CA2189593C - Sulphonylaminocarbonyltriazolinones having substituents bonded via oxygen - Google Patents

Abstract

The invention relates to novel intermediates of formula II useful in the preparation of sulphonylamino-carbonyltriazolinones having substituents bonded via oxygen and to salts thereof and to processes for preparing the intermediates. A compound of formula II is a triazolinone of the general formula (II)

Description

s ~is~~~3 The present divisional application is divided out of parent application Serial No. 2,064,636 filed on April 1, 1992.
The invention of the parent application relates to compounds of formula I, processes for preparing compounds of formula I, herbicidal compositions containing compounds of formula I and uses of the compounds of formula I, and compositions thereof, as herbicides.
The invention relates to new sulphonyl-aminocarbonyltriazolinones having substituents bonded via oxygen, to a plurality of processes and novel intermediates for their preparation, and to their use as herbicides.
It has been disclosed that certain substituted sulphonylaminocarbonyltriazolinones such as, for example, 2-(2-chloro-phenylsulphonylaminocarbonyl)-4,5-dimethyl-2,4-dihydro-3H-1,2,4-triazol-3-one have herbicidal properties (cf.
EP-A 341,489). However, the action of these compounds is not satisfactory in all respects.
Further sulphonylaminocarbonyltriazolinones such as, for example, 2-(2-methoxycarbonyl-phenylsulphonylamino-carbonyl)-4-methyl-5-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one are the subject of an earlier, but non-prior-published Patent Application (cf. German Patent 3,934,081 dated 12.10.1989).

~
~189~93 In accordance with one aspect of the parent application, there is--provided a sulphonylaminocarbonyl-triazolinone having a substituent bonded via oxygen, of the general formula (I) R3_gp2_ (I) in which R1 represents hydrogen, amino, C1-C4-alkyl which is optionally substituted by fluorine, cyano, methoxy or ethoxy, or represents allyl, C3-C6-cycloalkyl, benzyl, phenyl, C1-C3-alkylamino, C3-C6-cycloalkylamino or di-(C~_-C3-alkyl)-amino, R2 represents hydrogen, C1-C4-alkyl-which is optionally substituted by fluorine and/or chlorine, methoxy or ethoxy, or represents C3-C4-alkenyl which is optionally substituted by fluorine and/or chlorine, or represents C3-C6-cycloalkyl, or -represents phenyl or benzyl which is optionally substituted by fluorine, chlorine and/or methyl, and R3 represents the group RS _ ~ ~ 89393 where R4 represents fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, 2-chloro-ethoxy, 2-methoxy-ethoxy, Cl-C3-alkylthio, C1-C3-alkyl-sulphinyl, C1-C3-alkylsulphonyl, dimethylaminosulphonyl, diethylaminosulphonyl, N-methoxy-N-methylaminosulphonyl, methoxyaminosulphonyl, phenyl, phenoxy or C1-C3-alkoxy-carbonyl and R5 represents hydrogen, fluorine, chlorine or bromine, furthermore R3 represents the radical yo where _ _ R1~ represents hydrogen, R11 represents fluorine, chlorine, bromine, methyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, methoxy-carbonyl, ethoxycarbonyl, methylsulphonyl or dimethylamino-sulphonyl and R12 represents hydrogen;
furthermore R3 represents the radical -RO-C S
I I
O

i ~~8~593 where R represents Cl-C4-alkyl or represents the radical where R represents C1-C4-alkyl or a salt thereof, with the exception of the compounds 2-(2-methoxycarbonyl-phenylsulphonylaminocarbonyl)-4-methyl-5-methoxy-2,4-dihydro-3H-1,2,4-triazol-3.-one, 2-(2-trifluoro-_ methoxy-phenylsulphonylaminocarbonyl)-4-cyclopropyl-5-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one and 2-(2-difluoromethoxy-phenylsulphonylaminocarbonyl)-4-cyclobutyl-5-ethoxy-2,4-dihydro-3H-1,2,4-triazol-3-one.
In accordance with another aspect of the parent application there is provided a process for preparing a compound of formula I as defined above which process comprises (a) reacting a triazolinone of the general formula (II) (Id) 2_ ~~89593 in which Rl and R2 have the meanings given above with a sulphonyl isocyanate of the general formula (III) R3-S02-N=C=O (III) in which R3 has the meaning given above, or (b) reacting a triazolinone derivative of the general formula (IV) in which Rl and R2 have the meanings given above, and Z represents chlorine, Cl-C4-alkoxy, benzyloxy or phenoxy, with a sulphonamide of the general formula (V) R3-S02-NR2 (V) in which R3 has the meaning given above, or (c) reacting a triazolinone of the general formula (II) ~ ~18~~93 in which Rl and R2 have the meanings given above with a sulphonamide derivative of the general formula (VI) R3-S02-NH-CO-Z (VI}
in which R3 has the meaning given above and Z represents chlorine, Cl-C~-alkoxy, benzyloxy or phenoxy, and, where required, forming a salt thereof.
In accordance with one aspect of the divisional application, there is provided a triazolinone of the general formula (II) in which R1 represents amino, Cl-Cg-alkyl which is optionally substituted by fluorine, cyano, methoxy or ethoxy, or represents a11y1, C3-C6-cycloalkyl, benzyl, phenyl, C1-C3 alkylamino, C3-C6-cycloalkylamino or di-(Cl-C3-alkyl)-amino, ~1885~3 and R2 represents C3-C6-cycloaikyl, or represents phenyl or benzyl which is optionally substituted by fluorine, chlorine and/or methyl.
In accordance with another aspect of the divisional application there is provided a process for preparing a triazolinone of the general formula (II) O
H-N~N-R1 N
~Q_Rz in which R1 represents hydrogen, amino, Cl-C4-alkyl which is optionally substituted by fluorine, cyano, methoxy or ethoxy, or represents allyl, C3-C6-cycloalkyl-, benzyl, phenyl, Cl-C3-alkylamino, C3-C6-cycloalkylamino or di-(Cl-C3-alkyl)-amino, and R2 represents hydrogen, C1-C4-alkyl, which is optionally substituted by fluorine and/or chlorine, methoxy or ethoxy, or represents C3-C4-alkenyl which is optionally substituted by fluorine and/or chlorine, or represents C3-C6-cycloalkyl, or represents phenyl or benzyl which is optionally substituted by fluorine, chlorine and/or methyl, which process comprises heating a compound of the general formula (IX) C)-Rz Rz'-0-CO-NH-N=C ~ (IX) ~-Ri in which R1 represents hydrogen, amino, C~-C4-alkyl which is optionally substituted by fluorine, cyano, met:hoxy or ethoxy, or represents allyl, C'3-C6-cycloalkyl, benzyl, phenyl, C1-C3-alkyl amino, C3-C6-cycloalkylamino or di- (C1-C3-alkyl)-amino;
Rz represents hydrogen, C1-C4-alkyl which is optionally substituted by fluorine and/or chlorine, methoxy or ethoxy, or represents C3-C4-a:Lkenyl which is optionally substituted by fluorine and/or chlorine, or represents C3-C6-cycloalkyl, or represents phenyl or benzyl which is optionally substituted by fluorine, chlorine and/or methyl;
and Rz' represents methyl, ethyl or phenyl, at a temperature of from 50°C to 150°C.
In accordance with another aspect of the divisional application there :is provided a compound of the general formula (IX) O-Rz Rz'-O-CO-NH-N=C ~ (IX) in which Rl red?resents hydrogen, amino, C1-C4-alkyl which is optionally substituted by fluorine, cyano, methoxy or ethoxy, or represents al:lyl, C3-C6-cycloalkyl, benzyl, phenyl, C1-C3-alkyl.ami no, C3-C~;-cycloalkylamino or di- (C1-C3-alkyl)-amino; and R2 :represents C1-C4-alkyl which is optionally substituted by fluorine and/or chlorine, methoxy or ethoxy, or represents C3-C4-al7~;enyl which is optionally substituted by fluorine and/or chlorine, or represents C~-C6-cycloalkyl, ~~ or represents phenyl or benzyl which is optionally substituted by fluorine, chlorine and/or methyl; and R2' represents methyl, ethyl or phenyl.
In accordance with another aspect of the divisional application. there is provided a process for preparing a compound of the general formula (IX) as def_Lned above 8a _~~~9~~3 wherein R1 represents hydrogen, amino, C1-C4-alkyl which is optionally substituted by fluorine, cyano, methoxy or ethoxy, or repcesents allyl, C3-CS-cycloalkyl, benzyl, phenyl, C1-C3-alkylamino, C3-C6-cycloalkylamino or di-(C1-C3-alkyl)-amino, and R2 represents hydrogen, C1-C4-alkyl, which is optionally substituted by fluorine and/or chlorine, methoxy or ethoxy, or represents C3-C4-alkenyl which is optionally substituted by fluorine and/or chlorine, or represents C3-C6-cycloalkyl, or represents phenyl or benzyl which is optionally substituted by fluorine, chlorine and/or methyl, and ~189~93 RZ~ represents methyl, ethyl or phenyl, which process comprises reacting a hydrazinoformic ester of the general formula (VII) H2N-NH-CO-O-R2~ (VII) in which R2~ is as defined above, with an alkyliminocarbonic diester of the general formula (VIII) R1-N=C ' (VIII) ~ O-R2 in which R1 and R2 are as defined above, at a temperature of from 0°C to 50°C.

