IE921836A1

IE921836A1 - Sulfonylformamidrazones, their preparation, agents¹containing them, and their use against pests of plants

Info

Publication number: IE921836A1
Application number: IE921836A
Authority: IE
Inventors: Hilmar Mildenberger; Frank Zurmuhlen; Peter Braun; Burkhard Sachse
Original assignee: Hoechst Ag
Priority date: 1991-06-08
Filing date: 1992-07-01
Publication date: 1992-12-16
Also published as: AU1920792A; WO1992022526A1; EP0589932A1; EP0518215A1; JPH0686420B2; JPH06502656A

Abstract

The invention relates to sulphonylformamidrazones of the general formula (I) and to their tautomers of the general formula (II) in which R<1> denotes optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, phenyl, or a radical of the formula -A-NR<2>2, -A-CO-R<4>, -A-SO2R<4>, -A-SOR<4>, -A-SR<4> or -S-P(O)R<4>2, which is as defined in the description, and R<2> represents optionally substituted alkyl, alkenyl, alkynyl, phenyl, benzyl or a radical of the formula -CO-R<2> or -SO2R<2>, which is as defined in the description. The invention furthermore relates to a process for their preparation, to compositions containing them, and to their use for controlling pests of plants and as an insecticide.

Description

HOECHST AKTIENGESELLSCHAFT HOE 91/F 173 Dr. WS/rh Description Sulfonylformamidrazones, their preparation, agents containing them, and their use against pests of plants The present invention relates to sulfonylformamidrazones, to processes for their preparation, to agents containing them, and to their use against pests of plants, in particular as fungicides.

The invention relates to sulfonylformamidrazones of the formula (I) and their tautomers of the formula (II) NH2 NH N-NHR2 (0 NH-NHR2 (II), in which R1 is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, it being possible for the 5 groups independently of one another to be unsubstituted or monosubstituted or polysubstituted by the radicals halogen, cyano, nitro, mono- and dialkylamino, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkenylthio or alkynylthio, or a radical of the formula R2 is alkyl, alkenyl, alkynyl, phenyl and benzyl, it being possible for the 5 groups independently of one another to be unsubstituted or monosubstituted or polysubstituted by the radicals halogen, cyano, nitro, mono- and dialkylamino, alkoxy and haloalkyl, or a radical of the formula - 2 -C(O)R2 or -SO2R2 ’, where R2' is alkyl, alkenyl, alkynyl, phenyl and benzyl, it being possible for the 5 groups independently of one another to be unsubstituted or monosubstitu5 ted or polysubstituted by the radicals halogen, cyano, nitro, mono- and dialkylamino, alkoxy and haloalkyl, n is an integer from 0-5, A is a direct bond, a saturated or unsaturated, 10 branched or unbranched, alkyl chain, Z is hydrogen, halogen, nitro, cyano, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkoxy, alkenyloxy, alkynyloxy, phenyl, phenoxy, haloalkyl, haloalkoxy, alkylthio or haloalkylthio, or a radical of the formula -A-NR32, where R3 radicals independently of one another are alkyl, alkenyl, alkynyl, cycloalkyl, phenyl, benzyl, alkoxy, alkenyloxy, alkynyloxy, phenyloxy, benzyl20 oxy, alkoxyalkyl, alkylthioalkyl, haloalkoxyalkyl, haloalkylthioalkyl, haloalkyl, hydrogen or a radical of the formula -C(O)R4, -SO2R4, -SOR4 or SR*, or NR32 is morpholino, dialkylmorpholino, piperidino, piperazino, hydrazino, hydroxylamino, phthalimido, maleinimido or dihydrophthalimido, or a radical of the formula -A-C (0) R4, where R4 is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, phenyl, phenoxy, phenylthio, OH, SH, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkenylthio, alkynylthio, cycloalkylthio, cycloalkoxy, haloalkoxy, haloalkylthio, alkoxyalkyl or alkylthioalkyl, or -NR52, where R5 radicals independently of one another are alkyl, alkenyl, alkynyl, cycloalkyl, phenyl, benzyl, hydrogen, alkoxyalkyl or alkylthioalkyl, or NR52 is piperidino, morpholino, piperazino, hydrazino or hydroxylamino, or a radical of the formula -A-SO2R\ -A-SOR4, -A-SR* or -A-P(0)R*2.

