WO1997000247A1

WO1997000247A1 - Substituted hydrazinophenylsulfonyl ureas, a process for preparing the same and their use as herbicides and plant growth regulators

Info

Publication number: WO1997000247A1
Application number: PCT/EP1996/002513
Authority: WO
Inventors: Heinz Kehne; Lothar Willms; Klaus Bauer; Hermann Bieringer; Christopher Rosinger
Original assignee: Hoechst Schering Agrevo Gmbh
Priority date: 1995-06-14
Filing date: 1996-06-10
Publication date: 1997-01-03
Also published as: DE19521668A1; AU6302096A; ZA965015B; CA2224612A1; PL324181A1; BR9608572A; EP0842154A1; JPH11507658A

Abstract

Compounds have the formula (I), in which R1 stands for S(O)¿nR?4, SO2NR5R6 or CONR5R6; A stands for a residue having the formula A1 or, should R1 stand for S(O)¿nR?4 or SO¿2NR?5R6, may also stand for a residue having the formula A?2 R7R8C=N-NR9- (A1), R10R11N-NR9- (A2¿); and R?2 to R11¿, W, X, Y and Z have the definitions given in the first claim. These compounds are suitable as selective herbicides or plant growth regulators. The compounds having the formula (I) may be prepared in an analogous manner to known processes by using at least some new intermediate products (see process described in claim 5 and intermediate products having the formulas (II), (IV) and (VI)).

Description

description

Substituted hydrazinophenylsulfonylureas, process for their preparation and their use as herbicides and plant growth regulators

It is known that phenylsulfonylureas with hydrazine partial structures have herbicidal properties. It is primarily about

Hydrazones (EP-A-382 437, EP-A-562 575) or heterocycles with incorporated hyrazine structure (EP-A-382 436, EP-A-384 602). The known compounds each carry halogen, alkyl or alkoxycarbonyl radicals in the para position to the substituted hydrazine groups.

Surprisingly, phenylsulfonylureas with substituted hydrazine residues and sulfonyl or carbamoyl groups para to them have now been found, which are particularly useful as herbicides or

Plant growth regulators are suitable.

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

wherein

R ¹ S (O) _n R ⁴ , SO ₂ NR ⁵ R ⁶ or CONR ⁵ R ⁶ ,

R ² H, halogen, NO ₂ , CN, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, [(C ₁ -C ₄ ) alkyljcarbonyl or [(C ₁ -C ₄ ) alkoxy] carbonyl , where each of the latter four radicals is unsubstituted or substituted in the alkyl part by one or more halogen atoms, R ^{3 is} H or (C ₁ -C ₄ ) alkyl, preferably H or CH ₃ ,

R ^{4 is} an aliphatic hydrocarbon radical or aryl, each of the latter two radicals being unsubstituted or substituted,

R ⁵ , R ⁶ independently of one another H, an aliphatic hydrocarbon radical or aryl, where each of the latter two radicals is unsubstituted or substituted or

R ⁵ and R ⁶ together with the N atom represent a heterocyclic radical which

is unsubstituted or substituted,

A is a radical of the formula A ¹ or in the event that R ¹ = S (O) _n R ⁴ or

SO ₂ NR ⁵ R ⁶ , also A ² ,

R ⁷ , R ⁸ independently of one another H, NO ₂ , CN, an aliphatic

Hydrocarbon radical, a heterocyclic radical or aryl, where each of the last three radicals is unsubstituted or substituted, or an acyl radical, where C-containing radicals R ⁷ , R ⁸ preferably have 1 to 20 C atoms, or

R ⁷ and R ⁸ together with the carbon atom are a carbocyclic or

heterocyclic ring which is unsubstituted or substituted,

R ⁹ H, an aliphatic hydrocarbon radical which is unsubstituted or substituted, or an acyl radical, where C-containing radicals R ⁹

preferably have 1 to 20 carbon atoms,

R ^{10 is} an acyl radical which is unsubstituted or substituted and preferably has 1 to 20 C atoms,

R ^{1 1} H or an aliphatic hydrocarbon radical which is unsubstituted or substituted and preferably has 1 to 12 C atoms,

W is an oxygen or sulfur atom,

X, Y independently of one another H, halogen, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) alkylthio, each of the latter three residues being unsubstituted or by one or more residues from the group halogen,

(C ₁ -C ₄ ) alkoxy and (C ₁ -C ₄ ) alkylthio is substituted, or mono- or di - [(C ₁ -C ₄ ) alkyl] amino, (C ₃ -C ₆ ) cycloalkyl, (C ₂ -C ₅ ) alkenyl, (C ₂ -C ₅ ) alkynyl, (C ₂ -C ₅ ) alkenyloxy or (C ₂ -C ₅ ) alkynyloxy,

Z CH or N and

n 0, 1 or 2

mean.

The compounds of formula (I) can form salts in which the hydrogen of the -SO ₂ -NH group is replaced by a cation suitable for agriculture. These salts are, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or also ammonium salts or salts with organic amines. You can also

Compounds of formula (I) by addition of a suitable inorganic or organic acid, such as HCl, HBr, H ₂ SO ₄ or HNO ₃ , but also oxalic acid or sulfonic acids to a basic group, such as amino or alkylamino, form salts. Suitable substituents, which may be in deprotonated form, such as, for example, sulfonic acids or carboxylic acids, can form internal salts with groups that can be protonated, such as amino groups. Salts can also be formed by the fact that at suitable

Substituents such as Sulfonic acids or carboxylic acids, the hydrogen is replaced by a cation suitable for agriculture. These salts are, for example, metal salts, in particular alkali metal salts or

Alkaline earth metal salts, especially sodium and potassium salts, or also

Ammonium salts or salts with organic amines.

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 are, for example, with 1 to 6 carbon atoms or at unsaturated groups with 2 to 6 carbon atoms, preferred. Alkyl radicals, also in the composite meanings such as alkoxy, haloalkyl, etc., mean, for example, 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; Aikenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals; Aikenyl means, for example, 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, for example, propargyl, but-2-in-1-yl, but-3-in-1-yl, 1-methyl-but-3-in-1-yl.

Aikenyl in the form of (C ₃ -C ₄ ) alkenyl preferably means an alkenyl radical having 3 or 4 carbon atoms, in which the multiple bond is not bound to the carbon atom, to which the radical is linked to the rest of the molecule ("yl "Position). The same applies to (C ₃ -C ₄ ) alkynyl.

Cycloalkyl means a carbocyclic, saturated ring system with

preferably 3-8 C atoms, e.g. Cyclopropyl, cyclopentyl or cyclohexyl.

Halogen means, for example, fluorine, chlorine, bromine or iodine. Haloalkyl, aikenyl 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 e.g. Monohaloalkyl

(= Monohalalkyl), perhaloalkyl, CF ₃ , CHF ₂ , CH ₂ F, CF ₃ CF ₂ , CH ₂ FCHCl, CCI ₃ , CHCl 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, aikenyl, 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;

preferably a hydrocarbon radical means alkyl, aikenyl or alkynyl up to 12 carbon atoms or cycloalkyl with 3, 4, 5, 6 or 7 ring atoms or phenyl; the same applies to a hydrocarbon residue in one

Hydrocarbonoxy group.

A heterocyclic radical or ring (heterocyclyl) can be saturated, unsaturated or heteroaromatic; it preferably contains one or more

Hetero units in the ring, ie hetero atoms or ring members, which also include substituted hetero atoms, preferably from the group N, O, S, SO, SO ₂ ; it is preferably an aliphatic heterocyclyl radical with 3 to 7 ring atoms or a heteroaromatic radical with 5 or 6 ring atoms and contains 1, 2 or 3 hetero units. 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. As

Substituents for a substituted heterocyclic radical are the substituents mentioned below, in addition also oxo. The oxo group can also be attached to the hetero ring atoms, which can exist in different oxidation states, e.g. at N and S, occur.

Substituted residues such as substituted hydrocarbon residues e.g. Substituted alkyl, aikenyl, alkynyl, aryl, phenyl and benzyl, or substituted heterocyclyl or heteroaryl mean, for example, one of the unsubstituted

Base derived derivative radical, where the substituents

for example one or more, preferably 1, 2 or 3, radicals from the group halogen, alkoxy, haloalkoxy, alkylthio, hydroxy, amino, nitro,

Carboxy, 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 radicals, also alkyl and haloalkyl mean; in the term "substituted radicals" such as substituted alkyl etc. are saturated as substituents in addition to the above

hydrocarbon-containing radicals corresponding unsaturated aliphatic and aromatic radicals, such as optionally substituted aikenyl, alkynyl,

Alkenyloxy, alkynyloxy, phenyl, phenoxy etc. included. In the case of radicals with carbon atoms, those with 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, are preferred. Substituents from the group halogen, for example fluorine and chlorine, (C ₁ -C ₄ ) alkyl, preferably methyl or ethyl, are generally preferred,

(C ₁ -C ₄ ) haloalkyl, preferably trifluoromethyl, (C ₁ -C ₄ ) alkoxy, preferably methoxy or ethoxy, (C ₁ -C ₄ ) haloalkoxy, nitro and cyano. Especially

the substituents methyl, methoxy and chlorine are preferred.

