CH574215A5 - 0-(2-Alkenylphenyl) O,S-dialkyl thiophosphates - with insecticidal, acaricidal, fungicidal and nematocidal activity - Google Patents

Abstract

New cpds. of formula (I): (where R1 is Me or Et; R2 is n-Pr, i-Pr, i-Bu, s-Bu or n-amyl; R3 is H or Me; X is H, halogen, Me MeS, MeSO7, MeO or MeCO; n = 1-3) are pref. prepd. by reacting R1O (R2S)POCl with a cpd. (II): (where M is H, alkali metal, NH4 or alkylammonium), opt. in the presence of an acid binder (when M = H).

Description

  

  
 



   The present invention relates to a pest control agent containing a thiol phosphoric acid ester as the active component and its use for pest control.



   The thiol phosphoric acid esters have the formula
EMI1.1
 where Rt is methyl or ethyl,
R2 n-propyl, isobutyl, sec-butyl or n-pentyl,
R3 hydrogen or methyl,
X is hydrogen, halogen, C144-alkyl, methylthio, methylsulfinyl, Ci-C4-alkoxy or acetyl n denotes the numbers 1 to 4, where, when n denotes 2, 3 or 4, the substituents X can be identical or different.



   Halogen is to be understood as meaning fluorine, chlorine, bromine and / or iodine.



   The alkyl or alkoxy groups that come into consideration for X can be branched or straight-chain. Examples of such groups are: methyl, ethyl, propyl, isopropyl, n-, i-, sec-, tert-butyl, methoxy, ethoxy and n-propoxy, but methyl and methoxy are preferred.



   Because of their action, compounds of the formula I are preferred in which
R1 ethyl,
R2 n-propyl,
X is hydrogen, chlorine, methyl, methoxy, methylthio or methylsulfinyl and n is 1 or 2.



   The compounds of the formula I can be prepared by the following methods known per se:
EMI1.2


<tb> <SEP> 0 <SEP> R
<tb> la) <SEP> R; y01 <SEP> + <SEP> GH = C-CH? <SEP> bd <Ie
<tb> <SEP>) P-C1
<tb> <SEP> (11) <SEP> medium
<tb> <SEP> (iii) <SEP> (X) n
<tb> <SEP> R
<tb> <SEP> I
<tb> <SEP> lb <SEP>) PC1 <SEP> + <SEP> CH = C-CH3
<tb> <SEP> MeO
<tb> <SEP> (IV) <SEP> (i
<tb> <SEP> R
<tb> <SEP> R <SEP> 0
<tb> <SEP> 2) <SEP> + <SEP> H <SEP> acid-binding agent of <SEP>> <SEP> VI
<tb> <SEP> (<SEP> III) <SEP> (X)
<tb> <SEP> R13
<tb> <SEP> R10 <SEP> E <SEP> CHsCH3
<tb> <SEP> \ p-O- (3- <SEP> + <SEP> of the <SEP>
<tb> <SEP> (VI) <SEP> (X) n <SEP> (VII)
<tb> <SEP> (vi) <SEP> (X) <SEP> (vii)
<tb>
EMI2.1

In formulas II to XI, R1, R2, R3, X and n have the meaning given for formula I and Me stands for an alkali metal,

   in particular for sodium or potassium, ammonium or alkylammonium and Hal for a halogen atom, such as fluorine, chlorine, bromine or iodine.



   Suitable acid-binding agents are tertiary amines, e.g. B. trialkylamines, pyridine, dialkylanilines; inorganic bases such as hydrides, hydroxides; Carbonates and bicarbonates of alkali and alkaline earth metals.



   In the reactions it is sometimes advantageous to use catalysts, such as. B. copper or copper chloride to be used.



  Processes la and Ib, 2 and 3 are carried out at a reaction temperature between 0-130 ° C., at 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, 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 and methyl ethyl ketone; Water. Ethanol is also suitable for method 3.



   The starting materials of the formulas II, V and VIII can analogously known, for. B. in the Organic Reactions II pages 1 to 48 described methods can be prepared.



   The compounds of the formula I have a broad biocidal action and can be used to control various types of plant and animal pests. But, surprisingly, they work better z. B.



  against larvae of Spodoptera littoralis as analogous compounds from German Patent 1,164,408. However, they are also suitable for combating all stages of development, such as e.g. B. Eggs, larvae, pupae, nymphs and adults of insects belonging to the following families: Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Pyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae, Cocidae, Daircinidae, Pseudococcidae. Tenebrionidae, Curculionidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleriidae, Culicidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae, Pulicidae as well as acarids of the families: Ixodidae, Tetermanyssychidae.



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



   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.



   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, for. B. in the work-up forms described in German Offenlegungsschrift No. 2 248 307 on pages 12 to 18 are available and used.



   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 of 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:
To produce a) 40%, b) and c) 25% d) 10% wettable powder, the following ingredients 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 of sodium aluminum silicate
16.5 parts of diatomaceous earth
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 mixed with the in suitable mixers
The aggregates are intimately mixed 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:
The following ingredients are used to make a 5% spray:
5 parts active ingredient,
1 part epichlorohydrin,
94 parts of gasoline (boiling point 1601900 C);
Manufacturing example
O-ethyl-S-n-propyl-O- [2-propenyl-4-methylphenyl] thiol phosphate
8.08 g of triethylamine are added to a solution of 11.85 g of 2-propenyl-4-methylphenol (boiling point 90 ° C./0.05 Torr) in 120 ml of benzene. At 10-15 ° C., 16.24 g of O-ethyl-S-n-propylthiolphosphoric acid chloride are added dropwise with constant stirring. Stirring is continued for 12 hours at room temperature. The triethylamine hydrochloride is filtered off with suction and the filtrate is washed with water, 2N soda solution and water.

  After drying the solution over sodium sulfate and distilling off the benzene, the compound of the formula is obtained
EMI3.1
 as a yellow oil with a refraction of nD20 = 1.5345.



   The following connections are also established in the same way:
EMI3.2
 R1 R2 R3 X n nD20 C2H5 (n) C3H7 H 4-SCH3 1 1.565 C2H5 (sec) C4Hg H 4-SCH3 1 1.5654 C2H5 (i) C4H9 H 4-SCH3 1 1.5552 C2H5 (n) C3H7 H 6 -C1 1 1.5478 C2Hs (sec) C4Hg H 6-Cl 1 1.5379 C2H5 (i) C4H9 H 6-C1 1 1.5423 C2H5 (n) C3H7 H 4-C1 1 1.544 C2H5 (i) C4H9 H 4 -C1 1 1.5409 C2115 (n) C3H7 HH 1 1.5375 C2H5 (i) C4H9 HH 1 C2H5 (n) C3H7 H 4,6-Cl2 2 1.5568 C2H5 (n) C3H7 H 4,5-Cl2 2 1.5538 C2H5 (n) C3H7 H 3.5-Cl2 2 1.5518

     C2H5 (n) C3H7 H 3,6-Cl2 2 1.5532 QH5 (n) C3H7 H 4-Br, 6-C1 2 1.5692 C2H5 (n) C3H7 H 4-Cl, 6-Br 2 1.5692 C2H5 (n) C3H7 H 4-SCH3, 5-CH3 2 1.5668 C2H5 (n) C3H7 H 4,6-Br2 2 1.5801 C2H5 (n) C3H7 H 5,6- (CH3) 2 2 1.5410 C2H5 (n) C3H7 H 4-Br 1 1.557 C2H3 (n) C3H7 H 4-OCH3 1 1.539 C2H5 (n) C3H7 H 4-F 1 1.527 C2H5 (n) C3H7 H 5-OCH3 1 1.5435 C2H5 (n) C3H7 H 4-Cl,

   5-CH3 2 1.541 C2H5 (n) C3H7 H 4-COCH3 1 1.550 C2H5 (n) C3H7 H 4,5- (CH3) 2 2 1,5335 C2H5 (n) C3H7 H 3,4,6-Cl3 3 1, 5614 C2H5 (i) C4H9 H 3,4,6-Cl3 3 C2H5 (n) C3H7 H 3,6-C12, 4-Br 3 1,578 C2H5 (i) C4H9 H 3,6-Cl2, 4-Br 3 1, 5614 C2H5 (n) C3H7 CH3 4-SCH3 1 1.5598 C2H5 (n) C3H7 CH3 6-C1 1 1.5389 C2H5 (n) C3H7 CH3 4-C1 1 1.5368 C2H5 (n) C3H7 H 3.5- (CH3) 2,

   4-C1 3 1.5405 C2H5 (n) C3H7 H 3,4,5-Cl3 3 1.5618 C2H5 (n) C3H7 H 4-SOCH3 1 1.5619 C2H5 (n) C5H11 H 4-SCH3 1 1.5614 C2H5 (n) C5H11 H 3,4,6-Cl3 3 1.5581
example 1
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 vires cens larvae L3. The experiment was carried out at 24 C and 60% relative humidity.



   In the above test, the compounds according to the preparation example showed a good insecticidal feed poison action against Spodoptera and Heliothis larvae.



   Example 2
Effect against Chilo suppressalis
Rice seedlings of the Caloro variety were grown in a plastic cup in such a way that their roots were matted into a disc. This was exchanged for an emulsion of the test preparation in a concentration of 800 ppm and allowed to drain. Then 5 test animals (L2 larvae) were placed in the beaker and the treated plants were placed on top. The percent kill of the animals was determined 5 days later.



   The compounds according to the preparation example showed a good effect in this test against Chilo suppressalis.



   Example 3
Effect against ticks
A. Rhipicephalus bursa
5 adult ticks or 50 tick larvae were counted in a glass tube and immersed for 1 to 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, tests were carried out with 20 sensitive or OP-resistant larvae. (The resistance relates to the tolerance of Diazinon).



   The compounds according to the preparation example acted in these tests against adults and larvae of Rhipicephalus bursa and sensitive or OP-resistant larvae of Boophilus microplus.



   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 two to 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.



   In the above test, the compounds according to the preparation example acted against adults, larvae and eggs of Tetranychus urticae.



   PATENT CLAIM I
Pesticides containing as active component a compound of the formula (I)
EMI4.1
 wherein
R1 methyl or ethyl,
R2 n-propyl, isobutyl, sec-butyl or n-pentyl,
R3 hydrogen or methyl,
X is hydrogen, halogen, C1-C4-alkyl, methylthio, methylsulfinyl, C1-C4-alkoxy or acetyl and n denotes the numbers 1 to 4, where, when n denotes 2, 3 or 4, the substituents X can be identical or different .

 

   SUBCLAIMS
1. Means according to claim I containing a compound of the formula (I), wherein R1 is ethyl,
R2 n-propyl,
X denotes hydrogen, chlorine, methyl, methoxy, methylthio or methylsulfinyl and n denotes the numbers 1 or 2.



   2. Means according to dependent claim 1, containing the compound of the formula
EMI4.2

3. Means according to dependent claim 1, containing the compound of the formula
EMI4.3

4. Means according to dependent claim 1, containing the compound of the formula
EMI4.4

5. Means according to dependent claim 1, containing 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 **. Active substance emulsion (obtained from a 10% emulsifiable concentrate) sprayed. After the covering had dried on, the cotton plants were each populated with Spodoptera littoralis and Heliothis vires cens larvae L3. The experiment was carried out at 24 C and 60% relative humidity. In the above test, the compounds according to the preparation example showed a good insecticidal feed poison action against Spodoptera and Heliothis larvae. Example 2 Effect against Chilo suppressalis Rice seedlings of the Caloro variety were grown in a plastic cup in such a way that their roots were matted into a disc. This was exchanged for an emulsion of the test preparation in a concentration of 800 ppm and allowed to drain. Then 5 test animals (L2 larvae) were placed in the beaker and the treated plants were placed on top. The percent kill of the animals was determined 5 days later. The compounds according to the preparation example showed a good effect in this test against Chilo suppressalis. Example 3 Effect against ticks A. Rhipicephalus bursa 5 adult ticks or 50 tick larvae were counted in a glass tube and immersed for 1 to 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, tests were carried out with 20 sensitive or OP-resistant larvae. (The resistance relates to the tolerance of Diazinon). The compounds according to the preparation example acted in these tests against adults and larvae of Rhipicephalus bursa and sensitive or OP-resistant larvae of Boophilus microplus. 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 two to 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. In the above test, the compounds according to the preparation example acted against adults, larvae and eggs of Tetranychus urticae. PATENT CLAIM I Pesticides containing as active component a compound of the formula (I) EMI4.1 wherein R1 methyl or ethyl, R2 n-propyl, isobutyl, sec-butyl or n-pentyl, R3 hydrogen or methyl, X is hydrogen, halogen, C1-C4-alkyl, methylthio, methylsulfinyl, C1-C4-alkoxy or acetyl and n denotes the numbers 1 to 4, where, when n denotes 2, 3 or 4, the substituents X can be identical or different . SUBCLAIMS 1. Means according to claim I containing a compound of the formula (I), wherein R1 is ethyl, R2 n-propyl, X is hydrogen, chlorine, methyl, methoxy, methylthio or methylsulfinyl and n is 1 or 2. 2. Means according to dependent claim 1, containing the compound of the formula EMI4.2 3. Means according to dependent claim 1, containing the compound of the formula EMI4.3 4. Means according to dependent claim 1, containing the compound of the formula EMI4.4 5. Means according to dependent claim 1, containing the compound of the formula EMI5.1 PATENT CLAIM II Use of an agent according to claim I for combating insects and representatives of the Akarina order.