Sulfonylaminocarbony-triazolinones having substituents attached through sulfur.

0001The invention relates to new sulfonylaminocarbonyltriazolinones with substituents bonded via sulfur, several processes for their preparation and their use as herbicides.

0002It is known that certain substituted aminocarbonylimidazolidinones, such as. B. 1-isobutylaminocarbonyl-2-imidazolidinone (isocarbamide), have herbicidal properties (see R. Wegler, Chemistry of Plant Protection and Pest Control, Volume 5, p. 219, Springer-Verlag, Berlin-Heidelberg-New York, 1977) . However, the effect of this compound is not satisfactory in all respects.

0003The new sulfonylaminocarbonyl-triazolinones with sulfur-bonded substituents of the general formula (I)<chemistry id="chem0001" num="0001"><img file="EP0431291A2_D0001.tif" /></chemistry> in which n represents the numbers 0, 1 or 2, R¹ represents hydrogen, hydroxy, amino or an optionally substituted radical from the series alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl, aryl, alkoxy, alkenyloxy, alkylamino, cycloalkylamino, dialkylamino, R² is an optionally substituted radical from the series alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aralkyl, aryl, and R³ for an optionally substituted radical from the series alkyl, aralkyl, aryl, Heteroaryl stands, as well as salts of compounds of formula (I) found.

0004The new sulfonylaminocarbonyltriazolinones with sulfur-bonded substituents of the general formula (I) are obtained if<ul id="ul0001" list-style="none"><li>a) triazolinones of the general formula (II)<chemistry id="chem0002" num="0002"><img file="EP0431291A2_D0002.tif" /></chemistry> in which n, R¹ and R² have the meanings given above, with sulfonyl isocyanates of the general formula (III) R³-SO₂-N = C = O (III) in which R³ has the meaning given above, if appropriate in the presence of a diluent, or if one</li><li>b) triazolinone derivatives of the general formula (IV)<chemistry id="chem0003" num="0003"><img file="EP0431291A2_D0003.tif" /></chemistry> in which n, R¹ and R² have the meanings given above and Z represents halogen, alkoxy, aralkoxy or aryloxy, with sulfonic acid amides of the general formula (V) R³-SO₂-NH₂ (V) in which R³ has the meaning given above, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or if</li><li>c) triazolinones of the general formula (II)<chemistry id="chem0004" num="0004"><img file="EP0431291A2_D0004.tif" /></chemistry> in which n, R¹ and R² have the meanings given above, with sulfonic acid amide derivatives of the general formula (VI) R³-SO₂-NH-CO-Z (VI) in which R³ has the meaning given above 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 from the processes (a), (b) or (c) compounds of formula (I) produced by conventional methods salts.</li></ul>

0005The new sulfonylaminocarbonyltriazolinones with sulfur-bonded substituents of the general formula (I) and their salts are notable for strong herbicidal activity.

0006Surprisingly, the new compounds of the formula (I) show considerably better herbicidal activity than the structurally similar known herbicide 1-isobutylaminocarbonyl-2-imidazolidinone (isocarbamide).

