CA2224612A1 - Substituted hydrazinophenylsulfonylureas, processes for their preparation and their use as herbicides and plant growth regulators - Google Patents

Abstract

Compounds have the formula (I), in which R1 stands for S(O)nR4, SO2NR5R6 or CONR5R6; A stands for a residue having the formula A1 or, should R1 stand for S(O)nR4 or SO2NR5R6, may also stand for a residue having the formula A2 R7R8C=N-NR9- (A1), R10R11N-NR9- (A2); and R2 to R11, W, X, Y and Z have the definitions given in the first claim. These compounds are suitable as selective herbicides or plant growth regulators. The compounds having the formula (I) may be prepared in an analogous manner to known processes by using at least some new intermediate products (see process described in claim 5 and intermediate products having the formulas (II), (IV) and (VI)).

Description

CA 022246l2 l997-l2-l2 ~nD 97/00247 - 1 - ~ P ~ /~P96/02513 De~cription Substituted hydrazinophenylsulfonylureas, processes for their preparation and their use as herbicides and plant growth regulators It is known that phenylsulfonylureas having hydrazine partial structures have herbicidal properties. These are chiefly hydrazones (EP-A-382 437, EP-A-562 575) or heterocyclic compounds having an incorporated hydrazine structure (EP-A-382 436, EP-A-384 602). The known com-~0 pounds in each case carry halogen, alkyl or alkoxy-carbonyl radicals in the para-position relative to the substituted hydrazine groups.

Surprisingly, phenylQulfonylureas which contain substi-tuted hydrazine radicals and sulfonyl or carbamoyl groups in the para-position relative to these radicals and are particularly suitable as herbicides or plant growth regulators have now been found.

The present invention relates to compounds of the formula (I) or salts thereof A~ S O ~- N H - C - N ~ (~Z ( I ) in which R1 is S(o)nR4, So2NR5R6 or CoNR5R6, R2 is H, halogen, NO2, CN, (Cl-C4)alkyl, (C1-C4)alkoxy, [(Cl-C4)alkyl]carbonyl or ~(Cl-C4)alkoxy]carbonyl, where each of the last four radical~ mentioned i~
unsubstituted or substituted in the alkyl part by one or more halogen atoms, R3 is H or (Cl-C4)alkyl, preferably H or CH3, R4 is an aliphatic hydrocarbon radical or aryl, where each of the last two radicals mentioned is unsubsti-tuted or substituted, R5 and R6 independently of one another are H, an aliphatic hydrocarbon radical or aryl, where each of the last two radicals mentioned is unsubstituted or substituted, or~0 R5 and R6, together with the N atom, are a heterocyclic radical, which is unsubstituted or substituted, A is a radical of the formula Al or, in the case that Rl = S(o)nR4 or So2NR5R6, also A2, R~ Rl~
C~ N-N- N --N --R8/ l9 1 11 1 9 R7 and R3 independently of one another are H, NO2, CN, an aliphatic hydrocarbon radical, a heterocyclic radical or aryl, where each of the last three radi-cals mentioned is unsubstituted or substituted, or an acyl radical, where carbon-cont~;ning radicals R7 and R9 preferably contain 1 to 20 carbon atoms, or R7 and R8, together with the carbon atom, are a carbo-cyclic or heterocyclic ring, which is unsubstituted or substituted, R9 is H, an aliphatic hydrocarbon radical, which is unsubstituted or substituted, or an acyl radical, where carbon-cont~;ning radicals R9 preferably contain 1 to 20 carbon atoms, Rl~ is an acyl radical, which is unsubstituted or sub-stituted and preferably contains 1 to 20 carbon atoms, Rll is H or an aliphatic hydrocarbon radical, which is unsubstituted or substituted and preferably contains 1 to 12 carbon atoms, W is an oxygen or sulfur atom, X and Y independently of one another are H, halogen, (C1-C4)alkyl, (Cl-C4)alkoxy, (C1-C4)alkylthio, where each of 'he last three radicals mentioned i8 unsub-stituted or substituted by one or more radicals from the group consisting of halogen, (Cl-C4)alkoxy and (Cl-C4)alkylthio, or mono- or di-[(Cl-C4)alkyl]amino, (C3-C6)cycloalkyl, (C2-C5)alkenyl, (C2-C5)alkynyl, (C2-C5)alkenyloxy or (C2-C5)alkynyloxy, Z is CH or N and n is 0, 1 or 2.

The compounds of the formula (I) can form salts in which the hydrogen of the -S02-NH group is replaced by a cation suitable for agriculture. These salts are, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or also a onium salts or salts with organic amines. Compounds of the formula (I) can also form salts by addition of a suitable inorganic or organic acid, such as, for example, HCl, HBr, H2S04 or HN03, or also oxalic acid or sulfonic acids, onto a basic group, such as, for example, amino or alkylamino. Suitable substituents, which can be present in deprotonated form, such as, for example, sulfonic acids or carboxylic acids, can form inner salts with groups which in turn can be protonated, such as amino groups. Salts can also be formed by replac-ing the hydrogen in suitable substituents, such as, for example, sulfonic acids or carboxylic acids, by a cation suitable for agriculture. These salts are, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or also ammonium salts or salts with organic amines.

In formula (I) and all the following formulae, the alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio radicals and the corresponding unsaturated and/or sub-stituted radicals can in each case be straight-chain or branched in the carbon skeleton. Unless stated specifi-cally, 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 radicals. Alkyl radicals, also in the composite meAn;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 l,3-dimethylbutyl, and heptyl radicals, such as n-heptyl, 1-methylhexyl and 1,4-dimethylpentyl; alkenyl and alkynyl radicals have the meAn;ng of the possible unsaturated radicals correspo~;ng to the alkyl radicals;
alkenyl is, for example, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methyl-but-3-en-1-yl and 1-methyl-but-2-en-1-yl; and alkynyl is, for example, propargyl, but-2-in-1-yl, but-3-in-1-yl and 1-methyl-but-3-in-1-yl. Alkenyl in the form of (C3-C4) alkenyl is preferably an alkenyl radical having 3 or 4 carbon atoms in which the multiple bond is not ho~e~ to the carbon atom to which the radical conta;n;ng the remaining part of the molecule ("yl~ position) is bonded. Correspon~l;ng statements apply to (C3-C4) alkynyl.
Cycloalkyl is a carbocyclic, saturated ring system having preferably 3-8 carbon atoms, for example cyclopropyl, cyclopentyl or cyclohexyl.

Halogen is, for example, fluorine, chlorine, bromine or iodine. Haloalkyl, -alkenyl and-alkynyl are alkyl, alkenyl or alkynyl which is partially or completely substituted by halogen, preferably by fluorine, chlorine and/or bromine, in particular by fluorine or chlorine, for example mo~ohAloalkyl (= monohalog~noAlkyl), perhalo-alkyl, CF3, CHF2, CH2F, CF3CF2, CH2FCHCl, CCl3, CHCl2, CH2CH2Cl; haloalkoxy is for example OCF3, OCHF2, OCH2F, CF3CF2O, OCH2CF3 and OCH2CH2Cl; correspon~;ng statements apply to haloalkenyl and other radicals substituted by halogen.

A hydrocarbon radical is a straight-chain, branched or cyclic and 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, pentalenyl, fluorenyl and the like, preferably phenyl;
a hydrocarbon radical i8 preferably alkyl, alkenyl or Alkynyl having up to 12 carbon atoms or cycloalkyl having 3, 4, 5, 6 or 7 ring atoms or phenyl; correspo~;ng statements apply to a hydrocarbon radical in a hydro-carbonoxy radical.

A heterocyclic radical or ring (heterocyclyl) can be saturated, unsaturated or heteroaromatic; it preferably contains one or more hetero-units in ~he ring, i.e.
heteroatoms or ring members which also include substi-tuted heteroatoms, preferably from the group consisting of N, 0, S, S0 and S02; preferably, it is an aliphatic heterocyclyl radical ha~ing 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 heteroaromatic radical or ring (heteroaryl), such as, for example, a mono-, bi- or polycyclic aromatic system, in which at least 1 ring contains one or more heteroatoms, for example pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, thienyl, thiazolyl, oxazolyl, furyl, pyrrolyl, pyrazolyl and imidazolyl, or is a partly or completely hydrogenated radical such as oxiranyl, pyrrolidinyl, piperidyl, piperazinyl, dioxolanyl, morpholinyl, and tetrahydrofuryl. Possible substituents for a substituted heterocyclic radical are the substituents mentioned below, and in addition also oxo. The oxo group can also occur on the hetero-ring atoms, which can exist in various oxidation states, for example in the case of N and S.

Substituted radicals, such as substituted hydrocarbon radicals, for example substituted alkyl, alkenyl, Alkynyl, aryl, phenyl and benzyl, or substituted hetero-cyclyl or heteroaryl, are, for example, a substituted radical derived from the unsubstituted parent substance, where the substituents are, for example, one or more, preferably 1, 2 or 3, radicals from the group consisting of halogen, alkoxy, haloalkoxy, alkylthio, hydroxyl, amino, nitro, carboxyl, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylamino-carbonyl, substituted amino, such as acylamino and mono-and dialkylamino, and alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and, in the case of cyclic radicals, also alkyl and haloalkyl; the term Hsubstituted radicals" such as substituted alkyl and the like, includes as substituent~ in addition to the saturated hydrocarbon-cont~;n;ng radicals mentioned, correspon~; ng unsaturated aliphatic and aromatic radi-cals, such as optionally substituted alkenyl, alkynyl, alkenyloxy, alkynyloxy, phenyl, ph~no~y and the like.
Preferred radicals with carbon atoms are those having from 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms. Preferred substituents are as a rule those from the group consisting of halogen, for example fluorine and chlorine, (Cl-C4)alkyl, preferably methyl or ethyl, (Cl-C4)haloalkyl, preferably trifluoromethyl, (Cl-C4)-alkoxy, preferably methoxy or ethoxy, (Cl-C4)halo~1koYy, nitro and cyano. The substituents methyl, methoxy and chlorine are particularly preferred here.

Mono- or disubstituted amino is a chemically stable radical from the group consisting of the substituted amino radicals, which are N-substituted, for example, by one or two identical or different radicals from the group consisting of alkyl, alkoxy, acyl and aryl; preferably mono~lkylamino, 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)~1k~noyl. Correspon~; ng statements apply to sub-stituted hydroxylamino or hydrazino.

Optionally substituted phenyl is preferably phenyl which is unsubstituted or substituted once or several time~, preferably up to three times, by identical or different radicals from the group consisting of halogen, (C1-C4)-5 alkyl, (C1-C4)alkoxy, (C1-C4)haloalkyl, (C1-C4)haloalkoxy and nitro, for example o-, m- and p-tolyl, dimethylphenyl radicals, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-tri-fluoro- 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 a~ 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 or phosphinic acids. Ac-~l is, for example, formyl, alkylcarbonyl such as [(Cl-C4)al~yl]-carbonyl, phenylcarbonyl, alkyloxycarbonyl, phenyloxy-carbonyl, benzyloxycarbonyl, alkylsulfonyl, alkyl-sulfinyl, N-alkyl-1-iminoalkyl and other radicals of organic acids. The radicals can in each case also be further substituted here in the alkyl or phenyl part, for example in the alkyl part by one or more radicals from the group consisting of halogen, alkoxy, phenyl and p~oxy; examples of substituents in the phenyl part are the substituents already mentioned above generally for substituted phenyl.

The invention also relate~ to all the stereoisomers included in formula (I) and mixtures thereof. Such compounds of the formula (I) contain one or more asym-metric carbon atoms or also double bonds, which are not ~hown separately in the formulae (I). The po~sible stereoisomers defined by their specific spatial form, such a~ enantiomers, diastereomers and Z isomers and E isomers, are all included by the formula (I) and can be obtained from mixtures of the stereoisomers by customary methods, or can also be prepared by stereoselective reaction~ in combination with the use of stereochemically pure starting substances.

Compounds of the formula (I) according to the invention, or salts thereof, which are of particular interest, above all for reasons of higher herbicidal action, better selectivity and/or easier preparation, are those in which Rl is S(o)nR4, So2NR5R6 or CoNR5R6, R2 is H, halogen, N02, CN, (Cl-C4)alkyl, (Cl-C4)alkoxy, ~(Cl-C4)alkyl]carbonyl or ~(C1-C4)alkoxy]carbonyl, where each of the last four radicals mentioned is unsubstituted or ~ubstituted in the alkyl part by one or more halogen atoms, R3 is H or (C1-C4)alkyl, preferably H or CH3, R4 is (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C3-C7) cycloalkyl, (C3-C7) cycloalkyl-(Cl-C3)alkyl or phenyl, where each of the last six rad;.cals men-tioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (Cl-C4)alkoxy, (Cl-C4)alkylthio, (Cl-C4)alkyl-sulfinyl, (Cl-C4)alkylsulfonyl, unsubstituted or substituted phenyl, ~(Cl-C4)alkoxy]carbonyl and, in the case of cyclic radicals, also (Cl-C4)alkyl and (Cl-C4) haloalkyl, R5 and R6 independently of one another are H, (Cl-C6)-alkyl, (C3-C6)alkenyl, (C3-C6)alkynyl, where each of the last three radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (Cl-C4)alkoxy, (Cl-C4) alkylthio and ~(Cl- C4) alkoxy]carbonyl, or unsubstituted or substituted phenyl, or R5 and R6, together with the N atom, are a heterocyclic ring having 5 or 6 ring members, which can option-ally contain further heteroatoms from the group consisting of N, 0 and S and is unsubstituted or mono- or polysubstituted by (Cl-C4)alkyl or an oxo group, A is a group of the formula A1 mentioned or, in the case that Rl = S(o)nR4 or So2NR5R6, also a group of the formula A2 mentioned, R7 and R3 independently of one another are H, (Cl-C6)-alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl or (C3-C6)-cycloalkyl, where each of the last four radicals S mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (Cl-C4)alkoxy, (Cl-C4)alkylthio and ~(Cl-C4)alkoxy]-carbonyl, phenyl, and, in the case of cycloalkyl, also (Cl-C4)alkyl and (Cl-C4)haloalkyl, or phenyl or phenylcarbonyl, where each of the last two radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, CN~ NO2, (Cl-C4)alkyl, (cl-c4)haloalkyl~ (Cl-C4)- .
alkoxy, (Cl-C4)haloalkoxy, (Cl-C4)alkylthio and [(Cl-C4)alkoxy]carbonyl, or heterocyclyl having 3 to 6 ring atoms, which is unsubsti-uted or substituted by one or more radicals from the group consisting of halogen, (Cl-C4)alkyl, (Cl-C4)haloalkyl, (Cl-C4)alkoxy and (cl-c4)halo~lk~Yy~
or [(Cl-C4)alkoxy]carbonyl, [(Cl-C4)alkyl]carbonyl, CN, (Cl-C4)alkylsulfonyl, NO2 or COOH, or carbamoyl, which is unsubstituted or contains, on the N atom, one or two substituents from the group consisting of the radicals (Cl-C4)alkyl, (C3-C4)alkenyl, (C3-C4)-alkynyl and phenyl, which is unsubstituted or sub-stituted by one or more radicals from the group consisting of halogen, (Cl-C4)alkyl, (Cl-C4)halo-alkyl, (Cl-C4)alkoxy, (Cl-C4)alkylthio, (Cl-C4)alkyl-sulfonyl, [(Cl- C4) alkoxy]-carbonyl, CN and NO2, or di-[(Cl-C4)alkoxy]-phosphinyl or R7 and R8, together with the carbon atom, are a ring having 4 to 8 ring atoms, which is carbocyclic or is heterocyclic and has one or two heteroatoms from the group consisting of N, O and S, and which is unsub-stituted or substituted by one or more radicals from the group consisting of (Cl-C4)alkyl, halogen and oxo or is also benzo-fused, R9 is H or (Cl-C6)alkyl, which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (Cl-C4)alkoxy, (C1-C4)alkyl-thio, (C1-C4)alkylsulfonyl, [(Cl-C4)alkoxy]carbonyl, CN, phenyl and (C3-C6)-cycloalkyl, or (C3-C6)alkenyl, (C3-C6)alkynyl, where each of the last two radicals mentioned is unsubstituted or substituted by one or more halogen atoms, or a group of the formula o ll or -SO2R , in which -C-R~

R is H, (Cl-C8)alkyl, (C2-C6)alkenyl or (C2-C6)alkynyl, where each of the last three radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkoxy, (C1-C4)alkylthio, phenoxy, [(C1-C4)alkoxy]-carbonyl, unsubstituted or substituted hetero-cyclyl and unsubstituted or substituted phenyl, or unsubstituted or substituted (C3-C6) cycloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted hetero-cyclyl or [(C1-C4)alkoxy]carbonyl, R is (Cl-C6)alkyl, (C3-C6)alkenyl or (C3-C6)alkynyl, where each of the last three radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkoxy, (C1-C4)alkylthio and phenyl, or phenyl which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, CN~ NO2~ (Cl-C4)alkyl, (cl-c4)haloalkyl and (C1-C4)alkoxy, Rl~ i8 an acyl radical of the formula W' W- W' c-R12,-c-T-R13~-so2Rl4~-c-NRl5Rl6,-so2NRl5Rl6~

R11 is H, (C1-C6)alkyl, (C3-C6)alkenyl or (C3-C6)alkynyl, .

where each of the last three radicals mentioned is unsubstituted or substituted by one or more of the radicals from the group consisting of halogen, ~C1-C4)alkoxy, (C1-C4)alkylthio, [(C1-C4)alkoxy]-carbonyl, (C3-C6)cycloalkyl, unsubstituted or substituted phenyl and CN, R12 is H, (C1-C8)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, where each of the last three radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkoxy, (C1-C4)alkylthio, p~enoxy, [(C1-C4)alkoxy]carbonyl, unsubstituted or substituted heterocyclyl and unsub-stituted or substituted phenyl, or unsubstituted or-substituted (C3-C6)cycloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted heterocyclyl or [(C1-C4)alkoxy]carbonyl, R13 is (C1-C6)alkyl, (C3-C6)alkenyl, (C3-C6)alkynyl, where each of the last three radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkoxy, (C1-C4)alkylthio, [(C1-C4)alkoxy]carbonyl, unsub-stituted or substituted phenyl and unsubstituted or substituted (C3-C6)cycloalkyl, or (C3-C6)cycloalkyl, which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkyl and (C1-C4)alkoxy, R14 is a radical from the group of radicals possible for R4, R15 is a radical from the group of radicals possible for R5, R16 is a radical from the group of radicals possible for R6, or R15 and R16, together with the N atom, are a heterocyclic radical such as is possible for NR5R6, W is an oxygen atom or a sulfur atom, preferably an oxygen atom, W is an oxygen atom or a sulfur atom, preferably O, T is an oxygen atom or a sulfur atom, preferably O, n is 0, 1 or 2, X and Y independently of one another are H, halogen, (C1-C4)alkyl, (Cl-C4)alkoxy, (C1-C4)alkylthio, where each of the last three radicals mentioned is unsub-stituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkoxy and (C1-C4)alkylthio, or mono- or di-[(C1-C4)alkyl]amino, (C3-C6)-cycloalkyl, (C3-C5) alkenyl, (C3-C5) alkynyl, (C3-C5) alkenyloxy or (C3-C5) alkynyloxy and Z is CH or N.

Compounds of the formula (I) according to the invention, and salts thereof, which are of particular interest are those in which R2 is H, (Cl-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy or halogen, R4 is (C1-C4)alkyl, (C2-C4)alkenyl, (C2-C4)alkynyl, (C3-C6)cycloalkyl, (C3-C6)cycloalkyl-(C1-C2)alkyl,or phenyl, where each of the last 8ix radicals men-tioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (Cl-C4) alkoxy, phenyl and [(C1-C4)alkoxy]carbonyl and, in the case of cyclic radicals, also (C1-C4)-alkyl and (C1-C4)haloalkyl, R5 and R6 independently of one another are H, (C1-C6)-alkyl, which is unsubstituted or substituted by one or more radicals from the group consisting of halogen and (C1-C4)alkoxy, or (C3-C4) alkenyl or (C3-C4) alkynyl,or R5 and R6, together with the N atom, are a heterocyclic ring ha~ring 5 or 6 ring members, which can option-ally contain 1 or 2 further heteroatoms from the group consisting of N, 0 and S, R7 and R8 independently of one another are H, (C1-C4)-alkyl, (C2-C4)alkenyl, where each of the last two radicals mentioned is substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkoxy and phenyl, or (C3-C6)-cycloalkyl, (C3-C6)alkynyl, phenyl or phenylcarbonyl, where each of the last two radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of fluorine, chlorine, CN, NO2, (C1-C4)haloalkyl, (C1-C4)alkoxy, (C1-C4)alkylthio and ~(C1-C4)alkoxy]carbonyl, or furyl, pyridyl, thienyl, tetrahydrofuryl, [(C1-C4)alkoxy]carbonyl or COOH or CN, NO2, carbamoyl, which is unsubstituted or is mono- or disubstituted by radicals from the group consisting of (C1-C4)alkyl or is monosubstituted by phenyl, or -PO(OCH3)2 or -PO(OC2H5)2 or R7 and R8, together with the carbon atom, are a ring having 4 to 8 ring m~m~ers~ which is carbocyclic or heterocyclic with a heteroatom from the group con-sisting of N, O and S and is unsubstituted or mono-or polysubstituted by (C1-C4)alkyl or halogen or an oxo group, R9 is H, (C1-C4)alkyl, which is unsubstituted or sub-stituted by one or more radicals from the group con-sisting of halogen, (C1-C4)alkoxy, (Cl-C4)alkylthio, [(C1-C4)alkoxy]carbonyl and phenyl, or (C3-C4)alkenyl or (C3-C4)alkynyl, R10 is a radical of the formula O W' W--C-Rl 2, -C-ORl 3, -C-NRl 5R16 R11 is H, (C1-C4)alkyl, which is unsubstituted or sub-stituted by one or more radicals from the group con-sisting of halogen, (C1-C4)alkoxy, (C1-C4)alkylthio, [(C1-C4)alkoxy]carbonyl and phenyl, or (C3-C4)alkenyl or (C3-C4)alkynyl, R12 is H, (C1-C6)alkyl which is unsubstituted or substi-tuted by one or more radicals from the group con-sisting of halogen, (C1-C6)alkoxy, (C1-C4)alkylthio, ~(C1-C4)alkoxy]carbonyl and unsubstituted or substi-tuted phenyl, or (C2-C4)alkenyl or (C2-C4)alkynyl, (C3-C6)-cycloalkyl, [(C1-C4)alkoxy]carbonyl, un~ub-stituted or substituted phenyl or unsubstituted or substituted heterocyclyl, CA 022246l2 l997-l2-l2 Rl3 is (C1- C4) alkyl, (Cl- C4) haloalkyl, ( C3-C4) alkenyl, (C3-C4) alkynyl or (C3-C6)-cycloalkyl, R15 is a radical from the group of radicals possible for R5, Rl6 is a radical from the group of radicals possible for R6, or Rl5 and Rl6, together with the N atom, are a heterocyclic radical such as is possible for NR5R6, W~ is an oxygen atom or a sulfur atom and~0 X and Y independently of one another are (C1-C4)alkyl, (C1-C4)alkoxy, where each of the last two radicals mentioned is unsubstituted or sub~tituted by one or more halogen atoms, or (C1-C4)alkylthio, halogen or mono- or di-[(C1-C2)alkyl]amino.
~5 Preferred compounds of the formula (I) according to the invention, or sa'ts thereof, are those in which R2 is H, halogen or (C1-C2)alkyl, R4 is (C1-C4) alkyl, (C1-C4) haloalkyl, (C3-C4) alkenyl or ~C3-C4) alkynyl or R5 and R6 independently of one another are H, (C1-C4)-alkyl, (C3-C4) alkenyl or (C3-C4) alkynyl or R5 and R6, together with the N atom, are a heterocyclic ring having 5 or 6 ring members, R7 and R3 independently of one another are H, (C1-C4)-alkyl, (C1- C4) haloalkyl, (C1-C2)alkoxy-(C1-C2)alkyl, (C2-C4)alkenyl, (C2-C4)alkynyl, (C3-C6)-cycloalkyl or [(C1-C4)alkoxy]carbonyl or R7 and R8, together with the carbon atom, are a ring having 5 or 6 ring m~mhers, R9 is H or (C1-C3)alkyl, R10 is a radical of the formula O O
C R12 C oR13 R11 is H or (C1-C4)alkyl, Rl2 i8 H or (Cl-C6)alkyl, which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkoxy and phenyl, or (C2-C4)alkenyl, (C3-C6)cycloalkyl or phenyl, which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (Cl-C4)alkyl and (C1-C3)alkoxy, R13 is (C1-C4)alkyl or (C1-C4)haloalkyl, n is 2, X is (C1-C2)alkyl, (C1-C2)alkoxy, (C1-C2)alkylthio, (C1-C2)haloalkyl or (cl-c2)halo~lkoyy and Y is (C1-C2)alkyl, (C1-C2)alkoxy, halogen, NHCH3 or N(CH3) 2-Particularly preferred compounds of the formula (I) according to the invention, or salts thereof, are those in which R2 is H
R4 is (C1-C4)alkyl and R5 and R6 independently of one another are H or (C1-C4)-alkyl.

Preferred compounds of the formula (I) according to the invention are also those which contain one or some of the features from the abovementioned preferred compounds.

The present invention also relates to processes for the preparation of the compounds of the formula (I) or salts thereof, which comprise a) reacting a compound of the formula (II) R2 Rl "~ ( I I ) A S~2NH2 with a heterocyclic carbamate of the formula (III) - CA 022246l2 l997-l2-l2 R -o-co-,~lR3~ Z ( I I I ) N~

in which R is unsubstituted or substituted phenyl or (Cl-C4)alkyl, or b) reacting a sulfonylcarbamate of the formula (IV) Rl O ( IV) A~S ~ 2 N H /II\o /

in which R~ is unsubstituted or substituted phenyl or (Cl-C4)alkyl, with an amino-heterocyclic compound of the formula (V) X

H-N~(~Z (V) or c) reacting a sulfonyl isocyanate of the formula (VI) ~R (Vl) A SO2-N ~ C ~ O

with an amino-heterocyclic compound of the formula (V) or d) reacting a sulfonamide of the formula (II) with a (thio)-isocyanate of the formula (VII) X

W~C=N~(~Z (Vl I ) N~
y in the presence of a base or e) first reacting an amino-heterocyclic compound of the formula (V) with a carbonic acid ester, for example diphenyl carbonate, under base catalysis and react-ing the intermediate formed with a sulfonamide of the formula (II) in a one-pot reac~ion, in which, in the formulae (II)-(VII), the radicals and groupn Rl-R3, A, W, X, Y and Z are defined as in formula (I), and in proces~ variants a) to c) and e), compounds (I) with W = O are initially obtained.

The reaction of the compound~ of the formulae (II) and (III) is preferably carried out under base catalynis in lS an inert organic solvent, such as, for example, methylene chloride, acetonitrile, dioxane or tetrahydrofuran (THF) at temperatures between 0~C and the boiling point of the solvent. Ba~e~ which are used here are, for example, organic amine ba~e~, such as 1,8-diazabicyclo[5.4Ø]-undec-7-ene (DBU), in particular if R~ = (~ubstituted) phenyl (cf. EP-A-44807), or alkali metal hydroxides, such as, for example, NaOH, or trimethylaluminum or triethyl-aluminum, the latter in particular if R~ = alkyl (cf.
EP-A-166 516). The particular base i~ employed here, for example, in the range from 1 to 3 molar equivalents, based on the compound of the formula (II).

The sulfonamides (II) are novel compounds. This invention - CA 022246l2 l997-l2-l2 also relates to them and their preparation.

The compounds of the formula (II) are obtained, for example, starting from compounds of the formula (VIII) ~R (Vl I I ) I ~), .
A~ 'SO2NH- t -C~,Hg in which Rl and R2 are defined as in formula (I), by reaction with a strong acid (in this context cf.
WO 89/10921).

Possible strong acids are, for example, mineral acids, such as H2SO4 or HCl, or strong organic acids, such as trifluoroacetic acid. The tert-butyl protective group is split off, for example, at temperatures from -20~C to 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 solvent, such as, for example, methylene chloride or chloroform.

The compounds of the formula (VIII) where A = A1 are obt~;ne~, for example, from suitable hydrazine precursors by reaction with suitable electrophiles, such as, for example, aldehydes or ketones. Suitable hydrazine pre-cursors are, for example, those in which R9 is defined as in formula (I), but in particular R9 = H; for reaction of the hydrazine precursors with electrophiles cf.:
V. Lerch, J. Konig, Synthesis, 157 (1983), Houben-Weyl, "Methoden der organischen Chemie" [Method~ of Organic Chemistry], 4th Edition, Volume 10/2, page 396 et seq., page 410 et seq..

The compounds of the formula (VIII) where A = A2 are obtained, for example, from suitable hydrazine precursors by reaction with suitable electrophiles, such as, for example, acid chlorides, acid anhydrides, isocyanates, i60thiocyanates , sulfochlorides or sulfamoyl chlorides.
Suitable hydrazine precursors are, for example, those in which R10 = H and R9 and R11 are defined as in formula (I), R9 and R10 = H and R11 is defined as in formula (I), R10 and R11 = H and R9 is defined as in formula (I), but in particular R9, R10 and R11 = H.

For the reaction of the hydrazine precursors with electrophiles cf.:
R.H. Pilgram, Synth. Commun. 15, 697 (1985), J. Rnabe, W. Wunn, Arch. Pharm. 313, 577 (1980), V. Lerch, J. Ronig, Synthesis, 157 (1983), R.F. Smith et al., J. Org. Chem. 33, 851 (1968), R.H. Pilgram, J. Org. Chem. 53, 38 (1988), US-A-4 619 689, EP-A-562 575, Houben-Weyl, "Methoden der organischen Chemie" [Methods of Organic Chemistry], 4th Edition, Volume 10/2, page 355 et seq., page 383 et seq., page 396 et seq., page 406 et seq., page 391 et seq..

In some cases it is possible to carry out further deriva-tizations by methods known from the literature after the reaction with electrophiles, for example alkylations or acylations (cf. Houben-Weyl, "Metho~n der organischen Chemie" [Methods of Organic Chemi~try], 4th Edition, Volume 10/2, page 402 et seq. and page 385).

The phenylhydrazines of the formula (VIII) where R2, R3 and R4 = H are accessible starting from the aniline derivati~es (IX) R2 Rl (Vl I la) N-NSO2NH- t -C4Hg I
H

/[~R ( I X ) H2N SO2NH- t -C4Hg in which Rl and R2 are defined as in formula (I), by diazotization and subsequent reduction. Suitable reducing agents are, for example, SnCl2, SO2 or sodium dithionite (cf. Houben-Weyl, "Methoden der organischen Chemie"
[Methods of Organic Chemistry], 4th Edition, Volume 10/2, page 180 et seq.; EP-A-562 575).

The aniline derivatives of the formula (IX) mentioned are obtained by processes known from the literature by reduction of the nitro group of the compounds (X), for example by hydrogenation with hydrogen in the presence of a suitable catalyst, such as Pd-C or Raney Nickel, or by reduction with iron in an acetic acid medium (in this context cf.: H. Berrie, G.T. Neuhold, F.S. Spring, J. Chem. Soc. (1952), 2042; M. Freifelder, "Catalytic Hydrogenation in Organic Synthesis: Procedures and Commentaryn, J. Wiley and Sons, New York (1978), Chapter 5).

l~R ( X ) 02N SO2NH- t -C,,Hg The sulfonamides of the formula (X) where Rl = -S(o)nR4 are obtainable, for example, by the following route (cf.
Equation 1):

The reaction of the sulfonic acids (XI) or alkali metal CA 022246l2 l997-l2-l2 salts thereof with a chlorinating agent - such as, for example, PCl3, POCl3 or SOCl2 - leads to the sulfochloride of the formula (XII). This reaction is 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 tert-butylamine leads to the sulfonamides of the formula (XIII). These compounds can be converted, with mercaptans in solvents, such as, for example, dimethylformamide, N,N-dimethylacetamide or N-methyl-pyrrolidinone, in the presence of suitable bases, such as, for example, sodium carbonate or potassium carbonate, into the correspo~; ng mercaptans of the formula (Xa) (= formula (X) where R1 = S(o)nR4 and n = O). By choosing suitable oxidizing agents (for example potassium per-oxomonosulfate, 30xone) and reaction conditions, the correspo~; ng compounds of the formula (Xb) where n = 1 and 2 can be prepared by methods analogous to known methods.

2 0 Equation 1:
R2 503H ~2~ 502CI

(Xl) (Xll) R2 5O2NH-~-C~H9 ~22 502NH-t-C~H9 (Xl I 1) (X~) ~5 ( ~ ) n R ~
02N SO2NH-t-C~Hg (Xb; n ~ 1, 2) The sulfonamides of the formula (X) where Rl = -So2NR5R6 are obtainable, for example, by the following route (Equation 2).

Equation 2 R~ SO~NH-t-C,H~ OC I ~2N SO~NN-t-C~Hg (X~. n s O) (XIV) HNR5R6 2~ SO2NRsR6 02N 502NH- t -C,H9 ( X C ) The compounds of the formula (Xa) (= formula (X) where Rl = S(o)nR4 and n = 0), for example where R4 = benzyl, are converted into the sulfochlorides of the formula (XIV) by this reaction via oxidated chlorination with chlorine or sodium hypochlorite. The sulfonamides of the formula (Xc) are accessible by reaction of (XIV) with amines.

The sulfonamides of the formula (X) where Rl = -CoNR5R6 are obtained, for example, by the following route, starting from commercially available 2-amino-5-nitro-benzoic acid, it being possible for all the reaction steps to be carried out by methods analogous to those known from the literature (cf. E~uation 3).

Equation 3 ~ C02H esterification ~ COOR'l. NaNO2 02N NH2 02N NH2 2. No2s2os/cucl2 R2 COOR' H2N-t-c4H9 R~ COOR' 02N S02CI 02N SO2NH-t-C,H9 ( X V ) The compound (XV; R' = Me) is a suitable precursor for the preparation of the amides (Xd). They are likewise obt~ineA by methods analogous to those known from the literature, from (XV) by reaction with the particular amine.

R~ COO~ HN~ R~ CoN~RR5 02N SO2NH-t-C4H9 ~2N SO,~H-t-C4Hg (XV, R' . ~) (Xd) The carbamates of the formula (III) can be prepared by methods which are described in South African Patent Applications 82/5671 and 82/5045 or EP-A 70804 (US-A-4 480 101) or RD 275056.

The reaction of the compounds (IV) with the amino-heterocyclic compounds (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 starting materials (V) required are known from the literature or can be prepared by proces~es known from the literature.
The phenylsulfonylcarbamates of the formula (IV) are obtained analogously to US-A-4 684 393 or US-A-4 743 290.

The phenylsulfonyl isocyanates of the formula (VI) can be prepared analogously to US-A-4 481 029 and reacted with the amino-heterocyclic compounds (V).

The (thio)isocyanates of the formula (VII) are obtainable by processes known from the literature (EP-A-232067, EP-A-166516). The reaction of the (thio)-isocyanates (VII) with compounds (II) is carried out, for example, at 5 -10 to 100~C, preferably 20 to 100~C, in an inert aprotic solvent, such as, for example, acetone or acetonitrile, in the presence of a suitable base, for example N(C2H5) 3 or R2C03.

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

The salts of the compounds of the formula (I) are prefer-ably prepared in inert polar solvents, such as, for exampl~, water, methanol or acetone, at te~.p2~_tures 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 pota~sium carbonate, alkali metal and alkaline earth metal hydroxides, for example NaOH or ROH, or ammonia or ethanolamine.

The term n inert solvents" in the above process variants in each case means solvents which are inert under the particular reaction conditions but do not have to be inert under any desired reaction conditions.

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. Even perennial weeds which shoot from rhizomes, pieces of root or other persistent organs and are difficult to control are combated well by the active compounds. Tt is irrelevant here whether the substances are applied before sowing, pre-emergence or post-emergence.

Some representatives of the mono- and dicotyledon weed CA 022246l2 l997-l2-l2 flora which can be controlled by the compounds according to the invention may be mentioned specifically as examples, without a limitation to certain species being intended by nAm; ng of these.
On the part of monocotyledon weed species, 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 per-sistent Cyperus species are combated well.
In the case of dicotyledon weed species, the actionspectrum extends to species such as, for example, Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Matricaria, Abutilon and Sida on the AnnnAl 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 in an outstAn~ling manner by the active compounds accord-ing 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 completely prevented, or the weeds grow to the cotyledon stage, but then halt their growth and finally die completely after a period of three to four weeks.

If the active compounds are applied to the green parts of the plants by the post-emergence method, a drastic stop in growth likewise occurs very rapidly after the treat-ment and the weed plants remain in the growth stage which existed at the time of application or die completely after a certain period of time, 80 that weed competition which is harmful to crop plants is eliminated very early on and in a lasting manner in this way.

Although the compound8 according to the invention show an excellent herbicidal activity again~t mono- and dicotyledon weeds, crop plants of economically important crops, such as, for example, wheat, barley, rye, rice, maize, sugar beet, cotton and soya, are damaged only insignificantly or not at all. For these reasons, the present compounds are particularly suitable for select-ively controlling undesirable plant growth in agricul-tural crop plantations.

The substances according to the invention furthermore have outst~;ng growth-regulating properties on crop plants. They intervene in a regulatory manner in the endogenous metabolism of the plant and can thus be employed for influencing plant contents in a controlled manner and for facilitating harvesting, such as, for example, by triggering desiccation and stunting growth.
They are furthermore also suitable for general control and inhibition of undesirable vegetative growth without killing the plants at the same time. Inhibition of 2 0 vegetative growth plays a major role in many mono- and dicotyledon crops, since lodging can be reduced or completely prevented by-this means.

The compounds according to the invention can be used in the customary formulations 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 compounds of the formula (I).

The compounds of the formula (I) can be formulated in various ways, dep~n~;ng on the given biological and/or chemico-physical parameters. Example~ of formulation possibilities are: 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, sprayable solutions, su~pen-sion concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusting powders (DP), dressing agents, granules for application by spreading and to the soil, granules (GR) in the form of microgranulea, spray granules, adsorption granules and absorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, micro-capsules and waxes.

These individual formulation types 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 Formulations", Marcel Dekker, N.Y., 1973; R. Martens, "Spray Drying" uAn~hook, 3rd Edition 1979, G. Goodwin Ltd. To~o~.

The necessary formulating auxiliaries, such as inert materials, surfactants, solvents and further additives, are likewise known and are described, for example, in:
Watkins, "Handbook of Insecticide Dust Diluents and 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, "Encyclopedia of Surface Active Agents", Chem. Publ. Co.
Inc., N.Y. 1964; Schonfeldt, 'lGrenzflachenAktive Athylen-oxi~A~ te" [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 pesticide 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.

- CA 022246l2 l997-l2-l2 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 anionic and/or nonionic nature (wetting agents, dispersing agents), for example polyoxyethylated alkyl phenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether-sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium ligninsulfonate, sodium 2,2'-~;nAphthylmethane-6, 6'-disulfonate,sodiumdibutyln-aphthalene-sulfonate or else sodium oleoylmethyltauride.
To prepare the wettable powders, for example, the herbicidal active compounds are finely ground in customary apparatuses, such as hammer mills, blast mills and air jet mills, and are mixed with the formulation auxiliaries at the same time or subsequently.

Emulsifiable concentrates are prepared by dissolving the active compound in an organic solvent, for example butanol, cycloh~yano~e~ dimethylformamide, xylene or also 2 0 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 (emulsi-fiers). Emulsifiers which can be used are, for example:
calcium alkylarylsulfonates, such as Ca dodecylbenzene-sulfonate, or nonionic emulsifiers, such as fatty acidpolyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide co~den~ation 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 grin~; 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 grinding 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 formulation.

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 granular inert material capable of adsorption or by applying active-compound concentrates to the surface of carrier substances, such as sand, kaolin-ites or granular inert material, by means of adhesives, for example polyvinyl alcohol, sodium polyacrylate or mineral oils. Suitable active compounds can also be granulated in the manner customary for the preparation of fertilizer granules - if desired as a mixture with ferti-lizers.

Water-dispersible granules are as a rule prepared by the customary processes, such as spray-drying, fluidized-bed granulation, disk granulation, mixing 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 u~n~hook" 3rd Edition, 1979, G. Goodwin Ltd., To~o~; J.E. BLo~n;ng, "Agglomeration", Chemical and Engineering 1967, pages 147 et. seq.; "Perry's Chemical Engineer'~ 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. Rl;n~An, "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 comprises customary formulation constituents. In emulsifiable concentrates, the active compound concentration 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 from 5 to 20% by weight of active compound, and sprayable solutions comprise about 0.05 to 80%, preferably from 2 to 50%, by weight of active compound. In water-dispers-ible 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 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, emulsi-fiers, penetration agents, preservatives, antifreezes and solvents, fillers, carrier substances and dyestuffs, de-foamers, evaporation inhibitors and agents which influ-ence the pH and viscosity.