~ 2~89~~3 The compound 2-(2-metfoxycarbonyl-phenylsulphonyl-aminocarbonyl)-4-methyl-5-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one is disclosed in German Patent 3,934,081.
The new sulphonylaminocarbonyltriazolinones having substituents bonded via oxygen, of the general formula (I), are obtained when (a) triazolinones of the general formula (II) H-N~N-R' ~y~
~~-Rx ~189~93 in which R1 and R2 have the abovementioned meanings are reacted with sulphonyl isocyanates of the general formula (III) R3-S02-N=C=O (III) in which R3 has the abovementioned meaning, if appropriate in the presence=of a diluent, or when (b) triazolinone derivatives of the general formula (IV) O
Z-CO-N ~N-Rk ~O-Rz ~ 2189593 in which R1 and R2 have the abovementioned meanings and Z represents halogen, alkoxy, aralkoxy or aryloxy, are reacted with sulphonamides of the general formula (Vy, R3-s~2'NH2 (V) in which R3 has the abovementioned meaning, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or when (c) trlazolinones of the general formula (II) O
H-N. 'N-R1 N---~
~O-R2 in which R1 and R2 have the abovementioned meanings are reacted with sulphonamide derivatives of the general formula (VI) R3-802=NH-CO-Z (VI) in which R3 has the abovementioned meaning and ~~8~~~3 Z represents halogen, alkoxy, aralkoxy or aryloxy, if appropriate in the presence of an acid acceptor and it appropriate in the presence of a diluent and, if appropriate, salts are formed, by customary methods, of the compounds of the formula (I) which have been prepared by process (a), (b) or (c).

~
~i89593 The new sulphonylaminocarbonyltriazolinones having substituents bonded via oxygen, of the general formula (I), .and their salts are distinguished by a powerful herbicidal activity.
Surprisingly, the new compounds of the formula (I) show a considerably better herbicidal-action than the known compound 2-(2-chlorophenylsulphonylaminocarbonyl)4,5-dimethyl-2,4-dihydro-3H-1,2,4-triazol-3-one, which has a similar structure.

~
~I89593 Preferred salts are sodium, potassium, magnesium, calcium, ammonium, C1-C4-alkyl-ammonium, di-(Cl-C4-alkyl)-ammonium, tri-(C1-G4-alkyl)-ammonium, C5- or C6-cycloalkyl-ammonium and di-(C1-C2-alkyl)-benzyl-ammonium salts of compounds of the formula (I) in which R1, R2 and R3 have the meanings mentioned above as being preferred.
The abovementioned definitions of radicals, in general or mentioned in preferred ranges, can be combined with each other In any desired way, that is to say also between the particular preferred ranges.

~ ~i89~93 Examples of tkie compounds are listed in Table 1 below - cf. also trie Preparation Examples.
R3_SOx_NH_CO_N ~N_Ri I _ ~O_R2 231$9-7322D

~ ~I89593 Table 1: Examples of the compounds of the formula (I) F

CH3 C2H5 \

CH3 CH2-CH=CH2 ~2N(CH3)2 CH3 CH3 HZ_ NON
Cfi3 ~e 1~ ~~ ~~B - 19 -Table 1: (Continuation) CH3 C H ~

C H C3H i CF3 CH3 ( 'r--CH
~~/ 2 _~~ON(CH3J2 CH(CH3)2 ~N
Le A 28 3~8 - 20 -~ ~~89593 Table 1: .._(Continuation) CH3 CH(CH3)2 ~ I S02NH2 ~H(CH3)2 CH3 CH2-CH=CH2 ~2CH3 F
C2H5 C2fi5 Si(CH3f3 CH3 CzHS

C2H5 . C3H7 Hz_ CON(CH3f2 z~e~zasza -zi-~~.8~5~~
Table: (Continuation) f~ Br CHZ-( ') CH3 -._ ~HZCHZ-OCH3 .
,~~\\

CH3 ~ ~ r PIN

~2N(CH3)Z

_ OCHFZ
CSH7_n HZ_ CH(CH3)2 CH3 CzHS \

Le A B 'W 8 _ 22 _ 2~89~g~
Fable 1:_ (Continuation) CH3 S-CHZ-C~CH
~S
N

- COOCfi3 N~N~
iC00CH3 NON
N~ w ' i Ire ~ 2 ~ m $

- ~189~93 Tab s_ (Continuation) TI~S
CH3 i CON(CH3)2 C3H7 w I

CHZ-CH=CH2 CZHS HZ-r CHZ-CH=CHZ CH3 1J~N~
( CzHS CH3 SOZNCH3(OCH3) C2H5 C2H ~-~~(5 Le A 28 ~~8 - 24 -~1895~3 Table is (Continuation) C3Hy CHZ-CH=CHz CZHS

C2H5 \

JJ~N

SOZ--( ') Le A 8 '~ta _ - -25 - _ ' 2.89593 Table 1: (Continuation) , CH3 C3H' H
C3Hy CH3 ~
~OOCH3 C3H7 C2H5 ~\
F
C3H~ CZHS

N
O
CH3 CH3 ~ I CF3 ~N
Le A 28 ~ - a6 -Tabhs (Continuation) N(CH3)z CH

CH i SOZNH2 C2H5 C2H5 i I SOZNH2 ~N
CH3 ~~SOZNH2 S~~O-CF2-CF2C 1 N(CN3)2 C (,~~('~H

~e ~ 2e aie _ 1 2~893g3 If, ~or-example, 2,6-difluoro-phenylsulphonyl isocyanate and 5-ethoxy-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one are used as starting substances, the course of the reaction in process (a) can be outlined by the following equation:
F O
_ H. CHs SOz-N=C=O + N
N
F OCzHs -CO
If, for example, 2-methylthio-benzeneaulphonamide and 2-chlorocarbonyl-4-dimethylamino-5-propyloxy-2,4-dihydro-3H-1,2,4-triazol-3-one are used as starting substances, the course of the reaction in process (b) can be outlined by the following equation:

_ Cl-CO~ ~ ~N(CH3)z SOz NHz N ----a N -HCl OC3H~
...".

