SUBSTITUTED PYRAZOLYL-PYRAZOLE DERIVATIVES, PROCESSES FOR THEIR PREPARATION AND THEIR USE AS AGENTS WITH HERBICIDAL ACTION

Abstract: The invention relates to new substituted pyrazol derivatives of general formula (I) in which: R<1>, R<2>, R<3>, R<4>, R<5> and R<6> have the meanings given in the description, agents with herbicidal action containing at least one compound of formula (I), and their use as herbicides.

Description: Substituted pyrazolyl-pyrazole derivatives, processes for their preparation and their use as agents with herbicidal action The invention concerns new substituted pyrazolyl-pyrazole derivatives, their preparation as well as intermediate products for their preparation, and their use as agents with herbicidal action. It is already known that pyrazoles possess herbicidal properties (WO 9408999). It frequently occurs however that the herbicidal action of the known compounds is not sufficient or selectivity problems occur with the relevant herbicidal action in main agricultural crops. The problem of the present invention is to prepare new substituted pyτazole derivatives which do not exhibit these disadvantages and whose biological properties are superior to those of the currently known compounds. It has now been found that substituted pyrazole derivatives of the general formula (I) have a superior herbicidal action: in which R 1 = C C-4 alkyl, R 2 ■ C r C_, alkyl, C r C 4 alkylthio, C r C 4 alkoxy; or C r C 4 alkyl, C r C<. alkytthio, C C 4 alkoxy all substituted one or more times with halogen, R 1 and R 2 together form the group - .CH 2 ) m -, R 3 " hydrogen or halogen, R " hydrogen or C r C 4 alkyl, R 5 " hydrogen, nitro, cyano or the groups - COOR 7 , R 8 -C - N or - C - R 10 li \ 0 II X R 9 X ■ 0 - R 11 , - CH 2 - CH - COOR 7 or one of the groups 3 R 7 , R 8 and R 9 , independent of one another, are hydrogen or C,- C 4 alkyl, R 8 and R 9 , together with the adjacent nitrogen atom, form a 5-membered or 6-membered saturated heterocyclic ring, R 10 = hydrogen, C, - C A alkyl, or a C r C 4 alkyl substituted one or more times by halogen, R 11 = hydrogen, C t - C β alkyl, C 3 - C e cydoalkyl, C j - C e alkenyl, C 3 - C 6 alkynyi ; or C - C 6 alkyl, C 3 - C e cydoalkyl, C 2 - C 6 alkenyl, C 3 - C 6 alkynyi all substituted similarly or differently one or more times by halogen, hydroxy or C r C_ j alkoxy; or C 2 - C 8 alkyl, C 3 - C 8 cydoalkyl, C 3 - C 8 alkenyl. C 3 - C 6 alkynyi all interrupted one or more times by oxygen; or the group OR 12 , R 12 = hydrogen, C, - C e alkyl, C 3 - C e cydoalkyl, C 2 - C e alkenyl, C 3 - C e alkynyi; C - C e alkyl substituted similarly or differently one or more times by halogen, hydroxy or C, - C t alkoxycarbonyl, C, - C 4 alkyl or C, - C A alkoxy, R Y = oxygen, sulphur, - N - OR 13 and -C x R ts R 13 = hydrogen, C< - C β alkyl, C 3 - C β cydoalkyl, C 2 - C β alkenyl, C 3 - C β alkynyi; C - C β alkyl, C 3 - C β cydoalkyl, C^ - C β alkenyl, C 3 - Cg alkynyi all substituted similarly or differently one or more times by halogen, cyano, hydroxy or C t - C 4 alkoxy; C 2 - C 8 alkyl, C 3 - C 8 cydoalkyl, C 3 - C 8 alkenyl, C 3 - C 8 alkynyi all interrupted one or more times by oxygen; C, - C 4 alkoxycarbonyl-C 1 - C 4 alkyl, which can optionally be substituted by halogen atoms; C, - C 4 alkoxycarbonyl-C - C 4 alkenyl, which can optionally be substituted by halogen atoms; C, - C 4 alkoxycarbonyl, R and R 5 , independent of one another, are hydrogen, halogen, cyano, carboxyl, formyl, C r Cg alkyl, C 3 - C 6 cydoalkyl, C 2 - C 6 alkenyl, C 3 - C β alkynyi; C r C β alkyl, C 3 - C 6 cydoalkyl, C 2 - C β alkenyl, C 3 - C 8 alkynyi all substituted similarly or differently one or more times by halogen, cyano, hydroxy or C i - C 4 alkoxy; C 2 - C 8 alkyl, C 3 - C 8 cydoalkyl, C 3 - C 8 alkenyl, C 3 - C 8 alkynyi all interrupted one or more times by oxygen; C 1 - C 4 alkoxycarbonyl-C 1 - C 4 alkyl, which can optionally be substituted by halogen atoms; C, - C 4 alkoxycarbonyl-C 2 - C 4 alkenyl, which can optionally be substituted by halogen atoms; C 1 - C 4 alkoxycarbonyl, C, - C alkoxy or C 1 - C 4 alkylthio, R and R 15 together with the carbon atom form a saturated carbocydic C 3 - C β ring which can be interrupted one or more times by oxygen or sulphur, R 16 = hydrogen or C, - C 4 alkyl, R 17 = hydrogen. C | - C 4 alkyl or halogen-C, - C 4 alkyl, R 18 , R 19 , R 20 , R 21 , R 22 and R 23 , independent if one another, are hydrogen, halogen, C, - C 4 alkyl, C 2 - C 4 alkenyl or C 3 - C 4 alkynyi; C r C 4 alkyl, C 2 - C 4 alkenyl, C 3 - C 4 alkynyi, carboxyl or C j - C 4 alkoxycarbonyl all substituted similarly or differently one or more times by halogen, cyano, nitro, hydroxy or by C, - C alkoxy, R 2 * = C, - C alkyl, or C 1 - C 4 alkyl substituted one or more times by halogen, m = 3 or 4, n = 0, 1, 2 or 3, p = 0 or 1, X = oxygen or sulphur, 2 = oxygen, sulphur or N - R 25 , R 25 = hydrogen or C t - C 4 alkyl, W = oxygen, sulphur or carbon. The tern, "halogen" indudes fluorine, chlorine and iodine. The term "alkyl". "alkylene" and "alkynyi" implies that the carbon chain can be branched o unbranched. The compounds of formula (I) which are preferred are those wherein: R 1 = methyl. R 2 = methylthio or difluormethoxy, R 1 and R 2 together form the group -(CH 2 ) 4 -. R 3 = hydrogen, chlorine or bromine. R* = hydrogen. R 5 = hydrogen, nitro, cyano or the groups -COOR 7 or - CXR 10 , R β = - C - R 11 , n Y or one of the groups R 7 = hydrogen or C r C 4 alkyl, R 10 = hydrogen, C, - C 4 alkyl. or a C r C 4 alkyl substituted one or more times by halogen, R 11 = hydrogen, C. - C β alkyl or the group - OR 12 , R 12 = C r C β alkyl, C 3 - C β cydoalkyl, C 2 - C β alkenyl, C 3 - C β alkynyi; a C. - C β alkyl substituted similarly or differently one or more times by halogen, hydroxy or C 1 - C 4 alkoxy, R u Y = oxygen, sulphur, - N - OR 13 and - C V, R 13 = hydrogen, C, - C β alkyl, C 3 - C β cydoalkyl, C 2 - C 9 alkenyl, C 3 - C β alkynyi; C 2 - C 8 alkyl, C 3 - C 8 cydoalkyl, C 3 - C 8 alkenyl, C 3 - C 8 alkynyi all interrupted one or more times by oxygen; C, - C 4 alkoxycartoonyl-C, - C alkyl, which can optionally be substituted by halogen atoms; C, - C 4 alkoxycarbonyl-C 2 - C alkenyl, which can optionally be substituted by halogen atoms; C, - C 4 alkoxycarbonyl, R u and R 1S , independent of one another, are hydrogen, halogen, cyano, carboxyl, formyl, C, - C β alkyl, C 3 - C β cydoalkyl, C 2 - C β alkenyl, C 3 - C β alkynyi; C 1 - C 4 alkoxycarbonyl-C 1 - C 4 alkyl, which can optionally be substituted by halogen atoms; C, - C 4 alkoxycarbonyl, C 1 - C 4 alkoxy or C, - C 4 alkylthio, R 1β = hydrogen or C 1 - C 4 alkyl, R 7 = hydrogen, C t - C 4 alkyl or halogen-^ - C 4 alkyl, R 18 , R 19 , R 20 , R 21 , R 22 and R 23 , independent if one another, are hydrogen, halogen, C, - C 4 alkyl, C 2 - C alkenyl or C 3 - C 4 alkynyi; C r C 4 alkyl. C^ - C 4 alkenyl, C 3 - C 4 alkynyi, carboxyl or C, - C 4 alkoxycarbonyl all substituted similarly or differently one or more times by halogen, cyano, nitro, hydroxy or by C 1 - C 4 alkoxy, R 24 = C 1 - C 4 alkyl, or C 1 - C 4 alkyl substituted one or more times by halogen, m = 3 or 4, n = 0, 1 , 2 or 3, p = 0 or 1 , X = oxygen or sulphur, Z = oxygen, sulphur or N - R 25 , R 25 ** hydrogen or C r C alkyl, W = oxygen, sulphur or carbon. Especially preferred are such compounds of formula (I) in which R 1 = methyl, R 2 - difluormethoxy, R 1 and R 2 together form the group -(CH jj ^-, R 3 = chlorine, R 4 = hydrogen, R 5 = nitro or cyano, R β = - R 1 = hydrogen or the group - OR 12 , R 12 = C r C β alkyl. R 14 Y = oxygen, - N - OR 13 and C V 5 . R 13 = C C 6 alkyl, R 14 and R 15 , independent of one another, are hydrogen, halogen or C. - C 4 alkoxy, R 1β = hydrogen, R 17 = hydrogen, R 18 , R 19 . R 20 , R 21 , R 22 and R 23 , independent if one another, are hydrogen, halogen, C r C alkyl, C r C 4 -alkoxycarbonyl- C r C 4 -alkyl, or C r C 4 -haloalkyl, n = 0, p = 0 or 1 , and X = oxygen. The compounds of the general formula (I) according to the invention can be prepared as follows: A) a compound of the general formula (II) R HNH j || in which R 1 , R 2 and R 3 have the meanings given in the general formula (I), is readed with a compound of the general formula (III) X R 8 , _ W / in which R 3 stands for the group -COOR' or the group - C - N whereby R 9 R 7 . R 8 and R 9 have the meaning given in the general formula (1) and X stands for oxygen. R β has the meaning given in the general formula (I) but contains no formyl groups R 27 and B stands for the group - OR or N whereby N R 2β R ■ >2 Λ β,- p Rr27 f a __nd__ independent of one another mean C, - C 4 alkyl. or B) in the case where R β stands for the formyl group, a compound of the general formula (la) in which R 1 , R 2 , R 3 , R 4 and R 5 have the meaning given in the general formula (I), and A stands for hydrogen, halogen, hydroxy, an alkyl- or aryl-sulphonyl group, is reacted with a suitable oxidising agent, or C) in the case where R β stands for the group - CYR 11 , whereby R 11 has the meaning given in the general formula (I) and Y stands for oxygen, a compound of the general formula (lb) in which R 1 , R 2 , R 3 , R 4 and R 5 have the meaning given in the general formula (I), is metallise with a suitable base and is then (readed) with an acyl compound of the general formula IV or in which R 11 has the meaning given in the general formula (I) R 30 and D stands for chlorine, bromine, - OR-" or - N R 31 whereby R 29 , R 30 and R 31 stand for C 1 - C 4 alkyl. Should R 1 stand for hydrogen, then th R 30 meaning of D is constrained to - OR 29 and to - N N R 31 or, Y .1 D) in the case where R β stands for the group - C - R 11 , in which R 11 has the meaning given in the general formula (I) and Y stands for sulphur, a compound o the general formula (lc) in which R 1 . R 2 , R 3 , R 4 . R 5 and R 11 have the meaning given in the general formula (I), is readed with Lawessons reagent, or Y II E) in the case where R β stands for the group - C - R 11 , in which R 11 has the meaning given in the general formula (I) and Y stands for the group - N-OR 13 , in which R 13 has the meaning given in the general formula (I), a compound of the general formula (lc) in which R 1 , R 2 , R 3 , R 4 , R 5 and R 11 have the meaning given in the general formula (I), is readed with a compound of the general formula VI H 2 N - OR 13 VI in which R 13 has the meaning given in the general formula (I), or Y u F) in the case where R 6 stands for the group - C - R 11 , in which R 11 has the meaning R 14 I given in the general formula (I) and Y stands for = C - R 15 , whereby R 14 and R 15 have the meaning given in the general formula (I), a compound of the general formula (lc) in which R 1 , R 2 , R 3 , R 4 , R 5 and R 11 have the meaning given in the general formula (I), is readed with a compound of the general formula VII or VIII R 14 ° R 14 Ph 3 P=* j5 vπ .R M O. 2 - p -~ vιπ R ,S Θ R Metal Q in which R 14 and R 15 have the meaning given in the general formula (I) and where R 32 stands for C, - C 4 alkyl, or G) in the case where R 0 stands for halogen, a compound of the general formula (Id) in which R 1 , R 2 , R 3 , R 4 , R 5 and R β have the meaning given in the general foπnula (I), is reade with a suitable halogenating agent, or H) in the case where R β stands for one of the groups in which R 1β , R 17 . R 18 , R 19 , R 20 . R 21 . R 22 . R 23 . R 24 , n. p and W have the meaning given in the general formula (I), a compound of the general formula (le) in which R 1 , R 2 , R 3 , R 4 , R 5, R 1β , R 17 and n have the meaning given in the general formula (I), is readed with a compound of the general formula IX, X or XI 2 xi, in which R 18 , R 1β , R 20 , R 21 , R 22 , R 23 . R 24 , p and W have the meaning given in the general formula (I), or I) in the case where R β stands for the group in which R 1β , R 18 , R 19 , R 20 , R 2 , R 22 , R 23 , n and p have the meaning given in the general foπnula (I), a compound of the general formula (If) in which R 1 , R 2 , R 3 , R 4 , R 5, R 1β and n have the meaning given in the general formula (I), is readed with a compound of the general foπnula XII where R 18 , R 19 , R 20 , R 21 , R 22 , R 23 . Z and p have the meaning given in the general formula (I). or J) a compound of the general formula (Ig) in which R 1 , R 2 . R 3 , R 4 and R 5 have the meaning given in the general formula (I), is firstl diazotised to give a compound of the general formula (Ih) in which R 1 , R 2 , R 3 , R 4 and R 5 have the meaning given in the general formula (I), and is the readed with a Michael-acceptor of the general formula XIII in which R 33 and R 34 , independent of one another, mean hydrogen, C, - C 4 alkyl or halogen, an R 35 means C - C 4 alkyl, or K) a compound of the general foπnula (If) is esterified with an alcohol of the general formula XI R 12 - OH XIV in which R 12 has the meaning given in the general formula (I). The compounds of the general formula (I) according to the invention, in which R 5 stands for th groups - COOR 7 or - CXNR 8 R 9 , can be prepared by the process described by Bisagni et al i Tetrahedron, 29 , 435 (1973). The oxidation according to process variant B) may be carried out by the processes such as are described for example in Houben-Wehl, Vd VII, , page 135 et seq (1954) or in Vol E3, page 231 et seq (1983). The compounds of general formula (la) used as starting materials are known (WO 9408 999). The process variant C) is carried out effedively by reading the starting material of foπnula (lb) in a suitable solvent at a temperature from - 100 to + 40 °C with a suitable base to give a compound of the general formula (li) in which R 1 , R 2 . R 3 . R 4 and R 5 have the meaning given in the general foπnula (I) and metal® stands for a metal cation such as for example lithium, sodium or potassium. The intermediate compound of the formula ('«) is readed diredly, ie, without any further processing, with a compound of foπnula IV or V at a temperature from - 100 to + 100 °C . Ethers, such as for example diethyl ether, tetrahydrofuran or 1,4-dioxane, may be dted as suitable solvents. Butyl lithium, lithium diisopropylamide, sodium hydride or potassium tert. butylate may be dted as bases. The compounds of the general formula (lb) used as starting materials are known. Their preparation is described in WO 9408 999. The process variant D) can be carried out for example according to the methods described in Bull Soc Chim Belg, 87, 223, 229, 299 or 525, (1978). The formation of oxime-ether in process variant E) can be earned out according to known processes such as are described for example in Houben-Wehl, Vol X4, page 55 et seq (1968). The compounds involved in process variant F) can be prepared by the methods described in "Advanced Organic Chemistry", 1985, page 864 et seq and in the literature cited therein. Sulphuryl chloride, sodium hypochlorite, N-chlorosuccinimide, N-bromosuccinimide, chlorine or bromine are examples of halogenating agents which may be used. The acetals or ketais may be prepared by the methods described by T W Greene in "Protective Groups in Organic Synthesis", 1980, page 116 et seq. The compounds according to the invention in accordance with process variant I) can be prepared by the process described by A I Meyers in J Am Chem Soc, 92, 6644 (1970). The compounds according to the process variant J) can be prepared according to the process cited in US Patent 5250504. The esterifications according to the last process stage are known per se and they can be carried out according to the usual methods, such as for example those described in Houben-Wehl, Vol E5, page 659 et seq (1985). The preparation can be carried out with or without solvents whereby if necessary such solvents or diluents which are inert with regard to the respedive readants may be used. .Examples of such solvents or diluents respedively are aliphatic and aromatic hydrocarbons each of which may optionally be chlorinated, such as for example hexane, cydohexane, petroleum ether, white spirit, benzene, toluene, xylene, methyiene chloride, chloroform, carbon tetrachioride, ethyiene chloride, trichioroethylene and chlorobenzene; ethers such as for example diethyl ether, methyl ethyl ether, methyl t-butyl ether, diisopropyl ether, dibutyl ether, dioxane and tetrohydrofuran; ketones such as for example acetone, methyl ethyl ketone, methyiisopropyl ketone, methylisobutyl ketone; nitriles such as for example acetonitrile and propionitrile; alcohols such as for example methanol, ethanol, isopropanol, butanol, tert-butanol, tert-amyi alcohol and ethyiene glycol; esters such as for example ethyl acetate and amyl acetate, acid amides such as for example dimethyl formamide and dimethyl acetamide, sulphoxides such as for example dimethyl sulphoxide, sulphones such as for example sulpholane, bases such as for example pyridine and triethyiamine, carboxylic acids such as for example acetic acid, and mineral acids such as for example sulphuric add and hydrochloric acid. The usual procedures are used for working-up the compounds according to the invention. Purification is carried out by crystallisation or by column chromatography. The compounds according to the invention are generally colourless or slightly yellow-coloured crystalline or viscous substances which for the most part are readily soluble in chlorinated hydrocarbons, such as for example methyiene 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 dimethyl. ormamide and also sulphoxides such as for example dimethyl sulphoxide. The compounds according to the invention display good herbiddal adion on broad-leaved weeds and grasses. Selective application is possible with various crops, for example rape, beet, soya beans, cotton, rice, maize, barley, wheat and other kinds of cereals. Individual compounds are also suitable as seledive herbiddes for beet, cotton, soya, maize and cereal. Furthermore the compounds can be used for weed-killing during long-term cultivation such as for example in plantations for forestry, decorative wood, fruit, wine, citrus, nuts, bananas, coffee, tea, rubber, oil-palm, cocoa, fruit berries and hops. The compounds according to the invention can be used for example for the following plant species: Dicotyledonous weeds of genus such as Sinapis, Lepidium, Gaiium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Brassica, Urtica, Senedo, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Potygonum, Sesbania, Ambrosia, Cirsium, Sonchus, Solanum, Lamium, Veronica, Abutilon, Datura, Viola, Galeopsis, Papaver, Centaurea and Chrysanthemum; monocotyledonous weeds of genus such as Avena, Alopecurus, Echinochloa, Sataria, Panicum, Digitaria, Poa, Eleusine, Brachiaria, Lolium, Bromus, Cyperus, Elymus, Sagittaria, Monochoria, Fimbristylis, Eleocharis, Ischaemum and Apera. T e applied amounts vary depending on the type of use and the stage of growth between 0.001 and 5 kg ha. The adive agents according to the invention can also be used as defoliants, desiccants and weed-killing agents. Enhancement of the intensity of adion and the speed of adion can be achieved for example by the use of additives which magnify the effect, such as organic solvents, wetting agents and oils. The use of such additives therefore optionally leads to a redudion in the dosage of the active material. The adive agents according to the invention or their mixtures are desirably applied in the form of preparations such as powders, spreading agents, granulates, solutions, emulsions or suspensions, with the addition of liquid and/or solid carriers or diluents respectively and optionally with bonding agents, wetting agents, emulsifying agents and/or dispersion aids. Suitable liquid carriers are for example aliphatic and aromatic hydrocarbons such as benzene, toluene, xyiene, cydohexanone, isophorone, dimethyl sulphoxide, dimethyl foπnamide and also mineral oil fractions and vegetable oils. Suitable solid carriers are minerals such as for example beπtonite, silica gel, talc, kaolin, Attapulgit, chalk and vegetable produds such as for example flour. Examples of surfadants are calcium lignin sulphonate, polyethylene alkylphenyl ether, naphthalene sulphonic adds and their salts, phenol sulphonic acids and their salts, condensates of formaldehyde, fatty alcohol sulphates as well as substituted benzene sulphonic acids and their salts. The amount of the respective adive agent(s) in the various preparations can vary over a wide range. For example, the material contains about 10 to 90 weight 0 /, adive agent, about 90 to 10 weight 0 /, liquid or solid earner and optionally up to 20 weight 0 /, surfadant. Application of the material can occur in the usual way, for example with water as the carrier in spraying amounts of about 100 to 1000 litre/ha. Application of the material in the so-called Low- Voiume-Process and the Ultra-Low-Volume-Process is also possible as is its application in the form of so-called micro-granules. The preparation of these mixtures can be carried out in a way known per se, for example by milling or mixing processes. If desired, preparations of the individual components can be mixed shortly before their use, as carried out in practice for example in the so-called tank-mix process. The following Examples describe the preparation of the compounds according to the invention. Example 1 (Process B) H4-chlor-5-difluoπnemoxy- 1 -memyl-3-py-___oty 29 g (9.6 mmol) H4*-*chlcr-5**difluormethoxy-1-memyl-3-pyι_^^ carbonitrile is added to 30 ml dichioromethane and 15.2 g pyridinium chlorochromate on aluminium oxide is then added. Stirring continues for 1 hour at room temperature and then the readion mixture is vacuum filtered through Celite and purified by means of column chromatography using hexane/ethyl acetate. Yield: 1.8 g = 62% of theory n D ∞ = 1.54066 Example 2 (Process E) (E/Z) 1 -(4-chlor-5-difluormethoxy-1 -methyl-3-pyι__zolyl)-o^methoxyiminomethyl-4-cart)onitrile. 0.46 g (1.5 mmol) 1-(4-chlor-5-difluoπnethoxy-1-methyl-3-pyrazolyl)-5-fonrnyl-4-pyrazol- carbonitrile is added to 4 ml pyridine at room temperature and 0.25 g (3.0 mmol) O-methyl- hydroxylamine hydrochloride is added. The mixture is stirred for 2 hours at room temperature, poured into water and shaken with ethyl acetate. It is dried over magnesium sulphate and concentrated. Purification is by column chromatography using hexane/ethyl acetate. Yield: 0.3 g = 60% of theory Freeze point: 95-98 °C Example 3 (Process F) 1 -(4-chlor-5-difluormethoxy- 1 -methyl-3-pyrazolyl)-5-(2-methoxyvinyl)-4-pyrazol-carbonitrile. 2.9 g (8.4 mmol) methoxymethylene-triphenylphosphonium chloride is added to 10 ml tetrahydrofuran and 5.6 ml (9.0 mmol) of a 1 ,6 molar solution of butyl lithium in hexane is slowly added dropwise at 0 °C. The orange-coloured solution is stiπed for another 30 minutes and then 1.0 g (3.3 mmol) 1-(4-c^lor-5-difluormethoxy-1-methyl-3-pyrazolyl)-5-foπnyl-4-pyrazol- carbonitrile is slowly added dropwise. Stirring continues for 2 hours at room temperature. The readion mixture is then added to water, shaken with ethyl acetate, dried over magnesium sulphate and concentrated. Purification is by column chromatography using a hexane/ethyl acetate mixture. Example 4 (Process H) H4-chlor-5-dffluc*rmethoxy-1-methyl-3^^ 0.6 g (2.0 mmol) H4-*c _or-5-*difUκ m e ^ is dissolved in 30 ml toluene and 0.14 g (2.2 mmol) ethyiene glycol and a catalytic amount of p- toluene sulphonic add are added. The mixture is heated for 2 hours on the water-separator, the cooled solution is washed with sodium chloride solution, and it is then dried and concentrated. Yield: 0.68 g = 98% of theory Freeze point: 70-72 °C Example 5 (Process H) 1-(4-chlor-5-difluc_ methoxy-1-methyl-3-pyrazoly 5 ml acetic anhydride is cooled to 0-5 °C and 2 drops boron trifluoride-etherate are added. Then 2.3 g (7.6 mmol) 1-(4-ch_w-5-diflι_ormethoxy-1-methyl-3-pyr__!θlyl^_^^^ is slowly added dropwise and stirring is continued for another 1.5 hours at room temperature. 9 ml of 10% sodium acetate solution is added, stirring is continued for 20 minutes at room temperature and then the mixture is shaken up with ethyl acetate. The combined ethyl acetate phases are washed with a solution of sodium hydrogen carbonate and sodium chloride, dried and concentrated. Purification is by column chromatography using a hexane/ethyl acetate mixture. Yield: 2.5 g = 80% of theory Freeze point: 84-85 °C Example 6 (Process J) 2*-chlor-3-{1*' 3***chlor^5,6,7-tetraty propionic add ethyl ester. 1.6 g (15.5 mmol) tert-butyl nitrite, 20 ml ethyl methacrylate and 1.52 g copper-ll-chloride is added to 20 ml acetonitrile and 2.62 g (10 mmol) 5-amino-1-(3-chlor-4,5,6,7-tetrahydropyrazolo- [1 ,5-a}-pyridin-2-yl)-4-pyrazol-carbonitrile is added in 3 portions. The mixture is stirred at room temperature for 20 hours, added to 50 ml 2N hydrochloric acid, extraded 3 times with dichloromethane, dried over magnesium sulphate and concentrated. Purification is by column chromatography using a hexane/ethyl acetate mixture. Yield: 1.6 g = 40% of theory no 20 = 1.54164 Example 7 (Process K) H3-chlor-4,5,6,7-tetrahydropyrazolo-[1,5-a]-pyridiιv2-yl)-4^^ isopropylester. 757 mg (2.7 mmol) of azodicarboxylic acid diethylester is added dropwise to 800 mg (2.7 mmol) H3-chlor*-4,5,6,7-tetrahydropyrazolo-{1 ,5-a]-pyridir-2-ylH-cyan-5-pyrazol-__ιi-)oxylic-add. The mixture is stirred for 2 hours at this temperature, then concentrated and purified by column chromatography using SiO 2 / hexane / ethyl acetate. The residue is recrystallised from diisopropyl ether. Yield: 570 mg = 62% of theory no 0 = 1.53942 The following compounds of formula (I) are prepared in an analogous fashion, wherein R 4 is just hydrogen. R 2 R 3 R 5 R β Freeze pt. [ °CJ or CH3 OCHF 2 Cl CN CH3 OCHF Cl CN CH3 OCHF 2 Cl CN CH3 OCHF 2 Cl CN -(CH 2 >4- Br CN -(CH 2 ) 4 - Cl N0 2 -a CH3 OCHF 2 Cl N0 2 - CH a--^ N \^CH CH, CH3 OCHF 2 Cl CN -(CH 2 ) 4 - Cl CN -CH f CH. 0 -(CH 2 )4- Cl CN -CH, .0 ^ CH 3 OCHF 2 Cl N0 2 73-75 -O CH 3 OCHF 2 Cl N0 2 CH, 1,516 (20.2) CH 3 OCHF 2 Cl N0 2 o«__. ~CH r o J 88 -(CH 2 ) 4 - Br NO 2 -CH.-< C n — i Θ9 -(CH 2 )4- Br NO 2 -CH. o.^ CH J 1.521 (24) CH 3 OCHF 2 Cl CN -CO2-.-C3H7 92-94 NO. R 3 R β Freeze pt. [ °CJ or n o (0 C> 123 CH 3 OCHF 2 Cl CN -C0-CH 3 The following Examples explain the invention: 0 = No damage 1 = 1- 24% damage 2 = 25 - 74% damage 3 = 75 -89% damage 4 = 90- 100% damage Example of application The indicated plant spedes in the greenhouse were treated after germination with the indicated compounds in application amounts of 0.1 kg adive agent/ha. For this purpose, the compounds were used as an emulsion with 500 litre waterha and were sprayed uniformly over the plants. 2 weeks after treatment, the compounds according to the invention showed an outstanding action against weeds as is shown in the following Table.

Claims: PATENT CLAIMS Substituted pyrazol derivatives of the general formula (I) in which R 1 = C r C 4 alkyl, R 2 " C r C 4 alkyl, C r C 4 alkylthio, C r C alkoxy; or C r C 4 alkyl, C r C 4 alkylthio, C r C 4 alkoxy ail substituted one or more times with halogen, R 1 and R 2 together form the group -(CH 2 ) m -, R 3 β hydrogen or halogen, R 4 " hydrogen or C r C 4 alkyl, R 5 " hydrogen, nitro, cyano or the groups -COOR 7 , or ■ C - R 10 u X R 8 " - OOR 7 or one of the groups R 7 , R 8 and R 9 , independent of one another, are hydrogen or C r C 4 alkyl, R 8 and R 9 . together with the adjacent nitrogen atom, form a 5-membered or 6-membered saturated heterocydic ring, R 10 = hydrogen, C r C 4 alkyl, or a C r C 4 alkyl substituted one or more times by halogen, R 11 = hydrogen, C r C β alkyl, C 3 - C β cydoalkyl, C 2 - C β alkenyl, C 3 - C 6 alkynyi ; or C r C β alkyl. C 3 - C β cydoalkyl, C 2 - C β alkenyl, C 3 - C β alkynyi all substituted similarty or differently one or more times by halogen, hydroxy or C C 4 alkoxy; or C 2 - C 8 alkyl, C 3 - C β cydoalkyl, C 3 - C 8 alkenyl, C 3 - C β alkynyi all inteπupted one or more times by oxygen; or the group OR 12 , R 12 = C, - C 6 alkyl, C 3 - C β cydoalkyl, (^ - C β alkenyl, C 3 - C β alkynyi; C, - C β alkyl substituted similarly or differently one or more times by halogen, hydroxy or by C 1 - C 4 alkoxy Y = oxygen, sulphur, - N - OR 13 and C \ R 15 R 13 = hydrogen, C, - C 6 alkyl, C 3 - C β cydoalkyl, C 2 - C 6 alkenyl, C 3 - C 6 alkynyi; C j - C 6 alkyl, C 3 - C 6 cydoalkyl, C^ - C 6 alkenyl, C 3 - C 6 alkynyi all substituted similarly or differently one or more times by halogen, cyano, hydroxy or C t - C 4 alkoxy; C 2 - C 8 alkyl, C 3 - C 8 cydoalkyl, C 3 - C 8 alkenyl, C 3 - C 8 alkynyi all interrupted one or more times by oxygen; C t - C 4 alkoxycarbonyl-^ - C 4 alkyl, which can optionally be substituted by halogen atoms; C, - C 4 alkoxycarbonyl-C 2 - C 4 alkenyl, which can optionally be substituted by halogen atoms; C, - C 4 alkoxycarbonyl, R 14 and R 15 , independent of one another, are hydrogen, halogen, cyano, carboxyl, formyl, C, - C 6 alkyl, C 3 - C 6 cydoalkyl, C 2 - C β alkenyl, C 3 - C β alkynyi; C, - C β alkyl, C 3 - C β cydoalkyl, (^ - C 6 alkenyl, C 3 - C 6 alkynyi all substituted similarty or differently one or more times by halogen, cyano, hydroxy or C^ - C 4 alkoxy; C 2 - C 8 alkyl, C 3 - C 8 cydoalkyl, C 3 - C 8 alkenyl. C 3 - C 8 alkynyi all inteπrupted one or more times by oxygen; C. - C 4 alkoxycarbonyl-C, - C 4 alkyl, which can optionally be substituted by halogen atoms; C, - C 4 alkoxycarbonyW^ - C 4 alkenyl, which can optionally be substituted by halogen atoms; C 1 - C alkoxycarbonyl, C^ - C 4 alkoxy or C, - C 4 alkylthio, R 14 and R 15 together with the carbon atom form a saturated carbocydic C 3 - C β ring which can be interrupted one or more times by oxygen or sulphur, R 1β = hydrogen or C t - C 4 alkyl, R 17 = hydrogen, C - C 4 alkyl or halogen-C, - C 4 alkyl, R ι β R 19 R 2o R 21 ^ an< j ^3 independent if one another, are hydrogen, halogen, C, - C 4 alkyl, C 2 - C 4 alkenyl or C 3 - C 4 alkynyi; C, - C 4 alkyl, C 2 - C 4 alkenyl, C 3 - C 4 alkynyi, carboxyl or C. - C 4 alkoxycarbonyl all substituted similarly or differently one or more times by halogen, cyano, nitro, hydroxy or by C, - C 4 alkoxy, R 24 = C t - C 4 alkyl, or C- - C 4 alkyl substituted one or more times by halogen, m = 3 or 4, n = 0, 1, 2 or 3, p = 0 or 1, X = oxygen or sulphur, Z = oxygen, sulphur or N - R 25 , R 25 = hydrogen or C 1 - C 4 alkyl, W = oxygen, sulphur or carbon. Substituted pyrazol derivatives of the general formula (I) in which R 1 = methyl, R 2 = methylthio or difluormethoxy, R 1 and R 2 together form the group -(CH 2 ) 4 -, R 3 = hydrogen, chlorine or bromine, R 4 = hydrogen, R 5 = hydrogen, nitro, cyano or the groups -COOR 7 or - CXR 10 , R β = . C - R 11 , - CH, - CH - COOR 7 II I , Y R or one of the groups R 7 = hydrogen or C r C 4 alkyl, R 10 = hydrogen, C, - C alkyl, or a C r C alkyl substituted one or more times by halogen, R 11 = hydrogen, C t - C 6 alkyl or the group - OR 12 , R 12 = hydrogen, C - C 6 alkyl, C 3 - C 6 cydoalkyl, C 2 - C 6 alkenyl, C 3 - C 6 alkynyi; C - C β alkyl substituted similarty or differently one or more times by halogen, hydroxy, C, - C alkoxycarbonyl-C, - C 4 alkyl or C 1 - C 4 alkoxy, Y = oxygen, sulphur, - N - OR 13 and C C u R 15 , R 13 = hydrogen, C 1 - C β alkyl, C 3 - C β cydoalkyl, C 2 - C β alkenyl, C 3 - C β alkynyi; C 2 - C 8 alkyl, C 3 - C 8 cydoalkyl, C 3 - C 8 alkenyl, C 3 - C 8 alkynyi all interrupted one or more times by oxygen; C, - C 4 alkoxycarbonyl-C, - C 4 alkyl, which can optionally be substituted by halogen atoms; C 1 - C 4 alkoxycarbonyl-C 2 - C 4 alkenyl, which can optionally be substituted by halogen atoms; C, - C 4 alkoxycarbonyl, R 14 and R 15 , independent of one another, are hydrogen, halogen, cyano, carboxyl, formyl, C t - C β alkyl, C 3 - C 6 cydoalkyl, C 2 - C β alkenyl, C 3 - C 6 alkynyi; C 1 - C alkoxycarbonyl-C ! - C 4 alkyl, which can optionally be substituted by halogen atoms; C t - C 4 alkoxycarbonyl, C 1 - C 4 alkoxy or C t - C 4 alkylthio, R 1β = hydrogen or C 1 - C 4 alkyl. R 17 = hydrogen. C - C 4 alkyl or halogen-C, - C 4 alkyl, R 18 , R 19 , R 20 , R 21 , R 22 and R 23 , independent if one another, are hydrogen, halogen, C 1 - C 4 alkyl, C_, - C 4 alkenyl or C 3 - C 4 alkynyi; C, - C 4 alkyl, C 2 - C 4 alkenyl, C 3 - C 4 alkynyi, carboxyl or C, - C 4 alkoxycarbonyl all substituted similarly or differently one or more times by halogen, cyano, nitro, hydroxy or by C, - C 4 alkoxy, R 24 = C, - C 4 alkyl, or C * - C 4 alkyl substituted one or more times by halogen, m = 3 or 4, n = 0. 1. 2 or 3, p = 0 or 1, X = oxygen or sulphur, Z = oxygen, sulphur or N - R 25 , R 25 = hydrogen or C 1 - C 4 alkyl, W = oxygen, sulphur or carbon. Substituted pyrazol derivatives of the general formula (I) in which R 1 = methyl, R 2 = difluormethoxy, R 1 and R 2 together form the group -(CH_,) 4 -, R 3 = chlorine, R 4 = hydrogen, R 5 = nitro or cyano, R β = - C - R 11 , orthe p R 11 = hydrogen orthe group - OR 12 , R 12 = C^ Cg alkyl. Y = oxygen, - N - OR 13 and C ^ >15 R 13 = - Cg alkyl, R 14 and R 15 , independent of one another, are hydrogen, halogen or C t - C alkoxy. R 1β = hydrogen, R 17 = hydrogen, R 18 , R 1β , R 20 , R 21 , R 22 and R 23 , independent if one another, are hydrogen, halogen, C, - C 4 alkyl, C 1 - C alkoxycarbonyl-C 1 - C 4 alkyl, or C * - C 4 haloalkyl, n = 0, p = 0 or 1, and X = oxygen. . Agent with herbiddal adion charaderised by containing at least one compound in accordance with the Claims 1 to 3. . Agent with herbiddal adion in accordance with Claim 4, in admixture with carriers and/or auxiliary materials. . Use of compounds in accordance with the Claims 1 to 3 for combating monocotyledonous and dicotyledonous weeds in main agricultural crops.

Inventors: BOHNER JUERGEN, FRANKE HELGA, GANZER MICHAEL, GEISLER JENS, HARTFIEL UWE, REES RICHARD, BOHNER, JUERGEN, FRANKE, HELGA, GANZER, MICHAEL, GEISLER, JENS, HARTFIEL, UWE, REES, RICHARD
Applicants: BOHNER JUERGEN, FRANKE HELGA, GANZER MICHAEL, GEISLER JENS, HARTFIEL UWE, HOECHST SCHERING AGREVO GMBH, REES RICHARD, BOHNER, JUERGEN, FRANKE, HELGA, GANZER, MICHAEL, GEISLER, JENS, HARTFIEL, UWE, REES, RICHARD
Application year: 1995
Main classification: C07D471
IPC codes: A01N43, A01P13, C07D231, C07D405, C07D409, C07D411, C07D413, C07D471