RU2047607C1 - Fluoroalkoxyaminotriazines - Google Patents

Abstract

FIELD: organic chemistry. SUBSTANCE: product: fluoroalkoxyaminotriazines of the formula (I)

where R C₁-C₄-alkyl; R₁ methyl, CH₂-CN, CH₂-OCH₃, CH₂-O-CH₂-CH₃, C₁-C₃-alkoxy, CH₂F, CHFCH₃ or CF₂H;; X NHCH₃, N(CH₃)₂. Reagent 1: heterocyclic carbamates. Reagent 2: sulfamides. Synthesized compounds were used in agriculture as herbicides. EFFECT: improved method of synthesis. 2 cl, 7 tbl

Description

SO₂NH

NH

(I) где R С₁-С₄ алкил;
R₁ СН₃, СН₂СN, CH₂OCH₃, CH₂OCH₂CH₃, C_1-C₃ алкокси, СН₂F, СНFCH₃ или СF₂H;
Х NHCH₃ или N(CH₃)₂, при условии, что если R₁ является ОСН₂СН₃ или СН₂ОСН₃, то R отличен от СН₃, которые могут найти применение в сельском хозяйстве, так как проявляют гербицидную активность.The invention relates to sulfonylureas, in particular to new fluoroalkoxyaminotriazines of the general formula I:

SO ₂ NH

NH

(I) where R ₁ -C ₄ alkyl;
R ₁ CH ₃ , CH ₂ CN, CH ₂ OCH ₃ , CH ₂ OCH ₂ CH ₃ , C ₁ -C ₃ alkoxy, CH ₂ F, CHFCH ₃ or CF ₂ H;
X NHCH ₃ or N (CH ₃ ) ₂ , provided that if R ₁ is OCH ₂ CH ₃ or CH ₂ OCH ₃ , then R is different from CH ₃ , which can be used in agriculture, since they exhibit herbicidal activity.

 Sulfonylureas having herbicidal activity are known.

SO₂NH

NH

Z где R₁ например, СО₂R₁₀;
R₂ Н, F, Cl, Br, CF₃, CH₃, C₂H₅, OCH₃, OC₂H₅, SCH₃ или SC₂H₅;
R₁₀ C₁-C₄ алкил, СН₂СН₂ОСН₃, СН₂СН₂Сl, CH₂CH=CH₂ или СН₂С СН;
R₁₄ H или С₁-С₂ алкил;
R₁₅ C₁-C₂ алкил, ОСН₃, ОС₂Н₅ или СН₂СN;
Х NR₁₄R₁₅;
Y OCH₂CH₂F, OCH₂CHF₂ или ОСН₂СF₃;
Z CH или N.So, in US patent 4,744,816 and application EP 164269 disclosed herbicidal sulfonylureas of the formula

SO ₂ NH

NH

Z where R ₁ for example, CO ₂ R ₁₀ ;
R ₂ 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 C ₁ -C ₄ alkyl, CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ Cl, CH ₂ CH = CH ₂ or CH ₂ C CH;
R ₁₄ H or C ₁ -C ₂ alkyl;
R ₁₅ C ₁ -C ₂ alkyl, OCH ₃ , OC ₂ H ₅ or CH ₂ CN;
X NR ₁₄ R ₁₅ ;
Y OCH ₂ CH ₂ F, OCH ₂ CHF ₂ or OCH ₂ CF ₃ ;
Z CH or N.

SO₂NH

NH

А С₁-С₆ галогеналкил;
Z O или S;
Е СН или N;
R₁ например, Н, СОR₆;
R₂ например, Н;
R₃ и R₄ независимо являются Н, галогеном, С₁-С₄ алкилом, С₂-С₄галогеналкокси, NR₁₂R₁₃ и т.п.In the patent application of South Africa 84/2245, published September 28, 1984. herbicidal sulfomoureas of the formula are disclosed

SO ₂ NH

NH

A ₁ -C ₆ haloalkyl;
ZO or S;
E CH or N;
R ₁ for example, H, COR ₆ ;
R ₂ for example, H;
R ₃ and R ₄ are independently H, halogen, C ₁ -C ₄ alkyl, C ₂ -C ₄ haloalkoxy, NR ₁₂ R ₁₃ and the like.

R ₅ for example, C ₁ -C ₄ alkorksi, C ₁ -C ₄ haloalkoxy, C ₂ -C ₆ alkoxyalkoxy, and the like. and
R ₁₂ and R ₁₃ are independently H or C ₁ -C ₄ alkyl.

 Although these two works disclose certain compounds related to the compounds of the invention, however, in these works there is no specific mention of the compounds of the invention or their use for controlling sugar beet weeds.

