Derivatives of acrylic acid
(57) Abstract:Usage: the synthesis of organic compounds having pesticidal activity. The essence of the invention: derivatives of acrylic acid total f-ly C6H4(A-W)C(CO2CH3)=CHOCH3, where W is pyridyl, substituted 1 to 4 times with substituents selected from halogen, C1-C4-alkyl, possibly substituted with halogen, C1-C4-alkoxy, phenyl, phenoxy, amino, formamido, nitro, cyano, N-oxide; pyrimidinyl, substituted 1 to 2 times by halogen, C1-C4-alkyl, possibly substituted with halogen, C1-C4-alkoxy, phenyl, phenoxy, possibly substituted by nitro, cyano; chinoline or halogencontaining associated with And using one of the ring atoms of carbon And oxygen, S(O)n, n 0, 1, 2, provided that when W S-triptorelin-2-yl, And is different from oxygen. 3 Il. 9 table. The invention relates to a derivative of acrylic acid, useful in agriculture (especially as fungicides but also as plant growth regulators, insecticides and nematicides), to the processes of their production, agricultural (especially fungi) compositions containing them and to methods of their use for b is s or suppress insect and nematode pests.The invention is compounds having the formula 1
and their stereoisomers, where W is a substituted pyridinyl or substituted pyrimidinyl group associated with While using any of its ring carbon atoms; And a represents or oxygen, or S/O/n, where n is 0,1 or 2; X, Y and Z, which are identical or different, represent hydrogen atoms or halogen, or hydroxy, optionally substituted alkyl (including haloalkyl), optionally substituted alkenylphenol, optionally substituted alkylamino, optionally substituted alkoxy, (including haloalkoxy), optionally substituted, alkylthio, optionally substituted, aryloxy, optionally substituted, Allakaket, optionally substituted, acyloxy, optionally substituted amino, optionally substituted, acylamino, nitro, cyano, -CO2R3, -NR4R5, -COR6or S/O/mR7where m is 0,1 or 2 groups, or any two of the groups X, Y and Z, when they are in adjacent positions on the phenyl ring, can be connected, forming a condensed ring, or an aromatic or aliphatic optionally containing one or more heteroatom the military alkyl (including the alkyl fluoride) group, provided that when W represents a 5-triptorelin-2-yl, And does not represent oxygen, X is hydrogen and R1and R2both represent methyl, Y and Z are not both hydrogen, Y is not F, CL, stands, nitro, 5-CF3A 5-SCH3or 4/CH3/2N, if Z is a hydrogen, Y and Z together are not 3-nitro-5-chloro, 3,5-dinitro, 4,5-dimethoxy or 4.5-methylendioxy; and R3, R4, R5, R6and R7which are the same or different, represent hydrogen atoms or optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkyl, optionally substituted alkeneamine, optionally substituted alkyline, optionally substituted aryl or optionally substituted kalkilya group, and their complexes with metals.The compounds of this invention contain at least one carbon-carbon double bond, and sometimes in the form of mixtures of geometric isomers. However, these mixtures can be separated into individual isomers; and the invention includes such isomers and mixtures thereof in all ratios, including mixtures, which consist, with the which are the result of asymmetrically substituted double bond of acrylate groups, are identified by the commonly used terms "" and "". These terms are defined in accordance with the system of Cahn Ingold-Prelog, which is fully described in the literature (see, for example, J. March. Advanced Organic Chemistry 3rd edition, Wiley-Jnterscience page 109 onwards).Usually one isomer is more fungicide active than the other; and is more active isomer, in which the group-OR2is on the same side of the double bond, and the phenyl ring. In the case of compounds of the present invention is //-isomer. //-isomers form a preferred group of compounds of this invention.Formula
used here, means a partial mixture of both geometric isomers relative to the acrylate double bond, that is,
< / BR>Alkyl groups, wherever they are present in the form of group or fragment, for example, radicals "alkoxy", "alkylthio and aralkyl", can be in the form of straight or branched chains and contain preferably 1-6, more preferably 1-4, carbon atoms; examples are methyl, ethyl, propyl, n - or isopropyl/ and butyl /n-, ISO - or tert-butyl/.R1and R2which are optionally substituted alkyl GRU is performance communications group. The preferred Deputy is fluorine, which may be present in the amount of one or more atoms. Especially preferred that R1and R2both represent methyl, and or one or both methyl groups are optionally substituted one, two or three fluorine atoms.The atoms of halogen, wherever they have not been given any reference, are especially fluorine atoms, chlorine or bromine, especially fluorine atoms or chlorine.Cycloalkyl represents preferably3-C6cycloalkyl, for example, cyclohexyl, and cycloalkenyl represents preferably3-C6cycloalkyl (C1-C4)alkyl, for example, cyclopropylethyl. Alkeneamine and alkyline groups preferably contain 2-6, more preferably 2-4, carbon atoms in a straight or branched chains. Examples are ethynyl, allyl and propargyl. The aryl is preferably phenyl and aralkyl is preferably benzyl, phenylethyl or phenyl-n-propyl. Optionally substituted alkyl includes, in particular, haloalkyl, hydroxyalkyl, alkoxyalkyl, optionally substituted aralkyl, especially optionally substituted phenylalkyl, and neobyazatelnoe, especially optionally substituted - tion phenylethenyl; optionally substituted, aryloxy includes optionally substituted, phenyloxy; and optionally substituted, Allakaket includes optionally substituted benzyloxy. Optional substituents for the "alkoxy" and "alkylthio include the substituents described above for "alkyl".The substituents that may be present in any optionally substituted aryl or heteroaryl fragment include one or more of the following: halogen, hydroxy, C1-C4alkyl (especially methyl or ethyl), C1-C4alkoxy (especially methoxy), halogen (C1-C4) alkyl (especially trifluoromethyl), halogen (C1-C4) alkoxy (especially triptoreline)1-C4alkylthio (especially methylthio), (C1-C4) alkoxy (C1-C4) alkyl, C3-C6cycloalkyl,3-C6cycloalkyl (C1-C4) alkyl, aryl (especially phenyl), aryloxy( especially phenyloxy), aryl (C1-C4) alkyl (especially benzyl), phenylethyl and phenyl-n-propyl-), aryl WITH1-C4alkoxy (especially benzyloxy), aryloxy (C1-C4) alkyl (especially vinyloxymethyl), siloxy (especially the atomic charges and benzoyloxy), -SO2R1, -SO2R1, -COR1, -OCOR1, -CR1=NR11or-N=CR1R11in which R1and R11are independently hydrogen, C1-C4alkyl, C1-C4- alkoxy,C1-C4alkylthio,3-C6cycloalkyl,3-C6cycloalkyl (C1-C4) alkyl, phenyl or benzyl, and phenyl and benzyl groups optionally substituted with halogen, C1-C4the alkyl or C1-C4alkoxy. Optionally substituted amino, acylamino, acyloxy groups include-NR1R11, -NHCOR1and-R1in which R1and R11have the above values.The substituents in the substituted pyridinoline or substituted pyrimidinyl ring W, which are the same or different, include any of the values given for X, Y and Z. In particular, they include the halogen atoms, or hydroxy, optionally substituted alkyl (including haloalkyl), especially WITH1-C4alkyl, optionally substituted of alkenyl, especially WITH3-C4alkenyl, optionally substituted aryl, optionally substituted quinil, especially WITH3-C4quinil, optionally substituted alcox is Ino replaced aryloxy, optionally substituted, heterocyclic (especially heteroaromatic), optionally substituted aryl, optionally substituted heterocyclyl (particularly 5 - and 6-membered carbon-nitrogen