TETRAZOLINONE DERIVATIVES

Abstract: According to the instant invention there have been found novel tetrazolinone derivatives represented by formula (I) wherein R<1> represents methyl or ethyl, R<2> represents halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, alkylsulfonyl, phenyl, phenoxy, alkoxycarbonyl, nitro or cyano, and n represents 0, 1, 2, 3, 4 or 5, processes and intermediates for their preparation and their use as herbicides.

Description: TETRAZOLINONE DERIVATIVES The present invention relates to novel tetrazolinone derivatives, to processes for their preparation and to their use as herbicides. In Japanese Laid-Open Patent Publications No. 82258/1995, No. 97372/1995 and No. 118246/1995 there are disclosed preparation processes of some tetrazolinone derivatives and a preparation process of l-substituted-5(4H)-tetrazolinones, the intermediates thereof. Moreover, the EP-A- 146,279 discloses that some tetrazolinone derivatives have herbicidal activities. However, the known tetrazolinone derivatives are not fully satisfactory with regard to their herbicidal activity and their phytotoxicity against crops. According to the invention there have now been found novel tetrazolinone derivatives of the general formula (I) wherein R 1 represents methyl or ethyl, R 2 represents halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, halo- alkylthio, alkylsulfinyl, alkylsulfonyl, phenyl, phenoxy, alkoxycarbonyl, nitro or cyano, and n represents 0, 1, 2, 3, 4 or 5. The compounds of the formula (I), according to the invention, can be obtained by a process in which a) compounds of the general formula (II) wherein R is defined as mentioned above, are reacted with compounds of the general formula (III) wherein R and n are defined as mentioned above, and M represents a leaving group such as chloro or bromo in the presence of an inert solvent and, if appropriate, in the presence of a base. The compounds of the formula (I) of the present invention posses strong herbicidal activities and especially demonstrate an excellent herbicidal effect compared with the known compounds described in the aforementioned EP-A-146,279 which are similar to the compounds of the formula (I). The compounds of the invention nevertheless also show a good compatibility with crops. Therefore, the compounds of the present invention can be potentially employed as agrochemicals, specifically as herbicides. In the formulae mentioned above: Halogen in "halogen", "haloalkyl", "haloalkoxy" and "haloalkylthio" represents fluoro, chloro, bromo or iodo, and preferably fluoro, chloro or bromo. "Alkyl" may be straight chain or branched chain and there may be mentioned, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n- or iso-pentyl, tert-amyl, pentan-3-yl, neopentyl and n-hexyl. "Alkoxy" may be straight chain or branched chain and there may be mentioned, for example, methoxy, ethoxy, propoxy, isopropoxy, n-, iso-, sec- or tert-butoxy, n- pentyloxy and n-hexyloxy. "Alkylthio" may be straight chain or branched chain and there may be mentioned, for example, methylthio, ethylthio, n-propylthio, isopropylthio and n-butylthio. "Alkylsulfinyl" may be straight chain or branched chain and there may be mentioned, for example, methylsulfinyl, ethylsulfmyl, n-propylsulfinyl, isopropylsulfinyl and n- butylsulfmyl. "Alkylsulfonyl" may be straight chain or branched chain and there may be mentioned, for example, methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropyl- sulfonyl and n-butylsulfonyl. "Haloalkyl" may be straight chain or branched chain and there may be mentioned, for example, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromo- ethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, 1,1,2,2,2-pentafluoroethyl, 2,2,3, 3,3-pentafluoropropyl, 3-chloropropyl, l,3-difluoropropan-2-yl, 1,1,1-trifluoro- propan-2-yl, 2,2,3,3,4,4,4-heptafluorobutyl and 3-bromopropyl. The Haloalkyl part of "haloalkoxy" and "haloalkylthio" may be as defined in the above-mentioned "haloalkyl". As "alkoxycarbonyl" there may be mentioned, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl and n-butoxycarbonyl. As a preferable group of compounds of the present invention there can be mentioned the compounds of the aforementioned formula (I) wherein R 1 represents methyl or ethyl, R 2 represents fluoro, chloro, bromo, Cι- alkyl, C haloalkyl, C alkoxy, C haloalkoxy, Cι- 4 alkylthio, Cj- 4 haloalkylthio, C alkylsulfinyl, Cι- 4 alkylsulfonyl, phenyl, phenoxy, Cι- 4 alkoxycarbonyl, nitro or cyano, and n represents 0, 1, 2, 3 or 4. As a more preferable group of compounds of the present invention there can be mentioned the compounds of the aforementioned formula (I) wherein R 1 represents methyl, R represents fluoro, chloro, methyl, ethyl, n-propyl, isopropyl, tert-butyl, tri- fluoromethyl, methoxy, ethoxy, isopropoxy, trifiuoromethoxy, difluoro- methoxy, 2,2,2-trifiuoroethoxy, methylthio, ethylthio, isopropylthio, methy- sulfinyl, methylsulfonyl, phenyl, phenoxy, methoxycarbonyl, ethoxycarbonyl, nitro or cyano, and n represents 