O₂NH

NH

R₁ H, галоген, NO₂, C₁-C₄ галогеналкил, С₁-С₄ алкил, С₁-С₄алкокси, С₂-С₅ алкенил или С₁-С₄ алкоксикарбонил;
Х О, S, -SO- или SO₂;
m 0 или 1;
Q например, имеет значение R₁₃;
R₁₃ фенил или фенил, замещенный галогеном, NO₂, CN, С₁-С₄алкилом, С₁-С₄ алкоксилом, С₁-С₄ алкилтио, С₂-С₅ алкенилом, С₁-С₄галогеналкилом, С₁-С₄ алкоксикарбонилом, -NR₄₅R₄₆,-SO₃H или -SO₃H или -SO₂NR₄₇R₄₈;
R₂-C₁-C₃ алкил или С₁-С₃ алкокси, каждый из которых может быть замещен 1-3 атомами галогена;
R₃ например, -NR₄R₅, и т.п. и
Е N или СН.US Pat. No. 4,618,363 discloses herbicidal sulfonylureas of the formula

O ₂ NH

NH

R ₁ H, halogen, NO ₂ , C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₅ alkenyl or C ₁ -C ₄ alkoxycarbonyl;
X O, S, —SO— or SO ₂ ;
m is 0 or 1;
Q, for example, is R ₁₃ ;
R ₁₃ phenyl or phenyl substituted with halogen, NO ₂ , CN, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxyl, C ₁ -C ₄ alkylthio, C ₂ -C ₅ alkenyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxycarbonyl, -NR ₄₅ R ₄₆ , -SO ₃ H or -SO ₃ H or -SO ₂ NR ₄₇ R ₄₈ ;
R ₂ -C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy, each of which may be substituted by 1-3 halogen atoms;
R ₃ for example, —NR ₄ R ₅ , and the like. and
E N or CH.

 Although some compounds related to the compounds of the invention are disclosed in this work, however, in this work there is no specific mention of the compounds of the invention or their use for controlling sugar beet weeds.

 Moreover, the activity of the compounds described in the patent is not high enough, especially in relation to sugar beet weeds.

 The aim of the invention is the search for derivatives of sulfonylureas having a higher herbicidal activity.

 This goal is achieved by the proposed compounds of formula (I).

If we take into account the herbicidal activity, reliability in relation to sugar beets and the relative ease of synthesis, the preferred compounds are compounds of formula (I) in which
1. RC ₁ -C ₄ alkyl,
R ₁ methyl
X NHCH ₃ or N (CH ₃ ) ₂ .

2. RC ₁ -C ₄ alkyl,
R ₁ CHF, CHFCH ₃ , CF ₂ H,
X NHCH ₃ or N (CH ₃ ) ₂ .

3. R ₁ -C ₃ alkyl, and
X NHCH ₃ .

4. RC ₁ -C ₃ alkyl; and
X N (CH ₃ ) ₂ .

As specific preferred compounds in the light of the foregoing, the following compounds may be mentioned:
ethyl-2 - [[[[[4- (dimethylamino) -6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfonyl] -3- methyl benzoate, mp 134-142 ^about C; and
methyl-2 - [[[[[4- (dimethylamino) -6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfonyl] -3- methyl benzoate, mp 150-150 ^о С.

 Synthesis.

 The proposed compounds of formula (I) can be obtained by multistage synthesis using one or more of the methods listed below for each stage. This allows you to vary the synthesis pathway as a whole when obtaining specific compounds and each specialist will be able to choose the appropriate synthesis pathway and reaction sequence to obtain a specific compound.

 Compounds of formula (I) can be prepared by the methods described in equations 1 and 2.

+

I
Указанную реакцию проводят при 0-50^оС в растворителе, таком как ацетонитрил, диоксан или тетрагидрофуран, и в присутствии источника фторида-иона, такого как фторид цезия или фторид тетрабутиламмония, в течение 0,1-2 ч.Many of the compounds of formula (I) can be prepared by reacting a silylsulfonamide of formula (II) with a heterocyclic carbamate of formula (III)

+

I
The reaction is conducted at 0-50 ^{° C} in a solvent such as acetonitrile, dioxane or tetrahydrofuran and in the presence of a fluoride ion source such as cesium fluoride or tetrabutylammonium fluoride, for 0.1-2 hours.

 Alternatively, certain compounds of formula (I) can be prepared by reacting certain sulfonamides of formula (IV) with a heterocyclic carbamate of formula (III), as shown in equation 2.

+

I
Реакцию проводят при 0-50^оС в растворителе, таком как ацетонитрил, диоксан или тетрагидрофуран, и в присутствии ненуклеофильного основания, такого как ДБМ, в течение 0,2-2 ч.

+

I
The reaction is carried out at 0-50 ^{° C} in a solvent such as acetonitrile, dioxane or tetrahydrofuran and in the presence of a non-nucleophilic base such as DBM, for 0.2-2 hours.

, 1882 (1978)), как показано в уравнении 3.Many silylsulfonamides of formula (II) can be prepared by reacting a sulfonyl chloride of formula (V) with tert-butyldimethylsilylamine (JR Bowser et al. Inorganic Chemistry,

, 1882 (1978)), as shown in equation 3.

+ H

i

II
Реакцию проводят при 0-30^оС в растворителе, таком как дихлорметан, и в присутствии 1-2 эквивалентов амина и 1 эквивалента бикарбоната натрия.

+ H

i

II
The reaction is carried out at 0-30 ^{° C} in a solvent such as dichloromethane and in the presence of 1-2 equivalents of the amine and 1 equivalent of sodium bicarbonate.

 Alternatively, many silylsulfonamides of formula (II) can be prepared by reacting a silylsulfonamide of formula (IV) with an alkyl chloroformate, as shown in equation 4.

