MXPA98006657A - 2-metoxybenzofenone fungicide - Google Patents

Abstract

The present invention relates to: Substituted benzophenone compounds having the formula: The compounds are useful as fungicides having high systemicity

Description

2-FUNGICIDE METOXYBENZOPHENONES BACKGROUND OF THE INVENTION This invention relates to certain compounds of berzophenone, a process for their preparation, compositions containing said compounds, a method for combating a hopg in a place comprising treating the place with said compounds, and their use as fungicides. Food production depends on a variety of agricultural technologies to ensure that the growing population's dietary needs remain within reach, nutrients and readily available on store shelves. Fungicides are one of these agricultural technologies that are available to the world community. Fungicides are agrochemical compounds that protect crops and food against fungi and fungal diseases. Crops and food are constantly threatened by a variety of fungal organisms, which, if left unchecked, can cause the ruination of devastated crops and crops. In particular, ascomycefes, the causative agent of powdery mildew diseases, is always a threat. present especially for fruit and cereal crops. However, applications of fungicidal agents at disease control rates can cause phytotoxic damage to target plants. The compounds of the present invention are described in a general formula of the European patent application ("EP") EP 0 727 141, published on August 21, 1996. The EP application describes compounds having activity against phytopathogenic fungi, but systemicity relatively low REF. 28010 There is no disclosure in the EP application of substituted bepzcienes, wherein the first phenyl group is substituted with a methoxy group in the 2-position, and with a halogen atom or an alkyl group in the 6-position, and the second phenyl group is substituted with three alkoxy groups and one methyl group.

SUMMARY OF THE INVENTION The present invention provides a compound of formula I l ft (!) 0 wherein R 1 represents a halogen atom or an alkyl group; R 2 represents a halogen atom or hydrogen, or a nitro, alkoxy or alkyl group; or R1 and R2 together represent a group of the formula -CH = CH-CH = CH-; R3 and R4 each independently represent an optionally substituted alkyl group; and n is an integer from 0 to 3. The compounds combine relatively excellent fungicide activities in several crops with comparably high systemicities. It is an object of the present invention to provide highly systemic fungicidal compounds. Furthermore, it is an object of the invention to provide methods for controlling an undesired fungus by contacting said plants with a fupically effective amount of the compounds. It is another object of the invention to provide selective fungicidal compositions containing the compounds as active ingredients. These and other objects and features of the invention will be more apparent from the detailed description set forth below, and from the appended claims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS It has surprisingly been found that the compounds of formula I (1) in which R1 to R4 and n have the meaning given above, combine a relatively excellent fungicidal activity against phytopathogenic fungi, in particular those that cause powdery mildew diseases, and have a comparably high systemicity. Generally speaking, unless stated otherwise, as used herein, the term "halogen atom" may denote a bromine, iodine, chlorine or fluorine atom, and is especially a bromine, chlorine or fluorine atom, in particular a bromine or chlorine atom. The optionally substituted portions may be unsubstituted or have from one to the maximum possible number of substituents. Typically, 0 to 2 substitutes are present. Each optionally substituted group is independently substituted with one or more halogen atoms or nitro groups, cyano, cycloalkyl, preferably C3-6 cycloalkyl, cycloalkenyl, preferably C3-6 cycloalkenyl, haloalkyl, preferably C1-5 haloalkyl, halocycloalkyl, preferably C3-6 halocycloalkyl, alkoxy, preferably C? -Salkoxy, haloalkoxy, preferably -haloalkoxy C1-6, phenyl, halo- or dihalo-phenyl or pyridyl In general terms, unless otherwise stated herein, the terms "alkyl" and "alkoxy" as used herein with respect to a radical or portion are refer to a straight or branched chain radical or portion. As a rule, said radicals have up to 10, in particular up to 6 carbon atoms. Suitably, an alkyl or alkoxy moiety has from 1 to 6 carbon atoms, preferably from 1 to 5 carbon atoms. A preferred alkyl portion is the methyl, ethyl, n-propyl, isopropyl or n-butyl group. The invention relates especially to compounds of the general formula I in which an alkyl part of the groups R1 to R4, which may be straight or branched chain, contains up to 10 carbon atoms, preferably up to 9 carbon atoms, with more preferably up to 6 carbon atoms, and in which each optionally substituted group is independently substituted with one or more halogen atoms or nitro, cyano, cycloalkyl, preferably cycloalkyl, cycloalkenyl, preferably C 3-6 cycloalkenyl, haloalkyl, preferably haloalkyl halocycloalkyl, preferably halocycloalkyl C ", alkoxy, preferably C1-5 alkoxy, haloalkoxy, preferably haloalkoxy Ci-s, phenyl, or pyridyl, wherein the phenyl portion is optically substituted with one or two substituents selected from halogen atoms , cyano, alkyl and C 1-6 alkoxy groups. The invention relates especially to compounds of the general formula I in which R 1 represents a halogen atom, in particular chlorine, a straight or branched chain C 1-10 alkyl, in particular a straight chain C 1 .3 alkyl group, more preferably it is a methyl group which is unsubstituted or substituted with at least one optionally substituted phenyl group. The invention relates especially to compounds of the general formula I in which R.sup.2 represents UFG 'a halogen atom or hydrogen, in particular a chlorine, bromine or iodine atom, a nitro group, a C1.10 alkyl or a C1 haloalkyl. 10, most preferably a bromine, chlorine or hydrogen atom. If R2 is different from hydrogen, it is more preferably adhered in the ortho position to the radical R1. The invention relates especially to compounds of the general formula I in which R3 and R4 each independently represents an optionally substituted straight or branched chain C1.5 alkyl, in particular a straight chain C1.3 alkyl group, more preferably an methyl group unsubstituted or substituted. This methyl group is preferably unsubstituted or substituted with a phenyl group which is unsubstituted or substituted by one to five, preferably one or two halogen atoms or C1.4 alkyl or C1-6 alkoxy groups.

