HERBICIDALLY ACTIVE BICYCLIC BENZAMIDES

Abstract

Benzoylamides of the general formula (I) are described as herbicides. In this formula (I),

##STR00001##

B represents N or X.sup.1 and X.sup.2 represents O or S(O).sub.n. R, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e, R.sup.f and R.sup.x represent radicals such as hydrogen, fluorine, chlorine, hydroxyl, (C.sub.1-C.sub.6)-alkyl, halo-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkyloxy, (C.sub.1-C.sub.6)-alkylthio and cyano, or R.sup.a and R.sup.b or R.sup.c and R.sup.d or R.sup.e and R.sup.f in each case together represent an oxo or a thiooxo group.

Claims

1. A compound of formula (I) and/or an agrochemically acceptable salt thereof, in which the symbols and indices have the following meanings: ##STR00030## B represents N or CH, X.sup.1, X.sup.2 independently of one another each represent O or S(O).sub.n, R represents halo-(C.sub.1-C.sub.6)-alkyl, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e, R.sup.f independently of one another each represent hydrogen, fluorine, chlorine, hydroxy, (C.sub.1-C.sub.6)-alkyl, halo-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkyloxy, (C.sub.1-C.sub.6)-alkylthio, cyano, or R.sup.a and R.sup.b or R.sup.c and R.sup.d or R.sup.e and R.sup.f together represent an oxo or a thioxo group, R.sup.x represents (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkyl-O(C.sub.1-C.sub.6)-alkyl, n represents 0, 1 or 2.

2. The compound as claimed in claim 1, wherein B represents N or CH, X.sup.1, X.sup.2 independently of one another each represent O or S(O).sub.n, R represents halo-(C.sub.1-C.sub.3)-alkyl, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e, R.sup.f independently of one another each represent hydrogen, fluorine, chlorine, hydroxy, (C.sub.1-C.sub.6)-alkyl, halo-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkyloxy, (C.sub.1-C.sub.6)-alkylthio, cyano, or R.sup.a and R.sup.b or R.sup.c and R.sup.d or R.sup.e and R.sup.f together may represent a carbonyl or a thiocarbonyl group, R.sup.x represents (C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-alkyl-O(C.sub.1-C.sub.3)-alkyl, phenyl, n represents 0, 1 or 2.

3. The compound as claimed in claim 1, in which B represents N or CH, X.sup.1, X.sup.2 independently of one another each represent O or S(O).sub.n, R represents trifluoromethyl, difluoromethyl or pentafluoroethyl, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e, R.sup.f independently of one another each represent hydrogen, fluorine, chlorine, hydroxy, methyl, ethyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, methylthio, ethylthio, cyano, or R.sup.a and R.sup.b or R.sup.c and R.sup.d or R.sup.e and R.sup.f together represent an oxo or a thiooxo group, R.sup.x represents methyl, ethyl, propyl, methoxymethyl, methoxyethyl, 2-methoxy-2-methyl-1-propyl, phenyl, n represents 0, 1 or 2.

4. An herbicidal composition comprising at least one compound as claimed in claim 1 mixed with one or more formulation auxiliaries.

5. The herbicidal composition as claimed in claim 4, comprising at least one further pesticidally active substance selected from the group consisting of insecticides, acaricides, herbicides, fungicides, safeners, and growth regulators.

6. A method for controlling one or more unwanted plants, comprising applying an effective amount of at least one compound as claimed in claim 1 or an herbicidal composition thereof to the plants or a site of unwanted vegetation.

7. A product comprising one or more compounds of as claimed in claim 1 or an herbicidal composition thereof for controlling one or more unwanted plants.

8. The product as claimed in claim 7, wherein the compound is for controlling one or more unwanted plants in one or more crops of useful plants.

9. The product as claimed in claim 8, wherein the useful plants are transgenic useful plants.

10. A compound of formula (II) wherein ##STR00031## L represents halogen or R.sup.3O, R.sup.3 represents hydrogen or (C.sub.1-C.sub.6)-alkyl, X.sup.1, X.sup.2 represent O or S(O).sub.n, where X.sup.1 and X.sup.2 are not simultaneously O or S(O).sub.n, R represents difluoromethyl, trifluoromethyl, 1,1,2,2-tetrafluoroethyl, pentafluoroethyl, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e, R.sup.f independently of one another each represent hydrogen, fluorine, chlorine, hydroxy, (C.sub.1-C.sub.6)-alkyl, halo-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)alkyloxy, (C.sub.1-C.sub.6)-alkylthio, cyano, or R.sup.a and R.sup.b or R.sup.c and R.sup.d or R.sup.e and R.sup.f together represent an oxo or a thiooxo group, n represents 0, 1 or 2.

11. The compound as claimed in claim 10, wherein L represents chlorine, methoxy, ethoxy, hydroxy, X.sup.1, X.sup.2 represent O or S(O).sub.n, in which X.sup.1 and X.sup.2 are not simultaneously O or S(O).sub.n, R represents trifluoromethyl, difluoromethyl or pentafluoroethyl, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e, R.sup.f independently of one another each represent hydrogen, fluorine, chlorine, hydroxy, methyl, ethyl, trifluoromethyl, difluoromethyl, methyoxy, ethoxy, methylthio, ethylthio, cyano, or R.sup.a and R.sup.b or R.sup.c and R.sup.d or R.sup.e and R.sup.f together represent an oxo or a thiooxo group, n represents 0, 1 or 2.

Description

A. CHEMICAL EXAMPLES

Example 2-13: Synthesis of 6-(trifluoromethyl)-3,4-dihydro-2H-1,5-benzoxathiepine-N-(1-methyltetrazol-5-yl)-8-carboxamide

[0398] ##STR00029##

[0399] 96 mg (0.75 mmol) of oxalyl chloride are added dropwise to 150 mg (0.52 mmol, purity: 96%) of 6-(trifluoromethyl)-3,4-dihydro-2H-1,5-benzoxathiepine-9-carboxylic acid, 71 mg (0.7 mmol) of 5-amino-1-methyltetrazole and .42 ml (5.2 mmol) of pyridine in 1 ml of acetonitrile. After 24 hours at room temperature (RT), water and 2N hydrochloric acid are added and the mixture is diluted with ethyl acetate. The organic phase is washed with sat. sodium chloride solution, dried and substantially concentrated and the residue obtained is washed with heptane/ethyl acetate (1/1). Yield 96 mg.

Intermediate 2-13A: Synthesis of 6-(trifluoromethyl)-3,4-dihydro-2H-1,5-benozoxathiepine-9-carboxylic acid

[0400] A mixture of 800 mg (2.4 mmol, purity 80%) of ethyl 2-hydroxy-3-mercapto-4-(trifluoromethyl)benzoate, 1.7 ml (7.2 mmol) of tributylamine and 0.73 g (3.6 mmol) of 1,3-dibromopropane in 5 ml of acetonitrile is stirred at 70 C. for 3 h. 15 g of 10% strength aqueous sodium hydroxide solution are then added and the mixture is stirred at 50 C. for 3 h. The mixture is then concentrated and acidified with hydrochloric acid and the resulting solid is filtered off with suction and washed with water. Yield 0.69 g (purity: 80%).

[0401] The NMR data of disclosed examples are listed either in conventional form (6 values, number of hydrogen atoms, multiplet splitting) or as so-called NMR peak lists. In the NMR peak list method, the NMR data of selected examples are recorded in the form of NMR peak lists, where for each signal peak first the 6 value in ppm and then, separated by a space, the signal intensity are listed. The 6 value/signal intensity number pairs for different signal peaks are listed with separation from one another by semicolons.

[0402] The peak list for one example therefore takes the form of:

[0403] .sub.1 (intensity.sub.1); .sub.2 (intensity.sub.2); . . . ; .sub.i (intensity.sub.i); . . . ; .sub.n (intensity.sub.n)

[0404] The intensity of sharp signals correlates with the height of the signals in a printed example of an NMR spectrum in cm and shows the true ratios of the signal intensities. In the case of broad signals, several peaks or the middle of the signal and the relative intensity thereof may be shown in comparison to the most intense signal in the spectrum.

[0405] Calibration of the chemical shift of .sup.1H NMR spectra is accomplished using tetramethylsilane and/or the chemical shift of the solvent, particularly in the case of spectra which are measured in DMSO. Therefore, the tetramethylsilane peak may but need not occur in NMR peak lists.

[0406] The lists of the .sup.1H NMR peaks are similar to the conventional .sup.1H NMR printouts and thus usually contain all peaks listed in a conventional NMR interpretation.

[0407] In addition, like conventional .sup.1H NMR printouts, they may show solvent signals, signals of stereoisomers of the target compounds which are likewise provided by the invention, and/or peaks of impurities.

[0408] In the reporting of compound signals within the delta range of solvents and/or water, our lists of .sup.1H NMR peaks show the standard solvent peaks, for example peaks of DMSO in DMSO-D.sub.6 and the peak of water, which usually have a high intensity on average.

[0409] Such stereoisomers and/or impurities may be typical of the particular preparation process. Their peaks can thus help in identifying reproduction of our preparation process with reference to by-product fingerprints.

[0410] An expert calculating the peaks of the target compounds by known methods (MestreC, ACD simulation, but also with empirically evaluated expected values) can, if required, isolate the peaks of the target compounds, optionally using additional intensity filters. This isolation would be similar to the relevant peak picking in conventional 1H NMR interpretation.

[0411] Further details of .sup.1H NMR peak lists can be found in the Research Disclosure Database Number 564025.

[0412] Analytical Data (Conventional Evaluation)

TABLE-US-00008 No. NMR 2-5 .sup.1H-NMR(400.0 MHz, DMSO-d.sub.6): = 11.72 (br s, 1H); 7.89 (d, 1H); 7.73 (d, 1H); 4.04 (s, 3H); 2.95-2.80 (m, 4H); 2.35-2.25 (m, 2H) 2-11 .sup.1H-NMR(400.0 MHz, DMSO-d.sub.6): = 12.04 (br s, 1H); 8.49 (d, 1H); 8.28 (d, 1H); 4.04 (br s, 4H): 3.92 (s, 3H); 2.46 (br s, 2H) 2-13 .sup.1H-NMR(400.0 MHz, DMSO-d.sub.6): =11.55 (br s, 1H); 7.72 (d, 1H); 7.64 (d, 1H); 4.24 (m, 2H); 3.98 (s, 3H); 3.00 (m, 2H); 2.22 (m, 2H) 2-16 .sup.1H-NMR(400.0 MHz, DMSO-d.sub.6): = 11.64 (br s, 1H); 8.01 (d, 1H); 7.77 (d, 1H); 4.64 (m, 1H); 4.17 (m, 1H): 3.99 (s, 3H); 3.63 (m, 1H); 3.11 (m, 1H); 2.81 (m, 1H); 2.19 (m, 1H) 2-19 .sup.1H-NMR(400.0 MHz, DMSO-d.sub.6): = 11.72 (br s, 1H); 8.12 (d, 1H); 7.92 (d, 1H); 4.39 (m, 2H); 3.99 (s, 3H); 3.80 (m, 2H); 2.29 (m, 2H) 2-76 .sup.1H-NMR(400.0 MHz, DMSO-d.sub.6): = 8.05 (d, 1H); 7.88 (d, 1H); 4.06 (s, 3H); 3.50-3.05 (m, 4H); 2.35-2.10 (m, 2H) 5-64 .sup.1H-NMR(400.0 MHz, CDC1.sub.3): = 7.68 (d, 1H); 7.43 (dd, 1H); 3.95 (s, 3H); 2.85 (br s, 4H); 2.32 (m, 2H) 6-1 .sup.1H-NMR(400.0 MHz, DMSO-d.sub.6): = 13.41 (br s, 1H); 7.66 (d, 1H); 7.56 (d, 1H); 4.13 (m, 2H); 2.94 (m, 2H); 2.19 (m, 2H) 6-64 .sup.1H-NMR(400.0 MHz, CDCl.sub.3): = 7.90 (dd, 1H); 7.76 (d, 1H); 2.98-2.83 (m, 4H); 2.35 (m, 2H)

B. FORMULATION EXAMPLES

[0413] 1. Dusting Products

[0414] A dusting product is obtained by mixing 10 parts by weight of a compound of the formula (I) and 90% parts by weight of talc as an inert substance and comminuting the mixture in a hammer mill.

[0415] 2. Dispersible Powder

[0416] A readily water-dispersible wettable powder is obtained by mixing 25 parts by weight of a compound of the formula (I), 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.

[0417] 3. Dispersion Concentrate

[0418] A readily water-dispersible dispersion concentrate is obtained by mixing 20 parts by weight of a compound of the formula (I), 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 more than 277 C.) and grinding the mixture in a friction ball mill to a fineness of below 5 microns.

[0419] 4. Emulsifiable Concentrate

[0420] An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I), 75 parts by weight of cyclohexanone as a solvent and 10 parts by weight of ethoxylated nonylphenol as an emulsifier.

[0421] 5. Water-Dispersible Granules

[0422] Water-dispersible granules are obtained by mixing

TABLE-US-00009 75 parts by weight of a compound of the formula (I), 10 of calcium lignosulfonate, 5 of sodium laurylsulfate, 3 of polyvinyl alcohol and 7 of kaolin,

[0423] 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.

[0424] Water-dispersible granules are also obtained by homogenizing and precomminuting, in a colloid mill,

TABLE-US-00010 25 parts by weight of a compound of the formula (I), 5 of sodium 2,2-dinaphthylmethane-6,6-disulfonate, 2 of sodium oleoylmethyltaurinate, 1 of polyvinyl alcohol, 17 of calcium carbonate and 50 of water,

[0425] then grinding the mixture in a bead mill and atomizing and drying the suspension thus obtained in a spray tower by means of a one-phase nozzle.

C. BIOLOGICAL EXAMPLES

[0426] Test Description

[0427] In the tables below, the following abbreviations are used:

[0428] Undesired Plants/Weeds:

TABLE-US-00011 ABUTH: Abutilon theophrasti AMARE: Amaranthus retroflexus ALOMY Alopecurus myosuroides AVEFA: Avena fatua CYPES: Cyperus esculentus ECHCG: Echinochloa crus-galli LOLMU: Lolium multiflorum MATIN: Matricaria inodora PHBPU: Ipomoea purpurea POLCO: Polygonum convolvulus SETVI: Setaria viridis STEME: Stellaria media VERPE: Veronica persica VIOTR: Viola tricolor

[0429] 1. Pre-Emergence Herbicidal Action and Crop Plant Compatibility

[0430] Seeds of monocotyledonous and dicotyledonous weed plants and crop plants are placed in plastic or organic planting 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 onto the surface of the covering soil as aqueous suspension or emulsion with addition of 0.5% additive at a water application rate of 6001/ha (converted). After the treatment, the pots are placed in a greenhouse and kept under good growth conditions for the trial plants. After about 3 weeks, the effect of the preparations is scored visually in comparison with untreated controls as percentages. The tables below show the herbicidal activity of numerous compounds according to the invention against important harmful plants. For example, 100% activity=the plants have died, 0% activity=like control plants.

PE

[0431]

TABLE-US-00012 Example Application number rate AVEFA CYPES ECHCG SETVI ABUTH AMARE MATIN PHBPU POLCO STEME VIOTR VERPE 2-13 320 100 90 100 100 100 100 100 100 100 100 100 100 2-16 320 80 100 100 100 100 100 100 80 80 100 100 100 2-19 320 80 100 100 100 100 100 100 100 90 100 100 100

PE

[0432]

TABLE-US-00013 Example Application number rate AVEFA CYPES ECHCG SETVI ABUTH AMARE MATIN PHBPU POLCO STEME VIOTR VERPE 2-5 80 100 100 100 100 100 100 100 2-76 80 90 90

[0433] In a comparative experiment, by way of example, the herbicidal activity of compound No. 2-13 according to the invention was compared to that of compound No. A-117 known from WO 2013/076315 A2. Here, the superiority of the compound according to the invention was demonstrated clearly on the basis of numerous harmful plants:

TABLE-US-00014 Dosage Herbicidal action against Example No. [g/ha] SETVI ALOMY AVEFA ABUTH MATIN 2-13 320 100% 100% 100% 100% 1000% A-117 320 0% 0% 0% 0% 30%

[0434] 2. Post-Emergence Herbicidal Action and Crop Plant Compatibility

[0435] Seeds of monocotyledonous and dicotyledonous weeds and crop plants are placed in sandy loam in plastic or organic planting pots, covered with soil and cultivated in a greenhouse under controlled 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 as aqueous suspension or emulsion with addition of 0.5% additive at a water application rate of 6001/ha (converted). After the test plants had been kept in the greenhouse under optimum growth conditions for about 3 weeks, the activity of the preparations is rated visually in comparison to untreated controls. The tables below show the herbicidal activity of numerous compounds according to the invention against important harmful plants. For example, 100% activity=the plants have died, 0% activity=like control plants.

PO

[0436]

TABLE-US-00015 Example Application number rate ECHCG SETVI ABUTH AMARE MATIN STEME VIOTR VERPE 2-13 80 100 100 100 100 80 100 100 100 2-16 80 100 90 100 100 100 100 100 90 2-19 80 100 90 100 100 90 100 100 100

PO

[0437]

TABLE-US-00016 Example Application number rate ECHCG SETVI ABUTH AMARE MATIN STEME VIOTR VERPE 2-5 20 90 90 90 80 2-76 20 90 80

[0438] In a comparative experiment, by way of example, the herbicidal activity of compound No. 2-13 according to the invention was compared to that of compound No. A-117 known from WO 2013/076315 A2. Here, the superiority of the compound according to the invention was demonstrated clearly on the basis of numerous harmful plants.

TABLE-US-00017 Dosage Herbicidal action against Example No. [g/ha] PHPBU ALOMY AVEFA ABUTH POLCO 2-13 80 90% 90% 1000% 100% 80% A-117 80 30% 20% 0% 50% 10%