RU2044723C1 - Derivatives of acrylic acid - Google Patents

Abstract

FIELD: organic chemistry, substituted benzoylcarboxylic acids. SUBSTANCE: product: compound of the formula (I) (X-Y-Z)O₆H₂-C(C(O)OCH₃) (double bond) CH-OCH₃ where X hydrogen, fluorine, MeO, chlorine, bromine, (C₁-C₆)-alkyl; Ph(C₁-C₄)-alkyl; CH₂ (double bond)CH-; Ph-CH(double bond)CH-; NC-(C₁-C₃)-alkyl-O-C(O)-CH(double bond)CH-; Ph-CH₂CH(double bond)CH-; CH₃-C(O)-CH(double bond)CH-; furylethenyl; benzthiazolylethenyl; Ph-C(triple bond)C-; t-By-C(triple bond)C-; phenyl; (C₁-C₆)-alkyl-O-; CH₂(double bond)CH-CH(O)-; PhCH(double bond)CH-CH(O)-; PhCH₂O; PhO-; F-C₆H₄-O-; Cl-C₆H₄-O-; Br-C₆H₄-O-; HO-C₆H₄-O-; CH₃-C₆-H₄-O-; CF₃-CC₆H₄-O-; CH(O)-C₆H₄-O-; propenyl- or propargylhydroxyphenoxy; CH₃-C(O)C₆H₄-O-; methylsulfonylhydroxyphenoxy; Ph-C₆H₄-O-; PhO-C₆H₄-O-; NO₂-C₆H₄-O-; NH₂-C₆H₄-O-; HC(O)-NH-C₆H₄-O-; CH₃-C(O)-O-NH-C₆H₄-O-; C₁-C₆-alkyl-C₆H₄-O-; PhS-; phenylsulphinyl; F(C₁-C₆)-alkyl--O-C₆H₄-O-; pyridyloxy; trifluoromethylpyridyloxy; phenylsulfinyl; isobutyryloxy; naphthyloxy; Ph-C(O)-O-; t-Bu-Ph-C(O)-O-; HC(O)-; Ph-C(O)-; MeO-C₆H₄C(O)-; (C₁-C₃)-alkyl-O-C(O)-; cyclohexylhydroxycarbonyl; CH₂CH(double bond)CH-O-C(O)-; Ph-O-C(O)-; MeO-C₆H₄-O-C(O); NO₂; PhC(O)-NH-; furoylamino; N-thienylcarbonyl-N-methylamino-group; Y at ortho-, meta- or para-position relative to acrylate group H; F; Cl; Br; Me; Ph-CH(double bond)CH; NO_2/ ; Ph-O; Z hydrogen; if X and Z are at the neighboring position of phenyl ring then they form fused benzene ring nonobligatory substituted with phenyl, fused naphthalene ring, benzofuranyl ring or one of groups of the formula (II)

, (III)

, (IV)

Description

 The invention relates to derivatives of acrylic acid, useful in agriculture and, in particular, suitable for use as fungicides, insecticides or plant growth regulators.

(1) и его стереоизомеры, где Х, находящийся в орто-положении относительно акрилатной группы, представляет собой водород, фтор, хлор, бром, С₁-С₆-алкил, фенил (С₁-С₄)-алкил, в котором фенильная группа не обязательно может быть замещена фтором, хлором или метоксигруппой; трифторметил; бромметил, диметоксиметил, феноксиметил, не обязательно замещенный хлором; пиридилэтил; фуранилэтил; тиенилэтил; этоксикарбонилэтил; этенил, не обязательно замещенный фенилом, циано-С₁-С₃-алкоксикарбонилом, бензилоксикарбонилом, ацетилом, фурилом или бензтиазолилом, этинил, замещенный фенилом или третбутилом; фенил; С₁-С₆-алкокси; аллилокси, не обязательно замещенный фенилом; бензилокси, фенокси, не обязательно замещенный фтором, хлором, бромом, гидрокси, метилом, трифторметилом, формилом, С₁-С₆-алкокси, не обязательно замещенным фтором, пропенилокси, пропаргилокси, ацетокси, метилсульфонилокси, фенилом, фенокси, нитро, амино, формиламино или ацетиламино; фенилтио, фенилсульфинил; нафтилокси, пиридилокси, не обязательно замещенный трифторметилом, изобутирилокси, бензоилокси, не обязательно замещенный трет-бутилом, формилом, бензоил, не обязательно замещенный метокси, С₁-С₃-алкоксикарбонил; циклогексилоксикарбонил; аллилоксикарбонил; феноксикарбонил, замещенный метокси, нитро, бензоиламино, фуроиламино или N-тиенилкарбонил-N-метиламино;
Y, находящийся в орто-, мета- или пара-положении относительно акрилатной группы, представляет собой водород, фтор, хлор, бром, метил, фенилэтенил, нитро или фенокси;
Z представляет собой атом водорода или Х и Y, когда они находятся в соседних положениях фенильного кольца, вместе друг с другом образуют конденсированное бензольное кольцо, не обязательно замещенное фенилом, конденсированное нафталиновое кольцо, конденсированное бензофуранильное кольцо, конденсированное бензотиенильное кольцо, или группу

или

или группы Y и Z, когда они находятся в соседних положениях фенильного кольца, вместе друг с другом образуют конденсированное бензольное кольцо, за исключением того, что, когда Х представляет водород, Y не является водородом или пара-хлором.The invention provides a compound of general formula
Y

(1) and its stereoisomers, where X, which is in the ortho position relative to the acrylate group, is hydrogen, fluorine, chlorine, bromine, C ₁ -C ₆ alkyl, phenyl (C ₁ -C ₄ ) alkyl, in which the phenyl group may not necessarily be substituted with fluorine, chlorine or methoxy; trifluoromethyl; bromomethyl, dimethoxymethyl, phenoxymethyl, optionally substituted with chlorine; pyridylethyl; furanylethyl; thienylethyl; ethoxycarbonylethyl; ethenyl optionally substituted with phenyl, cyano-C ₁ -C ₃ alkoxycarbonyl, benzyloxycarbonyl, acetyl, furyl or benzthiazolyl, ethynyl substituted with phenyl or tert-butyl; phenyl; C ₁ -C ₆ alkoxy; allyloxy optionally substituted with phenyl; benzyloxy, phenoxy, optionally substituted with fluorine, chlorine, bromine, hydroxy, methyl, trifluoromethyl, formyl, C ₁ -C ₆ alkoxy, optionally substituted with fluorine, propenyloxy, propargyloxy, acetoxy, methylsulfonyloxy, phenyl, phenoxy, nitro, amino, formylamino or acetylamino; phenylthio, phenylsulfinyl; naphthyloxy, pyridyloxy, optionally substituted with trifluoromethyl, isobutyryloxy, benzoyloxy, optionally substituted with tert-butyl, formyl, benzoyl, optionally substituted with methoxy, C ₁ -C ₃ alkoxycarbonyl; cyclohexyloxycarbonyl; allyloxycarbonyl; phenoxycarbonyl substituted with methoxy, nitro, benzoylamino, furoylamino or N-thienylcarbonyl-N-methylamino;
Y located in the ortho, meta, or para position relative to the acrylate group, is hydrogen, fluoro, chloro, bromo, methyl, phenylethenyl, nitro or phenoxy;
Z represents a hydrogen atom or X and Y, when they are in adjacent positions of the phenyl ring, together with each other form a fused benzene ring, optionally substituted with phenyl, a fused naphthalene ring, a fused benzofuranyl ring, a fused benzothienyl ring, or a group

or

or groups Y and Z, when they are in adjacent positions of the phenyl ring, together form a fused benzene ring with each other, except that when X is hydrogen, Y is not hydrogen or para-chlorine.

