HERBICIDAL COMPOUNDS

Abstract

The present invention relates to herbicidal substituted phenyl-pyridazine-diones and substituted phenyl-pyridazinone derivatives of formula (I), as well as to processes and intermediates used for the preparation of such derivatives. The invention further extends to herbicidal compositions comprising such derivatives, as well as to the use of such compounds and compositions in controlling undesirable plant growth: in particular the use in controlling weeds, such as broad-leaved dicotyledonous weeds, in crops of useful plants.

Claims

1. A compound of formula (I) ##STR00071## 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)=NOC.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.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.1-C.sub.6alkyl-S, C.sub.1-C.sub.6alkoxy, 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; and, R.sup.6 is selected from the group consisting of halogen, cyano, nitro, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, 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)=NOC.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), ##STR00072## 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 the group consisting of hydrogen, cyano, amino, C.sub.1-C.sub.3dialkylamino, hydroxy, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.4 alkoxy, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3haloalkoxy, and halogen; and, W is either ##STR00073## wherein a denotes the point of attachment to the phenyl-pyridazine dione/phenyl-pyridazinone 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.

2. The compound according to claim 1, wherein G is hydrogen or C(O)R.sup.3, and R.sup.3 is C.sub.1-C.sub.4 alkyl, C.sub.2-C.sub.3alkenyl, C.sub.2-C.sub.3alkynyl, C.sub.1-C.sub.4alkoxy, NR.sup.4R.sup.5 wherein R.sup.4 and R.sup.5 together form a morpholinyl ring, or phenyl

3. The compound according to claim 1, wherein G is hydrogen or C(O)R.sup.3 wherein R.sup.3 is isopropyl, t-butyl, methyl, ethyl, propargyl, methoxy, ethoxy, or tert-butoxy.

4. The compound of claim 1 wherein X is hydrogen, halogen, or C.sub.1haloalkyl.

5. The compound of claim 1 wherein Y is hydrogen, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3haloalkyl, or halogen.

6. The compound according to claim 1 wherein R.sup.1 is methyl, ethyl, n-propyl, cyclopropyl, propargyl, or C.sub.1haloalkyl.

7. The compound according to claim 1 wherein R.sup.2 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, 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 and C.sub.2-C.sub.6 haloalkynyl.

8. The compound according to claim 1 wherein D is a substituted or unsubstituted

9. The compound according to claim 1 wherein each R.sup.8 is independently.

10. The compound according to claim 1 wherein D is Dp and each Z is independently selected from hydrogen, cyano, halogen, methyl, methoxy, and trifluoromethyl.

11. The compound according to claim 1 wherein W is W1 and each of R.sup.10, R.sup.11, R.sup.12, and R.sup.13 is hydrogen.

12. The compound according to claim 1 wherein W is W2 and each of R.sup.14 and R.sup.15 is hydrogen.

13. The compound according to claim 1 wherein W is W3.

14. A herbicidal composition comprising a herbicidal compound according to claim 1 and an agriculturally acceptable formulation adjuvant.

15. A herbicidal composition according to claim 14, further comprising at least one additional pesticide.

16. A herbicidal composition according to claim 15, wherein the additional pesticide is a herbicide or herbicide safener.

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

18. Use of a compound of Formula (I) as defined in claim 1 as a herbicide.

19. The compound according to claim 2, wherein G is hydrogen or C(O)R.sup.3 wherein R.sup.3 is isopropyl, t-butyl, methyl, ethyl, propargyl, methoxy, ethoxy, or tert-butoxy.

20. A method of controlling unwanted plant growth, comprising applying a herbicidal composition according to claim 14, to the unwanted plants or to the locus thereof.

Description

PREPARATION EXAMPLES

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

[0138] ##STR00045##

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

[0139] 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.

##STR00046##

[0140] .sup.1H NMR (400 MHz, CDCl.sub.3) .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

[0141] 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.

[0142] The mixture was washed with brine (2100 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.

[0143] 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 (3100 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 (3200 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.

##STR00047##

[0144] .sup.1H NMR (400 MHz, DMSO-d6) .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

[0145] 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.

##STR00048##

[0146] .sup.1H NMR (400 MHz, DMSO-d6) .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

[0147] 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.

##STR00049##

[0148] .sup.1H NMR (400 MHz, CDCl.sub.3) .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

[0149] 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.

##STR00050##

[0150] .sup.1H NMR (400 MHz, DMSO-d6) .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

[0151] 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).

[0152] 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%).

##STR00051##

[0153] .sup.1H NMR (400 MHz, CDCl.sub.3) .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

[0154] 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.

[0155] 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%).

##STR00052##

[0156] .sup.1H NMR (DMSO-d6) .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

[0157] A stirred mixture of 4-[3-chloro-6-fluoro-2-[(E)-styryl]phenyl]-5-hydroxy-2,6-dimethyl-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.

[0158] 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.

##STR00053##

[0159] .sup.1H NMR (DMSO-d6) .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

[0160] ##STR00054##

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

[0161] 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.

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.

##STR00055##

[0162] .sup.1H NMR (400 MHz, CDCl.sub.3) .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

[0163] [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 bar H.sub.2.

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.

[0164] 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.

##STR00056##

[0165] .sup.1H NMR (400 MHz, CDCl.sub.3) .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

[0166] [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.

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 (330 mL). The combined organics were dried over MgSO.sub.4, filtered and concentrated in-vacuo to afford crude product.
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.

##STR00057##

[0167] .sup.1H NMR (400 MHz, CDCl.sub.3) .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

[0168] ##STR00058##

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

[0169] 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.

[0170] 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.

##STR00059##

[0171] .sup.1H NMR (400 MHz, CDCl.sub.3) 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

[0172] 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.

[0173] 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.

##STR00060##

[0174] .sup.1H NMR (400 MHz, CDCl.sub.3) 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

[0175] 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.

[0176] 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.

##STR00061##

[0177] .sup.1H NMR (400 MHz, CDCl.sub.3) 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).

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

[0178] ##STR00062##

4.1 [5-[3-chloro-6-fluoro-2-[(E)-2-(6-methyl-4,8-dioxo-1,3,6,2-dioxazaborocan-2-yl)vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate

[0179] [5-(2-bromo-3-chloro-6-fluoro-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (5.00 g, 11.97 mmol, 1.0 eq), 6-methyl-2-vinyl-1,3,6,2-dioxazaborocane-4,8-dione (2.63 g, 14.36 mmol, 1.2 eq) and chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)] palladium(II) (307 mg, 0.60 mmol, 0.05 eq) were charged into a 250 ml round bottom flask fitted with a condenser, stirrer bar and nitrogen bubbler. THE (100 mL) was added followed by N,N-diisopropylethylamine (4.2 mL, 23.94 mmol, 2.0 eq) against a flow of nitrogen and the mixture heated to reflux for 3 h.

[0180] The reaction mixture was allowed to cool to room temperature then diluted in DCM and filtered through Celite, washing with further portions of DCM. The eluent was then concentrated to dryness.

[0181] The crude product purified by flash column chromatography to afford [5-[3-chloro-6-fluoro-2-[(E)-2-(6-methyl-4,8-dioxo-1,3,6,2-dioxazaborocan-2-yl)vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (5.91 g, 11.4 mmol, 95% yield) as an off white solid.

##STR00063##

[0182] .sup.1H NMR (400 MHz, DMSO-d.sub.6) =7.63 (dd, J=5.1, 8.9 Hz, 1H), 7.31 (t, J=8.9 Hz, 1H), 6.65 (d, J=18.3 Hz, 1H), 5.68 (d, J=18.3 Hz, 1H), 4.24 (dd, J=11.9, 17.2 Hz, 2H), 3.95-3.83 (m, 2H), 3.70 (s, 3H), 2.66 (spt, J=7.0 Hz, 1H), 2.16 (s, 3H), 0.90 (d, J=7.0 Hz, 3H), 0.89 (d, J=7.0 Hz, 3H)

4.2 4-[3-chloro-2-[(E)-2-(2-chloro-4-pyridyl)vinyl]-6-fluoro-phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one

[0183] [5-[3-Chloro-6-fluoro-2-[(E)-2-(6-methyl-4,8-dioxo-1,3,6,2-dioxazaborocan-2-yl)vinyl]phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (10.0 g, 19.24 mmol, 1.0 eq), potassium carbonate (8.06 g, 3.0 eq) and 1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex [PdCl2(dppf).DCM] (786 mg, 0.96 mmol, 0.05 eq) were charged into a 250 mL flask equipped with a stirrer bar, condenser and nitrogen inlet. The reaction vessel was evacuated and back-filled with nitrogen three times. Acetonitrile (192 mL, de-oxygenated by sparging with N.sub.2(g)) was added by cannula followed by 4-bromo-2-chloro-pyridine (5.55 g, 1.5 eq) and water (6.93 mL, 20 eq). The reaction mixture was then heated at reflux for 17 hrs.

[0184] The reaction mixture was allowed to cool to room temperature then concentrated in vacuo. The residue was diluted with water (50 mL) and DCM (100 mL) and the aqueous phase carefully acidified to pH 3 by slow addition of 2M HCl (aq.). The organic layer was separated and the aqueous phase extracted with a further two portions of DCM (50 mL). The combined organic extracts were dried by passing through a phase separation cartridge then concentrated in vacuo.

[0185] The crude product was purified by flash column chromatography to afford 4-[3-chloro-2-[(E)-2-(2-chloro-4-pyridyl)vinyl]-6-fluoro-phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (5.79 g, 74% yield) as a pink solid.

##STR00064##

[0186] .sup.1H NMR (500 MHz, DMSO-d.sub.6) =10.85 (br s, 1H), 8.34 (d, J=5.1 Hz, 1H), 7.63 (dd, J=5.1, 8.9 Hz, 1H), 7.54 (d, J=1.4 Hz, 1H), 7.39 (dd, J=1.4, 5.1 Hz, 1H), 7.33 (t, J=8.9 Hz, 1H), 7.31 (d, J=16.5 Hz, 1H), 6.56 (d, J=16.5 Hz, 1H), 3.53 (s, 3H), 2.19 (s, 3H)

4.3 4-[3-chloro-2-[2-(2-chloro-4-pyridyl)ethyl]-6-fluoro-phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one

[0187] 4-[3-Chloro-2-[(E)-2-(2-chloro-4-pyridyl)vinyl]-6-fluoro-phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (5.00 g) was subjected to catalytic hydrogenation in a 2:1 mixture of EtOAc:MeOH (150 mL) over 5% Rh/Al.sub.2O.sub.3 catalyst (1.27 g) at 4 bar H.sub.2.

[0188] After 8.5 hrs, the reaction mixture was filtered through a pad of Celite, washing with ethyl acetate/methanol (1:1). The filtrate was concentrated in-vacuo to afford a crude residue.

[0189] The crude product was purified by flash column chromatography to afford 4-[3-chloro-2-[2-(2-chloro-4-pyridyl)ethyl]-6-fluoro-phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (2.33 g, 46% yield) as a white solid.

##STR00065##

[0190] .sup.1H NMR (400 MHz, DMSO-d.sub.6) =10.83 (br s, 1H), 8.24 (d, J=5.1 Hz, 1H), 7.54 (dd, J=5.3, 8.9 Hz, 1H), 7.23 (t, J=8.9 Hz, 1H), 7.16 (br s, 1H), 7.08 (dd, J=1.4, 5.1 Hz, 1H), 3.60 (s, 3H), 2.84-2.65 (m, 4H), 2.25 (s, 3H)

Example 5 Preparation of [5-[3-chloro-2-[(E)-2-(4-cyclopropylphenyl)vinyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate

[0191] ##STR00066##

5.1 [5-(3-chloro-6-fluoro-2-vinyl-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate

[0192] [5-(2-bromo-3-chloro-6-fluoro-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (4.177 g, 10.00 mmol, 1.0 eq) and tributyl(vinyl)stannane (4.384 mL, 15.00 mmol, 1.50 eq) were dissolved in toluene (60.00 mL) then 1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex [PdCl2(dppf).DCM] (408 mg, 0.50 mmol, 0.05 eq) was added. The reaction mixture was heated at reflux overnight.

