GB2249092A - Oxime ether fungicides - Google Patents
Oxime ether fungicides Download PDFInfo
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- GB2249092A GB2249092A GB9120643A GB9120643A GB2249092A GB 2249092 A GB2249092 A GB 2249092A GB 9120643 A GB9120643 A GB 9120643A GB 9120643 A GB9120643 A GB 9120643A GB 2249092 A GB2249092 A GB 2249092A
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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
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
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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
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
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- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
- C07D251/20—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom with no nitrogen atoms directly attached to a ring carbon atom
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- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
- C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
- C07D253/06—1,2,4-Triazines
- C07D253/065—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members
- C07D253/07—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members 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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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
- C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
- C07D253/06—1,2,4-Triazines
- C07D253/065—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members
- C07D253/07—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members 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
- C07D253/075—Two hetero atoms, in positions 3 and 5
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- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C—CHEMISTRY; METALLURGY
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- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
Fungicidal compounds having the formula (i): <IMAGE> in which any two of K, L and M are nitrogen and the other is CY wherein Y is H, halogen, C1-4 alkyl, C1-4 alkoxy, cyano, nitro or trifluoromethyl; n is 0 or 1 and X is an optionally substituted aromatic or heteroaromatic ring.
Description
FUNGICIDES
This invention relates to derivatives of propenoic acid useful as fungicides, to processes for preparing them, to fungicidal compositions containing them, and to methods of using them to combat fungi, especially fungal infections of plants.
There is described in EP-A-0260794 a range of fungicidal compounds which are methyl 2-(optionally substituted)heterocyclyloxy(or thio)phenyl-3methoxypropenoates. The heterocyclic ring is six-membered, C-linked and contains 2 to 4 nitrogen atoms.
Included are triazinyloxy compounds.
According to the present invention there are provided compounds having the formula (I):
in which any two of K, L and N are nitrogen and the other is CY wherein Y is H, halogen, C14 alkyl (for example, methyl), C14 alkoxy (for example, methoxy), cyano, nitro or trifluoromethyl; n is 0 or 1; and x is an optionally substituted aromatic or heteroaromatic ring.
Because of the unsymmetrically substituted double bond of the oxime ether group, 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 including those which consist substantially of the (Z)-isomer and those which consist substantially of the (E)-isomer. The (E)-isomer, in which the groups -CO2CH3 and -OCH3 are on opposite sides of the carbon-nitrogen bond of the oxime ether group, are generally the more fungicidally active and form a preferred embodiment of the invention.
Geometric pairs of isomers of the compounds listed later in Tables I, II and III are identified by the letters A and B. In many instances, using solvent systems such as ether or ethyl acetate or mixtures of one of these with petrol, the isomers A and B of a compound have significantly different Rf values when analysed by thin-layer chromatography on silica gel. Of each pair of isomers, the isomer which is the less polar on silica gel is termed Isomer A and the more polar one, Isomer B. In the case of the two geometric isomers of methyl O-methyl(2-phenoxy-phenyl)oximino-acetate (compounds numbers 5 and 6 of Table I of EP-A-0254426), Isomer B has been shown unambiguously by X-ray analysis to be the (E)-isomer. It is believed that for every isomer pair,
Isomer B corresponds to the (E)-isomer and Isomer A corresponds to the (Z)-isomer but this has not been proven.Generally the B isomers are the more active ones fungicidally and form a preferred embodiment of the invention.
The ring
in formula (I) is a triazine ring. It may be a symmetrical triazine ring in which K and M are both nitrogen and L is CY or an unsymmetrical triazine ring in which either K and L are both nitrogen and M is CY or L and m are both nitrogen and K is CY.
The group Y is typically H or halogen, suitably chlorine.
The group X may be any optionally substituted aromatic or heteroaromatic ring. When it is an optionally substituted aromatic ring the aromatic ring is suitably phenyl. When it is an optionally substituted heteroaromatic ring the heteroaromatic ring may be, for example, one of the following rings, in each case linked from any atom of the ring X which valency allows: furan, thiophene, pyrrole, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, 1,2,4-triazole, 1,2,3-triazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, pyridine, pyrimidine, pyrazine, pyridazine, 1,2,4-triazine or 1,3,5-triazine.
Optional substituents of the aromatic or heteroaromatic ring X include one or more of halogen, C1-4 alkyl, C3-6 cycloalkyl, C2-4 alkenyl, C2-4 alkynyl, C24 alkenyloxy, C24 alkynyloxy, phenyl, benzyloxy, cyano, isocyano, isothiocyanato, nitro, NR1R2, NR1OR2, N3,
NHCOR1 NR1COR2, NHCONR1R2, N=CHNR1R2, NHSO2R1 O OCOR1, OS02R1, SR1, SOR1, SO2R11 SO2OR1, SO NR1R2, COR1, CR1=NOR2, CHR1CO2R2, CO2R1, CONR1R2, CSNR1R2, CH3O2C.C:CH.OCH3, CH3O2C.C::N.OCH3, 1-(imidazol-1-yl)vinyl, a 5-membered heterocyclic ring containing one, two or three nitrogen heteroatoms, or a 5- or 6-membered heterocyclic ring containing one or two oxygen or sulphur heteroatoms, optionally a nitrogen heteroatom and optionally one or two oxo or thioxo substituents; or two substituents when ortho to one another, join to form a 5or 6-membered aliphatic or aromatic ring optionally containing one or more oxygen, sulphur or nitrogen atoms.
R1 and R2 are independently hydrogen, C14 alkyl, C24 alkenyl or phenyl. The aliphatic moieties of any of the substituents may themselves be substituted with one or more of halogen, cyano, OR1, SR1, NR1R2, SiR13 or OCOR1 and the phenyl moieties of any of the substituents may themselves be substituted with one or more of halogen,
C1-4 alkyl, C1-4 alkoxy, nitro or cyano.
Alkyl groups contain from 1 to 4 carbon atoms and may be in the form of straight or branched chains. Examples are methyl, ethyl, iso-propyl, n-butyl and t-butyl.
Cycloalkyl groups contain from 3 to 6 carbon atoms and include cyclopropyl and cyclohexyl.
