CA2398159C - Sulphonylaminocarbonyltriazolinones having substitutents bonded via oxygen - Google Patents

Abstract

The invention relates to novel intermediates of formula II useful in the preparation of sulphonylamino-carbonyltriazolinones herbicides having substituents bonded via oxygen and to salts thereof and to processes for preparing the intermediates:

(see formula I) in which R1 represents 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, and R2 represents C3-C6-cycloalkyl, or represents phenyl or benzyl which is optionally substituted by fluorine, chlorine and/or methyl.

Description

,, 23189-7322E
This application is a divisional application of copending application 2,189,593, filed November 5, 1996, which is a divisional application of parent application Serial No. 2,064,636, filed April 1, 1992, and issued December 23, 1997.
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).

v 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-SOZ-NH-CO-N ~N-Rl N--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-(C~.-C3-alkyl)-amino, R2 represents hydrogen, Cl-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 where R4 represents fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, 2-chloro-ethoxy, 2-methoxy-ethoxy, C1-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 Ri i -CH
R io 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 ~J
RO-C S
I
O

where R represents C1-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) O
H-N~N-R1 N---in which R1 and R2 have the meanings given above with a sulphonyl isocyanate of the general formula (III) R3-S02-N=C=O (IIT) in which R3 has the meaning given above, or (b) reacting a triazolinone derivative of the general formula (IV) O
7,~C0-N ~N-Rl I
N---in which RI 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-NH2 (V) in which R3 has the meaning given above, or (c) reacting a triazolinone of the general formula (II) J
23189-?322L

a H-N~N-R1 I
N----in which R1 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 reguired, forming a salt thereof.
In accordance with one aspect of the divisional application, there is provided a triazolinone of the general formula (II) O
H-N~N-R1 I
N-in which R1 represents amino, C1-C4-alkyl which is optionally substituted by fluorine, cyano, methoxy or ethoxy, or represents allyi, C3-CS-cycloalkyl, benzyl, phenyl, C1-C3-alkylamino, C3-CS-cycloalkylamino or di-(C1-C.~-alkyl)-amino, 23189- i,322D

and R2 represents C3-CS-cycloalkyl, 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 I~,,~
z O-R
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, C1-C3 alkylamino, C3-C6-cycloalkylamino or di-(C1-C3-alkyl)-amino, and R2 represents hydrogen, Cl-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) i 23189-i322L~

R2'-0-CO-NH-N=C ~ ( IX) NH-Rl in which R1 represents hydrogen, amino, C1-CQ-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;
RZ 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 R2' 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) NH_Rl in which R1 represents hydrogen, amino, C1-CQ-alkyl which is optionally substituted by fluorine, cyano, methoxy or ethoxy, or represents allyl, C3-C6-cycloalkyl, benzyl, phenyl, C1-C3-alkylami no, C3-C6-cycloalkylamino or di- (C1-C3-alkyl)-amino; and RZ represents hydrogen, C1-CQ-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 RZ' 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 defined above 8a wherein 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, 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 R2~ 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) 1 ~ O_R2 R -N=C (VIII) ~-R2 in which R1 and R2 are as defined above, at a temperature of from 0°C to 50°C.

The compound 2-(2-methoxycarbonyl-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) triazollnanes of the general formula (II) O
H-N~N-R~
I
N---O-RZ

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) 7rC0-N ~N-Rl I
N---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 (V), R3-s~2-NH2 (~) 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) tria2olinones of the general formula (II) O
H-N- _N-R1 I
N----in which R1 and R2 have the abovementioned meanings are reacted with sulphonamide derivatives of the general formula (VI) R3-S02-NH-CO-Z (VI) in which R3 has the abovementioned meaning and Z represents halogen, alkoxy, aralkoxy or aryloxy, if appropriate in the presence of an acid acceptor and if 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).

The new sulphonylaminocarbonyltriazolinones having substituents bonded via oxygen, of the general formula (I), and their salts are distinguished by a powerful herbicidal act ivit y .
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.

