United9 States Patent Office 3,845,171E. 1. 2 3 3,845,171 (3) / O-ETHYL-S-n PROPYL-S-CARBAMOYLALKYL (C2H5O)2P-S CH-CON -- (R)3N E rnstREFESSEE Beriger, Grabenmattweg 29,29 Y, Aishwil, Switzerland 5 (IV) (XIV) No Drawing. Filed Dec. 18, 1972, Ser. No. 315,973 Claims priority, application Switzerland, Dec. 24, 1971, 18,909/71; Nov. 3, 1972, 16,041/72 CH5 Int, C.A01n 9/36, C07f 9/16 (R0. Go s R U.S. C. 260-943 4 Claims 0 D-S-CH-C oNC -- (n) C3HHal ABSTRACT OF THE DISCLOSURE CH5O R S-carbamoylalkyl-O-ethyl - S - (n)-propyldithiophos-- (XV)XV (IX)X phoric esters having the formula 5 CEO O R. YP-S-CH-C O-N In the formulae II to XV, R1 and R have the mean ings given for the formula I and R4 represents a lower 20 alkyl radical, X represents oxygen or sulphur, Hal rep resents fluorine, chlorine, bromine or iodine, in particul wherein R represents hydrogen, methyl or allyl and R2 lar chlorine, and Me represents ammonium, alkyl-am represents -CHOCH, -CHAOCH, -CHsOCH3, monium or an alkali metal. Processes 1, 2 and 3 can be - CHCN, CHCN, -OCH or allyl a process for their carried out at normal pressure, at a temperature of 0-80 manufacture and their use in pest control. 25 C., preferably 20-50° C., and in solvents and diluents which are inert towards the reactants. The present invention relates to S-carbamoylalkyl-O- Examples of suitable solvents or diluents are: ether and ethyl - S - (n)-propyl dithiophosphoric esters, a process ethereal compounds, such as diethyl ether, dipropyl ether, for their manufacture and their use in pest control. dioxan, tetrahydrofuran; amides, such as N,N-dialkylated The S-carbamoylalkyl-O-ethyl-S-(n)- propyl - dithio- 30 carboxylic amides; aliphatic, aromatic and halogenated phosphoric esters have the formula hydrocarbons, in particular benzene, toluene, Xylenes, chloroform, chlorobenzene; nitriles, such as acetonitrile. Some of the starting materials of the formulae II, III CEO R and IV are known or they can be manufactured by meth P-S-OH,- C o-N 35 ods analogous to those known in the art. (n) C3H S R (I) The active substances of the formula I are suitable for combating animal and plant pests of the most diverse wherein R represents hydrogen, methyl or allyl and R2 kinds and can be used partly as well for regulating repris. cE"bch, -CHAOCH3, S. 3 CHOCH3,36 40 growth,The insecticidal aS abscission action agents of analogousand defoliants. compounds is disa The compounds of the formula I can be manufactured closed in the literature, but by comparison the com by methods which are known per se, e.g. as follows: pounds of the formula I have surprisingly a markedly stronger and more lasting action against all development stages, such as eggs, nymphs, pupae and adults, of insects, () C.H.0, R. 45 such for example as those of the families: P-SMe -- HalCE-CON - Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tetti (n) C.H.'s? Y, goniidae, Cimicidae, Phyrrhocoridae, Reduviidae, Aphi (II) (III) didae, Delphacidae, Diaspididae, Pseudoccidae, Chrysome lidae, Coccinellidae, Bruchidae, Scarabaeidae, Dermes (2) s R. s 50 tidae, Tenebrionidae, Curculionidae, Tineidae, Noctuidae, YX w. o Lymantriidae, Pyralidae, Galleriidae, Cuicidae, Tipuli (CH5O)2P-S CH-CON -- ROC-SMe (W) dae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae, R or Pulicidae. (IV) The compounds of the formula I also act against eggs, MeSR (VI) 55 larvae and adults of representatives of the order Acarina, or -- (n) C3HHal (IX) such as mites, spider mites and ticks, e.g. of the families Mes (VII) Ixodidae, Argasidae, Tetranychidae and Demanyssidae. By addition of other insecticides and/or acaricides it is (R,0)-sMe (VIII) possible to broaden substantially the insecticidal or X 60 acarcicidal action and to adapt it to given circumstances. S The following active substances are examples of suit able additives: RO t-s Cats (X) O Organic Phoshporus Compounds C2H5SR (XI) 65 Bis-O,O-diethylphosphoric acid anhydride (TEPP) -- Dimethyl-(2,2,2-trichloro-1-hydroxyethyl)-phosphonate 0. (TRICHLORFON) m CH5S CH (XII) 1,2-dibromo-2,2-dichloroethyldimetyhlphosphate Or (NALED) (R0)--sc.H. (XIII) 70 2,2-dichlorovinyldimethylphosphate2-methoxycarbamyl-1-methylvinyldimethylphosphate (DICHLORVOS) (MEVINPHOS)

3,845,171 5 6 O,O-diethyl-7-hydroxy-3,4-tetramethylene-coumarinyl 2-cyclohexyl-4,6-dinitrophenyl Dinex thiophosphate (COUMITHOATE) 2-(1-methylheptyl)-4,6-dinitrophenyl-crotonate Dino 2-methoxy-4-H-1,3,2-benzodioxaphosphorin-2-sulphide cap O,O-diethyl-O-(5-phenyl-3-isooxazolyl)thiophosphate 2-sec.-butyl-4,6-dinitrophenyl-3-methyl-butenoate 2-(diethoxyphosphinylimino)-4-methyl-1,3-dithiolane Binapacryl tris-(2-methyl-1-aziridinyl)-phosphine oxide (METEPA) 5 2-sec.-butyl-4,6-dinitrophenyl-cyclopropionate S-(2-chloro-1-phthalimidoethyl)-O,O-diethyldithio 2-sec.-butyl-4,6-dinitrophenylisopropylcarbonate Dino phosphate buton N-hydroxynaphthalimido-diethylphosphate Miscellaneous dimethyl-3,5,6-trichloro-2-pyridylphosphate O pyrethin I O,O-dimethyl-O-(3,5,6-trichloro-2-pyridyl)thiophos pyrethin II phate 3-allyl-2-methyl-4-oxo-2-cyclopentan-1-yl-chrysan S-2-(ethylsulphonyl)ethyl dimethylthiolphosphate (DI themumate (Allerthrin) OXYDEMETON-S-METHYL) 6-chloropiperonyl-chrysanthemumate (Barthrin) diethyl-S-2-(ethylsulphinyl)ethyl dithiophosphate (OXI 5 2,4-dimethylbenzyl-chrysanthemumate (Dimethrin ) DISULFOTON) 2,3,4,5-tetrahydrophthalimidomethylchrysanthemumate bis-O,O-diethylthiophosphoric acid anhydride (SUL 4-chlorobenzyl-4-chlorophenylsulphide Chlorobensid FOTEP) 6-methyl-2-oxo-1,3-dithiolo-4,5-bloguinoxaline (Quino dimethyl-1,3-di(carbomethoxy)-1-propen-2-yl-phosphate methionate) dimethyl-(2,2,2-trichloro-1-butyroyloxyethyl)phosphate 20 (I)-3-(2-furfuryl)-2-methyl-4-oxocyclopent-2-enyl(I)- (BUTONATE) (cis--trans)-chrysanthemum-monocarboxylate O,O-dimethyl-O-(2,2-dichloro-1-methoxy-vinyl)phos Furethrin phate 2-pivaloyl-indane-1,3-dione Pindon bis-(dimethylamido) fluorphosphate (DIMEFOX) N'-(4-chloro-2-methylphenyl)-N,N-dimethylform 3,4-dichlorobenzyl-triphenylphosphoniumchloride 25 amidine Chlorophenamidin dimethyl-N-methoxymethylcarbamoylmethyl-dithiophos 4-chlorobenzyl-4-fluorophenyl-sulphide Fluorobenside phate (FORMOCARBAM) 5,6-dichloro-1-phenoxycarbamyl-2-trifluoromethyl-benz O,O-diethyl-O-(2,2-dichloro-1-chloroethoxyvinyl) phos imidazole Fenozafor phate p-chlorophenyl-p-chlorobenzenesulphonate Ovex O,O-dimethyl-O-(2,2-dichloro-1-chloroethoxyvinyl) 30 p-chlorophenyl-benzenesulphonate Fenson phosphate p-chlorophenyl-2,4,5-trichlorophenylsulphone Tetradi O-ethyl-S,S-diphenyldithiolphosphate fon O-ethyl-S-benzyl-phenyldithiophosphonate p-chlorophenyl-2,4,5-trichlorophenylsulphide Tetrasul O,O-diethyl-S-benzyl-thiolphosphate p-chlorobenzyl-p-chlorophenylsulphide Chlorobenside O,O-dimethyl-S-(4-chlorophenylthiomethyl) dithiophos 2-thio-1,3-ditiholo-(5,6)-quinoxaline Thiochinox phate (METHYLCARBOPHENOTHION) O,O-dimethyl-S-(ethylthiomethyl) dithiophosphate prop-2-ynyl-(4-t-butylphenoxy)-cyclohexylsulphite diisopropylaminofluorphosphate (MIPAFOX) Propargil. O,O-dimethyl-S-(morpholinylcarbamoylmethyl) dithio Formamidines MORPHOTHION) 40 1-dimethyl-2-(2-methyl-4'-chlorophenyl)-formamidine bismethylamido-phenylphosphate (CHLORPHENAMIDIN) O,O-dimethyl-S-(benzenesulphonyl) dithiophosphate 1-methyl-2-(2-methyl-4'-chlorophenyl)-formamidine O,O-dimethyl-(S and O)-ethylsulphinylethylthiophos 1-methyl-2-(2-methyl-4'-bromophenyl)-formamidine phate 1-methyl-2-(2,4'-dimethylphenyl)-formamidine O,O-diethyl-O-4-nitrophenylphosphate 1-n-butyy-1-methyl-2-(2-methyl-4'-chlorophenyl)-form triethoxy-isopropoxy-bis(thiophosphinyl) disulphide amidine 2-methoxy-4H-1,3,2-benzodioxaphosphorin-2-oxide 1-methyl-1-(2-methyl-4'-chloroaniline-methylene)- octamethylpyrophosphoramide (SCHRADAN) formamidine bis-(dimethoxythiophosphinylsulphido)-phenylmethane 2-(2'-methyl-4'-chlorophenyl-formamidine N,N,N',N'-tetramethyldiamidofluorophosphate (DI 50 1-n-butyl-2-(2-methyl-4'-chlorophenyl-imino)pyrol MEFOX) idine. O-phenyl-O-p-nitrophenyl-methanethiophosphate Urea (COLEP) N-2-methyl-4-chlorophenyl-N,N-dimethyl-thiourea. O-methyl-O-(2-chloro-4-tert.butyl-phenyl)-N-methyl