Mono- or disubstituted amino means a chemically stable radical from the group of substituted amino radicals which are, for example, N-substituted by one or two identical or different radicals from the group alkyl, alkoxy, acyl and aryl; preferably monoalkylamino, dialkylamino, acylamino, arylamino, N-alkyl-N-arylamino and N-heterocycles; alkyl radicals having 1 to 4 carbon atoms are preferred; Aryl is preferably phenyl or substituted phenyl; for acyl the following applies

Definition, preferably (C ₁ -C ₄ ) alkanoyl. The same applies to substituted hydroxylamino or hydrazino.

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 ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) haloalkyl, (C ₁ -C ₄ ) haloalkoxy and nitro, for example o-, m- and p-tolyl, dimethylphenyl, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4- Trifluoro- and -Trichlorphenyl, 2,4-, 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 acids 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, alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, N-alkyl-1-iminoalkyl and other residues of

organic acids. The radicals in each case in the alkyl or phenyl part can be further substituted, for example in the alkyl part by one or more radicals from the group halogen, alkoxy, phenyl and phenoxy; Examples of substituents in the phenyl part are those already general above for

substituted phenyl mentioned substituents.

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.

Mainly because of the higher herbicidal effects, better ones

Selectivity and / or better manufacturability are inventive

Compounds of the formula (I) or their salts of particular interest, in which R ¹ S (O) _n R ⁴ , SO ₂ NR ⁵ R ⁶ or CONR ⁵ R ⁶ ,

R ² H, halogen, NO ₂ , CN, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, [(C ₁ -C ₄ ) alkyl] carbonyl or [(C ₁ -C ₄ ) alkoxy ] carbonyl, each of the latter four radicals being unsubstituted or substituted in the alkyl part by one or more halogen atoms,

R ^{3 is} H or (C ₁ -C ₄ ) alkyl, preferably H or CH ₃ ,

R ⁴ (C ₁ -C ₆ ) alkyl, (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆ ) alkynyl, (C ₃ -C ₇ ) cycloalkyl, (C ₃ -C ₇ ) cycloalkyl- (C ₁ -C ₃ ) alkyl, phenyl, each of the latter six residues being unsubstituted or by one or more residues from the group halogen, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) alkylthio, (C ₁ -C ₄ ) alkylsulfinyl, (C ₁ -C ₄ ) aikylsulfonyl, unsubstituted or substituted phenyl,

[(C ₁ -C ₄ ) alkoxy] carbonyl and in the case of cyclic radicals also (C ₁ -C ₄ ) alkyl and (C ₁ -C ₄ ) haloalkyl is substituted,

R ⁵ , R ⁶ independently of one another are H, (C ₁ -C ₆ ) alkyl, (C ₃ -C ₆ ) alkenyl, (C ₃ -C ₆ ) alkynyl, each of the last three radicals being unsubstituted or by one or more radicals the group halogen, (C ₁ -C ₄ ) alkoxy,

(C ₁ -C ₄ ) alkylthio and [(C ₁ -C ₄ ) alkoxy] carbonyl, or unsubstituted or substituted phenyl or

R ⁵ and R ⁶ together with the N atom form a heterocyclic ring with 5 or 6 ring members, which may optionally contain further heteroatoms from the group N, O or S and are unsubstituted or one or more times by (C ₁ -C ₄ ) alkyl or an oxo group is substituted,

A is a group of the formula A ¹ or, if R ¹ = S (O) _n R ⁴ or SO ₂ NR ⁵ R ⁶ , a group of the formula A ^{2 mentioned} ,

R ⁷ , R ^{8 are} independently H, (C ₁ -C ₆ ) alkyl, (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆ ) alkynyl, (C ₃ -C ₆ ) cycloalkyl, each of the latter four Leftovers

unsubstituted or by one or more radicals from the group halogen, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) alkylthio, [(C ₁ -C ₄ ) alkoxy] carbonyl, phenyl and in the case of cycloalkyl also (C ₁ -C ₄ ) alkyl and (C ₁ -C ₄ ) haloalkyl, or phenyl or phenylcarbonyl, where each of the latter two residues is unsubstituted or by one or more residues from the group halogen, CN, NO ₂ , (C ₁ - C ₄ ) alkyl, (C ₁ -C ₄ ) haloalkyl, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) haloalkoxy, (C ₁ -C ₄ ) alkylthio and

[(C ₁ -C ₄ ) alkoxy] carbonyl is substituted,

or heterocyclyl with 3 to 6 ring atoms, which is unsubstituted or by one or more radicals from the group halogen, (C ₁ -C ₄ ) alkyl,

(C ₁ -C ₄ ) haloalkyl, (C ₁ -C ₄ ) alkoxy and (C ₁ -C ₄ ) haloalkoxy is substituted, or [(C ₁ -C ₄ ) alkoxy] carbonyl, [(C ₁ -C ₄ ) Alkyl] carbonyl, CN,

(C ₁ -C ₄ ) alkylsulfonyl, NO ₂ or COOH or carbamoyl which is unsubstituted is or on the N atom one or two substituents from the group of the radicals (C ₁ -C ₄ ) alkyl, (C ₃ -C ₄ ) alkenyl, (C ₃ -C ₄ ) alkynyl and phenyl, which is unsubstituted or by one or more Radicals from the group halogen, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) haloalkyl, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) alkylthio, (C ₁ -C ₄ ) alkylsulfonyl , [(C ₁ -C ₄ ) alkoxy] carbonyl, CN and NO _{2 is} substituted, or di - [(C ₁ -C ₄ ) alkoxy] phosphinyl or

R ⁷ and R ⁸ together with the C atom are a ring with 4 to 8 ring atoms, which is carbocyclic or heterocyclic with one or two heteroatoms from the group N, O and S and which is unsubstituted or by one or more radicals from the group (C ₁ -C ₄ ) alkyl, halogen and oxo is substituted or is also benzo-fused,

R ^{9 is} H or (C ₁ -C ₆ ) alkyl which is unsubstituted or by one or more radicals from the group halogen, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) alkylthio,

(C ₁ -C ₄ ) alkylsulfonyl, [(C ₁ -C ₄ ) alkoxy] carbonyl, CN, phenyl and

(C ₃ -C ₆ ) cycloalkyl is substituted, or (C ₃ -C ₆ ) alkenyl, (C ₃ -C ₆ ) alkynyl, each of the latter two radicals being unsubstituted or substituted by one or more halogen atoms, or a group of formula

or -SO ₂ R ^** , wherein

R ^* H, (C ₁ -C ₈ ) alkyl, (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆ ) alkynyl, each of the last three radicals being unsubstituted or by one or more radicals from the group halogen, ( C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) alkylthio, phenoxy, [(C ₁ -C ₄ ) alkoxy] carbonyl, unsubstituted or substituted heterocyclyl and

unsubstituted or substituted phenyl, or unsubstituted or substituted (C ₃ -C ₆ ) cycloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted heterocyclyl or [(C ₁ -C ₄ ) alkoxy] carbonyl,

R ^** (C ₁ -C ₆ ) alkyl, (C ₃ -C ₆ ) alkenyl, (C ₃ -C ₆ ) alkynyl, where each of the latter three radicals is unsubstituted or by one or more radicals from the group halogen, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) alkylthio and phenyl is substituted, or phenyl which is unsubstituted or by one or more radicals from the group halogen, CN, NO ₂ , (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) haloalkyl and (C ₁ -C ₄ ) Alkoxy is substituted,

R ^{10 is} an acyl radical of the formula

R ^{1 1} H, (C ₁ -C ₆ ) alkyl, (C ₃ -C ₆ ) alkenyl, (C ₃ -C ₆ ) alkynyl, each of the three

the latter radicals unsubstituted or by one or more of the radicals from the group halogen, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) alkylthio,

[(C ₁ -C ₄ ) alkoxy] carbonyl, (C ₃ -C ₆ ) cycloalkyl, unsubstituted or substituted phenyl and CN is substituted,

R ¹² H, (C ₁ -C ₈ ) alkyl, (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆ ) alkynyl, each of the three

the latter radicals unsubstituted or by one or more radicals from the group halogen, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) alkylthio, phenoxy,

[(C ₁ -C ₄ ) alkoxy] carbonyl, unsubstituted or substituted heterocyclyl and unsubstituted or substituted phenyl, or unsubstituted or substituted (C ₃ -C ₆ ) cycloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted

Heterocyclyl or [(C ₁ -C ₄ ) alkoxy] carbonyl,

R ^{13 is} (C ₁ -C ₆ ) alkyl, (C ₃ -C ₆ ) alkenyl, (C ₃ -C ₆ ) alkynyl, each of the three

the latter radicals unsubstituted or by one or more radicals from the group halogen, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) aikylthio,

[(C ₁ -C ₄ ) Alkoxy] carbonyl, unsubstituted or substituted phenyl and unsubstituted or substituted (C ₃ -C ₆ ) cycloalkyl, or (C ₃ -C ₆ ) cycloalkyl which is unsubstituted or substituted by one or more radicals the group halogen, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, R ^{14 is} a radical from the group of the radicals possible for R ⁴ ,

R ^{15 is} a radical from the group of the radicals which are possible for R ⁵ ,

R ^{16 is} a radical from the group of the radicals possible for R ⁶ or

R ¹⁵ and R ¹⁶ together with the N atom form a heterocycle such as that for NR ⁵ R ⁶ is possible,

W is an oxygen atom or a sulfur atom, preferably a

Oxygen atom,

W ^{* is} an oxygen atom or a sulfur atom, preferably O,

T is an oxygen atom or a sulfur atom, preferably O,

n 0, 1 or 2,

X, Y independently of one another H, halogen, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy,

(C ₁ -C ₄ ) alkylthio, each of the latter three residues being unsubstituted or by one or more residues from the group halogen,

(C ₁ -C ₄ ) alkoxy and (C ₁ -C ₄ ) alkylthio is substituted, or mono- or di - [(C ₁ -C ₄ ) alkyl] amino, (C ₃ -C ₆ ) cycloalkyl, (C ₃ -C ₅ ) alkenyl, (C ₃ -C ₅ ) alkynyl, (C ₃ -C ₅ ) alkenyloxy or (C ₃ -C ₅ ) alkynyloxy and

Z is CH or N.