0, 1, 2, or 3. Among the compounds of the aforementioned formula (I) there may be especially pointed out the compounds which are represented by the following formula wherein the carbon atom marked with * represents an asymmetric carbon atom and R 1 and R 2 have the same meaning as mentioned above. Based on this fact the compounds of the present invention can exist as pure optically active enantiomers or in a form of optional mixtures of optically active enantiomers. Therefore, the compounds of the aforementioned formula (I) of the present invention include optically active substances and mixtures thereof. Using, for example, l-((S)-α-methylbenzyl)-5(4H)-tetrazolinone and N-isopropyl-N- phenylcarbamoyl chloride as the starting materials according to preparation process a), the said preparation process can be illustrated by the following reaction scheme: The compounds of the formula (II), which are used as the starting materials in the aforementioned preparation process a) are novel compounds, which were not described in literature, and can be prepared, for example, by the following proccesses in which according to process variant b) compounds of the general formula (IV) R 1 wherein R is defined as mentioned above, are reacted with trimethylsilyl azide in the presence of a catalytic amount of boron trifluoride-ether-complex, or according to process variant c) compounds of the above-mentioned general formula (IV) are reacted with sodium azide in a polar solvent in the presence of a catalytic quantity of aluminium chloride. The compounds of the general formula (IN) which are used as the starting material in the above-mentioned preparation process variants b) and c) include isocyanates known in the area of organic chemistry and can be easily obtained, for example, by reacting amines of the general formula (V) R 1 wherein R 1 is as defined above, with, for example, phosgene according to known methods described, for example, in "SHIN JIKKEN KAGAKU KOUZA" (New experimental chemistry lecture) Vol. 14, III, pp.1490-1496 (published by Maruzen Ltd. on February 20, 1978). The compounds of the above-mentioned formula (V) can be synthesized, for example, similarly to the methods described in "SHIN JIKKEN KAGAKU KOUZA" (New experimental chemistry lecture) Vol. 14, III, pp.1332-1398 (published by Maruzen Ltd. on February 20, 1978) or Organic Reactions, Vol. 5, 1949, 301-330 (John Wiley & Sons, Inc.). As compounds of the above-mentioned formula (II) there can be mentioned the following species: l-((S)-α-methylbenzyl)-5(4H)-tetrazolinone, l-((R)-α-methylbenzyl)-5(4H)-tetrazolinone, 1 -((S)-α-ethylbenzyl)-5(4H)-tetrazolinone, l-((R)-α-ethylbenzyl)-5(4H)-tetrazolinone. The compounds of the formula (III) to be reacted with the compounds of the above- mentioned formula (II) include N-isopropyl-N-(substituted)phenylcarbamoyl halides which are well known in the area of organic chemistry. As typical examples of them there can be mentioned the following compounds: N-isopropyl-N-phenylcarbamoyl chloride, N-isopropyl-N-(4-fluorophenyl)carbamoyl chloride, N-isopropyl-N-(3-methylphenyl)carbamoyl chloride, N-isopropyl-N-(4-trifluoromethylphenyl)carbamoyl chloride, N-isopropyl-N (2-ethoxyphenyl)carbamoyl chloride, N-isopropyl-N-' (4-difluoromethoxyphenyl)carbamoyl chloride, N-isopropyl-N-' (4-isopropylthiophenyl)carbamoyl chloride, N-isopropyl-N- ( ' 4-methylsulfmylphenyl)carbamoyl chloride, N-isopropyl-N (4-methylsulfonylphenyl)carbamoyl chloride, N-isopropyl-N (4-2,2,2-trifluoroethylthiophenyl)carbamoyl chloride, N-isopropyl-N (4-phenylphenyl)carbamoyl chloride, N-isopropyl-N (3-phenoxyphenyl)carbamoyl chloride, N-isopropyl-N-' (2-ethoxycarbonylphenyl)carbamoyl chloride, N-isopropyl-N (4-nitrophenyl)carbamoyl chloride, N-isopropyl-N- (4-cyanophenyl)carbamoyl chloride and the bromides corresponding to these chlorides. The reaction of the preparation process a) is usually conducted in an inert organic solvent. As examples of such inert organic solvents there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (which may optionally be chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene; ethers, for example, diethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, dioxane, dimethoxyethane (DME), tetra- hydrofuran (THF), diethylene glycol dimethyl ether (DGM); nitriles, for example, acetonitrile, propionitrile; acid amides, for example, dimethyl formamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, 1.3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide (HMPA). The preparation process a) may be conducted in the presence of a base, preferable in the presence of the base 4-dimethylaminopyridine (DMAP). In case of using DMAP as a base, the reaction of the preparation process a) is usually conducted at about -10 to about 200°C, preferably about 25 to about 140°C under normal pressure. Optionally it is possible to conduct the reaction under elevated pressure or under reduced pressure. Moreover, it is possible to conduct the reaction of the preparation process a) using other bases than DMAP. As such bases there can be mentioned inorganic salts (for example, sodium carbonate, potassium carbonate etc.), alkyl alcoholates (for example, sodium methoxide, sodium ethoxide, potassium tert-butoxide), sodium hydroxide, potassium hydroxide, lithium hydroxide, organic bases (for example, triethylamine, 1,1,4,4-tetramethylethylenediamine, N,N-dimethylaniline, pyridine etc.). In case of conducting said reaction using these bases, the compounds of the formula (I) can be selectively obtained by using DMAP as a catalyst. The reaction temperature in this case may be in the range of usually about 0 to about 150°C, preferably about 25 to about 100°C. Said reaction is conducted desirably under normal pressure. Optionally, however, it is possible to conduct it under elevated pressure or under reduced pressure. The desired compounds of the formula (I), according to the present invention, can be obtained, for example, by reacting 1 mole of a compound of the formula (II) with about 1 mole to about 1.5 moles of a compound of the formula (III) in the presence of about 1 mole to about 1.5 moles of DMAP as a base and in such an inert solvent as mentioned above. The compounds of the formula (I) can also be prepared by reacting 1 mole of a compound of the formula (II) with about 1 mole to about 1.5 moles of a compound of the formula (III) in the presence of about 0.01 mole to about 0.3 moles of DMAP as a catalyst and, for example, about 1 mole to about 1.5 moles of potassium carbonate as a base and in an inert solvent of the kind as mentioned above. The compounds of the formula (I), according to the present invention thus obtained can be isolated and purified, for example, by means of crystallization, chromato- graphy etc. The reaction of the aforementioned preparation process b) can be conducted using a boron trifluoride-ether-complex as a catalyst. The reaction temperature is usually kept at about 0 to about 200°C, preferably about 50 to about 150°C. The reaction may be conducted desirably under normal pressure. Optionally, however, it is possible to conduct it under elevated pressure or under reduced pressure. The preparation process b) is usually conducted by reacting 1 mole of a compound of the formula (IV) with about 1 mole to about 2 moles of trimethylsilyl azide in the presence of about 0.005 moles to about 0.01 mole of boron trifluoride-ether-complex as a catalyst. The reaction of the preparation process c) is usually conducted in a polar solvent. As such polar solvent there can be mentioned, for example, acid amides such as dimethylformamide, dimethylacetamide and sufoxides such as dimethylsulfoxide, sulfolane. The reaction temperature may be generally about 0 to about 200°C, preferably about 20 to about 150°C. The reaction may be conducted desirably under normal pressure. Optionally, however, it is possible to conduct it under elevated pressure or under reduced pressure. The preparation process c) can be conducted by reacting 1 mole of a compound of the formula (IV) with about 1 mole to about 1.5 moles of sodium azide in the presence of about 0.05 moles to about 1 mole of aluminum chloride as a catalyst and in a polar solvent, for example, dimethylformamide. The compounds of the formula (I), according to the present invention, have, as shown in the test examples to be described later, excellent herbicidal activities and can be used as herbicidal agents for controlling weeds. "Weeds" in this regard mean, in the broadest sense, all plants which grow in locations where they are undesired. The compounds, according to the present invention act as total or selective herbicides depending upon the applied concentration. The active compounds of the present invention can be used, for example, as selective herbicides between the following weeds and cultures. Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Ipomoea, Polygonum, Ambrosia, Cirsium, Sonchus, Solanum, Rorippa, Lamium, Veronica, Datura, Viola, Galeopsis, Papaver,Centaurea, Galinsoga, Rotala, Lindernia etc. Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita etc. Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Agrostis, Alopecurus, Cynodon etc. Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium etc. According to the invention all plants and plant parts can be treated. The term plants includes all plants and plant populations, such as desired or undesired wild plants and cultivated plants (including naturally occurring cultivated varieties). Cultivated plants can be plant varieties that were obtained by conventional bredding and optimizing processes or by biotechnological and genetic engineering methods or a combination of such processes and methods, including transgenic plants and including plant varieties that cannot or can be protected by plant patents or plant variety rights. Plant parts are all parts and organs of plants occurring above or below the surface of the soil, e.g. shoots, leaves, needles, stalks and stems, trunks, flowers, fruits and seeds as well as roots, tubers, bulbs and rhizomes. The term plant parts also includes harvested crops and propagation material, e.g. cuttings, tubers, bulbs, rhizomes, shoots and seeds. According to the invention the plants and plants parts are treated using the usual methods by applying the active ingredients or compositions containing them directly to the plants or plant parts or to their surroundings (including the soil) or storeroom, e.g. by dipping, spraying, dusting, fogging, spreading and in the case of propagation material also by coating using one or multiple layers. The use of the compounds of the formula (I), according to the present, invention is not restricted to the above-mentioned plants, but may be applied to other plants in the same manner. The active compounds can, depending upon the applied concentration, non-selectively control weeds and may be used, for example, on industrial terrain, rail tracks, paths, places with or without planted trees. Moreover, the compounds, according to the present invention, can be used for controlling weeds in perennial cultures and applied in, 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, hopfields etc. and can be applied for the selective controlling of weeds in annual cultures. The compounds of the formula (I), according to the present invention, can be made into customary agrochemical formulations for their application. As such formulations there can be mentioned, for example, solutions, emulsions, wettable powders, suspensions, powders, soluble powders, granules, tablets, suspension- emulsion concentrates, microcapsules in polymeric substances, jumbo formulations etc. The formulations can be prepared according to known methods, for example, by mixing the compounds of the formula (I) of the present invention with extenders, namely liquid diluents and/or solid diluents or carriers, optionally with surface-active agents, namely emulsifiers and/or dispersants and/or foam-forming agents. When water is used as an extender, for example, organic solvents can be used as auxiliary solvents. As liquid diluents or carriers there can be mentioned aromatic hydrocarbons (for example, xylene, toluene, alkylnaphthalene etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chlorides, methylene chloride etc.), aliphatic hydrocarbons [for example, cyclohexane etc. or paraffins (for example, mineral oil fractions etc.)], alcohols (for example, butanol, glycols and their ethers and esters etc.), ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone etc.), strongly polar solvents (for example, dimethylformamide, dimethylsulphoxide etc.) and water. As solid diluents there can be mentioned, for example, ground natural minerals (for example, kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth etc.), ground synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates etc.) etc. As solid carriers for granules there can be mentioned, for example, crushed and fractionated rocks (for example, calcite, marble, pumice, sepiolite, dolomite etc.), synthetic granules of inorganic and organic meals, particles of organic materials (for example, sawdust, coconut shells, maize cobs and tobacco stalks etc.) etc. As emulsifiers and/or foam-forming agents there can be mentioned nonionic and anionic emulsifiers [for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (for example, alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates etc.)], albumin hydrolysis products etc. As dispersants there are included, for example, ligninsulphite waste liquor and methyl cellulose. Tackifiers may also be used in the formulations (powders, granules, emulsions). As usable tackifiers there can be mentioned, for example, carboxymethyl cellulose, natural and synthetic polymers (for example, gum arabic, polyvinyl alcohol, polyvinyl acetate etc.). Colorants may also be used. As said colorants there can be mentioned, for example, inorganic pigments (for example, iron oxide, titanium oxide, Prussian Blue etc.), organic dyestuffs such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and further trace nutrients such as salts of metals such as iron, manganese, boron, copper, cobalt, molybdenum, zinc etc. Said formulations can contain in a range of generally 0.1-95% by weight, preferably 0.5-90% by weight of the compounds of the aforementioned formula (I). The compounds of the formula (I) of the present invention can be used as such or in their formulated forms for controlling weeds. They can be used also as a mixed composition with known herbicides. Such a mixed composition can be previously prepared as a final formulation form or can be prepared by tank-mixing on the occasion of the application. The compounds of the formula (I) of the present invention can be used also with a safener and their application as a selective herbicide may be broadened by such a mixing. As an example of such safener l-(α,α-dimethylbenzyl)-3-p-tolylurea can be mentioned. As herbicides, which can be combined with the compounds of the formula (I) of the present invention there can be mentioned, for example, the following known herbicides: 