CA2144769A1 - Hydroxylaminophenylsulfonylureas, their synthesis, and their use as herbicides and plant growth regulators - Google Patents

Abstract

Hydroxylaminophenylsulfonylureas, their synthesis, and their use as herbicides and plant growth regulators The sulfonylureas of the formula (I) and the salts thereof (I) are suitable as selective herbicides for controlling noxious plants in crops of useful plants. The inter-mediates of the formulae (II) and (IV) (II)

Description

-- ~ILE. P~N ~H~S 4~ r~r~ 1 4 ~7 6 ~ T T~ANSLA~

Description ~ydroxylaminophenylsulfonylureas, their synthesis, and their use as herbicides and plant growth regulators The invention relates to the technical field of herbicides and plant growth regulators, in particular the herbicides for selectively controlling broad-leaved weeds and grass weeds in crops of useful plants.

It has been disclosed that heterocyclically substituted phenylsulfonylureas which have an amino or a functional-ized amino group on the phenyl ring have herbicidal and plant-growth-regulating properties (US-A-4,892,946;
US-A-4,981,509; EP-A-169,815).

Furthermore, WO-89/10921 discloses phenylsulfonylurea herbicides in which the phenyl ring is 2,4-disubstituted or 2,4,6-trisubstituted and can have, inter alia, an alkylamino or (substituted) hydroxylamino group in the 4-position.

Surprisingly, it has now been found that certain hetero-cyclically substituted phenylsulfonylureas which have an unsubstituted or a substituted hydroxyl~;no function are particularly suitable as herbicides or plant growth regulators.

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

- 2 - ~1447 N(0R2)Rl W R4 ~ S02- N~ - C - N ~ ( ~ (I) in which Rl is Co-R5, CO-OR6, CO-NR'R8, CS-R9, CS-OR', CS-NR'R8, SO2Rll, SOR", So2NR7R8 or CO-COR'2, R2 is hydrogen, C,-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl, the last-mentioned 3 radicals independently of one another being unsubstituted or substituted by one or more radicals selected from the group com-prising halogen, C,-C4-alkoxy and C,-C4-alkylthio, R3 is halogen, C,-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C,-C6-alkoxy, C2-C6-alkenyloxy or C2-C6-alkynyloxy, the last-mentioned 6 radicals independently of one another being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, C,-C4-alkoxy and alkylthio, or is CO-CO-R'6, CS-R'6, CO-CO-OR", CS-OR'7, CS-SR'7, CO-NR'8R'9, CS-NRl8Rl9, NR'8R'9, SO2NR'8R'9, cyano, S(O)o~R20, CO-R'6, CO-OR", NO2 or C(R21)=N-R22 or a 5- or 6-membered saturated, unsaturated or hetero-aromatic heterocycle having up to 4 hetero atoms selected from the group comprising N, O and S, which is unsubstituted or substituted by one or more radicals selected from the group comprising halogen, C,-C4-alkyl, C,-C4-alkoxy, C1-C4-alkylthio, C,-C4-haloalkyl, CN, NO2, C~O, (C,-C4-alkyl)-carbonyl and (C,-C4-alkoxy)-carbonyl and in which up to 2 carbon ring positions can be replaced by CO and up to two sulfur atoms in the hetero ring can be replaced by _ 3 _ 2~ ~ ~769 so2l R4 is hydrogen or C,-C,-alkyl, R5 is hydrogen or C,-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl, the last-mentioned 3 radicals being unsub-stituted or substituted by one or more radicals selected from the group comprising halogen, Cl-C4-alkoxy, C,-C4-alkylthio, NR13R'4 and NR'52, or is C3-C,-cycloalkyl which is unsubstituted or substituted by one or more radicals selected from the group com-prising halogen, C,-C4-alkyl, C,-C4-alkoxy, C,-C4-alkylthio, NR'3R'4 and NR'52, or is benzyl, unsubstituted or substituted aryl or an unsubstituted or substituted heterocyclic radical, R6 is C,-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl, the last-mentioned 3 radicals being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, C,-C4-alkoxy, C,-C4-alkylthio, NR'3Rl4 and NR'52, R' is hydrogen or C,-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl or C,-C6-alkoxy, the last-mentioned 4 radi-cals being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, C,-C4-alkoxy, Cl-C4-alkylthio and NR'3R'4, R8 is hydrogen or C,-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl, the last-mentioned 3 radicals being unsub-stituted or substituted by one or more rA~;cAls selected from the group comprising halogen, Cl-C4-alkoxy and C1-C4-alkylthio, or is CoR23, Co2R24, CoNR'3R'4 or SO2R'l, 0 R9 is analogous to R5, preferably hydrogen, C,-C6-alkyl or C3-C6-alkenyl, the last-mentioned 2 radicals being unsubstituted or substituted by one or more halogen atoms or by one or two radicals selected from the _ 4 _ 2 1 4 4~ 6~
group comprising C,-C4-alkoxy, alkylthio and NRl3R~4, Rl is analogous to ~6, preferably C,-C6-alkyl or C3-C6-alkenyl, the last-mentioned 2 radicals being unsub-stituted or substituted by one or more halogen atoms or by one or two radicals selected from the group comprising Cl-C4-alkoxy and Cl-C4-alkylthio, Rll is Cl-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl, the last-mentioned 3 radicals being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, Cl-C4-alkoxy and Cl-C4-- alkylthio, Rl2 is hydrogen, OH, NH2, mono- or di(C,-C4-alkyl)amino, C,-C4-alkyl or Cl-C4-alkoxy, the last-mentioned 2 radicals being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, Cl-C4-alkoxy and Cl-C4-alkylthio, the Rl3 radicals independently of one another are hydrogen or Cl-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl, the last-mentioned 3 radicals being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, Cl-C4-alkoxy and Cl-C4-alkylthio, or are COR2s or CO2R26, the Rl4 radicals independently of one another are hydrogen or Cl-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl, the last-mentioned 3 radicals being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, Cl-C4-alkoxy and Cl-C4-alkylthio, NRls2 radicals independently of one another are a hetero-cyclic 3- to 7-membered ring which can contain, besides the nitrogen atom, one or two further hetero ring atoms selected from the group comprising N, O
and S and which is unsubstituted or substituted, 2i~7~3 Rl6 is a rA~;c~l analogous to R5, Rl' is hydrogen, Cl-C6-alkyl, C2-C6-alkyl or C2-C6-alkynyl, the last-mentioned 3 radicals being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, Cl-C4-alkoxy, Cl-C4-alkylthio, NRl3Rl4 and NRl52, Rl8 is a radical analogous to R', Rl9 is a radical analogous to R8, R2C is a radical analogous to Rll, R2l is hydrogen or Cl-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl, the last-mentioned 3 rA~irAls being unsub-stituted or substituted by one-or more radicals selected from the group comprising halogen, Cl-C4-alkoxy and Cl-C4-alkylthio, or is C,-C4-alkoxy, O~, N~2, mono- or di(Cl-C4-alkyl)amino, CO-Rl6, CO2-Rl' or SO2 -R20, R22 is hydrogen, OH, N~2, mono- or di(Cl-C4-alkyl)amino, Cl-C4-alkyl or Cl-C4-alkoxy, the last-mentioned 2 radicals being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, Cl-C4-alkoxy and C,-C4-alkylthio, R23 is a radical analogous to R9, R24 is a radical analogous to Rl, R2s is a radical analogous to R9, .

R26 is a radical analogous to Rl, X and Y independently o~ one another are hydrogen, halogen, Cl-C6-alkyl, Cl-C6-alkoxy or Cl-C6-alkylthio, the last-mentioned 3 radicals being unsubstituted or - 21~76~

substituted by one or more radicals selected from the group comprising halogen, Cl-C4-alkoxy and C1-C4-alkylthio, or are mono- or di ( C,-C4-alkyl ) amino, C3-C6-cyClOalkyl, C3-c5-alkenyl ~ C3-C6-alkynyl ~ C3-C5-alkenyloxy or C3-C5-alkynyloxy, Z is CH or N, W is O or S, n is 0, l, 2 or 3 and o is 0, l, 2 or 3.

lO In formula (I) and hereinafter, the radicals alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio and the corresponding unsaturated and/or substituted radicals can in each case be straight-chain or branched in the carbon skeleton. Unless specifically indicated, 15 preferred among these radicals are carbon skeletons having l to 4 carbon atoms or, in the case of unsaturated groups, 2 to 4 carbon atoms. Alkyl radicals, also in composite lneA~; ngs, such as alkoxy, haloalkyl and the like, are, f or example, methyl, ethyl, n- or i-propyl, 20 n-, i-, t- or 2-butyl, pentyl radicals, hexyl radicals, such as n-hexyl, i-hexyl and l, 3-dimethylbutyl, heptyl radicals, such as n-heptyl, l-methylhexyl and l, 4-di-methylpentyl; alkenyl and alkynyl radicals have the meaning of the unsaturated radicals which are possible, 25 corresponding to the alkyl radicals; alkenyl is, for example, allyl, l-methylprop-2-en- l-yl, 2 -methyl-prop-2 -en-l-yl, but-2-en-l-yl, but-3-en-l-yl, l-methyl-but-3-en-l-yl and l-methyl-but-2-en-l-yl; alkynyl is, for example, propargyl, but-2 -yn- l-yl, but- 3 -yn- l -yl,

3 0 l-methyl-but- 3 -yn- l -yl .

Halogen is f luorine, chlorine, bromine or iodine . Halo-alkyl, haloalkenyl and haloalkynyl are alkyl, alkenyl or alkynyl, each of which is partially or fully substituted - 7 - 2~4 f~7 ~
by halogen, preferably by fluorine, chlorine and/or bromine, in particular by fluorine or chlorine, for example CF3, C~F2, C~2F, CF3CF2, CH2FCHCl, CCl3, CHCl2, C~2C~2Cl; halo~lkoYy is, for example, OCF3, OCHF2, OCH2F, CF3CF20, OC~2CF3 and OC~2C~2Cl. The same applies analogously for haloalkenyl and other halogen-substituted radicals.

Aryl is a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl, fluorenyl and the like, preferably phenyl; aryloxy is preferably the oxy radicals which correspond to the abovementioned aryl radicals, in particular phenoxy.

Heteroaryl or a heteroaromatic radical is a mono-, bi- or polycyclic aromatic system in which at least 1 ring has one or more hetero atoms, for example pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, thienyl, thiazolyl, oxazolyl, furyl, pyrrolyl, pyrazolyl and imidazolyl, but also bicyclic or polycyclic aromatic or araliphatic compounds, for example quinolinyl, benzoxazolyl and the like.

Substituted aryl, heteroaryl, phenyl, benzyl, or substi-tuted bicyclic radicals having aromatic moieties are, for example, a substituted radical derived from an unsubsti-tuted basic structure, the substituents being, forexample, one or more, preferably 1, 2 or 3, radicals selected from the group comprising halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, hydroxyl, amino, nitro, cyano, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, mono-and dialkyl~;no, alkylsulfinyl and alkylsulfonyl,~lhere, in the case of radicals which have carbon atoms, those having 1 to 4 carbon atoms, in particular 1 or 2 carbon . . .
atoms, are preferred. As a~rule, preferred substituents are those selected from the group comprising halogen, for example fluorine and chlorine, C1-C4-alkyl, preferably 8 21~69 methyl or ethyl, Cl-C4-haloalkyl, preferably trifluoro-methyl, Cl-C4-alkoxy, preferably methoxy or ethoxy, Cl-C4-halo~lko~y, nitro and cyano. Particularly preferred are the substituents methyl, methoxy and chlorine.

Optionally substituted phenyl is, for example, phenyl which is unsubstituted or monosubstituted or polysubstituted, preferably up to trisubstituted, by identical or different radicals selected from the group comprising halogen, C~-C4-alkyl, Cl-C4-alkoxy, Cl-C4-halo-alkyl, Cl-C4-haloalkoxy and nitro, for example o-, m- and p-tolyl, dimethylphenyl radicals, 2-, 3- and 4-chloro-phenyl, 2-, 3- and 4-trifluoromethyl- and -trichlorometh-ylphenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl and o-, m- and p-methoxyphenyl.

A heterocyclic radical is preferably 5- or 6-membered and heteroaromatic, saturated or unsaturated and contains 1, 2 or 3 hetero atoms, preferably selected from the group comprising N, O and S. The radical can be benzo-fused.
Radicals such as oxiranyl, pyrrolidyl, dioxolanyl, pyrazolyl, morpholyl, furyl, tetrahydrofuryl, indolyl, quinolinyl, pyrimidyl, azepinyl, imidazolyl, triazolyl, thienyl and oxazolyl are suitable.

The invention also relates to all stereoisomers which are embraced by the formula (I) and to mixtures of these.
Such compounds of the formula (I) contain one or more asymmetric carbon atoms or else double bonds which are not indicated separately in the formulae (I). Formula (I) embraces all the possible stereoisomers which are defined by their specific spatial shape, such as enantiomers, diastereomers and Z- and E-isomers, and these can be obtained from the stereoisomer mixtures by conventional methods or else by stereoselective reactions in combina-tion with the use of stereoch~ lly pure starting .
- materials.

The compounds of the formula (I) can form salts in which 2~4~7fi~
_ 9 _ the hydrogen of the -SO2-N~- group or else other acidic hydrogen atoms (for example from, inter alia, COOH) is replaced by an agriculturally suitable cation. Examples of these salts are metal salts, in particular alkali metal salts (for example sodium or potassium salts) or alkaline earth salts, or else ammonium salts or salts with organic ~m; nes. Salt formation can also be effected by an addition reaction of an acid with basic groups, for example amino and alkyl~;no. Acids which are suitable for this purpose are strong inorganic and organic acids, for example HCl, HBr, ~2SO4 or HNO3.

