Herbicidal Compositions

Abstract

The present invention relates to the use of herbicidal substituted phenyl-pyridazinediones and substituted phenyl-pyridazinone derivatives of formula (I), in combination with herbicidal pyrrolidinone derivatives of the formula (II) to control undesirable plant growth, in controlling weeds, including broad-leaved and/or narrow-leaved, monocotyledonous and/or dicotyledonous weeds, in crops of useful plants.

Claims

1. A composition comprising: (A) a compound of formula (I) ##STR00077## or a salt or N-oxide thereof, wherein R.sup.1 is selected from the group consisting of C.sub.1-C.sub.4 alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6alkoxy, C.sub.1-C.sub.2 alkoxy-C.sub.1-C.sub.2 alkyl, C.sub.2-C.sub.4 alkenyl, C.sub.1-C.sub.4 haloalkyl, cyano-C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4 haloalkenyl, C.sub.2-C.sub.4 alkynyl and C.sub.2-C.sub.4 haloalkynyl; R.sup.2 is selected from the group consisting of hydrogen, halogen, cyano, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6haloalkoxy, C.sub.1-C.sub.3haloalkoxy-C.sub.1-C.sub.3alkyl-, C.sub.1-C.sub.6alkoxy, C.sub.1-C.sub.3alkoxy-C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3alkoxy-C.sub.1-C.sub.3alkoxy-C.sub.1-C.sub.3alkyl-, C.sub.3-C.sub.6cycloalkyl, C.sub.2-C.sub.6 alkenyl, C.sub.2-C.sub.6 haloalkenyl, C.sub.2-C.sub.6 alkynyl, C.sub.1-C.sub.6hydroxyalkyl-, C.sub.1-C.sub.6alkylcarbonyl-, —S(O).sub.mC.sub.1-C.sub.6alkyl, amino, C.sub.1-C.sub.6alkylamino, C.sub.1-C.sub.6dialkylamino, —C(C.sub.1-C.sub.3alkyl)=N—O—C.sub.1-C.sub.3alkyl and C.sub.2-C.sub.6 haloalkynyl; G is hydrogen, or C(O)R.sup.3; R.sup.3 is selected from the group consisting of C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkenyl, C.sub.1-C.sub.6alkynyl, C.sub.1-C.sub.6alkyl-S—, —NR.sup.4R.sup.5 and phenyl optionally substituted by one or more R.sup.6; R.sup.4 and R.sup.5 are independently selected from the group consisting of C.sub.1-C.sub.6 alkyl and C.sub.1-C.sub.6 alkoxy, or R.sup.4 and R.sup.5 together can form a morpholinyl ring; R.sup.6 is selected from the group consisting of halogen, cyano, nitro, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalky, C.sub.1-C.sub.3alkoxy and C.sub.1-C.sub.3haloalkoxy; X and Y are each independently hydrogen, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3haloalkoxy, or halogen; D is a substituted or unsubstituted monocyclic heteroaryl ring containing 1, 2, or 3 heteroatoms independently selected from oxygen, nitrogen and sulphur, and wherein when D is substituted it is substituted on at least one ring carbon atom with R.sup.8 and/or on a ring nitrogen atom with R.sup.9; each R.sup.8 is independently oxygen, hydroxyl, halogen, cyano, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6haloalkoxy, C.sub.1-C.sub.3haloalkoxy-C.sub.1-C.sub.3alkyl-, C.sub.1-C.sub.6alkoxy, C.sub.1-C.sub.3alkoxy-C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3alkoxy-C.sub.1-C.sub.3alkoxy-C.sub.1-C.sub.3alkyl-, C.sub.3-C.sub.6cycloalkyl, C.sub.2-C.sub.6 alkenyl, C.sub.2-C.sub.6 haloalkenyl, C.sub.2-C.sub.6 alkynyl, C.sub.1-C.sub.6hydroxyalkyl-, C.sub.1-C.sub.6alkylcarbonyl-, C.sub.1-C.sub.6alkyl-S(O).sub.m—, amino, C.sub.1-C.sub.6alkylamino, C.sub.1-C.sub.6dialkylamino, —C(C.sub.1-C.sub.3alkyl)=N—O—C.sub.1-C.sub.3alkyl and C.sub.2-C.sub.6 haloalkynyl; m is an integer of 0, 1, or 2; and each R.sup.9 is independently, C.sub.1-C.sub.4 alkyl, C.sub.3-C.sub.6alkoxy, C.sub.1-C.sub.2 alkoxy-C.sub.1-C.sub.2 alkyl, C.sub.2-C.sub.4 alkenyl, C.sub.1-C.sub.4 haloalkyl, C.sub.2-C.sub.4 haloalkenyl, C.sub.2-C.sub.4 alkynyl or C.sub.2-C.sub.4 haloalkynyl; or, D is a substituted or unsubstituted phenyl ring (Dp), ##STR00078## wherein p denotes the point of attachment of (Dp) to the rest of the molecule; Z.sup.1, Z.sup.2, Z.sup.3, Z.sup.4, and Z.sup.5 are each independently selected from hydrogen, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3haloalkoxy, or halogen; and W is either ##STR00079##  wherein “a” denotes the point of attachment to the phenyl-pyridazinone/phenyl-pyridazine dione moiety, “b” denotes the point of attachment to ring D, R.sup.10, R.sup.12, R.sup.14 and R.sup.15 are each independently hydrogen, C.sub.1-C.sub.3alkyl, or C.sub.1-C.sub.3haloalkyl; or R.sup.10 and R.sup.12 together with the carbon atoms to which they are joined forma a C.sub.3-C.sub.6 carbocyclic ring; R.sup.11 and R.sup.13 are each independently hydrogen, halogen, C.sub.1-C.sub.3alkyl, or C.sub.1-C.sub.3haloalkyl, provided that when one of R.sup.11 or R.sup.13 is halogen, C.sub.1-C.sub.3alkyl or C.sub.1-C.sub.3 haloalkyl, the other is hydrogen; and (B) one or more compounds of formula (II) ##STR00080## wherein, R.sup.B11 is H, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6 haloalkyl or C.sub.4-C.sub.8 cycloalkyl; R.sup.B6 is H, C.sub.1-C.sub.6alkyl, or C.sub.1-C.sub.6alkoxy; Q.sup.B1 is an optionally substituted ring system, selected from the group consisting of phenyl, thienyl, pyridinyl, benzodioxolyl, naphthyl, naphthalenyl, benzofuranyl, furanyl, benzothiophenyl, and pyrazolyl, wherein when substituted said ring system is substituted by 1 to 3 R.sup.B4; Q.sup.B2 is an optionally substituted ring system, selected from the group consisting of phenyl, pyridinyl, benzodioxolyl, pyridinone, thiadazolyl, thiazolyl, and oxazolyl, wherein when substituted said ring system is substituted by 1 to 3 R.sup.B5; each R.sup.B4 is independently halogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, C.sub.1-C.sub.6haloalkoxy, C.sub.3-C.sub.8cycloalkyl, cyano, C.sub.1-C.sub.6alkylthio, C.sub.1-C.sub.6alkylsulphinyl, C.sub.1-C.sub.6alkylsulphonyl, SF.sub.5, NHR.sup.B8, phenyl optionally substituted by 1-3 R.sup.B7, or pyrazolyl optionally substituted by 1-3 R.sup.B7; each R.sup.B5 is independently halogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, C.sub.1-C.sub.6haloalkoxy, cyano, nitro, C.sub.1-C.sub.6alkylthio, C.sub.1-C.sub.6alkylsulphinyl, or C.sub.1-C.sub.6alkylsulphonyl; each R.sup.B7 is independently C.sub.1-C.sub.6alkyl, halogen, or C.sub.1-C.sub.6haloalkyl; and R.sup.B8 is C.sub.1-C.sub.4alkoxycarbonyl; or an N-oxide, or a salt form thereof.

