CA2201596A1 - Sulfonylaminocarbonyltriazolinones with substituents bound by oxygen and sulphur - Google Patents

Abstract

New sulfonylaminocarbonyltriazolinones with substituents bound by oxygen and sulphur have the formula (I), in which n equals 0, 1 or 2; R1 stands for hydrogen or an optionally substituted rest from the group alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, aryl, aralkyl; R2 stands for an optionally substituted rest from the group alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, aralkyl, aryl; and R3 stands for an optionally substituted rest from the group alkyl, aralkyl, aryl, heteroaryl. Certain new compounds having the formula (I) but already disclosed in EP-A 431291, are excluded. Also disclosed are salts of the new compounds having the formula (I), several processes and various new intermediate products for preparing the new compounds and their use - possibly as salts - as herbicides and fungicides.

Description

rr ^~ s~ ~ - ' -t ~ ~ LE, ~,~3 ~ 3 T.. ~
~ LeA30586-PCT ~J~ s 11 i~ I '201596 Sulphonylaminoca~o~lll;~olinones with ~ lilu~ bonded via oxygen and JLu-The invention relates to novel sulphonylaminocarbonylkiazolinones with sub-stituP~t~ bonded via oxygen and sulphur, to several processes and various novel S intermediates for their pl~al~Lion and to their use as herbicides and fungicides.

Certain sulphonylaminocarbonylkiazolinones, e.g. the compound 4-amino-5-methylthio-2-(2-kifluoromethoxy-phenylsulphonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one, are known to have herbicidal properties (cf. EP-A 341489; EP-A 422469, EP-A 425948, EP-A 431291). The last of these documents has also 10 already disclosed some sulphonylaminocarbonyltriazolinones with substituents bonded via oxygen and sulphur (cf. the following disclaimer). However, the action of these previously known compounds is not satisfactory in all respects.

The novel sulphonylaminocarbonylkiazolinones with substituents bonded via oxygen and sulphur of the general formula (I):

3 0 ~

SO2_N ~N~ ~N (I) S()n~R

15 in which n is the number 0, 1 or 2, R' is hydrogen or an optionally substituted radical from the group comprising alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, aryl and aralkyl, R2 is an optionally substituted radical from the group comprising alkyl, 20 alkenyl, alkinyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, aralkyl and aryl, and ~` ~ LeA30586 -2- 22015~6 R3 is an optionally substituted radical from the group comprising alkyl, aralkyl, aryl and heteroaryl, and salts of compounds of the formula (I), have now been found, the following compounds - known from EP-A 431291 - being excluded by dis-5 claimer: 4-methoxy-5-methylthio-2-(2-methoxycarbonyl-phenylsulphonyl-amino-carbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one, 4-ethoxy-S-ethylthio-2-[2-(N-methoxy)-methylaminosulphonyl-phenylsulphonyl-aminocarbonyl] -2,4-dihydro-3H-1,2,4-triazol-3-one, 4-propoxy-5-allylthio-2-(2-methyl-phenylsulphonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one, 4-methoxy-5-methylthio-2-(2-methoxycarbonyl-thien-3-yl-sulphonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one, 4-ethoxy-5-methylthio-2-(2-methoxy-phenylsulphonyl-amino-carbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one, 4-ethoxy-5-ethylthio-2-[2-(2-chloro-ethoxy)-phenyl~lllphonyl-aminocarbonyl]-2,4-dihydro-3H-1 ,2,4-triazol-3-one, 4-allyloxy-5-ethylthio-2-(2-fluoro-phenylsulphonyl-aminocarbonyl)-2,4-dihydro-3H-1 ,2,4-triazol-3-one, 4-methoxy-5-ethylthio-2-(3-aminosulphonyl-pyridin-2-yl-sulphonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one and 4-methoxy-5-ethylthio-2-(2,6-difluoro-phenylsulphonyl-aminocarbonyl)-2,4-dihyd-ro-3H-1 ,2,4-triæol-3-one.

The novel sulphonylaminocarbonyltriazolinones with substituents bonded via 20 oxygen and sulphur of the formula (I) are obtained by (a) reacting triazolinones of the general formula (II):
o H--NJ~N--O-R
N =~ (I l) S(O)n-R2 r~
~ Le A 30 586 - 3 -~2~ 1 596 in which n, R' and R2 are as defined above, with sulphonyl isocyanates of the general forrnula (III):

R3-So2-N=C=o (III) in which R3 is as defined above, - optionally in the presence of a reaction auxiliary and optionally in the presence of a diluent, or by 10 (b) reacting triazolinone derivatives of the general formula (IV):

o .
,~NlN_O-R1 Z ~ =(, (IV) S(O)n-R2 in which n, Rl and R2 are as defined above and Z is halogen, alkoxy, aralkoxy or aryloxy, with sulphonamides of the general formula (V):

220 ~ ~39~
~ LeA30 586 -4-,, .

R;-SO2-NH2 (V) in which R3 is as defined above, optionally in the presence of an acid acceptor and optionally in the 5 presence of a diluent, or by (c) reacting triazolinones of the general formula (II):
o H--N N--O-R
N=~ (Il) S~O)n-R2 in which n, Rl and R~ are as defined above, with sulphonamide derivatives of the general formula (VI):

R3-So2-NH-Co-Z (VI) in which R3 is a defined above and Z is halogen, alkoxy, aralkoxy or aryloxy, LeA30586 -5-220 1 5 q6 optionally in the presence of an acid acceptor and optionally in the presence of a diluent, or by (d) reacting triazolinones of the general formula (II):
o H_NlN_O-R1 =~ (I l) S(O)n-R2 in which n, R' and R2 are as defined above, with sulphonyl halides of the general formula (VII):

R3-So2-X (VII) in which R3 is as defined above and X is halogen, and with metal cyanates of the general formula (VIII):

MOCN (VIII) in which ~ Le A 30 586 - 6 - 2 2 0 1 5 ~ 6 M is an aLkali metal or ~Ik~line earth metal equivalent, optionally in the presence of a reaction auxiliary and optionally in the presence of a diluent, and the compounds of the formula (I) obtained by process (a), (b), (c) or 5 (d) are optionally converted to salts by conventional methods.

If R2 is propargyl in the novel compounds of the formulae (I), (II) and (IV), they can be isomerized to corresponding compounds in which R2 is allenyl (= propa-1,2-dienyl) by treatment with bases (cf. the Preparatory Examples).

A feature of the novel sulphonylaminocarbonyltriazolinones with substituents 10 bonded via oxygen and sulphur of the general formula (I) is their potent herbicidal and fungicidal activity.

Surprisingly, the novel compounds of the formula (I) exhibit a considerably morepotent herbicidal action than structurally similar compounds representative of the state of the art, e.g. the known 4-amino-5-methylthio-2-(2-trifluoromethoxy-phenylsulphonyl-aminocarbonyl)-2,4-dihydro-3H- 1 ,2,4-triazol-3-one.

The invention plefeLellLially provides compounds of the formula (I) in which n is the number 0, 1 or 2, R' is hydrogen, C,-C6-alkyl optionally substituted by fluorine, chlorine, bromine, cyano, Cl-C4-alkoxy, Cl-C4-alkyl-carbonyl or Cl-C4-alkoxy-carbonyl, 20 C2-C6-alkenyl or C2-C6-alkinyl, each of which is optionally substituted by fluorine, chlorine and/or bromine, C3-C6-cycloalkyl or C5-C6-cycloalkenyl, each of which is optionally substituted by fluorine, chlorine, bromine and/or Cl-C4-alkyl, or phenyl or phenyl-Cl-C3-alkyl, each of which is optionally substituted by ~ Le A 30 586 - 7 -fluorine, chlorine, bromine, cyano, niko, Cl-C4-alkyl, trifluoromethyl, C~-C~-alkoxy and/or Cl-C4-alkoxy-carbonyl, R2 is Cl-C6-alkyl optionally substituted by fluorine, chlorine, bromine, cyano, C3-C6-cycloalkyl, Cl-C4-alkoxy, Cl-C4-alkylthio or Cl-C4-alkoxy-carbonyl, C2-C6-S alkenyl or C2-C6-alkinyl, each of which is optionally substituted by fluorine,chlorine and/or bromine, C3-C6-cycloalkyl, Cs-C6-cycloalkenyl or C3-C6-cycloalkyl-C,-C3-alkyl, each of which is optionally substituted by fluorine, chlorine, bromine and/or Cl-C4-alkyl, phenyl-CI-C3-alkyl optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C,-C4-alkyl, trifluoromethyl, Cl-C4-10 alkoxy and/or Cl-C4-alkoxy-carbonyl, or phenyl optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C,-C4-alkyl, trifluoromethyl, Cl-C4-alkoxy, fluorine- and/or chlorine-substituted C,-C3-alkoxy, Cl-C4-alkylthio, fluorine- and/or chlorine-substituted Cl-C3-alkylthio, Cl-C4-alkyl-sulphinyl, Cl-C4-alkylsulphonyl and/or Cl-C4-alkoxy-carbonyl, and /~ R
lS R3 is the grouping ~

