PL169882B1 - Method of obtaining novel derivatives of aryl halogenoalkyl pyrazoles - Google Patents

Abstract

1. A method for preparing new aryl-haloalkylpyrazoles of formula Z wherein, R1 is C1-5 alkyl; R2 is C1-5 haloalkyl; R3 is halogen; R5 is a halogen or hydrogen atom, R6 is a halogen atom, R38 is -OC1-5 alkyl, -OCH(CH3)CO2CH3, -O- CH(CH3)CO2CH2CH3, -OCH2CH2OCH3, -OCH2CO2CH2CH3, -OCH2C=CH, - O C H 2 O C H 3 or -O - CF H C O 2 C H 2 C H 3 , optionally their agriculturally acceptable salts or hydrates, characterized in that the compound of formula Y in which R1, R2, R3, R5 and R6 have the above-mentioned meaning is subjected to esterification 1) with a C1-5 alcohol, HOCH(CH3)CO2CH3, HOCH(CH3)CO2CH2CH3, HOCH2CH2OCH3, H OCH 2 CO2 CH2CH3) HOCH2C =CH , HOCH2OCH3 or HOCFH CO2CH2CH3 in the presence of a mineral acid or 2) with a halogenating agent in the presence of an amine-type base and then reacted with a C 1 - 5 alcohol, HOCH(CH3)CO2CH3, HOCH(CH3)CO2CH2CH3, HOCH2CH2OCH3, HOCH2CO2CH2CH3, HOCH2C=CH, HOCH2OCH3 or HOCFH CO2CH2CH3 in the presence of a base.

Description

The subject of the invention is a process for the preparation of new herbicidal aryl-haloalkylpyrazoles, used as an active ingredient of herbicides.

Various compounds of the substituted 3-aryl- and 5-arylpyrazole type are known from the literature. Such compounds have various uses, e.g. as synthesis intermediates, pharmaceuticals and herbicides.

Among the art-known substituted 3-aryl-5-haloarylpyrazoles and 5-aryl-3-haloalkylpyrazoles are compounds having different radicals as substituents for the aryl and / or pyrazole moiety, e.g., alkyl, carboxyl, alkoxycarbonyl, formyl, phenyl and phenyl substituted with various groups, such as alkyl, halogen or nitro, etc. Compounds of this type are known, for example, in which the aryl moiety is substituted with b 1 and 1 et r

................. othernn dc? ^ tnv1 ry UMrn cq <l1Vl 1 yvHrxp1 Lii c Usarv1 rhlorine wrom ^ a

1UU IU »ł 1VX1 j ŁVilj 1, tV Rwijlll VU tt llllYULll Ukj IllKil) wj u <· -7 -U, trifluoromethyl, etc., v the pyrazoyl radical is substituted at various positions at nitrogen or carbon atoms by alkyl, halogen, alkoxy, heterocyclic groups, S (O) nR groups where n is 0-2, and R may be various radicals such as those that are substituents on an arylation or pyrazole moiety.

With known compounds of the above type useful as herbicides, it is generally necessary to apply rates as high as 5 or 10 or more kilograms per hectare in order to obtain proper weed control. Thus, it is an object of the present invention to provide a new group of arylpyrazo compounds having a uniquely high unit phytotoxic activity against a spectrum of weeds, including narrowleaf and broadleaf weeds, and a high degree of protection for many crops, especially cereals and / or row crops such as wheat barley, corn, soybeans, peanuts, etc.

The compounds of the invention optionally in the form of agriculturally acceptable salts or hydrates have the general formula Z

wherein, R1 is C1-5 alkyl; R2 is C1-5 haloalkyl, R3 is halogen; R5 is halogen or hydrogen, Re is halogen, R38 is -OC1-5 alkyl, -OCH (CHa) CO2CH3, -OCH (CH3) CO2CH2CH3, -OCH2CH2OCH3, -OCH2CO2CH2CH3, -OCH ₂ C = CH, -OCH2OCH3 or -O-CFHCO2CH2CH3.

Preferred compounds are compounds of formula Z in which R1 is methyl, R2 is CF3, CF2Cl or CF2H, R3 is chlorine or bromine, R5 is fluoro.

Especially preferred are the compounds:

Ethyl 2-chloro-5- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3) -4-fluorobenzoate,

1-Methylethyl 2-Chloro-5- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolium-3) -4-fluorobenzoate.

While all of the above compounds have been shown to be of particular utility in a variety of crops, trials so far have shown Compounds Nos. 135 and 137 to be of greatest interest. These compounds provide exceptional control of resistant broadleaf weeds such as amaranth, turnip, velveteen and sessile in various crops such as like corn, soybeans and nuts, as well as trees and vines in forest management. The other compounds of the present invention show excellent herbicidal activity against weeds in other crops such as wheat and barley.

Certain of the compounds of the invention may have more than one possible stereoisomer and the stereoisomers may differ in herbicidal effectiveness. The structures shown in the drawings include all possible stereoisomers.

