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3,058,879 vin Patented 0ct._'16,v'1'962~ 2 The production thus is “carried out by reacting the corre sponding diphenyl ester monochlorides of phosphoric acid ' 3,058,879 ' or thiophosphoric acid with ammonia or the correspond ing amines in an aqueous or inert medium, or also by ACARICIDAL AND OVICIDAL AGENTS Hugo Malz and Richard Wegler, Leverkusen, and Giinter Untersteuhtifer, ()pladen, Germany, assignors to Far esteri?cation of the corresponding amido- or arnidothio benfabriken Bayer Aktiengesellschaft, Leverkusen, phosphoric acid dichlorides-with the corresponding phe Germany, a corporation of Germany nols or alkali metal phenolates. No Drawing. Filed Sept. 16, 1959, Ser. No. 840,253 Claims priority, application Germany Oct. 3, 1958 6 Claims. (Cl. 167-33) The present invention relates to and has ‘as its objects new and useful pesticidal agents with acaricidal and ovicidal action containing as active ingredients com pounds of the following general formula R1 invention are barely water-soluble and can therefore be separated in a simple manner from the aqueous mother liquors. - sidered talc, chalk, bentonite, k-ieselguhr and the like. N-P(o R3): . in which R, and R2 stand for hydrogen, alkyl or alkenyl radicals, R1 and?Rz together with the nitrogen atom may When emu-lsi?able dusts are to be prepared, it is advisable to use suitable emulsi?ers, particularly those having a non-ionogenic basis such as aryl-hydroxy-polyglycol ethers of which various types are on the market. also form a 5- or 6~member ring system, which also may For the preparation of liquid combinations it is possible be interrupted by further hetero atoms; R, ‘furthermore may be a lower alkylene radical bearing another to‘ employ solutions of the phosphoric acid or thiophos phoric acid esters to be used according to the invention not only in suitable inert organic solvents, but also in water in combination with suitable emulsi?ers and aux iliary solvents. Organic ‘solvents are for'example alco 0(s) ' —III—P (OR3)z—group Ra ' The plant protective agents claimed are applied in usual manner in the ‘form of solutions or dusts. As solid ex tenders or diluents for dusts there are chie?y to be con 0 (S) R2 In this case it is ex pedient ‘to add the acid chlorides dropwise to aqueous solutions of the phenolates or to ‘aqueous-alkaline solu 10 tions of the phenols. All compounds according to the hols, hydrocarbons, chie?y chlorinated low molecular - weight hydrocarbons such as chloroform, trichloro~eth ylene and the like. For the preparation of aqueous dilu R3 at last stands for a halo-substituted phenyl radical. This invention further relates to the protection of plant against attack by the above mentioned pests. tions it is advantageous to start from a mixture of active In accordance with the present invention it has been found that these compounds show an exceedingly strong substance, emulsi?er, auxiliary solvent, the auxiliary sol vents chie?y to be considered being dimethylformamide, acaricidal and especially ovicidal activity. Since this acetone, xylene or o-dichlorobenzene and the emulsi?ers used being those described above. The agents are aplied in the manner customary for other phosphoric acid esters. The following examples are given for the purpose of ~ _ activity also exists against pests which have become resistant to plant protective agents based on present com merical phosphoric acid esters, these agents may e?ec tively be used for combating, for example, spider mites in which such resistance phenomena have chie?y been observed. As acaricidal or ovicidal plant protective agents in the illustrating the invention. Example 1 40' sense of the present invention there are chie?y to be ,Test on spider mites (Tetranychus telarius) which are considered the above amidophosphoric ‘acid or amidothio highly resistant to organic phosphoric acid esters. phosphoric acid esters of the following formula Bean plants which were strongly infested with spider mites-of all stages of development were sprayed with 45 R1 0(5) aqueous emulsions at various concentrations of the fol ,N—P (0 R3). _ lowing active substance. 1.: More particularly in this formula R1 and R2 denote sim ilar or di?erent radicals such as hydrogen or a saturated 50 or unsaturated alkyl radical which eventually may be substituted. R1 and R2 may also form a heterocyclic ring together with the nitrogen atom, for example an ethylene amounts by weight of acetone and a commercial benzyl hydroxy-diphenyl polyglycol ether-emulsi?er type. idine ring. Finally, K; may also denote an alkylene such 55 as a methylene, ethylene or propylene radical serving for ,_ the linkage of two molecule radicals of the above ‘for mula via nitrogen _atoms._ The alkylene chain also may be i?terruptedby heteroatoms such as nitrogen, oxygen, , “ . Thecompounds according to the invention are crys talline products or oily, in some cases distilla-ble liquids. Some are known from the literature, eg from US. Percent active substance Percent mor tality of mov- Degree of (pure active able stages infestation subst. in after 48 after 8 aqueous hours days 80 20 10 0 0 2 emulsion) sulfur and the like. As substituents for R1 or R2 there may be considered inter alia halogens, amino groups, other or thioether radicals and the like. R3 in the above formula denotes a‘ halophenyl radical which may further more be substituted by nitro or amino groups, but also and the like. O The emulsions were prepared with the use of same imine, morpholine, thiamorpholine, piperazine or piper by alkyl, alkoxy, alkylmercapto, sulfoxide, sul'fone groups (Giana-halogen, 0.05 0. 025 0.0125 65 Mortality of movable stages after 48 hours means that all pests which still showed some movement were counted as living pests. The damage of infestation has been counted by the damaging numbers. Patents 2,615,038and 2,615,037. If they are novel they 70 0=no damage maybe prepared exactly by the same methodsas they 1=very slight infestation are known for’the preparation of the known substances. " 7 v ' 3,058,879 2=slight infestation 3=medium infestation 4=heavy infestation 5 =very heavy infestation. 0 Example 2 vOvicidal action against eggs of highly resistant spider mites (Tetfanychus telarius): 0(8) 7 Eggs on Phaseolus vulgaris (string beans) which were 24 hours old were sprayed with aqueous emulsions of the 10 above mentioned active substance and the mortality was determined after 8 days. 0(s) 7 ' ' Percent active ' Percent; active subst. in aqueous after 8 days substance (pure 0(S) 15 killed emulsion) 07(3) 0.05 0. 02,5 97 50 We claim: 20 ' . ' , 1. A method of combating mites and eggs thereof on a plant which comprises treating the plant'with an active amount of a compound of the following’ formula The emulsions have been prepared’ as described in Ex ample 1., 0(5) r V E'Jéample 3 25 7 Permanent ovicidal action against eggs of highly re-' sistant spider mites (Tetranychus telarius): ] V it 0 V V V 2. A method 'of combating mitestand eggs thereof-on a plant which comprises treating the plant with an actlve amount of a compound of ‘the Vfollowing formula a In order to determine the permanent etfect of the above mentioned compound, sprayed bean plants were infested after 24 hours, 3 days and 9 days with females laying eggs on the sprayed plants. The table shows the per centage of eggs killed'which had been laid'during the} aforesaid periods. 7 Percent active 7 " 3, A method of combating mites and eggs thereof _on Percent eggs killed which hag, been laidaiter; 35 a plant which comprises treating the plant with an active amount of a compound of the followingrformular ‘ substance 24 hours _ 3 days 0. 05 V O. 025 97" 50 V t, r 94 38 N—P(O Rs)? 9 days '40 V " ' 7 V R27 ,_ . t V , in which R1 stands for a member selected’ from. the group 41.5, 732.5 consisting of hydrogen,’ a lower alkyl, a lower alkenyl and ; ' a a The emulsions have been prepared as described: in’ Ex- “45 ' amplel. 7' V - 11?- , lower allzylene-IYI-P (0 R3): Similarly good combating results can be achieved with 7 theme of other representatives of the claimed class of ' ' R57 ‘ _ , R2 stands for a member selected from the; group con compounds; In the following table some of thesecom sisting of hydrogen, lower alkyl and lower alkenyl; and pounds are listed by way of example, without however limiting the claimed classrof compounds in any way'byv 50 when R1 and R2 areataken together with the nitrogen this compilation. atom, they form a, member selected from the group con sisting oftethyleneimino, morpholino, ,thia’morpholino, V , 'Epiperazino 'and p 'perjidino radicals; and R3 ‘stands for a halo-substituted phenyl radical. 9(3) 7 7 , r » V a p 4; An acaricidal androvicidal agent’ containing, (a) an active substance of'the, grouplof;;an1idophos-' ' phoric acid 'diaryl esters of the followingkformula r in which R1 stands for ameinberrselecterddfrom the ' ‘ group consisting of hydrogen,- a'lowe'rrallqfl,v a lower alkenyl and T '1 r ' . V ‘ '5 lower elkylene-lr‘r-gw Ra)’: or J'l ' t 7c " ' R2 stands for a member selected, from thepgroup con ~- sisting of hydrogen, lower alkyl andrrlower ,alkenyl; and 'whenRL and R2 are takengtogether with the O V nitrogen atom',¢they form a member selected from a; the group consisting ofjethyleneiminmimorpholino, 0(8) thiamorpholino, piperazino and piperidino radicals; is}- and’ R3 vstands for a ‘halo-‘substituted phenyl radical; 3,058,879 References Cited in the ?le of this patent UNITED STATES PATENTS (b) a commercially non-ionic emulsi?er; (c) an auxiliary solvent; (d) water. 5. An acaricidal and ovicidal agent containing (a) an active substance of the following formula 2,615,037 2,615,038 2,615,039 2,635,112 2,759,937 2,802,823 (b) a commercially non-ionic emulsi?er; (c) an auxiliary solvent; (d) water. 6. An acaricidal and ovicidal agent containing (a) ‘an active substance of the ‘following formula 2,862,017 1° 2,994,638 Moyle _______________ .._ Oct. 21, Moyle _______________ __ Oct. 21, Drake _______________ __ Oct. 21, Fields _______________ ___ Apr. 14, Du Breuil ____________ __ Aug. 21, 1952 1952 ‘1952 1953 1956 Tolkmith et al ________ __ Aug. 13, 1957 Schrader et a1 _________ .__ Nov. 25, 1958 Malz et al ____________ __ Aug. '1, 1961 OTHER REFERENCES Sexton: “The Organic Chemist’s Approach to Chemo therapy,” pages 1-13 of “Selective Toxicity and Anti “ biotics,” Society of Experimental Biology (S.E.B.) Symp. No.1II, vol. III, 1949. (b) a commercially non-ionic emulsi?er; (c) an auxiliary solvent; (d) water.