GB2329180A - Imidazoline 5-one compounds as anti-fungal agents - Google Patents

Abstract

Compounds of formula (I) and fungicidal compositions thereof: wherein X<1> is O, S, SO or NR<17>; R<2> is optionally substituted hydroxylamino, hydroxylimino, R<13>C(=O)NHO, R<13>R<14>C=NN=C(R<12>) or R<13>HNC(=X<2>)NHN=C(R<12>); R<3> is a bond or optionally substituted methylene or ethylene; R<5> is NH, NR<11> or NC(=O)R<11> and all other R groups comprise standard substituents, e.g. hydrogen, cyano or optionally substituted alkyl, alkoxy, thoialkyl, aryl, heteroaryl, alkenyl or alkynyl; processes for preparing said compounds, fungicidal compositions comprising them and methods of using them to combat fungi, especially fungal infections of plants.

Description

CHEMICAL COMPOUNDS The present invention relates to imidazolinone compounds, to processes for preparing them, to fungicidal compositions comprising them and to methods of using them to combat fungi, especially fungal infections of plants.

Fungicidal imidazolinone compounds are disclosed in WO 93/24467.

The present invention provides a compound of formula (I):

wherein R' is hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkenyl or optionally substituted alkynyl; R2 is H2NO, R'3R'4C=NO, R13C(=O)NHO, Rl3Rl4C--NN=C(R'2) or R'3HNC(=X2)NHN=C(R12); R3 is (CR7R8)n, where n is 0 or 1, or CR7R8CR9R'0; R4 is hydrogen, alkyl, haloalkyl, alkylthio, alkoxy haloalkoxy, haloalkylthio, cyano, SOalkyl or SO2alkyl; R5 is NH, NRI' or NC-O)R11; R6, R7, R8, R9, R10 and R" are, independently, hydrogen, alkyl, optionally substituted aryl, optionally substituted heteroaryl or optionally substituted arylalkyl; R12 is hydrogen, alkyl, haloalkyl, alkylthio, alkoxy, haloalkoxy, haloalkylthio, cyano, NR'5R'6, optionally substituted aryl or optionally substituted heteroaryl; R'3, R14, Ris and Rl6 are, independently, hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted heteroaryl, acyl or haloacyl; or R'3 and R'4, together with the carbon atom to which they are both attached, form an optionally substituted 5-, 6-, 7- or 8-membered carbocyclic or heterocyclic ring; X' and X2 are, independently, 0, S, SO, or NR17; and R'7 is hydrogen, alkyl, alkenyl, optionally substituted aryl, optionally substituted arylalkyl or optionally substituted pyridinyl.

The compounds of formula (I) can exist in different isomeric forms. This invention covers all such isomers and mixtures thereof in all proportions.

Halogen includes fluorine, chlorine, bromine and iodine.

Optionally substituted alkyl is, for example, haloalkyl, hydroxyalkyl, alkoxyalkyl, optionally substituted arylalkyl, optionally substituted heteroarylalkyl, optionally substituted aryloxyalkyl, optionally substituted heteroaryloxyalkyl, cyanoalkyl or cycloalkylalkyl.

Alkyl moieties, and the alkyl moiety of alkoxy, haloalkoxy, alkylthio, haloalkyl, cycloalkylalkyl, optionally substituted arylalkyl, optionally substituted heteroarylalkyl, optionally substituted aryloxyalkyl and optionally substituted heteroaryloxyalkyl, preferably contain from 1 to 6, more preferably from 1 to 4, carbon atoms. They can be in the form of straight or branched chains and are, for example, methyl, ethyl, n- or iso-propyl, or n-, sec-, iso- or tert-butyl.

Cycloalkyl is preferably C34 cycloalkyl (such as cyclopentyl or cyclohexyl).

Haloalkyl moieties are preferably fluoroalkyl (for example, trifluoromethyl) or chioroalkyl moieties.

Haloalkoxy moieties are preferably fluoroalkoxy (for example trifluoromethoxy) or chloroalkoxy moieties.

Haloalkylthio moieties are preferably fluoroalkylthio (for example trifluoromethylthio) or chloroalkylthio moieties.

Alkoxyalkyl is preferably C,4 alkoxy(CI4)alkyl, for example methoxyethyl.

Cycloalkylalkyl is preferably C34 cycloalkyl(C,4)alkyl, for example cyclopropylmethyl or l-(cyclopropyl)eth-l -yl.

Alkenyl and alkynyl moieties preferably contain from 2 to 6, more preferably from 2 to 4, carbon atoms. They can be in the form of straight or branched chains, and the alkenyl moieties, where appropriate, can be of either the (D- or (Z)-configuration. Examples are vinyl, allyl and propargyl. optional substituents on alkenyl or alkynyl include halogen or aryl.

Acyl moieties are preferably alkanoyl (preferably containing from 1 to 6 carbon atoms, for example acetyl) or optionally substituted benzoyl (wherein the phenyl ring is optionally substituted as described below for aryl).

Haloacyl moieties are preferably fluoroacyl (for example, trifluoroacetyl) or chloroacyl moieties.

Aryl includes naphthyl, anthracyl (from anthracene), fluorenyl and indenyl but is preferably phenyl.

Heteroaryl includes 5- and 6-membered aromatic rings containing one, two, three or four heteroatoms selected from the list comprising oxygen, sulphur and nitrogen and can be fused to benzenoid ring systems. Examples of heteroaryl are pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl (1,2,3-, 1,2,4- and 1,3,5-), furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl (1,2,3- and 1,2,4-), tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, indolinyl, isoindolinyl, benzofuranyl, benzothienyl and benzimidazolinyl.

Aryloxyalkyl is, for example, aryloxy(C1-4)alkyl (such as phenoxy(C,4)alkyl).

Heteroaryloxyalkyl is, for example, heteroaryloxy(C1-4)alkyl (such as pyridinyloxy (C1-4)alkyl or pyrimidinyloxy(C1-4)alkyl).

The alkyl moiety of arylalkyl, heteroarylalkyl, aryloxyalkyl and heteroaryloxyalkyl is optionally substituted with C,4 alkoxy, optionally substituted aryl or optionally substituted heteroaryl. Arylalkyl is, for example, aryl(C1)alkyl (such as phenyl(C1-4)alkyl) and heteroarylalkyl is, for example, heteroaryl(C,)alkyl (such as pyridinyl(C1-4)alkyl or pyrimidinyl(C 1A)alkyl). Phenyl(C1-4)alkyl is especially benzyl, l-phenyleth-l-yl or 2 -phenylprop-2-yl.

When R'3 and R'4join to form a ring, such ring can be optionally substituted with C,4 alkyl and the ring is preferably a cyclopentyl, cyclohexyl, cyclohexenyl, cycloheptyl or cyclooctyl ring or a non-aromatic 5- or 6-membered heterocyclic ring comprising one or two oxygen, sulphur or nitrogen atoms. Heterocyclic rings include piperidine, morpholine, pyrrolidine, piperazine, pyrroline, isoxazoline or oxazoline.

Substituents which may be present on the aryl or heteroaryl rings (such as the aryl or heteroaryl rings listed above) of any of the foregoing substituents include one or more of the following: halogen, hydroxy, mercapto, C, 4 alkyl, C2A alkenyl, C2-4 alkynyl, C, @ alkoxy, C2-5 alkenyloxy, C2-5 alkynyloxy, halo(C1-4)alkyl, halo(C1-4)alkoxy, C1-4 alkylthio, halo(C1-4)alkylthio, hydroxy(C1-4)alkyl, C1-4 alkoxy(C1-4)alkyl, C3-6 cycloalkyl, C3-6 cycloalkyl(C1-4)alkyl, phenyl, phenoxy, acyl, SF5, cyano, thiocyanato, nitro, -NR'R", -NHCOR', -NHCONRtR", -CONR'R", -COOR', -SOR', -SO2R', -SO2(C34)alkenyl, -OSO2R', -NHSO2R', -SO2NR'R", -COR', -CR'=NR", -CR'=NOR" or -N=CR'R"; two substituents, when they are in adjacent positions on the aryl or heteroaryl ring can join to form a fished aliphatic ring (especially to form a fused 6-membered carbon aliphatic ring); R' and R" are independently hydrogen, C1-4 alkyl, C1-4 alkoxy, C1-4 alkylthio, C3-6 cycloalkyl, C3-6 cycloalkyl(C1-4)alkyl, phenyl or benzyl; the phenyl, phenoxy and benzyl groups being optionally substituted with halogen, C1-4 alkyl, halo(C1-4)alkyl, C1-4 alkoxy or C1-4 haloalkoxy; when R' and R" are in -NR'R", -CONR'R", -NHCONR'R" or -SO2NR'R" they can together form a 5- or 6-membered heterocyclic ring (for example a pyrrole, imidazole, pyrrolidine, piperidine or morpholine ring).

In one particular aspect, the present invention provides a compound of formula (I) wherein R1 is hydrogen or C1A alkyl (especially methyl); R3 is CH2; R4 is C1-4 alkylthio (especially methylthio) or C1-4 alkoxy (especially methoxy); RS is NH; R6 is optionally substituted phenyl (especially unsubstituted phenyl); and X' is oxygen.

In an additional aspect, the present invention provides a compound of formula (I) wherein R1 is hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkenyl or optionally substituted alkynyl; R2 is H2NO, R13R14C=NO, R13C(=O)NHO, R13R14C=NN=C(R12) or R13HNC(=X2)NHN=C(R12); R3 is (CR7R8)n, where n is 0 or 1, or CR7R8CR9R10; R4 is CIA alkylthio (especially methylthio) or C1-4 alkoxy (especially methoxy); Ras is NH; R6 is optionally substituted phenyl (especially unsubstituted phenyl); R, R8, R9, R10 and R" are, independently, hydrogen, alkyl, optionally substituted aryl, optionally substituted heteroaryl or optionally substituted arylalkyl; Rl2 is hydrogen, alkyl, haloalkyl, alkylthio, alkoxy, haloalkoxy, cyano, NR'5R'6, optionally substituted aryl or optionally substituted heteroaryl; R'3, R14, R15 and Rl6 are, independently, hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted heteroaryl, acyl or haloacyl; or R'3 and R'4, together with the carbon atom to which they are both attached, form an optionally substituted 5-, 6-, 7- or 8-membered carbocyclic or heterocyclic ring; X' and X2 are, independently, 0, S, SO, or NR17; and R17 is hydrogen, alkyl, alkenyl, optionally substituted aryl, optionally substituted arylalkyl or optionally substituted pyridinyl.