The above compounds can be applied in various ways, e.g. pre-emergence and / or post-emergence, superficially, to soil prior to plant emergence, etc.

The term "alkyl, as used herein, whether used alone or in combination terms, e.g., haloalkyl, includes straight and branched chain radicals. The preferred alkyl radicals are lower alkyls having 1-4 carbon atoms.

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The term "chloroalkyl" denotes alkyl radicals substituted with one or more halogen atoms (chlorine, bromine, iodine or fluorine); preferred radicals of this group are those having 1-4 carbon atoms, in particular halogenomethyl radicals, e.g. trifluoromethyl. In polyhaloalkyl radicals, the halogen atoms can be the same or different.

Representative, non-limiting examples of alkyl radicals are methyl, ethyl, isomeric propyls, butyls, and pentyls.

Representative mono-, di- and trihaloalkyl radicals include: chloromethyl, chloroethyl, bromomethyl, bromoethyl, iodomethyl, iodoethyl, chloropropyl, bromopropyl, iodopropyl, 1,1-dichloromethyl, 1,1-dubromomethyl, 1,1-dichloropropyl, 1,2 -dibromopropyl, 2,3-dibromopropyl, 1-chloro-2-bromoethyl, 2-chloro-3-bromopropyl, trifluoromethyl, trichloromethyl, etc.

The term "agriculturally acceptable salts" of the compounds represented by the above formulas as used herein means a salt or salts which readily ionize in an aqueous medium to form the cation or anion of these compounds and the corresponding anion or cation salt, which salts do not adversely affect the herbicidal properties of the herbicide in question. and which allow various mixtures, e.g. herbicide-antidote formulations, to be formulated without the problems of mixing, slurrying, stability, application equipment, packaging, etc.

The term "herbicidally effective amount" means the amount of a herbicide needed to cause significant damage or destruction to a significant proportion of the undesirable plants or weeds treated. Although there is no strict rule, it is economically desirable that 80-85% or more of the weeds be destroyed, although economically significant suppression of weed growth may occur at much lower levels, especially with some very harmful herbicide tolerant plants. .

Process for the preparation of compounds of formula Z

wherein, Ri is C1-5 alkyl; R2 is C1-5 haloalkyl, R3 is halogen; R5 is halogen or hydrogen, Re is halogen, R38 is -OC1-5 alkyl, -OCH (CH3) CO ₂ CH3, -O-CH (CH3) CO2CH ₂ CH3, -OCH ₂ CH ₂ OCH3, -OCH ₂ CO ₂ CH ₂ CH3, -OCH ₂ C = CH, -OCH2OCH3 or -O-CFHCO2CH2CH3, and optionally their agriculturally acceptable salts or hydrates, comprises that the compound of formula Y

in which R1, R2, R3, R5 and R6 are as defined above is subjected to esterification

1) with C1-5 alcohol, HOCH (CH3) CO ₂ CH3, HOCH (CH3) CO2CH ₂ CH3, HOCH2CH2OCH3,

HOCH2CO ₂ CH ₂ CH3, HOCH ₂ C = CH, HOCH ₂ OCH3 or HOCFHCO2CH2CH3 in the presence of mineral acid or

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2) with a chlorinator of the amine base present, and then reacted with a C 1-5 alcohol, HOCH (CHa) CO2CH3, HOCH (CH3) CO2CH2CH3, HOCH2CH2OCH3, HOCH2CO2CH2CH3, HOCH2C = CH, HOCH2OCH3 or HOCFHCO2CH2 base in the presence of a base.

Sulfuric acid may be used as the mineral acid, thionyl chloride, phosphorus pentachloride or oxalyl chloride as the halogenating agent, and as the amine base, trisalamine, pyridine, an alkali metal benoaltaalkylammonium salt or dimetalformamide.

The process diagram for the preparation of the starting compounds and the process according to the invention is shown below.

WITH

Y

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In the first step of this process, compounds of Formula T are converted to compounds of Formula W. Any solvent that does not interfere with the reaction can be used in this reaction. Such solvents include, but are not limited to, organic acids, inorganic acids, hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, ethers and sulfides, sulfoxides, and sulfones. Halogenating agents suitable for this reaction are bromine, chlorine, N-bromosuccinimide, N-chlorosuccinimide, sulfuryl chloride and the like. For some halogenating agents it is preferred to use an organic peroxide or light as a catalyst. The halogenating agent may be used in an amount less than an equimolar to the excess. The reaction temperature is -78 ° C to 200 ° C, preferably 10-120 ° C. The reaction can be carried out in a period ranging from a few minutes to several weeks depending on the amount of reagents, reaction temperature, etc. After completion of the reaction, the product or products are isolated by diluting the reaction mixture with water, and the product (s) is isolated by methods such as crystallization or extraction. solvent based. If necessary, the product (s) are purified by known methods.