rings).nitro, cyano, -NR1R11, -NHCOR1, -CONR1R11, -OCOR1, -CO2R1CH= NOR11CH2NR1R11, -CH2OR1, -CH2NHCOR1, -CH2CR1or S/O/mR1/where m represents 0, 1 or 2/ group, or any two of the substituents in pyridinoline or pyrimidinyl rings when they are in adjacent positions in the ring, can be connected, forming an optionally substituted condensed ring, or an aromatic or aliphatic, optionally containing one or more heteroatoms; and R1, R2, R3, R4, R5, R6and R7have the meanings given above.Pyridine and pyrimidines with hydroxyl substituents in the relevant provisions may also exist in the corresponding tautomeric oxo-forms, i.e. in the form of the corresponding pyridines and pyrimidines, respectively. Have in mind that when pyridinoline or pyrimidinyl ring W has a hydroxy Deputy, us is Chemistry c, Wiley-Jnterscience pages 236-241).Preferred substituted haloidalkyls, haloalkoxy groups are1-C4alkyl and halogen (C1-C4) alkoxy group. Haloalkyl includes especially trihalomethyl and especially trifluoromethyl (except when stated otherwise).Preferred aryl groups or fragments (e.g., in the form of fragments in aryloxy group are phenyl, and the substituents in the substituted amino group, or fragment is preferably1-C4alkyl.Preferred heterocyclic groups, or fragments (e.g., as in heterocyclyl or heterocyclic) are, for example, 2-; 3 - or 4 - optionally substituted pyridine, or 2-, 4 - or 5 - optionally substituted pyrimidines.In one of the private aspects of the invention is compounds having the formula 1
and their stereoisomers, where W is a substituted pyridinyl or substituted pyrimidinyl group associated with While using any of its carbon atoms and bearing the substituents defined above; a represents a or an oxygen atom or S/O/n, where n is 0, 1 or 2; X, Y, Z, to the 1-C4alkyl, C2-C5alkeneamine,2-C5alkyline, phenyl, C1-C4haloalkylthio,1-C4alkoxy, phenoxy, benzyloxy or mono - or dialkylamino group, or any two of the groups X, Y and Z, when they are in adjacent positions in the phenyl ring, are connected, forming a condensed aromatic ring; where the aliphatic fragments of any of the above groups are optionally substituted by one or more1-C4alkoxy groups, fluorine atoms, chlorine or bromine, phenyl rings, which are themselves optionally substituted,heterocyclic rings, which are either aromatic or not aromatic and of themselves optionally substituted, nitro, amino, cyano, hydroxyl or carboxyl groups, and where the phenyl fragments of any of the following radicals optionally substituted by one or more fluorine atoms, chlorine or bromine, phenyl rings, WITH1-C4alkyl, C1-C4alkoxy, cyano, amino, nitrile, hydroxyl or carboxyl groups; and R1and R2which are the same or different, represent a1-C4Alami halogen (especially fluorine), provided that when W represents a 5-triptorelin-2-yl, And presented results in oxygen, X is hydrogen; and R1and R2both are metelli, Y and Z both are not simultaneously hydrogens, Y is not F, Cl, stands, nitro, 5-CF3A 5-SCH3or 4-(CH3)2N, if Z is hydrogen and Y and Z together are not 3-nitro-5-chloro-, 3,5-dinitro, 4,5-dimethoxy or 4=5-methylendioxy.When one or more of the radicals X, Y and Z are other than hydrogen, it is preferable that they are the only atoms or sterically small groups, such as fluorine, chlorine, bromine, hydroxy, methyl, methoxy, trifluoromethyl, methylamino and dimethylamino. Further, it is preferable that one of these deputies took the 5-position of the phenyl ring (acrylate group attached at the 1-position), as this may provide advantages in terms of phytotoxicity, especially when there is only one Deputy, such as chlorine.In the following aspect, the invention provides compounds having the formula 1A:
and their stereoisomers, where a is an S/O/n, where n represents 0, 1 or 2, or preferably an oxygen atom; W represents then Deputy pyridinoline or pyrimidinyl rings, which are the same or different, represent one or more halogen atoms or hydroxyl, optionally substituted alkyl (including haloalkyl), optionally substituted alkeneamine, optionally substituted aryl, optionally substituted alkyline, optionally substituted alkoxy (including haloalkoxy), optionally substituted, aryloxy, optionally substituted, heterocyclic, optionally substituted aryl, optionally substituted heterocyclyl, optionally substituted, acyloxy, optionally substituted amino, optionally substituted, acylamino, nitro, cyano, -CO2R3, -CONR4R5, -COR6or S/0/mR7(where m=0, 1 or 2) groups; provided that when a represents a 5-triptorelin-2-yl; And presented results in a oxygen; X is hydrogen, and R1and R2both represent methyl, Y and Z are not both hydrogen, Y is not F, Cl, stands, nitro, 5-CF3A 5-SCH3or 4/CH2/2N, if Z is hydrogen, and Y and Z together are not 3-nitro-5-chloro-3,5-dinitro-4,5-dimethoxy or 4,5-methylene-dioxy; and R3, R4, R5, R6, R7and R7have the meanings given above.Freeformer (except, when stated otherwise), trichloromethyl and methoxy.According to another aspect of the invention is compounds having the formula (I):
in which Q represents a methyl, trifluoromethyl (but not 5-trifluoromethyl), methoxy, bromine, fluorine or especially chlorine.Q is preferably 2-, 5 - or 6-position of the pyridine ring, and more preferably in 4-position, when he represents methyl, for example.This invention is illustrated in the compounds represented in table. 1-4.Table. 4 shows selected proton NMR data of some of the compounds described in table. 1, 2 and 3 and described them as oil or resin. Chemical shifts are measured in million shares from tetramethylsilane, and as a solvent, the following compounds:
Shir. wide so a triplet
C. singlet square the Quaternary
D. doublet m multiplet
Compounds of the invention having the General formula I, can be prepared from phenylacetate General formula XII with the stages shown in figure 11 (see Fig. 1). For figure 11, the symbols R1, R2, R8, A, W, X, Y, Z and L have the meanings defined above, and M represents a protective group for a phenolic or typenoneornot IX with compounds of General formula VI in the presence of a base (such as potassium carbonate) and, if necessary, the catalyst is a transition metal or transition metal salt in a suitable solvent (such as N, N-dimethylformamide) (stage h scheme II).Compounds of General formula IX can be prepared from a protected phenolic or thiophenols derivatives of the General formula X using standard methods of removing protection, described in the chemical literature (stage i scheme II). For example, phenols of General formula (IX, is) can be obtained from the simple benzyl ethers of the General formula (X, A represents O, M represents CH2Ph) c by hydrogenolysis in the presence of a suitable catalyst (such as palladium, deposited on the carrier coal).Compounds of General formula X, in which the group M is a standard protective group of the phenol or thiophenol, such as benzyl, can be obtained by processing phenylacetate formula XII base (such as sodium hydride or sodium methylate) and ether formic acid (such as methylformate) in a suitable solvent such as N,N-dimethylformamide, and at a suitable temperature (stage To scheme II). If the reaction mixture is then added to the compound of formula R2-L, where L has a value, set the ton acid, are obtained the compounds of formula XI in which R8represents hydrogen. Alternatively, the compound of formula XI in which R8represents a metal atom (particularly the alkali metal atom such as sodium atom), can be isolated from the reaction mixture.The compounds of formula XI in which R8represents a metal atom, can be converted into compounds of formula