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), the Mediterranean be distilled without decomposition even under greatly fruit fly (Ceratitis capitata), the house fly (Musca reduced pressure. Where this is the case the products can, domestica) the little house fly (Fannia canicularis), the however, be freed of the last volatile constituents by so black blow fly (Phormia aegina) and bluebottle fly called "slight distillation,” that is to say brief heating to (Calliphora erythrocephala) as well as the stable fly a slightly to moderately elevated temperature, and can (Stomoxys calcitrans); further, gnats, for example be purified in this way. As already mentioned above, the 40 mosquitoes such as the yellow fever mosquito (Aedes amidothionophosphoric acid phenyl esters according to aegypti), the northern house mosquito (Culex pipiens) the invention, while in part having an extremly low and the malaria mosquito (Anopheles stephensi); and the phytotoxicity, possess an outstanding, rapidly starting and like. long-lasting insecticidal and acaricidal action. The With the mites (Acari) there are classed, in particular, products are therefore successfully employed in plant 45 the spider mites (Tetranychidae) such as the two-spotted protection for combating harmful sucking and biting Spider mite (Tetranychus tellarius=Tetranychus althaeae insects, Diptera and mites (Acarina). or Tetranychus urticae) and the European red mite (Para To the sucking insects contemplated herein there be tetranychus pilosus=Panonychus ulmi), blister mites, for long, in the main, aphids (Aphidae) such as the green example the currant blister mite (Eriophyes ribis) and peach aphid (Myzus persicae), the bean aphid (Doralis 50 tarSonemids, for example the broad mite (Hemi fabae), the bird cherry aphid (Rhopalosiphum padi.), the tarsonemus latus) and the cyclamen mite (Tarsonemus pea aphid (Macrosiphun pisi) and the potato aphid pallidus); finally, ticks, such as the relapsing fever tick (Macrosiphum solanifolii), the current gall aphid (Ornithodorus moubata); and the like. (Cryptomyzus korschelti), the mealy apple aphid (Sap The active compounds according to the instant invention pahsis mali) the mealy plum aphid (Hyaltopterus 55 can be utilized, if desired, in the form of the usual formu arundinis) and the cherry black-fly (Myzus cerasi); in lations or compositions with conventional inert (i.e. plant addition, scales and mealybugs (Coccina), for example compatible or herbicidally inert) pesticidal diluents or the oleander scale (Aspidiotus hederae) and the soft scale extenders, i.e. diluents or extenders of the type usable in (Lecanium hesperidum) as well as the grape mealybug conventional pesticidal formulations or compositions, e.g. (Pseudococcus maritimus); thrips (Thysanoptera), such 60 conventional pesticidal dispersible carrier vehicles such as as Hercinothrips femoralis, and bugs, for example the Solutions, emulsions, suspensions, emulsifiable concen beet bug (Piesma quadrata), the cotton bug (Dysdercus -trates, spray powders, pastes, soluble powders, dusting intermedius), the bed bug (Cimex lectularius), the assas agents, granules, etc. These are prepared in known man sin bug (Rhodnius prolixus) and Chagas' bug (Triatoma ner, for instance by extending the active compounds with infestans) and, further, cicadas, such as Euscelis bilo 65 conventional pesticidal dispersible liquid diluent carriers batus and Nephotettix bipunctatus, and the like. and/or dispersible solid carriers optionally with the use With the biting insects contemplated herein there are of carrier vehicle assistants, e.g. conventional pesticidal classes, in the main, butterfly caterpillars (Lepidoptera) surface-active agents, including emulsifying agents and/or such as the diamond-back moth (Plutella maculipennis), dispersing agents, whereby, for example, in the case where the gypsy moth (Lymantria dispar), the brown-tail moth 70 water is used as diluent, organic solvents may be added as (Euproctis chrysorrhoea) and tent caterpillar (Malaco auxiliary solvents. The following may be chiefly con Soma