JPS5959602A - Aurographa gamma composite inducer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to the male silver Y-moth (Aurographa gamma).
This invention relates to a mixed insect compound that attracts grapha gamma). More particularly, the present invention relates to compositions containing a synergistic combination of two active agents. Another subject of the invention is a mixed insect trap containing the composition.

A further subject of the invention relates to a method for attracting and collecting silver Y-moths and a method for controlling their mating by means of aerial dispersion techniques.

BACKGROUND OF THE INVENTION Silver Y-moths are widespread pests that infest and damage reeds, many plants, primarily vegetables, tobacco, sugar beets, and other productive plants throughout the year.

Phosphate esters have been applied to control this pest. However, these compounds do not exhibit a selective effect and, moreover, they are clearly toxic to humans.

The application of phosphorous esters to silver Y-moths is further limited by the following facts. That is, the pest is unable to hibernate in some countries, for example in Hungary. Initial damage is caused annually by larvae that hatch from moth eggs migrating from Mediterranean countries, so the effective eradication period varies throughout the year depending on climate.

By using traps that attract sex pheromones,
It is possible to predict the appearance time of pre-selected pests. Another method, the so-called airborne diffusion method, can solve most of the problems of environmental pollution associated with the use of conventional chemical pesticides.

The advantage of pheromone-containing traps over other trap-based prediction methods is their high selectivity. In most cases, they crowd out preselected or somewhat closely related pest species. Therefore, special skills and knowledge of inseminology are not required to evaluate collection methods. Another advantage of these traps over optical and UV wraps is that they are independent of energy sources or electrical wires. They can therefore be placed anywhere on the plantation to be protected, so that the emergence of pests can be precisely partially stopped.

When controlling the emergence of silver Y-moths, which are attracted with tiger and puerile pheromones, it is possible to choose a retention period with conventional insecticides, which should coincide with the appearance of the caterpillars. In this way, control becomes more effective.

When pheromocenes are used by airborne diffusion, males and females are prevented from finding each other, thus disrupting their mating and further reducing the number of generations. In this case, relatively large amounts of pheromones are emitted into the atmosphere of the plantation to be protected, where mosquitoes! , are aware of the presence of pheromones everywhere and are therefore confused and unable to find females and mate.

The advantages of this method include high selectivity (the active agent only controls the preselected insect pest spouse, but the vital functions of other living organisms are not affected) and low toxicity. Furthermore, when using pheromones in this way, they can be applied in much lower doses than classical insecticides, and therefore one does not have to take into account environmental pollution problems (Blrch M, C, (a
d) Pheromones.

North Holland Publ., Co., New York, 1974, 495 pages].

(Acta Phytopaph, lj, 453(1
979) ) tJ, silvery Y-report on the extraction of moth pheromones1, but they do not disclose the structure of the pheromone.

Ghizdavu etc. (Rev, Room
, Biol.

Anlms-2-4, 87 (1979)), 7)-dodecen-1-ol acedate produces an irritant response in male silver moths in field tests.

Object and Structure of the Invention According to the present invention, the following facts were discovered. That is,
When the following formula (1): % formula % 99.83 quantity Q is combined with the following formula (■): 7[F])-dodecen-1-ol 10-0.2N A composition is obtained which has an enhanced effect on male silver moths, which produces a much stronger irritant response than dodecen-1-ol acetate (7) on male silver moths.

This observation is quite surprising. Because two related villages (Trichop
lus nl) and Autographa cRlifornica
) Two types of sex pheromones have already been disclosed, and their tit main component 7) -Dobsen-1-
In addition to all acetate, dodecyl acetate and 7-phosphorus-tetradecen-1-ol acetate (
In other words, it contains (Bjo8tad)
etc.: +LChem, Eco1. ,6,727(1
981): 5teck etc.: Can, Ent,, l
]l.

1263 (1979)). In contrast, the compositions of the present invention contain 7(Z)-dovcen-1-ol, ie alcohol, as a synergistic second component.

According to a feature of the invention, the formula (1)% 99.8% by weight and the formula (It) 7)-dodecene-
Autog Y-moth (Autog.
A composite insect attractant is provided that attracts P. rapha gar+yna).

A preferred form of the composition according to the invention comprises 95% by weight of 7(Z)-dodecen-1-ol acetate and 7)-
Contains 5% by weight of dodecen-1-ol.

The composition according to the present invention can be prepared by dissolving the 211 components in an inert solvent to prepare a solution, and then charging the solution into a capsule or microcapsule or absorbing it into a capillary or microcapillary. It can be manufactured by Inert hydrocarbon solvents (for example hexane), non-organized hydrocarbons (for example dichloromethane), alcohols (for example methanol) or ketones (for example acetone) can be applied. The composition thus obtained is preferably used in a mixed insect trap. The solvent quickly evaporates from the trap and the remaining activator combination exerts its attraction effect through gradual evaporation.

To better slow the evaporation of the active agent, inert, non-volatile liquids of varying viscosities relative to the ingredients can preferably be added to the composition. For this purpose, for example, sunflower oil, olive oil, soraffin oil, mineral oil, etc. can be applied. These liquids do not have any influence on the attractive effect; moreover, they keep the evaporation rate of the active agent constant and thus avoid a reduction in the effect that would otherwise occur as a result of repulsive effects in the case of high doses of the ingredients. be able to.

Sunflower oil 12~67wt] 1%, hexane 80~30M
Compositions of the invention containing from 8 to 3% by weight of the combination of two active agents are particularly preferred.
A volume of solution prepared to support a dose of oi to 10 m7 is applied.

The presence of a viscous liquid is not essential for full effectiveness. A further preferred form of the composition according to the invention is an inert solvent, preferably hexano or dichloromethane 50 to 90 i! r (Q %) and a solution containing 50-10 folds of active agent JFfLi6 with a valuable attraction effect; this solution contains active ingredients o, ooi
~10. While administering the dose of Om9, appropriate adjuvants are applied (for example absorbed in rubber + flV paragum or I-lyethene capsules).

According to another aspect of the invention, a mixed insect trap for collecting silver moths is provided, which is optionally dissolved in a cineactive solvent and/or a viscous liquid and/or previously prepared. Formula (1) 7)-dodecen-1-ol acetate 90-99.8i and formula (It) 7)-dodecen-1-ol 10 ~0
．． 2% by weight, total volume 0.00)-10.0ml1. It is characterized by preferably containing 0.05 to 3.0 m9.

According to yet another feature of the invention, there is provided a method for attracting and collecting -Jl-silverY- moths, which method comprises 7(z)-dodecene-1- of formula (1) as the active ingredient. 7ri)-
Dodecen-1-ol 10~0.2 heavy use 1% in total amount 0
．． The method is characterized in that the moth is exposed to a mixed insect trap containing 0.001 to 10.0.19.

The composite insect attractant according to the present invention can permeate into the air to prevent the mating of silver Y-ga. The combination of two active agents is preferably introduced into the atmosphere at a rate of 10 to 50.0 my/ha/h, more preferably from 5.0 to 20.0 In9/ha/h. radiated.

According to yet another feature of the invention, a method is provided for disrupting mating in silver Y-moths, which method comprises formula (1) % formula %) 99.81i quantity coefficient and formula (II) 7 (Z) − Tochi′
The combination of Sen-1-ol 10-0.2 weight cake is preferably 1.0-500, more preferably 5.0-20.
It is characterized by radiating into the atmosphere at a rate of Omy/hectare/hour.

7(Oi-dodecen-1-ol acetate of formula (I) and 7(3)-dodecen-1-ol of formula (11) can be produced by methods known per se.

Pro- and rugyl alcohol is used as a starting material. The hydroxyl group of this alcohol is first masked and thus obtained: R-0-CH2C=CH(Ill) (wherein R represents 2-tetrahydropyranyl, 1-ethoxy-ethyl or benzyl group) The compound represented by is converted to the corresponding anion using a strong base, preferably butyllithium, in an aprotic solvent. The anion can be formed without isolation into the general formula (■): X-(Jl2-(CH2)3-CH3(IV), where
X is a base, a bromine or iodine atom, or a tosyloxy or mesyloxy group).

General formula (■) thus obtained: R-0-(Jl
The compound coated with 2-CEC-(CH2)4-CH3(V), where R has the meaning defined above, is isolated from the reaction mixture and then treated with a catalytic amount of acid in aqueous alcohol. in the presence of hydrogen chloride, preferably in methanol, to 2-octyn-1-ol (a compound represented by the formula (1), in which R represents hydrogen). The thus obtained 2-octyn-1-ol was converted to the general formula (Vl) a-o-CH2-('cu2) 5-C=CH(Vf) using potassium salt of 1,3-diaminopropane.
(In the formula, R is hydrogen.) Next, the hydroxyl group of the compound is masked, and the thus obtained compound of the general formula (■) (wherein R is a chlorine, bromine or iodine atom, or a tosyloxy or mesyloxy group) is treated with a strong base, preferably a tranquilizer. is converted to the corresponding anion using an alkyl lithium.

Without isolating the anion, the general formula (Vll)
:X-CH2-(CH2) 2-CH,, (Vll)(
(wherein, X is a chlorine, iodine or bromine atom, or a tosyloxy or mesyloxy group).

The general formula (■) thus obtained: o-cn2-(Cr-r2)5-CEC-(CuI2
)3-C113(~n+) (wherein R has the meaning defined above) was extracted from the reaction mixture with the
2, preferably C''J in methanol, . . . 11
It is removed using a hydrochloric acid solution, and the compound of the general formula (1) (in the formula, R is hydrogen) is formed! '+: a has an active state of medium zej' degree and is made to have a 114 form and is reduced in contact with +9114 using γ·P radium (suspended in a medium, preferably barium sulfate). , 7(Z)-dodecen-■-ol of formula (II) is prepared.

7(Z)-dodecen-1-ol acet-1 of formula (1)
・To obtain the general formula ■1 (in the formula, Tl is hydrogen)
The compound of is acylated using anhydrous t11', preferably in pyridine, in the presence of a base, and
) formula (■): CH, -C-0-CH2-(CH2)5-C-EC-(
The compound C112)3-C113(13)1 is catalytically reduced using a catalyst having an activity of (middle 1) and applied to a carrier, preferably .P radium supported on barium sulfate.

Effects of the Invention The effects of the composition according to the present invention will be clarified through experiments.

-t+jiyo%□r4-lee;: j:I) $% i
C1-111≧, (1 S・J Ride (11=71-()
-3;1-Ha,-,B-Determination of reactions G1,-time real brain j I;J:, 197shi] July 10th
Approximately 35 hectares of cabbage between July 30th and July 30th
: ili, the second actual thickness is 198J4
"Between August 26th and October 27th, approximately 180 hectares of cabbage fields were covered, and the third distribution of fruit was carried out between August 26th and October 27th, 1981." This is done with 300 hectares of cabbage.

The trap is bent in the shape of the top of the tent, 20X30
Consists of two plastic seams 1.cln.

One sheet has two tent-shaped tops 118 hanging on the car.
They are firmly attached to each other as shown in C1. The inside of the lower sheet is coated with adhesive to trap moths that fly into the trap. The moth's 113 attracting substance is the one hanging in the trap in the center of the two-part sheet. It is 25m away from.

In the first experiment, the dose of attractant was 1 m? and
I replaced it with a new one every 15 days. In the second and third experiments, the attractant η was 0.5 m9, and no reloading was done during the test.

In the first experiment, 91 traps per treatment were applied, while in the second and third experiments, 93 traps per treatment were used.

The primed moths were collected weekly and their glazes identified.

The final data was subjected to the Duncans New Multiple Range Test (Duncans New Multi Range Test).
It was statistically evaluated using Plelange Te5t).

In the first experiment, 16 male Y-moths were recruited in a mixture containing 95% by weight of 7φ)-dodecen-1-ol acetate and 5% by weight of 7@)-dodecen-1-ol. It was done. 7(z)-dodecen-1-ol only,
Furthermore, 7φ)-dodecen-1-ol in another bile combination showed no attracting effect.

Table 1 7(2))-Dodecene-1-7(2))-1Acene-1
-All aceol acetate date and 7 (2))
-Do1sen-1-all? R, combination 1:1 4:1 95:5 In the second experiment 1.7 (Z)-dodecene-1-
All acetate only, plus 7(Z)-dodecene-1-
ols and mixtures thereof (73 and 1, respectively:
A weight ratio of 1) showed a weak attraction, but most moths were captured using a 95:5 mixture of 21jh components. The number of moths captured is as follows: J41j, (p =
This is significantly different from that in Section 5).

Table 2 7(Z)-) N-7-1-7(Z)-) Asen-
]-All aceol acetate Tato 7 (Z)-
Mixture with F acen-1-ol 1:1 4:1 95:5 Data indicated with the same symbol (a or b) do not differ significantly from each other.

Similar results were obtained in the third test. A 95:5 mixture of the two components was found to be most effective, but
Significantly (p=5) fewer moths than 7:3 and 1
:1 mixture and 7)-dodecen-1-ol acetate alone were naturally captured in this j order.

Table 3 All Acetate Mixtures of tate and 7)-ζ-2-1-ol In each case, a 95:5 mixture of the two components can be said to be the most effective. 7)-dodecen-1-ol acetate showed the lowest activity when applied alone.

The present invention will be explained in a non-limiting manner by the following examples.O Examples of the invention Example 1 12 parts by weight of sunflower oil or nosorafin oil, 8 parts by weight of hexane
0 parts by weight and a mixture of active ingredients (compound 9 of formula (1)
5% by weight and 5M amount of the compound of formula (n))8
Mix parts by weight. A quantity of the solution obtained in this way, corresponding to 1 to 3 m9 of the active ingredient combination, is placed in a trap previously made available (e.g. placed in a rubber capsule or polyethylene capillary to collect the moths). or adsorbed onto textiles or porous natural or synthetic materials.

Example 2 Paraffin oil 1ON and butyl-hydroxy-toluene IM and an anti-fade agent (e.g. Uvi
The same procedure as described in Example 1 is carried out, except that 1 part by weight of ron.

Example 3 98% by weight of compound of formula CI) and compound 2 of formula (n)
10 parts by weight of the mixture were mixed with 90 parts by weight of hexane, and with the solution thus obtained the parts corresponding to the active ingredient combinations 1 to 2n17 were drawn into a capillary with a diameter of 0.31 and then Place it inside the trap.

Example 4 Compound 99.8m of formula (1), iu and formula (II)
10 parts by weight of a mixture of active ingredients, consisting of 0.2 parts by weight of the compound of Mix with glue.

Example 5 A piece of flannel (width = 2 cm) is impregnated with the solution obtained as described in Example 3. Evaporate the hexane. 9. The strip is then brought into close contact with the polyethylene mass.

The moldings obtained earlier were heated to 7″ so that the active acid entered the air at a concentration of 10–3 Q nU9 /h/hectare.
"゛""r*sK*fM!t;bo, 15. Eh.

Is the ratio of hexane 30 to 50 parts by weight? The method described in Example 5 is carried out, except that paraffin oil or colorless Japanese oil is mixed into the hexane solution such that the proportion of rough-in oil or kerosene is 40-60 ff, uJi parts.

Example 7 The process described in Example 1 is carried out, with the exception that a mixture of active ingredients consisting of 97% by weight of a compound of formula (RI) and 3i% by weight of a compound of formula (II) is applied.

Example 8 Compound 99% by weight of formula (I) and compound 1 of formula ([)
The method described in Example 1 is carried out with the exception that a mixture consisting of weight fractions is applied.

xl'F 211; Budapest, White Hungary 3 Szentendrej Utsza 24 0 Inventor Felenc Jyrak Budapest, Hungary 10 Rabinovic Giely Utsza 14 0 Inventor István Uyvari Budapest, Hungary 12 Zaratoly Utsza 5

Claims (1)

[Scope of Claims] 1. The following formula (I): OHH's 7)-dodecen-1-ol acetate-)90-9c as an active ingredient together with a desired liquid or solid scavenging agent.
i, sx amount Q and the following formula (■): HH 07 (Z)-door'-+L'/-1-all 20-0.
Male silver Y-moth Autographa gamma (Autographa gam) characterized by containing 2ftft%
A complex mixed insect attractant for ma). 2. 7)-dodecen-1-ol acetate 95
% by weight and 5% by weight of 7)-dodecen-1-ol. 3. As the liquid auxiliary agent, an inert solvent, preferably n
2. A complex mixed insect attractant according to claim 1, characterized in that - hexane or dichloromethane and/or a non-volatile liquid, preferably sunflower oil or paraffin oil. 4. As an activator, a combination of the following formula (1): 99.8% by weight and the following formula (■): 72)-dodecen-1-ol 10 to 0.2% by weight of HH in the total amount 0.001 to 10.0 m9, preferably 0.05 to 3.0 m9. Autographa 77 ga 72, characterized in that it is optionally dissolved in a cineactive solvent and/or a viscous liquid and/or formulated as a capsule.
A mixed insect trap for collecting mma)). 5. 99.8% by weight of the following formula (1) and the following formula (■):
The total quantity is 0.001 to 10.0mfi'
, is characterized by exposing the moth to the action of a mixed insect trap containing preferably 0.05 to 3.0 m9 of silver moth,
Silver Y - Method of attracting and collecting moths. 6. 7(Z)-dodecen-1-ol acetate 90-9 of the following formula (■);
9.8ffi quantity coefficient and the following formula (■): H 7)-dodecen-1-ol 10~02
% combination into the atmosphere at a rate of preferably 10 to 50.0 mg/ha/h, particularly preferably 5.0 to 20.0 m97 ha/h. 4 ways to prevent damage to your spouse