Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2001-11-09
2004-08-31
Raymond, Richard L. (Department: 1624)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Heterocyclic carbon compounds containing a hetero ring...
C544S182000
Reexamination Certificate
active
06784176
ABSTRACT:
The present invention relates to novel, insecticidally active solvates of pymetrozine, a method of producing them, compositions containing these compounds, a method of producing these compositions, a method of controlling pests with the said compositions, and their use in the control of animal pests, especially insects and members of the order Acarina, particularly in crops of cultivated plants.
Various solvates, for example hydrates, of a chemical compound can exhibit very different physical properties, which may lead to unforeseeable problems during technical preparation and processing of these compounds. The characteristics of such solvates frequently have a crucial influence on the separating ability (filtration), stirrability (crystal volume), surface activity (foaming), rate of drying, solubility, quality, formulating ability and storage stability (e.g. hygroscopy) of for example pesticidally active compounds. For example, the grinding and formulating properties, as well as the handling ability of such pesticidal mixtures, may be completely different depending on the respective solvatising. Since, in the various stages of synthesis of a preparation process, different physical properties of the respective synthesis products are of importance, it is especially advantageous to find the optimally suited solvation form for the respective stage of synthesis.
Pymetrozine is known for example from U.S. Pat. No. 4,931,439, in which the preparation is described in example P3. However, it cannot be assumed from this example that the product obtained had been solvated with ethanol, diethylether or water, even though the product had come into contact with ethanol, diethylether and water in the course of its preparation. At the end of the preparation process, the compound was dried, and it was used in the formulation examples as an essentially water-free and solvent-free product. Physical parameters such as temperature, humidity and pressure, which are crucial for the specific preparation of certain solvates, are not indicated anywhere in the said patent specification.
It is therefore the aim of the present invention to prepare solvates, in particular hydrates, and salts of such solvates of pymetrozine, the characteristics of which show the advantages mentioned initially, especially in the production and handling of pesticidal mixtures, particularly granulates.
Accordingly, the present invention relates to compounds of formula
wherein
r and s, independently of each other, signify any value between 0.00 and 12.00; and
L is methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, cyclohexanol, atetrahydrofurfuryl alcohol, ethylene glycol, glycerol, methyl acetate, ethyl acetate, ethyl lactate, butyrolactone, ethylene carbonate, propylene carbonate, acetonitrile, dimethyl sulphoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, N-octyl-2-pyrrolidone, N-decyl-2-pyrrolidone, acetone, butanone, methyl isobutyl ketone, methylpropyl ketone, acetophenone, cyclohexanone, methylene chloride, trichloromethane, trichloroethane, tetrahydrofuran, diethylether, 1,2-dimethoxyethane, dioxane, methyl-tert.-butylether, ethanolamine, pyridine, chlorobenzene, toluene, xylene or tetramethylurea; with the proviso that r and s are not simultaneously 0;
in each case in free form or in salt form, and their tautomers, in each case in free form or in salt form, a method for the preparation and usage of these compounds, their salts and their tautomers; pesticides whose active ingredient is selected from these compounds and their tautomers; and a method for the preparation of these solvates and where appropriate their salts, a method for the preparation of these compositions and their usage.
In the following, a distinction will be made between the compound of formula (I) or the salts thereof, in which r and s are not simultaneously 0, and pymetrozine, which is the solvate-free compound (in which r and s are simultaneously 0).
Compounds of formula (I) have several basic centres. They may therefore form acid addition salts. These are formed for example with strong inorganic acids, such as mineral acids, e.g. perchloric acid, sulphuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as C
1
-C
4
-alkanecarboxylic acids optionally substituted for example by halogen, e.g. acetic acid, such as optionally unsaturated dicarboxylic acids, e.g. oxalic, malonic, succinic, maleic, fumaric or phthalic acid, such as hydroxycarboxylic acids, e.g. ascorbic, lactic, malic, tartaric or citric acid, or benzoic acid, or with organic sulphonic acids, such as C
1
-C
4
alkanesulphonic or arylsulphonic acids optionally substituted for example by halogen, e.g. methanesulphonic or p-toluenesulphonic acid. In addition, compounds of formula (I) may form salts with bases. Suitable salts with bases are for example metal salts, such as alkali or alkaline earth metal salts, e.g. sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g. ethyl, diethyl, triethyl or dimethylpropylamine, or a mono-, di- or trihydroxy-lower alkylamine, e.g. mono-, di- or triethanolamine.
In this case, on the one hand salts with formic acid, acetic acid and lactic acid are preferred, and on the other hand the sodium, potassium, magnesium and calcium salts are preferred, especially sodium salts. On the other hand, the compound of formula (I) in free form, i.e. in which r is 0, is also preferred.
Compounds (I) have also one acid group and can therefore form salts with bases. Suitable salts with bases are, for example, metal salts including metal complexes, such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, but also comples salts with for instance copper, nickel of iron; or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, for example ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- or trihydroxy-lower alkylamine, for example mono-, di- or triethanolamine. If appropriate, corresponding inner salts can furthermore be formed. Agrochemically advantageous salts are preferred in the context of the invention. Hereinabove and hereinbelow, the compounds (I) in free form are to be understood as including the corresponding salts, and the salts are to be understood as including the free compounds (I). In each case the free form is in general preferred.
Further preferred compounds of formula (I) are characterised in that L signifies methanol; especially wherein L is methanol and s is 0.
Additionally preferred compounds of formula (I) are characterised in that r signifies 0 and s is 0.5, 0.75, 1, 1.25, 1.5, 1.75, 2, 2.25, 2.5, 2.75, 3, 3.25, 3.5, 3.75, 4, 5, 6, 7, 8 or 12; especially 1, 1.25, 1.5, 1.75, 2, 2.25, 2.5, 2.75, 3, 3.25, 3.5, 3.75, 4, 5, 6, 7, 8 or 12; in particular 1.5, 1.75, 2, 2.25, 2.5, 2.75, 3, 3.25, 3.5, 3.75, 4, 5 or 6; most preferably 1.5, 2, 2.5, 3, 3.5 or 4; most particularly 2.
One especially preferred object of the invention is a compound of formula (I), in which r is 0 and s is 2 (pymetrozine dihydrate), and which shows the reflections listed in table 1 in the X-ray powder pattern.
TABLE 1
X-ray powder data of pymetrozine dihydrate
d (Å)
Intensity
12.4
average
7.1
weak
6.8
very strong
6.3
weak
6.2
average
5.82
very weak
5.40
average
5.14
very weak
4.85
weak
4.68
very weak
4.52
very weak
4.31
very weak
4.14
weak
4.08
very weak
3.96
very weak
3.83
very weak
3.71
very weak
3.58
weak
3.47
very strong
3.44
very strong
3.25
strong
3.21
weak
3.09
average
3.03
weak
2.99
weak
2.90
weak
2.82
weak
2.76
weak
2.57
weak
A further preferred object of the invention is a compound of formula (I) in which r is 1 and s is 0 and L is methanol (pymetrozine methanolate), and which shows the following reflections in the X-ray powder pattern:
TABLE 2
X-ray powder data of pymetrozine methanolate
d (Å)
Intensity
8.4
strong
Allen Rose M.
Balasubramanian Venkataraman
Raymond Richard L.
Syngenta Crop Protection Inc.
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