CS244658B2 - Agents with rodenticide effect and production method of the effective substance - Google Patents

Abstract

Compounds of the general formula (I), <IMAGE> (wherein A is oxygen or a valence bond, R<1> is a 1-tetralyl group or a group of the general formula (IV) or (V), <IMAGE> wherein Y stands for tert.-butyl, isobutyl, diphenylmethyl, 4-methyl- diphenylmethyl, 4-chloro-diphenylmethyl or 4-bromo-diphenylmethyl group and Q stands for phenyl, 4-chloro-phenyl or 2-furyl group, with the proviso that if A is a valence bond, R<1> represents a group of the general formula (IV), whereas if A is oxygen, R<1> represents the 1-tetralyl group or a group of the general formula (V), R<2> is hydrogen or a straight-chained or branched C1-22 alkyl or C12-20 alkenyl group, and R<3> and R<4> each stand for a straight-chained or branched C1-22 alkyl or C12-20 alkenyl group, and the total number of carbon atoms contained by the R<2>, R<3> and R<4> groups is more than 12) are rodenticides.

Description

BACKGROUND OF THE INVENTION The present invention relates to compositions having a redenticidal action and to a process for the manufacture of active substances containing them.

As is well known, the most effective anti-rodent formulations contain anticoagulants because they do not have a rapid effect and therefore do not raise suspicion of animals against baits. The most widespread compounds of this type are 4-hydroxycoumarin and 1,3-indanedione derivatives.

The enol tautomeric forms of 4-hydroxycoumarins and 1,3-indanediones are slightly acid in nature ₄ and therefore form salts with strong inorganic and organic bases. These salts are better soluble in water than the free 4-hydroxycoumarins and 1,3-indanediones and therefore are primarily applied in aqueous solutions, whereas aqueous agents, for example solutions in oil or other organic solvents, are usually prepared from the free compounds as described in U.S. Patent Nos. 2,687,365 and 2,900,302.

Various anti-rodent concentrates having 1-hydroxycoumarin or 1,3-indanedione derivatives have been described as active ingredients. German Patent Specification No. 2,227,843 discloses a concentrated solution of 2- (2,2-diphenylacetyl) -1,3-indanedione (difacinone) and 2- (2- (4-chlorophenyl) 2-phenylacetyl) -1,3-indanedione. (chlorfacinone) in polyethylene glycol, this solution contains 0.01-15 g / kg of active ingredient.

Concentrated solutions of chlorfacinone in compounds which are homologues of benzene have also been described, these solutions containing 50 to 100 g / liter of active ingredient and have been described in German Patent Specification No. 2,341,835.

The concentrates can be diluted with water before use and the diluted solutions are applied as a spray, added to drinking water or used to impregnate cereals.

French Patent No. 95,858 discloses a rat control compound in a formulation consisting of dehydrated different vegetables that are impregnated with an oil solution of chlorfacinone. The active ingredient content of the oil solution is 0.25 to 0.75 g / liter and the bait is 0.002 to 0.0065%.

French Patent No. 1 601 076 discloses oil solutions containing 0.25 to 0.75 g / liter of warfarin, i.e. 2-oxo-3- (1-phenyl-3-oxobutyl) -4-hydroxycoumarin, this oil solution can be used to prepare baits.

Oil concentrates of difacinone have also been described in German Patent Specification No. 2,218,893. Less toxic concentrates contain 0.1 to 2.5 g / liter of active ingredient, more toxic concentrates contain 2.5 to 5.0 g / liter of active ingredient .

This high active ingredient content can only be kept dissolved in the hot state, so that the heated solution is needed immediately for bait preparation.

Oil concentrates of 1,3-indanedione and derivatives thereof are also described in German Patent No. 2,753,183. These concentrates contain up to 50 g / liter, i.e. up to 5% by weight of the active ingredient and have an increased shelf life. Permanent and storable oil concentrates of 1,4-indanedione derivatives with a content of more than 5% have not been described in the literature.

The prior art concentrates containing organic solvents, for example benzene homologs, polyglycols and the like, have the disadvantage that they do not form stable emulsions upon dilution with water. A further disadvantage is that when these aqueous emulsions are applied to cereals and other consumables, such as dried apples, dried carrots and the like, the water content increases so that these baits need to be dried again to prevent mold production and growth. It is therefore a very complicated method of making baits, consuming a great deal of time and energy, and is therefore not economically applicable to large-scale rodent baits.

Oil concentrates have some advantages over concentrates in organic solvents. One of the main advantages is that the oil impregnated with oil concentrate does not need to be dried and the baits prepared with the oil concentrate are much more resistant to moisture than the baits in organic solvents.

