BG61491B2 - Fluoroalkoxy amino triazines for control of weeds in sugar beets - Google Patents

Abstract

This invention comprises novel fluoroalkoxy amino triazines, agriculturally, suitable compositions containing them, and their method-of-use as preemergence and/or postemergence herbicides or plant growth regulants.

Description

TECHNICAL FIELD

The invention relates to a compound suitable for use in plant protection compositions and methods, and in particular to a method for combating undesirable vegetation.

BACKGROUND OF THE INVENTION

From (1) and (2) known are herbicidal sulfonylureas of the general formula halogen, C ₍ -C ₄ alkyl, C ₂ -C ₄ haloalkoxy, NR ₁₂ R ₁₃ , etc .;

R ₆ is, among other things, C 1-6 alkoxy, C, C, haloalkoxy, C-C. alkoxyalkoxy and the like; and

R ₁₂ and R ₁₃ independently of one another are H or C 1 -C ₄ alkyl.

[1], [2] and [3] generally disclose some of the compounds according to the invention, but they do not contain data on these compounds or on them in sugar beet plantations.

In [4], herbicidal sulfonylureas of the general formula are disclosed

* 1

wherein

Rj means, together with all other meanings, CO ₂ R ₁₀ , etc.,

R ₂ is H, F, Cl, Br, CF ₃ , CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , SCH ₃ or SC ₂ H ₅ ;

R ₁₀ is C 1 -C ₄ alkyl, CH ₂ CH ₂ OCH ₃ , CH ₂ CH, Cl, CH ₂ CH = CH ₂ or CH ₂ C = CH;

R _u is H or C 1 -C ₂ alkyl;

R ₁₅ is a C _t -C ₂ alkyl, OCH _3, OC ₂ H ₅ or CH ₂ CN;

x is NR ₁₄ R _1j;

Y is OCH ₂ CH ₂ F, OCH ₂ CHF ₂ or OCH ₂ CF ₃ ;

and

Z is CH or N.

[3] discloses herbicidal sulfonylureas of the general formula

U in which

A means C-C, haloalkyl,

Z is O or S;

E is CH or N;

R 1 is, among other things, H, COR ₆ , etc .;

R ₂ is, among other things, H, etc .;

R ₃ and R ₄ independently of one another are H in which

R is H, halogen, N0 _2, C ₁ -C ₄ haloalkyl, Cj-C ₄ alkyl, Cj-C ₄ alkoxy, C ₂ -C ₅ alkenyl or C] -C ₄ alkoxycarbonyl;

X is O, S, -SO- or SO ₂ ;

m is 0 or 1;

Q is, among other things, R ₁₃ , etc .;

R ₁₃ is phenyl or phenyl substituted by halogen, NO ₂ , CN, C 1 -C ₄ alkyl, C 1 -C ₄ alkoxy, C 1 -C ₄ alkylthio, C ₂ -C ₅ alkenyl, C 1 -C ₄ haloalkyl, C 1 -C ₄ alkoxycarbonyl, -NR 4 R 4, -SO ₃ H or -SO ₂ R ₄₇ R ₄₈ ;

R ₂ is C 1 -C 6 alkyl or C 1 -C 6 alkoxy, each of which is unsubstituted from 1 to 3 halogen atoms;

R ₃ is, inter alia, -NR ₄ R ₅ and the like;

E is N or CH.

In general, some of the compounds of the invention are disclosed in [4], but there are no data on the compounds or their usefulness in sugar beet plantations.

SUMMARY OF THE INVENTION

The invention provides novel compounds, as well as mixtures containing them, which are suitable for soil treatment as pre-emergence and / or post-emergence herbicides or as growth regulators.

The compounds of the invention have the general Formula I

wherein

R is C (-C ₄ alkyl, CH ₂ CH = CH ₂ , CH ₂ C = CH, cyclopropylmethyl or CH ₂ CH ₂ R ₂

R ₁ is C ₁ -C ₂ alkyl, C 1 -C ₂ haloalkyl, CH ₂ CN, CH ₂ OCH ₃ , C 1 -C ₃ alkoxy, C 1 -C ₃ alkylthio, phenylthio or R ₃ R ₄ ;

R ₂ is C ₍ -C ₂ alkoxy, C 1 -C ₂ alkylthio, CN or halogen;

R ₃ and R ₄ are independently H or CH ₃

X is NHCH ₃ , N (CH ₃ ) ₂ or N (CH ₃ ) OCH, taking into account that when R! is OCH ₂ CH ₃ or CH ₂ OCH ₃ , R is other than CH ₃ .

In the above definitions, the term "alkyl" includes straight chain or branched chain alkyl, i.e. methyl, ethyl, monomeric propyl, isopropyl or various isomers of butyl.

Alkoxyl means methoxy and ethoxyl.

Alkylthio includes methylthio and ethylthio.

The term " halogen ", whether as a stand alone word or a combined word as " halogenalkyl " means fluorine, chlorine, bromine or iodine. Further, when a complex combination such as "haloalkyl" is used, said alkyl may be partially or fully substituted by halogen atoms, which may be the same or different.

Examples of haloalkyl are CF ₃ , CH ₂ CH ₂ F, CF ₂ CF ₃ , and CH ₂ CHFC.

The total number of carbon atoms in the substituent group is denoted by the prefix C.-C., where i and j are numbers from 1 to 4.