0007The invention preferably relates to compounds of the formula (I) in which n represents the numbers 0, 1 or 2, R¹ for hydrogen, hydroxy, amino, optionally substituted by fluorine, chlorine, bromine, cyano, C₁-C₄-alkoxy, C₁-C₄-alkylcarbonyl or C₁-C₄-alkoxy-carbonyl C₁-C₆-alkyl, each optionally substituted by fluorine , Chlorine and / or bromine substituted C₃-C₆-alkenyl or C₃-C₆-alkynyl, optionally with fluorine, chlorine, Bromine and / or C₁-C₄-alkyl substituted C₃-C₆-cycloalkyl, for optionally by fluorine, chlorine, bromine, cyano, nitro, C₁-C₄-alkyl, trifluoromethyl, C₁-C₄-alkoxy and / or C₁-C₄-alkoxy -carbonyl-substituted phenyl-C₁-C₃-alkyl, optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C₁-C₄-alkyl, trifluoromethyl, C₁-C₄-alkoxy, fluorine and / or chlorine-substituted C₁-C₃- Alkoxy, C₁-C₄-alkylthio, fluorine and / or chlorine-substituted C₁-C₃-alkylthio, C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl and / or C₁-C₄-alkoxy-carbonyl-substituted phenyl, for optionally substituted by fluorine, chlorine, cyano, phenyl, C₁-C₄-alkoxy or C₁-C₄-alkoxy-carbonyl-substituted C₁-C₆-alkoxy, for C₃-C₄-alkenyloxy, for optionally substituted by fluorine, cyano, C₁-C₄-alkoxy or C₁-C₄-alkoxy-carbonyl, C₁-C₄-alkylamino, C₃-C₆-cycloalkylamino or for di- (C₁-C₄-alkyl) - amino stands, R² for optionally by fluorine, chlorine, bromine, cyano, C₃-C₆-cycloalkyl, C₁-C₄-alkoxy or C₁-C₄-alkoxycarbonyl substituted C₁-C₆-alkyl, for each optionally substituted by fluorine, chlorine and / or bromine substituted C₃-C₆-alkenyl or C₃-C₆-alkynyl, optionally substituted by fluorine, chlorine, bromine and / or C₁-C₄-alkyl substituted C₃-C₆-cycloalkyl, for cyclohexenyl, for optionally by fluorine, chlorine, bromine, cyano, nitro, C₁-C₄-alkyl, trifluoromethyl, C₁-C₄-alkoxy and / or C₁-C₄ -Alkoxycarbonyl-substituted phenyl-C₁-C₃-alkyl, or for optionally fluorine, Chlorine, bromine, cyano, nitro, C₁-C₄-alkyl, trifluoromethyl, C₁-C₄-alkoxy, fluorine and / or chlorine-substituted C₁-C₃-alkoxy, C₁-C₄-alkylthio, fluorine and / or chlorine-substituted C₁-C₃-alkylthio, C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl and / or C₁-C₄-alkoxy-carbonyl substituted phenyl and R³ for grouping<chemistry id="chem0005" num="0005"><img file="EP0431291A2_D0005.tif" /></chemistry> stands in what R⁴ and R⁵ are the same or different and represent hydrogen, fluorine, chlorine, bromine, iodine, nitro, C₁-C₆-alkyl (which may be replaced by fluorine, chlorine, bromine, cyano, carboxy, C₁-C₄-alkoxycarbonyl, C₁-C₄- Alkylamino-carbonyl, di- (C₁-C₄-alkyl) amino-carbonyl, hydroxy, C₁-C₄-alkoxy, formyloxy, C₁-C₄-alkyl-carbonyloxy, C₁-C₄-alkoxy-carbonyloxy, C₁-C₄-alkylamino-carbonyloxy , C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl, di- (C₁-C₄-alkyl) -aminosulfonyl, C₃-C₆-cycloalkyl or phenyl is substituted) for C₂-C₆-alkenyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, C₁-C₄-alkoxy-carbonyl, carboxy or phenyl), for C₂-C₆-alkynyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, C₁-C₄alkoxycarbonyl, carboxy or phenyl) for C₁-C₄alkoxy (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxy, C₁-C₄ -Alkoxy-carbonyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl or C₁-C₄-alkylsulfonyl is substituted) for C₁-C₄-alkylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxy, C₁-C₄-alkoxy-carbonyl, C₁-C₄-alkylthio, C₁ -C₄-alkylsulfinyl or C₁-C₄-alkylsulfonyl is substituted) for C₃-C₆-alkenyloxy (which is optionally substituted by fluorine, chlorine, bromine, cyano or C₁-C₄-alkoxy-carbonyl), for C₂-C₆-alkenylthio ( which may be by fluorine, chlorine, bromine, cyano, nitro, C₁-C₃-alkylthio or C₁-C₄-alkoxycarbonyl is substituted), C₃-C₆-alkynyloxy, C₃-C₆-alkynylthio or for the rest -S (O)_p-R⁶ stand, whereby p represents the numbers 1 or 2 and R⁶ for C₁-C₄-alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano or C₁-C₄-alkoxy-carbonyl), C₃-C₆-alkenyl, C₃-C₆-alkynyl, C₁-C₄-alkoxy, C₁- C₄-alkoxy-C₁-C₄-alkylamino, C₁-C₄-alkylamino, di- (C₁-C₄-alkyl) -amino, phenyl or for the radical -NHOR⁷, where R⁷ for C₁-C₁₂-alkyl (which may be fluorine, chlorine, cyano, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl, C₁-C₄-alkyl-carbonyl, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylamino-carbonyl or di- (C₁-C₄-alkyl) -amino-carbonyl is substituted) for C₃-C₆-alkenyl (which is optionally substituted by fluorine , Chlorine or bromine is substituted), C₃-C₆-alkynyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₂-alkyl, phenyl-C₁-C₂-alkyl (which may be substituted by fluorine, chlorine, nitro, cyano , C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-alkoxy-carbonyl is substituted), for benzhydryl or for phenyl (which is optionally substituted by fluorine, Chlorine, nitro, cyano, C₁-C₄-alkyl, trifluoromethyl, C₁-C₄-alkoxy, C₁-C₂-fluoroalkoxy, C₁-C₄-alkylthio, trifluoromethylthio or C₁-C₄-alkoxycarbonyl is substituted), R⁴ and / or R⁵for phenyl or phenoxy, for C₁-C₄-alkylcarbonylamino, C₁-C₄-alkoxycarbonylamino, C₁-C₄-alkylamino-carbonylamino, di- (C₁-C₄-alkyl) -amino-carbonylamino, or for the Rest -CO-R⁸ are, wherein R⁸ for C₁-C₆ alkyl, C₁-C₆ alkoxy, C₃-C₆ cycloalkoxy, C₃-C₆ alkenyloxy, C₁-C₄ alkylthio, C₁-C₄ alkylamino C₁-C₄-alkoxyamino, C₁-C₄-alkoxy-C₁-C₄-alkyl-amino or di- (C₁-C₄-alkyl) -amino (which are optionally substituted by fluorine and / or chlorine), R⁴ and / or R⁵ furthermore for trimethylsilyl, thiazolinyl, C₁-C₄-alkylsulfonyloxy, di- (C₁-C₄-alkyl) -aminosulfonylamino or for the radical -CH = N-R⁹, where R⁹ for C₁-C₆-alkyl optionally substituted by fluorine, chlorine, cyano, carboxy, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl or C₁-C₄-alkylsulfonyl, for optionally substituted by fluorine or chlorine benzyl, for optionally substituted by fluorine or chlorine C₃-C₆-alkenyl or C₃-C₆-alkynyl, for optionally by fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, trifluoromethyl , Trifluoromethoxy or trifluoromethylthio substituted phenyl, for optionally substituted by fluorine and / or chlorine C₁-C₆-alkoxy, C₃-C₆-alkenoxy, C₃-C₆-alkynoxy or benzyloxy for amino, C₁-C₄-alkylamino, di- (C₁-C₄ alkyl) amino, phenylamino, C₁-C₄-alkyl-carbonyl-amino, C₁-C₄-alkoxy-carbonylamino, C₁-C₄-alkyl-sulfonylamino or phenylsulfonylamino optionally substituted by fluorine, chlorine, bromine or methyl, Farther R³ for the rest<chemistry id="chem0006" num="0006"><img file="EP0431291A2_D0006.tif" /></chemistry> stands in what R¹⁰ represents hydrogen or C₁-C₄ alkyl, R¹¹ and R¹² are the same or different and are hydrogen, fluorine, chlorine, bromine, nitro, cyano, C₁-C₄-alkyl (which is optionally substituted by fluorine and / or chlorine), C₁-C₄-alkoxy (which is optionally substituted by fluorine and / or chlorine is substituted), carboxy, C₁-C₄-alkoxy-carbonyl, dimethylaminocarbonyl, C₁-C₄-alkylsulfonyl or di- (C₁-C₄-alkyl) -aminosulfonyl; Farther R³ for the rest<chemistry id="chem0007" num="0007"><img file="EP0431291A2_D0007.tif" /></chemistry> stands in what R¹³ and R¹⁴ are the same or different and are hydrogen, fluorine, chlorine, bromine, nitro, cyano, C₁-C₄-alkyl (which is optionally substituted by fluorine and / or chlorine) or C₁-C₄-alkoxy (which is optionally substituted by fluorine and / or chlorine is substituted); Farther R³ for the rest<chemistry id="chem0008" num="0008"><img file="EP0431291A2_D0008.tif" /></chemistry> stands in what R¹⁵ and R¹⁶ are the same or different and are hydrogen, fluorine, chlorine, bromine, nitro, cyano, C₁-C₄-alkyl (which is optionally substituted by fluorine and / or chlorine), C₁-C₄-Al koxy (which is optionally substituted by fluorine and / or chlorine is substituted), for C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl or C₁-C₄-alkylsulfonyl (which are optionally substituted by fluorine and / or chlorine), for aminosulfonyl, mono- (C₁-C₄-alkyl ) aminosulfonyl, represent di- (C₁-C₄-alkyl) -aminosulfonyl or C₁-C₄-alkoxycarbonyl or dimethylaminocarbonyl; Farther R³ for the rest<chemistry id="chem0009" num="0009"><img file="EP0431291A2_D0009.tif" /></chemistry> stands in what R¹⁷ and R¹⁸ are the same or different and are hydrogen, fluorine, chlorine, bromine, C₁-C₄-alkyl (which is optionally substituted by fluorine and / or bromine), C₁-C₄-alkoxy (which is optionally substituted by fluorine and / or chlorine is) for C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl or C₁-C₄-alkylsulfonyl (which are optionally substituted by fluorine and / or chlorine), or for di- (C₁-C₄-alkyl) -aminosulfonyl; Farther R³ for the rest<chemistry id="chem0010" num="0010"><img file="EP0431291A2_D0010.tif" /></chemistry> stands in what R¹⁹ and R²⁰ are the same or different and are hydrogen, fluorine, chlorine, bromine, cyano, nitro, C₁-C₄-alkyl (which is optionally substituted by fluorine and / or chlorine), C₁-C₄-alkoxy (which is optionally substituted by fluorine and / or chlorine is substituted), C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl or C₁-C₄-alkylsulfonyl (which is optionally substituted by fluorine and / or chlorine), di- (C₁-C₄-alkyl) -aminosulfonyl , C₁-C₄-alkoxy-carbonyl or dimethylaminocarbonyl, and A represents oxygen, sulfur or the grouping N-Z¹, where Z¹ for hydrogen, C₁-C₄-alkyl (which is optionally substituted by fluorine, chlorine, bromine or cyano), C₃-C₆-cycloalkyl, benzyl, phenyl (which is optionally substituted by fluorine, chlorine, bromine or nitro), C₁- C₄-alkylcarbonyl, C₁-C₄-alkoxy-carbonyl or di- (C₁-C₄-alkyl) -aminocarbonyl; Farther R³ for the rest<chemistry id="chem0011" num="0011"><img file="EP0431291A2_D0011.tif" /></chemistry> stands in what R²¹ and R²² are the same or different and represent hydrogen, C₁-C₄-alkyl, halogen, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy, Y¹ is sulfur or the grouping N-R²³, in which R²³ represents hydrogen or C₁-C₄ alkyl; Farther R³ for the rest<chemistry id="chem0012" num="0012"><img file="EP0431291A2_D0012.tif" /></chemistry> stands in what R²⁴ represents hydrogen, C₁-C₄ alkyl, benzyl, pyridyl, quinolinyl or phenyl, R²⁵ for hydrogen, halogen, cyano, nitro, C₁-C₄-alkyl (which is optionally substituted by fluorine and / or chlorine), C₁-C₄-alkoxy (which is optionally substituted by fluorine and / or chlorine), dioxolanyl or C₁- C₄-Alkoxy-carbonyl is and R²⁶ represents hydrogen, halogen or C₁-C₄ alkyl; Farther R³ represents one of the groups listed below,<chemistry id="chem0013" num="0013"><img file="EP0431291A2_D0013.tif" /></chemistry> The invention further preferably sodium, potassium, magnesium, calcium, ammonium, C₁-C₄-alkyl-ammonium, di- (C₁-C₄-alkyl) -ammonium-, tri- (C₁-C₄- alkyl) ammonium, C₅ or C₆ cycloalkylammonium and di (C₁-C₂alkyl) benzylammonium salts of compounds of formula (I) in which n, R¹, R² and R³ are the above preferably have the meanings given.