II
Реакцию проводят взаимодействием соответствующего силилсульфонамида формулы (VI) с литийорганическим реагентом, таким как н-бутиллитий, в инертном апротонном растворителе, таком как тетрагидродфуран, при (-78) (0)^оС, в течение 0,5-3 ч. Образовавшееся промежуточное дитиосоединение формулы (VIа) затем подвергают взаимодействию с алкил-хлорформиатом в течение 0,5-5 ч при (-78) (0)^оС. Силилсульфонамиды формулы (II) выделяют обычными способами, хорошо известными специалистам.

II
The reaction is conducted by reacting the corresponding silyl sulfonamides of formula (VI) with an organolithium reagent such as n-butyllithium, in an inert aprotic solvent such as tetragidrodfuran at (-78) (0) ^{° C,} for 0.5-3 hours. The resulting intermediate ditiosoedinenie formula (VIa) is then reacted with an alkyl chloroformate for 0.5-5 hours at (-78) (0) ^C. silyl sulfonamides of formula (II) is isolated by conventional methods well known in the art.

 Many silylsulfonamides of the formula (II) can be obtained indirectly, as shown in equation 5.

II
Первые две стадии этого уравнения аналогичны описанному выше уравнению 4. J. C. Lombardio в Org.Chem.

, 1843, (1971) также описывает способы получения промежуточного соединения формулы (VII), которое этерифицируют кислотами формулы (VII). Способы этерификации кислот в мягких условиях хорошо известны специалистам.

II
The first two stages of this equation are similar to Equation 4 above. JC Lombardio in Org.Chem.

, 1843, (1971) also describes methods for preparing an intermediate of formula (VII), which is esterified with acids of formula (VII). Methods for the esterification of acids under mild conditions are well known in the art.

 Many sulfonamides of formula (IV) can be obtained by the deprotection of tert-butyl sulfonamides of formula (IIa), as shown in equation 6.

Реакцию проводят при (-78) (30)^оС в инертном растворителе, таком как гексан, и в присутствии кислоты, такой как трифторуксуснаяя кислота. Результат этой реакции зависит от природы R₁ и R.

The reaction is carried out at (-78) (30) ^C in an inert solvent such as hexane in the presence of an acid such as triftoruksusnayaya acid. The result of this reaction depends on the nature of R ₁ and R.

 The sulfonamides of formula (IIa) can be prepared by methods analogous to the methods presented in equations 3, 4 and 5, in which the tert-butyldimethylsilyl group is replaced by a tert-butyl group.

Sulfonyl chlorides of the formula (V) can be obtained by oxychlorination of the corresponding sulfur-containing compound of the formula (VII) as shown in equation 7. R ₁ is H, alkyl, benzyl or carbamoyl.

V
Реакцию по уравнению 7 проводят при взаимодействии соединения формулы (VIII) в растворителе, таком как уксусная кислота или пропионовая кислота, по крайней мере с 3,0 эквивалентами хлора в присутствии по крайней мере 2,5 эквивалентов воды приблизительно при (-20) (30)^оС в течение 0,2-5 ч. В работе A. Wagenaar, Red. Trav. Chim. Pays Bas

, 91 (1982) описана аналогичная реакция.

V
The reaction of equation 7 is carried out by reacting a compound of formula (VIII) in a solvent such as acetic acid or propionic acid with at least 3.0 equivalents of chlorine in the presence of at least 2.5 equivalents of water at about (-20) (30 ) ^o C for 0.2-5 hours. In the work of A. Wagenaar, Red. Trav. Chim. Pays bas

91 (1982) describes a similar reaction.

Alternatively, by reacting a compound of formula (VIII), where R ₁ is H or benzyl, with a hypochlorite solution such as 5% NaOCl, sulfonyl chlorides of formula (V) can be obtained. The reaction conditions for such reactions are described in patent application South Africa 84/8845 and application for EP 142152.

 As shown in equation 8, many sulfonyl chlorides of the formula (V) can be obtained from the corresponding amines of the formula (IX) Meerwein reactions.

V
Указанная реакция заключается в диазотировании амина IX нитритом натрия в водной НСl c последующей реакцией соли диазония с двуокисью серы и хлоридом меди в уксусной кислоте, аналогично способу, описанному в работе Vale и Sowinski J. Org. Chem.

, 1824 (1960).

V
This reaction consists in the diazotization of amine IX with sodium nitrite in aqueous HCl followed by the reaction of a diazonium salt with sulfur dioxide and copper chloride in acetic acid, similarly to the method described by Vale and Sowinski J. Org. Chem.

, 1824 (1960).

 Alternatively, sulfonyl chlorides of formula (V) can be obtained by modifying the above procedure, as shown in equation 9.

V
В указанной реакции хлористоводородная соль амина диазотируется алкилнитритом в органическом растворителе, таком как ацетонитрил или ацетон, и полученная в результате соль взаимодействует с диоксидом серы и хлоридом меди, в результате чего образуется сульфонилхлорид J.M.Doyle в J.Org. Chem.

, 2426, 2431 (1977) описывает реакционные условия осуществления реакций, подобных реакциям Меервейна.

V
In this reaction, the amine hydrochloride salt is diazotized with alkyl nitrite in an organic solvent such as acetonitrile or acetone, and the resulting salt is reacted with sulfur dioxide and copper chloride to form JMDoyle sulfonyl chloride in J. Org. Chem.