The benzophenone compounds according to formula I are oils, gums, or predominantly crystalline solid materials - and possess valuable fungicidal properties. For example, they can be used in agriculture, or related fields such as horticulture and viticulture, for the control of phytopathogenic fungi, especially ascomycetes, in particular powdery mildew diseases such as those caused by Erysiphe graminis, Podosphaera leucotricha, Uncinula necator and the like. Said benzophenone compounds possess a high fungicidal activity with a wide range of concentrations, and can be used in agriculture without harmful phytotoxic effects. Furthermore, the compounds according to the invention show enhanced residual and curative control of fungi and fungal diseases, such as powdery mildew of cereal, cucumber and grape,. and an improved systemicity compared to conventional fungicides. Useful results in terms of control of phytopathogenic fungi are obtained with a compound as defined in formula I wherein: R 1 represents a chlorine atom or a methyl group; R2 represents a chlorine or bromine atom or hydrogen; • R3 represents an alkyl group Ci.s; • R4 represents a C1.5 alkyl group or a benzyl group which is optionally Q substituted with one or more halogen atoms or one or more C1-4 alkyl or alkoxy groups; and n is 0 or 2, in particular 0. If R2 represents Cl or Br, it is preferably adhered to the benzene ring in the ortho position with respect to the radical R1. In particular the compounds of formula IA are preferred: OA) wherein R represents a chlorine atom or a methyl group; R2 represents a chlorine or bromine atom or hydrogen or a methyl group, and R 'represents a hydrogen atom or a C1-4 alkyl group or phenyl which is optionally substituted with one or more fluorine atoms or one or more C1 alkyl groups -4. In particular, the compounds of formula IB are preferred: (IB) in which R 'represents a hydrogen atom or a Ci-, alkyl or phenyl group which is optionally substituted with one or more fluorine atoms or one or more C1-4 alkyl groups. Especially good results are obtained in terms of control of phytopathogenic fungi using, for example, the following compounds of formula ? .ß'-dimethyl ^ '. S' ^ '- tetramethoxy-bepzofeonase,? .ß'-dimethyl-S'-pentoxy ^^' ^ '- trimethoxy-benzophenone, 5-bromo-6,6'- dimethyl-2,2 ', 3', 4'-tetramethoxy-benzophenone, 5-chloro-6,6'-dimethyl-2,2 ', 3', 4'-tetramethoxy-benzophenone, 5-iodo-6,6 '-dimethyl-2,2', 3 ', 4'-tetramethoxy-benzophenone,? -chloro-d-methyl ^^'. S '^' - tetramethoxy-benzofenopa, 5-bromo-6-chloro-6 ' -meti I-2, 2 ', 3', 4'-tetramethoxy-benzophenone, iSβ-chloro-S.e'-dimethyl ^^ '. S' ^ '- tetramethoxy-benzophenone, 2'-n-butoxy- 6-Chloro-6'-metii-2,3 ', 4'-trimethoxy-bep-phoenone, 2'-n-butoxy-6-chloro-5,6'-dimethyl-2,2', 3'-trimethoxy -benzophenone, 6-chloro-2, - (2-fluorobenzyloxy) -6'-methylene-2,3 ', 4'-trimethoxy-bep-ophenone, 6-chloro-2' - (4-fluorobenzyloxy) -6, -methyl-2,3 ', 4'-trimethoxy-bepzophenone, 5-bromo-6,6'-dimethyl-3'-n-pentyloxy-2,2', 4'-trimethoxy-benzophenone, d-chloro- ß'-methyl ^ '- n-pentyloxy ^ .S' ^ '- trimethoxy-benzophenone, 6-chloro-2' - (3-methylbutyloxy) -6'-methyl-2,3 ', 4'-trimethoxy-benzophenone , 2'-benzyloxy-6-chloro-6'-methyl-2,3 ', 4'-trimethoxy-benzophenone, 6-chloro-2' - (3 -methylbenzyloxy) -6'-methyl-2,3 ', 4'-trimethoxy-bepzophenone, 6-chloro-2' - (4-methylbenzyloxy) -6'-methyl-2,3 ', 4'-trimethoxy-benzophenone , S6-chloro-2-difluoromethoxy-6'-methyl-2,3 ', 4'-trimethoxy-benzophenone, 1- (6-methyl-2,3,4-trimethoxy-cepoyl) -2-methoxynaphthalene, - (6-methyl-2,3,4-trimethoxybenzoyl) -2-difluoromethoxynaphthalene, The present invention further provides a process (A) for the preparation of a compound of formula I, wherein n is 0, which comprises. Treat a compound of the general formula II (ID s wherein R1, R2, R3 and R4 have the meaning given above, and X represents a fluorine or chlorine atom, with an alkali metal methylate, preferably sodium methylate. Another possibility for the preparation of the compounds of formula I is an urocess (B) comprising the steps of (a) reacting a compound of formula III, (III) wherein R1, R2 and n have the meaning given above, and Y represents an leaving group, in particular a chlorine atom or a hydroxy group, with a compound of formula IV, (IV) wherein R3 has the meaning given for claim 1; in the presence of a Lewis acid (Y = leaving group) or a dehydrating agent (Y = OH), preferably phosphorus pentoxide or POCU; and (b) optically treating the resulting benzophenone of formula I, wherein R4 represents a methyl group, with a compound of formula V, R4-O-Met,)) wherein R4 represents an optionally substituted alkyl group, which is different from methyl, and Met denotes an alkali metal atom, preferably sodium. The compounds of formula III, wherein R 2 represents a halogen atom, are preferably obtained by a process (C) comprising the steps of (a) reacting a compound of formula VI, (VI) where R and n have the meaning given for claim 1, and "represents a hydrogen atom or an alkyl group, with a halogenating agent, (b) optionally hydrolyze the resulting halogenated alkyl benzoate (R" = alkyl), and (c) optionally treating the resulting halogenated benzoic acid with thionyl chloride. The starting materials of the formulas II, IV, V and VI are known products, the initial materials of formula III are partly known and in part new products. Accordingly, the invention provides novel intermediates of formula IIIA 0 wherein R represents an alkyl group, in particular a methyl group. The initial materials of formulas II, IV, V and VI can be prepared according to established methods or routine adaptations thereof. Substituents that are not compatible with the selected reaction conditions S can be introduced after the formation of the benzophenone. They can be generated by known methods, such as subsequent derivatization or substitution of an appropriate group, or by decomposing a suitable protecting group. The reaction between the 2-halobenzophenone of formula 11 and the alkali metal methylate is preferably carried out in the presence of a solvent, such as ethers such as tetrahydrofuran, diethyl ether, fer-butyl methyl ether, or dimethoxyethane or methanol or in mixtures of these solvents. The molar ratio between formula II and the alkali metal methylate is preferably in the range of 0.3 to 1.9 at a temperature between 25 and 120 ° C. The Friedel Crafts reaction between formula II and IV is carried out in the presence of a Lewis acid catalyst according to well-established procedures (Y = Cl). Suitable catalysts include FeCl3, AICI3, SnCl4, ZnCl2, TiCU, SbC and BF3, which may be in a molar equivalent amount (based on the benzoyl chloride of formula III). However, it is also possible to use smaller amounts of catalyst at elevated temperatures, suitably under reflux temperatures, with the preferred catalysts under these conditions being FeCl 3, 12, ZnCl 2, iron, copper, strong sulfonic acids such as F 3 C SO 3 H, and ion exchange reams as Amberlyst® 15 and Nafion ©. The preferred catalyst is FeCl3 in a molar ratio of 0.001 to 0.2 at a temperature of about 50 to 180 ° C. The reaction can be carried out in an inert solvent under the reaction conditions, for example methylene chloride or ethylene, benzene, octane, decane or mixtures of solvents, or in the presence of solvent, conveniently using one of the excess reagents, for example in the range of 1: 5 to 5: 1. If AICI3 is being used, the molar ratio is preferably in the range of 0.5 to 2 and suitable solvents are for example, methylene chloride or ethylene chloride at a temperature usually between -10 and 70 ° C.

In another preferred process according to the invention, the benzoic acid of formula III (Y = OH) is reacted with a compound of formula IV in the presence of phosphorus pentoxide at temperatures of about 0 to 50 ° C., preferably at room temperature or in the presence of POCI3 at temperatures of about 50 to 150 ° C, preferably under reflux. The halogenation of the benzoate of formula VI is preferably carried out in the presence of an inert solvent. Preferred halogenating agents are for example sulfurium chloride, bromine and N-iodo-succinimide. If R 1 represents a halogen atom, highly polar solvents are preferred, such as alcohols or carboxylic acids, in particular acetic acid. If R1 represents an alkyl group, in particular a methyl group, apolar solvents such as tetrachloromethapo are preferred. If the reaction is carried out with b? At a temperature between 0 and 40 ° C, preferably at room temperature, the halogenation is carried out predominantly in the ortho position with respect to the radical R1. In a preferred embodiment the compounds of formula li, wherein R 2 represents a bromine atom, are prepared by reacting a compound of formula VI, wherein R 1 represents an alkyl group, n is 0 and R "represents a hydrogen atom This bromination step is preferably carried out in the presence of a protic polar solvent, such as an aliphatic alcohol or an aliphatic carboxylic acid, in particular acetic acid, The bromination can be carried out conveniently in the presence of a weak base or a buffer system, such as sodium acetate or sodium carbonate One embodiment of the process of the present invention is a process wherein bromine is employed in a selected amount of a value in the range between 1.0 to 1, 5, in particular 1, 05 to 1, 2 molar equivalents with respect to the initial compound of formula VI.