0008The invention relates in particular to compounds of the formula (I) in which n represents the numbers 0, 1 or 2, R¹ for hydrogen, amino, optionally substituted by fluorine, cyano, methoxy or ethoxy-substituted C₁-C₄-alkyl, for allyl, for C₃-C₆-cycloalkyl, for benzyl, for phenyl, for C₁-C₄-alkoxy, for C₃-C₄ -Alkenyloxy, represents C₁-C₃-alkylamino, C₃-C₆-cycloalkylamino or di- (C₁-C₃-alkyl) -amino, R² is hydrogen, optionally by fluorine and / or chlorine, Methoxy or ethoxy substituted C₁-C₄-alkyl, optionally substituted by fluorine and / or chlorine, C₃-C₄-alkenyl, C₃-C₆-cycloalkyl or optionally substituted by fluorine, chlorine and / or methyl, and R³ for grouping<chemistry id="chem0014" num="0014"><img file="EP0431291A2_D0014.tif" /></chemistry> stands in what R⁴ for fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, 2-chloro-ethoxy, 2-methoxy-ethoxy, C₁-C₃-alkylthio, C₁-C₃-alkylsulfinyl, C₁-C₃-alkylsulfonyl, dimethylaminosulfonyl, Diethylaminosulfonyl, N-methoxy-N-methylaminosulfonyl, methoxyaminosulfonyl, phenyl, phenoxy or C₁-C₃-alkoxy-carbonyl and R⁵ represents hydrogen, fluorine, chlorine or bromine; Farther R³ for the rest<chemistry id="chem0015" num="0015"><img file="EP0431291A2_D0015.tif" /></chemistry> stands in what R¹⁰ represents hydrogen, R¹¹ represents fluorine, chlorine, bromine, methyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methylsulfonyl or dimethylaminosulfonyl and R¹² is hydrogen; Farther R³ for the rest<chemistry id="chem0016" num="0016"><img file="EP0431291A2_D0016.tif" /></chemistry> stands, wherein R is C₁-C₄ alkyl, or for the rest<chemistry id="chem0017" num="0017"><img file="EP0431291A2_D0017.tif" /></chemistry> stands, wherein R is C₁-C₄ alkyl.

