EP0763027A1 - Phenylsulfonyl ureas with nitrogen substituents, method for their preparation and use as herbicides and plant growth regulators - Google Patents

Abstract

Salts of formula (I), wherein n is 0, 1, 2 or 3; R is a halogen, alkyl or alkoxy, independently of one another when n is greater than 1; R1 is a substituted or unsubstituted hydrocarbon radical or a substituted or unsubstituted heterocyclic radical; R2 is an acyl radical; R3 is hydrogen or C¿1?-C5 alkyl; MO is a metal or ammonium ion; X, Y are, independently of each other, a halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, each of the last three radicals being unsubstituted or substituted by one or more radicals from the group of halogen, C1-C4 alkoxy and C1-C4 alkoxy and C1-C4 alkylthio, or C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 alkinyl, C3-C6 alkenyloxy, C3-C6 alkinyloxy, mono- or di- (C1-C4-alkyl)-amino, and Z is CH or N, can be used as herbicides and plant growth regulators. The compounds (I) can be produced by the method disclosed in claims 5-7, for example by hydrogenation of 2-alkoxycarbonyl-5-nitrophenylsulfonyl ureas in the presence of anhydrides.

Description

description

Phenylsulfonylureas with nitrogen substituents; Process for their preparation and use as herbicides and plant growth regulators

The invention relates to the technical field of herbicides and plant growth regulators, in particular herbicides for the selective control of weeds and weeds in crops of useful plants.

It is known that heterocyclically substituted phenylsulfonylureas which have an amino or a functionalized amino group on the phenyl ring have herbicidal and plant growth-regulating properties; see EP-A-1515, US-A-4,892,946, US-A-4,981, 509, EP-A-1 16 518 (= US-A-4,664,695, US-A-4,632,695), DE-A-4236902 (WO 94/10154).

Surprisingly, it has now been found that salts of certain heterocyclically substituted phenylsulfonylureas are particularly suitable as herbicides or plant growth regulators.

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

where n is 0, 1, 2 or 3,

R is halogen, alkyl or alkoxy, each independently of the other

Substituents R, if n is greater than 1, R ^{1 is} an unsubstituted or substituted hydrocarbon radical or an unsubstituted or substituted heterocyclic radical,

R ^{2 is} an acyl radical,

R ^{3 is} hydrogen or C _r C ₅ alkyl,

MΘ an equivalent of a cation,

X, Y independently of one another halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C * -C ₆ -alkylthio, where each of the three last-mentioned radicals is unsubstituted or by one or more radicals from the group halogen, C --C ₄ alkoxy and C - * - C ₄ alkylthio, or C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ alkenyloxy , C ₂ -C ₆ alkynyloxy, mono- or di- (C., -C ₄ alkyl) amino and

Z is CH or N.

In formula (I) and all the following formulas, the alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio radicals and the corresponding unsaturated and / or substituted radicals in the carbon skeleton can each be straight-chain or branched. Unless specifically stated, the lower carbon skeletons, e.g. with 1 to 4 carbon atoms or in the case of unsaturated groups with 2 to 4 carbon atoms, preferred. Alkyl radicals, also in the composite meanings such as alkoxy, haloalkyl etc., mean e.g. Methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, i-hexyl and 1,3-dimethylbutyl, heptyls, such as n-heptyl, 1-methylhexyl and 1, 4-dimethylpentyl; Alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals; Alkenyl means e.g. Allyl, 1-methylprop-2-en-1 -yl, 2-methyl-prop-2-en-1 -yl, but-2-en-1 -yl, but-3-en-1 -yl, 1 - Methyl-but-3-en-1-yl and 1-methyl-but-2-en-1-yl; Alkynyl means e.g. Propargyl, but-2-in-1-yl, but-3-in-1-yl, 1-methyl-but-3-in-1-yl.

Halogen means, for example, fluorine, chlorine, bromine or iodine. Haloalkyl, alkenyl and alkynyl mean partly or completely by halogen, preferably by fluorine, chlorine and / or bromine, in particular by fluorine or chlorine substituted alkyl, alkenyl or alkynyl, for example CF ₃ , CHF ₂ , CH ₂ F, CF ₃ CF ₂ , CH ₂ FCHCI, CCI ₃ , CHCI ₂ , CH ₂ CH ₂ CI; Haloalkoxy is, for example, OCF ₃ , OCHF ₂ , OCH ₂ F, CF ₃ CF ₂ O, OCH ₂ CF ₃ and OCH ₂ CH ₂ CI; The same applies to haloalkenyl and other halogen-substituted radicals.

A hydrocarbon residue is a straight chain, branched or cyclic and saturated or unsaturated aliphatic or aromatic hydrocarbon residue, e.g. Alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or aryl; Aryl here means a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl, fluorenyl and the like, preferably phenyl; a hydrocarbon radical is preferably alkyl, alkenyl or alkynyl having up to 12 carbon atoms or cycloalkyl having 5 or 6 ring atoms or phenyl;

A heterocyclic radical or ring can be saturated, unsaturated or heteroaromatic; it contains one or more hetero ring atoms, preferably from the group N, O and S; for example, it has 3 to 8 ring atoms; it is preferably 5 or 6-membered and contains 1, 2 or 3 hetero ring atoms. The heterocyclic radical can be, for example, a heteroaromatic radical or ring (heteroaryl), such as, for example, a mono-, bi- or polycyclic aromatic system in which at least 1 ring contains one or more heteroatoms, for example pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, thienyl, Thiazolyl, oxazolyl, furyl, pyrrolyl, pyrazolyl and imidazolyl, or is a partially or completely hydrogenated radical such as oxiranyl, pyrrolidyl, piperidyl, piperazinyl, dioxolanyl, morpholinyl, tetrahydrofuryl. Possible substituents for a substituted heterocyclic radical are the substituents mentioned below, and additionally oxo. The oxo group can also occur on the hetero ring atoms, which can exist in different oxidation states, for example in the case of N and S. Substituted radicals, such as substituted hydrocarbon radicals, for example substituted alkyl, alkenyl, alkynyl, aryl, phenyl and benzyl, or substituted heteroaryl, mean, for example, a substituted radical derived from the unsubstituted basic body, the substituents in principle being able to be selected from a wide range of structurally very different radicals ; Substituents on the main body are, for example, functional groups, including hydrocarbon radicals or heterocyclic radicals which are each connected to the main body by heteroatoms or other functional groups, or are carbocyclic or heterocyclic radicals which are directly linked to the main body, or, in the case of cyclic main bodies, also acyclic hydrocarbon residues that are directly connected to the base body. In principle, the substituents mentioned can have further substituents. Substituents on the base body mean, for example, one or more, preferably 1, 2 or 3, radicals from the group halogen, alkoxy, haloalkoxy, alkylthio, hydroxy, amino, nitro, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino such as acylamino, mono- and dialkylamino, and alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and, in the case of cyclic bases, also alkyl and haloalkyl as well as unsaturated aliphatic radicals corresponding to the saturated hydrocarbon-containing radicals mentioned, such as alkenyl, alkynyl, alkenyloxy, etc. ; in the case of radicals with carbon atoms, those with 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, are preferred. As a rule, preferred substituents are selected from the group halogen, for example fluorine and chlorine, C - C ₄ alkyl, preferably methyl or ethyl, C, -C ₄ - haloalkyl, preferably trifluoromethyl, C ** - C ₄ alkoxy, preferably Methoxy or ethoxy, C- _] -C ₄ haloalkoxy, nitro and cyano. The substituents methyl, methoxy and chlorine are particularly preferred. Substituents on the base body are, for example, also heterocyclic radicals, preferably saturated heterocyclic radicals having 3 to 6 ring atoms and an oxygen atom as a hetero ring atom, which may also be substituted by further substituents such as C ₁ -C ₄ alkyl. Optionally substituted phenyl is preferably phenyl which is unsubstituted or one or more times, preferably up to three times, by identical or different radicals from the group halogen, C -C ₄ alkyl, CC ₄ alkoxy, C ₁ -C ₄ haloalkyl, C ., - C ₄ -haloalkoxy and nitro is substituted, for example o-, m- and p-tolyl, dimethylphenyls, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoro- and trichlorophenyl, 2nd , 4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl.