The reaction between the compound of formula VI and bromine, as a rule, is carried out at a temperature sufficient to optimally convert the compound of formula VI to the compound of formula 111. This term represents a temperature high enough to maintain the conversion, but also low enough to avoid decomposition of the initial material and the product. The reaction is preferably carried out at temperatures between 0 ° C and 40 ° C, in particular at room temperature. The reaction between the compound of formula VI and bromine as a rule is carried out for a time sufficient to optimally convert the compound of formula VI to the compound of formula III. This term represents a period of time long enough to convert the maximum amount of starting material to the compound of formula III. The reaction is preferably carried out in a reaction time between 1 and 40 hours, in particular between 5 and 24 hours. The processes described below can be applied analogously to other initial compounds, if desired. Due to the excellent tolerance of the plants, the compounds of formula I can be used in the cultivation of all plants where infection of the controlled fungi is not desired, for example, cereals, vegetables, legumes, apples, vines. The absence of phytotoxicity from target cultures to fungal control rates is a feature of the present invention. Accordingly, the invention further provides a fungicidal composition comprising a carrier and, as an active ingredient, at least one compound of formula I as previously defined. Also provided is a method for making said composition, which comprises associating a compound of formula I as defined above, with at least one carrier. Said composition may contain a single compound or a mixture of several compounds of the present invention It is further contemplated that different isomers or mixtures of isomers may have different levels or activity spectra, and consequently the compositions may comprise individual isomers or mixtures thereof. isomers A composition according to the invention preferably contains from 0.5% to 95% by weight of active ingredient A carrier in a composition according to the invention is any material with which the active ingredient is formulated to facilitate application to the place to be treated, which may for example be a plant, seeds or soil, or to facilitate storage, transport or handling A carrier can be a solid or a liquid, including material that is normally gaseous but has been compressed to form a liquid, and any of the carriers normally used in the formula can be used tion * of fungicidal compositions. The compositions can be manufactured in, for example, emulsion concentrates, solutions that can be sprayed directly or diluted, diluted emulsions, powders for mixing with water, soluble powders, fine powders, granulates, water-dispersible granules, microencapsulated, by means of well established. The form of application such as spraying, atomization, dispersion, pouring, such as the compositions according to the desired objectives and the determined circumstances can be selected. The formulations, that is, the compositions comprising at least one compound according to the general formula 1, and optionally auxiliaries and solid and / or liquid adjuvants, can be prepared by means of well-established procedures, for example intensive mixing and / or grinding of the active ingredients with other substances, such as fillers, solvents, solid carriers and optionally surfactant compounds or adjuvants.

The solvents can be aromatic hydrocarbons, preferably C8 to C2 fractions, for example xylenes or mixtures of xylene, substituted paphthalenesesters of phthalic acid, such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons, for example cyclohexane or paraffins, alcohols and glycols, as well as their ethers and esters, for example ethanol, ethylene glycol mono- and dimethyl ether, ketones such as cyclohexanone, solvents strongly such as N-methyl-2-pyrrolidone, dimethyl sulfoxide, alkyl formamides, epoxidized vegetable oils, for example soybean oil or epoxidized coconut oil, water. Mixtures of different liquids are often suitable. The solid carriers that can be used for fine powders or dispersible powders can be mineral fillers, such as calcite, talc, kaolin, moptmorillonite, attapulguite. The physical properties can be perfected by the addition of highly dispersed silica gel or highly dispersed polymers. The carriers for granules can be porous material, for example pumice, broken brick, sepiolite, bentonite; Non-absorbent carriers can be calcite or sand. Additionally, a multitude of pre-granulated organic or inorganic materials, such as dolomite or ground plant residues, can be used. The fungicidal compositions are often formulated and transported in concentrated form, which is subsequently diluted by the user before application. The presence of small amounts of a carrier that is a surfactant facilitates this dilution process. Thus, preferably a carrier in a composition according to the invention is a surfactant. For example, the composition may contain at least two carriers, at least one of which is a tepsioactive agent. Suitable surfactants can be nonionic, anionic or cationic surfactants with good dispersion properties, emulsifiers and humectants according to the nature of the compound according to the general formula I to be formulated. Surfactants can also mean mixtures of surfactants. Suitable surfactants can be the so-called water-soluble soaps, as well as water-soluble synthetic tepsioactive compounds.

The soaps are usually alkali metal salts, optionally substituted aralipotrans or ammonium salts of higher fatty acids (C 10 -C 20), for example the potassium or sodium salts of stearic or oleic acid or mixtures of natural fatty acids which are prepared, for example, of tallow or coconut oil. In addition, methyl taurine salts of fatty acids can be used. However, so-called synthetic surfactants are used, especially fatty sulfonates, fatty suifatides, sulfonated benzimidazole derivatives or alkylaryl sulphonates. Fatty sulfates or fatty sulfonates are usually used as optionally substituted alkaline, alkaline earth or ammonium salts, and have an alkyl portion of 8 to 22 carbon atoms, whereby alkyl also means the alkyl portion of acyl residues, such as the salt of sodium or calcium of ugg-sulphonic acid, of sulfuric acid dodecylate or of a mixture of fatty alcohols prepared from natural fatty acids. This also includes the salts of sulfuric acid esters, sulfonic acids and adducts of fatty alcohols and ethylene oxide. The sulfonated benzimide-ol derivatives preferably contain 2 sulfonic acid residues and a fatty acid residue with 8 to 22 carbon atoms. Alkylaryl sulphonates are, for example, the sodium, calcium or t-ethyl ammonium salts of dodecylbenzene sulfopic acid, dibutylpaphthalene sulfonic acid or a condensate of paftanedosuiphonic acid and formaldehyde.

