GB2055831A - Amine salts - 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

SPECIFICATION Rodenticidal compounds, concentrates containing them and compositions prepared therefrom The invention relates to new compounds of rodenticidal effects. The invention also relates to concentrates which contain the new compounds, and to compositions prepared from the new compounds or the concentrates. The invention relates further to a process for the preparation of the new compounds.

As is known, the most active rodenticidal compositions are the ones containing anticoagulant agents, since they have no prompt effect and thus do not raise the animals' suspicion towards the baits. The most widespread representatives of these anticoagulant agents are the derivatives of 4-hydroxy-coumarine and 1 3-indanedione.

The enol tautomeric forms of 4-hydroxycoumarines and 1 ,3-indanediones are of slightly acidic character, thus they form salts with strong inorganic and organic bases. The salts are better soluble in water than the 4-hydroxycoumarines and 1 ,3-indanediones themselves, thus they are applied primarily in the preparation of aqueous formulations, whereas non-aqueous formulations (such as solutions formed with oils or other organic solvents) are prepared generally from the acidic active agents (US patent specifications Nos.

2,687,365 and 2,900,302).

Various rodenticidal concentrates, containing as active agent a 4-hydroxycoumarine or 1,3-indanedione derivative, have been described in the literature. The published German patent application No. 2,227,843 discloses concentrated polyethylene glycol solutions of 2-(2,2-diphenylacetyl)-1 ,3-indanedione (difacinone) and 2-[2-(4-chlorophenyl )-2-phenylacetyl]- 1,3-indanedione (chlorofacinone), containing 0.01 to 15 g/kg of active agent. Concentrated solutions of chlorofacinone formed with benzene homologues, containing 50 to 100 g/l of active agent, have also been described (see published German patent application No. 2,341,835).

These concentrates are diluted with water prior to use, and the dilute solutions are applied to kill rodents in the form of spray liquids, drinking mixtures or as impregnating agents for cereals.

French patent of addition No. 95,858 describes a substance for killing musk-rats, which is composed of dehydrated vegetables impregnated with an oily solution of chlorofacinone. The active agent content of the oily solution is 0.25 to 0.75 girl, and that of the bait varies between 0.002 and 0.0065 %.

French patent specification No. 1,601,076 discloses oily solutions containing 0.25 to 0.75 g/l of warfarine [2-oxo-3-(1 -phenyl-3-oxo-butyl)-4-hydroxycoumarine] which can be applied to prepare rodenticidal baits.

Oily concentrates of difacinone have also been described (published German patent application No.

2,218,893). The less toxic concentrates contain 0.1-2.5 g/l of the active agent, whereas the active content of the more toxic ones varies between 2.5 and 5.0 g/l. However, this relatively great amount of active agent can be maintained in dissolved state only when the mixture is warm, thus the solution should be applied immediately to prepare baits.

Oily concentrates of 1,3-indanedione derivatives are also disclosed in the published German patent application No. 2,753,183. These concentrates contain up to 50 g/l (i.e. up to 5 % by weight) of the active agent and have improved storage stability. Stable and storable oily concentrates of 1,3-indanedione derivatives with an active agent content higher than 5 % have not been disclosed in the literature so far.

Those of the known concentrates which contain organic solvents (such as benzene homologues, polyglycols, etc.) have the disadvantage that they do not form stable emulsion upon diluting them with water. It is a further disadvantage that when the aqueous emulsions are applied to impregnate cereal grains and other foodstuffs (e.g. dried apple, dried carrots, etc.), the water content of the resulting bait increases to such an extent that it must be dried in order to avoid rotting and mould formation. This method is therefore very complex, time and energy consuming, and cannot be economically applied to the mass production of rodenticidal baits.

