WO1995004718A1 - 4-methyleneproline derivatives as fungicides - Google Patents
4-methyleneproline derivatives as fungicides Download PDFInfo
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- WO1995004718A1 WO1995004718A1 PCT/GB1994/001497 GB9401497W WO9504718A1 WO 1995004718 A1 WO1995004718 A1 WO 1995004718A1 GB 9401497 W GB9401497 W GB 9401497W WO 9504718 A1 WO9504718 A1 WO 9504718A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K7/00—Peptides having 5 to 20 amino acids in a fully defined sequence; Derivatives thereof
- C07K7/04—Linear peptides containing only normal peptide links
- C07K7/06—Linear peptides containing only normal peptide links having 5 to 11 amino acids
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
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- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07K5/00—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof
- C07K5/04—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof containing only normal peptide links
- C07K5/06—Dipeptides
- C07K5/06139—Dipeptides with the first amino acid being heterocyclic
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- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K5/00—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof
- C07K5/04—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof containing only normal peptide links
- C07K5/08—Tripeptides
- C07K5/0821—Tripeptides with the first amino acid being heterocyclic, e.g. His, Pro, Trp
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- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K5/00—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof
- C07K5/04—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof containing only normal peptide links
- C07K5/10—Tetrapeptides
- C07K5/1024—Tetrapeptides with the first amino acid being heterocyclic
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Abstract
A fungicidal composition comprising a fungicidally effective amount of a compound of formula (I), wherein R is OH, optionally substituted alkoxy, optionally substituted phenoxy, optionally substituted phenylalkoxy, alkenyloxy, NR<5>R<6> (wherein R<5> and R<6> are, independently, hydrogen, optionally substituted alkyl, optionally substituted phenyl or optionally substituted phenylalkyl) or a nitrogen atom which is included in a peptide residue; or a salt thereof, and a fungicidally acceptable carrier or diluent therefor.
Description
4-METHYLENEPROLINE DERIVATIVES AS FUNGICIDES The present invention relates to fungicidal compositions comprising 4-methyleneproline derivatives, to the use of said compositions and derivatives in combating fungi (especially fungal infections of plants) and to certain 4-methyleneproline derivatives and process for preparing them. 4-Methylene-DL-proline is a naturally occurring racemic amino acid that can be isolated from loquat seed FEriobotrva japonica; see Nature AQA 388-9 (1964), ibid 193 1285-6 (1962) and Phytochemistry ii 745-50 (1972)]. It is known that 4-methyleneproline inhibits the growth of the roots of Phaseolus aureus seedlings [Journal of Experimental Botany 14 387-98 (1963)]. According to the present invention there is provided a fungicidal composition comprising a fungicidally effective amount of a compound of formula (I) wherein R is OH, optionally substituted alkoxy, optionally substituted phenoxy, optionally substituted phenylalkoxy, alkenyloxy, NR5R6 (wherein R5 and R6 are, independently, hydrogen, optionally substituted alkyl, optionally substituted phenyl or optionally substituted phenylalkyl), or a nitrogen atom which is included in a peptide residue; or a salt thereof; and a fungicidally acceptable carrier or diluent therefor. Alkyl groups and the alkyl part of alkoxy, phenylalkyl and phenylalkoxy groups are straight or branched chains and contain (unless otherwise stated) preferably from 1 to 10, especially from 1 to 6 (such as from 1 to 4) carbon atoms. Alkyl is, for example, methyl, ethyl or n- or iso-propyl. It is preferred that.alkyl and alkoxy groups, and the alkoxy part of phenylalkoxy, are optionally substituted by halogen, C16 alkoxy, C16 haloalkoxy, C16 alkoxy(C1 6)alkoxy or phenylalkoxy (in which the phenyl group is optionally substituted). The alkenyl part of the alkenyloxy group is a straight or branch chain having, preferably, up to three double bonds and preferably containing from 3 to 20 carbon atoms. Alkenyl is, for example, allyl, but-2-enyl or farnesyl. Phenyl groups and the phenyl part of phenylalkyl, phenoxy and phenylalkoxy are optionally substituted, and are preferably substituted with one or more of halogen, hydroxy, C1-6 alkyl, C1-6 alkoxy, C16 haloalkyl, C16 haloalkoxy, nitro, cyano, phenyl or halophenyl. As the 2 position of the ring of the compounds of formula (I) is not symmetrically substituted, the compounds of formula (I) can exist as either (D) or (L) (that is either (B) or (S) respectively) isomers and, unless otherwise stated, a reference to a compound of formula (I) includes the (D) and (L) isomers individually and mixtures of these isomers in all proportions. The (L) (that is the (S)) isomers of compounds of formula (I) form a preferred embodiment of the present invention. Peptide residues include glycine, alanine, valine, leucine, isoleucine, serine, threonine, cysteine, methionine, phenylalanine, tyrosine, lysine or norvaline. Salts of a compound of formula (I), when in the form of an acid, ester or amide, include salts of a mineral or an organic acid (for example, a hydrochloride, acetate, hydrobromide, hydroiodide, trifluoroacetate, sulphate, nitrate, oxalate, malonate, fumarate or citrate) or, when R is OH, an alkali metal, alkaline earth metal or amine salt of the acid. In one aspect the present invention provides a fungicidal composition comprising a fungicidally effective amount of a compound of formula (I) wherein R is OH, optionally substituted alkoxy, optionally substituted phenoxy, optionally substituted phenylalkoxy or alkenyloxy; or a salt thereof; and a fungicidally acceptable carrier or diluent therefor. In another aspect the present invention provides a fungicidal composition comprising a fungicidally effective amount of a compound of formula (I) wherein R is OH or unsubstituted C16 alkoxy; or a salt thereof; and a fungicidally acceptable carrier or diluent therefor. In a further aspect the present invention provides a fungicidal composition comprising a fungicidally effective amount of a compound of formula (I) as hereinbefore defined, wherein the compound of formula (I) is the (L) (that is the (±)) isomer; or a salt therof; and a fungicidally acceptable carrier or diluent therefor. In a still further aspect the present invention provides a fungicidal composition comprising a fungicidally effective amount of a compound of formula (I) wherein R is OH, methoxy or ethoxy; the compound of formula (I) being the (L) (that is the (S)) isomer; or a salt (such as the hydrochloride) salt thereof; and a fungicidally acceptable carrier or diluent therefor. In another aspect the present invention provides a fungicidal composition comprising a fungicidally effective amount of the hydrochloride salt of a compound of formula (I) as hereinbefore defined; and a fungicidally acceptable carrier or diluent therefor. It is preferred that the composition of the present invention comprises 4-methylene-(L)-proline as a fungicidal active ingredient. In one aspect the present invention provides a method of combating fungi which comprises applying to plants, to seeds of plants or to the locus of the plants or seeds a compound of formula (I) or a composition, both as hereinbefore defined. In another aspect the present invention provides a compound of formula (I) wherein R is OH, optionally substituted alkoxy, optionally substituted phenoxy, optionally substituted phenylalkoxy, alkenyloxy, NR5R6 (wherein R5 and R6 are, independently, hydrogen, optionally substituted alkyl1 optionally substituted phenyl or optionally substituted phenylalkyl), or a nitrogen atom which is included in a peptide residue; or a salt thereof; provided that when R is OH the compound is in the form of a salt, but not a hydrochloride salt, and that when R is methoxy and the compound is in the L configuration then the compound is in the form of a salt, but not a hydrochloride salt. In a further aspect the present invention provides a compound of formula (I) wherein R is OH, optionally substituted alkoxy, optionally substituted phenoxy, optionally substituted phenylalkoxy or alkenyloxy, or a salt thereof; provided that when R is OH the compound is in the form of a salt, but not a hydrochloride salt, and that when R is methoxy and the compound is in the L configuration then the compound is in the form of a salt, but not a hydrochloride salt. In a still further aspect the present invention provides a compound of formula (I) wherein R is unsubstituted C26 alkoxy, or a salt thereof. In another aspect the present invention provides a salt of a compound of formula (I) wherein R is OH or methoxy, provided that the salt is not a hydrochloride salt. In a further aspect-the present invention provides a salt of a compound of formula (I) wherein R is OH, the compound being the (L) (that is the (S)) isomer. In a still further aspect the present invention provides a salt of a compound of formula (I) wherein R is methoxy, the compound being the (L) (that is the (S)) isomer; provided that it is not a hydrochloride salt. The composition of the present invention preferably comprises a compound of formula (I) as described in Tables I, II or III. TABLE I Compounds listed in Table I are of formula (I). Compound R mpt ( C) Comments No. 1 OH 229 2S (that is L) 2 OH 233 2B (that is D) 3 OH 2R:2S (1:1) 4 OCH3 5 OCH3 2R 6 OCH3 2R:2S 7 farnesyloxy 2S 8 farnesyloxy 2B 9 farnesyloxy oxy 10 OCH3 150-152 2S,HCl salt 11 OCH2CH3 12 OnPr 13 OiPr gum 2S, TFA salt 14 OnBu 15 oiBu 2i 16 otBu 2S 17 O-n-Pentyl 18 O-n-Hexyl 19 O-n-Heptyl 20 O-ff-Octyl 2S 21 O-n-Nonyl 2S 22 O-n-Decyl gum 2S, TFA salt 23 O-n-Undecyl 24 O-n-Dodecyl 25 OCH2CF3 Compound R mpt ( C) Comments No. 26 OCH2C 27 OCH2OCH3 28 OCH2OCH2C 29 OAllyl 30 0-2-Butenyl 31 0-3-Butenyl 32 O-(2-Methylallyl) 33 O-(3,3-Dimethylall 34 O-Geranyl 2S 35 O-Cinnamyl 2S 36 OCH2CH2C6H5 37 OCH2CH2 