LT3014B - Herbicidal pyridine sulfonamide - Google Patents

Abstract

Herbicidal pyridine sulfonamide, this is a composition and usage method for the inhibition of alopecurus pratensis growth in corn crops as well as for the inhibition of plant vegetation in general.

Description

There is a constant need for new substances that effectively control unwanted vegetation. More generally, such materials are intended to selectively control weed growth in useful crops such as cotton, rice, corn, wheat, soy, and the like. Uncontrolled f

the growth of weeds in such crops can result in significant losses - reducing profit for the grower and increasing the price for the consumer. In other cases, herbicides are needed which can control all vegetation. Examples of areas where 'vegetation' control is required are vegetation areas, railways, storage areas, and industrial warehouses. Despite the fact that there are many commercially available products used for these purposes, there is a continuing search for more efficient, cheaper and environmentally friendly products. ,

Sulfonylurea herbicides which generally contain a sulfonylurea bridge *

SO ₂ NHCONH--, linking two aromatic or heterocyclic rings, belongs to a particular group of 'strong% active herbicides' found in recent years. '.

This application is in part part of U.S. Patent Application Serial No. 07 / 666.109 filed in 1991. ' March 7

continuation.

Application. WO 88/042977 'includes -herbicidal pyridine-sulfonylureas of formula'! L

JSO NHCN-Λ ² I

R where J is one of

R _x is -R _f or R _g ;

R _g is one of alkyl halides; and

R ₂ is one of CO ₂ R ₉ ,.

Although the compound of the present invention,. belongs to the above group, it is .here -not separately defined *. ·

EP-327.251 includes pyridinesulfonylureas of the general formula

where

R is C 1 -C 1 alkyl; and

R _T is C _X “C _Z alkyl fluorides and their use in limiting the growth of the mouse sperm.

The present invention relates to a compound of formula I-

ίο and its salts, hydrates and lower alcohol complexes, applicable to the earth.

The compound of the invention is a very active herbicide used before and / or after emergence of the plants. is applied to the growth of the fern. It is especially useful for selective ^f Pelin foxtail .augimo restriction cereal crops.

The present invention also encompasses a novel compound represented by Formula II, which is a useful intermediate for the preparation of a compound represented by fo'rmule I. '

CO ₂ CK ₃

II

SO ₂ NH ₂ ^;

Synthesis.

The compound represented by Formula i may be synthesized by one or more of the major routes described in U.S. Patent 4,774,337, or by the reaction schemes depicted in Equations la and 1b. Reaction of the sulfonamide II with the corresponding carboxylic acid IIIa phehyloester in the presence of basic bases such as tertiary amines such as 1,8-diazobicyclo [5.4.0] undec-7-ene (DBU) is represented by equation la.

The equation la

1) Base

2) H ₃ 0 ⁺

A

OCHj

The reaction represented by Equation la is preferably carried out in an inert gas atmosphere for 0.5-24 hours at '' 25 ° C 'using solvents such as dioxane,' - tetrahydrofuran, dimethylformamide, dimethylacetamide or acetonitrile, but not limited to those described in Europe. patent application no. .70,804 (published Jan. 26, 1983). It is useful to carry out the reaction with some base involved. Particularly suitable bases are 1.5-diazobicyclo [4.3.0] -non-5-ene (DBN), 1.5-diazobicyclo [5.4.0] undec-5-ene. (DBU). or triethylamine. It is convenient to isolate the reaction product represented by Formula I by acidifying the reaction solution with dilute hydrochloric acid or by extracting the reaction solution with a dilute hydrochloric acid such as methyleneopathic acid! aqueous solvent, chloride or ethyl acetate. Evaporation of the solvent to dryness gives the desired product. Phenylcarbamate can be synthesized by the reaction of the corresponding heterocyclic amine represented by the formula

A-NH.

diphenicarbonate or phenyl chloroformate in the presence of bases such as sodium hydride, pyridine or potassium carbonate in the presence of a catalytic amount of a catalyst such as 4-dimethylaminopyridine. The mixture is stirred for 12-36 'hours at 25-65 ° C in the appropriate solvent, tetrahydrofuran such as the compound of Formula I can also be synthesized. by reacting 'the corresponding arylsulfonylcarbamates represented by the formula' IIIc with heterocyclic amines · INId · as shown in equation 1b. This reaction can be carried out at various ^z '. * for bases, ·. as depicted in the equation * la, ąrba, by boiling in a suitable high-volatile solvent such as dioxane. Arylsulfonylcarbamates can be synthesized by reaction of sulfonamide II with alkyl carbonates

Illb (or chloroformates) at various bases.

phenyl or the corresponding

The equation lb.

J50įNH ₂

H

O

II

R ₂ 0C0R ₂ mb o

H

JS0 ₂ NHG0R ₂

IIIC

IIIC a-nh ₂

Hld where

R ₂ is phenyl or C 1 -C 1 alkyl; and

The required sulfonamide represented by Formula II can be synthesized by one of the methods shown in Equations 2 and 3 below.

Equation 2 - describes the reaction of -sulfonyl chloride (Formula IV) with ammonia to give the sulfonamide designated Formula I.

equation

8¾

JSO ^ Cl JS0 ₂ KH ₂ iv n where

J is as noted above.

The aminolysis reaction described in equation 2 is carried out at 20-30-25 ° C by adding at least two molar equivalents of anhydrous ammonia or. of concentrated amine hydroxide,. to a solution of the sulfonyl chloride (IV) in a suitable solvent such as diethyl ether, tetrahydrofuran or methylene chloride. The required sulfonamide of Formula II is isolated or. by filtration. In this case, the by-product ammonium chloride · is removed by washing with water or by extraction with a suitable organic solvent such as methylene chloride or ethyl acetate. After evaporation of the solvent to. dryness, resulting in product II, which is generally sufficiently pure to be used directly in the step. J

The sulfonamide represented by Formula II may also be present. · * »Synthesized as shown in Equation .3 under the action of the corresponding N-tert-butylsulfonamide VI. with an appropriate acid such as trifluoroacetic acid (TFR), polyphosphorus (PFR), or p-toluenesulfonic acid (p-TSR).

Equation 3 where

JS0 ₂ NH-t-BU. VI or p-TSR

JŠ0 ₂ NH ₂

Π ''

J is as noted above

The reaction described in equation 3 is convenient to perform,. stirring a solution of the compound of Formula VI in an excess of trifluoroacetic acid (about 0.3M) at '25 ° C for 1-7 hours. The required sulfonamide of formula II is then isolated by removal of the volatiles in vacuo and crystallization from an appropriate solvent such as diethyl ether, Ί-chlorobutane, or. ethyl acetate. . Alternatively, N-tert-butylsulfonamide / · represented by Formula VI may be treated with a catalytic amount of p-toluenesulfonic acid monohydrate by boiling for 1-6 hours in solvents such as toluene or xylene. The product is isolated as described above. On the use of polyphosphoric acid for the deprotection of N-tert-butylsulfonamide, see J.

G. Lombardino, 'J. ^Org:. Chem., 36, 1843-1845 (1971): On the use of trifluoroacetic acid, see JD Catt and

W.L. Matier, J. Org. Chem., 1974, 39, 566-568. The sulfonamide represented by Formula VI may be obtained by reaction of the sulfonyl chloride represented by Formula IV with an excess of sutret-butylamine as shown in equation 4 ·.

'35

Equation t-BūNH ₂ jso ₂ ci -------- IV

JSO ₂ NH-t ~ BU

VI where

J is as noted above.

xO The sulfonyl chloride labeled is obtained according to the '' method, 4,456,469, or according to the patent 4,741,764, which is the conversion of arylmethylthio compounds into a solution of hypochlorite.

The methodology presented in the formula describes

IV, may have a U.S. patent containing 'mercapto' or sulfonyl chloride,

The sulfides represented by the formula V can be obtained by reacting halides with pyridine. 'derivatives' represented by Formula VII with the appropriate mercaptan in the presence of bases as described in U.S. Patent 4,456,469 and shown in Equation 5.

The equation,

R * SB j_p.

base

VII V where

X 'is F, Cl, Br; and

R 'is C 1 -C 4 alkyl or benzyl.

The method for obtaining the sulfonamide represented by the formula VIIIIe is shown in equation 6. Trifluoromethyl ketone intermediate

Wille is obtained according to Lang et al., Hely. Chim. Act. 1988, 71, 596-601. After changing this procedure, Willie is further exposed to ethyl malonic acid monoarnide (or ethylcarbamoyl acetate), r

in the presence of sodium methylate. to obtain trifluoromethyl-pyridinone methyl ester VIIIIb. Heating of VIIIIb with -phosphorus oxalyl bromide / dimethylformamide chloride affords bromopyridine VIIIc. The following synthesis of the sulfonamide VIIIIe and the benzylsulfide VHId is carried out as described above.

or methylene oxybromide.

(DMF)

Equation 6 '»BuO' + CT ₃ COCCF ₃

CF,

VUIb

YUId

Willie

Willie

CO ^ CH

POBr or (COBr) ₂ / DMT

Ph £ H or koibu iph »phenyl!

co ₂ cb ₃

1) HaOClp

KC1

2} 1BuHH ₂

VIII ·

Also suitable as agricultural herbicides are salts of the compound of formula I, which may be obtained by all methods known in the art. For example,. metal salts may be prepared by reacting a compound represented by Formula I with an alkali or alkaline earth metal salt having a sufficiently basic anion (e.g., - »hydroxide, alkoxide, carbonate or hydroxide). Quaternary ammonium salts may be obtained in an analogous manner.

The compound represented by the formula 1 / salts may also be obtained by substituting one cation for another.

For example, the cation exchange may be effected directly by treating a salt of a compound represented by Formula I (e.g., an alkali metal or quaternary ammonium salt) with another solution containing the cation we wish to introduce. This method is' most appropriate *

when the salt formed to replace the cation is insoluble and can be separated by filtration.

The conversion can also be accomplished by passing an aqueous solution of the salt of the compound of Formula I (e.g., an alkali metal or a quaternary ammonium salt) through the column. · With cationic resin, equilibrated with the cations we wish to introduce into the parent salt, and required. the product is queued directly from the column. This method is particularly useful when the resulting salt is soluble in water, such as potassium, sodium, or calcium salts.

The salts obtained by the addition of the acid described in the present invention can be synthesized by reacting a compound of formula I with. corresponds to morphic acids such as p-toluene sulfuric acid, trichloroacetic acid and the like.

1.1

The preparation of the compounds of the present invention is further illustrated by the following individual examples. by examples. Temperatures are given in degrees Celsius, and abbreviations for nuclear magnetic resonance (NMR) spectra are as follows:

S-singlet, d-doublet, t-triplet, 'm-multiplet', signal positions expressed in 'parts per million' to the weaker side of the field, minus the internal tetramethylsilane standard, with signal positions in centimeters (cm * ¹ ),

The infrared (IR) spectrum is shown in reverse

EXAMPLE

Methyl 1,2-dihydro-2-oxy-6- (trifluoromethyl) -3-pyridinecarboxylate (VHIb). receipt

To a stirred solution of 10 g of methanol was dissolved 2.0 g (0.0102 mol) of 4-butoxy-1,1. 1,1-Trifluoro-3-buten-2-one (Vil) and 1.3 g * (0.0102 'm) of ethyl malonate monoamide were added 2.2 ml (0.0102 mol) of a 25% solution of n-atrium methylate in methanol. The solution turns into a thick yellow suspension which is refluxed overnight. The suspension is then cooled to room temperature, poured into water, acidified with 1N hydrochloric acid and extracted with methylene chloride. The combined organic layer is washed with brine and dried. magnesium sulfate and evaporation of the solvent afforded 1.7 g · (74%) of a solid. yellow substances. Mp 63-64 ° C; ¹ H NMR (CDCl 3) δ 4.0 (3H, s), 7.33 (1H, d, J = 8Hz), 8.4 (1H, d, J = 8Hz); IR (mineral oil) 3080, 1675 (br) 1.605, 1450, 1375 cm * ¹ .

EXAMPLE 2A

Preparation of methyl 2-bromo-6- (trifluoromethyl) -3-pyridine carboxylate (VIIIc)

A suspension prepared from 22.0 g (0.100 mol) of the product of Example 1 and. 28.7 g (0.100 mol) of phosphorus oxybromide are heated at 75-120 ° C for 45 minutes using an oil bath. The reaction vessel is also connected to a drainage tank filled with water for the capture of gaseous by-products. The mixture is then cooled to room temperature, diluted with water and 'extracted' with methylene chloride. The organic layers are combined and washed

15. dilute sodium bicarbonate solution, brine, dry over magnesium sulfate and evaporate to an oil which is further purified by flash chromatography using 20% ethyl acetate / petroleum ether as eluent to give 3.8 g (13%) of oil, NMR (CDCl ₃ ) @ 4.0 (3H, s), 7.72 '(1H, d, J = 8 Hz); IR (solid phase) 1740, 1590, 1455, 1335,

1275, 1140, 1100, 105Ό cm⁻¹ ^first

EXAMPLE * 2b '

Preparation of 2-Bromo-6- (trifluoromethyl) -3-pyridine carboxylate methyl (VIIc)

To the stirred solution / obtained after dissolving 2 g (0, 0091 mol of the product of Example 1) in 2.5 ml of methylene chloride, under nitrogen was added 0.92 ml (0.0118 mol) of dimethylformamide, followed by another 1.57 ml. (0.011 mol) of oxalyl bromide which causes an exothermic reaction (the temperature rises to 35 ° C) and gas evolution which continues until all the oxalyl is added The reaction mixture is cooled to room temperature and the remaining oxalyl is added and the solution is stirred at room temperature for 1 hour. During the orange-yellow suspension .Reactions boiled for 3 hours, cooled to -temperature and added 0.7S ml of the resulting mixture was stirred overnight .Addition (0.0055 mol) of oxalyl bromide and 0.46 ml (0, 0055 mol) dimethylformamide and reflux for 5 hours. The reaction mixture is poured into approximately 50 ml of water and 150 ml of ether is added, the organic layer is separated, washed with brine, dried over magnesium lfate is evaporated to an oil which is purified by flash chromatography using 20% ethyl acetate / hexane as the eluent to give. 1.53 g (55%) of an oil 'having a NMR spectrum similar to that described in Example 2a except that about 10% of the impurity dimethyl oxalate is observed.

EXAMPLE 3a

Preparation of Methyl 2- [[{(phenylmethyl) thio] -6- (trifluoromethyl) -3-pyridinecarboxylate (VIIIIId) · into a stirred suspension obtained by suspending 0.28 g (0. 008 mol) in 60% sodium hydride (in mineral oil). followed by washing with hexane) 7 ml of dry dimethylformamide to

0.8 ml (0.0067 mol) of benzylmercaptan were added under 0 ° C under nitrogen, keeping the temperature below 10 ° C. The suspension is warmed to room temperature and stirred for a further 45 minutes, then cooled again to '0 ° C. Then, a solution of 2 g (0, 0067 mol) of the material * prepared according to Examples 2a or 2b in 5'ml of dry dimethylformamide is added dropwise and stirred for 30 minutes at 0 ° C. The reaction mixture was poured into ice-water and 'extracted eteriuOrganiniai layers combined, washed' with brine, dried over magnesium sulfate, 'and' evaporation, yielding 2.3 g (100%) 'Ui NMR (CDC1 ₃₎ 6 3.94 (3H, s ),

4.43 (2H, s), 7.2-7, 6 '(6H, m), 8.38 (1H, d, j = 8Hz).

EXAMPLE 3b

Methyl 2 - [(phenylmethyl) thio] -6- (trifluoromethyl) -3-thi ...

Preparation of pyridine carboxylate (VIIIIId). To a suspension of 6.55 g (0.0584 mol) of potassium tert-butoxide in 60 ml of dry dimethylformamide is added 6.84 ml (0.0584 mol) of nitrogen at -Q. ) benzyl mercaptan, dissolved in 20 ml of dimethylformamide, under reflux, so that the temperature does not rise above 15 ° C. . Then. a solution of the solution obtained by dissolving 20 ml of dry dimethylformamide 15.83 g (0.053 mol) in either 2a or 2b at 0 ° C ^; and then stirred for an additional 30 minutes at 0 ° C. The reaction mixture was poured into ice water and extracted with ether. Combine the organic layers, wash with water, brine, dry over magnesium sulfate and evaporate to give 17.84 g (100%). ¹ K 'NMR spectrum - similar to Example 3, IR (solid phase) 1725-, 1675, 1575,

11-53, 850 cm @ ^-1 . EXAMPLE '4.

.

Preparation of Methyl 2 - [[{1,1-dimethylethyl) amino] sulfonyl] -6,6 (trifluoromethyl) -3-pyridinecarboxylate (VIIIIe)

To a stirred mixture of 75 ml of methylene chloride dissolved in 2.3 g (0.007 mol) of the substance prepared according to Examples 3a or 3b and 35 ml of water cooled to 0 ° C was added 2.1 ml (0.025 mol) of concentrated hydrochloric acid and a dropwise addition of 36 ml (0, 0245 mol) of 5% sodium hypochlorite. solution, 'following,.

that. the temperature would not rise above 10 ° C. After stirring for a further 15 minutes at 0 ° C, the reaction mixture is poured into water and. .extracted with methylene chloride. Organic

LT i:

the layers are combined, washed with brine, dried over magnesium sulfate and filtered. While stirring,

2.6 g '(0.035 mol) of tert-butylamine are added dropwise to the filtrate, cooled to -70 ° C, under nitrogen. The mixture is warmed to '-30 ° C, poured into water' and extracted with methylene chloride. The organic layers are combined, washed with brine, dried over magnesium sulfate and evaporated. purified by flash chromatography to give 20% ether as eluent

L.t. chromatography 10 acetate / petroleum (45%) solids. 1, -. 25 (9H, s), 4.0 (3H, (mineral oil) 3320,. Ethyl) 1.07 g

76-83 ° C; ^X H NMR (CDCl ₃ ) €

s), 5.35 (NH), 7-9. <1H, m); IR 1745, 1335, 1140 cm ^-1 . .

EXAMPLE 5

Preparation of methyl 2- (aminosulfonyl) -6- (trifluoromethyl) -3-pyridinecarboxylate (II) 'Solution obtained by dissolving 40.0 ml of trifluoroacetic acid in -0.95 g (2.79'mol) of the material prepared according to the procedure of Example 4. , stirred at room temperature overnight. The solution is then evaporated,. The oil is precipitated with ether and obtained. 0.46 g (58%) of a solid. 187-188 £ ^. ^ NMR (CDCl ₃₎ @ 4.05 (3H, s), 5.5 (NH _2), 7.95 (1H, d, J = 8 Hz), 8.35 (1H, .d, J = 8 Hz); IR (mineral oil) 3390, 3280, 1.725, 1340,

1140 cm ¹ . '

EXAMPLE 6

Preparation of methyl 2 - [[[[(4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] '-6- (trifluoromethyl) -3-pyrimidine carboxylate (I)

To a stirred solution of 0.5 ml of 0.05 g (0.175 mmol) of the product obtained in Example 5 and 0.06 g (0.211 mmol) of phenyl (4,6-dimethoxypyrimidin-2-yl) carbamate are added 0.028 g. g (0.185 mmol) of 1,8-diazobicyclo [5,4,4,3 undec-7-eno] is stirred for 15 minutes · The solution is diluted with water, acidified with 1N hydrochloric acid and extracted with methylene chloride. Combine the organic / layers, wash with brine, dry over magnesium sulfate, and evaporate to an oil which gives 0.03 g (54%) of a solid after settling with ether. Mp 130-137 ° C. ¹ H NMR (CDCl ₃ )? 3.96 (6H, 's),' 4.0.5 (3R, 's), 5.82 (1H, s), 7.3 (NH), 7.93' ( 1H, d, J = about 8Hz), "8.4 · (1H, d, J = about 8Hz), 13.1 (NH); IR (mineral oil)

3180, 1745, 1370, 1140 _I cmr ¹ . '

EXAMPLE. 7th

- Φ

Preparation of Methyl 2 - [[[[(4,6-Dimethoxy-2-piperidinyl) amino] carbonyl] amino] sulfonyl] -6- (trifluoromethyl) -3-pyrimidinecarboxylate Sodium (II)

To a stirred solution obtained by dissolution. 75 ml of dimethylformamide -50 g (0.175 mol) of methyl 2- (aminosulfonyl) -6- (trifluoromethyl) -pyridinecarboxylate and 55.0 g (0.200 mol) of phenyl-4,6-dimethoxy-pyrimidin-2-yl-carbamate at room temperature, 30 'ml of triethylamine is added. After the solids have dissolved, the amber solution is diluted with 150 ml of methanol. The resulting solution was slowly added with 40 g (0.185 mol) of 25% sodium methylate at room temperature. After addition of 1.0 g of sodium methylate, 1 g of the previously prepared substance named as crystallization starting material is added to the solution. The resulting precipitate was cooled to 10 ° C and stirred for 30 min. The precipitate was filtered off, washed with cold methanol (2x50ml) to give 75.7g of a solid, m.p. temp. 176 -77 ° C (dec.). The precipitate contained 3.0% water (determined by Karl Fischer titration method) and 89.2% of the target material as given in the name (high performance liquid chromatography data). yield, including methyl 2- (aminosulfonyl) -6- (trifluoromethyl) -3-pyridinecarboxylate and added. crystallization starting 5 was 81.4%. ...

EXAMPLE 8

Methyl 2 - [[[[(4,6-dimethoxy-210 pyrimidinyl) amino] carbonyl] amino] sulfonyl) -6- ,.

Preparation of (trifluoromethyl) -3-pyrimidine carboxylate sodium salt

To a solution of 40 ml of methanol was dissolved 9.5. g 15 (0.021 mol) · · ', methyl 2 - [[[[(4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] -6- (trifluoromethyl) -3-pyridinecarboxylate added 5.0 ml (0.023 mol) of a 25% solution of sodium methylate in methanol.

The resulting liquid mass is stirred at room temperature for 40 min, filtered to give 8> 3 g of sodium salt; 172-173 ° C (dec.). Water content; determined by the Karl 'Fisher titration method was 5.9%.

Applying the methodology described in U.S. 4, / 774,337 or 25 Examples 1-8 and Equations. 1-6, the compound represented by Formula I (Compound 1) may be prepared by one of the methods described.

CO ₂ CH ₃ OC1SPase form o

I!

SO ₂ HIICiHS - ((3) y

K

OCH.Communication-1

Suitable forms of use of the compounds (Formula 1) may be formulated according to known methods, including powders, granules, tablets, solutions, suspensions, emulsions, hygroscopic powders, emulsifiable concentrates and the like. Many of them can be used directly. The spray formulations can be: · prepared using suitable media, · applied by spraying from several liters to hundreds of liters per hectare .. Concentrated formulations are mainly used as intermediate forms for further application. % to 99% by weight of the active ingredient (s) and at least one of (a) 0.1% to 20% of the surfactant (s); and

b) 0% to 99) 5% 'solid or liquid. Specifically, they will contain the following ingredients in the following ratios:

Weight percentage *

Active ingredient • or ' Solvent Surface s active * material Hygroscopic powder 20-90 0-74 1-10 Oil suspension · emulsions, ~ 3-50 40-95 0-15 solutions (including emulsify the ducks- concentrates) 'Suspension in water 10-50 40-84 1-20, Powder 1-25 70-99 0-5. Granules- and tablets 0.1-95 5-99.9 .1-15 Concentrated 90-99 0-10 0-2 composition Filled Films · 0.1-90 10-90 0-10

* The sum of the active ingredient and one of the surfactants or solvents is 100% by weight

Of course, depending on the intended use and the physical properties of the compounds, lower or * higher amounts of the active ingredient may be present. Sometimes a larger surface may be desirable. - the ratio of active substance to active ingredient which is either created immediately upon application, -. or, achieved by mixing in tanks.

Typical solid diluents are described in Watkins, et al. Handbook. of Isecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey, however, other solids, whether natural, of origin, or of industrial origin, may be used. Diluents having 'enhanced absorbent properties are more desirable for' hygroscopic powder and higher density 'powder. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Intersience, New York, 1950. Suspension concentrates 'preferably have a solubility lower than' 0.1%; it is also desirable that the solution concentrates be stable (phase separation) at -0 ° C. McCutcheon's Detergents and Emulsifiers Annual MC 'Publishing' Corp., Ridgewood, New Jersey, and Sisely and Wodd ^ '' Encyclopedia of Surface Active Agents, Chemical Publication Co., Ine., New York, 1964, are listed as surfactants and . recommended areas of application. All forms of use may contain small amounts of additives for reducing foaming, sintering, corrosion, - growth of microorganisms and the like.

In such compositions, methods of preparation ^- is well known. Solutions are prepared simply by mixing the ingredients. Fine solid compositions - are prepared by mixing, usually and crushing with presses or hydrodynamic mills. The suspensions are prepared by wet milling (see, e.g., Litter, U.S. Patent 3,060,084). Granules and tablets may be prepared by spraying the active ingredient onto the formed granular carriers or by agglomeration. See JEBrovning, - ~ Agglomeration,

Chemical Angling, December 4, 1967, pp.l47ff and

Perry’s Chemical Engineer’s Handbook, 5th. Ed.,

McGraw-Hili, Nev York, 1963, p. 8-57ff.

Additional information regarding the use of 'forms' can be found, for example:

M.H '. Lous, U.Si-Patent '3,235,361 _t 1966m- Feb

15d., From column 6, line 16 to column 7, line 19, and.examples 10 to 41;

R., W. Luękenbaugh, Ū.S. Patent 3,309,192, 1967. March

14d, column 5, line 43 to column 7, line 62, and examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167, and 169-182 ;

H. Gysin · and E.- Khusli, U.S. Patent 2, 891, 855,

1959 June 23, 1959, column 3, line 66 to column 5, line 17, 'and examples 1-4; GC Klingman, ^!: W / nd Control as a Science, John Wiley 25 and Sons..Ine., New York, 1961, p. 81-96; and

-J. D. Fryer and S. A. Evans, Weed Control Handbook,

5th Ed., Blackwell Scientific Publications, Oxford, '1968, p. 101-103.

In the following examples, all components, unless otherwise stated, are expressed as a percentage by weight.

EXAMPLE A 35

Concentrate

Methyl 2 - [[[[(4,6-dimethoxy-2-pyrimidinyl) a-mino]. Carbonyl] amino] sulfonyl] -6- (trifluoromethyl) -3-pyridinocarboxyl-99% 'trimethylonyl polyethylene glycol ether - 1%

The surfactant is sprayed onto the active ingredient in a mixer and the mixture is sieved through a mesh before packing in D.S.S. No.40 <0.42: mm pairs).

The concentrate can be further prepared for practical use.

EXAMPLE B

Hygroscopic powder z

Methyl 2 - [[[[(4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] -6- (trifluoromethyl) -3-pyridinocarboxylic acid '-65%' dodecylphenol- polyethylene 2% glycol ether sodium 'lignin sulphonate 4% sodium aluminosilicate 6% montmorillonite (calcined) 23%

The ingredients are thoroughly mixed; The liquid surfactant is sprayed. in a blender on solid ingredients. Grinding> with a hammer mill results in the major · particles smaller than 100 microns, which are again mixed and passed through; network U.S.S. No.50 (0, 3 -mm pairs) Ū.S.S. and packed '.

EXAMPLE C

Aqueous suspension

Methyl 2 - [[[[(4,6-dimethoxy-2-pyrimidinyl) amino} carbonyl] amino] sulfonyl] -6- (trifluoromethyl} -3-pxridinocarboxylate 50.0% polyacrylic acid (thickener) 0.3% dodecylphenyl -'Polyethyl.leri- 0.5% glycol ether patri hydrophosphate · 1% sodium aluminum silicate '6% sodium dihydrophosphate - · 0.5% polyvinyl alcohol 1.0'% water% <6.7%

The ingredients are mixed and then ground together in a sand mill (generally up to 5 microns in size).

EXAMPLE. D · ⁵

Suspension in oil

Methyl 2 - [[[[(4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] -6 (trifluoromethyl) 3-pyridinocarboxylate 35% polycarboxylic alcohol ester, and oil-soluble petroleum sulfonates , mixture 6% xylene 55%

The ingredients are mixed and co-ground in a sand mill to produce particles substantially smaller than 3 microns. The product can be used directly, diluted in oil or suspended in water.

EXAMPLE E 15

Suspension in oil of methyl 2 ~ [[[[(4,6-dimethoxy-2 'pyridinidin)]. , Λ r * _ amino] carbonyl] amino] sulfonyl] -6-. . .

(Trifluoromethyl) -3-pyridinocarboxylate · 25% Polyoxyethylene Sorbitol '' 5% Hexalate ...

higher aliphatic hydrocarbons · oil 70%

All ingredients are sand milled until 'solids become less than 5 microns'. The resulting slurry may be used directly, but preferably diluted in oil, or suspended in water. .

. · 'EXAMPLE F

Suspension in water 1C

Ketyl 2 - [, [(((4,6-dimethoxy-2-pyrimidinyl) amino] carbonylamino] sulfonyl] -6- {trifluoromethyl) -3-pyridinocarboxylate '-25% hydrated' atapulgite '.3% crude' calcium lignin sulfonate 10% e

sodium dihydrogen phosphate 0.5% water 63.5%

The mixed ingredients are milled in a ball or roll mill until the particle diameter is less than 10 microns. \

Ί c

X

EXAMPLE G

Hygroscopic powder - Vol

Methyl 2 - [[I [<4,6-dimethoxy-2-pyrimidinyl ') amino] carbonyl]' amino] sulfonyl] -6- (trifluoromethyl) -3-pyridinocarboxylate '' ^ 40% sodium dioct .ylsulfonsuccinate. 1.5% sodium lignin sulfonate 3% low viscosity methylcellulose 1.5% at sDulciita. s 54%

The ingredients are thoroughly mixed, air-milled, the resulting particles of about 15 microns re-mixed and sieved through a mesh U.S.S.No. before packing. 50. (0.3 mm pores).

All compounds in the same way. to describe can be obtained in the invention. 10th EXAMPLE H Granules hygroscopic powder 15% plaster 69% potassium suifate 16% C- 15th Ingredients are mixed rotary mixer and, by pulverization water,  granules are formed '. When most • Materials granulate j.ama to the desired

with a particle size of 1.0 to 0.42 mm (U.S.S. No. 18 to 40 mesh), the pellets are removed, dried, and

2 (0 sieved. The remaining larger particles are comminuted to the desired size. These granules contain% 'active ingredient.

• EXAMPLE I ·

Hygroscopic Powder • Methyl 2 - [[[[(4,6-Dimethoxy-.2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] -6- (trifluoromethyl) -3-pyridinocarboxylate 50% Sodium Alkyl Naphthalenesulfonate. 2% low viscosity methylcellulose 2% diatomaceous earth 46%

The ingredients are mixed, coarsely comminuted and then milled in an air mill to obtain particles of active ingredient smaller than 10 microns in diameter. The product is mixed again before packing.

EXAMPLE J

Pills

Methyl 2 - ['[[[(4,6-dimethoxy-2-pyrimidinyl)] -. amino] catbonyl] amino] sulfonyl] -S- (trifluoromethyl) -3-pyridinocarboxylate.s. 25% anhydrous sodium sulphate .10% crude calcium lignin sulphate 5% sodium alkylnaphthalenesulphonate 1% calcium / magnesium bentonate 59%

The ingredients are mixed, crushed and 'moistened (approximately' to 12% 'water). The mixture is compressed into cylinders of approximately 3 mm diameter *, which are cut into tablets of approximately 3 mm height.' e

Once dried, they can be used immediately, or the dried tablets can be crushed and sieved through a U.S.S. No. 20 (0/84 mm pores) Granules retained in O.S.S. No. 40 (0.42 mm pores) mesh are packaged for use and finer processed in the following cycle.

EXAMPLE K 'Hygroscopic Powder

Methyl 2 - [[[[(4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] -6- (trifluoromethyl) -3-pyridinocarboxylate -80% sodium alkylnaphthalinosulfonate '2% sodium lignin sulfonate 2% synthetic amorphous silica 3% kaolinifc 13%

The ingredients are mixed and then ground in a hammer mill to obtain particles having an average diameter of less than 25 mm. Before packing,% is mixed and sieved through a mesh U.S.S. No: 50 (0.3 mm pores).

EXAMPLE L

Concentrated Powder '

Methyl 2 - [[[[(4,6-Dimethoxy] 2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] -6- (trifluoromethyl) -3-pyridinocarboxylate 98.5% Silica Aerog 0.5% Purified synthetic amorphous silica 1.0% oxide

The ingredients are mixed and then ground in a hammer mill until almost all of the concentrated powder particles pass through U.S.S. No. 50 (0.3 mm pair) grid. Then . this material can take many forms.

EXAMPLE M

The solution

Methyl 2 - [[[[(4,6-Dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] -6 (trifluoromethyl) -3-pyridinocarboxylate Sodium 5% Water 95%

The salt is added directly to the water, mixing with the resulting solution, which can be dispensed into the user.

EXAMPLE N

The solution

Methyl 2 - [[[[(4,6-dimethoxy-2-pyrimidinyl) z-amino] carbonyl] amino] sulfonyl] -6- (trifluoromethyl) -3-pyridinocarboxylate sodium salt 50% aqueous solution of polyvinyl alcohol- 49% Sodium dodecylbenzene sulfonate. 1% Initially mix dry ingredients, add polyvinyl alcohol solution and mix. 10-40 ml • «· of the mixture is poured into a thin layer on a flat surface and dried to remove excess water.

Use imams

The test results show that the compounds described herein are active herbicides used before germination of plants. either after sprouting or as growth regulators of the twigs. The compound is used to limit the growth of various herbs and broadleaves in cereal crops before and after emergence. The compound is particularly effective in controlling the growth of the mothweed (Alopecurus mycsuroides), a cereal such as wheat (Triticum aest-ivum), barley. (Hordeum vulgare), oats ^: (Avena sativa), rye (Secale cereale) .and hybrid, triticale (Tri * ticum x secale) in crops.

The effective amount of the compound described in the present invention depends on a number of 'factors.' They. factors include: selected form of application, method of application, amount of vegetation available, growing conditions and p'an. In general, an effective application rate of the compound of the present invention is from 0.001 to 20 kg / ha, usually from 0.002 to 0.25 kg / ha. The compound of the present invention may be used alone or in compositions with other commercial herbicides, insecticides or

C

Suitable below are the 'fungicides' of the present invention.

in the list. listed herbicides, mixtures. - 'The combination of the compound as claimed with. one or more of the herbicides listed below may. be particularly useful for regulating weed growth in cereal crops.

Main title

Chemical name amidosulfuron barban bensulfuronmethyl bentazone 'benzoylprop biphenox bromoxynil

-butachlor chlorprotam

N - [[[[(4,6-Dimethoxy-2'-pyrimidinyl) amino] carbonyl] amino] sulfonyl] -N-methyl methanesulfonamide

4-Chloro-2-butyl-3-chloro-carbamate 2 [[. [[(4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] methyl] benzoic acid methyl ester f

3- (1-Methylethyl) - (1H) -2,1,3-benzothiadiazin-4 (3H) -one 2,2-dioxide N-benzoyl-N- (3,4-dichlorophenyl) -DL-alanine methyl 5- (2,4-Dichlorophenoxy) -2-nitrobenzoate

3,5-Dibromo-4-hydroxybenzonitrile N- (butoxymethyl) -2-chloro-N- (2,6-diethylphenyl) acetamide

1-Methylethyl 3-chlorophenylcarbamate

chlorosulfuron 2-chloro-N - [[(4-methoxy-6-methyl- i, A »' 1,3,5-triazin-2-yl) amino] - carbonyl] benzenesulfonamide chlortoluron • N- (3-chloro-4-methylphenyl) .N, N- ' 'dimethylurea cinmethylin exo-1-methyl-4- (1-methylethyl) -2 [(2-methylphenyl) methyl] oxy] -4-oxobicyclo [2,2,1] heptane DCPA dimethyl-2,3,5,6-tetrachloro-1,4- benzene dicarboxylate. ... diallate S- (2,3-Dichloro-2-propenyl) bis (1-methylethyl) carbamothioate dicamba 3,6-dichloro-2-i such benzoine «·» acid dichlobenyl '2) 6i ~ dichlorobenzonitrile dichlorprop. (+) - 2- (2,4-Dichlorophenoxy) propane acid dichlofop (+) - 2- (4- (2,4- " d'ichl'orophenoxy) phenoxylpropane acid ' difenzocato 1,2-dimethyl-3,5,5-diphenyl-1H-pyrazolium diflufenican 2 ', 4'-difluoro-2 - (&, &, & - trifluoro- m-toluoloxy) nicotinanilide DNOC 2-methyl-4,6-dinitrophenol - phenoxaprop-ethyl ethyl (±) -2- [4 - [- (6- (chloro-2-benzoxazolyl) oxy] phenoxy] propane 'atas f enoxaprop-ethyl flamprop with Harvest Protector! N-benzoyl-N- (3-chloro-4-fluoro) - t phenyl) DL-alanine ' fluazifop (±) -2- [4 - [[5- (trifluoromethyl) -2- pyridinyl] oxy] phenoxy] propanoic acid fluazifop ~ P (R) ~ 2- [4 - [[5- (trifluoromethyl) -2-pyridinyl] oxy] phenoxy] propanoic acid

fluchloraline fluorochloridine fluroxypyr takes z amene aboxidant isoproturon linuron

MCPA

MCPB mecoprop mefluidide metabenzothiozuron methoxuron metribuzin

N- (2-Chloroethyl) -2,6-dinitro-Npropyl-4- (trifluoromethyl) benzenamine

3-Chloro-4- (chloromethyl) -1- [3- (trifluoromethyl) phenyl] -2-pyrrolidinone

4-Amino-3,5-dichloro-6-fluoro-2-pyridyloxyacetic acid

6- (4-Isopropyl-4-methyl-5-oxy-2-imidazolin-2-yl) -m-toluic acid methyl ester and 6- (4-isopropyl-4-methyl-5-oxy-2-imidazolin-2-yl) -p -toluene acid methyl ester

4-Hydroxy-3,5-di odobenzonitrile N- (4-isopropylphenyl) -N ¹ , N'-dimethylurea

N '- (3,4-Dichlorophenyl) -N-methoxy-N'-methylurea. (4-Chloro-2-methylphenoxy) acetic acid

4- {4-chloro-2-methylphenoxy) butanoic acid (+) - 2- (4-chloro-2-methylphenoxy) propanoic acid N- [2,4-dimethyl-5 - [[trifluoromethyl) sulfonyl] amino] phenyl] acetamide

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

N '- (3-Chloro-4-methoxyphenyl) -N / N-dimethyl urea

J

4-Amino- ¹ '6- (1,1-dimethylethyl) -3 * ^-1 (methylthio) -1,2,4-triazine-5 (4H) -one Metsulfuron Monuron Neburon Picloram

PPG-1013 propanil with 1f tome t ron methyl terbuthylazirias terbutryl thifensulfuron methyl trialate tribenuron methyl trifluralin

[[['(4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] carbonyl] amino] -. sulfonyl] berizoic acid methyl ester.

N '(4-chlorophenyl) -N, N-dimethylurea

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

4-amino ~ 3 _f 5,6-trichloro-2-. piri din o-ka rb onic acid

5- [2-Chloro-4- (trifluoromethyl) phenoxy] -2-nitroacetophenone oxirao-O-acetic acid methyl ester

K ~ 13 _f 4-dichlorophenyl) propanamide • k

4 iii (4 _f 6-Dimethyl-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] benzoic acid methyl ester '

2 (tert-butylamino) -4-chloro-6 {e t i 1 a m i n o) - s -1 r i a z i n a s

N- (1,1-dimethylethyl) -N'-ethyl-6 (methylthio) -i, 3,5-triazine-2,4-diamine [[[(4-methoxy-6-methyl-1,3 _f] triazine) -2 '(ii) amino] carbonyl] amino] sulfonyl] -2-thiophenocarboxylic acid methyl ester

S- (2,3,3-trichloro-2-propenyl) -3 * bis (1-methylethyl) carbamothioate 2 - [[[[K-H-methoxy] G-methyl-1,3,5-triazin-2-yl] ) -N-methylamino] carbonyl] amino] sulfonyl]] benzoic acid methyl ester

2,6-Dinitro-N, N-dipropyl-4- (trifluoromethyl) benzenamine

2.4- D (2,4-Dichlorophenoxy) acetic acid

2.4-DB (2,4-Dichlorophenoxy) butanoic acid

The herbicidal properties of the compound of the present invention have been tested in a series of greenhouse and field studies. '

Significant growth restriction of the mouse moth (Alopecurus myosurides) using the compound described in the present invention is illustrated by the results of the assays performed in the three test plots * in Tables D, E and F. The description and results are given below.

Test A

3.5

Hordeum vulgare, Echinochloacrus-galli, Bromus Secslonus, Pennsylvania Thistle. (Kanthium pensylvançcum), · 'maize (Zea mays), cotton (Gossypium' birsutum), gloves (Digitaria spp.), Bristle (Setaria faberi), batato (Ipomoea spp.j, rice) (Oryzaya sativa), sorghum ( Sorghum bicolor), soybean (Glycine max), sugar beet (Beta vulgaris), galen (Abutilon theophrasti), wheat (Triticum aestivųm), wild oat (Avena fatua) and roundworm (Cyperaus rotundus). At the same time, these crop and weed species were exposed to the test chemicals and post-emergence.

In these experiments, the size of the plants after germination reached potted plants up to eighteen centimeters (two to three leaf phase). Control plants were also affected. ' were kept in a greenhouse for approximately sixteen days, after which all species were compared with 'control plants' and. .Z '*' visually rated. The plant response rating, summarized in Table A, is presented on a scale of 0 to 10, where 0 indicates no effect and 10 represents complete growth restriction. 'A dash (-) indicates that. no test results-

Table A The compound Χ- Tape A Compound ' 1 Rate (g / ha) ⁵⁰ ΙΟ Quantity (g.ha.) '50 10th Postpartum Postpartum operation functioning's Barley .6 2 Barley 7th 4 Roller coaster ? 9th Roller coaster » 9 ' 5 Dirse 8th 7th Dirse  7th 2 Shit 10th Ί0 Shit 9 ' - Corn 9th ₇ - Corn 9th 7th .Cotton 9th 9th Cotton 8 ' 7th The glove 7th 7th The glove 8th 8th Sherry 7th '.4 Sherry 5 • 3 Batatas 3 5 Batman 9th 8th Strawberry · - · 10th Weasel 10th 19th Rice' 9th 9th Rice 10th 9th Sorg Ί 2 Rice. 10th 9th Soya »* 9th 9th Soya 9th 8th Sugar Sugar beets 9th 9th beets 9th 9th Galenis 9th 8th Galenis 9th 7th Wheat j. 0 ' Wheat * 0 0 Wild - Wild oats 3 0 oats 3 0

Test B

Barley (Hordeum vulgare), Echinochloacrus-galli, Alopecurus myosuroidesj, Medellin, Stellaria (Xanthium)

pensylvanium), Zea mays, Gossypium hirsutūm, Digitaria spp., Bromus tectorum, Setaria viridis _f Datura stramonium, Sorghum halo (Chenopodium album), sweet potato (Ipomoea spp.), Rape (Brassica patus), rice (Oryzava sativa), cassia (Cassita obtusifolia), soy. (Glycine max), · sugar beet '(Beta vulgaris), fibrous' galenium (Abūtilon theophrasti), wheat (Triticum a detailedivum),. tubers of wild buckwheat (Polygonum convolvulus), wild oats (Avena fatua) and cypress (Cyperus rotundus} were planted and exposed to the test chemicals dissolved in a non-phytotoxic solvent prior to germination. In these experiments, the post-emergence plant size ranged from two to eighteen centimeters (two to three leaf phase) .The exposed and control plants were kept in a greenhouse for approximately twenty-four days, after which all species were compared with the control plants and visually. The plant response score, summarized in Table B, is given on a scale of 0 to 10, where 0 means no effect and 10 indicates no growth.

restriction full. Dash test results. (-) means that Table B The compound 1 Rate (g / ha) After germination 62 16th 4 1 Barley 3 0 0 0 OwnFarm 10th 10th 10th 8th The gnome 10th 10th 1 ° 9th Shit 10th 10th 10th 10th Corn 10th 8th 7th 7th Cotton 10th 10th 10th 8th The glove 10th 6th 5 4. Dirse 9th 3 0 0

Colored bristle 6th 3 0 0 Green sherry 9th 6th 4 - 3 Durnarope 10th 1 ( 10th .10 Sorg 5 * 3 0 0 Dove 10th 10th 10th 7th Batman θ. '5 5 2 Weasel 10th 10th 10th 5 Rape 10th 10th 10th : 10 Rice dry seeds 10th 9th 7th 5 Cassia 10th 10th 10th 10th Soya 10th .10 10-  9th sugar beet 10th 10th r 10th Sida prickly 10th 10th 10th 9th Galenis 10th 10th 10th 7th Wheat 3 .0 0 0 Wild buckwheat 10th 10th 10th 10th Wild Oats 4 ' 0 0 0 Roller coaster '1.0' 10th 10th 10th Leritel B · The compound 1 Rate '(g / ha) Before germination 62 16th 4 1 Barley 6th 5 3 0 A fagot 7th 6th 5 3 The gnome 8th 7th 7 5 Shit 10th 8th 7th 7th Corn '7 6th 0 0 Cotton 8th 8th 7 5 The glove. 9th 8th 7 6 Dirse -5 3 0 0 Colored bristle 7th 5 0 0 The Green Bristle 9 ' 7th 5 0 Durnarope 9th 9th 9 9 Sorg 8th 6th 3 0 Dove - -  _ Batman 8th 6th 3 0 Weasel 10th 10th 8 6

Rape 10th 10th 10th 10th Rice dry seeds. in- 10th 10th 7th Cassia 9th 8th 8th 3 Soya 8th 6th 5 3 ' sugar beet 10th 10th 10th 10th Sida prickly .8 7th 7th 6th Galenis 10th Ϊ0 8th 7th Wheat 3 0 . 0 ' 0 Wild buckwheat 10th 10th 9th 9 ' Wild oats 6th 3.. 0 · 0 Roller coaster 10th 10th 8th '4

-Testing C

The compounds tested in this assay were in a non-phytotoxic solvent and were 'germinated germinated plants to prepare the affected seeds for 1-4 leaves.

The pre-emergence soil was the soil surface before (pre-emergence application) and the phase (post-emergence application) used in the pre-emergence test, where a 60:40 mixture of pre-emergence and greenhouse soil was used in post-emergence testing. In the pre-emergence test, test compounds were used approximately one day after inoculation. Crop and weed sprouts were grown to a certain size All plant species. was common greenhouse practice, covered winter barley? buckwheat (Galium subspecies), grown using crop and weed species (Hordeum vulgare '' Igri '', (Alopecurus myosuroides), media), linden (Bromus (Viola arvensis), green asparagus) (Stellaria tectorum), Orphaned Setter (Setaria viridis), Persian Veronica (Veronicaca Persica), Rape (Brassica natus 'Jet.' Neuf), Reed (Lolium mutiflorum), Sugar Beet (Beta vulgaris US1), Sunflower? Helianthus anpuus Russian

L gin), spring - wheat. (Triticum aestivum ERA)., Winter wheat (Triticum aestivum

Talent), wild buckwheat (Polygonum convolvulus), wild mustard (Sinapis arvensis), wild oats (Avena fatuą) 'and wild radish (Raphahus. Raphanistrum). Post-emergence oocytes and wild oats were treated with test compounds at two stages of growth. In stage 1 the plants had 2-3 leaves, in stage II the plants had. 3-4. leaves or began to shoot shoots. The affected and control plants were kept in the greenhouse for approximately '21-28 days, after. the species were compared with control plants and visually evaluated. The plant response score, summarized in Table B, * is plotted on a scale from 0. to 10, where 0 indicates no effect and 10 'indicates complete restriction. A dash (-) indicates that there are no test results.

Table C The compound 1 Quantity ^; (g / ha) After germination 125 64 32 - 16th 8th 4. Nutcracker (1) - - - - - -. Nutcracker (2) 10th 10th 10th 8th 6th 5 The gnome 10th 8th 6th 4 2 0 Dirse - 2 · Uh .. 0 0 0 0 Orphaned Orphan 4 2- 0 0 0 .0 Sticker (1) 10th .7 5 4. 2 0 The Green Bristle 10th 9th 8th 6th 4 3 Persian Veronica 3 2 O . 0 0 0 Rape 10th 10th ^E 10 .10 : io 10th Sweed 6th 5 ' 3- 0 '0 0 sugar beet 10th 8th 6th 6th 5 4 Sunflower 10th 10th 10th 10 ' . 10th  10th Wheat. (Summer) 2 0 0 0 0. 0 Wheat (Winter) 2 0 0 0 ' 0 0 Wild buckwheat 10th 10th 8th 6th .4 2 Wild mustard 10th 10th 10th 10th 10th 0

Wild Oats (1) 0 0 0 0 0 Wild Oats (2) 0 .0 ⁰ 0 0 Wild horseradish 10th 10th 10th 10th 10th Winter barley 4 2 0 0 • 0 Table C ' The yoke 1 Rate (g / ha) ' Pre-emergence action 125 64 ³² 16 - 8th 4 Nutcracker (1) 10th 8th 7th 7th 3 .2 Doggie (2) 10th 10th 8th 7th 4 3 The gnome 10th 10th 10th 10th 9 - 8th Dirse 7th 5 4 . 2. 0 0 Orphaned Orphan. 10th 10th 10th .10 9 ' 7th Lipic (1) 10 10th 10th 10th S 6th Green Ishershire 10th 8th 7th 6th 4 .2 Persian Veronica 10th . 10th 10 · 8th 7th 6th Rape 10th 10th 10th  10th 10th 9th Sweed 7th 6th 5 3 2 · 0 sugar beet 10th 10th 10th 10th .9 8th Sunflower -. 10th 10th 10th 10th 8th 6th Wheat (Summer) · 2 1 0 0 .0- 0 Wheat (winter) 2 2. 0 0 0 0 Wild buckwheat '10 10th 8th 7th 5 3 Wild mustard 10th 10th 10th 10th 9 · 8th Wild Oats (1) 3 2 0 0 0 0 Wild Oats (2) 4 2 0 0 0 0 Wild horseradish 10th 10th 10th 10th 8th 6th Winter barley 6th 4 2 r 0 ' , 0

Test D

The trial plot was sown with winter wheat z

(Triticum astivum), winter barley (Hordeum vulgare) and fescue (Alopecurus mysuroide's) seeds and after germination were treated with test chemicals dissolved in non-toxic solvents. After thirty-six days, the affected plants were compared with control plants and visually evaluated. The plant response rating, summarized in Table D, is given up to 10, where 0. means. that there is no effect, 0 10 is completely limited.

ine from 0 growth

Table D

Compound 1 (36 days)

Rate (g / ha)

18 '

Winter wheat winter barley ♦

Mousehole '

. 10th

Testing _t .E

The test plot was seeded with winter wheat (Tritieum astivum) and fodder seed (Alopecurus myšuroides) seeds and under test chemicals in non-toxicotoxic solvents. Nine-day exposed plants with control plants, response assessment, germination treated.

dissolved After forty were compared with and visually evaluated. 'The sum of the plants in Table E is that it is not on the scale from ^: 0 to 10, where 0 means ->

and 10 is the full restriction on growth. .

Table E

Compound 1 (49 days)

Rate (g / ha) Winter wheat- Mouseworm 64 ⁰ 10th 32 ⁰ 10th 16th ⁰ 10th 8th 0 9th

Test F

The test plot was sown with seeds of winter wheat 5 (Triticum - astivum), winter barley (Hordeum vulgare) and Alopecurus mysuroides. sprouting was treated with test chemicals dissolved in non-phytotoxic solvents. Sixty-six days later affected

plants were compared to control plants and visually evaluated. The plant-response rating, summarized in Table D, is given on a scale from 0 up to 10, where 0 means restricted entirely. that there is no effect and 10 is growth Table F Compound 1 {49 days) Rate (g / ha) Winter Winter Pelinis .64 wheat 0 barley ⁵ fagot '10 32 0 • 5 9th 16th 0 4 8th 8 ' 0 3 7th .4 0 2 4 Test G Trial mouse rancher (Alopecurus mysuroides), Talent winter wheat (Triticum

aestevum) and Igri winter barley (Hordeum vulgare) · kuitūrs were grown under greenhouse conditions Up to 2 leaf phase. .The standard 4-inch dishes filled with Matapeake-sandy soil, sand and a Μίκ mixture (approximately 50:10:40 by volume) were used.

Concentrated solutions of juginib 1 - and its sodium salt were prepared by dissolving these substances in a small amount of acetone and water (1 mL), respectively. The appropriate volume of each concentrated solution was dissolved in surface (28 mL) / diluted. deionized water containing 0/25% (w / v) ”X-s77 active substance,., up to normal volume for spray application. The test plants were treated with the following solutions <2,4,8 and 16 g of active ingredient per formulation. tested on a mouse seed and 8, 16, '32 and '64 g active ingredient / ha on a cereal crop. Each treatment was repeated ^ 4 times. '

After treatment, the test plants were returned 'to e

a greenhouse for periodic observations. After 21 days, limb growth and damage to cereal crop. were evaluated visually. Use a visual rating from 0 to 100%. scale, where 0 indicates no visual changes in the test plant compared to controls, and 100% indicates that the plant has died. On this scale, a threshold of 20% or higher corresponds to a.-Unacceptable-crop damage * level.

Lj © rit © l0 G COMPOUND '1- IR COMPOUND 1 PRODUCT OR PVOH FILMS Compound 1 · Quantity form (g / ha) Untreated. . 0 Protective 'PVOH · film 0 Compound 1 {95% ai) ² , - 4 8th 16th 32- 64 Compound 1 Quantity form . (g ai / ha) 1 of the compound Sodium salt (95% ai) ' 2 4 8th 16th 32 64 Compound 1 PVOH - (approx 45% ai) 2 4 '8 16th 32 ' 64

SODIUM. SALT IN INDUSTRIAL FORM

Weed ' and cultures species * 'bkg MWT BWI -— (phytotoxicity, - no? %) --- Q * * 0 0 0 'o 0. 60 - - 74 ' 86 0 3 90 0 10th - · Ίο ' 23rd - 25th 38 Weed hardware cultures .species * BKG . MWT · BWI --- (phytotoxicity, %) -

60 - 78 - t- 88 o 3 93 3 13th - 8th 23rd 23rd 40

60 - 75 - - 85 0 .3 90  , 0 10th - 5 25th 20th . 38

Continuation of Table G

Compound Sodium PVOH · ...

(around

45% ai) 2 58 - - • 4 79 ' λ * -. 8th 88 . 0 ' 3 * 16th 90 .0 18 ' 32 - 5 23rd 64 . - 13th 35 PVOH = Polyvinyl alcohol, ♦ ai = active ingrad.ient-as * Weeds and crops species; BKG mouse foxglove, WWT = winter wheat Talent ,. BWI =

winter barley ”Igri ** Each number. corresponds to an average of four measurements ...

Claims (6)

DEFINITION OF INVENTION ' A compound of the formula and its salts, hydrates and complexes with lower alcohols, for use in agriculture. 15th Composition of a desirable vegetation component suitable for agriculture and at least one surfactant, diluent, b. 3. A method for limiting the growth of unwanted vegetation by> treating the site of the pesticide to be protected by applying 25 an effective amount of a compound as defined in claim 1 '. 4. A method of limiting the growth of unwanted vegetation in cereal crops by applying a herbicide treatment to a site that we want to protect, 30 effective amount] of a compound as defined in claim 1. . 5. A method for limiting the growth of a mothbird by applying a herbicide treatment at a site where the desired effect is achieved by applying an effective 35 is the amount of a compound as defined in claim 1. '6. A compound of the formula