Rnown active compounds such as are described, for example, in Weed Research 26, 441-445 (1986), or "The Pesticide ~AnllAl n, 9th Edition, The British Crop Protection Council, 1990/91, Bracknell, England, and literature mentioned therein can be employed as combination partners for the active compounds according to the invention in mixed 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 denoted either by the "common name n according to the International Organization for StAn~Ardization (ISO) or by the chemical name, if appropriate together with a customary code number):
acetochlor; acifluorfen; aclonifen; ARH 7088, i.e.
[~[1-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitro-phenyl]-2-methoxyethylidene]amino]oxy] acetic acid and -acetic acid methyl ester; alachlor; alloxyd m; 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; ben-furesate; bensulfuron-methyl; bensulide; bentazone;
benzofenap; benzofluor; benzoylprop-ethyl; benzthiazuron;
bialaphos; bifenox; bromacil; bromobutide; bromofenoxim;
bromoxynil; bromuron; buminafos; busox;no~e; butachlor;
butamifos; butenachlor; buthidazole; butralin; butylate;
cafenstrole (CH-900); carbetamide; cafentrazone (ICI-A0051); CDAA, i.e. 2-chloro-N,N-di-2-propenylacetamide;
CDEC, i.e. diethyldithiocarbamic acid 2-chloroallyl ester; chlomethoxyfen; chloramben; chlorazifop-butyl, chlormesulon (ICI-A0051); chlorbromuron; chlorbufam;
chlorfenac; chlorflurecol-methyl; chloridazon; chlor-imuron ethyl; chlornitrofen; chlorotoluron; chloroxuron;
chlorpropham; chlorsulfuron; chlorthal-dimethyl; chlor-thiamid; cinmethylin; cinosulfuron; clethodim; clodinafop and ester derivates thereof (for example clodinafop-propargyl); clomazone; clomeprop; cloproxydim; clo-pyralid; cumyluron (JC 940); cyanazine; cycloate; cyclo-sulfamuron (AC 104); cycloxydim; cycluron; cyhalofop and ester derivatives thereof (for example butyl ester, DEH-112); cyperquat; cyprazine; cyprazole; daimuron;
2,4-DB; dalapon; desmedipham; desmetryn; di-allate;
dicamha; 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; esprocarb; ethalfluralin;
ethametsulfuron-methyl; ethidimuron; ethiozin;
ethofumesate; F5231, i.e. N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-lH-tetrazol-1-yl]phenyl]ethanesulfonamide; ethoxyfen and esters th~reof (for example ethyl ester, HN-2~2~- e~obenzanid (HW 52); fenoprop; f~nQYAn, fenoxaprop and fenoxAprop-P
and esters thereof, for example f~noYArrop-P-ethyl and f~noYAprop-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 pentyl ester, S-23031);
flumioxazin (S-482); flumipropyn; flupoxam (KNW-739);
fluorodifen; fluoroglycofen-ethyl; flupropacil (UBIC-4243); fluridone; flurochloridone; fluroxypyr;
flurtamone; fomesafen; fosamine; furyloxyfen; glufosi-nate; glyphosate; halosafen; halosulfuron and esters thereof (for example 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; imazetha-methapyr; imazethapyr; imazosulfuron; ioxynil; isocar-bamid; 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; metsulfuronmethyl; MH;
molinate; monalide; monocarbamide dihydrogensulfate;
monolinuron; monuron; MT 128, i.e. 6-chloro-N-(3-chloro-2-propenyl)-5-methyl-N-phenyl-3-pyridazin~;ne; NT 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); oY~ 7On; oxyfluorfen;
paraquat; pebulate; pendimethalin; per$1uidone;
phenisopham; phenmedipham; picloram; piperophoR;
piributicarb; pirifenop-butyl; pretilachlor;
primisulfuron-methyl; procyazine; prodiamine; pro-fluralin; proglinazine-ethyl; prometon; prometryn;
propachlor; propanil; propaquizafop and esters thereof;
propazine; propham; propisochlor; propyzamide; pro-sulfalin; prosulfocarb; prosulfuron (CGA-152005);
prynachlor; pyrazolinate; pyrazon; pyrazosulfuron-ethyl;
pyrazoxyfen; pyridate; pyrithiobac (KIH-2031); pyroxofop and esters thereof (for example propargyl ester); quin-clorac; quinmerac; quinofop and ester derivatives thereof, quizalofop and quizalofop-P and ester deriv-atives 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-[t7-[2-Chloro-4-(trifluoromethyl)-phenoxy]-2-naphthalenyl]oxy]propanoic acid and -propanoic acid methyl ester; sulfentrazon (FMC-97285, F-6285);
sulfazuron; sulfometuron-methyl; sulfosate (ICI-A0224);
TCA; tebutam (GCP-5544); tebuthiuron; terbacil;
terbucarb; terbuchlor; terbumeton; - terbuthylazine;
terbutryn; TFH 450, i.e. N,N-diethyl-3-[(2-ethyl--6-methylphenyl)sulfonyl]-lH-1,2,4-triazole-1-carbox~;de;
thenylchlor (NSR-850); thiazafluron; thizopyr (Mon-13200); thidiazimin (SN-124085); thifensulfuron-methyl;
thiobencarb; tiocarbazil; tralkoxydim; tri-allate;
triasulfuron; triazofenamide; tribenuron-methyl;
triclopyr; tridiphane; trietazine; trifluralin; triflu-sulfuron and esters (for example methyl ester, DPX-66037); trimeturon; tsitodef; vernolate; 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. Dusts-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 vary within wide limits, for example between 0.001 and 10.0 kg/ha or more of active substance, but is preferably between 0.005 and 5 kg/ha.

A. Chemical Examples Example A1:
N-tert-Butyl-2-chloro-5-nitrobenzenesulfonamide 165 g of dried 2-chloro-5-nitrobenzenesulfonic acid sodium salt (90% pure) are initially introduced into 264 ml of acetonitrile, 264 ml of sulfolane and 16.5 ml - CA 022246l2 l997-l2-l2 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, 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 wA~h;ng with dilute hydrochloric acid and drying over MgS04, the organic phase i~ 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 second fraction of the product of comparable quality (46.7 g) can be isolated analogously from the mother liquor.

Example A2 N-tert-Butyl-2-ethylmercapto-5-nitrobenzenesulfonamide 5.6 ml of ethylmercaptan are added to a suspension of 20.0 g of N-tert-butyl-2-chloro-5-nitrobenzenesulfon-amide, 18.9 g of potassium carbonate and 100 ml of DMF at room temperature. After the mixture has been stirred for 3 hours, it is concentrated under a high vacuum. The residue is taken up in water and is acidified with concentrated hydrochloric acid (pH 1 to 2). The aqueous phase 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.

Example A3 N-tert-Butyl-2-ethylsulfonyl-5-nitrobenzenesulfonamide A solution of 180 g of ~Oxone (potassium peroxomono-sulfate) 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 ethyl sulfone are thus obtained; melting point: 108 to 111 ~ C .

Example A4 5-Amino-N-tert-butyl-2-ethylsulfonylbenzenesulfonamide 9.3 g (165.7 mmol) of iron powder are added in portions to a solution of 17.6 g (50.2 mmol) of N-tert-butyl-2-ethylsulfonyl-5-nitrobenzenesulfonamide in 70 ml of acetic acid and 23 ml of water at 80 to 85~C. When the addition has ended, the mixture is subsequently stirred at 80~C for 4.5 hours, 30 ml of 2N HCl are added and the mixture is allowed to cool to 25~C. It is filtered with suction, the residue is rinsed three times with water and the washed solid is dissolved in ethyl acetate. After the organic phase has been washed with water, dried and evaporated, 12.3 g (76% of theory) of 5-amino-N-tert-butyl-2-ethylsulfonylbenzenesulfonamide of melting point 193 to 194~C are obtained.

Example A5 N-tert-Butyl-2-ethylsulfonyl-5-hydrazinobenzenesulfon-amide 4.0 g (12.5 mmol) of 5-amino-N-tert-butyl-2-ethyl-sulfonylbenzenesulfonamide are initially introduced into 14 ml of concentrated HCl at O to 5~C, and 1.0 g (13.7 mmol) of NaNO2 dissolved in 5 ml of water is added in the course of 5 minutes. The mixture is subsequently stirred at 0~C for 10 minutes and the resulting solution is added, at O to 5~C, to a solution of 8.5 g (37.5 mmol) of tin(II) chloride dihydrate dissolved in 9 ml of con-centrated HCl. After the mixture has been stirred for18 hours, it is poured onto ice and the pH is adjusted to 5 to 6 first with 6N NaOH and then with solid NaHCO3. The mixture is extracted several times with ethyl acetate and the organic phase is dried and evaporated. 2.4 g (58% of theory) of N-tert-butyl-2-ethylsulfonyl-5-hydrazino-benzenesulfonamide of melting point 136 to 140~C are obtained.

Example A6 N-tert-Butyl-2-ethylsulfonyl-5-(2-propionylhydrazino)-benzenesulfonamide 0.58 g (6.3 mmol) of propionyl chloride is added dropwiseto 2.0 g (6 mmol) of N-tert-butyl-2-ethylsulfonyl-5-hydrazinobenzenesulfonamide in 27 ml of pyridine at -30~C. The mixture is stirred at -30~C for 2 hours, allowed to come slowly to 0~C and poured into ice-water and the pH is brought to 1 with 2N HCl. After extraction with CH2Cl2, drying and evaporation, 1.6 g (69% of theory) of N-tert-butyl-2-ethylsulfonyl-5-(2-propionyl-hydrazino)benzenesulfonamide are obtained, with the following lH-NMR signals:
lH-NMR (d6-DMSO): ~ = 1.08 (t, 3H, CH2C_3); 1.10 (t, 3H, CH2C_3), 1.15 (8, 9H, C(CH3)3); 2.22 (q, 2H, COCH2); 3.49 (q, 2H, SO2CH2); 6.52 (8, lH, SO2NH); 6.93 (dd, lH aroma-tic 4-H); 7.47 (d, lH, aromatic 6-H); 7.88 (d, lH, aromatic 3-H); 9.04 (8, lH, NH); 9.96 (lH, 8, NH).

Example A7 N-tert-Butyl-2-ethylsulfonyl-5-isopropylidenehydrazino-benzenesulfonamide A solution of 2.4 g (7.5 mmol) of N-tert-butyl-2-ethyl-sulfonyl-5-hydrazinobenzenesulfonamide and 2.2 g (37.5 mmol) of acetone in 40 ml of methanol is stirred at 25~C for 2 hours. After evaporation, 2.7 g (95% of theory)ofN-tert-butyl-2-ethylsulfonyl-5-isopropylidene-hydrazinobenzenesulfonamide of melting point 177 to 178~C
remain.

_ Example A8 2-Ethyl~ulfonyl-5-(2-propionylhydrazino)benzene-sulfonamide A mixture of 1.6 g (4 mmol) of N-tert-butyl-2-ethyl-sulfonyl-5-(2-propionylhydrazino)benzenesulfonamide and 20 ml of trichloroacetic acid is stirred at 25~C for 2.5 hours. It is evaporated and the residue is triturated with diethyl ether to give, after filtration and drying, 1.25 g (91% of theory) of 2-ethyl~ulfonyl-5-(2-propionyl-hydrazino)benzenesulfonamide of melting point 198 to200~C.

Example A9 3-(4,6-Dimethoxypyrimidin-2-yl)-1-~2-ethyl~ulfonyl-5-(2-propionylhydrazino)phenylsulfonyl]urea, sodium salt 0.2 g (5.4 mmol) of powdered sodium hydroxide is added to a mixture of 1.2 g (3.6 mmol) of 2-ethylsulfonyl-5-(2-propionylhydrazino)benzenesulfonamide, 1.4 g (5 mmol) of phenyl N-(4,6-dimethoxypyrimidin-2-yl)-carbamate and 30 ml of acetonitrile at 25~C. The mixture is stirred at 25~C for 2.5 hours and evaporated and the residue i~ triturated with diethyl ether. After filtra-tion and drying, 1.5 g (75% of theory) of 3-(4,6-dimeth--oxypyrimidin-2-yl)-1-[2-ethylsulfonyl-5-(2-propionyl-hydrazino)phenylsulfonyl]urea are obtained as the sodium salt, of melting point 219 to 221~C.

Example A10 2-tert-Butylsulfamoyl-4-nitrobenzoic acid dimethylamide About 210 g (4.5 mol) of gaseous dimethylamine are passed into a solution of 69.0 g (0.22 mol) of methyl 2-tert-butylsulfamoyl-4-nitrobenzoate and 900 ml of methanol at 25~C. The mixture is stirred at 25~C for 5 days and evaporated and the residue is crystallized by trituration with diisopropyl ether. The resulting solid is dissolved in methylene chloride and the organic phase is washed four times with bicarbonate solution. It is dried and evaporated to give, as the residue, 39.0 g (54% of theory) of 2-tert-butylsulfamoyl-4-nitrobenzoic acid dimethylamide of melting point 143 to 145~C (decomposi-tion).

Example A11 4-Amino-2-tert-butylsulfamoylbenzoic acid dimethylamide 22.5 g (0.4 mol) of iron powder are added in portions to a mixture of 40.2 g (0.12 mol) of 2-tert-butylsulfamoyl-4-nitrobenzoic acid dimethylamide, 165 ml of glacial acetic acid and 50 ml of water at 80~C. The mixture is subsequently stirred at 80 to 85~C for 4 hours and 70 ml of 2N HCl are then added to the still hot solution. After cooling to room temperature, the mixture is filtered with suction and the solid is washed several times with water.
The solid is stirred with ethyl acetate and filtered off and the organic phase is dried and evaporated. The solid which remains is triturated with diisopropyl ether.
24.1 g (66% of theory) of 4-amino-2-tert-butyl3ulfamoyl-benzoic acid dimethylamide of melting point 205 to 206~C
are obtained.

Example A12 2-tert-Butylsulfamoyl-4-hydrazinobenzoic acid dimethyl-amide 5.0 g (16.7 mmol) of4-amino-2-tert-butylsulfamoylbenzoic acid dimethylamide are suspended in 6.7 ml of concen-trated HCl and 8 ml of water. A solution of 1.3 g (18.4 mmol) of sodium nitrite in 6 ml of water i8 added dropwise at O to 5~C. After 5 minutes, the undissolved residue is filtered off and the liquid phase is added to a solution of 11.3 g (50 mmol) of tin(II) chloride dihydrate in 12 ml of concentrated HCl at 0~C. The reaction mixture is kept at 0~C for 16 hours and the pH
is then brought to 6 to 7 by addition of 47 g of 6N NaOH
solution and 5 g of solid NaHCO3. The mixture is extracted with ethyl acetate and the extract is dried and evaporated. 3.5 g (66% of theory) of 2-tert-butyl-sulfamoyl-4-hydrazinobenzoic acid dimethylamide remain as a yellow oil;
lH-NMR (CDCl3): ~ = 1.23 (8, 9H, C(CH3)3); 2.87 (8, 3H, NCH3); 3.07 (8, 3H, NCH3); 3.65 (broad, 2H, NH2); 6.02 (broad, lH, phenyl NH); 6.04 (8, lH, SO2NH); 7.01 (dd, lH, phenyl 5H); 7.11 (d, lH, phenyl 6H); 7.44 (d, lH, phenyl 3H).

Example A13 2-tert-Butylsulfamoyl-4-ethylidenehydrazinobenzoic acid dimethylamide 3.5 g (11 mmol) of 2-tert-butylsulfamoyl-4-hydrazino-benzoic acid dimethylamide in 70 ml of methanol are stirred with 1.2 g (22 mmol) of acetaldehyde at 25~C for 3 hours. The mixture is evaporated and the residue is triturated with diisopropyl ether to give, after filtra-tion and drying, 2.6 g (69% of theory) of 2-tert-butyl-sulfamoyl-4-ethylidenehydrazinobenzoicaciddimethylamide of melting point 187 to 189~C.

~ CA 02224612 1997-12-12 , Example A14 4-Ethylidenehydrazino-2-sulfamoylbenzoic acid dimethyl-amide 2.0 g (5.9 mmol) of 2-tert-Butylsulfamoyl-4-ethylidene-hydrazinobenzoic acid dimethylamide are stirred in 30 mlof trifluoroacetic acid at 25~C for 2 hours. The mixture is evaporated and the residue is triturated with diethyl ether. 0.8 g (48% of theory) of 4-ethylidenehyrazino-2-sulfamoylbenzoic acid dimethylamide of melting point 188 to 192~C are obtained.

Example A15 2-[3-(4,6-Dimethoxypyrimidin-2-yl)ureidosulfonyl]-4-ethylidenehydrazinobenzoic acid dimethylamide 0.8 g (5.4 mmol) of 1,8-diazabicyclot5.4.0]undec-7-ene (DBU) is added to a mixture of 0.7 g (2.5 mmol) of 4-ethylidenehydrazino-2-sulfamoylbenzoic acid dimethyl-amide, 0.8 g (3.0 mmol) of phenyl N-(4,6-dimethoxy-pyrimidin-2-yl)carbamate and 20 ml of acetonitrile at 0~C. The mixture is stirred at 0~C for 2 hours and then poured into ice-water, the pH is brought to 2 with 2N HCl and the mixture is extracted with methylene chloride. The organic phase is washed with 2N HCl, dried and evapor-ated. After trituration with diisopropyl ether, 0.45 g (39% of theory) of 2-t3-(4,6-dimethoxypyrimidin-2-yl)-ureidosulfonyl]-4-ethylidenehydrazinobenzoic acid dimethylamide of melting point 127 to 129~C (decomposi-tion) is obtained.

The compounds described in the following Tables 1, 2 and 3 are obtained in accordance with or analogously to the above Examples A1 to A15.

Abbreviations in the tables:

m.p. = solidification point in ~C = melting point in ~C
(d) = melting point with decomposition 5 Ac = acetyl Bu = nBu = n-butyl i-Bu = isobutyl t-Bu = t-butyl Et = ethyl 10 Me = methyl Pg = propargyl Ph = phenyl Pr = nPr = n-propyl i-Pr = isopropyl 15 cPr = cyclopropyl Het = heterocyclic radical, where Het repre-sents one of the radicals T1 to T15 O~e O~e OUe OEt N~ N~ N~ N~
--<0~ ~ ~0 N ~ --(O> , --<O N
N~ N~ N~ N~
O~e ~e ~e ~e Tl T2 T3 T~
~e O~e O~e OCH2C~3 N~ N~ N~ N~
--< O~ ~ ~ O~ , ~ O N ' ~ o N
N~ N~ N~ N~
~e Cl OUe N~e2 OEt O~e OEt CE3 N-~ N-~ N ~ N
~ ~ ~ O ~ . ~ O N , N-~ N ~ N ~ N-~
OEt S~e NH~e O~e rg rlO Tl~ rl2 C~3 N ~ N-~ N-~
N , ~ O ~ , ~ O
N ~ N-~ N-~
O~e OCH~2 Cl For easier legibility of index numbers, contrary to the usual manner of writing, formula radicals such as NH4, CH2CO2Me, CH3SCH2CH2- and the like are shown in the tables with atom symbols and index numbers at the same level, i.e. as NH4, CH2C02Me, CH3SCH2CH2- and the like.

A divalent radical such as -(CH2)4- in coln~ns for R7, R8 means that R7 and R3 together are the divalent radical bridge and form an alkylidene radical with the carbon atom of the group R7R8C=. Correspo~; ng statements apply to other entries which apply to two columns.

~ CA 02224612 1997-12-12 .

Table 1: Compounds of the formula (Ia) S ( ~ ) n R

'NJ~S' ~ 'H e t 8 19 o O o R R

. R n R3 R7 R3 R9 ~ Het ~.p.

1-1 Me O H Me H H H Tl 1-2 Me O H Me H H Na T1 1-3 Me O H Me Me H H T1 1-4 Me O H Me Me H Na T1 1-5 Me O H -(CH2~4- H H T1 1-6 Me O H -~CH2~4- H Na T1 1-7 Me 1 H Me H H H T1 1-8 Me 1 H Me H H Na T1 1-9 Me 1 H Me Me H H T l 1-10 Me 1 H Me Me H Na T1 1-11 Me 1 H -(CH2)4- H H Tl 1-12 Me 1 H -(CH2)4- H Na Tl 1-13 Me 2 H Me H H H T1 1.14 Me 2 H Me H H Na T1 1-15 Me 2 H Me Me H H Tl 1-16 Me 2 H Me Me H Na Tl 1-17 Me 2 H -(CH2~4- H H T 1 1-18 Me 2 H -(CH214- H Na T1 1-19 Me 2 H Me H H H T2 1-20 Me 2 H Me H H Na T2 1-21 Me 2 H Me Me H H T2 1-22 Me 2 H Me Me H Na T2 1-23 Me 2 H -(CH2)4- H H T2 1-24 Me 2 H -(CH2)4- H Na T2 1-25 Et 0 H Me H H H T 1 1-26 Et 0 H Me H H Na Tl 1-27 Et 0 H Me Me H H T1 1-28 Et 0 H Me Me H Na T1 1-29 Et 0 H -(CH2)4- H H Tl 1-30 Et 0 H -(CH2)4- H Na Tl 1-31 Et 1 H Me H H H T1 1-32 Et 1 H Me H H Na T1 ~x. R n R3 R7 R8 R9 ~ H~t m.p.

1-33 Et 1 H Me Me H H Tl 1 -34 Et 1 H Me Me H Na T 1 1-35 Et 1 H -~CH2)4- H H T1 1-36 Et 1 H -(CH2)4- H Na T1 1-37 Et 2 H Me H H H T1 149-151 (d) 1-38 Et 2 H Me H H Na Tl 238-239 (d~
1-39 Et 2 H Me H H K T1 1-40 Et 2 H Me H H NH4 Tl 141 Et 2 H Me H H NMe4 Tl 1-42 Et 2 H Me H H NHEt3 Tl 1-43 Et 2 H Me H H H T2 1-44 Et 2 H Me H H Na T2 1-45 Et 2 H Me H H K T2 1 46 Et 2 H Me H H NH4 T2 1 47 Et 2 H Me H H NMe4 T2 1-48 Et 2 H Me H H NHEt3 T2 1-49 Et 2 H Me H H H TS
1-50 Et 2 H Me H H Na T5 1 -51 Et 2 H Me H H K T5 1-52 Et 2 H Me H H NH4 T5 1-53 Et 2 H Me H H NMe4 T5 1-54 Et 2 H Me H H NHEt3 T5 1 -55 Et 2 H Me H H H T6 1-56 Et 2 H Me H H Na T6 1-57 Et 2 H Me H H K T6 1-58 Et 2 H Me H H NH4 T6 1-59 Et 2 H Me H H NMe4 T6 1-60 Et 2 H Me H H NHEt3 T6 1 -61 Et 2 H Me H H H ., 1-62 Et 2 H Me H H Na T7 1-63 Et 2 H Me H H K T7 1-64 Et 2 H Me H H NH4 T7 1-65 Et 2 H Me H H NMe4 T7 1-66 Et 2 H Me H H NHEt3 T7 1-67 Et 2 H Me H H H T8 1-68 Et 2 H Me H H Na T8 1-69 Et 2 H Me H H K T8 1-70 Et 2 H Me H H NH4 T8 1-71 Et 2 H Et H H H T1 ~. R n Ra R7 R3 R9 ~ ~et m.p.

1-72 Et 2 H Bu H H Na T1 1-73 Et 2 H Me H H H T3 1-74 Et 2 H MR H H Na T3 1-75 Et 2 H Me H H H T4 1-76 Et 2 H Me H H Na T4 1-77 Et 2 H Me H H H T9 1-78 Et 2 H Me H H Na T9 1 -79 Et 2 H Me H H H T10 1 -80 Et 2 H Me H H Na T 10 1-81 Et 2 H Me H H H T11 1-82 Et 2 H Me H H Na T11 1 -83 Et 2 H Me H H H T12 1-84 Et 2 H Me H H Na T12 1-85 Et 2 H Me H H H T13 1 -86 Et 2 H Me H H Na T13 1-87 Et 2 H Me H H H T14 1-88 ~t 2 H Me H H Na T14 1-89 Et 2 H Me H H H T15 1 90 Et 2 H Me H H Na T15 1-91 Et 2 H Me Me H H T1 145-148 ~d) 1 -92 Et 2 H Me Me H Na Tl 199-201 ~d~
1-93 Et 2 H Me Me H K T1 1-94 Et 2 H Me Mo H NH4 Tl 1-95 Et 2 H Me Me H NMe4 Tl 1-96 Et 2 H Me Me H NHEt3 Tl 1-97 Et 2 H Me Me H H T2 1-98 Et 2 H Me Me H Na T2 1-99 Et 2 H Me Me H K T2 1 -100 Et 2 H Me Me H NH4 T2 1-101 Et 2 H Me Me H NMe4 T2 1-102 Et 2 H Me Me H NHEt3 T2 1-103 Et 2 H Me Me H H T5 1-104 Et 2 H Me Me H Na T5 1-105 Et 2 H Me Me H K T5 1 - 106 Et 2 H Me Me H NH4 T5 1-107 Et 2 H Me Me H NMe4 T5 1-108 Et 2 H Me Me H NHEt3 T5 1 - 109 Et 2 H Me Me H H T6 1-110 Et 2 H Me Me H Na T6 k~. R n R3 R7 R3 R9 ~ ~et m.p.

1 - 111 Et 2 H Me Me H K T6 1-112 Et 2 H Me Me H NH4 T6 1 - 113 Et 2 H Me Me H NMe4 T6 1-114 Et 2 H Me Me H NHEt3 T6 1 - 115 Et 2 H Me Me H H T7 1 -116 Et 2 H Me Me H Na T7 1 - 117 Et 2 H Me Me H K T7 1 -118 Et 2 H Me Me H NH4 T7 1 - 119 Et 2 H Me Me H NMe4 T7 1 -120 Et 2 H Me Me H NHEt3 T7 1 - 121 Et 2 H Me Me H H T8 1 -123 Et 2 H Me Me H Na T8 1 - 124 Et 2 H Me Me H K T8 1-125 Et 2 H Me Me H NH4 T8 1 -126 Et 2 H Me Me H NMe4 T8 1-127 Et 2 H Me Me H NHEt3 T8 1 - 128 Et 2 H Me Me H H T3 1 -129 Et 2 H Me Me H Na T3 1 - 130 Et 2 H Me Me H H T4 1 - 131 Et 2 H Me Me H Na T4 1 - 132 Et 2 H Me Me H H T9 1-1~3 Et 2 H Me Me H Na T9 1-134 Et 2 H Me Me H H T10 1 -135 Et 2 H Me Me H Na T10 1 -136 Et 2 H Me Me H H T11 1 -137 Et 2 H Me Me H Na Tl l 1 -138 Et 2 H Me Me H H T12 1 -139 Et 2 H Me Me H Na T12 1 - 140 Et 2 H Me Me H H T 13 1-141 Et 2 H Me Me H Na T13 1-142 Et 2 H Me Me H H T14 1-143 Et 2 H Me Me H Na T14 1-144 Et 2 H Me Me H H T15 1-145 Et 2 H Me Me H Na T15 1 -146 Et 2 H -(CH2~4- H H T1 164-166 ~d) 1-147 Et 2 H -ICH2)4- H Na T1 223-226 Id) 1-148 Et 2 H -ICH2)4- H K T1 1 -149 Et 2 H -ICH2)4- H NH4 T1 1-150 Et 2 H -ICH2)4- H NMe4 Tl k~. R n R3 R7 R3 R9 ~ ~et m.p.

1 -t 51 Et 2 H -~CH2~4- H NHEt3 T1 1-152 Et 2 H -(CH2~4- H H T2 1 -153 Et 2 H -ICH2)4- H Na T2 1-154 Et 2 H -(CH2)4- H K T2 1-155 Et 2 H -(CH214- H NH4 T2 1-156 Et 2 H -tCH2)4- H NMe4 T2 1-157 Et 2 H -~CH2)4- H NHEt3 T2 1-158 Et 2 H -(CH2)4- H H T5 1 -l S9 Et 2 H -(CH2)4- H Na T5 1 -160 Et 2 H -~CH2)4- H K T5 1-161 Et 2 H -~CH2)4- H NH4 TS
1 - 162 Et 2 H -~CH2)4- H NMe4 TS
1 -163 Et 2 H -~CH2)4- H NHEt3 TS
1 -164 Et 2 H -(CH2)4- H H T6 1-165 Et 2 H -(CH2)4- H Na T6 1 - 166 Et 2 H -(CH2)4- H K T6 1 -167 Et 2 H -(CH2)4- H NH4 T6 1 - 168 Et 2 H -(CH2)4- H NMe4 T6 1 -169 Et 2 H -ICH2)4- H NHEt3 T6 1 -170 Et 2 H -~CH2)4- H H T7 1 - 171 Et 2 H -(CH2)4- H Na T7 1 -172 Et 2 H -(CH2)4- H K T7 1-173 Et 2 H -(CH2)4- H NH4 T7 1 - 174 Et 2 H -(CH2)4- H NMe4 T7 1 -175 Et 2 H -(CH2)4- H NHEt3 T7 1-176 Et 2 H -(CH2)4- H H T8 1 -177 Et 2 H -(CH2)4- H Na T8 1 -178 Et 2 H -(CH2)4- H K T8 1 -179 Et 2 H -(CH2)4- H NH4 T8 1 -180 Et 2 H -(CH2)4- H NMe4 T8 1-181 Et 2 H -(CH2)4- H NHEt3 T8 1-182 Et 2 H -(CH2)4- H H T3 1 -183 Et 2 H -(CH2)4- H Na T3 1-184 Et 2 H -(CH2)4- H H T4 1 -185 Et 2 H -(CH2)4- H Na T4 1-186 Et 2 H -~CH2)4- H H T9 1-187 Et 2 H -(CH2)4- H Na T9 1-188 Et 2 H -(CH2)4- H H T10 1-189 Et 2 H -(CH2)4- H Na T10 1-190 Et 2 H -(CH2)4- H H Tl l 1-191 Et 2 H -(CH2)4- H Na T11 . R n R3 R7 R8 R9 ~ Het ~.p.

1-192 Et 2 H -~CH2)4- H H T12 1-193 Et 2 H -~CH2)4- H Na T12 1 -194 Et 2 H -~CH2)4- H H T13 1 -195 Et 2 H -ICH2)4- H Na T13 1 -196 Et 2 H -~CH2)4- H H T14 1 -197 Et 2 H -~CH2~4- H Na T14 1 -198 Et 2 H -(CH2)4- H H T15 1 -199 Et 2 H -(CH2)4- H Na T15 1-200 Et 2 Me Me H H H T2 1-201 Et 2 Me Me H H Na T2 1-202 Et 2 Me Me Me H H T2 1-203 Et 2 Me Me Me H Na T2 1-204 Et 2 Me -(CH2~4- H H T2 1-205 Et 2 Me -(CH2~4- H Na T2 1-206 Pr 2 H Me H H H T1 1-207 Pr 2 H Me H H Na Tl 1-208 Pr 2 H Me Me H H Tl 1 -209 Pr 2 H Me Me H Na T 1 1-210 Pr 2 H -(CH2~4- H H Tl 1-211 Pr 2 H -~CH2~4- H Na Tl 1 -212 Pr 2 H Me H H H T2 1 -213 Pr 2 H Me H H Na T2 1 -214 Pr 2 H Me Me H H T2 1 -215 Pr 2 H Me Me H Na T2 1-216 Pr 2 H -(CH2~4- H H T2 1-217 Pr 2 H -~CH2~4- H Na T2 1 -218 i-Pr 2 H Me H H H T 1 1 -219 i-Pr 2 H Me H H Na T 1 1 -220 i-Pr 2 H Me Me H H T 1 1-221 i-Pr 2 H Me Me H Na Tl 1-222 i-Pr 2 H -~CH2i4- H H Tl 1-223 i-Pr 2 H -~CH2~4- H NA T1 1-224 i-Pr 2 H Me H H H T2 1-225 i-Pr 2 H Me H H Na T2 1-226 i-Pr 2 H Me Me H H T2 1-227 i-Pr 2 H Me Me H Na T2 1-228 i-Pr 2 H -~CH2~4- H H T2 1-229 i-Pr 2 H -(CH2~4- H Na T2 1-230 CH2C02Me 2 H Me H H H Tl 1-231 CH2C02Me 2 H Me H H H T2 1-232 CH2-c-Pr 2 H Me Me H H Tl -RX. R n R3 R7 R8 R9 ~ ~et ~.P.

1-233 CH2-c-Pr 2 H Me Me ~ H T2 1-234 CH2F 2 H -~CH2)4- H H T1 1-235 CH2F 2 H -ICH2~4- H H T2 1-236 CH2CI 2 H Me H H H T1 1-237 CH2CI 2 H Me H H H T2 1-238 CH2CH2F 2 H Me Me H H T1 1-239 CH2CH2F 2 H Me Me H H T2 1-240 CH2CF3 2 H -ICH2~4- H H Tt 1-241 CH2CF3 2 H -ICH2~4- H H T2 1-242 CH2CH20Me 2 H Me H H H Tl 1-243 CH2CH20Me 2 H Me H H H T2 1-244 CH2CH2SMe 2 H Me Me H H Tl 1-245 CH2CH2SMe 2 H Me Me H H T2 1-246 ~ 2 H -ICH2)4- H H Tl 1-247 ~ 2 H -ICH2)4- H H T2 1-248 t-Bu 2 H Me H H H Tl 1-249 t-Bu 2 H Me H H H T2 1-250 C~_lo~.ttl 2 H Me Me H H Tl 1-251 CYL'D~ ,t~tl 2 H Me Me H H T2 1-252 Cvclohexyl 2 H -ICH2~4- H H T1 1-253 Cyclohexyl 2 H -ICH2~4- H H T2 1-254 CH2CH=CH2 2 H Me H H H T1 1-255 CH2CH=CH2 2 H Me H H H T2 1-256 CH2C-CH 2 H Me Me H H T1 1-257 CH2C-CH 2 H Me Me H H T2 1-258 CH2Ph 2 H -~CH2~4- H H T1 1-259 CH2~ 2 H -(CH2)4- H H T2 1-260 NMe2 2 H Me H H H T1 1-261 NMe2 2 H Me H H Na T1 1-262 NMe2 2 H Me Me H H T1 1-263 NMe2 2 H Me Me H Na T1 1-264 NMe2 2 H -(CH2)4- H H T1 1-265 NMe2 2 H -(CH2~4- H Na T1 1-266 NMe2 2 H Me H H H T2 1-267 NMe2 2 H Me H H Na T2 1-268 NMe2 2 H Me Me H H T2 1-269 NMe2 2 H Me Me H Na T2 1-270 NMe2 2 H -~CH2~4- H H T2 1-271 NMe2 2 H -ICH2~4- H Na T2 1-272 NEt2 2 H Me H H H T1 1-273 NEt2 2 H Me H H H T2 CA 022246l2 l997-l2-l2 . R n R3 R7 R8 R9 ~ ~et m.p.

1-274 NHPh 2 H Me Me H H T1 1-275 NHPh 2 H Me Me H H T2 1-276 NHMe 2 H -~CH2)4- H H T1 1-277 NHMe 2 H -~CH2~4- H H T2 1-278 NHEt 2 H Me H H H T1 1-279 NHEt 2 H Me H H H T2 1-280 NHCH2C--CH 2 H Me Me H H T1 1 -281 NHCH2C ~ CH 2 H Me Me H H T2 1-282 N~Allyl)2 2 H -lCH2)4- H H T1 1-283 N(Allyl)2 2 H -(CH2)4- H H T2 1-284 Ft.-l ~ 2 H Me H H H T1 1-285 Py.-. 1 \o 2 H Me H H H T2 1-286 ' ~ ~ 2 H Me Me H H T1 1-287 Ma ~ )o 2 H Me Me H H T2 C02Me 2 H -(CH2~4- H H T1 C02Me 2 H -(CH2~4- H H T2 1-290 Et 2 H CF3 H H H T1 1 -291 Et 2 H CF3 H H Na T 1 1-292 Et 2 H CF3 H H H T2 1-293 Et 2 H CF3 H H Na T2 1-294 Et 2 H CF3 H H H T5 1-295 Et 2 H CF3 H H Na T5 1-296 Et 2 H CF3 H H H T6 1-297 Et 2 H CF3 H H Ns T6 1-298 Et 2 H CF3 H H H T7 1-299 Et 2 H CF3 H H Na T7 1-29Q Et 2 H CF3 CH3 H H T1 1-291 Et 2 H CF3 CH3 H Na T1 1-292 Et 2 H CF3 CH3 H H T2 1-293 Et 2 H CF3 CH3 H Na T2 1-294 Et 2 H CF3 CH3 H H T5 1-295 Et 2 H CF3 CH3 H Na T5 1-296 Et 2 H CF3 CH3 H H T6 1-297 Et 2 H CF3 CH3 H Na T6 1-298 Et 2 H CF3 CH3 H H T7 1-299 Et 2 H CF3 CH3 H Na T7 1-300 Et 2 H C02H H H H T1 1-301 Et 2 H C02H H H Na T1 1-302 Et 2 H C02H H H H T2 RX. R n R9 R7 R3 R9 ~ Het m.p.

1-303 Et 2 H C02H H H Na T2 1-304 Et 2 H C02H H H H T5 1-305 Et 2 H C02H H H Na T5 1-306 Et 2 H C02H H H H T6 1-307 Et 2 H C02H H H Na T6 1-308 Et 2 H C02H H H H T7 1-309 Et 2 H C02H H H Na T7 1-310 Et 2 H -ICH2)5- H H Tl 1-311 Et 2 H -ICH2)5- H H T2 1-312 Et 2 H CH3CH=CH- H H H Tl 1 -313 Et 2 H CH3CH = CH- H H H T2 1 -314 Et 2 H CH30CH2- H H H T1 1 -315 Et 2 H CH30CH2- H H H T2 1-3t6 Et 2 H C02Me H H H T1 1 -317 Et 2 H C02Me H H H T2 1-318 Et 2 H C02Me Me H H T1 1 -319 Et 2 H C02Me Me H H T2 1-320 Et 2 H 2-Thienyl H H H T1 1-321 Et 2 H 2-Thienyl H H H T2 1-322 Et 2 H 2-Pyridyl H H H T1 1-323 Et 2 H 2-Pyridyl H H H T2 1-324 Et 2 H 3-Pyridyl H H H T1 1-325 Et 2 H 3-Pyridyl H H H T2 1-326 Et 2 H CH3SCH2CH2- H H H T1 1-327 Et 2 H CH35CH2CH2- H H H T2 1-328 Et 2 H 2-T~t~ yd ~ H H H T1 furyl 1-329 Et 2 H 2-Tet-h,d~o- H H H T2 furyl 1-330 Et 2 H Ph H H H Tl 1-331 Et 2 H Ph H H H T2 1-332 Et 2 H 2-CI-Ph H H H Tl 1-333 Et 2 H 2-CI-Ph H H H T2 1 -334 Et 2 H 3-CI-Ph H H H T 1 1-335 Et 2 H 3-CI-Ph H H H T2 1-336 Et 2 H 4-CI-Ph H H H Tl 1-337 Et 2 H 4CI-Ph H H H T2 1-338 Et 2 H 2-Me-Ph H H H T1 1-339 Et 2 H 2-Me-Ph H H H T2 1-340 Et 2 H 3-Me-Ph H H H T1 1-341 Et 2 H 3-Me-Ph H H H T2 R~. R n R8 R7 R3 R9 ~ ~et m.p.

1-342 Et 2 H 4-Me-~ H H H Tl 1-343 Et 2 H 4-Me-Ph H H H T2 1-344 Et 2 H 4-MeO-Ph H H H Tl 1-345 Et 2 H 4-M~O-~ H H H T2 1-346 Et 2 H 4-F-~ H H H Tl 1-347 Et 2 H 4-F-Ph H H H T2 1-348 Et 2 H 3-CF3-~ H H H Tl 1-349 Et 2 H 3-CF3-Ph H H H T2 1-350 Et 2 H CH2CI H H H Tl 1-351 Et 2 H CH2CI H H H T2 1-352 Et 2 H Me H Me H Tl 1-353 Et 2 H Ma H Et Na T2 1-354 Et 2 H Me Me Me H T1 1-355 Et 2 H Me Me ~ Na Tl 1-356 Et 2 H -(CH2)4 Me H T1 1-357 Et 2 H -~CH2)4- Me Na T2 1-358 Me 2 H COMe COOMe H H T1 1-359 Me 2 H COMe COOMe H Na T1 1-360 Me 2 H COMe COOMe H H T2 1-361 Me 2 H COMe COOMe H Na T2 1-362 Me 2 H CN COOMe H H T1 1-363 Me 2 H CN COOMe H N8 Tl 1-364 Me 2 H CN COOMb H H T2 1-365 Me 2 H CN COOMe H Na T2 1-366 Me 2 H CN COOEt H H T1 1-367 Me 2 H CN COOEt H Na T1 1-368 Me 2 H CN COOEt H H T2 1-369 Me 2 H CN COOEt H Na T2 1-370 Me 2 H N02 COOEt H H T1 1-371 Me 2 H N02 COOEt H Na Tl 1-372 Me 2 H N02 COOEt H H T2 1-373 Me 2 H N02 COOEt H Na T2 1-374 Et 2 H COMe COOEt H H T1 1-375 Et 2 H COMe COOEt H Na T1 1-376 Et 2 H COMe COOEt H H T2 1-377 Et 2 H COMe COOEt H Na T2 1-378 Et 2 H COMe COOMe H H T1 1-379 Et 2 H COM~ COOMe H Na T1 1-380 Et 2 H COMe COOMe H H T2 1-381 Et 2 H COMe COOMe H Na T2 1-382 Et 2 H COEt COOMe H H T1 ~x. R n R3 R7 R3 R9 ~ ~et ~.p.

1-383 Et 2 H COEt COOMe H Na Tl 1-384 Et 2 H COEt COOMe H H T2 1-385 Et 2 H COEt COOMe H Na T2 1-386 Et 2 H COMe Me H H T1 1-387 Et 2 H COMe Me H Na T1 1-388 Et 2 H COMe Me H H T2 1-389 Et 2 H COMe Me H Na T2 1-390 Et 2 H COMe COMe H H T1 1-391 Et 2 H COMe COMe H Na T1 1-392 Et 2 H COMe COMe H H T2 1-393 Et 2 H COMe COMe H Na T2 1-394 Et 2 H COMe CONH2 H H T1 1-395 Et 2 H COMe CONH2 H Na T1 1-396 Et 2 H COMe CONH2 H H T2 1-397 Et 2 H COMe CONH2 H Na T2 1-398 Et 2 H COMe CONH~ H H Tl 1-399 Et 2 H COMe CONHPh H Na Tl 1-400 Et 2 H COMe CONHPh H H T2 1-401 Et 2 H COMe CONHPh H NA T2 1-402 Et 2 H COMe CONHMe H H Tl 1-403 Et 2 H COMe CONHMe H Na Tl 1-404 Et 2 H COMe CONHMe H h T2 1405 Et 2 H COMe CONHMe H Na T2 1406 Et 2 H COMe CONMe2 H H T1 1407 Et 2 H COMe CONMe2 H Na T1 1-408 Et 2 H COMe CONMe2 H H T2 1-409 Et 2 H COMe CONMe2 H Na T2 1-410 Et 2 H COOMe COOMe H H Tl 1-411 Et 2 H COOMe COOMe H Na T1 1-412 Et 2 H COOMe COOMe H H T2 1413 Et 2 H COOMe COOMe H Na T2 1-414 Et 2 H COOMe COOMe H H T5 1415 Et 2 H COOMe COOMe H Na T5 1-416 Et 2 H COOMe COOMe H H T6 1417 Et 2 H COOMe COOMe H Na T6 1418 Et 2 H COOEt COOEt H H Tl 1419 Et 2 H COOEt COOEt H Na T1 1-420 Et 2 H COOEt COOEt H H T2 1-421 Et 2 H COOEt COOEt H Na T2 1-422 Et 2 H COOEt COOEt H H T5 1423 Et 2 H COOEt COOEt H Na T5 ~ CA 02224612 1997-12-12 ~s. R n Ra R7 R8 R9 ~ HQt ~.p.

1-424 Et 2 H COOEt COOEt H H T6 1-425 Et 2 H COOEt COOEt H Na T6 1-426 Et 2 H COOEt CONH2 H H Tl 1-427 Et 2 H COOEt CONH2 H Na Tl 1 428 Et 2 H COOEt CONH2 H H T2 1-429 Et 2 H COOEt CONH2 H Na T2 1-430 Et 2 H COOMe CN H H Tl 1-431 Et 2 H COOMe CN H Na Tl 1-432 Et 2 H COOMe CN H H T2 1-433 Et 2 H COOMe CN H Na T2 1 434 Et 2 H COOMe CN H H T5 1-435 Et 2 H COOMe CN H Na T5 1 436 Et 2 H COOMe CN H H T6 1 437 Et 2 H COOMo CN H Na T6 1 438 Et 2 H COOEt CN H H Tl 1 439 Et 2 H COOEt CN H Na Tl 1 440 Et 2 H COOEt CN H H T2 1 -441 Et 2 H COOEt CN H Na T2 1-442 Et 2 H COOEt CN H H T5 1 443 Et 2 H COOEt CN H Na T5 1 444 Et 2 H COOEt CN H H T6 1 445 Et 2 H COOEt CN H hs T6 1-446 Et 2 H COOEt N02 H H Tl 1 447 Et 2 H COOEt N02 H Na Tl 1-448 Et 2 H COOEt N02 H H T2 1-449 Et 2 H COOEt N02 H Na T2 1 450 Et 2 H COOEt N02 H H TS
1451 Et 2 H COOEt N02 H Na T5 1 452 Et 2 H COOEt N02 H H T6 1 453 Et 2 H COOEt N02 H Na T6 1-454 Et 2 H COOMe S02Me H H Tl 1-455 Et 2 H COOMe S02Me H Na Tl 1 456 Et 2 H COOMe S02Me H H T2 1-457 Et 2 H COOMe S02Me H Na T2 1-458 Et 2 H COOMe S02Et H H Tl 1 459 Et 2 H COOMe S02Et H Na Tl 1-460 Et 2 H COOMo S02Et H H T2 1 461 Et 2 H COOMe S02Et H Na T2 1-462 Et 2 H COOEt S02Me H H Tl 1-463 Et 2 H COOEt S02Me H Na Tl 1-464 Et 2 H COOEt S02Me H H T2 ~x. R n R3 R7 R3 R9 ~ ~et ~.p.

1-465 Et 2 H COOEt SO2Me H Na T2 1-466 Et 2 H COOEt PO(OEt~2 H H T1 1-467 Et 2 H COOEt PO(OEt~2 H Na Tl 1-468 Et 2 H COOEt PO(OEt~2 H H T2 1-469 Et 2 H COOEt PO(OEt)2 H Na T2 1-470 Et 2 H CONH2 CONH2 H H Tl 1-471 Et 2 H CONH2 CONH2 H Na T1 1-472 Et 2 H CONH2 CONH2 H H T2 1-473 Et 2 H CONH2 CONH2 H Na T2 1-474 Et 2 H CONMe2 CONMe2 H H T1 1-475 Et 2 H CONMe2 CONMe2 H Na T1 1-476 Et 2 H CONMe2 CONMe2 H H T2 1-477 Et 2 H CONMe2 CONMe2 H Na T2 1478 Et 2 H CONH2 CN H H Tl 1-479 Et 2 H CONH2 CN H Na T1 1-480 Et 2 H CONH2 CN H H T2 1481 Et 2 H CONH2 CN H Na T2 1-482 Et 2 H CN CN H H T1 1-483 Et 2 H CN CN H Na T1 1484 Et 2 H CN CN H H T2 1-485 Et 2 H CN CN H Na T2 1486 Et 2 H CN ~h H H T1 1487 Et 2 H CN Ph H Na T1 1488 Et 2 H CN Ph H H T2 1489 Et 2 H CN Ph H Na T2 1490 Et 2 H N02 H H H T1 1-491 Et 2 H N02 H H Na Tl 1-492 Et 2 H N02 H H H T2 1-493 Et 2 H NO2 H H Na T2 1-494 Et 2 H NO2 Me H H T1 1-495 Et 2 H NC2 Me H Na T1 1-496 Et 2 H N02 Me H H T2 1-497 Et 2 H N02 Me H Na T2 1-498 Et 2 H -CO-CH2CH2CO- H H T1 1-499 Et 2 H -CO-CH2CH2CO- H Na T1 1-500 Et 2 H -CO-CH2CH2CO- H H T2 1-501 Et 2 H -CO-CH2CH2CO- H Na T2 1-502 Et 2 H -COCH =CH-CO- H H Tl 1-503 Et 2 H -C0CH =CH-CO- H Na Tl 1-504 Et 2 H -COCH = CH-CO- H H T2 1-505 Et 2 H -COCH = CH-CO- H Na T2 ~ CA 02224612 1997-12-12 ~. R n Ra R7 R8 R9 ~ ~et ~.p.

1-5V6 Et 2 H -CO(CH2)3CO- H H T1 1-507 Et 2 H -CO~CH213CO- H Na Tl 1-508 Et 2 H -CO~CH2~3CO- H H T2 1-509 Et 2 H -CO(CH2)3CO- H Na T2 1-510 Et 2 H -COOC~CH3120CO- H H Tl 1-511 Et 2 H -COOC~CH3t20CO- H Ns Tt 1-512 Et 2 H -COOC~CH3)20CO- H H T2 1-513 Et 2 H -COOC~CH3)20CO- H Na T2 1-514 Et 2 H -~CH2)4CO- H H Tl 1-515 Et 2 H -ICH2)4CO- H Na T1 1-516 Et 2 H -(CH2~4CO- H H T2 1-517 Et 2 H -(CH2~4CO- H Na T2 1-518 Et 2 H -(CH213NHCO- H H T1 1-519 Et 2 H -(CH2~3NHCO- H Na Tl 1-520 Et 2 H -(CH2)3NHCO- H H T2 1-521 Et 2 H -(CH2)3NHCO- H Na T2 1-522 Et 2 H -C~CH3~=NN~CH3)-CO- H H T1 1-523 Et 2 H -C(CH3)=NN(CH3~-CO- H Na T1 1-524 Et 2 H -C(CH31 NN(CH31-CO- H H T2 1-525 Et 2 H C(CH3)~NN~CH3)-CO- H Na T2 1-526 Et 2 H -NsC(CH3)-OCO- H H Tl 1-527 Et 2 H -N~C(CH3)-OCO- H Na T1 1-528 Et 2 H -N--C~CH3)-OCO- H H T2 1-529 Et 2 H -N=UCH3)-OCO- H Na T2 1-530 Et 2 H -COCH2N~CH3)-CO- H H T1 1-531 Et 2 H -COCH2N~CH3)-CO- H Na T1 1-532 Et 2 H -COCH2N~CH3)-CO- H H T2 1-533 Et 2 H -COCH2N~CH3)-CO- H Na T2 1-534 Et 2 H 1.2-(-CO-C6H4-CO-) H H T1 1-535 Et 2 H 1,2-(-CO-C6H4-CO-) H Na T1 1-536 Et 2 H 1,2-~-CO-C6H4-CO-) H H T2 1-537 Et 2 H 1,2-~-CO-C6H4-CO-) H Na T2 Table 2: Compounds of the formula (lb) S ( ~ ) n R
R~l ~/ M IR3 ( l b ) 'N'N~o o o k~. R n R3 Rlo Rll R9 ~ ~et m.p.

2-1 Me O H CHO H H H Tl 2-2 Me 0 H CHO Me H Ns Tl 2-3 Me O H MeCO H H H T 1 2-4 Me O H MeCO Me H Na Tl 2-5 Me O H MaOCO H H H Tl 2-6 Me 0 H i-PrCO H H Na Tl 2-7 Me 1 H CHO H H H Tl 2-8 Me 1 H CHO Me H Na Tl 2-9 Me 1 H MeCO H H H Tl 2-10 Me 1 H MeCO Me H Na Tl 2-11 Me 1 H MeOCO H H H Tl 2-12 Me 1 H i-PrCO H H Na T1 2-13 Me 2 H CHO H H H T1 2-14 Me 2 H CHO Me H Na Tl 2-15 Me 2 H MeCO H H H Tl 2-16 Me 2 H MeCO Me H Na Tl 2-17 Me 2 H MeOCO H H H Tl 2-18 Me 2 H i-PrCO H H Na Tl 2-19 Me 2 H CHO H H H T2 2-20 Me 2 H CHO Me H Na T2 2-21 Me 2 H MeCO H H H T2 2-22 Me 2 H MeCO Me H Na T2 2-23 Me 2 H MeOCO H H H T2 2-24 Me 2 H i-PrCO H H Na T2 2-25 Et O H CHO H H H T 1 2-26 Et 0 H CHO Me H Na Tl 2-27 Et 0 H MeCO H H H T1 2-28 Et 0 H MeCO Me H Na T1 2-29 Et 0 H MeOCO H H H Tl 2-30 Et 0 H i-PrCO H H Na Tl 2-31 ~t 1 H CHO H H H Tl 2-32 Et 1 H CHO Me H Na Tl 13x. R n R3 Rlo Rll R9 M ~et m.p.

2-33 Et 1 H MeCO H H H T1 2-34 Et 1 H MeCO Me H Na T 1 2-35 Et 1 H MeOCO H H H T1 2-36 Et 1 H i-PrCO H H Na T1 2-37 Et 2 H CHO H H H T1 2-38 Et 2 H CHO H H Na T 1 2-39 Et 2 H CHO H H K T1 2-40 Et 2 H CHO Me H H T1 2-41 Et 2 H CHO Me H Na T1 2-42 Et 2 H CHO H H NHEt3 T1 2-43 Et 2 H CHO H H H T2 2-44 Et 2 H CHO H H Na T2 245 Et 2 H CHO Me H H T2 2-46 Et 2 H CHO H H NH4 T2 2-47 Et 2 H CHO H H NMe4 T2 2-48 Et 2 H CHO Me H Na T2 2-49 Et 2 H CHO H H H T5 2-50 Et 2 H CHO Me H Na T5 2-51 Et 2 H CHO Me H H T5 2-52 Et 2 H CHO H H NH4 T5 2-53 Et 2 H CHO H H NMe4 T5 2-54 Et 2 H CHO H H NHEt3 T5 2-55 Et 2 H CHO H H H T6 2-56 Et 2 H CHO H H Na T6 2-57 Et 2 H CHO H H K T6 2-58 Et 2 H CHO H H NH4 T6 2-59 Et 2 H CHO Me H H T6 2-60 Et 2 H CHO Me H Na T6 2-61 Et 2 H CHO H H H T7 2-62 Et 2 H CHO H H Na T7 2-63 Et 2 H CHO H H K T7 2-64 Et 2 H CHO Me H H T7 2-65 Et 2 H CHO Me H Na T7 2-66 Et 2 H CHO H H NHEt3 T7 2-67 Et 2 H CHO H H H T8 2-68 Et 2 H CHO H H Na T8 2-69 Et 2 H CHO Me H H T8 2-70 Et 2 H CHO H H NH4 T8 2-71 Et 2 H CHO Me H Na T8 2-72 Et 2 H CHO H H NHEt3 T8 2-73 Et 2 H CHO Me H H T3 ~x . R n R3 Rlo Rll R9 M ~et m . p .

2-74 Et 2 H CH0 H H Na T3 2-75 Et 2 H CHO H H H T4 2-76 Et 2 H CHO Me H Na T4 2-77 Et 2 H CHO Me H H T9 2-78 Et 2 H CHO H H Na T9 2-79 Et 2 H CH0 H H H T10 2-80 Et 2 H CH0 Me H Na T10 2-81 Et 2 H CH0 Me H H Tl l 2-B2 Et 2 H CH0 H H Na Tl l 2-83 Et 2 H CH0 H H H T 12 2-84 Et 2 H CH0 Me H Na T12 2-85 Et 2 H CHO Me H H T13 2-86 Et 2 H CH0 H H Na T13 2-87 Et 2 H CH0 H H H T14 2-88 Et 2 H CH0 Me H Na T14 2-89 Et 2 H CH0 Me H H T15 2-90 Et 2 H CHO H H Na T15 2-91 Et 2 H CHO Et H H Tl 2-92 Et 2 H CHO Et H Na T2 2-93 Et 2 H CH0 Pr H H T2 2-94 Et 2 H CH0 Pr H Na Tl 2-95 Et 2 H CHO i-Pr H H Tl 2-96 Et 2 H CHO i-Pr H Na T2 2-97 Et 2 H MeC0 H H H Tl 154-156 ~d) 2-98 Et 2 H MeC0 H H Na Tl 207-209 ~dl 2-99 Et 2 H MeC0 H H K Tl 2- 100 Et 2 H MeC0 Me H H T 1 2-101 Et 2 H MeC0 Me H Na Tl 2-102 Et 2 H MeC0 H H NHEt3 Tl 2-103 Et 2 H MeC0 H H H T2 2-104 Et 2 H MeC0 H H Na T2 2-105 Et 2 H MeC0 Me H H T2 2-106 Et 2 H MeC0 H H NH4 T2 2-107 Et 2 H MeC0 H H NMe4 T2 2-108 Et 2 H MeC0 Me H Na T2 2-109 Et 2 H MeC0 H H H T5 2-110 Et 2 H MeC0 Me H Na T5 2-111 Et 2 H MeC0 Me H H T5 2-112 Et 2 H MeC0 H H NH4 TS

13x. R n R3 Rlo Rll R9 M Elet m.p.

2-113 Et 2 H MeC0 H H NMe4 T5 2-114 Et 2 H MeC0 H H NHEt3 T5 2-115 Et 2 H MeCO H H H T6 2-116 Et 2 H MeC0 H H Ns T6 2-117 Et 2 H MeC0 H H K T6 2-118 Et 2 H MeC0 H H NH4 T6 2-119 Et 2 H MaC0 Me H H T6 2-120 Et 2 H MeC0 Me H Na T6 2-121 Et 2 H MeC0 H H H T7 2-122 Et 2 H MeC0 H H Na T7 2-123 Et 2 H MeC0 H H K T7 2-124 Et 2 H MeC0 . Me H H T7 2-125 Et 2 H MeC0 Me H Na T7 2-126 Et 2 H MeC0 H H NHEt3 T7 2-127 Et 2 H MeC0 H H H T8 2-128 Et 2 H MeC0 H H Na T8 2- 129 Et 2 H MeC0 Me H H T8 2-130 Et 2 H MeC0 H H NH4 T8 2-131 Et 2 H MeC0 Me H Na T8 2-132 Et 2 H MeC0 H H NHEt3 T8 2- 133 Et 2 H MeC0 Me H H T3 2- 134 Et 2 H MeC0 H H Na T3 2-135 Et 2 H MeC0 H H H T4 2- 136 Et 2 H MeC0 Me H Na T4 2-137 Et 2 H MeC0 Me H H T9 2-138 Et 2 H MeC0 H H Na T9 2-139 Et 2 H MeC0 H H H T10 2-140 Et 2 H MeC0 Me H Na T10 2-141 Et 2 H MeC0 Me H H Tl l 2-142 Et 2 H MeC0 H H Na Tl l 2-143 Et 2 H MeC0 H H H T12 2- 144 Et 2 H MeC0 Me H Na T 12 2-145 Et 2 H MeC0 Me H H T13 2- 146 Et 2 H MeC0 H H Na T 13 2- 147 Et 2 H MeC0 H H H T 14 2-148 Et 2 H MeC0 Me H Na T14 2- 149 Et 2 H MeC0 Me H H T 15 2-150 Et 2 H MeC0 H H Na T15 2-151 Et 2 H MeC0 Et H H Tl 2-152 Et 2 H MeC0 Et H Na T2 13x. R n R3 Rl~ Rll R9 M ~et m.p.

2-153 Et 2 H MeCO Pr H H T2 2-154 Et 2 H MeCO Pr H Na Tl 2-15$ Et 2 H MeCO i-Pr H H Tl 2-156 Et 2 H MeCO i-Pr H Na T2 2-157 Et 2 Me CHO H H H Tl 2-158 Et 2 Me CHO Me H Na T2 2-159 Et 2 Me MeCO H H H T2 2-160 Et 2 Me MeCO Me H Na T1 2-161 Et 2 Me EtCO H H H T2 2-162 Et 2 Me EtCO Me H Na T2 2-163 Pr 2 H CHO H H H Tl 2-164 Pr 2 H CHO Me H Na Tl 2-165 Pr 2 H MeCO Me H H Tl 2-166 Pr 2 H MeCO H H Na T1 2-167 Pr 2 H MeOCO H H H Tl 2-168 Pr 2 H i-PrCO H H Na Tl 2-169 Pr 2 H CHO H H H T2 2-170 Pr 2 H CHO Me H Na T2 2-171 P~ 2 H MeCO Me H H T2 2-172 Pr 2 H MeCO H H Na T2 2-173 Pr 2 H MeOCO H H H T2 2-174 rr 2 H i-PrCO H H Na T~
2-175 i-Pr 2 H CHO H H H Tl 2-176 i-Pr 2 H CHO Me H Na Tl 2-177 i-p~ 2 H MeCO Mo H H Tl 2-178 i-Pr 2 H MeCO H H Na Tl 2-179 j-p~ 2 H MeOCO H H H Tl 2-180 i-Pr 2 H i-PrCO H H Na Tl 2-181 i-Pr 2 H CHO H H H T2 2-182 i-Pr 2 H CHO Me H Na T2 2-183 i-Pr 2 H MeCO Me H H T2 2-184 i-Pr 2 H MeCO H H Na T2 2-185 i-Pr 2 H MeOCO H H H T2 2-186 i-Pr 2 H i-PrCO H H Na T2 2-187 CH2C02Me 2 H CHO H H H Tl 2-188 CH2C02Me 2 H MeCO H H H T2 2-189 CH2~-Pr 2 H CHO Me H H T1 2-190 CH2~-Pr 2 H MeCO Me H H T2 2-191 CH2F 2 H CHO Me H H Tl 2-192 CH2F 2 H MeCO H H H T2 2-193 CH2CI 2 H CHO H H H Tl E~c. R n R3 Rlo Rll R9 M EIet m.p.

2-194 CH2CI 2 H MeCO H H H T2 2-195 CH2CH2F 2 H CHO Me H H T1 2-196 CH2CH2F 2 H MeCO Me H H T2 2-198 CH2CF3 2 H MeCOH H H T2 2-199 CH2CH20Me 2 H CHO H H H Tl 2-200 CH2CH20Me 2 H MeCO H H H T2 2-201 CH2CH2SMe 2 H CHO Me H H Tl 2-202 CH2CH2SMe 2 H MeCO Me H H T2 2-203 Ph 2 H CHO H H H Tl 2-204 Ph 2 H MeCO H H H T2 2-205 t-Bu 2 H CHO H H H Tl 2-206 t-Bu 2 H MeCO H H H T2 2-207 C~_lùp ,t~l 2 H CHO Mo H H Tl 2-208 Cy')~ Ityl 2 H MeCO Me H H T2 2-209 C~clol-? yl 2 H CHO H H H Tl 2-210 C~_lul, ~l 2 H MeCO H H H T2 2-211 CH2CH=CH2 2 H CHO H H H Tl 2-212 CH2CH=CH2 2 H MeCO H H H T2 2-213 CH2C~CH 2 H CHO Me H H Tl 2-214 CH2C-CH 2 H MeCO Me H H T2 2-215 CH2Ph 2 H CHO H H H Tl 2-216 CH2Ph 2 H MeCO H H H T2 2-217 NMe2 2 H CHO H H H Tl 2-218 NMe2 2 H CHO Me H Na T1 2-219 NMe2 2 H MeCO Me H H T1 2-220 NMe2 2 H MeCO H H Na Tl 2-221 NMe2 2 H MeOC0 H H H Tl 2-222 NMe2 2 H i-~CO H H Na Tl 2-223 NMe2 2 H CHO H H H T2 2-224 NMe2 2 H CHO Me H Na T2 2-225 NMe2 2 H MeCO Me H H T2 2-226 NMe2 2 H MeCO H H Na T2 2-227 NMe2 2 H MeOCO H H H T2 2-228 NMe2 2 H i-PrCO H H Na T2 2-229 NEt2 2 H CHO H H H Tl 2-230 NEt2 2 H MeCO H H H T2 2-231 NHPh 2 H CHO Me H H Tl 2-232 NHPh 2 H MeCO Me H H T2 2-233 NHMe 2 H CHO H H H Tt 2-234 NHMe 2 H MeCO Me H H T2 lS~c. R n R3 Rlo Rll R9 M Elet m.p.

2-235 NHEt 2 H CH0 H H H T1 2-236 NHEt 2 H MeC0 H H H T2 2-237 NHCH2C-CH 2 H CH0 Me H H T1 2-238 NHCH2C-CH 2 H MeC0 Mb H H T2 2-239 N(A11~1)2 2 H CH0 Me H H T1 2-240 N(AI1~)2 2 H MeC0 H H H T2 2-241 P~ o 2 H CH0 H H H T1 2-242 ~ "")o 2 H MeC0 H H H T2 2-243 Mc ~I,'.o 2 H CH0 Me H H T1 2-244 ~ ~ ,0 2 H MeC0 Me H H T2 C02Me 2 H CH0 Me H H T1 C02Me 2 H MeC0 H H H T2 2-247 Et 2 H EtC0 H H H T1 154-156 /d) 2-248 Et 2 H EtC0 H H Na T1 219-221 (d 2-249 Et 2 H EtC0 H H H T2 2-250 Et 2 H EtC0 H H Na T2 2-251 Et 2 H EtC0 Me H H T1 2-252 Et 2 H EtC0 Me H Na T1 2-253 Et 2 H EtC0 Me H H T2 2-254 Et 2 H EtC0 Me H Na T2 2-255 R 2 H EtC0 H H H T6 2-256 Et 2 H EtC0 H H Na T6 2-257 Et 2 H EtC0 H H H T7 2-258 Et 2 H EtC0 H H Na T7 2-259 Et 2 H i-PrCO H H H T1 2-260 Et 2 H i-PrCO H H Na T1 194-196 (d 2-261 Et 2 H i-PrCO H H H T2 2-262 Et 2 H i-PrCO H H Na T2 2-263 Et 2 H i-PrCO Me H H T1 2-264 Et 2 H i-PrC0 Me H Na T1 2-265 Et 2 H i-PrCO Me H H T2 2-266 Et 2 H i-PrCO Me H Na T2 2-267 Et 2 H i-PrCO H H H T6 2-268 Et 2 H i-PrCO H H Na T6 2-269 Et 2 H i-PrCO H H H T7 2-270 Et 2 H i-PrCO H H Na T7 1~ . R n R3 Rlo Rll R9 M Het m . p .

2-271 Et 2 H BuC0 H H H T1 2-272 Et 2 H BuC0 H H Na T1 2-273 Et 2 H BuC0 H H H T2 2-274 Et 2 H BuCO H H Na T2 2-275 Et 2 H BuC0 Me H H Tl 2-276 Et 2 H BuC0 Me H Na Tl 2-277 Et 2 H BuC0 Me H H T2 2-278 Et 2 H BuC0 Me H Na T2 2-279 Et 2 H BuC0 H H H T6 2-280 Et 2 H BuC0 H H Na T6 2-281 Et 2 H BuC0 H H H T7 2-282 Et 2 H BuCO H H Na T7 2-283 Et 2 H Cyl.lcp ~IylC0 H H H T1 2-284 Et 2 H Cy ~p~ IC0 H H Na Tl 2-285 Et 2 H C~t~lC0 H H H T2 2-286 Et 2 H C~CO H H Na T2 2-287 Et 2 H Cyc'~, It~11CO M~ H H T1 2-289 Et 2 H Cy_lo"r.-l~lC0 Me H Na Tl 2-290 Et 2 H Cyc!e~ lC0 Me H H T2 2-291 Et 2 H Cy_lopc.-l~lC0 Me H Na T2 2-292 Et 2 H Cyc'~, .t~;C0 H H H T6 2-293 Et 2 H C~olop_.-tylC0 H H Na T6 2-294 Et 2 H Cy~ ~, ~t~CO H H H T7 2-295 Et 2 H C~ ICO H H Na T7 2-296 Et 2 H CF3C0 H H H T1 2-297 Et 2 H CF3C0 H H H T2 2-298 Et 2 H CICH2CO H H H T1 2-299 Et 2 H CICH2C0 H H H T2 2-~00 Et 2 H CIICH2)3C0 H H H T1 2-301 Et 2 H CIICH2~3C0 H H H T2 2-302 Et 2 H PhC0 H H H T1 2-303 Et 2 H PhC0 H H Na Tl 2-304 Et 2 H PhC0 H H H T2 2-305 Et 2 H PhC0 H H Na T2 2-306 Et 2 H PhC0 Me H H T1 2-307 Et 2 H PhCO Me H Na Tl 2-308 Et 2 H PhC0 Me H H T2 2-309 Et 2 H PhC0 Me H Na T2 2-310 Et 2 H PhC0 H H H T6 2-311 Et 2 H PhCO H H Na T6 2-312 Et 2 H PhC0 H H H T7 13x. R n R3 Rl~ Rll R9 M ~Iet m.p.

2-313 Et 2 H PhCO H H Na T7 2-314 Et 2 H 4-ClPhCO H H H T1 2-315 Et 2 H 4-ClPhCO H H H T2 2-316 Et 2 H 3-MePhCO H H H T1 2-317 Et 2 H 3-MePhCO H H H T2 2-318 Et 2 H 2-MeOPhCO H H H T1 2-319 Et 2 H 2-MeOPhCO H H H T2 2-320 Et 2 H 4-CF3PhCO H H H T1 2-321 Et 2 H 4-CF3PhCO H H H T2 2-322 Et 2 H 2-ThienylCO H H H T1 2-323 Et 2 H 2-Thien~lCO H H H T2 2-324 Et 2 H 2-FurylCO H H H T1 2-325 Et 2 H 2-FurylCO H H H T2 2-326 Et 2 H 3-PyridylCO H H H T1 2-327 Et 2 H 3-PyridylCO H H H T2 2-328 Et 2 H H2C = CHCO H H H T1 2-329 Et 2 H H2C = CHCO H H H T2 2-330 Et 2 H HC~CCO H H H T1 2-331 Et 2 H HC ~ CCO H H H T2 2-332 Et 2 H MeOCH2CO H H H T1 2-333 Et 2 H MeOCH2CO H H H T2 2-334 Et 2 H MeSCH2CO H H H T1 2-335 Et 2 H MeSCH2CO H H H T2 2-336 Et 2 H MeO-CO- H H H T1 (CH2~2CO
2-337 Et 2 H MeO-CO- H H H T2 ~CH2)2CO
2-338 Et 2 H MeO-CO-CO H H H T1 2-339 Et 2 H MeO-CO-CO H H H T2 2-340 Et 2 H PhCH2CO H H H T1 2-341 Et 2 H PhCH2CO H H H T2 2-342 Et 2 H 3-ClPhCH2CO H H H T1 2-343 Et 2 H 3-ClPhCH2CO H H H T2 2-344 Et 2 H 3-MePhCH2CO H H H T1 2-345 Et 2 H 3-MePhCH2CO H H H T2 2-346 Et 2 H 2-Thienyl- H H H T1 2-347 Et 2 H 2-Thien~ H H H T2 2-348 Et 2 H MeOCO H H H T1 13~c. R n R3 R10 Rll R9 M ~et m.p.

2-349 Et 2 H MeOCO H H Na T1 206-209 (d) 2-350 Et 2 H MeOCO H H K T1 2-351 Et 2 H MeOCO Me H H T1 2-352 Et 2 H MeOCO Me H Na T1 2-353 Et 2 H MeOCO H H NHEt3 Tl 2-354 Et 2 H MeOCO H H H T2 2-355 Et 2 H MeOCO H H Na T2 2-356 Et 2 H MeOCO Me H H T2 2-357 Et 2 H MeOCO H H NH4 T2 2-358 Et 2 H MeOCO H H NMe4 T2 2-359 Et 2 H MeOCO Me H Ns T2 2-360 Et 2 H MeOCO H H H T5 2-361 Et 2 H MeOCO Me H Na T5 2-362 Et 2 H M~OCO Me H H T5 2-363 Et 2 H MeOCO H H NH4 T5 2-364 Et 2 H MeOCO H H NMe4 T5 2-365 Et 2 H MeOCO H H NHEt3 T5 2-366 Et 2 H MeOCO H H H T6 2-367 Et 2 H MeOCO H H Na T6 2-368 Et 2 H MeOCO H H K T6 2-369 Et 2 H MeOCO H H NH4 T6 2-370 Et 2 H MeOCO Me H H T6 2-371 Et 2 H MeOCO Me H Na T6 2-372 Et 2 H MeOCO H H H T7 2-373 Et 2 H MeOCO H H Na T7 2-374 Et 2 H MeOCO H H K T7 2-375 Et 2 H MeOCO Me H H T7 2-376 Et 2 H MeOCO Me H Na T7 2-377 Et 2 H MeOCO H H NHEt3 T7 2-378 Et 2 H MeOCO H H H T8 2-379 Et 2 H MeOCO H H Na T8 2-380 Et 2 H MeOCO Me H H T8 2-381 Et 2 H MeOCO H H NH4 T8 2-382 Et 2 H MeOCO Me H Na T8 2-383 Et 2 H MeOCO H H NHEt3 T8 2-384 Et 2 H MeOCO Me H H T3 2-385 Et 2 H MeOCO H H Na T3 2-386 Et 2 H MeOCO H H H T4 2-387 Et 2 H MeOCO Me H Na T4 2-388 Et 2 H MeOCO Me H H T9 . R n R3 Rlo Rll R9 M lIet m . p .

2-389 Et 2 H MeOCO H H Na T9 2-390 Et 2 H MeOCO H H H T10 2-391 Et 2 H MeOCO Me H Na T10 2-392 Et 2 H MeOCO Me H H Tll 2-393 Et 2 H MeOCO H H Na T11 2-394 Et 2 H MeOCO H H H T12 2-395 Et 2 H MeOCO Me H Na T12 2-396 Et 2 H MeOCO Me H H T13 2-397 Et 2 H MeOCO H H Na T13 2-398 Et 2 H MeOCO H H H T14 2-393 Et 2 H MeOCO Me H Na T14 2-400 Et 2 H MeOCO Me H H T15 2-401 Et 2 H MeOCO H H Na T15 2-402 Et 2 H MeOCO Et H H T1 2-403 Et 2 H MeOCO Et H Na T2 2-404 Et 2 H MeOCO Pr H H T2 2-403 Et 2 H MeOCO Pr H Na T1 2-406 Et 2 H MeOCO i-Pr H H Tl 2-407 Et 2 H MeOCO i-Pr H Na T2 2-408 Et 2 H EtOCO H H H Tl 2-409 Et 2 H EtOCO H H Na Tl 2-410 Et 2 H EtOCO H H H T2 2-411 Et 2 H EtOCO H H Na T2 2-412 Et 2 H EtOCO Me H H Tl 2-413 Et 2 H EtOCO Me H Na Tl 2-414 Et 2 H EtOCO Me H H T2 2-415 Et 2 H EtOCO Me H Na t2 2416 Et 2 H EtOCO H H H T6 2-417 Et 2 H EtOCO H H Na T6 2-418 Et 2 H EtOCO H H H T7 2419 Et 2 H EtOCO H H Na T7 2420 Et 2 H PrOCO H H H Tl 2-421 Et 2 H PrOCO H H H T2 2-422 Et 2 H MeSCO H H H Tl 2423 Et 2 H MeSCO H H H T2 2-424 Et 2 H MeNHCO H H H Tl 2-425 Et 2 H MeNHCO H H H T2 2-426 Et 2 H BuNHCO H H H Tl 2-427 Et 2 H BuNHCO H H H T2 2-428 Et 2 H Me2NCO H H H Tl 2-429 Et 2 H Me2NCO H H H T2 CA 022246l2 l997-l2-l2 13x . R n R3 Rlo Rll R9 M Het m. p .

2-430 Et 2 H EtNHCS H H H T1 2-431 Et 2 H EtNHCS H H H T2 2-432 Et 2 H MeS02 H H H T1 2-433 Et 2 H MeS02 H H Na T1 2-434 Et 2 H MeS02 H H H T2 2-435 Et 2 H MeS02 H H Na T2 2-436 Et 2 H MeS02 Me H H T1 2-437 Et 2 H MeS02 Me H Na T1 2-438 Et 2 H MeS02 Me H H T2 2439 Et 2 H MeS02 Me H Na T2 2440 Et 2 H MeS02 Me H H T6 2-441 Et 2 H MeS02 Me H Ns T6 2442 Et 2 H EtS02 Me H H T1 2-443 Et 2 H EtS02 Me H H T2 2-444 Et 2 H PhS02 Me H H T1 2445 Et 2 H PhS02 Me H H T2 2-446 Et 2 H CICH2S02 Me H H T1 2-447 Et 2 H CICH2S02 Me H H T2 2448 Et 2 H Me2NS02 Me H H T1 2-449 Et 2 H Me2NS02 Me H H T2 2-450 Et 2 H MeCO Allyl H H T1 2-451 Et 2 H MeCO Allyl H H T2 2-452 Et 2 H MeCO P~ H H T1 2-453 Et 2 H MeCO Pg H H T2 2-454 Et 2 H CHO Me Me H T1 2-455 Et 2 H MeCO H Et Na T1 2456 Et 2 H MeOCO H Pr H T2 2-457 Et 2 H i-PrCO H i-Pr Na T2 2-458 Et 2 H MeCO Me Allyl H T1 2-459 Et 2 H CHO H Ac H T1 2-460 Et 2 H MeCO H Ac H T1 CA 022246l2 l997-l2-l2 Table 3: Compounds of the formula (Ic) R s_ N

\~- 'N~ ~ 'H e t 8 19 0 0 o R R

. R5 R6 R3 R7 R3 R9 ~ Het ~.p.

3-1 Me H H Me H H H Tt 3-2 Me H H Me H H Na Tl 3-3 Me H H Me Me H H Tl 34 Me H H Ms Me H Na Tl 3-5 Me H H -~CH2)4- H H Tl 3-6 Me H H -~CH2)4- H N~ Tl 3-7 Me H H Me H H H T2 3-8 Me H H Me H H Na T2 3-9 Me H H Me Me H H T2 3-10 Me H H Me Me H Na T2 3-11 Me H H -~CH2~4- H H T2 3-12 Me H H -~CH2t4- H Na T2 3-13 Et H H Me H H H Tl 3-14 Et H H Me H H Na Tl 3-15 Et H H Me Me H H Tl 3-16 Et H H Me Me H Na Tl 3-17 Et H H -~CH2)4- H H Tl 3-18 Et H H -~CH2)4- H Na Tl 3-19 Me Me H Me H H H Tl 127-129(d) 3-20 Me Me H Me H H Na T1 3-21 Me Me H Me H H K T1 3-22 Me Me H Me H H NH4 Tl 3-23 Me Me H Me H H NMe4 Tl 3-24 Me Me H Me H H NHEt3 Tl 3-25 Me Me H Me H H H T2 3-26 Me Me H Me H H Na T2 3-27 Me Me H Me H H K T2 3-28 Me Me H Me H h NH4 T2 3-29 Me Me H Me H H NMe4 T2 -lbc. R5 R6R3R7 R5 R9 ll }Iet~.p.

3-30 Me MeMeMe H H NHEt3T2 3-31 Me MeHMe H H H T5 3-32 Me MeHMe H H Na T5 3-33 Me MeHMe H H K T5 3-34 Me MeHMe H H NH4-~s 3-35 Me MeHMe H H NMe4T5 3-36 Me MeHMe H H NHEt3T5 3-37 Me MeHMe H H H T6 3-38 Me MeHMe H H Na T6 3-39 Me MeHMe H H K T6 3-40 Me MeHMe H H NH4T6 3-41 Me MeHMe H H NMe4T6 3-42 Me MeHMe -H H NHEt3T6 3-43 Me MeHMe H H H T7 3-44 Me MeHMe H H Na T7 3-45 Me MeHMe H H K T7 3-46 Me MeHMe H H NH4T7 3-47 Me MeHMe H H NMe4T7 3-48 Me MeHMe H H NHEt3T~
3-49 Me MeHMe H H H T8 3-50 Me MeHMe H H Na T8 3-51 Me MeHMe H H K T8 3-52 Me MeHMe H H NH4 T8 3-53 Me MeHEt H H H T1 3-54 Me MeHBu H H Na T1 3-55 Me MeHMe H H H T3 3-56 Me MeHMe H H Na T3 3-57 Me MeHMe H H H T4 3-58 Me MeHMe H H Na T4 3-59 Me MeHMe H H H T9 3-60 Me MeHMe H H Na T9 3-61 Me MeHMe H H H T10 3-62 Me MeHMe H H Na T10 3-63 Me MeHMe H H H T11 3-64 Me MeHMe H H Na T11 3-65 Me MeHMe H H H T12 3-66 Me MeHMe H H Na T12 3-67 Me MeHMe H H H T13 3-68 Me MeHMe H H Na T13 3-69 Me MeHMe H H H T14 3-70 Me MeHMe H H Na T14 ~x. R5 R6 R3 R7 R8 R9 ~ Het ~.p.

3-71 Me Me H Me H H H T15 3-72 Me Me H Me H H Na T15 3-73 Me Me H Me Me H H Tl 3-74 Me Me H Me Me H Na T1 3-75 Ms Me H Me MB H K Tl 3-76 Me Me H Me Me H NH4 Tl 3-77 Me Me H Me Me H NMe4 Tl 3-78 Me Me H Me Me H NHEt3 Tl 3-79 Me Me H Me Me H H T2 3-80 Me Me H Me Me H Na T2 3-81 Me Me Me Me Me H K T2 3-82 Me Me H Me Me H NH4 T2 3-83 Me Me H Me Me H NMe4 T2 3-84 Me Me H Me Me H NHEt3 T2 3-85 Me Me H Me Me H H T5 3-86 Me Me H Me Me H Na T5 3-87 Me Me H Me Me H K T5 3-88 Me Me H Me Me H NH4 T5 3-89 Me Me H Me Me H NMe4 T5 3-90 Me Me H Me Me H NHEt3 T5 3-91 Me Me H Me Me H H T6 3-92 Me Me H Me Me H Na T6 3-93 Me Me H Me Me H K T6 3-94 Me Me H Me Me H NH4 T6 3-95 Me Me H Me Me H NMe4 T6 3-96 Me Me H Me Me H NHEt3 T6 3-97 Me Me H Me Me H H T7 3-98 Me Me H Me Me H Na T7 3-99 Me Me H Me Me H K T7 3-100 Me Me H Me Me H NH4 T7 3-101 Me Me H M9 Me H NMe4 T7 3-102 Me Me H Me Me H NHEt3 T7 3-103 Me Me H Me Me H H T8 3-104 Me Me H Me Me H Na T8 3-105 Me Me H Me Me H K T8 3-106 Me Me H Me Me H NH4 T8 3-107 Me Me H Me Me H NMe4 T8 3-108 Me Me H Me Me H NHEt3 T8 3-109 Me Me H Me Me H H T3 3-110 Me Me H Me Me H Na T3 3-111 Me Me H Me Me H H T4 CA 022246l2 l997-l2-l2 B~. R5 R6 R3 R7 RS R9 ~ ~et m.p.

3-112 Me Me H Me Me H Na T4 3-113 Me Me H Me Me H H T9 3-114 Me Me H Me Me H Na T9 3-115 Mo Me H Me Me H H T10 3-116 Me Me H Me Me H Na T10 3-117 Me Me H Me Me H H T11 3-118 Me Me H Me Me H Na T11 3-119 Me MeH Me Me H H T12 3-120 Me Me H Me Me H Na T12 3-121 Me Me H Me Me H H T13 3-122 Me Me H Me Me H Na T13 3-123 Me Me H Me Me H H T14 3-124 Me Me H Me Me H Na T14 3-125 Me Mo H Me Me H H T15 3-126 Me Me H Me Me H Na T15 3-127 Me Me H -ICH2)4- H H T1 3-128 Me Me H -(CH2)4- H Na T1 223-226 Id) 3-129 Me Me H -(CH2)4- H K T1 3-130 Me Me H -ICH2)4- H NH4 T1 3-131 Me Me H -ICH2)4- H NMe4 T1 3-132 Me Me H -ICH2)4- H NHEt3 T1 3-133 Me Me H -ICH2)4- H H T2 3-134 Me Me H -~CH2)4- H Na T2 3-135 Me Me H -(CH2)4- H K T2 3-136 Me Me H -ICH2)4- H NH4 T2 3-137 Me Me H -ICH2)4- H NMe4 T2 3-138 Me Me H -(CH2)4- H NHEt3 T2 3-139 Me Me H -ICH2)4- H H T5 3-140 Me Me H -ICH2)4- H Na T5 3-141 Me Me H -~CH2)4- H K T5 3-142 Me Me H -~CH2)4- H NH4 T5 3-143 Me Me H -(CH2)4- H NMe4 T5 3-144 Me Me H -ICH2)4- H NHEt3 T5 3-145 Me Me H -ICH2)4- H H T6 3-146 Me Me H -(CH2)4- H N~ T6 3-147 Me Me H -ICH2)4- H K T6 3-148 Me Me H -ICH2)4- H NH4 T6 3-149 Me Me H -~CH2)4- H NMe4 T6 3-150 Me Me H -(CH2)4- H NHEt3 T6 3-151 Me Me H -ICH2)4- H H T7 .

~x. R5 R6 R3 R7 R5 R9 ~ ~et m.p.

3-152 Me Me H -(CH2)4- H Na T7 3-153 Me Me H -ICH2)4- H K T7 3-154 Me Me H -(CH2)4- H NH4 T7 3-155 Me Me H -(CH2)4- H NMe4 T7 3-156 Me Me H -(CH2)4- H NHEt3 T7 3-157 Me Me H -(CH2)4- H H T8 3-158 Me Me H -(CH2)4- H Na T8 3-159 Me Me H -(CH2)4- H K T8 3-160 Me Me H -(CH2)4- H NH4 T8 3-161 Me Me H -(CH2)4- H NMe4 T8 3-162 Me Me H -(CH2)4- H NHEt3 T8 3-163 Me Me H -(CH2)4- H H T3 3-164 Me Me H -(CH2)4- H Na T3 3-165 Me Me H -(CH2)4- H H T4 3-166 Me Me H -(CH2~4- H Na T4 3-167 Me Me H -(CH2)4- H H T9 3-168 Me Me H -(CH2)4- H Na T9 3-169 Me Me H -(CH2)4- H H T10 3-170 Me Me H -(CH2)4- H Na T10 3-171 Me Me H -(CH2)4- H H T11 3-172 Me Me H -(CH2)4- H Na T11 3-173 Me Me H -(CH2)4- H 1~ T12 3-174 Me Me H -(CH2)4- H Na T12 3 175 Me Me H -(CH2)4- H H T13 3-176 Me Me H -(CH2)4- H Na T13 3-177 Me Me H -(CH2)4- H H T14 3-178 Me Me H -(CH2)~ H Na T14 3-179 Me Me H -(CH2)4- H H T15 3-180 Me Me H -(CH2)4- H Na T15 3-181 Me Me Me Me H H H T2 3-182 Me Me Me Me H H Na T2 3-183 Me Me Me Me Me H H T2 3-184 Me Me Me Me Me H Na T2 3-185 Me Me Me -(CH2)4- H H T2 3-186 Me Me Me -(CH2)4- H Na T2 3-187 Me Me H CF3 H H H T1 3-188 Me Me H CF3 H H Na T1 3-189 Me Me H CF3 H H H T2 3-190 Me Me H CF3 H H Na T2 3-191 Me Me H CF3 H H H T5 3-192 Me Me H CF3 H H Na T5 ~. R5 R6 R3 R7 R3 R9 Y ~et ~.p, 3-1g3 Me Me H CF3 H H H T6 3-194 Me Me H CF3 H H Na T6 3-195 Me Me H CF3 H H H T7 3-196 Me Me H CF3 H H Na T7 3-197 Me Me H CF3 CH3 H H T1 3-198 Me Me H CF3 CH3 H Na T1 3-199 Me Me H CF3 CH3 H H T2 3-200 Me Me H CF3 CH3 H Na T2 3-201 Me Me H CF3 CH3 H H T5 3-202 Me Me H CF3 CH3 H Na T5 3-203 Me Me H CF3 CH3 H H T6 3-204 Me Me H CF3 CH3 H Na T6 3-205 Me Me H CF3 CH3 H H T7 3-206 Me Me H CF3 CH3 H Na T7 3-207 Me Me H C02H H H H T1 3-208 Me Me H C02H H H Na T1 3-209 Me Me H C02H H H H T2 3-210 Me Me H C02H H H Na T2 3-211 Me Me H C02H H H H T5 3-212 Me Me H C02H H H Na T5 3-213 Me Me H C02H H H H T6 3-214 Me Me H C02H H H Na T6 3-215 Me Me H C02H H H H T7 3-216 Me Me H C02H H H Na T7 3-217 Me Me H -(CH2)4- H H T1 3-218 Me Me H -(CH2)4- H H T2 3-219 Me Me H CH3CH=CH- H H H T1 3-220 Me Me H CH3CH=CH- H H H T2 3-221 Me Me H CH30CH2- H H H T1 3-222 Me Me H CH30CH2- H H H T2 3-223 Me Me H C02Me H H H T1 3-224 Me Me H C02Me H H H T2 3-225 Me Me H C02Me Me H H T1 3-226 Me Me H C02Me Me H H T2 3-227 Me Me H 2Thienyl H H H T1 3-228 Me Me H 2-Thienyl H H H T2 3-229 Me Me H 2-PyridYl H H H T1 3-230 Me Me H 2-F~yridyl H H H T2 3-231 Me Me H 3-Pyridyl H H H T1 3-232 Me Me H 3-Pyridyl H H H T2 3-233 Me Me H CH3SCH2CH2- H H H T1 ~x. R5 R6 R3 R7 R3 R9 ~ ~et m.p.

3-234 Me Me H CH3SCH2CH2- H H H T2 3-235 Me Me H 2-Tetrahydro- H H H T1 furyl 3-236 Me Me H 2-Tstl~h1dr~ H H H T2 furyl 3-237 Me Me H Ph H H H T1 3-238 Me Me H Ph H H H T2 3-239 Me Me H 2-CI-Ph H H H T1 3-240 Me Me H 2-CI-Ph H H H T2 3-241 Me Me H 3-CI-Ph H H H T1 3-242 Me Me H 3-CI-Ph H H H T2 3-243 Me Me H 4-CI-Ph H H H T1 3-244 Me Me H 4-CI-Ph H H H T2 3-245 Me Me H 2-Me-Ph H H H T1 3-246 Me Me H 2-Me-Ph H H H T2 3-247 Me Me H 3-Me-Ph H H H T1 3-248 Me Me H 3-Me-Ph H H H T2 3-249 Me Me H 4-Me-Ph H H H T1 3-250 Me Me H 4-Me-Ph H H H T2 3-251 Me Me H 4-MeO-Ph H H H T1 3-252 Me Me H 4-MeO-Ph H H H T2 3-253 Me Me H 4-F-Ph H H H T1 3-254 Me Me H 4-F-Ph H H H T2 3-255 Me Me H 3-CF3-Ph H H H T1 3-256 Me Me H 3-CF3 H H H T2 3-257 Me Me H CH2CI H H H T1 3-258 Me Me H CH2CI H H H T2 3-259 Me Me H Me H Me H T1 3-260 Me Me H Me H Et Na T2 3-261 Me Me H Me Me Me H T1 3-262 Me Me H Me Me Pr Na Tl 3-263 Me Me H -(CH2~4- Me H Tl 3-264 Me Me H -~CH2)4- Me Na T2 3-265 Et Me H Me H H H T1 3-266 Et Me H Me H H Na T1 3-267 Et Me H Me Me H H T1 3-268 Et Me H Me Me H Na T1 3-269 Et Me H -(CH2~4- H H T1 3-270 Et Me H -~CH214- H Na T1 3-271 Et Me H Me H H H T2 3-272 Et Me H Me H H Na T2 . R5 R6 R3 R7 R3 R9 ~ Het m.p.

3-273 Et Me H Me Me H H T2 3-274 Et Me H Me Me H Na T2 3-275 Et Me H -(CH2)4- H H T2 3-276 Et Me H -(CH2~4- H Na T2 3-277 Et Et H Me H H H Tl 3-278 Et Et H Me H H Na T1 3-279 Et Et H Me Me H H T1 3-280 Et Et H Me Me H Na T1 3-281 Et Et H -(CH2)4- H H T1 3-282 Et Et H -(CH2)4- H Na T1 3-283 Et Et H Me H H H T2 3-284 Et Et H Me H H Na T2 3-285 Et Et H Me Me H H T2 3-286 Et Et H Me Me H Na T2 3-287 Et Et H -(CH2)4- H H T2 3-288 Et Et H -(CH2)4- H Na T2 3-289 Ph H H Me H H H T1 3-290 Ph H H Me H H Na T1 3-291 Ph H H Me Me H H T1 3-292 Ph H H Me Me H Na T1 3-293 Ph H H -(CH2~4- H H T1 3-~94 Pl H H -(CH2)4- H Na M
3-295 Ph H H Me H H H T2 3-296 Ph H H Me H H Na T2 3-297 Ph H H Me Me H H T2 3-298 Ph H H Me Me H Na T2 3-299 Ph H H -(CH2)4- H H T2 3-300 Ph H H -~CH2)4- H Na T2 3-301 Allyl Allyl H Me H H H T1 3-302 Allyl Allyl H Me H H Na T1 3-303 Allyl Allyl H Me Me H H T1 3-304 Allyl Allyl H Me Me H Na Tl 3-305 Allyl Allyl H -(CH2)4- H H T1 3-306 Ally~ Allyl H -tCH2)4- H Na T1 3-307 Pg Pg H Me H H H T1 3-308 Pg Pg H Me H H Na T1 3-309 Pg Pg H Me Me H H T1 3-310 Pg Pg H Me Me H Na Tl 3-311 Pg Pg H -~CH2)4- H H T1 3-312 Pg Pg H -(CH2)4- H Na T1 3-313 CH2CH20Me H H Me H H H T1 -. R5 R6 R3 R7 R8 R9 ~ Het m.p.

3-314 CH2CH20Me H H Me H H Na T1 3-315 CH2CH20Me H H Me Me H H T1 3-316 CH2CH20Me H H Me Me H Na Tl 3-317 CH2CH20Me H H -~CH2)4- H H Tl 3-318 CH2CH20Me H H -(CH2)4- H Na Tl 3-319 CH2C02Me H H Me H H H T1 3-320 CH2C02Me H H Me H H Na Tl 3-321 CH2C02Me H H Me Me H H T1 3-322 CH2C02Me H H Me Me H Na Tl 3-323 CH2C02Me H H -(CH2)4- H H T1 3-324 CH2C02Me H H -(CH2)4 H Na Tl 3-325 Py . )o H Me H H H T1 3-326 Fy.. ~ o H Me H H Na T1 3-327 Fy.. ~ o H Me Me H H T1 3-328 Fy. ~ o H Me Me H Na T1 3-329 Py. ~~o H -ICH2)4- H H T1 3-330 Py.: ~o H -(CH2)4- H Na T1 3-331 Py. o H Me H H H T2 3-332 Fy.. c'~o H Me H H Na T2 3-333 Py..... ~o H Me Me H H T2 3-334 P~ o H Me Me H Na T2 3- 35 Pyrrolidino H -~CH2)4- H H T2 3-336 Py.-. ~o H -(CH2)4- H Na T2 3-337 ~iper;r ~o H Me H H H T1 3-338 ripe~ 0 H Me H H Na T1 3-339 Piper ~ ~o H Me Me H H T1 3-340 riperid .o H Me Me H Na T1 3-341 Piper;d ~o H -(CH2)4- H H T1 3-342 Fipsri~ ~o H -~CH2)4- H Na T1 3-343 Mor~ o H Me H H H T 1 3-344 Mc ~Jh~ o H Me H H Na T1 3-345 Mc ~Jh o H Me Me H H T1 3-346 Morpholino H Me Me H Na T1 3-347 l~a ~h -o H -(CH2)4- H H T1 3-348 Mc ~ I r o H -(CH214- H Na T1 3-349 Me H H COMe COOMe H H T1 3-350 Me H H COMe COOMe H Na T1 3-351 Me H H COMe COOMe H H T2 3-352 Me H H COMe COOMe H Na T2 3-353 Me H H CN COOMe H H T1 3-354 Me H H CN COOMe H Na T1 . - 79 ~
~x. R5 R6 R3 R7 R8 R9 ~ H~t m.p.

3-355 Me H H CN COOMe H H T2 3-356 Me H H CN COOMe H Na T2 3-357 Me H H CN C O O Et H H Tl 3-358 Me H H CN C O O Et H Na Tl 3-359 Me H H CN C O O Et H H r2 3-360 Me H H CN C O O Et H Na T2 3-361 Me H H N02 C O O Et H H Tl 3-362 Me H H N02 C O O Et H Na T1 3-363 Me H H N02 C O O Et H H T2 3-364 Me H H N02 C O O Et H Na T2 3-365 Me Me H COMo C O O Et H H Tl 3-366 Me Me H COMe C O O Et H Na Tl 3-367 Me Me H COMe - C O O Et H H T2 3-368 Me Me H COMe C O O Et H Na T2 3-369 Me Me H COMe COOMe H H T1 3-370 Me Me H COMo COOMe H Na Tl 3-371 Me Me H COMe COOMe H H T2 3-372 Me Me H COMe COOMe H Na T2 3-373 Me Me H C O Et COOMe H H T1 3-374 Me Me H C O Et COOMe H Na Tl 3-375 Me Me H C O Et COOMe H H T2 3-376 Me Me H C O Et COOMe H Na T2 3-377 Me Me H COMe Me H H Tl 3-378 Me Me H COMe Me H Na Tl 3-379 Me Me H COMe Me H H T2 3-380 Me Me H COMe Me H Na T2 3-381 Me Me H COMe COMe H H Tl 3-382 Me Me H COMe COMe H Na Tl 3-383 Me Me H COMe COMe H H T2 3-384 Me Me H COMe COMe H Na T2 3-385 Me Me H COMe CONH2 H H Tl 3-386 Me Me H COMe CONH2 H Na Tl 3-387 Me Me H COMe CONH2 H H T2 3-388 Me Me H COMe CONH2 H Na T2 3-389 Me Me H COMe CONH~ H H Tl 3-390 Me Me H COMo CONH~ H Na Tl 3-391 Me Me H COMe CONH~ H H T2 3-392 Me Me H COMe CONHPh H Na T2 3-393 Me Me H COMe CONHMe H H Tl 3-394 Me Me H COMe CONHMe H Na Tl 3-395 Me Me H COMe CONHMe H H T2 ~x. R5 R6 R3 R7 R3 R9 ~ Het m.p.

3-396 Me Me H COMe CONHMe H Na T2 3-397 Me Me H COMe CONMe2 H H T1 3-398 Me Me H COMe CONMe2 H Na T1 3-399 Me Me H COMe CONMe2 H H T2 3-400 Me Me H COMe CONMe2 H Na T2 3-401 Me Me H COOMe COOMe H H T1 3-402 Me Me H COOMe COOMe H Na T1 3-403 Me Me H COOMe COOMe H H T2 3-404 Me Me H COOMe COOMe H Na T2 3-405 Me Me H COOMe COOMe H H T5 3-406 Me Me H COOMe COOMe H Na T5 3-407 Me Me H COOMe COOMe H H T6 3-408 Me Ms H COOMe COOMe H Na T6 3409 Me Me H COOEt COOEt H H T1 3-410 Me Me H COOEt COOEt H Na Tl 3-411 Me Me H COOEt COOEt H H T2 3-412 Me Me H COOEt COOEt H Na T2 3-413 Me Me H COOEt COOEt H H T5 3-414 Me Me H COOEt COOEt H Na T5 3-415 Me Me H COOEt COOEt H H T6 3-416 Me Me H COOEt COOEt H Na T6 3-417 Me Me H COOEt CONH2 H H T1 3-418 Me Me H COOEt CONH2 H Na T1 3-419 Me Me H COOEt CONH2 H H T2 3-420 Me Me H COOEt CONH2 H Na T2 3-421 Me Me H COOMe CN H H Tl 3-422 Me Me H COOMe CN H Na Tl 3-423 Me Me H COOMe CN H H T2 3-424 Me Me H COOMe CN H Na T2 3-425 Me Me H COOMe CN H H T5 3-426 Me Me H COOMe CN H Na T5 3-427 Me Me H COOMe CN H H T6 3-428 Me Me H COOMe CN H Na T6 3-429 Me Me H COOEt CN H H T1 3-430 Me Me H COOEt CN H Na T1 3-431 Me Me H COOEt CN H H T2 3-432 Me Me H COOEt CN H Na T2 3-433 Me Me H COOEt CN H H T5 3-434 Me Me H COOEt CN H Na T5 3-435 Me Me H COOEt CN H H T6 3-436 Me Me H COOEt CN H Na T6 CA 022246l2 l997-l2-l2 ~. R5 R6 R3 R7 R8 R9 ~ ~t m.p.

3-437 Me Me H COOEt N02 H H Tl 3-438 Me Me H COOEt N02 H Na T1 3-439 Me Me H COOE~ N02 H H T2 3-440 Me Me H COOEt N02 H Na T2 3-441 Me Me H COOEt N02 H H T5 3-442 Me Me H COOEt N02 H Na T5 3-443 Me Me H COOEt N02 H H T6 3444 EMe Me H COOEt N02 H Na T6 3-445 Me Me H COOMe S02Me H H Tl 3-446 Me Me H COOMe S02Me H Na T1 3-447 Me Me H COOMe S02Me H H T2 3448 Me Me H COOMe S02Me H Na T2 3449 Me Me H COOMe S02Et H H Tl 3450 Me Me H COOMe S02Et H Na Tl 3-451 Me Me H COOMe S02Et H H T2 3-452 Me Me H COOMe S02Et H Na T2 3-453 Me Me H COOEt S02Mo H H T1 3-454 Me Me H COOEt S02Me H Na T1 3-455 Me Me H COOEt S02Me H H T2 3-456 Me Me H COOEt S02Me H Na T2 3-457 Me Me H COOEt PO(OEt)2 H H T1 3-458 Me Me H COOEt PO(OEt)2 H Na T1 3-459 Me Me H COOEt PO(OEt~2 H H T2 3460 Me Me H COOEt PO(OEt)2 H Na T2 3461 Me Me H CONH2 CONH2 H H T1 3-462 Me Me H CONH2 CONH2 H Na Tl 3-463 Me Me H CONH2 CONH2 H H T2 3-464 Me Me H CONH2 CONH2 H Na T2 -~-465 Me Me H CONMe2 CONMe2 H H Tl 3-466 Me Me H CONM~2 CONMe2 H Na Tl 3-467 Me Me H CONMe2 CONMe2 H H T2 3468 Me Me H CONMe2 CONMe2 H Na T2 3-469 Me Me H CONH2 CN H H Tl 3-470 Me Me H CONH2 CN H Na Tl 3-471 Me Me H CONH2 CN H H T2 3472 Me Me H CONH2 CN H Na T2 3-473 Me Me H CN CN H H Tl 3 474 Me Me H CN CN H Na Tl 3475 Me Me H CN CN H H T2 3-476 Me Me H CN CN H Na T2 3477 Me Me H CN Ph H H Tl . R5 R6 R3 a7 R3 R9 ~ Het m.p.

3-478 Me ~e H CN Ph H Na T1 3-479 Me Me H CN Ph H H T2 3-480 Me Me H CN Ph H Na T2 3-481 Me Me H N02 H H H Tl 3-482 Me Me H N02 H H Na Tl 3-483 Me Me H N02 H H H T2 3-484 Me Me H N02 H H Nfl T2 3485 Me Me H N02 Me H H T1 3-486 Me Me H N02 Me H Na Tt 3-487 Me Me H N02 Me H H T2 3-488 Me Me H N02 Me H Na T2 3-489 Me Me H -CO-CH2CH2CO- H H T1 3-490 Me Me H -CO-CH2CH2CO- H Na Tl 3491 Me Me H -CO-CH2CH2CO- H H T2 3-492 Me Me H -CO-CH2CH2CO- H Na T2 3-493 Me Me H -COCH=CH-CO- H H T1 3-494 Me Me H -COCH=CH-CO- H Na T1 3-495 Me Me H -COCH=CH-CO- H H T2 3-496 Me Me H -COCH=CH-CO- H Na T2 3-497 Me Me H -CO~CH2)3CO- H H T1 3-498 Me Me H -CO(CH2)3CO- H Na T1 3-499 Me Me H -CO~CH2)3CO- H H T2 3-500 Me Me H -CO~CH2)3CO- H Na T2 3-501 Me Mb H -COOC~CH3)20CO- H H T1 3-502 Me Me H -COOCICH3)20CO- H Na T1 3-503 Me Me H -COOC~CH3)20CO- H H T2 3-504 Me Me H -COOC~CH3)20CO- H Na T2 3-505 Me Me H -~CH2)4CO- H H T1 3-506 Me Me H -~CH2)4CO- H Na T1 3-507 Me Me H -~CH2)4CO- H H T2 3-508 Me Me H -~CH2)4CO- H Na T2 3-509 Me Me H -(CH2)3NHCO- H H T1 3-510 Me Me H -~CH2)3NHCO- H Na T1 3-511 Me Me H -(CH2)3NHCO- H H T2 3-512 Me Me H -~CH2)3NHCO- H Na T2 3-513 Me Me H -C~CH3)=NN(CH3~-CO- H H T1 3-514 Me Me H -C~CH3)=NN(CH3)-CO- H Na T1 3-515 Me Me H -C~CH3)=NN~CH3)-CO- H H T2 3-516 Me Me H -C~CH3)=NN~CH3)-CO- H Na T2 3-517 Me Me H -N=C(CH3)-OCO- H H T1 3-518 Me Me H -N=C~CH3)-OCO- H Na T1 Ex. R5 R6 R3 R7 R8 R9 M Het m.p.

3-519 Me Me H -N=C~CH3)-OCO- H H T2 3-520 Me Me H -NzC~CH3)-OCO- H Na T2 3-521 Me Me H -COCH2N(CH3)-CO- H H Tl 3-522 Me Me H -COCH2N(CH3)-CO- H Na Tl 3-523 Me Me H -COCH2N(CH3)-CO- H H T2 3-524 Me Me H -COCH2N(CH3)-CO- H Na T2 3-525 Me Me H 1,2-(-CO-C6H4-CO-) H H Tl 3-526 Me Me H 1,2-(-CO-C6H4-CO-~ H Na Tl 3-527 Me Me H 1,2-(-CO-C6H4-CO-) H H T2 3-528 Me Me H 1.2-(-CO-C6H4-CO-) H Na T2 B. Formulation Examples a) A dusting powder i8 obtained by mixing 10 parts by weight of a compound of formula (I) and 90 parts by weight of talc, as the inert substance, and com-minuting the mixture 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 lignin sulfonate and 1 part by weight of sodium oleoylmethyltauride, as-wetting and dispersing agent, and gri n~; ng the mix-ture in a pinned-disk mill.

c~ A dispersion concentrate which is readily ~ispers-ible in water is obt~;ne~ by mixing 20 parts by weight of a compound of the formula (I) with 6 parts by weight of alkylphenyl 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 ball mill.

d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I), 75 parts by weight of cyclohpy~no~e as the solvent, and 10 parts by weight of oxyethylated nonylphenol as the emulsifier.

e) Water-dispersible granules are obtained by mixing 75 parts by weight of a compound of the formula (I), 10 part~ by weight of calcium lignin sulfonate 5 parts by weight of sodium lauryl sulfate 3 parts by weight of polyvinyl alcohol and 7 parts by weight of kaolin, gr; n~; ng the mixture in a pinned-disk mill and granulating the powder in a fluidized bed by spray-ing on water as 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'-~;n~phthylmethane-6,6'-disulfonate, 2 parts by weight of sodium oleoylmethyltaurite 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 in a bead mill and atomizing and drying the suspen-~ion 'hus obtained in a spray tower, hy me~n~ 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 80il. 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 compound~ according to the invention have a good herbicidal pre-emergence activity against a broad spectrum of graminaceous and broad-leaved weeds. For example, the compounds of Examples 1-37, 1-38, 1-91, 1-92, 1-146, 1-147, 2-97, 2-98, 2-247, 2-248, 2-260, 2-349, 3-19 and 3-128 (cf. Tables l to 3) have a very good herbicidal action against harmful plants such as Sinapis alba, Chrysanthemum segetum, Avena sativa, Stellaria media, Echinochloa crus-galli, Lolium multi-florum, Setaria spp., Matricaria inodora, 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 substance per hectare.

2. Action on weeds by the post-emergence method Seeds or pieces of rhizome of monocotyledon and dicotyledon weeds are laid out in sandy loam soil in plastic pots, cov red 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 import-ant graminaceous and broad-leaved weeds in the post-emergence method. For example, the compounds of Examples 1-37, 1-38, 1-91, 1-92, 1-146, 1-147, 2-97, 2-98, 2-247, 2-248, 2-260, 2-349, 3-19 and 3-128 (cf. Tables 1 to 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., Matricaria inodora, 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 ~ubstance 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 i ediately as described under Section 1, and the others are placed in a greenhouse until the plants have 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~; 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, oilseed rape, sugar beet and potatoes undamaged by the pre- and post-emergence methods even at high dosages of active compound. Some substances furthermore also protect graminaceous crops, such as, for example, barley, wheat, rye, Sorghum species, 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 (9)

claims:

1. A compound of the formula (I) or a salt thereof in which R1 is S(o)nR4, SO2NR5R6 or CONR5R6, R2 is H, halogen, NO2, CN, (C1-C4)alkyl, (C1-C4)-alkoxy, [(C1-C4)alkyl]carbonyl or [(C1-C4)-alkoxy]carbonyl, where each of the last four radicals mentioned is unsubstituted or substituted tuted in the alkyl part by one or more halogen atoms, R3 is H or (C1-C4)alkyl, R4 is an aliphatic hydrocarbon radical or aryl, where each of the last two radicals mentioned is unsubstituted or substituted, R5 and R6 independently of one another are H, an aliphatic hydrocarbon radical or aryl, where each of the last two radicals mentioned is unsubstituted or substituted, or R5 and R6, together with the N atom, are a heterocyclic radical, which is unsubstituted or substituted, A is a radical of the formula A1 or, in the case that R1 = S(O)nR4 or SO2NR5R6, also A2, R7 and R8 independently of one another are H, NO2, CN, an aliphatic hydrocarbon radical, a heterocyclic radical or aryl, where each of the last three radicals mentioned is unsubstituted tuted or substituted, or an acyl radical, or R7 and R8, together with the carbon atom, are a carbocyclic or heterocyclic ring, which is unsubstituted or substituted, R9 is H, an aliphatic hydrocarbon radical, which is unsubstituted or substituted, or an acyl radical, R10 is an acyl radical, which is unsubstituted or substituted, R11 is H or an aliphatic hydrocarbon radical, which is unsubstituted or substituted, W is an oxygen or sulfur atom, X and Y independently of one another are H, halogen, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkylthio, where each of the last three radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkoxy and (C1-C4)alkylthio, or mono- or di-[(C1-C4)alkyl]amino, (C3-C6)cyclo-alkyl, (C2-C5)alkenyl, (C2-C5)alkynyl, (C2-C5)-alkenyloxy or (C2-C5)alkynyloxy, Z is CH or N and n is 0, 1 or 2.

2. A compound of the formula (I) or a salt thereof as claimed in claim 1, in which R1 is S(O)nR4, SO2NR5R6 or CONR5R6, R2 is H, halogen, NO2, CN, (C1-C4)alkyl, (C1-C4)-alkoxy, [(C1-C4)alkyl]carbonyl or [(C1-C4)-alkoxy]carbonyl, where each of the last four radicals mentioned is unsubstituted or substituted in the alkyl part by one or more halogen atoms, R3 is H or (C1-C4)alkyl, R4 is (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C3-C7)cycloalkyl, (C3-C7)cycloalkyl-(C1-C3)-alkyl or phenyl, 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, (C1-C4)alkylthio, (C1-C4)alkylsulfinyl, (C1-C4)-alkylsulfonyl, unsubstituted or substituted phenyl, [(C1-C4)alkoxy]carbonyl and, in the case of cyclic radicals, also (C1-C4)alkyl and (C1-C4)haloalkyl, R5 and R6 independently of one another are H, (C1-C6)alkyl, (C3-C6)alkenyl, (C3-C6)alkynyl, where each of the last three radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkoxy, (C1-C4)alkylthio and [(C1-C4)alkoxy]carbonyl, or unsubstituted or substituted phenyl, or R5 and R6, together with the N atom, are a heterocyclic ring having 5 or 6 ring members, which can optionally contain further hetero-atoms from the group consisting of N, O and S
and is unsubstituted or mono- or polysubstituted by (C1-C4)alkyl or an oxo group, A is a group of the formula A1 mentioned or, in the case that R1 = S(O)nR4 or SO2NR5R6, also a group of the formula A2 mentioned, R7 and R3 independently of one another are H, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl or (C3-C6)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-C4)alkoxy, (C1-C4)alkylthio and [(C1-C4)alkoxy]carbonyl, phenyl, and, in the case of cycloalkyl, also (C1-C4)alkyl and (C1-C4)haloalkyl, or phenyl or phenylcarbonyl, where each of the last two radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, CN, NO2, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy, (C1-C4) halo-alkoxy, (C1-C4)alkylthio and [(C1-C4)alkoxy]-carbonyl, or heterocyclyl having 3 to 6 ring atoms, which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4) alkoxy and (C1-C4) haloalkyl, or [(C1-C4)alkoxy]carbonyl, [(C1-C4)alkyl]-carbonyl, CN, (C1-C4)alkylsulfonyl, NO2 or COOH, or carbamoyl, which is unsubstituted or contains, on the N atom, one or two substituents from the group consisting of the radicals (C1-C4)alkyl, (C3-C4) alkenyl, (C3-C4) alkynyl and phenyl, which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfonyl, [(C1-C4)alkoxy]-carbonyl, CN and NO2, or di[(C1-C4)alkoxy]-phosphinyl or R7 and R8, together with the carbon atom, are a ring having 4 to 8 ring atoms, which is carbocyclic or is heterocyclic and has one or two heteroatoms from the group consisting of N, O and S, and which is unsubstituted or substituted by one or more radicals from the group consisting of (C1-C4)alkyl, halogen and oxo or is also benzo-fused, R9 is H or (C1-C6)alkyl, which unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfonyl, [(C1-C4)alkoxy]carbonyl, CN, phenyl and (C3-C6)-cycloalkyl, or (C3-C6)alkenyl, (C3-C6)-alkynyl, where each of the last two radicals mentioned is unsubstituted or substituted by one or more halogen atoms, or a group of the formula or SO2R**-, in which R* is H, (C1-C8)alkyl, (C2-C6)alkenyl or (C2-C6)alkynyl, where each of the last three radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkoxy, (C1-C4) alkyl-thio, phenoxy, [(C1-C4)alkoxy]-carbonyl, unsubstituted or substituted heterocyclyl and unsubstituted or substituted phenyl, or unsubstituted or substituted (C3-C6)cycloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted heterocyclyl or [(C1-C4)alkoxy]carbonyl, R** is (C1-C6)alkyl, (C3-c6)alkenyl or (C3-C6) alkynyl, where each of the last three radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkoxy, (C1-C4)alkylthio and phenyl, or phenyl which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, CN, NO2, (C1-C4)alkyl, (C1- C4) haloalkyl and (C1- C4) alkoxy, R10 is an acyl radical of the formula , , -SO2R14, , SO2R15R16, R11 is H, (C1-C6)alkyl, (C3-C6)alkenyl or (C3 -C6)alkynyl, where each of the last three radicals mentioned is unsubstituted or substituted by one or more of the radicals from the group consisting of halogen, (C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkoxy]
carbonyl, (C3-C6) cycloalkyl, unsubstituted or substituted phenyl and CN, R12 is H, (C1-C8)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, where each or the last three radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkoxy, (C1-C4)alkylthio, phenoxy, [(C1-C4)alkoxy]
carbonyl, unsubstituted or substituted heterocyclyl and unsubstituted or substituted phenyl, or unsubstituted or substituted (C3-C6)cycloalkyl, unsubstituted or substituted phenyl, unsubstituted or substituted heterocyclyl or [(C1-C4)alkoxy]carbonyl, R13 is (C1-C6)alkyl, (C3-C6)alkenyl, (C3-C6) alkynyl, where each of the last three radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkoxy, (C1-C4)alkyl-thio, [(C1-C4)alkoxy]carbonyl, unsubstituted or substituted phenyl and unsubstituted or substituted (C3-C6)-cycloalkyl, or (C3-C6)cycloalkyl, which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkyl and (C1- C4) alkoxy, R14 is a radical from the group of radicals possible for R4, R15 is a radical from the group of radicals possible for R5, R16 is a radical from the group of radicals possible for R6, or R15 and R16, together with the N atom, are a heterocyclic radical such as is possible for NR5R6, W is an oxygen atom or a sulfur atom, preferably an oxygen atom, W* is an oxygen atom or a sulfur atom, preferably O, T is an oxygen atom or a sulfur atom, preferably O, n is 0, 1 or 2, X and Y independently of one another are H, halogen, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)-alkylthio, where each of the last three radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkoxy and (C1-C4)alkylthio, or mono- or di-[(C1-C4)-alkyl]
amino, (C3-C6)-cycloalkyl, (C3-C5)-alkenyl, (C3-C5)alkynyl, (C3-C5)alkenyloxy or (C3-C5)alkynyloxy and Z is CH or N.

3. A compound of the formula (I) or a salt thereof as claimed in claim 1 or 2, in which R2 is H, (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)-alkoxy or halogen, R4 is (C1-C4)alkyl, (C2-C4)alkenyl, (C2-C4)alkynyl, (C3-C6)cycloalkyl, (C3-C6)cycloalkyl-(C1-C2)-alkyl, or phenyl, 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, phenyl and [(C1-C4)alkoxy]carbonyl and, in the case of cyclic radicals, also (C1-C4)alkyl and (C1-C4)-haloalkyl, R5 and R6 independently of one another are H, (C1-C6)alkyl, which is unsubstituted or substituted by one or more radicals from the group consisting of halogen and (C1-C4)alkoxy, or (C3-C4)alkenyl or (C3-C4)alkynyl,or R5 and R6, together with the N atom, are a heterocyclic ring having 5 or 6 ring members, which can optionally contain 1 or 2 further heteroatoms from the group consisting of N, O
and S, R7 and R8 independently of one another are H, (C1-C4)alkyl, (C2-C4)alkenyl, where each of the last two radicals mentioned is substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkoxy and phenyl, or (C3-C6)-cycloalkyl, (C3-C6)alkynyl, phenyl or phenylcarbonyl, where each of the last two radicals mentioned is unsubstituted or substituted by one or more radicals from the group consisting of fluorine, chlorine, CN, NO2, (C1-C4)haloalkyl, (C1-C4)alkoxy, (C1-C4)alkyl-thio and [(C1-C4)alkoxy]carbonyl, or furyl, pyridyl, thienyl, tetrahydrofuryl, [(C1-C4)-alkoxy]
carbonyl or COOH or CN, NO2, carbamoyl, which is unsubstituted or is mono- or disubstituted by radicals from the group consisting of (C1-C4)alkyl or is monosubstituted by phenyl, or -PO(OCH3)2 or -PO(OC2H5)2 or R7 and R8, together with the carbon atom, are a ring having 4 to 8 ring members, which is carbocyclic or heterocyclic with a heteroatom from the group consisting of N, O and S and is unsubstituted or mono- or polysubstituted by (C1-C4)alkyl or halogen or an oxo group, R9 is H, (C1-C4)alkyl, which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkoxy, (C1-C4)alkylthio, [(C1-C4)alkoxy]carbonyl and phenyl, or (C3-C4) alkenyl or (C3-C4) alkynyl, R10 is a radical of the formula , , , R11 is H, (C1-C4)alkyl, which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkoxy, (C1-C4)alkylthio, [(C1-C4)alkoxy]carbonyl and phenyl, or (C3-C4) alkenyl or (C3-C4) alkynyl, R12 is H, (C1-C6)alkyl which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C6)alkoxy, (C1-C4)alkylthio, [(C1-C4)alkoxy]carbonyl and unsubstituted or substituted phenyl, or (C2-C4)-alkenyl or (C2-C4)alkynyl, (C3-C6)-cycloalkyl, [(C1-C4)alkoxy]carbonyl, unsubstituted or substituted phenyl or unsbstituted or substituted heterocyclyl, R13 is (C1-C4)alkyl, (C1-C4)haloalkyl, (C3-C4)-alkenyl, (C3-C4) alkynyl or (C3-C6)-cycloalkyl, R15 is a radical from the group of radicals possible for R5, R16 is a radical from the group of radicals possible for R6, or R15 and R16, together with the N atom, are a heterocyclic radical such as is possible for NR5R6, W* is an oxygen atom or a sulfur atom and X and Y independently of one another are (C1-C4)-alkyl, (C1-C4)alkoxy, where each of the last .

two radicals mentioned is unsubstituted or substituted by one or more halogen atoms, or (C1-C4)alkylthio, halogen or mono- or di-[(C1-C2)alkyl]amino.

4. A compound of the formula (I) or a salt thereof as claimed in one of claims 1 to 3, in which R2 is H, halogen or (C1-C2)alkyl, R4 is (C1-C4) alkyl, (C1-C4)haloalkyl, (C3-C4)-alkenyl or (C3-C4)alkynyl or R5 and R6 independently of one another are H, (C1-C4)alkyl, (C3-C4)alkenyl or (C3-C4)alkynyl or R5 and R6, together with the N atom, are a heterocyclic ring having 5 or 6 ring members, R7 and R8 independently of one another are H, (C1-C4)alkyl, (C1-C4) haloalkyl, (C1-C2) alkoxy-(C1-C2)alkyl, (C2-C4)alkenyl, (C2-C4)alkynyl, (C3-C6)-cycloalkyl or [(C1-C4)alkoxy]carbonyl or R7 and R8, together with the carbon atom, are a ring having 5 or 6 ring members, R9 is H or (C1-C3)alkyl, R10 is a radical of the formula , , R11 is H or (C1-C4)alkyl, R12 is H or (C1-C6)alkyl, which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkoxy and phenyl, or (C2-C4)alkenyl, (C3-C6)cycloalkyl or phenyl, which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)alkyl and (C1-C3)-alkoxy, R13 is (C1-C4)alkyl or (C1-C4)haloalkyl, n is 2, X is (C1-C2)alkyl, (C1-C2)alkoxy, (C1-C2)alkyl-thio, (C1-C2)haloalkyl or (C1-C2)haloalkoxy and Y is (C1-C2)alkyl, (C1-C2)alkoxy, halogen, NHCH3 or N(CH3) 2.

5. A process for the preparation of a compound of the formula (I) or a salt thereof as defined in one of claims 1 to 4, which comprises a) reacting a compound of the formula (II) ( I I ) with a heterocyclic carbamate of the formula (III) ( I I I ) in which R* is unsubstituted or substituted phenyl or (C1-C4)alkyl, or b) reacting a sulfonylcarbamate of the formula (IV) (IV) in which R0 is unsubstituted or substituted phenyl or (C1-C4)alkyl, with an amino-heterocyclic compound of the formula (V) (V) or c) reacting a sulfonyl isocyanate of the formula (VI) <IMG< (VI) with an amino-heterocyclic compound of the formula (V) or d) reacting a sulfonamide of the formula (II) with a (thio)-isocyanate of the formula (VII) (VII) in the presence of a base or e) first reacting an amino-heterocyclic compound of the formula (V) with a carbonic acid ester under base catalysis and reacting the intermediate formed with a sulfonamide of the formula (II) in a one-pot reaction, in which, in the formulae (II)-(VII), the radicals and groups R1-R3, A, W, X, Y and Z are defined as in formula (I), and in process variants a) to c) and e), compounds (I) with W = O are initially obtained.

6. 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 4 and formulation auxiliaries customary in plant protection.

7. 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 a salt thereof as claimed in one of claims 1 to 4 to the harmful plants or plants, plant seeds thereof or the area on which they grow.

8. The use of a compound of the formula (I) or of a salt thereof as claimed in one of claims 1 to 4 as a herbicide or plant growth regulator.

9. A compound of the formula (II), (IV) and (VI) as defined in claim 5.