DD260645A5 - HERBICIDAL COMPOSITION - Google Patents

Abstract

The invention includes a herbicidal composition. According to the invention, as active ingredient in the novel herbicidal compositions certain triazolesulphonamides of the formula (I) are used and their salts, wherein, for example: Ra is hydrogen and Rb is a group R3CONHCR2CR1 or Ra and Rb together represent a chain having the formula C (R3) NC (R 2) C (R 1) or C (Y) N (R 6) C (R 2) C (R 1), wherein R 1, R 2 and R 3, which may be the same or different, are each hydrogen, hydroxy, mercapto, halo -, cyano, amino, alkylamino, dialkylamino or a substituted or unsubstituted alkyl, aryl, aralkyl, alkoxy or alkylthio group, Y is oxygen or sulfur and R6 is hydrogen or a substituted or unsubstituted alkyl or aryl group u. a. Formula (I)

Description

- 2 - ZbU b4Ö Field of application of the invention

The invention relates to a herbicidal composition containing new Triazolsulfonamiden and process for preparing these compounds.

Characteristic of the known state of the art

There is no information available which compounds have hitherto been used as active ingredient in herbicidal compositions.

Object of the invention

The aim of the invention is to provide novel compositions having a strong herbicidal action and good compatibility with crops which are suitable for selective weed control in crops of useful plants.

Explanation of the essence of the invention

The invention has for its object to find new compounds which are suitable as active ingredient in herbicidal compositions having the desired properties.

According to the invention, as active ingredient in the novel herbicidal compositions, triazolesulphonamides of the formula:

^ N N

R ^b

and salts thereof wherein R ^{a is} hydrogen and R ^{b is} a group R ³ CONHCR ² = CR ¹ - or R ^a and R ^b together represent a chain of the formula -C (R ³ I = NC (R ² ) = C (R ¹ ) - or -C (= Y) -N (R ⁶ ) -C (R ² ) = C (R ¹ ) -, wherein R ¹ , R ² and R ³ , which may be the same or different, each represents hydrogen, a hydroxy, mercapto, halo, cyano, amino, alkylamino, dialkylamino or substituted or unsubstituted alkyl, aryl, aralkyl, alkoxy or alkylthio group, Y is oxygen or sulfur, R ^{6 is} hydrogen or represents a substituted or unsubstituted alkyl or aryl group, or R ¹ and R ² together represent -CH = CH-CH = CH- or- (CH ₂ ) _n , where η is equal to 3,4 or 5; R ^{4 is} substituted phenyl or represents a substituted or unsubstituted aralkyl or heteroaryl group and R ^{5 is} hydrogen, acyl, carboxy group, alkoxycarbonyl, alkylsulfonyl or a substituted or unsubstituted alkyl, alkenyl, alkynyl , Aryl or aralkyl group or a group represented by the formula:

wherein R ^a and R ^{b are} as defined above.

R ^a and R ^b together preferably represent a chain of the formula -C (R ³ I = NC (R ² I = C (R ¹ ) -.

When R ¹ , R ² or R ^{3 represents} a halo group, it is preferably a chloro or bromo group.

When R ¹ , R ² , R ³ , R ⁵ or R ⁶ represent or contain an alkyl group, this group preferably has 1 to 6 carbon atoms, especially 1 to 4 carbon atoms. Specific, preferred, unsubstituted, alkyl-containing groups include methyl, ethyl, n -propyl, isopropyl, η-butyl, t-butyl, methoxy, ethoxy, n-propoxy, methylamino, dimethylamino, methylthio, ethylthio , The alkyl group may, if desired, be substituted, for example by one or more halogen atoms, e.g. As fluorine, chlorine or bromine, or by alkoxy groups having 1 to 4 carbon atoms, ζ. Β. Methoxy or ethoxy groups. Specific, preferred, substituted, alkyl-containing groups include chloromethyl, bromomethyl, dichloromethyl, trifluoromethyl, methoxyethyl and ethoxyethyl.

When R ¹ , R ² , R ³ , R ⁵ or R ^{6 represent} an aryl or aralkyl group, it is preferably a phenyl group or an aralkyl group having 7 to 10 carbon atoms, especially benzyl substituted by, for example, one or more halogen atoms, e.g. As fluorine, chlorine or bromine, nitro groups, cyano groups or alkyl or alkoxy groups having 1 to 4 carbon atoms, ζ. Β. Methyl, ethyl, methoxy or ethoxy groups.

R ¹ , R ² and R ³ independently of one another preferably represent hydrogen, methyl, ethyl, phenyl, trifluoromethyl, chloro or bromo.

It can be seen that when R ^{3 is} a hydroxy or mercapto group, the compounds may be present in either of the two keto or enol forms or as an equilibrium mixture of both.

When R ⁴ or R ^{5 is} an aralkyl group, it is preferably benzyl which may be substituted by one or more alkyl or alkoxy groups having 1 to 4 carbon atoms, halogen atoms or nitro groups.

When R ^{4 is a} heteroaryl group, it is preferably a five- or six-membered heterocyclic compound containing one or more nitrogen, oxygen or sulfur atoms. Preferred of these groups include pyridyl, pyrrolyl, furyl and thienyl.

R ⁴ preferably represents a phenyl group substituted by one or more halogen atoms (e.g., chlorine, bromine or fluorine atoms), alkyl groups of 1 to 4 carbon atoms (eg, methyl or ethyl), alkoxy or alkylthio groups of 1 to 4 carbon atoms (eg methoxy, ethoxy or methylthio groups), trifluoromethyl groups, alkoxycarbonyl groups having from 2 to 5 carbon atoms (eg methoxy carbonyl or ethoxy carbonyl) or nitro groups.

When R ^{5 is an} alkyl group, it is preferably methyl or ethyl; however, when it is an alkenyl or alkynal group, this group is preferably unsubstituted and preferably has 2 to 6 carbon atoms, for example vinyl, allyl or propargyl. Preferred acyl, alkoxycarbonyl and alkylsulfonyl groups which may be represented by R ⁵ are those in which the alkyl moiety has from 1 to 4 carbon atoms, including formyl, acetyl, propanoyl, methoxycarbonyl, ethoxycarbonyl and methylsulfonyl.

R ⁵ is preferably hydrogen.

Preferred salts of compounds of formula I are alkali metal salts, e.g. B! Sodium or potassium salts, ammonium salts, trialkylammonium salts and salts with heterocyclic bases, e.g. B. pyridinium salts.

In a particularly preferred group of compounds of the formula I, R ^a and R ^b together represent a chain having the formula -C (R ³ ) = NC (R ² ) = C (R ¹ ) -, wherein R ¹ , R ² and R ³ each represents hydrogen, methyl, ethyl, phenyl, trifluoromethyl or a chloro group, R ^{4 is} a phenyl group substituted by one or more halogen atoms, alkyl, alkoxy or alkylthio groups having 1 to 4 carbon atoms, trifluoromethyl groups, alkoxy carbonyl groups having 2 to 5 carbon atoms or nitro groups and R ⁵ is hydrogen.

Particularly preferred compounds according to the invention are those mentioned in the examples below.

Specifically, however, N- (2,6-difluorophenyl) -5,7-dimethyl [1,2,4] triazolo [1,5-c] pyrimidine-2-sulfonamide and 5- (2-acetamido-1 propenyl) -N- (2,6-difluorophenyl) -1H-1,2,4-triazole-3-sulfonamide.

In another aspect, the invention provides a process for the preparation of a triazolesulfonamide of the formula I, wherein R ^a and R ^b together represent a chain of the formula -C (R ³ I = NC (R ² I = C (R ¹ ) - or -C (= Y) -N (R ⁶ ) -C (R ² ) = C (R ¹ ) -, wherein R ¹ , R ² , R ³ , R ⁶ and Y are as defined above, according to which a sulfonyl halide having the formula:

wherein R ^a and R ^{b are} as defined above and Hal is halo in the presence of a base with an amine of the formula

R ⁴ R ⁵ NH is reacted, wherein R ⁴ and R ^{5 are} as defined above to give the desired compound. '

The reaction is advantageously carried out at a temperature between 0 ° and 100 ⁰ C, for example between 0 ° and 50 ° C, especially at room temperature. It is preferably carried out in a suitable solvent, in particular pyridine, which can also serve as base.

The reaction can be catalyzed by a stronger base, especially a tertiary organic base such as 4-dimethylaminopyridine.

The compounds of formula II, in turn, can be prepared by reaction of a compound of the formula:

(IN THE)

- SR

wherein R ^a and R ^b together represent a chain having the formula -C (R ³ ) = NC (R ² ) = C (R ¹ ) - or-C (= Y) -N (R ^e ) -C (R ² ) = C (R ¹ ) -, wherein R ¹ , R ² , R ³ , R ⁶ and Y are as defined above and R represents hydrogen, alkyl, aryl or aralkyl, with the appropriate halogen or sulfuryl halide in a suitable solvent to give the desired compound.

The reaction is preferably carried out with cooling to less than room temperature, e.g. B. a temperature of -10 ° to

When working with a halogen, it is preferably dissolved in a solution or suspension of the appropriate starting material in an aqueous medium, e.g. As aqueous acetic acid or hydrochloric acid, initiated.

When working with a sulfuryl halide, the reaction is preferably carried out in the presence of wet silica gel and in a suitable solvent, e.g. For example, dichloromethane.

The compounds of formula I wherein R ^{a is} hydrogen and R ^b is R ³ CONHCR ² = CR ¹ - can be prepared by a process consisting in reacting the corresponding compounds of formula I wherein R ^a and R ^b together-C (R ³ J = NC (R ² J = C (R ¹ ) -represent the action of a base under mild conditions to produce the desired compound.

The base is desirably an inorganic base, preferably an alkali metal hydroxide, e.g. As sodium or potassium hydroxide, and it is advantageously used in an aqueous solution.

The reaction is advantageously carried out at a temperature of 0 ° to 50 ⁰ C, preferably at room temperature. At higher temperatures or under tougher conditions, the reaction goes one step further than described herein. The compounds of the formula I in which R ^a and R ^b together represent a chain -C (R ³ ) = NC (R ² ) = C (R ¹ ) -, in which R ^{3 has} a meaning other than hydroxy, mercapto or amino group, may alternatively be prepared by a process in which a compound having the formula:

(IV)

R ² COCHR ^{1 H} "SO ₂ NR ⁴ R ⁵

wherein R ¹ , R ² , R ⁴ and R ^{5 are} as defined above, is reacted with an amide of the formula R ³ CONH ₂ wherein R ^{3 is} as defined above to give the desired compound.

The reaction is advantageously carried out by heating the mixture of the reactants, e.g. B. to 50 ° to 200 ⁰ C performed.

The compounds of formula I wherein R ^a and R ^b together represent a chain -C (R ³ ) = NC (R ² ) = C (R ¹ ) - wherein R ^{3 is} a hydroxy, mercapto or amino group , can be prepared by reacting a compound of formula IV, as defined above, with urea, thiourea or guanidine to give the desired compound.

The reaction is advantageously carried out by heating a mixture of the reactants, e.g. B. to 50 ° to 200 ⁰ C, executed.

In turn, the compounds of formula IV may be prepared by a process wherein a compound of formula I in which R ^{a is} hydrogen and R ^{b is} a group R ³ CONHCR ² = CR ¹ -, the action of a suitable base under suitable conditions Exposed to conditions to give the desired compound.

The base used is advantageously an alkali metal base, for. Example, an alkali metal hydroxide, and the reaction is advantageously in a suitable solvent, for. As water, and carried out with heating to a temperature of 60 ° to 100 ° C.

The compounds of formula III in which R ^a and R ^b together represent a chain having the formula -CI = Y) -N (R ⁶ JC (R ² J = C (R ¹ K wherein Y, R ¹ , R ² and R ^{6 are} as defined above, are themselves novel compounds which can be prepared from the corresponding compounds in which R ^{a is} hydrogen and R ^{b is} a group R ² COCHR ¹ -, by their reaction with an isocyanate or an isothiocyanate with the Formula R ⁶ NCY, wherein R ⁶ and Y are as defined above.

These starting materials in turn can be prepared by reaction of thiosemicarbazide with a compound having the formula:

/ - \

wherein R ¹ and R ^{2 are} as defined above, which product, if desired, can be reacted with a compound of the formula RHAII in which R is as defined above, and the protecting group can be removed by acid.

Salts of compounds of formula I may be prepared by their reaction with a suitable base containing the desired cation, e.g. B. the corresponding trialkylamine.

The compounds of the formula I can also be interchanged with one another by the known methods.

For example, the compounds of formula I in which R ^{B is} not hydrogen may be prepared from the corresponding compounds of formula I in which R ^{5 is} hydrogen by their reaction in the presence of a strong base, for example sodium hydride, with a HaMd with the formula R ⁵ shark.

Carboxy groups present in the compounds of formula I may be esterified, existing ester groups may be hydrolyzed to give the corresponding acids, and cyano or ester groups may be converted to amido or substituted amido groups. These conversions, like many others, can be carried out by methods well known to those skilled in the art, and various examples of such conversions are given below. Particular mention should be made of the conversion of compounds of the formula I in which R ² or R ^{3 is} a hydroxy group into the corresponding compounds in which R ^{3 is} a chloro group by the reaction of the former with phosphorus oxychloride and the subsequent reaction of the chloro compounds in the presence of a base with a corresponding alcohol, alkanethiol, amine or cyanide to give the corresponding compounds of formula I in which R ^{3 represents} an alkoxy, alkylthio, amino or cyano group.

The compounds of formula I are herbicidally active against a broad range of broadleaf and grassy weeds, comparatively safe, however, to certain crop species. They are therefore useful as selective herbicides, especially in the control of a wide range of weeds in cereals or other crop plants, e.g. Wheat, barley, corn, soybeans, oilseed rape, cotton or sugar beet.

In particular, the invention provides a herbicidal composition consisting of one or more compounds of the invention in association with a suitable carrier and / or surface active agent.

The compositions typically contain from 0.01% to 99% by weight of the instant compounds and are normally prepared initially as concentrates containing from 0.5 to 99% by weight, preferably between 0.5 and 85% by weight, and especially between 10 and 50 wt .-% of the compounds. These concentrates are diluted, if necessary, to the site to be treated prior to application so that the active ingredient is between 0.01 and 5% by weight of the applied composite.

The carrier may be water, in which case an organic solvent may also be present, but this is not usually used. A flowable suspension concentrate may be prepared by grinding the compound with water, a wetting agent and a suspending agent, e.g. Xanthan gum.

Alternatively, the carrier may be a water-immiscible organic solvent, e.g. A hydrocarbon boiling at 120 ° -270 ° C, e.g. B. xylene, in which the compound is dissolved or brought to suspension. An emulsifiable concentrate containing a water-immiscible solvent can be prepared with a surfactant so that the concentrate acts as a self-emulsifiable oil in admixture with water.

Alternatively, the carrier may be a water-miscible organic solvent, e.g. For example, 2-methoxyethanol, methanol, propylene glycol, diethylene glycol, diethylene glycol monoethyl ether, methyl formamide or dimethylformamide.

Alternatively, the carrier may be a solid which may be finely divided or granulated. Examples of suitable solid materials are lime sandstone, clays, sand, mica, chalk, attapulgite, diatomite, perlite, sepiolite, silicas, silicates, lignosulfonates and solid fertilizers. The carrier may be of natural or synthetic origin, or it may be a modified natural material.

Wettable powders which are soluble or dispersible in water may be prepared by incorporating the compound in particulate form into a particulate carrier or by spraying the molten compound onto the particulate carrier, admixing a wetting agent and a dispersible, and finely grinding the entire powder mixture getting produced.

An aerosol composition can be prepared by mixing the compound with a propellant, e.g. a polyhalogenated alkane, such as dichlorofluoromethane, and possibly also with a solvent.

The term "surfactant" is used broadly herein and also includes substances which are variously referred to as emulsifiers, dispersants and wetting agents Such agents are well known in the art.

The surfactants used may be anionic surfactants, for example mono- or diesters of phosphoric acid with fatty alcohol ethoxylate, or salts of such esters, fatty alcohol sulfates such as sodium dodecyl sulfate, ethoxylated fatty alcohol sulfates, ethoxylated alkylphenol sulfates, lignin sulfates, petroleum sulfates, alkylaryl sulfonates such as alkyl benzene sulfonates or lower alkyl naphthalene sulfonates, salts of sulfonated naphthalene formaldehyde condensates , Salts of sulfonated phenol-formaldehyde condensates or more complex sulfonates such as the amide sulfonates, e.g. Example, the sulfonated condensation product of oleic acid and N-methyl taurine, or the Dialkylsulfosukzinate, z. For example, the sodium sulfonate of dioctyl succinate.

The surfactants may also be nonionic agents, for example, condensation products or fatty acid esters, fatty alcohols, fatty acid or alkyl-substituted phenols with ethylene oxide, fatty esters of polyhydric alcohol ethers, e.g. B. sorbitan fatty acid esters, condensation products of such esters with ethylene oxide, for. B.

Polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, acetylene glycols such as 2,4,7,9-tetramethyl-5-decyn-4,7-diol or ethoxylated acetylene glycols.

The surfactants may also be cationic agents, for example alkyl- and / or aryl-substituted quaternary ammonium compounds such as zetyrtrimethylammonium bromide or ethoxylated tertiary fatty amines.

Preferred surfactants include ethoxylated fatty alcohol sulfates, lignosulfonates, alkylarylsulfonates, salts of sulfonated naphthalene-formaldehyde condensates, salts of sulfonated phenol-formaldehyde condensates, sodium oleoyl-N-methyltauride, dialkylsulfosuccinates, alkylphenolethoxylates and fatty alkylethoxylates.

The present active compounds, in particular those of the examples given below and in particular N- (2,6-difluorophenyl) -5,7-dimethyl [1,2,4] triazolo [1,5-c] pyrimidine-2-sulfonamide and 5- (2-Acetamido-1-propenyl) -N- (2,6-difluorophenyl) -1H-1,2,4-triazole-3-sulfonamide may be mixed with another herbicide, eg a herbicide, fungicide or pesticide and insecticide, or a plant growth regulator, but especially a different herbicide. Other suitable herbicides include trietazine, linuron, MCPA, dichlorprop, isoxaben, diflufenican, metochlor, fluometuron, oxyfluorfen, fomesafen, bentazone, prometryn, norflurazon, chlomazone, EPTC, imazaquin, and especially isoproturon, methabenzthiazuron, trifluralin, joxynil, bromoxynil, Benazoline, mecoprop, Fluorxypyr, Alachlor, Azifluorfen, Lactofen, Metribuzin and Pendimethalin.

The present compounds may be planted, the soil, land or water surfaces, and particularly applied to a site where a culture is to grow or grow. The connections are active both before and after the formation.

embodiment

The invention is illustrated by the following examples. The following abbreviations are used in the examples: Me = methyl, Et = ethyl, Ph = phenyl.

Example of the preparation A:

N- (2-chlorophenyl) -5,7-dimethyl [1,2,4] triazolo [1,5-c] pyrimidine-2-sulfonamide (Compound A)

a) 5,7-Dimethyl [1,2,4] triazolo [1,5-c] pyrimidine-2-sulfonyl chloride

Chlorine gas was added to a suspension of 5,7-dimethyl [1,2,4] triazolo [1,5-c] pyrimidine-2-thiol (5.4g) in water (50ml) at a temperature of 5 ° C 1O ⁰ C over 30 minutes with vigorous stirring. The solid was filtered off and dissolved in dichloromethane (80 ml). The organic solution was washed with water (10 ml), dried over magnesium sulfate and concentrated in vacuo to give a yellow, gummy solid, 2.7 g, which was shown by spectroscopy to be the desired product.

(b) N- (2-Chloro-phenyl) -5,7-dimethyl-1,2,4-triazolo-1,5-c-pyrimidine-2-sulfonamide A solution of sulfonyl chloride (2.7g) in dichloromethane (10ml) was added at 10 ° Slowly add C-15 ° C to a stirred solution of 2-chloroaniline (1.54 g) in pyridine (20 ml). The temperature was kept below 15 ° C. Upon completion of the addition, the mixture was allowed to return to ambient temperature and stirred overnight. It was then concentrated in vacuo and to the residue was added 5% hydrochloric acid (15 ml) and ether (10 ml). The resulting solid was filtered and subjected to flash chromatography on silica gel using petroleum ether (b.p. 60 ° C-80 ° C) / ethyl acetate in the ratio of 1: 1 as eluent. The desired sulfonamide was obtained as a creamy solid, mp 19O ⁰ C to 192 ° C, in 1 g yield. Examples A2 to A49:

The following compounds of the formula I in which R ^{5 is} hydrogen were prepared by analogous methods to those of Example A:

No. R ¹ R ^ R ³ R ⁴ (Ph substituted :) Melting point ( ⁰ C) A2 , H me me 2,6-Dici 279-282 A3 H me me 2-Cl, 6-Me 238-239 A4 H me me 2.6 -diF 229-231 A5 H me M3 2-NO ₂ 189-192 A6 H me me 2-CF ₃ 193-195 A7 H me me 2-COOMe 180-182 A8 H me me 2,6-di-Cl, 3-Me 242-244 A9 H me me 2,3-DICI 176-178 A10 me me me 2,6-Dici 241-243 A11 me me me 2-CI-6-Me 212-214 A12 Me. me me _T 2,6-diCl, 3-Me 232-234 A13 Cl me 'Me 2.6 -diF 214-216 A14 H me me 2-Cl, 6-F 253-255 A15 H me me 2-Me, 6-NO ₂ 248-250 A16 Cl me H 2.6 -diF 235-238 A17 H me - Ph 2.6 -diF 266-269 A18 H me me 2,3,5,6-tetra-F 236-239 A.19 H Ph me 2.6 -diF 269-275 A 20 H Ph me 2-Cl, 6-Me 272-275 A21 H me Ph 2-Cl, 6-Me 275-276 A 22 H CF ₃ me 2.6 -diF 165-167 A 23 me me me 2,6-di-F 220-223 A 24 H me me 2-CI, 6-SMe 233-235 A 25 H et me 2.6 -diF 190-192 A 26 H me OH 2.6 -diF > 350 A 27 H me me 2-Me, 6-COOMe 195-197 A 28 H me me 2.6 -diBr 276-278 A 29 H H me 2.6 -diF 203-205 A 30 br me H 2.6 -diF 219-221 A31 H me me 2,3-diMe, 6-NO ₂ 177-179 A 32 H H me 2,6-Dici 222-224 A 33 H me me 2-F, 6-COOMe 213-215 A34 H H me 2-Cl, 6-Me 218-219 A35 H me me 2,5-diMe, 6-COOMe 207-209 A 36 H me H 2.6 -diF 202-204 A 37 H me me 2-F, 6-COOEt 160-163 A 38 H me me 2-OCHF ₂ 160-162 A 39 H me me 2,3-diCl-6-NO ₂ 229-234 A 40 H me me 2-OMe 178-180 A 41 H me me 2-CN 235-236 A 42 H me me 3,5-DICI 267-269 A 43 H me me 2-SO ₂ NH ₂ 208-210 A44 H me me 2.6 -diMe "235-237 A45 H me me 2,5-diCOOMe 176-179 A 46 H me me 2,5-DICI 198-201

The following compound of the formula I was also prepared by a method analogous to that in Example A: No. R ¹ R ² R ³ R ⁴ (Ph.subst.) R ⁵ melting point ( ⁰ C)

me

me

2.6 -diF

me

168-170

The following compound of the formula I in which R ^{4 represents} 2-pyridyl was likewise prepared by a method analogous to that in Example A:

No. R ¹ R ² R ³ R ⁵ Melting point ( ⁰ C)

A48 H Me Me H 246-247

Examples A 49-A 52:

The following compounds of formula I in which R ^{5 represents} a group of formula A wherein R ¹ , R ² and R ^a are the same as the corresponding groups in the remainder of the molecule were prepared by methods analogous to those in the example A made:

No. R ¹ R ^ ^RJ R ⁴ (Ph substituted :) Melting point ( ⁰ C) A 49 H me me 2,6-Dici, 3-Me 278-282 A 50 H me me 2-Me, 6-NO ₂ 244-246 A51 H me me 2-F, 6-COOMe 255-257 A 52 H me me 2-F, 6-COOEt 259-261

Example of Preparation B: 5- (2-Acetamido-2-propenyl) -N- (2,6-difluorophenyl) -1H-1,2,4-triazole-3-sulfonamide (Compound B1) A solution of the product Example A4 (2.4 g) in 5% aqueous sodium hydroxide solution (20 ml) was stirred at room temperature for one and a half hours and allowed to stand for a further 18 hours. The solution was then acidified and adjusted to pH 2 with concentrated hydrochloric acid to precipitate a solid. This was distilled off, washed with water (2 x 10 ml) and ether (2 x 10 ml) to give 2.1 g of the desired product as a white solid, mp 226 ° C to 228 ° C

 Examples B 2-B 7:

The following compounds of formula I in which R ⁵ and R ^{a are} hydrogen and R ^{b is} a group R ³ CONHCR ² = CR ¹ - were prepared by methods analogous to those in Example B:

No. R ' R " ^RJ R * (Ph substituted :) Melting point ( ⁰ C) B2 H me me ' 2-Cl, 6-Me 234-236 B3 H CF ₃ me 2.6 -diF 141-145 B4 H me me 2-CI 162-164 B5 H me me 2,6-Dici, 3-Me 234-235 B6 H me me 2,6-Dici 282-283 B7 H me me 2-Me, 6-NO ₂ 242-245

Example of Preparation C: N- (2,6-Difluorophenyl) -5,6-dihydro-7-methyl-5-oxo [1,2,4] triazolo [1,5-c3pyrimidine-2-sulfonamide An aqueous solution The product from Example A4 (15 g) in 5% aqueous sodium hydroxide (25 ml) was heated at reflux for 4 hours. Then the solution was cooled and acidified with concentrated hydrochloric acid to a pH of 4 to precipitate a creamy solid. This was filtered and washed with water and ether to give 11g of N- (2,6-difluorophenyl) -5- (2-oxopropyl) -1H-1,2,4-triazole-3-sulfonamide, melting point 182 ⁰ C to 184 ⁰ C, yielded. An intimate mixture of the produced sulfonamide (2g) and urea (10 g) was stirred at 150 ^° C. for 3 hours, then the mixture was cooled to 70 ^° C. and water (40 ml) was added. The solution was acidified to pH 1 by the addition of concentrated hydrochloric acid to precipitate a solid which was removed by filtering. The solid was extracted with boiling acetonitrile, filtered hot and allowed to cool to give a solid precipitate. This was filtered and yielded 0.48 g of the desired product as a white solid, mp> 35O ⁰ C, which was identical to the product from Example 26th

Example of preparation D:

(a) 5- (2-Methyl-1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole-3-thiol

Ethyl (2-methyl-1,3-dioxolan-2-ylmethyl) acetate (43.5g) was added dropwise to a suspension of thiosemicarbazide (22.8g) in sodium ethoxide solution (6.04g sodium in 500ml absolute alcohol) at room temperature added. The suspension was heated at reflux for 18 hours. After cooling, the solid was removed by filtration and the filtrate was concentrated in vacuo. The oily residue was dissolved in water (60 ml), acidified to pH 5 with acetic acid and concentrated in vacuo. Trituration of the residue with propan-2-ol (50 mL) followed by filtration gave 11.6 g of the desired product, mp 168 ° C-173 °, as a white solid.

(b) 3-Benzylthio-5- (2-methyl-1,3-dioxolan-2-ylmethyl) -1H-1,2,4-triazole

Benzyl chloride (8.07g) was added dropwise at room temperature to a solution of the product of step (a) (11.6g) in sodium ethoxide solution (1.4g sodium in 100ml absolute alcohol) and the mixture was stirred for 18 hours. The precipitated solid was removed by filtration and the filtrate was concentrated in vacuo. The resulting oil was partitioned between water (60ml) and petroleum ether (b.p. 60 ° C-80 ° C) (50ml) and the solid was removed by filtration. This gave 13.9 g of the desired product, mp 96 ° C-98 ° C, as a white solid.

(c) 1- (5-Benzylthio-1H-1,2,4-triazol-3-yl) propan-2-one

A suspension of the product from step (b) (9.9g) in 1% hydrochloric acid (110ml) was heated at reflux for 30 minutes. The mixture was cooled and the solid was removed by filtration. This solid was identified as the desired product, 7.6 g, mp 125 ⁰ C to 127 ⁰ C.

Example of production E: N-acetyl-N- (2,6-difluorophenyl) -5,7-dimethyl [1,2,4] triazolo [1,5-c] pyrimidine-2-sulfonamide

The product from Example A4 (2g) was refluxed with acetic anhydride (12 ml) for 2 hours and the reaction was allowed to cool. The precipitated solid was precipitated by filtering to give 1.2 g of the desired product, mp 171 ° to 173 ° C.

Example of the production F: N-ethoxycarbonyl-N- (2,6-difluorophenyl) -5,7-dimethyl [1,2,4] triazolo [1,5-c] pyrimidine-2-sulfonamide

Ethyl chloroformate (1.3 g) was added dropwise to a suspension of the product of Example A4 (2.5g) in pyridine (13 ml) was added at 22 ⁰ C and the mixture was stirred at room temperature for 2 days. After filtering out the remaining solid, the filtrate was acidified with hydrochloric acid and the resulting solid was removed by filtering, with dilute ammonia (20ml), dried and recrystallized from ethyl acetate to give 1.9 g of the desired product, mp 155 ⁰ C to 157 ° C.

Examples of compositions:

A 10% suspension concentrate composition was prepared from the following ingredients:

component

g / i

Connection from example A4

PluronicP75

Polyphone H

propylene glycol

Foaming oppressor 1520

Veegum R

Kelzan

Formaldehyde (40%)

water

100 30 20 105 0.5 7.5 1.0 1.0

up to 11

Corresponding compositions containing 5, 10, 25, 50, 200 and 500 g / l of the compounds of Examples A1-A53, B1 to B7, C, D and E were also prepared.

Herbicidal Example A (before formation):

Seeds of the weed species listed below were sown into anodized aluminum vessels 19 cm long, 9.5 cm wide and 6 cm deep, containing sterilized sandy loam soil. They were watered and then sprayed with the compounds of Examples listed below and prepared as a solution / suspension in the volume ratio of 1: 1 with acetone and the wetting agent polyoxyethylene (20 moles) monolaurate solution (2 g / l).

The concentration of each test compound and the application volume were calculated to achieve the desired compound application rate in 4501 per ha. After 3 to 4 weeks growth in a controlled environment (2O ⁰ C; 75-95% relative humidity; 14 hours a day artificial illumination) the plants were visually assessed for herbicidal response.

All differences from an untreated control sample were rated by an index where 0 = no effect, 1 = 1-24% effect, 2 = 25-69% effect, 3 = 70-89% effect and 4 = 90-100% effect. In the table below, the following letters are used to denote the plant species:

a - Polygonum lapathifolium

b - Galium aparine (labweed)

c-Chrysanthemum segetum (Yellow Spiderwort)

d - Alopecurus myosuroides (Black Grass)

e - Elymprepens (Common Wheatgrass)

f - Avenafatua (wild oats).

g - abutiion theophrasti

h - Cyperus rotundus (Purple sedge)

i - Pharitis purpurea (purple winds)

j - Echinochloa curs-galli

k - Setariaviridis (Green Foxtail)

I - Solanum nigrum (Black Nightshade)

The following results were determined:

Ex.

kg / ha

1 2.5 4 4 4 3 2 2 4 4 3 2 2 3 2 2.5 4 4 4 3 0 0 4 4 4 4 4 4 3 2.5 4 4 4 4 4 2 4 4 4 4 4 4 4 1.0 4 4 4 4 2 4 4 4 3 4 4 5 1.0 4 4 1 0 1 .4 4 3 2 2 3 6 1.0 4 4 4 3 2 1 4 0 4 3 3 4 7 1.0 3 3 2 2 2 2 2 4 0 2 2 4 8th 1.0 4 4 4 '3 3 0 4 0 3 3 3 10 1.0 2 3 4 2 0 0 2 0 1 0 0 3 11 1.0 2 4 2 0 0 0 2 0 1 2 0 4 12 1.0 2 4 3 0 0 2 2 0 0 0 0 4 13 1.0 4 4 4 2 2 1 4 4 3 2 1 4 14 1.0 4 4 4 3 3 3 4 4 2 2 15 1.0 4 4 4 3 3 0 4 0 4 4 4 16 1.0 3 4 4 2 2 0 3 0 2 0 0 4 17 1.0 2 3 4 2 2 0 2 0 0 0

Ex.

kg / ha

18 1.0 4 3 2 2 0 0 0 0 0 0 0 3 22 1.0 4 4 4 2 0 0 2 0 0 0 4 2 23 1.0 4 3 2 0 0. 0 2 O 0 0 2 4 24 1.0 4 4 4 0 2 0 0 3 0 2 3 3 25 0.5 3 3 4 0 0 0 1 0 0 0 0 4 29 0.5 3 4 4 2 2 2 4 4 4 2 0 4 30 0.5 2 4 2 2 2 0 2 0 3 0 0 4 31 0.5 2 4 4 2 2 0 4 4 4 3 2 40 1.0 3 4 4 0 0 0 2 2 0 0 0 0 41 0.5 4 "4 4 2 0 0 4 4 2 3 0 B1 1.0 4 4 4 4 3 2 4 4 4 3 4 4 B2 1.0 4 4 4 0 0 4 3 4 2 4 3 4 B3 1.0 4 4 4 2 0 0 0 0 2 0 0 4 B5 0.5 4 4 4 3 0 3 2 0 0 2 4 B6 0.5 4 4 4 2 3 0 2 4 2 2 0 B7 0.5 4 4 4 2 2 2 0 3 0 2 2

Herbic Example B (After Formation):

Seeds of the plant species listed below were sown in anodized aluminum vessels 19cm long, 9.5cm wide and 6cm deep containing sterilized sandy loam soil. They were then watered and placed in a controlled environment room (2O ⁰ C, 75-95% relative humidity, artificial lighting for 14 hours daily). Fourteen or twenty days after sowing (depending on the species, but generally when most plants had 2 to 3 true leaves), the seedlings were foliar-sprayed with the compounds of the examples below, which were in solution / suspension in a volume ratio of 1: 1 in acetone and with the wetting agent polyoxyethylene (20 mol) Monolauratlösung (2g each I) were prepared.

The concentration of each test compound was calculated to determine the desired rate of application of the compound in 450 l / ha. After 2 to 3 weeks of growth under the controlled environment, the plants were visually checked for the response to the herbicide.

All differences from an untreated control sample were rated by an index where 0 = no effect, 1 = 1-24% effect, 2 = 25-69% effect, 3 = 70-89% effect and 4 = 90-100% effect. In the table below (the following letters were used to indicate the plant species:

a - Polygonum lapathifolium

b - Galium aparine (labweed)

c-Chrysanthemum segetum (Yellow Spiderwort)

d -Alopecurus myosuroides (Black Grass)

e - Elymprepens (Common Wheatgrass).

f - Avenafatua (wild oats)

g - Abutilon theoiphrasti

h - Cyperus rotundus (Purple sedge)

i - Pharbitis purpurea (purple winds)

j - Echinochloa crus-galli

k - S'etaria viridis (Green Foxtail)

I - Solanum nigrum (Black Nightshade)

The following results were achieved:

Ex.

kg / ha

1 . 2.5 4 3 4 2 0 0 1 3 1 1 2 4 2 2.5 4 4 4 3 1 2 4 2 4 4 3 4 3 2.5 3 4 3 3 2 2 4 1 3 4 4 3 4 1.0 3 3 3 3 2 2 4 0 2 2 2 3 5 1.0 3 3 2 0 0 1 1 1 1 1 2 0 6 1.0 4 3 2 2 0 1 1 1 1 1 1 2 8th 1.0 4 3 2 2 1 4 1 2 1 1 3 10 1.0 1 4 2 0 0 0 1 0 - 1 1 1 2 12 1.0 2 4 3 0 0 2 2 0 0 0 0 4 13 1.0 1 4 4 2 .0 2 2 0 1 1 2 2 14 1.0 2 4 3 2 1 2 3 0 2 2 2 2 15 1.0 3 4 4 2 0 2 4 0 2 2 2 2 16 1.0 2 3 3 2 0 0 4 0 2 1 0 2 22 0.5 3 4 3 0 0 0 0 3 1 0 α 0 24 1.0. 4 4 4 0 2 0 0 1 0 2 3 3 27 0.5 2 4 4 3 3 3 2 0 1 2 0 0 40 1.0 1 4 3 0 0 0 1 2 0 1 0 2 41 0.5 2 4 2 1 0 0 2 1 1 1 0 2 B1 1.0 2 4 4 2 0 2 3 4 2 3 2 3 B2 1.0 4 4 4 0 0 4 3 0 2 4 3 0 B5 0.5 1 4 3 0 0 2 2 2 2 0 0 3 B6 0.5 2 4 2 2 2 0 0 3 0 2 0th 2 B7 0.5 2 3 4 0 0 0 0 0 0 0 0

Claims (8)

1. A herbicidal composition, characterized in that it consists of 0.5 to 99 wt .-% of one or more Triazolsulfonamide with the formula (I) and their salts, wherein R ^{a is} hydrogen and R ^{b is} a group R ³ CONHCR ² = CR ¹ -, or R ^a and R ^b together form a chain having the formula -C (R ³ ) = NC (R ² ) = C (R ¹ ) - or -C (= Y) -N (R ⁶ ) -C (R ² ) = C (R ¹ ) -, wherein R ¹ , R ² and R ³ , which may be the same or different, each represents hydrogen, a hydroxy, mercapto, halo, cyano, amino, alkylamino, dialkylamino or substituted or unsubstituted alkyl, aryl, araikyl, alkoxy or alkylthio group, Y is oxygen or sulfur and R ^{6 is} hydrogen or a substituted or unsubstituted alkyl or aryl group; or R ¹ and R ² together represent -CH = CH-CH = CH- or- (CH ₂ ) _n - wherein η is 3,4 or 5; R ^{4 is} substituted phenyl or a substituted or unsubstituted aralkyl or heteroaryl group; and R ^{5 is} hydrogen, azyl, carboxy, alkoxycarbonyl, alkylsulfonyl or a substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl or aralkyl group or a group having the formula: (A) wherein R ^a and R ^{b are} as defined above, in addition to a conventional carrier and / or surface active agent. 2. A herbicidal composition according to claim 1, characterized in that R ^{1 represents} hydrogen, a chloro, bromo or an alkyl having 1 to 6 carbon atoms, which are optionally substituted by one or more halogen atoms or alkoxy groups having 1 to 4 carbon atoms. 3. A herbicidal composition according to claim 1 or 2, characterized in that R ^{2 is} hydrogen, phenyl or an alkyl having 1 to 6 carbon atoms, optionally substituted by one or more halogen atoms or alkoxy groups having 1 to 4 carbon atoms. 4. A herbicidal composition according to any one of claims 1 to 3, characterized in that R ^{3 is} hydrogen, phenyl or an alkyl having 1 to 6 carbon atoms, optionally substituted by one or more halogen atoms or alkoxy groups having 1 to 4 carbon atoms. 5. A herbicidal composition according to any one of claims 1 to 4, characterized in that R ^{4 represents} a phenyl group substituted by one or more halogen atoms, alkyl groups having 1 to 4 carbon atoms, alkoxy or alkylthio groups having 1 to 4 carbon atoms, alkoxy carbonyl groups having 2 to 5 carbon atoms or nitro groups. 6. A herbicidal composition according to any one of claims 1 to 5, characterized in that R ^{5 is} hydrogen, alkyl having 1 to 6 carbon atoms, alkenyl or alkynyl having 2 to 6 carbon atoms or acyl, alkoxycarbonyl or alkylsulfonyl wherein the alkyl moiety is 1 to 4 carbon contains atoms. 7. A herbicidal composition according to any one of claims 1 to 6, characterized in that R ^a and R ^b together represent a chain having the formula -C (R ³ ) = NC (R ² ) = C (R ¹ ) -, R ¹ , R ² and R ^{3 are} each hydrogen, methyl, ethyl, phenyl, trifluoromethyl or a chloro group, R ^{4 is} a phenyl group substituted by one or more halogen atoms, alkyl, alkoxy or alkylthio groups having 1 to 4 carbon atoms, trifluoromethyl groups, alkoxycarbonyl groups with 2 to 5 carbon atoms or nitro groups and R ^{5 is} hydrogen. 8. A herbicidal composition according to claim 1, characterized in that the triazolesulfonamide N- (2,6-difluorophenyl) -5,7-dimethyl [1,2,4] triazolo [1,5-c] pyrimidine-2-sulfonamide or5 Is - (2-acetamido-1-propenyl) -N- (2,6-di-fluorophenyl) -1H-1,2,4-triazole-3-sulfonamide.