WO2015121802A1 - Benzoylphenyl-formamidines having a fungicidal activity, their agronomic compositions and relative use - Google Patents

Abstract

New benzoylphenyl-formamidines having general formula (I): (I) fungicidal compositions containing them, and their use for the control of phytopathogenic fungi of agricultural crops, are described.

Description

BENZOYLPHE YL-FORMAMIDINES HAVING A FUNGICIDAL ACTIVITY, THEIR AGRONOMIC COMPOSITIONS AND RELATIVE USE.

The present invention relates to phenylamidines having a high fungicidal activity; in particular, it relates to benzoylphenyl-formamidines having a high fungicidal activity and their use for the control of phytopathogenic fungi of important agricultural crops.

Arylamidines with a fungicidal activity are already known and are described, in particular, in international patent application WO 2000/46184. Among the numerous compounds described in the above patent application, N,N-dimethyl-N'-[4-(3-trifluoromethylbenzoyl)-2,5- xylyl-form-amidine (compound n. 398, Tab. 1, page 47) is exemplified.

This compound, however, in addition to numerous other compounds described in this document, is not satisfactory from the point of view of activity with respect to phytopathogenic fungi. In many cases, moreover, these products are phytotoxic with respect to important agricultural crops and show a marked leaf necrosis on cereals, cucumbers, tomatoes and other important crops, at the doses that allow a good fungicidal activity to be obtained: these effects make their use as fungicides for agricultural use practically impossible.

The Applicant has now surprisingly found that new phenyl-formamidines characterized by the presence of specific alkyl groups on the nitrogen atom and a benzoyl optionally substituted in position 4 of the phenyl ring, show an excellent fungicidal activity also at low doses and at the same time, are well tolerated by numerous important agrarian crops. They are also extremely favourable from an environmental point of view, as they have a low toxicity for mammals, fish, birds and other animal species.

A first object of the present invention therefore relates to new benzoylphenyl- formamidines having general formula (I):

(I)

wherein: Ri represents a C2-C6 alkyl, a C3-C6 cycloalkyl or a C4-C7 cycloalkylalkyl;

R2 represents a Ci-C alkyl;

or Ri and R₂, together with the N atom to which they are bound, form a heterocyclic ring containing from 4 to 7 atoms, possibly substituted by halogen atoms;

- R3 and R4, equal to or different from each other, represent a hydrogen atom, a halogen atom, a C1-C6 alkyl, a C1-C6 alkoxyl, a C1-C6 haloalkoxyl, a CF₃ group, a CF₂H group, a CFH₂ group or a cyano group;

R, equal or different when n > 2, represents a halogen atom, a C₁-C4 alkyl group, a C₁-C4 haloalkyl group, a C₁-C₄ alkoxyl group, a C₁-C₄ haloalkoxyl group, a C₁-C4 alkylthio group, a C₃- C cycloalkoxyl group, a carboxyl group, a C₂-C7 alkoxycarbonyl group, a benzyloxy group; a phenyl group optionally substituted; or two R substituents represent together a C1-C4 alkylenedi- oxy group;

n represents an integer from 0 to 4.

Examples of halogen are fluorine, chlorine, bromine, iodine.

Examples of C₁-C6 alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- butyl, tert-butyl, n-pentyl, 3-methylbutyl, n-hexyl, 3,3-dimethylbutyl.

Examples of C₃-C6 cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl. Examples of C₄-C7 cycloalkylalkyl are cyclopropylmethyl, cyclobutylmethyl, cyclopen- tylmethyl, cyclohexylmethyl.

Examples of C₁-C6 alkoxyl are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy.

Examples of C1-C6 haloalkoxyl are trifluoromethoxy, 1 , 1 ,2,2-tetrafluoroethoxy, 1 , 1 ,2,3 ,3 ,3 -hexa-fluoro-propoxy.

Examples of C₁-C4 alkylthio are methylthio, ethylthio, propylthio, isopropylthio.

Examples of C₂-C7 alkoxycarbonyl are methoxy-carbonyl, ethoxy carbonyl.

Examples of C₁-C4 alkylenedioxy are methylenedioxy, ethylenedioxy, propylenedioxy.

Examples of C3-C6 cycloalkoxyl are cyclopropoxy, cyclopentoxy, cyclohexyloxy.

Examples of heterocyclic rings having from 4 to 7 atoms, possibly halogenated, are: azet- idine, 3,3-difluoroazetidine, pyrrolidine, piperidine, 4-fluoropiperidine, morpholine.

Phenyl optionally substituted refers to a phenyl group which can have one or more sub- stituents, the same or different, preferably selected from the following groups: halogen atoms, Ci-C4 alkyls, Ci-C4 haloalkyls, C1-C4 alkoxyl s, Ci-C4 haloalkoxyls. The following also fall within the scope of the present invention:

a) all possible geometrical isomers of compounds having general formula (I) deriving from particular meanings of the substituents R-R4;

b) salts of the compounds having formula (I) obtained by the addition of inorganic or organ- ic acids;

c) crystalline adducts of the compounds having formula (I) with urea, in any ratio (molar or weight), preferably ranging from 1 : 1 to 1 :5;

d) inclusion compounds of the compounds having formula (I) with substances having a solubility in water lower than 150 g/1 and a melting point higher than 85°C, such as, for example, dimethylsulfone.

An object of the present invention therefore also relates to benzoylphenyl-formamidines that are a) mixtures of unseparated geometrical isomers, mixtures of partially separated geometrical isomers, single geometrical isomers; b) in the form of salts obtained by the addition of inorganic or organic acids; c) in the form of crystalline adducts with urea, in any molar or weight ra- tio, preferably from 1 : 1 to 1 :5; d) in the form of inclusion compounds with substances having a solubility in water lower than 150 g/1 and a melting point higher than 85°C, such as, for example, dimethylsulfone.

Examples of compounds having general formula (I) of particular interest for their biological activity are compounds wherein R_1; R₂, R3, R4, R and n have the meanings indicated in Ta- ble 1

(I)

Table 1

Examples of salts of compounds having general formula (I) of particular interest for their biological activity are compounds having formula (I) wherein Ri, R2, R3, Rt, R and n have the meanings specified hereunder, salified by addition with the acid specified hereunder, in

Tabl

Tabl

Preferred compounds having general formula (I) are those wherein Ri represents ethyl, R_2, R₃ and R4 represent methyl, R represents a halogen, a CF₃ group, an OCF₃ group or an OCH₃ group and n has the values 0-2, R being equal or different when n is equal to 2.

Compounds wherein Ri represents ethyl, R₂, R₃ and R4 represent methyl, R represents a CI or Br atom, a CF₃ group or an OCF₃ group and n has the values 0-2, R being equal or different when n is equal to 2, are even more preferred.

Compounds particularly preferred for their biological activity are indicated in Table 3 hereunder:

Table 3

The compounds having general formula (I) are prepared from the corresponding aniline having formula (II), according to reaction scheme 1.

Scheme 1

Various methods for effecting this transformation are known in literature; the most widely-used are the following:

a) treatment of aniline having formula (II) with an acetal having formula RiR₂NC(OR5), wherein R5 represents an alkyl, according to what is described in "Synthetic Communications", 24 (1994), pages 1617-1624; b) treatment of aniline having formula (II) with an amide having formula HCONR1R2 in the presence of POCI₃ or SOCI2_, according to what is described in "Tetrahedron", 46 (1990), pages 6058-61 12;

c) treatment of aniline having formula (II) with an orthoester having formula HC(ORs), wherein R5 represents an alkyl, to form the corresponding imino-ether and subsequently heating the same in the presence of an amine having formula HNRiR_2, according to what is described in US4209319;

d) treatment of aniline having formula (II) with phosgene to form the corresponding isocyanate and subsequent reaction with an amide having formula HCONR1R2, according to what is described in WO 00/46184;

e) treatment of aniline having formula (II) with

to form an N- cyanoamidine and subsequent reaction with an amine having formula HN ^_, according to what is described in WO 00/46184;

f) treatment of aniline having formula (II) with Ν,Ν-dimethylformamide in the pres- ence of a sulfonyl-chloride, such as for example 2-pyridylsulfonylchloride or phenylsulfonylchloride, to form the corresponding dimethylamidine (Ri=R₂=Me) and subsequent reaction with an amine having formula HNR^_, according to what is described in "Tetrahedron", 56 (2000), pages 8253-8262 and in "Journal Combinatorial Chemistry" 11 (2009), pages 126-130.

The compound having formula (II) can be prepared by acylation of the corresponding aniline, protected as carbamate having formula (IV) with a derivative of benzoic acid (VI), in the presence of a Lewis acid and subsequent deprotection of the compound (III) in the presence of a base, as indicated in reaction scheme 2, according to methods well-known in organic chemistry.

Scheme 2

(V) (IV) (ill)

The preferred reaction conditions for these substrates envisage the use of benzoylchloride (V) as acylating agent in the presence of zinc chloride as catalyst in an organic solvent, for example dichloroethane or methylene chloride, according to what is described in "Helvetica Chim- ica Acta", XXIX (1946), pages 1413-1424.

