Claims
- 1. A compound of the formula ##STR398## in which R.sup.1 represents the radical ##STR399## where R.sup.7 and R.sup.8 are identical or different and represent hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, C.sub.1 -C.sub.6 -alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C.sub.1 -C.sub.4 -alkoxycarbonyl, C.sub.1 -C.sub.4 -alkylaminocarbonyl, di-(C.sub.1 -C.sub.4 -alkyl)aminocarbonyl, hydroxyl, C.sub.1 -C.sub.4 -alkoxy, formyloxy, C.sub.1 -C.sub.4 -alkyl-carbonyloxy, C.sub.1 -C.sub.4 -alkoxycarbonyloxy, C.sub.1 -C.sub.4 -alkylamino-carbonyloxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.1 -C.sub.4 -alkylsulphinyl, C.sub.1 -C.sub.4 -alkylsulphonyl, di-(C.sub.1 -C.sub.4 -alkyl)aminosulphonyl, C.sub.3 -C.sub.6 -cycloalkyl or phenyl), represent C.sub.2 -C.sub.6 -alkenyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, C.sub.1 -C.sub.4 -alkoxycarbonyl, carboxyl or phenyl), represent C.sub.2 -C.sub.6 -alkenyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, C.sub.1 -C.sub.4 -alkoxy-carbonyl, carboxyl or phenyl), represent C.sub.1 -C.sub.4 -alkoxy (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C.sub.1 -C.sub.4 -alkoxy-carbonyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.1 -C.sub.4 -alkylsulphinyl or C.sub.1 -C.sub.4 -alkylsulphonyl), represent C.sub.1 -C.sub.4 -alkylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C.sub.1 -C.sub.4 -alkoxy-carbonyl, C.sub.1 -C.sub.4 -alkylthio, C.sub.1 -C.sub.4 -alkylsulphinyl or C.sub.1 -C.sub.4 -alkylsulphonyl), represent C.sub.3 -C.sub.6 -alkenyloxy (which is optionally substituted by fluorine, chlorine, bromine, cyano or C.sub.1 -C.sub.4 -cyano or C.sub.1 -C.sub.4 -alkoxy-carbonyl), represent C.sub.2 -C.sub.6 -alkenylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C.sub.1 -C.sub.3 -alkylthio or C.sub.1 -C.sub.4 -alkoxycarbonyl), C.sub.3 -C.sub.6 -alkinyloxy, C.sub.3 -C.sub.6 -alkinylthio or represent the radical --S(O).sub.p --R.sup.9, where
- P represents the numbers 1 or 2 and
- R.sup.9 represents fluorine, C.sub.1 -C.sub.4 alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano or C.sub.1 -C.sub.4 -alkoxy-carbonyl), C.sub.3 -C.sub.6 -alkenyl, C.sub.3 -C.sub.6 -alkinyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkoxy-C.sub.1 -C.sub.4 -alkylamino, C.sub.1 -C.sub.4 -alkylamino, di-(C.sub.1 -c.sub.4 -alkyl-amino or represents the radical --NHOR.sup.10, where
- R.sup.10 represents C.sub.1 -C.sub.6 -alkyl (which is optionally substituted by fluorine, chlorine, cyano, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.1 -C.sub.4 -allylsulphinyl, C.sub.1 -C.sub.4 -alkylsulphonyl, C.sub.1 -C.sub.4 -alkyl-carbonyl, C.sub.1 -C.sub.4 -alkoxycarbonyl, C.sub.1 -C.sub.4 -alkylaminocarbonyl or di-(C.sub.1 -C.sub.4 -alkyl)amino-carbonyl), represents C.sub.3 -C.sub.6 -alkenyl (which is optionally substituted by fluorine, chlorine or bromine), C.sub.3 -C.sub.6 -alkinyl, C.sub.3 -C.sub.6 -cycloalkyl, C.sub.3 -C.sub.6 -cycloalkyl-C.sub.1 -C.sub.2 -alkyl, phenyl-C.sub.1 -C.sub.2 -alkyl (which is optionally substituted by fluorine, chlorine, nitro, cyano, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy or C.sub.1 -C.sub.4 -alkoxy-carbonyl), represents benzyhydryl or represents phenyl (which is optionally substituted by fluorine, chlorine, nitro, cyano, C.sub.1 -C.sub.4 -alkyl, trifluoromethyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.2 -fluoroalkoxy, C.sub.1 -C.sub.4 -alkylthio, trifluoromethylthio or C.sub.1 -C.sub.4 -alkoxycarbonyl),
