CA2204610A1 - N-acyl-n-alkylaminophenylsulfonylureas with sulfur substituents, processes for their preparation and their use as herbicides and plant growth regulators - Google Patents
N-acyl-n-alkylaminophenylsulfonylureas with sulfur substituents, processes for their preparation and their use as herbicides and plant growth regulatorsInfo
- Publication number
- CA2204610A1 CA2204610A1 CA 2204610 CA2204610A CA2204610A1 CA 2204610 A1 CA2204610 A1 CA 2204610A1 CA 2204610 CA2204610 CA 2204610 CA 2204610 A CA2204610 A CA 2204610A CA 2204610 A1 CA2204610 A1 CA 2204610A1
- Authority
- CA
- Canada
- Prior art keywords
- alkyl
- alkoxy
- haloalkyl
- ome
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D521/00—Heterocyclic compounds containing unspecified hetero rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
Abstract
N-acyl-N-alkylamino phenyl sulphonyl ureas with sulphur substituents, process for their production and use as herbicides and plant growth regulators.
Compounds of formula (I) and thier salts, in which R1, R2, R3, R4, R5, X, Y, Z, W, n and m as defined in claim 1 are suitable as herbicides and plant growth regulators. They are produced by prior-art-like methods, partially with the use of novel intermediate products of the formula (XIX) in which U*=NH2, Cl, (substituted) amino and R1 to R4, n and m are defined as in formula (I).
Compounds of formula (I) and thier salts, in which R1, R2, R3, R4, R5, X, Y, Z, W, n and m as defined in claim 1 are suitable as herbicides and plant growth regulators. They are produced by prior-art-like methods, partially with the use of novel intermediate products of the formula (XIX) in which U*=NH2, Cl, (substituted) amino and R1 to R4, n and m are defined as in formula (I).
Description
~ CA 02204610 1997-0~-06 .; ~
- WO 96/14304 ~ ~ ~~~~ PCT/~P95/04183 .
Description N-Acyl-N-alkylaminophenylsulfonylureas with sulfur substituents, processes for their preparation and their use as herbicides and plant growth regulators.
The invention relates to the technical field of herbicides and plant growth regulators, in particular herbicides for selective control of broad-leaved weeds and graminaceous weeds in crops of useful plants.
It is known that phenylsulfonylureas which have heterocyclic substituents and carry an amino or a func-tionalized amino group or a sulfur substituent on the phenyl ring have herbicidal and plant growth-regulating properties (EP-A-1515; EP-A-7687; EP-A-30138; US-A-4,892,946; US-A-4,981,509, US-A-4,664,695; US-A-4,632,695, EP-A-116518; EP-A-23142 (= US-A-4,310,346);
US-A-4,369,058; EP-A-84020; EP-A-192489; DE 42 36 902 Al).
Surprisingly, it has now been found that certain phenyl-sulfonylureas with heterocyclic substituents are particu-larly suitable as herbicides and plant growth regulators.
The present invention relates to compounds of the for-mula (I) and salts thereof \ ~S0 -NH-C-NRs ~(~ ( I ) in which W is an oxygen or sulfur atom, preferably O, CA 02204610 1997-0~-06 m is 0, 1, 2 or 3, n is 0, 1 or 2, R1 is hydroxyl, amino, mono- or disubstituted amino, hydroxylamino, substituted hydroxylamino, hydrazino, substituted hydrazino, an aliphatic hydrocarbon or hydrocarbonoxy radical, aryl, heteroaryl, aryloxy or heteroaryloxy, where each of the last 6 radicals mentioned is unsubstituted or substituted, R2 is halogen, CN, NO2, amino, mono- or disubstituted amino, alkyl or alkoxy, where each of the last two radicals mentioned is unsubstituted or substituted, R3 is an aliphatic hydrocarbon radical, which is un-substituted or substituted, preferably having a total of 1 to 12 carbon atoms, R4 is an acyl radical, R5 is hydrogen, hydroxyl, (Cl-C~)alkyl, (C1-C~)alkoxy, (C2-C4)alkenyl or (C2-C4)alkynyl, where each of the last 4 radicals mentioned is unsubstituted or sub-stituted by halogen, preferably F, Cl or Br, X and Y independently of one another are hydrogen, hydroxyl, amino, mono- or disubstituted amino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy or alkylthio, where each of the last 9 radicals mentioned is unsubstituted or substituted, and Z is CH, N or C - R ~ ~, in which R~ is halogen, /
cyano, alkyl, alkoxy, haloalkyl or haloalkoxy.
In formula (I) and all the formulae below, the alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio radicals and the correspo~ing unsaturated and/or substi-tuted radicals can in each case be straight-chain or branched in the carbon skeleton. Unless specifically ~tated, the lower carbon skeletons, for example having 1 to 6 carbon atoms, or in the case of unsaturated groups having 2 to 6 carbon atoms, are preferred for these CA 02204610 1997-0~-06 , radicals. Alkyl radicals, including in the composite me~n;ngs, such as alkoxy, haloalkyl and the like, are, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyl radicals, hexyl radicals, such as n-hexyl, i-hexyl and 1,3-dimethylbutyl, or heptyl radicals, such as n-heptyl, l-methylhexyl and 1,4-dimethylpentyl;
alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals correspo~ing to the alkyl radicals; alkenyl is, for example, allyl, 1-methylprop-2-en-l-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methyl-but-3-en-1-yl and 1-methyl-but-2-en-1-yl; and alkynyl is, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl and 1-methyl-but-3-yn-1-yl.
Halogen is, for example, fluorine, chlorine, bromine or iodine. Haloalkyl, -alkenyl and -alkynyl are alkyl, alkenyl or alkynyl respectively which are partly or completely substituted by halogen, preferably by fluor-ine, chlorine and/or bromine, in particular by fluorine or chlorine, for example CF3, CHF2, CH2F, CF3CF2, CH2FCHCl, CCl3, CHCl2 and CH2CH2Cl; haloalkoxy is, for example, OCF3, OCHF2, OCH2F, CF3CF2O, OCH2CF3 and OCH2CH2Cl; the correspo~;ng definition applies to haloalkenyl and other radicals substituted by halogen.
A hydrocarbon radical iB a straight-chain, branched or cyclic, saturated or unsaturated aliphatic or aromatic hydrocarbon radical, for example alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or aryl; aryl here is a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, penta-lenyl, fluorenyl and the like, preferably phenyl; a hydrocarbon radical i~ preferably alkyl, alkenyl or alkynyl having up to 12 carbon atoms or cycloalkyl having 3, 4, 5, 6 or 7 ring atoms or phenyl;
the corresponding definition applies to a hydrocarbon radical in a hydrocarbonoxy radical.
A heterocyclic radical or ring (heterocyclyl) can be CA 02204610 1997-0~-06 saturated, unsaturated or heteroaromatic; it preferably contains one or more hetero units in the ring, preferably from the group consisting of N, 0, S, S0 and S02; prefer-ably, it is an aliphatic heterocyclyl radical having 3 to 7 ring atoms or a heteroaromatic radical having 5 or 6 ring atoms and contains 1, 2 or 3 hetero units. The heterocyclic radical can be, for example, a hetero-aromatic radical or ring (heteroaryl), such as, for example, a mono-, bi- or polycyclic aromatic system in which at least 1 ring contains one or more hetero atoms, for example pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, thienyl, thiazolyl, oxazolyl, furyl, pyrrolyl, pyrazolyl and imidazolyl, or is a partly hydrogenated radical, such as oxiranyl, pyrrolidyl, piperidyl, piperazinyl, dioxo-lanyl, morpholinyl or tetrahydrofuryl. Possible sub-stituents for a substituted heterocyclic radical are the substituents mentioned below, and in addition also oxo.
The oxo group can alQo occur on the hetero ring atoms which can exi~t in different oxidation states, for example in the case of N and S.
Substituted radicals, such as substituted hydrocarbon radicals, for example substituted alkyl, alkenyl, al-kynyl, aryl, phenyl and benzyl, or substituted hetero-cyclyl or heteroaryl, are, for example, a substituted radical derived from the unsubstituted parent substance, the substituents being, for example, one or more, prefer-ably 1, 2 or 3, radicals from the group consisting of halogen, alkoxy, halo~lkoxy, alkylthio, hydroxyl, amino, nitro, carboxyl, cyano, azido, alkoxycarbonyl, alkyl-carbonyl, formyl, carbamoyl, mono- and dialkylamino-carbonyl, substituted amino, such as acylamino and mono-and dialkylamino, and alkyl~ulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and, in the case of cyclic radicals, also alkyl and haloalkyl, as well as the unsaturated aliphatic radicals correspo~;ng to the saturated hydrocarbon-containing radical 8 mentioned, such as alkenyl, alkynyl, alkenyloxy, alkynyloxy and the like.
In the case of radicals with carbon atoms, those having CA 02204610 1997-0~-06 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, are preferred. Substituents from the group consisting of halogen, for example fluorine and chlorine, (Cl-C4)alkyl, preferably methyl or ethyl, (C1-C~)haloalkyl, preferably trifluoromethyl, (Cl-C4)alkoxy, preferably methoxy or ethoxy, (Cl-C~)haloalkoxy, nitro and cyano, are as a rule preferred. The substituents methyl, methoxy and chlorine are particularly preferred here.
Mono- or disubstituted amino is a chemically stable radical from the group consisting of substituted amino radicals which are N-subRtituted, for example, by one or two identical or different radicals from the group consisting of alkyl, alkoxy, acyl and aryl; preferably monoalkylamino, dialkylamino, acylamino, arylamino, N-alkyl-N-arylamino and N-heterocyclic radicals; alkyl radicals having 1 to 4 carbon atoms are preferred here;
aryl here is preferably phenyl or substituted phenyl; the definition given below applies here to acyl, preferably (Cl-C4)alkanoyl. A correspo~;ng definition applies to substituted hydroxylamino or hydrazino.
Optionally substituted phenyl is preferably phenyl which is unsubstituted or mono- or polysubstituted, preferably up to three times, by identical or different radicals from the group consisting of halogen, (Cl-C4)alkyl, (Cl-C4) alkoxy, (Cl-C4)haloalkyl, (Cl-C4)haloalkoxy and nitro, for example o-, m- and p-tolyl, dimethylphenyl radicals, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoro- and -trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl and o-, m- and p-methoxyphenyl.
An acyl radical is the radical of an organic acid, for example the radical of a carboxylic acid and radicals of acids derived therefrom, such as the thiocarboxylic acid, optionally N-substituted iminocarboxylic acids or the radical of carbonic acid monoesters, optionally N-substi-tuted carbamic acid, sulfonic acids, sulfinic acids,phosphonic acids and phosphinic acids. Acyl is, for CA 02204610 1997-0~-06 example, formyl, alkylcarbonyl, such as (Cl-C4-alkyl)-carbonyl, phenylcarbonyl, in which the phenyl ring can be substituted, for example as shown above for phenyl, or alkoxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, N-alkyl-1-iminoalkyl and other radicals of organic acids.
The above examples of general terms, such as alkyl, acyl, aryl, substituted radicals and the like, are not a complete list; in particular the terms also include me~n;ngs of the same type which are given below for the preferred compounds.
The invention also relates to all the stereoisomers included by the formula (I) and mixtures thereof. Such compounds of the formula (I) contain one or more asymmet-ric carbon atoms or al~o double bonds which are not shownseparately in the general formula (I). The possible stereoisomers defined by their ~pecific ~patial form, such as enantiomers, diastereomers and Z and E isomers, are all included by the formula (I) and can be obtained from mixtures of the stereoisomer6 by customary methods or also prepared by stereoselective reactions in combina-tion with the u~e of stereochemically pure starting substances.
The compounds of the formula (I) can form salt~ in which the hydrogen of the -SO2-NH- group is replaced by a cation ~uitable for agriculture. These salt~ are, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium ~alt~, or also ammonium salts or salts with organic amines.
Compounds of the formula (I) according to the invention or ~alts thereof which are of particular interest are those in which R1 is OH, NR6R7 (C1-C6)alkyl, (C2-C6)alkenyl, CA 02204610 1997-0~-06 (C2-C6)alkynyl, (Cl-C6)alkoxy, (C2-C6)alkenoxy, (C2-C6)alkynoxy, (C3-C7) cycloalkyl, (C3-C7) -cyclo-alkoxy, (C3-C7) cycloalkyl-(Cl-C2)alkyl, (C3-C7), cyclo-alkyl-(Cl-C2)alkoxy, phenoxy, phenyl, thienyl or pyridyl, where each of the last fourteen radicals mentioned i8 unsubstituted or substituted by one or more radicals from the group consisting of halogen, (Cl-C4)alkoxy, (Cl-C4)haloalkyl, (C2-C4)alkenoxy, (C2-C4)haloalkenoxy, (C2-C~)alkynoxy, (C2-C~)halo-alkynoxy, CN, NO2, N3, SCN, OCN, OH, NR3R9, CO-Rl~, (C1-C4)alkylthio, (Cl-C~)haloalkylthio, unsubstituted and substituted phenyl, SO-Rll and SO2Rl2, and in the case of cyclic radicals also (Cl-C4)alkyl and (Cl-C4)haloalkyl, R2 is halogen, (Cl-C3)alkyl, (Cl-C3)haloalkyl, (Cl-C5)-alkoxyalkyl, NO2, NRl3Rl4, CN, (Cl-C3) alkoxy or (Cl-C3)haloalkoxy, R3 is (Cl-C6)-alkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, (C3-C7) -cycloalkyl or (C3-C7) -cycloalkyl-(Cl-C2)alkyl, where each of the last five radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (Cl-C7)alkoxy, ( Cl- C4) haloalkoxy, ( C2- C4) alkenoxy, (C2-C4)haloalkenoxy, (C2-C4)alkynoxy, (C2-C4)halo-alkynoxy, (Cl-C~)alkylthio, (C2-C4)-haloalkylthio, (C2-C4)alkenylthio, (C2-C4)-haloalkenylthio, (C2-C4)-alkynylthio, (C2-C4)haloalkynylthio, CN, NO2, N3, SCN, OCN, OH, NRl5Rl6, SoRl7, SO Rl8 and CO Rl9 R4 i CO H CO R20 CO-OR2l, Co-NR22R23, Co-SR24, CS-R, CS-OR26, CS-NR27R23, CS-SR29, C(=NR30)R3l, SO2R32 or R5 is H, OH, (Cl-C3) alkyl, (C2-C3)alkenyl, (C2-C3)alkynyl or (Cl-C3)alkoxy, preferably H or (Cl-C4) alkyl, R6 is H, OH, NH2, mono- or di-[(Cl-C3)alkyl]amino, CA 02204610 1997-0~-06 (Cl-C~)alkyl, (C2-C4)alkenyl, (C2-C~)alkynyl, (Cl-C4)alkoxy, (C2-C4)alkenoxy or (C2-C~)alkynoxy, where each of the last eight radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (Cl-C3)alkoxy, (Cl- C3) haloalkoxy, (Cl-C 3) alkylthio and (Cl-C3)haloalkylthio, R7 H, (cl-c4)alkyl~ (c2-c4)alkenyl~ (C2-C~)alkynyl, [(Cl-C4)alkyl]-carbonyl, [(C2-C~)alkenyl]-carbonyl, [(C2-C~)alkynyl]-carbonyl, [(Cl-C~)alkoxy]-carbonyl, [(C2-C4)alkenoxy]-carbonyl, [(C2-C~)alkynyloxy]-carbonyl, [(Cl-C4)alkyl]-aminocarbonyl, di[(Cl-C4)-alkyl]amino-carbonyl, (Cl-C~)alkyl-sulfonyl, (C2-C4)-alkenyl-sulfonyl, (C2-C4)alkynylsulfonyl, (Cl-C4)-alkylaminosulfonyl or di-[(Cl- C4) alkyl]-aminosulfonyl, where each of the last sixteen rad-icals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, OH, (Cl-C3) alkoxy, (Cl-C3)halo~lkoxy, (Cl- C3) alkylthio and (Cl- C3) haloalkylthio, or NR6R7 together is a heterocyclic radical which, in addition to the N atom, can contain further hetero units from the group consisting of 0, N, S, SO and SO2 in the ring skeleton and which is unsubstituted or substituted by radicals from the group consisting of the oxo function, halogen, OH, NH2, NO2, NHCH3, N(CH3) 2~ CN, CONH2, CONHCH3, CO2CH3, CON(CH3) 2~ COCH3, CHO, (Cl-C3) alkyl, (Cl-C3)-haloalkyl, (Cl-C3)alkoxy and (Cl- C3) haloalkyl, R3 is H, (cl-c4)alkyl~ (cl-c4)haloalkyl~ (c2-c4)alken (C2-C4) haloalkenyl, (C2-C")alkynyl, (C2-C4) halo alkynyl, OH, (Cl-C3) alkoxy or (C2-C3)haloalkoxy and R9 is H, (Cl-C4) alkyl, (Cl-C4)haloalkyl, (C2-C4)alkenyl, (C2-C4) haloalkenyl, (C2-C4) alkynyl, (C2-C4) halo-alkynyl, CO-H, CO2CH3, CO2CH3, CO-CH3, CO-NH2, CO-NHCH3 CA 02204610 1997-0~-06 g or CON(CH3) 2~
or NRsR9 together iB a heterocyclic radical which, in addition to the N atom, can contain further hetero units from the group consisting of O, N, S, SO or So2 in the ring skeleton and is unsubstituted or substituted by one or more radicals from the group con~isting of halogen, OH, NH2, NO2, CONH2, CONHCH3, CON(CH3) 2~ NHCH3, N(CH3) 2~ CN, CQ2CH3, COCH3, CO-H, (Cl-C3)alkyl, (Cl-C3)haloalkyl, (Cl-C3)alkoxy, (Cl-C3)haloalkoxy and the oxo function, Rl~ is H, (Cl-C3) alkyl, (Cl-C3)haloalkyl, (Cl-C3)alkoxy, (Cl-C3)haloalkoxy, (Cl-C3)alkylthio, (Cl-C3)halo-alkylthio, NH2, NHCH3, N(CH3) 2 or OH, Rll is (Cl-C4)alkyl, (Cl-C4)haloalkyl, (C2-Cs)alkoxyalkyl, (C2-C~)alkenyl, (C2-C~)haloalkenyl, (C2-C~)alkynyl or ( C2 - C4 ) haloalkynyl, Rl2 is (Cl-C4)alkyl, (Cl-C~)haloalkyl, (C2-C4)alkenyl, (C2-Cs)haloalkenyl, (Cl-C~)alkoxy, (Cl-C4)haloalkoxy, ( C2 - C4 ) alkenoxy, (C2-C~)haloalkenoxy, NH2 or mono- or di[(Cl-Cs)alkyl]amino, Rl3 is H, (cl-c3)alkyl~ (cl-c3)haloalkyl~ (cl-c3)alk (Cl-C3)haloalkoxy or OH and Rl4 is H, (Cl-C3) alkyl, (Cl-C3)haloalkyl, CHO, COCH3, CO2CH3, CO2C2Hs~ SO2CH3, SO2C2Hs or CN, or NRl3Rl4 together is a heterocyclic radical which, in addition to the N atom, can contain further hetero units from the group consisting of O, N, S, SO and SO2 in the ring skeleton and is unsubstituted or substituted by one or more radicals from the group consisting of halogen, OH, NH2, NO2, NHCH3, N(CH3) 2~
CN, CONHCH3, CO2CH3, COCH3, CON(CH3) 2 ~ C~ - H, (Cl-C3)-alkyl, CONH2, (Cl- C3) alkoxy, (Cl- C3) haloalkyl, (Cl-C3)haloalkoxy and the oxo function, CA 02204610 1997-0~-06 Rl5 is H, (Cl-C3)alkyl, (Cl-C3)haloalkyl, (Cl-C3)alkoxy, (Cl-C3)haloalkoxy, OH, NH2 or mono- or di-[(Cl-C2)alkyl]amino and Rl6 is H, Cl-C3-alkyl, Cl-C3-haloalkyl, CHO, COCH3, CO2CH3, CO2C2H5, SO2CH3 or CN, or NRlsRl6 together is a heterocyclic radical which, in addition to the N atom, can contain further hetero units from the group consisting of O, N, S, SO and SO2 in the ring skeleton and is unsubstituted or substituted by one or more radicals from the group consisting of halogen, OH, NH2, NO2, NHCH3, N(CH3) 2~
CN, CONHCH3, CO2CH3, COCH3, CON(CH3) 2~ CO-H, (Cl-C3)-alkyl, CONH2, (Cl-C3)alkoxy, (Cl-C3)haloalkyl, (Cl-C3)haloAlkoxy and the oxo function, Rl7 is (Cl-C6)alkyl, (Cl-C6)haloalkyl, (Cl-C6)alkoxyalkyl, (C3-C6)cycloalkyl, (C3-C6)halocycloalkyl, (C2-C6)-alkenyl, (C2-C6)haloalkenyl, (C2-C6)alkynyl or (C2-C6)-haloalkynyl.
Rl8 is (Cl-C6~alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C3-C,)cycloalkyl, (Cl-C6)alkoxy, (C2-C6)alkenoxy, (C2-C6)alkynoxy or mono- or di[(Cl-C6)alkyl]amino, where each of the last nine radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, OH, (Cl-C3)-alkoxy, (Cl-C3)halo~1ko~y, (Cl-C3)alkylthio, (Cl-C3)-haloalkylthio, NH2, mono- or di[(Cl-C4)alkyl]amino, NO2, CN, CO2CH3, CO2C2H5, CN, SO2CH3, SO2C2Hs, CONH2, CON(CH3) 2~ CONHCH3, COCH3, CO-H and CO-CF3, Rl9 is H, (Cl-C~)alkyl, (Cl-C~)haloalkyl, (C2-C~)alkenyl, (C2-C4)haloalkenyl, (C2-C~)alkynyl, (C2-C4)-haloalkynyl, (C3-C6)cycloalkyl, (C3-C6)-halocycloalkyl, (Cl-C~)alkoxy, (Cl-C~)haloalkoxy, (C2-C4)alkenoxy, (C2-C4)haloalkenoxy, (C2-C4)alkynoxy, (C2-C4)haloalkynoxy, NH2, (Cl-C~)alkylamino, CA 02204610 1997-0~-06 (C1-C~)haloalkylamino, di[(Cl-C~)alkyl]- or di[(C1-C4) haloalkyl]amino.
R20 is (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl or (C3-C,)cycloalkyl, where each of the last four radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C3)alkoxy, (C1-C3)haloalkoxy, (C2-C3)-alkenoxy, (C2-C3)haloalkenoxy, OH, (C1-C4)alkylthio, (C1-C4)-haloalkylthio, NH2, mono- and di[(C1-C~)-alkyl]-amino, NHCOOCH3, NHCOCH3, NHCO-H, N(CH3)CO2CH3, N(CH3)CO-H, CN, NO2, COOCH3, COOC2Hs, CO-CH3, CO-H, CONH2, CONHCH3, CON(CH3) 2, SO2CH3, SOCH3 and SO2N(CH3) 2 ' R21 is a radical analogous to R20, R22 is a radical analogous to R6 and R23 is a radical analogous to R' or NR22R23 together is a radical analogous to NR6R7, R24 is a radical analogous to R21, R25 is a radical analogous to R20, R26 is a radical analogous to R21, R27 is a radical analogous to R6 and R28 is a radical analogous to R7 or NR27R28 together is a radical analogous to NR6R', R29 is a radical analogous to R21, R30 is H, OH, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C2-C4)-alkenyloxy, (C2-C~)haloalkenoxy, (Cl- C4) alkyl, (Cl-C4)haloalkyl, (C2-C~)alkenyl, (C2-C4)haloalkenyl, CA 02204610 1997-0~-06 j (C2-C4) alkynyl, (C2-C4) haloalkynyl, (C3-C6)cycloalkyl, NH2, mono- or di[(Cl-C~)alkyl]amino or mono- or di[(C1-C4)haloalkyl]amino, R31 is H, (C1-C4)alkyl, (C1- C4) haloalkyl, (C2-C4) alkenyl, (C2-C4)haloalkenyl, (C2-C")alkynyl, (C2-C4)halo-alkynyl, (C1-C4)alkoxy, (Cl-CI)haloalkoxy, (C2-C4)-alkenoxy, (C2-C4)haloalkenoxy, (C2-C4)alkynoxy, (C2- C") haloalkynoxy ~ NH2~ mono - or di[(C1-C4)alkyl]amino or mono- or di[(C1-C~)-haloalkyl]amino, R32 i8 (Cl-C4) alkyl, (C2-C4)alkenyl, (C2-C4)-alkynyl, (C2-C4)alkoxy, (C2-C~)alkenoxy or (C2-C4)alkynoxy, where each of the last six radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (Cl-C~)alkoxy, OH, NH2, CN, NO2 and mono- and di[(C1-C4)alkyl]amino, R33 is a radical analogous to R6 and R3~ is a radical R7 or NR33R34 together is a radical analogou~ to NR6R'.
Of the general definitions of the compounds according to the invention mentioned above, those in which the generally defined radicals generally comprise, and in particular narrowly comprise, the corresponding radicals in the examples listed in Tables 1 to 7 (see below) are preferred.
Compounds of the formula (I) according to the invention and salts thereof which are al~o preferred are those in which one of the radicals X and Y is halogen, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C")haloalkyl, (C1-C,)haloalkoxy or mono- or di-[(C1-C4)alkyl]-amino and the other of the - CA 02204610 1997-0~-06 radicals X and Y is (Cl-C~)alkyl, (Cl-C4)alkoxy or (C1-C~)haloalkoxy and Z is CH or N.
Compounds of the formula (I) according to the invention and salts thereof which are of particular interest are also those in which the group S(O)nR1 is in the 2-position and the group NR3R4 is in the 5-position relative to the sulfonylurea radical.
Compounds of the formula (I) according to the invention and salts thereof which are of particular interest are also those in which R1 is (C1-C4)-alkyl, (C1-C~)haloalkyl or mono- or di-[(C1-C4)alkyl]-amino, R2 is halogen, (C1-C2)alkyl, (C1-C2)alkoxy, N02, CN or N(CH3) 2' m is 0 or 1, R3 is (C1-C4)alkyl, (C1-C4)haloalkyl or cyclopropyl, R4 i8 CH0~ COR , COOR2l, CONR22R23, SO R32 or S0 NR33R34 R20 i8 (C1-C~)alkyl, (C1-C~)haloalkyl, cyclopropyl, (C2-C~)alkenyl, (C2-C~)alkenyl or (C1-C3)alkoxy-(C1-C~)alkyl, R2l is (Cl-C~)alkyl, (Cl-C4)haloalkyl or (Cl-C3)alkoxy-(Cl-C~)alkyl, R22 is H or (Cl-C4)alkyl, R23 is H or (Cl-C4)alkyl, R32 i8 (Cl-C4) alkyl, (C2-C4)alkenyl, (C2-C4)alkynyl, (Cl-C4)haloalkyl or (Cl-C3)alkoxy-(Cl-C~)alkyl, R33 is H or (Cl-C4)alkyl, and R34 is H, (Cl-C4)alkyl or (Cl-C")alkoxy.
Preferred compounds of the formula (I) according to the invention and salts thereof are those in which Rl is dimethylamino, methyl, ethyl, n-propyl, isopropyl or cyclopropyl, m is zero, R3 is (Cl-C4)alkyl, and CA 02204610 1997-0~-06 , R4 i~ CHO, COCH3, COC2H5, CO2CH3, CO2C2H5, CO-CPr, COiPr, COnPr, CO-CH2CH=CH2, CO-CH2C-CH, [(Cl-C2)haloalkyl~-carbonyl, SO2NH2, SO2NHCH3 or SO2N(CH3) 2 .
Compounds (I) according to the invention and salts thereof which are also preferred are those in which one of the radicals X and Y is methyl, ethyl, meth-oxy, ethoxy, chloro, methylamino, dimethylamino, (Cl-C2)haloalkyl or (Cl-C2)haloalkoxy and the other of the radicals X and Y is methyl, ethyl, methoxy, ethoxy or 2,2,2-trifluoroethoxy and Z is CH or N.
Compounds of the formula (I) according to the invention and salts thereof which are also preferred are those in which the group S(O)n-Rl is in the 2-position and the group NR3R4 is in the 5-position relative to the sulfonylurea radical.
The present invention furthermore also relates to pro-cesses for the preparation of the compounds of the formula (I) according to the invention or salts thereof which comprises a) reacting a compound of the formula (II) (R2) R --N ~ S ( ~ ) n R I ( I I ) R~ S~2NH2 with a heterocyclic carbamate of the formula (III) N ~
R o-Co-NR5 ~ ( ~ Z (lll) N~X
CA 02204610 1997-0~-06 in which R~ is unsubstituted or substituted phenyl or Cl-C4-alkyl, or b) reacting a sulfochloride of the formula (IV) (R2~
R~-N ~ S(O)nR (IV) with a heterocyclic amine of the formula (V) N~r R5HN~(~ ( V ) N~X
in the presence of a cyanate, for example an alkali metal cyanate, ~uch as ~odium cyanate or pota~sium cyanate, or c) reacting a sulfonamide of the formula (II) (cf.
variant a) succes~ively with a chloroformic acid aryl ester of the formula (VI) aryl-O-CO-Cl (VI) and with a heterocyclic amine of the formula (V), or d) reacting a sulfonylurea of the formula (VII) ( R 2 ) S ( ~ ) n R
H-N ~'So2NHCWNR5~(~z (V I I ) R N--<~
CA 02204610 1997-0~-06 with an acylating agent R4-Nuc, in which Nuc iB a leaving group, or e) reacting a sulfonamide of the formula (II) with a (thio)isocyanate of the formula (VIII) y W ~ C ~ N~l~ (Vl I 1) N~X
in the presence of a suitable base, such as, for example, potassium carbonate or triethylamine, or f) reacting a sulfonyl isocyanate of the formula (IX) 3 ( ~ S(O)nR
\N ~ S02N~C-0 (IX) with a heterocyclic amine of the formula (V) (cf.
the formula in variant b), in which, in the above formulae (II) to (IX), the rad-icals Rl, R2, R3, R4, Rs, W, X, Y and Z and the indices m and n are defined as in formula (I), and in the variants a) - c) and f), initially compounds of the formula (I) where W = 0 are obtained.
The reaction of the compounds of the formulae (II) and (III) is preferably carried out under base catalysis in inert solvents, such as, for example, methylene chloride, acetonitrile, dioxane, dimethylformamide (DMF) or dimethylacetamide or T~F, at temperature~ from -10~C up to the boiling point of the particular solvent. Base~
which are used here are, for example, organic amine bases, such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or triethylamine, or also hydroxides, ~uch a~, for CA 02204610 1997-0~-06 example, sodium hydroxide or potassium hydroxide, or alcoholates, such as, for example, sodium methylate, potassium tert-butylate or sodium phenolate, or carbon-ates, such as, for example, sodium carbonate or potassium carbonate, in particular in the case where R~ = (substi-tuted) phenyl (cf., for example, EP-A-44807), or tri-methyl- or triethylaluminum, the latter in particular in the case where R = alkyl (cf. EP-A-166516).
The sulfonamides of the formula (II) are obt~;n~hle~ for example, by the following route (cf. Equation 1): The reaction of the sulfonic acids (X) or alkali metal salts thereof with a chlorinating agent - such as, for example, PCl3, POCl3 or SOCl2 - leads to the sulfochloride of the formula (XI). This reaction iB carried out in bulk or in inert solvents, such as, for example, methylene chloride, sulfolane or acetonitrile or in a solvent mixture of inert components. The subsequent reaction with ~mmonia or tert-butylamine leads to the sulfonamides of the for-mula (XII) where R = H or tert-butyl. These compounds can be converted with mercaptans in solvents, such as, for example, dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidinone, in the presence of suitable bases, such as, for example, sodium carbonate or potassium carbonate, into the correspo~;ng mercaptans of the formula (XIII) (n = O). By the choice of suitable oxidiz-ing agents and reaction conditions, the correspo~;ng compounds of the formula (XIII) where n = 1 and 2 can be prepared analogously to known methods.
After the reduction of the nitro group from the compounds of the formula (XIII), for example with iron in an acetic acid medium or other customary methods (for example hydrogenation with Pd-C/hydrogen), the aniline of the formula (XIV) is obtained (in this context cf.: H. Berri, G.T. Neuhold, F.S. Spring, J. Chem. Soc. 1952, 2042;
M. Freifelder, "Catalytic Hydrogenation in Organic Synthesis: Procedures and Commentary", J. Wiley and Sons, New York (1978), Chapter 5).
CA 02204610 1997-0~-06 , The alkyl group (R3) is introduced by processes known from the literature by mo~o~lkylation of anilines. For this, the aniline of the formula (XIV) is acylated, for example with an acid chloride or acid anhydride, and the amide function formed is subsequently transformed with suitable reducing agents, such as, for example, borane-dimethylsulfide complex, to give the N-alkylaniline (cf.
S. Kri~nAml~rty, Tetrahedron Lett. 23 3315 (1982)).
The N-alkylanilines of the formula (XV) thus obtained, where R = t-butyl or R = H, are reacted with suitable electrophiles, such as, for example, acid chlorides, acid anhydrides, isocyanates, thioisocyanates, sulfochlorides or amidosulfochlorides, to give the compounds of the formula (XVI) or to give the sulfonamides of the for-mula (II) (in this context cf.: A.L. Beckniter in J.