Compounds of the formula (I) or salts thereof which are of particular interest, mainly because they have a better herbicidal activity and selectivity and/or can be pre-pared more readily are those in which Rl is Co-R5, CO-OR6, CO-NR'R8, CS-R9, CS-NR'R8, SO2Rll, So2NR7R~ or CO-COR~2 or R2 is hydrogen, Cl-C6-alkyl, C3-Cs-alkenyl or C3-Cs-alkynyl, the last-mentioned 3 radicals independently of one another being unsubstituted or substituted by one or more halogen atoms or by one or two radicals selected from the group comprising Cl-C4-alkoxy and Cl-C4-alkylthio, or R3 is halogen, Cl-C4-alkyl, C2-Cs-alkenyl, C2-Cs-alkynyl, Cl-C4-alkoxy, C3-Cs-alkenyloxy or C3-Cs-alkynyloxy, the last-mentioned 6 radicals independently of one another being unsubstituted or substituted by one or more halogen atoms or by one or two radicals selected from the group comprising Cl-C4-alkoxy and alkylthio, or is CO-CO-Rl6, CO-CO-ORl', CO-NRl~Rl9, NRl~Rl9, SO2NRl~Rl9, cyano, S(O)o~R20, CO-Rl6, CO-ORl', NO2 or C(R2l)=N_R22 or is a 5- or 6-membered saturated, unsaturated or heteroaromatic heterocycle having up to 3 hetero atoms selected from the group comprising N, O and S, which is unsubstituted or substituted by one or more - 10 - 2 t IL ~17 6 ~1 radicals selected from the group comprising halogen, Cl-C4-alkyl, such as methyl, Cl-C4-alkoxy, such as methoxy, Cl-C4-alkylthio, Cl-C4-haloalkyl, such as CF3, CN, NO2, C~O, (Cl-C4-alkyl)carbonyl, such as acetyl, and (C1-C4-alkoxy)carbonyl, such as CO2C~3, and in which up to 2 carbon ring positions can be replaced by CO and up to two sulfur atoms in the hetero ring can be replaced by SO2, R4 is hydrogen or methyl, R5 is hydrogen or Cl-C6-alkyl which is unsubstituted or substituted by one or more halogen atoms or by one or two radicals selected from the group comprising Cl-C4-alkoxy, Cl-C4-alkylthio, NRl3Rl4 and NRl52, or is C3-C,-cycloalkyl, benzyl, unsubstituted or substituted aryl or unsubstituted or substituted heteroaryl, preferably H, Cl-C6-alkyl, Cl-C6-haloalkyl, C3-C6-cycloalkyl, benzyl, phenyl which is unsubstituted or substituted by one or more, preferably up to 3, radicals selected from the group comprising halogen, methoxy or methyl, or is a 5- or 6-membered heteroaromatic radical which has up to

4 hetero atoms selected from the group comprising N, O and S and which is unsubstituted or substituted by one or more radicals selected from the group comprising halogen, NO2, CN, CHO, COCH3, CO2CH3, OCH3 and SCH3, or R6 is Cl-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl, the last-mentioned 3 radicals being unsubstituted or substituted by one or more halogen atoms or by one or two radicals selected from the group comprising Cl-C4-alkoxy, Cl-C4-alkylthio, NRl3Rl4 and NRls2, pre-ferably Cl-C6-alkyl, Cl-C6-haloalkyl, C3-C6-alkenyl or C3-C6-haloalkenyl, or R' is hydrogen or Cl-C6-alkyl which is unsubstituted or substituted by one or~more halogen atoms or by one or two rA~icAls selected from the group comprising C1-C,-alkoxy, Cl-C4-alkylthio and NRl3Rl4, preferably - 21~76g H, cl-c4-alkyl or Cl-C4-haloalkyl, or Rs is hydrogen or Cl-C4-alkyl which is unsubstituted or substituted by one or more halogen atoms or by one or two radicals selected from the group comprising C1-C4-alkoxy and Cl-C4-alkylthio, or is CoR23, Co2R24-or SO2Rll, preferably H, CH3, C2H5, CHO, COCH3 or CO2CH3, or R9 is analogous to R5, preferably hydrogen, Cl-C6-alkyl or Cl-C6-haloalkyl, orO Rl is analogous to R6, preferably Cl-C4-alkyl or Cl-C4-haloalkyl, or Rll is Cl-C4-alkyl or Cl-C4-haloalkyl, or Rl2 is hydrogen, OH, cl-c4-alkyl, cl-c4-alkoxy or Cl-C4-haloalkyl, preferably ~ or Cl-C4-alkyl, or5 the Rl3 radicals independently of one another are hydrogen or Cl-C4-alkyl, CoR25 or CO2R26, preferably H, C~3, C2E5, CHO, COC~3, CO-OCH3 or CO-OC2~5, the Rl4 radicals independently of one another are hydrogen or Cl-C4-alkyl, preferably H, CH3 or C2H5, NRl52 radicals independently of one another are a hetero-cyclic 3- to 7-membered ring which can contain, besides the nitrogen atom, a further hetero ring atom selected from the group comprising N, O and S
and which is unsubstituted or substituted by one or more radicals selected from the group comprising Cl-C4-alkyl and oxo, for example heterocyclic radi-cals of the formulae Al to A5 o --N3 --N~ _ N~ - N,~

A ~ Az A3 A~

N~ N~ N,~

o O O

A5 A6 A~ 9 or R16 is a radical analogous to R5, Rl' is hydrogen, C,-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, the last-mentioned 3 radicals being unsubstituted or substituted by one or more halogen atoms or by one or two rA~;c~ls selected from the group comprising C,-C4-alkoxy, C,-C,-alkylthio, NR'3R'4 and NR'52, preferably H, C,-C6-alkyl, C,-C6-haloalkyl, C3-C6-alkenyl or C3-C6-haloalkenyl, Rl8 is a radical analogous to R', R15 is a radical analogous to R8, R20 is a radical analogous to R", R2l is hydrogen, C,-C4-alkyl, Cl-C4-haloalkyl,C,-C4-alkoxy, OH, NH2, mono- or di-(C,-C4-alkyl)-amino, preferably H, methyl, ethyl, n- or i-propyl, meth-oxy, ethoxy, hydroxyl, amino, methylamino or dimethylamino, R22 is hydrogen, OH, NH2, mono- or di(C,-C4-alkyl)-amino, Cl-C4-alkyl or Cl-C4-alkoxy, preferably H, OH, NH2, NHCH3, N(CH3) 2 ~ CH3 or OCH3, R23 is a radical analogous to R5, R24 is a radical analogous to R', R25 is a radical analogous to R9, R26 is a radical analogous to Rl, X and Y independently of one another are hydrogen, ~ - 13 - 2~1~7~
halogen, Cl-C4-alkyl, Cl-C4-alkoxy or Cl-C,-alkylthio, the last-mentioned 3 rA~icAls being unsubstituted or substituted by one or more halogen atoms, or are mono- or di(Cl-C2-alkyl)~m; no, one of the radicals X
and Y preferably being CH3, C2Hs, OCH3 or OC2Hs and the other radical preferably being CH3, C2H5, OCH3, OC2H5 ~ Cl ~ CF3 ~ OCF3C ~ OCF2H ~ N ( CH3 ) 2 1 NHCH3 or N(C2Hs)2/ or Z is CH or N, W is O or S, preferably O, n is 0, 1 or 2 or o is 0, 1 or 2, or preferably those compounds of the formula (I) or salts thereof in which two or more of the abovementioned particular or preferred meanings of the general radicals or indices Rl to o in formula (I) are combined.

Preferred compounds of the abovementioned formula (I) or salts thereof are those in which R1 is CoR5, CO2R6, Co-NR7R8, CO-CO-Rl2, CS-NR'R~, SO2R11 or SO2-NR'R8 and/or R2 is hydrogen or C1-C4-alkyl, preferably H~ CH3~ C2H5 or n- or i-C3H7, in particular H.

Other preferred compounds of the formula (I) according to the invention or salts thereof are those in which Rs is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, such as CF3, cyclopropyl, cyclopentyl, cyclohexyl, benzyl, phenyl which is unsubstituted or substituted by 1 to 3 radicals selected from the group comprising halogen, preferably fluorine or chlorine, methyl and methoxy, or is thienyl, furyl or pyridyl, the above heteroaromatic radicals being unsubstituted or substituted by one or more rA~icAls selected from the group comprising halogen, C,-C4-alkyl and Cl-C4-alkoxy, or R6 is Cl-C4-alkyl, C,-C4-haloalkyl, C3-C4-alkenyl or - 14 - ~g ~ 6 C3-C4-alkynyl, R' is H, C1-C4-alkyl or Cl-C4-haloalkyl or R3 is ~, Cl-C4-alkyl, COCH3, CO2C~3 or CO2C2~s~
or which contain a combination of the abovementioned preferred radicals.

- Other preferred compounds are compounds of the formula (I) according to the invention or salts thereof in which the group of the formula N(OR2)Rl is in the 2-, 3-, 5- or 6-position on the phenyl ring and n is 0 or 1.

Particularly preferably, the group of the formula N(OR2)R1 is in the 2-position on the phenyl ring and n is 0 or 1 or the group of the formula N(OR2)Rl is in the 5-position (or 3-position) on the phenyl ring, n is 0 or 1 and the radical R3 is in the 2-position (or 6-position) on the phenyl ring .
Particularly preferably, R3 is a group of the formula CO-ORl' in the 2- or 6-position on the phenyl radical and n is 1.

The present invention furthermore relates to processes for the preparation of the compounds of the formula (I) according to the invention or of the salts thereof, which comprises a) reacting a compound of the formula (II) N(oR2~Rl ~ S2-NH2 ( I I ) (R ) n with a heterocyclic carbamate of the formula (III) 7 ~ 3 International Patent Application No. PCT/EP93/02469 (Our Ref: HOE 92/F300 WO) Annex to the submission of 19.9. 94 I~ _ I

c) reacting a compound of the formula (II) with a (thio)isocyanate of the formula (X) X

W ~ C ~ N ~ (X) in the presence of a base, where in formulae (II) - (V) and (X) the radicals Rl to R4 and n are as defined in formula (I) and in process variants a) and b) compounds of the formula (I) are initially obtained in which W is O.
AMENDED SHEET

~14~76~

The compounds of the formulae (II) and (III) are prefer-ably reacted in an inert organic solvent, such as, for example, dichloromethane, acetonitrile, dioxane or THF, at temperatures between 0C, preferably 20C, and the boiling point of the solvent, with base catalysis.
Examples of bases which are used are organic ~m;ne bases, such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), in particular when R* is (substituted) phenyl (cf.
EP-A-44,807), or trimethylaluminum or triethylaluminum, the latter substances in particular when R* is alkyl (cf.
EP-A-166,516).

Two sulfonamides of the formula (II) are known from Chem.
Abstr. 99:37857e (1983), that is 4-(N-acetyl-N-hydroxy-or -N-methoxy-amino)-benzenesulfon~ide. New compounds (II) and their preparation are also provided by the invention.

The compounds of the formula (II) are obtained, for example, starting from compounds of the formula (VI) N(OR2)R1 (R )n~ (Yl) S02NH- t -C4H9 by reacting them with a strong acid.

AMENDED S~EET

-C2l~7~g presence of a base, such as, for example, potassium carbonate or sodium hydride, in an inert solvent, such as, for example, DMF (dimethylformamide) or DMSO (dimeth-yl sulfoxide), TH~ (tetrahydrofuran) or 1,2-dimethoxyethane. Suitable alkylating agents are dialkyl sulfates or corresponding alkyl halides (cf.
Houben-Weyl-Klamann, "Methoden der organischen Chemie"
[Methods of Organic Chemistry], 4th Ed., Vol. E XVI/a, p. 271, Thieme Verlag Stuttgart, 1990).

The substituent R' can be introduced by reacting the hydroxylamine aromatics (VI) in which R1 = R2 = H with suitable electrophilic substances, such as, for example, acid chlorides, acid anhydrides, isocyanates and thioiso-cyanates (cf. Houben-Weyl-~l A~ nn, "Methoden der organischen Chemie" [Methods of Organic Chemistry], 4th Ed., Vol. E XVIa/1, p. 199 et seq., Thieme Verlag Stuttgart, 1990).

The hydroxylamine derivative of the formula (VI) in which Rl = R2 = H is accessible from the corresponding nitro compound (VII) by reduction, for example using zinc powder in ethanol buffered with ammonium chloride. Other examples of suitable reducing agents for this transforma-tion are: platinum/tributyl phosphite/4-dimethylamino-pyridine, hydrazine hydrate or hydrogen/Raney nickel-/ethanol, hydra~ine hydrate/rhodium, sodium dihydrogenphosphate/palladium, and the like (cf., in this context:
Houben-Weyl-Kl ~nn ~ "Methoden der organischen Chemie"
~Methods of Organic Chemistry], 4th Ed., Vol. E XVIa/l, p. 49 et seq., Thieme Verlag Stuttgart, 1990).

The abovementioned nitro compound of the formula (VII) can be prepared from the corresponding nitrobenzenesul-fonic acid (VIII) 18 2~ 7~

~,~ S03H ~ SO2NH-t-C4H9 (R )n ~R3) ( V I I I ) ( V I I ) First, the sulfo group of the compounds (VIII) is con-verted into the sulfonyl chlorides, for example by standard methods, such as reaction of phosphorus oxy-chloride or thionyl chloride with potassium salts of the corresponding sulfonic acids in inert solvents, such as acetonitrile and/or sulfolane or in substance by reflux-ing (cf. Houben-Weyl-Klamann, "Metho~e~ der organischen Chemie" ~Methods of Organic Chemistry], 4th Ed., Vol. E XI/2, p. 1067-1073, Thieme Verlag Stuttgart, 1985).

The formation of sulfonamide from the sulfonyl chlorides with tert.-butylamine in ethanol gives the com-pounds (VII) in good yields (cf. analogous reactions in WO 89/10921).

Alternatively, the sulfo~A~i~es of the for~ll A II in which Rl and R2 are other than ~ can be obtained by A~;nolysis of the corresponding sulfonyl chlorides of the fo~mula (IXb) N ( O R 2 j R 1 ( IXa, X' OH) S02X' ( IXb, X' Cl ) ( R3 ) which, in turn, are readily obtAinAhle from the sulfonic acids ~IXa) by the abovementioned stAn~Ard methods (see reactions of (VIII) to give (VII)).

