CH602012A5 - (5)-Alkylthio-(1,2,4)-triazolyl-(3)-(thio)phosphates - Google Patents

Abstract

(5)-Alkylthio-(1,2,4)-triazolyl-(3)-(thio)phosphates parasiticides, insecticides, acaricides, nematocides, fungicides, herbicides, plant growth regulators, antibacterials and antivirals

Description

  

  
 



   The present invention relates to a pest control agent which, as the active component, is a compound of the formula
EMI1.1
 contains, in which Rl, R3, R4 and R5 are each C1-C6-alkyl, R2 is hydrogen or C1-C6-alkyl and X is oxygen or sulfur. The alkyl groups that come into consideration in R1-R5 can be straight-chain or branched.



   Examples of such groups include: a. Methyl, methyl, propyl, isopropyl, n-, i-, sec-, tert-butyl, n-pentyl, n-hexyl and their isomers.



   Because of their action, compounds of the formula I are preferred in which R1, R3, R4 and Ras joe are methyl or ethyl, R2 are methyl and X is sulfur.



   The compounds of formula I can, according to methods known per se, for. B. be manufactured as follows:
EMI1.2
 In the formulas II, III and IV, R1 to R5 and X have the meaning given for the formula I and Hal stands for halogen, preferably for chlorine or bromine, and Me for a metal, in particular an alkali metal, ammonium or trialkylammonium.



   The following bases, for example, can be used as acid-binding agents: tertiary amines, such as triethylamine, dimethylaniline, pyridine; inorganic bases, such as hydroxides and carbonates of alkali and alkaline earth metals, preferably sodium and potassium carbonate.



   Processes A and B are carried out at a reaction temperature of 0-120 ° C., preferably 20-80 ° C., under normal pressure and in solvents or diluents. Suitable solvents or diluents are, for. B. ethers and ethereal compounds such as diethyl ether, dipropyl ether, dioxane, dimethoxyethane, tetrahydrofuran; Amides such as N, N-dialkylated carboxamides; aliphatic, aromatic and halogenated hydrocarbons, in particular benzene, toluene, xylenes, chloroform, chlorobenzene; Nitriles such as acetonitrile; Dimethyl sulfoxide, ketones such as acetone, methyl ethyl ketone and water.



   The starting materials of the formula III are known. They can be produced analogously to known processes.



   The starting materials of formulas II and IV are new and can, for. B. be produced according to the following known scheme:
EMI1.3
  
EMI2.1
 In formulas II, IV to VII, R1-R3 have the meaning given for formula I and Me stands for a metal, in particular an alkali metal. The reaction of the compound VII with the compound VIII is carried out in a solvent at 10-120 ° C., preferably at 20-90 ° C., and takes a few minutes to a few hours, depending on the substituents and the reaction conditions. Suitable solvents are, for example, ketones such as acetone or methyl ethyl ketone; Tetrahydrofuran and water.



   The active ingredients of the formula I are suitable for controlling various types of animal and plant pests.



   They have nematicidal properties and can be used, for example, to control phytopathogenic nematodes. Some of the active compounds of the formula I are also suitable as herbicides and plant regulators and for combating viruses, bacteria and phytopathogenic fungi. But above all they act against all stages of development, such as eggs, larvae, nymphs, pupae and adults of insects and representatives of the order Acarina, such as mites and ticks.



   The compounds of the formula I have a lethal or repellent effect, for example, against the following insects or representatives of the order Akarina: Insects of the families: Tettigoniidae, Gryllidae, Gryllotalpidae, Blattidae, Reduviidae, Pyrrhocoridae, Cimicidae, Delphacidae, Aphididae, Diaspididae, Daspididae, Pseudococestidae , Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Culicidae, Tipulidae, Stomocydae, Trypetidae, Muscidae, Calliphoridae and Pulicidae as well as Akarines of the families: Ixodidae, Argasychidae,. The insecticidal and / or acaricidal effect can be significantly broadened by adding other insecticides and / or acaricides and adapted to the given circumstances.



   Suitable additives are, for. B.u. a .: org. Phosphorus compounds, nitrophenols and their derivatives, formamidines, pyrethrin-like compounds, ureas, carbamates and chlorinated hydrocarbons.



  The compounds of the formula I can be used alone or together with suitable carriers and / or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances customary in formulation technology, such as. B. natural or regenerated substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders and / or diing agents. For application, the compounds of the formula I can be processed into dusts, emulsion concentrates, granules, dispersions, sprays, into solutions or slurries in customary formulations which are part of general knowledge in application technology.

  Furthermore, cattle dips, i. H. Viehbader, and spray races, d. H. To mention spray courses in which aqueous preparations are used.



   Agents according to the invention are produced in a manner known per se by intimately mixing and / or grinding active ingredients of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active ingredients. The active ingredients can be present and used in the following working-up forms: Solid working-up forms: dusting agents, scattering agents, granules (encapsulating granules, impregnating granules and homogeneous granules); Liquid processing forms: a) Active substance concentrates dispersible in water:
Wettable powders, pastes, emulsions; b) Solutions.

 

   The content of active ingredient in the agents described above is between 0.1-95%.



   The active ingredients of the formula I can be formulated as follows, for example: Dusting agents: The following substances are used to produce a) 5% and b) 20% dusting agent: a) 5 parts of active ingredient,
95 parts of talc; b) 2 parts of active ingredient,
1 part of highly dispersed silica,
97 parts of talc.



   The active ingredients are mixed and ground with the carrier substances.



  Granules: The following substances are used to produce 5% granules:
5 parts active ingredient,
0.25 parts epichlorohydrin,
$ 0.25 part of cetyl polyglycol ether,
3.50 parts of polyethylene glycol, 91 parts of kaolin (grain size 0.3-0.8 mm).



   The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The solution obtained in this way is sprayed onto kaolin and then the acetone is evaporated in vacuo.



   Wettable powder: To produce a) 40%, b) and c) 25%, d) 10% wettable powder, the following components are used: a) 40 parts of active ingredient,
5 parts of lignin sulfonic acid sodium salt,
1 part dibutylnaphthalenesulfonic acid sodium salt,
54 parts of silica; b) 25 parts of active ingredient,
4.5 parts calcium lignosulfonate,
1.9 parts of champagne chalk / hydroxyethyl cellulose mixture (1: 1),
1.5 parts of sodium dibutyl naphthalene sulfonate,
19.5 parts of silica,
19.5 parts of champagne chalk,
28.1 parts of kaolin; c) 25 parts of active ingredient,
2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol,
1.7 parts of champagne chalk / hydroxyethyl cellulose mixture (1: 1),
8.3 parts sodium aluminum silicate,
16.5 parts kieselguhr,
46 parts of kaolin;

   d) 10 parts of active ingredient,
3 parts mixture of the sodium salts of saturated
Fatty alcohol sulfates,
5 parts of naphthalenesulfonic acid / formaldehyde
Condensate,
82 parts of kaolin.



  The active ingredients are intimately mixed with the additives in suitable mixers and ground on the appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to form suspensions of any desired concentration.



  Emulsifiable concentrates: The following substances are used to produce a) 100%, b) 25% and c) 500% emulsifiable concentrate: a) 10 parts of active ingredient,
3A parts epoxidized vegetable oil,
3.4 parts of a combination emulsifier, consisting of fatty alcohol polyglycol ethers and alkylarylsulfonate calcium salt,
40 parts of dimethylformamide,
43.2 parts of xylene; b) 25 parts of active ingredient,
2.5 parts epoxidized vegetable oil,
10 parts of an alkylarylsulfonate / fatty alcohol polyglycol ether mixture,
5 parts of dimethylformamide,
57.5 parts of xylene.



  c) 50 parts of active ingredient,
4.2 parts of tributylphenol polyglycol ethers,
5.8 parts calcium dodecylbenzenesulfonate,
20 parts of cyclohexanone,
20 parts of xylene.



  Emulsions of any desired concentration can be produced from such concentrates by diluting them with water. Injectables: To produce a) 50% and b) 95% spray, the following ingredients are used: a) 5 parts of active ingredient,
1 part epichlorohydrin,
94 parts of gasoline (boiling point 160-190 C); b) 95 parts of active ingredient,
5 parts of epichlorohydrin.



  Example 1 a) Preparation of 1- (1'Methyl-2'-methoxy-ethyl) -3-hydroxy-5-methylthio-1,2,4-triazole.



   0.5 moles of the compound of the formula CH3OCH2 # CH3
CH
N-NHCOOC2H5
CN
20 = 1.4712) are added dropwise at room temperature to a solution consisting of 0.5 mol of sodium hydroxide in 100 ml of water into which 0.5 mol of CH3SH had been introduced. The reaction is exothermic (70 ° C.). The reaction mixture is held at 80 ° C. for a further hour. After cooling, the product which crystallizes out is filtered off and recrystallized from ether / hexane. The compound of the formula is obtained
EMI3.1
 with a melting point of 102-104 C. In an analogous manner, the compound of the formula
EMI3.2
 (M.p. 94-96 C).



  b) Preparation of 0,0-diethyl-0- (1- (1'-methyl-2'-methoxyethyl) -5-methylthio-1,2,4-triazoly- (3)) -thiophosphoric acid ester.



   0.1 mol of 1-) 1'-methyl-2'-methoxy-ethyl) -3-hydroxy-5-methylthio-1,2,4-triazole and 0.1 mol of potassium carbonate in 200 ml of methyl ethyl ketone are for 2 hours on Reflux heated.



  After 0.1 mol of diethylthiophosphoric acid chloride has been added dropwise at 40.degree. C., the mixture is refluxed for another 2 hours and then left to stand at 20.degree. The salts are filtered off and the filtrate is concentrated in vacuo. The remaining residue is purified over silica gel with chloroform as the mobile phase.



   The compound of the formula is obtained
EMI4.1
 as an oil with a refraction of nD2 = 1.5033.



   The following connections are also established in the same way:
EMI4.2
 Example 2 A) Insecticidal feed poison effect
Cotton plants were sprayed with a 0.05% aqueous active ingredient emulsion (obtained from a 10% emulsifiable concentrate).



   After the covering had dried on, the cotton plants were each populated with Spodoptera littoralis and Heloithis virescens larvae L3. The experiment was carried out at 24 C and 60% relative humidity.



   Compounds according to Example 1b showed in the above test a good insecticidal feed poison action against Spodoptera and Heliothis larvae.



  B) Systemic insecticidal effect
To determine the systemic effect, rooted bean plants (Vicia faba) were placed in a 0.01% strength aqueous active ingredient solution (obtained from a 110% strength emulsifiable concentrate). After 24 hours, aphids (Aphis fabae) were placed on the above-ground parts of the plant. The animals were protected from contact and gas effects by a special device. The experiment was carried out at 24 C and 70% relative humidity.



   Compounds according to Example ib showed systemic insecticidal action against Aphis fabae in the above test.



  Example 3 Action against Chilo suppressalis
6 rice plants of the Caloro variety were transplanted into plastic pots with an upper diameter of 17 cm and raised to a height of about 60 cm. The infestation with Chilo suppressalis larvae (L,; 3-4 mm long) took place 2 days after the addition of the active ingredient in granulate form (application rate 8 kg active ingredient per hectare) in the paddy water. The insecticidal activity was evaluated 10 days after the granules had been added.



   Compounds according to Example 1b acted against Chilo suppressalis in the above test.



  Example 4
Acaricidal effect
Phaseolus vulgaris (plants) were covered with an infested piece of leaf from a mass cultivation of Tetranychus urticae 12 hours before the test for acaricidal activity.



  The overflowing mobile stages were sprayed with the emulsified test preparations from a chromatography nebulizer in such a way that the syringe liquor did not run off. After two and seven days, larvae, adults and eggs were evaluated for living and dead individuals under the dissecting microscope, and the result was expressed as a percentage.



  During the holding time, the treated plants stood in greenhouse cabins at 25 C.



   Compounds according to Example 1b were active in the above test against adults, larvae and eggs of Tetranychus urticae.



  Example 5 Action against soil nematodes
To test the action against soil nematodes, the active ingredients were added to soil infected by root cell nematodes (Meloidogyne arenaria) and mixed thoroughly.

 

  Immediately afterwards tomato seedlings were planted in the soil prepared in this way in one test series and tomatoes swat in after a waiting time of 8 days in another test series.



   To assess the nematicidal effect, the galls present on the roots were counted 28 days after planting or after sowing. In this test, active ingredients according to Example 1b showed a good action against Meloidogyne arenaria.



  Example 6 Action against Zecker A) Rhipicephalus bursa
5 adult ticks or 50 tick larvae were counted in a glass tube and immersed for 1-2 minutes in 2 ml of an aqueous emulsion from a dilution series with 100, 10.1 or 0.1 ppm test substance each. The tube was then closed with a standardized cotton ball and turned upside down so that the active ingredient emulsion could be absorbed by the cotton wool.



   The evaluation was carried out after 2 weeks for the adults and after 2 days for the larvae. Two repetitions were run for each attempt.



  B) Boophilus microplus (larvae)
With an analogous dilution series as in test A), 20 sensitive resp. OP-resistant larvae trials carried out (the resistance relates to the tolerance of diazinon) Compounds according to Example 1b were effective in these tests against adults and larvae of Rhipi cephalus bursa and sensitive resp. OP-resistant larvae of
Boophilus microplus.

 

  Example 7 Action against Erysiphe graminis on Hordeum vulgare
Barley plants about 8 cm high were sprayed with a spray mixture (0.05% active substance) made from wettable powder of the active ingredient. After 48 hours, the treated plants were dusted with conidia of the fungus. The infected barley plants were placed in a greenhouse at about 22 ° C. and the fungal attack was assessed after 10 days. Compounds according to Example 1b acted against Erysiphe graminis in this test.



   PATENT CLAIM I
A A pesticide. which as the active component is a compound of the formula
EMI5.1
 contains, where R ,, R3, R4 and Rs are each C1-C6-alkyl, R2 is hydrogen or Cl-C6-alkyl and X is oxygen or sulfur.

 

Claims (1)

SUBClaims 1. An agent according to claim I, which contains the compound of the formula CH3OCH2-CH-CH3 N-N S Contains CH3S-N-O-P (OC2H5) 2 2. A means according to claim I, which is the active component of the compound of formula EMI5.2 contains. PATENT CLAIM II Use of an agent according to claim I for combating insects and representatives of the order Akarina 40