ANILIDE DERIVATIVES AS FUNGICIDES

Abstract: Compounds of formula (I), wherein: 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 R<2>; R<1> is alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl or amino, (each of which is optionally substituted), Y<1>-X-, 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; R<2> has the same meaning as R<1> 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; Y<1> has the same meaning as Y or is optionally substituted phenyl or optionally substituted heterocyclyl; Z is C(=X<1>)-X<2>-R<3>, cyano, nitro, amino, acyl, optionally substituted heterocyclyl, -C(R<5>)=N-OR<6> or -C(R<5>)=N-NR<6>R<7>; R<3> is alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, phenyl or heterocyclyl, each of which is optionally substituted, hydrogen or an inorganic or organic cationic group ; X<1> and X<2>, which may be the same or different, are O or S , R<5>, R<6> and R<7>, 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 R<6> and R<7> together with the atom(s) 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 acids and salts with acids of compounds which are bases, have fungidal activity.

Description: Title: ANILIDE DERIVATIVES AS FUNGICIDES Field of the invention This invention relates to new derivatives of anthranilic acid useful as fungicides . Prior Art In GB 1,563,664 and Japanese Kokai 53130655, there are disclosed fungicidal esters of anthranilic acid. We have found that certain novel anthranilic acid derivatives also have valuable fungicidal activity and also have advantages over compounds disclosed in these publications. Disclosure of the invention According to the invention there is provided a compound of 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 n or more of the group R ,* R 1 is alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, or amino, (each of which is optionally substituted) , Y l -X- , 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; R 2 has the same meaning as R 1 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; Y 1 has the same meaning as Y or is optionally substituted phenyl or optionally substituted heterocyclyl; Z is C(=X 1 )-X 2 -R 3 , cyano, nitro, amino, acyl, optionally substituted heterocyclyl, -C(R 5 )=N-OR 6 or -C(R 5 )=N-NR 6 R 7 ; R J is alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, phenyl or heterocyclyl, each of which is optionally substituted, hydrogen or an inorganic or organic cationic group; X 1 and X 2 , which may be the same or different, are O or S; R 5 , R 6 and R 7 , 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 R 6 and R 7 together with the atom(s) to which they are attached can form a ring; and 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 compounds which are bases, with the proviso that when Y is hydrogen and i) when Z is carboxy, methoxycarbonyl or ethoxycarbony1 ring A is not unsubstituted 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. Alkyl groups are preferably of 1 to 20, eg 1 to 6, carbon atoms. Alkenyl and alkynyl groups are generally of 3 to 6 carbon atoms. Cycloalkyl or cycloalkenyl groups are preferably of 3 to 8 carbon atoms. Substituents, when present on any alkyl, cycloalkyl, cycloalkenyl, alkenyl or alkynyl moiety include halogen, azido, cyano, optionally substituted alkoxy, optionally substituted alkylthio, hydroxy, nitro, optionally substituted amino, acyl, acyloxy, optionally substituted phenyl, optionally substituted heterocyclyl, optionally substituted phenoxy and optionally substituted heterocyclyloxy. Cycloalkyl or cycloalkenyl groups may also be substituted by alkyl. Substituents when present on any phenyl group are usually one or more of the same groups as defined for R . The term heterocyclyl includes both aromatic and non- aromatic heterocyclyl groups. Heterocyclyl groups are generally 5, 6 or 7-membered rings containing up to 4 hetero atoms selected from nitrogen, oxygen and sulfur. Examples of heterocyclyl groups are furyl, thienyl, pyrrolyl, pyrrolinyl, pyrrolidinyl, imidazolyl, dioxolanyl, oxazolyl, thiazolyl, imidazolyl, imidazolinyl, i idazolidinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, pyranyl, pyridyl, piperidinyl, dioxanyl, orpholino, dithianyl, thio orpholino, pyridazinyl, pyriroidinyl, pyrazinyl, piperazinyl, triazinyl, thiazolinyl, benzimidazolyl, tetrazolyl, benzoxazolyl, i