CH671320A5 - - Google Patents

Description

DESCRIPTION

Grape wrappers are among the most important insect pests in viticulture worldwide. The two butterfly species found in Europe and the Near East are Eupoecilia (Clysia) ambiguella (Hb.) And Lobesia (Polychrosis) botrana (Schiff.).

Lobesia occurs in all classic winegrowing countries and can cause considerable yield losses. So far, grape winders have been made using the usual means, i.e. controlled non-specifically by using insecticides. Targeted control while sparing beneficial organisms (e.g. parasitic wasp species) is urgently required.

It is known per se that sex attractants from the group of the pheromones are produced in butterflies of female animals ready to mate and are excreted into the environment; male butterflies of the same type can then find the females with the help of this attractant.

There are basically three different ways to use sex attractants in crop protection:

- So-called pheromone traps, equipped with synthetic sex-attractant baits, are displayed in potential areas of infestation. Trapping male moths provides evidence of the occurrence of the pest. It is an important tool in integrated crop protection to determine the best time to fight using conventional methods (monitor technology). In this method of predicting the occurrence of Lobesia, the Lobesia sex attractant E7-Z9-Dodecadien-l-ylacetate, used as bait in traps, is used in viticulture, as described in DE-PS 2 440 759.

- by combining an attractant with insecticidal agents. It is possible to add insecticides to the bait / trap or to treat the trap only in the immediate vicinity. Most of the male moth population attracted from a distance can thus be killed (interception technique). The biotope load is reduced to an acceptable level.

- by the process of air space saturation with sex attractants or similar substances. The male butterflies are disturbed when the females are found, thus preventing the animals from mating. In this case, a larger amount of the attractant is evenly distributed in the air space throughout the entire crop to be protected, so that the males can feel the presence of the fragrance everywhere and their normal orientation behavior is disturbed (confusion method).

Even with this latter method of using sex attractants, only relatively small amounts of the active ingredients, which often only correspond to fractions of the usual doses of the classic insecticidal active ingredients, are required. (Birch (de.): Pheromones North Holland Pubi. Co. 1974). It is an extremely selective, non-toxic control method with the greatest possible protection of the non-target organisms, especially the beneficial organisms.

However, the natural sex attractants that are produced by the corresponding organs of the female animals are often difficult to access synthetically.

In addition, reliably effective control of Lobesia botrana with the aid of the known substance based on the confusion method mentioned has not been possible until now. Laboratory and small-scale experiments on influencing Lobesia botrana males with the confusion technique using the species' own sexual attractant, EZ, Z9-dodecadiene-nyl-l-acetate and with similar substances, namely Z-9-dode-cenyl-l-acetate, E -7-Dodecenyl-1-acetate and E7, E9-dode-cadienyl-1-acetate were carried out with unsuccessful success (ROEHRICH at. Al., Ann. Zool, Ecol. Quim. 1979, p. 659 ff. And the there indicated sites, GURE-VITZ and GOTHILF, Phytoparasitica 10, p. 140 (1982).

It is therefore an object of the invention to provide a compound effective as a confusion material and a method for its production, by means of which the control of the pests mentioned can be done more economically and reliably than before using the confusion technique.

It has now been found that preparations containing an alkylene in the formula I

ch3ch2ch = CH-C s C- (CH2) 6-OR

in which R stands for hydrogen or acetyl and in which the double bond in position 9 is either conf or trans

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671 320

guriert, or mixtures of the above compounds, an effective means of minimizing the population of Lobesia botrana due to a direct behavioral influence of the male moth. It has also been found that compounds of the formula I are suitable as sex attractants for pheromone traps for catching Lobesia botrana.

Form I alcohol and its acetate are described by Gazz. Chim. Italian 1982, 112 (5-6) 231-3. Biomed. Mass Spectrom. 1985, 12 (5) 200-7).

The known production method for the alcohol or its acetate proceeds with an unsatisfactory yield. A cheap manufacturing method for the two substances was therefore still sought.

