INSECTICIDE MEANS

The invention concerns a new N, N-Dimethyl-O-PYRAZOLYL-more carbaminsäureester than active substances containing insecticide means. It is already well-known that N, N-Dimethyl-O-PYRAZOLYL-more carbaminsäureester, like e.g. N, N-Dimethyl-o (l-phenyl-3-methyl-pyrazol yl) - and N, N-Dimethyl-o (l-iso-propyl-3-methyl-pyrazol yl) - 5-earbaminsäureester, insecticides characteristics exhibit (VG!. CH-PS Nr.279553 - Chem. Abstraets 47, 10172 a). It the new N.N Dimethyl O pyrazolylearbaminsäureester the general formula R I O-CO-N (CHù) 2 R-S (O) n-CI 2 in which R ffir hydrogen or if necessary by CN substituted Alky], R* for alkyl and n for 1 or 2 stands, found. The new connections are characterised by strong insecticides effectiveness. The new N, N-Dimethyl-O-PYRAZOLYL-more earbaminsäureester the formula (l) knowing by one a) Hydroxy pyrazole of the general formula (I) received. B I OH R-S (O) n-eH2 (II] where R, R* and n have the meaning indicated above, with N, N-Dimethyl-carbaminsäurehalogeniden the general formula shark CO n (CH 3) 2 (III) where Hal for chlorine or bromine, if necessary in presence of an acid acceptor and if necessary in presence of a diluent or b) Hydroxy pyrazole of of the general formula (II), where R, R* and n to have, with phosgene and afterwards with Dimethylamin in presence of a Säureakzepters and in presence of a Verdünnungsmlttels convert the meaning indicated above if necessary if necessary, stands converts c) N, N-Dimethyl-O-pyrazol yl-earbaminsäureester the general formula (I), where B and R* have the meaning indicated above and n for Nu!! , with the äquimolaren quantity of the Oxydationsmlttels Wass8rsteffperoxyd, if necessary in presence of a diluent converts or d) N stands, N-Dfmethyl-O-pyrazol yl-more carbaminsäureester for the general formula (1), where B and B* di whether n indicated meaning have and n for zero stands, with at least two equivalents of the oxidising agent m-chlorine-perbenzoesäure, if necessary in presence of a diluent it converts. Surprisingly, N-Dimethyl-O-PYRAZOLYL-more carbaminsäureester better insecticides show the N which can be used according to invention an effect than the appropriate connections of similar constitution and same direction of action before-well-known from the state of the art. The products in accordance with the invention represent thus a genuine enrichment of the technology. Connections of the formula (I), in which R, R* and n for the output products of the procedures a) until d) indicated the preferredwise meanings possess (see below) are preferential. Uses one in procedures (A) l-Nethyl-3-äthylsulfinyl-methyl-5-hydroxy-pyrazol and I0 N, N-Dimethyl-carbaminsäurechlorid, in procedure (C) N, N-DimeLhyl-o (l-meLhyl-3-äLhyILhiomeLhyl - pyrazol yl-carbaminsäureester and hydrogen peroxide, in procedure (D) N, N-Dimethyl-o (1-propyl-3-äthylthiomethyl-pyrazol yl-carbaminsäureester and in procedure (B) 1-tert. Butyl-3-methylsulfinyl-methyl-5-hydroxy-pyrazol, phosgene and DimeLhylamin as basic materials, then can be shown the expirations of reaction by the following formula patterns: a) I OH O-C0-N ù'" \/\ °ù. H C2 - SO-CH 2 H5C2-S0-CH 2 b) C Hg-tert. f OH H3C-S0-CH 2 I) + COCl2 2) + HN (CH) 2 C4Hg-tert. . O-CO-N (CH,) 2 [!GT!] N/H3C-SO-CH2 c) H, O-CO-N (CH 3) 2 N/N/+ H202) tl H sC2 - S-CH2 CH3 I. O-CO-N (CH ù) 2 ttsC2-SO-Ctt2 d) C3HT-n I O-CO-N (CH 3) 2 N/N//Il IL H5C2-S-CHa Cl CùH - n I o-CO-n (cN,) 2 N/N \/O-OH H5 C2 - SOS-CH22 the “Hydroxy pyrazole which can be used with procedures (A) and (B) as basic materials are by formula (II) defined. Preferably in it R stand for 1 to 5 carbon atoms for hydrogen as well as for geradkettiges or branched alkyl with I to 8, in particular and for cyanogen ethyl, R” for geradkettiges alkyl with 1 to 5, in particular 1 to 3 carbon atoms and n for 1 or 2. The Bydroxy pyrazole of the formula (II) one receives by conversion from hydrazine or hydrazine derivatives with A-Alkylthio-aeetessigsäureestern with 0 to 40°C in inert diluents and following oxidation of the 3-Alkylthiomethyl-5-hydroxy-pyrazole with hydrogen peroxide or m-CH, received thereby! orperbenzoesäure, likewise with 0 to 40°G and likewise in presence of diluents. As Carbaminsäureha] ogenid the formula (III) with procedures {a) and frequently the N used producible in literature-well-known procedures in the technology, N-Bimethyl-carbaminsäurechlorid is preferably used. With the procedures (C) and (D) when basic materials N which can be used, N-Dimethyl-o (3-alkyltbiomethyl-pyrazol yl) - it is more carbaminsäureester by formula (I) under the condition that n stands for zero, defined. They can be made similar to procedure (A) of the appropriate 3-Alkylthiomethyl -5-hydroxy-pyrazolen and N, N-Dimethyl-carbaminsäurechlorid, preferably become *5 in procedures (C) and (D) connections of the formula (I}, in which n stands for zero, and where R for hydrogen and geradkettiges or branched alkyl with 1 to 8 stands, in particular for 1 to carbon atoms as well as for Cyanoäthyl and stands for R for geradkettiges alkyl with 1 to 5, in particular 1 to 3 carbon atoms, as basic materials assigned. In procedure (A} and used (B) oxidation center! Hydrogen peroxide and m-chlorine - by benzoic acid well-known connections are and can in literature-well-known procedures be manufactured. The procedures (A), (B), (C) and (D) for the production of the new N, N-Dimethyl-O-PYRAZOLYL-more carbaminsäureester are accomplished preferentially using diluents, than such are applicable practically all inert organic solvents. Biezu belong in particular aliphatic and aromatic, if necessary chlorinated hydrocarbons, like gasoline, benzene, toluol, xylene, dichloromethane, chloroform, Tetracblorkohlenstoff, Chlorbenzo] and to o-Bichlorbenzol, ether such as Diäthylund Dibutyläther, tetrahydrofurane and Dioxan, Ketone such as acetone, methyl ethyl, Methylisopropylund Methylisobutylketon as well as nitriles such as Aeetonitril and Propionitril. For procedures (C) aliphatic carbonic acids e.g. become, like acetic acid. as solvent prefers. Procedures (A) and (B) are accomplished preferentially using acid acceptors. As acid acceptors all usual acid bonding agents use can find. Particularly worked satisfactorily alkali carbonates äthylat themselves and - alcoholates, as Natriumund potassium carbonate, Natriumund Kaiiummethylat and/or -, furthermore aliphatic, aromatic or heteroeyelisehe Amiae, for example tri methyl amine, tri methyl amine, Dimethylanilin, Dimethylbenzylamin and Pyridin. The reactions are accomplished, preferred generally at temperatures between 0 and 80 " C for procedures {a) the range between 20 and 60 " C, for procedures (B), (C) and (D) the range between 5 and 25 “C. The conversions are accomplished generally with normal print. For the execution of procedures (A) and (B) the basic materials into äquimolaren quantities are usually used. A surplus or other reaction component does not bring substantial advantages. The conversion is accomplished generally in a suitable diluent in presence of an acid acceptor. After reaction end one pours the mixture in water and vibrates with an organic solvent, e.g. toluol out. The organic phase is then regenerated as usual by washing, drying and Abdestillieren of the solvent. With procedure (C) the reaction partners are used likewise preferentially into äquimolaren quantities. Those hiebei as diluent used acetic acid is usually abdestilliert after reaction end in the vacuum. Afterwards one adds an organic solvent, z, B. Methylenchlorid and regenerates the organic phase as usual by washing, drying and Abdestillieren of the solvent. With procedures (D) the m-chlorine-perbenzoesäure used as oxidising agents usually in the surplus is inserted, u.zw between 2 and 3 gets per mol of o (3-AlkylLhiomethyl-pyrazol yl) - 5-N, N-dimethyl-more carbaminsäureester. The conversion is usually not accomplished in solvents mixable with water. One washes then neutrally and regenerates as under (A) and (C) described. The new connections result partially in the form of oils, which cannot be distilled partially without decomposition, however by so-called “Andesti] lieren”, i.e. by longer heating up under decreased pressure on moderately increased temperatures from the last volatile portions to be released and cleaned in this way. For its characterisation the refractive index serves. As far as the new products anfaIlen after the Abdestillieren of the solvent in firm form, they are cleaned by recrystallization. For the characterisation the fusion point serves. As mentions already several times, the new are characterised outstanding insecticides N.N Dimethyl O PYRAZOLYL more carbaminsäureester by an effect. The means according to invention are suitable from there with good plant compatibility and favorable Warmblütertoxizität for the fight against animal parasits, in particular insects, which seem to material protection in the agriculture, in princes, in Vorratsund as well as on the hygiene sector. They are effective against normally sensitive and resistant kinds as well as against all or individual development stages. To the parasits mentioned above belong: From the order of the Isopoda e.g. Oniscus asellus, ArmadilIidium vulgare, Porcellio more scaber. From the order of the Diplopoda e.g. Blaniulus guttulatus. From the order of the Chilopoda e.g. Geophilus carpophaus, Scutigera spec. From the order of the Symphyla e.g. ScutigereIla immaculata. From the order of the Thysanura e.g. Lepisma saccharina. From the order that CO] lembola e.g. Onychiurus armatus. From the order of the Orthoptera e.g. Blatta orientalis, Periplaneta americana. Leucophaea maderae, Blatella germanica, Acheta domesticus. Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria. From the order of the Dermaptera z, B. Forficula auricu] aria. From the order of the Isoptera e.g. Reticulitermes spp. From the order of the Anop] ura e.g. Phylloxera vastatrfx, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp. From the order of the Mallophaga e.g. Trichodectes spp., Damalinea spp. From the order of the Thysanoptera e.g. Hercinothrips fermoralis, Thrips tabaci. From the order of the Heteroptera e.g. Eurygaster spp., Dysdercus intermedius. Piesma quadrata, Cimex lectularius, Bhodnfus pr “lixus, Trfatoma spp. From the order of the Homoptera e.g. Aleurodes brassicae. Bemisia tabaci. Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma] anigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Bhopalosiphum padi. Empoasca spp., Euscelis bilobatus. Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striate] lus, Nilaparvata of peeping, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psylla spp. From the order of the Lepidoptera e.g. Pectinophora gossypiella, Bupalus piniarius, Cbeimatobia brumata, Lfthocolletis blancardella, Hyponomeuta padella, P1utella maculipennis. Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxna spp., Peltia spp. Earias insu] ana. Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura. Spodoptera spp. Trichoplusia nl. Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana. From the order of the Coleoptera e.g. Anobium punctatum, Rhizopertha dominioa, Bruchidius obtectus, Acanthoscelides obLectus, Bylotrupes bajulus, Agelastica alni. Leptin tarsa deeemlineata, Phaedon cochleariae, Dfabrotica spp. Psylliodes chrysocephala. Epilachna varivestis. Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus suloatus, Cosmopolltes sordidus. Ceuthorrhynchus assimilis, Hypera postica. Merdestes spp., Trogoderma spp. Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Pfinus spp. Niptus hololeucus, Gibbium of psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis. Costelytra zealandica. From the order of the Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp. From the order of the Diptera e.g. Aedes spp., Anopheles spp., Culex spp., Drosophila melanoI0 more gaster, Musca spp., Fannia spp., Calliphora erythrocephala, Luci] ia spp. Chrysomyia spp. Cuterebra spp. Gastrophilus spp. Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp. Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata. Dacus eleaa. Tipula paludosa. From the order of the Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp. Bie according to invention into the usual formulations transferred. like solutions, emulsions, Spritzpulver, suspensions, powder, types of dust means, foam, pastes, soluble powders, granulates, aerosols, suspension emulsion concentrates, seeds propellant, active substance-impregnated Naturund snythetische materials, purifying encapsulations in polymere materials and in I] fillmassen for seeds, furthermore in formulations with fuel sets, like smoking cartridges, - doses, - spirals u.ähnl. as well as ULV Kaltund Warmnebel Formulierungsn. These formulations in well-known way manufactured, e.g. by mixing the active substances with stretching means, thus liquid solvents, under pressure standing liquefied gases and/or firm carrier materials, if necessary using surface-active means, thus emulsifying means and/or dispersing agents and/or foam-producing means. In case of the use of water as stretching means e.g. also organic solvents can be used as auxiliary solvents. As liquid solvents are essentially applicable: Aromatics, like xylene, toluol, or alkyl naphtha LINE. chlorinated aromatics or ehlorierte aliphatic hydrocarbons, like chlorine benzene. Chlorine ethylens or dichloromethane. aliphatic Kohlenwasserstofte, like cyclohexane or paraffins, e.g. Erdölfraktionen, alcohols, like butanol or glycol as well as their ether nnd esters. Ketone, like acetone. Methylethylketone, Methylisobutylketon or cyclohexanes, strongly polar solvents, like dimethylformamide and Dimethylsulfoxyd, as well as water; with liquefied gaseous stretching means or carrier materials such liquids are meant, which are gaseous under normal print at normal temperature and, e.g. aerosol propulsion gases, like halogen hydrocarbons as well as butane. Propane, nitrogen and carbon dioxide; as firm carrier materials kornmen in question: e.g. natural powdered minerals, like Kaoline. Aluminas, talcum powder, chalk, quartz. Attapulgit, Montmorillonit or Diatomeenerde and synthetic powdered minerals, like hochdisperse silicic acid, alumina and Silikata; as carrier materials for granulates chamfered are applicable: e.g. broken and fractionated natural rocks such as Calcit, marble, pumice, Sepiolith, dolomite as well as synthetic granulates from inorganic and organic meals as well as granulates from organic material such as Sägemehl, coconut bowls, ears of corn and tobacco stacks; as Emulgierund/or foam-producing means are applicable; e.g. nichtionogene and anion-active emulsifying agents, like Polyoxyäthylen fatty acid ester, Polyoxyäthylen Fettalkohol ether, z, B. Alkylarylpolyglykol ethers, Alkylsulfonate, alkyl sulfates, Arylsulfonate as well as Eiweißhxdrolysate; as Dispcrgiermittel are applicable: e.g. lignin Sulfitablaugen and methyl cellulose. Polyvinylacetat can be used in the formulations llaftmittel like Carboxymethylcellulose, natural and synthetic powdery, granular or latexförmige polymers, like Gummiarabicum, polyvinyl alcohol. Also coloring materials can be e.g. added like inorganic pigments, ferric oxide, titanium oxide, ferrous cyan blue and organic coloring materials, like alizarine, Azol Metallphthalocyaninfarbstoffe nnd trace nutrients such as salts by iron, manganese, Ber, copper, cobalt, molybdenum and zinc. Bie formulations contain generally between 0, I and 95 Gew, - % active substance, preferably between 0.5 and 90 Gew. - %. The application of the new active substances effected in form of its commercial formulations Nr.362620 and/or out these formulations prepared the Anwendungsfermen. The active substance content of the application forms prepared from the commercial formulations can vary within wide ranges. The active substance concentration of the application forms knows active substance of 0,0000001 up to I00 Gew, -, preferably between 0,01 and 10 Gew. - % lie. Application happens in the application forms adapted a usual way. With application against IIygieneund food pests are characterised the active substances by a outstanding Residualwirkung on wood and clay/tone as well as by a good alkali stability on gekälkten documents. Example 1: Myzus test solvent: 3 Gew. - Parts dimethylformamide emulsifying agent: I Gew. - Part of Alkylarylpolyglykoläther for the production of an appropriate active substance preparation one mixes I Gew. - Tell active substance with the indicated quantity of solvents and the indicated quantity emulsifying agent and dilutes the concentrate with water on the desired concentration. Kohl sheets (Brasslca oleracea), which are strongly by the peach sheet louse (Myzus persicae) stricken, by dipping into the active substance preparation of the desired concentration are treated. According to the desired time killing in % is determined. Means 100 that all sheet lice were killed; 0% mean that no sheet lice were killed. With this test the connections stated in the following table e.g. show superior effectiveness in relation to the state of the art. Table 1 Myzus TesL active substance connection CH! \ J \. O-CO-N (CH s la CH (CH 3) 2 (admits) CHs II I N n O-CO-N (GH s) 2 CH SO-CH3 I O-CO-N CH, CH Wirkstoffkonzentr ation in Gew. - % 0, I O, Ol 0, [in after 1 day lOO 0 98 o 10o I00 table 1 (continuation) Wirkstoffkonzentr ation Vernlchtungsgrad work 0,01 0.1 0,01 Vernlchtungsgrad ffverbindung in Gew. - % in % after 1 day CH2 - SO-C 3 H 7 CH3 CH3 CH - SO-CH 3 I -- O-OO-N C2H CH3 CHe-SO-C2 Hs C2 Hs CH NCH - CH3 C H, i CH3 CH2 - SO-CH3 C H, i CH3 C O-C2Hs II lJ C, H i CH, 0, i 0.01 0, I 0.01 0, I 0.01 0, i 0.01 0.1 0.01 0, I 0.01 0, I 0.01 C O-OH 3 .OH3 C " Hgn CH Nr.362620 i00 99 ioo i00 IOO ioo 100 IOO ioo I0O I0O i00 i00 I0O table 1 (continuation) active substance concentration destruction degree of active substance connection in Gew. - % in % after 1 day OH 2 - SO-OH I I” H9 i CH3 CH2 - SO-CH3 I O-CO-N C “H CH3 N CH3 oo N 0.I 0.01 0, I 0,01 0, I 0.01 0,1 0.01 Nr.362620 lOO lOO lOO lO0 100 98 lOO 90 example 2: Grenzkonzentrations Test/Wurzelsystemisohe effect test insect: Myzus persicae solvents: 3 Gew. - Parts acetone emulsifying agent: 1 Gew. - Part of Alkylarylpolyglykoläther for the production of an appropriate active substance preparation one mixes 1 Gew. - Part active substance with the indicated quantity of solvent, admits the indicated quantity emulsifying agent and dilutes the concentrate with water on the desired concentration. The active substance preparation is mixed intimately with ground. The concentration of the I0 of active substance in the preparation plays practically no role, crucially is alone the active substance weight quantity per unit volume ground, which in ppm (= mg/l) one indicates. One fills the treated ground into pots and bepflanzt these with Kohl (Brassiea oleracea). The active substance can be taken up in such a way by the plant roots from the ground and transported to the sheets. For that. Proof of the root-systemic effect after 7 days excluding the sheets are occupied with the test animals specified above. After further 2 days the evaluation takes place via counting or estimating the dead animals. From the killing numbers the root-systemic effect of the active substance is derived. It is i00%, if all test animals are killed and 0%. if still exactly the same many test insects live as with untreated control. With this test the following connections e.g. show superior effect in relation to the state of the art. Table 2 root-systemic effect Myzus persicae is dung destruction degree in o with an active substance concentration of ppm CH3 well-known! II O-CO-N (CH3) 2 CH (CH3) 2 CH3 admits of C CH I]]] o N N'/C o - N (CH 3) 2C H ISO JCH3] O-CO-N CH 2 - SO-CH s C O-CH CH 3 CH3 o o% i00 lOO% 100% table 2 (continuation) active substance connection destruction degree in % with an active substance concentration of ppm CH2 - Then-Gis O-CO-N< C Hg (n) CH, - ° ' “_£' C3H ISO CH3 CH2-SO-C3 H n 01t 3 CH lOO% 100% 100% example 3: Grenzkonzentrations Test/Wurze] systemic effect test insect: Phaedon cochleariae larvae solvents: 3 Gew. - Parts acetone emulsifying agent: 1 Gew. - Part of Alkylarylpolyglykol ethers for the production of an appropriate active substance preparation one mixes] Gew. - Part active substance with the indicated quantity of solvent, admits the indicated quantity emulsifying agent and dilutes the concentrate with water on the desired concentration. The active substance preparation is mixed intimately with ground. The concentration lo of the active substance in the preparation plays practically no role, crucially is alone the active substance weight quantity per unit volume ground, yields in ppm (= mg/l) one indicates. One fills the treated ground into pots and bepflanzt these with Kohl (Brassica oleracea). The active substance can be taken up in such a way by the plant roots from the ground and transported to the sheets. For the proof of the root-systemic effect after 7 days excluding the sheets are occupied with the test animals specified above. After further 2 days the evaluation takes place via counting or estimating the dead animals. From the killing numbers the root-systemic effect of the active substance abge is eitet]. It is I00%, if all test animals are killed and 0%, if still exactly the same many test insects live as with untreated control. With this test the following connections e.g. show superior effect in relation to the state of the art. Table 3 Nr.362620 root-systemic effect Phaedon cochleariae larvae active substance connection destruction degree in % with a Wirkstoffkonzentr ation of ppm CH3 admits of I] I N N i O-CO-N (CH3) CH (CH 3) CH admits - SO-SCH 3 I O-CO-N C H ISO CH3 H5 C 3 H7 ISO CH3 o% o% 100% 95% regulations for the production of the active substances 1. C” H - to ISO down I O-CO-N (CH3) 2 H3C-SO-CH2 connection Nr.l a suspension from I0, I g (50 mMol) l-iso-Propyl-3-methyl-sulfinylmethyl-5-hydroxy-pyrazol, 8.4 g (60 mMol) of gemahlener potash and 200 ml acetonitrile lets one 1 h with 500C agitate, cools her afterwards on ambient temperature and adds 5.4 g (50 mMo]) N, N-Dimethyl-carbaminsäurechlorid. After hour agitating with 50°C the reaction solution with 200 is shifted ml water and out-vibrated with 300 ml toluol. The organic phase is dried, filtered over magnesium sulfate and taken off the Solvens at the rotation evaporator in the vacuum. 11.8 g (87% of the theory) remain to N, N-Dimethyl-o (1-iso-propyl-3-methylsulfinyl-methyl-pyrazol yl) - carbaminsäureester in form of weakly violet crystals with the fusion point 69°C. 2. H3 C-SO-CH2 CH3 I O-CO-N (CH3) 2 connection Nr.2 H 3 C-SO - CH a solution of II, 5 g (0.05 mol) N, N-Dimethyl-o (l-methyl-3-methylthiomethyl-pyrazol yl) - - more carbaminsäureester in 50 ml glacial acetic acid is shifted with 5 to 10°C with 3,4 g (0,05 mol) 50%igem hydrogen peroxide. One agitates the mixture 6 h at ambient temperature after and distills then the solvent in the vacuum off. The arrears are solved in i00 ml dichloromethane and washed with I0 of a solution from I0 g potassium carbonate in 15 ml water. The organic phase is separated and dried over sodium sulfate. Then one distills the solvent in the vacuum off. One keeps so 12 g, (98% of the theory) more earbaminsäureester to N.N Dimethyl o (l-methyl-3-methyl-sulfinylmethyl-pyrazol21 yl) - in form of a brown oil with the refractive index lp " 1,5362. 3. C3 H, - ISO O-CO-N (CH,) 2 N/N/IL! Connection Nr.3 to a solution of 12,9 g (0.05 [, 1ol) N.N Dimethyl o (l-iso-propyl-3-methylthiomethyl-pyrazol yl) - more carbaminsäureester in 50 ml chloroform drips one with 5°C a solution of 21,3 g m-Chlorperbenzoesäure in 150 ml chloroform. The mixture is after-agitated over night at ambient temperature and filtered then. One washes the filtrate with 10 ml konz. Potassium carbonate solution and dry it over Natriumsu] fat. Then the solvent in the vacuum is taken off. Back 13 g (90% of the theory) remain N, N-Dimethyl-o {l-iso-propyl-3-methylsulfonylmethy] - pyrazol yl) - more carbaminsäureester in form of beige crystals with the fusion point I020C. Similar to one of the regulations 1 to 3 the following know connections of the formula R [O-CO-N (CH,) 2 N/N/R * - SOn Cft CD to be manufactured: Connection No. 4 6 7 8 9 11 12 13 14 17 18 19 21 22 23 24 R C Hù - ISO C H9 - n C H - ISO C H9 - sec. C2Hs CH (C2H5) 2 C2H CzH CH, C 3 H - ISO CH3 H CH2-CH2 - CN CH 2 - CH2-CN CH2 - CH2-CN C H C4H9 - sec. CH (C2Hs) 2C H, - ISO C 9 - n C B, - tert. C H9 - tert. G 1 CH, CH, C2H5 CH3 OH3 GH C2Hs C2 H5 OH, 02H5 n-C3 H7 OH3 12 [- I3 C2Hs CH3 C [-. I3 CH3 CH3 CH, CI-I3 CIt3 CH3 1 1 1 1 1 1 1 2 2 2 1 1 1 1 2 2 2 2 2 2 1 2 bumps (% of the theory) 95 91 77 87 76 87 90 94 88 61 69 90 61 physical data out (refractive index: Fusion point °C) 21 lp: 1,5198 2, 1.5209 lp • 82 lp: 1.5042 lp; 1.5107 lp: 1.5084 n21: 1,5272 69 123 79 lp: I, 5252 lp: 1.4973 n2: 1,5304 102 82 lp: 1,5028 94 the substituted 5-Hydroxypyrazole which can be used as raw materials can e.g. to be manufactured as follows: a) H - iSoOH N/N@ I Ith stage: To a solution of 18,6 g (0.11 mol) to Isepropylhydrazinsulfat in 30 ml methanol gives one under cooling 0.11 mol of a solution of Natriummethylat in methanol. Then one shifts the mixture at ambient temperature miL 17.6 g (0.1 mol) A-Methylthioacetessigsäure-more äthylesLer and agitates 6 h after. Subsequently, the solvent in the vacuum is abdestilliert, the arrears with water verI0 rubbed and after crystallization sucked off. One receives in such a way 13,4 g (73% of the theory) to 1-1sopropyl -3-methylLhiomethyl-5-hydroxypyr azol • 2nd stage: To a solution of 27,2 g (0.2 mol) one gives 50%iges hydrogen peroxide to this connection in 150 ml Eisesslg with to 10°C 13.6 g (0.2 mol). One agitates the mixture 4 h at ambient temperature after and distills the solvent in the vacuum off. The arrears sucked off with ether rubbed • and after Krlstallisation. One receives in this way l-lsopropyl-3-methylsulfinylmethyl-5-hydroxy-pyrazol to 25,8 g (64% of the theory) in form of a pink colored powder with the fusion point I17°C, in similar way can the following connections of the formula be manufactured: R [oH N/N II II R*-SO - CH b C D e f Cù H9 - ISO C H9 - n CH H CH2 CH2 - CN CH3 CH, u-C3 H CH3 CH, yield (% of the theory) 39 44 98 87 56 fusion point (°C) 114 89 103,160 58