idazopyridinyl, 1,3-benzoxazinyl, 1,3-benzothiazinyl, oxazolopyridinyl, benzofuranyl, quinolinyl, quinazolinyl, quinoxalinyl, sulfolanyl, dihydroquinazolinyl, benzothiazolyl, phthalimido, benzofuranyl, azepinyl, oxazepinyl, thiazepinyl, diazepinyl and benzodiazepinyl. Heterocyclyl groups may themselves be substituted for example as for phenyl. Amino groups may be substituted for example by one or two optionally substituted alkyl or acyl, or two substituents can form a ring, preferably a 5 to 7-memberεd ring, which may be substituted and may contain other heteroatoms, for example morpholine, thiomorpholine, or piperidine. The term acyl includes the residue of sulfur and phosphorus-containing acids as well as carboxylic acids. Examples of acyl groups are thus -COR 15 , -COOR 5 , -CXNR 5 R 6 , -CON(R 5 )OR 6 , -COONR 5 R 6 , -CON(R 5 )NR 6 R 7 , -COSR 5 , -CSSR 5 , -S(0) p R 5 , -S(0) 2 OR 5 , -S(0) p NR 5 R 6 , -P(=X) (OR 5 ) (OR 6 ) , -CO-COOR 5 , where R 5 , R 6 and R 7 are as defined previously, or R 6 and R 7 together with the atom(s) to which they are attached can form a ring, p is 1 or 2 and X is O or S. It is generally preferred that A is a pyridine, (especially 3-pyridyl) , a pyrimidine (especially 5-pyrimidinyl) , or a pyrazine ring. A may also be for example a tetrazine, pyridazine or triazine ring. R 2 is preferably selected from halogen and alkoxy, especially methoxy. R 1 is preferably selected from halogen, especially fluorine, and alkyl, especially methyl. Z is preferably C(=X 1 ) -X 2 -R 3 . X 1 and X 2 are both preferably 0 and R 3 is generally alkyl, alkenyl or alkynyl, each of which is optionally substituted, and is especially methyl. Y is preferably hydrogen, alkyl, especially methyl or acyl, especially alkanoyl or alkoxycarbonyl. X is preferably O. n is preferably 0. Complexes of compounds of the invention are usually formed from a salt of formula Man 2 , in which M is a divalent metal cation, e.g. copper, manganese, cobalt, nickel, iron or zinc and An is an anion, e.g. chloride, nitrate or sulfate. The compounds of the invention have activity against a wide range of pathogens of Deuteromycete, Ascomycete, Phyco ycete and Basidiomycete origin, especially against fungal diseases of plants, e.g. mildews and particularly barley powdery mildew (∑rysiphe graminis ) cucumber powdery mildew (∑rysiphe cichoracaerum) and vine downy mildews (Plasmopara viticola and Uncinula necator) , rice blast (Pyricularia oryzae) , cereal eyespot (Pseudocercosporella herpotrichoides ) , rice sheath blight (Pellicularia sasakii ) , grey mould (Botrytis cinerea) , wheat brown rust (P ccinia recondita) , late tomato or potato blight (Phytophthora infestans) , apple scab (Venturia inaequalis) and glume blotch (Leptosphaeria nodorum) . Some compounds may be active against only a few pathogens whereas others may have a broader spectrum of activity. Some novel compounds of formula I have weak pesticidal activity but still have utility as intermediates and such compounds also form one aspect of the invention. The compounds of the invention are generally formulated in conventional compositions used for fungicides. These compositions can contain one or more additional pesticides, for example 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, emulsifying agent or wetting agent. Suitable surface-active agents include anionic compounds such as a carboxylate, for example a metal carboxylate of a long chain fatty acid; an N-acylsarcosinate; mono- or di-esters of phosphoric acid with fatty alcohol ethoxylates or salts of such esters; fatty alcohol sulfates such as sodium dodecyl sulfate, sodium octadecyl sulfate or sodium cetyl sulfate; ethoxylated fatty alcohol sulfates; ethoxylatεd alkylphenol sulfates; lignin sulfonates; petroleum sulfonates; alkyl-aryl sulfonates such as alkyl-benzene sulfonates or lower alkylnaphthalene sulfonates, e.g. butyl-naphthalene sulfonatε; salts of sulfonated naphthalene-formaldehyde condensates; salts of sulfonated phenol-formaldehyde condensates; or more complex sulfonates such as the amide sulfonates, e.g. the sulfonated condensation product of oleic acid and N-methyl taurine or the dialkyl sulfosuccinates, e.g. the sodium sulfonate of dioctyl succinate. Nonionic agents include condensation products of fatty acid