CH617706A5 - Process for the preparation of novel alkyl N-((thiono)thiol-phosphoryl)iminoformates and their use as ingredients in insecticides and acaricides. - Google Patents

Description

The present invention relates to a process for the preparation of new alkyl N - [(thiono) thiolphosphoryl] imino ants, which have an insecticidal and acaricidal action, and their use as a component in appropriate compositions.

brings to reaction, in the formulas (II) and (III) R, R ', alk and X have the meaning given above.

Surprisingly, the N- [(thiono) thiolphosphoryl] -imino formic acid 4-alkyl esters have a significantly better insecticidal, especially systemic, insecticidal and acaricidal action than the previously known N- [0, S-dimethyl-thionothiolphosphoryl] formic acid ethyl ester of analogous constitution and the same direction of action.

The fabrics produced according to the invention thus represent a real enrichment of technology.

If you use e.g. B. O-methyl-S-äthylmercaptoäthyl-thiolphosphorsäurediesteramide and ortho-formic acid ethyl ester as starting materials, the course of the reaction can be represented by the following formula:

CHsO O C2H5O

\ ll \

P-NH2 + CH-OC2H5

/ /

C2H5S-C2H4S C2H5O

• 2 X CzHsOH

CHsO O

\ ll p-N = CH-OCaHs

/

C2H5S-C2H4S

The starting materials to be used are generally clearly defined by the formulas (II) and (III). R is preferably straight-chain or branched alkyl having 1 to 4, R 'is alkenyl or alkynyl having preferably 2 to 4 carbon atoms, N-monomethyl or N-monoethylcarbamoyl-60 methyl, methylmercaptoethyl and ethylmercaptoethyl, while alk is preferably straight-chain or means branched alkyl having 1 to 3 carbon atoms.

Most of the 0-alkyl (thiono) thiol-phosphoric acid ester amides (II) required as starting materials are known and 65 can easily be prepared by generally customary methods (cf. e.g. DT-AS 1216 835, NL-OS 6 911925 and DT- OS 2 135 349). The ortho-formic acid alkyl esters (III)

and the methods for their preparation have also been described in the literature.

Examples of 0-alkyl (thiono) thiolphosphoric acid ester amides (II) and ortho-formic acid alkyl esters (III) to be used in the process according to the invention are:

O-methyl-S-allyl, O-ethyl-S-allyl, on-propyl-S-allyl, O-iso-propyl-S-allyl, on-butyl-S-allyl, O-sec .-Butyl-S-allyl-, O-iso-butyl-S-allyl-, O-tert.-butyl-S-allyl-, O-methyl-S-prop-argyl-, O-ethyl-S-propargyl -, On-Propyl-S-propargyl-, O-iso-Propyl-S-propargyl-, On-Butyl-S-propargyl-, O-sec.-Butyl-S-propargyl-, O-iso-Butyl-S -propargyl-, O-tert.-butyl-S-prop-argyl-, 0-methyl-S- (N-monomethylcarbamoylmethyl) -thiol-

3rd

617 706

phosphoric acid diester amide and the corresponding thiono-analog, and the methyl, ethyl or propyl ester of ortho-formic acid.

The production method according to the invention can be carried out using suitable solvents or diluents S. Practically all inert organic solvents can be considered as such. These include above all aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, gasoline, furthermore alcohols, such as ethanol, n-butanol, and also nitriles, such as aceto- and propionitrile. io In general, however, one works without solvents. Optionally, in the presence of acidic catalysts, such as. B. p-toluenesulfonic acid.

The reaction temperature can be varied over a wide range. In general, one works between 15 100 and 250 ° C; preferably between 140 to 160 ° C.

The reaction is generally carried out under normal pressure.

To carry out the reaction, the ortho-formic acid component is generally used in a 10 to 20% excess and the reaction mixture is heated, usually without a solvent, to the stated temperatures for several hours. Here, too, the mixture is usually worked up by distilling off the alcohol formed and distilling the reaction solution. 2s

The new substances mostly come in the form of colorless or light yellow oils and cannot be distilled without decomposing; therefore they are so-called «distillation», i. H. freed from the last volatile components by prolonged heating under reduced pressure to moderately elevated temperatures and cleaned in this way. The refractive index is used to characterize them.

As already mentioned several times, the alkyl N - [(thi-ono) thiolphosphonyl] imino formate is distinguished by an excellent insecticidal, in particular systemic, 35 secticidal and acaricidal activity against plant, hygiene and stored pests. They have a good effect against sucking as well as eating insects and mites (Acarina). They also have a low toxicity to warm-blooded animals; d. H. mostly a 5 to 10 times lower toxicity to warm-blooded animals than the starting products (II).

For this reason, the compounds which can be prepared according to the invention can be successfully used as pesticides, especially in crop protection. 45

Sucking insects mainly include aphids (Aphidae) such as green peach aphid (Myzus persicae), black bean (Doralis fabae), oat (Rhopalosiphum padi), pea (Macrosiphum pisi) and potato (Macrosiphum solanifolii), as well the currant 50 gall (Cryptomyzus korschelti), floury apple (Sappaphis mali), floury plum (Hyalopterus arundinis) and black cherry aphid (Myzus cerasi), as well as scale and mealybugs (Coccina), e.g. B. the ivy shield (Aspidiotus hederae) and bowl scale louse (Lecanium hesperidum) and 55 the mealybug (Pseudococcus maritimus); Bladder feet (Thy-sanoptera) such as Hercinothrips femoralis and bedbugs, such as the beet (Piesma quadrata), cotton (Dys-dercus intermedius), bed (Cimex lectularius), predatory (Rhod-nius prolixus) and Chagas bug (Triatoma infestans ), also 60 cicadas, such as Euscelis bilobatus and Nephotettix bipunctatus.

Among the biting insects, the caterpillars (Lepidoptera) such as the cabbage cockroach (Plu-tella maculipennis), the sponge spinner (Lymantria dispar), gold eater (Euproctis chrysorrhoea) and ring spinner (Ma- 65 lacosoma neustria), and the cabbage ( Mamestra brassicae) and the seed owl (Agrotis segetum), the large cabbage white (Pieris brassicae), small frost vices (Cheimatobia bramata), oak moths (Tortrix viridana), the army (Laphygma frugiperda) and Egyptian cottonworm (Prodenia litstura), and also the Gesodenpinura (Hyponomeuta padella), flour (Ephestia kühniella) and large wax moth (Galleria mellonella).

Furthermore, the biting insects include beetles (Co-leoptera), e.g. B. grain (Sitophilus granarius = Calandra granaria), potato (Leptinotarsa decemlineata), dock (Gastrophysa viridula), horseradish leaf (Phaedon cochlea-riae), rapeseed (Meligethes aeneus), raspberry (Byturus tomentosus), food - (Bruchidius = Acanthoscelides obtectus), bacon (Dermestes Frischi), khapra (Trogoderma granarium), red-brown rice flour (Tribolium castaneum), maize (Calandra or Sitophilus zeamais), bread (Stegobium paniceum), common flour (Tenebrio molitor) and cereal flat beetles (Oryzaephilus surinamensis), but also species living in the soil, e.g. B. Wireworms (Agriotes spec.) And white grubs (Melolontha melolontha); Cockroaches like the German (Blattella germanica), American (Periplaneta americana), Madeira (Leucophaea or Rhyparobia made-rae), Oriental (Blatta orientalis), giant (Blaberus gi-ganteus) and black giant cockroaches (Blaberus fuscus) as well as Henschoutedenia flexivitta ; further orthopters, e.g. B. the crickets (Gryllus domesticus); Termites such as the earth termite (Reticulitermes flavipes) and hymenoptera such as ants, for example the meadow ant (Lasius niger).

The Diptera essentially includes flies such as the tau (Drosophila melanogaster), Mediterranean fruit (Ceratitis capitata), parlor (Musca domestica), small parlor (Fannia canicularis), glossy (Phormia regina) and blowfly (Calliphora erythrocephala) as well as the Calf stick (Sto-moxys calcitrans); also mosquitoes, e.g. B. mosquitoes, such as the yellow fever (Aedes aegypti), house (Culex pipiens) and malaria mosquitoes (Anopheles stephensi).

The mites (Acari) include in particular the spider mites (Tetranychidae) such as the bean mites (Tetranychus telarius = Tetranychus althaeae or Tetranychus urticae) and the fruit tree spider mite (Paratetranychus pilosus = Panony-chus ulmi), gall mites, e.g. B. the currant mite (Erio-phyes ribis) and Tarsonemids, for example the spike mite (Hemitarsonemus latus) and cyclamen mite (Tar-sonemus pallidus); finally ticks like the leather tick (Ornithodorus moubata).

When used against hygiene and storage pests, especially flies and mosquitoes, the process products are also characterized by an excellent residual effect on wood and clay as well as a good stability to alkali on limed substrates.

The active substances which can be prepared according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, pastes and granules. These are manufactured in a known manner, e.g. B. by mixing the active ingredients with extenders, that is liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants. In the case of the use of water as an extender, e.g. B. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, benzene or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclo-hexane or paraffins, e.g. B. petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylform amide and dimethyl sulfoxide, and water; with liquefied

617 706

4th

Gaseous extenders or carriers are such preparations can be varied over a wide range of liquids, which are at normal temperature and. They are generally between 0.0001 and 10 "/ o, are gaseous under normal pressure, for example aerosol propellants, preferably between 0.01 and 1" / ». such as halogenated hydrocarbons, e.g. B. Freon; as a solid carrier- The active ingredients can also be used with great success in ultra fabrics: natural stone flours, such as kaolins, clays, Tal's low-volume process (ULV), where there is cum, chalk, quartz, attapulgite, montmorillonite, or Diato- is possible to apply formulations up to 95 "Io or even the meide, and synthetic rock flour, such as highly disperse 100 Voigen active ingredient alone.

Silica, alumina and silicates; as an emulsifier:

nonionic and anionic emulsifiers, such as polyoxy example 1

ethylene fatty acid ester, polyoxyethylene fatty alcohol ether, io Myzus test (contact effect)

e.g. B. alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates,

Solvent: 3 parts by weight of acetone.

Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, which contains the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

2D Cabbage plants (Brassica oleracea), which are heavily infested with peach aphids (Myzus persicae), are sprayed to runoff point with the preparation of active compound.

After the specified times, the degree of killing is determined in <Vo. 100% means that all aphids are turned away in the usual way, e.g. B. by spraying, 25 were killed, 0% means that no aphids were killed. Spraying, atomizing, dusting, scattering, misting.

marriage, gasification, pouring, pickling or incrustation. Active substances, active substance concentrations, evaluation times

The drug concentrations in the ready-to-use and results are shown in Table 1 below:

Table 1 (Myzus test)

and aryl sulfonates; as a dispersant: e.g. B. lignin, sulfite and methyl cellulose.

The active substances which can be prepared according to the invention can be present in the formulations in a mixture with other known active substances.

The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

The active compounds can be used as such, in the form of their formulations or in the use forms prepared from them, such as ready-to-use solutions, emulsifiable concentrates, emulsions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. The active ingredient. Drug killing level concentration in ° / o in 0 / o after 1 day

CHaS S

^ P — N == CH — OC2H5 0.1 100

/ 0.01 20 CHsO

(known) (A)

CH2 = CH-CH2S O

\ || 0.1 100

P-N = CH-OC2H5 0.01 100

C «, 7 ° '° 01 95

CH-CH — ems o 0I m

P-N = CH-OC2H5 0.01 98

^ TT y 0.001 60 C2H5O

CHsC-CHïS O 'ni

\ || 0.1 100

P-N = CH-OC2H5 0.01 95

a / ° '001 80

CH-C-CH ^ O 0> 1 m

P-N = CH-OC2H5 0.01 99

/ 0.001 95

C2H5O

CHa-NH-C-CH2S O 0.1 100

\ || 0.01 100

—N = CH — OC2H5 0.001 50

C2H5O

5

617 706

Active ingredient Active ingredient killing degree concentration in ■% in '% after. 1 day

C2H5S-CH2-CH2-S O

\ ü 0.1 100

p-N = CH-OC2HS 0.01 100

CzHsO

Example 2 (Vicia faba), which is strongly influenced by the black bean louse (Dora

Doralis test (systemic effect) ^ fabae) are cast on, so that the active ingredient preparation penetrates into the soil without the leaves of the solvent: 3 parts by weight of acetone. J5 to wet bean plants. The active ingredient is from the

Emulsifier: 1 part by weight of alkylaryl polyglycol ether. Bean plants are taken up from the soil and thus reach the infected leaves.

For the preparation of a suitable active ingredient preparation. After the times indicated, the degree of destruction is determined and 1 part by weight of active ingredient is mixed with the specified amount. 100 fl / o means that all the aphids give off the amount of solvent which the specified amount has been killed 0 0 / o means that no aphids have been killed

Contains emulsifier, and the concentrate was diluted with water.

to the desired concentration. Active substances, active substance concentrations, evaluation times

With the active ingredient preparation, bean plants and results are shown in Table 2 below:

Table 2 (Doralis test / systemic effect)

Active ingredient Active ingredient degree of killing in% in ° / o after 4 days

CHaS S

\ ll

P-N = CH-OC2H5

CHaO ^

(known) (A)

0.01

CH2 = CH-CH2S O

^ P-N = CH-OC2H5 0.01 100

/

CHsO

CH2 = CH-CH2S O

^ p — N = CH — OŒHs 0.01 100

C2HsO //

CH = C-CH2S O

^ P-N = CH-OCzHs 0.01 100

CHa </

CH = C - CH2S O

^ p — N = CH — OŒHs 0.01 100

CzHsO ^

O

II

CHa-NH-C-CH2S O 0.01 100

\! l

P-N = CH-OC2H5

/

C2HSO

C2H5S-CHz-CH2-S O

NP — N = CH — OC2HS 0.01 100

/

C2H50

617 706

6

Example 3 Tetranychus Test (Resistant)

Solvent: 3 parts by weight of acetone.

Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, which contains the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

With the active ingredient preparation, bean plants

10th

(Phaseolus vulgaris), which are about 10–30 cm high, sprayed to runoff. These bean plants are heavily infested with all stages of development of the common spider mite (Tetranychus urticae).

After the specified times, the effectiveness of the active ingredient preparation is determined by counting the dead animals. The degree of destruction obtained in this way is given in%. 100 «/ o means that all spider mites have been killed, 0% means that none of the spider mites have been killed.

Active substances, active substance concentrations, evaluation times and results are shown in Table 3 below:

Table 3 (Tetranychus test / resistant)

Active ingredient

Active ingredient concentration in o / o

Degree of killing in o / o after 2 days

CHaS S

\ l!

p-

/ CHsO

-N = CH-OC2H5

(known) (A)

0.1

CH2 = CH-CH2S o

\ ll

P-N = CH-OC2H5

/

CHsO

0.1

98

CH2 = CH-CH2S O

^ P — N = CH — OCaHs

/

C2H5O

0.1

99

CHssC-CH2S O

^ P-N = CH-OC2H5

cm </

0.1

98

CHssC-CH2S O

N? —N = CH — OC2H5 /

C2H5O

0.1

98

CîHîS — CHr-CHz — S O

\ ll

P-

/ C2H5O

■ N = CH — OC2HS

0.1 0.01

100 50

Example 4 LDioo test

60

Test animals: Sitophilus granarius.

Solvent: acetone.

2 parts by weight of active ingredient are taken up in 1000 volumes of solvent. The solution thus obtained is diluted to the desired concentrations with further solvent.

5.2 ml of the active ingredient solution are pipetted into a petri dish. On the bottom of the Petri dish is a filter paper with a diameter of approximately 9.5 cm. The petri dish remains open until the solvent has completely evaporated. Depending on the concentration of the active ingredient solution, the amount of active ingredient per m2 of filter paper varies. Then add about 25 test animals to the Petri dish and cover them with a glass lid.

The condition of the test animals is checked 3 days after starting the experiments. The death rate is determined in%.

Active substances, active substance concentrations, test animals and results are shown in Table 4 below:

7

617 706

Table 4 (LDioo test / Sitophilus granarius)

Active ingredient

Active substance concentration of the solution in%

Degree of killing in ■%

O

(CH3CO2P-S-CH2-CH2-SO-CîHS (known)

0.2

20th

CH2 == CH — CH2 — S o

^ p — N = CH — OC2HS /

CHsO

0.2

100

CH2 = CH-CH2S o

\ ll

P-N = CH-OC2HS

/

C2H5O

.0.2

100

CH = C-CH2-S O

^ P — N == CH — OCzHs /

CHsO

0.2 0.02

100 100

CHssC-CH2-S O

\ I1

P_N = CH-OC2H5

/

C2H50

0.2 0.02

100 100

C2H5S-CH2-CH2-S o

^ P — N = CH- ^ OC2HS /

C2H50

0.2 0.02

100 70

Example 5 LTioo Test for Diptera

Test animals: Musca domestica. 60

Solvent: acetone.

2 parts by weight of active ingredient are taken up in 1000 parts of solvent. The solution thus obtained is diluted with further solvent to the desired lower concentrations. 65

2.5 ml of the active ingredient solution are pipetted into a petri dish. On the bottom of the Petri dish is a filter paper with a diameter of approximately 9.5 cm. The petri dish remains open until the solvent has completely evaporated. Depending on the concentration of the active ingredient solution, the amount of active ingredient per m2 of filter paper varies. Then add about 25 test animals to the Petri dish and cover them with a glass lid.

The condition of the test animals is continuously checked. The time is determined which is necessary for a 100 «/» knock-down effect.

Test animals, active substances, active substance concentrations and times at which there is a 100% knock-down effect are shown in Table 5 below:

617706

8th

Table 5

(LTioo test for Diptera / Musca domestica)

Active ingredient concentration LTioo in minutes (')

of the solution in% or hours (h)

(CH30) 2P-S-CH2-CH2-SO-C2H5 (known)

0.2 195 '

CHz = CH-CH2-S O

\ ll 0.2 25 '

^ P — N == CH — OCÎHÎ o, 02 110 '

CHsO

CH2 = CH-CH2-S O

\ l | 0.2 100 '

/ P-N = CH-OC2H5 0.02 6 h

C2H5O

CHaC-CHz-S O

\ ll 0.2 20 '

P — N = CH — OC2H5 o, 02 100 '

CHsO

CHsssC-CH2-S O

\ ll 0.2 25 '

^ —N = CH — OC2H5 o, 02 6 h

C2H5O

CH3-NH-CO-CH2-S O

\ ll 0.2 100 '

P-N = CH-OC2HS o, 02 6 h

C2H5O

Production Examples Example 6

CHz-CH-CH2S O

\ ll

F-

/ CiHsO

-N == CH — OC2H5

40

45

A mixture of 36 g (0.2 mol) of O-ethyl-S-allylthiolphos-

phosphoric diester amide, 30 g of ortho-formic acid ethyl ester and 1 g of p-toluenesulfonic acid are boiled at 100 ° C. for 30 minutes (10 cm Vigreux column), then the reaction mixture is distilled. This gives 35 g (77% of theory) of the desired N- (0-ethyl! -S-allylthiolphosphoryl) -imino formic acid ethyl ester with the boiling point 96 ° C./0.01 Torr and the refractive index n ff: 1.4962.

The following connections can be made analogously:

9

617 706

constitution

Physical data [boiling point (° C); Refractive index]

Yield (%> of theory)

CïfesC— CH2S O

\ ll

P-N = CH-OC2H5

/

C2H5O

102 / 0.01 Torr nf? : 1.5049

68

CH2 = CH — CH2S o n,, nn1 "

\ t 96 / 0.01 Torr

/ P-N = CH-OC2Hs n 2t. 1; 50ii CHsO

81

CÄC-OTS O 102 / 0.01 Torr

P-N = CH-OC2HS n 21. 15118

CH30 //

63

CHa-NH-CO-CH2S O

\! i

P-

/ C2H5O

-N = CH-OC2H5

n d: 1.5032

39

C2HsS-CHz-CH2-S O

\ ll

P-

/ C2H5O

-N = CH-OC2HS

118 / 0.01 torr

74

CH2 = CH-CH2S see

\ ll p-

/

CHsO

-N = CH-OC2H5

CH2 = CH-CH2S S

\ ll

P-

/ C2H5O

-N = CH-OC2H5

C2H5S-CH2-CH2-S S

^ P — N = CH — OC2H5 /

CHsO

C2H5S-CH2-CH2S S

\ ll

P-

/ C2H5O

-N = CH-OC2H5

617 706

10th

The following connections can also be made:

0-ethyl-S- (N-monomethylcarbamoylmethyl) -, on-propyl-S- (N-monomethylcarbamoylmethyl) -, 0-iso-propyl-S- (N-monomethylcarbamoylmethyl) -, 0-butyl-S- ( N-monomethyl-carbamoylmethyl) -, 0-methyl-S- (N-monoethylcarbamoylmethyl) -, 0-ethyl-S- (N-monoethylcarbamoylmethyl) -, O-butyl-S- (N-monoethylcarbamoylmethyl) - , O-methyl-S-methyl-mercaptoethyl, O-iso-propyl-S-methylmercaptoethyl, O-ethyl-S-ethylmercaptoethyl, and Ö-sec.-butyl-S-ethylmer-captoethyl-thiophosphorylimino formic acid ethyl ester, other alkyl esters and their thiono analogues.

The required starting compounds (II) can, for. B. can be produced as follows:

CîHs-S-CHx-CH2S O

\ ll

P — NEfe (IIa)

C2HsO //

63 g of 2-chloroethylethylthioether are added to 105 g (0.5 mol) of the sodium salt of O-ethylthiol-phosphoric acid ester amide in 250 ml of methanol. The reaction mixture is stirred at 70 ° C. for 1 hour, poured into 200 ml of water after cooling and extracted 3 times with 200 ml of chloroform. After the organic phase has dried, the solvent is distilled off and the residue is distilled. 106 g (93% of theory) of O-ethyl-S-ethylmer-captoethylthiolphosphoric diesteramide with a refractive index n p0: 1.5334 are obtained. The oil obtained crystallizes and upon recrystallization from a mixture of ethyl acetate and ligroin, a product melting at 50-53 ° C. is obtained.

The following compounds can be obtained analogously:

Constitution physical data

[Melting point (° C); Refractive index]

47

40

82

n ff: 1.5296

10th

20th

30th

CH2 = CH-CH2S O

\ ll p-NH2

/

C2H50

(over)

CH = C-CH2S O

\ ll

P-NH2

15 /

C2H5O

(Ile)

CH2 = CH-CH2S o

\ ll p-NH2

/

CHaO aid)

25 CH = C-CH2S O

\ ll p-NH2

CHsO

35

(Hey)

CH3-NH-CO-CH2S or

\ ll p-NH2

C2HsO //

M

Claims (2)

617 706 2nd io PATENT CLAIMS 1. Process for the preparation of new compounds of the formula R'S X P — N — CH — OAlk (I) / RO in which R alkyl with 1 to 6 carbon atoms, R 'alkenyl or alkynyl with 2 to 6 C atoms, lower alkylmercaptoniederalkyl or N-alkylcarbamoylmethyl, while Alk stands for alkyl with 1 to 6 C atoms and X is an oxygen or sulfur atom, characterized in that compounds of the formula 15 RO X \ ll P — NH2 (II) R'S with ortho-formic acid alkyl esters of the formula AlkO — CH — OAlk (IH) I. OAlk 20th It is already known (cf. German Offenlegungsschrift 2 116 690) that the ethyl N- {0, S-dimethylthionothiolphosphoryl] formate (compound A) has insecticidal and acaricidal properties. It has now been found that the novel N- [(thiono) thiolphosphoryl] -iminoamei-alkyl acid esters of the formula which can be prepared according to the invention. R'S X \ ll P — N = CH — OAlk (I) RO in which R alkyl with 1 to 6 carbon atoms, R 'denotes alkenyl or alkynyl having 2 to 6 C atoms, lower alkylmercapton lower alkyl or N-alkylcarbamoylmethyl, while Alk represents alkyl having 1 to 6 C atoms and an X is an oxygen or sulfur atom, are characterized by superior insecticidal and acaricidal activity. The new N - [(thiono) thiolphosphoryl] -imino ants-acidic acid alkyl esters of the formula (I) are prepared according to the invention by reacting compounds of the formula, wherein in the formulas (II) and (III) R, R ', Alk and X are the have the meaning given above. 2. Use of new compounds of the formula (I) R'S X \ ll P-N = CH-OAlk / RO in which R alkyl with 1 to 6 carbon atoms, R 'is alkenyl or alkynyl with 2 to 6, lower alkylmercapto-lower alkyl or N-alkylcarbamoylmethyl, while Alk represents alkyl having 1 to 6 carbon atoms and X is an oxygen or sulfur atom, as at least one active component in insecticidal and acaricidal agents. 25th 30th RO X \ ll P — NH2 (II) / R'S with ortho-formic acid alkyl esters of the formula AlkO — CH — OAlk (III) OAlk 35