2-(HETERO)ARYLPYRIDAZINONES AND THEIR USE AS HERBICIDES

Abstract

2-(Hetero)arylpyradazinones of the general formula (I) are described as herbicides.

##STR00001##

In this formula (I), R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are each radicals such as hydrogen, organic radicals such as alkyl, and other radicals such as halogen. X.sup.1, X.sup.2 and X.sup.3 represent nitrogen or an optionally substituted carbon atom.

Claims

1. A 2-(hetero)arylpyridazinone of formula (I) or a salt thereof ##STR00012## in which R.sup.1 represents hydrogen, halogen, cyano (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.2-C.sub.6)-alkenyl, (C.sub.4-C.sub.6)-cycloalkenyl, (C.sub.2-C.sub.6)-alkynyl, halo-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.6)-alkoxy-(C.sub.2-C.sub.6)-alkoxy, (C.sub.1-C.sub.6)-alkoxy-(C.sub.2-C.sub.6)-alkoxy-(C.sub.1-C.sub.3)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl-(C.sub.1-C.sub.3)-alkyl, amino, (C.sub.1-C.sub.6)-alkylamino, di-(C.sub.1-C.sub.6)-alkylamino, (C.sub.1-C.sub.3)-alkyl-(O)C-amino-(C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.6)-alkyl-(O).sub.nS, (C.sub.1-C.sub.6)-alkyl-(O).sub.nS(C.sub.1-C.sub.3)-alkyl, halo-(C.sub.1-C.sub.6)-alkyl-(O).sub.nS or halo-(C.sub.1-C.sub.6)-alkyl-(O).sub.nS(C.sub.1-C.sub.3)-alkyl; R.sup.2 represents hydrogen, hydroxy, halogen, nitro, amino, cyano, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.3)-alkoxy, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.2-C.sub.6)-alkenyl, (C.sub.2-C.sub.6)-alkynyl, halo-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.3)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl-(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.6)-alkyl-(O).sub.nS, (C.sub.1-C.sub.6)-alkyl-(O).sub.nS(C.sub.1-C.sub.3)-alkyl, halo-(C.sub.1-C.sub.6)-alkyl-(O).sub.nS, halo-(C.sub.1-C.sub.6)-alkyl-(O).sub.nS(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-alkylamino or di-(C.sub.1-C.sub.3)-alkylamino; R.sup.3 represents hydrogen, (C.sub.1-C.sub.6)-alkyl-(O)C, aryl-(O)C, (C.sub.1-C.sub.6)-alkoxy-(O)C, (C.sub.1-C.sub.6)-alkyl-(O).sub.nS, (C.sub.1-C.sub.6)-alkyl-(O).sub.nS(O)C or aryl-(O).sub.nS, where the aryl groups are in each case substituted by s radicals R.sup.9; R.sup.4 represents hydroxy, halogen, cyano, nitro, (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, halo-(C.sub.1-C.sub.6)-alkyl, (C.sub.2-C.sub.6)-alkenyl, halo-(C.sub.2-C.sub.6)-alkenyl, (C.sub.2-C.sub.6)-alkynyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.2-C.sub.6)-alkenyloxy, (C.sub.3-C.sub.6)-cycloalkyl-(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.6)-alkoxy-(C.sub.2-C.sub.6)-alkoxy, (C.sub.1-C.sub.6)-alkoxy-(C.sub.2-C.sub.6)-alkoxy-(C.sub.1-C.sub.3)-alkyl, halo-(C.sub.1-C.sub.6)-alkoxy, halo-(C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.6)-alkyl-(O).sub.nS, halo-(C.sub.1-C.sub.6)-alkyl-(O).sub.nS, aryl, aryl-(O).sub.nS, heterocyclyl, heterocyclyl-(O).sub.nS, aryloxy, aryl-(C.sub.2-C.sub.6)-alkyl, aryl-(C.sub.1-C.sub.6)-alkoxy, heterocyclyloxy, heterocyclyl-(C.sub.1-C.sub.3)-alkoxy-(C.sub.1-C.sub.3)-alkyl, HO(O)C, HO(O)C(C.sub.1-C.sub.3)-alkoxy, (C.sub.1-C.sub.3)-alkoxy-(O)C, (C.sub.1-C.sub.3)-alkoxy-(O)C(C.sub.1-C.sub.3)-alkoxy, (C.sub.1-C.sub.3)-alkylamino, di-(C.sub.1-C.sub.3)-alkylamino, (C.sub.1-C.sub.3)-alkylamino-(O).sub.nS, (C.sub.1-C.sub.3)-alkylamino-(O).sub.nS(C.sub.1-C.sub.3)-alkyl, di-(C.sub.1-C.sub.3)-alkylamino-(O).sub.nS, di-(C.sub.1-C.sub.3)-alkylamino-(O).sub.nS(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-alkylamino-(O)C, (C.sub.1-C.sub.3)-alkylamino-(O)C(C.sub.1-C.sub.3)-alkyl, di-(C.sub.1-C.sub.3)-alkylamino-(O)C, di-(C.sub.1-C.sub.3)-alkylamino-(O)C(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-alkyl-(O)C-amino, (C.sub.1-C.sub.3)-alkyl-(O).sub.nS-amino, (C.sub.1-C.sub.3)-alkyl-(O).sub.nS(C.sub.1-C.sub.3)-alkylamino or (C.sub.1-C.sub.3)-alkyl-(O).sub.nS-amino-(C.sub.1-C.sub.3)-alkyl, where the heterocyclyl groups and aryl groups are substituted by s radicals from the group consisting of (C.sub.1-C.sub.3)-alkyl, halo-(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-alkoxy, halo-(C.sub.1-C.sub.3)-alkoxy, phenyl, cyano, nitro and halogen; A represents a direct bond or (C.sub.1-C.sub.4)-alkylene, where the methylene groups in (C.sub.1-C.sub.4)-alkylene independently of one another may carry n radicals from the group consisting of halogen, (C.sub.1-C.sub.4)-alkyl, halo-(C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, halo-(C.sub.1-C.sub.4)-alkoxy or (C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.4)-alkyl; R.sup.5 represents (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)-alkoxy-(C.sub.1-C.sub.6)-alkyl; X.sup.1 represents N or CR.sup.6; X.sup.2 represents N or CR.sup.7; X.sup.3 represents N or CR.sup.8; R.sup.6 represents hydrogen, halogen, (C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-alkoxy, (C.sub.2-C.sub.3)-alkenyl, (C.sub.2-C.sub.3)-alkynyl, halo-(C.sub.1-C.sub.3)-alkyl, halo-(C.sub.1-C.sub.3)-alkoxy; R.sup.7 represents hydrogen, halogen, (C.sub.1-C.sub.3)-alkyl; R.sup.8 represents hydrogen, hydroxy, halogen, cyano, nitro, (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, halo-(C.sub.1-C.sub.6)-alkyl, (C.sub.2-C.sub.6)-alkenyl, halo-(C.sub.2-C.sub.6)-alkenyl, (C.sub.2-C.sub.6)-alkynyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.2-C.sub.6)-alkenyloxy, (C.sub.3-C.sub.6)-cycloalkyl-(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.6)-alkoxy-(C.sub.2-C.sub.6)-alkoxy, (C.sub.1-C.sub.6)-alkoxy-(C.sub.2-C.sub.6)-alkoxy-(C.sub.1-C.sub.3)-alkyl, halo-(C.sub.1-C.sub.6)-alkoxy, halo-(C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.6)-alkyl-(O).sub.nS, halo-(C.sub.1-C.sub.6)-alkyl-(O).sub.nS, aryl, aryl-(O).sub.nS, heterocyclyl, heterocyclyl-(O).sub.nS, aryloxy, aryl-(C.sub.2-C.sub.6)-alkyl, aryl-(C.sub.1-C.sub.6)-alkoxy, heterocyclyloxy, heterocyclyl-(C.sub.1-C.sub.3)-alkoxy-(C.sub.1-C.sub.3)-alkyl, HO(O)C, HO(O)C(C.sub.1-C.sub.3)-alkoxy, (C.sub.1-C.sub.3)-alkoxy-(O)C, (C.sub.1-C.sub.3)-alkoxy-(O)C(C.sub.1-C.sub.3)-alkoxy, (C.sub.1-C.sub.3)-alkylamino, di-(C.sub.1-C.sub.3)-alkylamino, (C.sub.1-C.sub.3)-alkylamino-(O).sub.nS, (C.sub.1-C.sub.3)-alkylamino-(O).sub.nS(C.sub.1-C.sub.3)-alkyl, di-(C.sub.1C)-alkylamino-(O).sub.nS, di-(C.sub.1-C.sub.3)-alkylamino-(O).sub.nS(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-alkylamino-(O)C, (C.sub.1-C.sub.3)-alkylamino-(O)C(C.sub.1-C.sub.3)-alkyl, di-(C.sub.1-C.sub.3)-alkylamino-(O)C, di-(C.sub.1-C.sub.3)-alkylamino-(O)C(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-alkyl-(O)C-amino, (C.sub.1-C.sub.3)-alkyl-(O).sub.nS-amino, (C.sub.1-C.sub.3)-alkyl-(O).sub.nS(C.sub.1-C.sub.3)-alkylamino or (C.sub.1-C.sub.3)-alkyl-(O).sub.nS-amino-(C.sub.1-C.sub.3)-alkyl, where the heterocyclyl groups and aryl groups are substituted by s radicals from the group consisting of (C.sub.1-C.sub.3)-alkyl, halo-(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-alkoxy, halo-(C.sub.1-C.sub.3)-alkoxy, (C.sub.1-C.sub.6)-alkyl-(O).sub.nS, phenyl, cyano, nitro and halogen, or R.sup.7 and R.sup.8 together with the carbon atoms to which they are attached represent an unsaturated five- or six-membered ring which contains s nitrogen atoms and is substituted by s radicals R.sup.10; R.sup.9 represents halogen, (C.sub.1-C.sub.3)-alkyl, halo-(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.6)-alkoxy, R.sup.10 represents cyano, halogen, (C.sub.1-C.sub.3)-alkyl-(O).sub.nS, (C.sub.1-C.sub.3)-alkyl, (C.sub.2-C.sub.3)-alkenyl, (C.sub.2-C.sub.3)-alkynyl, halo-(C.sub.1-C.sub.3)-alkyl or morpholinyl; n represents 0, 1 or 2; s represents 0, 1, 2 or 3, with the proviso that R.sup.5 does not represent (C.sub.1-C.sub.6)-alkyl if A represents a direct bond.

2. The 2-(hetero)arylpyridazinone or salt as claimed in claim 1 in which R.sup.1 represents hydrogen, halogen, cyano, (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, (C.sub.2-C.sub.6)-alkenyl, (C.sub.2-C.sub.6)-alkynyl, halo-(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.3)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl-(C.sub.1-C.sub.3)-alkyl, amino or (C.sub.1-C.sub.6)-alkyl-(O).sub.nS; R.sup.2 represents hydrogen, halogen, cyano, (C.sub.1-C.sub.6)-alkyl, (C.sub.2-C.sub.6)-alkenyl, (C.sub.2-C.sub.6)-alkynyl, halo-(C.sub.1-C.sub.6)-alkyl or (C.sub.1-C.sub.6)-alkyl-(O).sub.nS; R.sup.3 represents hydrogen, R.sup.4 represents hydroxy, halogen, cyano, nitro, (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, halo-(C.sub.1-C.sub.6)-alkyl, (C.sub.2-C.sub.6)-alkenyl, (C.sub.2-C.sub.6)-alkynyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.6)-alkoxy-(C.sub.2-C.sub.6)-alkoxy, (C.sub.1-C.sub.6)-alkoxy-(C.sub.2-C.sub.6)-alkoxy-(C.sub.1-C.sub.3)-alkyl, halo-(C.sub.1-C.sub.6)-alkoxy, halo-(C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.6)-alkyl-(O)S, halo-(C.sub.1-C.sub.6)-alkyl-(O).sub.nS, aryl, heterocyclyl, aryloxy, heterocyclyl-(C.sub.1-C.sub.3)-alkoxy-(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-alkylamino, di-(C.sub.1-C.sub.3)-alkylamino, (C.sub.1-C.sub.3)-alkylamino-(O).sub.nS, (C.sub.1-C.sub.3)-alkylamino-(O).sub.nS(C.sub.1-C.sub.3)-alkyl, di-(C.sub.1-C.sub.3)-alkylamino-(O).sub.nS, di-(C.sub.1-C.sub.3)-alkylamino-(O).sub.nS(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-alkylamino-(O)C, di-(C.sub.1-C.sub.3)-alkylamino-(O)C, di-(C.sub.1-C.sub.3)-alkylamino-(O)C(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-alkyl-(O)C-amino or (C.sub.1-C.sub.3)-alkyl-(O).sub.nS-amino, where the heterocyclyl groups and aryl groups are substituted by s radicals from the group consisting of (C.sub.1-C.sub.3)-alkyl, halo-(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-alkoxy, halo-(C.sub.1-C.sub.3)-alkoxy, cyano, nitro and halogen; A represents a direct bond or (C.sub.1-C.sub.4)-alkylene; R.sup.5 represents (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)-alkoxy-(C.sub.1-C.sub.6)-alkyl; X.sup.1 represents CR.sup.6; X.sup.2 represents CR.sup.7; X.sup.3 represents CR.sup.8; R.sup.6 and R.sup.7 independently of one another represent hydrogen, halogen, or (C.sub.1-C.sub.3)-alkyl; R.sup.8 represents hydrogen, halogen, nitro, (C.sub.1-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl, halo-(C.sub.1-C.sub.6)-alkyl, (C.sub.2-C.sub.6)-alkenyl, halo-(C.sub.2-C.sub.6)-alkenyl, (C.sub.2-C.sub.6)-alkynyl, (C.sub.1-C.sub.6)-alkoxy, (C.sub.2-C.sub.6)-alkenyloxy, (C.sub.3-C.sub.6)-cycloalkyl-(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.6)-alkoxy-(C.sub.2-C.sub.6)-alkoxy, halo-(C.sub.1-C.sub.6)-alkoxy, (C.sub.1-C.sub.6)-alkyl-(O).sub.nS or phenyl, where the phenyl group is substituted by s radicals from the group consisting of (C.sub.1-C.sub.3)-alkyl, halo-(C.sub.1-C.sub.3)-alkyl, (C.sub.1-C.sub.3)-alkoxy, halo-(C.sub.1-C.sub.3)-alkoxy, (C.sub.1-C.sub.6)-alkyl-(O).sub.nS, phenyl, cyano, nitro and halogen; n represents 0, 1 or 2; s represents 0, 1, 2 or 3.

3. The 2-(hetero)arylpyridazinone or salt as claimed in claim 1 in which R.sup.1 represents hydrogen, amino, chlorine, bromine, cyano, methyl, ethyl, isopropyl, cyclopropyl, vinyl, propargyl, isopropenyl or methyl-(O).sub.nS; R.sup.2 represents hydrogen, halogen or (C.sub.1-C.sub.6)-alkyl, R.sup.3 represents hydrogen, R.sup.4 represents fluorine, chlorine, cyano, nitro, methyl, trifluoromethyl, 2-fluoroethyl, methoxyethoxymethyl, trifluoromethoxymethyl, methyl-(O).sub.nS, aryl, isoxazolinyl, morpholinyl or methyl-(O).sub.nS-amino, where the heterocyclyl groups and aryl groups are substituted by s radicals from the group consisting of methyl, trifluoromethyl and chlorine; A represents a direct bond or (C.sub.1-C.sub.4)-alkylene; R.sup.5 represents (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)-alkoxy-(C.sub.1-C.sub.6)-alkyl; X.sup.1 represents CR.sup.6; X.sup.2 represents CR.sup.7; X.sup.3 represents CR.sup.8; R.sup.6 and R.sup.7 represent hydrogen; R.sup.8 represents hydrogen, halogen, (C.sub.1-C.sub.6)-alkyl, halo-(C.sub.1-C.sub.6)-alkyl, (C.sub.2-C.sub.6)-alkenyl, (C.sub.2-C.sub.6)-alkynyl or (C.sub.1-C.sub.6)-alkyl-(O).sub.nS; n represents 0, 1 or 2; s represents 0, 1, 2 or 3.

4. The 2-(hetero)arylpyridazinone or salt as claimed in claim 1 in which R.sup.1 represents methyl or vinyl; R.sup.2 represents hydrogen; R.sup.3 represents hydrogen; R.sup.4 represents methyl, chlorine, trifluoromethyl or methyl-(O).sub.nS; A represents a direct bond, CH.sub.2 or CH.sub.2CH.sub.2; R.sup.5 represents methyl, ethyl, cyclopropyl, cyclopropylmethyl, methoxyethyl; X.sup.1 represents CR.sup.6; X.sup.2 represents CR.sup.7; X.sup.3 represents CR.sup.8; R.sup.6 and R.sup.7 represent hydrogen, R.sup.8 represents methyl, ethyl, chlorine, trifluoromethyl or methyl-(O).sub.nS; n represents 0, 1 or 2.

5. A herbicidal composition comprising a herbicidally active content of at least one compound of the formula (I) or salt as claimed in claim 1.

6. The herbicidal composition as claimed in claim 5 in a mixture with one or more formulation auxiliaries.

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

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

9. A product comprising a compound of the formula (I) or salt as claimed in claim 1 or herbicidal composition thereof adapted for controlling one or more unwanted plants.

10. The product as claimed in claim 9, wherein the compound of the formula (I) or salt is used for controlling unwanted plants in one or more crops of one or more useful plants.

11. The product as claimed in claim 10, wherein the useful plants are transgenic useful plants.

Description

A. CHEMICAL EXAMPLES

Preparation of 5-chloro-2-{3-[(cyclopropylmethyl)sulfanyl]-2-methyl-4-(trifluoromethyl)phenyl}-4-hydroxypyridazin-3(2H)-one (Example No. 1-499)

Step 1: Synthesis of 6-bromo-2-fluoro-3-(trifluoromethyl)benzaldehyde

[0081] At 78 C., 181.07 ml of a 2.5M (452.7 mmol) solution of n-butyllithium were added dropwise to a solution of 63.9 g (452.7 mmol) of 2,2,6,6-tetramethylpiperidine in 833 ml of dry THF. The mixture was stirred at this temperature for 30 min. 100.0 g (411.5 mmol) of 4-bromo-2-fluoro-1-(trifluoromethyl)benzene were then added dropwise at 78 C. The mixture was stirred at this temperature for 2 h. 33.1 g (452.7 mmol) of DMF were then added dropwise at 78 C. The reaction mixture was then stirred for 2 h. For work-up, 300 ml of water were added to the contents. The mixture was extracted three times with in each case 200 ml of dichloromethane. The combined organic phases were washed with 300 ml of 1M hydrochloric acid and then with 300 ml of a saturated aqueous sodium chloride solution. The organic phase was dried and the filtrate was freed of the solvent. 96.2 g of the desired product were obtained.

Step 2: Synthesis of 6-bromo-2-(tert-butylsulfanyl)-3-(trifluoromethyl)benzaldehyde

[0082] At 0 C., 30.3 g (335.8 mmol) of tert-butylmercaptan were added to a solution of 65.0 g (239.8 mmol) of 6-bromo-2-fluoro-3-(trifluoromethyl)benzaldehyde and 66.3 g (479.7 mmol) of potassium carbonate in 500 ml of N,N-dimethylformamide. The mixture was stirred at this temperature for 12 h. Subsequently, 15.6 g (48.0 mmol) of cesium carbonate were added and the mixture was stirred for a further 3 h. For work-up, 1 I of water was added to the contents. The mixture was extracted three times with in each case 300 ml of dichloromethane. The combined organic phases were washed four times with in each case 300 ml of a saturated aqueous sodium chloride solution. The organic phase was dried and the filtrate was freed of the solvent, giving 68 g of the desired product.

Step 3: Synthesis of [6-bromo-2-(tert-butylsulfanyl)-3-(trifluoromethyl)phenyl]methanol

[0083] At 10 C., 3.49 g (92.3 mmol) of sodium borohydride were added slowly to a solution of 63.0 g (184.7 mmol) of 6-bromo-2-(tert-butylsulfanyl)-3-(trifluoromethyl)benzaldehyde in 500 ml of methanol. After the reaction had been checked showing complete conversion, 3M hydrochloric acid was added to work-up the contents. The mixture was concentrated and the residue was poured onto 400 ml of water. The mixture was extracted twice with in each case 300 ml of dichloromethane. The combined organic phases were washed with a saturated aqueous sodium chloride solution and dried, and the filtrate was then freed of the solvent. 60.0 g of the desired product were obtained.

Step 4: Synthesis of 6-bromo-2-(tert-butylsulfanyl)-3-(trifluoromethyl)benzyl methanesulfonate

[0084] At 0 C., 31.3 g (272.8 mmol) of methanesulfonyl chloride were added dropwise to a solution of 60.0 g (174.8 mmol) of [6-bromo-2-(tert-butylsulfanyl)-3-(trifluoromethyl)phenyl]methanol and 44.2 g (437.1 mmol) of triethylamine in 500 ml of dichloromethane. After the reaction had been checked showing complete conversion, the solution was, for work-up, washed twice with in each case 300 ml of water and dried, and the filtrate was freed of the solvent. 70.0 g of the desired product were obtained.

Step 5: Synthesis of 1-bromo-3-(tert-butylsulfanyl)-2-methyl-4-(trifluoromethyl)benzene

[0085] At 10 C., a solution of 70.0 g (166.2 mmol) of 6-bromo-2-(tert-butylsulfanyl)-3-(trifluoromethyl)benzyl methanesulfonate in 100 ml of dry THF was added dropwise to a solution of 6.94 g (182.8 mmol) of lithium aluminum hydride in 500 ml of dry THF. The content was stirred for 1 h. For work-up, sodium sulfate decahydrate was added until no more evolution of gas could be observed. The mixture was filtered and the filtrate was dried. The filtrate was then freed of the solvent and the residue was purified chromatographically, giving 45.0 g of the desired product.

Step 6: Synthesis of 3-bromo-2-methyl-6-(trifluoromethyl)benzenethiol

[0086] 23.7 g (137.5 mmol) of 4-methylbenzenesulfonic acid were added to a solution of 45.0 g (137.5 mmol) of 1-bromo-3-(tert-butylsulfanyl)-2-methyl-4-(trifluoromethyl)benzene in 175 ml of toluene. The mixture was heated under reflux for 2 h. The solvent was removed on a rotary evaporator and the residue was dissolved in 200 ml of dichloromethane. The solution was extracted four times with 15% strength aqueous potassium hydroxide solution. The combined aqueous phases were acidified with concentrated hydrochloric acid and the product was then extracted with dichloromethane. The organic phase was dried and filtered and the filtrate was freed of the solvent, giving 32.0 g of the desired product.

Step 7: Synthesis of 1-bromo-3-[(cyclopropylmethyl)sulfanyl]-2-methyl-4-(trifluoromethyl)benzene

[0087] 14.0 g (103.6 mmol) of (bromomethyl)cyclopropane were added to a mixture of 20 g (74.1 mmol) of 3-bromo-2-methyl-6-(trifluoromethyl)benzenethiol and 36 g (111.1 mmol) of cesium carbonate in 80 ml of acetonitrile. The content was stirred at 80 C. for 2 h. For work-up, the mixture was filtered and the filtrate was freed from the solvent. The residue was purified chromatographically, which gave 20.0 g of the desired product.

Step 8: Synthesis of 1-{3-[(cyclopropylmethyl)sulfanyl]-2-methyl-4-(trifluoromethyl)phenyl}-2-(diphenylmethylene)hydrazine

[0088] A mixture of 20 mg (0.2 mmol) of sodium tert-butoxide and 33 mg (0.17 mmol) of benzophenone hydrazine was added to a solution of 50 mg (0.15 mmol) of 1-bromo-3-[(cyclopropylmethyl)sulfanyl]-2-methyl-4-(trifluoromethyl)benzene in 1 ml of toluene. To remove oxygen, the mixture was then degassed for 10 min. Subsequently, 1 mg (0.002 mmol) of 2,2-bis(diphenylphosphino)-1,1-binaphthyl was added under protective gas. To remove oxygen, the mixture was degassed for 15 min. Subsequently, 0.22 mg (0.001 mmol) of palladium(II) acetate was added under protective gas. Under protective gas, the content was heated to a temperature of 90 C. for 3 h. Work-up and purification gave 35 mg of the desired product.

Step 9: Synthesis of {3-[(cyclopropylmethyl)sulfanyl]-2-methyl-4-(trifluoromethyl)-phenyl}hydrazine

[0089] A solution of 30 mg (0.11 mmol) of 1-{3-[(cyclopropylmethyl)sulfanyl]-2-methyl-4-(trifluoromethyl)phenyl}-2-(diphenylmethylene)hydrazine in 2 ml of isopropyl alcohol and 2 ml of concentrated hydrochloric acid was stirred at room temperature for 48 h. Work-up and purification gave 10 mg of the desired product.

Step 10: Synthesis of 4,5-dichloro-2-{3-[(cyclopropylmethyl)sulfanyl]-2-methyl-4-(trifluoromethyl)phenyl}pyridazin-3(2H)-one

[0090] 34 mg (0.2 mmol, 1.1 eq) of 3,4-dichloro-5-hydroxyfuran-2(5H)-one were added to a solution of 50 mg (0.18 mmol) of {3-[(cyclopropylmethyl)sulfanyl]-2-methyl-4-(trifluoromethyl)phenyl}hydrazine in 1 ml of ethanol. The mixture was stirred at room temperature for 3 h. 1 ml of acetic acid was then added, and the mixture was heated under reflux for 3 h. Work-up and purification gave 40 mg of the desired product.

Step 11: Synthesis of 5-chloro-2-{3-[(cyclopropylmethyl)sulfanyl]-2-methyl-4-(trifluoromethyl)phenyl}-4-methoxypyridazin-3(2H)-one

[0091] 0.033 ml (20%, 0.12 mmol) of a solution of sodium methoxide in methanol was added to a solution of 50 mg (0.12 mmol) of 4,5-dichloro-2-{3-[(cyclopropylmethyl)sulfanyl]-2-methyl-4-(trifluoromethyl)phenyl}pyridazin-3(2H)-one in 2 ml of dry dioxane. At a temperature of 15 C., the mixture was diluted with 5 ml of dry dioxane. The reaction mixture was then stirred at a temperature of 15 C. for another 1 h. Work-up and purification gave 23 mg of the desired product.

Step 12: Synthesis of 5-chloro-2-{3-[(cyclopropylmethyl)sulfanyl]-2-methyl-4-(trifluoromethyl)phenyl}-4-hydroxypyridazin-3(2H)-one (Example No. 1-499)

[0092] At a temperature of 0 C., 18.6 mg (0.074 mmol) of boron tribromide, as a 1M solution in dichloromethane, were added to a solution of 10 mg (0.02 mmol) of 5-chloro-2-{3-[(cyclopropymethyl)sulfanyl]-2-methyl-4-(trifluoromethyl)phenyl}-4-methoxypyridazin-3(2H)-one in 1 ml of dichloromethane. The mixture was stirred at room temperature for 1 h. Work-up and purification gave 4 mg of the desired product.

[0093] NMR data of selected examples

[0094] NMR peak list method

[0095] The 1H NMR data of selected examples are stated in the form of 1H NMR peak lists. For each signal peak, first the 6 value in ppm and then the signal intensity in round brackets are listed. The pairs of 5 value-signal intensity numbers for different signal peaks are listed with separation from one another by semicolons.

[0096] The peak list for one example therefore has the form of:

.sub.1 (intensity.sub.1); .sub.2 (intensity.sub.2); . . . ; .sub.i (intensity.sub.i); . . . ; .sub.n (intensity.sub.n)

[0097] 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.

[0098] To calibrate the chemical shift of 1H NMR spectra, we used tetramethylsilane and/or the chemical shift of the solvent, in particular in the case of spectra measured in DMSO. Accordingly, the tetramethylsilane peak may be present in NMR peak lists, but it does not have to be.

[0099] The lists of the 1H NMR peaks are similar to the conventional .sup.1H-NMR printouts and thus usually contain all peaks listed in a conventional NMR interpretation.

[0100] In addition, like conventional 1H NMR printouts, they may show solvent signals, signals of stereoisomers of the target compounds which likewise form part of the subject matter of the invention, and/or peaks of impurities.

[0101] When stating compound signals in the delta range of solvents and/or water, in our lists of 1H NMR peaks, the usual solvent peaks, for example peaks of DMSO in DMSO-D.sub.6 and the peak of water are shown, which usually have on average a high intensity.

[0102] The peaks of stereoisomers of the target compounds and/or peaks of impurities usually have a lower intensity on average than the peaks of the target compounds (for example with a purity of >90%).

[0103] 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.

[0104] 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 peak picking in question in conventional 1H NMR interpretation.

[0105] Further details on 1H NMR peak lists are available from Research Disclosure Database Number 564025.

TABLE-US-00010 Example 1-499: .sup.1H NMP(400.0 MHz, CDCl.sub.3): = 7.910(11.2); 7.677(4.9); 7.656(4.8); 7.518(7.4); 7.380(1.2); 7.296(6.0); 7.290(4.4); 7.276(7.9); 7.259(1356.1); 7.226(2.8); 7.209(3.3); 7.140(1.7); 6.995(7.4); 3.731(3.6); 3.487(1.3); 2.629(2.7); 2.540(4.9); 2.314(2.0); 2.160(14.3); 1.679(2.9); 1.284(2.8); 1.254(16.0); 0.978(1.6); 0.877(3.9); 0.861(3.4); 0.503(2.6); 0.345(3.7); 0.146(3.3); 0.120(2.6); 0.008(16.4); 0.000(542.8); 0.009(21.4); 0.033(4.7); 0.150(2.3) Example 2-139: .sup.1H NMP(400.0 MHz, CDCl.sub.3): = 7.910(2.8); 7.783(2.2); 7.578(3.7); 7.518(5.6); 7.259(785.6); 6.995 (4.1); 3.878(4.5); 3.731(2.6); 2.887(1.5); 2.115(16.0); 2.003(6.0); 1.852 (4.2); 1.254(3.3); 0.146(1.4); 0.008(12.3); 0.000(389.1); 0.009 (13.9); 0.149(1.4)

B. FORMULATION EXAMPLES

[0106] 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. [0107] 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. [0108] c) A readily water-dispersible dispersion concentrate is obtained by mixing 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 ball mill to a fineness of below 5 microns. [0109] 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. [0110] e) Water-dispersible granules are obtained by mixing [0111] 75 parts by weight of a compound of the formula (I) and/or salts thereof, [0112] parts by weight of calcium lignosulfonate, [0113] parts by weight of sodium lauryl sulfate, [0114] 3 parts by weight of polyvinyl alcohol and [0115] 7 parts by weight of kaolin, [0116] 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. [0117] f) Water-dispersible granules are also obtained by homogenizing and precomminuting, in a colloid mill, [0118] parts by weight of a compound of the formula (I) and/or salts thereof, [0119] parts by weight of sodium 2,2-dinaphthylmethane-6,6-disulfonate [0120] 2 parts by weight of sodium oleoylmethyltaurate, [0121] 1 part by weight of polyvinyl alcohol [0122] 17 parts by weight of calcium carbonate and [0123] 50 parts by weight of water, [0124] 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

1. Pre-Emergence Herbicidal Action Against Harmful Plants

[0125] Seeds of monocotyledonous and dicotyledonous weed plants and crop plants are laid out in wood-fiber pots in sandy loam 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 equating to 600 to 800 I/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). Here, for example, the compounds Nos. 1-499 and 2-139 showed, at an application rate of 0.32 kg of active substance or less per hectare, very good activity (80% to 100% of herbicidal activity) against harmful plants such as Amaranthus retroflexus, Echinochloa crus-galli, Setaria viridis and Abutilon theophrasti. At the same time, the compounds according to the invention leave gramineous crops such as barley, wheat, rye, millet, corn or rice virtually undamaged even at high active compound dosages when applied by the pre-emergence method. In addition, some substances also spare dicotyledonous crops such as soybeans, cotton, oilseed rape, sugar beet or potatoes.

[0126] Some of the compounds according to the invention have high selectivity and are therefore suitable for controlling unwanted vegetation in agricultural crops by the pre-emergence method.

2. Post-Emergence Herbicidal Action Against Harmful Plants

[0127] Seeds of monocotyledonous and dicotyledonous weed and crop plants are laid out in sandy loam 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 equating to 600 to 800 I/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). Here, for example, the compounds Nos. 1-499 and 2-139 showed, at an application rate of 0.08 kg of active substance or less per hectare, very good herbicidal activity (80% to 100% herbicidal activity) against harmful plants such as Pharbitis purpureum, Echinochloa crus-galli, Setaria viridis, Amaranthus retroflexus, Abutilon theophrasti, Viola tricolor, Veronica persica and Stellaria media. At the same time, the compounds according to the invention leave gramineous crops such as barley, wheat, rye, millet, corn or rice virtually undamaged even at high active compound dosages when applied by the post-emergence method. In addition, some substances also spare dicotyledonous crops such as soybeans, cotton, oilseed rape, sugar beets or potatoes.

[0128] Some of the compounds according to the invention have high selectivity and are therefore suitable for controlling unwanted vegetation in agricultural crops by the post-emergence method.