United States Patent Office Patented Nov

3,773,859 United States Patent Office Patented Nov. 20, 1973 1 2 ticidal and acaricidal properties as well as, in some cases, 3,773,859 extremely low phytotoxicity. They possess a very good AMDOTHONOPHOSPHORIC ACID PHENYL action both against biting and against sucking and soil ESTERS inhabiting insects and are in this respect distinctly superior Gerhard Schrader, Wuppertal-Cronenberg, Ingeborg Hamr to the above-mentioned products of analogous constitu mann, Cologne, and Bernhard Homeyer, Opladen, Ger tion. Therefore, the new compounds of the present inven many, assignors to Bayer Aktiengesellschaft, Lever tion represent a valuable enrichment of the art. kusen, Germany No Drawing. Filed Apr. 7, 1970, Ser. No. 26,444 The course of the process may be represented by the Claims priority, application Germany, Apr. 14, 1969, following equation: P 19 18753.2 0 Int, CI. A01n 9/36; C07f 9/24 ro s R. -HEa U.S. C. 260-941 9 Claims P-0 --NH -) Eal R77 COOR ABSTRACT OF THE DISCLOSURE (II) Amidothionophosphoric acid phenyl esters, i.e. amido 15 Roy R thionophosphoric acid O-alkyl-O-(2-carbalkoxy-phenyl-)- p-o ester wherein the phenyl radical carries one or two halo NH R gen or lower alkyl substituents, or one alkylmercapto, COOR alkylsulphoxyl or alkylsulphonyl substituent, which 20 (I) (III) possess arthropodicidal, especially acaricidal and insec Advantageously, in accordance with the present inven ticidal, properties and to a process for their production. tion, in the various formulae herein: R represents straight and branched chain lower alkyl hy The present invention relates to and has for its objects drocarbon such as methyl, ethyl, n-, and iso-propyl, n the provision of particular new amidothionophosphoric 25 acid phenyl esters, i.e. amidothionophosphoric acid iso-, sec.- and tert-butyl, and the like, especially C1-4 O-alkyl-O-(2-carbalkoxy-phenyl-)-ester wherein the phen alkyl; yl radical carries one or two halogen or lower alkyl sub R represents straight and branched chain lower alkyl hy stituents, or one alkylmercapto, alkylsulphoxyl or alkyl drocarbons of at least 2 carbon atoms such as ethyl, n-, sulphonyl substituent, which possess arthropodicidal, espe 30 and iso-propyl, n-iso-, sec.- and tert-butyl, n-, iso cially insecticidal and acaricidal, properties, active com and the branched amyls, n-, iso- and the branched positions in the form of mixtures of such compounds hexyls, cyclohexyl, and the like, especially C-6 alkyl; with solid and liquid dispersible carrier vehicles, and R' represents a chlorine atom, or a lower alkyl or lower methods for producing such compounds and for using alkylmercapto group such as methyl, ethyl, n- and iso such compounds in a new way especially for combating 35 propyl, methylmercapto, ethylmercapto or propylmer pests, e.g. arthropods, with other and further objects capto, and the like, especially C-3 alkyl or C-3 alkyl becoming apparent from a study of the within specifica mercapto; tion and accompanying examples. R' represents hydrogen, chlorine or a lower alkyl group It has now been found, in accordance with the present such as methyl, ethyl, n- and isopropyl, and the like, invention, that the particular new amidothionophosphoric 40 especially C-3 alkyl; and Hal represents chlorine or acid phenyl esters of the general formula bromine. The O-alkyl-O-(2-carbalkoxy-phenyl - ) - thionophos RO S R phoric acid diester monohalides of Formula II required as 45 starting materials for the manufacture of the new com NE)-0 Riv pounds according to the invention have hitherto not been OOR (I) described in the literature; they are, however, easily ob in which tainable, even on an industrial scale, by reaction of O R represents a straight or branched alkyl residue, alkylthionophosphoric acid ester dihalides with the ap R" represents a straight-chain, branched-chain, or cyclic 50 propriate nuclear-substituted salicylic acid alkyl esters in alkyl group with 1 to 6 carbon atoms, the presence of solvents or diluents, and also using acid R' represents a halogen atom, a lower alkyl, alkylmer acceptors. Alkali hydroxides, carbonates and alcoholates, capto, alkylsulphoxyl or alkylsulphonyl group, and such as sodium and potassium hydroxides, methylates and R' represents a hydrogen or halogen atom or a lower ethylates, and tertiary bases such as triethylamine, diethyl alkyl residue, aniline, dimethylbenzylamine or pyridine, have proved 55 especially suitable as acid acceptors. Furthermore, it is exhibit strong arthropodicidal, especially insecticidal and possible, instead of working in the presence of acid-bind acaricidal, properties. O ing agents, to manufacture the starting products by reac It has been furthermore found, in accordance with the tion of the appropriate salts, preferably alkali metal or present invention, that a process for the production of ammonium salts of the particular nuclear-substituted sali the compounds of Formula I above may now be provided 60 cyclic acid esters. which comprises reacting an O-alkyl-O-(2-carbalkoxy It has proved appropriate to treat the mixture of sali phenyl-)-thionophosphoric acid diester monohalide of the cylic acid alkyl ester and acid acceptor (or the appropriate formula salt of the salicylic acid ester) and solvent with the O RO S R 65 alkyl-thionophosphoric acid ester dihalide, but the con verse addition can also be chosen. Hal R The reaction of the O-alkyl-O-(2-carbalkoxy-phenyl)- 2- OOR: (II) thionophosphoric acid diester monohalide (II) with am in which R, R, R'' and R' have the significance given monia also preferably takes place in the presence of sol above, and Hal represents a halogen atom, with ammo 70 vents or diluents, particularly those which are substantial nia. Advantageously, the particular new compounds of ly inert to the reagents. As such, it is, in particular, pos Formula I above are distinguished by outstanding insec sible to use water, low-boiling aliphatic alcohols such as 3,773,859 3 4. methanol, ethanol, propanol or butanol, ketones, for ex (Tortrix viridana), the fall armyworm (Laphygma frugi ample acetone, methylethyl ketone, methyl isopropyl ke perda) and cotton worm (Prodenia litura), the ermine tone or methyl isobutyl ketone, nitriles, for example aceto moth (Hyponomeuta padella), the Mediterranean flour nitrile and propionitrile, optionally chlorinated aliphatic moth (Ephestia kinniela) and greater wax month or aromatic hydrocarbons such as methylene chloride and (Galleria mellonella), and the like. ethylene chloride, chloroform, carbon tetrachloride, mono 5 Also to be classed with the biting insects are beetles chloroethylene, dichloroethylene and trichloroethylene, (Coleoptera), for example the granary weevil (Sito benzene, toluene, xylene and chlorobenzene, and ethers, philus granarius, Calandra granaria), the Colorado beetle for example, diethyl ether and di-n-butyl ether or dioxane. (Leptinotarsa decemlineata), the dock bettle (Gastrophysa Furthermore, in the process for the production of the 10 viridula), the mustard beetle (Phaedon cochleariae), the end products using an acid-binding agent, an excess of blossom bettle (Melligethes aeneus), the raspberry beetle ammonia may conveniently serve as the acid acceptor. (Byturus tomentosus), the bean weevil (Bruchidius= Either gaseous or aqueous ammonia can be used. Acanthoscelides obstectus), the leather beetle (Dermestes The process can be carried out within a wide temper frischi), the khapra bettle (Trogoderma granarium), ature range. In general, it is carried out at room temper the flour bettle (Tribolium castaneum), the northern ature or at a slightly to moderately elevated temperature, corn billbug (Calandra or Sitophilus zeamais), the drug and preferably at 20 to 60° C. Finally, it has proved store bettle (Stegobium paniceum), the yellow mealworm appropriate to stir the reaction mixture for a long period (Tenebrio molitor) and the saw-toothed grain beetle (say, between 1 and 12 hours) after combining the start (Oryzaephilus surinamensis), and also species living in ing materials, optionally with slight warming, in order to 20 the soil, for example wireworms (Agriotes spec.) and complete the reaction. larvae of the cockchafer (Melolontha melolontha); cock According to the Equation III given above, equimolar roaches, such as the Germany crockroach (Blattella amounts of the starting materials are theoretically neces germanica), American cockroach (Periplaneta ameri sary. The mixture is worked up in the usual manner, by cana), Madeira cockroach (Leucophaea or Rhypairobia taking it up, where the process has been carried out in 25 madeirae), Oriental cockroach (Blatta orientalis), the an aqueous medium, in a solvent which is immiscible with giant cockroach (Blaberus giganteus) and the black giant water, preferably a hydrocarbon or ether, washing the re cockroach (Blaberus fuscus) as well as Henschoutedenia sulting solution, and, after separation of the layers and flexivitta; further Orthoptera, for example the house drying of the organic phase, evaporating the solvent and cricket (Acheta domesticus); termites such as the eastern subjecting the residue, where possible, to fractional distil 30 subterranean termite (Reticuliterimes flavipes) and lation. Hymenoptera such as ants, for example the garden ant The amidothionophosphoric acid phenyl esters accord (Lasius niger); and the like. ing to the present invention are mostly colorless to The Diptera comprise essentially the flies, such as the slightly colored, water-insoluble oils which usually cannot vinegar fly (Drosophila melanogaster),

Load more