In addition, the mineral oil fraction attracts rodents. It is therefore very disadvantageous that the indandione and hydroxycoumarin derivatives are far less soluble in oils than in benzene, homologous compounds or polyglycols. Most of the known oil concentrates contain a maximum of 2 to 2.5 g / liter, i.e. 0.20 to 0.25% by weight of the active ingredient, and even this relatively low active ingredient content is excreted from solution upon storage.

Permanent oil concentrates having a higher active ingredient content of up to 5% by weight have been described only for certain derivatives of 2- (2,2-diphenylacetyl) -1,3-idanedione, in German Patent Specification No. 2,753,183.

The relatively low solubility results in the disadvantage that the concentrate has to be applied to a support, for example cereal grains, dried vegetables, dried fruits and the like in large amounts which are relatively slowly absorbed by hydrophilic materials or more concentrated but unstable solutions have to be used.

Both methods also contain a number of disadvantages that prevent the widespread use of oil concentrates in the large-scale production of rodent baits.

The relatively low active substance content of the known oil concentrates also makes it necessary to store large quantities of solutions and to transport these large quantities, which considerably increases the cost of rodent control.

SUMMARY OF THE INVENTION It is an object of the present invention to overcome the above disadvantages.

The invention is based on the discovery that 4-hydroxycoumarin and 1,3-indanedione derivatives commonly used against rodents form salts not only with inorganic bases and the lower alkylamines or alkanolamines described in the literature, but also with less basic aliphatic secondary and tertiary long chain amines with a steric gill, in this case adducts of an oily or waxy nature, which can be dissolved in oils and other organic liquids at any desired concentration.

These compounds can be represented by formula (I)

OH

where

A represents an oxygen atom or a chemical bond r! represents a 1-tetralyl group or a group of formula IV or V

o (IV)

Q

CH - CH ₂

C - CH • t 3 o (V)

where

Y is tert-butyl, isobutyl, diphenylmethyl, 4-methyldidienylmethyl, 4-chlorodiphenylmethyl or 4-bromodiphentylmethyl; and

Q is phenyl, 4-chlorophenyl,

R represents a hydrogen atom or a straight or branched chain alkyl of 1 to 22 carbon atoms or a straight or branched chain alkenyl of 12 to 20 carbon atoms, and

4

R and R are independently straight or branched chain alkyl of 1 to 22 carbon atoms or straight or branched chain alkenyl of 12 to 20 carbon atoms, provided that when:

A means a chemical bond, means

R ¹ SKU ^pi nu ^{b h} Proceed with the Formula IV and if

A is an oxygen atom,

R ³ mean ^s sk.upinu formula ^IV or ^V, wherein p ^{s o} ce AC number in ^hlík ovýc ^h ome ^t in tuentec subst ^{i H} R R R ^{R 3} and ^Y are education ^Ys Width than ^{the 12th}

Similar salts of the derivatives of 2- (2,2-diphenyl hacetyh ^yl) -1,3-indandione formula VI wherein

R ^X and R ^Y and ^t om ^y vocMu atom ^yh and ^l ogen or a ^lkyl b ^s ZB ^{yt alkyl} of ^{1 and} 4 atomec ^H atoms formed with secondary or tertiary amines have been described in German Pat. A molar equivalent of the indandione derivative of formula (VI) is contacted with 0.2 to 10 molar equivalents of the amine in an oil solvent to form an oil concentrate having an active ingredient content of up to 5% by weight, expressed as the free indandione compound.

Some of these amine salts were also isolated in pure form and identified.

However, those compounds which have been identified are salts with lower acyclic or cyclic amines and are crystalline.

The addition compounds of the above 2- (2,2-diphenthacetyl) -1,3-indanedione derivatives with higher acyclic amines have never been isolated or described in the above literature, so it has also not been known that these addition compounds are oily or waxy substances. which can be mixed with oils in any desired ratio to form stable materials. In the patent specification, there is an upper limit of 5% by weight of the active ingredient content, i.e. the authors considered it to be a solubility limit and that it is not possible to obtain higher active ingredient oil solutions from amine salts.

Thus, it is evident that the addition compounds of the 2- (2,2-diphenylacetyl) -1,3-indanedione derivatives of the general formula VI with higher acyclic amines are novel compounds because their physicochemical properties have not yet been known and given the expected highest concentration reported in the aforementioned patent, there is no indication of the advantageous solubility of these compounds.

The compounds may be used for the production of rodent-containing concentrates, the concentrates containing one or more compounds of the formula I in an amount of 0.3 to 95% by weight, preferably 1 to 95% by weight, in particular 10 to 95% by weight, most preferably 20 to 95% by weight together with the liquid organic diluent and optionally other additives such as coloring agents, flavoring agents, fragrances, preservatives and potency enhancers and / or agents having a similar effect, attractants rodents or repel other animals and the like.