 The compound contains at least one carbon-carbon double bond, and is sometimes prepared as mixtures of geometric isomers. However, these mixtures can be divided into individual isomers and the present invention covers similar isomers.

 Alkyl groups can be represented as straight chain or branched radicals, and examples are methyl, ethyl, propyl (n- or iso-propyl) and butyl (n-sec, iso- or tert-butyl).

(Соединение N 1 в приведенной ниже табл.1)
(ii)

(Соединение N 5 в приведенной ниже табл.1)
(iii)

OCH₃ (Соединение N 9 в приведенной ниже табл.1)
(iv)

(Соединение N 1 в приведенной ниже табл.2).As examples, compounds are provided:
(i)

(Compound N 1 in the following table 1)
(ii)

(Compound N 5 in the following table 1)
(iii)

OCH ₃ (Compound N 9 in the following table 1)
(iv)

(Compound N 1 in the following table.2).

OCH₃ (Соединение N 1 в приведенной ниже табл.4).(v)

OCH ₃ (Compound N 1 in the following table 4).

OCH₃

Приведенная ниже табл.3 охватывает соединения общей формулы:
Y

где группа R включает все группы R, приведенные в табл.2 для каждой из нижеследующих схем замещения на приведенном выше фенильном кольце. Акрилатная группа может иметь в каждом случае либо Е-геометрию, либо Z-геометрию.

Och ₃

The following table 3 covers the compounds of General formula:
Y

where the R group includes all the R groups shown in Table 2 for each of the following substitution patterns on the phenyl ring above. The acrylate group in each case can have either an E-geometry or a Z-geometry.

где группа R включает все группы R/ приведенные в табл.4/ для каждого из нижеследующих характеров замещения на приведенном выше фенильном кольце. В каждом случае акрилатная группа может иметь либо Е-геометрию/ либо Z-геометрию.Tab. 5 covers compounds of the general formula

where the R group includes all the R groups / shown in Table 4 / for each of the following substitution patterns on the phenyl ring above. In each case, the acrylate group may have either an E-geometry / or Z-geometry.

Table 6 shows the selected proton Nuclear Magnetic Resonance Spectroscopy data for some compounds / described in Table. 1-5 and characterized in them as oils. Chemical shift is measured in million dollars. relative to tetramethylsioane / a, deuterochloroform was used as a solvent. The following abbreviations are used:
br = wide (wide) t triplet (t)
s singlet (s) q quartet (sq.)
d doublet (d) m multiplet (m)
Hz = Hertz (Hz)
Compounds having the general formula (I) can be prepared from substituted benzenes of the general formula (IV) using the steps shown in Scheme 1. In the materials of Scheme 1, the radicals R ₁ and R ₂ represent methyl, X, Y and Z, have the following as defined above, L is a halogen atom (bromine or chlorine iodine) or a hydrogen atom, and M is a metal atom (e.g., a lithium atom) or a metal atom plus an associated halogen atom (e.g., MgI, MgBr or MgCl).

 Thus, compounds of general formula (I) can be prepared by treating ketoesters of general formula (II) with phosphorans of general formula (V) in a common solvent such as diethyl ether (see, for example, W. Steglich, G. Schramm, T. Anke, K Oberwinkler, European Patent No. 0044448, 4780).

 Ketoesters of the general formula (II) can be prepared by treating the metallized materials (III) with oxalate (VI) in a suitable solvent, such as diethyl ether or tetrahydrofuran. A preferred method often involves slowly adding a solution of metallized substances (III) to a stirred solution of excess oxalate (VI) (see, for example, L.M. Weinstock, R. B. Currie, A. V. Lowell, Synthetic Cummunications, 1981, II, 943 and references therein).

 Metallized substances (III) in which M MgI, MgBr or MgCl (Grignard reagents) can be obtained by standard methods from the corresponding aromatic halides (IV), where L I, Br or Cl, respectively. In the case of certain substituents X, Y and Z, metallized substances (III) in which M Li can be obtained by direct lithium substitution of compounds (IV), in which LH using a strong lithium base such as n-butyl lithium or lithium di -isopropylamide E (see, for example, HW Grehwend, HR Rodriguez, Organic Reactions, 1879, 26, 1).

 Compounds of general formula (IV) can be prepared by standard methods described in the chemical literature.

Альтернативные методы получения кетоэфиров общей формулы (II) описаны в химической литературе (см. например, D.C. Atkison, K.F. Godfrey, B. Meek, J. F. Saville, M. R. Stillings, J. Med. Chem. 1983, 26, 1353, D. Horne, J. Gandino, W. J. Thompson Tetrahedron Lett 1984, 25, 3529 и G.P. Axiotis, Tethrahedron Lett, 1981, 22, 1509).Scheme I

Alternative methods for the preparation of ketoesters of the general formula (II) are described in the chemical literature (see, for example, DC Atkison, KF Godfrey, B. Meek, JF Saville, MR Stillings, J. Med. Chem. 1983, 26, 1353, D. Horne, J. Gandino, WJ Thompson Tetrahedron Lett 1984, 25, 3529 and GP Axiotis, Tethrahedron Lett, 1981, 22, 1509).

Alternative methods for preparing the compounds of the invention having the general formula (I) are illustrated by the scheme. In Scheme II, the radicals R, R ₂ , X, Y, and Z have the above definitions.

Соединения общей формулы (I) могут быть получены обработкой фенилацетатов общей формулы (VII) основанием или эфиром муравьиной кислоты, таким как метилформиат или HCO₂R₁, где R₁ определен выше в подходящем растворителе. Если реакцию гасят веществом общей формулы R₂, где R₂ определен выше, а Q отщепляемая группа, такая как атом галогена, то могут быть получены соединения общей формулы (I).Scheme II:

Compounds of general formula (I) can be prepared by treating phenylacetates of general formula (VII) with a base or formic acid ester such as methyl formate or HCO ₂ R ₁ , where R _{1 is as} defined above in a suitable solvent. If the reaction is quenched with a substance of the general formula R ₂ , where R _{2 is} defined above and Q is a leaving group, such as a halogen atom, compounds of the general formula (I) can be obtained.

Compounds of general formula (I) in which R ₂ H can be converted to compounds (I) in which R _{2 is} not a hydrogen atom, sequential treatment with a base (e.g. potassium carbonate or sodium hydride) and a substance of general formula R ₂ Q where R ₂ and Q are as defined above, in a suitable solvent.

 Compounds of general formula (I) can be prepared from acetals of general formula (VIII), under basic or acidic conditions, in a suitable solvent and at suitable temperatures. An example of a suitable base is lithium diisopropylamide, and potassium sulfate is an example of a suitable acidic reagent (see T. Yamada, H. Hagiwara, H. Uda, J. of Chem. Soc, Chem. Commun, 1980, 838 and references therein) .

 Acetals of the general formula (VIII) can be prepared from phenylacetic acid esters having the general formula (VII) by treating the alkylsilyl-ketone-acetal derivatives of the compounds (VII) with trialkyl orthoformates in the presence of Lewis acid in a suitable solvent and at a suitable temperature (see, for example, R. Saigo, M. Osaki, T. Makaiyama, Chem. Lett, 1976, 769).

 Compounds of general formula (VII) can be prepared by standard methods described in the chemical literature.

 The metal compounds and complexes of the invention are active fungicides, especially in relation to the following diseases: Pyricularia oryzae in rice, Puccinia recondita, Puccinia stiiformis and other rusts on wheat, Puccinia hardci, Puccinia stiiformis and other rusts on barley and rusts on other crops, for example coffee, pears, apple trees, nuts, vegetables and ornamental plants. Eryziphe graminis (powdery mildew) on barley and wheat and other powdery mildew on various crops, such as Sphaerotheca macularis on hops, Sphaerotheca fuliginea on pumpkin (e.g. cucumbers), Podosphaera leucotricha on apple trees and Uncinula necatorthium on grapes. Rhynohosporium spp., Septoria spp. Pseudocercosporella herpotrichoides and Ganomannonyces graminis on cereals, Cercospora arachidicola and Cercosporidium personota on nuts and other species of Cercospora on other crops, such as sugar beets, bananas, soybeans and rice, other grapes, botrytis cinerea, sulfur cultures, Alternaria spp. on vegetables (for example, cucumbers), rape seed oilseed, apple trees, tomatoes and other crops, Venturia inaequnalis (scab on apple trees); Plasmopara viticola on the grape.

 Other downy mildew, such as Bremia lactucae on lettuce, Peronospora spp, on soybeans, tobacco, onions and other crops and Pseudoperonospora bunueli on hops and Pseudoperonospora cubensis on pumpkin, Phytophtora infestausph on potato and potato and strawberries, avocados, peppers, ornamental plants, tobacco, cocoa and other crops. Thanatephorus cucumeris on rice and other Rhizoctonia spp on various crops such as wheat and barley, vegetables, cotton and lawn grasses.

 Some of the compounds also exhibit a wide spectrum of activity against fungi in vitro. They are active against post-harvest fetal diseases (e.g. Penicillium digitatium and italicum and Prichoderma viride on oranges and Gloesporium musarum (on bananas).

 Some of the compounds can be used as seed dressing against Fusarium spp, Septoria spp, Fillectia spp (wheat smut), Rhizoctonia solouci on cotton and Pyricularia oryzae in rice.

 Compounds can move acropetally in plant tissues. In addition, the compounds may be volatile enough to be active in the vapor phase against fungi on the plant.

 The compounds may be suitable as industrial (as opposed to agricultural) fungicides, for example, to protect against the action of fungi on wood, hides, leather, and especially on colorful films.

 Some of the compounds exhibit herbicidal activity and, at an increased application rate, can be used to control weeds.

 Similarly, some compounds are active in regulating plant growth and can be used for this purpose at an appropriate application rate.

 The compounds can be used for fungicidal purposes per se, but it is more convenient to formulate them in the form of compositions containing a compound of general formula (I) as defined above, or a metal complex thereof, and optionally a carrier or diluent.

 The compounds can be used to control fungi by applying metal to the plants, seeds of plants or to the places of growth of plants or seeds, the compound or its complexes.

 Metal compounds and complexes can be applied in various ways.

 For example, they can be applied in the form of a composition or directly on the leaves of plants, or they can be applied to bushes or trees, to seeds or to another medium in which plants, bushes or trees are grown or planted, or they can be sprayed, sprayed or applied in the form of a cream or paste, in the form of vapors or in the form of granules with a slow release of the active substance on any part of the plant, bush and / or tree, for example on leaves, stems, branches or roots, or on the soil surrounding the roots or seeds in front of them draft, or to the soil generally, introduced into the water of the irrigated field or in hydroponic culture systems. The compounds can also be used for injection into plants or trees and sprayed onto vegetation using electrodynamic spraying methods or other low-volume application methods.

 The compounds are used for agricultural, field and horticultural purposes in the form of a composition. The type of composition used in any case is determined by the specific intended use.

 The compositions may be presented in the form of dusting powders or granules containing the active ingredient and a solid diluent, or a carrier, for example, fillers such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powder magnesia, fuller’s earth, gypsum, Hewitt’s earth, diatomite and alumina. Such granules can be in the form of preformed granules suitable for application to the soil without further processing. These granules can be prepared either by soaking the filler pellets with the active ingredient, or granulating a mixture of the active ingredient and the powder filler. Seed dressing compositions, for example, may contain a substance (e.g., mineral oil) that promotes the adhesion of the composition to seeds, in the alternative, the active ingredient can be formulated for seed treatment using an organic solvent (e.g., N-methyl-pyrrolidone or dimethylformamide )

 The compositions may also be in the form of dispersible powders, granules or grains containing a wetting agent to facilitate dispersion in liquids of the powder or grains, which may also contain fillers and suspending agents.

 Aqueous dispersions or emulsions can be prepared by dissolving the active ingredient in an organic solvent, optionally containing wetting, dispersing or emulsifying substances. Suitable organic solvents are ethylene chloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylenes, trichlorethylene, furfuryl alcohol, tetrahydrofurfuryl alcohol and glycol ethers (e.g. 2-ethoxyethanol and).

 Compositions intended for use by spraying may be in the form of aerosols, in which case the composition is contained in a container under pressure in the presence of a propellant, for example fluorotrichloromethane or dichlorodifluoromethane.

 The compounds can be mixed in a dry state with a pyrotechnic mixture to form a composition suitable for creating smoke containing compounds in confined spaces.

 The compounds may be used in microencapsulated form. They can also be formulated as biodegradable polymer formulations providing a slow, controlled release of the active substance.

 By including suitable additives, for example, additives to improve distribution, adhesion strength and rain resistance on treated surfaces, different compositions can be better adapted to different purposes.

 The compounds can be used in mixtures with fertilizers (for example, nitrogen, potassium or phosphorus fertilizers). Compositions containing only fertilizer granules comprising compounds, for example, coated with it, are preferred. Such granules usually contain up to 25 wt. connections. Therefore, a fertilizer composition is proposed comprising a compound of general formula (I) or a metal complex thereof.

 The compositions may also be presented as liquid preparations for use by immersion or spraying, which are usually aqueous dispersions or emulsions containing the active ingredient, in the presence of one or more surfactants, for example, a wetting, dispersing, emulsifying or suspending substance, or are sprayable formulations suitable for use in electrodynamic sprayers. These substances may be cationic, anionic or nonionic. Suitable cationic substances are quaternary ammonium compounds, for example cetyltrimethylammonium bromide.

 Suitable anionic substances are soaps, salts of aliphatic sulfuric acid monoesters, for example sodium lauryl sulfate, and salts of sulfated aromatic compounds (for example, sodium dodecylbenzenesulfonate, sodium, calcium or ammonium lignosulfonate, butylnaphthalene sulfonate and a mixture of diisopropyl and triisopropyl naphthalene).

 Suitable non-ionic substances are the condensation products of ethylene oxide with fatty alcohols, such as oleyl or cetyl alcohol, or with alkyl phenols, such as octyl or nonyl phenol and octyl cresol. Other non-ionic substances are partial esters based on long chain fatty acids and hexitanhydrides, condensation products of these partial esters with ethylene oxide and lecithins. Suitable suspending agents are hydrophilic colloids (e.g., polyvinylpyrrolidone and sodium carboxymethyl cellulose) and vegetable gums (e.g., Arabian gum and tragacanth).

 Compositions for use as aqueous dispersions or emulsions are usually supplied in the form of a concentrate containing a high proportion of active ingredients, and the concentrate must be diluted with water before use. These concentrates often must withstand storage for a long time and after such storage must allow dilution with water to obtain aqueous preparations that remain uniform for a time sufficient for their application by traditional and electrodynamic-spray equipment. Concentrates may typically contain up to 95%, more preferably 10-85%, for example 25-60% by weight of the active ingredients. These concentrates usually contain organic acids (for example, alkaryl or aryl sulfonic acids, such as xylene sulfonic acids or dodecylbenzenesulfonic acid), since the presence of such acids can increase the solubility of the active ingredients in polar solvents often used in concentrates. Concentrates usually also contain a high proportion of surfactants, so that sufficiently stable emulsions in water are obtained. After dilution to form aqueous preparations, they may contain various amounts of active ingredients depending on the purpose, but aqueous preparations containing from 0.0005 or 0.01 to 10% by weight of active ingredients may also be used.

 The compositions may also contain other compounds having biological activity, for example, compounds having similar or additional fungicidal activity, or compounds exhibiting herbicidal or insecticidal activity or plant growth regulating activity.

 Another fungicidal compound may be, for example, a compound capable of suppressing diseases of the ears of cereals (e.g. wheat) caused, for example, by Septoria, Gibberella and Helminthosporium spp. diseases that occur in seeds and soils, and downy and true powdery mildew on grapes, powdery mildew and steam on apple trees, etc. These fungicide mixtures may have a wider spectrum of activity than the compound of general formula (I) per se, in addition, another fungicide may have a synergistic effect on the fungicidal activity of the compound of general formula (I).

 Examples of other fungicidal compounds are carbendazim, benomyl, thiofanate methyl, thiabendazole, fuberidazole, etridazole, dichlorofluanide, cymoxanil, oxadixyl, ofuras, metalaxyl, furalaxyl, benalaxyl, fenolonolone, microfinolonolinolinolonolinolonolinolinolonolinolinolinolinolinolinolonolinolinolinolinolonolinolinolinolonolinolinolinolinolinolinolinolinolinolinolinolin 0151297, S 3308, pyrazophos, ethyrimol, ditalimphos, tridomorph, triforin, noarimyl, triazbutyl, guazatin, propicopazole, prochlorase, flutriafol, chlorotriafol, i.e. chemical substance 1 (1,2,4-triazol-1-yl) 2- (2,4-dichlorophenyl) hexan-2-ol, DPX H6573 (1 - ((bis-4-fluorophenyl) methyl silylmethyl) -1H-1,2,4-triazole-triadimefon, triadimenol, dichlorobutrazole, fenpropimorph, fenpropidin, triademorph, imizalil, fenfuram, carboxin, oxycarboxin, metfuroxam, dodemorph, BAS 454, blastidin, kasugamycin, indy , phthalide, probenazole, isoprothiolan, tricyclazole, pyroquilane, chlorobenzthiazone, neoasosin, polyoxin D, validamycin A, repronil, flutolanil, pencisuron, dicyclomesin, phenazin oxide, dimethyldithiophenoltitolazolitolitoltamtolazolitolitonolitonolitonolitonolitonolitolitonolitolitonolitolitonolitolit dimethyrim l, phenapanil, tolilofols-methyl, pyroxyfur, poliram, maneb, mancozeb, captafol, chlorothalonil, anilazine, tyram, captan, folpet, cineb, pronineb, sulfur, dinocap, binapacryl, nitrotal-isopropyl, dodin, fentynoc, dithianone, dithianon, fentin acetate, tecnazene, quintozene, dichloran, copper compounds such as copper oxychloride, copper sulfate and Bordeaux mixture, and organic mercury compounds such as 1- (2-cyano-2-methoxy-iminoacetyl) -3-ethylurea.

 The compounds of the general formula (I) can be mixed with soil, peat or another medium for locating the root system, for protecting plants from fungal diseases, the causative agents of which are located in seeds, soil or foliage.

 Suitable insecticides are pyrimicarb, dimethoate, demeton, -S-methyl, formotion, carbaryl, isoprocarb, HMS, VRMS, carbofuran, carbosulfan, diazinon, fenthion, phenytrotion, fentioat, chlorpyrifos, isoxathio, propafrosfinoprofroprofr, etocroprofros, monocoprotsfroprofrozoprotsfroprofrotsfroprofrozoprotsfroprofrozoprotsfroprofrozoprotsfroprofrozoprotsfroprofrotsfroprofros.

 A plant growth regulator may be a compound that regulates weed growth or seed cap formation, or selectively regulates the growth of less desirable plants (e.g. grasses).

Examples of suitable plant growth regulating compounds for use in conjunction with the compounds of the invention are giberellins (e.g. GA ₃ , GA ₄ or GA ₇ ), auxins (e.g. indoleacetic acid, indolbutic, naphthoxyacetic or naphthyloacetic acid), cytokinins (e.g. kinetin, diphenylurea, benzimidazole benzyladenine or benzylaminopurine), phenoxyacetic acids (e.g. 2,4-D or MCPA), substituted benzoic acids (e.g. triiodobenzoic acid), morphactins (e.g. chlorofluorecol), maleic hydrazine, lyphosphate, glyphosine, long chain fatty acids and acids, degulac, paclobutrazole, flurprimidol, fluoridamide, mefluidide, substituted quaternary ammonium and phosphonium compounds (e.g. chloromequate, chlorfonium or mepiquatchloride), ethephon, carbetamide, methyl-aniside-aniside-3,6-aniside , asulam, abscisic acid, isopyrimol, 1- (4-chlorophenyl) -4,6-dimethyl-2-oxo-1,2-dihydro-pyridin-3-carboxylic acid, hydroxybenzonitriles (e.g. bromoxynil), diphenzenquat, benzoylprop- ethyl 3,6-dichloropicolinic acid, paclobutrazole, fenpentesol, inabenf d, and triapentonol teknazen.

 The following examples illustrate the invention. In the examples, the term “ether” refers to diethyl ether, magnesium sulfate is used to dry solutions and reactions involving water-sensitive intermediates are carried out in a nitrogen atmosphere. Unless otherwise indicated, chromatography is performed using silica gel as the stationary phase. Where the data of IR and NMR spectroscopy are given are selective, no attempt was made to indicate each absorption line. The following abbreviations were used: THF tetrahydrofuran (THF) S singlet (s); DMF N, N-dimethylformamide (DMF) d doublet (d); GC gas chromatography t triplet (t); MS mass spectrum m multiplet (m).

 PRI me R 1. An example illustrates the preparation of 2 E, 1 "Z-methyl-3-methoxy-2- [2 '- (2" -phenylethenyl) phenyl] propenoate (compound No. 5 in table 1).

 Potassium tert-butylate (5.30 g) is added in one portion to a vigorously stirred suspension of benzyl triphenylphosphonium chloride (21.02 g) in dry ether (250 ml). After 25 minutes, the resulting orange mixture was treated with a solution of 2-bromo-benzaldehyde (5.00 g) in dry ether (50 ml) and the mixture lightens in color. After another hour, the mixture was poured into water and extracted with ether. The extracts are washed with water, dried, concentrated under reduced pressure and chromatographed using dichloromethane as an eluent to give 1-phenyl-2- (2-bromophenyl) ethylene (5.95 g, 85% yield), an almost colorless oil as a mixture of 5: 1 Z: E-isomers (according to GC / MS).

A solution of Grignard reagent, obtained from part of a mixture of isomers of the above 1-phenyl-2- (2-bromophenyl) ethylene (5.58 g) and magnesium in dry THF (20 ml), is added dropwise over 30 min to a stirred solution of dimethyl oxalate ( 5.06 g) in dry THF (40 mL) cooled to -15 ° ^C. The resulting mixture was stirred at -15 ^{° C} for 30 min, then at room temperature for 1 hour, then poured into dilute hydrochloric acid and extracted with ether . The extracts are washed with water, dried, concentrated under reduced pressure, then chromatographed twice with [(i) 30% ether in gasoline: (ii) 20% hexane in dichloromethane] to give isomeric pure Z-methyl-2- (2 ' -pheniethenyl) phenylglyoxalate (1.76 g yield 31%) as a yellow oil NMR (CDCl ₃₎ : δ 3.87 (3H, s), 6.78 (center of 2 doublets each, 1H, J 12 Hz) ppm ^-1 .

Potassium tert-butylate (2.00 g) is added in one portion to a stirred suspension of (methoxymethyl) triphenylphosphonium chloride (6.78 g) in dry ether (80 ml). After 25 minutes, the resulting red suspension was treated with a solution of Z-methyl 2- (2'-phenylenethenyl) phenylglyoxalate (1.76 g) in dry ether (20 ml), and the color brightened. After 1.5 hours, the reaction mixture was poured into water and extracted with ether. The extracts are washed with water, dried, passed through a short column of silica gel using dichloromethane, then carefully chromatographed using 30% ether in gasoline as eluent to obtain the target compound (0.46 g, 24% yield) as an oil, IR -spectrum (film): 1715, 1635 cm ^-1 , ¹ NMR (CDCl ₃ ): δ 3.62 (3H, s), 3.73 (3H, s), 6.48 (2H, s), 7, 50 (1H, s) mn ^-1.

 Example 2. This example illustrates the preparation of 2E, 1 "E- and 2Z 1" E-methyl-3-methoxy-2- [2- (2 "-phenylethenyl) phenyl] propenoate (compounds NN 1 and 2 in table 1).

A solution of 2-bromobenzaldehyde (18.50 g) in dry ether (20 ml) was added dropwise to a stirred solution of benzyl magnesium chloride (obtained from benzyl chloride (12.64 g) and magnesium (2.68 g) in dry ether (120 ml), moreover a thick precipitate forms during the addition.The mixture is stirred for 1 h at room temperature, then poured into water, acidified with 2M hydrochloric acid and extracted with ether. The mixture is stirred for 1 h at room temperature, then poured into water, acidified with 2M hydrochloric acid and extracted with ether. stirred for 1 h at room temperature, then poured into water, acidified with 2M hydrochloric acid and extracted with ether.The extracts are washed with water, dried, concentrated and chromatographed using dichloromethane-gasoline (1: 1) as eluent to obtain 1- (2-bromophenyl) -2- phenylethan-1-ol (10.95 g 40%) as a white solid, melting point 84-85 ^about C.

A stirred mixture of 1- (2-bromo (phenyl) -2-phenylethane-1-ol (15.50 g) and orthophosphoric acid (150 ml) was heated at 170 ° ^C for 1 hour and then poured into ice water and extracted with ether. The extracts were washed with water, dried and concentrated to give the crude product as an orange oil (14.29 g). Evaporative distillation (0.3 torr, the temperature in the oven 140 ° ^C) gives E-1-phenyl-2- ( 2-bromophenyl) ethylene (12.53 g, 86% yield) as a pale yellow oil with a purity of 97% according to gas chromatography.

A solution of Grignard reagent obtained from E-1-phenyl-2- (2-bromophenyl) ethylene (8.56 g), magnesium (0.96 g) in dry tetrahydrofuran (20 ml) is added dropwise over 30 minutes to the stirred a solution of dimethyl oxalate (7.76 g) in dry tetrahydrofuran (70 mL) cooled to -15 ° ^C. The resulting mixture was stirred at -15 ^{° C} for 30 min, then at room temperature for 1 hour, then poured into dilute hydrochloric acid and extracted with ether. The extracts were washed with water, dried and concentrated to give the crude product as a yellow oil (17.22 g). Purification by column chromatography using dichloromethane and petrol (1: 1) as eluent, and subsequent evaporative distillation (0.07 torr, oven temperature 170 ^{° C)} gave E-methyl-2- (2'-phenylethenyl) phenylglyoxalates (2 , 01 g, yield 23%) as a yellow oil, pure by gas chromatography, NMR (CDCl ₃ ): δ 3.78 (3H, s), 6.88 (center of 2 doublets, each 1H, J 1, 6Hz) mn ^-1.

Potassium tert-butylate (2.19 g) is added in one portion to a stirred suspension of (methoxymethyl) triphenylphosphonium chloride (7.41 g) in dry ether (100 ml). After 25 minutes, the resulting red suspension was treated with a solution of E-methyl-2- (2-phenylenethenyl) phenylhexglyoxalate (1.92 g) in dry ether (20 ml), the color being clear. After 15 minutes, the mixture was poured into water and extracted with ether. The extracts are washed with water, dried and chromatographed using 30% ether in gasoline as an eluent to obtain the (i) 2E 1 "E-isomer of the target compound, eluting first, as a pale yellow oil (1.06 g, yield 50 %), which crystallizes upon standing, giving a white solid, melting point 103-104 ^о С. An analytical sample recrystallized from ether-gasoline has a melting point 107-108 ^о С, IR-spectrum: 1700 1630 cm ^-1 НМР (CDCl _3): δ 3,68 (3H, s), 3.80 (3H, s), 7.06 (2H, s), 7.63 (1H, s) mn ^-1 and (ii) 2Z, 1 "E-isomer of the target compound eluted in second, in the form of a viscous oil (0.260 g, 12% yield, IR spectrum (film) 1710, 1625 cm ^{-1 1} NMR (CDCl ₃ ) δ 3.65 (3H, s), 3.92 (3H, s), 6.57 (1H, s), 6.99 and 7.24 (each 1H, d, J 1,6 Hz) ppm ^-1.

PRI me R 3. An example is illustrated by the preparation of E-methyl 2- (2-) chloro-6-fluorophenyl) -3-methoxypropenoate (compound No. 16 in table 1). A mixture of methyl (2-chloro-6-fluorophenyl) acetate (5.20 g and methyl formate (31.4 ml in dry) in dimethylformamide (40 ml) is added dropwise to a stirred suspension of sodium hydride (1.23 g) in dry DMF ( 40 ml) at 0 to 5 ^o C. There intensive gas evolution. The reaction mixture was stirred at room temperature for 3.5 hours, then poured into a mixture of ice and aqueous sodium carbonate and washed with ether. The resulting aqueous mixture was acidified with concentrated hydrochloric acid and extracted with ether. The extracts are washed with water, draining concentrated and concentrated to give methyl 2- (2-chloro-5-fluorophenyl) -3-hydroxypropenoate (3.44 g) as a white solid.

A stirred solution of this crude product in dry DMF (30 ml) was successively treated with potassium carbonate (4.11 g) and dimethyl sulfate (1.34 ml). The resulting mixture was stirred for 1 h at room temperature, poured into water and extracted with ether. The extracts were washed with water, dried and concentrated to give the title compound (2.91 g) as a white solid, mp 77-78 ° ^C. Crystallization from petrol (60-80 ° ^C) gave colorless crystals (2.61 g, 52% yield from methyl (2-chloro-6-ftorfnil) -acetate), melting point 79-80 ° ^C.

NMR (CDCl ₃ ): δ 3.69 (3H, s); 3.84 (3H, s); 7.62 (1H, s) million.

 PRI me R 4. An example is illustrated by the preparation of E-methyl 2- (2-phenoxy) phenyl-3-methoxyacrylate (compound N 1 in table 2).

Potassium tert-butoxide (5.6 g) was added to a stirred solution of diphenyl ether (12.3 g) in dry ether (150 ml) at -70 ^C. The resulting mixture was stirred at this temperature for 15 minutes, then added N-butyllithium ( 30.5 ml of a 1.62 M solution in hexane) to give a red-brown suspension, which was allowed to warm to room temperature. This mixture was added to a stirred suspension of dimethyl oxalate (11.8 g) in ether (250 ml) at -10 over 20 minutes, after which it was allowed to warm to room temperature. After 30 minutes, the mixture was poured into water and extracted with ether. The combined extracts were washed with water, dried, then concentrated to give a red oil (14.21 g). Chromatography using 20% ether in gasoline as an eluent gives methyl 2-phenoxybenzoyl formate (2.23 g) as a yellow oil.

Potassium tert-butylate (2.64 g) was added to a vigorously stirred suspension of (methoxymethyl) triphenylphosphonium chloride (8.93 g) in dry ether (100 ml). After 20 minutes, the resulting red suspension was treated with a solution of methyl 2-phenoxybenzoyl formate (2.23 g) in dry ether (20 ml), the color being clear. After 15 minutes, the mixture was poured into water and extracted with ether. The combined extracts were washed with water, dried and concentrated to give a yellow oil (7.30 g). Chromatography using dichloromethane as an eluent afforded the title compound (0.61 g) as a colorless oil. IR (film) 1710, 1835 cm ^-1 , NMR (CDCl ₃ ): δ 3.60 (3H, s); 3.75 (3H, s); 7.47 (1H, s) million.

PRI me R 5. An example describes an alternative method of obtaining E-methyl-2- (2-phenoxy) phenyl-3-methoxypropenoate (compound N 1 in table 2). A 1M solution of borane-tetrahydrofuran complex (30 ml) was added dropwise to a stirred solution of 2-phenoxybenzoic acid (5.35 g) in dry THF (50 mL) cooled ^to 0 ° C (effervescence). After addition the mixture was stirred for 15 min at ⁰ ° C then 1.5 hours at room temperature. It is poured into water and extracted with ether. The extracts were washed successively with water, aqueous sodium bicarbonate, aqueous sodium carbonate, then dried and concentrated under reduced pressure to obtain 2-phenoxybenzyl alcohol (4.83 g of 97% as a colorless oil, to a solution of 2-phenoxybenzyl alcohol (4.80 d) in dry dichloromethane (50 ml), the resulting mixture was stirred for 2 hours at room temperature, then washed with water, aqueous sodium bicarbonate and aqueous sodium chloride, dried and concentrated under reduced pressure to obtain 2-phenoxybenzyl chloride (4.87 g 93%) in the form of a demon colored oil.

Carbon dioxide was bubbled into a solution of 2-fenoksibenzilmagniyhlorida (from 2-fenoksibenzilhlorida (4.80 g) and magnesium turnings (0.64 g) in dry ether (15 mL) cooled ^to 0 ° C. To improve the solubility of dry THF was added. After the cessation of the exothermic reaction through the mixture of carbon dioxide is no longer passed and the mixture allow to warm to room temperature.

The mixture was poured into water, washed with ether, then treated with hydrochloric acid and extracted with ether. The extracts were washed with water, dried and concentrated under reduced pressure to give 2-fenoksifeniluksusnoy acid (3.0 6 g 61%) as a solid, melting point 82-85 ° ^C. The analytical sample, recrystallized from ether / petrol, had a melting point 85-86 ^about S.

 A solution of 2-phenoxyphenylacetic acid (2.75 g) in dry methanol (30 ml) containing concentrated sulfuric acid (0.3 ml) was heated under reflux for 2 hours and then allowed to cool, poured into water and extracted with ether . The extracts were washed with water, dried and concentrated under reduced pressure to obtain methyl 2-phenoxyphenyl acetate (2.65 g 91%) as a pale yellow oil.

 This ester is converted in 2 stages into the target compound according to the procedure described in example 3, that is, by reaction of sodium hydride and methyl formate, and processing the resulting enol with potassium carbonate and dimethyl sulfate (overall yield 65%).

PRI me R 6. An example illustrates the preparation of E-methyl-2- (2-benzyl-hydroxy) phenyl-3-methoxyacrylate (compound N 145 in table 2). A mixture of methyl formate (24.4 ml) and methyl o- (benzyloxy) phenyl acetate (5.10 g) in dry DMF (30 ml) was added dropwise to a stirred suspension of sodium hydride (0.95 g) in dry DMF (30 ml) at 0 to 5 ^° C vigorous gas evolution is observed. The reaction mixture was stirred for 3.5 hours at room temperature, then poured into a mixture of ice and aqueous sodium carbonate. The resulting aqueous solution was washed with ether, then acidified with concentrated hydrochloric acid and extracted with ether. The extracts were washed with water, dried and concentrated to give methyl 2- (2-benzyloxy) phenyl-3-hydroxyacrylate (4.38 g) as a yellow oil.

Potassium carbonate (4.26 g) and dimethyl sulfate (1.38 g) are successively added to a stirred solution of methyl 2- (2-benzyloxy) phenyl-3-hydroxyacrylate (4.38 g) in dry DMF (40 ml). After 1 h at room temperature, the reaction mixture was poured into water and extracted with ether. The extracts were washed with water, dried, concentrated and triturated with benzyl, to give the title compound (3.38 g, 57% yield from methyl o- (benzyloxy) phenylacetate) as a white solid, mp 74-75 ° ^C. Crystallization of the entire sample from methanol gave colorless crystals (2.35 g), melting point 76-77 ^{° C, 1} NYAMR (CDCl _3): δ 3,63 (3H, s); 3.76 (3H, s); 5.05 (2H, s); 7.49 (1H, s) mn ^-1.

 PRI me R 7. An example describes the preparation of E-methyl-2-2- (4-methyl-phenoxy) phenyl-3-methoxypropenoate (compound N 13 in table 2).

4-methylphenol (8.40 g) was added to a stirred methanol solution of sodium methylate (from sodium (1.78 g) and dry methanol (50 ml)). After 0.5 h, methanol was removed under reduced pressure and the mixture was stirred with 4-methylphenol (4.20 g), 2-chloro-acetophenol (6.00 g) and a catalytic amount of copper bronze. The resulting mixture was heated at ¹³⁵ ° C for 1.5 hours, then allowed to cool, diluted with water and extracted with ether. The extracts were washed successively with aqueous sodium hydroxide and aqueous sodium chloride, then dried and concentrated under reduced pressure to obtain a dark oil (8.20 g). This crude product was purified by evaporative distillation (130-135 ^C at 0.02 torr) to yield 2- (4-methylphenoxy) atsetofenina (7.29 g 83%) as a colorless liquid. IR spectrum (film) 1670 cm ^-1 .

A solution of boron trifluoride etherate (18.06 g) and 2- (4-methylphenoxy) acetophenone (7.29 g) in dry methanol (8.3 ml) was added to an ice-cooled suspension of lead tetraacetate (14.97 g) in dry ether (70 ml). The resulting mixture was stirred at room temperature for 18 hours, then poured into water and extracted with ether. The extracts were washed successively with water and aqueous sodium bicarbonate, dried and concentrated under reduced pressure to obtain a red oil (7.35 g) containing methyl 2- (4-methylphenoxy) phenylacetate and the starting acetophenone (4: 1 according to gas chromatography). The mixture was treated with aqueous potassium hydroxide and the resulting substituted phenylacetic acid was purified by acid-base extraction and re-esterified in acid methanol to give methyl 2- (4-methylphenoxy) phenylacetate (5.00 g) as a thick oil, IR spectrum (film) ) 1730 cm ^-1 .

This ester is converted in 2 stages to the target compound according to the procedure described in examples 3 and 6, i.e. by reaction with sodium hydride and methyl formate, and processing the resulting enol with potassium carbonate and dimethyl sulfate (overall yield 32%). The product after recrystallization from methanol has a melting point of 80-81 ^about C, IR spectrum (nujol) 1690, 1620 cm ^-1 , ¹ NMR (CDCl ₃ ): δ 2.30 (3H, s); 3.62 (3H, s); 3.77 (3H, s); 7.50 (11H, s) mn ^-1.

 Example 8. An example describes the preparation of E- and Z-methyl-3-methoxy-2- (2-phenylethyl) phenylpropenoate (compounds NN 1 and 76) in Table 4. Trifluoroacetic acid (46 ml) is added in a single portion in a stirred mixture of 1- (2-bromophenyl) 2-phenyl-ethan-1-ol (16.51 g), which was obtained by the method of example 3), and triethylsilane (13, 80 g).

