MXPA96003735A - Fungicide compounds - Google Patents

Abstract

A compound of the formula (I): X is O or S, A is a 6-membered heteroaryl group, comprising at least one nitrogen atom, which is optionally substituted by one or more of the group R2, R 1 is alkyl, cycloalkyl , cycloalkenyl, alkenyl, alkynyl, Y1-X- or amino, (each of which is optionally substituted), halogen, cyano, nitro, acyl, acyloxy, optionally substituted heterocyclyl or optionally substituted phenyl, or two adjacent groups together with the carbon to which they are attached, can form an optionally substituted benzo ring, R2 has the same meaning as R1 or two adjacent groups together with the carbon atoms to which they are attached, can form an optionally substituted heterocyclic ring, and is alkyl, cycloalkyl , cycloalkenyl, alkenyl or alkynyl, each of which is optionally substituted, hydrogen or acyl, Y1 has the same meaning as Y or is optionally substituted phenyl or heterocyclic optionally substituted clyl: Z is C (= X1) -X2-R3, cyano, optionally substituted het- citcylyl, -C (R5) = N-OR6 or -C (R5) = N-HR6R7; R3 is cycloalkyl, cycloalkenyl, alkenyl alkyl , alkynyl, phenyl or heterocyclyl, each of which is optionally substituted, hydrogen or an inorganic or organic cationic group. X1 and X2, which may be the same or different, are O or S, R5, R6 and R7, which may be the same or different, are alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, phenyl or heterocyclyl, each of which which is optionally substituted or hydrogen or R6 and R7 together with the whole atom to which they are attached can form a ring, n is 0 to 4, together with complexes with metal salts, as well as salts with bases of compounds, which are acidic and the salts conacids of the compounds which are bases, have fungici activity

Description

»• FUNGICIDAL COMPOUNDS FIELD OF THE INVENTION 5 This invention relates to new anthranilic acid derivatives useful as fungicides.

PREVIOUS TECHNIQUE 10 DE 2417216 describes inter alia, N-phenylcarbamoylpyridine compounds as fungicides, in which the pyridine is substituted by chlorine and the phenyl may be substituted by carboxy. In J. Agrie. Biol. Chem 44 (9), 2143, In 1980, certain N-benzoylanthranylates are described as fungicides. Similar compounds are described in GB 1,563,664 and Japanese Ko ai 53130655. It has been found that certain new anthranilic acid derivatives also have valuable fungicidal activity and also have advantages over the compounds described in these publications.

DESCRIPTION OF THE INVENTION According to the invention, a compound of the formula I (R ') is provided X is O or S; A is a 6-membered heteroaryl group, comprising at least one nitrogen atom, which is optionally substituted by one or more of the group R2; R1 is alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, Y1-X- or amino, (each of which is optionally substituted), halogen, cyano, nitro, acyl, acyloxy, optionally substituted heterocyclyl or optionally substituted phenyl; or two adjacent groups together with the carbon atoms to which they are attached, can form an optionally substituted benzo ring; R2 has the same meaning as R1 or two adjacent groups together with the carbon atoms to which they are attached, can form an optionally substituted heterocyclic ring; Y is alkyl, cycloalkyl, cycloalkenyl, alkenyl or alkynyl, each of which is optionally substituted, hydrogen or acyl; Y1 has the same meaning as Y or is optionally substituted phenyl or optionally substituted heterocyclyl; Z is C (= X1) -X2-R3, cyano, optionally substituted heterocyclyl, -C (R5) = N-OR6 or -C (R5) = N-NR6R7; R3 is alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, phenyl or heterocyclyl, each of which is optionally substituted, hydrogen or an inorganic or organic cationic group. X1 and X2, which may be the same or different, are 0 or S; R5, R6 and R7, which may be the same or different, are alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, phenyl or heterocyclyl, each of which is optionally substituted or hydrogen or R6 and R7 together with the atom or atoms which are joined together can form a ring; n is 0 to 4, together with complexes with metal salts, as well as salts with bases of compounds, which are acids and salts with acids of the compounds which are bases, with the proviso that when Y is hydrogen and i) when Z is carboxy, ethoxycarbonyl or ethoxycarbonyl, ring A is not substituted with pyridyl or pyrazinyl; and ii) when Z is carboxy and n is 0, A is not 2-chloro-3-pyridyl, 6- (2-diethylaminoethoxy) -3-pyridyl or a 2-pyridyl group. The alkyl groups are preferably from 1 to 20, for example from 1 to 6 carbon atoms. The alkenyl and alkynyl groups are generally from 3 to 6 carbon atoms. The cycloalkyl or cycloalkenyl groups are preferably from 3 to 8 carbon atoms. Substituents, when present in any alkyl, cycloalkyl, cycloalkenyl, alkenyl or alkynyl moiety include optionally substituted halogen, azido, cyano, optionally substituted alkoxy, alkylthio, hydroxy, nitro, amino, acyl, optionally substituted acyloxy, optionally substituted phenyl, heterocyclyl optionally substituted, optionally substituted phenoxy and optionally substituted heterocyclyloxy. The cycloalkyl or cycloalkenyl groups can also be substituted by alkyl. Substituents when present in any phenyl group, are usually one or more of the same groups as defined for R1. The term "heterocyclyl" includes both heterocyclyl aromatic and non-aromatic groups. Heterocyclyl groups are generally rings of 5, 6 or 7 members containing up to 4 heteroatoms selected from nitrogen, oxygen and sulfur. Examples of heterocyclyl groups are furyl, thienyl, pyrrolyl, pyrrolinyl, pyrrolidinyl, imidazolyl, dioxolanyl, oxazolyl, thiazolyl, imidazolyl, imidazolinyl, imidazolidinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, pyranyl, pyridyl, piperidinyl, dioxanyl, morpholino, dithianyl, thiomorpholino, pyridazinyl, pyrimidinyl, pyrazinyl, piperazinyl, triazinyl, thiazolinyl, benzimidazolyl, tetrazolyl, benzoxazolyl, imidazopyridinyl, 1,3-benzoxazinyl, 1,3-benzothiazinyl, oxazolopyridinyl, benzofuranyl, quinolinyl, quinazolinyl, quinoxalinyl, sulfolanil, dihydroquinazolinyl, benzothiazolyl, phthalimido, benzofuranyl, azepinyl, oxazepinyl, thiazepinyl, diazepinyl and benzodiazepinyl. The heterocyclyl groups themselves may be substituted, for example by phenyl. Amino groups may be substituted, for example, by one or two optionally substituted alkyl or acyl or two substituents may form a ring, preferably a 5- to 7-membered ring, which may be 'substituted and may contain other heteroatoms, by example morpholine, thiomorpholine or piperidine. The term "acyl" includes the residue of the acids containing sulfur and phosphorus, as well as carboxylic acids. Examples of acyl groups are -COR5, -COOR5, -CXNR5R6, -CON (R5) OR6, -COONR5R6, -CON (R5) NR6R7, -COSR5, -CSSR5, -S (0) pR5, -S (0) 2OR5 , -S (0) pNR5R6, -P (= X) (OR5) (OR6, -CO-COOR5, where R5, R6 and R7 are as previously defined, or R6 and R7 together with the atom or atoms to which they are joined, they can form a ring, p is 1 or 2 and X is 0 or S. It is generally preferred that A is a pyridine, (especially 3-pyridyl), a pyrimidine (especially 5-pyrimidinyl) or a pyrazine ring. it can be, for example, a tetrazine, pyridazine or triazine ring, R2 is preferably selected from halogen and alkoxy, especially methoxy, R1 is preferably selected from halogen, especially fluorine and alkyl, especially methyl, Z is preferably C (= X1) -X2-R3 X1 and X2 are both preferably O and R3 is generally alkyl, alkenyl or alkynyl, each of which is optionally substituted and is especially methyl, and is preferably hydrogen, alkyl, and especially methyl or acyl, especially alkanoyl or alkoxycarbonyl. X is preferably 0. n is preferably 0.

