NEW SUBSTITUTED PYRAZOLE DERIVATIVES, PROCESSES FOR THEIR PREPARATION AND THEIR USE AS HERBICIDES

Abstract: New substituted pyrazole derivatives of general formula (I) are described in which R<1>, R<2>, R<3>, R<4>, R<5> and R<6> have the meanings given in the description, processes for their preparation, as well as intermediates, and their use as herbicides.

Description: Title: New substituted oyrazole derivatives, processes fo; their preparation and their use as herbicides Field of the invention This invention relates to new substituted pyrazole derivatives, their preparation, as well as intermediates, and their use as herbicides. Prior Art It is known that 1-phenylpyrazoles possess herbicidal activity (EP 154115) . However the herbicidal activity of these compounds in not high enough or selectivity problems can occur in important crops. The object of the present invention is to make new compounds that have improved biological properties over the known compounds. It has now been found that substituted pyrazole derivatives of general formula I in which STITUTE SHEET R 2 is C 1 -C 4 -alkyl, C 1 -C 4 -alkylthio, C 1 -C 4 -alkoxy, each of which is optionally substituted by one or more halogen atoms, or R 1 and R 2 together form the group -(CH 2 )m' R 3 is hydrogen or halogen, R 4 is hydrogen or C 1 -C 4 -alkyl / R 5 is hydrogen, nitro, cyano or the groups -COOR 7 , -C(=X)NR 7 R 8 or -C(=X)R 10 , R 6 is hydrogen, halogen, cyano, C 1 -C 4 -alkyl, (optionally substituted by one or more halogen or hydroxy groups) , C 1 -C 4 -alkoxy, phenyl, (optionally substituted by one or more halogen, nitro, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or halo-C 1 -C 4 -alkyl groups) , pyrrolyl, or is a C 2 -C 8 -alkyl, C j -Cg-alkenyl, C 3 -C 8 -alkynyl or C 3 -C 8 - lko y group, each of which is interrupted by one or more oxygen atoms, or is the group; -(CH 2 ) a -A, -(CH,) ; -0-(CH 2 ) b -R 22 , -(CH 2 ) a -0-R 23 or -COR- 24 R 7 , R 8 and R 9 , which may be the same or different, are hydrogen or C 1 -C 4 -alkyl or R 8 and R 9 together with the nitrogen to which they are attached form a 5 or 6 membered saturated carbocyclic ring; R 10 is hydrogen or C 1 -C 4 -alkyl, optionally substituted by one or more halogen atoms, R 11 is hydrogen, C 1 -C 4 -alkyl, C 2 -C 6 -alkenyl, C 3 -C 6 -alkynyl or phenyl (each of which is optionally substituted by one or more halogen atoms) , C 3 -C 8 -cycloalkyl, cyanomethyl or the group R 21 CO-; R 12 is C j -C 8 -alkyl, C 2 -C 6 -alkenyl, C 3 -C 6 -alkynyl or phenyl (each of which is optionally substituted by one or more halogen atoms) , C 3 -C 8 -cycloalkyl, cyanomethyl, C 1 -C 4 -alkoxy-C 1 -C 6 -alkyl, di-C 1 -C 4 -alkylamino- C 1 -C 4 -alkyl, tetrahydrofurfurylmethyl, C 3 -C 6 -alkynyl- oxy-C 1 -C 4 -alkyl, benzyl, (optionally substituted by one or more halogen, nitro, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or halo-C 1 -C 4 -alkyl groups) , or is the group -C(=X)R 21 , -(CH 2 ) a -(O) d -R 28 , - (CH 2 ) a -0-(CH 2 ) b .R 28 or -(CH 2 ) a -X-R 34 , and when R 5 is -C(=0)R 10 , and/or when R 1 is C 1 -C 4 -alkyl, R 2 is difluoromethoxy, R 3 is bromo and R 5 is nitro or cyano, R 12 can also be hydrogen; or R 11 and R 12 together with the nitrogen to which they are attached form a 3, 5 or 6 membered saturated carbocyclic or aromatic ring, in which a carbon atom is optionally substituted by an oxygen atom; R 13 is hydrogen, C 1 -C 4 -alkyl, C 2 -C 6 -alkenyl or C 3 -C 6 -alkynyl; or R 13 and R 14 together form the group -(CH 2 ) ; R 14 and R 15 , which may be the same or different, are C 1 -C 4 -alkyl, C 2 -C 6 -alkenyl, C 3 -C 6 -alkynyl or phenyl (each of which is optionally substituted by one or more halogen atoms) , hydrogen, C 3 -C 6 -cycloalkyl or the groups -XR 18 or -NR 19 R 20 ; R 16 is hydrogen, C j -Cg-alkyl, C 2 -C 6 -alkenyl, C 3 -C 6 -alkynyl, C 1 -C 4 -alkylcarbonyl , cyano-C j -C j -alkyl , C 1 -C 4 -alkoxycarbonyl-C 1 -C 4 -alkyl , di-C 1 -C 4 -alkoxy- carbonyl-C 1 -C 4 -alkyl, benzyl, C 1 -C 4 -alkoxy- C j -C-alkynyl, or the group -(CH 2 ) a -R 33 , -(CH 2 ) a -X-R 30 , -(CH 2 ) a -X-(CH 2 ) b -R 30 or -(CH 2 ) a -X-(CH 2 ) b -X-(CH 2 ) c -R 30 / R 17 is hydrogen, C 1 -C 4 -alkyl, C 2 -C 6 -alkenyl, C 3 -C 6 -alkynyl, cyano-C 1 -C 3 -alkyl, C 1 -C 4 -alkylcarbonyl-C 1 -C 3 -alkyl or phenyl, R 18 is C 1 -C 4 -alkyl, optionally substituted by one or more halogens; R 19 and R 20 , which may be the same or different, are hydrogen or C 1 -C 4 -alkyl; R 21 is C 1 -C -alkyl, (optionally substituted by one or more halogens) , C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkylthio- C 1 -C 4 -alkyl, C 3 -C 6 .cycloalkyl, phenyl, (optionally substituted by one or more halogen, nitro, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or halo-C 1 -C 4 -alkyl groups) , or is the group -NR 31 R 32 or -(CH 2 ) a -(0) d -R 33 ; R 22 is C 1 -C 4 -alkoxycarbonyl or carboxy, R 23 is chloro ethyl , cyanomethyl, C 3 -C 6 -cycloalkyl (optionally interrupted by one or more oxygen atoms) , or C 1 -C 4 -alkoxycarbonyl-C 1 -C 4 -alkyl, R 24 is hydroxy or the group -NR^R 26 ; A is -NR 25 R 26 or -S(0) n -R 27 ; R 25 and R 26 , which may be the same or different, are hydrogen or C 1 -C 4 -alkyl; R 27 is C j -C 4 -alkyl, C 1 -C 4 -alkoxycarbonyl-C 1 -C 4 -alkyl or carboxy , R 28 is hydrogen, hydroxy, halogen, C 1 -C 4 -alkyl, (optionally substituted by one or more C 1 -C 4 -alkoxy groups) , C 3 -C 6 -cycloalkyl (optionally interrupted by one or more oxygen atoms and optionally substituted by dimethyl), furyl, thienyl or -C(=0)R 29 ; R 29 and R 30 , which may be the same or different, are C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy; R 31 and R 32 , which may be the same or different, are C ] ,-C 4 -al yl or phenyl; R 33 is C 3 -C 6 -cycloalkyl (optionally interrupted by one or more oxygen atoms and optionally substituted by dimethyl), furyl, thienyl or -C(=0)R 29 ; R 34 is C 1 -C 4 -alkyl; a, b and c are 1, 2 or 3; d is 0 or 1; m is 3 or 4; p is 2 or 3; and X is oxygen or sulfur, possess better herbicide properties than the known compounds of related structure. Particularly active are those pyrazole derivatives as defined above, in which R 1 is methyl; R 2 is methylthio or difluoromethoxy (and especially difluoromethoxy) ; or R 1 and R 2 together form the group -(CH 2 ) 4 ; R 3 is hydrogen, chloro or bromo; R 4 is hydrogen; R 5 is hydrogen, nitro, cyano or -C(=X)R 10 . In a particularly preferred group of compounds, R 6 is hydrogen, halogen, cyano, C 1 -C 4 -alkyl, C^-alkylthio or -NR π R 12 , with R 11 and R 12 preferably being hydrogen, C^-alkyl or C 1-4 -alkoxycarbonyl. The term "halogen" means fluorine, chlorine, bromine and iodine . It is to be understood that the term "alkyl", "alkenyl" and "alkynyl" includes branched as well as straight chained hydrocarbon groups. The invention also includes intermediates of general formula II in which R 1 , R 2 and R 3 have the meanings given in general formula I, intermediates of general formula Ii in which R 1 and R- have the meanings given in general formula I, intermediates of general formula Ij i i R in which R 1 , R 2 and R have the meanings given in general formula I, intermediates of general formula Ik in which R 1 , R 2 and R 6 have the meanings given in general formula I, intermediates of general formula II I 1 in which R 1 , R 2 and R 3 have the meanings given in general formula I, and intermediates of general formula Im in which R 1 , R 2 , R 3 and R 6 have the meanings given in general formula I. The compounds of the invention of general formula I can be prepared, by a process in which A) a compound of σeneral formula II in which R 1 , R 2 and R have the meanings given in general formula I, is reacted with a compound of general formula III R R 5 Y CN in which R 4 and R ~ - have the meanings given in general formula I and Y is C 1 -C 6 -alkoxy, hydroxy or halogen, 02 when R 5 is hydrogen, B) a compound of general formula II TE SHEET in which R 1 , R 2 and R J have the meanings given in general formula I, is reacted with a 2-haloacrylonitrile of formula Ilia or with a 2, 3-dihalopropionitrile of formula Illb / C / Hal-CΗ 2 —CH ( I II b ), Hal in which Hal is halogen, or when R J is halogen, C) a compound of general formula la in which R 1 , R 2 , R 5 , R 11 and R 12 have the meanings given in general formula I, is reacted first with a halogenating agent to give a compound of formula lb SUBSTITUTE SHEET in which R 1 , R 2 , R 5 , R 11 and R 12 have the meanings given in general formula I, and Hal is halogen, and then further treated to give the desired compound, or when R 5 is -C(=S)R 10 and R 6 is a ino, D) a compound of general formula Ic in which R 1 , R 2 , R 3 , R 4 and R 10 have the meanings given in general formula I, is treated with Lawesson's reagent, or when R 3 is -OR 16 , E) a compound of general formula Id in which R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given in general formula I, is first diazotised to give a compound of formula le in which R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given in general formula I, and then by heating to give a compound of formula If in which R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given in general formula I, which is then reacted with a compound of general formula IV in which R 16 has the meaning given in general formula I, and Q is a leaving group, or when R 5 is nitro and R 6 is -SR 17 , F) a compound of general formula Ig in which R 1 , R 2 , R J and R 4 have the meanings given in general formula I and Hal is halogen is reacted with a nucleophile of general formula V Θ SR 17 (V) in which R 17 has the meaning given in general formula I, or when R 5 is nitro and R 6 is -S(0) R 17 , in which n is 1 or 2, G) a compound of general formula Ih in which R 1 , R 2 , R J , R 4 and R 17 