The compounds (IXa), in turn, can be obtained from the - 21~4~S9 nitrobenzenesulfonic acid (VIII) by the reaction sequence (1) reduction analogous to the reduction of (VII), (2) N-acylation and (3) O-acylation, the latter as described in the preparation of (VI).

The abovementioned starting compounds of the formula (VIII) or the sulfonyl chlorides thereof are either known or commercially available compounds or they can be prepared in a simple manner, for example by 10 - nitration (cf. ~ouben-Weyl-Muller, ~Methoden der organischen Chemie" [Methods of Organic Chemistry~, 4th Ed., Vol. X/1, p. 463 et seq., Thieme Verlag Stuttgart, 1971), - sulfonation (cf. Houben-Weyl-Klamann, "Methoden der organischen Chemie" [Methods of Organic Chemistry], 4th Ed., Vol. E XI/2, p. 1055 et seq., Thieme Verlag Stuttgart, 1985); ~ouben-Weyl-Muller, "Methoden der organischen Chemie" [Methods of Organic Chemistry], 4th Ed., Vol. IX, p. 435 et seq., Thieme Verlag Stuttgart, 1955), - sulfochlorination (Houben-Weyl Rlamann, "Methoden der organischen Chemie" tMethods of Organic Chemistry], 4th Ed., Vol. E XI/2, p. 1067 et seq., Thieme Verlag Stuttgart, 1985; ~ouben-Weyl-Muller, "Methoden der organischen Chemie~ ~Methods of Organic Chemistry], 4th Ed., Vol. IX, p. 563 et seq., Thieme Verlag Stuttgart, 1955), - introduction of a radical R3, for example by halo-genation (~ouben-Weyl-Muller: "Methoden der organis-chen Chemie" [Methods of Organic Chemistry], 4th Ed., Vol. V/3, p. 213 et seq., Thieme Verlag Stuttgart, 1962; Houben-Weyl-Muller, "Methoden der organischen Chemie" [Methods of Organic Chemistry], 4th Ed., Vol. V/3, p. 556-561 and 845-853, Thieme Verlag Stuttgart, 1962; Houben-Weyl-Muller, "Methoden der organischen Chemie" [Methods of Organic Chemistry], 4th Ed., Vol. V/4, p. 233-299 and 437-447, Thieme Verlag Stuttgart, 1960;

~i~476 Rouben-Weyl-Muller, "Methoden der organischen Chemie" [Methods of Organic Chemistry], 4th Ed., Vol. V/4, p. 557-593 and 639-647, Thieme Verlag Stuttgart, 1960) or alkylation (G.A. Olah, "Friedel-Crafts-Chemistry", Wiley-Interscience, New York, 1973), - or by derivatization of an already existing third substituent, for example by oxidation of an alkyl group (R3) to give a carboxylic acid, followed by an esterification (R3 s CO2-alkyl) (Houben-Weyl-Falbe:
"Methoden der organischen Chemie~' [Methods of Organic Chemistry], 4th Ed. Vol. EV/l, Thieme Verlag Stuttgart, 1985, p. 199 - 202 and references cited therein).

The carbamates of the formula (III) required for the reaction of the compounds (II) by variant a) are known from the literature or can be prepared analogously to known processes (cf. EP-A-70804 or US-A-4,480,101).

The compounds of the formulae (IV) and (V), which can be employed in process variant b), can also be prepared from the abovementioned compounds of the formulae (III) and (VIII) and from their precursors by, or analogous to, generally ~nown methods.

The phenylsulfonyl isocyanates of the formula (IV) where R2 is other than H can be prepared, for example, analo-gously to the processes in EP-A-184,385 from com-pounds (II), for example using phosgene.

The reaction of the compounds (IV) with the amino hetero-cycles (V) is preferably carried out in inert, aprotic solvents, such as, for example, dioxane, acetonitrile or tetrahydrofuran, at temperatures between 0C and the boiling point of the solvent.

The (thio)isocyanates of the formula (X) can be synthe-sized by processes known from the literature (cf.

- 21 _ 2 1 ~ ~7 6 9 EP-A-232,067A, EP-A-166,516).
The reaction of compounds of the formula (X) with sulfon-amides of the formula (II) is carried out at temperatures between -10C and 100C, preferably between 20 and 80C, in an inert aprotic æolvent, such as, for example, acetone or acetonitrile, in the presence of a suitable base, such as, for example, triethylamine or potassium carbonate.

The salts of the compounds of the formula (I) are prefer-ably prepared in inert solvents, such as, for example, water, methanol, acetone, dichloromethane, tetrahydro-furan, toluene or heptane, at temperatures from 0 to 100C. Suitable bases for the preparation of the salts according to the invention are, for example, alkali metal carbonates, such as potassium carbonate, alkali metal hydroxides and alkaline earth metal hydroxides, ammonia or a suitable amine base, such as triethyl~m;ne or ethanolamine. Acids which are suitable for salt formation are, for example, ~Cl, ~Br, ~2SO4 or HN03 -The solvents termed "inert solvents~ in the above processvariants are understood as meaning in each case solvents which are inert under the reaction conditions in ques-tion, but which need not be inert under any reaction conditions.

The compounds of the for~lllA (I) according to the inven-tion or salts thereof have an outst~n~;ng herbicidal activity against a broad range of economically important monocotyledon and dicotyledon harmful plants. The active substances also act efficiently on pere~ni Al weeds which produce shoots from rhizomes, rootstocks or other perennial organs and which are difficult to control. In this context, it does not matter whether the substances are applied by the pre-plant, pre-emergence or post-emergence method. Specifically, examples may be mentioned of some representatives of the monocotyledon and dicotyl-edon weed flora which can be controlled by the ccmpounds 2 1 9L .1 7 ~a ~

according to the invention, without the enumeration being a restriction to certain species.

Examples of weed species on which the active substances act efficiently are, from amongst the monocotyledons,

5 - Avena, Lolium, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria and Cyperus species from the annual sector and, from amongst the perenn;~l species, Agropyron, Cynodon, Imperata and Sorghum, and also perennial Cyperus species.

In the case of the dicotyledon weed species, the range of action extends to species such as, for example, Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Matricaria, Abutilon and Sida from amongst the annuals, and Convolvulus, Cirsium, Rumex and Artemisia in the case of the perenn;~l weeds.

The active substances according to the invention also effect an outst~n~;ng control of weeds which occur under the specific conditions of rice growing, such as, for example, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus.

If the compounds according to the invention are applied to the surface ~efore ger~;n~tion, then the weed seedlings are either prevented completely from emerging, or the weeds grow until they have re~ched the cotyledon stage but then their growth stops, and, eventualIy, after three to four weeks have elapsed, they die completely.

If the active substances are applied post-emergence to the green parts of the plants, growth also stops drastic-211y a very short time after the treatment and the weed plants remain at the growth stage of the point of time of application, or they die completely after a certain time, so that, in this manner, competition by the weeds, which is harmful to the crop plants, is eliminated at a very early point in time and in a sustained manner.

21447~

Even though the compounds according to the invention have an excellent herbicidal activity against monocotyledon and dicotyledon weeds, crop plants of economically important crops, such as, for example, wheat, barley, rye, rice, maize, sugar beet, cotton and soya, are not-damaged at all, or only to a negligible extent. For these reasons, the present compounds are highly suitable for selectively controlling undesired vegetation in plantings for agricultural use.

Moreover, the substances according to the invention have excellent growth-regulating properties in crop plants.
They engage in the plant metabolism in a regulating manner and can thus be employed for the targeted control of plant constituents and for facilitating harvesting, for ex2mple by provoking desiccation and stunted growth.
Furthermore, they are also suitable for generally regul-ating and inhibiting undesired vegetative growth without simultaneously destroying the plants. Inhibition of vegetative growth plays an important role in many mono-cotyledon and dicotyledon crops since lodging can bereduced hereby, or prevented completely.

The compounds according to the invention can be employed in the conventional preparations as wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules. The invention therefore also relates to herbi-cidal and plant-growth-regulating composit~ons which comprise compounds of the formula (I) or salts thereof.

The compounds of the formula (I) or the salts thereof can be formulated in various ways, depe~;ng on the prevail-ing biological and/or chemico-physical parameters.
Examples of possible formulations which are suitable are:
wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concen-trates (EC), emulsions (E~), such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), dispersions on an oil or water basis, 2~7~9 oil-miscible solutions, capsule suspensions (CS), dusts (DP), seed-dressing products, granules for broad-casting and soil application, granules (GR) in the form of microgranules, spray granules, coated granules and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcap-sules and waxes.

These individual formulation types are known in principle and described, for example, in:
Winnacker-Kuchler, "Chemische Technologie" [Chemical Technology], Volume 7, C. Hauser Verlag, Munich, 4th Edition 1986; Wade van Valkenburg, "Pesticide Formulations" Marcel Dekker, N.Y., 1973; R. Martens, -Spray Drying ~andbook", 3rd Ed. 1979, G. Goodwin Ltd.
London.

The necessary formulation a~xil;~ries such as inert materials, surfactants, solvents and other additives are also known and 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; Schonfeldt, "Grenzflachenaktive Athylenoxi~A~-lkte" tSurface-active Ethylene Oxide Adducts], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Kuchler, ~'Chemische Technologie" [Chem-ical Technology], Volume 7, C. ~auser Verlag, Munich, 4thEd. 1986.

Based on these formulations, it is also possible to prepare combinations with other pesticidally active substances, such as, for èxzmple, insecticides, acari-cides, herbicides, fungicides, safeners, fertilizersand/or growth regulators, for example in the form of a - 21~476~

readymix or a tank mix.

Wettable powders are preparations which are uniformly dispersible in water and which, besides the active substance, also contain ionic and/or nonionic surfactants (wetting agents, dispersants), for example polyoxy-ethylated alkylphenols, polyoxyethylated fatty alcohols and, polyoxyethylated fatty amines, fatty alcohol poly-glycol ether sulfates, alkanesulfonates, alkyl-benzenesulfonates, sodium ligninsulfonate, sodium 2,2'-dinaphthylmethane-6,6~-disulfonate, sodium dibutylnaph-thalenesulfonate or else sodium oleoylmethyltaurinate, in addition to a diluent or inert substance. To prepare the wettable powders, the herbicidal active substances are ground finely, for example in conventional apparatuses, such as hammer mills, blowing mills and air-jet mills and mixed with the formulation auxiliaries, either simul-taneously or subsequently.

Emulsifiable concentrates are prepared by dissolving the active substance in an organic solvent, for example butanol, cyclohexanone, dimethylforr-m;~e, xylene or else higher-boiling aromatics or hydrocarbons or mixtures of the organic solvents, with an addition of one or more ionic and/or non-ionic surfactants (emulsifiers). Emulsi-fiers which can be used are, for example: calcium salts of alkylarylsulfonic acids, such as calcium dodecyl-benzenesulfonate, or non-ionic 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, for example, sorbitan fatty acid esters or polyoxethylene sorbitan esters, such as, for example, polyoxyethylene sorbitan fatty acid esters.

Dusts are obtained by grinting the active substance with finely divided solid substances, for example talc, natural clays, such as kaolin, bentonite and pyrophyl-lite, or diatomaceous earth.

`- 21~76~

Suspension concentrates can be oil- or water-based. They can be prepared, for example, by wet grinding using commercially available bead mills, optionally with an addition of surfactants, such as those already listed above for the other types of formulation.

Emulsions, for example oil-in-water emulsions tEW), can be prepared, for example, using aqueous organic solvents, optionally together with surfactants, such as those already listed above for the other types of formulation by means of stirrers, colloid mills and/or static mixers.

Granules can be produced either by spraying the active substance onto adsorptive, granulated inert material or by applying active substance concentrates onto the surface of carriers such as sand, kaolinites or of granulated inert material, by means of binders, for example polyvinyl alcohol, sodium polyacrylate or alter-natively mineral oils. Suitable active substances can also be granulated in the manner which is conventional for the production of fertilizer granules, if desired in a mixture with fertilizers.

Water-dispersible granules are prepared, as a rule, by the customary methods such as spray drying, fluidized-bed granulation, disk granulation, mixing using high-speed mixers and extrusion without solid inert material.

The agrochemical preparations comprise, as a rule, 0.1 to 99 % by weight, in particular 0.1 to 95 % by weight, of active substance of the formula (I) or salts thereof.

The active substance concentration in wettable powders i~, for example, about 10 to 90 % by weight; the remain-der to 100 % by weight is composed of conventionalformulation components. In the case of emulsifiable concentrates, the active sùbstance concentration can be about 1 to 90, preferably 5 to 80 % by weight. Formula-tions in the form of dusts usually contain 1 to 30, - 27 - 2 1 4 1 7~ 3 usually preferably 5 to 20 % by weight of active sub-stance, sprayable solutions about 0.05 to 80, preferably 2 to 50 % by weight. In the case of water-dispersible granules, the active substance content depends partly on whether the active compound is liquid or solid and on which granulation all~il;Aries, fillers and the like are used. It is for example between 1 and 95 % by weight, preferably between 10 and 80 % by weight in the case of the water-dispersible granules.

In addition, the active substance formulations mentioned comprise, if appropriate, the adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, defoamers, evaporation inhibitors and pH and viscosity regulators which are conventional in each case.