Preferred salts are sodium, potassium, magnesium, calcium, ammonium, C1-C4-alkyl-ammonium, di-(C1-C4-alkyl)-ammonium, tri-(C1-C4-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.

Examples of the compounds are listed in Table 1 below - cf. also the Preparation Examples.
R3-SOZ-NH-CO-N N Rl N--O-RZ

' Tab : Examples of the comgour~ds of the formula (I) F

OCHF'2 CH3 CH2-CH=CH2 SOZN(CH3)2 CH3 , CH3 ~H2-.. OOC2H5 N~

Le ~ 28 ~~~ - 19 -T 1 : (Continuation) Rl R2 R3 i F3 CH3 \ H2-_ \
~zHs CH(CH3)2 ~ ( CON(CH3)2 ~.e A 28 318 _ - 20 -ab a : (Continuation) CH3 , CH(CH3)2 SCH(CH3)2 CH3 CHZ-CH=CHZ

C2H5 ~ CH3 \
F

Si(CH3)3 CHa C2H5 1 , \

C2H5 . C3H' ~HZ_ CH3 C2H5 ' i , ON(CH3)2 ~e A 28 318 - 21 -Teb-le : (Continuation) Br CHZ-~ CH3 \

-~ \

r N~

502N(CH3)2 C3H'_n \ HZ_ COOCH(CH3)2 CH3 ~ C2H8 \
.- ~ Cl Le A 28 318 - 22 -T b a : (Continuation) Ri R2 ~3 COOC2Hs CH3 CH3 \
~-CH3 C2H5 \
O
CH3 S-CH2-C~CH \
S
N_ CH3 C2H5 ;\

T1~N
w Ii''~N
i ~e A 28 318 - 23 -Tabl : (Continuation) N'~S
CON(CH3)2 CH3 C3H~
H3C y CH2-CH=CH2 C2H5 ~H2_ r CH2-CH=CH2 CH3 Id~N

.. SOZNCH3(OCH3) Le A 28 318 - 24 -s Table 1: (Continuation) C3H' CH2-CH*CH2 --0 \

8r NON

CH3. C2H5 . \
S02-( Le A 28 X18 ~ - 25 - -~~ble s (Continuation) CH3 C3H~ \ HZ-C3H~ CH3 C3H? CH3 \

C3H~ C2H5 F

CH3 C2H5 \
' N

CH3 CH3 i ' CF3 Le A 28 318 - 26 -fable l: (Continuation) N(CH3)2 CH3 CH3 C2H5 i ' SO~NHZ
SO~NH2 C2H5 CZHS ~Tl S02NH~

S~0-CF2-CF2C1 N(CH3)2 CH3 I~,e A 28 318 - 27 -If, for 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~N~N~~3 / S02-N=C=O
N
~2Hs F
F O
S02-NH-CO~N~N~~3 I
F N--~
~OC H -If, for example, 2-methylthio-benzenesulphonamide 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:

C1-CO~N~N~N(CH3~
I -N ~3H~

O
S02-NH-CO..,N~N~N(CH3~
I
N---~
~OC H

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:
O
H~N~N~CHF2 S02-NH-COOCH 3 + I
N

-HOCH S02-NH-CO~.N~N~C~2 N--~3 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.

Examples of the starting substances of the fonaula (II) are listed in Table 2 b~low.
O
HN~NiRl 2 III) -R
Le A 28 318 ~ - 30 -Table : Examples of the etarti~g substances of the formula (II) H C~13 C3H' CH3 CHtCH3)2 CH3 CH3 C3H~

CH3 CHtCH3)2 CH3 CH2-CH=CH2 Le A 28 318 - 31 -w Tab : (Continuation) CH3 CH2-C~CH

