Pyridine derivatives as fungicides

A fungicidal compound having general formula (I) ##STR1## or a stereoisomer thereof, wherein A is CH or N, B is OCH.sub.3 or NHCH.sub.3, R.sup.1 is H, chloro or methyl and R.sup.2 is H, fluoro, chloro or methyl.

The present invention relates to novel nitrogen-containing heterocyclic 
 compounds, to processes for preparing them, to compositions containing 
 them and to methods of using them to combat fungi, especially fungal 
 infections of plants. 
 More particularly, the invention relates to fungicidal compounds in which a
 substituted pyridine ring is attached through an oxymethylene linking 
 group to a phenyl ring containing an ortho methyl .beta.-methoxyacrylate 
 group or methyl .beta.-methoxyirninoacetate group or an amide derivative 
 thereof. 
 Fungicidal compounds in which a substituted pyridine ring is linked through
 an oxymethylene group to a phenyl ring containing an ortho methyl 
 .beta.-methoxyacrylate group are described in, for example, EP-A-0278595 
 and EP-A-0350691. Such compounds include those in which the pyridine 
 carries a 6-trifluoromethyl substituent. Similar compounds containing a 
 methyl .beta.-methoxyiminoacetate group and amide derivatives are 
 described in, for example, EP-A-0363818 and EP-A-0398692. The compounds of
 the present invention show an unexpected advantage over the known 
 compounds in respect of certain fungicidal properties. 
 According to the present invention there is provided a compound having the 
 general formula (I): 
 ##STR2## 
 or a stereoisomer thereof, wherein A is CH or N, X is OCH.sub.3 or 
 NHCH.sub.3, R.sup.1 is H, chloro or methyl and R.sup.2 is H, fluoro, 
 chloro or methyl. 
 Of particular interest are compounds where A is N and X is OCH.sub.3 or 
 NHCH.sub.3 and more particularly where A is CH and X is OCH.sub.3. 
 Because the carbon-carbon double bond of the group XOC.C.dbd.A.OCH.sub.3 is
 unsymmetrically substituted, the compounds of the invention may be 
 obtained in the form of mixtures of (E)- and (Z)-geometric isomers. 
 However, these mixtures can be separated into individual isomers, and this
 invention embraces such isomers and mixtures thereof in all proportions. 
 The (E)-isomers with respect to the group XOC.C.dbd.A.OCH.sub.3 are 
 usually the more fungicidally active and form a preferred embodiment of 
 the invention. 
 Further, when R.sup.1 is not the same as R.sup.2 and R.sup.2 is not fluoro,
 the compounds of the invention may exist in the form of mixtures of 
 optical isomers. However, these mixtures can be separated into the 
 component isomers by known methods and this invention embraces such 
 isomers and mixtures thereof in all proportions. 
 In one aspect the invention includes a compound of formula (I) or a 
 stereoisomer thereof, wherein A is CH or N, X is OCH.sub.3 or NHCH.sub.3, 
 R.sup.1 is H, chloro or methyl and R.sup.2 is fluoro or methyl. Suitably, 
 A is N and X is OCH.sub.3 or NHCH.sub.3. Preferably A is CH and B is 
 OCH.sub.3. 
 In another aspect the invention includes a compound having the general 
 formula (I) or a stereoisomer thereof, wherein A is CH or N, X is 
 OCH.sub.3 or NHCH.sub.3, R1 is H or methyl and R.sup.2 is fluoro or 
 methyl. Suitably, A is N and X is OCH.sub.3 or NHCH.sub.3. Preferably A is
 CH and X is OCH.sub.3. 
 In yet another aspect the invention includes a compound having the general 
 formula (I) or a stereoisomer thereof, wherein A is CH or N and X is 
 OCH.sub.3 or NHCH.sub.3, R.sup.1 is H or chloro and R.sup.2 is fluoro or 
 methyl. Suitably, A is N and X is OCH.sub.3 or NHCH.sub.3. Preferably A is
 CH and X is OCH.sub.3. 
 The present invention is illustrated by compounds of the general formula 
 (II) listed in Tables 1 to 4. Throughout the Tables the W group has the 
 (E)-configuration. 
 In the compounds of Table 1, W is CH.sub.3 O.CH.dbd.C.CO.sub.2 CH.sub.3. 
 TABLE 1 
 (II) 
 ##STR3## 
 Compound Compound 
 No R.sup.1 R.sup.2 No R.sup.1 R.sup.2 
 1 H H 6 Cl Cl 
 2 H F 7 Cl CH.sub.3 
 3 H Cl 8 CH.sub.3 F 
 4 H CH.sub.3 9 CH.sub.3 CH.sub.3 
 5 Cl F 
 Table 2 
 Table 2 comprises 9 compounds having the same structural formulae and the 
 same values of R.sup.1 and R.sup.2 as the correspondingly numbered 
 compounds in Table 1, but in this case W is CH.sub.3 
 O.CH.dbd.C.CONHCH.sub.3. 
 Table 3 
 Table 3 comprises 9 compounds having the same structural formulae and the 
 same values of R.sup.1 and R.sup.2 as the correspondingly numbered 
 compound in Table 1, but in this case W is CH.sub.3 O.N.dbd.CO.sub.2 
 CH.sub.3. 
 Table 4 
 Table 4 comprises 9 compounds having the same structural formulae and the 
 same values of R.sup.1 and R.sup.2 as the correspondingly numbered 
 compound in Table 1, but in this case W is CH.sub.3 
 O.N.dbd.C.CONHCH.sub.3. 
 Table 5 
 Table 5 shows melting points where measurable or selected proton NMR data 
 obtained at 270 MHz for certain compounds described in Tables 1 to 4. 
 Chemical shifts are measured at 20.degree. C. in ppm from 
 tetramethylsilane and deuterochloroform was used as solvent, unless 
 otherwise stated. The following abbreviations are used: 
 
 Compound Melting 
 No. Point Proton NMR Data (.delta.) 
 (Table No.) .degree. C. ppm 
 2(1) Oil 3.64(3H, s); 3.81(3H, s); 5.29(2H, s); 6.28, 6.49, 
 6.70(1H, t); 7.1-7.4(4H, m); 7.55(1H, s); 
 7.56(1H, m); 7.67(1H, t). 