0009Examples of the compounds according to the invention are listed in Table 1 below - cf. also the manufacturing examples.<chemistry id="chem0018" num="0018"><img file="EP0431291A2_D0018.tif" /></chemistry><tables id="tabl0001" num="0001"><img file="EP0431291A2_D0019.tif" /></tables><tables id="tabl0002" num="0002"><img file="EP0431291A2_D0020.tif" /></tables><tables id="tabl0003" num="0003"><img file="EP0431291A2_D0021.tif" /></tables><tables id="tabl0004" num="0004"><img file="EP0431291A2_D0022.tif" /></tables><tables id="tabl0005" num="0005"><img file="EP0431291A2_D0023.tif" /></tables><tables id="tabl0006" num="0006"><img file="EP0431291A2_D0024.tif" /></tables><tables id="tabl0007" num="0007"><img file="EP0431291A2_D0025.tif" /></tables><tables id="tabl0008" num="0008"><img file="EP0431291A2_D0026.tif" /></tables><tables id="tabl0009" num="0009"><img file="EP0431291A2_D0027.tif" /></tables>

0010If, for example, 2,6-difluorophenyl isocyanate and 5-ethylthio-4-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one are used as starting materials, the course of the reaction in the process according to the invention (a ) are outlined using the following formula:<chemistry id="chem0019" num="0019"><img file="EP0431291A2_D0028.tif" /></chemistry>

0011If, for example, 2-methylthio-benzenesulfonamide and 2-chlorocarbonyl-4-dimethylamino-5-propylthio-2,4-dihydro-3H-1,2,4-triazol-3-one are used as starting materials, the course of the reaction in the process according to the invention can be carried out (b) are sketched by the following formula scheme:<chemistry id="chem0020" num="0020"><img file="EP0431291A2_D0029.tif" /></chemistry>

0012If, for example, N-methoxycarbonyl-2-methoxy-benzenesulfonamide and 5-methylsulfonyl-4-difluoromethyl-2,4-dihydro-3H-1,2,4-triazol-3-one are used as starting materials, the course of the reaction in the process according to the invention can (c) are sketched by the following formula scheme:<chemistry id="chem0021" num="0021"><img file="EP0431291A2_D0030.tif" /></chemistry>

0013Formula (II) provides a general definition of the triazolinones to be used as starting materials in processes (a) and (c) for the preparation of compounds of the formula (I).

0014In formula (II), n, R¹ and R² preferably or in particular have those meanings which have already been given above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for n, R¹ and R².

0015Examples of the starting materials of the formula (II) are listed in Table 2 below.<chemistry id="chem0022" num="0022"><img file="EP0431291A2_D0031.tif" /></chemistry><tables id="tabl0010" num="0010"><img file="EP0431291A2_D0032.tif" /></tables><tables id="tabl0011" num="0011"><img file="EP0431291A2_D0033.tif" /></tables><tables id="tabl0012" num="0012"><img file="EP0431291A2_D0034.tif" /></tables>

0016The starting materials of the formula (III) are known and / or can be prepared by processes known per se (cf. J. Heterocycl. Chem. 15 (1978), pp. 377-384; DE-OS 2 250 572; DE-OS 2,527,676; DE-OS 3,709,574; US-P 4,098,896; US-P 4,110,332; JP-A-52-125 168).

0017Formula (III) provides a general definition of the sulfonyl isocyanates to be used as starting materials in process (a) according to the invention for the preparation of compounds of the formula (I).

0018In formula (III), R³ preferably or in particular has the meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R³.

0019Examples of the starting materials of the formula (III) are: 2-fluoro, 2-chloro, 2-bromo, 2-methyl, 2-methoxy, 2-trifluoromethyl, 2-difluoromethoxy, 2-trifluoromethoxy, 2-methylthio, 2-ethylthio -, 2-propylthio, 2-methylsulfinyl, 2-methylsulfonyl, 2-dimethylaminosulfonyl, 2-diethylaminosulfonyl, 2- (N-methoxy-N-methyl) -aminosulfonyl-, 2-phenyl-, 2-phenoxy -, 2-methoxycarbonyl, 2-ethoxycarbonyl, 2-propoxycarbonyl and 2-isopropoxycarbonylphenylsulfonyl isocyanate, 2-fluoro, 2-chloro, 2-difluoromethoxy, 2-trifluoromethoxy, 2-methoxycarbonyl and 2-ethoxycarbonylbenzylsulfonyl isocyanate, 2-methoxycarbonyl-3-thienylsulfonyl isocyanate, 4-methoxycarbonyl and 4-ethoxycarbonyl-1-methyl-pyrazol-5-yl-sulfonyl isocyanate.