, 2426, 2431 (1977) describes the reaction conditions for the implementation of reactions similar to the Meerwein reactions.

 Heterocyclic carbamates of formula (III) in equations 1 and 2 can be obtained by the methods described in US patent 4,744,816.

 The following are examples illustrating the preparation of compounds of the invention.

PRI me R 1. Complex methyl ethyl 3-methyl-2- (phenylmethylthio) -benzoic acid,
To a stirred suspension of dry tetrahydrofuran (125 ml) and 35% potassium hydride in oil (6.3 g) was slowly added benzyl mercaptan (6.1 mL) at 0 ^C and under an inert atmosphere. After 15 minutes, 3-methyl-2-nitrobenzoic acid methyl ethyl ester (11.23 g) was added and the resulting mixture was stirred overnight at room temperature. The reaction mixture was partitioned between 6N. sodium hydroxide (25 ml) and ethyl acetate (150 ml). The organic phase is dried with magnesium sulfate, filtered, concentrated and chromatographed on silica gel, eluting with 5% ethyl acetate in hexane, to give 13.7 g of the target compound as a yellow oily substance, n _D 1.5642.

NMR (90 MHz, 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.).

 IR (clear) 1720 cm.

 PRI me R 2. Methyl 2- (chlorosulfonyl) -3-methylbenzoate.

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) was stored at ⁰ ° C, was slowly added 5 % sodium hypochlorite (450 ml). The resulting yellow suspension was stirred 1 hour at 0 ° ^C. The dichloromethane layer was dried with magnesium sulfate, filtered, concentrated, and triturated with chlorobutane and hexane mixture, to give 14 g of the title compound as a white solid, m.p. 114-116 ^about S.

NMR (90 MHz, CDCl ₃ ) δ: 2.82 (s, 3H, CH ₃ ); 3.97 (s, 3H, OCH ₃ ); 7.5 (m, 3H, arom.).

IR (nuzhol) 1730, 1360 and 1175 cm ^-1 .

 PRI me R 3. Ethyl-2 - [((dimethyl) - (1,1-dimethylethyl) silylamino) -sulfonyl] -3-nit-robenzoate.

Suspension of ethyl 2- (chlorosulfonyl) -3-nitrobenzoate (14.7 g), amino-tert. β-butyldimethylsilane (15.4 g) and sodium bicarbonate (3.5 g) in dichloromethane (300 ml) are stirred in a flask, closed with a stopper, for 4 days at room temperature. Then add water (90 ml), saturated aqueous bicarbonate (45 ml) and the resulting mixture was stirred. After which the dichloromethane phase is dried with magnesium sulfate, filtered, concentrated and chromatographed on silica gel, eluting with 20% ethyl acetate in hexane, whereby 12.9 g of the target compound are obtained in the form of a white solid, mp 101-102 ^about S.

NMR (90 MHz, CDCl ₃ ) δ 0.30 (s, 6H, 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 (nuzhol) 3200, 1730 and 1700 cm ^-1 .

 Example 4. Methyl-2 - [((dimethyl) -1,1-dimethylethyl) silylamino) sulfonyl] -3-trifluoromethylbenzoate.

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

NMR (90 MHz, CDCl ₃ ) δ: 0.29 (s, 6H, 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 (nuzhol) 3250, 1725 cm ^-1 .

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

A solution of 2- (dimethyl- (1,1-dimethylethyl) -silylamino) -3-methylbenzoic acid ethyl ester (0.36 g) and O-phenyl-N- [4-dimethylamino-6- (2,2,2 trifluoroethoxy-1,3,5-triazin-2-yl] carbamate (0.39 g) in acetonitrile (10 ml) was treated with 1M tetrabutylammonium fluoride in tetrahydrofuran (1.1 ml) and the mixture was stirred for 2 hours. After the reaction mixture was diluted with water (20 ml) and acidified with 1N hydrochloric acid, the resulting precipitate was filtered, washed with water and hexane / ether, dried with air, and 0.28 g of the target compound was obtained in the form of a white solid, mp 134-14 2 ^about S.

NMR (200 MHz, 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 (m, 4H, arom. And NH); 12.38 (s, 1H, NH).

MK (nuzhol): 1710, 1695 cm ^-1 .

 PRI me R 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 O-phenyl-N- [4-dimethylamino-6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] carbamate (0.79 g) in tetrahydrofuran (10 ml) is treated with 1M tetrabutylammonium fluoride in tetrahydrofuran (2.2 ml). The resulting mixture was stirred for 1 hour. After diluting the mixture with water (30 ml) and acidifying with 1N. With hydrochloric acid, the resulting precipitate is filtered, washed with water and chlorobutanehexane and dried with air, whereby 0.58 g of the target compound is obtained in the form of a white solid, mp 151-159 ^{° C} (dec.). Another sample previously prepared by this method melted at 150-160 ^{° C} (dec.).

NMR (300 MHz, DMSO) δ 3.04 (s. 3H, CH ₃ ); 3.46 (s, 6H, NCH ₃ ); 4.10 (s, 3H, OCH ₃ ); 5.32 (m, 2H, CH ₂ ); 7.78 (d, 1H, arom.); 7.84 (d, 1H, arom.); 7.98 (m, 1H, arom.); 11.1 (s, 1H, NH); 13.1 (s, 1H, NH).

IR (nuzhol) 1730 cm ^-1 .

