DD212640A5 - LOCKSTOFFPRAEPARAT FOR THE SELECTIVE ANALYSIS OF MALE GAMMAEULES - Google Patents

Abstract

The invention relates to a Lockstoffpraeparat for selectively attracting male Gammaeulen (Autographa gamma). The aim of the invention is to provide a novel preparation with increased effectiveness. According to the invention, the new preparation contains as active ingredient a mixture of 90 to 99.8% by weight of 7 (Z) -dodecen-1-ol-acetate and 10 to 0.2% by weight of 7 (Z) -dodecene-1. ol, optionally together with liquid and / or solid thickening agents and / or other excipients. The preparation according to the invention exerts a synergistic effect.

Description

"'Berlin, 20.12.1983

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Attractant preparation for the selective attraction of male gamma columns

Field of application of the invention

The invention relates to an attractant preparation for selectively attracting male gamma columns, insect containing trap containing this preparation, a method of selectively attracting and capturing the male gamma columns, and further to a method for preventing mating of these insects using the air space saturation method.

Characteristic of the known technical solutions

As is well known, the gamma owl (Autographa gamma) is one of the most important and widespread pests that consumes several plant species and causes annually recurring damage in the production of several plants - particularly vegetables, tobacco, sugar beet and other crops. Phosphoric acid ester derivatives have hitherto been used mainly to combat this pest, but they also have a pronounced toxicity on other living beings and also on humans. The use of phosphoric acid esters is also hindered by the fact that the gamma column can not overwinter in several countries (as in Hungary); therefore, the first damage is caused by caterpillars crawling out of the eggs of moths migrating from Mediterranean countries. The time of effective insect protection depends on the weather conditions.

Using pheromone-containing compositions in one case, the time of appearance of the pest may be predicted. The application of pheromones using the airspace saturation method allows for elimination

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a large part of the environmental problems associated with the use of conventional chemical insecticides. . "

The great advantage of the pheromone-containing traps compared to the known methods is the very high selectivity · In most cases, only the sought-after pest - sometimes together with some individuals of the closely related species - captured · For the preparation and evaluation of trapped insects are experts Another major advantage of the pheromone traps over the known light and UV traps is that no energy source is necessary so that the pheromone-containing traps can be kept in use at any point in the crop to be protected and the appearance of the Pests can be precisely located ·

By determining the appearance of the gull owl by means of the pheromone traps, the timing of the pest control to be carried out with conventional insecticides can be selected so that the effective control can be realized in the period of occurrence of the caterpillars.

By using the pheromones with the so-called "air space saturation", the male owls can be disturbed on finding the females and thus the mating of the animals can be prevented. In this case, a larger amount of the sexual attractant is uniformly distributed in the airspace throughout the area of the plant culture to be protected, so that the male animals everywhere can feel the presence of the sexual attractant, they become confused and can not find the sought females.

In summary, the application of pheromones have the

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following advantages:

- high selectivity (4-compound prevents the mating of only the selected pest and does not affect the life of other animals);

- low toxicity;

no environmental problems (the dose applied is one or two orders of magnitude less than that of the conventional insecticides) (Birch HC (ed.) Pheromones, North Holland Publ. Co _β London-New York, 1974, 495 PP)

The sex pheromone of the gamma owl was isolated from the female owls (Szöcs and Toth: Acta Phytopath., JJ _- , 453, (1979)). These authors have not determined the structure of the pheromone. "According to Ghizdavu and coworkers (Rev. Roum., Biol., Anim., 2, 87 (1979)), the 7 ($ - dodecen-1-ol acetate lures the male gamma columns in the field in the trap.

Object of the invention

The aim of the invention is to provide an attractant preparation for selectively attracting male gamma columns with greater effectiveness.

Explanation of the essence of the invention,

The invention has for its object to find suitable components and proportions of the components which give a attractant preparation with greater effectiveness. '

The invention is based on the finding that a certain combination of 7 (Z) -dodecen-1-ol-acetate and 7 (Z) -dodecen-1-ol shows a synergism and in the case of a stronger.

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attracting the male gamma columns as the 7 (Z) -dodecen-1-ol acetate per se.

This finding is surprising based on the teaching of the prior art. Two-component sex pheromone compositions · are known in two related moth species - Trichopusiani and Autographa californica. In the first moth, the dodecyl acetate is used in addition to the 7 (Z) -dodecen-1-ol-acetate, and the 7 (Z) - 'J' etradecen-1-ol ~ acetate in the second owl both cases an ester and / or an alcohol, as in the present invention,

The invention provides an attractant preparation for selectively attracting male gamma columns (Autographa gamma), characterized in that it comprises as active ingredient a mixture of 90 to 99.8% by weight of 7 (Z) -dodecen-1-ol-acetate and 10 to 0.2% by weight of 7 (Z) -dodecen-1-ol, optionally together with liquid and / or solid diluents and / or other excipients,

The synergistic preparation according to the invention

contains advantageously 95% by weight of fo (Z) -dodecene-1-ol-acetate and 5% by weight of fo- 7 (z) -dodecen-1-ol,

The inventive preparation can, for. B.

can be prepared by preparing a solution of the two components in an inert solvent, which is formulated in the form of capsules or microcapsules. As the inert solvent, hydrocarbons (eg hexane), halogenated hydrocarbons (eg. Dichloromethane), alcohols (eg, methanol), ketones

(eg, acetone), etc. are used. For the preparation of the solutions, any organic solvent is suitable which is inert to the two components and. in which these components are sufficiently soluble. Particularly advantageously, the preparation thus prepared can be used in. Insect traps. From the trap, the solvent evaporates rapidly and the remaining active ingredient combination gradually exerts its attractive effect by slow vaporization.

In order to avoid the evaporation of the active substance

In order to make it bulky, various viscous, nonvolatile liquids which are inert to the active compounds can advantageously be added to the preparation. For this purpose, z. As sunflower oil, olive oil, paraffin oil, mineral oils, etc. are used. This liquid does not affect the attracting effect at all, but keeps the Vaporisierungsgeschwind.igkeit the active ingredients at a uniform level, so that with the use of high drug concentrations possibly occurring activity reductions can be avoided.

Very good results can which 12-67 percent with a erfind.ungsgemässen preparation. Fo sunflower oil, 80-30 wt. Fo η-hexane and 8-3 wt. Fo contains active ingredient can be achieved. From this solution, such an amount is advantageously used, which corresponds to an active ingredient dose of 0.001 to 10.0 mg.

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In order to achieve the desired effect, the use of the viscous liquid is not absolutely necessary. According to a further advantageous embodiment of the present invention, solutions containing 50 to 90% by weight of an inert solvent (in particular hexane or dichloromethane) and 50 to 10 wt% ~ contain "the active combination in a suitable form completed. (for example, in rubber -., - Polyäthylenkapseln rubber or absorb) and inserted into one of a drug dose of 0.001 to 10.0 mg appropriate amount.

The invention further relates to an insect trap for the selective attracting and capturing of male gamma columns, characterized in that it contains in an amount of 0.001 to 10 mg - advantageously 0.05 to 3.0 mg - a composition according to the invention, optionally in an inert .Lösungsmittel or "dissolved in a viscous liquid and / or formulated in a capsule.

The invention further relates to a method for attracting and trapping male gamma columns, characterized in that exposing these insects to the effect of an above case.

The invention furthermore relates to a method of preventing the pairing of gamma columns, characterized in that a composition according to the invention is produced at a rate of 1.0 to 50.0 mg / hour / ha - advantageously 5.0 to 20.0 mg / Hour / ha * sent into the airspace ·

The 7 (Z) -dodecen-1-ol of the formula

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HO-CH ₀ - (CH ₉ ) CG = C- (CH ₉ ) ^ - CH. (I)

Ά ti

and the 7 (Z) -dodecen-1-ol-acetate of formula II

CH - C- _O -CH _o - (GH ₀ ) _ς -9 = 9- <GH ₉ ) - GH_ (II) j <; ._ ^ HH '

O can be prepared in a conventional manner.

, The starting material used is propargyl alcohol. The hydroxy group of this compound is first masked. From the compound of general formula III thus obtained

RO-CH ₂ -C =CH (III),

(where R is 2-tetrahydropyranyl, 1-ethoxyethyl or benzyl), an anion is formed in an aprotic solvent with a strong base (eg butyllithium)

formed, which - without isolation - with a compound ^ of the general formula IV

X-CH ₂ - (CH ₂ J ₃ -CH ₃ (IV)

is reacted (wherein X is chlorine, bromine, iodine, tosyloxy or mesyloxy). The compound isolated from the reaction mixture of the general formula V

, RO-CH ₂ -G = C- (CH ₂ J ₄ -CH ₃ (V)

(in which R has the above meaning) is in an aqueous solution by acid catalysis acid (z, B. hydrochloric acid

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• " jf

in methanol) into the 2-0ktin-1-ol of the formula V (R is hydrogen), which is reacted with the potassium salt of 1,3-diaminopropane »The hydroxy group of the compound of formula VI