The invention therefore provides a composition having a rodenticidal action, characterized in that it contains a compound of the formula I as active substance.

where

A represents an oxygen atom or a chemical bond,

R ¹ is 1-tetralyl group or a group of formula IV or V

-C - Y i (IV)

Q

AND

- CH - CH _n - C - CH ..

il o (V) where

Y is tert-butyl, isobutyl, diphenylmethyl, 4-methyldiphenylmethyl, 4-chlorodiphenylmethyl or 4-bromodiphenylmethyl _; la

Q is phenyl, 4-chlorophenyl,

R ² is hydrogen or alkyl of 1 to 22 carbon atoms in a straight or branched alkenyl or straight or branched chain of 12-20 carbon atoms,

R ³ and R ⁴ are each independently straight or branched chain alkyl of 1 to 22 carbon atoms or straight or branched chain alkenyl of 12 to 20 carbon atoms, provided that when:

A means a chemical bond, means

R ^{1 is a} group of formula (IV) and, if:

A is oxygen, ^R is not ^plated sk.u ^pi nu formula IV or V,

Wherein the total number of carbon atoms in the R, R and R substituents is always greater than 12 in an amount of 0.001 to 95% by weight in admixture with a solid, liquid and / or gaseous carrier and / or other conventional additive, If the amount of active ingredient in the composition is greater than 0.3% by weight, the carrier is always liquid.

The invention also relates to a process for the preparation of active compounds of the formula I, characterized in that a compound of the formula II is reacted

(II) where

A and R 'are as defined above, with an amine of formula III

(III) where

3 4 _z

R, R, and R are as defined above.

Especially preferred compositions of this type are baits ready for use and containing a compound of formula I or a concentrate thereof on a conventional carrier surface, such as cereal grain, dried vegetables and the like.

The compounds of formula (I) can be obtained by reacting a compound of formula (II) in the process of the invention

OH

where

R ¹ and A maj ^s Uve ^d Eny above meanings, with an amine of formula III

(III) where

234

R, R and R are as defined above.

It will be appreciated that the compounds of formula (II) and hence the compounds of formula (I) may exist as enol tautomers and oxotautomers. For simplicity, both the starting materials and the resulting products have been designated as enol tautomers. It will be understood, however, that the process of the invention also relates to oxotautomers and mixtures of both tautomers. That is, the terms of the compound of formula (I) and the compound of formula (II) include both the above tautomers and mixtures thereof in any ratio.

Some of the compounds of formula (II) used as starting materials are listed in Table 1 below.

Tabu1 кa 1

AR ¹ Common name

oxygen 1-phenyl-3-oxobutyl Warfarine oxygen 1- (4-chlorophenyl) -3-oxobutyl Cumachlor oxygen 1- (2-Furyl) -3-oxobutyl Fumarine oxygen 1,2,3,4-tetrahydro-1-naphthyl Cumatetralyl chemical bond 2,2-dimethylpropionyl Pindone chemical bond 2,2-Diphenylacetyl Difacinone chemical bond 2- (4-chlorophenyl) -2-phenylacetyl Chlorofacinone chemical bond 2- (4-bromophenyl) -2-phenylacetyl Bromfacinone chemical bond 2- (4-methylphenyl) -2-phenylacetyl Fentolactine chemical bond 3-methylbutyryl Valone

All of the compounds of formula II listed in Table 1 are known and used as rodent control agents, as disclosed in R. Wegler: Chemieder Pflanzenschutz- und Schadlingsbekampfungsmittel; Springer Verlag, 1970, Vol. I, pp. 614-627.

Preferred aliphatic amines of formula III used as reactants in the process of the invention are the following compounds: N, N-dimethyldodecylamine, N, N-dimethyltridecylamine, N, N-dimethylhexadecylamine, trioctylamine, bis (dodecyl) amine, tris (dodecyl) amine, bis (tridecyl) amine, tris (tridecyl) amine, bis (hexadecyl) amine and bis (octadecyl) amine.

The addition compounds of the formula I are prepared by the process according to the invention in a simple manner by adding an equimolar amount of the amine of the formula III to the starting material of the formula II and converting this mixture into a homogeneous melt, preferably by stirring or heating.

The reaction can also be carried out in the presence of an inert solvent and can be removed after completion of the reaction, for example by evaporation. The small amount of heat generated by mixing the two components is usually sufficient to provide a sufficient reaction rate, but in some cases the reaction may be accelerated or completed by heating the reaction mixture.

Heating of the mixture is particularly advantageous if any of the reactants do not dissolve sufficiently.

If less pure reagents are used, for example technical grade, one of the reagents may be used in excess and the reaction may be carried out in an inert liquid which is a less suitable solvent for the amine of formula III or the starting material. of formula II.