 2(3) Oil 3.86(3H, s); 4.03(3H, s); 5.28(2H, s); 6.37, 6.47, 
 6.68(1H, t); 6.80(1H, d); 7.2-7.6(4H, m); 
 7.68(1H, t); 7.70(1H, d). 
 2(4) 68-70 2.91(3H, d); 3.93(3H, s); 5.28(2H, s); 6.29, 6.49, 
 6.70(1H, t); 6.75(1H, brs); 6.80(1H, d); 7.19(1H, 
 d); 7.2-7.6(4H, m); 7.68(1H, t). 
 4(1) Oil [1.60(d), 1.68(d) - 3H]; 3.68(3H, s); 3.81(3H, s); 
 5.25(2H, s); [5.45(q), 5.45(q)-1H]; 6.65(1H, d); 
 7.01(1H, d); 7.1-7.6(5H, m); 7.57(1H, s). 
 5(1) Oil 3.68(3H, s); 3.82(3H, s); 5.33(2H, s); 6.84(1H, 
 d); 7.1-7.7(6H, m); 7.56(1H, s). 
 8(1) Oil 1.94(3H, t); 3.67(3H, s); 3.78(3H, s); 5.30(2H, s); 
 6.78(1H, d); 7.1-7.7(7H, m); 7.56(1H, s). 
 9(1) Oil 1.58(3H, s); 1.68(3H, s); 3.68(3H, s); 3.80(3H, s); 
 5.25(2H, s); 6.61(1H, d); 7.1-7.6(6H, m); 
 7.57(1H, s). 
 s = singlet 
 d = doublet 
 t = triplet 
 q = quartet 
 m = multiplet 
 br = broad 
 ppm = parts per million 
 The compounds of formula (I) may be prepared by methods well documented in 
 the literature. Suitable methods are disclosed, for example, in 
 EP-A-0278595 and EP-A-0350691, the contents of which are incorporated here
 by reference. 
 Thus, compounds of formula (I) may be prepared by reacting the metal salt 
 of a pyridone of formula (III): 
 ##STR4## 
 wherein R.sup.1 and R.sup.2 are as defined above and M is a metal atom, 
 with a compound of formula (IV): 
 ##STR5## 
 wherein A and X are as defined above and L is a suitable leaving group. 
 In practice, a hydroxypyridine of formula (V): 
 ##STR6## 
 or the tautomeric pyridone is reacted with the compound (IV) in the 
 presence of a suitable base such as silver carbonate in a suitable solvent
 such as toluene. In this case reaction proceeds via the compound III where
 M is silver. The leaving group L in the compound (IV) is suitably a 
 halogen, (chloro, iodine or preferably bromine) or OSO.sub.2 CF.sub.3. 
 Typically, the reactants are refluxed in the toluene solvent for 3-4 
 hours. 
 Alternatively, the compounds of formula (I) may be prepared by reacting a 
 pyridine of formula (VI): 
 ##STR7## 
 wherein R.sup.1, R.sup.2 and L are as defined above, with the metal salt of
 a compound of formula (VII): 
 ##STR8## 
 wherein A, X and M are as defined above. Here the metal atom M is typically
 an alkali or alkaline earth metal, or it could be another metal such as 
 silver. 
 Compounds of formula (IV), particularly where L is bromo, are well 
 documented in the literature and can be prepared by the methods described 
 therein; see for example EP-A-0203606 (where A is CH and X is OCH.sub.3), 
 EP-A-0363818 (where A is N and X is OCH.sub.3) and EP-A-0398692 (where A 
 is N and X is NHCH.sub.3). The amides (where X is NHCH.sub.3) may readily 
 be prepared from the corresponding esters (where X is OCH.sub.3) by 
 treating the ester with methylamine in a suitable solvent such as 
 methanol. 
 Compounds of formula (VII) can be prepared by forming the metal salt of the
 corresponding hydroxymethyl compound using conventional techniques. The 
 hydroxymethyl compounds can be prepared, for example, by the methods 
 described in WO 9307116. 
 The pyridines of formula (V) and (VI) are either commerically available or 
 can be prepared from commerically available materials by methods described
 in the chemical literature. A novel method which is particularly 
 convenient for preparing pyridines of formula (V) where R.sup.1 is fluoro 
 and R.sup.2 is H or chloro, and which may be adapted to prepare other 
 pyridines (V) or the tautomeric pyridones, involves the route displayed in
 Scheme 1. 
 In Scheme 1, the pyridone tautomer (V.1) of the pyridine (V) where R.sup.1 
 is fluoro and R.sup.2 is chloro and the pyridone tautomer (V.2) of the 
 pyridine (V) where R.sup.1 is fluoro and R.sup.2 is H can be prepared from
 acyclic starting materials and used to make the compounds (I) where 
 R.sup.1 is fluoro and R.sup.2 is chloro (I.1) or where R.sup.1 is fluoro 
 and R.sup.2 is H (I.2). 
 The compound (I.2) can be made either by reacting the pyridone (V.2) with 
 methyl 2-[2-(bromomethyl)phenyl]-3-methoxypropenoate (Compound (IV) where 
 A is CH, X is OCH.sub.3 and L is Br) or by reduction of the compound (I.1)
 using, for example, zinc dust. The pyridones (V.1) and (V.2) are prepared 
 by decarboxylating the corresponding 2-hydroxy-nicotinic acid (VIII.1) or 
 (VIII.2) at an elevated temperature above 190.degree. C., typically at 
 250.degree. C. Alternatively, the pyridone (V.2) is prepared by reduction 
 of the pyridone (V.1). The 2-hydroxy-nicotinic acids (VIII.1) and (VIII.2)
 can be prepared by the general method described by R W Lang and P F Wenk 
 in Helv.Chim.Acta., 1988, 71(3), 596-601, involving the acidification of 
 the corresponding nicotinamide (IX.1) or (IX.2). Alternatively, the 
 2-hydroxynicotinic acid (VIII.2) can be prepared by reduction of the 
 2-hydroxynicotinic acid (VIII.1). 
 ##STR9## 
 The 2-hydroxynicotinamide (IX.1) can be prepared according to Lang & Wenk 
 by cyclising a compound of formula (XI) with malonamide (X). The 
 2-hydroxynicotinamide (IX.2) can be prepared by reduction of the 
 2-hydroxynicotinamide (IX.1). The compound (XI) can be prepared by 
 reacting chlorodifluoroacetic anhydride (XII), which is commercially 
 available, with ethyl vinyl ether (XIII). 
 Alternatively, the compounds of formula (I) wherein R.sup.1 and R.sup.2 are
 as defined above, A is CH and X is OCH.sub.3 can be prepared from a 
 phenylacetate of formula (XIV) or a ketoester of formula (XV) by the steps
 shown in Scheme 2. Throughout Scheme 2 the terms R.sup.1 and R.sup.2 are 
 as defined above, R.sup.3 is hydrogen or a metal such as sodium or 
 potassium and R is an alkyl group. Each transformation is performed at a 
 suitable temperature and usually, though not always, in a suitable 
 solvent. 
 Thus, a compound of formula (I) can be prepared by treatment of a 
 phenylacetate of formula (XIV) with a base, such as sodium hydride or 
 sodium methoxide, and methyl formate. If a species of formula CH.sub.3 
 L.sup.1, wherein L.sup.1 is a leaving group such as a halide (for example 
 chloride, bromide or iodide), or a CH.sub.3 SO.sub.4 anion, is then added 
 to the reaction mixture, a compound of formula (I) is obtained. If a 
 protic acid is added to the reaction mixture, a compound of formula (XVI),
 wherein R.sup.3 is hydrogen, is obtained. Alternatively, the compound of 
 formula (XVI) wherein R.sup.3 is a metal such as sodium can be isolated 
 from the reaction mixture. 
 A compound of formula (XVI) wherein R.sup.3 is a metal can be converted 
 into a compound of formula (I) by treatment with a species CH.sub.3 
 L.sup.1, wherein L is as defined above. A compound of formula (XVI) 
 wherein R.sup.1 is hydrogen can be converted into a compound of formula 
 (I) by successive treatment with a base, such as potassium carbonate, and 
 a species of general formula CH.sub.3 L.sup.1. 
 Alternatively, a compound of formula (I) can be prepared from an acetal of 
 formula (XVII) by elimination of methanol under either acidic or basic 
 conditions. Examples of reagents or reagent mixtures which can be used for
 this transformation are lithium diisopropylamide, potassium hydrogen 
 sulphate (see, for example, T Yamada, H Hagiwara and H Uda, 
 J.Chem.Soc.Chemical Communications, 1980, 838 and references therein, and 
 triethylamine, often in the presence of a Lewis acid such as titanium 
 tetrachloride (see, for example, K Nsunda and L Heresi, 
 J.Chem.Soc.Chemical Communications, 1985, 1000). 
 ##STR10## 
 Acetals of formula (XVII) can be prepared by treatment of a methyl silyl 
 ketene acetal of formula (XVIII) with trimethyl orthoformate in the 
 presence of a Lewis acid such as titanium tetrachloride (see, for example,
 K Saigo, M Osaki and T Mukaiyama, Chemistry Letters, 1976, 769). 
 A methyl silyl ketene acetal of formula (XVIII) can be prepared by treating
 a phenylacetate of formula (XIV) with a base and a trialkylsilyl halide of
 formula R.sub.3 SiCl or R.sub.3 SiBr, such as trimethylsilyl chloride, or 
 a base, such as triethylamine, and a trialkylsilyl triflate of formula 
 R.sub.3 Si--OSO.sub.2 CF.sub.3 (see, for example, C Ainsworth, F Chen and 
 Y Kuo, J.Organometallic Chemistry, 1972, 46, 59). 
 It is not always necessary to isolate the intermediates (XVII) and (XVIII).
 Under appropriate conditions a compound of formula (I) can be prepared 
 from a phenylacetate of formula (XIV) in "one pot" by the successive 
 addition of suitable reagents listed above. 
 A phenylacetate of formula (XIV) can be prepared from a phenylacetate of 
 formula (XIX). Thus, if a compound of formula (V) is treated with a 
 suitable base such as silver carbonate and a phenyl acetate of formula 
 (XIX) added, a phenylacetate of formula (XIV) is obtained. 
 A phenylacetate of formula (XIX) can be prepared by treating an 
 isochromanone of formula (XX) with HL, wherein L is preferably bromine, in
 methanol. This transformation can also be accomplished in 2 steps if the 
 isochromanone of formula (XX) is treated with HL in a non-alcoholic 
 solvent, and the resulting phenylacetic acid is then esterified using 
 standard procedures (see, for example, I Matsumoto and J Yoshizawa, Jpn. 
 Kokai (Tokkyo Koho) 79138536,27.10.1979, ChemAbs., 1980, 92, 180829h; and 
 G M Lim, Y G Perron and R D Droghini, Res.Discl., 1979, 188, 672, 
 Chem.Abs., 1980, 92, 128526t). Isochromanones of formula (XX) are well 
 known in the chemical literature. 
 Alternatively, a compound of formula (I) can be prepared by treatment of a 
 ketoester of formula (XV) with a methoxymethylenation reagent such as 
 methoxymethylenetriphenyl-phosphorane (see, for example, EP-A-0044448). 
 A ketoester of formula (XV) can be prepared from a ketoester of formula 
 (XXI), by treatment with a compound of formula (V) as described above. 
 Ketoesters of formula (XXI) are described in EP-A-0331061. 
 Compounds of formula (I) where R.sup.1 and R.sup.2 are as defined above, A 
 is N and B is OCH.sub.3 may be prepared from ketoesters of formula (XV) by
 treatment with methoxylamine (or a salt of methoxylamine). Moreover these 
 same compounds of formula (I) may be prepared by nitrosation of 
 phenylacetates of formula (XIV) using nitrous acid or an ester of nitrous 
 acid, in the presence of a base such as sodium methoxide, (see for 
 example, O Touster, Organic Reactions, 1953, 7, 327 and S Kukolja et al, 
 J.Med.Chem., 1985, 28, 1896). 
 Compounds of formula (I) where A is N and X is the group NHCH.sub.3, may be
 prepared by treating a compound of formula (I) where A is N and X is 
 OCH.sub.3 with methylamine in a suitable solvent such as methanol. 
