RU2088583C1 - Derivatives of sulfamidosulfonylurea and selective herbicide composition - Google Patents

Abstract

FIELD: organic chemistry. SUBSTANCE: product of the formula: Q-SO₂-NHC(=O)-N(L)-G where: Q - N-[SO₂N(CH₃)₂]-OR^″-OR'' or N-

-R'''; R'' - C₁ - C₄-alkyl, C₂ - C₄-alkenyl, C₁ - C₄-alkyl substituted with C₁ - C₄-alkoxy, phenyl; R''' - C₁ - C₄-alkyl; L - hydrogen, C₁ - C₄-alkyl; G -

Description

 The invention relates to new derivatives of sulfamidosulfonylureas and herbicides containing them as active ingredients.

 To protect important crops, such as rice, wheat, corn, soybeans, cotton and sugar beets, from weeds and, therefore, to increase the yield, it is absolutely necessary to use herbicides. Particularly recently, selective herbicides are needed that can selectively kill weeds without showing phytotoxicity to cultivated plants when applied to leaves of cultivated plants and weeds simultaneously on fields in which such useful agricultural crops and weeds coexist. In addition, in order to avoid environmental pollution and reduce the cost of transportation and use, research and development has been carried out for many years on compounds having high herbicidal activity at low doses. Some of the compounds possessing such properties are currently used as selective herbicides. However, there is still a need for better compounds having such properties.

 As an example, a prior art source showing a chemical structure similar to that of the compounds of the present invention, Japanese Unexamined Patent Publications Nos. 103371/1983, 48973/1985 and 151577/1989 disclose compounds having an sulfonylurea bonded to an atom nitrogen.

 Unexamined Japanese patent publications NN 48973/1985 and 151577/1989 disclose compounds having a sulfonylurea attached to a nitrogen atom of a sulfonamide structure. However, the compounds of the present invention, in which the sulfonylurea is attached to the nitrogen atom of a specific sulfamide structure, were completely unknown, and they are new compounds.

 The present inventors over the years have conducted extensive research on the development of selective herbicides for important agricultural crops and studied the herbicidal properties of many compounds in order to search for compounds having higher herbicidal activity as well as selectivity. As a result, it was found that sulfamidosulfonylurea derivatives of the following formula [1] and their agriculturally suitable salts (hereinafter referred to as the compounds of the present invention) exhibit unusually strong herbicidal activity against many weeds when processing the soil or when treating foliage, and at the same time they have high safety for important crops such as wheat, corn, cotton, soybeans, sugar beets and rice. The present invention has been achieved based on this finding. On the other hand, since the compounds of the present invention show herbicidal activity at a very low dose compared to conventional herbicides, they are also useful as herbicides for orchards or non-agricultural land.

где Q представляет собой (см. фиг.1).Namely, the present invention provides derivatives of sulfamidosulfonylureas of the formula / 1 / or their salts:

where Q represents (see figure 1).