In this case, the component which has been used in excess and which has not reacted can be removed very easily simultaneously with the impurities cd of the dissolved final product. It is sometimes advantageous to carry out the reaction in the presence of an inert liquid which does not dissolve or dissolves the prospective product very little.

In this case, the addition compound of the formula I precipitates out of solution as a waxy substance or as an immiscible oil phase and can be removed very easily, for example, by alloying.

The order of the reactants and the solvent or solvent mixture must be chosen on a case-by-case basis depending on the reaction conditions and the nature of the reactants. If the compounds of the formula I are to be obtained in pure form, solubility must be considered, since once the resulting product is oily or resinous, the impurity is very difficult to remove.

It is clear that for the use of the compounds of the formula I against rodents, it is not necessary that the compounds are obtained in pure form. Thus, low purity compounds of formula (I) prepared from 4-hydroxycoumarin or 1,3-indanedione and an amine of technical grade can be used.

Typically, the amines of formula III contain an isomeric compound or lower or higher homologues as an impurity. If such a mixture of amines is used, the resulting product is also a mixture of addition compounds of formula I.

However, these mixtures can advantageously be used for the production of concentrates and anti-rodent compositions. In particular, the technical product genamine (Hoechst A.B.), aliphatic amines of 14 to 40 carbon atoms, individually or in the form of a mixture, can be used advantageously in the process according to the invention.

As mentioned above, the anti-rodent compositions and concentrates may contain one or more compounds of the formula I as active ingredient in a total amount of 0.3 to 95% by weight. This amount corresponds to 0.2 to 60% by weight of the compounds of formula II.

When the active ingredient is a mixture of compounds of formula I, it may be, for example, a mixture of addition compounds obtained from various compounds of formula II with a given amine of formula III or a mixture of addition compounds obtained from a given compound of formula II and a greater number amines of formula III.

These mixtures can be obtained in a single reaction step. Alternatively, the individual compounds of formula (I) are obtained first, and the resulting compounds are then mixed together in the desired ratio.

The rodenticidal concentrates according to the invention contain, in addition to the active compound of the formula I, one or more organic diluents. It is preferred to use high boiling hydrocarbons such as mineral oil fractions such as paraffin, petrolatum, spindle oil and the like, vegetable oils such as sunflower oil, rapeseed oil, flaxseed oil and the like, animal fats such as various fish oils, synthetic oils such as silicone oils, glycerides of fatty acids, aliphatic alcohols, in ^one network aliphatic acid, preferably a unsaturated or a mixture of these compounds.

The concentrates, especially those with a high active ingredient content, can also contain free amines of the general formula III as diluents. In addition, organic solvents which are non-toxic to plants, for example alcohols, ketones, hydrocarbons, esters or mixtures thereof, may be used as liquid diluents, individually or in admixture or in admixture with the aforementioned diluents. Particularly preferred diluents are mineral oil fractions, in particular petrolatum.

The anti-rodent concentrates of the invention may also contain conventional additives, for example, flavoring agents such as sweeteners, fragrances, coloring agents, preservatives, wetting agents or substances having a similar effect or extending the effectiveness of the above active agents such as calciferol, sulfonamides, acetylsalicylic acid , phenylbutazone and the like.

In addition to the concentrates, other anti-rodent compositions can be obtained from the compounds of formula (I). These compositions can be obtained in a known manner using compounds of the formula I or concentrates as starting materials.

Oil concentrates may be used, optionally after dilution, and applied to cereal grains, dried vegetables, dried fruits and the like to provide rodent baits. The concentrates may be mixed with a propellant such as difluorodichloromethane to form aerosols.

The compounds of formula (I) or oil concentrates thereof may be mixed with inert, non-toxic organic solvents such as alcohols, esters, ketones, hydrocarbons, or mixtures thereof to provide a crop protection spray.

. The emulsifiable concentrates may contain, in addition to the active ingredients and solvents, for example oils, esters, ketones and the like, one or more surfactants. These emulsifiable concentrates are diluted with water to the desired concentration before use and then used as a spray onto the treated areas.

The compounds of formula (I) may also be dissolved in organic solvents of a non-oil nature, for example alcohols, ketones, lower hydrocarbons, to form concentrates which can be used, for example, for the manufacture of baits as described above.

The anti - rodent composition may contain, in addition to the active ingredient, a liquid, solid and / or gaseous carrier, conventional additives and auxiliaries such as wetting agents, flavorings, fragrances,. dyes or preservatives.

These compositions contain the active compound of the formula I in an amount of 0.001 to 95% by weight.

The main advantages of the invention over the prior art are as follows:

1) It is possible to obtain concentrates having a very high active substance content, several orders of magnitude higher than usual, these concentrates of the compounds of formula I being stable even without heating and can be stored for a long period of time unchanged. This avoids the difficulties commonly encountered in the storage of concentrates.