have the meanings given in general formula I, is subjected to a stepwise oxidation with m-chloroperbenzoic acid, or when R 5 is cyano H) a compound of general formula Ila 2 in which R 1 and R 2 have the meanings given in general formula I, is reacted with a compound of general formula in which Y is C^Cg-alkoxy, hydroxy or halogen, or when R 5 is nitro, I) a compound of general formula Ii 2 NH 2 in which R 1 and R 2 have the meanings given in general formula I, is nitrated in known manner, or J) a compound of general formula Ij I 1 p in which R 1 , R- and R- 3 have the meanings given in general formula I, is brominated in known manner, or when when R- 3 is halogen, K) a compound of general formula II in which R 1 , R 2 and R J have the meanings given in general formula I, is reacted with a compound of general formula Illc in which Y' is C^Cg-alkoxy , dimethylamino or halogen , o f irst give compound of formula II i 1 R UBSTITUTE SHEET in which R 1 , R 2 and R have the meanings given in general formula I, and this compound is then diazotised in known manner with sodium nitrite and converted to the corresponding halide, or L) a compound of general formula Ik in which R 1 , R 2 and R 6 have the meanings given in general formula I, is treated with a halogenating agent, or M) a compound of general formula Im in which R 1 , R 2 and R J have the meanings given in general formula I, and R 6 is C 1 -C 4 -alkyl, (optionally substituted by one or more halogens) or is a C--C 8 -alkyl, interrupted by one or more oxygens, is converted in known manner to the nitrile of general formula I, or when R 6 is -NR π R 12 , N) a compound of general formula In in which R 1 , R 2 and R 3 have the meanings given in general formula I, is reacted with an a ine in a solvent, or when R 6 is -NR π R 12 , in which R 11 is hydrogen and R 12 is -Cg-alkyl, 0) a compound of general formula II in which R 1 , R 2 and R 3 have the meanings given in general formula I, is reacted with a trialkyl ortho ester and then reduced, or P) a compound of general formula Io in which R 1 , R 2 and R 3 have the meanings given in general formula I, and R 12 is C -r,- c C6 6 --alkyl is reacted with an base and an alkylating agent or an acid chloride, or when R 6 is -NR π R 12 , in which R 11 and R 12 are C^Cg-alkyl, Q) a compound of general formula II I 1 R in which R 1 , R 2 and R 3 have the meanings given in general formula I, is reacted with approximately 2 mole of base and 2 mole of a suitable alkylating agent, or R) a compound of general formula II I 1 R in which R 1 , R 2 and R J have the meanings given in general formula I, is reacted with or without a base and a suitable acid chloride, or S) a compound of general formula Ip in which R 1 , R 2 , R 3 and R 21 have the meanings given in general formula I, is reacted with a base and a suitable alkylating agent, or T) a compound of general formula In I 1 R in which R 1 , R 2 and R J have the meanings given in general formula I and R 5 is cyano or nitro, is reacted with an oxygen , nitrogen , sulfur or carbon nucleophile , or when R 6 is substituted methyl U) a compound of general formula Iq in which R 1 , R 2 , R J , R 4 and R 5 have the meanings given in general formula I, is reacted with a Lewis acid, or V) a compound of general formula Ir in which R 1 , R 2 , R J , R 4 and R 5 have the meanings given in general formula I, is treated with a halogenating agent, or W) a compound of general formula Is SUBSTITUTE SHEET in which R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given in general formula I, is reacted with an oxygen, nitrogen, sulfur or carbon nucleophile, or when R 6 is mercapto X) a compound of general formula It in which R 1 , R 2 , R J and R have the meanings given in general formula I, is -created with sodium hydrogen sulfide, or Y) a compound of general formula Iu Λ in which R 1 , R 2 , R J and R 4 have the meanings given in general formula I, is treated with a suitable alkylating agent, or Z) a compound of general formula Iv in which R 1 , R 2 , R 3 and R 4 have the meanings given in general formula I, and R x is C 1 -C 4 -alkyl, is oxidised in stages. The compounds of the invention of general formula I, in which R 5 is nitro and R 6 is halogen, can also be prepared according to the process described in DE 3501323. The compounds of the invention of general formula I, in which R 5 is the group -C(0)R 10 and R 6 is amino, can also be prepared according to the process described in Collect. Czech. Chem. Commun. 5_5, 1038-48 (1990) . The compounds of the invention of general formula I, in which R 6 is the group -NR π R 12 , can also be prepared according to the known processes described in DE 3 707 686, DE 3 543 034, EP 224 831, DE 3 543 035, JP 57167972 and DE 2 747 531. The compounds of the invention of general formula I, in which R 14 is the group -OR 18 or -NR 19 R 20 , can be prepared from compounds of general formula I, in which R 6 is amino according to the known processes described in Chem. Soc. Rev. 4., 231-50 (1975) and J. March, Advanced Organic Chemistry, 1985, p. 370. The compounds of the invention of general formula I, in which R 5 is cyano or nitro and R 6 is C j -C -alkyl, can be prepared according to known processes (J. Heterocyclic Chem. 2_4, 1669 (1987), ibid. 24, 739 (1987). The reactions are suitably carried out by reacting the compounds of formulae II, Ila or III in a suitable solvent at a temperature between -30 and 150°C, preferably at room temperature. As halogenating agent there can be used for example sulfuryl chloride, sodium hypochlorite, N-chlorosuccinimide, N-bromosuccinimide, bromine or chlorine. Leaving groups in process variant E are chloro or bromo. The nitration in process variant I) is suitably carried out in known manner with nitric acid in acetic anhydride. The reaction temperature lies in the region of -10 to 140°C. The process variant J) is suitably carried out in a solvent at a temperature of -20°C up to the boiling point of the solvent. As brominating agent in process variant J) there can be used, for example N-bromosuccinimide or bromine. The reaction of compounds of general formula II is suitably carried by the method described in J. March, Advanced Organic Chemistry, 1985. p. 647. The process variant L) is generally carried out in a suitable solvent, preferably acetonitrile or dichloromethane, at a temperature of between -10°C and 80°C. Process variant M) is generally carried out according to the method described in Tetrahedron Letters, 1977 p. 1813. Process variant O) is generally carried out according to the known methods (J. March, Advanced Organic Chemistry, 1985. p. 798-800 and literature cited there) . Suitable bases for process variants P) , Q) , R) and S) include for example alkali metal and alkaline earth metal hydroxides, sodium methanolate, alkali metal hydrides, alkali metal and alkaline earth metal carbonates, tertiary aliphatic and aromatic amines, such as triethylamine and pyridine as well as heterocyclic bases. Process variant T) is generally carried out for example according to methods described in J. Heterocyclic Chem. 25, 555 (1988) . The preparation can be carried out with or without a solvent. Should need arise, such solvent or diluents can be used which are inert to the reactants. Examples of such solvents or diluents are aliphatic, alicyclic and aromatic hydrocarbons, each of which can be optionally chlorinated, such as for example hexane, cyclohexane, petroleum ether, naphtha, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene dichloride, trichloroethane 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 ethanol, ethanol, isopropanol, butanol, tert- butanol, tert-amyl alcohol and ethylene glycol, esters, such as for example ethyl acetate and amyl acetate, amides, such as for example dimethylforma ide and dimethylacetamide, sulfoxides, such as for example dimethyl sulfoxide and 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 sulfuric acid and hydrochloric acid. The compounds of the invention can be worked up in conventional manner. Purification can be achieved by crystallisation or column chromatography. The compounds of the invention are, as a rule, colourless or slightly yellow crystalline or liquids or substances that are highly soluble in halogenated hydrocarbons, such as methylene chloride or chloroform, Ethers, such as diethyl ether or tetrahydrofuran, alcohols, such as methanol or ethanol, ketones, such as acetone or. butanone, amides, such as dimethylformamide, and also sulfoxides, such as dimethyl sulfoxide. The intermediate compounds of general formula II in which R 1 , R 2 and R 3 have the meanings given in general formula I can be prepared in known manner (e.g. JP 62158260) from compounds of general formula VI in which R 1 , R 2 and R have the meanings given in general formula I. The compounds of general formula II in which R 1 and R 2 together form the group -(CH 2 ) m - and R 3 is hydrogen, can be prepared by treating a compound of general formula Illc ( 1 1 1 c ), with hydrazine with addition of a base. The compound of general formula Illc can be prepared by reacting a compound of general formula Hid and a 1,1-dihaloethylene. The compounds of general formula VI, in which R 1 and R 2 have the meanings given in general formula I and R 3 is halogen, can be prepared by reacting a compound of general formula VI in which R 3 is hydrogen, with a halogenating agent. The compounds used as starting materials for compounds of general formula VI, are of general formula VII in which R 1 has the meaning given in general formula I , and can be prepared for example, by a process in which, in the case when R 2 is C 1 -C 4 -alkyl , optionally substituted by halogen, a) a compound of general formula VIII, Villa or IX in which R 2 is C 1 -C 4 -alkyl , optionally