GB2253624A - Pyrimidine fungicides - Google Patents
Pyrimidine fungicides Download PDFInfo
- Publication number
- GB2253624A GB2253624A GB9200404A GB9200404A GB2253624A GB 2253624 A GB2253624 A GB 2253624A GB 9200404 A GB9200404 A GB 9200404A GB 9200404 A GB9200404 A GB 9200404A GB 2253624 A GB2253624 A GB 2253624A
- Authority
- GB
- United Kingdom
- Prior art keywords
- cyano
- alkyl
- compound
- compounds
- nitrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/52—Two oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- 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
- C07D409/12—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
Landscapes
- Chemical & Material Sciences (AREA)
- 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)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Compounds having the formula (I): <IMAGE> in which any two of K, L and M are nitrogen and the other is CE; X and Y are independently hydrogen, halogen, C1-4 alkyl, C3-6 cycloalkyl, C2-8 alkenyl, C2-8 alkynyl, C2-4 alkynloxl, phenyl, benzyloxy, cyano, isocyano, isothiocyanato, nitro, NR<1>R<2>, NR<1>OR<2>, N3, NHCOR<1>, NR<1>CO2R<2>, NHCONR<1>R<2>, N=CHNR<1>R<2>, NHSO2R<1>, OR<1>, OCOR<1>, OSO2R<1>, SR<1>, SOR<1>, SO2R<1>, SO2OR<1>, SO2NR<1>R<2>, COR<1>, CR<1>=NOR<2>, CHR<1>CO2R<2>, CO2R<1>, CONR<1>R<2>, CSNR<1>R<2>, CH3O2C.C:CH.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 X and Y, when ortho to one another, join to form a 5- or 6-membered aliphatic or aromatic ring optionally containing one or two oxygen, sulphur or nitrogen atoms or one, two or three nitrogen atoms; A, B, D, E, G, U and V are independently hydrogen, halogen, C1-4 alkyl, C1-4 alkoxy, cyano, nitro or trifluromethyl; and R<1> and R<2> are independently hydrogen, C1-4 alkyl, C2-8 alkenyl or phenyl, can be applied to plants or seeds for the control of fungi.
Description
FUNGICIDES
This invention relates to derivatives of 0-methyl oxyiminoacetamide 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.
According to the present invention there are provided pyrimidines having the formula (I), in which any two of K, L and M are nitrogen and the other is CE; X and Y are independently hydrogen, halogen, C14 alkyl, C3-6 cycloalkyl, C2-8 alkenyl (including C2-4 alkenyl), C2-8 alkynyl (including
C2-4 alkynyl), C2-4 alkynyloxy, phenyl, benzyloxy, cyano, isocyano, thiocyanato, isothiocyanato, nitro, NR1R2, NR1OR2, N3, NHCOR1, NR1CO2R2, NHCONR1R2, N=CHNR1R2, NHSO2R1, OR1, OCOR1, OSO2R1, SR1, SOR1, SO2R1,
SO2OR1, SO2NR1R2, COR1, CR1=NOR2, CHR1CO , CO2R2, CO2R1, CONR1R2, CSNR1R2, CH3O2C.C::CH.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 X and Y, when ortho to one another, join to form a 5- or 6-membered aliphatic or aromatic ring optionally containing one or two oxygen, sulphur or nitrogen atoms or one, two or three nitrogen atoms;A,
B, D, E, G, U and V are independently hydrogen, halogen (especially fluorine and chlorine), C1-4 alkyl (especially methyl), C1-4 alkoxy (especially methoxy), cyano, nitro or trifluoromethyl; R1 and R2 are independently hydrogen, C1-4 alkyl, C2-8 alkenyl (including C24 alkenyl) or phenyl; the aliphatic moieties of any of the foregoing being optionally substituted with one or more of halogen, cyano, OR1, SR1, NR1R2, SiR13 or
OCOR1 and the phenyl moieties of any of the foregoing being optionally substituted with one or more of halogen, C1-4 alkyl, C1-4 alkoxy, nitro or cyano; and R3 and R4 are independently hydrogen or C1-4 alkyl.
Because of the unsymmetrically substituted double bond of the oxime 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 -CONR3R4 and -OCH3 are on opposite sides of the double bond of the oxime group, are the more fungicidally active and form a preferred embodiment of the invention.
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.
Alkyl and alkynyl groups contain from 2 to 8 carbon atoms, typically 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.
Substituted aliphatic moieties include, in particular, halo(C1-4)alkyl, halo(C1 -4)alkoxy, halo(C1 4)alkylthio, CH2OR1, CH2SR1 and 12 1 2
CH2NR R , wherein R and R are H, C14 alkyl or phenyl.
Typical optional substituents of phenyl moieties are fluorine, chlorine, methyl, methoxy, nitro and cyano.
The ring containing K, L and M in formula (I) is a pyrimidine ring which may be joined to the phenoxy groups by any two of its ring carbon atoms adjacent to a ring nitrogen atom. Of particular interest are those compounds of formula (I) in which K and L are both nitrogen and M is CH.
