Derivatives of pyrimidine
(57) Abstract:Usage: in agriculture, as compounds with fungicidal activity to combat fungal infections. The essence of the invention: fungicidal compounds - derivatives of pyrimidinethione propionate f-crystals, where any two of K, L, M is nitrogen, the third group-CH-; G is H, halogen; X is hydroxy group, H, halogen; C1-C4-alkyl, unsubstituted or substituted with halogen, hydroxyl or cyano; C2-C4alkenyl; C2-C4quinil, trimethylsilylmethyl C2-C4quinil; C2-C4alkenylamine; C2-C4alkyloxy; phenyl; cyano-, thiocyanato-, nitro-group; NRR , where R and R H, C1-C4alkyl; group C1-C4alkylcarboxylic, asiagraph, C1-C4alkoxy, phenoxy, benzyloxy, C1-C4alkoxycarbonyl; C1-C4alkoxycarbonylmethyl; C1-C4alkanoyloxy; C1-C4alkylsulfonate; C1-C4alkylthio; C1-C4alkylsulfanyl; C1-C4alkylsulfonyl; formyl, C1-C4alkanoyl, hydroximino C1-C4alkyl; carbarnoyl, thiocarbamoyl or group Y is halogen, C1-C4alkyl, C
(I) where any two of K, L and M are nitrogen and the third group is-CH= G is hydrogen or halogen, X is hydroxy group, hydrogen, halogen, unsubstituted WITH1-C4-alkyl or C1-C4is alkyl, substituted with halogen, hydroxyl or cyano; (C2-C4alkenyl,2-C4-quinil, trimethylsilylmethyl2-C4-quinil,2-C4-alkenylamine; C2-C4-alkyloxy, phenyl, cyano-, thiocyanato, the nitro group; NR1R2where R1and R2represent hydrogen or C1-C4-alkyl; group C1-C4-alkylcarboxylic, asiagraph,1-C4-alkoxy, phenoxy, benzyloxy,1-C4-alkoxy - carbonyl, C1<1-C4-alkylthio,1-C4-alkylsulfonyl,1-C4-alkylsulfonyl, formyl, C1-C4alkanoyl, hydroximino-C1-C4-alkyl, carbarnoyl, thiocarbamoyl, or group of CH3ABOUT2WITH C=CH-OCH3, Y is halogen, C1-C4- alkyl, C1-C4-alkoxy, nitro, CI-C1-C4-alkylamino or hydrogen, or X and Y when they are in anthopology relative to each other, together with the phenyl ring to which they are attached, form a naphthalene ring, And is halogen, hydrogen, C1-C4-alkyl or C1-C4-alkoxy group.The invention is illustrated by the compounds shown in the table. 1-3. In these tables methyl-3-methoxypropionate group is (E)-configuration, and the substituents E, G, U, and V are all hydrogens.Table. 2 includes 199 compounds of the General structure with all the values of X and Y, are given in table. 1, i.e., compounds 1-199 table. 2 are the same as in table. 1, except that the pyrimidine ring in the table. 1 is a 4,6-disubstituted, 2,4-disubstituted (as shown in the table. 2.Table. 3 includes 199 connection specified total structure with all the importance of that the pyrimidine ring is 4,6-disubstituted in table. 1 and 2,4-disubstituted as shown in the table. 3.In table. 4 shows the NMR data for protons of some of the compounds described in table. 1 (unless otherwise noted). Chemical shifts are measured in ppm (ppm) relative to tetramethylsilane was using deuterochloroform as solvent. Unless otherwise noted, spectra were taken on the device, operating at 270 MHz. Used the following abbreviations: S, singlet, d, t triplet, m, multiplet, d, dd = double doublet, br broad, ppm millionths.Compounds of the invention of formula (I) (equivalent to (IA)) when W is the group CH3ABOUT2WITH.WITH CH OCH3(can be obtained according to the methods shown in schemes I and II. In these schemes, the symbols X, Y, A, B, D, G, U, K, V, L, and M have the previously indicated meanings; W is CH3ABOUT2SS OF SNON3or a group that can be converted into CH3ABOUT2SS OF SNON3using well-known methods; Z1and Z2that may be the same or different, are atmasamyama groups (such as halogen or CH3SO2-), Z1is tsepliaeva group that legco are available in various compounds by the reaction of the combination; T1is hydrogen or a metal (such as sodium); and T2is hydrogen, a metal (such as sodium) or protecting group (such as benzyl). Each reaction shown in schemes I and II, are making, or in a suitable solvent or without solvent and at a suitable temperature.Compounds of the invention of formula (IA): W is a group CH3ABOUT2SS OF SNON3) can be prepared by two sequential reactions by reaction type of Ullmann when using the correspondingly functionalized derivatives of benzene and pyrimidine. The paths shown in schemes I and II illustrate that (i) the order of the stages, which can be combined these benzene and pyrimidine fragments may change; and (ii) functional groups that react with a combination of Ullmann, namely nucleophilic oxygen and tsepliaeva group in the aromatic ring, can be located on the substrate at each individual stage. For example, the compounds of formula (IA) can be prepared from compounds of formula (II) in the processing of phenols of the formula (III), where T1is hydrogen, in the presence of a base (such as potassium carbonate). Alternatively, the compounds of formula (IA)is a metal (such as sodium). The compounds of formula (II) can be obtained by treating compounds of formula (IV) phenols of the formula (V), where T1is hydrogen, in the presence of a base (such as potassium carbonate). Alternatively, the compounds of formula (II) can be obtained by treating compounds of formula (IV) phenolate salts of the formula (V), where T1is a metal (such as sodium). Similarly, the compounds of formula (II) can be prepared by the interaction of compounds of the formula (VI) with compounds of the formula (VII); when T1is hydrogen, the reaction is carried out in the presence of a base (such as potassium carbonate). Obtaining compounds of formula (IA) from intermediates (VIII), (XI) and (XII), as well as getting these intermediate products from monocyclic precursors do similar ways.Modification of the group W can be made at any suitable stage of the routes shown in schemes I and II. For example, during one or more combinations of Ullmann W can be a group of CH2CO2R (where R is H, CH3or metal), which can be turned on later stages of the synthesis group SN3ABOUT2SS= SNON3using, for example, known methods. When T2 The substituents X, Y, A, B, D, E (one of K, L or M, with the value of CE, where e has the previously indicated values), G, U and V can also be modified at any appropriate reaction stage. For example, if X is NO2it can be turned by restoring or diazotization in halogen, JV or an Oh group, and this can be done in the intermediate products, such as (XI) or (XII), or in compounds of formula (IA). Or, for example, if G is a halogen, such as chlorine, it can be removed at an appropriate stage of the synthesis (such as the last stage) to get the corresponding pyrimidine, in which G is hydrogen.Intermediates of formula (II) and (VII) can be mutually transformed into each other using standard techniques. Intermediates of formula (XI) and (XII) are also vzaimoprevrascheny. Compounds of formula (III), (IV), (VI), (IX), (X), (XIII), (XIV), (XV), (XVI) and (XVII) can be obtained by standard methods described in the chemical literature. Compounds of formulas (V) and (VII) or can be obtained by standard methods described in the chemical literature, or, when W is CH3ABOUT2SS=SNON3can be obtained according to the methods described in EP-A-0242081 and the active fungicides and may be used to suppress one or more of the following pathogens: Pyricularia oryzae on rice. Puccinia recondita, Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts e.g. coffee, pear, Apple, groundnut, vegetables and ornamental plants. Erysiphe graminis true powdery mildew on barley and wheat and other real powdery mildew on various hosts such as Sphaerotheca macularis on hops, Sphaerotheca fuliginea on cucurbits (e.g. cucumber), Podosphaera leucotricha on Apple and Uncinula necator on grapes. Helminthosporium spp. Rhynchosporium spp. Septoria spp. Pyrenophora spp. Pseudocercosporella herpotrichoides and gaeumannomyces graminis on cereals. Cercospora arachidicola and Cercosporidium personata on groundnut and other Cercospora species on other hosts, for example sugar beet, bananas, soya and rice. Botrytis cenerea (grey mildew) on tomatoes, strawberries, vegetables, vines and other hosts. Alternaria spp. on vegetables (e.g. cucumber), oil seed rape, apples, tomatoes and other hosts. Venturia inaequalis on apples. Plasmopara viticola on grapes. Other false-powdery mildew, such as Bremia lactucae on lettuce, Peronospora. spp. on soybeans, tobacco, onions and other hosts, Pseudoperonospora humuli on hops and Pseudoperonospora cubensis on the pumpkin. Phytophthora infestans on potatoes and tomatoes and other Phytophthora spp. on vegetables, strawberries, avocado, pepper, decorative, tobacco, cocoa and other hosts. Thanatephorus cucumeris on rice and Orie of the compounds show a broad spectrum of activity against fungi in vitro. They may also have activity against various diseases of fruit after harvest (for example, Penicillium digitatum and italicum and Trichoderma viride on oranges, Glaeosporium musarum on bananas and Botrytis cinerea on grapes). Some of the compounds may be active for seed treatment against pathogens, including Fusarium spp. Septoria spp. Tilletia spp. (bunt of wheat, a disease of the seeds of wheat), Ustilago spp. and Helminthosporium spp. on the cereal Rhizoctonia solani on cotton and Pyricularia oryzae on rice.Connections can have systemic movement in plants. In addition, connections can be volatile and be active in the vapour phase against fungi on the plant.Therefore, the invention provides a method of combating fungi, which consists in applying to a plant, to plant seeds or to place the locus of the plant or seed fungicide-effective amount of the above defined compounds or compositions containing it.The compounds may be used directly for agricultural purposes, but it is more convenient to formulate the composition, using a carrier or solvent. Therefore, the invention provides a fungicidal composition comprising a compound as described above, and priemlemim compositions or by themselves, directly to the foliage of plants, to seeds or to other medium in which plants are growing or planted, or they can be applied by spraying or coating in the form of formulations in the form of a cream or paste, or they can be applied in the form of vapor or granules with prolonged action. The application can be carried out on any part of the plant, including leaves, stems, branches or roots, or to soil surrounding the roots, or seeds before sowing, or in the soil, usually in irrigation water or in systems for hydroponic culture. The claimed compounds can also be injected into plants or sprayed onto vegetation using electrodynamic technique of spraying or other low volume methods. The term "plant" as used here, includes seedlings, shrubs, and trees. In addition, fungicidal method of the invention includes preventive, protective, helpful and will eradicate processing.Compounds preferably used for agricultural and horticultural purposes in the form of a composition. The type of composition in any case will depend on the specific destination. The composition can be in the form of gustovich powders or granules containing the active ingredient (with Seliger, dolomite, calcium carbonate, talc, powdered magnesia, mullerova earth, gypsum, hard-shelled earth and China clay. Such granules may be present in the form of granules, suitable for application to the soil without additional processing. These granules can be made or impregnated beads filling the active ingredient or by granulating a mixture of the active ingredient and powdered filler. The composition for seed treatment may include the agent (e.g., mineral oil) to promote adhesion of the composition on the seeds of an alternative active ingredient can be formulated for seed treatment using an organic solvent (for example, N-organic, propylene glycol or dimethylformamide). The composition can also be in the form of wettable powders or dispergiruyushchie granules in water containing a wetting or dispersing agent to facilitate the dispersion in liquids. Powders and granules may also contain fillers and suspendresume agents.Mulgirigala concentrates or emulsions can be prepared by dissolving the active ingredient in an organic solvent, does not necessarily contain Simachev and emulsifying agent. Suitable organic solvents are aromatic solvents, such as alkyl benzenes and alkylnaphthalene, ketones such as cyclohexanone and methylcyclohexanone, chlorinated hydrocarbons, such as chlorobenzene and dichloromethane, and alcohols such as benzyl alcohol, furfuryl alcohol, butanol and simple glycol ethers. Suspension concentrates most of the insoluble solids can be prepared by grinding in a ball or ball mill with a dispersing agent, suspenders agent included to prevent settling of the solid product. The composition used in the form of respecively mixtures can be in the form of aerosols, whose formula is placed in the container under pressure of a propellant, for example, tortiglioni or DICHLORODIFLUOROMETHANE. Compounds of the invention can be mixed in the dry state with a pyrotechnic mixture to form compositions suitable for the generation in confined spaces smoke containing compounds. Alternatively, the compounds may be used in microencapsulated form. They can also be formulated in biorazlagaemykh polymer formulations to get a slow, controlled separation of gational power and resistance to rain on treated surfaces, various compositions may be better suited for different applications.Compounds of the invention can be used as mixtures with fertilizers (e.g., nitrogen-, potassium - or phosphorus fertilizers). Compositions consisting only of granules of fertilizer, including, for example, coating compound, are preferred. These granules typically contain up to 25 wt. connection. Thus, the invention also provides a fertilizer composition containing fertilizer and compound of General formula (I) or its salt or complex with the metal. Wettable powders, mulgirigala concentrates and suspension concentrates usually can contain surfactants such as wetting agent, dispersing agent, emulsifier or suspendisse agent. These agents can be cationic, anionic or non-ionic agents. Suitable agents are Quaternary ammonium compounds, such as cetyltrimethylammonium bromide. Suitable anionic agents are Soaps, salts of aliphatic monoamino sulfuric acid (for example, laurylsulphate sodium) and salt from sulphonated aromatic compounds (for example, dodecylbenzenesulfonate sodium, sodium lignosulphonate, to the">Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols, as oleic or cetyl alcohol, or with alkyl phenols such as octyl or Nonylphenol and artilcles. Other non-ionic agents are the partial esters derived from long chain fatty acids and exitloop anhydride condensation products of these partial esters with ethylene oxide and lecithin. Suitable suspendresume agents are hydrophilic colloids (e.g., polyvinylpyrrolidone and sodium carboxymethylcellulose) and swelling clay, such as bentonite or attapulgite.Compositions for use in aqueous dispersions or emulsions are generally supplied in the form of concentrates containing a high concentration of the active ingredient, the concentrate is diluted with water before use. Preferably, the concentrates can be stored for a long period of time and after such storage can be diluted with water with the formation of aqueous formulations, which remain homogeneous for a time sufficient for applying them using appropriate spray equipment.Concentrates can usually dederich preparations, such preparations may contain varying quantities of the active ingredient depending on a particular purpose, but can be used in aqueous preparations containing 0,0005 or 0.01 to 10 wt. the active ingredient.Compositions of the invention may contain other compounds having biological activity, e.g. compounds having similar or complementary fungicidal activity, or which have astragalina, herbicide or insecticide activity. Fungicidal compound which may be present in compositions of the invention may be such that is able to fight diseases of the ear of cereals (e.g. wheat) such as Septoria, Gibberella and Helmintosporium spp. diseases of seeds and contamination of soil and false and powdery mildew on grapes and powdery mildew and scab on Apple trees, etc. When another fungicide composition can have a broader spectrum of activity than one of the compounds of General formula (I). Examples of fungicidal compounds which may be included in compositions of the invention are (RS)-1-linepro - pervozvanovka acid, (RS)-4-(4-chlorophenyl)-2-phenyl-2-(1H-1,2,4-triazole-1-ylmethyl)- butyronitrile, (RS)-4-chloro-N-(cyano/amoxi/methyl)benzamide, (Z)-N-but-2-Unlocker-2-chloro-2', 6'-diethylacetanilide, 1-(2 - cyano-2-methoxyimino)-3-atroce - fault, 1-[azolin-4-(3H)-he 3-chloro-4-(4-methyl-2)-1H-1,2,4-triazole-1-methyl)-1,3 - dioxolane-2-yl(phenyl)- 4-hlorfenilovy ether, 4-bromo-2-cyano-N, N-dimethyl-6-triftoratsetata-1-sulfonamide, 4-Chlorobenzyl-N-(2,4-dichlorophenyl)-2-(1H, 1,2,4 - triazole-1-yl(thioacetamide), 5-ethyl-5,8-dihydro-8-oxo/1,3-dioxolo(4,5-g)quinoline - 7-carboxylic acid, alpha-[N-(3-chloro-2,6-xylyl)-2-methoxyacetate] -gamma-Buti - Rolston, anilazine, benalaxyl, benomyl, bisoxazole, binapacryl, bitertanol, blasticidin S, bupirimate, butiaba, captafol, Captan, carbendazim, carboxin, chlorination, chloroneb, CHLOROTHALONIL, CHLOROTHALONIL, copper compounds such as copper oxychloride, copper sulphate and Bordeaux mixture, cycloheximide, having cymoxanil, tsyprokonazolu, zipform, di-2-pyridyl disulfide 1,1'-dioxide, dichlofluanid, Dylan, diclobutrazol, declomycin, dicloran, dimethomorph, dimethirimol, diniconazole, dinocap, datalists, dithianon, dodemont, Dodin, edifenphos, itaconate, ethirimol, ethyl-(Z)-N-benzyl-N-[(methyl[methyldiethylamine-oxycarbonyl] amino] thio)-be TA-etridiazole, verapamil, fenarimol, fanforum, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, pectin hydroxide, flutolanil, flutriafol, flusilazol, folpet, fosetyl-aluminum, fuberidazole, parallaxis, vorconizole-CIS, gastrosil, metalaxyl, mefenoxam, metalhawk, myclobutanil, N-(4-methyl-6-prop-1-vinylpyridin-2-yl)aniline, paasonen, dimethyldithio - carbamate, Nickel, nitratenitrogen, nuarimol, operas, organomercury compounds, oxadixyl, oxycarboxin, peyratout, penconazole, pencycuron, fenesin oxide, phtalic, polyoxin D, polishers, provenzal, prochloraz, procymidone, propamocarb, propiconazol, propineb, protocorm, pyrazophos, pirivenas, pyroxylin, proxyfor, pyrrolnitrin, chinomethionat, hintzen, streptomycin, sulfur, technicall, tecnazene, tebuconazole, tetraconazole, thiabendazol, thiophanate-methyl, thiram, tolclofos-methyl, triacetate salt, 1,1'-iminodi(octamethylene)guanidine, triadimefon, triadimenol, triazolyl, tricyclazole, tridemorph, triforine, validamycin And, vinclozolin and zineb. Compounds of General formula (I) can be mixed with soil, peat or other medium for rooting for protection of plants against fungal diseases, carried by the soil, seeds or leaves.Suitable insecticides that can be entered into the composition of the invention are buprofezin, carbaryl, carbofuran, carbosulfan, chlorpyrifos, cicloprofen, demeton-dimetil, diazinon, dimethoate, etofenprox, fenitrothion, fenomenologicheski compounds are compounds controlling weeds or seed heads (Seedhead), education or selectively control the growth of less desirable plants (e.g. grasses).Examples of suitable astragulus compounds for use with the compounds of the invention are 3,6-dichlorphenoxy acid, 1-(4-chlorophenyl)-4,6-dimethyl-2-oxo-1,2-digitope - ridin-3-carboxylic acid, methyl-3,6-dichloracetate, abscisic acid, Azul, benzoylpropionic, carbetamide, daminozide, difenzoquat, dikegulac, ethephon, fenbendazol, floridated, glyphosate, glitsin, oxybenzone (for example, bromoxynil), invented, isoperibol, long-chain fatty alcohols and acids, hydrazide maleic acid, mefluidide, morphactin (for example, chlorofluorocarbon), paclobutrazol, ferociously acid (for example, 2,4-D or MSRA), substituted benzoic acid (for example, triiodobenzoic acid), substituted Quaternary ammonium and postname connection (for example, chlormequat, hortonian or meekathara), tecnazene, the auxins (e.g. indelicacy acid, indolylmethane acid, naphthyloxy acid or naftussya acid), the cytokinins (e.g. benzimidazole, benzyladenine, benzylaminopurine, diphenylacetone or E. In the examples, the term "ether" refers to diethyl ether; drying solutions using anhydrous magnesium sulfate, and the solution concentrated under reduced pressure. Reactions involving sensitive to water or air intermediate products, is carried out in nitrogen atmosphere, and the solvent is dried before using, where necessary. Unless otherwise noted, the chromatography is performed on a column of silica gel as a stationary phase. The NMR data are selective; no attempt to list all acquisitions in all cases.1H-NMR spectra were taken in solutions CDCl3on the device, operating at 270 MHz, unless otherwise noted. We used the following abbreviations:
DMSO dimethyl sulfoxide
NMR nuclear magnetic resonance
GC gas chromatography
TLC thin layer chromatography
so pl. melting point
P R I m e R 1. Obtaining (E)-methyl 2-[2-(4-phenoxypyridine-2-yloxy)phenyl]-3-methoxypropionate (compound 1 in table. 3).To a suspension of 0.3 g (6,85 mmol, 50% dispersion in oil, pre-washed with n-hexane) in 4 ml of DMF is added until it stopped bubbling gas. The resulting mixture was diluted with 3 ml of dry DMF, and then added dropwise to a stirred solution of 1.0 g of 4-chloro-2-methylthiopyrimidine (6,23 mmol) in 3 ml of dry DMF at 0aboutC. exothermic reaction Occurs and the temperature of the reaction mixture rises to 5aboutC. After stirring under nitrogen atmosphere for 30 min with 10aboutWith GC-analysis indicates the formation of one product (98,8%). The reaction mixture was diluted with 15 ml of water and extracted with 2 x 20 ml ether. The combined ether extracts are washed with 2 x 15 ml of 5% sodium hydroxide solution and 15 ml of brine, and then dried. Evaporation of the solvent leads to obtain 1.40 g (purity according to GC 94%) of 2-methylthio-4-phenoxypyridine in the form of a light yellow oil which is used directly in the next stage.1H NMR Delta: is 2.37 (3H,S) ppm.To a stirred solution of 1.0 g (4.5 mmol) of 2-methylthio-4-phenoxypyridine in 15 ml of chloroform at -15aboutTo add 2,88 g (9,17 mmol) m-chloroperbenzoic acid in 35 ml of chloroform. Formed white turbid suspension. The reaction mixture is allowed to warm to room temperature and continue stirring for 4 h GC analysis indicates the formation of one product (95% ). The reaction mixture was washed with 2 x 2 is tdelay chloroform solution and dried. The solvent is evaporated, receive a colorless oil, which crystallizes upon cooling and the seed, get 1,05 g 2-methanesulfonyl-4-phenoxypyridine in the form of a white solid product. Recrystallization from a mixture of fluoroform: n-hexane gives white finely ground powder, so pl. 113-116aboutC,1H NMR Delta; 3,17 (3H,S) ppm; IR-spectrum (nujol): Max. 1133, 1315 cm-1.To a solution of 200 mg of 2-methanesulfonyl-4-phenoxypyridine (0.80 mmol) in 2 ml dry DMF at 0aboutC in an atmosphere of nitrogen was added 110 mg (0.80 mmol) of anhydrous potassium carbonate. A solution of 166 mg (0.80 mmol) of (E)-methyl 2-(2 oksifenil)-3-methoxy-propenoate, obtained as described in example 3 of EP-A-0242081 in 1 ml of dry DMF is then added dropwise with stirring. The reaction mixture is allowed to warm to room temperature, and then stirred over the weekend. The mixture is diluted with 15 ml of water, and then extracted with 2 x 20 ml ether. The combined ether extracts are washed with brine, dried and evaporated, receives a yellow oil. Chromatography (eluent ether:n-hexane 5:1) to give light yellow turbid oil, which is triturated with ether, to obtain 0.10 g of a solid white product of the target compound. Recrystallization from ether: n-hexane give 65 mg (yield H,d), ppm. IR range Max. 1708, 1632 cm-1.P R I m m e R 2. Obtaining (E)-methyl 2-[2-(2-phenoxypyridine-4-yloxy)phenyl]-3-methoxypropionate (compound 1 in table. 2).To a stirred solution of 10.00 g (62,3 mmol) 4-chloro-2-methylthiopyrimidine in 50 ml of glacial acetic acid at 10-15aboutWith added solution 12,50 g (79,15 mmol) of potassium permanganate in 100 ml of water. The reaction mixture was stirred overnight at room temperature, cooled to 5aboutC, and then treated with gaseous sulfur trioxide to until dark solution become colourless. Add water and the mixture extracted with chloroform. The combined organic layers washed with saturated aqueous sodium bicarbonate and then with water and dried. Upon evaporation of the receive 10,84 g of 4-chloro-2-methanesulfonamido in the form of a white solid product, so pl. 91-93aboutC. Process of 7.00 g (36,33 mmol) 4-chloro-2-methanesulfonamido tenoxicam sodium (3,41 g (36,33 mmol) of phenol and of 1.74 g (39,97 mmol) of a 50% dispersion in oil of sodium hydride in 100 ml dry DMF) at 0-5aboutC. After 30 min all starting material was consumed (GC-analysis). The reaction mixture is diluted with water, and then extracted twice with ether. The combined extracts are washed with 2 RT 5.35 g of a very light yellow mobile oil. Chromatography (eluent ether:n-hexane 2:3) followed by crystallization give 3.50 g (84% pure by GC) 4-chloro-2-phenoxypyridine in the form of a white solid product. Subsequent chromatography gives pure product (2.50 g, 33% ), so pl. 59-60aboutC. To a stirred solution of 2.00 g (9,68 mmol) 4-chloro-2-phenoxypyridine in 15 ml of dry DMSO and 10 ml of DMF at 10aboutC in an atmosphere of nitrogen was added dropwise a solution of suspension of 0.77 g (9,68 mmol) methanolate of sodium in 15 ml of dry DMSO and 5 ml of DMF. After about one hour at a temperature below 15aboutWith the reaction mixture is diluted with water, and then extracted 3 times with ether. The combined extracts washed with brine, and then dried. Evaporation of the solvent leads to a 2.00 g (87% pure by GC) 4-methylthio-2-phenoxypyridine in the form of a thick light yellow oil, which was used in the next stage without additional purification. Process of 2.00 g (of 7.96 mmol) of 4-methylthio-2-phenoxypyridine in 12 ml of glacial acetic acid with a solution of 1.60 g (10,11 mmol) of potassium permanganate in 20 ml of water as described above for 4-chloro-2-methylthiopyrimidine. After processing as described above, receive a light yellow oil, which was triturated with ether and n-hexane, obtaining a light yellow, slightly dense powder (1,00 g). the hanil-2-phenoxypyridine in the form of a white powder, so pl. 86-87aboutC,1H NMR Delta: 3,19 (3H,S) ppm; IR-spectrum (nujol) Max. 1135, 1305 cm-1.To a solution of 300 mg (1.20 mmol) of 4-methanesulfonyl-2-phenoxypyridine in 4 ml dry DMF was added 116 mg (1.20 mmol) of anhydrous potassium carbonate. A solution of 0.250 g (1.20 mmol) of (E)-methyl 2-(2 oksifenil)-3-methoxypropionate, obtained as described in example 3 of EP-A-0242081, in DMF) was added and the reaction mixture was stirred overnight at room temperature. It was poured into water and extracted with ether. The ether extracts washed with brine, dried and concentrated, obtaining of 0.48 g of a yellow oil. Chromatography (eluent ether:n-hexane, 3:1) leads to a 0.34 g of a white solid product. Recrystallization from carbon tetrachloride (dichloromethane (traces)) n-hexane leads to the target product as a white powder (0.31 g, 69% yield); so pl. 114-115aboutC,1NMR (270 MHz) Delta: of 3.60 (3H,S), 3,74 (3H,S), to 6.43 (1H,d), 7,11-7,42 (9H, m) 7,46 (1H,S), of 8.28 (2H,d) ppm. Mass spectrum m/e 378 (M+).P R I m e R 3. Obtaining (E)-methyl-2-[2-[6-(2-cianfrocca)pyrimidine-4-yloxy)- phenyl]-3-methoxypropionate (compound 9 of table. 1).To a solution 0,76 g (5,10 mmol) of 4,6-dichloropyrimidine in 4 ml of dry DMF at 0aboutTo add 0,70 g (5,10 mmol) of anhydrous potassium carbonate. Then dropwise portable described in example 3 of EP-A-0242081, in 2 ml of DMF. Upon completion of addition, the reaction mixture is allowed to warm to room temperature and continue stirring over the weekend. Then the reaction mixture was diluted with 15 ml of water and extracted with 3 x 20 ml ether. The combined ether extracts washed with brine and dried. After evaporation obtain 1.10 g of a brown liquid, which chromatographic (eluent ether:n-hexane, 3:2) to obtain (E)-methyl 2-(2-(6-chloropyrimidine-4-yloxy)phenyl)- 3-methoxypropionate in the form of a thick light yellow oil (0,58 g, 71% yield), which crystallizes in the state. Recrystallization from ether dichloromethane (traces)) n-hexane at -78aboutTo get the product in the form of 0.25 g of white powder, so pl. 94-95aboutC. In a separate preparation obtain 15 g of the product from 15,90 g of 4,6-dichloropyrimidine, (E)-methyl 2-(2 oksifenil)-3-methoxypropionate (14,80 g) and 19,64 g of anhydrous potassium carbonate. Heat during the night of 1.50 g (to 4.68 mmol) of (E)-methyl 2-(2-(6-chloropyrimidine-4-yloxy)Fe - Neil)-3-methoxypropionate at 95-100aboutWith 0,61 g (5,15 mmol) of 2-cyanophora and 0.71 g (5,15 mmol) of potassium carbonate in 35 ml of DMF in the presence of catalytic amounts odnoklasniki copper. Cool the reaction mixture was diluted with water, and then extracted with ether. United efern the light yellow oil. Recrystallization from ether (dichloromethane) n-hexane leads to the target product as a pale yellow powder (1.20 g, yield 64%), so pl. 110-111about;1NMR Delta: 3,63 (3H,S), 3,74 (3H,S), 6.42 per (1H,S) 7,19-7,47 (6H,m), 7,50 (1H,S), 7,62 to 7.75 (2H, m), 8,40 (1H,S) ppm. Subsequent preparation of the target compounds recrystallization gives a white crystalline product, so pl. 118-119aboutC.P R I m e R 4. Obtaining (E)-methyl-2-[2-(6(2-oxygenase)pyrimidine-4-yloxy)Fe - Neil]-3-methoxypropionate (compound 26 table. 1).A mixture of 6.6 g (0.06 mmol) of catechol and of 8.28 g (0.06 mmol) of anhydrous potassium carbonate in 100 ml of DMF is heated 1 h at 110aboutC. Then was added a catalytic amount (0.2 g) odnoklasniki copper, then the solution 12,82 g (0.04 mol) of (E)-methyl 2-[2-(6-chloropyrimidine-4-yloxy)phenyl]-3-me - oxypropane, obtained as described in example 3 in 50 ml of dry DMF. The reaction mixture is heated for 2 hours at 110aboutWith, leave overnight, and then poured into water. The resulting mixture was extracted with ether (extract). The remaining aqueous layer was acidified with concentrated hydrochloric acid, and then extracted with ether, then both of the extract washed with water (X3), dried and evaporated, get to 6.78 g of a brown resin ("extract"). Extract "And" washed RA is Oh and extracted with ethyl acetate, this an ethyl acetate extract is then washed with water, dried and evaporated, get of 6.68 g of a brown resin ("extract"). Extracts from "b" and "C" are combined and chromatographic (eluent ether), gain of 7.8 g (yield of 49.5%) of target compound in the form of a yellow solid product, which is identical to the sample obtained previously on a small scale, so pl. 159-161aboutWith IR range Max. 3100, 1712, 1642 cm-1;1H NMR Delta: 3,61 (3H,S in), 3.75 (3H,S), 6,30 (1H,S), of 6.52 (1H,S), 6,91-6,97 (1H,m), 7,05-7,21 (4H,m), 7,26-of 7.48 (3H,m), 7,45 (1H,S), 8,44 (1H, S) ppm.P R I m e R 5. Obtaining (E)-methyl-2-[2-(6-(2-methoxyphenoxy)pyrimidine-4-ilok - si)phenyl]-3 - methoxypropionate (compound 29 table. 1).To a stirred solution of 0.50 g (1,27 mmol) of (E)-methyl-2-[2-(6-(2-oxygenase)pyrimidine-4-yloxy)phenyl] -3-methoxy - propenoate, obtained as described in example 4 in 15 ml of dry DMF at 0aboutWith added 0.17 g (1,27 mmol) of anhydrous potassium carbonate and 0.22 g (of 1.52 mmol) under the conditions. The reaction mixture is allowed to warm to room temperature, stirred for two hours and then leave to stand on the weekend. The mixture is diluted with 20 ml of water, and then extracted with 3 x 25 ml ether. The combined ether extracts are washed with 2 x 20 ml of dilute sodium hydroxide solution and 20 ml of brine, and then dried. After vypaivanie in the form of a white foam (0.21 g, 40% yield);1H NMR Delta: of 3.60 (3H,S), 3,76 (3H,S), of 3.78 (3H,S), and 6.25 (1H,S), 6,95-7,52 (3H,m), 7,49 (1H,S), 8,42 (1H,S) ppm.In an alternate preparation of (E)-methyl 2-[2-(6-chloropyrimidine-4-yloxy)phenyl] -3-methoxypropane (1,00 g of 3.12 mmol), obtained as described in example 3, the process of 1.09 g (15,60 mmol) methanolate sodium at room temperature in 15 ml of chloroform and 10 ml of water in the presence of catalytic amounts of tetrabutylammonium. After stirring over night separate the chloroform layer and the remaining aqueous layer was then extracted with chloroform. The combined chloroform layers are washed with water, dried and evaporated, receiving, 1.56 g of orange oil. Chromatography (eluent ether-hexane, 2:1) leads to 0.92 g (yield 89%) of (E)-methyl 2-[2-(6-methylthiopyrimidine-4-yloxy)phenyl]-3-methoxypropionate in the form of a light yellow oil;1H NMR Delta: of 2.25 (3H, S) and 3.59 (3H,S), of 3.73 (3H,S) 6,55 (1H,S), 7,17 (1H,d), 7,20-of 7.55 (3H,m) was 7.45 (1H,S), to 8.57 (1H,S) ppm. Mix 0.20 g (0.6 mmol) of the product and 0.38 g (55% pure material) of meta-chloroperbenzoic acid in 25 ml of chloroform overnight at room temperature. Processing gives 0.26 g of the corresponding sulfone (purity 94% by GC) as a thick colorless oil, which was directly used in the next stage without dopolnitelnyiy in 6 ml of dry DMF was added 0,091 g of anhydrous potassium carbonate and the solution 0,082 g of 2-methoxyphenol in 2 ml dry DMF. The reaction mixture is stirred for 4 h and then overnight at room temperature, diluted with 15 ml water, then extracted with 3 x 20 ml ether. The combined ether extracts are washed with 2 x 15 ml of dilute sodium hydroxide solution and 15 ml of brine, and then dried. Upon evaporation of the receive 0.25 g thick light yellow oil. Chromatography (eluent-hexane, 7:1) leads to the target compound in the form of dense white foam (0.17 g, yield 63%).1H NMR as previously.P R I m e R 6. Obtain (E)-methyl-2-[2-(6-(2-dicarboxyphenoxy)pyrimidine- -4-yloxy)phenyl]-3-methoxy-propenoate (compound 59 table. 1).Excess gaseous hydrogen sulfide is bubbled through a stirred solution of 2.09 g (15,19 mmol) of (E)-methyl 2-[2-(6-2-cianfrocca)pyrimidine-4-yloxy] phenyl-3-methoxypropane and obtained as in example 3, and 0.52 g of triethylamine in 45 ml of dry pyridine at 50aboutC. After 4.5 h at 50aboutWith and for one week at room temperature, the excess hydrogen sulfide is removed by blowing air through the reaction mixture. The resulting brown solution is evaporated and the azeotropic dispersed with toluene (2 x 50 ml) to obtain a brown oil, which was triturated with (3 x x40 ml) water. The remainder chromatographic (eluent acetone-Gyu in the form of a light orange powder (0.68 g, yield 30%), so pl. 125-128aboutC. the Sample prepared after had so pl. 131-133aboutC,1H NMR Delta: 3,63 (3H,S), of 3.78 (3H, S), 6,27 (1H, S), 7,18 (1H,d), 7,10-of 7.60 (6H,m), 7,49 (1H,S), 7,71 (1H,S), to $ 7.91 (1H,S), with 8.05 (1H,dd), 8,39 (1H,S) ppm.P R I m e R 7. Getting
< / BR>and
< / BR>To stir the mixture 2,43 g (E)-methyl 2-(2 oksifenil)-3-methoxypropionate, obtained as described in example 3 of EP-A-0242081, and 1.61 g of anhydrous potassium carbonate in 25 ml of dry DMF at 0aboutWith added dropwise a solution of 2,4,6-trichloropyridine in 5 ml of dry DMF. The reaction mixture was stirred for 30 min at 0aboutAnd over the weekend at room temperature, and then poured into water and extracted three times with ether. The combined ether extracts washed with diluted sodium hydroxide solution and three times with water, then dried. After evaporation receive 2,62 g orange resin that chromatographic (eluent a mixture of ether-hexane), to obtain 0.65 g (E)-methyl 2-[2-(2,4 - dichloropyrimidine-6-yloxy)phenyl]-3-methoxypropane - ATA in the form of a whitish solid product, so pl. 88-90aboutWith and 10.7 g of a mixture of approximately 1:1 (GC/ gas chromatography capillary column showed that the two compounds are mixed in the ratio of 52:48).GC/MS showed M+526 for both compounds.Compel on glass): Solvent RfEt2O 0,44 Et2O:hexane (1:1) 0,08 so pl. 75-83aboutWITH
IR (oil nujol): 1707, 1637 cm-1< / BR>Study 1H NMR (CDCl3/270 MHz) gave the following peaks in parentheses are the approximate ratio
3,60 (3), 3,61 (3), 3,62* (6), 3,73 (3), 3,75 (3), 3,77* (6), 5,99* (1), 6,32 (1), 7,45* (1), 7,46 (2), 7,48 (1). It is assumed that the peaks marked with * correspond to the symmetric connection, the other connection for single-ended structure), containing
< / BR>and
< / BR>To a stirred solution of this mixture (0.97 g) in 25 ml THF was added 0.11 g of 5% Pd/C catalyst, and then within 5 minutes and added dropwise 0,405 g hypophosphite in 5 ml of water. After 2 h stirring at room temperature raise temperature to 60aboutWith and add additional portion of 0.41 g of hypophosphite of sodium in 5 ml of water after an additional 30 min) and from 0.76 g of potassium carbonate and 0.11 g of the catalyst (after hours). When starting material was consumed (GC and TLC analysis), the reaction mixture was filtered through celite, washed on the filter with ether and water. Separate the layers of the filtrate and the aqueous layer was extracted more than once with ether. The combined ether layers washed twice with water, dried and evaporated, get 0,78 g of white foam. Chromatograph The P>aboutWith IR range Max. 1705, 1693, 1636 cm-1,1H NMR Delta: 3,59 (6N,S in), 3.75 (6H, S), 6,16 (1H,S), 7,14-to 7.18 (2H,m), 7.24 to 7,41 (6H,m), 7,45 (2H,S), 8,39 (1H, S) ppm, and the connection 125 table. 2 in the form of 0.23 g of a white foam, so pl. 60-70aboutWith IR range Max. 1706, 1632 cm-1,1H NMR Delta: of 3.56 (3H,S), to 3.58 (3H,S), 3,70 (3H, S), 3,74 (3H,S), 6,34-6,37 (1H,d), 7,15-to 7.35 (8H,m), 7,44 (1H,S), 7,47 (1H,S), 8,21-8,24 (1H,S) ppm.P R I m e R 8. Obtaining (E)-methyl 2-[2-(4-ftorpirimidinu-6-yloxy)phenyl] -3-meth - oxopropionate, an intermediate product for the synthesis of compounds of the invention.A mixture of 6.50 g of 4,6-dichloropyrimidine, 20,8 g of sulfur tetrafluoride and 35 ml of Arcton 113 is heated at 50aboutWith stirring the reactor Monela capacity of 100 ml for 3,3 o'clock Raise the temperature to 100aboutC for 25 min and maintained at 100aboutC for an additional 3 hours the Temperature was raised to 151aboutC for 20 min and incubated at 151aboutC for 3 hours and Then the reactor was allowed to cool to room temperature. The reaction mixture was poured into saturated aqueous sodium bicarbonate solution and extracted with dichloromethane. On the interface see solid product removed by filtration. Then separate layer. The organic layer is washed with water, then distilled at atmospheric pressure as a light yellow oil (7.3% of output),1H NMR Delta: is 6.61 (1H,S) and 8,69 (1H, S) ppm. To a solution of 359 mg (1,724 mmol) of (E)-methyl 2-(2 oksifenil)-3-methoxypropionate, prepared as described in example 3 of EP-A-0242081, in 3 ml of dry DMF at room temperature was added in one step 476 mg (of 3.45 mmol) of anhydrous potassium carbonate. The reaction mixture is stirred for 20 minutes at room temperature, then added a solution of 200 mg of 4,6-giftability in 2 ml of dry DMF through a syringe for about 1 min. Then the reaction mixture is stirred for another 20 min at room temperature, poured into 20 ml of water and extracted with 4 x 30 ml ethyl acetate. The combined extracts are successively washed with 2 x 100 ml of water and 1 × 100 ml saturated brine, then dried and concentrated, getting 464 mg of the target compound in the form of a thick yellow oil (yield 88%), 1H NMR Delta: 3,59 (3H,S), of 3.73 (3H,S), 6,32 (1H,S), 7,16-the 7.43 (4H,m), 7,45 (1H,S), 8,51 (1H,d) ppm. The following examples are examples of compositions suitable for agricultural and horticultural purposes, which can be prepared from the compounds of the invention. Such compositions comprise another aspect of the invention.P R I m e R 9. Emulgirujushchie concentrate is prepared by mixing and stirring the ingredients until complete dissolution, wt. Connected is Olya these - nanoxide) 10 alkyl benzenes 45
P R I m e R 10. The active ingredient is dissolved in methylenechloride and the resulting liquid is sprayed on the granules of attapulgite clay. Then allow the solvent to evaporate, get a granulated composition, wt. Compound 9 of table. 5 Attapulgite granules 95
P R I m e R 11. A composition suitable for use for seed treatment, is prepared by grinding and mixing the three ingredients, wt. Compound 9 of table. 1 50 Mineral oil 2 Chinese clay 48
P R I m e R 12. Dostawy powder is prepared by grinding and mixing the active ingredient with talc, wt. Compound 9 of table. 1 5 Talc 95
P R I m e p 13. The suspension concentrate is prepared by grinding in a ball mill ingredients with the formation of the aqueous slurry of the crushed mixture in water, wt. Compound 9 of table. 1 40 sodium Lignosulphonate 10 Bentonite clay 1 Water 49
This recipe can be used for dispersion when diluted with water or applied directly to the seeds.P R I m e R 14. Formulation wettable powder is prepared by mixing together with the grinding of the ingredients up until they are thoroughly mixed, wt. Compound 9 of table. 1 25 Laurylsulphate sodium 2 Ligno fungal diseases of leaves of plants. Used the following method. The plants were grown in pot compost John Inna (N is 1 or 2) in minihorse 4 diameter see compound formulated or by mixing in a ball mill with water Dispersol T or in the form of a solution in acetone or acetone/ethanol, which is then diluted to the desired concentration immediately before use. Diseases leaf recipes (100 ppm active ingredient) is sprayed on the leaves and applied to the plant roots in the soil. Raspylyaemye solutions are applied to the maximum retention, and roots irrigate up to the maximum concentration, equivalent to about 40 ppm.th. in dry soil. Add tween-20 to obtain a final concentration of 0.05% when the spray is applied on the cereal. For most of the test compound applied to the soil (roots) and leaves (spray) for one or two days before inoculation of plants with disease. The exception is the test on Erysiphe graminis in which plants inoculant for 24 h before processing. Leaf pathogens is applied by spraying a suspension of spores on the leaves of test plants. After inoculation plants are placed in the appropriate environment, in order to develop the infection, and then the four to fourteen days, depending on disease and environmental conditions.Evaluate the suppression of the disease according to the following scale:
4 there is no disease
3 marks 5% of disease on untreated plants
2 6-25% of disease on untreated plants
1 26-59% of disease on untreated plants
0 60-100% of disease on untreated plants
The results are shown in table. 5-6.Because of the claimed compounds have a wide range of actions, performed their comparison with MANCOZEB, which is one of the fungicides with the widest spectrum of activity, is commercially available. With regard to structural analogue, are available for comparison carboxin and proxyfor. Data biological activity of MANCOZEB, carboxin and proxyfor are given in table. 7. Also included are data on the activity of these compounds, taken from the Handbook of pesticides The Pesticide Manual (8th edition). Test their activity was performed according to the method of example 15. The results when compared with table. 5-6 show mainly offer connections on a wide range of diseases. The concentration of active substance in the table. 5-6 is 100 ppm (see example 15), except as provided in (a)-(C). DERIVATIVES of PYRIMIDINE General formula
< / BR>where SUB>1WITH4-alkyl, unsubstituted or substituted with halogen, hydroxyl, langsupport,2WITH4alkenyl,2- C4-quinil, trimethylsilyl, substituted C2-C4-quinil,2-C4-alkenylamine; C2-C4-alkyloxy, phenyl, cyano-, thiocyanato, the nitro-group; NR1R2where R1and R2hydrogen or C1-C4-alkyl; group C1-C4-alkylcarboxylic, asiagraph,1-C4-alkoxy, phenoxy, benzyloxy, C1-C4-alkoxycarbonyl,1-C4-alkoxycarbonylmethyl,1-C4-alkanoyloxy,1WITH4-alkylsulfonate,1WITH4-alkylthio,1WITH4-alkylsulfonyl,1WITH4-alkylsulfonyl, formyl, C1- C4-alkanoyl, hydroximino-C1WITH4-alkyl, carbarnoyl, thiocarbamoyl, or group of CH3ABOUT2C. CH-och3;
Y is halogen, C1WITH4-alkyl, C1WITH4-alkoxy, nitro, CI-C1- C4-alkylamino or hydrogen,
or X and Y when they are in anthopology relative to each other, together with the phenyl ring to which they are attached, form a naphthalene ring; And halogen, in
(I) where ring a is selected from the group comprising residues:
b) five-membered heteroaromatic ring containing oxygen, sulfur or nitrogen as a heteroatom;
R cyano, formyl, ketonuria group, carboxyl group, which may be in the form of the free acid, ester or salt, carnemolla group or mono - or disubstituted carnemolla group or ring
Y1, Y2and Y3attached to carbon atoms and are independently hydrogen, halogen, hydroxyl, C1-8-alkyl, C2-8-alkenyl,2-8-quinil,1-8-alkoxy, C2-8-alkenylamine,2-8-alkyloxy,1-8-alkylsulfonate, each of which may be substituted by 1 to 6 halogen atoms and conjugated WITH1-8-alkoxyl,2-8-acyl, phenyl WITH1-8-alkoxyl, phenylthio, each of which can be substituted one or three halogen atoms;
Y1and Y2>W3, W4and W5independently is CH, CR3or N;
Z is a bridge consisting of elements selected from the group of methylene, substituted methylene, -C(O)-;
R1and R2each independently hydrogen, halogen, C1-8-alkyl, C1-8-alkoxy, C2-8-alkenylamine,2-8-alkyloxy, each of which may be substituted by 1 to 6 halogen atoms, 5 - or 6-membered heterocycle-C1-8-alkoxy, phenyloxy or phenyl-C1-8-alkoxy, each of which may be substituted by 1-3 substituents selected from halogen or1-8-alkyl; R2WITH1-8-alkyl, phenyl-C1-8-alkoxy or phenyl;
X and Y each independently hydrogen, hydroxyl, halogen, cyano, C1-8-alkyl, C1-8-alkoxy, C1-8-alkoxycarbonyl,2-8-acyloxy, carbamoylated,1-8-alkylthio, phenyloxy, phenyl S, each of which may be substituted by 1-3 halogen atoms, or together they predstavljaet,S,NH,NOR12илиCR13R14;
or X and R together may form a bridge having the formula-C(O)-O - or-C(O)-NR2where the carbonyl is attached to A; with the proviso that when R carboxyl in free ether or salt and X and Y together javlautsa, one of the rings a and b contains a heteroatom
where R1- alkyl-(C1-C4), O-alkyl-(C1-C4), halogen;
R2- alkyl-(C1-C4), O-alkyl-(C1-C4);
n = 3-5;
Z = COOH, COO-alkyl-(C1-C4), CONHSO2C6H5with herbicide activity, and to a method of controlling undesirable vegetation by processing them in the locus, namely, that the treatment is carried out pyrimidine derivatives of General formula I:
where R1- alkyl-(C1-C4), O-alkyl-(C1-C4), halogen;
R2- alkyl-(C1-C4), O-alkyl(C1-C4);
n = 3-5;
Z = COOH, COO-alkyl-(C1-C4), CONHSO2C6H5in the amount of 1-10 kg/ha
< / BR>where Ia 4-CL; 2-o-HOC6H6; R = 6-CH3< / BR>IB 4-CL; 2-o-HOC6H4; R = 6-CF3< / BR>IB 4-Cl; 2-o-HOC6H4; R = 6-C6H5< / BR>Iك 4-Cl; 2-o-HOC6H4; R = 5-CN
Ia 4-Cl; 2-o-HOC6H4; R = 5-COOC2H5< / BR>Ie 4-Cl; 2-o-HOC6H4; R = 5-C6H5< / BR>If 4-Cl; 2-o-HOC6H4; R = H
Z 4-Cl; 6-o-HOC6H4; R = H
AI 2-Cl; 4-o-HOC6H4; R = H
IC 2-Cl; 4-o-HOC6H4; R = 6-C6H5< / BR>IIa R = H
IIb R = 4' -OC3H7< / BR>IIb R = 5' -Br
G R = 5' -NO2< / BR>D R = 3' , 5' -Cl2< / BR>IIIa R = H is used as intermediate products in the synthesis of universal stabilizers for polyethylene, i.e
NNwhere R1hydrogen, halogen; C1-C3-alkyl, C1-C2-halogenated,1-C3-alkoxy;
R3WITH1-C4-alkyl, C1-C3-halogenated, cyclopropyl;
R4unsubstituted or substituted with halogen, methyl cyclopropyl
FIELD: organic chemistry, herbicides, agriculture.
SUBSTANCE: invention describes substituted benzoylcyclohexanediones of the general formula (I):
wherein m = 0 or 1; n = 0 or 1; A means a single bond or alkanediyl (alkylene) with 1-4 carbon atoms; R1 means hydrogen atom or unsubstituted alkyl with from 1 to 6 carbon atoms; R2 means methyl; R3 means hydrogen atom, nitro-, cyano-group, halogen atom, alkyl with from 1 to 4 carbon atoms substituted with halogen atom, alkoxy-group with from 1 to 4 carbon atoms or alkyl sulfonyl with from 1 to 4 carbon atoms; R4 means nitro-group, halogen atom, unsubstituted alkyl with from 1 to 4 carbon atoms of that substituted with halogen atom; Z means heterocycle, and herbicide agent based on thereof. Also, invention describes substituted derivatives of benzoic acid of the general formula (III):
wherein values n, A, R3, R4 and Z are given above. These compounds represent the parent substances used for preparing compound of the formula (I). Compounds of the formula (I) elicit high and selective herbicide activity.
EFFECT: valuable properties of compounds.
7 cl, 8 tbl, 7 ex
FIELD: agriculture, in particular herbicide compositions.
SUBSTANCE: invention relates to weed controlling method for tolerant cotton crops using (A) road spectrum herbicides selected from group (A1) glufosinate (salt) and related compounds; (A2) glyphosate (salt) and related compounds; and (B) herbicides selected from group containing diurone, trifluraeline, linuron, and pendimethalin; lactofen, oxyfluoren, bispiribac and salts thereof, pyrithiobac and salts thereof; setoxydim, cyclosidim, and cletodim; wherein components (A) and (B) are used in synergistically effective ratio. Also are described herbicide compositions containing compound from group (A1) or (A2) and herbicide from group (B).
EFFECT: effective controlling of weeds in cotton crops.
9 cl, 12 tbl, 3 ex
FIELD: organic chemistry, agriculture.
SUBSTANCE: method involves carrying out a seasonal single treatment of plant leaves with asymmetrical derivative of 4,6-bis-(aryloxy)pyrimidine of the formula: wherein X means chlorine atom (Cl), nitro- or cyano-group. Invention provides enhancing the long-term time of plants protection.
EFFECT: enhanced effectiveness and valuable properties of compounds.
6 cl, 6 tbl