It was found that the two substances can be obtained in good overall yield starting from tetrahydropyran-2-yl ether of oct-7-in-l-ol, according to the scheme below. According to this, two process variants are possible, namely either reacting 7-octyn-1-yl-tetrahydropy-ran-2-yl ether with butyllithium and ethyl formate in tetrahydrofuran to give (7-formyl-7-octyn-1-y]) - tetrahydro-

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pyran-2-yl ether, reacting (7-formyl-7-octyn-l-yl) tetrahydropyran-2 ether with n-propyl triphenylphosphonium bromide and potassium tert-butoxide in ether to form the 1-te tra-hydropyranyloxy-Z-9-dodecen-7-in, reaction of 1-Te-trahydropyranyloxy-Z-9-dodecen-7-in or with acetyl chloride in glacial acetic acid to l-acetoxy-Z-9-dodecen-7-in or Reaction of 7-octyn-l-yl-tetrahydropyran-2-yl ether with ethyl magnesium bromide, acrolein and acetyl chloride in tetrahydrofuran to l-tetrahydropyranyloxy-9-acetoxy-10-unde-cen-7-in, reaction of l- Tetrahydropyranyloxy-9-acetoxy-10-undecen-7-in with methylmagnesium chloride in tetrahydrofuran and diethyl ether to 1-tetrahydropyranyloxy-Z-9-dodecen-7-in, reacting 1-tetrahydropyranyloxy-Z-9-dodecen-7-in with Acetyl chloride in glacial acetic acid to 1-acetoxy-Z-9-dodecen-7-in.

The technically unsatisfactory production method for the natural attractant by partial hydrogenation of the corresponding acetylenically unsaturated compound can thus be substituted by an inexpensive production method for the substitute attractant (I).

Scheme

'0THP II

• no o

+ ch3coci ju

'0THP III

OAc

'0THP

© Br © + Ph3P ---

CH3HgCl

+ CH3COCI

-0THP IV

V

la

(Na2C03 / H201

Ib

Procedure 1

Procedure 2

THP =

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Synthesis of the compound of formula I according to Scheme 1

Method 1 l-tetrahydropyranyloxy-octin-7 (II)

8 moles of acetylene are introduced at 15 ° C. into a suspension of 184 g of 8 moles of LÌNH2 in 3 liters of DMSO. Then 1588 g (7.2 mol) of 1-tetra-hydropyranyloxyhexyl chloride are added dropwise with ice cooling. You stir overnight and work up as usual.

Distillation gives 250 gli. Bp 85-87 ° / 0.01 mbar l-tetrahydropyranyloxy-non-7-in-9-al (III) To a solution of 205 g 0.98 mol (II) in 1 liter tetrahydrofuran 700 ml n -Butyllithium added dropwise. The mixture is stirred at RT for 30 min and 148 g (2.0 mol) of ethyl formate in 150 ml of THF are added dropwise at −30 ° C. The mixture is stirred at 30 ° C. for 1 h, allowed to warm to RT and worked up as usual.

Yield 243 g (81.8% pure), which is further reacted without purification.

1-tetrahydropyranyloxy-Z-9-dodecen-7-in (IV) 168 g of potassium tert-butylate are added to a suspension of 481 g of n-propyl-triphenylphos-phonium bromide in 3 liters of ether. After stirring for 30 minutes at room temperature, 243 g (III) are added dropwise at 10 ° C. in the course of 3 minutes. After stirring for a further 30 min, the mixture is worked up in the customary manner. The crude product obtained is purified by chromatography (SiO 2 / cyclohexyan: ethyl acetate 4: 1). Yield: 187 g IV.

l-acetoxy-Z-9-dodecen-7-in (Ia)

27.5 g of acetyl chloride are added to 76 g (IV) in 300 ml of glacial acetic acid. The mixture is stirred for 5 h at 50 ° C., 15 h at room temperature, poured onto 1.5 liters of ice water and extracted with n-pentane. The extract is mixed with water and aqueous Na-CO3 solution. washed, dried over Na2SC> 4 and concentrated. Distillation gives 52 g la, bp 115 ° / 0.4 mbar.

Procedure 2

1 -T etrahydropyranyloxy-9-acetoxy-10-undecen-7-in (V) A solution of 170 mg (II) in 360 ml THF is added dropwise to a solution of 0.9 mol ethylmagnesium bromide in 300 ml THF. The mixture is heated to reflux for 1 hour, allowed to cool and a solution of 44 g of acrolein in 90 ml of THF is added dropwise at −30 ° C. The mixture is stirred at 0 ° C. for 2.5 h and 61.2 g of acetyl chloride are added dropwise at −20 °. After warming to room temperature and hydrolysis with saturated aqueous NH4C1 solution, the mixture is worked up as usual.

226 g of crude product are obtained, which can be converted further to (IV) without further purification.

1-tetrahydropyranyloxy-Z-9-dodecen-7-in (IV) To a solution of 2.7 g Q1Cl2, 1.7 g LiCl and 154 g (V) in 400 ml THF is at -25 ° -30 ° C a suspension of 0.8 mol of methyl magnesium chloride in 500 ml of diethyl ether was added dropwise. The mixture is stirred for 15 h at room temperature, hydrolyzed with saturated aqueous NH4C1 solution and worked up as usual. The crude product obtained is converted to Ia without further purification (see process 1).

Z-9-dodecen-7-in-ol-l (Ib)

100 g of la are heated in reflux in 500 ml of ethanol, 500 ml of water with addition of 200 g of Na2C03 for 5 h. After the usual work-up, the distillation of the crude product gives 83 g Ib bp 10170.3 mbar.

Both liquid and solid formulations are suitable for the use of the active ingredient as pheromone. High-boiling, aromatic, aliphatic or cycloaliphatic compounds are suitable as solvents. In addition to hydrocarbons, esters, ethers or ketones are particularly suitable. Typical representatives of these classes are e.g. Xylene, methylnaphthalenes, paraffin oils, cyclo-hexanone, ethyl glycol acetate, isophorone and dibutyl phthalate. These solvents can be used alone or in mixtures with other components. The saturated Ci2 esters corresponding to the compounds I and II and their homologs are particularly suitable formulation auxiliaries and can be regarded as synergists since they enhance the action of I and II.

Solutions can also be prepared in vegetable, animal or synthetic oils or fats and other evaporation-inhibiting solvents with low vapor pressure (such as dioctyl phthalate) for the purpose of prolonging the action.

It is also possible to bind the active ingredient in or to natural or synthetic solid carriers such as rubber, cork, cellulose, plastics, ground coal, wood flour, silicates, pumice, burnt clay or similar solid carriers or to use them in special capsule formulations or plastic containers to achieve an even release into the air over longer periods of time. In addition, the active ingredient can be evaporated from suitable containers (capillaries or other vessels) through narrow openings, whereby particularly uniform release is achieved over longer periods of time, and from multilayer plastic flakes.

The active substance content of these preparations can vary within wide limits. In general, the ratio of active ingredient to z. B. in the range of z. B. 10: 1 to 1: 103. In capsule formulations or other suitable containers, e.g. B. the active ingredient can be used in pure, undiluted form and its proportion by weight, based on the overall formulation, can be very high and amount to up to 90%. In general, however, very low concentrations of active ingredient in the preparations are sufficient to exert the desired effect on Lobesia males. A ratio of active substance to additive of 1: 3 to 1:10 2 is preferred.

The active ingredient can also be applied in comparatively high concentrations to prevent the males from mating by disorientation and confusion. Formulations with low-volatility additives that release the active ingredient in a protracted manner, such as rubber, cellulose, waxes, polymers or evaporation-inhibiting, low-volatility oils or paraffins, are best suited for this method, as are formulations in capsules or other containers (capillaries) that either loosen the attractant give up their wall or through narrow openings. The active ingredient concentration here is generally in the range from 1:10 to 1:103.

Application example

Field studies in potential Lobesia botrana infested areas prove the biological function of the claimed compound.

For this purpose, carrier strips made of rubber were impregnated with the compound I according to the invention and placed in trap bodies of the delta type with an adhesive surface. For comparison, trap bodies are hung with the species-specific active ingredient. At predetermined time intervals, the experiment was evaluated by counting the Lobesia males caught in the pheromone traps and arranged in Table 1 below.

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Table 1

Sum of Lobesia males caught in the period 14.05.-05.06.86 average of 2 repetitions

Bait Wachenheim Mussbach loading

Compound I [1.5 mg] 151.5 275.5

Compound I [4.0 mg] 177.0 236.5

Species active ingredient

E7Z9-12 AC [1mg] 233.0 272.0

(Comparison)

Application example 2 The experiments were carried out between 16.05. and 05.06.86 in Wachenheim / Weinstrasse.

Compound I was formulated in a suitable dispenser and applied by hand at a density of 1000 sources / ha in accordance with the confusion technique. Plots with a size of 900 m2 were treated with an application rate of 50 g or 100 g (I) / ha, as well as with 500 g / h of the active substance of the species. An untreated area served as a further comparison. The success of the confusion was evaluated by counting captured Lobesia males in pheromone traps, baited with the species' own attractant, which were distributed in a grid over the entire large area (treated plots / untreated areas). Success is measured by relating the trap catch in treated areas to catch in untreated areas. 100% success means that no males fly to the trap.

Table 2

Effect based on captured Lobesia males in pheromone traps; placed in the parcel center compared to traps in the parcel edge area

Concentration, trap parcels-% effect calculates parcel- center gradderVer-

edge

confusion

control

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_

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75.7

species-specific active ingredient

(Comparison)

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Claims (5)

671 320 1. Agent for combating the crossed grape moth Lobesia botrana, containing at least one active ingredient of the formula I. CH3CH2CH = CH - C = C - (CH2) 6 - OR (I), in which R represents hydrogen or acetyl and in which the double bond can be ice or trans-configured. 2. Composition according to claim 1, containing an active ingredient of formula I and additives, packaging aids and optionally synergists and production-related impurities. 2nd PATENT CLAIMS 3. A method for influencing the propagation rate of the crossed grape moth, characterized in that one uses an agent according to one of claims 1 and 2 or a mixture of these agents in such an amount that the male animals of the species are disturbed in the detection of the female animals . 4. A process for the preparation of a compound of formula I to be used as an active ingredient in an agent according to claim 1, characterized by the following steps: a) reacting 7-octyn-l-yl-tetrahydropyran-2-yl ether with butyllithium and ethyl formate in tetra-hydrofuran to give (7-formyl-7-octin-l-yl) tetrahydropyran-2-yl ether, b) Reaction of (7-formyl-7-octyn-l-yl) tetrahydro-pyran-2-yl ether with n-propyl triphenylphosphonium bromide and potassium tert-butylate in ether to give 1-tetra-hydropyra-nyloxy-Z- 9-dodecen-7-in, c) Reaction of l-tetrahydropyranyloxy-Z-9-dodecen-7-in with acetyl chloride in glacial acetic acid to l-acetoxy-Z-9-dode-cen-7-in. 5. A process for the preparation of a compound of formula 1 to be used as an active ingredient in an agent according to claim 1, characterized by the following steps: a) reacting 7-octyn-l-yl-tetrahydropyran-2-yl ether with ethyl magnesium bromide, acrolein and acetyl chloride in tetrahydrofuran to give l-tetrahydropyranyloxy-9-acetoxy-10-undecen-7-in, b) reacting l-tetrahydropyranyloxy-9-acetoxy-10-undecen-7-in with methyl magnesium chloride in tetrahydrofuran and diethyl ether to give l-tetrahydropyranyloxy-Z-9-dodecen-7-in, c) Reacting l-tetrahydropyranyloxy-7-9-dodecen-7-in with acetyl chloride in glacial acetic acid to give l-acetoxy-Z-9-dode-cen-7-in.