CH583518A5 - 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 pesticide containing as active component a thiol phosphoric acid ester and its use for pest control.



   The thiol phosphoric acid esters contained in the agent according to the invention have the formula
EMI1.1
 where Rl is methyl or ethyl,
R2 isopropyl,
R3 hydrogen or methyl,
X denotes hydrogen, halogen, methyl, methylthio, methyl sulfinyl, methoxy or acetyl and n denotes the numbers 1 to 3.



   Halogen is understood to mean fluorine, chlorine and / or bromine.



   Because of their action, compounds of the formula I are preferred in which R is ethyl and
X denotes hydrogen, chlorine, methyl, methylthio or methyl sulfinyl.



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


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<tb> <SEP> IoII
<tb> la) <SEP> RlOE-Cl <SEP> CH = CCH
<tb> <SEP> R2 <SEP> + <SEP> - <SEP> acid bath
<tb> <SEP> means
<tb> <SEP> (III) <SEP> (X)
<tb> <SEP> 0 <SEP> R3
<tb> <SEP> R1Os <SEP> 1I <SEP> CH - CCH.
<tb>



   <SEP> ib) <SEP> + <SEP> -CH,
<tb> <SEP> CH-C
<tb> <SEP> L <SEP> (II)
<tb> <SEP> n
<tb> <SEP> R
<tb> <SEP> R <SEP> O
<tb> <SEP> 2) <SEP> Ä'Ol <SEP> cI = ocN
<tb> <SEP> (v) <SEP> + <SEP> Ht <SEP> acid-binding <SEP> V1
<tb> <SEP> (v) <SEP>
<tb> <SEP> (III) <SEP> (X)
<tb> <SEP> (X)
<tb> <SEP> 13
<tb> <SEP> R <SEP> oO <SEP> CH = CH3
<tb> <SEP> 1 \ II <SEP> - <SEP> acid-binding
<tb> <SEP> + <SEP> R2 <SEP> Medium <SEP> / 1
<tb> <SEP> cl
<tb> <SEP> (vi) <SEP> (X) n <SEP> (vII)
<tb>
EMI2.1

In formulas II to XI, R1, R2, R3, X and n have the meanings 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 lb, 2 and 3 are carried out at a reaction temperature between 0-130 ° 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, 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; 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 Offenlegungsschrift No. 2 163 391.



   Furthermore, they are also suitable for combating all stages of development such. B. Eggs, larvae, pupae, nymphs and adults of insects of the families: Acridididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Pyrrhocoridae, Reduvviidae, Aphididae, Delphacidae, Diaspididae, Scarysidae, Chrysocomidae, Chrysocomidae, Pseudococcellidae 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.



   Suitable additives are, for. E.g .: organic phosphorus compounds;
Nitrophenols and derivatives;
Formamidine;
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.



   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%, it should be mentioned that when applied from an airplane or by means of other suitable application devices, concentrations of up to 99.5% can be 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 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 Ch ampagne 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 ether and alkylaryl sulfonate calcium salt,
40 parts of dimethylformamide,
43 parts of xylene; b) 25 parts of active ingredient,
2.5 parts epoxidized vegetable oil,
10 parts of an alkylarylsulfonate / fatty alcohol poly glycol 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 160-190 C).



   example 1
O-ethyl-S-isopropyl-O- [2-propenyl-4-methylthiophenyl] thiol phosphate
8.08 g of triethylamine are added to a solution of 12.4 g of 2-propenyl-4-methylthiophenol in 120 ml of benzene. At 10-15 ° C., 16.24 g of O-ethyl-S-isopropylthiolphosphoric 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

Example 2
Insecticidal food 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 L3 Spodoptera littoralis or Haliothis virescens larvae. The experiment was carried out at 24 C and 60% relative humidity. In the above test, the compounds according to Example 1 showed a good insecticidal feed poison action against Spodoptera and Heliothis larvae.



   Example 3
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 Example 1 showed a good effect in this test against Chilo suppressalis.



   Example 4
Action 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 addults 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 larval experiments were carried out. (The resistance refers to the tolerance of Diazinon.)
The compounds according to Example 1 showed in these tests a good effect against adults and larvae of Rhipicephalus bursa and sensitive resp. OP-resistant larvae of Boophilus microplus.



   Example 5
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 in a concentration of 400 ppm from a chromatography atomizer, so that no runoff of the spray mixture occurred. After two to 7 days, larvae, adults and individuals 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 Example 1 showed a good action against adults, larvae and eggs of Tetranychus urticae.

 

   PATENT CLAIM 1
Pesticides containing as active component a compound of the formula (I)
EMI4.1
   wonn
R1 methyl or ethyl,
R2 isopropyl,
R3 hydrogen or methyl,
X denotes hydrogen, halogen, methyl, methylthio, methylsulfinyl, methoxy or acetyl and n denotes the numbers 1 to 3.



   SUBCLAIMS
1. Means according to claim I containing a compound of the formula I, wherein Ra and ethyl
X denotes hydrogen, chlorine, methyl, methylthio or methylsulfinyl.



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

PATENT CLAIM II
Use of an agent according to claim I for combating insects and representatives of the order Akarina.

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



   

 

Claims (1)

** WARNING ** Beginning of CLMS field could overlap end of DESC **. After the covering had dried on, the cotton plants were each populated with L3 Spodoptera littoralis or Haliothis virescens larvae. The experiment was carried out at 24 C and 60% relative humidity. In the above test, the compounds according to Example 1 showed a good insecticidal feed poison action against Spodoptera and Heliothis larvae. Example 3 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 Example 1 showed a good effect in this test against Chilo suppressalis. Example 4 Action 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 addults 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 larval experiments were carried out. (The resistance refers to the tolerance of Diazinon.) The compounds according to Example 1 showed in these tests a good effect against adults and larvae of Rhipicephalus bursa and sensitive resp. OP-resistant larvae of Boophilus microplus. Example 5 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 from a chromatography atomizer with the emulsified test preparations in a concentration of 400 ppm, so that the spray mixture did not run off. After two to 7 days, larvae, adults and individuals 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, the compounds according to Example 1 showed a good action against adults, larvae and eggs of Tetranychus urticae. PATENT CLAIM 1 Pesticides containing as active component a compound of the formula (I) EMI4.1 wonn R1 methyl or ethyl, R2 isopropyl, R3 hydrogen or methyl, X denotes hydrogen, halogen, methyl, methylthio, methylsulfinyl, methoxy or acetyl and n denotes the numbers 1 to 3. SUBCLAIMS 1. Agent according to claim I containing a compound of the formula I wherein Ra and ethyl X denotes hydrogen, chlorine, methyl, methylthio or methylsulfinyl. 2. Means according to dependent claim 1 containing the compound of the formula EMI4.2 PATENT CLAIM II Use of an agent according to claim I for combating insects and representatives of the order Akarina.