4-amino-6-(l,l-dimethylethyl)-3-ethylthio-l,2,4-triazin-5(4H)-one, l-amino-6-ethyl- thio-3-(2,2-dimethylpropyl)-l,3,5-triazin-2,4(lH,3H)-dione, or N-(2-benzothiazolyl)- N,N'-dimethylurea etc. (eg. for controlling weeds in cereal cultures); 4-amino-3-methyl-6-phenyl-l,2,4-triazin-5(4H)-one etc. (e.g. for controlling weeds in sugar cane cultures); 4-amino-6-(l,l-dimethylethyl)-3-methylthio-l,2,4-triazin-5(4H)-one etc. (e.g. for controlling weeds in soybean cultures); methyl α-(4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)-o-toluate etc. (e.g. for controlling weeds in paddy rice culture). Surprisingly, some of these herbicidal combinations of these herbicides with compounds of the formula (I) of the present invention show synergistic effects. Compounds of the formula (I) of the present invention can be applied directly as such or in formulated forms such as ready-to-use solutions, emulsions, suspensions, powders, granules or used in the use forms prepared by further dilution. The compounds of the formula (I) of the present invention can be applied by means of, for example, watering, spraying, atomizing, dusting or granule application etc. The compounds of the formula (I) of the present invention can be used at any stages before and after germination of plants. They may also be mixed into the soil before sowing. The application rate of the compounds of the formula (I) of the present invention may be varied in a substantial range and is fundamentally different according to the nature of the desired effect. In case of herbicidal use, as a suitable application rate there can be mentioned, for example, a range of about 0.01 to about 5 kg, preferably about 0.1 to about 3 kg of the compounds of the formula (I) of the present invention per hectare. The preparations and applications of the compounds of the present invention are described more specifically in the following examples. However, the present invention should not be restricted to them in any way. "Parts" mean "parts by weight" unless specified. Synthesis Example 1 l-((S)-α-methylbenzyl)-5(4H)-tetrazolinon (1.00 g), N,N-dimethylaminopyridine (0.77 g) and N-isopropyl-N-phenylcarbamoyl chloride (1.25 g) were dissolved in toluene (20 ml) and stirred at 80°C for 8 hours on heating. After naturally cooling the reaction mixture was washed with water (2 times with 10 ml), dried with anhydrous sodium sulfate and then the solvent was distilled off under reduced pressure. The residue was treated by silica gel column chromatography (eluant: hexane : ethyl acetate = 3 : 1) to obtain l-((S)-α-methylbenzyl)-4-(N-isopropyl-N- phenylcarbamoyl)-5(4H)-tetrazolinone (1.72 g). mp: 79-81°C. The compounds obtained in the same manner as the above-mentioned Synthesis Example are shown in the following Table 1 together with the compound obtained in the above-mentioned Synthesis Example 1. Table 1 No. R 1 (R 2 )n *R/S Property 1 CH 3 H racemate 2 CH 3 H R mp 79-81°C 3 CH 3 H S mp 79-81°C 4 CH 3 2-F racemate 5 CH 3 2-F R n D 20 1.5421 6 CH 3 2-F S n D 20 1.5386 7 CH 3 3-F racemate 8 CH 3 3-F R mp 84-86°C 9 CH 3 3-F S mp 83-85°C 10 CH 3 4-F racemate 11 CH 3 4-F R mp 68-71°C 12 CH 3 4-F S mp 67-69°C 13 CH 3 2-C1 racemate 14 CH 3 2-C1 R mp 79-81°C 15 CH 3 2-C1 S mp 78-81°C 16 CH 3 3-C1 racemate 17 CH 3 3-C1 R mp 75-77°C 18 CH 3 3-C1 S mp 76-78°C 19 CH 3 4-C1 racemate 20 CH 3 4-C1 R mp 68-70°C Table 1 (continued) Compound No. R 1 (R 2 )n *R/S Property 21 CH 3 4-C1 S mp 68-70°C 22 CH 3 2-Br racemate 23 CH 3 2-Br R 24 CH 3 2-Br S 25 CH 3 3-Br racemate 26 CH 3 3-Br R 27 CH 3 3-Br S 28 CH 3 4-Br racemate 29 CH 3 2-1 racemate 30 CH 3 3-1 racemate 31 CH 3 4-1 racemate 32 CH 3 4-Br R 33 CH 3 4-Br S 34 CH 3 2-CH 3 racemate 35 CH 3 2-CH 3 R mp 97-100°C 36 CH 3 2-CH 3 S mp 94-95°C 37 CH 3 3-CH 3 racemate 38 CH 3 3-CH 3 R mp 48-52°C 39 CH 3 3-CH 3 S mp 55-58°C 40 CH 3 4-CH 3 racemate 41 CH 3 4-CH 3 R mp 45-50°C 42 CH 3 4-CH 3 S mp 44-47°C 43 CH 3 3-C 2 H 5 racemate 44 CH 3 4-C 2 H 5 racemate 45 CH 3 4-C 3 H 7 -n racemate Table 1 (continued) Compound No. R 1 (R 2 )n *R/S Property 46 CH 3 2-C 3 H 7 -iso racemate 47 CH 3 4-C 3 H 7 -iso racemate 48 CH 3 4-C 4 H 9 -tert racemate 49 CH 3 2-CF 3 racemate 50 CH 3 2-CF 3 R mp 79-81°C 51 CH 3 2-CF 3 S mp 78-81°C 52 CH 3 3-CF 3 racemate 53 CH 3 3-CF 3 R n D 20 1.5209 54 CH 3 3-CF 3 S n D 20 1.5194 55 CH 3 4-CF 3 racemate 56 CH 3 4-CF 3 R mp l l8-121°C 57 CH 3 4-CF 3 S mp l l6-118°C 58 CH 3 4-OCH 3 racemate 59 CH 3 4-OCH 3 R 60 CH 3 4-OCH 3 S 61 CH 3 2-OC 2 H 5 racemate 62 CH 3 3-OC 2 H 5 racemate 63 CH 3 4-OC 2 H 5 racemate 64 CH 3 4-OC 3 H 7 -iso racemate 65 CH 3 3-OCF 3 racemate 66 CH 3 4-OCF 3 racemate 67 CH 3 4-OCHF 2 racemate 68 CH 3 4-OCH 2 CF 3 racemate 69 CH 3 2-SCH 3 racemate 70 CH 3 3-SCH 3 racemate Table 1 (continued) Compound No. R 1 (R 2 )n "R/S Property 71 CH 3 4-SCH 3 racemate 72 CH 3 4-SC 2 H 5 racemate 73 CH 3 4-SC 3 H 7 -iso racemate 74 CH 3 4-S(O)CH 3 racemate 75 CH 3 4-SO 2 CH 3 racemate 76 CH 3 4-SCF 3 racemate 77 CH 3 4-SCH 2 CF 3 racemate 78 CH 3 racemate 79 CH 3 racemate 80 CH 3 racemate 