In another aspect, the present invention provides a compound of formula (I) wherein R1 is hydrogen or C1-4 alkyl (especially methyl); R2 is R13R14C=NO; R3 is C H2; R4 is C1-4 alkylthio (especially methylthio) or C1-4 alkoxy (especially methoxy); R5 is NH; R6 is optionally substituted phenyl (especially unsubstituted phenyl); P13 is hydrogen or C1-4 alkyl (especially methyl, ethyl or tert-butyl); R14 is CIA alkyl, 2-4 alkenyl, optionally substituted phenyl, optionally substituted pyridinyl, optionally substituted pyrimidinyl, optionally substituted oxazolyl, optionally substituted isoxazolyl, optionally substituted phenyl(C1-4)alkyl, optionally substituted pyridinyl(C1-4)alkyl, optionally substituted pyrimidinyl(C1-4)alkyl, optionally substituted oxazolyl(C1-4)alkyl, optionally substituted isoxazolyl(C 1-4)alkyl, optionally substituted thiazolyl(C1 A)alkyl or optionally substituted isothiazolyl(C1-4)alkyl (the foregoing aryl and heteroaryl rings are preferably substituted with one or more of cyano, halogen, nitro, C1-4 alkyl, C1-4 alkoxy, C1-4 alkylthio, C1-4 haloalkyl (for example CF3) or C1-4 haloalkoxy (for example OCF3)); and X' is oxygen.

In a further aspect, the present invention provides a compound of formula (I) wherein R' is C1-4 alkyl (especially methyl); R2 is R13R14C=NO; R3 is CH2; R4 is C1-4 alkylthio (especially methylthio) or C1-4 alkoxy (especially methoxy); R5 is NH; R6 is optionally substituted phenyl (especially unsubstituted phenyl); R'3 is hydrogen, C1-4 alkyl (especially methyl, ethyl or tert-butyl); R'4 is C1-4 alkyl, C2A alkenyl, optionally substituted phenyl, optionally substituted benzyl, optionally substituted pyridinyl, optionally substituted pyrimidinyl, optionally substituted pyridinyl(C,4)alkyl or optionally substituted pyrimidinyl (C-14)alkyl (the foregoing aryl and heteroaryl rings are preferably substituted with one or more of cyano, halogen, nitro, C1-4 alkyl (for example methyl), CiA alkoxy (for example OCH3) or C1-4 haloalkyl (for example CF3)); or Rl3 and R14, together with the carbon atom to which they are both attached, form an optionally substituted 5-, 6-, 7- or 8-membered carbocyclic ring, for example cyclopentyl or cyclohexyl; and X' is oxygen.

Table I provides examples of compounds of formula (I) wherein R' is methyl; R3 is CH2; R4 is CH3S; P5 is NH; R6 is phenyl; X1 is oxygen; and R2 is Rl3Rl4C=No wherein Rl3 and Rl4 are as defined in the Table.

Table I

Compound Number R13 R14 1 H CH3 2 H CH3CH2 3 H CH2=CHCH2 4 H (CH3kCH 5 H CH3(CH2)3CH2 6 H C6H5 7 H 2-CN-C6H4 8 H 3-CN-C6H4 9 H 4-CN-C6H4 10 H 2-Br-C6H4 11 H 3-Br-C6H4 12 H 4-Br-C6H4

13 H 2-Cl-C6H4 14 H 3-C1-C6H4 15 H 4-Cl-C6H4 16 H 2-F-C6H4 17 H 3-F-C6H4 18 H 4-F-C6H4 19 H 2-NO2-C6H4 20 H 3-NO2-C6H4 21 H 4-NO2-C6H4 22 H 2-CH3-C6H4 23 H 3-CH3-C6H4 24 H 4-CH3-C6H4 25 H 2-C2H5-C6H4 26 H 3-C2H5-C6H4 27 H 4-C2H5-C6H4 28 H 2-CF3-C6H4 29 H 3-CF3-C6H4 30 H 4-CF3-C6H4 31 H 2-CH3O-C6H4 32 H 3-CH3O-C6H4 33 H 4-CH3O-C6H4 34 H 2-CH3S-C6H4 35 H 3-CH3S-C6H4 36 H 4-CH3S-C6H4 37 H 2-CO2H-C6H4 38 H 3-CO2H-C6H4 39 H 4-CO2H-C6H4 40 H 2-C6H5O-C6H4 41 H 3-C6H5O-C6H4 42 H 4-C6H5O-C6H4 43 # H 2-(CH3)2N-C6H4 44 H 3-(CH3)2N-C6H4 45 H 4-(CH3)2N-C6H4 46 H 2-H2NC=ONH-C6H4 47 H 3-H2NC=ONH-C6H4 48 H 4-H2NC=ONH-C6H4 49 H 2,3-diF-C6H3 50 H 2,4-diF-C6H3 51 H 2,5-diF-C6H3 52 H 2,6-diF-C6H3 53 H 3,4-diF-C6H3 54 H 3,5-diF-C6H3 55 H 2,3-diCl-C6H3

56 H 2,4-diCl-C6H3 57 H 2,5-diCl-C6H3 58 H 2,6-diCl-C6H3 59 H 3,4-diCl-C6H3 60 H 3,SdiC1-C6H3 61 H 2-Cl-3-F-C6H3 62 H 2-F-3-Cl-C6H3 63 H 2-Cl-4-F-C6H3 64 H 2-F-4-Cl-C6H3 65 H 2-Cl-5-Cl-C6H3 66 H 2-F-5-Cl-C6H3 67 H 2-Cl-6-F-C6H3 68 H 3-Cl-4-F-C6H3 69 H 3-F-4-Cl-C6H3 70 H 3-Cl-5-F-C6H3 71 H 2-Cl-3-OH-C6H3 72 H 2-OH-3-Cl0C6H3 73 H 2-CI-4-OH-C6H3 74 H 2-OH-4-Cl-C6H3 75 H 2-Cl-5-OH-C6H3 76 H 2-OH-5-Cl-C6H3 77 H 2-Cl-6-OH-C6H3 78 H 3-Cl-4-OH-C6H3 79 H 3-OHA-C1-C6H3 80 H 3-Cl-5-OH-C6H3 81 H 2-C6H5O-3-F-C6H3 82 H 2-F-3-C6HsO-C6H3 83 H 2-C6H5O-4-F-C6H3 84 H 2-F-4-C6H5O-C6H3 85 H 2-C6H5O-5-F-C6H3 86 H 2-F-5-C6H5O-C6H3 87 H 2-C6H5O-4-F-C6H3 88 H 3-C6H5O-4-F-C6H3 89 H 3-F-4-C6H5O-C6H3 90 H 3-C6H5O-5-F-C6H3 91 H CJI5CH2 92 H 2-CH3-C6H4CH2 93 H 3-CH3-C6H4CH2 94 H 4-CH3-C6H4CH2 95 H 2-NO2-C6H4CH2 96 H 3-NO2-C6H4CH2 97 H 4-NO2-C6H4CH2 98 H 2-CH3O-C6H4CH2

99 H 3-CH3O-C6H4CH2 100 H 4-CH3O-C6H4CH2 101 H 2-CH3S-CEH4CH2 102 H 3-CH3S-C6H4CH2 103 H 4-CH3S-C6H4CH2 104 H 3-CN-C6H4CH2 105 H 3-CN-C6H4CH2 106 H 4-CN-C6H4CH2 107 H 2-F-C6H4CH2 108 H 3-F-C6H4CH2 109 H 4-F-C6H4CH2 110 H 2-Cl-C6H4CH2 111 H 3-Cl-C6H4CH2 112 H 4-Cl-C6H4CH2 113 H pyridin-2-yl 114 H 4-CN-pyridin-2-yl 115 H 4-(CH3)3C-pyridin-2-yl 116 H 4-CF3-pyridin-2-yl 117 H 6-CH3O-pyridin-2-yl 118 H 6-CF3-pyridin-2-yl 119 H 6-F-pyridin-2-yl 120 H 6-Cl-pyridin-3-yl 121 H 4-CF3-pyridin-2-ylmethyl 122 H 6-CH3-pyridin-2-ylmethyl 123 H pyrimidin-2-yl 124 H pyrimidin-5-yl 125 H 4-(CH3)2CHO-pyrimidin-2-yl 126 H 6-Cl-pyrimidin-4-yl 127 H 6-CH3O-pyrimidinA-yl 128 H 6-CH,O-pyrimidin4-ylmethyl 129 # H 4-CH,O-6-CH,-pyrimidin-2-ylmethyl 130 H fluoren-2-yl 131 H 2-CH3-indol-3-yl 132 CH3 CH3 133 CH3 CH3CH2 134 CH3 CH2=CHCH2 135 CH3 (CH3)2CH 136 CH3 CH3(CH2)3CH2 137 CH3 C6H5 138 CH3 2-CN-C6H4 139 CH3 3-CN-C6H4 140 CH3 4-CN-C6H4 141 CH3 2-Br-C6H4

142 CH3 3-Br-C6H4 143 CH3 4-Br-C6H4 144 CH3 2-Cl-C6H4 145 CH3 3-Cl-C6H4 146 CH3 3-Cl-C6H4 147 CH3 2-F-C6H4 148 CH3 3-F-C6H4 149 CH3 4-F-C6H4 150 CH3 2-NO2-C6H4 151 CH3 3-NO2-C6H4 152 CH3 4-NO2-C6H4 153 CH3 2-CH3-C6H4 154 CH3 3-CH3-C6H4 155 CH3 4-CH3-C6H4 156 CH3 2-C2H5-C6H4 157 CH3 3-C2H5-C6H4 158 CH3 4-C2H5-C6H4 159 CH3 2-CF3-C6H4 160 CH3 3-CF3-C6H4 161 CH3 4-CF3-C6H4 162 CH3 2-CH3O-C6H4 163 CH3 3-CH3O-C6H4 164 CH3 4-CH3O-C6H4 165 CH3 2-CH3S-C6H4 166 CH3 3-CH3S-C6H4 167 CH3 4-CH3S-C6H4 168 CH3 2-CO2H-C6H4 169 CH3 3-CO2H-C6H4 170 CH3 4-CO2H-C6H4 171 CH3 2-C6H5O-C6H4 172 CH3 3-C6H5O-C6H4 173 CH3 4-C6H5O-C6H4 174 CH3 2-(CH3)2N-C6H4 175 CH3 3-(CH3)2N-C6H4 176 CH3 4-(CH3)2N-C6H4 177 CH3 2-H2NC=ONH-C6H4 178 CH3 3-H2NC=ONH-C6H4 179 CH3 4-H2NC=ONH-C6H4 180 CH3 2,3-diF-C6H3 181 CH3 2,4-diF-C6H4 182 CH3 2,5-diF-C6H4 183 CH3 2,6-diF-C6H4 184 CH3 3,4-diF-C6H4