neustria); further, the cabbage moth (Mamestra sidered for use as conventional carrier vehicles for this brassicae) and the cutworm (Agrotis segetum), the large purpose: inert dispersible liquid diluent carriers, includ white butterfly (Pieris brassicae), the small winter moth ing inert organic solvents, such as aromatic hydrocarbons (Cheimatobia brumata), the green oak tortrix moth 75 (e.g. benzene, toluene, xylene, etc.), halogenated, espe 3,778,859 5 6 cially chlorinated, aromatic hydrocarbons (e.g. chloro and acarids which comprise applying to at least one of benzenes, etc.), paraffins (e.g. petroleum fractions), chlo correspondingly (a) such insects, (b) such acarids, and rinated aliphatic hydrocarbons (e.g. methylene chloride, (c) the corresponding habitat, i.e. the locus to be pro etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, tected, a correspondingly combative or toxic amount, etc.), amines (e.g. ethanolamine, etc.) ethers, etheralco i.e. an arthropodicidally, especially insecticidally or hols (e.g. glycol monomethyl ether, etc.), amides (e.g. acaricidally, effective amount of the particular active com dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sul pound of the invention alone or together with a carrier foxide, etc.), ketones (e.g. acetone, etc.) and/or water; vehicle as noted above. The instant formulations or com as well as inert dispersible finely divided solid carriers, positions are applied in the usual manner, for instance such as ground natural minerals (e.g. kaolins, alumina, 0. by spraying, atomizing, vaporizing, scattering, dusting, silica, chalk, i.e. calcium carbonate, talc, kieselguhr, etc.) watering, sprinkling, pouring, fumigating, and the like. and ground synthetic minerals (e.g. highly dispersed silicic It will be realized, of course, that the concentration of acid, silicates, e.g. alkali silicates, etc.); whereas the fol the particular active compound utilized in admixture with lowing may be chiefly considered for use as conventional the carrier vehicle will depend upon the intended appli carrier vehicle assistants, e.g. surface-active agents, for 15 cation. Therefore, in special cases it is possible to go this purpose: emulsifying agents, such as non-ionic and/or above or below the aforementioned concentration ranges. anionic emulsifying agents (e.g. polyethylene oxide esters The unexpected superiority and outsanding activity of of fatty acids, polyethylene oxide ethers of fatty alcohols, the particular new compounds of the present invention is alkyl sulfonates, aryl sulfonates, etc., and especially alkyl illustrated without limitation by the following examples. arylpolyglycol ethers, magnesium stearate, sodium oleate, 20 EXAMPLE 1. etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc. Phaedon larvae test Such active compounds may be employed alone or in Solvent: 3 parts by weight of acetone the form of mixtures with one another and/or with such Emulsifier: 1 part by weight of alkylaryl polyglycol ether. solid and/or liquid dispersible carrier vehicles and/or 25 To produce a suitable preparation of active compound, with other known compatible active agents, especially 1 part by weight of the active compound is mixed with the plant protection agents, such as other acaricides and in stated amount of solvent containing the stated amount of secticides, or fungicides, herbicides, bactericides, etc., if emulsifier, and the concentrate is diluted with water to desired, or in the form of particular dosage preparations the desired final concentration. for specific application made therefrom, such as solutions, 30 Cabbage leaves (Brassica oleracea) are sprayed with emulsions, powders, pastes, and granules which are thus the preparation of the active compound until dripping wet ready for use. As concerns commercially marketed preparations, these and then infested with mustard bettle larvae (Phaedon generally contemplate carrier composition mixtures in cochleariae). which the active compound is present in an amount sub 35 : After the specified periods of time, the degree of stantially between about 0.1-95% by weight, and prefer destruction is determined as a percentage: 100% means ably 0.5-90% by weight, of the mixture, whereas carrier that all the bettle larvae are killed. 0% means that none composition mixtures suitable for direct application or of the bettle larvae are killed. field application generally contemplate those in which the The active compounds, the concentration of the active active compound is present in an amount substantially 40 compounds, the times of evaluation and the results can between about 0.001-5%, preferably 0.002-1%, by weight be seen from the following Table 1: of the mixture. Thus, the present invention contemplates TABLE 1. over-all compositions which comprise mixtures of a con (Phaedon larvae test) ventional dispersible carrier vehicle such as (1) a dispersi Active Degree of 45 compound destruction ble inert finely divided carrier solid, and/or (2) a dispersi concentra- - in percent ble carrier liquid such as an inert organic solvent and/or tion in after 3 water preferably including a surface-active effective Active compound (constitution) percent days amount of a carrier vehicle assistant, e.g. a surface-active (CH3)N 0. (A) 0. 0 agent, such as an emulsifying agent and/or a dispersing N agent, and an amount of the active compound which is 50. / -O (CHS)N effective for the purpose in question and which is generally CO-O CH between about 0.00001 to 95%, preferably 0.00001 to 20% and most preferably 0.0. to 5% by weight of the (known) - mixture. (CH3)N O (B) 0. 100 The active compounds can also be used in accordance 55 0.01 O with the well known ultra-low-volume process with good 3-0 success, i.e. by applying such compound if normally a CHO liquid, or by applying a liquid composition containing O-O CH the same, via very effective atomizing equipment in finely (known) divided form, e.g. average particle diameter of from 50 60 (C) 0. 0. 100 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most (CHO)P-O about a few liters/hectare are needed, and often amounts CO-O CH only up to about 1 quart/acre, preferably 2-16 fluid 65 (known) ounces/acre, are sufficient. In this process it is possible to CHO S (1) 0. 100 use highly concentrated liquid compositions with said N 0.01 100 liquid carrier vehicles containing from about 20 to about P-O Cl 0.001 100 95% by weight of active compound or even the 100% Ní, O-O CH-iso active substance alone, e.g. about 20-100% by weight of 70 the active compound. Cl (2) 0,1 100 In particular, the present invention comtemplates cHo, 8 methods of selectively killing, combating or controlling P-O pests, e.g. arthropods, i.e. insects and acarids, and more Ná, particularly, methods of combating at least one of insects 75 CO-O CH-iso 3,773,859 8 TABLE 1-Continued TABLE 2-Continued Active Degree of Active Degree of compound destruction compound destruction concentra- in percent concentrar in percent tion in after 3 tion in after 3 Active compound (constitution) percent days Active compound (constitution) percent days C (3) 0. 100 CaO S () 0. 100 CHO S O, O, 65 NI 0.00 100 N P-O -Cl P-O / / NE N CO-O CH-iso C O C1 (2) 0. 00 CO-O CH-iso Chio, G. B. CHO S (4) 0, 100 P-O wo N O, O. 100 / P-O -S-CH NE / CO-OC is NH CO-OC-iso CE (3) 0, 100 CHO S (5) O. 00 Chio, 0.01 5 N 0.0 100 P-O -S-CH N P-0 Ná, CH CO-O C-Sec, 20 CO-O Criso CE (6) 0.1 00 C.H.0, s 0.01 00 CHOinva SI (5)5 0.010. 10075 P-O S-C -O -CE N?í, 25 Ná, O-O C-Sec, O-O C-Sec. CE (6) 0, 100 EXAMPLE 2 C.H.O. 0,,O 75 Plutella test 30 P-0 S-C N Solvent: 3 parts by weight of acetone O-O CH-sec. Emulsifier: 1 part by weight of alkylaryl polyglycol ether. To produce a suitable preparation of active compound, EXAMPLE 3 1 part by weight of the active compound is mixed with Myzus test (contact action) the stated amount of solvent containing the stated amount Solvent: 3 parts by weight of acetone of emulsifier and the concentrate is diluted with water Emulsifier: 1 part by weight of alkylary polyglycol ether. to the desired final concentration. Cabbage leaves (Brassica oleracea) are sprayed with 40 To produce a suitable preparation of active compound, the preparation of the active compound until dew moist 1 part by weight of the active compound is mixed with and are then infested with caterpillars of the diamond the stated amount of solvent containing the stated amount back moth (Plutella maculipennis). of emulsifier and the concentrate is diluted with water to After the specified periods of time, the degree of de the desired final concentration. struction is determined as a percentage: 100% means Cabbage plants (Brassica oleracea) which have been that all the caterpillars are killed whereas 0% means that 45 heavily infested with peach aphids (Myzus persicae) are none of the caterpillars are killed. sprayed with the preparation of the active compound The active compounds, the concentration of the active until dripping wet. . . compounds, the evaluation times and the results can be After the specified periods of time, the degree of de seen from the following Table 2: struction is determined as a percentage: 100% means that 50 all the aphids are killed whereas 0% means that none TABLE 2 of the aphids are killed. The active compounds, the concentrations of the active (Plutella test) compounds, the evaluation times and the results can be Active Degree of compound destruction seen from the following Table 3: concentra- in percent 55 tion in after 3 TABLE 3 Active compound (constitution) percent days (Myzus test) (CH3)N O (A) 0.1 O N Active poundOe Degree of P-0 60 concent destruction CE)N tration in percent (CH3) CO-OCs in after (known) Active compound (constitution) percent 24 hours (CH)N, O (A) 0. O (CH3)CH3)N N O (B) 0.00. 30O 65 P-0 CE)N 3-0 CEO C a) CO-OCs CO-O CH (known) (known) S (C) 0,1 80 (CH)N O (B) , O I 0.01 O 70 (CHO). P-O CEO 3-0 CO-OCH Es CO-OCs (known) (known) 75 3,773,859 9 10 TABLE 3-Continued compounds, the evaluation times and the results can be Active seen from the following Table 4: poundCO Degree of concens destruction tration in percent in after Active compound (constitution) percent 24 hours i (C) 0.1 0 TABLE 4 (Tetranychus test) O Active (CHO) !-->O-O CH poundcons Degree of (known) concen- destruction tration in percent CHO S (1) 0.1 100 in after N 0.01 99 Active compound (constitution) percent 48 hours P-O -C 5 / NE (CH3)N O (A) 0. 0 O-OC-iso N CEO S 2) 0.1 100 P-0 3 N ( 0.01 100 (CH3)CH)N O-O CH M --O 0.001 40 20 N (known) CO-O CH-iso (CH3)N O (B) 0.1 0 CH (3) 0.1 99 N CH.0, 0.0 40 CHO P-0 1-0 25 O-O CH Ná, CH (known) O-O CH-iso CHO S (4) 0. 100 s (C) 0.1 0. N 0.0 100 / -O -S-CH 30 N O-O C3-iso ol-->O-O CHs CHO S (5) 0.1 100 (known) N 0.0 99 CIO S (1) 0.1 100 N 0.01 99 P-0- S-CH 35 P-O -Cl N O-OC-sec. N?, CH (6) 0.1 100 C-O C3H-iso Cas o, C (2) 0. 65 1-0 -S-C 40 CH.0, P-O Ná, O-O CH-sec. N?, O-O C3H7-iso

50 EXAMPLE 5 Critical concentration test/soil insects Test insect: Cabbable fly maggots (Phorbia brassicae) EXAMPLE 4 Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylary polyglycol ether. Tetranychus test 55 To produce a suitable preparation of active compound, Solvent: 3 parts by weight of acetone 1 part by weight of active compound is mixed with the Emulsifier: 1 part by weight of alkylaryl polyglycol ether. stated amount of solvent, the stated amount of emulsifier To produce a suitable preparation of active compound, is added and the concentrate is diluted with water to the 1 part by weight of the active compound is mixed with the 60 desired final concentration. The preparation of active com stated amount of solvent containing the stated amount pound is intimately mixed with the soil. The concentra of emulsifier and the concentrate so obtained is diluted tion of the active compound in the preparation is of prac with water to the desired final concentration. tically no importance; only the amount by weight of active . Bean plants (Phaseolus vulgaris), which have a height compound per unit volume of soil, which is given in of approximately 10-30 cm., are sprayed with the prepara 65 p.p.m. (e.g. mg/1.), is decisive. The soil is filled into pots tion of the active compound until dripping wet. These and the pots are left to stand at room temperature. After bean plants are heavily infested with spider mites 24 hours the test insects are put into the treated soil and (Tetranychus urticae) in all stages of development. after a further 48 hours the degree of effectiveness of the After the specified periods of time, the effectiveness active compound is determined as a percentage by count of the preparation of active compound is determined by 70 ing the dead and live test insects. The degree of effective counting the dead mites. The degree of destruction thus ness is 100% when all the test insects have been killed; obtained is expressed as a percentage: 100% means that it is 0% when exactly as many test insects are still alive all the spider mites are killed whereas 0% means that as in the case of the control. none of the spider mites are killed. The active compounds, the amounts applied and the The active compounds, the concentrations of the active 75 results can be seen from the following Table 5: 3,773,859 12 TABLE 5 as a pale yellow, water-insoluble oil having a refractive index n=1.5245. (Phorbia test) EXAMPLE 7 Active compound CHO S concentra- Degree of tion in destruction 5 Active compound (constitution) p.p.m. in percent NE CHO S 20 100 O-O CH-so (4) N (1) O 100 P-O -C 5 50 0.35 molar batch: / 133 g. of O-ethyl-(2-carbisopropoxy-4-methylmercap N O CO-OC-iso tophenyl-)-thionophosphoric acid diester monochloride of C1 20 100 the following formula: CEO S (2) 100 S. N 5 50 P-O CS -O- 1-0 Cs / 5 NE b CO-O CH-iso CO-O CH-iso (IIb) The following further examples are set forth to illus (manufactured according to the process of Example 6 by trate, without limitation, the process for producing the reaction of the corresponding potassium salt of 5-methyl active compounds according to the present invention, 20 mercapto-salicylic acid isopropyl ester with O-ethylthio nophosphoric acid ester dichloride) are stirred for 1 hour EXAMPLE 6 at 25 to 30 C, with 100 cc. of 25% strength aqueous CHs ammonia. Thereafter a further 25 cc. of ammonia-water CH o, s are added to the reaction mixture and this is stirred for a 25 further 10 hours. The batch is then taken up in 300 cc. of NH P-0- N ether and the ether solution is washed with water, sep CH arated off and dried over sodium sulphate. After distilling off the solvent, 85 g. (70% of theory) CO-O C3H7-iso (3) of amidothionophosphoric acid O-ethyl-O-(2-carbisopro 0.35 molar batch: 30 poxy-4-methylmercaptophenyl-)-ester are obtained in the 119 g, of O-methyl-O-(2-carbisopropoxy-3,5-dimethyl form of a yellow, water-soluble oil of refractive index phenyl-)-thionophosphoric acid diester monochloride are n23-15678. dissolved in 600 cc. of benzene. Dry ammonia is passed Calculated for a molecular weight of 349 (percent): into this solution at 20° C. (slight external cooling), while P, 8.9; S, 18.3; N, 4.0. Found (percent): P, 8.6; S, 18.0; stirring, until the reaction is complete, and the mixture is 35 N, 3.9. stirred for a further hour after the introduction. The reac EXAMPLE 8 tion mixture is then twice washed with 30 cc. of water each time, the benzene layer is separated off and dried over C sodium sulphate, and the solvent is subsequently evapo rated under reduced pressure. The residue is briefly heated 40 S-CH at a pressure of 0.3 mm. Hg to a bath temperature of 100° C. O-O CH-Sec. (5) 75 g. (68% of theory) of the amidothionophosphoric 0.39 molar batch: acid O-methyl-O-(2-carbisopropoxy-3,5-dimethylphenyl-)- 149 g. of O-ethyl-O-(2-carb-sec.-butoxy-4-methylmer ester of refractive index n-1.5302 are thus obtained. 45 captophenyl-)-thionophosphoric acid diester monochlo Calculated for a molecular weight of 317 (percent): ride of the following formula: P, 9.8; S, 10.1; N, 4.4. Found (percent): P, 9.6; S, 9.9; C N, 4.1. 