The products of Formula X can be prepared by acidic hydrolysis of compounds of Formula W. To effect acid hydrolysis, compounds of Formula W are treated with an excess of a mineral acid such as hydrochloric acid or sulfuric acid, with a large excess of sulfuric acid being preferred. The reaction temperature is between 0 ° C and the boiling point of an inert solvent, preferably 10-100 ° C. The reaction may be carried out in a period ranging from a few minutes to several weeks depending on the quantity of reagents, reaction temperature, etc. After completion of the reaction, the product or products are isolated by diluting the reaction mixture with water and isolated by methods such as crystallization or solvent extraction. If necessary, the product (s) are purified by known methods.

Compounds of Formula Y are obtained by oxidizing compounds of Formula X. Any inert solvent such as hydrocarbons, aromatic hydrocarbons, pyridine and its derivatives, water, etc. may be used in this reaction.

The oxidizing agents used are peroxides such as, but not limited to, potassium permanganate or potassium dichromate. The reaction temperature is -50 ° C to the reflux temperature of an inert solvent, preferably 10-100 ° C. The reaction may be carried out in a period ranging from a few minutes to several weeks depending on the quantity of reagents, reaction temperature, etc. After completion of the reaction, the product or products are isolated by diluting the reaction mixture with water and isolated by methods such as crystallization or solvent extraction. If necessary, the product (s) are purified by known methods.

The last step in this process involves converting compounds of Formula Y to compounds of Formula Z by any known method for producing carboxylic acid derivatives. In this step, esterification is carried out. This can be carried out directly using compound Y or via an alkali metal salt of compound Y. The esterification may be performed using an excess of alcohol corresponding to the desired ester in the presence of a mineral acid (e.g. sulfuric acid). The esterification reaction can also be carried out in the presence of an inert solvent or a dehydrating agent.

Alternatively, compounds of Formula Y can be converted to an acid halide or anhydride and treated with an alcohol. The acid halide formation reaction can be performed in the presence of a halogenating agent such as, but not limited to, thionyl chloride, phosphorus pentachloride, oxalyl chloride, etc., with or without an inert solvent. Any solvent that does not interfere with the reaction can be used. A catalytic amount of an amine base such as triethylamine, pyridine or dimethylformamide or the like can be added to accelerate this reaction. The reaction is carried out at a temperature of -20 ° C to the boiling point of the solvent used. The reaction time is from a few minutes to 48 hours depending on the amount of reagents used and the reaction temperature. After completion of the reaction, excess halogenating reagent and solvent (s) are removed from the reaction product by evaporation or distillation. The resulting acid halide can be reacted with an alcohol to provide a compound of Formula Z. The reaction can be carried out in the absence of a solvent, or any inert solvent or solvent mixture can be used, including two-phase mixtures (such as water and methylene chloride or other organic solvent).

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A catalytic amount of an amine type base such as triethylamine, pyridine or an alkali metal hydroxide and / or a catalytic amount of a phase transfer catalyst such as benzyl trialkyl ammonium halide or other ammonium salt may be added to accelerate the reaction. The reaction temperature is from -20 ° C to the boiling point of the solvent used. The reaction is carried out in a period ranging from a few minutes to 48 hours depending on the amount of reactants and the reaction temperature. After the reaction is complete, the product is isolated by filtering and / or concentrating the reaction mixture. If necessary, the product is purified by known methods such as extraction, crystallization, column chromatography, etc. In the examples, the abbreviation mp. Represents the melting point; Vol. Sep. - boiling point.

Example 1. This example describes the preparation of 2-chloro-5- (4-amino-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3 -) - 4-fluorobenzoic acid (Compound No. 149).

To a solution of 2-chloro-5- (4-chloro-Tmethyl-5-trifluoromethyl-TH-pyrazoyl-3 -) - 4-fluorobenzaldehyde (4.5 g, 13.2 mmol) in 40 ml of acetone was added 13 ml (26 mmol) ) Jones reagent. The solution was stirred at room temperature for 2 hours and poured into 4000 ml of water. The resulting solid was filtered and after drying in air overnight, 4.5 g (96%) of 2-chloro-5- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3 -) - 4- acid were obtained. fluorobenzoate as a white solid. An analytical sample was recrystallized from ether / hexanes, mp 179-181 ° C.

Analysis for C13H θΝ 2O2F 4CI2:

Calculated C Ή), 36; H 1.66; N 7.84.

Found: C 40.49; H 1/77; N 7.77.

Example 2. This example describes the preparation of 1-methylethyl 2-chloro-5- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3-) -1-fluorobenzoate (Compound No. 135).

To a solution of 4.3 g, (0.012) of 2-chloro-5- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazo] yl-3 -) - 4-fluorobenzoic acid in 50 ml of methylene chloride was added 3.1 ml (0.036 mmol) of oxalyl chloride which resulted in gas evolution. After gas evolution had ceased, 1 drop of DMF was added and the solution was stirred until gas evolution ceased. The solution was concentrated in vacuo and the resulting residue was dissolved in 25 ml of isopropanol and heated to 60 ° C for 1 hour. The solution was cooled, poured into 200 ml of cold water, and the solid was filtered off and dried. The product was crystallized from ethanol / water to obtain 1.69 g (70%) of 1-methylethyl 2-chloro-5- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3 -) - 4-fluorobenzoate as white solid, mp 69 ° C.

