Patent Application
20090105235
The present invention relates to increasing the activity of crop protection compositions comprising inhibitors of the nicotinic acetylcholine receptor (for example neonicotinoids) through the addition of ammonium salts and/or phosphonium salts or through the addition of ammonium or phosphonium salts and penetrants, to the corresponding compositions, to processes for preparing them and to their use in crop protection.
All inhibitors according to the invention of the nicotinic acetylcholine receptor are already known as agents for controlling animal pests, in particular insects, and can be prepared by processes described in the prior art. The activity of these compounds is good; however, in particular at low application rates and concentrations, it is not always entirely satisfactory. Furthermore, the compatibility of these compounds with plants is not always sufficient. There was therefore a need for increasing the activity of the crop protection compositions comprising the compounds.
Neonicotinoids can be described by the formula (Ia)
in which
A represents in each case optionally substituted cycloalkyl, heterocyclyl, aryl or hetaryl,
R1 represents hydrogen or alkyl,
R2 represents hydrogen or alkyl,
X represents ═N—NO2, ═N—CN or ═CH—NO2,
E represents methyl, OR3, SR3 or NR4R5,
Neonicotinoids can be furthermore be described by the formula (Ib)
in which
Furthermore, neonicotinoids can be described by the formula (Ic)
in which
In addition, neonicotinoids can be described by the formula (Id)
in which
In addition, neonicotinoids can be described by the formula (Ie)
in which
Q is as defined above,
T-U represents C(CHO)—NO2,
R20, R21 and R22 each independently of one another represent
Furthermore, neonicotinoids can be described by the formula (If)
in which
Furthermore, neonicotinoids can be described by the formula (Ig)
in which
Further inhibitors of the nicotinic acetylcholine receptor are taught in WO 05/055715. They are described by the formula (Ih)
in which
Preferred substituents or ranges of the radicals listed in the formulae (Ia) to (Ih) mentioned above and below are illustrated below.
Preferred ranges for the radicals listed in formula (Ia) are given below:
In a group of outstanding compounds, R1 represents hydrogen.
Preferred substituents or ranges of the radicals listed in formula (Ib) mentioned above and below are given below.
In an outstanding group of compounds of the formula (Ib), B represents
2-chloropyrid-5-yl
In a further outstanding group of compounds of the formula (Ib),
B represents
2-chloro-1,3-thiazol-5-yl
The general or preferred radical definitions or illustrations given above apply to the end products and, correspondingly, to the starting materials and intermediates. These radical definitions can be combined with one another as desired, i.e. including combinations between the respective preferred ranges.
Preference according to the invention is given to compounds of the formulae (Ia) to (Ih) which contain a combination of the meanings given above as being preferred.
Particular preference according to the invention is given to compounds of the formulae (Ia) to (Ih) which contain a combination of the meanings given above as being particularly preferred.
Very particular preference according to the invention is given to compounds of the formulae (Ia) to (Ih) which contain a combination of the meanings given above as being very particularly preferred.
In the radical definitions given above and below, hydrocarbon radicals, such as alkyl, are in each case straight-chain or branched as far as this is possible—including in combination with heteroatoms, such as alkoxy.
Specific mention may be made of the following compounds of the general formula (Ia) from the class of the neonicotinoids:
Furthermore, mention may be made of the following compounds of the general formula (Ib) from the class of the neonicotinoids:
Furthermore, mention may be made of the following compounds of the general formula (Ic) from the class of the neonicotinoids:
Furthermore, mention may be made of the following compounds of the general formula (Id) from the class of the neonicotinoids:
Furthermore, mention may be made of the following compounds of the general formula (Ie) from the class of the neonicotinoids, which may also be present as geometrical isomers (A/B):
Furthermore, mention may be made of the following compounds of the general formula (If):
Furthermore, mention may be made of the following compounds of the general formula (Ig):
Furthermore, mention may be made of the following compounds of the general formula (Ih) from the class of the neonicotinoids
Inhibitors of the nicotinic acetylcholine receptor have broad insecticidal activity; however, in specific cases the activity is unsatisfactory.
