CH590007A5 - 1-(2-Cyanoethyl)-1,2,4-triazol-3-yl (thio)phosph(on)ates - prepd. by reacting 3-hydroxy cpds. with (thio)phosphor(on)yl halides - Google Patents

Abstract

Esters of formula (I) (where R1 is 1-6C alkyl, alkoxy or alkylthio; R2 is 1-6C alkyl; R3 is H, Cl, Br, 1-6C alkyl, 1-6C alkylthio, 3-5C alkenylthio or 3-5C alkynylthio; and X is O or S), e.g. (I; R1 = OEt, R2 = Et, R3 = H, X = S), are new cpds. which may be prepd. by reacting halides of formula (II) (where Hal is halogen) with cpds. of formula (III) (where M is H or metal, ammonium or trialkyl-ammonium), the reaction being carried out in the presence of an acid-binding agent when M is H. (I) are biocidal agents having nematocidal, insecticidal, acaricidal and, in some cases, herbicidal and plant growth regulating activity, as well as activity against viruses, bacteria and phytopathogenic fungi.

Description

  

  
 



   The present invention relates to a pesticide which, as the active component, is a 1,2,4-triazole derivative of the formula
EMI1.1
   emnalt, worm
R1 C1-C6-alkyl, C1-C6-alkoxy or C1-C6-alkylthio,
R2 Cl-C6-alkyl, R3 hydrogen, chlorine, bromine, C1-C6-alkyl, C, -C6-alkylthio, C3-Cs-alkenylthio or C3-C5-alkynylthio and
X represent oxygen or sulfur.



   The alkyl, alkoxy, alkylthio, alkenylthio or alkynylthio groups which come into consideration for R1, R2 and R3 can be straight-chain or branched. Examples of such groups include: a. Methyl, methoxy, methylthio, ethyl, ethoxy, ethylthio, propyl, propoxy, propylthio, isopropyl, n-, i-, sec-, tert-butyl, n-pentyl, n-hexyl and their isomers, allylthio, methallylthio, Propargylthio.



   Because of their action, compounds of the formula 1 are preferred in which
R1 ethyl, methoxy, ethoxy or (n) propylthio,
R2 methyl or ethyl,
R3 hydrogen, chlorine, bromine, methyl, methylthio, ethylthio or allylthio and
X mean sulfur.



   However, compounds of the formula I in which
R1 ethyl, ethoxy or (n) propylthio,
R2 ethyl,
R3 is hydrogen, methyl, methylthio or ethylthio and
X mean 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, R2, R3 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 are suitable 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 generally carried out at a reaction temperature of 0-120 C, preferably at 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 formulas II and IV are new and those of the formula III are known. However, they can be prepared in any analogous known process.



   The active ingredients of the formula I are suitable for combating animal and vegetable 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 fatal or repellent effect, for example, on the following insects or representatives of the order Akarina: Insects of the families: Tettigoniidae, Gryllidae, Gryllotalpidae, Blattidae, Reduviidae, Pyrrhocoridae, Cimicidae, Delphacidae, Aphididae, Diaspididae, Pseudococcidae , Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Culicidae, Tipulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridae and Pulicidae and acarids of the families: Ixodidae, Argasychidae,.



   The insecticidal and / or acaricidal effect can be significantly broadened and adapted to the given circumstances by adding other insecticides and / or acaricides.



   Suitable additives are, for. B. u. a .: org. Phosphorus compounds,
Nitrophenols and their derivatives,
Formamidines, pyrethroid-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 fertilizers. For application, the compounds of the formula I can be processed into dusts, emulsion concentrates, granules, dispersions, sprays, into solutions or slurries in the customary formulation, which are part of general knowledge in application technology. Furthermore, cattle dips, i. H. Cattle baths, and spray races, d. H. Mention should be made of spray courses in which aqueous preparations are used.



   The agents according to the invention are prepared 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:
Dusts, grit, granules (coating granules, impregnation 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 and 95%.



