Herbicides

The present invention relates to novel 6H-1,2,4,6-thiatriazine-1,1-dioxides, processes for the preparation of these compounds, herbicides which contain these compounds, and the use of the compounds as herbicides.
The herbicidal action of substituted 6H-1,2,4,6-thiatriazin-5-one-1,1-dioxide derivatives is disclosed in German Laid-Open Application DOS No. 2,508,832.
We have found that substituted 6H-1,2,4,6-thiatriazine-1,1-dioxides of the general formula I ##STR2## where R.sup.1 and R.sup.2 independently of one another are a saturated or unsaturated straight-chain aliphatic radical of 1 to 10 carbon atoms, a cycloaliphatic radical of 3 to 7 carbon atoms, a branched saturated or unsaturated aliphatic radical of 3 to 10 carbon atoms, a halogen-, alkoxy- or alkylmercapto-substituted aliphatic radical of 2 to 10 carbon atoms or a cycloalkoxy-substituted aliphatic radical of 4 to 10 carbon atoms,
R.sup.1 may also be unsubstituted or halogen, lower alkyl- or lower alkoxy-substituted phenyl, unsubstituted or halogen-substituted benzyl or tetrahydrofurylmethyl,
R.sup.2 may also be a halogen-, alkoxy-, dialkylketone- or alkylmercapto-substituted unsaturated aliphatic radical or a dialkylketone-substituted aliphatic radical of 3 to 10 carbon atoms, lower alkoxy-carbo-lower alkoxy, lower alkylmercapto-carbo-lower alkoxy, lower alkoxy-carbo-lower alkylmercapto, lower alkylmercapto-carbo-lower alkylmercapto, aryl which is unsubstituted or substituted by halogen, lower alkyl, halo-lower alkyl, lower alkoxy, halo-lower alkoxy, lower alkylmercapto halo-lower alkylmercapto, lower alkylsulfinyl, halo-lower alkylsulfinyl, lower alkylsulfonyl, halo-lower alkylsulfonyl, nitro, cyano, azido, carboxyl, SCN, ##STR3## SO.sub.2 OR.sup.4, ##STR4## CH.dbd.NOH or CHO, or by lower alkoxy-carbo-lower alkoxy, lower alkylmercapto-carbo-lower alkoxy, lower alkoxy-carbo-lower alkylmercapto or lower alkylmercapto-carbo-lower alkylmercapto; R.sup.2 may further denote benzyl which is unsubstituted or substituted by halogen, lower alkyl, halo-lower alkyl, lower alkoxy, halo-lower alkoxy or halo-lower alkylmercapto,
R.sup.3 is hydrogen, a straight-chain aliphatic radical of 1 to 10 carbon atoms, a cycloaliphatic radical of 3 to 7 carbon atoms, a branched aliphatic radical of 3 to 10 carbon atoms or halogen- or alkoxy-substituted alkyl of 2 to 10 carbon atoms,
R.sup.4 and R.sup.5 are lower alkyl and R.sup.5 may also be hydrogen,
X and Y are oxygen, sulfur, sulfinyl or sulfonyl and
X.sup.1 is oxygen or sulfur have a powerful herbicidal action and are tolerated by various crop plants.
In formula I, R.sup.1, R.sup.2 and R.sup.3 are, for example, methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, sec.-butyl, tert.-butyl, 1-pentyl, cyclopentyl, hexyl, cyclohexyl, 3-pentyl, 1,2-dimethylpropyl, 1,3-dimethylbutyl, 2-chloroethyl, 2-chloropropyl, 3-chloropropyl, 2-chloroisopropyl, 1-chloromethylpropyl, 1-ethyl-2-methylpropyl, 1,2,2-trimethylpropyl, 1,2-dimethylhexyl, 1-cyclohexylethyl, 2-chlorobut-3-yl, 2-chloro-2-methylpropyl, 2-fluorobut-3-yl, 2-fluoro-2-methylpropyl, 2-fluoroisopropyl, tert.-amyl, chloro-tert.-butyl, 2,2,2-trifluoroethyl, methoxyethyl, ethoxyethyl, 3-methoxypropyl, methoxyisopropyl, 3-methoxybutyl, 1-methoxy-but-2-yl, ethoxy-tert.-butyl, methoxy-tert.-butyl, 2-methoxy-butyl and 4-methoxy-butyl.
Further, R.sup.1 and R.sup.2 may be, for example, allyl, methallyl, crotyl, 2-ethylhex-2-en-1-yl, hex-5-en-1-yl, 2-methyl-but-2-en-1-yl, 2-methyl-but-1-en-3-yl, but-1-yn-3-yl, but-2-yn-1-yl, but-1-en-3-yl, propargyl, 2-methyl-but-1-en-4-yl, 2-methyl-but-2-en-4-yl, 3-methyl-but-1-en-3-yl, methylmercaptoethyl, ethylmercapto-ethyl, 3-methylmercapto-propyl, 3-methylmercapto-butyl, 1-methylmercapto-but-2-yl, methylmercapto-tert.-butyl, 2-methylmercapto-butyl, cyclohexoxy-ethyl, benzyl, 2,6-dichlorobenzyl, 2-chloro-6-fluorobenzyl, 2,6-difluorobenzyl, phenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 4-tert.-butylphenyl, 4-methoxy-3-chlorophenyl, 4-methoxyphenyl, 2-methylphenyl and 2-methyl-4-chlorophenyl.
Further, R.sup.2 may be, for example, 3-chloroprop-1-en-1-yl, 2-chloroprop-1-en-1-yl, 2-chloroprop-2-en-1-yl, chloropropargyl, 4-chloro-but-2-yn-1-yl, 4-chloro-but-1-yn-3-yl, 3-methoxy-prop-1-en-1-yl, 2-methoxy-prop-1-en-1-yl, 2-methoxy-prop-2-en-1-yl, methoxy-propargyl, 4-methoxybut-2-ynyl, 4-methoxy-but-1-yn-3-yl, 3-methylmercapto-prop-1-en-1-yl, 2-methylmercapto-prop-1-en-1-yl, pent-2-en-4-on-1-yl, propan-2-on-1-yl, o-, m- or p-trifluoromethylphenyl, o-, m- or p-chlorodifluoromethoxyphenyl, o-, m- or p-trifluoromethoxyphenyl, o-, m- or p-methylmercaptophenyl, o-, m- or p-trifluoromethylmercaptophenyl, o-, m- or p-methylsulfinylphenyl, o-, m- or p-trifluoromethylsulfinylphenyl, o-, m- or p-methylsulfonylphenyl, o-, m- or p-trifluoromethylsulfonylphenyl, o-, m- or p-nitrophenyl, o-, m- or p-cyanophenyl, o-, m- or p-azidophenyl, o-, m- or p-carboxyphenyl, o-, m- or p-thiocyanatophenyl, o-, m- or p-methoxycarbophenyl, o-m- or p-methylmercaptocarbophenyl, o-, m- or p-methylamidophenyl, o-, m- or p-dimethylamidophenyl, o-, m- or p-acetamidophenyl, o-, m- or p-methoxycarbamyl, o-, m- or p-methylmercaptocarbamyl, o-, m- or p-N'-methylsulfamido-N-phenyl, o-, m- or p-N',N'-dimethylsulfamido-N-phenyl, o-, m- or p-N'-methylureido-N-phenyl, o-, m- or p-N'-methylthioureido-N-phenyl, o-, m- or p-N',N'-dimethylureido-N-phenyl, o-, m- or p-N',N'-dimethylthioureido-N-phenyl, o-, m- or p-methylsulfamyl-phenyl, o-, m- or p-dimethylsulfamyl-phenyl, o-, m- or p-methoxysulfonylphenyl, o-, m- or p-methoxycarbamyl-sulfonylphenyl, o-, m- or p-N-hydroxylamino-benzylidene, o-, m- or p-methoxycarbonylmethoxyphenyl, o-, m- or p-methoxycarbonyl-methylmercaptophenyl, o-, m- or p-(.alpha.-methoxycarbonyl)-ethoxyphenyl with the radical ##STR5## o-, m- or p(.alpha.-methoxycarbonyl)-ethylmercaptophenyl, o-, m- or p-methylmercapto-carbonylmethoxyphenyl, o-, m- or p-(.alpha.-methylmercaptocarbonyl)-ethoxyphenyl, 2-methyl-6-chlorobenzyl, o-, m- or p-chlorobenzyl, o-, m- or p-trifluoromethylbenzyl, o-, m- or p-trifluoromethoxybenzyl, o-, m- or p-chlorodifluoromethoxybenzyl, o-, m- or p-trifluoromethyl-mercaptobenzyl, 2-methyl-6-fluorobenzyl, 3,4-dichlorobenzyl, o-, m- or p-bromophenyl, 2,3-, 2,4-, 2,6-, 3,4- or 3,5-dichlorophenyl, 2,4,5-trichlorophenyl, 3,4-difluorophenyl, 3-chloro-4-fluorophenyl, 3-fluoro-4-chlorophenyl, 3-chloro-4-methoxyphenyl, 3-chloro-4-bromophenyl, 3-chloro-4-methylphenyl, o-, m- or p-isopropylphenyl, o-, m- or p-tert.-butylphenyl, 2,4-dinitrophenyl, 2-chloro-4-nitrophenyl, 2,4-dinitro-6-sec.-butylphenyl, 2,6-dibromo-4-cyanophenyl, 2,6-diiodo-4-cyanophenyl, 2,4-dinitro-6-methylphenyl, 3-carboxy-4-nitrophenyl, 2,4-dinitro-6-tert.-butylphenyl, o-, m- or p-formylphenyl, o-, m- or p-4'-methyl-1',2',4'-oxadiazolidin-2-yl-3',5'-dione, 2,4-dichloro-6-methylphenyl, 2-chloro-4-trifluoromethylphenyl and 3-methoxycarbo-4-nitrophenyl.
Further, we have found that the novel compounds are obtained in a simple manner by a method wherein a compound of the general formula II ##STR6## where R.sup.1, X and R.sup.3 have the above meanings and Hal is halogen, is reacted with a compound of the formula III
H--Y--R.sup.2 III
where R.sup.2 and Y have the above meanings, or with an alkali metal salt, alkaline earth metal salt or ammonium salt of this compound, in the presence or absence of an inert organic solvent, and in the presence or absence of an acid acceptor, at from -50.degree. to 150.degree. C., under atmospheric or superatmospheric pressure, continuously or batchwise.
If 5-chloro-6-isopropyl-3-methoxy-6H-1,2,4,6-thiatriazine-1,1-dioxide and propanol are used as starting materials, the course of the reaction can be represented by the following equation: ##STR7##
If 5-chloro-6-isopropyl-3-ethoxy-6H-1,2,4,6-thiatriazine-1,1-dioxide and sodium 4-chlorobenzenesulfinate are used, the course of the reaction can be represented by the following equation: ##STR8##
If 5-chloro-6-isopropyl-3-methylmercapto-6H-1,2,4,6-thiatriazine-1,1-dioxideand 2,4-dichlorophenol are used, the course of the reaction can be represented by the following equation: ##STR9##
Advantageously, the reaction is carried out in a solvent or diluent which is insert under the particular reaction conditions. Examples of suitable solvents are halohydrocarbons, especially chlorohydrocarbons, e.g. tetrachloroethylene, 1,1,2,2- or 1,1,1,2-tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane, chloroform, chloronaphthalene, dichloronaphthalene, carbon tetrachloride, 1,1,1- or 1,1,2-trichloroethane, trichloroethylene, pentachloroethane, o-, m- and p-difluorobenzene, 1,2-dichloroethane, 1,1-dichloroethane, 1,2-cis-dichloroethylene, chlorobenzene, fluorobenzene, bromobenzene, iodobenzene, o-, m- and p-dichlorobenzene, o-, m- and p-dibromobenzene, o-, m- and p-chlorotoluene and 1,2,4-trichlorobenzene; ethers, e.g. ethyl propyl ether, methyl tert.-butyl ether, n-butyl, ethyl ether, di-n-butyl ether, diisobutyl ether, diisoamyl ether, diisopropyl ether, anisole, phenetole, cyclohexyl methyl ether, diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, thioanisole and .beta., .beta.'-dichlorodiethyl ether; nitrohydrocarbons e.g. nitromethane, nitroethane, nitrobenzene, o-, m- and p-chloronitrobenzene and o-nitrotoluene; nitriles, e.g. acetonitrile, butyronitrile, isobutyronitrile, benzonitrile and m-chlorobenzonitrile; aliphatic or cycloaliphatic hydrocarbons, e.g. heptane, pinane, nonane, o-, m- and p-cymene, gasoline fractions boiling within a range of from 70.degree. to 190.degree. C., cyclohexane, methylcyclohexane, decalin, petroleum ether, hexane, naphtha, 2,2,4-trimethylpentane, 2,2,3-trimethylpentane, 2,3,3-trimethylpentane and octane; esters, e.g. ethyl acetate, ethyl acetoacetate and isobutyl acetate; amides, e.g. formamide, methylformamide and dimethylformamide; ketones, e.g. acetone and methyl ethyl ketone; and at times also water, and mixtures of the above. Advantageously, the solvent is used in an amount of from 100 to 2,000% by weight, preferably from 200 to 700% by weight, based on starting material II.
All conventional acid-binding agents can be used as the acid acceptors. Preferred examples are tertiary amines, alkaline earth metal compounds, ammonium compounds, alkali metal compounds and mixtures of these. However, zinc compounds may also be used. Specific examples of basic compounds are potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, lithium hydroxide, lithium carbonate, sodium bicarbonate, potassium bicarbonate, calcium hydroxide, calcium oxide, barium oxide, magnesium hydroxide, magnesium oxide, barium hydroxide, calcium carbonate, magnesium carbonate, magnesium bicarbonate, magnesium acetate, zinc hydroxide, zinc oxide, zinc carbonate, zinc bicarbonate, zinc acetate, sodium formate, sodium acetate, trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, triisobutylamine, tri-sec.-butylamine, tri-tert.-butylamine, tribenzylamine, tricyclohexylamine, triamylamine, trihexylamine, N,N-dimethylaniline, N,N-diethylaniline, N,N-dipropylaniline, N,N-dimethyltoluidine, N,N-diethyltoluidine, N,N-dipropyltoluidine, N,N-dimethyl-p-aminopyridine, N,N-diethyl-p-aminopyridine, N,N-dipropyl-p-aminopyridine, N-methylpyrrolidone, N-ethylpyrrolidone, N-methylpiperidine, N-ethylpiperidine, N-methyl-pyrrolidone, N-ethylpyrrolidine, N-methylimidazole, N-ethylimidazole, N-methylpyrrole, N-ethylpyrrole, N-methylmorpholine, N-ethylmorpholine, N-methylhexamethyleneimine, N-ethylhexamethyleneimine, pyridine, quinoline, .alpha.-picoline,.beta.-picoline,.gamma.-picoline,isoquinoline, pyrimidine, acridine, N,N,N',N'-tetramethylethylenediamine, N,N,N'N'-tetraethylethylenediamine, quinoxaline, quinazoline, N-propyldiisopropylamine, N,N-dimethylcyclohexylamine, 2,6-lutidine, 2,4-lutidine, trifurfurylamine and triethylenediamine.
The acid acceptors are advantageously used in from 80 to 120% of the amount equivalent to the starting material II. However, the hydrogen halide formed can also be removed by sweeping with an inert gas, for example nitrogen.
The starting materials III required for the reaction are in general employed in from 80 to 120% of the amount equivalent to the starting material II. However, the starting material II may also be employed directly as the solvent. Alternatively, the starting material III can be initially introduced into one of the above diluents, after which the starting material II and an acid acceptor are added, simultaneously or in any order, through two separate lines.
An advantageous method of preparing the novel compounds is to take the starting material II, in the presence or absence of one of the above diluents, and then to add the starting material III and an acid.
In many cases, the reaction is complete immediately after addition of the components; if not, the mixture is stirred further for from 10 minutes to 10 hours at from -50.degree. to 150.degree. C., preferably from 0.degree. to 120.degree. C., especially from 20.degree. to 100.degree. C.
If an inert gas is used to remove the hydrogen halide, it is advantageous to stir the mixture, after addition of the components, for from 0.2 to 10 hours at from 40.degree. to 100.degree. C.
The end product I is isolated from the reaction mixture in a conventional manner, for example after distilling off the solvent or excess starting material III, or directly, by filtering off.
In the latter case, the residue is washed with water or dilute alkali to remove acidic impurities, and is dried. In the case of water-immiscible diluents, the reaction mixture can also be extracted direct with water or with dilute alkali, and then be dried and evaporated down. However, it is also possible to dissolve the residue from filtration in a water-immiscible solvent, and wash this solution as described. The desired end products are obtained in a pure form; if desired, they can be purified further by recrystallization, chromatograpy or distillation.
The methods which follow relate to the preparation of the starting compounds of the formula II, and to the compounds from which they themselves are prepared.
METHOD 1
198 parts by weight of methylaminosulfonyl chloride and 162 parts of triethylamine were introduced simultaneously, through 2 separate lines, into a stirred mixture of 202 parts of N-carbomethoxy-O-methylisourea in 1,570 parts of acetonitrile, at 25.degree.-30.degree. C. After 3 hours' stirring at 25.degree. C., the hydrochloride which had precipitated was filtered off and the filtrate was evaporated down under reduced pressure. The residue was dissolved in 1,500 parts of 1,2-dichloroethane and the solution was extracted once with water and twice with 0.5 N hydrochloric acid. The extract was then dried over magnesium sulfate and evaporated down under reduced pressure, giving 257 parts of N-carbomethoxy-N'-methylsulfamyl-O-methylurea, of n.sub.D.sup.25 =1.4851.
96 parts of this product were dissolved in 235 parts of absolutely dry methanol, 153.5 parts of a 30 percent strength by weight solution of sodium methylate in methanol were added, and the mixture was stirred under reflux for 3 hours. It was then evaporated down under reduced pressure, the residue was dissolved in water, and the solution was extracted once with ether and then acidified with dilute sulfuric acid. The product was filtered off, washed with water and dried, giving 68 parts (=82.5% of theory) of 6-methyl-3-methoxy-6H-1,2,4,6-thiatriazin-5-one-1,1-dioxide, of melting point 198.degree.-202.degree. C.
METHOD 2
37.9 parts of isopropylaminosulfonyl chloride and 26.3 parts of triethylamine were added simultaneously, through two separate lines, to a stirred mixture of 54 parts of N-carbomethoxy-S-benzyl-isothiourea in 740 parts of 1,2-dichloroethane, at 5.degree.-10.degree. C. After 4 hours' stirring at 25.degree. C., the reaction mixture was extracted once with 200 parts of water and twice with 100 parts of 0.5 N hydrochloric acid at a time. The mixture was then dried and evaporated down under reduced pressure, giving 79 parts of N-carbomethoxy-N'-isopropylsulfamyl-S-benzylisothiourea, of n.sub.D.sup.25 =1.5598. This material crystallized on trituration with hexane; melting point 76.degree.-78.degree. C. 76 parts of the N-carbomethoxy-N'-isopropylsulfamyl-S-benzyl-isothiourea obtained were dissolved in a mixture of 44 parts of 50 percent strength by weight sodium hydroxide solution and 200 parts of water, and the batch was stirred for 5 minutes at 85.degree. C. It was then cooled and acidified with 15% strength hydrochloric acid, and the oil which precipitated was taken up in methylene chloride. The solution was dried over magnesium sulfate, filtered through neutral alumina and evaporated down under reduced pressure, giving 59.5 parts of 6-isopropyl-3-benzylmercapto-6H-1,2,4,6-thiatriazin-5-one-1,1-dioxide (86.3% of theory), of melting point 124.degree.-130.degree. C.
METHOD 3
59.6 parts of cyclohexylaminosulfonyl chloride and 26.9 parts of pyridine were introduced, through two separate lines, into a stirred solution of 39.6 parts of N-carbomethoxy-O-methyl-isourea in 300 parts of ethyl acetate, at 15.degree.-20.degree. C. After having been stirred for 4 hours at 25.degree. C., the reaction mixture was extracted once with water and once with 0.5 N hydrochloric acid, dried and then evaporated down under reduced pressure. This gave 79 parts of N-carbomethoxy-N'-cyclohexylsulfamyl-O-methyl-isourea, of n.sub.D.sup.25 =1.4970. After trituration with a small amount of ether, the compound crystallized; melting point 84.degree.-86.degree. C. 15 parts of the N-carbomethoxy-N'-cyclohexyl-sulfamyl-O-methyl-isourea obtained were dissolved in a mixture of 9 parts of 50 percent strength by weight sodium hydroxide solution and 20 parts of water and the reaction solution was stirred for 4 minutes at 55.degree.-60.degree. C. After cooling, it was extracted once with ether and then stirred into a mixture of 9.5 parts of concentrated hydrochloric acid in 10 parts of water. The product was filtered off, washed with water and dried, giving 9 parts of 6-cyclohexyl-3-methoxy-6H-1,2,4,6-thiatriazin-5-one-1,1-dioxide of melting point 173.degree.-177.degree. C.
METHOD 4
95 parts of isopropylaminosulfonyl chloride were stirred into a mixture of 96 parts of N-carbomethoxy-O-isopropyl-isourea and 73 parts of triethylamine in 700 parts of tetrahydrofuran at 10.degree.-15.degree. C., in the course of 25 minutes. After having been stirred for one hour at 25.degree. C., the reaction mixture was extracted once with water and once with 0.5 N hydrochloric acid, dried and evaporated down under reduced pressure. 130 parts of N-carbomethoxy-N'-isopropylsulfamyl-O-isopropylisourea, of melting point 62.degree.-64.degree. C., were obtained. 33.7 parts of this product were cyclized with 17.6 parts of 50 percent strength by weight sodium hydroxide solution in 30 parts of water for 5 minutes at 55.degree.-60.degree. C. After extraction with ether, acidification, filtering, washing the residue with water and drying, 22 parts of 6-isopropyl-3-isopropoxy-6H-1,2,4,6-thiatriazin-5-one-1,1-dioxide, of melting point 164.degree.-167.degree. C., were obtained.
METHOD 5
12 parts of 6-isopropyl-3-isopropoxy-6H-1,2,4-thiatriazin-5-one-1,1-dioxide were dissolved in a mixture of 10.4 parts of a 30 percent strength by weight solution of sodium methylate in methanol and 64 parts of methanol at 25.degree. C. After evaporating down, 13.8 parts of the 2-sodium salt of 6-isopropyl-3-isopropoxy-6H-1,2,4,6-thiatriazin-5-one-1,1-dioxide were obtained; melting point 123.degree. C., with decomposition.
METHOD 6
140 parts of N-carboxymethyl-N'-methylsulfamyl-O-methyl-urea, in a mixture of 79.5 parts of sodium carbonate, 450 parts of water and 31 parts by volume of 2 N sodium hydroxide solution, were stirred for 10 minutes at 45.degree. C. The reaction mixture was then cooled, extracted with ether, and stirred slowly into a mixture of 78 parts of concentrated sulfuric acid and 150 parts of ice water. The product was filtered off, washed with water and dried, giving 81 parts of 6-methyl-3-methoxy-6H-1,2,4,6-thiatriazin-5-one-1,1-dioxide (68% of theory), of melting point 195.degree.-199.degree. C.
METHOD 7
215 parts of 6-methyl-3-methoxy-6H-1,2,4,6-thiatriazin-5-one-1,1-dioxide were introduced into a stirred mixture of 275 parts of phosphorous pentachloride in 1,480 parts of phosphorus oxychloride at room temperature, and the batch was heated to 110.degree. C. in the course of 30 minutes. After 4 hours' stirring under reflux, the reaction mixture was concentrated under reduced pressure, giving 235 parts (99.6% of theory) of 5-chloro-6-methyl-3-methoxy-6H-1,2,4,6-thiatriazine-1,1-dioxide, of melting point 77.degree.-83.degree. C.
METHOD 8
154 parts of phosphorus pentachloride were added, in the course of 2 minutes, to a stirred mixture of 128 parts of 6-ethyl-3-methoxy-6H-1,2,4,6-thiatriazin-5-one-1,1-dioxide in 840 parts of phosphorus oxychloride, at 25.degree. C. The reaction mixture was stirred under reflux for 51/2 hours and then concentrated under reduced pressure. The oil which remained was taken up in 300 parts of 1,2-dichloroethane and chromatographed over neutral alumina (activity I). The solution was then evaporated down, giving 127.5 parts (91% of theory) of 5-chloro-6-ethyl-3-methoxy-6H-1,2,4,6-thiatriazine-1,1-dioxide, of melting point 63.degree.-70.degree. C.
METHOD 9
50 parts of phosphorus pentachloride were introduced into a stirred mixture of 41.4 parts of 6-methyl-3-ethoxy-6H-1,2,4,6-thiatriazin-5-one-1,1-dioxide in 100 parts of 1,2-dichloroethane and 100 parts of phosphorus oxychloride at room temperature. The reaction mixture was stirred under reflux for 12 hours and then evaporated down under reduced pressure, giving 43.5 parts (96.5% of theory) of 5-chloro-6-methyl-3-ethoxy-6H-1,2,4,6-thiatriazine-1,1-dioxide, of melting point 75.degree.-80.degree. C.
METHOD 10
50 parts of phosphorus pentachloride were added to a stirred mixture of 44 parts of 6-n-propyl-3-methoxy-6H-1,2,4,6-thiatriazin-5-one-1,1-dioxide and 268 parts of phosphorus oxychloride at 22.degree. C., and the batch was heated to 110.degree. C. in the course of 20 minutes. After 7 hours' stirring under reflux, it was evaporated down under reduced pressure, giving 45 parts of oily 5-chloro-6-n-propyl-3-methoxy-6H-1,2,4,6-thiatriazine-1,1-dioxide; NMR (CDCl.sub.3): N-CH.sub.2 4.0-4.28.
Distillation at 125.degree.-130.degree. C./0.01 mbar gave 40.3 parts (84% of theory) of pure product.
METHOD 11
A suspension of 25 parts of 6-ethyl-3-methylmercapto-6H-1,2,4,6-thiatriazin-5-one-1,1-dioxide in 2.5 parts of DMF and 245 parts of 1,2-dichloroethane, at 83.degree. C., was gassed with phosgene for 14 hours, whilst stirring. It was then evaporated down under reduced pressure, giving 27 parts of a viscous oil, which according to the NMR spectrum contained about 45% of 5-chloro-6-ethyl-3-methylmercapto-6H-1,2,4,6-thiatriazine-1,1-dioxide. A sample was distilled at 136.degree.-144.degree. C./0.01 mbar; NMR (CDCl.sub.3): N-CH.sub.2 4.04-4.42 .delta. (q), CH.sub.3 S 2.52 .delta. (s).

The Examples which follow relate to the preparation of the novel compounds.
EXAMPLE 1
6-Isopropyl-3-methoxy-5-ethoxy-6H-1,2,4,6-thiatriazine-1,1-dioxide (No. 1)
28.7 parts by weight of 5-chloro-6-isopropyl-3- methoxy-6H-1,2,4,6-thiatriazine-1,1-dioxide were added, a little at a time, in the course of 10 minutes, to a stirred mixture of 12.2 parts of triethylamine and 90 parts of absolute ethanol at 20.degree.-25.degree. C. After 3 hours' stirring at 25.degree. C., the reaction mixture was evaporated down under reduced pressure, the residue was taken up in methylene chloride and the solution was washed with 10% strength sodium carbonate solution. After drying over magnesium sulfate, chromatography over alumina and evaporating down under reduced presure, 24 parts of 6-isopropyl-33-methoxy-5-ethoxy-6H-1,2,4,6-thiatriazine-1,1-dioxide, of melting point 81.degree.-85.degree. C. were obtained.
EXAMPLE 2
6-Methyl-3-methoxy-5-octadecyloxycarbo-methylmercapto-6H-1,2,4,6-thiatriazine-1,1-dioxide (No. 2)
34.5 parts of octadecyl mercaptoacetate in 45 parts of ethyl acetate, and 10.2 parts of triethylamine, were introduced simultaneously through 2 separate lines, in the course of 15 minutes, into a stirred mixture of 21.2 parts of 5-chloro-6-methyl-3-methoxy-6H-1,2,4,6-thiatriazine-1,1-dioxide in 90 parts of ethyl acetate at 20.degree.-25.degree. C. The reaction mixture was stirred for 1 hour at 25.degree. C. and the precipitate was then filtered off and washed with water to remove the triethylamine hydrochloride, then with dilute sodium carbonate solution and then again with water. The organic filtrate was evaporated down and the residue was also washed as above. After drying, a total of 41 parts of 6-methyl-3-methoxy-5-octadecyloxycarbomethylmercapto-6H-1,2,4,6-thiatriazine-1,1-dioxide, of melting point 74.degree.-80.degree. C., were obtained.
EXAMPLE 3
6-Methyl-3-n-propoxy-5-p-nitrophenoxy-6H-1,2,4,6-thiatriazine-1,1-dioxide (No. 3)
13.9 parts of p-nitrophenol in 40 parts of methylene chloride, and 10.2 parts of triethylamine, were introduced simultaneously through 2 separate lines, in the course of 10 minutes, into a stirred solution of 23.9 parts of 5-chloro-6-methyl-3-n-propoxy-6H-1,2,4,6-thiatriazine-1,1-dioxide in 180 parts of methylene chloride at 20.degree.-25.degree. C. The reaction mixture was stirred under reflux for 3 hours, cooled, washed with water and then 3 times with dilute sodium hydroxide solution, dried over magnesium sulfate and evaporated down under reduced pressure. 31 parts of 6-methyl-3-n-propoxy-5-p-nitrophenoxy-6H-1,2,4,6-thiatriazine-1,1-dioxide, of melting point 129.degree.-131.degree. C., were obtained.
EXAMPLE 4
6-Methyl-3-ethoxy-5-allyloxy-6H-1,2,4,6-thiatriazine-1,1-dioxide (No. 166)
7 parts of allyl alcohol and 12.9 parts of 2,6-dimethylpyridine were introduced simultaneously through 2 separate lines, in the course of 6 minutes, into a stirred mixture of 22.6 parts of 5-chloro-6-methyl-3-ethoxy-6H-1,2,4,6-thiatriazine-1,1-dioxide in 140 parts of tetrahydrofuran at 25.degree.-35.degree. C. After having been stirred for 30 minutes at 50.degree. C., the reaction mixture was evaporated down, the residue was taken up in methylene chloride and this solution was washed 3 times with 10% strength sodium carbonate solution. It was then dried over magnesium sulfate and evaporated down under reduced pressure, giving 14 parts of 6-methyl-3-ethoxy-5-allyloxy-6H-1,2,4,6-thiatriazine-1,1-dioxide, of melting point 56.degree.-60.degree. C.
The following novel compounds were obtained similarly.
__________________________________________________________________________Compoundno. R.sup.1 X Y R.sup.2 R.sup.3 M.p.[.degree.C.]/n.sub.D.sup.2 5__________________________________________________________________________4 CH.sub.3 O O CH.sub.3 H5 CH.sub.3 O O CH.sub.3 CH.sub.3 100-1046 CH.sub.3 O O C.sub.2 H.sub.5 CH.sub.3 108-1127 CH.sub.3 O O C.sub.2 H.sub.5 C.sub.2 H.sub.5 77-808 CH.sub.3 O O C.sub.2 H.sub.5 i-C.sub.3 H.sub.79 CH.sub.3 O O CH.sub.2CHCH.sub.2 C.sub.2 H.sub.5 69-7210 CH.sub.3 S O CH.sub.3 CH.sub.3 129-13311 CH.sub.3 S S CH.sub.3 CH.sub.312 CH.sub.3 S SO.sub.2 CH.sub.3 CH.sub.313 CH.sub.3 O O CH.sub.2CHCH.sub.2 H14 C.sub.2 H.sub.5 O O CH.sub.3 CH.sub.315 C.sub.2 H.sub.5 O S C.sub.2 H.sub.5 CH.sub.316 C.sub.2 H.sub.5 O O C.sub.2 H.sub.5 C.sub.2 H.sub.517 C.sub.2 H.sub. 5 O O CH.sub.2CHCH.sub.2 C.sub.2 H.sub.518 C.sub.2 H.sub.5 O O 1-Propyn-yl-3 CH.sub.3 78-8119 C.sub.2 H.sub.5 S O CH.sub.2CHCH.sub.2 CH.sub.320 C.sub.2 H.sub.5 O S CH.sub.2CHCH.sub.2 CH.sub.321 C.sub.2 H.sub.5 O O CHCHCH.sub.2 Cl CH.sub.322 C.sub.2 H.sub.5 O S ##STR10## CH.sub.323 n-C.sub.3 H.sub.7 O O CH.sub.2CH.sub.2OCH.sub.3 CH.sub.324 n-C.sub.3 H.sub.7 O O 1-Chloro-2-butyn-yl-4 CH.sub.325 i-C.sub.3 H.sub.7 O O 1-Methoxy-2-butyn-yl-4 C.sub.2 H.sub.526 CH.sub.3 O O 1-Methylmercapto-2- CH.sub.3 butyn-yl-427 n-C.sub.3 H.sub.7 O O 1-Chloro-3-buty-n-yl-2 C.sub.2 H.sub.528 CH.sub.3 O S ##STR11## CH.sub.329 C.sub.2 H.sub.5 O O ##STR12## CH.sub.330 CH.sub.3 O O ##STR13## CH.sub.331 CH.sub.3 O O CH.sub.2CH.sub.2SCH.sub.3 CH.sub.332 i-C.sub.3 H.sub.7 O O CH.sub.3 CH.sub.333 n-C.sub.4 H.sub.9 O O C.sub.2 H.sub.5 CH.sub.334 sec-C.sub.4 H.sub.9 O O n-C.sub.3 H.sub.7 CH.sub.335 ##STR14## O O CH.sub.3 CH.sub.336 CH.sub.3 O O ##STR15## CH.sub.3 1.482937 CH.sub.3 O O 4-CF.sub.3phenyl CH.sub.338 CH.sub.3 O O 3-OCHF.sub.2Phenyl CH.sub.339 CH.sub.3 O S 3-Chlorophenyl CH.sub.340 CH.sub.3 O O n-C.sub.3 H.sub.7 CH.sub.3 50-5441 C.sub.2 H.sub.5 O O n-C.sub.4 H.sub.9 C.sub.2 H.sub.542 CH.sub.3 O O 4-Methylmercaptophenyl C.sub.2 H.sub.543 CH.sub.3 O O 4-Methoxyphenyl CH.sub.344 CH.sub.3 O O CH.sub.3 C.sub.2 H.sub.5 102-10445 i-C.sub.3 H.sub.7 O S CH.sub.3 CH.sub.346 n-C.sub.4 H.sub.9 O O C.sub.2 H.sub.5 C.sub.2 H.sub.547 CH.sub.3 O S CH.sub.3 CH.sub.3 125-12848 CH.sub.3 O O 2-Butyn-yl-4 CH.sub.349 CH.sub.3 O O 1-Butyn-yl-3 CH.sub.350 C.sub.2 H.sub.5 S O 1-Butyn-yl-3 CH.sub.351 CH.sub.3 O O CH.sub.2CHCH.sub.2 CH.sub.3 55-5752 i-C.sub.3 H.sub.7 O O ##STR16## CH.sub.353 CH.sub.2CHCH.sub.2 O O CH.sub.3 CH.sub.354 Propargyl O O CH.sub.3 C.sub.2 H.sub.555 CH.sub.2CH.sub.2 Cl O O C.sub.2 H.sub.5 CH.sub.356 Cyclohexyl O S CH.sub.3 i-C.sub.3 H.sub.757 3-Chlorophenyl O O CH.sub.3 CH.sub.358 CH.sub.3 O O i-C.sub.3 H.sub.7 CH.sub.3 73-7759 C.sub.2 H.sub.5 O S n-C.sub.4 H.sub.9 C.sub.2 H.sub.560 n-C.sub.3 H.sub.7 O O C.sub.2 H.sub.5 CH.sub.3 49-5161 CH.sub.3 O O 4-Methylphenyl C.sub.2 H.sub.562 CH.sub.3 O O 4-CF.sub.3 Sphenyl CH.sub.363 C.sub.2 H.sub.5 S O CH.sub.3 CH.sub.364 C.sub.2 H.sub.5 O O C.sub.2 H.sub.5 i-C.sub.3 H.sub.7 40-4665 tert.C.sub.4 H.sub.9 S O CH.sub.3 CH.sub.366 C.sub.2 H.sub.5 O O CH.sub.3 i-C.sub.3 H.sub.7 74-7867 C.sub.2 H.sub.5 O SO.sub.2 CH.sub.3 CH.sub.368 CH.sub.3OCH.sub.2 CH.sub.2 O O CH.sub.3 CH.sub.369 C.sub.2 H.sub.5 O O C.sub.2 H.sub.5 CH.sub.3 72-7570 C.sub.6 H.sub.5CH.sub.2 O O CH.sub.3 CH.sub.371 4-Chlorobenzyl O O CH.sub.3 CH.sub.372 4-Methoxy- O O C.sub.2 H.sub.5 CH.sub.3 phenyl73 i-C.sub.3 H.sub.7 O O CH.sub.3 n-C.sub.3 H.sub.7 71-7574 CH.sub.3 S O CH.sub.2CHCH.sub.2 CH.sub.3 90-9375 CH.sub.3 O S 1-Propyn-yl-3 CH.sub.376 CH.sub.3 O O CH.sub.3 i-C.sub.3 H.sub.7 108-11177 CH.sub.3 O O CH.sub.3 sec-C.sub.4 H.sub.978 CH.sub.3 O O C.sub.2 H.sub.5 tert.-C.sub.4 H.sub.979 CH.sub.3 O O 1-Propyn-yl-3 H80 C.sub.2 H.sub.5 O O ##STR17## C.sub.2 H.sub.581 CH.sub.3SCH.sub.2 CH.sub.2 O O CH.sub.3 CH.sub.382 CH.sub.3 O O CH.sub.2CHCH.sub.2 CH.sub.2CHCH.sub.283 CH.sub.3 S O CH.sub.3 CH.sub.2CHCH.sub.284 CH.sub.3 O O CH.sub.3 Cyclohexyl85 i-C.sub.3 H.sub.7 S O CH.sub.3 Cyclohexyl86 CH.sub.3 O O CH.sub.3 CH.sub.2 OCH.sub.387 CH.sub.3 O O CH.sub.3 CH.sub.2CH.sub.2 Cl88 C.sub.2 H.sub.5 O O CH.sub.3 CH.sub.2CH.sub.2 F89 CH.sub.3 O O 4-Nitrophenyl CH.sub.3 235-24090 CH.sub.3 O O ##STR18## CH.sub.391 C.sub.2 H.sub.5 S O ##STR19## CH.sub.392 C.sub.2 H.sub.5 O O 4-Cyanophenyl CH.sub.393 CH.sub.3 O O 4-Thiocyanophenyl CH.sub.394 i-C.sub.3 H.sub.7 O O 3-Carboxyphenyl CH.sub.395 CH.sub. 3 O O 4-Nitro-3-carboxyphenyl CH.sub.396 CH.sub.3 O O 2-Methyl-4,6-dinitro- CH.sub.3 160-163 phenyl97 C.sub.2 H.sub.5 O S 4-Nitrophenyl CH.sub.398 n-C.sub.3 H.sub.7 O O ##STR20## CH.sub.399 CH.sub.3 O O 2,4-Dichlorophenyl CH.sub.3 189-194100 CH.sub.3 O O 3,5-Dichlorophenyl C.sub.2 H.sub.5101 CH.sub.3 O O 2,3-Dichlorophenyl n-C.sub.3 H.sub.7102 CH.sub.3 O S ##STR21## CH.sub.3103 CH.sub.3 O O 2,4,6-Trichlorophenyl CH.sub.3 221-226104 CH.sub.3 S O ##STR22## CH.sub.3105 C.sub.2 H.sub.5 O O ##STR23## C.sub.2 H.sub.5106 CH.sub.3 S O ##STR24## CH.sub.3107 CH.sub.3 O O 2,4-Dinitro-6-tert- CH.sub.3 156-161 butylphenyl108 CH.sub.2CHCH.sub.2 O O ##STR25## C.sub.2 H.sub.5109 i-C.sub.3 H.sub.7 O O ##STR26## CH.sub.3110 CH.sub.3 O O ##STR27## CH.sub.3 151-156111 n-C.sub.3 H.sub.7 O O ##STR28## CH.sub.3112 CH.sub.3 S O ##STR29## CH.sub.3113 CH.sub.3 O O 2,6-Dibromo-4-cyano- CH.sub.3 242-246 phenyl114 C.sub.2 H.sub.5 O O ##STR30## C.sub.2 H.sub.5115 CH.sub.3 O O ##STR31## C.sub.2 H.sub.5116 C.sub.2 H.sub.5 S O Benzyl CH.sub.3117 CH.sub. 3 O O 2,6-Diiodo-4-cyanophenyl CH.sub.3 276-281118 CH.sub.3 O O 2-Nitrophenyl C.sub.2 H.sub.5119 CH.sub.3 O O 3-Nitrophenyl CH.sub.3 213-218120 C.sub.2 H.sub.5 O O ##STR32## CH.sub.3121 CH.sub.3 S O ##STR33## CH.sub.3122 C.sub.2 H.sub.5 O O ##STR34## CH.sub.3123 CH.sub.3 O O 4-Chlorophenyl CH.sub.3 199-202124 CH.sub.3 O O ##STR35## i-C.sub.3 H.sub.7125 C.sub.2 H.sub.5 S O ##STR36## CH.sub.3126 CH.sub.3 O O 4-Nitrophenyl C.sub.2 H.sub.5 176-178127 CH.sub.3 S O ##STR37## CH.sub.3128 C.sub.2 H.sub.5 O O ##STR38## CH.sub.3129 CH.sub.3 O O 4-tert.-butylphenyl CH.sub.3 155-158130 C.sub.2 H.sub.5 O S 2,6-Dimethylphenyl CH.sub.3131 CH.sub.3 O O 4-Chlorobenzyl CH.sub.3132 CH.sub.3 O O 4-Cyanophenyl CH.sub.3 219-221133 CH.sub.3 O O 3,4-Difluorophenyl CH.sub.3134 CH.sub.3 O O 3-tert.-butylphenyl CH.sub.3 113-116135 C.sub.2 H.sub.5 O O 4-tert.-butylphenyl CH.sub.3136 CH.sub.3 O O 2,4-Dichloro-6-methyl- CH.sub.3 194-196 phenyl137 C.sub.2 H.sub.5 O O 2-Chloro-4-nitrophenyl CH.sub.3138 CH.sub.3 O O 4-Nitrophenyl H139 CH.sub.3 O O 4-CF.sub.3 2-chlorophenyl CH.sub.3 178-179140 CH.sub.3 O O 3-Chloro-4-methoxyphenyl H141 C.sub.2 H.sub.5 O O 3-CF.sub.3phenyl H142 CH.sub.3 O O ##STR39## CH.sub.3 199-204143 CH.sub.3 O O ##STR40## CH.sub.3 216-220144 CH.sub.3 O O ##STR41## CH.sub.3 134-138145 CH.sub.3 S O 3,4-Dichlorobenzyl CH.sub.3146 C.sub.2 H.sub.5 O O 4-Nitrophenyl CH.sub.3 146-150147 i-C.sub.3 H.sub.7 O O 2-Chloro-4-nitrophenyl CH.sub.3148 C.sub.2 H.sub.5 O O 4-Nitrophenyl i-C.sub.3 H.sub.7 150-154149 CH.sub.3 O O ##STR42## CH.sub.3150 sec.C.sub.4 H.sub.9 O O 4-Nitrophenyl i-C.sub.3 H.sub.7 138-144151 C.sub.2 H.sub.5 O S Benzyl CH.sub.3152 CH.sub.3 O O 4-Nitrophenyl i-C.sub.3 H.sub.7 200-204153 CH.sub.3 O O 4-Nitrophenyl n-C.sub.3 H.sub.7 152-155154 CH.sub.3 S O Benzyl CH.sub.3155 CH.sub.3 O O Benzyl CH.sub.3 141-145156 CH.sub.3 O O 3-CF.sub.3 OPhenyl CH.sub.3157 CH.sub.3 O O sec.-Butyl CH.sub.3 1.4904158 CH.sub.3 O O 1-Propyn-yl-3 CH.sub.3 98-102159 CH.sub.3 O O 1-Propyn-yl-3 C.sub.2 H.sub.5160 C.sub.2 H.sub.5 O O 1-Propyn-yl-3 C.sub.2 H.sub.5161 C.sub. 2 H.sub.5 O O Benzyl CH.sub.3 73-75162 CH.sub.3 O O 2,6-Dichlorobenzyl CH.sub.3 104-107163 n-C.sub.3 H.sub.7 O O CH.sub.2CHCH.sub.2 CH.sub.3 43-47164 n-C.sub.3 H.sub.7 O O 1-Propyn-yl-3 CH.sub.3 98-103165 C.sub.2 H.sub.5 O O 2,6-Dichlorbenzyl CH.sub.3 119-123166 C.sub.2 H.sub.5 O O Allyl CH.sub.3 56-60__________________________________________________________________________
The novel active ingredients can be converted into the conventional formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes and granules. The form of application depends entirely on the purpose for which the agents are being used; it should, however, ensure a fine and uniform distribution of the active ingredient. The formulations are prepared in the conventional manner, for example by diluting the active ingredient with solvent and/or carriers, with or without the addition of emulsifiers and dispersants and, where water is used as the diluent, with or without organic auxiliary solvents. Suitable auxiliaries are, essentially, solvents, for example aromatics, e.g., xylene and benzene, chloroaromatics, e.g. chlorobenzene, paraffins, e.g. petroleum fractions, alcohols, e.g. methanol and butanol, amines, e.g., ethanolamine, dimethylformamide, and water; solid carriers, for example natural rock powders, e.g., kaolin, alumina, talc and chalk, and synthetic rock powders, e.g. highly disperse silica and silicates; emulsifiers, for example non-ionic and anionic emulsifiers, e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates, and dispersants, for example lignin, sulfite waste liquors and methylcellulose.
To initiate the herbicidal action, wetting agents, adherents, and non-phytotoxic oils and oil concentrates may be added.
The herbicidal agents in general contain from 0.1 to 95% by weight of active ingredients, preferably from 0.5 to 90%.
The application rates depend on the composition and growth stages of the weed flora, and vary from 0.1 to 15, and preferably from 0.2 to 5.0, kg of active ingredients per hectare, the higher rates being used for total plant destruction.
The agents, and the ready-to-use preparations obtained therefrom, e.g., solutions, emulsions, suspensions, powders, dusts, pastes or granules, are applied in conventional manner, e.g. by spraying, atomizing, dusting, broadcasting or watering.
Examples of such formulations are given below.
I. 90 parts by weight of the compound of Example 1 is mixed with 10 parts by weight of N-methyl-.alpha.-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
II. 80 parts by weight of the compound of Example 2 is mixed with 20 parts by weight of cyclohexanone. The composition may be sprayed as fine drops.
III. 20 parts by weight of the compound of Example 3 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.
IV. 3 parts by weight of the compound of Example 2 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.
V. 30 parts by weight of the compound of Example 3 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.
VI. 20 parts of the compound of Example 1 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.
It may also be useful to apply the active ingredients, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g., agents for combating pests or phytopathogenic fungi or bacteria. The compounds may also be mixed with solutions of mineral matters used to remedy nutritional or trace element deficiencies.
The influence of representatives of the novel, herbicidal, substituted 6H-1,2,4,6-thiatriazine-1,1-dioxides on the growth of unwanted and crop plants is demonstrated in greenhouse experiments.
The vessels employed were plastic flowerpots having a volume of 300 cm.sup.3, and which were filled with a sandy loam containing about 1.5% humus. To ensure good growth of Cyperus esculentus, Glycine max. and Oryza sativa, peat was added. The seeds of the test plants given in Table 1 were sown shallow, and separately, according to species. In the case of Cyperus esculentus, pregerminated tubers were employed. In the preemergence treatment, the active ingredients were immediately applied to the surface of the soil as a suspension or emulsion in water by spraying through finely distributing nozzles.
The application rates varied, depending on the active ingredient. Rates employed were 0.5, 1.0, 2.0 and 4.0 kg of active ingredient per hectare.
After the agents had been applied, the vessels were lightly sprinkler-irrigated to induce germination and growth and to activate the chemical agents. Transparent plastic covers were then placed on the vessels until the plants had taken root. The cover ensured uniform germination of the plants, insofar as this was not impaired by the chemicals.
For the postemergence treatment, the plants were first grown in the vessels to a height of from 3 to 10 cm, depending on growth form, before being treated. For this treatment, either plants which were sown directly in the pots and grew there were selected, or plants which were grown separately as seedlings and transplanted to the experiment vessels a few days before treatment. The amounts of active ingredient applied in this treatment also differed from ingredient to ingredient, and were either 0.5, 1.0 or 2.0 kg/ha.
The agent used for comparison purposes was compound A: ##STR43## (disclosed in German Laid-Open Application DE-OS 2,508,832).
No cover was placed on the vessels in the postemergence treatment. The pots were set up in the greenhouse - species from warmer areas at from 20.degree. to 35.degree. C., and species from moderate climates at 10.degree. to 20.degree. C. The experiments were run for from 2 to 4 weeks. During this period, the plants were tended and their reactions to the various treatments assessed. The scale used for assessment was 0 to 100, 0 denoting no damage or normal emergence, and 100 denoting nonemergence or complete destruction of at least the visible plant parts.
The results show that the novel compounds according to the invention are suitable for combating broadleaved unwanted plants and annual and perennial Cyperaceae in crop plants, or for total elimination of vegetation either on pre- or postemergence treatment. That the compounds are also effective against unwanted grasses is worthy of note.
TABLE 1______________________________________List of plant namesBotanical name Common name______________________________________Chenopodium album lambsquartersCyperus spp. annual sedges(C. iria, C. ferax,C. difformis)Cyperus esculentus yellow nutsedgeDatura stramonium jimson weedGlycine max soybeansGossypium hirsutum cottonMatricaria spp. chamomile spp.Nicandra physaloides apple of PeruOryza sativa riceSolanum nigrum black nightshadeZea mays Indian corn, maize______________________________________
In an experiment to test the herbicidal action (postemergence application in the greenhouse), new compounds 51, 146 and 69 exhibited, at rates of 0.5 to 1.0 kg/ha, a better selective herbicidal action than the prior art compound A.
In an experiment to control unwanted broadleaved plants in soybeans (preemergence application in the greenhouse), new compounds 113, 36, 142, 119, 129, 136, 139 and 123 exhibited, at rates of 0.5 and 1.0 kg/ha, a better selective herbicidal action than prior art compound A.
In an experiment to control Cyperaceae in rice (preemergence treatment in the greenhouse), new compounds 40, 92, 144, 69, 89 and 155 exhibited, at rates of 4.0 and 2.0 kg/ha, a good selective herbicidal action.
In an experiment to test the selective control of broadleaved unwanted plants in crops (preemergence treatment in the greenhouse), new compounds 143, 144, 139 and 110 exhibited, at rates of 1.0 and 2.0 kg/ha, a good selective herbicidal action.
Compounds 89 and 155, for instance, also had an excellent action for the selective control of Cyperus esculentus in rice (postemergence application in the greenhouse).
If certain crop plants tolerate the active ingredients less well, application techniques may be used in which the agents are sprayed from suitable equipment in such a manner that the leaves of sensitive crop plants are if possible not touched, and the agents reach the soil or the unwanted plants growing beneath the crop plants (post-directed, lay-by treatment). In view of the good tolerance of the active ingredients and the many application methods possible, the agents according to the invention, or mixtures containing them, may be used not only on the crop plants listed in Table 1, but also in a much larger range of crops for removing unwanted plants. Application rates may vary from 0.1 to 15 kg/ha and more.
The following crop plants may be mentioned by way of example:
______________________________________Botanical name Common name______________________________________Allium cepa onionsAnanas comosus pineapplesArachis hypogaea peanuts (groundnuts)Asparagus officinalis asparagusAvena sativa oatsBeta vulgaris spp. altissima sugarbeetsBeta vulgaris spp. rapa fodder beetsBeta vulgaris spp. esculenta table beets, red beetsBrassica napus var. napus rapeBrassica napus var. napobrassicaBrassica napus var. rapa turnipsBrassica rapa var. silvestrisCamellia sinensis tea plantsCarthamus tinctorius safflowerCarya illinoinensis pecan treesCitrus limon lemonsCitrus maxima grapefruitsCitrus reticulata mandarinsCitrus sinensis orange treesCoffea arabica (Coffea canephora, coffee plantsCoffea liberica)Cucumis melo melonsCucumis sativus cucumbersCynodon dactylon Bermudagrass in turf and lawnsDaucus carota carrotsElais guineensis oil palmsFragaria vesca strawberriesGlycine max soybeansGossypium hirsutum cotton(Gossypium arboreumGossypium herbaceumGossypium vitifolium)Helianthus annuus sunflowersHelianthus tuberosusHevea brasiliensis rubber plantsHordeum vulgare barleyHumulus lupulus hopsIpomoea batatas sweet potatoesJuglans regia walnut treesLactuca sativa lettuceLens culinaris lentilsLinum usitatissimum flaxLycopersicon lycopersicum tomatoesMalus spp. apple treesManihot esculenta cassavaMedicago sativa alfalfa (lucerne)Mentha piperita peppermintMusa spp. banana plantsNicothiana tabacum tobacco(N. rustica)Olea europaea olive treesOryza sativa ricePanicum miliaceumPhaseolus lunatus limabeansPhaseolus mungo mungbeansPhaseolus vulgaris snapbeans, green beans, dry beansPennisetum glaucumPetroselinum crispum parsleyspp. tuberosumPicea abies Norway spruceAbies alba fir treesPinus spp. pine treesPisum sativum English peasPrunus avium cherry treesPrunus domestica plum treesPrunus dulcis almond treesPrunus persica peach treesPyrus communis pear treesRibes sylvestre redcurrantsRibes uva-crispa gooseberriesRicinus communis castor-oil plantsSaccharum officinarum sugar caneSecale cereale ryeSesamum indicum sesameSolanum tuberosum Irish potatoesSorghum bicolor (s. vulgare) sorghumSorghum dochnaSpinacia oleracea spinachTheobroma cacao cacao plantsTrifolium pratense red cloverTriticum aestivum wheatVaccinium corymbosum blueberriesVaccinium vitis-idaea cranberriesVicia faba tick beansVigna sinensis (V. unguiculata) cow peasVitis vinifera grapesZea mays Indian corn, sweet corn, maize______________________________________
To increase the spectrum of activity and to achieve synergistic effects, the novel active ingredients may be mixed among themselves or with numerous representatives of other herbicidal or growth-regulating active ingredient groups and applied in such mixtures. Examples of suitable mixture components are diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives, cyclohexane-1,3-dione derivatives, etc. A number of active ingredients which, when combined with the new compounds, give mixtures useful for widely varying applications are given below by way of example:
5-amino-4-chloro-2-phenyl-3(2H)-pyridazinone
5-amino-4-bromo-2-phenyl-3(2H)-pyridazinone
5-amino-4-chloro-2-cyclohexyl-3(2H)-pyridazinone
5-amino-4-bromo-2-cyclohexyl-3(2H)-pyridazinone
5-methylamino-4-chloro-2-(3-trifluoromethylphenyl)-3(2H)-pyridazinone
5-methylamino-4-chloro-2-(3-.alpha.,.alpha.,.beta.,.beta.-tetrafluoroethoxyphenyl)-3(2H)-pyridazinone
5-dimethylamino-4-chloro-2-phenyl-3(2H)-pyridazinone
4,5-dimethoxy-2-phenyl-3(2H)-pyridazinone
4,5-dimethoxy-2-cyclohexyl-3(2H)-pyridazinone
4,5-dimethoxy-2-(3-trifluoromethylphenyl)-3(2H)-pyridazinone
5-methoxy-4-chloro-2-(3-trifluoromethylphenyl)-3(2H)-pyridazinone
5-amino-4-bromo-2(3-methylphenyl)-3(2H)-pyridazinone
3-(1-methylethyl)-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide and salts
3-(1-methylethyl)-8-chloro-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide and salts
3-(1-methylethyl)-8-fluoro-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide and salts
3-(1-methylethyl)-8-methyl-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide and salts
1-methoxymethyl-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide
1-methoxymethyl-8-chloro-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide
1-methoxymethyl-8-fluoro-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide
1-cyano-8-chloro-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide
1-cyano-8-fluoro-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide
1-cyano-8-methyl-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide
1-cyano-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide
1-azidomethyl-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide
3-(1-methylethyl)-1H-pyridino-[3,2-e]-2,1,3-thiadiazin-(4)-one-2,2-dioxide
N-(1-ethylpropyl)-2,6-dinitro-3,4-dimethylaniline
N-(1-methylethyl)-N-ethyl-2,6-dinitro-4-trifluoromethylaniline
N-n-propyl-N-.beta.-chloroethyl-2,6-dinitro-4-trifluoromethylaniline
N-n-propyl-N-cyclopropylmethyl-2,6-dinitro-4-trifluoromethylaniline
N-bis-(n-propyl)-2,8-dinitro-3-amino-4-trifluoromethylaniline
N-bis-(n-propyl)-2,6-dinitro-4-methylaniline
N-bis-(n-propyl)-2,6-dinitro-4-methylsulfonylaniline
N-bis-(n-propyl)-2,6-dinitro-4-aminosulfonylaniline
bis-(.beta.-chloroethyl)-2,6-dinitro-4-methylaniline
N-ethyl-N-(2-methylallyl)-2,6-dinitro-4-trifluoromethylaniline
3,4-dichlorobenzyl N-methylcarbamate
2,6-di-tert.butyl-4-methylphenyl N-methylcarbamate isopropyl N-phenylcarbamate
3-methoxyprop-2-yl N-3-fluorophenylcarbamate
isopropyl N-3-chlorophenylcarbamate
but-1-yn-3-yl N-3-chlorophenylcarbamate
4-chlorobut-2-yn-1-yl N-3-chlorophenylcarbamate
methyl N-3,4-dichlorophenylcarbamate
methyl N-(4-aminobenzenesulfonyl)-carbamate
0-(n-phenylcarbamoyl)-propanone oxime
N-ethyl-2-(phenylcarbamoyl)-oxypropionic acid amide
3'-N-isopropylcarbamoyloxypropionanilide
ethyl-N-(3-(N'-phenylcarbamoyloxy)-phenyl)-carbamate
methyl-N-(3-(N'-methyl-N'-phenylcarbamoyloxy)-phenyl)-carbamate
isopropyl-N-(3-(N'-ethyl-N'-phenylcarbamoyloxy)-phenyl)-carbamate
methyl-N-(3-(N'-3-methylphenylcarbamoyloxy)-phenyl)-carbamate
methyl-N-(3-(N'-4-fluorophenylcarbamoyloxy)-phenyl)-carbamate
methyl-N-(3-(N'-3-chloro-4-fluorophenylcarbamoyloxy)-phenyl)-carbamate
ethyl-N-[3-N'-(3-chloro-4-fluorophenylcarbamoxyloxy)-phenyl]-carbamate
ethyl-N-[3-N'-(3,4-difluorophenylcarbamoyloxy)-phenyl]-carbamate
methyl-N-[3-(N'-3,4-difluorophenylcarbamoyloxy)-phenyl]-carbamate
methyl N-3-(4'-fluorophenoxycarbonylamino)-phenylcarbamate
ethyl N-3-(2'-methylphenoxycarbonylamino)-phenylcarbamate
methyl N-3-(4'-fluorophenoxycarbonylamino)-phenylthiolcarbamate
methyl N-3-(2',4',5'-trimethylphenoxycarbonylamino)-phenylthiolcarbamate
methyl N-3-(phenoxycarbonylamino)-phenylthiolcarbamate
p-chlorobenzyl N,N-diethylthiolcarbamate
ethyl N,N-di-n-propylthiolcarbamate
n-propyl N,N-di-n-propylthiolcarbamate
2,3-dichloroallyl N,N-diisopropylthiolcarbamate
2,3,3-trichloroallyl N,N-diisopropylthiolcarbamate
3-methyl-5-isoxazolylmethyl N,N-diisopropylthiolcarbamate
3-ethyl-5-isoxazolylmethyl N,N-diisopropylthiolcarbamate
ethyl N,N-di-sec.-butylthiolcarbamate
benzyl N,N-di-sec.-butylthiolcarbamate
ethyl N-ethyl-N-cyclohexylthiolcarbamate
ethyl N-ethyl-N-bicyclo-[2.1.1]-heptylthiolcarbamate
S-(2,3-dichloroallyl)-(2,2,4-trimethylazetidine)-1-carbothiolate
S-(2,3,3-trichloroallyl)-(2,2,4-trimethylazetidine)-1-carbothiolate
S-ethylhexahydro-1-H-azepine-1-carbothiolate
S-benzyl-(3-methylhexahydro-1-H-azepine-1)-carbothiolate
S-benzyl-(2,3-dimethylhexahydro-1-H-azepine-1)-carbothiolate
n-propyl N-ethyl-N-n-butylthiolcarbamate
2-chloroallyl N,N-dimethyldithiocarbamate
N-methyldithiocarbamic acid, sodium salt
triichloroacetic acid, sodium salt
.alpha.,.alpha.-dichloropropionic acid, sodium salt
.alpha.,.alpha.-dichlorobutyric acid, sodium salt
.alpha.,.alpha.-.beta.,.beta.-tetrafluoropropionic acid, sodium salt .alpha.-methyl-.alpha.,.beta.-dichloropropionic acid, sodium salt
methyl .alpha.-chloro-.beta.-(4-chlorophenyl)-propionate
methyl .alpha.,.beta.-dichloro-.beta.-phenylpropionate
benzamido oxyacetic acid
2,3,5-triiodobenzoic acid (salts, esters, amides)
2,3,6-trichlorobenzoic acid (salts, esters, amides)
2,3,5,6-tetrachlorobenzoic acid (salts, esters, amides)
2-methoxy-3,6-dichlorobenzoic acid (salts, esters, amides)
2-methoxy-3,5,6-trichlorobenzoic acid (salts, esters, amides)
3-amino-2,5,6-trichlorobenzoic acid (salts, esters, amides)
O,S-dimethyltetrachlorothioterephthalate
dimethyl-2,3,5,6-tetrachloroterephthalate
disodium 3,6-endoxohexahydrophthalate
4-amino-3,5,6-trichloropicolinic acid (salts)
ethyl 2-cyano-3-(N-methyl-N-phenyl)-aminoacrylate
isobutyl 2-[4-(4'-chlorophenoxy)-phenoxy]-propionate
methyl 2-[4-(2',4'-dichlorophenoxy)-phenoxy]-propionate
methyl 2-[4-(4'-trifluoromethylphenoxy)-phenoxy]-propionate
2-[4-(2'-chloro-4'-trifluorophenoxy)-phenoxy]-propionic acid, sodium salt
2-[4-(3',5'-dichloropyridyl-2-oxy)-phenoxy]-propionic acid, sodium salt
ethyl 2-(N-benzoyl-3,4-dichlorophenylamino)-propionate
methyl 2-(N-benzoyl-3-chloro-4-fluorophenylamino)-propionate
isopropyl 2-(N-benzoyl-3-chloro-4-fluorophenylamino)-propionate
2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine
2-chloro-4-ethylamino-6-(amino-2'-propionitrile)-1,3,5-triazine
2-chloro-4-ethylamino-6-(2-methoxypropyl)-2-amino-1,3,5-triazine
2-chloro-4-ethylamino-6-butyn-1-yl-2-amino-1,3,5-triazine
2-chloro-4,6-bisethylamino-1,3,5-triazine
2-chloro-4,6-bisisopropylamino-1,3,5-triazine
2-chloro-4-isopropylamino-6-cyclopropylamino-1,3,5-triazine
2-azido-4-methylamino-6-isopropylamino-1,3,5-triazine
2-methylthio-4-ethylamino-6-isopropylamino-1,3,5-triazine
2-methylthio-4-ethylamino-6-tert.butylamino-1,3,5-triazine
2-methylthio-4,6-bisethylamino-1,3,5-triazine
2-methylthio-4,6-bisisopropylamino-1,3,5-triazine
2-methoxy-4-ethylamino-6-isopropylamino-1,3,5-triazine
2-methoxy-4,6-bisethylamino-1,3,5-triazine
2-methoxy-4,6-bisisopropylamino-1,3,5-triazine
4-amino-6-tert.butyl-3-methylthio-4,5-dihydro-1,2,4-triazin-5-one
4-amino-6-phenyl-3-methyl-4,5-dihydro-1,2,4-triazin-5-one
4-isobutylidenamino-6-tert.butyl-3-methylthio-4,5-dihydro-1,2,4-triazin-5-one
1-methyl-3-cyclohexyl-6-dimethylamino-1,3,5-triazin-2,4-dione
3-tert.butyl-5-chloro-6-methyluracil
3-tert.butyl-5-bromo-6-methyluracil
3-isopropyl-5-bromo-6-methyluracil
3-sec.butyl-5-bromo-6-methyluracil
3-(2-tetrahydropyranyl)-5-chloro-6-methyluracil
3-(2-tetrahydropyranyl)-5,6-trimethyleneuracil
3-cyclohexyl-5,6-trimethyleneuracil
2-methyl-4-(3'-trifluoromethylphenyl)-tetrahydro-1,2,4-oxadiazine-3,5-dione
2-methyl-4-(4'-fluorophenyl)-tetrahydro-1,2,4-oxadiazine-3,5-dione
3-amino-1,2,4-triazole
1-allyloxy-1-(4-bromophenyl)-2-[1',2',4'-triazolyl-(1')]-ethane (salts)
1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,3-triazol-1-yl)-butan-2-one
N,N-diallylchloroacetamide
N-isopropyl-2-chloroacetanilide
N-(but-1-yn-3-yl)-2-chloroacetanilide
2-methyl-6-ethyl-N-propargyl-2-chloroacetanilide
2-methyl-6-ethyl-N-ethoxymethyl-2-chloroacetanilide
2-methyl-6-ethyl-N-(2-methoxy-1-methylethyl)-2-chloroacetanilide
2-methyl-6-ethyl-N-(isopropoxycarbonylethyl)-2-chloroacetanilide
2-methyl-6-ethyl-N-(4-methoxypyrazol-1-yl-methyl)-2-chloroacetanilide
2-methyl-6-ethyl-N-(pyrazol-1-yl-methyl)-2-chloroacetanilide
2,6-dimethyl-N-(pyrazon-1-yl-methyl)-2-chloroacetanilide
2,6-dimethyl-N-(4-methylpyrazol-1-yl-methyl)-2-chloro-acetanilide
2,6-dimethyl-N-(1,2,4-triazol-1-yl-methyl)-2-chloroacetanilide
2,6-dimethyl-N-(3,5-dimethylpyrazol-1-yl-methyl)-2-chloroacetanilide
2,6-dimethyl-N-(1,3-dioxolan-2-yl-methyl)-2-chloroacetanilide
2,6-dimethyl-N-(2-methoxyethyl)-2-chloroacetanilide
2,6-dimethyl-N-isobutoxymethyl-2-chloroacetanilide
2,6-diethyl-N-methoxymethyl-2-chloroacetanilide
2,6-diethyl-N-n-butoxymethyl-2-chloroacetanilide
2,6-diethyl-N-ethoxycarbonylmethyl-2-chloroacetanilide
2,3,6-trimethyl-N-(pyrazol-1-yl-methyl)-2-chloroacetanilide
2,3-dimethyl-N-isopropyl-2-chloroacetanilide
2,6-diethyl-N-(2-n-propoxyethyl)-2-chloroacetanilide
2-(2-methyl-4-chlorophenoxy-N-methoxyacetamide
2-(.alpha.-naphthoxy)-N,N-diethylpropionamide
2,2-diphenyl-N,N-dimethylacetamide
.alpha.-(3,4,5-tribromopyrazol-1-yl)-N,N-dimethylpropionamide
N-(1,1-dimethylpropynyl)-3,5-dichlorobenzamide
N-1-naphthylphthalamic acid
propionic acid 3,4-dichloroanilide
cyclopropanecarboxylic acid 3,4-dichloroanilide
methacrylic acid 3,4-dichloroanilide
2-methylpentanecarboxylic acid 3,4-dichloroanilide
5-acetamido-2,4-dimethyltrifluoromethanesulfone anilide
5-acetamido-4-methyltrifluoromethanesulfone anilide
2-propionylamino-4-methyl-5-chlorothiazole
0-(methylsulfonyl)-glycolic acid N-ethoxymethyl-2,6-dimethylanilide
0-(methylaminosulfonyl)-glycolic acid N-isopropylanilide
0-(isopropylaminosulfonyl)-glycolic acid N-but-1-yn-3-yl-anilide
0-(methylaminosulfonyl)-glycolic acid hexamethyleneamide
2,6-dichlorothiobenzamide
2,6-dichlorobenzonitrile
3,5-dibromo-4-hydroxybenzonitrile (salts)
3,5-diiodo-4-hydroxybenzonitrile (salts)
3,5-dibromo-4-hydroxy-0-2,4-dinitrophenylbenzaldoxime (salts)
3,5-dibromo-4-hydroxy-0-2-cyano-4-nitrophenylbenzaldoxime (salts)
pentachlorophenol, sodium salt
2,4-dichlorophenyl-4'-nitrophenyl ether
2,4,6-trichlorophenyl-4'-nitrophenyl ether
2-fluoro-4,6-dichlorophenyl-4'-nitrophenyl ether
2-chloro-4-trifluoromethylphenyl-4'-nitrophenyl ether
2,4'-dinitro-4-trifluoromethyl-diphenyl ether
2,4-dichlorophenyl-3'-methoxy-4'-nitro-phenyl ether
2-chloro-4-trifluoromethylphenyl-3'-ethoxy-4'-nitro-phenyl ether
2-chloro-4-trifluoromethylphenyl-3'-carboxy-4'-nitro-phenyl ether (salts)
2,4-dichlorophenyl-3'-methoxycarbonyl-4'-nitro-phenyl ether
2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxadiazolidine-3,5-dione
2-(3-tert.butylcarbamoyloxyphenyl)-4-methyl-1,2,4-oxadiazolidine-3,5-dione
2-(3-isopropylcarbamoyloxyphenyl)-4-methyl-1,2,4-oxadiazolidine-3,5-dione
2-phenyl-3,1-benzoxazinone-(4)
(4-bromophenyl)-3,4,5,9,10-pentaazatetracyclo-[5,4,1,0.sup.2,6,0,.sup.8,11 ]-dodeca-3,9-diene
2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranylmethane sulfonate
2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyldimethylaminosulfate
2-ethoxy-2,3-dihydro-3,3-didmethyl-5-benzofuranyl-(N-methyl-N-acetyl)-aminosulfonate
3,4-dichloro-1,2-benzisothiazole
N-4-chlorophenyl-allylsuccinimide
2-methyl-4,6-dinitrophenol (salts, esters)
2-sec.butyl-4,6-dinitrophenol (salts, esters)
2-sec.butyl-4,6-dinitrophenol acetate
2-tert.butyl-4,6-dinitrophenol acetate
2-tert.butyl-4,6-dinitrophenol (salts)
2-tert.butyl-5-methyl-4,6-dinitrophenol (salts)
2-tert.butyl-5-methyl-4,6-dinitrophenol acetate
2-sec.amyl-4,6-dinitrophenol (salts, esters)
1-(.alpha.,.alpha.-dimethylbenzyl)-3-(4-methylphenyl)-urea
1-phenyl-3-(2-methylycyclohexyl)-urea
1-phenyl-1-benzoyl-3,3-dimethylurea
1-(4-chlorophenyl)-1-benzoyl-3,3,-dimethylurea
1-(4-chlorophenyl)-3,3-dimethylurea
1-(4-chlorophenyl)-3-methyl-3-but-1-yn-3-yl-urea
1-(3,4-dichlorophenyl)-3,3-dimethylurea
1-(3,4-dichlorophenyl)-1-benzoyl-3,3-dimethylurea
1-(3,4-dichlorophenyl)-3-methyl-3-n.butylurea
1-(4-isopropylphenyl)-3,3-dimethylurea
1-(3-trifluoromethylphenyl)-3,3-dimethylurea
1-(.alpha.,.alpha.,.beta.,.beta.-tetrafluoroethoxyphenyl)-3,3-dimethylurea
1-(3-tert.butylcarbamoyloxyphenyl)-3,3-dimethylurea
1-(3-chloro-4-methylphenyl)-3,3-dimethylurea
1-(3-chloro-4-methoxyphenyl)-3,3-dimethylurea
1-(3,5-dichloro-4-methoxyphenyl)-3,3-dimethylurea
1-[4-(4'-chlorophenoxy)-phenyl]-3,3-dimethylurea
1-[4-(4'-methoxyphenoxy)-phenyl]-3,3-dimethylurea
1-cyclooctyl-3,3-dimethylurea
1-(hexahydro-4,7-methanoindan-5-yl)-3,3-dimethylurea
1-[1- or 2-(3a,4,5,7,7a-hexahydro)-4,7-methanoindanyl]-3,3-dimethylurea
1-(4-fluorophenyl)-3-carboxymethoxy-3-methylurea
1-phenyl-3-methyl-3-methoxyurea
1-(4-chlorophenyl)-3-methyl-3-methoxyurea
1-(4-bromophenyl)-3-methyl-3-methoxyurea
1-(3,4-dichlorophenyl)-3-methyl-3-methoxyurea
1-(3-chloro-4-bromophenyl)-3-methyl-3-methoxyurea
1-(3-chloro-4-isopropylphenyl)-3-methyl-3-methoxyurea
1-(3-chloro-4-methoxyphenyl)-3-methyl-3-methoxyurea
1-(3-tert.butylphenyl)-3-methyl-3-methoxyurea
1-(2-benzthiazolyl)-1,3-dimethylurea
1-(2-benzthiazolyl)-3-methylurea
1-(5-trifluoromethyl-1,3,4-thiadiazolyl)-1,3-dimethylurea
imidazolidin-2-one-1-carboxylic acid isobutylamide
1,2-dimethyl-3,5-diphenylpyrazolium-methylsulfate
1,2,4-trimethyl-3,5-diphenylpyrazolium-methylsulfate
1,2-dimethyl-4-bromo-3,5-diphenylpyrazolium-methylsulfate
1,3-dimethyl-4-(3,4-dichlorobenzoyl)-5-(4-methylphenylsulfonyloxy)-pyrazole
2,3,5-trichloropyridinol-(4)
1-methyl-3-phenyl-5-(3'-trifluoromethylphenyl)-pyridone-(4)
1-methyl-4-phenylpyridinium chloride
1,1-dimethylpyridinium chloride
3-phenyl-4-hydroxy-6-chloropyridazine
1,1'-dimethyl-4,4'-dipyridylium-di(methylsulfate)
1,1'-di-(3,5-dimethylmorpholine-carbonylmethyl)-4,4'-dipyridylium dichloride
1,1'-ethylene-2,2'-dipyridylium dibromide
3-[1-(N-ethoxyamino)-propylidene]-6-ethyl-3,4-dihydro-2H-pyran-2,4-dione
3-[1-(N-allyloxyamino)-propylidene]-6-ethyl-3,4-dihydro-2H-pyran-2,4-dione
2-[1-(N-allyloxyamino)-propylidene]-5,5-dimethylcyclohexane-1,3-dione (salts)
2-[1-(N-allyloxyamino-butylidene]-5,5-dimethylcyclohexane-1,3-dione (salts)
2-[1-(N-allyloxyamino-butylidene]-5,5-dimethyl-4-methoxycarbonyl-cyclohexane-1,3-dione (salts)
2-chlorophenoxyacetic acid (salts, esters, amides)
4-chlorophenoxyacetic acid (salts, esters, amides)
2,4-dichlorophenoxyacetic acid (salts, esters, amides)
2,4,5-trichlorophenoxyacetic acid (salts, esters, amides)
2-methyl-4-chlorophenoxyacetic acid (salts, esters, amides)
3,5,6-trichloro-2-pyridinyl-oxyacetic acid (salts, esters, amides)
methyl .alpha.-naphthoxyacetate
2-(2-methylphenoxy)-propionic acid (salts, esters, amides)
2-(4-chlorophenoxy)-propionic acid (salts, esters, amides)
2-(2,4-dichlorophenoxy)-propionic acid (salts, esters, amides)
2-(2,4,5-trichlorophenoxy)-propionic acid (salts, esters, amides)
2-(2-methyl-4-chlorophenoxy)-propionic acid (salts, esters, amides)
4-(2,4-dichlorophenoxy)-butyric acid (salts, esters, amides)
4-(2-methyl-4-chlorophenoxy)-butyric acid (salts, esters, amides)
cyclohexyl-3-(2,4-dichlorophenoxy)-acrylate
9-hydroxyfluorenecarboxylic acid-(9) (salts, esters)
2,3,6-trichlorophenylacetic acid (salts, esters)
4-chloro-2-oxobenzothiazolin-3-yl-acetic acid (salts, esters)
gibelleric acid (salts)
disodium methylarsonate
monosodium salt of methylarsonic acid
N-phosphonomethyl-glycine (salts)
N,N-bis-(phosphonomethyl)-glycine (salts)
2-chloroethyl 2-chloroethanephosphonate
ammonium-ethyl-carbamoyl-phosphonate
di-n-butyl-1-n-butylamino-cyclohexyl-phosphonate
trithiobutylphosphite
0,0-diisopropyl-5-(2-benzosulfonylaminoethyl)-phosphorodithionate
2,3-dihydro-5,6-dimethyl-1,4-dithiin-1,1,4,4-tetraoxide
5-tert.butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxadiazolone-(2)
4,5-dichloro-2-trifluoromethylbenzimidazole (salts)
1,2,3,6-tetrahydropyridazine-3,6-dione (salts)
succinic acid mono-N-dimethylhydrazide (salts)
(2-chloroethyl)-trimethylammonium chloride
(2-methyl-4-phenylsulfonyl)-trifluoromethanesulfone anilide
1,1-dimethyl-4,6-diisopropyl-5-indanyl ethyl ketone
sodium chlorate
ammonium thiocyanate
calcium cyanamide
2-chloro-4-trifluoromethyl-3-ethoxycarbonyl-4'-nitrophenyl ether
1-(4-benzoyloxyphenyl)-3-methyl-3-methoxyurea
2-[1-(2,5-dimethylphenyl)-ethylsulfonyl]-pyridine-N-oxide
1-acetyl-3-anilino-4-methoxycarbonyl-5-methylpyrazole
3-anilino-4-methoxycarbonyl-5-methylpyrazole
3-tert.butylamino-4-methoxycarbonyl-5-methylpyrazole
N-benzyl-N-isopropyl-trimethylacetamide
methyl 2-[4-(4'-chlorophenoxymethyl)-phenoxy]-propionate
ethyl 2-[4-(5'-bromopyridyl-2-oxy)-phenoxy]-propionate
ethyl 2-[4-(5'-iodopyridyl-2-oxy)-phenoxy]-propionate
n-butyl 2-[4-(5'-iodopyridyl-2-oxy)-phenoxy]-propionate
2-chloro-4-trifluoromethylphenyl-3'-(2-fluoroethoxy)-4'-nitrophenyl ether
2-chloro-4-trifluoromethylphenyl-3(ethoxycarbonyl)-methylthio-4-nitrophenyl ether
2,4,6-trichlorophenyl-3'-(ethoxycarbonyl)-methylthio-4-nitrophenyl ether
2-[1-(N-ethoxyamino)-butylidene]-5-(2-ethylthiopropyl)-3-hydroxy-cyclohex-2-en-1-one (salts)
2-[1-(N-ethoxyamino)-butylidene]-5-(2-phenylthiopropyl)-3-hydroxy-cyclohex-2-en-1-one (salts)
4-[4-(4'-trifluoromethyl)-phenoxy]-pentene-2-carboxylic acid ethyl ester
2-chloro-4-trifluoromethyl-3'-methoxycarbonyl-4'-nitrophenyl ether
2,4-dichlorphenyl-3'-carboxy-4'-nitrophenyl ether (salts)
4,5-dimethoxy-2-(3-.alpha.,.alpha.,.beta.-trifluoro-.beta.-bromoethoxyphenyl)-3-(2H)-pyridazinone
2,4-dichlorophenyl-3'-ethoxy-ethoxy-ethoxy-4'-nitrophenyl ether
2,3-dihydro-3,3-dimethyl-5-benzofuranyl-ethane sulfonate
N-[4-methoxy-6-methyl-1,3,5-triazin-2-yl-aminocarbonyl]-2-chlorobenzene sulfonamide
1(3-chloro-4-ethoxyphenyl)-3,3-dimethylurea
ethyl 2-methyl-4-chlorophenoxythioacetate.

Number	Name	Date
2449520	Walter	Sep 1943
2454261	Walter	Nov 1948
4013477	Kay	Mar 1977

Number	Date	Country
1946262	Sep 1969	DEX
2026625	May 1970	DEX
2508832	Sep 1975	DEX

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