DE2426609A1 - PYRIMIDINE DERIVATIVES - Google Patents

Description

PATENT LAWYERS
DP.-ING.H, FINCKE Dl PL.-I NG. H. BOHR DIPL.-ING. S. STAEGER

Telephone: »26 40 60

Telegrams: Claims Munich Postal checking account: Munich 270 44-802

Bank details Bayer. Vereinsbank Munich, account 620 404

23531 - Dr.F / hr

Folder No. Qa Sp PP.26177

Please indicate in the answer

8 M'JNCHEN 5, Müllerstrasse 31

31. May

IMPERIAL CHEMICAL INDUSTRIES LIMITED, London, S.W. 1 / ENGLAND

"Pyrimidine derivatives"

Priority ; 4th June 1973, ENGLAND No. 26555/73

The invention relates to new pyrimidine derivatives, which are useful as an insecticide.

In particular, the invention relates to the compound 0,0 · dimethyl-2- diethylaininopyrimidin-4-yl-phosphorothionate.

409881/1258

This compound, which is a member of a group of compounds described in detail in GB-PS 1,019,227 stands out over closely related 2-r-aminopyrimidin-4-yl-phosphorus esters including some especially listed in the above description esters by a remarkably lower toxicity to warm-blooded animals. This property enables it to be used the compound as an insecticide in many cases where closely related compounds are not used can, for example, for the disinfection of human and animal living spaces and grocery stores.

The favorable warm-blooded toxicity of the compound according to the Invention and the toxicities of certain closely related compounds measured as a single dose L.D.c-q for female Batten, measured in milligrams of substance administered orally per kilogram of live weight, is as follows Given in the table.

409881/1258

Tabel

link L.I (mg / kg) 0 _i 0 ~ dimethyl-2-diethylaminopyrimidine
^ -yl-phosphorothionate 800 OjO-diethyl ^ -diraethylaminopyrimidine-
4-yl phosphate - 200 On-Butyl ^ -dimethylaminopyrimidine - ^ -
yl methylphosphonate - 25th 0,0-diethyl-2-ethylaminopyrimidin-4-yl-
phosphate - 3.0 0,0-diethyl-2- (N-ethyl-N-methylamino) -
pyrimidin-4-yl-phosphorothionate - 50 0, O-diet hyl-2-di me thylami no pyrimi din-4—
yl phosphorothionate - 50 0,0-diethyl-2-diethylaminopyrimidin ~ 4-yl-
phosphorothionate - 50 0,0-diethyl-2-diethylaminopyrimidin-4-yl
phosphate 10 0, O-diethyl-2-ethylaminopyrimidine - ^ - yl-
phosphorothionate 10 So 100 12.5 '1.5 25th 25th 10 approx. approx.

The compound of the present invention can be prepared by treating 2-diethylamino - ^ - hydroxypyridimine or an alkali metal salt the same with dimethylphosphorochloridethionate, preferably in a diluent and solvent, and optionally in the presence of a base. Suitable Solvents are ketones, for example acetone, or methyl isobutylene ketone, and esters, for example ethyl acetate, -but any non-reactive solution or diluents can be used. Suitable bases include alkali metal carbonates, for example Potassium carbonate, and tertiary amines, for example Tiääthylamin or diethylaniline. The reaction between the hydroxypyrimidine derivative and the halophosphorus compound

AO 9 8-8.1; / 125 8

can be accelerated or terminated by heating, for example by refluxing the mixture of the reactants and the solvent or diluent under the reflux temperature of the solvent or diluent.

When using the compound, it can be used in undiluted form to control insect pests, however, it is best used in conjunction with a diluent or carrier in the form of a composition of matter applied.

According to a further feature of the invention, pesticides are substances Suggested compositions containing O, 0-Dimethyl-2-diethylaminopyrimidin ~ 4-yl-phosphorothionate in connection with a diluent or carrier material.

The compositions of matter can be in the form of granules are present, the active ingredient being absorbed by a porous granular material such as pumice stone.

If necessary, the compositions of matter can also be used in The form of liquid preparations can be used as dipping or rinsing agents, which are generally aqueous dispersions or emulsions of the active ingredient in the presence of one or more known wetting agents or dispersants or emulsifiers. These compositions of matter are prepared in that the active ingredient in a suitable solvent, for example a ketonic Solvents, such as diacetone alcohol, dissolved and the like The resulting mixture is added to water, which contains one or more known wetting agents, dispersants or emulsifiers may contain.

409881/1258

The compositions of matter, which are in the form of aqueous Dispersions or emulsions are generally supplied in the form of a concentrate, which a high proportion of the active ingredient or ingredients This concentrate is diluted with water before use. Such concentrates are often required in order to survive a longer storage time, whereby they must be suitable after storage with water to be diluted to form aqueous preparations which will remain homogeneous for a sufficient period of time to permeate the usual spray devices can be used to control the pests. These concentrates can 10 to 85 Gew .- ^ contain the active ingredients. When they go to Formation of aqueous preparations are diluted, so these preparations can contain different amounts of the active ingredient included, which depends on the purpose for which they are to be used.

For agricultural or horticultural purposes, an aqueous preparation can be used between 0.0001 and 0.1 wt .- ^ of the active ingredient or ingredients.

The compositions of matter according to the invention can be desired tenf a Ils also in addition to the one according to the invention Compound at least one other biologically active agent, for example an insecticide or fungicide, contain.

In use, the compositions of matter are applied to the Pests, the whereabouts of the pests or the pest carriers or applied to growing plants, subject to pest infestation by any of the known means for applying pest control material compositions, for example by dusting or spraying.

409881/1258

The compound according to the invention and containing them Compositions of substances are very toxic to diverse ones Insects or other invertebrate pests, such as the following:

Tetranychus telarius (red spider mites) Aphis fabae (aphids)

Megoura viceae (aphids)

Aedes aegypti (mosquitoes)

Musc8 domestica (house flies)

Pieris brassicae (larvae of the white butterfly) Plutella maculipennis (larvae of the diamond-backed moth) Phaedon cochleariae (mustard beetle)

Calandra granaria (grain beetle).

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

example 1

5 parts by weight of OjO-dimethyl ^ -diäthylaminopyrimidin - ^ - ylphosphorthionat were in a suitable mixing device carefully mixed with 95 parts by weight of talc. In this way, a dust powder was obtained.

Example 2

10 parts by weight of OjO-dimethyl ^ -diäthylaminopyrimidin - ^ - ylphosphorthionat, 10 parts of an ethylene oxide / octylphenol condensate (sold as the trademark "Lissapol" NX Medium) and 80 parts by weight of diacetone alcohol were carefully mixed. In this way a concentrate was obtained which, after mixing with water, gave an aqueous dispersion that could be used as a spray for combating insect pests could be used.

409881 / 12S8

Example 3

A granular composition was made by dissolving the active ingredient in a solvent and spraying the obtained solution on pumice granules, whereupon the solvent was evaporated.

Wt .- ^

O, O-Dimethyl-S-diethylaminopyrimidin - ^ - ylphosphorothionate 5

Pumice granules 95

100

Example 4-

An aqueous dispersion was made by mixing and grinding of the following ingredients in the specified quantities.

Wt .- ^

0,0-Dimethyl ~ 2-diethylaminopyrimidin-4-ylphosphorothionate 40

Calcium lignosulfonate 10

Water '50

100

Example 5 ■

The effectiveness of 0,0 ~ dimethyl-2-diethylaminopyrimidin-4-yl-phosphorothionate was examined against various insects and other invertebrate pests. The compound was used in the form of a liquid preparation containing 0.1 wt .- ^ containing the compound except for the test with Aedes aegypti, where the drug only 0.01 wt -% of the compound contained.. The preparations were made by 'that the compound in a solution

409881/1258

Medium mixture was dissolved, which consists of 4 parts by volume Acetone and 1 part by volume of diacetone alcohol. The solutions were then diluted with water containing 0.01 wt .- # of a wetting agent known under the designation "LISSAPOL" NX (registered trademark) is sold and that the required concentration of the compound contained.

The investigation with regard to the individual pests was basically the same and consisted of the fact that one Number of pests were on a medium, usually from a host plant or food insisted on which the pests feed and where either the pests and the medium with the Preparations or these have been treated individually.

The kill of the pests was then determined after certain periods, which range from 1 to 3 days after the treatment cheat.

The results of the tests are compiled in the table below. In this table is in the first Column indicates the type of pest in question. Each of the following columns gives the host plant or medium on which the pests are located, the number of days that have passed after the treatment before the pests killed were counted and the results for each compound are compiled in the last column. The evaluation is expressed in whole numbers from 0 to 3

0 denotes a kill of less than 30 %

Λ denotes a kill of 30 to 49 %

2 denotes a kill of 50 to 90 %

3 indicates a kill of over 90 #.

4098 81/1258

In Table 2, the designation "contact experiment" means that both the pests and the medium are treated
were, "residual experiment" denoted that the medium was treated with the pests prior to infection and
"Systematic trial" means that the leaves of the host plant became infected after the roots of the
Plant have been treated with the aqueous preparation.

409881/1258

Table 2

Pests

Host plant

Number of ¹ Te ge

HS;

Tetranychus telarius (adult red spider mites)

Aphis fabae
(Aphids)

Msgoura viceae (aphids)

Dys-iercws 5 ¹ Sεc..atas (Capsids)

üedes a ^ ypti (Küclcenlar ven)

Aedes aeppyti (exc. "chsene chicks)

Musca '^ f

i Franaosisc ne ί beans 1

broad

■ ^: wages

Ί width ι drilling

' Grain

water . plywood

■ milk /; sugar

Contact)

liusca domesti ·. 3 (fly out test)

Blattella gericanica (Bedbugs)

Pieris brassicae (Larvae of the cabbage whitefly - systematic 7e rs u c-h)

Pieris brcssicae (Larv3u of the cabbage whitefly - contact attempt)

i -

j cabbage

Cabbage

Plutella raaculipennis j mustard

νLarvae of the diamond j

r ^: j.ck3nmotte - syste- j

rratis ^ her attempt) i

Plutella maculipennis j mustard (Larvae of the diamond moth - test)

Fhaedon cochleariae mustard

(Mustard beetle - sjrsteiaatic experiment) 2 2

409881/1258

- Tl -

Table 2 (continued)

Pests Host plant number of
Days valuation Phaedon cochleariae
(Mustard beetle - leftover
search) mustard 2 3 Calandra granaria
(Grain beetle) grain 2 * I Tribolium confusum
(Flour beetle) grain 2 3 Meloidogyne incognita
(Roundworms) tomato . 14th 5

Example 6

This' example illustrates the preparation of O, O-dimethyl-2-diethylaminopyriinidin-4-yl-phosphorothionate.

4.96 g of anhydrous potassium carbonate and 3.03 S of dimethylphosphorochloride thionate were added to a solution of 3.0 g of 2-diethylamino-4-hydroxypyrimidine in 50 ecm of dry acetone. The mixture was stirred at room temperature for 24 hours and then filtered to remove the insoluble material. The filtrate was evaporated under reduced pressure at 35 ⁰ G and the residual oil was dissolved in 50 ecm methylene chloride. The solution was washed successively twice with 15 ecm 1 # aqueous sodium hydroxide solution, twice with 15 ecm water and 20 ecm brine and then dried over anhydrous magnesium sulfate. After filtering and evaporation of the solvent, the residual oil was purified, and between by preparative thin layer chromatography to OjO-dimethyl ^ -diäthylaminopyrimidin - ^ - ylphosphorthionat in the form of a yellow oil with a refractive

24
index n- ^ ί to result in 5340.

409881/1258

The structure of the product was confirmed by infrared and nuclear magnetic spectroscopy.

Claims

409881/1258

Claims (19)

PATENT CLAIMS: 1. OjO-Dimethyl ^ -diethylaminopyrimidin - ^ - yl-phosphorothionate. 2. Process for the preparation of O, O-dimethyl-2-diethylaminopyrimidin-4-yl-phosphorothionate, characterized in that 2-diethylamino-4-hydroxypyrimidine or an alkali metal salt the same rait dimethy iphosphorochlorothionate is treated. 3. The method according to claim 2, characterized in that that a solvent or diluent is used. 4-, method according to claim 3, characterized in, that the solvent or diluent consists of a ketone. 5. The method according to claim 4, characterized in that that the ketone consists of acetone or methyl isobutyl ketone. 6. The method according to any one of claims 2 to 5, characterized characterized in that it is carried out in the presence of a base. 7- method according to claim 6, characterized in that that the base is an alkali metal carbonate. 8. The method according to claim 7 »characterized in that that the alkali metal carbonate consists of potassium carbonate. 9. - Pesticides, characterized in that 409881/1258 that the active ingredient is OjO-Dimethyl ^ -diäthylaminopyriinidin-4-yl-phosphorothionate in conjunction with a diluent or carrier. 10. Pesticides according to claim. 9, thereby characterized in that it contains one or more wetting, dispersing or emulsifying agents. 11. Pesticide according to one of claims 9 and 10, characterized in that the diluent or carrier is a liquid diluent. 12. Pesticide according to one of claims 9 and 10, characterized in that the diluent
or carrier is a solid diluent or carrier. 13. Pesticide according to claim 12, characterized in that the carrier means is a porous, pithy
Material is. 14. Pesticide according to one of claims 9 to 13, characterized in that it contains 10 to 85 wt .- #
of the active ingredient. 15- pesticide according to any one of claims 9 to 13, characterized in that it is 0.0001 to 1.0
Contains% of the active agent - wt.. 16. Pesticide according to one of claims 9 to 15 »characterized in that there is at least one
contains another biologically active agent. 17. Pesticides according to claim 16, characterized marked that the further biologically effective smock 409881/1258 is an insecticide. 18. Pesticide according to claim 16, characterized in that the further biologically active agent is a fungicide. 19. A method for controlling pests, characterized in that that on the pests themselves: <bder the place of their occurrence or the whereabouts of the pests or on plants which are exposed to pest infestation, a pesticide according to one of the claims 9 to 18 is applied. t ■>"ic«. = ■ ». ·· ♦ 1- y -. 'ΐ. VC; .H. ····. ·; ■. "*. =. C, "L.-il.sO Δ09-881 / 1258