Of particular interest are compounds of formula (I) according to the invention and their salts, in which

R ² H, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) haloalkyl, (C ₁ -C ₄ ) alkoxy or halogen,

R ⁴ (C ₁ -C ₄ ) alkyl, (C ₂ -C ₄ ) alkenyl, (C ₂ -C ₄ ) alkynyl, (C ₃ -C ₆ ) cycloalkyl,

(C ₃ -C ₆ ) cycloalkyl- (C ₁ -C ₂ ) alkyl, phenyl, each of the latter six residues being unsubstituted or by one or more residues from the group halogen, (C ₁ -C ₄ ) alkoxy, phenyl and [ (C ₁ -C ₄ ) alkoxy] carbonyl, and in the case of cyclic radicals also (C ₁ -C ₄ ) alkyl and (C ₁ -C ₄ ) haloalkyl is substituted,

R ⁵ , R ⁶ independently of one another are H, (C ₁ -C ₆ ) alkyl which is unsubstituted or substituted by one or more radicals from the group halogen and (C ₁ -C ₄ ) alkoxy, or (C ₃ -C ₄ ) Alkenyl or (C ₃ -C ₄ ) alkynyl or

R ⁵ and R ⁶ together with the N atom form a heterocyclic ring with 5 or 6 ring members, which may optionally contain 1 or 2 further heteroatoms from the group N, O or S,

R ⁷ , R ⁸ independently of one another are H, (C ₁ -C ₄ ) alkyl, (C ₂ -C ₄ ) alkenyl, each of the latter two radicals being substituted by one or more radicals from the group halogen, (C ₁ -C ₄ ) Alkoxy and phenyl is substituted, or (C ₃ -C ₆ ) cycloalkyl, (C ₃ -C ₄ ) alkynyl, phenyl or phenylcarbonyl, each of the latter two radicals being unsubstituted or by one or more radicals from the group consisting of fluorine, chlorine, CN, NO ₂ ,

(C ₁ -C ₄ ) haloalkyl, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) alkylthio and

[(C ₁ -C ₄ ) alkoxy] carbonyl, or furyl, pyridyl, thienyl, tetrahydrofuryl, [(C ₁ -C ₄ ) alkoxy] carbonyl or COOH or CN, NO ₂ , carbamoyl, which is unsubstituted or by residues from the group (Cm- C ₄ ) alkyl is mono- or disubstituted or is monosubstituted by phenyl, or -PO (OCH ₃ ) ₂ or -PO (OC ₂ H ₅ ) ₂ or

R ⁷ and R ⁸ together with a C atom form a ring with 4 to 8 ring members, which is carbocyclic or heterocyclic with a hetero atom from the group N, O and S and is unsubstituted or one or more times by (C ₁ -C ₄ ) Alkyl or halogen or an oxo group is substituted,

R ⁹ H, (C ₁ -C ₄ ) alkyl which is unsubstituted or by one or more radicals from the group halogen, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) alkylthio,

[(C ₁ -C ₄ ) alkoxy] carbonyl and phenyl is substituted, or (C ₃ -C ₄ ) alkenyl or (C ₃ -C ₄ ) alkynyl,

R ^{10 is} a radical of the formula

R ^{1 1} H, (C ₁ -C ₄ ) alkyl which is unsubstituted or by one or more radicals from the group halogen, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) alkylthio,

R ¹² H, (C ₁ -C ₆ ) alkyl which is unsubstituted or by one or more radicals from the group halogen, (C ₁ -C ₆ ) alkoxy, (C ₁ -C ₄ ) alkylthio,

[(C ₁ -C ₄ ) alkoxy] carbonyl and unsubstituted or substituted phenyl, or (C ₂ -C ₄ ) alkenyl, (C ₂ -C ₄ ) alkynyl, (C ₃ -C ₆ ) cycloalkyl, [(C ₁ -C ₄ ) alkoxy] carbonyl, unsubstituted or substituted phenyl or unsubstituted or substituted heterocycyl,

R ^{13 is} (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) haloalkyl, (C ₃ -C ₄ ) alkenyl, (C ₃ -C ₄ ) alkynyl or (C ₃ -C ₆ ) cycloalkyl,

R ^{16 is} a radical from the group of the radicals possible for R ⁶ , or

R ¹⁵ and R ¹⁶ together with the N atom form a heterocycle as is possible for NR ⁵ R ⁶ ,

W ^{* is} an oxygen atom or a sulfur atom and

X, Y independently of one another (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, each of the latter two radicals being unsubstituted or by one or more

Halogen atoms is substituted, or (C ₁ -C ₄ ) alkylthio, halogen, or mono- or di - [(C ₁ -C ₂ ) alkyl] amino

mean.

Preferred compounds of the formula (I) according to the invention or their salts are those in which

R ² H, halogen or (C ₁ -C ₂ ) alkyl,

R ⁴ (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) haloalkyl, (C ₃ -C ₄ ) alkenyl or (C ₃ -C ₄ ) alkynyl,

R ⁵ , R ⁶ independently of one another are H, (C ₁ -C ₄ ) alkyl, (C ₃ -C ₄ ) alkenyl or

(C ₃ -C ₄ ) alkynyl or

R ⁵ and R ⁶ together with the N atom form a heterocyclic ring with 5 or

6 ring links,

R ⁷ , R ⁸ independently of one another are H, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) haloalkyl,

(C ₁ -C ₂ ) alkoxy- (C ₁ -C ₂ ) alkyl, (C ₂ -C ₄ ) alkenyl, (C ₂ -C ₄ ) alkynyl,

(C ₃ -C ₆ ) cycloalkyl or [(C ₁ -C ₄ ) alkoxy] carbonyl or

R ⁷ and R ⁸ together with the C atom form a ring with 5 or 6 ring members, R ⁹ H or (C ₁ -C ₃ ) alkyl,

R ^{10 is} a radical of the formula

R ^{1 1} H or (C ₁ -C ₄ ) alkyl,

R ¹² H, (C ₁ -C ₆ ) alkyl which is unsubstituted or substituted by one or more radicals from the group halogen, (C ₁ -C ₄ ) alkoxy or phenyl, or (C ₂ -C ₄ ) alkenyl, (C ₃ -C ₆ ) cycloalkyl or phenyl which is unsubstituted or by one or more radicals from the group halogen, (C ₁ -C ₄ ) alkyl and (C ₁ -C ₃ ) alkoxy is substituted,

R ¹³ (C ₁ -C ₄ ) alkyl or (C ₁ -C ₄ ) haloalkyl,

n 2,

X (C ₁ -C ₂ ) alkyl, (C ₁ -C ₂ ) alkoxy, (C ₁ -C ₂ ) alkylthio, (C ₁ -C ₂ ) haloalkyl or

(C ₁ -C ₂ ) haloalkoxy and

Y (C ₁ -C ₂ ) alkyl, (C ₁ -C ₂ ) alkoxy, halogen, NHCH ₃ or N (CH ₃ ) ₂

mean.

Particularly preferred compounds of the formula (I) according to the invention or their salts are those in which

R ² H,

R ⁴ (C ₁ -C ₄ ) alkyl and

R ⁵ , R ⁶ independently of one another are H or (C ₁ -C ₄ ) alkyl

mean.

Preference is also given to compounds of the formula (I) according to the invention in which one or some of the features from the abovementioned preferred

Connections are included.

The present invention also relates to processes for the preparation of the compounds of the general formula (I) or their salts, thereby

characterized in that a) a compound of the formula (II)

with a heterocyclic carbamate of the formula (III),

in which R ^* denotes unsubstituted or substituted phenyl or (C ₁ -C ₄ ) alkyl, or b) a sulfonyl carbamate of the formula (IV)

wherein R ° is unsubstituted or substituted phenyl or (C ₁ -C ₄ ) alkyl, with an amino heterocycle of the formula (V)

converts or c) a sulfonyiisocyanate of the formula (VI)

with an amino heterocycle of the formula (V) or d) a sulfonamide of the formula (II) with a (thio) isocyanate of the formula (VII)

in the presence of a base or e) first reacting an amino heterocycle of the formula (V) with base catalysis with a carbonic acid ester, for example diphenyl carbonate, and reacting the intermediate formed in a one-pot reaction with a sulfonamide of the formula (II), in the formulas (II) - (VII) the radicals or groups R ¹ -R ³ , A, W, X, Y and Z are as defined in formula (I) and in process variants a) to c) and e) initially compounds (I) with W = O be obtained.

The reaction of the compounds of the formulas (II) and (III) is preferably base-catalyzed in an inert organic solvent, such as e.g.

Dichloromethane, acetonitrile, dioxane or tetrahydrofuran (THF) at temperatures between 0ºC and the boiling point of the solvent. Organic amine bases such as 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) are used as the base, in particular at Rº = (subst.) Phenyl (cf. EP-A-44807), or

Alkali metal hydroxides such as e.g. NaOH or trimethyl aluminum or

Triethylaluminium, the latter used in particular at Rº = alkyl (see. EP-A-166 516). The base in question is used, for example, in the range from 1 to 3 molar equivalents, based on the compound of the formula (II).