wherein R4 and R5 are identical or dirrelellt and are hydrogen, fluorine, chlorine, bromine, iodine, nitro, Cj-C6-alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, Cl-C4-alkoxycarbonyl, Cl-C4-alkylamino-carbonyl, di-(C,-C4-alkyl)amino-carbonyl, hydroxyl, C,-C ,-alkoxy, formyloxy, Cl-C4-alkyl-carbonyloxy, Cl-C4-alkoxy-carbonyloxy, Cl-C4-alkylarnino-carbonyloxy, Cl-C4-alkylthio, Cl-C4-alkylsulphinyl, Cl-C4-alkylsulphonyl, di-(CI-C4-alkyl)-arninosulphonyl, C3-C6-cycloalkyl or Le A 30 586 - 8 - 20 1 5 9 6 phenyl), C2-C6-alkenyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, Cl-C4-alkoxy-carbonyl, carboxyl or phenyl), C2-C6-alkinyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, Cl-C4-alkoxy-carbonyl, carboxyl or phenyl), Cl-C4-alkoxy (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, Cl-C4-alkoxy-carbonyl, Cl-C4-alkoxy, C,-C4-alkylthio, Cl-C4-alkylsulphinyl or Cl-C4-alkylsulphonyl), Cl-C4-alkylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, Cl-C4-alkoxy-carbonyl, Cl-C4-alkylthio, Cl-C4-alkylsulphinyl or Cl-C4-alkylsulphonyl), C2-C6-alkenyloxy (which is optionally substituted by fluorine, chlorine, bromine, cyano or Cl-C4-alkoxy-carbonyl), C2-C6-alkenylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, Cl-C3-alkylthio or Cl-C4-alkoxycarbonyl), C3-C6-alkinyloxy, C3-C6-alkinylthio or the radical -S(O)p-R6, in which p is the number 1 or 2 and R6 is Cl-C4-alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano or Cl-C4-alkoxy-carbonyl), C3-C6-alkenyl, C3-C6-alkinyl, Cl-C4-alkoxy, Cl-C4-alkoxy-CI-C4-alkylamino, Cl-C4-alkylamino, di-(CI-C4-alkyl)-amino, phenyl or the radical -NHoR7, in which R7 is Cl-CI2-alkyl (which is optionally substituted by fluorine, chlorine, cyano, Cl-C4-alkoxy, Cl-C4-alkylthio, Cl-C4-alkylsulphin-yl, Cl-C4-alkylsulphonyl, Cl-C4-alkyl-carbonyl, Cl-C4-alkoxy-carbonyl, Cl-C4-alkylamino-carbonyl or di-(CI-C4-alkyl)-amino-2 carbonyl), C3-C6-alkenyl (which is optionally substituted by fluorine, chlorine or bromine), C3-C6-alkinyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-CI-C2-alkyl, phenyl-CI-C2-alkyl (which is optionally substituted by fluorine, chlorine, nitro, cyano, C,-C4-alkyl, Cl-C4-Le A 30 586 - 9 -22015q6 alkoxy or C~-C4-alkoxy-carbonyl), benzhydryl or phenyl (which is optionally substituted by fluorine, chlorine, nitro, cyano, Cl-C4-alkyl, trifluoromethyl, C,-C4-alkoxy, Cl-C2-fluoroalkoxy, Cl-C4-alkylthio, trifluoromethylthio or Cl-C4-alkoxy-carbonyl), R4 and/or R5 are also phenyl or phenoxy, Cl-C4-alkyl-carbonylamino, Cl-C4-alkoxy-carbonylamino, C,-C4-alkylamino-carbonyl-amino, di-(CI-C4-alkyl)-amino-carbonylamino or the radical -Co-R3, in which R3 is hydrogen, Cl-C6-alkyl, C3-C6-cycloalkyl, Cl-C6-alkoxy, C3-C6-cycloalkoxy, C3-C6-alkenyloxy, Cl-C4-alkylthio, Cl-C4-alkylamino, Cl-C4-alkoxyamino, Cl-C4-alkoxy-CI-C4-alkylamino or di-(CI-C4-alkyl)-amino (which are optionally substituted by fluorine and/or chlorine), or R4 and/or R5 are also trimethylsilyl, thiazolinyl, Cl-C4-alkylsulphonyloxy, di-(CI-C4-alkyl)-aminosulphonylamino or the radical -CH=N-R9, in which R9 is Cl-C6-alkyl optionally substituted by fluorine, chlorine, cyano, carboxyl, Cl-C4-alkoxy, Cl-C4-alkylthio, Cl-C4-alkylsulphin-yl or Cl-C4-alkylsulphonyl, benzyl optionally substituted by fluorine or chlorine, C3-C6-alkenyl or C3-C6-alkinyl, each of which is optionally substituted by fluorine or chlorine, phenyl optionally substituted by fluorine, chlorine, bromine, Cl-C4-alkyl, Cl-C4-alkoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, Cl-~ O-alkoxy, C3-C6-alkenoxy, C3-C6-alkinoxy or benzyloxy, each of which is optionally substituted by fluorine and/or chlorine, amino, C,-C4-alkylamino, di-(CI-C4-alkyl)-amino, phenylamino, Cl-C4-alkyl-carbonylamino, Cl-C4-alkoxy-carbonylamino, Cl-C4-alkyl-Le A 30 586 - 10 - 22 0 1 5 9 6 sulphonylamino, orphenylsulphonylamino optionally substituted by fluorine, chlorine, bromine or methyl, or R3 is the radical -1H ;~R12 S wherein R' is hydrogen or Cl-C4-alkyl and R~l and Rl2 are identical or dir~,elll and are hydrogen, fluorine, chlorine, bromine, nitro, cyano, Cl-C4-alkyl (which is optionally substituted by fluorine and/or chlorine), Cl-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), carboxyl, C,-C4-alkoxycarbonyl, dimethylaminocarbonyl, Cl-C4-alkylsulphonyl or di-(C,-C4-alkyl)-aminosulphonyl, or R3 is the radical R'3--~3R14 1 5 wherein Le A 30 586 - 11 -Rl3 and R~4 are identical or dirr~ and are hydrogen, fluorine, chlorine, bromine, nitro, cyano, Cl-C4-alkyl (which is optionally substituted by fluorine and/or chlorine) or Cl-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), S or R3 is the radical [~}

wherein Rl5 and Rl6 are identical or different and are hydrogen, fluorine, chlorine, bromine, nitro, cyano, Cl-C4-alkyl (which is optionally substituted by fluorine and/or chlorine), Cl-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), Cl-C4-alkylthio, C~-C4-alkylsulphinyl or C~-C4-alkylsulphonyl (which are optionally substituted by fluorine and/or chlorine), aminosulphonyl, mono-(CI-C4-alkyl)-aminosulphonyl, di-(CI-C4-alkyl)-aminosulphonyl, Cl-C4-alkoxy-carbonyl or dimethylaminocarbonyl, 15 or R3 is the radical R1 ~R,B

wherein Rl7 and Rl8 are identical or different and are hydrogen, fluorine, chlorine, ~ ~ LeA30586 -12- 2201 596 bromine, Cl-C4-aLkyl (which is optionally substituted by fluorine and/or bromine), C,-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), C,-C4-alkylthio, Cl-C4-alkylsulphinyl or Cl-C4-alkylsulphonyl (which are optionally substituted by fluorine and/or chlorine) or di-(C,-C4-alkyl)-aminosulphonyl, or Rl9 R3 is the radical {~ R20 wherem Rl9 and R20 are identical or dirr~.ellt and are hydrogen, fluorine, chlorine, bromine, cyano, nitro, C,-C4-alkyl (which is optionally substituted by fluorine and/or chlorine), Cl-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), Cl-C4-alkylthio, Cl-C4-alkylsulphinyl or Cl-C4-alkylsulphonyl (which is optionally substituted by fluorine and/or chlorine), di-(CI-C4-alkyl)-amino-sulphonyl, Cl-C4-alkoxy-carbonyl or dimethylaminocarbonyl, and A is oxygen, sulphur or the grouping N-ZI, in which Z' is hydrogen, Cl-C4-alkyl (which is optionally substituted by fluorine, chlorine, bromine or cyano), C3-C6-cycloalkyl, benzyl, - phenyl (which is optionally substituted by fluorine, chlorine, bromine or nitro), Cl-C4-alkylcarbonyl, Cl-C4-alkoxycarbonyl or di-(C,-C4-alkyl)-aminocarbonyl, LeA30586 - 13- 2~0~ 5q6 or R3 is the radical ~L~R22 wherein R2l and R22 are identical or different and are hydrogen, Cl-C4-alkyl, halogen, Cl-C4-alkoxycarbonyl, C,-C4-alkoxy or C,-C4-halogenoalkoxy, and Y' is sulphur or the grouping N-R23, in which R23 is hydrogen or C,-C4-alkyl, or 10 R3 is the radical ~ ~R25 wherein R24 is hydrogen, C,-C4-alkyl, benzyl, pyridyl, quinolinyl or phenyl, R25 is hydrogen, halogen, cyano, nitro, Cl-C4-alkyl (which is optionally substituted by fluorine and/or chlorine), C,-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), dioxolanyl or Cl-C4-alkoxy-~ Le A 30 586 - 14 -~231 596 carbonyl, and R26 is hydrogen, halogen or Cl-C4-alkyl, or R3 is one of the groupings listed below:

H3CO ~ H

S with the exGeptic)n othe ~mpol~nds ex~!uded by disclaimer ab~ve.

The invention also L)l~rel~lllially provides sodium, potassium, m~ne~ium, calcium, ammonium, Cl-C4-alkyl-ammonium, di-(C,-C4-alkyl)-ammonium, tri-(Cl-C4-alkyl)-ammonium, tetra-(C,-C4-alkyl)-ammonium, tri-(Cl-C4-alkyl)-sulphonium, C5- or C6-cycloalkyl-ammonium and di-(C,-C2-alkyl)-benzyl-arnmonium salts of compounds 10 of the formula (I), in which n, R', R2 and R3 have the plef~ d meanings given above.

The invention especially provides compounds of the formula (I) in which n is the number 0, 1 or 2, R' is methyl, ethyl, n- or i-propyl or n-, i-, s- or t-butyl, each of which is 15 optionally substituted by fluorine, chlorine, cyano, methoxy or ethoxy, propenyl, butenyl, propin~ or butinyl, each of which is optionally substituted by fluorine, chlorine or bromine, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, each ofwhich is optionally substituted by fluorine, chlorine, bromine, methyl or ethyl, or benzyl or phenyl, each of which is optionally substituted by fluorine, chlorine, LeA30586 -15- '-20~J~6 bromine, cyano, methyl, trifluoromethyl or methoxy, R2 is methyl, ethyl, n- or i-propyl or n-, i-, s- or t-butyl, each of which is optionally substituted by fluorine, chlorine, cyano, methoxy, ethoxy, methylthio or ethylthio, propenyl, butenyl, propinyl, butinyl or allenyl, each of which is S optionally substituted by fluorine, chlorine or bromine, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, each of which is optionally substituted by fluorine, chlorine, bromine, methyl or ethyl, or phenyl or benzyl, each of which is optionally substituted by fluorine, chlorine, bromine, cyano, methyl, trifluoromethyl or 10 methoxy, and /~R
R3 is the radical ~

wherein R4 is fluorine, chlorine, bromine, methyl, ethyl, propyl, trifluoromethyl, butoxy, allyloxy, propargyloxy, methoxy, ethoxy, propoxy, isopropoxy, difluoromethoxy, trifluoromethoxy, 2-chloro-ethoxy, 2-methoxy-ethoxy, C,-C3-alkylthio, C,-C3-alkylsulphinyl, C,-C3-alkylsulphonyl, dimethylaminosulphonyl, diethylaminosulphonyl, N-methoxy-N-methylaminosulphonyl, methoxyaminosulphonyl, phenyl, phenoxy or C,-C3-alkoxycarbonyl, and Rs is hydrogen, methyl, ethyl, fluorine, chlorine or bromine, or 220 ~ ~96 Le A 30 586 - 16 -R3 is the radical CH~

wherein R' is hydrogen, Rll is fluorine, chlorine, bromine, methyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methyl-sulphonyl or dimethylaminosulphonyl, and Rl2 is hydrogen, or R3 is the radical Ro-C~3 wherein R is Cl-C4-alkyl, or --Le A 30 586 - 17 -R26 R2s R3 is the radical )~
N

wherein R24 is C,-C3-alkyl, phenyl or pyridyl, S
R2s is hydrogen, fluorine, chlorine or bromine and R26 is fluorine, chlorine, bromine or C,-C3-alkoxy-carbonyl, with the exception of the compounds excluded by ~ çl~imer above.

The general or plerell~d radical definitions listed above apply both to the end products of the formula (I) and to the corresponding starting m~teri~l~ or 15 intermediates required for their preparation. These radical definitions can be freely combined with one another, including between the l~Lefcl.~d mt-~nin~;~ indicated.

The hydrocarbon radicals mentioned in the radical definitions, such as alkyl, alkenyl or alkinyl, and their forms combined with heteroatoms, such as alkoxy, 20 alkylthio or alkylamino, are linear or branched, even when this is not expressly indicated.

Halogen is generally fluorine, chlorine, bromine or iodine, preferably fluorine,chlorine or bromine and especially fluorine or chlorine.
If, for example, 2-kifluoromethoxy-phenylsulphonyl isocyanate and 4-methoxy-5-propylthio-2,4-dihydro-3H-1,2,4-kiazol-3-one are used as starting materials, the LeA 30 586 - 18 - 2201 ~9~
course of the reaction in process (a) according to the invention can be outlined by the following equation:

H_N)~N-O-cH3 ~SO C - N~N - o-cH3 S~3H7 S-C3H, If, for example, 2-ethylthio-benzenesulphonamide and 2-chlorocarbonyl-4-ethoxy-5-methylsulphonyl-2,4-dihydro-3H-1,2,4-triazol-3-one are used as starting materials, 5 the course of the reaction in process (b) according to the invention can be outlined by the following equation:

Cl ~ ~`S2 ~--N N--O C2Hs S02-NH2 N=( - HCI NH
SO-CH

If, for example, N-methoxycarbonyl-2-methoxy-benzenesulphonamide and 5-ethylsulphinyl-4-propoxy-2,4-dihydro-3H-1,2,4-triazol-3-one are used as startingm~t~ , the course of the reaction in process (c) according to the invention can 10 be outlined by the following equation:

~O-CH3 t --N N_O-C3H, ~"S02 ~--NJ~N---C3H7 SO2-NH-COOCH3 SO-C2H5 SO-CzHs If, for example, 2-chloro-6-methyl-benzenesulphonyl chloride, 4-allyloxy-5-benzylthio-2,4-dihydro-3H-1,2,4-triazol-3-one and sodium cyanate are used as starting materials, the course of the reaction in process (d) according to the invention can be outlined by the following equation:
. ~ ~

LeA30586 -19- 220 l 596 ,~ CH3 , ~,~ CH3 L !~ t H_NJ~N,~O-CH2CH=CH2 Cl S-CH-C H -NaCI Cl ~N=~
S-cH2-csHs The triazolinones to be used as starting m~teri~l~ in processes (a), (c) and (d)according to the invention for the pl~dlion of compounds of the forrnula (I) aregenerally defined by the formula (II).

5 In the formula (II), the ~lc;f~lled or particularly ~lef~lled me~nings of n, Rl and R2 are those which have already been indicated above as the pler~ d or particularlyp.~re-.ed m~nin~.~ of n, R~ and R2 in connection with the description of the compounds of the formula (I) according to the invention.

10 The triazolinones of the general formula (II) are not yet known from the literature;
they are also provided by the present patent application as novel substances.

The novel triazolinones of the formula (II) are obtained by reacting mercapto-triazolinones of the general formula (IX):
o N =~ (~x) S~
in which Rl is as defined above, - or metal salts of compounds of the formula (IX) -25 with compounds of the general formula (X):

x R2 (X) Le A 30 586 - 20 - 22 0 1 5 9 6 in which R2 is as defined above and 5 X is halogen or the grouping -O-SO2-OR2, optionally in the presence of an acid acceptor, e.g. potassium hydroxide, potassium t-butylate or potassium carbonate, and optionally in the presence of a diluent, e.g.
methanol or ethanol, at temperatures between 0C and 100C, and then optionally 10 oxitli7:ing the products to corresponding sulphoxides or sulphones in conventional manner (cf. the Preparatory Examples).

In the formula (X), the pler~lled or particularly plefelled me~ning of R~ is that which has already been indicated above as the ~l~felled or particularly pl~f~lled 15 meaning of Rl in connection with the description of the compounds of the formula (I) according to the invention.

The alkali metal salts and ~lk~line earth metal salts, especially the sodium, potassium, m~gnecium and calcium salts, may be singled out as pl~f~lled metal 20 salts of the compounds of the formula (IX).

The mercapto-triazolinones of the general formula (IX) - and their metal salts - are not yet known from the literature; they are also provided by the present patent application as novel substances.
The novel mercaptotriazolinones of the formula (IX) are obtained by reacting semi-carbazide derivatives of the general formula (XI):
o N NH (Xl) , N ~ Y

LeA30586 -21- 22~1 5q6 in which Rl is as defined above and S Y is halogen, imidazolyl, alkoxy, aralkoxy or aryloxy, optionally in the presence of a reaction auxiliary, e.g. potassium carbonate, and optionally in the presence of a diluent, e.g. methanol or ethanol, at temperatures between 20C and 150C (cf. the Pl~p~dloly Examples).
In the formula (XI), the plefelled or particularly plef~..ed me~ning of Rl is that which has already been indicated above as the plert:lled or particularly plc:fel~ed me~ning of Rl in connection with the description of the compounds of the formula(I) according to the invention; Y is preferably fluorine, chlorine, bromine, iodine, 15 methoxy, ethoxy, benzyloxy or phenoxy, especially methoxy or phenoxy.

The semicarbazide derivatives of the general formula (XI) are not yet known fromthe lile,alule, they are also provided by the present patent application as novel substances.
The novel semicarbæide derivatives of the formula (XI) are obtained by reacting semicarbazides of the general forrnula (XII):
o H ~ J~ ~ o-R1 N NH (Xll) Ntl2 in which R' is as defined above, with acylating agents of the general formula (XIII):

` ~ LeA30586 -22- 2201 596 Xl-CS-Y (XIII) in which 5 Y is as defined above and Xl is halogen, optionally in the presence of an acid acceptor, e.g. triethylamine, and optionally in 10 the presence of a diluent, e.g. methylene chloride, at temperatures between 0C and 100C (cf. the Preparatory Examples).

The precursors of the formula (XII) are known and/or can be prepared by processes known per se (cf. J. Prakt. Chem.313 (1971), 636-641; DE-A 2044834; Preparatory lS Examples).

The precursors of the formula (XIII) are known synthetic chemicals.

The alkylating agents required for the preparation of the starting materials of the 20 formula (II) are generally defined by the formula (X). In the formula (X), the plef~ d or particularly pler~ d meaning of R2 is that which has already been indicated above as the plerel.ed or particularly plere.,ed me~nin~ of R2 in cormection with the description of the compounds of the formula (I) according tothe invention, X is preferably fluorine, chlorine, bromine or iodine, especially25 chlorine, bromine or iodine.

The compounds of the formula (X) are known synthetic chemicals.

The sulphonyl isocyanates also to be used as starting materials in process (a) 30 according to the invention for the preparation of compounds of the formula (I) are generally defined by the formula (III).

Le A 30 586 - 23 -In the formula (III), the yl~:rt;ll- d or particularly ple~ d m~nin~ of R3 is that which has already been indicated above as the pler~"ed or particularly pl~"ed me~ninE of R3 in connection with the description of the compounds of the formula(I) according to the invention.
S' The starting materials of the formula (III) are known and/or can be prepared by processes known per se (cf. US-P 4127405, US-P 4169719, US-P 4371391, EP-A 7687, EP-A 13480, EP-A 21641, EP-A 23141, EP-A 23422, EP-A 30139, EP-A 35893, EP-A 44808, EP-A 44809, EP-A 48143, EP-A 51466, EP-A 64322, EP-A 70041, EP-A 173312).

The triazolinone d~,;v~lives to be used as starting materials in process (b) according to the invention for the p,~al~lion of the compounds of the general formula (I) are generally defined by the formula (IV). In the formula (IV), the plere,led or 15 particularly ~l~r~;l,ed meanings of n, Rl and R2 are those which have already been indicated above as the ~lefelled or particularly pLefell~d me~nin~ of n, Rl and R2 in connection with the description of the compounds of the formula (I); Z is preferably fluorine, chlorine, bromine, methoxy, ethoxy, benzyloxy, phenoxy, halogeno-phenoxy or nitro-phenoxy, especially methoxy, phenoxy or 4-nitro-20 phenoxy.

The starting m~teri~l~ of the formula (IV) are not yet known from the literature,they are provided by the present patent application as novel substances.

25 The novel compounds of the formula (IV) are obtained by reacting triazolinones of the general formula (II):
o H - N N-- R
~, ~ =~ (I l) S(O)n-R2 in which 220 1 5~6 Le A 30 586 -24-n, Rl and R2 are as defined above, with carbonic acid derivatives of the general formula (XIV):

S Z-CO-Z' (XIV) in which Z is as defined above and zl is halogen, alkoxy, aralkoxy or aryloxy, optionally in the presence of an acid acceptor, e.g. potassium t-butylate, and optionally in the presence of a diluent, e.g. tetrahydrofuran or dimethoxyethane, at temperatures between 0C and 100C.

The sulphonamides also to be used as starting m~tçri~l~ in process (b) accordingto the invention for the preparation of the compounds of the general formula (I) are generally defined by the formula (V). In the formula (V), the p~ef~ d or particularly pr~felled meaning of R3 is that which has already been indicated above as the plerell~d or particularly ~ f~lled meaning of R3 in connection with the description of the compounds of the formula (I).

The starting m~tçri~l~ of the formula (V) are known and/or can be prepared by processes known per se (cf. US-P 4127405, US-P 4169719, US-P 4371391, EP-A 7687, EP-A 13480, EP-A 21641, EP-A 23141,EP-A 23422, EP-A 30139, EP-A 35893,EP-A 44808,EP-A 44809,EP-A 48143,EP-A 51466,EP-A 64322, EP-A 70041,EP-A 173312).

The sulphonamide derivatives to be used as starting materials in process (c) according to the invention for the preparation of the compounds of the formula (I) are generally defined by the formula (VI). In the formula (VI), the p.e~lled or 220 1 5q6 Le A 30 586 - 25 -particularly ~lefel,cd me~nin~ of R3 is that which has already been indicated above as the plef~lled or particularly ~ler~lled me~ninE of R3 in connection with the description of the compounds of the formula (I); Z is preferably fluorine, chlorine, bromine, methoxy, ethoxy, benzyloxy or phenoxy, especially methoxy or phenoxy.
The starting m~teri~lc of the formula (VI) are known and/or can be prepared by processes known per se.

The sulphonyl halides to be used as starting m~t~ri~l~ in process (d) according to 10 the invention for the ~L~aL~lion of the compounds of the formula (I) are generally defined by the formula (VII). In the formula (VII), the plef~lled or particularly ed me~nin~ of R3 is that which has already been indicated above as the pler~lled or particularly pler~;lled mP~ning of R3 in connection with the description of the compounds of the formula (I); X is preferably fluorine, chlorine or bromine, 15 especially chlorine.

The starting m~teri~l~ of the formula (VII) are known and/or can be prepared by processes known per se.

20 Processes (a), (b), (c) and (d) according to the invention for the pl~l)~alion of the novel compounds of the formula (I) are preferably carried out using diluents, suitable diluents being practically any inert organic solvents. These preferablyinclude optionally halogenated aliphatic and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, 25 toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetra-chloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, esters such as ~ethyl and ethyl acetate, nikiles such as e.g.
30 acetonitrile and propionitrile, amides such as e.g. dimethylformamide, dimethyl-acetamide and N-methylpyrrolidone, and dimethyl sulphoxide, tetramethylene sulphone and hexamethylphosphorotriamide.

220 1 5~6 Le A 30 586 - 26 -The reaction ~llxili~ries or acid acceptors used in processes (a), (b), (c) and (d) according to the invention can be any of the acid binding agents conventionally usable for such reactions, suitable agents preferably being alkali metal hydroxides such as e.g. sodium and potassium hydroxide, ~lk~line earth metal hydroxides such 5 as e.g. calcium hydroxide, alkali metal carbonates and alcoholates such as sodium and potassium carbonate and sodium and potassium tert-butylate, and also basic nitrogen compounds such as trimethylamine, triethylamine, Lliplo~ylamine, tributylamine, diisobutylamine, dicyclohexylamine, ethyldiisopropylamine, ethyl-dicyclohexylamine, N,N-dimethylbenzylamine, N,N-dimethyl-aniline, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 2-ethyl-, 4-ethyl- and 5-ethyl-2-methyl-pyridine, 1,5-diazabicyclo[4.3.0]-non-5-ene (DBN), 1,8-di~7~-bicyclo-[5.4.0]-undec-7-ene (DBU) and 1,4-diazabicyclo-[2.2.2]-octane (DABCO).

The reaction temperatures in processes (a), (b), (c) and (d) according to the 15 invention can be varied within relatively wide limits. The reactions are generally carried out at temperatures between -20C and +100C, preferably at temperaturesbetween 0C and +80C.

Processes (a), (b), (c) and (d) according to the invention are generally carried out 20 under normal pressure, although they can also be carried out under elevated or reduced pressure.

I'Q Garry ~ut processes ~a), ~b)7 (~c) and ~d~ according to the invention, the a~plv~liate starting materials required are generally used in approximately 25 equimolar amounts, although it is also possible to use one of the a~ opliate components in relatively large excess. The reactions are generally carried out in a suitable diluent, in the presence of an acid acceptor, and the reaction mixture is stirred for several hours at the appLo~liate required temperature. Working-up inprocesses (a), (b), (c~ and (d) according to the invention is eff~cted by appropriate 30 conventional methods (cf. the Preparatory Examples).

Salts can optionally be prepared from the compounds of the general formula (I) Le A 30 586 - 27 -according to the invention. Such salts are easily obtained by conventional s~lific~tion methods, for example by dissolving or dispersing a compound of the formula (I) in a suitable solvent, e.g. methylene chloride, acetone, tert-butyl met_yl ether or toluene, and adding a suitable base. The salts can then be isolated by 5 concentration or suction filtration, after prolonged stirring if necessary.

The active substances according to the invention can be used as defoliants, desiccants, herbicides and, in particular, weedkillers. Weeds in the broadest sense are to be understood as meaning any plants which grow in places where they are 10 not desired. Whether the substances according to the invention act as total or selective herbicides depends essçnti~lly on the amount applied.

The active substances according to the invention can be used e.g. on the following plants:
Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, ~nthemi~, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xal.~"ulll, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, T in-lçrni~ Lamium, 20 Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.

Dicotyledonous crops of the ~;enera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisurn, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, 25 Brassica, Lactuca, Cucumis, Cucurbita.

Monocotyledonous weeds of the ~;enera: Echinochloa, Setaria, Panicurn, Di~it~ri~, Phleum, Poa, Festuca, Eleusine, Br~chi~ri~ Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, 30 Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.

- ~ 220~ 596 Le A 30 586 - 28 -Monocot,vledonous crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.

However, the use of the active sllbst~nces according to the invention is in no way 5 restricted to these genera but also covers other plants in the same way.

Depending on the concentration, the compounds are suitable for total weed control.
e.g. on intlll~tn~l sites, along railway tracks and on paths and other locations, whether they are planted with trees or not. The compounds can also be used for 10 weed control in perm~nent crops, e.g. forest, orn~ment~l copses, orchards.
vineyards, citrus fruit, nut, banana, coffee, tea, rubber, oil palm, cocoa and berry plantations and hop fields, and on lawns, sports turf and pastures, and for selective weed control in annual crops.

15 The compounds of the formula (I) according to the invention are particularly suitable for the selective control of dicotyledonous weeds in monocotyledonous crops, both as a pre-emergence treatment and as a post-emergence treatment.

Furthermore, the active substances of the formula (I) according to the invention20 also exhibit an h~lele~ g fungicidal action against phytopathogenic fungi, especially Venturia inaequalis, and also to a certain extent against Pyriculariaoryzae, e.g. on rice.

The active substances can be converted to the conventional formulations such as 25 solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension/emulsion concentrates, natural and synthetic substances impregnated with active substance, and very small polymer capsules.

These formulations are prepared in known manner, e.g. by mixing the active 30 substances with extenders, i.e. liquid solvents and/or solid carriers, optionally with the use of surface-active agents, i.e. emulsifiers and/or dispersants and/or foaming agents.

Le A 30 586 - 29 - 2 2 0 1 5 q 6 In the case where water is used as an e~t~n~ler, it is also possible to use e.g.organic solvents as co-solvents. Suitable liquid solvents are essentially aromatics such as xylene, toluene or alkyln~rhth~lenes~ chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chloroben7enes, chloroethylenes or methylene 5 chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutylketone or cyclohexanone, strongly polar solvents such as dimethylform~mi~le and dimethyl sulphoxide, and water.
Suitable solid carriers are e.g. amrnonium salts, natural crushed rocks such as kaolins, clays, talcum, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic crushed rocks such as highly disperse silicic acid, aluminium oxide and silicates; suitable 15 solid carriers for granules are e.g. broken and fractionated natural rocks such as calcite, marble, purnice, sepiolite and dolomite, synthetic granules of inorganic and organic flours and ~r~nllles of organic m~teri~l such as sawdust, coconut shells, maize cobs and tobacco stems, suitable em~ ifiers and/or foaming agents are e.g.non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, 20 polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkylsulphonates, alkylslllph~tes, arylsulphonates and protein hydrolyzates; andsuitable dispersants are e.g. lignin sulphite spent liquors and methyl cellulose.

The formulations can contain tackifiers such as carboxymethyl cellulose, natural25 and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, natural phospholipids such as cephalins and lecithins, and synthetic phospholipids. Other possible additives are mineral and vegetable oils.

30 It is possible to use colorants such as inorganic pigments, e.g. iron oxide, titanium oxide and Prussian blue, and organic dyes such as alizarin, azo and metal phthalo-cyanine dyes, and kace nutrients such as salts of iron, m~ng~nese, boron, copper, ~ Le A 30 586 ~ - 30 - 2 2 0 ~ 5 ~) ~
cobalt, molybdenum and zinc.

The formulations generally contain between 0.1 and 95 per cent by weight of active substance, preferably between 0.5 and 90%.

The active substances according to the invention, either as such or in their formulations, can also be used as a mixture with known herbicides for controlling weeds, possible compositions being finished formulations or tank lni2~lules.

10 The mixtures can contain known herbicides, for example anilides such as e.g.
diLlurenican and propanil; arylcarboxylic acids such as e.g. dichloropicolinic acid, dicamba and picloram; aryloxyalkanoic acids such as e.g. 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoic acid esters such as e.g. diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and15 quizalofop-ethyl; azinones such as e.g. chloridazone and norflurazone; carbamates such as e.g. chlorpropham, desmedipham, phenmedipham and propham; chloro-acetanilides such as e.g. alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; dinitroanilines such as e.g. oryzalin, pendimethalin and trifluralin; diphenyl ethers such as e.g. acifluorfen, bifenox, fluoroglycofen, 20 fomesafen, halosafen, lactofen and oxyfluorfen; ureas such as e.g. chlortoluron, diuron, fluometuron, isoproturon, linuron and methabçn7thi~7llron; hydroxylamines such as e.g. alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim;
imidazolinones such as e.g. imazethapyr, im~7~methabenz, imazapyr and imazaquin;nitriles such as e.g. bromoxynil, dichlobenil and ioxynil; oxy~et~mides such as e.g.
25 mefenacet; sulphonylureas such as e.g. amidosulfuron; bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, metsulfuron-methyl, nicosul~uron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasul~ron and tribenuron-methyl; thiolcarbamates such as e.g. butylate, cycloate, ~ te, EPTC, esprocarb, molinate, prosulfocarb, thi~hencarb and triallate; triazines such as e.g.
30 atrazine, cy~n~7ine, ~im~7ine, simetryne, terbutryne and terbutylazine; triazinones such as e.g. hexazinone, metamitron and metribuzin; and other herbicides such ase.g. aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopyralid, 220~596 LeA30586 -31 -difenzoquat, dithiopyr, etho~lm~c~te, fluorochloridone, glufosinate, glyphosate,isoxaben, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.

The active substances according to the invention can also be mixed with other 5 known active substances such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and soil conditioners.

The active substances can be applied as such, as their formulations or as application forms prepared theLerlo,l, by fi~rther dilution, such as ready-to-use solutions,10 suspensions, emulsions, powders, pastes and granules. They are applied in conventional manner, e.g. by watering, spraying (large or small volume application) or sc~tterin~

The active substances according to the invention can be applied to the plants either 15 as a pre-emergence tre~tment or as a post-emergence tre~tment They can also be incorporated into the soil prior to sowing.

The amount of active substance used can vary within relatively wide limits. It depends essentially on the type of effect desired. The amounts applied are 20 generally between 10 g and 10 kg of active substance per hectare of soil surface, preferably between 50 g and 5 kg per ha.

The Examples which follow illustrate the preparation and use of the active substances according to the invention.

Le A 30 586 - 32 -Plc~ ~oly FY~n~rles:

F,Y~mrle 1 )~
N=~

10 (Process (a)) A mixture of 1.9 g (10 mmol) of 4-ethoxy-S-ethylthio-2,4-dihydro-3H-1,2,4-triazol-3-one, 2.7 g (11 mmol) of 2-methoxycarbonyl-phenylsulphonyl isocyanate and 50 ml of acetonitrile is stirred for 16 hours at 20C. After concentration under a 15 water-~et vacuum, the residue is digested with diethyl ether and the crystalline product is isolated by suction filtration.

This gives 3.9 g (91% of theory) of 4-ethoxy-5-ethylthio-2-(2-methoxycarbonyl-phenylsulphonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one melting at 162C.

FY~nrle 2 ,~ COOCH3 o N =~
S-CH=C=CH2 (Isomerization) A mixture of 2.8 g (6 mmol) of 4-ethoxy-5-propargylthio-2-(2-methoxycarbonyl-phenylsulphonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one (8), 50 ml of 220 1 5q6 LeA30586 -33 -methylene chloride, 50 ml of water, 0.3 g (7.5 mmol) of sodium hydroxide and 50 mg of tetrabutylammonium bromide is stirred for 16 hours at 20C. It is then acidified with 2 N hydrochloric acid and the organic phase is separated off, dried over m~gnecium sulphate and filtered. The filtrate is conc~ d, the residue is digested with diethyl ether and the crystalline product obtained is isolated by suction filtration.

This gives 2.0 g (71% of theory) of 4-ethoxy-5-(propa-1,2-dienylthio)-2-(2-methoxycarbonyl-phenylsulphonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one melting at 144C.

FY~mllle 3 H3C~ ~OCH3 ~ o N=~

(Process (d)) A mixture of 3.2 g (20 mmol) of 4-methoxy-5-methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one, 7.6 g (24 mmol) of 2-(N-methoxy-N-methylaminosulphonyl)-benzenesulphonyl chloride (95%), 2.6 g (40 mmol) of sodium cyanate, 1.2 g (15 rnrnol) of pyridine and 50 ml of acetonitrile is stirred for 2 days at 20C. After concentration under a waterjet vacuum, the residue is taken up with methylene chloride/water and adjusted to pH 3 with 2 N hydrochloric acid. The organic phase is then separated off, dried over sodiurn sulphate and filtered. The filtrate isconcentrated under a waterjet vacuurn and the residue is cr~stallized by treatment with methanol.

This gives 5.7 g (61% of theory) of 4-methoxy-5-methylthio-2-[2-(N-methoxy-N-Le A 30 586 ~ - 34 - 220 1 S q6 methyl-aminosulphonyl)-phenylsulphonyl-aminocarbonyl]-2,4-dihydro-3H-1,2,4-triazol-3-one melting at 185C.

The compounds of the formula (I) listed in Table 1 below can also be prepared, for 5 example, analogously to these Examples and in accordance with the general description of the preparatory processes according to the invention.

So2_N ~N N--O R (I) ~S(O)n-R2 220~596 Le A 30 586 - 35 -Table 1: Preparatory Examples of the compounds of the formula (I) Ex n Rl R2 R3 Physical no data 4 0C2H5 CH8 ~COOCH3 m.p.: 179C

0C2H5C3H7~n [~COOCH3 m.p.: 150C

6 C2H5CH(CH3)2 ~COOCH3 m.p.: 124C

7 0C2H5CH2-CH=CH2[~COOCH3 m.p.: 142C

8 C2H5CH2-C_CH ~COOCH3 m.p.: 133C

9 0C2H5 CH3 ~OCHF2 m.p.: 163C

C2Hs CH3 ~CF3 m.p.: 193C

Il C2Hs CH3 ~OCF3 m.p.: 165C

220 l 596 Le A 30 586 - 36 -Table 1 (Continl-~tion) no n Rl R2 R3 Physical 12 C2H5 CH3 ~Br m.p.: 188C

13 C2H5 CH3 ~COOC2Hs m.p.: 156C

14 C2H5 CH3 ~COOC3H7 m.p.: 108C

15 C2Hs CH3 [~OC2Hs m.p.: 140C

16 C2H5 CH3 ~SCH3 m.p.: 188C

17 C2H5 CH3 ~SC2Hs m.p.: 147C

18 C2Hs CH3 ~CH3 m.p.: 134C

19 C2H5 C2H5 [~OCHF2 m.p.: 143C

=
22o l5~6 Le A 30 586 - 3;' -Table 1 (Continn~tion) Ex. n Rl R2 R3 Physical no. data 20 C2H5 C2H5 [~CF3 m.p.: 163C

21 C2H5 C2Hs ~OCF3 m.p.: 141C

22 C2H5 C2Hs ~COOC2Hs m.p.: 92C

23 C2H5 C2Hs 3~COOC3H7n m.p.: 95C

24 C2H5 C2Hs ~OCH3 m.p.: 132C

25 C2H5 C2H5 [~OC2H5 m.p.: 138C

26 C2H5 C2H5 [~SCH3 m.p.: 180C

27 C2H5 C2H5 [~SC2Hs m.p.: 143C

28 CH3 C3H7-n 3~COOCH3 m.p.: 129C

Le A 3Q 586 - 38 - i~21~ 1 5 96 Table 1 (Co~ lion) ~. n Rl R2 R3 Physical no. data 29 CH3 CH3 ~COOCH3 m.p.:159C

0 C2H5 C2Hs ~ Br m.p.:157C

31 0 CH3 CH3 ~ COOC2Hs m.p.:178C

32 CH3 CH3 ~ COOC3H7-n m.p.:148C

33 0 CH3 CH3 ~ Br m.p.:183C

34 0 CH3 CH3 ~CF3 m.p.:l85C

0 CH3 CH3 ~OCF3 m.p.:l60C

36 CH3 CH3 ~OCH3 m.p. 149C

37 0 CH3 CH3 ~ OC2Hs m.p.:175C

220 15q6 Le A 30 586 - 39 -Table 1 (Continll~tion) Ex. n Rl R2 R3 Physical no. data 38 CH3 CH3 0~SCH3 m.p.: 192C

39 0 CH3 CH3 ~SC2Hs m.p.: 144C

0 CH3 CH3 . ~OCHF2 m.p.: 159C

41 CH3 CH3 ~CH3 . m.p.: 130C

42 CH3 CH3 ~ 3 m.p.: 151C

43 0 CH3 CH3 ~CI m.p.: 168C

44 0 CH3C3E~7~ COOCH3 m.p.: 156C

0 CH3 CH3 ~CI m.p.: 170C

~ 220 1 5 96 Le A 30 586 - 40 -Table 1 (Continl~tion) Ex. n Rl R2 R3 Physical no. data 46 CH3CH2-CH=CH2[~COOCH3 m.p.: 126C

47 0 CH3C2Hs 0~COOCH3 m.p.: 151'C

48 CH3C2Hs ~COOC2Hs m.p.: 129C

49 0 CH3C2Hs ~COOC3H7-n m.p.: 105C

SO CH3C2H5 . [3~Br m.p.: 137C

51 0 CH3C2H5 [~CF3 m.p.: 150C

52 CH3C2Hs @~OCF3 m.p.: 135C

53 0 CH3C2Hs ~[~OCH3 m.p.: 158C

54 0 CH3C2Hs ~OC2Hs m.p.: 164C

220 1 5 q6 Le A 30 586 - 41 -Table 1 (Contiml~tiQn) Ex. n Rl R2 R3 Physical no. data 55 0 CH3 C2Hs~SCH3 m.p.:l72C

56 CH3 C2Hs~ SC2Hs m.p.:148C

57 0 CH3 C2H5~ OCHF2 m.p.:l27C

58 0 CH3 C2H5~CH3 m.p.:124C

59 0 CH3 C2H5~ ,OCH3 m.p.:161C

CH30 ~
60 CH3 C2HS~ Cl m.p.:138C
~`

61 CH3 C2Hs~CI m.p.:124C

62 CH3 C2HS / m.p.:153C

~ COOCH3 220 1 5~6 LeA30586 -42-Table 1 (continll~tion) Ex. n Rl R2 R3 Physical no. data 63 CH3 CH3 ~ m.p.: 146C

~ N CH3 64 CH3 CH3 ~CF3 m.p.: 156C

~CH2-CH3CH2-CaCH ~COOCH3 m.p.: 110C

66 CH3CH2-CH2-F 3~COOCH3 m.p.: 148C

67 CH3CH2~ ~COOCH3 m.p.: 133C

68 CH3CH2-CH2-CI [~COOCH3 m.p.: 100C

69 CH3CH2CI ~COOCH3 m.p.: 142C

0 CH3C2Hs ~ m.p.: 153C

2 2 0 1 5 9 ~

Le A 30 586 - 43 -Table 1 (Continll~tion) Ex. n Rl R2 R3 Physical no. data 71 0 CH3 C2Hs ~OCHF2 m.p.: 124C

72 CH3 C2Hs ~ocH2-cH=cH2 m.p. 136C

73 0 CH3 C2Hs ~F m.p.: 149C

74 0 -C(CH3)3 CH3~COOCH3 m.p.: 139C

75 0 -C(CH3)3 C2Hs ~COOCH3 m.p.: 133C

22~) ~ 596 ., LeA30586 -44-The compound listed in Table 1 as Example 62 can be prepared for example as follows:
O o /S2 - NH~--N N--OCH3 ~COOCH3 S-C2Hs (Process b) A lni~Lu~c~ of 3.8 g (13 mmol) of 5-ethylthio-4-methoxy-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one,2.9 g (13.1 mmol) of 2-methoxycarbonyl-thiophene-3-sulphonamide, 2.0 g (13.2 mmol) of diazabicycloundecene (DBU) and 50 ml of acetonitrile is stirred for 3 days at 20C. It is then poured into a mixture of methylene chloride and aqueous hydrochloric acid (ca. 10%) and stirred thoroughly.
The organic phase is separated off, washed with water, dried and concentrated.
The residue is crystallized from diethyl ether.

This gives 2.0 g (36.5% of theory) of 5-ethylthio-4-methoxy-2-(2-methoxycarbonyl-thiophen-3-yl-sulphonylaminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one in the form of colourless crystals melting at 153C.

Startin~ materials of the formula (II):

Example (II-l) o H NJI\N - o-c2H5 N :=~

A mixture of 4.0 g (20 rnmol) of the potassium salt of 4-ethoxy-5-mercapto-2,4-dihydro-3H-1,2,4-triazol-3-one, 4.3 g (30 mmol) of methyl iodide and 50 ml of ''- 2201596 LeA30586 -45 -methanol is stirred for 16 hours at 20C and then concentrated. The residue is shaken with methylene chloride/water and the organic phase is separated off, dried over m~gn~sium s7llph~te and filtered. The filtrate is concentrated, the residue is digested with diethyl ether and the crystalline product obtained is isolated by 5 suction filtration.

This gives 1.8 g (51% of theory) of 4-ethoxy-5-methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one melting at 99C.

10 The compounds of the formula (II) listed in Table 2 below can also be prepared, for example, analogously to Example (II-l).

Le A 30 586 - 46 -Table 2: Examples of ~e compounds of the formula (II) H_NlN_O-R' N ~ (Il) S(O)n-R2 Ex. n Rl R2 R3 Physical no. data II-2 C2H5 C2H5 m.p.: 83C
II-3 C2H5 C3H7-n (amorphous) II~ C2H5 C3H7-i (amorphous) II-S C2H5 CH2-CH=CH2 m.p: 30CC
II-6 C2H5 CH2-C=CH m.p.: 77C
II-7 CH3 CH3 m.p.: 156C
II-8 CH3 C2H5 m.p.: 135C
II-9 0 c~3 C3H7~n m.p.: 90C
II-10 CH3 C3H7-i m.p.: 89C
II-ll CH3 CH2-CH=CH2 m.p.: 70C
II-12 CH3 CH2-CsCH m.p.: 134C

~e A 30 586 - 47 -Table 2 (Continll~tion) no n Rl R2 R3 data II-14 CH3 CH2-CI m.p.: 94C
II-15 CH3 CH2-CH2-F m.p.: 96C
II-16 CH3 CH2-CH2-Cl m.p.: 152C

II- 19 0 CH3 . CH2-CF3 II-25 C2H~ CH2-CH2-II-26 C2H5. CH2-CHF2 II-28 oC3H7~n CH3 II-29 C3H7-i CH3 II-30 0C4Hg-n CH3 ~I-3 1 0CH2-CH=CH2 CH3 ~-~ 220 ~ 5 96 Le A 30 586 ~ - 48 -Table 2 (Continuation) Ex. n Rl R2 R3 Physicai no. data II-32 0 C3H7-n C2H5 II-33 0 C3H7-i C2H5 II-34 0 C4Hg-n C2H5 II-35 oCH2-CH=CH2 C2H5 II-42 CH3 CH2--<1 m.p.: 108C

II-43 C2Hs CH

II-44 0C3H7-n CH2--<1 LI-45 0C3H7-i CH2 <¦

II-46 0CH2-CH=CH2 CH2--<

220 7 5'~G
Le A 30 586 - 49 -Startin~ materials of the formula (IX):

Example (IX-1) o H--N J~ N--O-C2Hs N =~
SK

A mixture of 25.5 g (100 mmol) of 4-ethoxy-1-(phenoxythiocarbonyl)-semicarbæide, 6.9 g (50 mmol) of potassium carbonate and 150 ml of methanol is refluxed for ca. 10 nlillu~es. It is then concentrated, the residue is digested with isopropanol and the crystalline product is isolated by suction filtration.

This gives 21 g (100% of theory) of the potassium salt of 4-ethoxy-5-mercapto-2,4-dihydro-3H-1,2,4-triazol-3-one melting at 123C.

The compounds of the formula (IX) listed in Table 3 below can also be plepaled, for example, analogously to Example (IX-1):
o H--N J~ N--OR' (IX) N=~
SH

` 220~5~6 Le A 30 586 ~ - 50 -Table 3: Examples of the compounds of the formula (IX) Ex. no. Rl Physical data s IX-2CH3 (potassium salt~ m.p.: 221c IX-3C3H7-n (potassium salt) IX-4C3H7-i (potassium salt~
IX-5CH2-CH=CH2 (potassium salt) IX-6C4H9-n (potassium salt) IX-7C4H9-i (potassium salt) IX-8C4H9-s (potassium salt) IX-9~ (potassium salt) 15 Starting materials of the formula (XI):

Example (XI-l) H ~ ~ , O-C2H5 ~N~O-c6H5 70 g (0.4 mol) of phenyl chloro-thioformate are added dropwise at 0C to 15C
to a mixture of 47.6 g (0.4 mol) of 4-ethoxy-semicarbazide, 41 g (0.4 mol) of triethylamine and 400 ml of methylene chloride and the mixture is then stirred for a further 16 hours at 15C to 20C. The crystalline product obtained is then isolated by suction filtration.

This gives 85.7 g (84% of theory) of 4-ethoxy-1-(phenoxythiocarbonyl)-semicarbazide melting at 153C.

~ 2201596 Le A 30 586 - 5 1 -The compounds of the formula (XI) listed in Table 4 below can also be pl~aled, for example, analogously to Example (XI~

N NH (Xl) ~ . 22~)l5~6 LeA30586 -52-Table 4: Examples of the compounds of ~e formula (XI) E,Y. Rl Y data no.

Xl-2 CH3 0~ m.p.: 172C

~ 3 C3H7~n o~

XI-5 C4Hg-n XI-6 CH2-CH=CH2 CH2~ ~

XI-8 CH3 Cl X[-9 C2H5 Cl ~-10 C3H7~n Cl Xl-l 1 C3~7-i Cl XI-12 C4Hg-n Cl XI-13CH2-CH=CH2 Cl 220 7 5~6 Le A 30 586 - 53 -Table 4 (Continl.~tion) Ex. Rl Y Physical no. data X~-14 CH3 O-CH2~

~-16 CH3 OCH3 X~-17 C2H5 OCH3 XI-l 9 C2H5 OC2H5 XI-20 CH3 N ~ N

X~-2 1 C2H5 N ~ N

~-22 C3H7~n N ~ N

X~-23 CH2-CH=CH2 ~ N ~ N

XI-24 ~ O-CH

Le A 30 586 - 54 -Startin~ materials of the formula (XII):

Example (XII-l) 1~ / O-C2H~
NH NH

31 g (0.2 mol) of phenyl chloroformate are added dropwise at 0C, with stirring,to a mixture of 24.4 g (0.2 mol) of ethoxy~nine (50% aqueous solution), 100 ml of diethyl ether, 28 g (0.2 mol) of potassium carbonate and 10 ml of water. Whenthe evolution of gas has ceased, the organic phase is separated off, the aqueousphase is re-extracted with ethyl acetate and the combined organic phases are dried over m~gnesium sulphate and filtered. The filtrate is concentrated, the residue is taken up with 50 ml of ethanol, and 10 g (0.2 mol) of hydrazine hydrate are added.
After l~Lluxing for one hour, the reaction nlix~ is cooled and filtered. The filtrate is concentrated, the residue is digested with diisopropyl ether and thecrystalline product obtained is isolated by suction filtration.

This gives 23.4 g (98% of theory) of 4-ethoxy-semicarbazide melting at 83C.

The compounds of the formula (XII) listed in Table 5 below can also be prepared,fo~ çxalnple, 2nalog~u~1y to E~ampl~ 13:
o J~ / OR
H--N NH (Xll) ? 2 2 0 1 5 9 6 Le A 30 586 - 55 -Table 5: Fx~mples of the compounds of the f~rmlll~ (XII) Ex. Rl Physical data no.
XII-2 CH3 m.p.: 73C
XII-3 C3H7~n XII-4 C3H7-i XlI-5 C4Hg-n XII-6 CH2-CH=CH2 XII-7 ~= \

Starting materials of the formula IV:
Example (IV-1):
o, N =~

17.2 g (0.11 mol) of phenyl chloroformate are added dropwise at 20C to a thoroughly stirred mixture of 16.2 g (0.1 mol) of 4-methoxy-5-methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one, 4.4 g (0.11 mol) of sodium hydroxide, 100 mg of tetrabutylammonium bromide, 250 ml of water and 500 ml of methylene chloride and the reaction mixture is subsequently stirred for a further 16 hours. The organic 15 phase is separated off, washed with water, dried and concentrated. The oily residue is crys~lli7e-1 from ether.

LeA30586 -56-This gives 24.0 g (85% of theory) of 4-methoxy-5-methylthio-2-phenoxyc~l~ollyl-2,4-dihydro-3H-1,2,4-triazol-3-one in the form of colourless crystals melting at113C.

5 The compounds of the formula (IV) listed in Table 6 below can also be prepared, for example, analogously to Example (IV-l).

- ~ 2201~96 Le A 30 586 ~ - 57 -Table 6: Examples of the compounds of the formula (IV) where n = O

O

S N~( S(O)n-R

Ex no. Rl R2 Z Physical da~

IV-2 CH3 C2H5 ~0-IV-3 CH3 C3H7-n ~o IV~ CH3 C3H7-i ~0 IV-5 CH3 CH2-CH=CH2 ~o IV-6 CH3 CH2-C_CH

Le A 30 586 - - 58 -Table 6 (contin7l~tion) Ex no. Rl R~ Z Physical da~a IV-9 CH3 CHF2 ~o IV-l 1 CH3 CH2-CH2-CI ~

IV-12 CH3 CH2-CHF2 ~o-IV-13 CH3 CH2-CF3 ~0-IV-14 CH3 CH2-cH2-cF3 <~

IV-15 CH3 CH=C=CH2 ~0 IV- 16 CH3 CH2~ ~ O-IV-17 CH3 cH2~ ~o-Le A 30 586 - - 59 - 220 1 5 9 6 Table 6 (continll~tion) Ex no. R' R2 Z Physical da~

IV-18 CH3 C4Hg-n ~O

IV-19 C2H5 C2H5 ~O-IV-20 C2H5 C3H7-n ~O

IV-21 C2H5 C3H7-i ~o_ IV-22 C2H5 CH2-CH=CH2 ~o_ IV-23 C2H5 CH2-C_CH ~

IV-24 C2H5 CH2-F ~O

IV-25 C2H5 CH2-Cl ~o IV-26 C2H5 CHF2 ~o Le A 30 586 - 60 -Table 6 (co,,~ion) Ex no. Rl R2 Z Physical da~a IV-28 C2H5 CH2-CH2-Cl ~

IV-29 C2H~ CH2-CHF2 ~O-IV-30 C2H5 CH2-CF3 ~o IV-3 I C2H5 CH2-CH2-CF3 ~

IV-32 C2H5 CH=C=CH2 ~O

IV-3 3 C2H5 CH2~ ~ O

IV-34 C2H5 ~ ~

IV-35 C2H5 C4Hg-n ~o 7~ 220 1596 LeA30 586 - -61 -Table 6 (continll~tion) Ex no. Rl R2 Z Physical da~

IV-36 C2H5 C2H5 ~O-IV-37 C3H7~n C3H7-n ~O

IV-38 C3H7~n C3H7-i ~o_ IV-39 C3H7~n CH2-CH=CH2 ~o_ IV-40 C3H7~n CH2-C-CH ~

IV~lC3H7~n CH2-F ~O-IV~2 C3H7~n CH2-CI ~o_ IV-43 C3H7~n CHF2 ~O_ IV~4 C3H7-n CH2-CH2-F ~

~?2 J 1 5 ~6 LeA30586 -62-Table 6 (Continll~tion) Ex no. R' R2 Z Physical data IV-4~ C3H7~n CH2-CH2-Cl ~__ IV-46 C3H7~n CH2-CHF2 ~o-IV~7 C3H7~n CH2-CF3 IV~8 C3H7-n CH2-CH2-CF3 ~

IV~9 C3H7~n CH=C=CH2 ~O

IV-50 C3H7-n CH2 <I ~o IV-5 1 C3H7-n cH2~ ~o-IV-52 C3H7~n C4Hg-n <~o IV-53 C3H7~n C2Hs ~o--220~596 Le A 30 586 - 63 -Table 6 (Continll~tion) Ex no. R' R2 Z Physical data IV 54C3H7~n C3H7-n ~o IV-55CH2-CH=CH2 C3H7-i ~O

IV-56CH2-CH=CH2 CH2-CH=CH2 ~O

IV-57CH2-CH=CH2 CH2-C_CH ~

IV-58CH2-CH=CH2 CH2-F ~O

IV-59CH2-CH=CH2 CH2-CI ~o_ IV-60CH2-CH=CH2 CHF2 ~ o_ IV-6 ICH2-CH=CH2 CH2-C~2-F ~ O-IV-62CH2-cH=cH2 CH2-CH2-CI ~

Le A 30 586 - 64 - 22 0 ¦ 5 '~ 6 Table 6 (continll~tion) Ex no. Rl R2 Z Physical da~a IV-63 CH2-CH=CH2 CH2-CHF2 ~o IV-64 CH2-CH=CH2 CH2-CF3 ~o IV-65 CH2-cH=cH2CH2-CH2-CF3 ~

IV-66 CH2-CH=CH2CH=C=CH2 ~ 0 IV-67 CH2-cH=cH2 C~t2~ ~o IV-68 CH2-CH=CH2 CH ~ ~o-IV-69 CH2-CH=CH2 C4H9~n ~

LeA30586 -65- 22015~6 Application Examples:

The following compound:

SO2 - NH \ (A) N =(~

i.e. 4-amino-5-methylthio-2-(2-trifluoromethoxy-phenylsulphonyl-aminocarbonyl)-2,4-dihydro-3H- 1,2,4-triazol-3-one (known from EP-A 431291 /LeA 27156), is usedfor comparison in the Application Examples below.

15 Example A

Post-emergence test Solvent: 5 parts by weight of acetone 20 Emulsifier: 1 part by weight of alkylaryl polyglycol ether An a~plol)liate active substance formulation is prepared by mixing 1 part by weight of active substance with the indicated amount of solvent, adding the indicated amount of em~ ifier and diluting the concentrate to the desired concentration with 25 water.

The active substance formulation is sprayed onto test plants with a height of 5 -15 cm so that the apprul liate desired amounts of active substance are distributed per unit area. The concentratior of the spraying mixture is chosen so that the 30 al~l,lopliate desired amounts of active substance are distributed in 2000 l of water/ha. After three weeks the degree of damage to the plants is evaluated in %damage compared with the development of the untreated control.

LeA30586 - -66- 2231 596 0% = no action (as ~ ea~d control) 100% = total destruction In this test the compounds of Preparatory Examples 1, 2, 4, 5, 6, 7 and 8, for 5 example, all exhibit very good compatibility with crop plants, e.g. wheat, but an appreciably more potent action on weeds than the known compound (A). The same also applies to the compounds of Preparatory Examples 22, 29, 31 and 48 (see Table A).

Le A 30 586 - 67 - 2201 ~ 9 ~
Table A: Post-emergence test/greenhouse ~ E O c~

~C , O o cn 3 .
O

O o o ~3 o ~

V r' ,~ s ~ ~ o ~ o Q
Q ~ n s O

~ =< ~ ~ O=~ ~
~ 0~ ~ Z
~ ' O O

LeA30586 - -68- 2201 596 Table A (Co"~ u;1lion~

~ E ~n X ~
~ E O~ O
o c~
' o~ o _ ~ o o O E v. ~
O

W S C~ CJ~

w o .~
-- _ 3 w ~ ' C
N IU t~ I
O ~ O
o=~ 1, o=( ~1' 8 z~ Z ,_ z~Z

C, C~ C 0~

~ 2201 596 =
., ,~
Le A 30 586 - 69 -Table A (Continll~tion) c E o X ' O E ~ o v~ c ,, e O
cd 1 3 8 . 8 ~,, c _ _ c o ~ ~ o c .~ cr~ 00 v ~

E ' oo ~ V~ o .
Q U'~
Q ~ C`l W _ _ O ~
E ~" N

0~ ~ 0~ ~

,> 0=~ ~ =
I C /
~D oN oN
>~
/~

Le A 30 586 - 70 - ~ 2 0 1 5 q 6 Table A (Continuation) ~ E ~5~ o X c c~ ~ o ~, c~ c . ~ o o ~ t, G.~ , C O t_ C .3 o ~) ~

O ~_ O
.
~ ur~ v~
o ~

c,~ 1~, ~, O I O C~
o=( ~
Q =~ _ z_ _ o o~ O

Activesubs~ance (ofP,~pa,~lorv Amountapplied Whea~ Ama- Cheno- Heli- Matri- Sola- Xan- E- ~, Exampleno.) (olha) ranthus podlum r~nthus caria num thium ~ o i .

(22) 60 10 95 80 lO0 90 90 100 (29) 60 l 0 80 90 90 80 95 (3 1) 60 5 80 80 70 - 95 (48) 125 lO 80 80 tO0 90 80 lO0 ~1 o 2~0 ~ ~56 ~e A 30 586 - 72 -Example B

Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether An ~L,plopliate active substance formulation is prepared by mixing 1 part by weight of active substance with the indicated amount of solvent, adding the indicated 10 amount of emulsifier and diluting the concentrate to the desired concentration with water.

Seeds of the test plants are sown in normal soil. After 24 hours the soil is watered with the active substance formulation, the amount of water per unit area advantageously being kept constant. The active substance concentration in the formulation plays no part, the only decisive factor being the amount of active substance applied per unit area. After three weeks the degree of damage to the plants is evaluated in % damage compared with the development of the untreated control.
0% = no action (as untreated control) 100% = total destruction In this test the compounds of Preparatory Examples 1, 4, 5, 6, 7 and 8, for example, exhibit an appreciably more potent action on weeds than the known compound (A). The same also applies to the compounds of Preparatory Exarnples 11, 12, 22, 29, 31, 33, 34,35 and 47 (see Table B).

~2U I 5~6 LeA30586 -73 -Table B: Pre-emergence test/greenhouse a> ~
o o o ,,, ~Q ~ .
. u~
o o . ~ ~ O~

~-r ~ ~ o .
~ o ~

o o~

~ o .

¢ ~
I
O ~) a) 0~ 0=< ~/
Z Z
~ ~\-- _~Oa~I
a) ~o I

6 ~ o o~
~\ /> ~

Active substance Amount applicd Galium Galin- Matri- Sinapis Sola- Stel- w (~/ha) sogacaria num laria ~.

[~so, N)l N~ ~ ~ ' æ

S-C2Hs (1) 1:!5 8~ 9s 95 95 9~ 9S

so ~ j N
N=~
~C3H7-n 5) 1 25 90 95 95 -90 80 90 r~

O .

~n 220~ ~9i -- LeA30586 -75-Table B (co,~ lion) c~ ~ O OC

O E "0 ~
ul co ~_ O` `

3 o ~
-O ~ _ _ ~ ~ .

I~ I '' :r C, I
~o Z

o =~ `O =~
~ o~ ~

220 ~ 5q6 LeA30586 -76-Table B (continll~tion) ~ ~ o O r oo cn . u~

-r ce~ O

~ CC~ o .C' -c c ~

O

O =~ I
I Z
~ o ~

t Active substance (of PreparatoryAmount applied Galium Galin- Matri- Sinapis Sola- Stel- ~ ~
Example no.) (glha) soga caria num laria W O

o (I l) 125 - 95 95 95 95 95 (12) 125 - 95 95 90 95 (22) 250 95 95 95 70 95 95 (29) 125 - 95 95 9S 95 95 (31) 125 - - 100 100 95 95 70 (33) 250 - 80 90 95 80 (34) 125 - 100 95 95 95 go (35) 125 - 95 95 95 95 95 (47) 125 - 95 95 90 95 95 t~

2201 5q6 Le A 30 586 - 78 -Exa~nple C

Venturia test (apple)/protective 5 Solvent: 4.7 parts by weight of acetone F.m~ ifier: 0.3 part by weight of alkylaryl polyglycol ether An a~ropl;ate active substance form~ tion is prepared by mixing 1 part by weightof active substance with the indicated amounts of solvent and emlll~ifier and 10 diluting the concentrate to the desired concentration with water.

To test for protective efficacy, young plants are sprayed with the active substance formuiation until they are dripping wet. After the sprayed surface has dried, the plants are inoculated with an aqueous conidia suspension of the apple scab 15 pathogen Venturia inaequalis and are then left to stand for 1 day at 20C and 100% relative humidity in an incubation chamber.

The plants are then placed in the greenhouse at 20C and a relative humidity of ca. 70%.
They are evaluated 12 days after inoculation.

In this test the compounds of Preparatory Examples 1, 4, 5 and 6, for example, exhibit 100% efficacy at an active substance concentration of 10 ppm.

LeA30586 - 79 220~ ~96 Table C: Venturia test (apple)/protective Active substance Efficacy in % of the untreated control at an active substance concentration of 10 ppm]
~COOCH3 ~J\SO2_NH)~N N--~ 2 5 N=~

(1) 100 J~

(4) 100 ~52 N )~ N ~N 2 5 (5) 100 J~

S-CH(CH3)2 (6) 1 00

Claims (10)

claims

1. Sulphonylaminocarbonyltriazolinones with substituents bonded via oxygen and sulphur of the general formula (I):

(I) in which n is the number 0, 1 or 2, R1 is hydrogen or an optionally substituted radical from the group comprising alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, aryl and aralkyl, R is an optionally substituted radical from the group comprising alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, aralkyl and aryl, and R3 is an optionally substituted radical from the group comprising alkyl, aralkyl, aryl and heteroaryl, and salts of compounds of the formula (I), the following compounds being excluded: 4-methoxy-5-methylthio-2-(2-methoxycarbonyl-phenylsulphonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one, 4-ethoxy-5-ethylthio-2-[2-(N-methoxy)-methylaminosulphonyl-phenyl-sulphonyl-aminocarbonyl]-2,4-dihydro-3H-1,2,4-triazol-3-one, 4-propoxy-5-allyl-thio-2-(2-methyl-phenylsulphor l-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3 -one, 4-methoxy-5-methylthio-2-(2-methoxycarbonyl-thien-3-yl-sulphonyl-amino-carbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one, 4-ethoxy-5-methylthio-2-(2-methoxy-phenylsulphonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one, 4-ethoxy-5-ethylthio-2-[2-(2-chloro-ethoxy)-phenylsulphonyl-aminocarbonyl]-2,4-dihydro-3H-1,2,4-triazol-3-one, 4-allyloxy-5-ethylthio-2-(2-fluoro-phenyl.~nlrh~ nyl-aminoca l,ollyl)-2,4-dihydro-3H-1,2,4-triazol-3-one, 4-methoxy-5-ethylthio-2-(3 -aminosulphonyl-pyridin-2-yl-sulphonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one and 4-methoxy-5-ethylthio-2-(2,6-difluoro-phenylsulphonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one.

2. Compounds of the formula (I) according to Claim 1, characterized in that n is the number 0, 1 or 2, Rl is hydrogen, Cl-C6-alkyl optionally substituted by fluorine, chlorine, bromine, cyano, Cl-C4-alkoxy, Cl-C4-alkyl-carbonyl or Cl-C4-alkoxy-carbonyl, C2-C6-alkenyl or C2-C6-alkinyl, each of which is optionally substituted by fluorine, chlorine and/or bromine, C3-C6-cycloalkyl or Cs-C6-cycloalkenyl, each of which is optionally substituted by fluorine, chlorine, bromine and/or Cl-C4-alkyl, or phenyl or phenyl-CI-C3-alkyl, each of which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, Cl-C4-alkyl, trifluoromethyl, Cl-C4-alkoxy and/or Cl -C4-alkoxy-carbonyl, R2 is C,-C6-alkyl optionally substituted by fluorine, chlorine, bromine, cyano, C3-C6-cycloalkyl, C,-C4-alkoxy, C,-C4-alkylthio or C,-C4-alkoxy-carbonyl, C2-C6-alkenyl or C2-C6-alkinyl, each of which is optionally substituted by fluorine, chlorine and/or bromine, C3-C6-cycloalkyl, Cs-C6-cycloalkenyl or C3-C6-cycloalkyl-C,-C3-alkyl, each of which is optionally substituted by fluorine, chlorine, bromine and/or C,-C4-alkyl, phenyl-CI-C3-alkyl optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C,-C4-alkyl, trifluoromethyl, C,-C4-alkoxy and/or Cl-C4-alkoxy-carbonyl, or phenyl optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C~-C4-alkyl, trifluoromethyl, C~-C4-alkoxy fluorine- and/or chlorine-substituted C,-C3-alkoxy, C,-C4-alkylthio, fluorine- and/or chlorine-substituted C,-C3-alkylthio, C,-C4-alkyl-sulphinyl, C,-C4-alkylsulphonyl and/or C,-C4-alkoxy-carbonyl, and R3 is the grouping wherein R4 and R5 are identical or different and are hydrogen, fluorine, chlorine, bromine, iodine, nitro, C1-C6-alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C4-alkoxycarbonyl, C1-C4-alkylamino-carbonyl, di-(C1-C4-alkyl)amino-carbonyl, hydroxyl, C1-C4-alkoxy, formyloxy, C1-C4-alkyl-carbonyloxy, C1-C4-alkoxy-carbonyloxy, C1-C4-alkylamino-carbonyloxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, di-(C1-C4-alkyl)-aminosulphonyl, C3-C6-cycloalkyl or phenyl), C2-C6-alkenyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxy-carbonyl, carboxyl or phenyl), C2-C6-alkinyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxy-carbonyl, carboxyl or phenyl), C1-C4-alkoxy (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C4-alkoxy-carbonyl,C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl), C1-C4-alkylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C4-alkoxy-carbonyl, C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl), C2-C6-alkenyloxy (which is optionally substituted by fluorine, chlorine, bromine, cyano or C1-C4-alkoxy-carbonyl), C2-C6-alkenylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C1-C3-alkylthio or C1-C4-alkoxycarbonyl), C3-C6-alkinyloxy, C3-C6-alkinylthio or the radical -S(O)p-R6, in which p is the number 1 or 2 and R6 is C1-C4-alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano or C1-C4-alkoxy-carbonyl),C3-C6-alkenyl, C3-C6-alkinyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkylamino, C1-C4-alkylamino, di-(C1-C4-alkyl)-amino, phenyl or the radical -NHOR7, in which R7 is C1-C12-alkyl (which is optionally substituted by fluorine, chlorine, cyano, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkyl-carbonyl, C1-C4-alkoxy-carbonyl, C1-C4-alkylamino-carbonyl or di-(C1-C4-alkyl)-amino-carbonyl),C3-C6-alkenyl (which is optionally substituted by fluorine, chlorine or bromine), C3-C6-alkinyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C2-alkyl, phenyl-C1-C2-alkyl (which is optionally substituted by fluorine, chlorine, nitro, cyano, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkoxy-carbonyl), benzllydlyl or phenyl (which is optionally substituted by fluorine, chlorine, nitro, cyano, C1-C4-alkyl, trifluoromethyl, C1-C4-alkoxy, C1-C2-fluoroalkoxy, C1-C4-alkylthio, trifluoromethylthio or C1-C4-alkoxy-carbonyl), R4 and/or R5 are also phenyl or phenoxy, C1-C4-alkyl-carbonylamino, C1-C4-alkoxy-carbonylamino, C1-C4-alkylamino-carbonyl-amino, di-(C1-C4-alkyl)-amino-carbonylamino or the radical -CO-R8, in which R8 is hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C3-C6-cycloalkoxy, C3-C6-alkenyloxy, C1-C4-alkylthio, C1-C4-alkylamino, C1-C4-alkoxyamino, C1-C4-alkoxy-C1-C4-alkylamino or di-(C1-C4-alkyl)-amino (which are optionally substituted by fluorine and/or chlorine), or R4 and/or R5 are also trimethylsilyl, thiazolinyl, C1-C4-alkylsulphonyloxy, di-(C1-C4-alkyl)-aminosulphonylamino or the radical -CH=N-R9, in which R9 is C1-C6-alkyl optionally substituted by fluorine, chlorine, cyano, carboxyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkyl-sulphinyl or C1-C4-alkylsulphonyl, benzyl optionally substituted by fluorine or chlorine, C3-C6-alkenyl or C3-C6-alkinyl, each of which is optionally substituted by fluorine or chlorine, phenyl optionally substituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, C1-C6-alkoxy, C3-C6-alkenoxy, C3-C6-alkinoxy or benzyloxy, each of which is optionally substituted by fluorine and/or chlorine, amino, C1-C4-alkylamino, di-(C1-C4-alkyl)-amino, phenylamino, C1-C4-alkyl-carbonyl-amino, C1-C4-alkoxy-carbonylamino, C1-C4-alkyl-sulphonylamino, or phenylsulphonylamino optionally substituted by fluorine, chlorine, bromine or methyl, or R3 is the radical wherein R10 is hydrogen or C1-C4-alkyl and R11 and R12 are identical or different and are hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C4-alkyl (which is optionally substituted by fluorine and/or chlorine), C1-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), carboxyl, C1-C4-alkoxycarbonyl, dimethylaminocarbonyl, C1-C4-alkylsulphonyl or di-(C1-C4-alkyl)-aminosulphonyl, or R3 is the radical wherein R13 and R14 are identical or different and are hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C4-alkyl (which is optionally substited by fluorine and/or chlorine) or C1-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), or R3 is the radical wherein R15 and R16 are identical or different and are hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C4-alkyl (which is optionally substituted by fluorine and/or chlorine), C1-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl (which are optionally substituted by fluorine and/or chlorine), aminosulphonyl, mono-(C1-C4-alkyl)-aminosulphonyl,di-(C1-C4-alkyl)-aminosulphonyl, C1 -C4-alkoxy-carbonyl or dimethylarninocarbonyl, or R3 is the radical wherein R17 and R18 are identical or different and are hydrogen, fluorine, chlorine, bromine, C1-C4-alkyl (which is optionally substituted by fluorine and/or bromine), C1-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl (which are optionally substituted by fluorine and/or chlorine) or di-(C1-C4-alkyl)-aminosulphonyl, or R3 is the radical wherein R19 and R20 are identical or different and are hydrogen, fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl (which is optionally substituted by fluorine and/or chlorine), C1-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl (which is optionally substituted by fluorine and/or chlorine), di-(C1-C4-alkyl)-amino-sulphonyl, C1-C4-alkoxy-carbonyl or dimethylaminocarbonyl, and A is oxygen, sulphur or the grouping N-Z1, in which Z1 is hydrogen, C1-C4-alkyl (which is optionally substituted by fluorine, chlorine, bromine or cyano), C3-C6-cycloalkyl, benzyl, phenyl (which is optionally substituted by fluorine, chlorine, bromine or nitro), C1-C4-alkyl-carbonyl, C1-C4-alkoxy-carbonyl or di-(C1-C4-alkyl)-aminocarbonyl, or R3 is the radical wherein R21 and R22 are identical or different and are hydrogen, C1-C4-alkyl, halogen, C1-C4-alkoxycarbonyl, C1-C4-alkoxy or C1-C4-halogenoalkoxy, and Y1 is sulphur or the grouping N-R23, in which R23 is hydrogen or C1-C4-alkyl, or R3 is the radical wherein R24 is hydrogen, C1-C4-alkyl, benzyl, pyridyl, quinolinyl or phenyl, R25 is hydrogen, halogen, cyano, nitro, C1-C4-alkyl (which is optionally substituted by fluorine and/or chlorine), C1-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), dioxolanyl or C1-C4-alkoxy-carbonyl, and R26 is hydrogen, halogen or C1-C4-alkyl, or R3 is one of the groupings listed below:

with the exception of the compounds excluded by disclaimer in Claim 1.

3. Compounds of the formula (I) according to Claim 1, characterized in that n is the number 0, 1 or 2, R1 is methyl, ethyl, n- or i-propyl or n-, i-, s- or t-butyl, each of which is optionally substituted by fluorine, chlorine, cyano, methoxy or ethoxy, propenyl, butenyl, propinyl or butinyl, each of which is optionally substituted by fluorine, chlorine or bromine, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, each of which is optionally substituted by fluorine, chlorine, bromine, methyl or ethyl, or benzyl or phenyl, each of which is optionally substituted by fluorine,chlorine, bromine, cyano, methyl, trifluoromethyl or methoxy, R2 is methyl, ethyl, n- or i-propyl or n-, i-, s- or t-butyl, each of which is optionally substituted by fluorine, chlorine, cyano, methoxy, ethoxy, methylthioor ethylthio, propenyl, butenyl, propinyl, butinyl or allenyl, each of which is optionally substituted by fluorine, chlorine or bromine, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, each of which is optionally substituted by fluorine, chlorine, bromine, methyl or ethyl, or phenyl or benzyl, each of which is optionally substituted by fluorine, chlorine, bromine, cyano, methyl, trifluoromethyl or methoxy, and R3 is the radical wherein R4 is fluorine, chlorine, bromine, methyl, ethyl, propyl, trifluoromethyl, butoxy, allyloxy, propargyloxy, methoxy, ethoxy, propoxy, isopropoxy, difluoromethoxy, trifluoromethoxy, 2-chloro-ethoxy, 2-methoxy-ethoxy, C1-C3-alkylthio, C1-C3-alkylsulphinyl, C1-C3-alkylsulphonyl, dimethylaminosulphonyl, diethylaminosulphonyl, N-methoxy-N-methylaminosulphonyl, methoxyaminosulphonyl, phenyl, phenoxy or C1-C3-alkoxy-carbonyl, and Rs is hydrogen, methyl, ethyl, fluorine, chlorine or bromine, or R3 is the radical wherein R10 is hydrogen, R11 is fluorine, chlorine, bromine, methyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methyl-sulphonyl or dimethylaminosulphonyl, and R12 is hydrogen, or R3 is the radical wherein R is C1-C4-alkyl, or R3 is the radical wherein R24 is C1-C3-alkyl, phenyl or pyridyl, R25 is hydrogen, fluorine, chlorine or bromine and R26 is fluorine, chlorine, bromine or C1-C3-alkoxy-carbonyl, with the exception of the compounds excluded by disclaimer in Claim 1.

4. Processes for the preparation of the compounds of the formula (I) according to Claim 1, characterized in that (a) triazolinones of the general formula (II):

(II) in which n, R1 and R2 are as defined in Claim 1, are reacted with sulphonyl isocyanates of the general formula (III):

R3-SO2-N=C=O (III) in which R3 is as defined in Claim 1, optionally in the presence of a reaction auxiliary and optionally in the presence of a diluent, or in that (b) triazolinone derivatives of the general formula (IV):

(IV) in which n, R1 and R2 are as defined above and Z is halogen, alkoxy, aralkoxy or aryloxy, are reacted with sulphonamides of the general forrnula (V):

R3-SO2-NH2 (V) in which R3 is as defined above, optionally in the presence of an acid acceptor and optionally in the presence of a diluent, or in that (c) triazolinones of the general formula (II):

(II) in which n, R1 and R2 are as defined above, are reacted with sulphonamide derivatives of the general formula (VI):

R3-SO2-NH-CO-Z (VI) in which R3 is as defined above and Z is halogen, alkoxy, aralkoxy or aryloxy, optionally in the presence of an acid acceptor and optionally in the presence of a diluent, or in that (d) triazolinones of the general formula (II):

(II) in which n, R1 and R2 are as defined above, are reacted with sulphonyl halides of the general formula (VII):

R3-SO2-X (VII) in which R3 is as defined above and X is halogen, and with metal cyanates of the general formula (VIII):

MOCN (VIII) in which M is an alkali metal or alkaline earth metal equivalent, optionally in the presence of a reaction auxiliary and optionally in the presence of a diluent, and the compounds of the formula (I) obtained by process (a),(b),(c) or (d) are optionally converted to salts by conventional methods.

5. Herbicidal and fungicidal compositions, characterized in that they contain at least one compound of the formula a) according to Claim 1.

6. Use of compounds of the general formula a) for controlling undesired plant growth and/or phytopathogenic fungi.

7. Triazolinones of the general formula (II):

(II) in which n is the number 0, 1 or 2, R1 is hydrogen or an optionally substituted radical from the group comprising alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, aryl and aralkyl, and R2 is an optionally substituted radical from the group comprising alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, aralkyl and aryl.

8. Triazolinone derivatives of the general formula (IV):

(IV) in which n is the number 0, 1 or 2, R1 is hydrogen or an optionally substituted radical from the group comprising alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, aryl and aralkyl, R2 is an optionally substituted radical from the group comprising alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, aralkyl and aryl, and Z is halogen, alkoxy, aralkoxy or aryloxy.

9. Mercapto-triazolinones of the general formula (IX):

(IX) in which R1 is hydrogen or an optionally substituted radical from the group comprising alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, aryl and aralkyl, and metal salts of compounds of the formula (IX):

10. Semicarbazide derivatives of the general formula (XI):

(XI) in which R1 is hydrogen or an optionally substituted radical from the group comprising alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, aryl and aralkyl, and Y is halogen, imidazolyl, alkoxy, aralkoxy or aryloxy.