MXPA98010393A - Derivatives of pirazolylpirazzol substituted and used as a herbici - Google Patents

Abstract

The invention relates to novel substituted pyrazole pyrazoles of the general formula I in which R1-R6 have the meanings given in the description, the invention also relates to processes and intermediates for their preparation, and their use as herbicides.

Description

DERIVATIVES OF PIRAZOLYLPIRAZZOL SUBSTITUTED AND USED AS HERBICIDES FIELD OF THE INVENTION The invention relates to novel substituted pyrazolylpyrazoles, to processes for their preparation, to intermediates for their preparation, and to their use as herbicides.

BACKGROUND OF THE INVENTION The patent of E.U. 5,405,829 describes pyrazolylpyrazoles having an unsubstituted amino group, as herbicidally active compounds. WO 94/08999 describes pyrazolylpyrazoles, among others, those having a substituted amino group, as herbicidally active compounds. WO 96/09303 also describes substituted pyrazolylpyrazoles having herbicidal properties. However, the herbicidal activity of the known compounds is often insufficient, or, when the herbicidal activity is appropriate, there are problems with the selectivity in the main agricultural crops. It is an object of the present invention to provide novel substituted pyrazolylpyrazoles which do not have these disadvantages, and which are superior to the prior art compounds in terms of biological properties. It has now been found that the substituted pyrazolylpyrazoles of formula I have superior herbicidal activity to that of the prior art compounds. wherein R is C 1 -C 4 alkyl, R is C 1 -C 4 alkyl, C 1 -C 4 alkyl, C 1 -C 4 alkylsulfinyl, C 2 -C 4 alkylsulfonyl, C 4 -C 4 alkoxy, or C 1 -C 4 alkyl C ^. , C 1 -C 4 alkylthio, CX-C 4 alkylsulfonyl, or C 1 -C 4 alkoxy, each of which is mono- or polysubstituted with halogen, R and R together form the group - (CH 2) m-, R is hydrogen or halogen, R4 is hydrogen or C1-C4 alkyl, R3 is hydrogen, nitro, cyano, -COOR, the group R is one of the groups R 7, R n and R 9 are, independently of one another, hydrogen or C 1 -C 4 alkyl, QQR and R, together with the adjacent nitrogen atom, form a 5 or 6 membered saturated heterocyclic ring, R is hydrogen, C -C4 alkyl, or Ct_C4 alkyl which is mono- or polysubstituted with halogen, R 11 is C5-C8 alkyl, cycloalkyl of (13-Cg, C2-C5 alkenyl, C3-C6 alkynyl, or is C ^ -Cg alkyl, C3-C5 cycloalkyl, C2-C5 alkenyl or C3-C5 alkynyl which is mono- or polysubstituted with identical substituents or different from the group consisting of halogen, cyano, hydroxyl and C1-alkoxy -C, or is C2-C8 alkyl, C3-C3 cycloalkyl, (C3-C8) cycloalkyl-C4-C4 alkyl, C3-C8 alkenyl or C3-C8 alkynyl which is interrupted once or more at one time for oxygen, or is (C1-C4) alkoxycarbonyl-C1-C4alkyl, which may be optionally substituted with halogen atoms, or is (C1-C4) alkoxycarbonyl-C2-C4alkenyl, which is optionally substituted with halogen, or is the group - (CH2) p-NR8R9, -1 -1 -3 R and R are independently from each other hydrogen, halogen, C1-C4 alkyl, C2-C4 alkenyl, C3 alkynyl -C 4 or C 1 -C 4 alkoxy, or C 1 -C 4 alkyl, C 2 -C 4 alkenyl or C 3 -C 4 alkynyl which is mono- or polysubstituted with identical substituents or different from the group consisting of halogen, cyano, carboxyl, hydroxyl , C4-C4 alkoxy and C1-C4 alkoxycarbonyl, A is cyano, XX II 14 AO ORR OI 15 R R and R are, independently of one another, hydrogen, C] _-Cg alkyl, C3-Cg cycloalkyl, C2 ~ C alkenyl or