5-Acylamino pyrazole derivatives.

The invention relates to new 5-acylamino-pyrazole derivatives, several processes for their preparation and their use as herbicides and growth regulators.

It is already known that certain 5-acylamido-1-aryl-pyrazoles, such as 4-cyano-5-propionamido-1- (2,4,6-trichlorophenyl) pyrazole, have herbicidal properties (see, for example, DE- OS 3 226 513).

However, the herbicidal activity of these previously known compounds against weeds, as well as their tolerance to important crop plants, is not always completely satisfactory in all fields of application.

New 5-acylamino-pyrazole derivatives of the general formula (I)<chemistry id="chem0001" num="0001"><img file="EP0248315A2_D0001.tif" /></chemistry> in which R¹ represents hydrogen, halogen or nitro, R² represents hydrogen, alkyl, alkenyl, alkynyl or optionally substituted cycloalkyl, Ar represents in each case optionally substituted phenyl or pyridyl, X represents oxygen or sulfur, A represents a straight-chain or branched, optionally substituted alkylene bridge, n stands for the numbers 0 or 1 and Y for cyano or the grouping<chemistry id="chem0002" num="0002"><img file="EP0248315A2_D0002.tif" /></chemistry> stands, where X¹ represents oxygen or sulfur and R³ represents hydroxy, alkoxy, alkenyloxy, alkynyloxy, alkylthio, amino, alkylamino, dialkylamino, alkenylamino, dialkenylamino, alkyl-alkenylamino or a radical -OM, where M represents an equivalent of the cation of an inorganic or organic base, found.

It was also found that the new 5-acylamino-pyrazole derivatives of the formula (I)<chemistry id="chem0003" num="0003"><img file="EP0248315A2_D0003.tif" /></chemistry> in which R¹ represents hydrogen, halogen or nitro, R² represents hydrogen, alkyl, alkenyl, alkynyl or optionally substituted cycloalkyl, Ar represents in each case optionally substituted phenyl or pyridyl, X represents oxygen or sulfur, A represents a straight-chain or branched, optionally substituted alkylene bridge, n stands for the numbers 0 or 1 and Y for cyano or the grouping<chemistry id="chem0004" num="0004"><img file="EP0248315A2_D0004.tif" /></chemistry> stands, where X¹ represents oxygen or sulfur and R³ represents hydroxy, alkoxy, alkenyloxy, alkynyloxy, alkylthio, amino, alkylamino, dialkylamino, alkenylamino, dialkenylamino, alkyl-alkenylamino or a radical OM, where M represents an equivalent of the cation of an inorganic or organic base, using the procedures described below:<ul id="ul0001" list-style="none"><li>a) 5-acylamino-pyrazole derivatives of the formula (Ia) are obtained<chemistry id="chem0005" num="0005"><img file="EP0248315A2_D0005.tif" /></chemistry> in which R¹, X, Y, A, Ar and the index n have the meaning given above, if 5-amino-1-aryl-pyrazoles of the formula (II)<chemistry id="chem0006" num="0006"><img file="EP0248315A2_D0006.tif" /></chemistry> in which R¹ and Ar have the meaning given above, with acylating agents of the formula (III) E¹ - <img file="EP0248315A2_D0007.tif" /> - (A)_n - Y (III) in which X, Y, A and the index n have the meaning given above and E¹ represents an electron-withdrawing leaving group, if appropriate in the presence of a diluent, if appropriate in the presence of an acid binder and if appropriate in the presence of a catalyst;</li><li>b) 5-acylamino-pyrazole derivatives of the formula (Ib) are obtained<chemistry id="chem0007" num="0007"><img file="EP0248315A2_D0008.tif" /></chemistry> in which R¹, X, Y, A, the index n and Ar have the meaning given above and R²⁻¹ represents alkyl, alkenyl, alkynyl or optionally substituted cycloalkyl, if the 5-acylamino-pyrazole derivatives of the formula (Ia) obtainable by process (a)<chemistry id="chem0008" num="0008"><img file="EP0248315A2_D0009.tif" /></chemistry> in which R¹, X, Y, A, Ar and the index n have the meaning given above, with alkylating agents of the formula (IV) E² - R²⁻¹ (IV) in which R²⁻¹ has the meaning given above and E² represents halogen, optionally substituted alkoxysulfonyloxy or optionally substituted arylsulfonyloxy, if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder and if appropriate in the presence of a catalyst;</li><li>c) 5-acylamino-pyrazole derivatives of the formula (Ic) are obtained<chemistry id="chem0009" num="0009"><img file="EP0248315A2_D0010.tif" /></chemistry> in which R¹, R², Ar, X, A and the index n have the meaning given above, if 5-acylamido-1-aryl-pyrazoles of the formula (V)<chemistry id="chem0010" num="0010"><img file="EP0248315A2_D0011.tif" /></chemistry> in which R¹, R², Ar, X, A and the index n have the meaning given above and E³ represents halogen, with cyan derivatives of the formula (VI) W-CN (VI) in which W represents hydrogen, an equivalent of an alkaline earth or alkali metal cation or an equivalent of the cation of an organic base, if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder and if appropriate in the presence of a catalyst;</li><li>d) 5-acylamino-pyrazole derivatives of the formula (Id) are obtained<chemistry id="chem0011" num="0011"><img file="EP0248315A2_D0012.tif" /></chemistry> in which R², X, A, Y, Ar and the index n have the meaning given above and R¹⁻¹ represents halogen or nitro, if the 5-acylamino-pyrazole derivatives of the formula (Ie) obtainable with the aid of processes (a), (b), (c), (e) or (f),<chemistry id="chem0012" num="0012"><img file="EP0248315A2_D0013.tif" /></chemistry> in which R², X, Y, A, Ar and the index n have the meaning given above, with halogenating or nitrating agents of the formula (VII) R¹⁻¹ - E⁴ (VII) in which R¹⁻¹ has the meaning given above and E⁴ stands for an electron-withdrawing leaving group, if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst or reaction auxiliary;</li><li>e) 5-acylamino-pyrazole derivatives of the formula (If)<chemistry id="chem0013" num="0013"><img file="EP0248315A2_D0014.tif" /></chemistry> in which R¹, R³ and Ar have the meaning given above and A¹ represents straight-chain or branched alkylene with 1 to 6 carbon atoms, if 5-imido-pyrazoles of the formula (VIII)<chemistry id="chem0014" num="0014"><img file="EP0248315A2_D0015.tif" /></chemistry> in which R¹, Ar, and A¹ have the meaning given above, with nucleophilic compounds of the formula (IX) R³ - H (IX) in which R³ has the meaning given above, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary;</li><li>f) 5-acylamino-pyrazole derivatives of the formula (Ig) are obtained<chemistry id="chem0015" num="0015"><img file="EP0248315A2_D0016.tif" /></chemistry> in which R¹, R², Ar, A, X, X¹, M and the index n have the meaning given above if the 5-acylamino-pyrazole derivatives of the formula (Ih) obtainable by processes (a), (b), (d) or (e) are<chemistry id="chem0016" num="0016"><img file="EP0248315A2_D0017.tif" /></chemistry> in which R¹, R², Ar, X, X¹, A and the index n have the meaning given above and R³⁻¹ represents hydroxy or alkoxy, neutralized or saponified with the hydroxides or carbonates of alkali or alkaline earth metals, or neutralized with organic bases.</li></ul>