2. The composition of claim 1, wherein W is W1 and each of R.sup.10, R.sup.11, R.sup.12, and R.sup.13 is hydrogen.

3. The composition of claim 1, wherein W is W2 and each of R.sup.14 and R.sup.15 is hydrogen.

4. The composition of claim 1, wherein W is ##STR00081##

5. The composition of claim 1, wherein component (A) is a compound of formula (I) or a salt or N-oxide thereof, selected from the group consisting of 1.001, 1.002, 1.012, 1.018, 1.024, 1.042, 1.048, 1.054, 1.060, 1.066, 1.089, 1.095, 1.125, and 1.149 as defined in the table below: TABLE-US-00020 Compound No. Name Structure 1.001 4-[3-chloro-6-fluoro-2-(2- phenylethyl)pheny1]-5-hydroxy-2,6- dimethyl-pyridazin-3-one 1.002 4-[3-chloro-6-fluoro-2-[(E)- styryl]pheny1]-5-hydroxy-2,6- dimethyl-pyridazin-3-one 1.012 4-[3-chloro-2-[2-(4- chlorophenyl)ethy1]-6-fluoro-phenyl]- 5-hydroxy-2,6-dimethyl-pyridazin-3- one 1.018 4-[3-chloro-6-fluoro-2-[2-[4- (trifluoromethyl)phenyflethyl]pheny1]- 5-hydroxy-2,6-dimethyl-pyridazin-3- one 1.024 4-[3-chloro-6-fluoro-2-[2-[4- (cyano)phenyl]ethyl]pheny1]-5- hydroxy-2,6-dimethyl-pyridazin-3-one 1.042 4-[3-chloro-6-fluoro-2-[2-[6- (trifluoromethyl)-3- pyridyl]ethyl]pheny1]-5-hydroxy-2,6- dimethyl-pyridazin-3-one 1.048 4-[3-chloro-6-fluoro-2-[2-(4- fluorophenyl)ethyl]pheny1]-5- hydroxy-2,6-dimethyl-pyridazin-3-one 1.054 4-[3-chloro-6-fluoro-2-[2-(3- pyridyl)ethyl]pheny1]-5-hydroxy-2,6- dimethyl-pyridazin-3-one 1.060 4-[3-chloro-2-[2-(3,4- difluorophenyl)ethy1]-6-fluoro- pheny1]-5-hydroxy-2,6-dimethyl- pyridazin-3-one 1.066 4-[3-chloro-6-fluoro-2-[2-[2- (trifluoromethyl)phenyflethyl]pheny1]- 5-hydroxy-2,6-dimethyl-pyridazin-3- one 1.089 [5-[3-chloro-2-[2-(4- chlorophenyl)ethy1]-6-fluoro-pheny1]- 1,3-dimethyl-6-oxo-pyridazin-4-yl] methylpropanoate 1.095 [5-[3-chloro-6-fluoro-2-[2-[4- (trifluoromethyl)phenyflethyl]pheny1]- 1,3-dimethyl-6-oxo-pyridazin-4-yl] 2- methylpropanoate 1.125 [5-[3-chloro-6-fluoro-2-[2-(4- fluorophenyl)ethyl]pheny1]-1,3- dimethyl-6-oxo-pyridazin-4-yl] 2- methylpropanoate 1.149 [5-[3-chloro-6-fluoro-2-[2-(p- tolyl)ethyl]pheny1]-1,3-dimethyl-6- oxo-pyridazin-4-yl] 2- methylpropanoate

6. The composition of claim 1, wherein component (B) is selected from the group of compounds consisting of 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 2.10, 2.11, 2.12, 2.13, 2.14, 2.15, 2.16, 2.17, and 2.18, as defined in the table below: TABLE-US-00021 Compound No. Name Structure 2.1 N-(2-fluorophenyl)-2-oxo-4-[3- (trifluoromethyl)phenyl]pyrrolidine- 3-carboxamide 2.2 N-(2,3-difluoropheny1)-2-oxo-4-[3- (trifluoromethyl)phenyl]pyrrolidine- 3-carboxamide 2.3 2-oxo-4-[3- (trifluoromethyl)pheny1]-N-(2,3,4- trifluorophenyl)pyrrolidine-3- carboxamide 2.4 N-(2-fluoropheny1)-1-methy1-2- oxo-4-[3- (trifluoromethyl)phenyl]pyrrolidine- 3-carboxamide 2.5 N-(2-fluorophenyl)-2-oxo-4-[4- (trifluoromethyl)phenyl]pyrrolidine- 3-carboxamide 2.6 N-(2-fluoropheny1)-1-methy1-2- oxo-4-[4- (trifluoromethyl)phenyl]pyrrolidine- 3-carboxamide 2.7 N-(2,3-difluoropheny1)-2-oxo-4-[4- (trifluoromethyl)phenyl]pyrrolidine- 3-carboxamide 2.8 N-(2,3-difluoropheny1)-1-methy1-2- oxo-4-[4- (trifluoromethyl)phenyl]pyrrolidine- 3-carboxamide 2.9 2-oxo-4-[4- (trifluoromethyl)pheny1]-N-(2,3,4- trifluorophenyl)pyrrolidine-3- carboxamide 2.10 N-(2-fluorophenyl)-4-(4- fluoropheny1)-1-methy1-2-oxo- pyrrolidine-3-carboxamide 2.11 N-(2,3-difluoropheny1)-4-(3,4- difluoropheny1)-2-oxo-pyrrolidine- 3-carboxamide 2.12 4-(3,4-difluoropheny1)-N-(2- fluorophenyl)-2-oxo-pyrrolidine-3- carboxamide 2.13 N-(2,4-difluoropheny1)-4-(3,5- difluoropheny1)-2-oxo-pyrrolidine- 3-carboxamide 2.14 N-(2,3-difluoropheny1)-4-(3- isopropylpheny1)-2-oxo- pyrrolidine-3-carboxamide 2.15 N-(2,3-difluoropheny1)-2-oxo-4[6- (trifluoromethyl)-3- pyridyl]pyrrolidine-3-carboxamide 2.16 4-(3,5-difluoropheny1)-N-[3-fluoro- 2-(trifluoromethyl)pheny1]-1- methyl-2-oxo-pyrrolidine-3- carboxamide 2.17 N-(2,4-difluoropheny1)-4-(3,5- difluoropheny1)-1-methy1-2-oxo- pyrrolidine-3-carboxamide 2.18 N-(2,3-difluoropheny1)-4-(3,5- difluoropheny1)-1-methy1-2-oxo- pyrrolidine-3-carboxamide