2) It is easy to prepare rodent baits inexpensively and on a large scale.

The selection of carriers for these baits can be expanded, since the concentrates produced by the process of the invention can be easily applied to carriers that have not previously been used because they are unable to absorb large amounts of oil. However, from another point of view, for example due to rodent habits and the like, it would be advantageous to use such carriers. In addition, the novel compounds of the formula I are much better soluble in organic liquids of a non-oil nature than the corresponding 4-hydroxycoumarin and 1,3-indanedione derivatives of the formula II, which is very advantageous, for example, when used in spray form.

3) The novel compounds of the formula I and their oil concentrates can be mixed very well with the diluents without long stirring or heating, so that dilute formulations can be easily obtained, for example in the form of a spray.

The invention will be illustrated by the following examples.

Example 1

A mixture of 1 g (3.42 mmol) coumatetralyl and 1.3 g (3.42 mmol) of bis (tridecyl) amine are stirred for ^instance IT ^e fence 12 ° to ¹³⁰ ° C ^d of MMN ^also in homogeneous ^or Tave ^ n ^ which ^A then ZCH ad ^{i l} te ^pl ol room. Coumatetralyl salt with bis (tridecyl) -amine was obtained as a colorless, sticky resin ^{and L, and} weave. Product ^H not have ^at that ^I lo ^{p -} 1 ² ° C and the ^ARI sUovkou ^yl ^ HMO.

The resulting product readily dissolves at room temperature in 5 volumes of petrolatum, sunflower oil or glycrol trioleate. In contrast, the starting cumatetralyl can be dissolved at room temperature. ρο! ΐ: ν in 2,500 parts by volume petroleum jelly, 920 parts by sunflower oil, 150 parts by volume. glycerol trioleate.

Example 2

A mixture of 4.18 g (15.5 mmol) of dimethylhexadecylamine, 5.82 g (15.5 mmol) of chlorofacinone and 20 ml of n-hexane was heated at reflux for 1 hour. During this time, solid chlorfacinone dissolves completely and a clear, orange-yellow solution is formed. The solvent was evaporated to give the chlorfacinone salt with dimethylhexadecylamine as a yellow-brown thick oily residue, ηθ = 1.5731.

The product does not crystallize upon cooling but forms a glassy substance at -32 ° C.

H, 8.45; Cl, 5.50. Found: C, 76.53; H, 8.52; Cl, 5.46. .

Example. 3

A mixture of 2 g (3.83 mmol) of tris (dodecyl) amine and 40 ml of hexane is heated to reflux. Divacinone is added in small portions of 0.1 g until the last portion dissolves when boiling. A total of 1.43 g of difacinone is added. The mixture was cooled and allowed to stand for 2 days to eliminate excess difacinone in crystalline form. The crystals were collected by filtration, passed through a small amount of hexane, the filtrate was combined with the wash liquid and the solvent was evaporated.

0.11 g of unreacted difacinone was removed. That is, 1.32 g (3.87 mmol) of difacinone, equivalent to the amine used, was involved in the reaction.

In this way, the tris (dodecyl) amine salt with difacinone is obtained as a tan oil.

0 η _β = 1.5348. The product does not crystallize upon cooling but forms a glassy solid at -55 ° C.

Example 4

A mixture of 1 g (2.67 mmol) of chlorfacinone, 1.14 g (3.2 mmol) of tris (octyl) amine and 50 ml of acetonitrile is refluxed until the amount of tris (octyl) amine present as a separate the phase no longer shrinks and a nearly homogeneous solution is formed.

The mixture was cooled to room temperature, the excess tris (octyl) amine was separated and the acetonitrile solution was cooled to -18 ° C. The tris (octyl) amine salt with chlorfacinone is deposited on the walls of the vessel as a tan resin. The solvent is decanted off, the resin product is washed twice with 15 ml of acetonitrile, the product is always dissolved and then frozen and traces of solvent are then removed in vacuo.

0.51 g of a resin is obtained. ηθ ° = 1.5582. The product does not crystallize upon cooling, but forms a glassy solid at -10 ° C.

H, 8.76; Cl, 4.89%. Found: C, 77.87; H, 8.81; Cl, 4.78%.

The resulting product is well soluble in alcohols, acetone, hexane and dichloromethane even at room temperature. 1 g of the starting chlorofacinone can be dissolved only in 1000 ml of n-hexane at room temperature.