X by treatment of the compound of formula R2-L, in a suitable solvent. The compounds of formula XI in which R8represents hydrogen, can be converted into compounds of formula X using sequential processing of a base (such as potassium carbonate) and a compound of formula R2-L.Compounds of General formula XII can be obtained from compounds of General formula VIII using standard methods described in the chemical literature.Alternatively, compounds of the invention having the General formula I can be obtained from substituted benzenes of General formula XIX using the stages shown in scheme III (see Fig. 2).In scheme III, the symbols R1, R2, A, W, X, Y and Z have the meanings given above represents hydrogen or halogen, and E, not only is Lee MgCl).Thus, compounds of General formula I can be obtained by processing complex ketoesters of General formula XY phosphorane General formula XVI in a suitable solvent, such as diethyl ether (see, for example, EP-A-0044448 and EP-A-0178826) (stage with scheme III).Complex ketoesters of General formula XV can be obtained by treatment of substituted metal compounds XVII oxalate XVIII in a suitable solvent, such as diethyl ether or tetrahydrofuran. The preferred method often involves the slow addition of a solution of substituted metal compound XVII to a stirred solution of excess oxalate XVIII (see for example, L. M. Weinstock, R. B. Curric u A. V. Zovell, Synthetic Communication 1981, II, 943, and references cited there) (stage m scheme III).Substituted metal compound XVII in which E represents MgI, MgBr or MgCl (Grignard reagents) can be obtained using standard methods from the corresponding aromatic halides XIX, in which D represents I. Br or Cl, respectively. Some of the substituents X, Y and Z substituted metal compound XVII in which E represents lithium, can be obtained by the reaction of the direct connection of lithium (litrovaya) to compounds HHI or lithium di-Isopropylamine (see for example, H. W. Gschwend u H. R. Rodriguez, Organic Reactions 1979, , 1) (stage n scheme III).Compounds of General formula XIX can be obtained using standard methods described in the chemical literature.In the chemical literature describes alternative ways to get complicated ketoesters of General formula XV (see for example, D. Atkinson, K. E. Godfrey, B. Meek, I. E. Saville u M. R. Stillings, and I. Med. Chem, 1983, , 1353; D. Horne, I. Caudino and W. I. Thompson, Tet, Lett. 1984, 25, 3529; and Axiotis, Tetrahedron Lett. 1981, 22, 1509).Methods for obtaining compounds of the invention having the General formula I described in schemes I and II, usually applicable when W in the General formula I is a substituted 2-pyridinyl, or 2 - or 4-pyrimidinyl group, and when W is a 4-pyridinyl group containing strong electron-dilatory substituents, such as nitro, trifluoromethyl or fluorine. However, for compounds of General formula I, in which W represents a substituted 3 - or 4-pyridinyl group, the methods shown in scheme II, usually can not be applied.Also, although the compounds of the invention having the General formula I, in which W represents a substituted 3 - or 4-pyridinyl group can be obtained from compounds of General formula IV with phases a, b and C, as showing the PU, not usually can be obtained through the stages e and f, shown in scheme I. Therefore, it may be necessary to use an alternative method of obtaining compounds of General formula IV.Typically, the compounds of formula IV, in which W represents a substituted 3 - or 4-pyridinyl group can preferably be obtained by using method shown in scheme IV (see Fig. 2, 3).So, scheme IV, compounds of formula IV, in which W represents a substituted 3 - or 4-pyridinyl group can be obtained from compounds of formula XX, in which W represents a substituted 3 - or 4-pyridinyl group.For scheme IV, the symbols A, X, Y, Z and L have the meanings given above for schemes I-III, and T represents any group which can be transformed using standard methods described in the literature, using one or more stages in acetic ether side chain structure of CH2OOR, as shown in formula IV. For example, T may be a formyl group or any group that is able to transform into a formyl group, such as formylacetate, which can be either hydrolyzed with aqueous acid formyl group, or such as nitrile, which can vos and L. H. Sehwartzmann J.Org. Chem. 1959, , 627) or by using a Raney alloy in formic acid (see, for example, van ES u Staskun, J. Chem. Soc. 1965, 5775). When T represents a formyl group, she can then turn in the remainder of ester acetic acid CH2COOR1c by reaction with methyl-methylsulfonylmethane (CH3SOCH2S CH3) (see, for example, K. Ogura u G. Tsuchihashi, Tetrahedron Lett. 1972, 1383-6), with subsequent hydrolysis of the alcohol R1OH in the presence of an acid such as hydrogen chloride. For example, T can also be a group such as a methyl group, which may helodermatidae, for example, bromine or N-bromosuccinimide, giving kaleidotile group, which can then be processed by cyanide ion, giving cyanomethylene group, which in turn can be either hydrolyzed in the remainder of the acetic ester CH2OOR1using methods well known in the literature. T can also be, for example, a carboxylic acid group or a hard-essential group, which can be restored in hydroxymethylene group, which in turn can turn into cyanomethylene group using methods well known in the literature.The compounds of formula XX, in which W represents a substituted what volumes I, through reaction with compounds of formula XXII in which W represents a substituted 3-pyridinyl group, under conditions normally used for the well-known synthesis Ullman. For example, the compounds of formula XXI can be processed metal salt (preferably the sodium salt or potassium) compounds of formula XXII, or in mass, or in a suitable solvent such as N,N-dimethylformamide or dimethylsulfoxide, at 50-250aboutC, but preferably at 100-180aboutSince, in the presence of a catalyst of a transition metal, such as copper bronze or copper halides.Compounds of General formula XXI can be obtained using standard methods known from the chemical literature.The compounds of formula XX, where W is a substituted 4-pyridinyl group can be obtained by the interaction of the metal salt (preferably sodium or potassium) compounds of the formula (XXIII) with compounds of formula VI in which X represents a substituted 4-pyridinyl group in a suitable solvent such as N,N-dimethylformamide or dimethylsulfoxide, at 20-200aboutWith, and preferably at 50-150aboutAnd optionally in the presence of transition metal catalysts, tachoni formula XXV, in which R is defined as a pyridyl, N-oxide, associated with a 4-position. R may or may not be substituted by the substituents defined for W in compounds of formula I. If the group R in compounds of formula XXV is substituted, the subsequent deoksigenirovanii N-oxide using standard methods, for example, phosphorus trichloride, gives compounds of formula XX, in which W represents a substituted 4-pyridinyl. When R in the compounds of formula XXV is substituted or unsubstituted, further well-known reaction of N-oxide of pyridine with phosphoryl or thionyl-halides can be used to obtain compounds of the formula XX, containing more halogen atom in the 2 - or 6-position, with simultaneous loss of the N-oxide function (see, for example, "The chemistry of The Heterocyclic Compounds; Pyridine and Its Perivatives", Ed.E.Klingsberg, Part 2, page 121).The compounds of formula XXV can be achieved with the cooperation of the metal salt (preferably sodium or potassium) compounds of the formula XXIII with compounds of formula XXIV in which R and L have the meanings given above, in a suitable solvent such as N,N-dimethylformamide or dimethylsulfoxide, at 20-200aboutC and preferably at 50-150aboutWith that optional is inane formula XXIII can be obtained using standard methods, described in the chemical literature. According to additional aspects of the invention is the methods described.Compounds according to the invention are active fungicides and may be used to combat one or more of the following pathogens:
Pyrucularia oryzal on rice Puccinia ruondita, Puccinia striiformis and other rusts on wheat. Puccinia hordeli, Puccunia striiformis and other rusts on barley, and rust diseases on other crops, such as coffee, pears, apples, groundnut, vegetable crops and ornamental plants.Erysiphe graminis (powdery mildew) on barley and wheat and other powdery mildew on various crops, such as
Sphaerotheca malutaris on the hops,
Sphaerotheca fuliginea on cucurbits (e.g. cucumber), Podosphaera lucotrisha on Apple trees and Ulcinulla necator on grape vine, Helminthosporium spp, Rhynochosporium spp, Septoria spp. Pseudocercosporella herpotrichoides and Galumannomyces graminis on cereals.Cercospora arachidscola and Arcosporidium personata on groundnut and other Cercospora species on other crops such as sugar beet, bananas, soya beans and rice. Botrytis cinerea (grey mould) on tomatoes, strawberries, vegetables and other crops.Alternaria species on vegetables (ndegualis (scab) on apples.Plasmopara viticola on grapevine.Other types of downy mildew, such as Bremia lactical on the lettuce Peronospora., soybeans, tobacco, onions and other crops and Pseudoperonospora humuli on hops and Pseudoperonospora cubensis on pumpkin, Phytophthora infestans on potatoes and tomatoes and other Phytophthora spp. vegetables, strawberries, avocado, pepper, ornamental crops, tobacco, cocoa and others.Thanatephorus cucumeris on rice and other types Phizoctonia on different crops-hosts such as wheat and barley, vegetables, cotton and turf.Some of the compounds also showed broad spectrum activity against fungi in vitro. They may be active against various diseases of fruits after harvest (for example, Penicillium digitatum and Trichoderma viride on oranges and Gloesporium musarum on bananas).Further, some of the compounds may be active as seed treaters against Fusanum spp. Septoria spp. Tilletia spp. (bunt of wheat, diseases of wheat seeds), Ustillago spp. Helminthosporium spp. on cereals, Rhizoctonia solani on cotton and Pyricularia oryzae on rice.These compounds may advance in plant tissues acropetal. In addition, they can be volatile enough to be active in the vapour phase against the manual of combating fungi, which provides the application with regard to plants, to the seeds of plants, or to the locations of the plant or seed, an effective amount of the fungicidal compounds of formula I.The compounds may also be useful as industrial (as opposed to agricultural) fungicides, for example, to prevent fungal wood, hides and skins, leather and especially coatings of paint.Some of the compounds of the invention are insecticidal and nematocidal activity.Therefore, according to an additional aspect of the invention proposes a method of destroying or insect or nematode pests which comprises applying in relation to the pests or to the place of their distribution effective amount of insecticide/nematocide the compounds of formula I.A preferred group of compounds for use in this aspect of the invention are the compounds of formula I in which X is a substituted pyridinyl, in which the substituents are substituents, preferably selected from halogen or haloalkyl.Particularly preferred compounds for ispolzovanie compounds exhibit activity regulation of plant growth and can be used for this purpose with the relevant norms of consumption. Therefore, according to another aspect of the invention is the method of regulating plant growth which comprises applying to the plant an effective amount of the compounds of formula I, regulating the growth of plants.Connections can be used directly for agricultural purposes, but it is more convenient to convert the composition using a carrier or diluent. Therefore, according to an additional aspect of the invention are represented fungicidal, insecticidal/nematocide and regulating the plant growth composition comprising a compound of General formula I, described here above, and an acceptable carrier or diluent for this connection.As fungicides compounds can be applied using several methods. For example, they can be used after prior conversion into finished preparative form or without it, directly to the foliage of a plant, to seeds or to other medium in which plants are grown or they are to be planted, or they can be sprayed or spray, be applied in the form of dust or applied in the form of creams or pastes preparative forms, or they can primenyatsya in relation to any part of the plant, including leaves, stems, branches or roots, or to soil surrounding the roots, or seeds before sowing or planting; or in General, to soil, to water, flooded areas or systems hydroponic culture. Compounds of the invention can also be inetservices into plants or sprayed onto vegetation using electrodynamic techniques such as spraying or other methods use a small amount.The term "plant" as used here, includes seedlings, shrubs and trees. In addition, fungicidal method of the present invention includes preventive, protective, preventive or therapeutic treatment.Compounds preferably used for agricultural purposes and goals of horticulture in the form of compositions. The type of composition in any case will depend on the specific purpose.These compositions can be in the form capable of dispersion in the form of dust powders or granules comprising the active ingredient (compound of the invention) and a solid diluent or carrier, for example, such fillers like kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, fallerovo land, hightime to be applied to the soil without additional processing. These granules can be produced, or by impregnation of the pellets filling the active ingredient, or by using a tabletting mixture of the active ingredient and powdered filler. The composition for seed treatment may include the agent (e.g., mineral oil), promoting adhesion of the composition to the seed; alternatively, the active ingredient can be transformed in preparative form for the purposes of seed treatment using an organic solvent (for example, N-methylpyrrolidone, propylene glycol or dimethylformamide). The composition may also be in the form of wettable powders or dispersible in water, the granules comprising a wetting or dispersing agent to facilitate the dispersion in liquids. Powders and granules may also contain fillers and suspendresume agents.Emulsifiable concentrates or emulsions can be prepared by dissolving the active ingredient in an organic solvent optionally containing wetting or emulsifying agent, and then adding the mixture to water which may also contain wetting or emulsifying agent. Suitable organic solvents are, knee hydrocarbons, such as chlorobenzene and dichloromethane, and alcohols such as benzyl alcohol, furfuryl alcohol, butanol and glycol ethers.Suspension concentrates largely insoluble solids can be prepared using ball grinding with dispersing agent and include a suspending agent to prevent settling of solids.Compositions intended for use as sprays, can be in the form of aerosols, in which the finished form of the drug contained in the container under pressure in the presence 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 a composition suitable for generating in confined spaces smoke containing compounds.Alternative connections may be used in microencapsulation. They can also be converted into biodegradable polymer formulation to obtain drugs with slow, controlled release of the active substance.Thanks to the inclusion of suitable additives, for example, additives that improve the R is ucse to adapt for various utilitarian purposes.Compounds of the invention can be used as mixtures with fertilizers (e.g., nitrogen-, potassium - or phosphorus-containing fertilisers). Compositions comprising only the fertilizer granules, for example, coating compound, is preferred. These granules suitably contain up to 25% by weight of the connection. The invention therefore also provides a fertilizer composition comprising a fertilizer and compound of General formula I or its salt or a metal complex.Wettable powders, emulsifiable concentrates and suspension concentrates usually contain surfactants, for example, wetting agent, dispersing agent, emulsifying agent or suspendisse agent. These agents can be cationic, anionic or non-ionic agents.Suitable cationic agents are Quaternary ammonium compounds, for example, acetyltributyl - ammoniumbromide. Suitable anionic agents are Soaps, salts of aliphatic monoamino sulfuric acid (for example sodium lauryl sulphate), and salt from sulphonated aromatic compounds (for example, dodecylbenzenesulfonate sodium, sodium lignosulphonate, calcium, or ammonium, butylnaphthalene, and Claudia condensation products of ethylene oxide with fatty alcohols, such as alerby or cetyl alcohol, or with alkyl phenols such as octyl or ionil-phenol and extinciton. Other non-ionic agents are the partial esters derived from fatty acids with long chain and hexitol-anhydrides, condensation products of these partial esters with ethylene oxide, and lecithins. Suitable suspendresume agents are hydrophilic colloids (e.g., polyvinylpyrrolidone and sodium carboxymethylcellulose), and swelling clay, such as bentonil or attapulgite.Compositions for use in the form of aqueous suspensions or emulsions are generally supplied in the form of a concentrate containing a large amount of the active ingredient, and the concentrate is diluted before use with water. These concentrates should preferably be able to withstand storage for prolonged periods and after such storage, to be capable of dilution with water to form aqueous preparations which remain homogeneous for a sufficient time, giving you the ability to apply them using conventional spraying equipment. The concentrates may conveniently contain up to 95% in a suitable manner the preparations may contain varying amounts of the active ingredient depending on the purpose, and can be used in aqueous preparations containing 0,0005 or 0.01-10% by weight of 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 activity regulation of plant growth, herbicide or insecticide activity.Fungicidal compound which may be present in the compositions of this invention may be a compound which is capable of suppressing the diseases of the ears of cereals (e.g. wheat) such as Septoria, Giblerella, Helminthosporium spp. diseases of seeds and diseases that occur in the soil, and false and powdery mildew on grapevine and powdery mildew and parse Apple and other Thanks to the inclusion of another fungicide composition can have a broader spectrum of activity than the compound of General formula I, taken one. In addition, the other fungicide can have Energeticheskie effect on the fungicidal activity of the compounds of General formula I. Examples of fungicidal compounds which may be included in the composition of this invention are carbendazim, benomyl, telfa is, -chloro-N-/1-cyano-1-ethoxymethyl/benzamid, benalaxyl, positionwise, fenarimol, iprodione, protocorm, procymidon, vinclozolin, penconazole, micromotor, propamocarb. R 0151297, miconazol, Parisio, ethirimol, datalists, butiaba, tridemorph, triforine, nuarimol, triazolyl, guazatine, triacetate salt, 1,1'-iminodi/octane - tilen/biguanidine, propiconazol, prochloraz, flutriafol, hexaconazole, (2RS, 3RS)-(4-chlorophenyl/-3-cyclopropyl-1-)1H-1,2,4-triazole-1-yl/butane-2-ol: /RS/-1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazole-1-yl methyl)pentane-3-ol, flusilazol, triadimefon, triadimenol, diclobutrazol, fenpropimorph, pirivenas, fenpropidin, CHLOROTHALONIL, Omisalj, fanforum, carboxin, oxycarboxin, mefenoxam, dodemont, BAS 454, blasticidin S, kasugamycin, edifenphos, Kitazin P, cycloheximide, phtalic, provenzal, isoprothiolane, tricyclazole, pyroquilon, chlorbenzene, paasonen, polyoxin D, validamycin And mepronil, flutolanil, pancoran, declomycin, fenesin-oxide, the Nickel dimethyldithiocarbamate, thorpdale, bitertanol, bupirimate, itaconate, hydroxyethoxy, streptomycin, zipform, bilocate, chinomethionat, dimethirimol, 1-(2-cyano-2-methoxyimino)-3-ethyl-mo - Cavina, verapamil, tolclofos-methyl, proxyfor, polishers, MANEB, MANCOZEB, pakil, nitratenitrogen, Dodin, dithianon, fentin-hydroxide, fentin-acetate, tecnazene, hintzen, dicloran, stranded-containing compounds such as copper oxychloride, copper sulphate and Bordeaux mixture, and mercury-organic compounds.Compounds of General formula 1 can be mixed with soil, peat or other environments for the growth of the roots for the protection of plants emerging from seeds in the soil diseases and fungal diseases of foliage.Suitable insecticides that can be entered into the composition of this invention include pirimicarb, dimethoate, demeton-S-methyl, formation, carbaryl, isoprocarb, CMS, VRMS, carbofuran, carbosulfan, diazinon, fenthion, fenitrothion, pentat, chlorpyrifos, isoxathion, propafol, monocrotophos, buprofezin, Atropatene and cicloprofen.Compounds that regulate the growth of plants, are compounds that suppress weeds or the formation of seed panicles, or selectively regulate the growth of less desirable plants (e.g. grasses).Examples of suitable compounds that regulate the growth of plants, for use with the compounds of the invention are giberellin (for example, GA3, GA4or GA7), the auxins (e.g. andaluces the EP, kinetin, diphenylacetone, benzimidazole, benedictin or benzylaminopurine), venexiana acid (for example, 2,4-D or MSRA), substituted benzoic acid (for example, triiodobenzoic acid), morphactin (for example, gliptoteka), maleic hydrazide, glyphosate, glitsin, long chain fatty alcohols and acids, dikegulac, paclobutrazol, fluoridated; mefluidide, substituted Quaternary ammonium and postname connection (for example, chlormequat Floriani or meekathara), ethephon, carbetamide, methyl-3,6-dichloracetate, daminozide, Azul, abscisic acid, isoperibol, 1-(4-chlorophenyl)-4,6-dimethyl-2-oxo-1, 2-dihydropyridines-3-carboxylic acid, hydroxyben - isonitrile (for example, bromoxynil), difenzoquat, benzoylperoxy-ethyl-3,6-dichlorphenoxy acid, fenbendazol, invented, thiapentanal and tecnazene.The following examples illustrate this invention. In all these examples, the term "simple ester" or "ester" refers to diethyl ether; chromatography was performed using silica gel as the solid phase; magnesium sulfate was used to dry solutions; and reactions involving sensitive to water or air intermediate products, was carried out in nitrogen atmosphere and in osseni iSlate each absorption. Unless otherwise stated, NMR spectra were recorded using solutions in deuterium chloroform. Throughout the examples the following abbreviations are used:
δ=chemical shift, SDS3=deuterochloroform, s=singlet, d=doublet, T= triplet, Shir.wide;
DMF= N, N-Dimethylformamide, max maximum or maxima LC=liquid chromatography high resolution;
NMR nuclear magnetic resonance.P R I m e R 1. This example illustrates the preparation of (E)-methyl-2-[2'-(5"-nitropyridine-2"-yloxy)phenyl]-3-metocean - relate (Compound N 133, PL. 1).2-(Hydroxyphenyl)acetic acid (50 g) was added to a solution of hydrogen chloride in methanol (prepared from acetylchloride (25 ml) and methanol (250 ml). This solution was stirred at room temperature for 3 h, and then it was allowed to stand over night (15 h). The resulting mixture was concentrated under reduced pressure, and the residue was taken up in a simple ether (250 ml) and was washed with an aqueous solution of sodium bicarbonate until then, until the continued rapid evolution of gas. The ether solution was dried, and then concentrated under reduced pressure, and the resulting firmly the 2% yield) as white powdery crystals, so pl. 70-72aboutC; IR max (nujol): 3420, 1715 cm-1;
IH NMR (90 MHz): Delta 3,70 (2H,/, of 3.75 (3H,s), 6,80-to 6.95 (2H, m), 7,05-7,10 (1H, m), 7,15-of 7.25 (1H, m), 7,40 (IH, s) ppm.Methyl (2-hydroxyphenyl)acetate (21,0 g) was dissolved in dimethylformamide (200 ml), was added potassium carbonate (19,35 g) in one portion. To this mixture was added dropwise benzylbromide (23,94 g) in dimethylformamide (50 ml) under stirring at room temperature. After 18 h the mixture was poured into water (500 ml) and was extracted with diethyl ether (CH ml). The extracts were washed with water (I ml) and brine (100 ml), dried and filtered through silica gel (50 g, Merck 60), then concentrated under reduced pressure, giving a yellow oil. Distillation at 160aboutC and a pressure of 0.05 mm. RT. Art. gave methyl 2-benzyloxyaniline in the form of a clear, colourless oil (26,99 g, 83% yield), IR max (film): 1730 cm-1;IH NMR (90 MHz): Delta of 3.60 (3H, in), 3.75 (2H, s), 4,10 (2H, s), 6,80-7,40 (9H, m) million dollars.A mixture of methyl 2-benzyloxybenzoate (26,99 g) and methylformate (126,62 g) in dry dimethylformamide (300 ml) was added dropwise to a stirred suspension of sodium hydride (50% dispersion in oil, 10,13 g) in DMF (300 ml) at 0aboutC. After peredney layer was pagkilala to pH 4 with 6 M hydrochloric acid, then was extracted with diethyl ether (CH ml). The extracts were dried and concentrated under reduced pressure, giving crude methyl 2-(2'-benzyloxyphenyl)-3-hydroxy-acrylate as a yellow oil, IR max (film): 1720, 1660 cm-1.The crude methyl 2-(2'-benzyloxyphenyl)-3-hydroxyacrylates was dissolved in dry dimethylformamide (100 ml), and one portion was added potassium carbonate (29.0 g). Then dropwise added dimethylsulfate (16,00 g) in dry DMF (10 ml) under stirring. After ninety minutes, water was added, and the solution was extracted with diethyl ether (CH ml). After washing with water (I ml) and saline extracts were dried and concentrated under reduced pressure, and the resulting yellow oil was hardened after trituration with a mixture of diethyl ether and benzyl. Recrystallization from dry methanol gave (N)-methyl-2-/2'-benzyloxyphenyl/-3-metocean - relat in the form of a white crystalline solid (5,44 g, 17% yield from methyl 2-benzyloxybenzoate), so pl. 76-77aboutC; IR max /nujol/: 1710, 1640 cm-1;IH NMR (90 MHz): Delta 3,63 (3H, in), 3.75 (3H, s), is 5.06 (2H, s), 6,80-7,40 (N, m) to 7.50 (IH, s) million dollars./E/-Methyl-2-/2'-benzyloxyphenyl/-3-ect was gerasoulis at a pressure of three atmospheres, under stirring until then, until no more was absorbed hydrogen was then filtered through celite and silica gel (50 g, Merck 60). Concentration of the filtrate under reduced pressure gave /E/-methyl-2-/2'-hydroxyphenyl/-3-ethoxyacrylate in the form of a white crystalline solid /3,76 g, 99% yield/, so pl. 125-126aboutC; IR max /nujol/: 3400, 1670 cm-1;
IH NMR (270 MHz): Delta of 3.80 (3H, s), 3,90 (3H, s), of 6.20 (1H, s), 6,80-7,00 (2H, m), 7,10-7,30 (2H, m), 7,60 (1H, s), M. D./E/-Methyl 2-/2'-hydroxyphenyl/-3-ethoxyacrylate /0,30 g, 1.44 mmole/, 2-chloro-5-nitropyridine /0,48 g, 2.88 mmole) and potassium carbonate /0.40 g, 2.88 mmole/ were mixed together in DMF /20 ml at room temperature in a nitrogen atmosphere. After 18 h the reaction mixture was poured into water and then extracted twice with diethyl ether. The combined ether layers were washed twice with water and brine, and then dried. The resulting solution was filtered through a plug of silica gel and then concentrated, giving a pink solid. Chromatography /eluent: diethyl ether/ gave /E/-methyl 2-[2'-(5"-nitropyridine-2"-yloxy)phenyl]-3-ethoxyacrylate (240 mg) as a yellow resin, which crystallized upon standing, so pl. 107-109aboutC;
IH NMR", yloxy)phenyl] -3-label - diacrylate (Compound 61 table. 1/.E-Methyl 2-/2'-hydroxyphenyl/-3-ethoxyacrylate (0,63 g), 2,4-dichloropyrimidine (0.75 g) and potassium carbonate (0,69 g) were mixed together in DMF at room temperature. After 2 h the reaction mixture was poured into water (50 ml) and was extracted twice with diethyl ether. The combined ether layers were washed with water /X3/ and the yellow solution /x1/, and then dried. Filtration and evaporation of the solvent under reduced pressure gave a light oil. Chromatography using as eluent diethyl ether gave /E/-methyl-2-[2'(4"-chloropyrimidine-2"-yloxy)phenyl]-3-ethoxyacrylate /0,35 g/ in the form of oil, which crystallized after trituration with ether; so pl. 120-121,5aboutC;
IH NMR: Delta of 3.60 (3H, s), of 3.80 (3H, s), 6,60 (1H, d J=4 Hz), 7,40 (1H, s), 8,40 (1H, d J=4 Hz) M. D.P R I m e R 3. This example illustrates the preparation of /E/-methyl 2-[2'-(6"-methylpyridin-3"-yloxy)phenyl] -3-metocean - relata /Connection 45 of the Table. 1/.6-Methyl-3-hydroxypyridine (9.5 g) was suspenderbelt in toluene (30 ml) and was treated aqueous potassium hydroxide (4.9 g in water 3 ml). The mixture was mixed vigorously for 15 min, then was perivolas under reduced pressure. The last traces of water were removed by repeated evaporation in Presolana (10.0 g/, chloride copper /60 mg/ and Tris[2-(2-methoxyethoxy)-ethyl] amine /0,194 g/ to solubilize the copper salt in dry DMF /25 ml, and the mixture was heated to 155aboutWith under stirring in nitrogen atmosphere for 30 hours was Added advanced copper chloride (60 mg), and heating was continued for 14 hThe mixture was cooled, poured into water and was extracted with ethyl acetate. The extract was washed 2 N. aqueous sodium hydroxide solution and water, followed by extraction 2 N. hydrochloric acid. The acidified aqueous extract was treated with solid potassium carbonate until until the pH will not be 8, and then was extracted with ethyl acetate. This organic extract was dried, and then supariwala under reduced pressure, yielding 2-/6'-methyl - pyridine-3'- yloxy/-benzaldehyde /2.2 g/ in the form of an oil; IR max /film/: 1697, 1606, 1480 cm-1;
IH NMR: Delta of 2.58 (3H, s) 6,86 (1H, s), 7.23 percent (3H, m), 7,55 (1H,t), 7,95 (2H, m), 8,35 (IH, m), 10,53 (IH, s), mln.2-(6'-Methylpyridin-3'-yloxy)benzal - digid (2,08 g) and methyl methylsulfonylmethyl (1,21 g) was dissolved in dry THF (15 ml), and Triton B (1.5 ml) was added slowly dropwise with stirring at room temperature. The mixture was defended during the night, it was diluted with water and extras what about the brown oil (3.2 g). The oil was processed methanol solution of hydrogen chloride (25 ml 2,6 BC) and stood at room temperature overnight. The solution then was diluted with water and brought to pH 8 by adding sodium carbonate. The mixture was extracted with ethyl acetate and the extract was dried and supariwala, giving a brown oil (2,23 g) which was purified using liquid chromatography high resolution /eluent a 1: 1 mixture of ethyl acetate:hexane/, giving methyl[2-(6'-methylpyridin-3'-yloxy)phenyl] acetate as a yellow oil /1,53 g/, infrared max /film/: 1747, 1488, 1237 cm-1;
IH NMR: Delta of 2.54 (3H, s), 3,63 (3H, s) to 3.64 (2H, s), at 6.84 (1H, d), from 7.24 (5H, m), and 8.3 (1H, d), mln.A mixture of methyl [2-(6'-methylpyridin-3'-yloxy)phenyl] acetate (1.3 g) and methylformate (1.52 g) in DMF (5 ml) was added dropwise to a suspension of sodium hydride (316 mg, 50% dispersion in oil) in DMF (5 ml) under stirring at 5aboutC. After stirring for 4 h the mixture was diluted with water, made weakly acidic by the addition of glacial acetic acid /pH 4-5/ and was extracted with ethyl acetate. This extract after drying and evaporation under reduced pressure gave methyl 2-[2'-(6"-methylpyridin-3"-yloxy)phenyl]-3 - hydroxyacrylates in the form of a yellow oil (1.15 halos in DMF (15 ml), was added potassium carbonate (1.1 g) and the mixture stirred for 15 minutes. Dimethylsulfate (0,53 g) was dissolved in DMF (5 ml) and this solution was added to the mixture. The resulting mixture was mixed for 30 minutes, then was diluted with water and the resulting emulsion was extracted with ethyl acetate. This extract was dried and supariwala under reduced pressure, giving a yellow oil (of 2.06 g) which was purified using LC/eluent: ethyl acetate/ giving /E/-methyl-2-[2'-(6"-methylpyridin-3"-yloxy)Fe - Neil]-3-methoxyaniline in the form of a pale yellow oil (0.73 g), IR max (film): 1705, 1642, 1488 cm-1;
IH NMR: Delta 2,52 (3H, s), 3,63 (3H, s), 3,81 (3H, s), to 6.88 (1H, d),? 7.04 baby mortality-to 7.32 (5H, m), 7,51 (1H, s), compared to 8.26 (1H, d) mln.P R I m e R 4. Using the methodology of example 1, there are obtained the following compounds; 1. /E/-methyl 2-[2'-(5"-chloropyridin-2"-yloxy)phenyl]-3-ethoxyacrylate, so pl. 77-78aboutC;
infrared max 1700, 1625, 1260, 1200 cm-1;
1H NMR: Delta /SDS3/3, 57 (3H, s), 3,74 (3H, s), of 6.75 (1H, d), 7,41 (1H, s), 8,10 (1H, Shir,) and 7.1-7,65 (m) M. D.2. /E/-methyl-2-[2'-(5"-cyano-2"-yloxy)phenyl]-3-ethoxyacrylate (compound 127 table. 1), in the form of white crystals, so pl. 108,5-109,5aboutC;
1H NMR Delta to 3.58 (3H, in), 3.75 (3H, ), 6,9 (1�] -3-ethoxyacrylate (compound 14 of table. 2), in the form of a thick resin, infrared max 1700, 1630 cm-1;
1H NMR: as in table. 4.4. /E/-methyl 2-[2'(5"-pampered-2"-ylsulphonyl)phenyl]-3-ethoxyacrylate resin;
1H NMR: as in table. 4.5. /E/-methyl 2-[2'(5"-pampered-2"-ylsulphonyl)phenyl]-3-ethoxyacrylate in the form of amorphous solids;
1H NMR: as in table. 4.6. /E/-Methyl 2-[2'-(5"-methoxycarbonylmethyl-2"-yloxy)phenyl] 3-ethoxyacrylate (compound 141 table. 1).1H NMR: Delta 3,47 (3H, s), 3,62 (3H, s), 3,82 (3H, s), 6.75 in with 7.3 (5H, m), 7,32 (1H, s), 8,15 (1H, square), 8,72 (1,N, d), M. D.7. /E/-Methyl 2-[2'-(5"-benzyloxycarbonylamino-2"-yloxy)phenyl]-3-metocean - relate (compound N 184 table 1), in the form of resin;
1H NMR: Delta 3,55 (3H, s), of 3.60 (3H, s), to 5.35 (2H, s), PC 6.82 (1H, d), 7,18-of 7.48 (m), including one proton singlet at 7,39), to 8.25 (1H, square), of 8.25 (1H, d), M. D.The following are examples of compositions suitable for agricultural and horticultural use, which can be converted into ready preparative forms of the compounds of the present invention. Such compositions form another aspect of the present invention.P R I m e R 5. Emulsifiable concentrate is prepared by mixing and stirring ingresoll - methanesulphonate calcium 5%
lat (13 moles ethylene oxide) 10% alkyl benzenes 45%
P R I m e R 6. The active ingredient is dissolved in methylenechloride, and the resulting liquid is sprayed on the granules attapulgite clay. The solvent then allow to evaporate, receiving the composition in the form of granules. Compound 14 of table. 1 5% Granules apparelget 95%
P R I m e R 7. Composition suitable for use as a seed dressing, prepared by grinding and mixing the three ingredients. The connection 61 table. 1 50% Mineral oil 2% China clay 48%
P R I m e R 8. Dostawy powder is prepared by grinding and blending the active ingredient with talc. The connection 61 table. 1 5% Talc 95%
P R I m e R 9. The suspension concentrate is prepared using ball grinding ingredients with the formation of the aqueous slurry of the crushed mixture with water. The connection 61 40% sodium Lignosulphonate 10% bentonite compounds, preventing clay 1% Water 49%
This new form can be used in the form of a spray by diluting it with water or applied directly to the seed.P R I m e R 10. The form of a wettable powder is made by serenawilliams sodium 2% sodium Lignosulphonate 5% Silica 25% China clay 43%
P R I m e R 11. Compounds were tested against a variety of fungal diseases of foliage plants. The technology used in the tests was as follows.Plants were grown in compost pots for John Jnnes /1 or 2/ minihorse diameter 4 see Test compounds were transformed into finished form of the drug or grinding balls with water Dispersol T or in the form of a solution in acetone or a mixture of acetone and ethanol, which was diluted to the required concentration immediately before use. In the case of diseases of foliage drugs (100 h per million of active ingredient) was sprayed on the leaves and applied to plant roots in the soil. Sprays were applied to the maximum retention on the surface, and the roots were moist to a final concentration equivalent to approximately 40 frequent. per million of active ingredient in dry soil. When the sprays were applied to the cereal, add tween-20 to obtain a final concentration of 0.05
In the case of most of the test compound was applied to the soil and roots to the leaves /spray/ for one or two days before infection of a plant disease. The exception was the test against Erysiphe graminis, which plants in the s spores on the leaves of the test plants. After inoculation the plants were placed in a suitable environment to enable development of the disease, and then were incubated up until inoculation was not ready for evaluation. The period between inoculation and evaluation varied from 4 to 14 days, depending on disease and environmental conditions.The disease was recorded according to the following scale;
3=traces -5% of disease on untreated plants;