7. The composition of claim 1, selected from the group consisting of composition 1 to composition 252 as defined in the table below: TABLE-US-00022 Composition A Cmpd B Cmpd Number of formula (I) of formula (II) 1 1.001 2.1 2 1.002 2.1 3 1.012 2.1 4 1.018 2.1 5 1.024 2.1 6 1.042 2.1 7 1.048 2.1 8 1.054 2.1 9 1.060 2.1 10 1.066 2.1 11 1.089 2.1 12 1.095 2.1 13 1.125 2.1 14 1.149 2.1 15 1.001 2.2 16 1.002 2.2 17 1.012 2.2 18 1.018 2.2 19 1.024 2.2 20 1.042 2.2 21 1.048 2.2 22 1.054 2.2 23 1.060 2.2 24 1.066 2.2 25 1.089 2.2 26 1.095 2.2 27 1.125 2.2 28 1.149 2.2 29 1.001 2.3 30 1.002 2.3 31 1.012 2.3 32 1.018 2. 33 1.024 2.3 34 1.042 2.3 35 1.048 2.3 36 1.054 2.3 37 1.060 2.3 38 1.066 2.3 39 1.089 2.3 40 1.095 2.3 41 1.125 2.3 42 1.149 2.3 43 1.001 2.4 44 1.002 2.4 45 1.012 2.4 46 1.018 2.4 47 1.024 2.4 48 1.042 2.4 49 1.048 2.4 50 1.054 2.4 51 1.060 2.4 52 1.066 2.4 53 1.089 2.4 54 1.095 2.4 55 1.125 2.4 56 1.149 2.4 57 1.001 2.5 58 1.002 2.5 59 1.012 2.5 60 1.018 2.5 61 1.024 2.5 62 1.042 2.5 63 1.048 2.5 64 1.054 2.5 65 1.060 2.5 66 1.066 2.5 67 1.089 2.5 68 1.095 2.5 69 1.125 2.5 70 1.149 2.5 71 1.001 2.6 72 1.002 2.6 73 1.012 2.6 74 1.018 2.6 75 1.024 2.6 76 1.042 2.6 77 1.048 2.6 78 1.054 2.6 79 1.060 2.6 80 1.066 2.6 81 1.089 2.6 82 1.095 2.6 83 1.125 2.6 84 1.149 2.6 85 1.001 2.7 86 1.002 2.7 87 1.012 2.7 88 1.018 2.7 89 1.024 2.7 90 1.042 2.7 91 1.048 2.7 92 1.054 2.7 93 1.060 2.7 94 1.066 2.7 95 1.089 2.7 96 1.095 2.7 97 1.125 2.7 98 1.149 2.7 99 1.001 2.8 100 1.002 2.8 101 1.012 2.8 102 1.018 2.8 103 1.024 2.8 104 1.042 2.8 105 1.048 2.8 106 1.054 2.8 107 1.060 2.8 108 1.066 2.8 109 1.089 2.8 110 1.095 2.8 111 1.125 2.8 112 1.149 2.8 113 1.001 2.9 114 1.002 2.9 115 1.012 2.9 116 1.018 2.9 117 1.024 2.9 118 1.042 2.9 119 1.048 2.9 120 1.054 2.9 121 1.060 2.9 122 1.066 2.9 123 1.089 2.9 124 1.095 2.9 125 1.125 2.9 126 1.149 2.9 127 1.001 2.10 128 1.002 2.10 129 1.012 2.10 130 1.018 2.10 131 1.024 2.10 132 1.042 2.10 133 1.048 2.10 134 1.054 2.10 135 1.060 2.10 136 1.066 2.10 137 1.089 2.10 138 1.095 2.10 139 1.125 2.10 140 1.149 2.10 141 1.001 2.11 142 1.002 2.11 143 1.012 2.11 144 1.018 2.11 145 1.024 2.11 146 1.042 2.11 147 1.048 2.11 148 1.054 2.11 149 1.060 2.11 150 1.066 2.11 151 1.089 2.11 152 1.095 2.11 153 1.125 2.11 154 1.149 2.11 155 1.001 2.12 156 1.002 2.12 157 1.012 2.12 158 1.018 2.12 159 1.024 2.12 160 1.042 2.12 161 1.048 2.12 162 1.054 2.12 163 1.060 2.12 164 1.066 2.12 165 1.089 2.12 166 1.095 2.12 167 1.125 2.12 168 1.149 2.12 169 1.001 2.13 170 1.002 2.13 171 1.012 2.13 172 1.018 2.13 173 1.024 2.13 174 1.042 2.13 175 1.048 2.13 176 1.054 2.13 177 1.060 2.13 178 1.066 2.13 179 1.089 2.13 180 1.095 2.13 181 1.125 2.13 182 1.149 2.13 183 1.001 2.14 184 1.002 2.14 185 1.012 2.14 186 1.018 2.14 187 1.024 2.14 188 1.042 2.14 189 1.048 2.14 190 1.054 2.14 191 1.060 2.14 192 1.066 2.14 193 1.089 2.14 194 1.095 2.14 195 1.125 2.14 196 1.149 2.14 197 1.001 2.15 198 1.002 2.15 199 1.012 2.15 200 1.018 2.15 201 1.024 2.15 202 1.042 2.15 203 1.048 2.15 204 1.054 2.15 205 1.060 2.15 206 1.066 2.15 207 1.089 2.15 208 1.095 2.15 209 1.125 2.15 210 1.149 2.15 211 1.001 2.16 212 1.002 2.16 213 1.012 2.16 214 1.018 2.16 215 1.024 2.16 216 1.042 2.16 217 1.048 2.16 218 1.054 2.16 219 1.060 2.16 220 1.066 2.16 221 1.089 2.16 222 1.095 2.16 223 1.125 2.16 224 1.149 2.16 225 1.001 2.17 226 1.002 2.17 227 1.012 2.17 228 1.018 2.17 229 1.024 2.17 230 1.042 2.17 231 1.048 2.17 232 1.054 2.17 233 1.060 2.17 234 1.066 2.17 235 1.089 2.17 236 1.095 2.17 237 1.125 2.17 238 1.149 2.17 239 1.001 2.18 240 1.002 2.18 241 1.012 2.18 242 1.018 2.18 243 1.024 2.18 244 1.042 2.18 245 1.048 2.18 246 1.054 2.18 247 1.060 2.18 248 1.066 2.18 249 1.089 2.18 250 1.095 2.18 251 1.125 2.18 252 1.149 2.18 wherein compounds 1.001, 1.002, 1.012, 1.018, 1.024, 1.042, 1.048, 1.054, 1.060, 1.066, 1.089, 1.095, 1.125, and 1.149 are as defined in claim 5, and compounds 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 2.10, 2.11, 2.12, 2.13, 2.14, 2.15, 2.16, 2.17, and 2.18 are as defined in claim 6.

8. The composition of claim 1, wherein the weight ratio of component (A) to component (B) is from 0.01:1 to 100:1.

9. The composition of claim 1, wherein the weight ratio of component (A) to component (B) is from 0.05:1 to 20:1.

10. The composition of claim 1, wherein the weight ratio of component (A) to component (B) is from 0.1:1 to 20:1.

11. The herbicidal composition of claim 1, additionally comprising an agriculturally acceptable formulation adjuvant.

12. The herbicidal composition of claim 11, further comprising at least one additional pesticide.

13. The herbicidal composition according to claim 12, wherein the additional pesticide is a herbicide or herbicide safener.

14. A method of controlling unwanted plant growth, comprising applying (A) a compound of formula (I) as defined in claim 1, and (B) a compound of formula (II) as defined in claim 1, to the unwanted plants or to the locus thereof.

15. The method of claim 14, wherein the compounds of formula (I) and formula (II) are applied in the form of a composition as defined in claim 1.

Description

PREPARATION EXAMPLES FOR COMPOUNDS OF FORMULA (1)

Example 1 Preparation of 4-(3-chloro-6-fluoro-2-phenethyl-phenyl)-5-hydroxy-2,6-dimethyl-pyridazin-3-one

[0226] ##STR00059##

1.1 3-allyl-2-bromo-1-chloro-4-fluoro-benzene

[0227] A solution of lithium diisopropylamide (2M in tetrahydrofuran, 3.6 ml, 7.2 mmol) was cooled to −78° C. under N.sub.2. A solution of 2-bromo-1-chloro-4-fluoro-benzene (1.0 g, 4.8 mmol) in tetrahydrofuran was added dropwise at −78° C. The mixture was stirred for 45 minutes at the same temperature before being treated with allyl bromide (0.3 ml, 5.7 mmol). The reaction was continued at −78° C. for 2 h then allowed to warm to rt. The reaction was quenched with sat. NH.sub.4Cl (aq) and extracted with ethyl acetate. The organics were separated and kept, then washed with brine. The organics were dried over sodium sulfate and concentrated under reduced pressure to give 3-allyl-2-bromo-1-chloro-4-fluoro-benzene (1.2 g, 100%) as an oil.

##STR00060##

[0228] .sup.1H NMR (400 MHz, CDCl.sub.3) δ.sub.H: 7.34-7.30 (m, 1H), 7.01-6.96 (m, 1H), 5.94-5.83 (m, 1H), 5.10-5.00 (m, 2H), 3.64-3.58 (m, 2H).

1.2 2-(2-bromo-3-chloro-6-fluoro-phenyl)acetic Acid

[0229] A solution of 3-allyl-2-bromo-1-chloro-4-fluoro-benzene (15.0 g, 60.1 mmol) in dichloromethane (200 mL) in a 2-necked flask was cooled to −78° C. One side neck was connected to a trap containing an aqueous solution of KI. Ozone was bubbled through the solution until the starting material was fully consumed (5 hours). Air was bubbled through the solution for 10 minutes to remove excess ozone. Dimethyl sulfide (44 ml, 601 mmol) was added and the mixture allowed to warm to rt. The reaction was continued for 16 h at rt.