substituted by halogen , is reacted with a compound of general formula X R 1 - NHNH2 (X) in which R 1 has the meaning given in general formula I, optionally in the presence of a solvent, or when R 2 is C 1 -C 4 -alkylthio, optionally substituted by one or more halogens, b) a compound of general formula XI in which R 35 is cyano or the group -COOR 36 , in which R 36 is C 1 -C 4 -alkyl, is reacted with a compound of general formula X, optionally in the presence of a solvent, e.g. water, to give first a compound of general formula XII in which R 1 has the meaning given in general formula I and R 35 has the meaning given above, which is then reacted with a compound of general formula XIII R 37 Q (XIII) in which R 37 is C 1 -C 4 -alkyl, optionally substituted by one or more halogens, and Q is a leaving group, and the resulting compound of general formula XIV is saponified and decarboxylated according to known literature methods (e.g. Zeitschrift fur Che ie 420, (1968)), or c) a compound of general formula XV in which R 35 is cyano or the group -COOR 36 , in which R 36 is C 1 -C 4 -alkyl, and R 37 is C 1 -C 4 -alkyl, optionally substituted by one or more halogens, is reacted with a compound of general formula X, optionally in the presence of a solvent, e.g. water, to give a compound of general formula XIV, or when R 2 is C 1 -C 4 -alkoxy, optionally substituted by one or more halogens d) a compound of general formula XVI in which R 1 has the meaning given in general formula I, is reacted with a compound of general formula XIII, in the presence of a base, or h) a compound of general formula XVII in which R 1 has the meaning given in general formula I and Z is C 1 -C 4 -alkyl, is reacted, in the presence of a base, with a compound of general formula XIII R 37 Q (XIII) in which R 37 is C 1 -C 4 -alkyl, optionally substituted by one or more halogens, and Q is a leaving group, and the resulting compound of general formula XVIII in which R 1 has the meaning given in general formula I, R ,37 is C 1 -C 4 -alkyl, optionally substituted by one or more halogens, ' and Z is C 1 -C 4 -alkyl, is reacted with ammonia and the resulting compound of general formula XIX 0 II in which R 1 has the meaning given in general formula I and R 37 is C 1 -C 4 -alkyl, optionally substituted by one or more halogens, is reacted with sodium hydroxide and a halogen, or when R 3 in general formula I is halogen, f) a compound of general formula XVIII or XIX O in which R 1 has the meaning given in general formula I, R 37 is C 1 -C 4 -alkyl, optionally substituted by one or more halogens, and Z is C 1 -C 4 -alkyl, is reacted with a halogenating agent to give a compound of general formula XVIIIa and XlXb SUBSTITUTE SHEET in which R > 1, rR>37 and Z have the meanings given in general formula XVIII and XIX, or g) a compound of general formula XlXa in which R 1 has the meaning given in general formula I, R 37 is C 1 -C 4 -alkyl, optionally substituted by one or more halogens, and Hal is halogen, is reacted with sodium hydroxide and bromine to give a compound of general formula XX in which R 1 , R 37 and Hal have the meanings given in formula XlXa, or when R 1 and R 2 together form a tri- or tetramethylene group h) a compound of general formula XXI in which n is 2 or 3, is reacted with hydrazine and the resulting 3(5)-amino-5(3)-hydroxyalkylpyrazole of general formula XXII H in which n is 2 or 3, is reacted with hexane-2,5-dione, phthalic anhydride or tetrahydrophthalic anhydride, in a similar manner to known literature methods (Bull. Chem. Soc. Jp., ________ 2856-8 (1971), or EP 305826), to give a compound of general formula XXIII (XXIII). H in which n is 2 or 3 and Q is an amino protecting group, such as e.g. Q l r Q 2 or Q 3 and this is cyclised using the Mitsunobu variant (Synthesis, 1 (1981)), to give a compound of general formula XXIV in which n is 2 or 3, and then in the case when Q is Q. , this is treated with hydroxylamine as described in J. Org. Chem., ! , 1224-1227 (1984), and in the case when Q is Q 2 or Q 3 , this is treated with hydrazine, in a similar manner to known literature methods (Org. Synthesis, Coll. Vol., 2, 148 (1955)). The starting materials of general formula XXI can be prepared in known manner (Chem. Ber. , 109(1), 253-60, 1976) . The compounds of general formula li, used as starting materials, can be prepared by decarboxylating a compound of general formula XXV I 1 R in which R 1 and R 2 have the meanings given in general formula I. The compounds of general formula XXV can be prepared by saponifying a compound of general formula XXVI n R in which R 1 and R 2 , have the meanings given under general formula I and R 7 is C 1 -C 4 -alkyl. The compounds of general formula XXVI can be prepared by reacting a compound of general Ila, in which R 1 and R 2 have the meanings given under general formula I with a compound of general formula XXVII ( XXVII ) , in which R 7 is C 1 -C 4 -alkyl and Y is C j -Cg-alkoxy, hydroxy or halogen. The intermediates of general formula Ij , can be prepared in an analogous way to process described above in which instead of the compounds of general formulae Ila and li the corresponding compounds of general formula XXVIII and/or XXIX are used. The intermediates of general formula Ik, can be prepared by reacting a compound of general formula lib in which R 1 and R 2 have the meanings given in general formula lib in an analogous way to processes described above. The intermediates of general formula Im, in which R 6 is C 1 -C 4 -alkyl, optionally substituted by one or more halogens or C 2 -C 8 -alkyl, interrupted by one or more oxygen atoms, can be prepared converting a compound of general formula iq in which R 1 , R 2 and R 3 have the meanings given in general formula I, R 6 is C 1 -C 4 -alkyl, optionally substituted by one or more halogens or C 2 -C 8 -alkyl, interrupted by one or more oxygen atoms, and R 7 is C 1 -C 4 -alkyl, in known manner to the amide. The compounds of general formula Iq can be prepared in known manner (J. Heterocyclic Chem 2±, 1669 (1987) , ibid. 24 , 739 ( 1987 ) ) . The preparation of the intermediates can be carried out with or without a solvent. Should need arise, a solvent mentioned above can be used. The named starting materials are either known in the or can be prepared in similar manner to known methods. The compounds of the invention show a good herbicidal activity against broad leaved weeds and grasses. A selective use of the compounds of the invention in various crops is possible for example in rape, beet, soya beans, cotton, rice, barley, wheat and other cereals. Individual active substances are particularly suitable as selective herbicides in beet, cotton, soya, maize and cereals. However the compounds can be used for control of weeds in permanent crops, such as for example forestry, ornamental trees, fruit, vine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plantations. The compounds of the invention can used for example against the following plant species: Dicotyledonous weeds of the species: Sinapis, Lepidiu , Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Brassica, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipo oea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Lamium, Veronica, Abutilon, Datura, Viola, Galeopsis, Papaver, Centaurea and Chrysanthemum. Monocotyledonous weeds of the species: Avena, Alopecurus, Echinochloa, Setaria, Panicum, Digitaria, Poa, Eleusine, Brachiaria, Lolium, Bromus, Cyperus, Agropyron, Sagittaria, Monocharia, Fimbristylis, Eleocharis, Ischaemum and Apera. The rates of use vary depending on the manner of pre- and poste ergent use between 0.001 and 5 kg/ha. The compounds of the invention can also be used as defoliants, desiccants and total herbicides. The compounds of the invention can be used either alone or in admixture with one another or with other active agents. Optionally, other plant-protective agents or pesticides can be added, depending on the purpose for the treatment. When it is desired to broaden the spectrum of activity, other herbicides can also be added. Herbicidally active mixing partners suitable in this connection include for example, the active agents listed in Weed Abstracts, vol. 40, No. 1, 1991, under the heading "Lists of common names and abbreviations employed for currently used herbicides and plant growth regulators in Weed Abstracts". An improvement in the intensity and speed of action can be obtained, for example, by addition of suitable adjuvants, such as organic solvents, wetting agents and oils. Such additives may allow a decrease in the dose. The designated active ingredients or their mixtures can suitably be used, for example, as powders, dusts, granules, solutions, emulsions or suspensions, with the addition of liquid and/or solid carriers and/or diluents and, optionally, binding, wetting, emulsifying and/or dispersing adjuvants. Suitable liquid carriers are, for example aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene. cyclohexanone, isophorone, dimethyl sulfoxide, dimethylformamide and other mineral-oil fractions and plant oils. Suitable solid carriers include mineral earths, e.g. bentonite, silica gel, talcum, kaolin, attapulgite, limestone, silicic acid and plant products, e.g. flours. As surface-active agents there can be used for example calcium lignosulfonate, polyoxyethylenealkylphenyl ethers, naphthalenesulfonic acids and their salts, phenolsulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates, as well as substituted benzenesulfonic acids and their salts. The percentage of the active ingredient(s) in the various preparations can vary within wide limits. For example, the compositions can contain about 10 to 90 percent by weight active ingredients, and about 90 to 10 percent by weight liquid or solid carriers, as well