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