a suitable adhesive substance. By doing so, the Chinese snails are attracted and fall into the container or become trapped in the sticky substance and die.

The present invention will be described in detail below in one order. In order to clarify the chemical structure of the sex attractant of the P. chinensis, we adsorbed the components released by virgin female adults onto filter paper and extracted them. The presence or absence of activity was determined using the following assay method. A glass cylinder with a diameter of 7 cm and a length of 60 cm was used, and wind was flowed at a rate of 25 cm per minute. The sample was placed on the windward side and the male adult was released from the leeward side. If active, male adults were attracted to the sample and judged by their behavior indicating excitement.

Filter paper extracts obtained from approximately 3,000 virgin female adults were concentrated, dehydrated with anhydrous sodium sulfate, and fractionated by column chromatography using a column packed with Florisil. The active fraction was eluted with 5% ether/hexane. The active fraction was purified by gas chromatography. When using a column packed with 10% Schiller 10C, the activity showed a relative retention time of 1.84 to 2.20 and 2.65 to 2.87 with tetradodecyl 7cetate.
Activity was observed only when the two parts were combined. Let us assume that the former is the A peak and the latter is the B peak. The quantitative ratio of the two peaks was 100:3.

Next, the following analysis was performed to determine the chemical structure of each component of these peaks. When the A peak was analyzed using a gas chromatograph mass spectrometer, a characteristic fragment ion with m/z 89.164 was observed, indicating that the number of carbon atoms is 12.
It turned out to be a butyric acid ester of alcohol with two double bonds. Since ω-butoxynonanal was detected when ozonolyzed, it was estimated that the double bond was at the 9th position, so the other double bond was at the 10th or 1st position.
It was considered to be in first place. When analyzed by capillary column gas chromatography, when a Schiller 10C column was used, the retention time was 13.79 minutes, and the retention time of the synthesized 9,11-dodecadien-1-ol butyrate was 13.68 minutes. -I lost. From these results, Beak A was confirmed to be 9.11-dodecadien-1-ol butyrate. When the B peak was analyzed using a gas chromatography mass spectrometer, m/zl
Since a characteristic fragment ion of 17.164 was observed, it was found that it was an alcohol hexanoate ester with 12 carbon atoms and 2 double bonds. When ozonolysis was performed, ω-hexanoxynonanal was detected, and the double bond was estimated to be at the 9th position.
The double bond was thought to be at the 10th or 11th position. Schiller 10 in capillary column gas chromatography
When analyzed using a C column, the retention time was 20.1
The retention time of 4 minutes was in good agreement with the retention time of synthesized 9,11-dodecadien-1-olhexanoate, which was 20.18 minutes.

From these results, Beak B was confirmed to be 9.11-dodecadien-1-ol hexanoate.

Based on the above, it is determined that the attractant for the Prunus chinensis consists of a mixture of the two compounds represented by formula (1) and (■).

Test Example 1 The attracting activity of both components, which were fractionated by natural gas chromatography, was confirmed in an indoor attracting test. The test was conducted as follows. A glass cylinder with a diameter of 7 cm and a length of 60 cm was used, and wind was flowed at a rate of 25 cm per minute. Place a sample of 0.01 female equivalent on the windward side and
Two male adults were released. If active, male adults were attracted to the sample and judged by their behavior indicating excitement. From the results in Table 1, the peak A proboscis isolated from the natural product has activity, and the combination of the peak A substance and the peak B substance has an attracting effect equivalent to that of the crude extract.

Crude extract 37% Beak A substance 20 Beak B substance O Mixture of Beak A substance and Peak B substance 40% Relaxation complex Compounds (1) and (I) chemically synthesized by the above method
An outdoor attraction test was actually conducted using I). A trap with a rubber cap impregnated with a hexane solution of the compound to be tested or a net cage containing a virgin female placed on a water basin was placed in a sugarcane field at a height of about 30 to 40 cm above the ground for 10 minutes.
They were installed at m intervals. Attractive activity was determined by counting the number of insects caught and killed by the sticky substance. Compounds (1) and ((1) were mixed at a ratio of 100:3 and the concentration was varied between 1 w and 10 mg to compare the attraction to virgin females. As shown in Table 2, the mixture of 10 μ They showed the same level of attraction as females.

10mg 963
■ 371■
8 virgin females 5
94 Example In order to investigate the attractive activity of the Z isomer and E isomer of the U compounds (+) and (+1), a mixture of these was impregnated into a rubber cap, and the attractive force was measured as a test example. Similar to 2, a comparison was made in a sugarcane field. Compounds (1) and (II
) were mixed at a ratio of 100:3. As shown in Table 3, these results showed that the combination of the Z isomer of compound (1) and the E isomer of compound (n) had the strongest arching force. However, there is no major difference in attractivity between this combination and other combinations, and any geometric isomer of compounds (1) and (II) can be used as an attractant for this pest.

Claims (4)

[Claims] (1) 9,11-dodecadien-1-ol butyrate. (2) 9,11-dodecadien-1-olhexanoate. (3) 9,11-dodecadien-1-ol butyrate and 9,11-dodecadien-1-ol hexa0000
Insect attractant containing 00. (4) The insect attractant according to claim 3, wherein the insect to be attracted is the Chinese cypress.