185 CH3 3,5-diF-C6H3 186 CH3 2,3-diCl-C6H3 187 CH3 2,4-diCl-C6H3 188 CH3 2,5-diCl-C6H3 189 CH3 2,6-diCl-C6H3 190 CH3 3,4-diCl-C6H3 191 CH3 3,5-diCl-C6H3 192 CH3 2-C1-3-F-C6H3 193 CH3 2-F-3-C1-C6H3 194 CH3 2-Cl-4-F-C6H3 195 CH3 2-F-4-Cl-C6H3 196 CH3 2-C1-5-F-C6H3 197 CH3 2-F-5-C1-C6H3 198 CH3 2-CL-6-F-C6H3 199 CH3 3-Cl-4-F-C6H3 200 CH3 3-F-4-Cl-C6H3 201 CH3 3-Cl-5-F-C6H3 202 CH3 2-Cl-3-OH-C6H3 203 CH3 2-OH-3-Cl-C6H3 204 CH3 2-Cl-4-OH-C6H3 205 CH3 2-OH-4-Cl-C6H3 206 CH3 2-Cl-5-OH-C6H3 207 CH3 2-OH-5-Cl-C6H3 208 CH3 2-Cl-6-OH-C6H3 209 CH3 3-Cl-4-OH-C6H3 210 CH3 3-OH-4-Cl-C6H3 211 CH3 3-Cl-5-OH-C6H3 212 CH3 2-CC6H5O-3-F-C6H3 213 CH3 2-F-3-C6H5O-C6H3 214 CH3 2-C6H5O-4-F-C6H3 215 CH3 2-F-4-C6H5O-C6H3 216 CH3 2-C6H5O-5-F-C6H3 217 CH3 2-F-5-C6H5O-C6H3 218 CH3 3-C6H5O-6-F-C6H3 219 CH3 3-C6H5O-4-F-C6H3 220 CH3 3-F-4-C6H5O-C6H3 221 CH3 3-C6H5O-5-F-C6H3 222 CH3 C6H5CH2 223 CH3 2-CH3-C6H4CH2 224 CH3 3-CH3-C6H4CH2 225 CH3 4-CH3-C6H4CH2 226 CH3 2-NO2-C6H4CH2 227 CH3 3-NO2-C6H4CH2

228 CH3 # 4-No2-C6H4CH2 229 CH3 2-CH3O-C6H4CH2 230 CH3 3-CH3O-C6H4CH2 231 CH3 4-CH3O-C6H4CH2 232 CH3 2-CH3S-C6H4CH2 233 CH3 3-CH3S-C6H4CH2 234 CH3 2-CH3S-C6H4CH2 235 CH3 2-CN-C6H4CH2 236 CH3 3-CN-C6H4CH2 237 CH3 4-CN-C6H4CH2 238 CH3 2-F-C6H4CH2 239 CH3 3-F-C6H4CH2 240 CH3 4-F-C6H4CH2 241 CH3 2-Cl-C6H4CH2 242 CH3 3-Cl-C6H4CH2 243 CH3 4-Cl-C6H4CH2 244 CH3 pyridin-2-yl 245 CH3 4-CN-pyridin-2-yl 246 CH3 4-(CH3)3C-pyridin-2-yl 247 CH3 4-CF3-pyridin-2-yl 248 CH3 6-CH3O-pyridin-2-yl 249 CH3 6-CF3-pyridin-2-yl 250 CH3 6-F-pyridin-2-yl 251 CH3 6-Cl-pyridin-3-yl 252 CH3 4-CF3-pyridin-2-ylmethyl 253 CH3 CH3-pyridin-2-ylmethyl 254 CH3 pyridin-2-yl 255 CH3 pyridin-5-yl 256 CH3 4-(CH3)2CHO-pyrimidin-2-yl 257 CH3 6-Cl-pyrimidin-4-yl 258 CH3 6-CH3O-pyrimidin-4-yl 259 CH3 6-CH3O-pyrimidin-4-ylmethyl 260 CH3 4-CH3O-6-CH3-pyrimidin-2-ylmethyl 261 CH3 fluoren-2-yl 262 CH3 2-CH3-indol-3-yl 263 C(CH3)3 CH3 264 C(CH3)3 CH3CH2 265 C(CH3)3 CH2=CHCH2 266 C(CH3)3 (CH3)2CH 267 C(CH3)3 CH3(CH2)3CH2 268 C(CH3)3 C6H5 269 C(CH3)3 2-CN-C6H4 270 C(CH3)3 3-CN-C6H4

271 C(CH3)3 4-CN-C6H4 272 C(CH3)3 2-Br-C6H4 273 C(CH3)3 3-Br-C6H4 274 C(CH3)3 4-Br-C6H4 275 C(CH3)3 2-Cl-C6H4 276 C(CH3)3 3-CI-C6H4 277 C(CH3)3 4-Cl-C6H4 278 C(CH3)3 2-F-C6H4 279 C(CH3)3 3-F-C6H4 280 C(CH3)3 4-F-C6H4 281 C(CH,)3 2-NO2-C6H4 282 C(CH3)3 3-NO2-C6H4 283 C(CH3)3 4-NO2-C6H4 284 C(CH3)3 2-CH3=C6H4 285 C(CH3)3 3-CH3-C6H4 286 C(CH3)3 4-CH3-C6H4 287 C(CH3)3 2-C2H5-C6H4 288 C(CH3)3 3-C2H5-C6H4 289 C(CH3)3 4-C2H5-C6H4 290 C(CH3)3 2-CF3-C6H4 291 C(CH3)3 3-CF3-C6H4 292 C(CH3)3 4-CF3-C6H4 293 C(CH3)3 2-CH3O-C6H4 294 C(CH3)3 3-CH3O-C6H4 295 C(CH3)3 4-CH3O-C6H4 296 C(CH3)3 2-CH3S-C6H4 297 C(CH3)3 3-CH3S-C6H4 298 C(CH3)3 4-CH3s-C6H4 299 C(CH3)3 2-CO2H-C6H4 300 C(CH3)3 3-CO2H-C6H4 301 C(CH3)3 4-CO2H-C6H4 302 C(CH3)3 2-C6H5O-C6H4 303 C(CH3)3 3-C6H5O-C6H4 304 C(CH3)3 4-C6H5O-C6H4 305 C(CH3)3 2-(CH3)2N-C6H4 306 C(CH3)3 3-(CH3)2N-C6H4 307 C(CH3)3 4-(CH3)2N-C6H4 308 C(CH3)3 2-H2NC=ONH-C6H4 309 C(CH3)3 3-H2NC=ONH-C6H4 310 C(CH3)3 4-H2NC=ONH-C6H4 311 C(CH3)3 2,3diF-C6H3 312 C(CH3)3 2,4-diF-C6H3 313 C(CH3)3 2,5-diF-C6H3

314 C(CH3)3 2,6-diF-C6H3 315 C(CH3)3 # 3,4-diF-C6H3 316 C(CH3)3 3,5-diF-C6H3 317 C(CH3)3 2,3-diCl-C6H3 318 # C(CH3)3 2,4-diCl-C6H3 319 # C(CH3)3 2,5-diCl-C6H3 320 C(CH3)3 2,6-diCl-C6H3 321 C(CH3)# 3,4-diCl-C6H3 322 C(CH3)3 3,5-diCl-C6H3 323 C(CH3)3 2-Cl-3-F-C6H3 324 C(CH3)3 2-F-3-Cl-C6H3 325 C(CH3)3 2-F-3-CL-C6H3 326 C(CH3)3 2-F-4-C1-C6H3 327 C(CH3)3 2-Cl-4-F-C6H3 328 C(CH3)3 2-F-5-C1-C6H3 329 C(CH3)3 2-C1-6-F-C6H3 330 C(CH3)3 3-Cl-4-F-C6H3 331 C(CH3)3 3-F-4-C1-C6H3 332 C(CH3)3 3-Cl-5-F-C6H3 333 C(CH3)3 # 2-C1-3-OH-C6H3 334 C(CH3)3 2-OH-3-Cl-C6H3 335 C(CH3)3 2-Cl-4-OH-C6H3 336 C(CH3)3 2-OH-4-CL-C6H3 337 C(CH3)3 2-Cl-5-OH-C6H3 338 C(CH3)3 2-OH-5-C1-C6H3 339 C(CH3)3 2-Cl-6-OH-C6H3 340 C(CH3)3 3-Cl-4-OH-C6H3 341 C(CH3)3 3-OH-4-CL-C6H3 342 C(CH3)3 3-C1-5-OH-C6H3 343 C(CH3)3 2-C6H5O-3-F-C6H3 344 C(CH3)3 2-F-3-C6H5O-C6H3 345 C(CH3)3 2-C6H5O-4-F-C6H3 346 C(CH3) 3 2-F-4-C6H5O-C6H3 347 C(CH3)3 2-C6H5O-5-F-C6H3 348 C(CH3)3 2-F-5-C6H5O-C6H3 349 C(CH3)3 2-C6H5O-6-F-C6H3 350 C(CH3)3 3-C6HSO-4-F-C6H3 351 C(CH3)3 # 3-F-4-C6H5O-C6H3 352 C(CH3)3 3-C6H3O-5-F-C6H3 353 C(CH3)3 C6HSCH2 354 C(CH3)3 2-CH3-C6H4CH2 355 C(CH3)3 2-CH3-C6H4CH2 356 C(CH3)3 4-CH3-C6H4CH2

