DE4335587A1 - N-heteroaryl-N'-(pyrid-2-ylsulfonyl)ureas, their preparation, and their use as herbicides and plant growth regulators - Google Patents

Abstract

Compounds of the formula (I) or their salts <IMAGE> in which R<1>-R<4>, W, A, n and m are as defined in Claim 1, for example R<1> and R<2> are H, (substituted) alkyl, (substituted) alkenyl or alkynyl, (substituted) cycloalkyl, (substituted) aryl or acyl and A is (substituted) pyrimidinyl or triazinyl, are suitable as selective sulphonylurea herbicides and plant growth regulators. They are prepared analogously to known processes, via intermediates, some of which are novel, for example suitably substituted pyridylsulphonamides (II) and N-tert-butylsulphonamides (VIII) according to Claim 5.

Description

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

It is known that some 2-pyridylsulfonylureas are herbicidal and possess plant growth regulating properties; compare EP-A-13 480, EP-A-272 855, EP-A-84224, US-A-4421550, EP-A-103543 (US-A-4 579 583) US-A-4487626, EP-A-125864, WO 88/04297 and WO 91/10660 (ZA 91/0173).

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

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

wherein
R¹ H, (C₁-C₆) alkyl which is unsubstituted or substituted by one or more radicals from the group halogen, nitro, (C₁-C₄) alkoxy, (C₃-C₆) cycloalkyl, cyano, aryl and substituted aryl, (C₃ -C₆) cycloalkyl which is unsubstituted or substituted by one or more radicals from the group halogen, (C₁-C₄) alkyl and (C₁-C₄) alkoxy, or (C₂-C₆) alkenyl or (C₂-C₆) alkynyl, where each of the latter two radicals is unsubstituted or substituted by one or more radicals from the group halogen, (C₁-C₄) alkoxy and (C₃-C₆) cycloalkyl, or aryl, substituted aryl, or an acyl radical of the formula

-CO-R *,

wherein
R * H, (C₁-C₆) alkyl, (C₂-C₆) alkenyl or (C₂-C₆) alkynyl, each of the latter three radicals unsubstituted or by one or more radicals from the group halogen, (C₁-C₄) alkoxy, (C₁- C₄) alkylthio, (C₁-C₄) alkylsulfinyl, (C₁-C₄) alkylsulfonyl, nitro, cyano, thiocyanato, aryl and substituted aryl, or (C₁-C₄) alkoxy, (C₂-C₄) alkenyloxy, ( C₂-C₄) alkynyloxy or (C₁-C₄) alkylthio, each of the latter four radicals being unsubstituted or substituted by one or more radicals from the group halogen, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, aryl and substituted aryl is, or (C₃-C₆) cycloalkyl or (C₃- C₆) cycloalkoxy, each of the latter two radicals unsubstituted or by one or more radicals from the group (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁- C₄) alkylthio, (C₁-C₄) haloalkyl, and halogen is substituted, or is a radical of the formula NRaR ^b ,
R² H, (C₁-C₆) alkyl which is unsubstituted or substituted by one or more radicals from the group halogen, nitro, (C₁-C₄) alkoxy, (C₃-C₆) cycloalkyl, aryl and substituted aryl, or (C₃- C₆) cycloalkyl which is unsubstituted or substituted by one or more radicals from the group halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₄) haloalkyl, aryl and substituted aryl, or (C₂-C₆ ) Alkenyl or (C₂- C₆) alkynyl, each of the latter two radicals being unsubstituted or substituted by one or more radicals from the group (C₁-C₄) alkoxy, (C₁- C₄) haloalkyl, (C₃-C₆) cycloalkyl and halogen , or aryl, substituted aryl or a radical of the formula R'R''R '''Si, where R', R '', R '''independently of one another are (C₁-C₄) alkyl, or an acyl radical of the formula

-CO-R **

wherein
R ** H, (C₁-C₆) alkyl, (C₂-C₆) alkenyl or (C₂-C₆) alkynyl, each of the latter three radicals unsubstituted or by one or more radicals from the group halogen, (C₁-C₄) alkoxy , (C₁-C₄) alkylthio, (C₁-C₄) alkylsulfinyl, (C₁-C₄) alkylsulfonyl, nitro, cyano, thiocyanato, aryl and substituted aryl, or (C₁-C₄) alkoxy, (C₂-C₄) alkenyloxy or (C₂-C₄) alkynyloxy, each of the latter three radicals being unsubstituted or substituted by one or more radicals from the group halogen, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, aryl and substituted aryl, or (C₃- C₆) cycloalkyl or (C₃-C₆) cycloalkoxy, each of the latter two radicals unsubstituted or by one or more radicals from the group halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio and (C₁-C₄) haloalkyl is substituted or is a radical of the formula NR ^c R ^d ,
R³ C₁-C₄) alkyl, (C₁-C₃) haloalkyl, halogen, NO₂, CN, (C₁-C₃) alkoxy, (C₁-C₃) haloalkoxy, (C₁-C₃) alkylthio, (C₁-C₃) alkoxy- (C₁ -C₃) alkyl, [(C₁-C₃) alkoxy] carbonyl, (C₁-C₃) alkylamino, di [(C₁-C₃) alkyl] amino, (C₁- C₃) alkylsulfinyl, (C₁-C₃) alkylsulfonyl, SO₂NR ^e R ^f or C (O) NR ^g R ^h ,
Ra, R ^b , R ^c , R ^d , R ^e , R ^f , R ^g and R ^h independently of one another H, (C₁-C₄) alkyl, (C₃- C₆) alkenyl, (C₃-C₆) alkynyl, [(C₁ -C₄) alkyl] carbonyl, arylcarbonyl, which is unsubstituted in the aryl radical or substituted by one or more radicals from the group halogen, (C₁-C₄) alkyl and (C₁-C₄) alkoxy, or in pairs Ra and R ^b , R ^c and R ^d , R ^e and R ^f or R ^g and R ^h together with the N atom connecting them form a heterocyclic saturated or unsaturated ring with 3 to 7 ring atoms, which in addition to the N atom has 1 or 2 further heteroatoms from the group May contain N, O and S in the possible oxidation states and which is unsubstituted or substituted,
R⁴ H or (C₁-C₄) alkyl, preferably H or CH₃, in particular H, m 0 or 1, preferably 0,
n 0, 1 or 2, preferably 0 or 1,
A is a residue of the formula

X, Y independently of one another are H, halogen, (C₁-C₃) alkyl, (C₁-C₃) alkoxy or (C₁-C₃) alkylthio, where the abovementioned alkyl-containing radicals are unsubstituted or mono- or polysubstituted by halogen or mono- or polysubstituted by ( C₁-C₃) alkoxy or (C₁-C₃) alkylthio are substituted, or a radical of the formula NR⁵R⁶, (C₃-C₆) cycloalkyl, (C₂-C₄) alkenyl, (C₂-C₄) alkynyl, (C₃-C₄) - Alkenyloxy or (C₃-C₄) alkynyloxy,
R⁵, R⁶ independently of one another H, (C₁-C₃) alkyl or (C₃-C₄) alkenyl,
WO or S, preferably O,
Z is CH or N, preferably CH,
X¹ CH₃, OCH₃, OC₂H₅ or OCF₂H,
Y¹ -O- or -CH₂-,
X² CH₃, C₂H₅ or CH₂CF₃,
Y²CH₃, OC₂H₅, SCH₃, SC₂H₅, CH₃ or C₂H₅,
X³ CH₃ or OCH₃,
Y³ H or CH₃,
X⁴ CH₃, OCH₃, OC₂H₅, CH₂OCH₃ or Cl,
Y⁴ CH₃, OCH₃, OC₂H₅ or Cl,
Y⁵ CH₃, C₂H₅, OCH₃ or Cl
mean.