Example 5

A mixture of 1 g (2.67 mmol) of chlorofacinone, 0.7 g (3.28 mmol) of dimethyldodecylamine and 100 ml of n-hexane is heated to reflux. Solid chlorfacinone dissolves completely within 20 minutes while precipitating the resulting product as a tan oil phase. The reaction mixture was cooled and the hexane phase containing excess amine was decanted. 20 ml of hexane are added to the oily product, the mixture is boiled and left. and the hexane phase is decanted. This purification is carried out two more times and finally the oil product is freed of solvent residues under vacuum.

0.81 g of the dimethyldodecylamine salt of chlorofacinone is obtained as a yellow-brown thick oil. η ^ θ = 1.5858. The product does not crystallize po'zchlazení, but forms a glassy ^{solid at} u te ^{P I} lo ^-22 ° C.

Analysis for C37H ₄ gClNO3 'Calculated: C 75.55%, H 7.88%, Cl: 6.03% Found C: 75.70%, H 8.12%, Cl: 5.90 %. .

The product dissolves very well at room temperature in 1 volume of methanol, acetone or benzene. In contrast to this solubility, 1 g of the starting chlorfacinone can be dissolved only in 1370 ml of methanol, 41 ml of acetone or 8 ml of benzene at room temperature.

Examples 6 to 10

The procedure of the previous examples was carried out to obtain the products listed in Table 2 using the starting materials of Table 2.

Table 2

Example number Starting materials (II) (III) Method (example) Properties of the resulting product 20 Color Appearance η _β Freezing temperature (° C) 6 chlorofacinone bis (tridecyl) amine 5 yellow-brown. . resin 1.5445 +20 7 chlorofacinone tris (dodecyl) amine 2 orange-yellow oil 1.5420 0 8 chlorofacinone tris (octyl) amine me ^l t * buff oil 1,5600 + 10 9 ‘Difacinone dimethyl dodecylamine 2 brown oil 1,5800 + 10 10 difacinone dimethyl-hexadecylamine 2 dark brown oil 1.5648 + 17 11 valone dimethyl dodecylamine 5 lemon yellow kryst. substance 57-59 12 valone tris (octyl) amine ₁ mel t brown-red oil 1.5192 -15 13 valone tris (dodecyl) amine i me ^lt brown-red oil 1.4955 -15 14 coumatetralyl tris (dodecyl) amine 1 orange yellow oil 1.5215 + 4 15 Dec coumatetralyl dimethyl-hexadecylamine 1 light cream kryst. substance 70-71 16 coumatetralyl dimethyl dodecylamine 1 light cream kryst. substance 52-53 17 warfarine dimethyl dodecylamine me ^l .t ^X golden yellow oil 1,5527 0

continuation of Table 2

Example number Starting materials (II) (III) Method (example) Properties of the resulting product 20 Color vzMed n _D Freezing temperature ( ^O C) 18 warfarine tris (olctyl) amine 1 yellow-brown oil 1.5322 -12 19 Dec warfarine tris (dodecyl) amine 1 orange yellow oil 1,5188 + 2 20 May coumachlor dimethth-dcdectla4in me ^l t * yellow-brown

Oil 1.5439 * The same procedure as in Example 1 or 2 was followed except that no solvent was used. The reaction is carried out in the melt of the starting materials.

Example 11.

A concentrate is prepared by mixing the following ingredients at the indicated ratio:

% by weight

91.8

8.2

Chlorofacinone salt with amine mixture (Genamin SO 302D)

Genamine SO 302D

Genamine SO 302D is a mixture of dimethtl- (larger alkylamines and dimethth (higher alkenylamines). Higher alkyl and alkenyl groups contain 14, 16 and 18 carbon atoms. This mixture is supplied by Hoechst A.G.

The concentrate contained 91.8% by weight of the salt mixture, corresponding to 50% by weight of chlorfacinone.

The concentrate is a homogeneous, clear, orange-yellow thick oily liquid that remains in a liquid state when stored at room temperature. The concentrate can be easily diluted with alcohols, aromatic solvents and ketones. Physical properties of the concentrate are as follows: s ^p ecific ^K and ^H Weigth ^{0.939 i} «^ / ш ^1, η ^ = ^ ^5711, vis ^{OZ and} the ^p s = ⁵⁰ ° C" 790 cSt.

Example 12

The concentrate is obtained by mixing the following components in the indicated ratio:

Diphacinone salt with Sudan Rot 7B trioctylamine (BASF AG) Vaseline oil

10.4 g g

990 ml

The concentrate contains said salt in an amount of 5 g / liter, i.e. 0.58% by weight of difacinone. The concentrate is a completely clear, dark red solution that does not contain sediment. Specific motnos ^K and ^{H t} is ^0.854 «^ / ш ¹ vistoz and ^{at t} ^ e ^{I pl} of ⁵⁰ ° C is ^10.1 cSt. ^The oncentr mcréno ^and T is used without dilution ^к production of rodenticidal baits.