The complexes of the compounds of the invention are usually formed of a salt of the formula Man2, in which it is a divalent metal cation, for example copper, manganese, cobalt, nickel, iron or zinc and An is an anion, for example chloride, nitrate or sulfate. The compounds of the invention have activity against a wide range of pathogens of Deuteromycete, Ascomycete, Ficomycete and Basidiomycete origin, especially against fungal plant diseases, for example mildews and particularly barley powdery mildew. { Erysiphe graminis), powdery mildew of cucumber (Erysiphe cichoracaerum) and mildews of wine (Plas opara tícola and Uncinula necator), wilt of rice husk (Pyricularia oryzae), cereal spots (Pseudocercosporella herpotrichoides), blight of rice husk . { Pellicularia sasakii), gray mold (Botrytis cinerea), coffee brown rust [Puccinia recóndi ta), late blight of tomato or potato (Phytophthora infestans), apple scab (Venturia inaequalis) and spotting of the glume (Leptosphaeria nodorum). Some compounds may be active against only a few pathogens, while others may have a broader spectrum of activity. Some new compounds of the formula I have weak pesticidal activity, but still have utility as intermediates and such compounds also form an aspect of the invention.

The compounds of the invention are generally formulated in conventional compositions used for fungicides. These compositions may contain one or more additional pesticides, for example the compounds known to possess herbicidal, fungicidal, insecticidal, acaricidal or nematicidal properties. The diluent or carrier in the composition of the invention can be a solid or a liquid optionally in association with a surface active agent, for example a dispersing agent, an emulsifying agent or a wetting agent. Suitable surface active agents include anionic compounds such as carboxylate, for example metal carboxylate of a long-chain fatty acid; an N-acyl sarcosinate; mono- or di-esters of phosphoric acid with fatty alcohol ethoxylates or salts of such esters; fatty alcohol sulfates such as sodium dodecylsulfate, sodium octadecylsulfate or sodium cetyl sulfate; ethoxylated fatty alcohol sulfates; ethoxylated alkylphenol sulfates; lignin sulfonates; petroleum sulfonates; alkyl arylsulfonates such as alkyl-benzene sulfonates or lower alkyl sulfonates naphthalene, for example butyl naphthalene sulfonate; salts of naphthalene sulfonated-formaldehyde condensates; salts of sulfonated phenol-formaldehyde condensates; or more complex sulfonates such as amide sulfonates, for example the product of sulfonated condensation of oleic acid and N-methyltaurine or dialkylsulfosuccinates, for example sodium sulfonate of dioctyl succinate. Nonionic agents include products of the condensation of fatty acid esters, fatty alcohols, fatty acid amides or phenols substituted with fatty alkyl or alkynyl with ethylene oxide, fatty esters of polyhydric alcohol ethers, for example acid esters fatty sorbitan, products of the condensation of such esters with ethylene oxide, for example polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, acetylenic glycols, such as 2,4,7,9-tetramethyl -5-decin-4, 7-diol, or ethoxylated acetylenic glycols. Examples of a cationic surfactant include, for example, a mono-, di-aliphatic or polyamine such as an acetate, naphthenate or oleate; an oxygen-containing amine such as an amine oxide or polyoxyethylene-alkylamine; an amine attached to an amide prepared by the condensation of a carboxylic acid with di- or polyamine; or a quaternary ammonium salt. The compositions of the invention can take any form known in the art for the formulation of agrochemicals, for example, a solution, a dispersion, an aqueous emulsion, a powder for sprinkling, a seed coat, a fumigant, a smoke, a dispersible powder, a concentrate or emulsifiable granules. In addition, it may be in a form suitable for direct application or as a concentrate or primary composition, which requires a dilution with an adequate amount of water or other diluent before application. As a dispersion, the composition comprises a compound of the invention dispersed in a liquid medium, preferably water. It is often convenient to supply the consumer with a primary composition, which can be diluted with water to form a dispersion having the desired concentration. The primary composition can be provided in any one of the following ways. It can be a dispersible solution which comprises a compound of the invention dissolved in a water-miscible solvent with the addition of a dispersing agent. Another alternative comprises a compound of the invention in the form of a finely ground powder in association with a dispersing agent and intimately mixed with water to give a paste or cream, which may if desired, be added to an oil-in-water emulsion to give a dispersion of the active ingredient in a water-in-oil emulsion. An emulsifiable concentrate comprises a compound of the invention dissolved in a water-immiscible solvent together with an emulsifying agent, which was formed in an emulsion during mixing with water.