[0230] The mixture was washed with brine (2×100 mL) and the organic layer kept. The organics were dried over Na.sub.2SO.sub.4, filtered and concentrated under reduced pressure to give crude 2-(2-bromo-3-chloro-6-fluoro-phenyl)acetaldehyde (15.3 g) which was used for the next step without further purification.

[0231] Crude 2-(2-bromo-3-chloro-6-fluoro-phenyl)acetaldehyde (15.3 g, 60.8 mmol) was dissolved in a mixture of tert-butanol (92 mL) and water (46 mL) then cooled to 0° C. 2-methylbut-2-ene (64.5 mL, 608 mmol), sodium dihydrogen phosphate (34.6 g, 243 mmol) and sodium chlorite (16.5 g, 163 mmol) were added. The mixture was stirred for 2 h then diluted with brine (150 mL) and 2M hydrochloric acid (150 mL). The mixture was extracted with ethyl acetate (3×100 mL). The combined organic extracts were washed with a saturated aqueous solution of sodium metabisulfite (100 mL) then dried over Na.sub.2SO.sub.4, filtered and concentrated under reduced pressure to provide a pale yellow solid. The crude solid was dissolved in a mixture of water (100 mL) and 2.0M NaOH (30 mL). The aqueous solution was washed with ethyl acetate (100 mL) and the organics discarded. The aqueous layer was acidified by addition of concentrated hydrochloric acid (20 mL) resulting in the formation of a white suspension. The mixture was extracted with ethyl acetate (3×200 mL). The combined organics were washed with brine, dried over Na.sub.2SO.sub.4, filtered and evaporated to provide 2-(2-bromo-3-chloro-6-fluoro-phenyl)acetic acid (8.0 g, 49%) as a white solid.

##STR00061##

[0232] .sup.1H NMR (400 MHz, DMSO-d6) δ.sub.H: 12.79 (br.s, 1H), 7.67-7.59 (m, 1H), 7.39-7.31 (m, 1H), 3.82 (s, 2H).

1.3 2-(2-bromo-3-chloro-6-fluoro-phenyl)-N-methyl-acetohydrazide

[0233] To a stirred solution of 2-(2-bromo-3-chloro-6-fluoro-phenyl)acetic acid (2.0 g, 7.5 mmol) in dichloromethane (20 ml) at 0° C. was added N-(3-Dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride [EDC.HCl] (1.4 g, 9.0 mmol), followed by dropwise addition of methyl hydrazine (0.4 ml, 7.5 mmol). The temperature of the reaction mixture was maintained at 0° C. for 3 h. The reaction was then quenched with water and extracted into dichloromethane. The organics were separated, washed with brine and dried over Na.sub.2SO.sub.4. Concentration under reduced pressure gave crude 2-(2-bromo-3-chloro-6-fluoro-phenyl)-N-methyl-acetohydrazide (1.8 g, 81%) which was used in the next step without further purification.

##STR00062##

[0234] .sup.1H NMR (400 MHz, DMSO-d6) δ.sub.H: 7.59 (dd, J=8.9 and 5.4, 1H), 7.30 (t, J=8.9, 1H), 4.91 (s, 2H), 4.10 (br. s, 2H), 3.02 (s, 3H).

1.4 2-{[2-(2-Bromo-3-chloro-6-fluoro-phenyl)-acetyl]-methyl-hydrazono}-propionic Acid ethyl ester

[0235] To a stirred solution of 2-(2-bromo-3-chloro-6-fluoro-phenyl)-N-methyl-acetohydrazide (1.8 g, 6.09 mmol) in ethanol (5 ml) was added ethyl pyruvate (0.7 ml, 6.7 mmol) dropwise. The reaction was heated at 80° C. for 4 h. The reaction mixture was then allowed to cool to rt, and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel (eluent an ethyl acetate/hexane gradient) to give the desired compound 2-{[2-(2-Bromo-3-chloro-6-fluoro-phenyl)-acetyl]-methyl-hydrazono}-propionic acid ethyl ester (1.8 g, 75%) as an off-white solid.

##STR00063##

[0236] .sup.1H NMR (400 MHz, CDCl.sub.3) δ.sub.H:7.40-7.35 (m, 1H), 7.04-6.98 (m, 1H), 4.32 (q, J=7.1, 2H), 4.24 (s, 2H), 3.41 (s, 3H), 2.32 (s, 3H), 1.36 (t, J=7.1, 3H).

1.5 4-(2-bromo-3-chloro-6-fluoro-phenyl)-5-hydroxy-2,6-dimethyl-pyridazin-3-one

[0237] 2-{[2-(2-Bromo-3-chloro-6-fluoro-phenyl)-acetyl]-methyl-hydrazono}-propionic acid ethyl ester (500 mg, 1.27 mmol) was dissolved in acetonitrile (2.5 ml) and treated with 1,8-diazabicyclo[5.4.0]undec-7-ene [DBU] (0.47 ml, 3.2 mmol). The mixture was heated to 125° C. using microwave irradiation for 1 h. The reaction mixture was then evaporated under reduced pressure. The residue was dissolved in water and acidified to pH 1 with 2N hydrochloric acid. The mixture was extracted with DCM, the organics separated and washed with brine solution. The organic solution was dried over Na.sub.2SO.sub.4 and concentrated under reduced pressure to give crude product. The crude was purified by column chromatography on silica gel (eluent an ethyl acetate/hexane gradient) to give 4-(2-bromo-3-chloro-6-fluoro-phenyl)-5-hydroxy-2,6-dimethyl-pyridazin-3-one (340 mg, 77.1%) as an off-white solid.

##STR00064##

[0238] .sup.1H NMR (400 MHz, DMSO-d6) δ.sub.H: 11.01 (s, 1H), 7.77-7.73 (m, 1H), 7.39 (t, J=8.7, 1H), 3.58 (s, 3H), 2.24 (s, 3H).

1.6 [5-(2-bromo-3-chloro-6-fluoro-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate

[0239] To a stirred solution of 4-(2-bromo-3-chloro-6-fluoro-phenyl)-5-hydroxy-2,6-dimethyl-pyridazin-3-one (1.4 g, 4.02 mmol) in dichloromethane (32 ml) at rt were added triethylamine (1.1 ml, 8.06 mmol), 4-(dimethylamino)pyridine [DMAP] (49 mg, 0.40 mmol) and isobutyryl chloride (0.6 ml, 4.83 mmol).

[0240] Once judged complete, the reaction was diluted with dichloromethane and water. The organic layer was separated, dried over Na.sub.2SO.sub.4, and concentrated under reduced pressure to give crude product. The crude was purified by column chromatography on silica gel (eluent an ethyl acetate/hexane gradient) to give [5-(2-bromo-3-chloro-6-fluoro-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (1.47 g, 87%).

##STR00065##

[0241] .sup.1H NMR (400 MHz, CDCl.sub.3) δ.sub.H: 7.51-7.47 (m, 1H), 7.10-7.05 (m, 1H), 3.82 (s, 3H), 2.60-2.55 (m, 1H), 2.25 (s, 3H), 1.02-0.98 (m, 6H).

1.7 4-[3-chloro-6-fluoro-2-[(E)-styryl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one

[0242] Solid K.sub.2CO.sub.3 (298 mg, 2.16 mmol), trans-2-phenylvinylboronic acid (213 mg, 1.43 mmol) and PdCl.sub.2(dppf).DCM (118 mg, 0.143 mmol) were placed under argon atmosphere. A solution of [5-(2-bromo-3-chloro-6-fluoro-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (250 mg, 0.72 mmol) in 1,4-dioxane (4 ml) was added and the mixture stirred at 95° C. for 18 h.

[0243] The reaction mixture was evaporated directly under reduced pressure to give a residue which was purified by column chromatography on silica gel (eluent an ethyl acetate/hexane gradient to give 4-[3-chloro-6-fluoro-2-[(E)-styryl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (160 mg, 72%).

##STR00066##

[0244] .sup.1H NMR (DMSO-d6) δ.sub.H: 10.8 (s, 1H), 7.62 (m, 1H), 7.37-7.24 (m, 6H), 6.94 (d, J=16.5, 1H), 6.57 (d, J=16.5, 1H), 6.53 (s, 3H), 2.18 (s, 3H).