357 C(CH3)3 2-NO2-C6H4CH2 358 C(CH3)3 3-NO2-C6H4CH2 359 C(CH3)3 4-NO2-C6H4CH2 360 C(CH3)3 2-CH3O-C6H4CH2 361 C(CH3)3 3-CH3O-C6H4CH2 362 C(CH3)3 4-CH3O-C6H4CH2 363 C(CH3)3 2-CH3S-C6H4CH2 364 C(CH3)3 3-CH3S-C6H4CH2 365 C(CH3)3 4-CH3S-C6H4CH2 366 C(CH3)3 2-Cl-C6H4CH2 367 C(CH3)3 3-CN-C6H4CH2 368 C(CH3)3 4-CN-C^H$CH2 369 C(CH3)3 2-F-C6H4CH2 370 C(CH,)3 3-F-C6H4CH2 371 C(CH3)3 4-F-C6H4CH2 372 C(CH3)3 2-Cl-C6H4CH2 373 C(CH3)3 3-Cl-C6H4CH2 374 C(CH3)3 4-Cl-C6H4CH2 375 C(CH3)3 pyndin-2-yl 376 C(CH3)3 4-CN-pyridin-2-yl 377 C(CH3)3 4-C(CH3)3C-pyridin-2-yl 378 C(CH3)3 4-CF3-pyridin-2-yl 379 C(CH3)3 6-CH3O-pyridin-2-yl 380 C(CH3)3 6-CF3-pyridin-2-yl 381 C(CH3)3 6-F-pyridin-2-yl 382 C(CH3)3 6-Cl-pyridin-3-yl 383 C(CH3)3 4-CF3-pyridin-2-yl 384 C(CH3)3 6-CH,-pyridin-2-ylmethyl 385 C(CH3)3 pyrimidin-2-yl 386 C(CH3)3 pyrimidin-5-yl 387 ç C(CH3)3 4-(CH,XCHO-pyrimidin-2-yl 388 C(CH3)3 6-Cl-pyrimidin-4-yl 389 C(CH3)3 6-CH3O-pyrimidin-4-yl 390 C(CH3)3 6-CH3O-Pyrimidin-4-ylmethyl 391 C(CH3)3 4-CH3O-6-CH3-pyrimidin-2-ylmethyl 392 C(CH3)3 fluoren-2-yl 393 C(CH3)3 2-CH3-indol-3-yl 394 H naphth-1-yl 395 CH3 naphth-1-yl 396 C(CH3)3 naphth-l-yl 397 H naphth-2-yl 398 CH3 naphth-2-yl 399 C(CH3)3 naphth-2-yl

400 H anthrac-9-yl 401 CH3 anthrac-9-yl 402 C(CH3)3 anthrac-9-yl 403 404 -(CH2)5 Table II Table II provides 404 examples of compounds of formula (I) wherein R' is methyl; R3 is CH2; R4 is CH3O; P5 is NH; R6 is phenyl; Xis oxygen; and R2 is R13R14C=NO wherein the values of Rl3 and R14 match the correspondingly numbered compounds in Table I.

The following abbreviations are used throughout this description: mp = melting point s= singlet d= doublet t = triplet q= quartet 2s = two singlets (due to isomers) 2t = two triplets (due to isomers) 2m = two multiplets (due to isomers) 3s = three singlets (due to isomers) ppm = parts per million br = broad dd = doublet of doublets dt = doublet of triplets m= multiplet 2d = two doublets (due to isomers) 2q = two quartets (due to isomers) 2dd = two doublet of doublets (due to isomers) 3dd = three doublet of doublets (due to isomers) Table III shows selected melting point and selected NMR data, all with CDCl3 as the solvent (unless otherwise stated), (no attempt is made to list every absorption in all cases) for compounds of Tables I and II.

Table III

Compound Melting NMR proton shifts (/ppm). Comments No (Table No) point (rC) 1 (I) 1.39 & 1.40(3H,2s); 1.81(3H,d); 2.52(3H,s); Isomers 4.32(s) & 4.40(dd)(2H); 6.09 & 6.10(1H,2s); 1:1 6.71 & 7.38(1H,2q); 6.81(2H,t); 6.97(1H,t); E:Z 7.23(2H,t).

1 (I) 1.39 & 1.40(3H,2s); 1.80 & 1.81(3H,2d); 2.52 & Isomers 2.53(3H,2s); 4.33(s) & 4.34(d) & 4.44(d)(2H); 5:11 6.11 & 6.13(1H,2s); 6,71 & 7,38(1H,2q); E:Z 6,81(2H,m); 6.97(1H,m); 7.22(2H,m).

2 (I) 1.04(3H,t); 1.38 & 1.39(3H,2s); Isomers 2.17 & 2.29(2H,2m); 2.51 & 2.52(3H,2s); 17:10 4.33(s) & 4.36(dd)(2H); 6.09 & 6.11(1H,2s); E:Z 6.81(2H,m); 6.97(1H,m); 7.23(2H,m); 6.58 & 7.35(1H,2t).

4 (I) 1.01B1.06(6H,2d); 1.38 & 1.39(3H,2s); Isomers 2.46 & 3.02(1H,2m); 2.52(3H,s); 4:1 4.32(s) & 4.36(dd)(2H); 6.07 & 6.10(1H,2s); E:Z 6.42 & 7.26(1H,2d); 6.81 (2H,m); 6.98(1H,m); 7.20-7.29(2H,m).

6 (I) 1.43(3H,s); 2.50(3H,s); 4.50(2H,m); One isomer 6.06(1H,s); 6.81(2H,d); 6.93(1H,t); 7.19(2H,t); 7.37(3H,m); 7.55(2H,m); 8.04(1H,s).

18 (1) 1.38(3H,s); 2.44(3H,s); 4.43(2H,dd); # One isomer 6.74(2H,d); 6.81(1H,t); 7.12(4H,t); 7.62(2H,m); 8.08(1Hs).(CD3OD) 27 (I) 163.5-168.7 1.24(3H,t); 1.42(3H,s); 2.49(3H,s); One isomer 2.67(2H,q); 4.48(2H,dd); 6.10(1H,s); 6.80(2H,d); 6.92(1H,t); 7. 19(2H,d); 7.20(2H,t); 7.46(2Ft,d); 8.01(1 H,s).

29 (I) 150.9-154.4 1.43(3H,s); 2.50(3H,s); 4.51(2H,dd); One isomer 6.10(1H,s); 6.81(2H,d); 6.92(1H,t); 7.19(2H,t); 7.48(1H,t); 7.61(1H,d); 7.69(1H,d); 7.8(1H, br.s); 8.05(1H,s).

33 (I) 1.38(3H,s); 2.45(3H,s); 3.81(3H,s); One isomer 4.43(2H,dd); 6.08(1H,br.s); 6.76(2H,d); 6.82(1H,t); 6.92(2H,d); 7.12(2H,t); 7.48(2H,m); 7.99(1H,s).

37 (1) 1.34(3H,s); 2.44(3H,s); 4.37-4.56(2H,m); One isomer 6.60-6.88(3H,m); 7.20(2H,t); 7.50-7.67(2H,m); 7.82(1H,d); 7.96(1H,d); 8.81(1H,s); 8.96(1H,s).

76 (I) 166.4-171.0 1.42(3H,s); 2.51(3H,s); 4.48(2H,q); One isomer 6.15(1H,s); 6.78(2H,d); 6.90(1H,d); 6.93(1H,t); 7.10(1H,d); 7.18(2H,t); 7.21(1H,dd); 8.04(1H,s); 9.42(1H,s).

88 (I) 142.0-144.7 1.40(3H,s); 2.45(3H,s); 4.44(2H,m); One isomer 6.26(1H,s); 6.78(2H,d); 6.90(1H,t); 6.96(2H,m); 7.06-7.20(4H,m); 7.21-7.39(4H,m); 7.91(1H,s).

124 (I) E isomer: 1.44(3H,s); 2.51(3H,s); Isomers 4.56(2H,dd); 6.23(1H,s); 6.68(2H,d); 3:2 6.92(1H,m); 7.09(2H,t); 7.27(1H,s); E:Z 8.84(2H,s); 9.18(1H,s).

Z isomer: 1.46(3H,s); 2.52(3H,s); 4.58(2H,dd); 6.32(1H,s); 6.81(2H,d); 6.92(1H,m); 7.18(2H,t); 7.99(1H,s); 9.12(2H,s); 9.21(1H,s).

130 (I) 1.43(3H,s); 2.49(3H,s); 4.52(2H,dd); Isomers 6.09(1H,s); 6.82(2H,d); 6.91(1H,t); 7.18(2H,t); 7.30-7.45(2H,m); 7.50-7.60(2H,t); 7.75-7.85(3H,m); 8.11(1H,s).

131 (1) 1.45(3H,s); 2.48(3H,s); 2.51(3H,s); One isomer 4.48(2H,dd); 5.94(1H,br.s); 6.68(1H,br.s); 6.90(1H,t); 7.1-7.35(6H,m); 8.08(2H,m); 8.30(1H,s).

136 (I) 54.0-55.7 0.89(3H,t); 1.18-1.52(6H,m); 1.39(3H,s); Isomers 1.79 & 1.80(3H,2s); 2.11 & 2.25(2H,m); 7:2 2.51 & 2.52(3H,2s); 4.30 & 4.33(2H,2dd); 6.13 & 6.20(1H,2s); 6.79(2H,t); 6.96(1H,t); 7.21(2H,t).

142 (I) 1.45 & 1.53(3H,2s); 2.18 & 2.27(3H,2s); 2.41 & 2.51(3H,2s); 4.50(2H,2dd); it 5.18 & 5.98(1H,2s); 6.70-7.85(9H,m).

146 (I) 128.4-129.5|1.41(3H,s); 2.18(3H,s); 2.48(3H,s); One isomer 4.50(2H,q); 6.09(1H,s); 6.71(2H,d); 6.90(1H,t); 7.15(2H,t); 7.30(2H,dd); 7.52(2H,dd).

160 (1) 1.43(3H,s); 2.22(3H,s); 2.50(3H,s); One isomer 4.55(2H,dd); 6.07(1H,s); 6.75(2H,d); 6.90(1H,t); 7.16(2H,t); 7.46(1H,t); 7.60(1H,d); 7.78(1H,d); 7.85(1H,s).

173 (I) 148.9-149.5 1.41(3H,s); 2.19(3H,s); 2.50(3H,s); One isomer 4.49(2H,dd):6.05(1H,s); 6.72(2H,d); 6.90(1H,t); 6.98(2H,d); 6.99-7.06(2H,m); 7.10-7.20(3H,m); 7.35(2H,m); 7.59(2H,d).

175 (I) 1.40 & 1.50(3H,2s); 2.19 & 2.29(3H,2s); 2.41 & 2.50(3H,2s); 2.98(6H,s); it 4.50(2H,2dd); 5.56 & 5.80(1H,2s); 6.61-7.60(9H,m).

179 (I) 1.44 & 1.52(3H,2s); 2.15 & 2.24(3H,2s); Isomers 2.51 & 2.56(3H,2s); 4.26-4.65(2H,m); 3:2 4.97(3H,m); 5.38 & 6.30(1H,2s); 6.70(2H,d); 6.89(1H,t); 7.05-7.59(6H,m).

180 (I) 1.42(3H,s); 2.22(3H,d); 2.52(3H,s); One isomer 4.51(2H,q); 6.02(1H,s); 6.79(2H,d); 6.95(1H,t); 6.99-7.07(1H,m); 7.10-7.25(4H,m).