38 OCH2CH2 39 OCH2CF2 40 0-(3-Methyl-3-butenyl) 2S 41 OC6H5 42 O-(2-F-C6H4) 43 O-(2-CF3-C6H 44 O-(2-C1-C6H4 45 O-(2-OCH3-C6 46 O-(2-CH3-C6H4) 47 O-(2-NO2-C6H 48 O-(3-F-C6H4) 49 O-(3-CF3-C6H 50 O-(3-Cl-C6H4 51 O-(3-OCH3-C6 52 O-(3-CH3-C6H 53 O-(3-NO2-C6H 54 O-(4-F-C6H4) 55 O-(4-CF3-C6H 56 O-(4-Cl-C6H4 Compound R mpt ( C) Comments No. 57 O-(4-OCH3-C6H4 58 O-(4-CH3-C3-C6 59 O-(4-NO2-C6H4 60 O-(3,6-di-F-C6 61 O-(2,6-di-Cl-C6H3) 62 O-(3,5-di-CF3-C6H 63 O-(3,5-di-F-C6H3) 64 O-(3,5-di-OCH3-C6 65 O-(2,4-di-CH3-C6H 66 O-(2,4-di-CH3-C6H 67 O-(2-CH3-4-F-C6H3 68 O-(2-F-4-Cl-C6H3) 69 O-(2-Cl-4-F-C6H3) 70 O-(3-Cl-5-OCH3-C6 71 OCH2C6H5 gum 72 OCH2-(2-F-C6 73 OCH2-(2-CF3-C6H4) 74 OCH2-(2-F-C6 75 OCH2-(2-Cl-C6H4) 2S 76 OCH2-(2-OCH3-C6 77 OCH2-(2-NO2-C6H 78 OCH2-(3-F-C6H4) 79 OCH2-(3-CF3-C6H 80 OCH2-(3-F-C6H4) 81 OCH2-(3-Cl-C6H4 82 OCH2-(3-OCH3-C6 83 OCH2-(3-NO2-C6H 84 OCH2-(4-F-C6H4) 85 OCH2-(4-CF3-C6H 86 OCH2-(4-F-C6H4) 87 OCH2-(4-Cl-C6H4 Compound R mpt ( C) Comments No. 88 OCH2-(4-OCH3-C6H4) 89 OCH2-(4-NO2-C6H4) 90 OCH2-(2,6-di-F-C6H3) 91 0CH2-(2,6-di-Cl-C6H3) 92 OCH2-(3,5-di-F-C6H3) 93 OCH2-(3,5-di-CF3-C6H3) 94 OCH2-(3,5-di-OCH3-C6H3) 95 CH2-(3,4-di-Cl-C6H3) 95 OCH2-(3,4-di-Cl-C6H3) 96 OCH2-(2,4-di-Cl-C6H3) 97 OCH2-(2,4-di-CH3-C6H3) 2S 98 OCH2-(2-Cl-6-F-C6H3) 99 OCH2-(1-Naphthalenyl) 100 OCH2-(2-Naphtahalenyl) 101 OCH(CH3)C6H5 102 OCH(CH3)-(2-CF3-C6H4) 2i 103 OCH(CH3)-(3-CF3-C6H4) 104 OCH(CH3)-(4-CF3-C6H4) TABLE 11 Compounds listed in Table II are of formula (Ia) Compound R1 R2 mpt( C) Comments No. 1 H H oil 2 CH3 H oil 3 CH2CH3 H 4 npr H 5 iPr H 6 nBu H Compound R1 R2 mpt( C) Comments No. 7 iBu H 8 tBu H 9 CH2C6H5 H 10 C6H5 H 11 CH3 CH3 oil 12 CH2CH3 CH2CH3 13 nPr nPr 14 iPr iPr 15 nBu nBu 16 iBu iBu 17 CH2C6H5 CH2C6H5 18 CH3 CH2CH3 19 CH2CH3 iPr 20 CH3 CH2C6H5 TABLE III Compounds listed in Table III are of formula (I). Compound R mpt ( C) Comments No. 1 gly 2 ala 3 norvaline 4 val 5 leu 6 ile 7 ser 8 thr 9 norleucine 10 sarcosine Compound R mpt ( C) Comments No. 11 lys 12 asp 13 glu 14 met 15 16 asn 17 18 arg 19 his 20 phe 21 tyr 22 phenylglycine 23 gly-gly 24 ala-ala gum 2S, TFA salt 25 leu-ala 26 ala-norvaline 27 gly-leu 28 gly-glu 29 glu-glu 30 ala 31 glu-phe 32 asp-phe 33 ala-ala 34 gly-gly-gly-gly The following abbreviations have been used throughout the Tables : : n Pr = n-propyl Pr = iso-propyl nBu-n-bu Bu = iso-butyl tBu-tert-bu TFA = trifluoroacetate gly = N-linked glycine ala = linked alanine val = linked valine leu = N-1liked leucine ile = linked isoleucine ser = linked serine thr = N-linked threonine lys = lysine linked through nitrogen asp = N-linked aspartic acid glu = linked glutamic acid met = N-linked methionine cys = N-linked cysteine asn = N-linked asparagine gln = glutamine linked through α ;-nitrogen arg = N-linked arginine his = N-linked histidine phe = N-linked phenylalanine tyr = N-linked tyrosine TABLE IV Table IV shows selected proton NMR data for certain compounds described in the Tables above. Chemical shifts are measured in ppm from tetramethylsilane. Unless otherwise stated, spectra were recorded on an instrument operating at 270 MHz. The following abbreviations are used s = singlet d = doublet t = triplet m = multiplet q = quartet dd = double doublet br = broad ppm = parts per million Compound No 1H NMR (solvent) 13 (CDCl3) 5.23(2H,d), 5.12(1H,m), 4.52(1H,m), 4.06(2H,br s), (Table I) 3.13(1H,br d), 2.84(1H,br d), 1.28(6H,m)ppm. 22 (CDCl3) 10.08(1H,br s), 8.11(1H,br s), 5.24(2H,d),4.60(1H,dd) (Table I) 4.23(1H,m), 4.10(2H,br s), 3.16(1H,dd), 2.88(1H,dd), 1.66(2H,m), 1.27(14H,m), 0.89(3H,t)ppm. 71 (CDCl3) 7.35(5H,m), 5.22(2H,q), 5.18(2H,m), 4.58(1H,dd), 4.01 (Table I) (2H,m), 3.10(1H,dd), 2.84(1H,dd)ppm. 1 (CD3OD) 5.21(2H,m),4.45(1H,t), 4.00(2H,q),3.15(1H,dd), (Table II) 2.84(1H,m)ppm. 2 (CD3OD) 5.21(2H,m), 4.37(1H,t), 3.98(2H,q),3.23(1H,dd), (Table II) 2.90(3H,s), 2.80(1H,m)ppm. 11 (CD30D) 5.23(2H,m), 4.81(1H,t), 4.00(2H,q), (Table II) 3.23(1H,dd), 3.08(3H,s), 3.00(3H,s), 2.65(1H,m)ppm. 24 (CD30D) 5.28(2H,br s), 4.42(3H,m), 4.01(2H,q), 3.15(1H,dd), (Table III) 2.80(1H,dd), 1.40(6H,d)ppm. A compound of formula (I), wherein R is OH, can be prepared by the method shown in Scheme I. A compound of formula (I), wherein R is OH, can be prepared by deprotecting a compound of formula (II), wherein R' is an alkoxycarbonyl group or arylalkoxycarbonyl group or other suitable protecting group. For example, when R' is a tert-butoxycarbonyl group or benzyloxycarbonyl group deprotection can be effected by contacting the compound of formula (II) with a suitable acid (such as 85% aqueous formic acid). A compound of formula (II) can be prepared by contacting a compound of formula (III), wherein R' is as defined above, with a mixture of methyltriphenylphosphonium bromide and a suitable base (such as sodium hydride) in a suitable solvent (such as an ethereal solvent, for example tetrahydrofuran). A compound of formula (III) can be prepared by oxidising a compound of formula (IV) using a suitable oxidising agent (such as chromium trioxide) in a suitable solvent (such as a mixture of pyridine and dichloromethane). A compound of formula (IV) can be prepared using standard