An acyl residue means the residue of an organic acid, for example the residue of a carboxylic acid and residues of derivatives derived therefrom such as thiocarboxylic acid, optionally N-substituted iminocarboxylic acids, or the rest of carbonic acid monoesters, optionally N-substituted carbamic acid, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids. Acyl means, for example, formyl, alkylcarbonyl such as (C 1 -C ₄ -alkyl) carbonyl, phenylcarbonyl, where the phenyl ring can be substituted, for example as shown above for phenyl, or alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, N-alkyl -1-aminoalkyl and other residues of organic acids.

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

The compounds of formula (I) are salts in which the cation is preferably a cation which can be used in the field of agriculture. These salts are, for example, metal salts, preferably alkali or alkaline earth salts, in particular sodium and potassium salts, or also ammonium salts and ammonium salts substituted by organic radicals.

Of particular interest are compounds of the formula (i) according to the invention in which n is 0, 1 or 2, preferably 0 and 1, in particular 0,

R halogen, C, -C ₃ alkyl or C ₁ -C ₃ alkoxy,

R ^{1 is} an aliphatic or cycloaliphatic hydrocarbon radical with up to 24 C atoms which is unsubstituted or substituted, or an unsubstituted or substituted saturated heterocyclic radical with 3 to 6 ring atoms, preferably C -C ₆ alkyl, C ₂ -C ₆ - Alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, each of the four last-mentioned radicals being unsubstituted or by one or more radicals from the group halogen, CN, C ₁ -C ₄ -alkoxy, C, -C _4- haloalkoxy, mono- (C ₁ -C ₄ alkyl) amino, di- (C., - C ₄ alkyl) amino, C _r C ₄ alkylsulfonyl, C ₁ -C ₄ alkylsulfinyl, (C ₁ -C ₄ alkoxy) carbonyl, aminocarbonyl, mono- (C- _| -C ₄ alkyl) aminocarbonyl, di- (C- _| -C ₄ alkyl) - aminocarbonyl, unsubstituted phenyl, substituted phenyl, unsubstituted heterocyclic Radical and substituted heterocyclic radical is substituted, or a heterocyclic radical having 3, 4, 5 or 6 ring atoms and an oxygen atom as a hetero ring atom, the rest being unsubstituted ized or substituted by one or more radicals from the group C ₁ -C ₄ alkyl,

R ² CO-R ⁴ , CO-OR ⁵ , CO-NR ⁶ R ⁷ , SO ₂ -R ⁸ ,

R ³ H, C _r C ₄ alkyl,

R ^{4 is} hydrogen, C _r C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, where each of the four last-mentioned radicals is unsubstituted or by one or more radicals from the Group halogen, CN, C _r C ₄ alkoxy, C, -C ₄ haloalkoxy, mono- (C ** - C ₄ alkyl) amino, di (C _r C ₄ alkyl) amino, C _r C ₄ - alkylsulfonyl, C _r C ₄ alkylsulfinyl, (C _r C ₄ alkoxy) carbonyl, aminocarbonyl, mono- (C, -C ₄ alkyl) aminocarbonyl, di (C ₁ -C ₄ alkyl) a is substituted in inocarbonyl, phenyl and substituted phenyl, or phenyl which is unsubstituted or substituted,

R ⁵ analogous to R ⁴ , except hydrogen,

R ⁶ and R ⁷ are independently H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ - alkynyl, where each of the three last-mentioned radicals is unsubstituted or substituted by one or more radicals from the group halogen such as F, Cl and Br, and CN, C _r C ₄ alkoxy, C _r C ₄ haloalkoxy, mono- (C _r C ₄ alkyl) amino, di (C _r C ₄ alkyl) amino , C _r C ₄ alkylsulfonyl, C _r C ₄ alkylsulfinyl, (C _r C ₄ alkoxy) carbonyl, aminocarbonyl, mono- (C ₁ -C ₄ alkyl) aminocarbonyl and di- (C _r C alkyl) ) -aminocarbonyl is substituted, or

R ⁶ and R ⁷ together with the N atom bonded to them form an unsubstituted or substituted heterocyclic ring of four to eight ring atoms which, including the substituents, contains up to 1 8 C atoms, preferably up to 12 C atoms,

R ⁸ C-. -Cg-alkyl, C ₂ -C ₅ alkenyl, each of the latter two radicals unsubstituted or by one or more radicals from the group halogen, C _r C ₄ alkoxy, C _r C ₄ haloalkoxy, mono- (C _r C ₄ -alkyl) -amino and di- (C- _| -C -alkyl) -amino is substituted,

Mθ the cation equivalent of an alkali or alkaline earth metal, such as Na ^+, K ^+, y ₂ Mg ^{2 +} and y ₂ Ca ^{2 +,} or NH ₄ ^{+ _1/2} Zn ^{2 +,} R ° NH ₃ ^+, R ° ₂ NH ₂ ⁺ , R ° ₃ NH ⁺ or R ° ₄ N ⁺ ,

R ° C _r C ₆ alkyl or benzyl,

X, Y independently of one another halogen, C - * - C ₄ alkyl, C- _| -C ₄ -alkoxy, C * -C ₄ - alkylthio, where each of the last three radicals is unsubstituted or substituted by one or more radicals from the group halogen, C., - C ₄ -alkoxy and C ** - C ₄ -alkylthio is mono- or di (C ₁ -C ₄ alkyl) amino, C ₃ -C ₆ cycloalkyl, C ₂ -C ₅ alkenyl or C ₂ -C ₅ alkynyloxy and

Z is CH or N.