- R.sup.7 and/or R.sup.8 furthermore represent phenyl or phenoxy, C.sub.1 -C.sub.4 -alkylcarbonylamino, C.sub.1 -C.sub.4 -alkoxy-carbonylamino, C.sub.1 -C.sub.4 -alkylaminocarbonyl-amino, di-(C.sub.1 -C.sub.4 -alkyl)-aminocarbonylamino, or represent the radical --CO--R.sup.11, where
- R.sup.11 represents C.sub.1 -C.sub.6 -alkyl, C.sub.1 -C.sub.6 -alkoxy, C.sub.3 -C.sub.6 -cycloalkoxy, C.sub.3 -C.sub.6 -alkenyloxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.1 -C.sub.4 -alkylamino, C.sub.1 -C.sub.4 -alkoxyamino, C.sub.1 -C.sub.4 -alkoxy-C.sub.1 -C.sub.4 alkyl-amino or di-(C.sub.1 -C.sub.4 -alkyl)-amino (which are optionally substituted by fluorine and/or chlorine),
- R.sup.7 and/or R.sup.8 furthermore represent C.sub.1 -C.sub.4 -alkylsulphonyloxy, di-(C.sub.1 -C.sub.4 -alkyl)-aminosulphonylamino or the radical --CH.dbd.N--R.sup.12, where
- R.sup.12 represents C.sub.1 -C.sub.6 -alkyl which is optionally substituted by fluorine, chlorine, cyano, carboxyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.1 -C.sub.4 -alkylsulphinyl or C.sub.1 -C.sub.4 -alkylsulphonyl, represents benzyl which is optionally substituted by fluorine or chlorine, represents C.sub.3 -C.sub.6 -alkenyl or C.sub.3 -C.sub.6 -alkinyl, each of which is optionally substituted by fluorine or chlorine, represents phenyl which is optionally substituted by fluorine, chlorine, bromine, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, represents C.sub.1 -C.sub.6 -alkoxy, C.sub.3 -C.sub.6 -alkenoxy, C.sub.3 -C.sub.6 -alkinoxy or benzyloxy, each of which is optionally substituted by fluorine and/or chlorine, represents amino, C.sub.1 -C.sub.4 -alkylamino, di-(C.sub.1 -C.sub.4 -alkyl)-amino, phenylamino, C.sub.1 -C.sub.4 -alkyl-carbonylamino, C.sub.1 -C.sub.4 -alkoxy-carbonylamino, C.sub.1 -C.sub.4 -alkylsulphonylamino or represents phenylsulphonylamino which is optionally substituted by fluorine, chlorine, bromine or methyl, or
- where furthermore
- R.sup.1 represents the radical ##STR400## where R.sup.13 represents hydrogen or C.sub.1 -C.sub.4 -alkyl,
- R.sup.14 and R.sup.15 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C.sub.1 -C.sub.4 -alkyl (which is optionally substituted by fluorine and/or chlorine), C.sub.1 -C.sub.4 -alkoxy (which is optionally substituted by fluorine and/or chlorine), carboxyl, C.sub.1 -C.sub.4 -alkoxycarbonyl, C.sub.1 -C.sub.4 -alkylsulphonyl or di-(C.sub.1 -C.sub.4 -alkyl)-aminosulphonyl; where furthermore
- R.sup.1 represents the radical ##STR401## where R.sup.16 and R.sup.17 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C.sub.1 -C.sub.4 -alkyl (which is optionally substituted by fluorine and/or chlorine) or C.sub.1 -C.sub.4 -alkoxy (which is optionally substituted by fluorine and/or chlorine);
- R.sup.2 represents hydrogen or the group --SO.sub.2 --R.sup.1, and
- in which furthermore
- R.sup.3 represents hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, mercapto, amino or an optionally fluorine- and/or chlorine-substituted radical selected from the group consisting of C.sub.1 -C.sub.4 -alkyl, C.sub.3 -C.sub.6 -cycloalkyl, benzyl, phenyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.3 -C.sub.4 -alkenyloxy, C.sub.3 -C.sub.4 -alkinyloxy, C.sub.1 -C.sub.4 -alkylthio, C.sub.1 -C.sub.4 -alkylsulphinyl, C.sub.1 -C.sub.4 -alkylsulphonyl, C.sub.3 -C.sub.4 -alkenylthio, C.sub.3 -C.sub.4 -alkinylthio, benzyloxy, benzylthio, C.sub.1 -C.sub.4 -alkylamino and di-(C.sub.1 -C.sub.4 -alkyl)-amino.