   The active ingredients of the formula I can be formulated as follows, for example: Dusts:
The following substances are used to produce a) 5% and b) 2% dust: 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 the acetone is then evaporated in vacuo.



  Wettable powder:
The following ingredients are used to produce a) 40%, b) and c) 25%, d) 10% wettable powder: 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 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) 10% and b) 25% emulsifiable concentrate: a) 10 parts of active ingredient,
3.4 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.



   Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.



  Spray:
To produce a 5- resp. 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) or b) 95 parts of active ingredient
5 parts of epichlorohydrin.

 

   example 1
Preparation of O, O-diethyl-O- [1-cyanoethyl-1,2,4-triazolyl- (3)] -thiophosphoric acid ester 1 a) 1-cyanoethyl semicarbazide
1672 g of semicarbazide hydrochloride are dissolved in 2 liters of water and neutralized with 600 g of sodium hydroxide in 1 liter of water while cooling. After 795 g of acrylonitrile have been added dropwise, the mixture is heated to 80 ° C. for 7 hours.



   After standing for 4 hours at 0 C, the precipitated, crystalline product is filtered off and dried under vacuum.



  1152 g of white product with a melting point of 125-128 ° C. are obtained. Analysis:
Calc .: C 37.5 H 6.3 N 43.7%
Found: C 37.2 H 6.3 N 43.4%
1b) 1-cyanoethyl-3-hydroxy-1,2,4-triazole
512 g of 1-cyanoethyl semicarbazide in 1990 ml of ethyl orthoformate are heated to 110 ° C. for 45 minutes. 900 g of the resulting ethanol are distilled off at a temperature between 110-130 C. After cooling to 20 ° C., the precipitated crystalline product is filtered off, washed with ether and dried under vacuum. 530 g of white product with a melting point of 182-184 ° C. are obtained.



  Analysis:
Calc .: C 43.5 H 4.35 N 40.5%
Found: C 43.4 H 4.4 N 41.0% lc) O, O-diethyl-O- [1-cyanoethyl-1,2,4-triazolyl- (3)] thiophosphoric acid ester
27.6 g of 1-cyanoethyl-3-hydroxy-1,2,4-triazole and 27.6 g of potassium carbonate in 1000 ml of methyl ethyl ketone are refluxed for 2 hours. After 37.6 g of diethylthiophosphoric acid chloride have been added dropwise at 40 ° C., the mixture is refluxed for another 2 hours, then left to stand for 15 hours at 20 ° C. The salts are filtered off and the filtrate is concentrated in vacuo. The oily residue is poured over Chromatographed silica gel with methyl ethyl ketone as the mobile phase.

  55.6 g of an oily compound of the formula are obtained
EMI3.1
 np20 = 1.4980 Analysis:
Calc .: C 37.2 H 5.2 N 19.3 S 11.0%
Found: C 37.4 H 5.3 N 18.2 S 11.4%
The following connections are also established in the same way:
EMI3.2
 nD20 = 1.5336 nD20 = 1.4990 nD20 = 1.5000 nD20 = 1.4664 nD20 = 1.5299 nD20 = 1.5085 nD20 = 1.5159
EMI4.1

Example 2
A. Insecticidal feed poison effect
Cotton plants were sprayed with a 0.05% aqueous active substance emulsion (obtained from a 10% emulsifiable concentrate).



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



   In the above test, compounds according to Example 1 showed 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 10% 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 1 acted against Aphis fabae in the above test.



   Example 3
Effect 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 (L1; 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 evaluation of the insecticidal effect he followed 10 days after the addition of the granules.



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



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



  The overflowing mobile stages were dusted with the emulsified test preparations from a chromatography atomizer so that the spray mixture did not run off. After 2 and 7 days, larvae, adults and eggs were evaluated under the binocular for living and dead individuals and the result was expressed as a percentage. During the holding time, the treated plants stood in greenhouse cabins at 25 "C.



   In the above test, compounds according to Example 1 were effective against adults, larvae and eggs of Tetranychus urticae.



   Example 5
Effect 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.



  Tomato seedlings were planted immediately afterwards in the soil prepared in this way in one test series and tomatoes were sown in another test series after a waiting period of 8 days.



   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 1 showed a good effect against Meloidogyne arenaria.



   PATENT CLAIM 1
Pesticide, the active component of which is a 1,2,4-triazole derivative of the formula
EMI4.2
 contains where
R1 C1-C6-alkyl, C1-C6-alkoxy or C1-C6-alkylthio,
R2 C1-C6-alkyl,
R3 is hydrogen, chlorine, bromine, C1-C6-alkyl, C-C6-alkylthio, C3-Cs-alkenylthio or C3-Cs-alkynylthio and
X represent oxygen or sulfur.

 

   SUBCLAIMS
1. Means according to claim I, which is a compound of the formula as active component
EMI4.3
 contains where
R1 ethyl, methoxy, ethoxy or (n) propylthio,
R2 methyl or ethyl,
R3 hydrogen, chlorine, bromine, methyl, methylthio, ethylthio or allylthio and
X mean sulfur.



   2. Agent according to claim I, which is the compound of the formula

** WARNING ** End of DESC field could overlap beginning of CLMS **.



   

 

Claims (1)

** WARNING ** Beginning of CLMS field could overlap end of DESC **. EMI4.1 Example 2 A. Insecticidal feed poison effect Cotton plants were sprayed with a 0.05% aqueous active substance emulsion (obtained from a 10% emulsifiable concentrate). After the covering had dried on, the cotton plants were each populated with Spodoptera littoralis and Heliothis virescens larvae L3. The experiment was carried out at 24 C and 60% relative humidity. In the above test, compounds according to Example 1 showed 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 10% 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 1 acted against Aphis fabae in the above test. Example 3 Effect 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 (L1; 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 evaluation of the insecticidal effect he followed 10 days after the addition of the granules. Compounds according to Example 1 acted against Chilo suppressalis in the above test. Example 4 Acaricidal effect Phaseolus vulgaris (plants) were covered with an infected piece of leaf from a mass cultivation of Tetranychus urticae 12 hours before the test for acaricidal activity. The overflowing mobile stages were dusted with the emulsified test preparations from a chromatography atomizer so that the spray mixture did not run off. After 2 and 7 days, larvae, adults and eggs were evaluated under the binocular for living and dead individuals and the result was expressed as a percentage. During the holding time, the treated plants stood in greenhouse cabins at 25 "C. In the above test, compounds according to Example 1 were effective against adults, larvae and eggs of Tetranychus urticae. Example 5 Effect 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. Tomato seedlings were planted immediately afterwards in the soil prepared in this way in one test series and tomatoes were sown in another test series after a waiting period of 8 days. 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 1 showed a good effect against Meloidogyne arenaria. PATENT CLAIM 1 Pesticide, the active component of which is a 1,2,4-triazole derivative of the formula EMI4.2 contains where R1 C1-C6-alkyl, C1-C6-alkoxy or C1-C6-alkylthio, R2 C1-C6-alkyl, R3 is hydrogen, chlorine, bromine, C1-C6-alkyl, C-C6-alkylthio, C3-Cs-alkenylthio or C3-Cs-alkynylthio and X represent oxygen or sulfur. SUBCLAIMS 1. Means according to claim I, which is a compound of the formula as active component EMI4.3 contains where R1 ethyl, methoxy, ethoxy or (n) propylthio, R2 methyl or ethyl, R3 hydrogen, chlorine, bromine, methyl, methylthio, ethylthio or allylthio and X mean sulfur. 2. Means according to claim I, which is the active component of the compound of formula EMI5.1 contains. 3. Agent according to claim I, which is the compound of the formula EMI5.2 contains. 4. Means according to claim I, which is the compound of the formula EMI5.3 5. Agent according to claim I, which is the compound of the formula EMI5.4 contains. PATENT CLAIM II Use of an agent according to claim I for combating pests. SUBClaim 6. Use according to claim II for combating insects and representatives of the Akarina order.