DE19963395A1 - New ammonium salt derivatives of sulfonyl urea compounds, useful as herbicides or plant growth regulators providing stable formulations, especially emulsifiable concentrates - Google Patents

Abstract

Ammonium salts (I) of N'-(triazinyl or pyrimidinyl)-sulfonyl urea compounds are new. Sulfonylurea salts of formula (I) are new. Ra = -N(R3)-SO2R2 or a group of formula (a)-(d); R1 = H or 1-10C hydrocarbyl, e.g. 1-6C alkyl; R2, R3 = optionally substituted (os) 1-20C hydrocarbyl, e.g. 1-6C alkyl, 2-6C alkenyl, 2-6C alkynyl or 3-7C cycloalkyl (all os); R4 = halo, os 1-20C hydrocarbyl or os 1-20C hydrocarbyloxy, e.g. 1-6C alkyl, 2-6C alkenyl, 2-6C alkynyl, 1-6C alkoxy, 3-6C alkenyloxy or 3-6C alkynyloxy (all os by one or more of halo and 1-3C alkoxy); R5 = H, halo, os 1-20C hydrocarbyl or os 1-20C hydrocarbyloxy, e.g. 1-6C alkyl or 1-5C alkoxy (both os by one or more of halo and 1-3C alkoxy); or as R4; R6, R'6 = H or os 1-20C hydrocarbyl (e.g. 1-3C alkyl or cyclopropyl); or together form an os ring; R7, R'7 = H, halo, OH, NRxRy, N-(1-3C alkyl)-N-acylamino, N-acylamino, os 1-20C hydrocarbyl or os 1-20C hydrocarbyloxy, e.g. 1-3C alkyl, 1-3C haloalkyl, (1-3C) alkyl-(N-(1-3C) alkyl-N-acylamino), (1-3C) alkyl-(N-acylamino) or 1-3C alkoxy; Rx, Ry = H or 1-3C alkyl; R''6 = os 1-20C hydrocarbyl, e.g. 1-6C alkyl, (3-6C) alkenyloxycarbonyl, 3-6C cycloalkyl, 3-7C alkynyl or 4-8C cycloalkylalkyl (all os); R'''6 = halo or group containing optionally substituted 1-20C hydrocarbyl, e.g. 1-6C alkyl or 1-6C alkoxy (both os by one or more of halo and 1-3C alkoxy), os alkoxycarbonyl, mono- or di-(1-6C alkyl)-amino, N-(1-6C alkyl)-N-acylamino or N-acylamino; R''7 = H, halo, OH, NRxRy, os 1-20C hydrocarbyl or os 1-20C hydrocarbyloxy, e.g. 1-6C alkyl, 1-6C haloalkyl, 1-6C alkoxy or 1-6C haloalkoxy; M<+> = primary, secondary, tertiary or preferably quaternary ammonium ion; X, Y = halo, mono- or di-(1-3C alkyl)-amino or (all os) 1-6C alkyl, 1-6C alkoxy or 1-6C alkylthio; Z' = C-(halo), CH or N. An Independent claim is included for the use of ammonium or metal salts of formula (XVIII) for the preparation of an agrochemical formulation. w, x, y, z = 0-50; R = optionally substituted 8-40C hydrocarbyl; or -CH2CH2NR'R''R'''; R', R'', R''' = optionally substituted 1-100C hydrocarbyl; EO = ethoxy unit; PO = propoxy unit; M'<+> = ammonium ion or metal cation.

Description

The invention relates to the technical field of the formulation of herbicides and Plant growth regulators, in particular herbicides for controlling undesirable plant growth, e.g. B. of weeds and grasses in Crop crops.

It is known that sulfonylureas and herbicides possess plant growth regulating properties. For use in In the agrochemical field, the sulfonylureas are usually formulated. The chemical stability and the active ingredient concentration are in the formulation important for their effectiveness.

Surprisingly, it has now been found that formulations based on certain sulfonylurea salts have excellent properties.

The present invention therefore relates to formulations, in particular agrochemical, for. B. herbicidal formulations containing a sulfonylurea salt of the formula (Ia),

wherein
R ^{a is} a grouping of the formula II-IVc,

R ¹ H or a C ₁ -C ₁₀ hydrocarbon radical such as (C ₁ -C ₆ ) alkyl,
R ^{2 is} a substituted or unsubstituted C ₁ -C ₂₀ -hydrocarbon radical such as substituted or unsubstituted (C ₁ -C ₆ ) alkyl, substituted or unsubstituted (C ₂ -C ₆ ) alkenyl, substituted or unsubstituted (C ₂ -C ₆ ) - is alkynyl, substituted or unsubstituted (C ₃ -C ₇ ) cycloalkyl;
R ^{3 is} a substituted or unsubstituted C ₁ -C ₂₀ hydrocarbon radical such as substituted or unsubstituted (C ₁ -C ₆ ) alkyl, substituted or unsubstituted (C ₂ -C ₆ ) alkenyl, substituted or unsubstituted (C ₂ -C ₆ ) Is alkynyl, substituted or unsubstituted (C ₃ -C ₇ ) cycloalkyl,
R ⁴ halogen such as F, Cl, Br, J or a substituted or unsubstituted C ₁ -C ₂₀ -hydrocarbon radical or C ₁ -C ₂₀ -hydrocarbonoxy radical such as (C ₁ -C ₆ ) - alkyl, (C ₂ -C ₆ ) - Alkenyl, (C ₂ -C ₆ ) alkynyl, (C ₁ -C ₆ ) alkoxy, (C ₃ -C ₆ ) alkenyloxy, (C ₃ -C ₆ ) alkynyloxy, the latter 6 radicals being substituted by one or several radicals, preferably from the group halogen, such as F, Cl, Br or I or (C ₁ -C ₃ ) alkoxy, can be substituted,
R ⁵ H, halogen such as F, Cl, Br, J or a substituted or unsubstituted C ₁ -C ₂₀ -hydrocarbon radical or C ₁ -C ₂₀ -hydrocarbonoxy radical such as (C ₁ -C ₆ ) - alkyl, which is substituted by one or more radicals from the group halogen such as F, Cl, Br or J or (C ₁ -C ₃ ) alkoxy or (C ₁ -C ₅ ) alkoxy which can be substituted by one or more radicals from the group halogen (F, Cl , Br, I) or (C ₁ -C ₃ ) alkoxy may be substituted
R ⁶ and R ^{6 ',} identical or different, are H or a substituted or unsubstituted C ₁ -C ₂₀ -hydrocarbon radical such as C ₁ -C ₆ -alkyl (e.g. Me, Et, ⁿ Pr, ⁱ Pr, ^c Pr), where R ⁶ and R ^{6 '} can form a ring which is unsubstituted or substituted,
R ⁷ H, halogen such as F, Cl, Br or J, OH, NR ^X R ^Y , where R ^X and R ^{Y are} H or (C ₁ -C ₃ ) alkyl, or R ⁷ N- (C ₁ -C ₃ ) -alkyl-N-acylamino, N-acylamino, or a substituted or unsubstituted C ₁ -C ₂₀ -hydrocarbon radical or hydrocarbonoxy radical such as (C ₁ -C ₃ ) -alkyl, (C ₁ -C ₃ ) -haloalkyl, halogen, (C ₁ -C ₃ ) alkyl- (N- (C ₁ -C ₃ ) alkyl-N-acylamino), (C ₁ -C ₃ ) alkyl- (N-acylamino) or (C ₁ -C ₃ ) Alkyl,
R ^{6 ″ is} a substituted or unsubstituted C ₁ -C ₂₀ -hydrocarbonoxy radical such as substituted or unsubstituted (C ₁ -C ₆ ) -alkyl, substituted or unsubstituted (C ₃ -C ₆ ) -alkenyloxycarbony, substituted or unsubstituted (C ₃ -C ₆ ) -cycloalkyl, substituted or unsubstituted (C ₃ -C ₇ ) -alkynyl, substituted or unsubstituted (C ₄ -C ₈ ) -cycloalkylalkyl,
R ^{7 '} halogen such as F, Cl, Br or J, OH, NR ^X R ^Y , where R ^X and R ^{Y are} H or (C ₁ -C ₃ ) alkyl, or R ^7' N- (C ₁ -C ₃ ) -alkyl-N-acylamino or a substituted or unsubstituted C ₁ -C ₂₀ -hydrocarbon radical or C ₁ -C ₂₀ -hydrocarbon oxy radical such as (C ₁ -C ₃ ) -alkyl, (C ₁ -C ₃ ) -haloalkyl, (C ₁ -C ₃ ) alkyl- (N- (C ₁ -C ₃ ) alkyl-N-acylamino), (C ₁ -C ₃ ) alkyl- (N-acylamino) or (C ₁ -C ₃ ) Alkyl, is
R ^{6 '''} halogen such as F, Cl, Br or J or a substituted or unsubstituted C ₁ -C ₂₀ carbon-containing radical such as (C ₁ -C ₆ ) alkyl, which is substituted by one or more radicals from the group halogen (F , Cl, Br, I) or (C ₁ -C ₃ ) alkoxy can be substituted, (C ₁ -C ₆ ) alkoxy, which is substituted by one or more radicals from the group halogen (F, Cl, Br, J) or (C ₁ -C ₃ ) alkoxy may be substituted, substituted or unsubstituted alkoxycarbonyl, (C ₁ -C ₆ ) mono- or dialkylamino, N- (C ₁ -C ₆ ) alkyl-N-acylamino or N- Acylamino, is,
R ^{7 ''} halogen such as F, Cl, Br or J, OH, NR ^X R ^Y , where R ^X and R ^{Y are} H or (C ₁ -C ₃ ) alkyl or R ^{7 'is} a substituted or unsubstituted C ₁ - C _{20 is a} hydrocarbon radical or hydrocarbonoxy radical such as (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) haloalkyl, (C ₁ -C ₆ ) alkoxy or (C ₁ -C ₆ ) haloalkoxy,
M ^{+ is} a primary, secondary, tertiary or quaternary, preferably a quaternary ammonium ion,
X substituted or unsubstituted (C ₁ -C ₆ ) alkyl, substituted or unsubstituted (C ₁ -C ₆ ) alkoxyl, halogen such as F, Cl, Br or J, substituted or unsubstituted (C ₁ -C ₆ ) mercapto is alkyl or (C ₁ -C ₃ ) mono- or (C ₁ -C ₃ ) dialkylamino,
Y substituted or unsubstituted (C ₁ -C ₆ ) alkyl, substituted or unsubstituted (C ₁ -C ₆ ) alkoxyl, halogen such as F, Cl, Br or J, substituted or unsubstituted (C ₁ -C ₆ ) mercapto- is alkyl or (C ₁ -C ₃ ) mono- or (C ₁ -C ₃ ) dialkylamino, and
Z is C-halogen such as CF, CCl, CBr or CJ, CH, or N and
b) usual auxiliaries and additives.

The sulfonylurea salts of the formula (Ia) are new and also the subject of these Invention.