222 (I) 116.6-119.2 1.40(3H,s); 1.72 & 1.76(3H,2s); 2.52(3H,s); Isomers 3.42 & 3.61(2H,m); 4.32-4.50(2H,dd); 3:1 5.81 & 5.99(1 H,2s); 6.69-6.82(2H,m); E:Z 6.88-6.99(1H,m); 7.10-7.36(7H,m).

245 (I) 159.2-160.6 1.44(3H,s); 2.29(3H,s); 2.52(3H,s); One isomer 4.55(2H,dd); 6.10(1H,s); 6.76(2H,m); 6.80(1H,m); 7.10(2H,t); 7.40(1H,dd); 7.92(1H,br.s); 8.70(1H,d).

246 (I) 174.4-1764 1.29(9H,s); 1.44(3H,s); 2.30(3H,s); One isomer 2.51(3H,s); 4.55(2H,dd); 6.20(1H,s); 6.71(2H,d); 6.86(1H,t); 7.11(2H,t); 7.24(1H,dd); 7.76(1H,br.s); 8.50(1H,d).

251 (1) 133.2-135.61.40 & 1 .42(3H,2s); 2.19 & 2.20(3H,2s); Isomers 2.48 & 2.5 1 (3H,2s);4.37 & 4.52(2H,2dd); 11:1 6.16 & 6.39(1H,2s); 6.67 & 6.73(2H,2d); 6.89(1H,m); 7.13(2H,m); 7.23 & 7.33(1H,2d); 7.79 & 7.85(1H,2dd); 8.48 & 8.52(1H,2d).

256 (I) 114.8-117.0 1.39(6H,m); 1.45(3H,s); 2.28(3H,s); One isomer 2.51 (3H,s); 4.52(2H,dd); 5.40(1H,m); 6.66(1H,d); 6.80(2H,d); 6.92(1H,t); 7.24(2H,t); 7.48(1H,br.s); 8.51(1H,d).

257 (I) 136.4-137.8 1.44(3H,s); 2.25(3H,s); 2.52(3H,s); One isomer 4.57(2H,dd); 6.10(1H,s); 6.75(2H,m); 6.83(1H,t); 7.12(2H,t); 7.67(1H,br.s); 8.93(1H,d).

386 (I) 1.15(9H,s); 1.33 & 1.39 & 1 .44(3H,3s); 2.40 & 2.46 & 2.49(3H,3s); 3 .85 & 4.28 & 4.30(2H,3dd); 4.92 & 5.08 & 6.44(1H,3br.s); it 6.65-7.60(5H,m); 8.40 & 8.50(2H,3s); 9.08 & 9.1 8 & 9.20(1H,3s).

394 (I) 1.48(3H,s); 2.49(3H,s); 4.58(2H,dd); 6.04(1H,s); 6.78(2H,d); 6.89(1H,t); 7.18(2H,t); 7.43-7.63(3H,m); 7.68(1H,dd); 7.88(2H,m); 8.55(1H,d); 8.64(1H,s).

397 (I) 1 .45(3H,s); 2.49(3H,s); 4.52(2H,dd); 6.08(1H,s); 6.82(2H,d); 6.92(1H,t); 7.18(2H,t); 7.48-7.54(2H,m); 7.82(4H,d); 8.18(1H,s).

400 (I) 1.48(3H,s); 2.51(3H,s); 4.68(2H,dd); 6.07(1H,s),6.80-6.92(3H,m); 7.18(2H,t); 7.51(1H,s); 7.44-7.58(3H,m); 8.02(2H,m); 8.41(2H,m); 8.51(1H,s); 9.17(1H,s).

403 (I) 1.39(3H,s); 1.64-1.82(4H,m); 2.28-2.40(4H,m); 2.52(3H,s); 4.34(2H,dd); 6.09(1H,s); 6.81(2H,d); 6.98(1H,t); 7.22(2H,dd). it Contains corresponding 1,3,4-triazine compound as an impurity.

Throughout this description, compounds are named according to the IUPAC system, with the ring atoms numbered as shown below.

The compounds of the present invention can be made by adapting processes disclosed in the art (for example W093/24467).

Compounds of lorriiula (I), wherein R1 is alkyl; R2 is R'3R'4C=NO; R3 is CH2; R4 is alkylthio; P5 is NH; R6 is optionally substituted phenyl; R'3 and R14 are as defined above; and X' is oxygen, can also be prepared as described below. In the process schemes shown below, R is hydrogen or a substituent for R6 as defined above.

NHNH2 H cs, /Me~l s"" R R CO2Me R1'NH,.HCI R1 soci2 HO R1 HO\ HOX )C02H R32 R1 S NH2.HCI MeOH NH2.HCI / gN- ~R (2) H H (5) HOR)N?D\/R J/\ N /S)tR R 0 k~ a R N8 HO R3'N (4) NHff\iR Compounds of formula (1) can be prepared by the method of Anthoni (Acta Chem.

Scand. 1966, vol. 20, p2742) whereby a phenyl hydrazine is reacted with iodomethane and carbon disulphide in water, in the presence of a strong base (such as sodium or potassium hydroxide). Substitution on the aryl ring of the starting phenyl hydrazine enables varation in that portion of the molecule.

A compound of formula (1) can be reacted with an amino acid ester hydrochloride (which can be prepared, for example, according to the procedure of Guttmann (Helv.

Chimica Acta, 1958, vol 41, pal852}) to give a thionoimidazolin-5-one (a compound of formula (2) or (5)). It is preferred that the reaction is carried out in an inert solvent (such as dimethylformamide) and in the presence of a strong organic base (such as triethylamine).

The temperature of the reaction is preferably between 20"C and 1200C and it is preferred that an inert atmosphere of nitrogen or argon is employed to minimise aerial decomposition.

Since the amino acid ester hydrochloride chosen has a direct bearing on the 4-substituent of the imidazolin-5-one ring, it will be appreciated that a range of different 4-substituted imidazolin-5-ones can be prepared. For example, use of methyl serine as amino acid ester hydrochloride provides 4-hydroxymethyl-4-methyl thionoimidazolin-5-one, while the use of alanine provides a 4-methyl thionoimidazolin-5-one which is open to fUrther substitution at the 4-position.

An alternative preparation of the thioimidazolinone heterocycle (2) is to adapt the work of Jefferys (J. Chem. Soc., 1954, p2227), whereby a phenyl hydrazine is reacted with an N-thiocarbamylglycine (6) (or other N-thiocarbamyl amino acid).

A compound of formula (3) or (4) can be prepared by reacting a compound of formula (2) or (5) with an alkylating agent (such as iodomethane) in the presence of a strong inorganic base (such as sodium or potassium carbonate) in a suitable solvent (such as acetone or tetrahydrofuran) at a temperature up to the boiling point of the solvent. It is particularly important to exclude atmospheric oxygen, by use of an inert gas such as nitrogen or argon, to prevent oxidation of the product under the alkaline conditions of the reaction.

A compound of formula (4) can be prepared by alkylation of a compound of formula (5).

A compound of formula (4) can also be prepared by reacting a compound of formula (3) with a suitable aldehyde or ketone in the presence of a strong base (such as lithium diisopropylamide, potassium carbonate or diisopropylethylamine) in a suitable solvent (for example tetrahydrofuran or diethyl ether).

Reaction of a compound of formula (4) with N-hydroxyphthalimide, under Mitsunobu conditions, gives a compound of formula (7) which can be reacted with hydrazine (Grochowski at al, Synthesis, 1976, p682), to give rise to a compound of formula (8), which can then be reacted with aldehydes or ketones to give a fmal a compound of formula (9). It is preferred that the final step involves the use of glacial acetic acid as both solvent and acid catalyst.

0 4)N-OH 0 HOY)NH%kYI/R SAlky SAlkyl 0 &num; MitsulOR (4) (7) NH2NH2 R4 fl l R14 zRs3 > 0 R130 R1 H,NCpji II R ~~~~~~~~~~~~~~ HNO R N N- 20NNH (9) (8) A compound of formula (I) wherein R4 is alkoxy can be prepared by reacting a compound of formula (I) wherein R4 is alkylthio, with an alkoxide (such as sodium methoxide).

In a further aspect the present invention provides processes, as hereinbefore described, for preparing a compound of formula (I) and a process for preparing a compound of formula (5) from a compound of formula (1).

In a still further aspect the present invention provides the intermediate compounds of formulae (2), (3), (4), (5), (7) and (8).

The compounds of formula (I) are active fungicides and may be used to control one or more of the following pathogens: Pyricularia oryzae on rice and wheat and other Pyricularia spp. on other hosts; Puccirfa recondita, Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts e.g. turf, rye, coffee, pears, apples, peanuts, sugar beet, vegetables and ornamental plants; Erysiphe graminis (powdery mildew) on barley, wheat, rye and turf and other powdery mildews on various hosts such as Sphaerotheca macularis on hops, Sphaerotheca fuliginea on cucurbits (for example cucumber), Podosphaera leucotricha on apple and Uncinula necator on vines; Cochliobolus spp., Helminthosporium spp., Drechslera spp. (Pyrenophora spp.), Rhynchosporium spp., Septoria spp. (including Mycosphaerella graminicola and Leptosphaeria nodonun), Pseudocercosporella herpotrichoides and Gaeumannomyces graminis on cereals (for example wheat, barley, rye), turf and other hosts; Cercospora arachidicola and Cercosporidium personatum on peanuts and other Cercospora species on other hosts, for example, sugar beet, bananas, soya beans and rice; Botrytis cinerea (grey mould) on tomatoes, strawberries, vegetables, vines and other hosts and other Botrytis spp. on other hosts; Alternaria spp. on vegetables (for example cucumber), oil-seed rape, apples, tomatoes, cereals (for example wheat) and other hosts; Venturia spp. (including Venturia inaequalis (scab)) on apples, pears, stone fruit, tree nuts and other hosts; Cladosporium spp. on a range of hosts including cereals (for example wheat); Monilinia spp. on stone fruit, tree nuts and other hosts; Didymella spp. on tomatoes, turf, wheat and other hosts; Phoma spp. on oil-seed rape, turf, rice, potatoes, wheat and other hosts; Aspergillus spp. and Aureobasidium spp. on wheat, lumber and other hosts; Ascochyta spp. on peas, wheat, barley and other hosts; Plasmopara viticola on vines; other downy mildews such as Bremia lactucae on lettuce, Peronospora spp. on soybeans, tobacco, onions and other hosts, Pseudoperonospora humuli on hops and Pseudoperonospora cubensis on cucurbits; Pythium spp. (including Pythium ultimum) on turf and other hosts; Phytophthora infestans on potatoes and tomatoes and other Phytophthora spp. on vegetables, strawberries, avocado, pepper, omamentals, tobacco, cocoa and other hosts; Thanatephorus cucumeris on rice and turf and other Rhizoctonia species on various hosts such as wheat and barley, vegetables, cotton and turf; Sclerotinia spp. on turf, peanuts, oil-seed rape and other hosts; Sclerotium spp. on turf, peanuts and other hosts; Colletotrichum spp. on a range of hosts including turf, coffee and vegetables; Laetisaria fucifonnis on turf, Mycosphaerella spp. on banana, peanut, citrus, pecan, papaya and other hosts; Diaporthe spp. on citrus, soybean, melon, pear, lupin and other hosts; Elsinoe spp. on citrus, vines, olives pecans, roses and other hosts; Pyrenopeziza spp. on oil-seed rape and other hosts; Oncobasidium theobromae on cocoa causing vascular streak dieback; Fusarium spp., Typhula spp., Microdochium nivale, Ustilago spp., Urocystis spp., Tilletia spp., and Claviceps purpurea on a variety of hosts but particularly wheat, barley, turf and maize; Ramularia spp. on sugar beet and other hosts; post-harvest diseases particularly of fruit (for example Penicillium digitatum and P. italicum and Trichoderma viride on oranges, Colletotrichum musae and Gloeosporium musarum on bananas and Botrytis cinerea on grapes); other pathogens on vines, notably Eutypa lata, Guignardia bidwellii, Phellinus igniarus, Phomopsis viticola, Pseudopezicula tracheiphila and Stereum hirsutum; other pathogens on lumber, notably Cephaloascus fragrans, Ceratocystis spp., Ophiostoma piceae, Penicillium spp., Trichoderma pseudokoningii, Trichoderma viride, Trichoderma harzianum, Aspergillus niger, Leptographium lindbergi and Aureobasidium pullulans; and fungal vectors of viral diseases for example Polymyxa graminis on cereals as the vector of barley yellow mosaic virus (BYMV).

Further, some of the compounds may be useful as seed dressings against pathogens including Fusarium spp., Septoria spp., Tilletia spp., (for example 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. It is preferred that all compositions, both solid and liquid formulations, comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 1 to 25% or 25 to 60%, of a compound as hereinbefore defined.

When applied to the foliage of plants, the compounds of the invention are applied at rates of 0.1 g to 10kg, preferably 1 g to 8kg, more preferably lOg to 4kg, of active ingredient (invention compound) per hectare.

When used as seed dressings, the compounds of the invention are used at rates of 0.0001g to 10g (for example 0.001g or 0.05g), preferably 0.005g to 8g, more preferably 0.005g to 4g, of active ingredient (invention compound) per kilogram of seed.

The compounds can be applied in a number of ways. For example, they can be applied, formulated or unformulated, directly to the foliage of a plant, to seeds or to other medium in which plants are growing or are to be planted, or they can be sprayed on, dusted on or applied as a cream or paste formulation, or they can be applied as a vapour or as slow release granules.

Application can be to any part of the plant including the foliage, stems, branches or roots, or to soil surrounding the roots, or to the seed before it is planted, or to the soil generally, to paddy water or to hydroponic culture systems. The invention compounds may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.

The term "plant" as used herein includes seedlings, bushes and trees. Furthermore, the fungicidal method of the invention includes preventative, protectant, prophylactic, systemic and eradicant treatments.

The compounds are preferably used for agricultural and horticultural purposes in the form of a composition. The type of composition used in any instance will depend upon the particular purpose envisaged.

The compositions may be in the form of dustable powders or granules comprising an active ingredient (invention compound) and a solid diluent or carrier, for example, a filler such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, fuller's earth, gypsum, diatomaceous earth or 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. C

Solutions may be prepared by dissolving the active ingredient in polar solvents such as ketones, alcohols and glycol ethers. These solutions may contain surface active agents to improve water dilution and prevent crystallisation in a spray tank.

Emulsifiable concentrates or emulsions may be prepared by dissolving an active ingredient in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents) and, for an emulsion, subsequently adding the mixture to water (which may contain one or more wetting agents, one or more emulsifying agents or a mixture of said agents). Suitable organic solvents are aromatic solvents such as alkylbenzenes and alkylnaphthalenes, ketones such as cyclohexanone and methylcyclohexanone, chlorinated hydrocarbons such as chlorobenzene and trichloroethane, and alcohols such as benzyl alcohol, furfuryl alcohol, butanol and glycol ethers.

Aqueous suspension concentrates of largely insoluble solids may be prepared by ball or bead milling with a dispersing agent with an antisettling agent included to stop the insoluble 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 suitable propellant.

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 invention compounds may be used in micro-encapsulated form.

They may also be formulated in biodegradable polymeric formulations to obtain a slow, controlled release of the active substance.

By including suitable additives, for example additives for improving the uptake, distribution, adhesive power or resistance to rain on treated surfaces, the different compositions can be better adapted for various utilities. Other additives may be included to improve the biological efficacy of the various formulations. Such additives can be surface active materials to improve the wetting or retention on surfaces treated with the formulation or the uptake or mobility of the active material, or additionally can include oil based spray additives, for example, certain mineral oil and natural plant oil (such as soya bean and rape seed oil) additives, or blends of them with other bio-enhancing adjuvants.

The invention compounds can be used as mixtures with fertilisers (for example nitrogen-, potassium- or phosphorus-containing fertilisers), such as granules of fertiliser comprising a compound of formula (I). 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 formula (I).

Water dispersible powders, emulsifiable concentrates and suspension concentrates optionally contain a surfactant (for example one or more wetting agents, one or more dispersing agents, or one or more emulsifying agents or a mixture of said agents, in which each agent can be, independently, cationic, anionic or non-ionic) and optionally contains one or more antisettling agents.

Suitable cationic agents are quaternary ammonium compounds, for example, cetyltrimethylammonium bromide. Suitable anionic agents are soaps, salts of aliphatic monoesters of sulphuric acid (for example, sodium lauryl sulphate), and salts of sulphonated aromatic compounds (for example, sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of sodium diisopropyl- and triisopropylnaphthalene sulphonates).

Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkyl phenols such as octyl- or nonylphenol and octylcresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, alkyl glucosides, polysaccharides and the lecithins and the condensation products of the said partial esters with ethylene oxide. Suitable suspending agents are hydrophilic colloids (for example, polyvinylpyrrolidone and sodium carboxymethylcellulose), and swelling clays such as bentonite or attapulgite.

Compositions for use as aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being diluted with water before use. These concentrates should preferably be able to withstand storage for prolonged periods and after such storage be capable of dilution with water in order to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may conveniently contain up to 95%, suitably 1-85%, for example 1-25% or 2560%, by weight of the active ingredient. After dilution to form aqueous preparations, such preparations may contain varying amounts of the active ingredient depending upon the intended purpose, but an aqueous preparation containing 0.0001 to 10%, for example 0.005 to 10%, by weight of active ingredient may be used.

The compositions of this invention may contain other compounds having biological activity, for example compounds having similar or complementary fungicidal activity or which possess plant growth regulating, herbicidal or insecticidal activity.

By including another fungicide, the resulting composition can have a broader spectrum of activity or a greater level of intrinsic activity than the compound of formula (I) alone.

Further the other fungicide can have a synergistic effect on the fungicidal activity of the compound of formula (I). Examples of fungicidal compounds which may be included in the composition of the invention are (E)-N-methyl-2-(2-phenoxyphenyl)-2 methoxyiminoacetamide, (O-N-methyl-2-[2 < 2,5-dimethylphenoxymethyl)phenyl]-2- methoxy-iminoacetamide, (RS)-1-aminopropylphosphonic acid, (RS)-4-(4-chlorophenyl) -2-phenyl-2-(1 H- 1,2,4-triazol- 1 -ylmethyl)butyronitrile, WZ-N-but-2-enyloxymethyl -2-chloro-2',6'-diethylacetanilide, 1 -(2-cyano-2-methoxyiminoacetyl)-3-ethyl urea, 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile, 4-bromo-2-cyano-N,N-dimethyl -6-trifluoromethylbenzimidazole- l-sulphonamide, 5-ethyl-5, 8-dihydro-8-oxo(l,3 )-dioxol- (4,5 -g)quinoline-7-carboxylic acid, a-[N-(3 -chloro-2,6-xylyl)-2-methoxy- acetamido]-y-butyroiactone, N-(2-methoxy- 5 -pyridyl)-cyclopropane carboxamide, alanycarb, aldimorph, ampropylfos, anilazine, azaconazole, azoxystrobin, benalaxyl, benomyl, biloxazol, binapacryl, bitertanol, blasticidin S, bromuconazole, bupirimate, butenachlor, buthiobate, captafol, captan, carbendazim, carbendazim chlorhydrate, carboxin, CGA245704, chinomethionate, chlorbenzthiazone, chloroneb, chlorothalonil, chlorozolinate, c lozy lacon, copper containing compounds such as copper oxychloride, copper oxyquinolate, copper sulphate, copper tallate, and Bordeaux mixture, cycloheximide, cymoxanil, cyproconazole, cyprodinyl, cyprofuram, desbacarb, di-2-pyridyl disulphide 1,1 '-dioxide, dichlofluanid, dichlone, diclobutrazol, diclomezine, dicloran, didecyl dimethyl ammonium chloride, diethofencarb, difenoconazole, O,O-di-iso-propyl-S-benzyl thiophosphate, dimefluazole, dimetconazole, dimethomorph, dimethirimol, diniconazole, dinocap, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, doguadine, edifenphos, epoxiconazole, etaconazole, ethirimol, ethoxyquin, ethyl (Z)-N-benzyl-N-( [methyl(methyl-thioethylideneamino- oxycarbonyl)amino]thio)-p-alaninate, etridiazole, famoxadone, fenaminosulph, fenapanil, fenarimol, fenbuconazole, fenfuram, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluoroimide, fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fuberidazole, furalaxyl, furametpyr, furconazole-cis, guazatine, hexaconazole, hydroxyisoxazole, hymexazole, imazalil, imibenconazole, ipconazole, iprobenfos, iprodione, isopropanyl butyl carbamate, isoprothiolane, kasugamycin, kresoxim-methyl, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole, methfuroxam, metiram, metiram-zinc, metsulfovax, myclobutanil, NTN0301, neoasozin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, organomercury compounds, oxadixyl, oxolinic acid, oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, phosetyl-Al, phosphorus acids, phthalide, polyoxin D, polyram, probenazole, prochloraz, procymidone, proparnocarb, propamocarb hydrochloride, propiconazole, propineb, propionic acid, prothiocarb, pyracarbolid, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinconazole, quinomethionate, quintozene, rabenazole, sodium pentachlorophenate, streptomycin, sulphur, tebuconazole, techlofthalam, tecnazene, tetraconazole, thiabendazole, thicyofen, thifluzamide, 2-(thiocyanomethylthio)benzothiazole, thiophanatemethyl, thiram, timibenconazole, tolclofos-methyl, tolylfluanid, triacetate salt of 1,1'-iminodi(octamethylene)diguanidine, triadimefon, triadimenol, triazbutyl, triazoxide, tricyclazole, tridemorph, triforine, triflumizole, triticonazole, validamycin A, vapam, vinclozolin, XRD-563, zineb and ziram. The compounds of formula (I) can be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.

The following Examples illustrate the invention.

EXAMPLE 1 This Example illustrates the preparationf 4-(5-chloro-2- hydroxybenzaldoximinom thyl)-4-methyl-2-methylthio-1 -phenylamino-2-imidazolin-5-one (Compound No.76 in Table I ).

Methvl-3 -ohenyldithiocarbazate.

A solution of potassium hydroxide (2.80g, 0.05M) in water (7.5ml) was added simultaneously with carbon disulphide (5.70g, 0.075M, 4.50ml), dropwise, to a mechanically stirred solution of phenylhydrazine (5.40g, 0.05M) in ethanol (130ml), with ice-water cooling to maintain the reaction mixture temperature at 20-250C. The initial orange solution became a thick, buff-coloured suspension. The mixture was stirred at room temperature for ninety minutes, then methyl iodide (7.10g, 0.05M, 3.11 my) was added in one portion. There was an exothermic reaction, the reaction mixture temperature rising to 280C and all solids went back into solution. After stirring for a further two hours at room temperature the solvent was removed by evaporation under reduced pressure (at 400C) to give a yellowish-green solid. This was triturated with water, filtered off, washed copiously with water and then air dried to give a sand coloured solid. The crude product was stirred in dichioromethane (100ml) and the mixture heated to reflux. Hexane was slowly added and the dichloromethane allowed to boil away until the boiling point of the mixture was 55"C and a lot of solid had precipitated out. The mixture was cooled and filtered, leaving a solid, which was washed with hexane (4x75ml) and air-dried to yield the title compound as an off-white solid (8.22g; 83%).

'H NMR (CDCl3): 8 8.58(1H,s), 7.29(2H,t), 7.00(1H,t), 6.84(2H,d), 6.02(1H,s), 2.60(3H,s)ppm.

4-Methyl- 1 -Dhenvlamino-2-thionoimidazolidin-5-one.

Alanine methyl ester hydrochloride (2.79g, 0.02M) and methyl-3phenyldithiocarbazate (1.98g, 0.01M) were stirred in dimethylformamide (DMF) (40ml) under a nitrogen atmosphere. Triethylamine (2.02g, 0.02M, 2.79ml) was added in one portion and the resultant thick green suspension heated to 11 00C for five hours. The reaction mixture was allowed to cool to room temperature and left to stand overnight. The bulk of the DMF solvent was removed by evaporation under reduced pressure with a water bath at 70 80"C, using an in-line bleach trap to scrub out methanethiol. The oily residue was diluted with water (20ml) and extracted with diethyl ether (3x150ml). The organic extracts were combined, washed with saturated brine solution (2xlOOml) then dried over MgSO4 and filtered. Removal of the solvent by evaporationnder reduced pressure (at 400C) gave a pale yellow gummy solid. This crude solid was triturated with 10% by volume diethyl ether in hexane, filtered off, washed with 10% by volume diethyl ether in hexane, then further washed with a small amount of diethyl ether, and finally dried under suction to give an offwhite powdery solid (1.572g; 71%). Recrystallisation of a 0.46g sample of this solid from ethyl acetate (using decolourising charcoal) gave 0.233g of the title compound as a white, powdery solid (mp 190.6-192.2"C).

'H NMR (CDC13): 5 7.35(1H,s), 7.27(2H,m), 7.00(1H,t), 6.81(2H,d), 6.48(1H,s), 4.30(1H,q), 1.60(3H,d)ppm.

4-Methvl-2-methvlthio- 1 -phenvlamino-2-imidazolin-5 -one.

To a stirred solution of 4-methyl-1-phenylamino-2-thionoimidazolidin-5-one (1.105g, 0.005M) in acetone (25ml) under a nitrogen atmosphere was added potassium carbonate (0.68g, 0.0049M) and iodomethane (0.70g, 0.0049M, 0.31ml). The mixture was heated to reflux with stirring for four hours, then allowed to cool to room temperature. The mixture was filtered and the filter-cake washed through with further portions of acetone. The solvent was removed from the combined filtrate and washings, by evaporation under reduced pressure, to give a gritty orange-brown oil. The crude product was partitioned between diethylether (30ml) and water (20ml), the organic layer being separated and the aqueous layer being further extracted with diethyl ether (2x20ml). The organic extracts were combined, washed with water (2xl5ml), dried over MgSO4 and filtered, the solvent being removed by evaporation under reduced pressure to give a yellowish gum that crystallised.

The solid was triturated with hexane containing 10% by volume diethyl ether and filtered off, washed twice with hexane containing 10% by volume diethyl ether and then dried at the pump to yield the title compound as a cream powdery solid (0.883g; 75%).

'H NMR (CDCl3): # 7.26(2H,t), 6.99(1H,t), 6.77(2H,d), 6.12(1H,s), 4.22(1H,q), 2.51(3H,s), 1 .50(3H,d)ppm.

4-(Hydroxymethyl)-4-methyl-2-methylthio-1-phenylamino-2-imidazolin-5-one.

The reaction apparatus was dried by heating under vacuum then purging with dry nitrogen prior to use. A solution of lithium bis(trimethylsilyl)amide (0.0049M; 4.9ml of 1 .0M in hexane stock solution) and dry tetramethylethylenediamine (0.82g, 0.00705M, 1 .0Srn1) in dry tetrahydrofuran (lOml), was added dropwise with stirring under a nitrogen atmosphere, to a solution of 4-methyl-2-methylthio- 1 -phenylamino-2-imidazolin-5 -one (1.18g, 0.005M) in dry tetrahydrofuran (65ml), previously cooled to -70 C in an acetone/solid carbon dioxide bath, at such a rate as to maintain a reaction temperature of less than -65 C. The reaction mixture turned from a pale yellow solution through a pale salmon pink to a very deep salmon pink suspension. After one and a half hours, formaldehyde gas was bubbled through the reaction mixture, with vigorous stirring, for approximately five minutes. The reaction mixture was then allowed to warm to +15 C, the deep salmon pink colour changing to deep cherry-red at approximately -40 C to -30 C, and paling to a light orange at 0 C to +100C. Saturated aqueous ammonium chloride solution (lSml) was added and the two phase mixture stirred for one hour. Dilute aqueous hydrochloric acid (5ml) was added and stirring continued for ten minutes. The organic phase was then separated. The aqueous phase was further extracted with dichloromethane (2x50ml). All the organic extracts were then combined, washed with brine (2x70ml), dried over MgSO4 and filtered. The solvent was removed from the filtrate by evaporation under reduced pressure to give a yellow oil, 2.10g. Column chromatography (silica, ethyl acetate as eluent) furnished the product as a pale yellow oil that crystallised. The solid was triturated with hexane containing 5% by volume diethyl ether, filtered off, washed with hexane containing 5% by volume diethyl ether and dried at the pump to yield the title compound as a pale yellow powdery solid (0.849g; 64%).

'H NMR (CDCl3): 6 7.25(2H,m), 6.97(1H,m), 6.79(2H,d), 6.19(1H,s), 3.93- 3.76(2H,m), 2.52(3H,s), 2.03(1H,s), 1.37(3H,s)ppm.

4-(Phthalimidooxvmethyl)A-methyl-2-methylthio- l-phenvlamino-2-imidazolin-5-one.

The reaction apparatus was dried by heating under vacuum then purging with dry nitrogen prior to use. To a stirred room temperature solution of 4-(hydroxymethyl)4 methyl-2-methylthio-1 -phenylamino-2-imidazolin-5-one (3.98g, 0.015M) in dry tetrahydrofuran under a nitrogen atmosphere, was added N-hydroxyphthalimide (2.45g, 0.015M), triphenylphosphine (3.93g, 0.015M), and diisopropylazodicarboxylate (3.34g, 0.0165M, 3.25ml). The reaction mixture turned from a pale yellow solution through orange and deep red, to a thick orange-brown slurry, darkening to a deep brown, the temperature rising to +39"C. After four hours of stirring, the reaction mixture had become a pale golden solution. This was allowed to stand at room temperature for sixteen hours. The solvent was removed by evaporation under reduced pressure to give a viscous yellow oil. Column chromatography on silica, using a 1:1 by volume mixture of ethyl acetate : hexane as eluent, furnished a solid which was triturated with diethyl ether, collected at the pump, washed with diethyl ether and dried at the pump to yield the title compound as a pale cream powdery solid, 3.40g (55%). lH NMR (CDC13): 6 7.87-7.70(4H,m), 7.26(2H,t), 6.96(1H,t), 6.84(2H,d), 6.39(1H,s), 4.55(2H,q), 2.37(3H,s), 1.41(3H,s) ppm.

4-(Aminooxvmethvl)-4-methvl-2-methvlthio 1 -Dhenvlamino-2-imidazolin-5-one.

To a stirred suspension of 4-(phthalimidooxymethyl)-4-methyl-2-methylthio-1- phenylamino-2-imidazolin-5-one (1.50g, 0.00366M) in dry tetrahydrofuran (30ml) was added hydrazine monohydrate (0.183g, 0.00366M, 0.18ml) to give, after a few minutes, a bright yellow mixture. This was stirred at room temperature for 19 hours, Diethylether (looms) was added and after a further 30 minutes stirring, the mixture was filtered at the pump, washing the filter-cake with diethylether (2x50ml). The solvent was removed by evaporation under reduced pressure to give a yellow gum. Column chromatography on silica using ethyl acetate as eluent furnished the product as a yellow powder. This was washed with hexane containing 10% by volume diethyl ether and dried at the pump to yield the title compound as a cream powdery solid, 0.73g (71%).

'H NMR (CDCl3): 6 7.25(2H,t), 6.97(1H,t), 6.80(2H,d), 6.12(1H,s), 5.54(2H,s), 3.99(2H,q), 2.52(3H,s), 1.35(3H,s) ppm.

C5-Chloro-2-hvdroxvbenzaldoximinomethyl)A-methyl-2-methvlthio- 1 -phenYlamino-2- imidazolin-5-one To a stirred solution of 4-(aminooxymethyl)-4-methyl-2-methylthio-1-phenylamino- 2-imidazolin-5-one (0.075g, 0.000268M) in glacial acetic acid (1.5ml) was added 5chlorosalicylaldehyde (0.05g, 0.00032M). The reaction mixture was stirred at room temperature for four hours, left to stand for sixteen hours, then diluted with ethylacetate (25ml) and washed with water (4x 15ml), The organic phase was dried over magnesium sulphate, filtered and evaporated under reduced pressure to yield the desired compound as a yellow oil which crystallised (0.062g; 55%).

EXAMPLE 2 This Example illustrates the preparation of 4-(4-chlorophenylacetoximinomethyl)4- methyl-2-methylthio-l-phenylamino-2-imidazolin-5-one (Compound No.146 in Table I).

4-(4-Chloronlienvlacetoximinomethvl)A-methvlt2-methvlthio- 1 -t,henylarnino-2-irnidazolin- 5-one.

To a stirred solution of 4-(aminooxymethyl)-4-methyl-2-methylthio 1 -phenylamino2-imidazolin-5-one (0.075g, 0.000268M, prepared as described in Example 1) in glacial acetic acid (1.5ml) was addedp-chloroacetophenone (0.05g, 0.00032M). The reaction mixture was stirred at room temperature for four hours, left to stand for 16 hours, then diluted with ethyl acetate (25ml) and washed with water (4xl5ml). The organic phase was dried over magnesium sulphate, filtered and evaporated under reduced pressure to give a yellow gum. Column chromatography on silica, using a 3:7 by volume mixture of ethyl acetate and hexane as eluent, gave the product as a yellow gum which crystallised. The solid was triturated with 10% by volume diethyl ether in hexane, filtered off, washed with 10% by volume diethylether in hexane and dried at the pump to yield the desired compound as a pale yellow powdery solid (0.0373g; 33%).

EXAMPLE 3 The compounds were tested against a variety of foliar fungal diseases of plants. The technique employed was as follows.

Plants were grown in John Innes Potting Compost (No. 1 or 2) in 4cm diameter, 3.5cm depth minipots. The test compounds were individually formulated as a solution either in acetone or acetone/ethanol (1:1 by volume) which was diluted in deionised water to a concentration of 100ppm (that is, 1 mg of compound in a final volume of 1 Oml) immediately before use. When foliar sprays were applied to monocotyledonous crops, Tween 20 (0.1% by volume) was added.

Individual compounds were applied as a foliar (Folr) application (where the chemical solution was applied to the foliage of the test plants by spraying the plant to maximum droplet retention); or as a systemic (Syst) application (where the chemical solution, 10ml, was applied as a root drench treatment).

These tests were carried out against Plasmopara viticola, on vines; Phvtophthora infestans lvcopersici on tomatoes; Venturia inaeaualis. on apples; Ervsiphe graminis tritici, on wheat; and Puccinia recondita, on wheat. Each treatment was applied to two or more replicate plants for Plasmopara viticolas Phvtophthora infestans lvcopersici and Venturia inaeaualis. In tests on Puccinia recondita two replicate pots each containing 6 tolO plants were used for each treatment. The plants were inoculated with a calibrated fungal spore suspension one or two days before (Erad) or one pr two days after (Prot) chemical application.

After chemical application and inoculation, the plants were incubated under high humidity conditions and then put into an appropriate environment to allow infection to proceed, until the disease was ready for assessment. For Plasmopara viticola, the plants were reincubated under high humidity conditions for 24 hours prior to assessment. The time period between inoculation and assessment varied from four to fourteen days according to the disease and environment. However, each individual disease was assessed after the same time period for all compounds.

Assessments were performed on a single leaf of each of the two replicate plants for Plasmopara viticola and Venturia inaeaualis and on each of two leaves on each of the replicate plants for Phvtophthora infestans lycopersici. For Puccinia recondita and Erysiphe graminis tritici assessments were carried out collectively on the plants in each replicate pot.

The disease level present (that is, the percentage leaf area covered by actively sporulating disease) was assessed visually. For each treatment, the assessed value for each replicate was then meaned before being expressed as a percentage of the mean level of disease present on the untreated control plants. This calculated value is referred to as a POCO (Percentage of Control) value.

An example of a typical calculation is as follows: Mean disease level for treatment A = 25 Mean disease level on untreated controls = 90 POCO = Mean disease level for treatment A x 100 =25 x 100 = 27.8 Mean disease level on untreated controls 90 This POCO value is then rounded to the nearest of the points in the 9-point banded assessment scale shown below, to give a banded POCO figure; in this particular example, the banded POCO result will be 30. If the POCO value falls exactly mid-way between two of the points, the banded POCO result will be the lower of the two points.

0= 0% disease present 10 = 5.1 - 10% disease present 1 = 0.1-1% disease present 20 = 10.1-20% disease present 3 = 1.1-3% disease present 30 = 20.1-30% disease present 5 = 3.1-5% disease present 60 = 30. 1-60% disease present 90 = 60.1-100% disease present The banded POCO results are shown in Table IV.

TABLEIV

Compound No PLASVI PLASVI PHYTIN ERYSGT VENTIN PUCCRT PUCCRT (Table No) * (Prot/Folr) (Prot/Syst) (Prot/Folr) (Prot/Folr) (Prot/Folr) (Erad/Folr) (Prot/Folr) 1 (I) * 0 30 90 90 90 2 (I) 90 90 < 90 4 (I) 10 10 90 90 90 6 (I) 0 30 10 60 60 90 3 18 (I) 3 10 90 90 60 10 27 (I) 10 90 90 60 60 60 1 29 (I) 0 90 90 60 60 33 (I) 10 5 90 90 90 20 37 (I) 60 90 90 90 90 76 (I) 0 90 90 90 90 88 (I) 0 90 90 90 30 130 (I) 90 90 90 90 90 90 131 (I) 90 90 90 90 90 90 90 136 (I) 20 90 90

Compound No PLASVI PLASVI PHYTIN PHYTIN VENTIN PUCCRT PUCCRT (Table No) * (Prot/Folr) (Prot/Syst) (Prot/Folr) (Prot/Syst) (Prot/Folr) (Erad/Folr) (Prot/Folr) 173 (I) 0 90 90 60 20 90 60 175 (I) 90 90 90 20 90 90 179 (I) 90 90 90 90 90 90 180 (I) 0 90 90 90 90 222 (I) 10 90 90 90 90 90 90 245 (I) 90 90 90 90 90 90 90 246 (I) 90 90 90 60 90 90 90 251 (I) 20 90 90 90 90 90 90 256 (I) 90 90 90 20 60 90 90 257 (I) 20 90 90 90 90 90 90 386 (I) 90 90 90 90 90 90 403 (I) 90 90 90 60 90 90 90 * Isomer information as in Table III, compound 1(I) only tested as 1:1 ratio of E:Z isomers.

Key to Diseases: PLASVI Plasmopara viticola VENTIN Venturia inaequalis PUCCRT Puccinia recondita PHYTIN Phytophthora infestans lycopersici ERYSGT Erysiphe graminis tritici

Claims (6)

1. CLAIMS 1. A compound of formula (I):

   wherein R' is hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkenyl or optionally substituted alkynyl; R2 is H2NO, R13R14C=NO, R'3C(=O)NHO, R'3R'4C=NN=C(R'2) or P'3HNC(=X2)NHN=C(P12); R3 is (CR7R8)n, where n is 0 or 1, or CR'R8CR9R'0; R4 is hydrogen, alkyl, haloalkyl, alkylthio, alkoxy, haloalkoxy, haloalkylthio, cyano, SOalkyl or SO2alkyl; P5 is NH, NR11 or NC(=O)R"; R6, R7, R8, R9, R10 and R11 are, independently, hydrogen, alkyl, optionally substituted aryl, optionally substituted heteroaryl or optionally substituted arylalkyl; Rl2 is hydrogen, alkyl, haloalkyl, alkylthio, alkoxy, haloalkoxy, haloalkylthio, cyano, NR'5R'6, optionally substituted aryl or optionally substituted heteroaryl; R'3, R'4, P15 and R16 are, independently, hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl, optionally substituted alkynyl, optionally substituted heteroaryl, acyl or haloacyl; or R'3 and R'4, together with the carbon atom to which they are both attached, form an optionally substituted 5-, 6-, 7- or 8-membered carbocyclic or heterocyclic ring; X' and X2 are, independently, 0, S, SO, or NRI7; and P17 is hydrogen, alkyl, alkenyl, optionally substituted aryl, optionally substituted arylalkyl or optionally substituted pyridinyl.
2. 2. Processes for preparing a compound as claimed in claim 1 as herein described.
3. 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. 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.
5. 5. A process for preparing a compound of formula (5):

   comprising reacting a compound of formula (1):

   with an intermediate:

   wherein R' is as defined in claim 1 and R is hydrogen, halogen, hydroxy, mercapto, C1-4alkyl, C2-4 alkenyl, C2-4 alkynyl, C1-4 alkoxy, C2-5 alkenyloxy, C2-5 alkynyloxy, halo(C1-4)alkyl, halo(C1-4)alkoxy, C1-4 alkylthio, halo(C1-4)alkylthio, hydroxy(C1-4)alkyl, C1-4 alkoxy(C1-4)alkyl, C3-6 cycloalkyl, C3-6 cycloalkyl(C1-4)alkyl, phenyl, phenoxy, acyl, SF5, cyano, thiocyanato, nitro, -NR'R", -NHCOR', -NHCONR'R", -CONR'R", -COOR', -SOR', -SO2R', -SO2(C34)alkenyl, -OSO2R', -NHSO2R', -SO2NR'R", -COR', -CR'=NR", -CR'=NOR" or -N=CR'R"; two substituents, when they are in adjacent positions on the aryl or heteroaryl ring can join to form a fused aliphatic ring (especially to form a fused 6-membered carbon aliphatic ring); R' and R" are independently hydrogen, C1-4 alkyl, C1-4 alkoxy, C1-4 alkylthio, C3-6 cycloalkyl, C3-6 cycloalkyl(C1-4)alkyl, phenyl or benzyl; the phenyl, phenoxy and benzyl groups being optionally substituted with halogen, C1-4 alkyl, halo(Co4)alkyl, C1-4 alkoxy or C1-4 haloalkoxy; when R' and R" are in -NR'R", -CONR'R", -NHCONR'R" or -SO2NR'R" they can together form a 5- or 6-membered heterocyclic ring.
6. 6. Intermediate compounds of formulae (2), (3), (4), (5), (7) and (8), as herein described.