,
где A представляет CH группу или атом азота, и каждый из B и C независимо представляет /1-4/C алкильную группу, /1-4/C алкокси, /1-4/C моно- или поли-галоидалкокси группу, атом галогена, или /1-4/C моно-алкиламино группу.where R ¹¹ represents a / 1-6 / C alkyl group, / 3-7 / C cycloalkyl group, / 3-7 / C cycloalkenyl group, / 1-6 / C alkyl group substituted by / 3-7 / C cycloalkyl group , / 1-6 / C alkyl group substituted by / 3-7 / C mono or polyhalo cycloalkyl group, / 2-6 / C alkenyl group, / 2-6 / C alkynyl group, / 1-6 / C alkyl group, substituted / 1-6 / C alkoxy group, / 1-6 / C alkyl group, substituted / 1-6 / C alkylthio group, / 1-6 / C alkyl group, substituted / 1-6 / C mono- or di-alkylamino group, / 1-6 / C mono- or polyhaloalkyl group, / 2-6 / C mono- or poly-haloalkyl a alkyl group, a / 1-6 / C alkyl group substituted by a cyano group, / 1-6 / C alkyl group substituted by a / 1-6 / C alkoxycarbonyl group, / 2-6 / C alkenyl group substituted by / 1-6 / C alkoxycarbonyl group, / 1-6 / C mono- or poly-haloalkyl group substituted by / 1-6 / C alkoxycarbonyl group, / 1-6 / C alkyl group, substituted / 1-6 / C mono- or di-alkylaminocarbonyl group, / 1-6 / C alkoxycarbonyl group, / 1-6 / C mono- or di-alkylaminocarbonyl group, cyano group, / 1-6 / C alkyl group, substituted by / 1-6 / C alkylcarbonyl group, / 1- 6 / C alkylcarbon l group, / 1-6 / C mono- or poly-haloalkylcarbonyl group, phenyl or benzyl group (provided that such a phenyl or benzyl group can be mono- or poly-substituted by a halogen atom, trifluoromethyl group, nitro group, / 1 -6 / C alkyl group, / 1-6 / C alkoxy group or / 1-6 / C alkoxycarbonyl group), a 3-6-membered heterocyclic group (provided that such a heterocyclic group contains 1-3 heteroatoms selected from the groups consisting of nitrogen, oxygen and sulfur atoms in the ring and may be mono- or poly-substituted halogen atom, trifluoromethyl group, nitro group, / 1-6 / C alkoxy group, / 1-6 / C alkoxy group or / 1-6 / C alkoxycarbonyl group, / 1-6 / C alkyl group substituted with 3- A 6-membered heterocyclic group (provided that such a heterocyclic group contains from 1 to 3 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur atoms in the ring and may be mono- or poly-substituted by a halogen atom, trifluoromethyl group, nitro group, / 1-6 / C alkyl group, / 1-6 / C alkoxy group or / 1-6 / C alkoxycarbonyl group )
R ¹² represents a hydrogen atom, a / 1-6 / C alkyl group, / 2-6 / C alkenyl group, / 2-6 / C alkynyl group, phenyl or benzyl group (provided that such a phenyl group or benzyl group substituted by a halogen atom, trifluoromethyl group, (1-6 / C alkyl, / 1-6 / C alkoxy group or / 1-6 / C alkoxycarbonyl group),
R ¹³ represents a / 1-6 / C alkyl group, a phenyl or benzyl group (provided that such a phenyl or benzyl group may be substituted by a halogen atom, a trifluoromethyl group, / 1-6 / C alkyl group, / 1-6 / C alkoxy group, (1-6 / C alkoxycarbonyl group or nitro group),
or R ¹² and R ¹³ form together with the nitrogen atom to which they are attached a saturated 5-7 membered heterocyclic group, or R ¹² and R ¹³ form together with the oxygen atom and the nitrogen atom to which they are attached, 5-7- heterocyclic membered group,
R ²¹ represents a / 1-6 / C alkyl group, / 3-7 / C cycloalkyl group, / 1-6 / C alkyl group substituted by / 3-7 / C cycloalkyl group, / 1-6 / C alkyl group substituted / 3-7 / C mono- or poly-halo-cycloalkyl group, / 2-6 / C alkenyl group, / 2-6 / C alkynyl group, / 1-6 / C alkyl group, substituted by / 1-6 / C alkoxy group , / 1-6 / C alkyl group substituted by / 1-6 / C alkylthio group, / 1-6 / C alkyl group substituted by / 1-6 / C mono- or di-alkylamino group, / 1-6 / C mono- or poly-haloalkyl group, / 2-6 / C mono- or poly-haloalkenyl group, / 1-6 / C alkyl group, s substituted with a cyano group, / 1-6 / C alkyl group, substituted with / 1-6 / C alkoxycarbonyl group, / 2-6 / C alkenyl group, substituted with / 1-6 / C alkoxycarbonyl group, / 1-6 / C alkyl group substituted with a / 1-6 / C mono- or di-alkylaminocarbonyl group, / 1-6 / C alkoxycarbonyl group, / 1-6 / C mono- or di-alkylaminocarbonyl group, cyano group, / 1-6 / C alkyl group substituted with a / 1-6 / C alkylcarbonyl group, / 1-6 / C alkylcarbonyl group, / 1-6 / C mono- or poly-haloalkylcarbonyl group, phenyl or benzyl group (provided that such phenyl The n-benzyl group may be a mono- or poly-substituted halogen atom, a trifluoromethyl group, a nitro group, a 1-6 / C alkyl group, a 1-6 / C alkoxy or a 1-6 / C alkoxycarbonyl group), 5- 6-membered heterocyclic group (provided that such a heterocyclic group contains from 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur atoms in the ring, and such a heterocyclic group can be mono- or poly-substituted by a halogen atom , trifluoromethyl group, nitro group, / 1-6 / C alkyl, / 1-6 / C alkoxy or (1-6 / C alkoxycarbonyl group),
R ²² represents a hydrogen atom or a / 1-6 / C alkyl group,
R ²³ represents a hydrogen atom or a / 1-6 / C alkyl group,
R ²⁴ represents a hydrogen atom, a / 1-6 / C alkyl group, a halogen atom, / 1-6 / C mono- or poly-haloalkyl group, / 1-6 / C alkyl group substituted by a / 1-5 / C alkoxy group , / 1-6 / C alkyl group, substituted / 2-6 / C alkenyloxy group, / 1-6 / C alkyl group, substituted / 2-6 / C alkynyloxy group, / 1-6 / C alkyl group, substituted / 1-6 / C mono- or poly-haloalkoxy group, / 1-6 / C alkyl group substituted by / 1-6 / C-alkylthio group, / 1-6 / C alkyl group substituted by / 1-6 / C alkylsulfonyl group, / 1-6 / C alkyl group, substituted cyano group, / 1-6 / C alkoxycarbonyl a group, / 1-6 / C alkyl group, substituted by / 1-6 / C alkoxycarbonyl group, / 1-6 / C alkoxycarbonyl group, or / 1-6 / C alkyl group, substituted by / 1-6 / C alkylcarbonyl group ,
R ²⁵ represents a hydrogen atom or a / 1-6 / C alkyl group,
R ²⁶ represents a hydrogen atom or a / 1-6 / C alkyl group,
R ²⁷ represents a hydrogen atom or a / 1-6 / C alkyl group,
R ²⁸ represents a hydrogen atom, a / 1-6 / C alkyl group, / 1-6 / C mono- or poly-haloalkyl group, / 1-6 / C alkyl group, substituted by / 1-6 / C alkoxy group, / 1 -6 / C alkyl group substituted by / 2-6 / C alkenyloxy group, / 1-6 / C alkyl group substituted by / 2-6 / C alkynyloxy group, / 1-6 / C alkyl group substituted by / 1-6 / C alkylthio group, / 1-6 / C alkyl group substituted by / 1-6 / C alkylsulfonyl group, / 1-6 / C alkyl group substituted by cyano group, / 1-6 / C alkoxycarbonyl group, / 1-6 / C alkylcarbonyl group, / 1-6 / C alkyl group, substituted / 1-6 / C alkoxy a rbonyl group, or a / 1-6 / C alkyl group substituted with a / 1-6 / C alkylcarbonyl group;
L represents a hydrogen atom, a / 1-6 / C alkyl group, / 2-6 / C alkenyl group or / 2-6 / C alkynyl group;
X represents an oxygen or sulfur atom;
G represents a group

,
where A represents a CH group or a nitrogen atom, and each of B and C independently represents a / 1-4 / C alkyl group, / 1-4 / C alkoxy, / 1-4 / C mono- or poly-haloalkoxy group, a halogen atom or / 1-4 / C mono-alkylamino group.

 The present invention also provides a selective herbicide containing one or more compounds of the present invention as active ingredients.

 Further, the present invention provides a herbicidal composition comprising one or more compounds of the present invention and one representative selected from the group consisting of alachlor, acetochlor, metochlor, primisulfuron and nicholsufuron as active ingredients.

 Now the present invention will be described in detail with reference to preferred embodiments of the invention.

 The compounds of formula (I) of the present invention can be easily obtained using any of the following reaction schemes 1 to 6.

В приведенных выше формулах Q, G, L и X имеют значения, определенные выше.Reaction Scheme 1

In the above formulas, Q, G, L, and X have the meanings defined above.

 In particular, the sulfamidosulfonyliso (thio) cyanate derivative / II / is dissolved in a sufficiently dried inert solvent such as dioxane, acetonitrile or acetone, then a pyrimidine or triazine derivative of the formula / III / is added to it, and the mixture is stirred, whereby the reaction usually proceeds smoothly , and the compound (I) of the present invention is obtained. When the reaction is difficult, a very small amount of a suitable base may be added, such as triethylamine, triethylenediamine, pyridine, sodium methylate, sodium hydrate or potassium carbonate, whereby the reaction proceeds freely.

В приведенных выше формулах Q, G, L и X имеют значения, определенные выше, и Y представляет /1-6/C алкильную группу или фенильную группу.Reaction Scheme 2

In the above formulas, Q, G, L, and X are as defined above, and Y represents a / 1-6 / C alkyl group or phenyl group.

 Namely, the sulfamidosulfonamide derivative / IV / is reacted with a chloro / thio / formic acid ester or di / thio / carboxylic acid ester in a solvent such as acetone, methyl ethyl ketone or acetonitrile in the presence of a base such as potassium carbonate to give a compound / X /. Then it is heated together with compound / III / in a solvent such as toluene, to obtain compound / I / of the present invention.

В приведенных выше формулах Q, G, L и Y имеют значения, определенные выше.Reaction Scheme 3

In the above formulas, Q, G, L, and Y have the meanings defined above.

 The reaction of sulfamide (VI) with phenyl N-chlorosulfonylcarbamate (VII; Y phenyl group) or alkyl N-chlorosulfonylcarbamate (VII; Y / 1-6 / C alkyl group) is usually carried out using 0.5 to 3.0 mol, preferably from 0.9 to 1.2 mol of the carbamate derivative / VII / per mole of sulfamide / VI /.

The reaction temperature may optionally be selected in the range from -50 ^° C to 100 ^° C, preferably from -20 ^° C to 30 ^° C.

 This reaction is carried out using a variety of bases. The base is used in an amount of from 0.5 to 4.0 mol per mol of sulfamide / VI /.

 Suitable bases include metal hydrides such as sodium hydride, metal alcoholates such as sodium ethylate, alkyl metals such as n-butyl lithium, organic bases such as triethylamine, pyridine and 1,8-diazabicyclo / 5.4.0 / -7 -undecene (DWI), and inorganic bases such as potassium hydroxide and sodium hydroxide. Metal hydride is particularly preferred.

 A suitable solvent for this reaction is a reaction inert solvent which includes aromatic hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons such as dichloromethane, chloroform or carbon tetrachloride, ethers such as ethyl ether, isopropyl ether, dioxane or tetrahydrofuran, a nitrile such as acetonitrile or propionitrile, a hydrocarbon such as petroleum ether, petroleum gasoline or hexane, a ketone such as acetone or methyl ethyl ketone, an ester, such as ethyl acetate, and amides such as N, N-dimethylformamide, N, N-dimethylacetamide or N, N, N ', N'-hexamethylphosphoric triamide. These solvents can be used singly or in combination as a mixture. An ether or amide is particularly preferred.

 Then phenyl N-sulfamidosulfonylcarbamate (Y; X = 0, Y is a phenyl group) or alkyl N-sulfamidosulfonylcarbamate (Y; X = 0, Y is a lower alkyl group) and compound / III / is heated in a solvent such as benzene or toluene, with obtaining the compounds of the present invention (1; X = 0).

В приведенных выше формулах Q, G, L и Y имеют значения, определенные выше.Reaction Scheme 4

In the above formulas, Q, G, L, and Y have the meanings defined above.

 Namely, the sulfamidosulfonamide derivative / IV / is reacted with the carbamate derivative / VIII / in a solvent such as acetone, acetonitrile or dioxane in the presence of an inorganic base such as potassium carbonate or an organic base such as triethylamine or DVI to give compounds of the present invention (1; X = 0).

В приведенных выше формулах Q, G и L имеют значения, определенные выше.Reaction Scheme 5

In the above formulas, Q, G and L have the meanings defined above.

 Namely, amine / III / is reacted with chlorosulfonyl isocyanate in a solvent such as tetrahydrofuran, dimethoxyethane, acetonitrile, propionitrile, N, N-dimethylformamide, dichloromethane, dichloroethane, benzene or toluene, and then reacted with sulfamide / VI / in the presence of a base, such as triethylamine, pyridine, sodium hydride, sodium methylate, sodium ethylate, sodium hydroxide, potassium hydroxide or potassium carbonate, to obtain the compounds of the present invention (1; X = 0).

В приведенных выше формулах Q и G имеют значения, определенные выше.Reaction Scheme 6

In the above formulas, Q and G have the meanings defined above.

 In particular, the sulfamidosulfonamide derivative / IV / is reacted with an isothiocyanate derivative / IX / in a solvent such as acetone, acetonitrile or dioxane in the presence of an inorganic base such as potassium carbonate or an organic base such as triethylamine or DVI to give a compound of the present invention (1; X = S, L = H).

 The sulfamidosulfonyliso / thio / cyanate derivative / II / used as starting material in Reaction Scheme 1 can be synthesized from the sulfamidosulfonamide / IV derivative in accordance with methods described, for example, in Japanese Patent Publication No. 148879/1983, 31775 / 1984 and 13266/1980.

 Further, sulfamidosulfonyl isocyanate (II; X = 0) can also be synthesized according to the method of reaction scheme 7 in accordance with the method described, for example, in unexamined Japanese patent publication N 81320/1974.

В приведенных выше формулах Q имеет значения, определенные выше.Reaction Scheme 7

In the above formulas, Q has the meanings defined above.

 Derivative sulfamidosulfonyliso / thio / cyanate / II /, sulfamidosulfonamide derivative / IV /, phenyl N-sulfamidosulfonyl / thio / carbamate (V; K phenyl group) and alkyl N-sulfamidosulfonyl / thio / carbamate (V; Y lower alkyl) used in as intermediates in the present invention are also new compounds. The sulfamidosulfonamide derivative / IV / can be synthesized from the sulfamide derivative / VI / according to the methods of reaction schemes 8 and 9.

В приведенных выше формулах Q имеет значения, определенные выше.Reaction Scheme 8

In the above formulas, Q has the meanings defined above.

 According to reaction scheme 8, the removal of the tert-butyl group is carried out using trifluoroacetic acid. The amount of trifluoroacetic acid may optionally be selected in the range from an equimolar amount to an excess amount. Trifluoroacetic acid can also be used as a solvent without any problems.

The reaction temperature may optionally be selected in the range from -50 ^° C to 80 ^° C, preferably from -20 ^° C to 30 ^° C.

 When a solvent is used for this reaction, it is a reaction inert solvent which includes aromatic hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons such as dichloromethane, chloroform or carbon tetrachloride, ethers such as ethyl ether, isopropyl ether, dioxane or tetrahydrofuran, nitriles such as acetonitrile or propionitrile, hydrocarbons such as petroleum ether, petroleum gasoline or hexane, ketones such as acetone or methyl ethyl ketone, cl fatty esters such as ethyl acetate and amides such as N, N-dimethylformamide, N, N-dimethylacetamide or triamide of N, H, N ', N'-hexamethylphosphoric acid. These solvents can be used singly or in combination as mixtures.

В приведенных формулах Q имеет значения, определенные выше.The reaction scheme 9

In the above formulas, Q has the meanings defined above.

 According to reaction scheme 9, the reaction of tert-butanol with chlorosulfonyl isocyanate can be carried out according to a method known per se, for example, in accordance with Japanese patent publication No. 101323/1975, which has not passed examination.

 The reaction of sulfamide / VI / with tert-butyl sulfamoyl chloride is carried out using 0.5 to 3.0 mol, preferably 0.9 to 1.2 mol, of tert-butyl sulfamoyl chloride per mole of sulfamide / VI /.

The reaction temperature may optionally be selected in the range from -50 ^° C to 100 ^° C, preferably from -20 ^° C to 30 ^° C.

 The reaction may be carried out using various bases. The base is used in an amount of from 0.5 to 4.0 mol, preferably from 0.8 to 2.2 mol, per mol of sulfamide / VI /. Passing bases include metal hydrides such as sodium hydride, metal alcoholates such as sodium ethylate, alkyl metals such as n-butyllithium, organic bases such as triethylamine, pyridine, 1,8-disabicyclo / 5.4.0 / -7 Undecene (DBU) and inorganic bases such as potassium hydroxide or sodium hydroxide. Metal hydride is particularly preferred.

 A suitable solvent for the reaction is a reaction inert solvent that includes aromatic hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons such as dichloromethane, chloroform or carbon tetrachloride, ethers such as ethyl ether, isopropyl ether, dioxane or tetrahydrofuran, nitriles such as acetonitrile or propionitrile, hydrocarbons such as petroleum ether, petroleum gasoline or hexane, ketones such as acetone or methyl ethyl ketone, esters, such as ethyl acetate, and amides such as N, N-dimethylformamide, N, N-dimethylacetamide or N, N, N ′, N′-hexamethylphosphoric triamide. These solvents may be used singly or in combination as mixtures. An ether or amide is particularly preferred.

 According to reaction scheme 3, phenyl N-chlorosulfonylcarbamate (VII; Y lower alkyl group) can be prepared by methods known per se, in accordance with, for example, Chemische Berichte, vol. 96, p. 56/1963 /. Sulfamide / VI /, used as starting material in the above reaction, can be prepared according to, for example, the description in the Jourmal of American Chemical Society, vol. 66, p. 1242/1944 /, U.S. Patent 2,826,594, Journal of Synthetic Organic Chemistry, Japan, Vol. 27 (No. 10), p. 980/1969 /, U.S. Patent 2,624,729, Chemische Berichti, T. 111, p. 1915/1978 /, which did not pass the examination of Japanese patent publications N 79894/1978 and N 208289/1983, in the Jndian Journal of Chemistry, Section B. T. 21B, p. 941/1982 /. As typical examples, syntheses of N, N-dimethyl-N'-methoxy sulfamide, N-methyl-N-methoxy-N'-ethyl sulfamide, N-methyl-N-methoxy-N'-methoxy sulfamide, N, N-dimethyl- N'-trifluoromethylthiosulfamide, N-methyl-N-methoxy-N'-trichloromethylthiosulfamide and 2-methoxy-1,2,5-thiadiazolidine-1,1-dioxide in the form of reaction schemes 10-15.

В настоящее время синтезы соединений настоящего изобретения будут описаны в виде примеров. Однако, следует понимать, что настоящее изобретение никоим образом не ограничивается такими конкретными примерами.

Currently, the syntheses of the compounds of the present invention will be described as examples. However, it should be understood that the present invention is in no way limited to such specific examples.

К 100 мл сухого тетрагидрофурана (ТГФ), содержащего 1,87 г (42,9 ммоль) 55% гидрида натрия, добавлялось 3,0 г (19,5 ммоль) N,N-диметил-N'-метоксисульфамида, растворенного в 20 мл сухого ТГФ, при охлаждении льдом, и смесь непрерывно перешивалась при той же температуре в течение 10 мин.Example 1
Preparation of 1 - [(N-dimethylsulfamoyl-N-methoxyamino) sulfonyl] -3- / 4,6-dimethoxypyrimidin-2-yl / urea

To 100 ml of dry tetrahydrofuran (THF) containing 1.87 g (42.9 mmol) of 55% sodium hydride, 3.0 g (19.5 mmol) of N, N-dimethyl-N'-methoxysulfamide dissolved in 20 were added. ml of dry THF, while cooling with ice, and the mixture was continuously stirred at the same temperature for 10 minutes.

 Then, 50 ml of tetrahydrofuran (THF) containing 4.83 g (20.5 mmol) of phenyl-N-chlorosulfonylcarbamate was added dropwise to the mixture, and the mixture was gradually warmed to room temperature and continuously stirred at room temperature for one hour.

 The reaction mixture was poured into 500 ml of ice water containing 5 g of 35% hydrochloric acid, and was extracted with diethyl ether. The diethyl ether layer was washed successively with water and a saturated aqueous solution of sodium chloride, and then dried over anhydrous magnesium sulfate. Then, the solvent was distilled off under reduced pressure to give 5.4 g of phenyl N - [(N-dimethylsulfamoyl-N-methoxyamino) sulfonyl] carbamate as an orange colored oil.