as, optionally up to 20 percent by weight of surfactant. The agents can be applied in customary fashion, for example with water as the carrier in spray mixture volumes of approximately 100 to 1,000 1/ha. The agents can be applied using low-volume or ultra-low-volume techniques or in the form of so-called microgranules. The preparation of these formulations can be carried out in known manner, for example by milling or mixing processes. Optionally, individual components can be mixed just before use for example by the so-called commonly used tank-mixing method. Formulations can be prepared, for example, from the following ingredients. A) Wettable Powder 20 percent by weight active ingredient 35 percent by weight fuller's earth 8 percent by weight calcium lignosulfonate 2 percent by weight sodium salt of N-methyl-N-oleyltaurine 25 percent by weight silicic acid B) Paste 45 percent by weight active ingredient 5 percent by weight sodium aluminium silicate 15 percent by weight cetyl polyglycol ether with 8 mole ethylene oxide 2 percent by weight spindle oil 10 percent by weight polyethylene glycol 23 percent by weight water C) Emulsifiable Concentrate 20 percent by weight active ingredient 75 percent by weight isophorone 5 percent by weight of a mixture of the sodium salt of N-methyl-N-oleyltaurine and calcium lignosulfonate The following examples illustrate the preparation of compounds according to the invention. Example 1.0 4-Acetyl-5-amino-l-C3-chloro-4.5.6,7-tetrahvdropyrazolo- ri.5-al yridin-2-yl)pyrazole 0.56 g (3 mmol) 3-Chloro-2-hydrazino-4, 5, 6,7-tetrahydro- pyrazolo[l,5-a]pyridine was dissolved in 5 ml ethanol and treated with 0.42 g (3 mmol) 2-ethoxymethylen-3-oxobutyro- nitrile. After heating under reflux for 3 hours, the mixture was concentrated and the residue purified by silica gel chromatography (hexane/ethyl acetate 1:1) . Yield: 0.75 g = 89.4% of theory mp: 153-154°C Example 1.1 5-Amino-l-C3-chloro-4 , 5.6,7-tetrahvdropyrazolo- n,5-alpyridin-2-vH -4-thioacetylpyrazole 0.28 g (1 mmol) 4-Acetyl-5-amino-l-(3-chloro- 4,5,6,7-tetrahydrqpyrazolo[1,5-a]pyridin-2-yl)pyrazole was dissolved in 5 ml dimethoxyethane and treated with 0.28 (0.6 mmol) Lawesson's reagent. After heating under reflux for 2 hours with stirring, the reaction solution was poured into water and extracted with ethyl acetate. The organic phase was washed with saturated aqueous sodium chloride, dried over magnesium sulfate and concentrated. The residue was purified by silica gel column chromatography. (Hexane/ethyl acetate 1:1) . Yield: 0.21 g = 71% of theory mp: 166-167°C Example 1.2 N-ri-C3-Chloro-4.5, 6,7-tetrahydropyrazolor1, 5-alpyridin- 2-yl)-4-nitro-5-pyrazolyl]propionamide 8.72 g (29.7 mmol) N-[l-(3-Chloro-4,5, 6,7-tetrahydro- pyrazolo[l,5-a]pyridin-2-yl)-5-pyrazolyl]propionamide was suspended in 33 ml acetic acid. Under ice cooling, at 0-5°C, 3.31 g (32.5 mmol) acetic anhydride was added. 1.93 g (31 mmol) Fuming nitric acid was added dropwise. After stirring for 6 hours at room temperature, the mixture was concentrated. The residue was taken up in dichloromethane, neutralised with aqueous sodium hydrogen carbonate and washed with aqueous sodium chloride. The organic phase was dried over magnesium sulfate and concentrated. The residue was purified by silica gel chromatography (hexane/ethyl acetate 1:1). Yield: 6.03 g = 60% of theory mp: 46-49°C Example 2.0 N-f1-(4-Chloro-5-difluoromethoxy-l-methyl-3-pyrazolyl ) - 4-nitro-5-pyrazolyl1-2.2 ,2-trifluoroacetamide 0.79 g (2.1 mmol) N-[l-(5-Difluoromethoxy-1-methyl- 3-pyrazolyl) -4-nitro-5-pyrazolyl]-2-2, 2-trifluoroacetamide was suspended in 35 ml dichloromethane and treated with 0.17 ml sulfuryl chloride. The mixture was stirred for one hour at room temperature and concentrated. Yield: 0.77 g = 89.5% of theory mp: 136-139°C Example 2.1 N-ri-C4-Chloro-5-difluoromethoxy-l-methyl-3-pyrazolyl) - 4-nitro-5-pyrazolyl1acetamide 1.3 g (5.0 mmol) 5-Amino-l-(4-chloro-5-difluoromethoxy- l-methyl-3-pyrazolyl)pyrazole was dissolved in 20 ml acetic acid and treated with 0.55 g (5.4 mmol) acetic anhydride. After stirring for 2 hours at room temperature the reaction solution was cooled to 0°C and 0.4 g (6.4 mmol) concentrated nitric acid added. After stirring for 8 hours at room temperature, the reaction mixture was poured into ice water and extracted with ethyl acetate. The organic phase was dried over magnesium sulfate and concentrated. The residue was purified by silica gel column chromatography (hexane/ethyl acetate 1:1). Yield: 1.4 g = 81.5% of theory mp: 132°C Example 3.1 5-Amino-4-nitro-l-f4-bromo-5-difluoromethoxy-1-methyl- 3-pyrazolyl)pyrazole 8.3 g (0.052 ol) Bromine was added dropwise at room temperature to 13 g (0.047 mol) 5-amino-4-nitro- l-(5-difluoromethoxy-l-methyl-3-pyrazolyl)pyrazole dissolved in 260 ml acetic acid and the mixture stirred for 30 minutes. It was then concentrated and the residue taken up in the ethyl acetate and shaken with 5% aqueous sodium hydrogen carbonate. The phases were separated and the organic phase dried over magnesium sulfate. This was concentrated and the residue purified by silica gel column chromatography (hexane/ethyl acetate 3:1). Yield: 8.3 g = 49.6% of theory mp: 148°C Preparation of the starting materials 1. 5-Amino-4-nitro-l-f5-difluoromethoxy-1-methyl- 3-pyrazolyl) -pyrazole 15 g (0.065 mol) 5-Amino-l-(5-difluoromethoxy-1-methyl- 3-pyrazolyl)pyrazole was dissolved in 60 ml acetic acid and treated with 7.35 g (0.072 mol) acetic anhydride. After stirring at room temperature for 3 hours, the reaction mixture was cooled to 10°C. 4.95 g (0.078 mol) Fuming nitric acid was added dropwise and the mixture treated with 8.0 g (0.078 mol) acetic anhydride. After stirring for 18 hours at room temperature, the reaction mixture was added to 500 ml ice-water. It was extracted three times with ethyl acetate, the organic phases were washed with water and concentrated. The residue was treated with 80 ml ethanol and 40 ml concentrated hydrochloric acid. After heating for 8 hours under reflux, the ethanol was removed and the residue extracted with ethyl acetate. The concentrated ethyl acetate phases were washed with saturated aqueous sodium hydrogen carbonate, dried over magnesium sulfate and concentrated. The residue was recrystallised from diisopropyl ether and ethyl acetate. Yield: 10 g = 56% of theory mp: 140°C 2. 5-Amino-l-(5-difluoromethoxy-l-methyl-3-pyrazolyl - pyrazole 16.5 (0.06 mol) 5-Amino-l-(5-difluoromethoxy-1-methyl- 3-pyrazolyl) -4-pyrazolecarboxylic acid was heated at 210°C for 5 minutes and then cooled. The congealed melt was recrystallised from diisopropyl ether. Yield: 12.6 g = 92% of theory mp: 106-107°C 3. 5-Amino-l- (5-difluoromethoxy-l-methyl- 3-pyrazolyl') -4-pyrazolecarboxylic acid 18.9 g (0.06 mol) Ethyl 5-Amino-l-(5-difluoromethoxy- l-methyl-3-pyrazolyl) -4-pyrazolyl-4-pyrazolecarboxylate was dissolved in 150 ml 50% ethanol and treated with 15 ml 45% caustic soda. The mixture was heated for 2 hours at 80°C, the ethanol distilled, the residue treated with ice- water and acidified with concentrated hydrochloric acid. The residue was removed by suction filtration, washed with water and dried in vacuo at 75°C. Yield: 16.7 g = 97% of theory mp: 173°C (dec.) 4. Ethyl 5-Amino-l- (5-difluoromethoxy-1-methyl- 3-pyrazolyH -4-pyrazolyl-4-pyrazolecarboxylate 19 g (0.1 mol) 5-Difluoromethoxy-3-hydrazino-l-methyl- pyrazole was dissolved in 100 ml ethanol. 18.05 g (0.1 mol) Ethyl ethoxymethylenecyanoacetate was added and the mixture heated for 1.5 hours at boiling. After cooling, the precipitated product was removed by suction filtration, washed with some ethanol and dried. Yield: 18.95 g = 59% of theory mp: 168-169°C 5-Difluoromethoχy-3-hydrazino-l-methylpyrazole 39.8 g (0.25 mol) 3-Amino-5-difluoromethoxy-1-methyl- pyrazole was dissolved in 224 ml water and 450 ml concentrated hydrochloric acid. At -10°C, 18.55 g (0.27 mol) sodium nitrite in 80 ml water was added dropwise. After stirring for 1 hour at -10°C, 137.6 g tin(II) chloride, dissolved in 180 ml concentrated hydrochloric acid, was added, dropwise, at this temperature. After a further hour stirring at -10°C, 805 ml 32% caustic soda was added dropwise at this temperature. The reaction mixture was shaken 8 times with ethyl acetate, the combined organic phases washed with saturated aqueous sodium chloride, dried over magnesium sulfate and concentrated. Yield: 42.24 g = 97.2% of theory Example 3.2 5-Amino-l-f4-bromo-5-difluoromethoxy-l-methyl- 3-pyrazolyl)-4-pyrazolecarbonitrile 5.0 g (20 mmol) 5-Amino-l-(5-difluoromethoxy-1-methyl- 3-pyrazolyl)-4-pyrazolecarbonitrile was dissolved in 80 ml acetic acid. At room temperature, 1.2 ml (23 mmol) bromine was added, dropwise. After stirring for 15 minutes, the mixture was concentrated and stirred with diisopropyl ether/propanol. The solid material was suction filtered and dried. Yield: 5.7 g = 87% of theory mp: 160°C Example 3.3 5-Amino-l-f3-bromo-4.5.6 ,7-tetrahydropyrazolo- ri.5-a1-pyridin-2-yl) -4-nitropyrazole 3.6 g (12.7 mmol) 5-Amino-l-(3-bromo-4, 5, 6,7-tetrahydro- pyrazolo[l, 5-a]pyridin-2-yl)pyrazole was suspended in 15 ml acetic acid and treated with 1.23 ml (13.0 mmol) acetic anhydride. The mixture was stirred for 5 hours at room temperature. 1.5 ml (15.9 mmol) acetic anhydride was added and then, with ice-bath cooling, 0.66 ml (15.5 mmol) fuming nitric acid was added, dropwise. After stirring for 12 hours at room temperature, the mixture was concentrated. The residue was dissolved in 30 ml ethanol and treated with 11.2 ml concentrated hydrochloric acid. After heating for 3 hours under reflux, the mixture was concentrated and the residue taken up in water and ethyl acetate. It was made basic with 2N aqueous sodium hydroxide and the organic phase separated. The aqueous phase was extracted twice with ethyl acetate. The combined organic phases were washed once with water and once with saturated aqueous sodium chloride. The organic phase was dried and concentrated. The residue was recrystallised from ethyl acetate. Example 4.1 1- (3-Chloro-4. 5 . 6 ,7-tetrahvdropyrazoloT1_ 5-a1pyridin- 2-yl) -5-diethylamino-4-pyrazolecarbonitrile 10.45 g (0.35 mol) Sodium hydride (80%) was added to 100 ml tetrahydrofuran and cooled to 0°C. In a nitrogen atmosphere, a suspension of 43.6 g (0.17 mol) 5-amino-l-(3-chloro-4,5,6,7-tetrahydropyrazolo- [l,5-a]pyridin-2-yl)-4-pyrazolecarbonitrile in 500 ml tetrahydrofuran was added dropwise. The mixture was stirred for 1.5 hours. Then 31.4 ml (0.38 mol) iodoethane in 20 ml tetrahydrofuran was added dropwise at 15°C. After stirring for three hours at 15°C, the mixture was cooled. Water was then added dropwise and the mixture extracted with ethyl acetate. The organic phase was separated, dried and concentrated. The residue was recrystallised from ethyl acetate. Yield: 47.3 g = 89.4% of theory mp: 68-70 °C Example 4.2 l-(3-Chloro-4 ,5,6 ,7-tetrahydropyrazolo ϊ1, 5-alPyridin- 2-yl)-5-(ethylmethylamino) -4-pyrazolecarbonitrile 23.3 g (88.7 mmol) 5-Amino-l-(3-chloro-4,5, 6,7-tetrahydro- pyrazolo[l,5-a]pyridin-2-yl)-4-pyrazolecarbonitrile, 202 ml (1,21 mmol) triethyl orthoformate and 10 drops trifluoroacetic acid was heated for 5 hours with removal of water in a water bath at a temperature of 150°C. The reaction solution was concentrated, the residue was suspended in 250 ml ethanol and treated, portionwise, with cooling with 4.2 g (106.4 mmol) sodium borohydride. The mixture was heated to reflux until no more gas evolution was observed. Then the mixture was concentrated and the residue carefully added to ice-water. The mixture was extracted 3 times with methylene chloride and the extracts dried. The organic phase was concentrated. 2.61 g (87.1 mmol) Sodium hydride (80%) was added to 150 ml tetrahydrofuran and at 0°C, 24.1 g (87.1 mmol) of the resulting 1-(3-chloro-4,5,6,7-tetrahydropyrazolo- [1,5-a]pyridin-2-yl) -5-methylamino-4-pyrazolecarbonitrile in 500 ml tetrahydrofuran was added dropwise. After stirring for 1 hour at room temperature, 7.82 ml (95.8 mmol) iodoethane was added and the mixture heated at 70°C for 3 hours. Water was added dropwise and the mixture extracted 3 times with ethyl acetate. The organic phase was separated, dried and concentrated. The residue was recrystallised from ethyl acetate. Yield: 18.97 g = 71% of theory mp: 68-69 °C Example 4.3 5-Bromo-l- t4-chloro-5-difluoromethoxy-1-methyl- 3-pyrazolyl) -4-pyrazolecarbonitrile 5.68 g (19.7 mmol) 5-Amino-l-(4-chloro-5-difluoromethoxy- l-methyl-3-pyrazolyl) -4-pyrazolecarbonitrile was dissolved in 66.3 ml hydrobromic acid (47%) and the mixture cooled to -6°C. Under a nitrogen atmosphere, 2.36 g (34.2 mmol) sodium nitrite in 5.9 ml water was added dropwise. The mixture was stirred for 15 minutes at this temperature and heated to room temperature. 200 ml water was then added and the mixture extracted 4 times with methylene chloride. The organic phase was washed with saturated aqueous sodium hydrogen carbonate, dried over magnesium sulfate and concentrated. Yield: 6.94 g = 99.5% of theory mp: 78 °C Preparation of the starting materials 1. 5-Amino-l-f4-chloro-5-difluoromethoxy-1-methy1- 3-pyrazolyl) -4-pyrazolecarbonitrile 5.0 g (19.7 mmol) 5-Amino-l-(5-difluoromethoxy-1-methyl- 3-pyrazolyl) -4-pyrazolecarbonitrile was dissolved in 180 ml acetonitrile and 2.65 g (19.7 mmol) sulfuryl chloride added dropwise. The mixture was stirred for one hour at room temperature and concentrated. Yield: 5.68 g = 99.5% of theory mp: 140-142°C 2. 5-Amino-l-(5-difluoromethoxy-l-methyl-3-pyrazolyl - 4-pyrazolecarbonitrile 22.5 g (0.13 mol) 5-Difluoromethoxy-3-hydrazino-l-methyl- pyrazole was dissolved in 310 ml ethanol and treated with 15.4 g (0.13 mol) ethoxymethylenemalononitrile. After the mixture had been heated under reflux for one hour it was cooled. The precipitate was suction filtered and washed with a small amount of ethanol. Yield: 19.28 g = 60% of theory mp: 141-143°C 3. 5-Difluoromethoxy-3-hvdrazino-l-methylpyrazole 39.8 g (0.25 mol) 3-Amino-5-difluoromethoxy-1-methyl- pyrazole was dissolved in 225 ml water and 450 ml concentrated hydrochloric acid. At -10 β C, 18.55 g (0.27 mol) sodium nitrite in 80 ml water was added dropwise. After stirring for one hour at -10°C, 137.6 g tin(II)chloride, dissolved in 180 ml concentrated hydrochloric acid, was added dropwise at this temperature. After stirring for a further hour at -10°C, 805 ml 32% caustic soda was added dropwise at this temperature to the reaction mixture. The mixture was shaken 8 times with ethyl acetate, the combined organic phases washed with aqueous saturated sodium chloride, dried over magnesium sulfate and concentrated. Yield: 42.24 g = 97.2% of theory 4. 3-Amino-5-difluoromethoxy-l-methylpyrazole 71.7 g (1.79 mol) Sodium hydroxide was added to 600 ml water and the mixture cooled to -5°C. At this temperature, 57.3 g (0.36 mol) bromine was added dropwise at such a rate that the temperature did not rise above 0°C. Then 57.1 g (0.3 mol) 3-carbamoyl-5-difluoromethoxy-1-methyl- pyrazole was added portionwise at 0°C. The reaction mixture was stirred for one hour at 80°C and then saturated with sodium chloride. The precipitate which formed was suction filtered off. The filtrate was shaken 6 times with the ethyl acetate. The organic phase was dried over magnesium sulfate and concentrated. The precipitate which had been removed was dissolved in 500 ml water and the solution heated to boiling point for one hour. The reaction solution was saturated with sodium chloride and shaken 6 times with ethyl acetate. The organic phase was dried with magnesium sulfate and concentrated. Yield: 34.2 g = 70.5% of theory mp: 57 °C 5. 3-Carbamoyl-5-dif luoromethoxy-1-methylpyrazole 80.6 g (0.39 mol) 3-Methoxycarbonyl-5-difluoromethoxy- 1-methylpyrazole and 300 ml aqueous ammonia (33%) was stirred for one hour under reflux. The reaction solution was cooled, the precipitate suction filtered off and washed with water and diisopropyl ether. Yield: 58.9 g = 78.8% of theory mp: 154°C 6. 5-Difluoromethoxy-3-methoxycarbonyl-l-methylpyrazole 67.6 g (0.43 mol) 5-Hydroxy-3-methoxycarbonyl-l-methyl- pyrazole and 299.2 g (2.17 mol) potassium carbonate was dissolved in 1500 ml dimethylformamide and heated to 70°C. At this temperature chlorodifluoromethane was introduced over 2 hours and the mixture stirred at 80°C for 1.5 hours. The reaction mixture was added to water and extracted 6 times with ethyl acetate. The combined organic phases were washed with saturated aqueous sodium chloride and dried over magnesium sulfate. The reaction solution was concentrated. Yield: 80.6 g = 90.3% of theory 7. 5-Hvdroxy-3-methoxycarbonyl-l-methylpyrazole 102.3 g (0.72 mol) Dimethyl acetylenedicarboxylate was added to 1000 ml ether and the mixture cooled to -5°C in an ice-methanol bath. 33 g (0.72 mol) methylhydrazine in 100 ml ether was added dropwise at a rate that the inner temperature did not rise above 0°C. The mixture was stirred for one hour at 0°C, the precipitate suction filtered off, washed with ether and dried at 40°C in vacuo . The intermediate was immersed in an oil-bath heated to 120°C. The reaction product was recrystallised from methanol. Yield: 67.6 g = 60.1% of theory mp: 197 °C 8. 4-Chloro-5-difluoromethoxy-3-methoxycarbonyl- 1-methv1-pyrazo1e 2.1 g (10 mmol) 5-Difluoromethoxy-3-methoxycarbonyl- 1-methylpyrazole, dissolved in 30 ml methylene chloride, was treated with 1.35 g (10 mmol) sulfuryl chloride and the mixture stirred at room temperature for 10 minutes. It was then concentrated and the residue recrystallised from diisopropyl ether/ethyl acetate. Yield: 1.8 g = 74.8% of theory mp: 51°C Example 4.4 l- t4-Chloro-5-difluoromethoxy-l-methyl-3-pyrazolvH- 5-methyl-4-pyrazolecarbonitrile 0.57 g (2.25 mmol) 1-(5-Difluoromethoxy-1-methyl- 3-pyrazolyl) -5-methyl-4-pyrazolecarbonitrile was dissolved in 30 ml methylene chloride and at room temperature was treated with 0.30 g (2.25 mmol) sulfuryl chloride. The mixture was stirred for one hour and then concentrated. Yield: 0.65 g = 99.8% of theory mp: 69-70°C Preparation of the starting materials 1. 1-f5-Difluoromethoxy-l-methyl-3-pyrazolyl) -5-methyl- 4-pyrazolecarbonitrile A mixture of 0.79 g (2.91 mmol) 1-(5-difluoromethoxy- l-methyl-3-pyrazolyl) -5-methyl-4-pyrazolecarboxamide, 0.46 g (5.85 mmol) pyridine and 20 ml 1,4-dioxane was cooled to 5°C and 0.74 g (3.51 mmol) trifluoroacetic anhydride was added dropwise. The mixture was stirred for 3 hours at room temperature. It was then added to 100 ml water and extracted 4 times with ethyl acetate. The organic phase was dried over magnesium sulfate and concentrated. Yield: 0.74 = 99.8% of theory mp: 106-107°C 2. 1-(5-Difluoromethoxy-l-methyl-3-pyrazolyl) -5-methyl- 4-pyrazolecarboxamide 0.98 g (3.38 mmol) 1-(5-Difluoromethoxy-l-methyl- 3-pyrazolyl) -5-methyl-4-pyrazolecarbonyl chloride was dissolved in 20 ml tetrahydrofuran and 50 ml aqueous ammonia (33%) was added with stirring. After stirring for 3 hours at room temperature, the mixture was concentrated to half and acidified with dilute hydrochloric acid. The precipitate was suction filtered off, washed with a small amount of water and dried. Yield: 0.27 g = 73% of theory mp: 116-118 °C 3. 1- (5-Difluoromethoxy-l-methyl-3-pyrazolyl)-5-methyl- 4-pyrazolecarbonyl chloride 0.2 g (3.8 mmol) 1-(5-Difluoromethoxy-1-methyl- 3-pyrazolyl) -5-methyl-4-pyrazolecarboxylic acid was suspended in 30 ml 1, 2-dichloroethane and 1.19 g (10.0 mmol) thionyl chloride was added at room temperature, dropwise. The mixture was heated for 1 hour under reflux and concentrated. Yield: 0.98 g = 100% of theory 4. 1-(5-Difluoron.ethoxy-l-methyl-3-pyrazolyl) -5-methyl- 4-pyrazolecarboxylic acid A mixture of 1.25 g (4.16 mmol) Ethyl 1-(5-difluoro¬ methoxy-1-methy1-3-pyrazolyl)-5-methy1-4-pyrazole- carboxylate, 20 ml ethanol and 0.97 ml aqueous sodium hydroxide (45%) was stirred for 1 hour at 80°C. The reaction solution was concentrated to a half and acidified with hydrochloric acid (37%) . The precipitate was suction filtered off, washed with water and dried. Yield: 1.05 g = 93% of theory mp: 205-207°C 5. Ethyl 1-(5-difluoromethoxy-l-methyl-3-pyrazolvH- 5-methyl-4-pyrazolecarboxylate 3.0 g (16.8 mmol) 5-Difluoromethoxy-3-hydrazino-l-methyl- pyrazole was added to 25 ml ethanol and treated dropwise with 2.96 g (16.0 mmol) ethyl dimethylaminomethylenacetate dissolved in 25 ml ethanol. The mixture was heated under reflux for 2 hours. After cooling the precipitate was suction filtered off. Yield: 2.52 g = 53% of theory mp: 100°C Further starting materials were prepared as follows: 1. 1,1,7-Trichloro-l-hepten-3-one 100 g (0.62 mol) 5-Chlorovaleroyl chloride was added dropwise to 78.53 g (0.589 mmol) aluminium chloride in 150 ml methylene chloride at room temperature. After stirring for 1 hour, 45 ml (0.558 mol) 1, 1-dichloroethylene in 25 ml methylene chloride was added dropwise. Under ice- cooling 100 ml water was added dropwise and solid material suction filtered on Celite.The filtrate was washed with water and the organic phase dried and concentrated. The residue was distilled in a rotary evaporator. Yield: 112.76 g = 93.8% of theory. b.p.: 125°C/0.4 mbar 2. 2-Hvdrazino-4.5.6,7-tetrahydropyrazolor1, 5-alpyridine 261.9 ml (5.4 mol) Hydrazine hydrate was added dropwise to 116.6 g (0.54 mol) 1, 1,7-trichloro-l-hepten-3-one in 2000 ml 2-propanol at -2° C (acetone/dry-ice) . After stirring for 12 hours at room temperature 60.6 g (1,08 mmol) potassium hydroxide was added and the mixture heated for 5 hours under reflux. The reaction mixture was evaporated to dryness and the residue treated with 100 ml water and 100 ml brine. It was extracted 9 times with ethyl acetate and the and the organic phase washed with brine, dried over sodium sulfate and concentrated. Yield: 29.29 g = 35.6% of theory. Yellow oil 3. 5-Amino-4-cvano-l-(l-methyl-5-methylmercapto- 3-pyrazolyl yrazole A mixture of 2.0 g (13.1 mmol) 3-Hydrazino-l-methyl- 5-methylmercaptopyrazole and 1.8 g (14.4 mmol) ethoxymethylenemalononitrile in 25 ml ethanol was stirred for 30 minutes at room temperature and heated at boiling point for 3 hours. The reaction mixture was concentrated and the residue purified by silica gel chromatography (hexane/ethyl acetate 1:1). Yield 2.8 g = 91% of theory, mp: 165-166° C. 4. 3-Hvdrazino-l-methyl-5-methylmercaptopyrazole 1.1 g (15.8 mmol) sodium nitrite in 4 ml water was added dropwise to 1.9 g (13.1 mmol) 3-amino-l-methyl-5-methyl- mercaptopyrazole in 28 ml concentrated hydrochloric acid at 0° C and the mixture stirred for 2 hours at 0°C. Then, at -30°C, a solution of 7.4 g (32.8 mmol) SnCl 2 .2H 2 0 in 5.5 ml concentrated hydrochloric acid was added dropwise and the mixture stirred for 3 hours at this temperature. The reaction mixture was then made basic with 32% caustic soda and extracted with methylene chloride. The organic phase was dried over sodium sulfate and concentrated. 2.0 g of product was obtained which was used without further purification. 5. 3-Amino-l-methyI-5-methylmercaptopyrazole 5.55 g (33.0 mmol) 3-amino-4-cyano-l-methyl-5-methyl- mercaptopyrazole heated with 50 ml 32% caustic soda at boiling for 24 hours. The reaction mixture was cooled, made slightly acidic with aqueous sodium hydrogen phosphate, heated for 8 hours at 50°C and extracted with ethyl acetate. The organic phase was dried over sodium sulfate, concentrated and the residue purified by silica gel chromatography (hexane/ethyl acetate 1:1) . Yield: 19 g = 398% of theory, mp: 164-166° C. 6- 3-Amino-4-cvano-l-methyl-5-methylmercaptopyrazole 9.63 g (56.6 mmol) [Bis(methylmercapto)methylene]- malononitrile was suspended in 50 ml water and treated with 3.7 ml (67.9 mmol) methylhydrazine. The mixture was heated at boiling for 1 hour, the reaction solution cooled, the precipitate suction filtered and recrystallised from ethanol. Yield: 6.5 g = 68.% of theory, mp: 120-121° C. 7. 5-Amino-l-(4 ,5.6 ,7-tetrahydropyrazolo- [1, 5-a1pyridin-2-yl)-4-pyrazolecarboxylic acid and 2-hydrazino-4 ,5,6,7-tetrahydro-pyrazolor1, 5-a1pyridine These were prepared according to known methods as follows: a) 2-Amino-4 ,5,6 ,7-tetrahydropyrazolori, 5-a1pyridine A solution of 8.19 g (146 mmol) potassium hydroxide in 122 ml water and 122 ml ethanol was added to 19.19 g (292 mmol) hydroxylamine hydrochloride in 200 ml ethanol. The mixture was stirred for 15 minutes, 12.5 g (58 mmol) 2-(2,5-dimethyl-l-pyrrolyl)-4,5,6-7-tetrahydro- pyrazolo[l,5-a]pyridine added and the mixture heated under reflux for 30 hours. After distilling the ethanol, the mixture was treated with ethyl acetate, solid material filtered off, the aqueous phase saturated with sodium chloride and extracted with ethyl acetate. The organic phase was washed with saturated aqueous sodium chloride, dried over sodium sulfate and concentrated. The crude product was purified by silica gel chromatography (ethyl acetate/methanol) . Yield: 6.12 g = 77% of theory NMR (CDC1 3 , 300MHz) : 5=1.75-1.85 (m,2H) , 1.95-2 , 05 (m,2H) 2.68(t,2H,J=7.5Hz) , 3.5 (s(wide) ,2H) , 3.92 (t, 2H,J=7.5Hz) , 5.33(s,lH) b) 2-(2.5-Dimethyl-l-pyrrolyl) -4,5,6,7-tetrahvdro- pyrazolon.5-alpyridine 16 g (92 mmol) diethyl azodicarboxylate was added dropwise to 19.7 g (84 mmol) 3 (5)-(4-hydroxybutyl) -5(3)- (2,5-dimethyl-l-pyrrolyl)pyrazole and 22.1 g (84 mmol) triphenylphosphine in 300 ml tetrahydrofuran under ice cooling. The mixture was stirred for 4 hours at room temperature. It was then concentrated and the residue purified by silica gel chromatography (hexane/ethyl acetate) . Yield: 14.27 g = 79% of theory c) 3(5)-(4-Hvdroxybutyl)-5(3)-(2.5-dimethyl- 1-pyrrolyl)pyrazole A mixture of 18 g (116 mmol) 3 (5)-amino-5(3)-(hydroxy- butyl)pyrazole, 14.6 g (128 mmol) 2,5-hexanedione and 3.2 ml acetic acid in 100 ml toluene was heated under reflux with removal of water for 8 hours. The resulting precipitate was suction filtered, washed with toluene and dried. Yield: 19.7 g = 72% of theory mp: 147-148°C d) 3(5) -Amino-5(3) -(hvdroxybutyl)pyrazole 4,8 ml Hydrazine monohydrate was added to a solution of 12.3 g (0.1 mol) tetrahydro-2H-pyran-2-ylidenacetonitrile in 100 ml toluene at room temperature and the mixture heated under reflux for 5 hours, A dark yellow oil separated. The reaction mixture was concentrated and the residue purified by silica gel chromatography (ethyl acetate/methanol) . Yield: 11 g = 71% of theory In a similar manner to that described in the previous Examples, the following compounds were prepared. General formula General formula SUBSTITUTE SHEET General formula 2.49 Cl CH 2 SCH 2 CO 2 Et 1.52740 CH NH 2 1.53932 CH 2 NHMe CH 2 NHEt CH 2 NH 1.51362 CH 2 NMe 2 CH 2 NEt 2 CH2N prop2 Physical Constant mp[°C] 2.61 Cl CH. ° 2.62 Cl CH 2 OCH2CO 2 Et 2.63 Cl CH 2 OCH 2 C0 2 <^ General formula N 4.25 CH 3 OCHF 2 Br Br 96-97 General formula 4.49 4.50 4.51 4.52 4.53 4.54 4.55 4.56 General formula 4.78 Cl . 156 4.79 Cl -O 84 — N o 4.80 α 107 4.81 α CN 123 4.82 Cl N(C 2 H5)CH2CH 2 N(CH 3 )2 1.5559 4.83 Cl N(CH 2 -CH=CH 2 ) 2 79 4.85 Cl NHCH 2 -C≡CH 145 4.86 Cl NHCH(C 2 H 5 ) 2 96 4.87 Cl 139-142 Example R 3 R 6 Physical Constant No. mp [°C] n D ^ 4.106 Cl 4.109 4.110 4.112 Cl ■ oσ General formula Example R 3 R6 Physical Constant No. mp: [°C] ΠD 4.113 Cl NHC 3 H 7 80 NH- 4.114 Cl 77 4.115 Cl NH(CH 2 ) 2 OCH 3 78-79 4.116 Cl N(CH 3 )C 2 H 5 1.52076 (20 °q 4.117 Cl N(C 2 H 5 ) 2 1.49924 (20 °C) 4.118 Cl N(CH 3 )CH(CH 3 ) 2 1.51528 (20 °C) 4.119 Br N(CH 3 )CH(CH 3 ) 2 1.51258 (20,3 °C) 4.120 Cl N(C 2 H 5 )CH(CH 3 ) 2 52 4.121 Cl N(C 3 H 7 ) 2 1.49338 (20 °C) Example R3 R^ Physical Constant No. mp: [°C] πj) -N 4.122 Cl 100 - 102 NH— <^ 4.123 BBrr ^- 70 - 72 4.124 α Cl ^ ^^ 1.53388 (21,6 °Q General formula NHCH 2 CN 183 NHCH 2 -OC-CH 3 171.5-173.5 NHCH 2 CsC-CH 3 NHCH 2 -C≡C-C 2 H5 NHCH 2 -C≡C-CH 2 -OCH 3 General formula Example Rl R 2 R3 R6 Physical Constant No. mp: [°C] n-Q 4.135 -(CH2) 4 - Cl N(CH 3 )C 2 H 5 69 4.136 -(CH2)4- Cl N(CH 3 )C 3 H 7 89 4.137 -(CH2)4- α N(CH 3 )C 4 H 9 72 4.138 -(CH2) 4 - Cl N(CH 3 )CH(CH 3 )C 2 H 5 68 4.139 -(CH2) 4 - Cl N(CH 3 )CH(CH 3 )CH(CH 3 ) 2 70 4.140 -(CH2) 4 - α N(CH 3 )CH 2 CH 2 OCH 3 80 4.141 • (CH2)4- α N(C 2 H 5 )C 3 H 7 92 4.142 -(CH2) 4 - Cl N(C 2 H5)C 4 H9 1.5471 (22.9 °C) Cl N(C 2 H 5 )CH(CH 3 )C 2 H 5 115 Cl N(C 2 H 5 )CH(CH 3 )CH(CH 3 ) 2 130-133 Cl N(C 2 H 5 )CH 2 CH 2 OCH 3 58 Cl N(C 2 H 5 )CH 2 Ph 110 Cl N(CH 3 )CH 2 CH 2 OC 2 H 5 1.5559 4.148 -(CH 2 ) 4 - Cl N(C 2 H 5 )CH 2 CH 2 OC 2 H 5 1.5484 (20 °C) 4-150 -(CH2)4- Cl N(CH 2 -C≡CH)CH 2 CH 2 OC 2 H 5 1.55688 (20 °C) 4.151 -(CH )4- Cl N(CH 3 )CH(CH 3 )CH 2 OCH 3 1.55644 (20 °C) 4.152 -(CH2)4- Cl N(C 2 H5)CH(CH 3 )CH 2 OCH3 94 - 95 4.153 -(CH2)4- Cl N(CH 2 -C≡CH)CH(CH 3 )CH 2 OCH 3 124-126 4.154 CH 3 OCHF 2 Cl N(C 2 H 5 )CH 2 CH 2 OCH 3 1.51744 (19,9 °C) 4.155 CH 3 OCHF 2 Cl N(CH 2 -C≡CH)CH 2 CH 2 OCH 3 1.51376 (20°C) 4.156 -(CH 2 ) 4 - Cl NH(CH 2 -C≡CH) 145 4.157 -(CH 2 ) 4 - Cl N(CH(CH 3 )C 2 H 5 )CH 2 -C≡CH 142 N(CH 3 )CH 2 fi 4.158 -(CH 2 ) 4 - Cl \=/ 108 4.159 -(CH 2 ) 4 - Cl N(C 2 H5)CH(CH 3 )CH 3 106 4.166 -(CH9)4- Cl N(CH 2 -C≡CH)CH 2 CH(OCH 3 ) 2 111-113 CH, 4.167 -(CH2) - Cl O 97-99 4.168 -(CH2)4- l 169-171 4.169 -(CH2) 4 - Cl 140-142 4.170 -(CH2)4- Cl N(CH 3 )CH2CH 2 SC2H5 1.5855 (22.4°C) 4.171 N(CH 3 )CH 2 -C≡C-CH 3 4.172 N(CH 3 )CH 2 -C≡C-C 2 H 5 4.173 N(CH 3 )CH 2 -C≡C-CH 2 -OCH 3 General formula Example R 3 R6 Physical Constant No. mp: [°C] nj) 4.177 Br N(C 2 H 5 ) 2 71 - 72 4.178 Cl N(CH 2 -C≡CH) 2 1,5739 (22,8 °C) 4.179 Cl N(CH 2 C02C 2 H 5 ) 2 1.5427 (20 °C) 4.181 Cl N(CH 2 -C≡C-CH 3 ) 2 4.182 Cl N(CH 2 -C≡C-C 2 H 5 ) 2 4.183 Cl N(CH 2 -C=C-CH 2 OCH 3 )2 General formula Example R 3 R6 Physical Constant No. mp: [°C] nj) 4.184 4.185 4.186 4.187 4.188 4.189 4.190 4.191 4.193 Example R 3 R 6 Physical Constant No. mp: [°C] n j) 4.199 Cl NHCON(CH 3 ) 2 168 4.200 Cl NHCSN(CH 3 ) 2 170 4.201 Cl NHCON(CH 3 )Ph 62-64 General formula Example R 3 R 6 Physical Constant No. mp: [°C] nj) ncochysccH, 4.202 4.203 4.204 4.205 Cl N(Et)COCH 3 78-80 4.206 Cl N(Et)COCH 2 Cl 1.53412 4.208 Cl N(Et)COEt 1.51132 N (_< ) COE. 4.209 1.51214 4.210 Cl N (^) COB 1.52582 4.211 Cl N(CH 2 C0 2 Me)COEt 87-90 4.212 Br NHCOEt 120-122 Example R 3 R6 Physical Constant No. mp: [°C] nj) 4.213 Br NHCOnbutyl 100-104 4.214 Br 103 4.215 4.216 4.217 4.218 4.219 4.220 4.221 4.222 4.223 4.224 4.225 General formula N(CH )CO 4.246 Cl ■ 4 121 N (CH -C = CH)CO_ ] 4.248 Cl * 191 4.249 Cl N(CH 3 )OOC 4 H 9 1.5427 (23.2 °C) 4.250 Cl N(C 2 H 5 )COC 4 H9 1.5386 (23.3 °C) 4.251 Cl N(COCH 3 )CH 2 OCH 3 109 4.252 Cl N[CH(CH 3 ) 2 ]COCH 3 112-114 4.253 Cl N(CH 2 CH 2 OC 2 H 5 )COCH 3 100-103 4.254 Cl N[CH(CH 3 )CH(CH 3 ) 2 ]COCH 3 93 4.255 Cl N[CH(CH 3 ) 2 ]COCH 2 CI 146-149 4.256 Cl N[CH(CH 3 )C 2 H 5 ]COCH 2 Cl 109-111 4.257 Cl N[CH(CH 3 )CH 2 OCH 3 ]COCH2Cl 126 4.258 Cl N(CH 2 CH 2 SC 2 H5)COCH3 1.5655 (22,4 °C) General formula Example R 3 R6 Physical Constant No. mp: [°C] ΠD 4.259 4.260 4.261 4.262 4.263 4.264 4.265 1.5168 4.266 1.51532 4.267 r 1.53406 4.268 Br N(CH 2 CN)COEt 95-98 4.269 Br N(Me)COC 3 H 7 1.55112 4.270 Br N(CH 2 OCH 3 )COC 3 H 7 1.53024 4.271 Br N(CH 2 CO 2 Et)COC3H 7 1.52918 General formula 4.278 Cl OCH 2 -C^CH 123 4.279 Cl OC4H9 74-76 4.280 Cl C<j° 99.5-101.5 4.281 Cl °X<> 102-104 Example R 3 R 6 Physical Constant No. mp: [°C] nj) 4.282 Cl " 1.5575 (21.8 °g 4.283 Cl C3 1.5520 (22 °C) 4.284 Cl Λ? 1.5524 (21.8 °C) 4.286 Cl OCH2CH2CH(OC 2 H5)2 1.5306 (20 °C) (22.7 °C) 4.289 Cl SCH 2 COOCH(CH 3 ) 2 125 4.290 Cl \=/ 1.6136 (21.5 °C) 4.297 4.298 4.299 4.300 4.301 4.302 4.303 4.304 4.305 4.306 TE SHEET Example R 3 R<» Physical Constant No. mp: [°C] nj 4.308 Cl > 4.309 4.310 4.311 General formula Example- R6 Physical Constant No. mp: [°C] nj) 4.312 SCH 2 CO 2 Et 1.53242 (20.2 °C) 4.313 SCH 3 4.314 SEt 4.315 Sprop S 4.316 4.317 S nbutyl s"N 4.318 4.320 OCH 3 4.321 OEt 4.322 O prop Example R* Physical Constant No. mp: [°C] n D 4.324 O nbutyl cTs 4.325 4.329 4.330 3 ^ 4.331 C^ 4.333 Example R^ Physical Constant No. mp: [°C] n£> 4.334 4.335 4.336 4.338 A 4.339 _- .oet cet 4.340 λ CO. Me A3AA ^- o- 103-105 Example R6 Physical Constant No. mp: [°C ΠD 4.346 H V ° HN 4.351 ^ OH HN-" 4.353 H ^ &. 4.354 General formula Example R5 R6 Physical Constant No. mp: [°C] ΠD 4.355 CN N(C 2 H 5 ) 2 89-90 NHjjCH 4.356 CN 123-124 4.357 CN CH 3 4.358 CN CH 2 OCH 3 4.359 CN Br 4.360 CN Cl 4.361 CN OCH 2 CH 2 OCH 3 NHCEt II 4.362 NO 2 o The following examples illustrate the possibilities for use of the compounds of the invention. In these Examples, herbicidal activity is denoted on a score of 0 to 4 in which: 0 = no damage 1 = 1 - 24% damage 2 = 25 - 74% damage 3 = 75 - 89% damage 4 = 90 - 100% damage The abbreviations used for the various plant species have the following meanings ABUTH = Abutilon theophrasti VERPE = Veronica persica AGR E = ∑lymus repens VIOSS = Viola sp ALOMY = Alopecurus myosuroides AVEFA = Avena fatua B OTE = Bromus tectorum CYPDI = Cyperus difformis CYPES = Cyperus eεculentus ECHGH = Echinochloa crus-galli GALAP = Galium aparine GOSHI = Goεsypium hirsutum IPOSS = Ipomea purpurea MATCH = Matricaria chamomilla MOOVA = Monochoria vaginaliε ORYSA = Oryza εativa PANSS = Panicujπ maximum PASDS = Paspalum distichum POLSS = Polygonum sp . SCPJU = Scirpus juncoides SEBEX = Sesbania exaltata SETVI = Setaria viridis SORHA = Sorghum halepense SOLSS = Solanum sp . Test Example A In a greenhouse, the noted plant species were treated pre-emergently with the noted compounds, at a rate of 0.1 kg active ingredient/ha. The compounds were sprayed evenly over the soil as emulsions in 500 litres water/ha. Three weeks after the treatment, the compounds of the invention showed excellent activity against the weeds. The comparison material did not show the same high activity. Test Example B In a greenhouse, the noted plant species were treated post-emergently with the noted compounds, at a rate of 0.3 kg active ingredient/ha. The compounds were sprayed evenly over the plants as emulsions in 500 litres water/ha. Two weeks after the treatment, the compounds of the invention showed activity against the weeds. The comparison material did not show the same high activity. Test Example C In a greenhouse, the compounds noted in the table were applied at the rates mentioned. For this the formulated active ingredients were pipetted onto the water surface The test plants were treated pre-emergently and in the 1 3 leaf stage. 0 As the table shows, the compounds of the invention show good activity against Echinochloa crus-galli (ECHGH) C yperuε d ifformiε (CYPDI) , Scirpus juncoides (SCPJU) and Monochoria vaginalis (MOOVA) . Example D In a greenhouse, the noted plant species were treated with the noted compounds, at a rate of 0.03 kg active ingredient/ha. The compounds were sprayed evenly over the plants as emulsions in 500 litres water/ha. Two weeks after the treatment, the compounds of the invention showed excellent activity against the weeds. The comparison material did not show the same high activity. Example E In a greenhouse, the noted plan- species were treated with the noted compounds, at a rate of 0.1 kg active ingredient/ha. The compounds were sprayed evenly over the plants as emulsions in 500 litres water/ha. Two weeks after the t reatment, the compounds of the invention showed excellent activity against the weeds. The comparison material did not show the same high activity. HEET

Claims: CLAIMS Substituted pyrazole derivatives of general formula I in which R 1 is C 1 -C -alkyl; R 2 is C 1 -C 4 -alkyl, C 1 -C 4 -alkylthio, C 1 -C 4 -alkoxy, each of which is optionally substituted by one or more halogen atoms, or R 1 and R 2 together form the group -(CH 2 ) m ; R 3 is hydrogen or halogen, R 4 is hydrogen or C 1 -C 4 -alkyl, R 5 is hydrogen, nitro, cyano or the groups -COOR 7 , -C(=X)NR 7 R 8 or -C(=X)R 10 , R 6 is hydrogen, halogen, cyano, C 1 -C 4 -alkyl, (optionally substituted by one or more halogen or hydroxy groups) , C j -C 4 -alkoxy, phenyl, (optionally substituted by one or more halogen, nitro, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or halo-C 1 -C 4 -alkyl groups) , pyrrolyl, or is a C 2 -C 8 -alkyl, C 3 -C 8 -alkenyl, C 3 -C 8 -alkynyl or C 3 -C 8 -alkoxy group, each of which is interrupted by one or more oxygen atoms, or is the group; -(CH 2 ) a -A, -(CH 2 ) a -0-(CH 2 ) b -R 22-, or -COR 3 24 R 7 , R s and R 9 , which may be the same or different, are hydrogen or C 1 -C 4 -alkyl or R 8 and R 9 together with the nitrogen to which they are attached form a 5 or 6 membered saturated carbocyclic ring; R 10 is hydrogen or C 1 -C 4 -alkyl, optionally substituted by one or more halogen atoms, R 11 is hydrogen, C j - ^-alkyl, C 2 -C 6 -alkenyl, C 3 -C 6 -alkynyl or phenyl (each of which is optionally substituted by one or more halogen atoms) , C 3 -C 8 -cycloalkyl, cyanomethyl or the group R 21 CO-; .12 is C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 3 -C 6 -alkynyl or phenyl (each of which is optionally substituted by one or more halogen atoms), C 3 -C 8 -cycloalkyl, cyanomethyl, C 1 -C 4 -alkoxy-C 1 -C 6 -alkyl, di-C 1 -C 4 -alkylamino- C 1 -C 4 -alkyl, tetrahydrofurfuryl ethyl, C 3 -C 6 -alkynyl- oxy-C 1 -C 4 -alkyl, benzyl, (optionally substituted by one or more halogen, nitro, cyano, C 1 -C -alkyl, C j -C^alkoxy or halo-C j -C 4 -alkyl groups) , or is the group -C(=X)R 21 , -(CH 2 ) a -(0) d -R 2S , -(CH 2 ) a -0-(CH 2 ) b .R 2S or -(CH 2 ) a -X-R 34 , and when R 5 is -C(=0)R 10 , and/or when R 1 is C j -C 4 -alkyl, R 2 is difluoromethoxy, R 3 is bromo and R 5 is nitro or cyano, R 12 can also be hydrogen; or R 11 and R 12 together with the nitrogen to which they are attached form a 3, 5 or 6 membered saturated carbocyclic or aromatic ring, in which a carbon atom is optionally substituted by an oxygen atom; R 13 is hydrogen, C 1 -C 4 -alkyl, C 2 -C 6 -alkenyl or C 3 -C 6 -alkynyl; or R 13 and R 14 together form the group -(CH 2 ) ; R 14 and R 15 , which may be the same or different, are C 1 -C 4 -alkyl, C 2 -C 6 -alkenyl, C 3 -C 6 -alkynyl or phenyl (each of which is optionally substituted by one or more halogen atoms) , hydrogen, C 3 -C 6 -cycloalkyl or the groups -XR 1S or -NR 19 R 20 ; R 16 is hydrogen, C j -Cg-alkyl, C 2 -C 6 -alkenyl, C 3 -C 6 -alkynyl, C 1 -C 4 -alkylcarbonyl, cyano-C 1 -C 3 -alky1, C 1 -C 4 -alkoxycarbonyl-C 1 -C 4 -alkyl, di-C 1 -C 4 -alkoxy- carbonyl-C 1 -C 4 -alkyl, benzyl, C 1 -C 4 -alkoxy- -C-alkynyl, or the group -(CH 2 ) a -R 33 , -(CH 2 ) a -X-R 30 , -(CH 2 ) a -X-(CH 2 ) b -R 30 or -(CH 2 ) a -X-(CH 2 ) b -X-(CH 2 ) c -R 30 , R 17 is hydrogen, C 1 -C 4 -alkyl, C 2 -C 6 -alkenyl, C 3 -C 6 -alkynyl, cyano-C 1 -C 3 -alkyl, C 1 -C 4 -alkylcarbonyl-C 1 -C 3 -alkyl or phenyl, R 18 is C j :-C 4 -alkyl, optionally substituted by one or more halogens; R 19 anridd RR 2200 ,, wwhhiich may be the same or different, are hydrogen or C 1 -C 4 -alkyl; R 21 is C 1 -C 4 -alkyl, (optionally substituted by one or more halogens), C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkyl, C 3 -C 6 .cycloalkyl, phenyl, (optionally substituted by one or more halogen, nitro, cyano, C 1 -C 4 -alkyl, C j -C 4 -alkoxy or halo-C 1 -C 4 -alkyl groups) , or is the group -NR 31 R 32 or -(CH 2 ) a -(0) d -R 33 ; R 22 is C 1 -C 4 -alkoxycarbonyl or carboxy, R 23 is chloromethyl, cyanomethyl, C 3 -C 6 -cycloalkyl (optionally interrupted by one or more oxygen atoms) , or C 1 -C 4 -alkoxycarbonyl-C 1 -C 4 -alkyl, R 24 is hydroxy or the group -NR^R 26 ; A is -NR^R 26 or -S(0) n -R 27 ; R 25 and R 26 , which may be the same or different, are hydrogen or C j -^-alkyl; R 27 is C 1 -C 4 -alkyl, C 1 -C 4 -alkoxycarbonyl-C 1 -C 4 -alkyl or carboxy, R 28 is hydrogen, hydroxy, halogen, C 1 -C 4 -alkyl, (optionally substituted by one or more C 1 -C 4 -alkoxy groups) , C 3 -C 6 -cycloalkyl (optionally interrupted by one or more oxygen atoms and optionally substituted by dimethyl), furyl, thienyl or -C(=0)R 29 ; R 29 and R 30 , which may be the same or different, are C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy; R 31 and R 32 , which may be the same or different, are C 1 -C 4 -alkyl or phenyl; R 33 is C 3 -C 6 -cycloalkyl (optionally interrupted by one or more oxygen atoms and optionally substituted by dimethyl), furyl, thienyl or -C(=0)R 29 ; R 34 is C 1 -C 4 -alkyl; a, b and c are 1, 2 or 3; d is 0 or 1; m is 3 or 4; p is 2 or 3; and X is oxygen or sulfur. 2. Substituted pyrazolyl derivatives according to claim 1 in which R 1 is methyl; R 2 is methylthio or difluoromethoxy (and especially difluoromethoxy) ; or R 1 and R 2 together form the group -(CH 2 ) 4 ; R 3 is hydrogen, chloro or bromo; R 4 is hydrogen; R 5 is hydrogen, nitro, cyano or -C(=X)R 10 . 3. Substituted pyrazolyl derivatives according to claim 1 or 2 in which R 6 is hydrogen, halogen, cyano, C 1 -C 4 -alkyl, C^-alkylthio or -NR n R 12 , 4. Substituted pyrazolyl derivatives according to claim 3 in which R 11 and R 12 , which may be the same or different are hydrogen, C^-alkyl or C^-alkoxycarbonyl. Compounds of general formula Ila in which R 1 , R 2 and R 3 have the meanings given in general formula I in claim 1, as intermediates for preparation of compounds claimed in claim 1. 6. Compounds of general formula li NH, in which R 1 and R 2 have the meanings given in general formula I in claim 1, as intermediates for preparation of compounds claimed in claim 1. 7. Compounds of general formula Ij I R in which R 1 , R 2 and R 5 have the meanings given in general formula I in claim 1, as intermediates for preparation of compounds claimed in claim 1. 114 8. Compounds of general formula Ik in which R 1 , R 2 and R 6 have the meanings given in general formula I in claim 1, as intermediates for preparation of compounds claimed in claim 1. 9. Compounds of general formula II 11 R in which R , R- and R J have the meanings given in general formula I in claim 1, as intermediates for preparation of compounds claimed in claim 1. 10. Compounds of general formula Im in which R 1 , R 2 , R 3 and R 6 have the meanings given in general formula I in claim 1, as intermediates for preparation of compounds claimed in claim 1. 11. A herbicidal composition which comprises a compound according to any one of claim 1 to 4, in admixture with agriculturally acceptable carriers and diluents. 12. A method of combating weeds which comprises applying to the weeds or their locus a compound according to any one of claims 1 to 4. 13. A process for the preparation of a compound of general formula I as claimed in claim 1, in which . A) a compound of general formula II in which R 1 , R 2 and R 3 have the meanings given in general formula I, is reacted with a compound of general formula III in which R 4 and R 5 have the meanings given in general formula I and Y is C j -Cg-alkoxy, hydroxy or halogen, or when R 5 is hydrogen, B) a compound of general formula II in which R 1 , R 2 and R 3 have the meanings given in general formula I, is reacted with a 2-haloacrylonitrile of formula Ilia or with a 2,3-dihalopropionitrile of formula Illb Ha!-C-! 2 —CH (1Mb), Ha! in which Hal is halogen, or when R 3 is halogen, C) a compound of general formula la in which R 1 , R 2 , R 5 , R 11 and R 12 have the meanings given in general formula I, is reacted first with a halogenating agent to give a compound of formula lb given in general formula I, and Hal is halogen, and then further treated to give the desired compound, or when R 5 is -C(=S)R 10 and R 6 is amino, D) a compound of general formula Ic in which R 1 , R 2 , R 3 , R 4 and R 10 have the meanings given in general formula I, is treated with Lawesson's reagent, or when R 3 is -OR 16 , E) a compound of general formula Id i « R' in which R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given in general formula I, is first diazotised to give a compound of formula le in which R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given in general formula I, and then by heating to give a compound of formula If I in which R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given in general formula I, which is then reacted with a compound of general formula IV in which R 16 has the meaning given in general formula I, and Q is a leaving group, or when R 5 is nitro and R 6 is -SR 17 , F) a compound of general formula Ig in which R 1 , R 2 , R 3 and R 4 have the meanings given in general formula I and Hal is halogen is reacted with a nucleophile of general formula V Θ SR 17 (V) in which R 17 has the meaning given in general formula I, or when R 5 is nitro and R 6 is -S(0) n R 17 , in which n is 1 or 2, G) a compound of general formula Ih in which R 1 , R 2 , R 3 , R 4 and R 17 have the meanings given in general formula I, is subjected to a stepwise oxidation with m-chloroperbenzoic acid, or when R 5 is cyano H) a compound of general formula Ila in which R 1 and R- have the meanings given in general formula I, is reacted with a compound of general formula in which Y is C j -Cg-alkoxy, hydroxy or halogen, or when R 5 is nitro, I) a compound of general formula li in which R 1 and R 2 have the meanings given in general formula I, is nitrated in known manner, or J) a compound of general formula Ij I i R in which R 1 , R 2 and R 5 have the meanings given in general formula I, is brominated in known manner, or when when R 5 is halogen, K) a compound of general formula II in which R 1 , R 2 and R 3 have the meanings given in general formula I, is reacted with a compound of general formula Illc CN r (Illc) Y CN in which Y' is C j -Cg-alkoxy, dimethylamino or halogen, to first give compound of formula II I 1 R in which R 1 , R 2 and R 3 have the meanings given in general formula I, and this compound is then diazotised in known manner with sodium nitrite and converted to the corresponding halide, or L) a compound of general formula Ik in which R 1 , R 2 and R 6 have the meanings given in general formula I, is treated with a halogenating agent, or M) a compound of general formula Im in which R 1 , R 2 and R 3 have the meanings given in general formula I, and R 6 is C 1 -C 4 -alkyl, (optionally substituted by one or more halogens) or is a C 2 -C 8 -alkyl, interrupted by one or more oxygens, is converted in known manner to the nitrile of general formula I, or when R 6 is -NR π R 12 , N) a compound of general formula In l ι R in which R 1 , R 2 and R 3 have the meanings given in general formula I, is reacted with an amine in a solvent, or when R 6 is -NR n R 12 , in which R 11 is hydrogen and R 12 is C j -C 6 -alkyl, O) a compound of general formula II I ι R in which R 1 , R 2 and R 3 have the meanings given in general formula I, is reacted with a trialkyl ortho ester and then reduced, or P) a compound of general formula Io in which R 1 , R 2 and R 3 have the meanings given in general formula I, and R 12 is C j -Cg-alkyl is reacted with an base and an alkylating agent or an acid chloride, or when R 6 is -NR π R 12 , in which R 11 and R 12 are C j -Cg-alkyl, Q) a compound of general formula II in which R 1 , R 2 and R 3 have the meanings given in general formula I, is reacted with approximately 2 mole of base and 2 mole of a suitable alkylating agent, or R) a compound of general formula II R in which R 1 , R- and R have the meanings given in general formula I, is reacted with or without a base and a suitable acid chloride, or in which R 1 , R 2 , R J and R 21 have the meanings given in general formula I, is reacted with a base and a suitable alkylating agent, or T) a compound of general formula In R in which R 1 , R 2 and R 3 have the meanings given in general formula I and R 5 is cyano or nitro, is reacted with an oxygen, nitrogen, sulfur or carbon nucleophile, or when R 6 is substituted methyl U) a compound of general formula Iq in which R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given in general formula I, is reacted with a Lewis acid, or V) a compound of general formula Ir in which R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given in general formula I, is treated with a halogenating agent, or ) a compound of general formula Is 4 in which ings given in general formula I, is reacted with an oxygen, nitrogen, sulfur or carbon nucleophile, or when R 6 is mercapto X) a compound of general formula It R in which R 1 , R 2 , R 3 and R 4 have the meanings given in general formula I, is treated with sodium hydrogen sulfide, or Y) a compound of general formula Iu in which R 1 , R 2 , R 3 and R 4 have the meanings given in general formula I, is treated with a suitable alkylating agent, or Z) a compound of general formula Iv in which R 1 , R 2 , R 3 and R 4 have the meanings given in general formula I, and R x is C 1 -C 4 -alkyl, is oxidised in stages.

Inventors: BOHNER JUERGEN, DORFMEISTER GABRIELE, FRANKE HELGA, GEISLER JENS, HARTFIEL UWE, REES RICHARD, BOHNER, JUERGEN, DORFMEISTER, GABRIELE, FRANKE, HELGA, GEISLER, JENS, HARTFIEL, UWE, REES, RICHARD
Applicants: BOHNER JUERGEN, DORFMEISTER GABRIELE, FRANKE HELGA, GEISLER JENS, HARTFIEL UWE, REES RICHARD, SCHERING AG, SCHERING AKTIENGESELLSCHAFT
Application year: 1993
Main classification: C07D471
IPC codes: A01N43, A01N47, A01P13, C07D231, C07D403, C07D405, C07D409, C07D471, C07D491