Preferably, compounds of the invention of formula (I) wherein R ¹ is C _r C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ -cycloalkyl, where each of the four last-mentioned radicals are unsubstituted or by one or more radicals from the group F, Cl, Br, I, CN, OCH ₃ , OCF ₃ , N (CH ₃ ) ₂ , SO ₂ CH ₃ , CO ₂ CH ₃ , CO ₂ N (CH ₃ ) ₂ and phenyl, or a radical of the formulas A- to A ₇

(A,) (A ₂ ) (A ₃ ) (A ₄ )

(A ₅ ) (A ₆ ) (A ₇ )

CO-R ⁴ , CO-OR ⁵ , CO-NR ⁶ R ⁷ , SO ₂ -R ⁸ , H or CH ₃ ,

Hydrogen, C _r C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, each of the four last-mentioned radicals unsubstituted or by one or more radicals from group F , Cl, Br, I, CN, OCH ₃ , OCF ₃ , N (CH ₃ ) ₂ , SO ₂ CH ₃ , CO ₂ CH ₃ , CON (CH ₃ ) ₂ and phenyl, or phenyl which is unsubstituted or bis three times substituted by identical or different radicals from the group halogen, CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , CF ₃ , C ₂ H ₅ CI, OCHF ₃ , OCHF ₂ ,

R analogous to R ⁴ , except hydrogen,

R ⁶ and R ⁷ are independently H, C, -. C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ - alkynyl, where each of the three last-mentioned radicals is unsubstituted or substituted by one or more radicals from the group F, Cl, Br, CN, OCH ₃ , OCF ₃ , N (CH ₃ ) ₂ , SO ₂ CH ₃ , CO ₂ CH ₃ and CON (CH ₃ ) ₂ , and

R ⁸ C _r C ₅ alkyl or C ₂ -C ₅ alkenyl, each of the latter two

Residues unsubstituted or substituted by one or more radicals from the group F, Cl, Br, OCH ₃ or N (CH ₃ ) ₂ . Preferred compounds of the formula (I) according to the invention are those in which

R ¹ C- _j -C ₆ alkyl, preferably CH ₃ , or

R ² CO-R ⁴ , preferably CHO, CO-CH ₃ , CO-CH ₂ CH ₃ , cyclopropyl-carbonyl,

Isopropyl-carbonyl or t-butyl-carbonyl, or R ² CO-OR ⁵ , preferably COOCH ₃ , COOC ₂ H ₅ and COOCH ₂ CH ₂ CI, or R ² CO-NR ⁶ R ⁷ , preferably CONH ₂ , CONHCH ₃ , CO-NH-C ₂ H ₅ , CON (CH ₃ ) ₂ , or R ² SO ₂ -R ⁸ , preferably SO ₂ CH ₃ , SO ₂ C ₂ H ₅ , SO ₂ CH ₂ F, SO ₂ CH ₂ CI, or R ³ is H or Mθ Na ^+, K ^{+ _1/2} Mg ^{2 +,} y ₂ Ca ^{2 +,} NH ₄ ^+, H ₂ NEt ₂ ^+, H ₃ NC ₄ H ₉ ^+, NH (C ₂ H _{5) 3} ⁺ ,

N (C ₂ H ₅ ) ₄ ⁺ , N (CH ₃ ) ₄ ⁺ , HN (CH ₃ ) ₃ ⁺ , preferably Na ⁺ , K ⁺ , ^η / ₂ Mg ^{2 +} ,

_^1/2 Ca ^2+, NH ₄ ⁺ -, NH (C ₂ H _{5) 3} ^+, or R ° C- _j -CG alkyl, preferably isopropyl, methyl, ethyl, n-propyl, n-butyl, or X , Y OCH ₃ , OC ₂ H ₅ , SCH ₃ , NHCH ₃ , N (CH ₃ ) ₂ , CH ₃ , OCH ₂ CF ₃ , in particular

OCH ₃ , Me or Cl or a combination of the above preferred radicals.

Compounds of the formula (I) in which

R CH ₃ ,

R ² CO-CH ₃ , CO-CH ₂ CH ₃ , isopropyl-carbonyl, cyclopropyl-carbonyl,

COOCH ₃ , COOC ₂ H ₅ , in particular COCH ₃ , COCH ₂ CH ₃ or COOCH ₃ ,

R ³ H, one of the radicals X and Y

Halogen, C ₁ -C ₂ -alkyl, C ₁ -C ₂ -alkoxy, C., - C -alkylthio, where each of the last three radicals unsubstituted or by one or more radicals from the group halogen, C - C ₂ - Alkoxy and C ₁ -C ₂ alkylthio is substituted, or mono- or di (C ₁ -C ₂ alkyl) amino, preferably halogen, methyl or methoxy, and the other of the radicals X and Y

C _r C ₂ alkyl, C _r C ₂ haloalkyl, C _r C ₂ alkoxy, C, -C ₂ haloalkoxy or C - C ₂ alkylthio, preferably methyl or methoxy, Z is CH or N, preferably CH.

Examples of compounds according to the invention are, in particular, compounds of the formula (I) in which

R ¹ = methyl, R ² = acetyl, R ³ = H, X = methoxy, Y = methoxy,

Z = CH and M ⁺ = Na ⁺ ;

R ¹ = methyl, R ² = acetyl, R ³ = H, X = methoxy, Y = methoxy,

Z = CH and M ⁺ = K ⁺ ;

R ¹ = methyl, R ² = acetyl, R ³ = H, X = methoxy, Y = methoxy,

Z = CH and M ⁺ = NH ₄ ⁺ ;

R ¹ = methyl, R ² = acetyl, R ³ = H, X = methoxy, Y = methyl, Z = CH and M ⁺ = Na ⁺ ;

R ¹ = methyl, R ² = acetyl, R ³ = H, X = methoxy, Y = methyl, Z = CH and M ⁺ = K ⁺ ;

R ¹ = methyl, R ² = acetyl, R ³ = H, X = methoxy, Y = methyl, Z = CH and M ⁺ = NH ₄ ⁺ ;

R ¹ = methyl, R ² = acetyl, R ³ = H, X = methyl, Y = methyl, Z = CH and M ⁺ = Na ⁺ ;

R ¹ = methyl, R ² = acetyl, R ³ = H, X = methyl, Y = methyl, Z = CH and M ⁺ = K ⁺ ;

R ¹ = methyl, R ² = acetyl, R ³ = H, X = methyl, Y = methyl, Z = CH and M ⁺ = NH ₄ ⁺ ;

R = methyl, R ² = propionyl, R ³ = H, X = methoxy, Y = methoxy,

Z = CH and M ⁺ = Na ⁺ ;

R ¹ = methyl, R ² = propionyl, R ³ = H, X = methoxy, Y = methyl,

Z = CH and M ⁺ = Na ⁺ ;