0020The sulfonyl isocyanates of the formula (III) are known and / or can be prepared by processes known per se (cf. US Pat. Nos. 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).

0021Process (a) according to the invention for the preparation of the new compounds of the formula (I) is preferably carried out using diluents. Practically all inert organic solvents can be used as diluents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl and Dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, Esters such as methyl acetate and ethyl ester, nitriles such as acetonitrile and propionitrile, amides such as. B. dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone and dimethyl sulfoxide, tetramethylene sulfone and hexamethylphosphoric triamide.

0022The reaction temperatures can be varied within a substantial range in process (a) according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably at temperatures between 10 ° C and 80 ° C.

0023Process (a) according to the invention is generally carried out at atmospheric pressure.

0024To carry out process (a) according to the invention, generally between 1 and 3 mol, preferably between 1 and 2 mol, of sulfonyl isocyanate of the formula (III) are used per mol of triazolinone of the formula (II).

0025The reaction components can be combined in any order. The reaction mixture is stirred until the reaction is complete and the product is isolated by suction. In another work-up variant, the mixture is concentrated and the crude product remaining in the residue with a suitable solvent, such as. B. diethyl ether, brought to crystallization. The crystalline product of formula (I) is isolated by suction.

0026Formula (IV) provides a general definition of the triazolinone derivatives to be used as starting materials in process (b) according to the invention for the preparation of compounds of the formula (I).

0027In formula (IV), n, R¹ and R² preferably or in particular have those meanings which have already been given above or in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for n, R¹ and R² and Z preferably represents chlorine, C₁-C₄ alkoxy, benzyloxy or phenoxy, in particular methoxy or phenoxy.

0028Possible examples of the starting materials of the formula (IV) are the compounds of the formula (IV) to be prepared from the compounds of the formula (II) listed in Table 2 and phosgene, methyl chloroformate, benzyl chloroformate, phenyl chloroformate or diphenyl carbonate.

0029The starting materials of the formula (IV) are not yet known.

0030The new triazolinone derivatives of the formula (IV) are obtained if triazolinones of the general formula (II)<chemistry id="chem0023" num="0023"><img file="EP0431291A2_D0035.tif" /></chemistry> in which n, R¹ and R² have the meanings given above, with carbonic acid derivatives of the general formula (XI) Z-CO-Z¹ (XI) in which Z has the meaning given above and Z¹ represents a leaving group such as chlorine, methoxy, benzyloxy or phenoxy, optionally in the presence of a diluent such as tetrahydrofuran and optionally in the presence of an acid acceptor such as Sodium hydride or potassium tert-butoxide, at temperatures between -20 ° C and + 100 ° C (see also the manufacturing examples).

0031Formula (V) provides a general definition of the sulfonamides to be used as starting materials in process (b) according to the invention for the preparation of compounds of the formula (I).

0032In formula (V), R³ preferably or in particular has the meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R³.

0033The following are examples of the starting materials of the formula (V): 2-fluoro, 2-chloro, 2-bromo, 2-methyl, 2-methoxy, 2-trifluoromethyl, 2-difluoromethoxy, 2-trifluoromethoxy, 2-methylthio, 2-ethylthio -, 2-propylthio, 2-methylsulfinyl, 2-methylsulfonyl, 2-dimethylaminosulfonyl, 2-diethylaminosulfonyl, 2- (N-methoxy-N-methyl) aminosulfonyl, 2-phenyl, 2-phenoxy -, 2-methoxycarbonyl-, 2-ethoxycarbonyl-, 2-propoxycarbonyl- and 2-isopropoxycarbonyl-benzenesulfonamide, 2-fluoro-, 2-chloro-, 2-difluoromethoxy-, 2-trifluoromethoxy-, 2-methoxycarbonyl and 2-ethoxycarbonyl-phenylmethanesulfonic acid amide, 2-methoxycarbonyl-3-thiophene sulfonic acid amide, 4-methoxycarbonyl and 4-ethoxycarbonyl-1-methyl-pyrazole-5-sulfonic acid amide.

0034The sulfonic acid amides of the formula (V) are known and / or can be prepared by processes known per se (cf. US Pat. No. 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).

0035Process (b) according to the invention for the preparation of the new compounds of the formula (I) is preferably carried out using diluents. Practically all inert organic solvents, such as those specified above for process (a) according to the invention, are suitable as diluents.

0036Acid acceptors which can be used in process (b) according to the invention are all acid binders which can customarily be used for such reactions. Alkali metal hydroxides such as, for. B. sodium and potassium hydroxide, alkaline earth metal hydroxides such. B. Calcium hydroxide, alkali carbonates and alcoholates such as sodium and potassium carbonate, sodium and potassium tert-butoxide, 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).

0037The reaction temperatures in process (b) according to the invention can be varied within a substantial range. In general, temperatures between 0 ° C and 100 ° C, preferably at temperatures between 10 ° C and 60 ° C.

0038Process (b) according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.

0039To carry out process (b) according to the invention, the starting materials required in each case are generally used in approximately equimolar amounts. However, it is also possible to use one of the two components used 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 temperature required in each case. Working up in process (b) according to the invention is carried out in each case by customary methods.

0040The triazolinones of the formula (II) to be used as starting materials in the process (c) according to the invention for the preparation of compounds of the formula (I) have already been described as starting materials for the process (a) according to the invention.

0041Formula (VI) provides a general definition of the sulfonamide derivatives to be used as starting materials in process (c) according to the invention for the preparation of compounds of the formula (I).

0042In 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) according to the invention preferably or as particularly preferred for R³ and Z.

0043Process (c) according to the invention is preferably carried out using diluents. The same organic solvents that are mentioned above in connection with the description of process (a) according to the invention can be used here.

0044Process (c) is optionally carried out in the presence of an acid acceptor. The same acid binders come into consideration here, which were mentioned above in connection with the description of process (b) according to the invention.

