DE1445946C - O methyl S alkyl square bracket on 2,4 diamino s triazinyl (6) methyl square bracket on dithiophosphate - Google Patents

Description

The invention relates to O-methyl-S-alkyl-S- [2,4-diamino-s-triazinyl- (6) -methyl] -dithiophosphoric acid esters of the general formula I.

H _{; 1} CO, O, NH ₂

RS ^N S-CH ₂ -C "Ν (I)

NH

₂ .

wherein R is a methyl, ethyl or propyl group.

The compounds of the general formula I according to the invention can be prepared by a process be, in which a compound of the general formula

20th

HoCO,

RS '

SM

where R has the meaning given above and M is an alkali metal, such as sodium, or an ammonium radical with a compound of the general formula

NH ₂

35

Hal-CH ₂ -C.

^X NH ₂

is implemented, wherein Hai is a hemogen atom, preferably a chlorine atom.

A modified process for the preparation of these compounds can be that the O-methyl-S- [2,4-diamino-s-triazinyl- (6) - methyl] - dithiophosphoric acid, which is referred to below as "Desmethylmenazon", with an alkylation ■ medium, in which the alkyl group has the meaning of R, is treated. Suitable alkylating agents are alkyl halides and alkyl p-toluenesulfonates.

The compounds according to the invention of the general. my formula I have insecticidal properties and are therefore used as active ingredients in pesticides used, being mixed with inert diluents. The inert Diluent can be a solid or a liquid.

The pesticides can be, for example, liquid compositions in where the active ingredient is dissolved in water or a non-phytotoxic organic liquid or (is dispersed. Aqueous dispersions of a compound according to the invention can thereby be obtained be that the compound in a small amount of an organic liquid mixed with water is immiscible, dissolved and then the resulting solution in water, preferably with the help a dispersant.

The pesticides can also be in powder form by combining the active ingredient with a powdery diluent is mixed. The pesticides according to the invention can, regardless of whether they are liquid or powdery, contain a wetting or dispersing agent to the Use the same as a spray or dust to facilitate, or you can also use more Contain substances that can be used in the manufacture of pesticides, such as binders, Adhesives, corrosion inhibitors and stabilizers.

Solid compositions of matter which are used as dust powders can be used as diluents Contains kaolin, fuller's earth, gypsum, chalk and hewter's earth. When powder for dispersion in a If fluid is required, the following diluents will give particularly good results Achieved: kaolin, fuller's earth, light magnesium carbonate, inorganic and water-soluble fillers, such as sodium sulfate, sodium chloride and sodium bicarbonate. For the production of liquid compositions of matter are certain aromatic and aliphatic liquids such as B. trimethylbenzene, Xylene, solvent naphtha and methylnaphthalene are suitable, but aliphatic liquids can also be used including mineral oil and petroleum. Suitable wetting and emulsifying agents are Calcium and sodium dodecylbenzenesulfonate, butylnaphthalene sulfonate and various condensation products of ethylene oxide with octylphenol, nonylphenol, Sorbitan monolaurate, oleal alcohol or cetyl alcohol. Other benefits can also be achieved when certain dispersants, such as glue and the calcium, sodium or ammonium salts of Lignosulfonic acid, can be used.

The compositions of matter which are used in the form of a liquid are generally supplied to the consumer in the form of concentrated compositions of matter which contain a high proportion of the active ingredients, for example from 10 to 80 percent by weight. The concentrated solid compositions can be in the form of dispersible powders, creams, pastes or even liquids. These can then be diluted with water to give liquid compositions of matter which generally contain from 0.01 to 0.5 percent by weight of the active ingredient. ^ And which are then ^ ready for use. '.' ■ ■

The compounds according to the invention and the compositions of matter produced from them are especially useful for combating aphids, red spiders and Dysdercus, which are numerous Infested crops such as potatoes, sugar beets, beans, horticultural products, tobacco, cotton, Apples and plums.

Such treatment of the useful plants kills the pests and the weight yield of useful plants is greater than that of untreated ones and plants infested by the pests is the case. The invention thus also relates to the treatment of crops that are infested by pests.

The invention is explained in more detail in the 'following examples.

example 1

This example describes the preparation of O-methyl-S-methyl-S- [2,4-diamino-s-triazinyl- (6) methylj-dithiophosphoric acid ester.

8.01 g of desmethylmenazone were dissolved in a solution of sodium methoxide (prepared from 0.69 g of sodium) in 60 ecm of methanol. The resulting solution was cooled in an ice bath and 4.5 g of methyl iodide was added dropwise thereto, and the mixture was refluxed for 2 hours. An oil separated out on cooling and crystallized out overnight. The crystalline solid was collected, slurried with water, filtered again and dried to give O-methyl-S-methyl-S- [2,4-diamino-s-triazinyl- (6) -methyl] phosphorodithioate, its melting point after recrystallization from a large amount of 95% aqueous methanol was 180 ⁰ C (decomposition). It has been found that this product can be used as a pesticide against aphids, red spider and Dysdercus.

The desmethylmenazone used as starting material in this example was derived from the as Menazon known 0,0-dimethyl-S- [2,4-diamino-striazinyl- (6) -methyl] -dithiophosphoric acid ester manufactured as follows:

112 g of menazone were heated to 85 to 90 ° C for 4 ^ hours with 80.6 g of Ο, Ο-dimethyl phosphorodithioate, 20 g of sodium hydroxide and 1500 ecm of water. After cooling to room temperature, the liquid product was filtered to remove the gray solid present in the product, the filtrate was extracted with chloroform, and the resulting aqueous layer was acidified to pH 3-4 with glacial acetic acid. The acidified aqueous liquid was kept for 2 days at 0 ° C, and thereby separates solid was filtered off, washed with a small amount of cold water and dried in a vacuum desiccator to 67 g Desmethylmenazon having a melting point 195-204 ⁰ C ( Decomposition).

Example 2

This example describes another procedure for the preparation of O-methyl-S-methyl-S- [2,4-diammo-s-triazinyl- (6) -methyl] -di thiophosphoric acid ester.

8.01 g of desmethylmenazone were dissolved in a solution of sodium methoxide, which was obtained by reacting of 0.69 g of sodium metal with 60 ecm of methanol was obtained. The solution of desmethylmenazone and the sodium salt was then treated with 5.75 g of methyl p-toluenesulfonate /, taking care that the temperature of the reaction mixture was below 7 ° C. The mixture was then refluxed for 2 hours and finally allowed to cool calmly. On cooling, 4.0 gji crystals separated away. These were filtered off, washed with water and dried. They were then made of ethanol, which contained little water, recrystallized. That from O-methyl-S-methyl- [2,4-diamino-s-triazinyl- (6) -methylj-dithiophosphoric acid ester existing product was obtained in the form of colorless needles which melted at 180 ° C. with decomposition.

Example 3

This example describes the preparation of 0-methyl-S-ethyl-S- [2,4-diamino-s-triazinyl- (6) -methyl] -dithiophosphoric acid ester. 8.01 g of desmethylmer nazon were dissolved in a solution of sodium methoxide which was obtained by dissolving 0.69 g of sodium metal in 60 ecm of methanol. Which in this case resulting solution was cooled to 7 ⁰ C, and then 6.0 g were ethyl p-toluenesulfonate was added. The mixture was then heated under reflux for 2 hours, after which the methanol was distilled off under reduced pressure. The resulting product was then slurried with 100 cc of water, filtered and dried. 1.7 g of white crystals were obtained which melted at 150 to 151 ° C and were essentially composed of O-methyl-S-ethyl - S - [2,4 - diamino-s-triazinyl- (6) -methyl] - dithiophosphoric acid ester passed.

Example 4

This example describes the preparation of O - methyl - S - propyl -S- [2,4-diamino-s-triazinyl- (6) -methyl] -dithiophosphoric acid ester.

The procedure was similar to that described in Example 3, with the difference that 9.5 g of propyl p-toluenesulfonate were used as alkylating agents. 3.2 g of a product were obtained that essentially consists of O-methyl-S-propyl-S- [2,4-diamino-s-triazinyl- (6) -methyl] -dithiophosphoric acid ester and melted at 96 ° C.

Example 5

The following example illustrates the effectiveness of those prepared according to the previous examples Compound as a means for combating various pests.

The compositions of matter examined in the experiments consisted of dispersions that Contained 0.05 and 0.01 percent by weight of the active ingredient dispersed in water, which is 4 percent by weight a mixture of equal amounts of ethyl alcohol and acetone and 0.01 percent by weight contained a wetting agent.

The compounds in the above concentrations have been found to be effective in all cases The pests listed in the following table have been shown to affect the specified Useful plants.

pest

Aphis fabae
Macrosiphum pisi

Tetranychus (mites
the red spider)

Dysdercus

Plutella
Calandra

Phaedon

Musca

Infested plant / medium

Bean plants
Bean plants
Bean plants

.iiit, _OjfJj:.

Cotton seedlings
Cabbage plants
Wheat seeds
Mustard plants
Cotton, soaked
with sugar and milk

The compound of Example 4 showed a much greater range of action, and all of them Compounds were also effective against mosquitoes at a concentration of 0.01%.

5 6

Example 6 Example 8

Composition of a pest control concentrate of a pesticide

means, consisting of a dispersible powder. O-methyl-S-propyl-S- [2,4-diamino-s-triazinyl-

O-methyl-S-methyl-S- [2,4-diamino-s-triazinyl- ⁵ (6) -methyl] -dithiophosphoric acid ester 25 ° /

(6) methyl] dithiophosphoric acid ester 25% talc 75%

Calcium lignosulfonate 10% ~. " _± , .,. .

K _o r 65 0 / This concentrate can be mixed with a suitable

Filler can be diluted to produce a dusting powder

This powder is delivered in the usual way with io.

Water is diluted so that a dispersion is obtained. Attempts have been made to which contains 0.025 ° A> of the active ingredient. This possibility of the pesticide according to. Dilution can be used directly. Example 4 of the description compared to that in de;

Auslegeschrift- 1118 789 mentioned connection

■ ■. . 15 2-dimethoxyphosphinothioylthiomethyl-4,6-diamino example / s-triazine to be detected. From the experiments, the ir pesticides in the form of a ^d / ^r _o ^ I ¹ ^ Table are laid down, there is Stäubpulvers that reasonable without further dilution that the pesticides according to the Erwendet not only against aphids is the invention effective son

20 which also in its effect on the known

O-methyl-S-ethyl-S- [2,4-diamino-s-triazinyl- th compound in the fight against Dysdercu

(6) -methyl] -dithiophosphoric acid ester 2% fasciatus (D), Plutella maculipennis (P) and Muse;

Kaolin 98% domestica (M) is superior.

Investigated connection

Concentration in parts / million

Killing of pests in ° / o

A (Aphis fabae)

Connection according to German

Interpretation document 1118 789 (lines 9-10, p. 3)

Compound according to example 4 of description J

1000 500

1000 500

0 0

100 100

0 0

100 100

0 0

100 100

100

100

Claims (1)

Claim: O-methyl-S-alkyl-S- [2,4-diamino-s-triazinyl- (6) -methyl] -dithiophosphoric acid ester
of the general formula I. H ₃ CO, rs s — CH ₂ ^ c: , NH, ¹ NH, wherein R is a methyl, ethyl or propyl group.