The sulfonamides (II) are new compounds. They and their manufacture are also the subject of this invention. The compounds of the formula (II) are obtained, for example, starting from compounds of the formula (VIII)

wherein R ¹ , R ^{2 are} as defined in formula (I), by reaction with a strong acid (cf. WO 89/10921).

Examples of possible strong acids are mineral acids, such as H ₂ SO ₄ or HCl, or strong organic acids, such as trifluoroacetic acid. The tert-butyl protective group is cleaved off, for example, at temperatures from -20 ° C. to the respective reflux temperature of the reaction mixture, preferably at 0 ° C. to 40 ° C. The reaction can be carried out in bulk or in an inert solvent, such as dichloromethane or trichloromethane.

The compounds of formula (VIII) with A = A ¹ are, for example, from suitable hydrazine precursors by reaction with suitable electrophiles, such as

Obtain aldehydes or ketones. Suitable hydrazine precursors are, for example, those in which R ^{9 is} as defined in formula (I), but in particular R ⁹ = H; for the implementation of the hydrazine precursors with electrophiles see:

V. Lerch, J. König, Synthesis, 157 (1983), Houben-Weyl, "Methods of Organic Chemistry", 4th edition, Vol. 10/2, pp. 396 ff, p. 410 ff.

The compounds of formula (VIII) with A = A ² are, for example, from suitable

Hydrazine precursors by reaction with suitable electrophiles, e.g.

Acid chlorides, acid anhydrides, isocyanates, isothiocyanates, sulfochlorides or sulfamoyl chlorides obtained. Suitable hydrazine precursors are, for example, those in which R ¹⁰ = H and R ⁹ and R ^{1 1 are} as defined in formula (I),

R ⁹ and R ¹⁰ = H and R ^{1 1 are} as defined in formula (I),

R ¹⁰ and R ^{1 1} = H and R ^{9 are} as defined in formula (I), but in particular R ⁹ , R ¹⁰ and R ^{1 1} = H.

For the implementation of the hydrazine precursors with electrophiles see:

K.H. Pilgram, Synth. Commun. 15, 697 (1985),

J. Knabe, W. Wunn, Arch. Pharm. 313, 577 (1980),

V. Lerch, J. König, Synthesis, 157 (1983),

R. F. Smith et al., J. Org. Chem. 33, 851 (1968),

K.H. Pilgram, J. Org. Chem. 53, 38 (1988),

US-A-4 619 689, EP-A-562 575,

Houben-Weyl, "Methods of Organic Chemistry", 4th ed., Vol. 10/2, p. 355 ff, p. 383 ff, p. 396 ff, p. 406 ff, p. 391 ff.

In some cases it is possible to carry out further derivatizations following the reaction with electrophiles using methods known from the literature, e.g. Alkylations or acylations (cf. Houben-Weyl, "Methods of Organic Chemistry", 4th edition vol. 10/2, pp. 402 ff and p. 385).

The phenylhydrazines of the formula (VIII) with R ² , R ³ and R ⁴ = H are accessible starting from the aniline derivatives (IX),

wherein R ¹ and R ^{2 are} as defined in formula (I), by diazotization and subsequent reduction. Suitable reducing agents are, for example, SnCl ₂ , SO ₂ or sodium dithionite (cf. Houben-Weyl, "Methods of Organic Chemistry", 4th edition vol. 10/2, p. 180 ff .; EP-A-562 575). The aniline derivatives of the formula (IX) mentioned are obtained by processes known from the literature by reducing the nitro group of the compounds (X), for example by hydrogenation with hydrogen in the presence of a suitable catalyst, such as Pd-C or Raney nickel, or by reduction with iron in obtained acetic acid medium (see: H. Berrie, GT Neuhold, FS Spring, J. Chem. Soc.

(1952), 2042; M. Freifelder, "Catalytic Hydrogenation in Organic Synthesis: Procedures and Commentary", J. Wiley and Sons, New York (1978), chap. 5).

The sulfonamides of the formula (X) with R ¹ = -S (O) _n R ⁴ can be obtained, for example, in the following way (cf. Scheme 1):

The reaction of the sulfonic acids (XI) or their alkali salts with a

Chlorinating agents - such as PCI ₃ , POCI ₃ or SOCI ₂ - lead to the sulfochloride of the formula (XII). This reaction takes place in bulk or in inert solvents such as dichloromethane, sulfolane, acetonitrile or in a solvent mixture of inert components. The subsequent reaction with tert-butylamine leads to the sulfonamides of the formula (XIII). These connections can be made with

Mercaptans in solvents such as e.g. Dimethylformamide,

N, N-dimethylacetic acid amide or N-methylpyrroiidinone, in the presence

suitable bases, such as sodium or potassium carbonate, are converted into the corresponding mercaptans of the formula (Xa) (= formula (X) with R ¹ = S (O) _n R ⁴ and n = 0). By choosing suitable oxidizing agents (e.g.

Potassium peroxomonosulfate, oxones) and reaction conditions, the corresponding compounds of formula (Xb) can be prepared with n = 1 and 2 analogously to known methods.

The sulfonamides of the formula (X) with R ¹ = -SO ₂ NR ⁵ R ⁶ can be obtained, for example, in the following way (Scheme 2).

The compounds of formula (Xa) (= formula (X) with R ¹ = S (O) _n R ⁴ and n = 0), for example with R ⁴ = benzyl, by an oxidative

Chlorination with chlorine or sodium hypochlorite is converted into the sulfochlorides of the formula (XIV). The sulfonamides of the formula (Xc) are accessible by reacting (XIV) with amines.

The sulfonamides of the formula (X) with R ¹ = -CONR ⁵ R ^{6 are} obtained, for example, in the following way, starting from the commercially available 2-amino-5-nitrobenzoic acid, it being possible for all reaction steps to be carried out analogously to methods known from the literature (cf. Scheme 3 ).

The compound (XV; R '= Me) is a suitable starting material for the preparation of the amides (Xd). They are also obtained analogously to methods known from the literature from (XV) by reaction with the respective amine.

The carbamates of the formula (III) can be prepared by methods which are described in South African patent applications 82/5671 and 82/5045 or

EP-A 70804 (US-A-4 480 101) or RD 275056. The reaction of the compounds (IV) with the amino heterocycles (V) 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. The required starting materials (V) are known from the literature or can be prepared by processes known from the literature. The phenylsulfonylcarbamates of the formula (IV) are obtained analogously

US-A-4 684 393 or US-A-4 743 290.

The phenylsulfonyl isocyanates of the formula (VI) can be analogously

Prepare US-A-4 481 029 and react with the amino heterocycles (V).

The (thio) isocyanates of the formula (VII) can be obtained by processes known from the literature (EP-A-232067, EP-A-166516). The reaction of the (thio) isocyanates (VII) with compounds (II) takes place, for example, at -10 to 100 ° C,

preferably 20 to 100 ° C, in an inert aprotic solvent such as acetone or acetonitrile in the presence of a suitable base such as N (C ₂ H ₅ ) ₃ or K ₂ CO ₃ .

The reaction of an amino heterocycle of the formula (V) with diphenyl carbonate and a sulfonamide of the formula (II) in a one-pot reaction can be carried out in accordance with EP-A-562 575.

The salts of the compounds of formula (I) are preferably in inert polar solvents such as e.g. Water, methanol or acetone

Temperatures from 0 to 100 ° C. Suitable bases for the preparation of the salts according to the invention are, for example, alkali metal carbonates, such as

Potassium carbonate, alkali and alkaline earth hydroxides, e.g. NaOH or KOH, or ammonia or ethanolamine.

With the "inert" designated in the above process variants

Solvents "mean solvents which are inert under the respective reaction conditions, but not under any Reaction conditions must be inert.

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. Even difficult to fight

perennial weeds made from rhizomes, rhizomes or others

Expelling 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.

Some representatives of mono- and dicotyledons are examples

Weed flora called by the compounds of the invention

can be checked without being restricted to certain species by the naming.

On the side of the monocot weed species, e.g. 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 as well as sorghum and perennial Cyperus species 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 in 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.

Are the compounds of the invention prior to germination on the

Applied to the earth's surface, either weed seedlings are completely prevented from growing or the weeds grow up to the cotyledon stage, but then stop growing and eventually die after they have expired from three to four weeks.

When applying the active ingredients to the green parts of the plant in

Post-emergence also occurs very rapidly after the treatment and the weed plants remain in the growth stage at the time of application or die completely after a certain time, so that one for the

Crops harmful weed competition is eliminated very early and sustainably.

Although the compounds of the invention have excellent herbicidal activity against mono- and dicotyledon weeds, they will

Cultivated plants of economically important crops such as Wheat, barley, rye, rice, corn, sugar beet, cotton and soy are only slightly or not at all damaged. The present compounds are suitable from these

Reasons very well for selective control of undesirable

Plant growth in agricultural crops.

In addition, the substances according to the invention have excellent growth-regulating properties in crop plants. They intervene in the plant's metabolism in a regulating manner and can thus be used to influence plant constituents in a targeted manner and to facilitate harvesting, e.g. by triggering desiccation and stunted growth. Furthermore, they are also suitable for general control and

Inhibiting unwanted 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. Subject of The invention is therefore also herbicidal and plant growth-regulating compositions which contain 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 powder

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 , 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 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, NY 1963; McCutcheon's Detergents and Emulsifiers Annual, MC Publ. Corp., Ridgewood NJ; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., NY 1964; Schönfeldt, "Interface-active ethylene oxide adducts", Wiss. Publishing company, Stuttgart 1976; Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th edition 1986.

Based on these formulations, combinations with other pesticidally active substances, e.g. Insecticides, acaricides,

Herbicides, fungicides, as well as with safeners, fertilizers and / or

Create 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 inert substance, but also ionic and / or nonionic surfactants (wetting agents, dispersing agents), e.g. polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines,

Fatty alcohol polyglykoiether sulfates, alkanesulfonates, alkylbenzenesulfonates, ligninsulfonic acid sodium, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, dibutylnaphthalenesulfonic acid sodium or oleoylmethyl tauric acid sodium. To produce the wettable powders, the herbicidal active ingredients are used, for example, in customary equipment such as hammer mills,

Blower mills and air jet mills are finely ground and mixed simultaneously 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). 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. 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, for example 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 bead mills and optionally adding surfactants, such as those e.g. upstairs with the others

Formulation types already listed can be produced.

Emulsions, e.g. Oil-in-water emulsions (EW) can be used, for example, with stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, such as those e.g. already listed above for the other types of formulation,

produce.

Granules can either by spraying the active ingredient

adsorbable, granulated inert material or by applying active ingredient concentrates by means of adhesives, e.g.

Polyvinyl alcohol, polyacrylic acid sodium or mineral oils on which

Surface of carriers such as sand, kaoiinite 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 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.

For the production of plate, fluidized bed, extruder and spray granules, see e.g. Procedure in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; J.E. Browning, "Agglomeration", Chemical and Engineering 1967, pages

147 ff; "Perry's Chemical Engineer's Handbook," 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.

For more details on the formulation of crop protection products see e.g. G.C. Klingman, "Weed Control as a Science," John Wiley and Sons, Inc., New York, 1961, pages 81-96, and J.D. Freyer, S.A. Evans, "Weed Control

Handbook ", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

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

The active substance concentration in wettable powders is e.g. about 10 to 90 wt .-%, the rest of 100 wt .-% consists of conventional 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% by weight of active ingredient, preferably mostly 5 to 20% by weight of active ingredient, sprayable solutions contain 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. The active ingredient content of the water-dispersible granules 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 usual adhesive, wetting, dispersing, emulsifying, penetrating,

Preservatives, antifreeze and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and agents that influence pH and viscosity.

As a combination partner for the active substances according to the invention in

Mixture formulations or in the tank mix can be used, for example, known active ingredients, as described, for example, in Weed Research 26, 441 -445 (1986), or "The Pesticide Manual", 9th edition, The British Crop Protection 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 , if necessary together with a usual code number):

acetochlor; acifluorfen; aclonifen; AKH 7088, d. H. [[[1- [5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrophenyl] -2-methoxyethylidenes] amino] -oxy] - acetic acid and methyl acetate; alachlor; alloxydim; ametryn;

amidosulfuron; amitrole; AMS, i.e. H. Ammonium sulfamate; anilofos; asulam;

atrazine; azimsulfurone (DPX-A8947); aziprotryn; barban; BAS 516 H, i.e. H.

5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; benazolin; benfluralin; benfuresate; bensulfuron-methyl; bensulide; bentazone; benzofenap; benzofluor; benzoyl-prop-ethyl; benzthiazuron; bialaphos; bifenox; bromacil; bromobutide;

bromofenoxim; bromoxynil; bromuron; buminafos; busoxinone; butachlor;

butamifos; butenachlor; buthidazole; butralin; butylates; cafenstrole (CH-900); carbetamide; cafentrazone (ICI-A0051); CDAA, i.e. H. 2-chloro-N, N-di-2-propenylacetamide; CDEC, i.e. H. 2-chloroallyl ester of diethyldithiocarbamic acid; chlomethoxyfen; chloramben; chlorazifop-butyl, chloromesulone (ICI-A0051);

chlorbromuron; chlorobufam; chlorfenac; chlorflurecol-methyl; chloridazon;

chlorimuron ethyl; chloronitrofen; chlorotoluron; chloroxuron; chlorpropham;

chlorsulfuron; chlororthal dimethyl; chlorothiamide; cinmethylin; cinosulfuron;

clethodim; clodinafop and its ester derivatives (e.g. clodinafop-propargyl);

clomazone; clomeprop; cloproxydim; clopyralid; cumyluron (JC 940); cyanazine; cycloate; cyclosulfamuron (AC 104); cycloxydim; cycluron; cyhalofop and its ester derivatives (e.g. butyl ester, DEH-1 12); cyperquat; cyprazine;

cyprazole; daimuron; 2,4-DB; dalapon; desmedipham; desmetryn; di-allate;

dicamba; dichlobenil; dichlorprop; diclofop and its esters such as

diclofop-methyl; diethatyl; difenoxuron; difenzoquat; diflufenican; dimefuron; dimethachlor; dimethametryn; dimethenamid (SAN-582H); dimethazone, clomazone; dimethipin; dimetrasulfuron, dinitramine; dinoseb; dinoterb; diphenamide; dipropetryn; diquat; dithiopyr; diuron; DNOC; eglinazine-ethyl;

EL 177, i.e. H. 5-cyano-1- (1, 1-dimethylethyl) -N-methyl-1H-pyrazole-4-carboxamide; endothal; EPTC; esprocarb; ethalfluralin; ethametsulfuron-methyl; ethidimuron; ethiozin; ethofumesate; F5231, i.e. H. N- [2-chloro-4-fluoro-5- [4- (3-fluoropropyl) -4,5-dihydro-5-oxo-1 H-tetrazol-1-yl] phenyl] ethanesulfonamide;

ethoxyfen and its esters (e.g. ethyl ester, HN-252); etobenzanide (HW 52); fenoprop; fenoxan, fenoxaprop and fenoxaprop-P and their esters, e.g.

fenoxaprop-P-ethyl and fenoxaprop-ethyl; fenoxydim; fenuron; flamprop-methyl; flazasulfuron; fluazifop and fluazifop-P and their esters, e.g. fluazifop-butyl and fluazifop-P-butyl; fluchloralin; flumetsulam; flumeturon; flumiclorac and its esters (e.g. pentyl ester, S-23031); flumioxazin (S-482); flumipropyn; flupoxam (KNW-739); fluorodifen; fluoroglycofen-ethyl; flupropacil (UBIC-4243); fluridone; flurochloridone; fluroxypyr; flurtamone; fomesafen; fosamine; furyloxyfen;

glufosinate; glyphosate; halosafen; halosulfuron and its esters (e.g.

Methyl ester, NC-319); haloxyfop and its esters; haloxyfop-P

(= R-haloxyfop) and its ester; hexazinone; imazamethabenz-methyl;

imazapγr; imazaquin and salts such as the ammonium salt; 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; metabenzuron, methobenzuron; metobromuron; metolachlor; metosulam

(XRD 511); metoxuron; metribuzin; metsulfuron-methyl; MH; molinate;

monalide; monocarbamide dihydrogen sulfates; monolinuron; monuron; MT 128, i.e. H. 6-chloro-N- (3-chloro-2-propenyl) -5-methyl-N-phenyl-3-pyridazinamine;

MT 5950, i.e. H. N- [3-chloro-4- (1-methylethyl) phenyl] -2-methylpentanamide;

naproanilide; napropamide; naptalam; NC 310, i.e. H. 4- (2,4-dichlorobenzoyl) -1 - methyl-5-benzyloxypyrazole; neburon; nicosulfuron; nipyraclophen; nitraline;

nitrofen; nitrofluorfen; norflurazon; orbencarb; oryzalin; oxadiargyl (RP-020630); oxadiazon; oxyfluorfen; paraquat; pebulate; pendimethalin; perfluidone;

phenisopham; phenmedipham; picloram; piperophos; piributicarb; pirifenop-butyl; pretilachlor; primisulfuron-methyl; procyazine; prodiamine; profluralin; proglinazine-ethyl; prometon; prometryn; propachlor; propanil; propaquizafop and its esters; propazine; propham; propisochlor; propyzamide; prosulfalin; prosulfocarb; prosulfuron (CGA-152005); prynachlor; pyrazolinates; pyrazone; pyrazosulfuron-ethyl; pyrazoxyfen; pyridate; pyrithiobac (KIH-2031); pyroxofop and its esters (eg propargyl esters); quinclorac; quinmerac; quinofop and its ester derivatives, quizalofop and quizalofop-P and their ester derivatives, for example quizalofop-ethyl; quizalofop-P-tefuryl and ethyl; renriduron; rimsulfuron (DPX-E 9636); S 275, ie 2- [4-chloro-2-fluoro-5- (2-propynyloxy) phenyl] -4,5,6,7-tetrahydro-2H-indazole; secbumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, ie 2 - [[7- [2-chloro-4- (trifluoromethyl) phenoxy] -2-naphthalenyl] oxy] propanoic acid and methyl ester; sulfentrazone (FMC-97285, F-6285);

sulfazuron; sulfometuron-methyl; sulfosate (ICI-A0224); TCA; tebutam (GCP-5544); tebuthiuron; terbacil; terbucarb; terbuchlor; terbumeton; terbuthylazine; terbutryn; TFH 450, i.e. H. N, N-Diethyl-3 - [(2-ethyl-6-methylphenyl) sulfonyl] -1 H-1, 2,4-triazole-1-carboxamide; thenylchlor (NSK-850); thiazafluron; thizopyr (Mon-13200); thidiazimin (SN-124085); thifensulfuron-methyl; thiobencarb;

tiocarbazil; tralkoxydim; tri-allate; triasulfuron; triazofenamide;

tribenuron-methyl; triclopyr; tridiphane; trietazine; trifluralin; triflusulfuron and esters (e.g. methyl ester, DPX-66037); trimeturon; tsitodef; vernolate;

WL 1 10547, i.e. H. 5-phenoxy-1- [3- (trifluoromethyl) phenyl] -1 H-tetrazole;

UBH-509; D-489; LS 82-556; KPP-300; NC-324; NC-330; KH-218;

DPX-N8189; SC-0774; DOWCO-535; DK-8910; V-53482; PP-600; MBH-001; KIH-9201; ET-751; KIH-6127 and KIH-2023.

Those available in the commercial form are used

Formulations optionally diluted in the usual way e.g. for wettable powders, emulsifiable concentrates, dispersions and water-dispersible

Granules using water. Dust-like preparations, soil or

Scatter granules and sprayable solutions are usually no longer diluted with other inert substances before use. With the external conditions such as temperature, humidity, the type of herbicide used, among other things, the required application rate varies

Compounds of formula (I). It can fluctuate within wide limits, e.g. between 0.001 and 10.0 kg / ha or more of active substance, but it is preferably between 0.005 and 5 kg / ha.

A. Chemical examples

Example A1

N-tert-butyl-2-chloro-5-nitrobenzenesulfonamide

165 g of dried 2-chloro-5-nitrobenzenesulfonic acid sodium salt (90%) are placed in 264 ml of acetonitrile, 264 ml of sulfolane and 16.5 ml of dimethylformamide (DMF). After the dropwise addition of 198 ml of phosphorus oxychloride, the mixture is heated to boiling for 2 hours. After the mixture has cooled, it is poured into cold water, extracted with ethyl acetate, the combined organic phases are dried over sodium sulfate and concentrated. The

Residue (mixture of sulfolane and 2-chloro-5-nitrobenzenesulfochloride) is taken up in 1500 ml dichloromethane, with 130 ml tert-butylamine

(Ice bath cooling) and stirred for about 2 hours at room temperature. After washing with dilute hydrochloric acid and drying over MgSO ₄ , the organic phase is concentrated. The residue is stirred with methanol and cooled to 0 ° C. The separated solid (109 g, mp 168-171 ° C) is separated and dried. A second fraction of the product of comparable quality (46.7 g) can be obtained analogously from the mother liquor.

Example A2

N-tert-butyl-2-ethylmercapto-5-nitrobenzenesulfonamide

5.6 ml of ethyl mercaptan are added at room temperature to a suspension of 20.0 g of N-tert-butyl-2-chloro-5-nitrobenzenesulfonamide, 18.9 g of potassium carbonate and 100 ml of DMF. After 3 hours of stirring, the mixture in High vacuum concentrated. The residue is taken up in water and concentrated with. Acidified hydrochloric acid (pH 1 to 2). The aqueous phase is with

Extracted ethyl acetate. The combined organic phases are dried over magnesium sulfate and then concentrated under reduced pressure. This gives 21, 25 g of the desired ethyl mercaptan;

Melting point: 172 to 174 ° C.

Example A3

N-tert-butyl-2-ethylsulfonyl-5-nitrobenzenesulfonamide

G To a solution of 60.0 N-tert-butyl-2-ethylmercapto-5-nitrobenzenesulfonamide in 900 ml of methanol a solution of 180 g of Oxone ^® (potassium peroxymonosulfate) is then added dropwise in 600 ml of water at a temperature of 65 ° C. After stirring for 5 hours at this temperature, this is cooled

Reaction mixture, poured onto water and extracted with ethyl acetate. The combined organic phases are washed with water, dried over magnesium sulfate and then concentrated. This gives 60.6 g of the ethyl sulfone; Melting point: 108 to 1 1 1 ° C.

Example A4

5-amino-N-tert-butyl-2-ethylsulfonylbenzenesulfonamide

To a solution of 17.6 g (50.2 mmol) of N-tert-butyl-2-ethylsulfonyl-5-nitrobenzenesulfonamide in 70 ml of acetic acid and 23 ml of water, 9.3 g (165, 7 mmol) iron powder. When the addition is complete, the mixture is stirred at 80 ° C for 4.5 hours, 30 ml of 2N HCl are added and the mixture is allowed to cool to 25 ° C. It is suctioned off, washed 3 times with water and the washed solid is dissolved in ethyl acetate. After washing the organic phase with water, drying and evaporation, 12.3 g (76% of theory) of 5-amino-N-tert-butyl-2-ethylsulfonylbenzenesulfonamide are obtained, melting point 193 to 194 ° C. Example A5

N-tert-butyl-2-ethylsulfonyl-5-hydrazinobenzenesulfonamide

4.0 g (12.5 mmol) of 5-amino-N-tert-butyl-2-ethylsulfonylbenzenesulfonamide are concentrated in 14 ml. HCl submitted at 0 to 5 ° C and 1.0 g (13.7 mmol) of NaNO ₂ dissolved in 5 ml of water were added within 5 minutes. The mixture is stirred at 0 ° C for 10 minutes and the resulting solution is added at 0 to 5 ° C to a solution of 8.5 g (37.5 mmol) of tin (II) chloride dihydrate, dissolved in 9 ml of conc. HCl. After stirring for 18 hours, pour on ice and put first

6n NaOH, then the pH to 5 to 6 with solid NaHCO ₃ . It is extracted several times with ethyl acetate, the organic phase is dried and evaporated. 2.4 g (58% of theory) of N-tert-butyl-2-ethylsulfonyl-5-hydrazinobenzenesulfonamide are obtained, melting point 136 to 140 ° C.

Example A6

N-tert-butyl-2-ethylsulfonyl-5- (2-propionylhydrazino) benzenesulfonamide

To 2.0 g (6 mmol) of N-tert-butyl-2-ethylsulfonyl-5-hydrazinobenzenesulfonamide in 27 ml of pyridine is added dropwise 0.58 g (6.3 mmol) of propionyl chloride at -30 ° C. The mixture is stirred at -30 ° C. for 2 hours, slowly brought to 0 ° C., poured into ice water and brought to pH 1 with 2N HCl. After extraction with CH ₂ Cl ₂ , drying and evaporation, 1.6 g (69% of theory) are obtained. ) N-tert-butyl-2-ethylsulfonyl-5- (2-propionylhydrazino) benzenesulfonamide with the following ¹ H-NMR signals:

1H NMR (d ₆ -DMSO): δ = 1.08 (t, 3H, CH ₂ CH ₃ ); 1, 10 (t, 3H, CH ₂ CH ₃ ),

1, 15 (s, 9H, C (CH ₃₎ _3); 2.22 (q, 2H, COCH ₂ ); 3.49 (q, 2H, SO ₂ CH _2);

6.52 (s, 1 H, SO ₂ NH); 6.93 (dd, 1H, Aromat-4-H); 7.47 (d, 1H, Aromat-6-H); 7.88 (d, 1H, Aromat-3-H); 9.04 (s, 1H, NH); 9.96 (1H, s, NH). Example A7

N-tert-butyl-2-ethylsulfonyl-5-isopropylidene hydrazinobenzenesulfonamide

A solution of 2.4 g (7.5 mmol) of N-tert-butyl-2-ethylsulfonyl-5-hydrazinobenzenesulfonamide and 2.2 g (37.5 mmol) of acetone in 40 ml of methanol is stirred for 2 hours at 25 ° C. After evaporation, 2.7 g (95% of theory) of N-tert-butyl-2-ethylsulfonyl-5-isopropylidene hydrazinobenzenesulfonamide from

Melting point 177 to 178 ° C.

Example A8

2-ethylsulfonyl-5- (2-propionylhydrazino) benzenesulfonamide

A mixture of 1.6 g (4 mmol) of N-tert-butyl-2-ethylsulfonyl-5- (2-propionylhydrazino) benzenesulfonamide and 20 ml of trifluoroacetic acid is stirred for 2.5 hours at 25 ° C. It is evaporated, the residue is triturated with diethyl ether and, after filtering and drying, 1.25 g (91% of theory) of 2-ethylsulfonyl-5- (2-propionylhydrazino) benzenesulfonamide are obtained, melting point 198 to 200 ° C.

Example A9

3- (4,6-Dimethoxypyrimidin-2-yl) -1- [2-ethylsulfonyl-5- (2-propionylhydrazino) phenylsulfonyl] urea, sodium salt

To a mixture of 1.2 g (3.6 mmol) of 2-ethylsulfonyl-5- (2-propionylhydrazino) benzenesulfonamide, 1.4 g (5 mmol) of phenyl-N- (4,6-dimethoxypyrimidin-2-yl) carbamate and 30 ml of acetonitrile are added at 25 ° C 0.2 g (5.4 mmol) of powdered sodium hydroxide. The mixture is stirred at 25 ° C. for 2.5 hours, evaporated and the residue is triturated with diethyl ether. After filtering off and drying, 1.5 g (75% of theory) of 3- (4,6-dimethoxypyrimidin-2-yl) -1- [2-ethylsulfonyl-5- (2-propionylhydrazino) phenylsulfonyl] urea are obtained as Sodium salt, melting point 219 to 221 ° C. Example A10

2-tert-butylsulfamoyl-4-nitrobenzoic acid dimethylamide

A solution of 69.0 g (0.22 mol) of methyl 2-tert-butylsulfamoyl-4-nitrobenzoate and 900 ml of methanol is passed at about 25 ° C.