The oily concentrates have several advantages in comparison to those formed with organic solvents. Of the major advantages e.g. the following are to be mentioned: the foodstuffs impregnated with oily concentrates need not be dried, the baits prepared with oily concentrates resist the action of moisture far better than those formed with organic solvents, furthermore the mineral oil fractions applied as carriers in such concentrates attract the rodents. It is, however, a significant disadvantage that the indanedione and hydroxycoumarine derivatives are far less soluble in oils than in benzene homologues or polyglycols. The majority of the known oil concentrates contain maximum 2 to 2.5 g/l (i.e. 0.20 to 0.25 % by weight) of active agent, and even this low amount of active agent is liable to deposit from the solution upon storage.Stable oily concentrates with higher active agent contents (up to 5 % by weight) were described only for some 2-(2,2-diphenyl-acetyl)-1 ,3-indanedione derivatives (published German patent application No. 2,753,183).

The relatively low solubility causes the disadvantage that the concentrate should be applied onto the supports (such as cereal grains, dried vegetables, dried fruits, etc.) either in large amounts which can be absorbed only slowly by the generally hydrophilic support, or a more concentrated but instable solution should be applied. Both methods involve several difficulties, which greatly impede the use of oily concentrates in the large-scale production of rodenticidal baits.

The relatively low active agent contents of the known oily concentrates involves the additional disadvantage that very great amounts of solutions should be stored, transported and handled, which greatly increases the costs of preventing the damages caused by rodents.

The present invention aims at the elimination of the above difficulties.

The invention is based on the recognition that the 4-hydroxycoumarine and 1,3-indanedione derivatives, applied as rodenticidal substances, form salts not only with inorganic bases and lower alkyl- or alkanolamines described in the literature, but enter an acid-base interaction with less basic, sterically hindered long-chain secondary and tertiary aliphatic amines as well, and form addition compounds of oily or waxy consistence, which can be dissolved in or diluted with oils and other organic liquids at any desired concentration.

Thus, in one aspect, the invention relates to new addition compounds of rodenticidal agents with anticoagulant effects, said addition compounds having the general formula (I),

or a tautomer or mixture of tautomers thereof wherein A is oxygen or a valence bond, R' is a 1-tetralyl group or a group of the general formula (IV) or (V),

wherein Y stands for tert.-butyl, isobutyl, diphenyl-methyl, 4-methyl-diphenylmethyl, 4-ch loro- diphenylmethyl or4-bromo-diphenylmethyl group and 0 stands for phenyl, 4-chlorophenyl or 2-furyl group, with the proviso that if A is a valence bond, R1 represents a group of the general formula (IV), whereas if A is oxygen, R1 represents the 1-tetralyl group or a group of the general formula (V), R2 is hydrogen or a straight-chained or branched C1 22 alkyl or C12 20 alkenyl group, and R3 and R4 each stand for a straight-chained or branched Cur 22 alkyl or C12 20 alkenyl group, and the total number of carbon atoms contained by the B2, B3 and R4 groups is more than 12.

Salt-like compounds of 2-(2,2-diphenylacetyl)-1 ,3-indanedione derivatives having the general formula (VI),

wherein RX and RY each stand for hydrogen, halogen or C1 4 alkyl, formed with secondary or tertiary amines have already been referred to in the published German patent application No. 2,753,183. According to this reference one molar equivalent of an indanedione derivative of the general formula (VI) is contacted with 0.2 to 10 molar equivalents ofthe respective amine in an oily solvent to form an oily concentrate with an active agent content of up to 5 % by weight, expressed as free indanedione compound. Some of the amine salts were also isolated in pure state and identified. The actually isolated and identified compounds were, however, salts formed with lower acyclic or cyclic amines, which proved to be crystalline substances.

Addition compounds of the above 2-(2,2-diphenylacetyl)-1,3.indanedione derivatives formed with higher acyclic amines were neither isolated nor identified in the cited reference, thus it was not known before that these addition compounds are oily or waxy substances which can be admixed with oils at any desired ratio to form stable compositions. Even more, the upper limit of active agent content (5 % by weight) fixed in the cited reference suggests that it is an absolute limit of solubility, and oily solutions with higher active agent contents cannot be prepared from the amine salts.Thus the addition compounds of the 2-(2,2 diphenylacetyl)-1,3-indanedione derivatives having the general formula (VI) formed with higher acyclic amines should be regarded as new, since their physico-chemical constants were not disclosed in the cited reference, and, based on the concentration values discussed in that reference, one could not conclude to the consistence and favourable solubility characteristics of these compounds.