 The following compounds can be obtained using the methods described previously and illustrated in examples 1-6.

 Compositions.

 Compositions containing compounds of formula (I) can be prepared by standard methods. They can be made in the form of dusts, granules, tablets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, etc. Many of these compositions can be used directly. Sprayable compositions can be diluted with the appropriate medium and used for spraying in a volume of from several liters to several hundredths of a liter per hectare. Highly concentrated compositions are primarily used as intermediates for the manufacture of preparations. Such preparations contain mainly from 0.1 to 99 wt. active ingredient and at least one of: (a) from about 0.1 to 20% one surfactant (or substances) and (b) from about 1 to 99.9% of a solid or liquid inert diluent (or diluents). In particular, the preparations may contain these ingredients, approximately in the following composition, wt. (see table 2).

 The level of active ingredients in the composition depends on the purpose of use of the composition and the physical properties of the compounds. It is sometimes desirable that the ratio of surfactant to active ingredient be higher, which can be achieved by introducing this substance into the preparation or into the reservoir mixture.

Typical solid diluents are described in Watkins et al. "Handbook of Insecticide Dust Diluent and Carriers", 2nd edition, Dorland Book, Caldwrll, New Jersey, but other solid diluents can also be used. For wettable powders, it is preferable to use more absorption diluents, and for dusts it is desirable to use denser diluents. Typical liquid diluents and solvents are described in Marsden "Solvents Guide", 2nd edition , Inretscience, New York, 1950. For suspension concentrates preferred solubility of 0.1% and preferably to concentrate solutions are stable against phase separation at 0 ^C. In McCutcheons' Detergents and Emulsifiers, Annual McPublishing Corp. Ridgewood, New Jersey, and Sisely and Wood "Encyclopedia of Surface Active Agents", Chemical Pyblishing Co. Inc. New York, 1964, lists recommended surfactants. All preparations may contain small amounts of additives to reduce foaming, clumping, corrosion, microbial growth, etc.

 Methods for making said compositions are well known. Solutions can be obtained simply by mixing the ingredients. Fine solid compositions can be obtained by mixing and grinding in a hammer mill or jet mill. Suspensions can be obtained by wet grinding (see, for example, US patent 3,060,084). Granules and tablets can be prepared by spraying the active ingredients into pre-prepared granular carriers or using an agglomeration technique (see Browning "Agglomeration", Chemical Engineering, December 4, 1967, p. 147, and "Perry's Chemical Engineer's Handbook", 5th edition , McGraw Hill, New York, 1973, pp. 8-57).

 In the examples below, all parts are given by weight, unless otherwise indicated.

PRI me R 7. Wettable powder, wt. Methyl-2 - [[[[[4- (dimethylamino) -6- (2,2,2-trifluoroethoxy) -1,3,5-triazine-
-2-yl] amino] carbonyl] amino]
-sulfonyl] -3- -methylbenzoate 80
Sodium Alkyl Naphthalenesulfonate 2
Sodium lignosulfonate 2
Synthetic amorphous silica 3 Kaolinite 13
These ingredients are mixed and crushed in a hammer mill until the size of the solid particles reaches 50 microns, then mixed again and packaged.

 PRI me R 8. Wettable powder, wt.

Ethyl-2 - [[[[[4- (dimethylamino) -6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfonyl] -3 - methyl benzoate 50
Sodium Alkyl Naphthalenesulfonate 2
Low viscosity methyl cellulose 2
Diatomaceous earth 46
These ingredients are mixed, first coarsely ground in a hammer mill, and then in an air-jet mill to obtain particles with a diameter of 10 microns or less. After this, the product is mixed again and then packaged.

 PRI me R 9. Granules, wt.

Wettable powder from Example 8-5
Attapulgite granules
(US standard 20-40 mesh; 0.84-0.42 mm) 95
A suspension of a wettable powder containing solid particles is sprayed over the surface of the attapulgite granules in a double cone type drum mixer. Then the granules are dried and packaged.

PRI me R 10. Extruding tablets, wt. Methyl-2 - [[[[[4- (dimethylamino) -6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfonyl] -3 - methylbenzoate 25
Anhydrous Sodium Sulfate 10
Coarse Calcium Lignosulfonate 5
Sodium Alkyl Naphthalenesulfonate 1
Calcium / Magnesium Bentonite 59
These ingredients are mixed, crushed in a hammer mill, and then moistened with about 12% water. The mixture is extruded, after which a cylindrical extrudate with a diameter of 3 mm is cut into tablets about 3 mm long. The resulting tablets can be used immediately after drying, or these tablets are crushed and passed through a No. 20 US standard sieve (0.84 mm). Granules held up by a No. 40 sieve (US standard 0.42 mm) may be packaged for use or for further grinding.

 PRI me R 11. Low concentrated granules, wt.

Ethyl-2 - [[[[[4- (dimethylamino) -6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfonyl] -3 - -methyl benzoate 0.1
Attapulgite granules
(20-40 mesh, U.S. standard, 0.42-0.84 mm) 99.9
The active ingredient is dissolved in a solvent and the resulting solution is sprayed onto dust free granules placed in a double cone type drum mixer. After spraying the solution, the resulting material is heated in order to evaporate the solvent. Then the material is cooled and packaged.

