CH573710A5 - S-diphenylmethyl phosphorodithioates - with insecticidal, acaricidal, bactericidal, fungicidal and nematocidal activity - Google Patents

Abstract

New cpds. of formula (I): (where R1 is 1-5C alkyl; R2 is 1-5C alkyl (opt. substd. by 1-5C alkylthio), 3-5C alkenyl or 3-5C alkynyl; R3-R12 are each H, halogen or 1-5C alkoxy) are pref. prepd. by reacting the corresp. diphenylmethyl halide with MS(O)P(SR2)OR1 (where M = alkali metal).

Description

  

  
 



   The present invention relates to pesticides containing an S-diphenylmethyldithiophosphate as the active component, and to their use in pest control.



   The S-diphenylmethyl-dithiophosphates have the formula (I)
EMI1.1
 wherein
R1 C1-Cs-alkyl,
R2 C1-CS-alkyl, C1-CS-alkylthio-C1-C5-alkyl, C3-Cs-alkenyl or C3-Cs-alkynyl and
R3 to R12 each denote hydrogen, halogen or C1-Cs-alkoxy.



   Halogen is to be understood as meaning fluorine, chlorine, bromine and iodine, but in particular chlorine and bromine.



   The alkyl, alkoxy, alkylthioalkyl, alkenyl or alkynyl groups which come into consideration for R1 to R12 can be straight-chain or branched. Examples of such groups include: a .: methyl, methoxy, methylthiomethyl, ethyl, ethoxy, propyl, isopropyl, n-, i-, sec-, tert-butyl, n-pentyl and its isomers, allyl, propargyl.



   Because of their action, compounds of the formula (I) in which
R1 ethyl,
R2 C1-Cs-alkyl, methylthio-methyl or propargyl,
R3, R6, R7, R8, R9, R11 and R12 are each hydrogen and
R4, R5 and Rlo each denote hydrogen, chlorine or methoxy, especially those compounds in which
R2 n-propyl, n-butyl or iso-butyl and
R4, R5 and R1o each represent hydrogen or chlorine.



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


<tb> <SEP> R <SEP> R8RR6 <SEP> 0
<tb> 1C <4 <SEP> + <SEP> ae-s
<tb> <SEP> (ITI)
<tb> <SEP> (11)
<tb> <SEP> ¸,
<tb> <SEP> (<SEP> I) <SEP> + <SEP> MeHal
<tb> <SEP> (u)
<tb>
In the formulas II to IV, R1 to R12 have the meaning given for the formula I, Hal stands for a halogen atom, in particular chlorine or bromine, and Me stands for an alkali metal, in particular sodium or potassium.



   The process is carried out at normal pressure, a temperature between 0 and 150 ° C., preferably between 20 and 800 ° C., and in solvents or diluents which are inert towards the reactants. The following are, for example, suitable: aromatic hydrocarbons, such as benzene, toluene; halogenated hydrocarbons , Chlorobenzene, polychlorobenzenes, bromobenzene, chlorinated alkanes with 1 to 3 carbon atoms; ethers such as dioxane, tetrahydrofuran; esters such as ethyl acetate; ketones such as acetone, methyl ethyl ketone, diethyl ketone; nitriles, e.g. acetonitrile, etc.



   The compounds of the formula I have a broad biocidal action and can be used to control various types of plant and animal pests.



   In particular, they are suitable for combating insects of the families: Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Pyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae, Pseudococcidae, Curysomelion, Tenestidae, Tenestidae, Cocaestidae , Noctuidae, Lymantriidae, Pyralidae, Galleriidae, Culicidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypefidae.



  Pulicidae as well as acarids of the families: Ixodidae, Argasidae, Tetranchidae, Dermanyssidae.



   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. 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, for. B. in the processing forms described in the German Offenlegungsschrift 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 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 ether and alkylaryl sulfonate 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 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 gasoline (boiling limits 160-190 "C).

 

   example 1
Preparation of the O-ethyl-S-n-propyl-S-diphenylmethyl dithiophosphoric acid ester
To a solution of 18.5 g of bromodiphenylmethyl in 100 ml of absolute acetonitrile, 19 g of O-ethyl-S-propyl-dithiophosphate potassium salt are added in portions at room temperature. The reaction mixture is then stirred for 12 hours and filtered. After the filtrate has been evaporated, the residue is taken up in ether, washed twice with 100 ml of water each time and the organic phase is dried with sodium sulfate. The product obtained is crude O-ethyl-S-propyl-S-diphenylmethyl-dithiophosphoric acid ester, which can be purified by chromatography through a silica gel acid.



  Refraction: nD20 = 1.5878.



   The following connections are also established in the same way:
EMI2.1
  
EMI3.1

Example 2
Insecticidal food poison effect Cotton plants and potato 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 or Heliothis virescens larvae LS and the potato plants with Colorado beetle larvae (Leptinotarsa decemlineata). The experiment was carried out at 24 C and 60% relative humidity.



   In the remainder above, the compounds according to Example 1 showed a good insecticidal feed poison action against Spodoptera, Heliothis and Leptinotarsa decemlineata larvae.



   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 insecticidal activity was evaluated 10 days after the granules had been added.



   The compounds according to Example 1 were effective against Chilo suppressalis in the above test.



   Example 4
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, 20 sensitive resp. OP-resistant larval experiments were carried out. (The resistance refers to the tolerance of Diazinon.)
The compounds according to Example 1 were active in these tests against adults and larvae of Rhipicephalus bursa and sensitive, respectively. 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 from a chromatography atomizer so that the spray mixture did not run off.



  After two to 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, the compounds according to Example 1 were effective against adults, larvae and eggs of Tetranychus urticae.



   PATENT CLAIM 1
Pesticides containing as active component a compound of the formula (I)
EMI4.1
 wherein
R1 Cl-Cs-alkyl,
R2 Cl-Cs-alkyl, C1-CS-alkylthio-C1-C5-alkyl, C3-Cs-alkenyl or C3-Cs-alkynyl and
R3 to R12 each denote hydrogen, halogen or Cl-Cs-alkoxy.

 

   SUBCLAIMS
1. Agent according to claim I, containing a compound of the formula (I) in which
R1 ethyl,
R2 C1-C5-alkyl, methylthiomethyl or propargyl,
R3, R6, R7, R8, Rg, R11 and R12 each hydrogen and
R4, R5 and R1o each denote hydrogen, chlorine or methoxy.



   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

PATENT CLAIM II
Use of an agent according to claim I for combating pests.

 

Claims (1)

SUBClaim 5. Use according to claim II for combating insects and representatives of the Akarina order.