A dusting powder comprising a compound of the invention, intimately mixed with a solid powdery diluent, for example kaolin. A granular solid comprising a compound of the invention associated with diluents similar to those which can be used in dusts to dust, but the mixture is granulated by known methods. Alternatively, it comprises the active ingredient adsorbed or absorbed in a pregranular diluent, for example, Fuller's earth, attapulgite or powdered limestone. A wettable powder usually comprises the active ingredient in admixture with a suitable surfactant and an inert powder diluent, such as clay. Another suitable concentrate, particularly when the product is a solid, is a flowable suspension concentrate which is formed by grinding the compound with water, a wetting agent and a suspending agent. The concentration of the active ingredient in the composition of the present invention is preferably within the range of 1 to 30 percent by weight, especially 5 to 30 percent by weight. In a primary composition, the amount of the active ingredient can vary widely and can be, for example, from 5 to 95 percent by weight of the composition.

The compounds of the invention can be prepared in a known manner, for example by reacting a compound of the formula II, (R1) with a compound of formula III 0 II¡¡-C-A (III) where Q is a leaving group, preferably a halogen and especially chloro, to give a compound of the formula I, wherein X is 0 and Y is hydrogen, and if it is desired to modify this compound in known manner to give other compounds where X and Y have other desired values and if desired, modify the compounds of the formula I in known manner, to give the compounds where R1, R2 and Z have other values. The reaction between the compounds II and III is generally carried out in the presence of a base, for example an organic tertiary amine and preferably in the presence of a solvent, for example an ether.

The compounds of formula II and III are either known or can be prepared in a known manner. The resulting compounds of the formula I can be modified in a known manner to give other compounds of the formula I, wherein one of the groups is modified to other desired groups. For example, an ester can be converted into a known form to a free acid or a salt. The thio groups can be oxidized using a suitable oxidizing agent, for example m-chloroperbenzoic acid, to give sulfinyl or sulfonyl groups. The carbonyl groups can be converted to thiocarbonyl groups by sulfurization in a known manner, for example using Lawesson's reagent or phosphorus pentasulfide. The alkylsulfonyl groups in ring A can be replaced by a suitable nucleophile such as an aryloxy or arylthio group by reaction with the appropriate hydroxy or mercapto compound. The invention is illustrated in the following examples. The structures of the isolated new compounds were confirmed by elemental analysis and / or other appropriate analyzes. The temperatures are in ° C.

Example 1 Triethylamine (28.4 g) is added to a solution of 6-chloronicotinic acid (40 g) in dry dichloromethane (900 ml). The mixture is cooled in an ice bath and methyl chloroformate (26.8 g) is added dropwise. The mixture is stirred at room temperature overnight, washed in turn with water, aqueous sodium hydrogen carbonate and brine. The organic phase is dried over magnesium sulfate, filtered and evaporated to give methyl 6-chloronicotinate. 10 g of this product are added to sodium methanolate (obtained from 1.61 g of sodium and 100 ml of dry methanol). The mixture is heated under reflux for 3 hours and allowed to stand at room temperature overnight. The aqueous potassium hydroxide (10 g in 30 ml of water) is added and the mixture is heated under reflux for 8 hours. Let it rest overnight at room temperature, it evaporates and the residue is added to the water (120 ml). The mixture is acidified to pH 3 with hydrochloric acid. The precipitate is filtered and dried to give the 6-methoxynicotinic acid. p.f. 175-177 °. This acid (6 g) is heated under reflux with an excess amount of thionyl chloride for 2 hours. The mixture is cooled, evaporated and the residue (comprising 6-methoxynicotinoyl chloride without purification) is dissolved in dry tetrahydrofuran (10 ml). This solution is added dropwise to a solution of methyl anthranilate (6.22 g) and triethylamine (7.92 g) in dry tetrahydrofuran (200 ml). The mixture is stirred at room temperature overnight, evaporated and extracted with ethyl acetate. The extracts are washed with water, dried and evaporated and the residue is purified by column chromatography on silica gel to give methyl N- (6-methoxynicotinoyl) anthranilate, m.p. 121-3 °. (compound 1) Methyl N- (2-methylthio-5-pyrimidinecarbonyl) anthranilate, m.p. 166-8 ° (composed the) Example 2 Sodium hydride (0.15 g of a 60% oil solution) is added to a solution of compound 1 of Example 1 (1 g) in dry tetrahydrofuran (25 ml) which had been cooled in an ice bath. The mixture is stirred for 20 minutes and then methyl iodide (0.44 ml) is added. The mixture is stirred at room temperature for 48 hours, evaporated and extracted with ethyl acetate. The extract is washed in turn with water and brine, dried over magnesium sulfate and evaporated. The residue is purified by column chromatography on silica gel to give methyl N- (6-ethoxynicotinoyl) -N-methylanthranilate, m.p. 68-70 °. (compound 2) Example 3 To a solution of compound 2 of Example 2 (0.6 g) in ethanol (20 ml) copper (II) chloride is added (0.134 g). The mixture is allowed to stand overnight, is evaporated and the residue triturated with ethyl acetate gives the complex bis- [N- (6-methoxynicotinoyl) -N-methylanthranilate methyl] copper (II) chloride, m.p. 196-8 °. (compound 3) Example 4 Acid -chloroperbenzoic acid (13.7 g) is added with stirring to a solution of the compound (6 g) in dichloromethane. The mixture is stirred overnight at room temperature, sodium sulfate is added and it is extracted with dichloromethane. The extract is manipulated to give methyl N- (2-methylsulfonyl-5-pyrimidinecarbonyl) anthranilate, m.p. 187-9 °. (compound 4) Example 5 Sodium hydride (0.24 g of a dispersion in 60% oil) is added to a solution of 2-mercaptopyridine (0.33 g) dissolved in dry dimethylformamide (20 ml). The mixture is stirred for half an hour at room temperature. A solution of compound 4 (1 g) in dry dimethylformamide (20 ml) is added dropwise with stirring. The mixture is stirred overnight at room temperature, cooled and quenched with methanol. The mixture is poured into water and made acidic with dilute hydrochloric acid. The precipitate is collected, dissolved in dichloromethane and the solution is washed with brine and evaporated to give methyl N- [2- (2-pyridylthio) -5-pyrimidinecarbonyl] -anthranilate, m.p. 145-147 ° (compound 5) In a similar manner using potassium carbonate as the base in place of sodium hydride, methyl N- [2- (4-methoxyphenoxy) -5-pyrimidinecarbonyl) -anthranilate was obtained as a oil (compound 5a).

For example, $ Compound 1 is heated with an equimolar amount of aqueous sodium hydroxide to give the N- (6-methoxy-nicotinoyl) -anthranilic acid, m.p. 224-3 ° (compound 6). This compound in turn is treated with more sodium hydroxide to give the sodium N- (6-methoxynicotinoyl) -anthranilate, m.p. > 250 ° (compound 6a).

Example 7 Lawesson's reagent (2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphtane-2,4-disulfide, 5.09 g) is added to a solution of compound 1 (3g) in tetrahydrofuran dry (100 mi). The mixture is stirred under nitrogen for 20 hours. More Lawesson's reagent (2.6 g) is added and the mixture is heated under reflux for 13 hours, evaporated and the residue is purified by column chromatography on silica gel, to give the N- (6-methoxy-3-pyridiniumcarbonyl) ) -methyl methacrylate, mp 133-4 °. (compound 7) Example 8 In a manner similar to one of the processes described in the previous Examples, the following compounds of the formula I are obtained.

Comp (R1) ». Z Y? p.f. (•) ß - COOMe H 6-EtO-3-pyridyl 150-2 9 -. 9 - COOEt H 6-Me? -3-pyridyl 129-30 -. 10 - COOEt Me 6-MeO-3-pyridyl 91-2 eleven - . 11 - COOMe -CH2CN 6-MeO-3-pyridyl oil 12 -. 12 - COOMe -COOMe 6-MeO-3-pyridyl gum 13 3-Me COOMe H 6-MeO-3-pyridyl 111-2 14 5-C1 COOMe H 6-MeO-3-pyridyl 172-3 4, 5- (MeO) 2 COOMe H 6 -MeO-3-pyridyl 173-5 16 -. 16 - coo benzyl Me 6-MeO-3-Ho 110-3 17 5-Cl COOMe Me 6-MeO-3-? Iridflo 89-91 18 4, 5- (MeO) 2 COOMe Me 6 -MeO-3-pyridyl 147-50 9 5-MeS COOMe H 6-Me? -3-iridyl 135-7 0 5-MeS COOMe Me 6-MeO-3-; Pridrid 78-80 1-CN H 6-Meo-3- Pyr? "Lo 163-6 2 - CN Me 6 -MeO-3- pWdH? 90.5-3 3 - COOMe H 5-MeO-2-pyrazinyl 169-70 4 6-Me COOMe H 6-MeO-3-pyridyl 102.5-5 5-COOMe H 5-Cl-6-MeO-165-6 3 -pyridyl Comp. (R1) »pf (ß) 26 -. 26 - COOMe Me 5-Cl-6-MeO-110-2 3-pyridyl 27 6-Me COOMe Me 6-MeO-3-pyridyl 117.5-8.5 28 -. 28 - COOPrj H 6-MeO-3-Pyridyl 107-9 29 -. 29 - COOMe H 6 -MeS -3 - pyridyl 102.5-5 -. 30 - COOMe Me 6-EtO-3- Pyridyl oil 31 «. COOMe K 4, 6- (MeO) 2- iridyl 125-7 5 -pyrimidinyl 32 COOMe H 5, 6- (Meo) 2- 156-9 2-pyrazinyl 33 - COOMe Me 3 -pyridyl 86-8 34 4-NOx COOMe Me 6-MeO-3-pyridyl 110-2 - COOH 2-F- 6 -MeO-3-pyridyl 195-7 benzyl 36 4-MeOCO COOMe Me 6 -MeO-3-pyridyl 109-12 37 ß COOMe H 5- (3-thienyl) - 149-50 3 - pyridyl 38 - COOMe Me 6-NH2-3- Pyridyl 119-22 39 -. 39 - COOMe H $ -pr »0-3-Pyridyl 15-7 40 -. 40 - tetrazole - Me 6_Me0-3 -pyridyl 198-200 5-yl 1 - COOMe H 6 -MeCOO-3-pyridyl 109-12 2 3-Cl COOMe H 6-MeO-3-pWdilo 106-10 3 - COOMe H 4-Cl-2-pyridyl 158-60 4-COOPr H 6-MeO-3-pWdilo 107-9 5 - COOBu H 6-MeO-3-pyridyl 57-60 6 - COOPr Me 6-MeO-3 - pyridyl 81.5-4 7 - COOBu Me 6-MeO-3-pyridyl 72-6 Comp. (H)] P-f. (') 48 3-C1 COOMe Me 6-MeO-3 -pyridyl 84-7 49 -. 49 - COO-allyl H 6-MeO-3-pyridyl 98-9.5 50 4-C1 COOMe Me 6-MeO-3-pyridflo 98-100 51 -. 51 - COOMe -CH2C «CH 6 -MeO-3-Piriyl 84.5-87 52 ß H 6-MeO-3 -pyridyl 124-34 53 ** H 6-Me? -3-pyridyl 115-6 54 4-F COOMe H 6-Me? -3-pyridyl 125-6 55 -. 55 - COOHH4 H 6 -MeO-3-pyridyl 250-2 56 5, 6 -benzo COOMe H 6-MeO-3-p? Ridi, ° 157-61 57 4-C73 COOMe H 6-MeO-3-Piridi | 0 139-42 58 COOMe 4-CF3- 6-Me? -3-pyridyl 111-3 b? Ncyl 59 - COOMe H 6-MeNH-3-P? Pdyl 187-89 60 - COOMe 2-Me- 6-MeO- -pyridyl 112-4 benzyl 1 -COOMe 4-MeO- 6-Me? -3-pyridyl 119-21 benzyl 2 -COOMe Me 2 -pyridyl 80-2 3 COOMe H 2 -MeO-4-pyridyl 132-5 4-COOMe H 5,6-dichloro-161-2 3 -pyridyl 5-COO 'N + Bu 4 H 6 -MeO-3-pyridyl 250- 2 6 - COOMe H 2-cl-3-P'ridyl 120-1 Cpd (R1),. z Y A m.p. ( H.H) 67 -. 67 - COOMe H 2 -MeO-3 -pyridyl 78-81 68 -. 68 - CH "N-0H H 6-Me? -3-pyridyl 145-6 69 - C «N-NMe2 H 6-MeO-3-PirWi, ° 87-9 Me 0 - COOMe H 2 -MeS-3-pyridyl 117-9 1 COOMe H 5-Br-6-MeO-Pyridyl 164-5 3- pyridyl 2 COOMe Me 5-Br-6-MeO-pyridyl 112-4 3 -pyridyl 3-COOMe H 5-MeO-2-pyridyl 141-3 4 -COOMe H 6 -Me-3 -.pyridyl 125-6 5 5-Me COOMe H 2 -MeO-3 -Piridyl 139-40 6 - COOC5H11 H 6 -MeO-3-pyridyl 49-52 7 * • COOCH2- H 6-MeO-3-pyridyl 125-7 COOMe 8"" COOCH2- H 6-Me0-3-phidyl 129-32 OCH 9 - COOBu 'H 6-MeO-3-phenyldo 81-3 0 COOMe H 5-P -6-MeO-pyridyl 159-61 -pyridyl 1 - COOMe -CH2C00Me 6-Me0-3-pyridyl Oil 2 - COObessil H 2 -MeO-3-pyridyl 79-80 3 N-OMe Me 6-Me? -3-pyridyl oil 4 5- (4-Cl- H 6-Me? -3-pyridyl 193-7 Ph) -1, 3, 4 oxadiazole -2- -yl Comp. CR1) p.f. C) cyclohexyl 85 COO- H 6 -MßO- 3 -pyridyl 203-5 cyclohexyl 86 4-F, 5-Mß COOMe H 2-MßO-3-pyridyl glass 87 -. 87 - 2-fylryl H 6-MeO-3-Plridyl 112-7 88 COOCH2- H 6-MeO-3-pyridyl 155-8 CH2C1 89 - COOMe Me 2 -MeO- 3 -pyridyl oil 90 5-F COOMe H ß-MeO-S- W ilo 125-6 91 -. 91 - COOMe allyl ß-MeO-S-iridyl oil 92 -. 92 - COOMe acetyl 6-MeO-3-PÍpdilo oil 93 -. 93 - COOMe benzoyl 6-MeO-3-plridyl 117-8 94 • COOMe 3, 4-Me02- 6-Me? -3-pyridyl 116-8 P -CH2CH2- 95 - COOMe H 5-Me? -3-iridyl 117-9 96 mm COOMe -CH2Ph 5-Cl-6-MßO- 126-8 3 -pyridyl 97 - COOMe Me 5,6-Cl 2 -3-pyridium 103-4 98 «~ COOMe H 5-Cl-6-MeS-167-9 3 -pyridyl 99 -COOMe H 5-Br-3-pWdllo 122-3 100 5- (4-Cl- Me 6-Meo-3-pJldidyl 188-91 Ph) -l, 3 f4 oxadiazole -2-Bo 101 ^ COOMe Me 4, 6- (Meo) 2- 111-3 2 -pyrimidinyl 102 -Me COOMe H 6 -MßO- 3 -pyridyl 116-9 103 COOMe Me 5-Me -2-pyridHo 82-4 104 5-Mß COOMe H 6-MeO-3-pyrldyl 160-2 105 -. 