~ 2189593 If, for example, N-methoxycarbonyl-2-methoxy-benzenesulphonamide and 5-methoxy-4-difluoromethyl-2,4-dihydro-3H-1,2,4-triazol-3-one are used as starting substances, the course of the reaction in process (c) can be outlined by the following equation:

H\N~N~CHFz SOZ-NH-COOCH3 +
N--~
~OCH3 Formula (II) provides a general definition of the triazolinones to be used as starting substances in processes (a) and (c) for the preparation of compounds of the formula (I) .
In formula (II), R1 and R2 preferably, or in particular, have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) as being preferred, or particularly preferred, for R1 and R2.

~i8~593 Examples of the starting substances of the formula (II) are listed in Table 2 below.
0~' HN~NiRl _ Z (II) R
Le ~ 28 318 - 30 -aT ble2: Examples of the starting substances of the formula (II) CH(CH3)2 CH

CH3 C3H~

CH3 CH(CH3)2 CH3 CH2-CH=CH2 CH3 CH2--C ') _ X18 ___ ~- 31 -T~ 7~ a (Continuation) R

CI13 CH2-C~CIi CZHS CZiis C3li~
C2tIg Cfiz-CH=CHZ ~ZFis Cit2-CtfBr-CFi~Ftr Cztis C~(i~

Cfi2-Cfl=Cfi2 CH(Cfi3f2 Cztis Cf; ( Cfi3 ) z C3H~ CH ( CH3 ) 2 CH2-CH=CHZ C ti C2fi5 C3ti~

czlis -crrz-cscH

C3N~ C3ii Le 1~~ _ 3 Some of the starting substances of the formul<~
(II) are the subject c~f an earlier, but non-prior-published, Patent application (cf. German patent 4,030,063, which was published 26.03.1992).
The compounds of the general formula (II) in which R1 has the a.bovementioned meaning and R2 represents in each case optionally substituted cycloalkyl, cycloalkenyl, aralkyl or aryl, are new and a subject of the present divisional patent. application.
The compounds of the formula (II) are obtained when hydrazinoformic esters of the general formula (VIII
H2N-NH-CO-O-:R~'"~' ( VI I ) in which R2' represents methyl, ethyl or phenyl are reacted with alkyliminocarboni.c diesters of the genexal formula (VIII) ,/
R1-:~T=C ~~ ( VI I I
\ O_R.a in which R1 represents hydrogen, amino, C1-C4-alkyl which is optionally substituted by fluorine, cyano, methoxy or ethoxy, or represents allyl, C3-C6-cycloalkyl, benzyl, phenyl, C1-C3--alkyl amino, C3-C6-Cycloalkylamino or di- (C1-C3-alkyl)-amino;
R2' represents hydrogen, C1-C4-alkyl which is optionally substituted by fluorine and/or chlorine, methoxy or ethoxy, or represents C_3-C4-alkenyl which is optionally substituted by fluorine and/or chlorine, or represents C3-C6-cycloalkyl, or represents phenyl or benzyi which is optionally substituted by fluorine, chlorine and/or methyl;
in the presence of a diluent. such as, for example, methanol, at temperatures between 0°C and 50°C, and the compounds formed .in this process, of the general formula ( IX) O-Rz Rz'-O-CO-NH-N=C ~ ( IX) NH-Rl 33a ~' 2~89~93 in which R1, R2 and R2~ have the abovementioned meaning, are, if appropriate, isolated by customary methods and heated to temperatures between SO°C and 150°C, if appropriatein the presence of a diluent such as, for example, toluene, xylene or o-dichlorobenzene (cf. Preparation Examples).
The starting substances of the formulae (VII) and (VIII) are known chemicals.
The intermediates of the formula (IX) are new compounds.
Formula (III) provides a general definition of the sulphonyl isocyanates furthermore to be used as starting substances in process (a) for the preparation of compounds of the formula (I).
In formula (III), R3 preferably, or in particular, has that meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) as being preferred, or particularly preferred, for R3.
Examples of the starting substances of the formula (III) which may be mentioned are:
2-fluoro-, 2-chloro-, 2-bromo-, 2-methyl-, 2-methoxy-, 2-trifluoromethyl-, 2-difluoro-methoxy-, 2-trifluoromethoxy-, 2-methylthio-, 2-ethylthio-, 2-propylthio-, 2-methylsulphinyl-, 2-methylsulphonyl-, 2-dimethylaminosulphonyl-, 2-diethylaminoaulphonyl-, 2-(N-methoxy-N-methyl)-aminosulphonyl-, 2-phenyl-, 2-phenoxy-, ~, 2~89~93 2-methoxycarbonyl-,2-ethoxycarbonyl-,2-propoxycarbonyl and 2-isopropoxycarbonyl-phenylsulphonyl isocyanate, 2-fluoro-, -chloro-, 2-difluoromethoxy-, 2-trifluoromethoxy-, 2-methoxycarbonyl- and 2-ethoxycarbonyl-benzylsulphonyl isocyanate, 2-methoxycarbonyl-3-thienyl-sulphonyl isocyanate, 4-methoxycarbonyl- and 4-ethoxycarbonyl-1-methyl-pyrazol-5-yl-sulphonyl isocyanate.
The sulphonyl isocyanates of the formula (III) are kcnown and/or can be prepared by processes known per se (cf. US
Patent 4,127,405, 4,169,719, 4,371,391; EP-A 7,687, 13,480, 21,641, 23,141, 23,422, 30,139, 35,893, 44,808, 44,809, 48,143, 51,466, 64,322, 70,041, 173,312).
Process (a) for the preparation of the new compounds of the formula (I) is preferably carried out using diluents.
Diluents which are suitable for this purpose are virtually all inert organic solvents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroine, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl ether 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, eaters such as methyl acetate and ethyl acetate, nitriles such as, for example, acetonitrile and propionitrile, amides such as, for example, dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and also dimethyl _ , ~ X189593 sulphoxide, tetramethylene sulphone and hexamethylphosphoric triamide.
When carrying out process (a) the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0°C and 150°C, preferably at temperatures between 10°C
and 80°C.
In general, process (a) is carried out under atmospheric pressure.
For carrying out process (a) between 1 and 3 moles, preferably between 1 and 2 moles, of sulphonyl isocyanate of the formula (III) are generally employed per mole of triazolinone of the formula (II).
The reactants can be combined in any desired sequence. The reaction mixture is stirred until the reaction is complete and the product is isolated by filtration with suction. In another processing variant, the mixture is concentrated, and the crude product which remains in the residue is brought to crystallisation with a suitable solvent such as, for example, diethyl ether. The product of the formula (I) which is obtained in this way in crystalline form is isolated by filtration with auction.
Formula (IV) provides a general definition of the triazolinone derivatives to be used as starting substances in process (b) for the preparation of compounds of the formula (I).

23189-7' ~ 2189593 In formula (IV), R1 and R2 preferably, or in particular, have those meanings which have already been mentioned above in connection with description of the compounds of the formula (I) as being preferred, or particularly preferred, for Rl and R2 and Z preferably represents chlorine, C1-C4-alkoxy, benzyloxy or phenoxy, in particular methoxy or phenoxy.
Examples of tk~e starting substances of tine formula (IV) which are possible are the compounds of the formula (IV) which are to be prepared from the compounds of the ' ~~~~593~
. . 1~
formula (II) listed in Table 2 and phosgene, methyl chloroformate, benzyl chloroformate~ phenyl chloroformate or diphenyl carbonate.
The starting substances of the formula (IV) were hitherto unknown.
The new triazolinone derivatives of the formula (IV) are obtained when triazolinones of the general formula (II) HI~NIRI III) ~_R2 in which R' and RZ have the abovementioned meanings are reacted with carbonic acid derivatives of the general formula (X) Z-CO-Z' (X) in which Z has the abovementioned meaning and Z1- represents a leaving group such as chlorine, Le ~ 2B 3~8 _ 3g _ Y
~~$93~3 methoxy, benzyloxy or phenoxy, if appropriate iri the presence of a diluent such as, for example, tetrahydrofuran, and, if appropriate, in the presence of an acid acceptor such as, for example, sodium hydride or potassium tert-butylate, at temperatures between -20°C and +100°C.
Formula (V) provides a general definition of the sulphonamides furthermore to be used as starting substances in process (b) for the preparation of compounds of the formula (I) .
In formula (V), R3 preferably, or in particular, has that meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) as being preferred, or particularly preferred, for R3.
The following may be mentioned as examples of the starting substances of the formula (V):
2-fluoro-, 2-chloro-, 2-bromo-, 2-methyl-, 2-methoxy-, 2-trifluoromethyl-, 2-difluoro-methoxy-, 2-trifluoromethoxy-, 2-methylthio-, 2-ethylthio-, 2-propylthio-, 2-methylaulphinyl-, 2-methylsulphonyl-, 2-dimethylaminosulphonyl-, 2-diethylaminosulphonyl-, 2-(N-methoxy-N-methyl)-aminosulphonyl-, 2-phenyl-, 2-phenoxy-, 2-methoxycarbonyl-,2-ethoxycarbonyl-,2-propoxycarbonyl and 2-isopropoxycarbonyl-benzenesulphonamide, 2-fluoro-, 2-chloro-, 2-difluoromethoxy-, 2-trifluoromethoxy-, 2-methoxycarbonyl- and 2-ethoxycarbonyl-phenylmethane-~ ~~89~93 sulphonamide, 2-methoxycarbonyl-3-thiopheneaulphonamide, 4-methoxycarbonyl- and 4-ethoxycarbonyl-1-methyl-pyrazole-5-sulphonamide.
The sulphonamides of the formula (V) are known and/or can be prepared by processes known per se (cf. US
Patent 4,127,405, 4,169,719, 4,371,391; EP-A 7,687, 13,480, 21,641, 23,141, 23,422, 30,139, 35,893, 44,808, 44,809, 48,143, 51,466, 64,322, 70;041, 173,312).
Process (b) for the-preparation of the new compounds of the formula (I) is preferably carried out using diluents.
Diluents which are suitable for this purpose are virtually all inert organic solvents as have been indicated, for example, above -in the case of process (a).
Acid acceptors which can be employed in process (b) are all acid-binding agents which can customarily be employed for reactions of this type. The following are preferably suit-able: alkali metal hydroxides such as, for example, sodium hy-droxide and potassium hydroxide, alkaline earth metal hydrox-idea such as, for example, calcium hydroxide, alkali metal carbonates and alkali metal alcoholates such as sodium carbon-ate, potassium carbonate, sodium tart-butylate and potassium tart-butylate, furthermore aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine, pyridine, 1,5-diazabicyclo-[4.3.0]-non-5-ene (DBN), 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) and 1,4-diazabicyclo(2.2.2]-octane (DABCO).

~189~93 When carrying out process (b), the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0°C and 100°C, preferably at temperatures between 10°C
and 60°C. ' Process (b) is generally carried out under atmospheric pressure. However, it can also be carried out under increased or reduced pzessure.
For carrying out process (b) the starting substances required in each case are generally employed in approximately equimolar amounts. However, it is also possible to use one of the two components employed in each case in a larger excess.
In general, the reactions are carried out in a suitable diluent_in the presence of an acid acceptor, and the reaction mixture is stirred for several hours at the particular temperature required. Working-up in process (b) is carried out in each case by customary methods.
The triazolinones of the formula (II) to be used as starting substances in process (c) for the preparation of compounds of the formula (I) have already been described as starting substances for process (a).
Formula (VI) provides a general definition of the sulphonamide derivatives furthermore to be used as starting substances in process (c) for the preparation of compounds of the formula (I).
In formula (VI), R3 and Z preferably, or in particular, have those meanings which have already been .. i ~i~~~93 mentioned above in connection with the description of the compounds of the formula (I) or (IV) as being preferred, or particularly preferred, for R3 and Z.
Process (c) is preferably carried out using diluents. Solvents which are suitable for this purpose are the same organic solvents as have been mentioned above in connection with the description of process (a).
If appropriate, process (c) is carried out in the presence of an acid acceptor. Acid-binding agents which are suitable for this purpose are the same as have been mentioned above in connection with.the description of process (b).
When carrying out process (c), the reaction temperatures can vary within a substantial range. In general, the process is carried out at temperatures between 0°C and 100°C, preferably at temperatures between 10°C and 60°C.
In general, process (c) is carried out under atmospheric pressure. However, the process can also be carried out under increased or-reduced pressure.
For carrying out process (c), the starting substances required in each case are generally employed in approximately equimolar amounts. However, it is also possible to use oneof the two components employed in each case in a larger 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 particular temperature required. Working-up is carried out in process (c) in each case by customary methods.

_ , ~ ~is~~s3 To convert the compounds of the formula (I) into salts, they are stirred with suitable salt formers such as, for example, sodium hydroxide, sodium methylate, sodium ethylate, potassium hydroxide, potassium methylate or potassium ethylate, ammonia, isopropylamine, dibutylamine or triethylamine, in suitable diluents such as, for example, water, methanol or ethanol. The salts can be isolated in the form of crystalline products, if appropriate after concentration.
The active compounds can be used as defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weed-killers. By weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are undesired. Whether the substances act as total or selective herbicides depends essentially on the amount used.
The active compounds can be used, for example, in connection with the following plants:
Dicotvledon weeds of the aenera~ Sinapis, Lepidium, Galium, Stellaria, Natricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotyledon l a res of the aenerav Gosaypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum,-Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
~cotyledcn wee of the aenera~ Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, ~18~593 Agropyron, Cynodon, Monochorla, fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalmm, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera..
Monocotvledon Cultures of the aenera~ Oryz_a, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the concentration, for the total combating of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for combating weeds in perennial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves., nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, on lawns, turf and pasture-land, and for the selective combating of weeds in annual cultures.