[0193] The reaction mixture was allowed to cool to room temperature then concentrated in vacuo. The crude product was then purified by flash column chromatography to afford [5-(3-chloro-6-fluoro-2-vinyl-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate as an off-white solid (3.02 g, 83% yield).

##STR00067##

[0194] .sup.1H NMR (400 MHz, CDCl.sub.3) =7.40 (dd, J=5.1, 8.7 Hz, 1H), 6.99 (t, J=8.7 Hz, 1H), 6.65 (dd, J=11.6, 17.6 Hz, 1H), 5.37-5.30 (m, 2H), 3.79 (s, 3H), 2.59 (spt, J=7.0 Hz, 1H), 2.23 (s, 3H), 1.04 (d, J=7.0 Hz, 4H), 1.03 (d, J=7.0 Hz, 1H)

5.2 [5-[3-chloro-2-[(E)-2-(4-cyclopropylphenyl)vinyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate

[0195] A stirred mixture of [5-(3-chloro-6-fluoro-2-vinyl-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (300 mg, 1.0 eq), chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)]palladium(II) (21 mg, 0.05 eq), 1-bromo-4-cyclopropylbenzene (243 mg, 1.5 eq) and N,N-diisopropylethylamine (0.29 mL, 2.0 eq) in toluene (5 mL) under N.sub.2 was heated at reflux for 3 hrs.

[0196] The reaction mixture was allowed to cool to room temperature then diluted with DCM and filtered through a pad of Celite, eluting with further portions of DCM. The filtrate was concentrated in vacuo to give the crude product.

[0197] The crude product was purified by flash column chromatography to give [5-[3-chloro-2-[(E)-2-(4-cyclopropylphenyl)vinyl]-6-fluoro-phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (285 mg, 72% yield) as a pale yellow gum.

##STR00068##

[0198] .sup.1H NMR (400 MHz, CDCl.sub.3) =7.41 (dd, J=5.1, 8.9 Hz, 1H), 7.26-7.22 (m, 2H), 7.02-6.98 (m, 2H), 6.99 (t, J=8.9 Hz, 1H), 6.93 (d, J=16.5 Hz, 1H), 6.59 (d, J=16.5 Hz, 1H), 3.71 (s, 3H), 2.62 (spt, J=7.0 Hz, 1H), 2.19 (s, 3H), 1.87 (tt, J=5.0, 8.4 Hz, 1H), 1.07 (d, J=7.0 Hz, 3H), 1.06 (d, J=7.0 Hz, 1H), 0.99-0.93 (m, J=2.0, 8.4 Hz, 2H), 0.73-0.64 (m, 2H).

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

[0199] A stirred mixture of [5-(2-bromo-3-chloro-6-fluoro-phenyl)-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (400 mg, 1.0 eq), copper (1) iodide (11 mg, 0.06 eq), chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)] palladium(II) (37 mg, 0.075 eq) and diisopropylamine (9 mL) was heated at 120 C. for 1 hr in a sealed vessel under microwave irradiation.

[0200] After cooling to room temperature the reaction mixture was concentrated in vacuo then diluted with DCM before filtering through a pad of Celite. The filtrate was concentrated in vacuo to give the crude product.

[0201] The crude product was purified by mass-directed reverse-phase prep HPLC to afford [5-[3-chloro-6-fluoro-2-(2-phenylethynyl)phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate (57 mg, 14% yield).

[0202] [5-[3-chloro-6-fluoro-2-(2-phenylethynyl)phenyl]-1,3-dimethyl-6-oxo-pyridazin-4-yl] 2-methylpropanoate was dissolved in ethanol (5 mL) then water (0.9 mL) and lithium hydroxide monohydrate (15 mg, 3.0 eq) were added. The reaction mixture was stirred at room temperature for 2 hrs, then concentrated in vacuo to remove the ethanol. The remaining aqueous phase was acidified to pH 3 by addition of 2M HCl then extracted with DCM (10 mL then 25 mL). The combined organics were dried by passage through a phase separating cartridge then concentrated in vacuo to give the crude product.

[0203] The crude product was purified by flash column chromatography to afford 4-[3-chloro-6-fluoro-2-(2-phenylethynyl)phenyl]-5-hydroxy-2,6-dimethyl-pyridazin-3-one (30 mg, 69% yield) as a white solid.

##STR00069##

[0204] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 7.35 (dd, J=8.00, 5.00 Hz, 1H), 7.33-7.27 (m, 5H), 6.98 (t, J=8.60 Hz, 1H), 3.71-3.63 (m, 3H), 2.32-2.26 (m, 3H).

[0205] Compounds 1.0001, 1.0002, 1.0012, 1.0018, 1.0024, 1.0042, 1.0048, 1.0054, 1.0060, 1.0066, 1.0072, 1.0089, 1.0101, 1.0119, 1.0095, 1.0143, 1.0125, 1.0327, 1.0333, 1.0339, 1.0345, 1.0351, 1.0357, 1.0363, 1.0369, 1.0375, 1.0387, 1.0417, 1.0429, 1.0441, 1.0597, 1.0603, 1.0609, 1.0615, 1.0621, 1.0627, 1.0633, 1.0639, 1.0645, 1.0651, 1.0657, 1.0663, 1.0669, 1.0675, 1.0681, 1.0687, 1.0693, 1.0789, 1.0885, 1.0891, 1.0897, 1.0903, 1.0915, 1.0921, 1.0933, 1.0149, 1.0969, 1.0975, 1.0975, 1.0981, 1.0993, 1.0999, 1.1005, 1.1011, 1.1185, 1.1191, 1.1257, 1.1258, 1.1259, 1.1261, 1.1265, 1.1267, 1.1269, 1.1270, 1.1271, 1.1282, 1.1293, 1.1294, 1.1348, 1.1351, 1.1352, 1.1357, 1.1363, 1.1367, 1.1369, 1.1370, 1.1371, 1.1372, 1.1373, 1.1383, 1.1387, 1.1391, 1.1392, 1.1393, 1.1394, 1.1447, 1.1454, 1.1457, 1.1458, 1.1556, 1.1560, 1.1651, 1.1652, 1.1653, 1.1654, 1.1655, 1.1656 were prepared using the general methods as described supra. Table 2 below shows the structure of these compounds and NMR characterising data.

TABLE-US-00002 TABLE 2 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. (I) [00070] Cmpd R.sup.1 R.sup.2 G X Y W D NMR details 1.001 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 Ph .sup.1H NMR (DMSO-d6) .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). 1.0002 Me Me H 6-F 3-Cl (E)-CHCH Ph .sup.1H NMR (DMSO-d6) .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). 1.0012 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 4-chloro- .sup.1H NMR (400 MHz, chloroform) = phenyl- 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). 1.0018 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 4- .sup.1H NMR (400 MHz, CDCl.sub.3) ppm trifluoro- 2.29 (d, J = 4.16 Hz, 3 H) 2.70-2.93 methyl- (m, 4 H) 3.65-3.81 (m, 3 H) 6.95- phenyl- 7.06 (m, 1 H) 7.12 (br d, J = 6.48 Hz, 2 H) 7.48 (d, J = 8.07 Hz, 3 H). 1.0024 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 4-cyano- .sup.1H NMR (400 MHz, CDCl3) ppm phenyl- 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). 1.0042 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 4- .sup.1H NMR (400 MHz, CDCl.sub.3) = 8.30 trifluoro- (s, 1H), 7.54 (d, J = 1.2, 2H), 7.37 methyl-3- (dd, J = 8.8 and 5.1, 1H), 6.95 (t, J = pyridyl- 8.5, 1H), 3.69 (s, 3H), 2.92-2.65 (m, 4H), 2.28 (s, 3H). 1.0048 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 4-fluoro- .sup.1H NMR (400 MHz, CDCl.sub.3) ppm phenyl- 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). 1.0054 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 3-pyridyl- .sup.1H NMR (400 MHz, DMSO-d6) 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). 1.0060 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 3,4- .sup.1H NMR (400 MHz, CDCl.sub.3) = 7.44 difluoro- (dd, J = 5.2, 8.6 Hz, 1H), 7.04-6.95 phenyl- (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). 1.0066 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 2- .sup.1H NMR (400 MHz, CDCl.sub.3) = 7.53 trifluoro- (br. d, J = 7.5 Hz, 1H), 7.43 (br. t, methyl- J = 7.5 Hz, 1H), 7.33 (dd, J = 5.1, 8.5 phenyl- 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). 1.0072 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 4-chloro- .sup.1H NMR (400 MHz, CDCl.sub.3) = 7.41 phenyl- (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). 1.0089 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 4-chloro- .sup.1H NMR (400 MHz, CDCl.sub.3) = 7.41 phenyl- (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). 1.0101 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 4-fluoro- .sup.1H NMR (400 MHz, CDCl.sub.3) = 7.42 phenyl- (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). 1.0119 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 4-tolyl- .sup.1H NMR (400 MHz, CDCl.sub.3) = 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). 1.0095 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 4- .sup.1H NMR (400 MHz, CDCl.sub.3) d.sub.H = 7.50 trifluoro- (d, J = 8.0, 2H), 7.43 (dd, J = 8.9 & 5.1, methyl- 1H), 7.24 (d, J = 8.0, 2H), 7.00 (t, phenyl- 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). 1.0143 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 2- .sup.1H NMR (400 MHz, chloroform) = trifluoro- 7.56 (d, J = 7.8 Hz, 1H), 7.49-7.37 methyl- (m, 3H), 7.28 (t, J = 7.2 Hz, 1H), 7.00 phenyl (t, J = 8.6 Hz, 1H), 3.84 (s, 3H), 2.99- 2.77 (m, 4H), 2.53 (spt, J = 7.0 Hz, 1H), 2.26 (s, 3H), 0.96 (app. t, J = 7.0 Hz, 6H) 1.0125 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 4-fluoro- .sup.1H NMR (400 MHz, CDCl.sub.3) = 7.42 phenyl- (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). 1.0327 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 3-chloro- .sup.1H NMR (400 MHz, chloroform) = 4-fluoro- 7.34 (dd, J = 5.1, 8.9 Hz, 1H), 6.99 phenyl (dd, J = 2.0, 7.3 Hz, 1H), 6.96 (t, J = 8.6 Hz, 1H), 6.90 (t, J = 8.9 Hz, 1H), 6.82 (ddd, J = 2.0, 4.8, 8.6 Hz, 1H), 3.66 (s, 3H), 2.75-2.55 (m, 4H), 2.25 (s, 3H) 1.0333 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 3-chloro- .sup.1H NMR (400 MHz, chloroform) = 4-pyridyl 8.14 (d, J = 5.0 Hz, 1H), 7.38 (dd, J = 5.1, 8.9 Hz, 1H), 7.01 (d, J = 1.2 Hz, 1H), 6.98 (t, J = 8.9 Hz, 1H), 6.89 (dd, J = 1.2, 5.0 Hz, 1H), 3.74 (s, 3H), 2.89- 2.65 (m, 4H), 2.32 (s, 3H) 1.0339 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 4- .sup.1H NMR (400 MHz, DMSO-d6) = hydroxy- 10.82 (br s, 1H), 9.17 (s, 1H), 7.54 phenyl (dd, J = 5.2, 8.9 Hz, 1H), 7.20 (t, J = 8.9 Hz, 1H), 6.82-6.75 (m, 2H), 6.65- 6.60 (m, 2H), 3.61 (s, 3H), , 2.69- 2.43 (m, 4H), 2.26 (s, 3H) 1.0345 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 4-cyclo- .sup.1H NMR (400 MHz, chloroform) = propyl- 7.37 (dd, J = 5.2, 8.8 Hz, 1H), 6.96- phenyl 6.88 (m, 2H), 6.91 (t, J = 8.8 Hz, 1H), 6.88-6.83 (m, 2H), 3.67 (s, 3H), 2.82- 2.62 (m, 4H), 2.25 (s, 3H), 1.84 (tt, J = 5.0, 8.5 Hz, 1H), 0.95-0.88 (m, 2H), 0.68-0.60 (m, 2H) 1.0351 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 1-methyl- .sup.1H NMR (400 MHz, chloroform) 3- ppm 7.39-7.27 (m, 1H), 7.08 (br s, (trifluoro- 1H), 6.96-6.79 (m, 1H), 3.86-3.76 methyl)- (m, 3H), 3.71-3.52 (m, 3H), 2.75- pyrazol- 2.40 (m, 4H), 2.32-3.16 (m, 3H) 4-yl 1.0357 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 thiazol-2- .sup.1H NMR (400 MHz, chloroform) yl ppm 7.38 (d, J = 3.30 Hz, 1 H), 7.16- 7.11 (m, 2H), 6.89 (t, J = 8.50 Hz, 1 H), 3.52-3.39 (m, 2 H), 3.22-3.08 (m, 1H), 3.06-2.94 (m, 1H), 2.35 (s, 3H) 1.0363 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 pyrimidin- .sup.1H NMR (400 MHz, methanol) = 5-yl 8.95 (s, 1H), 8.46 (s, 2H), 7.46 (dd, J = 5.2, 8.8 Hz, 1H), 7.11 (t, J = 8.7 Hz, 1H), 3.72 (s, 3H), 2.99-2.75 (m, 4H), 2.32 (s, 3H) 1.0369 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 4-(tert- .sup.1H NMR (400 MHz, chloroform) = butoxy)- 7.28 (dd, J = 5.2, 8.9 Hz, 1H), 6.82 (s, phenyl 5H), 3.62 (s, 3H), 2.73-2.50 (m, 4H), 2.23 (s, 3H) 1.0375 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 thiazol-5- .sup.1H NMR (400 MHz, chloroform) yl ppm 8.54 (s, 1 H), 7.38 (s, 2H), 7.03- 6.91 (m, 1H), 3.70 (s, 3H), 3.04-2.93 (m, 2H), 2.87-2.79 (m, 2H), 2.28 (s, 3H) 1.0387 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 2-chloro- .sup.1H NMR (400 MHz, chloroform) = 3-pyridyl 8.23 (dd, J = 1.9, 4.7 Hz, 1H), 7.51 (dd, J = 1.9, 7.5 Hz, 1H), 7.41 (dd, J = 5.1, 8.6 Hz, 1H), 7.13 (dd, J = 4.7, 7.5 Hz, 1H), 7.00 (t, J = 8.6 Hz, 1H), 3.84 (s, 3H), 2.98-2.76 (m, 4H), 2.54 (spt, J = 7.0 Hz, 1H), 2.26 (s, 3H), 0.97 (d, J = 7.0 Hz, 3H), 0.96 (d, J = 7.0 Hz, 1H) 1.0417 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 4-cyclo- .sup.1H NMR (400 MHz, chloroform) = propyl- 7.41 (dd, J = 5.2, 8.8 Hz, 1H), 7.04- phenyl 7.00 (m, 2H), 6.98-6.94 (m, 2H), 6.97 (t, J = 8.8 Hz, 1H), 3.83 (s, 3H), 2.84-2.67 (m, 4H), 2.53 (spt, J = 7.0 Hz, 1H), 2.24 (s, 3H), 1.85 (tt, J = 5.1, 8.4 Hz, 1H), 0.96 (d, J = 7.0 Hz, 3H), 0.96 (d, J = 7.0 Hz, 3H), 0.94-0.88 (m, J = 1.9, 8.5 Hz, 2H), 0.68-0.61 (m, 2H) 1.0429 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 thiazol-2- .sup.1H NMR (400 MHz, chloroform) yl ppm 7.65 (d, J = 3.30 Hz, 1 H), 7.43 (dd, J = 8.93, 5.14 Hz, 1 H), 7.17 (d, J = 3.30 Hz, 1 H), 7.04-6.97 (m, 1H), 3.83 (s, 3H), 3.30 (ddd, J = 10.82, 7.03, 5.87 Hz, 2 H), 3.19-3006 (m, 1H), 2.98-2.87 (m, 1H), 2.60-2.50 (m, 1H), 2.25 (s 3H), 0.97 (dd, J = 6.97, 2.57 Hz, 6 H) 1.0441 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 4-(tert- .sup.1H NMR (400 MHz, chloroform) = butoxy)- 7.40 (dd, J = 5.1, 8.8 Hz, 1H), 7.03- phenyl 6.99 (m, 2H), 6.97 (t, J = 8.8 Hz, 1H), 6.90-6.83 (m, 2H), 3.84 (s, 3H), 2.85- 2.68 (m, 4H), 2.55 (spt, J = 7.0 Hz, 1H), 2.25 (s, 3H), 1.32 (s, 9H), 0.97 (d, J = 7.0 Hz, 3H), 0.97 (d, J = 7.0 Hz, 3H) 1.0597 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 2-cyano- .sup.1H NMR (400 MHz, chloroform) = phenyl 7.51-7.44 (m, 2H), 7.33-7.24 (m, 3H + CHCl3 peak), 6.95 (t, J = 8.6 Hz, 1H), 3.69 (s, 3H), 2.95-2.79 (m, 4H), 2.30 (s, 3H). 1.0603 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 3-cyano- .sup.1H NMR (400 MHz, chloroform) = phenyl 7.46 (td, J = 1.4, 7.6 Hz, 1H), 7.37 (dd, J = 5.2, 8.9 Hz, 1H), 7.35-7.28 (m, 2H), 7.26-7.23 (m, 1H), 6.95 (t, J = 8.6 Hz, 1H), 3.69 (s, 3H), 2.82- 2.63 (m, 4H), 2.28 (s, 3H). 1.0609 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 3- .sup.1H NMR (400 MHz, chloroform) = trifluoro- 7.46-7.38 (m, 2H), 7.33 (t, J = 7.6 methyl- Hz, 1H), 7.25-7.16 (m, 2H), 6.98 (t, J = phenyl 8.5 Hz, 1H), 6.13 (br s, 1H), 3.71 (s, 3H), 2.92-2.66 (m, 4H), 2.28 (s, 3H). 1.0615 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 o-tolyl .sup.1H NMR (400 MHz, chloroform) = 7.37 (dd, J = 5.1, 8.8 Hz, 1H), 7.11- 7.02 (m, 3H), 6.97-6.87 (m, 2H), 3.67 (s, 3H), 2.76-2.58 (m, 4H), 2.26 (s, 3H), 2.05 (s, 3H). 1.0621 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 m-tolyl .sup.1H NMR (400 MHz, chloroform) = 7.40 (dd, J = 5.1, 8.8 Hz, 1H), 7.14- 7.07 (m, 1H), 7.01-6.90 (m, 2H), 6.83-6.74 (m, 2H), 6.21 (brd s, 1H), 3.70 (s, 3H), 2.86-2.59 (m, 4H), 2.28 (s, 3H), 2.26 (s, 3H). 1.0627 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 2-methyl- .sup.1H NMR (400 MHz, chloroform) 4-pyridyl ppm 8.41 (d, J = 5.99 Hz, 1 H), 7.36 (dd, J = 8.86, 5.07 Hz, 1 H), 7.30 (d, J = 5.99 Hz, 1 H), 7.23 (s, 1H), 6.98 (t, J = 8.56 Hz, 1H), 3.69 (s, 3H), 3.03 (s, 2H), 2.97-2.82 (m, 2H), 2.67 (s, 3H), 2.27 (s, 3H) 1.0633 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 2- .sup.1H NMR (400 MHz, chloroform) = trifluoro- 8.48 (d, J = 5.0 Hz, 1H), 7.26 (dd, J = methyl-4- 5.6, 8.5 Hz, 1H), 7.26 (br s, 1H), 7.13 pyridyl (d, J = 5.0 Hz, 1H), 6.85 (t, J = 8.5 Hz, 1H), 3.63 (s, 3H), 2.82-2.69 (m, 3H), 2.69-2.56 (m, 1H), 2.24 (s, 3H) 1.0639 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 2-amino- .sup.1H NMR (400 MHz, DMSO-d6) ppm 4-pyridyl 7.73 (d, J = 5.26 Hz, 1 H) 7.50 (dd, J = 8.86, 5.20 Hz, 1 H) 7.16 (t, J = 8.62 Hz, 1 H) 6.18 (s, 2 H) 3.57 (s, 3 H) 2.60-2.69 (m, 2 H) 2.40-2.47 (m, 2 H) 2.20 (s, 3 H) 1.0645 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 2-fluoro- .sup.1H NMR (400 MHz, chloroform) 4-pyridyl ppm 8.01 (d, J = 5.13 Hz, 1 H) 7.42 (dd, J = 8.86, 5.20 Hz, 1 H) 6.98-7.07 (m, 1 H) 6.84-6.90 (m, 1 H) 6.62 (s, 1 H) 3.74 (s, 3 H) 2.71-2.94 (m, 4 H) 2.31 (s, 3 H) 1.0651 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 4-pyridyl .sup.1H NMR (400 MHz, DMSO-d6) = 8.66 (d, J = 6.4 Hz, 2H), 7.55 (d, J = 6.4 Hz, 2H), 7.54 (dd, J = 5.0, 8.8 Hz, 1H), 7.23 (t, J = 8.8 Hz, 1H), 3.59 (s, 3H), 2.98-2.75 (m, 4H), 2.26 (s, 3H) 1.0657 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 4- .sup.1H NMR (400 MHz, chloroform) (methyl- ppm 7.43 (dd, J = 8.86, 5.20 Hz, 1 H), amino)- 6.97 (t, J = 8.56 Hz, 1 H), 6.81 (d, phenyl J = 8.44 Hz, 2 H), 6.48 (d, J = 8.44 Hz, 2 H), 3.72 (s, 3H), 2.80 (s, 4H), 2.75- 2.56 (m, 3H), 2.28 (s, 3H) 1.0663 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 4-amino- .sup.1H NMR (400 MHz, chloroform) phenyl ppm 7.37 (dd, J = 8.80, 5.26 Hz, 1 H), 6.95 (s, 1 H), 6.80 (d, J = 8.31 Hz, 2 H), 6.55 (d, J = 8.31 Hz, 2 H), 3.70 (s, 3 H), 2.71 (br s, 2 H), 2.59 (s, 2 H), 2.28 (s, 3 H) 1.0669 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 2-cyano- .sup.1H NMR (400 MHz, chloroform) = phenyl 7.56 (dd, J = 1.1, 7.7 Hz, 1H), 7.51- 7.46 (m, 1H), 7.43 (dd, J = 5.1, 8.8 Hz, 1H), 7.32 (d, J = 7.7 Hz, 1H), 7.30-7.26 (m, 1H + CHCl3 peak), 7.01 (t, J = 8.6 Hz, 1H), 3.85 (s, 3H), 3.15-3.05 (m, 1H), 3.04-2.80 (m, 3H), 2.55 (spt, J = 7.0 Hz, 1H), 2.27 (s, 3H), 0.97 (dd, J = 1.1, 7.0 Hz, 6H). 1.0675 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 3-cyano- .sup.1H NMR (400 MHz, chloroform) = phenyl 7.50-7.46 (m, 1H), 7.46-7.37 (m, 3H), 7.37-7.31 (m, 1H), 7.00 (t, J = 8.6 Hz, 1H), 3.86 (s, 3H), 3.00-2.78 (m, 3H), 2.73-2.63 (m, 1H), 2.55 (quin, J = 7.0 Hz, 1H), 2.26 (s, 3H), 0.97 (dd, J = 7.0, 13.5 Hz, 6H). 1.0681 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 3- .sup.1H NMR (400 MHz, chloroform) = trifluoro- 7.47-7.39 (m, 2H), 7.39-7.30 (m, methyl- 3H), 7.00 (t, J = 8.6 Hz, 1H), 3.86 (s, phenyl 3H), 2.96-2.83 (m, 3H), 2.74-2.65 (m, 1H), 2.55 (spt, J = 7.0 Hz, 1H), 2.26 (s, 3H), 0.97 (t, J = 7.2 Hz, 6H). 1.0687 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 o-tolyl .sup.1H NMR (400 MHz, chloroform) = 7.43 (dd, J = 5.1, 8.8 Hz, 1H), 7.15- 7.04 (m, 4H), 6.99 (t, J = 8.6 Hz, 1H), 3.84 (s, 3H), 2.88-2.64 (m, 4H), 2.54 (spt, J = 7.0 Hz, 1H), 2.25 (s, 3H), 2.18 (s, 3H), 0.96 (d, J = 7.0 Hz, 6H). 1.0693 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 m-tolyl .sup.1H NMR (400 MHz, chloroform) = 7.42 (dd, J = 5.1, 8.8 Hz, 1H), 7.18- 7.11 (m, 1H), 7.02-6.89 (m, 4H), 3.84 (s, 3H), 2.88-2.65 (m, 4H), 2.54 (spt, J = 7.0 Hz, 1H), 2.31 (s, 3H), 2.25 (s, 3H), 0.97 (d, J = 7.0 Hz, 6H). 1.0789 Me Me H 6-F H CH.sub.2CH.sub.2 2-fluoro- .sup.1H NMR (400 MHz, chloroform) 4-pyridyl ppm 8.02 (d, J = 5.14 Hz, 1 H), 7.33 (dd, J = 7.89, 5.93 Hz, 1 H), 7.09- 6.98 (m, 2 H), 6.89 (d, J = 5.01 Hz, 1 H) ,6.64 (s, 1H), 3.76 (s, 3H), 2.95- 2.68 (m, 4H), 2.33 (s, 3H) 1.0885 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 4- .sup.1H NMR (400 MHz, chloroform) (dimethyl- ppm 7.42 (dd, J = 8.80, 5.14 Hz, 1 H), amino)- 6.96 (t, J = 8.56 Hz, 1 H), 6.86 (d, phenyl J = 8.68 Hz, 2 H), 6.65-6.59 (m, 2H), 3.72 (s, 3H), 2.90 (s, 6H), 2.87-2.80 (m, 1H), 2.77-2.62 (m, 3H), 2.27 (s, 3H) 1.0891 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 3-methyl- .sup.1H NMR (400 MHz, chloroform) 4-amino- ppm 7.38 (dd, J = 8.86, 5.20 Hz, 1 H), phenyl 6.93 (t, J = 8.56 Hz, 1 H), 6.73-6.59 (m, 2H), 6.52 (d, J = 7.83 Hz, 1 H), 3.70 (s, 3H), 2.83-2.50 (m, 4H), 2.27 (s, 3H), 2.09 (s, 3H) 1.0897 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 thiophen- .sup.1H NMR (400 MHz, chloroform) = 3-yl 7.39 (dd, J = 5.2, 8.9 Hz, 1H), 7.19 (dd, J = 2.9, 4.9 Hz, 1H), 6.95 (t, J = 8.6 Hz, 1H), 6.84-6.79 (m, 1H), 6.74 (dd, J = 1.2, 4.9 Hz, 1H), 6.42 (br s, 1H), 3.68 (s, 3H), 2.88-2.63 (m, 4H), 2.27 (s, 3H). 1.0903 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 1-methyl- .sup.1H NMR (400 MHz, DMSO-d6) = pyrazol- 7.54 (dd, J = 5.3, 8.9 Hz, 1H), 7.35 (s, 4-yl 1H), 7.20 (t, J = 8.9 Hz, 1H), 7.05 (s, 1H), 3.73 (s, 3H), 3.59 (s, 3H), 2.70- 2.57 (m, 2H), 2.53-2.37 (m, 2H), 2.24 (s, 3H) 1.0915 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 5-methyl- .sup.1H NMR (400 MHz, chloroform) 1,3,4- ppm 7.34-7.27 (m, 1 H), 7.03-6.94 oxadiazol- (m, 1H), 3.76-3.68 (m, 3H), 3.22 (s, 2-yl 4H), 2.47 (s, 3H), 2.36-2.27 (m, 3H) 1.0921 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 5-methyl- .sup.1H NMR (400 MHz, chloroform) 3-pyridyl ppm 7.64-7.84 (m, 2 H) 7.34 (s, 1 H) 7.09-7.19 (m, 1 H) 6.79 (br s, 1 H) 3.74 (s, 3 H) 2.65-2.87 (m, 4 H) 2.34 (s, 3 H) 2.28 (s, 3 H) 1.0933 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 6-methyl- .sup.1H NMR (400 MHz, chloroform) 2-pyridyl ppm 7.49-7.64 (m, 1 H) 7.21 (br s, 1 H) 6.99 (br d, J = 3.67 Hz, 2 H) 6.84 (s, 1 H) 3.76 (s, 4 H) 3.39-3.54 (m, 1 H) 3.05-3.19 (m, 1 H) 2.81-3.02 (m, 2 H) 2.36 (s, 4 H) 2.24 (br s, 3 H) 1.0149 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 4-tolyl- .sup.1H NMR (400 MHz, CDCl.sub.3) = 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). 1.0969 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 thiophen- .sup.1H NMR (400 MHz, chloroform) = 3-yl 7.41 (dd, J = 5.1, 8.8 Hz, 1H), 7.22 (dd, J = 2.9, 4.9 Hz, 1H), 6.98 (t, J = 8.6 Hz, 1H), 6.94-6.91 (m, 1H), 6.88 (dd, J = 1.2, 4.9 Hz, 1H), 3.83 (s, 3H), 2.92-2.72 (m, 4H), 2.55 (spt, J = 7.0 Hz, 1H), 2.25 (s, 3H), 0.97 (dd, J = 3.9, 7.0 Hz, 6H). 1.0975 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 1-methyl- .sup.1H NMR (400 MHz, chloroform) pyrazol- ppm 7.41 (dd, J = 8.93, 5.14 Hz, 1 H), 4-yl 7.21 (d, J = 2.20 Hz, 1 H), 6.97 (t, J = 8.62 Hz, 1 H), 5.95 (d, J = 2.20 Hz, 1 H), 3.82 (d, J = 1.83 Hz, 6 H), 2.78- 3.00 (m, 5 H), 2.49-2.62 (m, 1 H), 2.24 (s, 3 H), 0.97 (t, J = 7.15 Hz, 6 H) 1.0975 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 1-methyl- .sup.1H NMR (400 MHz, chloroform) = pyrazol- 7.40 (dd, J = 5.2, 8.9 Hz, 1H), 7.23 (s, 4-yl 1H), 7.10 (s, 1H), 6.97 (t, J = 8.9 Hz, 1H), 3.83 (s, 3H), 3.82 (s, 3H), 2.86- 2.75 (m, 1H), 2.74-2.59 (m, 3H), 2.55 (spt, J = 7.0 Hz, 1H), 2.24 (s, 3H), 0.98 (d, J = 7.0 Hz, 3H), 0.97 (d, J = 7.0 Hz, 1H) 1.0981 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 2-methyl- .sup.1H NMR (400 MHz, chloroform) triazol-4- ppm 7.42 (dd, J = 8.93, 5.14 Hz, 1 H), yl 7.26 (s, 1 H), 6.99 (t, J = 8.62 Hz, 1 H), 3.83 (s, 3 H), 4.12 (s, 3 H), 2.72- 3.01 (m, 4 H), 2.47-2.63 (m, 1 H), 2.25 (s, 3 H), 0.97 (dd, J = 6.97, 2.20 Hz, 6 H) 1.0993 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 5-methyl- .sup.1H NMR (400 MHz, chloroform) 3-pyridyl ppm 8.25 (d, J = 1.47 Hz, 1 H) 8.18 (d, J = 1.71 Hz, 1 H) 7.42 (dd, J = 8.80, 5.14 Hz, 1 H) 7.26 (s, 1 H) 7.00 (t, J = 8.62 Hz, 1 H) 3.85 (s, 3 H) 2.64- 2.91 (m, 4 H) 2.54 (d, J = 6.97 Hz, 1 H) 2.29 (s, 3 H) 2.25 (s, 3 H) 0.97 (dd, J = 8.01, 7.03 Hz, 6 H) 1.0999 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 5-methyl- .sup.1H NMR (400 MHz, chloroform) 2-pyridyl ppm 8.30 (dd, J = 1.53, 0.67 Hz, 1 H) 7.40 (dd, J = 8.80, 5.14 Hz, 1 H) 7.32- 7.37 (m, 1 H) 6.91-7.00 (m, 2 H) 3.81 (s, 3 H) 2.81-3.07 (m, 4 H) 2.54 (quin, J = 6.97 Hz, 1 H) 2.28 (s, 3 H) 2.24 (s, 3 H) 0.96 (dd, J = 6.97, 5.01 Hz, 6 H) 1.1005 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 6-methyl- .sup.1H NMR (400 MHz, chloroform) 2-pyridyl ppm 7.36-7.45 (m, 2 H) 6.97 (t, J = 8.62 Hz, 1 H) 6.93 (d, J = 7.58 Hz, 1 H) 6.82 (d, J = 7.58 Hz, 1 H) 3.81 (s, 3 H) 2.92 (s, 4 H) 2.50-2.61 (m, 1 H) 2.47 (s, 3 H) 2.25 (s, 3 H) 0.98 (dd, J = 8.25, 7.03 Hz, 6 H) 1.1011 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 3-methyl- .sup.1H NMR (400 MHz, chloroform) 2-pyridyl ppm 8.34 (dd, J = 4.77, 1.22 Hz, 1 H) 7.42 (dd, J = 8.93, 5.14 Hz, 1 H) 7.35 (dd, J = 7.58, 0.86 Hz, 1 H) 6.94-7.02 (m, 2 H) 3.79 (s, 3 H) 2.97 (t, J = 7.95 Hz, 4 H) 2.46-2.60 (m, 1 H) 2.23 (s, 3 H) 2.13 (s, 3 H) 0.97 (dd, J = 7.03, 3.97 Hz, 6 H) 1.1185 Me Me H 6-F 3-Cl CH.sub.2CH.sub.2 2- .sup.1H NMR (400 MHz, chloroform) acetamido- ppm 7.41 (dd, J = 8.86, 5.07 Hz, 1 H) thiazol- 6.97-7.03 (m, 2 H) 3.73 (s, 3 H) 2.84- 5-yl 3.06 (m, 3 H) 2.72 (s, 1 H) 2.37 (s, 3 H) 2.30 (s, 4 H) 1.1191 Me Me (CO).sup.iPr 6-F 3-Cl CH.sub.2CH.sub.2 3,5- .sup.1H NMR (400 MHz, chloroform) = difluoro- 7.42 (dd, J = 5.1, 8.9 Hz, 1H), 6.99 (t, phenyl J = 8.9 Hz, 1H), 6.69-6.58 (m, 3H), 3.87-3.84 (m, 3H), 2.93-2.77 (m, 3H), 2.75-2.62 (m, 1H), 2.54 (spt, J = 7.0 Hz, 1H), 2.25 (s, 3H), 0.98 (d, J = 7.0 Hz, 3H), 0.95 (d, J = 7.0 Hz, 3H) 1.1257 Me Me H 6-F 3-Cl (E)-CHCH 2-chloro- .sup.1H NMR (400 MHz, DMSO-d6) = 3-pyridyl 10.94 (br s, 1H), 8.33 (dd, J = 1.6, 4.6 Hz, 1H), 8.17 (dd, J = 1.7, 7.3 Hz, 1H), 7.64 (dd, J = 5.1, 8.8 Hz, 1H), 7.46 (dd, J = 4.6, 7.3 Hz, 1H), 7.33 (t, J = 8.8 Hz, 1H), 7.17 (d, J = 16.5 Hz, 1H), 6.76 (d, J = 16.5 Hz, 1H), 3.53 (s, 3H), 2.19 (s, 3H) 1.1258 Me Me H 6-F 3-Cl (E)-CHCH 2-chloro- .sup.1H NMR (400 MHz, chloroform) = 4-pyridyl 8.20 (d, J = 5.3 Hz, 1H), 7.29 (dd, J = 5.3, 8.5 Hz, 1H), 7.14 (d, J = 1.3 Hz, 1H), 7.10 (d, J = 16.5 Hz, 1H), 7.05 (dd, J = 1.3, 5.3 Hz, 1H), 6.91 (t, J = 8.5 Hz, 1H), 6.44 (d, J = 16.5 Hz, 1H), 3.61 (s, 3H), 2.24 (s, 3H) 1.1259 Me Me H 6-F 3-Cl (E)-CHCH 3-chloro- .sup.1H NMR (400 MHz, chloroform) = 4-fluoro- 7.39 (dd, J = 5.1, 8.9 Hz, 1H), 7.30 phenyl (dd, J = 2.2, 6.9 Hz, 1H), 7.11 (ddd, J = 2.2, 5.0, 8.6 Hz, 1H), 7.06 (t, J = 8.6 Hz, 1H), 6.97 (t, J = 8.9 Hz, 1H), 6.82 (d, J = 16.5 Hz, 1H), 6.44 (d, J = 16.5 Hz, 1H), 3.63 (s, 3H), 2.24 (s, 3H) 1.1261 Me Me H 6-F 3-Cl (E)-CHCH 4- .sup.1H NMR (400 MHz, DMSO-d6) = hydroxy- 10.75 (br s, 1H), 9.67 (s, 1H), 7.58 phenyl (dd, J = 5.3, 8.8 Hz, 1H), 7.23 (t, J = 8.8 Hz, 1H), 7.19-7.13 (m, 2H), 6.75- 6.72 (m, 2H), 6.73 (d, J = 16.5 Hz, 1H), 6.48 (d, J = 16.5 Hz, 1H), 3.55 (s, 3H), 2.19 (s, 3H) 1.1265 Me Me H 6-F 3-Cl (E)-CHCH pyrimidin- .sup.1H NMR (400 MHz, DMSO-d6) = 5-yl 9.08 (s, 1H), 8.86 (s, 2H), 7.63 (dd, J = 5.2, 8.9 Hz, 1H), 7.32 (t, J = 8.9 Hz, 1H), 7.23 (d, J = 16.8 Hz, 1H), 6.60 (d, J = 16.8 Hz, 1H), 3.54 (s, 3H), 2.19 (s, 3H) 1.1267 Me Me H 6-F 3-Cl (E)-CHCH thiazol-5- .sup.1H NMR (400 MHz, chloroform) yl ppm 8.66 (s, 1 H), 7.67 (s, 1 H), 7.49 (dd, J = 8.86, 5.20 Hz, 1 H), 7.36- 7.29 (m, 3H), 7.13-7.05 (m, 3H), 6.89-6.81 (m, 1H). 6.78-6.63 (m, 1H), 4.77-4.55 (m, 2H), 3.75 (s, 3H), 2.24 (s, 3H) 1.1269 Me Me H 6-F 3-Cl (E)-CHCH 3-cyano- .sup.1H NMR (400 MHz, chloroform) = phenyl 7.56-7.47 (m, 3H), 7.44-7.38 (m, 2H), 7.04-6.93 (m, 2H), 6.53 (d, J = 16.5 Hz, 1H), 3.64 (s, 3H), 2.25 (s, 3H). 1.1270 Me Me H 6-F 3-Cl (E)-CHCH 3- .sup.1H NMR (400 MHz, chloroform) = trifluoro- 7.55-7.49 (m, 2H), 7.46-7.39 (m, methyl- 3H), 7.05-6.94 (m, 2H), 6.60 (d, J = phenyl 16.4 Hz, 2H), 3.65 (s, 3H), 2.25 (s, 3H). 1.1271 Me Me H 6-F 3-Cl o-tolyl .sup.1H NMR (400 MHz, chloroform) = 7.43 (dd, J = 3.7, 5.4 Hz, 1H), 7.37 (dd, J = 5.1, 8.8 Hz, 1H), 7.21-7.13 (m, 2H), 7.12-7.05 (m, 1H), 6.94 (t, J = 8.6 Hz, 1H), 6.84 (d, J = 1.0 Hz, 1H), 6.77 (d, J = 1.0 Hz, 1H), 6.70 (br s, 1H), 3.64 (s, 3H), 2.23 (s, 3H), 2.04 (s, 3H). 1.1282 Me Me H 6-F 3-Cl (E)-CHCH thiophen- .sup.1H NMR (400 MHz, chloroform) = 3-yl 7.39 (dd, J = 5.2, 8.9 Hz, 1H), 7.29- 7.24 (m, 1H + CHCl3 peak), 7.17 (dd, J = 1.0, 5.0 Hz, 1H), 7.10 (dd, J = 1.1, 2.8 Hz, 1H), 6.95 (t, J = 8.6 Hz, 1H), 6.82-6.73 (m, 1H), 6.65-6.58 (m, 1H), 3.65 (s, 3H), 2.24 (s, 3H). 1.1293 Me Me H 6-F 3-Cl (E)-CHCH 4-methyl- .sup.1H NMR (400 MHz, chloroform) 2-pyridyl ppm 8.09 (d, J = 5.26 Hz, 1 H) 7.22 (d, J = 16.63 Hz, 1 H) 7.19 (br s, 1 H) 7.01 (dd, J = 8.74, 5.32 Hz, 1 H) 6.95 (d, J = 5.87 Hz, 1 H) 6.53-6.66 (m, 2 H) 3.64 (s, 4 H) 2.35 (d, J = 9.17 Hz, 6 H) 1.1294 Me Me H 6-F 3-Cl (E)-CHCH 2- .sup.1H NMR (400 MHz, chloroform) acetamido- ppm 7.44 (dd, J = 8.93, 5.14 Hz, 1 H) thiazol- 7.16-7.21 (m, 1 H) 7.04 (t, J = 8.56 5-yl Hz, 1 H) 6.71 (d, J = 4.65 Hz, 2 H) 3.72 (s, 3 H) 2.28 (s, 3 H) 2.26 (s, 3 H) 1.1348 Me Me (CO).sup.iPr 6-F 3-Cl (E)-CHCH 4-cyano- .sup.1H NMR (400 MHz, chloroform) = phenyl 7.62-7.55 (m, 2H), 7.45 (dd, J = 5.0, 8.5 Hz, 1H), 7.45-7.40 (m, 1H), 7.13 (d, J = 16.5 Hz, 1H), 7.05 (t, J = 8.5 Hz, 1H), 6.68 (d, J = 16.5 Hz, 1H), 3.69 (s, 3H), 2.65 (spt, J = 7.0 Hz, 1H), 2.23 (s, 3H), 1.11 (d, J = 7.0 Hz, 3H), 1.07 (d, J = 7.0 Hz, 3H) 1.1351 Me Me (CO).sup.iPr 6-F 3-Cl (E)-CHCH 4- .sup.1H NMR (400 MHz, CDCl3) H: 8.65 trifluoro- (d, J = 1.6, 1H), 7.87 (dd, J = 8.2 and methyl-3- 2.1, 1H), 7.64 (d, J = 8.2, 1H), 7.47 pyridyl- (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). 1.1352 Me Me (CO).sup.iPr 6-F 3-Cl (E)-CHCH 4-fluoro- .sup.1H NMR (400 MHz, CDCl3) ppm phenyl 7.45 (dd, 1 H) 7.29-7.37 (m, 2 H) 6.96-7.07 (m, 3 H) 6.92 (d, 1 H) 6.59 (d, 1 H) 3.75 (s, 3 H) 2.66 (sept, 1 H) 2.26 (s, 3 H) 1.09 (dd, 6 H). 1.1357 Me Me (CO).sup.iPr 6-F 3-Cl (E)-CHCH 4- .sup.1H NMR (400 MHz, chloroform) = (trifluoro- 7.43 (dd, J = 5.1, 8.9 Hz, 1H), 7.40- methoxy) 7.34 (m, 2H), 7.18-7.11 (m, J = 7.9 phenyl Hz, 2H), 7.03 (t, J = 8.9 Hz, 1H), 6.98 (d, J = 16.5 Hz, 1H), 6.64 (d, J = 16.5 Hz, 1H), 3.71 (s, 3H), 2.64 (spt, J = 7.0 Hz, 1H), 2.22 (s, 3H), 1.09 (d, J = 7.0 Hz, 3H), 1.07 (d, J = 7.0 Hz, 3H) 1.1363 Me Me (CO).sup.iPr 6-F 3-Cl (E)-CHCH 4-cyclo- .sup.1H NMR (400 MHz, chloroform) = propyl- 7.41 (dd, J = 5.1, 8.9 Hz, 1H), 7.26- phenyl 7.22 (m, 2H), 7.02-6.98 (m, 2H), 6.99 (t, J = 8.9 Hz, 1H), 6.93 (d, J = 16.5 Hz, 1H), 6.59 (d, J = 16.5 Hz, 1H), 3.71 (s, 3H), 2.62 (spt, J = 7.0 Hz, 1H), 2.19 (s, 3H), 1.87 (tt, J = 5.0, 8.4 Hz, 1H), 1.07 (d, J = 7.0 Hz, 3H), 1.06 (d, J = 7.0 Hz, 1H), 0.99-0.93 (m, J = 2.0, 8.4 Hz, 2H), 0.73-0.64 (m, 2H) 1.1367 Me Me (CO).sup.iPr 6-F 3-Cl (E)-CHCH 4-(tert- .sup.1H NMR (400 MHz, chloroform) = butoxy)- 7.41 (dd, J = 5.0, 8.6 Hz, 1H), 7.26- phenyl 7.23 (m, 2H), 6.99 (t, J = 8.6 Hz, 1H), 6.94-6.90 (m, 1H), 6.91 (d, J = 16.5 Hz, 1H), 6.60 (d, J = 16.5 Hz, 1H), 3.71 (s, 3H), 2.63 (spt, J = 7.0 Hz, 1H), 2.22 (s, 3H), 1.35 (s, 9H), 1.08 (d, J = 7.0 Hz, 3H), 1.06 (d, J = 7.0 Hz, 1H) 1.1369 Me Me (CO).sup.iPr 6-F 3-Cl (E)-CHCH 2-cyano- .sup.1H NMR (400 MHz, chloroform) = phenyl 7.70 (d, J = 8.1 Hz, 1H), 7.61-7.53 (m, 2H), 7.46 (dd, J = 5.1, 8.9 Hz, 1H), 7.34 (dt, J = 1.0, 7.6 Hz, 1H), 7.24 (d, J = 16.5 Hz, 1H), 7.10-6.97 (m, 2H), 3.76 (s, 3H), 2.65 (spt, J = 7.0 Hz, 1H), 2.26 (s, 3H), 1.08 (dd, J = 3.0, 7.0 Hz, 6H). 1.1370 Me Me (CO).sup.iPr 6-F 3-Cl (E)-CHCH 3-cyano- .sup.1H NMR (400 MHz, chloroform) = phenyl 7.63-7.55 (m, 2H), 7.55-7.50 (m, 1H), 7.48-7.38 (m, 2H), 7.12-7.00 (m, 2H), 6.65 (d, J = 16.5 Hz, 1H), 3.70 (s, 3H), 2.65 (spt, J = 7.0 Hz, 1H), 2.24 (s, 3H), 1.09 (dd, J = 7.0, 12.5 Hz, 6H). 1.1371 Me Me (CO).sup.iPr 6-F 3-Cl (E)-CHCH 3- .sup.1H NMR (400 MHz, chloroform) = trifluoro- 7.57 (s, 1H), 7.54-7.48 (m, 2H), 7.47- methyl- 7.39 (m, 2H), 7.10-7.00 (m, 2H), phenyl 6.68 (d, J = 16.5 Hz, 1H), 3.72 (s, 3H), 2.65 (spt, J = 7.0 Hz, 1H), 2.24 (s, 3H), 1.09 (t, J = 7.4 Hz, 6H). 1.1372 Me Me (CO).sup.iPr 6-F 3-Cl (E)-CHCH o-tolyl .sup.1H NMR (400 MHz, chloroform) = 7.51-7.39 (m, 2H), 7.22-7.13 (m, 2H), 7.13-7.08 (m, 1H), 7.01 (t, J = 8.7 Hz, 1H), 6.94-6.78 (m, 2H), 3.75 (s, 3H), 2.61 (spt, J = 7.0 Hz, 1H), 2.22 (s, 3H), 2.12 (s, 3H), 1.06 (dd, J = 0.6, 7.0 Hz, 6H). 1.1373 Me Me (CO).sup.iPr 6-F 3-Cl (E)-CHCH m-tolyl .sup.1H NMR (400 MHz, chloroform) = 7.42 (dd, J = 5.1, 8.9 Hz, 1H), 7.23- 7.10 (m, 3H), 7.07 (d, J = 7.3 Hz, 1H), 7.04-6.94 (m, 2H), 6.59 (d, J = 16.5 Hz, 1H), 3.73 (s, 3H), 2.63 (quin, J = 7.0 Hz, 1H), 2.34 (s, 3H), 2.21 (s, 3H), 1.08 (dd, J = 2.8, 7.0 Hz, 6H). 1.1383 Me Me (CO).sup.iPr 6-F 3-Cl (E)-CHCH thiophen- .sup.1H NMR (400 MHz, chloroform) = 3-yl 7.42 (dd, J = 5.1, 8.8 Hz, 1H), 7.30- 7.21 (m, 2H + CHCl3 peak), 7.15 (dd, J = 1.2, 2.8 Hz, 1H), 7.00 (t, J = 8.7 Hz, 1H), 6.89-6.80 (m, 1H), 6.69- 6.61 (m, 1H), 3.74 (s, 3H), 2.62 (spt, J = 7.0 Hz, 1H), 2.23 (s, 3H), 1.06 (dd, J = 5.5, 7.0 Hz, 6H). 1.1387 Me Me (CO).sup.iPr 6-F 3-Cl (E)-CHCH 5-methyl- .sup.1H NMR (400 MHz, chloroform) 3-pyridyl ppm 8.32 (s, 2 H), 7.52 (s, 1 H), 7.44 (dd, J = 8.93, 5.14 Hz, 1 H), 7.10- 6.99 (m, 2 H), 6.63 (d, J = 16.51 Hz, 1 H), 3.71 (s, 3 H), 2.65 (quin, J = 7.00 Hz, 1 H), 2.34 (s, 3 H) 2.23 (s, 3 H) 1.09 (t, J = 7.15 Hz, 6 H) 1.1391 Me Me (CO).sup.iPr 6-F 3-Cl (E)-CHCH 6-chloro- .sup.1H NMR (400 MHz, chloroform) 3-pyridyl ppm 8.28 (d, J = 2.45 Hz, 1 H) 7.68 (dd, J = 8.31, 2.45 Hz, 1 H) 7.45 (dd, J = 8.86, 5.07 Hz, 1 H) 7.26-7.29 (m, 1 H) 7.00-7.10 (m, 2 H) 6.64 (d, J = 16.63 Hz, 1 H) 3.70 (s, 3 H) 2.54- 2.74 (m, 1 H) 2.23 (s, 3 H) 1.08 (dd, J = 11.80, 7.03 Hz, 6 H) 1.1392 Me Me (CO).sup.iPr 6-F 3-Cl (E)-CHCH 2- .sup.1H NMR (400 MHz, chloroform) = trifluoro- 8.57 (dd, J = 1.2, 4.7 Hz, 1H), 8.05 methyl-3- (dd, J = 1.2, 7.9 Hz, 1H), 7.50 (dd, J = pyridyl 4.7, 7.9 Hz, 1H), 7.46 (dd, J = 5.1, 8.9 Hz, 1H), 7.11 (d, J = 16.2 Hz, 1H), 7.07 (t, J = 8.9 Hz, 1H), 7.03 (qd, J = 2.0, 16.2 Hz, 1H), 3.74 (s, 3H), 2.63 (spt, J = 7.0 Hz, 1H), 2.24 (s, 3H), 1.07 (d, J = 7.0 Hz, 6H) 1.1393 Me Me (CO).sup.iPr 6-F 3-Cl (E)-CHCH 3,5- .sup.1H NMR (400 MHz, chloroform) = difluoro- 7.44 (dd, J = 5.1, 8.9 Hz, 1H), 7.04 (t, phenyl J = 8.9 Hz, 1H), 7.01 (d, J = 16.4 Hz, 1H), 6.89-6.83 (m, 2H), 6.69 (tt, J = 2.3, 8.8 Hz, 1H), 6.58 (d, J = 16.4 Hz, 1H), 3.72 (s, 3H), 2.64 (spt, J = 7.0 Hz, 1H), 2.23 (s, 3H), 1.10 (d, J = 7.0 Hz, 3H), 1.07 (d, J = 7.0 Hz, 3H) 1.1394 Me Me (CO).sup.iPr 6-F 3-Cl (E)-CHCH 4-methyl- .sup.1H NMR (400 MHz, chloroform) 2-pyridyl ppm 8.41 (d, J = 5.01 Hz, 1 H) 7.50 (d, J = 16.26 Hz, 1 H) 7.43 (dd, J = 8.86, 5.07 Hz, 1 H) 6.93-7.07 (m, 3 H) 6.68 (d, J = 16.26 Hz, 1 H) 3.74 (s, 3 H) 2.62 (dt, J = 13.94, 6.97 Hz, 1 H) 2.32 (s, 3 H) 2.21 (s, 3 H) 1.06 (dd, J = 6.97, 5.62 Hz, 6 H) 1.1447 Me Me H 6-F 3-Cl CC phenyl .sup.1H NMR (400 MHz, chloroform) ppm 7.35 (dd, J = 8.00, 5.00 Hz, 1 H), 7.33-7.27 (m, 5H), 6.98 (t, J = 8.60 Hz, 1H), 3.71-3.63 (m, 3H), 2.32- 2.26 (m, 3H) 1.1454 Me Me H 6-F 3-Cl CC 4-fluoro- .sup.1H NMR (400 MHz, chloroform) phenyl ppm 7.47 (dd, J = 8.93, 5.01 Hz, 1 H), 7/35-7/28 (m, 2H), 7.10 (t, J = 8.50 Hz, 1H), 7.05-6.98 (m, 2H), 3.73 (s, 3H), 2.34 (s, 3H) 1.1457 Me Me H 6-F 3-Cl CC 2- .sup.1H NMR (400 MHz, chloroform) trifluoro- ppm 7.61-7.37 (m, 4 H), 7.23 (dd, methyl- J = 8.00, 5.00 Hz, 1 H), 6.88 (br t, phenyl J = 8.44 Hz, 1 H), 3.58 (s, 3H), 2.22 (s, 3H) 1.1458 Me Me H 6-F 3-Cl CC p-tolyl .sup.1H NMR (400 MHz, chloroform) ppm 7.36 (dd, J = 9.00, 5.00 Hz, 1 H), 7.22-7.16 (m, 2H), 7.14-7.08 (m, 2H), 6.98 (t, J = 8.50 Hz, 1 H), 3.68 (s, 3H), 2.35 (s, 3H), 2.29 (s, 3H) 1.1556 Me Me (CO).sup.iPr 6-F 3-Cl CC 4-fluoro- .sup.1H NMR (400 MHz, CDCl3) ppm phenyl 7.46 (dd, 1 H) 7.31-7.38 (m, 2 H) 7.08 (t, 1 H) 6.99-7.06 (m, 2 H) 3.83 (s, 3 H) 2.61 (sept, 1 H) 2.28 (s, 3 H) 1.04 (dd, 6 H). 1.1560 Me Me (CO).sup.iPr 6-F 3-Cl CC p-tolyl .sup.1H NMR (400 MHz, chloroform) ppm 7.44 (dd, J = 9.00, 5.00 Hz, 1 H), 7.26-7.20 (m, 2H), 7.16-7.09 (m, 2H), 7.06 (t, J = 8.50 Hz, 1 H), 3.82 (s, H), 2.60 (spt, J = 7.00 Hz, 1H), 2.35 (s, 3H), 2.27 (s, 3H), 1.04 (d, J = 7.00 Hz, 3 H), 1.03 (d, J = 7.00 Hz, 3 H) 1.1651 Me Me (CO)Me 6-F 3-Cl CH.sub.2CH.sub.2 p-tolyl .sup.1H NMR (400 MHz, chloroform) ppm 7.44 (dd, J = 8.86, 5.20 Hz, 1 H), 7.11-6.94 (m, 5H), 3.84 (s, H), 2.89-2.69 (m, 4H), 2.32 (s, 3H), 2.06 (s, 3H) 1.1652 Me Me (CO).sup.OtBu 6-F 3-Cl CH.sub.2CH.sub.2 p-tolyl .sup.1H NMR (400 MHz, chloroform) ppm 7.42 (dd, J = 8.80, 5.14 Hz, 1 H), 7.10-7.04 (m, 2H), 7.04-6.94 (m, 3H), 3.78 (s, 3H), 2.88 (br d, J = 7.83 Hz, 2 H), 2.69 (td, J = 12.72, 11.37 Hz, 2 H), 2.36 (s, 3 H), 2.31 (s, 3 H), 1.10 (s, 9 H) 1.1653 Me Me (CO)O- 6-F 3-Cl CH.sub.2CH.sub.2 p-tolyl .sup.1H NMR (400 MHz, chloroform) me ppm 7.44 (dd, J = 8.86, 5.20 Hz, 1 H), 7.12-6.94 (m, 5H), 3.83 (s, 3H), 3.76 (s, 3H), 2.88-2.70 (m, 4H), 2.38- 2.24 (m, 6H) 1.1654 Me Me (CO)tBu 6-F 3-Cl CH.sub.2CH.sub.2 p-tolyl .sup.1H NMR (400 MHz, chloroform) ppm 7.42 (dd, J = 8.80, 5.14 Hz, 1 H), 7.11-6.94 (m, 5H), 3.85 (s, 3H), 2.90- 2.68 (m, 4H), 2.32 (s, 3H), 2.24 (s, 3H), 1.03 (s, 9H) 1.1655 Me Me (CO)Ph 6-F 3-Cl CH.sub.2CH.sub.2 p-tolyl .sup.1H NMR (400 MHz, chloroform) ppm 7.90 (dd, J = 8.38, 1.28 Hz, 2 H), 7.65-7.57 (m, 1H), 7.48-7.39 (m, 2H), 7.32 (dd, J = 8.80, 5.14 Hz, 1 H), 7.13-7.02 (m, 4H), 6.91 (t, J = 8.68 Hz, 1 H), 3.87 (s, 3H), 2.92-2.70 (m, 4H), 2.28-2.23 (m, 6H) 1.1656 Me Me (CO)4- 6-F 3-Cl CH.sub.2CH.sub.2 p-tolyl .sup.1H NMR (400 MHz, chloroform) morph- ppm 7.46 (dd, J = 8.86, 5.20 Hz, 1 H), olino 7.11-6.96 (m, 5H), 3.85 (s, 3H), 3.59- 3.20 (m, 8H), 2.96-2.67 (m, 4H), 2.40-2.22 (m, 6H)

Biological Examples

B1 Post-Emergence EfficacyTest 1

[0206] 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%). A blank value in the table is indicative that the compound was not tested on that species.

TABLE-US-00003 TABLE 3 Control of weed species by compounds of formula (I) after post-emergence application Compound AMARE SOLNI SETFA LOLPE ECHCG IPOHE 1.0001 5 5 5 5 5 5 1.0002 4 5 3 4 4 5 1.0012 5 5 5 5 5 5 1.0018 5 5 5 5 5 5 1.0024 5 5 5 5 5 5 1.0042 5 5 5 5 5 5 1.0048 5 5 5 5 5 5 1.0054 5 5 5 5 5 5 1.0060 5 5 5 5 5 5 1.0066 5 5 5 4 5 5 1.0089 5 5 5 5 5 5 1.0095 5 5 5 5 5 1.0125 5 5 5 5 5 5 1.0149 5 5 5 5 5 5

B2 Post-Emergence EfficacyTest 2

[0207] 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 250 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%). A blank value in the table is indicative that the compound was not tested on that species.

TABLE-US-00004 TABLE 4 Control of weed species by compounds of formula (I) after post-emergence application Compound AMARE SOLNI SETFA LOLPE ECHCG IPOHE 1.0001 4 5 5 5 5 5 1.0002 1 5 1 1 0 5 1.0012 4 5 5 5 5 5 1.0018 5 5 5 5 5 5 1.0024 5 5 5 5 5 5 1.0042 5 5 5 5 5 5 1.0048 4 5 5 5 5 5 1.0054 4 5 5 4 4 3 1.0060 4 5 5 5 5 5 1.0066 5 5 4 2 3 5 1.0072 5 5 5 5 5 5 1.0089 4 5 5 5 5 5 1.0101 5 5 4 4 4 5 1.0119 3 5 4 4 3 4 1.0095 5 5 5 5 5 1.0143 5 5 2 2 2 5 1.0125 3 5 5 5 5 5 1.0327 5 5 5 5 5 5 1.0333 5 5 5 5 5 5 1.0339 1 5 5 1 3 5 1.0345 5 5 5 5 5 5 1.0351 5 5 5 5 5 5 1.0363 4 5 5 5 5 4 1.0369 4 5 4 4 4 4 1.0375 5 5 5 5 5 5 1.0387 5 5 5 5 5 5 1.0417 5 5 5 5 2 5 1.0429 5 5 5 5 5 5 1.0441 5 5 5 5 4 5 1.0597 4 5 4 4 2 5 1.0603 4 5 4 5 4 5 1.0609 5 5 2 4 3 5 1.0615 4 5 5 5 4 5 1.0621 5 5 4 4 4 5 1.0627 5 5 5 5 5 5 1.0633 5 5 5 5 5 5 1.0639 4 5 2 2 2 1 1.0645 5 5 5 5 5 5 1.0651 4 5 4 4 4 5 1.0657 5 5 5 5 1 5 1.0663 5 5 5 4 2 5 1.0669 4 5 2 2 1 5 1.0675 5 5 5 4 2 5 1.0681 3 5 2 3 3 5 1.0687 4 5 5 5 5 5 1.0693 4 4 4 4 4 1.0789 5 5 5 5 5 5 1.0885 5 5 5 5 4 5 1.0891 5 5 4 4 4 4 1.0897 4 5 4 4 4 5 1.0149 4 5 5 5 5 5 1.0969 5 5 4 4 4 4 1.0999 5 5 5 5 4 5 1.1005 4 5 4 4 3 3 1.1257 4 5 5 5 5 4 1.1258 3 5 5 5 5 5 1.1259 1 5 1 2 2 2 1.1265 2 5 1 2 2 3 1.1267 4 5 0 1 1 3 1.1269 3 4 0 1 0 4 1.1270 2 4 0 0 0 0 1.1271 0 5 1 1 0 4 1.1348 2 5 1 3 3 4 1.1351 3 5 4 4 4 4 1.1352 2 4 2 2 3 4 1.1357 2 5 3 2 5 3 1.1363 1 5 0 1 1 2 1.1367 1 3 0 0 0 3 1.1369 4 4 0 1 1 4 1.1370 2 3 0 1 1 3 1.1372 1 1 2 2 5 1.1383 2 5 0 0 0 4 1.1387 0 0 0 0 0 2 1.1454 4 5 4 5 5 5 1.1457 4 5 1 1 1 4 1.1556 3 5 4 5 5 5 1.1651 4 5 5 5 5 4 1.1652 3 3 3 1 0 1 1.1653 4 5 5 5 5 5 1.1654 4 5 5 3 5 5 1.1655 3 5 2 1 3 1 1.1656 3 5 2 1 2 4

B3 Post-Emergence EfficacyTest 3

[0208] 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-00005 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-00006 TABLE B2 Chemical composition of IF50 Chemical CAS Registry Amount Component description Function number (% w/w) Emulsogen Castor oil Emulsifier 61791-12-6 11.12 EL360 ethoxylate N-methyl- 1-Methyl- Solvent 872-50-4 44.44 pyrrolidone 2-pyrrolidone Dowanol DPM Dipropylene Solvent 34590-94-8 44.44 glycol ether glycol monomethyl ether

[0209] 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 5 to 8. A blank value in the table is indicative that the compound was not tested on that species.

TABLE-US-00007 TABLE 5 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 1.0001 500 20 90 0 90 100 20 70 90 80 30 250 10 80 0 90 90 10 70 80 70 125 10 80 0 80 80 10 70 80 50 60 10 80 0 80 80 0 80 50 30 0 60 0 70 70 0 70 30 15 0 0 40 50 0 50 70 50 30 1.0012 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 1.0018 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 1.0024 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 1.0042 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 1.0048 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 1.0066 500 60 90 10 10 50 10 10 80 10 0 250 40 90 0 0 20 10 0 60 0 0 125 30 80 0 0 0 10 0 60 0 0 60 20 80 0 0 0 0 0 40 0 0 30 10 40 0 0 0 0 0 30 0 0 15 10 40 0 0 0 0 0 10 0 0 1.0072 500 20 40 0 80 70 0 20 70 40 0 250 0 40 0 60 20 0 10 60 20 0 125 0 30 0 30 10 0 60 10 0 60 0 30 0 20 0 0 0 50 10 0 30 0 20 0 0 0 0 40 20 0 15 0 10 0 0 0 0 0 0 0 1.0095 500 30 50 30 60 70 60 60 80 80 30 250 10 50 10 40 40 50 30 80 70 125 0 40 0 40 10 40 70 70 60 0 30 0 20 20 50 60 60 20 30 0 20 0 10 10 20 10 50 50 15 0 10 0 0 0 0 30 10 1.0101 500 10 90 20 90 70 70 70 50 80 20 250 0 80 0 50 70 0 10 60 60 125 0 40 0 50 0 0 0 40 70 10 60 0 50 0 30 30 0 0 60 0 30 0 30 0 20 60 0 0 40 60 15 0 30 0 0 0 0 30 40 1.0125 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 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 1.0149 500 0 40 10 20 40 0 10 80 10 0 250 0 30 10 20 40 0 10 70 10 0 125 0 30 0 10 10 0 0 70 0 0 60 0 20 0 0 0 0 0 70 0 0 30 0 20 0 0 0 0 0 70 0 0 15 0 10 0 0 0 0 0 60 0 0 1.0327 500 70 90 0 80 90 80 30 90 90 40 250 10 90 0 60 70 40 70 80 30 125 0 80 0 30 10 10 50 20 60 0 60 0 20 10 10 30 40 30 0 40 0 0 80 20 0 20 30 15 0 20 0 0 0 0 10 0 1.0333 500 90 90 0 90 100 90 90 90 90 70 250 70 90 0 80 90 80 50 80 80 125 40 90 0 80 100 70 40 80 80 60 10 80 0 60 70 10 60 70 10 30 0 80 0 30 80 20 0 60 70 15 0 70 0 0 0 10 0 30 70 0 1.0345 500 20 60 30 50 10 20 0 30 0 30 250 0 30 20 30 20 0 0 20 125 0 40 0 0 0 10 0 20 0 20 60 0 40 0 0 0 0 20 0 20 30 0 20 0 0 0 0 0 0 0 0 15 0 10 0 0 0 0 0 0 0 1.0351 500 20 80 10 80 100 50 0 70 60 20 250 10 70 10 70 90 0 40 50 10 125 0 60 0 60 50 0 0 50 60 60 0 40 0 40 60 0 0 50 60 30 0 20 0 30 100 0 0 40 0 15 0 10 0 0 10 0 0 0 0 1.0387 500 60 90 0 100 100 90 100 100 100 50 250 40 90 0 90 80 70 80 90 100 50 125 20 90 0 90 70 60 40 90 100 40 60 10 90 0 90 70 40 90 30 30 0 90 0 80 60 30 30 80 90 20 15 0 90 0 80 60 10 0 60 90 10 1.0417 500 30 40 0 0 0 0 0 0 10 10 250 0 20 0 0 0 0 0 0 0 125 0 10 0 0 0 0 0 0 0 10 60 0 10 0 0 0 0 0 0 0 10 30 0 10 0 0 0 0 0 0 0 15 0 10 0 0 0 0 0 0 0 1.0429 500 20 60 30 90 70 0 0 60 70 30 250 0 50 20 60 80 0 0 50 30 20 125 0 40 0 50 20 0 0 30 10 60 0 20 0 20 0 0 0 20 0 30 0 10 0 30 0 0 0 10 0 10 15 0 10 0 10 0 0 0 0 0 1.0615 500 50 50 30 80 60 20 30 80 90 0 250 10 40 20 70 50 10 30 70 80 0 125 0 30 0 50 40 0 30 60 70 0 60 20 20 0 40 30 0 20 60 60 0 30 0 10 0 30 20 0 20 60 0 15 0 10 0 10 10 0 0 10 0 1.0633 500 40 100 30 90 70 80 90 100 100 50 250 30 90 20 80 60 70 80 90 100 50 125 20 80 10 70 60 70 80 80 90 60 10 80 10 70 50 50 50 80 90 30 30 0 70 0 10 30 20 80 80 20 15 0 40 0 20 0 0 10 80 0 1.1653 500 10 30 0 40 10 30 0 40 30 10 250 0 10 0 30 60 0 0 30 0 125 0 10 0 20 80 0 40 0 60 0 10 0 60 10 0 0 0 0 30 0 10 0 50 0 0 0 0 15 0 10 0 20 0 0 0 40 0

TABLE-US-00008 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 EPHHL SIDSP ABUTH XANST IPOHE BIDPI AMARE 1.0001 500 100 70 100 90 90 90 80 100 70 100 250 90 60 90 90 80 50 70 90 60 90 125 90 60 90 90 80 40 70 90 60 90 60 80 60 90 90 80 40 70 80 60 90 30 30 60 90 90 80 30 70 30 60 90 15 20 40 80 90 80 20 60 20 40 80 1.0012 500 100 90 100 100 100 100 100 100 90 100 250 100 90 90 90 100 100 100 100 90 90 125 90 90 90 90 100 70 90 90 90 90 60 90 80 90 90 100 70 90 90 80 90 30 70 80 80 80 70 80 70 80 80 15 50 80 60 70 70 60 50 80 60 1.0018 500 100 100 100 100 100 90 100 100 100 100 250 100 90 90 100 100 90 100 100 90 90 125 90 90 90 100 80 100 90 90 90 60 80 80 50 90 90 70 90 80 80 50 30 70 80 50 90 60 90 70 80 50 15 60 40 20 70 50 90 60 40 20 1.0024 500 100 100 100 100 100 90 100 100 100 100 250 100 100 100 100 100 80 100 100 100 100 125 100 100 90 100 70 100 100 100 60 90 100 100 100 70 100 90 100 100 30 90 90 90 100 70 100 90 90 90 15 80 90 80 80 100 70 80 90 80 1.0042 500 100 100 100 100 100 90 100 100 100 100 250 100 100 100 100 80 100 100 100 100 125 90 100 100 80 100 80 100 90 100 100 60 90 90 100 80 100 80 90 90 90 100 30 90 90 90 100 80 90 90 90 90 15 70 80 90 80 80 70 80 90 1.0048 500 100 100 100 100 100 100 100 100 100 100 250 100 100 100 90 100 80 100 100 100 100 125 100 100 100 90 100 80 100 100 100 100 60 100 90 100 80 100 70 90 100 90 100 30 100 80 90 90 100 60 80 100 80 90 15 80 70 100 70 80 80 70 1.0066 500 70 90 90 80 90 70 80 70 90 90 250 70 90 80 80 90 50 80 70 90 80 125 60 80 80 80 80 50 80 60 80 80 60 60 80 80 70 80 40 70 60 80 80 30 30 60 70 70 80 40 80 30 60 70 15 30 60 60 70 60 40 80 30 60 60 1.0072 500 70 50 90 90 60 80 70 50 90 250 70 80 90 10 80 70 80 125 60 20 80 80 10 80 60 20 80 60 80 70 10 70 80 30 20 10 70 60 0 50 20 10 70 15 10 70 30 0 40 10 70 1.0095 500 90 70 80 70 30 80 90 70 80 250 60 40 30 0 80 60 40 125 50 30 60 30 0 80 50 30 60 60 50 20 60 40 0 80 50 20 60 30 40 40 20 0 70 40 40 15 40 20 10 0 70 40 20 1.0101 500 70 70 90 90 30 80 70 70 90 250 50 60 80 80 0 80 50 60 80 125 40 80 60 0 80 40 80 60 80 80 0 80 80 30 50 30 70 90 0 80 50 30 70 15 20 30 70 80 0 80 20 30 70 1.0125 500 100 100 100 100 100 100 100 100 100 100 250 100 90 100 90 100 80 100 100 90 100 125 100 90 90 90 100 70 100 100 90 90 60 100 80 90 90 100 70 90 100 80 90 30 90 90 90 100 60 90 90 90 15 90 80 90 60 80 90 80 1.0149 500 80 50 80 80 80 60 90 80 50 80 250 70 50 70 70 70 50 80 70 50 70 125 70 40 70 70 70 40 80 70 40 70 60 60 50 70 60 50 40 80 60 50 70 30 40 50 70 60 30 30 70 40 50 70 15 40 40 70 60 30 30 50 40 40 70 1.0327 500 80 90 90 90 70 80 80 90 90 250 80 20 80 90 40 70 80 20 80 125 60 30 80 90 20 50 60 30 80 60 60 20 80 90 10 50 60 20 80 30 40 40 30 0 40 40 40 15 20 10 20 20 0 30 20 10 20 1.0333 500 100 80 100 90 60 90 100 80 100 250 80 80 90 90 40 90 80 80 90 125 70 80 90 90 30 90 70 80 90 60 60 30 80 90 0 80 60 30 80 30 50 80 90 80 50 80 15 50 70 90 80 50 70 1.0345 500 80 40 80 80 30 80 80 40 80 250 70 70 80 80 70 70 125 60 60 70 80 60 60 60 50 40 60 60 0 80 50 40 60 30 30 50 40 0 80 30 50 15 30 20 20 0 80 30 20 1.0351 500 80 80 90 90 30 80 80 80 90 250 60 20 80 90 20 70 60 20 80 125 60 20 80 90 10 60 60 20 80 60 70 60 80 0 60 70 60 30 50 60 90 0 50 50 60 15 40 10 80 0 50 40 10 1.0387 500 100 90 90 100 50 90 100 90 90 250 90 80 90 90 40 90 90 80 90 125 90 70 90 90 30 90 90 70 90 60 80 60 90 90 20 90 80 60 90 30 70 50 80 90 10 80 70 50 80 15 50 80 90 10 80 50 80 1.0417 500 60 60 60 80 0 70 60 60 60 250 60 0 70 70 0 60 60 0 70 125 40 0 60 60 0 50 40 0 60 60 30 50 10 0 40 30 50 30 30 40 0 0 50 30 40 15 20 0 0 0 30 20 0 1.0429 500 70 50 90 90 40 80 70 50 90 250 40 60 80 90 30 80 40 60 80 125 30 80 90 10 70 30 80 60 20 70 90 0 50 20 70 30 10 0 70 90 0 50 10 0 70 15 0 0 60 90 0 40 0 0 60 1.0615 500 80 60 90 100 60 70 80 60 90 250 70 50 80 90 40 60 70 50 80 125 50 40 80 90 30 40 50 40 80 60 40 20 80 90 20 40 20 80 30 30 20 70 80 10 40 30 20 70 15 20 50 60 10 30 20 50 1.0633 500 90 90 90 100 70 90 90 90 90 250 80 90 90 100 50 80 80 90 90 125 70 80 80 90 80 70 80 80 60 60 80 70 90 40 80 60 80 70 30 40 60 70 90 20 60 40 60 70 15 40 50 60 80 10 60 40 50 60 1.1653 500 60 30 80 90 90 70 60 30 80 250 60 20 70 80 40 80 60 20 70 125 40 70 30 60 40 70 60 40 70 70 20 60 40 70 30 30 10 70 70 10 50 30 10 70 15 20 70 50 10 40 20 70

TABLE-US-00009 TABLE 7 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 1.0001 500 20 20 100 100 80 90 60 80 60 100 250 10 20 100 100 60 80 40 80 30 100 125 0 10 100 100 30 70 20 80 10 100 60 0 0 100 90 20 60 10 70 10 100 30 0 0 90 90 0 50 20 70 0 100 15 0 0 90 100 0 30 20 60 0 1.0012 500 30 40 90 70 50 70 30 60 50 100 250 20 30 90 50 50 50 20 40 30 80 125 10 10 80 50 20 40 0 50 10 80 60 0 10 80 50 10 30 0 50 10 70 30 0 0 80 40 10 20 0 30 20 50 15 0 0 80 30 20 10 0 30 10 1.0018 500 0 0 100 100 0 10 20 50 10 80 250 0 0 100 100 0 10 20 50 0 70 125 0 0 100 100 0 0 0 40 0 70 60 0 0 80 80 0 0 0 40 0 30 30 0 0 60 80 0 0 0 20 0 15 0 0 40 80 0 0 0 0 1.0024 500 40 50 100 60 60 60 30 70 90 90 250 20 30 90 50 50 50 10 70 80 90 125 10 20 90 40 30 30 0 40 50 80 60 0 10 80 30 20 10 0 30 10 50 30 0 10 80 20 0 0 0 10 0 10 15 0 0 70 0 0 0 0 0 0 0 1.0042 500 250 0 0 40 20 10 0 0 10 10 10 125 0 0 20 10 10 0 0 0 0 0 60 0 0 30 0 0 0 0 0 0 0 30 0 0 30 0 0 0 0 0 0 0 15 0 0 30 0 0 0 0 0 0 0 1.0048 500 30 60 90 70 10 20 10 40 20 80 250 10 40 80 50 0 30 10 50 10 70 125 0 10 90 60 0 20 0 50 10 50 60 0 20 80 50 0 20 0 30 0 60 30 0 0 80 50 0 10 0 20 0 10 15 0 0 80 40 0 0 0 10 0 0 1.0066 500 10 0 100 60 10 10 10 20 20 80 250 10 0 90 50 10 0 0 30 0 50 125 0 0 90 30 0 0 0 10 0 40 60 0 0 90 10 0 0 0 10 0 20 30 0 0 90 0 0 0 0 0 0 0 15 0 0 70 0 0 0 0 0 0 0 1.0072 500 50 70 90 80 90 80 40 90 90 100 250 30 60 90 70 80 70 50 90 90 100 125 10 60 90 60 80 70 30 90 80 90 60 20 40 90 50 60 60 10 80 50 90 30 0 30 80 40 30 40 0 70 40 90 15 0 0 80 40 10 10 0 50 10 60 1.0095 500 60 70 90 100 90 90 20 90 90 90 250 30 50 90 70 80 80 10 80 90 90 125 20 50 80 60 70 70 0 60 90 60 10 20 90 70 70 50 0 50 80 80 30 0 20 80 70 40 20 0 40 70 70 15 0 0 70 50 10 0 0 20 10 1.0101 500 0 10 90 40 50 20 10 60 50 80 250 0 10 80 40 40 10 0 40 50 80 125 0 0 80 20 30 0 0 30 30 60 60 0 0 60 10 20 0 0 20 10 20 30 0 0 40 10 0 0 0 0 0 10 15 0 0 30 0 0 0 0 0 0 0 1.0125 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 1.0149 500 30 0 100 80 20 30 40 20 10 90 250 10 0 100 50 10 20 10 20 10 90 125 0 0 90 40 0 10 10 10 0 100 60 0 0 80 40 0 10 0 10 0 100 30 0 0 80 40 0 10 0 10 0 80 15 0 0 80 0 0 0 0 0 80 1.0327 500 20 0 90 40 20 10 0 70 30 90 250 20 0 90 40 10 10 0 20 10 90 125 0 0 80 40 10 0 0 10 0 50 60 0 0 50 20 0 0 0 10 0 40 30 0 0 40 30 0 0 0 0 0 0 15 0 0 30 30 0 0 0 0 0 0 1.0333 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 1.0345 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 1.0351 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 1.0387 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 1.0417 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 1.0429 500 20 50 90 80 60 60 20 40 80 80 250 20 0 90 60 70 60 10 50 70 70 125 0 0 90 50 40 40 0 40 80 80 60 0 0 90 40 50 40 0 50 80 80 30 0 0 70 40 50 30 0 40 70 60 15 0 0 80 30 10 10 0 30 50 60 1.0615 500 50 60 100 100 50 90 60 70 250 30 40 100 100 30 90 40 70 125 10 30 90 100 20 70 30 60 60 10 10 80 100 20 60 40 40 30 0 0 60 100 10 30 30 40 15 0 0 50 80 0 0 0 20 1.0633 500 250 10 50 90 70 40 70 20 40 70 80 125 0 50 90 50 20 50 10 20 50 70 60 0 20 80 50 10 20 0 20 20 30 0 0 80 50 0 10 0 0 0 80 15 0 0 60 40 0 0 0 0 0 1.1653 500 20 40 100 100 20 70 30 60 80 90 250 0 30 100 100 30 60 40 60 80 90 125 0 40 90 80 20 20 40 30 60 80 60 0 0 90 70 0 10 0 10 50 80 30 0 0 70 70 0 0 0 0 10 70 15 0 0 60 70 0 0 0 0 0

TABLE-US-00010 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 POLCO KCHSC SINAR STEME GALAP VERPE 1.0001 500 20 20 100 80 100 100 90 90 250 10 20 100 80 100 100 90 90 125 0 10 100 70 90 100 80 80 60 0 0 100 50 90 80 80 30 0 0 100 40 90 100 70 15 0 0 90 30 90 100 20 60 1.0012 500 30 40 100 70 90 90 80 90 250 20 30 100 60 80 80 40 80 125 10 10 90 30 80 70 50 70 60 0 10 90 10 80 80 30 60 30 0 0 90 0 70 20 60 15 0 0 100 0 80 0 60 1.0018 500 0 0 100 60 100 100 90 90 250 0 0 100 60 90 90 90 90 125 0 0 100 40 90 90 60 80 60 0 0 90 10 40 90 80 30 0 0 100 10 20 90 20 70 15 0 0 80 0 20 80 0 40 1.0024 500 40 50 100 80 100 90 50 90 250 20 30 100 80 90 80 60 70 125 10 20 80 80 90 80 30 60 60 0 10 80 50 80 80 30 30 0 10 80 30 80 70 20 15 0 0 70 10 80 50 10 1.0042 500 250 0 0 40 20 20 50 30 40 125 0 0 20 10 10 60 40 30 60 0 0 30 10 60 20 30 30 0 0 30 0 10 60 20 20 15 0 0 0 0 0 30 0 20 1.0048 500 30 60 90 40 90 90 60 80 250 10 40 90 50 80 80 70 80 125 0 10 90 40 80 80 70 70 60 0 20 80 20 70 50 60 30 0 0 80 30 70 70 50 40 15 0 0 50 10 70 20 20 1.0066 500 10 0 80 70 80 70 40 40 250 10 0 60 60 80 70 50 20 125 0 0 50 80 70 30 20 60 0 0 20 60 40 10 30 0 0 0 70 50 30 0 15 0 0 0 40 30 20 0 1.0072 500 50 70 100 90 90 90 90 100 250 30 60 100 90 90 90 90 100 125 10 60 100 80 80 90 50 90 60 20 40 70 70 80 60 80 30 0 30 90 30 70 20 70 15 0 0 90 20 70 30 60 1.0095 500 60 70 100 60 100 100 90 90 250 30 50 100 30 80 90 70 90 125 20 50 100 30 70 80 60 80 60 10 20 90 20 80 40 80 30 0 20 90 0 70 70 50 15 0 0 90 0 50 80 30 30 1.0101 500 0 10 80 90 70 70 70 80 250 0 10 90 70 50 80 50 70 125 0 0 80 70 40 70 70 60 0 0 70 30 60 20 50 30 0 0 50 10 0 60 15 0 0 0 0 0 30 20 1.0125 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 1.0149 500 30 0 90 70 100 100 70 100 250 10 0 90 50 90 100 40 80 125 0 0 90 50 80 90 40 80 60 0 0 80 30 80 90 40 80 30 0 0 30 0 60 90 40 60 15 0 0 20 0 50 80 20 40 1.0327 500 20 0 70 60 60 90 30 70 250 20 0 30 50 40 70 30 50 125 0 0 20 40 40 70 30 40 60 0 0 20 30 30 40 30 40 30 0 0 10 20 20 40 20 30 15 0 0 10 10 0 20 10 20 1.0333 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 1.0345 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 1.0351 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 1.0387 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 1.0417 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 1.0429 500 20 50 100 30 60 80 20 90 250 20 0 90 20 70 80 10 60 125 0 0 90 20 60 70 20 60 60 0 0 90 10 40 70 20 70 30 0 0 60 0 60 15 0 0 0 40 70 20 60 1.0615 500 50 60 100 100 100 100 100 90 250 30 40 100 100 100 100 100 80 125 10 30 100 100 100 100 60 60 10 10 90 80 100 60 30 0 0 100 80 100 50 15 0 0 100 70 60 100 40 1.0633 500 250 10 50 90 80 90 80 70 80 125 0 50 90 80 80 80 60 70 60 0 20 80 60 70 80 60 60 30 0 0 90 60 90 50 50 15 0 0 80 20 40 80 10 20 1.1653 500 20 40 100 70 90 100 80 90 250 0 30 100 60 100 100 50 80 125 0 40 90 50 90 100 50 70 60 0 0 100 40 90 90 40 60 30 0 0 100 30 90 40 50 15 0 0 90 20 80 20 30