R ¹ = methyl, R ² = propionyl, R ³ = H, X = methyl, Y = methyl,

Z = CH and M ⁺ = Na ⁺ ;

R ¹ = methyl, R ² = acetyl, R ³ = H, X = methoxy, Y = methoxy,

Z = CH and M ⁺ = NH (C ₂ H ₅ ) ₃ ⁺ ; R ¹ = methyl, R ² = acetyl, R ³ = H, X = methoxy, Y = methoxy,

Z = CH and M ⁺ = N (CH ₃ ) ₄ ⁺ ;

R ¹ = methyl, R ² = methoxycarbonyl, R ³ = H, X = methoxy,

Y = methoxy, Z = CH and M ⁺ = Na ⁺ ;

R ¹ = methyl, R ² = methoxycarbonyl, R ³ = H, X = methoxy,

Y = methoxy, Z = CH and M ⁺ = K ⁺ ;

R ¹ = methyl, R ² = methoxycarbonyl, R ³ = H, X = methoxy,

Y = methoxy, Z = CH and M ⁺ = NH ₄ ⁺ ;

R ¹ = methyl, R ² = methoxycarbonyl, R ³ = H, X = methoxy,

Y = methyl, Z = CH and M ⁺ = Na ⁺ ;

R = methyl, R ² = methoxycarbonyl, R ³ = H, X = methoxy,

Y = methyl, Z = CH and M ⁺ = K ⁺ ;

R ¹ = methyl, R ² = methoxycarbonyl, R ³ = H, X = methoxy,

Y = methyl, Z = CH and M ⁺ = NH ₄ ⁺ ;

R ¹ = methyl, R ² = methoxycarbonyl, R ³ = H, X = methyl, Y = methyl,

Z = CH and M ⁺ = Na ⁺ ;

R ¹ = methyl, R ² = methoxycarbonyl, R ³ = H, X = methyl, Y = methyl,

Z = CH and M ⁺ = K ⁺ ;

R ¹ = methyl, R ² = methoxycarbonyl, R ³ = H, X = methyl, Y = methyl,

Z = CH and M ⁺ = NH ₄ ⁺ ;

R ¹ = methyl, R ² = ethoxycarbonyl, R ³ = H, X = methoxy,

Y = methoxy, Z = CH and M ⁺ = Na ⁺ ;

R ¹ = methyl, R ² = ethoxycarbonyl, R ³ = H, X = methoxy, Y = methyl,

Z = CH and M ⁺ = Na ⁺ ;

R ¹ = methyl, R ² = ethoxycarbonyl, R ³ = H, X = methyl, Y = methyl,

Z = CH and M ⁺ = Na ⁺ ;

R ¹ = methyl, R ² = methoxycarbonyl, R ³ = H, X = methoxy,

Y = methoxy, Z = CH and M ⁺ = NH (C ₂ H ₅ ) ₃ ⁺ ;

R ¹ = methyl, R ² = methoxycarbonyl, R ³ = H, X = methoxy,

Y = methoxy, Z = CH and M ⁺ = N (CH ₃ ) ₄ ⁺ ; The present invention further provides processes for the preparation of the compounds of the formula (I) according to the invention, characterized in that a compound of the formula

with a suitable base of the formula (IM)

M ^Θ X ^θ (III),

wherein X ^{θ is} an anion equivalent, eg ^θ OH, / ₂ CO ₃ ^{2 θ} , ^θ O- (C _r C ₄ ) alkyl, ^θ O-Ar or H ^θ , and

M ^θ as defined in said formula (I), and

Ar means aryl

or, in the case of an ammonium salt, correspondingly with ammonia or an organic amine, preferably a compound of the formula (IV)

H _m NR ° ₃ - _m (IV),

wherein m = 0, 1, 2 or 3 and R ° is as defined in formula (I).

The reaction of the compounds (II) with the bases of the formula (III) or the amines of the formula (IV) to give the salts of the formula (I) is preferably carried out in inert solvents, such as, for example, dichloromethane, acetonitrile, dioxane, tetrahydrofuran (THF) , N-methylpyrrolidine, dimethylformamide, dimethylacetamide, water or alcohols, such as methanol, ethanol or isopropanol, or also in solvent mixtures at temperatures from -20 ° C to the boiling point of the particular solvent, preferably from -10 to 80 ° C. The salts of the formula (I) can be prepared from the sulfonylureas (II) by adding suitable bases to the formulation auxiliaries or in a tank mix, ie the compounds of the formula (I) are only in the formulation or shortly before application in Tank mix formed from the sulfonylureas of the formula (II).

The compounds of the formula (II) are known from the literature mentioned above or can be prepared analogously to the processes described there.

The following reaction sequences (1) to (8) are examples of different ways of producing the intermediates of the formula (II):

Scheme 1: Synthetic routes to compounds of the formula (II)

(V) (VI)

(V) (VI I)

⁽³⁾

(4) - * (II)

(IX) (VI I)

(X) (V I I)

(X I)

(x i l)

In the formulas (V) - (XIII), R, R ¹ , R ² , R ³ , X, Y, Z and n have the meaning given in (II), with R ² = COR ⁴ in the reaction sequence (6) and in the reaction sequences (7) and (8) the acylating agent or addition reagent must be selected in the usual manner in accordance with the meaning of R ² .

The reaction of compounds of formula (V) with isocyanates of formula (VI) is carried out analogously to processes known from the literature (EP-A-232 067, EP-A-166 516) at -10 ° C. to 150 ° C., preferably 20 to 100 ° C, in an inert solvent, such as acetone or acetonitrile, in the presence of a suitable base, such as triethylamine or potassium carbonate (Scheme 1, (1)). The reaction of the sulfonamides of the formula (V) with aryl chloroformate and heterocyclic amines (VII) gives the sulfonylureas (II) (cf. US Pat. No. 4,994,571). First, the corresponding sulfonyl carbamates (XIV) are formed from the sulfonamides (V) and, for example, phenyl chloroformate in the presence of a suitable base, such as triethylamine or potassium carbonate. The compounds (XIV) can be converted with heterocyclic amines to the sulfonylureas (II) (Scheme 1, (2)).

Heterocyclic carbamates of formula (VIII) react with sulfonamides (II) in the presence of suitable bases, e.g. organic nitrogen bases (e.g. 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) or triethylamine), carbonates (e.g. potassium carbonate, sodium carbonate), alcoholates (e.g. sodium methoxide, sodium ethanolate) or phenolates (e.g. sodium phenolate) in inert solvents , such as Acetonitrile, methylene chloride, dioxane or THF, at temperatures from -10 ° C to the boiling point of the respective solvent. The carbamates required for the reaction are known from the literature or can be prepared analogously to known processes (cf. EP-A-70 804; US-A-4,480, 101; EP-A-562 575; EP-A-562 576) (see scheme 1, (3)).

The reaction of the sulfochlorides (IX) with the amino heterocycles of the formula (VII) and cyanates such as sodium cyanate and potassium cyanate takes place, for example, in aprotic solvents, such as, for example, acetonitrile, optionally in the presence of bases, for example 0.5 to 2 equivalents of base, or in basic aprotic ones Solvents at temperatures between -10 and 100 ° C, preferably between -10 and 60 ° C, in particular at 15 to 40 ° C. Suitable bases or basic aprotic solvents are, for example, pyridine, picoline or lutidine or a mixture of these (cf. US Pat. No. 5,157,119) (Scheme 1, (4)). The phenylsulfonyl isocyanates of the formula (X) can be prepared, for example, analogously to the processes from EP-A-184 385 from compounds of the formula (V), for example with phosgene. The reaction of the compounds (X) with the amino heterocycles of the formula (VII) is preferably carried out in inert, aprotic solvents, such as, for example, dioxane, acetonitrile or tetrahydrofuran, at temperatures between 0 ° C. and the boiling point of the solvent (Scheme 1, (5) ).

The above-mentioned syntheses of the sulfonylureas of the formula (II) according to Schemes 1, (1) to (5) are new and likewise a subject of the invention. The invention also relates to a process for the preparation of the intermediates of the formula (II), characterized in that a nitro-substituted phenylsulfonylurea of the formula (XI) mentioned is catalytically hydrogenated on the nitro group in the presence of an acylating agent of the formula (R ⁴ CO) ₂ O and reacted with the acylating agent (Scheme 1, (6)).

The catalytic hydrogenation of the nitro group can be carried out analogously to customary conditions for catalytic hydrogenations with hydrogen in the presence of a suitable hydrogenation catalyst, for example from group VIII of the periodic table, such as Ni, Pd, Pt and Rh, but the hydrogenation is carried out in the presence of the acylating agent with which the nitro group reduced to the amino group is to be acylated. For example, a suspension of a compound of the formula (XI), a suitable anhydride, such as, for example, acetic anhydride, and a suitable catalyst, such as, for example, Raney-Ni or palladium on carbon, is carried out under a hydrogen atmosphere with, for example, 1 to 100 atm of H ₂ - Pressure, preferably 1 to 10 atm H ₂ pressure stirred. The reaction can also be carried out with the addition of inert solvents, such as, for example, acetic acid, propionic acid, dimethylformamide, N-methylpyrrolidone or acetic acid dimethylamide. Hydrogenolysis of the nitro group of compounds (XI) in the presence of acid anhydrides (Scheme 1, (6)) enables the sulfonylureas (II) to be prepared according to a new one and inventive method, which is an advantageously short synthesis route with surprisingly good yields.

In addition, there are two other processes for obtaining compounds of the formula (II); see Schemes 1, (7) and (8). These methods are described in the literature (US-A-4,892,946).

The eight processes mentioned for the synthesis of compounds of the formula (II) (Scheme 1) can be combined directly with the deprotonation to prepare the salts of the formula (I), for example by isolating the salts of the formula (I) from a basic reaction medium instead of neutral compounds of formula (II), which are obtained from neutral or acidic reaction medium. Suitable one-pot syntheses are characterized, for example, by adding suitable bases, such as Na ₂ CO ₃ , NaOH, NaOCH ₃ , etc., to the reaction mixtures from the preparation of compounds of the formula (II) and subsequent isolation of the salts of the formula (I). These processes for the direct recovery of the compounds of formula (I) are also new and the subject of this invention.

The “inert solvents” referred to in the above process variants mean in each case solvents which are inert under the respective reaction conditions but do not have to be inert under any reaction conditions.

The compounds of formula (I) according to the invention have excellent herbicidal activity against a broad spectrum of economically important mono- and dicotyledonous harmful plants. Perennial weeds that are difficult to control and that sprout from rhizomes, rhizomes or other permanent organs are also well captured by the active ingredients. It does not matter whether the substances are applied by pre-sowing, pre-emergence or post-emergence. In particular, some representatives of the monocotyledonous and dicotyledonous weed flora, which are caused by Compounds according to the invention can be controlled without any restriction to certain types being intended by the naming.

On the side of the monocot weed species, e.g. Avena, Lolium, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria as well as Cyperus species from the annual group and on the part of the perennial species Agropyron, Cynodon, Imperata and Sorghum as well as perennial Cyperus species are well recorded.

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

Weeds occurring in rice under the specific crop conditions, e.g. Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus are also superbly controlled by the active compounds according to the invention.

If the compounds according to the invention are applied to the surface of the earth before germination, either the weed seedlings emerge completely or the weeds grow to the cotyledon stage, but then stop growing and finally die completely after three to four weeks.

When the active ingredients are applied to the green parts of the plants in the post-emergence process, there is also a drastic growth stop very quickly after the treatment and the weed plants remain at the growth stage at the time of application or die completely after a certain time, so that one for the crop plants harmful weed competition is eliminated very early and sustainably. Although the compounds according to the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, crop plants of economically important crops such as, for example, wheat, barley, rye, rice, maize, sugar beet, cotton and soybeans are only insignificantly or not at all damaged. For these reasons, the present compounds are very suitable for the selective control of undesired plant growth in agricultural crops.

In addition, the substances according to the invention have excellent growth-regulating properties in crop plants. They intervene to regulate the plant's own metabolism and can thus be used to specifically influence plant constituents and to facilitate harvesting, e.g. by triggering desiccation and stunted growth. Furthermore, they are also suitable for general control and inhibition of undesirable vegetative growth without killing the plants. Inhibiting vegetative growth plays a major role in many monocotyledonous and dicotyledonous crops, as this can reduce or completely prevent storage.

The compounds according to the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the customary formulations. The invention therefore also relates to herbicidal and plant growth-regulating compositions which comprise compounds of the formula (I).

The compounds of formula (I) can be formulated in different ways, depending on which biological and / or chemical-physical parameters are specified. Possible formulation options are, for example: 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 formulation types are known in principle and are described, for example, in: Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th Edition 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, NY , 1 973; K. Martens, "Spray Drying" Handbook, 3rd Ed. 1 979, G. Goodwin Ltd. London.

The necessary formulation aids such as inert materials, surfactants, solvents and other additives are also known and are 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. 1,963; 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. 1,964; Schönfeldt, "Interface-active ethylene oxide adducts", Wiss. Publishing company, Stuttgart 1976; Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986.

On. Based on these formulations, combinations with other pesticidally active substances, e.g. Manufacture insecticides, acaricides, other herbicides, fungicides, safeners, fertilizers and / or growth regulators, e.g. in the form of a finished formulation or as a tank mix.

Spray powders are preparations which are uniformly dispersible in water and which, in addition to the active substance, contain not only a diluent or an inert substance, but also ionic and / or nonionic surfactants (wetting agents, dispersants), for example polyoxyethylated ones Alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkane sulfonates, alkylbenzenesulfonates, sodium lignin sulfonate, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, sodium dibutylnaphthalene sulfonate or also oleoyl acid. For the preparation of the wettable powders, the herbicidal active ingredients are finely ground, for example in conventional apparatus such as hammer mills, blower mills and air jet mills, and mixed at the same time or subsequently with the formulation auxiliaries.

Emulsifiable concentrates are made by dissolving the active ingredient in an organic solvent e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of the organic solvents with the addition of one or more surfactants of ionic and / or nonionic type (emulsifiers). Examples of emulsifiers which can be used are: 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. Sorbitan fatty acid esters or polyoxethylene sorbitan esters such as e.g. Polyoxyethylene sorbitan fatty acid esters.

Dusts are obtained by grinding the active ingredient with finely divided solid substances, e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.

Suspension concentrates can be water or oil based. They can be prepared, for example, by wet grinding using commercially available bead mills and, if appropriate, addition of surfactants, such as those already listed above for the other types of formulation. Emulsions, for example oil-in-water emulsions (EW), can be prepared, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, such as those already listed above for the other types of formulation.

Granules can either be produced by spraying the active ingredient onto adsorbable, granulated inert material or by applying active ingredient concentrates by means of adhesives, e.g. Polyvinyl alcohol, sodium polyacrylic acid or mineral oils, on the surface of carriers such as sand, kaolinite or granulated inert material. Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules, if desired in a mixture with fertilizers.

Water-dispersible granules are generally produced using the customary methods, such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material.

The agrochemical preparations generally contain 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of active compound of the formula (I).

The active ingredient concentration in wettable powders is, for example, about 10 to 90% by weight, the remainder to 100% by weight consists of customary formulation components. In the case of emulsifiable concentrates, the active substance concentration can be about 1 to 90, preferably 5 to 80,% by weight. Dust-like formulations contain 1 to 30, preferably mostly 5 to 20% by weight of active ingredient, sprayable solutions 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 in liquid or solid form and which granulating aids, fillers, etc. are used. With those in water In dispersible granules, the active ingredient content is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.

In addition, the active ingredient formulations mentioned may contain the customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreezes and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and the pH and Agents influencing viscosity.

Known active ingredients, such as those described, for example, in Weed Research 26, 441 -445 (1 986), or "The Pesticide Manual", 9th edition, The British Crop Protection, can be used as combination partners for the active ingredients according to the invention in mixture formulations or in the tank mix Council, 1990/91, Brackneil, England, and the literature cited therein. Examples of herbicides known from the literature which can be combined with the compounds of the formula (I) are the following active ingredients (note: the compounds are 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 51 6 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 1 84927, ie 2- [4 - [(5-chloro-3-fluoro-2-pyridinyl) -oxy] - phenoxy-propanoic acid and 2-propynyl ester; chlomethoxyfen; chloramben; chlorazifop-butyl, pirifenop-butyl; chlorbromuroπ; chlorobufam; chlorfenac; chlorflurecol-methyl; chloridazon; chlorimuron ethyl; chlorπitrofen; 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; desmedipham; 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 1 77, 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-1 H-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, p. clomazone; fenoxaprop-ethyl; fenuron; flamprop-methyl; flazasulfuron; fluazifop and its ester derivatives; fluchloralin; flumetsulam; N- [2,6-difluorophenyl] -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; halosates; 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-1 H-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] -1 H-1, 2,4-triazole-1-carboxamide; thiazafluron; thifensulfuron-methyl; thiobencarb; tiocarbazil; tralkoxydim; tri-allate; triasulfuron; triazofenamide; tribenuron-methyl; triclopyr; tridiphane; trietazine; trifluralin; trimeturon; vernolate; WL 1 10547, ie 5-phenoxy-1 -3_ (trifluoromethyl) phenyl_-1 H-tetrazole.

For use, the formulations present in the commercial form are optionally diluted in the customary manner, for example in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules by means of water, and then onto the plants, parts of plants or the agricultural or industrial soil on which the plants stand or in which they grow or are available as seeds. Preparations in the form of dust, ground or scatter granules and sprayable solutions are usually no longer diluted with other inert substances before use. The required application rate of the compounds of formula (I) varies with the external conditions, such as temperature, humidity, the type of herbicide used, and others. It can vary within wide limits, for example between 0.001 and 10.0 kg / ha or more of active substance, but is preferably between 0.005 and 5 kg / ha.

A. Chemical examples

A1) 5-Acetylamino-N - [(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2-methoxycarbonyl-benzenesulfonamide sodium salt (Table 1, No. 1)

12.0 g of 5-acetylamino-N - [(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2-methoxycarbonyl-benzenesulfonamide (obtained according to US Pat. No. 4,892,946) are placed in 80 ml of CH ₂ Cl ₂ and mixed with 26.5 ml of 1 N sodium hydroxide solution. The clear mixture is concentrated and stirred with a little methanol. 10.5 g of the title product are obtained as a colorless salt with a melting point of 210 to 212 ° C. with decomposition.

A2) N - [(4,6-Dimethoxypyrimidin-2-yl) aminocarbonyl] -5-formylamino-2-methoxycarbonyl-benzenesulfonamide sodium salt (Table 1, No. 57)

1.40 g of N - [(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -5-formylamino-2-methoxycarbonyl-benzenesulfonamide are placed in 20 ml of methanol and mixed with 0.58 ml of 30% sodium methylate solution. After stirring for 30 minutes, methanol is distilled off. The residue is dried under high vacuum. This gives 1.31 g of the desired salt with a melting point of 202 ° C. with decomposition. A3) N - [(4,6-Dimethoxypyrimidin-2-yl) aminocarbonyl] -5-methoxycarbonylamino-2-methoxycarbonyl-benzenesulfonamide sodium salt (Table 1, No. 28)

0.5 g of N - [(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -5-methoxycarbonylamino-2-methoxycarbonyl-benzenesulfonamide are analogously to Example 2 in 1 3 ml of methanol with 0.20 ml of 30% sodium methylate solution appropriate salt implemented. This gives 0.5 g of the desired compound with a melting point of 1 73 ° C (Z).

The compounds described in Table 1 below are obtained in an analogous manner.

The following abbreviations are used in Table 1:

No. = example number

Mp. = Fixed point (melting point)

Me = methyl

Et = ethyl

Pr = ⁿ Pr = n-propyl

'Pr = i-propyl ^c Pr = cyclopropyl

* Bu = tert-butyl

(Z) = decomposition

Table 1

Mθ X

B. Formulation examples

a) A dusting agent is obtained by mixing 10 parts by weight of a compound of the formula (I) and 90 parts by weight of talc as an inert substance and comminuting in a hammer mill.

b) A wettable powder which is readily dispersible in water is obtained 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 of potassium lignosulfonate and 1 part by weight of oleoylmethyl tauric acid

Mixes sodium as a wetting and dispersing agent and grinds it in a pin mill.

c) A dispersion concentrate which is readily dispersible in water is obtained by mixing 20 parts by weight of a compound of the formula (I) with

® 6 parts by weight of alkylphenol polyglycol ether (Triton X 207),

3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range e.g. approx. 255 to above 277 ° C) are mixed and ground in a attritor to a fineness of less than 5 microns.

d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of formula (I), 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxyethylated 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 lignosulfonate, 5 parts by weight of sodium lauryl sulfate,

3 parts by weight of polyvinyl alcohol and 7 parts by weight of kaolin are mixed, ground on a pin mill and the powder is granulated in a fluidized bed by spraying water as the granulating liquid.

f) A water-dispersible granulate is also obtained by

25 parts by weight of a compound of formula (I), 5 parts by weight of 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, 2 parts by weight of sodium oieoylmethyl taurine, 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 dicotyledon weed plants are grown in

Plastic pots laid out in sandy loam and covered with earth. The compounds according to the invention formulated in the form of wettable powders or emulsion concentrates are then applied as an aqueous suspension or emulsion with a water application rate of the equivalent of 600 to 800 l / ha in different dosages to the surface of the covering earth.

After the treatment, the pots are placed in the greenhouse and kept under good growth conditions for the weeds. After the test plants have emerged, the optical damage to the plants or the emergence damage occurs after a test period of 3 to 4 weeks in comparison to untreated controls. As the test results show, the compounds according to the invention have good herbicidal pre-emergence activity against a wide range of grasses and weeds. For example, the compounds of Examples 1, 2, 1, 7, 24, 27, 28, 35, 37, 57, 64, 72, 73, 74 and 75 from Table 1 have very good herbicidal activity against harmful plants such as Alopecurus myosuroides, Sinapis alba , Chrysanthemum segetum, Avena sativa, Stellaria media, Echinochlora crus-galli and Lolium multiflorum in the pre-emergence process with an 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 are placed in sandy loam soil in plastic pots, covered with soil and grown in the greenhouse under good growth conditions. Three weeks after sowing, the test plants are treated at the three-leaf stage.

The compounds according to the invention formulated as wettable powder or as emulsion concentrates are sprayed onto the green parts of the plant in various dosages with a water application rate of the equivalent of 600 to 800 l / ha and after about 3 to 4 weeks of standing of the test plants in the greenhouse under optimal growth conditions

Effect of the preparations rated visually in comparison to untreated controls. The agents according to the invention also have good herbicidal activity against a broad spectrum of economically important grasses and weeds, even after emergence. For example, the compounds of Examples 1, 2, 1, 7, 24, 27, 28, 35, 37, 57, 64, 72, 73, 74 and 75 from the

Table 1 very good herbicidal activity against harmful plants such as Alopecurus myosuroides, Sinapis alba, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Chrysanthemum segetum and Avena sativa in the post-emergence process with an application rate of 0.3 kg and less active substance per hectare. 3. Crop tolerance

In further experiments in the greenhouse, seeds of a larger number of crop plants and weeds are planted in sandy loam soil and covered with soil. Some of the pots are immediately treated as described in Section 1, the rest are placed in the greenhouse until the plants have developed two to three true leaves and then sprayed as described in Section 2 with the substances of the formula (I) according to the invention in different dosages. Four to five weeks after application and standing in the greenhouse, it is determined by means of an optical evaluation that the compounds according to the invention have dicotyledonous cultures such as e.g. Leave soy, cotton, rapeseed, sugar beet and potatoes undamaged in the pre- and post-emergence process, even with high active ingredient doses. Some substances also protect Gramineae crops such as Barley, wheat, rye, sorghum, corn or rice. The

Compounds of the formula (I) thus have a high selectivity when used to combat undesirable plant growth in agricultural crops.

Claims

Claims:

where n is 0, 1, 2 or 3,

R is halogen, alkyl or alkoxy, each independently of the other

Substituents R, if n is greater than 1,

R is an unsubstituted or substituted hydrocarbon radical or an unsubstituted or substituted heterocyclic radical,

R ^{2 is} an acyl radical,

R ^{3 is} hydrogen or C ₁ -C ₅ alkyl,

Mθ is a metal or ammonium ion,

X, Y independently of one another halogen, C ** - C ₆ alkyl. C., - C ₆ -alkoxy, C, -C ₆ - alkylthio, where each of the latter three radicals unsubstituted or by one or more radicals from the group halogen, C., - C ₄ -alkoxy, and C- _| -C ₄ alkylthio is substituted, or C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ alkenyloxy, C ₃ -C ₆ alkynyloxy, mono - or DMC- C ^ alkyO-amino and

Z is CH or N.

2. Compounds of formula (I) according to claim 1, characterized in that n is 0, 1 or 2,

R is halogen, C ₁ -C ₃ alkyl or C _j -C ₃ alkoxy, R ¹ C _j -CG alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ Cycloalkyl, each of the four last-mentioned radicals being unsubstituted or by one or more radicals from the group halogen, CN, C _r C ₄ alkoxy, C _r C ₄ - Haloalkoxy, mono- (C., - C ₄ -alkyl) -amino, di- (C _r C ₄ -alkyl) -amino, C -, - C ₄ - alkylsulfonyl, C. * - C ₄ -alkylsulfinyl, (C ₁ -C ₄ alkoxy) carbonyl, aminocarbonyl, mono- (C ₁ -C ₄ alkyl) aminocarbonyl, di (C ₁ -C ₄ alkyl) aminocarbonyl, unsubstituted phenyl, substituted phenyl, unsubstituted heterocyclic radical and substituted heterocyclic

Radical is substituted, or a heterocyclic radical with 3, 4, 5 or 6 ring atoms and an oxygen atom as a hetero ring atom, the radical being unsubstituted or substituted by one or more radicals from the group C _r C ₄ alkyl, R ² CO-R ⁴ , CO-OR ⁵ , CO-NR ⁶ R ⁷ or SO ₂ -R ⁸ ,

R ³ H, C _r C ₄ alkyl,

R ^{4 is} hydrogen, C _r C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, where each of the four last-mentioned radicals is unsubstituted or by one or more radicals from the Group halogen, CN, C., - C ₄ -alkoxy, C, -C ₄ - haloalkoxy, mono- (C. * - C ₄ -alkyl) -arr.ino, di- (C., -C ₄ -alkyl ) -amino, C, -C ₄ -

Alkylsulfonyl, C. * - C ₄ alkylsulfinyl, (C ₁ -C ₄ alkoxy) carbonyl, aminocarbonyl, mono- (C *, - C ₄ alkyl) -anninocarbonyl, di- (C ₁ -C ₄ alkyl) ) - aminocarbonyl, phenyl and substituted phenyl, or phenyl which is unsubstituted or substituted, R ⁵ analogously to R ⁴ , except hydrogen,

R ⁶ and R ⁷ are independently H, C _j -CG alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ - alkynyl, where each of the three last-mentioned radicals is unsubstituted or substituted by one or more radicals from the group halogen such as F, Cl and Br, CN, C _r C ₄ alkoxy, C _r C ₄ haloalkoxy, mono- (C _r C ₄ alkyl) amino, di- (C. * - C ₄ alkyl) - anr.ino, C _r C ₄ alkylsulfonyl, C _r C ₄ alkylsulfinyl, (C _r C ₄ -

Alkoxy) carbonyl, aminocarbonyl, mono- (C ₁ -C ₄ alkyl) aminocarbonyl and di- (C. _| -C ₄ alkyl) -anr.inocarbonyl, or R ⁶ and R ⁷ together with the they bond an unsubstituted or substituted heterocyclic ring of four to eight ring atoms to the N atom, which contains up to 18 C atoms including the substituents, R ^{8 is} C *, - C ₅ alkyl, C ₂ -C ₅ alkenyl, where each of the latter two radicals is unsubstituted or by one or more radicals from the group halogen, C ..- C ₄ alkoxy, C * -C ₄ -haloalkoxy, mono- (C ₁ -C ₄ alkyl) amino and di- (C ₁ -C ₄ alkyl) amino is substituted,

MΘ the cation equivalent of an alkali or alkaline earth metal or NH ₄ ^{+ _1/2} Zn ^{+ 2} -, R ° NH ₃ ^+, R ₂ NH ₂ ⁺ °, R ° or R ₃ NH ⁺ ₄ ° ⁺ N,

R ° C _r C ₆ alkyl or benzyl,

X, Y independently of one another halogen, C. _| -C ₄ alkyl, C _r C ₄ alkoxy, C _r C ₄ alkylthio, where each of the last three radicals unsubstituted or by one or more radicals from the group halogen, CC ₄ alkoxy and C - C ₄ alkylthio is substituted, mono- or di (C ₁ -C ₄ alkyl) amino, C ₃ -C ₆ cycloalkyl, C ₂ -C ₅ alkenyl or C ₂ -C ₅ alkynyloxy and

Z is CH or N.

3. Compounds of formula (I) according to claim 1 or 2, characterized in that

R ¹ C _r C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, each of the four last-mentioned radicals unsubstituted or by one or more radicals from group F , Cl, Br, I, CN, OCH ₃ , OCF ₃ , N (CH ₃ ) ₂ , SO ₂ CH ₃ , CO ₂ CH ₃ , CO ₂ N (CH ₃ ) ₂ and phenyl, or a

Remainder of formulas A- to A ₇

(A,) (A ₂ ) (A ₃ ) (A ₄ )

₂ -

(A ₅ ) (A ₆ ) (A ₇ ) R ² CO-R ⁴ , CO-OR ⁵ , CO-NR ⁶ R ⁷ or SO ₂ -R ⁸ ,

R ³ H or CH ₃ ,

R ^{4 is} hydrogen, C.-Cg-alkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, C ₃ -C ₆ -cycloalkyl, where each of the four last-mentioned radicals is unsubstituted or by one or more radicals from the Group F, Cl, Br, I, CN, OCH ₃ , OCF ₃ ,

N (CH ₃ ) ₂ , SO ₂ CH ₃ , CO ₂ CH ₃ , CON (CH ₃ ) ₂ and phenyl, or phenyl which is unsubstituted or up to three times by identical or different radicals from the group halogen, CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , CF ₃ , C ₂ H ₅ CI, OCHF ₃ , OCHF _{2 is} substituted, R ⁵ analogously to R ⁴ , except hydrogen,

R ⁶ and R ⁷ independently of one another H, C- _| -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, each of the three last-mentioned radicals unsubstituted or by one or more radicals from the group F, Cl, Br, CN, OCH ₃ , OCF ₃ , N (CH ₃ ) ₂ , SO ₂ CH ₃ , CO ₂ CH ₃ and CON (CH ₃ ) ₂ , and R ^{8 is} C - C ₅ alkyl or C ₂ -C ₅ alkenyl, each of which two latter

Residues unsubstituted or substituted by one or more radicals from the group F, Cl, Br, OCH ₃ or N (CH ₃ ) ₂ .

4. Compounds of formula (I) according to any one of claims 1 to 3, characterized in that

R ¹ C _r C ₆ alkyl,

R ² CO-R ⁴ , CO-OR ⁵ , CO-NR ⁶ R ⁷ or SO ₂ -R ⁸ ,

R ³ H, MΘ Na ^+, K ^{+ _1/2} Mg ^{2 + _1/2} Ca ^{2 +,} NH ₄ ^+, H ₂ NEt ₂ ^+, H ₃ NC ₄ H ₉ ^+, NH (C ₂ H _{5) 3} ⁺ ,

N (C ₂ H ₅ ) ₄ ⁺ , N (CH ₃ ) ₄ ⁺ , HN (CH ₃ ) ₃ ⁺

R ° C _r C ₆ alkyl,

X, Y OCH ₃ , OC ₂ H ₅ , SCH ₃ , NHCH ₃ , N (CH ₃ ) ₂ , CH ₃ or OCH ₂ CF ₃ .

5. A process for the preparation of the compounds of formula (I) as defined in any one of claims 1 to 4, characterized in that compounds of formula (II)

R ' wherein

R, R ¹ , R ² , R ³ , X, Y, Z and n are as defined in formula (I),

with a suitable base of the formula (III)

M ^θ X ^θ (III),

wherein X ^{θ is} an anion equivalent and M® is as defined in said formula (I) and Ar is aryl

or, in the case of an ammonium salt, is reacted accordingly with ammonia or an organic amine.

6. Process for the preparation of compounds of formula (II),

characterized in that a reaction according to one of the following

Performs reaction equations (1) to (6):

(V) (V I)

(2) + CI -CO-0-Ar + HNR (ι i) NH _:

(V) (V I I)

(3) (ι ι)

(V) (V I I I)

(4) + NαOCN HNR (II)

(x) (V I I)

(XI) where in the reaction sequence (6) R ² in formula (II) has the meaning of the formula COR ⁴ and in the formulas (II), (V) - (XIII) and (R ⁴ CO) ₂ O the radicals R, R ¹ , R ² , R ³ , R ^4, X, Y, Z and the index n as defined in formula (I) according to any one of claims 1 to 4.

7. The method according to claim 6, characterized in that a compound of formula (XI)

catalytically hydrogenated in the presence of an acylating agent of the formula (R CO) ₂ O on the nitro group and reacted with the acylating agent.

8. Herbicidal or plant-regulating agent, characterized in that it contains at least one compound of the formula (I) according to one of Claims 1 to 4 and formulation auxiliaries customary in crop protection.

9. A method for controlling harmful plants or for regulating the growth of plants, characterized in that an effective amount of at least one compound of the formula (I) according to one of Claims 1 to 4 is applied to the harmful plants or plants, their plant seeds or the area, on which the plants grow.

10. Use of the compounds of formula (I) according to one of claims 1 to 4 as herbicides or plant growth regulators.