Preferred compounds of the formula (I) and (II) are those in which R1 is (Ci-Cg)-alkyl, (C2-C4)-alkenyl, (C2-CA)-alkynyl, 15 (C3-C6)-cycloalkyl or (C3-C6)-cycloalkenyl, it being possible for the 5 groups to be independently of one another unsubstituted or monosubstituted or polysubstituted by the radicals halogen, cyano, nitro, mono- and di-(Cx-C6)-alkylamino, (Ci—CA) -alkoxy, (C2-C4)-alkenyloxy, (C2-C J-alkynyloxy, (Cx-CJ -alkylthio, (C2-C4)-alkenylthio and (C2-C4)-alkynylthio, or is a radical of the formula R2 is (Ci-Cg)-alkyl, (C2-CA) -alkenyl, (C2-C4) -alkynyl, phenyl and benzyl, it being possible for the groups independently of one another to be unsubstituted or monosubstituted or polysubstituted by the radicals halogen, cyano, nitro, mono- and di(Ci-CJ-alkylamino, (Cx-C<)-alkoxy or halo-fCi-CJIE 921836 - 4 alkyl, or a radical of the formula -C(O)R2' or -SO2R2’, where R2’ is (Cx-C6)-alkyl, (C2-CA)-alkenyl, (C2-C4)-alkynyl, phenyl and benzyl, it being possible for the groups independently of one another to be unsubstituted or monosubstituted or polysubstituted by the radicals halogen, cyano, nitro, mono- and di(Cx-C4)-alkylamino, (Cx-C4)-alkoxy or halo-(Cx-C4)alkyl, n is an integer from 0-5, A is a direct bond, a saturated or unsaturated, branched or unbranched, alkyl chain, Z is hydrogen, halogen, nitro, cyano, (¢^-C6)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C3-C6)-cycloalkyl, 15 (C3-C6)-cycloalkenyl, (Cx-C4)-alkoxy, (C2-C4) -alkenyloxy, (C2-C4)-alkynyloxy, phenyl, phenoxy, halo(Cx-C4)-alkyl, halo-(Cx-C4)-alkoxy, (Cx-C4)-alkylthio or halo-(Cx-C4)-alkylthio, or a radical of the formula 0 - A-NR32, where R3 radicals independently of one another are (Cx-C6)alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C3-C6)cycloalkyl, phenyl, benzyl, (Cx-C4)-alkoxy, (C2-C4)alkenyloxy, (C2-C4)-alkynyloxy, phenyloxy, benzyloxy, (Cx-C4)-alkoxy-(Cx-C4)-alkyl, (Cx-C4)-alkylthio(Cx-C4)-alkyl, halo-(Cx-C4)-alkoxy-(Cx-C4)-alkyl, halo(Cx-C4) -alkylthio- (Cx-C4) -alkyl or halo- (Cx-C4) -alkyl, hydrogen or a radical of the formula -C(O)R4, -SO2R4, -SOR4 or SR4, or NR32 is morpholino, dialkylmorpholino, piperidino, piperazino, hydrazino, hydroxylamino, phthalimido, maleinimido or dihydrophthalimido, or a radical of the formula -A-C (0) R4, where R4 is hydrogen, (Cx-Cg)-alkyl, (C2-C4)-alkenyl, (C2-C4)alkynyl, (C3-C6)-cycloalkyl, phenyl, phenoxy, phenyl5 thio, OH, SH, (Ci-C,) -alkoxy, (C2-C4)-alkyloxy, C2-C4)-alkynyloxy, (Ci-CJ-alkylthio, (C2-C4)-alkenylthio, (C2-CA)-alkynylthio, (C3-C6)-cycloalkylthio, (C3-C6) -cycloalkyloxy, halo- -alkoxy, halo(Cx-C4) -alkylthio, (Cx-C4) -alkoxy- (Cx-C4) -alkyl, (Cx-C4) -alkylthio- (Cx-C4) -alkyl or -NR52, where R5 radicals independently of one another are (Cx-C6)alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C3-C6)cycloalkyl, phenyl, benzyl, hydrogen, (Cx-C4)-alkoxy(Ci-CJ-alkyl, (Cx-C4)-alkylthio-(Cx—CA)-alkyl or NR52 is piperidino, morpholino, piperazino, hydrazino or hydroxylamino, or a radical of the formula -A-SO2R4, -A-SOR4, -A-SR4 or -A-P(O)R42.

In formula (I) and (II), alkyl, alkoxy and alkylthio radicals and the corresponding unsaturated radicals can in each case be straight-chain or branched. Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.

In particular, the invention relates to all stereoisomers and their mixtures which are embraced by formula (I) or (II), but not defined specifically.

The present invention also relates to the process for the preparation of the novel compound of the formula (I) or (II), which comprises reacting a compound of the formula (III) - 6 R1-SO2-CN (III) in which R1 has the meaning mentioned under formulae (I) and (II), with a compound of the formula (IV) R2-NH-NH2 (IV) in which R2 has the meaning described under the formulae (I) and (II), or of a salt of this compound, in a polar solvent, for example H20, CH3OH, C2HSOH or CH3CN, in the presence of a suitable base, for example NaHCO3, K2CO3 or NEt3.

The compounds of the formula (III) can be prepared by various methods alz a2, a3 and a4, which are known from the literature, and by a novel method a5, following the equation below: a, R - SO2Na + XCNC1)_ -4 (0 R1 - SCN + 2 coooh- -> (III)33 R1 - SO2H + -> (III) a4 — PPh3 R1 - + NOCI - -* (III)a5 R1 - SO2CI + LiCN —> (III) (V) - Ί in which R1 radicals are as defined under formulae (I) and (II) and X is Cl or Br.

References (aj-a4): Tetrahedron Lett. Vol. 39, 3351 (1969) .

J. Chem. Soc. Sect. D. Chem. Commun. 1969, 1187.

DE 2,248,940 US 3,755,306 DE 1,930,014 Organic Synthesis Vol. 57, 88 (1977) J. Chem. Soc. Royal Netherlands 94 (1), 12 (1975) J. Chem. Soc., Chem. Commun. 1968, 440.

The compounds of the formulae (I) and (II) according to the invention are distinguished by an outstanding pesticidal, in particular fungicidal, action. Fungal pathogens which have already penetrated the plant tissue can be successfully controlled curatively. This is particularly important and advantageous in the case of those fungal diseases which can no longer be effectively controlled with the other customary fungicides once infection has occurred. The spectrum of action of the claimed compounds embraces a large number of economically important phytopathogenic fungi such as, for example, Pyricularia oryzae, Phytophthora infestans, Plasmopara viticola, Leptosphaeria nodorum and various rusts.

Besides this, the compounds according to the invention are also suitable for use in industrial areas, for example as wood perservatives, preservatives in paints, in cooling lubricants for metalworking, or as preservatives in drilling and cutting oils.

The invention also relates to compositions which contain the compounds of the formula (I) or (II), besides suitable formulation auxiliaries. The compositions according to the invention generally contain 1 to 95 % by weight of the active substances of the formula (I) or (II).

They can be formulated in various ways, depending on the prevailing biological and/or chemico-physical parameters. The following possibilities are therefore suitable for formulation: Wettable powders (WP), emulsifiable concentrates (EC), aqueous dispersions based on oil or water (SC), suspoemulsions (SC), dusts (DP), seed-dressing agents, granules in the form of water-dispersible granules (WG), ULV formulations, microcapsules, waxes or baits.

These individual formulation types are known in principle and described, for example, in: Winnacker-Kiichler, Chemische Technologie [Chemical Technology], Volume 7, C. Hauser Verlag, Munich, 4th Edition 1986; van Falkenberg, Pesticide Formulations Marcel Dekker N.Y., 2nd Ed. 1972-73; K. Martens, Spray Drying Handbook, 3rd Ed. 1979, G. Goodwin Ltd., London.

The formulation auxiliaries required, such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in: Watkins, Handbook of Insecticide Dust Diluents and Carrier, 2nd Ed., Darland Books, Caldwell N.J.; H. v. Olphen, Introduction to Clay Colloid Chemistry, 2nd Ed., J. Wiley & Sons, N.Y.; Mardsen, Solvents Guide, 2nd Ed., Interscience, N.Y. 1950; McCutcheon's Detergents and Emulsifiers Annual, MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, Encyclopedia of Surface Active Agents, Chem. Publ. Co. Inc., N.Y. 1961; Schonfeldt, GrenzflAchenaktive Xthylenoxidaddukte [Surface-Active Ethylene Oxide Adducts], Wiss. Verlags35 gesell., Stuttgart 1916; Winnacker-Kiichler, Chemische Technologie [Chemical Technology], Volume 7, C. Hauser Verlag Munich, 1st Edition, 1986.

Based on these formulations, it is also possible to prepare combinations with other pesticidally active substances, fertilizers and/or growth regulators, for example in the form of a ready mix or a tank mix.

Wettable powders are preparations which are uniformly dispersible in water and which, besides the active substance, also contain wetting agents, for example, polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, alkyl- or alkylphenylsulfonates, and dispersing agents, for example sodium ligninsulfonate, sodium 2,2'dinaphthylmethane-6,6'-disulfonate, sodium dibutylnaphthalenesulfonate and also sodium oleylmethyltaurinate, in addition to a diluent or inert substance. Emulsifiable concentrates can be prepared by dissolving the active substance in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene and also higherboiling aromatics or hydrocarbons, with the addition of one or more emulsifiers. Emulsifiers which can be used are, for example: calcium salts of alkylarylsulfonic acids, such as calcium dodecylbenzenesulfonate or non-ionic emulsifiers, such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide sorbitan fatty acid esters or polyoxyethylene sorbitol esters.

Dusts are obtained by grinding the active substance with finely divided solid substances, for example talc or natural clays, such as kaolin, bentonite or pyrophyllite, or diatomaceous earth. Granules can be produced either by spraying the active substance onto adsorptive, granulated inert material or by applying active substance concentrates onto the surface of carriers such as sand, kaolin35 ites or of granulated inert material, by means of - 10 binders, for example polyvinyl alcohol, sodium polyacrylate or alternatively mineral oils. Suitable active substances can also be granulated in the manner which is conventional for the production of fertilizer granules, if desired in a mixture with fertilizers.

The active substance concentration in wettable powders is, for example, about 10 to 90 % by weight; the remainder to 100 % by weight is composed of conventional formulation components. In the case of emulsifiable concen10 trates, the active substance concentration can be about 5 to 80 % by weight. Formulations in the form of dusts usually contain 5 to 20 % by weight. In the case of granules, the active substance content depends partly on whether the active compound is liquid or solid and on which compound is liquid or solid and on which granulation auxiliaries, fillers etc., are used.

In addition, the active substance formulations mentioned contain, if appropriate, the adhesives, wetting agents, dispersing agents, emulsifiers, penetrants, solvents, fillers or carriers which are conventional in each case.

For use, the concentrates, present in commercially available form, are diluted, if appropriate, in a conventional manner, for example using water in the case of wettable powders, emulsifiable concentrates, dispersions and, in some cases, also in the case of microgranules.

Preparations in the form of dusts and granules and also sprayable solutions are usually not further diluted with other inert substances before use.

The application rate required varies with the external conditions, such as, inter alia, temperature and humidity. It can vary within wide limits, for example between 0.005 and 10.0 kg/ha or more of active ingredient; preferably, however, it is between 0.01 and 5 kg/ha.

The active substances according to the invention can be applied in their commercially available formulations either alone or in combination with other fungicides known from the literature.

Fungicides which are known from the literature and which can be combined according to the invention with the compounds of the formulae (I) and (II) are, for example, the following products : Anilazine, benalaxyl, benodanil, benomyl, binapacryl, 10 bitertanol, buthiobat, captafol, captan, carbendazim, carboxin, CGD-94240 F, chlobenzthiazone, chlorthalonil, cymoxanil, cyproconazole, cyprofuram, dichlofluanid, dichlomezin, diclobutrazol, diethofencarb, difluconazole, dimethirimol, dimethomorph, diniconazole, dinocap, dithianon, dodemorph, dodine, edifenfos, ethirimol, etridiazol, fenarimol, fenfuram, fenpiclonil, fenpropidin, fenpropomorph, fentin acetate, fentin hydroxide, fluaziram, fluobenzimine, fluorimide, flusilazole, flutolanil, flutriafol, folpet, fosetyl-aluminum, fuber20 idazole, furalaxyl, furmecyclox, guazatine, hexaconazole, imazalil, iprobenfos, prodione, isoprothiolane, copper compounds such as copper oxychloride, oxine-copper, copper oxides, mancozeb, maneb, mepronil, metalaxyl, methasulfocarb, methfuroxam, myclobutanil, nabam, nitro25 thalidopropyl, nuarimol, ofurace, oxadixyl, oxycarboxin, penconazol, pencycuron, PP 969, probenazole, probineb, prochloraz, procymidon, propamocarb, propiconazol, prothiocarb, pyracarbolid, pyrifenox, pyroquilon, rabenzazole, sulfur, tebuconazole, thiabendazole, thiofanate30 methal, thiram, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, tricyclazole, tridemorph, triflumizol, triforine, vinchlozolin, zineb, sodium dodecylsulfonate, sodium dodecylsulfate, sodium C13/C15-alcohol ether sulfonate, sodium cetostearyl phosphate, dioctyl35 sodium sulfosuccinate, sodium isopropylnaphthalenesulfonate, sodium methylenebisnaphthalenesulfonate, cetyltrimethylammonium chloride, salts of long-chain primary, secondary or tertiary amines, alkylpropyleneamines, laurylpyrimidinium bromide, ethoxylated quaternized fatty amines, alkyldimethylbenzylammonium chloride and l-hydroxyethyl-2-alkylimidazoline.

The abovementioned components are known active substances, most of which are described in C.R. Worthing, S.B. Walker, The Pesticide Manual, 7th Ed. (1983), British Crop Protection Council.

Moreover, the active substances according to the invention, in particular those of the examples given, can exist in their commercially available formulations and in their use forms, prepared from these formulations, as a mixture with other active substances such as insect15 icides, attractants, sterilants, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. The insecticides include, for example, phosphoric esters, carbamates, carboxylic esters, formamides, tin compounds, substances produced by microorganisms, inter alia. The following are preferred components: 1. from the group of the phosphoric esters azinphos-ethyl, azinphos-methyl, l-(4-chlorophenyl-4-(0ethyl, S-propyl)phosphoryloxypyrazole (TIA 230), chlorpyrifos, coumaphos, demeton, demeton-S-methyl, diazinon, dichlorvos, dimethoate, ethoprophos, etrimfos, fenitrothion, fenthion, heptenophos, parathion, parathion-methyl, phosalone, pirimiphos-ethyl, pirimiphosmethyl, profenofos, prothiofos, sulprofos, triazophos and trichlorphon. 2. from the group of the carbamates aldicarb, bendiocarb, BPMC (2-(1-methylpropyl)phenylmethylcarbamate), butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarb. 3. from the group of the carboxylic esters allethrin, alphamethrin, bioallethrin, bioresmethrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl 2,25 dimethyl-3-(2-chloro-2-trifluoromethylvinyl)-cyclopropanecarboxylate (FMC 54800), fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin, resmethrin, tralomethrin. 4. from the group of the formamidines 10 amitraz and chlordimeform . from the group of the tin compounds azocyclotin, cyhexatin and fenbutatin oxide 6. others abamectin, Bacillus thuringiensis, bensultap, binapacyl, 15 bromopropylate, buprofecin, camphechlor, cartap, chlorbenzilate, chlorfluazuron, 2-(4-chlorophenyl)-4,5diphenylthiophene (UBI-T 930), chlofentezine, 2-naphthylmethyl cyclopropanecarboxylate (Ro 12-0470), cyromacin, DDT, dicofol, N-(3,5-dichloro-4-(l,l,2,2-tetrafluoro20 ethoxy) phenylamino) carbonyl )-2,6-difluorobenzamide (XRD 473), diflubenzuron, N-(2,3-dihydro-3-methyl-l,2thiazol-2-ylidene)-2,4-xylidine, dinobuton, dinocap, endosulfan, fenoxycarb, fenthiocarb, flubenzimine, flufenoxuron, gamma-HCH, hexythiazox, hydramethylnon (AC 217 300), ivermectin, 2-nitromethyl-4,5-dihydro-6Hthiazine (SD 52618), 2-nitromethyl-3,4-dihydrothiazole (SD 35651), 2-nitromethylene-1,3-thiazinan-3-ylcarbamaldehyde (WL 108 471), propargite, teflubenzuron, tetradifon, tetrasul, thiocyclam, triflumaron, and nuclear polyhedrosis and granulosis viruses.

The active substance content of the use forms, prepared from the commercially available formulations, can vary within wide limits, the active substance concentrations of the use forms can be from 0.0001 up to 100 % by weight of active substance, preferably between 0.0001 to 1 % by weight. Application is effected in one of the customary manners adapted to suit the use forms.

The following examples serve to elucidate the invention.

A. Formulation Examples a) A dust is obtained by mixing 10 parts by weight of active substance and 90 parts by weight of talc as inert substance, and comminuting the mixture in a hammer mill. b) A wettable powder which is readily dispersible in water is obtained by mixing 25 parts by weight of active substance, 65 parts by weight of kaolin-containing quartz as inert substance, 10 parts by weight of potassium ligninsulfonate and 1 part by weight of sodium oleoylmethyltaurinate as wetting and dispersing agent, and grinding the mixture in a pinned-disk mill. c) A dispersion concentrate which is readily dispersible in water is prepared by mixing 40 parts by weight of active substance with 1 part by weight of a sulfosuccinic monoester, 2 parts by weight of a sodium ligninsulfonate and 51 parts by weight of water, and grinding the mixture in a ball mill to a fineness of below 5 microns. d) An emulsifiable concentrate can be prepared from 15 parts by weight of active substance, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxethylated nonylphenol (10 EO) as emulsifier. e) Granules can be prepared from 2 to 15 parts by weight of active substance and an inert granule carrier material such as attapulgite, pumice granules and/or quartz sand. It is expedient to use a suspension of the wettable powder from Example b) with a solids content of 30 %, and to spray this suspension onto the surface of attapulgite granules and to dry and intimately mix the batch. The amount of wettable powder here is approximately 5 % by weight, and that of the inert carrier materials approximately 95 % by weight of the finished granules.

B. Chemical Examples Example 7 of Table I n-Propylsulfonyl cyanide 63.7 g (0.447 mol) of n-propyl sulfochloride are added 15 dropwise at 20°C to a solution of 56.4 g (0.447 mol) of Na2SO3 and 75.1 g (0.894 mol) of NaHCO3 in 1000 ml of water. After a clear solution has formed, 55 g (0.894 mol) of liquid C1CN are rapidly added dropwise at 0-5 °C and the mixture is subsequently stirred for 1 hour at 20°C. After extraction with CH2C12, evaporation and distillation, 51.1 g of colorless oil of b.p. 135°C/10 torr are obtained. n22D = 1.4282 Example 55 of Table I N-3,4-Dichlorophenyl-methylsulfonylformamidrazone 4.2 g (0.05 mol) of NaHCO3 are added with ice-cooling to a solution of 5 g (0.048 mol) of methylsulfonyl cyanide and 12.5 g (0.048 mol) of 3,4-dichlorophenylhydrazine hydrochloride in 80 ml of MeOH. When the evolution of gas has ceased, the mixture is poured into ice-water, and solids are filtered off with suction and subsequently purified by stirring with n-heptane.

Yield: 9.9 g of m.p.: 149-151°C (decomp.) Example 28 of Table I N-3-chlorobenzoyl-tosylformamidrazone 4.8 g (0.028 mol) of 3-chlorobenzoyl hydrazide in 15 ml 5 of MeOH are added dropwise at 0°C to a solution of 5 g (0.028 mol) of tosyl cyanide in 50 ml of MeOH. The solution is stirred for 2 hours at 20°C and then poured into ice-water, solids are filtered off with suction and stirred with n-heptane for purification.

Yield: 6.0 g of m.p.: 202-204eC (decomp.) The compounds of the formulae (I) and (II) (see page 1) which are defined in Table I below were obtained analogously.

Table I Ex. No. R1 R2 m.p. (°C) (decomp.) 1 c6h5 ch3 2 II c6h5 3 II 4-CIC6H4 4 41 2,4-CI(2)C6H3 70 - 72 5 ti 3,5-CI(2)C6H3 6 »1 3,4-CI(2)C6H3 7 II 4-Br-CeH4 8 II CH2CeH5 9 It C(O)C6H5 10 4-H3CC(O)NHC6H4 ch3 240 - 242 11 II CeK6 ,E 921836 Ex. No. R1 m.p. (°C) (decomp.) 12 m 4-CIC6H4 155 - 157 13 »1 2,4-CI(2)C6H3 186 - 188 14 « 3,5-CI(2)C6H3 178 - 180 15 »1 3,4-CI(2)C6K3 186 - 188 16 II 4-Br-C6H4 17 4-H3CC(O)NHC6H4 ch2c6h5 180 - 182 18 II Ο(Ο)Ο6Η6 19 4-H3CC6H4 ch3 77 - 79 20 M CeH6 169 - 171 21 H 4-CICeH4 141 - 142 22 μ 2,4-CI(2)C6K3 141 - 143 23 ' 3,5-CI(2)C6K3 148 - 150 24 II 3,4-CI(2)C6H3 150 - 152 25 II 4-BrCeH4 157 - 159 26 II ch2c6h6 94-96 27 II C(O)CeHs 129 - 131 28 II C(O)C6H4-3CI 202 - 204 29 It C(O)CH2C6Hs 131 - 133 30 II C(O)CH2CH3 126 - 128 31 II 3-BrC6H4 132 - 134 32 4-tBuC6H4 ch3 33 II c6h5 135 - 137 34 II 4-CIC6H4 Ex. No. R1 R2 m.p. (°C) (decomp.) 35 M 2,4-CI(2)C6H3 71 - 73 36 II 3,5-CI(2)C6H3 37 II 3,4-CI(2)C6H3 38 H 4-BrCeH4 39 4-tBuC6H4 ch2c6hs 40 II C(O)CeHs 41 4-F3CC6H4 CHa 42 »1 c6h5 43 II 4-CICeH4 44 •1 2,4-CI(2)C6H3 135 - 137 45 II 3,5-CI(2)C6H3 46 II 3,4-CI(2)C6H3 47 II 4-BrC6H4 48 ll ch2c6h5 49 II C(O)C6Hs 50 ch3 ch3 51 II c6h5 52 II 4-CIC6H4 156 - 158 53 II 2,4-CI(2)C6H3 139 - 141 54 II 3,5-CI(2)C6H3 55 II 3,4-CI(2)C6H3 149 - 151 56 II 4-BrC6H4 57 11 ch2c6h5 19-- Ex. No. R1 R2 m.p. (°C) (decomp. )1 58 u C(O)C6H5 59 »1 2,6-CI(2)-4-CF3C6H2 135 - 137 60 C2H5 ch3 61 C2Hs c,h5 62 »1 4-CICeH4 63 h 2,4-CI(2)C6H3 126 - 182 64 M 3,5-CI(2)CeH3 65 ii 3,4-CI(2)CeH3 140 - 142 66 1« 4-BrC6H4 67 II ch2c6h5 68 It C(O)C6H5 69 n-C3H7 ch3 70 II c6h6 71 II 4-CIC6H4 72 II 2,4-CI(2)C6H3 142 - 144 73 II 3,5-CI(2)C6H3 74 3,4-CI(2)C6H3 158 - 160 75 (1 4-Br-CeH4 76 H ch2c6h5 77 n C(O)C6H5 78 4-H3COC6H4 CHg 79 II C6H6 80 II 4-CI-C6H4 Ex. No. R1 R2 m.p. (°C) (decomp.) 81 2,4-CI(2)CeH3 140 * 142 82 *1 3,5-CI(2)C6H3 83 4-H3COCeH4 3,4-CI(2)C6H3 84 II 4-Br CeH4 85 M ch2c6h5 86 II C(O)C6H5 87 4-O2NC6H4 ch3 155 - 157 88 II c6h5 89 »1 4-CIC6H4 90 It 2,4-CI(2)C6H3 91 It 3,5-CI(2)C6H3 92 II 3,4-CI(2)C6H3 93 II 4-BrCeH4 94 II ch2c6h5 95 II C(O)C6H5 96 3-CI, 4-H3C(C6H3) ch3 97 II c6h5 98 II 4-CIC6H4 99 II 2,4-CI(2)C6H3 157 - 159 100 II 3,5-CI(2)C6H3 101 II 3,4-CI(2)C6H3 102 4-BrC6H4 103 II ch2c6h5 104 I II C(O)C6Hs Ex. No. R1 R2 m.p. (°C) (decomp.) 105 3-F3CC6H4 ch3 106 H C,HS 107 U 4-CIC6H4 108 »1 2,4-CI(2)C6H3 197 - 199 109 •1 3,5-CI(2)CeH3 110 II 3,4-CI(2)CeH3 111 II 4-BrC6H4 112 II CHjCgHg 113 II C(O)C6Hs 114 2,4,6-CH3(3)C6H4 ch3 115 tl c6h£ 116 II 4-CIC6H4 117 ii 2,4-CI(2)CeH3 167 - 169 118 II 3,5-CI(2)C6H3 119 II 3,4-CI(2)C6H3 120 II 4-BrC6H4 121 »1 ch2c6h5 122 II C(O)C6Hs 123 c6h5ch2 ch3 124 »1 c6h5 125 II 4-CI C6H4 126 II 2,4-CI(2)C6H3 112- 114 Ex. No. R1 R2 m.p. (°C) (decomp.) 127 c6h5ch2 3,5-CI(2)C6H3 128 II 3,4-CI(2)CeH3 129 H 4-BrCeH4 130 H CH2CeH5 131 It C(O)C,HS 132 4-FC6H4 ch3 133 II CeH6 134 II 4-CIC6H4 146 - 148 135 1, 2,4-CI(2)-C6H3 136 II 3,5-CI(2)C6H3 137 II 3,4-CI(2)C6H3 138 II 4-BrC6H4 139 II ch2c6h5 140 II C(O)C6H5 141 4-Br-C6H4 ch3 142 II c6h6 143 II 4-CIC6H4 144 - 146 144 II 2,4-CI(2)CeH3 145 It 3,5-CI(2)CeH3 146 II 3,4-CI(2)C6H3 147 II 4-BrC6H4 148 It ch2c6h5 Ex. No. R1 R2 m.p. (°C) (decomp.) 149 4-Br-C6H4 C(O)C6H5 150 3,4-CI(2)C6H3 ch3 151 N CeHs 152 »1 4-CIC6H4 142 · 144 153 n 2,4-CI(2)CeH3 154 »» 3,5-CI(2)CeH3 155 II 3,4-CI(2)C6H3 143 - 145 156 n 4-BrC6H4 157 II ch2c6h5 158 II C(O)C6Hs 159 4-nHeC4O-C6H4 ch3 160 II CeH5 161 (1 4-CICeHs 141 - 143 162 It 2,4-CI(2)C6H3 163 •I 3,5-CI(2)C6H3 164 II 3,4-CI(2)C6H3 165 II 4-BrC6H4 166 II ch2c6h5 167 n C(O)C6H5 168 ch3 169 II c6h5 170 II 4-CIC6H4 a Ex . No . R1 R2 m.p.(°C)(decomp.) 171 2,4-C!(2)C6H3 136 - 138 172 II 3,5-CI(2)C5H3 173 II 3,4-CI(2)C6H3 174 II 4-BrC6H4 175 II CH2C6H5 176 II C(O)C6Hs 177 IW ch3 178 It c6h5 179 II 4-CIC6H4 180 (1 2,4-CI(2)C6H3 135 - 137 181 II 3,5-CI(2)C6H3 182 II 3,4-CI(2)C6H3 183 II 4-BrC6H4 184 II CH2C6H5 185 II C(O)C6Hs 186 4-H3CC(O)NCH3C6H4 ch3 187 II c6hs 188 II 4-CIC6H4 189 II 2,4-CI(2)C6H3 188 - 190 190 II 3,5-CI(2)CsH3 191 II 3,4-CI(2)C6H3 192 II 4-BrC6H4 Ex. No. R1 R2 m.p. (°C) (decomp. )| 193 4-H3CC(O)NCH3C6H4 ch2c6h5 194 M C(O)C6Hs C) Biological Examples Example 1 Approximately 5-week-old rice plants cv. Ballila were treated with the compounds according to the invention at the concentrations mentioned below. After the spray coating had dried on, the plants were inoculated uniformly with a spore suspension of Pyricularia oryzae and placed into a darkened controlled-environment cabinet at a temperature of 25°C and 100 % relative atmospheric humidity, where they remained for 48 hours. The rice plants were then grown on in a greenhouse at a temperature of 25°C and 80 % relative atmospheric humidity. The disease was evaluated after 5 days. The disease level was expressed in diseased leaf area compared with untreated, infected control plants. The results are compiled in Table II.

Table II Compound according to Example Leaf areas diseased with Pyricularia oryzae in % at mg of active liter spray liquor substance/ 125 500 250 21 0 0 0 22 0 0 0 23 0 0 0 24 0 0 0 25 0 0 0 55 0 0 0 63 0 0 0 72 0 0 0 99 0 0 0 126 0 0 0 143 0 0 0 untreated, infected plants 100 Example 2 Tomato plants cv. Rheinlands Ruhm in the 3-4-leaf stage were wetted uniformly to runoff point with aqueous suspensions of the compounds according to the invention.

After the plants had dried off, they were inoculated with a Zoosporangia suspension of Phytophthora infestans and kept for 2 days under ideal infection conditions in a controlled-environment cabinet. The plants were then grown on in the greenhouse until the symptoms appeared.

Approx. 1 week after inoculation, the plants were scored for disease. The disease level of the plants was expressed in disease leaf area, relative to untreated infected plants, and is represented in Table III.

Table III Compound according to Example Leaf area diseased with Phytophthora infestans in % at mg of active substance/ liter spray liquor 125 500 250 25 0 0 0 55 0 0 0 15 63 0 0 0 72 0 0 0 143 0 0 0 untreated, 100 20 infected plants Example 3 Approx. 6 weeks after sowing, grapevine seedlings cv. Riesling/Ehrenfelder were treated to runoff point with aqueous suspensions of the compounds according to the invention. After the spray coating had dried on, the plants were inoculated with a Zoosporangia suspension of Plasmopara viticola and, in the dripping wet stage, placed in a controlled-environment cabinet at 23“C and 80-90 % relative atmospheric humidity.

After an incubation time of 7 days, the plants were once more placed in the controlled-environment cabinet overnight so as to stimulate sporulation of the fungus. The disease was then evaluated. The disease level was expressed in diseased leaf area compared with the untreated, infected control plants and is shown in Table IV.

Table IV Compound according to Example Leaf area diseased with Plasmopara viticola in % at mg of active substance/ liter spray liquor 500 250 21 0 0 55 0 0 63 0 0 72 0 0 108 0 0 143 0 0 untreated, 100 infected plants

Claims

1. Patent claims

1. A sulfonylformamidrazone of the formula (I) and tautomers thereof, of the formula (II) NH 2 R’SoR N-NHR 2 (I) R’SO NH J NH-NHR 2 in which 5 R 1 is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, it being possible for the 5 groups independently of one another to be unsubstituted or monosubstituted or polysubstituted by the radicals halogen, cyano, nitro, mono- and 10 dialkylamino, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkenylthio or alkynylthio, or a radical of the formula // (n) R 2 is alkyl, alkenyl, alkynyl, phenyl and benzyl, it being possible for the 5 groups independent15 ly of one another to be unsubstituted or monosubstituted or polysubstituted by the radicals halogen, cyano, nitro, mono- and dialkylamino, alkoxy and haloalkyl, or a radical of the formula -C(O)R 2 or -SO Z R 2 , where R 2 is alkyl, alkenyl, alkynyl, phenyl and benzyl, it being possible for the 5 groups independently of one another to be unsubstituted or monosubstituted or polysubstituted by the radicals halogen, cyano, nitro, mono- and dialkylamino, alkoxy and haloalkyl, n is an integer from 0-5, A is a direct bond, a saturated or unsaturated, branched or unbranched, alkyl chain, Z is hydrogen, halogen, nitro, cyano, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkoxy, alkenyloxy, alkynyloxy, phenyl, phenoxy, haloalkyl, haloalkoxy, alkylthio or haloalkylthio, or a radical of the formula -A-NR 3 2, where R 3 radicals independently of one another are alkyl, alkenyl, alkynyl, cycloalkyl, phenyl, benzyl, alkoxy, alkenyloxy, alkynyloxy, phenyloxy, benzyloxy, alkoxyalkyl, alkylthioalkyl, haloalkoxyalkyl, haloalkylthioalkyl, haloalkyl, hydrogen or a radical of the formula -C(O)R 4 , -S0 2 R*, -SOR* or SR*, or NR 3 2 is morpholino, dialkylmorpholino, piperidino, piperazino, hydrazino, hydroxylamino, phthalimido, maleinimido or dihydrophthalimido, or a radical of the formula -A-C(0)R 4 , where R* is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, phenyl, phenoxy, phenylthio, OH, SH, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkenylthio, alkynylthio, cycloalkylthio, cycloalkoxy, haloalkoxy, haloalkylthio, alkoxyalkyl or alkylthioalkyl, or -NR 5 2, where R 5 radicals independently of one another are alkyl, alkenyl, alkynyl, cycloalkyl, phenyl, benzyl, hydrogen, alkoxyalkyl or alkylthioalkyl, or NR 5 2 is piperidino, morpholino, piperazino, hydrazino or hydroxylamino, or a radical of the formula -A-SO 2 R 4 , -A-SOR*, -A-SR* or -A-P(O)R* 2 .

2. A compound of the formula (I) or (II) as claimed in claim 1, in which R 1 is (Ci-Cg)-alkyl, (C 2 -C 4 )-alkenyl, (C 2 -C 4 )alkynyl, (C 3 -C B )-cycloalkyl or (C 3 -C 6 ) -cycloalkenyl, it being possible for the 5 groups to be independently of one another unsubstituted or monosubstituted or polysubstituted by the radicals halogen, cyano, nitro, mono- and di(Cx-Cg)-alkylamino, (Cx-C 4 )-alkoxy, (C 2 -C 4 ) alkenyloxy, (C 2 -C 4 )-alkynyloxy, (Cx-C 4 )-alkylthio, (C 2 -C 4 )-alkenylthio and (C 2 -C 4 )-alkynylthio, or is a radical of the formula (n) R 2 is (Ci-C 6 )-alkyl, (C 2 -C 4 )-alkenyl, (C 2 -C 4 )alkynyl, phenyl and benzyl, it being possible for the 5 groups independently of one another to be unsubstituted or monosubstituted or polysubstituted by the radicals halogen, cyano, nitro, mono- and di-(C x -C 4 )-alkylamino, (C x -C 4 )-alkoxy or halo-(C x -C 4 )-alkyl, or a radical of the formula -C(O)R 2 ' or -SO 2 R 2 ', where R 2 ‘ is (Ci-Cg)-alkyl, (C 2 -C 4 )-alkenyl, (C 2 -CJ5 alkynyl, phenyl and benzyl, it being possible for the 5 groups independently of one another to be unsubstituted or monosubstituted or polysubstituted by the radicals halogen, cyano, nitro, mono- and di-(C x —C 4 )-alkylamino, (Ci-C*)10 alkoxy or halo-(Cx-CJ-alkyl, n is an integer from 0-5, A is a direct bond, a saturated or unsaturated, branched or unbranched, alkyl chain, Z is hydrogen, halogen, nitro, cyano, (C]-C 6 )15 alkyl, (C 2 -C 4 )-alkenyl, (C 2 -C 4 )-alkynyl, (C 3 -C 6 )cycloalkyl, (C 3 -C 6 )-cycloalkenyl, (Ci-CJ-alkoxy, (C 2 -C 4 )-alkenyloxy, (C 2 -C 4 )-alkynyloxy, phenyl, phenoxy, halo-(Cx-C*)-alkyl, halo-(Cx-C 4 )-alkoxy, (Ci-CJ-alkylthio or halo-(Cx-C 4 )-alkylthio, or 20 a radical of the formula -A-NR 3 2, where R 3 radicals independently of one another are (Cx-Cg)-alkyl, (C 2 -C 4 )-alkenyl, (C 2 -C 4 )-alkynyl, (C 3 -C 6 ) -cycloalkyl, phenyl, benzyl, (Cx-C 4 )25 alkoxy, (C 2 -C 4 )-alkenyloxy, (C 2 -C 4 )-alkynyloxy, phenyloxy, benzyloxy, (Cx-C,,)-alkoxy-(Cx-C 4 )alkyl, (Cx-C 4 )-alkylthio- (Cx-C 4 ) -alkyl, halo(Cj-C 4 ) -alkoxy- (C x -C 4 ) -alkyl, halo- (C x -C 4 ) -alkylthio- (C x -C 4 ) -alkyl or halo-(C x -C 4 )-alkyl, 30 hydrogen or a radical of the formula -C(O)R 4 , -SO 2 R 4 , -SOR* or SR 4 , or NR 3 2 is morpholino, dialkylmorpholino, piperidino, piperazino, hydrazino, hydroxylamino, phthalimido, maleinimido or dihydrophthalimido, or a radical of the formula -A-C (0) R 4 , where R 4 is hydrogen, (Cj-Cg)-alkyl, (C 2 -C 4 )-alkenyl, (C 2 -C 4 )-alkynyl, (C 3 -C 6 )-cycloalkyl, phenyl, phenoxy, phenylthio, OH, SH, (Ci-CJ -alkoxy, (C 2 -C 4 )-alkyloxy, C 2 -C 4 )-alkynyloxy, (C x -C 4 )alkylthio, (C 2 -C 4 )-alkenylthio, (C 2 -C 4 ) -alkynylthio, (C 3 -C 6 )-cycloalkylthio, (C 3 -C 6 )-cycloalkyloxy, halo-(C x -C 4 )-alkoxy, halo-fCi-CJalkylthio, (Ci-CJ-alkoxy-(C x -C 4 )-alkyl, (C x -C 4 )alkylthio-(C x -C 4 ) -alkyl or -NR 5 2, where R 5 radicals independently of one another are (C x —C 6 )—alkyl, (C 2 -C 4 )-alkenyl, (C 2 -C 4 )-alkynyl, (C 3 -C 6 )-eyeloalkyl, phenyl, benzyl, hydrogen, (C x -C 4 ) -alkoxy- (C x -C 4 ) -alkyl, (C x -C 4 ) -alkyl thio(C x -C 4 )-alkyl or NR 5 2 is piperidino, morpholino, piperazino, hydrazino or hydroxylamino, or a radical of the formula -A-SO 2 R 4 , -A-SOR 4 , -A-SR 4 or -A-P(O)R 4 2.

3. A process for the preparation of compounds of the 25 formulae (I) and (II) as claimed in claim 1 or 2, which comprises reacting a compound of the formula (III) R 1 -SO 2 -CN (III) in which R 1 has the meaning mentioned under for30 mulae (I) and (II), with a compound of the formula (IV) R 2 -NH-NH 2 (IV) in which R 2 has the meaning described under formulae (I) and (II), or of a salt of this compound, in a polar solvent in the presence of a suitable 5 base.

4. A pesticide which comprises an effective amount of a compound of the formula I or II as claimed in claim 1 or 2, and the customary formulation aids.

5. A fungicidal agent, which comprises an effective 10 amount of a compound of the formula I or II as claimed in claim 1 or 2, and the customary formulation aids .

6. The use of compounds of the formula I or II as claimed in claim 1 or 2 for controlling pests of 15 plants.

7. The use of compounds of the formula I or II as claimed in claim 1 or 2 for controlling pathogenic fungi.

8. A method of controlling pests of plants, which com20 prises applying an effective amount of a compound of the formula I or II as claimed in claim 1 or 2 to these pests or to the plants, areas or substrates which are attacked by them.

9. A method of controlling pathogenic fungi, which com25 prises applying an effective amount of a compound of the formula I or II as claimed in claim 1 or 2 to these fungi or to the plants, areas or substrates which are attacked by them. 10.

10.

11. . 11 .

12. 12.

13. 13.

14. 14.

15. 15.

16. 16. A compound as claimed in claim 1, substantially as hereinbefore described and exemplified. A process for the preparation of a compound as claimed in claim 1, substantially as hereinbefore described and exemplified. A compound as claimed in claim 1, whenever prepared by a process claimed in claim 3 or 11. A pesticide according to claim 4, substantially as hereinbefore described and exemplified. A fungicidal agent according to claim 5, substantially as hereinbefore described and exemplified. Use according to claim 6 or 7, substantially as hereinbefore described. A method according to claim 8 or 9, substantially as hereinbefore described and exemplified.