Active substances which can be employed in combination with the active substances according to the invention in formulation mixtures or in a tank mix are, for example, known active substances as they are described, for example, in Weed Research 26, 441-445 (1986), or "The Pesticide Manual", 9th Edition, The British Crop Protection Council, 1990/91, Bracknell, England, and in the literature cited therein. Active substances which may be mentioned as examples of herbicides which are known from the literature and which can be combined with the compounds of the formula (I) are the following (note: the compounds are either given by their common name, using the terminology of the International Organization for StA~Ardization (ISO), or by their chemical name, if appropriate together with a conventional code number):
acetochlor; acifluorfen; aclonifen; AR~ 7088, i.e. [[[1-[5-[2-chloxo-4-(trifluoromethyl)phenoxy]-2-nitrophenyll-2-methoxyethylidene]amino]oxylacetic acid and its methyl ester; alachlor; alloxydim; ametryn; amidosulfuron;
amitrol; AMS, i.e. ammonium sulfamate; anilofos; asulam;
atrazine; aziprotryn; barban; BAS 516 ~, i.e. 5-fluoro-2-phenyl-4~-3,1-benzoxazin-4-one; benazolin; benfluralin;

- 28 - ~ 1769 benfuresate; bensulfuron-methyl; bensulide; bentazone;
benzofenap; benzofluor; benzoylprop-ethyl; benzthiazuron;
bialaphos; bifenox; bromacil; bromobutide; bromofenoxim;
bromoxynil; bromuron; buminafos; busoxinone; butachlor;
butamifos; butenachlor; buthi~zole; butralin; butylate;
carbetamide; CDAA, i.e. 2-chloro-N,N-di-2-propenylacet-A~; de; CDECl i.e. 2-chloroallyl diethyldithiocarbamate;
CGA 184927, i.e. 2-~4-t(5-chloro-3-fluoro-2-pyridinyl)-oxy]phenoxy]propanoic acid and its 2-propynyl ester;
chlomethoxyfen; chloramben; chlorazifop-butyl,pirifenop-butyl; chlorbromuron; chlorbufam; chlorfenac; chlor-flurecol-methyl; chloridazon; chlorimuron-ethyl; chlor-nitrofen; chlorotoluron; chloroxuron; chlorpropham;
chlorsulfuron; chlorthal-dimethyl; chlorthi~;d; cin-methylin; 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, clomazon;
dimethipin; dimetrasulfuron, cinosulfuron; dinitramine;
dinoseb; dinoterb; diphenamid; dipropetryn; diquat;
dithiopyr; diuron; DNOC; eglinazine-ethyl; EL 177, i.e.
5-cyano-1-(1,1-dimethylethyl)-N-methyl-3H-pyrazole-4-carboxamide; endothal; EPTC; esprocarb; ethalfluralin;
ethametsulfuron-methyl; ethidimuron; ethiozin; ethofume-sate; F5231, i.e. N-[2-chloro-4-fluoro-5-[4-(3-fluoro-propyl)-4,5-dihydro-5-oxo-lH-tetrazol-1-yl]phenyl]ethane-sulfonamide, F6285, i.e. 1-[5-(N-methylsulfonyl)-amino-2,4-dichlorophenyl]-3-methyl-4-difluoromethyl-1,2,4-triazol-5-one, fenoprop; fenoxan, clomazon;
fenoxaprop-ethyl; fenuron; flamprop-methyl; flaza-sulfuron; 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; flurt-amone; fomesafen; fos~;ne; furyloxyfen; glufosinate;

- 214 17~9 glyphosate; halosafen; haloxyfop and its ester derivatives; hexazinone; Hw 52, i.e. N-(2,3-dichloro-phenyl)-4-(ethoxymethoxy)benzamide; imdazamethAhçnz-methyl; imazapyr; imazaquin; imazethamethapyr; imaze-thapyr; imazosulfuron; ioxynil; isocarbamid; isopropalin;isoproturon; isouron; isoxaben; isoxapyrifop; karbutil-ate; lactofen; lenacil; linuron; MCPA; MCPB; mecoprop;
mefenacet; mefluidid; metAm;tron; metazachlor; meth~hen thiazuron; metham; methazole; methoxyphenone; methyldym-ron; metobromuron; metolachlor; metoxuron; metribuzin;
metsulfuron-methyl; M~; molinate; monalide; monocarbamide dihydrogensulfate; monolinuron; monuron; MT 128, i.e. 6-chloro-N-(3-chloro-2-propenyl)-5-methyl-N-phenyl-3-pyridaz;n~m;ne; MT 5950, i.e. N-[3-chloro-4-(1-methyl-ethyl)phenyl]-2-methylpentAnAm;~e; naproAn;l;~e; naprop-amide; naptalam; NC 310, i.e. 4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole; neburon; nicosulfuron;
nipyraclophen; nitralin; nitrofen; nitrofluorfen; nor-flurazon; orbencarb; oryzalin; o~;Azon; oxyfluorfen;
paraquat; pebulate; pendimethalin; perfluidone; phen-medipham; phenisopham; phe~ ;pham; picloram; pipero-phos; piributicarb; pirifenop-butyl; pretilachlor;
primisulfuron-methyl; procyazine; pro~;A~;ne; proflura-lin; proglinazine-ethyl; prometon; prometryn; propachlor;
propanil; propaquizafop and its ester derivatives;
propazine; propham; propyzamide; prosulfalin; prosulfo-carb; prynachlor; pyrazolinate; pyrazon; pyrazosulfuron-ethyl; pyrazoxyfen; pyridate; quinclorac; quinmerac;
quinofop and its ester derivatives, quizalofop and its ester derivatives, quizalofop-ethyl; quizalofop-p-tefur-yl; renriduron; dymron; S 275, i.e. 2-[4-chloro-2-fluoro-5-(2-p-o~yll~loxy)phenyl]-4,5,6,7-tetrahydro-2~-indazole;
S 482,i.e.2-[7-fluoro-3,4-dihydro-3-oxo-4-(2-propynyl)-2~-1,4-benzoxazin-6-yl]-4,5,6,7-tetrahydro-lH-isoindole-1,3(2~)-dione, secbumeton; sethoxydim; siduron; simazine;
simetryn; SN 106279, i.e. 2~[[7-[2-chloro-4-(trifluoro-methyl)phenoxy]-2-naphthalenyl]oxy]propanoic acid and its methyl ester; sulfometuron-methyl; sulfazuron; flazasul-furon; TCA; tebutam; tebuthiuron; terbacil; terbucarb;

214~`763 terbuchlor; terbumeton; terbuthylazine; terbutryn;
TF~ 450,i.e.N,N-diethyl-3-[(2-ethyl-6-methylphenyl)sul-fonyl]-l~-1,2,4-triazole-1-carboxamide, thiazafluron;
thifensulfuron-methyl; thiobencarb; tiocarbazil; tral-koxydim; tri-allate; triasulfuron; triazofenamide;
tribenuron-methyl; triclopyr; tridiphane; trietazine;
trifluralin; trimeturon; vernolate; WL 110547, i.e.
5-phenoxy-1-t3-(trifluoromethyl)phenyl]-lH-tetrazole.

For use, the formulations which are present in commer-cially available form are, if appropriate, diluted in the customary manner, for example using water in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules. Preparations in the form of dusts, granules for cell application and for broad-casting, and sprayable solutions are conventionally notdiluted further with other inert substances prior to use.
The application rate required of the compounds of the formula (I) varies with the external conditions, such as, inter alia, temperature, humidity and the type of herbi-cide used. It can vary within wide limits, for examplebetween 0.001 and 10.0 kg/ha or more of active ingredi-ent, but it is preferably between 0.005 and 5 kg/ha.

A. Chemical Examples a) 2-Carboxy-5-nitrobenzenesulfonic acid 25 400.0 g (2.53 mol) of potassium permanganate are added in portions in the course of 2 hours at 80C to a solution of 106.0 g (0.40 mol) of 2-methyl-5-nitrobenzenesulfonic acid and 80.0 g (0.58 mol) of potassium carbonate in 1300 ml of water. The reaction temperature is maint~;ne~
between 80 and 95C. After stirring has been continued for a further 4 hours, the solid which has formed is removed by filtration. The filtrate is acidified using concentrated hydrochloric -acid (p~ = 1). The colorless 2-carboxy-5-nitrobenzenesulfonic acid which has precipitated is filtered off with suction using a Buchner - 214~769 funnel and dried at approximately 50C/100 torr (82.0 g;
83.7 % of theory). m.p. >300C.

b) 2-Methoxycarbonyl-5-nitrobenzenesulfonic acid A suspension of 190.0 g (0.77 mol) of 2-hydroxycarbonyl-5-nitrobenzenesulfonic acid, 10 ml of dimethylforr-miAe and 250 ml (3.43 mol) of thionyl chloride is heated at the boil for 3 hours. After the insoluble components have been removed by means of filtration, the filtrate is concentrated. 200 ml (4.94 mol) of methanol are added dropwise to the resulting residue. After the addition has ended, the reaction mixture is cooled to 0C. The solid which has precipitated is filtered off and dried. This gives 70.9 g (35.3 % of theory) of colorless, crystalline 2-methoxycarbonyl-5-nitrobenzenesulfonic acid (m.p.: 92-94C).

A second fraction (62.5 g, 31.1 % of theory) is obtained by removing the volatile components of the mother liquor by distillation on a rotary evaporator.

c) 2-Methoxycarbonyl-5-nitrobenzenesulfonyl chloride A solution of 70.9 g (0.27 mol) of 2-methoxycarbonyl-5-nitrobenzenesulfonic acid in 300 ml of methanol is treated carefully with a solution of 17.3 g (0.27 mol) of potassium hydroxide (88 % strength) and 100 ml of methanol, with vigorous stirring. After the mixture has been cooled to 0C, the salt which has formed is filtered off, dried and subsequently suspended in 150 ml of sulfolane, 150 ml of acetonitrile and 10 ml of dimethyl-formamide. After 100 ml (1.07 mol~ of phosphorus oxychloride have been added, the mixture is heated at the boil for 2.5 hours and subsequently poured into ice-water. The 2-methoxycarbonyl-5-nitro-benzenesulfonyl chloride which has precipitated (60.1 g, 70 ~ of theory) is filtered off with suction using a Buchner funnel and freed from traces of solvent under reduced pressure.

21447~9 M.p.: 86-88C.

d) N-tert.-Butyl-2-methoxycarbonyl-5-nitrobenzene-sulfon~m;de 50 ml (0.48 mol) of tert.-butylamine are slowly added dropwise at 0C to a solution of 34.4 g (0.12 mol) of 2-methoxycarbonyl-5-nitro-benzenesulfonyl chloride in 200 ml of ethyl acetate and 250 ml of ethanol. Stirring of the reaction solution is subsequently continued for 10 minutes at room temperature. After 500 ml of water have been added, a colorless solid crystallizes out.
After filtration and drying, 28.1 g (89 %) of N-tert.-butyl-2-methoxycar~onyl-5-nitrobenzenesulfonamide are obtained. M.p.: 121-124C.

e) N-tert.-Butyl-5-hydroxylamino-2-methoxycarbonyl-benzenesulfonamide 23.4 g tO.08 mol) of N-tert.-butyl-2-methoxycarbonyl-5-nitrobenzenesulfonamide are introduced into 600 ml of ethanol at 40C. After the mixture has been buffered with 42.1 g (0.79 mol) of ammonium chloride and 170 ml of water, 32.0 g (0.49 mol) of zinc powder are added in - portions. Stirring of the mixture is subsequently continued for 4 hours at approximately 55C. The solid is removed by filtration, and the filtrate is evaporated on a rotary evaporator. The residue is taken up in 800 ml of ethyl acetate, and the mixture is washed with 300 ml of water. The aqueous phase is re-extracted three times using 300 ml of dichloromethane. The combined organic phases are dried over magnesium sulfate. Volatile components are subsequently removed by distillation on a rotary evaporator. The crystalline residue is extracted by stirring with a little ethyl acetate: heptane (1:1).
In this manner, 17.2 g (77 %) of N-tert.-butyl-S-hydroxylamino-2-methoxycarbonyl-benzenesulfonamide are ob~A;ne~. M.p.: 190-195C.

- 21447~9 f) N-tert.-Butyl-5-(N-acetylhydroxylamino)-2-methoxy-carbonylbenzenesulfo~ATni~le 3.31 g (0.01 mol) of N-tert.-butyl-5-hydroxylamino-2-methoxycarbonylbenzenesulfonamide are briefly heated in 20 ml of acetonitrile to obtain a homogeneous solution.
0.94 g (0.01 mol) of acetyl chloride and 1.30 g (0.01 mol) of triethylamine are then added, with ice-bath cooling. After 2 hours, the mixture is taken up in ethyl acetate and washed in succession with 1 N hydrochloric acid and saturated sodium chloride solution. After the organic phase has been dried over magnesium sulfate, the solvent is removed by distillation on a rotary evaporator. After recrystallization o~ the residue from ethyl acetate/heptane, 3.12 g (82 %) of N-tert.-butyl-5-(N-acetylhydroxylamino)-2-methoxycarbonylbenzenesulfon-amide are obtained. M.p.: 168-169C.

g) 5-(N-Acetylhydroxylamino)-2-methoxycarbonyl-benzenesulfonamide 1.70 g (4.9 mmol) of N-tert.-butyl-5-(N-acetylhydroxyl-amino)-2-methoxycarbonylbenzenesulfonamide are dissolved in 20 ml of trifluoroacetic acid. After 18 hours at 25C, the volatile components are removed by distillation under reduced pressure. This gives 1.48 g of 5-N-(acetylhydrox-ylamino)-2-methoxycarbonylbenzenesulfonamide.
M.p.: 246-247C.

h) 5-(N-Acetylhydroxylamino)-N-[(4,6-dimethoxypyrimid-in-2-yl)aminocarbonyl]-2-methoxycarbonylbenzene-sulfonamide (corresponds to Example 192 in Table 1) 0.8 ml of DBU are added to a mixture of 1.00 g (4.4 mmol) of 5-(N-acetylhydroxylamino)-2-methoxycarbonylbenzene-sulfonamide and 0.65 g (2.4 mmol) of 4,6-dimethoxy-2-(phenoxycarbonyl~;no)pyrimidine in 50 ml of acetonit-rile. After the mixture has been stirred for 18 hours, the solvent is removed by distillation on a rotary 21~476~

evaporator. The residue is taken up in water and washed with diethyl ether. The aqueous phase is acidified using concentrated hydrochloric acid (pH = 1). The colorless solid is removed by filtration and extracted by stirring with a little methanol. The resulting 5-(N-acetylhydrox-ylamino)-N-[(dimethoxypyrimidin-2-yl)aminocar~onyl]-2-methoxycarbonylbenzenesulfonamide (0.81 g, 79 % of theory) has a melting point of 205-208C.

i) N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-methoxycarbonyl-5-(N-methoxycarbonylhydroxylamino)-benzenesulfonamide (Ex. 238, Table 1) 0.75 ml of DBU are added to a mixture of 0.74 g (2.43 mmol) of 2-methoxycarbonyl-5-(N-methoxycarbonyl-hydroxylamino)benzenesulfonamide and 0.67 g (2.43 mmol) of 4,6-dimethoxy-2-(phenoxycarbonylamino)pyrimidine in 50 ml of CH3CN. After the mixture has been stirred for 18 hours, the solvent is removed by distillation on a rotary evaporator. The residue is taken up in water and washed with diethyl ether. After the aqueous phase has been acidified with concentrated hydrochloric acid (p~ = 1) a colorless solid precipitates. After filtration with suction and washing with methanol, 0.66 g of the above-designated sulfonylurea is obtained; colorless crystals of m.p. 192-193C.

j) N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-methoxycarbonyl-4-(N-methoxycarbonylhydroxyl~;no)-benzenesulfonamide (Examples 3-9, Table 3) 1.2 ml of DBU are added dropwise to a suspension of 1.2 g of 2-methoxycarbonyl-4-(N-methoxycarbonylhydroxylamino)-benzenesulfon~;de and 1.1 g of 4,6-dimethoxy-2-(phenoxy-carbonylamino)pyr;mi~;ne in 30 ml of C~3CN. After a reaction time of 4 hours, the mixture is worked up analogously to Example i). 1.09 g of the above-designated sulfonylurea are obtained; colorless crystals of m.p.
171-174C.