1.8 4-(3-chloro-6-fluoro-2-phenethyl-phenyl)-5-hydroxy-2,6-dimethyl-pyridazin-3-one

[0245] A stirred mixture of 4-[3-chloro-6-fluoro-2-[(E)-styryl]phenyl]-5-hydroxy-2,6-di methyl-pyridazin-3-one (200 mg, 0.54 mmol) and Pd/C (40 mg) in tetrahydrofuran (10 ml) was treated with hydrogen under balloon pressure for 21 h.

[0246] The catalyst was removed by filtration and the reaction solution evaporated to dryness. The residue was purified by flash column chromatography on silica gel (eluent an ethyl acetate/hexanes gradient) to give 4-(3-chloro-6-fluoro-2-phenethyl-phenyl)-5-hydroxy-2,6-dimethyl-pyridazin-3-one (110 mg, 55%) as a white solid.

##STR00067##

[0247] .sup.1H NMR (DMSO-d6) δ.sub.H: 10.85 (s, 1H), 7.57-7.53 (m, 1H), 7.27-7.15 (m, 4H), 7.0 (d, J=7.2, 2H), 3.60 (s, 3H), 2.73-2.50 (m, 4H), 2.25 (s, 3H).

Example 2 Preparation of 4-[3-chloro-6-fluoro-2-[2-(4-fluorophenyl)ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one

[0248] ##STR00068##

2.1 [5-[3-chloro-6-fluoro-2-[(E)-2-(4-fluorophenyl)vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate

[0249] A mixture of [5-(2-bromo-3-chloro-6-fluoro-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (0.50 g, 1.20 mmol, 1.0 equiv.) [prepared as described in Example 1], tris(dibenzylideneacetone)dipalladium(0) (27 mg, 0.030 mmol, 0.025 equiv.) and tri-tertbutylphosphonium tetrafluoroborate (35 mg, 0.12 mmol, 0.1 equiv.) was treated with degassed triethylamine (12 mL). 1-fluoro-4-vinyl-benzene (0.43 mL, 0.44 g, 3.59 mmol, 3.0 equiv.) was added and the mixture heated to 95° C. for 18.5 hrs.

[0250] Heating was halted and LC/MS analysis showed high conversion to the target stilbene. The reaction mixture was diluted with dichloromethane and filtered through celite, washing with further dichloromethane. The liquors were concentrated to dryness. The crude product was partially purified by flash column chromatography (silica, eluent ethyl acetate/isohexane) to afford desired stilbene [5-[3-chloro-6-fluoro-2-[(E)-2-(4-fluorophenyl)vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (0.36 g, 0.774 mmol, 65% yield) as a colourless gum.

##STR00069##

[0251] .sup.1H NMR (400 MHz, CDCl.sub.3) δ.sub.H=7.45-7.41 (m, 1H), 7.35-7.30 (m, 2H), 7.04-6.98 (m, 3H), 6.93 (d, 1H), 6.61 (d, 1H), 3.71 (s, 3H), 2.64 (sept, 1H), 2.23 (s, 3H), 1.09 (dd, 6H).

2.2 [5-[3-chloro-6-fluoro-2-[2-(4-fluorophenyl)ethyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate

[0252] [5-[3-chloro-6-fluoro-2-[(E)-2-(4-fluorophenyl)vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (130 mg, 0.283 mmol) was subjected to catalytic hydrogenation in tetrahydrofuran (3 mL) over 5% Pd/C catalyst (60 mg) at 3 barg H.sub.2.

[0253] After 1.5 hrs, LC/MS showed complete reaction. The reaction mixture was filtered through a pad of celite, washing with ethyl acetate. The liquors were concentrated in-vacuo to afford a crude residue.

[0254] The residue was adsorbed onto silica and purified by flash column chromatography (silica, eluent ethyl acetate/isohexane) to give [5-[3-chloro-6-fluoro-2-[2-(4-fluorophenyl)ethyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (85 mg, 65% yield) as a colourless gum.

##STR00070##

[0255] .sup.1H NMR (400 MHz, CDCl.sub.3) δ.sub.H=7.42 (dd, 1H), 7.11-7.06 (m, 2H), 6.99 (t, 1H), 6.97-6.90 (m, 2H), 3.84 (s, 3H), 2.86-2.68 (m, 4H), 2.55 (sept, 1H), 2.26 (s, 3H), 0.98 (dd, 6H).

2.3 4-[3-chloro-6-fluoro-2-[2-(4-fluorophenyl)ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one

[0256] [5-[3-chloro-6-fluoro-2-[2-(4-fluorophenyl)ethyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl]2-methylpropanoate (108 mg, 0.234 mmol, 1.0 equiv.) was dissolved in ethanol (7.5 mL). The mixture was treated with a solution of lithium hydroxide (17 mg, 0.703 mmol, 3.0 equiv.) in water (2.5 mL). The reaction was stirred at rt for 2 hrs.

[0257] LC/MS showed complete conversion. The reaction mixture was concentrated in-vacuo to remove ethanol. The remaining aqueous solution was acidified with 1M HCl (30 mL) and extracted with EtOAc (3×30 mL). The combined organics were dried over MgSO.sub.4, filtered and concentrated in-vacuo to afford crude product.

[0258] Purification by flash column chromatography (silica, eluent ethyl acetate/isohexane) gave 4-[3-chloro-6-fluoro-2-[2-(4-fluorophenyl)ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (83 mg, 91% yield) as a white solid.

##STR00071##

[0259] .sup.1H NMR (400 MHz, CDCl.sub.3) δ.sub.H=7.44 (dd, 1H), 7.01-6.88 (m, 5H), 5.91 (br s, 1H), 3.73 (s, 3H), 2.81-2.65 (m 4H), 2.30 (s, 3H).

Example 3 Preparation of 4-[3-chloro-6-fluoro-2-[2-[6-(trifluoromethyl)-3-pyridyl]ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one

[0260] ##STR00072##

3.1 [5-[3-chloro-6-fluoro-2-[(E)-2-[6-(trifluoromethyl)-3-pyridyl]vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate

[0261] Triethylamine (12 mL) was sparged with nitrogen for 2 minutes. It was then added to a mixture of [5-(2-bromo-3-chloro-6-fluoro-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (1.65 g, 3.95 mmol, 1.0 eq.) [prepared as described in Example 1], Pd.sub.2(dba).sub.3 (90 mg, 0.099 mmol, 0.025 eq.) and tri tert-butylphosphonium tetrafluoroborate (115 mg, 0.40 mmol, 0.1 eq.). 2-(trifluoromethyl)-5-vinyl-pyridine (1.71 g, 9.88 mmol, 2.5 eq.) was added and the mixture heated at 95° C. for 6 hours.

[0262] The mixture was allowed to cool to room temperature then diluted with dichloromethane (20 mL). The mixture was washed with hydrochloric acid (20 mL, 2.0 M). The organics were dried over MgSO.sub.4, filtered and concentrated in vacuo. The crude product was purified by flash column chromatography to provide [5-[3-chloro-6-fluoro-2-[(E)-2-[6-(trifluoromethyl)-3-pyridyl]vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (1.41 g, 2.76 mmol, 70% yield) as an orange oil.

##STR00073##

[0263] .sup.1H NMR (400 MHz, CDCl.sub.3) δ.sub.H: 8.65 (d, J=1.6, 1H), 7.87 (dd, J=8.2 and 2.1, 1H), 7.64 (d, J=8.2, 1H), 7.47 (dd, J=8.9 and 5.0, 1H), 7.17 (d, J=16.5, 1H), 7.08 (t, J=8.7, 1H), 6.75 (d, J=16.5, 1H), 3.71 (s, 3H), 2.66 (spt, J=7.0, 1H), 2.24 (s, 3H), 1.11 (d, J=7.0, 3H), 1.08 (d, J=7.1, 3H).