esters, fatty alcohols, fatty acid amides or fatty-alkyl- or alkenyl-substituted phenols with ethylene oxide, fatty esters of polyhydric alcohol ethers, e.g. sorbitan fatty acid esters, condensation products of such esters with ethylene oxide, e.g. polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, acetylenic glycols such as 2,4,7,9-tetramethyl- 5-decyne-4,7-diol, or ethoxylated acetylenic glycols. Examples of a cationic surface-active agent include, for instance, an aliphatic mono-, di-, or polya ine as an acetate, naphthenate or oleate; an oxygen-containing amine such as an amine oxide or polyoxyethylene alkylamine; an amide-linked amine prepared by the condensation of a carboxylic acid with a 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 dusting powder, a seed dressing, a fumigant, a smoke, a dispersible powder, an emulsifiable concentrate or granules. Moreover it can be in a suitable form for direct application or as a concentrate or primary composition which requires dilution with a suitable quantity 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 forms. 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.' A further 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 can if desired be added to an emulsion of oil in water to give a dispersion of active ingredient in an aqueous oil emulsion. An emulsifiable concentrate comprises a compound of the invention dissolved in a water-immiscible solvent together with an emulsifying agent and which is formed into an emulsion on mixing with water. A dusting powder comprises a compound of the invention intimately mixed with a solid pulverulent diluent, for example, kaolin. A granular solid comprises a compound of the invention associated with similar diluents to those which may be employed in dusting powders, but the mixture is granulated by known methods. Alternatively it comprises the active ingredient adsorbed or absorbed on a pre-granular diluent, for example, Fuller's earth, attapulgite or limestone grit. A we * ctable powder usually comprises the active ingredient in admixture with a suitable surfactant and an inert powder diluent such as china 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 per cent by weight, especially 5 to 30 per cent by weight. In a primary composition the amount of active ingredient can vary widely and can be, for example, from 5 to 95 per cent by weight of the composition. The compounds of the invention may be prepared in known manner, for example by reacting a compound of formula II, ( Rl )n with a compound of formula III 0 II Q—C— (III) where Q is a leaving group, preferably a halogen and especially chlorine, to give a compound of formula I, where X is 0 and Y is hydrogen, and if desired modifying this compound in known manner to give other compounds where X and/or Y have other desired values, and if desired modifying compounds of formula I in known manner to give compounds where R 1 , R- and Z have other values. The reaction between compounds II and III is generally carried out in the presence of a base, e.g. an organic tertiary amine and preferably in the presence of a solvent, e.g. an ether. The compounds of formula II and III are either known or can be prepared in known manner. The resulting compounds of formula I may be modified in known manner to give other compounds of formula I where one of the groups are modified to other desired groups. For example an ester may be converted in known manner to a free acid or a salt. Thio groups may be oxidised using a suitable oxidising agent, eg m-chloroperbenzoic acid, to give sulfinyl and sulfonyl groups. Carbonyl groups may be converted to thiocarbonyl groups by sulfurising in known manner, e.g. using Lawesson's reagent or phosphorus pentasulfide. Alkylsulfonyl groups on ring A may 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. Structures of isolated novel compounds were confirmed by elemental and/or other appropriate analyses. Temperatures are in °C. Example 1 Triethylamine (28.4 g) was added to a solution of 6-chloronicotinic acid (40 g) in dry dichloromethane (900 ml) . The mixture was cooled in an ice bath and methyl chloroformate (26.8 g) was added dropwise. The mixture was stirred at room temperature overnight, washed in turn with water, aqueous sodium hydrogen carbonate and brine. The organic phase was dried over magnesium sulfate, filtered and evaporated to give methyl 6-chloronicotinate. 10 g of this product was added to sodium methanolate (obtained from 1.61 g sodium and 100 ml dried methanol) . The mixture was heated under reflux for 3 hours and allowed to stand at room temperature overnight. Aqueous potassium hydroxide (10 g in 30 ml water) was added and the mixture was heated under reflux for 8 hours. It was left to stand overnight at room temperature, evaporated and the residue added to water (120 ml) . The mixture was acidified to pH 3 with hydrochloric acid. The precipitate was filtered and dried to give 6-methoxynicotinic acid, .p. 175-177°. This acid (6 g) was heated under reflux with an excess amount of thionyl chloride for 2 hours. The mixture was cooled, evaporated and the residue (comprising crude 6-methoxynicotinoyl chloride) was dissolved in dry tetrahydrofuran (10 ml) . This solution was added dropwise to a solution of methyl anthranilat≤ (6.22 g) and triethylamine (7.92 g) in dry tetrahydrofuran (200 ml) . The mixture was stirred at room temperature overnight, evaporated and extracted with ethyl acetate. The extracts were washed with water, dried and evaporated and the residue purified by silica gel column chromatography to give methyl N-(6-methoxynicotinoyl)anthranilate, m.p. 121-3°. (compound 1) In a similar manner there was obtained methyl N-(2-methylthio-5-pyrimidinecarbonyl)anthranilate, m.p. 166-8°. (compound la) Example 2 Sodium hydride (0.15 g of a 60% solution in oil) was added to a solution of the compound 1 from Example 1 (1 g) in dry tetrahydrofuran (25 ml) which had been cooled on an ice bath. The mixture was stirred for 20 minutes and then methyl iodide (0.44 ml) was added. The mixture was stirred at room'temperature for 48 hours, evaporated and extracted with ethyl acetate. The extract was washed in turn with water and brine, dried over magnesium sulfate and evaporated. The residue was purified by silica gel column chromatography to give methyl N-(6-methoxynicotinoyl)- N-methylanthranilate) , m.p. 68-70°. (compound 2) Example 3 To a solution of compound 2 from Example 2 (0.6 g) in ethanol (20 ml) was added copper(II)chloride (0.134 g) . The mixture was allowed to stand overnight, evaporated and the residue triturated with ethyl acetate to give bis-[methyl N-(6-methoxynicotinoyl)-N-methylanthranilate] copper(II)chloride complex, m.p. 196-8°. (compound 3) Example 4 -Chloroperbenzoic acid (13.7 g) was added with stirring to a solution of compound la (6 g) in dichloromethane. The mixture was stirred overnight at room temperature, sodium sulfate added and extracted with dichloromethane. The extract was worked up to give methyl N-(2-methylsulfonyl- 5-pyrimidinecarbonyl)anthranilate, m.p. 187-9°. (compound 4) Example 5 Sodium hydride (0.24 g of a 60% dispersion in oil) was added to a solution of 2-mercaptopyridine (0.33 g) dissolved in dry di ethylforma ide (20 ml) . The mixture was stirred for half an hour at room temperature. A solution of compound 4 (1 g) in dry dimethylformamide (20 ml) was added dropwise with stirring. The mixture was stirred overnight at room temperature. It was cooled and quenched with methanol. The mixture was poured into water and made acidic with dilute hydrochloric acid. The precipitate was collected, dissolved in dichloromethane and the solution washed with brine and evaporated to give methyl N-[2-(2-pyridylthio)-5-pyrimidinecarbonyl]- anthranilate, mp. 145-147° (compound 5) In a similar manner using potassium carbonate as the base instead of sodium hydride there was obtained methyl N-[2-(4-methoxyphenoxy)-5-pyrimidinecarbonyl]- anthranilate, as an oil (compound 5a) . Example 6 Compound 1 was heated with an equimolar amount of aqueous sodium hydroxide to give N-(6-methoxynicotinoyl)- anthranilic acid m.p. 224-3° (compound 6). This compound in turn was treated with further sodium hydroxide to give 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-diphosphetane 2,4-disulfide; 5.09 g) was added to a solution of compound 1 (3 g) in dry tetrahydrofuran (100 ml) . The mixture was stirred under nitrogen for 20 hours. More Lawesson's reagent (2,6 g) was added and the mixture heated under reflux for 13 hours, evaporated and the residue purified by silica gel column chromatography to give methyl N-(6-methoxy-3-pyridinethiocarbonyl)- anthranilate, m.p. 133-4°. (compound 7) Example 8 In a similar manner to one of the processes disclosed in t he previous Examples, the following compounds of formula I were obtained. Cpd (R 1 )*! Z Y A m.p. (°) 8 — COOMe H 6-EtO-3-pyridyl 150-2 9 - COOEt H 6-MeO-3-pyridyl 129-30 10 - COOEt Me 6-Meθ-3-pyridyl 91-2 11 - COOMe -CH 2 CN 6-MeO-3-pyridyl oil 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-pyridy1 172-3 15 4 ,5-(MeO) 2 COOMe H 6-MeO-3-pyridy1 173-5 16 - COObenzyl Me 6-MeO-3-pyridyl 110-3 17 5-C1 COOMe Me 6-MeO-3-pyridy1 89-91 18 4 ,5-(MeO) 2 COOMe Me 6-MeO-3-pyridy1 147-50 19 5-MeS COOMe H 6-Meθ-3-pyridyl 135-7 20 5-MeS COOMe Me 6-MeO-3-pyridyl 78-80 21 - CN H 6-MeO-3-pyridyl 163-6 22 - CN Me 6-MeO-3-pyridy1 90.5-3 23 - COMe H 6-MeO-3-pyridy1 131.5-4 24 - N0 2 H 6-MeO-3-pyridy1 125-7 25 - COOMe H 5-MeO-2-pyrazinyl 169-70 26 6-Me COOMe H 6-Meθ-3-pyridyl 102.5-5 27 — COOMe H 5-Cl-6-MeO- 165-6 3-pyridyl Cpd (R 1 ) .. m.p . ( ° ) 28 - COOMe Me 5-Cl-6-MeO- 110-2 3-pyridyl 29 6-Me COOMe Me 6-MeO-3-pyridyl 117.5-8.5 30 - COOPr; H 6-MeO-3-pyridy1 107-9 31 - COOMe H 6-MeS-3-pyridyl 102.5-5 32 - COOMe Me 6-EtO-3-pyridyl oil 33 — COOMe H 4, 6-(MeO) 2 - 125-7 5-pyrimidinyl 34 — COOMe H 5, 6-(MeO) 2 - 156-9 2-pyrazinyl 35 - COOMe Me 3-pyridyl 86-8 36 - S0 2 Me H 6-MeO-3-pyridyl 148.5-50. 37 - SOMe H 6-MeO-3-pyridyl 111-3 38 4-N0 2 COOMe Me 6-MeO-3-pyridyl 110-2 39 - COOH 2-F- 6-MeO-3-pyridyl 195-7 benzyl 40 4-MeOCO COOMe Me 6-MeO-3-pyridyl 109-12 41 - CONH-OMe H 6-MeO-3-pyridyl 152-3 42 — COOMe H 5-(3-thienyl)- 149-50 3-pyridyl 43 - COOMe Me 6-NH 2 -3-pyridyl 119-22 44 - COOMe H 6-Pr * 0-3-pyridyl 15-7 45 - tetrazol- Me 6-MeO-3-pyridyl 198-200 5-yl 46 - S0 2 Me Me 6-MeO-3-pyridy1 100-2 47 - COOMe H 6-MeCOO-3-pyridyl 109-12 48 3-C1 COOMe H 6-Meθ-3-pyridyl 106-10 49 - COOMe H 4-Cl-2-pyridyl 158-60 50 - COOPr H 6-MeO-3-pyridyl 107-9 51 - COOBu H 6-MeO-3-pyridyl 57-60 52 - COOPr Me 6-MeO-3-pyridyl 81.5-4 53 - COOBu Me 6-MeO-3-pyridyl 72-6 54 3-C1 COOMe Me 6-MeO-3-pyridyl 84-7 Cpd (R 1 ) .. m.p . ( ° ) 55 - CON-OMe Me 6-Meθ-3-pyridyl 147-50 56 - CHO H 6-MeO-3-pyridyl 117-20 57 - COO-allyl H 6-MeO-3-pyridy1 98-9.5 58 4-C1 COOMe Me 6-Meθ-3-pyridy1 98-100 59 - COOMe -CH 2 C≡CH 6-MeO-3-pyridyl 84.5-87 60 "" C=N-NHMe H 6-MeO-3-pyridyl 124-34 61 N-OMe H 6-MeO-3-pyridyl 115-6 62 4-F COOMe H 6-MeO-3-pyridyl 125-6 63 - COONH 4 H 6-MeO-3-pyridyl 250-2 64 5, 6-benzo COOMe H 6-MeO-3-pyridyl 157-61 65 4-CF 3 COOMe H 6-MeO-3-pyridyl 139-42 66 — COOMe 4-CF3- 6-MeO-3-pyridy1 111-3 benzyl 67 CON-OMe H 6-MeO-3-pyridyl 102-4 68 - COOMe H 6-MeNH-3-pyridy1 187-89 69 — COOMe 2-Me- 6-MeO-3-pyridyl 112-4 benzyl 70 — COOMe 4-MeO- 6-MeO-3-pyridy1 119-21 benzyl 71 CONH H 6-MeO-3-pyridyl 165-7 " 72 - COOMe Me 2-pyridyl 80-2 73 - COOMe H 2-MeO-4-pyridyl 132-5 74 - COOMe H 5, 6-Cl -3-pyridyl 161-2 75 - COO " N + Bu 4 H 6-MeO-3-pyridy1 250-2 76 - COOMe H 2-C1-3-pyridyl 120-1 77 _ COOMe H 2-MeO-3-pyridyl 78-81 Cpd ( Rl >n m.p. (°) 78 CHO Me 6-MeO-3-pyridy1 83-4 79 CH=N-OH H 6-MeO-3-pyridyl 145-6 80 H 6-MeO-3-pyridy1 87-9 81 I H 6-MeO-3-pyridyl 140-2 82 COOMe H 2-MeS-3-pyridyl 117-9 83 COOMe H 5-Br-6-MeO- 164-5 3-pyridyl 84 COOMe Me 5-Br-6-MeO- 112-4 3-pyridyl 85 COOMe H 5-Meθ-2-pyridyl 141-3 86 COOMe H 6-Me-3-pyridyl 125-6 87 5-Me COOMe H 2-MeO-3-pyridyl 139-40 88 COOC 5 H 11 H 6-MeO-3-pyridyl 49-52 89 COOCH 2 - H 6-Meθ-3-pyridyl 125-7 COOMe 90 COOCH - H 6-MeO-3-pyridyl 129-32 C≡CH 91 COOBu 1 H 6-MeO-3-pyridyl 81-3 92 COOMe H 5-Ph-6-MeO- 159-61 3-pyridyl 93 COOMe -CH 2 COOMe 6-MeO-3-pyridyl oil 94 COObenzyl H 2-MeO-3-pyridyl 79-80 95 CONHMe H 6-MeO-3-pyridyl 162-4 96 C=N-OMe Me 6-MeO-3-pyridyl oil 97 Ph H 6-MeO-3-pyridyl 107-9 98 5-(4-Cl- H 6-MeO-3-pyridyl 193-7 Ph)-1,3,4- oxadiazol- -2-yl Cpd (R 1 ) n m.p. (°) cyclohexyl 1 99 - COO " N + H ? H 6-MeO-3-pyridy1 203-5 cyclohexyl 100 4-F,5-Me COOMe H 2-MeO-3-pyridy1 glass 101 - 2-fury1 H 6-MeO-3-pyridy1 112-7 102 COOCH 2 - H 6-MeO-3-pyridyl 155-8 CH 2 C1 103 - COOMe Me 2-MeO-3-pyridyl oil 104 5-F COOMe H 6-MeO-3-pyridyl 125-6 105 - COOMe allyl 6-MeO-3-pyridyl oil 106 - COOMe acetyl 6-MeO-3-pyridyl oil 107 - COOMe benzoyl 6-Meθ-3-pyridyl 117-8 108 COOMe 3,4-Me0 2 - 6-MeO-3-pyridy1 116-8 Ph-CH 2 CH 2 - 109 - COOMe H 5-Meθ-3-pyridyl 117-9 110 •*" COOMe -CH 2 Ph 5-Cl-6-MeO- 126-8 3-pyridyl 111 - COOMe Me 5, 6-Cl- > -3-pyridyl 103-4 112 — COOMe H 5-Cl-6-MeS- 167-9 3-pyridyl 113 - COOMe H 5-Br-3-pyridy1 122-3 114 — 5-(4-Cl- Me 6-MeO-3-pyridyl 188-91 Ph)-1,3,4- oxadiazol-2-yl 115 COOMe Me 4, 6-(MeO) 2 - 111-3 2-pyrimidiny1 116 4-Me COOMe H 6-MeO-3-pyridy1 116-9 117 COOMe Me 5-MeO-2-pyridyl 82-4 118 S0 2 NHMe H 6-MeO-3-pyridyl solid 119 5-Me COOMe H 6-Meθ-3-pyridyl 160-2 120 COOMe Me 5-MeO-3-pyridy1 60-2 121 6-C1 COOMe H 6-MeO-3-pyridyl 160-2 Cpd (R 1 ) n m.p. (°) 122 COOMe H 5,6-(MeO) 2 - 155-7 3-pyridyl 123 5-(4-Cl- H 6-MeO-3-pyridyl 215-7 Ph)-1,3,4- thiadiazol-2-yl 124 CONH H 6-MeO-3-pyridyl 140-2 COOMe 125 4-C1 COOMe H 2-(MeS0 2 )- 183-5 5-pyrimidinyl 126 5-N0 2 COOMe H 6-MeO-3-pyridyl 197-9 127 3,5-Me 2 COOMe H 6-MeO-3-pyridyl 131-3 128 - COOMe S0 2 Me 6-MeO-3-pyridyl 125-8 129 - COOMe H 4-MeO-2-MeS0 2 - 187-90 5-pyrimidinyl 130 - 1-pyrrolyl H 6-MeO-3-pyridyl 113-6 131 4-C1 COOMe H 2-MeO-5-pyrimidinyl 175-7 132 6-F COOMe H 6-MeO-3-pyridyl 177- -9 133 4-MeO COOMe H 6-MeO-3-pyridyl 164- -5 134 - COOMe -CH(Me)Ph 6-MeO-3-pyridyl 132- -3 135 - COOMe Me 5 ,6- (MeO) _- 110- -2 3-pyridyl 136 - COCH 2 OMe H 6-MeO-3-pyridyl 110- -2 137 - CONH 2 H 6-MeO-3-pyridyl 224- -8 138 — COOMe H 4-Cl-6-[N-(2-MeOCO- 210- -2 Ph)NHCO]- -pyridyl 139 COOMe H 4-MeO-6-[N-(2-MeO- 195- -9 CO-Ph) NHCO]-2-pyridyl 140 COOMe H 6-[N-(2-MeOCO-Ph)- 198- -200 NHCO]-3-pyridyl 141 COOMe H 6-CF3CH 2 0-3-pyridy1 173- -4 Cpd ( Rl ) n m.p . ( ° ) 142 - COOMe H 2,5-(MeO) 2 -6-[N- 195-9 (2-MeOCO-Ph)NHCO]- 3-pyridyl 143 COOMe H 4,6-(EtO) 2 - 115-6 2-pyridyl 144 - CONEt 2 H 6-MeO-3-pyridyl oil 145 - CONHNH 2 H 6-MeO-3-pyridy1 188-9 146 — CONH- H 6-MeO-3-pyridy1 174-7 N=CMe 2 147 — COOMe 2-Me- 2-MeO-3-pyridyl 101-3 benzyl 148 5-NH 2 COOMe H 6-Meθ-3-pyridyl 171-3 149 — COOMe H 6-(2,3,4-Cl 3 -l- 183 pyrrolyl) -3-pyridyl 150 - SCH-iCHoCN H 6-MeO-3-pyridyl 113-5 O II 151 _ 2-benz- H 6-MeO-3-pyridyl 272-5 imidazolyl 0 152 - S IICH-iCH-iCN H 6-MeO-3-pyridyl 141-3 153 - CONHNH- H 6-MeO-3-pyridyl 193-7 COMe 154 — COO-allyl H 5-Cl-6-MeO- 113-5 3-pyridyl 155 — COOCH 2 - H 5-Cl-6-MeO- 163-5 C≡CH 3-pyridyl 156 3-F COOMe H 6-MeO-3-pyridyl 107-9 157 5-OH COOMe H 6-MeO-3-pyridy1 203-5 158 5-1 COOMe H 6-MeO-3-pyridyl 154-6 159 5-MeOCO COOMe H 6-MeO-3-pyridyl 155-6 Cpd (R 1 ) * ! Z Y A m.p. (°) 160 5-MeCONH COOMe H 6-MeO-3-pyridyl 253-6 161 — COOMe -CH(Me)- 6-MeO-3-pyridy1 134-5 COOMe 162 "" COOMe 2-Me- 5-Cl-6-MeO- oil benzyl 3-pyridyl 163 *-**• COOEt H 5-Cl-6-Me0- 136-8 3-pyridyl 164 COOH H 5-Cl-6-MeO- 247-50 3-pyridyl 165 5-MeS0 2 NH COOMe H 6-MeO-3-pyridyl 184-5 166 - COOMe H 5-cyano-3-pyridyl 190-2 167 - COOMe H 6-formy1-3-pyridyl 153-7 168 — CONH- H 6-MeO-3-pyridyl 188-90 (4-Cl-Ph) 169 — COOMe H 5-Br-2-MeO- 180-2 3-pyridyl 170 4-C1 COOMe Me 2-MeO-5-pyrimidinyl 86-8 171 - COOMe H 2-Cl-4-pyridyl 108-10 172 — COOMe H 2-Cl-6-MeO- 144-5 3-pyridyl 173 COOMe H 6-(2,3,4,5-Cl 4 - 289 1-pyrrolyl)-3-pyridyl 174 COONa H 6-C1-3-pyridyl 300 175 COOMe H 6-MeOCH 2 -3-pyridyl 117-8 176 COOMe H 5-cyano-6-MeO- 247-50 3-pyridyl 177 5-Me- H 6-MeO-3-pyridyl 143-5 1,3,4- thiadiazol-2-yl 178 COOMe H 5-cyano-6-Me 2 N- 190-2 3-pyridyl 179 COOMe H 5-MeS0 2 0-3-pyridyl 149-51 Cpd (R 1 ).. m.p. (°) 180 COOMe H 6-(2,3,5-Cl 3 - 134-5 1-pyrrolyl)-3-pyridyl 181 COOMe H 6-MeOCO-3-pyridyl 141 182 COOMe H 5-PhCH 2 0-3-pyridyl 123-31 183 COOMe H 5-MeS-3-pyridyl 122-3 184 COOMe H 5-MeOCO-2-pyridyl 187-8 185 COOMe H 2,6-(MeO) 2 - 141-3 3-pyridyl 136 COOMe H 5-MeS0 7 -3-pyridyl 168-70 187 COOMe H 5-MeSO-3-pyridyl 130-2 188 COOMe Me 5-MeS-3-pyridyl oil 189 COOMe H 5-(N≡C-CH 2 0)- solid 3-pyridyl 190 COOMe Me 5-MeS0 2 -3-pyridyl 109-11 191 COOMe H 5-ClCH 2 S-3-pyridyl 112-4 192 COOH H 6-C1-3-pyridyl 240 193 COOMe H 5-MeOCO-3-pyridyl 147-8 194 COOMe H 6-[N-(2-MeOCO-Ph) - 195-9 NHCO]-3-pyridyl 195 COOMe H 5-Me-3-pyridy1 116-7 196 COOMe H 6-MeO-5-N0 2 - 150-1 3-pyridyl 197 COOMe H 6-Ph0-3-pyridy1 97-8 198 COOMe H 5,6-(MeS) 2 - 157-8 3-pyridyl 199 -CO-COOMe H 6-MeO-3-pyridyl 133-6 200 COOMe Me 2, 6-(MeO) 2 - 103-5 3-pyridyl 201 COOMe Me 5-MeOCO-3-pyridyl Oil 202 COOMe Me 5-Me-3-pyridyl 114-5 203 COOH H 5-HOCO-3-pyridyl 275 Cpd (R l ) n m.p. (°) 204 COOMe H 5-acetyl-6-Me- 144-5 3-pyridyl 205 COOMe H 5-Ph-3-pyridyl 124-5 206 COOMe Me 6-PhO-3-pyridyl 114-5 207 COOMe H 5-[N-(2-MeOCO-Ph)- 180-2 NHCO] -3-pyridylthio 208 COOMe H 5-PhCH 2 S-3-pyridyl 104-6 209 COOMe Me 5-Meθ-2-pyrazinyl 81-3 210 4-F COOMe Me 6-MeO-3-pyridyl 102-4 211 COOMe Et 6-MeO-3-pyridyl 53-5 212 COOMe H 2-MeO-5-pyrimidinyl 164-5 213 COOMe Me 2-MeO-5-pyrimidinyl 128-30 214 COOMe H 4,6-(MeO) 2 -2-PhCH 2 0- 127-9 5-pyrimidinyl 215 COOMe H 2-Cl-4CF 3 - 139-40 5-pyrimidiny1 216 COOMe H 2-Me 2 N-4CF 3 - 133-6 5-pyrimidinyl 217 COOMe H 2-MeO-4CF 3 - 13940 5-pyrimidinyl 218 COOMe H 6-Cl-5-MeO- 168-71 2-pyrazinyl 219 COOMe H 5-Br-2-Me- 165-6 4-pyrimidiny1 220 COOMe H 2,4, 6-(MeO)3- 153-5 5-pyrimidinyl 221 COOMe Me 6-Cl-3-pyridyl 84-6 222 COOMe H 2-Cl-4-pyrimidinyl 159-61 223 COOMe H 5-Me-2-pyrazinyl 158-60.5 224 COOMe H 2-MeO-4-pyrimidinyl 135-6 225 COOPr H 2-MeS0 2 - 129-31 5-pyrimidinyl Cpd (R 1 ).. m.p. (•) 226 COOPr H 2-MeSO- 116-8 5-pyrimidinyl 227 COOPr H 2-MeO-5-pyrimidinyl 104-5 228 COOEt H 2-EtO-5-pyrimidiny1 134-5 229 COOH H 2-EtO-5-pyrimidinyl 150-62 230 COOMe H 2-Me-5-pyrimidinyl 141-3 231 COOMe H 5-pyrimidinyl 158-61 232 COOMe Me 2-Me-5-pyrimidinyl 88-90 233 COOMe H 2-Cl-5-pyrimidinyl 159-61 234 COOMe H 2-Br-5-pyrimidinyl 177-8 235 COOMe H 2-PhCH 2 NH- 192-4 5-pyrimidinyl 236 COOMe H 2-morpholino- 222-3 5-pyrimidinyl 237 COOMe H 5-Br-2-MeS- 192-4 4-pyrimidiny1 238 COOMe H 5-Br-2-MeO- 178-80 4-pyrimidiny1 239 COOMe H 2-MeOCOCH NH- 194-7 5-pyrimidinyl 240 COOMe H 2,6-Cl 2 - 170- -5 4-pyrimidiny1 241 COOMe H 2-CF ~5-pyrimidiny1 143- -5 242 COOMe H 2-Ph-5-pyrimidiny1 151- -5 243 COOMe H 2,6-(MeO) 2 - 167- -9 4-pyrimidiny1 244 COOMe Me 2-Ph-5-pyrimidiny1 gum 245 COOMe H 2,6-Cl 2 - 135- -7 5-pyrimidiny1 246 COOMe H 2-NC-5-pyrimidiny1 186- -8 247 COOMe H 4,5-(MeO) 2 - 182- -3 2-pyrimidinyl Cpd (R 1 ) .. m. p. ( ° ) 248 COOMe H 4, 6-(MeO) 2 - 163-4 2-pyrimidiny1 249 COOMe H 2-MeONH- 194-6 5-pyrimidiny1 250 COOMe H 2-MeNH- 230-1 5-pyrimidiny1 251 COOMe H 2-Cl-4-(2-MeOCO- 190-2 PhNH) -5-pyrimidinyl 252 COOMe H 5-Cl-6-Me- 136-41 2-pyrazinyl 253 COOMe H 5-MeO-6-Me- 166-9 2-pyrazinyl 254 COOMe H 2-(N-methoxy- 151-2 N-methoxycarbonyl- amino) -5-pyrimidinyl 255 COOMe H 2-cyclopropyl 112-4 5-pyrimidinyl 256 3-MeOCO COOMe H 6-MeO-3-pyridyl 111-4 257 COOMe H 2-MeS-5-pyrimidiny1 160-2 258 COOMe H 5, 6-Cl-ι-2-pyrazinyl 143-8 259 COOMe H 5-(2-thienyl)- 148-9 3-pyridyl 260 COOMe H 5-(4-CF 3 -Ph)- 155-6 3-pyridyl 261 COOMe H 5-(C1S0 2 ) -3-pyridyl 144-5 262 COOMe H 5-(Cl 2 CHS)- 120-2 3-pyridyl 263 COOMe H 5-(NH 2 S0 2 ) - 185-7 3-pyridyl 264 COOMe H 5-Br-6-Cl-3-pyridyl 157-9 265 COOMe Me 5-Nθ 2 -6-MeO- 98-100 3-pyridyl Cpd (R l ) n m.p. (•) 266 - COOMe H 2-(l-imidazolyl) - 193-5 5-pyrimidinyl 267 - COOMe H 4-MeO-2-MeS- 140-2 5-pyrimidiny1 268 - COOMe Me 2, 6-(MeO) 2 - 101-3 4-pyrimidiny1 269 - CCOH 3,4-(MeO) _ • 6-MeO-3-pyridyl 123-4 benzyl 270 COCMe H 5-(Me 2 NS0 2 )- 169-70 3-pyridyl 271 - COOMe H 5-Br-6-MeO- 169-70 3-pyridyl 272 - COOMe H 5-Br-6-MeS0 2 - 223-5 3-pyridyl 273 - COOMe H 5-Br-6-MeSO- 160-2 3-pyridyl 274 COOC 5 H u H 2-MeO-3-pyridyl 47-8 275 COO-allyl H 2-MeO-3-pyridyl 80-1 276 COOMe 2-Me- 6-(2-Me-benzyl) - oil benzyl 3-pyridyl 277 COOMe H 2-Cl-4-quinolinyl 163-4 278 COOMe -CH 2 Ph 6-MeO-3-pyridyl 101-2 279 4,5-Me0 2 COOMe H 2-MeO-3-pyridyl 152-4 280 - COOMe H 5-NH 2 -6-MeO- 202-3 3-pyridyl 281 - COOMe Me 2,4-(MeO) 2 - 78-81 5-pyrimidinyl 282 - COOMe 2-MeO- 2-MeO-5-pyrimidinyl gum benzyl 283 - COOMe H 4-Me-2-MeS- 78-81 5-pyrimidiny1 Cpd (R l ) n m. p . ( ° ) 284 - COOMe H 2-(3-pyridyloxy) - 124-6 5-pyrimidinyl 285 - COOMe H 2-F-3-pyridyl 130-1 286 - COOMe 2- ■ Me- 5, 6-(MeO) 2 - oil benzyl 3-pyridyl 237 COOMe H 5, 6-methylenedioxy- 168-79 3-pyridyl 288 - COOMe H 5-I-6-MeO-pyridyl 173-5 289 3,4- -Me 2 COOMe H 2-MeO-3-pyridyl 126-7 290 4-C1 COOMe H 2-MeO-3-pyridyl 128-30 The following compounds were also prepared a) ethyl N-(6-methoxy-3-pyridinethiocarbonyl) anthranilate, as an oil, (compound 291) b) methyl N-(5, 6-dimethoxy-3-pyridinethiocarbonyl) -anthranilate, m.p. 154-5°, (compound 292) c) methyl N-(2-methoxy-5-pyrimidinethiocarbonyl) -anthranilate, m.p. 135-7°, (compound 293) , and d) isobutyl N-(6-methoxy-3-pyridinethiocarbonyl) -anthranilate, as an oil, (compound 294) . Test Example Compounds are assessed for activity against one or more of the following: Phytophthora infestans : late tomato blight Plasmopara viticola : vine downy mildew Erysiphe graminis : barley powdery mildew Pyricularia oryzae : rice blast Pellic laria sasakii : rice sheath blight Botrytis cinerea : grey mould Venturia inaequalis : apple scab Leptosphaeria nodorum : glume blotch Aqueous solutions or dispersions of the compounds at the desired concentration, including a wetting agent, were applied by spray or by drenching the stem base of the test plants, as appropriate. Plants or plant parts were then inoculated with appropriate test pathogens and kept under controlled environment conditions suitable for maintaining plant growth and development of the disease. After an appropriate time, the degree of infection of the affected part of the plant was visually estimated. Compounds were considered active if they gave greater than 50% control of the disease at a concentration of 500 ppm (w/v) or less. Compounds 30, 36, 43, 47, 58, 112, 115, 180, 242 and 286 showed activity against Phytophthora infestans ; Compounds 9, 30, 36, 40, 42, 57, 58, 59, 62, 64, 67-70, 76, 77, 82, 83, 96, 112, 115, 127, 129, 130, 132, 138, 139, 161, 163, 166, 181, 186, 200-204, 210, 213, 234, 248, 249, 261, 267, 266, 268, 271 and 277 showed activity against Plasmopara viticola ; Compounds 1-3, 9-12, 20, 23, 25, 27- 29, 32, 33, 34, 33, 39, 41, 46, 50, 52, 62, 66, 70, 73, 83, 84, 90, 91, 104- 108, 110, 113, 115, 121-123, 132, 135, 145, 154, 155, 163, 176, 177, 196, 200, 208, 209, 210-2, 213, 218, 228, 239, 243, 249, 250, 252-4, 258, 265, 268, 271-3, 275, 276, 278 and 286 showed activity against Erysiphe graminis ; Compounds 1, la, 2, 6a, 48, 49, 54-56, 65, 68, 72, 74, 75, 126, 129, 145, 146, 169, 171, 197, 230, 232, 249, and 277 showed activity against Pyricularia oryzae ; Compounds 14, 44, 49, 62, 114, 115, 152, 211, 215, 216 and 278 showed activity against Pellicularia sasakii ; Compounds 43, 51, 52, 53, 61, 63, 121, 129, 195, 228 and 251 showed activity against Botrytis cinerea ; Compounds 1, 8, 12, 17, 45, 63, 86, 104, 112, 119, 146, 149, 150, 151, 187, 189, 204, 211, 219, 224, 239, 244, 245, 248 and 250 showed activity against Vent ria inaequalis; and Compounds 24, 35, 60, 61, 71, 204, 216, 220 and 249 showed activity against Leptosphaeria nodorum .

Claims: CLAIMS 1. A compound of formula I (R l ) X is 0 or S; A is a 6 membered heteroaryl group comprising at least one nitrogen atom, which is optionally substituted by one n or more of the group R -** ; R 1 is alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl or amino, (each of which is optionally substituted) , Y---X-, 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; R 2 has the same meaning as R 1 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; Y 1 has the same meaning as Y or is optionally substituted phenyl or optionally substituted heterocyclyl; Z is C(=X 1 )-X 2 -R 3 , cyano, nitro, amino, acyl, optionally substituted heterocyclyl, -C(R 5 )=N-OR 6 or -C(R 5 )=N-NR 6 R 7 ; R 3 is alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, phenyl or heterocyclyl, each of which is optionally substituted, hydrogen or an inorganic or organic cationic group; X and X 2 , which may be the same or different, are 0 or S; R , R° and R 7 , which may be the same or different, are alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, phenyl or heterocyclyl, each of which is optionally £ 7 substituted or hydrogen or R υ and R' together with the atom(s) to which they are attached can form a ring; and 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 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 unsubstituted 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. Fungicidal compositions which comprise a compound as claimed in claim 1 in admixture with an agriculturally acceptable diluent or carrier. 3. A method of combating phytopathogenic fungi at a locus infested or liable to be infested therewith, which comprises applying to the locus a compound as claimed in claim 1.

Inventors: BODDY IAN KENNETH, OSBOURN SUSAN ELISABETH, RIORDAN PETER DOMINIC, BODDY, IAN, KENNETH, OSBOURN, SUSAN, ELISABETH, RIORDAN, PETER, DOMINIC
Applicants: AGREVO UK LTD, BODDY IAN KENNETH, OSBOURN SUSAN ELISABETH, RIORDAN PETER DOMINIC, AGREVO UK LIMITED, BODDY, IAN, KENNETH, OSBOURN, SUSAN, ELISABETH, RIORDAN, PETER, DOMINIC
Application year: 1995
Main classification: C07D213
IPC codes: A01N43, A01N47, A01N59, A61K31, A61P31, C07D213, C07D239, C07D241, C07D333, C07D401, C07D405, C07D413, C07D417, C07D521