C3 ~ C alkynyl, or a C] _-Cg alkyl, cycloalkyl C3 ~ Cg, C2-Cg alkenyl or C3-C0 alkynyl which is mono- or polysubstituted with identical substituents or different from the group consisting of halogen, cyano, hydroxyl or C1-C4 alkoxy, or a C2-C8 alkyl , C3-Cs cycloalkyl, C2-Cg alkenyl and C3-C8 alkynyl which is interrupted once or more than once by oxygen, or C1-C4 alkoxycarbonyl-C1-C4 alkyl, which may be optionally substituted with halogen or (C 1 -C 4) alkoxycarbonyl-C 2 -C 4 alkenyl, which may be optionally substituted with halogen, or C1-C4 alkoxycarbonyl, R14 and R1, together with the nitrogen atom, form a saturated heterocyclic ring of C3 ~ C which may be interrupted once or more than once by oxygen or sulfur, R is hydrogen or C1-C4, Ri v is hydrogen, C2-C4 alkyl or C1-C4 haloalkyl, R18, R19 ^ R20 ^ R21 ^ R22? R 24 are, independently of one another, hydrogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl or C 3 -C 4 alkynyl carboxyl or C 1 -C 4 alkoxycarbonyl, or a C 1 -C 4 alkyl, C 2 -C 4 alkenyl or alkynyl of C3-C4 which is mono- or polysubstituted with identical substituents or different from the group consisting of halogen, cyano, nitro, hydroxyl and C2.-C4 alkoxy, R and R are hydrogen, halogen, C1.-C4 alkyl, C2-C alkenyl or C3-C4 alkynyl, or R "and R" together form a saturated or unsaturated ring of 3 to 8 members optionally containing one or more of a sulfur or oxygen atom, QR is hydrogen or halogen R is hydrogen, C1-C4 alkyl, C5-C8 alkyl, C3-Cg cycloalkyl, C-C alkenyl or C3-C alkynyl, which is mono- or polysubstituted with identical substituents or different from the group consisting of of halogen, cyano, hydroxyl and C1-C4 alkoxy, or is a C2-Cg alkyl, cycloalkyl C3-C8, (C3-C8) cycloalkyl-C1-C4 alkyl, C2-C8 alkenyl or C3-C8 alkynyl which is interrupted once or more than once with oxygen, or is (C1-C4) alkoxycarbonyl- C] _ C4 alkyl which may be optionally substituted with halogen, or is C 1 -C 4 alkoxycarbonyl-C 2 -C alkenyl which may be optionally substituted with halogen, or is the group - (CH 2) p- NR ° R , with the proviso that if R and R are hydrogen, or R,? is hydrogen and RJJ_ is C1-C4 alkyl, R can not be hydrogen or halogen, 3 p R is hydrogen, C ^ -Cg alkyl, C3-Cg cycloalkyl, C2-Cg alkenyl, C3-Cg alkynyl, or is an alkyl of C] _-Cg, C3-Cg cycloalkyl, Cp-Cg alkenyl or C3-Cg alkynyl that is mono- or polysubstituted with identical substituents or different from the group consisting of halogen, cyano, hydroxyl and C1-C4 alkoxy, or is a C2-Cg alkyl, C3-C8 cycloalkyl, C2-Cg alkenyl or C3-C8 alkynyl, which is interrupted once or more than once with oxygen, or is alkoxycarbonyl ( C1-C4) -C1-C4 alkyl, which may be optionally substituted with halogen, or is C2-C4 alkoxycarbonyl, which may be optionally substituted with halogen, m is 3 or 4 n is 0, 1, 2 or 3, or is 1 or 3, p is 2, 3 or 4, and X is oxygen or sulfur, The term halogen covers fluorine, chlorine, bromine and iodine. The terms "alkyl", "alkenyl" and "alkynyl" embrace hydrocarbon radicals which may be branched or straight chain. Preference is given to those substituted pyrazolylpyrazoles of formula I in which: 1 R is methyl, p R is difluoromethoxy, cyano, hydroxyl and alkoxy C1-C4, with the proviso that, if R are hydrogen, or -1 p -i -1 -3 R is hydrogen and Ro is C1-C4 alkyl, R can not be hydrogen, X is oxygen, and n is 0 or is 1. The compounds of formula 1 according to the invention can be prepare: A) by reacting a compound of formula II: wherein R1, R and R are as defined in formula I, with a compound of formula III II R in which R5 is the group COOR7 or C-N where R, R8 and R9 are as defined in the formula I, and X is o and endn ddoonnddee RR226 °, RR2277 and R28 are, independently of each other, C1-C alkyl, or B) if Rb is the group - (CH2) 0-A 'wherein A is the cyano group and or is as defined in formula I, by reacting a compound of the formula wherein R1, R2, R3, R4 and R5 are as defined in formula I, and B is a leaving group such as chlorine, bromine, or methylsulfonyl, with an alkali metal salt of hydrocyanic acid, or C) if R is halogen, by reacting a compound of formula Ib wherein R, R, R, R and R are as defined in formula I, with a suitable halogenating agent, or D) if R is one of the groups wherein R16, R17, R18, R19, R20, R21, R22, R23, R24, R ^ 5, n and X are as defined in formula I, by reacting a compound of the formula le or Id, wherein R 1, R 2, R 3, R 4, R 5, Rld, R 17, and n are as defined in formula I, and R 30 is C 2 -C 4 alkyl, with a compound of formula IV or V (IV) (V), in which R18, R19, R20, R21, R22, R23, R24, R25, and X are as defined in formula I, or E) if R is the group, wherein R, R13 and R are as defined in formula I, and, 2A9y is chlorine or bromine, by first reacting, by diazotization, a compound of the formula wherein R, R, R3, R4 and R are as defined in formula I, to give a compound of the formula If wherein R, R, R, R and R are as defined in formula I, and then by reacting If with a Michael acceptor of formula VI wherein R is as defined in formula 1, or F) if Rb is the group in which R, R and R are as defined in formula I, by reacting a compound of the formula Ig wherein R1, R2, R3, R4, R5, R11, R12 and R13 are pQ as defined in formula I, and R is chloro or bromo, with a suitable base, or G) by reacting a compound of the Ih or Ii formula wherein R 1, R 2, R 3, R 4, R 5, R 12, R 13 and R 29 are as defined in formula I and R is hydroxy, chlorine, bromine or alkoxy of 0 ^ -04, with an alcohol of formula VII or an amine of formula VIII R 11 OH (VII) R 14 R 15 NH (VIII) wherein R1, R14 and R15 are as defined in formula I. The compounds of the formula II used as starting material according to process variant A are known. Its preparation is described in WO 94/08999.

The compounds of the formula I according to the invention in which R is the group -COOR or -CXNR R (process variant A) can be prepared by the method described by Bisagni et al. In Tetrahedron 29,435 (1973). ). Variant B) of the process is advantageously carried out by reacting the starting material of the formula la in a suitable solvent at a temperature of 20 to 180 ° C with a hydrocyanic acid salt. Suitable solvents are for example ethers such as diethyl ether, tetrahydrofuran or 1,4-dioxane, amides such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone, aromatic hydrocarbons such as benzene, toluene or xylene, or sulfoxides such as dimethyl sulfoxide. Suitable cyanides include lithium cyanide, sodium cyanide and potassium cyanide. The compounds of the formula I used as starting material are known. Its preparation is described in WO 94/08999. Halogenation in accordance with variant C) of the process can be carried out by methods known per se for halogenating heterocyclic aromatic compounds, as described for example in Houben-Weyl, Volume V / 4, p. 233 ff (1960) or Volume V / 3, p. 511 ff (1962), using a halogenating agent in a suitable inert solvent.

Suitable halogenating agents include, for example, sulfuryl chloride, sodium hypochlorite, N-chlorosuccinimide, N-bromosuccinimide, chlorine or bromine. The acetals or ketals can be prepared according to variant D) of the process by the methods described in T.W. Greene, "Protective Groups in Organic Synthesis", 1980 p. 116 ff. The compounds of the formulas Ie and Id used as starting material are known. Its preparation is described in WO 94/08999. The compounds according to variant E) of the process can be prepared by the process described in US Pat. No 5,250,504. The compounds of the formula used as starting material are known. Its preparation is described in WO 94/08999. The compounds according to variant F) of the process can be prepared by elimination processes known per se, as described for example in J. March "Advanced Organic Chemistry" 2nd edition 1977, p. 895 ff, and the literature cited therein. The esterifications according to step G) of the process are known per se and can be carried out by customary methods, as described for example in Houben-Weyl, Volume E5, p. 659 ff (1985). This also applies to the formation of amides, which is also described, for example, in Houben-Weyl, Volume E5, p. 934 ff (1985). The individual steps of the procedure can be carried out with or without solvent; if required, those solvents or diluents that are inert to the reagents in question are used. Examples of these solvents or diluents are aliphatic, alicyclic and aromatic hydrocarbons which in each case may be optionally chlorinated, for example hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride. , ethylene chloride, trichlorethylene and chlorobenzene, ethers such as for example diethyl ether, methyl ethyl ether, methyl t-butyl ether, diisopropyl ether, dibutyl ether, dioxane and tetrahydrofuran, ketones such as for example acetone, methyl ethyl ketone, methyl isopropyl ketone, and methyl isobutyl ketone, nitriles such as for example acetonitrile and propionitrile, alcohols such as for example methanol, ethanol, isopropanol, butanol, tert-butanol, tert -amyl alcohol and ethylene glycol, esters such as for example ethyl acetate and amyl acetate, acid amides such as for example dimethylformamide and dimethylacetamide, sulfoxides such as for example dimethyl sulfoxide, sulfones such as for example sulfolane, bases such as for example pyridine and triethylamine, carboxylic acids such as for example acetic acid, and mineral acids such as for example acid sulfuric acid and hydrochloric acid.

The compounds according to the invention are treated in the usual manner. They are purified by crystallization or column chromatography. In general, the compounds according to the invention are colorless or light yellow colored crystalline or viscous substances, some of which are readily soluble in chlorinated hydrocarbons such as, for example, methylene chloride or chloroform, ethers such as, for example, diethyl ether or tetrahydrofuran, alcohols such as for example methanol or ethanol, ketones such as for example acetone or butanone, amides such as for example dimethylformamide, or sulfoxides such as for example dimethyl sulfoxide. The compounds according to the invention show a good herbicidal activity on broadleaf weeds and on grasses. Selective use in a variety of crops is possible, for example in oilseed rape, beet, soybean, cotton, rice, corn, barley, wheat and other cereal species. The individual compounds are also suitable as selective herbicides in beet, cotton, soybean, corn and cereals. Likewise, the compounds can be used to control weeds in perennial crops such as, for example, afforestation, woody ornamental plantings, orchards, vineyards, citrus stands, walnut orchards, plantations of plantains, coffee plantations, tea plantations, plantations of rubber, oil palm plantations, cocoa plantations and in fields of honeyed fruit and hop plants. The compounds according to the invention can be used, for example, in the following genera of plants: Dicotyledonous weeds of genera such as Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoora, Chenopodium, Brassica, Urtica, Senecio, Amaranthus, Poertulaca, Xanthium, Convolvulus, Ipomea, Polygonum, Sesbania, Ambrosia, Cirsium, Sonchus, Solanum, Lamiun, Veronica, Abutilon, Datura, Viola, Galeopsis, Papaver, Centaurea and Crysanthemum; monocotyledonous weeds of genera such as: Oats, Alopecurus, Echinochloa, Setaria, Panicum, Digitaria, Poa, Eleusine, Brachiaria, Lolium, Bromus, Cyperus, Elymus, Sacrittaria, Monochoria, Fimbristylis, Eleocharis, Ischaemun and Apera. When applied pre- and post-emergency, the application regimes vary between 0.001 and 5 kg / ha, depending on the type of application. The intensity of action and speed of action can be promoted, for example, by means of activity-increasing additives such as organic solvents, wetting agents and oils. Therefore, these additives can allow a reduced dosage of the active substance. The active substances according to the invention, or mixtures thereof, are advantageously used in the form of preparations such as powders, spreading materials, granules, solutions, emulsions or suspensions, with the addition of liquid or solid carriers or diluents. , and it is appropriate, thickening agents, wetting agents, emulsifiers and / or dispersants. Examples of suitable liquid carriers are the aliphatic and aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethyl sulfoxide, dimethylformamide and further mineral oil fractions and vegetable oils.

EXAMPLE 1 (PROCEDURE D) 1- (4-Bromo-5-difluoromethoxy-1-methyl-3-pyrazolyl) -5- (4,7-dihydro-1,3-dioxepip-2-yl) -lH- pyrazol-4-sarbonitrile 3.0 g (7.1 mmol) of 1- (4-bromo-5-difluoromethoxy-1-methyl-3-pyrazolyl) -5- (1,1-diethoxyethyl) -1H-pyrazole-4-carbonitrile are dissolved in 50 ml of toluene, and 6.3 g (71 mmol) of cis-2,3-butene-1,4-diol and a catalytic amount of p-toluenesulfonic acid are then added thereto. The mixture is kept boiling for half an hour under a water separator, and the cooled solution is washed with sodium chloride solution, dried with magnesium sulfate and concentrated. The residue is purified by means of column chromatography.

Yield: 2.5 g to 83% of theory. P.f. : 90-91 ° C EXAMPLE 2 (PROCEDURE E) 3- [1- (4-Chloro-5-difluoromesthoxy-l-methyl-3-pyrazolyl) -4-cyano-5-pyrazolyl] -2-chloro-2- methyl methylpropionate 1.5 g (13 mmol) of tert-butyl nitrite, 15 ml of methyl methacrylate and 1.0 g of copper (II) chloride in 15 ml of acetonitrile are charged initially, and 2.55 g are added in three portions ( 10 mmoles) of 5-amino-l-4-chloro-5-difluoromethoxy-l-methyl-3-pyrazolyl) -4-pyrazole-carbonitrile. The mixture is stirred at room temperature for 2 hours, poured into 50 ml of 2N hydrochloric acid and extracted three times with diclor-methane, and the extract is dried over magnesium sulfate and concentrated. The product is purified by column chromatography with hexane / ethyl acetate mixtures. Yield: 1.65 g 46% theoretical. P.f. : 65 ° C EXAMPLE 4 (PROCEDURE G) (E) -3- Cl- (4-Chloro-5-di-1-methoxy-1-methyl-3-pyrazolyl) -4-cyano-5-pyrazolyl] 2-dimethoxyethyl ester 1 g (2.76 mmol) of 1- (4-chloro-5-difluoromethoxy-1-methyl-3-pyrazolyl) -4-cyano-5-pyrazolyl-3-propionyl chloride in 20 ml of dichloromethane are charged initially, and 0.28 g (2.76 mmoles) of triethylamine and 0.29 g (2.76 mmoles) of glycollaldehyde dimethylacetal are added at room temperature. The mixture is stirred at room temperature for 2 hours, the solvent is removed under reduced pressure, and the residue is purified by column chromatography using hexane / ethyl acetate mixtures. Yield: 0.80 g To 67% of theory. P.f. : 92 ° C The following compounds of formula I according to the invention are prepared in a similar manner, where R is hydrogen and "t" above a double bond means the trans configuration of this double bond: PICTURE PICTURE (CONTINUED) PICTURE (CONTINUED) PICTURE (CONTINUED) PICTURE (CONTINUED) PICTURE (CONTINUED) PICTURE (CONTINUED) PICTURE (CONTINUED) PICTURE (CONTINUED) PICTURE (CONTINUED) PICTURE (CONTINUED) PICTURE (CONTINUED) The following examples of use illustrate the invention: EXAMPLES OF USE Abbreviations ALOMY Alopecurus myosuroides AGREE Elymus repens AVEFA Avena fatua SETVI Setaria viridis PANSS Panicu sp. SORHA Sorahum halepense ECHCG Echinochloa crus-aalli DIGS Diataria sancruinalis POAAN Poa annua LOLMU Lolium multiflorum ABUTH Abutilon theophrasti GALAP Galium aparine PHBPU Pharbitis purpureum MATCH Matricaria chamomilla POLPE Polycronum sp. VERPE Veronica Persian CHEAL Chenopodium album AMARE Amaranthus retroflexus STEME Stellaria medium 0 = no damage 1 = 1-25% damage 2 = 25-74% damage 3 = 75-89% damage 4 = 90-100% damage The given plant species were treated postemergence in the greenhouse with the compounds given at an application rate of 0.03 kg of active compound per hectare. For this purpose, the compounds were evenly sprayed on the plants in the form of an emulsion with 500 liters of water / hectare. Two weeks after the treatment, the compounds according to the invention showed outstanding activity against the weed, as can be seen from the following table.

Claims (1)

1. NOVELTY OF THE INVENTION CLAIMS A substituted pyrazolylpyrazole of the formula I 1 wherein R is C1-C4 alkyl; R is C1-C4 alkyl, alkylthio of 1 - ^. , alkylsulfinyl of 0, -4, C 1 -C alkylsulfonyl, C 1 -C alkoxy, or is C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfonyl, or C 1 -C 4 alkoxy, each of which is mono- or polysubstituted with halogen; R and R together form the group - (CH2) m-; R is hydrogen or halogen; R4 is hi < drogeno or C1-C4 alkyl; R5 is hydrogen, nitro, cyano, -COOR7, the group R8 -C-N or -C- R X II XR9 Xl! It's one of the groups R7, R8 and R9 are, independently of one another, hydrogen or C1-C4 alkyl; R8 and R9, together with the adjacent nitrogen atom, form a 5- or 6-membered saturated heterocyclic ring; R is hydrogen, C 1 -C 4 alkyl, or C 4 -C 4 alkyl which is mono- or polysubstituted with halogen; R11 is C5-C8 alkyl, C3-C6 cycloalkyl, C2-Cg alkenyl, C3-C5 alkynyl, or is C alquilo-Cg alkyl, C3-Cg cycloalkyl, C2-C alkenyl or alkynyl C3 ~ C which is mono- or polysubstituted with identical substituents or different from the group consisting of halogen, cyano, hydroxyl and C1-C4 alkoxy, or is C2-C3 alkyl, C3-Cg cycloalkyl, C3-C8 cycloalkyl ) -C1-C alkyl, C3-C8 alkenyl or C3-C8 alkynyl which is interrupted once or more than once by oxygen, or is alkoxycarbonyl (0 ^ -04) -C3-C4 alkyl, which can be optionally substituted with halogen atoms, or is C 1 -C 4 alkoxycarbonyl-C 2 -C 4 alkenyl, which is optionally substituted with halogen, or is the group - (CH 2) -RR; R and R are, independently of one another, hydrogen, halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 3 -C 4 alkynyl or C 1 -C 4 alkoxy, or C 1 -C alkyl, C 2 -C 4 alkenyl or C3-C4 alkynyl which is mono- or polysubstituted with substituents identical or different from the group consisting of halogen, cyano, carboxyl, hydroxyl, C1-C4 alkoxy and C1-C4 alkoxycarbonyl; A is cyano, R 14 and R 15 are, independently of one another, hydrogen, C 1 -C 4 alkyl, C 3 C cycloalkyl, C 2 -C alkenyl or C 3 -C alkynyl, or a C 1 -Cg alkyl, cycloalkyl C3- Cg, C2-Cg alkenyl or C3-Cg alkynyl which is mono- or polysubstituted with identical substituents or different from the group consisting of halogen, cyano, hydroxyl or C1-C4 alkoxy, or a C2-C8 alkyl , C3-C8 cycloalkyl, C2-C8 alkenyl and C3-C8 alkynyl which is interrupted once or more than once by oxygen, or C1-C4 alkoxycarboxy-C1-C4 alkyl which may be optionally substituted with halogen or C 1 -C 4 alkoxycarbonyl-C 2 -C 4 alkenyl, which may be optionally substituted with halogen, or C 1 -C 4 alkoxycarbonyl; R and R, together with the nitrogen atom, form a heterocyclic ring saturated with C3-Cg which may be interrupted once or more than once by oxygen or sulfur; R is hydrogen or alkyl of ^ - ^.; R 17 is hydrogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl; R18 'R19, R20, R21, R22 and R24 are, independently of one another, hydrogen, halogen, C-C4 alkyl, C2-C4 alkenyl or C3-C4 alkynyl carboxyl or C1-C4 alkoxycarbonyl, or an alkyl of C 1 -C 4, C 2 -C 4 alkenyl or C 3 -C 4 alkynyl which is mono- or polysubstituted with identical substituents or different from the group consisting of halogen, cyano, nitro, hydroxyl and C 1 -C alkoxy; R23 and R25 are hydrogen, halogen, C3_-C4 alkyl, C2-C4 alkenyl or C3-C4 alkynyl, or cycloalkyl, C2-C alkenyl or C3-Cg alkynyl which is mono- or polysubstituted with identical substituents or different from the group consisting of halogen, cyano, hydroxyl and C1-C4 alkoxy, or is a C2-C3 alkyl, C3-C8 cycloalkyl, (C3-C8) cycloalkyl-C1-C4 alkyl, C2-alkenyl C8 or C3-C8 alkynyl, which is interrupted once or more than once with oxygen, or is C1-C4 alkoxycarbonyl-C1-C4 alkyl, which may be optionally substituted with halogen, or is alkoxycarbonyl (C2_- C4) -C2-C4 alkenyl, which may be optionally substituted with halogen, or is the group - (CH2) p-NR8R, with the proviso that, if R and R are hydrogen or 1 31 T 3 R is hydrogen and RJ J- is C1-C alkyl, R can not be 3 hydrogen or halogen; R is hydrogen, C ^ -Cg alkyl, C3-Cg cycloalkyl, C2 ~ C alkenyl, C3 ~ C alkynyl, or is a C 1 -Cg alkyl, C 3 -Cg cycloalkyl, C 2 alkenyl ~ C or C3 ~ Cg alkynyl which is mono- or polysubstituted with identical or different substituents from the group consisting of halogen, cyano, hydroxyl and C1-C4 alkoxy, or is a C2-C8 alkyl, C3-C8 cycloalkyl , C2-C8 alkenyl or C3-C8 alkynyl, which is interrupted once or more than once with oxygen, or is (C1-C4) alkoxycarbonyl-C ^ - ^ alkyl, which may be optionally substituted with halogen, or is (C 1 -C 4) alkoxycarbonyl-C 2 -C 4 alkenyl, which may be optionally substituted with halogen; m is 3 or 4; n is 0, 1, 2 or 3; or it is 1 or 3; p is 2, 3 or 4, and X is oxygen or sulfur. 2. - A substituted pyrazolylpyrazole of the formula I, in which: R1 is methyl, R is difluoromethoxy, R and R together form the group - (0112) 4-, R is chlorine or bromine, R is hydrogen, R is nitro or cyano, X is oxygen, and n is 0 or is 1. 3. A herbicidally active composition comprising at least one compound according to claim 1 or 2. 4. A herbicidally active composition according to claim 3 , in the form of a mixture with vehicles and / or auxiliaries. 5. The use of compounds according to claim 1 or 2, to control monocotyledonous and dicotyledonous weed species in the main agricultural crops.