Zabicky, "The Chemistry of Amides", p. 73-185, Interscience, New York, 1979; E.J. Corey et al., Tetrahedron Lett. 1978, 1051;
H.J. Saunders, R.J. Slocombe, Chem. Rev. 43, 203 (1948);
20 S. Ozaki, Chem. Rev. 72, 457, 469 (1972);
G. Zol~, Arzneim.-Forschung. 33, 2 (1983);
Houben-Weyl-Hagemann, "Methoden der organischen Chemie (Methods of organic chemistry)", 4th edition, volume E4, p. 485 et seq, Thieme Verlag Stuttgart, 1983;
25 J. Golinsky, M. Mahosza, Synthesis 1978, 823;
Houben-Weyl-Muller, "Methoden der organischen Chemie (Methods of organic chemistry) n, 4th edition, volume IX, pp. 338-400 and 605-622, Thieme Verlag Stuttgart, 1955;
Houben-Weyl-Rlarmann, "Methoden der organischen Chemie (Methods of organic chemistry) n, 4th edition, volume E 11/2, pp. 1020-22, Thieme Verlag Stuttgart, 1985; and S. Krishnamurthey, Tetrahedron Lett. 23, 3315 (1982)).
The sulfonamides (II) are obtained from the compounds of the formula (XVI) by reaction with strong acids. Possible strong acids are, for example, mineral acids, such as H2SO4 or HCl, or strong organic acids, such as trifluoro-acetic acid. The t-butyl protective group is split off, CA 02204610 1997-0~-06 for example, at temperatures from -20~C and the particular reflux temperature of the reaction mixture, preferably at 0~C to 40~C.
The reaction can be carried out in bulk or also in an inert sol~ent, such as, for example, methylene chloride or chloroform.
The carbamates of the formula (III) required for the reaction of the compounds (II) according to ~ariant a) are known from the literature or can be prepared by processes analogous to known processes (cf. EP-A-70 804 or US-A-4,480,101).
Equation 1 (R2) C I (R2) C I
~2N~so3H 02N~X I )so2c 1 (R2) Cl (R2)~ S(~)nR
02N SO2NH-R ~2N SO2NH-R
( X I I ) ( X I I I ) CA 02204610 1997-0~-06 ( R ~ ~ ) n R I ~ H N ~// S ( ~ ) n R
(XIV) R (XV) R,~ R ~ H
acylation . acylation ( R 2 ) m S ( ~ ) n R ( R 2 ) m S ( ~ ) n R
R~R4N ~S02NH ~ R~R4N~SO2NH2 (XVI ) + ( I I ) For compounds of the formula (I) where n = 2 and Rl = a nitrogen or oxygen function, a different synthesis route to that of Equation 1 is particularly suitable. Compounds of the formula (XIII) where n = 0 and, for example, Rl =
benzyl are converted into the correspo~;ng sulfo-chlorides of the formula (XVII) by oxidative chlorination with chlorine or hypochlorite. The nitroaromatics of the formula (XIII) (n = 2, Rl = O-R', Rl = NRnRn') are obtA;nAhle by reaction of alcoholates, phenolates M-OR' or amines HNR"R"' with the sulfochloride of the formula (XVII). The further synthesis sequence to give the correspo~;ng sulfonylureas of the formula (I) (n =
2, Rl = OR', Rl = NR"R"') can be carried out analogously to the transformation of compound (XIII) ~ compound (I) described above (cf. Equation 2).
CA 02204610 1997-0~-06 Equation 2 ~ ) n R ~ eg. C I 2 ( ~~ 2 C I ~,l O R
- WO 96/14304 ~ ~ ~~~~ PCT/~P95/04183 .
Description N-Acyl-N-alkylaminophenylsulfonylureas with sulfur substituents, processes for their preparation and their use as herbicides and plant growth regulators.
The invention relates to the technical field of herbicides and plant growth regulators, in particular herbicides for selective control of broad-leaved weeds and graminaceous weeds in crops of useful plants.
It is known that phenylsulfonylureas which have heterocyclic substituents and carry an amino or a func-tionalized amino group or a sulfur substituent on the phenyl ring have herbicidal and plant growth-regulating properties (EP-A-1515; EP-A-7687; EP-A-30138; US-A-4,892,946; US-A-4,981,509, US-A-4,664,695; US-A-4,632,695, EP-A-116518; EP-A-23142 (= US-A-4,310,346);
US-A-4,369,058; EP-A-84020; EP-A-192489; DE 42 36 902 Al).
Surprisingly, it has now been found that certain phenyl-sulfonylureas with heterocyclic substituents are particu-larly suitable as herbicides and plant growth regulators.
The present invention relates to compounds of the for-mula (I) and salts thereof \ ~S0 -NH-C-NRs ~(~ ( I ) in which W is an oxygen or sulfur atom, preferably O, CA 02204610 1997-0~-06 m is 0, 1, 2 or 3, n is 0, 1 or 2, R1 is hydroxyl, amino, mono- or disubstituted amino, hydroxylamino, substituted hydroxylamino, hydrazino, substituted hydrazino, an aliphatic hydrocarbon or hydrocarbonoxy radical, aryl, heteroaryl, aryloxy or heteroaryloxy, where each of the last 6 radicals mentioned is unsubstituted or substituted, R2 is halogen, CN, NO2, amino, mono- or disubstituted amino, alkyl or alkoxy, where each of the last two radicals mentioned is unsubstituted or substituted, R3 is an aliphatic hydrocarbon radical, which is un-substituted or substituted, preferably having a total of 1 to 12 carbon atoms, R4 is an acyl radical, R5 is hydrogen, hydroxyl, (Cl-C~)alkyl, (C1-C~)alkoxy, (C2-C4)alkenyl or (C2-C4)alkynyl, where each of the last 4 radicals mentioned is unsubstituted or sub-stituted by halogen, preferably F, Cl or Br, X and Y independently of one another are hydrogen, hydroxyl, amino, mono- or disubstituted amino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy or alkylthio, where each of the last 9 radicals mentioned is unsubstituted or substituted, and Z is CH, N or C - R ~ ~, in which R~ is halogen, /
cyano, alkyl, alkoxy, haloalkyl or haloalkoxy.
In formula (I) and all the formulae below, the alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio radicals and the correspo~ing unsaturated and/or substi-tuted radicals can in each case be straight-chain or branched in the carbon skeleton. Unless specifically ~tated, the lower carbon skeletons, for example having 1 to 6 carbon atoms, or in the case of unsaturated groups having 2 to 6 carbon atoms, are preferred for these CA 02204610 1997-0~-06 , radicals. Alkyl radicals, including in the composite me~n;ngs, such as alkoxy, haloalkyl and the like, are, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyl radicals, hexyl radicals, such as n-hexyl, i-hexyl and 1,3-dimethylbutyl, or heptyl radicals, such as n-heptyl, l-methylhexyl and 1,4-dimethylpentyl;
alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals correspo~ing to the alkyl radicals; alkenyl is, for example, allyl, 1-methylprop-2-en-l-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methyl-but-3-en-1-yl and 1-methyl-but-2-en-1-yl; and alkynyl is, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl and 1-methyl-but-3-yn-1-yl.
Halogen is, for example, fluorine, chlorine, bromine or iodine. Haloalkyl, -alkenyl and -alkynyl are alkyl, alkenyl or alkynyl respectively which are partly or completely substituted by halogen, preferably by fluor-ine, chlorine and/or bromine, in particular by fluorine or chlorine, for example CF3, CHF2, CH2F, CF3CF2, CH2FCHCl, CCl3, CHCl2 and CH2CH2Cl; haloalkoxy is, for example, OCF3, OCHF2, OCH2F, CF3CF2O, OCH2CF3 and OCH2CH2Cl; the correspo~;ng definition applies to haloalkenyl and other radicals substituted by halogen.
A hydrocarbon radical iB a straight-chain, branched or cyclic, saturated or unsaturated aliphatic or aromatic hydrocarbon radical, for example alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or aryl; aryl here is a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, penta-lenyl, fluorenyl and the like, preferably phenyl; a hydrocarbon radical i~ preferably alkyl, alkenyl or alkynyl having up to 12 carbon atoms or cycloalkyl having 3, 4, 5, 6 or 7 ring atoms or phenyl;
the corresponding definition applies to a hydrocarbon radical in a hydrocarbonoxy radical.
A heterocyclic radical or ring (heterocyclyl) can be CA 02204610 1997-0~-06 saturated, unsaturated or heteroaromatic; it preferably contains one or more hetero units in the ring, preferably from the group consisting of N, 0, S, S0 and S02; prefer-ably, it is an aliphatic heterocyclyl radical having 3 to 7 ring atoms or a heteroaromatic radical having 5 or 6 ring atoms and contains 1, 2 or 3 hetero units. The heterocyclic radical can be, for example, a hetero-aromatic radical or ring (heteroaryl), such as, for example, a mono-, bi- or polycyclic aromatic system in which at least 1 ring contains one or more hetero atoms, for example pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, thienyl, thiazolyl, oxazolyl, furyl, pyrrolyl, pyrazolyl and imidazolyl, or is a partly hydrogenated radical, such as oxiranyl, pyrrolidyl, piperidyl, piperazinyl, dioxo-lanyl, morpholinyl or tetrahydrofuryl. Possible sub-stituents for a substituted heterocyclic radical are the substituents mentioned below, and in addition also oxo.
The oxo group can alQo occur on the hetero ring atoms which can exi~t in different oxidation states, for example in the case of N and S.
Substituted radicals, such as substituted hydrocarbon radicals, for example substituted alkyl, alkenyl, al-kynyl, aryl, phenyl and benzyl, or substituted hetero-cyclyl or heteroaryl, are, for example, a substituted radical derived from the unsubstituted parent substance, the substituents being, for example, one or more, prefer-ably 1, 2 or 3, radicals from the group consisting of halogen, alkoxy, halo~lkoxy, alkylthio, hydroxyl, amino, nitro, carboxyl, cyano, azido, alkoxycarbonyl, alkyl-carbonyl, formyl, carbamoyl, mono- and dialkylamino-carbonyl, substituted amino, such as acylamino and mono-and dialkylamino, and alkyl~ulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and, in the case of cyclic radicals, also alkyl and haloalkyl, as well as the unsaturated aliphatic radicals correspo~;ng to the saturated hydrocarbon-containing radical 8 mentioned, such as alkenyl, alkynyl, alkenyloxy, alkynyloxy and the like.
In the case of radicals with carbon atoms, those having CA 02204610 1997-0~-06 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, are preferred. Substituents from the group consisting of halogen, for example fluorine and chlorine, (Cl-C4)alkyl, preferably methyl or ethyl, (C1-C~)haloalkyl, preferably trifluoromethyl, (Cl-C4)alkoxy, preferably methoxy or ethoxy, (Cl-C~)haloalkoxy, nitro and cyano, are as a rule preferred. The substituents methyl, methoxy and chlorine are particularly preferred here.
Mono- or disubstituted amino is a chemically stable radical from the group consisting of substituted amino radicals which are N-subRtituted, for example, by one or two identical or different radicals from the group consisting of alkyl, alkoxy, acyl and aryl; preferably monoalkylamino, dialkylamino, acylamino, arylamino, N-alkyl-N-arylamino and N-heterocyclic radicals; alkyl radicals having 1 to 4 carbon atoms are preferred here;
aryl here is preferably phenyl or substituted phenyl; the definition given below applies here to acyl, preferably (Cl-C4)alkanoyl. A correspo~;ng definition applies to substituted hydroxylamino or hydrazino.
Optionally substituted phenyl is preferably phenyl which is unsubstituted or mono- or polysubstituted, preferably up to three times, by identical or different radicals from the group consisting of halogen, (Cl-C4)alkyl, (Cl-C4) alkoxy, (Cl-C4)haloalkyl, (Cl-C4)haloalkoxy and nitro, for example o-, m- and p-tolyl, dimethylphenyl radicals, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoro- and -trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl and o-, m- and p-methoxyphenyl.
An acyl radical is the radical of an organic acid, for example the radical of a carboxylic acid and radicals of acids derived therefrom, such as the thiocarboxylic acid, optionally N-substituted iminocarboxylic acids or the radical of carbonic acid monoesters, optionally N-substi-tuted carbamic acid, sulfonic acids, sulfinic acids,phosphonic acids and phosphinic acids. Acyl is, for CA 02204610 1997-0~-06 example, formyl, alkylcarbonyl, such as (Cl-C4-alkyl)-carbonyl, phenylcarbonyl, in which the phenyl ring can be substituted, for example as shown above for phenyl, or alkoxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, N-alkyl-1-iminoalkyl and other radicals of organic acids.
The above examples of general terms, such as alkyl, acyl, aryl, substituted radicals and the like, are not a complete list; in particular the terms also include me~n;ngs of the same type which are given below for the preferred compounds.
The invention also relates to all the stereoisomers included by the formula (I) and mixtures thereof. Such compounds of the formula (I) contain one or more asymmet-ric carbon atoms or al~o double bonds which are not shownseparately in the general formula (I). The possible stereoisomers defined by their ~pecific ~patial form, such as enantiomers, diastereomers and Z and E isomers, are all included by the formula (I) and can be obtained from mixtures of the stereoisomer6 by customary methods or also prepared by stereoselective reactions in combina-tion with the u~e of stereochemically pure starting substances.
The compounds of the formula (I) can form salt~ in which the hydrogen of the -SO2-NH- group is replaced by a cation ~uitable for agriculture. These salt~ are, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium ~alt~, or also ammonium salts or salts with organic amines.
Compounds of the formula (I) according to the invention or ~alts thereof which are of particular interest are those in which R1 is OH, NR6R7 (C1-C6)alkyl, (C2-C6)alkenyl, CA 02204610 1997-0~-06 (C2-C6)alkynyl, (Cl-C6)alkoxy, (C2-C6)alkenoxy, (C2-C6)alkynoxy, (C3-C7) cycloalkyl, (C3-C7) -cyclo-alkoxy, (C3-C7) cycloalkyl-(Cl-C2)alkyl, (C3-C7), cyclo-alkyl-(Cl-C2)alkoxy, phenoxy, phenyl, thienyl or pyridyl, where each of the last fourteen radicals mentioned i8 unsubstituted or substituted by one or more radicals from the group consisting of halogen, (Cl-C4)alkoxy, (Cl-C4)haloalkyl, (C2-C4)alkenoxy, (C2-C4)haloalkenoxy, (C2-C~)alkynoxy, (C2-C~)halo-alkynoxy, CN, NO2, N3, SCN, OCN, OH, NR3R9, CO-Rl~, (C1-C4)alkylthio, (Cl-C~)haloalkylthio, unsubstituted and substituted phenyl, SO-Rll and SO2Rl2, and in the case of cyclic radicals also (Cl-C4)alkyl and (Cl-C4)haloalkyl, R2 is halogen, (Cl-C3)alkyl, (Cl-C3)haloalkyl, (Cl-C5)-alkoxyalkyl, NO2, NRl3Rl4, CN, (Cl-C3) alkoxy or (Cl-C3)haloalkoxy, R3 is (Cl-C6)-alkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, (C3-C7) -cycloalkyl or (C3-C7) -cycloalkyl-(Cl-C2)alkyl, where each of the last five radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (Cl-C7)alkoxy, ( Cl- C4) haloalkoxy, ( C2- C4) alkenoxy, (C2-C4)haloalkenoxy, (C2-C4)alkynoxy, (C2-C4)halo-alkynoxy, (Cl-C~)alkylthio, (C2-C4)-haloalkylthio, (C2-C4)alkenylthio, (C2-C4)-haloalkenylthio, (C2-C4)-alkynylthio, (C2-C4)haloalkynylthio, CN, NO2, N3, SCN, OCN, OH, NRl5Rl6, SoRl7, SO Rl8 and CO Rl9 R4 i CO H CO R20 CO-OR2l, Co-NR22R23, Co-SR24, CS-R, CS-OR26, CS-NR27R23, CS-SR29, C(=NR30)R3l, SO2R32 or R5 is H, OH, (Cl-C3) alkyl, (C2-C3)alkenyl, (C2-C3)alkynyl or (Cl-C3)alkoxy, preferably H or (Cl-C4) alkyl, R6 is H, OH, NH2, mono- or di-[(Cl-C3)alkyl]amino, CA 02204610 1997-0~-06 (Cl-C~)alkyl, (C2-C4)alkenyl, (C2-C~)alkynyl, (Cl-C4)alkoxy, (C2-C4)alkenoxy or (C2-C~)alkynoxy, where each of the last eight radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (Cl-C3)alkoxy, (Cl- C3) haloalkoxy, (Cl-C 3) alkylthio and (Cl-C3)haloalkylthio, R7 H, (cl-c4)alkyl~ (c2-c4)alkenyl~ (C2-C~)alkynyl, [(Cl-C4)alkyl]-carbonyl, [(C2-C~)alkenyl]-carbonyl, [(C2-C~)alkynyl]-carbonyl, [(Cl-C~)alkoxy]-carbonyl, [(C2-C4)alkenoxy]-carbonyl, [(C2-C~)alkynyloxy]-carbonyl, [(Cl-C4)alkyl]-aminocarbonyl, di[(Cl-C4)-alkyl]amino-carbonyl, (Cl-C~)alkyl-sulfonyl, (C2-C4)-alkenyl-sulfonyl, (C2-C4)alkynylsulfonyl, (Cl-C4)-alkylaminosulfonyl or di-[(Cl- C4) alkyl]-aminosulfonyl, where each of the last sixteen rad-icals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, OH, (Cl-C3) alkoxy, (Cl-C3)halo~lkoxy, (Cl- C3) alkylthio and (Cl- C3) haloalkylthio, or NR6R7 together is a heterocyclic radical which, in addition to the N atom, can contain further hetero units from the group consisting of 0, N, S, SO and SO2 in the ring skeleton and which is unsubstituted or substituted by radicals from the group consisting of the oxo function, halogen, OH, NH2, NO2, NHCH3, N(CH3) 2~ CN, CONH2, CONHCH3, CO2CH3, CON(CH3) 2~ COCH3, CHO, (Cl-C3) alkyl, (Cl-C3)-haloalkyl, (Cl-C3)alkoxy and (Cl- C3) haloalkyl, R3 is H, (cl-c4)alkyl~ (cl-c4)haloalkyl~ (c2-c4)alken (C2-C4) haloalkenyl, (C2-C")alkynyl, (C2-C4) halo alkynyl, OH, (Cl-C3) alkoxy or (C2-C3)haloalkoxy and R9 is H, (Cl-C4) alkyl, (Cl-C4)haloalkyl, (C2-C4)alkenyl, (C2-C4) haloalkenyl, (C2-C4) alkynyl, (C2-C4) halo-alkynyl, CO-H, CO2CH3, CO2CH3, CO-CH3, CO-NH2, CO-NHCH3 CA 02204610 1997-0~-06 g or CON(CH3) 2~
or NRsR9 together iB a heterocyclic radical which, in addition to the N atom, can contain further hetero units from the group consisting of O, N, S, SO or So2 in the ring skeleton and is unsubstituted or substituted by one or more radicals from the group con~isting of halogen, OH, NH2, NO2, CONH2, CONHCH3, CON(CH3) 2~ NHCH3, N(CH3) 2~ CN, CQ2CH3, COCH3, CO-H, (Cl-C3)alkyl, (Cl-C3)haloalkyl, (Cl-C3)alkoxy, (Cl-C3)haloalkoxy and the oxo function, Rl~ is H, (Cl-C3) alkyl, (Cl-C3)haloalkyl, (Cl-C3)alkoxy, (Cl-C3)haloalkoxy, (Cl-C3)alkylthio, (Cl-C3)halo-alkylthio, NH2, NHCH3, N(CH3) 2 or OH, Rll is (Cl-C4)alkyl, (Cl-C4)haloalkyl, (C2-Cs)alkoxyalkyl, (C2-C~)alkenyl, (C2-C~)haloalkenyl, (C2-C~)alkynyl or ( C2 - C4 ) haloalkynyl, Rl2 is (Cl-C4)alkyl, (Cl-C~)haloalkyl, (C2-C4)alkenyl, (C2-Cs)haloalkenyl, (Cl-C~)alkoxy, (Cl-C4)haloalkoxy, ( C2 - C4 ) alkenoxy, (C2-C~)haloalkenoxy, NH2 or mono- or di[(Cl-Cs)alkyl]amino, Rl3 is H, (cl-c3)alkyl~ (cl-c3)haloalkyl~ (cl-c3)alk (Cl-C3)haloalkoxy or OH and Rl4 is H, (Cl-C3) alkyl, (Cl-C3)haloalkyl, CHO, COCH3, CO2CH3, CO2C2Hs~ SO2CH3, SO2C2Hs or CN, or NRl3Rl4 together is a heterocyclic radical which, in addition to the N atom, can contain further hetero units from the group consisting of O, N, S, SO and SO2 in the ring skeleton and is unsubstituted or substituted by one or more radicals from the group consisting of halogen, OH, NH2, NO2, NHCH3, N(CH3) 2~
CN, CONHCH3, CO2CH3, COCH3, CON(CH3) 2 ~ C~ - H, (Cl-C3)-alkyl, CONH2, (Cl- C3) alkoxy, (Cl- C3) haloalkyl, (Cl-C3)haloalkoxy and the oxo function, CA 02204610 1997-0~-06 Rl5 is H, (Cl-C3)alkyl, (Cl-C3)haloalkyl, (Cl-C3)alkoxy, (Cl-C3)haloalkoxy, OH, NH2 or mono- or di-[(Cl-C2)alkyl]amino and Rl6 is H, Cl-C3-alkyl, Cl-C3-haloalkyl, CHO, COCH3, CO2CH3, CO2C2H5, SO2CH3 or CN, or NRlsRl6 together is a heterocyclic radical which, in addition to the N atom, can contain further hetero units from the group consisting of O, N, S, SO and SO2 in the ring skeleton and is unsubstituted or substituted by one or more radicals from the group consisting of halogen, OH, NH2, NO2, NHCH3, N(CH3) 2~
CN, CONHCH3, CO2CH3, COCH3, CON(CH3) 2~ CO-H, (Cl-C3)-alkyl, CONH2, (Cl-C3)alkoxy, (Cl-C3)haloalkyl, (Cl-C3)haloAlkoxy and the oxo function, Rl7 is (Cl-C6)alkyl, (Cl-C6)haloalkyl, (Cl-C6)alkoxyalkyl, (C3-C6)cycloalkyl, (C3-C6)halocycloalkyl, (C2-C6)-alkenyl, (C2-C6)haloalkenyl, (C2-C6)alkynyl or (C2-C6)-haloalkynyl.
Rl8 is (Cl-C6~alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C3-C,)cycloalkyl, (Cl-C6)alkoxy, (C2-C6)alkenoxy, (C2-C6)alkynoxy or mono- or di[(Cl-C6)alkyl]amino, where each of the last nine radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, OH, (Cl-C3)-alkoxy, (Cl-C3)halo~1ko~y, (Cl-C3)alkylthio, (Cl-C3)-haloalkylthio, NH2, mono- or di[(Cl-C4)alkyl]amino, NO2, CN, CO2CH3, CO2C2H5, CN, SO2CH3, SO2C2Hs, CONH2, CON(CH3) 2~ CONHCH3, COCH3, CO-H and CO-CF3, Rl9 is H, (Cl-C~)alkyl, (Cl-C~)haloalkyl, (C2-C~)alkenyl, (C2-C4)haloalkenyl, (C2-C~)alkynyl, (C2-C4)-haloalkynyl, (C3-C6)cycloalkyl, (C3-C6)-halocycloalkyl, (Cl-C~)alkoxy, (Cl-C~)haloalkoxy, (C2-C4)alkenoxy, (C2-C4)haloalkenoxy, (C2-C4)alkynoxy, (C2-C4)haloalkynoxy, NH2, (Cl-C~)alkylamino, CA 02204610 1997-0~-06 (C1-C~)haloalkylamino, di[(Cl-C~)alkyl]- or di[(C1-C4) haloalkyl]amino.
R20 is (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl or (C3-C,)cycloalkyl, where each of the last four radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C3)alkoxy, (C1-C3)haloalkoxy, (C2-C3)-alkenoxy, (C2-C3)haloalkenoxy, OH, (C1-C4)alkylthio, (C1-C4)-haloalkylthio, NH2, mono- and di[(C1-C~)-alkyl]-amino, NHCOOCH3, NHCOCH3, NHCO-H, N(CH3)CO2CH3, N(CH3)CO-H, CN, NO2, COOCH3, COOC2Hs, CO-CH3, CO-H, CONH2, CONHCH3, CON(CH3) 2, SO2CH3, SOCH3 and SO2N(CH3) 2 ' R21 is a radical analogous to R20, R22 is a radical analogous to R6 and R23 is a radical analogous to R' or NR22R23 together is a radical analogous to NR6R7, R24 is a radical analogous to R21, R25 is a radical analogous to R20, R26 is a radical analogous to R21, R27 is a radical analogous to R6 and R28 is a radical analogous to R7 or NR27R28 together is a radical analogous to NR6R', R29 is a radical analogous to R21, R30 is H, OH, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C2-C4)-alkenyloxy, (C2-C~)haloalkenoxy, (Cl- C4) alkyl, (Cl-C4)haloalkyl, (C2-C~)alkenyl, (C2-C4)haloalkenyl, CA 02204610 1997-0~-06 j (C2-C4) alkynyl, (C2-C4) haloalkynyl, (C3-C6)cycloalkyl, NH2, mono- or di[(Cl-C~)alkyl]amino or mono- or di[(C1-C4)haloalkyl]amino, R31 is H, (C1-C4)alkyl, (C1- C4) haloalkyl, (C2-C4) alkenyl, (C2-C4)haloalkenyl, (C2-C")alkynyl, (C2-C4)halo-alkynyl, (C1-C4)alkoxy, (Cl-CI)haloalkoxy, (C2-C4)-alkenoxy, (C2-C4)haloalkenoxy, (C2-C4)alkynoxy, (C2- C") haloalkynoxy ~ NH2~ mono - or di[(C1-C4)alkyl]amino or mono- or di[(C1-C~)-haloalkyl]amino, R32 i8 (Cl-C4) alkyl, (C2-C4)alkenyl, (C2-C4)-alkynyl, (C2-C4)alkoxy, (C2-C~)alkenoxy or (C2-C4)alkynoxy, where each of the last six radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (Cl-C~)alkoxy, OH, NH2, CN, NO2 and mono- and di[(C1-C4)alkyl]amino, R33 is a radical analogous to R6 and R3~ is a radical R7 or NR33R34 together is a radical analogou~ to NR6R'.
Of the general definitions of the compounds according to the invention mentioned above, those in which the generally defined radicals generally comprise, and in particular narrowly comprise, the corresponding radicals in the examples listed in Tables 1 to 7 (see below) are preferred.
Compounds of the formula (I) according to the invention and salts thereof which are al~o preferred are those in which one of the radicals X and Y is halogen, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C")haloalkyl, (C1-C,)haloalkoxy or mono- or di-[(C1-C4)alkyl]-amino and the other of the - CA 02204610 1997-0~-06 radicals X and Y is (Cl-C~)alkyl, (Cl-C4)alkoxy or (C1-C~)haloalkoxy and Z is CH or N.
Compounds of the formula (I) according to the invention and salts thereof which are of particular interest are also those in which the group S(O)nR1 is in the 2-position and the group NR3R4 is in the 5-position relative to the sulfonylurea radical.
Compounds of the formula (I) according to the invention and salts thereof which are of particular interest are also those in which R1 is (C1-C4)-alkyl, (C1-C~)haloalkyl or mono- or di-[(C1-C4)alkyl]-amino, R2 is halogen, (C1-C2)alkyl, (C1-C2)alkoxy, N02, CN or N(CH3) 2' m is 0 or 1, R3 is (C1-C4)alkyl, (C1-C4)haloalkyl or cyclopropyl, R4 i8 CH0~ COR , COOR2l, CONR22R23, SO R32 or S0 NR33R34 R20 i8 (C1-C~)alkyl, (C1-C~)haloalkyl, cyclopropyl, (C2-C~)alkenyl, (C2-C~)alkenyl or (C1-C3)alkoxy-(C1-C~)alkyl, R2l is (Cl-C~)alkyl, (Cl-C4)haloalkyl or (Cl-C3)alkoxy-(Cl-C~)alkyl, R22 is H or (Cl-C4)alkyl, R23 is H or (Cl-C4)alkyl, R32 i8 (Cl-C4) alkyl, (C2-C4)alkenyl, (C2-C4)alkynyl, (Cl-C4)haloalkyl or (Cl-C3)alkoxy-(Cl-C~)alkyl, R33 is H or (Cl-C4)alkyl, and R34 is H, (Cl-C4)alkyl or (Cl-C")alkoxy.
Preferred compounds of the formula (I) according to the invention and salts thereof are those in which Rl is dimethylamino, methyl, ethyl, n-propyl, isopropyl or cyclopropyl, m is zero, R3 is (Cl-C4)alkyl, and CA 02204610 1997-0~-06 , R4 i~ CHO, COCH3, COC2H5, CO2CH3, CO2C2H5, CO-CPr, COiPr, COnPr, CO-CH2CH=CH2, CO-CH2C-CH, [(Cl-C2)haloalkyl~-carbonyl, SO2NH2, SO2NHCH3 or SO2N(CH3) 2 .
Compounds (I) according to the invention and salts thereof which are also preferred are those in which one of the radicals X and Y is methyl, ethyl, meth-oxy, ethoxy, chloro, methylamino, dimethylamino, (Cl-C2)haloalkyl or (Cl-C2)haloalkoxy and the other of the radicals X and Y is methyl, ethyl, methoxy, ethoxy or 2,2,2-trifluoroethoxy and Z is CH or N.
Compounds of the formula (I) according to the invention and salts thereof which are also preferred are those in which the group S(O)n-Rl is in the 2-position and the group NR3R4 is in the 5-position relative to the sulfonylurea radical.
The present invention furthermore also relates to pro-cesses for the preparation of the compounds of the formula (I) according to the invention or salts thereof which comprises a) reacting a compound of the formula (II) (R2) R --N ~ S ( ~ ) n R I ( I I ) R~ S~2NH2 with a heterocyclic carbamate of the formula (III) N ~
R o-Co-NR5 ~ ( ~ Z (lll) N~X
CA 02204610 1997-0~-06 in which R~ is unsubstituted or substituted phenyl or Cl-C4-alkyl, or b) reacting a sulfochloride of the formula (IV) (R2~
R~-N ~ S(O)nR (IV) with a heterocyclic amine of the formula (V) N~r R5HN~(~ ( V ) N~X
in the presence of a cyanate, for example an alkali metal cyanate, ~uch as ~odium cyanate or pota~sium cyanate, or c) reacting a sulfonamide of the formula (II) (cf.
variant a) succes~ively with a chloroformic acid aryl ester of the formula (VI) aryl-O-CO-Cl (VI) and with a heterocyclic amine of the formula (V), or d) reacting a sulfonylurea of the formula (VII) ( R 2 ) S ( ~ ) n R
H-N ~'So2NHCWNR5~(~z (V I I ) R N--<~
CA 02204610 1997-0~-06 with an acylating agent R4-Nuc, in which Nuc iB a leaving group, or e) reacting a sulfonamide of the formula (II) with a (thio)isocyanate of the formula (VIII) y W ~ C ~ N~l~ (Vl I 1) N~X
in the presence of a suitable base, such as, for example, potassium carbonate or triethylamine, or f) reacting a sulfonyl isocyanate of the formula (IX) 3 ( ~ S(O)nR
\N ~ S02N~C-0 (IX) with a heterocyclic amine of the formula (V) (cf.
the formula in variant b), in which, in the above formulae (II) to (IX), the rad-icals Rl, R2, R3, R4, Rs, W, X, Y and Z and the indices m and n are defined as in formula (I), and in the variants a) - c) and f), initially compounds of the formula (I) where W = 0 are obtained.
The reaction of the compounds of the formulae (II) and (III) is preferably carried out under base catalysis in inert solvents, such as, for example, methylene chloride, acetonitrile, dioxane, dimethylformamide (DMF) or dimethylacetamide or T~F, at temperature~ from -10~C up to the boiling point of the particular solvent. Base~
which are used here are, for example, organic amine bases, such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or triethylamine, or also hydroxides, ~uch a~, for CA 02204610 1997-0~-06 example, sodium hydroxide or potassium hydroxide, or alcoholates, such as, for example, sodium methylate, potassium tert-butylate or sodium phenolate, or carbon-ates, such as, for example, sodium carbonate or potassium carbonate, in particular in the case where R~ = (substi-tuted) phenyl (cf., for example, EP-A-44807), or tri-methyl- or triethylaluminum, the latter in particular in the case where R = alkyl (cf. EP-A-166516).
