UA72521C2 - Pimetrozine solvates, pesticide composition and a method for preparing the same - Google Patents

Abstract

Compounds of formula (I) 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, tetrahydrofurfuryl 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, are described.

Description

alkali metal or alkaline earth metal salts, for example, sodium, potassium or magnesium salts, as well as complex salts, for example, copper, nickel or iron salts; or an ammonium or organic amine salt, such as, for example, morpholine, piperidine, pyrrolidine, mono-, di- or tri(lower) alkylamine, for example ethyl-, triethyl- or dimethylpropylamine, or mono-. di- or trihydroxy(lower) alkylamine, for example, mono-. di- or triethanolamine.

In addition, if necessary, the corresponding internal salts can be formed. In the context of this invention, salts having advantages from the point of view of agrochemistry are preferred. It will be understood below in this description that the compounds of formula (I) in free form also include the corresponding salts and it is meant that the salts include compounds of formula (I) in free form. In general, in each case the free form is preferable.

Other preferred compounds of formula (1) differ in that HER means methanol; primarily 1 stands for methanol and 5 is 0.

Other preferred compounds of formula (I) differ in that r is 0 and 5 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; mostly 1, 1,25, 1,5,1,75,2,2,25,2,5,2,15, 3, 3,25, 3,5, 3,75, 4, 5, 6, 7 , 8 or 12; more preferably 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; especially preferably 2.

One of the most preferred objects of the invention is the compound of the formula (I), where r is 0 and 5 is 2 (pymetrosine dihydrate), and what is the mass of the reflection characteristics obtained by X-ray diffraction on the powder, which are presented in Table 1.

Table 1

Powder X-ray diffraction pattern for pymetrozine dihydrate

NA) Intensity 124 medium 7 weak 6.8 very strong 6.3 weak 62 medium 5.82 very weak 5.40 medium 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

Another preferred object of the invention is a compound of formula (I) where r is 1 and 5 is 0 and Y is methanol (pymetrosine methanolate), and which has the reflectance characteristics obtained by X-ray powder diffraction shown in Table 2 .

Table 2

X-ray powder diffraction pattern for pymetrozine methanolate a(A) Intensity 8.4 strong 6.3 very weak 5.96 weak 5.51 very weak 5.31 very weak 5.18 very weak 4.97 very weak

4.81 very weak 4.55 medium 4.42 weak 4.22 weak 3.94 very weak 3.75 very weak 3.48 strong 3.38 very strong 3.25 weak 3.09 weak 3.04 weak 2, 98 very weak 2.94 very weak 2.84 very weak 2.81 very weak 2.77 very weak 2.74 very weak 271 very weak 2.66 weak

Another object of the invention is a new modification of pymetrozine (indicated below in this description as p-modification of pymetrozine), for which r and c are equal to 0. This new modification is obtained by drying at 120"0-1507С pymetrozine obtained by isolation in in the process of obtaining from a water-methanol suspension.

Table C

X-ray powder diffraction pattern for the B-modification of pymetrozine

I(A) Intensity 9.7 medium 8.4 very weak 5.87 strong 5.57 medium 5.14 very weak 4.96 weak 4.86 medium 4.69 very weak 4.40 medium 4.29 very weak 4 .23 very weak 3.83 weak 3.73 weak 3.66 weak 3.49 strong 3.34 very strong 3.28 shoulder 3.06 weak 2.95 very weak 2.82 medium 2.65 weak 2.60 very weak 2.53 very weak 2.48 very weak 2.30 weak 2.25 very weak 2.20 very weak 211 weak 2.07 weak 2.00 weak

For comparison, the X-ray diffraction diagram on the powder for the known α-modification of pymetrozine is given below:

Table 4

X-ray diffraction diagram on the powder for a-modification of pymetrozin

"(A) Intensity 11.9 weak 9.7 medium 7.6 medium 6.4 very weak bDd medium 5.95 medium 5.65 medium 5.26 medium 4.76 weak 4.49 weak 4.43 very weak 4 .37 weak 411 strong 3.99 very strong 3.81 weak 3.57 weak 3.52 weak 3.48 strong 3.34 very strong 3.26 very weak 3.14 strong 3.07 very weak 2.99 medium 2 .90 weak 2.82 medium 2.80 weak 2.75 weak 2.66 very weak 2.61 weak

X-ray diffraction patterns on the powder were measured using a X-Ray powder diffractometer (Rpiirz company), equipped with a TTK camera (Apyup Raai company), using radiation from a copper (Si) source (A-1.54060.E). Measurements for the dihydrate, the results of which are presented in Table 1, and for the anhydrous forms, the results of which are presented in Tables 3 and 4, were carried out at room temperature. Measurements for methanolate, the results of which are presented in Table 2, were carried out for a sample sealed with a Karyup-type film during cooling (57 - 8"7С).