 The compounds of formula (I) are active fungicides and may be used to 
 control one or more of the following pathogens: Pyricularia oryzae on rice
 and wheat and other Pyricularia spp. on other hosts; Puccinia recondita, 
 Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia 
 striiformis and other rusts on barley, and rusts on other hosts e.g. turf,
 rye, coffee, pears, apples, peanuts, sugar beet, vegetables and ornamental
 plants; Erysiphe graminis (powdery mildew) on barley, wheat, rye and turf 
 and other powdery mildews on various hosts such as Sphaerotheca macularis 
 on hops, Sphaerotheca fuliginea on cucurbits (e.g. cucumber), Podosphaera 
 leucotricha on apple and Uncinula necator on vines; Cochliobolus spp., 
 Helminthosporium spp., Drechslera spp. (Pyrenophora spp.), Rhynchosporium 
 spp., Septoria spp. (including Mycosphaerella graminicola and 
 Leptosphaeria nodorum), Pseudocercosporella herpotrichoides and 
 Gaeumannomyces graminis on cereals (e.g. wheat, barley, rye), turf and 
 other hosts; Cercospora arachidicola and Cercosporidium personatum on 
 peanuts and other Cercospora species on other hosts, for example, sugar 
 beet, bananas, soya beans and rice; Botrytis cinerea (grey mould) on 
 tomatoes, strawberries, vegetables, vines and other hosts and other 
 Botrytis spp. on other hosts; Alternaria spp. on vegetables (e.g. 
 cucumber), oil-seed rape, apples, tomatoes, cereals (e.g. wheat) and other
 hosts; Venturia spp. (including Venturia inaequalis (scab)) on apples, 
 pears, stone fruit, tree nuts and other hosts; Cladosporium spp. on a 
 range of hosts including cereals (e.g. wheat); Monilinia spp. on stone 
 fruit, tree nuts and other hosts; Didymella spp. on tomatoes, turf, wheat 
 and other hosts; Phoma spp. on oil-seed rape, turf, rice, potatoes, wheat 
 and other hosts; Aspergillus spp. and Aureobasidium spp. on wheat, lumber 
 and other hosts; Ascochyta spp. on peas, wheat, barley and other hosts; 
 Plasmopara viticola on vines; other downy mildews such as Bremia lactucae 
 on lettuce, Peronospora spp. on soybeans, tobacco, onions and other hosts,
 Pseudoperonospora humuli on hops and Pseudoperonospora cubensis on 
 cucurbits; Pythium spp. (including Pythium ultimum) on turf and other 
 hosts; Phytophthora infestans on potatoes and tomatoes and other 
 Phytophthora spp. on vegetables, strawberries, avocado, pepper, 
 ornamentals, tobacco, cocoa and other hosts; Thanatephorus cucumeris on 
 rice and turf and other Rhizoctonia species on various hosts such as wheat
 and barley, vegetables, cotton and turf; Sclerotinia spp. on turf, 
 peanuts, oil-seed rape and other hosts; Sclerotium spp. on turf, peanuts 
 and other hosts; Colletotrichum spp. on a range of hosts including turf, 
 coffee and vegetables; Laetisaria fuciformis on turf; Mycosphaerella spp. 
 on banana, peanut, citrus, pecan, papaya and other hosts; Diaporthe spp. 
 on citrus, soybean, melon, pear, lupin and other hosts; Elsinoe spp. on 
 citrus, vines, olives, pecans, roses and other hosts; Pyrenopeziza spp. on
 oil-seed rape and other hosts; Oncobasidium theobromae on cocoa causing 
 vascular streak dieback; Fusarium spp., Typhula spp., Microdochium nivale,
 Ustilago spp., Urocystis spp., Tilletia spp., and Claviceps purpurea on a 
 variety of hosts but particularly wheat, barley, turf and maize; Ramularia
 spp. on sugar beet and other hosts; post-harvest diseases particularly of 
 fruit (e.g. Pencillium digitatum and P. italicum and Trichoderma viride on
 oranges, Colletotrichum musae and Gloeosporium musarum on bananas and 
 Botrytis cinerea on grapes); other pathogens on vines, notably Eutypa 
 lata, Guignardia bidwellii, Phellinus igniarus, Phomopsis viticola, 
 Pseudopezicula tracheiphila and Stereum hirsutum; other pathogens on 
 lumber, notably Cephaloascus fragrans, Ceratocystis spp., Ophiostoma 
 piceae, Penicillium spp., Trichoderma pseudokoningii, Trichoderma viride, 
 Trichoderma harzianum, Aspergillus niger, Leptographium lindbergi and 
 Aureobasidium pullulans; and fungal vectors of viral diseases e.g. 
 Polymyxa graminis on cereals as the vector of barley yellow mosaic virus 
 (BYMV). 
 Further, some of the compounds may be useful as seed dressings against 
 pathogens including Fusarium spp., Septoria spp., Tilletia spp., (e.g. 
 bunt, a seed-borne disease of wheat), Ustilago spp. and Helminthosporium 
 spp. on cereals, Rhizoctonia solani on cotton and Pyricularia oryzae on 
 rice. In particular, some of the compounds show good eradicant activity 
 against Plasmopara viticola and Pythium ultimum. 
 The compounds may move acropetally/locally in plant tissue. Moreover, the 
 compounds may be volatile enough to be active in the vapour phase against 
 fungi on the plant. The invention therefore provides a method of combating
 fungi which comprises applying to a plant, to a seed of a plant or to the 
 locus of the plant or seed a fungicidally effective amount of a compound 
 as hereinbefore defined, or a composition containing the same. 
 The compounds may be used directly for agricultural purposes but are more 
 conveniently formulated into compositions using a carrier or diluent. The 
 invention thus provides fungicidal compositions comprising a compound as 
 hereinbefore defined and an acceptable carrier or diluent therefor. It is 
 preferred that all compositions, both solid and liquid formulations, 
 comprise 0.0001 to 95%, more preferably 1 to 85%, for example 1 to 25% or 
 25 to 60%, of a compound as hereinbefore defined. 
 When applied to the foliage of plants, the compounds of the invention are 
 applied at rates of 0.1 g to 10 kg, preferably 1 g to 8 kg, more 
 preferably 10 g to 4 kg, of active ingredient (invention compound) per 
 hectare. 
 When used as seed dressings, the compounds of the invention are used at 
 rates of 0.0001 g (for example 0.00 g or 0.05 g) to 10 g, preferably 0.005
 g to 8 g, more preferably 0.005 g to 4 g, of active ingredient (invention 
 compound) per kilogram of seed. 
 The compounds can be applied in a number of ways. For example, they can be 
 applied, formulated or unformulated, directly to the foliage of a plant, 
 to seeds or to other medium in which plants are growing or are to be 
 planted, or they can be sprayed on, dusted on or applied as a cream or 
 paste formulation, or they can be applied as a vapour or as slow release 
 granules. 
 Application can be to any part of the plant including the foliage, stems, 
 branches or roots, or to soil surrounding the roots, or to the seed before
 it is planted, or to the soil generally, to paddy water or to hydroponic 
 culture systems. The invention compounds may also be injected into plants 
 or sprayed onto vegetation using electrodynamic spraying techniques or 
 other low volume methods, or applied by land or aerial irrigation systems.
 The term "plant" as used herein includes seedlings, bushes and trees. 
 Furthermore, the fungicidal method of the invention includes preventative,
 protectant, prophylactic, systemic and eradicant treatments. 
 The compounds are preferably used for agricultural and horticultural 
 purposes in the form of a composition. The type of composition used in any
 instance will depend upon the particular purpose envisaged. 
 The compositions may be in the form of dustable powders or granules 
 comprising the active ingredient (invention compound) and a solid diluent 
 or carrier, for example, fillers such as kaolin, bentonite, kieselguhr, 
 dolomite, calcium carbonate, talc, powdered magnesia, fuller's earth, 
 gypsum, diatomaceous earth and china clay. Such granules can be preformed 
 granules suitable for application to the soil without further treatment. 
 These granules can be made either by impregnating pellets of filler with 
 the active ingredient or by pelleting a mixture of the active ingredient 
 and powdered filler. Compositions for dressing seed may include an agent 
 (for example, a mineral oil) for assisting the adhesion of the composition
 to the seed; alternatively the active ingredient can be formulated for 
 seed dressing purposes using an organic solvent (for example, 
 N-methylpyrrolidone, propylene glycol or N,N-dimethylformamide). The 
 compositions may also be in the form of water dispersible powders or water
 dispersible granules comprising wetting or dispersing agents to facilitate
 the dispersion in liquids. The powders and granules may also contain 
 fillers and suspending agents. 
 The compositions may also be in the form of soluble powders or granules, or
 in the form of solutions in polar solvents. 
 Soluble powders may be prepared by mixing the active ingredient with a 
 water-soluble salt such as sodium bicarbonate, sodium carbonate, magnesium
 sulphate or a polysaccharide, and a wetting or dispersing agent to improve
 water dispersibility/solubility. The mixture may then be ground to a fine 
 powder. Similar compositions may also be granulated to form water-soluble 
 granules. Solutions may be prepared by dissolving the active ingredient in
 polar solvents such as ketones, alcohols and glycol ethers. These 
 solutions may contain surface active agents to improve water dilution and 
 prevent crystallisation in a spray tank. 
 Emulsifiable concentrates or emulsions may be prepared by dissolving the 
 active ingredient in an organic solvent optionally containing a wetting or
 emulsifying agent and then adding the mixture to water which may also 
 contain a wetting or emulsifying agent. Suitable organic solvents are 
 aromatic solvents such as alkylbenzenes and alkylnaphthalenes, ketones 
 such as cyclohexanone and methylcyclohexanone, chlorinated hydrocarbons 
 such as chlorobenzene and trichlorethane, and alcohols such as benzyl 
 alcohol, furfuryl alcohol, butanol and glycol ethers. 
 Aqueous suspension concentrates of largely insoluble solids may be prepared
 by ball or bead milling with a dispersing agent with a suspending agent 
 included to stop the solid settling. 
 Compositions to be used as sprays may be in the form of aerosols wherein 
 the formulation is held in a container under pressure of a propellant, 
 e.g. fluorotrichloromethane or dichlorodifluoromethane. 
 The invention compounds can be mixed in the dry state with a pyrotechnic 
 mixture to form a composition suitable for generating in enclosed spaces a
 smoke containing the compounds. 
 Alternatively, the compounds may be used in micro-encapsulated form. They 
 may also be formulated in biodegradable polymeric formulations to obtain a
 slow, controlled release of the active substance. 
 By including suitable additives, for example additives for improving the 
 uptake, distribution, adhesive power and resistance to rain on treated 
 surfaces, the different compositions can be better adapted for various 
 utilities. Other additives may be included to improve the biological 
 efficacy of the various formulations. Such additives can be surface active
 materials to improve the wetting and retention on surfaces treated with 
 the formulation and also the uptake and mobility of the active material, 
 or additionally can include oil based spray additives, for example, 
 certain mineral oil and natural plant oil (such as soya bean and rape seed
 oil) additives, or blends of them with other adjuvants. 
 The invention compounds can be used as mixtures with fertilisers (e.g. 
 nitrogen-, potassium- or phosphorus-containing fertilisers). Compositions 
 comprising only granules of fertiliser incorporating, for example coated 
 with, a compound of formula (I) are preferred. Such granules suitably 
 contain up to 25% by weight of the compound. The invention therefore also 
 provides a fertiliser composition comprising a fertiliser and the compound
 of general formula (I) or a salt or metal complex thereof. 
 Water dispersible powders, emulsifiable concentrates and suspension 
 concentrates will normally contain surfactants, e.g. a wetting agent, 
 dispersing agent, emulsifying agent or suspending agent. These agents can 
 be cationic, anionic or non-ionic agents. 
 Suitable cationic agents are quaternary ammonium compounds, for example, 
 cetyltrimethylammonium bromide. Suitable anionic agents are soaps, salts 
 of aliphatic monoesters of sulphuric acid (for example, sodium lauryl 
 sulphate), and salts of sulphonated aromatic compounds (for example, 
 sodium dodecylbenzenesulphonate, sodium, calcium or ammonium 
 lignosulphonate, butylnaphthalene sulphonate, and a mixture of sodium 
 diisopropyl- and triisopropylnaphthalene sulphonates). 
 Suitable non-ionic agents are the condensation products of ethylene oxide 
 with fatty alcohols such as oleyl or cetyl alcohol, or with alkyl phenols 
 such as octyl- or nonylphenol and octylcresol. Other non-ionic agents are 
 the partial esters derived from long chain fatty acids and hexitol 
 anhydrides, alkyl glucosides, polysaccharides and the lecithins and the 
 condensation products of the said partial esters with ethylene oxide. 
 Suitable suspending agents are hydrophilic colloids (for example, 
 polyvinylpyrrolidone and sodium carboxymethylcellulose), and swelling 
 clays such as bentonite or attapulgite. 
 Compositions for use as aqueous dispersions or emulsions are generally 
 supplied in the form of a concentrate containing a high proportion of the 
 active ingredient, the concentrate being diluted with water before use, 
 these concentrates should preferably be able to withstand storage for 
 prolonged periods and after such storage be capable of dilution with water
 in order to form aqueous preparations which remain homogeneous for a 
 sufficient time to enable them to be applied by conventional spray 
 equipment. The concentrates may conveniently contain up to 95%, suitably 
 1-85%, for example 1-25% or 25-60%, by weight of the active ingredient. 
 After dilution to form aqueous preparations, such preparations may contain
 varying amounts of the active ingredient depending upon the intended 
 purpose, but an aqueous preparation containing 0.0001 to 10%, for example 
 0.005 to 10%, by weight of active ingredient may be used. 
 The compositions of this invention may contain other compounds having 
 biological activity, e.g. compounds having similar or complementary 
 fungicidal activity or which possess plant growth regulating, herbicidal 
 or insecticidal activity. 
 By including another fungicide, the resulting composition can have a 
 broader spectrum of activity or a greater level of intrinsic activity than
 the compound of general formula (I) alone. Further the other fungicide can
 have a synergistic effect on the fungicidal activity of the compound of 
 general formula (I). Examples of fungicidal compounds which may be 
 included in the composition of the invention are 
 (E)-N-methyl-2-(2-phenoxyphenyl)-2-methoxyiminoacetamide, 
 (E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxyiminoacetami
 de, (RS)-1-aminopropylphosphonic acid, 
 (RS)-4-(4-chlorophenyl)-2-phenyl-2-(1H-1,2,4-triazol-1-ylmethyl)butyronitr
 ile, Z)-N-but-2-enyloxymethyl-2-chloro-2',6'-diethylacetanilide, 
 1-(2-cyano-2-methoxyiminoacetyl)-3-ethyl urea, 
 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile, 
 4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole-1-sulphonamide
 , 5-ethyl-5,8-dihydro-8-oxo(1,3)-dioxol-(4,5-g)quinoline-7-carboxylic acid,
 .alpha.-[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]-.gamma.-butyrolactone,
 N-(2-methoxy-5-pyridyl)-cyclopropane carboxamide, alanycarb, aldimorph, 
 ampropylfos, anilazine, azaconazole, azafenidin, azoxystrobin, benalaxyl, 
 benomyl, biloxazol, binapacryl, bitertanol, blasticidin S, bromuconazole, 
 bupirimate, butenachlor, buthiobate, captafol, captan, carbendazim, 
 carbendazim chlorhydrate, carboxin, carvone, chinomethionate, 
 chlorbenzthiazone, chloroneb, chlorothalonil, chlorozolinate, clozylacon, 
 copper containing compounds such as copper oxychloride, copper 
 oxyquinolate, copper sulphate, copper tallate, and Bordeaux mixture, 
 cycloheximide, cymoxanil, cyproconazole, cyprofuram, debacarb, 
 di-2-pyridyl disulphide 1,1'-dioxide, dichlofluanid, dichlone, 
 diclobutrazol, diclomezine, dicloran, didecyl dimethyl ammonium chloride, 
 diethofencarb, difenoconazole, difenzoquat, diflumetorim, 
 O,O-di-iso-propyl-S-benzyl thiophosphate, dimefluazole, dimetconazole, 
 dimethon orph, dimethirimol, diniconazole, dinocap, dipyrithione, 
 ditalimfos, dithianon, dodemorph, dodine, doguadine, edifenphos, 
 epoxiconazole, etaconazole, ethirimol, ethoxyquin, ethyl 
 (Z)-N-benzyl-N-([methyl(methylthioethylideneamino-oxycarbonyl)amino]thio)-
 .beta.-alaninate, etridiazole, famoxadone, fenaminosulph, fenapanil, 
 fenarimol, fenbuconazole, fenfuram, fenpiclonil, fenpropidin, 
 fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, 
 fluazinam, fludioxonil, fluoroimide, flumetover, fluquinconazole, 
 flusilazole, flutolanil, flutriafol, folpet, fuberidazole, furalaxyl, 
 furametpyr, furconazole-cis, guazatine, hexaconazole, hydroxyisoxazole, 
 hymexazole, imazalil, imibenconazole, ipconazole, iprobenfos, iprodione, 
 isopropanyl butyl carbamate, isoprothiolane, kasugamycin, kresoxim-methyl,
 mancozeb, maneb, mefenoxam, mepanipyrim, mepronil, metalaxyl, metconazole,
 methfuroxam, metiram, metiram-zinc, metsulfovax, myclobutanil, NTN0301, 
 neoasozin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, 
 ofurace, organomercury compounds, oxadixyl, oxasulfuron, oxolinic acid, 
 oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, 
 phosetyl-A1, phosphorus acids, phthalide, polyoxin D, polyram, 
 probenazole, prochloraz, procymidone, propamocarb, propamocarb 
 hydrochloride, propiconazole, propineb, propionic acid, prothiocarb, 
 pyracarbolid, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, 
 pyrrolnitrin, quaternary ammonium compounds, quinconazole, 
 quinomethionate, quinoxyfen, quintozene, rabenazole, sodium 
 pentachlorophenate, spiroxamine, streptomycin, sulphur, tebuconazole, 
 techlofthalam, tecnazene, tetraconazole, thiabendazole, thicyofen, 
 thifluzamide, 2-(thiocyanomethylthio)benzothiazole, thiophanatemethyl, 
 thiram, timibenconazole, tolclofos-methyl, tolylfluanid, triacetate salt 
 of 1,1'-iminodi(octamethylene)diguanidine, triadimefon, triadimenol, 
 triazbutyl, triazoxide, tricyclazole, tridemorph, triforine, triflumizole,
 triticonazole, validamycin A, vapam, vinclozolin, XRD-563, zineb and 
 ziram. The compounds of general formula (I) can be mixed with soil, peat 
 or other rooting media for the protection of plants against seed-borne, 
 soil-borne or foliar fungal diseases. 
 The following Examples illustrate the invention. Throughout the Examples, 
 the term `ether` refers to diethyl ether, magnesium sulphate was used to 
 dry solutions except where otherwise indicated, and solutions were 
 concentrated under reduced pressure. All reactions were performed under an
 atmosphere of nitrogen and solvents were dried before use, where 
 appropriate. Unless otherwise stated, chromatography was performed on a 
 column of silica gel as the stationary phase. The following abbreviations 
 are used throughout: 
 ##EQU1## 
 Abbreviations for NMR data are as indicated in Table 5.

EXAMPLE 1 
 This Example illustrates the preparation of 6-difluoromethylpyrid-2-one. 
 6-Chlorodifluoromethyl-pyrid-2-one (0.3 g) was placed in a 3-necked flask 
 and dissolved in acetic acid (20 ml). To this solution zinc (1.0 g of 325 
 mesh dust) was added and the flask lowered into an ultra-sonic bath. The 
 reaction mixture was sonicated at room temperature for 90 minutes then 
 filtered through `Hyflo Supercel` which was washed through with ethyl 
 acetate. The filtrate was concentrated and the residue diluted with water 
 and neutralised with sodium bicarbonate and extracted with ethyl acetate. 
 The combined extracts were dried and concentrated to give a solid which 
 was washed with petrol and dried in air to give 
 6-difluoromethylpyrid-2-one (0.15 g, 67% yield) as a white solid m.p. 
 125-7.degree. C.; .sup.1 H NMR (270 MHz): .delta. 6.31, 6.53, 6.75 (1H,t),
 6.56(1H,m), 6.75(1H,m), 7.52(1H,m), 12.5(1H,brs) ppm. 
 6-Chlorodifluoromethyl-2-hydroxynicotinic acid (1.1 g) was heated to 
 250.degree. C. for 10 minutes until the effervescence had ceased. On 
 cooling it was taken up in ethyl acetate and the organic phase washed with
 saturated sodium bicarbonate solution. The combined organic phase was 
 dried, decolourised with activated charcoal and concentrated to give 
 6-chlorodifluoromethylpyrid-2-one (0.41 g, 47% yield) as an off white 
 solid; .sup.1 H NMR (270 MHz): .delta. 6.89(2H,m), 7.12(1H,t), 
 13.5(1H,brs) ppm. 
 6-Chlorodifluoromethyl-2-hydroxynicotinamide (48.5 g) was heated in dilute 
 sulphuric acid (36 ml in 250 ml water) for 12 hours. The reaction was 
 concentrated to about half the volume and cooled in ice. The precipitate 
 was filtered, washed with water and air dried to give 
 6-chlorodifluoromethyl-2-hydroxynicotinic acid (48.1 g, 98% yield) as a 
 pale brown solid mp.131-3.degree. C.; .sup.1 H NMR (270 MHz): .delta. 
 7.36(1H,d), 8.33(1H,d) ppm. 
 Malonamide (27.5 g) was added to a solution of sodium methoxide in methanol
 [prepared from sodium (8.7 g) and methanol (300 ml)]. After 15 minutes, 
 (E)-ethoxy-1,1,1-chlorodifluorobuten-2-one (50.2 g) was added and the 
 reaction mixture heated to reflux for 2 hours. After cooling, the reaction
 mixture was concentrated, then diluted with water, acidified with 
 concentrated hydrochloric acid and the precipitate filtered off. This was 
 washed with water and dried to give 
 6-chlorodifluoromethyl-2-hydroxynicotinamide (48.8 g, 81% yield) as a 
 white solid mp. 230-232.degree. C.; .sup.1 H NMR (270 MHz): .delta. 
 7.29(1H,brm), 8.03(1H,brs), 8.38(2H,d), 13.6(1H,brs) ppm. 
 Pyridine (24 g) was added to a solution of ethyl vinyl ether (22 g) in 
 chloroform (75 ml) under nitrogen keeping the temperature below 10.degree.
 C. Chlorodifluoroacetic anhydride (75 g) was added over 90 minutes keeping
 the temperature below 20.degree. C. The reaction was stirred for 16 hours 
 then quenched with water. The chloroform layer was washed with water, 
 dried and concentrated to give (E)-ethoxy-1,1,1-chlorodifluorobuten-2-one 
 (50.2 g, 91% yield) as an orange liquid; .sup.1 H NMR (270 mhz): .delta. 
 1.43(3H,t), 4.12(2H,q), 5.89(1H,d), 7.90(1H,d) ppm. 
 EXAMPLE 2 
 This Example illustrates the preparation of methyl 
 2-[2-(6-difluoromethylpyrid-2-yloxymethyl)phenyl]-3-methoxypropenoate 
 (Compound No 2 of Table 1). 
 6-Difluoromethylpyrid-2-one (3.2 g)(prepared as described in Example 1 or 
 as described below), methyl 2-[2-(bromomethyl)phenyl]-3-methoxypropenoate 
 (6.3 g) and silver carbonate (3.64 g) were refluxed together in toluene 
 (200 ml) for 4 hours. After cooling, the reaction mixture was filtered 
 through `Hyflo supercel` which was washed through with ethyl acetate. 
 Concentration and chromatography using dichloromethane as the eluant gave 
 the title compound (3.3 g, 42% yield) as a clear pale yellow oil; .sup.1 H
 NMR given in Table 5. 
 To a solution of 2-tert-butoxy-6-difluoromethylpyridine (4.3 g) in 
 dichloromethane (25 ml) trifluoroacetic acid (2 ml) was added. The 
 reaction was stirred for 16 hours and then concentrated. The residue was 
 diluted with water and neutralised with sodium bicarbonate. The solid 
 formed was extracted into ethyl acetate, dried and concentrated to give 
 6-difluoromethylpyrid-2-one (3.2 g, 72% yield) as a white solid; .sup.1 H 
 NMR (270 MHz): .delta. 6.31, 6.53, 6.75 (1H,t), 6.56(1H,m), 6.75(1H,m), 
 7.52(1H,m), 12.5(1H,brs) ppm. 
 Diethylaminosulphur trifluoride (2.5 ml) was added to a solution of 
 2-tert-butoxy-6-pyridine carboxaldehyde (1.5 g) in dichloromethane (20 ml)
 at -40.degree. C. The reaction was allowed to warm to room temperature 
 then stirred for 2 hours before being quenched with water and extracted 
 with dichloromethane. The organic extract was washed with brine, dried, 
 concentrated and chromatographed using dichloromethane as the eluant to 
 give 2-tert-butoxy-6-difluoromethylpyridine (1.1 g, 66% yield) as a pale 
 brown oil, .sup.1 H NMR (270 MHz): .delta. 1.58(9H,s), 6.26, 6.48, 
 6.69(1H,t), 6.71(1H,d), 7.11(1H,d), 7.61(1H,t) ppm. 
 "Butyl lithium (13.6 ml of a 2.5M solution in hexane) was added to a 
 solution of 2-bromo-6-tert-butylpyridine (4.0 g) in THF (100 ml) at 
 -90.degree. C. This was stirred for 30 minutes then DMF (3 ml) in THF (15 
 ml) was added quickly. The reaction was allowed to reach room temperature 
 then quenched with a saturated solution of ammonium chloride and extracted
 with ether. The combined organic extract was washed with brine, dried and 
 concentrated to give 2-tert-butoxy-6-pyridine carboxaldehyde (2.8 g, 93% 
 yield ) as a brown liquid; .sup.1 H NMR (270 MHz): .delta. 1.65(9H,s), 
 6.89(1H,s), 7.51(1H,d), 7.68(1H,t), 9.92(1H,s) ppm. 
 2,6-Dibromopyridine (50 g) was added to a solution of potassium 
 tert-butoxide (35.5 g) in tert-butanol (300 ml). The mixture was heated to
 reflux for 3.5 hours then cooled and concentrated. The residue was 
 quenched with water and extracted into ethyl acetate. The combined organic
 extracts were washed with brine, dried and concentrated to give 
 2-bromo-6-tert-butylpyridine (21.4 g, 44% yield ) as a clear oil; .sup.1 H
 NMR (270 MHz): .delta. 1.55(9H,s), 6.58(1H,d), 6.98(1H,d), 7.33(1H,t)ppm. 
 EXAMPLE 3 
 This Example illustrates the preparation of methyl 
 2-[2-(6-difluoromethylpyrid-2-yloxymethyl)phenyl]-(O-methyloximino)acetate
 . (Compound No 2 of Table 3). 
 6-Difluoromethylpyrid-2-one (1.45 g), 2-[2-(bromomethyl)phenyl]glyoxylate 
 O-methyloxime (2.5 g) and silver carbonate (1.3 g) were refluxed together 
 in toluene (200 ml) for 3 hours. A further portion of 
 6-difluoromethylpyrid-2-one (0.73 g), 2-[2-(bromomethyl)phenyl]glyoxylate 
 O-methyloxime (1.1 g) and silver carbonate (0.6 g) was added and the 
 mixture refluxed for a further 6 hours After cooling the reaction mixture 
 was filtered through `Hyflo supercel` which was washed through with ethyl 
 acetate. Concentration and chromatography using dichloromethane as the 
 eluant gave a yelow oil which was triturated with hexane and tert-butyl 
 methyl ether to give the title compound (0.89, 24% yield) as a white 
 solid; .sup.1 H NMR given in Table 5. 
 EXAMPLE 4 
 This Example illustrates the preparation of methyl 
 2-[2-(6-difluoromethylpyrid-2-yl-oxymethyl)phenyl]-(O-methyloximino)acetam
 ide. (Compound No 2 of Table 4). 
 Methyl 
 2-[2-(6-difluoromethylpyrid-2-yloxymethyl)phenyl]-(O-methyloximino)-acetat
 e (0.43 g, as prepared in Example 3) was dissolved in methylamine (20 ml of
 a 33% solution in ethanol) and stirred for 1 hour. The reaction mixture 
 was concentrated and the volatiles removed in vacuo to give the title 
 compound (0.41 g, 96% yield) as a pale brown oil; .sup.1 H NMR given in 
 Table 5. 
 EXAMPLE 5 
 The compounds were tested against a variety of foliar fungal diseases of 
 plants. The technique employed was as follows. 
 The plants were grown in John Innes Potting Compost (No 1 or 2) in 4 cm 
 diameter minipots. The test compounds were formulated either by bead 
 milling with aqueous Dispersol T or as a solution in acetone or 
 acetone/ethanol which was diluted to the required concentration 
 immediately before use. The formulations (100 ppm active ingredient) were 
 sprayed on to the foliage or applied to the roots of the plants in the 
 soil. The sprays were applied to maximum retention and the root drenches 
 to a final concentration equivalent to approximately 40 ppm a.i. in dry 
 soil. Tween 20 was added to give a final concentration of 0.05% when the 
 sprays were applied to cereals. 
 For most of the tests the compounds were applied to the soil (roots) or to 
 the foliage (by spraying) one or two days before the plant was inoculated 
 with the disease. Exceptions were the tests on Erysiphe graminis and 
 Puccinia recondita in which the plants were inoculated 24 hours and 48 
 hours, respectively, before treatment. Foliar pathogens were applied by 
 spray as zoosporangial suspensions onto the leaves of test plants. After 
 inoculation, the plants were put into an appropriate environment to allow 
 infection to proceed and then incubated until the disease was ready for 
 assessment. The period between inoculation and assessment varied from four
 to fourteen days according to the disease and environment. 
 The disease level present (i.e. leaf area covered by actively sporulating 
 disease) on each of the treated plants was recorded using the following 
 assessment scale: 
 ##EQU2## 
 Each assessment was then expressed as a percentage of the level of disease 
 present on the untreated control plants. This calculated value is referred
 to as a POCO (Percentage of Control) value. An example of a typical 
 calculation is as follows: 
 ##EQU3## 
 This calculated POCO value is then rounded to the nearest of the values in 
 the 9-point assessment scale shown above. In this particular example, the 
 POCO value would be rounded to 30. If the calculated POCO falls exactly 
 mid-way between two of the points, it is rounded to the lower of the two 
 values. 
 The results are shown in Table 6. 
 TABLE 6 
 Compound No 
 (Table No) ERYSGT LEPTNO PUCCRT PLASVI PHYTIN VENTIN 
 2(1) 0 0 0 0 0 0 
 2(3) 0 10 -- 0 0 0 
 2(4) 0 0 -- 0 5 0 
 4 0 0 0 0 -- 0 
 5 0 0 0 0 0 0 
 8 0 0 0 0 0 0 
 9 0 0 0 0 0 0 
 --No result 
 Unless stated otherwise, data represent activity following application as a
 combined foliar spray and root drench treatment at 100 ppm. 
 
 Keys to Diseases 
 ERYSGT Erysiphe graminis tritici PLASVI Plasmopara viticola 
 LEPTNO Septoria nodorum PHYTIN Phytophthora infestans 
 PUCCRT Puccinia recondita lycopersici 
 VENTIN Venturia inaequalis