RO-CH ₂ - (CH ₂ ) ₅ -.C ^ CH · · (VI)

(R = hydrogen) is masked. From the thus obtained compound of the general formula VI (in which R has the above meaning), an anion is formed with a strong base (advantageously with alkyllithium) in an aprotic solvent which, without isolation, is combined with a compound of the general formula. Formula VII

C-CH ₂ - (CH ₂ ) ₂ -CH ₃ (VII)

is implemented (where X has the above meaning). The protective group of isolated from the reaction mixture of the general formula VIII

RO-OH ₂ -CCHg) ₅ -OO-COHg) ₃ -CH ₃ (VIII)

(wherein R has the above meaning) is removed by acid hydrolysis in an alcoholic-aqueous solution (advantageously with hydrochloric acid in methanol). The resulting compound of the general formula VIII (R is hydrogen) is hydrogenated in the presence of a supported catalyst of moderate activity (advantageously palladium / barium sulfate) to 7 (Z) -dodecen-1-ol of the formula I. '

For the preparation of the 7 (Z) -dodecen-1-ol-acetate of the formula II, the compound of general formula VIII (R ~ is

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for hydrogen) in the presence of a base with an acylating agent (advantageously with acetic anhydride in pyridine), after which the resulting compound of formula IX

CH ₃ -CO-CH ₂ -CCH ₂ ) ₅ -C =C- (CH ₂ J ₃ -CH ₃ (IX)

with one, applied to a supported catalyst mäßi-S ^he (advantageously palladium / barium sulfate) is hydrogenated activity. "

The synergistic effect of the preparation according to the invention is demonstrated by means of the following experiments:

Determination; the attracting effect of 7 (Z) -dodecene-1-7pl-acetate (II) and / or 7 (Z) -dodecen-1-ol (I) in a field-exposed trap .

The preliminary test was carried out in Pestimre between 1 and 30 July 1979 on a cabbage field of about 35 ha, the second trial in place Pestimre, between 26 August and 27 October 1981 on a cabbage field of about 180 ha and the third attempt Place Vecses, between August 26 and October 27, 1981 on a cabbage field of about 300 ha performed.

The traps used consist of two, at the center roof-bent plastic plates with a size of about 20 cm χ 30 cm. The plates are joined at their corners, so that the roofs bent like a tent-roof are perpendicular to each other. "The inner part of the lower plate is smeared with an adhesive to trap the insects that are flying in. The bait is hung from the inside at the center of the upper plate. The traps

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are placed 25 m apart at a height of 0.5 m. · In the first test, the dose of the active substance is 1 mg and the bait is changed weekly. In the second and third trial, the drug dose is 0.5 mg and the bait is not exchanged during the trial. In the first trial, one trap is used for each treatment and in the second and third, three traps per treatment are used »

The trapped animals are collected weekly and determined by their species and genus. The results obtained are statistically evaluated according to the Duncan New Multiple Range Test. ·

In the traps containing as bait a 95: 5 wt .-% mixture of 7 (Z) -dodecen-1-ol-acetate (II) and 7 (Z) -dodecen-1-ol (I) are after the first attempt 16 male gamma columns imprisoned. The 7 (Z) -dodecene-1-ol-acetate (II) per se and together with other amounts of 7 (Z) -dodecen-1-ol (I) show no attractant effect. The results are summarized in Table I.

Table I

II Mixtures of II and I, in% by weight

1: 1 4: 1 95: 5

Average number - ' "- ~

the captive male 0 0 0 16 gamma columns

In the second experiment, this shows 7 (Z) -dodecen-1-ol acetate as such and in 7: 3 and 1: 1 mixtures with 7 (Z) -dodecene

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-1-ol a low attractant effect. The largest number of gamma columns are captured with a 95 s 5 mixture of 7 (Z) -dodecene-1-ol-acetate and 7 (Z) -dodecen-1-ol. The last value is significantly different from the results obtained with the other active substance combinations (P = 5%). »The results obtained are shown in Table II below.

Table II

II Mixtures of II and I, in wt.% 1: 1 7: 3 95: 5

Average - "........ -.,

Number of captured _Qa ^ _{6 &}

NEN male

Gamma columns.

The average values denoted by identical letters (a or b) in the same line do not differ significantly from each other at P = 5 %.

In the third experiment, similar results are obtained. The number of gamma columns trapped is greatest when using a 95: 5 mixture of 7 (Z) -dodecen-1-ol-acetate and 7 (Z) -dodecen-1-ol. Using 7: 3 ujid 1: 1 mixtures and 7 (Z) -dodecen-1-ol per se, the number of animals caught is significantly smaller (at P = 5%). The results obtained are summarized in Table III.