- 2. A compound or salt thereof of the formula ##STR402## in which R.sup.1 represents the radical ##STR403## where R.sup.7 represents fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, C.sub.1 -C.sub.3 -alkylthio, C.sub.1 -C.sub.3 -alkylsulphinyl, C.sub.1 -C.sub.3 -alkylsulphonyl, dimethylaminosulphonyl, N-methoxy-N-methylaminosulphonyl, phenyl, phenoxy or C.sub.1 -C.sub.3 -alkoxycarbonyl and
- R.sup.8 represents hydrogen, fluorine or chlorine; or where furthermore
- R.sup.1 represents the radical ##STR404## where R.sup.13 represents hydrogen,
- R.sup.14 represents fluorine, chlorine, bromine, methyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methylsulphonyl or dimethylaminosulphonyl and
- .sup.15 represents hydrogen; where furthermore
- R.sup.2 represents hydrogen or for the group --SO.sub.2 --R.sup.1, and
- R.sup.3 represents hydrogen, methyl, ethyl, propyl, isopropyl, trifluoromethyl, cyclopropyl, benzyl, phenyl, t-butyl, s-butyl, i-butyl, n-butyl, methoxy or methylthio.
Priority Claims (2)
| Number |
Date |
Country |
Kind |
| 3825602 |
Jul 1988 |
DEX |
|
| 3901084 |
Jan 1989 |
DEX |
|
Parent Case Info
This is a division of application Ser. No. 382,163, filed July 19, 1989, now issued U.S. Pat. No. 4,988,381. .spsb.
The invention relates to new substituted 4-sulphonylamino-2-azinyl-1,2,4-triazol-3-ones (hereinafter abbreviated to "substituted sulphonylaminotriazolinones"), processes and new intermediates for their preparation, and their use as herbicides.
It has been disclosed that certain substituted triazolinones, such as, for example, 4-(3-trifluoromethoxybenzylideneamino)-2,4-dihydro-3H-1,2,4-triazol-3-one, are herbicidally active (cf. U.S. Pat. No. 3,884,910). However, the action of these known compounds is not satisfactory in all respects.
The new substituted sulphonylaminotriazolinones of the general formula (I) ##STR3## in which R.sup.1 represents an optionally substituted radical from the series comprising alkyl, aralkyl, aryl and heteroaryl,
The new substituted sulphonylaminotriazolinones of the general formula (I) are obtained when
(a) substituted aminotriazolinones of the general formula (II) ##STR4## in which R.sup.3, R.sup.4, X, Y and Z have the abovementioned meanings,
b) sulphonylaminotriazolinones of the general formula (IV) ##STR5## in which R.sup.1, R.sup.2 and R.sup.3 have the above-mentioned meanings, are reacted with azines of the general formula (V) ##STR6## in which R.sup.4, X, Y and Z have the above-mentioned meanings and
The new substituted sulphonylaminotriazolinones of the general formula (I) are distinguished by powerful herbicidal activity. These compounds represent a chemically novel class of herbicides. Surprisingly, the new compounds of the formula (I) show a considerably better herbicidal action than 4-(3-trifluoromethoxy-benzylideneamino)-2,4-dihydro-3H-1,2,4-triazol-3-one, which is known and has similar structure.
The invention preferably relates to compounds of the formula (I) in which
The invention particularly relates to compounds of the formula (I) in which
The invention furthermore preferably relates to salts of compounds of the formula (I)
If, for example, 4-amino-5-methyl-2-(4,6-dimethoxy-s-triazin-2-yl)-2,4-dihydro-3H-1,2,4-triazol-3-one and 2-fluoro-benzenesulphonyl chloride (at least two mole equivalents) are used as starting substances in process (a) according to the invention, the course of the reaction in process (a) according to the invention can be outlined by the following equation: ##STR23##
If, for example, 4-(2-difluormethoxy-phenylsulphonylamino)-5-trifluormethyl-2,4-dihydro-3H-1,2,4-triazol-3-one and 4,6-dimethoxy-2-methylsulphonyl-pyrimidine are used as starting substances in process (b) according to the invention, the course of the reaction in process (b) according to the invention can be outlined by the following equation: ##STR24##
Formula (II) provides a general definition of the substituted aminotriazolinones to be used as starting substances in the process (a) according to the invention for the preparation of compounds of the formula (I).
In formula (II), R.sup.3, R.sup.4, X, Y 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) according to the invention as being preferred, or particularly preferred, for R.sup.3, R.sup.4, X, Y and Z.
Examples of the starting substances of the formula (II) are listed in Table 1 below.
The substituted aminotriazolinones of the formula (II), which are to be used as starting substances in process (a), were hitherto unknown from the literature. The new compounds of the formula (II) are obtained when
Some of the compounds of the formula (II) can be prepared using a synthesis route similar to the one described under (.alpha.) but without introducing protective groups using carbonyl compounds of the formula (VII), that is to say by directly reacting compounds of the formula (VI) with compounds of the formula (V) under the reaction conditions indicated under (.alpha.).
Formula (VI) provides a general definition of the aminotriazolinones, which are required as intermediates. In formula (VI), R.sup.3 preferably, or in particular, has the meaning which has already been indicated above in connection with the description of the compounds of the formula (I) according to the invention as being preferred, or particularly preferred, for R.sup.3.
Example of the compounds of the formula (VI) which may be mentioned are:
4-amino-2,4-dihydro-3-H-1,2,4-triazol-3-one, 4-amino-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 4-amino-5-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one, 4-amino-5-methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one, 4-amino-5-ethyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 4-amino-5-propyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 4-amino-5-cyclopropyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 4-amino-5-isopropyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 4-amino-5-butyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 4-amino-5-isobutyl-2,4-dihydro-3H-1,2,4-triazol-3-one and 4-amino-5-tert.-butyl-2,4-dihydro-3H-1,2,4-triazol-3-one.
The aminotriazolinones of the formula (VI) are known and/or can be prepared by processes known per se (cf. Chem. Ber. 98 (1965), 3025-3033; J.Heterocycl. Chem. 21 (1984), 1769-1774; Doga: Kim. Ser. 10 (1986), 34-39 -quoted in Chem. Abstracts 106: (1987), 138338e).
Formula (VII) provides a definition of the carbonyl compounds also required as intermediates.
In formula (VII),
Examples of the compounds of the formula (VII) which may be mentioned are:
The intermediates of the formula (VII) are known chemicals for organic synthesis.
Formula (V) provides a general definition of the azines also required as intermediates. In formula (V), R.sup.4, X, Y 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) according to the invention as being preferred, or particularly preferred, for R.sup.4, X, Y and Z, and Q.sup.1 preferably represents fluorine, chlorine, bromine, benzylsulphonyl or C.sub.1 -C.sub.4 -alkylsulphonyl, in particular represents chlorine or methylsulphonyl.
Examples of the compounds of the formula (V) which may be mentioned are: 2-chloro-, 2-benzylsulphonyl- and 2-methylsulphonyl-4,6-dimethyl-pyrimidine, -4-methyl-6-methoxy-pyrimidine, -4,6-dimethoxy-pyrimidine, -4-methyl-6-ethoxy-pyrimidine, -4-chloro-6-methoxy-pyrimidine, -4-methyl-pyrimidine, -4-chloro-6-methyl-pyrimidine, -4-trifluoromethyl-6-methoxypyrimidine, -4-methoxy-6-difluoromethoxy-pyrimidine, -4-methyl-6-difluoromethoxy-pyrimidine, -4,6-bis-difluoromethoxy-pyrimidine, -4-chloro-6-ethoxy-pyrimidine, -4-chloro-6-difluoromethoxy-pyrimidine, -4-methoxy-5-methylpyrimidine, -4-trifluoromethyl-6-difluoromethoxy-pyrimidine, -4,6-diethoxy-pyrimidine, -4,5-dichloro-6-methyl-pyrimidine, -4-methyl-5-chloro-6-methoxy-pyrimidine, -4,6-dichloropyrimidine, -4-ethyl-6-methoxy-pyrimidine, -5-chloro-4,6-dimethoxy-pyrimidine, -4-methoxy-6-methylamino-pyrimidine and -4,6-bis-trifluoromethyl-pyrimidine, furthermore 2-chloro-4,6-dimethyl-s-triazine, 2-chloro-4-methyl-6-methoxy-s-triazine, 2-chloro-4,6-dimethoxy-s-triazine, 2,4-dichloro-6-methoxy-s-triazine, 2-chloro-4-ethyl-6-methoxy-s-triazine, 2-chloro-4-methyl-6-ethoxy-s-triazine, 2-chloro-4-ethoxy-6-methylamino-s-triazine, 2-chloro-4-methoxy-6-methylamino-s-triazine, 2-chloro-4-methoxy-6-ethylamino-s-triazine and 2-chloro-4-ethoxy-6-ethylamino-s-triazine.
The azines of the formula (V) are known and/or can be prepared by processes known per se (cf., J. Chem. Soc. 1957, 1830, 1833; J. Org. Chem. 26 (1961), 792; U.S. Pat. No.3,308,119 and U.S. Pat. No. 4,711,959).
Formula (X) provides a general definition of the oxadiazolones also to be used as intermediates. In formula (X), R.sup.3 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 as being preferred, or particularly preferred, for R.sup.3.
Examples of the compounds of the formula (X) which may be mentioned are: 1,3,4-oxadiazol-2(3H)-one, 5-methyl-1,3,4-oxadiazol-2(3H)-one, 5-ethyl-1,3,4-oxadiazol-2(3H)-one, 5-propyl-1,3,4-oxadiazol-2(3H)-one, 5-isopropyl-1,3,4-oxadiazol-2(3H)-one, 5-butyl-1,3,4-oxadiazol-2(3H)-one, 5-trifluoromethyl-1,3,4-oxadiazol-2(3H)-one, 5-tert.-butyl-1,3,4-oxadiazol-2(3H)-one, 5-cyclopropyl-1,3,4-oxadiazol-2(3H)-one, 5-methoxy-1,3,4-oxadiazol-2(3H)-one and 5-methylthio-1,3,4-oxadiazol-2(3H)-one.
The oxadiazolones of the formula (X) are known and/or can be prepared by processes known per se (cf. Helv. Chim. Acta 55 (1972), 1174-1178).
Formula (III) provides a general definition of the sulphonyl halides or sulphonic anhydrides also to be used as starting substances in process (a) according to the invention for the preparation of the new compounds of the formula (I). In formula (III), R.sup.1 preferably, or in particular, has the meaning which has been indicated above in connection with the description of the compounds of the formula (I) according to the invention as being preferred, or particularly preferred, and Q preferably represents chlorine.
Starting substances of the formula (III) which may be mentioned by way of example are:
The sulphonyl halides or sulphonic anhydrides of the formula (III) are known and/or can be prepared by processes known per se (cf. J. Org. Chem. 33 (1968), 2104; J. Org. Chem. 25 (1960), 1824; DE-AS (German Published Specification) 2,308,262; EP-OS (European Published Specification) 23,140, 23,111, 23,422, 35,893, 48,143, 51,466, 64,322, 70,041, 44,808 and 44,809; U.S. Pat. No. 2,929,820, 4,282,242; 4,348,220 and 4,372,778 and Angew. Chem. 93 (1981), 151).
Process (a) according to the invention for the preparation of the new compounds of the formula (I) is preferably carried out using diluents. Suitable diluents for this process are virtually all inert organic solvents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-di-chlorobenzene, ethers, such as diethyl ether, dibutyl ether, glycol dimethyl ether, 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-methyl-pyrrolidone, and dimethyl sulphoxide, tetramethylene sulphone and hexamethylphosphoric triamide and pyridine.