210 g (4.5 mol) of gaseous dimethylamine. The mixture is stirred at 25 ° C for 5 days, evaporated and the residue is crystallized by trituration with diisopropyl ether. The resulting solid is dissolved in dichloromethane and the organic phase is washed four times with bicarbonate solution. It is dried, evaporated and 39.0 g (54% of theory) of 2-tert-butylsulfamoyl-4-nitrobenzoic acid dimethylamide are obtained as the residue, melting point 143 ° to 145 ° C. (dec.).

Example A1 1

4-Amino-2-tert-butylsulfamoylbenzoic acid dimethylamide

22.5 g (0.4 mol) of iron powder are added in portions at 80 ° C. to a mixture of 40.2 g (0.12 mol) of 2-tert-butylsulfamoyl-4-nitrobenzoic acid dimethylamide, 165 ml of glacial acetic acid and 50 ml of water. The mixture is stirred for 4 hours at 80 to 85 ° C and then 70 ml of 2N HCl are added to the still hot solution. After cooling to room temperature, the product is filtered off with suction and the solid is washed several times with water. The solid is stirred with ethyl acetate, filtered off, the organic phase is dried and evaporated. The remaining solid is triturated with diisopropyl ether. 24.1 g (66% of theory) of 4-amino-2-tert-butylsulfamoylbenzoic acid dimethylamide are obtained, melting point 205 to

206 ° C.

Example A12

2-tert-butylsulfamoyl-4-hydrazinobenzoic acid dimethylamide

5.0 g (16.7 mmol) of 4-amino-2-tert-butylsulfamoylbenzoic acid dimethylamide are concentrated in 6.7 ml. HCl and 8 ml of water suspended. A solution of 1.3 g (18.4 mmol) of sodium nitrite in 6 ml of water is added dropwise at 0 to 5 ° C. To For 5 minutes, the undissolved residue is filtered off and the liquid phase is added at 0 ° C. to a solution of 11.3 g (50 mmol) of stannous chloride dihydrate in 12 ml of conc. HCl. The reaction mixture is kept at 0 ° C. for 16 hours and the pH is then adjusted to 6-7 by adding 47 g of 6N NaOH solution and 5 g of solid NaHCO ₃ . It is extracted with ethyl acetate, dried and evaporated. There remain 3.5 g (66% of theory) of 2-tert-butylsulfamoyl-4-hγdrazinobenzoic acid dimethylamide as a yellow oil;

1H-NMR (CDCI ₃ ): δ = 1.23 (s, 9H, C (CH ₃ ) ₃ ); 2.87 (s, 3H, NCH _3);

3.07 (s, 3H, NCH _3); 3.65 (broad, 2H, NH ₂ ); 6.02 (broad, 1H, phenyl NH);

6:04 (s, 1 H, SO ₂ NH); 7.01 (dd, 1H, phenyl-5H); 7.1 1 (d, 1H, phenyl-6H);

7.44 (d, 1H; phenyl-3H).

Example A13

2-tert-butylsulfamoyl-4-ethylidene hydrazinobenzoic acid dimethylamide

3.5 g (1 1 mmol) of 2-tert-butylsulfamoyl-4-hydrazinobenzoic acid dimethylamide in 70 ml of methanol are stirred with 1.2 g (22 mmol) of acetaldehyde at 25 ° C. for 3 hours. It is evaporated, the residue is triturated with diisopropyl ether and, after filtering off and drying, 2.6 g (69% of theory) of 2-tert-butylsulfamoyl-4-ethylidene-hydrazinobenzoic acid dimethylamide are obtained, melting point 187 to 189 ° C.

Example A14

4-ethylidene hydrazino-2-sulfamoylbenzoic acid dimethylamide

2.0 g (5.9 mmol) of 2-tert-butylsulfamoyl-4-ethylidene hydrazinobenzoic acid dimethylamide are stirred in 30 ml of trifluoroacetic acid at 25 ° C for 2 hours. It is evaporated and the residue is triturated with diethyl ether. 0.8 g (48% of theory) of 4-ethylidene hyrazino-2-sulfamoylbenzoic acid dimethylamide are obtained, melting point 188 to 192 ° C. Example A15

2- [3- (4,6-Dimethoxypyrimidin-2-yl) ureidosulfonyl] -4-ethylidene hydrazinobenzoic acid dimethylamide

To a mixture of 0.7 g (2.5 mmol) of 4-ethylidene hydrazino-2-sulfamoylbenzoic acid dimethylamide, 0.8 g (3.0 mmol) of phenyl-N- (4,6-dimethoxypyrimidin-2-yl) carbamate and 20 ml of acetonitrile are added at 0 ° C to 0.8 g (5.4 mmol) of 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU). The mixture is stirred at 0 ° C. for 2 hours, then poured into ice water, brought to pH 2 with 2N HCl and extracted with dichloromethane. The organic phase is washed with 2N HCl, dried and evaporated. After trituration with diisopropyl ether, 0.45 g (39% of theory) of 2- [3- (4,6-dimethoxypyrimidin-2-yl) ureidosulfonyl] -4-ethylidene-hyrazinobenzoic acid dimethylamide with a melting point of 127 to 129 ° C. (decomp.) Is obtained.

The compounds described in Tables 1, 2 and 3 below are obtained according to or analogously to Examples A1 to A15 above.

Abbreviations in the tables:

M.p. = mp. Fixed point in ° C = melting point in ° C

(Z) = melting point with decomposition

Ac = acetyl

Bu = ⁿ Bu = n-butyl

i-Bu = isobutyl

t-Bu = t-butyl

Et = ethyl

Me = methyl

Pg = propargyl

Ph = phenyl

Pr = ⁿ Pr = n-propyl

i-Pr = isopropyl

c-Pr = cyclopropyl

Het = heterocycle, where Het stands for one of the radicals T1 to T15

For reasons of better readability of index numbers, the tables contain formula residues such as NH ₄ , CH ₂ CO ₂ Me, CH ₃ SCH ₂ CH ₂ - etc. contrary to the usual spelling with atomic symbols and index numbers in the same amount, ie as NH4, CH2CO2Me, CH3SCH2CH2- etc.

A diradical such as - (CH2) 4- in columns for R ⁷ , R ⁸ means that R ⁷ and R ⁸ together represent the diradical bridge and form an alkylidene radical with the carbon atom of the group R ⁷ R ⁸ C =. The same applies to other entries that apply to two columns.

B. Formulation Examples a) A dust is obtained by adding 10 parts by weight of a

Mixing compound of formula (I) and 90 parts by weight of talc as an inert substance and comminuted in a hammer mill. b) A wettable powder which is readily dispersible in water is obtained by mixing 25 parts by weight of a compound of the formula (I),

64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of ligninsulfonic acid potassium and 1 part by weight of oleoylmethyl tauric acid sodium as wetting and dispersing agent and mixed in a pin mill. c) A readily water-dispersible dispersion concentrate is obtained by mixing 20 parts by weight of a compound of formula (I) with 6 parts by weight of alkylphenol polyglycol ether (Triton ^® X 207), 3 wt. parts by

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 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 the 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 mixes, grinds on a pin mill and granulates the powder in a fluidized bed by spraying water as granulating liquid. f) A water-dispersible granulate is also obtained by

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

homogenized on a colloid mill and pre-comminuted, 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 are placed in sandy loam in plastic pots and covered with soil. 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. The visual assessment of the damage to the plants or the soiling occurs after the soiling

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, the compounds of Examples 1-37, 1-38, 1-91, 1-92, 1-146, 1-147, 2-97, 2-98, 2-247, 2-248, 2-260, 2-349, 3-19 and 3-128 (see tables 1 to 3) very good herbicidal activity against harmful plants such as Sinapis alba,

Chrysanthemum segetum, Avena sativa, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Setaria spp., Matricaria inodora, Abutilon theophrasti, Amaranthus retroflexus and Panicum miliaceum 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. Formulated as wettable powder or emulsion concentrates

Compounds according to the invention 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. After about 3 to 4 weeks of standing

Experimental plants in the greenhouse under optimal growth conditions, the effect of the preparations is visual compared to untreated

Controls rated. 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 1-37, 1-38, 1-91, 1-92, 1-146, 1-147, 2-97, 2-98, 2-247, 2-248, 2-260, 2-349, 3-19 and 3-128 (see Tables 1 to 3) very good herbicidal activity against harmful plants such as Sinapis alba, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Chrysanthemum segetum, Setaria spp., Matricaria inodora, Abutilon theophrasti, Amaranthus retroflexus, Panicum miliaceum 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. Part of the pots are immediately as described in section 1

described treated, the rest in the greenhouse until the plants had developed two to three real leaves and then as described in Section 2 with the substances of formula (I) according to the invention in

sprayed different doses. Four to five weeks after the

Application and service life in the greenhouse is determined by means of an optical rating that the compounds according to the invention dicotyledonous

Cultures such as Leaving 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) show in part a high selectivity and are therefore suitable for combating undesirable plant growth in

agricultural crops.

Claims

Claims: 1. Compounds of formula (I) or their salts,

wherein

R ¹ S (O) _n R ⁴ , SO ₂ NR ⁵ R ⁶ or CONR ⁵ R ⁶ ,

R ³ H or (C ₁ -C ₄ ) alkyl,

R ^{4 is} an aliphatic hydrocarbon radical or aryl, each of the

two latter radicals is unsubstituted or substituted,

R ⁵ and R ⁶ together with the N atom represent a heterocyclic radical which

is unsubstituted or substituted,

SO ₂ NR ⁵ R ⁶ , also A ² ,

R ⁷ , R ⁸ independently of one another H, NO ₂ , CN, an aliphatic

Hydrocarbon radical, a heterocyclic radical or aryl, each of the last three radicals being unsubstituted or substituted, or an acyl radical, or

R ⁷ and R ⁸ together with the carbon atom are a carbocyclic or

heterocyclic ring which is unsubstituted or substituted,

R ⁹ H, an aliphatic hydrocarbon residue which is unsubstituted or

is substituted, or an acyl radical,

R ^{10 is} an acyl radical which is unsubstituted or substituted,

R ¹¹ H or an aliphatic hydrocarbon radical which is unsubstituted or substituted,

W is an oxygen or sulfur atom,

Z CH or N and

n 0, 1 or 2

mean.

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

R ¹ S (O) _n R ⁴ , SO ₂ NR ⁵ R ⁶ or CONR ⁵ R ⁶ ,

R ³ H or (C ₁ -C ₄ ) alkyl,

R ⁴ (C ₁ -C ₆ ) alkyl, (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆ ) alkynyl, (C ₃ -C ₇ ) cycloalkyl,

(C ₃ -C ₇ ) cycloalkyl- (C ₁ -C ₃ ) alkyl, phenyl, each of the latter six residues unsubstituted or by one or more residues from the group halogen, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) alkylthio, (C. ₁ -C ₄ ) alkylsulfinyl, (C ₁ -C ₄ ) alkylsulfonyl , unsubstituted or substituted phenyl

[(C ₁ -C ₄ ) alkoxy] carbonyl and in the case of cyclic radicals also (C. ₁ -C ₄ ) alkyl and (C ₁ -C ₄ ) haloalkyl is substituted,

- [(C ₁ -C ₄ ) alkoxy] carbonyl is substituted,

(C ₁ -C ₄ ) alkylsulfonyl, NO ₂ or COOH or carbamoyl which is unsubstituted or one or two substituents from the group of Residues (C ₁ -C ₄ ) alkyl, (C ₃ -C ₄ ) aikenyl, (C ₃ -C ₄ ) alkynyl and phenyl which are unsubstituted or by one or more residues from the group halogen, (C ₁ -C ₄ ) Alkyl, (C ₁ -C ₄ ) haloalkyl, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) alkylthio, (C ₁ -C ₄ ) alkylsulfonyl, [(C ₁ -C ₄ ) alkoxy] carbonyl , CN and NO _{2 is} substituted, or di - [(C ₁ -C ₄ ) alkoxy] -phosphinyl or

wherein

R ^* H, (C ₁ -C ₈ ) alkyl, (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆ ) alkynyl, each of the last three radicals being unsubstituted or by one or more radicals from the group halogen, ( C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) alkylthio, phenoxy, [(C ₁ -C ₄ ) alkoxy] carbonyl, unsubstituted or substituted heterocyclyl and unsubstituted or substituted phenyl, or unsubstituted or substituted (C ₃ -C ₆ ) cycloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted heterocyclyl or [(C ₁ -C ₄ ) alkoxy] carbonyl,

R ^{* *} (C ₁ -C ₆ ) alkyl, (C ₃ -C ₆ ) alkenyl, (C ₃ -C ₆ ) alkynyl, each of the last three radicals unsubstituted or by one or more radicals from the group halogen, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) alkylthio and phenyl is substituted, or phenyl which is unsubstituted or by one or more radicals from the group halogen, CN, NO ₂ , (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) haloalkyl and (C ₁ -C ₄ ) Alkoxy is substituted,

R ^{10 is} an acyl radical of the formula

R ^{1 1} H, (C ₁ -C ₆ ) alkyl, (C ₃ -C ₆ ) aikenyl, (C ₃ -C ₆ ) alkynyl, each of the three

Heterocyclyl or [(C ₁ -C ₄ ) alkoxy] carbonyl,

the latter radicals unsubstituted or by one or more radicals from the group halogen, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) alkylthio,

R ^{16 is} a radical from the group of the radicals possible for R ⁶ or

W is an oxygen atom or a sulfur atom, preferably a

Oxygen atom,

W ^{* is} an oxygen atom or a sulfur atom, preferably O,

T is an oxygen atom or a sulfur atom, preferably O,

n 0, 1 or 2,

Z CH or N

mean.

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

R ⁷ , R ⁸ independently of one another are H, (C ₁ -C ₄ ) alkyl, (C ₂ -C ₄ ) alkenyl, each of the latter two radicals being separated by one or more radicals from the Halogen, (C ₁ -C ₄ ) alkoxy and phenyl group is substituted, or

(C ₃ -C ₆ ) cycloalkyl, (C ₃ -C ₄ ) alkynyl, phenyl or phenylcarbonyl, each of the latter two radicals being unsubstituted or by one or more radicals from the group consisting of fluorine, chlorine, CN, NO ₂ ,

[(C ₁ -C ₄ ) alkoxy] carbonyl, or furyl, pyridyl, thienyl, tetrahydrofuryl, [(C ₁ -C ₄ ) alkoxy] carbonyl or COOH or CN, NO ₂ , carbamoyl, which is unsubstituted or by residues from the group (C ₁ -C ₄ ) alkyl is mono- or disubstituted or is monosubstituted by phenyl, or -PO (OCH ₃ ) ₂ or -PO (OC ₂ H ₅ ) ₂ or

R ^{10 is} a radical of the formula

[(C ₁ -C ₄ ) alkoxy] carbonyl and unsubstituted or substituted phenyl, or (C ₂ -C ₄ ) alkenyl, (C ₂ -C ₄ ) alkynyl, (C ₃ -C ₆ ) cycloalkyl, [(C ₁ -C ₄ ) alkoxy] carbonyl, unsubstituted or substituted phenyl or unsubstituted or substituted heterocycyl, R ^{13 is} (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) haloalkyl, (C ₃ -C ₄ ) alkenyl, (C ₃ -C ₄ ) alkynyl or

(C ₃ -C ₆ ) cycloalkyl,

R ^{18 is} a radical from the group of the radicals possible for R ⁶ , or

R ¹⁵ and R ¹⁸ together with the N atom form a heterocycle as is possible for NR ⁵ R ⁸ ,

W ^{* is} an oxygen atom or a sulfur atom and

mean.

4. Compounds of formula (I) or their salts according to one of the claims

1 to 3, characterized in that

R ² H, halogen or (C ₁ -C ₂ ) alkyl,

R ⁵ , R ⁸ independently of one another are H, (C ₁ -C ₄ ) alkyl, (C ₃ -C ₄ ) alkenyl or

(C ₃ -C ₄ ) alkynyl or

R ⁵ and R ⁸ together with the N atom form a heterocyclic ring with 5 or

6 ring links,

(C ₃ -C ₆ ) cycloalkyl or [(C ₁ -C ₄ ) alkoxy] carbonyl or

R ^{10 is} a radical of the formula

R ^{1 1} H or (C ₁ -C ₄ ) alkyl, R ¹² H, (C ₁ -C ₆ ) alkyl which is unsubstituted or substituted by one or more radicals from the group halogen, (C ₁ -C ₄ ) alkoxy or phenyl, or (C ₂ -C ₄ ) alkenyl, ( C ₃ -C ₆ ) cycloalkyl or phenyl which is unsubstituted or substituted by one or more radicals from the group halogen, (C ₁ -C ₄ ) alkyl and (C ₁ -C ₃ ) alkoxy,

R ¹³ (C ₁ -C ₄ ) alkyl or (C ₁ -C ₄ ) haloalkyl,

n 2,

X (C ₁ -C ₂ ) alkyl, (C ₁ -C ₂ ) alkoxy, (C ₁ -C ₂ ) alkylthio, (C ₁ -C ₂ ) haloalkyl or (C ₁ -C ₂ ) haloalkoxy and

mean.

5. A process for the preparation of the compounds of general formula (I) or their salts, as defined in any of claims 1 to 4, characterized in that a) a compound of formula (II)

with a heterocyclic carbamate of the formula

wherein R ^* denotes unsubstituted or substituted phenyl or (C ₁ -C ₄ ) alkyl, or b) a sulfonyl carbamate of the formula (IV),

or c) a sulfonyl isocyanate of the formula (VI)

in the presence of a base or e) an amino heterocycle of the formula (V) is first base-catalyzed with a carbonic acid ester and the intermediate formed is reacted in a one-pot reaction with a sulfonamide of the formula (II), the radicals or groups R ¹ in the formulas (M) - (VII) -R ³ , A, W, X, Y and Z are as defined in formula (I) and in process variants a) to c) and e) compounds (I) with W = O are initially obtained.

6. Herbicidal or plant growth regulating agents, thereby

characterized in that it is at least one compound of formula (I) or its salt according to one of claims 1 to 4 and customary in crop protection

Contains formulation aids.

7. Methods for controlling harmful plants or

Regulating the growth of plants, characterized in that an effective amount of at least one compound of the formula (I) or its salt according to one of Claims 1 to 4 is applied to the harmful plants or plants, their plant seeds or the area on which they grow .

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

9. Compounds of formulas (II), (IV) and (VI) as defined in claim 5.