PRI me R 12. Granules, wt. Methyl-2 - [[[[[4- (dimethylamino) -6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfonyl] -3 - - methylbenzoate 80 Wettable agent 1
Crude salt
lignosulfonate
(containing 5-20% natural sugars) 10 Attapulgite clay 9
These ingredients are mixed and ground, followed by passing through a 100 mesh sieve. Then, the obtained material is placed in a fluidized bed granulator, while the air flow is regulated so as to obtain a slightly liquefied material, after which a thin stream of water is sprayed onto the fluidized material. Fluidization and spraying are continued until granules of the desired size are obtained. Then the spraying is stopped, but the fluidization is continued while heating (but not necessarily) until the water content drops to the desired level, usually <1%. Then the material is discharged, sieved to obtain particles of the desired size, mainly 14-100 mesh (1410 -149 microns) and pack for use.

 PRI me R 13. Low concentrated granules, wt.

Ethyl-2 - [[[[[4- (dimethylamino) -6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfonyl] -3 - -methylbenzoate 1 N, N-dimethylformamide 9
Attapulgite granules
(20-40 mesh US standard, 0.42-0.84 mm) 90
The active ingredient is dissolved in a solvent and the resulting solution is sprayed onto dust free granules in a double cone type drum mixer. After spraying the solution, the mixer is still left in operation for a short period of time, and then the granules are removed and packaged.

PRI me R 14. Aqueous suspension, wt. Methyl-2 - [[[[[4- (dimethylamino) -6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfonyl] -3 - -methylbenzoate 40 A thickening agent based on polyacrylic acid 0.3 Dodecylphenol ether of polyethylene glycol 0.5 Disodium phosphate 1 Monosodium phosphate 0.5 Polyvinyl alcohol 1.0 Water 56.7
These ingredients are mixed and ground in a sand mill, whereby particles are obtained that are generally <5 microns in size,
PRI me R 15, the Solution, wt.

Ethyl-2 - [[[[[4- (dimethylamino) -6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfonyl] -3 -
methylbenzoate sodium salt 5 water 95
Salt is added directly to water, while stirring, and the resulting solution is Packed for further use.

PRI me R 16. Highly concentrated concentrate, wt. Methyl-2 - [[[[[4- (dimethylamino) -6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfonyl] -3 - -methylbenzoate 99 Aerosilica gel 0.5
Synthetic Amorphous Silica 0.5
These ingredients are mixed and ground in a hammer mill, after which the material is passed through a No. 50 sieve (US standard, 0.3 mm). The resulting concentrate, if necessary, can be used for further manufacture of the drug.

 PRI me R 17. Wettable powder, wt.

Ethyl-2 - [[[[[4- (dimethylamino) -6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfonyl] -3 - -methylbenzoate 90 Dioctyl sodium sulfosuccinate 0.1 Synthetic finely divided silica 9.9
The ingredients are mixed and ground in a hammer mill until particles below 100 microns are obtained. Then the material is sieved through a sieve No. 50 (US standard), and then Packed.

PRI me R 18. Wettable powder, wt. Methyl-2 - [[[[[4- (dimethylamino) -6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfonyl] -3 - -methylbenzoate 40
Sodium ligninsulfonate 20
Montmorillonite Clay 40
These ingredients are thoroughly mixed, coarsely milled in a hammer mill, and then in an air-jet mill, whereby particles are obtained mainly in the size below 10 microns. After that, the material is mixed again, and then packaged.

 PRI me R 19. Oil suspension, wt.

Ethyl-2 - [[[[[4- (dimethylamino) -6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfonyl] -3 - methylbenzoate 35
A mixture of polyalcohol complex
carboxylic acid ester
and oil soluble petroleum sulfonates 6 Xylene 59
These ingredients are mixed and ground in a sand mill until particles are obtained which are generally below 5 microns in size. The resulting product can be used directly or in combination with an oil filler, or it can be emulsified in water.

PRI me R 20. Dust, wt. Methyl-2 - [[[[[4- (dimethylamino) -6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfonyl] -3 - -methylbenzoate 10 Attapulgite 10 Pyrophyllite 80
The active ingredient is mixed with attapulgite and ground in a hammer mill to produce particles generally below 200 microns in size. The ground concentrate is then mixed with pyrophyllite powder until the mixture is homogeneous.

 PRI me R 21. Oil suspension, wt.

Ethyl-2 - [[[[[4- (dimethylamino) -6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfonyl] -3 - methylbenzoate 25
Polyoxy ethylene sorbitol hexaoleate 5 Higher aliphatic hydrocarbon oil 70
These ingredients are ground in a sand mill until particles of about 5 microns are obtained. The resulting thick suspension can be used directly, but it is preferable that it be diluted with oil or emulsified in water before use.

PRI me R 22. Wettable powder, wt. Methyl-2 - [[[[[4- (dimethylamino) -6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] amino] carbonyl] amino] sulfonyl] -3 - -methylbenzoate 20
Sodium Alkyl Naphthalenesulfonate 4
Sodium ligninsulfonate 4
Low viscosity methylcellulose 3 Attapulgite 69
These ingredients are thoroughly mixed and then crushed in a hammer mill to obtain particles of a size generally below 100 microns. Then the material is again mixed and passed through a No. 50 sieve (US standard, 0.3 mm) and packaged.

