CA1053238A - O-ethyl-s-alkyl-s-picolyl-phosphoric thiolates - Google Patents

Abstract

Abstract of the Disclosure Picolyldithiophosphoric acid esters of the formula

Description

1()5~238 The present invention relates to picolyldithiophosphoric acid esters and to their use in pest control.
The picolyldithiophosphoric acid esters have the formula OC H (I) SR

Xl X2 wherein R represents an n-propyl, i-propyl, sec-butyl or propargyl group and Xl and X2 independently of one another represent a hydrogen or chlorine atom.
The compounds of the formula I can be manufactured by methods which are analogous to known ones, e.g. in the following manner:

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3~3~

~ 1 CH2-Hal + 5~ I + MeHal Xl X2 (II) ~III) wherein R, Xl and X2 have the meanings given for the formula I and Hal represents a halogen atom, e.g. fluorine, chlorine, bromine or iodine, in particular chlorine or bromine, and Me represents an alkali metal, especially sodium or potassium.
The process is carried out at normal pressure, at a temperature between 0 to 150C, preferably between 20 to 100C, and in solvents or diluents which are inert towards the reactants, Examples of suitable solvents and diluen~s are: aromatic hydrocarbons, e.g. benzene, toluene, halogenated hydrocarbons, chlorobenzene, polychlorobenzenes, bromobenzene, chlorinated alkanes with 1 ~o 3 carbon atoms, ethers, e.g. dioxan, tetrahydrofuran;
esters, e.g. ethyl acetate; ketones, e.g. acetone, methyl ethyl ketone, diethyl ketone; nitriles, e.g. acetonitrile etc.
Some of the starting materials of the formula II are known or can be manufactured by methods analogous to known ones.
The compounds of the formula I exhib;t a broad biocidal activity and can be used for the control or a variety of plant and animal pests, and , ' - ' ' ~)53'~319 as plant regulators.
In yarticular they are suitable for combating insects of the families: Acrididae, Blattidae, Gry]lidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Phyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae, Pseudococcidae, Chrysomelisae, Coccinellidae, Bruchidae, Scarabaeidae, Dermestidae, Tenebrionidae, Curculionidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleridae, Culicidae, Tipulidae, Stomoxydae, Muscidae, Calliphor-idae, Trypetidae, Pulicidae as well as Acaridae of the families: Ixodidae, Argasidae, Tetranchidae, Dermanyssidae.
By addition of other insecticides and/or acaricides it is possible ; to improve substantially the insecticidal or acaricidal action and to adapt it to given circumstances.
Examples of suitable additives are: organic phosphorus compounds, nitrophenols and derivatives thereof; formamidines; ureas; carbamates and chlorinated hydrocarbons.

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1~3Z38 The compounds of the formula I may be used as pure active substance or together with suitable carriers and/or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances convention-ally used in formulation technology, for example natural or regenerated sub-stances, solvents, dispersants, wetting agents, adhesives, thickeners, binders and/or fertilisers.
For application, the compounds of the formula I may be processed to dusts, emulsion concentrates, granules, dispersions, sprays, to solutions or suspensions, in the conventional formulation which is commonly employed in application technology. Mention is also to be made of cattle dips and spray races, in which aqueous preparations are used.
The agents according to the invention are manufactured in known manner by intimately mixing and/or grinding active substances of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents w-hich are inert towards the active substances. The active i ~ -5-","., -:

~053;~38 substances can take~ and be used in, the following forms:
Solid forms:
dusts~ tracking agents, granules, coated granules, impregnated granules and homogeneous granules.
Liquid forms:
a) active substances which are dispersable in water:
wettable powders, pastes, emulsions:
b) solutions.
The content of active substance in the above des-cribed agents is between 0.1% to 95~, in which connection it should be mentioned that, in the case of application ~
from aircraft or some other suitable means of application, it is possible to use concentrations of up to 99.5% or even pure active substance.
The active substances of the formula I can, for example, be formul~ted as follows:
Dusts me following substances are used to manufacture a) a 5% and b~ a 2% dust:

a) 5 parts of active substance 95 parts of talcum b) 2 parts of active subs~ance 1 part of highly disperse silicic acid 97 parts of talcum.
e active substances are mixed with the carriers - , . , ~:

~1~5~ 8 and ground.
Granules The following substances are used to produce 5%
granules:
parts of active substance, 0.25 parts of epichlorohydrin, 0.25 parts of cetyl polyglycol ether.
3.50 parts of polyethylene glycol, 91 parts of kaolin (particle size 0.3-0.8 ~m).
~he active substance is mixed with ~pichlorohydrin and dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The re-sulting solution is sprayed m kaolin, and the acetone is subsequently evapor~ted in vacuo.
Wettable Powder:
The following constituents are used for the pre-paration of a) a 40%, b) and c) a 25%, and d) a 10%
wettable powder:
a) 40 parts of active substance~
parts of sodium lignin sulphonate, 1 part of sodium dibutyl-naphthalene sulphonate, 54 parts of silicic acid.
b) 25 parts oP active substance 4.5 parts of calcium lignin sulphonate, ~(~5~Z3~
I.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 1.5 parts of sodium dibu*yl naphthalene sulphonate 19.5 parts of silicic acid, ;
19.5 parts of Champagne chalk, 28.1 parts of kaolin.
c) 25 parts of active substanceg

2.5 parts of iso~ctylphenoxy-polyoxyethylene-e~hanol, 1.7 parts of Champagne chalk/hydroxyethyl ~:
cellulose mixture (1:1), 8.3 parts of sodium aluminiumsilicate, 16.6 parts of kieselguhr, 46 parts of kaolin.
4d~ 10 parts of active substance,

3 F- parts of a mixture of the sodium salts of saturated fatty alcohol sulphates, :~ 5 parts of naphthalenesulphonic acid/
formaldehyde condensate, 82 parts of kaolin.
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The active substances are intimately mixed~ in suitable mi~ers7 with the additives~ the mixture being then ground in the appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to ~' ' ' -8~

-: , . ~ . . . . .

lQ~3Z38 give suspensions of any desired concentration~
Emulsifiable concentrates:
The following substances are used to produce a) a 10% and b) a 25%
emulsifiable concentrate:
a) 10 parts of active substance, 3.4 parts of epoxidised vegetable oil, 3.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylaryl sulphonate calcium salt, parts of dimethylformamide, 43.2 parts of xylene, :~
b) 25 parts of active substance, 2.5 parts of epoxidised vegetable oil, 10 parts of an alkylarylsulphonate/fatty alcoholglycol ether mixture, 5 parts of dimethylformamide, 57.5 parts of xylene.
From these concentrates it is possible to produce, by dilution with water, emulsions of any desired concentration.
Spray:
The following constituents are used to prepare a 5% spray:
5 parts of active substance, 1 part of epichlorohydrin, g4 parts of benzene ~boiling limits 160C-190C). ~ :

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3 ~5~Z38 Example 1 Manufacture of 0-ethyl-S-n-propyl-S-2,6-dichloropicolyl-3-phosphoric thiolate 14 g of 2,6-dichloropicolyl-3-chloride are dissolved in 150 ml of acetone, and to this solution are added by small amounts 16.9 g of potassium-0-ethyl-S-n-propyldithiophosphate. The reaction mixture is stirred for 16 hours at room temperature. After the solvent has been distilled off~ the residue is treated with ether, washed with water, and dried over anhydrous sodium sulphate.
The ether is evaporated off to yield the compound of the formula OC H

Cl Cl SC3H7(n) with a refractive index of n24 = 1.5740.
The following compounds are also manufactured in analogous manner:

n24 : 1,5617 -lQ-~,s:

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l~S;~238 Il <0;2H5 nD: 1,6004 )~S CH2-C--CH nD = 1, 5995 Cl N Cl Il <OC2H5 llD = 1, 5691 Cl N ClC2H5 !

Il <OC2H5 nD = 1, 5738 Cl Cl .

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Example 2 A) Insecticidal ingest poison action Cotton and potato plants were sprayed with a 0.05% aqueous emulsion ~obtained from a 10% emulsifiable concentrate). After the coating had dried, the cotton plants were populated with Spodoptera littoralis or Heliothis virescens larvae L3 and the potato plants with Colorado potato bettle larvae ~Leptino-tarsa decemlineata). The test was carried out at 24C and 60% relative humidity. In the above test, the compounds according to Example 1 displayed good ingest poison action against Spodoptera littoralis. Heliothis and Leptinotarsa decemlineata larvae.

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~53Z38 Example 3 Action against Chilo su~pressalis Six rice plants at a time of the variety Caloro were trans-planted into plastic pots (diameter at the top = 17 cm) and reared to a height of about 60 cm. Infestation with Chilo suppressalis larvae (Ll: 3~4 mm long) took place 2 days after the active substance had been applied in granule fo~m to the paddy water (rate of application: 8 kg of active substance per hectare). Evaluation of the insecticidal action took place 10 days after application of the granules.
The compounds according to ~xample 1 were active in the -above test against Chilo suppressalis.
Example 4 Action a~ainst ticks A) R~iPicephalus bursa Five adult ticks and 50 tick larvae were counted into a --glass tube and immersed for 1 to 2 minutes in 2 ml of an aqueous emulsion from an emulsion series each containing 100, 10, 1 or 0.1 ppm of test substance. The ~ube was then sealed with a standard cotton wool plug and placed on its head, so that the active substance emulsion could be absorbed by the cotton wool.
In the case of the adults evaluation took place after - : . , .
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1()53Z38 2 weeks, and in that of the larvae after 2 days. Each test was repeated twice.
B) Boophilus micro*lus (larvae) Tests were carried out in each case with 20 OP-sensitive larvae using a dilution series analogous to that of test A. (The resistance refers to the tolerability of Diazinon).
The compounds according to Example 1 ~cted in these tests against adults and larvae of Rhipicephalus bursa and sensitive and OP-resistant larvae of Boophilus microplus.
Example S
Acaricidal action -~
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Phaseolus vulgaris (dwarf beans) have an infested piece of leaf from a mass culture of Tetranychus urticae placed on them 12 hours before the test for the acaricidal action.
The mobile stages which have invaded the plants are sprayed with the emulsified test preparations from a chromatography atomiser so that the spray broth does not run off. me number of li~ing and dead larvae, adults and eggs are evaluated after-z~
2 to 7 days under a stereoscopic microscope and the result `
expressed in percentages. During the "wai~ing time~', the treated plants are kept in greenhouse compartments at 25 C.
The compounds according to Example 1 were active in the above test against eggs, larvae and adults of Tetranychus urticae.

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Claims (9)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PRIVILEGE OR PROPERTY IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Compounds of the formula I

(I) wherein R represents an n-propyl, i-propyl, sec.-butyl or propargyl group and X1 and X2 independently of one another represent a hydrogen or chlorine atom.

2. Compounds according to claim 1 wherein R represents an n-propyl or i-propyl group.

3. A compound according to claim 2 wherein R represents an n-propyl group and X1 and X2 both represent chlorine atoms.

4. A compound according to claim 2 wherein R represents an n-propyl group and X1 and X2 both represent hydrogen atoms.

5. A compound according to claim 2 wherein R represents an i-propyl group and X1 and X2 both represent chlorine atoms.

6. A method of combatting pests of the class Insecta or of the order Acarina at a locus, which method comprises applying to the locus a compound as claimed in any one of claims 1 to 3.

7. A method of combatting pests of the class Insecta or of the order Acarina at a locus, comprising growing agricultural or horticultural crops, plants or produce, which method comprises applying to the locus a compound as claimed in any one of claims 1 to 3.

8. A method of combatting pests of the class Insecta or of the order Acarina at a locus, which method comprises applying to the locus a compound as claimed in claim 4 or 5.

9. A method of combatting pests of the class Insecta or of the order Acarina at a locus, comprising growing agricultural or horticultural crops, plants or produce, which method comprises applying to the locus a compound as claimed in claim 4 or 5.