When creating the invention, it was unexpectedly established that dried pymetrozin, which does not contain water and

PE contains a solvent, has the ability to reversibly absorb water or solvent from the atmosphere or in the process of mixing or grinding. It was found that at room temperature and relative humidity less than about 1095, pymetrozin containing water is completely dehydrated, and at relative humidity from 60905 to 7095, it again includes up to about 16-17 wt.95 of water. The water content indicated above, which is 16-1795, is very close to the water content of the dihydrate. Even pesticidal compositions comprising pymetrozine, which do not contain water and do not contain a solvent, tend to absorb water or a suitable solvent from the atmosphere if they are kept at a sufficiently high vapor pressure. Such solvation, primarily the absorption of water, compositions, primarily water-dispersible powders and granules, primarily granules, can lead to problems in the processing and storage of pesticide compositions, but such problems do not arise if pymetrozin is in the form of a defined solvate or in the form of the above B -modifications are either introduced into the pesticide composition during the production process, or are obtained in a suitable way during the above-mentioned preparation process. For example, such compositions do not need to be stored in airtight containers, and if the containers have been opened, it is not necessary to hermetically seal them again in order to preserve the quality of the product.

In addition, the preparation of compositions according to the invention which have a relatively high water content or which include the B-modification of pymetrozine is simpler compared to the preparation of compositions which contain substantially no water or those which include the α-modification, since the preparation is usually carried out in such a way in such a way that at the stage of preparation of the composition, water is added, which must then be removed.

The need for complete or almost complete removal of water is a significant drawback, as it is accompanied by significant energy consumption, longer manufacturing time, more intensive use of equipment, etc.

A finished composition of pymetrozine with a water content of about 10 wt.95 under normal conditions has only a very slight tendency to absorb moisture from the air, whereas a composition in which the water content during preparation has been reduced to less than 5 wt.90 or which has been made using ingredients that practically do not contain water, is very hygroscopic. Long-term storage of compositions having a water content of less than about 5 wt.% requires hermetic packaging, impermeable to water vapor, which accordingly requires high manufacturing costs. After use, the disposal of such packaging is accompanied by great problems compared to the disposal of ordinary containers, which are not completely waterproof.

In addition, packages whose contents cannot be used immediately cannot usually be closed in a sufficiently hermetic manner. Therefore, water will inevitably be absorbed by a composition that does not contain water.

If the anhydrous composition absorbs water, its quality is significantly reduced over a period of time from several weeks to several months. This means that the official requirements regarding the proportion of the active substance in the composition may not be met under certain circumstances. Therefore, the absorption of water by the anhydrous composition can lead to the fact that the goods after being stored by the manufacturer or seller will not be in demand, despite the fact that the active substance has not actually undergone decomposition.

Spontaneity: The quality of water-dispersible granules is largely determined by the convenience of their use by the consumer. Thus, the consumer expects the granules to completely disintegrate into their original particles after mixing for a few minutes in the spray solution. When making a composition based on pymetrozine, this property, known as spontaneity, is not achieved if a composition is used that was originally anhydrous or had a low water content, but reabsorbed water during storage. In contrast to practically anhydrous compositions, it was found that the granules included in the composition according to the invention, after being stored for 7 days in the appropriate testing device, completely disintegrated into original particles within a few minutes.

Table 5

Comparison of the spontaneity of pymetrozine-based granules with an active substance content of 50 wt.oo at different time intervals (testing was carried out according to SIRAS MT 174)

Spontaneity at 95

Content Spontaneity after saving water in to immediately without packing mass; after 7 days during production at room temperature for 1 min. | water, 1 min. time minutes vu | MIN. mass. o sgranuli!| 51 | 95 | 98 | 13.2 | 25 | 31 pellets | 10.3 | 96 | 98 | 153.7 | 93 | 98

When assessing spontaneity, a solution for spraying is first obtained by shaking the composition in a cylindrical vessel in the presence of a certain amount of water. After 0.5 or 1 min. 9095 of the liquid is removed in vacuo, and the other part is concentrated by evaporation. After drying, the resulting residue is analyzed and calculated as 95% of the amount of the originally used product suspended in the liquid.

Excluding the water content, the granules have the composition indicated below in Example E10 and are prepared according to the method described in this Example.

Other advantages of the compositions according to the invention are a higher ability to suspend in a liquid for spraying and a higher dispersibility.

The necessary solvate can be obtained before combining the active substance with the excipients used in the composition, or alternatively, in the process of making the composition by bringing the active substance into contact with the required amount of the specified solvent or water. Therefore, it appears possible to use various processes for the special preparation of such solvates and pesticide compositions containing such solvates. For example, pymetrozine, which does not contain water and does not contain a solvent, can be mixed or ground in a mixer in an atmosphere with a defined content of water or solvent to obtain the required form. In another embodiment, pymetrozine having a high water or solvent content, formed during the production process or formed by mixing pymetrozine, which does not contain practically no solvent and does not contain water, with a large amount of solvent or water, is dried in a dryer until the required content of solvation is reached agent Thus, these methods of obtaining solvates, primarily hydrates, of pymetrozine represent another object of the invention.

Suitable compositions of compounds of formula (I) are described, for example, in O5-P 4931439. All of them differ in that they do not contain pymetrozine in solvated form.

Preparative forms, that is, agents, compositions or compositions containing the active substance of formula (I) and one or more solid and/or liquid excipients for the composition, are also an object of the invention. they are obtained by a well-known method, for example, by homogeneously mixing and/or grinding the active substance of formula (I) together with excipients for the composition, such as solvents or solid carriers. In an alternative new method, which is also an object of the invention, it is assumed that a solvating agent is added during the preparation of the composition, as a result of which a solvate is formed during the preparation. According to an important variant of this method, the solvating agent can be added in excess and then removed after completion of the preparation, for example, by evaporation until the required content is reached. For certain mixtures, this procedure can significantly simplify the preparation process. The corresponding compositions obtained according to this method are also an object of the invention.

Surface-active substances (detergents) can additionally be used when preparing compositions. Examples of solvents and solid carriers are given, in particular, in 0Ш5-Р 4931439. Suitable surfactants, depending on the type of active substance of formula (I) to be included in the composition, are ionogenic, cationogenic and/or anionic surfactants and mixtures surface-active substances with good dispersing and wetting properties. Examples of suitable anionic. of nonionic and/or cationic surfactants are given in O5-P 4931439.

Insecticidal and acaricidal compositions according to the invention, as a rule, contain from 0.1 to 99 wt.9o, preferably from

0.1 to 95 wt.9o of the compound of formula (I), from 1 to 99.9 wt.9o, preferably from 5 to 99.8 wt.9o of a solid or liquid excipient for the composition and from 0 to 25 wt.9o, the main in the manner from 0.1 to 20 wt.9o of surface-active substance. Also preferred are insecticidal and acaricidal compositions, which, as a rule, contain from 0.1 to 94 wt. 90, mainly from 0.1 to 90 wt. 90 of pymetrozin, from 5 to 30 wt. 90 of a solvating agent, from 1 to 94, 9 wt.bdo, mainly from 5 to 90 wt.9o of solid or liquid excipient for the composition and from 0 to 30 wt.9o, mainly from 0.1 to 25 wt.9o of surface-active substance.

In particular, the pesticide is preferred! compositions, primarily granules, containing from 3 to 5 wt.95 or from 30 to 50 wt.90 of imitrozine. Also preferred are powders that show the ability to disperse in water and contain from 25 to 50 wt.9o of pymetrozine.

Preferable are also pesticide compositions, primarily granules containing from 8 to 40 mabs.9r. preferably from 8 to 20 wt.9o, most preferably from 8 to 14 wt.9Uy of water. Pesticides are also preferable! compositions, primarily granules, containing from 40 to 60 wt.9o pymetrosin. preferably 50 wt. 90 pymetrosin.

Also preferred are wettable powders containing from b to 20 wt.90, preferably from 8 to 12 wt.90 of water and from 20 to 30 wt.90 of pymetrozine, preferably 25 wt.90 of imetrozine.

When determining the water content, one should take into account the fact that the excipients for the composition themselves often contain a residual amount of water. As a result, the actual water content in the compositions, as a rule, slightly exceeds the value calculated for the composition containing only hydrates. In general, the measured water contents exceed the calculated values by 1-5 wt.9o. The term "pymetrosine composition containing practically no water or a low water content", used above or below in this description, refers to a pesticide mixture containing a maximum of 6% by weight of water based on the total weight of the mixture.

Although concentrates are most preferred as products for sale, diluted formulations are generally used by the direct consumer. The compositions may also contain other ingredients, such as stabilizers, for example, optionally epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soybean oil), activators, defoamers, usually silicone oil, preservatives, viscosity regulators, binders , adhesives, as well as fertilizers or other active substances.

Compounds of formula (I) are usually applied to plants or to the place of their settlement in concentrations from 0.001 to 1.0 kg/ha, preferably from 0.1 to 0.6 kg/ha. The concentration required to achieve the desired effect can be determined experimentally. It depends on the type of action, the stage of development of the cultivated plant and the type of pest, as well as on the type of processing (place, time, method), while the result of processing depending on the specified parameters can vary widely, depending on the type of compositions according to according to the set goals and prevailing circumstances, appropriate application methods are chosen, such as spraying, spraying, dusting, wetting, scattering or watering.

Compositions containing compounds of formula (I) have high insecticidal properties, which allows them to be used on crops of agricultural plants, primarily such as cereals, cotton, soy, sugar beet, sugar cane, melon crops, rapeseed, corn and rice. Crops of agricultural plants mean crops that have acquired tolerance to pesticides as a result of conventional selection or with the help of genetic engineering methods. Pests, primarily insects and representatives of the Asagip family. to combat which the compositions according to the invention can be used, described, for example, in О5-Р 931439 and ЮБ-Р 46.145.

Below, the invention is illustrated by non-limiting examples.

Examples of compositions 95 means mass. 9o.

Example E1: Emulsifiable concentrates

Ingredients a) b) c) pymetrosin methanolate 2.590 4.095 0.590 calcium dodecylbenzenesulfonate Bo 85 0 bo polyethylene glycol ether of castor oil (36 Bo - - moles of EF) polyethylene glycol ether of tributylphenol (30 C:(ХА- 495 4965 moles of EF) lactic acid 80956 7196 00- - formic acid - - 6.564596

M-octylpyrrolidone 7.596 Was 2095

Emulsions of any required concentration can be obtained from such concentrates by dilution with water.

Example Eg2: Solutions

Ingredients a) b) c) pymetrosin trihydrate 3095 2095 1095 formic acid 7090 - - acetic acid - 8095 0-1 lactic acid - - 909о

Example EZ: Solutions

Ingredients a) 6) c) pymetrosin methanolate ZObyu 2095 1095 formic acid 709600 --- acetic acid - 8096 YDYU.A.-

lactic acid - - 9095

Solutions can be applied in the form of microdrops.

Example E4: Granules with coating

Ingredients a) b) c) pymetrozin-CHzZOnN Ббю Зб 02590 highly dispersed silicon dioxide бе 5 т polyethylene glycol 300 Бо 0495 Зоо calcium carbonate 8495 8895 90.59

The active substance is suspended in polyethylene glycol 300, sprayed on the carrier, and then the granules are dusted with silicon dioxide.

Example E5: Duets

Ingredients a) b) pymetrosin dihydrate 29 Bo highly dispersed silicon dioxide 176 5 talc 9790 - kaolin - 909

Ready-to-use duets are obtained by homogeneously mixing carriers with the active substance and subsequent grinding.

Example Eb: Wettable powders

Ingredients a) b) c) pymetrosin dihydrate 25 BOYU 7590 sodium lignosulfonate Bu - yuf F8ob sodium lauryl sulfate ZU 000 -- diisobutyl naphthalene sulfonate o o : - was (89 sodium polyethylene glycol ether pov. octylphenol (7-8 mol EF) ? highly dispersed silicon dioxide Bbv 1095 990 kaolin battle 2790

The compounds are mixed with adjuvants and the resulting mixture is ground in a suitable mill to obtain wettable powders that can be diluted with water to obtain suspensions of any required concentration.

Example E7: Wetting granules

Ingredients a) b) c) pymetrosin dihydrate ЗОбю 4095 8590 sodium lignosulfonate ЗОбю ЗОбю 12890 dibutyl naphthalene sulfonate o sodium Bub 00 -..2.095 block copolymer o o polyoxyalkylate B o T5zh - polymer organic o new 0 -- - carrier defoamer 0196 0.295 0 .29 kaolin 24995 - - talc - 22.39 -

The active substance is mixed and crushed with adjuvants, the mixture is moistened with water. The resulting mixture is extruded, granulated and then dried in a stream of air.