Typically, one or both of X and Y are hydrogen. When one of X and Y is not hydrogen it is preferably attached to the 2-position of the phenyl ring.
Thus, in one aspect, the invention provides compounds of formula (I) in which K, L and M have the meanings previously given; X, which is preferably attached to the 2-position of the phenyl ring, is hydrogen, halogen (e.g. fluorine, chlorine or bromine), C1-4 alkyl (e.g. methyl or ethyl), C14 alkyl (especially methyl) substituted with halogen (e.g.
fluorine, chlorine or bromine), hydroxy, cyano, C1-4 alkoxy (e.g. methoxy) or C14 alkanoyloxy (e.g. acetoxy), C24 alkenyl (e.g. ethenyl, allyl or methylallyl), C24 alkynyl (e.g. ethynyl or propargyl), C24 alkenyloxy (e.g. allyloxy), C2-4 alkynyloxy (e.g. propargyloxy), phenyl, benzyl, cyano, isocyano, thiocyanato, isothiocyanato, nitro, amino, mono- or di(C1 4)alkylamino (e.g. methylamino or dimethylamino), formylamino, C1-4 alkanoylamino (e.g. acetamido), benzoylamino, ureido, phenylureido, C14 alkylsulphonylamino (e.g. mesylamino), phenylsulphonylamino, hydroxy, C1-4 alkoxy (e.g. methoxy or ethoxy), phenoxy, C1-4 alkanoyloxy (e.g. acetoxy),
C1-4 alkylsulphonyloxy (e.g. mesyloxy), phenylsulphonyloxy, C1-4 alkylthio (e.g. methylthio), C1-4 alkylsulphinyl (e.g. methylsulphinyl), C1-4 alkyl sulphonyl (e.g. mesyl or n-butylsulphonyl), formyl, C14 alkanoyl (e.g.
acetyl), benzoyl, hydroxyimino(C1 4)alkyl (e.g. hydroxyiminomethyl), C14 alkoxyimino(C14)alkyl (e.g. methoxyiminomethyl), carbamoyl, C14 alkylcarbamoyl (e.g. methylcarbamoyl), thiocarbamoyl or C14 alkylthiocarbamoyl (e.g. methylthiocarbamoyl), the phenyl ring of any of the foregoing being optionally substituted with halogen (e.g. fluorine or chlorine), C1-4 alkyl (e.g. methyl), C1-4 alkoxy (e.g. methoxy), nitro or cyano; and Y is halogen (e.g. fluorine or chlorine), C1-4 alkyl (e.g.
methyl), C1-4 alkoxy (e.g. methoxy), nitro, cyano or preferably, hydrogen, or X and Y, when ortho to one another, together form methylenedioxy, or together with the phenyl ring to which they are attached form a naphthalene, quinoline, benzimidazole or benzothienyl ring; and R3 and R4 are independently hydrogen or C14 alkyl.
In another aspect the invention provides compounds of the formula (I.1), in which X is hydrogen, halogen (especially chlorine), C1-4 alkyl (especially methyl), C1-4 alkoxy (especially methoxy), trifluoromethyl, cyano, thiocarbamoyl or nitro; Y is hydrogen or fluoro; and R3 and R4 are independently hydrogen or C 1-4 alkyl.
The invention is illustrated by the compounds listed in Tables I to VI which follow. Compounds 1 to 160 in Table I have the general formula (I.2) in which X and Y have the values shown in that table. Compounds 161 to 200 in Table I have the general formula (I.3) in which Ar has the values show in in that table. The compounds in Tables II, III, IV, V and VI have the general formulae (I.4), (I.5), (I.6), (I.7) and (I.8), respectively, in which Z has the values shown in those tables. Throughout the tables the
O-methyl oximinoacetamide group has the (E)-configuration, unless otherwise stated.
TABLE I
Compound X Y Compound X Y
No (see Formula (1.2)) No (see Formula (1.2))
1 H H 31 4-OCH3 H
2 2-F H 32 2-OC2H5 H
3 3-F H 33 3-(2-F-C6H4O) H
4 4-F H 34 2-OCOCH3 H
5 2-Cl H 35 2-OS02CH3 H
6 3-Cl H 36 3-(4-CH3-C6H4S020) H
7 4-Cl H 37 2-thiocyanato H
8 2-Br H 38 3-thiocyanato H
9A 2-Cyano H 39 4-thiocyanato H
9B+ 2-Cyano H 40 2-SCH3 H
10 3-Cyano H 41 3-SCH3 H
11 4-Cyano H 42 4-SCH3 H
12 2-Isocyano H 43 2-S(O)CH3 H
13 2-NO2 H 44 2-SO2CH3 H
14 3-NO2 H 45 4-SO2(CH2)3CH3 H
15 4-NO2 H 46 2-CHO H
16 2-NH2 H 47 3-CHO H
17 3-NH(CH3) H 48 4-CHO H
18 2-N(CH3)2 H 49 2-COCH3 H
19 2-NH.CHO H 50 3-COC6H5 H
20 2-NH.COCH3 H 51 2-(E)-CH=NOH H
21 3-NH.COC6H5 H 52 3-(E)-CH=NOH H
22 2-NH.CONH2 H 53 4-(E)-CH=NOH H
23 3-NH.CONH(C2H5) H 54 2-(E)-CH=NOCH3 H
24 2-NH.SO2CH3 H 55 2-(E)-C(CH3)=NOH H
25 3-NH. SO2C6H5 H 56 2-CONH2 H
26 2-OH H 57 3-CONH(CH3) H
27 3-OH H 58 4-CON(CH3)2 H
28 4-OH H 59 2-CSNH2 H
29 2-OCH3 H 60 2-CSNH(CH3) H
30 2-0(CH2)2CH3 H 61 2-CH3 H
TABLE I (Contd.)