Alkenyl and alkynyl groups contain from 2 to 4 carbon atoms and may be in the form of straight or branched chains. Examples are ethenyl, allyl, methylallyl and propargyl.
Halogen is typically fluorine, chlorine or bromine.
Aliphatic moieties which may be substituted include, in particular, C14 alkyl groups.
Of particular interest are compounds of formula (I) in which X is unsubstituted phenyl or phenyl substituted by halogen (especially chlorine), C1-4 alkyl, C1-4 alkoxy, trifluoromethyl, cyano or nitro.
In one aspect the invention provides a compound of formula (I.1):
in which Y is H or chlorine and Q is H, halogen (especially chlorine), cyano, nitro or trifluoromethyl.
In another aspect the invention provides a compound of formula (I.2):
in which Y is H or chlorine and Q is halogen, C1-4 alkyl,
C1-4 alkoxy (especially methoxy), cyano, nitro, trifluoromethyl, CH302C.C:CH.OCH3 or CH302C.C:N.OCH3.
The invention is illustrated by the compounds listed in Tables I to III which follow. Unless otherwise stated, the carbon-nitrogen double bond has the (E)-configuration.
TABLE I
Compound X Melting Isomer* No. n Point ( C 1 C6H5- 0 2 2-F-C6H4- O 3 3-F-C6H4- 0 4 4-F-C6H4- 0 5 2-Cl-C6H4- 0 6 3-Cl-C6H4- 0 7 4-Cl-C6H4- O 8 2-Br-C6H4- 0 9 2-cyano-C6H4- 0 10 3-cyano-C6H4- 0 11 4-cyano-C6H4- O 12 2-isocyano-C6H4- O 13 2-NO2-C6H4- 0 14 3-N02-C6H4- 0 15 4-NO2-C6H4- 0 16 2-NH2-C6H4- 0 17 3-NH(CH3)-C6H4- 0 18 2-N(CH3)2-C6H4- 0 19 2-NH.CHO-C6H4- 0 20 2-CH3CO.NH-C6H4- 0 21 3-C6H5CO.NH-C6H4- 0 22 2-H2N.CoNH-C6H4- O 23 3-(C2H5)NH.CONH-C6H4- 0 24 2-CH3SO2NH-CH4- 0 25 3-C6H5SO2NH-C6H4- 0 26 2-HO-C6H4- 0 27 3-HO-C6H4- 0 28 4-HO-C6H4- 0 29 2-CH3O-C6H4- 0 30 3-CH3O-C6H4- 0 TABLE I (Contd.)
Compound X Melting No. n Point ( C) 31 4-CH30-C6H4- O 32 2-C2H5O-C6 H- 0 33 3-(2-F-C6H4O)-C6H4- 0 34 2-CH3C02-C6H4- 0 35 2-CH3SO2O-C6H4- 0 36 3-(4-CH3-C6H4S020)- 0 -C6H4- 37 2-thiocyanato-C6H4- 0 38 3-thiocyanato-C6H4- 0 39 4-thiocyanato-C6H4- 0 40 2-CH3S-C6H4- 0 41 3-CH3S-C6H4- 0 42 4-CH3S-C6H4- 0 43 2-CH3SO-C6H4- 0 44 2-CH3SO2-C6H4- 0 45 4-CH3(CH2)3SO2-C6H4- 0 46 2-CHO-C6H4- 0 47 3-CHO-C6H4- 0 48 4-CHO-C6H4- 0 49 2-CH3CO-C6 H- O 50 3-C6H5CO-C6H4- 0 51 2-(E)-HON:CH-C6H4- O 52 3-(E)-HON:CH-C6H4- O 53 4-(E)-HON:CH-C6H4- 0 54 2-(E)-CH3ON:CH-C6H4- 0 55 2-(E)-HON:C(CH3)-C6H4- 0 56 2-H2NCO-C6H4- 0 57 3-H(CH3)NCO-C6H4- 0 58 4-(CH3)2NCO-C6H4- 0 TABLE I (Contd.)
Compound X Melting Isomer* No. n Point ( C) 59 2-H2NCS-C6H4- 0 60 2-H(CH3)NCS-C6H4- 0 61 2-CH3-C6H4- 0 62 3-CH3-C6H4- O 63 4-CH3-C6H4- 0 64 2-C2H5-C6H4- 0 65 2-FCH2-C6H4- 0 66 2-BrCH2-C6H4- 0 67 2-ClCH2-C6H4- 0 68 2-cyanomethyl-C6H4- 0 69 2-HOCH2-C6H4- 0 70 2-CH3OCH2-C6H4- 0 71 2-CH3CO2CH2-C6H4- 0 72 3-cyanomethyl-C6H4- 0 73 4-HOCH2-C6H4- 0 74 3-CH3OCH2-C6H4- 0 75 2-CH2:CH-C6H4- 0 76 2-CH2:CHCH2-C6H4- 0 77 2-HC#C-C6H4- 0 78 2-HC#CCH2-C6H4- 0 79 3-CH2:C(CH3)CH2-C6H4- 0 80 2-CH2:CHCH2O-C6H4- 0 81 2-HC#-CCH2O-C6H4- 0 82 2-C6H5-C6H4- 0 83 3-C6H5-C6B4- 0 84 4-C6H5-C6H4- 0 85 2-C6H5O-C6H4- 0 86 3-C6H5O-C6H4- 0 87 4-C6H5O-C6H4- 0 TABLE I (Contd.)
