DE2119212A1 - Insecticidal agent - Google Patents

Description

LEVERKUSEN-layeiwerk Patent Department O O. ΜΗ2

The present invention relates to organic phosphoric acid esters and their use for combating harmful Insects and other pests.

In particular, the present invention relates to an insecticide which uses an organic phosphoric acid ester as an active ingredient of the following general formula (i)

C ₂ H ₅ OO

PS-CH ₀ -SR (I)

<L

contains where

R is a lower alkyl radical, a phenyl substituted with a halogen atom or a lower alkyl radical or benzyl radical or an unsubstituted phenyl or benzyl radical.

In Japanese rice growing means the damage caused by larvae of insects of the genus Lepidoptera, such as the double- or triple-breeding rice stem borer and the mites is a serious problem. There were extensive research carried out so far, which aimed at combating these harmful insects, but these are only a few of the insecticides available on the market that almost all of which are based on organic phosphorus

209808/1988

bindings are suitable for this purpose. Outside the ^V have the harmful insects, because these insecticides have been used in large quantities, see some Resitenz contrast established.

From Japanese Patent Publication No. 16875/63 is a process for the preparation of insecticidal compounds of the general formula (II) given below known:

Il

POR ₉ [S) ^ (II)

wherein

R and R. are optionally alkyl groups and

R ^ optionally an aliphatic, alicyclic

or aromatic radical, which can also be substituted

can means.

However, the above-cited patent publication does not teach against which insects the according to the above-mentioned formula produced compounds are to be used or what effect they have.

It has surprisingly been found that, among the compounds listed above, the organic phosphoric acid esters in fc which, as can be seen from formula (i), the alkyl group in the P-O-alkyl chain an ethyl group and the alkyl group in the P-S-alkyl chain is a saturated, straight-chain propyl group the formula below

is to have particularly excellent insecticidal effectiveness.

Nit 74 -2-

2 0 9 8Q 8/19 8 8

The compounds according to the invention: can therefore within a wide range of applications for combating harmful sucking and stinging insects, plant parasites, harmful insects and those that commanded stored grain are used.

The compounds according to the invention are particularly effective to combat harmful insects that occur in agriculture, such as the genera Coleoptera, Lepidoptera, Hemiptera, Orthoptera, Isoptera and Diptera, the spider mites and harmful nematodes occurring in the soil and can also be used as pesticides against them Pests are applied.

As can be seen from Table 2 below, the compounds according to the invention have a comparison analogous compounds have particularly strong insecticidal activity against insects of the genus Lepidoptera, whose Control with conventional insecticides has proven difficult. In addition, the compounds according to the invention have very strong insecticidal activity against insects, which are resistant to insecticides based on organic phosphorus have built. They are also extremely effective in combating the double-breeding rice stem borer and in contrast to parathion and methyl parathion, their use because of their direct and indirect strong toxic Effect on the human body is prohibited, only low toxicity. Even so, the insecticidal effectiveness of the compounds according to the invention comparable to or superior to those of parathion, they can therefore be used without danger as agricultural chemicals are used.

The compounds of the general formula (i) according to the invention can be prepared using the procedure below.

Nit 74 -3-

20980 3/1383

C H CU,

, Μ + Hal-CH ₂ -SR

(IV) O PS-CH ₂ -SR + M.Hal

R as defined above,

M is a metal atom or an ammonium residue and Hal is a halogen atom.

In the above reaction formula, R means a lower alkyl radical such as methyl, ethyl, n- or iso-propyl, n-, iso-, see. or tert-butyl, a phenyl or phenyl which is optionally substituted by chlorine and / or bromine Benzyl radical or a phenyl or benzyl radical substituted with the lower alkyl radicals listed above. M is a metal atom such as sodium or potassium or the ammonium residue, Shark is chlorine or bromine.

The following are examples of the halides of the formula (IV):

Ethylthiomethyl,

n-rutylthiometh / 1-,

Phenylthiomethyl,

4-chlorophenylthiomethyl-,

2,4-dichlorophenylthiomethyl-,

4-methylphenylthiomethyl-,

Benzylthiomethyl,

4-chlorobenzylthiomethyl-,

2,4-dichlorohenzylthiomophyl chloride or bromide.

The reaction for the production of the corresponding compounds

:: _ A. 74 -4-

BAD ORiGINAL

fertilizing is preferably done in a solvent or diluent carried out. For this purpose, any inert solvents can be used.