Compound X Y Compound X Y
No (see Formula (1.2)) No (see Formula (1.2))
62 3-CH3 H 93 2-OCH3 3-OCH3 63 4-CH3 H 94 2-Cyano 5-Cl
64 2-C2H5 H 95 2-Cyano 6-Cyano
65 2-CH2F H 96 2-F 5-Cl
66 2-CH2Br H 97 3-OCH3 5-OCH3
67 2-CH2Cl H 98 3-Cyano 4-F
68 2-CH2CN H 99 2-NO2 3-OCH3
69 2-CH2OH H 100 3-OCH3 5-Cyano
70 2-CH20CH3 H 101 2-CO 2CH3 H
71 2-CH20COCH3 H 102 2-I H
72 3-CH2CN H 103 2-CF3 H
73 4-CH20H H 104 2-i-C3H7 H
74 3-CH2OCH3 H 105 2-i-C3H7O H
75 2-CH=CH2 H 106 2-F 6-F
76 2-CH2CH=CH2 H 107 2-F 4-F
77 2-C#CH H 108 2-F 3-F
78 2-CH2C#CH H 109 2-n-C3H7O H
79 3-CH2C(CH3)=CH2 H 110 2-n-C4H9O H
80 2-OCH2CH=CH2 H 111 2-CH(OH)CH3 H
81 2-OCH2C#CH H 112 2-t-C4H9 H
82 2-C6H5 H 113 2-s-C4H9 H
83 3-C6H5 H 114 2-n-C3H7 H
84 4-C6H5 H 115 2-(E)-CH=CH(CH3) H
85 2-C6H50 H 116 2-Cyano 4-OCH3 86 C6 5o H 117 2-Cyano 5-OCH3 87 4-C6H50 H 118 2-Cyano 4-Cl
88 2-(4-Cl-C6H4O) H 119 2-Cyano 5-N(C2H5)2
89 2-C6H5CH20 H 120 2-C0NH2 H
90 2-Cyano 4-Cl 121 2-C-CSi(CH3)3 H
91 2-NO2 4-F 122 2-F 5-F
92 2-Cl 4-Cl
TABLE I (Contd.)
Compound X Y Compound X Y
No (see Formula (1.2)) No (see Formula (1.2)) 123 2-(E)- 152 2-Cyano 4-NO2
CH3O2C.C=NH.OCH3 H 153 2-Cyano 6-NO2 124 3-F 5-F 154 2-Cyano 6-OC2H5 125 2-NHOH H 155 2-Cyano 4-CO2CH3 126 2-CH20CH3 H 156 2-Cyano 6 C 2C2H5 127 2-CH2CN H 157 2-Cyano 6-CH3 128 2-N3 H 158 2-Cyano C 2C6 5 129 2-Cyano 6-F 159 2-Cyano 4-OCF3 130 2-NO2 6-F 160 2-Cyano 4-Cyano 131 2-CSNH2 6-F 132 2-Cyano 3-F Compound Ar 133 2-Cyano 5-F No (see Formula (1.3)) 134 2-Cyano 3-OCH3 135 2-Cyano 6-OCH3 161 * 136 2-NO2 4-OCH3 162 * 137 2-NO2 5-OCH3 163 * 138 2-NO2 6-OCH3 164 * 139 2-CSNH2 3-OCH3 165 * 140 2-CSNH2 4-OCH3 166 * 141 2-CSNH2 5-OCH3 167 Pentafluorophenyl 142 2-CSNH2 6-OCH3 168 2,4,6-Tri-F-C6H2 143 2-Cyano 3-Cyano 169 2,3,5,6-Tetra-F-C6H 144 2-F 3-Cyano 170 2,3,6-Tri-F-C6H2 144 2-OCH3 3-Cyano 171 2,3-Di-cyano-6-F-C6H2 145 3-Cyano 6-F 172 2,6-Di-F-3-CH30-C H 146 * H 173 2,6-Di-F-4-CH3O-C6H2 147 * H 174 2,6-Di-F-3-N02-C6H2 148 * H 175 2,6-Di-F-4-N02-C6H2 149 * H 177 4,6-Di-Br-2-cyano-C6H2 150 2-Cyano 4-Br 176 2,6-Di-F-3,5-di-CH3O-C6H 151 2-Cyano 6-Br 178 3-Cyano-2,6-di-F-C6H2
TABLE I (Contd.)