Compound X Melting Isomer* No. n Point (OC) 88 2-(4-Cl-C6H4O)-C6H- 0 89 2-C6H5CH2O-C6H4- 0 90 2-cyano-4-Cl-C6H3- O 91 2-N02-4-F-CgH3- 0 92 2,4-di-C1-C H - 0 93 2,3-di-CH3O-C6H3- 0 94 2-cyano-5-Cl-C6H3- 0 95 2,6di-cyano-CgH3 96 2-F-5-Cl-C6H3- 0 97 3,5-di-CH3O-C6H3- 0 98 3-cyano-4-F-C6H3- 0 99 2-NO2-3-CH3O-C6H3- O 100 3-CH3O-5-cyano-C6H3- o 101 0 0 102 103 0 104 2, 3-methylenedioxy -C6H3- 0 105 0 TABLE I Continued
Compound X I Melting Isomer* No. I n Point (OC1 106 0 Hun 107 Pyridin-2-yl 0 108 Pyridin-3-yl 0 109 Pyridin-4-yl O 110 Pyrimidin-2-yl O 111 Pyrimidin-4-yl O 112 Pyrimidin-5-yl O 113 Thien-2-yl O 114 Thien-3-yl O 115 C6H5- 1 116 2-F-C6H4- 1 117 3-F-C6H4- 1 118 4-F-C6H4- 1 119 2-C1-C6H4- 1 120 3-Cl-C6H4- 1 121 4-Cl-C6H4- 1 122 2-Br-C6H4- 1 123 2-cyano-C6H4- 1 124 3-cyano-C6H4- . 1 125 4-cyano-C6H4- 1 126 2-isocyano-C6H4- 1 127 2-N02-C6H4- 1 128 3-N02-C6H4- 1 129 4-N02-C6H4- 1 TABLE I Continued
Compound X Melting Isomer* No. n Point ( C) 130 2-NH2-C6H4- 1 131 3-NH(CH3)-C6H4- 1 132 2-N(CH3)2-C6H4- 1 133 2-NH.CHO-C6H4- 1 134 2-CH3CO.NH-C6H4- 1 135 3-C6H5CO.NH-C6H4- 1 136 2-H2N.CONH-C6H4- 1 137 3-(C2H5)NH.CONH-C6H4- 1 138 2-CH3SO2NH-C6H4- 1 139 3-C6H5SO2NH-C6H4- 1 140 2-HO-C6H4- 1 141 3-HO-C6H4- 1 142 4-HO-C6H4- 1 143 2-CH30-C6H4- 1 144 3-CH3O-C6H4- 1 145 4-CH3O-C6H4- 1 146 2-C2H5O-C6 H- 1 147 3-(2-F-C6H4O)-C6H4- 1 148 2-CH3CO2-C6H4- 1 149 2-CH3SO2O-C6H4- 1 150 3-(4-CH3-C6H4SO2O)- 1 -C6H4- 151 2-thiocyanato-C6H4- 1 152 3-thiocyanato-C6H4- 1 153 4-thiocyanato-C6H4- 1 154 2-CH3S-C6H4- 1 155 3-CH3S-C6H4- 1 156 4-CH3S-C6H4- 1 TABLE I (Contd.)
Compound X Melting Isomer* No. n Point ( C) 157 2-CH3SO-C6H4- 1 158 2-CH3SO2-C6H4- 1 159 4-CH3(CH2)3SO2-C6H- 1 160 2-CHO-C6H4- 1 161 3-CHO-C6H4- 1 162 4-CHO-C6H4- 1 163 2-CH3CO-C6H4- 1 164 3-C6H5CO-C6H4- 1 165 2-(E)-HON:CH-C6H4- 1 166 3-(E)-HON:CH-C6H4- 1 167 4-(E)-HON:CH-C6H4- 1 168 2-(E)-CH3ON:CH-C6H4- 1 169 2-(E)-HON::C(CH3)-C6H4- 1 170 2-H2NCO-C6H4- 1 171 3-H(CH3)NCO-C6H4- 1 172 4-(CH3)2NCO-C6H4- 1 173 2-H2NCS-C6H4- 1 174 2-H(CH3)NCS-C6H4- 1 175 2-CH3-C6H4- 1 176 3-CH3-C6H4- 1 177 4-CH3-C6H4- 1 178 2-C2H5-C6H4- 1 179 2-FCH2-C6H4- 1 180 2 BrCH2-C6H4- 1 181 2-ClCH2-C6 H- 1 182 2-cyanomethyl-C6H4- 1 183 2-HOCH2-C6 H- 1 184 2-CH3OCH2-C6H4- 1 185 2-CH3CO2CH2-C6H4- 1 TABLE I (Contd.)
Compound X Melting Isomer* No. n Point ( C) 186 3-cyanomethyl-C6H4- 1 187 4-HOCH2-C6 H- 1 188 3-CH3OCH2-C6H4- 1 189 2-CH2:CH-C6H- 1 190 2-CH2:CHCH2-C6H4- 1 191 2-HC#C-C6H4- 1 192 2-HC#CCH2-C6H4- 1 193 3-CH2:C(CH3)CH2-C6H4- 1 194 2-CH2::CHCH2O-C6H4 1 195 2-HC#CCH2O-C6H4- 1 196 2-C6H5-C6H4- 1 197 3-C6H5-C6H4- 1 198 4-C6H5-C6H4- 1 199 2-C6H5O-C6H4- 1 200 3-C6H5O-C6H4- 1 201 4-C6H5O-C6H4- 1 202 2-(4-Cl-C6H4O)-C6H4- 1 203 2-C6H5CH2O-C6H4- 1 204 2-cyano-4-Cl-C6H3- 1 205 2-NO2-4-F-C6H3- 1 206 2,4-di-Cl-C6H3- 1 207 2,3-di-CH3O-C6H3- 1 208 2-cyano-5-Cl-C6H3- 1 209 2,6-di-cyano-C6H3- 1 210 2-F-5-C1-C6H3- 1 211 3,5-di-CH3O-C6H3- 1 212 3-cyano-4-F-C6H3- 1 213 2-NO2-3-CH3O-C6H3- 1 TABLE I Continued
Compound x Melting Isomer* No. n Point (OC) 214 3-CH30-5-cyano-c6H3- 1 215 215 1 ,N 216 217 z 1 218 2, 2,3-methylened oxy- 1 -C H 1 219 220 HN9 > s 1 HNd 221 Pyridin-2-yl 1 222 Pyridin-3-yl 1 223 Pyridin-4-yl 1 224 Pyrimidin-2-yl 1 TABLE I Continued
Compound X Melting Isomer* No. n Point ( C) 225 Pyrimidin-4-yl 1 226 Pyrimidin-5-yl 1 227 Thien-2-y1 1 228 Thien-3-yl 1 229 2,6-di-F-C6H3- 1 230 2-n-C3H7-C6H4- 1 231 2-CF3-C6H4- 1 232 2-i-C3H7-C6H4- 1 233 2-n-C3H7O-C6H4 1 234 2-i-C3H7O-C6H4 1 235 2-n-C4H9O-C6H4- 1 236 2-I-C6H4- 1 237 2-n-C5H11 -C6H4- 1 238 2-1-C4H9O-C6H4- 1 239 2-s-C4H9O-C6H4- 1 240 2-t-C4H9O-C6H4- 1 241 2-n-C4H9-C6H4- 1 242 2-[(E)-CH3O2C.C#CH.