In a second aspect, the invention relates to a concentrate of rodenticidal effects, characterized by containing one or more compound(s) of the general formula (I) in an amount of 0.3 to 95 % by weight, preferably 1 to 95 % by weight, more preferably 10 to 95 % by weight, particularly 20 to 95 % by weight, together with a liquid organic diluent and optionally with one or more further additives, preferably colouring, flavouring, odouring, preserving, activity broadening and/or synergistic agents, agents which attract the rodents, agents which are repellants for other animals, etc.

Furthermore, the invention relates to rodenticidal compositions comprising a compound of the general formula (I) or a concentrate as defined above in admixture with a solid, liquid and/or gaseous carrier and/or another conventional additive. These rodenticidal compositions contain one or more active agent(s) of the general formula (I) in an amount of 0.001 to 95 % by weight. Particularly preferred representatives of the rodenticidal compositions are rodenticidal baits ready for use, which comprise a compound of the general formula (I) or a concentrate as defined above applied onto the surface of a conventional support, such as cereal grains, dried vegetabes, etc.

The compounds of the general formula (I) are prepared according to the invention so that a compound of the general formula (II),

wherein R1 and A are as defined above, is reacted with an amine of the general formula (III),

wherein R2, R3 and R4 are as defined above.

It is obvious to one skilled in the art that the compounds of the general formula (II), thus the compounds of the general formula (I) as well, may exist in the form of enol and oxo tautomers. In order to render the specification easy to survey, both the starting substances and the end-products were indicated as enol tautomers. The scope of the invention extends, however, to the respective oxo tautomers and enol-oxo tautomeric mixtures as well. The terms "a compound of the general formula (I)" and "a compound of the general formula (II)" are interpreted so that they encompass both the enol and the oxo tautomers, as well as any mixtures thereof.

Some of the compounds of the general formula (II) applied as starting substances in the process of the invention are listed in Table 1 below.

TABLE 1 A R1 International name oxygen 1-phenyl-3-oxo-butyl Warfarine " -(4-chlorophenyl)-3-oxo-butyl Cumachlor " 1,(2-furyl)-3-oxo-butyl Fumarine 1 ,2,3,44etrahydro-1 -naphthyl Cu matetralyl valence bond 2,2-dimethyl-propionyl Pindone 2,2-diphenylacetyl Difacinone 2-(4-chlorophenyl)-2-phenylacetyl Chlorofacinone 2-(4-bromophenyl)-2-phenylacetyl Bromofacinone " 2-(4-methylphenyl)-2-phenylacetyl Fentolactine 3-methyl-butyryl Via lone All of the compounds of the general formula (II) listed in Table 1 are known and applied as rodenticidal agents (R.Wegler: Chemie der Pflanzenschutz- und Schadlingsbekampfungsmittel; SpringerVerlag, 1970, Vol. I, pp. 614 to 627).

Preferred representatives of the aliphatic amines having the general formula (III), applied as reactants in the process of the invention, are as follows: N,N-dimethyl-dodecylamine, N,N-dimethyl-tridecylamine, N,N-dimethyl-hexadecylamine, 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 general formula (I) are prepared according to the invention most'simply so that an equimolar amount of an amine of the general formula (III) is added to the starting substance of the general formula (II), and the mixture is converted into a homogeneous melt, preferably under stirring and heating. The reaction can also be performed, however, in the presence of an inert solvent, and the solvent can be removed at the end of the reaction e.g. by evaporation. The slight evolution of heat which appears upon admixing the reactants with each other is generally sufficient to ensure an appropriate reaction rate, in some instances, however, the reaction can be accelerated or rendered complete by heating the mixture.

Heating of the mixture is preferred particularly when one of the reactants does not dissolve satisfactorily.

If less pure reactants (e.g. compounds of technical quality) are applied, one proceeds preferably so that one of the reactants is introduced in excess, and the reaction is performed in an inert liquid which is a poor solvent for eitherthe amine of the general formula (III) or the starting substance of the general formula (II). In this instance the excessive and non-reacted component and the impurities can be separated very easily from the dissolved end-product. Sometimes it is also preferred to perform the reaction in the presence of an inert liquid which is only a poor solvent for the end-product or does not dissolve the end-product at all.In such instances the addition compound of the general formula (I) separates from the solution as a tarry substance or as an immiscible oily phase, and can be isolated very easily e.g. by decanting the solution.

The order of introduction of the reactants and the solvent or solvent mixture is selected individually in accordance with the concrete reaction conditions and the nature of the reactants. If the compounds of the general formula (I) should be prepared in pure state, the solubility conditions should be considered thoroughly, since once an impurity appears in the end-product of oily or resinous consistence, it is rather difficult to remove it.

It is obvious for one skilled in the art that when the compounds of the general formula (I) are to be applied for killing rodents, they need not be prepared in completely pure state. Thus, impure compounds of the general formula (I), prepared from impure 4-hydroxycoumarine or 1,3-indanedione derivatives or from amines of technical quality can equally be applied as active agents in the rodenticidal concentrates and compositions. The amines of the general formula (III) contain as impurity generally isomeric compounds or lower or higher homologues. If such amine mixture is applied in the reaction, a mixture of the respective addition compounds of the general formula (I) is formed as end-product. Such mixtures can be applied to advantage in the preparation of rodenticidal concentrates and compositions.The technical products sold by the firm Hoechst A.G. under the trade name "Genamin" (Registered Trade Mark), which are C14 40 aliphatic amines either alone or as mixtures, can be applied to advantage as amine reactants in the process of the invention.

As mentioned above, the rodenticidal concentrates according to the invention contain one or more compound(s) of the general formula (I) as active agent in a total amount of 0.3 to 95 % by weight. This corresponds to about 0.2 to 60 % by weight of the compound having the general formula (II).

If the active agent is a mixture of compounds of the general formula (I), it may be e.g. a mixture of addition compounds formed from different compounds of the general formula (II) with a given amine of the general formula (III), or a mixture of addition compounds formed from a given compound of the general formula (II) with more amines of the general formula (III). These mixtures can be prepared in a single reaction step. Of course, one can also proceed so that the individual compounds of the general formula (I) are prepared first and then admixed with each other in the desired ratio.

The rodenticidal concentrates according to the invention contain, in addition to the active agent(s) of the general formula (I), one or more liquid organic diluent. It is preferred to apply hydrocarbons with high boiling points, such as mineral oil fractions (e.g. paraffine oil, Vaseline (Registered Trade Mark) oil, spindle oil, etc.), furthermore vegetable oils (e.g. sunflower oil, rape oil, linseed oil, etc.), oils of animal origin (e.g. various fish oils), synthetic oils (such as silicone oils, glycerides of fatty acids, fatty alcohols, higherfatty acids/preferably unsaturated acids/) or mixtures thereof as diluent. The concentrates, particularly those with high active agent content, may also contain free amines of the general formula (III) as diluents.Non-phytotoxic organic solvents, such as alcohols, ketones, hydrocarbons, esters or mixtures thereof can also be applied as liquid diluents either alone or in admixture with each other or with the diluents listed above. Mineral oil fractions, primarily Vaseline oil, proved to be particularly preferred diluants.

The rodenticidal concentrates according to the invention may also contain conventional additives, such as flavouring agents (e.g. sweetening agents), odouring agents, dyestuffs, preservatives, surfactants, furthermore synergistic and our activity-broadening agents (e.g. calciferol, sulfonamides, acetylsalicylic acid, phenylbutazone, etc.) and the like.

Besides the rodenticidal concentrates discussed above, other rodenticidal compositions can also be prepared from the new compounds of the general formula (I). These compositions are prepared by methods known peruse, utilizing either the compounds of the general formula (I) or the concentrates discussed above as starting substances. Thus e.g. the oily concentrates can be applied, optionally after dilution, onto cereal grains, dried vegetables, dried fruits or the like foodstuffs to prepare rodenticidal baits. The concentrates can be admixed with a propellant, such as difluorodichloromethane, to obtain an aerosol composition.The compounds of the general formula (I) or the oily concentrates containing the same can be admixed with non-phytotoxic, inert organic solvents (e.g. alcohols, esters, ketones, hydrocarbons or mixtures thereof) to obtain spray liquids usable in the protection of living plant cultures. Emulsifyable concentrates can also be presented for the same purpose; these compositions also contain one or more surfactant(s) beside the active compounds(s) and the solvent(s) (such as oils, esters, ketones, etc.). The emulsifyable concentrates are diluted with water to the required concentration prior to use, and sprayed then onto the area to be treated.

The compounds of the general formula (I) can also be dissolved in non-oily organic solvents, such as alcohols, ketones or lower hydrocarbons, to obtain concentrates which can be applied e.g. in the preparation of baits as described above.

The rodenticidal compositions may contain, beside the active agent and the liquid, solid and!or gaseous carrier, conventional additives or auxiliary agents (such as surfactants, flavouring agents, odouring agents, dyestuffs, preservatives, etc.) as well. The rodenticidal compositions contain the active agents of the general formula (I) in an amount of 0.001 to 95 % by weight.

The major advantages of the invention, as compared to the state of prior art, can be summarized in the following: 1) Concentrates of extremely high active agent contents, higher even by several orders of magnitude than the usual, can be prepared from the new active agents of the general formula (I). These concentrates are, in contrast to the majority of the known ones, stable even without warming, and can be stored for long periods of time without any detectable change. Thus the difficulties which emerge in connection with the storage of the concentrates can be eliminated completely by the invention.

2) Rodenticidal baits can be prepared very simply and economically even on large scale by utilizing the concentrates according to the invention. The scope of supports for baits can be broadened considerably by using the highly concentrated oily mixtures according to the invention, since they can be applied easily onto foodstuffs which could not be utilized before in preparing baits due to their low oil absorption capacities, despite of the fact that from other aspects (such as with regard of the nature of the dominant plant cultures, the consumption habits of the rodents, etc.) their use would have been beneficial and necessary.The new compounds of the general formula (I) are also far better soluble in non-oily organic liquids than the corresponding 4-hydroxycoumarine or 1,3-indanedione compounds of the general formula (II), which is very advantageous with respect of e.g. the ULV spraying technique.

3) The new compounds of the general formula (I) and the oily concentrates made therefrom can be admixed very easily with diluents, thus no lengthy stirring and heating is required to prepare more dilute compositions ready for use (e.g. spray liquids).

The invention is elucidated in detail by the aid of the following non-limiting Examples.

Example 1 A mixture of 1 g (3.42 mmoles) of coumatetralyl and 1.3 g (3.42 mmoles) of bis(tridecyl)-amine is stirred at 120 to 130-C until a homogeneous melt is formed, and then the melt is cooled to room temperature. The bis(tridecyl)-amine salt of coumatetralyl is obtained as an almost colourless, tacky, resinous substance. The product solidifies at -12C and forms a glassy substance.

The product dissolves at room temperature very easily in 5 parts by volume of Vaseline oil, sunflower oil or glycerol trioleate. On the contrary, the starting coumatetralyl can be dissolved at room temperature only in 2500 parts by volume of Vaseline oil, 920 parts by volume of sunflower oil or 150 parts by volume of glycerol trioleate, respectively.

Example 2 A mixture of 4.18 g (15.5 mmoles) of dimethyl-hexadecylamine, 5.82 g (15.5 mmoles) of chlorofacinone and 20 ml of n-hexane is refluxed for one hour. During this period the solid chlorofacinone dissolves completely in the reaction medium, and a clear, orange-yellow solution is formed. The solvent is evaporated to obtain the dimethyl-hexadecylamine salt of chiorofacinone as a yellowish-brown, thick, oily residue; nj, 1.5731. The product does not crystallize upon cooling, but forms a glassy solid at -32"C.

Analysis: calculated for C41H54C1NO3: C: 76.43 /0, 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 mmoles) of tris(dodecyl)-amine and 40 ml of hexane is refluxed. Difacinone is introduced into the mixture in small portions of about 0.1 g until the last portion does not dissolve upon the subsequent boiling. A total amount of 1.43 g of difacinone is introduced. The mixture is cooled and allowed to stand for 2 days in order to separate the excess of difacinone in crystalline state. The crystals are filtered off, washed with a small amount of hexane, the filtrate is combined with the wash, and the solvent is evaporated.

0.11 g of non-reacted difacinone are removed. This means that 1.32 g (3.87 mmoles) of difacinone participated in the reaction, which is practically equivalent with the amine applied.

The tris(dodecyl)-amine salt of difacinone is obtained as a yellowish-brown oil; nj = 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 mmoles) of chlorofacinone, 1.14 g (3.2 mmoles) of tris(octyl)-amine and 50 ml of acetonitrile is refluxed until the amount of tris(octyl)-amine, present as a separate phase, does not decrease further and an almost completely homogeneous solution is formed. The mixture is cooled to room temperature, the excess of tris(octyl)-amine is separated, and the actonitrile solution is cooled to - 1 80C. The tris(octyl)-amine salt of chlorofacinone deposits onto the wall of the flask as a yellowish-brown resin. The solvent is decanted, the resinous product is washed twice with 15 ml of acetonitrile (dissolution and freezing), and the traces of solvent are removed from the product in vacuo.

0.51 g of a resinous substance are obtained; n;) = 1.5582. The product does not crystallize upon cooling, but forms a glassy solid at -10"C.

Analysis: calculated for C47H66CINO3: C: 77.81 % H: 8.76 %, CI: 4.89 %; found: C: 77.87 %, H: 8.81 %, Cl: 4.78 %.

The 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 mmoles) of chlorofacinone, 0.7 g (3.28 mmoles) of dimethyl-dodecylamine and 100 ml of n-hexane is refluxed. The solid chlorofacinone dissolves completely within about 20 minutes, and the end-product separates simultaneously as a yellowish-brown, oily phase. The reaction mixture is cooled, and the hexane phase which contains the excess of the amine is decanted. 20 ml of hexane are added to the oily product, the mixture is boiled, then allowed to cool, and the hexane phase is decanted. This purification step is repeated twice more, finally the oily product is subjected to vacuum treatment in order to remove the solvent.

0.81 g of the dimethyl-dodecylamine salt of chlorofacinone are obtained as a yellowish-brown, thick oil; n20 = 1.5858. The product does not crystallize upon cooling, but forms a glassy solid at -22 C.

Analysis: calculated for C37H46CINO3: C: 75.55 %. H: 7.88 %, Cl: 6.03 %; found: C: 75.70 %, H: 8.12 %, Cl: 5.90 %.

The product dissolves very easily at room temperature in one part by volume of methanol, acetone or benzene. 1 g of the starting chlorofacinone 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 One proceeds as described in the previous Examples to obtain the compounds listed in Table 2.

TABLE 2 Example Starting substances Method Characteristics of the end-products Solidifica No. (II) (III) (Example) Colour Appear- n20 tion point ance 6 Chlorofacinone Bis(tridecyl)-amine 5 yellowish brown resin 1.5445 -10 C 7 Chlorofacinone Tris(dodecyl)-amine 2 orange yellow oil 1.5420 + 7 C 8 Difacinone Dimethyl-dodecylamine 2 brown oil 1.5800 -27 C 9 Difacinone Dimethyl-hexadecylamine 2 dark brown oil 1.5648 -14 C 10 Cumatetralyl Tris(dodecyl)-amine 1 orange yellow oil 1.5212 -36 C Example 17 A concentrate is prepared by admixing the following components in the ratios defined below:: Mixed amine salt of chlorofacinone formed with Genamin SO 302D 91.8 % by weight Genamin SO 302D 8.2 Genamin SO 302 D, applied as salt-forming component and diluent, is a mixture of dimethyl-(higher alkyl)-amines and dimethyl-(higher alkenyl)-amines; the higher alkyl and alkenyl groups contain 14, 16 and 18 carbon atoms. The amine mixture is produced and sold by the firm Hoechst A.G.

The concentrate contains 91.8 % by weight of the mixed salt, which corresponds to a chlorofacinone content of 50 % by weight.

The concentrate is a homogeneous, clear, orange yellow, thick oil, which retains its liquid state upon storage at room temperature. The concentrate can be diluted easily with alcohols, aromatic solvents and ketones. The physical characteristics of the concentrate are as follows: specific gravity: 0.939 g!ml, nj7-; = 1.5711, viscosity at 50"C: 790 cSt.

Example 12 A concentrate is prepared by admixing the following components in the ratios defined below: Trioctylamine salt of difacinone 10.4 g Sudan Rot 7B (sold by BASF AG) 2 g Vaseline oil 990 ml The concentrate contains the salt in an amount corresponding to 5 g-l (= 0.58 % by weight) of difacinone.

The concentrate is a dark red solution, completely clear and free of sediments in a thin layer. Specific gravity: 0.854 gimp, viscosity at 50"C: 10.1 cSt. The concentrate can be applied to prepare rodenticidal baits without dilution.

Example 13 A concentrate is prepared by admixing the following components in the ratios defined below: Tris(dodecyl)-amine salt of chlorofacinone 62.5 parts by wt.

Sudan Rot7Bflüssig (produced byBASFAG) 37.5 The concentrate contains the salt in an amount corresponding to 25 % by weight of chlorofacinone. The concentrate is a dark red, almost black, sediment-free thick oil. Specific gravity: 1.03 g ml viscosity at 50 C: 178 cSt. The concentract can be applied, after dilution, to prepare rodenticidal baits. Thus e.g. 1 kg of the concentrate can be diluted with paraffine oil or Vaseline oil to a final volume of 100 litres to obtain an oily solution of the usual concentration (0.25 z0 by weight of chlorofacinone). Cereal grains can be impregnated with this dilute solution in a known way to form rodenticidal baits.

Example 14 An emulsifyable concentrate is prepared by admixing the following components in the ratios defined below: Concentrate of Example 11 20 g Isopropanol 40 9 Non it (surfactant, sold by Egyesült Vegyimüvek) 40 g This emulsifyable concentrate contains the mixed amine salts of chlorofacinone in an amount corresponding to 10 % by weight of chlorofacinone. Prior to use the concentrate is diluted with water to the required final concentration. The amount of water to be added depends on the technique of spraying. Thus e.g. when 50 g of the above emulsifyable concentrate is poured into 100 ml of water with stirring, a milky, fine emulsion is obtained, which can be applied to spray green plants (e.g. alfalfa) in order to protect them from musk-rats. The emulsion ready for use contains the mixed amine salts of chlorofacinone in an amount eqivalent with 50 ppm of chlorofacinone.

Example 15 The concentrate prepared as described in Example 13 is diluted with a mixture of 1 part by volume of sunflower oil and 9 parts by volume of Vaseline oil to obtain a solution which contains the chlorofacinone salt in an amount corresponding to 10 g/l of chlorofacinone. 0.75 litres of the diluted solution are distributed evenly on 100 kg of wheat, rice or barley. The grains rapidly absorb the oily solution, and a product of dry character is obtained immediately, without waiting for several hours or even days. A reddish, granular rodenticidal bait is obtained, which contains the chlorofacinone salt in an amount corresponding to 75 ppm of chlorofacinone. The bait can be applied to kill musk-rats in dosages of about 15 to 20 kg/ha, depending on the extent of the damage. The effectivity of the bait is 95 to 100 %.

Example 16 1.5 litres of the oily concentrate prepared as described in Example 12 are distributed on 100 kg of crushed corn grains (particle size: 3-5 mm). The resulting rodenticidal bait contains the difacinone salt in an amount corresponding to 75 ppm of difacinone.

Example 17 The concentrate prepared as described in Example 13 is diluted with Vaseline oil to an active agent content of 10 g/l (expressed as chlorofacinone). The resulting oily solution is applied onto crushed corn grains at a ratio of 3 litres/100 kg in a continuously operating drum stirrer. The resulting rodenticidal bait contains 300 ppm of active agent (expressed as chlorofacinone) and can be applied with good results to kill hamsters.