amidothiophosphate (NARLENE) Carbamates O-ethyl-O-(2,4-dichlorophenyl)-phenylthiophosphate 1-naphthyl-N-methylcarbamate (CARBARYL) O,O-diethyl-O-(4-methylmercapto-3,5-dimethylphenyl)- 2-butinyl-4-chlorophenylcarbamate thiophosphate 4-dimethylamino-3,5-xylyl-N-methylcarbamate 4,4'-bis-(O,O-dimethylthiophosphoryloxy)-diphenyl di 4-dimethylamino-3-tolyl-N-methylcarbamate sulphide 60 (AMINOCARB) O,O-di-(B-chloroethyl)-O-(3-chloro-4-methyl-cou 4-methylthio-3,5-xylyl-N-methylcarbamate (METHO marinyl-7)phosphate CARB) S-(1-phthalimidoethyl)-O,O-diethyldithiophosphate 3,4,5-trimethylphenyl-N-methylcarbamate O,O-dimethyl-O-(3-chloro-4-diethylsulphamylphenyl)- 2-chlorophenyl-N-methylcarbamate (CPMC) thiophosphate 65 5-chloro-6-oxo-2-norborane-carbonitrile-O-(methylcarb O-methyl-O-(2-carbisopropoxyphenyl)-amidothiophos amoyl)-oxime phate 1-(dimethylcarbamoyl)-5-methyl-3-pyrazolyl-N,N-di 5-(O,O-dimethylphosphoryl)-6-chloro-bicyclo(3.2.0)- methylcarbamate (DIMETILAN) heptadiene(1,5) 2,3-dihydro-2,2-dimethyl-7-benzofuranyl-N-methylcarba O-methyl-O-(2-i-propoxycarbonyl-1-methylvinyl)-ethyl 70 mate (CARBOFURAN) amidothiophosphate. 2-methyl-2-methylthio-propionaldehyde-O-(methyl carbamoyl)-oxime (ALDICARB) Nitrophenols and Derivatives 8-quinaldyl-N-methylcarbamate and its salts 4,6-dinitro-6-methylphenol, sodium salt Dinitrocresoll methyl-2-isopropyl-4-(methylcarbamoyloxy) carbanilate dinitrobutylphenol-(2,2'2')-triethanolamine Salt 5 m-(1-ethylpropyl)phenyl-N-methylcarbamate 3,845,171 7 8 3,5-di-tert-butyl-N-methylcarbamate 3,5-dimethyl-4-methoxycarbonylamino-phenyl-N-methyl m-(1-methylbutyl)phenyl-N-methylcarbamate carbamate 2-isopropylphenyl-N-methylcarbamate 2-y-methylthiopropylphenyl-N-methyl-carbamate 2-sec.butylphenyl-N-methylcarbamate 3-(o-methoxymethyl-2-propenyl)-phenyl-N-methyl m-tolyl-N-methylcarbamate carbamate 2,3-xylyl-N-methylcarbamate 2-chloro-5-tert.-butyl-phenyl-N-methyl-carbamate 3-isopropylphenyl-N-methylcarbamate 4-(methyl-propargylamino)-3,5-xylyl-N-methyl-carba 3-tert.butylphenyl-N-methylcarbamate nate 3-sec.butylphenyl-N-methylcarbamate 4(methyl-y-chloroallylamino)-3,5-xylyl-N-methyl-carba 3-isopropyl-5-methylphenyl-N-methylcarbamate O mate (PROMECARB) 4-(methyl-3-chloroallylamino)-3,5-xylyl-N-methyl-carba 3,5-diisopropylphenyl-N-methylcarbamate mate 2-chloro-5-isopropylphenyl-N-methylcarbamate 1-(3-ethoxycarbonylethyl)-3-methyl-5-pyrazolyl-N,N- 2-chloro-4,5-dimethylphenyl-N-methylcarbamate dimethylcarbamate 2-(1,3-dioxolan-2-yl)phenyl-N-methylcarbamate 5 3-methyl-4-(dimethylamino-methylmercapto-methylene (DIXOXACARB) imino)phenyl-N-methylcarbamate 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl-N-methyl 1,3-bis(carbamoylthio)-2-(N,N-dimethylamino)-pro carbamate panehydrochloride 2-(1,3-dioxolan-2-yl)phenyl-N,N-dimethylcarbamate 5,5-dimethylhydroresorcinoldimethylcarbamate 2-(1,3-dithiolan-2-yl)-N,N-dimethylcarbamate 20 2-ethyl-propargylaminol-phenyl-N-methylcarbamate 2-(1,3-dithiolan-2-yl)phenyl-N,N-dimethylcarbamate 2-methyl-propargylamino]-phenyl-N-methylcarbamate 2-isopropoxyphenyl-N-methylcarbamate (APROCARB) 4-dipropargylamino)-3-tolyl-N-methylcarbamate 2-(2-propinyloxy)phenyl-N-methylcarbamate 4-dipropargylaminol-3,5-xylyl-N-methylcarbamate 3-(2-propinyloxy)phenyl-N-methylcarbamate 2-allyl-isopropylamino)-phenyl-N-methylcarbamate 2-dimethylaminophenyl-N-methylcarbamate 25 3-allyl-isopropylamino]-phenyl-N-methylcarbamate 2-diallylaminophenyl-N-methylcarbamate 4-diallylamino-3,5-xylyl-N-methylcarbamate (ALLYXI Chlorinated Hydrocarbons CARB) ?y-hexachlorocyclohexane GAMMEXANE; LINDAN; 4-benzothienyl-N-methylcarbamate ?y HCH 2,3-dihydro-2-methyl-7-benzofuranyl-N-methylcarbamate 30 1,2,4,5,6,7,8,8-octachloro-3ox,4,7,7a"tetrahydro-4,7-meth 3-methyl-1-phenylpyrazol-5-yl-N,N-dimethylcarbamate ylene indane (CHLORDAN) 1-isopropyl-3-methylpyrazol-5-yl-N,N-dimethylcarbamate 1,4,5,6,7,8,8-heptachloro,3ox,4,7,7a-tetrahydro-4,7-methyl (ISOLAN) ene indane HEPTACHLOR 2-dimethylamino-5,6-dimethylpyrimidin-4-yl-N,N-di 