Then, a mixture comprising 3 g (8.5 mmol) of the above compound, 0.93 g (6 mmol) of 2-amino-4,6-dimethoxypyrimidine and 20 ml of dry benzene was heated under reflux for 10 minutes. After cooling, the solvent was distilled off under reduced pressure. The residue was washed with diethyl ether and collected by filtration, to give 1.0 g of the desired product 1 - [(N-dimethylsulfamoyl-N-methoxyamino] sulfonyl-3- / 4,6-dimethoxypyrimidin-2-yl / urea. Melting point 166- 167 ^o C.

К 50 мл сухого тетрагидрофурана (ТГФ), содержащего 1,60 г (36,7 ммоль) 55% гидрида натрия, добавлялось 2,8 г (16,7 ммоль) N-метил-N-метокси-N'-этилсульфамида, растворенного в 20 мл сухого ТГФ, при охлаждении льдом, и смесь непрерывно перемешивалась при той же температуре в течение 10 мин.Example 2
Preparation of 1 - [(N- (N-methyl-N-methoxyaminosulfonyl) -N-ethylamino) sulfonyl] -3- / 4,6-dimethoxypyrimidin-2-yl / urea

To 50 ml of dry tetrahydrofuran (THF) containing 1.60 g (36.7 mmol) of 55% sodium hydride, 2.8 g (16.7 mmol) of N-methyl-N-methoxy-N'-ethylsulfamide dissolved in 20 ml of dry THF, while cooling with ice, and the mixture was continuously stirred at the same temperature for 10 minutes

 Then, 30 ml of dry THF containing 4.13 g (17.5 mmol) of phenyl-N-chlorosulfonylcarbamate was added dropwise, and the mixture was gradually warmed to room temperature and continuously stirred at room temperature for one hour.

 The reaction mixture was poured into 500 ml of ice water containing 4 g of 35% hydrochloric acid and extracted with diethyl ether. The diethyl ether layer was washed successively with water and a saturated aqueous solution of sodium chloride, and then dried over anhydrous magnesium sulfate. Then, the solvent was distilled off under reduced pressure to give 5.0 g of phenyl N - [(N- (N-methyl-N-methoxyaminosulfonyl) -N-ethylamino) sulfonyl] carbamate as an orange-colored oil.

Then, a mixture comprising 2.5 g (6.8 mmol) of the above compound, 0.74 g (4.8 mmol) of 2-amino-4,6-dimethoxypyrimidine and 50 ml of dry benzene was heated under reflux for 10 min After cooling the mixture, the solvent was distilled off under reduced pressure. The residue was washed with diethyl ether and collected by filtration, to give 1.2 g of the desired 1 - [(N- (N-methyl-N-methoxyaminosulfonyl) -N-ethylamino) sulfonyl] -3- (4,6-dimethoxypyrimidin-2-yl) urea. Melting point: 157-158 ^o C.

К 15 мл сухого тетрагидрофурана (ТГФ), содержащего 0,25 г (6,25 ммоль) 60% гидрида натрия, добавлялось 0,43 г (2,83 ммоль) 2-метокси-1,2,5 -тиадиазолидин-1,1-диоксида, растворенного в 5 мл сухого ТГФ при охлаждении льдом, и смесь перешивалась в токе азота при комнатной температуре в течение 14 ч.Example 3
Preparation of 1- / 2-methoxy-1,2,5-thiadiazolidin-1,1-dioxide-5-sulfonyl / -3- / 4,6-dimethoxypyrimidin-2-yl / urea

To 15 ml of dry tetrahydrofuran (THF) containing 0.25 g (6.25 mmol) of 60% sodium hydride was added 0.43 g (2.83 mmol) of 2-methoxy-1,2,5-thiadiazolidin-1, 1-dioxide dissolved in 5 ml of dry THF under ice cooling, and the mixture was stirred in a stream of nitrogen at room temperature for 14 hours.

The system was then cooled to 0 ^° C, and 10 ml of dry THF containing 0.7 g (3 mmol) of phenyl-N-chlorosulfonylcarbamate was added dropwise to it. The mixture was gradually warmed to room temperature and continuously stirred at room temperature for one hour.

 The reaction mixture was poured into 100 ml of ice water containing 0.6 g of 35% hydrochloric acid and extracted with diethyl ether. The diethyl ether layer was washed successively with water and a saturated aqueous solution of sodium chloride, and then dried over anhydrous magnesium sulfate. The solvent was then distilled off under reduced pressure to give 0.7 g of the desired phenyl N- / 2-methoxy-1,2,5-thiadiazolidine-1,1-dioxide-5-sulfonyl / carbamate as a yellow viscous oil.

Then, a mixture comprising 0.7 g (2 mmol) of the above compound, 0.31 g (2 mmol) of 2-amino-4,6-dimethoxypyrimidine and 10 ml of dry benzene was heated under reflux for 10 minutes. After cooling the mixture, the solvent was distilled off under reduced pressure, and the residue thus obtained was washed with diethyl ether, and 0.5 g of the desired 1- (2-methoxy-1,2,5-thiadiazolidine-1,1-dioxide-5- was obtained sulfonyl) -3- (4,6-dimethoxypyrimidin-2-yl) urea. Melting point: 162-163 ^o C.

 The structures and physical properties of the compounds obtained using the same method as described in the previous examples are shown in FIGS. 2-10.

 Now tab. 1-26 are examples of specific compounds of the present invention, including compounds obtained in the previous examples. However, it should be understood that the compounds of the present invention are not limited to such specific examples.

 The symbols used in the tables have the following meanings: Me: methyl group, Et: ethyl group, Pr n: propyl group, Pr i: isopropyl group, Pr c: cyclopropyl group, Bu n: n-butyl group, Bu s: sec . -butyl group, Bu i: isobutyl group, Bu t: tert-butyl group, Pen-n; an n-pentyl group, Ph: a phenyl group, and Gn has the same meanings as the aforementioned G symbol and includes Ga, Gb, Gc as defined below.

 Ga G1 G13 (i.e., it represents all of G1 G13).