The active compounds in the compositions according to the invention can be used in a broad concentration range. Here, the concentration of the active compounds in the formulation is usually 0.1-50% by weight.
Descriptions have already been given in the literature to the effect that the activity of various active compounds can be increased through addition of ammonium or phosphonium salts. The salts in question, however, are salts with a detergent effect (for example WO 95/017817) and/or salts having relatively long alkyl and/or aryl substituents, which have a permeabilizing effect or which increase the solubility of the active compound (for example EP-A 0 453 086, EP-A 0 664 081, FR-A 2 600 494, U.S. Pat. No. 4,844,734, U.S. Pat. No. 5,462,912, U.S. Pat. No. 5,538,937, US-A 03/0224939, US-A 05/0009880, US-A 05/0096386). Furthermore, the prior art describes the activity only for certain active compounds and/or certain applications of the composition in question. In still other cases, they are salts of sulphonic acids where the acids for their part have a paralysing action on insects (U.S. Pat. No. 2,842,476). An activity increase through ammonium sulphate is described for the herbicides glyphosate and phosphinothricin (U.S. Pat. No. 6,645,914, EP-A 0 036 106). However, this prior art neither discloses nor suggests a corresponding activity for insecticides.
Also, the use of ammonium sulphate as a formulating auxiliary has been described for certain active compounds and applications (WO 92/16108), but it is used there for the purpose of stabilizing the formulation, not for increasing activity.
It has now been found, entirely surprisingly, that the activity of insecticides which are inhibitors of the nicotinic acetylcholine receptor can be increased significantly through the addition of ammonium salts and/or phosphonium salts to the as-used solution (tank mix application) or through the incorporation of these salts into a formulation comprising such insecticides. Accordingly, the present invention provides the use of ammonium salts and/or phosphonium salts for increasing the activity of crop protection compositions comprising insecticidally active inhibitors of the nicotinic acetylcholine receptor as active compound. The invention also provides compositions comprising such insecticides and activity-increasing ammonium salts and/or phosphonium salts, specifically including not only formulated active compounds but also ready-to-use compositions (spray liquors). Finally, the invention also provides the use of these compositions for controlling harmful insects.
Ammonium salts and phosphonium salts which, according to the invention, increase the activity of crop protection compositions comprising inhibitors of the nicotinic acetylcholine receptor are defined by formula (II)
in which
The ammonium salts and phosphonium salts of the formula (II) can be used in a broad concentration range to increase the activity of crop protection compositions comprising insecticidally or acaracidally active compounds. In general, the ammonium salts or phosphonium salts are used in the ready-to-use crop protection composition in a concentration of from 0.5 to 80 mmol/l, preferably from 0.75 to 37.5 mmol/l, particularly preferably from 1.5 to 25 mmol/l. In the case of a formulated product, the ammonium salt concentration and/or phosphonium salt concentration in the formulation is chosen such that it is within these stated general, preferred or very preferred ranges after the formulation has been diluted to the desired active compound concentration. The concentration of the salt in the formulation here is typically 1-50% by weight.
In a preferred embodiment of the invention, the activity is increased by adding to the crop protection compositions not only an ammonium salt and/or phosphonium salt but also, additionally, a penetrant. It is considered entirely surprising that even in these cases an even greater activity increase is observed. The present invention therefore likewise provides the use of a combination of penetrant and ammonium salts and/or phosphonium salts for increasing the activity of crop protection compositions comprising insecticidally active inhibitors of the nicotinic acetylcholine receptor as active compound. The invention likewise provides compositions which comprise insecticidally active inhibitors of the nicotinic acetylcholine receptor, penetrants and ammonium salts and/or phosphonium salts, including specifically not only formulated active compounds but also ready-to-use compositions (spray liquors). The invention additionally provides, finally, for the use of these compositions for controlling harmful insects.
Suitable penetrants in the present context include all those substances which are typically used to enhance the penetration of agrochemically active compounds into plants. Penetrants are defined in this context by their ability to penetrate from the aqueous spray liquor and/or from the spray coating into the cuticle of the plant and thereby to increase the mobility of active compounds in the cuticle. The method described in the literature (Baur et al., 1997, Pesticide Science 51, 131-152) can be used in order to determine this property.
Suitable penetrants are, for example, alkanol alkoxylates. Penetrants according to the invention are alkanol alkoxylates of the formula
R—O—(-AO)v—R′ (III)
in which
A preferred group of penetrants are alkanol alkoxylates of the formula
R—O—(-EO—)n—R′ (III-a)
in which
A further preferred group of penetrants are alkanol alkoxylates of the formula
R—O—(-EO—)p—(—PO—)q—R′ (III-b)
in which
A further preferred group of penetrants are alkanol alkoxylates of the formula
R—O—(—PO—)r-(EO—)s—R′ (III-c)
in which
A further preferred group of penetrants are alkanol alkoxylates of the formula
R—O—(-EO—)p—(—BO—)q—R′ (III-d)
in which
A further preferred group of penetrants are alkanol alkoxylates of the formula
R—O—(—BO—)r—(-EO—)s—R′ (III-e)
in which
A further preferred group of penetrants are alkanol alkoxylates of the formula
CH3—(CH2)t—CH2—O—(—CH2—CH2—O—)u—R′ (III-f)
in which
In the formulae given above,
An example which may be mentioned of an alkanol alkoxylate of the formula (III-c) is 2-ethyl-hexyl alkoxylate of the formula
in which
the numbers 8 and 6 are average values.
An example which may be mentioned of an alkanol alkoxylate of the formula (III-d) is the formula
CH3—(CH2)10—O—(-EO—)6—(—BO—)2—CH3 (III-d-1)
in which
Particularly preferred alkanol alkoxylates of the formula (III-f) are compounds of this formula in which
The alkanol alkoxylate of the formula (III-f-1)
CH3—(CH2)t—CH2—O—(—CH2—CH2—O—)u—H (III-f-1)
in which
The above formulae provide a general definition of the alkanol alkoxylates. These substances are mixtures of substances of the stated type with different chain lengths. The indices therefore have average values which may also deviate from whole numbers.
The alkanol alkoxylates of the formulae stated are known and in some cases are available commercially or can be prepared by known methods (cf. WO 98-35 553, WO 00-35 278 and EP-A 0 681 865).
Suitable penetrants also include, for example, substances which promote the solubility of the compounds of the formula (I) in a spray coating. These include, for example, mineral and vegetable oils. Suitable oils are all mineral or vegetable oils—modified or otherwise—which can typically be used in agrochemical compositions. Mention may be made by way of example of sunflower oil, rapeseed oil, olive oil, castor oil, colza oil, maizeseed oil, cottonseed oil and soybean oil, or the esters of said oils. Preference is given to rapeseed oil, sunflower oil and their methyl or ethyl esters.
The concentration of penetrants in the compositions according to the invention can be varied within a wide range. In the case of a formulated crop protection composition, it is generally from 1 to 95% by weight, preferably from 1 to 55% by weight, particularly preferably from 15 to 40% by weight. In the ready-to-use compositions (spray liquors), the concentration is generally between 0.1 and 10 g/l, preferably between 0.5 and 5 g/l.
Inventively emphasized combinations of active compound, salt and penetrant are listed in the table below. Here, “penetrant as per test” means that any compound that acts as a penetrant in the cuticle penetration test (Baur et al., 1997, Pesticide Science 51, 131-152) is suitable.
Crop protection compositions according to the invention may also comprise further components, for example, surfactants and/or dispersing auxiliaries or emulsifiers.
Suitable nonionic surfactants and/or dispersing auxiliaries include all substances of this type that can usually be used in agrochemical compositions. Polyethylene oxide/polypropylene oxide block copolymers, polyethylene glycol ethers of straight-chain alcohols, reaction products of fatty acids with ethylene oxide and/or propylene oxide, furthermore polyvinyl alcohol, polyvinyl pyrrolidone, copolymers of polyvinyl alcohol and polyvinyl pyrrolidone and copolymers of (meth)acrylic acid and (meth)acrylic esters, and additionally alkyl ethoxylates and alkylaryl ethoxylates, which optionally may be phosphated and optionally may be neutralized with bases, examples of which may be mentioned being sorbitol ethoxylates, and also polyoxyalkyleneamine derivatives may be mentioned as being preferred.
Suitable anionic surfactants are all substances of this type that can usually be used in agrochemical compositions. Preference is given to alkali metal salts and alkaline earth metal salts of alkylsulphonic acids or alkylarylsulphonic acids.
A further preferred group of anionic surfactants and/or dispersing auxiliaries are the following salts that are of low solubility in plant oil: salts of polystyrenesulphonic acids, salts of polyvinylsulphonic acids, salts of naphthalenesulphonic acid/formaldehyde condensation products, salts of condensation products of naphthalenesulphonic acid, phenolsulphonic acid and formaldehyde, and salts of lignosulphonic acid.
Suitable additives which may be included in the formulations according to the invention are emulsifiers, foam inhibitors, preservatives, antioxidants, colorants and inert filling materials.
Preferred emulsifiers are ethoxylated nonylphenols, reaction products of alkylphenols with ethylene oxide and/or propylene oxide, ethoxylated arylalkylphenols, and also ethoxylated and propoxylated arylalkylphenols, and also sulphated or phosphated arylalkyl ethoxylates and/or arylalkyl ethoxypropoxylates, mention being made by way of example of sorbitan derivatives, such as polyethylene oxide sorbitan fatty acid esters and sorbitan fatty acid esters.
The examples below serve to illustrate the invention and should in no way be interpreted as being restrictive.
The activity increase through ammonium salts or phosphonium salts is evident from the examples below. Whereas the salts alone, at the application rates employed, have no insecticidal activity, they effect a considerable activity increase as additives for insecticidally active compounds.
Aphis gossypii test
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. If addition of ammonium salts, phosphonium salts or penetrants is required, the appropriate amount is added by pipette after dilution of the respective finished preparation solution.
Single-leaf cotton plants (Gossypium hirsutum) which are heavily infested by the cotton aphid (Aphis gossypii) are treated by spraying of the upper side of the leaf (spray volume 600 l/ha) with the active compound preparation at the desired concentration.
After the desired period of time, the kill in % is determined. 100% means that all animals have been killed; 0% means that none of the animals have been killed.
Activity Increase by Ammonium Salts/Phosphonium Salts in Combination with Penetrants
The data below confirm that ammonium salts or phosphonium salts are capable of increasing the activity even more, even when ready-to-use crop protection compositions comprising penetrants to increase activity are applied.
Myzus persicae test
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. If addition of ammonium salts, phosphonium salts or penetrants is required, the appropriate amount is added by pipette after dilution of the respective finished preparation solution. Single-leaf bell pepper plants (Capsicum annuum) which are heavily infested by the green peach aphid (Myzus persicaei) are treated by spraying of the upper side of the leaf (spray volume 600 l/ha) with the active compound preparation at the desired concentration. After the desired period of time, the kill in % is determined. 100% means that all animals have been killed; 0% means that none of the animals have been killed.
Aphis gossypii test
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. If addition of ammonium salts, phosphonium salts or penetrants is required, the appropriate amount is added by pipette after dilution of the respective finished preparation solution.