81 CH 3 2-CO 2 CH 3 racemate 82 CH 3 2-CO2C2H5 racemate 83 CH 3 4-NO 2 racemate 84 CH 3 4-CN racemate 85 CH 3 2,3-F 2 racemate 86 CH 3 2,4-F 2 racemate 87 CH 3 2,4-F 2 R n D 20 1.5319 88 CH 3 2,4-F 2 S n D 20 1.5329 89 CH 3 2,5-F 2 racemate 90 CH 3 2,6-F 2 racemate Table 1 (continued) Compound No. R 1 (R 2 )n *R/S Property 91 CH 3 2,6-F 2 R mp 56-60°C 92 CH 3 2,6-F 2 S mp 53-58°C 93 CH 3 3,4-F 2 racemate 94 CH 3 3,4-F 2 R 95 CH 3 3,4-F 2 S 96 CH 3 3,5-F 2 racemate 97 CH 3 2-F.4-C1 racemate 98 CH 3 2-F,4-Br racemate 99 CH 3 2-F,5-CF 3 racemate 100 CH 3 2-F,4-OCH 3 racemate 101 CH 3 3-F,6-CF 3 racemate 102 CH 3 3-F,3-CF 3 racemate 103 CH 3 3-F,4-CH 3 racemate 104 CH 3 3-F,5-CH 3 racemate 105 CH 3 2,3-Cl 2 racemate 106 CH 3 2,4-Cl 2 racemate 107 CH 3 2,4-Cl 2 R 108 CH 3 2,4-Cl 2 S 109 CH 3 2,6-Cl 2 racemate 110 CH 3 2,5-Cl 2 racemate 111 CH 3 3,4-Cl 2 racemate 112 CH 3 3,5-Cl 2 racemate 113 CH 3 3,4-Cl 2 R 114 CH 3 3,4-Cl 2 S 115 CH 3 2-Cl,4-F racemate Table 1 (continued) Compound No. R 1 (R 2 )n *R/S Property 116 CH 3 3-C1.4-F racemate 117 CH 3 2-Cl,4-Br racemate 118 CH 3 2-Cl,4-CH 3 racemate 119 CH 3 3-Cl,4-CH 3 racemate 120 CH 3 3-CI.5-CH3 racemate 121 CH 3 3-Cl,4-OCH 3 racemate 122 CH 3 2-Br,4-F racemate 123 CH 3 2-Br,4-CH 3 racemate 124 CH 3 2-CF 3 ,4-F racemate 125 CH 3 2-CF 3 ,4-Cl racemate 126 CH 3 2-CF 3 ,4-Br racemate 127 CH 3 3-CF 3 ,4-F racemate 128 CH 3 2,3-(CH 3 ) 2 racemate 129 CH 3 2,4-(CH 3 ) 2 racemate 130 CH 3 2,4-(CH 3 ) 2 R 131 CH 3 2,4-(CH 3 ) 2 S 132 CH 3 2,5-(CH 3 ) 2 racemate 133 CH 3 2,6-(CH 3 ) 2 racemate 134 CH 3 3,4-(CH 3 ) 2 racemate 135 CH 3 3,4-(CH 3 ) 2 R 136 CH 3 3,4-(CH 3 ) 2 S 137 CH 3 2-CH 3 ,6-C 2 H< ; racemate 138 CH 3 2-CH 3 ,3-F racemate 139 CH 3 2-CH 3 ,4-F racemate 140 CH 3 2-CH 3 ,5-F racemate Table 1 (continued) Compound No. R 1 (R 2 )n *R/S Property 141 CH 3 2-CH 3 ,3-Cl racemate 142 CH 3 2-CH 3 ,4-Cl racemate 143 CH 3 2-CH 3 ,5-Cl racemate 144 CH 3 2-CH 3 ,6-Cl racemate 145 CH 3 2-CH 3 ,4-OCH 3 racemate 146 CH 3 2-CH 3 ,6-OCH 3 racemate 147 CH 3 2,6-(C 2 H 5 ) 2 racemate 148 CH 3 2,5-(CF 3 ) 2 racemate 149 CH 3 3,5-(CF 3 ) 2 racemate 150 CH 3 3-CF 3 ,5-OCH 3 racemate 151 CH 3 3,5-(CF 3 ) 2 R 152 CH 3 3,5-(CF 3 ) 2 S 153 CH 3 2,4-(OCH 3 ) 2 racemate 154 CH 3 3,4-(OCH 3 ) 2 racemate 155 CH 3 3,4-(OCH 3 ) 2 R 156 CH 3 3,4-(OCH 3 ) 2 S 157 CH 3 2-OCH 3 ,4-F racemate 158 CH 3 2-OCH 3 ,5-Cl racemate 159 CH 3 2-OCH 3 ,5-CF 3 racemate 160 CH 3 2-OCH 3 ,5-CH 3 racemate 161 CH 3 2,3,4-F 3 racemate 162 CH 3 2Λ5-F 3 racemate 163 CH 3 2,3,4-Cl 3 racemate 164 CH 3 2,4,6-(CH 3 ) 3 racemate 165 C 2 H 5 H racemate mp 55-58°C Table 1 (continued) Compound No. R 1 (R 2 ) *R/S Property 166 C 2 H 5 H R 167 C 2 H 5 H S 168 C 2 H 5 2-F racemate 169 C 2 H 5 2-F R 170 C 2 H 5 2-F S 171 C 2 H 5 3-F racemate 172 C 2 H 5 3-F R 173 C 2 H 5 3-F S 174 C 2 H 5 4-F racemate 175 C 2 H 5 4-F R 176 C 2 H 5 4-F S 177 C 2 H 5 2-C1 racemate 178 C 2 H 5 2-C1 R 179 C 2 H 5 2-C1 S 180 C 2 H 5 3-C1 racemate 181 C 2 H 5 3-C1 R 182 C 2 H 5 3-C1 S 183 C 2 H 5 4-C1 racemate 184 C 2 H 5 4-C1 R 185 C 2 H 5 4-C1 S 186 C 2 H 5 2-Br racemate 187 C 2 H 5 2-Br R 188 C 2 H 5 2-Br S 189 C 2 H 5 3-Br racemate 190 C 2 H 5 3-Br R Table 1 (continued) Compound No. R 1 (R 2 )n *R/S Property 191 C 2 H 5 3-Br S 192 C 2 H 5 4-Br racemate 193 C 2 H 5 2-1 racemate 194 C 2 H 5 3-1 racemate 195 C 2 H 5 4-1 racemate 196 C 2 H 5 4-Br R 197 C 2 H 5 4-Br S 198 C 2 H 5 2-CH 3 racemate 199 C 2 H 5 2-CH 3 R 200 C 2 H 5 2-CH 3 S 201 C 2 H 5 3-CH 3 racemate 202 C 2 H 5 3-CH 3 R 203 C 2 H 5 3-CH 3 S 204 C 2 H 5 4-CH 3 racemate 205 C 2 H 5 4-CH 3 R 206 C 2 H 5 4-CH 3 S 207 C 2 H 5 3-C 2 H 5 racemate 208 C 2 H 5 4-C 2 H 5 racemate 209 C 2 H 5 4-C 3 H 7 -n racemate 210 C 2 H 5 2-C 3 H -iso racemate 211 C 2 H 5 4-C 3 H 7 -iso racemate 212 C 2 H 5 4-C 4 H 9 -tert racemate 213 C 2 H 5 3-CF 3 racemate 214 C 2 H 5 3-CF 3 R 215 C 2 H 5 3-CF 3 S Table 1 (continued) Compound No. R 1 (R 2 )n *R/S Property 216 C 2 H 5 4-CF 3 racemate 217 C 2 H 5 4-CF 3 R 218 C 2 H 5 4-CF 3 S 219 C 2 H 5 4-OCH 3 racemate 220 C 2 H 5 4-OCH 3 R 221 C 2 H 5 4-OCH 3 S 222 C 2 H 5 2-OC 2 H 5 racemate 223 C 2 H 5 3-OC 2 H 5 racemate 224 C 2 H 5 4-OC 2 H 5 racemate 225 C 2 H 5 4-OC 3 H 7 -iso racemate 226 C 2 H 5 3-OCF 3 racemate 227 C 2 H 5 4-OCF 3 racemate 228 C 2 H 5 4-OCHF2 racemate 229 C 2 H 5 4-OCH 2 CF 3 racemate 230 C 2 H 5 2-SCH 3 racemate 231 C 2 H 5 3-SCH 3 racemate 232 C 2 H5 4-SCH 3 racemate 233 C 2 H 5 4-SC 2 H 5 racemate 234 C 2 H 5 4-SC 3 H 7 -iso racemate 235 C 2 H 5 4-S(O)CH 3 racemate Table 1 (continued) Compound No. R 1 (R 2 )n /S Property 236 C 2 H 5 4-SO 2 CH 3 racemate 237 C 2 H 5 3-SCF 3 racemate 238 C 2 H 5 4-SCH 2 CF 3 racemate 239 C 2 H 5 racemate 240 C2H5 racemate 241 C 2 H 5 racemate 242 C 2 H 5 2-CO 2 CH 3 racemate 243 C 2 H 5 2-CO2C2H5 racemate 244 C 2 H 5 4-NO2 racemate 245 C 2 H 5 4-CN racemate 246 C 2 H 5 2,3-F 2 racemate 247 C2H5 2,4-F 2 racemate 248 C 2 H 5 2,4-F 2 R 249 C 2 H 5 2,4-F 2 S 250 C 2 H 5 2,5-F 2 racemate 251 C 2 H 5 2,6-F 2 racemate 252 C 2 H 5 3,4-F 2 racemate 253 C 2 H 5 3,4-F 2 R 254 C 2 H 5 3,4-F 2 S 255 C 2 H 5 3,5-F 2 racemate Table 1 (continued) Compound No. R 1 (R 2 )n *R/S Property 256 C 2 H 5 2-F.4-C1 racemate 257 C 2 H 5 2-F,4-Br racemate 258 C 2 H 5 2-F,5-CF 3 racemate 259 C 2 H 5 2-F,4-OCH 3 racemate 260 C 2 H 5 3-F,6-CF 3 racemate 261 C 2 H 5 3-F,3-CF 3 racemate 262 C 2 H 5 3-F,4-CH 3 racemate 263 C 2 H 5 3-F,5-CH 3 racemate 264 C 2 H 5 2,3-Cl 2 racemate 265 C 2 H 5 2,4-Cl2 racemate 266 C 2 H 5 2,4-Cl 2 R 267 C 2 H 5 2,4-Cl 2 S 268 C 2 H 5 2,6-Cl 2 racemate 269 C 2 H 5 2,5-Cl 2 racemate 270 C 2 H 5 3,4-Cl 2 racemate 271 C 2 H 5 3,5-Cl 2 racemate 272 C 2 H 5 3,4-Cl 2 R 273 C 2 H 5 3,4-Cl 2 S 274 C 2 H 5 2-Cl,4-F racemate 275 C 2 H 5 3-Cl,4-F racemate 276 C 2 H 5 2-Cl,4-Br racemate 277 C 2 H 5 2-Cl,4-CH 3 racemate 278 C 2 H 5 3-Cl,4-CH 3 racemate 279 C 2 H 5 3-Cl,5-CH 3 racemate 280 C 2 H 5 3-Cl,4-CH 3 O racemate Table 1 (continued) Compound No. R' (R 2 )n *R/S Property 281 C 2 H 5 2- Br,4-F racemate 282 C 2 H 5 2-Br,4-CH 3 racemate 283 C 2 H 5 2-CF 3 ,4-F racemate 284 C 2 H 5 2-CF 3 ,4-Cl racemate 285 C 2 H 5 2-CF 3 ,4-Br racemate 286 C 2 H5 3-CF 3 ,4-F racemate 287 C 2 H 5 2,3-(CH 3 ) 2 racemate 288 C 2 H 5 2,4-(CH 3 ) 2 racemate 289 C 2 H 5 2,4-(CH 3 ) 2 R 290 C 2 H 5 2,4-(CH 3 ) 2 S 291 C 2 H 5 2,5-(CH 3 ) 2 racemate 292 C 2 H 5 2,6-(CH 3 ) 2 racemate 293 C 2 H 5 3,4-(CH 3 ) 2 racemate 294 C 2 H 5 3,4-(CH 3 ) 2 R 295 C 2 H 5 3,4-(CH 3 ) 2 S 296 C 2 H 5 2-CH 3 ,6-C 2 H 5 racemate 297 C 2 H 5 2-CH 3 ,3-F racemate 298 C 2 H 5 2-CH 3 ,4-F racemate 299 C 2 H 5 2-CH 3 ,5-F racemate 300 C 2 H 5 2-CH 3 ,3-Cl racemate 301 C 2 H 5 2-CH 3 ,4-Cl racemate 302 C 2 H 5 2-CH 3 ,5-Cl racemate 303 C 2 H 5 2-CH 3 ,6-Cl racemate 304 C 2 H 5 2-CH 3 ,4-OCH 3 racemate 305 C 2 H 5 2-CH 3 ,6-OCH 3 racemate Table 1 (continued) Compound No. R 1 (R 2 )n *R/S Property 306 C 2 H 5 2,6-(C 2 H 5 ) 2 racemate 307 C 2 H 5 2,5-(CF 3 ) 2 racemate 308 C 2 H 5 3,5-(CF 3 ) 2 racemate 309 C 2 H 5 3-CF 3 ,5-OCH 3 racemate 310 C 2 H 5 3,5-(CF 3 ) 2 R 311 C 2 H 5 3,5-(CF 3 ) 2 S 312 C 2 H 5 2,4-(OCH 3 ) 2 racemate 313 C 2 H 5 3,4-(OCH 3 ) 2 racemate 314 C 2 H 5 3,4-(OCH 3 ) 2 R 315 C 2 H 5 3,4-(OCH 3 ) 2 S 316 C 2 H 5 2-OCH 3 ,4-F racemate 317 C 2 H 5 2-OCH 3 ,5-Cl racemate 318 C 2 H 5 2-OCH 3 ,5-CF 3 racemate 319 C 2 H 5 2-OCH 3 ,5-CH 3 racemate 320 C 2 H 5 2,3,4-F 3 racemate 321 C 2 H 5 2,4,5-F 3 racemate 322 C 2 H 5 2,3,4-Cl 3 racemate 323 C 2 H 5 2,4,6-(CH 3 ) 3 racemate Svnthesis Example 2 (Intermediate) (S)-α-methylbenzyl isocyanate (8.00 g), trimethylsilyl azide (9.40 g) and a catalytic amount of boron trifluoride-ether-complex were mixed and refluxed for 16 hours on heating. The excess amount of trimethylsilyl azide was distilled off under reduced pressure and the residue was treated by silica gel column chromatography (eluant: hexane : ethyl acetate = 3 : 2) to obtain l-((S)-α-methylbenzyl)-5(4H)-tetrazolinone (8.18 g). mp: 102-106 °C. Synthesis Example 3 (Intermediate) Sodium azide (1.95 g) was suspended in anhydrous dimethylformamide (18 ml) and anhydrous aluminium chloride (0.2 g) was added in an argon stream under ice cooling and stirred for 15 minutes. Then (S)-α-methylbenzyl isocyanate (4.85 g) was added drop by drop and the reaction mixture was stirred for 3 hours in argon stream on heating at 70-75 °C. After natural cooling, the reaction mixture was added to a mixture of sodium sulfite (0.5 g), water (100 ml) and ice (50 g) on stirring, acidified with 10%) hydrochloric acid and extracted with ethyl acetate. After drying the organic layer with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure and the residue was treated by silica gel column chromatography (eluant: hexane : ethyl acetate = 3 : 2) to obtain l-((S)-α-methylbenzyl)-5(4H)- tetrazolinone (3.20 g). mp: 102-106°C. The compounds obtained according in a similar way as the above-mentioned Synthesis Examples 2 or 3 are listed in the following Table 2 together with the compounds obtained in the Synthesis Examples 2 and 3. Table 2 Compound No. R 1 "R/S Property II- 1 CH 3 racemate π-2 CH 3 R mp 97-106°C II-3 CH 3 S mp 102-106°C π-4 C 2 H 5 racemate mp 103-106°C π-5 C 2 H 5 R π-6 C 2 H 5 S Test Example 1 : Test for herbicidal effect against paddy field weeds Preparation of formulation of the active compound Carrier: Acetone 5 parts by weight Emulsifier: Benzyloxypolyglycolether 1 part by weight A formulation of the active compound is obtained as an emulsion by mixing 1 part by weight of the active compound with the above-mentioned amount of carrier and emulsifier. A prescribed amount of said formulation is diluted with water to prepare a formulation for testing. Test method In a greenhouse 3 seedlings of paddy rice (cultivar: Nipponbare) of 2.5 leafstage (15 cm tall) were transplanted in a 500 cm 2 pot filled with paddy field soil. Then seeds of barnyard grass, smallflower, bulrush, monochoria and broad-leaved weeds (common false pimpernel, Indian toothcup, long stemmed water wort, Ammannia multiflora Roxb., Dopatrium junceum Hammilt etc.) were sown and water was poured on the soil to a depth of about 2-3 cm. 5 days after the rice transplantation a formulation of each active compound prepared according to the aforementioned preparation method was applied to the surface of the water. A water depth of 3 cm was maintained. The herbicidal effect was examined after 3 weeks from the treatment. The herbicidal effect was rated as 100%) in the case of complete death and as 0% in the case of no herbicidal effect. As a result, the compounds No. 2, 3, 11, 12, 42, 88 and 165 of the present invention showed at an application rate of 0.5 kg/ha sufficient herbicidal effect against paddy field weeds and showed safety to the transplanted paddy rice. Formulation Example 1 (Granule) To a mixture of 5 parts by weight of compound No. 165, 30 parts by weight of bentonite (montmorillonite), 58 parts by weight of talc and 2 parts by weight of ligninsulphonate, 25 parts by weight of water were added. The mixture is well kneaded, made into granules of 10-40 mesh by extrusion granulation and dried at 40- 50°C to obtain granules. Formulation Example 2 (Granule) 95 parts by weight of clay mineral particles having a particle size distribution of 0.2- 2 mm are put in a rotary mixer. While rotating it, 5 parts by weight of the compound No. 2 are sprayed together with a liquid diluent into the mixer, wetted uniformly and dried at 40-50°C to obtain granules. Formulation Example 3 (Emulsifiable concentrate) 30 parts by weight of the compound No. 3, 5 parts by weight of xylene, 8 parts by weight of polyoxyethylenealkyl phenyl ether and 7 parts by weight of calcium alkylbenzenesulphonate are mixed and stirred to obtain an emulsion. Formulation Example 4 (Wettable powder) 15 parts by weight of the compound No. 42, 80 parts by weight of a mixture of white carbon (hydrous amorphous silicon oxide fine particles) and powder clay (1 : 5), 2 parts by weight of sodium alkylbenzenesulphonate and 3 parts by weight of sodium alkylnaphthalenesulphonate-formalin-polymer are mixed in powder form and made into a wettable powder. Formulation Example 5 (Water dispersible granule) 20 parts by weight of the compound No. 2, 30 parts by weight of sodium ligninsulphonate, 15 parts by weight of bentonite and 35 parts by weight of calcined diatomaceous earth powder are well mixed, added with water, then extruded using a 0.3 mm screen and dried to obtain a water dispersible granule.

Claims: Claims 1. A compound according to the general formula (I) wherein R 1 represents methyl or ethyl, R 2 represents halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, alkylsulfonyl, phenyl, phenoxy, alkoxycarbonyl, nitro or cyano, and n represents 0, 1, 2, 3, 4 or 5. 2. A compound according to Claim 1 characterized in that R 1 represents methyl or ethyl, R 2 represents fluoro, chloro, bromo, Cι- 4 alkyl, C M haloalkyl, C M alkoxy, Cι- 4 haloalkoxy, Cι- 4 alkylthio, Cι- 4 haloalkylthio, Cι- alkylsulfinyl, Cι- 4 alkylsulfonyl, phenyl, phenoxy, Cι- 4 alkoxycarbonyl, nitro or cyano, and n represents 0, 1, 2, 3 or 4. 3. A compound according to Claim 1 characterized in that R represents methyl, R 2 represents fluoro, chloro, methyl, ethyl, n-propyl, isopropyl, tert-butyl, trifluoromethyl, methoxy, ethoxy, isopropoxy, trifluoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, iso- propylthio, methylsulfinyl, methylsulfonyl, phenyl, phenoxy, methoxycarbonyl, ethoxycarbonyl, nitro or cyano, and n represents 0,1,2, or 3. 4. A process for the preparation of the compounds of the formula (I) wherein R represents methyl or ethyl, R represents halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, alkylsulfonyl, phenyl, phenoxy, alkoxycarbonyl, nitro or cyano, and n represents 0, 1, 2, 3, 4 or 5, characterized in that a) compounds of the general formula (II) wherein R 1 is as defined above, are reacted with compounds of the general formula (III) wherein R and n are as defined above, and M represents a leaving group such as chloro, bromo in the presence of an inert solvent and, if appropriate, in the presence of a base. 5. Herbicidal composition characterized in that it contains at least one compound of the general formula (I) according to Claim 1. 6. Process for combating weeds characterized in that a compound of the general formula (I) according to Claim 1 is allowed to act on weeds and/or their habitat. 7. Use of a compound of the general formula (I) according to Claim 1 for combating weeds. 8. Process for the preparation of herbicidal compositions characterized in that a compound of the general formula (I) according to Claim 1 is mixed with extenders and/or surface active agents. 9. A compound according to general formula (II) wherein R is defined as in Claim 1.

Inventors: GOTO TOSHIO, ITO SEISHI, UENO CHIEKO, WATANABE YUKIYOSHI, GOTO, TOSHIO, ITO, SEISHI, UENO, CHIEKO, WATANABE, YUKIYOSHI
Applicants: BAYER AGROCHEM KK, GOTO TOSHIO, ITO SEISHI, UENO CHIEKO, WATANABE YUKIYOSHI, GOTO, TOSHIO, ITO, SEISHI, NIHON BAYER AGROCHEM K.K., UENO, CHIEKO, WATANABE, YUKIYOSHI
Application year: 2000
Main classification: C07D257
IPC codes: A01N43, A01N47, C07D257