0045The reaction temperatures can be varied within a substantial range in process (c) according to the invention. In general, temperatures between 0 ° C and 100 ° C, preferably at temperatures between 10 ° C and 60 ° C.

0046Process (c) according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.

0047To carry out process (c) according to the invention, the starting materials required in each case are generally used in approximately equimolar amounts. However, it is also possible to use one of the two components used 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 temperature required in each case. Working up in process (c) according to the invention is carried out in each case by customary methods.

0048For conversion into salts, the compounds of the formula (I) are mixed with suitable salt formers, such as sodium or potassium hydroxide, methylate or ethylate, ammonia, isopropylamine, dibutylamine or triethylamine, in suitable diluents, such as water, methanol or ethanol , stirred. The salts can then be isolated as crystalline products, if appropriate after concentration.

0049The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular as weed killers. Weeds in the broadest sense are understood to mean all plants that grow up in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.

0050The active compounds according to the invention can be used, for example, in the following plants:<u style="single">Dicot weeds of the genera:</u> Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippernia, Rorippa, Rorippa, Rorippa Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.<u style="single">Dicotyledon cultures of the genera:</u> Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.<u style="single">Monocot weeds of the genera:</u> Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Spochenium, Ischaeaeaum, Ischaeaumum Agrostis, Alopecurus, Apera.<u style="single">Monocot cultures of the genera:</u> Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

0051However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants.

0052Depending on the concentration, the compounds are suitable for total weed control, for example on industrial and rail tracks and on paths and squares with and without tree cover. The compounds for weed control in permanent crops, for example Forest, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants, on ornamental and sports turf and pasture land and for selective purposes Weed control can be used in annual crops.

0053The compounds of formula (I) according to the invention are particularly suitable for the selective control of monocotyledon and dicotyledon weeds in monocotyledon crops both in the pre-emergence and in the post-emergence process. They are significantly more effective than, for example, isocarbamide.

0054To a certain extent, the compounds according to the invention also show fungicidal activity, for example against Pyricularia on rice.

0055The active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances and very fine encapsulations in polymeric substances.

0056These formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, that is liquid solvents and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents.

0057If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water. Possible solid carriers are: e.g. Ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silicic acid, aluminum oxide and silicates, are suitable as solid carriers for granules: for example broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; Possible emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.

0058Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

0059Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

0060The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

0061The active compounds according to the invention, as such or in their formulations, can also be used in a mixture with known herbicides for weed control, finished formulations or tank mixes being possible.

0062Known herbicides such as, for example, come for the mixtures 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 weed control in cereals; 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5 (4H) -one (METAMITRON) for weed control in sugar beets and 4-amino-6- (1,1-dimethylethyl) -3- methylthio-1,2,4-triazin-5 (4H) -one (METRIBUZIN) for weed control in soybeans, in question; also 2,4-dichlorophenoxyacetic acid (2,4-D); 4- (2,4-dichlorophenoxy) butyric acid (2,4-DB); 2,4-dichlorophenoxypropionic acid (2,4-DP); 3-isopropyl-2,1,3-benzothiadiazin-4-one-2,2-dioxide (BENTAZON); Methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate (BIFENOX); 3,5-dibromo-4-hydroxy-benzonitrile (BROMOXYNIL); 2-chloro-N - {[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] carbonyl} benzenesulfonamide (CHLORSULFURON); N, N-Dimethyl-N ′ - (3-chloro-4-methylphenyl) urea (CHLORTOLURON); 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid, its methyl or its ethyl ester (DICLOFOP); 4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5 (4H) -one (ETHIOZIN); 2- {4 - [(6-chloro-2-benzoxazolyl) -oxy] -phenoxy} -propanoic acid, its methyl or its ethyl ester (FENOXAPROP); [(4-Amino-3,5-dichloro-6-fluoro-2-pyridin-yl) oxy] acetic acid or their 1-methylheptyl ester (FLUROXYPYR); N-phosphonomethylglycine (GLYPHOSATE); Methyl 2- [4,5-dihydro-4-methyl-4- (1-methylethyl) -5-oxo-1H-imidazol-2-yl] -4 (5) methylbenzoate (IMAZAMETHABENZ); 3,5-diiodo-4-hydroxybenzonitrile (IOXYNIL); N, N-Dimethyl-N ′ - (4-isopropylphenyl) urea (ISOPROTURON); (2-methyl-4-chlorophenoxy) acetic acid (MCPA); (4-chloro-2-methylphenoxy) propionic acid (MCPP); N-methyl-2- (1,3-benzothiazol-2-yloxy) acetanilide (MEFENACET); 2 - {[[((4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino) carbonyl] amino] sulfonyl} benzoic acid or its methyl ester (METSULFURON); N- (1-ethylpropyi) -3,4-dimethyl-2,6-dinitroaniline (PENDIMETHALINE); 0- (6-chloro-3-phenyl-pyridazin-4-yl) -S-octyl-thiocarbamate (PYRIDATE); 4-ethylamino-2-t-butylamino-6-methylthio-s-triazine (TERBUTRYNE); 3 - [[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] carbonyl] amino] sulfonyl] thiophene-2-carboxylic acid methyl ester (THIAMETURON) . Surprisingly, some mixtures also show a synergistic effect.

0063A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible.

0064The 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, spraying or scattering.

0065The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be worked into the soil before sowing.

0066The amount of active ingredient used can vary over a wide range. It essentially depends on the type of effect desired. In general, the application rates are between 0.01 and 15 kg of active ingredient per hectare of soil, preferably between 0.05 and 10 kg per ha.

0067The preparation and the use of the active compounds according to the invention are shown in the examples below.

Manufacturing examples

example 1

0068<chemistry id="chem0024" num="0024"><img file="EP0431291A2_D0036.tif" /></chemistry>

00693.0 g (20.7 mmol) of 4-methyl-5-methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one are dissolved in 60 ml of acetonitrile and, with stirring, 7.0 g (29 mmol) of 2-methoxycarbonylphenylsulfonyl isocyanate, dissolved in 20 ml of acetonitrile, were added to this solution. The reaction mixture is stirred at 20 ° C. for 6 hours. Then the crystalline product is isolated by suction.

00706.0 g (75% of theory) of 4-methyl-5-methylthio-2- (2-methoxycarbonylphenylsulfonylaminocarbonyl) -2,4-dihydro-3H-1,2,4-triazole-3- are obtained. on from melting point 184 ° C.

Example 2

0071<chemistry id="chem0025" num="0025"><img file="EP0431291A2_D0037.tif" /></chemistry>

00721.7 g (11.2 mmol) of 1,8-diazabicyclo [5.4.0] -undec-7-ene (DBU) and 2.7 g (11.2 mmol) of 2-trifluoromethoxybenzenesulfonamide become a solution 3.0 g (11.3 mmol) of 4-amino-5-methylthio-2-phenoxy-carbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one in 60 ml of methylene chloride. The reaction mixture is stirred for 4 hours at 20 ° C., then washed twice with 1% hydrochloric acid and three times with water, dried with sodium sulfate and filtered. The filtrate is concentrated, the residue is stirred with diethyl ether and the crystalline product is isolated by suction.

00732.1 g (45% of theory) of 4-amino-5-methylthio-2- (2-trifluoromethoxy-phenylsulfonyl-aminocarbonyl) -2,4-dihydro-3H-1,2,4-triazole-3- on from melting point 136 ° C.

0074Analogously to Examples 1 and 2 and in accordance with the general description of the production processes according to the invention, it is also possible, for example, to prepare the compounds of the formula (I) listed in Table 3 below.<chemistry id="chem0026" num="0026"><img file="EP0431291A2_D0038.tif" /></chemistry><tables id="tabl0013" num="0013"><img file="EP0431291A2_D0039.tif" /></tables><tables id="tabl0014" num="0014"><img file="EP0431291A2_D0040.tif" /></tables><tables id="tabl0015" num="0015"><img file="EP0431291A2_D0041.tif" /></tables><tables id="tabl0016" num="0016"><img file="EP0431291A2_D0042.tif" /></tables><tables id="tabl0017" num="0017"><img file="EP0431291A2_D0043.tif" /></tables><tables id="tabl0018" num="0018"><img file="EP0431291A2_D0044.tif" /></tables><tables id="tabl0019" num="0019"><img file="EP0431291A2_D0045.tif" /></tables><tables id="tabl0020" num="0020"><img file="EP0431291A2_D0046.tif" /></tables><tables id="tabl0021" num="0021"><img file="EP0431291A2_D0047.tif" /></tables><tables id="tabl0022" num="0022"><img file="EP0431291A2_D0048.tif" /></tables><tables id="tabl0023" num="0023"><img file="EP0431291A2_D0049.tif" /></tables><tables id="tabl0024" num="0024"><img file="EP0431291A2_D0050.tif" /></tables><tables id="tabl0025" num="0025"><img file="EP0431291A2_D0051.tif" /></tables><tables id="tabl0026" num="0026"><img file="EP0431291A2_D0052.tif" /></tables><tables id="tabl0027" num="0027"><img file="EP0431291A2_D0053.tif" /></tables><tables id="tabl0028" num="0028"><img file="EP0431291A2_D0054.tif" /></tables>

Starting materials of formula (II)

Example (II-1)

0075<chemistry id="chem0027" num="0027"><img file="EP0431291A2_D0055.tif" /></chemistry>

1. step

0076CH₃-NH-<img file="EP0431291A2_D0056.tif" />-NH-NH-COOC₂H₅ A solution of 175 g (2.4 mol) of methyl isothiocyanate in 300 ml of diethyl ether is added with stirring to a solution of 250 g (2.4 mol) of ethyl hydrazino formate. The reaction mixture is stirred for 12 hours at 20 ° C., then cooled to approx. 10 ° C. and the crystalline product obtained is isolated by suction. 404 g (95% of theory) of 4-methyl-1-ethoxycarbonyl-thiosemicarbazide with a melting point of 130 ° C. are obtained.

0077Analogously you get: 4-ethyl-1-methoxycarbonyl-thiosemicarbazide (melting point: 142 ° C); 4-propyl-1-methoxycarbonyl-thiosemicarbazide (melting point: 117 ° C); 4-cyclopropyl-1-methoxycarbonyl-thiosemicarbazide (melting point: 148 ° C); 4-allyl-1-methoxycarbonyl-thiosemicarbazide (melting point: 151 ° C); 4-dimethylamino-1-methoxycarbonyl-thiosemicarbazide (= 5,5-dimethyl-1-methoxycarbonyl-thiocarbohydrazide) (melting point: 144 ° C).

Level 2

0078<chemistry id="chem0028" num="0028"><img file="EP0431291A2_D0057.tif" /></chemistry>

0079A mixture of 10.0 g (56.5 mmol) of 4-methyl-1-ethoxycarbonyl-thiosemicarbazide (see 1st stage), 4.0 g (29 mmol) of potassium carbonate and 80 ml of ethanol is added until the evolution of gas has ceased Reflux heated to boiling (about 3 hours). After cooling, the mixture is concentrated, the residue is stirred with 50 ml of methylene chloride and the undissolved product is isolated by suction.

00809.2 g (96% of theory) of the potassium salt of 5-mercapto-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one (melting temperature> 230 ° C.) are obtained.

0081The potassium salts of 5-mercapto-4-ethyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 5-mercapto-4-propyl-2,4-dihydro-3H-1,2,4- triazol-3-one, 5-mercapto-4-cyclopropyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 5-mercapto-4-allyl-2,4-dihydro-3H- 1,2,4-triazol-3-one and 5-mercapto-4-dimethylamino-2,4-dihydro3H-1,2,4-triazol-3-one, all of which melt above 230 ° C.