Single-leaf cotton plants (Gossypium hirsutum) which are heavily infested by the cotton aphid (Aphis gossypii) are treated by spraying of the upper side of the leaf (spray volume 600 l/ha) with the active compound preparation at the desired concentration.
After the desired period of time, the kill in % is determined. 100% means that all animals have been killed; 0% means that none of the animals have been killed.
Myzus persicae test
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration. If addition of ammonium salts or ammonium salts and penetrant is required, the appropriate amount is added by pipette after dilution of the respective finished preparation solution (in each case 1000 ppm).
Bell pepper plants (Capsicum annuum) which are heavily infested by the green peach aphid (Myzus persicaei) are treated by spraying with the active compound preparation at the desired concentration.
After the desired period of time, the kill in % is determined. 100% means that all animals have been killed; 0% means that none of the animals have been killed.
In this test, for example, the following compounds of the preparation examples show good activity: see table
Aphis gossypii test
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration. If addition of ammonium salts or ammonium salts and penetrant is required, the appropriate amount is added by pipette after dilution of the respective finished preparation solution (in each case 1000 ppm).
Cotton leaves (Gossypium hirsutum) which are heavily infested by the cotton aphid (Aphis gossypii) are sprayed with an active compound preparation at the desired concentration.
After the desired period of time, the kill in % is determined. 100% means that all aphids have been killed; 0% means that none of the aphids have been killed.
In this test, for example, the following compounds show good activity: see table
Myzus persicae test
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. If addition of ammonium salts or ammonium salts and penetrant is required, the appropriate amount is added by pipette after dilution of the respective finished preparation solution (in each case 1000 ppm).
Single-leaf bell pepper plants (Capsicum annuum) which are heavily infested by the green peach aphid (Myzus persicaei) are treated by spraying of the underside of the leaf with the active compound preparation at the desired concentration.
After the desired period of time, the kill in % is determined. 100% means that all animals have been killed; 0% means that none of the animals have been killed.
In this test, for example, the following compounds show good activity: see table
Myzus persicae test
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. If addition of ammonium salts or ammonium salts and penetrant is required, the appropriate amount is added by pipette after dilution of the respective finished preparation solution (in each case 1000 ppm).
Single-leaf bell pepper plants (Capsicum annuum) which are heavily infested by the green peach aphid (Myzus persicaei) are treated by spraying of the upper side of the leaf with the active compound preparation at the desired concentration.
After the desired period of time, the kill in % is determined. 100% means that all animals have been killed; 0% means that none of the animals have been killed.
In this test, for example, the following compounds of the preparation examples show good activity: see table
Aphis gossypii test (APHIGO contact)
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. If addition of ammonium salts or ammonium salts and penetrant is required, the appropriate amount is added by pipette after dilution of the respective finished preparation solution (in each case 1000 ppm).
Single-leaf cotton plants (Gossypium hirsutum) which are heavily infested by the cotton aphid (Aphis gossypii) are treated by spraying of the underside of the leaf with the active compound preparation at the desired concentration.
After the desired period of time, the kill in % is determined. 100% means that all animals have been killed; 0% means that none of the animals have been killed.
In this test, for example, the following compounds show good activity: see table
Aphis gossypii test (APHIGO translaminar)
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. If addition of ammonium salts or ammonium salts and penetrant is required, the appropriate amount is added by pipette after dilution of the respective finished preparation solution (in each case 1000 ppm).
Single-leaf cotton plants (Gossypium hirsutum) which are heavily infested by the cotton aphid (Aphis gossypii) are treated by spraying of the upper side of the leaf with the active compound preparation at the desired concentration.
After the desired period of time, the kill in % is determined. 100% means that all animals have been killed; 0% means that none of the animals have been killed.
In this test, for example, the following compounds show good activity: see table
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2005 059 468.9 | Dec 2005 | DE | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2006/011468 | 11/30/2006 | WO | 00 | 10/24/2008 |