Claims (19)

1. A compound of the general formula (I),

or a tautomer or mixture of tautomers thereof wherein A is oxygen or a valence bond, R1 is a 1-tetralyl group or a group of the general formula (IV) or (V), - C - Y (IV) o Q -CH - CH2 - C - CH3 (V) o 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-chlorophenyl or 2-furyl group, with the proviso that if A is a valence bond, R1 represents a group of the general formula (IV), whereas if A is oxygen, R1 represents the 1-tetralyl group or a group of the general formula (V), R2 is hydrogen or a straight-chained or branched Cm 22 alkyl or C12.20 alkenyl group, and R3 and R4 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 R2, R3 and R4 groups is more than 12.

2. A compound as claimed in claim 1, wherein A is oxygen or a valence bond, R1 is a 1 -tetralyl group our a group of the general formula (IV) or (V), wherein Y stands fortert.-butyl or isobutyl and Q is as defined in claim 1, with the proviso that if A is a valence bond, R1 represents a group of the general formula (IV), whereas if A is oxygen, R1 represents the 1 -tetralyl group or a group of the general formula (V), and R2, B3 and R4 are as defined in claim 1.

3. A compound as claimed in claim 3, wherein A is oxygen.

R1 is a group of the general formula (IV), wherein Y stands for diphenylmethyl, 4-methyl-diphenylmethyl, 4-chloro-diphenylmethyl or 4-bromo-diphenylmethyl group, and R2, B3 and R4 are as defined in claim 1.

4. A concentrate of a rodenticidal agent, characterized by containing as active agent at least one compound of the general formula (I) as defined in claim 1 in an amount of 0.3 to 95 % by weight, together with a liquid organic diluent.

5. A concentrate as claimed in claim 4, characterized by further containing one or more additional rodenticidal agent(s) and/or synergistic agent(s) and/or activity-broadening agent(s) and/or attractant(s) for rodents and/or repellant(s) for other animals and/or other conventional additives for rodenticidal compositions.

6. A concentrate as claimed in claim 4 or 5, characterized by containing the active agent(s) in an amount of 1 to95%byweight.

7. A concentrate as claimed in any of claims 4 to 6, characterized by containing the active agent(s) in an amount of 20 to 95 % by weight.

8. A concentrate as claimed in any of claims 4 to 7, characterized by containing as active agent at least one compound as defined in claim 2.

9. A concentrate as claimed in claim 7, characterized by containing as active agent at least one compound as defined in claim 3.

10. A concentrate as claimed in any of claims 4 to 9, characterized by containing as liquid organic diluent an oil, particularly a mineral oil fraction, a vegetable oil, an animal oil, a synthetic oil or a mixture thereof, an amine of the general formula (III) or a non-phytotoxic organic solvent, preferably an alcohol, a ketone, a hydrocarbon, an ester or a mixture thereof.

11. A rodenticidal composition characterized by containing a compound as claimed in any of claims 1 to 3 or a concentrate as claimed in any of claims 4 to 10 in an amount corresponding to an active agent content of 0.001 to 95 % by weight, in admixture with a solid, liquid and/or gaseous carrier and/or another conventional additive.

12. A composition as claimed in claim 11, characterized in that the composition is a bait ready for use and contains a solid support.

13. A composition as claimed in claim 11 or 12, characterized by containing as active agent one or more compound(s) as defined in claim 2.

14. A process for the preparation of a compound of the general formula (I), wherein A, Ra, R2, R3 and R4 are as defined in claim 1, characterized in that a compound of the general formula (II),

wherein A and R1 are as defined in claim 1, is reacted with an amine of the general formula (III),

wherein R2, R3 and R4 are as defined in claim 1.

15. A process as claimed in claim 14 for the preparation of mixtures of compounds having the general formula (I), characterized in that more than one compounds of the general formula (II) and/or more than one compounds of the general formula (III) are applied in the reaction.

16. A process as claimed in claim 14 or 15, characterized in that one or more compound(s) of the general formula (II), wherein A and R1 are as defined in claim 2, is(are) applied as starting substance(s).

17. A compound of the general formula (I) as defined in claim 1 substantially as herein described with reference to Examples 1-10.

18. A concentrate of a rodenticidal agent substantially as herein described with reference to Examples 11-14.

19. A rodenticidal composition substantially as herein described with reference to Example 15-17.