Example 13

The concentrate is obtained by mixing the following components in the indicated ratio:

Component parts by weight

Tris (dodecyl) amine salt with chlorfacinone 62.5

Sudan Rot 7B Flussig (BASF AB) 37.5

The concentrate contains 25% by weight of chlorfacinone salt. The concentrate is a dark red, almost black, thick, oily liquid, free of sediment. The specific gravity is 1.03 g / ml, the viscosity at 50 ° C is 178 cSt. The concentrate can be used after dilution to produce rodent baits.

For example, 1 kg of concentrate can be diluted with paraffin or petrolatum oil to a volume of 100 liters to give an oil solution having a concentration of 0.25% by weight of chlorfacinone. With this solution it is possible to impregnate cereal grains with a known batch.

Example 14

An emulsifiable concentrate can be obtained by mixing the ratio of:

of the following ingredients in said

The concentrate component of Example 11 isopropanol

Nonit (wetting agent, Egyesult Vegyimuvek) g

This emulsifiable concentrate contains a mixture of amine salts with chlorfacinone in an amount corresponding to 10% by weight of chlorfacinone. Before use, this concentrate is diluted with water to the desired final concentration.

on

The amount of water added depends on the spraying technique. For example, when g of the above-mentioned emulsifiable concentrate is poured into 100 ml of water while stirring, a milk-like fine emulsion is obtained which can be used to spray green plants, for example with alfalfa, thereby protecting them against aphids.

The ready-to-use emulsion comprises a mixture of amine salts with chlorfacinone in an amount corresponding to 50 ppm of chlorfacinone.

Example 15

The concentrate prepared according to Example 13 was diluted with a mixture of 1 volume of sunflower oil and 9 volumes of petrolatum oil to form a solution containing the chlorfacinone salt in an amount corresponding to 10 g / liter of chlorfacinone. 0.75 liters of dilute solution is applied to 100 kg of wheat, rice or barley.

The grains quickly absorb an oily solution and almost immediately a dry product is obtained without nutrients or days. A red rodent bait is obtained which contains an amount equivalent to 75 ppm of chlorfacinone. This bait is used at a rate of 15 to 20 kg / ha depending on the extent of the damage. The effectiveness of the bait to wait several chlorfacinone salts in killing the bites in is 95-100%.

Example 16

1.5 liters of the oil concentrate prepared according to Example 12 are applied to 100 kg of ground maize having a particle size of 3 to 5 mm. The resulting rodent bait contains a salt of difacinone in an amount equivalent to 75 ppm of difacinone.

Example 17

The concentrate prepared according to the method of Example 13 is diluted with petrolatum oil to an active substance content of 10 g / liter expressed as chlorfacinone. The resulting oil solution was applied to crushed corn kernels in an amount of 1 liter per 100 kg in a rotating drum. The resulting bait for a dose contains 300 ppm of the active ingredient, expressed as chlorfacinone, and can be used with good results to control hamsters.

Example 28

A concentrate containing 20% by weight coumatetralyl is prepared by mixing the following components in the proportions indicated:

coumatetralyl salt with bis (tridecyl) amine vaseline oil liquid sudan blue B (liquid dye supplied by BASF AG) by weight% by weight% by weight

The concentrate is a dark blue, almost black, viscous oil that retains its liquid nature when stored at room temperature. This concentrate can only be used in the preparation of the compositions of the invention after dilution.

For example, 100 g of the above concentrate can be diluted to a final volume of 1 liter with vaseline oil, rapeseed oil or an oil of a similar type or mixtures thereof. The resulting oily mixture contains the active ingredient in an amount corresponding to a concentration of coumatetralyl of 20 g / liter and can be used directly for the manufacture of rodent baits or other compositions of a similar type.

Example 29

The diluted oily mixture prepared by the method of Example 28 containing 20 g / l (2 w / v%) of active ingredient, expressed as coumatetralyl, was applied to the surface of wheat or rice in an amount of 5 ml / 1 kg. The dried rodent bait has a characteristic blue color and contains 100 ppm, i.e. 0.01% of active ingredient, expressed as coumatetralyl.

Example 30

By combining the following ingredients, a concentrate containing the active ingredient in an amount of 20 g / liter can be obtained:

a salt of warfarin with a bis (tridecyl) amine

4.48 g

phenylbutazone 2 ₍ , 0 g sudan red 7B (supplied by BASF AG) 0, , 2 g cod oil liver 15 Dec ml horological oil 76 ml silicone oil 4 ml

The salt is obtained by reacting warfarin with a bis (tridecyl) amine. Salt is yellow honey-like substance that upon zcMazení not ^to single crystal ^{and lyophilized,} salt -tuhne EPLO ^{I at t 20} ° C ηθθ = 1, ⁵³⁴ second

Phenylbutazone is a substance that enhances the effectiveness of the composition. Cod liver oil also enhances efficacy due to its vitamin D content, in addition it forms part of the liquid diluent.