1,2,3,4,10,10-hexachloro-1,4,4-ox,5,8,8oz-hexahydro-endo methyl-carbamate 35 1,4-exo-5,8-dimethanonaphthalene ALDRIN 3-methyl-4-dimethylaminomethyleneiminophenyl-N- 1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4oz,5,6,7,8,8oz methylcarbamate octahydro-exo-1,4,endo-5,8-dimethanonaphthalene 3,4-dimethylphenyl-N-methylcarbamate DIFLORIN 2-cyclopentylphenyl-N-methylcarbamate 1,2,3,4,10,10-hexachloro-5,7-epoxy-1,4,4oz,5,6,7,8,8oz 3-dimethylamino-methyleneiminophenyl-N-methylcarba 40 octylhydro-endo-endo-5,8-dimethanonaphthalene mate (FORMETANATE) and its salts 1-methylthio-ethylimino-N-methylcarbamate ENDRIN (METHOMYL) In addition to the properties cited hereinabove, the 2-methylcarbamoyloximino-1,3-dithiolane compounds of the formula I also act against representa 5-methyl-2-methylcarbamoyloximino-1,3-oxythiolane tives of the division Thallophyta. Thus a number of these 2-(1-methoxy-2-propoxy) phenyl-N-methylcarbamate compounds display bactericidal action; but they are also 2-(1-butin-3-yl-oxy)phenyl-N-methylcarbamate active against fungi, e.g. against phytopathogenic fungi be 1-dimethylcarbamyl-1-methylthio-O-methylcarbamyl longing to the following classes: Oomycetes, Zygomycetes, formoxime Ascomycetes, Basidiomycetes, Denteromycetes. The com 1-(2-cyanoethylthio)-O-methylcarbamyl-acetaldoxime 50 pounds of the formula I are also suitable for combating 1-methylthio-O-carbamyl-acetaldoxime plant pathogenic nematodes. O-(3-sec.butylphenyl)-N-phenylthio-N-methylcarbamate The compounds of the formula I also possess in part 2,5-dimethyl-1,3-dithiolane-2-(O-methylcarbamyl)- herbicidal properties and are suitable in particular for aldoxime combating grass-like and latifoliate weeds in various crop O-2-diphenyl-N-methylcarbamate 55 plant cultures. When used in high concentrations the new 2-(N-methylcarbamyl-oximino)-3-chloro-bicyclo[2.2.1 compounds act as total herbicides; on the other hand, heptane when used in lower concentrations they act as selective 2-(N-methylcarbamyl-oximino)-bicyclo[2.2.1]heptane herbicides. Deep rooted, difficultly combatable weeds 3-isopropylphenyl-N-methyl-N-chloroacetal-carbamate which are one or more years old are successfully damaged 3-isopropylphenyl-N-methyl-N-methylthiomethyl-carba 60 in their growth or destroyed by the active substances of mate the formula I. The new active substances can be applied O-(2,2-dimethyl-4-chloro-2,3-dihydro-7-benzofuranyl)-N- with the same good success before germination (pre methylcarbamate emergence) and after germination (postemergence). Thus O-(2,2,4-trimethyl-2,3-dihydro-7-benzofuranyl)-N-meth meadow weeds, for example millet species (Panicum spp.), ylcarbamate 65 mustard species (Chenopodiaceae), slender foxtail (alope O-naphthyl-N-methyl-N-acetalcarbamate curus spp.) and other foxtail species, e.g. Amarantus spp., O-5,6,7,8-tetrahydronaphthyl-N-methyl-carbamate grasses, e.g. Lolium spp., Compositae, e.g. Taraxacum. 3-isopropyl-4-methylthio-phenyl-N-methylcarbamate spp., camomile species (Matricaria spp.), are destroyed or 3,5-dimethyl-4-methoxy-phenyl-N-methylcarbamate hindered in their growth without damage being caused to 3-methoxymethoxy-phenyl-N-methylcarbamate 70 cultivated plants, such as cereals, maize, cotton, sorghum, 3-allyloxyphenyl-N-methylcarbamate Soya beans and sugar beet. The rates of application vary 2-propargyloxymethoxy-phenyl-N-methyl-carbamate and are dependent on the time of application; they are 2-allyloxyphenyl-N-methyl-carbamate between 0.1 to 10 kg. of active substance per hectare, on A-methoxycarbonylamino-3-isopropylphenyl-N-methyl preemergence application up to 1 kg. per hectare and on carbamate 75 postenergence 3 to 10 kg. of active substance per hectare. 3,845,171 10 In order to totally destroy entire crops of weeds, for ex favourable predeterminable adsorption/desorption ratio, ample on fallow land neighbouring on the cultivated areas, with the active substances, for example in the form of it is necessary to use more than 10 kg. per hectare. The their solutions (in a low boiling solvent) and to remove usual crop rotation may proceed on application of the the solvent. Polymer granules of this kind in the form of new active substances without any detrimental effects. microgranules having a bulk density of 300 g./liter to In order to broaden the activity spectrum it is also pos 5 600 g/liter can also be manufactured with the aid of sible to admix the active substances of the formula I with atomisers. The dusting can be carried out from aircraft other herbicides, for example from the series of the tri over extensive areas of cultures of useful plants. azines, such as halogeno-diamino-s-triazines, alkoxy- and It is also possible to obtain granules by compacting the alkylthio-diamino-s-triazines, triazoles, diazines, such as O carrier with the active substance and carriers and subse uraciles, aliphatic carboxylic acids and halocarboxylic quently comminuting the product. acids, halogenated benzoic acids and phenylacetic acids, To these mixtures can also be added additives which aryloxyalkanecarbocylic acids, hydrazides, amides, nitriles, stabilise the active substance and/or non-ionic, anionic and esters of such carboxylic acids, carbamic and thiocarbamic cationic surface active substances, which, for example, im esters, ureas etc. prove the adhesion of the active ingredients on plants or The compounds of the formula I may be used as pure parts of plants (adhesives and agglutinants) and/or ensure active substance or together with suitable carriers and/or a better wettability (wetting agents) and dispersibility (dis additives. Suitable carriers and additives can be solid or persing agents). Examples of suitable adhesives are the liquid and correspond to the substances conventionally following: olein/chalk mixture, cellulose derivatives used in formulation technique such, for example, as Sol (methyl cellulose, carboxymethyl cellulose), hydroxyethyl vents, dispersants, wetting agents, adhesives, thickeners, glycol ethers of monoalkyl and dialkyl phenols having 5 binders and/or fertilisers. to 15 ethylene oxide radicals per molecule and 8 to 9 For application, the compounds of the formula I may carbon atoms in the alkyl radical, lignin sulphonic acids, be processed to dusts, emulsion concentrates, granules, dis their alkali metal and alkaline earth metal salts, polyethyl persions, sprays, to solutions, or suspensions, in the con 25 ene glycol ethers (carbowaxes), fatty alcohol polyethylene ventional formulation which is commonly employed in glycol ethers having 5 to 20 ethylene oxide radicals per application technology. Mention may also be made of molecule and 8 to 18 carbon atoms in the fatty alcohol cattle dips and spray races, in which aqueous preparations moiety, condensation products of ethylene oxide/propyl are used. ene oxide, polyvinyl pyrrolidones, polyvinyl alcohols, con The agents according to the invention are manufactured 30 densation products of urea and formaldehyde, and also in known manner by intimately mixing and/or grinding latex products. active substances of the formula with the suitable car The water-dispersible concentrates of the active sub riers, optionally with the addition of dispersants or sol stance, i.e. wettable powders, pastes and emulsifiable con vents which are inert towards the active substances. The centrates, are agents which can be diluted with water to active substances may take, and be used in, the follow any concentration desired. They consist of active sub ing forms. stance, carrier, optionally additives which stabilise the active substance, Surface-active substance and anti-foam Solid forms: agents and, optionally, solvents. Dusts, tracking agents, granules, coated granules, impreg Wettable powders and pastes are obtained by mixing nated granules and homogeneous granules. 40 and grinding the active substances with dispersing agents and pulverulent carriers in suitable apparatus until homo Liquid forms: geneity is attained. Suitable carriers are, for example, those mentioned for the solid forms of application. In (a) active substances which are dispersible in water: wet Some cases it is advantageous to use mixtures of different table powders, pastes, emulsions; carriers. As dispersing agents there can be used, for ex (b) solutions. ample, condensation products of sulphonated naphthalene To manufacture solid forms (dusts, tracking agents), and sulphonated naphthalene derivatives with formalde the active substances are mixed with solid carriers. Suit hyde, condensation products of naphthalene or naphtha able carriers are, for example: kaolin, talcum, bolus, loess, lene sulphonic acids with phenol and formaldehyde, as chalk, limestone, ground limestone, attaclay, dolomite, 50 well as alkali, ammonium and alkaline earth metal salts diatomaceous earth, precipitated silica, alkaline earth sili of lignin sulphonic acid, in addition, alkylaryl sui cates, sodium and potassium aluminium silicates (feldspar phonates, alkali and alkaline earth metal salts of dibutyl and mica), calcium and magnesium sulphates, magnesium naphthalene sulphonic acid, fatty alcohols sulphates such oxide, ground synthetic materials, fertilisers, for example as salts of sulphated hexadecanols, heptadecanols, octa ammonium sulphate, ammonium phosphate, ammonium 55 decanols, and salts of sulphated fatty alcohol glycol nitrate, urea, ground vegetable products, Such as corn ethers, the sodium salt of oleoyl ethionate, the sodium meal, bark dust, sawdust, nutshell meal, cellulose powder, salts of oleoyl methyl tauride, ditertiary acetylene glycols, residues of plant extractions, activated charcoal etc. These dialkyl dilauryl ammonium chloride and fatty acid alkali substances can either be used singly or in admixture with and alkaline earth metal salts. one another. 60 Suitable anti-foam agents are silicones. Granules can be very easily manufactured by dissolv The active substances are mixed, ground, sieved and ing an active substance of the formula I in an organic strained with the additives cited hereinabove in such a solvent and applying the resulting solution to a granulated manner that, the size of the solid particles does not exceed material, for example attapulgite, SiO2, granicalcium, 0.02 to 0.04u in wettable powders, and 0.03p, in pastes. bentonite etc. and then evaporating the solvent. 65 To produce emulsifiable concentrates and pastes, Polymer granules can also be manufactured by mixing dispersing agents such as those cited above, organic the active substances of the formula I with polymerisable solvents, and water are used. Examples of suitable compounds (urea/formaldehyde; dicyandiamide/formal solvents are: alcohols, benzene, xylene, toluene, dimethyl dehyde; melamine formaldehyde or others), whereupon sulphoxide, and mineral oil fractions which boil between a mild polymerisation is carried out that does not affect 70 120 and 350° C. The solvents must be practically odour the active substances and in the process of which the less, not phytotoxic, and inert to the active substances. granulation is carried out during the gel formation. It is Furthermore, the agents according to the invention can more advantageous to impregnate finished, porous poly be applied in the form of solutions. For this purpose the mer granules (urea/formaldehyde, polyacrylonitrile, poly active substances, or several active substances of the ester or others) which have a specific Surface area and a 5 general formula I, are dissolved in suitable organic 3,845,171 11 12 solvents, mixtures of solvents or in water. Aliphatic and (d) aromatic hydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes, and mineral oils, singly or in admix 10 parts of active substance, ture with each other, can be used as organic solvents. 3 parts of a mixture of the sodium salts of saturated fatty The content of active substance in the above described alcohol Sulphates, agents is between 0.1% to 95%, in which connection it 5 5 parts of naphthalenesulphonic acid/formaldehyde should be mentioned that, in the case of application from condensate, aircraft or some other suitable means of application, it 82 parts of kaolin, is possible to use concentrations of up to 99.5% or even The active substances are intimately mixed, in suitable pure active substance. O mixers, with the additives, the mixture being then ground The active substances of the formula I can, for ex in the appropriate mills and rollers. Wettable powders are ample, be formulated as follows: obtained which can be diluted with water to give suspen Dusts sions of any desired concentration. The following Substances are used to manufacture (a) 15 Emulsifiable Concentrates a 5% and (b) a 2% dust: The following substances are used to produce (a) a (a) 10% and (b) a 25% emulsifiable concentrate: 5 parts of active substance 20 (a) 95 parts of talcum 10 parts of active substance, (b) 3.4 parts of epoxidised vegetable oil, 13.4 parts of a combination emulsifier consisting of fatty 2 parts of active substance 25 alcohol polyglycol ether and alkylarylsulphonate 1 part of highly disperse silicic acid calcium salt, 97 parts of talcum. 40 parts of dimethylformamide, The active substances are mixed with the carriers and 43.2 parts of Xylene. grounds. (b) Granules 30 25 parts of active substance, The following substances are used to produce 5% 2.5 parts of epoxidised vegetable oil, granules: 10 parts of an alkylarylsulphonate/fatty alcohol-polygly col ether mixture 5 parts of active substance, 5 parts of dimethylformamide, 0.25 parts of epichlorohydrin, 57.5 parts of xylene. 0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, From these concentrates it is possible to produce, by 91 parts of kaolin (particle size 0.3-0.8 mm.). dilution with water, emulsions of any desired concen tration. The active substance is mixed with epichlorohydrin and 40 Spray dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The thus ob The following constituents are used to prepare a 5% tained solution is sprayed on kaolin, and the acetone sub Spray: sequently evaporated in vacuo. 5 parts of active substance, Wettable Powder 1 part of epichlorohydrin, 94 parts of benzine (boiling limits 160-190° C.). The following constituents are used for the preparation of (a) a 40%, (b) and (c) a 25%, and (d) a 10% EXAMPLE 1. wettable powder: 50 O-ethyl-S-propyl-S-(2-methoxyethylcarbamoylmethyl)- (a) dithiophosphoric ester 40 pars of active substance, 5 parts of sodium lignin sulphonate, 1 part of sodium dibutyl-naphthalene sulphonate, 54 parts of silicic acid. CEO (b) P-s CHCONHCHAOCH 25 parts of active substance, (n) C3H S 4.5 parts of calcium lignin sulphonate, 60 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 1.5 parts of sodium dibutyl naphthalene sulphonate, 30.3 g of chloroacetic-N-(2-methoxyethyl)-amide and 19.5 parts of silicic acid, 41 g, of the potassium salt of O-ethyl-S-propyl-thio-phos 19.5 parts of Champagne chalk, 65 phoric acid are stirred overnight at room temperature 28.1 parts of kaolin. in 200 ml. of acetonitrile and the mixture is subsequently (c) heated to the boil under reflux for 3 hours. After the mixture has cooled, the salts are filtered off with suction, 25 parts of active substance, the solvent is evaporated in vacuo and the residue is taken 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 70 up in 100 ml. of methylene chloride and washed in suc 1.7 parts of Champagne chalk/hydroxyethyl cellulose cession with 30 ml of normal sodium hydroxide solution mixture (1:1), and 30 ml. of water. The solvent is distilled off in vacuo 8.3 parts of sodium aluminium silicate, at 40-50 C. bath temperature to leave as residue 41.5 16.5 parts of kieselguhr, g. of phosphorus ester of the above described formula 46 parts of kaolin. with a refraction of n26=1.5115. 3,845,171 13 14 The following compounds are also manufactured in and sensitive and OP-resistant larvae of Boophilus micro analogous manner: plus. CEO. O. EXAMPLE 5 Y-s CHCOR Acaricidal Action (n) C3H S / Phaseolus vulgaris (plants) were overlaid with an in fested piece of leaf from a mass culture of Tetranychus R1 Physical data urticae 12 hours before the test for acaricidal action. The -NICO C3 inD26=5573 mobile stages which had spread over the plants were -N-CHCN D24 at 1.5252 O sprayed with the emulsified test preparations from a chromatography atomiser so that the spray broth did not &H, run off. The number of living and dead larvae, adults C D24 as 1.573 and eggs were evaluated after 2 to 7 days under a stereo -NH-C-CN scopic microscope and the result was expressed in per 5 centages. During the "interim,” the treated plants were bH, kept in greenhouse compartments at 25 C. -N(CH3CH=CH2) iD23=1.5221 In the above test, the compounds according to Exam -N-O CHs D23=1.518 ple 1 acted against adult larvae and eggs of Tetranychus &H, urticae. 20 EXAMPLE 6 CH3 26 s.5258 -N4CHON Action Against Soil Nematodes To test the action against soil nematodes, the active -NHCHOCs 27=1.5223 Substances were applied to, and intimately mixed with soil infected with root gall nematodes (Meloidgyne EXAMPLE 2 25 avenaria), in the specifically indicated concentrations. Immediately afterwards, tomato cuttings were planted in Insecticidal Ingest Poison Action the thus prepared soil in a series of tests, and after a Cotton plants were sprayed with a 0.05% aqueous waiting time of 8 days tomato seeds were sown in another active substance emulsion (obtained from 10% emulsifi 30 test series. able concentrate). In order to assess the nematocidal action, the galls pres After the spray coating had dried, the cotton plants ent on the roots were counted 28 days after planting and were populated with Spodoptera littoralis or Heliothis sowing respectively. virescens larvae (L). The test was carried out at 24°C. In this test, the active substances according to Example and 60% relative humidity. 1 display good action against Meloidgyne avenaria. In the above test, the compounds according to Example I claim: 1 displayed good insecticidal ingest poison action against 1. A compound of the formula Spodoptera and Heliothis larvae. EXAMPLE 3 40 R. Action Against Chilo suppressalis (n) CHS / R Six rice plants at a time of the variety Caloro were transplanted in plastic pots (diameter at the top-17 wherein R represents hydrogen or methyl and R2 rep cm.) and reared to a height of about 60 cm. Infestation resents -CHOCH, -CHAOCH or -CHOCH. with Chilo suppressalis larvae (L1: 3-4 mm. in length) 45 2. A compound according to claim 1 of the formula took place 2 days after the active substance had been applied in granule form to the paddy water (rate of CH5O O application: 8 kg. of active substance per hectare). Eval ation of the insecticidal action ensued 10 days after appli P-S-CH-C ON CHCHCHO Cs cation of the granules. 50 (n) C.H.'s? In the above test, the compounds according to Example 1 acted against Chilo suppressalis. 3. A compound according to claim 1 of the formula EXAMPLE 4 CEO O. Action Against Ticks 55 N/ -S CECON ECHO CH (A) Rhipicephalus bursa (n) CHS Five adult ticks or 50 tick larvae were counted into 4. A compound according to claim 1 of the formula a test tube and immersed for 1 to 2 minutes in 2 ml of an aqueous emulsion series each containing 100, 10, 1 60 and 0.1 p.p.m. of test substance. The tube was then CH5O O sealed with a standardised cotton wool plug and stood -S CECONEICECHO CH on its head so as to enable the cotton wool to absorb (n) CHS the active substance emulsion. In the case of the adults evaluation took place after 2 65 References Cited weeks, and in that of the larvae after 2 days. Each test UNITED STATES PATENTS was repeated twice. 3,092,649 6/1963 Schrader ------260-943 X (B) Boophilus microplus (larvae) 3,259,540 7/1966 Pianka et al. ------260-943X Tests were carried out with 20 sensitive and 20 OP O resistent larvae with a dilution series analogous to that ANTON H. SUTTO, Primary Examiner used in Test A. (The resistance refers to the tolerability of diazinon.) U.S. C. X.R. In these tests, the compounds according to Example 1 260-925, 940; 424-210, 212 acted against adults and larvae of Rhipicephalus bursa 75