Acid acceptors which can be employed in process (a) according to the invention are all acid-binding agents which can customarily be used for reactions of this type. Alkali metal hydroxides, such as, for example, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides, such as, for example, calcium hydroxide, alkali metal carbonates and alkali metal alkoxides, such as sodium carbonate and potassium carbonate, sodium tert.-butoxide and potassium tert.-butoxide, furthermore aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine, pyridine, picoline, 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), are preferably suitable.
In process (a) according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at temperatures between -50.degree. C. and +50.degree. C., preferably at temperatures between -40.degree. C. and +40.degree. C.
For carrying out process (a) according to the invention, between 1 and 5 moles, preferably between 1 and 4 moles, of sulphonyl halide or sulphonic anhydride of the formula (III) are generally employed per mole of aminotriazolinone of the formula (II). In the case where disulphonylated compounds of the formula (I, R.sup.2 =--SO.sub.2 --R.sup.1) are to be prepared in a one-pot reaction, at least 2 moles of sulphonyl halide or sulphonic anhydride (III) are to be employed per mole of aminotriazolinone (II).
The reactants can be combined in any desired sequence. In a preferred embodiment of process (a) according to the invention, the starting substances of the formula (II) and (III) are stirred at room temperature with a diluent, and the acid acceptor is slowly metered into this mixture, if appropriate after cooling. The reaction mixture is then stirred until the reaction is complete.
Working up can be carried out in a customary manner, for example by washing with water--if appropriate after concentrating and/or diluting the mixture with a virtually water-immiscible organic solvent, such as, for example, methylene chloride -, drying and filtering the mixture, and carefully distilling off the solvent from the filtrate. The crude product, which remains in the residue, can be purified further in a customary manner, for example by column chromatography and/or by recrystallization.
The compounds which can be obtained as described above of the formula (I) in which R.sup.2 represents the group --SO.sub.2 --R.sup.1 can be reacted to give compounds of the formula (I) in which R.sup.2 represents hydrogen by reaction with desulphonylating agents, if appropriate in the presence of diluents.
In this connection, desulphonylating agents are taken to mean substances which can eliminate a sulphonyl group from N,N-bis-sulphonyl-amino compounds. Suitable desulphonylating agents are above all alkali metal hydroxides or alkaline earth metal hydroxides, such as sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal alkoxides, such as sodium methoxide, potassium methoxide, sodium ethoxide and potassium ethoxide, furthermore ammonia, alkylamines, such as methylamine, ethylamine, propylamine and butylamine, and also dialkylamines, such as dimethylamine and diethylamine. It is preferred to employ ammonia as the desulphonylating agent.
The desulphonylation is preferably carried out in the presence of diluents. Preferred diluents, besides water, are polar organic solvents, such as methanol, ethanol, propanol, isopropanol, 2-methoxyethanol, 2-ethoxy-ethanol and dioxane.
The desulphonylation is generally carried out at temperatures between 0.degree. C. and 150.degree. C., preferably at temperatures between 20.degree. C. and 100.degree. C.
In general, the reactants for desulphonylation are mixed at room temperature and stirred until the reaction is complete, if appropriate at increased temperature. For working up, the mixture is concentrated, if appropriate, diluted with water, and acidified using a strong acid, such as, for example, hydrochloric acid. The product, which is obtained in this process in the form of crystals (I, R.sup.2 =H), can be isolated by filtering off with suction.
If desired, salts can be prepared from the compounds of the general formula (I) according to the invention. Such salts are obtained in a simple manner by customary salt formation methods, for example by dissolving or dispersing a compound of the formula (I) in a suitable solvent, such as, for example, water, methanol, ethanol or acetone, and adding a suitable acid or base. The salts can then be isolated by concentration or filtering off with suction, if appropriate after stirring for some time.
Formula (IV) provides a general definition of the sulphonylaminotriazolinones to be used as starting substances in process (b) according to the invention for the preparation of compounds of the formula (I).
In formula (IV), R.sup.1, R.sup.2 and R.sup.3 preferably, or in particular, have the meanings which have already been indicated above in connection with the description of the compounds of the formula (I) according to the invention as being preferred, or particularly preferred, for R.sup.1, R.sup.2 and R.sup.3.