~ ~~.~95~3 Some of the compounds of the formula (I) are suitable for total or semi-total weed control, some for the selective control of monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon cultures, both pre-emergence and post-emergence.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, ~i89593 soluble powders, granules, suspension-emulsion concen-trates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is emulsi fying agents and/or dispersing agents and/or foam-forming agents.
In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkyl-naphthalenea, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloro-ethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar sol-vents, such as dimethylformamide and dimethyl sulphoxide, as well as water.
As solid carriers there are suitable: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, mont-Le A 28 318 - 46 -~189~~3 morillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates, as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, 'pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks;
as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxy-ethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates ae well as albumen hydrolysis products;
as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in .the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipida, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pig-ments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dye-stuffs, and trace nutrients such as salts of iron, >~e A 28 3:g ~ ~18~~9~
manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90°s.
For combating weeds, the active compounds, as such or in the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Suitable herbicides for the mixtures are known herbicides, such as, for example, 1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(1H,3H)-dione (AMETHYDIONE) or N-(2-benzothiazolyl)-N, N'-dimethyl-urea (METABENZTHIAZURON) for combating weeds in cereals; 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one (METAMITRON) for combating weeds in sugar beet and 4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one (METRIBUZIN) for combating weeds in soya beans;
furthermore also 2,4-dichlorophenoxyacetic acid (2,4-D);
4-(2,4-dichlorophenoxy)-butyric-acid (2,4 -DB); 2,4-dichlorophenoxypropionic acid (2,4-DP); S-(2-chloro-4-trifluoromethyl-phenoxy)-2-nitro-benzoic acid (ACIFLUORFEN);
N-(methoxy-methyl)-2,6-diethyl-chloroacetanilide (ALACHLOR);
methyl-6,6-dimethyl-2,4-dioxo--3[1-(2-propenyloxyamino)-buty-lidene]-cyclohexanecarboxylic acid (ALLOXYDIM);
4-amino-benzenesulphonyl-methyl carbamate (ASULAM);
2-chloro-4-ethylamino-6-isopropylamino ~ X189593 1,3,5-triazine (ATRAZINE); methyl 2-[[[[[(4,6-dimethoxy-pyrimidin-2-yl)-amino]-carbonyl]-amino]-sulphonyl)-methyl}-benzoate (BENSULFURON); 3-isopropyl-2,1,3-benzo-thiadiazin-4-one 2,2-dioxide (HENTAZONE); methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate (BIFENOX); 3,5-dibromo-4-hydroxy-benzonitrile; (BROMOXYNIL); N-(butoxymethyl)-2-chloro-N-(2,6-diethylphenyl)-acetamide (BOTACHLOR);
5-amino-4-chloro-2-phenyl-2,3-dihydro-3-oxy-pyridazine (CHLORIDAZON); ethyl 2-{[(4-chloro-6-methoxy-2-pyrimi-dirsyl)-aminocarbonyl]-aminosulphonyl}-benzoate (CHLORIMURON); N-(3-chlorophenyl)-isopropyl carbamate (CHLOROPROPHAM); 2-chloro-N-{[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl}-benzenesulphonamide (CHLORSULFURON); N,N-dimethyl-N'-(3-chloro-4-methyl-phenyl)-urea (CHLORTOLURON); exo-I-methyl-4-(1-methyl-ethyl)-2-(2-methylphenyl-methoxy)-7-oxabicyclo-(2,2,1)-heptane (CINMETHYLIN); 3,6-dichloro-2-pyridinecarboxylic acid (CLOPYRALID); 2-chloro-4-ethylamino-6-(3-cyanopro-pylamino)-1,3,5-triazine (CYANAZINE); N,S-diethyl N-cyclohexyl-thiocarbamate(CYCLOATE);2-[1-(ethoximino)-butyl]-3-hydroxy-5-[tetrahydro-(2H)-thiopyran-3-yl)-2-cyclohexen-1-one (CYCLOXYDIM); 2-[4-(2,4-dichloro-phenoxy)-phenoxy}-propionic acid, its methyl ester or its ethyl ester (DICLOFOP); 2-[(2-chlorophenyl)-methyl]-4,4-dimethylisoxazolidin-3-one (DIMETHAZONE); S-ethyl N,N-di-n-propyl-thiocarbamidate (EPTAME); 4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5(4H)-one (ETHIOZIN); 2-{4-[(6-chloro-2-behzoxazolyl)-oxy]-phenoxy}-propanoic acid, its methyl ester or its ethyl ester (FENOXAPROP); 2-[4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]-propanoic acid or T~e A 2 8 318 - 49 -~ X189593 its butyl ester (FLUAZIFOP); N,N-dimethyl-N'-(3-tri-fluoromethylphenyl)-urea (FLUOMETURON); 1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4-pyridone (FLURIDONE); [(4-amino-3,5-dichloro-6-fluoro-2-pyri-dinyl)-oxyj-acetic acid or its 1-methylheptyl ester (FLUROXYPYR); 5-(2-chloro-4-trifluoromethyl-phenoxy)-N-methylsulphonyl-2-nitrobenzamide (FOMESAFEN); N-phos-phonomethyl-glycine (GLYPHOSATE); 2-{4-[(3-chloro-5-(trifluoromethyl)-2-pyridinyl)-oxy]-phenoxy}-propanoic acid or its ethyl ester (HALOXYFOP); 3-cyclohexyl-6-dimethylamino-1-methyl-1,3,5-triazine-2,4-dione (HEXAZINONE);methyl2-[4,5-dihydro-4-methyl-4-(1-methyl-ethyl)-5-oxo-1H-imidazol-2-ylj-4(5)-methylbenzoate (IMAZAMETHABENZ); 2-(4,5-dihydro-4-methyl-4-isopropyl-5-oxo-1H-imidazol-2-yl)-pyridine-3-carboxylic acid (IMAZAPYR); 2-[5-methyl-5-(1-methylethyl)-4-oxo-2-imida-zolin-2-yl]-3-quinolinecarboxylic acid (IMAZAQUIN); 2-[4,5-dihydro-4-methyl-4-isopropyl-5-oxo-(1H)-imidazol-2-yl]-5-ethylpyridin-3-carboxylic acid (IMAZETHAPYR); 3,5-diiodo-4-hydroxybenzonitrile (IOXYNIL); N,N-dimethyl-N'-(4-isopropylphenyl)-urea (ISOPROTURON); 2-ethoxy-1-methyl-2-oxo-ethyl 5-[2-chloro-4-(trifluoromethyl)-phenoxy]-2-nitrobenzoate (LACTOFEN); (2-methyl-4-chloro-phenoxy)-acetic acid (MCPA); (4-chloro-2-methylphenoxy)-propionic acid (MCPP); N-methyl-2-(1,3-benzothiazol-2-yloxy)-acetanilide(MEFENACET);2-chloro-N-(2,6-dimethyl-phenyl)-N-[(1H)-pyrazol-1-yl-methyl]-acetamide (METAZACHLOR); 2-ethyl-6-methyl-N-(1-methyl-2-methoxy-ethyl)-chloroacetanilide(METOLACHLOR);2-{((((4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino)-carbonyl]-amino]-Le A 28 3~g - 50 -~
~~.89593 sulphonyl}-benzoic acid or its methyl ester {METSULFURON); 5-ethyl N,N-hexamethylene-thiocarbamate (MOLINATE); 1-(3-trifluoromethyl-phenyl)-4-methylamino-5-chloro-6-pyridazone (NORFLURAZON); 4-(di-n-propyl-amino)-3,5-dinitrobenzenesulphonamide {ORYZALIN); 2-chloro-4-trifluoromethylphenyl 3-ethoxy-4-nitro-phenyl ether (OXYFLUORFEN); N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitroaniline (PENDIMETHALIN); 3-(ethoxycarbonylamino-phenyl) N-(3'-methylphenyl)-carbamate (PHENMEDIPHAM);
4-amino-3,5,6-trichloropyridine-2-carboxylic acid (PICLORAM); «-chloro-2',6'-diethyl-N-(2-propoxyethyl)-acetanilide (PRETILACHLOR); 2-chloro-N-isopropyl-acetanilide (PROPACHLOR); isopropyl-N-phenyl-carbamate (PROPHAM); O-(6-chloro-3-phenyl-pyridazin-4-yl) S-octyl thiocarbonate (PYRIDATE); ethyl 2-[4-(6-chloro-quinoxa-lin-2-yl-oxy)-phenoxy)-propionate (QUIZALOFOP-ETHYL); 2-[1-(ethoxamino)-butylidene)-5-(2-ethylthiopropyl)-1,3-cyclohexadione (SETHOXYDIM); 2-chloro-4,6-bis-(ethyl-amino)-1,3,5-triazine(SIMAZINE);2,4-bis-[N-ethylamino)-6-methylthio-1,3,5-triazine (SIMETRYNE); methyl 2-([(4,6-dimethyl-2-pyrimidinyl)-aminocarbonylj-amino-sulphonyl}-benzoate (SULFOMETURON); 4-ethylamino-2-t-butylamino-6-methylthio-s-triazine (TERBUTRYNE); methyl 3-[[([(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl)-amino]-sulphonylJ-thiophene-2-carboxylate (THIAMETURON); S-[(4-chlorophenyl)-methyl] N,N-diethyl-thiocarbamate (THIOBENCARB); S-(2,3,3-trichloroallyl) N,N-diisopropylthiocarbamate (TRIALLATE); 2,6-dinitro-4-trifluoromethyl-N,N-dipropylaniline (TRIFLURALIN).
Le A -S ~~8 _. - 51 -~ ~i89593 Surprisingly, some mixtures also show a synergistic action.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomising or scattering.
The active compounds can be applied either before or after emergence of the plants.
They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 1~ kg of active compound per hectare of soil surface,-preferably between 5 g and 5 kg per ha.
The preparation and use of the active compounds can be seen from the following examples.

X1$9593 Preparatson Ex mpie Example 1 SOZ-NH-CO-N~N-CH3 N ~
(Process (a)) A mixture-of 2.0 g (10.5 mmol) of 4-methyl-5-phenoxy-2,4-dihydro-3H-1,2,4-triazol-3-one, 3.5 g (14.5 mmol) of 2-methoxycarbonyl-phenylsulphonyl isocyanate and 60 ml of acetonitrile is stirred for 6 hours at 20°C and subsequently concentrated under a water pump vacuum. The residue is stirred with diethyl ether and the product which has precipitated in crystalline form is isolated by filtration with auction.
4.I g (90% of theory) of 2-(2-methoxycarbonyl-phenylsulphonylaminocarbonyl)-4-methyl-5-phenoxy-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 161°C are obtained.
Other examples ofcompounds of the formula (I) which can be prepared analogously to Example 1 and following the general description of the preparation processes are those listed in Table 3 below.

~ ~~89593 OII
R3-S02-NN-CO-N/\N-R1 -R2 (I) Tab s .Preparation Examples of the compounds of the formula (I) Example R1 RZ R3 Meltinq~
No. - point ( C) 2 C2H5 ~ 183 4 CH3 C3H~ 120 N~N~

F

5 CH3 C3H~ 134 Le A 28 ~ 8 __ _ 54 -T$ - Continuation Example RI R~ R' Melting N

o. point ( C

8r COOC H

NON

CH3 C2H5 ~ 131-132 F

CH3 C2H5 ~ 147-148 Br Le A 28 316 _ 5g _ Ta - Continuation Example R1 RZ R' Melting No. point ( C) CI
14 CH3 C2H5 ~ 188-189 ~OCF3 16 CH3 C2H5 ~ 152-153 i7 CH3 C2H5 ~ 172-173 18 CH3 C2H5 ~ 147-148 C2H'' ~H2- 183-184 CI

g OOCH3 iOCF3 21 C C./~'.'~~f.'1--C_H

Le A 29 '~~8 _ - 56 -~ ~~89593 Table 3 - Continuation Example R1 RZ R' Melting No. point ( C) 22 CH3 C2H5 \ ~ ~ 162-163 23 CH3 C2H5 ~ 146-147 COOCli3 F

Br ~e ~ 28 3~8 _ 5~ _ ab~ 1e 3 - Continuation Example R1 Ri R' Meltin No. point (~C) 3 7 CH3 ~ ~ 129-130 NON

34 C3H7 CN3 ~ 115-116 36 C3H7 CH3 ~ ~ 130-131 Le J~ 28 3~~ _ 5g _ T a - Contin uation Example R' RZ R' Melting No, point ( C) 38 C3H7 CH3 \ ~ ~ 122-123 41 CH3 C4H9 ~ ~

I~N

Br 42 CH3 CqHg ~ i53 43 CH3 C9H9 ~ 105 45 CH3 CQH9 ~ 137 Le .A 28 ~1~ _ 5g _ ~ ~~89593 Table ~ - Continuation Example R1 R2 R' Melting No. point ( C

48 CH3 C4H9 ~ ~ 147 OOCFi3 _ I I COOC2H5 50 C2H5 N~i 114 C2H5 ~ 135 Le A 28 3~8 - 60 -Tablg 3 - Continuation Example R1 RZ R' Melting No' point ( C

Hr Br CI

59 -CH2-CH=CH CH

60 -CH2-CH=CH2 CN

Br 61 -CH2-CH=CH2 CH

Le A 28 318 - 61 -~, ~189~93 Table 3- ~~~u~
~E~ mple Ri RZ R3 Melting Point UC'1 62 -CHa-CIi~CHz CH3 103 \
Ct's 63 -CH2-CIisCHz Clip 130 \ /
cta, G4 Clis Cli3 196 \ /
CFa 65 CH3 CH3 ~ /- 161-163 (Na-Sait) ~3 66 -Cliz-CH-CHZ Cli3 130 ~3 67 ~3 \ / ~ 211 ~~f~
68 CH3 \ / 179 OCIIF~
69 Cli3 CH3 171 \ /

., . r ~, zis9~~3 Tab - Continuation Example R1 Ra R3 Meltin~q No.
point ( C

70 -CH2-CH=CH2 CH3 '(~~~-(~ 115 71 CH3 ~ 162 72 CH3 C3H7 ~ 141 75 -Ctl2-CFi=CH2 CH3 138 CH3 ~ 150 Le A 28 31~ - b3 -Table - --Continuation Example R1 R2 R3 Melting N

o. point ( C) 78 -C H2-CH=CH2CH3 125 80 C2H5 CH3 ~ 153-154 F

81 C2H5 CH3 ~ 151-152 Br 82 C2H5 CH3 ~ 167-168 83 C2H5 CH3 ~ 155-156 89 C2H5 CH3 ~ 174-175 85. C2H5 CH3 ~ ~ 140-141 T1~N

Le A 2~ ~~B - 64 -Table 3 - Continuation Example R1 Ra R3 Melting No . point ( C) 90 C2H5 CH3 (. ,Y-CH2- 137-138 '~