2 s The O-methyl-O-(2-carbisopropoxy-3,5-dimethylphen CHS O-P-O Cas N yl-)-thionophosphoric acid diester monochloride required 50 C as the starting material can be obtained as follows: C S do-obH &H, (IIc) 55 are stirred with 100 cc. of 25% strength aqueous ammo nia. After one hour a further 20 cc. of ammonia-water are Yo O-O C3H-iso added to the reaction mixture which is stirred for a fur CH3 (IIa ther 10 hours at room temperature. After working up the 0.5 molar batch: mixture as described in Example 2, 112 g. (79% of 30 g. of potassium hydroxide are dissolved in 300 cc. 60 theory) of amidothionophosphoric acid O-ethyl-O-(2- of isopropanol and 104 g. of 4,6-dimethyl-salicylic acid carb-sec.-butoxy-4-methylmercaptophenyl-)-ester are ob isopropyl ester (boiling point: 100° C.; n=1.5141) tained as a yellow water-insoluble oil of refractive index are added to the solution. After adding 500 cc. of benzene, n22=1.5626 the water formed is distilled off azeotropically under re duced pressure and the potassium salt which remains is 65 Calculated for a molecular weight of 363 (percent): dissolved in 300 cc. of acetonitrile. 83 g. of O-methyl P, 8.5; S, 17.6; N, 3.8. Found (percent): P, 8.3; S, 17.4; thionophosphoric acid ester dichloride are now added to N, 3.7. the reaction mixture while stirring, the mixture is stirred EXAMPLE 9 for a further 12 hours at 30° C., and the batch is then CH diluted with 400 cc. of benzene. The benzene solution is O twice washed with 50 cc. of ice water and subsequently separated off and dried over sodium sulphate. After dis tilling off the benzene, 119 g. (71% of theory) of the d O-O CH-sec. (6) O-methyl-O-(2-carboisopropoxy - 3,5 - dimethylphenyl)- 0.24 molar batch: thionophosphoric acid diester monochloride are obtained 5 95 g. of O-ethyl-O-(2 - carb.-sec.-butoxy-4-methylmer 3,773,859 13 14 capto-5 - methyl-phenyl-)-thionophosphoric acid diester Calculated for a molecular weight of 323.5 (percent): monochloride of the following formula: P, 9.6; S, 9.9; N, 4.3; Cl, 11.0. Found (percent): P, 9.8; S, 9.6; N, 4.1; C1, 10.7. C3 As may be used herein, the terms "arthropod,” “arthro 2 s podical' and "arthropodicide” comtemplate specifically CH3S- -o-roch, both insects and acarids. Thus, the insects and acarids may Cl be considered herein collectively as arthropods to be com CF3 bated in accordance with the invention, and accordingly CO-O ch the insecticidal and/or acaricidal activity may be termed &H, (IId) O arthropodicidal activity, and the concomitant combative are stirred with 50 cc. of 25% strength aqueous ammonia, or effective amount used will be an arthropodicidally after one hour a further 10 cc. of aqueous ammonia are effective amount which in effect means an insecticidally added to the reaction mixture, and the mixture is then or acaricidally effective amount of the active compound stirred for a further 10 hours at room temperature. After for the desired purposes. working up the mixture as in Example 7, 77 g. (85% of 5 It will be appreciated that the instant specification and theory) of amidothionophosphoric acid O-ethyl-O-(2- examples are set forth by way of illustration and not carb-sec.-butoxy-4-methylmercapto - 5 - methyl-phenyl-)- limitation, and that various modifications and changes ester are obtained as a slightly yellow, water-insoluble may be made without departing from the spirit and scope oil of refractive index n=1.5602. of the present invention. Calculated for a molecular weight of 377 (percent): 20 What we claim is: P, 8.2; S, 17.0; N, 3.7. Found (percent): P, 8.6; S, 16.8; 1. Amidothionophosphoric acid phenyl esters of the N, 3.4. formula EXAMPLE 10 RO S RP 25 (I) O-O C37-iso (1) wherein 0.45 molar batch: R represents a lower alkyl group of 1 to 4 carbon 155 g. of O-methyl-O-(2-carbisopropoxy - 4 - chloro 30 atoms, phenyl-)-thionophosphoric acid diester monochloride of R’ represents a straight-chain, branched-chain or cyclic alkyl group with 1 to 6 carbon atoms, the following formula: R' represents a chlorine atom or an alkyl or alkyl S mercapto group with 1 to 5 carbon atoms, and 35 R' represents a hydrogen or halogen atom or a lower alkyl residue, the radicals R'' and R' being in the Cl 3, 4 or 5-positions. O-O CH-iso (IId) 2. Compound according to claim 1 in which R' repre are added at 30 to 45 C., while stirring, to 100 cc. of sents an alkyl group with 2 to 6 carbon atoms, and R' 20% strength aqueous ammonia, and the mixture is kept 40 represents hydrogen, chlorine, or an alkyl group having at 40 C. for a further hour and then worked up in the 1 to 3 carbon atoms. manner described in Example 7. 110 g. (72% of theory) 3. Compound according to claim 2 in which R repre of amidothionophosphoric acid O-methyl-O - (2 - carbiso sents a lower alkyl group with 1 or 2 carbon atoms and propoxy-4-chlorophenyl-)-ester are obtained in the form R represents a lower alkyl group with 2 to 4 carbon of a slightly yellow, water-insoluble oil of refractive index 45 atoms. n=1.5461. 4. Compound according to claim 1 wherein such com Calculated for a molecular weight of 323.5 (percent): pound is amidothionophosphoric acid O-methyl-O- P, 9.6; S, 9.9; N, 4.3; C1, 11.0. Found (percent): P, 9.4; (2-carbisopropoxy-4-chlorophenyl-)-ester of the formula: S, 9.7; N, 4.7; Cl, 11.4. EXAMPLE 11 50 C NI CHO S O-O C3-iso (i) 3-o-Ky. 5. Compound according to claim 1 wherein such com / 55 pound is amidothionophosphoric acid O-methyl-O-(2- NH 2 co-ociH-so (2) carbisopropoxy-5-chlorophenyl-)-ester of the formula: 0.22 molar batch: CEO S 77 g. of O-methyl-O-(2 - carbisopropoxy - 5 - chloro phenyl-)-thionophosphoric acid diester monochloride of 60 3-(/ > the following formula: O-O C3-iso (2) Cl 6. Compound according to claim 1 wherein such com pound is amidothionophosphoric acid O-methyl-O-(2- 65 carbisopropoxy - 3,5 - dimethylphenyl-)-ester of the for (D-o-oald Cl mula: O-O CH-so (CC) CH CHO S 8 are added at 25 to 30° C. to 60 cc. of 20% strength aqueous ammonia, while stirring. The mixture is stirred 70 for a further hour at 35 to 40° C. and is then worked up dri, as described in Example 7. 53 g (74% of theory) of the amidothionophosphoric acid O-methyl-O-(2 - carbisopro O-O C3-iso (3) poxy-5-chlorophenyl-)-ester are obtained as a yellow, 7. Compound according to claim 1 wherein such com water-insoluble oil of refractive index n22=1.5389. 75 pound is amidothionophosphoric acid O-ethyl-O-(2-carb 3,773,859 15 16 isopropoxy-4-methylmercapto phenyl-)-ester of the for- sec.-butoxy-4-methylmercapto-5-methylphenyl-)-ester of mula: the formula: CH CHO S CEO S NI N P-0 -S-CH 5 P-0 -S-C N NE CO-O C3-iso (4) O-O Co-Sec. (6) 8. Compound according to claim 1 wherein such com- References Cited pound is amidothionophosphoric acid O-ethyl-O-(2-carb- 10 UNITED STATES PATENTS sec.-butoxy-4-methylmercaptophenyl-)-ester of the for- 3,621,082 11/1971 Schrader et al 260-941 mula: Vas use vap as a no FOREIGN PATENTS onto, 6,744 4/1966 Japan ------260-941 Ní, -0-{ X-S-CH, 5 ANTON H. SUTTO, Primary Examiner Co-o CH-iso (5) U.S. C. X.R. 9. Compound according to claim 1 wherein such com- 260-984: 424-212 pound is amidothionophosphoric acid O-ethyl-O-(2-carb- 20 ; 42

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Col. lines. 54 &nd 55, correct spelling of 'sappaphis'. Col. 3, line. 55, correct spelling of "Hyalopterus". 4, line 4, change "nonth" to -- moth --. 9, Table 3, corpound (2), correct formula to read as follois :

O-O.Cis-so Col. 12, Example 8, Compound (IIc), correct formula to read "as follows : S' a CH- -o-rociti, C a - to-ortCI bit, UFAr" E) S.A.Q' ii.' ' ( ) ' ' N'' . . . . . i.. . r Fr. s r. " - " y "r, is (r CERTA ful. . . i. e. V.CA. A. A. .E. G.. . CC: Yá...... isECC. a . F S. a sist No. 3,a 73,85 28& star-----,n-at-a-wa-ce-or-les-n ens-re. passeracy spectrumkas KaraaceX readaka. Frf Iays to (s age 2f ofa 2 t secaresa memadanao assaward Arrorssmap-riser-ar Yasu. . . It is certified that error appears in the ab{}ve-idestifie

and that said is:ters latest air?; taxaby &ocirects: &S she's e.g.: ; - ...... e Col. 3, Exemple 10, compound (IId), correct fortula to read as follows : C S -

<>-of-cal . . - -- N -CO-O Calir-iso, --. Col. 13, line '68, Example 11, after the formula, insert 4 ed (IIe) --. Col. 14, line 32, claim 1, cancel "5" and insert therefor as 3 a. s. Col. 15, line 17, claim 8, in the formula, cancel "iso" and substitute therefor -- sec -e. signed and sealed this 22nd day of October 1974.

(SEAL) Attest : McCoy M. GIBSON JR. . c. MARSHALL DANN y Attesting Officer Coramissioner of Patents