3.2 [5-[3-chloro-6-fluoro-2-[2-[6-(trifluoromethyl)-3-pyridyl]ethyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate

[0264] Tetrahydrofuran (12 mL) was added to a mixture of [5-[3-chloro-6-fluoro-2-[(E)-2-[6-(trifluoromethyl)-3-pyridyl]vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (1.2 g, 2.4 mmol, 1.0 eq.) and 10% palladium on activated charcoal catalyst (0.25 g) under nitrogen atmosphere. The mixture was subjected to hydrogenation at 4 bar hydrogen for 16 hours.

[0265] The mixture was filtered through celite, washing with further tetrahydrofuran, and the filtrate was concentrated in vacuo. The crude product was purified by flash column chromatography to provide [5-[3-chloro-6-fluoro-2-[2-[6-(trifluoromethyl)-3-pyridyl]ethyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (1.1 g, 91% yield) as a colourless oil.

##STR00074##

[0266] .sup.1H NMR (400 MHz, CDCl.sub.3) δ.sub.H: 8.53 (d, J=1.2, 1H), 7.69-7.63 (m, 1H), 7.62-7.55 (m, 1H), 7.44 (dd, J=8.8 and 5.1, 1H), 7.02 (t, J=8.6, 1H), 3.86 (s, 3H), 3.10-2.98 (m, 1H), 2.97-2.81 (m, 2H), 2.76-2.64 (m, 1H), 2.55 (spt, J=7.0, 1H), 2.26 (s, 3H), 0.99 (d, J=7.0, 3H), 0.95 (d, J=7.0, 3H).

3.3 4-[3-chloro-6-fluoro-2-[2-[6-(trifluoromethyl)-3-pyridyl]ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one

[0267] Lithium hydroxide (0.13 g, 5.3 mmol, 3.0 eq.) was added to a solution of [5-[3-chloro-6-fluoro-2-[2-[6-(trifluoromethyl)-3-pyridyl]ethyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (0.90 g, 1.8 mmol, 1.0 eq.) in a mixture of ethanol (13 mL) and water (4.4 mL). The mixture was stirred at room temperature for 2 days.

[0268] The mixture was concentrated in vacuo. The mixture was acidified to pH 1 by addition of hydrochloric acid (6.0 mL, 2.0 M) resulting in formation of a precipitate. The solid was isolated by filtration and re-dissolved in dichloromethane (40 mL). The dichloromethane solution was dried over MgSO.sub.4, filtered and concentrated in vacuo to afford crude product. Purification by flash column chromatography gave impure title compound as a white foam. The material was further purified by reverse phase column chromatography to provide 4-[3-chloro-6-fluoro-2-[2-[6-(trifluoromethyl)-3-pyridyl]ethyl]phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (0.232 g, 0.525 mmol, 30% yield) as a white foam.

##STR00075##

[0269] .sup.1H NMR (400 MHz, CDCl.sub.3) δ.sub.H: 8.30 (s, 1H), 7.54 (d, J=1.2, 2H), 7.37 (dd, J=8.8 and 5.1, 1H), 6.95 (t, J=8.5, 1H), 3.69 (s, 3H), 2.92-2.65 (m, 4H), 2.28 (s, 3H).

[0270] Compounds 1.001, 1.002, 1.012, 1.018, 1.024, 1.042, 1.048, 1.054, 1.060, 1.066, 1.089, 1.095, 1.125 and 1.149 were prepared using the general methods as described supra. Table 4 below shows the structure of these compounds and NMR characterising data.

TABLE-US-00012 TABLE 4 Preparation examples of compounds of formula (I). The numbering system used to describe the positions of X and Y is shown for the purposes of clarity only. [00076] Compound R.sup.1 R.sup.2 G X Y W D NMR details 1.001 —Me —Me —H 6-F 3-Cl —CH.sub.2—CH.sub.2— —Ph .sup.1H NMR (DMSO-d6) δ.sub.H: 10.85 (s, 1H), 7.57-7.53 (m, 1H), 7.27-7.15 (m, 4H), 7.0 (d, J = 7.2, 2H), 3.60 (s, 3H), 2.73-2.50 (m, 4H), 2.25 (s, 3H). 1.002 —Me —Me —H 6-F 3-Cl (E)—CH═CH— —Ph .sup.1H NMR (DMSO-d6) δ.sub.H: 10.8 (s, 1H), 7.62 (m, 1H), 7.37-7.24 (m, 6H) 6.94 (d, J = 16.5, 1H), 6.57 (d, J = 16.5, 1H), 6.53 (s, 3H), 2.18 (s, 3H). 1.012 —Me —Me —H 6-F 3-Cl —CH.sub.2—CH.sub.2— 4-chloro- .sup.1H NMR (400 MHz, phenyl- chloroform) δ = 7.51- 7.44 (m, 1H), 7.21-7.15 (m, 2H), 7.07-6.98 (m, 1H), 6.93 (d, J = 8.4 Hz, 2H), 5.43-5.18 (m, 1H), 3.76 (s, 3H), 2.86-2.67 (m, 4H), 2.31 (s, 3H). 1.018 —Me —Me —H 6-F 3-Cl —CH.sub.2—CH.sub.2— 6- .sup.1H NMR (400 MHz, trifluoromethyl- CDCl.sub.3) δ ppm 2.29 (d, phenyl- J = 4.16 Hz, 3 H) 2.70- 2.93 (m, 4 H) 3.65-3.81 (m, 3 H) 6.95-7.06 (m, 1 H) 7.12 (br d, J = 6.48 Hz, 2 H) 7.48 (d, J = 8.07 Hz, 3 H). 1.024 —Me —Me —H 6-F 3-Cl —CH.sub.2—CH.sub.2— 4-cyano- .sup.1H NMR (400 MHz, phenyl- CDCl3) δ ppm 7.46- 7.51 (m, 2 H) 7.26-7.31 (m, 1 H) 7.08 (d, J = 8.19 Hz, 2 H) 6.86 (t, J = 8.50 Hz, 1 H) 3.63 (s, 3 H) 2.61-2.77 (m, 4 H) 2.24 (s, 3 H). 1.042 —Me —Me —H 6-F 3-Cl —CH.sub.2—CH.sub.2— 4- .sup.1H NMR (400 MHz, trifluoromethyl- CDCl.sub.3) δ = 8.30 (s, 1H), 3-pyridyl- 7.54 (d, J = 1.2, 2H), 7.37 (dd, J = 8.8 and 5.1, 1H), 6.95 (t, J = 8.5, 1H), 3.69 (s, 3H), 2.92-2.65 (m, 4H), 2.28 (s, 3H). 1.048 —Me —Me —H 6-F 3-Cl —CH.sub.2—CH.sub.2— 4-fluoro- .sup.1H NMR (400 MHz, phenyl- CDCl.sub.3) δ ppm 7.44 (dd, 1H), 7.01-6.88 (m, 5H), 5.91 (br s, 1H), 3.73 (s, 3H), 2.81-2.65 (m, 4H), 2.30 (s, 3H). 1.054 —Me —Me —H 6-F 3-Cl —CH.sub.2—CH.sub.2— 3-pyridyl- .sup.1H NMR (400 MHz, DMSO-d6) δ ppm 2.26 (s, 3 H) 2.58-2.82 (m, 4 H) 3.61 (s, 3 H) 7.22 (t, J = 8.80 Hz, 1 H) 7.26- 7.32 (m, 1 H) 7.46 (dt, J = 7.79, 1.79 Hz, 1 H) 7.43-7.49 (m, 1 H) 7.53 (dd, J = 8.86, 5.20 Hz, 1 H) 8.24 (s, 1 H) 8.40 (br d, J = 3.79 Hz, 1 H). 1.060 —Me —Me —H 6-F 3-Cl —CH.sub.2—CH.sub.2— 3,4-difluoro- .sup.1H NMR (400 MHz, phenyl- CDCl.sub.3) δ = 7.44 (dd, J = 5.2, 8.6 Hz, 1H), 7.04- 6.95 (m, 2H), 6.86- 6.77 (m, 1H), 6.77-6.63 (m, 1H), 3.78-3.70 (m, 3H), 2.83-2.64 (m, 4H), 2.31 (s, 3H). 1.066 —Me —Me —H 6-F 3-Cl —CH.sub.2—CH.sub.2— 2- .sup.1H NMR (400 MHz, trifluoromethyl- CDCl.sub.3) δ = 7.53 (br. d, phenyl- J = 7.5 Hz, 1H), 7.43 (br. t, J = 7.5 Hz, 1H), 7.33 (dd, J = 5.1, 8.5 Hz, 1H), 7.29-7.22 (m, 2H), 6.89 (t, J = 8.5 Hz, 1H), 3.65 (s, 3H), 2.83-2.65 (m, 4H), 2.26 (s, 3H). 1.089 —Me —Me —(C═O).sup.iPr 6-F 3-Cl —CH.sub.2—CH.sub.2— 4-chloro- .sup.1H NMR (400 MHz, phenyl- CDCl.sub.3) δ = 7.41 (dd, J = 5.1, 8.9 Hz, 1H), 7.23-7.18 (m, 2H), 7.07- 7.03 (m, 2H), 6.98 (t, J = 8.6 Hz, 1H), 3.83 (s, 3H), 2.86-2.67 (m, 4H), 2.54 (m, 1H), 2.24 (s, 3H), 0.97 (d, J = 7.0 Hz, 3H), 0.96 (d, J = 7.0 Hz, 3H). 1.095 —Me —Me —(C═O).sup.iPr 6-F 3-Cl —CH.sub.2—CH.sub.2— 4- .sup.1H NMR (400 MHz, trifluoromethyl- CDCl.sub.3) δ.sub.H = 7.50 (d, phenyl- J = 8.0, 2H), 7.43 (dd, J = 8.9 & 5.1, 1H), 7.24 (d, J = 8.0, 2H), 7.00 (t, J = 8.6, 1H), 3.84 (s, 3H), 2.99-2.80 (m, 3H), 2.73 (dd, J = 11.0 & 6.2, 1H), 2.54 (hep, J = 7.0, 1H), 2.25 (s, 3H), 0.98 (d, J = 7.0, 3H), 0.95 (d, J = 7.0, 3H). 1.125 —Me —Me —(C═O).sup.iPr 6-F 3-Cl —CH.sub.2—CH.sub.2— 4-fluoro- .sup.1H NMR (400 MHz, phenyl- CDCl.sub.3) δ = 7.42 (dd, 1H), 7.11-7.06 (m, 2H), 6.99 (t, 1H), 6.97-6.90 (m, 2H), 3.84 (s, 3H), 2.86- 2.68 (m, 4H), 2.55 (sept, 1H), 2.26 (s, 3H), 0.98 (dd, 6H). 1.149 —Me —Me —(C═O).sup.iPr 6-F 3-Cl —CH.sub.2—CH.sub.2— p-tolyl- .sup.1H NMR (400 MHz, CDCl.sub.3) δ = 7.41 (dd, J = 8.8 & 5.1, 1H), 7.10-6.92 (m, 5H), 3.83 (s, 3H), 2.86-2.68 (m, 4H), 2.54 (sep, J = 7.0, 1H), 2.31 (s, 3H), 2.24 (s, 3H), 0.96 (d, J = 7.0, 6H).