In addition to that indicated above, numerous other methods for effecting acylation reactions are known in literature; the most widely-used are the following:

a) treatment of the compound having formula (IV) or a precursor thereof, with a benzoic acid having formula (VI) in the presence of acid catalysts such as, for example, trifluo- romethanesulfonic acid, as described in "Tetrahedron", 56 (2000), pages 7199-7203; or graphite and methanesulfonic acid, as described in "Synthesis", 13 (2004), pages 2165-2168; or graphite and p-toluenesulfonic acid, as described in "Helvetiva Chimica Acta", 88 (2005), pages 2282- 2287; or 1-peifluorobutanesulfonic acid, as described in "Synthesis", 10 (2000), pages 1427- 1430; or trifluorosulfonylmethane as described in "Journal of Organic Chemistry", 26 (1990), pages 2031-2031;

b) treatment of the compound having formula (IV) or a precursor thereof, with a derivative of benzoic acid (V) in the presence of metal triflates such as, for example, copper triflate or gallium triflate or antimonium triflate or ytterbium triflate or scandium triflate or bismuth triflate, as described in "Green Chemistry", 4 (2002), pages 129-133 or in "Tetrahedron", 56 (2000), pages 6463-6465 or in "Bull. Chem. Soc Jpn", 73 (2000), pages 2325-2333;

c) treatment of the compound having formula (IV) or a precursor thereof, with a benzoic acid suitably substituted having formula (VI) in the presence of P2O5 as such or adsorbed on silica, as described in "Tetrahedron Letters", 49 (2008), pages 671 -6719;

d) treatment of a phenylboronic acid with a derivative of benzoic acid (VI) in the presence of a base such as, for example, sodium carbonate and a palladium-based catalyst, as de- scribed in "Tetrahedron Letters", 46 (2005), pages 7627-7630, or in "Synthesis", 13 (2007), pages 1970-1978;

e) treatment of a phenylboronic acid suitably substituted having formula (VII) with a derivative having formula (VIII) wherein X represents an activator group of the carboxylic function such as, for example, a chloride and Y represents a precursor of an amine group such as, for example, a nitro group or a HCOOR5 group, wherein R5 has the meaning already defined above, in the presence of a base such as, for example, sodium carbonate, a palladium-based cata- lyst and a surfactant such as, for example, sodium dodecyl sulfate, as described in "Synthesis", 13 (2007), pages 1970-1980, according to scheme 3.

Scheme 3

(VII) (VIII) (IX)

The product (IX) thus obtained, can be converted into the compound having formula (II) either by reduction of the nitro derivative if Y=NC>₂ according to methods well-known in organic chemistry, as described, for example, in "Advanced Organic Chemistry", Jerry March, 4^th Edition, 1992, John Wiley & Sons Pub., pages 1216-1217 and references cited therein, or by basic hydrolysis when Y corresponds to the group NHCOOR₅.

The compound having formula (III) can be easily deprotected to give the compound having formula (II) by reaction with a base such as sodium or potassium hydroxide in a mixture of water/alcohol according to what is described in "Protective groups in Organic Synthesis" Theodora W. Green, Third Edition (1999).

The compound having formula (IV) can be easily prepared by reaction of the commercial compound having formula (X) with a compound having formula CICOOR₅, wherein R₅ represents an alkyl group in the presence of a base, preferably potassium carbonate, according to reaction scheme 4.

Scheme 4

Alternatively, the compound having formula (II) can also be obtained by acylation of p- xylene with a derivative of benzoic acid (VI), for example a benzoyl chloride suitably substituted, in the presence of a Lewis acid, followed by the subsequent nitration of the product having formula (XI), thus obtained, and reduction of the nitro-derivative (XII) to give the corresponding aniline having formula (II), according to reaction scheme 5.

Scheme 5

(XII) (II) The preferred reaction conditions for obtaining compound (XI) are those already described above, compound (XII) can be easily prepared according to what is described in detail in international patent application WO 00/46184 or in "Tetrahedron Letters ", 37 (1996), pages 513-516.

The preferred reaction conditions for the reduction of compound (XII) envisage the use of zinc powder in glacial acetic acid according to what is described in "Comprehensive Organic Transformations", R. Larock (1999), Second Edition.

Compound (XI) can also be easily obtained by reaction between p-xylene and a benzo- nitrile suitably substituted, in the presence of palladium catalysts according to what is described in "J. Org. Chem.", 71 (2006), pages 3551-3558.

A further alternative for obtaining the compound having formula (II) is the reaction between the compound having formula (X) and a benzoyl chloride having formula (V), under such conditions as to obtain first the formation of the anilide and then acylation of the same to give compound (XIII) which, by reaction with KF and alumina, leads to the formation of compound (II), according to reaction scheme 6.

Scheme 6

The preferred reaction conditions for obtaining compound (II) from the product having formula (XIII) envisage the use of KF and alumina with the use of microwaves in the absence of a solvent, according to what is described in "Chin.J.Chem ", 29 (201 1), pages 2209-2212.

The compound having formula (II) can again be easily obtained by Fries rearrangement starting from compound (XIV), according to reaction scheme 7.

Scheme 7

The preferred reaction conditions for obtaining compound (II) from the product having formula (XIV) envisage the use of AICI₃ and irradiation of microwaves in the absence of a solvent, according to what is described in "Indian. J. Chem., Section B: Organic Chemistry Including Medicinal Chemistry", 44 (2005), pages 635-637.

As already indicated, the compounds having general formula (I) have an extremely high fungicidal activity which is exerted with respect to numerous phytopathogenic fungi that attack important agricultural crops.

A further object of the present invention therefore relates to the use of compounds having formula (I) for the control of phytopathogenic fungi of agricultural crops.

Examples of phytopathogenic fungi that can be effectively treated and fought with the compounds having general formula (I) are those belonging to the species of Basidiomycetes, As- corn cetes, Deuteromycetes or imperfect fungi, Ooraycetes: Puccinia spp., Ustilago spp., Tilletia spp., Uromyces spp., Phakopsora spp., Rhizoctonia spp., Erysiphe spp., Sphaerotheca spp., Pod- osphaera spp., Uncinula spp., Helminthosporium spp., Rhynchosporium spp., Pyrenophora spp., Monilinia spp., Sclerotinia spp., Septoria spp. (Mycosphaerella spp ), Venturia spp., Botrytis spp., Alternaria spp., Fusarium spp., Cercospora spp., Cercosporella herpotrichoides, Colleto- trichum spp., Pyricularia oryzae, Sderotium spp., Phytophtora spp., Pythium spp., Plasmopara viticola, Peronospora spp., Pseudoperonospora cubensis, Bremia lactucae.

The main crops that can be protected with the compounds according to the present inven- tion comprise cereals (wheat, barley, rye, oats, rice, corn, sorghum, etc.), fruit trees (apple-trees, pear-trees, plum-trees, peach-trees, almond-trees, cherry-trees, banana-trees, vines, strawberries, raspberries, blackberries, etc.), citrus fruits (orange-trees, lemon-trees, tangerine-trees, grape- fruit-trees, etc.), legumes (beans, peas, lentils, soybean, etc.), vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, aubergines, peppers, etc.), cucurbits (pump- kin, courgettes, cucumbers, melons, water-melons, etc.), oleoginous plants (sunflower, rape, peanut, castor-oil, coconut, etc.), tobacco, coffee tea, cocoa, sugar beet, sugar cane, cotton, nuts.

In particular, the compounds having formula (I) have proved to be extremely effective in the control of Plasmopara viticola on vines, Phytophtora infestans and Botrytis Cinerea on tomatoes, Puccinia recondita, Erysiphe graminis, Helminthosporium teres, Septoria nodorum and Fusarium spp. on cereals, in the control of Phakopsora pachyrhizi on soya, in the control of Uromyces Appendiculatus on beans, in the control of Venturia inaequalis on apple-trees, in the control of Sphaerotheca f liginea on cucumbers.

Furthermore, the compounds having general formula (I) are also effective in the control of phytopathogenic bacteria and viruses, such as, for example, Xanthomonas spp., Pseudomonas spp., Erwinia amylovora, the mosaic virus of tobacco.

The compounds having general formula (I) are capable of exerting a fungicidal action of both a curative and preventive nature and have an extremely low or zero phytotoxicity on the crops treated.

For practical uses in agriculture, it is often preferable to use the compounds of the present invention suitably formulated in compositions containing, in addition to one or more compounds having formula (I), agronomically acceptable co-formulants

A further object of the present invention therefore relates to fungicidal compositions comprising one or more compounds having formula (I), a solvent and/or a solid or liquid diluent, possibly one or more surfactants and other agronomically acceptable co-formulants.

The above compositions can be in the form of dry powders, wettable powders, emulsifia- ble concentrates, emulsions, microemulsions, pastes, granules, water-dispersible granules, solutions, suspensions, etc. : the selection of the type of composition depends on the specific use.

The fungicidal compositions are prepared in the known way, for example by diluting or dissolving the active substance with a solvent medium and/or a solid or liquid diluents, possibly in the presence of surfactants.

The following can be used, for example, as solid diluents, or carriers: silica, kaolin, ben- tonite, talc, fossil flour, dolomite, calcium carbonate, magnesia, gypsum, clays, synthetic silicates, attapulgite, seppiolite.

Liquid solvents or diluents that can be used are, for example, in addition to water, aromatic organic solvents (xylols or mixtures of alkylbenzenes, chlorobenzene, etc.), paraffins (oil fractions), alcohols (methanol, propanol, butanol, octanol, glycerine, etc.), esters (ethyl acetate, isobutyl acetate, alkyl carbonates, alkyl esters of adipic acid, alkyl esters of glutaric acid, alkyl esters of succinic acid, alkyl esters of lactic acid, etc.), vegetable oils (rape oil, sunflower oil, soybean oil, castor oil, corn oil, peanut oil, and their alkyl esters), ketones (cyclohexanone, acetone, acetophenone, isophorone, ethylamylketone, etc.), amides (Ν,Ν-dimethylformamide, N- methylpyrrolidone, etc.), sulfoxides and sulfones (dimethylsulfoxide, dimethylsulfone, etc.), and mixtures thereof. Surfactants that can be used are sodium, calcium, potassium salts, salts of triethylamine or triethanolamine of alkylnaphthalenesulfonates, polynaphthalenesulfonates, alkyl sulfonates, aryl sulfonates, alkylarylsulfonates, polycarboxylates, sulfosuccinates, alkylsulfosuccinates, lig- nin sulfonates, alkylsulfates; and again, polyethoxylated fatty alcohols, polyethoxylated al- kylphenols, polyethoxylated esters of sorbitol, polypropoxy polyethoxylates (block polymers), can be used.

The fungicidal compositions can also contain special additives for particular purposes, for example, antifreeze agents such as propylene glycol, or adhesion agents such as Arabic rubber, polyvinyl alcohol, polyvinylpyrrolidone, etc.

The concentration of the compounds having general formula (I) in the above compositions can vary within a wide range; they can generally range from 1% to 90% by weight with respect to the total weight of the composition, preferably from 5 to 50% by weight with respect to the total weight of the composition.

According to another aspect of the present invention, other active principles can be added to the fungicidal compositions containing the compounds having general formula (I), compatible therewith, such as, for example, fungicides different from those having general formula (I), phy- toregulators, antibiotics, herbicides, insecticides, fertilizers and/or mixtures thereof.

In particular, it is advantageous to add other fungicidal compounds to the above compositions. Examples of fungicides different from those having general formula (I) that can be includ- ed in the fungicidal compositions are:

3-difluoromethyl-N-(7-fluoro- 1 , 1 ,3-trimethyl-4-indanyl)- 1 -methyl-4-carboxamide, acibenzolar, ametoctradin, amisulbrom, ampropylfos, anilazine, azaconazole, azoxystrobin, benalaxyl, benal- axyl-M, benomyl, benthiavalicarb, benzo-vindiflupyr, bitertanol, bixafen, blasticidin-S, boscalid, bromuconazole, bupirimate, buthiobate, captafol, captan, carbendazim, carboxin, carpropamid, chinomethionat, chloroneb, chlorothalonil, chlozolinate, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, debacarb, dichlofluanid, dichlone, diclobutrazol, diclomezine, di- cloran, diclocymet, diethofencarb, difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxy-strobin, diniconazole, dinocap, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, edifenphos, epoxiconazole, etaconazole, ethaboxam, ethirimol, ethoxyquin, etridiazole, famox- adone, fenamidone, fenaminosulf, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, fluopicolide, fluopyram, fluoroimide, fluotrima- zole, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, furconazole, fur- conazole-cis, guazatine, hexaconazole, hymexazol, hydroxyquinoline sulfate, imazalil, imiben- conazole, iminoctadine, ipconazole, iprobenfos, iprodione, isoprothiolane, iprovalicarb, isopyra- zam, isotianil, kasugamycin, kresoxim-methyl, mancopper, mancozeb, mandipropamid, maneb, mebenil, mepanipyrim, mepronil, meptyldinocap, metalaxyl, metalaxyl-M, metconazole, meth- furoxam, metiram, metominostrobin, metrafenone, metsulfovax, myclobutanil, natamycin, nico- bifen, nitrothal-isopropyl, nuarimol, ofurace, orysastrobin, oxadixyl, oxathiapiproline, oxpocon- azole, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorofenol and its salts, penthiopyrad, phthalide, picoxystrobin, piperalin, Bordeaux mixture, polyoxins, probena- zole, prochloraz, procymidone, propamocarb, propiconazole, propineb, proquinazid, prothiocarb, prothioconazole, pyracarbolid, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, py- ribencarb, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, pyroxyfur, quinacetol, quinazamid, quinconazole, quinoxyfen, quintozene, rabenzazole, copper hydroxide, copper oxychloride, copper (I) oxide, copper sulfate, sedaxane, silthiofam, simeconazole, spiroxamine, streptomycin, tebuconazole, tebufloquin, tetraconazole, thiabendazole, thiadifluor, thicyofen, thifluzamide, thi- ophanate, thiophanate-methyl, thiram, tiadinil, tioxymid, tolclofos-methyl, tolylfluanid, triadime- fon, triadimenol, triarimol, triazbutil, triazoxide, tricyclazole, tridemorf, trifloxystrobin, triflumi- zole, triforine, triticonazole, uniconazole, uniconazole-P, validamycin, valifenalate, vinclozolin, zineb, ziram, sulfur, zoxamide.

A further object of the present invention therefore relates to fungicidal compositions comprising at least one compound having general formula (I) and at least one other known fungicide.

Fungicidal compositions containing at least one benzoylphenyl-formamidine having formula (I) and one or more known fungicides, particularly preferred for the particularly wide range of action and a marked synergic effect, are those wherein one or more compounds having general formula (I) are combined with one or more known fungicides belonging to the following classes:

a) azoles selected from azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, epoxy-conazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prochloraz, prothiocona- zole, simeconazole, tebu-conazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticon- azole;

b) amines inhibitors of ergosterol biosynthesis selected from aldimorph, dodemorph, fenpropi- morph, fenpropidin, spiroxamine, tridemorph;

c) inhibitors of succinate-dehydrogenase (SDHI) selected from benzovindiflupyr, bixafen, bos- calid, carboxin, fluopyram, flutolanil, fluxapyroxad, furametpyr, isopyrazam, oxycarboxin, pen- flufen, penthiopyrad, sedaxane, thifluzamide, 3-difluoromethyl-N-(7-fluoro-l, l,3-trimethyl-4- indanyl)-l-methyl-4-carboxamide;

d) strobilurins selected from azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrameto-strobin, pyraoxostrobin, trifloxystrobin;

e) specific antioidic compounds selected from cyflufenamid, flutianil, metrafenone, proquinazid, pyriofenone, quinoxyfen;

f) aniline-pyramidines selected from pyrimethanil, mepanipyrim, cyprodinil,

g) benzimidazoles and analogues thereof selected from carbendazim, benomyl, thiabendazole, thiophanate-methyl;

h) dicarboxyimides selected from iprodione, procymidone;

i) phtalimides selected from tra captafol, captan, folpet;

1) systemic acquired resistance (SAR) inductors selected from acibenzolar, probenazole, isotianil, tiadinil;

m) phenylpyrroles selected from fenpiclonil, fludioxonil;

n) acylalanines selected from benalaxyl, benalaxyl-M, furalaxyl, metalaxyl, metal axyl-M;

o) other specific antiperonosporic compounds selected from ametoctradin, amisulbrom, ben- thiavalicarb, cyazofamid, cymoxanil, dimethomorph, ethaboxam, famoxadone, fenamidone, flumetover, flumorph, fluopicolide, iprovalicarb, mandipropamid, oxathiapiproline, vali- fenalate;

p) dithiocarbamates selected from maneb, mancozeb, propineb, zineb;

q) phosphorous acid and its inorganic and organic salts, fosetyl-aluminium;

r) rameic compounds selected from Bordeaux mixture, carpropamid, copper hydroxide, copper oxychloride, copper sulfate, copper salycilate; s) other fungicides selected from chlorothalonil, fenhexamid, fenpyrazamine, fluazinam, sylthi- ofam, tebufloquin, zoxamide, dodine, guazatine, iminoctadine.

The fungicidal compounds are indicated in the present description with their ISO international name; the chemical structures and their CAS and IU AC names are indicated in Alan Wood's Website (www. alanwood. net). Compendium of Pesticide Common Names; the physic- chemical data and the biological characteristics of most of these compounds are indicated in "Pesticide Manual", C.D.S. Tomlin, 15^a Edition, 2009, British Crop Production Council.

The compound 3 -difluoromethyl-N-(7-fluoro- 1 ,1 ,3 -trimethyl-4-indanyl)- 1 -methyl-4- carboxamide has been described in patent application WO 2012/084812.

Preferred compositions containing at least one compound having formula (I) (component

A) and at least another known fungicide are those consisting of:

CI : compound 1 + tetraconazole;

C2: compound 1 + tebuconazole;

C3 : compound 1 + cyproconazole;

C4: compound 1 + difenoconazole;

C5 : compound 1 + epoxyconazole;

C6: compound 1 + flutriafol;

C7: compound 1 + penconazole;

C8 : compound 1 + prothioconazole;

C9: compound 1 + prochloraz;

CIO: compound 1 + fenpropimorph;

CI 1 : compound 1 + spiroxamine;

CI 2: compound 1 + bixafen;

C13 : compound 1 + boscalid;

C14: compound I + carboxin;

CI 5 : compound 1 + fluopyram;

CI 6: compound 1 + fluxapyroxad;

CI 7: compound 1 + isopyrazam;

CI 8: compound 1 + penthiopyrad;

CI 9: compound 1 + sedaxane;

C20: compound 1 + azoxystrobin; C21 : compound + dimoxystrobin;

C22: compound ] + fluoxastrobin;

C23 : compound ] + kresoxim-methyl;

C24: compound 1 + picoxystrobin;

C25 : compound + pyraclostrobin;

C26: compound + trifloxystrobin;

C27: compound ] + metrafenone;

C28: compound ] I + proquinazid;

C29: compound ] I + mepanipyrim;

C30: compound + cyprodinil;

C31 : compound ] + iprodione;

C32: compound ] + procymidone;

C33 : compound 1 + carbendazim;

C34: compound ] I + thiophanate-methyl

C35: compound 1 + 3-difluoromethyl-N-(7-£luoro-l, l,3-trimethyl-4-indanyl)-l-methyl-4- carboxamide,

C36: compound 1 + benalaxyl-M,

C37: compound 1 + benzovindiflupyr,

C38: compound 8 + tetraconazole,

C39: compound 8 + 3-difluoromethyl-N-(7-fluoro-l, l,3-trimethyl-4-indanyl)-l-methyl-4- carboxamide,

C40: compound 8 + azoxystrobin,

C41 : compound 8 + pyraclostrobin,

C42: compound 9 + tetraconazole,

C43 : compound 9 + 3-difluoromethyl-N-(7-fluoro-l, l,3-trimethyl-4-indanyl)-l-methyl-4- carboxamide,

C44: compound 9 + azoxystrobin,

C45: compound 9 + pyraclostrobin,

C46: compound 10 + tetraconazole,

C47: compound 10 + 3-difluoromethyl-N-(7-fluoro-l, l,3-trimethyl-4-indanyl)-l-methyl-4- carboxamide, C48: compound 10 + azoxystrobin,

C49: compound 10 + pyraclostrobin,

C50: compound 1.1 + tetraconazole,

C51 : compound 1.1 + 3-difluoromethyl-N-(7-fluoro-l, l,3-trimethyl-4-indanyl)-l-methyl-4- carboxamide,

C52: compound 1.1 + azoxystrobin,

C53 : compound 1.1 + pyraclostrobin,

C54: compound 1.1 + benzovindiflupyr,

C55: compound 1.1 + fluxapyroxad,

C56: compound 1 + tetraconazole + azoxystrobin,

C57: compound 1 + pyraclostrobin + tetraconazole,

C58: compound 1 + epoxyconazole + azoxystrobin,

C59: compound 1 + pyraclostrobin + epoxyconazole,

C60: compound 1 + azoxystrobin + 3-difluoromethyl-N-(7-fluoro-l, l,3-trimethyl-4-indanyl)-l- methyl-4-carboxamide,

C61 : compound 1 + pyraclostrobin + 3-difluoromethyl-N-(7-fluoro-l, l,3-trimethyl-4-indanyl)-l- methyl-4-carboxamide,

C62: compound 1 + 3-difluoromethyl-N-(7-fluoro-l, l,3-trimethyl-4-indanyl)-l-methyl-4- carboxamide + tetraconazole,

C63 : compound 1.1 + tetraconazole + azoxystrobin,

C64: compound 1.1 + pyraclostrobin + tetraconazole,

C65: compound 1.1 + epoxyconazole + azoxystrobin,

C66: compound 1.1 + pyraclostrobin + epoxyconazole,

C67: compound 1.1 + azoxystrobin + 3-difluoromethyl-N-(7-fluoro-l, l,3-trimethyl-4-indanyl)- l-methyl-4-carboxamide,

C68: compound 1.1 + pyraclostrobin + 3-difluoromethyl-N-(7-fluoro-l, l,3-trimethyl-4-indanyl)- l-methyl-4-carboxamide,

C69: compound 1.1 + 3-difluoromethyl-N-(7-fluoro-l, l,3-trimethyl-4-indanyl)-l-methyl-4- carboxamide + tetraconazole.

Component A, i.e. the compounds having general formula (I), of the previous compositions C1-C75 are described and exemplified in the following tables 4 and 6 and are specifically the following compounds having general formula (I) wherein the substituents have the meanings indicated hereunder:

The compound 1.1 is the salt of the compound having general formula (I) wherein the various substituents have the meanings indicated hereunder and the acid used for salification is hydrochloric acid:

The synergic effect of the compositions containing a compound having general formula (I) (component A) and a known fungicide (component B), can be evaluated by applying the Colby formula ("Weeds, 1967, 15, pages 20-22):

wherein E_t is the expected effectiveness percentage for the composition containing compounds A and B at doses d_A + de, EA is the effectiveness percentage observed for component A at a dose d_a, E_B is the effectiveness percentage observed for component B at a dose ds. When the effectiveness observed for the composition A + B (EA+B) is higher than the expected effectiveness according to the Colby formula (EA+B E₍ > 1), there is a synergic effect.

In the case of ternary combinations, the Colby formula has the form:

E, = E_A + EBI + E_B2 - (EAXEBI + E_AxE_B2 + E_BixE_B2)/100 wherein E_t is the expected effectiveness percentage for the composition containing compounds A, B l and B2 at doses dA + dei + dB2, EA is the effectiveness percentage observed for component A at a dose dA, EBI is the effectiveness percentage observed for component B l at a dose dei, EB2 is the effectiveness percentage observed for component B2 at a dose de2- When the effectiveness observed for the composition A + Bl + B2 (EA+BI+B2) is higher than the expected effectiveness according to the Colby formula (ΕΑ+ΒΙ+Β2 Έ₍ > 1), there is a synergic effect. The main crops that can be protected with the compositions comprising at least one compound having formula (I), alone or combined with at least one other known active principle, comprise cereals (wheat, barley, rye, oats, rice, corn, sorghum, etc.), fruit trees (apple-trees, pear- trees, plum-trees, peach-trees, almond-trees, cherry-trees, banana-trees, vines, strawberries, rasp- berries, blackberries, etc.), citrus fruits (orange-trees, lemon-trees, tangerine-trees, grapefruit- trees, etc.), legumes (beans, peas, lentils, soybean, etc.), vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, aubergines, peppers, etc.), cucurbits (pumpkin, courgettes, cucumbers, melons, water-melons, etc.), oleoginous plants (sunflower, rape, peanut, castor-oil, coconut, etc.), tobacco, coffee tea, cocoa, sugar beet, sugar cane, cotton, nuts.

In particular, the compositions of the present invention have proved to be extremely effective in the control of Plasmopara viticola on vines, Phytophtora infestans and Botrytis Ciner- ea on tomatoes, Puccinia recondita, Erysiphe graminis, Helminthosporium teres, Septoria no- dorum and Fusarium spp. on cereals, in the control of Phakopsora pachyrhizi on soya, in the control of Uromyces Appendiculatiis on beans, in the control of Venturia inaequalis on apple- trees, in the control of Sphaerotheca fuliginea on cucumbers.

Furthermore, the compounds having general formula (I) are also effective in the control of phytopathogenic bacteria and viruses, such as, for example, Xanthomonas spp., Pseudomonas spp., Erwinia amylovora, the mosaic virus of tobacco.

The compositions object of the present invention are capable of exerting a fungicidal ac- tion that can be of a curative, preventive or eradicating nature and generally have an extremely low or zero phytotoxicity on the crops treated.

A further object of the present invention therefore relates to the use of compositions comprising at least one benzoylphenyl-formamidine having general formula (I) for the control of phytopathogenic fungi of agricultural crops.

When the compositions comprise a compound having general formula (I) and at least one known active principle, the weight ratios in the above compositions vary according to the compounds preselected and can normally range from 1 : 100 to 100: 1, preferably from 1 : 10 to 10: 1.

The total concentration of active components in the above compositions can vary within a wide range; it generally varies from 1% to 99% by weight with respect to the total weight of the composition, preferably from 5% to 90% by weight with respect to the total weight of the composition. The application of these compositions can be effected on all parts of the plant, for example on the leaves, stems, branches and roots, or on the seeds themselves before being planted, or on the ground in which the plant grows.

A further object of the present invention therefore relates to a method for the control of phytopathogenic fungi in agricultural crops, which consists in applying, on any part of the plants to be protected, effective and non-phytotoxic doses of compositions comprising at least one compound having general formula (I) and, optionally, one or more known active principles, compatible therewith.

The quantity of compound to be applied for obtaining the desired effect can vary in rela- tion to various factors such as, for example, the compound(s) used, the crop to be preserved, the type of pathogen, the degree of infection, the climatic conditions, the application method, the formulation adopted.

Doses of compounds having formula (I) ranging from 10 g to 5 kg per hectare of agricultural crop or, in the case of compositions comprising other known active principles, overall doses of active principles ranging from 10 g to 10 kg per hectare of agricultural crop, generally provide a sufficient control.

The following examples are provided for a better understanding of the invention, which should be considered as being purely illustrative and non-limiting of the invention itself.

EXAMPLE 1

Preparation of N-ethyl-N-methyl-N'-[4-benzoyl-2,5-xylyl]-formamidine [Compound nr.l]. a) Preparation of N-methoxycarbonyl-2.5-dimethylaniline [carbamate having general formula (TV)l

68.43 g (0.495 moles) of potassium carbonate were added, at room temperature, to 50 g (0.413 moles) of 2,5-dimethylaniline dissolved in 350 ml of acetone.

46.79 g (0.495 moles) of methylchloroformiate were added dropwise, under stirring, to this solution and the whole mixture was heated to reflux temperature for 4 hours.

After GC-MS control, the reaction mixture was cooled to room temperature, most of the acetone was evaporated, the mixture was diluted with water and extracted with ethyl acetate.

The organic phase was anhy drifted with sodium sulfate, then filtered and evaporated. The raw product thus obtained was washed under reflux with 100-150 ml of hexane, then filtered and dried. 59.5 g of product (yield 80%) were obtained. GC-MS: M = 179.

b) Preparation of N-methoxycarbonyl-4-benzoyl-2.5-dimethylaniline [carbamate having general formula (III)l.

46.3 g (0.32 moles) of zinc chloride were added under stirring to a solution of 30 g (0.21 moles) of benzoyl chloride in dichloroethane anhydrified on molecular sieves (40 ml), 28.5 g (0.16 moles) of N-methoxycarbonyl-2,5-dimethylaniline dissolved in 40 ml of dichloroethane anhydrified on molecular sieves, were added to the reaction mixture, kept under stirring, at 60°C.

The temperature was brought to 90°C and the mixture was kept under stirring for 3 hours. When the reaction was complete (GC and TLC analyses), the mixture was cooled to room temperature; 200 ml of water were then added.

The phases were then separated, the organic phase was washed with 100 ml of a saturated solution of NaHCC , followed by a solution at 10% of HC1 and twice again with water.

After anhydrification on sodium sulfate, filtration and evaporation of the solvent at reduced pressure, 40.8 g (0.144 moles) of the desired product were obtained as a cream-coloured solid. Yield 90.2%, GC-MS: M⁺ = 283.

c) Preparation of 4-benzoyl-2.5-dimethylaniline [aniline having general formula (II)] : Method 1

A solution of sodium hydroxide obtained by dissolving 28.2 g (0.71 moles) of NaOH in 250 ml of water was trickled, under stirring, onto a solution of 40 g (0.14 moles) of N- methoxycarbonyl-4-benzoyl-2,5-dimethylaniline in 250 ml of ethanol.

The reaction mixture was maintained at 90°C for 40 minutes.

When the reaction was complete (GC and TLC analyses), the ethanol was evaporated at reduced pressure and a further 150 ml of water were added; the whole mixture was left under stirring at 70°C for 30 minutes, the solid obtained was then filtered again under heat and washed with additional water.

After drying in air, 30.8 g of the desired product were obtained as a yellow solid. Yield 97.8% GC-MS: M⁺= 225.

d) Preparation of N-ethyl-N-methyl-N'-[4-benzoyl-2,5-xylyl formamidine [Compound nr.l]

Catalytic / oluene-sulfonic acid was added to a mixture of 30 g of 4-benzoyl-2,5- dimethylaniline (0.133 moles) and 110 ml of triethyl-orthoformiate (0.67 moles).

The whole mixture was brought to reflux temperature and kept under stirring for 3 hours, controlling the course of the reaction by GC-MS.

When the reaction was complete, the reaction mixture was concentrated under reduced pressure and the raw product obtained was dissolved in methylene chloride (70 ml), to which 17.1 ml of N-ethyl-N-methylamine (0.20 moles) were added dropwise.

The mixture was left under stirring for 3 hours at 40°C, water was then added to the reaction mixture and the phases were separated.

After anhydrification of the organic phase on sodium sulfate, filtration and evaporation at reduced pressure, the solid product obtained was re-crystallized from hexane, obtaining 38.8 g (0.131 moles) of the desired product.

Yield 99.2% M.P.= 69-71°C.

GC-MS: M⁺ = 294. ¾-NMR (D-ppm, CDC1₃) = 1.21 (t, 3H); 2.20 (s, 3H); 2.35 (s,3H); 3.05 (s, 3H); 3.38 (q, 2H); 6.62 (s, 1H); 7.15 (s, 1H); 7.25 (s, 1H); 7.39-7.58 (m,3H); 7.78-7.80(d, 2H). EXAMPLE 2

Preparation of 4-benzoyl-2,5-dimethylaniline [aniline having general formula (II)] : Method 2.

a) Preparation of (2.5-dimethylphenyl)benzamide

85 g (0.60 moles) of potassium carbonate were added to a solution of 50 g (0.41 moles) of 2,5-dimethylaniline in 50 ml of acetone anhydrified on sieves.

47.4 ml (0.41 moles) of benzoyl chloride were poured dropwise, under vortex stirring at room temperature; after an hour, the solid present was filtered, washed with water and left to dry in air.

91.2 g (0.40 moles) of the desired product were obtained. Yield 99% GC: M⁺= 225. b) Preparation of (4-benzoyl-2,5-dimethylphenyl) benzamide Γ amide having general formula (XIII)l

1 12 g (0.82 moles) of zinc chloride were added, under stirring, to a solution of 74.6 g (0.53 moles) of benzoyl chloride in dichloroethane anhydrified on sieves (150 ml); 91.2 g (0.40 moles) of (2,5-dimethylphenyl)benzamide dissolved in 150 ml of dichloroethane anhydrified on sieves, were added to the reaction mixture, kept under stirring at 60°C.

The temperature was brought to 90°C and the mixture was kept under stirring for 8 hours; when the reaction was complete (GC and TLC analyses), the mixture was cooled to room temperature.

300 ml of water were added, the phases were separated and the organic phase washed with 100 ml of a saturated solution of NaHCC^, followed by a solution of HQ at 10%, then twice again with water.

After anhydrification of the organic phase on sodium sulfate, filtration and evaporation of the solvent at reduced pressure, 115 g of the desired product were obtained (0.36 moles) as a yel- low solid. Yield 87.4% GC-MS: M⁺= 329.

c) Preparation of 4-benzoyl-2,5-dimethylaniline [aniline having general formula (II)]

A mixture of 11.5 g (0.036 moles) of (4-benzoyl-2,5-dimethyl-phenyl)benzamide and 11 g of KF/AI2O₃ was placed in a microwave oven and subjected to irradiation at about 2,400 Hz for 4 minutes.

After cooling, the reaction mixture was diluted with water and ethyl ether, the phases were separated and the organic phase dried and evaporated to give 7.2 g of the desired aniline. Yield 90% GC-MS: M+ = 225.

EXAMPLE 3

Preparation of 4-benzoyl-2,5-dimethylaniline [aniline having general formula (II)]: Method 3.

a) Preparation of 2.5-dimethylbenzophenone [benzophenone having general formula (XI)]

32.8 g of P2O5/S1O2, obtained by mixing 16.4 g of P₂0₅ and 16.4 g of silica (0.063-0.200 mm) previously heated to 120°C for 24 hours, were added to a mixture of 10 g (0.082 moles) of benzoic acid and 53.0 g (0.50 moles) of /^-xylene.

After keeping the reaction mixture at reflux temperature for three hours and then bringing it back to room temperature, it was then diluted with 800 ml of dichloromethane and, after vigorous stirring, was filtered and washed with further dichloromethane.

The organic phase was treated with a solution of NaHCC>3 at 10%, anhydrified on sodium sulfate and evaporated at reduced pressure.

The product obtained was washed at room temperature with w-hexane, filtered and dried in air.

13.4 (0.064 moles) of 2,5-dimethylbenzophenone were obtained. Yield 78%. GC-MS: 1^= 210.

b) Preparation of 2,5-dimethyl-4-nitrobenzophenone [benzophenone having formula (XII)l

50.80 ml of glacial acetic acid and 6.46 ml of sulfuric acid at 95-97% were added to 13.4 g (0.064 moles) of 2,5-dimethylbenzophenone, maintained at about 4-5°C with an ice bath.

A sulfonitric mixture, obtained by mixing 6.46 ml of nitric acid at 65% and 26 ml of sulfuric acid 95-97%, was added dropwise to this mixture, maintained cold and under vigorous stirring.

After three hours, the reaction was complete, the mixture was then poured into a beaker containing ice, and the whole mixture was transferred to a separating funnel and extracted with ethyl acetate (3 x 300 ml).

After washing with a saturated solution of K2CO₃ and a large amount of water, the organic phase was anhydrified on sodium sulfate and evaporated at reduced pressure.

The raw product obtained was washed at room temperature with «-hexane, filtered and dried in air.

10.9 g (0.043 moles) of 2,5-dimethyl-4-nitrobenzophenone, with a purity of 95% of the desired isomer, were obtained. Yield 67%. GC-MS: M⁺= 255.

c) Preparation of 4-benzoyl-2.5-dimethylaniline [aniline having general formula (III)]

3.69 ml of glacial acetic acid (0.064 moles) were added to a solution of 10.9 g of 2,5- dimethyl-4-nitrobenzophenone (0.043 moles) in 190 ml of ethanol and 19 ml of water, 19.2 g of Zn powder (0.294 moles) were then carefully added to the reaction mixture kept under stirring at 60°C.

After bringing the temperature to 90°C and maintaining the reaction under these condi- tions for 3.5 hours, the mixture was cooled to room temperature.

The solid product was filtered on a celite bed and the ethanol concentrated at reduced pressure.

The raw product thus obtained was washed with a saturated solution of sodium bicarbonate and extracted with ethyl acetate.

The organic phase was washed thoroughly with water, anhydrified on sodium sulfate, fil- tered and evaporated to give 9.67 g of product, which was washed at room temperature with 150 ml of a mixture of hexane: ethyl ether 9: 1, and filtered to give 6.9 g of the desired product as a yellow solid. Yield 72% GC-MS: M⁺ = 225.

EXAMPLE 4

Preparation of compounds nr. 2 - 36.

Operating analogously to what is described in the previous examples, the compounds having formula (I) indicated in Table 4 were obtained, also comprising compound 1 in the first line.

(I)

Table 4

N° Ri Ri R₃ R4 R n

1 Et Me Me Me - 0

2 Bu Me Me Me - 0

3 iPr Me Me Me - 0

4 -CH₂CF₂CH₂- Me Me - 0

5 -(CH₂)₄- Me Me - 0

6 -(CH₂)₅- Me Me - 0

7 -CH₂CH₂OCH₂C¾- Me Me - 0

8 Et Me Me Me 2-Br 1

9 Et Me Me Me 3-CF₃ 1

10 Et Me Me Me 3 -Br 1

11 Et Me Me Me 2,5-CF₃ 2

12 Et Me Me Me 3-OCH₃ 1

13 Et Me Me Me 4-OCH₃ 1

14 Et Me Me Me 3,4-OCH₃ 2

15 Et Me Me Me 4-Z-Bu 1

16 Et Me Me Me 3,4-OC¾0- 2

17 Et Me Me Me 2-C1 1

18 Et Me Me Me 2,6-Cl- 2

19 Et Me Me Me 4-C1 1 20 Et Me Me Me 4-SCH₃ 1

21 Et Me Me Me 4-OCF₃ 1

22 Et Me Me Me 4-Br 1

23 Et Me Me Me 2-OCF₃ 1

24 Et Me Me Me 2,5-Br 2

25 Et Me Me Me 2-Cl-5-Br 2

26 Et Me Me Me 2-Cl-5-CF₃ 2

27 Et Me Me Me 2-Br-5-Cl 2

28 Et Me Me Me 3-Br-5-Cl 2

29 Et Me Me Me 3-Cl-5-Br 2

30 Et Me Me Me 3 -CI 1

31 Et Me Me Me 3-C1-4-C1 2

32 Et Me Me Me 4-CF₃ 1

33 Et Me Me Me 3-F-4-COOH 2

34 Et Me Me Me 3-CF3-4-COOH 2

35 Et Me Me Me 3-OCF₃ 1

36 Et Me Me Me 2,5-F-3 -OCH₃ 4

4-COOH

The results of the GC-MS analyses carried out on the synthesized products are indicated in Table 5.

Table 5

16 338

17 328

18 363

19 328

20 340

21 378

22 373

23 378

24 452

25 407

26 396

27 407

28 407

29 407

30 328

31 363

32 362

33 356

34 406

35 378

36 404

EXAMPLE 5

Preparation of N-ethyl-N-methyl-N'-[4-benzoyl-2,5-xylyl]-formamidine chlorohydrate [Compound nr.1.1].

4.25 ml of a 4M solution of hydrochloric acid in dioxane were added dropwise, at room temperature, to a solution of 5.0 g (0.017 moles) of N-ethyl-N-methyl-N'-[4-benzoyl-2,5-xylyl]- formamidine, dissolved in 37 ml of ethyl ether.

At the end of the dripping, the reaction mixture was further diluted with an additional 4.25 ml of dioxane and after 30' of stirring at room temperature, the precipitate formed was fil- tered.

The product was washed with about 20 ml of ethyl ether and left to dry in air. 5.54 g of a water-soluble product were obtained.

EXAMPLE 6

Preparation of compounds nr. 1.2-1.5.

Operating analogously to what is described in the previous examples, the salts of the com- pounds having formula (I) indicated in Table 6, were obtained, also comprising compound 1.1 in the first line.

Table 6

EXAMPLE 7

Preparation of the adduct of N-ethyl-N-methyl-N' [4-benzoyl-2,5-xylyl]-formamidine with urea.

3.06 g (0.051 moles) of urea were dissolved in 15 ml of methanol and 5 g (0.017 moles) of N-ethyl-N-methyl-N'[4-benzoyl-2,5-xylyl]-formamidine were added, maintaining room temperature values.

After 15 minutes under stirring at this temperature, the solvent was evaporated, obtaining 7.8 g of a yellowish solid product characterized by means of HPLC.

EXAMPLE 8

Preparation of the inclusion product of N-ethyl-N-methyl-N' [4-benzoyl-2,5-xylyl]- formamidine with dimethyl sulfone.

8 g (0.085 moles) of dimethyl sulfone were dissolved in 35 ml of methylene chloride and 5 g (0.017 moles) of N-ethyl-N-methyl-N' [4-benzoyl-2,5-xylyl]-formamidine were added, under stirring and at room temperature.

At the end of the addition, the whole mixture was kept under stirring for 15-20 minutes, the solvent was then evaporated obtaining 12.35 g of a solid product characterized by means of HPLC.

EXAMPLE 9

Determination of the fungicidal activity in preventive application (5 days) against Erysiphe graminis on wheat.

Leaves of wheat plants of the Salgemma species, grown in pots in a conditioned environment at 20°C and 70% of R.H. (Relative Humidity), were treated by spraying both sides with the compound under examination (see Table 7 hereunder), dispersed in a hydroacetone solution at 20% by volume of acetone.

After remaining 5 days in a conditioned environment, the plants were dry-infected by shaking plants previously infected by Erysiphe graminis over them, in order to spread the inoculum.

The plants were then kept in the same cell, in an environment saturated with humidity, at a temperature ranging from 18 to 24°C for 12 days.

After this period, the external symptoms of the pathogen appeared and it was consequent- ly possible to proceed with a visual evaluation of the intensity of the infection, both on the parts directly treated with the products (T), and also on the parts that had developed during the test period (NT).

The fungicidal activity is expressed as a reduction percentage with respect to the non- treated seedlings (comparison), of the leaf area infected by the disease (100 = complete effec- tiveness; 0 = zero effectiveness).

All compounds Nr. 1, 1.1, 8, 9, 10, 11 and 21 showed a full activity (100%) at a dosage of 250 ppm.

At the same time, the phytotoxicity (percentage of leaf necrosis) induced on the wheat seedlings by applying the products, was evaluated: in this case the evaluation scale ranges from 0 (completely healthy seedling) to 100 (completely necrotic seedling).

Table 7 indicates the results obtained by carrying out the test described on compounds Nr. 1, 1.1, 8, 9, 10, 11 and 21 compared with the following compounds described in WO 00/46184:

CR1 = N,N-dimethyl-N'-[4-(3-trifluoromethylbenzoyl)-2,5-xylyl-formamidine (compound Nr. 398); CR2 = N,N-dimethyl-N'-[4-benzoyl-2,5-xylyl]-formamidine;

CR3 = N-ethyl-N-methyl-N'-[4-(3-trifluoromethylphenoxy)-2,5-xylyl]formamidine (compound Nr. 45).

Table 7

Compounds Nr. 1, 1.1, 8, 9, 10, 11 and 21 proved to be less phytotoxic and/or more tive with respect to the reference products.

EXAMPLE 10

Determination of the preventive fungicidal activity (5 days) against Puccinia Recondita on wheat.

Leaves of wheat plants of the Salgemma species, grown in pots in a conditioned environment at 20°C and 70% of R.H. (Relative Humidity), were treated by spraying both sides with the compound under examination (see Table 8 hereunder), dispersed in a hydroacetone solution at 20% by volume of acetone.

After remaining 5 days in a conditioned environment, the plants were sprayed on both sides of the leaves with an aqueous suspension of conidia of Puccinia recondita (2 mg of inoculum per 1 ml of solution per infection).

After spraying, the plants were kept in an environment saturated with humidity, at a temperature ranging from 18 to 24°C for the incubation period of the fungus (1 day).

At the end of this period, the plants were put in a greenhouse with a R.H of 70% and a temperature of 18-24°C for 14 days.

After this period of time, the external symptoms of the pathogen appeared and it was consequently possible to proceed with a visual evaluation of the intensity of the infection, both on the parts directly treated with the products (T), and also on the parts that had developed during the test period (NT).

The fungicidal activity is expressed as a reduction percentage with respect to the non- treated seedlings (comparison), of the leaf area infected by the disease (100 = complete effectiveness; 0 = zero effectiveness).

All compounds nr. 1, 1.1, 8, 9, 10, 1 1 and 21 showed a full activity (100%) at a dosage of 250 ppm.

At the same time, the phytotoxicity (percentage of leaf necrosis) induced on the wheat seedlings by applying the products, was evaluated: in this case the evaluation scale ranges from 0

(completely healthy seedling) to 100 (completely necrotic seedling).

Table 8 indicates the results obtained by carrying out the test described on compounds nr.

1, 1.1, 8, 9, 10, 1 1 and 21 compared with the following compounds described in WO 00/46184: CR1 = N,N-dimethyl-N'-[4-(3-trifluoromethylbenzoyl)-2,5-xylyl-formamidine (compound Nr. 398);

CR2 = N,N-dimethyl-N'-[4-benzoyl-2,5-xylyl]-formamidine;

CR3 = N-ethyl-N-methyl-N'-[4-(3-trifluoromethylphenoxy)-2,5-xylyl]formamidine (compound Nr. 45).

Table 8

Compounds nr. 1, 1.1, 8, 9, 10, 1 1 and 21 proved to be less phytotoxic and/or more active with respect to the reference products.

EXAMPLE 1 1

Determination of the fungicidal activity in preventive application (5 days) of compositions containing benzoylphenyl-formamidines.

Leaves of wheat plants of the Salgemma cultivar, grown in pots in a conditioned environment at 20°C and 70% of R.H. (Relative Humidity), were treated by spraying both sides with the composition under examination (see Table 9 hereunder), dispersed in a hydroacetone solution at 20% by volume of acetone.

After remaining 5 days in a conditioned environment, the plants were either dry-infected by shaking plants previously infected by different phytopathogens over them in order to spread the inoculum, or infected by spraying a spore suspension of a defined concentration of the inoculum. The plants were then kept in the same cell, in an environment saturated with humidity, at a temperature ranging from 18 to 24°C for 12 days.

After this period, the external symptoms of the pathogen appeared and it was consequently possible to proceed with a visual evaluation of the intensity of the infection, both on the parts directly treated with the products (T), and also on the parts that had developed during the test period (NT).

The fungicidal activity is expressed as a reduction percentage with respect to the non-treated seedlings (comparison), of the leaf area infected by the disease (100 = complete effectiveness; 0 = zero effectiveness).

The synergism of the binary mixture (A+B) at the dose (dA+de) was evaluated according to the Colby's formula:

I, = IA + IB - (IAXIB/100)

Wherein I_t is the fungicidal activity of the mixture;

IA is the fungicidal activity observed for compound A at the dose d_A;

IB is the fungicidal activity observed for compound B at the dose de.

When the fungicidal activity observed for the composition (A+B) is higher than that calculated by the Colby's formula, a synergistic effect is confirmed (IA+B > ¾ Synergy factor = ΙΑ+Β ¾ > 1)· The following compositions have been prepared and tested on different fungi in order to evaluate their fungicidal activity in preventive application. CI : Compound 1 + tetraconazole;

C2: Compound 1 + tebuconazole;

C4: Compound 1 + difenoconazole;

C8: Compound 1 + prothioconazole;

C9: Compound 1 + prochloraz;

CI 1 : Compound 1 + spiroxamine;

CI 6: Compound 1 + fluxapyroxad;

CI 7: Compound 1 + isopyrazam;

C22: Compound 1 + fluoxastrobin;

C27: Compound 1 + metrafenone;

C28: Compound 1 + proquinazid;

C30: Compound 1 + cyprodinil;

C31 : Compound 1 + iprodione;

C34: Compound 1 + thiophanate-methyl;

C40: Compound 8 + azoxystrobin;

C43 : Compound 9 + 3-difluoromethyl-N-(7-fluoro-l, l,3-trimethyl-4-indanyl)-l-methyl-4- carboxamide;

C49: Compound 10 + pyraclostrobin;

C54: Compound 1.1 + benzovindiflupyr.

The results are reported in Table 9. The compositions of the present invention show a strong synergistic effect (synergy factor > 1) with compounds belonging to chemical classes having a very different mechanism of action.

Table 9

Fungus Compound / IA, IB, It Synergy fac¬

Dose (ppm) IA+B tor

Pyricularia oryzae Compound 1 / 15 40 - -

Pyricularia oryzae Tetraconazole / 50 30 - -

Pyricularia oryzae CI / 65 95 58 1.64

Pyricularia oryzae Tebuconazole / 50 36 - -

Pyricularia oryzae C2 / 65 96 62 1.58

Pyricularia oryzae Difenoconazole / 30 42 - - Pyricularia oryzae C4 / 45 92 71 1.3

Pyricularia oryzae Prothioconazole / 30 48 - -

Pyricularia oryzae C8 / 45 97 69 1.4

Pyricularia oryzae Prochloraz / 30 60 - -

Pyricularia oryzae C9 / 45 95 76 1.25

Pyricularia oryzae Spiroxamine / 50 30 - -

Pyricularia oryzae Cll / 65 93 58 1.6

Septoria tritici Compound 1 /15 50 - -

Septoria tritici Fluxapyroxad /1 65 - -

Septoria tritici C16 / 30 100 82 1.21

Septoria tritici Isopyrazam /15 70 - -

Septoria tritici C17 / 30 98 85 1.15

Puccinia recondite Compound 1 /30 75 - -

Puccinia recondite Fluoxastrobin /30 63 - -

Puccinia recondite C22 / 60 100 90 1.1

Erysiphe graminis Compound 1 / 15 50 - -

Erysiphe graminis Metrafenone / 30 40 - -

Erysiphe graminis C27 / 45 96 70 1.37

Erysiphe graminis Proquinazid / 30 60 - -

Erysiphe graminis C28 / 45 97 80 1.21

Botrytis cinerea Compound 1 / 15 53 - -

Botrytis cinerea Cyprodinil / 50 60 - -

Botrytis cinerea C30 / 65 85 81 1.04

Botrytis cinerea Iprodione / 50 50 - -

Botrytis cinerea C31 / 65 75 75 1

Rhizoctonia solani Compound 1 / 300 60 - -

Rhizoctonia solani Thiophanate-methyl / 250 60 - -

Rhizoctonia solani C34 / 550 88 84 1.05

Puccinia recondite Compound 8 /30 75 - -

Puccinia recondite Azoxystrobin / 30 50 - - Puccinia recondita C40 / 60 98 87 1.12

Septoria tritici Compound 9 / 15 50 - -

Septoria tritici 3-difluoromethyl-N-(7- 65

fluoro- 1 , 1 ,3 -trimethyl-4- indanyl)- 1 -methyl-4- carboxamide / 30

Septoria tritici C43 / 45 90 82 1.09

Puccinia recondita Compound 10 / 30 75 - -

Puccinia recondita Pyraclostrobin / 30 50 - -

Puccinia recondita C49 / 60 95 87 1.08

Septoria tritici Compound 1.1 / 15 50 - -

Septoria tritici Benzovindiflupyr / 30 60 - -

Septoria tritici C54 / 45 92 80 1.15

Claims

Claims

1. Benzoylphenyl-formamidine of general formula (I):

(I)

wherein:

Ri represents a C₂-C6 alkyl, a C3-C6 cycloalkyl or a C4-C7 cycloalkylalkyl;

R₂ represents a Ci-Ce alkyl;

or Ri and R2, together with the N atom to which they are bound, form a heterocyclic ring containing from 4 to 7 atoms, possibly substituted by halogen atoms;

R3 and R4, equal to or different from each other, represent a hydrogen atom, a halogen atom, a Ci-C₆ alkyl, a Ci-C₆ alkoxyl, a Ci-C₆ haloalkoxyl, a CF₃ group, a CF₂H group, a CFH₂ group or a cyano group;

- R, equal or different when n > 2, represents a halogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C1-C4 alkoxyl group, a C1-C4 haloalcoxyl group, a C1-C4 alkylthio group, a C3- Ce cycloalkoxyl group, a carboxyl group, a C2-C7 alkoxycarbonyl group_, a benzyloxy group; a phenyl group optionally substituted, or two substituents R represent together a C1-C4 al- kylendioxy group;

n represents an integer from 0 to 4.

2. Benzoylphenyl-formamidine according to claim 1 , selected from compounds of general formula (I) wherein R_1; R₂, R3, R4, R and n assume the reported below meanings:

Ri 2 3 4 R N

Et Me Me Me - 0

iPr Me Me Me - 0

Bu Me Me Me - 0

-CH₂CF₂CH₂- Me Me - 0

-(CH₂)₄- Me Me - 0

-(C¾)₅- Me Me - 0

-CH₂CH₂OCH₂CH₂- Me Me - 0

-(CH₂)₄- Me Me 2-Br ¹

-(C¾)₄- Me Me 4-Br ¹

-(CH₂)₄- Me Me 2,4-Br

-(CH₂)₄- Me Me 3-CF₃ ¹

-(CH₂)₄- Me Me 2-CF₃ ¹

-(CH₂)₄- Me Me 2-OCF₃ ¹

-(CH₂)₄- Me Me 3-OCF₃ ¹

-(CH₂)₄- Me Me 3 -CI ¹

-(CH₂)₄- Me Me 3,4-Cl

-(CH₂)₄- Me Me 3-OCF₂CF₂H ¹

Et Me Me Me 3-OCF₂CF₂H ¹

Et Me Me Me 4-OC₃H₅ ¹

Et Me Me Me 3-OC₃H₅ ¹

Et Me Me Me 4-OCH₂C₆H₅ ¹

Et Me Me Me 3-OCH₂C₆H₅ ¹

Et Me Me Me 4-C₆¾ ¹

Et Me Me Me 3-CeH₅ ¹

Et Me Me Me 2-C₆H₅ ¹

Et Me CI CI 2-Br ¹

Et Me CF₂H Me 2-Br ¹

Et Me Me CF₂H 2-Br ¹

Et Me CI CI 3-CF₃ ¹

Et Me CF₂H Me 3-CF₃ ¹

Et Me Me CF₂H 3-CF₃ ¹

3. Benzoylphenyl-formamidine according to any of the claims 1 or 2, selected from the compounds of general formula (I) wherein Ri represents ethyl, R_2, R3 and R4 represent methyl, R represents a halogen, a CF₃ group, a OCF₃ group or a OCH₃ group and n assumes the values 0-2, R being equal or different when n is equal to 2.

4. Benzoylphenyl-formamidine according to any of th claims 1-3, selected form compounds of general formula (I) wherein Ri represents ethyl, R₂, R3 and R4 represent methyl, R represents a CI or Br atom, a CF₃ group or a OCF₃ group and n assumes the values 0-2, R being equal or different when n is equal to 2.

5. Benzoylphenyl-formamidine according to one or more of the claims 1-4, selected from the compounds of general formula (I) wherein Ri, R₂, R₃, R4, R and n assume the below reported meanings:

1 Et Me Me Me - 0

2 Et Me Me Me 2-Br 1

3 Et Me Me Me 3-CF₃ 1

4 Et Me Me Me 3 -Br 1

5 Et Me Me Me 2,5-CF₃ 2

6 Et Me Me Me 4-OCF₃ 1

6. Benzoylphenyl-formamidine according to any of th claims from 1 to 5, which are a) mixtures of unseparated geometric isomers, mixtures of partially separated geometric isomers, single geometric isomers; b) in the form of salts obtained by addition of inorganic or organic acids; c) in the form of crystalline admixed with urea, in whichever molar or ponderal ratio, preferably from 1 : 1 to 1 :5; d) in the form of compounds of inclusion with substances having a solubility in water lower than 150g/l and a melting point higher than 85°C, preferably dimethylsulfone.

7. Benzoylphenyl-formamidine according to any of the claims 1 or 6, selected from compounds of general formula (I) wherein R_1; R₂, R3, R4, R and n assume the below reported mean- ings, salified by addition with the acid as below reported:

8. Fungicidal compositions comprising one or more compounds of formula (I) according to any or more of the claims from 1 to 7, a solid or liquid solvent and/or diluent, possibly one or more surfactants and other agronomically acceptable coformulant.

9. Fungicidal compositions according to claim 8, comprising one or more further active ingredients such as fungicides different from those of general formula (I), phytoregulators, antibiotics, herbicides, insecticides, fertilizers and/or mixtures thereof, preferably comprising at least another fungicide.

10. Fungicidal compositions according to claim 9, containing at least one benzoylphenyl- formamidine of formula (I) and one or more fungicides belonging to the following classes:

a) azoles selected from azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, epoxy-conazole, fenbuconazole, fluquinconazole, flusilazole, flutnafol, hexaconazole, imazalil, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prochloraz, prothiocona- zole, simeconazole, tebu-conazole, tetraconazole, tnadimefon, triadimenol, triflumizole, triticon- azole;

b) amines inhibiting the ergosterol biosynthesis selected from aldimorph, dodemorph, fenpropi- morph, fenpropidin, spiroxamine, tridemorph;

c) inhibitors of succinate-dehydrogenase (SDHI) selected from benzovindifiupyr, bixafen, bos- calid, carboxin, fluopyram, flutolanil, fluxapyroxad, furametpyr, isopyrazam, oxycarboxin, pen- flufen, penthiopyrad, sedaxane, thifluzamide, 3-difluoromethyl- N-(7-fluoro-l, l,3-trimethyl-4- indanil)- 1 -methyl-4-carboxamide;

d) strobilurins selected from azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysa-strobin, picoxystrobin, pyraclostrobin, pyrameto-strobin, pyraoxostrobin, trifloxystrobin;

e) specific antioidic compounds selected from cyflufenamid, flutianil, metrafenone, proquinazid, pyriofenone, quinoxyfen;

f) aniline-pyramidines selected from pyrimethanil, mepanipyrim, cyprodinil;

g) benzimidazoles and analogous thereof selected from carbendazim, benomyl, thiabendazole, thiophanate-methyl;

h) dicarboxyimides selected from iprodione, procymidone;

i) phtalimides selected from tra captafol, captan, folpet;

1) systemic acquired resistance (SAR) inductors selected from acibenzolar, probenazole, isotianil, tiadinil;

m) phenylpyrroles selected from fenpiclonil, fludioxonil;

n) acilalanines selected from benalaxyl, benalaxyl-M, furalaxyl, metalaxyl, metalaxyl-M;

o) other specific antiperonosporic compounds selected from ametoctradin, amisulbrom, ben- thiavalicarb, cyazofamid, cymoxanil, dimethomorph, ethaboxam, famoxadone, fenamidone, flumetover, flumorph, fluopicolide, iprovalicarb, mandipropamid, oxathiapiproline, vali- fenalate;

p) dithiocarbamates selected from maneb, mancozeb, propineb, zineb;

q) phosphorous acid and its inorganic and organic salts, fosetyl-aluminium;

r) rameic compounds selected from Bordeaux mixture, carpropamid, copper hydroxide, copper oxychloride, copper sulphate, copper salycilate;

s) other fungicides selected from chlorothalonil, fenhexamid, fenpyrazamine, fluazinam, sylthi- ofam, tebufloquin, zoxamide, dodine, guazatine, iminoctadine.

11. Fungicidal compositions according to one or more of the claims 8-10, consisting of:

CI : compound 1 + tetraconazole;

C2: compound 1 + tebuconazole;

C3 : compound 1 + cyproconazole;

C4: compound 1 + difenoconazole;

C5 : compound 1 + epoxyconazole; C6: compound 1 + flutriafol;

C7: compound 1 + penconazole;

C8 : compound 1 + prothioconazole;

C9: compound 1 + prochloraz;

CIO: compound 1 + fenpropimorph;

CI 1 : compound 1 + spiroxamine;

C12: compound 1 + bixafen;

C13 : compound 1 + boscalid;

C14: compound 1 + carboxin;

CI 5 : compound 1 + fluopyram;

CI 6: compound 1 + fluxapyroxad;

CI 7: compound 1 + isopyrazam;

CI 8: compound 1 + penthiopyrad;

CI 9: compound 1 + sedaxane;

C20: compound 1 + azoxystrobin;

C21 : compound 1 + dimoxystrobin;

C22: compound 1 + fluoxastrobin;

C23 : compound 1 + kresoxim-methyl;

C24: compound 1 + picoxystrobin;

C25 : compound 1 + pyraclostrobin;

C26: compound 1 + trifloxystrobin;

C27: compound 1 + metrafenone;

C28: compound 1 + proquinazid;

C29: compound 1 + mepanipyrim;

C30: compound 1 + cyprodinil;

C31 : compound 1 + iprodione;

C32: compound 1 + procymidone;

C33 : compound 1 + carbendazim;

C34: compound 1 + thiophanate-methyl;

C35: compound 1 + 3-difluoromethyl-N-(7-fluoro-l, l,3-trimethyl-4-indanyl)-l-methyl-4- carboxamide,

C36: compound 1 + benalaxyl-M,

C37: compound 1 + benzovindiflupyr,

C38: compound 8 + tetraconazole, C39: compound 8 + 3-difluoromethyl-N-(7-fluoro-l, l,3-trimethyl-4-indanyl)-l -methyl-4 carboxamide,

C40: compound 8 + azoxystrobin,

C41 : compound 8 + pyraclostrobin,

C42: compound 9 + tetraconazole,

C43 : compound 9 + 3-difluoromethyl-N-(7-fluoro-l, l,3-trimethyl-4-indanyl)-l -methyl-4 carboxamide,

C44: compound 9 + azoxystrobin,

C45 : compound 9 + pyraclostrobin,

C46: compound 10 + tetraconazole,

C47: compound 10 + 3-difluoromethyl-N-(7-fluoro-l, l,3-trimethyl-4-indanyl)-l -methyl-4 carboxamide,

C48: compound 10 + azoxystrobin,

C49: compound 10 + pyraclostrobin,

C50: compound 1.1 + tetraconazole,

C51 : compound 1.1 + 3-difluoromethyl-N-(7-fluoro-l, l,3-trimethyl-4-indanyl)-l -methyl-4 carboxamide,

C52: compound 1.1 + azoxystrobin,

C53 : compound 1.1 + pyraclostrobin,

C54: compound 1.1 + benzovindiflupyr,

C55 : compound 1.1 + fluxapyroxad,

C56: compound 1 + tetraconazole + azoxystrobin,

C57: compound 1 + pyraclostrobin + tetraconazole,

C58: compound 1 + epoxyconazole + azoxystrobin,

C59: compound 1 + pyraclostrobin + epoxyconazole,

C60: compound 1 + azoxystrobin + 3-difluoromethyl-N-(7-fluoro-l, l,3-trimethyl-4-indanyl)-l methyl-4-carboxamide,

C61 : compound 1 + pyraclostrobin + 3-difluoromethyl-N-(7-fluoro-l, l,3-trimethyl-4-indanyl)-l methyl-4-carboxamide,

C62: compound 1 + 3-difluoromethyl-N-(7-fluoro-l, l,3-trimethyl-4-indanyl)-l -methyl-4 carboxamide + tetraconazole,

C63 : compound 1.1 + tetraconazole + azoxystrobin,

C64: compound 1.1 + pyraclostrobin + tetraconazole,

C65 : compound 1.1 + epoxyconazole + azoxystrobin,

C66: compound 1.1 + pyraclostrobin + epoxyconazole, C67: compound 1.1 + azoxystrobin + 3-difluoromethyl-N-(7-fluoro-l, l,3-trimethyl-4-indanyl)- l-methyl-4-carboxamide,

C68: compound 1.1 + pyraclostrobin + 3-difluoromethyl-N-(7-fluoro-l, l,3-trimethyl-4-indanyl)- l-methyl-4-carboxamide,

C69: compound 1.1 + 3-difluoromethyl-N-(7-fluoro-l, l,3-trimethyl-4-indanyl)-l-methyl-4- carboxamide + tetraconazole;

wherein the compounds 1, 8, 9, 10 are compounds of general formula (I) in which the substituents assume the below reported meanings:

and the compound 1.1 is a salt of the compound of general formula (I) wherein the substituents assume the below reported meanings and the acid used for salification is hydrochloric acid:

12. Use of benzoylphenyl-formamidine of general formula (I) according to one or more of the claims 1-7, for the control of phytopathogenic fungi of agricultural crops.

13. Use of compositions comprising at least one benzoylphenyl-formamidine of general formula (I), according to one or more of the claims 8-11, for the control of phytopathogenic fungi of agricultural crops.

14. Method for the control of phytopathogenic fungi in agricultural crops, which consists in applying on any part of the plants to be protected, effective and not phytotoxic dosages of compositions comprising at least a compound of general formula (I), according to any of the preceding claims 8-11 and, optionally, one or more further active ingredients.