CH578305A5 - O-(Substd-propenyl) (thio) phosphates - insecticides and acaricides active against all growth stages - Google Patents

Abstract

New title cpds. are of formula: (R1 = Me or Et; R2 = 3-5C alkyl; R3 = 1-3C alkyl, allyl, 3-6C alkynyl, (alpha-methyl)benzyl MeOCH2.CH2, Me(O.CH2.CH2)2 or 1-methyl-2-methoxyethyl). They are prepd. by (a) reacting R1O.R2S.P(X)Cl with CH3CO.CH2.CO2R3 in presence of acid accepted or (b) by reacting Cl2.P(X).O.C(CH3)=CHCO2R3 with R1OH and R2SH in any order.

Description

  

  
 



   The present invention relates to pesticides containing as active component a Thiobzw. Phosphoric dithiophosphate, and their use in pest control. The thio and dithiophosphoric acid esters have the formula (I)
EMI1.1
   wherein
R1 methyl or ethyl,
R2 C3-C5-alkyl,
R3 methoxyethyl, methoxyethoxyethyl or 1-methyl2-methoxyethyl and
X represent oxygen or sulfur.



   The alkyl groups at R2 can be straight-chain or branched. Examples of such groups include: a .: n-propyl; Isopropyl; n-, i-, sec- and tert-butyl; and n-pentyl.



   Because of their action, compounds of the formula (I) in which
R1 ethyl,
R2 n-propyl, isobutyl or sec-butyl,
R3 1-methyl-2-methoxyethyl and
X represent oxygen or sulfur.



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


<tb> <SEP> x
<tb> R, <SEP> R1Oüi <SEP> X <SEP> II
<tb> <SEP> R2S <SEP> (11) <SEP> + <SEP> + <SEP> medium <SEP>> <SEP> I (iii)
<tb> 1) <SEP> Avg
<tb> 2) <SEP> PXC13 <SEP> + <SEP> CH3COCH2COOR3 <SEP> acid-binding
<tb> <SEP> Medium '\
<tb> <SEP> (iv) <SEP> (<SEP> III)
<tb> <SEP> X <SEP> CH
<tb> <SEP> ri <SEP> 1 <SEP> /
<tb> <SEP> (C1) <SEP> I "O-C = CH-COOR, <SEP> + <SEP> 1. <SEP> R1OH <SEP> (VI) <SEP> acid-binding <SEP> 1
<tb> <SEP> (v) <SEP> 2. <SEP> R2SH <SEP> (via) <SEP> means
<tb> <SEP> or
<tb> <SEP> 1. <SEP> R28H <SEP> (vii)
<tb> <SEP> 2. <SEP> R1OH <SEP> (VI)
<tb>
Suitable acid-binding agents are: tertiary amines, e.g. B.

  Trialkylamines, pyridine and dialkylanilines; and inorganic bases such as hydroxides; Carbonates and bicarbonates of alkali or alkaline earth metals.



   Processes 1 and 2 are carried out at a reaction temperature between -10-100 "C, in particular between 20 to 80" C, under normal or elevated 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-di-alkylated carboxamides; aliphatic, aromatic and halogenated hydrocarbons, in particular benzene, toluene, xylenes, chloroform, chlorobenzene; Nitriles such as acetonitrile; DMSO, ketones such as acetone, methyl ethyl ketone.



   Some of the starting materials of the formulas II, III and IV are known and can be prepared analogously to known methods.



   The compounds of the formula I have a broad biocidal action and are therefore suitable for combating various types of plant and animal pests.



   However, the compounds of formula I have in particular insecticidal and acaricidal properties and can be used against all stages of development, such as. B. eggs, larvae, pupae, nymphs and adults, are used by insects and representatives of the order Akarina, such as. B. against insects of the families Tettigoniidae, Gryllidae, Gryllotalpidae, Blattidae, Reduviidae, Pyrrhocoridae, Cimicidae, Delphacidae, Aphididae, Diaspididae, Pseudococcidae, Scarabaeidae, Dermestymaline Tile, Cincinellidae, Chrysidae, Chrysulidae, Crysulidae, Lysidae, Chrysulidae, Coccinellidae, Tenebromionelidae Tripulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridae and Pulicidae, as well as acarids of the families Tetranychidae and Dermanyssidae.



   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,
Derivatives of nitrophenols,
Formamidine,
Ureas,
Carbamates and chlorinated hydrocarbons.



   The compounds of the formula I can be used 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 here that concentrations of up to 99.5 weeks can be used for application from an aircraft or other suitable application devices.



   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) weigh 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 limit 160-190 C).

 

   example 1
Production of O-ethyl-S- (n) propyl-1-carbomethoxy 1-propen-2-yl-thiol phosphate
22.4 g of potassium t-butoxide and 23.2 g of methyl acetoacetate are placed in 100 ml of dimethylformamide.



  40 g of O-ethyl-S- (n) propyl-thiochlorophosphate are added dropwise at 20-30 ° C. and the reaction mixture is stirred for a further 16 hours at room temperature. The solvent is then removed in vacuo at a bath temperature of 60 ° C., the residue is taken up in 100 ml of methylene chloride and washed twice with 30 ml of 1N sodium hydroxide solution each time.



  After the solvent has been evaporated off in vacuo, the compound of the formula is obtained as the residue
EMI2.1
 with a boiling point of 90 "C / 0.001 Torr and a refraction of nD25 = 1.4818.



  The following compounds are prepared in an analogous manner: Compound No. 1
EMI3.1
 Connection No. 2
EMI3.2
 Compound No. 3
EMI3.3
 Compound No. 4
EMI3.4

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



   After the coating had dried on, the tobacco plants were populated with caterpillars of Spodoptera littoralis in the L3 stage or by Heliothis virescens in the L3 stage.



   The experiment was carried out at 24 C and 60% relative humidity.



   In the above test, compounds Nos. 1 to 4 according to Example 1 showed a good feed poison action against Spodoptera littoralis and Heliothis virescens.



  B. Insecticidal contact effect
One day before application, broad beans (Vicia faba) grown in pots were infected with about 200 aphids (Aphis fabae) per plant. The application was carried out by means of a Druckluitspntze on the leaves infected with lice with a spray mixture in a concentration of 1000 ppm (made from a 25% wettable powder).



   The rating took place 24 hours after the application.



   The compounds Nos. 1 to 4 according to Example 1 showed good contact action 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 insecticidal activity was evaluated 10 days after the granules had been added.



   Compounds nos. 1 to 4 according to Example 1 showed good activity against Chilo suppressalis in the above test.

 

   Example 4
Effect against spider mites
Phaseolus vulgaris (French beans) were coated 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.



   The compounds nos. 1 to 4 according to Example 1 showed good activity in the above test against eggs, larvae and adults of Tetranychus urticae.

 

Claims (1)

PATENT CLAIM I. Pesticides containing as active component a compound of the formula (I) EMI4.1 wherein R1 methyl or ethyl, R2 C3-C5-alkyl, R3 methoxyethyl, methoxyethoxyethyl or l-methyl2-methoxyethyl and X represent oxygen or sulfur. SUBCLAIMS 1. Agent according to claim I, containing a compound of the formula (I) in which R1 ethyl, R2 n-propyl, isobutyl or sec-butyl, R3 1-methyl-2-methoxyethyl and X represent oxygen or sulfur. 2. Means according to dependent claim 1, containing a compound of the formula EMI4.2 3. Means according to dependent claim 1, containing a compound of the formula EMI4.3 PATENT CLAIM II. Use of an agent according to claim I for combating insects and representatives of the order Akarina.