In formula (Ia) and in the other formulas used in this application the residues alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio and the corresponding unsaturated and / or substituted radicals in Carbon skeleton in each case be straight-chain or branched. Alkyl residues, also in the composite meanings such as alkoxy, haloalkyl, etc. mean z. B. Methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, i- Hexyl and 1,3-dimethylbutyl, heptyls such as n-heptyl, 1-methylhexyl and 1,4- Dimethylpentyl; Alkenyl and alkynyl radicals have the meaning of the alkyl radicals corresponding possible unsaturated radicals, alkenyl means, for. B. Allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methyl-but-3-en-1-yl and 1-methyl-but-2-en-1-yl; Alkynyl means e.g. B. propargyl, But-2-in-1-yl, but-3-in-1-yl, 1-methyl-but-3-in-1-yl.

The abbreviations used in this application have the following meaning:
Me = methyl, Et = ethyl, Pr = propyl, Bu = butyl, ⁿ Pr = n-propyl, ⁱ Pr = iso-propyl, ^c Pr = cyclopropyl, ⁿ Bu = n-butyl, ⁱ Bu = iso-butyl, ^s Bu = secondary butyl, ^t Bu = tertiary butyl, ^c Bu = cyclobutyl, Ph = phenyl.

The term ammonium ions also includes "quaternized" nitrogen systems with an sp ² -hybridized N atom, such as pyridinium ions.

Halogen means, for example, fluorine, chlorine, bromine or iodine. Haloalkyl, -alkenyl and -alkynyl are partially or fully substituted alkyl, alkenyl or alkynyl, for example by halogen, preferably by fluorine, chlorine and / or bromine, in particular by fluorine or chlorine. B. CF ₃ , CHF ₂ , CH ₂ F, CF ₃ CF ₂ , CH ₂ FCHCl, CCl ₃ , CHCl ₂ , CH ₂ CH ₂ Cl; Haloalkoxy is e.g. B. OCF ₃ , OCHF ₂ , OCH ₂ F, CF ₃ CF ₂ O, OCH ₂ CF ₃ and OCH ₂ CH ₂ Cl; The same applies to haloalkenyl and other halogen-substituted radicals.

Aryl means a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl, Fluorenyl and the like, preferably phenyl.

A heterocyclic radical or ring (heterocyclyl) can be saturated, unsaturated or be heteroaromatic and unsubstituted or substituted; it preferably contains one or more heteroatoms in the ring, preferably from the group N, O and S, it is preferably an aliphatic heterocyclyl radical having 3 to 7 ring atoms or a heteroaromatic radical with 5 or 6 ring atoms and contains 1, 2 or 3 Heteroatoms. The heterocyclic radical can e.g. B. a heteroaromatic residue or Ring (heteroaryl), such as. B. a mono-, bi- or polycyclic aromatic System in which at least 1 ring contains one or more hereo atoms, for example pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thienyl, Thiazolyl, oxazolyl, furyl, pyrrolyl, pyrazolyl and imidazolyl, or is a partial or fully hydrogenated radical such as oxiranyl, oxetanyl, pyrrolidyl, piperidyl, piperazinyl, Dioxolanyl, morpholinyl, tetrahydrofuryl. As a substituent for a substituted one heterocyclic radical are the substituents mentioned below, additionally also oxo. The oxo group can also be attached to the hetero ring atoms in different oxidation levels can exist, e.g. B. N and S occur.

Substituted radicals, such as substituted hydrocarbon radicals, e.g. B. substituted Alkyl, alkenyl, alkynyl, aryl, phenyl and benzyl, or substituted heteroaryl substituted bicyclic radical or ring or a substituted bicyclic radical, optionally with aromatic components, for example mean one of unsubstituted basic body derived substituted radical, the Substituents for example one or more, preferably 1, 2 or 3 radicals from the group halogen, alkoxy, haloalkoxy, alkylthio, hydroxy, amino, nitro, Cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and  Dialkylaminocarbonyl, substituted amino such as acylamino, mono- and dialkylamino, and alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and, in the case cyclic radicals, including alkyl and haloalkyl and the above-mentioned saturated hydrocarbon-containing residues corresponding unsaturated aliphatic residues, such as alkenyl, alkynyl, alkenyloxy, alkynyloxy etc. mean. For residues with carbon atoms those having 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, are preferred.

Mono- and disubstituted amino means e.g. B. alkylamino, dialkylamino, Acylamino, arylamino, N-aryl-N-alkylamino.

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

The formula (Ia) also includes all stereoisomers of the formula (Ia), as well their mixtures. Such compounds of formula (Ia) contain one or more asymmetric carbon atoms or double bonds in the general formula (Ia) are not specified separately. The through their specific spatial shape defined possible stereoisomers, such as enantiomers, diastereomers, Z and E Isomers are all encompassed by the formula (Ia) and can be prepared by customary methods obtained from mixtures of the stereoisomers or by stereoselective Reactions in combination with the use of stereochemically pure Starting materials are produced.

Of particular interest are formulations containing sulfonylurea salts of the formula (Ia), in which
R ¹ H or Me,
R ² (C ₁ -C ₃ ) alkyl or (C ₁ -C ₃ ) haloalkyl, in particular Me and Et,
R ³ (C ₁ -C ₃ ) alkyl or (C ₁ -C ₃ ) haloalkyl, in particular Me and Et,
R ⁴ (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) haloalkyl or (C ₁ -C ₆ ) alkoxy, in particular Me, Et, OMe, OEt or CF ₃ ,
R ⁵ H, halogen such as F, Cl, Br or J, OMe, OEt, Me, CF ₃ , where the radicals R ⁵ in formula (III) other than hydrogen are preferably in the 5-position on the phenyl ring,
R ⁶ and R ^{6 'are the} same or different C ₁ -C ₆ alkyl, preferably R ⁶ = Me, Et R ^6' = Me; R ⁶ = Me, R ^{6 '} = Et and R ⁶ = Et, R ⁶ = Et.
R ⁷ H, Me, Et, CF ₃ , F, Cl, Br, J, N [(C ₁ -C ₃ ) alkyl] -R ⁵ , NH-R ⁹ , CH ₂ N [(C ₁ -C ₃ ) -Alkyl] -R ¹⁰ , CH ₂ NH-R ¹¹ , CH ₂ CH ₂ N [(C ₁ -C ₃ ) -alkyl] -R ¹² , CH ₂ CH ₂ NH-R ¹³ , the radicals other than hydrogen R ⁷ in formula (IVa) are preferably in the 5-position on the phenyl ring, and the radicals R ⁸ to R ^{13 are} H, (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) haloalkyl, CHO, COO (C ₁ -C ₆ ) alkyl, COO (C ₁ -C ₆ ) haloalkyl, SO ₂ - (C ₁ -C ₆ ) alkyl, SO ₂ - (C ₁ -C ₆ ) haloalkyl, CO- ( Is C ₁ -C ₆ alkyl or CO (C ₁ -C ₆ ) haloalkyl,
R ^{6 ''} Me, Et, ⁿ Pr, ⁱ Pr, ^c Pr, ⁿ Bu, ⁱ Bu, ^s Bu, ^t Bu, ^c Bu, especially Me or Et
R ^{7 '} Me, Et, CF ₃ , F, Cl, Br, I, N [(C ₁ -C ₅ ) alkyl] -R ⁸ , NH- (C ₁ -C ₃ ) alkyl, CH ₂ N [ (C ₁ -C ₃ ) alkyl] -R ¹⁰ , CH ₂ NH-R ¹¹ , CH ₂ CH ₂ N [(C ₁ -C ₃ ) alkyl] -R ¹² , CH ₂ CH ₂ NH-R ¹³ , wherein the radicals R7 in formula (IVb) other than hydrogen are preferably in the 5-position on the phenyl ring, and the radicals R ⁸ and R ¹⁰ to R ¹³ H, (C ₁ -C ₆ ) -alkyl, (C ₁ -C ₆ ) - Haloalkyl, CHO, COO (C ₁ -C ₆ ) alkyl, COO (C ₁ -C ₆ ) haloalkyl, SO ₂ - (C ₁ -C ₆ ) alkyl, SO ₂ - (C ₁ -C ₆ ) -haloalkyl, CO- (C ₁ -C ₆ ) -alkyl or CO- (C ₁ -C ₆ ) -haloalkyl,
R ^{6 '''} Me, Et, Pr, CH ₂ CH ₂ CF ₃ , OMe, OEt, O ⁱ Pr, OCH ₂ CH ₂ Cl, F, Cl, COOMe, COOEt, COO ⁿ Pr, COO ⁱ Pr, unsubstituted or substituted NH- (C ₁ -C ₆ ) alkyl acyl, unsubstituted or substituted NH- (C ₃ -C ₇ ) cycloalkyl, unsubstituted or substituted (C ₄ -C ₈ ) cycloalkylalkyl, unsubstituted or substituted N- (C ₃ -C ₇ ) - Cycloalkyl-aryl, unsubstituted or substituted N- (C ₄ -C ₈ ) -cycloalkylalkyl-acyl, preferably
N- (C ₁ -C ₆ ) alkyl-CHO, N- (C ₁ -C ₆ ) -alkyl-CO-R, N- (C ₁ -C ₅ ) -alkyl-SO ₂ R, NH-CHO, NH-CO-R, NHSO ₂ R, where the radicals R (C ₁ -C ₆ ) - (halo) alkyl, (C ₁ -C ₆ ) - (halo) alkoxy, (C ₁ -C ₃ ) - Alkoxy- (C ₁ -C ₆ ) -alkyl, (C ₁ -C ₃ ) -alkoxy- (C ₁ -C ₆ ) -alkoxy or mono- and di- (C ₁ -C ₆ ) -alkylamino,
R ^{7 ''} F, Cl, Me, Et, CF ₃ , OCH ₃ , OEt, OCH ₂ CF ₃ ,
M ⁺ [NR ¹⁴ R ¹⁵ R ¹⁶ R ¹⁷ ] ⁺ , or a quaternized pyridinium ion [Py-R ²⁵ ] ⁺ , where R ¹⁴ to R ^{16 are} identical or different H or substituted or unsubstituted (C ₁ -C ₃₀ ) alkyl , substituted or unsubstituted (C ₁ -C ₁₀ ) alkyl- (hetero) aryl, substituted or unsubstituted (C ₃ -C ₃₀ ) - (oligo) alkenyl, substituted or unsubstituted (C ₃ -C ₁₀ ) - (oligo ) Alkenyl (hetero) aryl, substituted or unsubstituted (C ₃ -C ₃₀ ) - (oligo) alkynyl, substituted or unsubstituted (C ₃ -C ₁₀ ) - (oligo) alkynyl (hetero) aryl, are substituted or unsubstituted (hetero) aryl and
R ¹⁷ and R ²⁵ substituted or unsubstituted (C ₁ -C ₃₀ ) alkyl, substituted or unsubstituted (C ₁ -C ₁₀ ) alkyl (hetero) aryl, substituted or unsubstituted (C ₃ -C ₃₀ ) - (oligo ) Alkenyl, substituted or unsubstituted (C ₃ -C ₁₀ ) - (oligo) alkenyl (hetero) aryl, substituted or unsubstituted (C ₃ -C ₃₀ ) - (oligo) alkynyl, substituted or unsubstituted (C ₃ -C ₁₀ ) - (Oligo) -alkynyl- (hetero) aryl, substituted or unsubstituted (hetero) aryl and where two radicals R ¹⁴ / R ¹⁵ and R ¹⁶ / R ¹⁷ together can form an unsubstituted or substituted ring,
X Me, Et, Pr, ⁱ Pr, CF ₃ , CCl ₃ , OMe, OEt, O ⁱ Pr, OCHCl ₂ , OCH ₂ CCl ₃ , OCH ₂ CF ₃ , F, Cl, Br, SMe, SEt, NHMe, NMe ₂ , NHEt, preferably OMe, OEt, Me, Cl
Y Me, Et, Pr, ⁱ Pr, CF ₃ , CCl ₃ , OMe, OEt, O ⁱ Pr, OCHCl ₂ , OCH ₂ CCl ₃ , OCH ₂ CF ₃ , F, Cl, Br, SMe, SEt, NHMe, NMe ₂ , NHEt, preferably OMe, OEt, Me, Cl and
Z CH and N
mean.

Suitable cations M ⁺ are cyclic cations such as [Py-R ²⁵ ] ⁺ or the formula

[NR ¹⁴ R ¹⁵ R ¹⁶ R ¹⁷ ] ⁺

wherein two radicals R ¹⁴ / R ¹⁵ or R ¹⁶ / R ¹⁷ together form an unsubstituted or substituted ring.

For example, R ¹⁴ / R ^{15 may} form a heterocyclic ring together with the charge-bearing nitrogen atom, such as. B. represented in the formulas V-VII,

or
R ¹⁴ / R ¹⁵ and R ¹⁶ / R ¹⁷ together with the charge-bearing nitrogen atom form a bicyclic system, such as. B. represented in formulas VIII and IX,

Preferred ammonium cations M ^⊕ are characterized in that
R ¹⁴ substituted or unsubstituted (C ₁ -C ₃₀ ) alkyl, substituted or unsubstituted (C ₁ -C ₁₀ ) alkyl (hetero) aryl, substituted or unsubstituted (C ₃ -C ₃₀ ) - (oligo) alkenyl , substituted or unsubstituted (C ₃ -C ₁₀ ) - (oligo) alkenyl (hetero) aryl, substituted or unsubstituted (C ₃ -C ₃₀ ) - (oligo) alkynyl, substituted or unsubstituted (C ₃ -C ₁₀ ) - (Oligo) alkynyl (hetero) aryl, substituted or unsubstituted (hetero) aryl,
R ¹⁵ substituted or unsubstituted (C ₁ -C ₃₀ ) alkyl, substituted or unsubstituted (C ₁ -C ₁₀ ) alkyl (hetero) aryl, substituted or unsubstituted (C ₃ -C ₃₀ ) - (oligo) alkenyl , substituted or unsubstituted (C ₃ -C ₁₀ ) - (oligo) alkenyl (hetero) aryl, substituted or unsubstituted (C ₃ -C ₃₀ ) - (oligo) alkynyl, substituted or unsubstituted (C ₃ -C ₁₀ ) - (Oligo) alkynyl (hetero) aryl, substituted or unsubstituted (hetero) aryl or H,
R ¹⁶ substituted or unsubstituted (C ₁ -C ₃₀ ) alkyl, substituted or unsubstituted (C ₁ -C ₁₀ ) alkyl (hetero) aryl, substituted or unsubstituted (C ₃ -C ₃₀ ) - (oligo) alkenyl , substituted or unsubstituted (C ₃ -C ₁₀ ) - (oligo) alkenyl (hetero) aryl, substituted or unsubstituted (C ₃ -C ₃₀ ) - (oligo) alkynyl, substituted or unsubstituted (C ₃ -C ₁₀ ) - (Oligo) alkynyl (hetero) aryl, substituted or unsubstituted (hetero) aryl or H,
R ¹⁷ substituted or unsubstituted (C1 -C ₃₀ ) alkyl, substituted or unsubstituted (C ₁ -C ₁₀ ) alkyl (hetero) aryl, substituted or unsubstituted (C ₃ -C ₃₀ ) - (oligo) alkenyl, substituted or unsubstituted (C ₃ -C ₁₀ ) - (oligo) alkenyl (hetero) aryl, substituted or unsubstituted (C ₃ -C ₃₀ ) - (oligo) alkynyl, substituted or unsubstituted (C ₃ -C ₁₀ ) - (Oligo) alkynyl (hetero) aryl, substituted or unsubstituted (hetero) aryl or H,
or NR ¹⁴ R ^{15 form} a heterocyclic system, such as. B. in formula (V) or (VI)

Particularly preferred cations M ^⊕ are characterized in that the residues
R ¹⁴ (C ₁ -C ₂₂ ) alkyl, unsubstituted or substituted by one or more radicals from the group (C ₁ -C ₅ ) alkyl, (C ₁ -C ₅ ) alkoxy, (C ₁ -C ₅ ) - Haloalkoxy, halogen, such as fluorine, chlorine, bromine and iodine, O- (CH ₂ -CH ₂ -O) _x H, O- (CH ₂ -CH ₂ -O) _x - (C ₁ -C ₃ ) alkyl, O- (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkyl or O- (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkoxy, phenyl, unsubstituted or substituted by one or more radicals of the group (C ₁ -C ₅ ) alkyl, (C ₁ -C ₅ ) alkoxy, (C ₁ -C ₅ ) haloalkoxy, halogen, such as fluorine , Chlorine, bromine and iodine, O- (CH ₂ -CH ₂ -O) _x H, O- (CH ₂ -CH ₂ -O) _x (C ₁ -C ₃ ) alkyl, O- (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkyl, O- (CH ₂ -CH ₂ -O) _x (CO) - (C ₁ -C ₃ ) alkoxy, C ₁ -C ₁₀ -alkyl, which is likewise replaced by one of the radicals O- (CH ₂ -CH ₂ ) _x -OH, O- (CH ₂ -CH ₂ ) _x -O- (C ₁ -C ₃ ) -alkyl, O- (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkyl, or O- (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkoxy , can be substituted,
(C ₃ -C ₂₂ ) alkenyl, unsubstituted or substituted by one or more radicals from the group (C ₁ -C ₅ ) alkyl, (C ₁ -C ₅ ) alkoxy, (C ₁ -C ₅ ) haloalkoxy , Halogen, such as fluorine, chlorine, bromine and iodine, O- (CH ₂ -CH ₂ -O) _x H, O- (CH ₂ -CH ₂ -O) _x - (C ₁ -C ₃ ) alkyl, O - (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkyl or O- (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkoxy, and wherein the alkenyl radical is mono- or polyunsaturated, but preferably bears between one and three double bonds,
(C ₃ -C ₂₂ ) alkynyl, unsubstituted or substituted by one or more radicals from the group (C ₁ -C ₅ ) alkyl, (C ₁ -C ₅ ) alkoxy, (C ₁ -C ₅ ) haloalkoxy , Halogen, such as fluorine, chlorine, bromine and iodine, O- (CH ₂ -CH ₂ -O) _x H, O- (CH ₂ CH ₂ -O) _x - (C ₁ -C ₃ ) alkyl, O- (CH ₂ -CH ₂ ) _x - (CO) - (C ₁ -C ₃ ) alkyl or O- (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkoxy, and wherein the alkynyl radical is mono- or polyunsaturated, but preferably bears between one and three triple bonds, where
x is an integer from 1-40,
R ¹⁵ to R ^{17, the} same or differently substituted or unsubstituted (C ₁ -C ₃₀ ) alkyl, substituted or unsubstituted (C ₁ -C ₁₀ ) alkyl (hetero) aryl, substituted or unsubstituted (C ₃ -C ₃₀ ) - (Oligo) alkenyl, substituted or unsubstituted (C ₃ -C ₁₀ ) - (oligo) alkenyl (hetero) aryl, substituted or unsubstituted (C ₃ -C ₃₀ ) - (oligo) alkynyl, substituted or unsubstituted (C ₃ -C ₁₀ ) - (oligo) alkynyl (hetero) aryl, substituted or unsubstituted (hetero) aryl,
R ²⁵ (C ₁ -C ₂₂ ) alkyl, unsubstituted or substituted by one or more radicals from the group (C ₁ -C ₅ ) alkyl, (C ₁ -C ₅ ) alkoxy, (C ₁ -C ₅ ) - Haloalkoxy, halogen, such as fluorine, chlorine, bromine and iodine, O- (CH ₂ -CH ₂ -O) _x H, O- (CH ₂ -CH ₂ -O) _x - (C ₁ -C ₃ ) alkyl, O- (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkyl or O- (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkoxy, phenyl, unsubstituted or substituted by one or more radicals of the group (C ₁ -C ₅ ) alkyl, (C ₁ -C ₅ ) alkoxy, (C ₁ -C ₅ ) haloalkoxy, halogen, such as fluorine , Chlorine, bromine and iodine, O- (CH ₂ -CH ₂ -O) _x H, O- (CH ₂ -CH ₂ -O) _x - (C ₁ -C ₃ ) alkyl, O- (CH ₂ - CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkyl, O- (CH ₂ -CH ₂ -O) _x (CO) - (C ₁ -C ₃ ) alkoxy, C ₁ - C ₁₀ alkyl, which is likewise replaced by one of the radicals O- (CH ₂ -CH ₂ ) _x -OH, O- (CH ₂ -CH ₂ ) _x -O- (C ₁ -C ₃ ) alkyl, O- ( CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkyl, or O- (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) - alkoxy, can be substituted,
(C ₃ -C ₂₂ ) alkenyl, unsubstituted or substituted by one or more radicals from the group (C ₁ -C ₅ ) alkyl, (C ₁ -C ₅ ) alkoxy, (C ₁ -C ₅ ) haloalkoxy , Halogen, such as fluorine, chlorine, bromine and iodine, O- (CH ₂ -CH ₂ -O) _x H, O- (CH ₂ -CH ₂ -O) _x - (C ₁ -C ₃ ) alkyl, O - (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkyl or O- (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkoxy, and wherein the alkenyl radical is mono- or polyunsaturated, but preferably bears between one and three double bonds,
(C ₃ -C ₂₂ ) alkynyl, unsubstituted or substituted by one or more radicals from the group (C ₁ -C ₅ ) alkyl, (C ₁ -C ₅ ) alkoxy, (C ₁ -C ₅ ) haloalkoxy , Halogen, such as fluorine, chlorine, bromine and iodine, O- (CH ₂ -CH ₂ -O) _x H, O- (CH ₂ -CH ₂ -O) _x - (C ₁ -C ₃ ) alkyl, O - (CH ₂ -CH ₂ ) _x - (CO) - (C ₁ -C ₃ ) alkyl or O- (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkoxy , and wherein the alkynyl radical is mono- or polyunsaturated, but preferably bears between one and three triple bonds,
where x is an integer from 1 to 40,
mean.