OCH3]-C6H4- 1 243A 3-CF3-C6H4- 0 94-97 A 243B 3-CF3-C6H4- 0 gum B 244 2-CH3O-4-CH3-C6H3 1 245 2,4-di-CH3-C6H3- 1 246 2,4,6-tri-CH3-C6H2- 1 247 2,6-di-CH3-C6H3- 1 248 2-F-6-CH30-C6H3- 1 249 2-CH3-4-C1-C6H3- 1 250 C6F5- 1 251 3,4-methylenedioxy-C6H3- 1 252 3,4-di-Cl-C6H3- 1 TABLE I Continued
Compound X Melting Isomer No. n Point ( C) 253 2-CH3O-4-F-C6H3 1 254 3,4-di-CH3-C6H3- 1 255 2,3,5-tri-CH3-C6H2- 1 256 2,4-di-F-C6H3- 1 257 2,4-di-Cl-C6H3- 1 258 3,4,5-tri-CH3-C6H2- 1 259 3-cyanopyridin-2-yl 0 260 5-CF3-pyridin-2-yl 0 261 2-CH3-pyridin-3-yl 0 262 2-Cl-pyridin-3-yl 0 263 2-CH3O-pyridin-4-yl 0 264 5-Br-pyrimidin-2-yl 0 265 5-F-pyrimidin-2-yl 0 266 4-Cl-pyrimidin-2-yl 0 267 2-phenylpyrimidin-5-yl 0 268 6-Cl-pyrazin-2-yl 0 269 6-Cl-pyridazin-3-yl 0 270 3-cyanopyridin-2-yl 1 271 5-CF3-pyridin-2-yl 1 272 2-CH3-pyridin-3-yl 1 273 2-Cl-pyridin-3-yl 1 274 2-CH30-pyridin-4-yl 1 275 5-Br-pyrimidin-2-yl 1 276 5-F-pyrimidin-2-yl 1 277 4-Cl-pyrimidin-2-yl 1 278 2-phenylpyrimidin-5-yl 1 279 6-Cl-pyrazin-2-yl 1 280 6-Cl-pyridazin-3-yl 1 281 2-[2-[(z)-CH3O2C.C=N.OCH3]- C6H4 1 * This refers to the geometry about the carbon-nitrogen
bond. Isomer A is the less polar of the two isomers on
silica gel under the conditions described in Example 1.
TABLE II
Table II comprises 281 compounds of the general structure above with all the values of X and n listed in Table I.
That is, compounds numbers 1 to 281 of Table II are the same as those of Table I except that the 3- and 5-substituents of the 1,2,4-triazine ring in Table I are reversed in Table II.
TABLE III
Table III comprises 281 compounds of the general structure above with all the values of X and n listed in Table I.
That is, compounds numbers 1 to 281 of Table III are the same as those of Table I except that the triazine ring is a 3,5-disubstituted 1,2,4-triazine in Table I and a 2, 4-disubstituted 1,3,5-triazine in Table III.
Compound x n Melting Isomer* No. Point (OC) 175 2-CH3-C6H5 1 gum (Z) 281 2-[tZ)-CH302C.C=N.OCH3l- C6H4 1 gum (z) This refers to the probable geometry about the carbon-nitrogen bond.
The compounds of the invention of formula (I) lequivalent to (IA) when W is the group CH302C.C-N.OCH3] can be prepared by the steps shown in Schemes I, II and
III. In these Schemes, X1 is an optionally substituted aromatic or heteroaromatic ring or a group which can be converted into such a ring;W is CH302C.C-N.OCH3 or a group that can be transformed into CH302C.C=N.OCH3 using methods previously described such as in EP-A-0254426; z and z2 (which may be the same or different) are leaving groups (such as halogen or CH3SO2-), zl being the leaving group which is more readily displaced if (a) both Z and z2 are present in the same compound or (b) if zl and z2 are both present in different compounds of a coupling reaction; T is hydrogen or a metal (such as sodium) and any two of K, L and M are nitrogen and the other is CY (or a group that can be converted into CY).The reactions shown in Schemes I-III are performed either in a suitable solvent or without a solvent, and at a suitable temperature.
Thus compounds of the invention of formula (IA, n=O) can be prepared by treatment of substituted triazines of general formula (III) with phenols of formula (II) (wherein W is as defined above and T is hydrogen) in the presence of a base (such as potassium carbonate) (Scheme I).
Alternatively, compounds of formula (IA, n=0) can be prepared by treatment of substituted triazines of general formula (III) with phenolate salts of formula (II) (wherein W is as defined above and T is a metal, such as sodium).
Scheme I
Compounds of the invention of formula [(IA, n=1): W is the group CH302C.C-N.OCH3] can be prepared by two successive reactions of the Ullmann type, using appropriately functionalised benzene and triazine intermediates. The pathways shown in Schemes II and III illustrate that the order of the steps by which these benzene and triazine units are assembled can be varied.
For example, compounds of formula (IA, n=1) can be prepared from compounds of formula (IV) by treatment with phenols of formula (V), wherein T is hydrogen, in the presence of a base (such as potassium carbonate).
Alternatively, compounds of formula (IA, n=1) can be prepared from compounds of formula (IV) by treatment with phenolate salts of formula (V), wherein T is a metal (such as sodium) (Scheme II).
Compounds of formula (IV) can be prepared by treatment of compounds of formula (VI) with phenols of formula (II), wherein T is hydrogen, in the presence of a base (such as potassium carbonate). Alternatively, compounds of formula (IV) can be prepared by treatment of compounds of formula (VI) with phenolate salts of formula (II), wherein T is a metal (such as sodium).
Compounds of formula (IA, n=l) can also be prepared by treatment of compounds of formula (VII) with phenols of formula (II), wherein T is hydrogen, in the presence of a base (such as potassium carbonate). Alternatively, compounds of formula (IA, n=1) can be prepared by treatment of compounds of formula (VII) with phenolate salts of formula (II), wherein T is a metal (such as sodium) (Scheme III).
Compounds of formula (VII) can be prepared by treatment of triazines of formula (VIII) with compounds of formula (V), wherein T is hydrogen, in the presence of a base (such as potassium carbonate). Alternatively, compounds of formula (VII) can be prepared by treatment of triazines of formula (VIII) with compounds of formula (V), wherein T is a metal (such as sodium).
In some instances it is advantageous to use intermediates (IV) wherein z2 is the group 2-W-C6H4O, this group functioning as the leaving group on reaction with the compound (V). These intermediates (IV) wherein z2 is 2-W-C6E4O may be prepared by treatment of triazines (VI) with an excess of compound (II). Similarly, intermediates (VII) in which Z is XO may be used, the group XO functioning as the leaving group on reaction with the phenol or phenolate (II). These intermediates (VII) wherein Z is XO may be prepared by treatment of triazines (VIII) with an excess of compound (V).
Scheme II
Scheme III
The last stage of the synthesis of the compounds of the invention may therefore be one of the following:
(i) construction of the group CH3O2C.C=N.OCH3 [in which
case the group W in the compounds (II) and (IA)
represents an appropriate precursor to the group
CH3O2C.C=N.OCH3 during the coupling reaction shown
in Scheme I]; or
(ii) the final coupling reactions shown in Schemes I-III
[in which case the group W in the intermediate (II) represents the group CH302C.C=N.OCH3]; or (iii) modification to the group X1, either to convert it
into an aromatic or heteroaromatic ring or, if it is
already such a ring, to modify a substituent on it;;
or
(iv) removal of a substituent (such as halogen) from the
triazine ring of (IA) to afford a triazine wherein
any two of K, L and M are nitrogen and the other is
CH.
Triazines of formulae (III), (VI) and (VIII) and compounds of formula (V) can be prepared by standard methods described in the chemical literature. Compounds of formula (II) can either be prepared by standard methods described in the chemical literature, or when W is Cu302C.C=N.OCH3, can be prepared by methods described in
EP-A-0254426.
In a further aspect, the invention provides processes as herein described for preparing the compounds of the invention.
The compounds of the invention are active fungicides and may be used to control one or more of the following pathogens:
Pyricularia oryzae on rice.
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. coffee, pears, apples, peanuts, vegetables and ornamental plants.
Erysiphe graminis (powdery mildew) on barley and wheat 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.
Helminthosporium spp., Rhynchosporium spp., Septoria spp.,
Pyrenophora spp., Pseudocercosporella herpotrichoides and
Gaeumannomyces graminis on cereals.
Cercospora arachidicola and Cercosporidium personata 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.
Alternaria spp. on vegetables (e.g. cucumber), oil-seed rape, apples, tomatoes and other hosts.
Venturia inaequalis (scab) on apples.
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.
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 other Rhizoctonia species on various hosts such as wheat and barley, vegetables, cotton and turf.
Some of the compounds show a broad range of activities against fungi in vitro. They may also have activity against various post-harvest diseases of fruit (e.g. Penicillium digitatum and italicum and Trichoderma virile on oranges, Gloeosporium musarum on bananas and
Botrytis cinerea on grapes).
Further, some of the compounds may be active as seed dressings against pathogens including Fusarium spp.,
Septoria spp., Tilletia spp., (bunt, a seed-borne disease of wheat), Ustilago spp. and Helminthosporium spp. on cereals, Rhizoctonia solani on cotton and Pyricularia oryzae on rice.
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.
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.
The term "plant" as used herein includes seedlings, bushes and trees. Furthermore, the fungicidal method of the invention includes preventative, protectant, prophylactic 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 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.
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 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 distribution, adhesive power and resistance to rain on treated surfaces, the different compositions can be better adapted for var.ious utilities.
The invention compounds can be used as mixtures with fertilisers (e.g. nitrogen-, potassium- or phosphoruscontaining fertilisers). Compositions comprising only granules of fertiliser incorporating, for example coated with, the compound 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 triisopropyl- naphthalene 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 10-85%, for example 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 0.00058 or 0.01% 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.
A fungicidal compound which may be present in the composition of the invention may be one which is capable of combating ear diseases of cereals (e.g. wheat) such as
Septoria, Gibberella and Helminthosporium spp., seed and soil-borne diseases and downy and powdery mildews on grapes and powdery mildew and scab on apple, etc. By including another fungicide, the composition can have a broader spectrum of 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 (RS)-1-aminopropylphosphonic acid, (RS)-4 (4-chlorophenyl )-2-phenyl-2-(1H-1,2,4-triazol-1-yl- methyl)butyronitrile, (Z)-N-but-2-enyloxymethyl-2-chloro- 2',6'-diethylacetanilide, 1-(2-cyano-2-methoxyiminoacetyl)-3-ethyl urea, 1-[(2RS,4RS;;2RS,4RS)-4-bromo-2 (2,4-dichlorophenyl)tetrahydrofurfuryl]-lH-1,2,4-tri- azole, 3-(2,4-dichlorophenyl)-2-(lH-1,2,4-triazol-1-yl)- quinazolin-4(3H)-one, 3-chloro-5-ethylsulphinylthiophene2,4-dicarbonitrile, 4-bromo-2-cyano-N,N-dimethyl-6-tri fluoromethylbenzimidazole-1-sulphonamide, 5-ethyl-5,8 dihydro-8-oxo(1,3)-dioxolo(4,5-g)quinoline-7-carboxylic acid, a-[N-(3-chloro-2,6-xylyl)-2-methoxyacetamidoi- r-butyrolactone, aldimorph, anilazine, benalaxyl, benomyl, biloxazol, binapacryl, bitertanol, blasticidin S, bupirimate, buthiobate, captafol, captan, carbendazim, carboxin, chlorbenz-thiazone, chloroneb, chlorothalonil, chlorozolinate, copper containing compounds such as copper oxychloride, copper sulphate and Bordeaux mixture, cycloheximide, cymoxanil, cyproconazole, cyprofuram, di-2-pyridyl disulphide l,l'-dioxide, dichlofluanid, dichlone, diclobutrazol, diclomezine, dicloran, difenoconazole, dimethamorph, dimethirimol, diniconazole, dinocap, ditalimfos, dithianon, dodemorph, dodine, edifenphos, etaconazole, ethirimol, ethyl (Z)-N-benzyl N-( [methyl-(methylthioethylideneamino-oxycarbonyl )- aminolthio)-ss-alaninate, etridiazole, fenapanil, fenarimol, fenfuram, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, flutolanil, flutriafol, flusilazole, folpet, fosetyl-aluminium, fuberidazole, furalaxyl, furconazole-cis, guazatine, hexaconazole, hydroxyisoxazole, imazalil, imibenconazole, iprobenfos, iprodione, isoprothiolane, kasugamycin, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, methfuroxam, metsulfovax, myclobutanil, N-(4-methyl-6-prop-lynylpyrimidin-2-yl)aniline, neoasozin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, organomercury compounds, oxadixyl, oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, phthalide, polyoxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, prothiocarb, pyrazophos, pyrifenox, pyroquilon, pyroxyfur, pyrrolnitrin, quinomethionate, quintozene, SSF-109, streptomycin, sulphur, tebuconazole, techlofthalam, tecnazene, tetraconazole, thiabendazole, thiophanate-methyl, thiram, tolclofos-methyl, triacetate salt of 1,1'-iminodi(octa-methylene)diguanidine, triadimefon, triadimenol, triazbutyl, tricyclazole, tridemorph, triflumizole, triforine, validamycin A, vinclozolin, zarilamid and zineb.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.
Suitable insecticides which may be incorporated in the composition of the invention include buprofezin, carbaryl, carbofuran, carbosulfan, chlorpyrifos, cycloprothrin, demeton-s-methyl, diazinon, dimethoate, ethofenprox, fenitrothion, fenobucarb, fenthion, formothion, isoprocarb, isoxathion, monocrotophos, phenthoate, pirimicarb, propaphos and XMC.
Plant growth regulating compounds are compounds which control weeds or seedhead, formation, or selectively control the growth of less desirable plants (e.g.
grasses).
Examples of suitable plant growth regulating compounds for use with the invention compounds are 3,6-dichloropicolinic acid, 1-(4-chlorophenyl)-4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylic acid, methyl-3,6-dichloroanisate, abscisic acid, asulam, benzoylprop-ethyl, carbetamide, daminozide, difenzoquat, dikegulac, ethephon, fenpentezol, fluoridamid, glyphosate, glyphosine, hydroxybenzonitriles (e.g. bromoxynil), inabenfide, isopyrimol, long chain fatty alcohols and acids, maleic hydrazide, mefluidide, morphactins (e.g.
chlorfluoroecol), paclobutrazol, phenoxyacetic acids (e.g.
2,4-D or MCPA), substituted benzoic acid (e.g. triiodobenzoic acid), substituted quaternary ammonium and phosphonium compounds (e.g. chloromequat, chlorphonium or mepiquatchloride), tecnazene, the auxins (e.g.
indoleacetic acid, indolebutyric acid, naphthylacetic acid or naphthoxyacetic acid), the cytokinins (e.g.
benzimidazole, benzyladenine, benzylaminopurine, diphenylurea or kinetin), the gibberellins (e.g. GA3, GA4 or GA7) and triapenthenol.
The following Examples illustrate the invention. In the Examples, the term 'ether' refers to diethyl ether, anhydrous magnesium sulphate was used to dry solutions, and solutions were concentrated under reduced pressure.
Reactions involving air- or water-sensitive intermediates 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. NMR data are selective; no attempt is made to list every absorption in all cases. 1H NMR spectra were recorded at 270 MHz using
CDCl3-solutions.The following abbreviations are used:
DMF = N,N-dimethylformamide NMR = nuclear magnetic resonance
IR = infrared
GC = Gas chromatography s = singlet m = multiplet mp = melting point ppm = parts per million
EXAMPLE 1
This Example illustrates the preparation of (E)- and (Z)-methyl O-methyl 2-[(5-(3-trifluoromethylphenyl)-1,2,4- triazin-3-yloxy)phenyl]oximinoacetate (Compounds Nos 243B and 243A, respectively, of Table I).
To a solution of methyl (2-hydroxybenzoyl)formate (0.82g, 4.56 mmol) in dry methanol (20ml) was added
O-methylhydroxylamine hydrochloride (0.76g, 9.11 mmol).
The resulting mixture was heated at reflux for 6 hours, cooled and evaporated to dryness to afford a light yellow paste. The paste was dissolved in ethyl acetate (200 ml) and washed with water. The organic layer was dried, filtered and evaporated to give a light yellow oil (0.65g) which partially crystallised on standing. Trituration with hexane-ether and filtration gave (E)-methyl O-methyl 2-(2-hydroxyphenyl)oximinoacetate (0.2g, 21%) as a white -1 1 powder, mp 115-117 C; IR max (nujol) 3399, 1724cm ; 1H NMR 6 3.90(3H,s); 4.15(3H,s); 6.20(1H,s); 6.95-7.05(2H,m); 7.22-7.30(1H,m); 7.32-7.42(1H,m) ppm.Evaporation of the filtrate gave (Z)-methyl 0-methyl 2-(2-hydroxyphenyl)oximinoacetate (0.34g, 36%) as a yellow oil; IR max (film) 2945, 1744 cm 1H H NMR 6 3.86(3H,s); 3.92(3H,s); 6.75-6.96(3H,m); 7.16-7.25(1H,m); 9.75(1H,s) ppm. The (E)-isomer (100mg, 0.478 mmol) was stirred with triphenylbismuth diacetate (0.32g, 0.574 mmol) and a catalytic amount of copper bronze in dry dichloromethane (5ml) at room temperature. After stirring overnight, the reaction mixture was further diluted with dichloromethane, filtered and evaporated to give a cloudy yellow oil (0.18g).GC analysis showed the presence of (E)-methyl
O-methyl 2-(phenoxyphenyl)oximinoacetate and none of the corresponding (z)-isomer. Chromatography on silica gel (eluent ether-hexane, 1:3) afforded pure (E)-methyl
O-methyl 2-(2-phenoxyphenyl)oximinoacetate (0.07g), mp 108-1100C, identical with an authentic sample (see
EP-A-0254426). In another preparation, chromatography of the crude mixture of (E)- and (Z)-methyl O-methyl 2-(2-hydroxyphenyl)oximinoacetate on silica gel gave a mixture containing predominantly the (Z)-isomer.
To a stirred solution of (Z)-methyl O-methyl 2- ( 2-hydroxyphenyl ) oximinoacetate (0.6g, prepared as above) in DMF (30ml) containing potassium carbonate (0.4g) at OOC was added 3-methanesulphonyl-5-(3-trifluoromethylphenyl)-1,2,4-triazine (0.87g). The reaction mixture was allowed to warm to room temperature, poured into water and then extracted with ether (x3). The organic layer was washed with brine, dilute sodium hydroxide solution (x2) and water (x3) and then dried. Evaporation of the solvent gave a yellow oil (0.46g).Chromatography on silica gel (eluent ether-hexane, 9:1) afforded (Z)-methyl O-methyl 2-l(5-(3-trifluoromethylphenyl)-1,2,4-triazin-3-yloxy) phenylioximinoacetate (0.08g, 7%), eluted first, as a yellow gum which crystallised on standing to give a solid, mp 94-970C; IR max 1737, 1543 cml 1H NMR 6 3.82(3H,s); 3.86(3H,s); 7.25-7.34(1H,m); 7.35-7.43(1H,m); 7.50-7.58(1H,m); 7.63-7.74(1H,m); 7.78-7.90(2H,m); 8.23-8.30(1H,m); 8.33-8.40(1H,m); 9.55(1H,s) ppm; and (E)-methyl 0-methyl 2-[(5-(3-trifluoromethylphenyl)-1,2,4- -triazin-3-yloxy)phenyl]oximinoacetate (0.17g, 14%), eluted second, as a yellow gum;IR max 1729, 1542 cm 1; 1H
NMR 6 3.73 (3H,s); 3.88(3H,s); 7.34-7.50(3H,m); 7.52-7.60(1H,m); 7.65-7.75(1H,m); 7.82-7.89(1H,m); 8.26-8.33(1H,m); 8.37-8.41(1H,m); 9.55(1H,s) ppm; mass spectrum m/z 432 (M ).
EXAMPLE 2 This Example illustrates the preparation of (Z)-methyl O-methyl 2-[(6-(2-methylphenoxy)-1,3,5-triazin- 2-yloxy)phenyl]oximinoacetate and (Z,Z)-2,4-bis-[2- -(methoxycarbonyl O-methyloximino)phenoxy]-1,3,5-triazine (Compounds Nos. 175 and 281, respectively, of Table III).
To a solution of 2,4-dichloro-1,3,5-triazine (1.88g) in dry acetonitrile (150ml) at OOC was added potassium carbonate (1.73g) and (Z)-methyl O-methyl 2-(2-hydroxyphenyl)oximinoacetate (2.61g, prepared as described in
Example 1). Caesium fluoride (1.91g) and a catalytic amount of 18-crown-6 were added the resulting mixture was stirred at room temperature overnight. The reaction mixture was filtered and evaporated to give an oil.
Chromatography on silica gel (eluent ether-hexane, 1:1) gave a single stereoisomer, assumed to be the (Z)-isomer, of methyl O-methyl 2-[(6-chloro-1,3,5-triazin-2-yloxy)- phenyl]oximinoacetate as a white powder (2.4g, 60%); mp 112-1130C; IR max 1728 cm 1 1H NMR # 3.85(3H,s); 3.86(3H,s); 7.17-7.23(1H,m); 7.34-7.43(1H,m); 7.48-7.57(1H,m); 7.70-7.76(1H,m); 8.75(1H,s) ppm; mass spectrum m/z 322 (M+ ).
2-Methylphenol (0.16g) was heated with potassium carbonate (0.21g) in DMF (20ml) for 15 minutes with stirring. (Z)-Methyl O-methyl 2-[(6-chloro-1,3,5-triazin 2-yloxy)phenyl]oximinoacetate (0.44g, prepared as described above) was added and stirring at 600C was continued for 4 hours. The reaction mixture was diluted with water and then extracted with ether. The ether layer was washed successively with brine, dilute sodium hydroxide solution and water and then dried.Filtration and evaporation gave a light yellow gum (0.31g) which was purified by chromatography (eluent ether-hexane, 6:4) to afford a single stereoisomer, assumed to be the (Z)-isomer, of methyl O-methyl 2-[(6-(2-methylphenoxy)- -1,3,5-triazin-2-yloxy)phenyl]oximinoacetate (O.llg, 20%) as a light yellow gum, IR max 1740, 1552 cm-1; 1H NMR # 2.18(3H,s); 3.79(3H,s); 3.93(3H,s); 7.04-7.11 (1H,m); 7.14-7.3B(5H,m); 7.42-7.52(4H,m); 7.72-7.78(1H,m); 8.65(1H,s) ppm; and a single symmetrical stereoisomer, assumed to be the (Z,Z)-isomer, of 2,4-bis-[2-(methoxycarbonyl O-methyloximino)phenoxy]-1,3,5-triazine (0.04g, 6%) as a gum, IR max 1738, 1555cm-1; 1H NMR b 3.81(6H,s); 3.93(6H,s); 7.13-7.20(2H,m); 7.25-7.36(2H,m); 7.43-7.49(2H,m); 7.72-7.77(2H,m); 8.66(1H,s) ppm.
EXAMPLE 3
An emulsifiable concentrate is made up by mixing and stirring the ingredients until all are dissolved.
Compound No. 243 of Table I 10%
Benzyl alcohol 30%
Calcium dodecylbenzenesulphonate 5%
Nonylphenolethoxylate (13 mole 10%
ethylene oxide)
Alkyl benzenes 45%
EXAMPLE 4
The active ingredient is dissolved in methylene dichloride and the resultant liquid sprayed on to the granules of attapulgite clay. The solvent is then allowed to evaporate to produce a granular composition.
Compound No. 243 of Table I 5%
Attapulgite granules 95%
EXAMPLE 5
A composition suitable for use as a seed dressing is prepared by grinding and mixing the three ingredients.
Compound No. 243 of Table I 50%
Mineral oil 2%
China clay 48%
EXAMPLE 6
A dustable powder is prepared by grinding and mixing the active ingredient with talc.
Compound No. 243 of Table I 5%
Talc 95%
EXAMPLE 7
A suspension concentrate is prepared by ball milling the ingredients to form an aqueous suspension of the ground mixture with water.
Compound No. 243 of Table I 40%
Sodium lignosulphonate 10%
Bentonite clay 1%
Water 49%
This formulation can be used as a spray by diluting into water or applied directly to seed.
EXAMPLE 8
A wettable powder formulation is made by mixing together and grinding the ingredients until all are thoroughly mixed.
Compound No. 243 of Table I 25%
Sodium lauryl sulphate 2%
Sodium lignosulphonate 5%
Silica 25%
China clay 43%
EXAMPLE 9
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 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. For the foliage diseases, the formulations (100 ppm active ingredient) were sprayed onto the foliage and applied to the roots of the plants in the soil. Alternatively, the compounds were applied as a foliar spray only at a concentration of lOppm or 25ppm.
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, to give a final concentration of 0.05%, was added when the sprays were applied to cereals.
For most of the tests the compound was applied to the soil (roots) and to the foliage (by spraying) one or two days before the plant was inoculated with the disease. An exception was the test on Erysiphe graminis in which the plants were inoculated 24 hours before treatment. Foliar 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 fourteen days according to the disease and environment.
Claims (4)
1. Compounds having the formula (I):
in which any two of K, L and M are nitrogen and the
other is CY wherein Y is H, halogen, C14 alkyl, C14 alkoxy, cyano, nitro or trifluoromethyl; n is O or 1
and X is an optionally substituted aromatic or
heteroaromatic ring.
2. A process for preparing the compounds according to
claim 1 as herein described.
3. A fungicidal composition comprising a fungicidally
effective amount of a compound according to claim 1
and a fungicidally acceptable carrier or diluent
therefor.
4. A method of combating fungi which comprises applying
to plants, to the seeds of plants or to the locus of
the plants or seeds, a compound according to claim 1
or a composition according to claim 3.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB909023292A GB9023292D0 (en) | 1990-10-25 | 1990-10-25 | Fungicides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB9120643D0 GB9120643D0 (en) | 1991-11-06 |
| GB2249092A true GB2249092A (en) | 1992-04-29 |
Family
ID=10684375
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB909023292A Pending GB9023292D0 (en) | 1990-10-25 | 1990-10-25 | Fungicides |
| GB9120643A Withdrawn GB2249092A (en) | 1990-10-25 | 1991-09-27 | Oxime ether fungicides |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB909023292A Pending GB9023292D0 (en) | 1990-10-25 | 1990-10-25 | Fungicides |
Country Status (1)
| Country | Link |
|---|---|
| GB (2) | GB9023292D0 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0624570A3 (en) * | 1993-05-14 | 1995-01-11 | Bayer Ag | Process for the preparation of 2-oximino acetic acid derivatives. |
| WO1995006039A1 (en) * | 1993-08-24 | 1995-03-02 | Hoechst Schering Agrevo Gmbh | Novel phenyl glyoxylic acid derivatives, processes for producing them and their use as herbicides and plant growth regulators |
| WO2000026182A1 (en) * | 1998-11-04 | 2000-05-11 | Basf Aktiengesellschaft | 2-phenoxyphenylacetic acid derivatives, method and intermediate products for the production thereof, their use, and agents containing the same for combating fungicidal pests |
| US6348471B1 (en) | 1997-07-22 | 2002-02-19 | Bayer Aktiengesellschaft | Pyrimidyl oxyphenylacetic acid derivatives |
| US6821927B1 (en) | 1999-11-17 | 2004-11-23 | Bayer Aktiengesellschaft | Hydroxamic acid derivatives |
-
1990
- 1990-10-25 GB GB909023292A patent/GB9023292D0/en active Pending
-
1991
- 1991-09-27 GB GB9120643A patent/GB2249092A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0624570A3 (en) * | 1993-05-14 | 1995-01-11 | Bayer Ag | Process for the preparation of 2-oximino acetic acid derivatives. |
| US5412149A (en) * | 1993-05-14 | 1995-05-02 | Bayer Aktiengesellschaft | Process for the preparation of 2-oximinoacetic acid derivatives |
| WO1995006039A1 (en) * | 1993-08-24 | 1995-03-02 | Hoechst Schering Agrevo Gmbh | Novel phenyl glyoxylic acid derivatives, processes for producing them and their use as herbicides and plant growth regulators |
| US6348471B1 (en) | 1997-07-22 | 2002-02-19 | Bayer Aktiengesellschaft | Pyrimidyl oxyphenylacetic acid derivatives |
| WO2000026182A1 (en) * | 1998-11-04 | 2000-05-11 | Basf Aktiengesellschaft | 2-phenoxyphenylacetic acid derivatives, method and intermediate products for the production thereof, their use, and agents containing the same for combating fungicidal pests |
| US6469195B1 (en) | 1998-11-04 | 2002-10-22 | Basf Aktiengesellschaft | 2-phenoxyphenylacetic acid derivatives, method and intermediate products for the production thereof, their use, and agents containing the same for combating fungicidal pests |
| US6821927B1 (en) | 1999-11-17 | 2004-11-23 | Bayer Aktiengesellschaft | Hydroxamic acid derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9120643D0 (en) | 1991-11-06 |
| GB9023292D0 (en) | 1990-12-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |