2-PHENOXY-PYRIMIDINE DERIVATIVES AS HERBICIDAL COMPOUNDS

Abstract

The present invention relates to compounds of Formula (I), wherein A, R.sup.1, R.sup.2 n and p are as defined herein. The invention further relates to herbicidal compositions which comprise a compound of Formula (I) and to the use of compounds of Formula (I) for controlling weeds, in particular in crops of useful plants.

##STR00001##

Claims

1. A compound of Formula (I): ##STR00034## wherein A is selected from the group consisting of C.sub.3-C.sub.8 alkyl, C.sub.3-C.sub.8 alkenyl, C.sub.3-C.sub.8 alkynyl, C.sub.3-C.sub.8 haloalkyl, C.sub.3-C.sub.8 haloalkenyl, C.sub.3-C.sub.8 haloalkynyl, C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.3alkyl-, C.sub.1-C.sub.4haloalkoxy-C.sub.1-C.sub.3alkyl-, C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.3haloalkyl- and —(CH.sub.2).sub.mR.sup.3; R.sup.1 is independently selected from the group consisting of halogen, —CN, nitro, C.sub.1-C.sub.4alkyl-, C.sub.2-C.sub.4alkenyl-, C.sub.2-C.sub.4alkynyl-, C.sub.1-C.sub.4haloalkyl-, C.sub.1-C.sub.4 alkoxy-, C.sub.1-C.sub.4haloalkoxy-, —S(O).sub.nC.sub.1-C.sub.4alkyl and C.sub.3-C.sub.6cycloalkyl-; R.sup.2 is selected from the group consisting of halogen, —CN, nitro, C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl-, C.sub.1-C.sub.4alkynyl-, C.sub.1-C.sub.4haloalkyl-, C.sub.1-C.sub.4alkoxy-, C.sub.1-C.sub.4haloalkoxy-, —S(O).sub.nC.sub.1-C.sub.4alkyl and C.sub.3-C.sub.6cycloalkyl-; m is 1, 2, 3 or 4; n is 0, 1 or 2; p is 0, 1 or 2; R.sup.3 is selected from C.sub.3-C.sub.6cycloalkyl, phenyl and a 5 or 6 membered heteroaryl which comprises from 1 to 4 heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulphur, and wherein said phenyl or heteroaryl groups are optionally substituted by one, two or three substituents independently selected from the group consisting of halogen, cyano, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, C.sub.1-C.sub.4 alkoxy and C.sub.1-C.sub.4 haloalkoxy; or an agriculturally acceptable salt thereof.

2. A compound according to claim 1, wherein the compound of Formula (I) is a compound of Formula (Ia): ##STR00035##

3. A compound according to claim 1, wherein A is selected from the group consisting of C.sub.3-C.sub.8 alkyl, C.sub.3-C.sub.8 alkenyl, C.sub.3-C.sub.8 alkynyl, C.sub.3-C.sub.8 haloalkyl, C.sub.3-.sub.8 haloalkenyl, C.sub.3-.sub.8 haloalkynyl, C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.3alkyl-, C.sub.1-C.sub.4haloalkoxy-C.sub.1-C.sub.3alkyl- and C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.3haloalkyl-.

4. A compound according to claim 1, wherein A is selected from the group consisting of C.sub.3-.sub.8 alkyl, C.sub.3-.sub.8 haloalkyl, C.sub.3-.sub.8 haloalkenyl, C.sub.3-C.sub.8 haloalkynyl and C.sub.1-C.sub.4haloalkoxy-C.sub.1-C.sub.3alkyl-;

5. A compound according to claim 1, wherein R.sup.1 is halogen or —CN.

6. A compound according to claim 1, wherein R.sup.2 is selected from the group consisting of halogen, C.sub.1-C.sub.4 alkyl, C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.4 haloalkyl, C.sub.1-C.sub.4 alkoxy and C.sub.1-C.sub.4 haloalkoxy.

7. A compound according to claim 1, wherein R.sup.2 is selected from the group consisting of methyl, methoxy- and halogen.

8. A compound according to claim 1, wherein R.sup.2 is halogen.

9. A compound according to claim 1, wherein R.sup.2 is chloro.

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

11. A herbicidal composition according to claim 10, further comprising at least one additional pesticide.

12. A herbicidal composition according to claim 11, wherein the additional pesticide is a herbicide or herbicide safener.

13. A method of controlling weeds at a locus comprising application to the locus of a weed controlling amount of a composition according to claim 10.

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

15. A method of controlling weeds at a locus comprising application to the locus of a weed controlling amount of a composition according to claim 11.

16. A method of controlling weeds at a locus comprising application to the locus of a weed controlling amount of a composition according to claim 12.

Description

EXAMPLE 1

Synthesis of 3-(5-chloropyrimidin-2-yl)oxy-2-(4,4,4-trifluorobutylsulfanyl)benzonitrile—Compound A28

Step 1: Synthesis of 3-methoxy-2-(4,4,4-trifluorobutylsulfanyl)benzonitrile

[0111] ##STR00014##

[0112] To a stirred solution of 2-iodo-3-methoxy-benzonitrile (1.0 g, 3.9 mmol) and N,N-diisopropylethylamine (1.0 g, 1.3 mL, 7.7 mmol) in 1,4-dioxane (15 mL) under nitrogen was added [(4,5-bis(diphenylphosphino)-9,9-dimethylxanthene)-2-(2′-amino-1,1′-biphenyl)]palladium(II) methanesulfonate (0.39 g, 0.39 mmol) and 4,4,4-trifluorobutane-1-thiol (0.61 g, 4.2 mmol). The reaction was heated at 120° C. for 2 hours by microwave irradiation, after which the solvent was removed under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 0-30% ethyl acetate in cyclohexane as eluent to give the desired product (0.95 g, 72%).

[0113] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.44-7.37 (m, 1H), 7.30 (dd, 1H), 7.12 (dd, 1H), 3.94 (s, 3H), 3.01 (t, 2H), 2.40-2.24 (m, 2H), 1.83-1.70 (m, 2H)

Step 2: Synthesis of 3-hydroxy-2-(4,4,4-trifluorobutylsulfanyl)benzonitrile

[0114] ##STR00015##

[0115] To a stirred solution of 3-methoxy-2-(4,4,4-trifluorobutylsulfanyl)benzonitrile (0.95 g, 3.5 mmol) in DCM (35 mL) at 0° C. under an atmosphere of N.sub.2 was added BBr.sub.3 (8.6 mL of a 1M solution in DCM, 8.6 mmol). The reaction was allowed to warm to room temperature over 1 hour and was then stirred overnight after which the mixture was quenched with saturated NaHCO.sub.3 solution and extracted with DCM (×3). The combined organic extracts were passed through a hydrophobic frit and concentrated under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 0-60% EtOAc in cyclohexane as eluent to give the desired product (0.76 g, 84%).

[0116] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.42-7.37 (m, 1H), 7.32 (dd, 1H), 7.26 (dd, 1H), 6.93 (br s, 1H), 2.92 (t, 2H), 2.34-2.20 (m, 2H), 1.92-1.81 (m, 2H)

Step 3: Synthesis of 3-(5-chloropyrimidin-2-yl)oxy-2-(4,4,4-trifluorobutylsulfanyl)benzonitrile.

[0117] ##STR00016##

[0118] To a stirred solution of 3-hydroxy-2-(4,4,4-trifluorobutylsulfanyl)benzonitrile (0.30 g, 1.1 mmol) and potassium carbonate (0.32 g, 2.3 mmol) in dimethylformamide (3 mL) was added 2,5-dichloropyrimidine (0.21 g, 1.4 mmol). The reaction was heated at 80° C. for 4 hours and then allowed to cool to RT. The reaction mixture was diluted with EtOAc and H.sub.2O, the phases were separated and the aqueous phase was extracted with further EtOAc. The combined organics were dried over MgSO.sub.4, filtered and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography over silica gel using a gradient of 0-30% EtOAc in cyclohexane as eluent to give the desired product (0.33 g, 77%).

[0119] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.48 (s, 2H), 7.66 (dd, 1H), 7.53 (t, 1H), 7.48-7.42 (m, 1H), 3.05-2.99 (m, 2H), 2.35-2.17 (m, 2H), 1.81-1.72 (m, 2H)

EXAMPLE 2

Synthesis of 3-(5-chloropyrimidin-2-yl)oxy-2-(4,4,4-trifluorobutylsulfinyl)benzonitrile—Compound A29

[0120] ##STR00017##

[0121] To a stirred solution of 3-(5-chloropyrimidin-2-yl)oxy-2-(4,4,4-trifluorobutylsulfanyl)benzonitrile (0.10 g, 0.27 mmol) in DCM (2.7 mL) at 0° C. was added 3-chloroperbenzoic acid (≤77%, 0.060 g, 0.27 mmol). The reaction was stirred at 0° C. for 20 minutes and then diluted with DCM and saturated Na.sub.2S.sub.2O.sub.5 solution. The phases were separated and the organic phase washed with further portions of saturated Na.sub.2S.sub.2O.sub.5 solution (×2). The organic phase was then washed with saturated NaHCO.sub.3 solution, passed through a hydrophobic frit and concentrated under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 0-100% EtOAc in cyclohexane as eluent to give the desired product (0.089 g, 85%).

[0122] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.50 (s, 2H), 7.80 (dd, 1H), 7.70 (t, 1H), 7.47 (dd, 1H), 3.50-3.41 (m, 1H), 3.23-3.12 (m, 1H), 2.40-2.25 (m, 2H), 2.19-2.06 (m, 2H)

EXAMPLE 3

Synthesis of 3-(5-chloropyrimidin-2-yl)oxy-2-(4,4,4-trifluorobutylsulfonyl)benzonitrile—Compound A30

[0123] ##STR00018##

[0124] To a stirred solution of 3-(5-chloropyrimidin-2-yl)oxy-2-(4,4,4-trifluorobutylsulfanyl)benzonitrile (0.13 g, 0.35 mmol) in DCM (3.5 mL) at 0° C. was added 3-chloroperbenzoic acid (≤77%, 0.390 g, 1.74 mmol). The reaction was stirred at 0° C. for 3 hours and then diluted with DCM and saturated Na.sub.2S.sub.2O.sub.5 solution. The phases were separated and the organic phase washed with further portions of saturated Na.sub.2S.sub.2O.sub.5 solution (×2). The organic phase was then washed with saturated NaHCO.sub.3 solution, passed through a hydrophobic frit and concentrated under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 0-100% EtOAc in cyclohexane as eluent to give the desired product (0.129 g, 91%).

[0125] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.49 (s, 2H), 7.90-7.83 (m, 2H), 7.61 (dd, 1H), 3.59 (t, 2H), 2.42-2.29 (m, 2H), 2.16-2.07 (m, 2H)

EXAMPLE 4

Synthesis of 5-chloro-2-[3-chloro-2-(3,3,3-trifluoropropylsulfanyl) phenoxy]pyrimidine—Compound A10

Step 1: Synthesis of 1-chloro-3-methoxy-2-(3,3,3-trifluoropropylsulfanyl) benzene

[0126] ##STR00019##

[0127] To a stirred solution of 2-chloro-6-methoxy-benzenethiol (0.30 g, 1.7 mmol) and potassium carbonate (0.47 g, 3.4 mmol) in dimethylformamide (3 mL) was added 1,1,1-trifluoro-3-iodo-propane (0.46 g, 0.24 mL, 2.1 mmol). The reaction was stirred overnight at room temperature and then diluted with Et.sub.2O and water. The phases were separated and the aqueous was re-extracted with Et.sub.2O. The combined organics were dried over MgSO.sub.4 and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography over silica gel using a gradient of 0-20% EtOAc in cyclohexane as eluent to give the desired product (0.44 g, 94%).

[0128] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.32-7.28 (m, 1H), 7.14 (dd, 1H), 6.87 (dd, 1H), 3.95 (s, 3H), 3.09-3.02 (m, 2H), 2.41-2.27 (m, 2H)

Step 2: Synthesis of 3-chloro-2-(3,3,3-trifluoropropylsulfanyl)phenol

[0129] ##STR00020##

[0130] To a stirred solution of 1-chloro-3-methoxy-2-(3,3,3-trifluoropropylsulfanyl)benzene (0.40 g, 1.5 mmol) in DCM (15 mL) at 0° C. under an atmosphere of N.sub.2 was added BBr.sub.3 (3.7 mL of a 1M solution in DCM, 3.7 mmol). The reaction was allowed to warm to room temperature and was stirred for 4 hours after which the mixture was quenched with saturated NaHCO.sub.3 solution and extracted with DCM (×2). The combined organic extracts were passed through a hydrophobic frit and concentrated under reduced pressure. The crude residue was purified by flash chromatography on silica gel using a gradient of 0-15% EtOAc in cyclohexane as eluent to give the desired product (0.30 g, 78%).

[0131] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.25 (t, 1H), 7.06 (dd, 1H), 6.96 (dd, 1H), 6.94 (s, 1H), 3.00-2.92 (m, 2H), 2.42-2.28 (m, 2H)

Step 3: Synthesis of 5-chloro-2-[3-chloro-2-(3,3,3-trifluoropropylsulfanyl) phenoxy]pyrimidine

[0132] ##STR00021##

[0133] To a stirred solution of 3-chloro-2-(3,3,3-trifluoropropylsulfanyl)phenol (0.18 g, 0.70 mmol) and potassium carbonate (0.19 g, 1.4 mmol) in dimethylformamide (1.8 mL) was added 2,5-dichloropyrimidine (0.13 g, 0.84 mmol). The reaction was heated at 80° C. for 3 hours and then allowed to cool to RT. The reaction mixture was diluted with EtOAc and H.sub.2O, the phases were separated and the aqueous phase was extracted with further EtOAc. The combined organics were dried over MgSO.sub.4, filtered and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography over silica gel using a gradient of 0-20% EtOAc in cyclohexane as eluent to give the desired product (0.16 g, 63%).

[0134] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.48 (s, 2H), 7.49-7.43 (m, 1H), 7.43-7.37 (m, 1H), 7.18 (dd, 1H), 3.01-2.95 (m, 2H), 2.36-2.23 (m, 2H)

EXAMPLE 5:

Synthesis of 5-chloro-2-[2-(4,4,4-trifluorobutylsulfanyl)phenoxy] pyrimidine—Compound A4

[0135] ##STR00022##

[0136] To a stirred solution of 2-sulfanylphenol (0.75 g, 0.60 mL, 5.9 mmol) and potassium carbonate (0.82 g, 5.9 mmol) in dimethylformamide (7.5 mL) was added 4-bromo-1,1,1-trifluoro-butane (1.14 g, 0.74 mL, 5.9 mmol). The reaction was stirred at room temperature for 1.5 hours after which potassium carbonate (0.90 g, 6.5 mmol) and 2,5-dichloropyrimidine (1.06 g, 7.1 mmol) were added. The reaction was heated at 80° C. for 1 hour and then allowed to cool to RT. The reaction mixture was diluted with Et.sub.2O and H.sub.2O, the phases were separated and the aqueous phase was extracted with further Et.sub.2O. The combined organics were dried over MgSO.sub.4, filtered and evaporated to dryness under reduced pressure. The crude residue was purified by flash chromatography over silica gel using a gradient of 0-20% EtOAc in cyclohexane as eluent to give the desired product (1.38 g, 66%).

[0137] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.48 (s, 2H), 7.48 (dd, 1H), 7.40-7.31 (m, 1H), 7.31 -7.24 (m, 1H), 7.19 (dd, 1H), 2.92 (t, 2H), 2.25-2.12 (m, 2H), 1.85-1.77 (m, 2H)

EXAMPLE 6

Synthesis of 5-chloro-2-[3-chloro-2-(4,4-difluorobutylsulfanyl) phenoxy]pyrimidine—Compound A105

Step 1: Synthesis of 2-[3-(2-chloro-6-methoxy-phenyl)sulfanylpropyl]-1,3-dioxolane

[0138] ##STR00023##

[0139] To a stirred solution of 2-chloro-6-methoxybenzenethiol (0.75 g, 4.29 mmol) and 2-(3-chloropropyl)-1,3-dioxolane (0.776 g, 5.15 mmol) in DMF (7.5 mL) was added K.sub.2CO.sub.3 (1.19 g, 8.59 mmol). The reaction was stirred overnight at RT, then diluted with water and extracted with EtOAc (×3). The combined organic extracts were washed with brine, dried over MgSO.sub.4 and evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography on silica gel using a gradient of 0-20% EtOAc/cyclohexane as eluent to give the desired product (0.72 g, 58%) as a colourless oil.

[0140] .sup.1H NMR (400 MHz, CDCl.sub.3) d=7.19 (t, 1H), 7.07 (d, 1H), 6.79 (d, 1H), 4.81 (t, 1H), 3.94-3.85 (m, 2H), 3.88 (s, 3H), 3.84-3.78 (m, 2H), 2.90 (t, 2H), 1.82-1.73 (m, 2H), 1.68-1.58 (m, 2H)

Step 2: Synthesis of 4-(2-chloro-6-methoxy-phenyl)sulfanylbutanal

[0141] ##STR00024##

[0142] To a solution of 2-[3-(2-chloro-6-methoxy-phenyl)sulfanylpropyl]-1,3-dioxolane (0.72 g, 2.49 mmol) in CH.sub.3CN (6 mL) was added 2M HCl (2 mL). The reaction was stirred at RT overnight, further 2M HCl was added (1 mL) and the reaction heated at 60° C. overnight. The reaction was allowed to cool to RT, diluted with water and extracted with EtOAc (×3). The combined organic extracts were washed with brine, dried over MgSO.sub.4 and evaporated to dryness under reduced pressure to give the crude product (0.64 g) as an orange oil which was used without further purification.

[0143] .sup.1H NMR (400 MHz, CDCl.sub.3) δ=9.75 (s, 1H), 7.19 (t, 1H), 7.07 (d, 1H), 6.80 (d, 1H), 3.89 (s, 3H), 2.90 (t, 2H), 2.63 (t, 2H), 1.82-1.72 (m, 2H)

Step 3: Synthesis of 1-chloro-2-(4,4-difluorobutylsulfanyl)-3-methoxy-benzene

[0144] ##STR00025##

[0145] To a stirred solution of 4-(2-chloro-6-methoxy-phenyl)sulfanylbutanal (644 mg, 2.63 mmol) in DCM (10 mL) was added dropwise diaminosulfur trifluoride (0.773 mL, 5.26 mmol). The reaction was stirred at RT for 2 hours, then cooled to 0° C., quenched with water, diluted with saturated aqueous sodium bicarbonate solution then extracted with EtOAc (×3). The combined organic extracts were washed with brine, dried over MgSO.sub.4 and evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography on silica gel using a gradient of 0-50% EtOAc/cyclohexane as eluent to give the desired product (0.395 g, 56%) as a pale-yellow oil.

[0146] .sup.1H NMR (400 MHz, CDCl.sub.3) d=7.19 (t, 1H), 7.09 (d, 1H), 6.80 (d, 1H), 5.78 (tt, 1H), 3.90 (s, 3H), 2.90 (t, 3H), 1.91-2.09 (m, 2H), 1.69-1.58 (m, 2H)

Step 4: Synthesis of 3-chloro-2-(4,4-difluorobutylsulfanyl)phenol

[0147] ##STR00026##

[0148] To a stirred solution of 1-chloro-2-(4,4-difluorobutylsulfanyl)-3-methoxy-benzene (100 mg, 0.396 mmol) in DMF (1.14 mL) at RT, under an atmosphere of N.sub.2 was added 1-dodecanethiol (0.193 mL, 0.791 mmol) and LiO.sup.tBu (0.79 ml of a 1M solution in THF, 0.79 mmol). The reaction was heated at 100° C. for 90 minutes, allowed to cool to RT, diluted with water and extracted with EtOAc (×3). The combined organic extracts were washed with brine, dried over MgSO.sub.4 and evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography on silica gel using a gradient of 0-30% EtOAc/cyclohexane as eluent to give the desired product as a mixture with 1-dodecanethiol which was used without further purification.

[0149] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.19 (t, 1H), 7.02 (d, 1H), 7.00 (s, 1H), 6.91 (d, 1H), 5.79 (tt, 1H), 2.81 (t, 2H), 2.03-1.88 (m, 2H), 1.79-1.67 (m, 2H)

Step 5: Synthesis of 5-chloro-2-[3-chloro-2-(4,4-difluorobutylsulfanyl)phenoxy] pyrimidine—Compound A105

[0150] ##STR00027##

[0151] A mixture of 3-chloro-2-(4,4-difluorobutylsulfanyl)phenol (0.469 g, 1.86 mmol), 2,5-dichloropyrimidine (0.332 g, 2.23 mmol), K.sub.2CO.sub.3 (0.513 g, 3.71 mmol) in DMF (3 mL) was heated at 140° C. under microwave irradiation for 30 minutes. The reaction was diluted with water and extracted with EtOAc (×3). He combined organic extracts were washed with brine, dried over MgSO.sub.4 and evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography on silica gel using a gradient of 0-30% EtOAc/cyclohexane as eluent to give the desired product (0.0487 g, 72%) as an off-white semi-solid.

[0152] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.47 (s, 2H), 7.41 (d, 1H), 7.33 (t, 1H), 7.13 (d, 1H), 5.78 (tt, 1H), 2.89 (t, 2H), 2.00-1.85 (m, 2H), 1.67-1.58 (m, 2H)

EXAMPLE 7

Synthesis of 3-(5-chloropyrimidin-2-yl)oxy-2-[3-(trifluoromethoxy) propylsulfanyl]benzonitrile—Compound A116

Step 1: Synthesis of 2-fluoro-3-(2-trimethylsilylethoxymethoxy)benzonitrile

[0153] ##STR00028##

[0154] To a solution of 2-fluoro-3-hydroxy-benzonitrile (0.50 g, 3.60 mmol) in DCM (18 mL) was added Et.sub.3N (1.0 mL, 7.3 mL) and 2-(chloromethoxy)ethyl-trimethylsilane (0.70 mL, 4.0 mmol) and the reaction stirred at RT for 72 hours. The reaction was diluted with further DCM, washed with water and brine, dried over MgSO.sub.4 and evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography on silica gel using a gradient of 0-30% EtOAc/cyclohexane as eluent to give the desired product (0.50 g, 51%).

[0155] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.47 (dt, 1H), 7.25-7.19 (m, 1H), 7.16 (dd, 1H), 5.29 (s, 2H), 3.79 (dd, 2H), 0.99-0.91 (m, 2H), 0.02-−0.02 (m, 9H).

Step 2: Synthesis of 2-[3-(trifluoromethoxy)propylsulfanyl]-3-(2-trimethylsilyl ethoxymethoxy)benzonitrile

[0156] ##STR00029##

[0157] A mixture of 2-fluoro-3-(2-trimethylsilylethoxymethoxy)benzonitrile (0.25 g, 0.93 mmol), sodium sulfide (0.103 g, 1.87 mmol) in DMF (2.5 mL) under an N.sub.2 atmosphere was heated at 50° C. overnight. The reaction was allowed to cool to RT, then K.sub.2CO.sub.3 (0.129 g, 0.93 mmol) and 1-bromo-3-(trifluoromethoxy)propane (0.213 g, 1.03 mmol) were added and stirred at RT for 1.5 hours. The reaction was diluted with water and extracted with EtOAc (×3). The combined organic extracts were washed with brine, dried over MgSO.sub.4 and evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography on silica gel using a gradient of 0-20% EtOAc/cyclohexane as eluent to give the desired product (0.286 g, 61%).

[0158] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.32-7.42 (m, 3H) 5.32-5.35 (m, 2H) 4.12 (t, 2H) 3.79 (dd, 2H) 3.07 (t, 2H) 1.91 (t, 2H) 0.95 (dd, 2H) -0.01-0.02 (m, 9H).

[0159] Step 3: Synthesis of 3-hydroxy-2-[3-(trifluoromethoxy)propylsulfanyl]benzo nitrile

##STR00030##

[0160] To a stirred solution of 2-[3-(trifluoromethoxy)propylsulfanyl]-3-(2-trimethylsilylethoxymethoxy)benzonitrile (0.286 g, 0.70 mmol) in MeOH (2.1 mL) and THF (3.5 mL) was added 2M HCl (2.1 mL) and the reaction heated at 75° C. for 2 hours. The reaction was allowed to cool to RT, diluted with water and extracted with EtOAc (×3). The combined organic extracts were dried over MgSO.sub.4 and evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography on silica gel using a gradient of 0-30% EtOAc/cyclohexane as eluent to give the desired product (0.154 g, 79%).

[0161] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.35-7.42 (m, 1H) 7.28-7.33 (m, 1H) 7.22-7.27 (m, 1H) 6.96 (s, 1H) 4.10 (t, 2H) 2.96 (t, 2H) 1.98 (quin, 2H).

Step 4: Synthesis of 3-(5-chloropyrimidin-2-yl)oxy-2-[3-(trifluoromethoxy) propylsulfanyl]benzonitrile—Compound A116

[0162] ##STR00031##

[0163] A mixture of 3-hydroxy-2-[3-(trifluoromethoxy)propylsulfanyl]benzonitrile (0.154 g, 0.56 mmol), 5-chloro-2-methylsulfonyl-pyrimidine (0.128 g, 0.67 mmol) and K.sub.2CO.sub.3 (0.092 g, 0.67 mmol) in DMF (1.5 mL) was stirred at RT overnight. The reaction was diluted with water and extracted with EtOAc (×3). The combined organic extracts were dried over MgSO.sub.4 and evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography on silica gel using a gradient of 0-30% EtOAc/cyclohexane as eluent to give the desired product (0.175 g, 81%).

[0164] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.45-8.52 (m, 2H) 7.66 (dd, 1H) 7.53 (t, 1H) 7.43 -7.49 (m, 1H) 4.07 (t, 2H) 3.05 (t, 2H) 1.89 (quin, 2H)

[0165] The following tables provide examples of specific compounds of the present invention.

TABLE-US-00001 TABLE 1 [00032] Compound A 1.001 prop-1-yl 1.002 but-1-yl 1.003 pent-1-yl 1.004 hex-1-yl 1.005 3,3,3-trifluoroprop-1-yl 1.006 4,4,4-trifluorobut-1-yl 1.007 5,5,5-trifluoropent-1-yl 1.008 6,6,6-trifluorohex-1-yl 1.009 E-CH.sub.2CH═CHCF.sub.3 1.010 CH.sub.2CH.sub.2OCH.sub.2CF.sub.3 1.011 CH.sub.2CH.sub.2OCF.sub.3 1.012 Heptafluoroprop-1-yl 1.013 nonafluorobut-1-yl 1.014 3,3-difluoroprop-1-yl 1.015 4,4-difluorobut-1-yl 1.016 2,2,3,3-tetrafluoroprop-1-yl 1.017 2,2,3,3,3-pentafluoroprop-1-yl

[0166] Further compounds of the present invention are indicated via the additional tables provided below. Each table discloses various variations of n, R.sup.1 and R.sup.2 and should be interpreted as disclosing the A variants shown in Table 1 above. Thus, Table 2 discloses compounds 2.001 to 2.017, Table 3 discloses Compound 3.001 to 3.017 etc.

TABLE-US-00002 TABLE n R.sup.1 R.sup.2 2 1 H Cl 3 2 H Cl 4 0 F Cl 5 1 F Cl 6 2 F Cl 7 0 Cl Cl 8 1 Cl Cl 9 2 Cl Cl 10 0 Br Cl 11 1 Br Cl 12 2 Br Cl 13 0 CN Cl 14 1 CN Cl 15 2 CN Cl 16 0 H Br 17 1 H Br 18 2 H Br 19 0 F Br 20 1 F Br 21 2 F Br 22 0 Cl Br 23 1 Cl Br 24 2 Cl Br 25 0 Br Br 26 1 Br Br 27 2 Br Br 28 0 CN Br 29 1 CN Br 30 2 CN Br 31 0 H F 32 1 H F 33 2 H F 34 0 F F 35 1 F F 36 2 F F 37 0 Cl F 38 1 Cl F 39 2 Cl F 40 0 Br F 41 1 Br F 42 2 Br F 43 0 CN F 44 1 CN F 45 2 CN F

TABLE-US-00003 TABLE C1 Herbicidal compounds of the present invention. (I) [00033] .sup.1H NMR (400 MHz, Compound n A R.sup.2 R.sup.1 CDCl.sub.3 unless stated) A1 0 3,3,3-trifluoroprop-1-yl Cl — 8.48 (s, 2H), 7.51 (dd, 1H), 7.42-7.36 (m, 1H), 7.33- 7.27 (m, 1H), 7.21 (dd, 1H), 3.04-2.97 (m, 2H), 2.42-2.27 (m, 2H) A2 1 3,3,3-trifluoroprop-1-yl Cl — 8.52 (s, 2H), 7.92 (dd, 1H), 7.64-7.58 (m, 1H), 7.58- 7.52 (m, 1H), 7.23 (dd, 1H), 3.28 (ddd, 1H), 3.06 (ddd, 1H), 2.75-2.58 (m, 1H), 2.26-2.10 (m, 1H) A3 2 3,3,3-trifluoroprop-1-yl Cl — 8.49 (s, 2H), 8.06 (dd, 1H), 7.79 (dt, 1H), 7.52 (dt, 1H), 7.38 (dd, 1H), 3.66-3.58 (m, 2H), 2.63-2.50 (m, 2H) A4 0 4,4,4-trifluorobut-1-yl Cl — 8.48 (s, 2H), 7.48 (dd, 1H), 7.40-7.31 (m, 1H), 7.31- 7.24 (m, 1H), 7.19 (dd, 1H), 2.92 (t, 2H), 2.25- 2.12 (m, 2H), 1.85-1.77 (m, 2H) A5 1 4,4,4-trifluorobut-1-yl Cl — 8.51 (s, 2H), 7.95 (dd, 1H), 7.70-7.48 (m, 2H), 7.21 (dd, 1H), 3.10 (br d, 1H), 3.01-2.85 (m, 1H), 2.37- 1.77 (m, 4H) A6 2 4,4,4-trifluorobut-1-yl Cl — 8.49 (s, 2H), 8.07 (dd, 1H), 7.77 (dt, 1H), 7.51 (dt, 1H), 7.36 (dd, 1H), 3.48 (t, 2H), 2.36-2.21 (m, 2H), 2.07- 1.96 (m, 2H) A7 0 3,3,3-trifluoroprop-1-yl Cl 6-F 8.48 (s, 2H), 7.43 (dt, 1H), 7.14-7.05 (m, 2H), 2.98- 2.92 (m, 2H), 2.35-2.23 (m, 2H) A8 1 3,3,3-trifluoroprop-1-yl Cl 6-F 8.49 (s, 2H), 7.60 (dt, 1H), 7.18 (ddd, 1H), 7.10-7.05 (m, 1H), 3.73-3.64 (m, 1H), 3.34-3.25 (m, 1H), 2.66-2.54 (m, 2H) A9 2 3,3,3-trifluoroprop-1-yl Cl 6-F 8.49 (s, 2H), 7.74 (dt, 1H), 7.28-7.22 (m, 1H), 7.16 (td, 1H), 3.62-3.55 (m, 2H), 2.70-2.57 (m, 2H) A10 0 3,3,3-trifluoroprop-1-yl Cl 6-Cl 8.48 (s, 2H), 7.49-7.43 (m, 1H), 7.43-7.37 (m, 1H), 7.18 (dd, 1H), 3.01- 2.95 (m, 2H) 2.36-2.23 (m, 2H) A11 1 3,3,3-trifluoroprop-1-yl Cl 6-Cl 8.46 (s, 2H), 7.57-7.50 (m, 1H), 7.40 (dd, 1H), 7.19 (dd, 1H), 3.68 (ddd, 1H), 3.33 (ddd, 1H), 2.71- 2.55 (m, 2H) A12 2 3,3,3-trifluoroprop-1-yl Cl 6-Cl 8.48 (s, 2H), 7.68-7.62 (m, 1H), 7.55 (dd, 1H), 7.28-7.23 (m, 1H), 3.70- 3.63 (m, 2H), 2.70-2.58 (m, 2H) A13 0 3,3,3-trifluoroprop-1-yl Cl 6-CN 8.49 (s, 2H), 7.69 (dd, 1H), 7.57 (t, 1H), 7.48 (dd, 1H), 3.16-3.06 (m, 2H), 2.44- 2.28 (m, 2H) A14 1 3,3,3-trifluoroprop-1-yl Cl 6-CN 8.51 (s, 2H), 7.82 (dd, 1H), 7.72 (t, 1H), 7.48 (dd, 1H), 3.52 (ddd, 1H), 3.35 (ddd, 1H), 2.83-2.65 (m, 1H), 2.55 (m, 1H) A15 2 3,3,3-trifluoroprop-1-yl Cl 6-CN 8.50 (s, 2H), 7.92-7.85 (m, 2H), 7.62 (dd, 1H), 3.76-3.70 (m, 2H), 2.75- 2.63 (m, 2H) A16 0 benzyl Cl — 8.46 (s, 2H), 7.39-7.35 (m, 1H), 7.35-7.28 (m, 1H), 7.28-7.16 (m, 7H), 4.06 (s, 2H) A17 2 CH.sub.2(4-thiazolyl) Cl — 8.68 (d, 1H), 8.50 (s, 2H), 7.79 (dd, 1H), 7.74-7.66 (m, 1H), 7.40-7.33 (m, 3H), 4.95 (s, 2H) A18 0 CH.sub.2(4-thiazolyl) Cl — 8.73 (d, 1H), 8.48 (s, 2H), 7.43-7.35 (m, 1H), 7.32 (s, 1H), 7.22-7.15 (m, 2H), 7.07-7.03 (m, 1H), 4.26 (s, 2H) A19 2 benzyl Cl — 8.51 (s, 2H), 7.70-7.65 (m, 2H), 7.36-7.21 (m, 7H), 4.64 (s, 2H) A20 2 1-butyl Cl — 8.48 (s, 2H), 8.06 (dd, 1H), 7.74 (dt, 1H), 7.49 (dt, 1H), 7.33 (dd, 1H), 3.43-3.36 (m, 2H), 1.72-1.61 (m, 2H), 1.46-1.37 (m, 2H), 0.90 (t, 3H) A21 0 1-butyl Cl — 8.47 (s, 2H), 7.45 (dd, 1H), 7.32-7.22 (m, 2H), 7.20- 7.12 (m, 1H), 2.89-2.84 (m, 2H), 1.60-1.50 (m, 2H), 1.44-1.33 (m, 2H), 0.88 (t, 3H) A22 1 1-butyl Cl — 8.51 (s, 2H), 7.96 (dd, 1H), 7.59-7.49 (m, 2H), 7.19 (dd, 1H), 3.03 (m, 1H), 2.86 (m, 1H), 1.91-1.69 (m, 1H), 1.63-1.52 (m, 1H), 1.52-1.30 (m, 2H), 0.90 (t, 3H) A23 1 benzyl Cl — 8.52 (s, 2H), 7.54-7.47 (m, 2H), 7.36-7.29 (m, 1H), 7.28-7.19 (m, 4H), 7.09-7.03 (m, 2H), 4.31 (d, 1H), 4.02 (d, 1H) A24 2 4,4,4-trifluorobut-1-yl Cl 6-Cl 8.47 (s, 2H), 7.62 (t, 1H), 7.56-7.50 (m, 1H), 7.24 (dd, 1H), 3.52 (t, 2H), 2.37- 2.25 (m, 2H), 2.14-2.04 (m, 2H) A25 0 4,4,4-trifluorobut-1-yl Cl 6-Cl 8.48 (s, 2H), 7.47-7.40 (m, 1H), 7.40-7.33 (m, 1H), 7.16 (dd, 1H), 2.91 (t, 2H), 2.29-2.16 (m, 2H), 1.77-1.66 (m, 2H) A26 1 4,4,4-trifluorobut-1-yl Cl 6-Cl 8.46 (s, 2H), 7.55-7.48 (m, 1H), 7.39 (dd, 1H), 7.18 (dd, 1H), 3.67-3.54 (m, 1H), 3.20 (td, 1H), 2.41- 2.21 (m, 2H), 2.17-2.00 (m, 2H) A27 0 CH.sub.2(4-Cl-C.sub.6H.sub.4) Cl — 8.46 (s, 2H), 7.38-7.29 (m, 2H), 7.21-7.11 (m, 6H), 4.01 (s, 2H) A28 0 4,4,4-trifluorobut-1-yl Cl 6-CN 8.48 (s, 2H), 7.66 (dd, 1H), 7.53 (t, 1H), 7.48-7.42 (m, 1H), 3.05-2.99 (m, 2H), 2.35-2.17 (m, 2H), 1.81-1.72(m, 2H) A29 1 4,4,4-trifluorobut-1-yl Cl 6-CN 8.50 (s, 2H), 7.80 (dd, 1H), 7.70 (t, 1H), 7.47 (dd, 1H), 3.50-3.41 (m, 1H), 3.23- 3.12 (m, 1H), 2.40-2.25 (m, 2H), 2.19-2.06 (m, 2H) A30 2 4,4,4-trifluorobut-1-yl Cl 6-CN 8.49 (s, 2H), 7.90-7.83 (m, 2H), 7.61 (dd, 1H), 3.59 (t, 2H), 2.42-2.29 (m, 2H), 2.16-2.07 (m, 2H) A31 1 2-pentyl Cl — Characteristic signals: 8.52- 8.48 (m, 2H), 7.96-7.87 (m, 1H), 7.59-7.48 (m, 2H), 7.22-7.16 (m, 1H) A32 2 2-pentyl Cl — 8.47 (s, 2H), 8.05 (dd, 1H), 7.73 (dt, 1H), 7.48 (dt, 1H), 7.32 (dd, 1H), 3.62-3.54 (m, 1H), 1.90-1.69 (m, 1H), 1.56-1.42 (m, 2H), 1.28 (m, 4H), 0.90 (t, 3H) A33 0 2-pentyl Cl — 8.47 (s, 2H), 7.52 (dd, 1H), 7.38-7.29 (m, 1H), 7.28- 7.21 (m, 1H), 7.21-7.16 (m, 1H), 3.33-3.23 (m, 1H), 1.58-1.31 (m, 4H), 1.20 (d, 3H), 0.86 (s, 3H) A34 2 CH.sub.2(4-Cl-C.sub.6H.sub.4) Cl — 8.51 (s, 2H), 7.76-7.69 (m, 2H), 7.59-7.53 (m, 2H), 7.25-7.16 (m, 4H), 4.62 (s, 2H) A35 2 CH.sub.2(4-CN-C.sub.6H.sub.4) Cl — 8.51 (s, 2H), 7.76-7.69 (m, 2H), 7.59-7.53 (m, 2H), 7.41-7.34 (m, 4H), 4.70 (s, 2H) A36 0 CH.sub.2(4-CN-C.sub.6H.sub.4) Cl — 8.47 (s, 2H), 7.54-7.48 (m, 2H), 7.38-7.23 (m, 4H), 7.23-7.11 (m, 2H), 4.06 (s, 2H) A37 0 E-CH.sub.2CH═CHCl Cl — 8.48 (s, 2H), 7.48 (dd, 1H), 7.41-7.34 (m, 1H), 7.30- 7.23 (m, 1H), 7.20 (dd, 1H), 5.99-5.85 (m, 2H), 3.47 (dd, 2H) A38 2 E-CH2CH═CHCl Cl — 8.49 (s, 2H), 8.01 (dd, 1H), 7.79-7.72 (m, 1H), 7.50 (dt, 1H), 7.35 (dd, 1H), 6.23 (dt, 1H), 5.88 (dt, 1H), 4.13 (dd, 2H) A39 0 5,5,5-trifluoropent-1-yl Cl 6-CN 8.47 (s, 2H), 7.65 (dd, 1H), 7.52 (t, 1H), 7.49-7.42 (m, 1H), 2.97 (t, 2H), 2.13- 1.99 (m, 2H), 1.67-1.56 (m, 4H) A40 0 6,6,6-trifluorohex-1-yl Cl 6-CN 8.48 (s, 2H), 7.65 (dd, 1H), 7.53-7.47 (m, 1H), 7.47- 7.42 (m, 1H), 2.96 (t, 2H), 2.11-1.97 (m, 2H), 1.58- 1.44 (m, 6H) A41 0 2-methoxyethyl Cl — 8.48 (s, 2H), 7.53 (d, 1H), 7.32 (t, 1H), 7.25 (t, 1H), 7.17 (d, 1H), 3.53 (t, 2H), 3.31 (s, 3H), 3.04 (t, 2H) A42 2 2-methoxyethyl Cl — 8.48 (s, 2H), 8.06 (d, 1H), 7.72 (d, 1H), 7.48 (t, 1H), 7.32 (d, 1H), 3.76 (t, 2H), 3.68 (t, 2H) A43 2 pent-1-yl Cl — 8.48 (s, 2H), 8.06 (d, 1H), 7.73 (t, 1H), 7.48 (t, 1H), 7.33 (d, 1H), 3.48 (t, 2H), 1.72-1.65 (m, 2H), 1.39- 1.25 (m, 4H), 0.87 (t, 3H) A44 0 pent-1-yl Cl — 8.48 (s, 2H), 7.44 (d, 1H), 7.29-7.21 (m, 2H), 7.15 (d, 1H), 2.85 (t, 2H), 1.60-1.52 (m, 2H), 1.35-1.22 (m, 4H), 0.86 (t, 3H) A45 0 prop-2-ynyl Cl — 8.48 (s, 2H), 7.64 (d, 1H), 7.36 (t, 1H), 7.27 (t, 1H), 7.20 (d, 1H), 3.58 (s, 2H), 2.20 (t, 1H) A46 2 prop-2-ynyl Cl — 8.48 (s, 2H), 8.13 (d, 1H), 7.76 (t, 1H), 7.50 (t, 1H), 7.35 (d, 1H), 4.30 (s, 2H), 2.29 (t, 1H) A47 0 allyl Cl — 8.48 (s, 2H), 7.47 (d, 1H), 7.31 (t, 1H), 7.25 (t, 1H), 7.15 (d, 1H), 5.85-5.75 (m, 1H), 5.12 (d, 1H), 5.04 (d, 1H), 3.51 (d, 2H) A48 2 allyl Cl — 8.49 (s, 2H), 8.00 (d, 1H), 7.71 (t, 1H), 7.45 (t, 1H), 7.33 (d, 1H), 5.81-5.73 (m, 1H), 5.31-5.25 (m, 2H), 4.13 (d, 2H) A49 0 prop-1-yl Cl — 8.48 (s, 2H), 7.45 (d, 1H), 7.31-7.22 (m, 2H), 7.15 (d, 1H), 2.84 (t, 2H), 1.62-1.55 (m, 2H), 0.96 (t, 3H) A50 2 prop-1-yl Cl — 8.48 (s, 2H), 8.06 (d, 1H), 7.72 (t, 1H), 7.48 (t, 1H), 7.32 (d, 1H), 3.37 (t, 2H), 1.75-1.70 (m, 2H), 1.01 (t, 3H) A51 2 CH.sub.2cyclopropyl Cl — 8.48 (s, 2H), 8.11 (d, 1H), 7.73 (t, 1H), 7.48 (t, 1H), 7.31 (t, 1H), 3.33 (d, 2H), 1.05-0.97 (m, 1H), 0.55- 0.49 (m, 2H), 0.23-0.20 (m, 2H) A52 0 3-methylbut-2-enyl Cl — 8.48 (s, 2H), 7.46 (d, 1H), 7.31 (t, 1H), 7.24 (t, 1H), 7.15 (d, 1H), 5.22 (t, 1H), 3.49 (d, 2H), 1.68 (s, 3H), 1.55(s, 3H) A53 0 hex-1-yl Cl — 8.48 (s, 2H), 7.45 (d, 1H), 7.30-7.21 (m, 2H), 7.15 (d, 1H), 2.85 (t, 2H), 1.60-1.52 (m, 2H), 1.38-1.30 (m, 2H), 1.29-1.18 (m, 4H), 0.86 (t, 3H) A54 0 CH.sub.2CH.sub.2OCF.sub.3 Cl — 8.48 (s, 2H), 7.55 (dd, 1H), 7.39 (t, 1H), 7.30 (t, 1H), 7.21 (dd, 1H), 4.02 (t, 2H), 3.13 (t, 2H) A55 0 CH.sub.2CF.sub.3 Cl — 8.49 (s, 2H), 7.63 (d, 1H), 7.44 (t, 1H), 7.26 (t, 1H), 7.20 (d, 1H), 3.42 (q, 2H) A56 0 3-methoxyprop-1-yl Cl — 8.48 (s, 2H), 7.48 (d, 1H), 7.32-7.24 (m, 2H), 7.16 (d, 1H), 3.40 (t, 2H), 3.30 (s, 3H), 2.94 (t, 2H), 1.85-1.80 (m, 2H) A57 0 2-(4-chloropyrazol-1- Cl — 8.49 (s, 2H), 7.50 (d, 1H), yl)ethyl 7.40 (s, 1H), 7.38-7.34 (m, 3H), 7.25 (t, 1H), 7.20 (d, 1H), 4.20 (t, 2H), 3.25 (t, 2H) A58 0 CH.sub.2cyclohexyl Cl — 8.48 (s, 2H), 7.43 (d, 1H), 7.29-7.20 (m, 2H), 7.15 (d, 1H), 2.75 (d, 2H), 1.84- 1.80 (m, 2H), 1.71-1.60 (m, 3H), 1.50-1.40 (m, 1H), 1.25-1.10 (m, 3H), 0.95- 0.85 (m, 2H) A59 0 3-fluoroprop-1-yl Cl — 8.48 (s, 2H), 7.49 (d, 1H), 7.33 (t, 1H), 7.25 (t, 1H), 7.15 (d, 1H), 4.55 (t, 1H), 4.45 (t, 1H), 3.00 (t, 2H), 1.98-1.88 (m, 2H) A60 0 2-fluoroethyl Cl — 8.48 (s, 2H), 7.55 (d, 1H), 7.35 (t, 1H), 7.26 (t, 1H), 7.18 (d, 1H), 4.55 (t, 1H), 4.45 (t, 1H), 3.20-3.10 (m, 2H) A61 0 2,2-difluoroethyl Cl — 8.48 (s, 2H), 7.60 (d, 1H), 7.41 (t, 1H), 7.25 (t, 1H), 7.20 (d, 1H), 5.85 (dt, 1H), 3.19 (dq, 2H) A62 0 2-methylallyl Cl — 8.48 (s, 2H), 7.45 (d, 1H), 7.30 (t, 1H), 7.22 (t, 1H), 7.15 (d, 1H), 4.78 (d, 2H), 3.45 (s, 2H), 1.80 (s, 3H) A63 0 4-methylpent-3-enyl Cl — 8.48 (s, 2H), 7.46 (d, 1H), 7.30-7.20 (m, 2H), 7.15 (d, 1H), 5.10 (t, 1H), 2.85 (t, 2H), 2.25 (q, 2H), 1.66 (s, 3H), 1.55 (s, 3H) A64 0 2-ethylbut-1-yl Cl — 8.48 (s, 2H), 7.45 (d, 1H), 7.30-7.21 (m, 2H), 7.13 (d, 1H), 2.85 (d, 2H), 1.46- 1.30 (m, 5H), 0.84 (t, 6H) A65 0 secbutyl Cl — 8.48 (s, 2H), 7.54 (d, 1H), 7.33 (t, 1H), 7.23 (t, 1H), 7.18 (d, 1H), 3.27-3.20 (m, 1H), 1.62-1.55 (m, 1H), 1.50-1.43 (m, 1H), 1.20 (d, 3H), 0.92 (t, 3H) A66 0 (3-chlorophenyl)methyl Cl — 8.47 (s, 2H), 7.36-7.30 (m, 2H), 7.20-7.12 (m, 5H), 7.06 (d, 1H), 4.01 (s, 2H) A67 0 (2-chlorophenyl)methyl Cl — 8.45 (s, 2H), 7.38-7.30 (m, 3H), 7.20-7.05 (m, 5H), 4.14 (s, 2H) A68 0 3,4,4-trifluorobut-3-enyl Cl — 8.48 (s, 2H), 7.50 (d, 1H), 7.34 (t, 1H), 7.25 (t, 1H), 7.20 (d, 1H), 3.04 (t, 2H), 2.59-2.45 (m, 2H) A69 0 2-methylpent-1-yl Cl — 8.48 (s, 2H), 7.45 (d, 1H), 7.30-7.20 (m, 2H), 7.14 (d, 1H), 2.88 (dd, 1H), 2.66 (dd, 1H), 1.70-1.60 (m 1H), 1.40-1.10 (m, 4H), 0.94 (d, 3H), 0.85 (t, 3H) A70 0 Isopentyl Cl — 8.48 (s, 2H), 7.45 (d, 1H), 7.31-7.22 (m, 2H), 7.15 (d, 1H), 2.86 (t, 2H), 1.7-1.62 (m, 1H), 1.48-1.40 (m, 2H), 0.85 (d, 6H) A71 0 but-3-enyl Cl — 8.48 (s, 2H), 7.48 (d, 1H), 7.32-7.20 (m, 2H), 7.17 (d, 1H), 5.82-5.73 (m, 1H), 5.05-5.00 (m, 2H), 2.92 (t, 2H), 2.30 (q, 2H) A72 0 Isobutyl Cl — 8.48 (s, 2H), 7.45 (d, 1H), 7.30-7.20 (m, 2H), 7.15 (d, 1H), 2.75 (d, 2H), 1.81- 1.70 (m, 1H), 0.98 (d, 6H) A73 2 3,4,4-trifluorobut-3-enyl Cl — 8.49 (s, 2H), 8.08 (dd, 1H), 7.76 (t, 1H), 7.51 (t, 1H), 7.35 (d, 1H), 3.62 (t, 2H), 2.80-2.70 (m, 2H) A74 2 2-methylpent-1-yl Cl — 8.48 (s, 2H), 8.08 (d, 1H), 7.72 (t, 1H), 7.48 (t, 1H), 7.32 (d, 1H), 3.45 (dd, 1H), 3.23 (dd, 1H), 2.11-2.05 (m, 1H), 1.45-1.20 (m, 4H), 1.04 (d, 3H), 0.83 (t, 3H) A75 2 Isopentyl Cl — 8.48 (s, 2H), 8.05 (dd, 1H), 7.74 (t, 1H), 7.48 (t, 1H), 7.32 (d, 1H), 3.41-3.36 (m, 2H), 1.70-1.61 (m, 1H), 1.60-1.52 (m, 2H), 0.90 (d, 6H) A76 2 Isobutyl Cl — 8.48 (s, 2H), 8.06 (dd, 1H), 7.71 (t, 1H), 7.49 (t, 1H), 7.31 (d, 1H), 3.31 (d, 2H), 2.25-2.18 (m, 1H), 1.05 (d, 6H) A77 2 Hex-1-yl Cl — 8.48 (s, 2H), 8.05 (dd, 1H), 7.72 (t, 1H), 7.48 (t, 1H), 7.33 (d, 1H), 3.41-3.35 (m, 2H), 1.70-1.65 (m, 2H), 1.40-1.35 (m, 2H), 1.25- 1.20 (m, 4H), 0.85 (t, 3H) A78 2 2,2,2-trifluoroethyl Cl — 8.49 (s, 2H), 8.11 (dd, 1H), 7.80 (t, 1H), 7.52 (t, 1H), 7.48 (d, 1H), 4.26 (q, 2H) A79 2 3-methoxyprop-1-yl Cl — 8.48 (s, 2H), 8.05 (dd, 1H), 7.72 (t, 1H), 7.49 (t, 1H), 7.31 (d, 1H), 3.51-3.45 (m, 2H), 3.42 (t, 2H), 3.29 (s, 3H), 1.99-1.92 (m, 2H) A80 2-(4-chloropyrazol-1- Cl — 8.48 (s, 2H), 7.90 (dd, 1H), yl)ethyl 7.70 (t, 1H), 7.44 (t, 1H), 7.35 (s, 1H), 7.30 (d, 1H), 7.21 (s, 1H), 4.52 (t, 2H), 4.01 (t, 2H) A81 2 CH.sub.2cyclohexyl Cl — 8.48 (s, 2H), 8.07 (dd, 1H), 7.73 (t, 1H), 7.48 (t, 1H), 7.31 (d, 1H), 3.30 (d, 2H), 2.02-1.91 (m, 1H), 1.88- 1.80 (m, 2H), 1.70- 1.58 (m, 4H), 1.28-1.02 (m, 4H) A82 2 3-fluoroprop-1-yl Cl — 8.49 (s, 2H), 8.08 (dd, 1H), 7.73 (t, 1H), 7.50 (t, 1H), 7.33 (d, 1H), 4.58 (t, 1H), 4.48 (t, 1H), 3.54 (t, 2H), 2.20-2.05 (m, 2H) A83 2 2-fluoroethyl Cl — 8.48 (s, 2H), 8.08 (dd, 1H), 7.75 (t, 1H), 7.50 (t, 1H), 7.35 (d, 1H), 4.87 (t, 1H), 4.75 (t, 1H), 3.85 (t, 1H), 3.81 (t, 1H) A84 2 2,2-difluoroethyl Cl — 8.49 (s, 2H), 8.05 (dd, 1H), 7.89 (t, 1H), 7.51 (t, 1H), 7.38 (d, 1H), 6.22 (tt, 1H), 4.01 (dt, 2H) A85 2 2-methylallyl Cl — 8.48 (s, 2H), 8.08 (dd, 1H), 7.75 (t, 1H), 7.51 (t, 1H), 7.34 (d, 1H), 3.85 (d, 1H), 3.40 (d, 1H), 2.85 (d, 1H), 2.53 (d, 1H), 1.52 (s, 3H) A86 2 4-methylpent-3-enyl Cl — 8.48 (s, 2H), 8.04 (dd, 1H), 7.73 (t, 1H), 7.48 (t, 1H), 7.33 (d, 1H), 3.67 (t, 2H), 2.95 (t, 2H), 2.66-2.58 (m, 1H), 1.12 (s, 3H), 1.10 (s, 3H) A87 2 2-ethylbut-1-yl Cl — 8.48 (s, 2H), 8.07 (dd, 1H), 7.72 (t, 1H), 7.48 (t, 1H), 7.33 (d, 1H), 3.35 (d, 2H), 1.90-1.85 (m, 1H), 1.48- 1.40 (m, 4H), 0.84 (t, 6H) A88 2 sec-butyl Cl — 8.48 (s, 2H), 8.04 (dd, 1H), 7.73 (t, 1H), 7.48 (t, 1H), 7.32 (d, 1H), 3.55-3.45 (m, 1H), 1.98-1.85 (m, 1H), 1.60-1.50 (m, 1H) 1.30 (d, 3H), 1.01 (t, 3H) A89 2 (3-chlorophenyl)methyl Cl — 8.51 (s, 2H), 7.75-7.65 (m, 2H), 7.37-7.32 (m, 2H), 7.28-7.26 (m, 2H), 7.20- 7.12 (m 2H), 4.62 (s, 2H) A90 2 (2-chlorophenyl)methyl Cl — 8.49 (s, 2H), 7.77-7.68 (m, 2H), 7.38-7.30 (m, 4H), 7.27-7.15 (m, 2H), 4.85 (s, 2H) A91 2 5,5,5-trifluoropent-1-yl Cl 2-CN 8.48 (s, 2H), 7.90-7.81 (m, 2H), 7.59 (dd, 1H), 3.56-3.49 (m, 2H), 2.22- 2.07 (m, 2H), 1.93 (quin, 2H), 1.81-1.70 (m, 2H) A92 2 6,6,6-trifluorohex-1-yl Cl 2-CN 8.51-8.45 (m, 2H), 7.91- 7.80 (m, 2H), 7.58 (dd,, 1H), 3.55-3.46 (m, 2H), 2.16-1.99 (m, 2H), 1.93- 1.78 (m, 2H), 1.66-1.50 (m, 4H) A93 0 1,1,2,2,3,3,3- Cl 2-CN 8.48 (s, 2H), 7.70-7.77 (m, heptafluoroprop-1-yl 2H), 7.55-7.57 (dd, 1H) A94 0 3,3-difluoroprop-1-yl Cl 2-Cl 8.48 (s, 2H), 7.44 (d, 1H), 7.38 (t, 1H), 7.17 (d, 1H), 5.93 (tt, 1H), 2.93 (t, 2H), 2.06-1.91 (m, 2H) A95 1 3,3-difluoroprop-1-yl Cl 2-Cl 8.46 (s, 2H), 7.51 (t, 1H), 7.38 (d, 1H), 7.17 (d, 1H), 6.00 (tt, 1H), 3.65-3.57 (m, 1H), 3.33-3.23 (m, 1H), 2.42-2.38 (m, 2H) A96 2 3,3-difluoroprop-1-yl Cl 2-Cl 8.48 (s, 2H), 7.61 (t, 1H), 7.52 (d, 1H), 7.22 (d, 1H), 6.00 (tt, 1H), 3.60 (t, 2H), 2.42-2.28 (m, 2H) A97 2 3,3-difluoroprop-1-yl Cl 2-CN 8.48 (s, 2H), 7.90-7.81 (m, 2H), 7.59 (d, 1H), 6.03 (tt, 1H), 3.68 (t, 2H), 2.48-2.31 (m, 2H) A98 1 3,3-difluoroprop-1-yl Cl 2-CN 8.49 (s, 2H), 7.79 (d, 1H), 7.69 (t, 1H), 7.46 (d, 1H), 6.01 (tt, 1H), 3.51-3.41 (m, 1H), 3.34-3.23 (m, 1H), 2.53-2.21 (m, 2H) A99 0 3,3-difluoroprop-1-yl Cl 2-CN 8.48 (s, 2H), 7.68 (d, 1H), 7.56 (t, 1H), 7.48 (d, 1H), 5.94 (tt, 1H), 3.06 (t, 2H), 2.12-1.98 (m, 2H) A100 0 4,4-difluorobut-1-yl Cl 2-CN 8.48 (s, 2H), 7.63 (d, 1H), 7.52 (t, 1H), 7.42 (d, 1H), 5.79 (tt, 1H), 2.99 (t, 2H), 2.01-1.85 (m, 2H), 1.71- 1.61 (m, 2H) A101 1 4,4-difluorobut-1-yl Cl 2-CN 8.49 (s, 2H), 7.78 (d, 1H), 7.67 (t, 1H), 7.43 (d, 1H), 5.84 (tt, 1H), 3.49-3.39 (m, 1H), 3.22-3.12 (m, 1H), 2.12-1.91 (m, 4H) A102 2 4,4-difluorobut-1-yl Cl 2-CN 8.48 (s, 2H), 7.89-7.78 (m, 2H), 7.57 (d, 1H), 5.86 (tt, 1H), 3.54 (t, 2H), 2.12-1.98 (m, 4H) A103 2 4,4-difluorobut-1-yl Cl 2-Cl 8.48 (s, 2H), 7.60 (t, 1H), 7.52 (d, 1H), 7.21 (d, 1H), 5.81 (tt, 1H), 3.49 (t, 2H), 2.08-1.92 (m, 4H) A104 1 4,4-difluorobut-1-yl Cl 2-Cl 8.45 (s, 2H), 7.50 (t, 1H), 7.38 (d, 1H), 7.16 (d, 1H), 5.84 (tt, 1H), 3.61-3.52 (m, 1H), 3.24-3.15 (m, 1H), 2.11-1.89 (m, 4H) A105 0 4,4-difluorobut-1-yl Cl 2-Cl 8.47 (s, 2H), 7.41 (d, 1H), 7.33 (t, 1H), 7.13 (d, 1H), 5.78 (tt, 1H), 2.89 (t, 2H), 2.00-1.85 (m, 2H), 1.67- 1.58(m, 2H) A106 0 2-trifluoromethoxyethyl Cl 2-CN 8.49 (s, 2H), 7.65 (d, 1H), 7.53 (t, 1H), 7.45 (d, 1H), 4.05 (t, 2H), 3.22 (t, 2H) A107 0 2-(2,2,2- Cl 2-CN 8.51-8.45 (m, 2H), 7.65 trifluoroethoxy)ethyl (dd, 1H), 7.53 (t, 1H), 7.48- 7.42 (m, 1H), 3.89-3.69 (m, 4H), 3.14 (t, 2H) A108 2 2-(2,2,2- Cl 2-CN 8.52-8.46 (m, 2H), 7.85- trifluoroethoxy)ethyl 7.77 (m, 2H), 7.56 (dd, 1H), 4.17-4.07 (m, 2H), 3.84-3.79 (m, 2H), 3.75 (q, 2H) A109 2 1,1,2,2,3,3,3- Cl 2-CN 8.48 (s, 2H), 7.70-7.78 (m, heptafluoroprop-1-yl 2H), 7.55-7.57 (dd, 1H) A110 0 2,2,3,3,3- Cl 2-CN 8.48 (s, 2H), 7.65-7.67 (d, pentafluoroprop-1-yl 1H), 7.54-7.58 (t, 1H), 7.46-7.47 (d, 1H), 3.52 (t, 2H) A111 0 2,2,3,3-tetrafluoroprop-1- Cl 2-CN 8.47 (s, 2H), 7.65-7.66 (d, yl 1H), 7.54-7.58 (t, 1H), 7.46-7.48 (d, 1H), 6.06 (t, 1H), 3.46 (t, 2H) A112 2 4,4,4-trifluorobut-1-yl OCH.sub.3 2-CN 8.19-8.23 (m, 2H) 7.78- 7.85 (m, 2H) 7.58 (dd, 1H), 3.90 (s, 3H) 3.61 (t, 2H) 2.28-2.42 (m, 2H) 2.07-2.19 (m, 2H) A113 0 4,4,4-trifluorobut-1-yl OCH.sub.3 2-CN 8.21 (s, 2H) 7.62 (dd, 1H) 7.47-7.52 (m, 1H) 7.41- 7.47 (m, 1H) 3.89 (s, 3H) 3.04 (t, 2H) 2.16-2.29 (m, 2H) 1.72-1.81 (m, 2H) A114 0 4,4,4-trifluorobut-1-yl CH.sub.3 2-CN 8.36 (d, 2H) 7.63 (dd, 1H) 7.48-7.54 (m, 1H) 7.42- 7.48 (m, 1H) 3.03 (t, 2H) 2.29 (s, 3H) 2.15-2.27 (m, 2H) 1.70-1.81 (m, 2H) A115 2 4,4,4-trifluorobut-1-yl CH.sub.3 2-CN 8.37 (d, 2H) 7.80-7.86 (m, 2H) 7.59 (dd, 1H) 3.61 (t, 2 H) 2.35 (dt, 2H) 2.29 (s, 3H) 2.07-2.18 (m, 2H) A116 0 3-trifluoromethoxy-prop- Cl 2-CN 8.45-8.52 (m, 2H) 7.66 1-yl (dd, 1H) 7.53 (t, 1H) 7.43- 7.49 (m, 1H) 4.07 (t, 2H) 3.05 (t, 2H) 1.89 (quin, 2H) A117 2 3-trifluoromethoxy-prop- Cl 2-CN 8.47-8.51 (m, 2H) 7.82- 1-yl 7.90 (m, 2H) 7.60 (dd, 1H) 4.09-4.15 (m, 2H) 3.59- 3.66 (m, 2H) 2.19-2.33 (m, 2H) A118 2 4,4,4-trifluorobut-1-yl Br 2-CN 8.56-8.59 (m, 2H) 7.82- 7.90 (m, 2H) 7.60 (dd, 1H) 3.58 (t, 2H) 2.29-2.42 (m, 2H) 2.06-2.19 (m, 2H) A119 0 4,4,4-trifluorobut-1-yl Br 2-CN 8.53-8.59 (m, 2H) 7.66 (dd, 1H) 7.53 (t, 1H) 7.44- 7.49 (m, 1H) 3.03 (t, 2H) 2.17-2.30 (m, 2H) 1.72- 1.81 (m, 2H) A120 2 5,5,5-trifluoropent-1-yl Br 2-CN 8.57 (s, 2H), 7.88-7.81 (m, 2H), 7.58 (dd, 1H), 3.54- 3.50 (m, 2H), 2.17-2.10 (m, 2H), 1.95-1.91 (m, 2H), 1.78-1.70 (m, 2H) A121 0 5,5,5-trifluoropent-1-yl Br 2-CN 8.56 (s, 2H), 7.65 (dd, 1H), 7.51 (t, 1H), 7.49-7.43 (m, 1H), 2.97 (t, 2H), 2.08-2.03 (m, 2H), 1.65-1.58 (m, 4H)

Biological Examples

Test 1

[0167] Seeds of a variety of test species are sown in standard soil in pots (Lolium perenne (LOLPE), Solanum nigrum (SOLNI), Amaranthus retoflexus (AMARE), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG) and Ipomoea hederacea (IPOHE)). After cultivation for one day (pre-emergence) or 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 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005-64-5). Compounds are applied at 250 g/ha unless otherwise stated. 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 for pre and post-emergence, the test is evaluated for the percentage damage caused to the plant. The biological activities (% phytotoxicity) are shown in Tables B1 and B2 below using a five-point scale (5=81 to 100%; 4=61 to 80%; 3=41 to 60%; 2=21 to 40%; 1=0 to 20%).

TABLE-US-00004 TABLE B1 Post-emergence application. Compound AMARE SOLNI SETFA LOLPE ECHCG IPOHE Al 5 4 4 4 4 4 A2 5 5 4 4 4 4 A3 5 5 4 4 4 3 A4 5 5 5 4 4 4 A5 5 5 5 5 5 4 A6 5 5 4 2 3 3 A7 5 5 5 2 4 2 A8 5 4 3 1 1 2 A9 5 5 4 3 3 3 A10 5 5 5 5 5 4 A11 5 5 5 4 5 5 A12 5 5 5 5 5 4 A13 5 5 5 5 5 4 A14 5 5 5 4 5 5 A15 5 5 5 4 5 5 A16 4 3 2 1 1 1 A20 2 NT 3 NT 2 1 A21 4 NT 4 NT 4 3 A22 3 NT 4 NT 4 2 A24 5 5 5 5 5 5 A25 5 5 5 5 5 3 A26 5 5 5 5 5 5 A27 5 3 2 1 2 2 A28 5 5 5 5 5 5 A29 5 5 5 5 5 5 A30 5 5 5 5 5 4 A33 3 NT 2 NT 2 1 A36 5 NT 4 NT 3 3 A37 4 NT 2 NT 2 2 A38 2 NT 1 NT 1 3 A39 5 NT 5 NT 5 3 A40 5 NT 4 NT 4 3 A41 3 NT 2 NT 3 3 A42 2 NT 1 NT 1 1 A43 3 NT 2 NT 2 1 A44 5 NT 2 NT 4 1 A45 3 NT 2 NT 3 1 A46 1 NT 1 NT 1 1 A48 2 NT 1 NT 1 1 A49 4 NT 4 NT 4 4 A50 4 NT 1 NT 1 2 A51 3 NT 1 NT 1 1 A52 3 NT 3 NT 4 1 A53 4 NT 1 NT 1 1 A55 5 NT 4 NT 4 4 A56 2 NT 1 NT 1 1 A57 5 NT 4 NT 4 2 A59 5 NT 2 NT 4 2 A60 3 NT 1 NT 1 2 A61 5 NT 2 NT 2 2 A62 1 NT 3 NT 4 1 A64 2 NT 2 NT 1 2 A65 1 NT 3 NT 4 3 A66 4 NT 3 NT 4 2 A68 5 NT 4 NT 5 5 A69 4 NT 2 NT 4 1 A70 2 NT 4 NT 5 4 A71 5 NT 3 NT 4 4 A72 3 NT 2 NT 3 2 A73 4 NT 3 NT 3 1 A74 3 NT 1 NT 1 1 A75 2 NT 2 NT 3 2 A76 1 NT 1 NT 2 2 A77 2 NT 1 NT 1 1 A82 3 NT 1 NT 1 3 A87 1 NT 1 NT 1 1 A88 2 NT 1 NT 1 1 A89 3 NT 1 NT 1 1 A91 5 NT 4 NT 5 4 A92 5 NT 2 NT 3 2 A94 5 NT 5 NT 5 3 A95 4 NT 1 NT 2 4 A96 5 NT 5 NT 5 5 A97 5 NT 2 NT 4 4 A98 5 NT 4 NT 4 4 A99 5 NT 4 NT 5 4 A100 5 NT 4 NT 5 5 A101 5 NT 4 NT 4 4 A102 5 NT 4 NT 4 4 A103 4 NT 1 NT 1 2 A104 5 NT 5 NT 5 5 A105 5 NT 5 NT 5 4 A106 5 NT 4 NT 5 3 A107 5 NT 4 NT 5 2 A108 4 NT 1 NT 1 2 A112 2 NT 1 NT 1 2 A113 5 NT 2 NT 3 3 A114 3 NT 3 NT 4 4 A115 4 NT 3 NT 4 4 A116 5 NT 4 NT 4 4 A117 5 NT 4 NT 4 3 A118 5 NT 4 NT 4 4 A119 5 NT 4 NT 4 4 A120 4 NT 3 NT 3 4 A121 5 NT 4 NT 3 3

TABLE-US-00005 TABLE B2 Pre-emergence application. Compound AMARE SOLNI SETFA LOLPE ECHCG IPOHE A1 5 4 5 3 4 3 A2 5 5 5 3 5 2 A3 5 4 5 4 5 3 A4 5 4 5 4 5 3 A5 5 5 5 5 5 5 A6 5 3 5 2 4 2 A7 5 4 5 4 5 2 A8 5 4 4 2 2 2 A9 5 5 5 4 4 4 A10 5 4 5 4 5 3 A11 5 5 5 5 5 5 A12 5 5 5 5 5 5 A13 5 5 5 5 5 4 A14 5 5 5 3 5 5 A15 5 5 5 5 5 5 A16 4 1 2 1 2 1 A20 3 NT 4 NT 4 1 A21 4 NT 5 NT 5 2 A22 4 NT 5 NT 5 5 A24 5 5 5 4 5 5 A25 5 5 5 5 5 1 A26 5 5 5 5 5 5 A27 5 2 4 1 4 1 A28 5 5 5 5 5 5 A29 5 5 5 5 5 5 A30 5 5 5 5 5 5 A33 1 NT 3 NT 1 1 A36 5 NT 5 NT 4 2 A37 4 NT 3 NT 4 1 A38 2 NT 1 NT 1 1 A39 5 NT 5 NT 5 2 A40 5 NT 5 NT 4 1 A41 1 NT 2 NT 2 2 A42 1 NT 1 NT 1 1 A43 5 NT 4 NT 4 1 A44 5 NT 5 NT 5 1 A45 3 NT 3 NT 3 1 A46 1 NT 1 NT 1 1 A48 1 NT 1 NT 1 1 A49 5 NT 5 NT 5 3 A50 5 NT 5 NT 4 2 A51 4 NT 2 NT 1 1 A52 1 NT 1 NT 2 1 A53 3 NT 3 NT 2 1 A55 5 NT 5 NT 5 2 A56 2 NT 2 NT 1 2 A57 4 NT 4 NT 3 1 A59 5 NT 4 NT 5 2 A60 4 NT 3 NT 2 1 A61 5 NT 4 NT 3 2 A62 1 NT 3 NT 3 1 A64 1 NT 1 NT 1 1 A65 3 NT 4 NT 4 1 A66 1 NT 2 NT 2 1 A68 5 NT 5 NT 5 4 A69 1 NT 4 NT 3 1 A70 2 NT 5 NT 5 1 A71 5 NT 5 NT 5 1 A72 4 NT 4 NT 4 1 A73 5 NT 4 NT 5 1 A74 1 NT 1 NT 1 1 A75 5 NT 4 NT 4 1 A76 5 NT 4 NT 3 2 A77 4 NT 1 NT 3 1 A78 3 NT 1 NT 1 1 A82 5 NT 3 NT 3 1 A87 1 NT 1 NT 1 1 A88 5 NT 5 NT 1 2 A89 1 NT 1 NT 1 1 A91 5 NT 5 NT 5 5 A92 5 NT 4 NT 4 1 A94 5 NT 5 NT 5 3 A95 5 NT 5 NT 5 5 A96 5 NT 5 NT 5 5 A97 5 NT 4 NT 4 5 A98 5 NT 5 NT 5 5 A99 5 NT 5 NT 5 5 A100 5 NT 5 NT 5 5 A101 5 NT 5 NT 5 5 A102 5 NT 5 NT 5 5 A103 4 NT 2 NT 2 4 A104 5 NT 5 NT 5 5 A105 5 NT 5 NT 5 4 A106 5 NT 5 NT 5 2 A107 5 NT 5 NT 5 3 A108 5 NT 1 NT 1 1 A112 3 NT 1 NT 1 3 A113 5 NT 2 NT 4 3 A114 5 NT 4 NT 4 4 A115 5 NT 3 NT 4 5 A116 5 NT 5 NT 5 5 A117 5 NT 5 NT 4 5 A118 5 NT 5 NT 5 5 A119 5 NT 5 NT 5 5 A120 4 NT 4 NT 3 5 A121 5 NT 5 NT 3 2 NT = Not tested.