Analysis for C15H12CI2F4N2O2:

Calculated: C 4 ^, 1 ^ H 3.03; N 7.02.

Found: C 44.14; H 3, () 4; N 7.03.

Table 1 shows examples of 1-methyl-5-arylpyrazole compounds.

Table 1

1-Methyl-3-arylpyrazoles physical data

RR,

R, \\ //

CH,

R,

Relationship no R2 R3 R5 Re R7 Physical data (m.t., t. Sep., Sun) 1 2 3 4 5 6 7 135 CF3 Cl Γ Cl WHAT! Ii 0-1) 2 69.0 ° C 136 CF3 Cl F. Cl CO ₂ CH (CH ₃ ) CH ₂ CH ₃ nD, 1.5150 (25 ° C) 137 CF3 Cl F. Cl CO2CH (CH ₃ ) CO ₂ CH ₃ nD, 1.5190 (25 ° C) 138 CF3 Cl F. Cl CO ₂ CH (CH ₃ ) CO ₂ Et nD, 1.5119 (25 ° C) 139 CF3 Cl F. Cl CO2CH2CH (CH ₃ ) 2 nD, 1.5158 (25 ° C) 140 CF3 Cl F. Cl CO2CH2CH (CH ₃ ) CH2CH ₃ nD, 1.5145 (25 ° C) 141 CF3 Cl F. Cl CO ₂ CH ₂ CH ₂ CH (CH ₃ ) 2 nD, 1.5132 (25 ° C) 142 CF3 Cl F. Cl CO2CH2CH2OCH3 64.0 ° C 143 CF3 Cl F. Cl CO2CH ₂ CO ₂ Et 83.0 ° C 144 cf ₃ Cl F. Cl CO2CH ₂ C = CH 92.0 ° C 145 CF3 Cl F. Cl CO ₂ CH2OCH ₃ 77.0 ° C 146 CF3 Cl F. Cl every ₂ ch ₃ 78.0 ° C 147 CF3 Cl F. Cl CO2CHFCO ₂ Et nD, 1.5112 (25 ° C) 148 CF3 Cl F. Cl CO ₂ Et 88.0 ° C 149 CF3 Cl F. Cl CO2H 179.0-180.0 ° C 150 CF3 Cl F. Cl CO2 n-hutyl clear oil 151 cf ₃ Cl F. Cl CO ₂ t-butyl nD, 1.5130 (25 ° C)

TESTS OF THE PRE-EASTIC CICACIDAL ACTION.

As already mentioned, the compounds according to the invention have been found to be surprisingly effective as herbicides.

The pre-emergence herbicidal action trials were carried out as follows: the topsoil was placed in an aluminum pan and compacted so that the soil surface was 0.95 - 1.27 cm below the top of the pan. A certain number of seeds of individual species of annual monocotyledons and dicotyledons and / or vegetative shoots of perennials were placed on the soil surface. A known amount of the active ingredient is dissolved or dispersed in an organic solvent, e.g. acetone, or water as a carrier and then applied directly to the substrate with the seeds, which were covered with untreated topsoil until the pan was full. After treatment, the bowls were placed on a bench in the greenhouse, where the soil was irrigated from below as needed to ensure adequate moisture for germination and growth.

About 10-14 days (usually 11 days) after seeding and treatment, the bowls were observed and the results (percent inhibition) recorded.

Tables 2 and 2A below summarize the results of trials on the pre-emergence herbicidal activity of the compounds of the present invention against weeds. The herbicidal activity indices given in these tables relate to the percent inhibition of a particular plant species.

Plant species commonly considered to be weeds used in one trial series, the results of which are given in the tables, were identified by letter markings above the columns according to the following legend.

Yens - edible tibia

Anbg - annual panicle

Sejg - Alpine sorghum

Good - roof slope

Bygr - one-sided weed

Mogl - wolf

Cobu - yele velcro - fibrous velvet Inmu - Wibw white cabbage - wild buckwheat

In the tables below, when present, the symbol "C" represents 100% control.

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Table 2

Pre-emergence trials% plant inhibition

Relationship no Dose kg / ha Y e n s AND n b g s e J. g D about b r B y g r M. about g 1 C. 0 b at V e 1 e AND n m at in b in 135 1.12 0 C. C. C. C. 90 90 C. C. C. 137 1.12 twenty 70 50 80 80 C. C. C. C. 90 138 1.12 twenty 40 thirty 90 50 C. C. c C. C. 142 1.12 0 10 twenty 70 40 C. 60 c 90 50 143 1.12 10 10 40 twenty twenty 90 80 c C. C. 144 1.12 10 10 twenty 10 thirty 80 C. c 80 70 145 1.12 60 0 thirty twenty thirty C. 70 c C. 70 146 1.12 twenty C. C. C. C. C. 90 c C. C. 147 1.12 thirty 0 40 10 40 80 twenty c 80 70 148 1.12 0 70 50 80 90 C. 90 c C. C. 149 1.12 twenty 0 twenty 0 twenty 90 thirty c 70 60 150 1.12 0 70 90 80 60 40 60 90 80 C. 151 1.12 0 c C. C. 90 70 90 90 90 C.

Table 2A

Pre-emergence trials% plant inhibition

Relationship no Dose kg / ha Y e n s AND n b g S. e J. g D 0 b r B y g r M. about g 1 C. 0 b at V e 1 e AND n m at in 1 b in 136 1.12 0 90 90 C. 70 80 80 90 90 C. 139 1.12 twenty twenty 40 80 thirty 70 70 C. 90 90 140 1.12 0 thirty 70 60 0 70 80 90 70 70 141 1.12 0 twenty 50 70 twenty 80 70 70 80 90

EMERGENCY ACTION TESTS The post-emergence herbicidal activity of some of the different compounds according to the invention was demonstrated in greenhouse trials as follows. The soil from the top layer was placed in aluminum bowls with holes in the bottom and compacted so that the soil surface was 0.95 - 1.27 cm below the top edge of the bowl. A certain number of seeds of individual species of different annual dicotyledonous and monocotyledonous plants and / or vegetative suckers of perennials were placed and pressed into the soil surface. The seeds and / or vegetative shoots were covered with soil and its level was leveled. The bowls were placed on a bench in the greenhouse and the soil was irrigated from below as needed. When the plants reached the desired age (two to three weeks), each pan individually transferred to a spraying chamber and sprayed by means of spray, resulting in spraying at a pressure of 170.3 kPa (pressure 10 lb / ⁱⁿ²⁾ and noting the application rate. The spray liquid contains enough of a mixture of emulsifiers to obtain a spray liquid (solution or suspension) containing about 0.4% by volume of emulsifier. The spraying liquid contains sufficient test compound to achieve application rates of active ingredient corresponding to those in Tables 3 and 3A, with a total spray volume corresponding to an actual volume of 1,870 l / ha (200 gallons / acre). The bowls were placed back in the greenhouse and watered as before. In about 10-14 days (usually 11 days), and in some cases still 24-28 days (usually 25 days) after spraying, damage to the plants was observed as compared to the control plants. The herbicidal activity rates reported in these tables represent the percent inhibition of a particular plant species.

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Table 3

Post-emergence tests% inhibition of plants

Relationship no Dose kg / ha Y e n s AND n b 8 s e J. g D about b r B V g r M. about g 1 c about b at V e AND e AND n m at in 1 b in 135 1.12 twenty C. C. C. C. C. C. C. C. C. 137 1.12 twenty C. C. C. C. C. C. C. C. C. 138 1.12 twenty C. C. c c C. C. C. c c 142 1.12 thirty C. C. c c C. C. C. c c 143 1.12 twenty C. 0 c c c c c c c 144 1.12 twenty 60 90 c 70 c c c c c 145 1.12 twenty 80 80 c 70 80 c c c c 146 1.12 thirty 80 80 40 90 C. c c 90 c 147 1.12 thirty 0 70 0 80 C. c c 40 c 148 1.12 twenty C. C. c C. C. c c C. c 149 1.12 twenty 0 40 0 thirty C. 70 c 50 c 150 1.12 twenty c C. c C. C. c c 90 c 151 1.12 twenty c C. c C. C. c c 80 c

Table 3A

Post-emergence tests% inhibition of plants

Relationship no Dose kg / ha Y e n s AND n b g S. e J. g D about b r B y g r M. about g 1 c about b at V e 1 e AND n m at IN 1 b in 136 1.12 10 C. C. C. C. c C. C. C. C. 139 1.12 10 90 C. C. C. c 90 C. c C. 140 1.12 10 C. c c c c C. c 90 90 141 112 0 90 90 c 70 c 90 c 80 C.

Herbicides, including concentrate compositions which require dilution before use, may contain at least one active ingredient and a liquid or solid excipient. These compositions are prepared by mixing the active ingredient with an excipient such as a diluent, carrier or conditioning agent. The result is formulations in the form of fine powders, granules, pellets, solutions, dispersions or emulsions. Thus, the active ingredient can be combined with auxiliary substances such as fine solids, liquids of organic origin, water, wetting agents, dispersants, emulsifiers and any suitable mixtures thereof.

Suitable wetting agents include alkylbenzene and alkyl naphthalene sulphonates, sulfuric acid esters of fatty alcohols, amines, amino acids, sodium isothionate long chain acid esters, sodium sulphosuccinate esters, sulphated and sulphonated fatty acid esters, sulphonation products from petroleum refining, sulphonated vegetable oils di-tertiary acetylene glycols, polyoxyethylene alkyl phenols (especially isooctylphenol and nonylphenol) and polyoxyethylene mono fatty acid esters and hexite anhydride (e.g. sorbitan). Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium ligninsulfonates, polymeric alkyl naphthalene sulfonates, sodium naphthalene sulfonate and polymethylene bisnaphthalene sulfonate.

Wettable powders are water-dispersible formulations containing at least one active ingredient, an inert solid filler and one or more wetting agents and dispersants. The inert solid fillers are mostly substances of organic origin, such as natural clays, diatomaceous earth, synthetic silica-derived minerals, etc. Examples of such fillers are kaolinite, attapulgite clay and synthetic magnesium silicate. Wettable powder compositions usually contain from more than 0.5 to 60 parts by weight (preferably 5-20 parts by weight) of active ingredient, about 0.25 to 25 parts by weight (preferably 1-15 parts by weight) of a wetting agent, about 0.25 - 25 parts by weight (preferably 1-: 15 parts by weight) of a dispersant and from 5 to about 95 parts by weight (preferably 5-50 parts by weight) of an inert solid filler, based on the total weight of the formulation. If desired, about 0.1-2.0 parts by weight of the filler may be replaced with a corrosion inhibitor, an antifoam, or a mixture thereof.

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Other formulations of the composition include dust concentrates containing 0.1-60% by weight of the active ingredient on a suitable filler. These formulations may be diluted before use to a concentration of about 0.1-10% by weight.

Aqueous suspensions or emulsions can be prepared by mixing a non-aqueous solution of the water-insoluble active ingredient and emulsifier with water until homogeneous, followed by homogenization to obtain a stable very fine particle emulsion. The small particle size of the resulting concentrated suspension is its characteristic feature, thanks to which, after dilution and spraying, a very even coverage of the preparation is obtained. The active ingredient content of such formulations is about 0.1-60% by weight, preferably 5-50% by weight, with the upper limit of the concentration being determined by the solubility of the active ingredient in the solvent.

Concentrates are usually solutions of the active ingredient in non-water-miscible or only partially water-miscible solvents containing a surfactant. Suitable solvents for the active ingredient are dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, hydrocarbons, and water-immiscible ethers, esters and ketones. Other highly concentrated concentrates can be prepared by dissolving the active ingredient in a solvent and then diluting the solution, e.g. with kerosene, to a spray concentration.

Concentrated agent formulations generally contain about 0.1-95 parts (preferably 5-60 parts by weight) of active ingredient, about 0.24-50 (preferably 1-25 parts by weight) of surfactant and, optionally, about 4-94 parts by weight of solvent. based on the total weight of the emulsifiable oil.

Granules are physically solid particulate preparations containing the active ingredient adhering to or dispersed within a solid matrix. A surfactant, for example as mentioned above, may be present in the formulation to facilitate the release of the active ingredient from the granulate particles. Natural clays, pyrophyllites, illlite, vermiculite, etc. can be used as solid fillers. Preferred fillers are porous, readily absorbable prefabricated particles such as pre-fabricated and sieved attapulgite, thermally expanded particulate vermiculite and fine clays, e.g. kaolin clays, hydrated. attapulgite and bentonite clays. These fillers are sprayed on or mixed with the active ingredient to form granules.

The granular compositions may contain about 0.1-30 parts by weight of active ingredient per 100 parts by weight of clay, and up to about 5 parts by weight of surfactant per 100 parts by weight of clay.

The compositions may also contain other additives, e.g. fertilizers, other herbicides, other pesticides, antidotes, etc., as adjuvants or in admixture with any of the adjuvants mentioned above. The chemical compounds that may be included in the agents include, for example, triazines, ureas, sulfonylureas, carbamates, acetamides, acetamilides, uracils, acetic acid or phenol derivatives, tinlcarbamates, triazoles, benzoic acid derivatives, nitriles, heterophenyl ethers, nitrophenyl ethers, phenyl ethers, pyridines and the like, such as:

Heterocyclic Nitrogen / Sulfur Compounds

2-Chlorn-4-ethylamino-6-isopropaloamino-s.-triazines,

2-Ch1nrn-4,6-diisopropylaminn-S; -triazine,

2-Chlnro-4,6- (S'uethylamino-s-triazane,

3- Iznpropaln-2,2-dioxydo-1H, 3H-2,1,3-benzothiadiαzynnn-4,

3-Amino-1,2,4-triaznl,

6,7-dihydropyridine salt (1,2-: 2 ', Γ-c) pyraoadynine,

5- Bromo-3-isoprnpalo-6-methylurasyl,

1,1'-Dimethyl-4,4'-bispyridine,

2- (4-isopropyl-4-methyl-5-oxoimidazinlinyl-2) -shmolmocarboxylic acid-3,

Salt of ionprnpylamine and 2- (4-isoprnpyl-4-methyl-5-ketoimidazolmyln-2) nicotinic acid,

Methyl 6- (4-isoprnpaln-4-methyl-5-ketoimidazolinyl-2y-ro-oluenokαrboxylαn and methyl 2- (4 ^^ propal-4-metal-5-ketoimidazolinyl-2) -p-toluenecarboxalate.

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Ureas / Sulfonylureas.