The preferred solvents and diluents are water, aliphatic and aromatic hydrocarbons (which also halogenated), such as methylene chloride, di-, tri or tetra-chloroethylene, toluene, chloroform, carbon tetrachloride, Gasoline, benzene, chlorobenzene or xylene; Ethers such as diethyl ether, di-n-butyl ether, dioxane or tetrahydrofuran; low-boiling aliphatic ketones or nitriles such as aliphatic ketones or nitriles such as acetone, methyl ethyl ketone, Methyl isopropyl ketone, methyl isobutyl ketone, acetonitrile or propionitrile; and low boiling aliphatic alcohols such as e.g. methanol, ethanol or isopropanol are used.

After the above process, the reaction can be carried out within a wide temperature range, in general, however, it is carried out at temperatures from -20 C to the boiling point of the reaction mixture, preferably at temperatures of between 0 and 100 ⁰ C.

The reaction is preferably carried out under normal pressure, but it can also be carried out under increased or decreased Printing can be carried out. The preparation of the compounds according to the invention which are used as active ingredients is based on the experimental examples given below described in more detail.

Experimental example It ^C 2 ^H 5

PS-CH ₂ -SC ₂ H ₅

nC ₃ H ₇ S '

60 g of O-ethyl-Sn-propyldithiophosphoric acid potassium salt becomes Nit 74 -5-

209808/1988

dissolved in 200 ml of acetone, 28 g of ethylthiomethyl chloride are added dropwise to this solution at a temperature of 20 ° C. Then the temperature is gradually raised to 60 ⁰ C, the reaction is qeführt at this temperature under stirring for one hour to an end.

The acetonitrile is distilled off from the reaction mixture and the residue is dissolved in benzene, washed with water and 1% sodium carbonate, and over anhydrous sodium sulfate dried. After distilling off the benzene, 54 g of colorless, oily O-ethyl-S-n-propyl-S-ethylthiomethylphosphorodithiolate are obtained obtain. The product obtained has a boiling point of 131-135 ° C / 0.1 mm Hg and a

'20 refractive index η _D of 1.5391.

Test example 2t

C ₂ H ₅ O

60 g of O-ethyl-Sn-propyldithiophosphoric acid potassium salt are dissolved in 200 ml of alcohol, and 43.5 g of 4-chlorophenyl-thiomethyl chloride are added to this solution at room temperature. This mixture is stirred for some time at room temperature and then at 60 ^{° C. for one hour.} The alcohol is then distilled off from the reaction mixture and the residue is dissolved in benzene, washed with water and 1% sodium carbonate and dried over anhydrous sodium sulfate. After the benzene has been distilled off, 73 g of colorless, oily O-ethyl-Sn-propyl-S-4-chlorophenylthiomethylphosphorodithiolate are obtained. The product has a boiling point of 154-157 ° C / 0.1 mm Hg and a refractive index n ² ° of 1.5922,

Nit 74 -6-

209808/1988

Experimental example 3

60 g of O-ethyl-S-n-propyldithiophosphoric acid potassium salt are dissolved in 200 ml of acetonitrile, then 53.5 g of A-chlorobenzylthiornethyl chloride are added dropwise at room temperature. The reaction mixture is then stirred at a temperature of 60 ° C. for 1 hour. The acetonitrile is distilled off from the reaction mixture and the remainder is dissolved in benzene with water and 1% sodium carbonate washed and dried over anhydrous sodium sulfate, after the distillation of benzene, 70 q colorless, oily O-ethyl-S-n-propyl-S-4-chlorobenzylthiomethylphosphorodithiolate obtain.

20 The product has a refractive index n ~ of 1.5867.

The compounds listed below can be prepared by analogous processes.

Table 1

Connection no.

structure

Γ " O - \

physical characteristics

^K P 131-135 ° C / 0 _f l mm Hg

tip 1.5391

PS-CH ₉ -SC.H _q -n

Nit 74

-7-

209808/1 ^ 88

1.5885

²⁵ ^ PS-CH ₀ -S- / \ ci bp. 1L4-157 ° C / 0.1 mm Hg

η ²⁰ 1.5922

Cl

> -S-CH _o -S - / ^> η ²⁰ 1.6030

Cl

CHO ⁰

⁵ ^ PS-CH ₀ -S η-C ₃ H ₇ S / ^A

0
^ PS-CH ₂ -S-CH ₂ - / vS

1.5810

C ₂ H ₅ O

· * S — CH r \ ■ "S""

9D

Cl rip 1.5867

Cl

0
PS-CH ₂ -S-CH ₂

When using the compounds of the invention as
Insecticides this diluted either with water or applied dire'it vo ¹ - the application of various according to requirements co- solvents or adjuvants or

Nit 74

-8th-

209808/1988

inert gaseous, liquid or solid diluents and / or carrier means, optionally also with others Auxiliaries such as surface-active agents, emulsifiers, Dispersants, spreaders and glues mixed and used in the various, in the preparation of agricultural Chemicals used in common forms.

As examples of gaseous diluents and / or carriers. mediums are freon and other propellants for aerosols, which are gaseous under normal conditions. Liquid diluents and / or carriers are water, organic solvents such as aromatic hydrocarbons, for example xylene, toluene, benzene, dimethylnaphthalene or aromatic petroleum fractions, chlorinated aromatic or aliphatic hydrocarbons, such as chlorobenzene, chloromethylene, chloroethylene or carbon tetrachloride, aliphatic hydrocarbons, for example gasoline , Cyclohexane or paraffin, alcohols such as methanol, propanol or butanol, ketones such as acetone, methyl ethyl ketone or cyclohexanone, polar solvents such as acetonitrile, dimethylformamide and dimethyl sulfoxide. Examples of solid diluents and / or carriers are the powders of natural mineral substances such as attapulgite, clay, chalk, talc, kaolin, montmorillonite , diatomaceous earth and calcium carbonate and the powders of synthetic mineral substances such as highly disperse silica, aluminum oxides and silicates . Examples of auxiliaries are nonionic or anionic surface-active agents or emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, alkylaryl polyglycol ethers, alkylsulphonates and arylsulphonates and dispersants such as lignin, sulphite waste liquors and methyl cellulose. Depending on requirements, the compounds according to the invention can also be used together with other agricultural chemicals such as insecticides, mematocides, fungicides (including antibiotics), herbicides, plant growth agents

With 74 -9-

209808/1988

reoulatoren, fertilizers and fertilizers can be used.

The insecticides according to the invention contain 0.1-95% by weight, preferably 0.5-90% by weight of the above-mentioned active ingredient. The active ingredient content can be varied depending on the form of preparation, method, object, time and place of application and the degree of infestation.

The insecticides according to the invention can either only from the active ingredient, but they can also be used in any other agricultural chemical usual preparation form, e.g. as a liquid preparation, emulsifiable liquid, concentrated emulsion, wettable Powder, soluble powder, oily preparation, aerosol, paste, incense, dust, particles, encrusted Use particles, tablets, granules and meal.

The erfindupgsgemäßen insecticides can be either directly applied to the habitat of the harmful insects or by means of devices according to any method of spraying ₉ scattering, sputtering, Verne leg, scatter of powder, scattering before. Particles, mixing, smoking, injecting or covering with powder can be used. The insecticides according to the invention can also be used according to the so-called "ultra-low-volume" method, which allows concentrations of active ingredient between 95 and 100 % .

When actually used, the active ingredient content in the ready-to-use preparations can be varied within a wide range for the same reason that applies to the preparation form itself. Preferably, however, the content of active ingredient is generally 0.0001-20% by weight, in particular 0.001-5.0% by weight . The amount of application of the

Nit 74 -10-

209808/1988

the insecticide according to the invention is about 15-1000 g / 10 a, preferably 40-600 g / 10 a, based on the active ingredient. However, these quantities can be exceeded or undercut as required.

The present invention therefore relates to an insecticidal agent which, as an active ingredient, is a compound of the above given formula (i), a solid or liquid diluent and / or carrier and, as required, one Contains auxiliary material.

The present invention relates to a method for controlling insects, which consists in that on the Harmful insect habitat a compound of the above formula (i) alone or mixed with one solid or liquid diluents and / or carriers, as required together with an auxiliary, applied will.

The present invention is illustrated by the examples given below, which however are not restrictive, explained in more detail.

Example It

15 parts of the inventive compound no. 4, 80 parts of a mixture of kieselguhr and kaolin and 5 parts of the emulsifier ¹¹ RUNNOX ¹¹ (product of Toho Kagaku Kogyo Kabushiki Kaisha) were ground and mixed to form a wettable powder, which was applied diluted with water.

Example 2;

30 parts of the compound no. 1 according to the invention, 30 parts of xylene, 30 parts of "KAWAKASOL ¹¹ (product of Kawasaki Kasei

Nit 74 -11-

209808/1988

Kogyo Kabushiki Kaisha) and 10 parts of the emulsifier "SORPOL ¹¹ (product of Toho Kagaku Kogyo Kabushiki Kaisha) were converted, with stirring, into an emulsifiable preparation which was applied diluted with water.

Example 3:

10 parts of compound no. 2 according to the invention, 10 parts Bentonite, 78 parts of zeeklite and 2 parts of lignin sulfonate were mixed and then intimately mixed with 25 parts of water. The mixture was closed with an ejection granulate fine particles of 375 - 750 / U diameter (20-40 mesh)

processed and then dried at a temperature of 40-50 C.

Example 4 :

2 parts of the compound according to the invention Mr. 8 and 98 parts a mixture of talc and clay were ground together and mixed into dusts.

Compared to known compounds of analogous structure and compounds of similar biological activity the compounds according to the invention by significantly improved effectiveness and very low toxicity warm-blooded animals and therefore of great usefulness.

The unexpectedly great effect and the advantages of the invention Compounds are made from the results of tests for effectiveness gon various harmful insects of the Genus Lepidoptera can be seen.

Test 1 ■ '. ". =,

Test for effectiveness against the double-breeding rice stem borer:

Nit 74 -12-

209808/1988

Preparation of test chemicals;

Solvent; 3 parts by weight of dimethylformamide emulsifier: O ₁ L parts by weight of alkylaryl polyglycol ethers

To convert the active ingredient into a suitable preparation, 1 part by weight of active ingredient with the above amount of solvent containing the above amount of emulsifier contained, mixed, the resulting mixture was before use with water to the prescribed concentration diluted in active ingredient.

Test procedure :

Water rice seedlings were planted in a pot with a diameter of 12 cm and the egg soils of the double-brooding rice rod auger were applied. 7 days after the insects hatched, the emulsifiable liquid diluted to the prescribed amount of active ingredient was sprayed on in amounts of 40 ml per pot and the chemical-treated pot was kept in a glass house for 3 days. The stems of the rice plants thus treated were individually examined " ¹ " to determine the number of living and dead insects and to calculate the mortality rate

Test 2

Test of effectiveness against tobacco seed owl larvaeϊ

Test procedure:

Sweet potato leaves have been diluted in, emulsifiable Liquid containing the prescribed amount of the invention Compound and prepared as indicated in Test 1, immersed, air dried and placed in a petri dish with a diameter of 9 cm. Then 10 larvae of the tobacco seed owl were

Nit 74 -13-

2 09808/19 88

2119215

Winding stage placed in the shell and this held in a ^v thermostatic chamber for 24 hours at a temperature of 28 C. At the end of this period, the number of dead insects was determined and the kill rate calculated.

Test 3

Test for effectiveness against almond moths:

Test procedure on;

20 vol! Developed larvae of the almond moth were in a A container made of fine mesh wire, 7 cm in diameter and 0.9 cm high, was placed in the container for 10 seconds a liquid diluted with water which contained the prescribed amount of active ingredient according to the invention and manufactured in the same way as described in test 1, submerged, the container then allowed to stand in a thernostat chamber for 24 hours. Then the number of dead insects were found and the kill rate was calculated.

The results of the tests for effectiveness against harmful insects of the genus Lepidoptera such as the double-breeding rice stem borer and the larvae of the tobacco seed owl and of the almond moth can be seen from Table 2, which also contains the results of comparative tests with analogous compounds are listed.

Nit 74 -14-

09808/1988

T__a_b_Q, lie 2
T3bak <; a <"iteulenlarvae Harmful insects 0.1 % 0.03 % 0.01 ) ό Active ingredient concentration 50 OO
70 OO
100 100 100 link ο
^{2 5} ^ PS-CHo-S-CoH ₁ -
^C 2 ^H 5 ^S
Connection according to
NJ 'Pat.Publ. Sho 32-7520
O
°° ^C 2 ^H 5 ° \ "
⁰⁰ C H ^c i ^// ' 2 2 2 5
_ "Connection according to
to Pat.Publ. Sho 38-16875
OO
OO
O
^{2 5} ^ PS-CH ₂ -S-CoH ₅
Connection No. 1
according to the present 3r
invention

^ ^ 3 n.d °] ._ rno ^ tt ο

0.1 % 0.03 % 0.01 %

100

100

ZW ρ imn 1st brood ncljr Roissant Yellow Boliror

100

continuation

-15-

η-C ₄ H ₉ S Table 2 S 0.03 # 0.01 % Almond moth 0.03 % 0 .01 * twice breeding
the Reisstengei-
drill (Continuation) 15 0 0.1 % 0 0 0.03 % Harmful insects Tobacco seedulon larvae 75 20th Active ingredient concentration 0.1? 0 0 0 0 link 90 ■ 0 0 ^{2 5} 3-S-CH ₀ -SC ₀ H.
n-CH ^ r ^ 100 100 100 100 »> CHO ⁰ 25th 100 100 ο 2 5 ^ ₀ .3.CH -SZ ^- VCI
<ο ° 2 5 ^^^
ο Connection according to Pat.
to · PJbl. Shp 44-25348 100 50 0 0 0 _o 2 5 ^ .5.CH ₂ -SZ ^ -Cl 80 15th ° connection no. 4 according to
of the present invention Q 90

continuation

-16-

Harmful insects Table 2 0V03 % 0.01 % • Almond moth .01 % incubate twice
the rice stalk
drill Active ingredient concentration (Continuation) 0.1 % 0.03 % 0 0.03 % link Tobacco seed owl larvae 0 0 0 ro
ο C H 0 \ ° / - \ 0.1 % 100 100 0 0 100 0 3808/1 ^{2 5} ^ PS-CH ₂ -S-CH ₂ - / ^ Vcl 100 100 100 886 0 65 • Connection no. 8 according to
of the present invention 100 0 0 0 CHO ⁰ 7-λ 90 0 40 ^{2 5} ^ PS-CH ₂ -S-CH ₂ ^ VCl nC ₄ HgS ^ ^{= z} ^ 95

Au ·; the results listed in table 2 can be seen, that the invention has certain connections. Compared to analogous compounds, excellent effectiveness against show harmful insects of the genus Lepidoptera.

The results of tests with the inventive Listed compounds against various harmful insects.

Test for effectiveness against the tobacco seed:

Testyerfahf0ni · / ■,

The test was carried out in the same way as test 2, the results are shown in Table 3.

Table 3. .

Results of the Tesfs on effectiveness against the tobacco seed

Connection no * Kill rate (%) 100 ppm 300 ppm iöo 1 100 100 2 1Ö0 100 3 100 100 4th 100 100 5 100 100 6th 100 50 "7 100 100
100 G 100
^ont ioo 20th Sumithion (commercial
Comparison product) 80

Nit.74

-18-

209808/1988

Comments: 1.) The connection numbers correspond to those

in table 1

2.) Sumithione: dimethyl (3-methyl-4-nitrophenyl) thiophosphate

Test for effectiveness against house flies: Test method :

1 ml of a liquid diluted with water, which contained the active ingredient in a prescribed amount and was prepared as described in test 1, was added to eir. Filter paper dropped into a Petri dish with a diameter of 9 cm. Then, 10 female, fully developed domestic chairs were placed in d.re dish and this was for 24 hours qehalten in a thermostatic chamber at a temperature of 28 ⁰ C. At the end of this period, the dead insects were counted and the mortality rate calculated.

The results are shown in Table 4.

Table 4
Results of the tests for effectiveness against house flies:

link
No. Degree of destruction {%) 100 ppm 1
2
3
4th
5
6th
7th
8th
9 1000 ppm 100
100
100
100
70
70
80
70
90 100
100
100
100
100
100
100
100
100

Nit 74

-19-

continuation

209808/1988

Table 4 (continued)

link Degree of destruction (%) PS-CH ₂ -S- / J-Cl
nC ₄ H ₉ S ( _comparison ) 1000 ppm 100 ppm ^C 2 ^H 5 ° N °
PS-CH ₂ -SC ₂ H ₅
nC ₄ H ₉ S / (comparison) 0 0 100 0
C-

Test for effectiveness against the brown jumping fright test method!

A liquid diluted with water containing the prescribed amount of active ingredient and as in test 1 was prepared, was planted in quantities of 10 ml per pot on 10 cm high, in pots of 12 cm diameter Rice seedlings sprayed on. After the liquid had dried, the pots were covered with cylindrical wire nets of 7 cm in diameter and 14 cm in height, in which 30 female, fully developed brown jumpers are found found covered. The pots were kept in a thermostatic chamber for 24 hours, after which time it was the number of dead insects was determined and the kill rate was calculated.

The results are shown in Table 5. Nit 74 -20-

209808/1988

Ii

Table 5

Results of tests for effectiveness against the

Brown jumping insect

Connection no. Degree of destruction {%) Active substance concentration
0.05 % 1 100 2 100 3 96.7 7th 93.3 Malathion (commercially available
Comparison product) 60.5

Annotation? The connection numbers correspond to those in table 1.

Test 6

Test for effectiveness against the Green Reisspring Schrecke "

Test procedure ».

This test was carried out as described in Tect 5 with 30 females Green snap jumpers carried out.

The results are shown in Table 6.

Table

Results of the tests for effectiveness against the greens

Rice shrimp

Connection no. Killqsqrad {%) 1
2
3
7th Active ingredient concentration 0.05% 100
100
89.7
100

Nit 74

-21-

209808/1

Note: The connection numbers correspond to those in

Table 1. . ■,. ■ ^: .;.

T-est 7 ... ■: ■ "- ■■

Test for effectiveness against fully developed mosquito larvae «.

Test procedure; '.

100 ml of a liquid diluted with water, which the The prescribed amount of active ingredient and prepared as described in the test were placed in a Petri dish of 9 cm diameter and 6 cm depth * Then 25 fully developed mosquito larvae were placed in the dish and this was kept in a thermostatic chamber for 24 hours * At the end of this period, the number of deaths was determined Insects detected and the kill rate calculated.

The results are shown in Table 7.

Table 7

Results of 3 tests for effectiveness against fully developed

Mosquito larvae

Connection No, Degree of destruction (%) 1
2
4th
8th Active ingredient concentration
0.1 ppm 100
100
100
100

Note: The connection numbers correspond to those in Table 1.

Nit 74

-22-

209808/1988

Test 8

Test for action against the red spider mite:

Te stye driving;

Fjarx bean seedlings in the two-leaf stage were planted in a 6 cm diameter pot and infected with 50-10.0 adults and nymphs of the red spider mite. 2 days after infection, a lye diluted with water, which contained the active ingredient in the prescribed amount and was prepared as described in test 1, was sprayed onto the pots in amounts of 40 ml per pot. The pots were kept in a glass house for 10 Taoe, after which time the control effect was evaluated. The evaluation was carried out according to the index according to the following scale:
Index:

3: No live adults, nymphs, or eggs

2: less than 5 % live adults, nymphs and

Eggs compared to the untreated control area

Is 5 - 50 % live adults, nymphs and eggs compared to the untreated control area

0: more than b0 % live adults, nymphs and

Eggs compared to the untreated control area

The results are shown in Table 8.

Nit 74 - -23-

09 808/1988

Table 8

Results of tests for effectiveness against the red

Spider mite

link Active ingredient concentration 0.03 % 0.01 % 0.003 Si 0.1 % 3 3 3 No. 1 3 3 3 3 2 3 3 3 3 4th 3 3 O 2 8th 3 3 3 2 9 3 2 0 0 Sappiran 3

Remarks:

1) the connection numbers correspond to those in the table

2) Sappiran: chlorophenyl chlorobenzene sulfonate.

Nit 74

-24-

20 9808/1988

Claims (6)

Patent claims: "> ) Organic phosphoric acid esters of the general formula ^C 2 ^H 5 ° n-C PS-CH ₂ -SR wherein R is a lower alkyl radical, a phenyl substituted with a halogen atom or a lower alkyl radical or benzyl radical or an unsubstituted phenyl or benzyl radical. 2) Process for the production of organic phosphoric acid esters, characterized in that 0-ethyl-S-n-propyl-dithiophosphoric acid Metal or ammonium salts of the general formula . M. with alkyl mercaptomethyl halides of the formula Hal -CH ₂ - S - R converts, with in the aforementioned formulas R has the meaning given in claim 1, while M is a metal atom or the ammonium group and Hai is a halogen atom. Nit 74 - 25 - 2 0 9 8 0 8/1988 3) insecticidal, acaricidal and nematicidal agents characterized by a content of compounds according to claim 1, 4) method mr control of insects, mites and nematodes, characterized in that compounds according to claim 1 are applied to the said pests or their Lets living space act. 5) Use of compounds according to Claim 1 for combating of insects, mites and nematodes. 6) Process for the preparation of insecticides, acaricidal and nematicidal agents, characterized in that one Mixing compounds according to claim 1 with extenders and / or surface-active agents. Nit 74 - 26 - 209808/1388