CH2-CH=CH2 C2H5 CH2-CHBr-CH2Br CZHS

C3H~

CH2-CHsCH2 CH(CH3)2 C2H5 CHICH3)2 C3H~ CH(CH3)2 CH2-CH=CH2 C3H~

C2H5 , -CH2-C~CH

Le $ 2~ 318 - 32 -Some of the starting substances of the formula (II) are the subject of German application 4,030,063, published March 26, 1992.
The compounds of the general formula (II) in which Rl has the abovementioned 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 (VII) H2N-NH-CO-O-RZ' (VI I ) in which R2' represents methyl, ethyl or phenyl are reacted with alkyliminocarbonic diesters of the general formula (VIII) O-Ra Rl -N=C ~ ( V I I 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-alkyl amino, C3-C6-cycloalkylamino or di- (C~,-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-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;
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 R2'-O-CO-NH-N=C ~ ( IX) NH_Rl 33a in which R1, R2 and R2~ have the abovementioned meaning, are, if appropriate, isolated by customary methods and heated to temperatures between 50°C and 150°C, if appropriate in 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-diethylaminosulphonyl-, 2-(N-methoxy-N-methyl)-aminosulphonyl-, 2-phenyl-, 2-phenoxy-, 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 lsocyanate, 4-methoxycarbonyl- and 4-ethoxycarbonyl-1-methyl-pyrazol-5-yl-sulphonyl isocyanate.
The sulphonyl isocyanates of the formula (III) are known and/or can be prepared by processes known per se (cf. US
Patent 4,12?,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, esters 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 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 suction.
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).

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 R1 and R2 and Z preferably represents chlorine, C1-C4-alkoxy, benzyloxy or phenoxy, in partlcular methoxy or phenoxy.
Examples of the starting substances of the formula (IV) which are possible are the compounds of the formula (IV) which are to be prepared from the compounds of the formula (II) listed in Table 2 and phosgene, methyl chloroformate, benzyl chloroformate, phenyl chloroformate or Biphenyl 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) HN~NiR~ (II
) _R2 in which R1 and Rz have the abovementioned meanings are reacted with carbonic acid derivatives of the general formula (X) Z-CO-Z1 (X) in which Z has th~ abovemention~d meaning and Zi~~ represents a leaving group such as chlorine, 1!e A 28 31~ - 38 -methoxy, benzyloxy or phenoxy, if appropriate in 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-methylsulphinyl-, 2-methylsulphonyl-, 2-dimethylaminosulphonyl-, 2-diethylaminasulphonyl-, 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-sulphonamide, 2-methoxycarbonyl-3-thiophenesulphonamide, 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-ides such as, for example, calcium hydroxide, alkali metal carbonates and alkali metal alcoholates such as sodium carbon-ate, potassium carbonate, sodium tert-butylate and potassium tert-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) .

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 pressure.
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 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 one of 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.

r 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:
Dicotyledon weeds of the genera: 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 cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, a Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotvledon cultures of the aenera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds is in no way rest ricted 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 select ive combat ing of weeds in annual cultures .

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, 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-naphthalenes, 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-~,e A 28 318 - 46 -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 as 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 phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can b~ used in the fonaulations . 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 Hlue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dye-stuffs, and trace nutrients such as salts of iron, Le A 28 318 - 47 -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%.
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-d'ichlorophenoxypropionic acid (2,4-DP); 5-(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 1,3,5-triazine (ATRAZINS); methyl 2-[[[[[(4,6-dimethoxy-pyrimidin-2-yl)-amino]-carbonyl]-amino]-sulphonyl]-methyl]-benzoate (eENSULFURON); 3-isopropyl-2,1,3-benzo-thiadiazin-4-one 2,2-dioxide (BENTAZONE); methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate (BIFENOX); 3,5-dibromo-4-hydroxy-benzonitrile; (HROM08YNIL); N-(butoxymethyl)-2-chloro-N-(2,6-diethylph~nyl)-acetamide (BDTACHLOR);
5-amino-4-chloro-2-phenyl-2,3-dihydro-3-oxy-pyridazine (CHLORIDAZON); ethyl 2-~[(~-chloro-6-methoxy-2-pyrimi-dinyl)-aminocarbonyl]-aminosulphonyl~-benzoate (CHLORIMURON); N-(3-chlorophenyl)-isopropyl carbamate (CHLOROPROPHAM); 2-chloro-N-~[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyls-benzenesulphonamide (CHLORSULFURON); N,N-dimethyl-N'-(3-chloro-4-methyl-phenyl)-urea (CHLORTOLURON); exo-1-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)-thiopyian-3-ylj-2-cyclohexen-1-one (CYCLOXYDIM); 2-[4-(2,4-dichloro-phenoxy)-phenoxy]-propionfc 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-f4-[(6-chloro-2-benzoxazolyl)-oxy]-phenoxy~-propanoic acid, its methyl ester or its ethyl ester (FENOXAPROP); 2-[4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]-propanoic acid or Le A 28 318 - 49 -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)-oxy]-acetic acid or its 1-methylheptyl eater (FLUROXYPYR); 5-(2-chloro-4-trifluoromethyl-phenoxy)-N-methylsulphonyl-2-nitrobenzamide (FOMESAFEN); N-phos-phonomethyl-glycine (GLYPHOSATE); 2-i4-[(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);methyl 2-[4,5-dihydro-4-methyl-4-(1-methyl-ethyl)-5-oxo-iH-imidazol-2-yl]-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-ii~ethyl-1,3,5-triazii~-2-yl)-amino)-carbonyl]-amino]-Le A 28 318 . - 50 -sulphonyl}-benzoic acid or its methyl ester (METSULFURON); S-ethyl N,N-hexamethylene-thiocarbamate (MOLINATEj; 1-(3-trifluoromethyl-ghenyl)-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 (OXYFLUORFENj; N-(1~-ethylpropylj-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); a-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-ethylthiopropylj-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-pyrimidinylj-aminocarbonyl]-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-ylj-amino]-carbonyl]-amino]-sulphonyl]-thiophene-2-carboxylate (THIAMETURON); S-[(4-chlorophenyl)-methyl] N,N-diethyl-thiocarbamate (THIOHENCARB); S-(2,3,3-trichloroallyl) N,N-diisopropylthiocarbamate (TRIALLATE); 2,6-dinitro-4-trifluoromethyl-N,N-dipropylaniline (TRIFLURALIN).
L~ A 28 318 - 51 -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 10 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.

Preparation Examples Example 1 C~3 O
SO -NH-CO-N~N-CH

N
O
(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 suction.
4.1 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 of compounds 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.

R3-SOZ-NH-CO-N~N-R1 (I) -R
Table c Preparation Examples of the Comgounds of the formula (I) Example Ri R~ R9 Melting 5~ No.
point ( C) 3 CH3 ~ 190 ~

4 CH3 C3H~ 120 NON

CH3 C3H' 134 Le A 2~ 318 - 54 -Ta - Continuation Example R' Ra R9 M6ltint~

No. point ( C) 8r 7 CH3 C3H~ 125 8 CH3 C2H5 ! ( 166-167 NON

CH3 C2H5 ~' 131-132 F

CH3 C2H5 ~ 147-148 Hr _ 11 CH3 C2H5 186-187 12 CH3 C2H5 ~ 125-126 .. COOC2H5 Le A 28 318 - 55 -Tabl - Continuation Example R1 R2 R3 Meltin~

No. point ( C) 14 CH3 C2H5 ~ 188-189 Cl 15 CH3 C2H5 ~ 175-176 .OCF3 16 CH3 C2H5 ~ 152-153 17 CH3 C2H5 ~ 172-173 18 CH3 C2H5 ~ 147-148 19 GH3 C2H5 ~ 183-184 20 CH3 C2H5 ( g Le A 28 318 - 56 -Ta - Continuation Example R1 Ra R' Melting No. point ( C~

22 CH3 C2H5 ' ~ / lb2-163 24 C3H7 CN3 ~ 129-130 F

e~

Br 26 C3H7 CH3 ~ 130-131 ~s 28 C3H7 CH3 ~ 126-127 2.9 C3H7 CH3 ~ 116-117 Le A 28 318 - 57 -Ta - Continuation Example R1 Rz R' Melting No. point ( C) OOCZHS
30 C3H7 CH ~ 1 ~ -31 C3H7 CH3 ~ 156-157 32 C3H7 CH3 ~ 117-118 Cl 36 C3H7 CH3 ~ 3 -.. . OCF3 Le A 28 318 - 58 -Tabl - Continuation Exa~aple R1 R2 R' Meltinq~

No. point ( C) 38 C3H7 CH3 ' 122-123 ~
~

41 CH3 C4H9 ~ 197 ( N'~N

Br 42 CH3 C4H9 ~ 153 ~45 CH3 C4H9 137 Le A 28 318 - 59 -~a~le 3 - Continuation Example R1 Ri R' s ~

point No. ( C ) 46 CH3 C4Hq 148 47' CH3 C4H9 114 48 CH3 C4H9 ~ 147 50 CZHS Tl~i 1 14 Br 53- CH3 ~ 2D9 Le A 28 318 - 60 -Ta - Continuation Example Rl RZ R' ~ Melting No. point ( C) OCF"3 54 CH3 ~ 19i er 55 CH3 ~ 207 56 CH3 CH3 ~ 154 Br Cl 58 CH3 CH3 ~ 179 59 -CH2-CHsCH2 CH3 124 60 -CH2-CH=CH2 CH3 ~ 153 . Br 61 -CH2-CHaCH2 CH3 150 Le A 28 318 - 61 -Table 3. Co~ntinuatio~
Example Rl Rz R~ Melting No. Pnint AC'1 (GIs 62 -~2-~'~2 ~3 I03 ~1 63 -CHs-CH~CHZ CH3 130 \ /
c~~
~3 ~3 196 \ /
CPs 65 CH3 (~I3 \ / 161-I63 (Na-Salt) -~2-~'~2 ~9 130 \ /
CPs 67 CH3 \ / 211 \ /
68 CH3 ~ 179 \ /

Tabl - Continuation Example RZ R~ Melting No. point ( C) 70 -CH2-CH=CH2 CH3 115 OCHFZ

71 CH3 ~ 162 74 CH3 ~ 174 75 -CH2-CH=CH2 CH3 138 77 .. CH3 ~ 150 Le A 28 318 - 63 -Tab - Continuation Example Rl Ra Ra Meltinq ~
No. point ( C) ?8 -CH2 -CH=CH2 CH3 125 ?9 CH3 CH3 145 F

8c 82 C2H5 CH3 ~ 16?-168 gq ~ C2H5 CH3 ~ 1?4-1?5 ~

85.. C2H5 CH3 ~ 140-141 Le A 28 318 - 64 -Tab - Continuation Example R' Rz R~ s ~

point No. ( C ) F

92 CH3 C4H9 ~ 118-119 ~.e A 28 318 - 65 -Table 3 - Continuation Example R1 Ra R' Melting No. point ( C) GI

94 CH3 C4H9 ~ 110-111 F

96 C2H5 ~ 152-153 97 C2H5 ~ 116-117 98 C2H5 ~ 145-146 Cl 99 CZHS ~ 132-133 100 ~ C2H5 88-89 ~e A 28 318 - 66 -Table - Continuation Example Ri RZ R' Melting No. point ( C) 102 C2H5 ~ 79-77 103 -CH2-CH=CH2 C2H5 ~ 114-115 104 -CH2-CH=CH2 C2H5 ~ 104-106 ~
NON

F

105 -CH2-CH=CH2 C2H5 ~ 85-86 Br 106 -CH2-CH=CH2 C2H5 ~ 12I-122 COOC3H~

'107-CH2-CH=CH2 C2H5 ~ 107-108 108 -CH2-CH=CH2 C2H5 ~ 123-124 Le A 2 8 31,~

Tab - Continuation Example Rx R3 Melting No. . point ( C) Cl 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 C2H5 ~ 123-124 113 -CH2-CH=CH2 C2H5 ~ 103-104 114 -CH2-CH=CH2 C2H5 > >250 115 -CH2-CH=CH2 C2H5 ~ H2- 114-115 116 -CH2-CH=CH2 C2H5 ~ 122-123 Le A 28 318 - 68 -Tab -Continuation Examgle R2 R' Melting R' No. paint ( C) 117 CH(CH3)2 C2H5 ~~ 188-190 118 CH(CH3)2 C2H5 ( ~ 230-231 NON

F

119 CH(CH3)2 C2H5 ~ 129-130 Br 120 CH(CH3)2 C2H5 ~ 207 (Zers.) ~

121 CH(CH3)2 C2H5 113-114 U

122 CH(CH3)2 C2H5 195-200 123 CH(CH3)2 C2H5 133-134 CF3 _ __.

124 CH(CH3)2 C2H5 ~ 139-140 Le A 28 318 - 69 -Tabl - Continuation Example R1 RZ R3 Melting No. point ( C) 12S CH(CH3)2 C2H5 ~ 105-106 126 CH(CH3)2 C2H5 ~ 123-124 127 -(CH2)3-OCH3 CH3 ~ 112-114 128 -(CH2)3-OCH3 CH3 ( ~ 92-9S

NON

F

129 -(CH2)3-OCH3 CH3 126-127 Hr 130 -(CH2)3-OCH3 CH3 131 -(CH2)3-OCH3 CH3 132 -(CH2)3-OCH3 CH3 ~ 81-82 Le A 28 318 _ Tabl - Continuation Examp le Rl R2 R' Melting No. point ( C) 133 -(CH2)3-OCH3 CH3 ~ 104-105 134 -(CH2)3-OCH3 CH3 ~ 113-114 135 -(CH2)3-OCH3 CH3 91-92 136 n-C3H7 C2H5 ~ 108 (Zers.) 137 n-C3H7 C2H5 ~ ~ 212-213 NON

F

138 n-C3H7 C2H5 ~_ ~ 106-107 Br 139 n-C3H7 C2H5 127-128 190 n-C3H7 C2H5 ~ 95 (Zers.) Le A 28 318 _ ~1 _ Ta -Continuation Example R2 R3 s Ri ~

point No. ( C ) 141 n-C3H7 C2H5 ~ 132-135 142 n-C3H7 C2H5 ~ 138-140 143 n-C3H7 C2H5 ~ 87-88 .

144 n-C3H7 C2H5 ~ 108-109 145 n-C3H7 C2H5 ~ 154-157 14b n-C3H7 C2N5 ~ 130-133 147 CH(CH3)2 CH3 ~ 150-151 148 CH(CH3)2 CH3 ( ~ 160-161 __-N~N

Le A 28 318 - ?2 -Table - Continuation Example R2 R' Melting R' No. point ( C) F

149 CH(CH3)2 CH3 147-148 Br 150 CH(CH3)2 CH3 ~ 148-150 151 CH(CH3)2 CH3 143-144 152 CH(CH3)2 CH3 - ~ 134-135 153 CH(CH3)2 CH3 ~ 147-150 154 CH(CH3)2 CH3 148-150 ,155 CH(CH3)2 CH3 ~ 143-145 156 CH(CH3)2 CH3 ~ 114-116 .._.

Le A 28 318 73 -Tab - Continuation Example Rz R' Melting Rl No. point ( C) 157 CH(CH3)2 CH3 ~ 125-128 158 CH3 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 CH(CH3)2 ~ 128-130 163 CH3 CH(CH3)2 ~ 150-152 Le A 28 318 - 74 -Ta - Continuation Example Rs R3 Melting Ri No. point ( C?

165 CH ~ 130-132 166 ~ C2H5 ~ 148-150 ~

167 C2H5 CH3 ~ 172-173 168 -CH2-CH=CH2 C2H5 , 130-132 169 CHtCH3)2 C2H5 ' 142-144 OOCH

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

COOCH

171 n-C3H7 C2H5 ~ ~ 127-130 172 CH(CH3)2 CH3 ~ 156-157 173 CH3 CHtCH3)2 ~ 198-200 ~

COOC3H7 -n 174 CH(CH3)2 C2H5 ~ 122-124 Le A 28 318 - ~5 T$ble 3 - Continuation Example R' R2 R3 Melting No. point ( C) COOC3H7-n 175 -(CH2)3-OCH3 CH3 97-98 COOC3H7-n 176 n-C3H7 C2H5 ~ 128-130 COOC3H7-n 177 CH(CH3)2 CH3 148-150 COOC3H7-n 178 CH3 CH(CH3)2 ~ 154 COOC3H7-n 179 C2H5 CH3 ~ 145 180 CH3 C2H5 ~CH2- 134-136 S02N(CH3)2 181 CH3 C2H5 ~ 178 182 CH3 n-C4H9 ~ H2- 142-143 Le A 28 318 _ Table 3-Condawdo~

g~ple Rl RZ R3 Mcldng No.

o(~lPs 183 C.jI~ CH3 ~ _ lls-118 s ~s 184 -cH2~H-ci'12 CZHs ~ _ 98-99 18s c~9 C~

~ (Na-Sslt) ~H.~-n =

lss cx3 czx~ / 13s-14o ~

(Ns-salt) - ?? -Starting substances of the formula (II),:
Example (II 11 H-N~N-CHZ-CH~CHZ
~0-CH3 . A mixture of 5.0 g (0.02 mol) of 1-phenoxycarbonyl-4-allyl-0-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 (64% 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 28 318 - 78 -Exanple '~ II-,21 O
H-N~N-CH3 ~CH3 50.2 g (0.33 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 is 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 ( I I ) which can be prepared analogously to Examples (II-1) and (II-2) are those listed in Table 4 below, w H-N~N-R1 2 (II) -R
~: Examples of the starting substances of the formula (II) Example Ri Ra Melting No. point ( C) II-4 CH3 C3H~ ~2 II-7 CH(CH3)2 CH3 80-81 I I -8 C2H5 CH3 (b . p . : 120 C

at 1,5 mbar) tb-p.: 130-150 C
II-9 C3H~ CH3 at 1,5 mbar) II-11 (CH2)30CH3 CH3 84-85 'b a r . ) 1,5 mb:

II-13 CH(CH3)2 CZHS 66-67 II-14 C3H~ C2H5 ~ C
Cba ~
O

l,S
n,ba II-15 CH2=CH-CH2 CZHS tb p~

i,5 mbar) .
Intermediates of the formy~la iIXlt /~ ,O-CH3 ~-CO-NH-N=C., NH-CH2-CH=CH2 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 r _ R2 R27-0- CO- NH- N=C ~ I X) NH- R ~
Tabig 5s Examples of the compounds o~ the formula (1X) Example R~ ' R2 ~ R2~ . Melting No. , nnint r~r~

IX-3 C2Hg CH3 C~HS 137 .
ype Examples:
In the Use Examples, the following compound (A) is used as comparison substance:
ci p 502-NH-CO-NnN-CH3 (A) 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
Post-emergence test Solvent: 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.
Test plants-which have a height bf 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 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 water/ha.
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 denotes 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 Solvent: 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 test plants are sown in normal soil and, after 24 hours, watered with the preparation of the Le A 28 318 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 per 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 denotes 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.

Le A 28 318

Claims

CLAIMS:

1. A process for preparing a triazolinone of the general formula (II):

wherein:
R1 represents : (i) H, amino, allyl, C3-C6-cycloalkyl, benzyl, phenyl, C1-C3-alkylamino, C3-C6-cycloalkylamino or di- (C1-C3-alkyl) -amino, or (ii) C1-C4-alkyl which is optionally substituted by F, cyano, methoxy or ethoxy; and R2 represents: (i) C1-C4-alkyl which is optionally substituted by F, Cl or a combination thereof, methoxy or ethoxy, (ii) C3-C4-alkenyl which is optionally substituted by F, Cl or a combination thereof, (iii) C3-C6-cycloalkyl, or (iv) phenyl or benzyl which is optionally substituted by F, Cl, methyl or a combination thereof, which process comprises heating a compound of the general formula (IX):

wherein R1 and R2 are as defined above, and R27 represents methyl, ethyl or phenyl, at a temperature of from 50°C to 150°C.