Finally, it was found that the new 5-acylamino-pyrazole derivatives of the general formula (I) have herbicidal, in particular also selective herbicidal and growth-regulating properties. Surprisingly, the 5-acylamino-pyrazole derivatives according to the invention of the general formula (I) show a considerably better general herbicidal activity against difficult to control problem weeds and at the same time a significantly improved tolerance to important crop plants compared to the 5-acylamido known from the prior art -1-aryl-pyrazoles, such as 4-cyano-5-propionamido-1- (2,4,6-trichlorophenyl) pyrazole, which are chemically and functionally obvious compounds.

The 5-acylamino-pyrazole derivatives according to the invention are generally defined by the formula (I). Compounds of the formula (I) in which R1 is hydrogen, nitro, fluorine, chlorine, bromine or iodine; R² represents hydrogen, straight-chain or branched alkyl having 1 to 12 carbon atoms, each straight-chain or branched alkenyl and alkynyl each having 3 to 8 carbon atoms and also cycloalkyl having 3 to 8 carbon atoms optionally substituted by alkyl having 1 to 4 carbon atoms; Ar represents phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl, each of which is monosubstituted or polysubstituted by one or more substituents, the following being suitable in each case: Halogen, cyano, nitro, each straight-chain or branched alkyl, alkoxy or alkoxycarbonyl each having 1 to 4 carbon atoms in the alkyl parts, each straight-chain or branched haloalkyl or haloalkoxy each having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms or a radical - SO)_m - R⁴, in which R⁴ represents amino, each straight-chain or branched alkyl, alkylamino, dialkylamino or haloalkyl each having 1 to 4 carbon atoms in the individual alkyl parts and in the case of haloalkyl having 1 to 9 identical or different halogen atoms and m represents a number 0, 1 or 2 stands; such as X represents oxygen or sulfur; A represents a straight-chain or branched, optionally mono- or polysubstituted, identical or different, halogen or phenyl, which is optionally substituted by halogen or alkyl having 1 to 4 carbon atoms, substituted alkylene bridge having 1 to 6 carbon atoms; n stands for a number 0 or 1 and Y for cyano or the grouping<chemistry id="chem0017" num="0017"><img file="EP0248315A2_D0018.tif" /></chemistry> stands, in which X¹ represents oxygen or sulfur and R³ for hydroxy, each straight-chain or branched alkoxy and alkylthio each having 1 to 6 carbon atoms, each straight-chain or branched alkenyloxy and alkynyloxy each having 3 to 8 carbon atoms, amino, each straight-chain or branched alkylamino and dialkylamino each having 1 to 6 carbon atoms in the alkyl parts , in each case straight-chain or branched alkenylamino and dialkenylamino each having 3 to 8 carbon atoms in the alkenyl parts, straight-chain or branched alkyl alkenylamino having 1 to 6 carbon atoms in the alkyl part and 3 to 8 carbon atoms in the alkenyl part, or representing a radical -OM, in which M for an equivalent of an alkaline earth or alkali metal cation or for a one to four times, if appropriate, the same or different ammonium substituted by straight-chain or branched alkyl having 1 to 12 carbon atoms or benzyl.

5-Acylamino-pyrazole derivatives of the formula (I), in which R1 is hydrogen, nitro, chlorine or bromine; R² represents hydrogen, straight-chain or branched alkyl having 1 to 8 carbon atoms, each straight-chain or branched alkenyl and alkynyl each having 3 to 6 carbon atoms and also cycloalkyl having 3 to 6 carbon atoms optionally substituted by methyl, ethyl or isopropyl; Ar represents phenyl which is optionally mono- to pentasubstituted by identical or different substituents or represents 2-pyridyl, 3-pyridyl or 4-pyridyl which is monosubstituted or monosubstituted by four or more, the same or different, the substituents in each case being Cyano, nitro, fluorine, chlorine, bromine, iodine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, trifluoromethyl, trichloromethyl, dichlorofluoromethyl, Difluorochloromethyl, chloromethyl, dichloromethyl, difluoromethyl, pentafluoroethyl, tetrafluoroethyl, trifluorochloroethyl, trifluoroethyl, difluorodichloroethyl, trifluorodichloroethyl, pentachloroethyl, trifluoromethoxy, trichloromethoxy, dichlorofluoromethoxy, difoxychloroxy Dichloromethoxy, difluoromethoxy, pentafluoroethoxy, tetrafluoroethoxy, trifluorochloroethoxy, trifluoroethoxy, difluorodichloroethoxy, trifluorodichloroethoxy, pentachloroethoxy or a radical -S (O)_m-R⁴, in which R⁴ represents amino, methylamino, ethylamino, dimethylamino, diethylamino, fluorodichloromethyl, difluoromethyl, tetrafluoroethyl, trichloroethyl, trifluoromethyl, difluorochloromethyl, methyl or ethyl and m stands for a number 0, 1 or 2 and X represents oxygen or sulfur; A for a bridge member of the formula -CH₂-; -CH₂-CH₂-;<chemistry id="chem0018" num="0018"><img file="EP0248315A2_D0019.tif" /></chemistry><chemistry id="chem0019" num="0019"><img file="EP0248315A2_D0020.tif" /></chemistry> n stands for a number 0 or 1 and Y for cyano or the grouping<chemistry id="chem0020" num="0020"><img file="EP0248315A2_D0021.tif" /></chemistry> stands, in which X¹ represents oxygen and R³ is hydroxy, alkoxy of 1 to 3 carbon atoms, alkenyloxy and alkynyloxy each of 3 to 6 carbon atoms, amino, alkylamino and dialkylamino each of 1 to 3 carbon atoms in each alkyl part, alkenylamino and dialkenylamino each having 3 to 6 carbon atoms in each alkenyl part, alkyl -alkenylamino with 1 to 3 carbon atoms in the alkyl part and 3 to 6 carbon atoms in the alkenyl part, or represents a radical -OM, in which M stands for an equivalent of a sodium, potassium, calcium, magnesium or barium cation or for an isopropylammonium, dimethylbenzylammonium, triethylammonium or tributylammonium ion.