The sulfonamides of the formula (II) are obt~;n~hle~ for example, by the following route (cf. Equation 1): The reaction of the sulfonic acids (X) or alkali metal salts thereof with a chlorinating agent - such as, for example, PCl3, POCl3 or SOCl2 - leads to the sulfochloride of the formula (XI). This reaction iB carried out in bulk or in inert solvents, such as, for example, methylene chloride, sulfolane or acetonitrile or in a solvent mixture of inert components. The subsequent reaction with ~mmonia or tert-butylamine leads to the sulfonamides of the for-mula (XII) where R = H or tert-butyl. These compounds can be converted with mercaptans in solvents, such as, for example, dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidinone, in the presence of suitable bases, such as, for example, sodium carbonate or potassium carbonate, into the correspo~;ng mercaptans of the formula (XIII) (n = O). By the choice of suitable oxidiz-ing agents and reaction conditions, the correspo~;ng compounds of the formula (XIII) where n = 1 and 2 can be prepared analogously to known methods.
After the reduction of the nitro group from the compounds of the formula (XIII), for example with iron in an acetic acid medium or other customary methods (for example hydrogenation with Pd-C/hydrogen), the aniline of the formula (XIV) is obtained (in this context cf.: H. Berri, G.T. Neuhold, F.S. Spring, J. Chem. Soc. 1952, 2042;
M. Freifelder, "Catalytic Hydrogenation in Organic Synthesis: Procedures and Commentary", J. Wiley and Sons, New York (1978), Chapter 5).
CA 02204610 1997-0~-06 , The alkyl group (R3) is introduced by processes known from the literature by mo~o~lkylation of anilines. For this, the aniline of the formula (XIV) is acylated, for example with an acid chloride or acid anhydride, and the amide function formed is subsequently transformed with suitable reducing agents, such as, for example, borane-dimethylsulfide complex, to give the N-alkylaniline (cf.
S. Kri~nAml~rty, Tetrahedron Lett. 23 3315 (1982)).
The N-alkylanilines of the formula (XV) thus obtained, where R = t-butyl or R = H, are reacted with suitable electrophiles, such as, for example, acid chlorides, acid anhydrides, isocyanates, thioisocyanates, sulfochlorides or amidosulfochlorides, to give the compounds of the formula (XVI) or to give the sulfonamides of the for-mula (II) (in this context cf.: A.L. Beckniter in J.
Zabicky, "The Chemistry of Amides", p. 73-185, Interscience, New York, 1979; E.J. Corey et al., Tetrahedron Lett. 1978, 1051;
H.J. Saunders, R.J. Slocombe, Chem. Rev. 43, 203 (1948);
20 S. Ozaki, Chem. Rev. 72, 457, 469 (1972);
G. Zol~, Arzneim.-Forschung. 33, 2 (1983);
Houben-Weyl-Hagemann, "Methoden der organischen Chemie (Methods of organic chemistry)", 4th edition, volume E4, p. 485 et seq, Thieme Verlag Stuttgart, 1983;
25 J. Golinsky, M. Mahosza, Synthesis 1978, 823;
Houben-Weyl-Muller, "Methoden der organischen Chemie (Methods of organic chemistry) n, 4th edition, volume IX, pp. 338-400 and 605-622, Thieme Verlag Stuttgart, 1955;
Houben-Weyl-Rlarmann, "Methoden der organischen Chemie (Methods of organic chemistry) n, 4th edition, volume E 11/2, pp. 1020-22, Thieme Verlag Stuttgart, 1985; and S. Krishnamurthey, Tetrahedron Lett. 23, 3315 (1982)).
The sulfonamides (II) are obtained from the compounds of the formula (XVI) by reaction with strong acids. Possible strong acids are, for example, mineral acids, such as H2SO4 or HCl, or strong organic acids, such as trifluoro-acetic acid. The t-butyl protective group is split off, CA 02204610 1997-0~-06 for example, at temperatures from -20~C and the particular reflux temperature of the reaction mixture, preferably at 0~C to 40~C.
The reaction can be carried out in bulk or also in an inert sol~ent, such as, for example, methylene chloride or chloroform.
The carbamates of the formula (III) required for the reaction of the compounds (II) according to ~ariant a) are known from the literature or can be prepared by processes analogous to known processes (cf. EP-A-70 804 or US-A-4,480,101).
Equation 1 (R2) C I (R2) C I
~2N~so3H 02N~X I )so2c 1 (R2) Cl (R2)~ S(~)nR
02N SO2NH-R ~2N SO2NH-R
( X I I ) ( X I I I ) CA 02204610 1997-0~-06 ( R ~ ~ ) n R I ~ H N ~// S ( ~ ) n R
(XIV) R (XV) R,~ R ~ H
acylation . acylation ( R 2 ) m S ( ~ ) n R ( R 2 ) m S ( ~ ) n R
R~R4N ~S02NH ~ R~R4N~SO2NH2 (XVI ) + ( I I ) For compounds of the formula (I) where n = 2 and Rl = a nitrogen or oxygen function, a different synthesis route to that of Equation 1 is particularly suitable. Compounds of the formula (XIII) where n = 0 and, for example, Rl =
benzyl are converted into the correspo~;ng sulfo-chlorides of the formula (XVII) by oxidative chlorination with chlorine or hypochlorite. The nitroaromatics of the formula (XIII) (n = 2, Rl = O-R', Rl = NRnRn') are obtA;nAhle by reaction of alcoholates, phenolates M-OR' or amines HNR"R"' with the sulfochloride of the formula (XVII). The further synthesis sequence to give the correspo~;ng sulfonylureas of the formula (I) (n =
2, Rl = OR', Rl = NR"R"') can be carried out analogously to the transformation of compound (XIII) ~ compound (I) described above (cf. Equation 2).
CA 02204610 1997-0~-06 Equation 2 ~ ) n R ~ eg. C I 2 ( ~~ 2 C I ~,l O R
5 ~ 2 N H - R or N a O C I 5 ~ 2 N H - R H N R ' ' R
( R )"~~5 ( o ) R~
,~ _--~ ( I ) (XlII) n = 2; Rl = OR' or NRnR"' Alternatively, the sulfonylureas of the formula (I) can be obtained by reaction of sulfonylureas of the formula (VII) with an acylating reagent of the formula R4-Nuc.
( R~ S ( O )",R I
(Vl1) For this, the compounds of the formula (VII) are initially introduced into the reaction vessel at tempera-tures between -10~C and 150~C - preferably at 0~C to 80~C
in an inert solvent, such as, for example, methylene chloride, chloroform, dimethylformamide or N,N-dimethyl-acetamide - and are reacted with a suitable electrophile (in this context cf. the description of the reaction of compounds of the formula (XV) with electrophiles to give the sulfonamides of the formula (XVI) or (II)).
Compounds of the formula (VIII) are known from the literature (EP-A-23141, US-A-4,369,058) or can be pre-pared in an analogous manner.
The reaction of sulfonamides of the formula (II) with i CA 02204610 1997-0~-06 chloroformic acid aryl esters (VI) and heterocyclic amines of the formula (V) likewise leads to the compounds of the formula (I). From the sulfonamides of the for-mula (II) and chloroformic acid aryl ester~ (Ar is, for example, phenyl), the correspo~;ng sulfonyl carbamates of the formula (XVIII) ( R 2 ) S ( ~ ) n R
R3R4N ~ S02-NH-C00 Aryl (XVIII) Qg. Aryl ~ Ph are first formed in the presence of a suitable base, such as, for example, triethylamine or potassium carbamate.
These sulfonyl carbamates of the formula (XVIII) can then be reacted with heterocyclic amines (V) to give the sulfonylureas (I) (cf. US-A-4,994,57).
The phenylsulfonyl isocyanates of the formula (IX) can be prepared, for example, from compounds (II), for example with pho~gene, analogously to the processes from EP-A-184 385.
The reaction of the compounds (IX) with the aminohetero-cyclic compounds of the formula (V) is preferably carried out in inert aprotic solvents, such as, for example, dioxane, acetonitrile or tetrahydrofuran, at temperatures between 0~C and the boiling point of the solvent.
The reaction of the sulfochlorides (IV) with the amino-heterocyclic compounds of the formula (V) and cyanates, such as sodium cyanate and potassium cyanate, is carried out, for example, in aprotic solvents, such as, for example, acetonitrile, sulfolane, N-methylpyrrolidone, dimethylformamide, pyridine, picoline or lutidine, or a mixture of these components, at temperature~ between -10~C and 100~C, preferably at 0~C to 50~C (cf.
US-A-5,517,119).
CA 02204610 1997-0~-06 , The (thio)isocyanates of the formula (VIII) are obtain-able by processes known from the literature (EP-A-232067, EP-A-166516). The reaction of the (thio)isocyanates (VIII) with compounds (II) is carried out at -10~C to 100~C, preferably at 20 to 100~C, in an inert aprotic solvent, such as, for example, acetone or acetonitrile, in the presence of a ~uitable base, for example N(C2H5)3 or K2C03-The compounds of the formula (II), (IV), (XVI) and (XVIII) are novel and the invention likewise relates to them; they correspond to compounds of the formula (XIX) (R2) S(~)n~R
~SO2U~ (XIX) in which U~ is NH2, Cl or mono- or disubstituted amino, such as alkylamino or aryloxyamino, preferably NH2, Cl, t-butylamino or aryloxacarbonylamino, and Rl, R2, R3, R4, n and m are defined as in formula (I).
The salts of the compounds of the formula (I) are prefer-ably prepared in inert solvents, such as, for example, water, methanol, acetone, methylene chloride, tetra-hydrofuran, toluene or heptane, at temperature~ from O to 100~C. Suitable bases for the preparation of the salts according to the invention are, for example, alkali metal carbonates, such as potassium carbonate, alkali metal and alkaline earth metal hydroxides, such as NaOH, ROH and Ca(OH) 2~ ammonia or a suitable amine base, such as triethylamine or ethanolamine. Suitable acids for the salt formation are, for example, HCl, HBr, H2SO4 or HNO3.
The "inert solvents" mentioned in the above process variants mean in each case solvents which are inert under the particular reaction conditions but which do not have CA 02204610 1997-0~-06 , to be inert under any desired reaction conditions.
The term n compounds of the formula (I) according to the invention" below also relates to salts of the compounds of the formula (I).
The compounds of the formula (I) according to the inven-tion have an excellent herbicidal activity against a broad spectrum of economically important mono- and dicotyledon harmful plants. Perennial weeds which are difficult to control and shoot from rhizomes, rootstock or other permanent organisms are also readily attacked by the active compounds. It is irrelevant here whether the substances are applied by the pre-sowing, pre-emergence or post-emergence method.
Some representatives of monocotyledon and dicotyledon weed flora which can be controlled by the compounds according to the invention may be mentioned specifically by way of example, without a limitation to certain species being intended by the ~r ; ng of these.
On the part of the monocotyledon species of weeds, for example, Avena, Lolium, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria and Cyperus species from the annual group and on the part of the perennial species Agropyron, Cynodon, Imperata and Sorghum and also peren-nial Cyperus species are readily attacked.
In the case of dicotyledon species of weeds, the action spectrum extends to species such as, for example, Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Matricaria, Abutilon and Sida on the annual side and Convolvulus, Cirsium, Rumex and Artemisia in the case of perennial weeds.
Weeds which occur under the specific growing conditions in rice, such as, for example, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus, are likewise controlled CA 02204610 1997-0~-06 outstAn~;ngly by the active compounds according to the invention.
If the compounds according to the invention are applied to the soil surface before germination, either the emergence of the weed seedlings is prevented completely or the weeds grow to the cotyledon stage but then stop their growth and finally die completely at the end of three to four weeks.
If the active compounds are applied to the green parts of plants by the post-emergence method, a drastic stop in growth likewise occurs very rapidly after the treatment and the weed plants remain in the growth stage existing at the time of application or die completely after a certain period of time, 80 that weed competition, which is harmful to the crop plants, is eliminated very early and lastingly in this manner.
Although 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 harmed only insignificantly or not at all. For these reasons, the present compounds are particularly suitable for selective control of undesirable plant growth in agricultural crop plantations.
The substances according to the invention furthermore have out8tAn~; ng growth regulatory properties in crop plants. They intervene in the endogenous metabolism of the plants in a regulating manner and can therefore be employed for controlled influencing of plant contents and for facilitating harvesting, such as, for example, by inducing desiccation and stunted growth. They are fur-thermore also suitable for general control and inhibition of undesirable vegetative growth without killing the plants at the same time. Inhibition of vegetative growth CA 02204610 1997-0~-06 plays a major rôle in many monocotyledon and dicotyledon crops, since lodging can be reduced or prevented com-pletely by this means.
The compounds according to the invention can be used in the customary formulation~ in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusting powders or granules. The invention therefore also relates to herbicidal and plant growth-regulating compo-sitions which comprise the compounds of the formula (I).
The compounds of the formula (I) can be formulated in various ways, depen~;ng on the biological and/or chemico-physical parameters which exist. Suitable formulation possibilities are, for example: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, Aprayable solutions, suspension concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusting powders (DP), seed dressing~, granules for application by scattering and to the soil, granuleA (GR) in the form of microgranules, sprayed granules, absorption granules and adsorption granules, water-dispersible granules (WG), water-soluble granule~
(SG), ULV formulations, microcapsules and waxes.
The~e individual types of formulation are known in principle and are described, for example, in: Winnacker-Ruchler, "Chemische Technologie (Chemical technology)", Volume 7, C. Hauser Verlag Munich, 4th edition 1986, Wade van Valkenburg, "Pesticide Formulation~", Marcel Dekker, N.Y., 1973; R. Martens, "Spray Dryingn, Handbook, 3rd edition 1979, G. Goodwin Ltd. London.
The necessary formulating auxiliaries, such as inert materials, surfactants, solvent~ and further additives, are likewise known and are described, for example, in:
Watkins, "Handbook of Insecticide Dust Diluents and CA 02204610 1997-0~-06 Carriers", 2nd edition, Darland Books, Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid Chemistry";
2nd edition, J. Wiley ~ Sons, N.Y.; C. Marsden, "Solvents Guide"; 2nd edition, Interscience, N.Y. 1963;
McCutcheon's "Detergents and Emulsifiers Annual", MC
Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclo-pedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schonfeldt, "Grenzflachen~ktive Athylenoxid-addukte (Surface-active ethylene oxide adducts)", Wiss.
Verlagsgesell., Stuttgart 1976; Winnacker-Ruchler, "Chemische Technologie (Chemical technology)", Volume 7, C. Hauser Verlag Munich, 4th edition 1986.
Combinations with other substances having a pesticidal action, such as, for example, insecticides, acaricides, herbicides and fungicides, and with safeners, fertilizers and/or growth regulators, can also be prepared on the basis of these formulations, for example in the form of a ready-to-use formulation or as a tank mix.
Wettable powders are preparations which are uniformly dispersible in water and which, alongside the active compound, and in addition to a diluent or inert sub-stance, also comprise surfactants of an ionic and/or nonionic nature (wetting agents, dispersing agents), for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium ligninsulfonate, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, sodium dibutyl-naphthalene-sulfonate or sodium oleylmethyltauride. To prepare the wettable powders, for example, the herbicidal active compounds are finely ground in customary appar-atuses, such as hammer mills, blast mills and air jet mills, and are mixed with the formulating auxiliaries at the same time or subsequently.
Emulsifiable concentrates are prepared by dissolving the active compound in an organic solvent, for example CA 02204610 1997-0~-06 butanol, cycloh~Ano~e, dimethylformamide, xylene or also higher-boiling aromatics or hydrocarbons or mixtures of organic solvents, with the addition of one or more surfactants of an ionic and/or nonionic nature (emul-sifiers). Emulsifiers which can be used are, for example:calcium alkylarylsulfonates, such as Ca dodecylbenzene-sulfonate, or nonionic emulsifiers, such as fatty acid polyglycol esters, alkylarylpolyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide co~nQation products, alkyl polyethers, sorbitan esters, such as, for example, sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, such as, for example, polyoxyethylene sorbitan fatty acid esters.
Dusting powders are obtained by gr;n~;ng the active compound with finely divided solid substances, for example talc, naturally occurring clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
Suspension concentrates can be water- or oil-based. They can be prepared, for example, by wet gr;n~;ng by means of commercially available bead mills and, if appropriate, with the addition of surfactants, such as are already listed above, for example, for the other types of formu-lation.
Emulsions, for example oil-in-water emulsions (EW), can be prepared, for example, by means of stirrers, colloid mills and/or static mixers using aqueous organic solvents and if appropriate surfactants, such as are already listed above, for example, for the other types of formu-lation.
Granules can be prepared either by spraying the active compound onto adsorptive granular inert material or by applying active compound concentrates to the surface of carrier substances, such as sand, kaolinites or granular inert material, by means of adhesives, for example polyvinyl alcohol, sodium polyacrylate or else mineral CA 02204610 1997-0~-06 oils. Suitable active compounds can also be granulated in the manner customary for the preparation of fertilizer granules - if desired as a mixture with fertilizers.
Water-dispersible granules are as a rule prepared by customary processes, such as spray drying, fluidized bed granulation, disk granulation, m;Ying with high-speed mixers and extrusion, without a solid inert material.
For the preparation of disk, fluidized bed, extruder and sprayed granules cf., for example, processes in "Spray-Drying Handbook" 3rd edition 1979. G. Goodwin Ltd., London; J.E. BLo~--ni~g~ "Agglomeration", Chemical and Engineering 1967, pages 147 et seq; "Perry's Chemical Engineer's Handbook", 5th edition, McGraw-Hill, New York 1973, pages 8-57.
For further details on the formulation of plant protec-tion agents cf., for example, G.C. Rlingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pages 81-96 and J.D. Freyer, S.A. Evans, "Weed Control Handbook", 5th edition, Blackwell Scien-tific Publications, Oxford, 1968, pages 101-103.
The agrochemical formulations as a rule comprise 0.1 to 99 % by weight, in particular 0.1 to 95 % by weight, of active compound of the formula (I). In wettable powders, the active compound concentration is, for example, about 10 to 90 % by weight, the remainder to make up 100 % by weight comprising customary formulation constituents. In emulsifiable concentrates, the active compound concentra-tion can be about 1 to 90, preferably 5 to 80 % by weight. Dust-like formulations comprise 1 to 30 % by weight of active compound, preferably usually 5 to 20 %
by weight of active compound, and sprayable solutions comprise about 0.05 to 80, preferably 2 to 50 % by weight of active compound. In water-dispersible granules, the active compound content partly depends on whether the active compound is present in liquid or solid form and what granulating auxiliaries, fillers and the like are CA 02204610 1997-0~-06 used. In water-dispersible granules, the content of active compound is, for example, between 1 and 95 % by weight, preferably between 10 and 80 % by weight.
In addition, the active compound formulations mentioned comprise, if appropriate, the particular customary tackifiers, wetting agents, dispersing agents, emul-sifiers, penetration agent~, preservatives, antifreezes and solvents, fillers, carrier substances and dyestuffs, defoamers, evaporation inhibitors and agents which influence the pH and viscosity.
Rnown active compounds such as are described, for example, in Weed Research 26, 441-445 (1986), or "The Pesticide Manual", 9th edition, The British Crop Protec-tion Council, 1990/91, Bracknell, England, and literature mentioned therein can be employed, for example, as combination partners for the active compounds according to the invention in mixture formulations or in a tank mix. The following active compounds may be mentioned, for example, as herbicides which are known from the literature and can be combined with the compounds of the formula (I) (Note: the compounds are named either with the n common name n according to the International Organization for St~n~rdization (ISO) or with the chemical name, if appropriate together with a customary code number):
acetochlor; acifluorfen; aclonifen; ARH 7088, i.e. [[[1-[5-t2-chloro-4-(trifluoromethyl)-phenQYy]-2-nitrophenyl]-2-methoxyethylidene]-amino]-oxy]-acetic acid and -acetic acid methyl ester; alachlor; alloxydim; ametryn;
amidosulfuron; amitrol; AMS, i.e. ammonium sulfamate;
anilofos; asulam; atrazin; azimsulfurone (DPX-A8947);
aziprotryn; barban; BAS 516 H, i.e. 5-fluoro-2-phenyl-4H-3, 1-benzoxazin-4-one; benazolin; benfluralin;
benfuresate; bensulfuron-methyl; bensulide; bentazone;
benzofenap; benzofluor; benzoyl-prop-ethyl;
benzthiazuron; bialaphos; bifenox; bromacil; bromobutide;
bromofenoxim; bromoxynil; bromuron; b~i n ~ f08;
CA 02204610 1997-0~-06 busoxinone; butachlor; butamifos; butenachlor;
buthidazole; butralin; butylate; cafens~role (CH-900);
carbetamide; cafentrazone (ICI-A0051); CDAA, i.e. 2-chloro-N,N-di-2-propenylacetamid; CDEC, i.e. diethyl-dithiocarbamic acid 2-chloroallyl ester; chlomethoxyfen;
chloramben; chlorazifop-butyl, chlormesulon (ICI-A0051);
chlorbromuron; chlorbufam; chlorfenac; chlorflurecol-methyl; chloridazon; chlorimuron ethyl; chlornitrofen;
chlorotoluron; chloroxuron; chlorpropham; chlorsulfuron;
chlorthal-dimethyl; chlorthiamid; cinmethylin;
cinosulfuron; clethodim; clodinafop and ester derivatives thereof (for example clodinafop-propargyl); clomazone;
clomeprop; cloproxydim; clopyralid; cumyluron (JC 940);
cyanazine; cycloate; cyclosulfamuron (AC 104);
cycloxydim; cycluron; cyhalofop and ester derivatives thereof (for example butyl ester, DEH-112); cyperquat;
cyprazine; cyprazole; ~ ron; 2,4-DB; dalapon;
desmedipham; desmetryn; di-allate; dicamba; dichlobenil;
dichlorprop; diclofop and esters thereof, such as diclofop-methyl; diethatyl; difenoxuron; difenzoquat;
diflufenican; dimefuron; dimethachlor; dimethametryn;
dimethenamid (SAN-582H); dimethazone, clomazon;
dimethipin; dimetrasulfuron, dinitramine; dinoseb;
dinoterb; diphenamid; dipropetryn; diquat; dithiopyr;
diuron; DNOC; eglinazine-ethyl; EL 177, i.e. 5-cyano-1-(1,1-dimethylethyl)-N-methyl-lH-pyrazole-4-carboxamide;
endothal; EPTC; e~procarb; ethalfluralin;
ethametsulfuron-methyl; ethidimuron; ethiozin;
ethofumesate; F5231, i.e. N-t2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-lH-tetrazol-1-yl]-phenyl]-ethanesulfonamide; ethoxyfen and esters thereof (for example the ethyl ester, HN-252); etobenzanid (HW 52); fenoprop; f ~noy~n , fenoxaprop and fenoxaprop-P
and esters thereof, for example fenoxaprop-P-ethyl and fenoxaprop-ethyl; fenoxydim; fenuron; flamprop-methyl;
flazasulfuron; fluazifop and fluazifop-P and esters thereof, for example fluazifop-butyl and fluazifop-P-butyl; fluchloralin; flumetsulam; flumeturon; flumiclorac and esters thereof (for example the pentyl ester, CA 02204610 1997-0~-06 S-23031); flumioxazin (S-482); flumipropyn; flupoxam (RNW-739); fluorodifen; fluoroglycofen-ethyl; flupropacil (UBIC-4243); fluridone; flurochloridone; fluroxypyr;
flurtamone; fomesafen; fosamine; furyloxyfen;
glufosinate; glyphosate; halosaten; halosulfuron and esters thereof (for example the methyl ester, NC-319);
haloxyfop and esters thereof; haloxyfop-P (= R-haloxyfop) and esters thereof; hexazinone; imazamethabenz-methyl;
imazapyr; imazaquin and salts, such as the ammonium salt;
imazethamethapyr; imazethapyr; imazosulfuron; ioxynil;
isocarbamid; isopropalin; isoproturon; isouron; isoxaben;
isoxapyrifop; karbutilate; lactofen; lenacil; linuron;
MCPA; MCPB; mecoprop; mefenacet; mefluidid; metamitron;
metazachlor; methabenzthiazuron; metham; methazole;
methoxyphenone; methyldymron; metabenzuron, methobenzuron; metobromuron; metolachlor; metosulam (XRD 511); metoxuron; metribuzin; metsulfuron-methyl; MH;
molinate; monalide; monocarbamide dihydrogensulfate;
monolinuron; monuron; MT 128, i.e. 6-chloro-N-(3-chloro-2-propenyl)-5-methyl-N-phenyl-3-pyridazinamine; MT 5950, i.e. N-[3-chloro-4-(1-methylethyl)-phenyl]-2-methyl-pentanamide; naproanilide; napropamide; naptalam; NC 310, i.e. 4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxy-pyrazole; neburon; nicosulfuron; nipyraclophen; nitralin;
nitrofen; nitrofluorfen; norflurazon; orbencarb;
oryzalin; oxadiargyl (RP-020630); oxadiazon; oxyfluorfen;
paraquat; pebulate; pendimethalin; perfluidone;
phenisopham; phenmedipham; picloram; piperophos;
piributicarb; pirifenop-butyl; pretilachlor;
primisulfuron-methyl; procyazine; prodiamine;
profluralin; proglinazine-ethyl; prometon; prometryn;
propachlor: propanil: propaquizafop and esters thereof:
propazine; propham; propisochlor; propyzamide;
prosulfalin; prosulfocarb; prosulfuron (CGA-152005);
prynachlor; pyrazolinate; pyrazon; pyrazosulfuron-ethyl;
pyrazoxyfen; pyridate; pyrithiobac (RIH-2031); pyroxofop and e~ter~ thereof (for example the propargyl ester);
quinclorac; ~lin~erac; quinofop and e~ter derivatives thereof, quizalofop and quizalofop-P and ester deriva-CA 02204610 1997-0~-06 tives thereof, for example quizalofop-ethyl; quizalofop-P-tefuryl and -ethyl; renriduron; rimsulfuron (DPX-E-9636); S 275, i.e. 2-[4-chloro-2-fluoro-5-(2-propynyloxy)-phenyl]-4,5,6,7-tetrahydro-2H-indazole;
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; sulfentrazon (FMC-97285, F-6285);
sulfazuron; sulfometuron-methyl; sulfosate (ICI-A0224);
TCA; tebutam (GCP-5544); tebuthiuron; terbacil;
terbucarb; terbuchlor; terbumeton; terbuthylazine;
terbutryn; THF 450, i.e. N,N-diethyl-3-[(2-ethyl-6-methylphenyl)-sulfonyl]-lH-1,2,4-triazole-1-carboxamide;
thenylchlor (NSR-850); thiazafluoron; thizopyr (Mon-13200); thidiazimin (SN-124085); thifensulfuron-methyl; thiobencarb; tiocarbazil; tralkoxydim; tri-allate; triasulfuron; triazofenamide; tribenuron-methyl;
triclopyr; tridiphane; trietazine; trifluralin;
triflusulfuron and esters (for example the methyl ester, DPX-66037); trimeturon; tsitodef; ~ernolate; WL 110547, i.e. 5-phenoxy-1-[3-(trifluoromethyl)-phenyl]-lH-tetrazole; UBH-509; D-489; LS 82-556; RPP-300; NC-324;
NC-330; RH-218; DPX-N8189; SC-0774; DOWCO-535; DR-8910;
V-53482; PP-600; MBH-001; RIH-9201; ET-751; RIH-6127 and RIH-2023.
For use, the formulations in the commercially available form are diluted in the customary manner, if appropriate, for example by means of water in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules. Dust-like formulations, soil or scattering granules and sprayable solutions are usually not diluted further with additional inert sub-stances before use.
The required amount of compounds of the formula (I) to be applied varies with the outdoor conditions, such as temperature and humidity, the nature of the herbicide used and the like. It can ~ary within wide limits, for CA 02204610 1997-0~-06 example between 0.001 and 10.0 kg/ha or more of active substance, but is preferably between 0.005 and 5 kg/ha.
Chemical examples a) N-tert-butyl-2-Chloro-5-nitrobenzenesulfonamide 165 g of dried 2-chloro-5-nitrobenzenesulfonic acid sodium salt (90 % pure) are initially introduced into 264 ml of acetonitrile, 264 ml of sulfolane and 16.5 ml of dimethylformamide (DMF). After dropwise addition of 198 ml of phosphorus oxychloride, the mixture is heated at the boiling point for 2 hours. After the mixture has been cooled, it is poured onto cold water and extracted with ethyl acetate, and the combined organic phases are dried over sodium sulfate and concentrated. The residue (mixture of sulfolane and 2-chloro-5-nitrobenzenesulfonyl chloride) is taken up in 1500 ml of methylene chloride, 130 ml of tert-butylamine are added (ice-bath cooling) and the mixture is stirred at room temperature for about 2 hours. After w~ ~h; ng with dilute hydrochloric acid and drying over magnesium sulfate, the organic phase is concentrated. The residue is stirred with methanol and cooled to 0~C. The solid which has separated out (109 g, melting point 168 to 171~C) is separated off and dried.
A 2nd fraction of the product of comparable quality (46.7 g) can be isolated analogously from the mother liquor.
b) N-tert-Butyl-2-ethylmercapto-5-nitrobenzene-sulfonamide 5.6 ml of ethylmercaptan are added to a suspension of 20.0 g of N-tert-butyl-2-chloro-5-nitrobenzene-sulfonamide, 18.9 g of potassium carbonate and 100 ml of DMF at room temperature. After the mixture has been ~tirred for 3 hours, it is concentrated under a high vacuum. The residue is taken up in water and acidified with concentrated hydrochloric acid (pH 1 to 2). The CA 02204610 1997-0~-06 , aqueous pha~e is extracted with ethyl acetate. The combined organic phases are dried over magnesium sulfate and then concentrated under reduced pressure. 21.25 g of the desired ethylmercaptan are thus obtained;
Melting point: 172 to 174~C.
c) 5-Amino-2-ethylmercapto-N-tert-butylbenzene-sulfonamide 13.3 g of zink powder are added in portions to a mixture of 12 g of N-tert-butyl-2-ethylmercapto-5-nitrobenzene-sulfonamide, 17.7 g of ammonium chloride, 50 ml of water and 200 ml of ethanol and the mixture i~ stirred at 70~C
for 10 hours. After the solid has been filtered off and washed out with ethyl acetate, the filtrate is concen-trated under reduced pressure. The residue is taken up in ethyl acetate and the mixture is washed with water. After drying over magnesium sulfate, the organic phase is concentrated. 9.4 g of the desired aniline are thus obtained;
lH-NMR (80 MHz, D6-DMSO): ~ ppm = 1.10 (8, 9H, C(C_3)3);
1.15 (t, 2H, CH2C_3); 2.85 (q, 2H, C_2CH3); 5.60 (8, 2H, N_2); 6.60 (8, lH, N_); 6.70 (dd, lH, 4-H); 7.20 (d, lH, 6-H); 7.30 (d, lH, 3-H).
d) N-tert-Butyl-2-ethylmercapto-5-formylaminobenzo-sulfonamide 1.1 ml of formic acid are added dropwi~e to 2.5 ml of acetic anhydride. After the mixture has been heated at 50~C for 1 hour, the solution is cooled to room tempera-ture and 3.0 g of 5-amino-N-tert-butyl-2-ethylmercapto-benzenesulfonamide, dissolved in 10 ml of DMF, are added.
After the reaction mixture has been stirred at 50~C for 1 hour it i~ concentrated under a high vacuum. The residue i~ taken up in ethyl acetate and the mixture i~
washed with dilute hydrochloric acid and water. After drying over magnesium sulfate, the organic pha~e is concentrated. 3.13 g of the desired formylaniline CA 02204610 1997-0~-06 derivative, which can be employed for further reactions without further purification, are thus obtained (cf.
Example e)).
e) N-tert-Butyl-2-ethylmercapto-5-methylamino-benzenesulfonamide 5.0 g of N-tert-butyl-2-ethylmercapto-5-formylamino-benzenesulfonamide are dissolved in 28 ml of chloroform, and 5 ml of borane dimethyl sulfide complex are then added at 0~C. After 1 hour at 0~C and 3 hours at 50~C, the reaction mixture is cooled to 0~C and 30 ml of methanol are added. The mixture is taken up in chloroform and wa~hed with water. After the organic phase has been dried over magnesium sulfate and the solvent has been distilled off, 4.3 g of the methylaniline are obtained, and can be employed in the subsequent reactions without further purification (cf. Example f).
f) 5-(N-Acetyl-N-methylamino)-N-tert-butyl-2-ethyl-mercaptobenzenesulfonamide 3.0 g of N-tert-butyl-2-ethylmercapto-5-ethylamino-benzenesulfonamide are initially introduced into 15 ml of DMF at 0~C, and 0.78 ml of acetyl chloride and 1.70 ml of triethylamine are added in succession. After the reaction mixture has been stirred at this temperature for 3 hours, it is taken up in ethyl acetate and washed succe~sively with dilute hydrochloric acid, water and sodium bicarbon-ate solution. After the organic phase has been dried over magnesium sulfate and the solvent has been distilled off, 2.54 g of the acetyl compound, which ha~ an adequate purity for further reactions (cf. Example g)), are obtained.
g) 5-(N-Acetyl-N-methylamino)-2-ethylmercapto-benzenesulfonamide 2.3 g of 5-(N-acetyl-N-methylamino)-N-tert-butyl-2-CA 02204610 1997-0~-06 ethylmercaptobenzenesulfonamide are stirred in 30 ml of trifluoroacetic acid at room temperature for 3 days.