Compound Ar Compound Ar
No (see Formula (I.3)) No (see Formula I.3))
179 6-Br-2-cyano-4-CH30-C6H2 190 2-Cyano-4,6-di-N02-C6 H2 180 6-Br-4-Cl-2-cyano-C6H2 191 2-Cyano-4-CH3-6-N02-C6H2 181 6-Br-2-cyano-4-N02-C6H2 192 2-Cyano-4-CH30-6-N02 -C6H2 182 3-Br-2-cyano-6-CH30-C H 193 2-Cyano-5,6-di-CH30- C6H2 183 3,5-Di-Cl-2-cyano-C6H2 194 2-Cyano-5,6-di-CH30-3-CH3-C6H 184 4,6-Di-Cl-2-cyano-C H 195 3,4-Di-Br-2-cyano-6-CH30-C6H
185 3-Br-2-cyano-4-CH30-C6H2 196 3-Br-2-cyano-6-CH3 O-4-N02-C6H 186 4-Br-2-cyano-6-N02-C6H2 197 2-Cyano-6-CH3CH20-4-N02-C6H2
187 4-Br-2-cyano-6-CH30-C6H2 198 *
188 2-Cyano-4-I-6-CH30-C H 199 *
189 2-Cyano-6-CH30-4-NO2-C H 200 2-Cyano-3,4-di-CH3-C6 H2 * These values are given later under "Chemical Formulae".
+ The 0-methyl oxyiminoacetamide group has the (Z)-configuration.
TABLE II
Table II comprises 200 compounds of the general formula (I.4) wherein
Z is X-Y-C H or Ar which have all the values listed in Table I. That is, compounds numbers 1 to 200 of Table II are the same as those of Table I except that the compounds of Table I have an N-methyl substituent on the acetamide group whereas the compounds of Table II have not.
TABLE III
Table III comprises 200 compounds of the general formula (I.5) wherein
Z is X-Y-C6H3 or Ar which have all the values listed in Table I. That is, compounds numbers 1 to 200 of Table III are the same as those of Table I except that the pyrimidine ring is 4,6-disubstituted in Table I and 2,4-disubstituted as shown in Table III.
TABLE IV
Table IV comprises 200 compounds of the general formula (I.6) wherein
Z is X-Y-C H or Ar which have all the values listed in Table I. That is, compounds numbers 1 to 200 of Table IV are the same as those of Table II except that the pyrimidine ring is 4,6-disubstituted in Table I and 2,4-disubstituted as shown in Table IV.
TABLE V
Table V comprises 200 compounds of the general formula (I.7) wherein Z is X-Y-C6H3 or Ar which have all the values listed in Table I. That is, compounds numbers 1 to 200 of Table V are the same as those of Table I except that the pyrimidine ring is 4,6-disubstituted in Table I and 2,4-disubstituted as shown in Table V, and the compounds of Table I have an
N-methyl substituent on the acetamide group whereas the compounds of Table
V have not
TABLE VI
Table VI comprises 200 compounds of the general formula (I.8) wherein
Z is X-Y-C6H3 or Ar which have all the values listed in Table I.That is, compounds numbers 1 to 200 of Table VI are the same as those of Table I except that the pyrimidine ring is 4,6-disubstituted in Table I and 2,4-disubstituted as shown in Table VI, and the compounds of Table I have an N-methyl substituent on the acetamide group whereas the compounds of
Table VI have not.
The compounds of the invention can be prepared according to the methods described in EP-A-0382375 and EP-A-0398692. The former reference shows how to prepare similar compounds, but which have a methyl ss-methoxyacrylate group attached to the phenyl ring in formula I instead of an 0-methyl oxyiminoacetamide group. The latter reference shows how to construct the oxyiminoacetamide group.
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 viride 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, 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, 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 various utilities.
The invention compounds can be used as mixtures with fertilisers (e.g.
nitrogen-, potassium- or phosphorus-containing fertilisers). Compositions comprising only granules of fertiliser incorporating, for example coated with, 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 at tapulgi te.
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 0.0005% 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-2methoxyimino-acetyl)-3-ethyl urea, 1-[(2RS,4RS;;2RS,4RS)-4-bromo-2 (2,4-dichlorophenyl)tetrahydrofurfurylj-1H-1,2,4-triazole, 3-(2,4 dichlorophenyl)-2-(lH-1,2,4-triazol-1-yl)-quinazolin-4(3H)-one, 3-chloro-4-[4-methyl-2-(1H-1,2,4-triazol-1-yl-methyl)-l,3-dioxolan-2-ylj- phenyl-4-chlorophenyl ether, 4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole-I-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- methoxyacetamido]-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 1,1'-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-oxy- carbonyl)amino]thio)--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-1ynylpyrimidin-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, thicyofen, thiophanate-methyl, thiram, tolclofos-methyl, triacetate salt of 1,1'-iminoditoctamethylene)- diguanidine, triadimefon, triadimenol, triazbutyl, tricyclazole, tridemorph, 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-di-methyl-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. triiodo-benzoic 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 using CDCl3-solutions on an instrument operating at 270 MHz, unless otherwise stated.The following abbreviations are used
NMR = nuclear magnetic resonance br = broad
MS = mass spectrum s = singlet
IR = infrared d = doublet q = quartet m = multiplet dd = doublet of doublets mp = melting point ppm = parts per million CI = chemical ionisation EI = electron ionisation
EXAMPLE 1
This Example illustrates the preparation of the carboxamide (A) (see under "Chemical Formulae") and the corresponding (Z)-isomer (Compounds Nos.
9A and 9B of Table I).
To a vigorously stirred mixture of water (20ml) and a solution of (E)-methyl 2-[2-(6-(2-cyanophenoxy)pyrimidin-4-yloxy)phenylj-3-methoxy- propenoate (3.2g, 7.94 mmol, prepared as described in Example 3 of EP-A-O 382 375) in dichloromethane (20ml) was added potassium permanganate (2.5g, 15.9 mmol) in one portion and tetra-n-hexylammonium hydrogen sulphate (200mg). The reaction mixture was stirred overnight (16 hours) and then filtered. The filter was washed through with ether and water and then the combined liquid phases were extracted with ether (x3). The ether extracts were washed with water (x3) and brine (xl), dried, filtered and evaporated. The residue was chromatographed (eluent dichloromethaneacetone, 98:2).Recrystallisation (ether-pentane) of the major component afforded methyl 2-[2-(6-(2-cyanophenoxy)pyrimidin-4-yloxy)phenyl]keto acetate (2.105g, 71%) as a white crystalline solid, mp 96-970C; 1H NMR (CDC13) # 3.83(3H,s), 6.61(1H,s), 7.27-7.47(4H,m), 7.67-7.76(3H,m), 8.02(1H,dd), 8.39(1H,s) ppm; IR maxima 2234(CN), 1743(C0, ester), 1688(CO, ketone)cm-1.
To a solution of the ketoester (500mg, 1.33 mmol) in dry methanol (lOml) was added methoxylamine hydrochloride (112mg, 1.33 mmol). After stirring at room temperature for 4 hours, more methoxylamine hydrochloride (66mg) was added and stirring was continued overnight. The complete disappearance of the starting ketoester was demonstrated by loss of the peak at 1688 cm in the infrared spectrum.The reaction mixture was worked up and then repeatedly chromatographed (eluent dichloromethaneacetone mixtures) to afford, in order of increasing polarity, (Z)-methyl 0-methyl-2-[2-(6-(2-cyanophenoxy)pyrimidin-4-yloxy)phenyl]oxyiminoacetate as a white foam (75mg, 14%); H NMR (CDCl3) 8 3.78(3H,s), 3.98(3H,s), 6.50(1H,s), 7.18(1H,d), 7.31-7.41(3H,m), 7.48-7.54(1H,m), 7.66-7.81(3H,m), -1 + 8.38(1H,s) ppm; IR maxima 2242 (CN), 1741(CO) cm ;MS (EI) 404 (M ) and (CI) 422 (M+ NH4+), 405 (MH+); and (E)-methyl 0-methyl-2-[2-(6-(2-cyanophenoxy)pyrimidin-4-yloxy)phenyl]oxyiminoacetate as an off-white solid (403mg, 75%), mp 125-1270C; 1H NMR (CDCl3) 8 3.81(3H,s), 3.94(3H,s), 6.51(1H,s), 7.27-7.43(4H,m), 7.49-7.55(1H,m), 7.65-7.73(3H,m), 8.39(1H,s) -1 (M+); (CI) 422 + ppm; IR maxima 2234 (CN), 1728 (CO) cm ; MS (EI) 404 (M ); (Cl) 422 (M+ NH4+), 405 (MH+).
(E)-Methyl 0-methyl-2-[2-(6-(2-cyanophenoxy)pyrimidin-4-yloxy)phenylj- oxyiminoacetate (403 mg) was dissolved in a solution of methylamine in industrial methylated spirits (0.5ml, ca. 33% w/w) and the resulting mixture was stirred at room temperature for 8 hours, then allowed to stand overnight. The mixture was poured into water and extracted with ether.
The extracts were washed with water, dried, concentrated and then chromatographed twice using first ether and then 10% acetone in dichloromethane as eluants to give, in order of increasing polarity, the title compound (A) (295mg, 73% yield) as a clear gum which crystallised from a mixture of ether and pentane to give a white solid, mp 146-70C; 1H
NMR (CDC13) 6 2.88(3H,d), 3.82(3H,s), 6.52(1H,s), 6.70(1H,br q), 7.24-7.53(6H,m), 7.70(2H,m), 8.38(1H,s) ppm; IR maxima 3381, 2234, 1671, -l + and 1563 cm ; MS (EI) 403 (M ) and (Cl) 404 (MH+), 421 (M+NH4 ); and 4-(2-cyanophenoxy)-6-methylaminopyrimidine (22mg) as an off-white solid, mp 152-3 C.
Under similar conditions (3.5 hours reaction time), (Z)-methyl O-methyl-2-[2-(6-(2-cyanophenoxy)pyrimidin-4-yloxy)phenyl]oxyiminoacetate gave the (Z)-isomer corresponding to (A) (65% yield) as a clear gum, 1H NMR (CDCl3) s 2.87(3H,d), 3.94(3H,s), 6.42(1H, br q), 6.52(1H,s), 7.20(1H,d), 7.35(3H,m), 7.50(1H,m), 7.70(3H,m), 8.38(1H,s) ppm; MS (EI) 403 (M+).
The following are examples of compositions suitable for agricultural and horticultural purposes which can be formulated from the compounds of the invention. Such compositions form another aspect of the invention.
Percentges are by weight.
EXAMPLE 2
An emulsifiable concentrate is made up by mixing and stirring the ingredients until all are dissolved.
Compound No. 9A of Table I 10%
Benzyl alcohol 30%
Calcium dodecylbenzenesulphonate 5%
Nonylphenolethoxylate (13 mole ethylene oxide) 10%
Alkyl benzenes 45%
EXAMPLE 3
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. 9A of Table I 5%
Attapulgite granules 95%
EXAMPLE 4
A composition suitable for use as a seed dressing is prepared by grinding and mixing the three ingredients.
Compound No. 9A of Table I 50%
Mineral oil 2%
China clay 48%
EXAMPLE 5
A dustable powder is prepared by grinding and mixing the active ingredient with talc.
Compound No. 9A of Table I 5%
Talc 95%
EXAMPLE 6
A suspension concentrate is prepared by ball milling the ingredients to form an aqueous suspension of the ground mixture with water.
Compound No. 9A 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 7
A wettable powder formulation is made by mixing together and grinding the ingredients until all are thoroughly mixed.
Compound No. 6 of Table I 25%
Sodium lauryl sulphate 2%
Sodium lignosulphonate 5%
Silica 25%
China clay 43%
EXAMPLE 8
The compounds were tested against a variety of foliar fungal diseases of plants. The technique employed was as follows.
The plants were grown in John Innes Potting Compost (No 1 or 2) in 4 cm diameter minipots. The test compounds were formulated either by bead milling with aqueous Dispersol T or as a solution in acetone or acetone/ethanol which was diluted to the required concentration immediately before use. The formulations (100 ppm active ingredient) were sprayed on to the foliage or applied to the roots of the plants in the soil. The sprays were applied to maximum retention and the root drenches to a final concentration equivalent to approximately 40 ppm a.i. in dry soil. Tween 20 was added to give a final concentration of 0.05% when the sprays were applied to cereals.
For most of the tests the compounds were applied to the soil (roots) or to the foliage (by spraying) one or two days before the plant was inoculated with the disease. 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 zoosporangial suspensions onto the leaves of test plants. After inoculation, the plants were put into an appropriate environment to allow infection to proceed and then incubated until the disease was ready for assessment. The period between inoculation and assessment varied from four to fourteen days according to the disease and environment.
The disease level present (i.e. leaf area covered by actively sporulating disease) on each of the treated plants was recorded using the following assessment scale: 0 = 0% disease present 20 = 10.1-20% disease present
1 = 0.1-1% disease present 30 = 20.1-30% disease present
3 = 1.1-3% disease present 60 = 30.1-60% disease present
5 = 3.1-5% disease present 90 = 60.1-100% disease present 10 = 5.1-10% disease present
Each assessment was then expressed as a percentage of the level of disease present on the untreated control plants. This calculated value is referred to as a POCO (Percentage of Control) value.An example of a typical calculation is as follows:
Disease level on untreated control = 90
Disese level on treated plant = 30
POCO = disease level on treated plant x 100 = 30 x 100 = 33.3
disease level on untreated control 90
This calculated POCO value is then rounded to the nearest of the values in the 9-point assessment scale shown above. In this particular example, the POCO value would be rounded to 30. If the calculated POCO falls exactly mid-way between two of the points, it is rounded to the lower of the two values.
The results displayed in Table III below represent these rounded POCO values.
TABLE III
Compound
No of Table I Pr Egt Sn Po Tc Vi Pv Pil
9A 0 0 0 0 0 0 0 0
9B 90a 20a 90a 60a 90a 60a 90a 90a
a = 10 ppm foliar spray only.
Key to diseases
Pr Puccinia recondita
Egt Erysiphe graminis tritici
Sn Septoria nodorum
Po Pyricularia oryzae
Tc Thanetophorus cucumeris
Vi Venturia inaequalis
Pv Plasmopara viticola
Pil Phytophthora infestans lycopersici
CHEMICAL FORMULAE (in description)
TABLE I
TABLES II TO IV
EXAMPLE 1
* X of Compound No 146 is
X X of Compound No 147 is
X X of Compound No 148 is
X X of Compound No 149 is
* Ar of Compound No 161 is
Ar of Compound No 162 is
*
Ar of Compound No 163 is
* Ar of Compound No 164 is
Ar of Compound No 165 is
*
Ar of Compound No 166 is
Ar of Compound No 198 is
Ar of Compound No 199 is
Claims (4)
- CLAIMS 1. A compound having the formula (I):in which any two of K, L and M are nitrogen and the other is CE; X and Y are independently hydrogen, halogen, C1-4 alkyl, C3-6 cycloalkyl, C2-8 alkenyl, C2-8 alkynyl, C2-4 alkynyloxy, phenyl, benzyloxy, cyano, isocyano, isothiocyanato, nitro, NR1R2, NR1OR2, N3, NHCOR1, NR1CO2R2, NHC0NR12 N=CHNR1R2, NHSO2R1, OR1, OCOR1, OSO2R1, SR1, SOR1, SO2R1, SO2OR1, SO2NR1R2, COR1, CR1=NOR2, CHR1CO2R2, CO2R1, CON1R2, CSNR1R2, S020R ,S02NR R , COR1 , , C02R , C02R , C0NR R , CSNR R CH3O2C.C::CH.OCH3, 1-(imidazol-1-yl), vinyl, a 5-membered heterocyclic ring containing one, two or three nitrogen heteroatoms, or a 5- or6-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 X and Y, when ortho to one another, join to form a 5- or 6-membered aliphatic or aromatic ring optionally containing one or two oxygen, sulphur or nitrogen atoms or one, two or three nitrogen atoms;A, B, D, E, G, U and V are independently hydrogen, halogen, C1-4 alkyl, C1-4 alkoxy, cyano, nitro or trifluoromethyl; R1 and R2 are independently hydrogen, C1-4 alkyl, C2-8 alkenyl or phenyl; the aliphatic moieties of any of the foregoing being optionally substituted with one or more of halogen, cyano, OR SR1, NR1R2, SiR13 or OCOR1 and the phenyl moieties of any of the 3 foregoing being optionally substituted with one or more of halogen, C1-4 alkyl, C1-4 alkoxy, nitro or cyano; and R3 and R4 are independently hydrogen or C1-4 alkyl.
- 2. A process for preparing a compound according to claim 1 as herein defined.
- 3. A fungicidal composition comprising, as an active ingredient, a compound as defined in claim 1 and a fungicidally acceptable carrier or diluent therefor.
- 4. A process for combating fungi which comprises applying to plants or seeds, or to their locus, a compound as claimed in claim 1 or a composition as claimed in claim 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB919102036A GB9102036D0 (en) | 1991-01-30 | 1991-01-30 | Fungicides |
| GB919112425A GB9112425D0 (en) | 1991-06-10 | 1991-06-10 | Fungicides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB9200404D0 GB9200404D0 (en) | 1992-02-26 |
| GB2253624A true GB2253624A (en) | 1992-09-16 |
Family
ID=26298355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9200404A Withdrawn GB2253624A (en) | 1991-01-30 | 1992-01-09 | Pyrimidine fungicides |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2253624A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995024396A1 (en) * | 1994-03-07 | 1995-09-14 | Zeneca Limited | Pyrimidine fungicides |
| US5506254A (en) * | 1994-07-06 | 1996-04-09 | Kirstgen; Reinhard | Pyrazoyly derivatives and their use |
| WO1997000611A1 (en) * | 1995-06-22 | 1997-01-09 | Basf Aktiengesellschaft | Long shelf-life aqueous fungicidal formulation |
| WO1998021189A1 (en) * | 1996-11-11 | 1998-05-22 | Bayer Aktiengesellschaft | Halogen pyrimidinyl aryl (thio)ethers as pesticides |
| WO1998055461A1 (en) * | 1997-06-03 | 1998-12-10 | Bayer Aktiengesellschaft | Fluoromethoximino compounds |
| US6031110A (en) * | 1993-02-23 | 2000-02-29 | Basf Aktiengesellschaft | Ortho-substituted 2-methoxyiminophenyl-N-methylacetamides |
| WO2000071504A1 (en) * | 1999-05-25 | 2000-11-30 | Bayer Aktiengesellschaft | Method of producing methoxyimino acetic amide |
| WO2000078732A1 (en) * | 1999-06-18 | 2000-12-28 | Bayer Aktiengesellschaft | Halopyrimidines |
| US6559136B1 (en) * | 1998-11-20 | 2003-05-06 | Bayer Aktiengesellschaft | Fungicidal active substance combinations |
| WO2003077655A1 (en) * | 2002-03-15 | 2003-09-25 | Bayer Healthcare Ag | Controlling parasites on animals by using halogen pyrimidines |
| EP1506711A2 (en) * | 1998-11-20 | 2005-02-16 | Bayer CropScience AG | Fungicidal combinations of active agents |
| US7838464B2 (en) | 2002-11-12 | 2010-11-23 | Basf Aktiengesellschaft | Method for yield improvement in glyphosate-resistent legumes |
| US8217064B2 (en) | 2007-12-20 | 2012-07-10 | Envivo Pharmaceuticals, Inc. | Tetrasubstituted benzenes |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0398692A2 (en) * | 1989-05-17 | 1990-11-22 | SHIONOGI SEIYAKU KABUSHIKI KAISHA trading under the name of SHIONOGI & CO. LTD. | Alkoxyiminoacetamide derivatives and their use as fungicides |
-
1992
- 1992-01-09 GB GB9200404A patent/GB2253624A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0398692A2 (en) * | 1989-05-17 | 1990-11-22 | SHIONOGI SEIYAKU KABUSHIKI KAISHA trading under the name of SHIONOGI & CO. LTD. | Alkoxyiminoacetamide derivatives and their use as fungicides |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6031110A (en) * | 1993-02-23 | 2000-02-29 | Basf Aktiengesellschaft | Ortho-substituted 2-methoxyiminophenyl-N-methylacetamides |
| WO1995024396A1 (en) * | 1994-03-07 | 1995-09-14 | Zeneca Limited | Pyrimidine fungicides |
| US5506254A (en) * | 1994-07-06 | 1996-04-09 | Kirstgen; Reinhard | Pyrazoyly derivatives and their use |
| WO1997000611A1 (en) * | 1995-06-22 | 1997-01-09 | Basf Aktiengesellschaft | Long shelf-life aqueous fungicidal formulation |
| CN1117084C (en) * | 1996-11-11 | 2003-08-06 | 拜尔公司 | Halogen pyrimidinyl aryl (thio) ethers as pesticides |
| WO1998021189A1 (en) * | 1996-11-11 | 1998-05-22 | Bayer Aktiengesellschaft | Halogen pyrimidinyl aryl (thio)ethers as pesticides |
| WO1998055461A1 (en) * | 1997-06-03 | 1998-12-10 | Bayer Aktiengesellschaft | Fluoromethoximino compounds |
| US6632817B2 (en) | 1997-06-03 | 2003-10-14 | Bayer Ag | Fluoromethoximino compounds |
| US6306855B1 (en) * | 1997-06-03 | 2001-10-23 | Bayer Aktiengesellschaft | Fluoromethoximino compounds |
| EP1506711A2 (en) * | 1998-11-20 | 2005-02-16 | Bayer CropScience AG | Fungicidal combinations of active agents |
| US6559136B1 (en) * | 1998-11-20 | 2003-05-06 | Bayer Aktiengesellschaft | Fungicidal active substance combinations |
| EP1506711A3 (en) * | 1998-11-20 | 2005-04-27 | Bayer CropScience AG | Fungicidal combinations of active agents |
| US6660872B1 (en) | 1999-05-25 | 2003-12-09 | Bayer Aktiengesellschaft | Method of producing methoxyimino acetic amide |
| WO2000071504A1 (en) * | 1999-05-25 | 2000-11-30 | Bayer Aktiengesellschaft | Method of producing methoxyimino acetic amide |
| WO2000078732A1 (en) * | 1999-06-18 | 2000-12-28 | Bayer Aktiengesellschaft | Halopyrimidines |
| WO2003077655A1 (en) * | 2002-03-15 | 2003-09-25 | Bayer Healthcare Ag | Controlling parasites on animals by using halogen pyrimidines |
| US7838464B2 (en) | 2002-11-12 | 2010-11-23 | Basf Aktiengesellschaft | Method for yield improvement in glyphosate-resistent legumes |
| US8217064B2 (en) | 2007-12-20 | 2012-07-10 | Envivo Pharmaceuticals, Inc. | Tetrasubstituted benzenes |
| US8367863B2 (en) | 2007-12-20 | 2013-02-05 | Envivo Pharmaceuticals, Inc. | Tetrasubstituted benzenes |
| US8664249B2 (en) | 2007-12-20 | 2014-03-04 | Envivo Pharmaceuticals, Inc. | Tetrasubstituted benzenes |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9200404D0 (en) | 1992-02-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0569384B2 (en) | Fungicides | |
| AP126A (en) | Fungicides. | |
| CA1340412C (en) | Fungicides | |
| US5145856A (en) | Fungicides | |
| US5395837A (en) | Fungicides | |
| US5238956A (en) | Fungicidal aromatic dioxime | |
| EP0586393B1 (en) | Substituted-2-phenyl-3-methoxypropenoates as fungicides | |
| CA1304084C (en) | Fungicides | |
| US5206245A (en) | Fungicidal aromatic pyrimidinyl oxime ethers | |
| US5059605A (en) | Pyrimidine derivatives useful as fungicides | |
| GB2253624A (en) | Pyrimidine fungicides | |
| EP0436348B1 (en) | Pyridyl cyclopropane derivatives with fungicidal activity | |
| EP0405782A1 (en) | Fungicides | |
| EP0557291B1 (en) | Pyridil-pyrimidine derivatives as fungicidal compounds | |
| US5334722A (en) | Fungicides | |
| US5153199A (en) | Fungicidal compounds | |
| GB2238308A (en) | Methyl 2-substituted-3-methoxy-2-propenoates as fungicides | |
| GB2249092A (en) | Oxime ether fungicides | |
| GB2255092A (en) | 1,2,3-triazine fungicides | |
| EP0430471A1 (en) | Fungicides | |
| US5229391A (en) | Pyrimidine derivatives and their use as fungicidal agents | |
| GB2250987A (en) | Fungicidal thiazolyl-pyridines | |
| GB2218702A (en) | Fungicidal phenylacrylates | |
| GB2229720A (en) | Fungicides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |