DE4330893A1 - N-Heteroaryl-N'(pyrid-2-yl-sulphonyl)ureas, their preparation, and their use as herbicides and plant growth regulators - Google Patents

Abstract

Pyridylsulphonylureas of the formula (I) and their salts <IMAGE> in which R<1>, R<2>, R<3>, R<4>, A and n are as defined in Claim 1 are suitable for the selective control of harmful plants or for regulating the growth in crops of useful plants. The compounds (I) can be prepared analogously to known processes (see Claim 4) via intermediates, some of which are new, of the formulae benzenesulphonamides (II), carbamates (IV) or sulphonylisocyanates (VI) by reaction with carbamates (III) or with amines (V), the formulae (II) - (VI) being as defined in Claim 4.

Description

The invention relates to the technical field of herbicides and Plant growth regulators, especially herbicides for selective Control of weeds and grass weeds in crops.

It is known that some 2-pyridylsulfonylureas are herbicidal and possess plant growth regulating properties; compare EP-A- 13 480, EP-A-272 855, EP-A-84224, US-A-4421550, EP-A-103543 (US-A- 4,579,583) US-A-4487626, EP-A-1 25864, WO 88/04297 and WO 91/10660 (ZA 91/0173), WO 92/16522.

Further 2-pyridylsulfonylureas with special residues in 3- Position of the pyridyl residue found as herbicides and Plant growth regulators are suitable.

The present invention relates to compounds of the formula (I) or their salts,

wherein
R¹ and R² independently of one another (C₁-C₈) alkyl which is unsubstituted or by one or more radicals from the group halogen, nitro, cyano, (C₁-C₄) alkoxy, [(C₁-C₄) alkoxy] carbonyl, Aryl and substituted aryl is substituted, or (C₁-C₆) alkoxy, (C₃-C₆) alkenyl, (C₃-C₆) alkynyl or aryl, the aryl radical being unsubstituted or by one or more radicals from the group halogen, nitro , (C₁-C₄) alkyl, (C₁-C₄) alkoxy and [(C₁-C₄) alkoxy] carbonyl, or H, if the other of the substituents R² and R¹ on the N atom is not a hydrogen atom, or
R¹ and R² together with the N atom connecting them form a heterocyclic ring with 3-7 ring atoms and 0, 1 or 2 further heteroatoms from the group O, N and S, where the ring may be benzo-fused and unsubstituted or by one or more Radicals from the group (C₁-C₄) alkyl, (C₁-C₄) alkoxy, [(C₁-C₄) alkoxy] carbonyl and aryl is substituted,
R³ (C₁-C₄) alkyl, (C₁-C₃) haloalkyl, halogen, NO₂, CN, (C₁-C₃) alkoxy, (C₁- C₃) haloalkoxy, (C₁-C₃) alkylthio, (C₁- C₃) alkoxy- (C₁-C₃) alkyl, [(C₁-C₃) alkoxy] carbonyl, (C₁-C₃) alkylamino, di - [(C₁-C₃) alkyl] amino, (C₁- C₃) - alkylsulfonyl, SO₂NRaR ^b or C (O) NR ^c R ^d ,
Ra, R ^b , R ^c , R ^d independently of one another H, (C₁-C₄) alkyl, (C₃-C₆) alkenyl, (C₃- C₆) alkynyl, [(C₁-C₄) alkyl] carbonyl, Arylcarbonyl, which is unsubstituted or substituted in the aryl radical, or in pairs Ra and R ^b or R ^c and R ^d together with the N atom connecting them, a heterocyclic saturated or unsaturated ring with 3-7 ring atoms and 0, 1 or 2 further heteroatoms from the group N, O and S, where the ring is unsubstituted or substituted,
R⁴ H or (C₁-C₄) alkyl, preferably H or CH₃, in particular H,
n 0, 1 or 2, preferably 0 or 1,
A is a residue of the formula

X, Y independently of one another are H, halogen, (C₁-C₃) alkyl, (C₁-C₃) alkoxy or (C₁-C₃) alkylthio, the abovementioned alkyl-containing radicals being unsubstituted or singly or multiply by halogen or mono- or are substituted twice by radicals from the group (C₁-C₃) alkoxy and (C₁-C₃) alkylthio, or a radical of the formula NR⁵R⁶, (C₃-C₆) - cycloalkyl, (C₂-C₄) alkenyl, (C₂- C₄) alkynyl, (C₃-C₄) alkenyloxy or (C₃- C₄) alkynyloxy,
R⁵, R⁶ independently of one another H, (C₁-C₃) alkyl or (C₃-C₄) alkenyl,
Z is CH or N, preferably CH,
X¹ CH₃, OCH₃, OC₂H₅ or OCF₂H,
Y¹ -O- or -CH₂-,
X² CH₃, C₂H₅ or CH₂CF₃,
Y² OCH₃, OC₂H₅, SCH₃, SC₂H₅, CH₃ or C₂H₅,
X³ CH₃ or OCH₃,
Y³ H or CH₃,
X⁴ CH₃, OCH₃, OC₂H₅, CH₂OCH₃ or Cl,
Y⁴ CH₃, OCH₃, OC₂H₅ or Cl and
Y⁵ CH₃, C₂H₅, OCH₃ or Cl
mean.

In the formula (I) and below, hydrocarbon-containing radicals such as. B. alkyl, alkoxy, haloalkyl and alkylthio radicals and the corresponding unsaturated and / or substituted radicals in the hydrocarbon part may each be straight-chain or branched. If not specified in more detail, the hydrocarbon parts having up to 6, in particular up to 4, carbon atoms are preferred. Alkyl radicals, also in the composite meanings such as alkoxy, haloalkyl, etc. mean z. B. methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl; Alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals, such as, for. B. 2-propenyl, 2- or 3-butenyl, 2-propynyl, 2- or 3-butynyl. Halogen means fluorine, chlorine, bromine or iodine. Haloalkyl means alkyl which is substituted by one or more atoms from the group halogen; Haloalkyl is for example CF₃, CHF₂, CH₂CF₃, CH₂CH₂Cl. Aryl is, for example, a mononuclear, polynuclear or polynuclear aromatic radical such as phenyl, naphthyl, tetrahydronaphthyl, indanyl, fluorenyl and the like, preferably phenyl. Substituted aryl or substituted phenyl preferably means aryl or phenyl, which is substituted by one or more, preferably 1 to 3, radicals from the group halogen, alkyl, haloalkyl, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkanoyl, carbamoyl, mono- and dialkylaminocarbonyl, Mono- and dialkylamino, alkylsulfinyl and alkylsulfonyl is substituted, the alkyl-containing radicals having 1 to 4 carbon atoms, in particular 1 to 2 carbon atoms, being preferred; methyl, methoxy and chlorine are particularly preferred. Examples of heterocyclic rings or residues NR¹R², NRaR ^b , NR ^c R ^d , are pyrrole, imidazole, pyrazole, triazole, pyrazolone, oxazole, oxazolone, propane sultame, butane sultame, pyrrolidone, piperidine, piperazine and morpholine.

Benzo-fused heterocyclic residues are through one or two benzene nuclei preferably heterocycles fused to a benzene nucleus, which may also be hydrogenated  can, for example indoline, isoindoline, indazole, quinoline, isoquinoline, Phthalazine quinoxaline, quinazoline, cinnoline, benzoxazole, benzthiazole and hydrogenated or partially hydrogenated systems. As a substituent for the heterocyclic and benzo-fused heterocyclic radicals come e.g. B. the substituted phenyl radical, preferably alkyl, Haloalky and alkoxy.

The invention also relates to all stereoisomers which are derived from formula (I) are included, and mixtures thereof. Such compounds of formula (I) contain one or more asymmetric carbon atoms or double bonds, which in the general formulas (I) are not specified separately. The through their specific spatial form defined possible stereoisomers, such as enantiomers, However, diastereomers, Z and E isomers are all encompassed by formulas (I) and can be prepared from mixtures of the stereoisomers by customary methods be contained or by stereoselective reactions in combination with the use of stereochemically pure starting materials become.

The compounds of formula (I) can form salts in which the hydrogen the -SO₂-NH group replaced by a cation suitable for agriculture becomes. These salts are, for example, metal salts, in particular alkali salts (e.g. Na and K salts) or alkaline earth metal salts, or also ammonium salts or salts with organic amines. Salt formation can also be caused by the addition of a strong Acid to the pyridine portion of the compound of formula (I). Suitable Acids for this are strong inorganic and organic acids, for example HCl, HBr, H₂SO₄ or HNO₃.

Preferred compounds of the formula (I) or their salts are those in which
R¹H, (C₁-C₄) alkyl which is unsubstituted or substituted by one or more radicals from the group halogen, cyano and (C₁-C₄) alkoxy, or (C₁-C₄) alkoxy, (C₃-C₆) - Alkenyl or (C₃-C₆) alkynyl and
R² (C₁-C₄) alkyl which is unsubstituted or substituted by one or more radicals from the group halogen, nitro, cyano, (C₁-C₄) alkoxy and (C₁-C₄) alkoxycarbonyl, or (C₁-C₄) Alkoxy, aryl, the aryl radical being unsubstituted or substituted by one or more radicals from the group halogen, nitro and (C₁-C₄) alkyl, or (C₃-C₈) - alkenyl or (C₃-C₈) alkynyl, or
R¹ and R² together with the N atom connecting them form a heterocyclic ring with 5-7 ring atoms and in addition to the N atom up to a further heteroatom from the group O and N, the ring being unsubstituted or by one or more radicals from the Group (C₁-C₄) alkyl, (C₁-C₄) alkoxycarbonyl and aryl is substituted.

Further preferred compounds of the formula (I) according to the invention or their salts are those in which
R³ (C₁-C₄) alkyl, (C₁-C₃) haloalkyl, halogen or (C₁-C₃) alkoxy and
n is 0, 1 or 2, preferably 0 or 1, with R³ in the 6-position of the pyridin-2-yl radical and n 0 or 1 being particularly preferred.

Further preferred are compounds of formula (I) or their salts, wherein
R¹ (C₁-C₄) alkyl and
R² (C₁-C₄) alkyl, (C₁-C₄) alkoxy or aryl which is unsubstituted or substituted by one or more of the radicals halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy and nitro, or
R¹ and R² together with the N atom connecting them is an unsubstituted or substituted by (C₁-C₄) alkyl morpholine or piperidine ring
mean.

Compounds of the formula (I) or are also preferred their salts, wherein R¹ CH₃ or C₂H₅ and R² CH₃, C₂H₅, C₃H₇, C₄H₉ or Phenyl mean.  

Further preferred compounds of the formula (I) according to the invention or their salts are those in which
A is a residue of the formula

is.

Preferably one of the radicals X and Y is (C₁-C₃) alkyl, (C₁-C₃) alkoxy, (C₁-C₃) haloalkyl, (C₁-C₃) haloalkoxy or [(C₁-C₂) alkoxy] - (C₁-C₂) alkyl and the other radical Y or X is (C₁-C₃) alkyl, (C₁-C₃) alkoxy, (C₁-C₃) alkylthio, each of the latter 3 radicals unsubstituted or one or more times by halogen or once or twice by (C₁-C₃) alkoxy or (C₁-C₃) alkylthio is substituted, or halogen or a radical of the formula NR⁵R⁶, where R⁵ and R⁶ independently of one another are H, (C₁-C₃) alkyl or (C₃-C₄) - Are alkenyl, or (C₃-C₆) cycloalkyl, (C₂-C₄) alkenyl, (C₂-C₄) alkynyl, (C₃-C₄) alkenyloxy or (C₃-C₄) alkynyloxy.

Even more preferably one of the radicals X and Y is (C₁-C₂) alkyl, (C₁-C₂) alkoxy or OCF₂H, and the other radical Y or X means (C₁-C₂) - Alkyl, (C₁-C₂) alkoxy, halogen, OCF₂H, OCH₂CF₃ or CF₃.

In particular, X and Y are independently (C₁-C₂) alkyl or (C₁-C₂) alkoxy.

Compounds of the formula (I) or their compounds are also preferred Salts, which are a combination of two or more of the preferred Have meanings (features).

The present invention further relates to processes for the production of the compounds of formula (I) according to the invention or their salts, thereby characterized that one

• a) a compound of the formula (II), with a heterocyclic carbamate of the formula (III), wherein R * is optionally substituted phenyl or (C₁-C₄) alkyl, reacted or
• b) a pyridylsulfonylcarbamate of the formula (IV) with an amino heterocycle of the formula (V) H-NR⁴-A (V) or
• c) a sulfonyl isocyanate of the formula (VI) with an amino heterocycle of the formula (V) H-NR⁴-A (V) or
• d) in a one-pot reaction, first an amino heterocycle of the formula H-NR⁴-A (V) in the presence of a base, such as. B. triethylamine, with phosgene reacted and the intermediate formed with a pyridine sulfonamide Implements formula (II),

wherein in the formulas (II) - (VI) R¹, R², R³, R⁴, A and n as defined in formula (I) are.

The compounds of the formulas (II) and (III) are preferably reacted base catalyzed in an inert organic solvent, such as. B. Dichloromethane, acetonitrile, dioxane or THF, at temperatures between 0 ° C and the boiling point of the solvent. For example, 1.8- Diazabicyclo- [5.4.0] undec-7-ene (DBU) or trimethyl aluminum or Triethyl aluminum is used.

The sulfonamides (II) are new compounds. You and their manufacture are also subject of the invention.  

The compound of formula (II) z. B. starting from compounds of Formula (VII)

by reaction with carbamoyl halides of the formula

(Hal = halogen such as chlorine, bromine) or, in the case of R² = H, with isocyanates of Formula OCN-R¹, wherein R¹ and R² are as defined in formula (I), and subsequent reaction of the obtained 3- protected with the t-butyl group Carbamoyloxy-pyridine-2-sulfonamids with a strong acid (e.g. trifluor acetic acid) to free 3-carbamoyloxy-pyridine-2-sulfonamide of the formula (II).

Alternatively, at the stage of the t-butyl protected sulfonamide with R² = H by usual methods also to compounds with R² not equal to H be derivatized, e.g. B. by allylation and acylation, wherein after Removal of the protective group sulfonamide II with R² not equal to H can be obtained.

The individual reaction stages can be carried out analogously to conventional processes be performed. The sulfonamides of formula (VII) are after Process known from the literature from 2-chloro-3-hydroxypyridine after protecting the free hydroxy group (e.g. as benzyl ether) by reaction with sulfur Nucleophiles, e.g. B. benzyl mercaptan, subsequent oxidizing Chlorination of the sulfur atom with sodium hypochlorite or chlorine (formation of the Sulfochlorides analogous to EP-A-272 855) and implementation of the obtained Sulfochlorides with tert-butylamine and subsequent cleavage of the Protective group on oxygen (in the case of benzyl ether hydrogenolytic) producible.  

The carbamates of the formula (III) can be prepared by methods which are described in South African patent applications 82/5671 and 82/5045 and EP-A 70804 (US-A-4 480 101) or Research Disclosure RD 275056 are.

Carbamoyl chlorides of the formula

let up literature methods obtained from the amine hydrochlorides with phosgene (Liebigs Ann. Chemistry 299, 85).

The reaction of the compounds (IV) with the amino heterocycles (V) is carried out preferably in inert, aprotic solvents such as. B. dioxane, Acetonitrile or tetrahydrofuran at temperatures between 0 ° C and Boiling point of the solvent. The Pyridylsulfonylcarbamate the Formula (IV) is obtained analogously to EP-A-44 808 or EP-A-237 292.

The pyridylsulfonyl isocyanates of the formula (VI) can be prepared analogously to EP-A-1 84 385 produce and react with the amino heterocycles of the formula (V).

The salts of the compounds of formula (I) are preferably inert Solvents such as B. water, methanol or acetone at temperatures of 0 to 100 ° C manufactured. Suitable bases for the preparation of the Salts according to the invention are, for example, alkali carbonates, such as Potassium carbonate, alkali and alkaline earth hydroxides, ammonia or ethanolamine. When Acids for salt formation are particularly suitable for HCl, HBr, H₂SO₄ or HNO₃.

With the "inert" designated in the above process variants Solvents "are solvents that are meant under the respective Reaction conditions are inert, but not under any Reaction conditions must be inert.

The compounds of the formula (I) according to the invention or their salts have excellent herbicidal activity against a wide range  economically important mono- and dicotyledonous harmful plants. Difficult too controllable perennial weeds, which consist of rhizomes, rhizomes or expel other permanent organs, are well captured by the active ingredients. It does not matter whether the substances are pre-seeded, pre-emergence or Post-emergence procedures are applied. In particular, for example called some representatives of the monocotyledonous and dicotyledonous weed flora caused by the Compounds according to the invention can be controlled without the name should be restricted to certain species.

On the side of the monocot weed species, e.g. B. Avena, Lolium, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria and Cyperus species from the annual group and on the part of the perennial species Agropyron, Cynodon, imperata and sorghum as well as persistent cyperus species are good detected.

With dicotyledon weed species, the spectrum of activity extends to species such as e.g. B. Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Matricaria, Abutilon and Sida on the annual side and convolvulus, Cirsium, Rumex and Artemisia in the perennial weeds.

Weeds occurring in rice under the specific crop conditions such as e.g. B. Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus are from the Active ingredients according to the invention also fought excellently.

Are the compounds of the invention prior to germination on the Applied earth surface, so is either the emergence of the weed seedlings completely prevented or the weeds grow to the cotyledon stage approach, but then stop growing and eventually die after it expires from three to four weeks.

When applying the active ingredients to the green parts of the plant in Post-emergence procedures also occur very quickly after treatment  drastic growth stop and the weed plants stay in the for Application time stand or die existing growth stage after a certain time completely, so that one for the Crops harmful weed competition eliminated very early and sustainably becomes.

Although the compounds of the invention are excellent herbicidal Have activity against mono- and dicotyledon weeds Cultivated plants of economically important crops such as B. wheat, barley, Rye, rice, maize, sugar beet, cotton and soy only marginally or not at all not harmed. The present compounds are suitable from these Reasons very well for selective control of undesirable Plant growth in agricultural crops.

In addition, the compounds of the formula (I) according to the invention have excellent growth regulatory properties in crops. They intervene and can regulate the plant's own metabolism thus for the targeted influencing of plant ingredients and for Harvesting relief, e.g. B. by triggering desiccation and stunted growth, be used. Furthermore, they are also suitable for general control and inhibiting unwanted vegetative growth without sacrificing the To kill plants. An inhibition of vegetative growth plays with many monocotyledonous and dicotyledonous cultures play a major role because of the fact can be reduced or completely prevented.

The compounds of formula (I) according to the invention can be in the form of Wettable powders, emulsifiable concentrates, sprayable solutions, Dusts or granules are used in the usual preparations become. The invention therefore also relates to herbicides and plant growth regulating agents, the compounds of the formula (I) or containing their salts.  

The compounds of formula (I) or their salts can in various ways be formulated, depending on which biological and / or chemical physical parameters are specified. As formulation options Examples include: wettable powder (WP), water-soluble powder (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions, Suspension concentrates (SC), dispersions based on oil or water, oil-miscible solutions, capsule suspensions (CS), dusts (DP), mordants, Granules for spreading and soil application, granules (GR) in the form of Micro, spray, elevator and adsorption granules, water dispersible Granules (WG), water-soluble granules (SG), ULV formulations, Microcapsules and waxes.

These individual types of formulation are known in principle and will described for example in: Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th edition 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.V., 1973; K. Martens, "Spray Drying "Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.

The necessary formulation aids such as inert materials, surfactants, Solvents and other additives are also known and will be described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers ", 2nd Ed., Darland Books, Caldwell N.J., H.v. Olphen," Introduction to Clay Colloid Chemistry "; 2nd Ed., J. Wiley & Sons, N.Y .; C. Marsden, "Solvents Guide"; 2nd Ed., Interscience, N.Y. 1963; McCutcheon’s "Detergents and Emulsifiers Annual ", MC Publ. Corp., Ridgewood N.J .; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, "Interface-active ethylene oxide adducts", Wiss. Publishing company, Stuttgart 1976; Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986.

Based on these formulations, combinations can also be made with  other pesticidal substances, such as. B. insecticides, acaricides, Herbicides, fungicides, safeners, fertilizers and / or growth regulators produce, e.g. B. in the form of a finished formulation or as a tank mix.

Spray powders are preparations which are uniformly dispersible in water Active substance in addition to a diluent or an inert substance or ionic surfactants and / or nonionic type (wetting agents, dispersing agents), e.g. B. polyoxyethylated Alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines, Fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium lignosulfonate, 2,2′-dinaphthylmethane-6,6′-disulfonic acid sodium, dibutylnaphthalene-sulfonic acid sodium or oleoylmethyltauric acid Contain sodium. To make the wettable powders, the herbicides are used Active ingredients, for example in conventional equipment such as hammer mills, Fan mills and air jet mills finely ground and simultaneously or then mixed with the formulation auxiliaries.

Emulsifiable concentrates are made by dissolving the active ingredient in an organic solvent e.g. B. butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of organic solvents with the addition of one or more surfactants of ionic and / or nonionic type (emulsifiers). The following can be used as emulsifiers:
Alkylarylsulfonic acid calcium salts such as Ca-dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as e.g. B. sorbitan fatty acid esters or polyoxethylene sorbitan esters such. B. polyoxyethylene sorbitan fatty acid ester.

Dusts are obtained by grinding the active ingredient with finely divided solids, e.g. B. talc, natural clays such as kaolin, bentonite and Pyrophyllite, or diatomaceous earth.  

Suspension concentrates can be water or oil based. You can for example by wet grinding using commercially available pearl mills and optionally addition of surfactants, such as. B. above with the others Formulation types already listed can be produced.

Emulsions e.g. B. oil-in-water emulsions (EW), for example using stirrers, colloid mills and / or static mixers using of aqueous organic solvents and, if appropriate, surfactants, such as e.g. B. already listed above for the other formulation types, produce.

Granules can either by spraying the active ingredient adsorbable, granulated inert material or by Applying active ingredient concentrates using adhesives, e.g. B. Polyvinyl alcohol, polyacrylic acid sodium or mineral oils on which Surface of carriers such as sand, kaolinite or granulated Inert material. Suitable active ingredients can also be used in the production of Fertilizer granules in the usual way - if desired in a mixture with Fertilizers - be granulated.

Water-dispersible granules are usually made according to the usual Processes such as spray drying, fluidized bed granulation, plate granulation, Mixing with high speed mixers and extrusion without solid Made of inert material.

The agrochemical preparations usually contain 0.1 to 99 % By weight, in particular 0.1 to 95% by weight, of active compound of the formula (I) or its Salts.

In wettable powders, the active ingredient concentration is e.g. B. about 10 to 90% by weight, the rest of 100% by weight consists of customary formulation components. At emulsifiable concentrates, the active ingredient concentration can be about 1 to 90,  preferably 5 to 80 wt .-%. Dusty formulations contain 1 to 30, preferably mostly 5 to 20 wt .-% of active ingredient; sprayable solutions contain e.g. B. about 0.05 to 80, preferably 2 to 50 % By weight of active ingredient. In the case of water-dispersible granules, the Active ingredient content depends in part on whether the active compound is liquid or solid and which granulation aids, fillers etc. are used. The active ingredient content is in the water-dispersible granules for example between 1 and 95% by weight, preferably between 10 and 80 % By weight.

In addition, the active ingredient formulations mentioned optionally contain the usual adhesive, wetting, dispersing, emulsifying, penetrating, Preservatives, antifreeze and solvents, fillers, carriers and dyes, Defoamers, evaporation inhibitors and the pH and viscosity influencing means.

As a combination partner for the active substances according to the invention in mixture formulations or in the tank mix, known active substances can be used, for example, as described in e.g. B. from Weed Research 26, 441-445 (1986), or "The Pesticide Manual", 9th edition, The British Crop Protection Council, 1990/91, Bracknell, England, and literature cited therein. As herbicides known from the literature, which can be combined with the compounds of formula (I), z. For example, the following active substances are to be mentioned (note: the compounds are identified either with the "common name" according to the International Organization for Standardization (ISO) or with the chemical name, possibly together with a usual code number):
acetochlor; acifluorfen; aclonifen; AKH 7088, ie [[[1- [5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrophenyl] -2-methoxyethylidene] amino -] - oxy] - acetic acid and methyl acetate; alachlor; alloxydim; ametryn; amidosulfuron; amitrole; AMS, ie ammonium sulfamate; anilofos; asulam; atrazine; aziprotryn; barban; BAS 516 H, ie 5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; benazolin; benfluralin; benfuresate; bensulfuron-methyl; bensulide; bentazone; benzofenap; benzofluor; benzoylprop-ethyl; benzthiazuron; bialaphos; bifenox; bromacil; bromobutide; bromofenoxim; bromoxynil; bromuron; buminafos; busoxinone; butachlor; butamifos; butenachlor; buthidazole; butralin; butylates; carbetamide; CDAA, ie 2-chloro-N, N-di-2-propenylacetamide; CDEC, ie 2-chloroallyl ester of diethyldithiocarbamic acid; CGA 184927, ie 2- [4 - [(5-chloro-3-fluoro-2-pyridinyl) -oxy] phenoxy] propanoic acid and 2-propynyl ester; chlomethoxyfen; chloramben; chlorazifop-butyl, pirifenop-butyl; chlorbromuron; chlorobufam; chlorfenac; chlorflurecol-methyl; chloridazon; chlorimuron ethyl; chloronitrofen; chlorotoluron; chloroxuron; chlorpropham; chlorsulfuron; chlororthal dimethyl; chlorothiamide; cinmethylin; cinosulfuron; clethodim; clomazone; clomeprop; cloproxydim; clopyralid; cyanazine; cycloate; cycloxydim; cycluron; cyperquat; cyprazine; cyprazole; 2,4-DB; dalapon; desmediphan; desmetryn; di-allate; dicamba; dichlobenil; dichlorprop; diclofop-methyl; diethatyl; difenoxuron; difenzoquat; diflufenican; dimefuron; dimethachlor; dimethametryn; dimethazone, clomazone; dimethipin; dimetrasulfuron, cinosulfuron; dinitramine; dinoseb; dinoterb; diphenamide; dipropetryn; diquat; dithiopyr; diuron; DNOC; eglinazine-ethyl; EL 177, ie 5-cyano-1- (1,1-dimethylethyl) -N-methyl-3H-pyrazole-4-carboxamide; endothal; EPTC; esprocarb; ethalfluralin; ethametsulfuron-methyl; ethidimuron; ethiozin; ethofumesate; F5231, ie N- [2-chloro-4-fluoro-5- [4- (3-fluoropropyl) -4,5-dihydro-5-oxo-1H-tetrazol-1-yl] phenyl] ethanesulfonamide; F6285, ie 1- [5- (N-methylsulfonyl) amino-2,4-dichlorophenyl] -3-methyl-4-difluoromethyl-1,2,4-triazol-5-one; fenoprop; fenoxan, clomazone; fenoxaprop-ethyl; fenuron; flamprop-methyl; flazasulfuron; fluazifop and its ester derivatives; fluchloralin; flumetsulam; N- [2,6-difuorphenyl] -5-methyl- (1,2,4) -triazolo [1,5a] pyrimidine-2-sulfonamide; flumeturon; flumipropyn; fluorodifen; fluoroglycofen-ethyl; fluridone; flurochloridone; fluroxypyr; flurtamone; fomesafen; fosamine; furyloxyfen; glufosinate; glyphosate; halosafen; haloxyfop and its ester derivatives; hexazinone; Hw 52, ie N- (2,3-dichlorophenyl) -4- (ethoxymethoxy) benzamide; imazamethabenz-methyl; imazapyr; imazaquin; imazethamethapyr; imazethapyr; imazosulfuron; ioxynil; isocarbamide; isopropaline; isoproturon; isouron; isoxaben; isoxapyrifop; carbutilates; lactofen; lenacil; linuron; MCPA; MCPB; mecoprop; mefenacet; mefluidide; metamitron; metazachlor; methabenzthiazuron; metham; methazole; methoxyphenone; methyldymron; metobromuron; metolachlor; metoxuron; metribuzin; metsulfuron-methyl; MH; molinate; monalide; monocarbamide dihydrogen sulfates; monolinuron; monuron; MT 128, ie 6-chloro-N- (3-chloro-2-propenyl) -5-methyl-N-phenyl-3-pyridazinamine; MT 5950, ie N- [3-chloro-4- (1-methylethyl) phenyl] -2-methylpentanamide; naproanilide; napropamide; naptalam; NC 310, ie 4- (2,4-dichlorobenzoyl) -1-methyl-5-benzyloxypyrazole; neburon; nicosulfuron; nipyraclophen; nitraline; nitrofen; nitrofluorfen; norflurazon; orbencarb; oryzalin; oxadiazon; oxyfluorfen; paraquat; pebulate; pendimethalin; perfluidone; phenmedipham; phenisopham; phenmedipham; picloram; piperophos; piributicarb; pirifenop-butyl; pretilachlor; primisulfuron-methyl; procyazine; prodiamine; profluralin; proglinazine-ethyl; prometon; prometryn; propachlor; propanil; propaquizafop and its ester derivatives; propazine; propham; propyzamide; prosulfalin; prosulfocarb; prynachlor; pyrazolinates; pyrazone; pyrazosulfuron-ethyl; pyrazoxyfen; pyridate; quinclorac; quinmerac; quinofop and its ester derivatives, quizalofop and its ester derivatives; quizalofop-ethyl; quizalofop-p-tefuryl; renriduron; dymron; S 275, ie 2- [4-chloro-2-fluoro-5- (2-propynyloxy) phenyl] -4,5,6,7-tetrahydro-2H-indazole; S 482, ie 2- [7-fluoro-3,4-dihydro-3-oxo-4- (2-propynyl) -2H-1,4-benzoxazin-6-yl] -4,5,6,7- tetrahydro-1H-isoindole-1,3 (2H) -dione; secbumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, ie 2 - [[7- [2-chloro-4- (trifluoromethyl) phenoxy] -2-naphthalenyl] oxy] propanoic acid and methyl ester; sulfometuron-methyl; sulfazuron; flazasulfuron; TCA; tebutam; tebuthiuron; terbacil; terbucarb; terbuchlor; terbumeton; terbuthylazine; terbutryn; TFH 450, ie N, N-diethyl-3 - [(2-ethyl-6-methylphenyl) sulfonyl] -1H-1,2,4-triazole-1-carboxamide; thiazafluron; thifensulfuron-methyl; thiobencarb; tiocarbazil; tralkoxydim; tri-allate; triasulfuron; triazofenamide; tribenuron-methyl; triclopyr; tridiphane; trietazine; trifiuralin; trimeturon; vernolate; WL 110547, ie 5-phenoxy-1- [3- (trifluoromethyl) phenyl] -1H-tetrazole.

Those available in the commercial form are used  Formulations optionally diluted in the usual manner, e.g. B. with wettable powders, emulsifiable concentrates, dispersions and water-dispersible Granules using water. Dust-like preparations, soil or Scatter granules as well as sprayable solutions are used before use usually no longer diluted with other inert substances.

The compounds of the invention can, for example, directly on the Harmful plants or harmful plants and crops at the same time Post-emergence method or on the area on which the plants grow, e.g. B. on arable soil with plant seeds or emerged plants or on Cultivated areas, such as B. a rice-growing area, in pre- or post-emergence be applied.

With the external conditions such as temperature, humidity, the type of herbicide used, u. a. the required application rate varies Compounds of formula (I). It can fluctuate within wide limits, e.g. B. between 0.001 and 10.0 kg / ha or more of active substance, preferably however between 0.005 and 5 kg / ha.

A. Chemical examples Examples a) 3-Benzyloxy-3-chloropyridine

15.6 g (0.12 mol) of 2-chloro-3-hydroxypyridine are dissolved in 100 ml of acetone dissolved, 18.3 g (0.121 mol) potassium carbonate added, at 30 min Stirred at room temperature and then 20.6 g (0.12 mol) Benzyl bromide added dropwise. The mixture is heated to reflux for 4 h and the mixture is left on Cool to room temperature, filter off the precipitate and distill it Acetone under reduced pressure. The residue is in ethyl acetate  recorded, the organic phase once with saturated Sodium bicarbonate solution and water washed, the organic Phase dried over magnesium sulfate, filtered off from the desiccant and the ethyl acetate is removed under reduced pressure. 20.5 g (78% That is, 3-benzyloxy-2-chloropyridine as a viscous oil, which as a crude product is processed further.

b) 3-benzyloxy-2-benzylthiopyridine

19.5 g (0.089 mol) of 3-benzyloxy-2-chloropyridine are dissolved in 100 ml of dioxane dissolved, 13.6 g (0.093 mol) of sodium benzyl mercaptide added and 7 h heated to reflux. The solvent is applied under reduced pressure removed, the residue taken up in ethyl acetate and with water washed, the organic phase dried with magnesium sulfate, the Desiccant filtered off and the ethyl acetate under reduced pressure distilled off. 22.4 g (82% of theory) of 3-benzyloxy-2- are obtained benzylthiopyridine as a yellow oil.

c) 3-Benzyloxypyridine-2-tert-butylsulfonamide

5.7 g (18.5 mmol) of 3-benzyloxy-2-benzylthiopyridine are in 200 ml Dissolved dichloromethane and added 200 ml of phosphate buffer (pH 7). At 0 ° C 10.5 g of chlorine gas are introduced and 10 min. at 0 ° C stirred. A stream of nitrogen is then passed through the Solution until all excess chlorine is removed. You pour the approach in 300 ml ice water, separates the organic phase, dries the Dichloromethane solution with magnesium sulfate, filtered from the desiccant and cools the solution to -70 ° C. At this temperature 5.4 g (74 mmol) tert-butylamine was added dropwise and the mixture was then added slowly warmed to room temperature. The precipitate is filtered off,  the solvent was distilled off under reduced pressure and the residue Chromatographed on silica gel (eluent, ethyl acetate: n-heptane, 6: 4). 2.6 g (44% of theory) of 3-benzyloxypyridine-2-tert-butylsulfonamide are obtained melting point 83 ° C.

d) 3-hydroxy-2-pyridine-tert-butylsulfonamide

2.6 g (8.1 mmol) of 3-benzyloxy-2-pyridine-tert-butylsulfonamide are in 20 ml of ethanol dissolved, 0.2 g of palladium on carbon (10%) added and at room temperature hydrogen introduced until saturation. The ethanol is then distilled off under reduced pressure Residue mixed with diethyl ether, filtered off from the precipitate and the Distilled off ether under reduced pressure. The residue is Stirred heptane and 1.4 g (74% of theory) of 3- are obtained by filtration Hydroxy-2-pyridine-tert-butylsulfonamide with a melting point of 128 ° C.

e) 3-diallylaminocarbonyloxy-2-pyridine-tert-butylsulfonamide

0.4 g sodium hydride (60% suspension in mineral oil) are mixed with n-heptane washed oil-free and suspended in 40 ml of dimethylformamide. To this Suspension is added dropwise 2.3 g (10 mmol) of 3-hydroxy-2-pyridine-tert.- Butylsulfonamide added and heated to 70 ° C for 45 min. At this The temperature is added dropwise to 2.4 g (15 mmol) of diallylcarbamic acid chloride, stirred for 2 h at 80 ° C and allowed to cool to room temperature. The Solvent is distilled off under reduced pressure, the residue in Ethyl acetate and the organic phase with 2N sodium hydroxide solution washed. The organic phase is dried with magnesium sulfate, the desiccant is filtered off and the ethyl acetate at reduced pressure away. 3.17 g (90% of theory) of 3- Diallylaminocarbonyloxy-2-pyridine-tert-butylsulfonamide as a viscous oil.  

f) 3-diallylaminocarbonyloxy-2-pyridinesulfonamide

3.0 g (8.5 mmol) 3-diallylaminocarbonyloxy-2-pyridine-tert.- butylsulfonamide in 40 ml of trifluoroacetic acid for 4 days Room temperature stirred. The trifluoroacetic acid is reduced The pressure is distilled off and the residue is mixed with diethyl ether. By Filtration gives 2.1 g (83% of theory) of 3-diallylaminocarbonyloxy-2- pyridine sulfonamide, melting point 94 ° C.

g) N - [(4,6-Dimethoxypyrimidin-2-yl) aminocarbonyl] -3- diallylaminocarbonyloxy-2-pyridinesulfonamide (Example 6 from Table 1)

To a solution of 1.13 g (0.0038) 3-diallylaminocarbonyloxy-2- pyridine sulfonamide and 1.04 g (0.0038 mol) of N- (4,6-dimethoxypyrimidine-2- yl) phenyl carbamate in 40 ml of acetonitrile, 1.27 g (0.0084 mol) are added 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU). The solution is at 16 h Stirred at room temperature, then the acetonitrile under reduced Distilled off pressure, added 20 ml of water to the residue and with 2 acidified to pH 4 with normal hydrochloric acid. It is extracted with Dichloromethane, the organic phase dries over magnesium sulfate, filter off the desiccant and distill in the solvent reduced pressure. The residue is extracted with diethyl ether and is obtained after removal of the solvent residues under reduced Pressure 0.65 g (35.7% of theory) N - [(4,6-dimethoxypyrimidin-2-yl) - aminocarbonyl] -3-diallylaminocarbonyloxy-2-pyridinesulfonamide as tough Oil, the following chemical shifts in the 1 H-NMR spectrum (CDCl₃, 80 MHz) has: δ [ppm] = 3.80 (s, 6H, OCH₃), 3.75-4.20 (m, 4H, N-CH₂), 5.00-5.40 (m, 4H, CH₂ =), 5.50-6.10 (m, 2H, CH =), 5.90 (s, 1H, 5-H on pyrimidine), 7.70-8.00 (m, 2H, 4,5-H₂ on pyridine), 8.40 (m, 1H, 6-H on pyridine), 9.90 and 12.8 (broad, each 1H, NH).  

h) N - [(4,6-Dimethoxypyrimidin-2-yl) aminocarbonyl] -3- [N- (n-hexyl) -N- (methyl) aminocarbonyloxy] -2-pyridinesulfonamide (Example 29 from Table 1)

To a solution of 2.36 g (0.0075 mol) of 3- [N- (n-hexyl) -N- (methyl) - aminocarbonyloxy] -2-pyridinesulfonamide and 2.05 g (0.0075 mol) of N- (4,6- Dimethoxypyrimidin-2-yl) phenyl carbamate in 40 ml of acetonitrile is added 2.50 g (0.016 mol) of 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU). The solution is stirred for 16 h at room temperature, then 20 ml of water added and acidified to pH 4 with 2 normal hydrochloric acid. Man extracted with dichloromethane, the organic phase dries over MgSO₄, filter off the desiccant and distill in the solvent reduced pressure. The residue is treated with diisopropyl ether stirred and 2.8 g (75% of theory) of N - [(4.6- Dimethoxypyrimidin-2-yl) aminocarbonyl] -3- [N- (n-hexyl) -N- (methyl) - aminocarbonyloxy] -2-pyridinesulfonamide with a melting point of 100 ° C. (Dec.).

The other compounds in Table 1 below are analogous to Process of Examples a) to h) or those mentioned in the description Procedure received.

Abbreviations in Table 1:
Me = methyl
Et = ethyl
Pr = n-propyl,
Bu = butyl
Ph = phenyl
i-, s-, t-, c-alkyl = iso-, secondary, tertiary or cyclo-alkyl
Mp = melting point in ° C

Table 1

Compounds of formula (Ia)

B. Examples of formulation

• a) A dusting agent is obtained by adding 10 parts by weight of a Compound of formula (I) and 90 parts by weight of talc as an inert substance mixes and crushed in a hammer mill.
• b) a wettable powder which is readily dispersible in water is contained, by adding 25 parts by weight of a compound of the formula (I), 64 parts by weight of quartz containing kaolin as an inert substance, 10 parts by weight ligninsulfonic acid potassium and 1 part by weight of oleoylmethyl tauric acid Mixes sodium as a wetting and dispersing agent and in a pin mill grinds.
• c) A dispersion concentrate which is readily dispersible in water is obtained by 20 parts by weight of a compound of formula (I) with 6 parts by weight Parts of alkylphenol polyglycol ether (®Triton X 207), 3 parts by weight Isotridecanol polyglycol ether (8 EO) and 71 parts by weight paraffinic Mineral oil (boiling range e.g. approx. 255 to above 277 ° C) mixes and in one Grinding ball mill ground to a fineness of less than 5 microns.
• d) An emulsifiable concentrate is obtained from 15 parts by weight of one  Compound of formula (I), 75 parts by weight of cyclohexanone as Solvent and 10 parts by weight of ethylated nonylphenol as Emulsifier.
• e) A water-dispersible granulate is obtained by 75 parts by weight of a compound of formula (I),
  10 parts by weight of calcium lignosulfonic acid,
  5 parts by weight of sodium lauryl sulfate,
  3 parts by weight of polyvinyl alcohol and
  7 parts by weight of kaolin mixed, ground on a pin mill and the powder granulated in a fluidized bed by spraying water as the granulating liquid.
• f) Water-dispersible granules are also obtained by adding 25 parts by weight of a compound of the formula (I),
  5 parts by weight of 2,2′-dinaphthylmethane-6,6′-disulfonic acid sodium,
  2 parts by weight of oleoylmethyl tauric acid sodium,
  1 part by weight of polyvinyl alcohol,
  17 parts by weight of calcium carbonate and
  50 parts by weight of water are homogenized and pre-comminuted on a colloid mill, then ground on a bead mill and the suspension thus obtained is atomized and dried in a spray tower using a single-component nozzle.

C. Biological examples 1. Pre-emergence weed action

Seeds or rhizome pieces of monocotyledonous and dicotyledonous weed plants were grown in Plastic pots laid out in sandy loam and covered with earth. In the Formulated in the form of wettable powders or emulsion concentrates Compounds according to the invention were then in the form of an aqueous suspension or Emulsion with a water application rate of the equivalent of 600 to 800 l / ha in different doses applied to the surface of the earth. After the treatment, the pots were placed in the greenhouse and under good growing conditions for the weeds. The optical rating the damage to the plants or the emergence occurred after the emergence of the Test plants after a test period of 3 to 4 weeks compared to untreated controls. As the test results show, the Compounds according to the invention have a good herbicidal pre-emergence activity against a wide range of grasses and weeds. For example have the compounds of Examples 1-18, 21, 29, 32, 33, 34, 35, 51, 55, 58, 62, 70, 74, 82, 87 and 113 good herbicidal activity against harmful plants such as Sinapis alba, Chrysanthemum segetum, Avena sativa, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Setaria spp., Abutilon theophrasti, Amaranthus retroflexus and Panicum miliaceum pre-emergence in one Application rate of 0.3 kg and less active substance per hectare.

2. Post-emergence weed action

Seeds or rhizome pieces of monocotyledonous and dicotyledonous weeds were found in Plastic pots laid out in sandy clay soil, covered with earth and in Greenhouse grown under good growing conditions. Three weeks after sowing, the test plants were treated at the three-leaf stage. Formulated as wettable powder or emulsion concentrates Compounds according to the invention were in different doses  a water application rate of the equivalent of 600 to 800 l / ha to the green Plant parts sprayed and after about 3 to 4 weeks of standing Trial plants in the greenhouse under optimal growing conditions Effect of the preparations visually compared to untreated controls rated. The agents according to the invention also have good post-emergence properties herbicidal activity against a wide range of economically more important Grasses and weeds. For example, the connections of Examples 1-18, 21, 29, 32, 33, 34, 35, 51, 55, 58, 62, 70, 74, 82, 87 and 113 good herbicidal activity against harmful plants such as Sinapis alba, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Chrysanthemum segetum, Setaria spp., Abutilon theophrasti, Amaranthus retroflexus and Panicum miliaceum, Avena sativa in the post-emergence process with an application rate of 0.3 kg and less active ingredient per hectare.

3. Crop tolerance

In further experiments in the greenhouse, seeds of a larger number were found of crops and weeds laid out in sandy loam and with Earth covered. Some of the pots were immediately treated as described in section 1 treated, the rest set up in the greenhouse until the plants had developed two to three real leaves and then as described in section 2 described with the substances of the formula (I) according to the invention in sprayed different doses. Four to five weeks after the Application and service life in the greenhouse was assessed using an optical rating found that the compounds of the invention dicotyledonous Cultures such as B. Soy, cotton, rapeseed, sugar beet and potatoes in advance and post-emergence process undamaged even at high doses of active ingredient let. Some substances also spare from Gramineae crops such as e.g. B. barley, wheat, rye, sorghum, corn or rice. The connections of the formula (I) partly show a high selectivity and are therefore suitable for Combating unwanted plant growth in agricultural Cultures.

Claims (12)

1. Compounds of the formula (I) and their salts, wherein
R¹ and R² independently of one another (C₁-C₈) alkyl which is unsubstituted or by one or more radicals from the group halogen, nitro, cyano, (C₁-C₄) alkoxy, [(C₁-C₄) alkoxy] carbonyl, Aryl and substituted aryl is substituted, or (C₁-C₆) alkoxy, (C₃-C₆) alkenyl, (C₃-C₆) alkynyl or aryl, the aryl radical being unsubstituted or by one or more radicals from the group halogen, nitro , (C₁-C₄) alkyl, (C₁-C₄) alkoxy and [(C₁-C₄) alkoxy] carbonyl, or H, if the other of the substituents R² and R¹ on the N atom is not a hydrogen atom, or
R¹ and R² together with the N atom connecting them form a heterocyclic ring with 3-7 ring atoms and 0, 1 or 2 further heteroatoms from the group O, N and S, where the ring may be benzo-fused and unsubstituted or by one or more Radicals from the group (C₁-C₄) alkyl, (C₁-C₄) alkoxy, [(C₁-C₄) alkoxy] carbonyl and aryl is substituted,
R³ (C₁-C₄) alkyl, (C₁-C₃) haloalkyl, halogen, NO₂, CN, (C₁-C₃) alkoxy, (C₁-C₃) haloalkoxy, (C₁-C₃) alkylthio, (C₁- C₃) alkoxy- (C₁-C₃) alkyl, [(C₁-C₃) alkoxy] carbonyl, (C₁-C₃) alkylamino, di - [(C₁-C₃) alkyl] amino, (C₁- C₃) alkylsulfonyl, SO₂NRaR ^b or C (O) NR ^c R ^d ,
Ra, R ^b , R ^c , R ^d independently of one another H, (C₁-C₄) alkyl, (C₃-C₆) alkenyl, (C₃- C₆) alkynyl, [(C₁-C₄) alkyl] carbonyl, Arylcarbonyl, which is unsubstituted or substituted in the aryl radical, or in pairs Ra and R ^b or R ^c and R ^d together with the N atom connecting them, a heterocyclic saturated or unsaturated ring with 3-7 ring atoms and 0, 1 or 2 further heteroatoms from the group N, O and S, where the ring is unsubstituted or substituted,
R⁴ H or (C₁-C₄) alkyl, preferably H or CH₃, in particular H,
n 0, 1 or 2,
A is a residue of the formula X, Y independently of one another are H, halogen, (C₁-C₃) alkyl, (C₁-C₃) alkoxy or (C₁-C₃) alkylthio, the abovementioned alkyl-containing radicals being unsubstituted or singly or multiply by halogen or mono- or are substituted twice by radicals from the group (C₁-C₃) alkoxy and (C₁-C₃) alkylthio, or a radical of the formula NR⁵R⁶, (C₃-C₆) - cycloalkyl, (C₂-C₄) alkenyl, (C₂- C₄) alkynyl, (C₃-C₄) alkenyloxy or (C₃-C₄) alkynyloxy,
R⁵, R⁶ independently of one another H, (C₁-C₃) alkyl or (C₃-C₄) alkenyl,
Z CH or N,
X¹ CH₃, OCH₃, OC₂H₅ or OCF₂H,
Y¹ -O- or -CH₂-,
X² H₃, C₂H₅ or CH₂CF₃,
Y² OCH₃, OC₂H₅, SCH₃, SC₂H₅, CH₃ or C₂H₅,
X³ CH₃ or OCH₃,
Y³ H or CH₃,
X⁴ CH₃, OCH₃, OC₂H₅, CH₂OCH₃ or Cl,
Y⁴ CH₃, OCH₃, OC₂H₅ or Cl and
Y⁵ CH₃, C₂H₅, OCH₃ or Cl
mean. 2. Compounds and their salts according to claim 1, characterized in that
R¹ H, (C₁-C₄) alkyl which is unsubstituted or substituted by one or more radicals from the group halogen, cyano and (C₁-C₄) alkoxy, or (C₁-C₄) alkoxy, (C₃-C₆) -Alkenyl or (C₃-C₆) alkynyl and
R² (C₁-C₄) alkyl which is unsubstituted or substituted by one or more radicals from the group halogen, nitro, cyano, (C₁-C₄) alkoxy and (C₁-C₄) alkoxycarbonyl, or (C₁-C₄) Alkoxy, aryl, the aryl radical being unsubstituted or substituted by one or more radicals from the group halogen, nitro and (C₁-C₄) alkyl, or (C₃-C₆) - alkenyl or (C₃-C₆) alkynyl, or
R¹ and R² together with the N atom connecting them form a heterocyclic ring with 5-7 ring atoms and in addition to the N atom up to a further heteroatom from the group O and N, the ring being unsubstituted or by one or more radicals from the Group (C₁-C₄) alkyl, (C₁-C₄) alkoxycarbonyl and aryl is substituted,
mean. 3. Compounds and their salts according to claim 1 or 2, characterized in that
R¹ (C₁-C₄) alkyl and
R² (C₁-C₄) alkyl, (C₁-C₄) alkoxy or aryl which is unsubstituted or substituted by one or more of the radicals halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy and nitro, mean or
R¹ and R² together with the N atom connecting them represent an unsubstituted or substituted by (C₁-C₄) alkyl morpholine or piperidine ring and
R³ (C₁-C₄) alkyl, (C₁-C₃) haloalkyl, halogen or (C₁-C₃) alkoxy and
n 0, 1 or 2,
A is a residue of the formula one of the radicals X and Y (C₁-C₃) alkyl, (C₁-C₃) alkoxy, (C₁-C₃) haloalkyl, (C₁-C₃) haloalkoxy or [(C₁-C₂) alkoxy] - (C₁ -C₂) alkyl and the other radical Y or X (C₁-C₃) alkyl, (C₁-C₃) alkoxy, (C₁-C₃) - alkylthio, each of the latter 3 radicals unsubstituted or one or more times by Halogen or mono- or disubstituted by (C₁-C₃) alkoxy or (C₁-C₃) alkylthio, or halogen or a radical of the formula NR⁵R⁶, where R⁵ and R⁶ independently of one another H, (C₁-C₃) alkyl or Are (C₃-C₄) alkenyl, or (C₃-C₆) cycloalkyl, (C₂- C₄) alkenyl, (C₂-C₄) alkynyl, (C₃-C₄) alkenyloxy or (C₃-C₄) alkynyloxy
mean. 4. A process for the preparation of compounds of formula (I) and their salts, characterized in that

• a) a compound of the formula (II), with a heterocyclic carbamate of the formula (III), in which R * denotes optionally substituted phenyl or (C₁-C₄) alkyl,
  implements or
• b) a pyridylsulfonylcarbamate of the formula (IV) with an amino heterocycle of the formula (V) H-NR⁴-A (V) or
• c) a sulfonyl isocyanate of the formula (VI) with an amino heterocycle of the formula (V) H-NR⁴-A (V) or
• d) in a one-pot reaction, first reacting an amino heterocycle of the formula H-NR⁴-A (V) with phosgene in the presence of a base and reacting the intermediate formed with a pyridinesulfonamide of the formula (II),

where in the formulas (II) - (VI) R¹, R², R³, R⁴, A and n as in formula (I) are defined. 5. Compounds of formula (II) wherein R¹, R², R³ and n are as defined in formula (I) according to claim 1, 2 or 3. 6. A process for the preparation of a compound of formula (II) according to claim 5, characterized in that a compound of formula (VII)

• a) with a carbamoyl halide of the formula Hal-CO-NR¹R², in which Hal represents a halogen atom,

or

• b) in the case of R² = H with an isocyanate of the formula R¹-NC = O,

wherein in formula (VII) and the formulas under a) and b) R¹, R², R³ and n as are defined in formula (I), reacted and the obtained, with the t-butyl group protected sulfonamide with a strong acid to the sulfonamide of formula (II) implements. 7. Herbicides or plant growth regulators, thereby characterized in that it contains at least one compound of formula (I) or whose salt according to one of claims 1 to 3 and conventional Formulation aids included. 8. Use of the compounds of formula (I) or their salts after a of claims 1 to 3 as herbicides or plant growth regulators. 9. Procedures for controlling harmful plants or for Growth regulation of plants, characterized in that one or more compounds of formula (I) or their salts according to one of the Claims 1 to 3 on the plants, plant seeds or the soil or in which the plants grow.