literature methods (for example M. Itoh, D. Hagiwara and T. Kamiya, Bull. Chem. Soc. Japan (1977) fiQ 718) for protecting the ring nitrogen of 4-hydroxy-2pyrrolidine carboxylic acid. Alternatively a compound of formula (I), wherein R is hydroxy, can be prepared by the process described in Tetrahedron 48(31) 6529-6536, that is by reacting a compound of formula (X) with sodium amalgam and K2HP04 in a suitable solvent (such as an alcohol, for example methanol) at a suitable temperature (such as 0 C). Alternatively a compound of formula (I), wherein R is hydroxy, can be prepared by the process outlined in Scheme II. Throughout Scheme II R3 and R4 are, independently, unsubstituted C16 alkyl, and X' and X" are, independently, a leaving group (such as halogen, for example chlorine). Thus, a compound of formula (I) wherein R is hydroxy can be prepared by decarboxylating a compound of formula (V), preferably by using a suitable source of acid such as an ion exchange resin (for example Amberlite IR-120(H+)). A compound of formula (V) can be prepared by hydroysis of a compound of formula (VI), preferably by using a base (for example sodium hydroxide) in a suitable solvent. A compound of formula (VI) can be prepared by reacting a compound of formula (VII) with an acid (such as a strong mineral acid, for example hydrochloric acid) in a suitable solvent (such as an alcohol, for example ethanol). A compound of formula (VII) can be prepared by reacting a compound of formula (IX) with a compound of formula (VIII) in the presence of a suitable base (such as an alkali metal alkoxide, for example sodium ethoxide). A compound of formula (I), wherein R is other than OH but not a nitrogen atom which is included in a peptide residue, can be prepared from a compound of formula (I), wherein R is OH, using standard literature methods (such as B. Nieses and W. Steglich, Org. Synth. (1985) 63 183). They can also be prepared from a compound of formula (II), using standard methods, followed by deprotection of the resulting product. Salts of a compound of formula (I) can be prepared using standard methods. A compound of formula (I), wherein R is a nitrogen atom which is included in a peptide residue, can be made be reacting the peptide, which could have the carboxylic acid moiety suitably protected, with a compound of formula (II)or a derivative thereof (such as the acid chloride) using standard literature conditions (such as those in G.W. Anderson, J.E. Zimmerman and F.M. Callahan, J. Amer. Chem. Soc. (1964) 86 1839). The resulting product can then be deprotected using literature conditions (for example the conditions given above or R. Andruszkiewicz, S. Milewski, T. Zieniawa and E. Borowski, J. Med. Chem. (1990) 33 132). In a further aspect the present invention provides a method for preparing a compound of formula (I) as hereinbefore described. The compounds of formula (I) show fungicidal activity against the class of pathogens known as the phycomycetes (equivalent to the oomycetes). These include species of Phytophthora, Plasmopara, Peronospora and Pseudoperonospora. Examples of pathogens which the invention compounds are particularly useful for controlling are: Plasmopara viticola on vines; other downy mildews such as Bremia lactucae on lettuce; Peronosoora spp. on soybeans, tobacco, onions and other hosts; Pseudoperonospora humuli on hops and Pseudoperonospora cubensis on cucurbits; Phvtophthora infestans on potatoes and tomatoes and other Phvtonhthora spp. on vegetables, strawberries, avocado, pepper, ornamentals, tobacco, cocoa and other hosts; and Pvthium sp on rice, horticultural plants, vegetables and turf. 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 of formula (I). When applied to the foliage of plants, the compounds of the invention are applied at rates of O.1g to 1OKg, preferably 1g to 8Kg, more preferably 109 to 4Kg, of active ingredient per hectare. When used as seed dressings, the compounds of the invention are used at rates of 0.00019 (for example 0.001g or 0.05g) to 109, preferably 0.0059 to 89, more preferably 0.005g to 49, of active ingredient 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. The compositions of the present invention show exceptional activity against the pathogen Plasmopara viticola (vine downy mildew). Therefore, in another aspect the present invention provides a method for combating the pathogen Plasmorpara viticola which comprises applying to vines or to their locus a composition as hereinbefore defined. 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 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. 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 compositions may be in the form of dustable powders or granules comprising the active ingredient and a solid diluent or carrier, for example, fillers such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, fullers 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, li-methylpyrrol-idone, propylene glycol or N,N-dimethylformamide). The compositions may also be in the form of wettable 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 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 beyprepared 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. 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 compounds of formula (I) 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 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. Wettable 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, the condensation products of the said partial esters with ethylene oxide, and the lecithins. 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 containingeO.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. An additional fungicidal compound may be present in the composition of the invention. 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 formula (I) alone. Further the other fungicide can have a synergistic effect on the fungicidal activity of the compound of formula (I). Examples of fungicidal compounds which may be included in the composition of the invention are (RS)-1-aminopropyl- phosphonic acid, (RS)-4-(4-chlorophenyl)-2-phenyl-2-(lH-1,2,4-triazol-1-yl- methyl)butyronitrile, (Z)-N-but-2-enyloxymethyl-Z-chloro-2',6'-diethylacet- anilide, 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, -D!-(3-chloro-2,6- -xylyl)-2-methoxyacetamido]-g-butyrolactone, li-(2-methoxy-5-pyridyl)-cyclo- propane carboxamide, alanycarb, aldimorph, ampropylfos, anilazine, azaconazole, BAS 490F, benalaxyl, benomyl, biloxazol, binapacryl, bitertanol, blasticidin S, bromuconazole, bupirimate, butenachlor, buthiobate, captafol, captan, carbendazim, carbendazim chlorhydrate, carboxin, 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, Q,Q-di-iso-propyl-S-benzyl thiophosphate, dimefluazole, dimetconazole, dimethomorph, dimethirimol, diniconazole, dinocap, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, doguadine, edifenphos, epiconazole, etaconazole, ethirimol, ethoxyquin, ethyl (Z)-N-benzyl-N-([methyl(methyl-thioethylideneamino-oxyCarbonyl)amino]thio)- -p-alaninate, etridiazole, fenaminosulph, fenapanil, fenarimol, fenconazole, fenfuram, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluoroimide, fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fuberidazole, furalaxyl, furconazole-cis, guazatine, hexaconazole, hydroxyisoxazole, hymexazole, ICIA5504, imazalil, imibenconazole, ipconazole, iprobenfos, iprodione, isopropanyl butyl carbamate, isoprothiolane, kasugamycin, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole, methfuroxam, metiram, metiram-zinc, metsulfovax, myclobutanil, NTN0301, neoasozin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, organomercury compounds1 oxadixyl, oxolinic acid, oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, phosetyl-Al, phosphorus acids, phthalide, polyoxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, propionic acid, prothiocarb, pyracarbol id, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinconazole, quinomethionate, quintozene, rabenazole, sodium pentachlorophenate, streptomycin, sulphur, tebuconazole, techlofthalam, tecnazene, tetraconazole, thiabendazole, thicyofen, thifluzamide, 2-(thiocyanomethylthio)benzothiazole, thiophanate-methyl, 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 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. Examples 1 to 6 demonstrate the preparation of compounds of formula (I) while Example 7 illustrates the biological testing of compounds of formula (I). Abbreviations used in reporting the NMR data are as follows: s = singlet dd = double doublet d = doublet ddd = doublet of double doublets t = triplet ABq = AB quartet m = multiplet dt = double triplet q = quartet br = broad "DISPERSOL T" is a Trade Mark or Trade Name. EXAMPLE 1 Preparation of (2S)-4-methylene-2-pyrrolidinecarboxylic acid, alternatively named 4-methylene-(L)-proline (Compound No. 1 of Table I). Step 1 Preparation of (2S,4B)-N-tert-butoxycarbonyl-4-hydroxy-2-pyrrolidine- carboxylic acid. 2-(tert-Butoxycarbonyloxyimino)-2-phenylacetonitrile (49.259, 0.200 mole) was added to a rapidly stirred solution of (2S,4B)-4-hydroxy-2- pyrrolidinecarboxylic acid (26.23g, 0.200 mole) in a mixture of water (200ml), methanol (300ml), dioxane (lOOml), and triethylamine (42ml, 0.30mol). After 2 hours the solvent was evaporated under reduced pressure to provide a gum, which was dissolved in water (600ml). The solution was washed with diethyl ether, acidified to pH 3 by the addition of aqueous citric acid, saturated with sodium chloride, and extracted with ethyl acetate. The combined extracts were dried and evaporated to provide a gum, which was crystallised from diethyl ether to yield the title compound as a white solid (32.0g, 69%). mp 122"C. IR (nujol mull) 3364, 2620, 1734, 1660 cm 1; 1H NMR (CD3SOCD3):8 4.28(1H,m), 4.18(1H,t), 3.42(1H,dd), 3.28(1H,ddd), 2.10(1H,m), 1.95(1H,m), 1.39(9H,s) ppm. Step 2 Preparation of (2S)-N-tert-butoxycarbonyl-4-oxo-2-pyrrolidine- carboxylic acid. A solution of (2S,4B)-N-tert-butoxycarbonyl-4-hydroxy-2-pyrrolidine- carboxylic acid (26.0g, 0.113 mole) in pyridine (lOml) and dichloromethane (80ml) was added to a solution of chromium trioxide (67.2g, 0.672 mole) in pyridine (108ml) and dichloromethane (1400ml). After stirring for 5 hours, the solution was decanted and the residue washed with acetone. The combined organic washings were evaporated to leave a gum, which was dissolved in brine and ethyl acetate. The aqueous phase was adjusted to pH 3 by the addition of aqueous hydrogen chloride, both phases were filtered and then separated. The aqueous phase was extracted with ethyl acetate. The combined organic extracts were dried, treated with charcoal, filtered and evaporated to provide a gum. Crystallisation from dichloromthane-ether yielded the title compound as a solid (3.91g). Further product (8.0g) was recovered by evaporation of the mother liquors. mp 1300C (dec.); IR (CH2Cl2) 1766, 1700 cm 1; 1H NMR (CD3SOCD3):s 4.52(1H,d), 3.68(2H,ABq), 3.01(1H,dd), 2.39(1H,d), 1.35(9H,s) ppm. Step3 Preparation of (2)-li-tert-butoxycarbonyl-4-methylene-2-pyrrolidine- carboxylic acid. Methyltriphenylphosphonium bromide (49.5g, 0.139 mole) was added to a stirred suspension of hexane-washed sodium hydride (60% in oil, 5.5g, 0.14 mole) in tetrahydrofuran (350ml). The mixture was heated at 500C for 5 hours, then a solution of (2S)-N-tetr-butoxycarbonyl-4-oxo-2-pyrrolidine- carboxylic acid (7.99, 0.03 mole) in tetrahydrofuran (70ml) was added over 30 minutes. The mixture was stirred at 500C for 17 hours, then cooled and poured into aqueous sodium bicarbonate. The solution was washed with diethyl ether, acidified to pH 3 with aqueous citric acid, and extracted with ethyl acetate. The extract was dried and evaporated to provide an oil which was purified by column chromatography (eluant: ethyl acetate:acetic acid, 99:1) to yield the title compound as a gum (2.1g). IR (liquid) 2900, 1750, 1704, 1665 cm 1; 1H NMR (CDCl3):8 5.03(2H,s), 4.45(1H,m), 4.03(2H,m), 2.90(2H,m), 1.45(9H,d) ppm. Step 4 Preparation of (2S)-4-methylene-2-pyrrolidinecarboxylic acid. A solution of (2X)-N-tert-butoxycarbonyl-4-methylene-2-pyrrolidine- carboxylic acid (1.77g, 7.41 mmol) in 85% aqueous formic acid (55ml) was stirred for 5 hours, then the solvent was evaporated to leave a gum. Isopropanol was added, and the resulting solid filtered and dried to yield the title compound (782mg). mp 229 C. [α]D25 = -50.4 C (c=0.01 in H2O); ÚH NMR (D20):5 5.19(2H,dt), 4.26(1H,t), 3.98(2H,ABq), 2.90(2H,ABx) ppm. EXAMPLE 2 Preparation of methyl (2S)-4-methylene-2-pyrrolidinecarboxylate, hydrochloride salt (Compound No.10 in Table I). Acetyl chloride (0.64 ml, 8.96 mmol) was added dropwise to a solution of (2S)-N-tetr-butoxycarbonyl-4-methylene-2-pyrrolidinecarboxylic acid (370mg, 1.63 mmol) in methanol (10 ml). The solution was kept at 0OC for 30 minutes, then allowed to warm to ambient temperature over 1 hour. The solvent was evaporated to leave a solid which was crystallised from methanol:ether to yield the title compound (161 mg). mp 150-152 C. 1H NMR (CD30D): b 5.25(2H,m), 4.61(1H,t), 4.01(2H,q), 3.85(3H,s), 3.12(1H,dd), 2.85(1H,dd) ppm. EXAMPLE 3 Preparation of benzyl (2S)-4-methylene-2-pyrrolidinecarboxylate, hydrochloride salt (Compound No.71 in Table I). Steps Preparation of benzyl (2S)-N-tert-butoxycarbonyl-4-methylene-2- pyrrol idinecarboxylate. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (0.929 g, 4.85 mmol) was added in portions to a solution of (2X)- li-tert-butoxycarbonyl-4-methylene-2-pyrrolidinecarboxylic acid (0.50 g, 2.2 mmol), 4-dimethylaminopyridine (catalytic) and benzyl alcohol (0.476 g, 4.4 mmol) in dichloromethane (30 ml) and the mixture stirred under nitrogen for 2 hours. Water was added and the mixture extracted with dichloromethane. The extract was dried and evaporated to leave an oil, which was purified by column chromatography (eluant: ethyl acetate:hexane:acetic acid, 1:2:0.01) to yield the title compound (0.431 g). 1H NMR (CDCl3): 8 7.34(5H,s), 5.17(2H,m), 4.99(2H,m), 4.50(1H,ddd), 4.07(2H,d), 2.96(1H,m), 2.61(1H,br s), 1.47 and 1.35(9H,s) ppm. Step 2 Preparation of benzyl (2S)-4-methylene-2-pyrrolidinecarboxylate, hydrochloride salt. A solution of benzyl (2S)-N-tert-butoxycarbonyl-4-methylene-2- pyrrolidinecarboxylate (297 mg, 0.94 mmol) in trifluoroacetic acid (2 ml) was stirred under nitrogen at 0 C for 2 hours, then allowed to warm to ambient temperature and the solvent evaporated to yield the title compound as an oil (255 mg). 1H NMR (CDCl3): 8 7.35(5H,m), 5.22(2H,ABq), 5.18(2H,m), 4.58(1H,dd), 4.01(2H,m), 3.10(1H,dd), 2.84(1H,dd) ppm. EXAMPLE 4 Preparation of (2X)-4-methylene-2-pyrrolidine-N-methylcarboxamide, trifluoroacetate salt (Compound No.2 of Table II). Steps Preparation of li-hydroxysuccinimidyl (2) -li-tert-butoxycarbonyl -4- -methylene-2-pyrrolidinecarboxylate. Dicyclohexyl carbodiimide (2.04 g, 9.88 mmol) was added to a stirred solution of (2S)-N-tert-butoxycarbonyl-4-methylene-2-pyrrolidinecarboxylic acid (2.04 g, 8.98 mmol) and li-hydroxysuccinimide (1.03 g, 8.98 mmol) in ethyl acetate (20 ml). The mixture was stirred at 0 C under nitrogen for 2. hours and then allowed to stand at this temperature for 18 hours. The mixture was then filtered and the filtrate evaporated to provide an oil that was purified by column chromatography (eluant: ethyl acetate:hexane, 1:1) to yield a white solid. This was crystallised from ethyl acetate:hexane to yield the title compound (2.24 g). 1H NMR (CDCl3): 8 5.09(2H,m), 4.71(1H,dd), 4.12(2H,m), 3.18(1H,dd), 2.93(1H,br d), 2.86(4H,s), 1.49(9H,s) ppm. Step 2 Preparation of (2S)-N-tert-butoxycarbonyl-4-methylene-2-pyrrolidine- li-methyl carboxami de. Methyl amine was bubbled through a solution of triethylamine (374 mg, 6.17 mmol) in methanol (5 ml) at 0 C for 30 minutes. A solution of li-hydroxysuccinimidyl (2i -tert-butoxycarbonyl-4-methylene-2-pyrrolidinecarboxylate (1 g, 3.08 mmol) in methanol (5 ml) was added dropwise and the mixture stirred under nitrogen for 30 minutes. Water was added and the mixture extracted with ethyl acetate. The extract was dried and evaporated to leave an oil which was purified by column chromatography (eluant: ethyl acetate:hexane, 1:1) to yield the title compound as an oil (0.74 g). 1H NMR (CDCl3): 8 5.00(2H,m), 4.42(1H,br s), 4.05(2H,q), 2.86(2H,m), 2.79(3H,d), 1.47(9H,s) ppm. Step 3 Preparation of (2S)-4-methylene-2-pyrrolidine-N-methylcarboxamide, trifluoroacetate salt. A solution of (2S)-N-tert-butoxycarbonyl-4-methylene-2-pyrrolidine- li-methylcarboxamide (1.2 g, 5 mmol) in trifluoroacetic acid (3 ml) was allowed to stand for 18 hours, then the solvent was evaporated to yield the title compound as an oil (0.68 g). 1H NMR (CD3OD): 8 5.21(2H,m), 4.37(1H,t), 3.98(2H,q), 3.23(1H,dd), 2.90(3H,s), 2.80(1H,m) ppm. EXAMPLE 5 Preparation of ((S)-4-methyleneprolyl)-(S)-alanyl-(S)-alanine, trifluoroacetate salt (Compound No.24 in Table III). Step 1 Preparation of ((S)-N-tert-butoxycarbonyl-4-methyleneprolyl)-(S)alanyl-(S)-alanine. A solution of N-hydroxysuccinimidyl (2S)-N-tert-butoxycarbonyl-4- methylene-2-pyrrolidinecarboxylate (500 mg, 1.54 mmol) in methanol (10 ml) was added dropwise to a solution of (S)-alanyl-(X)-alanine (247 mg, 1.54 mmol) and triethylamine (312 mg, 3.09 mmol) in methanol (10 ml) and the mixture stirred under nitrogen at 5"C for 30 minutes, then at ambient temperature for 6 hours. The solvent was evaporated to leave a gum which was purified by column chromatography (eluant: ethyl acetate:hexane:acetic acid, 1:2:0.01) to yield the product (246 mg). 1H NMR (CD3SOCD3): 8 8.15(2H,m), 4.96(2H,d), 4.33(2H,m), 4.20(1H,m), 3.96(2H,br s), 3.39(1H,br s), 2.92(1H,m), 1.37(9H,s), 1.30(3H,d), 1.24(3H,d) ppm. Step2 Preparation of ((S)-4-methyleneprolyl)-(S)-alanyl-(S)-alanine, trifluoroacetate salt. A solution of (X)-N-tert-butoxycarbonyl-4-methyleneprolyl)-(S)-alanyl- (S)-alanine (100 mg, 0.26 mmol) in trifluoroacetic acid (2 ml) was stirred for 2 hours, then the solvent was evaporated to yield the title compound (68 mg). 1H NMR (CD3OD): 8 5.28(2H,br s), 4.42(3H,m), 4.01(2H,q), 3.15(1H,dd), 2.80(1H,dd), 1.40(6H,d) ppm. EXAMPLE 6 The compounds of formula (I) were tested against the diseases Plasmopora viticola on vine and Phytophthora infestans lvcooersici on tomato. The technique employed was as follows. The plants were grown in John Innes Potting Compost (No. 1 or 2) in 4cm 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 applied to the roots of the plants in the soil. The root drenches were applied to a final concentration equivalent to approximately 40 ppm a.i. in dry soil. For most of the tests the compounds were applied to the soil (roots) one or two days before the plant was inoculated with the disease. The pathogens were applied by spray as spore 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 seven days according to the disease and environment. The disease control was assessed by visual assessment of the percentage leaf area covered by actively sporulating disease. Assessments were performed on a single leaf of each of the two replicate plants, and the mean value of these two recordings was calculated for each treatment. The mean value for each treatment 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: Mean disease level on untreated Control = 90 Mean disease level on treatment A = 30 POCO Mean disease level on treatment A for treatment A = ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ x 100 Mean disease level on untreated Control 30 = ¯ x 100 = 33.3 90 Thus a POCO value of 0 indicates complete disease control. The results are shown in Table V. TABLE V Compound No. Pv syst Pil syst (Table No.) 1(I) O 7 2(I) 0 64 3(I) 0 lO(I) O 15 13(I) 0 4 22(I) 0 Compound No. Pv syst Pil syst (Table No.) 71(I) 0 20 1(II) 0 2(11) 75 100 11(II) 78 24(111) 0 48 Pv = Plasmopara viticol fil = Phvtophthora infestans lycopersici syst = root drench CHEMICAL FORMULA (IN DESCRIPTION) EMI26.1 CHEMICAL FORMULA (IN DESCRIPTION) Scheme I EMI27.1 CHEMICAL FORMULA (IN DESCRIPTION) Scheme II EMI28.1
Claims
CLAIMS 1. A fungicidal composition comprising a fungicidally effective amount of
a compound of formula (I):
EMI29.1
wherein R is OH, optionally substituted alkoxy, optionally substituted
phenoxy, optionally substituted phenylalkoxy, alkenyloxy, NR5R6
(wherein R5 and R6 are, independently, hydrogen, optionally
substituted alkyl, optionally substituted phenyl or optionally
substituted phenylalkyl) or a nitrogen atom which is included in a
peptide residue; or a salt thereof, and a fungicidally acceptable
carrier or diluent therefor.
2. A fungicidal composition as claimed in claim 1 wherein R is OH,
optionally substituted alkoxy, optionally substituted phenoxy,
optionally substituted phenylalkoxy, or alkenyloxy.
3. A fungicidal composition as claimed in claim 1 or 2 wherein R is OH or
unsubstituted C16 alkoxy.
4. A fungicidal composition as claimed in claim 1, 2 or 3 wherein the
compound of formula (I) is the (L) isomer.
5. A fungicidal composition as claimed in claim 1, 2, 3 or 4 wherein R is
OH, methoxy or ethoxy, the compound of formula (I) being the (L)
isomer.
6. A fungicidal composition as claimed in claim 1, 2, 3, 4 or 5 wherein
the compound of formula (I) is in the form of a hydrochloride salt.
7. A method of combating fungi which comprises applying to plants, to
seeds of plants or to the locus of the plants or seeds a compound of
formula (I) or a composition according to claim 1.
8. A compound of formula (I):
EMI30.1
wherein R is OH, optionally substituted alkoxy, optionally substituted
phenoxy, optionally substituted phenylalkoxy, alkenyloxy, NR5R6
(wherein R5 and R6 are, independently, hydrogen, optionally
substituted alkyl, optionally substituted phenyl or optionally
substituted phenylalkyl) or a nitrogen atom which is included in a
peptide residue; and salts thereof; provided that when R is OH then
the compound is in the form of a salt, but not a hydrochloride salt,
and that when R is methoxy and the compound is the L isomer then the
compound is in the form of a salt, but not a hydrochloride salt.
9. A compound of formula (I) as claimed in claim 8 wherein R is
unsubstituted C26 alkoxy, or a salt thereof.
10. A salt of a compound of formula (I) as claimed in claim 8 wherein R is
OH or methoxy; provided that the salt is not a hydrochloride salt.
11. A salt of a compound of formula (I) as claimed in claim 8 wherein R is
OH, the compound of formula (I) being the (L) isomer.
12. A salt of a compound of formula (I) as claimed in claim 8 wherein R is
methoxy, the compound of formula (I) being the (L) isomer; provided
that the salt is not a hydrochloride salt.
13. A process for preparing a compcund as claimed in claim 8, the process
comprising either:
a) deprotecting a compound of formula (II):
EMI31.1
b) decarboxylating a compound of formula (V):
EMI31.2
using a suitable source of acid; or c) reacting a compound of formula (X):
EMI31.3
with sodium amalgam and K2HPO4 in a suitable solvent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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AU71293/94A AU7129394A (en) | 1993-08-04 | 1994-07-11 | 4-methyleneproline derivatives as fungicides |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB939316162A GB9316162D0 (en) | 1993-08-04 | 1993-08-04 | Fungicides |
GB9316162.8 | 1993-08-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995004718A1 true WO1995004718A1 (en) | 1995-02-16 |
Family
ID=10739957
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1994/001497 WO1995004718A1 (en) | 1993-08-04 | 1994-07-11 | 4-methyleneproline derivatives as fungicides |
Country Status (5)
Country | Link |
---|---|
AU (1) | AU7129394A (en) |
GB (2) | GB9316162D0 (en) |
IL (1) | IL110308A0 (en) |
WO (1) | WO1995004718A1 (en) |
ZA (1) | ZA945259B (en) |
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US7211601B2 (en) | 2000-03-27 | 2007-05-01 | Applied Research Systems Ars Holding N.V. | Pharmaceutically active pyrrolidine derivatives |
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- 1994-07-19 ZA ZA945259A patent/ZA945259B/en unknown
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Also Published As
Publication number | Publication date |
---|---|
GB9316162D0 (en) | 1993-09-22 |
IL110308A0 (en) | 1994-10-21 |
ZA945259B (en) | 1995-02-06 |
AU7129394A (en) | 1995-02-28 |
GB9413861D0 (en) | 1994-08-24 |
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