1-(4-Chlorophenyl)-5-methyl-3-(0,0-diethylthiono phosphoryl)-1,2,4-triazole
United States Patent 1 Dawes et al.  
 [111 3,879,412 [4 1 Apr. 22, 1975 I l-(4-CHLOROPHENYL)-5-METHYL-3-(0,0-  
 DIETHYLTHIONO V PHOSPHORYL )-l .ZA-TRIAZOLE [75] Inventors: Dag Dawes. Prattele; Beat Boehner.  
 Binningen. both of Switzerland [73] Assignee: Ciba-Geigy Corporation, Ardsley.  
 [22] Filed: Apr. 1, 1974 [2]] Appl. No.: 456926 Related U.S. Application Data [63] Continuation-in-part of Scr. No. 217,289. Jan. 12  
 I972 abandoned.  
 [30] Foreign Application Priority Data Jun. 19. 1971 Switzerland 775/7] Oct. 22. l97l Switzerland l5409/7l Nov. 19, I97] Switzerland 16876/7] [52] U.S. Cl 260/308 R; 260/308 C;&#39;424/2OO [5 l] Int. Cl. C07f 9/16 [58] Field of Search 260/308 R [5 6] References Cited 8/l954 United Kingdom 260/308 R Primary Evaminer-Alton D. Rollins Attorney. Agent. or Firm-Harry Falber.  
 [57 ABSTRACT The l.2, 4-Triazolylphosphoric acid ester of the forits manufacture and its use in pest control.  
 , I Claim, No Drawings 1 l-(4-CHLOROPHENYL)-5-METHYL-3-(0,0- DIETHYLTHIONO PHOSPHORYL)-l ,2,4-TRIAZOLE RELATED APPLICATIONS l fi CH -C N}P (OC I-I (I) and may be manufactured by a. reacting the hydroxy-triazole of the formula Cl ON N (11) Mp.: 255-60C with the phosphoric halide of the formula ll 1&#39;10.1--P(OC H (III) in the presence of an acid binding agent, or  
  b. reacting a salt of the hydroxy-triazole of the formula II with aphosphoric halide of the formula III. In the formula III Hal represents chlorine or bromine.  
  As salts of hydroxy-triazoles of the formula II which are suitable for the process according to the invention there may be used, for example, salts of monovalent metals, in particular the alkali metal salts; besides these, however, there may be used other salts, for example those of monovalent heavy metals.  
  As acid binding agents the following bases may for example be used: tertiary amines, such as triethylamine, dimethyl aniline, pyridine bases, inorganic bases, for example hydroxides and carbonates of alkali and alkaline earth metals, preferably sodium and potassium carbonate.  
  The reactions may be carried out preferably in so]- vents or diluents which are inert towards the reactants. The following, for example, are suitable for this purpose: aromatic hydrocarbons, such as benzene, toluene, gasolines, halogenated hydrocarbons, chloroben zene, polychlorobenzenes, bromobenzene, chlorinated v alkanes containing 1 to 3 carbon atoms, ethers, such as dioxan, tetrahydrofuran; esters, for example ethyl acetate; ketones, for example methyl ethyl ketone, diethyl ketone, nitriles etc.  
  The starting material of the formula II is a known compound which can be manufactured according to methods which are known per se. This compound is obtained for example by reacting a correspondingly substituted semi-carbazide with ortho-carboxylic acid ethyl ester, or by firstly acylating a correspondingly substituted semi-carbazide and subsequently effecting cyclisation under alkaline conditions (cf. for example J. B. Chem. Ber. 56, 1797).  
  The compound of the formula I has a broad biocidal activity spectrum and may be used to combat vegetable and animal pests. I  
  Compared with analogous compounds from the US. Pat. No. 3,686,200 and the British Pat. No. 713,278, the compound of the formula I has a surprisingly better insecticidal action, particularly against AedesAegypti adults, Heliorhis zea larvae and Demestes frischii adults and a better acaricidal action, particularly against Rhipicephalus bursa larvae and adults. The compound of the formula I may be used, in addition, to combat all development stages, such as e.g., eggs, larvae, nymphs, pupae and adults of insects of the families: Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Diaspididae, Pseudococcidae, Chrysomelidae, Coccinellidae, Brucidae, Scarabaeidae; Dermestidae, Tenebrionidae, Curculionidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleridae, Culicidae, Tipulidae, Stomoxydae, Muscidae, Caliphoridae, Trypetidae, Pulicidae, as well as acarids of the families: Ioxodidae, Argasidae, Tetranychidae, Dermanyssidae.  
  The insecticidal or acaricidal action can be appreciably broadened and adapted to suit the given circumstances by the addition of other insecticides and/or acaricides. Suitable additives are, for example:  
 organic phosphorus compounds,  
 nitrophenols and derivatives,  
 formamidines,  
 carbarnates and chlorinated hydrocarbons.  
  Furthermore, the compound of the formula I possess extraordinarily good properties against plant parasitic nematodes.  
  The agents according to the invention are prepared in a known manner by the intimate mixing and/or grinding of the active substance of formula I with suitable carriers, optionally with the addition of dispersing agents or solvents which are inert to the active substances. The active substances can be obtained and used in the following forms: solid preparations:  
 dusts, scattering agents, granulates,  
 coated granulates, impregnated granulates, and homogeneous granulates; liquid preparations:  
 a. water-dispersible active-substance concentrates:  
 wettable powders, pastes or emulsions;  
 b. solutions.  
  The content of active substance in the described agents is between 0.1 and it is to be mentioned in this connection that in the case of application from an aeroplane, or by means of other suitable devices, concentrations of up to 99.5% can be employed, or even the pure active substance.  
  The active substance of formula I can be formulated. for example. as follows:  
 Dusts I The following substances are used in the preparation a) 57: dust. and b) a 29: dust: a) 5 parts of active substances.  
 )5 parts of talcum;  
 b) 2 parts of active substance.  
  1 part of highly dispersed silicic acid. 97 parts of talcum.  
 The active substances are mixed and ground with the carriers.  
 Granulate The following substances are used to produce a 5% granulatc:  
 5 parts of active substance.  
 0.25 parts of epichlorhydrin.  
 0.25 parts of cetyl polyglycol ether. 3.50 parts of polyethylene glycol. 1  
 parts of kaolin (particle size 0.30.8 mm).  
 a) a 4071. h) and c) a 25%, and d) a W: Wettable powder:  
 a) 40 parts of active substance.  
  5 parts of sodium lignin sulphonate, l part of sodium dibutyl-naphthalenc sulphonate. 54 parts of silicic acid. b) 25 parts of active substance,  
 4. parts of calcium lignin sulphonate 5 .9 parts of Champagne chalk/hydroxyethyl cellulose mixture (lzl l.5 parts of sodium dibutyl naphthalene sulphonate, 9.5 parts of silicic acid, 7 9 5 parts of Champagne chalk.  
  28. parts of kaolin. c) 25 parts of active substance.  
  2.5 parts of isooctylphenoxy-polyoxycthyleneethanol l.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (l:l 8.3 parts of sodium aluminium silicate, l6.5 parts of kieselguhr. 46 arts of kaolin. d) It) parts of active substance.  
 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates. 5 parts of naphthalenesulphonic acid/formaldehyde condensate. 82 parts of kaolin.  
  The active substance is intimately mixed, in suitable mixers, with the additives, and the mixture then ground in the appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to give suspensions of any desired concentration. Emulsifiable concentrates:  
  The following substances are used to produce a) a 10% and b) a 25% emulsifiahle concentrate: a) It) parts of active substance,  
  3.4 parts of epoxidised vegetable oil. l3.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylarylsulphonate calsium salt, 5 40 parts of dimethylformamide.  
  43.2 parts ol&#39;xylene. b) 25 parts of active substance.  
 2.5 parts of cpoxidised vegetable oil.  
 l0 parts of an alkylarylsulphonate/fatty alcoholpolyglycol ether-mixture.  
 parts of dimethylformamide.  
 parts of xylene.  
  From these concentrates it is possible to produce, by dilution with water, emulsions of any desired concentration.  
  Spray:  
  The following constituents are used to prepare a 5% spray:  
  5 pans of active substance,  
  1 part of cpichlorhydrin. 94 parts of ligroin (boiling limits l6()-l90C).  
 These solutions were sprayed with pressure sprays.  
 EXAMPLE 1 0,0-Diethyl-0-l-(4-chlorophenyl)-5-methyl-1,2,4- triazolyl-( 3 )-thiophosphate a. 18.65 Grams (0.1 M) of l-(4-chlorophenyl)- semicarbazide and l6.2 g (=l8.2 ml) of ortho-acetic triethyl ester are heated together with 40 ml of glycol monomethyl ether, in the process of which a clear yellow solution is obtained. The ethanol which forms is continually distilled off at an internal temperature of l20C. The residue is cooled after 4% hours and treated with 200 ml of ether, yielding l-(4- chlorophenyl )-3-hydroxy-5-methyll ,2,4-triazole (m.p.: 25560C.  
  b. 36 Grams 0.172 M) of 1-(4-chlorophenyl)-3- hydroxy-S-methyl-l,2,4-triazole and 23.6 g (0.172 M) of potassium carbonate are heated together with copper powder (from the tip of a spatula) in 400 ml of methyl ethyl ketone and the mixture is boiled for l hour under reflux. Then 32.3 g 0.172 M) of 0,0-diethylthiophosphoric chloride are added dropwise at C. The reaction mixture is refluxed for 3 hours and the solvent then evaporated in vacuo. The residue (59 g) is taken up in 500 ml of ether and washed successively with water, 0.5N HCI, saturated bicarbonate solution and sodium chloride solution. After drying the ether solution over sodium sulphate. The ether is evaporated in vacuo, leaving as residue 43.8 g of crude product. This product is filtered over 800 g of silica gel using methylene chloride as solvent, to yield 0,0- Diethyl-O- l 4-chlorophenyl )-5-methyll ,2 ,4-triazolyl- (3)-thiophoshpate (11 2 1.5484).  
 60 EXAMPLE 2 Comparative Test Test compounds:  
  &#39;N S v l H l N 2 5 2 Compound of formula II 3 a c1-On-n s oP oc a u.s. Patent No.3 686 200 Claim 7 Test animals Result Dermestes frischii Larvae Test preparation 10 l1 Mortality of 5 parts 1 ti i di Test compound Aedex uegypli adults in X time 95 parts of talc A 100 in I20 minutes Test B 0 in 24 hours The test preparation was applied to filter paper in a concentration of 12.5 mg per m Groups of 5 test anil5 Concluslon mals of the type indicated above are placed on the C d A i [00% i 120 in te effe tive treated substrates. After 24 hours the experiment against A d aegypli d l s, wh nd B i evaluated. ineffective (0%) in 24 hours against this insect. Results 71 mortality after 24 hours of EXAMPLE Test compound l)(&#39;!!1lt&#39;S!tSfI&#39;i.St/lii Larvae I Comparative Test A 100 B 0 Test compounds:  
 A C1 N-N S k ,l -O-P(0C R Compound of formula 1 3 2 5 2 L L n U. S. Patent No. 3 686 200 O-P 0C H Claim 3 I J 2 Conclusion Test animals The compound A is in a concentration of 12.5 mg/m Heliothis zea larvae 100% effective against Dermestes frischii Larvae Test preparation whereas compound B is at this concentration ineffec- 40 tlV against Dermestes frischii l .arvae. 1() 15 of active suhmuncc 3.4 parts of epoxidised vegetable oil. EXAMPLE 3 l3.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and aIkyl-arylsulphonate Comparatwe Test calcium salt.  
 &#39; 40 parts of dimethylformamide. Test compounds: 43.2 parts of xylene.  
 A at N S 0-- I&#34;(OC l-l Compound of formula I c11 B O 0--P (OC H British Patent Test animals Test Aedes aegypti adults Cottonplants were sprayed with a 0.05% aqueous Test preparation emulsion (obtained from a 10% emulsifiable concen- Acetonic solutions of the active ingredients A and B. m Aft r the coating has dried 10 Heliothis Zea vae were settled on each of the cotton plants.  
 Test The test was carried out at 24C and 60% relative hu- Coatmgs of the acetomc solution of test substances midity where applied in Petri dishes, whereby a concentration R It of 1 mg oftest substance per dish was used. 5  
 . 7! mortality after 48 hours of 20 Aedes aegyptz adults were placed in the dishes Test compound HeliUl/lis 20a larvae after 1 hour. The time is evaluated after which all iny A &#39;00 sects lying on their back. B 0  
 , 7 8 Conclusion Results Compound A is 100% in 48 hours effective against g g mvrlulily after 1 I uys of 2 weeks of [161101 118 Z larvde wlllcrcdscqmpound B mcffcctwe Test compounds Rhipicephalus burxa Rhipit&#39;eplmlus hurxa m 48 hours against this insect. larvae adults v A I00 100 B O 0 EXAMPLE 5 Conclusion Compamnve Test A 0.1 ppm emulsion of compound A is 100% active Test Compounds: against adults and 1 larvae of Rhipiceplzalus bursa A Cl N S H O-P (OC H Compound of formula I C 3 B Q1 Q ll O-P(OC H U.&#39;S. Patent No. 3 686 200 Claim 3 Test animals whereas compound B is at this concentration ineffec- Rhipicephalus bursa adults and larvae. tive. -Test preparation We claim:  
 &#39; l. The compound of the formula 10 parts of active substance.  
  3.4 parts of epoxidised vegetable oil. l3i4 parts of a combination emulsifier consisting of fatty 7 alcohol polyglycol ether and alkyl-arylsulphonate C1 NN 8 calcium salt, l I 40 parts of dimethylformamide. 43.2 parts of xylene. CH3 &#39;C 6-0.1? 2 )2 Test  5 Tick adults and 50 Tick larvae were dipped in an emulsion containing 0.1 ppm active ingredient. Evaluation 3 days after application for larvae and 2 weeks for adults.