21~il7~9 k) Sodium salt of N-[(4,6-dimethoxypyrimidin-2-yl)-aminocarbonyl]-2-methoxycarbonyl-5-(N-methoxy-carbonylhydroxylamino)benzenesulfonamide (Examples 4-10, $able 4) 1.2 ml of 1 N sodium hydroxide solution are added to a solution of 0.57 g of N-~(4,6-dimethoxypyri~i~in-2 yl)aminocarbonyl]-2-methoxycarbonyl-5-(N-methoxycarbonyl-hydroxylamino)benzenesulfonamide in 20 ml of CH2Cl2 and 20 ml of CH3CN. After the reaction mixture has been stirred for 2 hours, it is evaporated in vacuo. The resulting product (0.61 g) melts at 175-180C and is the above-designated sulfo~ylurea.

The rP~ining compounds described in Tables 1 - 4 are obtained analogously to Examples a) to k).

The following abbreviations are used in the tables:
M.p. = melting point in C
No. = Example No.
Et = ethyl (C2Hs) Me = methyl (CH3) Ph = phenyl c-Pr = cyclopropyl n-Pr = n-propyl i-Pr = i-propyl - 36 _ 21~4763 Table 1 R~ - N~2 ~ 5O2NHCONR4lN1X

No Rl R2 R3 R~ X Y Z M.p.

CHO H H H OMe OMe CH 150 2 CHO M~ H H OMe OMe CH
3 COCH3 H H H OMc OM~ CH 154 4 H H H OMc OMc N
H H H OMe Me CH

6 H H H Me Me CH

7 H H H OMe Cl CH

8 H H H OMe Me N

9 COCH3 H H H OMo OMe N

10 ~ H H H NHMc OCH2CF3 N

11 H H H NMc2 SMo N

12 H H Me OMe OMe CH

13 M~ H H OMc OMc CH

14 Mc H Mc OMe OMe CH

15 COCH2CH3 H H H OMe OMe CH 158-159

16 H H H OMe OM~ N

17 COCH2CH3 H H H OMe Cl CH

18 H H H OM~ Me N

19 Mc H H OMc OMe CH

20 COCF3 H H H OMII OM~ CH

21 COCF3 H H M~ OMe OM~ CH

22 COCF3 H H H OMc M~ N

23 COCH2Br H H H OMe OM~ CH

24 COCHCI2 H H H OMe OMe CH

25 COCH~CH312 H H H OMe OMI~ CH

26 COPh H H H OMc OMe CH

27 -t~O-c-Pr H H ~ H OMc OMe CH

-37 ~14~76~
No. Rl R2 R3 R~ X Y ZM.p.

28 CO c~Pr Mo H H OMo OMo CH
2g ~ Me H H OMe Mo N
30 H H H OMo M~ N
31 eo ~ H H H OM~ OMo CH

32 CO CH-CH2 H H H Mo OM- N
33 CO-CH -CH2 H H H OMo OMo CH
34 CO2CH3 H H H OMo OMo CH210 35 H H H OM- nM~ N

36 CO2CH3 Mo H H OMe OMo CH
37 CO2-i-Pr H H H OM~ OMe CH
38 CO2-i-Pr Mo H H OMo OMe CH
39 CS-NHEt H H H OMo OMo CH
40 CS-NHEt H H H Cl OMo CH
41 CS NHEt H H M~ OMo OMo CH
42 CS NH-CO2Et H H H OMe OMo CH
43 CS-NH-CO2Et Mo H H OMo OMo CH

44 H H H H OMo OMo CH
45 502CH2CI H H H OMo Me N
46 Mo H H OMe OMo CH
47 ' Mo H H Mo MoCH
48 SO2Me Me H H OMo OMe CH
49 SO2Me H H H OMe OMo CH
50 SO2NHMe H H H OMo OMe CH
51 502NHMo H H H SMo NM~2 N

52 SO2NMo H H H OMo OM~ CH
53 502NMo Mo H H OM- OMo CH
54 CHO H 6~Me H OMo OMo CH
55 H ' H OEt OEt CH
56 CHO H 6 Mo H NMe2 SMo N
57 ' H ' H OMo Mo N

2~4763 -- 38 ~
No, Rl R2 R3 R~ X Y Z M.p.

58 CHO Me H OMe OMe N
59 CHO H H OMo Cl CH
60 ~ H H OCF2H OCF2H CH
61 CO-CH3 H ~Me H OMe OMs CH 178-18Z
62 ' H ' H Me Me CH

63 ' H H NMo2 OCH2CF~ N
64 ' H H OMo Mo N
65 ' Mo 6 Mo H OMe OMe N
66 ' H Me OMo OMe N
67 CO CH~CH2 H ' H OMe OMe CH 178-180 68 CO-CH2CH~ H 6 M- H OMo OMo CH 180 69 CO CH2CH3 Me ' H OMe OMe CH
70 CO i Pr H H OMo OMo CH
71 CO-CH - CH2 H H ~ . CH

72 COCF3 H ' H ' ' CH
73 COCF3 H ' Me OMe Me N
74 CO-c Pr H 6 Mo H OMo Mo N
75 CO c-Pr H H ' OMe CH 127 130 76 ' H ' H Me Mo CH
77 COCsHll H 6-Me H OMe OMc CH 179 78 CO2Mo H 6-Me H OMc OMe CH 198~201 79 ' H ' H Mo Me CH
80 CO2Me H 6~Me H NEt2 SMe N

81 ~ Me ' H OM~ OMe CH
82 CO2CH2CH2CI H ' H OMo OM~ CH
83 CO2CH2- H ' H

84 C02CH2CCI~ H ' H
CO2CH2CH2OMe H ' H
86 CONHEt H ' H
87 CONHEt H 6 M- H OMo Mo N
88 CONHEt Me ' H
89 CONHPr H H OMe CH 204 21~69 -- 39 ~
NO. Rl R2 R3 R~ X Y Z M.p.

90 CONHPr H ' H OcH2cF3 NMe2 N
91 CSNHEt H 6-Me H OMe OMo CH 108 92 CSNHEt H 6~Me Me OMe Me N
93 CSNHCH2CH-CH2H 6-Me H OMc OMeCH 134-137 94 CSNHCO2Et H 6-Mo H OMe OM-CH 130-132 5O2Me H H
96 Me H
97 H H Cl OMe 98 SO~NHMq H 6-Me H OMe OM~ CH
99 H ' Me OMe M- N
100 SO2NMei H 6-Me H OMo OMe CH
101 SO2CH2CI Me 6~Me H OMe OMe CH

103 CHO H 6 CI H OMe OM- CH 203 104 CHO H 6-CI H SMe OM- N
105 H H OCH2CF~ NM~2 N
106 H H OMe a CH

1 Q7 COCH3 H 6-CI H OMe OMe CH 193 108 Me H
109 H H ' Me N
110 COCH2CH3 H H OMe N

1t2 CO-c-Pr H 6 CI H . CH 145 113 CO-c Pr Me ~CI H OMe OMe CH

115 COCF3 H M- OMe M~ N
116 COPh H 6-CI H OMe OM- CH

117 CO-C6H4-4-CI H H . 192 118 CO-C~sH3-2,4 C12 H ' H . 230 119 ~53_ H 6-CI H OM~ OMe CH 202 ~o~ tl 120 c~ ' 203 121 CO-C5Hll H H 158 122 CO-CMe3 H H 225 123 CO CHBr-CH2CH3 H 6-CI H OM~ OMe CH 194 21 4 ~7~

~ 40 ~
No. R1 R2 R3 R~ X Y Z M.p.

124 CO-CMs2-CH2CI H H . 195 125 COCICII - CCI2 H 6 CI H OM~OMo CH 203 126 COCH20Me H ' H
127 CO2Me H H 212 128 CO2Me Mo H
129 Co2cH2ccl3 H H
130 CSNHEt H 6-CI H OMe OMe CH

131 CSNHPr H H CH
132 CS NH- H 6-CI H OMe OM- CH

133 CSNHCO2Et H H 190 191 134 S02Mel H H
135 S02Me H 6 CI H NMs2 OCH2CF3 N
136 S02 i-Pr H H OMe OMe CH
137 SO~Nl lMe H 6-CI H . 140 138 ' H H Me M~ CH
139 ' OM~ M~ N

140 Cl OMe CH
141 SO~Nr~le2 OMe OM~ CH
142 Me H
143 SO2CH2CH3 Ms 144 CHO H 6 F H OMo OM- CH
145 COCH3 H 6-F H OM~ OM- CH
146 COCH3 Me 6-F H OMe OM~ CH
147 COCH3 H 6-F H OMe Me N
14~ C02Me H 6-F H OMe OMe CH

149 COCCI3 H 6-F H OMo OMe CH
150 CONHPr H 6-F H OMe OM~ CH
151 502Me H 6-F H OMe OM~ CH
152 502NI'M- H 6-F H OMe OMe CH
153 COCH3 H 6 Br H OMe OM~ CH
154 COCH3 H 6-Br H OMe Me N
155 S0~!Nl'r1e H 8 Br H 0Me OMe CH
156 SO~N MP2 H 6~6r H OMe OM~ CH
157 SO~N'Me~ M~ 6 Br H OM- OM~ CH

214~769 _ -- 41 ~
No Rl RZ R3 R~ X Y Z M.p.

158 C02Mo H 6-Bt H OMe OMe CH
159 CO2Me Me B-8r H OMe OMe CH
160 CHO H 6-OM~ H OMe OMe CH
161 COCH3 H ~OMo H OMe OMe CH
162 COCHMe2 H B-OM- H OMe OM~ CH
163 COCH3 Me 6-OMe H OMrt OMe CH
164 COCH3 H 6 OMe H OM- Me N
165 COCH3 H 6-OMe H Mo Me CH

166 CO2Me H 6-OMe H OMe OMe CH
167 C02M~ Me B-OMe H OMe OMe CH
168 C02Me H 6-OMe H NMe2 OCH2CF3 CH
169 so~rJ~ H 6-OMe H OM- OMo CH
170 502Me H 6-OMs H OMo OMe CH
171 COCH3 H 6-OEt H OMo OMe CH
172 COCH3 M- 6-Ok H OM~ OMe CH
173 C02Me H 6-OEt H OMe OMe CH
174 C02Mo H 6 0 i-Pr H OMe OM~ CH

175 C02M~ H 6-0-i-Pr H NMe2 OCHzCF3 N
176 CO ~ H 6-OEt H OMe OMe CH

177 C o ~ H B-OEt H OMe OMe CH

178 CHO H ~CO2Me H OMe OMe CH 161 t79 H H M~ Me CH
180 CHO H 6-C02Me H OMe Cl CH
181 H H OCH2CF3 NMe2 N
182 ~ H H OMe Me N

183 H ' M~ OMe Me N
184 CHO H 6-C02Me H NEt2 OMe N
185 CHO H 6~COzM- H SMe OMe N
186 CHO H 6 C02Ms H OMs OMe N
187 H H OEt OEt N
188 H H OEt OEt CH
189 Ms H OMe OMe CH
190 Me H OMe Me N

- 214~76~
- 42 ~
No. Rl R2 R3 R~ X Y Z M.p.

191 ' Mo H Mo Mo CH
192 COCH~ H 6-CO2Mo H OMo OMe CH 205-208 193 H H Ok OEt CH
194 H H NEt2 SM~ N
195 H H Cl OMo N
196 COCH3 M~ 6CO2Me H Cl OM~ N
197 H H OMe Mo N
198 H Mo OMo Me N
199 COCH3 H 6-CO2M- H Mo Mo CH 122 200 H H OCH2CF3 NMe2 N

202 COEt H 6-CO2Me H OMo OMs CH 117 203 Me H OMe OM- CH
204 Et H OMe OM- CH
205 COEt H 6-CO2Mo H OMo Mo N
206 COEt H ~CO2M~ H NMo2 OCH2CF3 N
207 C0 ~ H 6-CO2M- H OMo OMo CH 125-127 C0 ~ Et 6-CO2M~ H OM~ OM~ CH
209 C0 ~ Mo H OMe OMe CH

210 C0 ~ H H Mo Mo CH

211 C0 ~ H 6-CO2Me Me OMe OMe CH

212 C0 ~ H H OMo Me N

.213 C0 ~ H H OMo SM~ N

214 C0 ~ H H Cl OMe CH

215 C0 ~ H H NM~2 OCH2CF3 N

216 C0 ~ H H NHM~ SMo N

2tg.~7i~

No. Rl R2 R3 R~ X Y Z M.p.

217 C0 "~ H ~C02Me H OMe OMe CH 213 218 C0 "c~ H ' M~ OMe N

219 Co "c~ Me H OMe OM~ CH

220 CO ~ ~ Me H M~ Me CH

221 C0Ph H ' OMe OMe CW 218-220 222 eo ~ H 6-CO2Mc H OMe OMe CH

223 COCF3 H . OMe OMo CH 186-188 224 Me OM~ OMe CH
226 Me OM~ Me N
226 Mo . U OM~ CH
227 H ' Nk2 OM- CH
228 COCF~ H 6-CO2M- H NEt2 OMe N
229 ' Me OMe OMe N
230 ' ~ Me SMe OMe N

231 COCH2~ H 6-CO2M- H SM- OMe CH 110 232 COCH20Me H H
233 COCH2Br H H
234 COCHCI2 H 6-CO2Me H SMe OM~ CW
235 COCHCI2 H H OMo Mo CH
236 COCH2NM~2 H H OMe OMe CH
237 COCH2NHCO2Me H H
238 CO2Me H H 192-193 239 H H OMe OMo N

240 CO2Me H 6CO2M3 H Me M~ CH
241 Me H OMe OMe N
242 H H NEt2 SM- N
243 H H OCH2CF3 NHMe N
244 Me H OMe OM~ CW
245 C02CH2CH2CI H H . 182 246 CO2CHM~2 H H . 96-98 247 C02CHM-2 H 6CO2Me M~ OMe M~ N
. , , 214~76~
~ 44 --NO. R 1 R2 R3 R~ X Y ZM.p.

248 CO2CH2CH~ H H OMe OMe CH
249 CO2CH2CCI3 H H OMo OMe CH
250 CO2CH2CH2OM- H H OMe OMe CH
251 CO2CH2CHCH2 H H . CH
252 CO2CH2C-CH H 6-CO2M~ H OMe OMe CH

254 CONHPr 149-151 255 CONHEt 149-150 Z56 CONHSO2- H 6-CO2Me H OMe OMe CH 180-182 257 CONHSO2- H H OMe Me N
CH2CHCl2 258 CSNHEt H H OMe OMe N
259 Me CH
260 CSNHEt H 6 CO2Me H OMo OM~ CH
261 CSNHCH2CH - CH2 H ~ 115-117 262 CSNHCO2Et H . 190-191 263 CSNHCO2Et H Me N

264 SO2M~ H 6-CO2Mo H OMe OMe CH
265 5O2-i-Pr H
266 SO2NHM~ t43 267 Me M~
268 OMe OMe N
269 Cl OM~ CH
270 SO2NH2 ! . OMr~ OM- N
221 M~ NMQ2 OCH2CF~ N
272 H M- OMe Me N

2?3 COCH3 H 6-CO2 i-Pr H OMe OMe CH

275 H H OMe M~ N
276 CHO H 6-CO2-i-Pr H OMe OMe N
277 CHO H 6-CO2Et H

279 CO2Et H OM~ OM~ CH
280 CO2M~ . .
-~14~7~9 No. R 1 R2 R3 R~ X Y Z M.p.

281 COCH3 H 6-CN H OM~ OMa CH
282 CO2M~ H H OMe OM~ CH

284 CO2Mo H 6-l H
285 CO2M~ H 6-l H Mo OMo N
286 CHO H 6-l H Mo OMe N
287 CHO H OMo 288 COCH~ H 6-NIOHIC0CH3 H OM~ OMe CH
289 M- Me 290 OMo Me N
291 Me 6-NlOMe)COCH3 ~
292 ~ OMe CH
293 CHO H 6-NIOH)COCH
294 CHO Me ~N~OMe)COCH
295 CO2Me H 6-N~OH~CO2M~

299 COCH3 Mo 6-NM~-COCH3 H OMe OMe CH
300 CO2CHCI2 H 6-NMe-COCF3 H OMs OM~ CH
301 CO2CHCI2 H 6-NHCOCF3 H OM~ OMe CH
302 COCH3 H 2 CO2Me H OMe OMe CH
303 OMo Me N
304 CO-i-Pr OMe CH
305 CO2Mo 306 ' ' OMs Me N
307 ~ ~ Cl OMe CH

308 COCH3 ~ 2-CI OMo OMe CH
309 5O2NHMe ' OMe OMe CH
310 5O2NMo2 311 SO2Me 312 CHO H H H OMe OMo N
313 ' OMo Mc N
314 Me Me CH
315~' OMe CH
316 ' Cl CH

- 46 - 21~S9 -No. Rl R2 R3 R4 X Y Z M.p 317 Me ' ' OMe OMo N
318 ' ' ' OMo Mo N
319 Cl OMe N
320 Me Me N
321 Et ' OMe OMe CH
322 ' ' ' Me N
323 Me Mo CH
324 CHO Et H H Cl OMo CH
325 Pr OMe OMe CH

326 CO-CH3 Mo OM~ Mo N
327 Et OMe OMe CH
328 CO-CH2CH3 H OMe Mo N
329 Mo ' OMe OMo CH
330 ' Et 331 OM- OMo N
332 Mo Mo CH
333 ~ ' Cl OMo CH
334 COCF3 H H H Mo Mo CH

335 ' ' Cl OMo CH
336 COCF3 Me H H OMe OMe CH
337 Et ' ~ ' CH
338 Pr 339 COCH2Br H OMe Me N
340 ' Me Me CH
341 Me ' OMe OMo CH
342 Et 343 COCHCI2 H H H OMe OMe N

- 21447~9 No. Rl R2 R3 R~ X Y Z M.p.

344 Me N
345 ' Me ~ OMe CH
346 ' Et 348 COCH2CI Me H H OMe OMe CH
349 H ~ OMe Me N
350 Me Mo CH

352 ' OMe OMe CH

353 Me ' OMe OMe CH
354 ' Cl OMe CH
355 CO-CH(CH3)2 H H H OMe Me N
356 Mo Me N
357 Cl OM~ CH
358 ' Me OMe OMe CH
359 ~ ' Cl OMe CH
360 CO CH~CH3)2 Me H H OMe Me N
361 Et OMe CH

362 CO-c-Pr H H H OMe MQ N
362 ' OMe OMe N
363 Ct Ms CH
364 Me Me CH
365 Me OMo OMe N
366 OMe M~ N
367 Et ' ' ' OMe CH
368 ~ Me H H OMe OMe CH

. .

- 48 - 214476~
No. Rl R2 R3 R~ X Y Z M.p.

369 Et 370 CO2Me Et H H OMe OMe CH
371 ' Me N
372 ' Cl CH
373 Me Me CH
374 Me Me Me CH
375 Me OMe N
376 Et ~ OMe OMe CH
377 CO2Et H H H OMe OMe CH

378 OMe Me N
379 ~ M~ Me CH
380 Me OMe OMe CH
381 Et 382 CO2-n-Pr H H H OMo OMo CH
383 Me N
384 Mo OMe CH
385 Et 387 Me 388 Et -389 CHO H 6-CI Me N
390 M~ -391 OMe CH
392 Et 3g4 COCH3 H 6-CI H Me Me CH

- 21~4769 NO. R1 R2 R3 R~ X Y Z M.p.

395 ' M0 396 OMe N
397 ' Cl OMe CH
398 Et OMe OMe CH
399 n-Pr 400 COCH2CH3 H ~CI H OM0 MO N
401 OMO Cl CH

403 MO OM0 OM~ CH

404 ~ Et Me N
405 COCH2CH3 n-Pr 6-CI H OMO OMe CH
406 CO C-Pr H B-CI H OMe Mo N
407 H ~ Me M0 CH
408 Cl OMO CH
409 ~ MO MO OM0 N
410 ~ OMo OMe CH
411 ~ Et 412 ~ Et ~ OMe Me N
413 n-Pr ~ OM6 OM0 CH
414 CO-CF3 H 6 CI H OMe Cl CH
415 ~ Me MO CH
416 ~ M0 OMo OMe CH
417 CO-CF3 Me 6-CI H OMe Mo N
418 ' MO Me CH
419 Et 420 OMe OMO CH
421 ~ OM0 MO N

- 214~76~

No. R ~ R2 R3 R~ X Y Z M.p.

422 ' Cl OMe CH
423 ~_ Me 6 CI H OM~ Me N
co e, 424 ~3 H OMe CH

425 Me 426 CO~C5H11 Me 427 CO-CsH l l Me 6-CI H OMe Me N
42a CO-CMe3 Me ~ OMe CH

429 CO-CH2 0Me Me Me N
431 ~ Et OMe CH
432 CO2Me H Me N
433 ~ Me M- CH
434 ~ Cl OMe CH
435 Me ~ ~ -436 ~ Me N
437 ~ Et OMe OMe CH

438 CO2Me Et 6-CI H OMo Me N
439 n Pr OMe OMe CH
440 CO2Et H 6-CI H ' 441 ~ OMe M~l N
442 ~ ' Me Me CH
443 ' ~ Cl OMe CH
444 ~ Me OMe 446 ~ OMe Me N

214~769 No. Rl R2 R3 R~ X Y Z M.p.

447 Et OMe OMe CH
448 C02-i Pr H
449 ~ Me N
450 Mo ' ~ -451 C02-i-Pr Me 6-CI H . OMe OMe CH
452 Et 453 . . Me N
454 CHO H B-OMe H OMe Me N
455 ' OMe Cl CH

456 ' ' OCH2CF3 NMe2 N
457 Me ' OMe OMo CH
458 Et 459 ' n-Pr -460 Me Me N
461 Et 462 n Pr 463 CO CH3 H 6-OMe H Cl OMe CH
464 OCHzCF3 NMe2 N

465 Me 466 OMe Me N
467 Et 468 OMo OMe CH
469 CO-CHICH3~2 H 8-OMe OMe Me N
470 Mo 471 OMo OMe CH
472 C02Me H 8 0Me H OMe Me N
473 Me ~ ~ -474 Cl OMe CH

.

~lA~7~3 No. R ~ R2 R3 R~ X Y Z M.p.

475 CO2Me Et 6-OMa H Cl OMe CH
476 ' ~ OMa C!Me CH
477 " MB N
478 CO2Et H 6-OM~ H OMe OMe CH
479 Me N
480 ' Me 481 Et -482 OMe CH
483 CO2-i-Pr H . . CH
484 Me 485 CHO H 6-OEt H OMe OMe CH

486 Me 487 CHO Et 6-OEt H OMe OMe CH
488 CO-CH3 H OMe CH3 N
489 Cl OMe CH
490 Ms 492 Et OCH3 OCH3 CH
_ ~ ,~ .. . . . . .
493 ~,v-CH2vH3 n 494 Me 495 Et 496 CO-CHICH3)2 H
497 Me 498 CO2Me Me ~ ~ ~
499 CHO Me 6-CO2Me H Cl OMe CH
500 ' Et - 21~47`69 No. Rl Rl R3 R~ X Y z M.p.

501 ' ' ' OMs OMe CH
502 ~ Mo M~ CH
OMg Me N
504 ' nPr ' ' ' 505 ' ' OMs CH
506 CO-CH3 MB 6-CO2Mo H OM~ OMe CH
507 ' ' ' OMs Ms N
508 ' Ms Ms CH
509 ' Et ' ' OMs OMe CH
510 ' ' OMo Me N

511 CO-CH3 Et 6-CO2M8 H Ms Me CH
512 ' ' ' ' OMe Cl CH
513 Pr ~ ' OMs OMo CH
514 CO-CH2CH3 ~ MB Me CH
515 ' OMo Cl CH
516 ' Me ' OMe Me N
517 ~ ' Cl OMs CH
518 ' Me Me CH
519 Et 520 ' ' OMe Me N

521 n-Pr OMe OMs CH
522 CO-c-Pr MB 6-CO2Ms H OMs Me N
523 CO-c-Pr MB 6CO2Me H OMe Cl CH
524 ' Me Me CH
525 Et 526 ' ' ' OMo Cl 527 ' ' ' OMo Ms N
528 COCF3 H 6-CO2Me H OMe Me CH
529 ' ' ' Cl OMe CH

- 214~76~
~ 54 --No. pl R2 R3 R~ X Y Z M.p.

530 Et 531 OMe OMe 532 ' Me N
S33 ' ' Mo Me CH
534 CO-CH2 0Me H 6-CO2Me H OMe OMe CH
535 CO-CH2-OMe H 6-CO2Me H OMe M~ N
536 ' ' OMe Cl CH

537 ~ Mo Me CH
538 Me ' ' 539 OMe OMe 540 . . OMc M- N
541 ' Et 542 ~ OMo OMe CH
543 CO-CH2Br H 6 CO2M~

545 Et 546 CO-CHCI2 H 6-CO2Me 90-93 547 CO-CHCI2 Me 6-CO2Me H OMo OMe CH

548 Et 549 CO-CCI3 H ~ .
550 Me 551 Et ' -552 CO2M~ H 6-CO2Me H OMe Me N
553 Cl OM- CH
554 M~
555 ' OM~ Me N
556 Me Me CH
557 Et H OMe OMe CH

558 Pr 559 CO2CH2CH2CI H 6 CO2Me H OMe Me N
560 ' Me Me CH
561 Cl OMe CH
562 ' Me OMe OMe CH
563 OM~ M~ N
564 ' OM- Cl CH
565 Et 21~4~

No. R ~ R2 R3 R~ X Y Z M.p.

566 OM8 OMe CH
567 CO2CH2CH3 H ~ . . N
568 OMe M~ N
569 M~ -570 Cl CH
571 CO2CH2CH3 Mo 6-C02M~ H OMe OMe CH
572 Et 573 . . . Me N
674 CO2CHICH3)2 H Cl OMe CH
575 M. M~ CH

577 ~ OMe OM~ -578 OM. M~ N
579 Et OM. CH
580 CO2CH2CCI3 H OM. Me N
581 ~ Me 582 ' M~ OMe OM8 CH

5E3 CO2CH2Ccl3 Et 6-CO2M8 H OMe OM8 CH
584 Et MO N
585 CO2CH2CH2OMc Me OM~ N
586 CONHEt H ' M8 N
587 ~ M8 MB CH
5a8 CONHEt Me ~ OMe OMe CH
589 CO-NHPr H ' OM~ M8 N
590 CSNHMe H ~ ' OMo OM8 CH 132-135 591 ' ' ' ' ' Me N

592 ' ' ' ' M~ M- CH
593 ' ' a OMe CH
594 CSNMe2 Me ' ' OMe OMe CH
595 CSNMs2 Me 6CO2Me H OMe M~ N
596 CHO H 6-C02Et H OMe OMe CH
597 ~ OM8 Cl CH
598 ' ' ' ' M8 M- CH
599 ' M.
600 ' ' M- OMe CH

~ 56 _ 2 14 4~ 6 3 No. R ~ R2 R3 R~ X Y Z M.p.

601 ~ OMe OMe CH
602 OMI~ Me N
603 Es OM~ OM~ CH
604 OMe Me N

606 OMe CH
607 CO-CH~ H 6 CO2Et H OM~ Cl CH
608 Me M~ . CH

609 Me OMe OMe CH
610 ' Et 611 CO2Me Me 612 Et 813 CO2Et Me 614 Et ' 615 CO2-CH(CH3)2 Me 616 CHO Me 6-l W OMe OM~ CH
617 Et -618 Mo OMe Me N
619 CHO Et 6-l H OMe Me N

620 H Me Me CH
621 Me ~
622 Et 623 H Cl OMe CH
624 Me 625 Et 626 CO-CH3 H OMe OMe CH
627 ~ ~ OMe Me N
628 Me 629 OMe OMe CH

630 Et 631 C02Mo Me 6-l H OMe OMe CH
632 Et -633 CS-NHMe H H H OMe OMe CH
634 Me 635 Et ~
636 CS-NHEt Me - 21~6~

No. Rl R2 R3 R~ X Y ZM.p.

- 637 Et ' 638 CO-NHEt H H H
639 OMe Me N
640 Mo 641 OMs OMe CH
642 Et -643 CO NH-n Pr H H H OMe OMe CH
644 Me 645 Et ~ -646 CS-NHMe H 6-CI H OMe OMe CH
647 Me 648 Et 649 CS-NHEt Me 650 C0-NHEt H 6-CI H
651 H H OMe Me N
652 Me 653 Me OMe CH
6S4 Et 655 Co NH n-Pr H 6-CI H OMe OMe CH
6S6 Me 657 CS-NHMe H 6-OMe 658 ' Me 659 Me OMe N
660 CS-NHEt H 6-OMe - OMrs OMe CH
661 ~ Me 662 C0-NHEt H
663 Me 58 21g~769 Table 2 ~ 5 2 R H--C O --N ~Z

R1 ~oR2 )~

No. Rl R2 R3 R~ X Y Z M.p.

2-l COCH3 H H H 0Me OMe CH
2-2 ' Me OMe N
2-3 Me M~ aH
24 M~ OMe OMe CH

2-7 OMe Me N

2-8 CHO Me H H OMe Me N
2-9 ' H Me OMe Me N
2-10 COCH2CH3 H ' H OMe OMe CH 161 2-11 CO c-Pr H ' ' ' ' 154 2-12 COCF~ ' ' ' ' ' ' 158 2-13 ' M- M- OMe N

2-1~ ' H M- CH
215 OM- a 2-16 COCF3 H H H OMe Me N
2-17 CO2Me OM- OMo CH

2-19 CONHPr OMe CH

REPT ~ T SHEET

- 214~7~3 ~ 59 ~
No. Rl R2 R3 R~ X Y Z M.p.

2-20 CONHEt -2 21 CO2Me H ~CI H OMe OMe CH
2-22 Me 2-23 Me OMe OMe N
2-24 CHO Me CH

2-26 SO2Me H H H OMe OMo CH
2-27 SO2NHMIl H H H
2-28 NM~2 OCH2CF, N

2-2g 502NMo2 H . OM- OMe CH
2-30 Mc 2 31 CO2Me H 5-COIMe H OM- OM- CH
2-32 COCH~ H
2-33 CocH~ H 6-CF3 2-34 COCH~ M~ 5-CF~ H OMo OMe CH

2-36 Me 2 37 COCH3 H 5-F H OMe OM~ CH
2-38 COCH3 . Me 2-39 COCOOMe H H H 169-170 2-40 COCH~ Mc H H OM- Me N
2-41 a OMc CH
2-42 Et H H OM- OMc CH
2-43 ' OMe Mc N
2-44 CHO M- H H OMe OMc CH

REPLACEMENT SEIEET

~ 60 _ 21~7~3 No. Rl R2 R3 R~ x Y Z M.p.

2~5 ' Me Mo CH
246 '' Cl OMo CH
2-47 Et OMe OMe CH
2~8 '' Me N
2~9 CO-CH2CH3 H . OMe Mo N
2-50 Mo Me CH
2-51 Me -2-52 ~ ~ . OMe OMe CH
2-53 OMe Me N

2-54 ~ Cl OMe CH
2-55 Et OMe OMe CH
2-56 CO-CH2CH3 Et H H OMo Me N
2-57 COCF3 Me H
2-58 ' ' ' OMe OMe CH
2-59 Et 2-60 CO ~ H OMe Me N

2-61 Me 2-62 Me OMo CH
2-63 Et 2-64 CO2Me Me 2-65 Mo N
2-66 Et 2-67 CO2Me Et H H OMa OM~ CH

REPT ~r~M~NT SHEET

~ 61 - 214~763 No. Rl R2 R~ R~ X Y Z M.p 2~8 CONHEt H H H OMe OMo CH
2-69 ~ M- N
2-70 CONHEt Me 2 71 OMo OMo CH
2-72 CSNHMo H
2-73 ' ' ' ' OMo Me N
2-74 Me 2-75 ' ~ ' OMe OMo CH
2-78 CSNMe2 2-77 CSNHEt H
2-78 ~ Mo N
2-79 CSNHEt Me H H OMe OMe CH
2 80 CSNEt2 Et 2 81 COOCH2CH2CI H H OMo OMe CH
2-82 ' ' ' ' Cl CH
2-83 ' ' ' Me Me CH

2-84 ' Me ' OMe OMe CH
2-85 COOEt H H OMe OMe CH
2-86 ' ' ' Cl CH
2-87 COOiPr ' ' 2-88 ' OMe OMe 2~89 COOCH2CCI3 2-90 COOCH2CH2CI Mo H OMo Mo N

REPT.~r~M~NT SHEET

214~1763 Table 3 oR2 ~ 5 o ~ N H C O ~ R --~N~( No. Rl R2 R3 R~' X Y Z M.p.

3-1 CO-H H 2-CI H OMe Me N
3-2 COCH3 H 2-CI H OMo OMo CH

3-5 CO-c-Pr H 2-CI H
3-6 COCF3 H 2-CI H ~
3-7 CO2Me H 2-CI H ~ ~
3-8 Co2MB Me 2-CI H OMo OMo CH

3-9 CO2Me H 2-CO2Me H ~ -3-10 CO2Me H H Mo N
3-11 CO~-i-Pr H H ~ OM~ CH
3-12 CONHEt H ' H OMo CH
3-13 CONHPr H

3 14 CSNHEt ~

3-17 CO2Me Me 2-CO2Me H OMe OMo CH
31a ~ Me N

REPLACEMENT SHEET

-- 63 _ ~ 21 ~ 4 76 9 No. R~ R2 R3 R~ x Y Z M.p.

3 19 CO2Me Et 2-CO2Me H OM- Me N
3 20 ' ' ~ ~ ' OMs CH
3-21 CO2Et 3-22 ' Me 3-23 CHO H ' ' 3-24 ' Me ' ' ' 3-25 ' Et 3-26 ' H ' ' ' Me N
3-27 Me 3 28 ~ Et 3-30 ~ Me 3-31 CO CH3 Me 2CO2Me H OMe Me N
3-32 ~ H ~ ' OMe CH

3 33 ~ Me 3-34 ~ E~ ' ' ' 3-35 CO-OMe H 2-COOMe H Ma Me CH
3 36 COOMe H 2-COOMe H OMe Cl CH
3-37 COOMe Ms 2-COOMe H Me Me CH
3-38 COOMe Me 2-COOMe H OMe Cl CH

.

REPT ~CFMF NT SHEET

21447~9 -- 64 ~

No. Rl R2 R3 R~ x Y Z M.p.

3-39 COOEt H ' OMo OMe 3,40 ~ OMe Cl 341 ~ Me N
3-42 Me ' OMe M~ N
3-43 CHO Me ' OMe Cl CH

Ms M~ CH
3 45 COCH3 H . Cl OMs CH
3-46 ' M~ Me CH

REPLACEMENT SEIEET

21447~

Ta}: le 4 oR2 R3 R 1 _ N ~[~( S2N - CO - NR 4 ~
N
~ Y

No. Rl R2 R3 ~ M X Y Z M.p.

4-1 CHO H 2-COOMIl H N~ OMe OM~ CH
4-2 CHO H ' K ' ' 4-3 ' ~ ' N~ OM~ M~ N
4 4 ' M~ ' N~
4-5 OM~I CH

M~ N

4-8 ' M~
4-9 ' ' ' ' OM- CH
410 COOM- H ' 175 180 4-11 M~ N
4-12 M~ ' ~ -4-13 ' ' ' CH

REPr ~ NT S~EET

- 21~769 - 66 -B. Formulation Examples a) A dust is obtained by mixing 10 parts by weight of a compound of the formula (I) and 90 parts by weight of talc as inert substance and comminuting the mixture in a hammer mill.

b) A wettable powder which is readily dispersible in water is obtained by mixing 25 parts by weight of a compound of the formula (I), 64 parts by weight of kaolin-contAin;ng quartz as inert substance, 10 parts by weight of potassium ligninsulfonate and 1 part by weight of sodium oleoylmethyltaurinate as wetting agent and dispersant, and grinding the mixture in a pinned-disk mill.

c) A dispersion concentrate which is readily dispers-ible in water is obtained by mixing 20 parts by weight of a compound of the formula (I) with 6 parts by weight of alkylphenol polyglycol ether (-Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range for example approximately 255 to above 277C), and grinding the mixture in a ball mill to a fineness of below 5 microns.

d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I), 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol as emulsifier.

e) Water-dispersible granules are obtained by mixing 75 parts by weight of a compound of the formula (I), 10 " of ~calcium ligninsulfonate, 5 ~ of sodium lauryl sulfate, 3 ~ of polyvinyl alcohol and - 21~4769 7 " of kaolin, grinding the mixture on a pinned-disk mill, and granulating the powder in a fluidized bed by spray-ing on water as granulation liquid.

f) Water-dispersible granules are also obtained by homogenizing and precomminuting 25 parts by weight of a compound of the formula (I), " of sodium 2,2'-dinaphthyl-methane-6,6'-disulfonate, 2 " of sodium oleoylmethyltaurinate, 1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate and 50 " of water on a colloid mill, subsequently grinding the mixture on a bead mill, and atomizing and drying the result-ing suspension in a spray tower by means of a single-substance nozzle.

C. Biological Examples 1. Pre-emergence effect on weeds Seeds or rhizome pieces of monocotyledon and dicotyledon weed plants were placed in sandy loam soil in plastic pots and covered with soil. The compounds according to the invention which were formulated in the form of wettable powders or emulsion concentrates were then applied to the surface of the soil, in the form of aqueous suspensions or emulsions at an application rate of 600 to 800 l/ha (converted), in various dosages.

After the treatment, the pots were placed in a greenhouse and kept under good growth conditions for the weeds.
After the test plants had emerged, the damage to the plants or the negative effect on the emergence was scored - 21~7~

visually after a test period of 3 to 4 weeks by compari-son with untreated controls. A~ shown by the test results, the compounds according to the invention have a good herbicidal pre-emergence activity against a broad range of grass weeds and broad-leaved weeds. For example, the compounds of Examples 61, 192, 217, 238, 256 and 262 of Table 1, 3-9 and 3-29 of Table 3 and 4-9 of Table 4 have a very good herbicidal activity against noxious plants, such as Sinapis alba, Chrysanthemum segetum, Avena sativa, Stellaria media, Echinochloa crus-galli and Lolium multiflorum when applied pre-emergence at an application rate of 0.3 kg and less of active ingredient per hectare.

2. Post-emergence effect on weeds Seeds or rhizome pieces of monocotyledon and dicotyledon weeds were placed in sandy loam soil in plastic pots, covered with soil and grown in a greenhouse under good growth conditions. Three weeks after sowing, the test plants were treated in the three-leaf stage.

The compounds according to the invention which were formulated as wettable powders or as emulsion concen-trates were sprayed in various dosages onto the green parts of the plants at an application rate of 600 to 800 l/ha (converted) and, after the test plants had remained in the greenhouse for approx;~ately 3 to 4 weeks under ideal growth conditions, the effect of the prepara-tions was scored visually by comparison with untreated controls. The compositions according to the invention also have a good herbicidal post-emergence activity against a broad range of economically important grass weeds and broacl-leaved weeds. For example, the compounds of Examples 61, 192, 217, 238, 256 and 262 of Table 1, 3-9 and 3-29 of Table 3 and 4-9 of Table 4 have a very . .
good herbicidal activity against noxious plants such as Sinapis alba, Stellaria media, Echinochloa crus-galli, Lolium multlflorum, ChrysanthPmllm segetum and Avena 21~ 76~

sativa when applied post-emergence at an application rate of 0.3 kg and less of active ingredient per hectare.

- 3. Tolerance by crop plants In further greenhouse experiments, seeds of a substantial number of crop plants and weeds were placed in sandy loam soil and covered with soil. Some of the pots were treated immediately as described in Section 1, and the remaining pots were placed in a greenhouse until the plants had developed two to three true leaves and were then sprayed with various dosages of the substances of the formula (I) according to the invention as described in Section 2.
Visual scoring four to five weeks after the application and after the plant had been in the greenhouse revealed that the compounds according to the invention did not inflict any damage to dicotyledon crops such as, for example, soya, cotton, oilseed rape, sugar beet and potatoes when used pre- and post-emergence, even when high dosages of active substance were used. Some of the substances also left Gramineae crops such as, for example, barley, wheat, rye, sorghum species, maize or rice particularly unharmed.
The compounds of the formula (I) therefore have a high selectivity when used for controlling undesired vegeta-tion in agricultural crops.

Claims (12)

Patent claims:

1. A compound of the formula (I) or a salt thereof, (I) in which R1 is CO-R5, CO-OR6, CO-NR7R8, CS-R9, CS-OR10, CS-NR7R8, SO2R11, SOR11, SO2NR7R8 or CO-CORl2, R2 is hydrogen, C1-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl, the last-mentioned 3 radicals independ-ently of one another being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, C1-C4-alkoxy and C1-C4-alkylthio, R3 is halogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C2-C6-alkenyloxy or C2-C6-alkynyloxy, the last-mentioned 6 radicals inde-pendently of one another being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, C1-C4-alkoxy and alkylthio, or is CO-CO-Rl6, CS-Rl6, CO-CO-OR17, CS-OR17, CS-SR17, CO-NR18R19, CS-NR18R19, NR18R19, SO2NR18R19, cyano, S(O)o-R20, CO-Rl6, CO-OR17, NO2 or C(R22)=N-R22 or a 5- or 6-membered saturated, unsaturated or heteroaromatic heterocycle having up to 4 hetero-atoms selected from the group comprising N, O
and S, which is unsubstituted or substituted by one or more radicals selected from the group comprising halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl, CN, NO2, CHO, (C1-C4-alkyl)-carbonyl and (C1-C4-alkoxy)-carbonyl and in which up to 2 carbon ring positions can be replaced by CO and up to two sulfur atoms in the hetero ring can be replaced by SO2, R4 is hydrogen or C1-C4-alkyl, R5 is hydrogen or C1-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl, the last-mentioned 3 radicals being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, C1-C4-alkoxy, C1-C4-alkylthio, NR13R14 and NR152, or is C3-C7-cycloalkyl which is unsubstituted or substituted by one or more radicals selected from the group comprising halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, NR13R14 and NR152, or is benzyl, unsubstituted or substituted aryl or an unsubstituted or substituted heterocyclic radical, R6 is C1-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl, the last-mentioned 3 radicals being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, C1-C4-alkoxy, C1-C4-alkylthio, NR13R14 and NR152, R7 is hydrogen or C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl or C1-C6-alkoxy, the last-mentioned 4 radicals being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, C1-C4-alkoxy, C1-C4-alkylthio and NR13R14, R8 is hydrogen or C1-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl, the last-mentioned 3 radicals being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, C1-C4-alkoxy and C1-C4-alkylthio, or is COR23, CO2R24, CONR13R14 or SO2R11, R9 is analogous to R5, R10 is analogous to R6, R11 is C1-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl, the last-mentioned 3 radicals being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, C1-C4-alkoxy and C1-C4-alkylthio, R12 is hydrogen, OH, NH2, mono- or di(C1-C4-alkyl)-amino, C1-C4-alkyl or C1-C4-alkoxy, the last-mentioned 2 radicals being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, C1-C4-alkoxy and C1-C4-alkylthio, the R13 radicals independently of one another are hydrogen or C1-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl, the last-mentioned 3 radicals being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, C1-C4-alkoxy and C1-C4-alkylthio, or are COR25 or CO2R26, the R14 radicals independently of one another are hydrogen or C1-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl, the last-mentioned 3 radicals being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, C1-C4-alkoxy and C1-C4-alkylthio, NRl52 radicals independently of one another are a heterocyclic 3- to 7-membered ring which can contain, besides the nitrogen atom, one or two further hetero ring atoms selected from the group comprising N, O and S and which is unsubstituted or substituted, R16 is a radical analogous to R5, R17 is hydrogen, C1-C6-alkyl, C1-C6-alkenyl or C2-C6-alkynyl, the last-mentioned 3 radicals being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, C1-C4-alkoxy, C1-C4-alkyl-thio, NR13R14 and NR152, R18 is a radical analogous to R7, R19 is a radical analogous to R8, R20 is a radical analogous to R11, R21 is hydrogen or C1-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl, the last-mentioned 3 radicals being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, C1-C4-alkoxy and C1-C4-alkylthio, or is C1-C4-alkoxy, OH, NH2, mono- or di(C1-C4-alkyl)amino, CO-R16, CO2-R17 or SO2-R20, R22 is hydrogen, OH, NH2, mono- or di(C1-C4-alkyl)-amino, C1-C4-alkyl or C1-C4-alkoxy, the last-mentioned 2 radicals being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, C1-C4-alkoxy and C1-C4-alkylthio, R23 is a radical analogous to R9, R24 is a radical analogous to R10, R25 is a radical analogous to R9, R26 is a radical analogous to R10, X and Y independently of one another are hydrogen, halogen, C1-C6-alkyl, C1-C6-alkoxy or C1-C6-alkyl-thio, the last-mentioned 3 radicals being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, C1-C4-alkoxy and C1-C4-alkylthio, or are mono- or di(C1-C4-alkyl)amino, C3-C6-cycloalkyl, C3-C5-alkenyl, C3-C6-alkynyl, C3-C5-alkenyloxy or C3-C5-alkynyloxy, Z is CH or N, W is O or S, n is 0, 1, 2 or 3 and o is 0, 1, 2 or 3.

2. A compound of the formula (I) or a salt thereof as claimed in claim 1, wherein R1 is CO-R5, CO-OR6, CO-NR7R8, CS-R9, CS-NR7R8, SO2R11, SO2NR7R8 or CO-CORl2 or R2 is hydrogen, C1-C6-alkyl, C3-C5-alkenyl or C3-C5-alkynyl, the last-mentioned 3 radicals independ-ently of one another being unsubstituted or substituted by one or more halogen atoms or by one or two radicals selected from the group comprising C1-C4-alkoxy and C1-C4-alkylthio, or R3 is halogen, C1-C4-alkyl, C2-C5-alkenyl, C2-C5-alkynyl, C1-C4-alkoxy, C3-C5-alkenyloxy or C3-C5-alkynyloxy, the last-mentioned 6 radicals inde-pendently of one another being unsubstituted or substituted by one or more halogen atoms or by one or two radicals selected from the group comprising C1-C4-alkoxy and alkylthio, or is CO-CO-R16, CO-CO-ORl7, CO-NR18R19, NR18R19, SO2NR18R19, cyano, S(O)o-R20, CO-Rl6, CO-ORl7, NO2 or C(R21)=N-R22 or is a 5- or 6-membered saturated, unsaturated or heteroaromatic heterocycle having up to 3 hetero atoms selected from the group comprising N, O
and S, which is unsubstituted or substituted by one or more radicals selected from the group comprising halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl, CN, NO2, CHO, (C1-C4-alkyl)carbonyl, and (C1-C4-alkoxy)carbonyl, and in which up to 2 carbon ring positions can be replaced by CO and up to two sulfur atoms in the hetero ring can be replaced by SO2, R4 is hydrogen or methyl, R5 is hydrogen or C1-C6-alkyl which is unsubstituted or substituted by one or more halogen atoms or by one or two radicals selected from the group comprising C1-C4-alkoxy, C1-C4-alkylthio, NR13R14 and NR152, or is C3-C7-cycloalkyl, benzyl, unsub-stituted or substituted aryl or unsubstituted or substituted heteroaryl, R6 is C1-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl, the last-mentioned 3 radicals being unsubstituted or substituted by one or more halogen atoms or by one or two radicals selected from the group comprising C1-C4-alkoxy, C1-C4-alkylthio, NR13R14 and NR152, or R7 is hydrogen or C1-C6-alkyl which is unsubstituted or substituted by one or more halogen atoms or by one or two radicals selected from the group comprising C1-C4-alkoxy, C1-C4-alkylthio and NR13R14, or R8 is hydrogen or C1-C4-alkyl which is unsubstituted or substituted by one or more halogen atoms or by one or two radicals selected from the group comprising C1-C4-alkoxy and C1-C4-alkylthio, or is COR23, CO2R24 or SO2R11, or R9 is a radical analogous to R5 or R10 is a radical analogous to R6 or R11 is C1-C4-alkyl or C1-C4-haloalkyl, or R12 is hydrogen, OH, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-haloalkyl or the R13 radicals independently of one another are hydrogen or C1-C4-alkyl, COR25 or CO2R26 or the R14 radicals independently of one another are hydrogen or C1-C4-alkyl or NR152 radicals independently of one another are a heterocyclic 3- to 7-membered ring which can contain, besides the nitrogen atom, a further hetero ring atom selected from the group comprising N, O and S and which is unsubstituted or substituted by one or more radicals selected from the group comprising C1-C4-alkyl and oxo or R16 is a radical analogous to R5, R17 is hydrogen, C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, the last-mentioned 3 radicals being unsubstituted or substituted by one or more halogen atoms or by one or two radicals selected from the group comprising C1-C4-alkoxy, C1-C4-alkylthio, NR13R14 and NR152, R18 is a radical analogous to R7, R19 is a radical analogous to R8, R20 is a radical analogous to R11, or R21 is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl,C1-C4-alkoxy, OH, NH2, mono- or di-(C1-C4-alkyl)-amino or R22 is hydrogen, OH, NH2, mono- or di(C1-C4-alkyl)-amino, C1-C4-alkyl or C1-C4-alkoxy or R23 is a radical analogous to R9, R24 is a radical analogous to R10, R25 is a radical analogous to R9, R26 is a radical analogous to R10 or X and Y independently of one another are hydrogen, halogen, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkyl-thio, the last-mentioned 3 radicals being unsub-stituted or substituted by one or more halogen atoms, or are mono- or di(C1-C2-alkyl)amino or n is 0, 1 or 2 or o is 0, 1 or 2, or in which two or more of the abovementioned meanings of the general radicals or indices R1 to o in formula (I) are combined.

3. A compound of the formula (I) or a salt thereof as claimed in claim 1 or 2, wherein R1 is COR5, CO2R6, CO-NR7R8, CO-CO-R12, CS-NR7R8, SO2R11 or SO2-NR7R8 or R2 is hydrogen or C1-C4-alkyl or R5 is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, such as CF3, cyclopropyl, cyclopentyl, cyclohexyl, benzyl, phenyl which is unsubstituted or substituted by 1 to 3 radicals selected from the group comprising halogen, methyl and methoxy, or is thienyl, furyl or pyridyl, the above hetero-aromatic radicals being unsubstituted or substituted by one or more radicals selected from the group comprising halogen, C1-C4-alkyl and C1-C4-alkoxy, or R6 is C1-C4-alkyl, C1-C4-haloalkyl, C3-C4-alkenyl or C3-C4-alkynyl, R7 is H, C1-C4-alkyl or C1-C4-haloalkyl or R8 is H, C1-C4-alkyl, COCH3, CO2CH3 or CO2C2H5, or which contain a combination of the abovementioned preferred radicals.

4. A compound of the formula (I) or a salt thereof as claimed in any one of claims 1 to 3, wherein the group of the formula N(OR2)R1 is in the 2-, 3-, 5- or 6-position on the phenyl ring and n is 0 or 1.

5. A compound of the formula (I) or a salt thereof as claimed in one of claims 1 to 4, wherein R3 is a radical of the formula CO-OR17 and n is 1.

6. A process for the preparation of a compound of the formula (I) or a salt thereof as claimed in claim 1, which comprises a) reacting a compound of the formula (II) (II) with a heterocyclic carbamate of the formula (III) (III) in which R* is optionally substituted phenyl or (C1-C4)alkyl, or b) with the proviso that R2 is other than hydrogen, reacting a sulfonyl isocyanate of the formula (IV) (IV) with an amino heterocycle of the formula (V) (V) or c) reacting a compound of the formula (II) with a (thio)isocyanate of the formula (X) (X) in the presence of a base, where in formulae (II) - (V) and (X) the radicals R1 to R4 and n are as defined in formula (I) and in process variants a) and b) compounds of the formula (I) are initially obtained in which W
is 0.

7. A herbicidal or plant-growth-regulating composition, which comprises at least one compound of the formula (I) or a salt thereof as claimed in any one of claims 1 to 5 and formulation auxiliaries conven-tionally used in crop protection.

8. Method of controlling noxious plants or for regulat-ing the growth of plants, which comprises applying an effective amount of at least one compound of the formula (I) or a salt thereof as claimed in any one of claims 1 to 5 to the noxious plants or to plants, their seeds or the area under cultivation.

9. The use of a compound of the formula (I) or a salt thereof as claimed in any one of claims 1 to 5 as a herbicide or plant growth regulator.

New Claim 10

10. A compound of the formula (II) (II) in which R1, R2, R3 and n are as defined in formula (I) as claimed in any one of claims 1 to 5, with the exception of 4-(N-acetyl-N-hydroxy-amino)-benzenesulfonamide and 4-(N-acetyl-N-methoxy-amino)-benzenesulfonamide.

11. A process for the preparation of a compound of the formula (II) as claimed in claim 10, which comprises a) reacting compounds of the formula (VI) (VI) in which R1, R2, R3 and n are as defined in formula (II), with a strong acid, or b) subjecting compounds of the formula (IXb) (IXb) in which R1, R2, R3 and n are as defined on formula (II) to aminolysis.

12. A compound of the formula (IV) (IV) in which R1, R2, R3 and n are as defined in any one of claims 1 to 5.