2=6-25 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.P R I m e R 12. This example illustrates the properties of compounds 14-16, 22, 61, 132 and 138-140 table. 1 to regulate the growth of plants.These compounds was tested by screening for the activity of regulating the growth of plants on six species of plants. The plant species used in this screening are presented in table. 6, indicating leaf stage at which the plants were sprayed.The preparation of each chemical was applied in the amount of 4000 frequent. /million/4 kg/ha under field volume 1000 l/ha using a track sprayer and referred spraying, the plants were grown in a greenhouse with day temperatures of 25aboutAnd at night -22aboutC. with the Exception of this trial was the cereal of temperate climate, wheat and barley were grown at daytime temperatures 13-16aboutWith and the temperatures at night-11-13aboutC. When it was necessary to provide the average duration of the photoperiod 16 h /min 14 h/ used additional lighting.After 2-6 weeks spent in the greenhouse, depending on species and time of year, plants were evaluated visually in relation to morphological characteristics in comparison with the control plants, spray form drugs (without active substance). The results are presented in table. 7.P R I m e p 13. This example illustrates the insecticidal properties of some compounds of formula /1/.The activity of each compound was determined using various insects, mites and nematode pests. The compound was used in the form of liquid preparations containing 100-500 hours/million/ mass connection. The drugs were prepared by dissolving the compound in acetone and diluting the solutions with water containing 0.1% by weight of a wetting agent sold under the trade name "SYNPERONIC" MX, until then, until the liquid p is trademark howl.The test procedure used for each of the pests was basically the same and included the location of a number of pests on the environment, which was usually the host-plant or food that eat pests, and handling or environment, or pests, or both drugs. The mortality of the pests was assessed over periods generally ranging from one to seven days after treatment.The test results are given in table 9 for each of the products that are taken in an amount in parts per million given in the second column, and the rating scale mortality was designated as 9, 5 or 0, where 9 indicates 80-100% mortality (70-100%) reduction in regrowth of roots compared to untreated plants in the case of Meloidogyne incognita, 5 indicates 50-79% mortality (50-69% ) reduction in regrowth of roots in the case of Meloidogyne incognita and 0 means less than 50% mortality (decrease regrowth of roots for eloidogyne incognita).In table 9 used the pest organism is denoted by a letter code, and the kinds of pests, the environment or food, and the type and duration of the trials are given in table. 8.According to the applicant, structurally closest connection, which was previously known about the presence of a fungicide with Strobilurin-or muzigin" has the following structure:
It was first isolated in 1969 (Musilek et al. Folia Environ. (Prague) 1969, , 377; SA, 1970, , 11356h), and its fungicidal activity is described later (for example, J. Kejda Prakt. Lek. 1980, , 26; SA, 1980, , 143792r). It was stated that "muzigin" may be potentially useful in plant protection "(Sasuk and Musilek, Folia Environ. (Prague) 1974, , 139; CA, 1974, , 33868q). The structure of the compound, including the right (, , )-geometry, appeared in 1979 (patent Czechoslovakia N 180177; SA, 1980, , 20428). That strobilurin and muzigin are one and the same connection, it was found in 1981 (Sedmara et al J. Antibiol. 1981, , 1069).To illustrate the positive effect proposed by the applicant of the compounds of strobilurin-And can be mapped, for example, with the compound II of table. I, having the structure:
< / BR>The fungicidal activity of the two compounds on plants demonstrated by tests carried out using the General technique described in example 11 of the present application, except that both compounds were applied in the form of preparations containing 25 million-1the active ingredient. In the case of compound (11) the drug was applied only spraying on the foliage. In the case of strobilurin-And the drug was applied by spraying on foliage, analogic is described in example 11):
The results clearly show that the compound 11 of table. 1 bids more aggressively than strobilurin-And as a fungicide for plants, even when using strobilurin-A combined image spraying foliage/soaking the root layer, and a connection 11 only spraying the foliage.In terms of toxicity, the results of this work it was concluded that the compounds belong to the category of low. DERIVATIVES of ACRYLIC ACID of General formula
< / BR>where W is pyridyl, substituted once by halogen, C1- C4the alkyl(possibly substituted with halogen)phenyl, C1- C4-alkoxy, phenoxy(possibly substituted 1-methoxycarbonyl-2-methoxyethanol); amino-, formamido-, nitro-, cyano -, or N-oxide group, doubly substituted with substituents selected from the group of halogen, trifluoromethyl, C1WITH4-alkyl, cyano-, nitro-group, WITH1WITH4-alkoxy, phenoxy, triple-substituents selected from halogen, trifloromethyl, ceanography, a four-substituents selected from fluorine, trifloromethyl, ceanography, or W pyrimidinyl, once substituted by halogen, C1WITH4the alkyl(possibly substituted with halogen);11WITH4-alkyl, or chinoline, or halogencontaining associated with A with the help of one of the ring carbon atoms;
A is oxygen or S(O)nwhere n is 0,1 or 2, provided that when W 5-triptorelin-2-yl, A is different from the oxygen.Priority signs:
17.04.86 when W all values of pyridyl, in addition to substituted N-oxide group, all values of pyrimidinyl, A is oxygen.23.12.86 AND S(O)n, n 0, 1, 2.
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
FIELD: organic chemistry, herbicides, agriculture.
SUBSTANCE: invention describes a synergistic composition of herbicides comprising components (A) and (B) wherein (A) represents herbicide taken among the group of the formula (I):
wherein R1 means (C1-C4)-alkyl; R2 means (C1-C4)-alkyl; R3 means hydrogen atom; X and Y mean (C1-C4)-alkoxy-group; (B) represents one or two herbicides taken among the group of compounds or their acceptable forms: alachlor, metolachlor, acetochlor, dimetenamide, atrazine, cyanasin, metribusin, fluthiamide, nicosulfuron, rimsulfuron, primisulfuron, pendimetalin, sulcotrion, dicamba, mesotrion, isoxachlortol, metosulam, anilofos, fenoxaprop-ethyl, setoxydim, diclofop-methyl, MCPA, bromoxynil, pyridat, clopyralid, iodosulfuron-methyl, ethoxysulfuron, amidosulfuron, gluphosinat-amminium, isopropylammonium-glyphosate, imasetapir wherein components (A) and (B) are taken in the effective doses. Also, invention describes a method for control of weeds by using above indicated herbicide composition. Invention provides the development of the synergistic herbicide composition eliciting high activity.
EFFECT: improved method for control, valuable properties of composition.
6 cl, 26 tbl, 3 ex
FIELD: organic synthesis.
SUBSTANCE: invention provides substituted methyl-N-amidooxamoyl-N-phenyl-D,L-alaninates having general formula I:
where R1 and R2 represent C1-C4-alkyl, R3 and R4 either represent H, C1-C6-alkyl or form together group -(CH3)2-X-(CH2)2- wherein X is O or CH2. Compounds exhibit fungicide activity and can be used to prevent and treat plant diseases.
EFFECT: increased choice of fungicides.
5 cl, 1 tbl, 11 ex
FIELD: organic chemistry, chemical technology, fungicides.
SUBSTANCE: invention describes substituted 1-(pyridinyl-3)-2-phenoxyethanols-1 of the general formula (I):
wherein R1 means alkyl, cycloalkyl, substituted or unsubstituted phenyl; R2 and R3 mean hydrogen or halogen atom, These compounds are prepared by interaction of oxiranes of the formula (II) with phenols of the formula (III) in the presence of a base at 100-150oC. Also, invention describes a fungicide composition based on compounds said. Invention provides preparing compounds that are effective against harmful fungi.
EFFECT: improved preparing method, valuable properties of compounds.
4 cl, 1 tbl, 7 ex
FIELD: plant protection.
SUBSTANCE: invention provides composition comprising 24-36% 2,4-dichlorophenoxyacetic acid ethylhexyl ester, 3-6% 3,6-dichloropyridine-2-carboxylic acid dimethyl-C12-C14-alkylammonium salt, 10-15% oxyethylated alkylphenols or higher fatty acids, and aromatic hydrocarbons (to 100%) at weight ratio of the first component to the second (80-90):(10-20).
EFFECT: increased stability of preparation an negative temperatures and upon long-time storage.
2 cl, 2 tbl, 9 ex