In the formula (I) and below, hydrocarbon-containing radicals such as. B. alkyl, alkoxy, haloalkyl and alkylthio radicals and the corresponding unsaturated and / or substituted radicals in the hydrocarbon part may each be straight-chain or branched. Alkyl radicals, also in the composite meanings such as alkoxy, haloalkyl, etc., mean methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl; Alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals, such as 2-propenyl, 2- or 3-butenyl, 2-propynyl, 2- or 3-butynyl. Halogen means fluorine, chlorine, bromine or iodine. Haloalkyl means alkyl which is substituted by one or more atoms from the group halogen; Haloalkyl is for example CF₃, CHF₂, CH₂CF₃. Aryl is, for example, phenyl, naphthyl, tetrahydronaphthyl, indanyl, fluorenyl and the like, preferably phenyl. Substituted aryl or substituted phenyl preferably means aryl or phenyl, which is substituted by one or more, preferably 1 to 3, radicals from the group halogen, alkyl, haloalkyl, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkanoyl, carbamoyl, mono- and di-alkylaminocarbonyl , Mono- and dialkylamino, alkylsulfinyl or alkylsulfonyl is substituted, the alkyl-containing radicals having 1 to 4 carbon atoms, in particular 1 to 2 carbon atoms, being preferred; methyl, methoxy and chlorine are particularly preferred. Examples of heterocyclic residues NRaR ^b , NR ^c R ^d , NR ^e R ^f or NR ^g R ^h are optionally substituted pyrrole, imidazole, pyrazole, triazole, pyrazolone, oxazole, oxazolone, propane sultam, butane sultam, pyrrolidone, piperidine and morpholine. Suitable substituents in substituted heterocyclic radicals are those which have been mentioned for cycloalkyl and aryl radicals, in particular (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₄) haloalkyl, (C₁-C₄) haloalkoxy and halogen.

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

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

Of particular interest are compounds (I) according to the invention in which R 1 H, (C₁-C₄) alkyl which is unsubstituted or by one or more radicals from the  Halogen group, preferably F, Cl and Br, (C₁-C₄) alkoxy, (C₃-C₆) cycloalkyl or phenyl which is unsubstituted or by one or more radicals from the Group halogen, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl, (C₁-C₄) alkoxy, (C₁- C₄) Haloalkoxy and (C₁-C₄) alkylthio is substituted, or (C₃-C₆) cycloalkyl, (C₂-C₄) alkenyl, (C₂-C₄) haloalkenyl, (C₂-C₄) alkynyl, phenyl, substituted phenyl or a radical of the formula

-CO-R *

wherein
R * H, (C₁-C₄) alkyl, (C₂-C₄) alkenyl or (C₂-C₄) alkynyl, each of the latter three radicals unsubstituted or by one or more radicals from the group halogen, (C₁-C₄) alkoxy, (C₁-C₄) alkylsulfonyl, phenyl and substituted phenyl is substituted, or (C₁-C₄) alkoxy which is unsubstituted or by one or more radicals from the group halogen, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, phenyl and substituted aryl is substituted, or (C₃-C₆) cycloalkyl or (C₃-C₆) cycloalkoxy, each of the latter two radicals unsubstituted or by one or more radicals from the group (C₁-C₂) alkyl, (C₁-C₂) alkoxy and halogen is substituted, or is a radical of the formula NRaR ^b .

Preferred compounds of the formula (I) or their salts are those in which
R¹ H, (C₁-C₄) alkyl, which is unsubstituted or substituted by 1 to 3 radicals from the group halogen or by (C₁-C₂) alkoxy or (C₃-C₅) cycloalkyl.

Compounds of the formula (I) or their salts according to the invention are further preferred in which R¹ is a radical of the formula -CO-R *, in which R * is H, (C₁-C₄) alkyl which is unsubstituted or by one or more halogen atoms or by ( C₁-C₂) alkoxy is substituted, or (C₂-C₄) alkenyl, (C₂-C₃) alkynyl, (C₃-C₅) cycloalkyl, (C₁-C₄) alkoxy which is unsubstituted or substituted by one or more halogen atoms or by phenyl , or a radical of the formula NRaR ^b , in which Ra and R ^{b are} independently H or (C₁-C₄) alkyl.

Of particular interest are also compounds of formula (I) according to the invention and their salts, in which
R² H, (C₁-C₄) alkyl which is unsubstituted or substituted by one or more radicals from the group halogen, (C₁-C₄) alkoxy, (C₃-C₆) cycloalkyl, phenyl and substituted phenyl, or (C₃-C₆) Cycloalkyl which is unsubstituted or substituted by one or more radicals from the group halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy or (C₁-C₄) haloalkyl, or (C₂-C₄) alkenyl or (C₂-C₄ ) Alkynyl, where each of the latter two radicals is unsubstituted or substituted by one or more radicals from the group (C₁-C₄) alkoxy, (C₁-C₄) haloalkyl and halogen, or phenyl, substituted phenyl or a radical of the formula R′R '' R '''Si, wherein R', R '', R '''independently of one another are (C₁-C₄) alkyl, or an acyl radical of the formula

-CO-R **,

wherein
R ** H, (C₁-C₄) alkyl, (C₂-C₄) alkenyl or (C₂-C₄) alkynyl, each of the latter three radicals unsubstituted or by one or more radicals from the group halogen, (C₁-C₄) alkoxy , (C₁-C₄) - alkylsulfonyl, phenyl and substituted phenyl is substituted, or (C₁-C₄) alkoxy, (C₃-C₄) alkenyloxy or (C₃-C₄) alkynyloxy, each of the latter three radicals being unsubstituted or by one or more Residues from the group halogen, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, phenyl and substituted phenyl is substituted, or (C₃-C₆) cycloalkyl or (C₃-C₆) cycloalkoxy, each of the latter two residues being unsubstituted or is substituted by one or more radicals from the group halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, and (C₁-C₄) haloalkyl, or a radical of the formula NR _c R _d .

Further preferred compounds of the formula (I) according to the invention and their salts are those in which
R² H, (C₁-C₄) alkyl, (₁-C₄) haloalkyl, [(C₁-C₄) alkoxy] - (C₁-C₄) alkyl or a radical of the formula -CO-R **, wherein
R ** H, (C₁-C₄alkyl, (C₁-C₄) haloalkyl, (C₃-C₄) alkenyl, (C₃-C₄) alkynyl, (C₁-C₄) alkoxy, [(C₁-C₂) alkoxy] - (C₁- C₂) alkyl, (C₃-C₅) cycloalkyl or a radical of the formula NR ^c R ^d , wherein R ^c and R ^d independently of one another are H or (C₁-C₄) alkyl.

R³ is preferably (C₁-C₃) alkyl, (C₁-C₃) haloalkyl, halogen, NO₂, (C₁-C₃) alkoxy, (C₁-C₃) haloalkoxy, (C₁-C₂) alkoxy- (C₁-C₂) alkyl, acetyl , Propionyl, (C₁-C₂) alkylamino, di [(C₁-C₂) alkyl] amino, (C₁- C₃) alkylsulfonyl, SO₂NR ^e R ^f or C (O) NR ^g R ^h
Ra, R ^b , R ^c , R ^d , R ^e , R ^f , R ^g and R ^h are, independently of one another, preferably H, (C₁-C₄) alkyl, allyl, but-2-enyl, but-3-enyl, propargyl , But-2-ynyl, but-3-ynyl, propionyl, acetyl, phenylcarbonyl which is unsubstituted in the phenyl radical or substituted by one or more radicals from the group halogen, (C₁-C₄) alkyl and (C₁- C₄) alkoxy, or in pairs Ra and R ^b , R ^c and R ^d , R ^e and R ^g or R ^g and R ^h together with the N atom connecting them a heterocyclic saturated or unsaturated ring with 5 or 6 ring atoms, which in addition to the N- Atom 1 or 2 may contain further heteroatoms from the group N, O and S in the possible oxidation states and which is unsubstituted or substituted by one or more radicals from the group methyl, ethyl, methoxy, ethoxy, halogen, (C₁-C₂) haloalkyl .

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

Further preferred are compounds of formula (I) or their salts, wherein R¹ is H, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl or [(C₁-C₂) alkoxy] - (C₁-C₂) alkyl, or a radical of the formula -CO-R *, wherein
R * H, (C₁-C₄) alkyl, halo (C₁-C₄) alkyl, (C₂-C₄) alkenyl, (C₂-C₄) alkynyl, (C₁-C₄) alkoxy, [(C₁-C₂) alkoxy] - (C₁-C₂) alkyl, (C₃-C₅) cycloalkyl or a radical of the formula NRaR ^b , in which Ra and R ^b independently of one another are H or (C₁-C₄) alkyl,
R² H, (C₁-C₄) alkyl, (₁-C₄) haloalkyl, [(C₁-C₂) alkoxy] - (C₁-C₂) alkyl or a radical of the formula -CO-R **, wherein
R ** H, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl, (C₃-C₄) alkenyl, (C₃-C₄) alkynyl, (C₁-C₄) alkoxy, ((C₁-C₂) alkoxy] - ( C₁-C₂) alkyl, (C₃-C₅) cycloalkyl or a radical of the formula NR ^c R ^d , in which R ^c and R ^d independently of one another are H or (C₁-C₄) alkyl,
R³ (C₁-C₄) alkyl, halogen, nitro or (C₁-C₄) alkoxy and
n is 0 or 1.

Compounds of the formula (I) according to the invention are furthermore preferred or their salts, in which R¹ is H, CH₃ or C₂H₅ and R * H, (C₁-C₄) alkyl, (C₁- C₂) haloalkyl, vinyl, cyclopropyl, cyclobutyl, (C₁-C₂) alkoxy or N (CH₃) ₂, especially H, mean.

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

is.  

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

Even more preferably one of the radicals X and Y is (C₁-C₂) alkyl, (C₁- C₂) alkoxy or OCF₂H and the other radical Y or X (C₁-C₂) alkyl₁ (C₁- C₂) alkoxy, halogen, OCF₂H, OCH₂CF₃ or CF₃.

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

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

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

• a) a compound of the formula (II), with a heterocyclic carbamate of the formula (III), R ° -O-CO-NR⁴-A (III) in which R ° denotes optionally substituted phenyl or (C₁-C₄) alkyl, or
• b) a pyridylsulfonylcarbamate of the formula (IV), with an amino heterocycle of the formula (V) H-NR⁴-A (V) or
• c) a sulfonyl isocyanate of the formula (VI) with an amino heterocycle of the formula (V) H-NR⁴-A (V) or
• d) in a one-pot reaction, first an amino heterocycle of the formula H-NR⁴-A (V) in the presence of a base, such as. B. triethylamine, with phosgene reacted and the intermediate formed with a pyridine sulfonamide Implement formula (II), or
• e) a sulfonamide of the formula (II) mentioned with a (thio) isocyanate of the formula (VII) in the presence of a base, e.g. B. potassium carbonate or triethylamine,

wherein in the formulas (II) - (VII) the radicals R¹, R², R³, R⁴, A, W, X, Y and Z and m and n are as defined in formula (I).

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

The sulfonamides (II) can be obtained from N-protected 3- (N-hydroxylamino) pyrid-2-yl sulfonamides (VIII)

getting produced.  

The sulfonamides (II) and the protected sulfonamides (VIII) are new Links. They and their manufacture are also the subject of the invention.

The compounds of formula (II) z. B. starting from connections of formula (VIII) by reaction with carboxylic acid halides of the formula Hal-CO-R * (Hal = halogen, preferably chlorine) or symmetrical or mixed carboxylic acid anhydrides of the formula R * -CO-O-COR⁺ or Formula R ** - CO-O-COR⁺, wherein R⁺ is defined analogously to R * or R ** or a is another aliphatic or aromatic radical, being in a first step the O-acyl compounds are formed and with further addition of Acylation reagent which produces N, O-diacyl compounds (R¹ = COR, or R² = COR **) The initially obtained diacylated t-butyl protected Sulfonamides are mixed with acids, e.g. B. with trifluoroacetic acid (see below) in the free Sulfonamides (II) (R¹ = COR *, R² = COR **) transferred.

Structures of the formula (II) in which R¹ = COR * and R² = H are obtained by adding the N, O-diacyl compounds described above e.g. B. with dilute Sodium hydroxide solution (e.g. 2N NaOH) can be saponified. Structures of formula (II), where R¹ = H and R² = alkyl are obtained by the compounds of formula (VIII) with alkylating reagents such as. B. methyl iodide or Dimethyl sulfate with the addition of suitable bases such as. B. potassium hydroxide, DBU, Pyridine, triethylamine or sodium ethanolate are implemented. These could then in a further step with acylation reagents as above described to be converted into compounds in which R¹ = COR * and R² = alkyl or substituted alkyl.

Another derivatization is analogous to methods known from the literature (see Houben-Weyl, Methods of Organic Chemistry, Volume E 16a / Part I, pp. 1-419, Dieter Klamann, Georg Thieme Verlag Stuttgart, New York 1990) possible.

The N-tert-butylpyridylsulfonamides obtained in this way can be incorporated into the compounds of the general formula (II) by reaction with a strong acid (e.g.  Trifluoroacetic acid) are transferred.

The individual reaction stages can be carried out analogously to conventional processes become. The sulfonamides of the formula (VIII) are known from the literature Process can be prepared from optionally substituted 2-chloro-3-nitropyridines. First, the reaction with sulfur nucleophiles, such as. B. Benzyl mercaptan, and subsequent oxidative chlorination of the sulfur atom with sodium hypochlorite or chlorine (formation of the sulfochlorides analogous to EP-A- 272 855) and reaction of the sulfochlorides obtained with tert-butylamine 3-nitro-2-N-tert-butylsulfonylamidopyridines. The nitro group can then reduced to hydroxylamine (II) (R¹ = R² = H) and then in suitable form, e.g. B. by N- or O-acylation, to other compounds of the formula (II) can be derivatized.

Alternatively, compounds of formula (II) from 2-chloro-3-nitro-pyridines by reduction to hydroxylamine and subsequent derivatization are prepared, the derivatization z. B. an N- or O-acylation or N- or O-alkylation, then formation of the sulfochlorides as above described and subsequent implementation of the sulfochlorides directly with Contains ammonia according to or analogous to conventional methods.

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

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

The pyridylsulfonyl isocyanates of the formula (VI) can be prepared analogously to EP-A 184 385 produce and react with the amino heterocycles of the formula (V).

The (thio) isocyanates of the formula (VII) are by methods known from the literature available (EP-A 232067, EP-A 1 66516). Implementation of the (thio) isocyanates (VII) with compounds (II) takes place at -10 ° C and 100 ° C, preferably 20 to 100 ° C, in an inert aprotic solvent, such as. B. acetone or Acetonitrile, in the presence of a suitable base, e.g. B. N (C₂H₅) ₃ or K₂CO₃.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Emulsifiable concentrates are made by dissolving the active ingredient in one organic solvents e.g. B. butanol, cyclohexanone, dimethylformamide, Xylene or higher-boiling aromatics or hydrocarbons or Mixtures of organic solvents with the addition of one or several ionic and / or non-ionic surfactants (emulsifiers) manufactured. 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 B. sorbitan fatty acid esters or polyoxethylene sorbitan esters such. B. Polyoxyethylene sorbitan fatty acid esters.

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

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

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

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

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

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

In wettable powders, the active ingredient concentration is e.g. B. about 10 to 90 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, preferably mostly 5 to 20 wt .-% of active ingredient. sprayable solutions about 0.05 to 80, preferably 2 to 50 wt .-% 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 adhesives, wetting agents, dispersing agents, emulsifying agents, penetration agents, preservatives, antifreeze agents and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and the pH and Agents influencing viscosity.

As a combination partner for the active substances according to the invention in Mixture formulations or in the tank mix are known, for example Active ingredients can be used, as in z. B. from Weed Research 26, 441-445 (1986), or "The Pesticide Manual", 9th edition, The British Crop Protection Council, 1990/91, Bracknell, England, and the literature cited therein. When Herbicides known from the literature, which combine with the compounds of the formula (I) can be z. For example, to name the following active substances (Note: The Connections are either with the "common name" according to the International Organization for Standardization (ISO) or with the chemical name, if applicable 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] - methyl acetate and acetic acid; alachlor; alloxydim; ametryn; amidosulfuron; amitrole; AMS, i.e. H. Ammonium sulfamate; anilofos; asulam; atrazine; 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; benzoylprop-ethyl; benzthiazuron; bialaphos; bifenox; bromacil; bromobutide; bromofenoxim; bromoxynil; bromuron; buminafos; busoxinone; butachlor; butamifos; butenachlor; buthidazole; butralin; butylates; carbetamide; CDAA, i.e. H. 2-chlorine N, N-di-2-propenylacetamide; CDEC, i.e. H. Diethyldithiocarbamic acid 2- chlorallyl ester; CGA 184927, d. H. 2- [4 - [(5-chloro-3-fluoro-2-pyridinyl) -oxy] - phenoxy] propanoic acid and 2-propynyl ester; chlomethoxyfen; chloramben; chlorazifop-butyl, pirifenop-butyl; chlorbromuron; chlorobufam; chlorfenac; chlorflurecol-methyl; chloridazon; chlorimuron ethyl; chloronitrofen; chlorotoluron; chloroxuron; chlorpropham; chlorsulfuron; chlororthal dimethyl; chlorothiamide;  cinmethylin; cinosulfuron; clethodim; clomazone; clomeprop; cloproxydim; clopyralid; cyanazine; cycloate; cycloxydim; cycluron; cyperquat; cyprazine; cyprazole; 2,4-DB; dalapon; desmediphan; desmetryn; di-allate; dicamba; dichlobenil; dichlorprop; diclofop-methyl; diethatyl; difenoxuron; difenzoquat; diflufenican; dimefuron; dimethachlor; dimethametryn; dimethazone, clomazone; dimethipin; dimetrasulfuron, cinosulfuron; dinitramine; dinoseb; dinoterb; diphenamide; dipropetryn; diquat; dithiopyr; diuron; DNOC; eglinazine-ethyl; EL 177, d. H. 5-cyano-1- (1,1-dimethylethyl) -N-methyl-3H-pyrazole-4-carboxamide; endothal; EPTC; esprocarb; ethalfluralin; ethametsulfuron-methyl; ethidimuron; ethiozin; ethofumesate; F523 1, i.e. H. N- [2-chloro-4-fluoro-5- [4- (3-fluoropropyl) -4.5- dihydro-5-oxo-1 H-tetrazol-1-yl] phenyl] ethanesulfonamide; F6285, d. H. 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, d. H. 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; mefiuidid; metamitron; metazachlor; methabenzthiazuron; metham; methazole; methoxyphenone; methyldymron; metobromuron; metolachlor; metoxuron, metribuzin, metsulfuron-methyl, MH, molinate, monalide, monocarbamides dihydrogen sulfates, monolinuron, monuron, MT 128, d. 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, d. H. 4 (2,4-dichlorobenzoyl) -1-methyl-5 benzyloxypyrazole, neburon, nicosulfuron, nipyraclophen, nitralin, 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, d. H. 2- [4-chloro-2-fluoro-5- (2-propynyloxy) phenyl] -4,5,6,7-tetrahydro-2H- indazole; S 482, d. H. 2- [7-fluoro-3,4-dihydro-3-oxo-4- (2-propynyl) -2H-1,4- benzoxazin-6-yl] -4,5,6,7-tetrahydro-1H-isoindole-1,3 (2H) -dione; secbumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, i.e. H. 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, d. H. N, N-Diethyl-3 - [(2-ethyl-6-methylphenyl) sulfonyl] -1H-1,2,4- triazole-1-carboxamide; thiazafluron; thifensulfuron-methyl; thiobencarb; tiocarbazil; tralkoxydim; tri-allate; triasulfuron; triazofenamide; tribenuron-methyl; triclopyr; tridiphane; trietazine; trifluralin; trimeturon; vernolate; WL 110547, i.e. H. 5-phenoxy-1- [3- (trifluoromethyl) phenyl] -1H- tetrazole.

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

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

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

A. Chemical examples Examples a) 2-Benzylthio-3-nitropyridine

39.1 g (0.315 mol) of benzyl mercaptan are placed in 200 ml of acetonitrile and stirred with 47.8 g (0.346 mol) of K₂CO₃ at 600 C for 40 min. Subsequently 50.0 g (0.315 mol) of 2-chloro-3-nitropyridine are added dropwise in 150 ml of acetonitrile added and heated to reflux for 4 h. The acetonitrile is reduced Distilled off pressure, the residue taken up in dichloromethane, the organic phase once each with saturated sodium bicarbonate solution and washed with 1N hydrochloric acid, the organic phase over magnesium sulfate dried, filtered off from the drying agent and the dichloromethane under reduced pressure removed. After recrystallization from methanol 60.9 g (79% of theory) of 2-benzyl-3-nitropyridine with a melting point of 72 ° C.

b) 3-nitro-2-pyridine-tert-butylsulfonamide

24.6 g (0.1 mol) of 2-benzylthio-3-nitropyridine are dissolved in 360 ml of CH₂Cl₂. 280 ml of water were added and 44.9 ml of conc. HCl added dropwise. Then 550 ml of 5% sodium hypochlorite solution is allowed to so slowly  ensure that the internal temperature does not exceed 5 ° C. After 30 min further stirring at 0 ° C the mixture is added to 500 ml of water, the separated organic phase and the aqueous phase at 0 ° C with CH₂Cl₂ washed. The combined organic phases are with NaCl solution washed and dried over MgSO₄. 32.1 g are then added dropwise at 70.degree (0.44 mol) t-Butylamine added. The batch is left at room temperature warm up, pour into water and adjust to pH 2-3 with 1N HCl. After disconnection the organic phase, the aqueous phase is washed with CH₂Cl₂, the organic phases cleaned, dried and the solvent under subtracted reduced pressure. After stirring the residue with Diethyl ether and filtering off give 14.7 g (57% of theory) of 3-nitro-2-pyridine tert-butylsulfonamide with a melting point of 134 ° C.

c) 3-N-hydroxylamino-2-pyridine-tert-butylsulfonamide

To the homogeneous solution of 38.40 g (148.3 mmol) of 3-nitro-2-pyridine-tert.- butylsulfonamide and 21.89 g (409.2 mmol) ammonium chloride in 600 ml Ethanol and 150 ml of water were added in portions with ice cooling 45.70 g Zinc dust. After the addition had ended, stirring was continued for 30 min, followed by filtered excess zinc and the filtrate in vacuo to dryness constricted. Inorganic components of the residues could be separated by suspending the residue in a little ethyl acetate and over filter a silica gel column (h = 5 cm, ⌀ = 5 cm) in ethyl acetate. The filtrate was concentrated and crystallized from ethyl acetate, petroleum ether (1: 3). You got 32.9 g of 3-N-hydroxylamino-2-pyridine-tert.butylsulfonamide (yield 90%) with a melting point of 129 ° C.

d) 3-N- (O-acetyl) hydroxylamino-2-pyridine-tert-butylsulfonamide

In 10 ml of anhydrous tetrahydrofuran, 0.88 g (4.10 mmol) of 3-N- Hydroxylamino-2-pyridine-tert-butylsulfonamide together with 0.50 (4.9 mmol) Triethylamine dissolved and this solution with 0.32 g (4.1 mmol) of acetyl chloride  transferred. After 30 min, 100 ml of ethyl acetate were added and the mixture was extracted twice 2N HCl, the organic phase dried with Na₂SO₄, filtered from the solvent and concentrated the filtrate on the rotary evaporator. The raw product was crystallized from ethyl acetate / n-heptane. 1.10 g of 3-N- (O-acetyl) - were obtained. hydroxylamino-2-pyridine-tert-butylsulfonamide as a crystalline solid (mp. 147 ° C, yield 93%).

e) 3-N- (O-acetyl) hydroxylamino-2-pyridinesulfonamide

2.00 (6.97 mmol) 3-N- (O-acetyl) hydroxylamino-2-pyridine-tert-butylsulfonamide were heated in 3.0 ml of trifluoroacetic acid at 60 ° C for 3 h. After removing the Solvent in vacuo, the residue from ethyl acetate / ether be crystallized. 1.21 g (75% yield) of 3-N- (O-acetyl) were obtained. hydroxylamino-2-pyridinesulfonamide with a melting point of 121 ° C.

f) 3- (4,6-Dimethoxypyrimidin-2-yl) -1 - [(3-N- (O-acetyl) hydroxylamino) -2-- pyridylsulfonylurea

To a solution of 1.20 g (5.10 mmol) 3-N- (O-acetyl) hydroxylamino-2- pyridylsulfonamide and 2.00 g (7.3 mmol) of 1-phenyl-3-4,6-dimethoxypyrimidine-2- yl) carbamate in 20 ml of acetonitrile, 844 mg (6.12 mmol) of 1.5- Diazabicyclo- [5.4.0] undec-7-ene (DBU). After stirring for 30 min at room temperature was acidified with 2N hydrochloric acid, several times with ethyl acetate extracted, dried over Na₂SO₄, filtered and on a rotary evaporator constricted. The product crystallized from ethyl acetate / ethanol 1:10. This was obtained 0.93 g (44% yield) with a melting point of 122 ° C.

g) 3-N- (O-methyl) -hydroxylamino-2-pyridine-tert-butylsulfonamide

6.00 g (24.5 mmol) of 3-N-hydroxylamino-2-pyridine-tert-butylsulfonamide were in 200 ml of anhydrous THF together with 3.39 g (26.9 mmol) of dimethyl sulfate dissolved, cooled to -20 ° C and then in portions with 5.54 g  (49.0 mmol) potassium tert-butoxide added. The reaction solution warmed up to room temperature within 2 h. Then put 100 ml Water and extracted several times with ether. After drying the ethereal Phases over sodium sulfate gave a crude product which in silica gel Mobile phase ethyl acetate / n-heptane was chromatographed 1: 2. 2.56 g were obtained (40%) 3-N- (O-methyl) -hydroxylamino-2-pyridine-tert-butylsulfonamide as colorless crystals with a melting point of 128 ° C.

h) 3-N- (O-methyl) hydroxylamino-2-pyridinesulfonamide

1.00 g (3.86 mmol) of 3-N- (OMethyl) -hydroxylamino-2-pyridine-tert-butylsulfonamide were dissolved in 15 ml of trifluoroacetic acid and heated to 50 ° C for 8 h. The solvent was then removed in vacuo and crystallized the residue from ethyl acetate / cyclohexane. 470 mg were obtained (61%) 3-N- (O-methyl) hydroxylamino-2-pyridinesulfonamide with one Melting point of 149 ° C.

i) 3- (4, 6-Dimethoxypyrimidin-2-yl) -1- [3-N- [O-methyl] hydroxylamino) -2- pyridylsulfonyl] urea

430 mg (2.11 mmol) of 3-N- (O-methyl) -hydroxylamino-2-pyridinesulfonamide were together with 7.57 mg (2.75 mmol) 1-phenyl-3 (4,6-dimethoxypyrimidin-2-yl) - carbamate dissolved in 20 ml acetonitrile and at room temperature with 0.350 g (2.53 mmol) of 1,8-diazabicyclo [5-4-0] undec-7-ene added. After 30 min acidified with 2n Hydrochloric acid, extracted with ethyl acetate, dried over Na₂SO₄, filtered and concentrated on a rotary evaporator. The product crystallized out Methylene chloride / ether. 450 mg (55% of theory) of 3- (4.6- Dimethoxypyrimidin-2-yl) -1- [3-N [O-methyl] hydroxylamino) -2-pyridylsulfonyl] - urea with a melting point of 138 ° C.

The other compounds in Tables 1-5 below are analogous to obtained the procedure of Examples a to i.  

Abbreviations to Tables 1-5

Mp = mp = mp = melting point in ° C
Ph = phenyl
Bzl = benzyl
Me = methyl
Et = ethyl
Pr = propyl
Bu = butyl
n-alkyl = straight chain alkyl = alkyl
i-alkyl = iso-alkyl (e.g. i-Bu = isobutyl)
s-alkyl = secondary alkyl
t-alkyl = tertiary alkyl
c-alkyl = cycloalkyl (e.g. c-Pr = cyclopropyl)

Table 1: Compounds of the formula (Ia)

Table 2

Table 3

Table 4: Compounds of the formula (IIa) to formulas (II) and (VIII)

Table 5: Compounds of the formula (Ie)

B. Examples of formulation

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

b) a wettable powder which is readily dispersible in water is contained, by adding 25 parts by weight of a compound of the formula (I), 64 parts by weight of quartz containing kaolin as an inert substance, 10 parts by weight ligninsulfonic acid potassium and 1 part by weight of oleoylmethyl tauric acid Not sodium as a wetting and dispersing agent and in a pin mill grinds.

c) A dispersion concentrate which is readily dispersible in water is obtained by 20 parts by weight of a compound of formula (I) with 6 parts by weight Parts of alkylphenol polyglycol ether (®Triton X 207), 3 parts by weight Isotridecanol polyglycol ether (8 EO) and 71 parts by weight paraffinic Mineral oil (boiling range e.g. approx. 255 to above 277 ° C) mixes and in one Grinding ball mill ground to a fineness of less than 5 microns.

d) An emulsifiable concentrate is obtained from 15 parts by weight of one Compound of formula (I), 75 parts by weight of cyclohexanone as Solvent and 10 parts by weight of ethylated nonylphenol as Emulsifier.

e) A water-dispersible granulate is obtained by:

75 parts by weight of a compound of 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 the powder in a fluidized bed granulated 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 and pre-shredded on a colloid mill, then on a bead mill and the suspension thus obtained in one The spray tower is atomized and dried using a single-component nozzle.

C. Biological examples 1. Pre-emergence weed action

Seeds or rhizome pieces of monocotyledonous and dicotyledonous weed plants were grown in Plastic pots laid out in sandy loam and covered with earth. In the Formulated in the form of wettable powders or emulsion concentrates Compounds according to the invention were then in the form of an aqueous suspension or Emulsion with a water application rate of the equivalent of 600 to 800 l / ha in different doses applied to the surface of the earth. After the treatment, the pots were placed in the greenhouse and under good growing conditions for the weeds. The optical rating the damage to the plants or the emergence occurred after the emergence of the Test plants after a test period of 3 to 4 weeks compared to untreated controls. As the test results show, the Compounds according to the invention have a good herbicidal pre-emergence activity  against a wide range of grasses and weeds. For example have the compounds of the above examples (see Tables 1-3, 5) 1, 8, 15, 23, 29, 36, 43, 56, 69, 76, 90, 97, 111, 118, 125, 198, 333, 472, 500 and 553 very good herbicidal activity against harmful plants such as Sinapis alba, Chrysanthemum segetum, Avena sativa, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Setaria spp., Abutilon theophrasti, Amaranthus retroflexus and Panicum miliaceum in the pre-emergence process at an application rate of 0.3 kg and less of active ingredient per hectare.

2. Post-emergence weed action

Seeds or rhizome pieces of monocotyledonous and dicotyledonous weeds were found in Plastic pots laid out in sandy clay soil, covered with earth and in Greenhouse grown under good growing conditions. Three weeks after sowing, the test plants were treated at the three-leaf stage. Formulated as wettable powder or emulsion concentrates Compounds according to the invention were in different doses a water application rate of the equivalent of 600 to 800 l / ha to the green Plant parts sprayed and after about 3 to 4 weeks of standing Trial plants in the greenhouse under optimal growing conditions Effect of the preparations visually compared to untreated controls rated. The agents according to the invention also have good post-emergence properties herbicidal activity against a wide range of economically more important Grasses and weeds. For example, the connections of Examples mentioned (see tables 1-3, 5) 1, 8, 15, 23, 29, 36, 43, 56, 69, 76, 90, 97, 111, 118, 125, 198, 333, 472, 500 and 553 very good herbicides Effect against harmful plants such as Sinapis alba, Stellaria media, Echinochloa crus galli, Lolium multiflorum, Chrysanthemum segetum, Setaria spp., Abutilon theophrasti, Amaranthus retroflexus and Panicum miliaceum, Avena sativa im Post-emergence process with an application rate of 0.3 kg and less Active ingredient per hectare.

Claims (11)

1. Compounds of the formula (I) or their salts, wherein
R¹ H, (C₁-C₆) alkyl which is unsubstituted or substituted by one or more radicals from the group halogen, nitro, (C₁-C₄) alkoxy, (C₃-C₆) cycloalkyl, cyano, aryl and substituted aryl, (C₃ -C₆) cycloalkyl which is unsubstituted or substituted by one or more radicals from the group halogen, (C₁-C₄) alkyl and (C₁-C₄) alkoxy, or
(C₂-C₆) alkenyl or (C₂-C₆) alkynyl, each of the latter two radicals being unsubstituted or substituted by one or more radicals from the group halogen, (C₁-C₄) alkoxy and (C₃-C₆) cycloalkyl, or aryl , substituted aryl, or an acyl radical of the formula -CO-R *, wherein
R * H, (C₁-C₆) alkyl, (C₂-C₆) alkenyl or (C₂-C₆) alkynyl, each of the latter three radicals unsubstituted or by one or more radicals from the group halogen, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, (C₁- C₄) alkylsulfinyl, (C₁-C₄) alkylsulfonyl, nitro, cyano, thiocyanato, aryl and substituted aryl, or (C₁-C₄) alkoxy, (C₂- C₄) alkenyloxy, ( C₂-C₄) alkynyloxy or (C₁-C₄) alkylthio, each of the latter four radicals being unsubstituted or substituted by one or more radicals from the group halogen, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, aryl and substituted aryl is, or (C₃-C₆) cycloalkyl or (C₃-C₆) cycloalkoxy, each of the latter two radicals unsubstituted or by one or more radicals from the group (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁- C₄) alkylthio, (C₁-C₄) haloalkyl, and halogen is substituted, or is a radical of the formula NRaR ^b ,
R² H, (C₁-C₆) alkyl which is unsubstituted or substituted by one or more radicals from the group halogen, nitro, (C₁-C₄) alkoxy, (C₃-C₆) cycloalkyl, aryl and substituted aryl, or (C₃- C₆) cycloalkyl which is unsubstituted or substituted by one or more radicals from the group halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₄) haloalkyl, aryl and substituted aryl, or (C₂-C₆ ) Alkenyl or (C₂-C₆) alkynyl, each of the latter two radicals being unsubstituted or substituted by one or more radicals from the group (C₁-C₄) alkoxy, (C₁-C₄) haloalkyl, (C₃-C₆) cycloalkyl and halogen , or aryl, substituted aryl or a radical of the formula R′R′′R ′ ′ ′ Si, where R ′, R ′ ′, R ′ ′ ′ independently of one another are (C₁-C₄) alkyl, or an acyl radical of the formula CO-R **, wherein
R ** H, (C₁-C₆) alkyl, (C₂-C₆) alkenyl or (C₂-C₆) alkynyl, each of the latter three radicals unsubstituted or by one or more radicals from the group halogen, (C₁-C₄) alkoxy , (C₁-C₄) alkylthio, (C₁- C₄) alkylsulfinyl, (C₁-C₄) alkylsulfonyl, nitro, cyano, thiocyanato, aryl and substituted aryl, or (C₁-C₄) alkoxy, (C₂- C₄) alkenyloxy or (C₂-C₄) alkynyloxy, each of the latter three radicals being unsubstituted or substituted by one or more radicals from the group halogen, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, aryl and substituted aryl, or (C₃- C₆) cycloalkyl or (C₃- C₆) cycloalkoxy, each of the latter two radicals unsubstituted or by one or more radicals from the group halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio and (C₁-C₄) haloalkyl is substituted or is a radical of the formula NR ^c R ^d ,
R³ (C₁-C₄) alkyl, (C₁-C₃) haloalkyl, halogen, NO₂, CN, (C₁-C₃) alkoxy, (C₁-C₃) haloalkoxy, (C₁-C₃) alkylthio, (C₁-C₃) alkoxy- ( C₁-C₃) alkyl, [(C₁-C₃) alkoxy] carbonyl, (C₁-C₃) alkylamino, di [(C₁-C₃) alkyl] amino, (C₁-C₃) alkylsulfinyl, (C₁-C₃) alkylsulfonyl , SO₂NR ^e R ^f or C (O) NR ^g R ^h ,
Ra, R ^b , R ^c , R ^d , R ^e , R ^f , R ^g and R ^h independently of one another H, (C₁-C₄) alkyl, (C₃- C₆) alkenyl, (C₃-C₆) alkynyl, [(C₁ -C₄) alkyl] carbonyl, arylcarbonyl, which is unsubstituted in the aryl radical or substituted by one or more radicals from the group halogen, (C₁-C₄) alkyl and (C₁-C₄) alkoxy, or in pairs Ra and R ^b , R ^c and R ^d , R ^e and R ^f or R ^g and R ^h together with the N atom connecting them form a heterocyclic saturated or unsaturated ring with 3 to 7 ring atoms, which in addition to the N atom has 1 or 2 further heteroatoms from the group May contain N, O and S in the possible oxidation states and which is unsubstituted or substituted,
R⁴ H or (C₁-C₄) alkyl,
m 0 or 1,
n 0, 1 or 2,
A is a residue of the formula X, Y independently of one another are H, halogen, (C₁-C₃) alkyl, (C₁-C₃) alkoxy or (C₁-C₃) alkylthio, where the abovementioned alkyl-containing radicals are unsubstituted or mono- or polysubstituted by halogen or mono- or polysubstituted by ( C₁-C₃) alkoxy or (C₁-C₃) alkylthio are substituted, or a radical of the formula NR⁵R⁶, (C₃-C₆) cycloalkyl, (C₂-C₄) alkenyl, (C₂-C₄) alkynyl, (C₃-C₄) - Alkenyloxy or (C₃-C₄) alkynyloxy,
R⁵, R⁶ independently of one another H, (C₁-C₃) alkyl or (C₃-C₄) alkenyl,
WHERE or S,
Z CH or N,
X¹ CH₃, OCH₃, OC₂H₅ or OCF₂H,
Y¹ -O- or -CH₂-,
X² CH₃, C₂H₅ or CH₂CF₃,
Y² OCH₃, OC₂H₅, SCH₃, SC₂H₅, CH₃ or C₂H₅,
X³ CH₃ or OCH₃,
Y³ H or CH₃,
X⁴ CH₃, OCH₃, OC₂H₅, CH₂OCH₃ or Cl,
Y⁴ CH₃, OCH₃, OC₂H₅ or Cl,
Y⁵ CH₃, C₂H₅, OCH₃ or Cl
mean. 2. Compounds or their salts according to claim 1, characterized in that
R¹ H, (C₁-C₄) alkyl which is unsubstituted or by one or more radicals from the group halogen, (C₁-C₄) alkoxy, (C₃-C₆) cycloalkyl or phenyl which is unsubstituted or by one or more radicals from the group Halogen, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl, (C₁-C₄) alkoxy, (C₁-C₄) haloalkoxy and (C₁- C₄) alkylthio is substituted, or
(C₃-C₆) cycloalkyl, (C₂-C₄) alkenyl, (C₂-C₄) haloalkenyl, (C₂-C₄) alkynyl, phenyl, substituted phenyl or a radical of the formula -CO-R * wherein
R * H, (C₁-C₄) alkyl, (C₂-C₄) alkenyl or (C₂-C₄) alkynyl, each of the latter three radicals unsubstituted or by one or more radicals from the group halogen, (C₁-C₄) alkoxy, (C₁-C₄) alkylsulfonyl, phenyl and substituted phenyl is substituted, or (C₁-C₄) alkoxy which is unsubstituted or by one or more radicals from the group halogen, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, phenyl and substituted aryl is substituted, or (C₃-C₆) cycloalkyl or (C₃-C₆) cycloalkoxy, each of the latter two radicals unsubstituted or by one or more radicals from the group (C₁-C₂) alkyl, (C₁-C₂) alkoxy and halogen is substituted, or is a radical of the formula NRaR ^b . 3. Compounds or their salts according to claim 1 or 2, characterized in that
R¹ H, (C₁-C₄) alkyl which is unsubstituted or substituted by 1 to 3 radicals from the group halogen or by (C₁-C₂) alkoxy or (C₃-C₅) cycloalkyl, or a radical of the formula -CO-R * means what
R * H, (C₁-C₄) alkyl which is unsubstituted or substituted by one or more halogen atoms or by (C₁-C₂) alkoxy, or (C₂- C₄) alkenyl, (C₂-C₃) alkynyl, (C₃-C₅) Cycloalkyl, (C₁-C₄) alkoxy which is unsubstituted or substituted by one or more halogen atoms or by phenyl, or a radical of the formula NRaR ^b , in which Ra and R ^{b are} independently H or (C₁-C₄) alkyl. R² H, (C₁-C₄) alkyl which is unsubstituted or substituted by one or more radicals from the group halogen, (C₁-C₄) alkoxy, (C₃-C₆) cycloalkyl, phenyl and substituted phenyl, or (C₃-C₆) Cycloalkyl which is unsubstituted or substituted by one or more radicals from the group halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy or (C₁-C₄) haloalkyl, or (C₂- C₄) alkenyl or (C₂-C₄ ) Alkynyl, where each of the latter two radicals is unsubstituted or substituted by one or more radicals from the group (C₁-C₄) alkoxy, (C₁-C₄) haloalkyl and halogen, or phenyl, substituted phenyl or a radical of the formula R'R '' R '''Si, wherein R', R '', R '''independently of one another are (C₁-C₄) alkyl, or an acyl radical of the formula -CO-R **, wherein
R ** H, (C₁-C₄) alkyl, (C₂-C₄) alkenyl or (C₂-C₄) alkynyl, each of the latter three radicals unsubstituted or by one or more radicals from the group halogen, (C₁-C₄) alkoxy , (C₁-C₄) alkylsulfonyl, phenyl and substituted phenyl is substituted, or (C₁-C₄) alkoxy, (C₃- C₄) alkenyloxy or (C₃-C₄) alkynyloxy, each of the latter three radicals being unsubstituted or by one or more Residues from the group halogen, (C₁-C₄) alkoxy, (C₁-C₄) alkylthio, phenyl and substituted phenyl is substituted, or (C₃-C₆) cycloalkyl or (C₃- C Cycl) cycloalkoxy, each of the latter two residues being unsubstituted or is substituted by one or more radicals from the group halogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, and (C₁-C₄) haloalkyl, or a radical of the formula NR ^c R ^d , and
(C₁-C₃) alkyl, (C₁-C₃) haloalkyl, halogen, NO₂, (C₁-C₃) alkoxy, (C₁-C₃) haloalkoxy, (C₁-C₂) alkoxy- (C₁-C₂) alkyl, acetyl, propionyl, (C₁-C₂) alkylamino, di [(C₁-C₂) alkyl] amino, (C₁-C₃) alkylsulfonyl, SO₂NR ^e R ^f or C (O) NR ^g R ^h
interpret. 4. Compounds or their salts according to one of claims 1 to 3, characterized in that
R¹ H, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl or [(C₁-C₂) alkoxy] - (C₁-C₂) alkyl, or a radical of the formula -CO-R *, wherein
R * H, (C₁-C₄) alkyl, halo (C₁-C₄) alkyl, (C₂-C₄) alkenyl, (C₂-C₄) alkynyl, (C₁-C₄) alkoxy, [(C₁-C₂) alkoxy] - (C₁-C₂) alkyl, (C₃-C₅) cycloalkyl or a radical of the formula NRaR ^b , in which Ra and R ^b independently of one another are H or (C₁-C₄) alkyl,
R² H, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl, [(C₁-C₂) alkoxy] - (C₁-C₂) alkyl or a radical of the formula -CO-R **, wherein
R ** H, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl, (C₃-C₄) alkenyl, (C₃-C₄) alkynyl, (C₁- C₄) alkoxy, [(C₁-C₂) alkoxy] - ( Is C₁-C₂) alkyl, (C₃-C₅) cycloalkyl or a radical of the formula NR ^c R ^d , in which R ^c and R ^d independently of one another are H or (C₁-C₄) alkyl,
R³ (C₁-C₄) alkyl, halogen, nitro or (C₁-C₄) alkoxy
n 0 or 1 and
A is a radical of formula x wherein
one of the radicals X and Y is (C₁-C₃) alkyl, (C₁-C₃) alkoxy, (C₁-C₃) haloalkyl, (C₁-C₃) haloalkoxy or [(C₁-C₂) alkoxy] - (C₁-C₂) alkyl
and the other Y or X (C₁-C₃) alkyl, (C₁-C₃) alkoxy, (C₁-C₃) alkylthio, each of the latter 3 residues unsubstituted or one or more times by halogen or once or twice by ( C₁-C₃) alkoxy or (C₁-C₃) alkylthio is substituted, or halogen or a radical of the formula NR⁵R⁶, where R⁵ and R⁶ are independently H, (C₁-C₃) alkyl or (C₃- C₄) alkenyl, or (C₃ -C₆) cycloalkyl, (C₂-C₄) alkenyl, (C₂-C₄) alkynyl, (C₃- C₄) alkenyloxy or (C₃-C₄) alkynyloxy,
mean. 5. A process for the preparation of the compounds of formula (I) or their salts, characterized in that

• a) a compound of the formula (II), with a heterocyclic carbamate of the formula (III), R ° -O-CO-NR⁴-A (III) in which R ° denotes optionally substituted phenyl or (C₁-C₄) alkyl, or
• b) a pyridylsulfonylcarbamate of the formula (IV), with an amino heterocycle of the formula (V) H-NR⁴-A (V) or
• c) a sulfonyl isocyanate of the formula (VI) with an amino heterocycle of the formula (V) H-NR⁴-A (V) or
• d) in a one-pot reaction, first reacting an amino heterocycle of the formula H-NR⁴-A (V) with phosgene in the presence of a base and reacting the intermediate formed with a pyridinesulfonamide of the formula (II), or
• e) a sulfonamide of the formula (II) mentioned with a (thio) isocyanate of the formula (VII) in the presence of a base,
  wherein in the formulas (II) - (VII) the radicals R¹, R², R³, R⁴, A, W, X, Y and Z as well as m and n are as defined in formula (I).

6. Herbicidal or plant growth regulating agent, thereby characterized in that it is at least one compound of formula (I) or its Salts according to one of claims 1 to 4 and customary in crop protection Contains formulation aids. 7. Methods for controlling harmful plants or Growth regulation of plants, characterized in that one effective amount of at least one compound of formula (I) or its Salts according to one of Claims 1 to 4 on the harmful plants or plants, applied their plant seeds or the area on which the plants grow.   8. Use of the compounds of formula (I) or their salts after a of claims 1 to 4 as herbicides or plant growth regulators. 9. Compounds of the formula (II), wherein R¹, R², R³, n and m are as defined in formula (I) according to any one of claims 1 to 4. 10. Compounds of formula (VIII) wherein R¹, R², R³, n and m are as defined in formula (I) according to any one of claims 1 to 4.