91 C2H5 CH3 ~H2- 203-204 ~--( F

92 CH3 C4Hy ~ 118-119 93 CH3 C4H9 ~ 146-147 Le A ~8 '~18 - 65 -y , ~ ~~~Ja~3 Taklle 3 - Continuation Example R' RZ R' Melting No. - point ( C

99 CN3 CQHy ~ 110-111 95 CH3 C4Hy t"r-CH2- 123-124 l.~

F

96 C2H5 ~ 152-153 C2H5 ~ 116-117 C2H5 ~ 145-146 C2H5 ~ 132-133 100 C2H5 ~ 88-89 I,e A 28 318 - 66 -1 ~~8~593 Continuation Example R1 RZ R' Melting No. point ( C

~

~

102 C2H5 ~ 79-77 103 -CH2-CH=CH2 C2H8 114-115 104 -CH2-CH=CH2 C2H5 ~ 104-106 ~
lt~N

F

105 -CH2-CH=CFi2 C2H5 85-86 Br 106 -CH2-CH=CH2 C2H5 121-122 107 -CH2-CH=CH2 C2H5 107-108 108 -CH2-CH=CFi2 C2H8 ~ 123-124 Le A 28 318 _ 67 _ ~~89~93 Table 3 - Continuation Example R1 RZ R' Meltin No. . point (~C) 109 -CH2-CH=CH2 C2H5 - 131-132 110 -CH2-CH=CH2 C2H5 ~ 118-119 111 -CH2-CH=CH2 C2H5 ~ 110-111 112 -CH2-CH=CH2 C2Fi5 i23-124 113 -CH2-CH=CH2 C2H5 ~~ - 103-109 114 -CH2-CH=CFi2 C2H5 )250 115 -CH2-CH=CH2 C2H5 ~CH2- 114-115 l~J

116 -CH2-CH=Cli2 C2H5 ~ 122-123 Le A 28 31$ - 68 -~ X189593 T
a -Continuation Z

Example R' R2 R' Melting No . point ( C) CFi3 117 CH(CH3)2 C2H5 \ 188-190 118 CH(CH3) C ~
F) NON

F

119 CFi(CFi3)2 C2H5 ~ 129-130 Br 120 CH ( CH3 ) C2H5 ~ 207 (Zers.) 121 CH(CH3)2 C2H5 113-114 122 CH(CH3)2 C2H5 195-200 123 CH(CH3)2 C2H5 ~~ 133-134 CFi3 _ _ 124 CH(CH3)2 C2H5 139-140 Le I~ 2 31$ ~ _ - 69 -~~89593 Table - Continuation Example R1 R2 RS Melting No. point ( C) 125 Ci ( CH3 ) C2H5 105-106 126 CH(CH3)2 C2H5 123-124 127 -(CH2)3-OCH3 CH3 - 112-114 128 -(CH2)3-OCH3 CH3 ~~ 92-95 ~

N~

F

129 -(CH2)3-OCH3 CH3 126-127 Br 130 -(CH273-bCi3 CH3 115-116 131 -(CH2)3-OCH3 CH3 112-i13 132 -(CH2)3-OCH3 CH3 81-82 Le h 28 3t8 - 70 -. . ~ ~18~~93 Table 3 - Continuation Example R~ R' Melting R' N' point ( Cj 133 -(CH2)3-OCH3 CH3 ~ 104-105 134 -(CH2)3-OCH3 CFF3 ~ 113-114 135 -(Cfl2)3-OCH3 CH3 ~~ 91-92 CFi3 136 n-C3H7 C2H5 ~ 108 (Zers.) 137 n-C3F17 C2H5 ~ 212-213 I
NON

F

138 n-C3H7 C2H5 ~ 105-107 Br 139 n-C3H7 C2H5 127-128 140 n-C3H7 C2H5 98 .._ (Zers.) Le A 2~ ~tQ - 71 -~18J~93 Tah~e3 - Continuation Example R1 Rx R' Melting H

' point ( C) 141 n-C3H7 C2H5 - 132-135 142 n-C3H7 C2H5 138-140 Cfi3 143 n-C3H7 C2H5 87-88 144 n-C3H7 C2H5 108-109 145 n-C3H7 C2H5 154-157 146 n-C3H7 C2H5 130-133 147 CHiCH3)2 CH3 150-151 148 CH(CH3)2 Cfi3 ~ ~ 160-161 - ._.

Le A 2_8 ~Le _ ° ' Tab - Continuation Example RZ R3 Melting No. point ( C) F

149 CH(CH3)2 CH3 147-148 Br 150 CH(CH3)2 CFi3 148-150 151 CH(CH3)2 CH3 143-144 152 CH(CH3)2 CH3 134-135 CI

153 CH(CH3)2 CH3 147-150 154 CH(CH3)2 CH3 i48-150 ,155 CH(CH3)2 CH3 ~ 143-i45 156 CH(CH3)2 CH3 114-116- .__ Le A 2$ 318 _ - 73 -~
~~8J55~3 T a - Continuation Example R1 Ra R' Meltin No.
point (~C

157 CH(CH3)2 CH3 125-128 158 CHg CH(CH3)2 ~- 95-97 Br 159 CH3 CH(CH3)2 ~ 158-160 160 CH3 CH(CH3)2 ~ 152-153 161 CH3 CH(CH3)2 ~ 150-152 162 CH3 CFi(CH3)2 ~ 128-130 163 CH3 CH(CH3)2 ~ 150-152 164 CH3 117-i18 Le ~ 28 318 - 74 -Tab a 3 - Continuation Example R1 RZ R' Melting No. point ( C

-166~ C2H5 i 148-150 ~

167C2H5 CH3 ~ 172-173 ~

168-CH2-CH=C112 C2H5 ~ 130-132 ~

169CH(CH3)2 C2li~ ( 142-i44 ~

170-(CH2)3-OCH3 CH3 ~ 127-130 ~

171n-C3H7 C2H5 ~ 127-130 , 172CH(CH3)2 CH3 ~ 156-157 ~

173C113 CH(CH3)2 ~ 198-200 ~

174CH(CH3)2 C2H5 ~ 122-129 Le A 2E 318 . 75 _ ~~.8y593 Table 3 - Continuation Example R1 R2 R' Melting No. point ( C) COOC3H7-n 175 -(CH2)3-OCH3 CFi3 ~ 97-98 COOC3H7-n 176 n-C3H7 C2H5 ~ 128-130 C3H7_n 177 CH(CH3)2 CH3 ~ 148-150 178 CH3 CFi ( CH3 ~ 154 ) 2 COOC3H7-n 180 CH3 C2H5 ~CH2- 134-136 ~~//

502N(CH3)2 181 CFi3 C2H5 178 ,~

182 CH3 n-C4H9 C 7-CH2- 142-143 Le ~ 28 X18 - 76 -2~8~5~3 ..
Table 3. ~~
)?xampleRt Ra s MeitIng No. R Point pC?

183 /~~ /octiP, ..
Cn115 ~3 ~\

( 115-118 ~
~~1-~!

OCiiPa 184 -CHz-CI-i-CH2C2Iis CHl-~oocsi, 185 CE~3 C~i ~ ~ 114-115 (Na-Salt) ~ii~-n CH3 CZHs 135-140 (Na-Salt) _ 77 _ ~ 2~8J~93 S artine substances of th orm~ta rte;
Fxamnle IIT-11 H-i~N-CHZ-CH=CHZ

A mixture of 5.0 g (0.02 mol) of 1-phenoxycarbonyl-4-allyl-O-methyl-isosemicarbazide and 30 ml of toluene is refluxed for 15 minutes and subsequently concentrated under a water pump vacuum. The residue is triturated with diethyl ether/petroleum ether, and the product which has been obtained in crystalline form is isolated by filtra-tion with suction.
2.0 g (fi4% of theory) of 4-allyl-5-methoxy-2,4-dihydro 3H-1,2,4-triazol-3-one of melting point 111°C are obtained.
Le A 2$ 338 _ - 7$ -H-N~N-CH3 ~Cfi3 50.2 g (D.33 mol) of phenyl hydrazinoformate and 36.6 g (0.33 mol, 93% strength) of trimethyl iminocarbonate are heated to 60°C in 100 ml of absolute o-dichlorobenzene, and the mixture is stirred for 2 hours, during which process a clear solution is formed. In the course of two hours, it is heated to 120°C, during which process methanol distilled off. A vacuum ie applied carefully, during which process more methanol and finally phenol distil off. Further distillation results in a fraction which solidifies in the receiving vessel in crystalline form.
After recrystallisation from toluene, 7.0 g (0.054 mol, 16% of theory) of 4-methyl-5-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 142-144°C are obtained in the form of colourless crystals.
Other examples of compounds of the formula (II) which can be_prepared analogously to Examples (II-1) and (II-2) are those listed in Table 4 below.

Le h 29 318 ~

H- N-R
N

2 (II) R

Table Examples of the starting substances of the 4:

formula (II) Example R1 Ra Meltin~

No. point ( C) II-4 CH3 C3H~ ~2 II-5 ~ CH3 149 II-7 CH(CH3)2 CH3 80-81 II-8 C2H5 CH3 (b-P : 120C

at 1,5 mbar) II-9 C3H~ CH3 (b t.~

C

a 1,5 mbar ) II-11 (CH2)30CH3 CH3 84-85 II-12 CH3 C2H5 (b t ~

C

a 1,5 mbar ) II-13 CH(CH3)2 C2H5 66-67 II-14 C3H~ C2H5 (b~P~ 140-150C

at 1,5 mbar) II-15 CH2=CH-CH2 C2H5 (b~P- 150C

at 1,5 mbar) ~18J593 Intermediates of the formula (IX1:
Examples IX-11 i0_CH3 -CO-NH-N=C~
NH-CHZ-CH=CHz A mixture of 30.4 g (0.2 mol) of phenyl hydrazinoformate, 26.0 g (0.2 mol) of methyl N-allyl-iminocarbonate and 150 ml of methanol is stirred for 12 hours at 20°C and subsequently concentrated under a water pump vacuum. The residue is triturated with diethyl ether/ethanol (1/1 by vol.), and the crystalline product is isolated by filtra-tion with suction.
11.0 g (22% of theory) of 1-phenoxycarbonyl-4-allyl-O-methyl-isosemicarbazide of melting point 114°C are obtained.
Other examples of compounds of the formula (IX) which can be prepared analogously to Example (IX-1) are those listed in Table 5 below.

Le A 28 318 ~ X189593 ~_ E~2 RZ~-O-CO-NII-N=C (I X) Table 5, Examples of the compounds of, the formula (IX) Example f1~ Rz Rz~ Melting No, point (C) ix-a c2N5 c113 c21t5 13~

Ix-4 c113 ctl3 crl3 134 IX-5 Cfl3 CI13 CpNs 135 IX-6 CzFls CII3 133-134 ~18~593 Use Examples:
In the Uae Examples, the following compound (A) is used as comparison substances Ci p ("f-SOZ-NH-CO-N~N-CH3 (A) ~H3 2-(2-chloro-phenylsulphonylaminocarbonyl)-4,5-dimethyl-2,4-dihydro-3H-1,2,4-triazol-3-one (disclosed in EP-A 341,489).
Example A
Poet-emergence test Solvent: 5 parts by weight of acetone Emulsifiers 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Test plants-which have a height 8f 5 - 15 cm are sprayed with the preparation of the active compound in such a way as to apply the particular amounts of active compound Le A 28 318 ~~.$~~93 desired per unit area. The concentration of the spray liquor is so chosen that the particular amounts of active compound desired are applied in 1,000 1 of waterlha.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control. The figures denote:
0% = no action (like untreated control) 100% = total destruction In this test, a considerably more powerful action against weeds than the known compound (A) is shown, for example, by the compounds of Preparation Examples 1, 2, 3, 53, 54, 55, 56, 57, 58, 64, 65 and 67, while having, in some cases, good crop plant compatibility.
Example B
Pre-emergence test Solvents 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Seeds of the teat plants are sown in normal soil and, after 24 hours, watered with the preparation of the _-g4 _ Le A 28 318 . ~ 2~8~~93 active compound. It is expedient to keep constant the amount of water per unit area. The concentration of the active compound in the preparation is of no importance, only the amount of active compound applied par unit area being decisive. After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control. The figures denote:
0% = no action (like untreated control) 100% = total destruction In this test, a considerably more powerful action against weeds than the known compound (A) is shown, for example, by the compounds of Preparation Examples 2, 54 and 69, while having, in some cases, good crop plant compati-bility.

Claims (9)

1. A compound of the general formula (IX) in which R1 represents hydrogen, amino, C1-C4-alkyl which is optionally substituted. by fluorine, cyano, methoxy or ethoxy, or represents allyl, C3-C6-cycloalkyl, benzyl, phenyl, C1-C3--alkylamino, C3-C6-cycloalkylamino or di-(C1-C3-alkyl)-amino;
R2 represents C1-C4-alkyl which is optionally substituted by fluorine and/or chlorine, methoxy or ethoxy, or represents C3-C4-alkenyl which is optionally substituted by fluorine and/or chlorine, or represents C3-C6-cycloalkyl, or represents phenyl or benzyl which is optionally substituted by fluorine, chlorine and/or methyl; and R27 represents methyl, ethyl or phenyl, with the exception of those compounds of formula (IX) in which R1 represents hydrogen, R2 represents phenyl, and R27 represents methyl; or R1 represents hydrogen, R2 represents 2.2.2-trichloroethyl or 2.2.2-trifluoroethyl and R27 represents methyl or ethyl.

2. A compound according to claim 1 wherein R1 is and R2 is C2H5.

3. A compound according to claim 1 wherein R1 is CH3 and R2 is

4. A compound according to claim 1 wherein R1 is CH3 and R2 is CH3.

5. A compound according to claim 1 wherein R1 is CH3 and R1 is C2H5.

6. A compound according to claim 1 wherein R1 is CH3 and R2 is n-C3H7.

7. A compound according to claim 1 wherein R1 is CH3 and R2 is i-C3H7.

8. A compound according to claim 1 wherein R1 is and R2 is CH3.

9. A process for preparing a compound of the general formula (IX) according to claim 1 wherein R1, R2 and R27 are as defined in claim 1, which process comprises reacting a hydrazinoformic ester of the general formula (VII) H2N-NH-CO-O-R27 (VII) in which R27 is as defined above, with an alkyliminocarbonic diester of the general formula (VIII) in which R1 and R2 are as defined above, in the presence of a diluent at a temperature of from 0°C to 50°C.