SUBSTITUTED ISOPHTHALIC ACID DIAMIDES
20230150953 · 2023-05-18
Inventors
- Christian Waldraff (Bad Vilbel, DE)
- Hartmut AHRENS (Langen, DE)
- Arnim KOEHN (Klein-Winternheim, DE)
- Ralf Braun (Ramberg, DE)
- Elisabeth ASMUS (Hoesbach, DE)
- Birgit BOLLENBACH-WAHL (Weiler/Bingen, DE)
- Anu Bheemaiah Machettira (Frankfurt am Main, DE)
Cpc classification
C07D271/08
CHEMISTRY; METALLURGY
A01N43/713
HUMAN NECESSITIES
A01N25/32
HUMAN NECESSITIES
International classification
C07D257/06
CHEMISTRY; METALLURGY
A01N43/713
HUMAN NECESSITIES
Abstract
Isophthalamides of the general formula (I) are described as herbicides.
##STR00001##
In this formula (I), Z.sup.1 and Z.sup.2 represent radicals such as alkyl, cycloalkyl and phenyl. W.sup.1 and W.sup.2 represent radicals such as hydrogen, alkyl, cycloalkyl and halogen. Q represents a heterocyclic ring such as tetrazolyl.
Claims
1. An isophthalamide of formula (I) or salt thereof ##STR00020## in which the symbols and indices are defined as follows: Q is Q.sup.1 or Q.sup.2, ##STR00021## R.sup.x is (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkyl-O—(C.sub.1-C.sub.6)-alkyl or phenyl, X is halogen, (C.sub.1-C.sub.6)-alkyl, halo-(C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, R.sup.1O, R.sup.2(O).sub.nS, R.sup.1O—(C.sub.1-C.sub.6)-alkyl or R.sup.2S(O).sub.n—(C.sub.1-C.sub.6)-alkyl, Y is halogen, (C.sub.1-C.sub.6)-alkyl, halo-(C.sub.1-C.sub.6)-alkyl, R.sup.1O or R(O).sub.nS, Z.sup.1, Z.sup.2 are independently hydrogen or one of the following groups, each of which is substituted by s radicals from the group consisting of halogen, cyano, R.sup.1C(O), R.sup.1OC(O), R.sup.1O and R.sup.2(O).sub.nS:(C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.3-C.sub.6)-cycloalkyl-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkyl-O—(C.sub.1-C.sub.6)-alkyl, (C.sub.2-C.sub.6)-alkenyl, (C.sub.2-C.sub.6)-alkenyl-(C.sub.1-C.sub.6)-alkyl, (C.sub.2-C.sub.6)-alkynyl, (C.sub.2-C.sub.6)-alkynyl-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkoxy, R.sup.2S(O).sub.n—(C.sub.1-C.sub.6)-alkyl, R.sup.1C(O), R.sup.1OC(O), R.sup.1C(O)—(C.sub.1-C.sub.6)-alkyl, R.sup.1OC(O)—(C.sub.1-C.sub.6)-alkyl, R.sup.1NH—(C.sub.1-C.sub.6)-alkyl, R.sup.1.sub.2N—(C.sub.1-C.sub.6)-alkyl, R.sup.1NHC(O)—(C.sub.1-C.sub.6)-alkyl or R.sup.1.sub.2NC(O)—(C.sub.1-C.sub.6)-alkyl, or one of the following groups, each substituted by s radicals from the group consisting of halogen, (C.sub.1-C.sub.6)-alkyl, halo-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkoxy, halo-(C.sub.1-C.sub.6)-alkoxy, R.sup.1C(O) and R.sup.1OC(O):phenyl, benzyl, heterocyclyl or heterocyclyl-(C.sub.1-C.sub.6)-alkyl, or Z.sup.1 and Z.sup.2, together with the nitrogen atom to which they are bonded, form a four-, five-, six- or seven-membered heterocycle which contains n further heteroatoms from the group of O, S and N as ring members and which is substituted by m radicals from the group consisting of carbonyl, halogen, (C.sub.1-C.sub.6)-alkyl, halo-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkoxy and halo-(C.sub.1-C.sub.6)-alkoxy, R.sup.1 is (C.sub.1-C.sub.6)-alkyl, halo-(C.sub.1-C.sub.6)-alkyl or (C.sub.3-C.sub.6)-cycloalkyl, R.sup.2 is (C.sub.1-C.sub.6)-alkyl, W is nitrogen, W.sup.1 is hydrogen, halogen, cyano, (C.sub.1-C.sub.6)-alkyl, cyano, halo-(C.sub.1-C.sub.6)-alkyl or (C.sub.1-C.sub.6)-alkoxy, W.sup.2 is hydrogen, halogen, cyano, (C.sub.1-C.sub.6)-alkyl, halo-(C.sub.1-C.sub.6)-alkyl or (C.sub.1-C.sub.6)-alkoxy, with the proviso that W.sup.1 and W.sup.2 are not both hydrogen, m is 0, 1, 2 or 3, n is 0, 1 or 2, s is 0, 1, 2, 3 or 4.
2. The isophthalamide as claimed in claim 1, in which Q is Q.sup.1, R.sup.x is Me, Et, Pr, i-Pr, c-Pr, (CH.sub.2).sub.2OMe or Ph, X is halogen, (C.sub.1-C.sub.6)-alkyl, halo-(C.sub.1-C.sub.6)-alkyl, cPr, OMe, OEt, SMe, SEt, CH.sub.2OMe or CH.sub.2SMe, Y is halogen, halo-(C.sub.1-C.sub.6)-alkyl, OMe, SMe, S(O)Me, SO.sub.2Me, SEt, S(O)Et or SO.sub.2Et, W is nitrogen, W.sup.1 is hydrogen, F, Cl or Me, W.sup.2 is hydrogen, F, Cl or OMe, with the proviso that W.sup.1 and W.sup.2 are not both hydrogen.
3. The isophthalamide as claimed in claim 1, in which Q is Q.sup.1, R.sup.x is Me, Et, X is Cl, Br, Me, Et or c-Pr, Y is H, Cl, Br, I, CF.sub.3, CHF.sub.2 or SO.sub.2Me, Z.sup.1, Z.sup.2 are each independently hydrogen, Me, Et, c-Pr, CH.sub.2-c-Pr, CH.sub.2CHF.sub.2 or CH.sub.2CN, W is nitrogen, W.sup.1 is hydrogen, F, Cl or Me, W.sup.2 is hydrogen, F, Cl or OMe, with the proviso that W.sup.1 and W.sup.2 are not both hydrogen.
4. An herbicidal composition or plant growth-regulating composition, comprising one or more isophthalamides of formula (I) or salts thereof as claimed in claim 1.
5. The herbicidal composition as claimed in claim 4, further comprising a formulation auxiliary.
6. The herbicidal composition as claimed in claim 4, comprising at least one further active ingredient from the group of insecticides, acaricides, herbicides, fungicides, safeners and/or growth regulators.
7. The herbicidal composition as claimed in claim 4, comprising a safener.
8. The herbicidal composition as claimed in claim 7, in which the safener is selected from the group consisting of mefenpyr-diethyl, cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl, benoxacor and dichlormid.
9. A method of controlling one or more unwanted plants, comprising applying an effective amount of at least one isophthalamide of formula (I) and/or salt as claimed in claim 1 or an herbicidal composition to one or more plants or to a site of unwanted vegetation.
10. A product comprising one or more compounds of formula (I) and/or salts as claimed in claim 1 or an herbicidal composition thereof for controlling one or more unwanted plants.
11. The product as claimed in claim 10, wherein the one or more isophthalamides of formula (I) and/or salts are used for controlling one or more unwanted plants in one or more crops of one or more useful plants.
12. The product as claimed in claim 11, wherein the useful plants are transgenic useful plants.
Description
A. Chemical Examples
Preparation of N.SUP.1.-ethyl-N.SUP.3.-(1-ethyl-1H-tetrazol-5-yl)-4-fluoro-2-methyl-6-(trifluoromethyl)isophthalamide (Example No. 2-93)
Step 1: Synthesis of methyl 3-amino-2-bromo-6-fluoro-4-(trifluoromethyl)benzoate
[0395] To a solution of 510 g (2.15 mol) of commercially available methyl 5-amino-2-fluoro-4-(trifluoromethyl)benzoate in 5.1 l of tetrahydrofuran was added, at 0° C., 765.94 g (4.3 mol) of N-bromosuccinimide, and the reaction mixture was stirred at 40° C. for 2 h. At 0° C., water was added, followed by extraction with ethyl acetate. The organic phases were then washed with water and saturated aqueous NaCl solution. Drying with sodium sulfate was followed by concentration to dryness.
[0396] Purification by chromatography (6% ethyl acetate in hexane) afforded 320 g of methyl 3-amino-2-bromo-6-fluoro-4-(trifluoromethyl)benzoate.
[0397] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=7.59 (1H); 5.77 (br s, 2H); 3.92 (s, 3H).
Step 2: Synthesis of methyl 3-amino-6-fluoro-2-methyl-4-(trifluoromethyl)benzoate
[0398] 320 g (1.01 mol) of methyl 3-amino-2-bromo-6-fluoro-4-(trifluoromethyl)benzoate and 431.5 ml (3.04 mol) of 2,4,6-trimethyl-1,3,5,2,4,6-trioxatriborinane were dissolved in 2.56 l of an 8:2 mixture of 1,4-dioxane and water, and 993.13 g (3.04 mol) of cesium carbonate was added while stirring. The reaction mixture was sparged with nitrogen for 15 minutes, and 58.72 g (0.5 mol) of Pd(PPh.sub.3).sub.4 was added under nitrogen. In a closed apparatus, the reaction mixture was stirred at 110° C. for 16 h. Thereafter, the mixture was diluted with ethyl acetate, filtered through a Celite-filled frit and concentrated to dryness. Purification by chromatography (10-12% ethyl acetate in hexane) afforded 106 g of methyl 3-amino-6-fluoro-2-methyl-4-(trifluoromethyl)benzoate.
Step 3: Synthesis of methyl 6-fluoro-3-iodo-2-methyl-4-(trifluoromethyl)benzoate
[0399] 10 g (39.8 mmol) of methyl 3-amino-6-fluoro-2-methyl-4-(trifluoromethyl)benzoate was initially charged in 100 ml of water and 150 ml of conc. hydrochloric acid. The reaction mixture was cooled down to 5° C. and stirred at that temperature for 30 min. Then a solution of 3.02 g (43.7 mmol) of sodium nitrite in 20 ml of water was added dropwise at 5° C., and the mixture was stirred at that temperature for 2 h. Likewise at that temperature, a solution of 9.91 g (59.7 mmol) potassium iodide in 40 ml of water was added dropwise. The reaction mixture was warmed gradually to room temperature and stirred for 12 h. The mixture was poured on to 400 ml of ice-water and extracted with dichloromethane. The organic phases were washed with saturated aqueous sodium thiosulfate solution, dried and concentrated to dryness. The residue was purified by column chromatography (HPLC, normal phase, gradient: ethyl acetate/n-heptane: 5%.fwdarw.30% ethyl acetate). 8.83 g of methyl 6-fluoro-3-iodo-2-methyl-4-(trifluoromethyl)benzoate was obtained.
[0400] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=7.73 (d, 1H); 3.95 (s, 3H); 2.49 (s, 3H).
Step 4: Synthesis of 4-fluoro-3-(methoxycarbonyl)-2-methyl-6-(trifluoromethyl)benzoic acid
[0401] To an initial charge of 10.9 g (30.1 mmol) of methyl 6-fluoro-3-iodo-2-methyl-4-(trifluoromethyl)benzoate in 250 ml of dry THF was added, at −70° C. within 30 min, 30.1 ml (39.1 mmol) of a 1.3 molar solution of i-PrMgCl/LiCl in THF. The reaction solution was warmed to -30° C. and stirred at that temperature for a further 30 min. Thereafter, it was cooled back down to −40° C., and gaseous CO.sub.2 was introduced. Thereafter—with continued introduction of CO.sub.2 and monitoring of the reaction—the mixture was warmed to room temperature. After the conversion had ended, the reaction solution was degassed in an ultrasound bath and then concentrated to dryness. The residue was taken up with water, adjusted to pH 3-4 with 2 N HCl, and extracted with dichloromethane. The organic phases were dried and concentrated. The residue was purified by column chromatography (HPLC, normal phase, gradient: ethyl acetate/n-heptane: 5%.fwdarw.70% ethyl acetate). 6.3 g of 4-fluoro-3-(methoxycarbonyl)-2-methyl-6-(trifluoromethyl)benzoic acid was obtained.
[0402] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=7.81 (d, 1H); 3.95 (s, 3H); 2.33 (s, 3H).
Step 5: Synthesis of methyl 3-(ethylcarbamoyl)-6-fluoro-2-methyl-4-(trifluoromethyl)benzoate
[0403] 1 g (3.56 mmol) of 4-fluoro-3-(methoxycarbonyl)-2-methyl-6-(trifluoromethyl)benzoic acid was dissolved together with a catalytic amount of dimethylformamide in 50 ml of dichloromethane, and 0.47 ml (5.35 mmol) of oxalyl chloride was added at room temperature. The reaction mixture was stirred for 3 h and then concentrated to dryness and coevaporated twice with toluene. The residue was dissolved in 50 ml of dichloromethane and, at 5° C., added dropwise to a solution of 2.14 ml (4.28 mmol) of ethylamine and 1.24 ml (7.13 mmol) of Hünig's base in 50 ml of dichloromethane. The reaction mixture was warmed gradually to room temperature and stirred for 12 h. The mixture was concentrated to dryness, the residue was taken up with water and extracted with dichloromethane, and the organic phases were dried and concentrated to dryness. 913 mg of methyl 3-(ethylcarbamoyl)-6-fluoro-2-methyl-4-(trifluoromethyl)benzoate was obtained.
[0404] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=8.59 (t, 1H); 7.73 (d, 1H); 3.94 (s, 3H); 3.26 (m, 2H); 2.25 (s, 3H); 1.09 (t, 3H).
Step 6: Synthesis of 3-(ethylcarbamoyl)-6-fluoro-2-methyl-4-(trifluoromethyl)benzoic acid
[0405] To an initial charge of 900 mg (2.92 mmol) of methyl 3-(ethylcarbamoyl)-6-fluoro-2-methyl-4-(trifluoromethyl)benzoate in 10 ml of methanol was added dropwise, at room temperature, a solution of 175.7 mg (4.39 mmol) of sodium hydroxide in 3 ml of water. The reaction mixture was stirred at room temperature for 12 h. Thereafter, the reaction mixture was concentrated to dryness, and the residue was taken up in 20 ml of water. The mixture was adjusted to pH 3-4 with 2N HCl, and the precipitate formed was filtered off and dried. 690 mg of 3-(ethylcarbamoyl)-6-fluoro-2-methyl-4-(trifluoromethyl)benzoic acid was obtained.
[0406] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=14.21 (br s, 1H); 8.58 (t, 1H); 7.67 (d, 1H); 3.27 (m, 2H); 2.27 (s, 3H); 1.09 (t, 3H).
Step 7: Synthesis of N.SUP.1.-ethyl-N.SUP.3.-(1-ethyl-1H-tetrazol-5-yl)-4-fluoro-2-methyl-6-(trifluoromethyl)isophthalamide
[0407] To an initial charge of 200 mg (0.68 mmol) of 3-(ethylcarbamoyl)-6-fluoro-2-methyl-4-(trifluoromethyl)benzoic acid together with 94.5 mg (0.81 mmol) of 1-ethyl-1H-tetrazole-5-amine in 3 ml of pyridine at room temperature is added 0.1 ml (1.09 mmol) of oxalyl chloride. The reaction mixture was stirred at room temperature for 12 h. Then 8 ml of water was added and the mixture was extracted with dichloromethane. The organic phases were dried and concentrated to dryness. The residue was purified by column chromatography (HPLC, C18, gradient: acetonitrile/water (++0.05% trifluoroacetic acid), 20/80.fwdarw.100/0 in 30 min). 103 mg of N.sup.1-ethyl-N.sup.3-(1-ethyl-1H-tetrazol-5-yl)-4-fluoro-2-methyl-6-(trifluoromethyl)isophthalamide (Example No. 2-93) were obtained.
[0408] In an analogous manner, 200 mg (0.61 mmol) of 3-[(2,2-difluoroethyl)carbamoyl]-6-fluoro-2-methyl-4-(trifluoromethyl)benzoic acid was used to obtain 93 mg of N.sup.1-(2,2-difluoroethyl)-4-fluoro-2-methyl-N.sup.3-(1-methyl-1H-tetrazol-5-yl)-6-(trifluoromethyl)isophthalamide (Example No. 1-385).
[0409] In an analogous manner, 200 mg (0.68 mmol) of 3-(dimethylcarbamoyl)-6-fluoro-2-methyl-4-(trifluoromethyl)benzoic acid was used to obtain 89 mg of N′-(1-ethyl-1H-tetrazol-5-yl)-4-fluoro-N,N,2-trimethyl-6-(trifluoromethyl)isophthalamide (Example No. 2-95).
[0410] The examples listed in the tables below were prepared analogously to the methods mentioned above or can be obtained analogously to the methods mentioned above. These compounds are very particularly preferred.
[0411] The abbreviations used here mean:
[0412] Me=methyl Bu=butyl Et=ethyl Pr=propyl c=cyclo Ph=phenyl
TABLE-US-00001 TABLE 1 Inventive compounds of the general formula (1) in which Q is Q.sup.1 and R.sup.x is methyl, and the other substituents have the definitions given below.
TABLE-US-00002 TABLE 2 Inventive compounds of the general formula (1) in which Q is Q.sup.1 and R.sup.x is ethyl, and the other substituents have the definitions given below.
[0413] NMR data for numerous inventive compounds of the formula (I) mentioned in tables above are disclosed below for further characterization:
[0414] Ex. no. 1-85: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=12.09 (br s, 1H); 8.70 (d, 1H); 7.80 (d, 1H); 3.99 (s, 3H); 2.81 (m, 1H); 2.32 (s, 3H); 0.71 (m, 2H); 0.48 (br s, 2H);
[0415] Ex. no. 1-92: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=12.10 (br s, 1H); 8.56 (q, 1H); 7.80 d, 1H); 3.99 (s, 3H); 2.78 (d, 3H); 2.32 (s, 3H);
[0416] Ex. no. 1-93: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=12.10 (br s, 1H); 8.63 (t, 1H); 7.80 (d, 1H); 3.99 (s, 3H); 3.28 (m, 2H); 2.34 (s, 3H); 1.11 (t, 3H);
[0417] Ex. no. 1-95: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=12.10 (br s, 1H); 7.86 (d, 1H); 4.00 (s, 3H); 3.03 (s, 3H); 2.75 (s, 3H); 2.27 (s, 3H);
[0418] Ex. no. 1-96: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=12.09 (br s, 1H); 7.86 (d, 1H); 4.00 (s, 3H); 3.61 (m, 2H, isomer 1); 3.44 (m, 1H, isomer 2); 3.08 (m, 1H, isomer 2); 3.00 (s, 3H, isomer 2); 2.72 (s, 3H); 2.28 (s, 3H); 1.14 (t, 3H, isomer 1); 1.03 (t, 3H, isomer 2);
[0419] Ex. no. 1-97: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=12.12 and 12.09 (2×br s, 2×1H); 7.87 and 7.85 (2×d, 2×1H); 4.00 and 3.99 (2×s, 2×3H); 2.98 and 2.66 (2×s, 2×3H); 2.97 and 2.88 (2×m, 2×1H); 2.29 and 2.27 (2×s, 2×3H); 0.81 (m, 2×1H); 0.72 (m, 2×1H); 0.51 (m, 2×2H);
[0420] Ex. no. 1-180: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=12.32 (br s, 1H); 8.74 (q, 1H); 8.08 (d, 1H); 3.99 (s, 3H); 2.80 (d, 3H);
[0421] Ex. no. 1-181: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=12.33 (br s, 1H); 8.80 (t, 1H); 8.08 (d, 1H); 3.99 (s, 3H); 3.29 (m, 2H); 1.11 (t, 3H);
[0422] Ex. no. 1-182: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=12.32 (br s, 1H); 8.87 (d, 1H); 8.08 (d, 1H); 3.99 (s, 3H); 2.80 (m, 1H); 0.73 (m, 2H); 0.50 (br s, 2H);
[0423] Ex. no. 1-384: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=12.10 (br s, 1H); 8.75 (t, 1H); 7.79 (d, 1H); 3.99 (s, 3H); 3.13 (m, 2H); 2.36 (s, 3H); 1.00 (m, 1H); 0.45 (m, 2H); 0.22 (m, 2H);
[0424] Ex. no. 1-385: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=12.10 (br s, 1H); 9.11 (t, 1H); 7.83 (d, 1H); 6.14 (tt, 1H); 3.99 (s, 3H); 3.71 (m, 2H); 2.34 (s, 3H);
[0425] Ex. no. 1-386: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=12.12 (br s, 1H); 9.45 (t, 1H); 7.87 (d, 1H); 4.49 (br s, 2H); 4.00 (s, 3H); 2.33 (s, 3H);
[0426] Ex. no. 1-387: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=11.96 (br s, 1H); 8.60 (q, 1H); 7.49 (s, 1H); 3.99 (s, 3H); 3.98 (s, 3H); 2.77 (d, 3H);
[0427] Ex. no. 1-388: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=11.96 (br s, 1H); 8.67 (t, 1H); 7.49 (s, 1H); 3.99 (s, 3H); 3.98 (s, 3H); 3.26 (m, 2H); 1.10 (t, 3H);
[0428] Ex. no. 1-389: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=11.96 (br s, 1H); 8.74 (d, 1H); 7.49 (s, 1H); 3.99 (s, 3H); 3.98 (s, 3H); 2.79 (m, 1H); 0.71 (m, 2H); 0.49 (br s, 2H);
[0429] Ex. no. 2-85: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=11.99 (br s, 1H); 8.71 (d, 1H); 7.80 (d, 1H); 4.35 (q, 2H); 2.80 (m, 1H); 2.32 (s, 3H); 1.47 (t, 3H); 0.71 (m, 2H); 0.49 (br s, 2H);
[0430] Ex. no. 2-92: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=12.00 (br s, 1H); 8.56 (q, 1H); 7.80 (d, 1H); 4.35 (q, 2H); 2.78 (d, 3H); 2.31 (s, 3H); 1.47 (t, 3H);
[0431] Ex. no. 2-93: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=12.00 (br s, 1H); 8.63 (t, 1H); 7.80 (d, 1H); 4.35 (q, 2H); 3.28 (m, 2H); 2.33 (s, 3H); 1.47 (t, 3H); 1.11 (t, 3H);
[0432] Ex. no. 2-95: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=12.00 (br s, 1H); 7.86 (d, 1H); 4.35 (q, 2H); 3.03 (s, 3H); 2.75 (s, 3H); 2.27 (s, 3H); 1.48 (t, 3H);
[0433] Ex. no. 2-96: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=12.00 (br s, 1H); 7.86 (d, 1H); 4.35 (q, 2H); 3.60 (m, 1H, isomer 1); 3.41 (m, 1H), isomer 1); 3.07 (m, 2H, isomer 2); 2.99 (s, 3H, isomer 2); 2.73 (s, 3H, isomer 1); 2.28 (s, 3H); 1.47 (t, 3H); 1.14 (t, 3H, isomer 1); 1.03 (t, 3H, isomer 2);
[0434] Ex. no. 2-97: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=12.02 and 12.00 (2×br s, 2×, 1H); 7.88 and 7.86 (2×d, 2×1H); 4.36 (2×q, 2×2H); 2.98 and 2.2.66 (2×s, 2×3H); 2.98 and 2.2.88 (2×m, 2×1H); 2.29 and 2.26 (sx s, 2×3H); 1.48 (2×t, 2×3H); 0.81 (m, 2×1H); 0.73 (m, 2×1H); 0.51 (m, 2×2H);
[0435] Ex. no. 2-384: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=11.99 (br s, 1H); 8.75 (t, 1H); 7.80 (d, 1H); 4.35 (q, 2H); 3.13 (m, 2H); 2.36 (s, 3H); 1.47 (t, 3H); 1.01 (m, 1H); 0.46 (m, 1H); 0.22 (m, 2H);
[0436] Ex. no. 2-385: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=12.01 (br s, 1H); 9.11 (t, 1H); 7.84 (d, 1H); 6.14 (tt, 1H); 4.35 (q, 2H); 3.71 (m, 2H); 2.34 (s, 3H); 1.47 (t, 3H);
[0437] Ex. no. 2-386: .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ=12.02 (br s, 1H); 9.45 (t, 1H); 7.88 (d, 1H); 4.49 (m, 2H); 4.35 (q, 2H); 2.33 (s, 3H); 1.47 (t, 3H).
B. Formulation Examples
[0438] a) A dusting product is obtained by mixing 10 parts by weight of a compound of the formula (I) and/or salts thereof and 90 parts by weight of talc as an inert substance and comminuting the mixture in a hammer mill. [0439] b) A readily water-dispersible, wettable powder is obtained by mixing 25 parts by weight of a compound of the formula (I) and/or salts thereof, 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyltaurate as a wetting agent and dispersant, and grinding the mixture in a pinned-disk mill. [0440] c) A readily water-dispersible dispersion concentrate is obtained by mixing 20 parts by weight of a compound of the formula (I) and/or salts thereof with 6 parts by weight of alkylphenol polyglycol ether (@Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range for example about 255 to above 277 C), and grinding the mixture in a friction ball mill to a fineness of below 5 microns. [0441] d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I) and/or salts thereof, 75 parts by weight of cyclohexanone as a solvent and 10 parts by weight of ethoxylated nonylphenol as an emulsifier. [0442] e) Water-dispersible granules are obtained by mixing [0443] 75 parts by weight of a compound of the formula (I) and/or salts thereof, [0444] 10 parts by weight of calcium lignosulfonate, [0445] 5 parts by weight of sodium lauryl sulfate, [0446] 3 parts by weight of polyvinyl alcohol and [0447] 7 parts by weight of kaolin, [0448] grinding the mixture in a pinned-disk mill, and granulating the powder in a fluidized bed by spray application of water as a granulating liquid. [0449] f) Water-dispersible granules are also obtained by homogenizing and precomminuting, in a colloid mill, [0450] 25 parts by weight of a compound of the formula (I) and/or salts thereof, [0451] 5 parts by weight of sodium 2,2′-dinaphthylmethane-6,6′-disulfonate [0452] 2 parts by weight of sodium oleoylmethyltaurate, [0453] 1 part by weight of polyvinyl alcohol, [0454] 17 parts by weight of calcium carbonate and [0455] 50 parts by weight of water, [0456] then grinding the mixture in a bead mill and atomizing and drying the resulting suspension in a spray tower by means of a one-phase nozzle.
C. Biological Examples
[0457] The abbreviations used for the harmful plants mean: [0458] ABUTH Abutilon theophrasti ALOMY Alopecurus myosuroides [0459] AVEFA Avena fatua AMARE Amaranthus retroflexus [0460] CYPES Cyperus esculentus DIGSA Digitaria sanguinalis [0461] ECHCG Echinochloa crus-galli HORMU Hordeum murinum [0462] LOLMU Lolium multiflorum LOLRI Lolium rigidum [0463] MATIN Matricaria inodora PHBPU Pharbitis purpurea [0464] POLCO Polygonum convolvulus SETVI Setaria viridis [0465] STEME Stellaria media VERPE Veronica persica [0466] VIOTR Viola tricolor
[0467] 1. Pre-Emergence Herbicidal Action Against Harmful Plants
[0468] Seeds of monocotyledonous and dicotyledonous weed plants and crop plants are laid out in sandy loam soil in wood-fiber pots and covered with soil. The compounds of the invention, formulated in the form of wettable powders (WP) or as emulsion concentrates (EC), are then applied to the surface of the covering soil in the form of an aqueous suspension or emulsion at a water application rate equivalent to 600 to 800 l/ha, with addition of 0.2% wetting agent. After the treatment, the pots are placed in a greenhouse and kept under good growth conditions for the trial plants. The damage to the test plants is scored visually after a test period of 3 weeks by comparison with untreated controls (herbicidal activity in percent (%): 100% activity=the plants have died, 0% activity=like control plants). Numerous compounds of the invention showed very good action against a multitude of important harmful plants. The tables below illustrate, in an illustrative manner, the post-emergence herbicidal action of the compounds of the invention, the herbicidal activity being stated in percent.
TABLE-US-00003 TABLE 1a Pre-emergence action at 20 g/ha against ABUTH in % Example number Dosage [g/ha] ABUTH 1-93 20 100 2-384 20 90 1-97 20 100 2-97 20 100 2-85 20 80
TABLE-US-00004 TABLE 1b Pre-emergence action at 80 g/ha against ABUTH in % Example number Dosage [g/ha] ABUTH 1-92 80 100 2-92 80 80 1-93 80 100 2-93 80 100 1-384 80 100 2-384 80 100 1-385 80 80 2-385 80 100 2-95 80 100 1-97 80 100 2-97 80 100 1-96 80 100 2-96 80 90 1-85 80 100 2-85 80 100 1-180 80 100 1-181 80 100 1-182 80 100
TABLE-US-00005 TABLE 2a Pre-emergence action at 20 g/ha against ALOMY in % Example number Dosage [g/ha] ALOMY 2-85 20 80
TABLE-US-00006 TABLE 2b Pre-emergence action at 80 g/ha against ALOMY in % Example number Dosage [g/ha] ALOMY 1-92 80 80 1-93 80 80 2-93 80 90 1-384 80 80 2-384 80 80 1-385 80 90 1-95 80 90 2-95 80 90 1-97 80 80 1-96 80 80 2-96 80 80 1-85 80 80 2-85 80 90 1-182 80 80
TABLE-US-00007 TABLE 3a Pre-emergence action at 20 g/ha against AMARE in % Example number Dosage [g/ha] AMARE 1-92 20 90 2-92 20 100 1-93 20 100 2-93 20 100 1-384 20 100 2-384 20 100 1-385 20 90 1-95 20 90 1-97 20 100 2-97 20 100 2-96 20 100 1-85 20 100 2-85 20 100 1-180 20 100 1-181 20 100 1-182 20 100
TABLE-US-00008 TABLE 3b Pre-emergence action at 80 g/ha against AMARE in % Example number Dosage [g/ha] AMARE 1-92 80 100 2-92 80 100 1-93 80 100 2-93 80 100 1-384 80 100 2-384 80 100 1-385 80 100 2-385 80 100 1-95 80 100 2-95 80 100 1-97 80 100 2-97 80 100 2-386 80 100 1-96 80 100 2-96 80 100 1-85 80 100 2-85 80 100 1-180 80 100 1-181 80 100 1-182 80 100
TABLE-US-00009 TABLE 4 Pre-emergence action at 80 g/ha against AVEFA in % Example number Dosage [g/ha] AVEFA 1-384 80 80 2-85 80 80
TABLE-US-00010 TABLE 5a Pre-emergence action at 20 g/ha against DIGSA in % Example number Dosage [g/ha] DIGSA 2-92 20 80 1-93 20 80 1-384 20 100 2-384 20 80 1-385 20 80 2-385 20 90 1-95 20 80 2-95 20 90 1-97 20 80 2-97 20 90 2-96 20 80 1-85 20 100 2-85 20 80 1-180 20 80 1-182 20 90
TABLE-US-00011 TABLE 5b Pre-emergence action at 80 g/ha against DIGSA in % Example number Dosage [g/ha] DIGSA 1-92 80 100 2-92 80 100 1-93 80 100 2-93 80 100 1-384 80 100 2-384 80 100 1-385 80 100 2-385 80 100 1-95 80 90 2-95 80 100 1-97 80 100 2-97 80 100 1-96 80 100 2-96 80 90 1-85 80 100 2-85 80 100 1-180 80 80 1-181 80 80 1-182 80 100
TABLE-US-00012 TABLE 6 Pre-emergence action at 80 g/ha against ECHCG in % Example number Dosage [g/ha] ECHCG 1-93 80 90 2-93 80 80 1-384 80 100 2-384 80 80 2-385 80 80 2-95 80 80 1-97 80 90 2-97 80 80 1-96 80 80 2-96 80 80 1-85 80 80 2-85 80 80
TABLE-US-00013 TABLE 7 Pre-emergence action at 80 g/ha against LOLRI in % Example number Dosage [g/ha] LOLRI 2-92 80 90 1-93 80 80 2-95 80 80 2-85 80 80
TABLE-US-00014 TABLE 8a Pre-emergence action at 20 g/ha against MATIN in % Example number Dosage [g/ha] MATIN 1-92 20 90 2-92 20 90 2-93 20 80 2-385 20 80 1-97 20 90 2-97 20 90 1-96 20 80 2-96 20 80 1-85 20 80 2-85 20 90
TABLE-US-00015 TABLE 8b Pre-emergence action at 80 g/ha against MATIN in % Example number Dosage [g/ha] MATIN 1-92 80 90 2-92 80 90 1-93 80 90 2-93 80 90 1-384 80 80 2-384 80 100 1-385 80 90 2-385 80 90 1-95 80 90 2-95 80 90 1-97 80 100 2-97 80 100 2-386 80 80 1-96 80 100 2-96 80 90 1-85 80 100 2-85 80 100 1-180 80 100 1-181 80 100 1-182 80 100
TABLE-US-00016 TABLE 9a Pre-emergence action at 20 g/ha against PHBPU in % Example number Dosage [g/ha] PHBPU 2-93 20 80
TABLE-US-00017 TABLE 9b Pre-emergence action at 80 g/ha against PHBPU in % Example number Dosage [g/ha] PHBPU 2-92 80 80 1-93 80 90 2-93 80 90 2-384 80 80 1-385 80 80 2-96 80 80 1-85 80 80 2-85 80 90
TABLE-US-00018 TABLE 10a Pre-emergence action at 20 g/ha against POLCO in % Example number Dosage [g/ha] POLCO 2-92 20 80 2-384 20 90 2-95 20 80
TABLE-US-00019 TABLE 10b Pre-emergence action at 80 g/ha against POLCO in % Example number Dosage [g/ha] POLCO 2-92 80 90 1-93 80 80 1-384 80 90 2-384 80 100 2-385 80 90 1-95 80 80 2-95 80 100 2-386 80 80 2-96 80 80 1-85 80 80 2-85 80 80 1-182 80 90
TABLE-US-00020 TABLE 11a Pre-emergence action at 20 g/ha against SETVI in % Example number Dosage [g/ha] SETVI 1-92 20 80 1-95 20 100
TABLE-US-00021 TABLE 11b Pre-emergence action at 80 g/ha against SETVI in % Example number Dosage [g/ha] SETVI 1-92 80 100 1-93 80 80 2-93 80 80 1-384 80 90 2-384 80 80 1-385 80 90 1-95 80 100 2-95 80 90 1-97 80 80 1-96 80 100 1-85 80 100 2-85 80 100
TABLE-US-00022 TABLE 12a Pre-emergence action at 20 g/ha against VERPE in % Example number Dosage [g/ha] VERPE 2-97 20 80
TABLE-US-00023 TABLE 12b Pre-emergence action at 80 g/ha against VERPE in % Example number Dosage [g/ha] VERPE 2-97 80 80 1-182 80 100
[0469] 2. Post-Emergence Herbicidal Action Against Harmful Plants
[0470] Seeds of monocotyledonous and dicotyledonous weed and crop plants are laid out in sandy loam soil in wood-fiber pots, covered with soil and cultivated in a greenhouse under good growth conditions. 2 to 3 weeks after sowing, the test plants are treated at the one-leaf stage. The compounds of the invention, formulated in the form of wettable powders (WP) or as emulsion concentrates (EC), are then sprayed onto the green parts of the plants in the form of an aqueous suspension or emulsion at a water application rate equivalent to 600 to 800 l/ha, with addition of 0.2% wetting agent. After the test plants have been left to stand in the greenhouse under optimal growth conditions for about 3 weeks, the action of the preparations is assessed visually in comparison to untreated controls (herbicidal action in percent (%): 100% activity=the plants have died, 0% activity=like control plants). Numerous compounds of the invention showed very good action against a multitude of important harmful plants. The tables below illustrate, in an illustrative manner, the post-emergence herbicidal action of the compounds of the invention, the herbicidal activity being stated in percent.
TABLE-US-00024 TABLE 13 Post-emergence action at 20 g/ha against ABUTH in % Example number Dosage [g/ha] ABUTH 2-96 20 80 1-180 20 90 1-181 20 90
TABLE-US-00025 TABLE 14 Post-emergence action at 20 g/ha against ALOMY in % Example number Dosage [g/ha] ALOMY 1-384 20 80 1-85 20 80 2-85 20 80 1-182 20 80
TABLE-US-00026 TABLE 15a Post-emergence action at 5 g/ha against AMARE in % Example number Dosage [g/ha] AMARE 1-92 5 80 2-92 5 90 1-93 5 90 2-93 5 80 1-384 5 80 2-384 5 90 1-385 5 90 2-385 5 80 1-96 5 80 2-96 5 80 2-85 5 80 1-180 5 80 1-181 5 90 1-182 5 80
TABLE-US-00027 TABLE 15b Post-emergence action at 20 g/ha against AMARE in % Example number Dosage [g/ha] AMARE 1-92 20 90 2-92 20 90 1-93 20 90 2-93 20 90 1-384 20 90 2-384 20 90 1-385 20 90 2-385 20 90 1-95 20 90 1-96 20 90 2-96 20 90 1-85 20 80 2-85 20 90 1-180 20 90 1-181 20 90 1-182 20 100 1-388 20 80
TABLE-US-00028 TABLE 16 Post-emergence action at 20 g/ha against AVEFA in % Example number Dosage [g/ha] AVEFA 1-85 20 80
TABLE-US-00029 TABLE 17 Post-emergence action at 20 g/ha against DIGSA in % Example number Dosage [g/ha] DIGSA 1-96 20 90 2-96 20 90 1-85 20 90 2-85 20 90
TABLE-US-00030 TABLE 18a Post-emergence action at 5 g/ha against ECHCG in % Example number Dosage [g/ha] ECHCG 1-384 5 80
TABLE-US-00031 TABLE 18b Post-emergence action at 20 g/ha against ECHCG in % Example number Dosage [g/ha] ECHCG 1-92 20 80 2-92 20 80 1-384 20 80 2-384 20 80 1-96 20 80 1-182 20 80
TABLE-US-00032 TABLE 19 Post-emergence action at 20 g/ha against MATIN in % Example number Dosage [g/ha] MATIN 1-97 20 80 2-97 20 80 2-96 20 80 2-85 20 80
TABLE-US-00033 TABLE 20a Post-emergence action at 5 g/ha against PHBPU in % Example number Dosage [g/ha] PHBPU 1-93 5 80 2-85 5 80
TABLE-US-00034 TABLE 20b Post-emergence action at 20 g/ha against PHBPU in % Example number Dosage [g/ha] PHBPU 1-92 20 80 2-92 20 80 1-93 20 90 2-93 20 90 2-95 20 80 2-96 20 90 1-85 20 80 2-85 20 90
TABLE-US-00035 TABLE 21 Post-emergence action at 20 g/ha against POLCO in % Example number Dosage [g/ha] POLCO 1-97 20 100 1-85 20 80 2-85 20 80
TABLE-US-00036 TABLE 22 Post-emergence action at 20 g/ha against SETVI in % Example number Dosage [g/ha] SETVI 1-92 20 80 2-385 20 80 1-85 20 80
TABLE-US-00037 TABLE 23 Post-emergence action at 20 g/ha against VERPE in % Example number Dosage [g/ha] VERPE 2-96 20 80