 The resulting mixture was stirred at room temperature for 22 hours, then the excess trifluoroacetic acid was removed under reduced pressure. The residue was dissolved in ether and washed successively with water, aqueous sodium bicarbonate and water, then dried, concentrated under reduced pressure and chromatographed using 10% dichloromethane in gasoline as an eluent to give 1- (2-bromophenyl) -2-phenylethane ( 8.02 g 51%) as a colorless oil.

This sample of 1- (2-bromophenyl) -2-phenylethane is converted in 2 stages to the target compounds according to the method of examples 1 and 3, i.e. by the reaction of the magnesium derivative with dimethyl oxalate, and processing the resulting keto ester with methoxymethylene triphenylphosphorane. The E-isomer, eluted first in 30% ether in gasoline, is an oil, IR (film) 1705 and 1630 cm ^-1 , ¹ NMR (CDCl ₃ ): δ 2.79 (4H, s) ; 3.69 (3H, s); 3.79 (3H, s); 7.59 (1H, s) mn ^-1.

The Z-isomer eluted by the second is also an oil, IR (film) 1715, 1695 and 1630 cm ^-1 . ¹ NMR (CDCl ₃ ): δ 2.84 (4H, s); 3.68 (3H, s); 3.84 (3H, s); 6.24 (1H, s) mn ^-1.

 Example 9. The example illustrates the preparation of 2E, 1 "E and 2Z, 1'E-methyl 2-2 '- (2" - [2 "' - phenyl] ethenyl) phenyl] -3-methoxypropenoate (compounds NN 25 and 36 in table 1).

A mixture of 2-bromobenzyl bromide (12.10 g) and trimethylphosphite (8.56 ml) was stirred in a flask connected through a condenser head to a condenser. The reaction mixture was heated for 1 hour at ¹¹⁰ ° C (more trimethylphosphite is then added (5 mm), then 2.5 hours at 130 ^{° C,} wherein in the head of a distillation apparatus temperature maintained below 40 ^C. The mixture was allowed to cool, and the volatile fraction is removed under reduced pressure, leaving an almost colorless liquid (21.65 g). Evaporative distillation of a portion of this liquid (18.45 g) gives dimethyl 2-bromobenzylphosphonate (7.92 g 65%) as a colorless liquid, collected at 175-180 ^о С (0.15 mbar) with a purity of 78% according to gas chromatography. eskaya sample purified by flash chromatography using as eluent ethyl acetate: petrol (60-80 ° ^C) (2: 1), ¹ shows NYAMR (CDCl _3): δ 3,43 (2H, d, J 23 Hz) 3, 72 (D, J 11 Hz) ppm

A solution of dimethyl 2-bromobenzylphosphonate (10.35 g) in dry DMF (50 ml) was added dropwise at room temperature to a stirred suspension of sodium hydride (0.979 g) in dry DMF (100 ml) (vigorous gas evolution). After 20 minutes, a solution of furfural (3.56 g) in dry DMF (50 ml) was added (exothermic reaction), and the resulting mixture was stirred for 4 hours at room temperature, then diluted with water and extracted with ether. The extracts were washed with water, treated with magnesium sulphate and charcoal, filtered, concentrated under reduced pressure and chromatographed, using petrol (40-60 ° ^C) as eluant to give E-1 (2-furyl) -2- (2-bromophenyl) ethylene (3.755 g) of a pale yellow liquid (containing about 6% of the corresponding Z-isomer according to gas chromatography).

This ethylene is converted in 2 stages to the target compound by the reaction of a magnesium derivative with dimethyl oxalate and treatment of the obtained ketoester with methoxymethylene triphenylphosphorane. The E, E-isomer, eluted first in 30% ether in gasoline, is an oil; IR spectrum (film) 1715 and 1637 cm ¹ NMR (CDCl ₃ ): δ 3.68 (3H, s); 3.81 (3H, s); 6.31 (1H, d, J 3.5 Hz); 6.40 (1 H, doublet of 3.5 and 2 Hz); 6.83 and 6.98 (each 1H; d J 16 Hz); 7.63 (1H, s) ppm ^-1 Z, E-isomer is a solid, melting point 107.5-110 ^о С, IR spectrum (Nujol) 1717 and 1625 cm, НМР (CDCl ₃ ): δ 3, 65 (3H, s); 3.93 (3H, s); 6.33 (1H, d, J 3.5 Hz); 6.40 (1H, dd, 3.5 and 2 Hz); 6.56 (1H, s); 6.82 and 7.10 (each 1H, d, J 16 Hz) ppm ^-1.

 PRI me R 10. An emulsifiable concentrate is prepared by mixing the ingredients and mixing the mixture until the components are dissolved.

The compound of example 4, 10% Ethylene chloride, 40 Calcium dodecylbenzenesulfate 5 "Lubrol" L 10 "Aromazole" H 35
PRI me R 11. The composition in the form of grains, easily dispersible in a liquid, for example in water, is prepared with joint grinding of the first three ingredients in the presence of added water, followed by mixing in sodium acetate. The resulting mixture is dried and passed through a sieve, size 44-100 mesh (British standard) to obtain grains of the desired size.

The compound of example 2, 50% "Dispersol" T, 25 "Lubrol" APN 5, 1.5 Sodium acetate, 23.5
PRI me R 12. The ingredients are co-milled to obtain a powder preparation, easily dispersible in liquids:
The compound of example 4, 45% "Dispersol" T, 5 "Lissapol" NX, 0.5 "Cellophas" B 600, 2 Sodium acetate, 47.5
PRI me R 13. The active ingredient is dissolved in a solvent and the resulting liquid is sprayed onto kaolin clay granules. Then the solvent is allowed to evaporate to obtain a granular composition.

The compound of example 2, 5%
Granules of kaolin clay, 95
PRI me R 14. A composition suitable for use as a mordant for seeds, prepared by mixing the three ingredients.

The compound of example 4, 50% Mineral oil, 2 Kaolin clay, 48
PRI me R 15. A dusting powder is prepared by mixing the active ingredient with talc.

The compound of example 2, 5% Talc, 95
PRI me R 16. Col-composition is prepared by grinding in a mill the components indicated below, with the subsequent formation of an aqueous suspension of a milled mixture with water.

The compound of example 5, 40% Dispersol T, 10 Lubrol APN 5, 1 Water The rest
PRI me R 17. A dispersible powder preparation is prepared by mixing the following ingredients, followed by grinding the mixture until they are thoroughly mixed.

The compound of example 2, 25% Aerosol OT / B, 2 Dispersol A.S. 5 Kaolin clay, 28 Silica, 40
PRI me R 18. An example illustrates the preparation of a dispersible powder composition. The ingredients are mixed and the mixture is then milled in a grinding mill.

The compound of example 4, 25% Terminal BX, 1 Dispersol T, 5 Polyvinylpyrrolidone, 10 Silica, 25 Kaolin clay, 34
PRI me R 19. The following ingredients are made into a dispersible powder by mixing, followed by grinding of the ingredients.

The compound of example 2, 25% Aerosol OT / B, 2 Dispersol A, 5 Kaolin clay, 68
In examples 10-19, the proportions of the ingredients are indicated by weight.

 The compounds shown in tables 1-5, make up in a similar manner similar to that shown in examples 10-19.

 Here is an explanation of the compositions or substances represented by the various trademarks and trade names mentioned.

Lubrol L nonylphenol condensate (1 mol) with ethylene oxide (13 mmol);
"Aromazole" N a solvent mixture of alkylbenzenes;
Dispersol T and AC mixture of sodium sulfate and formaldehyde condensate with sodium naphthalenesulfonate;
Lubrol APN5 nonylphenol condensate (1 mol) with naphthalene oxide (5.5 mol);
Sellofas B 600 a thickener based on sodium carboxymethyl cellulose;
Lissapol NX nonylphenol condensate (1 mol) with ethylene oxide (8 mmol);
Aerosol OT / B dioctyl sodium sulfosuccinate;
"Terminal" BX sodium alkylnaphthalene sulfonate.

PRI me R 20. The compounds are tested against a number of fungal diseases of plant foliage. Method used: plants are grown in compost soil for pots of the John Innes type (N 1 or 2) in mini-pots with a diameter of 4 cm. The test compounds were converted into a preparative form either by grinding in a ball mill with an aqueous "dispersol" T, or in the form of a solution in acetone or a mixture of acetone / ethanol, which was diluted to the desired concentration immediately before use. In the case of leaf cover diseases, compositions (100 million active ingredient) are used to spray the leaves and applied to the roots of the plant in the soil. Spraying is done to maximize retention of the composition on the leaves and roots to irrigation to a final concentration equivalent to approximately 40 million ^-1 of active ingredient in dry soil. When sprayed onto cereals, tween-20 is added to obtain a final concentration of 0.05%
In most tests, the compound is introduced into the soil (root treatment) and applied to the leaves (by spraying) a day or two before the plants are inoculated with pathogens. An exception is the Erysiphe graminis test when plants are inoculated 24 hours before treatment. Deciduous pathogens are applied by spraying in the form of a suspension of pores on the leaves of experimental plants. After inoculation, the plants are placed in a suitable medium to ensure the development of infection, and then incubated until the disease manifests itself at a level suitable for evaluation. The period between inoculation and assessment ranges from four to fourteen days, depending on the disease and the environment.

The degree of suppression of the development of the disease is recorded on the following scale:
4 disease is absent; 3 tears 5% of the disease on untreated plants; 2 6-25% of the disease on untreated plants; 1 26-59% of the disease in untreated plants; 0 60-100% of the disease in untreated plants.

 The results are shown in table 7-11.

PRI me R 21. The test compounds were converted into preparative form or by grinding in a ball mill with an aqueous "Dispersol" T or in the form of a solution in acetone or in a mixture of acetone / ethanol. Then they were diluted with water to a degree of 100 ppm / and quantities / equal to 2/5 ml / were placed in Petri dishes. Then they were further diluted to 25 ppm (active ingredient) with potato-dextrose agar. The cups were inoculated with fungal pathogens (the list is given below (with the abbreviated designation / and the full Latin name on the left) / using a suspension of spores / or mycelial plugs. Then they were incubated at a temperature of 19-20 ° ^C / and / 2 days later / growth were evaluated using evaluation indices 0/2 and 4. The results are given in Table 2 / where indicated:
0 lack of inhibition of fungal growth;
2 partial inhibition of fungal growth;
4 complete inhibition of fungal growth.

Fungus test
Cs Cladosporium sphaerospermum
Pp Pullularia Pullulans
At alternaria tenuis
An aspergillus niger
Tv trichoderma viride
Pd penicillium digitatum
Cm colletotrichum musae
Bc Botrytis Cinerea
Fc fusarium culmorum
Gc Gedtrichum Candidum
Va Verticillium Albo-Atrum
Pc Phytophtora Cinnamoni
Cc colletotrichum coffeanum
Ch Pseudocercosporella Herpotrichoides
Cb Cercospora Beticola
Sn septoria nodorum

Claims (1)

ACRYLIC ACID DERIVATIVES of the general formula

or their stereoisomers,
wherein X is hydrogen, fluoro, chloro, bromo, C ₁ C ₆ -alkyl, phenyl-C ₁ - C ₄ alkyl, wherein the phenyl group may optionally be substituted by fluorine, chlorine or methoxy, trifluoromethyl, bromomethyl, dimethoxymethyl, phenoxymethyl optionally substituted chlorine, piridinetil, furaniletil, thienylethyl, ethoxycarbonylethyl, ethenyl, optionally substituted phenyl, cyano-C ₁ to C ₃ alkoxycarbonyl, benzyloxycarbonyl, acetyl, or furyl benztiazolilom, ethynyl, substituted phenyl or tert-butyl, phenyl, C ₁ - C ₆ - alkoxy, allyloxy, optionally substituted pheny scrap, benzyloxy, phenoxy, optionally substituted with fluorine, chlorine, bromine, hydroxy, methyl, trifluoromethyl, formyl, propenyloxy, propargyloxy, acetoxy, methylsulfonyloxy, phenyl, phenoxy, nitro, amino, formylamino, acetylamino or C ₁ C ₆ alkoxy, optionally fluorine-substituted, phenylthio, phenylsulfinyl, naphthyloxy, pyridyloxy optionally substituted by trifluoromethyl, isobutyryloxy, benzoyloxy optionally substituted tert-butyl, formyl, benzoyl, optionally substituted methoxy, C ₁ - C ₃ alkoxycarbonyl, tsiklogeksiloksika Bonilla, allyloxycarbonyl, phenoxycarbonyl substituted with methoxy, nitro, benzoylamino, furoilamino or N-thienyl-carbonyl-N-methyl-amino;
Y located in the o-, m- or p-position relative to the acrylate group represents hydrogen, fluorine, chlorine, bromine, methyl, phenylethenyl, nitro or phenoxy;
Z is hydrogen,
or X and Y, when they are adjacent to the phenolic ring, together form a fused benzene ring optionally substituted with phenyl, a fused naphthalene ring, a fused benzofuranyl ring, a fused benzothienyl ring, or a group

groups Y and Z, when they are in the adjacent position of the phenyl ring, form a fused benzene ring with each other, except that when X is hydrogen, Y is not hydrogen or para-chlorine. Priorities by feature:
10/19/84 at XH, F, Cl, Br, C ₁ C ₆ -alkyl, Ph-C ₁ C ₄ -alkyl. wherein the phenyl group may optionally be substituted with fluorine, chlorine or methoxy, trifluoromethyl, bromomethyl, dimethoxymethyl, phenoxymethyl, optionally substituted with chlorine, pyridinethyl, furanylethyl, thienylethyl, ethoxycarbonyl; ethenyl optionally substituted with phenyl, cyano-C ₁ -C ₃ alkoxycarbonyl, benzyloxycarbonyl, acetyl, furyl or benzthiazolyl, ethynyl substituted with phenyl and tert-butyl, phenyl, C ₁ -C ₆ alkoxy, benzyloxy, phenoxy, optionally substituted with fluorine , chlorine, bromine, hydroxy, methyl, trifluoromethyl, formyl, propenyloxy, propargyloxy, acetoxy, methylsulfonyloxy, phenyl, phenoxy, nitro, amino, formylamino, acetylamino or C ₁ C ₆ alkoxy, optionally substituted with fluorine, formyl, benzoyl, optionally substituted methoxy, C ₁ - C ₃ -al hydroxycarbonyl, cyclohexyloxycarbonyl, aminoxycarbonyl, phenoxycarbonyl, substituted methoxy, nitro, benzoylamino, furoylamino, Y located at the o-, m- or p-position relative to the acrylate group, represents H, F, Cl, Br, Me, phenylethenyl, nitro or phenoxy;
05.23.85 at X, allyloxy, optionally substituted with phenyl, pyridyloxy, optionally substituted with trifluoromethyl, isobutyryloxy, benzoyloxy, optionally substituted with tert-butyl, N-thienyl-carbonyl-N-methylamino, X and Y, when they are in the adjacent position of the phenolic ring, together with each other form a fused benzene ring optionally substituted with phenyl, a fused naphthalene ring, a fused benzofuranyl ring, a fused benzothienyl ring, or a group

groups Y and Z, when they are in the adjacent position of the phenyl ring, together with each other form a benzene ring.

Images