Substituted aromatic amides thiocarbonic acid and the herbicide agent containing them

 

(57) Abstract:

Describes substituted aromatic amides thiocarbonic acid of General formula I, where Z, R1, R2specified in paragraph 1 of the claims. The compounds exhibit herbicide activity. Describes also the herbicide agent containing the compound of formula I. 2 S. and 1 C.p. f-crystals, 5 PL.

The invention relates to new derivatives thiocarbonic acid having biological activity, in particular to substituted aromatic Amida thiocarbonic acid and the herbicide agent containing them.

From application EP N 0 370 332, published may 30, 1990, known derivatives thiocarbonic acid, which can be used as a herbicide.

Object of the invention is the expansion of the range derived thiocarbonic acid having biological activity, in particular herbicide activity.

The problem is solved proposed substituted aromatic inorganic salts thiocarbonic acid of General formula (1)

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in which R1is hydrogen or halogen:

R2group - A1- A2where

A1means of simple communication, collagen, alkyl with 1-4 carbon atoms, unsubstituted or substituted with halogen, alkoxygroup with 1-4 carbon atoms or alkoxyalkyl with 1-4 carbon atoms in each CNS part, quinil with 3 or 4 carbon atoms, alkylsulfonyl with 1 to 6 carbon atoms in the alkyl part,

Z is a heterocyclic radical of the formula

< / BR>
< / BR>
where Q denotes a carbonyl, thiocarbonyl or group C-N(R52where R5means alkyl with 1-4 carbon atoms, R3is hydrogen, halogen, alkyl with 1-4 carbon atoms, unsubstituted or substituted with halogen, cycloalkyl with 3-6 carbon atoms, a R4- amino, alkyl with 1-4 carbon atoms or alkylamino with 1-4 carbon atoms in the alkyl part, or two adjacent groups R3and R3or R3and R4together mean alcander with the number of carbon atoms up to 5, unsubstituted or substituted by alkyl with 1-4 carbon atoms.

Preferred are compounds of General formula (I), in which

R1is hydrogen, fluorine, chlorine or bromine;

R2group of the formula-A1-A2,

where A1means of a simple bond, oxygen or the group-N-A3where A3means hydrogen, methyl, ethyl, n - or isopropyl; A2is hydrogen, fluorine, tor.- or tert.-butyl;

Z is a heterocyclic radical of the formula

< / BR>
where Q denotes a carbonyl or thiocarbonyl, R3is hydrogen, chlorine, fluorine, bromine, methyl, ethyl and isopropyl, unsubstituted or substituted by fluorine, cyclopropyl, a R4-amino, methyl, ethyl, isopropyl, or two adjacent groups R3and R3or R3and R4together signify unsubstituted alcander with the number of carbon atoms up to 5.

New substituted aromatic amides thiocarbonic acid of General formula (I) belonging to the category of low-toxic substances can get that substituted aromatic NITRILES of General formula (II):

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in which R1, R2and Z have the above values, enter into interaction with hydrogen sulfide or thioacetamide, optionally in the presence of an auxiliary for the reaction means and in the presence of a diluent.

If used, for example, 2-(2-fluoro-4-cyano-5-methoxyphenyl)- 4-methyl-5-deformity-2,4-dihydro-3H-1,2,4-triazole-3-one and hydrogen as starting substances, the course of the reaction can be represented by the following scheme:

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Educt of the formula (II) are known and/or can be obtained according to known methods.

As diluents Primaticcio, possibly halogenated hydrocarbons, such as benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; ethers like diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or etilenglikolevye or etilenglikolevye simple ether; ketones, such as acetone, butanone or methyl isobutyl ketone: NITRILES like acetonitrile, propionitrile or benzonitrile; amides like N,N - dimethylformamide, N,N-dimethyl-ndimethylacetamide, N-methylformamide, N is an organic or triamide hexamethylphosphoric acid; esters as methyl acetate or ethyl acetate: sulfoxidov as dimethyl sulfoxide; azine as pyridine; alcohols as methanol, ethanol, n - or isopropanol; etilenglikolevye simple ether; etilenglikolevye simple ether; diethylethylenediamine simple ether; diethylethylenediamine simple ether; mixtures thereof with water or pure water.

The reaction is carried out preferably in the presence of a suitable helper for the reaction means. As such funds apply any inorganic or organic bases. These include, for example, hydrides, hydroxides, amides, alcoh the Tria, amide sodium, sodium methylate, sodium ethylate, tert.-butyl potassium, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate or ammonium carbonate, and basic organic nitrogen-containing compounds, as trimethylamine, triethylamine, tributylamine, N,N - dimethylaniline, pyridine, N-methylpiperidine, N,N-dimethylaminopyridine, diazabicyclo, Diisobutylene or databaseconnect.

The reaction temperature may vary within wide limits. In General operate at temperatures from 0oC to 100oC, preferably at temperatures between 10oC to 80oC and under atmospheric pressure.

However, it is also possible to work at elevated or reduced pressure, in General between 0.1 bar and 10 bar.

The new compounds of General formula (I) possess herbicide activity, so that they can represent the active substance contained in an effective amount in the herbicide agent, which is an additional object of the invention.

The proposed herbicide means may be in the form of any standard of drug, such as, nye powders, the granules, suspension-emulsion concentrates, impregnated with active ingredient of natural and synthetic substances, as well as microencapsulation in polymeric substances.

The drugs are prepared in a known manner, for example by mixing the active substances with solvents, that is liquid solvents and/or solid carriers, can be achieved by using surface-active agents, that is emulsifiers and/or dispersants and/or foam-forming means. In the case of using water as a diluent can be used, for example, organic solvents as auxiliary dissolving means. As liquid solvents used mainly aromatic hydrocarbons, such as xylene, toluene or alkylnaphthalenes; chlorinated aromatic hydrocarbons and chlorinated aliphatic hydrocarbons, such as chlorobenzene, chloroethylene or methylene chloride; aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and also their ethers and esters; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; strongly polar is th used, for example, ammonium salts and natural stone flour as kaolin, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic rock flours, such as highly dispersed silicic acid, alumina and silicates, as solid carriers for granules are used, for example, crushed and fractionated rocks as calcite, marble, pumice, thick, dolomite, and also synthetic granules of inorganic and organic flour, granules of organic material such as sawdust, coconut shell, corn cobs and stalks of the tobacco plants: as emulsifiers and/or foam-forming means is used, for example, nonionic and anionic emulsifiers, such as complex polyoxyethylene esters of fatty acids, simple polyoxyethylene ethers of fatty alcohols, for example, alkyldiphenylamine ethers, alkyl sulphonates, alkyl sulphates, arylsulfonate, and also protein hydrolysates; as a dispersant is used, for example, used ligninsulfonate liquors and methylcellulose.

The preparations may also contain adhesives, as carboxymethylcellulose, natural and synthetic powder, granular the haunted phospholipids, as Catalina and lecithins, and synthetic phospholipids. Other target additives can be mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyanide blue, and organic dyestuffs, such as alizarin dyes, azo dyes and metal-phthalocyanine dyes, and trace elements such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

Preparations include the total of 0.1 to 95 wt.% the active substance, preferably 0.5 to 90 wt. %.

The proposed tool can be applied both before and after emergence of the plants. It can also be incorporated into the soil before sowing. The tool used in concentrated or diluted form.

The used quantity of active substances may vary within wide limits. It depends essentially on the desired effect. In General, consumption rates range from 10 g to 10 kg of active substance per hectare of soil surface, preferably from 50 g to 5 kg per hectare.

Obtaining new compounds of the formula (I) is illustrated by the following examples:

Example 1

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In a mixture of 5.5 g (15 mmol) of 2-(4-cyano-2-fluoro-5 - atilanoC - 60oC enter the sulfide to saturation and the mixture is stirred for 30 min at 60oC. the mixture is Then concentrated in vacuo, the residue is stirred with 2 N. hydrochloric acid and filtered.

The solid product is recrystallized from isopropanol.

Obtain 4.8 g (80% of theory) of 2-(2-fluoro-5 - ethylsulfonyl-4-thiocarbamoyl)-5,6,7,8-tetrahydro - 1,2,4-triazolo [4,3-a] pyridine-3 (2H)-one with a melting point 220oC.

Example 2

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6.3 g (0.02 mol) of 2-(2-fluoro-4-cyano-5-AMINOPHENYL)-4-ethyl-5 - Cryptor-methyl-2,4-dihydro-3H-1,2,4-triazole-3-one in 100 ml of acetone is mixed with Android 4.04 g (0.04 mol) of triethylamine. At the 23oC now continuously introducing hydrogen sulfide, and the internal temperature rises up to the 33oC. After one hour the reaction was completed. The solution is concentrated on a rotary evaporator and the residue will recrystallized from isopropanol.

Obtain 2.9 g (42% of theory) of 2-(2-fluoro-4-thiocarbamoyl-5 - AMINOPHENYL)-4-ethyl-5-trifluoromethyl-2,4-dihydro-3H-1,2,4-triazole-3 - one with a melting point of 161oC.

Example 3

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11 g (0,0276 mol) of 2-(2-fluoro-4-cyano-5 - metilsulfonilmetane)-4-methyl-5-deformity-2,4-dihydro-3H - 1,2,4-triazole-3-thione in 100 ml of pyridine at wle, the residue is stirred with water, acidified with concentrated hydrochloric acid, precipitated precipitated product is filtered off, washed with water and recrystallized from isopropanol. Get 9 g (77% of theory) of 2-(2-fluoro-4 - thiocarbamoyl-5-ethylsulfonyl-AMINOPHENYL)-4-methyl-5-deformity - 2,4-dihydro-3H-1,2,4-tri-azole-3-thione with a melting point 183oC.

Analogously to examples 1, 2 and 3, and accordingly the above data by conducting the reaction can also get listed in table 1, the compounds of formula (I).

Getting the source compounds of the formula (II) is illustrated by the following examples.

An example of a

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To 6.3 g (0,034 mol) of 4-methyl-3-trifluoromethyl-1,2,4 - triazoline-5-it, and 5.4 g (0,034 mol) of 2,4,5-tripersonal in 150 ml of dimethyl sulfoxide at room temperature is added 5.8 g (0,042 mol) of potassium carbonate and then heated for 14 h at 100oC. processing the cooled reaction mixture is bring in water with diluted hydrochloric acid to establish a pH value equal to 2, and repeatedly extracted with dichloromethane. The combined organic phases are dried over sodium sulfate and concentrated in vacuo. The remainder chromatographic through silicagel (solvent: dichloro the melting point 74oC.

Example B

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To 1.52 g (0,005 mol) of 1-(4-cyano-2,5-differenl)-4-methyl-3 - Cryptor-methyl-1,2,4-triazoline-5-she 0,48 g (0,005 mol) amide, metasolv-acid in 50 ml of dimethyl sulfoxide at room temperature add 0,83 g (0,006 mol) of potassium carbonate and then heated for 12 h at 120oC. processing the cooled reaction mixture is bring in water with diluted hydrochloric acid to establish a pH value equal to 2, and repeatedly extracted with dichloromethane. The combined organic phases are dried over sodium sulfate and concentrated in vacuo. The remainder chromatographic through silica gel (solvent: a mixture of dichloromethane with methanol in a ratio of 20:1).

Obtain 0.55 g (28 % of theory) of 1-(4-cyano-2-fluoro-5 - methylsulphonyl-AMINOPHENYL)-4-methyl-3-trifluoromethyl-1,2,4 - triazoline-5-one with a melting point 67oC.