3rd step

0082<chemistry id="chem0029" num="0029"><img file="EP0431291A2_D0058.tif" /></chemistry>

0083A mixture of 4.0 g (23.7 mmol) of 5-mercapto-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one potassium salt (see 2nd stage), 4.1 g (28.9 mmol) of methyl iodide and 80 ml of methanol are stirred at 20 ° C. for 12 hours. It is then concentrated, the residue is stirred with methylene chloride and the undissolved potassium iodide is separated off by filtration. The filtrate is concentrated, the residue is stirred with 500 ml of diethyl ether / petroleum ether (vol. 1: 1) and the crystalline product is isolated by suction.

00843.4 g (99% of theory) of 4-methyl-5-methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one with a melting point of 97 ° C. are obtained.

0085Analogously to Example (II-1), the compounds of the formula (II) listed in Table 4 below can also be prepared, for example.<chemistry id="chem0030" num="0030"><img file="EP0431291A2_D0059.tif" /></chemistry><tables id="tabl0029" num="0029"><img file="EP0431291A2_D0060.tif" /></tables><tables id="tabl0030" num="0030"><img file="EP0431291A2_D0061.tif" /></tables>

Starting materials of formula (IV):

Example (IV-1)

0086<chemistry id="chem0031" num="0031"><img file="EP0431291A2_D0062.tif" /></chemistry>

0087A mixture of 20.0 g (0.137 mol) of 4-amino-5-methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one, 5.6 g (0.141 mol) of sodium hydroxide, 0 , 2 g of tetrabutylammonium bromide and 200 ml of methylene chloride / water (1: 1 by volume) are mixed with vigorous stirring with 22.1 g (0.141 mol) of phenyl chloroformate. The reaction mixture is stirred for 12 hours at 20 ° C. and the crystalline product is isolated by suction. 34.8 g (95% of theory) of 4-amino-5-methylthio-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one with a melting point of 211 ° C. are obtained.

0088Analogously to Example (IV-1), the compounds of the formula (IV) listed in Table 5 below can also be prepared, for example.<chemistry id="chem0032" num="0032"><img file="EP0431291A2_D0063.tif" /></chemistry><tables id="tabl0031" num="0031"><img file="EP0431291A2_D0064.tif" /></tables><tables id="tabl0032" num="0032"><img file="EP0431291A2_D0065.tif" /></tables><tables id="tabl0033" num="0033"><img file="EP0431291A2_D0066.tif" /></tables>

Examples of use:

0089In the following application examples, the known herbicide isocarbamide of the following formula (A) is used as a reference substance:<chemistry id="chem0033" num="0033"><img file="EP0431291A2_D0067.tif" /></chemistry> (known for example from DE-17 95 117).

0090The formulas of the compounds according to the invention used for the application examples are listed below with the numbering of the preparation examples:<chemistry id="chem0034" num="0034"><img file="EP0431291A2_D0068.tif" /></chemistry><chemistry id="chem0035" num="0035"><img file="EP0431291A2_D0069.tif" /></chemistry><chemistry id="chem0036" num="0036"><img file="EP0431291A2_D0070.tif" /></chemistry><chemistry id="chem0037" num="0037"><img file="EP0431291A2_D0071.tif" /></chemistry><chemistry id="chem0038" num="0038"><img file="EP0431291A2_D0072.tif" /></chemistry>

Example A

0091Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

0092To 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.

0093Seeds of the test plants are sown in normal soil and watered with the preparation of active compound after 24 hours. The amount of water per unit area is expediently kept constant. The concentration of active substance in the preparation is irrelevant, the only decisive factor is the amount of active substance applied per unit area. After three weeks, the degree of damage to the plants is rated in% 6 damage compared to the development of the untreated control. It means: 0% = no effect (like untreated control) 100% = total annihilation

0094In this test, for example, the compounds according to Preparation Examples 1, 3, 4, 5, 6, 7, 13, 17, 21, 22, 23, 24, 25, 26, 27 show a clear superiority in effectiveness compared to the prior art , 28, 29, 30, 31, 32, 34, 35, 37.

Example B

0095Post emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

0096To 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.

0097Test plants which have a height of 5-15 cm are sprayed with the active substance preparation in such a way that the desired amounts of active substance are applied per unit area. The concentration of the spray liquor is chosen so that the particular amounts of active compound desired are applied in 1000 l of water / ha. After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control. It means: 0% = no effect (like untreated control) 100% = total annihilation

0098In this test, for example, the compounds according to Preparation Examples 1, 3, 4, 5, 6, 7, 13, 14, 16, 17, 20, 21, 22, 23, 24 show a clear superiority in effectiveness over the prior art , 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 37, 38, 40.

Example C

0099Pyricularia test (rice) / protective Solvent: 12.5 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

0100To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted to the desired concentration with water and the stated amount of emulsifier.

0101To test for protective effectiveness, young rice plants are sprayed with the preparation of active compound to runoff. After the spray coating has dried, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae. The plants are then in a greenhouse at 100% rel. Humidity and 25 ° C.

01024th The disease infestation is evaluated days after the inoculation.

0103In this test, for example, the compounds according to the following preparation examples have a good effect: 1, 3, 4, 5, 7, 9.

Example D

0104Pyricularia test (rice) / systemic Solvent: 12.5 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

0105To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted with water and the stated amount of emulsifier to the desired concentration.

0106To test for systemic properties, 40 ml of the active ingredient preparation are poured onto common soil in which young rice plants have been grown. 7 days after the treatment, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae. Then the plants remain in a greenhouse at a temperature of 25 ° C and a rel. Air humidity of 100% until evaluation.

01074th The disease infestation is evaluated days after the inoculation.

0108In this test, for example, the compounds according to the following preparation examples show excellent activity: 1, 3, 4, 5, 7, 15, 17, 21, 22, 25.