The oily concentrate of the foregoing composition is a dark red, clear solution that can be stored unchanged for extended periods of time. The solution contains the active ingredient in an amount corresponding to 2.0% (w / v), i.e. 2.2% by weight of warfarin, and can be used directly for the manufacture of baits or other rodent control agents.

EXAMPLE 31 ml of an oily concentrate prepared according to the method of Example 30 containing 2% by weight of the active ingredient, expressed as warfarin, are applied to the surface of 1 kg of crushed dried vegetables. The resulting granulate is a suitable rodent bait and contains 200 ppm, that is, 0.02% warfarin.

When a highly concentrated oily concentrate of warfarin containing 0.75 g / liter of active ingredient is used in the above process, 1 kg of solid carrier is treated with 85 ml of an oil solution. The adsorption of this large proportion of oil solution requires several days.

When, 10 ml oily If the oil concentrate according to Example 30 is used, only a solution per 1 kg of carrier is required and adsorption occurs within minutes. Example 32 Concentrate containing a total of 25% by weight of the two active substances, expressed as

as coumatetralyl + chlorofacinone is obtained by mixing the following ingredients in the indicated amounts:

salt mixture, obtained from 1 g coumatetralyl, 1 g chlorfacinone and 3,3 g5,3 g tris (dodecyl) amine glycerol trioleate 1,2g liquid sudan red 7B (50% oil solution of red dye, supplied by BASF) 1,4g aniseed oil 0 , 1g

The concentrate is a dark red, thick oil that can be stored for a longer period of time unchanged.

When diluted with an oily substance such as glycerol trioleate, olive oil, sunflower oil and / or paraffin oil, it can be easily applied to the surface of the cereal seed to provide rodent bait.

Results of biological tests

The acute toxicity of the compounds listed in Table 3 below was determined in laboratory white rats of the LATI strain in domestic mice and musk rats as follows:

The compounds were dissolved in vaseline oil and the solutions were applied to the surface of the ground maize having a particle size of 3-5 mm. The animals were fed with this bait and given sufficient water. 100 animals were used for each test, 50 males and 50 females. The animals were followed for a week and then calculated according to the number of animals dead. The results are shown in Table 3 below.

Table 3

Compound ^LD 5 0 Laboratory white rats in mg / kg orally homemade mouse musk rats chlorfacinone TDOA 45-50 330-360 43-50 difacinone TDOA 40-45 380-420 warfarine TDOA approx. 500 approx. 1 000 coumatetralyl TDOA 45-50 60-70 valone TDOA approx. 150 coumachlor TDOA 900-1 000

TDOA = tris (dodecyl) amine salt

Claims (3)

A composition having a rodenticidal action, a compound of the general formula I, characterized in that it contains as active ingredient (I): A represents an oxygen atom or a bond, ^R1 is ^t l ^-t e r ^yl cord for ^{the PI} at a wall or a group otiecncho formula IV or V -C - Y i * 0 (IV) Q - CH - CH ₂ - C - CH ₃ 0 (V) where Y is tert-butyl, isobutyl, diphenylmethyl, 4-methyldiphenylmethyl, 4-chlorodiphenylmethyl or 4-bromodiphenylmethyl; and Q is phenyl, 4-chlorophenyl, R is hydrogen or alkyl of 1 to 22 carbon atoms, straight or branched chain or alkenyl straight or branched chain of 12-20 carbon atoms and ^R3 and ^R4 than ^ sle an alkyl of ^CMD mine or branched ^{ive out of five} down by RET ^of containing from ¹ to ²² carbon atoms or alkenyl straight or branched chain of 12-20 carbon atoms, provided that if A represents a chemical bond with ^{R1 to} u ^pi nu ^b ecného Formula ^IV and if A is an oxygen atom, ^R1 is not a group of formula IV or V, ^{m p} rice from ^{the CE} characterized ⁱⁿ LB ^N UMBER uh ^phorous ovýc ^H atoms ^at the subsUUente ^ ^{R2, R3} and ^{R4 f} dy ^j EV is higher than 12, in an amount of 0.001 to 95% by weight in the mixture of a solid, liquid and / or gaseous carrier and / or other conventional additive, provided that if the amount of active ingredient in the composition is greater than 0.3% by weight, the carrier is always liquid. in reaction 2. A process for the preparation of active compounds of the formula (II) I, characterized by bringing it with an amine wherein ^{R 1} have ^the meanings said preceding Uve ^{d b} o ^d u ^1, of the formula III, wherein (III) 3 4 R and R are as defined in point 1.