For example, C 1 -C ₄ alkyl should mean methyl, ethyl and the various isomers of propyl and butyl; C _t -C ₂ alkylthio should mean methylthio and ethylthio and C _t -C ₂ alkoxy methoxy and ethoxy.

The following compounds are preferably due to their higher herbicidal activity and greater safety in protecting sugar beet plantations and / or delaying synthesis;

1. Compounds of formula I, in which:

R is C1-C6 alkyl;

R 1 is C 1 -C ₂ alkyl;

X is NHCH ₃ or N (CH ₃ ) ₂ ,

2. Compounds of formula I, in which:

R is C 1 -C ₄ alkyl;

R 1 is halogenalkyl C 1 -C ₂ ;

X is NHCH ₃ or N (CH ₃ ) ₂ ,

3. Compounds of formula I, in which:

R represents a C _t -C ₃ alkyl;

X - NHCH ₃

4. Compounds of formula I in which

R is C 1 -C ₃ alkyl;

X - N (CH ₃ ) ₂ .

The following compounds are particularly preferred because of their highest herbicidal activity, highest security for the protection of sugar beet plantations and / or the most appropriate delay in synthesis:

Ethyl-2 [[[[[4- (dimethylamino) -6- (2,2,2trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfonyl] -3-methylbenzoate with point mp 134 - 142 ° C; and

Methyl-2-] [[[[4- (dimethylamino) -6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfonyl] -3- methylbenzoate with a melting point of 150-160 ° C.

DESCRIPTION OF THE INVENTION

Synthesis

The following is a general scheme for the preparation of the compounds of the invention. All synthesis processes as described are multistage, with one or more methods being studied at each step.

This allows for a wide variety of possible methods for synthesizing the preparation of a specific compound of formula I.

The compounds of formula I can be prepared by the methods specified in reactions 1 and 2.

As shown in reaction 1, many of the compounds of formula I can be prepared by reacting silylsulfonamide of formula II with a heterocyclic carbamate of formula III.

Reaction 1:

the reaction of silylsulfonamide of formula VI with alkyl chloroformates, as shown in reaction 4.

Reaction 4 ίΟιΝΗβζ ^w ->

Μι

VI η

The reaction is carried out at a temperature of from 0 to 50 ° C in a solvent such as acetonitrile, dioxane or tetrahydrofuran in the presence of a source of fluoride ions such as cesium fluoride or tetrabutylammonium fluoride for 0.1 to 2 hours.

Alternatively, some of the sulfonamides of formula IV can be prepared and exposed to heterocyclic carbamates of formula III to obtain the compounds of formula I, as shown in reaction 2.

Reaction 2:

«I

VI »

BH £ _ ^ 1

The reaction is carried out by reacting the appropriate silylsulfonamides of formula VI with an organolithium reagent such as n-butyllithium in an inert aprotic solvent such as tetrahydrofuran at -78 to 0 ° C for 0.5 to 3 hours.

Intermediate alkylthio compound 1a is reacted with alkylene orthoformate at -78 to 0 ° C for 0.5 to 5 hours. Silylsulfonamides II are isolated by known methods.

The silylsulfonamides of formula II can be obtained indirectly by reaction 5.

Reaction 5:

SOiNHS »^ Μ1. ·>

» ^{/ H} * 1

VI w

The reaction is carried out at a temperature of 30 ° C to 50 ° C in a solvent such as acetonitrile, dioxane or tetrahydrofuran in the presence of a non-nucleophilic base such as DBU for 0.2 to 2 hours.

Many of the silyl sulfonamides of Formula II can be prepared by reacting sulfonyl chlorides of formula V with t-butyldimethylsilylamine of formula V-see [5], as shown in reaction 3.

Reaction 3. 40

N »HCOj .. CHjCb

The reaction is carried out at a temperature of from 0 to 30 ° C in a solvent such as dichloromethane in the presence of 1 to 2 equivalents of amine and 1 equivalent of sodium bicarbonate. 50

Alternatively, many silyl sulfonamides of formula II can be prepared by

The first two steps are performed as described in reaction 4. Methods for the preparation of an acid intermediate similar to the acids of formula II are also disclosed in [6].

Many sulfonamides of formula IV can be prepared by unblocking t-butylsulfonamides of formula Pa as in reaction 6.

Reaction 6:

of the title compound as a yellow oily substance with nD 1.5642.

MHz NMR (CDCl ₃ ), δ 1.39 (d, 6H, CH ₃ ); 2.39 (s, 3H, CH ₃ ); 3.99 (s, 2H, CH ₂ ) 5.32 (m, 1H, CH); 7.26 (m, 8H, arom).

Spectral lines in the infrared region (1R) 1720 cm ¹ (without impurity).

Example 2.

Methyl-2- (chlorosulfonyl) -3-methyl benzoate To a stirred suspension of methyl 3-methyl-2- (phenylmethylthio) -benzoate (24 g), dichloromethane (700 ml) water (150 ml) and concentrated hydrochloric acid (34 ml) at 0 ° C, 5% sodium hypochlorite (450 ml) was slowly added. The resulting yellow suspension was stirred for 1 hour at 0 ° C. The dichloromethane phase was dried over magnesium sulfate, filtered, concentrated and triturated with a mixture of chlorobutane and hexane to give 14 g of the title compound as a white solid, m.p. 114-116 ° C.