105 - COOMe Me 5 -MeO- 3 -pyridyl 60-2 106 6-C1 COOMe H 6 -MeO-3-pyridyl 160-2 Comp. (R1) p.f. (') 107 COOMe H 5, 6- (MeO) 2- 155-7 3 -pyridyl 108 5- (4-Cl- H 6 -MeO-3-pyrid »0 215-7 Ph) -1, 3, 4-thiadiazole- 2-ylo 109 4-C1 COOMe H 2 - (MeS02) -pyridyl 183-5 5-pyrimidyl 110 5-N02 COOMe H 6-MeO-3-pyridyl 197-9 111 3.5-Me2 COOMe H 6 -MeO-3-pyridyl 131-3 112 COOMe S02Me 6-MeO-3H > iridyl 125-8 113 COOMe H 4-MeO-2-MeS? 2- 187-90 5-pyrimidyl 114 1-? Irolyl H 6 -MeO-3-pyridyl 113-6 115 4-C1 COOMe H 2 -MeO-5-? irimidyl 175-7 116 6-F COOMe H 6-MeO-3-pyridyl 177-9 117 4 -MeO COOMe H • 6-MeO-3-? iridyl 164-5 118 COOMe -CH (Me) Ph 6 -MeO- 3-pyridyl 132-3 119 COOMe Me 5, 6- (MeO) -pyridyl 110-2 3 -pyridyl 120 COOMe H 4-Cl-6- [N- (2-MeOCO-210-2 Ph) NHC03-2- pyridi, or 121-COOMe H 4-MeO-6- [N- (2-MeO-195-9 CO-P) NHCO J -2 -pyridyl 122 -COOMe H 6- [K- (2- MeOCO-Ph) - 198-200 NHCO] -3-pyridyl 23 _ COOMe H 6-CF3CH20-3-pyridH? 173-4 Comp. p.f. C) 124 -. 124 - COOMe H 2.5- (MeO) 2-6- [N-195-9 (2-MeOCO-Ph) NHCOJ-3 -pyridyl 125 • COOMe H 4 6- (EtO) 2- 115-6 2 - pyridyl 126 - COOMe 2-Me- 2 -MeO-3-pyridyl 101-3 benzyl 127 5-NH2 COOMe H 6-KeO-3-Pípdyl 171-3 128 -. 128 - COOMe H 6- (2, 3, 4-Cl3-l-183 pyrrolyl) -3-pyridyl 129 • 2-benz-H 6 -MeO-3-pyridyl 272-5 imidazolyl 30 • COO-allyl 5-Cl-6-MeO-113-5 3-pyridyl 31 COOCH2- H 5-Cl-6-MeO-163-5 * CßCH 3 -pyridyl 32 3-F COOMe H 6-MeO-3-pyridik > 107-9 33 5-0H COOHe H 6-MeO-3-PÍpdilo 203-5 34 5-1 COOMe H 6-Me? -3-pyridyl 154-6 5-MeOCO COOMe H 6-MeO-3-pyridyl -6 Comp. (R1) p.f. C) 136 5-MeCONH COOMe H 6-MeO-3-pyridyl 253-6 137 • COOMe -CH (Me) - 6-Me? -3-pyridyl 134-5 COOMe 138 _ COOMe 2-Me- 5-Cl-6-MeO- bßncyl-pyridyl oil 139 «• COOEt H 5-Cl-6 -MeO- 136-8 3 -pyridyl 140 COOH H 5-Cl-6-MeO-247-50 3 -pyridyl 141 5-MeS02NH COOMe H 6 -MeO-3 -pyridyl 184-5 142 -. 142 - COOM? H 5 -cyano-3-pyridyl 190-2 143 -. 143 - COOMe H 6-fopayl-3-pyridyl 153-7 144 COOMe H 5-Br-2-MeO- 180-2 3 -pyridyl 145 4-C1 COOMe Me 2 -MeO-5-pyrimidinyl 86-8 146 -. 146 - COOMe H 2-C1-4 -pyridyl 108-10 47 w COOMe H 2 -Cl-6-MeO-144-5 3 -pyridyl 48 COOMe H 6- (2, 3, 4, 5-Cl4- 289 1 -pyrrolyl) -3-pyridyl 49 -COOMa H 6-Cl-3-pyridyl 300 50 -COOMe H 6 -MeOCH 2 3- pyridyl 117-8 51 -COOMe H 5-cyano-6-Me? -247-50 3 -pyridyl 52 5-Me- H 6 -MeO-3-? iridyl 143-5 1, 3, 4- thiazol-2-yl 53 COOMe H 5-cyano-6-Me 2 N- 190-2 3 -pyridyl 54 -COOMe H 5-MeSO ^ O-3-pyridyl 149-51 Comp. (R1., Z Y A p.f. C) 155 -. 155 - COOMe H 6- (2, 3, 5-Cl3- 134-5 1-? Irolyl) -3-plrldllo 156 - COOMe H 6 -MeOCO- 3-pyridyl 141 157 -. 157 - COOMe H 5 -PhCH20- 3 -pyridyl 123-31 158 -. 158 - COOMe H 5 -MeS-3 -pyridyl 122-3 159 -. 159 - COOMe H 5-MeOCO-2- lridllo 187-8 160"" COOMe H 2 / 6- (MeO) 2-pyridyl 141-3 3 -pyridyl 161 -COOMe H 5 -MeS? 2-3 -pyridyl 168-70 162 -. 162 - COOMe H 5 -MeSO-3 -pyridyl 130-2 163 -. 163 - COOMe Me 5-MeS-3 -pyridyl oil 164 - COOMe H 5- (NsC-CH20) - solid 3-plridllo 165 - COOMe Me 5 -Me SO-j- 3 -pyridyl 109-11 166 -. 166 - COOMe H 5-ClCH2S-3-píridil0 112-4 167 -. 167 - COOH H 6-C1-3 -pyridyl 240 168 -. 168 - COOMe H 5-MeOCO-3-pyridyl? 147-8 169 - COOMe H 6 - [N- (2-MeOCO-Ph) - 195-9 NHCO] -3-pyridyl 170 - COOMe H 5 -Me-3-pyridyl 116-7 71 - COOMe H 6-MßO-5- N? 2- 150-1 3 -pyridyl 72 -COOMe H 6-PhO-3 -pyridyl 97-8 73 • > COOMe H 5, 6- (MeS) 2- 157-8 -pyridyl 74 COOMe Me 2, 6- (MeO) 2- 103-5 3 -pyridyl 75 -COOMe Me 5-MeOCO-3-f > Irdidyl oil 76 - COOMe Me 5-Me-3-pyridyl 114-5 77 - COOH H 5 -HOCO-3-pyridyl 275 Comp. (R) | p.f. OR 178 COOMe H 5- "cedl-6-Me- 144-5 3-pyridyl 179 COOMe H 5 -Ph-3- iridyl 124-5 180 COOMe Me 6-Ph? -3-pyridyl 114-5 181 COOMe H 5- [N- (2-MßOCO-Ph) - 180-2 NHC? J -3- pyridylthio 182 COOMe H 5-PhCH2S-3-pyridyl? 104-6 183 COOMe Me 5 -MeO-2-pyrazinyl 81-3 184 4-P COOMe Me 6-Mß? -3-pyridyl 102-4 185 COOMe Et 6 -MßO-3-pyridyl 53-5 186 COOMe H 2 -MeO-5-pyrimidinyl 164-5 187 COOMe Me 2 -Me? -5-pyrimidinyl 128-30 188 COOMe H 4, 6- (MßO) 2-2-PhCH20- - 127-9 5-pyrimidinyl 189 COOMe K 2-Cl-4CF3- 139-40 5-pyrimidinium 190 COOMe H 2- ß2N-4CF3- 133-6 5-pyrimidinyl 91 COOMe H 2 -Me0-4CP3- 13940 5-pyrimidinyl 92 COOMe H 6-Cl-5-MeO-168-71 2 -pyrazinyl 93 COOMe H 5-Br-2-Me- 165-6 4-pyrimidinho 94 COOMe H 2, 4, 6- (MßO) 3- 153-5 5-pirimWlnllo 95 COOMe Me 6-Cl-3-pyridyl? 84-6 96 COOMe H 2 -Cl- -pyrimidinyl 159-61 97 COOMe H 5-Me-2-? Irazil ilo 158-60.5 98 COOMe H 2 -MßO- 4 -pyrimidinyl 135-6 99 COOPr H 2 - eS ? "129-31 5-pyrimidinyl Comp. (R1) p.f. { •) 200 COOPr 2-MβSO-116-8 5-pyrimidinyl 201 COOPr H 2 -MeO-5- pyrimidinyl 104-5 202 COOEt H 2 -etO-5-pyrimidinyl 134-5 203 COOH H 2 -Et-5- irimidinyl 150- 62 204 COOMe H 2 -Me-5-? Irimidinium 141-3 205 COOMe H 5-plrimldlnllo 158-61 206 COOMe Me 2 -He- -pyrimidinyl 88-90 207 COOMe H 2 -Cl-5-pyrimidinyl 159- 61 208 COOMe H 2-Br-5-pyrimidinyl 177-8 209 COOMe H 2-PhCH2NH-192-4 5-pyrimidinyl 210 COOMe H 2 -morpholine-222-3 5-pyrimidinyl 211 COOMe H 5-Br -2-MßS- 192-4 4-pyrimidinyl 212 COOMe H 5-Br-2-MßO-178-80-pyrimidinyl 213 COOMe H 2-MβOCOCH 2 HH-194-7 5-pyrimidinyl 214 COOMe 2,6-Cl 2 -170- 5-pyrimidinyl 215 COOMe 2 -CF3-5-pyrimidinyl 143-5 216 COOMe K 2-Ph-5-pyrimidinyl 151-5 217 COOMe H 2, 6- (MeO) 2- 167-9 4-pyrimidinyl 218 COOMe Me 2-Ph-5-pyrimidyl rubber 219 COOMe H 2, 6-Cl2- 135-7 5-pyrimidinium 220 COOMe H 2 -NC-5-pyrimidinyl 186-8 221 COOMe H 4, 5- (MeO) 2- 182-3 2-pyrimidinyl Comp. < Rl) P-f. (H.H) 222 COOMe H 4, 6- (MeO) 2- 163-4 -pyrimidinyl 223 COOMe H 2 -MeONH-194-6 5-pyrimidinyl 224 COOMe H 2 -MeHH-230-1 5 -pyrimidinyl 225 COOMe H 2 -Cl- 4- (2-MeOCO-190-2 PhNH) -5-plrimldnyl 226 COOMe H 5-Cl-6-Me- 136-41 2-? Irazinyl 227 COOMe H 5-Me -6-Mß- 166-9 2 - pyrazinyl 228 COOMe H 2- (N-methoxy-151-2 N-methoxycarbonyl-amino) -5-; pipmidinyl 229 COOMe H 2 -cyclopropyl 112-4 5-pyrimidinyl 230 3-MeOCO COOMe H 6-Me? -3- iridyl 111-4 231 -. 231 - COOMe H 2 -MeS-5-pyrimidyl-yl 160-2 232 -. 232 - COOMe H 5, 6-CI2-2- pyrazinyl 143-8 233 _ COOMe H 5- (2-thienyl) - 148-9 3 -pyridyl 234 COOKe H 5- (4-CF3-Ph) - 155-6 -pyridyl 235 COOMe H 5- (C1S02) -3-pyridyl 144- 5 236 COOMe H 5- (Cl2CHS) - 120-2 3 -pyridyl 37 COOMe H 5- (NH2S02) - 185-7 3 -pyridyl 38 COOMe H 5-Br-6-Cl-3-plridll? 157-9 39 COOMe Me 5-N02-6-MeO- 98-100 3 -pyridyl Comp. (R1) .f. C) 240 -. 240 - COOMe H 2- a-imidazolyl) - 193-5 pyrimidinyl 241 m COOMe H 4-MeO-2-MeS-140-2 5-pyrimidinyl 242 mm COOMe Me 2, 6- (MeO) 2- 101- 3 4 -pyrimidinyl 243 COOH 3, 4- (MeO) 2-6-MeO-3-pyridyl 123-4 beneyl 244 - COOMe H 5- (Me2NS02) - 169-70 3-pyridyl 245 COOMe H 5-Br-6 -Me? - 169-70 3 -pyridyl 246 mm COOMe H 5-Br-6-MeS02- 223-5 3 -pyridyl 247 COOMe H 5-Br-6-MeSO-160-2 -pyridyl 248 - COOC5Hn H 2 - MeO-3 -pyridyl 47-8 249 -. 249 - coolaryl H 2-MßO-3-pJridyl 80-1 250 - COOMe 2-MßT 6- (2-Me-bßncil) - benzyl 3-pyridyl oil 251 - COOMe H 2 -Cl 4 - chinoHnyl 163-4 252 -. 252 - COOMe -CH2Ph 6-MeO-3-pyridyl 101-2 253, 5- 2 COOMe H 2 -MeO-3-pyridyl 152-4 254 • "COOMe H 5-NH2-6-MeO-202-3 3-pyridyl 255 •" COOMe Me 2, 4"(MeO) 2- 78-81 5- pyrimidinyl 256 mm COOMe 2-MeO- 2 -MeO- 5-pyrimidinyl benzyl gum 257 • "COOMe H 4-Me-2-MeS-78-81 5-pyrimidinyl Comp. (Rl) Q Z Y? p.f. (H.H) 258 -. 258 - COOMe fí 2- (3-pyridyloxy) - 124-6 5-pirim finflo 259 -. 259 - COOMe H 2-F-3-pyridyl 130-1 260 -. 260 - COOMe 2-Me- 5, 6- (MeO) 2- oil benzyl 3-pyridyl 261 -. 261 - COOMe H 5,6-methyndiioxi- 168-79 3-pyridyl 262 -. 262 - COOMe H 5-I-6-MeO-pyridium 173-5 263 3,4-Me2 COOMe H 2 -MeO-3-pyridyl 126-7 264 4-C1 COOMe H 2-MeO-3-pyridane 128-30 The following compounds are also prepared a) ethyl N- (6-methoxy-3-pyridiniumcarbonyl) anthranilate as an oil (compound 265) b) methyl N- (5,6-dimethoxy-3-pyridiniumcarbonyl) anthranilate, m.p. 154-5 °, (compound 266) c) Methyl N- (2-methoxy-5-pyrimidiniumcarbonyl) anthranilate, m.p. 135-7 °, (compound 267) d) N- (6-methoxy-3-pyridiniumcarbonyl) isobutyl anthranilate as an oil, (compound 268) The compounds are evaluated for activity against one or more of the following: Phytophthora infeßtans: late blight of the tomato Plastmo para vi tícola: mildew of the wine Erysiphe graminis: powdery mildew of the barley Pyricularia oryzae: wilt of the rice husk Pellicularia sasakii: blight of the rice husk Botrytie cin rea: gray mold Venturia inaequalis: apple scab Leptoßphaeria nodorum: spotting of glume Aqueous solutions or dispersions of the compounds in the desired concentration, including a wetting agent, are applied by sprinkling or soaking the base of the stem of the plants test, as appropriate. The plants or parts of the plant are then inoculated with appropriate test pathogens and kept under controlled environmental conditions suitable for maintaining the growth of the plant and the development of the disease. After an appropriate time, the degree of infection of the affected part of the plant is calculated visually. The compounds are considered active if they give more than 50% control of the disease at a concentration of 500 ppm (w / v) or less. Compounds 28, 38, 41, 50, 98, 101, 155, 216 and 260 showed activity against Phytophthora inf tin; Compounds 9, 28, 36, 37, 49-51, 54, 56, 59, 61, 66, 67, 70, 71, 83, 98, 101, 111, 113, 114, 116, 120, 121, 137, 139, 142, 156, 161, 174-178, 184, 187, 208, 222, 223, 235, 240-242, 245 and 251 showed activity against Plas opara viticola; Compounds 1-3, 9-12, 20, 23, 25-27, 29-31, 34, , 44, 46, 54, 58, 61, 63, 71, 72, 78, 79, 90-94, 96, 99, 101, 106-108, 116, 119, 130, 131, 139, 151, 152, 171, 174, 183-187, 192, 202, 213, 217, 223, 224, 226-228, 232, 239, 242, 245-247, 249, 250, 252 and 260 showed activity against Erysiphe graminiß; Compounds 1, la, 2, 6a, 42, 43, 48, 57, 59, 62, 64, 65, 110, 113, 144, 146, 172, 204, 206, 223 and 251 showed activity against Pyricularia aryzae; Compounds 14, 39, 43, 54, 100, 101, 185, 189, 190 and 252 showed activity against Pellicularia saßakii; Compounds 42, 45-47, 53, 55, 106, 113, 170, 202 and 225 showed activity against Botrytis cinerea; Compounds 1, 8, 12, 17, 40, 55, 74, 90, 98, 104, 127, 129, 162, 164, 178, 185, 193, 198, 213, 218, 219, 222 and 224 showed activity against Venturia inaequalie; and Compounds 33, 52, 53, 178, 190, 194 and 223 showed activity against Leptoßphaeria nodorum. Having described the invention as above, property is claimed as contained in the following:

Claims (3)

1. A compound of the formula I characterized in that X is O or S; A is a 6-membered heteroaryl group, comprising at least one nitrogen atom, which is optionally substituted by one or more of the group R2; R1 is alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, Y1-X- or amino, (each of which is optionally substituted), halogen, cyano, nitro, acyl, acyloxy, optionally substituted heterocyclyl or optionally substituted phenyl; or two adjacent groups together with the carbon atoms to which they are attached, can form an optionally substituted benzo ring; R2 has the same meaning as R1 or two adjacent groups together with the carbon atoms to which they are attached, can form an optionally substituted heterocyclic ring; Y is alkyl, cycloalkyl, cycloalkenyl, alkenyl or alkynyl, each of which is optionally substituted, hydrogen or acyl; Y1 has the same meaning as Y or is optionally substituted phenyl or optionally substituted heterocyclyl; Z is C (= X1) -X2-R3, cyano, optionally substituted heterocyclyl, -C (R5) = N-OR6 or -C (R5) = N-NR6R7; R3 is alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, phenyl or heterocyclyl, each of which is optionally substituted, hydrogen or an inorganic or organic cationic group. X1 and X2, which may be the same or different, are O or S; R5, R6 and R7, which may be the same or different, are alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, phenyl or heterocyclyl, each of which is optionally substituted or hydrogen or R6 and R7 together with the atom or atoms which are joined together can form a ring; n is 0 to 4, together with complexes with metal salts, as well as salts with bases of compounds, which are acids and salts with acids of the compounds which are bases, with the proviso that when Y is hydrogen and i) when Z is carboxy, methoxycarbonyl or ethoxycarbonyl, ring A is not substituted with pyridyl or pyrazinyl; and ii) when Z is carboxy and n is 0, A is not 2-chloro-3-pyridyl, 6- (2-diethylaminoethoxy) -3-pyridyl or a 2-pyridyl group.

2. The fungicidal compositions which are characterized in that they comprise a compound according to claim 1 in admixture with an agriculturally acceptable diluent or carrier.

3. A method for combating a phytopathogenic fungus in a site contaminated or exposed to be contaminated therein, which is characterized in that it comprises applying to the site a compound according to claim 1. SUMMARY OF THE INVENTION A compound of the formula I X is O OR S; A is a 6-membered heteroaryl group, comprising at least one nitrogen atom, which is optionally substituted by one or more of the group R2; R1 is alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, Y1-X- or amino, (each of which is optionally substituted), halogen, cyano, nitro, acyl, acyloxy, optionally substituted heterocyclyl or optionally substituted phenyl; or two adjacent groups together with the carbon atoms to which they are attached, can form an optionally substituted benzo ring; R2 has the same meaning as R1 or two adjacent groups together with the carbon atoms to which they are attached, can form an optionally substituted heterocyclic ring; Y is alkyl, cycloalkyl, cycloalkenyl, alkenyl or alkynyl, each of which is optionally substituted, hydrogen or acyl; Y1 has the same meaning as Y or is optionally substituted phenyl or optionally substituted heterocyclyl; Z is C (= ?!) -X2-R3, cyano, optionally substituted heterocyclyl, -C (R5) = N-OR6 or -C (R5) = N-NR6R7; R3 is alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, phenyl or heterocyclyl, each of which is optionally substituted, hydrogen or an inorganic or organic cationic group. X1 and X2, which may be the same or different, are 0 or S; R5, R6 and R7, which may be the same or different, are alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, phenyl or heterocyclyl, each of which is optionally substituted or hydrogen or R6 and R7 together with the atom or atoms which are joined together can form a ring; n is 0 to 4, together with complexes with metal salts, as well as salts with bases of compounds, which are acids and salts with acids of the compounds which are bases, have fungicidal activity.