Starting substances of the formula (IV) which may be mentioned by way of example are:
The sulphonylaminotriazolinones of the formula (IV) to be used as starting substances were hitherto unknown from the literature. The new compounds of the formula (IV) are obtained when aminotriazolinones of the general formula (VI) ##STR52## in which R.sup.3 has the above-mentioned meaning, are reacted with sulphonyl halides or sulphonic anhydrides of the general formula (III) ##STR53## in which R.sup.1 and Q have the above-mentioned meanings,
As far as the starting substances of the formulae (III) and (VI) are concerned, the instructions indicated above in the description of process (a) according to the invention, relating to these substances, are also true in this connection.
As far as the azines of the formula (V) are concerned, which are to be used as starting substances in process (b) according to the invention, the instructions indicated above in the description of process (a) according to the invention are also true in this connection.
Process (b) according to the invention is preferably carried out using diluents. Suitable solvents are those which have been indicated above as diluents in process (a).
Process (b) is preferably carried out in the presence of an acid acceptor. Suitable acid acceptors are the same acid-binding agents which have been indicated above in process (a).
In process (b) according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the process is carried out at temperatures between 0.degree. C. and +150.degree. C., preferably at temperatures between +20.degree. C. and +120.degree. C.
Process (b) according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process under increased or reduced pressure.
For carrying out process (b) according to the invention, 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 relatively large excess. The reactions are generally carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for several hours at the specific temperature required. Working-up in process (b) according to the invention is carried out in each case by customary methods.
The active compounds according to the invention can be used as defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weedkillers. By weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants: Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, 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 and Centaurea.
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, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the concentration, for the total combating of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for combating weeds in perennial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, and for the selective combating of weeds in annual cultures.
The compounds of the formula (I) according to the invention are particularly suitable for selectively combating dicotyledon weeds in monocotyledon crops, above all using the post-emergence method.
The active compounds can be converted to the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in 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 emulsifying 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 rain: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes 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 cyclohexanon:, strongly polar solvents, 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, montmorillonite 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, corn 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, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as albumin 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 latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, 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%.
The active compounds according to the invention, as such or in the form of their formulations, can also be used, for combating weeds, 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'-dimethylurea (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 beets, and 4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one (METRIBUZIN) for combating weeds in soy beans; 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-bensothiadiazin-4-one 2,2-dioxide (BENTAZONE); 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}benzenesulphonamide (CHLORSULFURON); N,N-dimethyl-N'-(3-chloro-4-methylphenyl)-urea (CHLORTOLURON); 2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionic acid, its methyl ester or its ethyl ester (DICLOFOP); 2-{4-[(6-chloro-2-benzoxazolyl)-oxy]-phenoxy}-propanoic acid, its methyl ester or its ethyl ester (FENOXAPROP); [(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)-oxy]-acetic acid or its 1-methylheptyl ester (FLUROXYPYR); methyl 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-4(5)-methylbenzoate (IMAZAMETHABENZ); 3,5-diodo-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]-sulphonyl}-benzoic acid or its methyl ester (METSULFURON); N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitroaniline (PENDIMETHALIN); 0-(6-chloro-3-phenyl-pyridazin-4-yl) S-octyl thiocarbonate (PYRIDATE); 2-[1-(ethoxamino)-butylidene]-5-(2-ethylthiopropyl)-1,3-cyclohexadione (SETHOXYDIM); 4-ethylamino-2-t-butylamino- 6-methylthio-s-triazine (TERBUTRYNE) and methyl 3-[[[[4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl]amino]-sulphonyl]-thiophene-2-carboxylate (THIAMETURON). Surprisingly, some mixtures also show 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, atomizing or scattering.
The active compounds according to the invention 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 0.01 and 10 kg of active compound per hectare of soil surface, preferably between 0.05 and 5 kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the following examples.
US Referenced Citations (1)
| Number |
Name |
Date |
Kind |
|
3884910 |
Pilgram |
May 1975 |
|
Divisions (1)
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Number |
Date |
Country |
| Parent |
382163 |
Jul 1989 |
|
Patent Grant
5089627