Biological Efficacy for Compounds of Formula (I)

B1 Post-Emergence Efficacy—Test 1

[0271] Seeds of a variety of test species are sown in standard soil in pots:—Solanum nigrum (SOLNI), Amaranthus retoflexus (AMARE), Setaria faberi (SETFA), Alopecurus myosuroides (ALOMY), Echinochloa crus-galli (ECHCG), Ipomoea hederacea (IPOHE), Lolium perenne (LOLPE). After 8 days cultivation (post-emergence) under controlled conditions in a glasshouse (at 24/16° C., day/night; 14 hours light; 65% humidity), the plants are sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in acetone/water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5). Compounds are applied at 1000 g/ha. The test plants are then grown in a glasshouse under controlled conditions in a glasshouse (at 24/16° C., day/night; 14 hours light; 65% humidity) and watered twice daily. After 13 days, the test is evaluated for the percentage damage caused to the plant. The biological activities are assessed on a five point scale (5=80-100%; 4=60-79%; 3=40-59%; 2=20-39%; 1=0-19%). Results are shown in Table 5 below. A blank value in the table is indicative that the compound was not tested on that species.

TABLE-US-00013 TABLE 5 Control of weed species by compounds of formula (I) after post-emergence application Compound AMARE SOLNI SETFA LOLPE ECHCG IPOHE 1.001 5 5 5 5 5 5 1.002 4 5 3 4 4 5 1.012 5 5 5 5 5 5 1.018 5 5 5 5 5 5 1.024 5 5 5 5 5 5 1.042 5 5 5 5 5 5 1.048 5 5 5 5 5 5 1.054 5 5 5 5 5 5 1.060 5 5 5 5 5 5 1.066 5 5 5 4 5 5 1.089 5 5 5 5 5 5 1.095 5 5 5 5 5 1.125 5 5 5 5 5 5 1.149 5 5 5 5 5 5

B2 Post-Emergence Efficacy—Test 2

[0272] Seeds of a variety of test species (see Table B1) were sown in standard soil in pots. After cultivation for 12 days (post-emergence) under controlled conditions in a glasshouse (at 24/18° C. or 20/16° C., at day/night; 16 hours light; 65% humidity), the plants were sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient dissolved in IF50 (see Table B2 for composition) and adjuvant (Genapol XO80) was added to the spray solution at a rate of 0.2% v/v.

TABLE-US-00014 TABLE B1 Plant species under test and abbreviations used Abbreviation Cool climate plant species: Hordeum vulgare HORVW Triticum aestivum TRZAW Brassica napus BRSNN Beta vulgaris BEAVA Alopecurus myosuroides ALOMY Avena fatua AVEFA Bromus tectorum BROTE Lolium perenne LOLPE Poa annua POAAN Chenopodium album CHEAL Galium aparine GALAP Kochia scoparia KSHSC Polygonum convolvulus POLCO Sinapis arvensis SINAR Stellaria media STEME Veronica persica VERPE Warm climate species: Orysa sativa ORYSA Zea mays ZEAMX Glycine max GLXMA Brachiaria plantaginea BRAPL Digitaria sanguinalis DIGSA Echinochloa crus galli ECHCG Eleisine indica ELEIN Panicum miliaceum PANMI Setaria faberi SETFA Sorghum bicolour SORVU Abutilon theophrasti ABUTH Amaranthus retroflexus AMARE Bidens pilosa BIDPI Euphorbia hetrophylla EPHHL Ipomoea hederacea IPOHE Sida spinosa SIDSP Xanthium strumarium XANST Cyperus esculentus CYPES

TABLE-US-00015 TABLE B2 Chemical composition of IF50 CAS Chemical Registry Amount Component description Function number (% w/w) Emulsogen Castor oil Emulsifier 61791-12-6 11.12 EL360 ™ ethoxylate N-methyl- 1-Methyl-2- Solvent 872-50-4 44.44 pyrrolidone pyrrolidone Dowanol DPM Dipropylene Solvent 34590-94-8 44.44 glycol ether glycol mono- methyl ether

[0273] After application, the test plants were grown in a glasshouse under controlled conditions (as above) and watered twice daily. Herbicidal activity was evaluated 15 days after application on a 0-100 scale. The results, where 0=no damage to test plant and 100=total kill of test plant are shown below in Tables 6 to 9.

TABLE-US-00016 TABLE 6 Control of warm season plant species by compounds of Formula (I) after post-emergence application Compound Rate Warm Season Plant Species ID (g/Ha) ZEAMX GLXMA ORYSA SETFA PANMI SORVU DIGSA ECHCG BRAPL ELEIN 1.024 500 100 100 40 100 100 100 90 100 90 80 250 70 100 20 90 90 90 90 90 70 80 125 40 90 0 90 90 80 80 90 70 60 60 20 90 0 80 80 70 40 80 70 40 30 10 80 0 70 70 10 20 80 60 40 15 0 70 0 20 0 0 0 70 30 0 1.042 500 90 100 50 100 100 100 90 100 90 90 250 70 100 20 90 100 90 80 100 90 80 125 60 90 0 90 90 90 70 90 90 80 60 20 90 0 90 80 80 70 90 90 70 30 10 80 0 80 60 70 60 90 80 70 15 0 60 0 40 10 0 0 80 80 0 1.048 500 100 100 30 100 100 90 70 100 100 80 250 70 90 10 80 100 80 50 90 90 80 125 50 90 0 70 80 70 20 90 80 60 60 50 90 0 40 30 70 20 80 80 60 30 10 80 0 40 20 30 10 80 60 50 15 0 70 0 0 0 0 0 60 20 0 1.066 500 70 90 40 90 100 100 70 90 100 80 250 30 90 20 90 100 90 70 90 70 70 125 20 70 10 80 80 80 40 90 80 70 60 20 70 0 70 60 60 20 90 — 70 30 20 40 0 70 50 20 20 80 60 20 15 0 20 0 0 0 0 0 20 0 0 1.089 500 100 100 50 80 90 90 30 100 90 90 250 90 100 20 60 80 90 40 90 90 90 125 30 — 10 60 60 90 10 90 — 80 60 30 80 0 30 50 70 0 80 — 70 30 20 70 0 20 20 60 0 80 90 0 15 0 — 0 0 0 0 0 80 80 0 1.125 500 70 90 0 100 80 90 70 100 80 80 250 40 90 0 20 70 80 30 90 70 80 125 20 — 0 20 50 70 10 80 80 70 1.125 60 30 70 0 20 50 50 0 80 80 70 30 20 70 0 10 30 50 0 80 — 40 15 0 40 0 0 20 0 0 70 80 40

TABLE-US-00017 TABLE 7 Control of warm season plant species by compounds of Formula (I) after post-emergence application Compound Rate Warm Season Plant Species ID (g/Ha) ZEAMX GLXMA ORYSA EPHHL SIDSP ABUTH XANST IPOHE BIDPI AMARE 1.024 500 100 100 40 100 100 100 100  100 90 100 250 70 100 20 100 100 100 — 100 80 100 125 40 90 0 90 100 100 80 100 80 100 60 20 90 0 90 90 100 80 100 80 90 30 10 80 0 90 90 90 — 100 80 90 15 0 70 0 70 80 90 — — 80 80 1.042 500 90 100 50 100 100 100 100  100 90 100 250 70 100 20 100 100 100 100  100 80 100 125 60 90 0 100 — 100 90 100 70 100 60 20 90 0 90 100 100 — 100 70 100 30 10 80 0 90 90 90 — 100 70 100 15 0 60 0 80 90 80 80 100 70 — 1.048 500 100 100 30 100 90 100 100  100 100 100 250 70 90 10 100 90 90 90 100 100 100 125 50 90 0 90 90 90 90 100 70 90 60 50 90 0 90 80 90 90 100 70 90 30 10 80 0 70 80 80 — 80 70 80 15 0 70 0 50 80 60 — 70 70 60 1.066 500 70 90 40 100 100 100 100  100 90 100 250 30 90 20 100 90 90 100  100 90 100 125 20 70 10 90 90 90 — 100 80 100 60 20 70 0 80 80 50 90 90 70 90 30 20 40 0 70 80 50 — 90 60 90 15 0 20 0 60 40 20 — 70 50 90 1.089 500 100 100 50 100 100 100 100  100 100 100 250 90 100 20 100 100 100 90 100 80 100 125 30 — 10 100 100 100 90 100 80 100 60 30 80 0 100 90 100 80 100 70 90 30 20 70 0 100 80 90 90 100 60 80 15 0 — 0 80 — 70 — 100 70 80 1.125 500 70 90 0 100 100 100 100  100 100 100 250 40 90 0 100 90 100 90 100 80 100 125 20 — 0 100 90 90 90 100 70 100 60 30 70 0 100 80 90 90 100 70 90 30 20 70 0 90 — 90 90 100 60 90 15 0 40 0 90 — 80 — 90 60 80

TABLE-US-00018 TABLE 8 Control of cool season plant species by compounds of Formula (I) after post-emergence application Compound Rate Cool Season Plant Species ID (g/Ha) HORVW TRZAW BRSNN BEAVA ALOMY AVEFA BROTE LOLPE POAAN CHEAL 1.024 500 20 70 90 100 70 80 70 90 90 100 250 10 60 90 80 70 70 40 90 80 90 125 10 30 90 80 70 60 20 90 80 90 60 10 20 90 80 50 30 10 70 30 90 30 10 0 90 70 30 20 0 70 20 90 15 0 0 80 70 10 10 0 10 10 60 1.042 500 80 80 90 90 90 90 90 90 90 100 250 80 80 90 90 90 90 80 90 90 100 125 40 70 90 90 80 80 80 90 90 90 60 20 60 90 80 80 80 70 70 80 90 30 20 30 90 70 60 60 30 70 70 90 15 10 20 90 80 20 30 20 60 20 — 1.048 500 80 80 90 90 90 90 70 90 90 100 250 40 50 90 90 80 90 60 90 90 90 125 40 20 90 90 80 80 50 90 80 70 60 10 20 90 80 70 60 20 90 80 — 30 10 10 90 80 30 30 10 40 30 — 15 10 0 90 70 20 10 0 20 30 — 1.066 500 90 80 90 90 90 90 90 100 90 100 250 80 70 90 80 90 90 80 90 90 100 125 70 60 90 80 80 90 70 90 90 90 60 20 40 90 80 70 40 60 80 80 90 30 10 10 90 80 50 20 20 20 70 90 15 0 0 90 80 20 0 0 10 20 — 1.089 500 60 70 90 90 90 90 70 90 70 100 250 30 60 90 90 80 90 60 90 80 100 125 20 30 90 80 80 80 30 90 90 100 60 20 20 90 80 50 70 10 80 70 90 30 10 0 80 80 50 70 0 70 40 90 15 10 0 80 90 20 30 0 40 20 80 1.125 500 10 50 90 70 40 80 10 90 60 90 250 10 30 90 70 60 70 10 80 70 90 125 10 20 90 70 30 70 0 70 60 90 60 10 10 80 60 30 60 0 60 20 90 30 0 10 80 60 10 40 0 50 10 90 15 0 0 80 70 10 30 0 40 0 90

TABLE-US-00019 TABLE 9 Control of cool season plant species by compounds of Formula (I) after post-emergence application Compound Rate Cool Season Plant Species ID (g/Ha) HORVW TRZAW POLCO KCHSC SINAR STEME GALAP VERPE 1.024 500 20 70 100 20 100  100 90 100 250 10 60 90 10 90 90 90 100 125 10 30 90 10 — 90 60 80 60 10 20 90 0 80 90 20 90 30 10 0 — 0 80 90 20 80 15 0 0 80 0 80 90 — 80 1.042 500 80 80 100 60 90 100 90 100 250 80 80 90 30 90 100 80 100 125 40 70 90 20 90 100 80 100 60 20 60 90 10 90 90 60 100 30 20 30 80 10 90 100 30 90 15 10 20 80 0 80 100 10 80 1.048 500 80 80 90 80 90 100 80 100 250 40 50 90 50 90 100 60 100 125 40 20 90 20 90 100 60 80 60 10 20 90 10 80 90 50 90 30 10 10 70 0 80 90 30 80 15 10 0 60 0 40 90 20 60 1.066 500 90 80 100 20 90 100 90 100 250 80 70 100 20 90 90 30 100 125 70 60 90 10 90 90 20 100 60 20 40 90 0 80 90 20 100 30 10 10 80 0 60 60 20 90 15 0 0 70 0 60 80 20 80 1.089 500 60 70 — 60 90 90 90 100 250 30 60 — 60 90 90 30 100 125 20 30 — 60 90 90 30 90 60 20 20 — 50 90 90 — 90 30 10 0 — 20 80 90 20 80 15 10 0 — 10 70 90 10 70 1.125 500 10 50 90 70 90 90 70 90 250 10 30 90 60 90 90 40 80 125 10 20 90 50 90 90 30 80 60 10 10 90 30 80 90 20 70 30 0 10 90 20 60 90 20 70 15 0 0 90 0 60 90 — 70