After the trifluoroacetic acid has been distilled off and the residue has been washed with diisopropyl ether, 2.05 g of the sulfonamide, which is used directly for preparation of sulfonylureas (cf. Example i), are obtained.
h) N-~(4,6-Dimethoxypyrimidin-2-yl)-aminocarbonyl]-2-ethylmercapto-S-(N-acetyl-N-methyl-amino]-benzenesulfonamide (Table 1, Example no. 1-204) 1.4 ml of DBU are added dropwise to a suspension of 2.0 g of 5-(N-acetyl-N-methylamino)-2-ethylmercaptobenzene-sulfonamide and 1.95 g of 4,6-dimethoxy-2 -p~enoxy-carbonylaminopyrimidine in 20 ml of acetonitrile at 0~C, while stirring vigorously. When the reaction has ended, the acetonitrile is distilled off, the residue is taken up in water and the mixture is washed with diethyl ether.
After the aqueous phase has been acidified with concen-trated hydrochloric acid (pH = 1 to 2), the solid (sulfonylurea) which has precipitated out is separated off and washed with methanol and diisopropyl ether. After drying, 1.85 g of the desired sulfonylurea are thus obtained; mass spectrum (M + 1): 289.
i) N-tert-Butyl-2-ethylsulfonyl-5-nitrobenzene-sulfonamide A solution of 180 g of ~Oxone (potassium peroxo-monosulfate) in 600 ml of water is added dropwise to a solution of 60.0 g of N-tert-butyl-2-ethylmercapto-5-nitrobenzenesulfonamide in 900 ml of methanol at a temperature of 65~C. After the reaction mixture has been stirred at this temperature for 5 hours it is cooled, poured onto water and extracted with ethyl acetate. The combined organic phases are washed with water, dried over magnesium sulfate and then concentrated. 60.6 g of the ethylsulfone are thus obtained; melting point: 108 to CA 02204610 1997-0~-06 .
111 ~ C .
j) 5-Amino-N-tert-butyl-2-ethylsulfonylbenzene-8ul fonamide A mixture of 40 g of N-tert-butyl-2-ethylsulfonyl-5-nitrobenzenesulfonamide is dissolved in 1500 ml of methanol, 0.5 g of palladium-on-charcoal (10 % strength) is added and the mixture is stirred under a hydrogen atmosphere (1 atm). When the uptake of hydrogen has ended, the catalyst is separated off and the solution is concentrated. 32.9 g of the aniline derivative are thus obtained;
Melting point: 193 to 195~C.
k) N-tert-butyl-2-Ethylsulfonyl-5-formylaminobenzene-sulfonamide 0.82 ml of formic acid is added dropwise to 1.85 ml of acetic anhydride. After the mixture has been stirred at 50~C for 2 hours, a solution of 2.5 g of 5-amino-N-tert-butyl-2-ethylsulfonylbenzenesulfonamide in 10 ml of DMF
is added dropwise at room temperature. The mixture is first stirred at 50~C for 3 hours and then concentrated under a high vacuum. The residue is taken up in water and the mixture is extracted with ethyl acetate. After the organic phase been dried over magnesium sulfate, the solvent is distilled off. The residue (3.0 g) contains the desired product and is of adequate purity for further reactions (cf. Example m).
m) N-tert-Butyl-2-ethylsulfonyl-5-(methylamino)-benzenesulfonamide 4.50 g of N-tert-butyl-2-ethylsulfonyl-5-formylamino-benzenesulfonamide are dissolved in 30 ml of chloroform and reacted (reduced) with 4.5 ml of borane dimethyl-sulfide complex analogously to the process described under Example d) to give the methylamino compound. The CA 02204610 1997-0~-06 resulting 4.03 g of the methylaniline compound are sufficiently pure for further reactions (cf. Example n)).
n) 5-(N-Acetyl-N-methylamino)-N-tert-butyl-2-ethyl-sulfonylbenzenesulfonamide 2.5 g of N-tert-butyl-2-ethyl~ulfonyl-5-methylamino-benzenesulfonamide are dissol~ed in 15 ml of DMF and reacted with 0.75 ml of acetyl chloride and 1.60 ml of triethylamine analogously to the process described under Example f) to give the correspo~ing acetylmethylaniline.
2.30 g of the desired compound are thus obtained with an adequate purity for further reactions (cf. Example o)).
o) 5-(N-Acetyl-N-methylamino)-2-ethylsulfonyl-benzenesulfonamide 2.2 g of 5-N-acetylmethylamino-N-tert-butyl-2-ethylsulfonyl-benzenesulfonamide are reacted with 20 ml of trifluoroacetic acid analogously to the process described under Example g). 1.98 g of the sulfonamide, which is sufficiently pure for reactions to give sulfonylureas (cf. Example p)) are thus obtained.
~0 p) 5-(N-Acetyl-N-methyl-amino)-N-[(4,6-dimethoxy-pyrimidin-2-yl)aminocarbonyl]-2-ethylsulfonyl-benzenesulfonamide [Table 3, Example no. 3-204]
1.5 g of 5-(N-acetyl-N-methylamino)-2-ethylsulfonyl-benzenesulfonamide are reacted with 1.35 g of 4,6-dimethoxy-2-phenoxycarbonylamino-pyrimidine and 1.1 ml of DBU in 15 ml of acetonitrile analogously to the process described under Example h). 1.46 g of the herbicidally acti~e title compound are thus obtained; ma~s spectrum (M + 1): 321; melting point 193-194~C (decomposition).
~0 q) 5-(N-Acetyl-N-methylamino)-N-[(4,6-dimethoxy-pyrimidin-2-yl]-2-ethylsulfonylbenzenesulfonamide sodium salt (Table 3, Example no. 3-20) CA 02204610 1997-0~-06 1.5 g of 5-(N-acetyl-N-methylamino)-N-~(4,6-dimethoxy-pyrimidin-2-yl)-aminocarbonyl]-2-ethylsulfonyl-benzenesulfonamide (Chemical Example p)) are initially introduced into 25 ml of methanol. For this purpose 0.55 ml of sodium methylate solution (30 % strength) is slowly added dropwise.
When the reaction has ended, the reaction mixture is concentrated under reduced pressure ~nd the residue is stirred with ethyl acetate. After drying, 1.47 g of the sulfonylurea are obtained.
Melting point: 158~C (decomposition).
The compounds described in the following Tables 1, 2, 3, 4, 5, 6 and 7 are obtained in accordance with or analog-ou~ly to the above Examples a) to q).
CA 02204610 1997-0~-06 Abbreviations for Tables 1-7 m.p. = solidification point in ~C = melting point in ~C
(d) = melting point with decomposition 5 Et = ethyl Me = methyl Pr = nPr = n-propyl iPr = isopropyl CPr = cyclopropyl 10 Bu = nBu = n-butyl iBu = isobutyl tBu = t-butyl Ph = phenyl Furthermore for Tables 4-7:
~5 (R2)m = Description of all the radicals R2; in this column "-" means no substituent (m = 0) and, for example, 4-Cl = "Cl in the 4-position"
(m = 1) Table 1: Compound~ of the formula (Ia) R3R~N~So~-N-Co-NR~ ( I a ) U N~X
Ex . R R2 R3 R4 R5 M X Y Z m . p no .
Me H Me CHO H tl OMe OMe CH
2 ~ N
~ ~ Na N
4 ' ~ ~ ~ ~ K ' ~ ~
CH
6 ' ~ ~ ~ ~ Na 7 ~ H ~ Me 8 ~ Na g ~ ~ ~ ~ H ~ Cl ~ Na ~ ~ ~
Me Me 12 ' ~ H ~ ~ ~
13 ~ " OMe ~ N
" ., ~ ~ Na ~ ~ OCH2CF3 NMe2 16 ~ H ~ ' ~
7 ~ ~ ~ ~ Me ~OMe OMe CH
18 OMe Me N
~ g Me H Et CHO H H OMe OMe CH
Ex, R R2 R3 R4 Rs M X YZ m. p .
no .
Me H Et CHO H Na OMe OMe CH
21 ' ' ' ~ H OMe Cl 22 ~ ' OMe Me N
23 ~ OMe N
24 ~ Me Me CH
2S nPr 26 ~ OMe OMe CH
27 Cl 28 ~ Me N
29 ' ~ OMe CH
3 1 .. ~ c p~ .. .. .. ~ "
32 ' CF3 33 ' ~CF2CF3 ' 34 ' 'CH2CF3 Me H Me CO-CH3 H H OMe OMe CH
36 ~ N
37 , . ~ ~ ~ Na CH
, . ~ ~ ~ Na ~ ~
41 ' ' ' ' ~ H ~ Me 42 ' ~ Na ' 4~ H ~ Cl 44 " . . ~ ~ Na ~ ~ r ~ Me Me Ex. R R2 R3 R~ Rs M X Y Z m.p.
no.
46 Me H Me CO-CH3 H H Me Me CH
47 ~ ~ ~ OMe ~ N
48 ~ ~ ~ ~ ~ Na 49 ~ ~ ~ ~ ~ ~ OCH2CF3 NMe2 -50 . . ~ ~ ~ H
51 ~ ~ ~ ~ Me ~ OMe OMe CH
52 ~ ~ ~ ~ ~ ~ OMe Me N
53 Me H Et CO-CH3 H H OMe OMe CH
54 ~ ~ ~ ~ ~ Na ~
55 ~ ~ H OMe Cl 56 ~ ~ ~ ~ ~ ~OMe Me N
5 7 ~ ~ r ~ OMe N
58 ~ Me Me CH
5 9 ~ ~ npr 60 ~ ~ ~ ~ ~ ~OMe OMe CH
61 ~ ~ ~ ~ ~ ~ Cl 62 ~ Me N
63 ~ OMe 64 ~ r Ipr ~ ~ r ~ ~ CH
~ ~ CPr 66 ~ ~ CF3 67 ~ ~ CFCF
68 ~ ~ CH2CF3 69 Me H Me CO2-Me H H OMe OMe CH
70 ~ N
71 ~ ~ ~ ~ ~ Na - 4~ -EX. R R2 R3 R~ Rs M X Y Z m.p.
no.
72 Me H Me CO2-Me H K OMe OMe N
CH
~ Na 75 ~ H ~ Me 76 ~ Na ' 77 ' ~ H ~ Cl 78 ~ ' Na 79 ~ Me Me 80 ~ H ~ ~ ~
81 ~ OCH3 ~ N
82 ~ Na 83 ~ OcH2cF3 NMe2 84 ~ H ~ ~ ~
85 ~ Me ~ OMeOMe CH
86 ~ OMe Me N
87 Me H Et CO-OMe H H OMeOMe CH
88 ~ Na 89 ~ ' H OMe Cl 9C ~ OMe Me N
91 ~ OMe N
92 ' ~ Me Me CH
( R )"~~5 ( o ) R~
,~ _--~ ( I ) (XlII) n = 2; Rl = OR' or NRnR"' Alternatively, the sulfonylureas of the formula (I) can be obtained by reaction of sulfonylureas of the formula (VII) with an acylating reagent of the formula R4-Nuc.
( R~ S ( O )",R I
(Vl1) For this, the compounds of the formula (VII) are initially introduced into the reaction vessel at tempera-tures between -10~C and 150~C - preferably at 0~C to 80~C
in an inert solvent, such as, for example, methylene chloride, chloroform, dimethylformamide or N,N-dimethyl-acetamide - and are reacted with a suitable electrophile (in this context cf. the description of the reaction of compounds of the formula (XV) with electrophiles to give the sulfonamides of the formula (XVI) or (II)).
Compounds of the formula (VIII) are known from the literature (EP-A-23141, US-A-4,369,058) or can be pre-pared in an analogous manner.
The reaction of sulfonamides of the formula (II) with i CA 02204610 1997-0~-06 chloroformic acid aryl esters (VI) and heterocyclic amines of the formula (V) likewise leads to the compounds of the formula (I). From the sulfonamides of the for-mula (II) and chloroformic acid aryl ester~ (Ar is, for example, phenyl), the correspo~;ng sulfonyl carbamates of the formula (XVIII) ( R 2 ) S ( ~ ) n R
R3R4N ~ S02-NH-C00 Aryl (XVIII) Qg. Aryl ~ Ph are first formed in the presence of a suitable base, such as, for example, triethylamine or potassium carbamate.
These sulfonyl carbamates of the formula (XVIII) can then be reacted with heterocyclic amines (V) to give the sulfonylureas (I) (cf. US-A-4,994,57).
The phenylsulfonyl isocyanates of the formula (IX) can be prepared, for example, from compounds (II), for example with pho~gene, analogously to the processes from EP-A-184 385.
The reaction of the compounds (IX) with the aminohetero-cyclic compounds of the formula (V) is preferably carried out in inert aprotic solvents, such as, for example, dioxane, acetonitrile or tetrahydrofuran, at temperatures between 0~C and the boiling point of the solvent.
The reaction of the sulfochlorides (IV) with the amino-heterocyclic compounds of the formula (V) and cyanates, such as sodium cyanate and potassium cyanate, is carried out, for example, in aprotic solvents, such as, for example, acetonitrile, sulfolane, N-methylpyrrolidone, dimethylformamide, pyridine, picoline or lutidine, or a mixture of these components, at temperature~ between -10~C and 100~C, preferably at 0~C to 50~C (cf.
US-A-5,517,119).
CA 02204610 1997-0~-06 , The (thio)isocyanates of the formula (VIII) are obtain-able by processes known from the literature (EP-A-232067, EP-A-166516). The reaction of the (thio)isocyanates (VIII) with compounds (II) is carried out at -10~C to 100~C, preferably at 20 to 100~C, in an inert aprotic solvent, such as, for example, acetone or acetonitrile, in the presence of a ~uitable base, for example N(C2H5)3 or K2C03-The compounds of the formula (II), (IV), (XVI) and (XVIII) are novel and the invention likewise relates to them; they correspond to compounds of the formula (XIX) (R2) S(~)n~R
~SO2U~ (XIX) in which U~ is NH2, Cl or mono- or disubstituted amino, such as alkylamino or aryloxyamino, preferably NH2, Cl, t-butylamino or aryloxacarbonylamino, and Rl, R2, R3, R4, n and m are defined as in formula (I).
The salts of the compounds of the formula (I) are prefer-ably prepared in inert solvents, such as, for example, water, methanol, acetone, methylene chloride, tetra-hydrofuran, toluene or heptane, at temperature~ from O to 100~C. Suitable bases for the preparation of the salts according to the invention are, for example, alkali metal carbonates, such as potassium carbonate, alkali metal and alkaline earth metal hydroxides, such as NaOH, ROH and Ca(OH) 2~ ammonia or a suitable amine base, such as triethylamine or ethanolamine. Suitable acids for the salt formation are, for example, HCl, HBr, H2SO4 or HNO3.
The "inert solvents" mentioned in the above process variants mean in each case solvents which are inert under the particular reaction conditions but which do not have CA 02204610 1997-0~-06 , to be inert under any desired reaction conditions.
The term n compounds of the formula (I) according to the invention" below also relates to salts of the compounds of the formula (I).
The compounds of the formula (I) according to the inven-tion have an excellent herbicidal activity against a broad spectrum of economically important mono- and dicotyledon harmful plants. Perennial weeds which are difficult to control and shoot from rhizomes, rootstock or other permanent organisms are also readily attacked by the active compounds. It is irrelevant here whether the substances are applied by the pre-sowing, pre-emergence or post-emergence method.
Some representatives of monocotyledon and dicotyledon weed flora which can be controlled by the compounds according to the invention may be mentioned specifically by way of example, without a limitation to certain species being intended by the ~r ; ng of these.
On the part of the monocotyledon species of weeds, for example, Avena, Lolium, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria and Cyperus species from the annual group and on the part of the perennial species Agropyron, Cynodon, Imperata and Sorghum and also peren-nial Cyperus species are readily attacked.
In the case of dicotyledon species of weeds, the action spectrum extends to species such as, for example, Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Matricaria, Abutilon and Sida on the annual side and Convolvulus, Cirsium, Rumex and Artemisia in the case of perennial weeds.
Weeds which occur under the specific growing conditions in rice, such as, for example, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus, are likewise controlled CA 02204610 1997-0~-06 outstAn~;ngly by the active compounds according to the invention.
If the compounds according to the invention are applied to the soil surface before germination, either the emergence of the weed seedlings is prevented completely or the weeds grow to the cotyledon stage but then stop their growth and finally die completely at the end of three to four weeks.
If the active compounds are applied to the green parts of plants by the post-emergence method, a drastic stop in growth likewise occurs very rapidly after the treatment and the weed plants remain in the growth stage existing at the time of application or die completely after a certain period of time, 80 that weed competition, which is harmful to the crop plants, is eliminated very early and lastingly in this manner.
Although 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 harmed only insignificantly or not at all. For these reasons, the present compounds are particularly suitable for selective control of undesirable plant growth in agricultural crop plantations.
The substances according to the invention furthermore have out8tAn~; ng growth regulatory properties in crop plants. They intervene in the endogenous metabolism of the plants in a regulating manner and can therefore be employed for controlled influencing of plant contents and for facilitating harvesting, such as, for example, by inducing desiccation and stunted growth. They are fur-thermore also suitable for general control and inhibition of undesirable vegetative growth without killing the plants at the same time. Inhibition of vegetative growth CA 02204610 1997-0~-06 plays a major rôle in many monocotyledon and dicotyledon crops, since lodging can be reduced or prevented com-pletely by this means.
The compounds according to the invention can be used in the customary formulation~ in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusting powders or granules. The invention therefore also relates to herbicidal and plant growth-regulating compo-sitions which comprise the compounds of the formula (I).
The compounds of the formula (I) can be formulated in various ways, depen~;ng on the biological and/or chemico-physical parameters which exist. Suitable formulation possibilities are, for example: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, Aprayable solutions, suspension concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusting powders (DP), seed dressing~, granules for application by scattering and to the soil, granuleA (GR) in the form of microgranules, sprayed granules, absorption granules and adsorption granules, water-dispersible granules (WG), water-soluble granule~
(SG), ULV formulations, microcapsules and waxes.
The~e individual types of formulation are known in principle and are described, for example, in: Winnacker-Ruchler, "Chemische Technologie (Chemical technology)", Volume 7, C. Hauser Verlag Munich, 4th edition 1986, Wade van Valkenburg, "Pesticide Formulation~", Marcel Dekker, N.Y., 1973; R. Martens, "Spray Dryingn, Handbook, 3rd edition 1979, G. Goodwin Ltd. London.
The necessary formulating auxiliaries, such as inert materials, surfactants, solvent~ and further additives, are likewise known and are described, for example, in:
Watkins, "Handbook of Insecticide Dust Diluents and CA 02204610 1997-0~-06 Carriers", 2nd edition, Darland Books, Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid Chemistry";
2nd edition, J. Wiley ~ Sons, N.Y.; C. Marsden, "Solvents Guide"; 2nd edition, Interscience, N.Y. 1963;
McCutcheon's "Detergents and Emulsifiers Annual", MC
Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclo-pedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schonfeldt, "Grenzflachen~ktive Athylenoxid-addukte (Surface-active ethylene oxide adducts)", Wiss.
Verlagsgesell., Stuttgart 1976; Winnacker-Ruchler, "Chemische Technologie (Chemical technology)", Volume 7, C. Hauser Verlag Munich, 4th edition 1986.
Combinations with other substances having a pesticidal action, such as, for example, insecticides, acaricides, herbicides and fungicides, and with safeners, fertilizers and/or growth regulators, can also be prepared on the basis of these formulations, for example in the form of a ready-to-use formulation or as a tank mix.
Wettable powders are preparations which are uniformly dispersible in water and which, alongside the active compound, and in addition to a diluent or inert sub-stance, also comprise surfactants of an ionic and/or nonionic nature (wetting agents, dispersing agents), for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium ligninsulfonate, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, sodium dibutyl-naphthalene-sulfonate or sodium oleylmethyltauride. To prepare the wettable powders, for example, the herbicidal active compounds are finely ground in customary appar-atuses, such as hammer mills, blast mills and air jet mills, and are mixed with the formulating auxiliaries at the same time or subsequently.
Emulsifiable concentrates are prepared by dissolving the active compound in an organic solvent, for example CA 02204610 1997-0~-06 butanol, cycloh~Ano~e, dimethylformamide, xylene or also higher-boiling aromatics or hydrocarbons or mixtures of organic solvents, with the addition of one or more surfactants of an ionic and/or nonionic nature (emul-sifiers). Emulsifiers which can be used are, for example:calcium alkylarylsulfonates, such as Ca dodecylbenzene-sulfonate, or nonionic emulsifiers, such as fatty acid polyglycol esters, alkylarylpolyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide co~nQation products, alkyl polyethers, sorbitan esters, such as, for example, sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, such as, for example, polyoxyethylene sorbitan fatty acid esters.
Dusting powders are obtained by gr;n~;ng the active compound with finely divided solid substances, for example talc, naturally occurring clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
Suspension concentrates can be water- or oil-based. They can be prepared, for example, by wet gr;n~;ng by means of commercially available bead mills and, if appropriate, with the addition of surfactants, such as are already listed above, for example, for the other types of formu-lation.
Emulsions, for example oil-in-water emulsions (EW), can be prepared, for example, by means of stirrers, colloid mills and/or static mixers using aqueous organic solvents and if appropriate surfactants, such as are already listed above, for example, for the other types of formu-lation.
Granules can be prepared either by spraying the active compound onto adsorptive granular inert material or by applying active compound concentrates to the surface of carrier substances, such as sand, kaolinites or granular inert material, by means of adhesives, for example polyvinyl alcohol, sodium polyacrylate or else mineral CA 02204610 1997-0~-06 oils. Suitable active compounds can also be granulated in the manner customary for the preparation of fertilizer granules - if desired as a mixture with fertilizers.
Water-dispersible granules are as a rule prepared by customary processes, such as spray drying, fluidized bed granulation, disk granulation, m;Ying with high-speed mixers and extrusion, without a solid inert material.
For the preparation of disk, fluidized bed, extruder and sprayed granules cf., for example, processes in "Spray-Drying Handbook" 3rd edition 1979. G. Goodwin Ltd., London; J.E. BLo~--ni~g~ "Agglomeration", Chemical and Engineering 1967, pages 147 et seq; "Perry's Chemical Engineer's Handbook", 5th edition, McGraw-Hill, New York 1973, pages 8-57.
For further details on the formulation of plant protec-tion agents cf., for example, G.C. Rlingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pages 81-96 and J.D. Freyer, S.A. Evans, "Weed Control Handbook", 5th edition, Blackwell Scien-tific Publications, Oxford, 1968, pages 101-103.
The agrochemical formulations as a rule comprise 0.1 to 99 % by weight, in particular 0.1 to 95 % by weight, of active compound of the formula (I). In wettable powders, the active compound concentration is, for example, about 10 to 90 % by weight, the remainder to make up 100 % by weight comprising customary formulation constituents. In emulsifiable concentrates, the active compound concentra-tion can be about 1 to 90, preferably 5 to 80 % by weight. Dust-like formulations comprise 1 to 30 % by weight of active compound, preferably usually 5 to 20 %
by weight of active compound, and sprayable solutions comprise about 0.05 to 80, preferably 2 to 50 % by weight of active compound. In water-dispersible granules, the active compound content partly depends on whether the active compound is present in liquid or solid form and what granulating auxiliaries, fillers and the like are CA 02204610 1997-0~-06 used. In water-dispersible granules, the content of active compound is, for example, between 1 and 95 % by weight, preferably between 10 and 80 % by weight.
In addition, the active compound formulations mentioned comprise, if appropriate, the particular customary tackifiers, wetting agents, dispersing agents, emul-sifiers, penetration agent~, preservatives, antifreezes and solvents, fillers, carrier substances and dyestuffs, defoamers, evaporation inhibitors and agents which influence the pH and viscosity.
Rnown active compounds such as are described, for example, in Weed Research 26, 441-445 (1986), or "The Pesticide Manual", 9th edition, The British Crop Protec-tion Council, 1990/91, Bracknell, England, and literature mentioned therein can be employed, for example, as combination partners for the active compounds according to the invention in mixture formulations or in a tank mix. The following active compounds may be mentioned, for example, as herbicides which are known from the literature and can be combined with the compounds of the formula (I) (Note: the compounds are named either with the n common name n according to the International Organization for St~n~rdization (ISO) or with the chemical name, if appropriate together with a customary code number):
acetochlor; acifluorfen; aclonifen; ARH 7088, i.e. [[[1-[5-t2-chloro-4-(trifluoromethyl)-phenQYy]-2-nitrophenyl]-2-methoxyethylidene]-amino]-oxy]-acetic acid and -acetic acid methyl ester; alachlor; alloxydim; ametryn;
amidosulfuron; amitrol; AMS, i.e. ammonium sulfamate;
anilofos; asulam; atrazin; azimsulfurone (DPX-A8947);
aziprotryn; barban; BAS 516 H, i.e. 5-fluoro-2-phenyl-4H-3, 1-benzoxazin-4-one; benazolin; benfluralin;
benfuresate; bensulfuron-methyl; bensulide; bentazone;
benzofenap; benzofluor; benzoyl-prop-ethyl;
benzthiazuron; bialaphos; bifenox; bromacil; bromobutide;
bromofenoxim; bromoxynil; bromuron; b~i n ~ f08;
CA 02204610 1997-0~-06 busoxinone; butachlor; butamifos; butenachlor;
buthidazole; butralin; butylate; cafens~role (CH-900);
carbetamide; cafentrazone (ICI-A0051); CDAA, i.e. 2-chloro-N,N-di-2-propenylacetamid; CDEC, i.e. diethyl-dithiocarbamic acid 2-chloroallyl ester; chlomethoxyfen;
chloramben; chlorazifop-butyl, chlormesulon (ICI-A0051);
chlorbromuron; chlorbufam; chlorfenac; chlorflurecol-methyl; chloridazon; chlorimuron ethyl; chlornitrofen;
chlorotoluron; chloroxuron; chlorpropham; chlorsulfuron;
chlorthal-dimethyl; chlorthiamid; cinmethylin;
cinosulfuron; clethodim; clodinafop and ester derivatives thereof (for example clodinafop-propargyl); clomazone;
clomeprop; cloproxydim; clopyralid; cumyluron (JC 940);
cyanazine; cycloate; cyclosulfamuron (AC 104);
cycloxydim; cycluron; cyhalofop and ester derivatives thereof (for example butyl ester, DEH-112); cyperquat;
cyprazine; cyprazole; ~ ron; 2,4-DB; dalapon;
desmedipham; desmetryn; di-allate; dicamba; dichlobenil;
dichlorprop; diclofop and esters thereof, such as diclofop-methyl; diethatyl; difenoxuron; difenzoquat;
diflufenican; dimefuron; dimethachlor; dimethametryn;
dimethenamid (SAN-582H); dimethazone, clomazon;
dimethipin; dimetrasulfuron, dinitramine; dinoseb;
dinoterb; diphenamid; dipropetryn; diquat; dithiopyr;
diuron; DNOC; eglinazine-ethyl; EL 177, i.e. 5-cyano-1-(1,1-dimethylethyl)-N-methyl-lH-pyrazole-4-carboxamide;
endothal; EPTC; e~procarb; ethalfluralin;
ethametsulfuron-methyl; ethidimuron; ethiozin;
ethofumesate; F5231, i.e. N-t2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-lH-tetrazol-1-yl]-phenyl]-ethanesulfonamide; ethoxyfen and esters thereof (for example the ethyl ester, HN-252); etobenzanid (HW 52); fenoprop; f ~noy~n , fenoxaprop and fenoxaprop-P
and esters thereof, for example fenoxaprop-P-ethyl and fenoxaprop-ethyl; fenoxydim; fenuron; flamprop-methyl;
flazasulfuron; fluazifop and fluazifop-P and esters thereof, for example fluazifop-butyl and fluazifop-P-butyl; fluchloralin; flumetsulam; flumeturon; flumiclorac and esters thereof (for example the pentyl ester, CA 02204610 1997-0~-06 S-23031); flumioxazin (S-482); flumipropyn; flupoxam (RNW-739); fluorodifen; fluoroglycofen-ethyl; flupropacil (UBIC-4243); fluridone; flurochloridone; fluroxypyr;
flurtamone; fomesafen; fosamine; furyloxyfen;
glufosinate; glyphosate; halosaten; halosulfuron and esters thereof (for example the methyl ester, NC-319);
haloxyfop and esters thereof; haloxyfop-P (= R-haloxyfop) and esters thereof; hexazinone; imazamethabenz-methyl;
imazapyr; imazaquin and salts, such as the ammonium salt;
imazethamethapyr; imazethapyr; imazosulfuron; ioxynil;
isocarbamid; isopropalin; isoproturon; isouron; isoxaben;
isoxapyrifop; karbutilate; lactofen; lenacil; linuron;
MCPA; MCPB; mecoprop; mefenacet; mefluidid; metamitron;
metazachlor; methabenzthiazuron; metham; methazole;
methoxyphenone; methyldymron; metabenzuron, methobenzuron; metobromuron; metolachlor; metosulam (XRD 511); metoxuron; metribuzin; metsulfuron-methyl; MH;
molinate; monalide; monocarbamide dihydrogensulfate;
monolinuron; monuron; MT 128, i.e. 6-chloro-N-(3-chloro-2-propenyl)-5-methyl-N-phenyl-3-pyridazinamine; MT 5950, i.e. N-[3-chloro-4-(1-methylethyl)-phenyl]-2-methyl-pentanamide; naproanilide; napropamide; naptalam; NC 310, i.e. 4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxy-pyrazole; neburon; nicosulfuron; nipyraclophen; nitralin;
nitrofen; nitrofluorfen; norflurazon; orbencarb;
oryzalin; oxadiargyl (RP-020630); oxadiazon; oxyfluorfen;
paraquat; pebulate; pendimethalin; perfluidone;
phenisopham; phenmedipham; picloram; piperophos;
piributicarb; pirifenop-butyl; pretilachlor;
primisulfuron-methyl; procyazine; prodiamine;
profluralin; proglinazine-ethyl; prometon; prometryn;
propachlor: propanil: propaquizafop and esters thereof:
propazine; propham; propisochlor; propyzamide;
prosulfalin; prosulfocarb; prosulfuron (CGA-152005);
prynachlor; pyrazolinate; pyrazon; pyrazosulfuron-ethyl;
pyrazoxyfen; pyridate; pyrithiobac (RIH-2031); pyroxofop and e~ter~ thereof (for example the propargyl ester);
quinclorac; ~lin~erac; quinofop and e~ter derivatives thereof, quizalofop and quizalofop-P and ester deriva-CA 02204610 1997-0~-06 tives thereof, for example quizalofop-ethyl; quizalofop-P-tefuryl and -ethyl; renriduron; rimsulfuron (DPX-E-9636); S 275, i.e. 2-[4-chloro-2-fluoro-5-(2-propynyloxy)-phenyl]-4,5,6,7-tetrahydro-2H-indazole;
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; sulfentrazon (FMC-97285, F-6285);
sulfazuron; sulfometuron-methyl; sulfosate (ICI-A0224);
TCA; tebutam (GCP-5544); tebuthiuron; terbacil;
terbucarb; terbuchlor; terbumeton; terbuthylazine;
terbutryn; THF 450, i.e. N,N-diethyl-3-[(2-ethyl-6-methylphenyl)-sulfonyl]-lH-1,2,4-triazole-1-carboxamide;
thenylchlor (NSR-850); thiazafluoron; thizopyr (Mon-13200); thidiazimin (SN-124085); thifensulfuron-methyl; thiobencarb; tiocarbazil; tralkoxydim; tri-allate; triasulfuron; triazofenamide; tribenuron-methyl;
triclopyr; tridiphane; trietazine; trifluralin;
triflusulfuron and esters (for example the methyl ester, DPX-66037); trimeturon; tsitodef; ~ernolate; WL 110547, i.e. 5-phenoxy-1-[3-(trifluoromethyl)-phenyl]-lH-tetrazole; UBH-509; D-489; LS 82-556; RPP-300; NC-324;
NC-330; RH-218; DPX-N8189; SC-0774; DOWCO-535; DR-8910;
V-53482; PP-600; MBH-001; RIH-9201; ET-751; RIH-6127 and RIH-2023.
For use, the formulations in the commercially available form are diluted in the customary manner, if appropriate, for example by means of water in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules. Dust-like formulations, soil or scattering granules and sprayable solutions are usually not diluted further with additional inert sub-stances before use.
The required amount of compounds of the formula (I) to be applied varies with the outdoor conditions, such as temperature and humidity, the nature of the herbicide used and the like. It can ~ary within wide limits, for CA 02204610 1997-0~-06 example between 0.001 and 10.0 kg/ha or more of active substance, but is preferably between 0.005 and 5 kg/ha.
Chemical examples a) N-tert-butyl-2-Chloro-5-nitrobenzenesulfonamide 165 g of dried 2-chloro-5-nitrobenzenesulfonic acid sodium salt (90 % pure) are initially introduced into 264 ml of acetonitrile, 264 ml of sulfolane and 16.5 ml of dimethylformamide (DMF). After dropwise addition of 198 ml of phosphorus oxychloride, the mixture is heated at the boiling point for 2 hours. After the mixture has been cooled, it is poured onto cold water and extracted with ethyl acetate, and the combined organic phases are dried over sodium sulfate and concentrated. The residue (mixture of sulfolane and 2-chloro-5-nitrobenzenesulfonyl chloride) is taken up in 1500 ml of methylene chloride, 130 ml of tert-butylamine are added (ice-bath cooling) and the mixture is stirred at room temperature for about 2 hours. After w~ ~h; ng with dilute hydrochloric acid and drying over magnesium sulfate, the organic phase is concentrated. The residue is stirred with methanol and cooled to 0~C. The solid which has separated out (109 g, melting point 168 to 171~C) is separated off and dried.
A 2nd fraction of the product of comparable quality (46.7 g) can be isolated analogously from the mother liquor.
b) N-tert-Butyl-2-ethylmercapto-5-nitrobenzene-sulfonamide 5.6 ml of ethylmercaptan are added to a suspension of 20.0 g of N-tert-butyl-2-chloro-5-nitrobenzene-sulfonamide, 18.9 g of potassium carbonate and 100 ml of DMF at room temperature. After the mixture has been ~tirred for 3 hours, it is concentrated under a high vacuum. The residue is taken up in water and acidified with concentrated hydrochloric acid (pH 1 to 2). The CA 02204610 1997-0~-06 , aqueous pha~e is extracted with ethyl acetate. The combined organic phases are dried over magnesium sulfate and then concentrated under reduced pressure. 21.25 g of the desired ethylmercaptan are thus obtained;
Melting point: 172 to 174~C.
c) 5-Amino-2-ethylmercapto-N-tert-butylbenzene-sulfonamide 13.3 g of zink powder are added in portions to a mixture of 12 g of N-tert-butyl-2-ethylmercapto-5-nitrobenzene-sulfonamide, 17.7 g of ammonium chloride, 50 ml of water and 200 ml of ethanol and the mixture i~ stirred at 70~C
for 10 hours. After the solid has been filtered off and washed out with ethyl acetate, the filtrate is concen-trated under reduced pressure. The residue is taken up in ethyl acetate and the mixture is washed with water. After drying over magnesium sulfate, the organic phase is concentrated. 9.4 g of the desired aniline are thus obtained;
lH-NMR (80 MHz, D6-DMSO): ~ ppm = 1.10 (8, 9H, C(C_3)3);
1.15 (t, 2H, CH2C_3); 2.85 (q, 2H, C_2CH3); 5.60 (8, 2H, N_2); 6.60 (8, lH, N_); 6.70 (dd, lH, 4-H); 7.20 (d, lH, 6-H); 7.30 (d, lH, 3-H).
d) N-tert-Butyl-2-ethylmercapto-5-formylaminobenzo-sulfonamide 1.1 ml of formic acid are added dropwi~e to 2.5 ml of acetic anhydride. After the mixture has been heated at 50~C for 1 hour, the solution is cooled to room tempera-ture and 3.0 g of 5-amino-N-tert-butyl-2-ethylmercapto-benzenesulfonamide, dissolved in 10 ml of DMF, are added.
After the reaction mixture has been stirred at 50~C for 1 hour it i~ concentrated under a high vacuum. The residue i~ taken up in ethyl acetate and the mixture i~
washed with dilute hydrochloric acid and water. After drying over magnesium sulfate, the organic pha~e is concentrated. 3.13 g of the desired formylaniline CA 02204610 1997-0~-06 derivative, which can be employed for further reactions without further purification, are thus obtained (cf.
Example e)).
e) N-tert-Butyl-2-ethylmercapto-5-methylamino-benzenesulfonamide 5.0 g of N-tert-butyl-2-ethylmercapto-5-formylamino-benzenesulfonamide are dissolved in 28 ml of chloroform, and 5 ml of borane dimethyl sulfide complex are then added at 0~C. After 1 hour at 0~C and 3 hours at 50~C, the reaction mixture is cooled to 0~C and 30 ml of methanol are added. The mixture is taken up in chloroform and wa~hed with water. After the organic phase has been dried over magnesium sulfate and the solvent has been distilled off, 4.3 g of the methylaniline are obtained, and can be employed in the subsequent reactions without further purification (cf. Example f).
f) 5-(N-Acetyl-N-methylamino)-N-tert-butyl-2-ethyl-mercaptobenzenesulfonamide 3.0 g of N-tert-butyl-2-ethylmercapto-5-ethylamino-benzenesulfonamide are initially introduced into 15 ml of DMF at 0~C, and 0.78 ml of acetyl chloride and 1.70 ml of triethylamine are added in succession. After the reaction mixture has been stirred at this temperature for 3 hours, it is taken up in ethyl acetate and washed succe~sively with dilute hydrochloric acid, water and sodium bicarbon-ate solution. After the organic phase has been dried over magnesium sulfate and the solvent has been distilled off, 2.54 g of the acetyl compound, which ha~ an adequate purity for further reactions (cf. Example g)), are obtained.
g) 5-(N-Acetyl-N-methylamino)-2-ethylmercapto-benzenesulfonamide 2.3 g of 5-(N-acetyl-N-methylamino)-N-tert-butyl-2-CA 02204610 1997-0~-06 ethylmercaptobenzenesulfonamide are stirred in 30 ml of trifluoroacetic acid at room temperature for 3 days.
After the trifluoroacetic acid has been distilled off and the residue has been washed with diisopropyl ether, 2.05 g of the sulfonamide, which is used directly for preparation of sulfonylureas (cf. Example i), are obtained.
h) N-~(4,6-Dimethoxypyrimidin-2-yl)-aminocarbonyl]-2-ethylmercapto-S-(N-acetyl-N-methyl-amino]-benzenesulfonamide (Table 1, Example no. 1-204) 1.4 ml of DBU are added dropwise to a suspension of 2.0 g of 5-(N-acetyl-N-methylamino)-2-ethylmercaptobenzene-sulfonamide and 1.95 g of 4,6-dimethoxy-2 -p~enoxy-carbonylaminopyrimidine in 20 ml of acetonitrile at 0~C, while stirring vigorously. When the reaction has ended, the acetonitrile is distilled off, the residue is taken up in water and the mixture is washed with diethyl ether.
After the aqueous phase has been acidified with concen-trated hydrochloric acid (pH = 1 to 2), the solid (sulfonylurea) which has precipitated out is separated off and washed with methanol and diisopropyl ether. After drying, 1.85 g of the desired sulfonylurea are thus obtained; mass spectrum (M + 1): 289.
i) N-tert-Butyl-2-ethylsulfonyl-5-nitrobenzene-sulfonamide A solution of 180 g of ~Oxone (potassium peroxo-monosulfate) in 600 ml of water is added dropwise to a solution of 60.0 g of N-tert-butyl-2-ethylmercapto-5-nitrobenzenesulfonamide in 900 ml of methanol at a temperature of 65~C. After the reaction mixture has been stirred at this temperature for 5 hours it is cooled, poured onto water and extracted with ethyl acetate. The combined organic phases are washed with water, dried over magnesium sulfate and then concentrated. 60.6 g of the ethylsulfone are thus obtained; melting point: 108 to CA 02204610 1997-0~-06 .
111 ~ C .
j) 5-Amino-N-tert-butyl-2-ethylsulfonylbenzene-8ul fonamide A mixture of 40 g of N-tert-butyl-2-ethylsulfonyl-5-nitrobenzenesulfonamide is dissolved in 1500 ml of methanol, 0.5 g of palladium-on-charcoal (10 % strength) is added and the mixture is stirred under a hydrogen atmosphere (1 atm). When the uptake of hydrogen has ended, the catalyst is separated off and the solution is concentrated. 32.9 g of the aniline derivative are thus obtained;
Melting point: 193 to 195~C.
k) N-tert-butyl-2-Ethylsulfonyl-5-formylaminobenzene-sulfonamide 0.82 ml of formic acid is added dropwise to 1.85 ml of acetic anhydride. After the mixture has been stirred at 50~C for 2 hours, a solution of 2.5 g of 5-amino-N-tert-butyl-2-ethylsulfonylbenzenesulfonamide in 10 ml of DMF
is added dropwise at room temperature. The mixture is first stirred at 50~C for 3 hours and then concentrated under a high vacuum. The residue is taken up in water and the mixture is extracted with ethyl acetate. After the organic phase been dried over magnesium sulfate, the solvent is distilled off. The residue (3.0 g) contains the desired product and is of adequate purity for further reactions (cf. Example m).
m) N-tert-Butyl-2-ethylsulfonyl-5-(methylamino)-benzenesulfonamide 4.50 g of N-tert-butyl-2-ethylsulfonyl-5-formylamino-benzenesulfonamide are dissolved in 30 ml of chloroform and reacted (reduced) with 4.5 ml of borane dimethyl-sulfide complex analogously to the process described under Example d) to give the methylamino compound. The CA 02204610 1997-0~-06 resulting 4.03 g of the methylaniline compound are sufficiently pure for further reactions (cf. Example n)).
n) 5-(N-Acetyl-N-methylamino)-N-tert-butyl-2-ethyl-sulfonylbenzenesulfonamide 2.5 g of N-tert-butyl-2-ethyl~ulfonyl-5-methylamino-benzenesulfonamide are dissol~ed in 15 ml of DMF and reacted with 0.75 ml of acetyl chloride and 1.60 ml of triethylamine analogously to the process described under Example f) to give the correspo~ing acetylmethylaniline.
2.30 g of the desired compound are thus obtained with an adequate purity for further reactions (cf. Example o)).
o) 5-(N-Acetyl-N-methylamino)-2-ethylsulfonyl-benzenesulfonamide 2.2 g of 5-N-acetylmethylamino-N-tert-butyl-2-ethylsulfonyl-benzenesulfonamide are reacted with 20 ml of trifluoroacetic acid analogously to the process described under Example g). 1.98 g of the sulfonamide, which is sufficiently pure for reactions to give sulfonylureas (cf. Example p)) are thus obtained.
~0 p) 5-(N-Acetyl-N-methyl-amino)-N-[(4,6-dimethoxy-pyrimidin-2-yl)aminocarbonyl]-2-ethylsulfonyl-benzenesulfonamide [Table 3, Example no. 3-204]
1.5 g of 5-(N-acetyl-N-methylamino)-2-ethylsulfonyl-benzenesulfonamide are reacted with 1.35 g of 4,6-dimethoxy-2-phenoxycarbonylamino-pyrimidine and 1.1 ml of DBU in 15 ml of acetonitrile analogously to the process described under Example h). 1.46 g of the herbicidally acti~e title compound are thus obtained; ma~s spectrum (M + 1): 321; melting point 193-194~C (decomposition).
~0 q) 5-(N-Acetyl-N-methylamino)-N-[(4,6-dimethoxy-pyrimidin-2-yl]-2-ethylsulfonylbenzenesulfonamide sodium salt (Table 3, Example no. 3-20) CA 02204610 1997-0~-06 1.5 g of 5-(N-acetyl-N-methylamino)-N-~(4,6-dimethoxy-pyrimidin-2-yl)-aminocarbonyl]-2-ethylsulfonyl-benzenesulfonamide (Chemical Example p)) are initially introduced into 25 ml of methanol. For this purpose 0.55 ml of sodium methylate solution (30 % strength) is slowly added dropwise.
When the reaction has ended, the reaction mixture is concentrated under reduced pressure ~nd the residue is stirred with ethyl acetate. After drying, 1.47 g of the sulfonylurea are obtained.
Melting point: 158~C (decomposition).
The compounds described in the following Tables 1, 2, 3, 4, 5, 6 and 7 are obtained in accordance with or analog-ou~ly to the above Examples a) to q).
CA 02204610 1997-0~-06 Abbreviations for Tables 1-7 m.p. = solidification point in ~C = melting point in ~C
(d) = melting point with decomposition 5 Et = ethyl Me = methyl Pr = nPr = n-propyl iPr = isopropyl CPr = cyclopropyl 10 Bu = nBu = n-butyl iBu = isobutyl tBu = t-butyl Ph = phenyl Furthermore for Tables 4-7:
~5 (R2)m = Description of all the radicals R2; in this column "-" means no substituent (m = 0) and, for example, 4-Cl = "Cl in the 4-position"
(m = 1) Table 1: Compound~ of the formula (Ia) R3R~N~So~-N-Co-NR~ ( I a ) U N~X
Ex . R R2 R3 R4 R5 M X Y Z m . p no .
Me H Me CHO H tl OMe OMe CH
2 ~ N
~ ~ Na N
4 ' ~ ~ ~ ~ K ' ~ ~
CH
6 ' ~ ~ ~ ~ Na 7 ~ H ~ Me 8 ~ Na g ~ ~ ~ ~ H ~ Cl ~ Na ~ ~ ~
Me Me 12 ' ~ H ~ ~ ~
13 ~ " OMe ~ N
" ., ~ ~ Na ~ ~ OCH2CF3 NMe2 16 ~ H ~ ' ~
7 ~ ~ ~ ~ Me ~OMe OMe CH
18 OMe Me N
~ g Me H Et CHO H H OMe OMe CH
Ex, R R2 R3 R4 Rs M X YZ m. p .
no .
Me H Et CHO H Na OMe OMe CH
21 ' ' ' ~ H OMe Cl 22 ~ ' OMe Me N
23 ~ OMe N
24 ~ Me Me CH
2S nPr 26 ~ OMe OMe CH
27 Cl 28 ~ Me N
29 ' ~ OMe CH
3 1 .. ~ c p~ .. .. .. ~ "
32 ' CF3 33 ' ~CF2CF3 ' 34 ' 'CH2CF3 Me H Me CO-CH3 H H OMe OMe CH
36 ~ N
37 , . ~ ~ ~ Na CH
, . ~ ~ ~ Na ~ ~
41 ' ' ' ' ~ H ~ Me 42 ' ~ Na ' 4~ H ~ Cl 44 " . . ~ ~ Na ~ ~ r ~ Me Me Ex. R R2 R3 R~ Rs M X Y Z m.p.
no.
46 Me H Me CO-CH3 H H Me Me CH
47 ~ ~ ~ OMe ~ N
48 ~ ~ ~ ~ ~ Na 49 ~ ~ ~ ~ ~ ~ OCH2CF3 NMe2 -50 . . ~ ~ ~ H
51 ~ ~ ~ ~ Me ~ OMe OMe CH
52 ~ ~ ~ ~ ~ ~ OMe Me N
53 Me H Et CO-CH3 H H OMe OMe CH
54 ~ ~ ~ ~ ~ Na ~
55 ~ ~ H OMe Cl 56 ~ ~ ~ ~ ~ ~OMe Me N
5 7 ~ ~ r ~ OMe N
58 ~ Me Me CH
5 9 ~ ~ npr 60 ~ ~ ~ ~ ~ ~OMe OMe CH
61 ~ ~ ~ ~ ~ ~ Cl 62 ~ Me N
63 ~ OMe 64 ~ r Ipr ~ ~ r ~ ~ CH
~ ~ CPr 66 ~ ~ CF3 67 ~ ~ CFCF
68 ~ ~ CH2CF3 69 Me H Me CO2-Me H H OMe OMe CH
70 ~ N
71 ~ ~ ~ ~ ~ Na - 4~ -EX. R R2 R3 R~ Rs M X Y Z m.p.
no.
72 Me H Me CO2-Me H K OMe OMe N
CH
~ Na 75 ~ H ~ Me 76 ~ Na ' 77 ' ~ H ~ Cl 78 ~ ' Na 79 ~ Me Me 80 ~ H ~ ~ ~
81 ~ OCH3 ~ N
82 ~ Na 83 ~ OcH2cF3 NMe2 84 ~ H ~ ~ ~
85 ~ Me ~ OMeOMe CH
86 ~ OMe Me N
87 Me H Et CO-OMe H H OMeOMe CH
88 ~ Na 89 ~ ' H OMe Cl 9C ~ OMe Me N
91 ~ OMe N
92 ' ~ Me Me CH
9 ~ "p~
94 ' ~ OMe OMle CH
Cl 96 ~ Me N
~ ~ ~ OMe ; CA 02204610 1997-05-06 Ex. Rl R2 R3 R4 R5 M X Y Z m.p.
no .
98 Me H iPr CO-OMe H H OMe OMe CH
99 ~ ~ CPr ~ ~ .. . ..
100 ~ ~ CF3 101 ~ ~CF2CF3 102 ~ ~CH2CF3 103 Me H Me CO-CF3 H H OMe OMe CH
104 ~ N
105 ~ ~ ~ ~ ~ Na 106 ~ ~ ~ ' ~ K ~ ~ ~
CH
108 ~ Na ~
l o~ H ~ Me 110 ~ ~ ~ ~ ~ Na ~
H ~ Cl 112 ~ Na 11 3 ~ Me Me 1 1 4 ~ ~ ~ ~ ~ H ~ ~ ~
OCH3 ~ N
116 ~ Na ~ OcH2cF3 NMe2 118 ~ ~ ~ ' ~ H
11 9 ~ ~ ~ ' Me ~ OMe OMe CH
120 ~ ~ ~ ~ ~ ~ OMe Me N
121 Me tl Et CO-CF3 H H OMe OMe CH
122 ~ ~ Na ~ ~
123 ~ OMe Cl Ex. Rl R2 R3 R4 R5 M X YZ m.p.
no .
124 Me H Et CO-CF3 H H OMe Me N
125 ~ ' ~ ' ~ ~ ' OMe 1~
126 ' ' ~ ' ~ ~ Me Me CH
t 27 nPr 128 ' ~ ' ~ ~ ~ OMe OMe CH
129 ~ ~ Cl 130 . . . ~ ~ ~ ~ Me N
131 ~ ~ ~ ~ ~ ' ' OMe 132 ' ' iPr ~ ' ' ~ ~ CH
133 ' " CPr ' ' ~ ~ ' 134 ~ ' CF3 135 ~ 'CF2CF3 137 Me H Me CO-nPr H H OMe OMe CH
138 ~ ~ ' CO-'Bu ' ~ ' ~ ' 139 ~ ~ ~ Co.Cp~ ~ . .. ..
140 ~ CO-CHCI2 ' ' ' 141 ~ ' ~ CO-CCI3 142 ~ ~ ~ CO-CH2CI
143 ~ ' ~ CO-CH2Br 144 ' ~ ' COCH20CH3 ' ' ~ ~
145 ~ ~ CO-iPr ' ~ ' ' 146 ~ ~ ' CO-CCI = CCI2 147 ' ' ' CO-CH = CH2 ' ~
148 ~ ~ CO-C ~ CH
149 ~ ~ ~ SO2NMe2 ~ ~ ~
Ex . R R2 R3 R'l R5 M X Y z m . p .
~o .
150 Me ff Me SO2NHMe H H OMe OMe CH
15 1 ' ~ ~ S~2NH2 152 ~ 5O2CH2F
153 ' ' ' SO2CF3 154 ~ ' ' CO-H Me ' ' ' N
155 ' ~ ' CO-Me ' ' ' ' N
156 ~ ~ ~ COOMe ~ N
157 Me 3-F Me COCH3 H H OMe OMè CH
1 5 9 ~4 - N 0 2 r 1 60 ~ 4-F
161 ' 4-OMe 162 ' 3-OMe 163 ~ 6-OMe 1 64 ~4 NMe2 ' 165 ~ 4-CN
166 ~ 6-Me 167 ~ H ~ CO-Et ~ ' ' ' ' 168 Et H Me CO-H H H OMe OMe CH
169 " ~ N
170 ' ~ Na ' 171 ' ' ~ ' ' K ' ~ ' 172 ~ CH
173 ' ~ Na 174 ~ H ~ Me 175 ~ ~ ~ ' ' Na ' Ex . Rl R2 R3 R4 R5 M X YZ m . p .
~o .
176 Et H ~le CO-H H H OMe Cl CH
. . . ~ ~ Na 178 ~ ' ' Me Me 179 ' ~ H ~ ~ ~
180 ~ ~ ' ' ' 'OCH3 ' N
181 ~ ~ ' ' ' Na ' ~
182 ' ~ OCH2CF3 NMe2 183 ~ H ~ ~ ~
184 ' ~ ' ' Me ' OMe OMe CH
185 ' ~ OMe Me N
186 Et H Me CO-OMe H H OMe OMe CH
187 ~ N
188 ~ Na 189 ' ' ' ' ~ K ~ ~ ~
CH
191 ~ ~ ' ' ~ Na 192 ~ H ' Me 193 ~ Na ~ ' 194 ~ H ~ Cl 195 ~ ~ ' ' ' Na ' 196 ' ' ~ ' ' ' Me Me 197 ~ ' H ~ ~ ~
198 ' ~ ~ ' ' 'OCH3 ~ N
199 ~ r ~ Na 200 ~ OCH2CF3 NMe2 201 ~ H
Ex . R R2 R3 R4 R5 M X Y z m. p .
no .
202 Et H Me CO-OMe Me H OMe OMe CH
203 ' ~ ~ ~ ~ ' OMe Me N
204 Et H Me CO-CH3 H H OMe OMe CH
205 ' ~ ' ~ N
206 ~ ' ~ ~ ' Na 207 ~ ~ ~ ~ ~ K ' ~ ~
208 ~ ~ ' ~ ~ ' ' ~ CH
209 ~ ' ' ~ ~ Na 210 ~ ~ ' ' ~ H ' Me 211 ~ Na ~ ' 212 ~ H ~ Cl 213 ~ ~ ~ ' ~ Na 214 ~ ' ~ ~ ~ ' Me Me 215 ' ' ~ ~ ' H
216 ' ~ ~ ~ ~ ~ OCH3 ' N
217 ~ Na ~ ' 218 ~ OCH2CF3 NMe2 219 ' ~ H ~ ~ ~
220 ~ Me ~ OMe OMe CH
221 ' ' ~ OMe Me N
222 Et H Me CO-CF3 H H OMe OMe CH
223 ~ ' ' ' ' ~ ' ~ N
224 ~ ~ ~ ~ ~ Na ' 225 ~ K ~ ~ -226 " ~ ~ CH
227 ~ ~ ~ ~ ~ Na CA 022046l0 l997-05-06 Ex . R R' R3 R4 Rs M X Y Z m. p .
I10 .
228 Et H Me CO-CF3 H H OMe Me CH
229 ' ' ~ ~ ~ Na ~ ' 230 ' ~ H ' Cl 231 ' ' ' ~ ~ Na ~ ~
232 ' ' ' ~ ~ ' Me Me 233 ~ ' ~ ~ ~ H ~ ~ -234 ~ ~ . . . .OCH3 ~ N
23~ ~ ' ' ~ ~ Na 236 ' ' ' ~ OCH2CF3 NMe2 237 ' ' ' ~ ' H
238 ' ~ ' ~ Me ~ OMe OMe CH
239 ' ~ ~ ~ ~ ~ OMe Me N
Table 2: Compounds of the fo~nula (Ib) R2 o R 3 R 4 N/~ ' ~ 2 - N - C O - N R S )~Nly Ex R l R2 R3 R4 R5 M X Y Z m . p .
2-1 Me H Me CO-H H H OMe OMe CH
2-2 ' ' ' ' ' ' ' ' N
2-3 ~ ~ ' ' ' Na ' ~
2-4 ' ~ K ~ ' ~
2-5 ~ ' ' ' ' CH
2-6 ' ~ Na 2-7 ~ H ' Me 2-8 ~ ' Na ~ ' 2-9 ' ~ H ' Cl 2-10 ~ ' ' ' ' Na 2~ ' ' Me Me 2- 1 2 ~ H ~ . .
2-13 ' ~ ' OCH3 ~ N
2-14 ' ~ Na ' 2-15 ~ OCH2CF3 NMe2 2-16 ~ H ~ ~ ~
2- 17 ' ~ ~ ' Me ' OMe OMe CH
2- 18 ' ~ ' OMe Me N
2-19 Me H Et CO-H H H OMe QMe CH
2-20 ~ Na no Rl R2 R3 R~ R5 M X Y Z m. p .
2-21 Me H Et CO-H H H OMe Cl CH
2-22 ~ ' ' ~ ~ ~ OMe Me N
2-23 ~ OMe N
2-24 ~ ' ~ ~ ~ ~ Me Me CH
2-25 nPr 2-26 ~ ' ~ ~ ~ ~ OMe OMe CH
2-27 ~ ' ' ~ ~ ~ ' Cl 2-28 ' ' ' ~ ~ ~ ~ Me N
2-29 ~ ~ ~ ~ ~ ~ ~ OMe 2-30 ' ' iPt ' ~ ' ' ' CH
2-31 ' ' 'Pr 2-32 ~ ' CF3 ' ' ' ~ ' 2-34 ~ CH2CF3 2-35 Me H Me CO-CH3 H H OMe OMe CH
2 - 36 ~ ' ~ r ~ N
2-37 ' ' ' ' ' Na 2-38 ' ' ~ ' ' K
2-39 ' ~ ' ' ' ' ~ ' CH
2-40 ' ' ' ~ ' Na 2-41 ~ ' ' ' ' H ~ Me 2-42 ' ' ' ' ' Na 2-43 ' ' ' ' ' H ' Cl 2-44 ' ~ ~ ~ ~ Na 2-45 ~ ' ' ' ~ ~ Me Me 2-46 ' ' ' ~ ~ H ' ~ ~
2-47 ~ ~ ' ~ ' ' OCH3 ~ N
2 -4 B ' ' ' ' ' Na ' 2-49 ~ ~ , , , OCH2CF3 NMe2 no R1 R2 R3 R4 R5 M X Y Z m.p.
2-50 Me H Me CO-CH3 H H OcH2cF3 NMe2 N
2-51 ~ ~ ~ ~ Me ~ OMe OMe CH
2-52 ~ ' ~ ~ ~ ~ OMe Me N
2-53 Me H Et CO-CH3 H H OMe OMe CH
2-54 ~ ' ~ ~ ~ Na ~ ~
2-55 ' ~ ~ ~ ' H OMe Cl 2-56 ' ' ' ' ' ' OMe Me N
2-57 ' ' ' ~ ~ ~ ~ OMe N
2-58 ~ ' ~ ~ ~ ~ Me Me CH
2-59 "Pr ' ' ~ ' ' -2-60 ' ' ' ' ' ~ OMe OMe CH
2-61 r ~ Cl 2-62 ' ' ~ ' ' ~ ~ Me N
2-63 ' ' ' ' ' ' ' OMe 2-64 ' ' iPr ' ~ ' ' ~ CH
2-65 ~ ~ CPr 2-66 ~ ' CF3 2-68 ~ CH CF
2-69 Me H Me CO-CF3 H H OMe OMe CH
2-71 ' ~ ~ ~ ' Na 2-72 ' ~ K ' ~ ~
2-73 ' ' ' ~ ~ ~ ~ ' CH
2-74 ~ ~ Na 2-75 ' ' ' ~ ~ H ~ Me 2-76 ' ' ' ' ' Na 2-77 ~ ' ~ ' ' H ' Cl 2-78 ' ' ~ ' ~ Na CA 02204610 1997-0~-06 Ex .
no . R 1 R2 R3 R4 Rs M X Y Z m . p .
2-79 Me H Me CO-CF3 H Na Me Me CH
2-80 ~ ~ ~ ~ ~ H ' ~ ~
2-81 ' ' ' ~ ' ' OCH3 ~ N
2-82 ~ ' ' ' ~ Na 2-83 ' ~ ~ ~ OCH2CF3 NMe2 2-84 ' ' ' ~ ~ H
2-85 ~ ' ' ~ Me ~ OMe OMe CH
2-86 ' ~ ' ' ~ ~ OMe Me N
2-87 Me H Et CO-CF3 H H OMe OMe CH
2-88 ' ~ ~ ' ~ Na 2-89 ' ' ' ' ' H OMe Cl 2-90 ' ' ' ' ' ' OMe Me N
2-91 ' ' ' ' ' ' ~ OMe N
2-92 ~ ' Me Me CH
2-93 nPr 2-94 ~ ~ ' ' ' ~ OMe OMe CH
2-95 ' ' ' ' ' ' ' Me 2-96 ' ' ' ~ ~ ' ' Me N
2-97 ' ' ' ~ ~ ' ~ OMe N
2-98 ' ' 'Pr ' ' ~ ' ' CH
2-99 ' ' CPr 2 - 100 ' ' CF3 2-101 ' ' CF CF ~ . . . .
2-t 02 ' ' CH CF
2-103 Me H Me CO-OMe H H OMe OMe CH
2-10~ ' ' ' ' ' ' ~ ' N
2- 105 ' ~ ~ ' ' Na ~ ' 2-106 ' ' ' ' ' K ' ~ ~
2- 107 ' ' ' ~ ~ ~ ' ' CH
CA 02204610 1997-0~-06 Ex Rl R2 R3 R4 R5 M X Y Z m.p.
2-108 Me H Me CO-OMe H ~a OMe OMe CH
2-tO9 ' ~ ' ' ' H ' Me 2-110 ' ' ' ~ ' Na 2-111 ' ~ ' ' ' H ' Cl 2-112 ' ~ Na 2-113 ' ' ' ' ' ' Me Me 2-114 ' ~ ~ ' ' H
2-115 ' ' ' ' ' ' OCH3 ' N
2-116 ' ~ ' ' ' Na 2-117 ' ~ ~ ~ OCH2CF3 NMe2 2-118 ' ' ' ' ~ H
2-119 ' ' ' ' Me ' OMe OMe CH
2-120 ' ' ' ~ ' ' OMe Me N
2-121 Me H Et CO-OMe H H OMe OMe CH
2-122 ' ' ' ' ~ Na 2-123 ' ' ~ ' ' H OMe Cl 2-124 ' ' ~ ' ' ' OMe Me N
2-125 ' ' ' ' ' ' ~ OMe N
2-126 ~ r ~ Me Me CH
2-127 nPr 2-128 ' ' ' ' ' ' OMe OMe CH
2-129 ' ' ' ' ' ' ' Me 2-130 ~ Me N
2-131 ' ' ' ' ~ ' ' OMe 2-132 ' ' iPr ~ CH
2-133 ' ' CPr 2-134 ' ~ CF3 2-135 ~ CF2C~3 2-136 ' ' CH CF ~ . . . .
EX.
no . F4 l R2 R3 R4 R5 M X Y Z 2. p .
2-137 Me H Me CO-nPr H H OMe OMe CH
2-138 ~ ' ' CO-~u 2-139 ' ' ' CO-'Pr 2-140 ~ ~ ' CO-cHCl2 2-141 ~ ~ CO CC13 2- 142 ' ' ' CO-CH2CI
2-143 ~ ' ~ CO-CH2Br 2-144 ~ ~ ~ COCH20CI-l3 2- 145 ' ~ ' CO-iPr 2- 146 ~ ' ' CO-CCI = ' ~ ' ' 2- 147 ~ . . CO-CH = CH2 2-148 ' " ~ CO-C~CH
2- 149 ~ ~ ~ S02NMe2 2-150 ~ ~ ~ SO2NHMe 2- 151 ' ~ ' 502NH2 2-152 ~ ~ ' SO2CH2F
2- 153 ~ ~ S02CF3 2-154 ' ~ ~ CO-H Me ' ~ ' 2-155 ' ' ~ CO-Me ' ' ' 2-156 ' ~ ~ COOMe 2 157 Me 3-F Me COCH3 H H OMe OMe CH
2-158 ' 3-CI ' ' ' ' ~ ' 2-159 ' 4-NO2 ' ' ' ' ~ ' 2-160 ' 4-F
2 - 161 ' 4-OMe 2-162 ' 3-OMe ' ~ " ' ' ' 2- 163 ' 6-OMe 2-164 ' 4-NMe2 ' ' ~ ' " ' ' Ex R1 R2 R3 R4 Rs M X Y Z m . p .
2-165 Me 4-CN Me COCH3 H H OMe OMe CH
2-166 ' 6-Me ' ~ . . . .
2-167 ' H ' COEt 2-168 Et H Me CO-H H H OMe OMe CH
2-169 ' ~ ' ~ ~ ' ' ' N
2-170 ' ~ ~ ' ' Na ~ ' 2-171 ' ' ~ ' ' K ~ ~ ~
2-172 ~ ' ' ' ' ~ ' CH
2-173 ' ' ' ' ' Na ~ ' 2-174 ' ' ' ' ' H ~ Me 2-175 ~ ' ' ' ' Na ' 2-176 ~ ' H ' Cl 2-177 ~ ' ' ~ ' Na ~ ' 2- 178 ' ' ' ' ~ ' Me Me 2-179 ' ~ ' ' ' H
2- 180 ' ' ~ ' ' ' OCH3 ' N
2-181 ~ ' ~ ' ' Na 2- 182 ' ' ' ' OCH2CF3 NMe2 2-183 ' ~ ' ~ ' H
2- 184 ~ ~ ' ' Me ' OMe OMe CH
2-185 ~ ~ ~ ' ' ' OMe Me N
2-186 Et H Me CO-OMe H H OMe OMe CH
2-187 ' ' ' ' ~ ' ' ' N
2- 188 ' ' ' ' ' Na ' 2-189 ' ' ' ' ' K ' ~ ~
2- 190 ' ' ' ' ' ' ' ' CH
2-l 91 ' ' ' ' ' Na ~ ' 2-192 ~ ' ~ ~ ~ H ~ Me 2-193 ~ ~ ' ~ ' Na _ 59 _ no Rl R2 R3 R~ Rs M X Y Z m.p.
2-194 Et H Me CO-OMe H H OMe Cl CH
2-195 ~ ' ' ' ' Na 2-16 ' ~ ' ' ' ' Me Me 2-197 ~ H
2-198 ' ' ' ' ' ' OCH3 ~ N
2-199 ' ' ~ ~ ~ Na 2-200 ' ~ ~ ~ OCH2CF3 NMe2 2-201 ' ~ ~ ' ~ H ~ ' ' 2-202 ~ ~ ' ~ Me ~ OMe OMe CH
2-203 ~ ' ' ~ ~ ' OMe Me N
2-204 Et H Me CO-CH3 H H OMe OMe CH
2-205 ~ N
2-206 ' ~ ' ' ' Na 2-207 ' ' ' ~ ~ K
2-208 ' ' ~ ' ' ' ' ' CH
2-209 ' ' ' ' ' Na 2-210 ' ' ' ~ ~ H ' Me 2-211 ' ' ' ' ' Na ' 2-212 ' ~ ~ ' ' H ~ Cl 2-213 ' ' ~ ~ ' Na ~ ' 2-214 ' ~ Me Me 2-215 ' ' ' ' ' H ' ~ ' 2-216 ' ' ' ' ~ ~ OCH3 ~ N
2 217 ' ' ' ' ' Na 2-218 ' ' ' ~ ' ~ OCH2CF3 NMe2 2-2t9 ' ' ' ' ~ H
2-220 ~ ~ ' ' Me ~ OMe OMe CH
2-221 ' ' ' ~ ~ ' OMe OMe N
2-222 Et H Me CO-CF3 H H OMe OMe CH
~X
~~ Rl R2 R3 R4 Rs M X Y Z m.p.
2-223 Et H Me CO-CF3 H H OMe OMe N
2 224 ~ ' ' ~ ' Na ~ ' 2-225 ~ ' ~ ~ ' K ~ ~ -2-226 ~ ' ' ~ ' ~ ~ ~ CH
2-227 ' ~ ~ ~ ~ Na ~ ' 2-228 ' ~ ' ' ' H ' Me 2-229 ' ~ ~ ~ ~ Na 2-230 ~ ~ ~ ~ ~ H ~ Cl 2-231 ~ ~ ~ ~ ~ Na ~ ' 2-232 ' ~ ~ ~ ~ ~ Me Me 2-233 ' ~ ~ ~ ~ H ~ ~ -2-234 ~ ~ ~ OCH3 ~ N
2-235 ~ ~ Na 2-236 ~ ~ ~ ~ OCH2Cf3 NMe2 2-237 ~ ~ H ~ ~ -2-238 ~ ~ ~ ~ Me ~ OMe OMe CH
Z-239 ~ ~ OMe Me N
Table 3: Com~ouDd~ of the f ormula ( Ic ) R2 o R3RIN~so~-N-Co-NRs~ z ( I c ) N--~
Ex . R R2 R3 R4 Rs M X Y Zm . p .
no .
3-1 Me H Me CO-H H H OMe OMe CH158-160 (d) 3-2 ~ ' ' ' ' N
3-3 ~ ~ ~ ' ~ Na 34 " . . ~ ~ K
3 5 ~ ' CH
3-6 ~ ' Na 3 7 ~ ~ ~ ~ ' H ' Me 3-8 ' ' ' ' ' Na 3 9 ~ ~ ~ ' ' H ' Cl O " " . ~ ' Na 3~ ' ' ' ' ' Me Me 3-12 ~ H
3-13 ~ ~ . . , , OCH3 ' N 189-191 (d) 3_14 . . ~ ~ ' Na 3-15 ~ ~ ' ' ' ' OCH2CF3 NMe2 3-16 ' ' ' ' ~ H
3-17 ' ' ~ ~ Me ~ OMe OMe CH
3-1 8 ~ ' OMe Me N
3-19 Me H Et CO-H H H OMe OMe CH
Ex . R R2 R3 R4 Rs M X Y Zm. p .
no .
3-20 Me H Et CO-H tlNa OMe OMe CH
3-21 ~ H OMe Cl 3-22 ' ~ ~ ~ ~ ~ OMe Me N
3-23 ~ ~ ~ ~ ~ ~ ~ OMe N
3-24 ' ~ ' ~ ~ ~ Me Me CH
3-25 ~ ~ nPr ~ ~ ~ . . .
3-26 ~ ~ ~ ~ ~ ~ OMe OMe CH
3-27 ~ ~ ~ ~ Cl 3-28 ~ ~ ~ ~ ~ ~ ~ Me N
3-29 ~ ' ' ~ ~ ~ ~ OMe CH
3-31 ~ ~ cp~ . . . . . ..
3-32 ' ~ CF3 ~ ~ ~ ~ ' 3-33 ' 'CF2CF3 3-34 ' 'CH2CF3 ' ' ' ~ ~ ~
3-35 Me H Me CO-CH3 H H OMe OMe CH217 3-36 ' ' ' ~ ' ' ' ~ N
3 37 . . ~ ~ Na 3-38 ' ' ' ' ' K
3 39 ~ ~ ~ ~ CH
3 40 ~ ~ ~ ~ ~ Na ' '180-184 (d) 3 41 ~ ~ ~ ~ ~ H ~ Me 3-42 ~ ~ ~ ~ ~ Na 3 43 ~ ~ ~ ~ H ~ Cl ~210-211 ~d) 3 44 ~ ~ ~ ~ Na 3 45 . . ~ ~ ~ ~ Me Me Ex. R R2 R3 R4 Rs M X Y Z ~-P-no.
3-46 Me H Me CO-CH3 H H Me Me CH
~ OCH3 N 188-190(d) 3-48 ~ Na 175(d) 3-49 ' ' ' '' ~ OCH2CF3 NMe2 3-50 ~ ' ~ ~' H ~ ~ ~
3-51 ' ~ ~ ~Me ' OMe OMe CH
3-52 ~ OMe Me N
3-53 Me H Et CO-CH3 H H OMe OMe CH
~ Na 3-55 ~ ~ ~ '' N OMe Cl 3-56 ~ ' OMe Me N
357 ~ OMe N
3-58 ~ Me Me CH
3-59 ~ nPr 3-60 ~ ' OMe OMe CH
3-61 Cl 3-62 ~ Me N
3-63 ~ ' OMe 3-64 ~ ~ 'Pr ~ CH
3-65 ~ ~ CPr 3-66 ' ' CF3 3-67 ~ ~ CFCF ~ . . . .
3-68 ' ' CH CF
3-69 Me H Me C~-CF3 H H OMe OMe CH
3-70 ~ ~ N
3-71 ~ ' Na ~ ' ~
Ex .Pl 1 R2 R3 R4 R5 M X Y Z m . p .
nc~ .
3-72 Me H Me CO-CF3 H K OMe OMe N
CH
~ ~ Na 3-75 '~ ~ H ~ Me 3-76 ' ~ ~ ' ~ Na 3-77 ~ ' ' ' ~ H ~ Cl 3 -78 ' ~ ~ ~ ~ Na 3-79 ~ ~ Me Me 3-80 ' ' ' ' ~ H
3-81 ~ , ,OCH3 ' N
3-82 ' ' ~ ' ' Na ' 3-83 ~ OCH2CF3 NMe2 3-84 ' ' ' ~ ' H ~ ~ -3-85 ' ' ' ~ Me ' OMe OMe CH
3-86 ' ~ ' ~ ' ' OMe Me N
3-87 Me H Et CO-CF3 H tl OMe OMe CH
3-88 ' ~ ' ~ ' Na ' 3-89 ' ~ ~ ~ ' H OMe Cl 3-90 ' ' ' ~ ' ' OMe Me N
3-91 ' ' ' ~ ' ' ' OMe N
3-g2 ~ Me Me CH
3-93 ~ ~ nPr ~ ~ ~ . ..
3 94 ~ ~ ~ ~ ~ ~ OMe OMe CH
3-95 ' ' ~ C~ ' 3-96 ' ' . ' ' ~ ~ ' Me N
OMe Ex. Rl R2 R3 R4 Rs M X Y Z m.p.
no .
3-98 Me H iPr CO-CF3 H H OMe OMe CH
3 99 . . ~p~ . . . . . ..
3- 100 ' ' CF3 3-101 ~ ~ CF CF ~ . . . .
3-102 ' CH CF ~ . . . . .
3-103 Me H Me CO-OMe H H OMe OMe CH 205-207 (d) 3-104 ~ ~ ' ' ' ' ~ ' N
3- 105 ' ' ' ~ ~ Na ' 3-106 ~ ' ' ' ' K ' ~ ' 3-107 ~ ~ ~ ' ' ~ ~ ' CH
3-108 ~ . , . ~ Na ~ ~ ~ 176-178 (d~
3- 109 ~ ~ ' ' ~ H ' Me 3-110 ~ ' ~ ~ ~ Na ~ ' 3-111 ~ ~ ~ ~ ' H ~ Cl 3-112 ~ ~ ~ ' ~ Na 3-113 ~ ~ ' ~ ~ ~ Me Me 3-114 ~ ' ~ ' ~ H "
3-115 ~ - " OCH3 ~ N
3-116 ~ ~ ~ ~ ~ Na 3-117 ~ ~ ~ ~ ~ OCH2CF3 NMe~
3-118 ~ ' ' ' ' H
3-119 ' ' ' ' Me ' OMe OMe CH
3-120 ' ' ' ' ' ' OMe Me N
3-121 Me H Et CO-OMe H H OMe OMe CH
3-122 ~ Na ~ ~
3-123 ~ ~ ~ ~ ' H OMe Cl Ex . Rl R2 R3 R4 R5 M X Y Z m . p .
no .
3-124 Me H Et CO-OMe H H OMe Me t\l 3-125 ' ~ ~ ~ ' ' ' OMe 1~
3-126 ~ ' ' ~ ~ ~ Me Me CH
3-127 "Pr 3-128 ~ ' OMe OMe CH
3-t29 ~ Cl 3-130 ' ' ~ ' ' ' ' Me N
3-131 ' ~ ' ' OMe 3-132 ' ~ iPr ' ~ CH
3-133 ~ ~ cp, 3-134 ~ ~ CF3 3-135 ~ ~ CF CF ~ ~ ~ . ..
3-136 ~ ~ CH CF
3- 137 Me H Me CO-nPr H H OMe OMe CH
3- 138 ~ ~ ~ CO-~Bu ~ ' ' ' 3-139 ' ' CO-'Pr 3- 140 ~ " ~ CO-CHCI2 3- 141 ~ ~ ~ CO-CCI3 3-142 ' ' ~ CO-CH2CI
3- 143 ~ ~ CO-CH2Br 3-144 ~ ~ ~ COCH2OCH3 3-145 ~ CO-iPr 3-146 ' ~ ' CO-CCI = CCI2 3-147 ~ ~ ' CO-CH-CH2 ~
3-148 CO-C~CH
Ex. Rl R2 R3 R4 R5 M X Y Z m.p.
no .
3-149 ~ ~ ~SO2NMe,, 3-150 Me H Me SO2NHMe H H OMe OMe CH
3-151 ~ ~ ~ S~2NH2 3-152 ' SO2CH2F A
3-153 ~ ~ ~ SO2CF3 ~ ~ . .. ..
3-154 ' ~ ' CO-H Me 3-155 ' CO-Me ' ~
3-156 ' ~ ' COOMe 3-157 Me 3-F Me COCH3 H H OMe OMe CH
3- 159 ~4-NO2 3- 160 ~ 4-F
3- 161 ~4-OMe 3 162 ~3-OMe 3-163 ~6-OMe 3-164 ~4 NMe 3-165 ~ 4-CN
3- 166 ~ 6-Me 3-167 ~ H ~ CO-Et 3-168 Et H Me CO-H H H OMe OMe CH 126-129 (d) 3-169 ~ N
3-170 ' ~ ' ' ' Na ' 3-171 ~ ' ' ' ' K
3-172 ~ CH
3-173 ~ Na 3-174 ~ ' H ~ Me Ex. Rl R2 R3 R" R5 M X Y Zm.p.
no .
3 17~ Na 3-176 Et H Me CO-H H H OMe Cl CH
7 , ,. . ~ ~ Na 3- 178 ~ ' ~ ~ ~ ~ Me Me 3 17g ~ ~ ~ H
3-180 ~ ~ ~ ~ ~ ~ OCH3 ~ N
3-181 ' ' ' ' ' Na ~ ~
3-182 ~ ~ 'OCH2CF3 NMe2 3-183 ~ ' ' ' ' H
3-184 ' ' ~ ' Me ' OMe OMe CH
3-185 ~ ' ' ' ~ ' OMe Me N
3-186 Et H Me CO-OMe H H OMe OMe CH98-101 (d) 3-187 ' ' ' ' ' ' ' ' N
3- 188 ~ ' ~ ' ' Na 3-189 ' ~ ' ~ ' K ' ~ ' 3- 190 ' ' ' ' ' ' ' ~ CH
3-191 ~ Na ' ~ ~168-171 (t) 3-192 ' " ~ ' ~ H ' Me 3-193 ~ Na 3- 194 ' ' ~ ' ' H ' Cl 3-195 ' ~ ' ' ' Na 3-196 ~ ' ' ' ' ' Me Me 3-197 ' ~ H
3-198 ~ ' ' ' ' 'OCH3 ' N
99 , " . ~ ' Na 3-200 ~ OcH2cF3 NMe2 ; CA 02204610 1997-05-06 Ex. R1 R2 R3 R4 Rs M X Y Zm.p.
no .
3-201 ~ ' ~ ~ ~ H
3-202 Et H Me CO-OMe Me H OMe OMe CH
3-203 ~ ~ ~ ~ ~ ~ OMe Me N
3-204 Et H Me CO-CH3 H HC)Me OMe CH193-195 (d) 3-205 ~ ~ ' ~ ~ ~ ' ~ N
3-206 ~ ' ' ~ ~ Na 3-207 ~ ~ ~ ~ ~ K
3-208 ~ ~ ~ ~ ~ ~ ~ ~ CH
3-209 ' ~ ~ . ~ Na ~ ~ ~1~8 (d) 3-210 ~ ~ ' ~ ' H ' Me 3-211 ~ ' ' ' ' Na 3-212 ' ' ' ' ' H ' Cl 3-213 ~ ' ~ ~ ~ Na ~ ~
3-214 ~ ' ' ' ~ ' Me Me 3-215 ' ' ' ~ ' H ~ ~ -3-216 ~ ~ ~ ~ ' ~ OCH3 ~ N
3-217 ~ ' ' ~ ~ Na 3-218 ' " ~ OCH2CE3 NMe2 3-219 ' ~ ' ' ' H
3-220 ~ ~ ' ' Me ' OMe OMe CH
3-221 ~ ~ ' ~ ~ ~ OMe Me N
3-222 Et H Me CO-CF3 H H OMe OMe CH
3-223 ' ' ~ ~ ~ ~ ' ~ N
3-224 ~ ' ' ' ' Na 3-225 ' ' ' ' ' K ~ ' ' 3-226 ' ' ' ~ ~ CH
~x. Rl R2 R3 R4 Rs M X Y Z ~-p-~c~ .
3-227 ' ~ Na 3-228 Et H Me CO-CF3 H H OMe Me CH
3-229 ' ' ~ ~ ' Na ~ ' 3-230 ~ ' ' ' ~ H ~ Cl 3-231 ' ' ~ ~ ~ Na 3-232 ' ' ' ~ ~ ~ Me Me 3-233 ~ ~ ' ~ ~ H ~ ' ' 3-234 ' ~ ~ ~ OCH3 ~ N
3-235 ' ' ' ' ' Na 3-236 ' ~ OCH2CF3 NMe2 3-237 ' ' ' ' ' H
3-238 ' ~ ' ' Me ' OMe OMe CH
3-239 ~ " ' ~ ~ ' OMe Me N
3-240 NMe2 H Me CO-H H H OMe OMe CH190-192 (d) 3 241 ' ' ~ ' ' ' ' ' N
3-242 ' ~ ' ' ' Na 3-243 ~ " ~ ~ ' K
3-244 ' ' ' ~ ' ' ' ' CH
3-245 ' ~ Na 3-246 ' ' ~ ' ' H ' Me 3-247 ~ Na 3-248 ' ~ ~ ~ ~ H ~ Cl 3-249 ' ' ' ~ ~ Na 3-250 ' ' ' ' ' ' Me Me 3-251 ' ' . ' ' ' H ~ ' ' 3-252 ' ~ 'OCH3 ' N
- 71 ~
E~C .R 1 R2 R3 R" R5 M X Y Zm . p .
no .
3-253 ' ~ ' ' ' Na 3-254NMe2 H Me CC)-H H NaOCH2CF3NMe2 N
3-255 ~ ' ' ' ' H
3-256 ' ' ' ' Me ' OMe OMe CH
3-257 ' ' ' ' ' ' OMe Me N
3-258NMe2 H Me CO-CH3 H H OMe OMe CH2~9-222 (d) 3-259 ' ' ' ' ' ' ' ~ N
3-260 ' ' ' ' ' Na 3-261 ' ' ~ ' ' K
3-262 ' ~ ' ' ' CH
3-263 ' ' ' ' ' Na 3-264 ' ' ~ ' ' H ' Me 3-265 ' ~ ' ' ' Na 3-266 ~ ' ' ' ' H ' Cl 3-267 ' " ' ' ' Na 3-268 ' ~ ' ' ' ' Me Me 3-269 ' ~ ' ~ ' H
3-270 ' ~ ~ ' ' 'OCH3 ~ N
3-271 ~ ~ r ~ Na 3-272 ' ~ OCH~CF3 NMe2 3-273 ' ' ' ' ' H
3-274 ' ' ' ~ Me ' OMe OMe CH
3-275 ' ' ' ' ' ' OMe Me N
3-276 NMe2 H Me CO-CF3 H H OMe OMe CH
3-277 ' ~ N
3-278 ' ' ' ' ' Na CA 02204610 1997-0~-06 E~c .R1 R2 R3 R4 R5 M X Y Z m . p .
~o .
3-279 ' ' ~ ~ ~ K ' ~ ' 3-280 NMe2 H Me CO-CF3 H H OMe OMe CH
3-281 ~ ' Na 3-282 ' ' ' ' ' H ' Me 3-283 ' ~ Na 3-284 ' ' ' ' ~ H ' Cl 3-285 ' ' '' ' ' Na 3-286 ' ' ' ' ' ' Me Me 3-287 ' . ' ' ' ' H
3-288 ' ' ' ' ' 'OCH3 ' N
3-289 ~ Na 3-290 ~ OCH2CF3 NMe2 3-291 ' ~ ' ~ ' H
3-292 ~ ' ' ' Me ~ OMe OMe CH
3-293 ' ' ' ' ' ' OMe Me N
3-294NMe2 H Me CO-OMe H H OMe OMe CH 147-150 ~d) 3-295 ' ' ' ' ' ' ' ' N
3-296 ' ' ' ' ' Na ~ ' 3-297 ' ' ' ' ' K
3-298 ' ~ ' ' ' ' ' ' CH
3-299 ' ~ ' ' ' Na 3 300 . . ~ ~ ' H ' Me 3-301 ~ ~ ~ ~ ' Na 3-302 ' ' ' ' ~ H ' Cl 3 . . ~ ~ ' Na 3 304 . . ~ ~ Me Me Ex . Rl R2 R3 R4 RS M X Y Z m. p .
no .
3 305 ~ ~ ~ ' H
3-306 NMe2 H Me CO-OMe H H OCH3 Me N
Na 3-308 ' ~ . , ' 'OCHzCF3 NMe2 3 309 ~ ~ ~ ~ ' H
3-310 ' ' ' ~ Me 'OMe OMe CH
3-3 11 ' ' ~ ' ' ' OMe Me N
Table 4: Compol~nds of the formula (Idj R3R~; 502-hH-CO-NH ~ ( OCH~
Ex . no . R l ~R2~m R3 R4 m.p.
4-1 n ~cH2)scH3 -- Me COMe 4-2 CH2C 5 CH2 -- Me COMe 4-3 CH-C ~ CH -- Me COMe 4-4 CH2Ph -- Me COMe 4-5 Ph -- Me COMe 4-6 CH2CH2CI -- Me COMe 4-7 CH2CH2OMe -- Me COMe 4-8 NHNH2 -- Me COMe 4-9 NHOH -- Me COMe 4-10 NHCOCH3 -- Me COMe 4-ll NHCOOMe -- Me COMe 4-12 NHSO2Me -- Me COMe 4-13 NHSO2NHMe -- Me COMe 4-14 morpholin-4-~1 -- Me COMe 4-15 piperid ~-1-yl -- Me COMe 4-16 Me 4,6-~2 Me COMe 4-17 Me 3-OMe-4-CH2CI Me COMe 4- 18 Me -- Me CO-NH2 4-19 Me -- Me CO-NHNH2 4-20 Me -- Me CO-NHCOOMe Ex.no. Rl ~R2~m R3 R4 m.p.
4-21 Me - Me CS-Me 4-22 Me - Me CS-OMe 4-23 Me - Me CS-SMe 4-24 Me - Me S~2NH2 4-25 Me - Me SO2NMe2 4-26 Me ~ (CH2~5CH3 CHO
4-27 Me - ~cH2~4cH3 C~2Me 4-28 Me - CH2so2cH3 SO2CH3 4-2~ Me - CH=CH2 CHO
4-30 Me - CH2CH=CH2 CHO
4-31 Me - CH2C~CH COMe 4-32 Me - CyclohexYl COMe 4-33 Me - Cycloper,lyl COMe 4-34 Me - Me C~=NH~CH3 4-35 Me - Me C(=NCH3~CH3 4-36 lCH2)3CH3 CH2CN SO2NHOH
4-37 Me - Me CONMe2 4-38 Me - ' Cl=N-OH)Me 4-3g Me - ~ C(=N-OMe)Me 4-40 Me - ~ Cl=N-NMe2)Me Table 5: Compound~ of the formula (Ie~
N R3R~ OCH3 ( R )r~ S02R1 1 ( I e ) Ex. no . Rl ~R2~m R3 R4 m.p.
5-1 Me -- Me CO-H
5-2 Et --5-3 "Pr --5-4 NMe2 -- ' 5-5 Me ~-F
5-7 ~ 5-OMe 5-8 ~ 6-OMe 5-10 Et -- Me CO-CH3 5- 11 ~ -- ~ COOMe 5- 12 ' -- ~ COCF3 5-13 Me -- ~ COCH3 5-14 ~ -- ~ COOMe 5_15 ~ -- ' COCF3 Table 6: Com~ounds of the formula (If ) R3R'N SO2NHCONH oc~3 Ex . no . R l IR2~m R3 R4 m . p .
6-1 Me -- Me CO-H
6-2 ~ _ . COCF3 6-3 ~ -- ~ COOMe 6-4 ' -- ~ COCH3 6-5 ~ -- ' COCH2CH3 6-6 ~ -- Et CO-H
6-7 Et -- Me 6-8 ' -- ~ COCH3 6-9 ~ -- ~ COOMe 6-10 NMe2 ~ ~ CO-H
6- 11 ~ -- ~ COOCH3 6- 12 ~ -- ~ COCH3 6-13 Me 3-F ~ CO-H
6- 15 ~ 5-CI
6-1 6 ~ 5 0Me ~
CA 02204610 l997-05-06 Table 7: Compound~ of the formula (Ig) R3RtlN SO2R' OCH3 ;~SO2NH,CONH /~N 9 ) Ex.no. R1 (R2)m R3 R4 m.p.
7-1 Me -- Me CO-H
7-2 Et -- '' 7-3 "Pr _ .. ..
7-4 NMe2 ~ "' 7-5 Me 5-F "' 7-6 5-CI '' 5-0Me 7-8 ' 6-OMe 6-F ~, , 7-10 Et -- Me CO-CH3 7- 11 '' -- ' COOMe 7-12 '' _ ~ COCF3 7-13 Me -- ' COCH3 7.~ 4 ~ -- ' COOMe 7 1 5 ~ _ ~ COCF3 CA 02204610 1997-0~-06 ) B. Formulation examples a) A dusting powder i8 obtained by mixing 10 parts by weight of a compound of the formula (I) and 90 parts by weight of talc, as the inert substance, and the mixture iB comminuted in an impact mill.
b) A wettable powder which is readily dispersible in water is obtained by mixing 25 parts by weight of a compound of the formula (I), 64 parts by weight of kaolin-containing quartz, as the inert substance, 10 parts by weight of potassium ligninsulfonate and 1 part by weight of sodium oleylmethyltauride, as the wetting and dispersing agent, and grin~;ng 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 poly-glycol ether (8 E0) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to above 277~C) and gr;n~;ng the mixture to a fineness of less than 5 microns in a gr;n~;ng bead mill.
d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I), 75 parts by weight of cycloheY~none, as the solvent, and 10 parts by weight of oxyethylated nonylphenol, as the emulsifier.
e) Water-dispersible granules are obtained by m; Y; ng 75 parts by weight of a compound of the formula (I), 10 parts by weight of calcium ligninsulfonate, 5 parts by weight of sodium lauryl sulfate, 3 parts by weight of polyvinyl alcohol and 7 parts by weight of kaolin, CA 02204610 1997-0~-06 .
the mixture is ground on a pinned disk mill and the powder is granulated in a fluidized bed by spraying on water as the granulating liquid.
~,..
f) Water-dispersible granules are also obtained by homogenizing and precomminuting 25 parts by weight of a compound of the formula (I), 5 parts by weight of sodium 2,2'-~;nAphthylmethane-6,6'-disulfonate, 2 parts by weight of sodium oleylmethyltauride, 1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate and 50 parts by weight of water on a colloid mill, subsequently gr;n~;ng the mixture on a bead mill and atomizing and drying the suspen-sion thus obtained in a spray tower by means of a one-component nozzle.
C. Biological examples 1. Action on weeds by the pre-emergence method Seeds or pieces of rhizome of monocotyledon and dicotyledon weed plants are laid out in sandy loam soil in plastic pots and covered with soil. The compounds according to the invention, formulated in the form of wettable powders or emulsion concentrates, are then applied to the surface of the covering soil as an aqueous suspension or emulsion in various dosages with an amount of water applied, when converted, of 600 to 800 l/ha.
After the treatment, the pots are placed in a greenhouse and are kept under good growth conditions for the weeds.
The plant damage or emergence damage is rated visually after emergence of the test plants after a test period of 3 to 4 weeks in comparison with untreated controls. As the test results show, the compounds according to the invention have a good herbicidal pre-emergence activity against a broad spectrum of graminaceous weeds and broad-CA 022046l0 l997-0~-06 leaved weeds. For example, the compounds of Examples 1-204, 3-1, 3-13, 3-35, 3-40, 3-43, 3-47, 3-48, 3-103, 3-108, 3-168, 3-186, 3-191, 3-204, 3-209, 3-240, 3-258 and 3-294 from Tables 1 and 3 have a very good herbicidal action against harmful plants such as Sinapis alba, Chrysanthemum segetum, Avena sativa, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Setaria spp., Abutilon theophrasti, Amaranthus retroflexus and Panicum miliaceum in the pre-emergence method when applied in an amount of 0.3 kg or less of active ~ubstance per hectare.
2. Action on weeds by the post-emergence method Seeds or pieces of rhizome of mono- and dicotyledon weeds are laid out 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 are treated in the trifoliate stage. The compounds according to the invention, formulated as wettable powders or as emulsion concentrates, are sprayed onto the green parts of the plants in various dosages with an amount of water applied, when converted, of 600 to 800 l/ha. After the test plants have stood in the greenhouse under optimum growth conditions for about 3 to 4 weeks, the action of the preparations is rated visually in comparison with untreated controls. The compositions according to the invention also have a good herbicidal activity against a broad spectrum of economically important graminaceous weeds and broad-leaved weeds in the post-emergence method. For example, the compounds of Examples 1-204, 3-1, 3-13, 3-35, 3-40, 3-43, 3-47, 3-48, 3-103, 3-108, 3-168, 3-186, 3-191, 3-204, 3-209, 3-240, 3-258 and 3-294 from Tables 1 and 3 have a very good herbicidal action against harmful plants such as Sinapis alba, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Chrysanthemum segetum, Setaria spp., Abutilon theophrasti, Amaranthus retroflexus, Panicum miliaceum and Avena sativa in the post-emergence method when applied in an amount of 0.3 kg or less of active CA 02204610 1997-0~-06 ., substance per hectare.
3. Crop plant tolerance ~
In further experiments in the greenhouse, seeds of a relatively large number of crop plants and weeds are laid out in sandy loam soil and covered with soil. Some of the pots are treated immediately as described under Section 1, and the others are placed in a greenhouse until the plants had developed two to three true leaves, and are then sprayed with the substances of the formula (I) according to the invention in various dosages as described under Section 2. Four to five weeks after the application and 8t~n~ i ng time in the greenhouse, it is found by visual rating that the compounds according to the invention leave dicotyledonous crops such as, for example, soya, cotton, rape, sugar beet and potatoes, unharmed by the pre- and post-emergence methods even at high dosages of active compound. Some substances further-more also protect graminaceous crops, such as, forexample, barley, wheat, rye, sorghum, millet, maize or rice. Some of the compounds of the formula (I) have a high selectivity and are therefore suitable for control-ling undesirable plant growth in agricultural crops.
94 ' ~ OMe OMle CH
Cl 96 ~ Me N
~ ~ ~ OMe ; CA 02204610 1997-05-06 Ex. Rl R2 R3 R4 R5 M X Y Z m.p.
no .
98 Me H iPr CO-OMe H H OMe OMe CH
99 ~ ~ CPr ~ ~ .. . ..
100 ~ ~ CF3 101 ~ ~CF2CF3 102 ~ ~CH2CF3 103 Me H Me CO-CF3 H H OMe OMe CH
104 ~ N
105 ~ ~ ~ ~ ~ Na 106 ~ ~ ~ ' ~ K ~ ~ ~
CH
108 ~ Na ~
l o~ H ~ Me 110 ~ ~ ~ ~ ~ Na ~
H ~ Cl 112 ~ Na 11 3 ~ Me Me 1 1 4 ~ ~ ~ ~ ~ H ~ ~ ~
OCH3 ~ N
116 ~ Na ~ OcH2cF3 NMe2 118 ~ ~ ~ ' ~ H
11 9 ~ ~ ~ ' Me ~ OMe OMe CH
120 ~ ~ ~ ~ ~ ~ OMe Me N
121 Me tl Et CO-CF3 H H OMe OMe CH
122 ~ ~ Na ~ ~
123 ~ OMe Cl Ex. Rl R2 R3 R4 R5 M X YZ m.p.
no .
124 Me H Et CO-CF3 H H OMe Me N
125 ~ ' ~ ' ~ ~ ' OMe 1~
126 ' ' ~ ' ~ ~ Me Me CH
t 27 nPr 128 ' ~ ' ~ ~ ~ OMe OMe CH
129 ~ ~ Cl 130 . . . ~ ~ ~ ~ Me N
131 ~ ~ ~ ~ ~ ' ' OMe 132 ' ' iPr ~ ' ' ~ ~ CH
133 ' " CPr ' ' ~ ~ ' 134 ~ ' CF3 135 ~ 'CF2CF3 137 Me H Me CO-nPr H H OMe OMe CH
138 ~ ~ ' CO-'Bu ' ~ ' ~ ' 139 ~ ~ ~ Co.Cp~ ~ . .. ..
140 ~ CO-CHCI2 ' ' ' 141 ~ ' ~ CO-CCI3 142 ~ ~ ~ CO-CH2CI
143 ~ ' ~ CO-CH2Br 144 ' ~ ' COCH20CH3 ' ' ~ ~
145 ~ ~ CO-iPr ' ~ ' ' 146 ~ ~ ' CO-CCI = CCI2 147 ' ' ' CO-CH = CH2 ' ~
148 ~ ~ CO-C ~ CH
149 ~ ~ ~ SO2NMe2 ~ ~ ~
Ex . R R2 R3 R'l R5 M X Y z m . p .
~o .
150 Me ff Me SO2NHMe H H OMe OMe CH
15 1 ' ~ ~ S~2NH2 152 ~ 5O2CH2F
153 ' ' ' SO2CF3 154 ~ ' ' CO-H Me ' ' ' N
155 ' ~ ' CO-Me ' ' ' ' N
156 ~ ~ ~ COOMe ~ N
157 Me 3-F Me COCH3 H H OMe OMè CH
1 5 9 ~4 - N 0 2 r 1 60 ~ 4-F
161 ' 4-OMe 162 ' 3-OMe 163 ~ 6-OMe 1 64 ~4 NMe2 ' 165 ~ 4-CN
166 ~ 6-Me 167 ~ H ~ CO-Et ~ ' ' ' ' 168 Et H Me CO-H H H OMe OMe CH
169 " ~ N
170 ' ~ Na ' 171 ' ' ~ ' ' K ' ~ ' 172 ~ CH
173 ' ~ Na 174 ~ H ~ Me 175 ~ ~ ~ ' ' Na ' Ex . Rl R2 R3 R4 R5 M X YZ m . p .
~o .
176 Et H ~le CO-H H H OMe Cl CH
. . . ~ ~ Na 178 ~ ' ' Me Me 179 ' ~ H ~ ~ ~
180 ~ ~ ' ' ' 'OCH3 ' N
181 ~ ~ ' ' ' Na ' ~
182 ' ~ OCH2CF3 NMe2 183 ~ H ~ ~ ~
184 ' ~ ' ' Me ' OMe OMe CH
185 ' ~ OMe Me N
186 Et H Me CO-OMe H H OMe OMe CH
187 ~ N
188 ~ Na 189 ' ' ' ' ~ K ~ ~ ~
CH
191 ~ ~ ' ' ~ Na 192 ~ H ' Me 193 ~ Na ~ ' 194 ~ H ~ Cl 195 ~ ~ ' ' ' Na ' 196 ' ' ~ ' ' ' Me Me 197 ~ ' H ~ ~ ~
198 ' ~ ~ ' ' 'OCH3 ~ N
199 ~ r ~ Na 200 ~ OCH2CF3 NMe2 201 ~ H
Ex . R R2 R3 R4 R5 M X Y z m. p .
no .
202 Et H Me CO-OMe Me H OMe OMe CH
203 ' ~ ~ ~ ~ ' OMe Me N
204 Et H Me CO-CH3 H H OMe OMe CH
205 ' ~ ' ~ N
206 ~ ' ~ ~ ' Na 207 ~ ~ ~ ~ ~ K ' ~ ~
208 ~ ~ ' ~ ~ ' ' ~ CH
209 ~ ' ' ~ ~ Na 210 ~ ~ ' ' ~ H ' Me 211 ~ Na ~ ' 212 ~ H ~ Cl 213 ~ ~ ~ ' ~ Na 214 ~ ' ~ ~ ~ ' Me Me 215 ' ' ~ ~ ' H
216 ' ~ ~ ~ ~ ~ OCH3 ' N
217 ~ Na ~ ' 218 ~ OCH2CF3 NMe2 219 ' ~ H ~ ~ ~
220 ~ Me ~ OMe OMe CH
221 ' ' ~ OMe Me N
222 Et H Me CO-CF3 H H OMe OMe CH
223 ~ ' ' ' ' ~ ' ~ N
224 ~ ~ ~ ~ ~ Na ' 225 ~ K ~ ~ -226 " ~ ~ CH
227 ~ ~ ~ ~ ~ Na CA 022046l0 l997-05-06 Ex . R R' R3 R4 Rs M X Y Z m. p .
I10 .
228 Et H Me CO-CF3 H H OMe Me CH
229 ' ' ~ ~ ~ Na ~ ' 230 ' ~ H ' Cl 231 ' ' ' ~ ~ Na ~ ~
232 ' ' ' ~ ~ ' Me Me 233 ~ ' ~ ~ ~ H ~ ~ -234 ~ ~ . . . .OCH3 ~ N
23~ ~ ' ' ~ ~ Na 236 ' ' ' ~ OCH2CF3 NMe2 237 ' ' ' ~ ' H
238 ' ~ ' ~ Me ~ OMe OMe CH
239 ' ~ ~ ~ ~ ~ OMe Me N
Table 2: Compounds of the fo~nula (Ib) R2 o R 3 R 4 N/~ ' ~ 2 - N - C O - N R S )~Nly Ex R l R2 R3 R4 R5 M X Y Z m . p .
2-1 Me H Me CO-H H H OMe OMe CH
2-2 ' ' ' ' ' ' ' ' N
2-3 ~ ~ ' ' ' Na ' ~
2-4 ' ~ K ~ ' ~
2-5 ~ ' ' ' ' CH
2-6 ' ~ Na 2-7 ~ H ' Me 2-8 ~ ' Na ~ ' 2-9 ' ~ H ' Cl 2-10 ~ ' ' ' ' Na 2~ ' ' Me Me 2- 1 2 ~ H ~ . .
2-13 ' ~ ' OCH3 ~ N
2-14 ' ~ Na ' 2-15 ~ OCH2CF3 NMe2 2-16 ~ H ~ ~ ~
2- 17 ' ~ ~ ' Me ' OMe OMe CH
2- 18 ' ~ ' OMe Me N
2-19 Me H Et CO-H H H OMe QMe CH
2-20 ~ Na no Rl R2 R3 R~ R5 M X Y Z m. p .
2-21 Me H Et CO-H H H OMe Cl CH
2-22 ~ ' ' ~ ~ ~ OMe Me N
2-23 ~ OMe N
2-24 ~ ' ~ ~ ~ ~ Me Me CH
2-25 nPr 2-26 ~ ' ~ ~ ~ ~ OMe OMe CH
2-27 ~ ' ' ~ ~ ~ ' Cl 2-28 ' ' ' ~ ~ ~ ~ Me N
2-29 ~ ~ ~ ~ ~ ~ ~ OMe 2-30 ' ' iPt ' ~ ' ' ' CH
2-31 ' ' 'Pr 2-32 ~ ' CF3 ' ' ' ~ ' 2-34 ~ CH2CF3 2-35 Me H Me CO-CH3 H H OMe OMe CH
2 - 36 ~ ' ~ r ~ N
2-37 ' ' ' ' ' Na 2-38 ' ' ~ ' ' K
2-39 ' ~ ' ' ' ' ~ ' CH
2-40 ' ' ' ~ ' Na 2-41 ~ ' ' ' ' H ~ Me 2-42 ' ' ' ' ' Na 2-43 ' ' ' ' ' H ' Cl 2-44 ' ~ ~ ~ ~ Na 2-45 ~ ' ' ' ~ ~ Me Me 2-46 ' ' ' ~ ~ H ' ~ ~
2-47 ~ ~ ' ~ ' ' OCH3 ~ N
2 -4 B ' ' ' ' ' Na ' 2-49 ~ ~ , , , OCH2CF3 NMe2 no R1 R2 R3 R4 R5 M X Y Z m.p.
2-50 Me H Me CO-CH3 H H OcH2cF3 NMe2 N
2-51 ~ ~ ~ ~ Me ~ OMe OMe CH
2-52 ~ ' ~ ~ ~ ~ OMe Me N
2-53 Me H Et CO-CH3 H H OMe OMe CH
2-54 ~ ' ~ ~ ~ Na ~ ~
2-55 ' ~ ~ ~ ' H OMe Cl 2-56 ' ' ' ' ' ' OMe Me N
2-57 ' ' ' ~ ~ ~ ~ OMe N
2-58 ~ ' ~ ~ ~ ~ Me Me CH
2-59 "Pr ' ' ~ ' ' -2-60 ' ' ' ' ' ~ OMe OMe CH
2-61 r ~ Cl 2-62 ' ' ~ ' ' ~ ~ Me N
2-63 ' ' ' ' ' ' ' OMe 2-64 ' ' iPr ' ~ ' ' ~ CH
2-65 ~ ~ CPr 2-66 ~ ' CF3 2-68 ~ CH CF
2-69 Me H Me CO-CF3 H H OMe OMe CH
2-71 ' ~ ~ ~ ' Na 2-72 ' ~ K ' ~ ~
2-73 ' ' ' ~ ~ ~ ~ ' CH
2-74 ~ ~ Na 2-75 ' ' ' ~ ~ H ~ Me 2-76 ' ' ' ' ' Na 2-77 ~ ' ~ ' ' H ' Cl 2-78 ' ' ~ ' ~ Na CA 02204610 1997-0~-06 Ex .
no . R 1 R2 R3 R4 Rs M X Y Z m . p .
2-79 Me H Me CO-CF3 H Na Me Me CH
2-80 ~ ~ ~ ~ ~ H ' ~ ~
2-81 ' ' ' ~ ' ' OCH3 ~ N
2-82 ~ ' ' ' ~ Na 2-83 ' ~ ~ ~ OCH2CF3 NMe2 2-84 ' ' ' ~ ~ H
2-85 ~ ' ' ~ Me ~ OMe OMe CH
2-86 ' ~ ' ' ~ ~ OMe Me N
2-87 Me H Et CO-CF3 H H OMe OMe CH
2-88 ' ~ ~ ' ~ Na 2-89 ' ' ' ' ' H OMe Cl 2-90 ' ' ' ' ' ' OMe Me N
2-91 ' ' ' ' ' ' ~ OMe N
2-92 ~ ' Me Me CH
2-93 nPr 2-94 ~ ~ ' ' ' ~ OMe OMe CH
2-95 ' ' ' ' ' ' ' Me 2-96 ' ' ' ~ ~ ' ' Me N
2-97 ' ' ' ~ ~ ' ~ OMe N
2-98 ' ' 'Pr ' ' ~ ' ' CH
2-99 ' ' CPr 2 - 100 ' ' CF3 2-101 ' ' CF CF ~ . . . .
2-t 02 ' ' CH CF
2-103 Me H Me CO-OMe H H OMe OMe CH
2-10~ ' ' ' ' ' ' ~ ' N
2- 105 ' ~ ~ ' ' Na ~ ' 2-106 ' ' ' ' ' K ' ~ ~
2- 107 ' ' ' ~ ~ ~ ' ' CH
CA 02204610 1997-0~-06 Ex Rl R2 R3 R4 R5 M X Y Z m.p.
2-108 Me H Me CO-OMe H ~a OMe OMe CH
2-tO9 ' ~ ' ' ' H ' Me 2-110 ' ' ' ~ ' Na 2-111 ' ~ ' ' ' H ' Cl 2-112 ' ~ Na 2-113 ' ' ' ' ' ' Me Me 2-114 ' ~ ~ ' ' H
2-115 ' ' ' ' ' ' OCH3 ' N
2-116 ' ~ ' ' ' Na 2-117 ' ~ ~ ~ OCH2CF3 NMe2 2-118 ' ' ' ' ~ H
2-119 ' ' ' ' Me ' OMe OMe CH
2-120 ' ' ' ~ ' ' OMe Me N
2-121 Me H Et CO-OMe H H OMe OMe CH
2-122 ' ' ' ' ~ Na 2-123 ' ' ~ ' ' H OMe Cl 2-124 ' ' ~ ' ' ' OMe Me N
2-125 ' ' ' ' ' ' ~ OMe N
2-126 ~ r ~ Me Me CH
2-127 nPr 2-128 ' ' ' ' ' ' OMe OMe CH
2-129 ' ' ' ' ' ' ' Me 2-130 ~ Me N
2-131 ' ' ' ' ~ ' ' OMe 2-132 ' ' iPr ~ CH
2-133 ' ' CPr 2-134 ' ~ CF3 2-135 ~ CF2C~3 2-136 ' ' CH CF ~ . . . .
EX.
no . F4 l R2 R3 R4 R5 M X Y Z 2. p .
2-137 Me H Me CO-nPr H H OMe OMe CH
2-138 ~ ' ' CO-~u 2-139 ' ' ' CO-'Pr 2-140 ~ ~ ' CO-cHCl2 2-141 ~ ~ CO CC13 2- 142 ' ' ' CO-CH2CI
2-143 ~ ' ~ CO-CH2Br 2-144 ~ ~ ~ COCH20CI-l3 2- 145 ' ~ ' CO-iPr 2- 146 ~ ' ' CO-CCI = ' ~ ' ' 2- 147 ~ . . CO-CH = CH2 2-148 ' " ~ CO-C~CH
2- 149 ~ ~ ~ S02NMe2 2-150 ~ ~ ~ SO2NHMe 2- 151 ' ~ ' 502NH2 2-152 ~ ~ ' SO2CH2F
2- 153 ~ ~ S02CF3 2-154 ' ~ ~ CO-H Me ' ~ ' 2-155 ' ' ~ CO-Me ' ' ' 2-156 ' ~ ~ COOMe 2 157 Me 3-F Me COCH3 H H OMe OMe CH
2-158 ' 3-CI ' ' ' ' ~ ' 2-159 ' 4-NO2 ' ' ' ' ~ ' 2-160 ' 4-F
2 - 161 ' 4-OMe 2-162 ' 3-OMe ' ~ " ' ' ' 2- 163 ' 6-OMe 2-164 ' 4-NMe2 ' ' ~ ' " ' ' Ex R1 R2 R3 R4 Rs M X Y Z m . p .
2-165 Me 4-CN Me COCH3 H H OMe OMe CH
2-166 ' 6-Me ' ~ . . . .
2-167 ' H ' COEt 2-168 Et H Me CO-H H H OMe OMe CH
2-169 ' ~ ' ~ ~ ' ' ' N
2-170 ' ~ ~ ' ' Na ~ ' 2-171 ' ' ~ ' ' K ~ ~ ~
2-172 ~ ' ' ' ' ~ ' CH
2-173 ' ' ' ' ' Na ~ ' 2-174 ' ' ' ' ' H ~ Me 2-175 ~ ' ' ' ' Na ' 2-176 ~ ' H ' Cl 2-177 ~ ' ' ~ ' Na ~ ' 2- 178 ' ' ' ' ~ ' Me Me 2-179 ' ~ ' ' ' H
2- 180 ' ' ~ ' ' ' OCH3 ' N
2-181 ~ ' ~ ' ' Na 2- 182 ' ' ' ' OCH2CF3 NMe2 2-183 ' ~ ' ~ ' H
2- 184 ~ ~ ' ' Me ' OMe OMe CH
2-185 ~ ~ ~ ' ' ' OMe Me N
2-186 Et H Me CO-OMe H H OMe OMe CH
2-187 ' ' ' ' ~ ' ' ' N
2- 188 ' ' ' ' ' Na ' 2-189 ' ' ' ' ' K ' ~ ~
2- 190 ' ' ' ' ' ' ' ' CH
2-l 91 ' ' ' ' ' Na ~ ' 2-192 ~ ' ~ ~ ~ H ~ Me 2-193 ~ ~ ' ~ ' Na _ 59 _ no Rl R2 R3 R~ Rs M X Y Z m.p.
2-194 Et H Me CO-OMe H H OMe Cl CH
2-195 ~ ' ' ' ' Na 2-16 ' ~ ' ' ' ' Me Me 2-197 ~ H
2-198 ' ' ' ' ' ' OCH3 ~ N
2-199 ' ' ~ ~ ~ Na 2-200 ' ~ ~ ~ OCH2CF3 NMe2 2-201 ' ~ ~ ' ~ H ~ ' ' 2-202 ~ ~ ' ~ Me ~ OMe OMe CH
2-203 ~ ' ' ~ ~ ' OMe Me N
2-204 Et H Me CO-CH3 H H OMe OMe CH
2-205 ~ N
2-206 ' ~ ' ' ' Na 2-207 ' ' ' ~ ~ K
2-208 ' ' ~ ' ' ' ' ' CH
2-209 ' ' ' ' ' Na 2-210 ' ' ' ~ ~ H ' Me 2-211 ' ' ' ' ' Na ' 2-212 ' ~ ~ ' ' H ~ Cl 2-213 ' ' ~ ~ ' Na ~ ' 2-214 ' ~ Me Me 2-215 ' ' ' ' ' H ' ~ ' 2-216 ' ' ' ' ~ ~ OCH3 ~ N
2 217 ' ' ' ' ' Na 2-218 ' ' ' ~ ' ~ OCH2CF3 NMe2 2-2t9 ' ' ' ' ~ H
2-220 ~ ~ ' ' Me ~ OMe OMe CH
2-221 ' ' ' ~ ~ ' OMe OMe N
2-222 Et H Me CO-CF3 H H OMe OMe CH
~X
~~ Rl R2 R3 R4 Rs M X Y Z m.p.
2-223 Et H Me CO-CF3 H H OMe OMe N
2 224 ~ ' ' ~ ' Na ~ ' 2-225 ~ ' ~ ~ ' K ~ ~ -2-226 ~ ' ' ~ ' ~ ~ ~ CH
2-227 ' ~ ~ ~ ~ Na ~ ' 2-228 ' ~ ' ' ' H ' Me 2-229 ' ~ ~ ~ ~ Na 2-230 ~ ~ ~ ~ ~ H ~ Cl 2-231 ~ ~ ~ ~ ~ Na ~ ' 2-232 ' ~ ~ ~ ~ ~ Me Me 2-233 ' ~ ~ ~ ~ H ~ ~ -2-234 ~ ~ ~ OCH3 ~ N
2-235 ~ ~ Na 2-236 ~ ~ ~ ~ OCH2Cf3 NMe2 2-237 ~ ~ H ~ ~ -2-238 ~ ~ ~ ~ Me ~ OMe OMe CH
Z-239 ~ ~ OMe Me N
Table 3: Com~ouDd~ of the f ormula ( Ic ) R2 o R3RIN~so~-N-Co-NRs~ z ( I c ) N--~
Ex . R R2 R3 R4 Rs M X Y Zm . p .
no .
3-1 Me H Me CO-H H H OMe OMe CH158-160 (d) 3-2 ~ ' ' ' ' N
3-3 ~ ~ ~ ' ~ Na 34 " . . ~ ~ K
3 5 ~ ' CH
3-6 ~ ' Na 3 7 ~ ~ ~ ~ ' H ' Me 3-8 ' ' ' ' ' Na 3 9 ~ ~ ~ ' ' H ' Cl O " " . ~ ' Na 3~ ' ' ' ' ' Me Me 3-12 ~ H
3-13 ~ ~ . . , , OCH3 ' N 189-191 (d) 3_14 . . ~ ~ ' Na 3-15 ~ ~ ' ' ' ' OCH2CF3 NMe2 3-16 ' ' ' ' ~ H
3-17 ' ' ~ ~ Me ~ OMe OMe CH
3-1 8 ~ ' OMe Me N
3-19 Me H Et CO-H H H OMe OMe CH
Ex . R R2 R3 R4 Rs M X Y Zm. p .
no .
3-20 Me H Et CO-H tlNa OMe OMe CH
3-21 ~ H OMe Cl 3-22 ' ~ ~ ~ ~ ~ OMe Me N
3-23 ~ ~ ~ ~ ~ ~ ~ OMe N
3-24 ' ~ ' ~ ~ ~ Me Me CH
3-25 ~ ~ nPr ~ ~ ~ . . .
3-26 ~ ~ ~ ~ ~ ~ OMe OMe CH
3-27 ~ ~ ~ ~ Cl 3-28 ~ ~ ~ ~ ~ ~ ~ Me N
3-29 ~ ' ' ~ ~ ~ ~ OMe CH
3-31 ~ ~ cp~ . . . . . ..
3-32 ' ~ CF3 ~ ~ ~ ~ ' 3-33 ' 'CF2CF3 3-34 ' 'CH2CF3 ' ' ' ~ ~ ~
3-35 Me H Me CO-CH3 H H OMe OMe CH217 3-36 ' ' ' ~ ' ' ' ~ N
3 37 . . ~ ~ Na 3-38 ' ' ' ' ' K
3 39 ~ ~ ~ ~ CH
3 40 ~ ~ ~ ~ ~ Na ' '180-184 (d) 3 41 ~ ~ ~ ~ ~ H ~ Me 3-42 ~ ~ ~ ~ ~ Na 3 43 ~ ~ ~ ~ H ~ Cl ~210-211 ~d) 3 44 ~ ~ ~ ~ Na 3 45 . . ~ ~ ~ ~ Me Me Ex. R R2 R3 R4 Rs M X Y Z ~-P-no.
3-46 Me H Me CO-CH3 H H Me Me CH
~ OCH3 N 188-190(d) 3-48 ~ Na 175(d) 3-49 ' ' ' '' ~ OCH2CF3 NMe2 3-50 ~ ' ~ ~' H ~ ~ ~
3-51 ' ~ ~ ~Me ' OMe OMe CH
3-52 ~ OMe Me N
3-53 Me H Et CO-CH3 H H OMe OMe CH
~ Na 3-55 ~ ~ ~ '' N OMe Cl 3-56 ~ ' OMe Me N
357 ~ OMe N
3-58 ~ Me Me CH
3-59 ~ nPr 3-60 ~ ' OMe OMe CH
3-61 Cl 3-62 ~ Me N
3-63 ~ ' OMe 3-64 ~ ~ 'Pr ~ CH
3-65 ~ ~ CPr 3-66 ' ' CF3 3-67 ~ ~ CFCF ~ . . . .
3-68 ' ' CH CF
3-69 Me H Me C~-CF3 H H OMe OMe CH
3-70 ~ ~ N
3-71 ~ ' Na ~ ' ~
Ex .Pl 1 R2 R3 R4 R5 M X Y Z m . p .
nc~ .
3-72 Me H Me CO-CF3 H K OMe OMe N
CH
~ ~ Na 3-75 '~ ~ H ~ Me 3-76 ' ~ ~ ' ~ Na 3-77 ~ ' ' ' ~ H ~ Cl 3 -78 ' ~ ~ ~ ~ Na 3-79 ~ ~ Me Me 3-80 ' ' ' ' ~ H
3-81 ~ , ,OCH3 ' N
3-82 ' ' ~ ' ' Na ' 3-83 ~ OCH2CF3 NMe2 3-84 ' ' ' ~ ' H ~ ~ -3-85 ' ' ' ~ Me ' OMe OMe CH
3-86 ' ~ ' ~ ' ' OMe Me N
3-87 Me H Et CO-CF3 H tl OMe OMe CH
3-88 ' ~ ' ~ ' Na ' 3-89 ' ~ ~ ~ ' H OMe Cl 3-90 ' ' ' ~ ' ' OMe Me N
3-91 ' ' ' ~ ' ' ' OMe N
3-g2 ~ Me Me CH
3-93 ~ ~ nPr ~ ~ ~ . ..
3 94 ~ ~ ~ ~ ~ ~ OMe OMe CH
3-95 ' ' ~ C~ ' 3-96 ' ' . ' ' ~ ~ ' Me N
OMe Ex. Rl R2 R3 R4 Rs M X Y Z m.p.
no .
3-98 Me H iPr CO-CF3 H H OMe OMe CH
3 99 . . ~p~ . . . . . ..
3- 100 ' ' CF3 3-101 ~ ~ CF CF ~ . . . .
3-102 ' CH CF ~ . . . . .
3-103 Me H Me CO-OMe H H OMe OMe CH 205-207 (d) 3-104 ~ ~ ' ' ' ' ~ ' N
3- 105 ' ' ' ~ ~ Na ' 3-106 ~ ' ' ' ' K ' ~ ' 3-107 ~ ~ ~ ' ' ~ ~ ' CH
3-108 ~ . , . ~ Na ~ ~ ~ 176-178 (d~
3- 109 ~ ~ ' ' ~ H ' Me 3-110 ~ ' ~ ~ ~ Na ~ ' 3-111 ~ ~ ~ ~ ' H ~ Cl 3-112 ~ ~ ~ ' ~ Na 3-113 ~ ~ ' ~ ~ ~ Me Me 3-114 ~ ' ~ ' ~ H "
3-115 ~ - " OCH3 ~ N
3-116 ~ ~ ~ ~ ~ Na 3-117 ~ ~ ~ ~ ~ OCH2CF3 NMe~
3-118 ~ ' ' ' ' H
3-119 ' ' ' ' Me ' OMe OMe CH
3-120 ' ' ' ' ' ' OMe Me N
3-121 Me H Et CO-OMe H H OMe OMe CH
3-122 ~ Na ~ ~
3-123 ~ ~ ~ ~ ' H OMe Cl Ex . Rl R2 R3 R4 R5 M X Y Z m . p .
no .
3-124 Me H Et CO-OMe H H OMe Me t\l 3-125 ' ~ ~ ~ ' ' ' OMe 1~
3-126 ~ ' ' ~ ~ ~ Me Me CH
3-127 "Pr 3-128 ~ ' OMe OMe CH
3-t29 ~ Cl 3-130 ' ' ~ ' ' ' ' Me N
3-131 ' ~ ' ' OMe 3-132 ' ~ iPr ' ~ CH
3-133 ~ ~ cp, 3-134 ~ ~ CF3 3-135 ~ ~ CF CF ~ ~ ~ . ..
3-136 ~ ~ CH CF
3- 137 Me H Me CO-nPr H H OMe OMe CH
3- 138 ~ ~ ~ CO-~Bu ~ ' ' ' 3-139 ' ' CO-'Pr 3- 140 ~ " ~ CO-CHCI2 3- 141 ~ ~ ~ CO-CCI3 3-142 ' ' ~ CO-CH2CI
3- 143 ~ ~ CO-CH2Br 3-144 ~ ~ ~ COCH2OCH3 3-145 ~ CO-iPr 3-146 ' ~ ' CO-CCI = CCI2 3-147 ~ ~ ' CO-CH-CH2 ~
3-148 CO-C~CH
Ex. Rl R2 R3 R4 R5 M X Y Z m.p.
no .
3-149 ~ ~ ~SO2NMe,, 3-150 Me H Me SO2NHMe H H OMe OMe CH
3-151 ~ ~ ~ S~2NH2 3-152 ' SO2CH2F A
3-153 ~ ~ ~ SO2CF3 ~ ~ . .. ..
3-154 ' ~ ' CO-H Me 3-155 ' CO-Me ' ~
3-156 ' ~ ' COOMe 3-157 Me 3-F Me COCH3 H H OMe OMe CH
3- 159 ~4-NO2 3- 160 ~ 4-F
3- 161 ~4-OMe 3 162 ~3-OMe 3-163 ~6-OMe 3-164 ~4 NMe 3-165 ~ 4-CN
3- 166 ~ 6-Me 3-167 ~ H ~ CO-Et 3-168 Et H Me CO-H H H OMe OMe CH 126-129 (d) 3-169 ~ N
3-170 ' ~ ' ' ' Na ' 3-171 ~ ' ' ' ' K
3-172 ~ CH
3-173 ~ Na 3-174 ~ ' H ~ Me Ex. Rl R2 R3 R" R5 M X Y Zm.p.
no .
3 17~ Na 3-176 Et H Me CO-H H H OMe Cl CH
7 , ,. . ~ ~ Na 3- 178 ~ ' ~ ~ ~ ~ Me Me 3 17g ~ ~ ~ H
3-180 ~ ~ ~ ~ ~ ~ OCH3 ~ N
3-181 ' ' ' ' ' Na ~ ~
3-182 ~ ~ 'OCH2CF3 NMe2 3-183 ~ ' ' ' ' H
3-184 ' ' ~ ' Me ' OMe OMe CH
3-185 ~ ' ' ' ~ ' OMe Me N
3-186 Et H Me CO-OMe H H OMe OMe CH98-101 (d) 3-187 ' ' ' ' ' ' ' ' N
3- 188 ~ ' ~ ' ' Na 3-189 ' ~ ' ~ ' K ' ~ ' 3- 190 ' ' ' ' ' ' ' ~ CH
3-191 ~ Na ' ~ ~168-171 (t) 3-192 ' " ~ ' ~ H ' Me 3-193 ~ Na 3- 194 ' ' ~ ' ' H ' Cl 3-195 ' ~ ' ' ' Na 3-196 ~ ' ' ' ' ' Me Me 3-197 ' ~ H
3-198 ~ ' ' ' ' 'OCH3 ' N
99 , " . ~ ' Na 3-200 ~ OcH2cF3 NMe2 ; CA 02204610 1997-05-06 Ex. R1 R2 R3 R4 Rs M X Y Zm.p.
no .
3-201 ~ ' ~ ~ ~ H
3-202 Et H Me CO-OMe Me H OMe OMe CH
3-203 ~ ~ ~ ~ ~ ~ OMe Me N
3-204 Et H Me CO-CH3 H HC)Me OMe CH193-195 (d) 3-205 ~ ~ ' ~ ~ ~ ' ~ N
3-206 ~ ' ' ~ ~ Na 3-207 ~ ~ ~ ~ ~ K
3-208 ~ ~ ~ ~ ~ ~ ~ ~ CH
3-209 ' ~ ~ . ~ Na ~ ~ ~1~8 (d) 3-210 ~ ~ ' ~ ' H ' Me 3-211 ~ ' ' ' ' Na 3-212 ' ' ' ' ' H ' Cl 3-213 ~ ' ~ ~ ~ Na ~ ~
3-214 ~ ' ' ' ~ ' Me Me 3-215 ' ' ' ~ ' H ~ ~ -3-216 ~ ~ ~ ~ ' ~ OCH3 ~ N
3-217 ~ ' ' ~ ~ Na 3-218 ' " ~ OCH2CE3 NMe2 3-219 ' ~ ' ' ' H
3-220 ~ ~ ' ' Me ' OMe OMe CH
3-221 ~ ~ ' ~ ~ ~ OMe Me N
3-222 Et H Me CO-CF3 H H OMe OMe CH
3-223 ' ' ~ ~ ~ ~ ' ~ N
3-224 ~ ' ' ' ' Na 3-225 ' ' ' ' ' K ~ ' ' 3-226 ' ' ' ~ ~ CH
~x. Rl R2 R3 R4 Rs M X Y Z ~-p-~c~ .
3-227 ' ~ Na 3-228 Et H Me CO-CF3 H H OMe Me CH
3-229 ' ' ~ ~ ' Na ~ ' 3-230 ~ ' ' ' ~ H ~ Cl 3-231 ' ' ~ ~ ~ Na 3-232 ' ' ' ~ ~ ~ Me Me 3-233 ~ ~ ' ~ ~ H ~ ' ' 3-234 ' ~ ~ ~ OCH3 ~ N
3-235 ' ' ' ' ' Na 3-236 ' ~ OCH2CF3 NMe2 3-237 ' ' ' ' ' H
3-238 ' ~ ' ' Me ' OMe OMe CH
3-239 ~ " ' ~ ~ ' OMe Me N
3-240 NMe2 H Me CO-H H H OMe OMe CH190-192 (d) 3 241 ' ' ~ ' ' ' ' ' N
3-242 ' ~ ' ' ' Na 3-243 ~ " ~ ~ ' K
3-244 ' ' ' ~ ' ' ' ' CH
3-245 ' ~ Na 3-246 ' ' ~ ' ' H ' Me 3-247 ~ Na 3-248 ' ~ ~ ~ ~ H ~ Cl 3-249 ' ' ' ~ ~ Na 3-250 ' ' ' ' ' ' Me Me 3-251 ' ' . ' ' ' H ~ ' ' 3-252 ' ~ 'OCH3 ' N
- 71 ~
E~C .R 1 R2 R3 R" R5 M X Y Zm . p .
no .
3-253 ' ~ ' ' ' Na 3-254NMe2 H Me CC)-H H NaOCH2CF3NMe2 N
3-255 ~ ' ' ' ' H
3-256 ' ' ' ' Me ' OMe OMe CH
3-257 ' ' ' ' ' ' OMe Me N
3-258NMe2 H Me CO-CH3 H H OMe OMe CH2~9-222 (d) 3-259 ' ' ' ' ' ' ' ~ N
3-260 ' ' ' ' ' Na 3-261 ' ' ~ ' ' K
3-262 ' ~ ' ' ' CH
3-263 ' ' ' ' ' Na 3-264 ' ' ~ ' ' H ' Me 3-265 ' ~ ' ' ' Na 3-266 ~ ' ' ' ' H ' Cl 3-267 ' " ' ' ' Na 3-268 ' ~ ' ' ' ' Me Me 3-269 ' ~ ' ~ ' H
3-270 ' ~ ~ ' ' 'OCH3 ~ N
3-271 ~ ~ r ~ Na 3-272 ' ~ OCH~CF3 NMe2 3-273 ' ' ' ' ' H
3-274 ' ' ' ~ Me ' OMe OMe CH
3-275 ' ' ' ' ' ' OMe Me N
3-276 NMe2 H Me CO-CF3 H H OMe OMe CH
3-277 ' ~ N
3-278 ' ' ' ' ' Na CA 02204610 1997-0~-06 E~c .R1 R2 R3 R4 R5 M X Y Z m . p .
~o .
3-279 ' ' ~ ~ ~ K ' ~ ' 3-280 NMe2 H Me CO-CF3 H H OMe OMe CH
3-281 ~ ' Na 3-282 ' ' ' ' ' H ' Me 3-283 ' ~ Na 3-284 ' ' ' ' ~ H ' Cl 3-285 ' ' '' ' ' Na 3-286 ' ' ' ' ' ' Me Me 3-287 ' . ' ' ' ' H
3-288 ' ' ' ' ' 'OCH3 ' N
3-289 ~ Na 3-290 ~ OCH2CF3 NMe2 3-291 ' ~ ' ~ ' H
3-292 ~ ' ' ' Me ~ OMe OMe CH
3-293 ' ' ' ' ' ' OMe Me N
3-294NMe2 H Me CO-OMe H H OMe OMe CH 147-150 ~d) 3-295 ' ' ' ' ' ' ' ' N
3-296 ' ' ' ' ' Na ~ ' 3-297 ' ' ' ' ' K
3-298 ' ~ ' ' ' ' ' ' CH
3-299 ' ~ ' ' ' Na 3 300 . . ~ ~ ' H ' Me 3-301 ~ ~ ~ ~ ' Na 3-302 ' ' ' ' ~ H ' Cl 3 . . ~ ~ ' Na 3 304 . . ~ ~ Me Me Ex . Rl R2 R3 R4 RS M X Y Z m. p .
no .
3 305 ~ ~ ~ ' H
3-306 NMe2 H Me CO-OMe H H OCH3 Me N
Na 3-308 ' ~ . , ' 'OCHzCF3 NMe2 3 309 ~ ~ ~ ~ ' H
3-310 ' ' ' ~ Me 'OMe OMe CH
3-3 11 ' ' ~ ' ' ' OMe Me N
Table 4: Compol~nds of the formula (Idj R3R~; 502-hH-CO-NH ~ ( OCH~
Ex . no . R l ~R2~m R3 R4 m.p.
4-1 n ~cH2)scH3 -- Me COMe 4-2 CH2C 5 CH2 -- Me COMe 4-3 CH-C ~ CH -- Me COMe 4-4 CH2Ph -- Me COMe 4-5 Ph -- Me COMe 4-6 CH2CH2CI -- Me COMe 4-7 CH2CH2OMe -- Me COMe 4-8 NHNH2 -- Me COMe 4-9 NHOH -- Me COMe 4-10 NHCOCH3 -- Me COMe 4-ll NHCOOMe -- Me COMe 4-12 NHSO2Me -- Me COMe 4-13 NHSO2NHMe -- Me COMe 4-14 morpholin-4-~1 -- Me COMe 4-15 piperid ~-1-yl -- Me COMe 4-16 Me 4,6-~2 Me COMe 4-17 Me 3-OMe-4-CH2CI Me COMe 4- 18 Me -- Me CO-NH2 4-19 Me -- Me CO-NHNH2 4-20 Me -- Me CO-NHCOOMe Ex.no. Rl ~R2~m R3 R4 m.p.
4-21 Me - Me CS-Me 4-22 Me - Me CS-OMe 4-23 Me - Me CS-SMe 4-24 Me - Me S~2NH2 4-25 Me - Me SO2NMe2 4-26 Me ~ (CH2~5CH3 CHO
4-27 Me - ~cH2~4cH3 C~2Me 4-28 Me - CH2so2cH3 SO2CH3 4-2~ Me - CH=CH2 CHO
4-30 Me - CH2CH=CH2 CHO
4-31 Me - CH2C~CH COMe 4-32 Me - CyclohexYl COMe 4-33 Me - Cycloper,lyl COMe 4-34 Me - Me C~=NH~CH3 4-35 Me - Me C(=NCH3~CH3 4-36 lCH2)3CH3 CH2CN SO2NHOH
4-37 Me - Me CONMe2 4-38 Me - ' Cl=N-OH)Me 4-3g Me - ~ C(=N-OMe)Me 4-40 Me - ~ Cl=N-NMe2)Me Table 5: Compound~ of the formula (Ie~
N R3R~ OCH3 ( R )r~ S02R1 1 ( I e ) Ex. no . Rl ~R2~m R3 R4 m.p.
5-1 Me -- Me CO-H
5-2 Et --5-3 "Pr --5-4 NMe2 -- ' 5-5 Me ~-F
5-7 ~ 5-OMe 5-8 ~ 6-OMe 5-10 Et -- Me CO-CH3 5- 11 ~ -- ~ COOMe 5- 12 ' -- ~ COCF3 5-13 Me -- ~ COCH3 5-14 ~ -- ~ COOMe 5_15 ~ -- ' COCF3 Table 6: Com~ounds of the formula (If ) R3R'N SO2NHCONH oc~3 Ex . no . R l IR2~m R3 R4 m . p .
6-1 Me -- Me CO-H
6-2 ~ _ . COCF3 6-3 ~ -- ~ COOMe 6-4 ' -- ~ COCH3 6-5 ~ -- ' COCH2CH3 6-6 ~ -- Et CO-H
6-7 Et -- Me 6-8 ' -- ~ COCH3 6-9 ~ -- ~ COOMe 6-10 NMe2 ~ ~ CO-H
6- 11 ~ -- ~ COOCH3 6- 12 ~ -- ~ COCH3 6-13 Me 3-F ~ CO-H
6- 15 ~ 5-CI
6-1 6 ~ 5 0Me ~
CA 02204610 l997-05-06 Table 7: Compound~ of the formula (Ig) R3RtlN SO2R' OCH3 ;~SO2NH,CONH /~N 9 ) Ex.no. R1 (R2)m R3 R4 m.p.
7-1 Me -- Me CO-H
7-2 Et -- '' 7-3 "Pr _ .. ..
7-4 NMe2 ~ "' 7-5 Me 5-F "' 7-6 5-CI '' 5-0Me 7-8 ' 6-OMe 6-F ~, , 7-10 Et -- Me CO-CH3 7- 11 '' -- ' COOMe 7-12 '' _ ~ COCF3 7-13 Me -- ' COCH3 7.~ 4 ~ -- ' COOMe 7 1 5 ~ _ ~ COCF3 CA 02204610 1997-0~-06 ) B. Formulation examples a) A dusting powder i8 obtained by mixing 10 parts by weight of a compound of the formula (I) and 90 parts by weight of talc, as the inert substance, and the mixture iB comminuted in an impact mill.
b) A wettable powder which is readily dispersible in water is obtained by mixing 25 parts by weight of a compound of the formula (I), 64 parts by weight of kaolin-containing quartz, as the inert substance, 10 parts by weight of potassium ligninsulfonate and 1 part by weight of sodium oleylmethyltauride, as the wetting and dispersing agent, and grin~;ng 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 poly-glycol ether (8 E0) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to above 277~C) and gr;n~;ng the mixture to a fineness of less than 5 microns in a gr;n~;ng bead mill.
d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I), 75 parts by weight of cycloheY~none, as the solvent, and 10 parts by weight of oxyethylated nonylphenol, as the emulsifier.
e) Water-dispersible granules are obtained by m; Y; ng 75 parts by weight of a compound of the formula (I), 10 parts by weight of calcium ligninsulfonate, 5 parts by weight of sodium lauryl sulfate, 3 parts by weight of polyvinyl alcohol and 7 parts by weight of kaolin, CA 02204610 1997-0~-06 .
the mixture is ground on a pinned disk mill and the powder is granulated in a fluidized bed by spraying on water as the granulating liquid.
~,..
f) Water-dispersible granules are also obtained by homogenizing and precomminuting 25 parts by weight of a compound of the formula (I), 5 parts by weight of sodium 2,2'-~;nAphthylmethane-6,6'-disulfonate, 2 parts by weight of sodium oleylmethyltauride, 1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate and 50 parts by weight of water on a colloid mill, subsequently gr;n~;ng the mixture on a bead mill and atomizing and drying the suspen-sion thus obtained in a spray tower by means of a one-component nozzle.
C. Biological examples 1. Action on weeds by the pre-emergence method Seeds or pieces of rhizome of monocotyledon and dicotyledon weed plants are laid out in sandy loam soil in plastic pots and covered with soil. The compounds according to the invention, formulated in the form of wettable powders or emulsion concentrates, are then applied to the surface of the covering soil as an aqueous suspension or emulsion in various dosages with an amount of water applied, when converted, of 600 to 800 l/ha.
After the treatment, the pots are placed in a greenhouse and are kept under good growth conditions for the weeds.
The plant damage or emergence damage is rated visually after emergence of the test plants after a test period of 3 to 4 weeks in comparison with untreated controls. As the test results show, the compounds according to the invention have a good herbicidal pre-emergence activity against a broad spectrum of graminaceous weeds and broad-CA 022046l0 l997-0~-06 leaved weeds. For example, the compounds of Examples 1-204, 3-1, 3-13, 3-35, 3-40, 3-43, 3-47, 3-48, 3-103, 3-108, 3-168, 3-186, 3-191, 3-204, 3-209, 3-240, 3-258 and 3-294 from Tables 1 and 3 have a very good herbicidal action against harmful plants such as Sinapis alba, Chrysanthemum segetum, Avena sativa, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Setaria spp., Abutilon theophrasti, Amaranthus retroflexus and Panicum miliaceum in the pre-emergence method when applied in an amount of 0.3 kg or less of active ~ubstance per hectare.
2. Action on weeds by the post-emergence method Seeds or pieces of rhizome of mono- and dicotyledon weeds are laid out 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 are treated in the trifoliate stage. The compounds according to the invention, formulated as wettable powders or as emulsion concentrates, are sprayed onto the green parts of the plants in various dosages with an amount of water applied, when converted, of 600 to 800 l/ha. After the test plants have stood in the greenhouse under optimum growth conditions for about 3 to 4 weeks, the action of the preparations is rated visually in comparison with untreated controls. The compositions according to the invention also have a good herbicidal activity against a broad spectrum of economically important graminaceous weeds and broad-leaved weeds in the post-emergence method. For example, the compounds of Examples 1-204, 3-1, 3-13, 3-35, 3-40, 3-43, 3-47, 3-48, 3-103, 3-108, 3-168, 3-186, 3-191, 3-204, 3-209, 3-240, 3-258 and 3-294 from Tables 1 and 3 have a very good herbicidal action against harmful plants such as Sinapis alba, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Chrysanthemum segetum, Setaria spp., Abutilon theophrasti, Amaranthus retroflexus, Panicum miliaceum and Avena sativa in the post-emergence method when applied in an amount of 0.3 kg or less of active CA 02204610 1997-0~-06 ., substance per hectare.
3. Crop plant tolerance ~
In further experiments in the greenhouse, seeds of a relatively large number of crop plants and weeds are laid out in sandy loam soil and covered with soil. Some of the pots are treated immediately as described under Section 1, and the others are placed in a greenhouse until the plants had developed two to three true leaves, and are then sprayed with the substances of the formula (I) according to the invention in various dosages as described under Section 2. Four to five weeks after the application and 8t~n~ i ng time in the greenhouse, it is found by visual rating that the compounds according to the invention leave dicotyledonous crops such as, for example, soya, cotton, rape, sugar beet and potatoes, unharmed by the pre- and post-emergence methods even at high dosages of active compound. Some substances further-more also protect graminaceous crops, such as, forexample, barley, wheat, rye, sorghum, millet, maize or rice. Some of the compounds of the formula (I) have a high selectivity and are therefore suitable for control-ling undesirable plant growth in agricultural crops.
Claims (8)
1. A compound of the formula (I) or a salt thereof (I) in which W is an oxygen or sulfur atom, m is 0, 1, 2 or 3, n is 0, 1 or 2, R1 is hydroxyl, amino, mono- or disubstituted amino, hydroxylamino, substituted hydroxylamino, hydrazino, substituted hydrazino, an aliphatic hydrocarbon or hydrocarbonoxy radical, aryl, heteroaryl, aryloxy or heteroaryloxy, where each of the last 6 radicals mentioned is unsubstituted or substituted, R2 is halogen, CN, NO2, amino, mono- or disubstituted amino, alkyl or alkoxy, where each of the last two radicals mentioned is unsubstituted or substituted, R3 is an aliphatic hydrocarbon radical, which is unsubstituted or substituted, R4 is an acyl radical, R5 is hydroyen, hydroxyl, (C1-C4)alkyl, (C1-C4)alkoxy, (C2-C4)alkenyl or (C2-C4)alkynyl, where each of the last 4 radicals mentioned Z is CH, N or , in which R° is halogen, cyano, alkyl, alkoxy, haloalkyl or haloalkoxy.
2. A compound or a salt thereof as claimed in claim 1, in which R1 is OH, NR6R7, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)alkoxy, (C2-C6)alkenoxy, (C2-C6)alkynoxy, (C3-C7) cycloalkyl, (C3-C7)cycloalkoxy, (C3-C7)cycloalkyl-(C1-C2)alkyl, (C3-C7)cycloalkyl-(Cl-C2)alkoxy, phenoxy, phenyl, thienyl or pyridyl, where each of the last fourteen radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkoxy, (C1-C4)haloalkyl, (C2-C4)alkenoxy, (C2-C4)haloalkenoxy, (C2-C4)alkynoxy, (C2-C4)haloalkynoxy, CN, NO2, N3, SCN, OCN, OH, NR8R9, CO-R10, (C1-C4)alkylthio, (C1-C4)haloalkylthio, unsubstituted and substituted phenyl, SO-R11 and SO2R12, and in the case of cyclic radicals also (C1-C4)alkyl and (C1-C4)haloalkyl, R2 is halogen, (C1-C3)alkyl, (C1-C3)haloalkyl, (C1-C5)alkoxyalkyl, NO2, NR13R14, CN, (C1-C3)alkoxy or (C1-C3)haloalkoxy, R3 is (C1-C6)-alkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, (C3-C7)-cycloalkyl or (C3-C7)-cycloalkyl-(C1-C2)alkyl, where each of the last five radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C7)alkoxy, (C1-C4)haloalkoxy, (C2-C4)alkenoxy, (C2-C4)haloalkenoxy, (C2-C4)alkynoxy, (C2-C4)haloalkynoxy, (C1-C4)alkylthio, (C2-C4)haloalkylthio, (C2-C4)alkenylthio, (C1-C4)-haloalkenylthio, (C2-C4)alkynylthio, (C2-C4)haloalkynylthio, CN, NO2, N3, SCN, OCN, OH, NR15R16, SOR17, SO2R18 and CO-R19, R4 is CO-H, CO-R20, CO-OR21, CO-NR22R23, CO-SR24, CS-R25, CS-OR26, CS-NR27R28, CS-SR29, C(=NR30)R31, SO2R32 or SO2NR33R34, R5 is H, OH, (C1-C3)alkyl, (C2-C3)alkenyl, (C2-C3)alkynyl or (C1-C3)alkoxy, R6 is H, OH, NH2, mono- or di-[(C1-C3)alkyl]amino, (C1-C4)alkyl, (C2-C4)alkenyl, (C2-C4)alkynyl, (C1-C4)alkoxy, (C2-C4)alkenoxy or (C2-C4)alkynoxy, where each of the last eight radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C3)alkoxy, (C1-C3)haloalkoxy, (C1-C3)alkylthio and (C1-C3)haloalkylthio, R7 H, (C1-C4)alkyl, (C2-C4)alkenyl, (C2-C4)alkynyl, [(C1-C4)alkyl]-carbonyl, [(C2-C4)alkenyl]-carbonyl, [(C2-C4)alkynyl]-carbonyl, [(C1-C4)alkoxy]-carbonyl, [(C2-C4)alkenoxy]-carbonyl, [(C2-C4)alkynyloxy]-carbonyl, [(C1-C4)alkyl]-aminocarbonyl, di[(C1-C4)alkyl]amino-carbonyl, (C1-C4)alkyl-sulfonyl, (C2-C4)alkenyl-sulfonyl, (C2-C4)alkynylsulfonyl, (C1-C4)alkylaminosulfonyl, or di-[(C1-C4)alkyl]aminosulfonyl, where each of the last sixteen radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, OH, (C1-C3)alkoxy, (C1-C3)haloalkoxy, (C1-C3)alkylthio and (C1-C3)haloalkylthio, or NR6R7 together is a heterocyclic radical which, in addition to the N atom, can contain further hetero units from the group consisting of O, N, S, SO and SO2 in the ring skeleton and which is unsubstituted or substituted by radicals from the group consisting of the oxo function, halogen, OH, NH2, NO2, NHCH3, N(CH3)2, CN, CONH2, CONHCH3, CO2CH3, CON(CH3)2, COCH3, CHO, (C1-C3)alkyl, (C1-C3)-haloalkyl, (C1-C3)alkoxy and (C1-C3)haloalkyl, R8 is H, (C1-C4)alkyl, (C1-C4)haloalkyl, (C2-C4)alkenyl, (C2-C4)haloalkenyl, (C2-C4)alkynyl, (C2-C4)haloalkynyl, OH, (C1-C3)alkoxy or (C2-C3)haloalkoxy and R9 is H, (C1-C4)alkyl, (C1-C4)haloalkyl, (C2-C4)alkenyl, (C2-C4)haloalkenyl, (C2-C4)alkynyl, (C2-C4)haloalkynyl, CO-H, CO2CH3, CO2CH3, CO-CH3, CO-NH2, CO-NHCH3 or CON(CH3)2, or NR8R9 together is a heterocyclic radical which, in addition to the N atom, can contain further hetero units from the group consisting of O, N, S, SO or SO2 in the ring skeleton and is unsubstituted or substituted by one or more radicals from the group consisting of halogen, OH, NH2, NO2, CONH2, CONHCH3, CON(CH3)2, NHCH3, N(CH3)2, CN, CO2CH3, COCH3, CO-H, (C1-C3)alkyl, (C1-C3)haloalkyl, (C1-C3)alkoxy, (C1-C3)haloalkoxy and the oxo function, R10 is H, (C1-C3)alkyl, (C1-C3)haloalkyl, (C1-C3)alkoxy, (C1-C3)haloalkoxy, (C1-C3)alkylthio, (C1-C3)haloalkylthio, NH2, NHCH3, N(CH3)2 or OH, R11 is (C1-C4)alkyl, (C1-C4)haloalkyl, (C2-C5)alkoxyalkyl, (C2-C4)alkenyl, (C2-C4)haloalkenyl, (C2-C4)alkynyl or (C2-C4)haloalkynyl, R12 is (C1-C4)alkyl, (C1-C4)haloalkyl, (C2-C4)alkenyl, (C2-C5)haloalkenyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C2-C4)alkenoxy, (C2-C4)haloalkenoxy, NH2 or mono- or di[(C1-C4)alkyl]amino, R13 is H, (C1-C3)alkyl, (C1-C3)haloalkyl, (C1-C3)alkoxy, (C1-C3)haloalkoxy or OH and R14 is H, (C1-C3)alkyl, (C1-C3)haloalkyl, CHO, COCH3, CO2CH3, COC2H5, SO2CH3, SO2C2H5 or CN, or NR13R14 together is a heterocyclic radical which, in addition to the N atom, can contain further hetero units from the group consisting of O, N, S, SO and SO2 in the ring skeleton and is unsubstituted or substituted by one or more radicals from the group consisting of halogen, OH, NH2, NO2, NHCH3, N(CH3)2, CN, CONHCH3, CO2CH3, COCH3, CON(CH3)2, CO-H, (C1-C3) alkyl, CONH2, (C1-C3) alkoxy, (C1-C3)haloalkyl, (C1-C3)haloalkoxy and the oxo function, R15 is H, (C1-C3)alkyl, (C1-C3)haloalkyl, (C1-C3)alkoxy, (C1-C3)haloalkoxy, OH, NH2 or mono- or di-[(C1-C2)alkyl]amino and R16 is H, C1-C3-alkyl, C1-C3-haloalkyl, CHO, COCH3, CO2CH3, CO2C2H5, SO2CH3 or CN, or NR15R16 together is a heterocyclic radical which, in addition to the N atom, can contain further hetero units from the group consisting of O, N, S, SO and SO2 in the ring skeleton and is unsubstituted or substituted by one or more radicals from the group consisting of halogen, OH, NH2, NO2, NHCH3, N(CH3)2, CN, CONHCH3, CO2CH3, COCH3, CON(CH3)2, CO-H, (C1-C3)alkyl, CONH2, (C1-C3)alkoxy, (C1-C3)haloalkyl, (C1-C3)haloalkoxy and the oxo function, R17 is (C1-C6)alkyl, (C1-C6)haloalkyl, (C1-C6)alkoxyalkyl, (C3-C6)cycloalkyl, (C3-C6)halocycloalkyl, (C2-C6)-alkenyl, (C2-C6)haloalkenyl, (C2-C6)alkynyl or (C2-C6)-haloalkynyl, R18 is (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C3-C7)cycloalkyl, (C1-C6)alkoxy, (C2-C6)alkenoxy, (C2-C6)alkynoxy or mono- or di[(C1-C6)alkyl]amino, where each of the last nine radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, OH, (C1-C3)alkoxy, (C1-C3)haloalkoxy, (C1-C3)alkylthio, (C1-C3)haloalkylthio, NH2, mono- or di[(C1-C4)alkyl]amino, NO2, CN, CO2CH3, CO2C2H5, CN, SO2CH3, SO2C2H5, CONH2, CON(CH3)2, CONHCH3, COCH3, CO-H
and CO-CF3, R19 is H, (C1-C4)alkyl, (C1-C4)haloalkyl, (C2-C4)alkenyl, (C2-C4)haloalkenyl, (C2-C4)alkynyl, (C2-C4)haloalkynyl, (C3-C6)cycloalkyl, (C3-C6)halocycloalkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C2-C4)alkenoxy, (C2-C4)haloalkenoxy, (C2-C4)alkynoxy, (C2-C4)haloalkynoxy, NH2, (C1-C4)alkylamino, (C1-C4)haloalkylamino, di[(C1-C4)alkyl]- or di[(C1-C4)haloalkyl]amino.
R20 is (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl or (C3-C7)cycloalkyl, where each of the last four radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C3)alkoxy, (C1-C3)haloalkoxy, (C2-C3)alkenoxy, (C2-C3)haloalkenoxy, OH, (C1-C4)alkylthio, (C1-C4)-haloalkylthio, NH2, mono- and di[(C1-C4)alkyl]amino NHCOOCH3, NHCOCH3, NHCO-H, N(CH3)CO2CH3, N(CH3)CO-H, CN, NO2, COOCH3, COOC2H5, CO-CH3, CO-H, CONH2, CONHCH3, CON(CH3)2, SO2CH3, SOCH3 and SO2N(CH3)2, R21 is a radical analogous to R20, R22 is a radical analogous to R6 and R23 is a radical analogous to R7, or NR22R23 together is a radical analogous to NR6R7, R24 is a radical analogous to R21, R25 is a radical analogous to R20, R26 is a radical analogous to R21, R27 is a radical analogous to R6 and R28 is a radical analogous to R7 or NR27R28 together is a radical analogous to NR6R7, R29 is a radical analogous to R21, R30 is H, OH, (C1-C4) alkoxy, (C1-C4)haloalkoxy, (C2-C4) alkenyloxy, (C2-C4) haloalkenoxy, (C1-C4)-alkyl, (C1-C4)haloalkyl, (C2-C4)alkenyl, (C2-C4)haloalkenyl, (C2-C4)alkynyl, (C2-C4)-haloalkynyl,(C3-C6)cycloalkyl, NH2, mono- or di[(C1-C4)alkyl]amino or mono- or di[(C1-C4)-haloalkyl]amino, R31 is H, (C1-C4)alkyl, (C1-C4)haloalkyl, (C2-C4)-alkenyl, (C2-C4)alkynyl, (C2-C4)haloalkynyl, (C2-C4)haloalkynyl, (C1-C4)alkoxy, (C1-C4)-haloalkoxy, (C2-C4)halo-alkenyl, (C2-C4)-alkenoxy, (C2-C4)haloalkenoxy, (C2-C4)alkynoxy, (C2-C4)haloalkynoxy, NH2, mono - or di[(C1-C4)alkyl]amino or mono- or di[(C1-C4)-haloalkyl]amino, R32 is (C1-C4)alkyl, (C2-C4)alkenyl, (C2-C4)-alknyl, (C2-C4)alkoxy, (C2-C4)alkenoxy or (C2-C4)alkynoxy, where each of the last six radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkoxy, OH, NH2, CN, NO2 and mono- and di[(C1-C4)alkyl]amino, R33 is a radical analogous to R6 and R34 is a radical R7 or NR33R34 together is a radical analogous to NR6R7.
and CO-CF3, R19 is H, (C1-C4)alkyl, (C1-C4)haloalkyl, (C2-C4)alkenyl, (C2-C4)haloalkenyl, (C2-C4)alkynyl, (C2-C4)haloalkynyl, (C3-C6)cycloalkyl, (C3-C6)halocycloalkyl, (C1-C4)alkoxy, (C1-C4)haloalkoxy, (C2-C4)alkenoxy, (C2-C4)haloalkenoxy, (C2-C4)alkynoxy, (C2-C4)haloalkynoxy, NH2, (C1-C4)alkylamino, (C1-C4)haloalkylamino, di[(C1-C4)alkyl]- or di[(C1-C4)haloalkyl]amino.
R20 is (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl or (C3-C7)cycloalkyl, where each of the last four radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C3)alkoxy, (C1-C3)haloalkoxy, (C2-C3)alkenoxy, (C2-C3)haloalkenoxy, OH, (C1-C4)alkylthio, (C1-C4)-haloalkylthio, NH2, mono- and di[(C1-C4)alkyl]amino NHCOOCH3, NHCOCH3, NHCO-H, N(CH3)CO2CH3, N(CH3)CO-H, CN, NO2, COOCH3, COOC2H5, CO-CH3, CO-H, CONH2, CONHCH3, CON(CH3)2, SO2CH3, SOCH3 and SO2N(CH3)2, R21 is a radical analogous to R20, R22 is a radical analogous to R6 and R23 is a radical analogous to R7, or NR22R23 together is a radical analogous to NR6R7, R24 is a radical analogous to R21, R25 is a radical analogous to R20, R26 is a radical analogous to R21, R27 is a radical analogous to R6 and R28 is a radical analogous to R7 or NR27R28 together is a radical analogous to NR6R7, R29 is a radical analogous to R21, R30 is H, OH, (C1-C4) alkoxy, (C1-C4)haloalkoxy, (C2-C4) alkenyloxy, (C2-C4) haloalkenoxy, (C1-C4)-alkyl, (C1-C4)haloalkyl, (C2-C4)alkenyl, (C2-C4)haloalkenyl, (C2-C4)alkynyl, (C2-C4)-haloalkynyl,(C3-C6)cycloalkyl, NH2, mono- or di[(C1-C4)alkyl]amino or mono- or di[(C1-C4)-haloalkyl]amino, R31 is H, (C1-C4)alkyl, (C1-C4)haloalkyl, (C2-C4)-alkenyl, (C2-C4)alkynyl, (C2-C4)haloalkynyl, (C2-C4)haloalkynyl, (C1-C4)alkoxy, (C1-C4)-haloalkoxy, (C2-C4)halo-alkenyl, (C2-C4)-alkenoxy, (C2-C4)haloalkenoxy, (C2-C4)alkynoxy, (C2-C4)haloalkynoxy, NH2, mono - or di[(C1-C4)alkyl]amino or mono- or di[(C1-C4)-haloalkyl]amino, R32 is (C1-C4)alkyl, (C2-C4)alkenyl, (C2-C4)-alknyl, (C2-C4)alkoxy, (C2-C4)alkenoxy or (C2-C4)alkynoxy, where each of the last six radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkoxy, OH, NH2, CN, NO2 and mono- and di[(C1-C4)alkyl]amino, R33 is a radical analogous to R6 and R34 is a radical R7 or NR33R34 together is a radical analogous to NR6R7.
3. A compound or a salt thereof as claimed in claim 1 or 2, in which R1 is (C1-c4)-alkyl, (C1-C4)haloalkyl or mono- or di-[(Cl-C4)alkyl]-amino, R2 is halogen, (C1-C2)alkyl, (C1-C2)alkoxy, NO2, CN
or N(CH3)2 m is 0 or 1, R3 is (C1-C4)alkyl, (C1-C4)haloalkyl or cyclopropyl, R4 is CHO, COR20, COOR21, CONR22R23, SO2R32 or SO2NR33R34, R20 is (C1-C4)alkyl, (C1-C4)haloalkyl, cyclopropyl, (C2-C4) alkenyl, (C2- C4) alkenyl or (C1-C3)alkoxy-(C1-C4)alkyl, R21 is (C1-C4)alkyl, (C1-C4)haloalkyl or (C1-C3)alkoxy-(C1-C4)alkyl, R22 is H or (C1-C4)alkyl, R23 is H or (C1-C4)alkyl, R32 is (C1-C4) alkyl, (C2-C4)alkenyl, (C2-C4)alkynyl, (C1-C4)haloalkyl or (C1-C3)alkoxy-(C1-C4)alkyl, R33 is H or (C1-C4)alkyl, and R34 is H, (C1-C4) alkyl or (C1-C4)alkoxy.
or N(CH3)2 m is 0 or 1, R3 is (C1-C4)alkyl, (C1-C4)haloalkyl or cyclopropyl, R4 is CHO, COR20, COOR21, CONR22R23, SO2R32 or SO2NR33R34, R20 is (C1-C4)alkyl, (C1-C4)haloalkyl, cyclopropyl, (C2-C4) alkenyl, (C2- C4) alkenyl or (C1-C3)alkoxy-(C1-C4)alkyl, R21 is (C1-C4)alkyl, (C1-C4)haloalkyl or (C1-C3)alkoxy-(C1-C4)alkyl, R22 is H or (C1-C4)alkyl, R23 is H or (C1-C4)alkyl, R32 is (C1-C4) alkyl, (C2-C4)alkenyl, (C2-C4)alkynyl, (C1-C4)haloalkyl or (C1-C3)alkoxy-(C1-C4)alkyl, R33 is H or (C1-C4)alkyl, and R34 is H, (C1-C4) alkyl or (C1-C4)alkoxy.
4. 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 unsubstituted or substituted phenyl or C1-C4-alkyl, or b) reacting a sulfochloride of the formula (IV) (IV) with a heterocyclic amine of the formula (V) (V) in the presence of a cyanate, or c) reacting a sulfonamide of the formula (II) successively with a chloroformic acid aryl ester of the formula aryl-O-CO-Cl (VI) and with a heterocyclic amine of the formula (V) or d) reacting a sulfonylurea of the formula (VII) (VII) with an acylating agent R4-Nuc, in which Nuc is a leaving group, or e) reacting a sulfonamide of the formula (II) with a (thio)isocyanate of the formula (VIII) (VIII) in the presence of a suitable base, or f) reacting a sulfonyl isocyanate of the formula (IX) (IX) with a heterocyclic amine of the formula (V), in which, in the above formulae (II) to (IX), the radicals R1, R2, R3, R4, R5, W, X, Y and Z and the indices m and n are defined as in formula (I), and in the variants a) - c) and f), initially compounds of the formula (I) where W = O are obtained.
5. A herbicidal or plant growth-regulating composition, which comprises at least one compound of the formula (I) or a salt thereof as claimed in one of claims 1 to 3 and formulating auxiliaries customary in plant protection.
6. A method of controlling harmful plants or regulating the growth of plants, which comprises applying an active amount of at least one compound of the formula (I) or of a salt thereof as claimed in any of claims 1 to 3 to the harmful plant or plants, plant seeds thereof or the area on which they grow.
7. The use of a compound of the formula (I) or a salt thereof as claimed in any of claims 1 to 3 as a herbicide or plant growth regulator.
8. A compound of the formula (XIX) (XIX) in which U* is NH2, Cl or mono- or disubstituted amino and R1, R2, R3, R4, n and m are defined as in formula (I) as claimed in claim 1, 2 or 3, with the exception of compounds of the formula (XVII) in which a) U* is amino, R1 is amino, R3 is ethyl, R4 is 4-[N-(diethylamino-2,6-demithylphenyl)-imino]-1,4-dihydro-1-oxo-naphthalen-2-ylcarbon, m is the number 0 and n is the number 2 or in which b) U* is n-butylamino, R1 is n-butulamino, R2 is n-butyl, R3 is n-propyl, R4 is n-dodecanoyl, m is the number 1 and n is the number 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4439675.9 | 1994-11-07 | ||
| DE19944439675 DE4439675A1 (en) | 1994-11-07 | 1994-11-07 | N-acyl-N-alkylaminophenylsulfonylureas with sulfur substituents, process for their preparation and use as herbicides and plant growth regulators |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2204610A1 true CA2204610A1 (en) | 1996-05-17 |
Family
ID=6532646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2204610 Abandoned CA2204610A1 (en) | 1994-11-07 | 1995-10-25 | N-acyl-n-alkylaminophenylsulfonylureas with sulfur substituents, processes for their preparation and their use as herbicides and plant growth regulators |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0790985A1 (en) |
| JP (1) | JPH10509443A (en) |
| AU (1) | AU3869595A (en) |
| BR (1) | BR9509609A (en) |
| CA (1) | CA2204610A1 (en) |
| DE (1) | DE4439675A1 (en) |
| WO (1) | WO1996014304A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19619628A1 (en) * | 1996-05-15 | 1997-11-20 | Hoechst Schering Agrevo Gmbh | (Hetero) arylsulfonylureas with an imino function, their preparation and use as herbicides and plant growth regulators |
| DE19702200A1 (en) | 1997-01-23 | 1998-07-30 | Hoechst Schering Agrevo Gmbh | Phenylsulfonylureas, process for their preparation and their use as herbicides and plant growth regulators |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK259280A (en) * | 1979-07-20 | 1981-01-21 | Du Pont | HERBICIDE SULPHONAMIDES |
| EP0116518B1 (en) * | 1983-02-04 | 1987-10-28 | Ciba-Geigy Ag | N-phenylsulfonyl-n'-pyrimidinyl- and -triazinylurea |
| DE4236902A1 (en) * | 1992-10-31 | 1994-05-05 | Hoechst Ag | New phenylsulfonylureas, preparation and use as herbicides and plant growth regulators |
-
1994
- 1994-11-07 DE DE19944439675 patent/DE4439675A1/en not_active Withdrawn
-
1995
- 1995-10-25 EP EP95937843A patent/EP0790985A1/en not_active Withdrawn
- 1995-10-25 JP JP8515006A patent/JPH10509443A/en active Pending
- 1995-10-25 CA CA 2204610 patent/CA2204610A1/en not_active Abandoned
- 1995-10-25 BR BR9509609A patent/BR9509609A/en unknown
- 1995-10-25 AU AU38695/95A patent/AU3869595A/en not_active Abandoned
- 1995-10-25 WO PCT/EP1995/004183 patent/WO1996014304A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| AU3869595A (en) | 1996-05-31 |
| EP0790985A1 (en) | 1997-08-27 |
| BR9509609A (en) | 1997-10-28 |
| JPH10509443A (en) | 1998-09-14 |
| WO1996014304A1 (en) | 1996-05-17 |
| DE4439675A1 (en) | 1996-05-09 |
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