HERBICIDAL COMPOUNDS

Abstract

The present invention related to compounds of Formula (I) or an agronomically acceptable salt thereof, wherein Q, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are as defined herein. The invention further relates to compositions comprising said compounds, to methods of controlling weeds using said compositions, to the use of compounds of Formula (I) as a herbicide, and to intermediate compounds used in the making of said compounds.

##STR00001##

Claims

1. A compound of Formula (I): ##STR00028## or an agronomically acceptable salt thereof, wherein: Q is Q.sup.1 or Q.sup.2; ##STR00029## R.sup.1a is selected from the group consisting of C.sub.1-C.sub.4alkyl-, C.sub.1-C.sub.4haloalkyl-, C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkyl- and C.sub.1-C.sub.4haloalkoxy-C.sub.1-C.sub.4alkyl-; R.sup.1b is selected from the group consisting of C.sub.1-C.sub.4alkyl-, C.sub.1-C.sub.4haloalkyl-, C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4alkyl- and C.sub.1-C.sub.4haloalkoxy-C.sub.1-C.sub.4alkyl-; R.sup.2 is selected from the group consisting of halogen, C.sub.1-C.sub.6alkyl-, C.sub.1-C.sub.3alkoxy-, C.sub.1-C.sub.6 haloalkyl-, C.sub.1-C.sub.3haloalkoxy- and S(O).sub.pC.sub.1-C.sub.6alkyl; R.sup.3 is C.sub.1-C.sub.3haloalkyl; R.sup.4 is selected from the group consisting of C.sub.1-C.sub.6alkyl-, C.sub.1-C.sub.6haloalkyl-, C.sub.3-C.sub.6cycloalkyl-, C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.3alkyl-, C.sub.1-C.sub.3alkoxy-C.sub.1-C.sub.3alkyl-, C.sub.1-C.sub.4haloalkoxy-C.sub.1-C.sub.4alkyl-, C.sub.1-C.sub.4alkoxy-C.sub.1-C.sub.4haloalkyl-, C.sub.1-C.sub.3alkyl-S(O).sub.pC.sub.1-C.sub.3alkyl-, and cyano-C.sub.1-C.sub.6alkyl; R.sup.5 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl-, C.sub.1-C.sub.6haloalkyl and C.sub.1-C.sub.6cycloalkyl; or R.sup.4 and R.sup.5 together with the nitrogen atom to which they are attached form an optionally substituted 5- or 6-membered saturated heterocycle; and p is 0, 1 or 2.

2. A compound according to claim 1, wherein Q is Q.sup.1.

3. A compound according to claim 1, wherein Q is Q.sup.2.

4. A compound according to claim 1, wherein R.sup.1a or R.sup.1b are selected from the group consisting of methyl, ethyl and n-propyl.

5. A compound according to claim 1, wherein R.sup.2 is selected from the group consisting of methyl, Cl, CF.sub.3 and SO.sub.2methyl.

6. A compound according to claim 5, wherein R.sup.2 is Cl.

7. A compound according to claim 1, wherein R.sup.3 is CF.sub.3 or CHF.sub.2.

8. A compound according to claim 1, wherein R.sup.4 is selected from the group consisting of hydrogen, methyl, ethyl and cyclopropyl-CH.sub.2.

9. A compound according to claim 1, wherein R.sup.5 is hydrogen or methyl.

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. A compound of Formula (II) ##STR00030## wherein R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are as defined in the compound of Formula (I) in claim 1.

15. A compound of Formula (V) ##STR00031## wherein Alk is C.sub.1-C.sub.6 alkyl and R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are as defined in the compound of Formula (I) in claim 1.

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

Description

EXAMPLE 1: PREPARATION OF COMPOUND 1.002

Step 1. Preparation of 3-benzylsulfanyl-1-bromo-2-chloro-4-(trifluoromethoxy)benzene

[0098] To a 3 necked flask, equipped with a thermometer, containing tetrahydrofuran (200 mL) (that was purged and filled with N2) was added diisopropylamine (6.68 g, 9.30 mL, 65.3 mmol). The reaction was stirred at ?78? C. using a dry ice/acetone bath for 30 min. n-Butyllithium in hexane (2.5 M, 23 mL, 58.1 mmol) was added dropwise, maintaining the temperature at ?78? C. and stirred for 40 min. A solution of 1-bromo-2-chloro-4-(trifluoromethoxy)benzene (10.0 g, 36.3 mmol) made up to 20 mL by addition of THF was added dropwise, maintaining the temperature at ?78? C. and stirred for 2 hr. Benzyldisulfanyl)methylbenzene (17.9 g, 72.6 mmol) in THF (30 mL) is added dropwise and the mixture was stirred at ?78? C. for 1 h. Whilst still cold, the reaction mixture was quenched by adding it into a stirred solution of iced water. 2 M HCl was added to acidify the solution and followed by Ethyl acetate extraction?3. The organic phase was concentrated in vacuo and purified by flash column chromatography (0-10% gradient of EtOAc in cyclohexane). Product-containing fractions were combined and partitioned with 1M NaOH, this added purification step removes the impurity phenylmethanethiol. The organics are again collected and concentrated in vacuo to afford 3-benzylsulfanyl-1-bromo-2-chloro-4-(trifluoromethoxy)benzene (8.5 g, 21 mmol, 56%) as a yellow oil. 1H NMR (CDCl.sub.3): 7.59 (d, 1H), 7.25-7.18 (m, 5H), 7.05 (m, 1H), 4.09 (s, 2H)

Step 2: Preparation of methyl 3-benzylsulfanyl-2-chloro-4-(trifluoromethoxy)benzoate

[0099] To a vessel charged with 3-benzylsulfanyl-1-bromo-2-chloro-4-(trifluoromethoxy)benzene (4.00 g, 10.0 mmol) was added methanol (67 mL), triethylamine (3.07 g, 30.2 mmol, 4.23 mL) and [(R)-BINAP Pd(allyl)]Cl (0.406 g, 0.503 mmol). Nitrogen was added to the vessel and the lid was sealed. The vessel was transferred to the Chemscan II and lines were connected and the system setup using 100? C. and 5 Bar as the reaction parameters. The reaction was set to stop when 3 hours had passed. Once the reaction had returned to ambient and the purge and venting cycles had successfully been completed the vessel was disconnected from the Chemscan II. The reaction mixture was concentrated in vacuo and was added EtOAc (100 mL), 2 M aq. HCl (80 mL) and brine (40 mL). The phases were separated and the aqueous phase was extracted with EtOAc (50 mL?3). The combined organic phases were dried (MgSO4) and filtered. The filtrate was adsorbed onto silica and the crude product was purified by flash column chromatography, (0-10% gradient of EtOAc in cyclohexane). Product containing fractions were combined and concentrated in vacuo to afford methyl 3-benzylsulfanyl-2-chloro-4-(trifluoromethoxy)benzoate (2.01 g, 4.80 mmol, 48%) as a yellow oil. 1H NMR (400 MHz, Dichloromethane-d2): 6=7.71 (d, J=8.8 Hz, 1H), 7.29-7.17 (m, 6H), 4.09 (s, 2H), 3.91 (s, 3H).

Step 3: Preparation of methyl 2-chloro-3-chlorosulfonyl-4-(trifluoromethoxy)benzoate

[0100] To a 3-necked flask containing 1,3-dichloro-5,5-dimethyl-imidazolidine-2,4-dione (2.09 g, 10.6 mmol) was added Acetonitrile (80 mL) and the reaction mixture was cooled to 0? C. Water (1.1 mL) and Acetic acid (1.6 mL) were then added. A solution of methyl 3-benzylsulfanyl-2-chloro-4-(trifluoromethoxy)benzoate (2.0 g, 5.3 mmol) in acetonitrile (80 mL) was added over 10 min via a dropping funnel. The rate of addition was limited to keep the temperature below 10? C. The reaction was warmed to RT. The reaction mixture was concentrated under reduced pressure with bath temperature of 30? C. The residue was taken up in dichloromethane, and added to cooled (0? C.), saturated aqueous sodium bicarbonate. The organic phase was separated and dried (MgSO.sub.4) and concentrated in vacuo to afford methyl 2-chloro-3-chlorosulfonyl-4-(trifluoromethoxy)benzoate as a yellow oil. The crude product is carried forward without further purification.

Step 4: Preparation of methyl 2-chloro-3-(ethylsulfamoyl)-4-(trifluoromethoxy)benzoate

[0101] To a flask containing a solution of methyl 2-chloro-3-chlorosulfonyl-4-(trifluoromethoxy)benzoate (0.936 g, 2.65 mmol) in acetonitrile (50 mL) was added ethylamine (2.65 mL, 5.30 mmol), then triethylamine (0.739 mL, 5.30 mmol). The reaction mixture was stirred at RT overnight. The reaction was concentrated in vacuo and quenched by addition of 2 M aq. HCl (100 mL) and extracted with ethyl acetate?3. The combined organic phases were dried (MgSO.sub.4), filtered and concentrated in vacuo and purified by chromatography, (0-50% gradient of EtOAc in cyclohexane). Product-containing fractions were combined are combined and reduced under vacuum to afford methyl 2-chloro-3-(ethylsulfamoyl)-4-(trifluoromethoxy)benzoate (0.8 g, 2.4 mmol, 90%). 1H NMR (400 MHz, chloroform) ? ppm 1.10-1.21 (m, 3H) 3.08-3.21 (m, 2H) 3.93-4.01 (m, 3H) 5.25 (t, 1H) 7.38-7.46 (m, 1H) 7.76-7.89 (m, 1H).

Step 5: Preparation of 2-chloro-3-(ethylsulfamoyl)-4-(trifluoromethoxy)benzoic acid

[0102] To a stirred solution of methyl 2-chloro-3-(ethylsulfamoyl)-4-(trifluoromethoxy)benzoate (0.8 g, 2 mmol) in tetrahydrofuran (10 mL) and water (2 mL) at room temperature was added lithium hydroxide monohydrate (0.3 g, 7 mmol). The mixture was stirred at room temperature overnight. The reaction was quenched by addition of 2 M aq. HCl (100 mL). The mixture was stirred at room temperature for a further 5 minutes. The mixture was then transferred to a separating funnel. EtOAc (100 mL) and brine (50 mL) were added and the phases were separated. The aqueous phase was extracted with EtOAc (100 mL). The combined organic phases were dried (MgSO.sub.4), filtered and concentrated in vacuo to afford 2-chloro-3-(ethylsulfamoyl)-4-(trifluoromethoxy)benzoic acid as a beige solid (0.6 g, 1.7 mmol, 80%). 1H NMR (d4-methanol): 7.95 (d, 1H), 7.56 (m, 1H), 3.07 (m, 2H), 1.10 (m, 3H).

Step 6: Preparation of 2-chloro-3-(ethylsulfamoyl)-N-(1-methyltetrazol-5-yl)-4-(trifluoromethoxy)benzamide

[0103] 2-chloro-3-(ethylsulfamoyl)-4-(trifluoromethoxy)benzoic acid (600 mg, 1.7256 mmol), 1-methyltetrazol-5-amine (205 mg, 2.069 mmol) and 3-methylpyridine (8 mL) were stirred for 10 mins under a nitrogen atmosphere. Triethylamine (0.36 mL, 2.6 mmol) followed by 1-Methylimidazole (0.15 mL, 1.9 mmol) were added and the reaction mixture was stirred at RT for 30 min. The reaction mixture was then cooled to 0? C. and thionyl chloride (0.25 mL, 3.4 mmol) was added, stirred at RT for 16 h. The reaction mixture was quenched with 2N HCl and stirred for 30 min. This is extracted with ethyl acetate?2 and the combined organics are collected and reduced under vacuum. The crude material is purified by reverse phase chromatography (0-100% Acetonitrile in water with 0.1% formic acid). Product containing fractions were combined and concentrated by freeze-drying to afford 2-chloro-3-(ethylsulfamoyl)-N-(1-methyltetrazol-5-yl)-4-(trifluoromethoxy)benzamide as a white solid (0.23 g, 0.65 mmol, 38%). 1H NMR (400 MHz, d4-methanol) ? ppm 1.13 (t, 3H) 3.10 (q, 2H) 4.10 (s, 3H) 7.61-7.69 (m, 1H) 7.89-8.02 (m, 1H).

TABLE-US-00001 TABLE 1 Examples of herbicidal compounds of the present invention. Compound Number Structure .sup.1H NMR 1.001 [00015] (d4-methanol): 7.92 (d, 1H), 7.62 (d, 1H), 4.07 (s, 3H), 2.92 (d, 2H), 0.90-0.80 (m, 1H), 0.42-0.35 (m, 2H), 0.14-0.10 (m, 2H) 1.002 [00016] (d4-methanol): 1.13 (t, 3 H) 3.10 (q, 2 H) 4.10 (s, 3 H) 7.61-7.69 (m, 1 H) 7.89- 8.02 (m, 1 H) 1.003 [00017] (d4-methanol) 2.96 (s, 6 H) 4.10 (s, 3 H) 7.64-7.74 (m, 1 H) 7.92-8.03 (m, 1 H) 1.004 [00018] (d4-methanol): 7.96 (d, 1H), 7.66 (d, 1H), 4.09 (s, 3H), 2.68 (s, 3H) 1.005 [00019] 1.006 [00020] 1.007 [00021] 1.008 [00022] 1.009 [00023] (DMSO-d6): 11.91 (brs, 1H), 8.02(d, 1H), 7.65-7.28(t, 1H), 7.53(d, 1H), 4.02(s, 3H), 2.89(s, 6H) 1.010 [00024] (DMSO-d6): 11.88 (brs, 1H), 7.99 (d, 1H), 7.63-7.27 (m, 2H), 4.00 (s, 3H), 3.28 (q, 2H), 2.88 (s, 3H), 1.12 (t, 3H) 1.011 [00025] 1.012 [00026] (DMSO-d6): 11.91(brs, 1H), 8.05(t, 1H), 7.97(d, 1H), 7.55-7.14(m, 2H), 4.01 (s, 3H), 3.00 (q, 2H), 1.04 (t, 3H) 1.013 [00027] (DMSO-d6): 11.92(brs, 1H), 8.06 (d, 1H), 7.58- 7.22(m, 2H), 4.02(s, 3H), 3.66(brs, 4H), 3.26(brs, 4H)

BIOLOGICAL EXAMPLES

[0104] Seeds of a variety of test species are sown in standard soil in pots (Lolium perenne (LOLPE), Amaranthus retroflexus (AMARE), Abutilon theophrasti (ABUTH), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Zea mays (ZEAMX)). After cultivation for one day under controlled conditions in a glasshouse (at 24/16? C., day/night; 14 hours light; 65% humidity), the plants were sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in 0.6 ml acetone and 45 ml formulation solution containing 10.6% Emulsogen EL (Registry number 61791-12-6), 42.2% N-methyl pyrrolidone, 42.2% dipropylene glycol monomethyl ether (CAS RN 34590-94-8) and 0.2% X-77 (CAS RN 11097-66-8).

[0105] The test plants were 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 14 days, the test was evaluated (100=total damage to plant; 0=no damage to plant, NC=data not captured). The compounds were applied at 130 g/ha unless otherwise stated.

TABLE-US-00002 TABLE B1 POST Application PRE Application Compound AMARE ABUTH SETFA ECHCG ZEAMX AMARE ABUTH SETFA ECHCG ZEAMX 1.001 100 80 20 60 0 100 100 0 20 0 1.002 100 90 70 90 0 100 80 0 10 0 1.003 100 100 100 100 0 90 90 0 70 0 1.004 80 80 80 80 10 100 100 90 90 0 1.009 100 NC 90 90 10 100 NC 100 100 10 1.010 100 NC 90 100 10 100 NC 100 100 10

[0106] The experimental data shows that the compounds of the present invention provide significantly less damage to the maize (ZEAMX) plants whilst still providing good control of many weed species.