In addition, phosphates can be used, such as the salts of the phosphoric acid ester of a p-nonylphenol- (4-14) -ethylene oxide adduct or phospholipids. Nonionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, having 3 to 10 glycol ether groups and 8 to 20 carbon atoms in the hydrocarbon (aliphatic) residue and 6 to 18 carbon atoms in the alkyl residue of the alkyl phenols. Other suitable nonionic surfactants are ethylene oxide and polypropylene glycol polyadducts containing 20 to 250 water-soluble ethylene glycol ether groups, ethylene diamine polypropylene glycol and alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl moiety, the substances usually contain 1 to 5. units of ethylene glycol per propylene glycol unit. Examples of nonionic surfactants are non-phenyl-polyethoxy ethanols, poly-glycolic ether of castor oil, polyadducts of ethylene oxide and polypropylene, tributyl phenoxy polyethoxy ethanol, polyethylene glycol, octyl phenoxy polyethoxy etapoi. In addition, polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan trioleate, can be used. The cationic surfactants are preferably quaternary ammonium salts, which have at least one alkyl residue with 8 to 22 carbon atoms, and, in addition, optionally halogenated, low hydroxyalkyl, benzyl or alkyl residues. The salts are preferably halides, methyl sulfates or alkyl sulfates, for example, stearyl trimethyl ammonium chloride, or bepcyl bis (2-chloroethyl) ethyl ammonium bromide. The compositions of the invention can be formulated, for example, as powders for mixing with water, fine powders, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols. The powders for mixing with water usually contain 25%, 50% or 75% w / w of active ingredient, and usually contain besides solid inert carrier, % - 10% w / w of a dispersing agent, and when necessary, 0% - 10% w / w of stabilizer (s) and / or other additives such as penetrants or adhesives. Fine powders are usually formulated as a fine powder concentrate having a composition similar to that of a powder for mixing with water, but without a dispersant, and can be further diluted with additional solid carrier to give a composition that usually contains 0.5% - 10% w / w of active ingredient. The granules are usually prepared to have a size between mesh and 100 ASTM (about 2.00 mm - 0.15 mm), and can be manufactured by agglomeration or impregnation techniques. In general, the granules will contain 0.5% - 75% of active ingredient, and 0 - 10% w / w of additives such as stabilizers, surfactants, slow release modifiers and agglutination agents. The so-called "dry flowable powders" consist of relatively small granules having a relatively high concentration of active ingredient. Emulsifiable concentrates usually contain, in addition to a solvent or mixture of solvents, 1% -50% w / v active ingredient, 2% -20% w / v emulsifiers and 0% -20% w / v other additives such as stabilizers, penetrants and inhibitors of corrosion. The suspension concentrates are usually combined in order to obtain a stable, non-sediment flowable product, and habitually contain 10% -75% w / w active ingredient, 0.5% -15% w / w dispersion agents , 0.1% - 10% w / w of suspending agents such as protective colloids and thixotropic agents, 0% - 10% of other additives such as defoamers, corrosion inhibitors, stabilizers, penetrants and adhesives, and water or an organic liquid in which the active ingredient is substantially insoluble; certain organic solids or inorganic salts may be present dissolved in the formulation to aid in the prevention of settling, or as antifreeze agents for water. Emulsions or aqueous dispersions, for example compositions obtained by diluting a powder for mixing with water or a concentrate according to the invention with water, are also within the scope of the invention. Said emulsions may be of the water-in-oil or oil-in-water type, and may have a thick mayonnaise-like consistency. The composition of the invention may also contain other ingredients, for example other compounds possessing herbicidal, insecticidal or fungicidal properties, It is of particular interest in the realization of the duration of the protective activity of the compounds of this invention, the use thereof. of a carrier that will provide a slow release of the fungicide compounds in the environment of a plant to be protected.

Slowly they could for example be inserted into the soil adjacent to the roots of a plant, or they could include an adhesive component that would allow them to be applied directly to the stem of a plant. For convenience the compositions may preferably be in a concentrated form, while the end user in general employs diluted compositions. The compositions can be diluted to a concentration of 0.001% active ingredient (i. A.). The doses are usually in the range from 0.01 to 10 kg i. to. / he has. The compositions of this invention may further comprise other compounds having biological activity, for example, compounds having similar or complementary activity or compounds having insecticidal, herbicidal or plant growth regulating activity.

The other fungicidal compounds can be, for example, one which is capable of combating cereal diseases (for example wheat), such as those caused by Erysipha, Puccinia, Septoria, Gibberella and Helminthosporium spp, diseases transported by seeds and soil and powdery and lanuginous downy mildew in vines and powdery mildew and scab in apples, etc. These mixtures of fungicides may have a broader spectrum of activity than the compound of general formula I alone. Examples of other fungicidal compounds are carbepdazim, bepomil, thiophanate-methyl, thiabendazole, fuberidazole, etridiazole, diclofluanid, cymoxanil, oxadixyl, ofurace, metalaxyl, furalaxii, benalaxyl, fosetyl-aluminum, fenarimol, iprodione, procymidone, vinclozoin, penconazole, myclobutanil, R0151297, S3308, pyrazophos, etirimol, ditalimfos, tridemorph, triforine, nuarimol, triazbutyl, guazatine, triacetate salt of 1, 1 '-minodi (octamethylene) -diguahydin, propiconazole, prochloraz, flutriafol, hexaconazole, flusilazole, triadimefon, triadimenol, diciobutrazol, fenpropimorf, pirifepox, ciproconazole, tebuconazole, epoxiconazole, 4-chloro-N- (cyano (etox?) Methyl) bepzamide, propidin, chlorozoinate, dinicopazole, imazalil, fenfuram, carboxin, oxycarboxin, metfuroxam, dodemorf, blasticidin S, kasugamicin, edifenfos, kitazin P, cycloheximide, phthaiide, probenazole , Soprotiolane, tricyclazole, piroquiion, chlorbenzthiazon, neoasozin, polyoxin D, validamicin A, mepronil, flutolanil, pencycuron, diclomezin, phenazineoxide, nickel dimethyldithiocarbamate, teclofthalam, bitertanol, bupirimate, etaconazole, streptomycin, cipofuram, biloxazole, quinomethionate, dimethirimol, - (2-cyano-2-methoxyimino-acetyl) -3-ethyl urea, fenapanil, tolclofosmetil, piroxifur, poliram, maneb, mancozeb, captafol, chlorothalonil, anilazin, thiram, captan, folpet, zipeb, propineb, sulfur, d inocap, bipapacnl, nitrotalisopropil, dodina, ditianon, fepestan hydroxide, fenestan acetate, tecnazene, quintozen, dichlor, copper-containing compounds such as copper oxychloride, copper sulfate and Bordeaux mixture, as well as organic mercury compounds, kresoxim -methyl, azoxystrobin, SSF-126, pyrimethanil, cyprodinil, spiroxamine, fludioxonil, quinoxifen, carpropamid, metconazole, dimetomorph, famoxadone, propanocarb, * flumetover, fenpiclonil, fluazinam, mepanipyrim, triazoxide, chlorothionil. In addition, the co-formulations according to the invention may contain at least one benzophenone of formula I and any of the following classes of biological control agents such as viruses, bacteria, nematodes, fungi and other microorganisms which are suitable for controlling insects. , weeds or plant diseases, or to introduce resistance to hosts in plants. Examples of such biological control agents are: Bacillus thuringiensis, Verticillium lecanii, Autographica californica NPV, Beauvapa bassiana, Ampelomyces quisqualis, Bacilis subtilis, Pseudomonas fluorescens, Steptomyces gnseoviridis and Trichoderma harzianum. Still further, the co-formulations according to the invention may contain at least one benzophenone of formula I and a chemical agent that induces the acquired stiatemic resistance in plants, such as for example nicotinic acid or derivatives thereof or BION. The compounds of general formula I can be mixed with soil, peat or other root medium for the protection of plants against foliar or fungal diseases or transported by the soil or seeds. The invention still further provides the use as a fungicide of a compound of the general formula I as defined above, or a composition as defined above, and a method for combating fungi in a location, which comprises treating the site, which may be for example plants 5 subject or subjected to the fungal attack, seeds of said plants or the medium in which said plants are growing or should grow, with said compound or composition.

The present invention is of broad applicability in the protection of crop or ornamental plants against fungal attack. Typical crops that can be protected include vines, grain crops such as wheat and barley, rice, sugar beets, top-sheet fruits, peanuts, potatoes, vegetables and tomatoes. The duration of protection usually depends on the individual compound selected, and also on a variety of external factors, such as climate, whose impact is normally mitigated by the use of an appropriate formulation. The following examples further illustrate the present invention. However, it should be understood that the invention is not limited only to the particular examples given below.

EXAMPLE 1 Preparation of 6,6'-dimethyl-2,2'.3'4'-tetramethoxy-benzophenone 1 A 2-Methoxy-6-methylbenzoic acid A mixture of ethyl 2-methoxy: > 6-methylbenzoate (5.0 g, 25 mmol), water (10 mL), methanoi (40 mL) and sodium hydroxide (2.1 g, 50 mmol) were heated under reflux with stirring. The reaction mixture is diluted with water (150 ml) and acidified with concentrated hydrochloric acid. The solid material is collected by filtration, washed with water and dried to give dark yellow crystals, 2.1 g, mp 136 ° C. 1 B 2-Methoxy-6-methylbenzoyl chloride A mixture of 1A (1.7 g, 10.2 mmol) and thiopyl chloride (2 mL) is heated under reflux for 1 hour. The mixture is concentrated and the resulting benzoylchloride is used without further purification. 1 C 6,6'-dimethyl-2,2 ', 3', 4'-tetramethoxy-benzophenone A mixture of 3,4,5-trimethoxytoluene (1.86 g, 10.2 mmol), IB (10.2 mmol) mmol), aluminum chloride (1.33 g, 10 mmol) and dichloromethane (20 ml) is stirred at 0 ° C. The reaction is set at 0 ° C with the formation of hydrogen chloride. Subsequently, the reaction mixture is stirred for another 4 hours at room temperature. Then a mixture of dilute hydrochloric acid and ethyl acetate (1: 1 v / v; 100 ml) is added slowly at 0 ° C. The organic phase is concentrated and the residue is recrystallized from methanol. The solid material is collected by vacuum filtration, washed three times with methanol / water (3: 1 v / v, 100 ml each) and dried, yielding white crystals, 1.0 g (30.3%), mp 84 ° C.

Example 2 Preparation of 6,6'-dimethyl-2'-n-butoxy-2,3 ', 4'-trimethoxy-benzophenone A mixture of n-butanol (5 ml) and sodium hydride (60% in oil, 10 mmol) is stirred until the formation of H2 gas ends. A mixture of 1 C (0.7 g, 2.2 mmol) and dimethoxyethane (15 mL) is added to the resulting reaction mixture. Subsequently, the reaction mixture is heated under reflux with stirring for 24 hours. Then a mixture of water and ethyl acetate (1: 1 v / v, 100 ml) is slowly added at room temperature. The organic phase is separated, concentrated and the residue is purified by column chromatography (petroleum ether: ethyl acetate, 95: 5 v / v), yielding the pure product as a yellow oil, 0.2 g (24, 4 %).

Example 3 A mixture of sodium methylate in methanol (5.4 mol / L, 19.6 mol), 2,6-dichloro-3 ', 4'-dimethoxy-6'-methyl-2'-pentyloxy-benzophenone ( obtained according to EP 0 727 141, 2.69 g, 6.5 mmol) and dimethoxyethane (20 ml) is heated to 80 ° C with stirring for 24 hours. Then a mixture of water and ethyl acetate (1: 1 v / v, 100 ml) is slowly added at room temperature. The organic phase is separated and concentrated and the residue is purified by column chromatography (dichloromethapo), yielding the pure product as a yellow oil, 0.52 g (19.7%).

Example 4 Preparation of 5-bromo-β-chloro-6'-methyl-2,2 ', 3', 4'-tetramethoxy-benzophenone «4AA Ethyl 5-bromo-6-chloro-2-methoxybenzoate A mixture of ethyl 6 2-Chloro-2-methoxybenzoate (1.8 g, 8.4 mmol), bromine (1.41 g, 8.8 mmol) and acetic acid (5 mL) are stirred at room temperature for 24 hours. The reaction mixture is poured into water and extracted with ethyl acetate. The organic phase is separated and concentrated and the residue is purified by column chromatography (petroleum ether: ethyl acetate., 95: 5, v / v), yielding the pure product as a yellow oil, 1.7 g (69%). 4B 5-Bromo-6-chloro-2-methoxybenzoic acid A mixture of 4A (1.7 g, 5.8 mmol), water (10 ml), ethanol (20 ml) and sodium hydroxide (0.5 g, 12.5 mmoi) is heated under reflux with stirring. The reaction mixture is diluted with water (80 ml) and acidified with concentrated hydrochloric acid. The solid material is collected by filtration, washed with water and dried, yielding white crystals, 1.3 g (85%), mp 186-188 ° C. 4C 5-Bromo-6-chloro-2-methoxybenzoic acid chloride A mixture of 4B (1.2 g, 4.6 mmol), dichloromethane (15 mL) and oxalyl chloride (1 mL) is stirred at room temperature for 2 hours. The mixture is concentrated and the resulting benzoylchloride is used without further purification. 4D 5-bromo-6-chloro-6'-methyl-2,2 ', 3', 4'-tetramethoxy-benzophenone A mixture of 3,4,5-trimethoxytoluene (0.83 g, 4.6 mmol), 4C (4.6 mmol), aluminum chloride (0.62 g, 4.6 mmol) and dichloromethane (20 ml) is stirred at room temperature for 3 hours. Then add a mixture of water and ethyl acetate (1: 1 v / v; 50 mi). The organic phase is concentrated and the residue is crystallized from diisopropyl ether and recrystallized from methanol. The solid material is collected by vacuum filtration, washed with. water and dried, yielding yellow crystals, 0.7 g (35.4%), mp 87-88 ° C.

Example 5 Preparation of 1- (6'-methyl-2'.3 ', 4'-trimethoxybenzoyl) -2-methoxynaphthalene 5A Methyl (2-methoxynaphth-1-yl) -carboxylate A mixture of 2-hydroxynaphth-1-acid iocarboxylic acid (18.82 g, 100 mmol), sodium hydroxide (8.8 g, 220 mmol), dimethylsulfate (31.5 g, 250 mmol) and water (200 mL) were heated to 70 ° C with stirring for 20 minutes. hours. Subsequently, the reaction mixture is cooled to room temperature and extracted with ethyl acetate twice. The combined organic fasrs are concentrated and the residue is used without further purification. 5B Methyl (2-methoxynaphth-1-yl) -carboxylic acid A mixture of crude 5A (10.5 g, 48 mmol), water (100 ml), methanol (150 ml) and sodium hydroxide (12 g, 300 mmol) ) is heated under reflux with stirring. The reaction mixture is extracted with diethyl ether twice. The aqueous reaction mixture is filtered and acidified with concentrated hydrochloric acid. The solid material is collected by filtration, washed with water and dried, yielding yellow crystals, 9.45 g (97.4%), mp 175-176 ° C. 5 1 - (6'-methyl-2 \ 3 \ 4 rimethoxybenzoyl) -2-methoxynaphthalene A mixture of 5B (2.02 g, 10 mmol), 3,4,5-trimethoxytoluene (1.82 g, mmol), P2Os (10.0 g) and dichloromethane is stirred at room temperature for 16 hours. Subsequently, the dichloromethane is distilled off and the residue is diluted with ethyl acetate. The organic phase is washed with water and concentrated. The residue is purified by column chromatography (petroleum ethers: ethyl acetate, 8: 2, v / v) and recrystallized from petroleum ether: diisopropyl ether (1: 1 v / v). The solid material is collected by vacuum filtration, washed with cold petroleum ether: diisopropyl ether (1: 1 v / v) and dried, yielding white crystals, 0.9 g (24.6%), mp 72 ° C.

Example 6 Preparation of 5-bromo-6,6'-dimethyl-2,2'.3'.4'-tetramethoxy-benzophenone 6A Ethyl 5-bromo-6-metit-2-methoxybenzoate A mixture of ethyl 6-methyl-2- methoxybenzoate (8.4 g, 43.2 mmol), bromine (6.9 g, 43.2 mmol) and tetrachloromethane (170 mL) is stirred at room temperature for 60 hours. The reaction mixture is poured into water and extracted with ethyl acetate. The organic phase is separated and concentrated. The crude product is obtained as a yellow oil, 1 f and 3 g (87%) and used without further purification. 6B 5-Bromo-6-metii-2-methoxybenzoic acid A mixture of 6A (9.8 g, 34.1 mmol), water (40 ml), ethanol (80 ml) and sodium hydroxide (2.7 g, 68.3 mmol) is heated under reflux with stirring for 42 hours. The reaction mixture is diluted with water (80 ml), acidified with concentrated hydrochloric acid and extracted with dichloromethane. The organic phase is separated and concentrated. The solid material is collected by filtration, washed with water and dried, yielding whitish crystals, 5.4 g (61%), mp 81-83 ° C. 6C S-bromo-e.?'-dimetil ^. .S '^' - tetramethoxy-benzophenone A mixture of 6B (24 g, 10 mmol), 3,4,5-trimethoxytoluene (1.82 g, 10 mmol), P2O5 (10.0 g) and dichloromethane (150 ml) ) is stirred at room temperature for 16 hours. Subsequently, the dichloromethane is distilled off and the residue is diluted with ethyl acetate. The organic phase is washed with water and concentrated. The residue is purified by column chromatography (petroleum ether: ethyl acetate, 8: 2, v / v) and recrystallized from diisopropyl ether. The solid material is collected by vacuum filtration, washed with cold petroleum ethers: diisopropyl ether (1: 1 v / v) and dried, yielding white crystals, 2.2 g (54%), mp 89-91 °. C.

Examples 7 - 49 Using essentially the same procedures as described above for Examples 1 to 6, and employing standard derivatization techniques where appropriate, the following compounds are prepared and shown in Tables I and ll: Table I s Table II fifteen 2S Example 50 Preparation of 5-bromo-6,6'-dimethyl-2,2'.3 ', 4'-tetramethoxy-benzophenone 50A 6-methy-2-methoxybenzoic acid A mixture of ethyl 6-methyl-2-methoxybenzoate ( 642, 0 g, 3.3 mmol), water (2.5 L), ethanol (4.0 L) and sodium hydroxide (270 g, 6.6 mmol) is heated under reflux with stirring for 20 hours. Subsequently, ethanol is removed by distillation and the reaction mixture is diluted with water, acidified with concentrated hydrochloric acid. The solid material is collected by vacuum filtration, washed with water and dried, yielding whitish crystals, 460.0 g (83.9%). 50B 5-Bromo-6-methyl-2-methoxybenzoic acid A mixture of bromine (102 ml, 2.0 mmol) and acetic acid (225 ml) is added to a mixture of 50A (304.0 g, 1.8 mole). ), sodium acetate (164.0 g ', 2.0 mol) and acetic acid (3.0 I) at a temperature of 10 to 15 ° C. The reaction mixture is stirred at room temperature for 16 hours. The solid material is collected by vacuum filtration, washed with water and dried, yielding whitish crystals, 321.0 g (72.6%), mp 81-83 ° C. 50C S-bromo-d.e'-dimethyl ^^ '. S' ^ '- tetramethoxy-benzophenone 50B (240 g, 1.0 mol) is reacted with 3,4,5-trimethoxytoluene (1.82 g, 10 mmol) in the presence of P2O5 (1.0 kg) and dichloromethane as described in Example 6, yielding white crystals, 220 g (54%), mp 89-91 ° C.

The sequence of the saponification steps (with sodium hydroxide) and bromination described above in Examples 50A and 50B, respectively, is reversed in Examples 6B and 6A above. The bromination described in Examples 50B and 6A is with the free acid and ester, respectively. The reaction conditions further differ, as in Example 50B which uses a polar protic solvent (acetic acid) and a buffer salt (sodium acetate). Example 6A uses a non-polar aprotic solvent (tetrachloromethane). , - ' Example 51 Preparation of 6,6'-dimethyl-5-fluoro-2,2 ', 3'4'-tetramethoxy-benzophenone 51A 2-tert-butyl-4-fluoro-5-methylphenol A mixture of 4-fluoro-3-methyphenol (12.60 g, 0.1 mol), tert-butylchloride (25 mL) and FeCl 3 is heated to reflux by 16 hours. The excess of tert-butylchloride is distilled off and the residue is purified by column chromatography (petroleum ether, ethyl acetate, 95: 5 v / v) yielding a pure product as a yellow oil, 15.3 g (84%). 51 B 6-Bromo-2-tert-butyl-4-fluoro-5-methylphenol A mixture of 5JA (0.91 g), tetractoromethane (20 mL), N-bromosuccinimide (0.89 g) and AICI3 is mixed with room temperature for 3 days. The reaction mixture is filtered and concentrated. The yellow oil obtained (1.25 g) is used without further purification. 51 C 2-bramo-4-fluoro-3-methylfepol A mixture of 51 B (18.5 g ^ 'benzene (120 mL) and AICI3 (6.5 g) is heated to reflux for 5 hours. it is cooled to room temperature and diluted with ethyl acetate and water.The organic phase is separated and concentrated.The residue is purified by column chromatography (petroleum ether: ethyl acetate, 95: 5 v / v) producing a pure product as white crystals, 9.0 g (62%) 51 D 2-bromo-6-fiuoro-3-methoxytoluene A mixture of 51C (9.0 g), potassium carbonate (6 g), dimethyl sulfate (6 g) and acetonitrile (150 mL) is heated at reflux for 1 hour.The reaction mixture is cooled to room temperature, diluted with water and extracted with diethylether twice.The organic phase is separated and concentrated and the residue (9.0 g) is used. without further purification. 51 E 3-Fluoro-6-methoxy-2-methylenebenzoic acid A solution of n-butyllithium in hexane (18.1 mL, 2.5 mol / L) is slowly added to a mixture of 51D (9.0 g) and tetrahydrofuran (90 mL) at -78 ° C. The resulting reaction mixture is saturated with carbon dioxide at -78 ° C and allowed to warm to room temperature. The reaction mixture is poured into water, acidified and extracted with diethylether twice. The organic phase is extracted with an aqueous solution of sodium hydroxide (5%). The aqueous extract is acidified and extracted with diethyl ether twice. The organic phase is dried and concentrated. The residue (3.9 g) is used without further purification. 51 F? .d'-dimethyl-S-fluoro ^^ '. S "-tetramethoxybenzophenone 51 E (3.9 g, 0.021 mol) is reacted with 3,4,5-trimethoxytoluene (3.85 g, 0.021 mol) ) in the presence of P2O5 (12.0 g) and dichloromethane (150 mL) as described in Example 6 yielding white crystals, 0.34 g, mp. 58 ° C.

Biological Research A Follicularity Mildiú Powder of Wheat (in English WPM): GUEST: Wheat (Triticum aestivum L.) variety Kanzler PATHOGEN: Erysiphe qraminis DC. F. sp. tritici E. Marchal EVALUATION PROCEDURE: 1. Wheat seeds (8 / pot) are planted in 8 cm diameter plastic pots in the greenhouse. 2. When the primary leaf is completely expanded, the plants are arranged in four in each pot, of which two are marked with a permanent marker 5 cm above the tip of the leaf on the surface of the upper leaf. Thus, there are two plants treated with bands and two untreated in each pot. 3. A pipette is used to apply 5 μl of the formulated compound in a band on the surface of the lower sheet opposite the mark. The application band should cover the width of the entire sheet. After application, the plants do not move until the bands are dry (about half an hour later). 4. After the treated plants have dried, they are moved to the greenhouse and kept there for 2 days to allow the movement of the compounds. The plants are kept with watering at the bottom. .

. Two days after the application, the plants are inoculated by sprinkling them with powdery mildew conidia in the greenhouse. Evaluations are typically done 7 - 8 days after inoculation.

Evaluation Three types of compound movements are evaluated by evaluating the disease in three areas of each leaf treated with band. Translaminar movement. The percentage of disease area for the translaminar band area (marked area of the surface of the upper sheet directly opposite to where the band was applied to the surface of the lower sheet, width of the band approximately 5 mm). Then the control of the translaminar disease is calculated using the following formula: % disease control = 100 -% disease in treated plants x 100% disease in untreated plants Distal movement and proximal movement. The areas free of distal and proximal disease on the surface of the upper leaf are measured in mm. The distal direction is from the band to the leaf axis, and the proximal direction is from the band to the base of the sheet. The percentage of the disease-free zone is calculated in relation to the total distance between the band and the base or axis of the leaf. If the disease is markedly inferior in the distal or proximal area, this is also observed.

FORMULATION AND CONTROLS: 1. The compounds are formulated in a solvent / surfactant system consisting of 5% acetone and 0.05% Tween 20 in deionized water. The formulated compounds are prepared using deionized water. The compounds are typically evaluated at 400 ppm. 2. Two types of controls are included: Plants treated with solvent / surfactant solution and inoculated bands (Solvent Blank) Untreated plants that are inoculated (Control Inoculated). The results of this evaluation are shown in Table III: Table III Foliar Systemicity The following compounds have been used as standards, which are known from EP 0 727 141: Standard 1 2,6-dichloro-6'-methyl-2 ', 3', 4'-trimethoxybenzophenone Standard 2 2 ', 3', 4'-trimethoxy-2,6,6'-trimethylbenzophenone B-1 Comparison of the fungicidal activity of 2-methoxy-benzophenones with 2,6-dichloro- and 2,6-dimethyl-benzophenone Diseases of evaluation: (a) Dusty Mildew of the Wheat (WPM): GUEST: Wheat (Triticum aestivum L.) variety Kanzler PATHOGEN: Ervsiphe qraminis DC. F. sp. tritici E. Marchal (b) Mildiú Polvoroso de la Barbada (BPM): GUEST: Barley (Hordeum vulqare L.) variety Golden Promise PATHOGEN: Ervsiphe qraminis DC. F. sp. E. Marchal hordei EVALUATION PROCEDURE: This evaluation is a zero-day protective test for the control of powdery mildew of wheat and barley. 1 . Wheat or barley seeds (approximately 8 - 10 / pot) are planted in 6 cm diameter plastic pots and kept in the greenhouse. 2. When the primary leaf is completely expanded, the formulated evaluation compounds are sprayed with a fingerprint sprayer with a single nozzle at the top, at an index of 200 l / ha. Then the plants are allowed to air dry. 3. The inoculation continues approximately three hours after the application of the compound. The plants are established in benches in the greenhouse with mats for watering the lower part, and they are inoculated by sprinkling them with conidia of plants infected with powdery mildew (cultures of material at an age of 10-14 days). disease in the primary leaf as the percentage of leaf area with symptoms / signs of disease, approximately 7 days after the inoculation.The tips and the bases of the leaves are excluded from the evaluation. the disease by means of the following formula:% disease control = 100 -% infection in treated plants x 100% infection in untreated plants FORMULATION, REFERENCE COMPOUNDS AND CONTROLS: 1. Technical compounds are formulated in a solvent / surfactant system consisting of 5% acetone and 0.05% Tween 20 in deionized water The compounds are dissolved in acetone before adding water; Tween 20 can be added through either acetone or water. The dilutions are made using the solvent / surfactant system. The evaluation compounds are typically evaluated with a range of concentrations that covers several kinds of magnitudes, and then the ED values are calculated for comparison of compounds. The formulated compounds are prepared using deionized water. 2. Two types of controls are included: Plants treated with solvent / surfactant solution and inoculated (Solvent Blank) Untreated plants that are inoculated (Control Inoculated). The results of this evaluation are shown in Table IV: Table IV Fungicidal activity of 2-methoxybenzofenopas (ED90 values) Comparison of the fungicidal activity of the 2-methoxy-bephophenones with a 2,6-dichloro- and 2,6-dimethyl benzophenone. The results are from day 0 protective tests in which all analogues were evaluated side by side.

Compounds applied as technical material formulated in 0.5% acetone 0.05% Tween 20 water.

B-2 Comparison of residual and curative fungicidal activity of 2-methoxy-benzophenones with a 2,6-dichloro- and 2,6-dimethyl-benzophenone Diseases of evaluation: (a) Dusty Mildew of the Wheat (WPM): GUEST: Wheat (Triticum aestivum L.) variety Kanzler PATHOGEN: Ervsiphe qraminis DC. F. sp. tritici E. Marchal (b) Mildiú Polvoroso del Cucumber (QPM): GUEST: Cucumber (Cucumis sativus L.) pickled variety Bush PATHOGEN: Ervsiphe cichoracearum DC EVALUATION PROCEDURE: This evaluation procedure is for the residual and curative control of powdery mildew diseases. 1 . Wheat seeds (approximately 8 - 10 / pot) or cucumber seeds (1 seed / pot) are planted in 6 cm diameter plastic pots and kept in the greenhouse. 2. When the primary leaf (wheat) or the cotyledons (cucumber) are fully expanded, the formulated evaluation compounds are sprayed with a fingerprint sprayer with a single nozzle at the top, at a rate of 200 I / he has. Then the plants are allowed to air dry. 3. The inoculation precedes the treatment 2 days in the case of the curative evaluations, and proceeds to the treatment 3 days in the case of residual evaluations. For inoculation, the plants are established in benches in the greenhouse with mats for watering the lower part, and are inoculated by sprinkling them with conidia of plants infected with powdery mildew (cultures of material at an age of 10-14 days). Between the inoculation and the treatment for the curative evaluations, and between the treatment and the inoculation for the residual evaluations, the plants are kept in the greenhouse with watering from the lower part. 4. The disease is evaluated in the primary leaf (wheat) or cotyledons (cucumber) as the percentage of leaf area with symptoms / signs of disease, approximately 7 days after inoculation. In the case of wheat, the tips and the bases of the leaves are excluded from the evaluation. Then the percentage of control of the disease is calculated by means of the following formula:% disease control = 100% infection in treated plants x 100% infection in untreated plants FORMULATION. REFERENCE COMPOUNDS AND CONTROLS: 1. The technical compounds are formulated in a solvent / surfactant system consisting of 5% acetone and 0.05% Tween 20 in deionized water. The compounds are dissolved in acetone before the addition of water; Tween 20 can be added through either acetone or water. The dilutions are made using the solvent / surfactapte system. The formulated compounds are prepared using deionized water. 2. Two kinds of controls are included: Plants treated with the solvent / surfactant solution and inoculated (Solvent Blank) Untreated plants that are inoculated (Control Inoculated). The results of this evaluation are shown in Table V: Table V Residual and curative fungicidal activity of 2-methoxybenzofeponas 2 days C = healing 2 days Inoculation 2 days BEFORE the application 3 days R = residual 3 days Inoculation 3 days AFTER the application It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention. Having described the invention as above, property is claimed as contained in the following:

Claims (19)

1. CLAIMS A compound of formula I: (0 characterized in that: R1 represents a halogen atom or an alkyl group; R 2 represents a halogen atom or hydrogen, or a nitro, alkoxy or alkyl group; or R1 and R2 together represent a group of the formula -CH = CH-CH = CH-; R3 and R4 each independently represent a benzyl or optionally substituted alkyl group; and n is an integer from 0 to 3.
2. 2. A compound as set forth in claim 1, character-io acq-e R1 represents a chlorine atom or a methyl group; R2 represents a bromine, chlorine or hydrogen atom; R represents a C, ^ alkyl group; R 4 represents a C 1-5 alkyl group or benzyl group, being optionally substituted with at least one halogen atom, or C 1 alkoxy or alkyl group; and n is 0.
3. 3. A compound as set forth in claim 2, characterized in that it is selected from the group consisting of: 6,6'-dimethyl-2,2 ', 3', 4'-tetramethoxy-benzofenopa, 6,6'-dimethy-3'-pentoxy-2,2 ', 4'-tp "methoxy-benzophenone, 5-bromo-6,6'-dimethyl-2,2', 3 ', 4'-tetramethoxy- benzophenone, 5-chloro-6,6'-dimethyl-2,2 ', 3', 4'-tetramethoxy-benzophenone, 5-iodo-6,6'-dimeti! -2,2 ', 3', 4 ' -tetramethoxy-bepsophenone, 6-chloro-6'-methyl-2,2 ', 3', 4'-tetramethoxy-benzophenone, 5-bromo-6-chloro-6'-rnetyl-2,2 ', 3', 4'-tetramethoxy-benzophenone, 6-chloro-5,6'-dimethyl-2,2 ', 3', 4'-tetramethoxy-benzophenone, 2'-butoxy-6-chloro-6'-methyl-2 , 3 ', 4'-trimethoxy-benzophenone, 2'-butoxy-6-chloro-5,6'-dimethyl-2,2', 3'-trimethoxy-benzophenone, 6-chloro-2 '- (2-fluorobenzyloxy) ) -6'-methyl-2,3 ', 4'-trimethoxy-benzophenone, 6-chloro-2' - (4-fluorobenzyloxy) -6'-methyl-2,3 ', 4'-trimethoxy-benzophenone, -bromo-6,6'-dimethyl-3'-n-pentyloxy-2,2 ', 4'-trimethoxy-benzophenone, 6-chloro-6'-methyl-2'-pentyloxy-2,3', 4 ' -trimethoxy-benzophenone, 6-chloro-2 '- (3 -methylbutyroxy) -6'-methyl-2,3 ', 4'-trimethoxy-benzophenone, 2'-benzylloxy-6-chloro-6'-methyl-2,3', 4'-trimethoxy -benzophenone, 6-chloro-2 '- (3-methylbenzyloxy) -6'-methyl-2,3', 4'-trimethoxy-benzophenone, 6-chloro-2 '- (4-methylbenzyloxy) -6' -methyl-2,3 ', 4'-trimethoxy-benzophenone, 6-chloro-2-difluoromethoxy-6'-methylene-2,3', 4'-trimethoxy-benzophenone, 1- (6'-methyl- 2 ', 3', 4'-trimethoxybenzoyl) -2-methoxypaphthalene, 1- (6'-methyl-2 ', 3', 4'-trimethoxy-cepzoyl) -2-difluoromethoxynaphthalene.
4. 4. A process for the preparation of the compound of formula I, character! - because n is 0, which comprises reacting a compound of formula II. (ll) wherein R1, R2, R3 and R4 are as described in claim 1, and X represents a fluorine or chlorine atom, with an alkali metal methanolate.
5. 5. A process for the pregaration of the compound of formula I, characterized in that it comprises (a) reacting a compound of formula III, (III) wherein R1, R2 and n are as described in claim 1, and Y represents an leaving group or a hydroxy group, with a compound of formula IV, (IV) wherein R3 is as described in claim 1; in the presence of a Lewis acid or a dehydrating agent; and (b) optionally treating the obtained product with a compound of formula V: R -O-Met (V) wherein R4 represents an optionally substituted alkyl or aryl group, with the proviso that the alkyl group is methyl, and Met denotes an alkaline metal atom.
6. 6. A process for the preparation of a compound of formula III of claim 5, which is a reprisal or at-risk to compliment), (a) reacting a compound of formula VI, (VI) wherein R1 and n are as described in claim 1, and R "represents a hydrogen atom or an alkyl group, with a halogenating agent
7. 7. A process for the preparation of a compound of formula III of the claim 5, it is possible that a R2 compound is added to a halogen atom, which can (a) react a compound of formula VI: (SAW) wherein R1 and n are as described in claim 1, and R "represents an alkyl group, with a halogenating agent, (b) opaquely hydrophilizing the resulting halogelated alkyl benzoate, and (c) optionally treating the resulting halogenated alkyl benzoic acid with thiopyl chloride.
8. 8. r r r r r r r r t r r t r r t r r t r t r t r t r t r t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t t 1 1 and a carrier.
9. 9 A method to fight fungi or a plant fupgal disease in a lirpr. acadB? zsüo p ^ f * »< -ui xt? ib tedU t the liryar an ua aacuasto de l 'ra.vxn.tica-tion 1.
10. 10. A method to combat fungi or a fungal disease of plants in a place, characterized because it comprises treating the place with a composition of claim 8.
11. 11. The method of claim 9, characterized in that fungal plant disease is ascomycetes.
12. The method of claim 10, characterized in that the plant fungal disease is ascomycetes.
13. The method according to claim 9, characterized in that the fungus is a member of the subgroup Erysiphales.
14. 14. The method of claim 13, characterized in that the fungus is selected from Erysiphe graminis, Erysiphe cichora-cearum, Podosphaera leucotricha or Uncinula necator.
15. 15. The method according to claim 10, characterized in that the fungus is a member of the subgroup Erysiphales.
16. 16. The method of claim 15, characterized in that the fungus is selected from Erysiphe graminis, Erysiphe cichoracearum, Podosphaera leucotricha or üncinula necator.
17. 17. A process for the preparation of a compound of formula III, characterized in that ^ R.R2 represents a bromine atom, according to claim 6, which comprises reacting a compound of formula VI, wherein R is an alkyl group; n is O; and R "represents a hydrogen atom, with bromine
18. 18. A process for the preparation of a compound of formula III according to claim 17, characterized in that the reaction between the compound of formula VI and bromine is carried out in the presence of a polar protic solvent
19. 19. A compound having the formula. < r 48 10 characterized in that R1 represents a μupu alkyl. fifteen 20 2S