DD222765A5 - LOCKSTOFFPRAEPARAT FOR THE SELECTIVE ANNOYING OF MAJOR WINTER SAUCE - Google Patents

Abstract

The invention relates to attractant preparation for the selective attracting of male winter sows (Scotia segetum), characterized in that it contains as active ingredient a mixture of 1-98% by weight of 5 (Z) -decene-1-ol-acetoacetate of the formula I, CH3- (CH2) 3-CC- (CH2) 3-CH2-OC-CH3 (I) HHO1-98% by weight of 7 (Z) -dodecene-1-ol-acetate of the formula II, CH3- (CH2) 3- CC- (CH 2) 5 -CH 2 O-C-CH 3 (II) H OH and 1-98% by weight of 9 (Z) -tetradecen-1-ol acetate of the formula III, CH 3 - (CH 2) 3 -CC- (CH 2 ) 7-CH 2 -OC-CH 3 (III) H-HO optionally together with liquid and / or solid disintegrants and / or other excipients. The inventive preparation exerts a synergistic effect.

Description

Berlin, 20.12.1983 AP A 01 H / 253 859/7 '\ ¹ 62 825/12

Attractant preparation for the selective attraction of male winter sows. '

Field of application of the invention

The invention relates to a fabric preparation for selectively attracting male winter sows, insect containing trap containing this preparation, a method for selectively attracting and capturing the male winter seedlings, 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, Scotia segetum is a widespread pest that consumes several plant species and causes annual recurrent damage in the production of almost all crops, particularly tobacco, sugar beets, other vegetables and cereals. Phosphoric acid ester derivatives have hitherto been mainly used to combat this pest; However, all such control agents have the disadvantage that they show no selective effect and also have a pronounced toxic effect on humans. The application of phosphoric acid esters to the v / intersaateule is also hindered by the fact that the older caterpillars in the soil lead a hidden lifestyle and are difficult to access for the insecticidal agent.

The environmental problems associated with the application of conventional chemical control methods can be remedied in the control of butterflies when natural sex attractants, so-called sex pheromones, are added

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Containing species containing control butterflies can be used as control agents. Such sex attractants are produced and excreted by the female animals; The male butterflies of the same species can then find the females with the help of this perfume and themselves. , with them. '

- 2 -

In principle, the sexual attractants can be used in crop protection in two different ways.

After the first procedure will be

Sexual attractants as Köd.er-containing traps, which trap the male butterflies attracted by the drug. In this way, information about the occurrence of the pests, -linge can be obtained immediately, so that one can already orient themselves on the expected damage in advance. This procedure has the advantage over other procedures, also based on the use of traps, that only the pests selected in the given case are trapped in the sex attractants as bait-containing traps, while.

In the light or UV traps practically all insects flying at night are caught. , The sex attractants as bait-containing traps generally indicate that the beginning of the swarming of the pests is more sensitive than the light traps (compare Manu and co-workers, Schweiz Z. Obst. Weinbau - 81 [197 * 0, pages 337 to 3 ^ 4). Then, when the immediate environment of the traps is treated with an insecticidal agent, in the "annihilation zones" thus produced, most of the lost male S-butterflies population is killed ; Thus, the risk of pollution with the insecticidal agent is limited to these annihilation zones: so largely reduced.

By applying the other procedure, the so-called "airspace saturation procedure".

The male butterflies may be disturbed and the females may be found. so prevents the mating of the animals. become. In this case, a larger amount of the sexual attractant is evenly distributed in the airspace in the entire area of the crop to be protected,

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so that the male animals everywhere can feel the presence of the sexual attractant; They are, so to speak, confused and can not find the wanted females. In this procedure, only relatively small amounts of the sex-blocking agents corresponding to only fractions of the conventional doses of the classical insecticidal active ingredients (see W. L, Roenols and R. T * Garde, Ann Rev, Entomol., 22 (1972), pages 377 to 405) is needed.

Through the application of the sex attractant of winter sowing, owl containing bait traps can also be the Jachteil the previous Bekämpfungsverfahrens-. that the onset of the pest was difficult to recognize in time, and that control could only be started when the older caterpillars had already exerted their harmful effect on the internal parts of the plant, which are practically unreachable for the classical insecticidal active ingredients. be resolved·

Lifting the heights. Selectivity of the sexual attractants, especially when used in the airspace saturation regime, is an important further advantage in that these agents are non-toxic to animals (M, G. Birch, Pheromones, North Holland Publishing Co., London-New Yorky 1974, page 495). .

The Sexpheromon of the Winter Sauleule would be by Bestmann and; Co-workers (Angew. Chemie JO, 315-816 (197S)). The structure of the pheromone was prepared as 5 (Z) -decene-1-ol-aoetate (compound of formula I) *

, CH - (CH ₀ KC = C- (GK ₀ ) - CH ₂ -QC-CH. '(I) Ή H-'

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By further experiments it was found that this pheromone consists of two components - namely 7 (Z) -dodecen-1-ol-acetate (compound of formula II)

CH-- (GH ₀ ) _- C = C- (CH ₅ ), - GH ₀ -OG-GH- (II).

and 9 &) - tetradecen-1-ol-acetate (compound of formula III)

CH 1 - (CH ₉ ) - C = G- (GH ₉ ), -CH ₉ OC-OH-, (III)

' HH. , 0 '·

exists (BE-PS No. 886 800).

Aim of the invention. , ^:

The aim of the invention is to provide a novel attractant preparation for selectively attracting male winter sows with greater effectiveness. , '.

Presentation of the essence of the invention

The invention is based on the object, aufaufufufinden suitable components and proportions of the components which give a attractant preparation with greater effectiveness. -

It has been found in accordance with the invention that the 5 (Z) -decene-1-ol-.acetate of the formula I · has only a very low attracting activity in the field, a mixture of the 7 (Z) -dodecene Although 1-olacetate of the formula II and of the 9 (Z) -tetradecen-1-ol-acetate of the formula II attracts the male individuals of the winter sowing owl, the trap also attracts male individuals of other related Saateulanarten. Dia evaluation of the

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This makes fishing difficult, «

Die.Erfindang based on the finding that one of 7 (Z) -dodecen-1-ol-acetate of the formula II, 9 (Z) -Tetradecen-1-ol-. Acetate of the formula III and 5 (Z) -decene-1-ol-acetate of the formula'Ί existing combination has a synergetic 'effect and' on the male winter oil oils an attractant effect 'which the effectiveness of the 5 (Z) -Decen-1-ol-acetate and the described in the BE-PS Nr · 886 800, two-component preparation far surpasses. The preparation according to the invention is ^as far as specifically specific in that it attracts and captures the male individuals in the insect trap, practically exclusively the winter sowing owl.

The invention relates to an attractant preparation for selectively attracting male winter

saateulen. (Scotia segetum), characterized gekennzeich.net that it contains as active ingredient a mixture of 1-93 fo 5 (Z) -. Decene-1-ol-acetate of formula I, 1-9 wt fo ö 7 (Z) -Dodecene-1-ol-acetate of the formula II and. l-9ö weight . fo 9 (z) -Tetrad.ecen-1-ol-acetate of formula III, optionally together with liquid and / or solid diluents and / or other Hilfstoffen.enthält. '

The inventive preparation contains vorteilhal't .5-90 wt. Fo compound of formula I. 5-9O wt. Fo compound of formula II and 5-9u wt. Fo · compound of formula III. · ·

Suitably, the attractant according to the invention contains prepared as diluent inert solvents, especially hydrocarbons, in particular n-hexane, and / or .Halogenkohlenwasserstoffe,. in particular dichloromethane and / or viscous liquids, in particular sunflower oil and / or paraffin oil. Further examples of inert solvents are alcohols, such as methanol, and. Ketones, like acetone. But for the solutions is any organic solvent which 'is inert to the two active ingredients and. in which they are sufficiently soluble suitable.

Thus, the attractant according to the invention can be prepared as a solution of the three active substances in an inert solvent, which is advantageously prepared in the form of capsules or microcapsules.

Such inventive preparations can be used particularly advantageously in winter seed traps. From the trap, the solvent evaporates rapidly and the remaining active ingredient combination exerts its attractant effect by slow evaporation. Gradually out.

In order to make the evaporation of the active ingredients uniformly slow, the attractant preparation according to the invention can be advantageous in various ways

The active substances contain inert viscous semi-volatile liquids, such as sunflower oil, olive oil, paraffin oil and / or mineral oils. These liquids do not influence ^x 'the anlockende'Wirkung but keep d.ie Verd.ampfungsgeschwindigkeit of the active ingredients in an even level, so that the Aktivitätstvermind.erungen when using high concentrations of active ingredient may occur otherwise avoided can be. To achieve the desired effect but is the counter. Do not wait for the viscous fluid. , '. '

As advantageous, has a erfind.ungs-> ', according to attractant, which 12 to 6? % By weight of sunflower oil, SO to 30% by weight of hexane and 8 to 3% by weight of the active compound according to the invention

, contains proven. From this solution will be. ^{vorzugsveise:} an amount ,. which corresponds to an active ingredient dose of 0.001-3) 0 mg. 'It is particularly advantageous also a erfind.ungsgemäßes attractant preparation comprising a solution containing up to 90 weight ^d o of an inert solvent, in particular η-hexane or dichloromethane, and 50 to 10 wt - o contains the active ingredient combination in a.? suitable form, ¹ ZXWa example in; Rubber, rubber or polyethylene capsules are sucked up, ready for use. Also of it

It is preferred to use an amount corresponding to an active ingredient dose of 0.001-3.0 mg. '

As an advantageous option can

 the attractant preparation according to the invention in winter Sauleulenfallen z \ un attracting and trapping v.on, male Wintersaateulen (Scotia segetum) are used.

As an alternative and distributive possibility, the attractant according to the invention can be prepared by the airspace saturation method known per se for preventing the mating of winter sows (Sc.otia segetum).

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be used. In this case, the active ingredient mixture of the inventive attractant preparation advantageously with Ge; speeds of 1.0 to 30.0 mg / ha / hour, preferably 5.0 to 20.0 mg / ha / hour, are emitted into the airspace.

The invention furthermore relates to an insect trap for the selective attracting and capturing of male winter sows, characterized in that it contains an amount of 0.001-3.0 mg, preferably 0.005-0.5 mg. Composition according to the invention, optionally dissolved in an inert solvent or dissolved in a viscous liquid and / or formulated in a capsule.

The invention further relates to a method of attracting and trapping male winter sows, characterized in that these insects are exposed to the action of an above trap. ;

The invention furthermore relates to a process for reducing the pairing of winter sows, characterized in that a composition according to the invention is produced at a rate of 1.0-30.0 mg / hour / ha - advantageously 5.0-20.0 mg / Hour / ha - sent out into the air.

The preparation of the 7 (Z) -dodecen-1-ol-acetate of the formula II and the 9 (Z) -tetradecen-1-ol-acetate of the formula III was prepared in 3E-PS'ir. 386,300.

The 5 (Z) -decene-1-ol-acetate of the formula 1 can be prepared in a manner known per se from the propargyl alcohol of the formula IV

RO-CH ₂ -G-CH '(IV)

(R is hydrogen) are prepared as follows; The hydroxy group of propargyl alcohol is

masked. From the thus-obtained compound of the formula IV (wherein R is the 2-tetrahydro-pyranyl or 1-ethoxy-ethyl) is formed with the aid of a strong base (advantageously alkyllithium), an anion which '5. - without isolation - mit'einer compound of the general formula V

, \. CH ₃ -CH ₉ -CH ₂ -X '• (V).

10 '{wherein X is chlorine, bromine, iodine, tosyloxy or mesyloxy bed. From the compound of general formula VI thus obtained. , ''

, ; , -RO-CH ₂ -C =C- (CH ₂ ) ρ-CH ₃ '(VI)

15; ', ·. ~

(wherein R d.xe has the above meaning) is removed, the protecting group by ¹ acid catalysis and. the resulting compound of general formula VI (wherein R is hydrogen) is reacted with the potassium salt of 1,3-diamino-propane. The hydroxy group of the "compound of general formula VII" isolated from the reaction mixture

RO-CH ₂ - (CHp) ₃ -C = CH (VTI)

(R is hydrogen) is masked. From the compound of the general formula VII thus obtained (in which R has the above meaning) an anion is formed with the aid of a strong base (preferably alkyllithium). which without isolation with a connection of the general

common formula VIII _v

'CH ₃ - (CH ₂ ) ₂ -CH ₂ -X (VIII.

(where X is as defined above.) The protecting group of ¹ isolated from the reaction mixture

Compound of the general formula IX

RO-CH ₂ - (CH ₂ ) ₃ -C = C- (CH ₂ ) ₃ -CH ₃ (IX)

(where R is as defined above) is removed by a seed-catalysed hydrolysis and. the resulting compound of general formula IX (wherein R is hydrogen) with an acetylating agent. preferably a mixture of acetic anhydride. and. Pyridine) acylated. The 10 compound of the formula X thus obtained

₃₂₂₃ ( ₂₃₃ (

0 '

1-5, hydrogenated in the presence of a catalyst of massive activity - preferably palladium / barium sulfate - to o (z) -decene -1-ol-acetate of the formula I.

The effect of the preparation according to the invention is demonstrated by the following test experiments. The first attempt was made in Pestimre, between 16, June and. 3. .Τ -.- Ή 1980 carried out on a cabbage field of about 50 ha. The traps used consisted of two, in the middle tent-like bent plastic plates with dimensions of about 20 cm χ-30 cm. The plates were linked at their corners so that the tent-like curved. Firstees were perpendicular to each other. The internal T _e il the lower plate wurd.e lengths smeared with an adhesive to einzuf d.ie AINF lying insects. The Köde-r wurd.e in the center of the top plate from the inside aufgehäagt. The traps were set up at distances of 25 m from each other and at a height of 0.5 m. One trap per treatment was used. ·

The second test was in Törökbalint, ⁱⁿ an orchard of. about 5oo ha, between ^ - '' and IS, August 1981. The above traps

β ^ -φ η ·

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They are hung at a height of about 1.5 mm in the crown of the trees. "Three traps were kept in operation per treatment." - "-"

The _: trapped animals were collected weekly and determined by their species and genus. The. The results obtained were statistically evaluated according to the "Duncan Multiple Range Test". . '"*.' *

In the first experiment, male intrabate satellites were prepared using only the mixture of 7 (Z) - * dodecen-1-ol acetate and 9 (Z) -tetradecen-i-ol acetate and that consisting of three components Captured composition. The 5 (Z) -decene-1-ol aetate per se did not show any attractive effect. "The three-component composition attracts nearly four times more male winter sawn latex than the ^: from 7 (, Z) -dodecene. 1-ol-acetate and 9 (Z) -tetradecen-1-ol-acetaV existing mixture.

The results obtained are summarized in Table I.

In the second experiment, this gave rise to 5 (Z) -decene-1-ol acetate ',>.

about the same result as the mixture consisting of 7 (Z) -dodecene-1-ol-acetate and 9CZ) -lecradecene-1-ol-ac'-acetate. The number of trapped cases containing the composition consisting of three components (I + II + III) is more than ten times higher; this value is significant (? = 5 %) in a significant way.

The results obtained are shown in Table II.

The average values denoted by identical letters (a and b) do not differ significantly from each other at P = 5%. '.

Table 1

Compound 1 k: l (wt. %) Mixture h: 1: 2.5 (wt. %) ' (L, 0 iiiss ¹ ) of. IX and. ITl "Mixture of II, IXl and I

(1.0%) (1.5 mg)

By means of I; The number of one-year-old animals is 1nan.Lillc.l1e ti W i 111 e j 's a a t e e 1 e 11

Table TI

Verbiaduag Ϊ Ve x * b indungen II + III Compounds II + III + I (.1,0 mg-) {kA Gewv fo) Gew. (1,5 ing)

1 mg · 0.1 mg 0.01 ιιι, χ. 1: 1: 1 _r \

Dui elaschnit t the number of included ini cial w ilteries 11

7 a

Oa

12? B

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From the two tables I and II shows that the present invention, consisting of three components composition exerts a significantly stronger attractant effect on male winter Saateulen than die.beiden two previously known preparations. The synergistic effect demonstrated in the second experiment is particularly convincing.

embodiment

The invention will be explained in more detail with reference to the following examples. ;

example 1

There were 120 parts by weight of sunflower oil or paraffin oil with 80 parts by weight of η-hexane and 8 parts by weight of a Wirfcstoffgemisches of 4 parts by weight of compound of formula II, '1.5 parts by weight of compound of formula III and 2.5 parts by weight of compound of the formula I (ie weight ratio 4: 1.5: 2.5). From the solution obtained, an amount corresponding to an active ingredient combination of 0.1 to 0.3 mg was weighed into the correspondingly formed part of a trap, for example a rubber capsule or a polyethylene capillary. The solution of the active ingredient combination could either be added to the adhesive used to trap the insects or absorbed by textiles or natural or artificial porous materials.

Beispiel'2

The procedure was as described in Example 1, but with the difference that 10 parts by weight of paraffin oil. 1 part by weight of butylhydroxytoluene (2,6-di-tert-butyl-4-methyl-phenol),

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1 part by weight of a light stabilizer, for example Uvizon, BO. Parts by weight of n-hexane and 8 parts by weight of the active compound mixture (2.66 parts by weight of compound II and 2.6.7 parts by weight of compound, III) were used. ..

Example ^ .

There were 10 parts by weight of a Winkstoffkombination of 4 wt .- 'Iile compound of formula II, 1 part by weight of compound ' der'.Formel III and \ 3 parts by weight of compound compound

, - ik -

of formula I (ie weight ratio 4: 1: 3) mixed with 90 parts by weight of α-hexane and weighed in each case 1 to 2 mg of the drug combination containing amounts of this solution in traps. The drug solution was allowed to soak in polyethylenes of polypropylene capillary lareas with an inside diameter of 0.3 mm.

Example k 9 parts by weight of an active ingredient combination

from 3 parts by weight of compound I, 3 parts by weight of compound ( ^{~) 1 μl} - 3 parts by weight of compound III with 91 parts by weight of silicone oil homogenized and the adhesive used in traps in such Amount that in die'Fallen each 1 to 5 nig drug mixture, arrived, added.

Example 5

It wujrd.e. a flannel stripe with a

Width of 2 cm impregnated with that of Example 3 prepared drug combination solution in η-hexane. After evaporation of the η-hexane, the strip was welded between polyethylene sheets having a thickness of 0.1 to 0.5 μm. The mold thus prepared was to be kept in even distribution on the insects. "

^v - '' applied 25 collapsing field in such a way that 1.0 to 30 'mg / ha / active ingredient mixture passed into the airspace.

Example 6 ι

, i

The procedure was as in Example 5, but with the difference that the active ingredient combination solution was added in α-hexane to paraffin oil or odorless kerosene in such an amount that the resulting solution contained 30 to 50% by weight. Parts of η-hexane and. % By weight of paraffin oil or kerosene.

Example 7

, The procedure was as described in Example 1, but with the difference that. -An active ingredient mixture of k parts by weight of compound I, 2 parts by weight of compound II and. 2 parts by weight of compound III wurd.e used (ie weight ratio of the active ingredients

Example 8 . .

The procedure was as described in Example 1, jed.och with the difference ,, that an active ingredient mixture of 1 part by weight of compound I, 5 parts by weight of compound II and. 2 parts by weight of compound III was used (ie weight ratio of the active ingredient components .1: 5: 2).

Claims (3)

1-98% by weight of 7 (2) -dodecen-1-ol-acetate of the formula II GH ^ - (CH ₉₎ - C = C- (CH _{9) C-9} OC-CH CH- (II) H'H. '. 0 and 1-98% by weight of 9 (Z) -tetradecen-1-ol-acetate of the formula: III '" CH - (CH ₉ ) -CsC- (CH ₉ J ₇ -CH ₉ -OC-CH- (III) HH 0 optionally together with liquid and / or solid compounds. 'contains fertilizers and / or other excipients. 1. Lockatoff preparation for the selective attracting male Wintersaateulen (Scotia segetuin), characterized in that it comprises as active ingredient a mixture of 1-98 Gew .- ^ 5 (Z) -Becen-1-ol-acetate of the formula I. CH 1 - (CH ₉ ) - CsC- (CH ₉ ) - CH ₉ -O-CH- (I), HH-: 0 2 .Lockstoffpräparat according to item 1, characterized in that it comprises a mixture of 5-90 wt .- % compound of formula I, 50 - 90 wt - . % Compound of formula II and 5 - 90 "wt .-% compound of Contains formula III, 3. attractant preparation according to item 1 or 2, characterized in that it is an inert diluent - advantageous. η-hexane or dichloromethane - and / or a viscous liquid - preferably contains sunflower oil or paraffin oil » ,