M ⁺ cations are particularly preferred, in which
R ¹⁴ to R ¹⁵ and R ^{25 are} identical or different from one another (C ₁ -C ₂₂ ) alkyl, unsubstituted or substituted by one or more radicals from the group (C ₁ -C ₅ ) alkyl, (C ₁ -C ₅ ) - Alkoxy, (C ₁ -C ₅ ) haloalkoxy, halogen, such as fluorine, chlorine, bromine and iodine, O- (CH ₂ -CH ₂ -O) _x H, O- (CH ₂ -CH ₂ -O) _x - (C ₁ -CH ₂ -O) _x - (C ₁ -C ₃ ) alkyl, O- (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkyl or O- (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkoxy, phenyl, unsubstituted or substituted by one or more radicals from the group (C ₁ -C ₅ ) alkyl, (C ₁ -C ₅ ) alkoxy, (C ₁ -C ₅ ) haloalkoxy, halogen such as fluorine, chlorine, bromine and iodine, O- (CH ₂ CH ₂ O) _x H, O- (CH ₂ CH ₂ O) _x - (C ₁ -C ₃ ) alkyl, O- (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkyl, O- (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkoxy, C ₁ -C ₁₀ alkyl, which is likewise replaced by one of the radicals O- (CH ₂ -CH ₂ ) _x -OH, O- (CH ₂ -CH ₂ ) _x -O- (C ₁ -C ₃ ) alkyl, O- (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkyl, or O- (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkoxy,
can be substituted
(C ₃ -C ₂₂ ) alkenyl, unsubstituted or substituted by one or more radicals from the group (C ₁ -C ₅ ) alkyl, (C ₁ -C ₅ ) alkoxy, (C ₁ -C ₅ ) haloalkoxy , Halogen, such as fluorine, chlorine, bromine and iodine, O- (CH ₂ -CH ₂ -O) _x H, O- (CH ₂ -CH ₂ -O) _x - (C ₁ -C ₃ ) alkyl, O - (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkyl or O- (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkoxy, and where the alkenly radical is mono- or polyunsaturated, but is preferably between one and three double bonds,
(C ₃ -C ₂₂ ) alkynyl, unsubstituted or substituted by one or more radicals from the group (C ₁ -C ₅ ) alkyl, (C ₁ -C ₅ ) alkoxy, (C ₁ -C ₅ ) haloalkoxy , Halogen, such as fluorine, chlorine, bromine and iodine, O- (CH ₂ -CH ₂ -O) _x H, O- (CH ₂ -CH ₂ -O) _x - (C ₁ -C ₃ ) alkyl, O - (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkyl or O- (CH ₂ -CH ₂ -O) _x - (CO) - (C ₁ -C ₃ ) alkoxy, and the alkynyl radical being mono- or polyunsaturated, but preferably having between one and three triple bonds,
where x is an integer from 1 to 40.

The above-mentioned sulfonylurea salts, preferably of the formula (Ia), in Combination with auxiliaries and additives are suitable for the production of Formulations especially for the production of EC formulations.

Possible formulation options are, for example: wettable powder (WP), water-soluble powder (SP), water-soluble concentrates, emulsifiable Concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil Emulsions, sprayable solutions, suspension concentrates (SC), dispersions based on oil or water, oil-miscible solutions, capsule suspensions (CS), Dusts (DP), pickling agents, 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 ed. 1986, Wade von Valkenburg, "Pesticide  Formulations ", Marcel Dekker, N.Y., 1973; K. Martens," Spray Drying "Handbook, 3rd ed. 1979, G. Goodwin Ltd. London.

Formulation aids such as inert materials, surfactants, solvents and others Additives are also known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers," 2nd Ed., Darland Books, Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y .; C. Marsden, "Solvents Guide"; 2nd Ed., Interscience, N.Y. 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, "Surface-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 with others can also be made pesticidal substances, such as. B. insecticides, acaricides, herbicides, Fungicides, and with safeners such as 1- (2,4-dichlorophenyl) -5- (ethoxycarbonyl) -5- methyl 2-pyrazoline-3-carboxylic acid ethyl ester (mefenpyr) or 5,5-diphenyl-2- isoxazoline-carboxylic acid ethyl ester, 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, also ionic and / or surfactants non-ionic type (wetting agent, dispersing agent), e.g. B. polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines, Fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium lignosulfonic acid, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, dibutylnaphthalene-sulfonic acid sodium or oleoylmethyltauric acid sodium contain. The herbicidal active ingredients are used to produce the wettable powders for example in conventional equipment such as hammer mills, fan mills and  Air jet mills finely ground and simultaneously or subsequently with the Formulation aids mixed.

Emulsifiable concentrates are made by dissolving the active ingredient in one organic solvents e.g. B. butanol, cyclohexanone, dimethylformamide, xylene or also higher-boiling aromatics or hydrocarbons or mixtures the organic solvent with the addition of one or more surfactants ionic and / or nonionic type (emulsifiers). As emulsifiers can be used for example: alkylarylsulfonic acid calcium salts such as Ca-dodecylbenzenesulfonate or nonionic emulsifiers such as Alkylaryl polyglycol ethers other than para-alkyl phenol ethoxylates, Fatty acid polyglycol esters, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide Condensation products, alkyl polyethers, sorbitan esters such as e.g. B. sorbitan fatty acid esters or polyoxethylene sorbitan esters such. B. Polyoxyethylene sorbitan fatty acid esters.

Dusts are obtained by grinding the active ingredient with finely divided solid Fabrics, 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) can be used, for example Stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants such as z. B. already listed above for the other formulation types.

Granules can either be sprayed onto the adsorbable, granulated inert material or by applying  Active ingredient concentrates by means of adhesives, e.g. B. sugar and pentoses and hexoses or mineral oils on the surface of carriers such as sand, kaolinite or of granulated inert material. Suitable active ingredients can also be used in the Production of fertilizer granules in the usual way - if desired in Mix with fertilizers - be granulated.

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

For the production of plate, fluidized bed, extruder and spray granules see e.g. B. 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. B. G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pp. 81-96 and J.D. Freyer, S.A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

In addition, the active ingredient formulations mentioned may each contain usual adhesive, wetting, dispersing, emulsifying, penetration, preservation, Antifreeze and solvents, fillers, carriers and dyes, defoamers, Evaporation inhibitors and agents that affect pH and viscosity.

New and also the subject of this invention is the use of the auxiliaries of the formulas (XVIII) and (XIX) as formulation auxiliaries for agrochemical formulations and their use in the synthesis of salts of agrochemical active ingredients with acidic proton / acidic protons.

The auxiliaries of the formula (XVIII) or (XIX) can be used as pure substance or in the form of a solid or liquid mixture. In the formulas (XVIII) and (XIX), the indices w, x, y, z can independently assume an integer value from 0 to 50. The radical R is a C ₈ -C ₄₀ alkyl radical. This can be saturated or unsaturated, linear or branched. M ^⊕ is an ammonium ion or a metal cation such as. B. an alkali metal ion such as sodium or potassium ion.

EO means ethoxy unit, PO means propoxy unit R ', R ", R""are substituted or unsubstituted (C ₁ -C ₁₀₀ ) alkyl radicals, where the alkyl radicals can be saturated or unsaturated, linear or branched. As substituents F, Cl, Br or I or a hydroxyl or amino function are possible, for example This definition also includes the substitution of one carbon atom of the alkyl chain by one or more oxygen or nitrogen atoms.

As a combination partner for the sulfonylurea salts in the formulations according to the invention, for example, known active ingredients can be used, such as those described, for. B. from Weed Research 26, 441-445 (1986) or "The Pesticide Manual", 11th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 1997 and the literature cited therein. As known herbicides, which can be combined with the sulfonylurea salts, z. For example, the following active substances are to be mentioned (note: the compounds are identified either with the "common name" according to the International Organization for Standardization (ISO) or with the chemical name, possibly together with a usual code number):
acetochlor; acifluorfen; aclonifen; AKH 7088, ie [[[1- [5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrophenyl] -2-methoxyethylidene] amino] oxy] acetic acid and methyl acetate; alachlor; alloxydim; ametryn; amidosulfuron; amitrole; AMS, ie ammonium sulfamate; anilofos; asulam; atrazine; azafenidin; azimsulfuron (DPX-A8947); aziprotryn; barban; BAS 516 H, ie 5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; BAS 620 H; BAS 6540OH; BAY FOE 5043; benazolin; benfluralin; benfuresate; bensulfuron-methyl; bensulide; bentazone; benzofenap; benzofluor; benzoylprop-ethyl; benzthiazuron; bialaphos; bifenox; bispyribac-Na; bromacil; bromobutide; bromofenoxim; bromoxynil; bromuron; buminafos; busoxinone; butachlor; butamifos; butenachlor; buthidazole; butralin; butroxydim; butylates; cafenstrole (CH-900); caloxydim; carbetamide; carfentrazone-ethyl; CDAA, ie 2-chloro-N, N-di-2-propenylacetamide; CDEC, ie 2-chloroallyl ester of diethyldithiocarbamic acid; chlomethoxyfen; chloramben; chlorazifop-butyl, chlorbromuron; chlorobufam; chlorfenac; chlorofiurecol-methyl; chloridazon; chlorimuron ethyl; chloronitrofen; chiorotoluron; chloroxuron; chlorpropham; chlorsulfuron; chlororthal dimethyl; chlorothiamide; cinmethylin; cinosulfuron; clethodim; clodinafop and its ester derivatives (e.g. clodinafop-propargyl); clomazone; clomeprop; cloproxydim; clopyralid; cloransulam-methyl; cumyluron (JC 940); cyanazine; cycloate; cyclosulfamuron (AC 104); cycloxydim; cycluron; cyhalofop and its ester derivatives (e.g. butyl ester, DEH-112); cyperquat; cyprazine; cyprazole; daimuron; 2,4-DB; dalapon; desmedipham; desmetryn; di-allate; dicamba; dichlobenil; dichlorprop; diclofop and its esters such as diclofop-methyl; diclosulam, ie N- (2,6-dichlorophenyl) -5-ethoxy-7-fluoro [1, 2,4] triazolo [1,5-c] pyrimidine-2-sulfonamide; diethatyl; difenoxuron; difenzoquat; diflufenican; diflufenzopyr (BAS 654 OOH), dimefuron; dimethachlor; dimethametryn; dimethenamid (SAN-582H); dimethazone, clomazone; dimethipin; dimetrasulfuron, dinitramine; dinoseb; dinoterb; diphenamide; dipropetryn; diquat; dithiopyr; diuron; DNOC; eglinazine-ethyl; EL 77, ie 5-cyano-1- (1,1-dimethylethyl) -N-methyl-1H-pyrazole-4-carboxamide; endothal; EPTC; esprocarb; ethalfluralin; ethametsulfuron-methyl; ethidimuron; ethiozin; ethofumesate; F5231, ie N- [2-chloro-4-fluoro-5- [4- (3-fluoropropyl) -4,5-dihydro-5-oxo-1 H-tetrazol-1-yl] phenyl] ethanesulfonamide; ethoxyfen and its esters (e.g. ethyl ester, HN-252); etobenzanide (HW 52); fenoprop; fenoxan, fenoxaprop and fenoxaprop-P and their esters, e.g. B. fenoxaprop-P-ethyl and fenoxaprop-ethyl; fenoxydim; fenuron; flamprop-methyl; flazasulfuron; fluazifop and fluazifop-P and their esters, e.g. B. 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); flupyrsulfuron-methyl-sodium; fluridone; flurochloridone; fluroxypyr; flurtamone; fluthiacet-methyl; 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 esters; hexazinone; imazamethabenz-methyl; imazamox; imazapyr; imazaquin and salts such as the ammonium salt; imazethamethapyr; imazethapyr; imazosulfuron; indanofan (MK-243), iodosulfuron, ioxynil; isocarbamide; isopropaline; isoproturon; isouron; isoxaben; isoxaflutole; isoxapyrifop; carbutilates; lactofen; lenacil; linuron; MCPA; MCPB; mecoprop; mefenacet; mefluidide; metamitron; metazachlor; methabenzthiazuron; metham; methazole; methoxyphenone; methyldymron; metobenzuron; metobromuron; metolachlor; metosulam (XRD 511); Aetoxuron; metribuzin; metsulfuron-methyl; MH; molinate; monalide; monocarbamide dihydrogen sulfates; monolinuron; monuron; MT 128, ie 6-chloro-N- (3-chloro-2-propenyl) -5-methyl-N-phenyl-3-pyridazinamine; MT 5950, ie N- [3-chloro-4- (1-methylethyl) phenyl] -2-methylpentanamide; naproanilide; napropamide; naptalam; NC 310, ie 4- (2,4-dichlorobenzoyl) -1-methyl-5-benzyloxypyrazole; neburon; nicosulfuron; nipyraclophen; nitraline; nitrofen; nitrofluorfen; norflurazon; orbencarb; oryzalin; oxadiargyl (RP-020630); oxadiazon; oxasulfuron; oxaziclomefone (MY-100); oxyfluorfen; paraquat; pebulate; pendimethalin; pentoxazone (KPP-314); 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; pyroflufen-ethyl; pyrazolinates; pyrazone; pyrazosulfuron-ethyl; pyrazoxyfen; pyribenzoxim (LGC-40836); pyributicarb; pyridate; pyriminobac-methyl; pyrithiobac (KIH-2031); pyroxofop and its esters (e.g. propargyl esters); quinclorac; quinmerac; quinofop and its ester derivatives, quizalofop and quizalofop-P and their ester derivatives z. B. 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; sixumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, ie 2 - [[7- [2-chloro-4- (trifluoromethyl) phenoxy] -2-naphthalenyl] oxy] propanoic acid and methyl ester; sulcotrione; sulfentrazone (FMC-97285, F-6285); sulfazuron; sulfometuron-methyl; sulfosate (ICI-A0224); sulfosulfuron; TCA; tebutam (GCP-5544); tebuthiuron; terbacil; terbucarb; terbuchlor; terbumeton; terbuthylazine; terbutryn; TFH 450, ie N, N-diethyl-3 - [(2-ethyl-6-methylphenyl) sulfonyl] -1H-1,2,4-triazole-1-carboxamide; thenylchlor (NSK-850); thiazafluron; thiazopyr (Mon-13200); thidiazimin (SN-24085); thifensulfuron-methyl; thiobencarb; tiocatbazil; tralkoxydim; tri-allate; triasulfuron; triaziflam, triazofenamide; tribenuron-methyl; triclopyr; tridiphane; trietazine; trifluralin; triflusulfuron and esters (e.g. methyl ester, DPX-66037); trimeturon; tsitodef; vernolate; WL 110547, ie 5-phenoxy-1- [3- (trifluoromethyl) phenyl] -1 H-tetrazole; JTC-101; 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.

The formulations available in commercial form are used optionally diluted in the usual manner, e.g. B. with wettable powders, emulsifiable Concentrates, dispersions and water-dispersible granules using water.

The formulations according to the invention generally contain 0.1 to 99% by weight, in particular 0.1 to 95 wt .-%, active ingredient, preferably a sulfonylurea salt of the formula (Ia). 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 ingredients. With emulsifiable concentrates Active ingredient concentration about 1 to 90, preferably 5 to 80 wt .-%. Dust-like formulations contain 1 to 30% by weight of active compound, preferably usually 5 to 20 wt .-% of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt .-% active ingredient. With water dispersible Granules, the active ingredient content depends in part on whether the effective  Connection is liquid or solid and which granulation aids, fillers etc. be used. The content is in the case of the water-dispersible granules of active ingredient, for example between 1 and 95% by weight, preferably between 10 and 80% by weight.

Dust-like formulations, soil or scatter granules as well as sprayable Solutions are usually no longer mixed with other inert solutions before use Diluted substances.

The EC formulations according to the invention are characterized in that the proportion of sulfonylurea salts is generally 00.1-70% by weight, preferably 0.1-70% by weight, particularly preferably 0.1-50% by weight. In addition, other agrochemicals from the field of crop protection - e.g. B. Herbicides, fungicides, insecticides, growth regulators, safeners or fertilizers - between 0 to 70 wt .-%. It can also contain between 1 and 40% by weight, preferably 2-40% by weight, of a surfactant system. The surfactant system can e.g. B. from

• a) one or more non-ionic surfactants,
• b) one or more betaine surfactants,
• c) one or more anionic surfactants,
• d) one or more cationic surfactants, or
• e) a mixture of the surfactants mentioned under a) -d)

put together.

The EC formulations can contain between 0 and 95% by weight, preferably between 5 and 95% by weight, of a solvent system. Suitable solvents are, for example

• a) a non-polar solvent, e.g. B. aromatic hydrocarbons such as Solvesso®, Esters of long-chain saturated or unsaturated (fatty) acids and / or Alcohols such as B. rapeseed oil methyl ester, or a mixture of non-polar Solvents  
• b) a polar protic or aprotic solvent e.g. B. gamma-butyrolactone, Propylene carbonate, propionitrile or methanol, ethanol, or mixtures from it or
• c) Mixtures of the solvent systems mentioned above under a) and b).

In addition, the EC formulations according to the invention can optionally 3-90% by weight a wetting agent that can have bioactivating properties, or one Mixture of different wetting agents that have bioactivating properties may contain or other bio-activating auxiliaries (adjuvants).

Optionally, other stabilizing compounds, e.g. B. stabilizing pH Reagents (e.g. PH 5-9), substances with defoaming properties, Acid scavengers, water scavengers or crystallization inhibitors can be included.

Another embodiment of the formulations according to the invention is characterized in that it is a dispersion, the liquid, homogeneous phase is constructed as described above and into the one or more insoluble compounds are dispersed. With the insoluble Substances can be agrochemicals such as B. herbicides, insecticides, fungicides, Act safener or fertilizer, or formulation aids, such as. B. Surfactants that do not dissolve in the organic phase, e.g. B. Netzer IS (Fa. Clariant).

The EC formulations according to the invention are therefore preferred characterized in that the proportion of the sulfonylurea salt, in particular the Formula (Ia) or the mixture of sulfonylurea salts in general 0.1-70.0% by weight, preferably 0.1-50.0% by weight. As suitable solvents are polar solvents such. B. gamma-butyrolactone, acetonitrile, propionitrile; their proportion is 5.0-95.0% by weight. To add a stable emulsion after adding To get water, the finished EC product should have a weight percentage of 2.0-40.0% by weight of a mixture of an anionic and a non-ionic  Surfactants or a mixture of cationic and non-ionic surfactants contain. In addition, additional components to the EC Formulations are added: By adding a hydrophobic solvent in the Emulsion formation in the aqueous can range from 1.0-90.0% by weight Spray mixtures are advantageously influenced. As solvent components is suitable for. B. rapeseed oil methyl ester, aromatic solvents such as. B. Solvesso, Esters of long-chain acids and alcohols, or a mixture of more hydrophobic ones Solvents.

The EC formulations described in this way can optionally have a proportion of 3.0-90.0% by weight of a wetting agent which can have bioactivating properties, or a mixture of wetting agents.

Combined agrochemicals can be obtained by agrochemical active substances that are chemically opposed to sulfonylurea salts behave inertly and in the typical for the formulation type according to the invention Solvent system are readily soluble, added in the range between 20.0-50.0 wt .-% become. This is the case for a large number of commercially available agrochemicals. The formulations according to the invention can optionally also contain stabilizers contain the z. B. stabilize the pH of the tank mix between 6 and 8 should.

EC formulations according to the invention preferably have the following composition:

• 1. the content of sulfonylurea salts is generally 0.1-70.0% by weight, preferably 0.1-50.0% by weight; one or more Active ingredients to be included in the formulation
• 2. Optionally, other agrochemicals (herbicides, insecticides, fungicides, Growth regulators, safeners, fertilizers) contain between 0 to 50.0 wt .-% his,
• 3. 5.0-95.0 wt .-% of a polar solvent, such as. B. gamma-butyrolactone, Acetonitrile, propionitrile, propylene carbonate, or mixtures thereof are included  
• 4. optionally between 1.0-90.0% by weight of a hydrophobic solvent, e.g. B. rapeseed oil methyl esters, aromatic solvents, esters of long chain acids and Alcohols
• 5. 2.0-40.0% by weight of a mixture of anionic and nonionic compounds are included or
• 6. 2.0-40.0% by weight of a mixture of cationic and nonionic compounds are included
• 7. Optional 3.0-90.0% by weight of a wetting agent that has bioactivating properties can have, or a mixture of different wetting agents that may have bioactivating properties.
• 8. optional additional stabilizing agents - e.g. B. pH stabilizing Reagents (pH between 6 and 8), substances with defoaming Properties, substances used as acid scavengers, water scavengers or Crystallization inhibitors can serve.

To produce an EC formulation, for example, between 0.1 to 15.0% by weight sulfonylurea salt in 15.0 to 25.0% by weight propylene carbonate and 30.0 to 50.0% by weight of an aromatic or aromatic mixture (boiling range 219-282 ° C) be dissolved with stirring at 20 ° C-30 ° C.

After the sulfonylurea salt is completely dissolved, 5.0 to 15.0% by weight of calcium or sodium salt of dodecylbenzenesulfonic acid or a salt mixture, 5.0 to 15.0% by weight of a (C ₁₂ -C ₁₈ ) - Fatty acid polyglycol ester 40 EO and 15.0 to 20.0% by weight of a fatty alcohol polyglycol ether with stirring to the solution.

Optionally, a water trap, an acid trap, a defoamer or a Crystallization inhibitors are used.

The sulfonylurea salts contained in the formulations according to the invention, e.g. B. of the formula (Ia) can be made from known sulfonylureas or sulfonylurea metal salts, in particular alkali metal salts (see, for example, EP-A-30138, EP-A-7687) or also starting from sulfonamide salts, for. B. Manufacture in the following ways:

• 1. Deprotonation of neutral sulfonylureas e.g. B. of the formula (XIII) with a suitable base of the formula M ⁺ B ^- (Eq. 1), where B ^{- represent,} for example, hydroxyl or alkoxy anions, such as methoxy, ethoxy, ⁿ propoxy, ⁱ propoxy, ⁿ butoxy or ^t butoxy or anions of formulation auxiliaries which carry at least one OH group, e.g. B. alcoholates that alkoxylated, e.g. B. may be ethoxylated or propoxylated, such as C ₈ H ₁₇ (OCH ₂ CH ₂ ) O ^⊖ and M ^{+ is} an ammonium ion.
  For this purpose, the sulfonylurea z. B. of formula (XIII) dissolved or suspended in an inert solvent or solvent mixture and with an equivalent of M ⁺ B ^- at temperatures between -20 ° C and 100 ° C, preferably between -10 ° C and 50 ° C.
• 2. Salting of metal salts of sulfonylureas z. B. of the formula (XIV), wherein Met ^{⊕ is} a metal cation, preferably an alkali metal ion such as Na ⁺ or K ⁺ with suitable reagents of the formula M ⁺ X ' ^- (Eq. 2), where M ^{+ is} an ammonium ion and X is an anion , for example a halogen anion such as F ^- , Cl ^- or Br ^- or may be a phosphate, sulfate or carboxylate anion, this definition including inorganic and organic salts, as described for. B. are common in surfactant chemistry (z. B. organic phosphate anions, phosphonate anions, sulfate anions, sulfonate anions, carboxylates).
  For this purpose, the metal salt known from the literature or shown in the manner known from the literature, e.g. As alkali metal salts (e.g., Met ^⊕ = Na ^+, K ^+.) Of the corresponding sulfonylureas in an inert solvent or mixture of solvents and treated with one equivalent of the reagent M ⁺ X ^'- implemented. After the reaction has ended, the salt obtained as a by-product, e.g. B. Alkali salt (such as NaCl) can be separated.
• 3. In-situ deprotonation and salting (Eq. 3), starting from neutral sulfonylureas z. B. of the formula (XIII) with suitable reagents a) of the formula M ⁺ X '^-; where M ^{+ is} an ammonium ion and X is an anion, for example a halogen anion such as F ^- , Cl ^- or Br ^- or can be a phosphate, sulfate or carboxylate anion, this definition including inorganic and organic salts, as described, for. B. are common in surfactant chemistry (z. B. organic phosphate anions, phosphonate anions, sulfate anions, sulfonate anions, carboxylates) and b) of the formula MetB, wherein Met is a metal cation, in particular an alkali metal cation such as Na ⁺ or K ⁺ and B is a suitable base e.g. B., a hydroxy or alkoxy anion such as methoxy, ethoxy, ⁿ propoxy, ⁱ propoxy or ⁿ butoxy or the anion of an alkoxylated, e.g. B. is ethoxylated or propoxylated, C ₈ -C ₄₀ alcohol.
  For this purpose, the sulfonylurea is dissolved in an inert solvent or solvent mixture and reacted with one equivalent each of the reagents M ⁺ X ' ^- and MetB. After the reaction has ended, the metal salt, in particular alkali salt (eg NaCl), which is obtained as a by-product, can be separated off by filtration.
• 4. Reactions of a sulfonylurea with suitable zwitterions, e.g. B.
  wherein R is a C ₁ -C ₂₀ hydrocarbon radical such as C ₁ -C ₁₀ alkyl, R 'and R "are identical or different and hydrogen or C ₁ -C ₃₀ hydrocarbon radicals such as C ₁ -C ₁₀ alkyl and m is an integer from 0 to 100.
  For this purpose, a sulfonylurea, e.g. B. the formula XIII with a zwitterion such. B. in equation (4) in an inert solvent z. B. MeOH, THF or CH ₂ Cl ₂ or solvent mixture at temperatures between -20 ° C and 100 ° C, preferably -10 ° C and 80 ° C in equimolar ratios.
• 5. Implementation of a sulfonamide salt z. B. the Formei XV with an isocyanate z. B. the formula XVI (Eq. 5).
  The reaction takes place in an inert solvent or solvent mixture - such as. B. tetrahydrofuran (THF) - at temperatures between -20 ° C and 100 ° C, preferably between -10 ° C and 70 ° C by the isocyanate z. B. the formula XVI equimolar with the sulfonamide salt z. B. Formula XV. The sulfone salt z. B. Formula XV used directly or formed in-situ - z. B. by reaction of the corresponding sulfonamide with a suitable base M ⁺ X ^- , wherein M ^{+ is} a phosphonium or sulfonium ion and X ^- z. B. a hydroxy or alkoxy anion. Isocyanates e.g. B. Formula XVI are well known in the literature. These reactions always lead to compounds in which R ¹ corresponds to hydrogen.
• 6. Implementation of a sulfonamide salt z. B. the formula XV with a carbamate z. B. the formula XVII (Eq. 6).
  The reaction takes place in an inert solvent (or solvent mixture) - such as tetrahydrofuran - at temperatures between -20 ° C and 100 ° C, preferably between -10 ° C and 70 ° C, by the carbamate z. B. the formula XVII equimolar with the sulfonamide salt z. B. Formula XV. The sulfonamide salt z. B. Formula XV used directly or formed in-situ - z. B. by reaction of the corresponding sulfonamide with a suitable base M ⁺ X ^- , wherein M ^{+ is} a phosphonium or sulfonium ion and X ^- z. B. a hydroxy or alkoxy anion. Carbamates e.g. B. Formula XVII are well known in the literature. Ar in formula XVII means a substituted or unsubstituted aromatic radical, such as phenyl or 2,4-dichlorophenyl.
• 7. Implementation of a sulfonylurea z. B. of the formula V with a primary, secondary or tertiary amine NRR'R "(Eq. 7), wherein R is a C ₁ -C ₂₀ hydrocarbon radical such as C ₁ -C ₁₀ alkyl and R 'and R" are the same or different from one another are different and are hydrogen or a C ₁ -C ₂₀ hydrocarbon radical such as C ₁ -C ₁₀ alkyl.
  This reaction takes place between temperatures of -20 ° C to + 100 ° C, preferably between -10 ° C and 50 ° C, in inert solvents such as. B. THF, CH ₂ Cl ₂ or MeOH or mixtures of solvents instead.

The definitions used in manufacturing processes 1) to 7) have - if not otherwise designated - the same meaning as above for formulas Ia and Ib specified.

Inert solvents mean that the solvents or Solvent mixtures chemically under the specified reaction conditions behave inertly.  

According to the production process 1) to 7), the sulfonylurea salts can be simple be made and isolated. Alternatively, the manufacture of the Sulfonylurea salts according to processes 1), 2), 3), 4) and 7) also during the Formulation process.

The preparation processes for the compounds of the formulas (Ia) according to the invention are also new and also the subject of this invention.

According to the above-mentioned manufacturing processes, e.g. B. in the Establish the connections specified in the following tables. Here are n, m and o integers between 1 and 100.

Compounds of the following formula (A) are listed in Table 1:

Table 1

Compounds of the following formula (B) are listed in Table 2:

Table 2

Compounds of the following formula (C) are listed in Table 3:

Table 3

Compounds of the following formula (D) are listed in Table 4:

Table 4

Compounds of the following formula (E) are listed in Table 5:

Table 5

The compounds of formula (Ia) according to the invention as well as the Formulations according to the invention can be used as herbicides against a broad range Spectrum of economically important mono- and dicotyledonous harmful plants used become. Perennial weeds that are difficult to control and are made from rhizomes, The active ingredients drive out rootstocks or other permanent organs well grasped. It does not matter whether the substances are pre-seeded, pre-emergence or Post-emergence procedures are applied. Some are examples in detail Representative of the monocotyledonous and dicotyledonous weed flora, caused by the Compounds according to the invention can be controlled without the Naming a restriction to certain types.

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

In dicotyledon weed species, the spectrum of activity extends to species such as: B. 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.

Harmful plants occurring in rice under the specific culture conditions such as B. Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus of the active compounds according to the invention also combated 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 up to the cotyledon stage,  however, they stop growing and eventually die after three up to four weeks.

When applying the active ingredients to the green parts of the plant in a post-emergence process there is also a drastic growth stop very quickly after the treatment and the weed plants remain in the existing at the time of application Stages of growth stand or die completely after a certain time, so that in this way weed competition harmful to crops very early and is permanently eliminated.

Although the compounds and formulations of the invention are one excellent herbicidal activity against mono- and dicotyledon weeds have, crops of economically important crops such. B. Wheat, barley, rye, rice, corn, sugar beet, cotton and soy only insignificant or not damaged at all. The present compounds are suitable for these reasons, very good for selective control of unwanted Plant growth in agricultural crops or in ornamental crops.

In addition, the substances and formulations according to the invention have excellent growth regulatory properties in crops. she intervene regulatively in the plant's own metabolism and can thus help targeted influencing of plant ingredients and to facilitate harvesting such as e.g. B. by triggering desiccation and stunted growth. Furthermore, they are also suitable for general control and inhibition of undesirable vegetative growth without killing the plants. A Inhibition of vegetative growth plays in many mono- and dicotyledons Cultures play a major role, as this reduces or completely prevents storage can be.

Because of their herbicidal and plant growth regulatory properties the active ingredients and formulations can also be used to combat Harmful plants in crops of known or still to be developed genetically  modified plants can be used. The transgenic plants are characterized in generally characterized by special advantageous properties, for example by Resistance to certain pesticides, especially certain herbicides, Resistance to plant diseases or pathogens causing plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses. Other special properties concern e.g. B. the crop in terms of quantity, Quality, shelf life, composition and special ingredients. So are transgenic plants with increased starch content or changed starch quality or known with a different fatty acid composition of the crop.

Preferred is the use of the compounds and Formulations in economically important transgenic cultures of crops and Ornamental plants, e.g. B. of cereals such as wheat, barley, rye, oats, millet, rice, Cassava and corn or crops of sugar beet, cotton, soybeans, rapeseed, Potato, tomato, pea and other vegetables.

The formulations and compounds according to the invention can preferably are used as herbicides in crops which are active against phytotoxic effects of herbicides are resistant or genetically resistant have been made.

Conventional ways of producing new plants which have modified properties in comparison to previously occurring plants are, for example, classic breeding methods and the generation of mutants. Alternatively, new plants with modified properties can be produced using genetic engineering methods (see, for example, EP-A-0221044, EP-A-0131624). For example, several cases have been described

• - genetic engineering of crops for the purpose of modifying the starch synthesized in the plants (e.g. WO 92/11376, WO 92/14827, WO 91/19806),
• - Transgenic crop plants which are active against certain herbicides of the type Glufosinate (see e.g. EP-A-0242236, EP-A-242246) or glyphosate (WO 92/00377) or the sulfonylureas (EP-A-0257993, US-A-5013659)  are resistant,
• - Transgenic crops, for example cotton, with the ability Bacillus thuringiensis toxins (Bt toxins) which the Making plants resistant to certain pests (EP-A-0142924, EP-A-0193259).
• - Transgenic crop plants with a modified fatty acid composition (WO 91113972).

Numerous molecular biological techniques that new transgenic plants use modified properties can be produced are known in principle; see e.g. B. Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed. Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker "Genes and Clones", VCH Weinheim 2nd edition 1996 or Christou, "Trends in Plant Science "1 (1996) 423-431.

For such genetic engineering manipulations, nucleic acid molecules in Plasmids are introduced that have a mutagenesis or a sequence change allow by recombination of DNA sequences. With the help of the above Standard procedures can e.g. B. base changes made, partial sequences removed or natural or synthetic sequences added. For the Connection of the DNA fragments to one another can be made to the fragments adapters or linker.

The production of plant cells with a reduced activity of one The gene product can be achieved, for example, by expression at least a corresponding antisense-RNA, a sense-RNA to achieve a Cosuppression effect or the expression of at least one accordingly constructed ribozyme that specifically transcripts the above Gene product splits.

On the one hand, DNA molecules can be used that cover the entire coding sequence of a gene product including any that are present  flanking sequences include, as well as DNA molecules that are only parts of the encoding sequence, these parts must be long enough to be in to cause the cells an antisense effect. It is also possible to use DNA sequences that have a high degree of homology to the coding Have sequences of a gene product, but are not completely identical.

In the expression of nucleic acid molecules in plants, the synthesized Protein can be located in any compartment of the plant cell. Around but to reach the localization in a certain compartment can e.g. B. the coding region can be linked to DNA sequences that localize in guarantee a certain compartment. Such sequences are Known to those skilled in the art (see for example Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85: 846-850 (1988); Sun forest et al., Plant J. 1: 95-106 (1991).

The transgenic plant cells can be whole according to known techniques Plants are regenerated. In principle, the transgenic plants can are plants of any plant species, d. H. both monocotyledon also dicotyledonous plants.

In this way, transgenic plants can be obtained that have changed properties Overexpression, suppression or inhibition of homologous (= natural) genes or Gene sequences or expression of heterologous (= foreign) genes or gene sequences exhibit.

The compounds and formulations according to the invention can preferably be used in transgenic crops are used which are active against herbicides from the group of Sulfonylureas, glufosinate-ammonium or glyphosate-isopropylammonium and analog active substances are resistant.

When using the active compounds according to the invention in transgenic cultures in addition to the effects observed in other cultures  Harmful plants often have effects on the application in the respective transgenic culture are specific, for example a modified or special expanded weed spectrum that can be controlled has changed Application rates that can be used for the application, preferably good combinability with the herbicides against which the transgenic culture is resistant, as well as influencing the growth and yield of the transgenic Crops.

The invention therefore also relates to the use of Formulations according to the invention as well as those of the invention Compounds of the formulas (Ia) and (Ib) as herbicides or as Plant growth regulators.

The EC formulations according to the invention have the advantage that they are in the general are very user-friendly and inexpensive to manufacture. In addition In principle, this type of formulation offers the possibility of a simple and inexpensive way to produce combination preparations. The prerequisite is that the combination partner in the chosen organic solvent system in the desired concentration dissolves and is chemically inert.

The formulations according to the invention, in particular the EC formulations are characterized by high chemical stability. In addition, the Formulations according to the invention, in particular the EC formulations, in addition to the chemical stability also a "higher load" (higher concentration) the Have formulation of active ingredient salts. They can also be Formulations according to the invention equally as a liquid formulation (e.g. EC wording) or as a fixed wording (e.g. WP or WG wording) produce.  

Examples example 1

The compound mentioned as Example 1 in Table 1 is obtained by Implementation of Amidosulfuron® with one equivalent Tetramethylammonium hydroxide (pure substance or aqueous or alcoholic Solution) z. B. in methylene chloride or in a mixture of methylene chloride and Methanol. For this, Amidosulfuron® (10 g) is added to the solvent (200 ml Methylene chloride, 50 ml of methanol) finely suspended and with stirring with a Equivalent to an aqueous solution of tetramethylammonium hydroxide Room temperature offset. When the reaction has ended, the mixture is sharply concentrated and the residue was freed from solvent amounts by standard methods.

Example 2

There are 5.0 wt .-% sulfonylurea salt, namely the sulfonylurea salt, which is described in Table 4 Example 3, in 20.0 wt .-% propylene carbonate and 40.0 wt .-% of an aromatic mixture (boiling range 219-282 ° C) dissolved with stirring at 20-30 ° C. After the sulfonylurea salt is completely dissolved, 10.0% by weight of calcium salt of dodecylbenzenesulfonic acid, 10.0% by weight of a (C ₁₂ -C ₁₈ ) fatty acid polycycloester 40 EO (®Emulsogen EL 400, Clariant GmbH) and 15 are added , 0 wt .-% of a fatty alcohol polyglycol ether with stirring to the solution. An emulsifiable concentrate (EC) is obtained which is clear, transparent and thin.

Example 3

There are 6.0 wt .-% sulfonylurea salt, namely the sulfonylurea salt, which is described in Table 5, Example 3, in 20.0 wt .-% propylene carbonate and 40.0 wt .-% of an aromatic mixture (boiling range 219-282 ° C) dissolved at 20-30 ° C with stirring. After the sulfonylurea salt is completely dissolved, 7.0 wt .-% calcium salt gives the Dodecylbenzolsulfonsäur 01185 00070 552 001000280000000200012000285910107400040 0002019963395 00004 01066e, 10.0 wt .-% of a (C ₁₂ -C ₁₈₎ -Fettsäurepolyglycolesters 40 EO (EL ®Emulsogen 400, Clariant GmbH) and 17.0% by weight of a fatty alcohol polyglycol ether with stirring to the solution. An emulsifiable concentrate (EC) is obtained which is clear, transparent and thin.

Formulation examples

The formulations mentioned in Table 6 are obtained by using the Solvent Dowanol PM submitted at room temperature and in succession mechanical stirring the sulfonylurea component and the specified Additive additives.

The examples from Table 6 show that, using special sulfonylurea ammonium salts, in contrast to the corresponding neutral sulfonylureas or their salts, stable EC formulations with an economically attractive loading of active ingredient (s) can be prepared.

Claims (16)

1. Containing formulation
a) at least one sulfonylurea salt of the formula (Ia)
wherein
R ^{a is} a grouping of the formula II-IVc,
R ¹ H or a C ₁ -C ₁₀ hydrocarbon radical such as (C ₁ -C ₆ ) alkyl,
R ^{2 is} a substituted or unsubstituted C ₁ -C ₂₀ -hydrocarbon radical such as substituted or unsubstituted (C ₁ -C ₆ ) alkyl, substituted or unsubstituted (C ₂ -C ₆ ) alkenyl, substituted or unsubstituted (C ₂ -C ₆ ) Alkynyl, substituted or unsubstituted (C ₃ -C ₇ ) cycloalkyl,
R ^{3 is} a substituted or unsubstituted C ₁ -C ₂₀ hydrocarbon radical such as substituted or unsubstituted (C ₁ -C ₆ ) alkyl, substituted or unsubstituted (C ₂ -C ₆ ) alkenyl, substituted or unsubstituted (C ₂ -C ₆ ) Alkynyl, substituted or unsubstituted (C ₃ -C ₇ ) cycloalkyl,
R ⁴ halogen such as F, Cl, Br, J or a substituted or unsubstituted C ₁ -C ₂₀ hydrocarbon radical or C ₁ -C ₂₀ hydrocarbonoxy radical such as (C ₁ -C ₆ ) alkyl, (C ₂ -C ₆ ) - Alkenyl, (C ₂ -C ₆ ) alkynyl, (C ₁ -C ₆ ) alkoxy, (C ₃ -C ₆ ) alkenyloxy, (C ₃ -C ₆ ) alkynyloxy, the latter 6 radicals being substituted by one or several radicals, preferably from the group halogen, such as F, Cl, Br or I or (C ₁ -C ₃ ) alkoxy, can be substituted,
R ⁵ H, halogen such as F, Cl, Br, J or a substituted or unsubstituted C ₁ -C ₂₀ -hydrocarbon radical or C ₁ -C ₂₀ -hydrocarbonoxy radical such as (C ₁ -C ₆ ) - alkyl, which is substituted by one or more radicals from the group halogen such as F, Cl, Br or J or (C ₁ -C ₃ ) alkoxy or (C ₁ -C ₅ ) alkoxy which can be substituted by one or more radicals from the group halogen (F, Cl , Br, I) or (C ₁ -C ₃ ) alkoxy may be substituted
R ⁶ and R ^{6 ',} identical or different, are H or a substituted or unsubstituted C ₁ -C ₂₀ -hydrocarbon radical such as C ₁ -C ₆ -alkyl (e.g. Me, Et, ⁿ Pr, ⁱ Pr, ^c Pr), where R ⁶ and R ^{6 '} can form a ring which is unsubstituted or substituted,
R ⁷ H, halogen such as F, Cl, Br or J, OH, NR ^X R ^Y , where R ^X and R ^{Y are} H or (C ₁ -C ₃ ) alkyl, or R ⁷ N- (C ₁ -C ₃ ) -alkyl-N-acylamino, N-acylamino, or a substituted or unsubstituted C ₁ -C ₂₀ -hydrocarbon radical or hydrocarbonoxy radical such as (C ₁ -C ₃ ) -alkyl, (C ₁ -C ₃ ) -haloalkyl, halogen, (C ₁ -C ₃ ) alkyl- (N- (C ₁ -C ₃ ) alkyl-N-acylamino), (C ₁ -C ₃ ) alkyl- (N-acylamino) or (C ₁ -C ₃ ) Alkyl,
R ^{6 ″ is} a substituted or unsubstituted C ₁ -C ₂₀ -hydrocarbonoxy radical such as substituted or unsubstituted (C ₁ -C ₆ ) -alkyl, substituted or unsubstituted (C ₃ -C ₆ ) -alkenyloxycarbony, substituted or unsubstituted (C ₃ -C ₆ ) -cycloalkyl, substituted or unsubstituted (C ₃ -C ₇ ) -alkynyl, substituted or unsubstituted (C ₄ -C ₈ ) -cycloalkylalkyl,
R ^{7 '} halogen such as F, Cl, Br or J, OH, NR ^X R ^Y , where R ^X and R ^{Y are} H or (C ₁ -C ₃ ) alkyl, or R ^7' N- (C ₁ -C ₃ ) -alkyl-N-acylamino or a substituted or unsubstituted C ₁ -C ₂₀ -hydrocarbon radical or C ₁ -C ₂₀ -hydrocarbon oxy radical such as (C ₁ -C ₃ ) -alkyl, (C ₁ -C ₃ ) -haloalkyl, (C ₁ -C ₃ ) alkyl- (N- (C ₁ -C ₃ ) alkyl-N-acylamino), (C ₁ -C ₃ ) alkyl- (N-acylamino) or (C ₁ -C ₃ ) Alkyl, is
R ^{6 '''} halogen such as F, Cl, Br or J or a substituted or unsubstituted C ₁ -C ₂₀ carbon-containing radical such as (C ₁ -C ₆ ) alkyl, which is substituted by one or more radicals from the group halogen (F , Cl, Br, I) or (C ₁ -C ₃ ) alkoxy can be substituted, (C ₁ -C ₆ ) alkoxy, which is substituted by one or more radicals from the group halogen (F, Cl, Br, J) or (C ₁ -C ₃ ) alkoxy may be substituted, substituted or unsubstituted alkoxycarbonyl, (C ₁ -C ₆ ) mono- or dialkylamino, N- (C ₁ -C ₆ ) alkyl-N-acylamino or N- Acylamino, is,
R ^{7 ″} halogen such as F, Cl, Br or J, OH, NR ^X R ^Y , where R ^X and R ^{Y are} H or (C ₁ -C ₃ ) alkyl, or R ^{7 ″ is} a substituted or unsubstituted C ₁ -C ₂₀ hydrocarbon radical or hydrocarbonoxy radical such as (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) haloalkyl, (C ₁ -C ₆ ) alkoxy or (C ₁ -C ₆ ) haloalkoxy,
M ^{+ is} a primary, secondary, tertiary or quaternary, preferably a quaternary ammonium ion,
X substituted or unsubstituted (C ₁ -C ₆ ) alkyl, substituted or unsubstituted (C ₁ -C ₆ ) alkoxyl, halogen such as F, Cl, Br or J, substituted or unsubstituted (C ₁ -C ₆ ) mercapto is alkyl or (C ₁ -C ₃ ) mono- or (C ₁ -C ₃ ) dialkylamino,
Y substituted or unsubstituted (C ₁ -C ₆ ) alkyl, substituted or unsubstituted (C ₁ -C ₆ ) alkoxyl, halogen such as F, Cl, Br or J, substituted or unsubstituted (C ₁ -C ₆ ) mercapto- is alkyl or (C ₁ -C ₃ ) mono- or (C ₁ -C ₃ ) dialkylamino, and
Z is C-halogen such as CF, CCl, CBr or CJ, CH, or N and
b) usual auxiliaries and additives. 2. Formulation according to claim 1, comprising one or more of the in Claim 1 defined sulfonylurea salt various agrochemicals such as Herbicides, fungicides, insecticides, growth regulators, safeners, fertilizers. 3. Formulation according to claim 1 to 2, containing a wetting agent, the has bioactivating properties or a mixture of different Wetting agents that have bioactivating properties. 4. Formulation according to one or more of claims 1 to 3, containing a pH-stabilizing substance or mixture of substances. 5. Formulation according to one or more of claims 1 to 4, containing a substance or mixture of substances with defoaming properties.   6. Formulation according to one or more of claims 1 to 5, containing a substance or mixture of substances that acts as an acid scavenger. 7. Formulation according to one or more of claims 1 to 6, containing a substance or mixture of substances that acts as a water scavenger. 8. Formulation according to one or more of claims 1 to 7, containing a substance or mixture of substances that acts as an inhibitor of crystallization. 9. Formulation according to one or more of claims 1 to 8, containing a surfactant or surfactant mixture. 10. Formulation according to one or more of claims 1 to 9, containing generally 0.1-70.0% by weight, preferably 0.1-50.0% by weight, one or several ammonium salts of sulfonylureas, generally 5.0-95.0% by weight of a polar and / or hydrophobic solvent, generally 2.0-40.0% by weight a mixture of anionic and nonionic surfactants or one Mixture of cationic and non-ionic surfactants. 11. Use of the formulation according to one or more of claims 1 to 10 as a herbicidal or plant growth regulating agent. 12. A compound of formula (Ia) as defined in claim 1. 13. A compound of formula (Ia) according to claim 12, wherein
R ¹ H or Me,
R ² (C ₁ -C ₃ ) alkyl or (C ₁ -C ₃ ) haloalkyl, in particular Me and Et,
R ³ (C ₁ -C ₃ ) alkyl or (C ₁ -C ₃ ) haloalkyl, in particular Me and Et,
R ⁴ (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) haloalkyl or (C ₁ -C ₆ ) alkoxy, in particular Me, Et, OMe, OEt or CF ₃ ,
R ⁵ H, halogen such as F, Cl, Br or J, OMe, OEt, Me, CF ₃ , where the radicals R ⁵ in formula (III) other than hydrogen are preferably in the 5-position on the phenyl ring,
R ⁶ and R ^{6 'are the} same or different C ₁ -C ₆ alkyl, preferably R ⁶ = Me, Et R ^6' = Me; R ⁶ = Me, R ^{6 '} = Et and R ^6' = Et, R ⁶ = Et.
R ⁷ H, Me, Et, CF ₃ , F, Cl, Br, J, N [(C ₁ -C ₃ ) alkyl] -R ⁸ , NH-R ⁹ , CH ₂ N [(C ₁ -C ₃ ) -Alkyl] -R ¹⁰ , CH ₂ NH-R ¹¹ , CH ₂ CH ₂ N [(C ₁ -C ₃ ) -alkyl] -R ¹² , CH ₂ CH ₂ NH-R ¹³ , the radicals other than hydrogen R ^{7 '} in formula (IVa) are preferably in the 5-position on the phenyl ring, and the radicals R ⁸ to R ^{13 are} H, (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) haloalkyl, CHO, COO (C ₁ -C ₆ ) alkyl, COO (C ₁ -C ₆ ) haloalkyl, SO ₂ - (C ₁ -C ₆ ) alkyl, SO ₂ - (C ₁ -C ₆ ) haloalkyl, CO- Is (C ₁ -C ₆ ) alkyl or CO- (C ₁ -C ₆ ) haloalkyl,
R ^{6 ''} Me, Et, ⁿ Pr, ⁱ Pr, ^c Pr, ⁿ Bu, ⁱ Bu, ^s Bu, ^t Bu, ^c Bu, especially Me or Et
R ^{7 '} Me, Et, CF ₃ , F, Cl, Br, I, N [(C ₁ -C ₃ ) alkyl] -R ⁸ , NH- (C ₁ -C ₃ ) alkyl, CH ₂ N [ (C ₁ -C ₃ ) alkyl] -R ¹⁰ , CH ₂ NH-R ¹¹ , CH ₂ CH ₂ N [(C ₁ -C ₃ ) alkyl] -R ¹² , CH ₂ CH ₂ NH-R ¹³ , where the radicals R ^{7 '} in formula (IVb) other than hydrogen are preferably in the 5-position on the phenyl ring, and the radicals R ⁸ and R ¹⁰ to R ¹³ H, (C ₁ -C ₆ ) -alkyl, (C ₁ -C ₆ ) - haloalkyl, CHO, COO (C ₁ -C ₆ ) alkyl, COO (C ₁ -C ₆ ) haloalkyl, SO ₂ - (C ₁ -C ₆ ) alkyl, SO ₂ - (C ₁ -C ₆ ) -haloalkyl, CO- (C ₁ -C ₆ ) -alkyl or CO- (C ₁ -C ₆ ) -haloalkyl,
R ^{6 '''} Me, Et, Pr, CH ₂ CH ₂ CF ₃ , OMe, OEt, O ⁱ Pr, OCH ₂ CH ₂ Cl, F, Cl, COOMe, COOEt, COO ⁿ Pr, COO ⁱ Pr, unsubstituted or substituted NH- (C ₁ -C ₆ ) alkyl acyl, unsubstituted or substituted NH- (C ₃ -C ₇ ) cycloalkyl, unsubstituted or substituted (C ₄ -C ₈ ) cycloalkylalkyl, unsubstituted or substituted N- (C ₃ -C ₇ ) - Cycloalkyl-aryl, unsubstituted or substituted N- (C ₄ -C ₈ ) -cycloalkylalkyl-acyl, preferably
N- (C ₁ -C ₆ ) -alkyl-CHO, N- (C ₁ -C ₆ ) -alkyl-CO-R, N- (C ₁ -C ₆ ) -alkyl-SO ₂ R, NH-CHO, NH-CO-R, NHSO ₂ R, where the radicals R (C ₁ -C ₆ ) - (halo) alkyl, (C ₁ -C ₆ ) - (halo) alkoxy, (C ₁ -C ₃ ) - Alkoxy- (C ₁ -C ₆ ) -alkyl, (C ₁ -C ₃ ) -alkoxy- (C ₁ -C ₆ ) -alkoxy or mono- and di- (C ₁ -C ₆ ) -alkylamino,
R ^{7 ''} F, Cl, Me, Et, CF ₃ , OCH ₃ , OEt, OCH ₂ CF ₃ ,
M ⁺ [NR ¹⁴ R ¹⁵ R ¹⁶ R ¹⁷ ] ⁺ , or a quaternized pyridinium ion [Py-R ²⁵ ] ⁺ , where R ¹⁴ to R ^{16 are} identical or different H or substituted or unsubstituted (C ₁ -C ₃₀ ) alkyl , substituted or unsubstituted (C ₁ -C ₁₀ ) alkyl- (hetero) aryl, substituted or unsubstituted (C ₃ -C ₃₀ ) - (oligo) alkenyl, substituted or unsubstituted (C ₃ -C ₁₀ ) - (oligo ) Alkenyl (hetero) aryl, substituted or unsubstituted (C ₃ -C ₃₀ ) - (oligo) alkynyl, substituted or unsubstituted (C ₃ -C ₁₀ ) - (oligo) alkynyl (hetero) aryl, are substituted or unsubstituted (hetero) aryl and
R ¹⁷ and R ²⁵ substituted or unsubstituted (C ₁ -C ₃₀ ) alkyl, substituted or unsubstituted (C ₁ -C ₁₀ ) alkyl (hetero) aryl, substituted or unsubstituted (C ₃ -C ₃₀ ) - (oligo ) Alkenyl, substituted or unsubstituted (C ₃ -C ₁₀ ) - (oligo) alkenyl (hetero) aryl, substituted or unsubstituted (C ₃ -C ₃₀ ) - (oligo) alkynyl, substituted or unsubstituted (C ₃ -C ₁₀ ) - (Oligo) -alkynyl- (hetero) aryl, substituted or unsubstituted (hetero) aryl and where two radicals R ¹⁴ / R ¹⁵ and R ¹⁶ / R ¹⁷ together can form an unsubstituted or substituted ring,
X Me, Et, Pr, ⁱ Pr, CF ₃ , CCl ₃ , OMe, OEt, O ⁱ Pr, OCHCl ₂ , OCH ₂ CCl ₃ , OCH ₂ CF ₃ , F, Cl, Br, SMe, SEt, NHMe, NMe ₂ , NHEt, preferably OMe, OEt, Me, Cl
Y Me, Et, Pr, ⁱ Pr, CF ₃ , CCl ₃ , OMe, OEt, O ⁱ Pr, OCHCl ₂ , OCH ₂ CCl ₃ , OCH ₂ CF ₃ , F, Cl, Br, SMe, SEt, NHMe, NMe ₂ , NHEt, preferably OMe, OEt, Me, Cl and
Z CH and N
mean. 14. Use of one or more compounds of the formula (Ia) according to Claim 12 or 13 as herbicidal or plant growth regulating agent. 15. A process for the preparation of a compound of formula (Ia) according to claim 12 or 13. 16. Use of a compound of the formula (XVIII) and / or (XIX)
wherein
W, X, Y and Z are independently an integer 0 to 50,
R is a C ₈ -C ₄₀ alkyl radical,
R ', R "and R""are independently of one another C ₁ -C ₁₀₀ alkyl radicals,
EO is an ethoxy unit,
PO is a propoxy unit, and
M ^{⊕ is} an ammonium ion or a metal cation,
for the production of an agrochemical formulation.