MHz NMR (CDCl ₃ ) δ 2.82 (s, 3H, CH ₃ ); 3.97 (s, 3H, OCH ₃ ); 7.5 (w, 3H, arom.).

IR (nujol) 1730, 1360 and 1175 cm ¹ . Example 3.

Ethyl-2- [((dimethyl) - (1,1-dimethylethyl) silylamino) -sulfonyl] -3-nitrobenzoate.

A suspension of ethyl-2- (chlorosulfonyl) -3-nitrobenzoate (14.7 g), amino-butyldimethylsilane (15.4 g) and sodium bicarbonate (3.5 g) in dichloromethane (300 ml) was stirred in a closed flask for 30 hours. 4 days at room temperature. Water (90 ml) and saturated aqueous bicarbonate solution (45 ml) were then added and the resulting mixture was stirred. The dichloromethane phase is then dried over magnesium sulfate, filtered, concentrated and chromatographed on silica gel, washed with 20% ethyl acetate in hexanes to give 12.9 g of the title compound as a white solid. mp 101 - 102 ° C.

MHz NMR (CDCL ₃ ) δ 0.30 (s, 6Η SiCH ₃ ); 0.97 (s, 9H, CH ₃ ) 1.41 (t, 3H, CH ₃ ); 4.48 (q, 2H, OCH ₂ ), 5.86 (s, 1H, NH); 7.7 (m, 3H, arom).

IR (nujol) 3200, 1730 and 1700 cm ¹ . Example 4.

Methyl-2 [(((dimethyl) -1,1 dimethylethyl) silylamino) -sulfonyl] -3-trifluoromethyl-benzoate.

A solution of N - [(dimethyl) -1,1- (dimethylethyl) silyl] -2-trifluoromethylbenzenesulfonamide (17.5 g) in dry tetrahydrofuran (250 ml) was reacted with 2.5 M butyllithium (46 ml) at 50 ° C and heated to 0 ° C for 1.5 h in an inert atmosphere. The mixture was then cooled to -78 ° C and added to a solution of methyl chloroformate in dry tetrahydrofuran (300 ml) at -78 ° C. The resulting mixture was stirred at -78 ° C for 1.5 h in an inert atmosphere and then quenched with saturated aqueous ammonium chloride (100 ml). After heating to 0 ° C, the tetrahydrofuran layer is dried with magnesium sulfate, filtered, evaporated and chromatographed on silica gel eluting with 20% chlorobutane, 10% tetrahydrofuran and 70% hexane to give 2.13 g of the title compound as a white solid, mp 80-84 ° C.

MHz NMR (CDCl ₃ ) δ 0.29 (s, 6Η, SiCH ₃ ); 0.96 (s, 9H, CH ₃ ); 4.02 (s, 3H, OCH ₃ ); 5.63 (s, 1H, NH); 7.8 (m, 2H, arom); 8 (m, 1H, arom).

IR (nujol) 3250, 1725 cm < ^{-1 >} .

Example 5.

Ethyl-2] [[[[4- (dimethylamino) -6- (2,2,2trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfonyl] -3-methylbenzoate

A solution of 2- [dimethyl- (1,1-dimethylethyl) -silylamino] -3-methyl benzoic acid (0.36 g) and O-phenyl-N- [4-dimethylamino-6- (2,2,2- trofluoroethoxy) -1,3,5-triazin-2-yl] carbamate (0.39 g) in acetonitrile (10 ml) was treated with a 1 M solution of tetrabutylammonium fluoride in tetrahydrofuran (1.1 ml). The mixture was stirred for 2 hours. After dilution of the reaction mixture with water (20 ml) and acidification with 1 N hydrochloric acid, the resulting precipitate was filtered off, washed with water and hexane / ether, dried with air, yielding 0.28 g of the title compound as white solid, mp 134-142 ° C.

200 MHz NMR (CDCl ₃ ) δ, 1, 38 (t, 3H, CH ₃ ), 2.89 (s, 3H, CH ₃ ); 3.24 (s, 6H, NCH ₃ ); 4.36 (q, 2H, OCH ₂ ); 4.74 (q, 2H, CH ₂ ); 7.4 (1H, 4H, arom. And NH), 12.38 (s, 1H, NH).

IR (nujol) 1710, 1695 cm < ^{-1 >} .

Example 6

Methyl-2- [[[[[4- (dimethylamino) -6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfonyl] -3- methylbenzoate

A solution of methyl 2- [dimethyl- (1,1-dimethylethyl) silylamino] -3-methylbenzoate (0.68 g) and 0-phenyl-N- (4-dimethylamino-6- (2,2,2-trifluoroethoxy) -1 , 3,5-triazin-2-yl / carbamate (0.79 g) in tetrahydrofuran (10 ml) was treated with a 1M solution of tetrabutylammonium fluoride in tetrahydrofuran (2.2 ml). The resulting mixture was stirred for 1 hour. h. After dilution of the reaction mixture with water (30 ml) and acidification with 1 N-hydrochloric acid, the resulting precipitate was filtered off, washed with water and chlorobutane / hexane and dried in air, resulting in 0.58 g. of the compound sought as -solid white solid, mp 151-159 ° C (dec). Another specimen, prepared in advance in the same way is melted at 150-160 ° C with decomposition.

300 MHz NMR (DMSO); δ, 3.04 (s, 3H,

CH ₃ ); 3.46 (s, 6H, NCH ₃ ); 4.10 (s, 3H, OCH ₃ ); 5.32 (m, 2H, C5 ₂ ); 7.78 (d, 1H, arom); 7.84 (d, 1H arom); 7.98 (m, 1H, arom); ll, l (s, 1H, NH); 13.1 (s, 1H, NH).

IR (nujol) 1730 cm ¹ .

The following compounds can be prepared by the known methods explained in Examples 1 to 6.

Ri

R

Table 1

X

CH3 CH3 NHCH3 CH3 CH3 N / CH3 / 2 CH3 CH3CH3 NHCH3 CH3 CH2CH3 N / CH3 / 2 CH3 CH2CH2CH3 NHCHs CH3 CH2CH2CH3 N / CH3 / 2 CH3 . CH / CH3 / 2 NHCHs CH3 CH / CH3 / 2 NHCHs CH3 CH2CH2CH2CH3 NHCHs CH3 CH2CH2CH2CH3 N / CH3 / 2 CH3 CH2CH / CH3 / 2 NHCHs CH3 CH2CH / CH3 / 2 N / CH3 / 2 CH3 CH / CH3 / CH2CH3 NHCH3 CH3 'CH / CH3 / CH2CH3 • N / CH3 / 2 CH3 CH ₂ CH »CH2 NHCHs CH3 CH ₂ CH = CH 2 N / CHF CH3 CH 2 Cl 2 CH NHCHs CH3 CH ₂ C = CH N / CH3 / 2 CH _{3 With} H2 ^ <] NHCHs CH3 dream, - <] N / CH3 / 2 CH3 CH2CH2OCH3 NHCH3 CH3 CH2CH2OCH3 N / CH3 / 2 CH3 CH2CH2OCH2CH3 N / CH3 / 2 CH3 CH2CH2SCH3 NHCH3 CH3 CH2CH2SCH3 N / CH3 / 2 CH3 CH2CH2SCH2CH3 NHCHs CH3 CH2CH2CN NHCH3 dream ₃ CH2CH2CN N / CH3 / 2

Table 1 (continued)

CH3 CH ₂ CH ₂ Cl N / CH3 / g CH ₃ ch ₂ ch ₂ f N / CHj / g CH3 CH ₂ CH ₂ Br N / CH3 / g CH2CH3 CH3 N / CHj / g CH2CH3 CH3 NHCHj CH ₂ CH 3 CH2CH3 NHCH ₃ CH2CH3 CH2CH3 N / CH3 / g CH ₂ CH ₃ CH3 / CH3 / g N / CH3 / g CH2CH3 CH2CH-CH2 N / CH3 / g CH ₂ CH 3 CH ₂ CH ₂ C! N / CH3 / g CF3 CH3 N / CH3 / g CFj CH3 NHCHj CFj CH2CH3 NHCHj CFj CH2CH3 N / CHj / g CF ₃ CH 2 - O N / CH3 / g CF ₃ dream ₂ - <] NHCHj CF ₃ ch ₂ cn NHCHj CH ₂ CH ₂ Cl CH3 NHCHj CH ₂ CH ₂ Cl CH2CH3 NHCHj CH ₂ CH ₂ Cl CH 2 CH 2 CH 3 CH 3 NHCHj ch ₂ cn CH3 NHCHj ch ₂ cn CH3 N / CH3 / g ch ₂ cn CH2CH3 N / CHj / g ch ₂ cn CH2CH3 NHCHj ch ₂ cn CH 2 CH 2 CH 3 nhch ₃ ch ₂ cn CH 2 CH 2 CH 3 CH 3 NHCHj ch ₂ cn . CH ₂ CH = CH ₂ NHCHj ch ₂ cn CH ₂ CH = CH ₂ N / CH3 / g ch ₂ cn CH2CHNOSOCCH3CH3 N / CHj / g ch ₂ cn CHgSNgOSHgSCH3 NHCHj CH2OCH3 CH2CH3 NHCHj CH ₂ OCH ₃ CH2CH3 N / CHj / g CH ₂ OCH 3 CH / CH3 / g N / CH3 / g CH ₂ OCH 3 CH / CH3 / g NHCH ₃ CH ₂ OCH 3 ^cng - < NHCHj CH ₂ OCH ₃ ^CH1 ~ <] N / CH3 / g OCH3 sns N / CHj / g OCH3 CH3 NHCHj OCH3 CH2CH3 NHCHj

Table 1 (continued)

OCHj CH2CH3 N / CH3 / 2 OCH3 CH / CH3 / 2 N / CH3 / 2 OCH3 CH / CH3 / 2 NHCH3 OCH3 CH2CH = CH2 NHCHj OCH3 CH ₂ CH »CH2 N / CH3 / 2 OCH3 sn .- <] N / CH3 / 2 OCH3 CH2CH2OCH2CH3 N / CH3 / 2 OCH3 CH2CH2CH3 N / CH3 / 2 OCH3 CH 2 CH 2 CH 3 CH 3 N / CH3 / 2 OCH3 CH2CH2C N / CH3 / 2 OCH2CH3 CH2CH3 NHCH3 OCH2CH3 CH2CH3 N / CH3 / 2 OCH2CH3 CH2CH2OCH3 NHCH3 OCH2CH3 CH2CH2BG NHCH3 OCH2CH2CH3 CH3 N / CH3 / 2 OCH2CH2CH3 CH2CH3 N / CH3 / 2 OCH / CH3 / 2 CH3 N / CH3 / 2 OCH / CH3 / 2 CHjCHa N / CH3 / 2 OCH / CH3 / 2 • CH2CH2OCH3 N / CH3 / 2 S <'Hz CH3 NHCH3 S (Nz CH3 N / CH3 / 2 S <Nz CH2CH3 N / CH3 / 2 SCH3 CH2CH3 NHCH3 sch ₃ CH2CH2CH3 NHCH3 SCH3 CH ₂ C-CH NHCH3 SCH3 CH2CH2OCH3 NHCH3 SCH2CH3 CH3 NHCH3 SCH2CH3 CH3 N / CH3 / 2 SCH2CH3 CH2CH3 N / CH3 / 2 SCH2CH3 CH2CH3 NHCH3 SCH2CH3 ^CH 2- <] NHCH3 SCH2CH3 With _H1 - <] • NH / CH3 / 2 SCH2CH3 CH2CH2CH3 N / CH3 / 2 S (H2CH3 CH2CH2OCH3 N / CH3 / 2 SC H2CH2CH3 CH3 N / CH3 / 2 SCH2CH2CH3 CH2CH3 N / CH3 / 2

Table 1 (continued)

SCH2CH2CH3 CH2CH2BG N / CH3 / 2 SCH / CH3 / 2 3 N / CH3 / 1 SCH / CH3 / 2 2CH2OCH3 N / CH3 / 2 SCH / CH3 / 2 N / CH3 / 1 SC ₆ Hj 3 NHCH3 SCsHj 3 N / CHa / a SC ₆ Hj gNz NHCH3 SCiHj 2CH3 N / CH3 / a

Formulations

Suitable formulations of the compounds of Formula I can be prepared by conventional means. These include powders, granules, flakes, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of them can be applied directly. The spray formulations can be diluted in suitable means and can be used in amounts of a few liters to several hundred liters per hectare. High-strength mixtures are mainly used as intermediates for other compositions. Generally, the formulations contain about 0.1% to 99% by weight. active ingredients and at least one of the two ingredients; (a) about 0.1 * / · to 20% of surface-active agents and / / / about 1% to 99.9% of solid or liquid inert solvents. In particular, they will contain these nigreditsites in the following approximate proportions:

Weight percentages *

We are the active ingredient

Solvent

Surfactant in the island

Wetting powders 20-90 0-74 1-10 Oil suspensions. emulsions, solutions / including and emulsifying con- centers / 3-50 40-95 0-15 Aqueous suspensions 10-50 40-84 1-20 Powders 1-25 70-99 The scoreboard changes to 0-5 Granules and pellets 0,1-95 5-99,9 0-15 High quality blends 90-99 0-10 The scoreboard is now 0-2

• The active ingredient plus at least one of the two surfactants or solvent is 100% by weight.

Lower or higher levels of active ingredients may exist depending on the use and the physical properties of the compound. Higher values of the ratio of surfactants to the active ingredients are sometimes desirable, which is achieved by compounding in a formulation or by mixing in a tank.

Typical solid solvents are described in [12], but other solvents, either fossil or industrially produced, may be used. For wettable powders, solvents with a higher absorbency are preferred, and for powders more dense solvents are preferred. Typical liquid solvents are described in [13], for concentrates as suspensions a solubility of less than 0.1% is preferred. These concentrates are preferably resistant to phase separation at 0 ° C. [14] and [15] describe surfactants and make recommendations for their use.

All formulations may contain minimal amounts of defoamers, sludge, chemical solubilization, microbial cultures, and more. Methods for preparing these compounds 5 are well known. The solutions are prepared with simple mixing of the ingredients.

The fine solid compounds are obtained by mixing and usually by grinding in a hammer mill or in a water-powered mill. The suspensions are prepared in wet mills as described in [16]. The granules and pellets can be prepared by spraying the active material on preformed tablet carriers or 15 by sintering processes. This is described in [17]. More information on how to prepare mixtures can be found in [18, 19, 20, 21, 22 and 23].

In the following examples, all 20 constituents are given in percent by weight, except those otherwise indicated.

Example 7. Wetting powder

Wetting powder Methyl 2- [[[[[4- (dimethylamino) -6- (2,2,2- trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl amino] sulfonyl] -3-methylbenzoate 80% Sodium alkylnaphthalenesulfonate 2% Sodium ligninsulfonate 2% Synthetic amorphous quartz 3% Kaolin 13%

The ingredients are mixed, milled in a hammer mill, until all solids reach a size below 50 microns, mixed again and packaged.

Example 8. Wetting powder

Wetting powder Ethyl 2- [[[[[4- (dimethylamino) -6- (2,2,2trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl amino] sulfonyl] -3-methylbenzoate 50% Sodium alkylnaphthalenesulfonate 2% Low viscous methylcellulose 2% Infuser finger 46%

The ingredients are mixed, coarsely ground in a hammer mill and then ground by air to produce particles smaller than 10 μ. The product is mixed again before packing.

Example 9. Granules

Granules Wetting powder of Example 8 Atapulgite granules (dustless) 5% (USS 20 to 40 mesh; 0.84 - 0.42 mm) 95%

The wet powder powder containing 25% solids was sprayed onto the surface of the attapulgite granules in a two-cone mixer. The granules are dried and packaged.

Example 10. Injected pellets

Injected pellets Methyl 2 - [[[[[4- (dimethylamino) -6- (2,2,2trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl amino] sulfonyl] -3-methylbenzoate 25% Anhydrous sodium sulphate Crude calcium ligninsulfonate 5% Sodium alkylnaphthalenesulfonate 1% Calcium / magnesium sulfonate 59%

The ingredients are mixed, milled in a hammer mill and moistened with about 12% water. The mixture is formed by compression into cylinders of 3 mm diameter, which are cut to form 3 mm pellets. The pellets can be used directly after drying or the dried pellets can be sutured to pass through USS sieve No. 20 (with 0.84 mm openings). Granules that have stuck to USS sieve No. 40 (with 0.42 mm openings) can be packaged for use and the fine fractions returned for re-cycle.

Example 11. Low-quality granules

Low quality granules Ethyl 2- [[[[[4- (dimethylamino) -6- (2,2,2trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl amino] sulfonyl] -3-methylbenzoate 0.1% Atapulgitic granules (USS 20 to 40 meshes, 0.42 - 0.84 mm) 99.9%

The active ingredient is dissolved in a solvent and the solution is sprayed onto the dusted granules in a two-cone mixer. After the spraying is complete, the material is warmed to evaporate the solvent, then cooled and packaged.

Example 12. Granules

Granules Methyl 2- [[[[[4- (dimethylamino) -6- (2,2,2- trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl amino] sulfonyl] -3-methylbenzoate 80% Humidification reagent 1% Crude ligninsulphonate salt (containing 5 to 12% natural sugars) 10% Atapulgitic clay 9%

The ingredients are mixed and ground to pass a 100 mesh sieve. The material is then introduced into a granulator with a layer of fluidized material, the air flow is adjusted to achieve gentle fluidization and a fine stream of water is sprayed onto the fluidized material. Fluidization and nebulization continue until granules of the desired size are obtained. Spraying stops, but fluidization continues (not necessarily with warming) until the water content is reduced to the required level, typically less than 1%. The material is unloaded, sieved to the desired range, typically 14 to 100 meshes (1410 to 149 μ) and packaged for use.

Example 13. Low-quality granules

Low quality granules Ethyl 2- [[[[[4- (dimethylamino) -6- (2,2,2trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl amino] sulfonyl] -3-methylbenzoate N, N - dimethylformamide Atapulgitic granules (USS 20 to 40 meshes, 0.42 - 0.84 mm) 1% 9% 90%

The active ingredient is dissolved in a solvent and the solution is sprayed onto the dusted granules in a two-cone mixer. After completion of the spraying, the mixtures35 are put into operation for a short time and then the granules are packed.

Example 14. Aqueous suspension

Aqueous suspension Methyl 2- [[[[[4- (dimethylamino) -6- (2,2,2- trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl amino] sulfonyl] -3-methylbenzoate 40% Polyacrylic acid as a thickener 0.3% Dodecylphenol polyethylene glycol ether 0.5% Disodium phosphate I% Monosodium phosphate 0.5% Polyvinyl alcohol 1.0% Water 56.7%

The ingredients are mixed and ground together in a sand mill to form particles with a size below 5 μ. Example 15. Solution

Solution Ethyl 2- [[[[(4- (dimethylamino) -6- (2,2,2trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl amino] sulfonyl] -3-methylbenzoate, sodium chloride Water 5% 95%

Sodium chloride is added directly to the water with stirring to obtain a solution that can be packaged for use.

Example 16. High-quality concentrate

High quality concentrate Methyl 2- [[[[[4- (dimethylamino) -6- (2,2,2trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl amino] sulfonyl] -3-methylbenzoate 99% Silica Airgel 0.5% Synthetic amorphous quartz 0.5%

The ingredients are mixed and milled in a hammer mill until a material is passed completely through USS No. 50 (aperture

0.3 mm).

Example 17. Wetting powder

Wetting powder Ethyl 2- [[[[[4- (dimethylamino) -6- (2,2,2trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl amino] sulfonyl] -3-methylbenzoate 90% Dioctyl sodium sulphosuccinate 0.1% Synthetic fine quartz 9.9%

The ingredients are mixed and milled in a hammer mill to form particles smaller than 100 μ. The material is sifted through

USS screen 50 and then packed

Example 18. Wetting powder

Wetting powder Methyl 2- [[[[[4- (dimethylamino) -6- (2,2,2- trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl amino] sulfonyl] -3-methylbenzoate 40% Sodium linguine sulfonate 20% Montmorillonite clay 40%

The ingredients are mixed, coarsely ground in a hammer mill and then ground in an air mill to form particles that are wholly smaller than 10 μ.

The material is returned for a repeat cycle and then packaged.

Example 19. Oil suspension

Oil suspension Ethyl 2- [[[[[4- (dimethylamino) -6- (2,2,2trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl amino] sulfonyl] -3-methylbenzoate 35% A mixture of polyalcoholic carboxyl esters and oil soluble sulfonates 6% Xylene 59%

The ingredients are mixed and ground together in a sand mill to form particles smaller than 5 μ. The product can be used directly, can be diluted with oils or emulsified in water.

Example 20. Powders

Powders Methyl 2- [[[[[4- (dimethylamino) -6- (2,2,2trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl amino] sulfonyl] -3-methylbenzoate % Atapulgit 10% Pyrophyllitis 80%

The active ingredient is mixed with attapulgite and then ground into a hammer mill to form particles smaller than 200 μ. The milled concentrate was mixed with the powdered pyrophyllite until a homogeneous mixture was obtained.

Example 21. Oil suspension

Oil suspension Ethyl 2- [[[[[4- (dimethylamino) -6- (2,2,2trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl amino] sulfonyl] -3-methylbenzoate 25% Polyoxyethylene sorbitol hexaoleate 5% High aliphatic hydrocarbon oil 70%

The ingredients are mixed together and ground in a sand mill until the solids have a size of less than 5 μ. The resulting slurry can be applied directly, but it is preferable to do so after it has been diluted with oil or emulsified in water.

Example 22. Wetting powder

Wetting powder Methyl 2- [[[[[4- (dimethylamino) -6- (2,2,2- trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl amino] sulfonyl] -3-methylbenzoate 20% Sodium alkylnaphthalenesulfonate 4% Sodium ligmimeulfonate 4% Low viscous methylcellulose 3% Atapulgit 69%

The ingredients are fully blended. After grinding in a hammer mill to obtain particles smaller than 100 μ, the material is ground again and sieved through USS No. 50 (0.3 mm hole) and then packaged.

Application

The compounds of the invention are particularly suitable for combating unwanted vegetation in sugar beet, fodder beet and red beet plantations. These crops take a long time to stabilize. In this interval, the sprouts should be grown very carefully, with particular attention to weed control in order to prevent damage and loss of yield. The compounds of the invention may be used before or after emergence and will control the growth of weeds including Galium aparine, Polygonum convolvulus, Sinapsis arvensis and Alopecurus myosuroides.

The mode of administration of the compounds is determined by many factors such as weed species, weather and climate, soil type, application time, age and size of the crops and weeds, method of application, etc. In general, the amount will vary between about 0.5 and 1000 g / ha, preferably between 10 and 125 g / ha. This standard in any particular situation can be determined by any ordinary specialist in the field.

These compounds can, and will often be, used in admixture with one or more other herbicides suitable for beet plantings, 42 such as metamitron, phenmedipham, desmedifam, chloridazone, lenacyl, ethofumesate, cycloate, chlorpyralide, dialate, trialate, dichloflopose -ethyl, fusalifop-butyl, haloxafop, setoxide and alloxide.

2Q The selective properties of these compounds have been studied in greenhouse tests. The results of these tests clearly show the activity and selectivity of the compounds and are given in the following tables.

OT ^R ί ^ SCO ^ NHCNH

Ri

Connect- opinion Ri R X Melting point 1 CH3 CH ₂ CH 3 M / CH3 / 2 134-142 ° C 2 CH3 CH3 NHCH3 123-129 ° C / d / 3 CH3 CH3 N / CHj / 2 15O-1 or ° C / a / 4 CH3 / CH2 / 2CH3 N / CH3 / 2 143-150 ° C / d / 5 en / CH2 / 2CH3 NHCHs Mp 159-163 ° C 6 CH3 CH / CH3 / 2 NHCHs 185-18b ° C 7 CH3 CH / CH3 / 2 N / CH3 / 2 155-15b ° C 8 CH3 CHi-c with o-CjHj N / CH3 / 2 105-115 ° C / a / 9 en CH2CH3 NHCH3 149-152 ° C 10 CH3 C / CH3 / 3 NHCH3 181-183 ° C 11 CH3 C / CH3 / C N / CH3 / 2 82-89 ° C

IeclA

Seeds from: Hordeum vulgare, Echinochloa crus-gally, Bromus tectorum, Xantium pensylvanicum, maize, cotton. Digitaria spp., Setaria faberi. Ipomoea spp., Rice, Sorghum bicolor, soybeans, sugar beet. Abutilon theophrasti, wheat, Avena fatua, Cyperls rotundus ca planted and treated before germination with test chemicals dissolved in a non-phytotoxic solvent. At the same time, these types of crops and weeds are treated with chemicals after emergence. Plants have a height of 2 to 18 cm (2 to 3 leaf stage) for post-emergence treatment. The treated plants were grown in greenhouses for 16 days, after which all species were compared with the control samples and evaluated visually.

The norms given in Table A are based on a scale from 0 to 10, where 0 means zero effect and 10 means complete control over the spread of weeds, The sign indicates that no test has been performed. Other terms have the following meaning:

C - chlorosis / necrosis;

G - growth retention;

H - forming effect

Test C

Seeds of Hordeum vulgare, Echinochloa crus-galli, Alopecurus myosutoides. Siellaria media, Xanthium pensytvarricum. corn, cotton. Digitaria spp., Bromus lectorum. Seiaria laberi, Seiaria viridis, Datura stramonium. Sorghum halepense. Chenopodium album. Imopoea spp., Rapeseed, rice. Cassia obtusifolia, soybean, sugar beet. Sida spinosa, Abutilon lheopivasli, wheat, Polygonum convolvulus, Avena lalua, Cyperus rotundus were planted and treated prior to emergence with test chemicals dissolved in a non-phytotoxic solvent. In time, these crops and weeds were treated with chemicals after emergence. The plants have a height of 2 to 18 cm (2 to 3 leaves stage) for post-emergence treatment.

The treated plants were grown in greenhouses for approximately 14 days, after which all species were compared with the control samples and evaluated visually. The characteristics listed in Table B are based on a scale from 0 to 100, where 0 means zero effect and 100 means complete control of weed distribution. The sign * indicates that no test has been performed.

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Run C

Selected crop and captive seeds including Poa annua, Hordeum vulgare. Solarium nigrum, Atopecurus myosuroides. Galium apparatus, Slellaria media. Seiaria viridis, Lolium mulliltorum, Polygonum aviculare, Kochia scoparia. Chenopodium album, Amaranihus reitoflexus, rapeseed, Matricaria inodora, Polygonum persicaria, Veronica persica, sugar beet, Viola arvensis, wheat, Polygonum convolvulus, Brassica spp., Avena fatua, Raphanus raphanisirum, planted and cultivated before cultivation non-phytotoxic solvent. Selected species in this list are treated with chemicals after emergence. The post-emergence treatment plants are 2 to 20 cm tall (stage 2 to 3 leaves). The treated plants and control samples were grown in greenhouses for 24 days, after which all species were compared with the control samples and evaluated visually. The characteristics listed in Table C are based on a scale from 0 to 100, where 0 indicates zero effect, 100 - complete control of undesirable vegetation growth. The sign means not in a test.

Table C

NORMA g / hl United. i AFTER PICKING 2 J 4 64 31 16 I IX) 125 And 31 16 ITO 115 64 31 IS 64 31 IS 1 AqauaJ b1iC £ hM 70 that 30 0 100 'Ιο 10 40 0 100 TO ω 10 10 Barley is » 71 TO 100 100 50 SO 70 10 SO are 70 TO BUck nifhuh & dc 100 100 100 75 BUckfrw 100 100 are TO 100 100 100 100 0 100 100 are 30 10 TO TO JO 0 Caleb weed bcdiuaw 100 $ 0 75 0 20 20 0 0 Cbiclweed IS TO 40 20 10 10 0 0 0 TO 50 10 20 0 30 20 0 0 Greca faiuil TO  0 0 0 10 w 40 40 40 are SO 40 40 10 Julian eycprus 100 50 50 0 • Knotweed 20 0 0 JCochu $ 0 ICO 50 20 LambaqwuUn 0 0 0 0 too 60 TO U TO 100 JO 0 0 0 20 0 -a - Pifwccd 40 40 30 0 100 ICO SO iO a 100 100 40 20 lUjx are $ 0 75 ¢ 0 SocodcM chaiaomik 100 100 $ 0 30 70 TO TO TO Sounwecd 100 ιοο '90 SO are 100 100 100 90 90 Speedwell 100 $ 0 TO » 10 JO TO 30 Supr bcci 0 0 0 0 50 JO 0 0 0 10 0 0 0 0 20 0 0 0 Love it 0 0 0 0 Wbcu 75 » 50 TO 40 40 30 30 Wild buckwheat ICO 10 TO 40 > 00 100. 100 100 are 400 ss 100 90 90 40 30 10 0 wud mustard 100 ICO 100 100 100 100 100 100 100 100 100 > 00 100 100 Wild-Ml 70 70 50 30 $ 0 ID 70 <0 are are are 0 0 0 are 40 40 40 Wild ndith 100 100 100 100

AFTER PICKING

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BEFORE PICKING

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Claims (7)

Claims amino] carbonyl] amino] sulfonyl] -3-methylbenzoate. A compound of the formula wherein: R is C 1 -C ₄ alkyl, CH ₂ CH = CH ₂ , CH ₂ C = CH, cyclopropylmethyl or CH ₂ CH ₂ R ₂ R _f is C 1 -C ₂ alkyl, C ₍ -C ₂ haloalkyl, CH ₂ CN, CH ₂ OCH ₃ , C 1 -C ₃ alkoxy, C 1 -C ₃ alkylthio, phenylthio or R ₃ R ₄ ; R ₂ is C ₁ -C ₂ alkoxy, C ₂ -C ₂ alkylthio, CN or halogen; R ₃ and R ₄ are independently H or CH ₃ X is NHCH ₃ , N (CH ₃ ) ₂ or N (CH ₃ ) OCH, bearing in mind that when R ₍ is OCH ₂ CH ₃ or CH ₂ OCH ₃ , R is different from CH ₃ . as well as its salts applicable to agro-culture. A compound according to claim 1, wherein R is C 1 -C ₄ alkyl; R ₁ is a C _t -C ₂ alkyl, and X is NHCH ₃ or N (CH ₃ ) ₂ The compound of claim 1, wherein R is C 1 -C ₄ alkyl; R 1 is C 1 -C ₂ haloalkyl and X is NHCH ₃ or N (CH ₃ ) ₂ The compound of claim 2, wherein R is C 1 -C ₃ alkyl and X is NH (CH ₃ ) ₂ The compound of claim 2, wherein R is C 1 -C ₃ alkyl and Xe N (CH ₃ ) ₂ A compound according to claim 1, which is ethyl-2 [[[[[4- (dimethylamino) -6- (2, 2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfonyl] -3-methylbenzoate. A compound according to claim 1 representing methyl-2- [[[[[4- (dimethylamino) -6 (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl]