5-phenyl substituted n- (tetrazol-5-yl)

专利摘要:
descriptive report of the invention patent for: “n- (tetrazol-5-yl) - and n- (triazol-5-yl) -arylcarboxamides substituted in 5-phenyl and its use as herbicides” the invention describes n- (tetrazol- 5-yl) - and n- (triazol-5-yl) -arylcarboxamides substituted with 5-phenyl of structural formula (i), and their use as herbicides. in this structural formula (i), the symbols w, x, y, z and r represent radicals such as hydrogen, organic radicals, such as alkyl, and other radicals, such as halogen. symbols a and b represent n and cy.
公开号:BR112014010813B1
申请号:R112014010813
申请日:2012-10-29
公开日:2019-12-17
发明作者:Van Almsick Andreas；Hugh Rosinger Christopher；Gatzweiler Elmar；Dietrich Hansjörg；Ahrens Hartmut；Heinemann Ines；Häuser-Hahn Isolde；Braun Ralf；Lehr Stefan
申请人:Bayer Ip Gmbh；
IPC主号:

专利说明:

Invention Patent Descriptive Report for: N- (TETRAZOL-5-IL) - OR N (TRIAZOL-5-IL) -ARYL CARBOXAMIDE REPLACED IN 5-PHENY, HERBICIDIC COMPOSITION, METHOD FOR THE CONTROL OF UNWANTED PLANTS AND THEIR USE.
Description [001] The invention concerns the technical area of herbicides, in particular, herbicides for the selective control of broadleaf herbs and lawn herbs in useful plant cultures.
[002] WO 2003/010143 and WO 2003/010153 describe, in particular, N- (tetrazol-5-yl) - and N- (triazol-5-yl) -benzamides and their pharmacological action. EP 0 049 071 A1 describes herbicidal active N-arylbenzamides. In particular, this publication refers to the compounds N- [5- (1-ethyl-1-methylpropyl) -4H-1,2,4-triazole-
3-yl] -2,6-dimethoxybenzamide (example n ° 118) and N- (1H-1,2,4-triazol-3-yl) -2,6dimethoxy-benzamide (example n ° 119). However, these compounds have insufficient herbicidal activity. In particular for reduced application rates, the herbicidal activity of the compounds known from EP 0 049 071 A1 is unsatisfactory.
[003] It is an objective of the present invention to provide compounds that have good activity against harmful plants, even at reduced application rates.
[004] It has now been found that N- (tetrazol-5-yl) - and N- (triazol-5-) arylcarboxamides which have certain substituents at the 5 position of the phenyl ring are particularly suitable as herbicides.
[005] Thus, the present invention provides N- (tetrazol-5-yl) - and N- (triazole-
5-yl) -arylcarboxamides substituted by 5-phenyl of structural formula (I) or its (I),
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2/51 salts in which, the symbol A represents N or CY, the symbol B represents N or CH, the symbol X represents nitro, halogen, cyano, formyl, thiocyanate, aquyl (C1-C6), halo-aquyl (C1- C6), alkenyl (C2-C6), halo-alkenyl (C2-C6), alkynyl (C2-C6), halo-alkynyl (C3-C6), cycloalkyl (C3-C6), halo-cycloalkyl (C3-C6) , cycloalkyl (C3-C6) -aquila (C1-C6), halo-cycloalkyl (C3-C6) -aquila (C1-C6), COLOR ¹ , COOR ¹ , OCOOR ¹ , NR1COOR ¹ , C (O) N (R ¹ ) 2, NR ¹ C (O) N (R ¹ ) 2, OC (O) N (R ¹ ) 2, C (O) NR ¹ OR ¹ , OR ¹ , OCOR ¹ , OSO2R ² , S (O) nR ² , SO2OR ¹ , SO2N (R ¹ ) 2, NR ¹ SO2R ² , NR ¹ COR ¹ , (C1-C6) alkyl -S (O) nR ² , (C1-C6) alkyl -OR ¹ , (C1C6 alkyl) ) -OCOR ¹ , (C1-C6) alkyl -OSO2R ² , (C1-C6) alkyl -CO2R ¹ , (C1-C6) alkyl SO2OR ¹ , (C1-C6) alkyl -CON (R ¹ ) 2, alkyl ( C1-C6) -SO2N (R ¹ ) 2, (C1-C6) alkyl NR ¹ COR ¹ , (C1-C6) alkyl -NR ¹ SO2R ² , NR1R2, P (O) (OR ⁵ ) 2, CH2P (O ) (OR ⁵ ) 2, (C1-C6) alkyl-heteroaryl, (C1-C6) alkyl-heterocyclyl, where each of the latter two radicals is replaced with s radicals of the group consisting of halogen, aquyl (C1-C6), halo-aquyl (C1-C6), S (O) n-aquyl (C1C6), alkoxy (C1-C6) and halo-alkoxy (C1-C6) , and where the heterocyclyl has n oxo groups, the symbol Y represents hydrogen, nitro, halogen, cyano, thiocyanate, aquyl (C1-C6), halo-aquyl (C1-C6), alkenyl (C2-C6), halo- alkenyl (C2C6), alkynyl (C2-C6), halo-alkynyl (C2-C6), cycloakyl (C3-C6), cycloalkenyl (C3-C6), halo-cycloakyl (C3-C6), cycloalkyl (C3-C6) -aquila (C1-C6), halo-cycloalkyl (C3C6) -aquila (C1-C6), COR ¹ , COOR ¹ , OCOOR ¹ , NR ¹ COOR ¹ , C (O) N (R ¹ ) 2, NR ¹ C (O) N (R ¹ ) 2, OC (O) N (R ¹ ) 2, CO (NOR ¹ ) R ¹ , NR ¹ SO2R ² , NR ¹ COR ¹ , OR ¹ , OSO2R ² , S (O) nR ² , SO2OR ¹ , SO2N (R ¹ ) 2, (C1-C6) alkylS (O) nR ² , (C1-C6) alkyl OR ¹ , (C1-C6) alkyl -OCOR ¹ , (C1-C6 alkyl) ) -OSO2R ² , (C1-C6) alkyl -CO2R ¹ , (C1-C6) alkyl -CN, (C1-C6) alkyl -SO2OR ¹ , (C1-C6) alkyl -CON (R ¹ ) 2, alkyl ( C1C6) -SO2N (R ¹ ) 2, (C1-C6) alkyl -NR ¹ COR ¹ , (C1-C6) alkyl -NR ¹ SO2R ² , N (R ¹ ) 2, P (O) (OR ⁵ ) 2 , Ç H2P (O) (OR ⁵ ) 2, (C1-C6) alkyl-phenyl, (C1-C6) alkyl-heteroaryl,
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3/51 (C1-C6) alkyl-heterocyclyl, phenyl, heteroaryl or heterocyclyl, in which each of the aforementioned radicals is replaced with radicals from the group consisting of halogen, nitro, cyano, aquyl (C1-C6), halo- aquyl (C1-C6), cycloakyl (C3-C6), S (O) n-aquyl (C1-C6), alkoxy (C1-C6), halo-alkoxy (C1-C6), alkoxy (C1-C6) - aquyl (C1-C4) and cyanomethyl, and where the heterocyclyl has n oxo groups, the symbol Z represents halogen, cyano, thiocyanate, halo-aquyl (C1Ce), alkenyl (C2-C6), halo-alkenyl (C2-C6 ), alkynyl (C2-C6), halo-alkynyl (C2-C6), cycloakyl (C3-C6), halo-cycloakyl (C3-C6), cycloalkyl (C3-C6) -aquyl (C1-C6), halo- cycloalkyl (C3-C6) -aquila (C1-C6), COR ¹ , COOR ¹ , OCOOR ¹ , NR1COOR ¹ , C (O) N (R ¹ ) 2, NR ¹ C (O) N (R ¹ ) 2, OC (O) N (R ¹ ) 2, C (O) NR ¹ OR ¹ , OSO2R ² , S (O) nR ² , SO2OR ¹ , SO2N (R ¹ ) 2, NR ¹ SO2R ² , NR ¹ COR ¹ , (C1-C6) alkyl -S (O) nR ² , (C1C6) alkyl -OR ¹ , (C1-C6) alkyl -OCOR ¹ , (C1-C6) alkyl -OSO2R ² , (C1-C6) alkyl -CO2R ¹ , (C1-C6) alkyl -SO2OR ¹ , alkyl a (C1-C6) -CON (R ¹ ) 2, (C1-C6) alkyl -SO2N (R ¹ ) 2, (C1-C6) alkyl -NR ¹ COR ¹ , (C1-C6) alkyl -NR ¹ SO2R ² , N (R1) 2, P (O) (OR ⁵ ) 2, heteroaryl, heterocyclyl or phenyl, in which each of the aforementioned three radicals is replaced with radicals from the set consisting of halogen, nitro, cyano, aquila ( C1-C6), halo-aquyl (C1-C6), cycloalkyl (C3-C6), S (O) in the alkyl (C1-C6), alkoxy (C1-C6) and halo-alkoxy (C1-C6), and in that heterocyclyl has n oxo groups, or the symbol Z can also represent hydrogen, aquyl (C1-C6) or alkoxy (C1-C6), if the symbol Y represents the radical S (O) nR ² , the symbol W represents aquila ( C1-C6), halo-aquyl (C1-C6), alkenyl (C2-C6), halo-alkenyl (C2-C6), alkynyl (C2-C6), halo-alkynyl (C2-C6), cycloalkyl (C3- C ), Halo-cycloalkyl (C3-C7), alkoxy (C1-C6), halo-alkoxy (C1-C6), S (O) n-aquyl (C1-C6), S (O) n-haloalkyl ( C1-C6), alkoxy (C1-C6) -alkyl (C1-C4), alkoxy (C1-C6) -haloalkyl (C1-C4), halogen, nitro, NR ³ COR ³ or cyan, the symbol R represents aquila ( C1-Cs), hal o-aquyl (C1-Cs), alkenyl (C2-Cs), halo-alkenyl (C2-C8), alkynyl (C2-C8), halo-alkynyl (C2-C8), each of these six radicals being replaced with radicals from
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4/51 set consisting of hydroxy, nitro, cyano, SiR ⁵ 3, PO (OR ⁵ ) 2, S (O) n-aquila (CiCe), S (O) n-haloaquila (Ci-Ce), alkoxy (Ci -Ce), halo-alkoxy (Ci-Ce), N (R ³ ) 2, COR ³ , COOR ³ , OCOR ³ , NR ³ COR ³ , NR3SO2R ⁴ , O-(C1-C2) -cycloaquila (C3-) Ce), cycloalkyl (C3-Ce), heteroaryl, heterocyclyl, phenyl, Q-heteroaryl, Q-heterocyclyl, Qphenyl and Q-benzyl, in which each of the last seven radicals is replaced with radicals from the set consisting of methyl, ethyl, methoxy, trifluoromethyl, cyano and halogen, and where heterocyclyl has n oxo groups, or the symbol R represents cycloalkyl (C3-C ), heteroaryl, heterocyclyl or phenyl, each of which is replaced with radicals from the set by halogen, nitro, cyano, aquyl (Ci-Ce), halo-aquyl (Ci-Ce), cycloalkyl (C3-Ce), S (O) n-aquyl (C1-C6), alkoxy (C1-C6), halo-alkoxy (C1-C6) and alkoxy (C1-C6) -alkyl (C1C4), where heterocyclyl has n oxo groups, the symbol Q represents O, S or NR ³ , the symbol R ¹ represents contains hydrogen, aquyl (C1-C6), haloalkyl (C1-C6), alkenyl (C2-C6), haloalkenyl (C2-C6), alkynyl (C2-C6), haloalkynyl (C2-C6), cycloalkyl (C3-C6) ), cycloalkenyl (C3-C6), halocycloakyl (C3-C6), alkyl (C1-C6) -Oaquyl (C1-C6), cycloalkyl (C3-C6) -aquyl (C1-C6), phenyl, phenyl-aquyl ( C1-C6), heteroaryl, (C1-C6) alkyl-heteroaryl, heterocyclyl, (C1-C6) alkyl-heterocyclyl, (C1-C6) alkyl -O-heteroaryl, (C1-C6) alkyl -O-heterocyclyl, alkyl (C1-C6) -NR ³ heteroaryl or (C1-C6) alkyl -NR ³ -heterocyclyl, in which each of the aforementioned 21 radicals is replaced with radicals from the group consisting of cyano, halogen, nitro, thiocyanate, OR ³ , S (O) nR ⁴ , N (R ³ ) 2, NR ³ OR ³ , COR ³ , OCOR ³ , SCOR ⁴ , NR ³ COR ³ , NR3SO2R ⁴ , CO2R ³ , COSR ⁴ , CON (R ³ ) 2 e alkoxy (C1 -C4) -alkoxy (C2-C6) -carbonyl, and where heterocyclyl has n oxo groups, the symbol R ² represents aquyl (Ci-Ce), haloaquyl (Ci-Ce), alkenyl (C2-C6), haloalkenyl (C2-C6), alkynyl (C2-C6), haloalkynyl (C2-C6), cyclohere yl (C3-C6), cycloalkenyl (C3-C6), halocycloaquila (C3-C6), alkyl (C1-C6) -Oaquila (C1-C6), cycloalkyl (C3-C6) -aquila (C1-C6), phenyl , phenyl-(C1-C6) -alkyl, heteroaryl, (C1-C6) -heteroaryl, heterocyclyl, (C1-C6) -heterocyclyl,
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5/51 (C 1 -C 6) -O-heteroaryl, (C 1 -C 6) -O-heterocyclyl, (C 1 -C 6) alkyl -N ³ heteroaryl or (C 1-C 6) -NR ³ -heterocyclyl, where each of the last 21 radicals is replaced with radicals from the group consisting of cyan, halogen, nitro, thiocyanate, OR ³ , S (O) nR4, N (R ³ ) 2, NR ³ OR ³ , COR ³ , OCOR ³ , SCOR4, NR ³ COR ³ , NR3SO2R4, CO2R ³ , COSR4, CON (R ³ ) 2 and alkoxy (C1C4) -alkoxy (C2-C6) -carbonyl, and where heterocyclyl has n oxo groups, the symbol R ³ represents hydrogen, aquyl (C1-C6), alkenyl (C2-C6), alkynyl (C2-C6), cycloalkyl (C3-C6), cycloalkyl (C3-C6) -aquyl (C1-C6) or phenyl, the symbol R4 represents aquyl (C1-C6), alkenyl (C2-C6), alkynyl (C2Ce), cycloakyl (C3-C6), cycloalkyl (C3-C6) -aquyl (C1-C6) or phenyl, the symbol R ⁵ represents aquyl (C1 -C4), n represents 0, 1 or 2; the symbol s represents 0, 1, 2 or 3.
[006] In the structural formula (I) and in all the following structural formulas, the alkyl radicals that have more than two carbon atoms can be straight or branched. Aquyl radicals include, for example, methyl, ethyl, n- or isopropyl, n-, iso-, tert- or 2-butyl, pentyls, hexyls, such as n-hexyl, thalhexyl and 1,3-dimethylbutyl. Similarly, as alkenyl, for example, allyl, 1-methylprop-2-ene-1-yl, 2methylprop-2-ene-1-yl, but-2-ene-1-yl, but- 3-ene-1-yl, 1-methylbut-3-ene-1-yl and 1methylbut-2-ene-1-yl. As alkynyl refers, for example, propargyl, but-2-inno-
1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl. The multiple bond can be in any position of the unsaturated radical. The term cycloakyl means a saturated carbocyclic ring system that has three to six carbon atoms, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Similarly, the term cycloalkenyl designates a monocyclic alkenyl group that has three to six members on the carbon ring, for example, cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl, where the double bond can be in any position.
[007] The term halogen means fluorine, chlorine, bromine or iodine.
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6/51 [008] The term heterocyclyl designates a saturated, semi-saturated or totally unsaturated cyclic radical that contains 3 to 6 ring atoms, 1 to 4 of which belong to the group consisting of oxygen, nitrogen and sulfur, and which can be optionally fused with a benzene ring. For example, heterocyclyl represents piperidinyl, pyrrolidinyl, tetrahydrofuranyl, dihydrofuranyl and oxetanyl.
[009] The term heteroaryl designates a cyclic aromatic radical that contains 3 to 6 atoms in the ring, of which 1 to 4 belong to the group consisting of oxygen, nitrogen and sulfur, and which can be optionally fused with a benzene ring. For example, heteroaryl represents benzimidazol-2-yl, furanyl, imidazolyl, isoxazolyl, isothiazolyl, oxazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyridinyl, benzisoxazolyl, thiazolyl, pyrrolyl, pyrazolyl, 1,2-thiophenyl, 1,2
1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,4-triazolyl, 1,2,3triazolyl, 1,2,5-triazolyl, 1,3, 4-triazolyl, 1,2,4-triazolyl, 1,2,4-thiadiazolyl, 1,3,4 thiadiazolyl, 1,2,3-thiadiazolyl, 1,2,5-thiadiazolyl, 2H-1,2,3, 4-tetrazolyl, 1H-1,2,3,4tetrazolyl, 1,2,3,4-oxatriazolyl, 1,2,3,5-oxatriazolyl, 1,2,3,4-thiatriazolyl and 1,2,3, 5tiatriazolil.
[010] In the event that a group is replaced by several radicals, this means that that group is replaced with one or more, the same or different, of the referred radicals. In a similar way, this applies to the construction of ring systems of several atoms and elements. In this case, it is intended to exclude from the scope of the claims compounds known to those skilled in the art as being chemically unstable under standard conditions.
[011] Depending on the nature and bond of the substituents, the compounds of formula (I) may be present in the form of stereoisomers. When, for example, one or more asymmetric carbon atoms are present, enantiomers and diastereoisomers can occur. Likewise, stereoisomers also occur when the symbol n represents 1 (sulfoxides). Stereoisomers can be obtained from
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7/51 mixtures obtained in the preparation by conventional separation methods, for example, by chromatographic separation processes. Likewise, it is possible to selectively prepare stereoisomers through the use of stereoselective reactions, using optically active starting materials and / or auxiliaries. The invention also concerns all stereoisomers and their mixtures that are covered by structural formula (I), although they are not specifically defined. Due to the ether oxime structure, the compounds according to the invention can also be present in the form of geometric isomers (E / Z isomers). The invention also concerns all E / Z isomers and their mixtures that are covered by structural formula (I), although they are not specifically defined.
[012] The compounds of formula (I) can form salts. The salts can be formed by the action of a base in the compounds of the structural formula (I) that support an acidic hydrogen atom, for example, in the case of the symbol R ¹ contains a COOH group or a sulfonamide group -NHSO2. Suitable bases include, for example, organic amines, such as trialkylamines, morpholine, piperidine or pyridine, as well as ammonium hydroxides, carbonates and hydrogen carbonates, alkali metals or alkaline earth metals, in particular hydroxide sodium and potassium, sodium and potassium carbonate and sodium and potassium hydrogen carbonate. These salts are compounds in which acidic hydrogen is replaced by an agriculturally suitable cation, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, or ammonium salts, salts with organic amines or quaternary ammonium salts, for example, with cations of the general formula [NRR'RR '] ⁺ , where each of the symbols R to R' independently represents an organic radical, in particular, aquila, aryl, araquila or alkylaryl. Alkylsulfonic and alkylsulfoxonic salts, such as trialkyl (C-C4) -sulfonic and
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8/51 (C 1 -C 4) -sulfoxonic trialkyl.
[013] The compounds of formula (I) can form salts by adding a suitable inorganic or organic acid, for example, mineral acids, for example, HCl, HBr, H2SO4, H3PO4 or HNO3, or organic acids, for example, carboxylic acids, such as formic acid, acetic acid, propionic acid, oxalic acid, lactic acid or salicylic acid, or sulfonic acids, for example, p-toluenesulfonic acid, in a basic group, for example, amino, alkylamino, dialkylamino , piperidine, morpholino or pyridine. These salts thus contain the conjugated base of the acid as an anion.
[014] The compounds of structural formula (I) are preferred, in which the symbol A represents N or CY, the symbol B represents N or CH, the symbol X represents nitro, halogen, cyano, thiocyanate, aquyl (C1Ce), halo -aquila (C1-C6), alkenyl (C2-C6), halo-alkenyl (C2-C6), alkynyl (C2-C6), halo-alkynyl (C3-C6), cycloakyl (C3-C6), halo-cycloakyl (C3-C6), (C1-C6) alkyl O-aquyl (C1-C6), cycloalkyl (C3-C6) -alkyl (C1-C6), halo-cycloalkyl (C3-C6) aquyl (Ci-Ce), COR ¹ , OR ¹ , OCOR ¹ , OSO2R ² , S (O) nR ² , SO2OR ¹ , SO2N (R1) 2, NR1SO2R ² , NR1COR ¹ , (C1-Ce) alkyl -S (O) nR ² , alkyl ( C1-Ce) -OR1, (C1C6) alkyl -OCOR ¹ , (C1-C6) alkyl -OSO2R ² , (C1-C6) alkyl -CO2R ¹ , (C1-C6) alkyl SO2OR ¹ , (C1-C6) alkyl -CON (R ¹ ) 2, (C1-C6) alkyl -SO2N (R ¹ ) 2, (C1-C6) alkyl NR ¹ COR ¹ or (C1-C6) alkyl -NR ¹ SO2R ² , (C1-C6 alkyl) ) -heteroaryl, (C1-C6) alkyl heterocyclyl, in which each of the aforementioned two radicals is replaced with radicals from the set consisting of halogen radicals, aquyl (C 1-Ce), halo-aquyl (C1-Ce), S (O) n-aquyl (C1-Ce), alkoxy (C1-Ce) and halo-alkoxy (C1-Ce), and where heterocyclyl has n groups oxo, the symbol Y represents hydrogen, nitro, halogen, cyano, thiocyanate, aquyl (C1-C6), halo-aquyl (C1-C6), alkenyl (C2-C6), halo-alkenyl (C2C6), alkynyl (C2- C6), halo-alkynyl (C3-C6), cycloakyl (C3-C6), cycloalkenyl (C3-C6), halo-cycloakyl (C3-C6), cycloalkyl (C3-C6) -aquyl (C1-C6), halo -cycloalkyl (C3C6) -aquila (C1-C6), COR ¹ , OR ¹ , COOR ¹ , OSO2R ² , S (O) nR ² , SO2OR ¹ , SO2
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9/51
N (R ¹ ) 2, N (R ¹ ) 2, NR ¹ SO2R ² , NR ¹ COR ¹ , (C 1 -C 6) alkyl -S (O) n R ² , (C 1 -C 6) alkyl OR ¹ , (C ¹ ) alkyl -C6) -OCOR1, (C1-C6) alkyl -OSO2R ² , (C1-C6) alkyl -CO2R1, (C1-C6) alkyl -SO2OR1, (C1-C6) alkyl -CON (R1) 2, (C1) alkyl -C6) -SO2N (R1) 2, (C1-C6) alkyl -NR ¹ COR ¹ , (C1-C6) alkyl -NR ¹ SO2R ² , (C1-C6) alkyl -phenyl, (C1-C6) alkyl - heteroaryl, (C1-C6) alkyl-heterocyclyl, phenyl, heteroaryl or heterocyclyl, wherein each of the aforementioned six radicals is replaced with radicals from the group consisting of halogen, nitro, cyano, (C1-C6), halo aquyl (C1-C6), cycloakyl (C3-C6), S (O) n-aquyl (C1-C6), alkoxy (C1-C6), haloalkoxy (C1-C6), alkoxy (C1-C6) -aquyl ( C1-C4) and cyanomethyl, and where heterocyclyl has n oxo groups, the symbol Z represents halogen, cyano, thiocyanate, halo-aquyl (C1C6), alkenyl (C2-C6), halo-alkenyl (C2-C6), alkynyl (C2-C6), halo-alkynyl (C3-C6), cycloakyl (C3-C6), halo-cycloakyl (C3-C6), cycloalkyl (C3-C6) -aquyl (C1 -Ce), halo-cycloalkyl (C3 -C6) -aquila (C1-C6), COR ¹ , COOR ¹ , C (O) N (R ¹ ) 2,
C (O) NR ¹ OR ¹ , OSO2R ² , S (O) nR ² , SO2OR ¹ , SO2N (R ¹ ) 2, NR ¹ SO2R ² , NR ¹ COR ¹ , (C1-C6) alkyl -S (O) nR ² , (C1-C6) alkyl -OR ¹ , (C1-C6) alkyl -OCOR ¹ , (C1C6) alkyl -OSO2R ² , (C1-C6) alkyl -CO2R ¹ , (C1-C6) alkyl -SO2OR ¹ , (C1-C6) alkyl CON (R ¹ ) 2, (C1-C6) alkyl -SO2N (R ¹ ) 2, (C1-C6) alkyl -NR ¹ COR ¹ , (C1-C6) alkyl NR1SO2R ² or 1 , 2,4-triazol-1-yl or the symbol Z can also represent hydrogen, aquyl (C1-C6) or alkoxy (C1-C6), if the symbol Y represents the radical S (O) nR ² , the symbol W represents aquyl (C1-C6), halo-aquyl (C1-C6), alkoxy (C1C6), halo-alkoxy (C1-C6), S (O) n-aquyl (C1-C6), S (O) n- haloaquila (C1-C6), alkoxy (C1C6) -aquila (C1-C4), halogen, nitro or cyano, the symbol R represents aquyl (C1-Cs), halo-aquyl (C1-Cs), alkenyl (C2-Cs) ), halo-alkenyl (C2-Cs), alkynyl (C2-Cs), halo-alkynyl (C2-Cs), where each of the last six radicals is replaced with radicals from the set consisting of nitro, cyan, SiR ⁵ 3, P (OR ⁵ ) 3, S (O) n-aquyl (C1-C6), alcohol xi (C1-C6) alkyl, halo (C1-C6) alkyl, N (R ³⁾ 2, COR ^3, COOR ^3, -OCOR ^3, NR3COR ^3, NR3SO2R ⁴ cicloaquila (C3 -C6), heteroaryl, heterocyclyl, phenyl , Q-heteroaryl, Q
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10/51 heterocyclyl, Q-phenyl and Q-benzyl, where each of the latter seven radicals is replaced with radicals from the group consisting of methyl, ethyl, methoxy, trifluoromethyl, cyano and halogen, and where heterocyclyl has n groups oxo, or the symbol R represents cycloalkyl (C3-C7), heteroaryl, heterocyclyl or phenyl, each of which is replaced with radicals from the group consisting of halogen, nitro, cyano, aquyl (C1-C6), halo-aquyl ( C1-C6), cycloakyl (C3-C6), S (O) n-aquyl (C1-C6), alkoxy (C1-C6), halo-alkoxy (C1-C6) and alkoxy (C1-C6) -aquyl ( C1C4), the symbol Q represents O, S or NR ³ , the symbol R ¹ represents hydrogen, aquyl (C1-C6), alkenyl (C2-C6), alkynyl (C2-C6), cycloalkyl (C3-C6), cycloalkyl (C3-C6) -alkyl (C1-C6), alkyl (C1C6) -O-aquyl (C1-C6), phenyl, phenyl-aquyl (C1-C6), heteroaryl, heteroaryl, heterocyclyl, (C1-C6) alkyl (C1-C6) alkyl-heterocyclyl, (C1-C6) alkyl -O-heteroaryl, (C1-C6) alkyl -O-heterocyclyl, (C1-C6) alkyl -NR ³ -heteroaryl or (C1-C6) alkyl NR ³ -heterocyclyl, where each of the aforementioned sixteen radicals is replaced with radicals from the group consisting of cyano, halogen, nitro, OR ³ , S (O) nR ⁴ , N (R ³ ) 2, NR3OR ³ , COR ³ , OCOR ³ , NR3COR ³ , NR3SO2R ⁴ , CO2R ³ , CON (R ³ ) 2 and alkoxy (C1-C4) -alkoxy (C2-C6) -carbonyl, and in which heterocyclyl has n oxo groups, the symbol R ² represents aquyl (C1-C6), alkenyl (C2-C6), alkynyl (C2C6), cycloalkyl (C3-C6), cycloalkyl (C3-C6) -aquyl (C1-C6), alkyl ( C1-C6) -Oquyl (C1-C6), phenyl, phenyl-aquyl (C1-C6), heteroaryl, alkyl (C1-C6) -heteroaryl, heterocyclyl, (C1-C6) alkyl-heterocyclyl, (C1-C6) alkyl ) -O-heteroaryl, (C1C6) alkyl -O-heterocyclyl, (C1-C6) alkyl -NR ³ -heteroaryl or (C1-C6) alkyl -NR ³ heterocyclyl, where each of the last sixteen radicals is replaced with s radicals of the set consisting of cyan, halogen, nitro, OR ³ , S (O) nR ⁴ , N (R ³ ) 2, NR ³ OR ³ , NR ³ SO2R ⁴ , COR ³ , OCOR ³ , NR ³ COR ³ , CO2R ³ , CON (R ³ ) 2 and (C1-C4) alkoxy (C2-C6) -carbonyl alkoxy, and where heterocyclyl has n oxo groups,
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11/51 the symbol R ³ represents hydrogen, aquyl (C-C6), alkenyl (C2-C6), alkynyl (C2-Ce), cycloalkyl (C3-C6) or cycloalkyl (C3-C6) -aquyl (C1-C6 ), the symbol R4 represents aquyl (C1-C6), alkenyl (C2-C6) or alkynyl (C2C6), the symbol R ⁵ represents methyl or ethyl, the symbol n represents 0, 1 or 2;
the symbol s represents 0, 1, 2 or 3.
[015] Particularly preferred are compounds of formula (I), in which the symbol A represents N or CY, the symbol B represents N or CH, the symbol X represents nitro, halogen, cyano, aquyl (C1-C6), haloakyl (C1-C6), cycloakyl (C3-C6), OR ¹ , S (O) nR ² , (C1-C6) alkyl -S (O) nR ² , (C1-C6) alkyl -OR ¹ , alkyl ( C1-C6) -CON (R ¹ ) 2, (C1-C6) alkyl -SO2N (R ¹ ) 2, (C1-C6) alkyl -NR ¹ COR ¹ , (C1-C6) alkyl -NR ¹ SO2R ² , alkyl (C1-C6) -heteroaryl, alkyl (C1-C6) -heterocyclyl, in which each of the latter two radicals is replaced with radicals from the group consisting of halogen, aquyl (C1C6), halo-aquyl (C1-C6 ), S (O) n-aquyl (C1-C6), alkoxy (C1-C6) and halo-alkoxy (C1-C6), and where heterocyclyl has n oxo groups, the symbol Y represents hydrogen, nitro, halogen, cyano, aquyl (C1Ce), haloaquyl (C1-C6), OR ¹ , S (O) nR ² , SO2N (R1) 2, N (R ¹ ) 2, NR1SO2R ² ,
NR ¹ COR ¹ , (C1-C6) alkyl -S (O) nR ² , (C1-C6) alkyl -OR ¹ , (C1-C6) alkyl -CON (R ¹ ) 2, (C1-C6) alkyl - SO2N (R ¹ ) 2, (C1-C6) alkyl -NR ¹ COR ¹ , (C1-C6) alkyl -NR ¹ SO2R ² , (C1-C6) alkyl-phenyl, (C1-C6) alkyl-heteroaryl, alkyl (C1-C6) -heterocyclyl, phenyl, heteroaryl or heterocyclyl, in which each of the aforementioned 6 radicals is replaced with radicals from the group consisting of halogen, nitro, cyano, aquyl (C1-C6), halo-aquyl (C1 -C6), cycloalkyl (C3-C6), S (O) n-aquyl (C1-C6), alkoxy (C1-C6), halo-alkoxy (C1-C6), alkoxy (C1-C6) -alkyl (C1 -C4) and cyanomethyl, and where heterocyclyl has n oxo groups, the symbol Z represents halogen, cyan, halo-aquyl (C1-C6),
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12/51 cycloalkyl (C3-Ce), S (O) nR ² , 1,2,4-triazol-1-yl or the symbol Z can also represent hydrogen, methyl, methoxy or ethoxy, if the symbol Y represents the radical S (O) nR ² , the symbol W represents methyl, ethyl, methoxymethyl, methoxy, fluorine, chlorine or S (O) nCH3, the symbol R represents aquyl (C1-C8), haloacyl (C1-C8), alkenyl (C2-C8), halo-alkenyl (C2-C8), alkynyl (C2-C8), halo-alkynyl (C2-C8), in which each of the last six radicals is replaced with radicals from the set consisting of cyano , S (O) n-aquyl (C1-Ce), alkoxy (C1-Ce), haloalkoxy (C1-C6), COR ³ , COOR ³ , OCOR ³ , NR ³ COR ³ , NR3SO2R ⁴ , cycloalkyl (C3Ce), heteroaryl, heterocyclyl and phenyl, where each of the latter three radicals is replaced with radicals from the set consisting of methyl, ethyl, methoxy, trifluoromethyl, cyano and halogen, and where heterocyclyl has 0 to 2 oxo groups, or the symbol R represents phenyl which is substituted with s radicals of the set consisting of p or halogen, nitro, cyano, aquyl (C1-Ce), halo-aquyl (C1Ce), cycloakyl (C3-Ce), S (O) n-aquyl (C1-Ce), alkoxy (C1-Ce), halo- alkoxy (C1-Ce) and alkoxy (C1 -Ce) -alkyl (C1 -C4), the symbol R ¹ represents hydrogen, aquyl (C1-Ce), alkenyl (C2-Ce), alkynyl (C2-Ce), cycloalkyl (C3-Ce), cycloalkyl (C3-C6) -alkyl (C1-Ce), alkyl (C1Ce) -O-aquyl (C1-Ce), phenyl, phenyl-aquyl (C1-Ce), heteroaryl, alkyl (C1 -Ce) heteroaryl, heterocyclyl, (C1-C6) alkyl-heterocyclyl, (C1-C6) alkyl -O-heteroaryl, (C1-C6) alkyl -O-heterocyclyl, (C1-C6) alkyl -NR ³ -heteroaryl or alkyl (C1-C6) NR ³ -heterocyclyl, where each of the aforementioned sixteen radicals is replaced with radicals from the group consisting of cyano, halogen, nitro, OR ³ , S (O) nR ⁴ , N (R ³ ) 2, NR ³ OR ³ , COR ³ , OCOR ³ , NR ³ COR ³ , NR3SO2R ⁴ , CO2R ³ , CON (R ³ ) 2 and alkoxy (C1-C4) -alkoxy (C2-Ce) -carbonyl, and where heterocyclyl has n oxo groups, the symbol R ² represents aquyl (C1-Ce), cycloalkyl (C3-Ce) or cycloalkyl (C3-C6) - aquila (C1-C6), each of which is replaced with s
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13/51 radicals of the set consisting of halogen and OR ³ , the symbol R ³ represents hydrogen or aquila (Ci-Ce), the symbol R ⁴ represents aquila (Ci-C6), the symbol R ⁵ represents methyl or ethyl, the symbol n represents 0, 1 or 2;
the symbol s represents 0, 1, 2 or 3.
[016] In all the structural formulas specified here below, the substituents and symbols have the same meanings as defined for structural formula (I), unless otherwise defined.
[017] The compounds according to the invention can also be prepared, for example, by the method shown in scheme 1, by means of a catalyzed reaction based on a piperidinecarbonyl chloride (II) with a 5-amino-1 H- 1,2,4-triazole or 5-amino-1 H-tetrazole (III):
Layout 1
(III) (II)
[018] Benzoyl chlorides of structural formula (II) or their original benzoic acids are known in principle and can be prepared, for example, by the methods described in JP 63122673, WO 99/54328 A1 and WO 97/46530 A1 .
[019] The compounds according to the invention can also be prepared by the method described in scheme 2, by reacting a benzoic acid of structural formula (IV) with a 5-amino-1 H-1,2,4- triazole or a 5-amino-1 H-tetrazole (III):
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14/51
Layout 2
carbonyldiimidazole (CDI), dicyclohexylcarbodiimide (DCC), 2,4,6-trioxide
2,4,6-tripropyl-1,3,5,2,4,6-trioxatrifosfinane (T3P), etc.
[021] The compounds according to the invention can also be prepared by the method shown in scheme 3, by reaction of an N- (1 H-1,2,4-triazol-5-yl) -benzamide, N- (1 H-tetrazol-5-yl) -benzamide, N- (1H-
1,2,4-triazol-5-yl) -nicotinamide or N- (1 H-tetrazol-5-yl) -nicotinamide:
Layout 3
(V) (I) [022] For this reaction shown in scheme 3, it is possible, for example, to use alkylating agents, for example, halides or aquyl sulfonates or diakyl sulfates, in the presence of a base.
[023] It may be expedient to change the order of the reaction steps. Thus, benzoic acid that has a sulfoxide cannot be converted directly to its acid chlorides. In this case, it is advisable to initially prepare the amide at the thioether stage and then oxidize the thioether to the sulfoxide.
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15/51 [024] The 5-amino-1H-tetrazols of structural formula (III) are either commercially available or can be prepared in an analogous manner with methods known from the literature. For example, 5-amino-1-Rtetrazols can be prepared from aminotetrazole by the method described in Journal of the American Chemical Society (1954), 76, 923-924:
N _{x X} N
N
NaOH / RX
[025]
In the structural formulas mentioned above, the symbol R represents, for example, an aquyl radical.
[026] The 5-amino-1-R-tetrazols can be synthesized, for example, as described in Journal of the American Chemical Society (1954) 76, 8889:
H
H
NaNO ₂ / HCl
[027] The 5-amino-1H-triazoles of structural formula (III) are either commercially available or can be prepared in an analogous manner with methods known from the literature. For example, 5-amino-1-Rtriazols can be prepared from aminotriazole by the method described in Zeitschrift füer Chemie (1990), 30 (12), 436 - 437:
H, ^NH 2 R NH2 ^N ^ NaOH / RX N— /
N ^ N ------- n Jn [028] The 5-amino-1-R-triazoles can also be synthesized, for example, as described in Chemische Berichte (1964), 97 (2), 396- 404:
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16/51
HCOOH
[029] 5-Amino-1-R-triazoles can also be synthesized, for example, as described in Angewandte Chemie (1963), 75, 918:
[030] The sets of compounds of structural formula (I) and / or their salts that can be synthesized by the aforementioned reactions can also be prepared in parallel, in which case this can be achieved in a manual, partially automated way. or fully automated. For example, it is possible to automate the course of the reaction, the processing or the purification of the products and / or the intermediates. Overall, this intends to designate a procedure described, for example, by D. Tiebes in Combinatorial Chemistry - Synthesis, Analysis, Screening (editor: Günther Jung), Wiley, 1999, on pages 1 to 34.
[031] For the parallelized reaction and processing course, it is possible to use several commercially available instruments, for example, Calypso reaction blocks from Barnstead International, Dubuque, Iowa 52004-0797, USA or reaction stations from Radleys, Shirehill, Saffron Walden , Essex, CB11 3AZ, England, or PerkinElmer MultiPROBE automated workstations, Waltham, Massachusetts 02451, USA. For the parallel purification of the compounds of structural formula (I) and their salts or intermediates that occur in the course of preparation, the available apparatus includes chromatography apparatus, for example, from ISCO, Inc.,
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17/51
4700 Superior Street, Lincoln, NE 68504, USA.
[032] The referred devices provide a modular procedure, in which the individual processing steps are automated, although manual operations have to be carried out between the processing steps. This can be overcome by using partly or fully integrated automation systems in which the respective automation modules are operated, for example, by robots. Automation systems of this type can be purchased, for example, from Caliper, Hopkinton, MA 01748, USA.
[033] The implementation of individual or multiple synthesis steps can be supported by the use of cleaning reagents / resins supported on polymers. In the specialized literature, sets of experimental protocols are described, for example, in ChemFiles, Vol. 4, No. 1, PolymerSupported Scavengers and Reagents for Solution-Phase Synthesis (SigmaAldrich).
[034] In addition to the methods described here, compounds of formula (I) and their salts can be prepared, in whole or in part, by solid phase support methods. For this purpose, the individual intermediates or all intermediates in the synthesis or in a synthesis adapted for the corresponding procedure are bonded to a synthetic resin. Synthesis methods supported by solid phase are adequately described in the technical literature, for example, by Barry A. Bunin in “The Combinatorial Index”, Academic Press, 1998 and in Combinatorial Chemistry Synthesis, Analysis, Screening (editor: Günther Jung), Wiley, 1999. The use of synthesis methods with solid phase support allows different protocols to be carried out, which are known from the literature and which, in turn, can be carried out manually or automatically . The reactions can be carried out, for example, using IRORI technology in micro-reactors from Nexus Biosystems, 12140 Community Road, Poway, CA92064, USA.
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18/51 [035] The solid phase and liquid phase procedures of individual or multiple synthesis steps can be supported through the use of microwave technology. In the specialized literature, sets of experimental protocols are described, for example, in Microwaves in Organic and Medicinal Chemistry (editor C. O. Kappe and A. Stadler), Wiley, 2005.
[036] The preparation using the processes described here provides compounds of structural formula (I) and their salts in the form of sets of substances, which are called bookstores. The present invention also provides bookstores comprising at least two compounds of formula (I) and their salts.
[037] The compounds of structural formula (I) according to the invention (and / or their salts), hereinafter collectively referred to as "compounds according to the invention", have an excellent herbicidal efficacy against a wide spectrum of harmful plants economically important monocotyledons and annual dicotyledons. The active compounds act effectively even on harmful perennial plants that produce shoots from rhizomes, rooted chips and other perennial organs that are difficult to control.
[038] Therefore, the present invention also relates to a method for controlling unwanted plants or for regulating plant growth, preferably in plant cultures, in which one or more compounds according to the invention are applied to plants (for example, harmful plants, such as monocots or dicots or unwanted crop plants), to seeds (for example, grains, seeds or vegetative propagules, such as tubers or shoots with buds) or to the area in which plants grow (for example, the area under cultivation). The compounds according to the invention can be applied, for example, before cultivation (if appropriate also by incorporation into the soil), before emergence or after emergence. As specific examples of some
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19/51 representatives of monocotyledonous and dicotyledonous herb flora that can be controlled by the compounds according to the invention refer to the following, although such enumeration is not intended to be a restriction to particular species:
harmful monocot plants of the genus: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Erochisyl Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum;
dicotyledonous herbs of the genus: Abutilan, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Euphorbia, Euphorbia , Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola , Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.
[039] When the compounds according to the invention are applied to the soil surface before germination, then the emergence of seed shoots is completely prevented or the seeds grow until they reach the cotyledonous stage, then stopping growth and eventually after three to four weeks they die completely.
[040] If the active compounds are applied post-emergence to the green parts of the plants, then the growth is interrupted after the treatment and the harmful plants remain in the growth stage of the moment of application, or they die completely after some time, in a way such that competition for weed parts, which is detrimental to crop plants, is thus eliminated very early and
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20/51 in an extended way.
[041] Although the compounds according to the invention have a remarkable herbicidal activity against monocotyledonous and dicotyledonous herbs, the crop plants of economically important crops, for example, dicotyledonous cultures of the genera Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia, or monocotyledon cultures of the genera Allium, Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Trale, Sorghum , Triticum, Zea, in particular Zea and Triticum, are damaged only to an insignificant degree or are not damaged at all, depending on the structure of the respective compound according to the invention and its rate of application. It is for this reason that the compounds of the present invention are quite suitable for the selective control of the growth of unwanted plants in crop plants, such as plants useful from an agricultural point of view or ornamental plants.
[042] In addition, the compounds according to the invention (depending on their particular structure and the rate of application used) have remarkable growth-regulating properties in crop plants. These are linked to the metabolism of the plant in a regulatory manner, and can thus be used to influence, in a targeted manner, the constituents of the plant or to facilitate harvesting, such as, for example, triggering desiccation and a delay in growth. Furthermore, in general, they are also suitable for controlling and inhibiting unwanted vegetative growth without destroying plants in the process. The inhibition of vegetative growth plays an important role for many monocot and dicot crops, since, for example, this can reduce or completely prevent lodging.
[043] Due to their herbicidal and plant growth regulation properties, the active compounds can also be used
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21/51 for the control of harmful plants in crops of genetically modified plants or plants modified by conventional mutagenesis. In general, transgenic plants are distinguished because of their particularly advantageous properties, for example, by resistance against certain pesticides, mainly certain herbicides, resistance to plant diseases or to organisms that cause plant diseases, such as certain insects or micro -organisms, such as fungi, bacteria or viruses. There are other particular properties that concern, for example, the material harvested in terms of quantity, quality, storage capacity, composition and specific constituents. For example, there are known transgenic plants with a high starch content or with an altered starch quality or with a different fatty acid composition in the harvested material.
[044] With regard to transgenic crops, it is preferable to use the compounds according to the invention in economically important transgenic crops of useful and ornamental plants, for example, cereals, such as wheat, barley, rye, oats, corn- kidney / sorghum, rice and corn, or crops of sugar beet, cotton, soy, rapeseed, potatoes, tomatoes, peas and other vegetables. It is preferable to use the compounds according to the invention as herbicides in useful plant cultures that are resistant or that have been made resistant, through recombination, to the phytotoxic effects of the herbicides.
[045] It is preferable to use the compounds according to the invention or their salts in economically important transgenic crops of useful and ornamental plants, for example, cereals, such as wheat, barley, rye, oats, millet / sorghum, rice , cassava and maize, or crops of sugar beet, cotton, soy, rapeseed, potatoes, tomatoes, peas and other vegetables. Preferably, the compounds according to the invention can be used as herbicides in useful plant cultures that are resistant or that have been made resistant, through recombination, to the phytotoxic effects of
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22/51 herbicides.
[046] Conventional methods for generating new plants that have modified properties compared to plants that have occurred to date consist, for example, of traditional culture methods and mutant generation. Alternatively, it is possible to generate new plants with modified properties with the aid of recombination methods (see, for example, documents EP-A-0221044, EP-A-0131624). For example, many descriptions of:
- recombinant modifications of crop plants for the purpose of modifying the starch synthesized in plants (e.g., WO 92/11376, WO 92/14827, WO 91/19806),
- transgenic crop plants that are resistant to particular herbicides of the glufosinate type (see, for example, EP-A-0242236, EP-A-242246) or of the glyphosate type (WO 92/00377) or the sulfonyl urea type ( EP-A-0257993, US-A-5013659),
- transgenic crop plants, for example, cotton, with the ability to produce Bacillus thuringiensis toxins (Bt toxins), which make plants resistant to particular pests (documents EP-A-0142924, EPA-0193259),
- transgenic crop plants with a modified fatty acid composition (WO 91/13972),
- genetically modified crop plants with new constituents or secondary metabolites, for example, new phytoalexins, which provides increased resistance to disease (documents EPA 309862, EPA0464461),
- genetically modified plants with reduced photorespiration that provide higher yields and a higher tolerance to stress (document EPA 0305398),
- transgenic crop plants that produce important proteins from a pharmaceutical or diagnostic point of view (“pharmacology
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Molecular 23/51 ”),
- transgenic crop plants that are distinguished by higher yields or better quality,
- transgenic crop plants that are distinguished by a combination, for example, of the new properties mentioned above (“gene stacking”).
[047] There are several techniques of molecular biology through which it is possible to generate new transgenic plants with modified properties that are known in principle; see, for example, I. Potrykus and G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg, or Christou, Trends in Plant Science 1 (1996) 423-431.
[048] To carry out such recombinant manipulations, it is possible to introduce nucleic acid molecules that allow mutagenesis or a sequence change by recombination of DNA sequences in plasmids. With the aid of conventional methods, it is possible, for example, to perform base exchanges, remove parts of sequences or add natural or synthetic sequences. For the joining of DNA fragments together, it is possible to attach adapters or ligators to the fragments; see, e.g., Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed. Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker Gene und Klone [Genes and Clones], VCH Weinheim 2nd edition, 1996.
[049] The production of plant cells with reduced activity of a gene product can be achieved, for example, by expression of at least one suitable antisense RNA or one sense RNA to obtain a co-effect. suppression or expression of at least one properly constructed ribozyme that specifically cleaves transcripts of the aforementioned gene product. For this purpose, it is possible to use, firstly, DNA molecules that comprise the entire coding sequence of a gene product including any flanking sequences present or else DNA molecules that comprise only parts of the
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24/51 coding sequence, in which case such parts must be long enough to produce an antisense effect on cells. The use of DNA sequences that have a high degree of homology with the coding sequences of a gene product, but which are not completely identical to this, is also possible.
[050] When nucleic acid molecules are expressed in plants, the synthesized protein can be located in any compartment of the plant cell. However, to achieve a location in a particular compartment, it is possible, for example, to link the coding region with DNA sequences that guarantee the location in a particular compartment. Such sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106). Nucleic acid molecules can also be expressed in the organelles of plant cells.
[051] The cells of transgenic plants can be regenerated by known techniques to obtain complete plants. In principle, transgenic plants can be plants of any desired plant species, that is, not only monocotyledonous plants, but also dicotyledonous plants.
[052] Thus, it is possible to obtain transgenic plants whose properties are altered by overexpression, suppression or inhibition of genes or sequences of homologous genes (= natural) or expression of genes or sequences of heterologous genes (= exogenous).
[053] Preferably, the compounds of the invention can be used in transgenic cultures that are resistant to growth regulators, for example, dicamba, or to herbicides that inhibit essential plant enzymes, for example, acetolactate synthases (ALS), EPSP synthases , glutamine synthases (GS) or hydroxyphenylpyruvate dioxigenases (HPPD), or to herbicides in the group consisting of sulfonyl ureas, glyphosates or benzoylisoxazoles and similar active ingredients.
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25/51 [054] When using the active compounds according to the invention in transgenic cultures, there are not only the effects against harmful plants observed in other cultures, but also, frequently, effects that are specific to the application in the particular transgenic culture, for example, an altered or specifically broad spectrum of herbs that can be controlled, altered application rates that can be used for application, preferably a good combining ability with herbicides for which the transgenic culture is resistant and influencing growth and the yield of transgenic crop plants.
[055] Therefore, the invention also provides the use of the compounds of the invention for the control of harmful plants in transgenic crop plants.
[056] The compounds according to the invention can be applied in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusting products or granules in conventional formulations. Thus, the invention also provides herbicidal compositions and plant growth regulators that comprise the compounds according to the invention.
[057] The compounds according to the invention can be formulated in several ways, according to the required biological and / or physicochemical parameters. Examples of possible formulations include: wetting powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil, spray solutions, suspension concentrates (SC), oil or water based dispersions, oil miscible solutions, capsule suspensions (CS), dusting products (DP), seed coating products , granules for dissemination and application to the soil, granules (GR) in the form of microgranules, spray granules, coated granules and adsorption granules, water dispersible granules (WG), water soluble granules (SG), formulations
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26/51
ULV, microcapsules and waxes.
[058] These individual formulation types are known in principle and are described, for example, in: Winnacker-Küchler, Chemische Technologie [Chemical Technology], Volume 7, C. Hanser Verlag Munich, 4th ed. 1986; Wade van Valkenburg, Pesticide Formulations, Marcel Dekker, NY, 1973; K. Martens, Spray Drying Handbook, 3rd ed. 1979, G. Goodwin Ltd. London.
[059] Necessary formulation aids, such as inert materials, surfactants, solvents and other additives, are also known and are described, for example, in: Watkins, Handbook of Insecticide Dust Diluents and Carriers, 2nd ed., Darland Books, Caldwell NJ, Hv Olphen, Introduction to Clay Colloid Chemistry; 2nd ed., J. Wiley & Sons, N.Y .; C. Marsden, Solvents Guide; 2nd ed., Interscience, N.Y. 1963; McCutcheon's Detergents and Emulsifiers Annual, MC Publ. Corp., Ridgewood N.J .; Sisley and Wood, Encyclopedia of Surface Active Agents, Chem. Publ. Co. Inc., N.Y. 1964; Schonfeldt, Grenzflachenaktive Athylenoxidaddukte [Ethylene interface oxide adducts], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küchler, Chemische Technologie [Chemical Engineering], volume 7, C. Hanser Verlag Munich, 4th ed. 1986.
[060] Based on these formulations, it is also possible to produce combinations with other pesticide-active compounds, such as, for example, insecticides, acaricides, herbicides, fungicides and also with phytoprotective agents, fertilizers and / or growth regulators , for example, in the form of a finished formulation or in the form of a tank mixture. Suitable phytoprotective agents include, for example, mefenpyr-diethyl, cypro-sulfamide, isoxadifene-ethyl, cloquintocet-mexyl and dichloromide.
[061] Wetting powders are preparations that can be dispersed evenly in water and, together with the active ingredient, in addition to a diluent or inert substance, also comprise surfactants of
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27/51 ionic and / or non-ionic (wetting agents, dispersants), for example, polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycolic ether sulphates, alkane sulphonates, benzene sulphonates, ligno sodium sulfonate, 2,2'dinaftymethane-6,6'-sodium disulfonate, sodium dibutylnaphthalene-sulfonate or sodium oleoylmethyltaurate. To produce wetting powders, the herbicidal active compounds are finely ground, for example, in conventional appliances, such as hammer mills, fan mills and air jet mills, and, simultaneously or subsequently, mixed with formulation aids. .
[062] Emulsifiable concentrates are produced by dissolving the active ingredient in an organic solvent, for example, butanol, cyclohexanone, dimethylformamide, xylene, or hydrocarbons or aromatics with relatively high boiling points or mixtures of organic solvents, with the addition of a or more ionic and / or non-ionic surfactants (emulsifiers). The emulsifiers used can be, for example: calcium alkylarylsulfonates, such as calcium dodecylbenzene sulfonate, or non-ionic emulsifiers, such as polyglycolic fatty acid esters, alkylaryl-polyglycolic ethers, polyglycolic ethers of fatty alcohols, oxide condensation products propylene-ethylene oxide, alkyl polyethers, sorbitan esters, for example, sorbitan fatty acid esters, or polyoxyethylene-sorbitan esters, for example, polyoxyethylene-sorbitan fatty acid esters.
[063] The dusting products are obtained by grinding the active compound with finely distributed solid substances, for example talc, natural clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
[064] Suspension concentrates can be based on water or oil. They can be prepared, for example, by wet grinding using commercial ball mills and, optionally, together with the addition
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28/51 of surfactants, such as, for example, those already listed above for other types of formulations.
[065] Emulsions, for example, oil-in-water (EW) emulsions, can be produced, for example, by means of agitators, colloid mills and / or static mixers, using aqueous organic solvents and, optionally, surfactants, such as those listed above, for example, for other types of formulation.
[066] The granules can be prepared by spraying the active compound on an inert granular material capable of adsorption or by applying concentrates of the active compound to the surface of carrier substances, such as sand, kaolinites or inert granular materials, using adhesives, for example, polyvinyl alcohol, sodium polyacrylate or mineral oils. Suitable active compounds can also be granulated in a conventional manner for the production of fertilizer granules - if desired in the form of a mixture with fertilizers.
[067] Water-dispersible granules are generally prepared by conventional processes, such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material.
[068] For the production of food granules, fluidized bed granules, extruder granules and spray granules, see, for example, processes in Spray-Drying Handbook, 3rd ed. 1979, G. Goodwin Ltd., London, JE Browning, Agglomeration, Chemical and Engineering 1967, pages 147 ff .; Perry's Chemical Engineer's Handbook, 5th Ed., McGraw-Hill, New York 1973, p. 8-57.
[069] For more details regarding the formulation of crop protection compositions, see, for example, GC Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pages 81-96 and JD Freyer, SA Evans, Weed Control Handbook, 5th ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.
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29/51 [070] In general, agrochemical formulations contain 0.1% to 99% by weight and, in particular, 0.1% to 95% by weight of the compounds according to the invention.
[071] In wetting powders, the concentration of active compound is comprised, for example, between about 10% and 90% by weight, the remainder up to 100% by weight consisting of conventional formulation components. In the case of emulsifiable concentrates, the concentration of active compound is between about 1% and 90% and, preferably, between 5% and 80% by weight. Formulations in the form of dusting products comprise between 1% and 30% by weight of active ingredient and, preferably, normally between 5% and 20% by weight of active ingredient; sprayable solutions contain between about 0.05% and 80% and preferably between 2% and 50% by weight of active ingredient. In the case of water-dispersible granules, the active ingredient content depends, in part, on whether the active compound is present in the form of a liquid or solid and on which granulation aids, fillers, etc. are used. In water-dispersible granules, the content of active compound is, for example, between 1% and 95% by weight and preferably between 10% and 80% by weight.
[072] In addition, the active compound formulations referred to include optionally the respective adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents and solvents, fillers, vehicles and dyes, defoamers, evaporation inhibitors and agents that influence conventional ph and viscosity.
[073] Based on these formulations, it is possible to produce combinations with other pesticide-active compounds, such as, for example, insecticides, acaricides, herbicides, fungicides and also with phytoprotective agents, fertilizers and / or growth regulators, for example, in the form of a finished formulation or a tank mix.
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30/51 [074] The active compounds which can be used in combination with the compounds according to the invention in mixed formulations or in tank mixtures include, for example, known active compounds based on inhibition, for example , acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase, enolpyruvylshiquime-3-phosphate synthase, glutamine synthetase, p-hydroxyphenylpyruvate dioxigenase, phytene desaturase, photosystem I, photosystem II, protoporphyrinogen oxidase, as described in Research by example, as described in Research by example 26 (1986) 441-445 or the Pesticide Manual, 15 ^the edition, the British Crop Protection Council and the Royal Soc. of Chemistry, 2009 and literature cited therein. Examples of known herbicides or plant growth regulators that can be combined with the compounds of the invention include the following active ingredients (the compounds are designated by the “common name” according to the 'International Organization for Standardization' (ISO) or by chemical name or code number) and always include all forms of Use, such as acids, salts, esters and isomers, such as stereoisomers and optical isomers. In this case, as an example, one and, in some cases, several forms of Use are mentioned:
[075] acetochlor, acibenzolar, acibenzolar-S-methyl, acifluorfen, acifluorfen-sodium, aclonifene, alachlor, alidochlor, aloxidime, aloxidime-sodium, ametrine, amicarbazone, amidochlor, starch-sulfurone, aminocyclohydrochloride, aminocyclopyracloride , ancimidol, anilofos, asulam, atrazine, azafenidin, azimsulfurone, aziprotrine, beflubutamide, benazoline, benazolin-ethyl, bencarbazone, benfluralin, benfuresate, bensulide, bensulfurone, bensulfurone-methyl, benzoform, benzene, benzene, benzene, benzene, benzene, benzene , bifenox, bilanafos, bilanafos-sodium, bispiribac, bispyribac-sodium, bromacil, bromobutide, bromophenoxime, bromoxynil, bromurone, bumina, busoxinone, butachloride, butafenacil, butamphonate, butylamine, carboxin, butylamine, carboxylic acid, butroen -ethyl, clomethoxyfen, chlorambene, chlorazifop, chlorazifop-butyl, chlorobromurone, chlororbam, chlorfenac,
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31/51 chlorfenac-sodium, chlorfenprop, chlorflurenol, chlorflurenol-methyl, chloridazone, chlorimurone, chlorimurone-ethyl, chlormequat chloride, chlornitrophen, chlorophthalim, chlortal-dimethyl, chlortolurone, clorsulfurone, cinidone, cinidone-cinidine, cinidone-cinidine, cinidona-cinidona-cinidona , cletodime, clodinafop, clodinafop-propargyl, clofencet, clomazone, clomeprop, cloprop, clopyralide, chloransulam, cloransulam-methyl, cumilurone, cyanamide, cyanazine, cyclanilide, cyclate, cyclo-sulfamurone, cycloxyme, cycloxyme, cycloxyme -butyl, cyperquat, cyprazine, cyprazole, 2,4-D, 2,4-DB, daimurone / dimrone, dalapone, daminozide, dazomet, n-decanol, demedipham, desmethrin, detosil-pyrazolate (DTP), dialate, dicamba, diclobenyl, dichlorprop, dichlorprop-P, diclofop, diclofop-methyl, diclofop-P-methyl, diclosulam, diethyl, diethyl-ethyl, diphenoxurone, difenzoquat, diflufenicano, diflufenzopir, diflufenzopir-sodium, dichlorpyrone, dimefurone, dimefurone, dimefurone, dimefurone, dimetachlor, dimetamethrin, dimet enamide, dimethenamide-P, dimethypine, dimetrosulfurone, dinitramine, dinoseb, dinoterb, diphenamide, dipropetrin, diquat, diquat dibromide, dithiopir, diurone, DNOC, eglinazineethyl, endothal, EPTC, esprocarbone, ethoxymethylamide, ethanolflamine, ethoxyamide, ethanol ethidimurone, ethiozine, etofumesate, ethoxyfene, ethoxyfen-ethyl, ethoxy-sulfurone, etobenzanide, F-5331, i.e., N- [2-chloro-4-fluoro-5- [4- (3fluoropropyl) -4,5-di -hydro-5-oxo-1 H-tetrazol-1-yl] -phenyl] -ethanesulfonamide, F7967, that is, 3- [7-chloro-5-fluoro-2- (trifluoromethyl) -1H-benzimidazole- 4-yl] -1-methyl-6 (trifluoromethyl) -pyrimidine-2,4 (1H, 3H) -dione, fenoprop, fenoxaprop, fenoxapropP, phenoxaprop-ethyl, fenoxaprop-P-ethyl, phenoxa-sulfone, fentrazamide, fenurone , flamprop, flamprop-M-isopropyl, flamprop-M-methyl, flaza-sulfurone, florasulam, fluazifop, fluazifop-P, fluazifop-butyl, fluazifop-P-butyl, fluazolate, flucarbazone, flucarbazone-sodium, fluceto-sulfurone, flucloralin , flufenacet (tiafluamide), flufenpir, fluf enpir-ethyl, flumetraline, flumetsulam, flumiclorac, flumicloracpentila, flumioxazin, flumipropyn, fluometurone, fluorodiphene, fluoroglycofen, fluoroglycofen-ethyl, flupoxam, flupropacil, flupropanate, flupirsulfuron, flufirsulfuron, flupirsulfurone, flupirsulfurone, fluroxypyr, fluroxypyr-meptyl, flurprimidol, flurtamone, flutiacet, flutiacet-methyl,
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32/51 flutiamide, fomesafen, foramsulfurone, forclorfenurone, phosamine, furyloxifene, gibberellic acid, glufosinate, glufosinate-ammonium, glufosinate-P, glufosinate-Pamonium, glufosinate-P-sodium, glyphosate, glyphosate-isopropyl-9, isopropyl-9-isopropyl that is, O- (2,4-dimethyl-6-nitrophenyl) -O-ethyl isopropylphosphoramidothioate, O-ethyl, halo-sapene, halo-sulfurone, halo-sulfurone-methyl, haloxifop, haloxifop-P, haloxifop-ethoxy, haloxifop-P -ethoxyethyl, haloxifop-methyl, haloxyfop-P-methyl, hexazinone, HW-02, i.e., 1- (dimethoxy-phosphoryl) -ethyl (2,4-dichlorophenoxy) -ethyl, imazametabenz, imazametabenz-methyl, imazamox, imazamox-ammonium, imazapic, imazapyr, imazapyr-isopropyl-ammonium, imazaquine, imazaquine-ammonium, imazetapyr, imazetapyr-ammonium, imazo-sulfurone, inabenfide, indanophane, indaziflam, indoleacetic acid-IA-3-indoleic acid 4-IAA (IBA), iodo-sulfurone, iodosulfurone-methyl-sodium, ioxynil, ipfencarbazone, isocarbamide, isopropaline, isoproturone, isourone, isoxabene, iso xaclortole, isoxaflutole, isoxapirifop, KUH043, i.e., 3 - ({[5- (difluoromethyl) -1-methyl-3- (trifluoromethyl) -1H-pyrazol-4-yl] -methyl} sulfonyl) -5,5- dimethyl-4,5-dihydro-1,2-oxazole, carbutylate, ketospiradox, lactophen, lenacil, linurone, maleic hydrazide, MCPA, MCPB, MCPB-methyl, ethyl and sodium, mecoprop, mecoprop-sodium, mecoprop- butotyl, mecoprop-Pbutotyl, mecoprop-P-dimethyl-ammonium, mecoprop-P-2-ethyl-hexyl, mecoprop-Ppotassium, mefenacet, mefluidide, mepiquat chloride, meso-sulfurone, mesosulfurone-methyl, mesotrione, metabenztiazurone metamifop, metamitrone, metazachlor, metaza-sulfurone, metazole, methypyrosulfurone, methozoline, methoxyphenone, methyldimrone, 1-methylcyclopropene, methyl isothiocyanate, metobenzurone, metobromurone, metolachlor, methoxymethyl, methoxymethyl, methoxymethloromethane, methoxymetho molinate, monalide, monocarbamide, monocarbamide dihydrogen sulfate, monolinurone, monosulfurone, monosulfurone ester, monurone, MT-128 , that is, 6-chloro-N - [(2E) -3-chloroprop-2-ene-1-yl] -5-methyl-N-phenyl-pyridazine-3-amine, MT-5950, that is, N - [3-chloro-4- (1-methylethyl) -phenyl] -2-methyl-pentanamide, NGGC011, naproanilide, napropamide, naptalam, NC-310, that is, 4- (2,4dichlorobenzoyl) -1-methyl- 5-benzyloxypyrazole, neburone, nico-sulfurone,
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33/51 nipyraclofen, nitralin, nitrophen, nitrophenolate-sodium (mixture of isomers), nitrofluorphene, nonanoic acid, norflurazone, orbencarb, orthosulfamurone, oryzine, oxadiargyl, oxadiazone, oxa-sulfurone, oxazyclomethane, oxazyclomethane of pdichloride, pelargonic acid (nonanoic acid), pendimethalin, pendralin, penoxsulam, pentanochloride, pentoxazone, perfluidone, petoxamide, fenisofam, fenmedifam, fenmedifamethyl, picloram, picolinafen, pinoxiphenyl, piperopyropyrine, piperopophos, piperophos, piperopyropyrus, piperopyropyropyrophenyl primi-sulfurone-methyl, probenazole, profluazole, prociazine, prodiamine, prifluralin, profoxidime, prohexadione, prohexadionacalium, prohydrojasmone, promethazine, promethine, propachlor, propanyl, propaquizafop, propazine, propam, propoxyazone, propoxyazone sodium, propyresulfurone, propizamide, pro-sulfalin, prosulfocarb, pro-sulfurone, prinachlor, pyraclonyl, piraflufene, piraflufene-ethyl a, pyra-sulfotole, pyrazolinate (pyrazolate), pyrazosulfurone, pyrazosulfurone-ethyl, pyrazoxifene, pyribambenz, pyribambenz-isopropyl, pyribambenz-propyl, pyribenzoxime, pyributicarb, pyridafol, pyridate, pyriftalide, pyriminobac, pyriminobac, pyriminobac, pyriminobac, pyriminobac, pyriminobac, pyriminobac, pyriminobac -sulfan, piritiobac, piritiobac-sodium, pyroxa-sulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuril, safyridone, rimsulfuron, safetyl , sidurone, simazine, symmetrine, SN106279, i.e., (2R) -2 - ({7- [2-chloro-4- (trifluoromethyl) -phenoxy] -2-naphthyl} -oxy) methyl propanoate, sulcotrione, sulfalate (CDEC), sulfentrazone, sulfometurone, sulfometurone-methyl, sulfosate (glyphosate-trimesium), sulfosulfurone, SYN-523, SYP-249, that is, 5- [2-chloro-4- (trifluoromethyl) -phenoxy] -2nitrobenzoate 1-ethoxy-3-methyl-1-oxobut-3-ene-2-yl, SYP-300, ie 1- [7fluoro-3-oxo-4- (prop-2-yne-1-yl) - 3,4-dihydro-2H-1,4-benzoxazine-6-yl] -3-propyl-2tioxo -imidazolidine-4,5-dione, tebutam, tebutiurone, tecnazene, tefuriltrione, tembotrione, tepraloxidime, terbacil, terbucarb, terbucloro, terbumetone, terbutilazine, terbutrin, tenilchlor, thiafluamide, thiazaflurone, thiazaururone, thiazaururone, thiazaururone, thiazaururone, thiazaururone , tifensulfurone, tifensulfurone
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34/51 methyl, thiobencarb, thiocarbazil, topramezone, tralcoxidime, trialate, triasulfurone, triaziflam, triazophenamide, tribenurone, tribenurone-methyl, trichloroacetic acid (TCA), triclopyr, tridiphane, trifluorine, trifluorine, trifluorohydride -sulfurone, triflu-sulfurone-methyl, trimeturone, trinexapac, trinexapac-ethyl, trito-sulfurone, tsitodef, uniconazole, uniconazoleP, vernolate, ZJ-0862, that is, 3,4-dichloro-N- {2 - [(4 , 6-dimethoxypyrimidine-2-yl) -oxy] benzyl} -aniline, and the following compounds:
[076] For application, formulations present in a commercial form are, if appropriate, diluted in a conventional manner, for example, with water, in the case of wetting powders, emulsifiable granules, dispersions and dispersible granules in water. Preparations in the form of dusting products, granules for application to the soil or granules for spreading and sprayable solutions are normally no longer diluted with other inert substances before application.
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35/51 [077] The application rates required for compounds of structural formula (I) vary with external conditions, including temperature, humidity and the type of herbicide used. They can vary in wide limits, for example, between 0,001 and 1,0 kg / ha or more of active substance; however, they are preferably between 0.005 and 750 g / ha. [078] The following examples illustrate the invention.
Chemical examples [079] Synthesis of 2-chloro-5-methyl-3-methylthio-N- (1-methylthetrazol-5-yl) benzamide (n ° 2-27)
Step 1: synthesis of N- (trifluoroacetyl) -2,6-dibromo-4-methylaniline [080] Under an argon atmosphere, 50.0 g (189 mmol) of
2,6-dibromo-4-methylaniline in 500 ml of anhydrous dichloromethane and cooled to a temperature between 0 ° C-5 ° C. At this temperature, 15.7 g (198 mmol) of pyridine was added. At a temperature of 5 ° C-7 ° C, 41.6 g (198 mmol) of trifluoroacetic anhydride was then added dropwise. The reaction mixture was stirred at this temperature for 1 hour and then at room temperature (RT) for 16 hours. For further processing, the contents were washed once with water and twice with 1 M hydrochloric acid. The organic phase was dried and the filtrate was freed from the solvent. 69.3 g of N (trifluoroacetyl) -2,6-dibromo-4-methylaniline were obtained as a residue.
Step 2: synthesis of N- (trifluoroacetyl) -2-bromo-4-methyl-6- (methylthio) -aniline [081] Under an argon atmosphere, 69.3 g (95% pure weight, 182 mmol) was prepared of N- (trifluoroacetyl) -2,6-dibromo-4-methylaniline in 900 ml of anhydrous diethyl ether and cooled to -70 ° C. At this temperature, 153 ml of a 2.5 M solution (382.5 mmol) of n-butyllithium in hexane was added dropwise. Subsequently, the mixture was stirred at this temperature for an additional 30 minutes. At this temperature, a solution of 51.5 g (547 mmol) of dimethyl disulfide in 100 ml of anhydrous diethyl ether was then added dropwise. The contents were stirred at this temperature and then at room temperature for 3 hours and subsequently poured
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36/51 in 1000 ml of 1 M hydrochloric acid. After phase separation, the aqueous phase was extracted with diethyl ether, the combined organic phases were dried and the filtrate was freed from the solvents. The residue was stirred with heptane for 30 minutes and then filtered. 46.6 g of N- (trifluoroacetyl) -2-bromo-
4-methyl-6- (methylthio) -aniline as a residue.
Step 3: synthesis of 5-methyl-3- (methylthio) -2- (trifluoroacetylamino) -benzoic acid [082] Under an argon atmosphere, 46.6 g (142 mmol) of N- (trifluoroacetyl) - 2-bromo-4-methyl-6- (methylthio) -aniline in 750 ml of anhydrous diethyl ether and cooled to a temperature of -65 ° C. At this temperature, 119 ml of a 2.5 M solution (297.5 mmol) of n-butyl lithium in hexane was added dropwise. Subsequently, the mixture was stirred at that temperature for 2 hours. The contents were then carefully poured into a mixture of 62.5 g (1.42 mol) of carbon dioxide (in the form of melting ice ground in a mortar) and 150 ml of anhydrous ether. The mixture was allowed to thaw to room temperature and extracted three times with water. The combined aqueous phases were acidified to pH <2 with dilute hydrochloric acid and cooled to a temperature of 0 ° C-5 ° C. The mixture was filtered and 31.0 g of 5-methyl-3- (methylthio) -2- (trifluoroacetylamino) benzoic acid was obtained as a residue.
Step 4: synthesis of 2-amino-5-methyl-3- (methylthio) -benzoic acid [083] 22.0 g (75.0 mmol) of 5-methyl-3- (methylthio) -2 was heated (trifluoro-acetylamino) -benzoic acid and 9.44 g (225 mmol) of refluxing lithium hydroxide monohydrate in a mixture of 200 ml of methanol and 30 ml of water for 4 hours. For further processing, the contents were cooled and released from solvents. The residue was taken up in water and the mixture was acidified to pH <3 with dilute hydrochloric acid. The mixture was stirred at 0 ° C-5 ° C for 30 minutes and then filtered. 15.0 g of 2-amino-5-methyl-3- (methylthio) -benzoic acid were obtained with a purity> 95% by weight as a residue.
Step 5: synthesis of 2-chloro-5-methyl-3- (methylthio) -benzoic acid
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37/51 [084] 13 ml of concentrated hydrochloric acid was added to 6.00 g (30.4 mmol) of 2-amino-5-methyl-3- (methylthio) -benzoic acid in 35 ml of water and heated mix at 60 ° C for a few minutes. The solution was then cooled to a temperature of 0 ° C-5 ° C and a solution of 2.31 g (33.5 mmol) of sodium nitrite in 10 ml of water was slowly added dropwise. at this temperature. Subsequently, the mixture was stirred at this temperature for an additional 1 hour. This solution was added dropwise to a mixture, at room temperature, of 4.52 g (45.6 mmol) of copper (I) chloride, 35 ml of water and 27 ml of concentrated hydrochloric acid. The mixture was stirred at room temperature for 15 minutes and then slowly heated to reflux. The contents were then heated under reflux for 15 minutes. For further processing, the reaction mixture was cooled, filtered and the residue was washed with water. 5.62 g of 2-chloro-5-methyl-3- (methylthio) -benzoic acid were obtained as a residue.
[085] Step 6: synthesis of 2-chloro-5-methyl-3-methylthio-N- (1-methylthetrazol-5-yl) benzamide (n ° 2-16) [086] 500 mg (2, 31 mmol) of 2-chloro-5-methyl-3 (methylthio) -benzoic acid and 320 mg (3.23 mmol) of 5-amino-1-methyltetrazole and a catalytic amount of 4- (dimethylamino) -pyridine in 10 ml of pyridine. 410 mg (3.23 mmol) of oxalyl chloride was then carefully added dropwise. After 10 minutes, the mixture was stirred at 80 ° C for 4 hours. To complete the reaction, an additional 137 mg (1.08 mmol) of oxalyl chloride was added at room temperature and the mixture was stirred at 80 ° C for an additional 4 hours. For further processing, the contents were cooled to room temperature, freed from solvent on a rotary evaporator and the residue was dissolved in dichloromethane. The solution was washed with a saturated aqueous solution of sodium bicarbonate and the organic phase was then freed from the solvent. The residue was purified by chromatography to obtain 495 mg of 2-chloro-5-methyl-3-methylthio-N- (1-methylthetrazol-5-yl) -benzamide.
[087] The examples presented in the following tables have been prepared
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38/51 in a manner analogous to the aforementioned methods or are obtained in a manner analogous to the aforementioned methods. The compounds listed in the following tables are more particularly preferred.
[088] The abbreviations used have the following meanings: Et = ethyl
Me = methyl
Table 1: compounds according to the invention of structural formula (I), in which the symbol A represents CY and the symbol B represents CH
R
W
No. R X Y Z W Physical data ( ¹ H NMR, DMSO-d6, 400 MHz) 1-1 Me I SMe H Me 7.37 (s, 1H), 7.05 (s, 1H), 7.00 (s, 1H), 3.97 (s, 3H), 2.50 (s, 3H), 2.36 (s , 3H) in CDCb 1-2 Me I SO2Me H Me 8.15 (s, 1H), 7.63 (s, 1H), 7.48 (s, 1H), 3.95 (s, 3H), 3.29 (s, 3H), 2.44 (s , 3H) in CDCb 1-3 Me I SOMe H Me 7.71 - 7.69 (m, 2H), 7.48 (s, 1H), 3.96 (s,3H), 2.76 (s, 3H), 2.49 (s, 3H) in CDCb 1-4 Me Br SMe H Me 7.34 (s, 1H), 7.12 (s, 1H), 7.05 (s, 1H), 3.92 (s, 3H), 2.51 (s, 3H), 2.36 (s , 3H) in CDCb 1-5 Me Br SOMe H Me 7.80 (s, 1H), 7.75 (s, 1H), 7.57 (s, 1H), 3.92 (s, 3H), 2.82 (s, 3H), 2.48 (s , 3H) in CDCb 1-6 Me Br SO2Me H Me 8.14 (s, 1H), 7.70 (s, 1H), 7.60 (s, 1H), 3.91 (s, 3H), 3.31 (s, 3H), 2.45 (s , 3H) in CDCb 1-7 Me Cl SMe H Me1-8 Me Cl SOMe H Me1-9 Me Cl SO2Me H Me1-10 Me Me SMe H Me
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No. R X Y Z W Physical data ( ¹ H NMR, DMSO-d6, 400 MHz) 1-11 Me Me SOMe H Me1-12 Me Me SO2Me H Me1-13 Me Cl H F Me 11.14 (s lr, 1H), 7.88 (s, 1H), 7.68 (d, 1H),7.53 (d, 1H), 3.75 (s, 3H), 2.56 (s, 3H), 2.28 (s, 3H) 1-14 Me Cl H SMe Me 11.04 (s lr, 1H), 7.88 (s, 1H), 7.51 (s, 1H),7.28 (s, 1H), 3.74 (s, 3H), 2.56 (s, 3H), 2.26 (s, 3H) 1-15 Me Cl H SO2Me Me 11.42 (s lr, 1H), 7.99 (s, 1H), 7.93 (s, 1H),7.88 (s, 1H), 3.78 (s, 3H), 3.34 (s, 3H), 2.68 (s, 3H)
Table 2: compounds according to the invention of structural formula (I), in which the symbol A represents CY and the symbol B represents N
W
No. R X Y Z W Physical data ( ¹ H NMR, DMSO-d6, 400 MHz) 2-1 Me Me SMe H Me 7.16 (s, 1H), 4.11 (s, 3H), 2.49 (s,3H), 2.45 (s, 3H), 2.40 (s, 3H) 2-2 Me Me SOMe H Me 7.92 (s, 1H), 7.59 (s, 1H), 4.11 (s, 3H), 2.70 (s, 3H), 2.50 (s, 3H), 2.42 (s , 3H) 2-3 Me Me SO2Me H Me 8.11 (s, 1H), 7.77 (s, 1H), 4.14 (s,3H), 3.14 (s, 3H), 2.82 (s, 3H), 2.49 (s, 3H)
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No. R X Y Z W Physical data ( ¹ H NMR, DMSO-d6, 400 MHz) 2-4 Et Me SMe H Me 7.16 (s, 1H), 4.47 (q, 2H), 2.49 (s, 3H), 2.44 (s, 3H), 2.40 (s, 3H), 1.63(t, 3H) 2-5 Et Me SOMe H Me 7.86 (s, 1H), 7.59 (s, 1H), 4.46 (q,2H), 2.69 (s, 3H), 2.50 (s, 3H), 2.41 (s, 3H), 1.64 (t, 3H) 2-6 Et Me SO ₂ Me H Me 8.11 (s, 1H), 7.74 (s, 1H), 4.51 (q,2H), 3.15 (s, 3H), 2.83 (s, 3H), 2.49 (s, 3H), 1.63 (t, 3H) 2-7 n-Pr Me SMe H Me2-8 n-Pr Me SOMe H Me2-9 n-Pr Me SO ₂ Me H Me2-10 Me NH2 SMe H Me2-11 Me NH2 SOMe H Me 8.06 (s, 1H), 7.29 (s, 1H), 4.05 (s,3H), 2.93 (s, 3H), 2.37 (s, 3H) 2-12 Me NH2 SO ₂ Me H Me2-13 Me NH (C = O) CF3 SMe H Me 7.55 (s, 1H), 7.35 (s, 1H), 4.08 (s,3H), 2.52 (s, 3H), 2.41 (s, 3H) 2-14 Me NH (C = O) CF3 SOMe H Me2-15 Me NH (C = O) CF3 SO ₂ Me H Me 8.01 (s lr, 2H), 4.03 (s lr, 3H), 3.13(s, 3H), 2.47 (s lr, 3H) 2-16 Me Cl SMe H Me 7.32 (s, 1H), 7.14 (s, 1H), 4.12 (s,3H), 2.52 (s, 3H), 2.41 (s, 3H) 2-17 Me Cl SOMe H Me 7.82 (s, 1H), 7.65 (s, 1H), 4.12 (s,3H), 2.83 (s, 3H), 2.52 (s, 3H) 2-18 Me Cl SO ₂ Me H Me 8.20 (s, 1H), 7.75 (s, 1H), 4.14 (s,3H), 3.32 (s, 3H), 2.51 (s, 3H)
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No. R X Y Z W Physical data ( ¹ H NMR, DMSO-d6, 400 MHz) 2-19 Et Cl SMe H Me 7.31 (s, 1H), 7.14 (s, 1H), 4.48 (q,2H), 2.52 (s, 3H), 2.41 (s, 3H), 1.63(t, 3H) 2-20 Et Cl SOMe H Me 7.77 (s, 1H), 7.63 (s, 1H), 4.48 (q,2H), 2.82 (s, 3H), 2.51 (s, 3H), 1.64 (t, 3H) 2-21 Et Cl SO ₂ Me H Me 8.18 (s, 1H), 7.75 (s, 1H), 4.51 (q, 2H), 3.34 (s, 3H), 2.51 (s, 3H), 1.62(t, 3H) 2-22 n-Pr Cl SMe H Me 7.31 (s, 1H), 7.13 (s, 1H), 4.41 (t,2H), 2.51 (s, 3H), 2.41 (s, 3H), 2.03(Fri, 2H), 0.99 (t, 3H) 2-23 n-Pr Cl SOMe H Me 7.77 (s, 1H), 7.63 (s, 1H), 4.41 (t,2H), 2.82 (s, 3H), 2.52 (s, 3H), 2.05(sex, 2H), 1.01 (t, 3H) 2-24 n-Pr Cl SO ₂ Me H Me 8.18 (s, 1H), 7.73 (s, 1H), 4.44 (t, 2H), 3.34 (s, 3H), 2.50 (s, 3H), 2.03 (sex , 2H), 0.99 (t, 3H) 2-25 Me Br SMe H Me 7.20 (s, 1H), 7.08 (s, 1H), 4.15 (s,3H), 2.51 (s, 3H), 2.39 (s, 3H) 2-26 Me Br SOMe H Me 7.82 (s, 1H), 7.57 (s, 1H), 4.15 (s,3H), 2.82 (s, 3H), 2.51 (s, 3H) 2-27 Me Br SO ₂ Me H Me 8.21 (s, 1H), 7.64 (s, 1H), 4.17 (s,3H), 3.33 (s, 3H), 2.49 (s, 3H) 2-28 Et Br SMe H Me 7.19 (s, 1H), 7.08 (s, 1H), 4.51 (q, 2H), 2.51 (s, 3H), 2.39 (s, 3H), 1.65(t, 3H) 2-29 Et Br SOMe H Me 7.72 (s, 1H), 7.55 (s, 1H), 4.50 (q, 2H), 2.79 (s, 3H), 2.51 (s, 3H), 1.66(t, 3H)
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No. R X Y Z W Physical data ( ¹ H NMR, DMSO-d6, 400 MHz) 2-30 Et Br SO2Me H Me 8.19 (s, 1H), 7.63 (s, 1H), 4.53 (q, 2H), 3.33 (s, 3H), 2.49 (s, 3H), 1.65(t, 3H) 2-31 n-Pr Br SMe H Me 7.19 (s, 1H), 7.08 (s, 1H), 4.44 (t,2H), 2.51 (s, 3H), 2.39 (s, 3H), 2.06(Fri, 2H), 1.00 (t, 3H) 2-32 n-Pr Br SOMe H Me 7.70 (s, 1H), 7.54 (s, 1H), 4.43 (t,2H), 2.78 (s, 3H), 2.51 (s, 3H), 2.07(sex, 2H), 1.03 (t, 3H) 2-33 n-Pr Br SO2Me H Me 8.20 (s, 1H), 7.62 (s, 1H), 4.45 (t, 2H), 3.33 (s, 3H), 2.49 (s, 3H), 2.06 (sex , 2H), 1.01 (t, 3H) 2-34 Me I SMe H Me 7.11 (s, 1H), 7.03 (s, 1H), 4.20 (s,3H), 2.50 (s, 3H), 2.39 (s, 3H) inCDCl3 2-35 Me I SOMe H Me 7.70 (s, 1H), 7.64 (s, 1H), 4.04 (s,3H), 2.79 (s, 3H), 2.45 (s, 3H) 2-36 Me I SO2Me H Me2-37 Me OMe SMe H F 11.45 (s lr, 1H), 7.29 (2d, 2H), 3.98(s, 3H), 3.80 (s, 3H), 2.5 (s, 3H) 2-38 Me OMe SO2Me H F 11.94 (s lr, 1H), 8.01 (dd, 1H), 7.80(dd, 1H), 4.02 (s, 3H), 3.94 (s, 3H), 3.37 (s, 3H) 2-39 Me Cl H SO2Me Me 11.96 (s lr, 1H), 8.00 (s, 1H), 7.91 (s,1H), 4.01 (s, 3H), 3.35 (s, 3H), 2.68 (s, 3H) 2-40 Me Cl H SOMe Cl 8.18 (s, 1H), 7.88 (s, 1H), 4.02 (s,3H), 2.90 (s, 3H) 2-41 Me Cl H SO2Me Cl 8.32 (s, 1H), 8.11 (s, 1H), 4.02 (s,3H), 3.48 (s, 3H)
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No. R X Y Z W Physical data(1H NMR, DMSO-d6, 400 MHz) 2-42 Me Cl Me F Me 7.56 (d, 1H), 3.98 (s, 3H), 2.31 (d,3H), 2.28 (d, 3H) 2-43 Me Cl Me SMe Me2-44 Me Cl Me SOMe Me 7.53 (s, 1H), 4.00 (s, 3H), 2.96 (s,3H), 2.66 (s, 3H), 2.57 (s, 3H) 2-45 Me Cl Me SO ₃ Me Me 11.88 (s lr, 1H), 7.69 (s, 1H), 4.01 (s,3H), 3.34 (s, 3H), 2.76 (s, 3H), 2.69(s, 3H) 2-46 Et Cl Me SMe Me2-47 Et Cl Me SOMe Me 7.53 (s, 1H), 4.36 (q, 2H), 2.96 (s,3H), 2.66 (s, 3H), 2.57 (s, 3H), 1.47(t, 3H) 2-48 Et Cl Me SO ₃ Me Me 11.78 (s lr, 1H), 7.68 (s, 1H), 4.37 (q, 2H), 3.34 (s, 3H), 2.76 (s, 3H), 2.69 ( s, 3H), 1.48 (t, 3H) 2-49 Pr Cl Me SMe Me2-50 Pr Cl Me SOMe Me 7.53 (s, 1H), 4.32 (t, 2H), 2.96 (s,3H), 2.66 (s, 3H), 2.57 (s, 3H), 1.88(m, 2H), 0.88 (t, 3H) 2-51 Pr Cl Me SO ₃ Me Me 7.66 (s, 1H), 4.32 (t, 2H), 3.31 (s,3H), 2.76 (s, 3H), 2.70 (s, 3H), 1.88 (m, 2H), 0.88 (t, 3H) 2-52 Me Cl OMe SMe OMe 9.95 (s lr, 1H), 7.14 (s, 1H), 4.11 (s, 3H), 3.97 (s, 3H), 3.94 (s, 3H), 2.50 ( s, 3H) 2-53 Me Cl OMe SO ₃ Me OMe 11.92 (s lr, 1H), 7.49 (s, 1H), 4.03 (s, 3H), 3.98 (s, 3H), 3.89 (s, 3H), 3.37 ( s, 3H) 2-54 Me Cl CO ₃ Me Cl Me2-55 Me Cl CO ₃ Me SMe Me
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No. R X Y Z W Physical data(1H NMR, DMSO-d6, 400 MHz) 2-56 Me Cl CO2Me SO2Me Me2-57 Me Cl CO2Me Cl Cl2-58 Me Cl CO2Me SMe Cl2-59 Me Cl CO2Me SO2Me Cl2-60 Me Me NH2 SO2Me Me 8.67 (s, 1H), 6.81 (s, 1H), 5.72 (s, 2H), 4.12 (s, 3H), 3.11 (s, 3H), 2.66 (s , 3H), 2.26 (s, 3H) 2-61 Me Me NMe2 SO2Me Me 11.65 (s lr, 1H), 7.48 (s, 1H), 4.00 (s, 3H), 3.38 (s, 3H), 2.80 (s, 6H), 2.62 ( s, 3H), 2.35 (s, 3H) 2-62 Me Me NHEt SO2Me Me 10.66 (s lr, 1H), 7.13 (s, 1H), 6.28 (s lr, 1H), 4.11 (s, 3H), 3.15 (q, 2H), 3.14 (s, 3H), 2.68 (s, 3H), 2.41 (s, 3H), 1.26 (t, 3H) 2-63 Me Cl H SMe Cl 11.82 (s lr, 1H), 7.90 (s, 1H), 7.41 (s,1H), 3.95 (s, 3H), 2.60 (s, 3H) 2-64 Me Cl H SMe Me 11.61 (s lr, 1H), 7.57 (s, 1H), 7.30 (s,1H), 3.97 (s, 3H), 2.57 (s, 3H), 2.27 (s, 3H) 2-65 Me Cl H SOMe Me 11.85 (s lr, 1H), 7.85 (s, 1H), 7.73 (s,1H), 4.00 (s, 3H), 2.75 (s, 3H), 2.38 (s, 3H) 2-66 Me F H CN F 11.95 (s lr, 1H), 8.25 (dd, 1H), 8.05(dd, 1H), 3.98 (s, 3H) 2-67 Et F H CN F 11.89 (s lr, 1H), 8.25 (dd, 1H), 8.06(dd, 1H), 4.33 (q, 2H), 1.45 (t, 3H) 2-68 Et Cl H SO2Me Cl
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No. R X Y Z W Physical data ( ¹ H NMR, DMSO-d6, 400 MHz) 2-69 Et Me NMe ₂ SO2Me Me 11.57 (s lr, 1H), 7.47 (s, 1H), 4.34 (q, 2H), 3.38 (s, 3H), 2.80 (s, 6H), 2.62 ( s, 3H), 2.35 (s, 3H), 1.48 (t, 3H) 2-70 Me Cl H F Me2-71 Et Cl H Cl Cl 11.85 (s lr, 1H), 8.17 (s, 1H), 8.07 (s,1H), 4.36 (q, 2H), 1.47 (t, 3H) 2-72 C2H4OMe Me SMe H Me2-73 C2H4OMe Me SOMe H Me2-74 C2H4OMe Me SO2Me H Me2-75 C2H4OMe Cl SMe H Me2-76 C2H4OMe Cl SOMe H Me2-77 C2H4OMe Cl SO2Me H Me2-78 C2H4OMe Br SMe H Me2-79 C2H4OMe Br SOMe H Me2-80 C2H4OMe Br SO2Me H Me2-81 C2H4OMe Cl Me SMe Me2-82 C2H4OMe Cl Me SO2Me Me
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No. R X Y Z W Physical data ( ¹ H NMR, DMSO-d6, 400 MHz) 2-83 C2H4OMe Me NMe2 SO ₂ Me Me 10.02 (s Ir, 1H), 7.31 (s, 1H), 4.64 (t, 4H), 3.84 (t, 2H), 3.37 (s, 3H), 3.33 ( s, 3H), 2.88 (s, 6H), 2.70 (s, 3H), 2.45 (s, 3H)
Table 3: compounds according to the invention of structural formula (I), in which the symbols A and B represent N
W
No. R X Z W Physical data(1H-NMR, DMSO-d6, 400 MHz) 3-1 Me Me CF3 Me3-2 Me Me CF3 F3-3 Me Me CF3 Cl3-4 Me Me Cl Me3-5 Me Me Cl Cl3-6 Me Me SMe Me3-7 Me Me SO ₂ Me Me3-8 Me Me SMe Cl3-9 Me Me SO ₂ Me Cl3-10 Me Cl CF3 Me3-11 Me Cl CF3 F3-12 Me Cl CF3 Cl3-13 Me Cl Cl Me3-14 Me Cl Cl F 12.08 (s lr, 1H), 8.61 (d, 1H), 4.01 (s, 3H) 3-15 Et Cl Cl F 11.99 (s lr, 1H), 8.62 (d, 1H), 4.37 (q, 2H),1.48 (t, 3H)
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No. R X Z W Physical data(1H-NMR, DMSO-d6, 400 MHz) 3-16 Me Cl Cl Cl3-17 Me Cl SMe Me3-18 Me Cl SO ₃ Me Me3-19 Me Cl SMe F3-20 Me Cl SO ₃ Me F3-21 Me Cl SMe Cl3-22 Me Cl SO ₃ Me Cl[089] B. Exemp formulation
a) A dusting product is obtained by mixing 10 parts by weight of a compound of structural formula (I) and / or its salts and 90 parts by weight of talc as an inert substance and comminution of the mixture in a hammer mill.
b) A water-dispersible humectable powder is obtained by mixing 25 parts by weight of a compound of structural formula (I) and / or its salts, 64 parts by weight of quartz containing kaolin as an inert substance, 10 parts by weight of potassium lignosulphonate and 1 part by weight of sodium oleoylmethyltaurate as a wetting and dispersing agent and grinding the mixture in a pin disc mill.
c) A water-dispersible dispersion concentrate is obtained by mixing 20 parts by weight of a compound of structural formula (I) and / or its salts with 6 parts by weight of polyphenolic alkylphenol ether (®Triton X 207), 3 parts by weight of polyglycolic isotridecanol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, between about 255 ° C and above 277 ° C) and grinding the mixture in a mill of beads up to a fineness of less than 5 microns.
d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of formula (I) and / or its salts, 75 parts by weight of cyclohexanone as a solvent and 10 parts by weight of ethoxylated nonylphenol as an emulsifier .
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e) Water-dispersible granules are obtained by mixing parts by weight of a compound of structural formula (I) and / or its salts, parts by weight of calcium lignosulphonate, parts by weight of sodium laurel sulphate, parts by weight of polyvinyl alcohol and parts by weight and kaolin, grinding the mixture in a pin disc mill and granulating the powder in a fluidized bed by applying a spray of water as the granulation liquid.
f) Water-dispersible granules are also obtained by homogenization and pre-comminution of parts by weight of a compound of structural formula (I) and / or its salts, parts by weight of 2,2'-dinaftymethane-6.6 ' -sodium disulfonate, parts by weight of sodium oleoylmethyltaurate, parts by weight of polyvinyl alcohol, parts by weight of calcium carbonate and parts by weight of water in a colloid mill, subsequent grinding of the mixture in a microsphere and atomization mill and drying of the resulting suspension in a spray tower via a single substance injector.
[090] C. Biological examples
1. Pre-emergence herbicidal action against harmful plants [091] Seeds of monocotyledonous and dicotyledonous herb plants and crop plants are placed in wooden fiber pots in slime soil and covered with soil. The compounds of the invention, formulated in the form of wetting powders (WP) or emulsion concentrates (EC), are then applied to the surface of the covering soil, in the form of an aqueous suspension or emulsion at an application rate of 600 to 800 water
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L / ha (converted) with the addition of 0.2% wetting agent. After the treatment, the pots are placed in a greenhouse and kept under good growth conditions for the plants under test. Test plant damage is assessed visually after a 3-week test period by comparison with untreated controls (percentage herbicidal activity (%): 100% action = plants have died, 0% action = equal to plants of control). In this case, for example, each of the compounds ^Nos 1-06, 2-01, 202, 2-03, 2-04, 2-05, 2-06, 2-16, 2-19, 2-21, 2-37, 2-43, 2-48, 2-49, 2-64 and 2-69, for an application rate of 320 g / ha, showed an activity of at least 80% against Alopecurus myosuroides and Amaranthus retroflexus. Each of the compounds ^Nos 2-17, 2-18, 2-20, 2-22, 2-23, 2-24, 2-27, 2-30, 2-33, 244, 2-45, 2- 46, 2-47 and 2-62, for an application rate of 320 g / ha, showed an activity of at least 80% against Cyperus serotinus and Setaria viridis. Each of the compounds ^Nos 2-25, 2-26, 2-28, 2-29, 2-37, 2-42 and
2-34, for an application rate of 320 g / ha, showed an activity of at least 80% against Abutilan theophrasti and Avena fatua. Each of the compounds ^Nos 2-32, 2-37, 2-39, 2-50, 2-51, 2-61, 2-69 and 2-83 to an application rate of 320 g / ha, presented an activity of at least 80% against Echinochloa crus galli and Veronica persica.
2. Post-emergence herbicidal action against harmful plants [092] Seeds of monocotyledonous and dicotyledonous herbs and crop plants are placed in wooden fiber pots in slime soil, covered with soil and grown in a greenhouse with good growth conditions. 2 to 3 weeks after sowing, the test plants are treated in one leaf stage. The compounds of the invention, formulated in the form of wetting powders (WP) or emulsion concentrates (EC), are then sprayed on the green parts of plants, in the form of an aqueous suspension or emulsion at a water application rate. 600 to 800 L / ha (converted) with the addition of 0.2% wetting agent. After allowing the test plants to rest in the greenhouse under optimal growth conditions for about 3 weeks,
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2-04, 2-05, 2-06, 2-16, 2-17, 2-18, 2-19, 2-20, 2-21, 2-22, 2-23, 2-24, 2- 25, 226, 2-27, 2-28, 2-29, 2-30, 2-31, 2-33, 2-34, 2-35, 2-39, 2-40, 2-41, 2- 43, 2-44,
2-45, 2-46, 2-47, 2-48, 2-49, 2-50, 2-51, 2-52, 2-53, 2-60, 2-61, 2-62, 2- 63, 264, 2-65, 2-69 and 2-83, for an application rate of 80 g / ha, showed an activity of at least 80% against Abutilan theophrasti and Veronica persica. Each of the compounds ^Nos 1-14, 2-32, 2-42, 2-66, 2-67, 2-69 and 2-83 to an application rate of 80 g / ha, the activity showed a minus 80% against Amaranthus retroflexus and Stellaria media.
3. Comparison tests [093] For comparison tests, compound No. 1-15 according to the invention and compounds No. 118 and No. 119 known from EP 0 049 071 A1 were tested by the method post-emergence in various dosages against various harmful plants. The classifications show that, unlike the compounds known from EP 0 049 071 A1, the compound according to the invention has a high herbicidal activity against harmful plants, even at very low dosages.
Compound Dose Herbicidal action against [g / ha] ABUTH PHBPU VERPE Compound No. 1-15 according to 80 90% 80% 80% 20 90% 80% 80% invention 5 90% 80% 40% Compound No. 118 known from 80 0% 0% 0% 20 0% 0% 0% EP 0 049 071 A1 5 0% 0% 0%
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Compound Dose Herbicidal action against [g / ha] ABUTH PHBPU VERPE Compound No. 119 known from 80 0% 0% 0% 20 0% 0% 0% EP 0 049 071 A1 5 0% 0% 0%
[094] The abbreviations used have the following meanings:
ABUTH Abutilan theophrasti
PHBPU Pharbitis purpureum
VERPE Veronica Persica

权利要求:
Claims (7)
[1]
1. N- (tetrazol-5-yl) - or N- (triazol-5-yl) -arylcarboxamide substituted in
5-phenyl of structural formula (I) or a salt thereof
W (I), characterized by the fact that the symbol A represents N or CY, the symbol B represents N or CH, the symbol X represents halogen, aquila (C1-C6), NH2, OR ¹ or NR1COR ¹ , the symbol Y represents hydrogen, (C1-C6), COOR ¹ , OR ¹ , S (O) nR ² , N (R1) 2, the symbol Z represents halogen, cyan, halo- (C1-C6) -alkyl, S (O ) nR ² , (C 1 -C 6) alkyl -OR ¹ , or the symbol Z can also represent hydrogen, if the symbol Y represents the radical S (O) nR ² , the symbol W represents aquila (C1-C6) or halogen, the symbol R represents aquila (C1-C3) which is unsubstituted or substituted by methoxy, the symbol R ¹ represents hydrogen, aquila (C1-C6) or haloaquila (C1-C6), the symbol R ² represents aquila (C1-C6 ), the symbol s represents 0, 1,2 or 3, and the symbol n represents 0, 1 or 2.
[2]
2. Herbicidal composition characterized by the fact that it has a herbicidal effective amount of at least one compound of structural formula (I) as defined in claim 1.
[3]
3. Herbicidal composition, according to claim 2, characterized by the fact that it is in a mixture with formulation aids.
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[4]
4. Method for the control of unwanted plants, characterized by the fact that an effective amount of at least one compound of structural formula (I), as defined in claim 1, or a herbicidal composition, as defined in claim 2 or 3, it is applied to plants or the location of unwanted vegetation.
[5]
5. Use of a compound of structural formula (I), as defined in claim 1 or a herbicidal composition, as defined in claim 2 or 3, characterized by the fact that it is for the control of unwanted plants.
[6]
6. Use according to claim 5, characterized by the fact that the compounds of structural formula (I) are used to control unwanted plants in useful plant cultures.
[7]
7. Use according to claim 6, characterized by the fact that useful plants are useful transgenic plants.

类似技术:

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公开号 | 公开日 | 专利标题

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BR112014010813B1|2019-12-17|5-phenyl substituted n- | - or 5-phenyl substituted n- | arylcarboxamide, herbicidal composition, method for controlling unwanted plants and their use

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DK2688885T3|2016-09-12|N- | ARYLCARBOXYLSYREAMIDER AND THEIR USE AS HERBICIDES

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同族专利:

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公开号 | 公开日

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CA2854098C|2019-03-26|

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AU2012331281B2|2017-06-15|

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CN104011031A|2014-08-27|

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ES2600082T3|2017-02-07|

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US9259001B2|2016-02-16|

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EP2773625B1|2016-08-24|

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MX353511B|2018-01-17|

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UA113861C2|2017-03-27|

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CN104011031B|2016-07-06|

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JP2015501325A|2015-01-15|

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EP2773625A1|2014-09-10|

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ZA201402993B|2015-11-25|

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IN2014CN03648A|2015-10-09|

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BR112014010813A2|2017-05-02|

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JP6082400B2|2017-02-15|

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RU2014122254A|2015-12-10|

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PL2773625T3|2017-03-31|

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HUE029419T2|2017-02-28|

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MX2014004955A|2014-05-28|

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WO2013064457A1|2013-05-10|

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AU2012331281A1|2014-05-15|

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US20140296069A1|2014-10-02|

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CA2854098A1|2013-05-10|

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EP2589598A1|2013-05-08|

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RU2629952C2|2017-09-05|

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法律状态:
2017-05-30| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2018-05-02| B07A| Technical examination (opinion): publication of technical examination (opinion)|

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2019-02-05| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|

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2019-10-08| B09A| Decision: intention to grant|

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2019-12-17| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/10/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP11187669.4A|EP2589598A1|2011-11-03|2011-11-03|5-phenyl substituted N-- and N-aryl carboxylic acid amides and use of same as herbicides|

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PCT/EP2012/071378|WO2013064457A1|2011-11-03|2012-10-29|5-phenyl-substituted n- aryl carboxylic acid amides and n- aryl carboxylic acid amides, and use thereof as herbicides|

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