The example IN

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1.8 g (10 mmol) of Ethyl ester of 3-amino-4,4,4 - trifurcating acids contribute in 30 ml of dimethylformamide and 2 ml of toluene and at 0 - 5oC is mixed with 0.3 g (10 mmol) of 80% sodium hydride. The mixture is stirred for 30 minutes at a temperature of 0 to 5oC. After cooling the mixture to a temperature of 70oC there was added a solution of 0.9 g (5 mmol) 4-cyano-2,5-d is UP>oC. After removal of the cooling bath add 2 ml of acetic acid. Then the reaction mixture is diluted with water to about twice the volume and extracted with ethyl acetate. The organic phase is concentrated and the residue is brought to crystallization with diisopropyl ether.

Obtain 1.1 g (69 % of theory) of 1-(4-cyano-2,5-differenl)- 3,6-di-hydro-2,6-dioxo-4-trifluoromethyl-1-(2H)-pyrimidine with a melting point of 194oC.

Example D

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The mixture of 0.83 g (3 mmol) of 1-(4-cyano-2,5-differenl)-3,6 - dihydro-2,6-dioxo-3,4-dimethyl-1(2H)-pyrimidine, 0.32 g (3 mmol) of methanesulfonamide, 0.6 g of potassium carbonate and 10 ml of dimethyl sulfoxide is heated for 10 h at 120oC. After cooling, the mixture was poured into ice water and acidified with 2 N. hydrochloric acid. Then extracted with ethyl acetate, the organic phase is washed with water, dried over sodium sulfate and filtered. From the filtrate carefully the solvent is distilled off in a water jet vacuum pump.

Obtain 0.8 g (76 % of theory) of 1-(4-cyano-2-fluoro-5 - methylsulphonyl-AMINOPHENYL)-3,6-dihydro-2,6-dioxo-3,4-dimethyl - 1(2H)-pyrimidine in the form of a crystalline residue of melting point above 250oC).

Activity proposed means of paanga substances mixed with 5 wt. including solvent, was added 1 wt. including alkylarylsulphonates simple ether as an emulsifier and the concentrate is diluted with water to the desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 h, poured preparative form of the active substance. The quantity of water per unit surface area would be maintained as a constant. The concentration of active substance in workplace drug does not play any role, decisive is only the consumption rate of the active substance per unit surface area. Three weeks later assess the degree of damage to the plants in% damage in comparison with the development of the untreated control plants.

If this

0% means no effect (as untreated control)

100% means complete destruction

The conditions and results are summarized in tables 2, 3.

Experience II

Post-harvest treatment in the greenhouse

1 wt. including the active substance is mixed with 5 wt. including solvent, was added 1 wt. including alkylarylsulphonates simple ether as an emulsifier and the concentrate is diluted with water to the desired concentration.

Received the active drug substance sprayed those whom esta active substances. Three weeks later assess the degree of damage to the plants in% damage in comparison with the development of the untreated control plants. If this

0% means no effect (as untreated control)

100 % means complete destruction

The conditions and results of the experiment are summarized in table 4.

Experience III

Pre-emergence treatment in the greenhouse

1 wt. including the active substance is mixed with 5 wt. including solvent, was added 1 wt. including alkylarylsulphonates simple ether as an emulsifier and the concentrate is diluted with water to the desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 h, poured preparative form of the active substance. The quantity of water per unit surface area would be maintained as a constant. The concentration of active substance in workplace drug does not play any role, decisive is only the consumption rate of the active substance per unit surface area. Three weeks later assess the degree of damage to the plants in% damage in comparison with the development of the untreated control plants.

If this

0% means no effect (as untreated control)

100% one aromatic amides thiocarbonic acid of General formula I

< / BR>
in which R1is hydrogen or halogen;

R2group-A1-A2,

A1means of a simple bond, oxygen or the group-A3where A3denotes hydrogen, alkyl with 1 to 4 carbon atoms, and A2hydrogen, halogen, alkyl with 1 to 4 carbon atoms, unsubstituted or substituted with halogen, alkoxygroup with 1 to 4 carbon atoms or alkoxyalkyl with 1 to 4 carbon atoms in each CNS part, quinil with 3 or 4 carbon atoms, alkylsulfonyl with 1 to 6 carbon atoms in the alkyl part,

Z is a heterocyclic radical of the formula

< / BR>
< / BR>
< / BR>
where Q denotes a carbonyl or thiocarbonyl;

Q1- group C-N(R5)2where R5means alkyl with 1 to 4 carbon atoms;

R3is hydrogen, halogen, alkyl with 1 to 4 carbon atoms, unsubstituted or substituted with halogen, cycloalkyl with 3 to 6 carbon atoms;

R4- amino, alkyl with 1 to 4 carbon atoms or alkylamino with 1 to 4 carbon atoms in the alkyl part, or two adjacent groups R3and R3or R3and R4together mean alcander with the number of carbon atoms up to 5, unsubstituted or substituted by alkyl with 1 to 4 carbon atoms.

2. Substituted aromaticheski the formulas-A1-A2where A1means of a simple bond, oxygen or the group-A3where A3means hydrogen, methyl, ethyl, n - or isopropyl; A2hydrogen, fluorine, chlorine, bromine; unsubstituted or substituted by fluorine, chlorine, methoxy group methyl, ethyl, n - or ISO-propyl, n-, ISO-, sec.- or tert-butyl; Z is a heterocyclic radical of the formula

< / BR>
< / BR>
< / BR>
where Q denotes a carbonyl or thiocarbonyl;

R3is hydrogen, chlorine, fluorine, bromine, methyl, ethyl and isopropyl, unsubstituted or substituted by fluorine, cyclopropyl;

R4- amino, methyl, ethyl, isopropyl or two adjacent groups R3and R3or R3and R4together signify unsubstituted alcander with the number of carbon atoms up to 5.

3. Herbicide remedy containing the active substance derived thiocarbonic acid and the target additives, characterized in that as derived thiocarbonic acid it contains a compound of General formula I

< / BR>
where R1is hydrogen or halogen;

R2- group A1-A2where A1means of a simple bond, oxygen, or the group-N-A3where A3denotes hydrogen, alkyl with 1 to 4 carbon atoms, and A2is hydrogen, halogen, alkyl with 1 to 4 atoms what uppoi 1 4 carbon atoms in each CNS part, quinil with 3 or 4 carbon atoms, alkylsulfonyl with 1 to 6 carbon atoms in the alkyl part;

Z is a heterocyclic radical of the formula

< / BR>
< / BR>
< / BR>
where Q denotes a carbonyl or thiocarbonyl;

Q1- group C-N(R5)2where R5means alkyl with 1 to 4 carbon atoms;

R3is hydrogen, halogen, alkyl with 1 to 4 carbon atoms, unsubstituted or substituted with halogen, cycloalkyl with 3 to 6 carbon atoms;

R4- amino, alkyl with 1 to 4 carbon atoms or alkylamino with 1 to 4 carbon atoms in the alkyl part, or two adjacent groups R3and R3or R3and R4together mean alcander with the number of carbon atoms up to 5, unsubstituted or substituted by alkyl with 1 to 4 carbon atoms,

in an effective amount.

Priority signs:

04.05.94 - R1- specified in the claims value; R2- specified in the claims values; Z - specified in the claims value; Q is specified in the claims value; R3- specified in the claims value; R4- specified in the claims values; two adjacent groups R3and R3or R 10.01.95 two adjacent groups R3and R3or R3and R4together mean alcander with the number of carbon atoms up to 4, substituted by alkyl with 1 to 4 carbon atoms, and alcander 5 carbon atoms, unsubstituted or substituted by alkyl with 1 to 4 carbon atoms.

 

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< / BR>
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