 The invention is intended for use in order to control the weeds of sugar beets, beet fodder and red beetroot. All of these cultures require a long period of time to accelerate growth. During this period of time, seedlings need careful care and top dressing; therefore, in order to prevent a decrease in yield, special attention should be paid to combating undesirable vegetation. The compounds of the invention can be used for pre-emergence or post-emergence treatments for weed control, such as tench (Galium aparine), highlander (Polygonum convolvulus), field mustard (Sinapsis arvensis), and mouse-tailed tail (Alopercurus neysoroides).

 The dose of the compounds used is determined by a number of different factors, for example, the type of weed, weather or climate, soil type, application time, age and size of weeds and crops, method of application, etc. Basically, the dose of the compounds used is within 0 5-1000 g / ha, and preferably about 10-125 g / ha. The necessary dose in any case can be chosen by a specialist agronomist.

 These compounds may be used in admixture with one or more other herbicides. They can be used with other herbicides that are selective for beetroot weeds, for example, metamitron, phenmedifam, desmedifam, chloridazone, lenacyl, etofumimesate cycloate, clopyramide diallate, triallate, dicloformyl, quisalofop-ethyl, bufaliphalop and alloxydim.

 The selective properties of these compounds were established using tests conducted in greenhouses. The results of these tests, presented in the table below, clearly confirm their activity and selectivity.

T e s t A. Seeds of barley (Hordeum vulgare), millet millet (Echinochloa crus-galli), rye fire (Bromus seculanus), or roof fire (Bromus tectaorum), cocklebur (Xanthium pensylcanilum), corn are sown. seed cotton (Gossypiym hirsutum), blood dewdrops (Digitarea spp.), common bristles (Setaria faberi), morning glory (Ipomea spp.), rice (Oryza sativa), sorghum (Sorghum bicolor), cultivated soy (Glycine max sugar), (Beta vulgaris), the teardrop of Theophrastus (Abutilon theophrasti), wheat (Triticum aestivum), common wild oat (Avena farua), and red raw tubers (Cyperus rotundus) and processed to germinate by test chemical compounds solutions dissolved in a non-phytotoxic solvent. At the same time, these cultivated plants and weeds are subjected to post-emergence treatment with test compounds. For post-emergence treatment take plants that have reached a height of 2-18 cm (stage 2-3 leaves). Treated and control plants are kept in the greenhouse for 16 days, after which all plant species are compared with control samples and visually evaluated. The results obtained are shown in table 3, evaluated on a ten-point scale, where 0 indicates the absence of effect, and 10 complete destruction of unwanted vegetation. A “-” sign indicates that no tests have been performed. The symbols used mean the following:
With chlorosis / necrosis
G growth retardation
H morphological effect
In the table. 3 shows the following plant names:
1 barley; 2 rooster millet; 3 rye bonfire; 4 fruit cock; 5 corn; 6 cotton seed; 7 blood dewdrop; 8 bonfire roofing; 9 bristles; 10 morning glory; 11 to eat red; 12 rice; 13 sorghum; 14 soybean; 15 sugar beets; 16 cable car of Theophrastus; 17 wheat; 18 common oatmeal.

 T e s t B. Seeds of barley (Hordeum vulgare), millet millet (Echinochloa crus-galli), mouse-tail foxtail (Alopecurus myosuroides), medium stellate (Stellaria media), cockroach (Xanthium pensylbanium), maize (Ze) are sown. seed (Gossypium hirsutum), blood dewdrops (Digitatia spp.), roof fire (Bromus tertarum), common bristles (Setaria faberi), green bristles (Setaria virides), smelly dope (Datura stramonium), wild sorghum halepot (Sotghum) white (Chenopodium album), morning glory (Ipomoea spp.), common radish (Brassica napus), rice (Oryza sativa), Canadian rind (Cassia obtusifolia), cultivated soy (Glycine max), sugar clods (Beta vulgaris), rhomboid sidas (Sida spinosa), Rope of Theophrastus (Abutilon theophrasti), wheat (Triticum aestivum), mountaineer Convolvulus (Polygonum convolvus), wild oatmeal (Alena fatua) and red spotted tubers (Cyperus rotundus) treatment with test chemical compounds dissolved in a non-phytotoxic solvent. At the same time, these cultivated plants are subjected to post-emergence treatment with test compounds. For post-emergence treatment, plants that have reached a height of 2-18 cm (stage 2-3 leaves) are selected. Treated and control plants are kept in the greenhouse for approximately 24 days, after which all plant species are compared with control samples and visually evaluated. Evaluation is carried out on a scale of 0-1000 where 0 means no effect, and 100 complete destruction of the plant. A “-” sign means that no tests have been performed.

 The test results are systematized in table 4.

 The following plant names are introduced in table 4: 1 barley; 2 rooster millet; 3 mouse-tailed foxtail; 4 asterisk medium; 5 cocklebur; 6 corn; 7 cotton seed; 8 blood dewdrop; 9 bonfire roofing; 10 bristles; 11 bristles green; 12 stinky dope; 13 wild sorghum; 14 gauze white; 15 morning glory; 16 to eat red; 17 ordinary radish; 18 rice; 19 Canadian canine; 20 soybean; 21 sugar beets; 22 rhomboid sid; 23 cable car of Theophrastus; 24 wheat; 25 highlander bindweed; 26 oats are empty.