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Table III

II mixtures of II and I, in wt -.%

1: 1

95: 5

Average number of male gamma columns caught

6a 8a

44b

The throughput values denoted by identical letters (a and b, respectively) in the same line do not differ significantly from each other at P = 5%.

Ss can be summed up that in all experiments the ^? 95: '5 mixture of the two components has proven most effective. The 7 (Z) -dodecen-1-ol-acetate (II) has a very low activity per se. - -

MLusführungsbeispiel

Further details of the invention can be found in the following examples, without limiting the scope of protection to these examples.

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example 1

There were 12 parts by weight of sunflower oil or paraffin oil with 80 parts by weight of η-hexane and 8 parts by weight of an active ingredient mixture of 95 wt. % Compound of formula II and. 5 wt. % Of the formula I (ie weight ratio of the two active substances = 95: 5) mixed. From the resulting solution, such an amount, which corresponded to a drug combination of 1 to 3 mg, in the corresponding trained part of a trap, for example, a rubber capsule or a polyethylene capillary weighed. The drug combination solution could either be added to the adhesive used to trap the insects or soaked in textiles or natural or artificial porous materials.

Example 2

The procedure was as described in Example 1, except that 10 parts by weight of paraffin oil, 1 part by weight of butylhydroxytoluene '[2,6-di-tert-butyl-4-methylphenol], 1 part by weight. Part of a sunscreen

R means of, for example Uvizon, 80 parts by weight of η-hexane and .8 parts by weight of the active ingredient mixture were used.

Example 3

There were 10 parts by weight of an active ingredient combination of 98 wt. <Fo compound, the formula II and. 2 wt fo compound of formula I (that is, weight ratio of the two active substances 98: 2). M ± t blended 90 parts by weight of η-hexane. each of 1 to 2 mg of the drug combination containing amounts of this solution weighed into traps. The drug solution was soaked in polyethylene or polypropylene capillaries with an inside diameter of 0.3 mm.

example H

There were 10 parts by weight of an active ingredient combination

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99.8 wt.% compound of formula II and. 0.2% by weight of compound of the formula I with 90 parts by weight of silicone oils ** and added to the adhesive used in traps in such an amount that 1 to 5 mg of active ingredient mixture were added to the traps.

Beispiel.5

A flannel strip having a width of 2 cm was impregnated with the active ingredient combination solution prepared in Example 3 in α-hexane. After evaporation of the n-hexane, the strip was welded between polyethylene sheets 0.1 to 0.5 mm in thickness, and the mold thus produced was applied uniformly to the area to be protected against the insects in such a manner that that 1.0 to 30 mg / ha / hour of active ingredient mixture got into the air space.

Example 6

The procedure was as described in Example 5, but with the difference that the active compound combination solution in η-hexane paraffin oil or odorless kerosene was added in such an amount "that the solution of 30 to 50 parts by weight of obtained α-hexane. Φ kO to 60 parts by weight of paraffin oil or kerosene contained

Example 7

The procedure was as in Example 1, but with the difference that an active ingredient mixture of 9.7 parts by weight of compound of formula II and 0.3 parts by weight of compound of formula I (ie weight ratio of the two active ingredients = 97: 3) was used.

Example 8 The procedure described in Example 1 was followed.

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gone, but with the difference that an active ingredient mixture of 7.92 parts by weight of compound of formula II and 0.08 part by weight of compound of formula I (ie weight ratio of the two active ingredients = 99: l) was used.

Claims (3)

• 14- 20.12.1983 AP Δ 01 H / 253 857/2 62 826/12 Invention proposal 1, iiockstoffpräparat for the selective attracting male gamma columns (Autographa gamma) -, characterized in that ea ala active ingredient is a mixture of 90 to 99.8 wt _e -% 7 (Z) -dodecen-i-ol-acetate and 10 to 0 , 2 wt .-% 7 (Z) -dodecene-1-ol, optionally together with liquid and / or solid diluents and / or other auxiliaries contains » 2 'attractant preparation according to item 1, characterized in that it contains a mixture of 95 wt .-% 7 (Z) -Dodecen-1-olacetat and 0.5 Gew _e - $ 7 (Z) -Dodecen-1-ol. 3 * Loekstoffpräparat according to item 1 or 2, characterized in that it contains an inert diluent - advantageous η-hexane or dichloromethane - and / or a viscous liquid - preferably sunflower oil or paraffin oil -