 Go G1 G6 (i.e. it represents everything from G1 G6).

 Gc G1 G3 (i.e., it represents all of G1 G3).

 When the compound of the present invention is intended to be used as a herbicide, it is usually mixed with a suitable carrier, for example, a solid carrier, such as clay, talc, bentonite or diatomaceous earth, or a liquid carrier, such as water, alcohol (such as methanol or ethanol), an aromatic hydrocarbon (such as benzene, toluene or xylene), a chlorinated hydrocarbon, ether, ketone, ester (such as ethyl acetate), or an acid amide (such as dimethylformamide). If desired, an emulsifier, dispersing agent, suspending agent, penetration, distribution promoting agent, or stabilizer may be added to form as necessary, such as a liquid formulation, emulsifiable concentrate, wettable powder, dust, granules or a flowable preparation.

 Examples will now be given of herbicide formulations containing the invention as active ingredients. However, it should be understood that the present invention is in no way limited to such specific examples. In the following formulation examples, “parts” mean “parts by weight”.

Example 1 of the formulation of the present invention:
Wettable powder
Compound N 1 of the present invention 20 parts
Zhiklit A (a trademark of kaolin type clay manufactured by Zhiklit Industries, Co. Ltd.) 76 parts
Sorpol 5039 (trademark for a mixture of non-ionic surfactant and anionic surfactant manufactured by Toho Chemical Industry Co. Ltd.) 2 parts
Karpleks (trademark of a coagulation-preventing agent consisting of a mixture of a surfactant and a finely divided silica powder manufactured by Sionogi Pharmaceutical Co., Ltd.) 2 parts
The above ingredients are homogeneously pulverized and mixed to form a wettable powder.

Formulation Example 2:
Wettable Powder
Compound N 2 of the present invention 40 parts
Zhiklin A (trade name for kaolin type clay produced by Zhiklit Industries, Co. Ltd.) 54 parts
Sorpol 5039 (trade name for a mixture of non-ionic and anionic surfactants manufactured by Toho Chemical Industry Co. Ltd.) - 2 parts
Carplex (trade name for an anti-coagulation agent consisting of a mixture of a surface-active agent and a fine silica powder manufactured by Sionogi Pharmaceutical Co., Ltd.) 4 parts
The above ingredients are homogeneously pulverized and mixed to form a wettable powder.

Formulation Example 3:
Emulsifiable Concentrate
Compound N 3 of the present invention 5 parts
Xylene 75 parts
N, N-dimethylformamide 15 parts
Soprol 2680 (trade name for a mixture of non-ionic and anionic surfactants manufactured by Toho Chemical Industry Co. Ltd.) - 5 parts
The above ingredients are mixed homogeneously to form an emulsifiable concentrate. When using it, the above emulsifiable concentrate is diluted 10-10000 times with water and used so that the amount of active ingredient is from 0.005 to 10 kg per hectare.

Formulation Example 4:
Fluid drug
Compound N 4 of the present invention 25 parts
Agrizole S-710 (trade name for the surfactant manufactured by Kao Corporation) 10 parts
Runox 1000C (trade name for anionic surfactant manufactured by Toho Chemical Industry Co. Ltd.) 0.5 parts
1% Rhodopol water (trade name of the thickener produced by Ron-Pulenk) 20 parts
Water 44.5 parts
The above ingredients are mixed homogeneously to form a flowable preparation.

Formulation Example 5:
Fluid drug
Compound N 20 of the present invention 40 parts
Agrizole S-710 10 parts
Runox 1000C 0.5 parts
1% Rhodopol water 20 parts
Water 29.5 parts
These ingredients are mixed homogeneously to form a flowable preparation.

Formulation Example 6:
Granules
Compound N 22 of the present invention 1 part
Bentonite 55 parts
Talc 44 parts
The above ingredients are mixed homogeneously and pulverized, and after adding a small amount of water, the mixture was mixed and granulated using an extrusion-type granulating mechanism, followed by drying to obtain granules.

 In addition, the compound of the present invention can be combined with other herbicides, with a variety of insecticides, fungicides and synergistic agents during the preparation of formulations or during use, as appropriate.

 As such other herbicides, for example, a compound described in Farm Chemicals Handbook (1989) may be mentioned.

 For example, the compound of the present invention can be mixed with herbicides such as alachlor, acetochlor, metal chlorine, primisulfuron, nicosulfuron, atrazine, cyanazine, EPTC, 2,4-D, butylate, dicamba, bromoxynil, tridifan, metsulfuron-methyl, tifensulfuron-methyl, triasulfuron, isoproturon, chlorotoluron, diflufenican, metabenzthiazuron, diclofop-methyl, diphenzoquat, phenoxapropethyl, bentazone, trifluralin, pendimethalin and N - [(4,6-dimethoxypyrimidin-2-yl) -methoxycarbonyl -1-methylpyrazole-5-sulfonamide as described in US Pat. 8277, or with an herbicide safety agent (antidote or antidote) such as 1,8-naphthoic anhydride or N, N-diallyl-2,2-dichloroacetamide.

 The compound of the present invention can be used to control a variety of weeds not only in agriculture and horticulture in fields such as upland fields, paddy fields, or in gardens, but also in non-agricultural land such as playgrounds, unused vacant land or sections along the railways.

 The dose varies depending on the place of application, season, method of application, type of weeds to be destroyed, type of crop, etc. However, usually the dose is in the range of 0.005 to 10 kg per hectare as the amount of active ingredient.

 Now, the herbicidal activity of the compounds of the present invention will be described in detail with reference to the following test examples. The numbers of the compounds referred to in the test examples correspond to the numbers of the compounds given above.

Test Example 1:
Tillage test
A plastic box having a length of 15 cm, a width of 22 cm and a depth of 6 cm is filled with sterilized diluvial soil and the seeds of Echinochloa crus-galli, Digitaria adscendens, Cyperus microiria, Solanum nigrum, Galinsoga ciliata, Rorippa indica, Oryza sativa, Zea mays, were sown Triticum aestivum, geycine max u Gossypium nerbaceum, and the soil was applied on them with a cover thickness of about 1.5 cm, and then the herbicide solution was applied uniformly on the soil surface so that the active ingredient was distributed in a given concentration. The herbicidal solution was prepared by diluting the wettable powder described in the preceding formulation examples with water and applied over the entire surface of the soil using a hand sprayer. Four weeks after the application of the herbicidal solution, the herbicidal effects against each of the weeds and the phytotoxicity indicators against cultivated plants were determined based on the following standard estimates. The results are shown in table.27. (The rate of the compounds correspond to the numbers of the compounds in the examples). Some of the compounds of the present invention exhibit selectivity for certain crop plants.

Standard grades:
5: Degree of growth inhibition of more than 90% (almost completely wilted)
4: Degree of growth inhibition from 70 to 90%
3: Degree of growth inhibition from 40 to 70%
2: The degree of inhibition of growth from 20 to 40%
1: The degree of inhibition of growth from 5 to 20%
0: Degree of growth inhibition of less than 5% (almost ineffective)
The above degrees of growth inhibition were calculated using the following equation:
The degree of inhibition of growth (%) (1 T / N) x 100
where T is the weight of weeds grown above the surface of the soil on the treated area;
N is the weight of the ground part of the weeds in the untreated area.

Test Example 2:
Herbicidal Test on Foliage
A plastic box 15 cm long, 22 cm wide and 6 cm deep was filled with sterilized diluvial soil, and seeds were sown with seeds Echinochloa crus-galli, Digitaria adscendens, Cyperus microiria, Solanum nigrum, Galinsoga ciliata, Rorippa indica, Oryza sativa, Zeaumestivrit, T , Glycine max, gossypium herbaceum and Beta vulgaris, and from above the seeds were covered with a layer of soil about 1.5 cm thick. When various weeds and cultivated plants grew to the stage of 2 or 3 leaves, the leaves were uniformly sprayed with the herbicide solution so that the active ingredient was applied in a given concentration.

 The herbicide solution was prepared by diluting with water a wettable powder, described in the above examples of preparative forms, and was applied to the entire surface of the foliage of weeds and cultivated plants using a small sprayer. Four weeks after the application of the herbicidal solution, the herbicidal action on weeds and phytotoxicity for each of the cultivated plants was determined based on the standard estimates described in test example 1. The results are shown in table 28. (Connection numbers correspond to connection numbers in the examples).

The following abbreviations are used in Tables 27 and 28
Dose: The dose of the active ingredient / kg / ha /
EC: Echinochloa crus-golli (barnyardgrass) bramble
DI: Digitaria adscendens (large crabgrass) dewdrop
CY: Cyperus microiria (annual sedge) sedge annual
SO: Solanum nigrum (black hightshade) nightshade black
GA: Galinsoga ciliata (hairy galinsoga)
RO: Rorippa indica (fieldcress) Indian Crusade
OR: Oryza sativa (rice) rice
ZE: Zea mays (corn) corn
TR: Triticum aestivum (wheat) wheat
GL: Glycine max (soybean) soy
GO: Gossypium herbaceum (cotton) cotton
BE: Beta vulgaris (sugar beet) sugar beet
Further, the present inventors conducted studies to increase the herbicidal effects of the compounds of the present invention. As a result, it was found that when one of alachlor, acetochlor, metalachlor, primisulfuron and nicosulfuron is added to the compound of the present invention, the herbicidal effect not only reaches the sum of the effects of the corresponding compounds, but also a synergistic effect is obtained without any phytotoxicity with respect to cultural plants.

 To prove the advantages of the claimed compounds, an experiment was conducted in accordance with the above methodology of test example N1. The results thus obtained are shown in the table.

 The comparison compound is compound N 73 described in EP 0131258 (p. 18, table 2) and N3 of USSR patent N 1466634 (p. 4, table 1) (known), as well as compound N 3 of this application.

 The main weeds found on the corn field are designated A, B, C, D.

 The results are presented in table A.

 From table A it is seen that the compounds of this application exceeded the known 2-8 times in herbicidal effect and 8 times in terms of safety in relation to corn.

A: Xanthium strumarium
B: Ipomoea purpurea
C: Chenopodium album
D: datura stramonium
ZE: Zea mays (corn)
The synergistic herbicidal effect of the mixture of herbicides will be explained below as follows.

 Namely, the individual active compounds may possibly find some of their own shortcomings in the sense of herbicidal activity in many cases. In this case, when two active compounds are combined, if the resulting herbicidal activity is more than a simple sum of the activities of the corresponding two compounds (i.e., the expected activity), then this is considered a synergistic effect. The expected activity for a particular combination of two herbicides is calculated as follows (Colby S. R. Calculation of the synergistic and antagonistic activities of combinations of herbicides. Weed, vol. 15, p. 20-22, 1967.

где α степень подавления, когда гербицид А применялся в дозе а в кг/га,
b степень подавления, когда гербицид В применялся в дозе b в кг/га,
E ожидаемое подавление, когда применяются a кг/га гербицида A и b кг/га гербицида B.

where α is the degree of suppression when the herbicide A was applied at a dose of a in kg / ha,
b degree of suppression when the herbicide B was applied at a dose b in kg / ha,
E expected suppression when a kg / ha of herbicide A and b kg / ha of herbicide B are applied.

 Namely, if the actual degree of suppression is greater than the degree of suppression calculated by the above formula, the activity during combination is considered as exhibiting a herbicidal effect.

 This will now be explained specifically with reference to examples. However, these compounds, their proportions in the formulations and types of formulations of the present invention should not be construed as limited by such specific examples. In these examples, “parts” means “parts by weight”.

Formulation Example 7:
Wettable Powder
Compound N3 of the present invention 10 parts
Primisulfuron 10 parts
Zhiklit PFP (a trademark of kaolin clay, manufactured by Zhiklin Industries Co., Ltd.) 72 parts
Sorpol 5039 (trademark for alkyl ether sulfate manufactured by Toho Chemical Industry Co. Ltd.) 2 parts
Soybean Oil 2 parts
Karpleks N 80 (trademark of fine silica powder manufactured by Sionogi Pharmaceutical Co. Ltd.) 4 parts
The above ingredients were homogeneously atomized and mixed to form a wettable powder.

Formulation Example 8:
Wettable Powder
Compound N3 of the present invention 10 parts
Nicosulfuron 10 parts
Zhiklit PFP (a trademark of kaolin type clay produced by Zhiklit Industries, Co., Ltd.) 72 parts
Sorpol 5039 (trademark for alkyl ether sulfate manufactured by Toho Chemical Industry Co. Ltd.) 2 parts
Soybean Oil 2 parts
Karpleks N 80 (trademark of fine silica powder manufactured by Sionogi Pharmaceutical Co. Ltd.) 4 parts
The above ingredients were homogeneously atomized and mixed to form a wettable powder.

Formulation Example 9:
Suspension concentrate
Compound N 3 of the present invention 2 parts
Alachlor 38 parts
Sorbon T-80 (trademark for polyoxyethylene sorbitan monooleate manufactured by Toho Chemical Industry Co. Ltd.) 5 parts
Wigum (trademark for magnesium-aluminum-silicate manufactured by Vanderbil Co.) 5 parts
Water 50 parts
The above ingredients were uniformly mixed and pulverized using a sand mill to obtain a suspension concentrate having a particle size of at most 5 μm.

Formulation Example 10:
Suspension concentrate
Compound N 3 of the present invention 2 parts
Acetochlor 38 parts
Sorbon T-80 5 parts
Wigum 5 parts
Water 50 parts
The above ingredients were uniformly mixed and pulverized using a sand mill to obtain a suspension concentrate having a particle size of at most 5 μm.

Formulation Example 11:
Granules
Compound N 3 of the present invention 5 parts
Metallochlor 75 parts
Aron A (trademark of polycarboxylate manufactured by Toagosei Chemical Industry Co. Ltd.) 7 parts
Sanekisu C (a trademark of ligninsulfonate manufactured by Sane Kokusaku Pulp Co. Ltd.) 10 parts
Newlex Powder (trademark DV-Pa manufactured by Nippon Oil & Feto Co. Ltd.) 2 parts
Zhiklit PFP (trademark of kaolin type clay manufactured by Zhiklit Industries, Co. Ltd.) 1 part
A suitable amount of water was added to the above ingredients, and the mixture was atomized and mixed to obtain a suspension, which was granulated to obtain granules, while the moisture was removed using a spray dryer:
Formulation Example 12:
Granules
Compound N 3 of the present invention 5 parts
Alachlor 75 parts
Aron A 7 parts
Sanekisu C 10 parts
Newlex Powder 2 parts
Zhiklit PFP (trademark clay kaolin type) 1 part
A suitable amount of water was added to the above ingredients, and the mixture was atomized and mixed to obtain a suspension, which was granulated into granules to remove moisture using a spray dryer.

Test Example 3:
Tillage test
A plastic box 30 cm long, 30 cm wide and 10 cm deep was filled with sterilized upland soil, and seeds were sown with seeds of corn (Zia mays), green bristles (Sitaria viridis), limoncharis (Abutilon theophrasti) and fruit cock (Xanthium strumarium), and the seeds were covered a layer of soil with a thickness of about 0.5 cm. On the day of sowing, a herbicidal solution in the amount of water was used for spraying at the rate of 5 l / ha. The herbicidal solution that was used was prepared by diluting the formulation described in the previous formulation examples with water, and was applied using a small sprayer. The weight of the ground portion of each weed was measured after three weeks after application, and the degree of regulation of growth (%) was calculated using the following equation.

The degree of regulation of growth (%) (1 T / N) x 100
where T is the weight of the ground part of the weed in the treated area;
N is the weight of the ground part of the weeds in the untreated area.

 The test results for the herbicidal effect exerted by the individual herbicides are shown in Table 29. The test results for the herbicidal effect of the mixture of herbicides are shown in table.30. (The numbers of the compounds correspond to the numbers given in the examples).

Test Example 4:
Herbicidal test for growth stage processing
A plastic box 30 cm long, 30 cm wide and 10 cm deep was filled with sterilized upland soil, and seeds were sown with seeds of corn (Zea mays), green bristles (Setaria viridis), limoncharis (Abutilon theophrasti) and fruit cock (Xanthium strumarium /, and the seeds were covered a layer of soil with a thickness of 0.5 cm. On the tenth day after sowing, the herbicidal solution was sprayed at the growth stage with an amount of sprayed water of 5 l / ha. The herbicidal spray solution was prepared by diluting the formulations obtained in accordance with the previous Formulation Examples with water and sprayed with a small sprayer. Weight ground part of each weed was measured after two weeks after application, and the degree of regulation or growth suppression (%) was obtained in the same manner as in Test Example 3.

 The test results for the herbicidal effect of individual herbicides are shown in table.31.

 The test results for the herbicidal action of the mixture of herbicides are shown in table. 32. (The compound numbers correspond to the compound numbers given in the examples).

In table 29-32 the following abbreviations are used:
Dose: Dose of the active ingredient (g / ar)
SE: Setaria viridis (bristle green)
AB: Abutilon theophrasti (limnocharis)
XA: Xanthium strumarium (fruit cock)
ZE: Zea mays (corn)
mV: measured value
W: Expected value.

Claims (2)

1. Derivatives of sulfamidosulfonylureas of the General formula I

where Q is

wherein R '' C ₁ C ₄ alkyl group, C ₂ - C ₄ alkenyl group, C ₂ C ₄ alkynyl group or a C ₁ C ₄ alkyl group substituted by a C ₁ - C ₄ alkoxy, phenyl;
R ″ ″ C ₁ C ₄ alkyl group;
L is hydrogen or C ₁ C ₄ alkyl group;
G -

where B is methyl or methoxy;
With methyl, methoxy or difluoromethoxy.  2. Selective herbicidal composition comprising the active ingredient - a sulfonylurea derivative and target additives, characterized in that as a sulfonylurea derivative it contains a compound of formula I according to claim 1 in the following ratio of ingredients, wt. Active ingredient 2 40
Target Supplements Else
Priority by signs:
12/04/89 when

or

2R '' C ₁ C ₄ -alkyl group, R '''C ₁ - C ₄ -alkyl group, L hydrogen, G

In methoxy, C methoxy, methyl;
12/04/89 at R ″ C ₂ C ₄ alkenyl group, phenyl.

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