N- (4-chlorophenoxy) phenyl) -N, N-dimethylurea,

N, N-dimethyl - \ '3-chloro - 4-methylphenyl) calculator,

3- (3,4-Dwuc! HlophenylG) -1,1-dimethylurea,

1,3-Dimethyl-3 (benzothiazolyl-2) urea,

3- (p-Chlorophenyl) -1,1-dimethylurea,

-Butyl-3- (3,4-dichlorophenyl) -1-methylurea,

2XCiioro-N- | / 4-netoxyXethylene-1 © Vriazinyl-dgaminocarbonyl] benzenesulfonaniide, N- (2-methoxyLarbo) thiylphenylsufionyl) -N '- (4,6-bisdi'uflu () romethoxypyrinidinyl-2) urea,

Methyl 2- (4,6-dimethylpyrimidinyl-2) aminocarbonylaminosulfonylbenzoate, methyl 2- (4,6-dimethylpyrimidinyl-2) aminocarbonylaminosiphonylmethibenzoate, methyl 2- (4,6-dimethoxypyrimidinyl-2) aminocarbonylaminiometylsulfonyl sulfonyl-

Methyl 2- (4-methoxy-6-methyl-1,3,5-triazinyl-2) aminocarbonylaminosulfonylbenzoate. Karbaminiany / Thiolocarbaminy

2-chloroallyl diethyldithiocarbamate,

S- (4-chlorobenzyl) N, N-Diethylthiolcarbamate,

Isopropyl N- (3-chlorophenyl) carbamate,

N, N-Diisopropylthiolcarbamate S-2,3 - ^ - ^^ and ^ u ^^ lyloroallyl, N, N-Dipropylthiolcarbamate S-,

S-Propyl N, N-dipropylthiolcarbamate,

S-2,3,3-trichloroallyl N, N-Diisopropylthiolcarbamate.

Acetamides / Acetanilides / Aniliny / Amidy.

2-Chloro-N, N-diallylacetamide,

N'-Dimethyl-J-diphenylacetamide,

N- (2,4-Dimethylthienyl-3) -N- (1-t-methoxypropopyio-2) -2-chlorcacetamide,

N- (1Htpyrazolyl-1-methyl-N- (2,4-dimethylthienyl-3) -2-chloroacetamide,

N- (1-Pyrazoiίlo-1-metyio) -N- (4,6-dimethoxypyridinyl-5) -2-chloroacetamide,

N- (2,4-Dimethyl-5-tΓfluoromethylcsulfonylaminephenyl) -acetamide,

N-thisoprcpyl-2-chloroacetanilide,

N-tearopropylth1- (3,5,5-trimethylcyclohexen-1-yl) -t2-chloroacetamide,

2 ', 6'-Diethio-N-butoxymetyic-2-chloroacetaniaid,

2 ', 6'-Diethyl-N- (2-n-propoxyethyl) -2-chloroacetanilide,

2 ', 6'-Dimethyl-N- (1-pyrazoleUo-1 tnlethio) -2-chlorine ((acetaniaide,

2 ', 6'-Diethyl-N-methoxymethyl-2-chloroacetamhd,

2'-Methyl-6'-ethyl-N- (2-methoxypropyl-2) -2-chloroacetanilide,

2'-Methyl-6'-ethyl-N-ethoxymethyl-2-chloroacetanilide, a, a, a-Trifluoro-2,6-dinitro-N, N-dipropyl-p-toluidine,

Nt (1,1tDimethyopropyl) -3,5-dichlorobenzamide.

Acids / Esters / Alcohols 2,2-Dichloropropionic acid,

2-Inethyl-4-chlorophenoxyclic acid,

2,4-dichlorophenoxyacetic acid,

Methyl 2- [4- (2,4-dichlorophenoxy) phenoxy] propionate,

3-amino-2,5-dichlorobenzoic acid,

2-methoxy-3,6-dichlorobenzoic acid,

2,3,6-trichlorophenylacetic acid,

N-1-naphthylphthalamic acid,

Sodium 5- (2-Chloro-4-triflucrometyicphenoxy) -2-nitrobenzoate, 4,6-dinitro-o-butylphenoxy,

Butyl N-Phosphonomethylglycine and its salts (R) -2- [Trifluoromethylpyridinyl-2-phenoxy] propionate.

169 882

Ethers

2,4-dichlorophenol-4-nitrophenyl ether,

2-chloro-6, <5, 8-trifluoro-p-tolyl-3-ethoxy-4-nitrophenyl phenyl ether,

5- (2-Chloro-4-trifluoromethylphenoxy) -N-methylsulfonyl-2-nitrobenzamide,

1-carboethoxyethyl 5- (2-Chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate.

Various

2,6-Dichlorobenzonitrile,

Sodium hydrogen methanarsonate,

Disodium methanarsonate,

2- (2-Chlorophenyl) methyl-4,4-dimethyl-3-isoxazolidinone-3-exo-1-methyl-4- (1-methylethyl) -2- (2-methylphenylmethoxy) -7-oxabicyclo [2.2.1 '| heptane,

Glyphosate and its salts.

As fertilizers useful in combination with the active ingredients, mention may be made of ammonium nitrate, urea, potash, and superphosphate. Other useful additives are materials in which plants take root and grow, such as compost, manure, humus, sand, etc.

The herbicidal formulations of the types described above are shown in the following examples which illustrate some of their variants.

I. Liquid preparations.

% by weight

A. Compound No. 135 213.0

Methylcellulose 0,: 5

Colloidal silica 2.0

Sodium Lignosulfonate 3.15

N-Methyl-N-oleylauric acid sodium salt 2.0

Water 69.0

100.0

B. Compound No. 148 45.0

Methylcellulose 0.3

Colloidal silica 1.5

Sodium lignosulfonate 3.5

N-Methyl-N-oleylauric acid sodium salt 1.0

Water 44.7

100.0

II. % W / w suspension concentrates

A. Compound No. 135 18 ,,

Nonylphenol ethoxylate (9.5 mol. Ethyl) Sterox NJ Μ, Ο

Sodium lignosulfonate (Reax 88B) 11,: 1

Water 56.0

100.0% by weight

B. Compound No. 482 11.0

Xylene 88.0

100.0

III. Microcapsules wt.%

A. Compound No. 135 encapsulated in a polyurea 4.5 shell

Reax® C-21 R,

NaCl 5.0

Water 89.0

100.0

169 882

B. Compound No. 137 encapsulated in a Reax® 88B polyurea shell NaNO3

K _sy l _en j business

Water

C. Compound No. 138 with Reax® 88B NaNO3 Polyurea Encapsulation Kerosene Water

D. Compound No. 148 with encapsulated in polyurea-formaldehyde casing) Reax® C-21

NaCl

Petroleum oil (Aromatic 200)

Water

22.0

2.0

10.0

30.0

33J)

100.0

4.8

1.2

5.0

20.0

69.0

100.0

50.0

1.5

8.5 2 (^ 0 20.0 100.0

Effective amounts of the compounds according to the invention are applied to soil containing seeds or vegetative shoots, or are incorporated into the soil by any known method. The application of liquid or solid formulations of the agent to the soil can be carried out, for example, with the use of motor sprayers, hand-held and boom sprayers, and duster-sprayers. The preparations can also be applied from airplanes as dusts and spray liquids, thanks to their effectiveness at low doses. The exact amount of active ingredient to be applied depends on many factors, including the plant species and stage of development, soil type and condition, amount of rainfall and the particular application of the compound. In the selective pre-emergence treatment, i.e. on the soil, a rate of from about 0.005 kg / ha (0.5 g / ha) to about 11.2 kg / ha is applied. A preferred rate is from about 3.301 kg / ha (1.0 g / ha) to about 0.50 kg / ha (500 g / ha). Higher or lower dosages may be required in some cases. One skilled in the art will readily determine the optimal dose upon reading this description and the examples therein.

The term "soil" is used herein in its broadest sense and includes all known "soils" as defined in Webster's New International Dictionary, Second Edition, Unabridged (1961). Thus, this term covers all substances or environments in which plants can take root or grow, not only "soil", but also compost, manure, muck, clay, silt, sludge, clay, humus, sand, etc. , adapted as carriers supporting plant growth.

Publishing Department of the UP RP. Circulation of 90 copies. Price PLN 4.00

Claims (2)

Patent claims 1. A process for the preparation of new aryl-haloalkylpyrazoles of formula Z R, wherein, Ri is C1-5 alkyl; R2 is C1-5 haloalkyl, R3 is halogen; R5 is halogen or hydrogen, Re is halogen, R38 is -OC1-5 alkyl, -OCH (CH3) CO ₂ CH ₃ , -O-CH (CH3) CO2CH2CH3, -OCH2CH2OCH3, -OCH2CO2CH2CH3, -OCH ₂ C = CH, -OCH2OCH3 or -O-CFHCO2CH2CH3, optionally their agriculturally acceptable salts or hydrates, characterized in that the compound of formula Y wherein R1, R2, R3, R5 and Re are as defined above is esterified 1) with C1-5 alcohol, HOCH (CH3) CO2CH3, HOCH (CH3) CO2CH2CH3, HOCH2CH2OCH3, HOCH2CO2CH2CH3, HOCH2C = CH, HOCH2OCH3 or HOCFHCO2CH2CH3 in the presence of a mineral acid or 2) with a halogenating agent in the presence of an amine base and then reacted with a C1-5 alcohol, HOCH (CH3) CO2CH3, HOCH (CH3) CO2CH2CH3, HOCH2CH2OCH3, HOCH2CO2CH2CH3, HOCH2C = CH, HOCH2OCH3 or HOCFHCO2CH2CH3 in the presence of a base. 2. The method according to p. The process of claim 1, wherein the mineral acid is sulfuric acid, the halogenating agent is thionyl chloride, phosphorus pentachloride or oxalyl chloride, and the amine base is triethylamine, pyridine, an alkali metal benzyl trialkylammonium salt or dimethylformamide.