Example D8: Suspension concentrate pymetrosin dihydrate 4090 propylene glycol Polyethylene glycol ether and nonylphenol (15 mol EF) ? triethanolamine phosphate of polyethylene-79 glycol ether of tristyrylphenol? heteropolysaccharide 196 2-benzisothiazol-3-one 0.290 silicone oil in the form of 7595 oil, water emulsion " water 4090

The finely divided active substance is mixed with adjuvants. In this way, a suspension concentrate is obtained, from which, by diluting with water, suspensions of any required concentration can be obtained.

Example 9: Preparation of water-dispersible granules containing the compound of formula (1):

The compounds listed below are mixed and then ground in a suitable mill. 6090 anhydrous pymetrosin 595 sodium dibutyl naphthalene sulfonate 1095 sodium lignosulfonate

For sodium sulfate 1595 polymeric organic carrier 0.190 perfluoroalkyl phosphoric acid 4.995 silicon dioxide

After that, the mixture is mixed with 35-45 wt.9o of water and granulated. After drying with a conventional continuous dryer to a residual moisture content of 8-1295, the resulting granules are sieved through a sieve to select granules of a specific size. As a result, granules containing compounds of formula (1) in hydrated form are obtained.

Example 10: Preparation of water-dispersible granules containing the compound of formula (1):

Mix the compounds listed below. 5095 anhydrous pymetrosin 595 sodium dibutyl naphthalene sulfonate 1095 sodium lignosulfonate 595 sodium sulfate 1595 polymeric organic carrier 0.195 perfluoroalkyl phosphoric acid required to bring the amount of silicon dioxide to 10095.

After that, the mixture is mixed with 50-70 wt.9o of water and granulated. After drying using a conventional continuous dryer to a residual moisture content of 8-12956, the resulting granules are sieved through a sieve to select granules of a specific size. As a result, granules containing the compound of formula (I) in hydrated form are obtained.

Examples of obtaining solvates of formula (I) and compositions containing such solvates:

Example P1: Preparation of the compound of formula (I), where r is 0 and c is 2 (pymetrosine dihydrate):

Pymetrozine is stored in a sealed container for 10 days in an atmosphere maintained at a relative humidity of 8995. The product is then removed from the container and equilibrated in a laboratory atmosphere.

When testing at different temperatures, it was found that the mass loss of the product obtained when the temperature changes from room temperature to 1257C is 13.995, which corresponds to two molecules of water (the theoretical loss of water is 14.295).

The diffraction diagram, obtained with the help of an X-ray diffractometer using a copper source of radioactive radiation (L-1.540607) at room temperature, is presented in Table 1.

Example P2: Preparation of the compound of formula (I), where r is 0 and c is 2 (pymetrosine dihydrate):

The specified amount of water (16 wt.9o based on the mass of pymetrozine, which does not contain water) is sprayed while cooling in the mixer only on the active substance, and then the powder is slowly stirred until it cools to room temperature.

Example Pb: Preparation of the compound of formula (I), where r is 0 and 5 is 2 (pymetrosine dihydrate):

The specified amount of water is sprayed in a high-speed mixer only on the mixture of the active substance and excipients for the composition, and after a short exposure, the powder is subjected to further processing to obtain the final composition.

Example P4: Preparation of the compound of formula (I), where r is 0 and c is 2 (pymetrosine dihydrate):

In a vessel equipped with a stirrer, pymetrozin is suspended in water in the presence of other components of the composition, and then the mixture is sprayed in an air stream and dried until the residual moisture content is 6-1595.

Example P5: 0.5 g of pymetrozine is mixed for 9 days at 25"C in 2.5 g of water; after that, the suspension is filtered. As a result, a dihydrate is obtained, which has a mass loss of 1295 according to thermogravimetry data.

Example Pb: Preparation of a compound of the formula (I), where r is 1 and 5 is 0, and Y stands for methanol (pymetrozine methanolate): 0.488 g of pymetrozine, which does not contain water, is added at 0"C to 1.909 g of anhydrous methanol and stirred for 7 days at 0"C. The suspension is filtered through a frit without vacuum. Then the residue on the filter is immediately analyzed using an X-ray diffractometer. The diagram is shown in Table 2. According to thermogravimetric analysis in the temperature range from 0"C to 100"C, the mass loss is 12.4965, which corresponds to one molecule of methanol (theoretically: 12.8 wt.9o).