5-Acylamino-pyrazole derivatives of the formula (I), in which are very particularly preferred R1 is hydrogen or nitro; R² represents hydrogen, methyl, ethyl, allyl, propargyl or cyclohexyl; Ar represents phenyl which is optionally mono- to pentasubstituted by identical or different substituents or represents 2-pyridyl, 3-pyridyl or 4-pyridyl which is monosubstituted to monosubstituted by four or four, identically or differently, the substituents in each case being: Cyano, nitro, fluorine, chlorine, bromine, iodine, methyl, ethyl, n- and i-propyl, n-, i-, s- and t-butyl, methoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, trifluoromethyl, trichloromethyl, difluorochloromethyl, Difluorochloroethyl, chloromethyl, dichloromethyl, difluoromethyl, pentafluoroethyl, tetrafluoroethyl, trifluorochloroethyl, trifluoroethyl, difluorodichloroethyl, trifluorodichloroethyl pentachloroethyl, trifluoromethoxy, trichloromethoxy, dichlorofluoromethoxy, difluorochloromethoxy, difluorochloromethyl Difluoromethoxy, pentafluoroethoxy, tetrafluoroethoxy, trifluorochloroethoxy, trifluoroethoxy, difluorodichloroethoxy, trifluorodichloroethoxy, pentachloroethoxy or a radical -S (O)_m-R⁴, in which R⁴ represents amino, methylamino, ethylamino, dimethylamino, diethylamino, fluorodichloromethyl, difluoromethyl, tetrafluoroethyl, trifluorochloroethyl, trifluoromethyl, methyl or ethyl and m stands for a number 0, 1 or 2 and X represents oxygen or sulfur; A for a bridge member of the formula - CH₂-; -CH₂-CH₂-;<chemistry id="chem0021" num="0021"><img file="EP0248315A2_D0022.tif" /></chemistry> n stands for a number 0 or 1 and Y for cyano or the grouping<chemistry id="chem0022" num="0022"><img file="EP0248315A2_D0023.tif" /></chemistry> stands, X¹ represents oxygen and R³ represents hydroxy, methoxy, ethoxy, n- and i-propoxy allyloxy, propargyloxy, amino, methylamino, dimethylamino, allylamino, diallylamino, methylethylamino, methyl-allylamino or the radical -OM, in which M represents an equivalent of a sodium, potassium or calcium cation or an isopropylammonium ion.

In addition to the compounds mentioned in the preparation examples, the following 5-acylaminopyrazole derivatives of the general formula (I) may be mentioned individually:<chemistry id="chem0023" num="0023"><img file="EP0248315A2_D0024.tif" /></chemistry><tables id="tabl0001" num="0001"><img file="EP0248315A2_D0025.tif" /></tables><tables id="tabl0002" num="0002"><img file="EP0248315A2_D0026.tif" /></tables><tables id="tabl0003" num="0003"><img file="EP0248315A2_D0027.tif" /></tables><tables id="tabl0004" num="0004"><img file="EP0248315A2_D0028.tif" /></tables><tables id="tabl0005" num="0005"><img file="EP0248315A2_D0029.tif" /></tables><tables id="tabl0006" num="0006"><img file="EP0248315A2_D0030.tif" /></tables><tables id="tabl0007" num="0007"><img file="EP0248315A2_D0031.tif" /></tables><tables id="tabl0008" num="0008"><img file="EP0248315A2_D0032.tif" /></tables><tables id="tabl0009" num="0009"><img file="EP0248315A2_D0033.tif" /></tables><tables id="tabl0010" num="0010"><img file="EP0248315A2_D0034.tif" /></tables><tables id="tabl0011" num="0011"><img file="EP0248315A2_D0035.tif" /></tables>

If, for example, 5-amino-1- (2-bromo-4-trifluoromethyl-phenyl) pyrazole and cyanoacetyl chloride are used as starting materials, the course of the reaction of process (a) according to the invention can be represented by the following formula:<chemistry id="chem0024" num="0024"><img file="EP0248315A2_D0036.tif" /></chemistry>

If, for example, 1- (2-chloro-4-trifluoromethoxyphenyl) -5-ethoxaloyl-amino-4-nitro-pyrazole and dimethyl sulfate are used as starting materials, the reaction sequence of process (b) according to the invention can be represented by the following formula:<chemistry id="chem0025" num="0025"><img file="EP0248315A2_D0037.tif" /></chemistry>

If, for example, 5-chloroacetylamino-4-nitro-1- (2,4,6-trichlorophenyl) pyrazole and tetrabutylammonium cyanide are used as starting materials, the course of the reaction of process (c) according to the invention can be illustrated by the following formula represent:<chemistry id="chem0026" num="0026"><img file="EP0248315A2_D0038.tif" /></chemistry>

If, for example, 1- (2,4-dichlorophenyl) -5-ethyl-malonoylamino-pyrazole and nitric acid are used as starting materials, the course of the reaction of process (d) according to the invention can be represented by the following formula:<chemistry id="chem0027" num="0027"><img file="EP0248315A2_D0039.tif" /></chemistry>

If, for example, 1- (2,6-dichloro-4-trifluoromethylthio-phenyl) -4-nitro-5-succinimido-pyrazole and ammonia are used as starting materials, the course of the reaction of process (e) according to the invention can be represented by the following formula:<chemistry id="chem0028" num="0028"><img file="EP0248315A2_D0040.tif" /></chemistry>

If, for example, 1- (2,4-dichlorophenyl) -5-ethylmalonoylamino-pyrazole and sodium hydroxide are used as starting materials, the course of the reaction of process (f) according to the invention can be represented by the following formula:<chemistry id="chem0029" num="0029"><img file="EP0248315A2_D0041.tif" /></chemistry>

Formula (II) provides a general definition of the 5-amino-1-aryl-pyrazoles required as starting materials for carrying out process (a) according to the invention. In this formula (II), R 1 and Ar preferably represent those radicals which have already been mentioned as preferred for these radicals in connection with the description of the substances of the formula (I) according to the invention.

Some of the 5-amino-1-aryl-pyrazoles of the formula (II) are known (cf., for example, DE-OS 3 402 308), and in part they are the subject of our own previously unpublished patent applications DE-Os 3 520 330 dated 07.06. 1985 and DE-OS 3 543 033 dated 05.12.1985 and obtainable in analogy to known processes (cf. DE-OS 3 402 308), for example if arylhydrazines of the formula (X) are Ar - NH - NH₂ (X) in which Ar has the meaning given above, with 2-haloacrylonitriles of the formula (XI),<chemistry id="chem0030" num="0030"><img file="EP0248315A2_D0042.tif" /></chemistry> in which Hal represents halogen, in particular chlorine or bromine, either first in a first stage, optionally in the presence of a diluent such as glacial acetic acid or ethanol, and optionally in the presence of a reaction auxiliary such as sodium acetate at temperatures between -20 ° C and +20 ° C to the arylhydrazine derivatives of the formula (XII) ,<chemistry id="chem0031" num="0031"><img file="EP0248315A2_D0043.tif" /></chemistry> in which Ar and Hal have the meaning given above, and this in a 2nd Stage, optionally cyclized in the presence of a diluent such as, for example, ethylene glycol monoethyl ether and optionally in the presence of an acidic catalyst such as, for example, sulfuric acid or phosphoric acid at temperatures between +50 ° C and +150 ° C, or directly in one reaction step without isolation of the intermediate of formula (XII), optionally cyclized in the presence of a diluent such as, for example, ethylene glycol monoethyl ether or ethanol at temperatures between +50 ° C. and +150 ° C., and the 4-unsubstituted 5-amino-1-aryl-pyrazoles of the formula (IIa) thus obtainable,<chemistry id="chem0032" num="0032"><img file="EP0248315A2_D0044.tif" /></chemistry> in which Ar has the meaning given above, in a subsequent reaction with a nitrating agent, such as, for example, nitric acid, optionally in the presence of a diluent such as, for example, glacial acetic acid and, if appropriate, in the presence of a reaction auxiliary, such as, for example, acetic anhydride, at temperatures between -20 ° C. and +50 ° C. or alternatively with a halogenating agent, such as chlorine, Sulfuryl chloride, phosphorus pentachloride, N-chlorosuccinimide, bromine, Phosphorus tribromide or N-bromosuccinimide, optionally halogenated in the presence of a diluent, such as methylene chloride or glacial acetic acid, and optionally in the presence of a reaction auxiliary such as boron trifluoride at temperatures between -20 ° C and +50 ° C.

It may be advantageous to protect the amino group in the 5-position of the pyrazole ring using conventional protective group technology, for example by acylation, before the halogenation or nitration reaction, and also to protect the amino protective group in the usual manner, for example, by using halogenation or nitration Splitting off saponification with an aqueous or alcoholic base.

The arylhydrazines (X) are known (cf., for example, US Pat. No. 4,127,575; US Pat. No. 3,609,158; DE-OS 2,558,399; J. Chem. Soc. C. <u style="single">1971</u>, 167-174) or can be obtained in a simple analogous manner by known processes (cf. for example Houben-Weyl "Methods of Organic Chemistry" Volume X / 2, p. 203, Thieme Verlag Stuttgart 1967; DE-OS 3 402 308) .

The haloacrylonitriles of the formula (XI) are generally known compounds of organic chemistry.

Formula (III) provides a general definition of the acylating agents which are furthermore required as starting materials for carrying out process (a) according to the invention. In this formula (III), X, Y, A and the index n preferably represent those meanings which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention.

E¹ preferably represents halogen, in particular chlorine or bromine, or a radical Y- (A)_n-<img file="EP0248315A2_D0045.tif" />-O- , where X, Y, A and the index n have the meanings given above. The acylating agents of the formula (III) are generally known compounds of organic chemistry.

Formula (Ia) provides a general definition of the 5-acylamino-pyrazole derivatives required as starting materials for carrying out process (b) according to the invention. In this formula (Ia), R 1, X, Y, A, the index n and Ar preferably represent those meanings which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention.

The 5-acylamino-pyrazole derivatives of the formula (Ia) are compounds according to the invention and can be obtained with the aid of processes (a), (c), (d) or (e) according to the invention.

Formula (IV) provides a general definition of the alkylating agents which are furthermore required as starting materials for carrying out process (b) according to the invention. In this formula (IV) R²⁻¹ preferably represents straight-chain or branched alkyl having 1 to 12 carbon atoms, in particular methyl, ethyl, n- or i-propyl and n-, i-, s- or t-butyl; furthermore for alkenyl or alkynyl each with 3 to 6 carbon atoms, in particular for allyl or propargyl, and for cycloalkyl with 3 to 6 carbon atoms, in particular for cyclopropyl, cyclopentyl or cyclohexyl, E² preferably stands for chlorine, bromine or iodine, for methoxysulfonyloxy or for p -Toluenesulfonyloxy.

The alkylating agents of formula (IV) are generally known compounds of organic chemistry.

Formula (V) provides a general definition of the 5-acylamido-1-aryl-pyrazoles required as starting materials for carrying out process (c) according to the invention. In this formula (V) R 1, R 2, X, A, Ar and the index n are preferably those meanings which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention. E³ preferably represents chlorine or bromine.

The 5-acylamido-1-aryl-pyrazoles of the formula (V) are known (cf. US Pat. No. 4,363,804 or DE-OS 3 402 308) or they are the subject of our own previously unpublished patent application DE-OS 3 520 330 dated 07.06.1985 and available in analogy to known processes (see, for example, DE-OS 3 402 308; see also preparation examples), for example if 5-amino-1-aryl-pyrazoles of the formula (II) are used,<chemistry id="chem0033" num="0033"><img file="EP0248315A2_D0046.tif" /></chemistry> in which R¹ and Ar have the meaning given above, with acylating agents of the formula (XIII), E⁵ - <img file="EP0248315A2_D0047.tif" /> - (A)_n - E³ (XIII) in which E³, X, A and the index n have the meaning given above and E⁵ for a leaving group such as halogen, especially chlorine or bromine, or for a residue E³- (A)_n-<img file="EP0248315A2_D0048.tif" />-O- stands, where E³, A, X and the Index n have the meaning given above, optionally acylated in the presence of a diluent, such as dichloromethane, and optionally in the presence of an acid binder, such as pyridine, at temperatures between -20 ° C and +120 ° C, and then optionally in analogy to known Ver and in analogy to the invention Method (b) in a second Step with alkylating agents of the formula (IV), E² - R²⁻¹ (IV) in which E² and R²⁻¹ have the meaning given above, optionally alkylated in the presence of a diluent such as acetonitrile and optionally in the presence of a catalyst such as sodium methylate at temperatures between 0 ° C and 80 ° C.

The acylating agents of the formula (XIII) are generally known compounds of organic chemistry.

Formula (VI) provides a general definition of the cyano derivatives which are furthermore required as starting materials for carrying out process (c) according to the invention. In this formula (VI), W preferably represents hydrogen, a sodium or potassium cation, or a tetrabutylammonium cation.

The cyan derivatives of the formula (VI) are generally known compounds of organic chemistry.

Formula (Ie) provides a general definition of the 5-acylamino-pyrazole derivatives required as starting materials for carrying out process (d) according to the invention. In this formula (Ie), R 2, X, Y, A, Ar and the index n preferably represent those meanings which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention.

The 5-acylamino-pyrazole derivatives of the formula (Ie) are compounds according to the invention and can be obtained with the aid of processes (a), (b), (c), (e) or (f) according to the invention.

Formula (VII) provides a general definition of the halogenating or nitrating agents which are furthermore required as starting materials for carrying out process (d) according to the invention. In this formula (VII) R¹⁻¹ is preferably chlorine, bromine or nitro. E⁴ preferably represents a common leaving group, such as halogen and halogenated phosphorus or sulfur-containing leaving groups. Suitable halogenating and nitrating agents are, for example, nitric acid, nitrating acid, sulfuryl chloride, phosphorus oxychloride, phosphorus oxybromide, phosphorus tribromide and similar commonly used halogenating and nitrating agents.

The halogenating and nitrating agents of the formula (VII) are generally known compounds.

Formula (VIII) provides a general definition of the 5-imido-pyrazoles required as starting materials for carrying out process (e) according to the invention. In this formula (VIII) R 1 and Ar preferably or particularly preferably represent those radicals which have already been mentioned as preferred or particularly preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention.

A¹ preferably represents the alkylene chains<chemistry id="chem0034" num="0034"><img file="EP0248315A2_D0049.tif" /></chemistry> The 5-imido-pyrazoles of the formula (VIII) are not yet known; however, they can be obtained in a conventional manner by using 5-amino-1-aryl-pyrazoles of the formula (II)<chemistry id="chem0035" num="0035"><img file="EP0248315A2_D0050.tif" /></chemistry> in which R¹ and Ar have the meaning given above, with cyclic dicarboxylic acid anhydrides of the formula (XIV)<chemistry id="chem0036" num="0036"><img file="EP0248315A2_D0051.tif" /></chemistry> in which A¹ has the meaning given above, if appropriate in the presence of a diluent and if appropriate in the presence of an acidic catalyst and in the presence of water-releasing reagents, the open-chain amidic acids of the formula (Ig) depending on the reaction conditions<chemistry id="chem0037" num="0037"><img file="EP0248315A2_D0052.tif" /></chemistry> in which R¹, A¹ and Ar have the meaning given above, can be isolated, which are then cyclized to the 5-imido-pyrazoles of the formula (VIII) in a second reaction step under water-releasing conditions with the addition of a reaction auxiliary or a catalyst, such as, for example, dicylohexylcarbodiimide, trifluoroacetic anhydride or p-toluenesulfonic acid.

Inert organic solvents are suitable as diluents for the preparation of the 5-imido-pyrazoles of the formula (VIII). The organic solvents mentioned in process (a) according to the invention are preferably used here. Organic solvents which are immiscible with water, such as toluene, chlorobenzene and carbon tetrachloride, or organic acids, such as acetic acid and propionic acid, are particularly preferred.

The 5-imido-pyrazoles of the formula (VIII) are optionally prepared using acidic catalysts, such as mineral acids, carboxylic acids and sulfonic acids, and in the presence of water-releasing reagents, such as dicyclohexylcarbodiimide or acid anhydrides and acid chlorides, such as phosphorus pentoxide, phosphorus oxychloride, thionyl chloride and trifluoride .

The temperatures can be varied within a substantial range in the process for the preparation of the 5-imido-pyrazoles of the formula (VIII). In general, temperatures between 20 ° C and 180 ° C, preferably between 50 ° C and 180 ° C.

To carry out the process for the preparation of the 5-imido-pyrazoles of the formula (VIII), 1 to 2 moles, preferably 1 to 1.2 moles, of dicarboxylic anhydride are used per mole of 5-amino-1-aryl-pyrazole of the formula (II) of the formula (XIV), 0.01 to 1 mol of acid catalyst and 1 to 15 mol, preferably 1 to 10 mol of water-releasing reagent.

The reaction, working up and isolation of the 5-imido-pyrazoles of the formula (VIII) is carried out in a generally customary manner.

The 5-imido-pyrazoles of the formula (VIII) not only represent interesting intermediates, but also show good herbicidal and plant growth-regulating properties in appropriate application rates.

Formula (IX) provides a general definition of the nucleophilic compounds which are further required as starting materials for carrying out process (e) according to the invention. In this formula, R 3 preferably represents those radicals which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention.

The nucleophilic compounds of the formula (IX) are generally known compounds of organic chemistry.

Formula (Ih) provides a general definition of the 5-acylamino-pyrazole derivatives required as starting materials for carrying out process (f) according to the invention. In this formula (Ih), R 1, R 2, X, X 1, A, Ar and the index n preferably represent those meanings which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention.

R³⁻¹ preferably represents hydroxy, methoxy, ethoxy, n- and i-propoxy. The compounds of formula (Ih) are substances according to the invention and can be obtained with the aid of processes (a), (b), (d) or (e) according to the invention.

Inert organic solvents are suitable as diluents for carrying out process (a) according to the invention. These include in particular aliphatic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, ethers, such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether, Ketones such as acetone or butanone, nitriles such as acetonitrile or propionitrile, amides such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide, esters such as ethyl acetate or sulfoxides such as dimethyl sulfoxide.

Process (a) according to the invention is optionally carried out in the presence of a suitable acid binder.

All conventional inorganic or organic bases are suitable as such. These include, for example, alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, alkali metal carbonates, such as sodium carbonate, potassium carbonate or sodium hydrogen carbonate, and also tertiary amines, such as triethylamine, N, N-dimethylaniline, pyridine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO) or diazabicyclooctane (DABCO), diazabicyclooctane (DABCO) or diazabicyclooctane (DABCO) Diazabicycloundecene (DBU).

Process (a) according to the invention can optionally also be carried out in the presence of a suitable acylation catalyst. Protonic acid such as sulfuric acid, hydrochloric acid, phosphoric acid, trifluoroacetic acid or Lewis acids such as aluminum trichloride, boron trifluoride or iron trichloride are preferably used as such.

The reaction temperatures can be varied within a substantial range when carrying out process (a) according to the invention. In general, temperatures between -20 ° C and +150 ° C, preferably at temperatures between 0 ° C and 100 ° C.

To carry out process (a) according to the invention, generally 1.0 to 15.0 mol, preferably 1.0 to 5.0 mol, of acylating agent of the formula (III), optionally 1.0 to 1 mol, are used per mol of 5-amino-1-aryl-pyrazole of the formula (II) 3.0 mol, preferably 1.0 to 2.0 mol of acid binder or optionally 0.1 to 3.0 mol, preferably 0.1 to 2.0 mol, of acylation catalyst. The reaction, working up and isolation of the reaction products of the formula (Ia) is carried out by customary, known methods.

Inert organic solvents are also suitable as diluents for carrying out process (b) according to the invention. The organic solvents mentioned in process (a) are preferably used.

If appropriate, process (b) according to the invention can also be carried out in a two-phase system, such as, for example, water / toluene or water / dichloromethane, if appropriate in the presence of a phase transfer catalyst. Examples of such catalysts are: tetrabutylammonium iodide, tetrabutylammonium bromide, tributyl-methylphosphonium bromide, trimethyl-C₁₃ / C₁₅-alkyl-ammonium chloride, dibenzyl- dimethyl-l-ammonium -methyl sulfate, dimethyl-C₁₂ / C₁ alkyl-alkyl-benzium-hydroxylammonium-5-benzylammonium , 18-crown-6, triethylbenzylammonium chloride, trimethylbenzylammonium chloride.

All commonly used inorganic and organic bases are suitable as acid binders for carrying out the production process (b). Alkali metal hydrides, hydroxides, amides, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, sodium hydroxide, sodium carbonate or sodium hydrogen carbonate or also tertiary amines, such as, for example, triethylamine, N, N-dimethylaniline, pyridine, 4- (N, N-dimethylamino) pyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

The reaction temperatures can be varied within a substantial range when carrying out process (b) according to the invention. In general, temperatures between -20 ° C and +150 ° C, preferably at temperatures between 0 ° C and +100 ° C.

To carry out process (b) according to the invention, in general 1.0 to 20.0 mol, preferably 1.0 to 15.0 mol of alkylating agent of the formula (IV) and, if appropriate, 1.0 to 3.0 are employed per mol of 5-acylamino-pyrazole derivatives of the formula (Ia) Mol, preferably 1.0 to 2.0 mol of acid binder and 0.01 to 1.0 mol of phase transfer catalyst. The reaction, working up and isolation of the reaction products of the formula (Ib) is carried out in a generally customary manner.

Inert organic solvents or aqueous systems are suitable as diluents for carrying out process (c) according to the invention. The organic solvents mentioned in process (a) are preferably used. Also preferred are polar organic solvents such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether or monoethyl ether, diethylene glycol monomethyl ether or monoethyl ether, their mixtures with water or also pure water as a diluent.

Process (c) according to the invention is optionally carried out in the presence of a suitable acid binder. All commonly used inorganic or organic bases are suitable as such. The bases listed in process (b) are preferably used as acid binders.

A particularly preferred embodiment of process (c) is that alkali metal, alkaline earth metal or tetraalkylammonium salts of hydrocyanic acid either in inert organic solvents or in a two-phase system, such as water / toluene or water / dichloromethane, optionally in the presence of a phase transfer - Catalyst, implemented. The catalysts mentioned in process (b) are preferably used.

The reaction temperatures can be varied within a substantial range when carrying out process (c) according to the invention. In general, temperatures between -20 ° C and +120 ° C, preferably at temperatures between 0 ° C and +100 ° C.

To carry out process (c) according to the invention, generally 1.0 to 5.0 mol, preferably 1.0 to 3.0 mol, of cyan derivative of the formula (VI) and, if appropriate, are employed per mol of 5-acylamido-1-aryl-pyrazole of the formula (V) 1.0 to 5.0 mol, preferably 1.0 to 3.0 mol of acid binder or 0.001 to 2.0 mol, preferably 0.01 to 1.0 mol of phase transfer catalyst. The reaction, working up and isolation of the reaction products of the formula (Ia) is carried out in analogy to generally known processes.

Suitable diluents for carrying out the production process (d) are all solvents which can customarily be used for such electrophilic substitutions. The acids or mixtures which are suitable as reagents, such as, for example, nitric acid, nitrating acid, sulfuryl chloride or nitrating acid, are preferably used simultaneously as diluents. Inert organic solvents such as glacial acetic acid or chlorinated hydrocarbons such as methylene chloride, chloroform or carbon tetrachloride may also be considered as diluents.

Suitable catalysts or reaction aids for carrying out the production process (d) are also the catalysts customary for such reactions; acidic catalysts such as sulfuric acid, ferric chloride or other Lewis acids or acetic anhydride are preferably used.

The reaction temperatures can be varied within a substantial range when carrying out the production process (d). Generally one works between -50 ° C and +200 ° C, preferably between -20 ° C and +150 ° C.

To carry out the preparation process (d), generally 1.0 to 10.0 mol, preferably 1.0 to 5.0 mol, of halogenating or nitrating agent of the formula (VII) and, if appropriate, 0.1 to 10, are employed per mol of 5-acylamino-pyrazole derivative of the formula (Ie) Mole of catalyst or reaction auxiliary. The reaction, work-up and isolation of the reaction products of the formula (Id) is carried out in a generally customary manner.

Inert organic solvents or aqueous systems are suitable as diluents for carrying out the production process (e). The organic solvents mentioned in process (a) are preferably used. The reaction can also be carried out in an excess of the nuclephilic compound (IX) as solvent.

Process (e) according to the invention is optionally carried out in the presence of an acid binder. All customary inorganic or organic bases, in particular those already mentioned in process (a), are suitable as such.

A preferred embodiment of process (e) is that the nuclophilic compounds of formula (IX) are used in the form of their salts.

Suitable salts here are in particular the alkali metal, alkaline earth metal and ammonium salts of the compounds of the formula (IX).

The reaction temperatures can be varied within a substantial range in carrying out process (e) according to the invention. In general, temperatures between 0 ° C and 180 ° C, preferably at temperatures between 20 ° C and 150 ° C.

To carry out process (e) according to the invention, 1 to 15 mol, preferably 1 to 5 mol, of nucleophilic compound of the formula (IX), if appropriate 1 to 3 mol, are generally employed per mol of 5-imino-pyrazole of the formula (VIII), preferably 1 to 2 mol of acid binder or optionally 1 to 3 mol, preferably 1 to 2 mol, of salt of the compound of formula (IX). The reaction, working up and isolation of the reaction products of the formula (If) is carried out by customary and known methods.

Inert organic solvents are suitable as diluents for carrying out process (f) according to the invention. The organic solvents mentioned in process (a) are preferably used. However, aqueous or aqueous-organic systems can also preferably be used as diluents.

All commonly used inorganic or organic bases can be used as salt formers. Examples of such bases are: sodium, potassium, lithium, calcium, barium and magnesium hydroxide, sodium, potassium and calcium carbonate; Sodium bicarbonate, potassium bicarbonate, sodium methylate, triethylamine, isopropylamine and dimethylbenzylamine.

The reaction temperatures can be varied within a substantial range when carrying out process (f) according to the invention. In general, temperatures between 0 ° C and 80 ° C, preferably at temperatures between 20 ° C and 50 ° C.

To carry out process (f) according to the invention, 1 to 5 mol, preferably 1 to 2 mol, of inorganic or organic base are generally employed per mol of 5-acylamino-pyrazole derivative of the formula (Ih). The reaction, working up and isolation of the reaction products of the formula (Ig) is carried out in a generally customary manner.

The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular as weed killers. Weeds in the broadest sense are understood to mean all plants that grow up in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, for example, in the following plants:

<u style="single">Dicot weeds of the genera:</u> Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippernia, Rorippa, Rorippa, Rorippa Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.

<u style="single">Dicotyledon cultures of the genera:</u> Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.

<u style="single">Monocot weeds of the genera:</u> Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Spochenium, Ischaeaeaum, Ischaeaumum Agrostis, Alopecurus, Apera.

<u style="single">Monocot cultures of the genera:</u> Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants.

Depending on the concentration, the compounds are suitable for total weed control, for example on industrial and rail tracks and on paths and squares with and without tree cover. Likewise, the compounds for weed control in permanent crops, for example forest, ornamental trees, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and Hop plants and for selective weed control in annual crops.

The active compounds according to the invention can be used with particularly good success for the selective control of monocotyledonous and dicotyledon weeds in monocotyledonous and dicotyledonous crops, such as, for example, wheat or cotton.

In addition, the active compounds according to the invention intervene in the metabolism of the plants and can therefore be used as growth regulators.

Experience has shown that the effect of plant growth regulators is that an active substance can also have several different effects on plants. The effects of the substances essentially depend on the point in time of use, based on the stage of development of the plant, on the amounts of active compound applied to the plants or their environment and on the type of application. In any case, growth regulators should influence the crop plants in a certain desired manner.

Under the influence of growth regulators, the number of leaves in the plants can be controlled in such a way that defoliation of the plants is achieved at a desired point in time. Such defoliation plays a major role in the mechanical harvesting of cotton, but is also of interest in other crops, such as, for example, in viticulture, to facilitate harvesting. Defoliation of the plants can also be carried out in order to reduce the transpiration of the plants before transplanting.

The active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, suspension emulsion concentrates, natural and synthetic substances impregnated with active ingredients, aerosols, very fine encapsulations in polymers Fabrics and in coating compositions for seeds, as well as ULV formulations.

These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. In the case of the use of water as an extender, for example organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water. Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example Aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. The following are suitable as solid carriers: for example natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates. Possible solid carriers for granules are: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems. Suitable emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates. Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

When used as herbicides, the active compounds according to the invention, as such or in their formulations, can also be used in a mixture with known herbicides for weed control, finished formulations or tank mixes being possible.

Known herbicides such as 1-amino-6-ethylthio-3- (2,2-dimethylpropyl) -1,3,5-triazine-2,4 (1H, 3H) -dione or N- (2- Benzthiazolyl) -N, Nʹ-dimethyl-urea for weed control in cereals; 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5 (4H) -one for weed control in sugar beets and 4-amino-6- (1,1-dimethylethyl) -3-methylthio-1 , 2,4-triazin-5 (4H) -one for weed control in soybeans, in question.

Mixtures with N, N-dimethyl-Nʹ- (3-trifluoromethylphenyl) urea; N, N-dimethyl-Nʹ- (4-isopropylphenyl) urea; 2,4-dichlorophenoxyacetic acid; 2,4-dichlorophenoxypropionic acid; (2-methyl-4-chlorophenoxy) acetic acid; (4-chloro-2-methylphenoxy) propionic acid; Chloroacetic acid-N- (methoxymethyl) -2,6-diethylanilide; 2-ethyl-6-methyl-N- (1-methyl-2-methoxyethyl) chloroacetanilide; 2,6-dinitro-4-trifluoromethyl-N, N-dipropylaniline; Methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate; 3,5-diiodo-4-hydroxybenzonitrile; 3-isopropyl-2,1,3-benzothiadiazin-4-one-2,2-dioxide; 2-chloro-N - {[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] carbonyl} benzenesulfonamide; 4-ethylamino-2-t-butylamino-6-methylthio-s-triazine; N-methyl-2- (1,3-benzothiazol-2-yloxy) acetanilide; exo-1-methyl-4- (1-methylethyl) -2 (2-methylphenyl-methoxy) -7-oxabicyclo- (2,2,1) -heptane; N, N-diisoproyl-S- (2,3,3-trichlorallyl) thiol carbamate; N- (1-ethylpropyl) -3,4-dimethyl-2,6-dinitroaniline; 1-methyl-3-phenyl-5- (3-trifluoromethylphenyl) -4-pyridone; 2- [5-methyl-5- (1-methylethyl) -4-oxo-2-imidazolin-2-yl] -3-quinolinecarboxylic acid; [(4-Amino-3,5-dichloro-6-fluoro-2-pyridinyl) -oxy] acetic acid; 3,5-dibromo-4-hydroxy-benzonitrile is possible.

Surprisingly, some mixtures also show a synergistic effect.

A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible.

The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, spraying or scattering.

The active compounds according to the invention can be applied both before and after emergence of the plants. When used in the post-emergence process, the compounds according to the invention can be applied on their own or in combination with emulsifiable oils, surface-active substances and other additives.

They can also be worked into the soil before sowing.

The amount of active ingredient used can vary over a wide range. It essentially depends on the type of effect desired. In general, the application rates are between 0.01 and 10 kg of active ingredient per hectare of soil, preferably between 0.05 and 5 kg per ha.

When used as growth regulators, the active compounds according to the invention can also be present in the formulations in a mixture with other known active compounds, such as fungicides, insecticides, acaricides and herbicides, and also in mixtures with fertilizers and other growth regulators.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, foams, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the customary manner, for example by watering, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients using the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient itself into the soil. The seeds of the plants can also be treated.

When treating parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.

In the case of seed treatment, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.

When treating the soil, active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are required at the site of action.

The application rates can be varied over a wide range. In general, 0.01 to 50 kg, preferably 0.05 to 10 kg, of active ingredient are used per hectare of soil.

For the application period, the growth regulators are used in a preferred period, the exact delimitation of which depends on the climatic and vegetative conditions.

The preparation and use of the active compounds according to the invention can be seen from the examples below.

Manufacturing examples

example 1

<chemistry id="chem0038" num="0038"><img file="EP0248315A2_D0053.tif" /></chemistry>

(Method a)

22.5 g (0.076 mol) of 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole and 8 g (0.1 mol) of pyridine are placed in 200 ml of acetonitrile and stirred and cooled at 20 - 25 ° C with 13.2 g (0.128 mol) of cyanoacetyl chloride added dropwise. The mixture is stirred for a further two hours at room temperature and then the reaction mixture is poured into water. After extraction with methylene chloride and drying of the organic phase over sodium sulfate, the solvent is distilled off in vacuo. The crystalline residue is stirred with a mixture of ligroin and diisopropyl ether and suction filtered.

22 g (80% of theory) of 5-cyanoacetylamino-1- (2,6-dichloro-4-trifluoromethyl-phenyl) pyrazole of melting point 169-175 ° C. are obtained.

Example 2

<chemistry id="chem0039" num="0039"><img file="EP0248315A2_D0054.tif" /></chemistry>

(Method d)

7.26 g (0.02 mol) of 5-cyanoacetylamino-1- (2,6-dichloro-4-trifluoromethyl-phenyl) pyrazole (Ex. 1) are placed in 70 ml of glacial acetic acid and added dropwise in succession at about 10 ° C with 2 ml of acetic anhydride and 2 ml of nitric acid. After stirring for a long time, a crystalline solid precipitates out of the initially clear solution. After suction, repeated washing with diisopropyl ether and drying, 2.9 g (36% of theory) of 5-cyanoacetylamino-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -4-nitro-pyrazole with a melting point of 221 - 223 ° C.

Example 3

<chemistry id="chem0040" num="0040"><img file="EP0248315A2_D0055.tif" /></chemistry>

(Method e)

To a solution of 8.25 g (0.0218 mol) of 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -5-succinimido-pyrazole in 50 ml of anhydrous methanol is added 1.3 g (0.024 Mol) of sodium methylate and stirred for 18 hours. The reaction mixture is then poured onto 200 ml of 2% ammonium chloride solution and 150 ml of dichloromethane. The organic phase is separated off, washed with water and brine, dried over magnesium sulfate and freed from the solvent in vacuo.

7.0 g (78.3% of theory) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -5- (2-methoxycarbonylpropionylamido) pyrazole with a melting point of 127-132 ° C. are obtained.

Manufacture of the starting product

<chemistry id="chem0041" num="0041"><img file="EP0248315A2_D0056.tif" /></chemistry>

To a solution of 20 g (0.0676 mol) of 5-amino-1- (2,6-dichloro-4-trifluoromethyl-phenyl) pyrazole in 150 ml of acetonitrile are successively added 42 g (0.42 mol) of succinic anhydride and 40.8 g (0.404 mol) of triethylamine and heated at 80 ° C for 16 hours. The solvent is removed in vacuo and the residue is taken up in water. The resulting precipitate is filtered off, washed with water and dried.

21.6 g (84.5% of theory) of 1- (2-6-dichloro-4-trifluoromethyl-phenyl) -5-succinimido-pyrazole of melting point 162-165 ° C. are obtained.

Example 4

<chemistry id="chem0042" num="0042"><img file="EP0248315A2_D0057.tif" /></chemistry>

(Method d)

To a solution of 4.1 g (0.01 mol) of 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -5- (2-methoxycarbonyl-propionylamido) pyrazole in 30 ml of glacial acetic acid are added at 15 ° - 20 ° C in succession 1.2 ml (0.013 mol) acetic anhydride and 0.5 ml (0.012 mol) 99% nitric acid. The mixture is stirred at room temperature for 14 hours. The reaction solution is then poured onto 100 ml of water. The precipitate is filtered off, washed neutral with water and dried in vacuo.

4.1 g (90% of theory) of 1- (2,6-dichloro-4-trifluoromethyl-phenyl) -5- (2-methoxycarbonyl-propionylamido) -4-nitro-pyrazole with a melting point of 149 ° -151 ° C. are obtained .

The following 5-acylamino-pyrazole derivatives of the general formula (I) are obtained in a corresponding manner and in accordance with the general information on the preparation:<chemistry id="chem0043" num="0043"><img file="EP0248315A2_D0058.tif" /></chemistry><tables id="tabl0012" num="0012"><img file="EP0248315A2_D0059.tif" /></tables><tables id="tabl0013" num="0013"><img file="EP0248315A2_D0060.tif" /></tables><tables id="tabl0014" num="0014"><img file="EP0248315A2_D0061.tif" /></tables><tables id="tabl0015" num="0015"><img file="EP0248315A2_D0062.tif" /></tables><tables id="tabl0016" num="0016"><img file="EP0248315A2_D0063.tif" /></tables><tables id="tabl0017" num="0017"><img file="EP0248315A2_D0064.tif" /></tables><tables id="tabl0018" num="0018"><img file="EP0248315A2_D0065.tif" /></tables>

According to Example VIII-1 and according to the general information on the preparation, the following starting compounds of the general formula (VIII) are obtained:<tables id="tabl0019" num="0019"><img file="EP0248315A2_D0066.tif" /></tables><tables id="tabl0020" num="0020"><img file="EP0248315A2_D0067.tif" /></tables>

Example A

Pre-emergence test

Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Seeds of the test plants are sown in normal soil and watered with the preparation of active compound after 24 hours. The amount of water per unit area is expediently kept constant. The concentration of active substance in the preparation is irrelevant, the only decisive factor is the amount of active substance applied per unit area. After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control. It means: 0% = no effect (like untreated control) 100% = total annihilation

In this test, for example, the compounds according to the preparation examples: 2, 6, 8, 13 and 14 show a clear superiority in effectiveness as well as in crop selectivity compared to the comparison substance (A).

Example B

Post emergence test

Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Test plants which have a height of 5-15 cm are sprayed with the active substance preparation in such a way that the desired amounts of active substance are applied per unit area. The concentration of the spray liquor is chosen so that the desired amounts of active compound are applied in 2000 l of water / ha. After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control. It means: 0% = no effect (like untreated control) 100% = total annihilation

In this test, for example, the compounds according to the preparation examples: 2, 4, 5, 6, 7, 8, 9, 13 and 14 show a clear superiority in effectiveness as well as in crop selectivity compared to the comparison substance (A).

Example C

Defoliation and drying of the leaves in cotton

Solvent: 30 parts by weight of dimethylformamide Emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the mixture is made up to the desired concentration with water.

Cotton plants are grown in the greenhouse until the 5th following leaf is fully developed. At this stage, the plants are sprayed dripping wet with the active ingredient preparations. After 1 week, the leaf fall and the drying out of the leaves are rated in comparison to the control plants. It means: 0 no drying out of the leaves, no falling leaves + slight drying of the leaves, little leaf fall ++ strong drying out of the leaves, heavy leaf fall +++ very strong drying of the leaves, very strong leaf fall

In this test, for example, the compounds according to Preparation Examples 2, 6, 7, 8 and 14 show a clear superiority compared to the untreated control.