 Test C. The seeds of cultivated plants and weeds are sown, namely the annual bluegrass (Poa annua), barley (Hordeum vulgare) black nightshade (Solanum nigrum), mouse-tail foxtail (Alopecurus myosuroides), tenor coot (Galium aparine), medium starlet (Stellaria media ), green bristles (Setaria virides), chaff multiflorous (Lolium multiflorum), mountaineer (Polygonum aviculare), cochia broom (Kochia scoparia), white maria (Chenopodium album), white quinoa (Amaranthus retroflexus), common radish (Brassica nap) , odorless chamomile (Matricaria inodora), rough mountaineer (Polygonum persicaria), veronica longifolia (Veronica persica), ca beetroot (Beta vulgaris), bicolor violets (Viola arvensis), wheat (Triticum aestivum), mountaineer convolvulus (Polygonum convolvus), white mustard (Brassica spp.), empty oats (Alena fatua) and wild radish (Raphanus raphanistrum) and exposed pre-emergence treatment with test chemical compounds dissolved in a non-phytotoxic solvent. Cultivated plants and weeds selected from the above list are also subjected to post-emergence treatment with test compounds. For post-emergence treatment using plants that have reached a height of 2-20 cm (stage 2-3 leaves). Treated and control plants are kept in the greenhouse for approximately 24 days, after which all plant species are compared with control samples and visually evaluated. The assessment is carried out on a scale of 0-100, where 0 is the absence of effect, and 100 is the complete destruction of the plant. A “-” sign means that no tests have been performed.

 The test results are systematized in table 5.

 The following plant names are listed in the table: 1 annual peppermint; 2 barley; 3 nightshade black; 4 mouse-tailed foxtail; 5 bedstraw tenacious; 6 asterisk medium; 7 bristle green; 8 Chaff multiflorous; 9 cochia broom; 10 gauze white; 11 white quinoa; 12 rapeseed; 13 odorless chamomile; 14 veronica longifolia; 15 sugar beets; 16 wheat; 17 highlander bindweed; 18 white mustard; 19 oats are empty; 20 wild radish; 21 highlander grungy; 22 bird highlander; 23 violet two-tone.

 Comparative activity data of the proposed compound and the known analogue are given in table.6.

Соединение по прототипу

Соединение по изобретению
Как видно, предлагаемое соединение демонстриует улучшение в защите сахарной свеклы по сравнению с аналогом и обладает лучшей гербицидной активностью по отношению к практически всем указанным видам сорняков. Предлагаемое соединение совершенно безопасно для сахарной свеклы, даже при дозе 62 г/га, в то время, как соединение прототипа повреждает сахарную свеклу даже при такой низкой дозе, как 16 г/га. Предвосходная гербицидная активность особенно проявляется в отношении сорняка "сыть красная". Предлагаемое соединение обеспечивает полный контроль над сытью красной в испытанных дозах, в то время, как соединение прототипа обеспечивает лишь умеренный контроль. Такой защитный эффект по отношению к сахарной свекле и улучшенная гербицидная активность удивительны и неожиданны, учитывая результаты, представленные в патенте США 4,744,816.

Prototype Compound

Compound of the Invention
As you can see, the proposed compound demonstrates an improvement in the protection of sugar beets in comparison with the analogue and has the best herbicidal activity in relation to almost all of these types of weeds. The proposed compound is completely safe for sugar beets, even at a dose of 62 g / ha, while the prototype compound damages sugar beets even at a dose as low as 16 g / ha. Superior herbicidal activity is especially evident in relation to the weed "red sativa". The proposed connection provides complete control over the saturation of red in tested doses, while the connection of the prototype provides only moderate control. Such a protective effect on sugar beets and improved herbicidal activity are surprising and unexpected, given the results presented in US patent 4,744,816.

Claims (7)

1. Fluoroalkoxyamino triazines of the general formula

where RC _{1 is} C ₄ alkyl;
R ₁ CH ₃ , CH ₂ CN, CH ₂ OCH ₃ , CH ₂ OCH ₂ CH ₃ , C ₁ C ₃ alkoxy, CH ₂ F, CHFCH ₃ or CF ₂ H;
X NHCH ₃ or N (CH ₃ ) ₂ , provided that if R ₁ is OCH ₂ CH ₃ or CH ₂ OCH ₃ , then R is different from CH ₃ . 2. The compound according to claim 1, where RC _{1 is} C ₄ -alkyl, R ₁ is CH ₃ , X NHCH ₃ or N (CH ₃ ) ₂ . 3. The compound according to claim 1, where RC _{1 is} C ₄ -alkyl, R ₁ is CH ₂ F, CHFCH ₃ or CF ₂ H, X NHCH ₃ or N (CH ₃ ) ₂ . 4. The compound according to claim 2, where RC _{1 is} C ₃ -alkyl, X is NHCH ₃ . 5. The compound according to claim 2, where RC _{1 is} C ₃ -alkyl, X is N (CH ₃ ) ₂ .  6. The 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-methylbenzoic atom.  7. The compound according to claim 1, which is methyl-2 - [[[[[4- (dimethylamino) -6- (2,2,2-trifluoroethoxy) -1,3,5-triazin-2-yl] - amino] carbonyl] amino] sulfonyl] -3-methylbenzoate.

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