DE2240031A1 - S- (N-ACYL-AMIDOCARBONYL) -METHYL-THIOPHOSPHORUS- OR -PHOSPHONIC ACID ESTERS, THE PROCESS FOR THEIR PRODUCTION AND THEIR USE AS INSECTICIDES AND ACARICIDES - Google Patents

Description

BAYER AKTIENGESELLSCHAFT 2240031

LEVERKUSEN-Bayerwerk ZentralbereiA 1 **> Patents, trademarks and licenses

Hu / MH Ia

S-CN-acyl-amidocarbonylJ-methyl-thiophosphorus or -phosphonic acid esters, process for their preparation and their use as insecticides and acaricides

The present invention relates to new S- (N-acyl-amido = carbonyl) -methyl-thiophosphorus or -phosphonic acid esters, which have insecticidal and acaricidal properties, and a method for their production.

It is already known that the reaction products of 0,0-dialkyl-thiophosphoric acids Salts with certain halogen = acetic acid-N-acyl-amides are insecticidal and Characterize the acaricidal effect (cf. German Auslegeschriften 1 148 806 and 1 143 052, British patent specification 867 780).

It has now been found that the new S- (N-acyl-amidooarbonyl) -methyl-mono- or dithiophosphorus or phosphonic acid esters of the formula

R-O X

X? ⁿ

R »S-CH ₉ -CN-acyl

have excellent insecticidal and acaricidal effectiveness.

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In the above formula, R, R ¹ and R ″ stand for identical or different, straight-chain or branched alkyl create with 1 to 6 carbon atoms; R ¹ can also be a straight-chain or branched alkoxy group with 1 to 6 carbon atoms and R ″ phenyl. Acyl stands for a lower alkylcarbonyl or phenylcarbonyl radical. X represents an oxygen or sulfur atom.

It has also been found that the new S- (N-acyl-amido = carbonyl) -methyl-mono- or -dithiophosphorus or -phosphon = Acid esters of the constitution (I) can be obtained if 0, O-dialkylmono- or dithiophosphorus (phosphonic) acid salts the formula

"Λ / ■

R ¹ SM

with haloacetic acid-N-acyl-amides of the formula

R ^H

Hal-CH ₂ -CN-acyl (III)

in which formulas R, R ', R ", acyl and X the above have given meaning, Hal is a halogen, preferably bromine or chlorine atom, and M is is an alkali, alkaline earth or optionally alkyl-substituted ammonium equivalent,

implements.

Surprisingly, the S- (N-acylamidocarbonyl) methyl thiophosphorus or phosphonic acid esters according to the invention have them of the formula (I) a much better insecticidal and acaricidal action than the known S- (N-acyl-amidocarbonyl) -methyl-thiophosphoric acid ester, which both with regard to Constitution and effect of comparable connections

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all the best-known commercial products in this class of materials represent and from which the compounds according to the invention differ by the nature of the acyl radical. the new substances thus represent an enrichment of technology.

If one uses the sodium salt of 0,0-Dimethyldithiophos = phosphoric acid and chloroacetic acid-N-acetyl-N-methylamide as Starting materials, the course of the reaction can be represented by the following equation:

CH, 0 S CH,

⁵ \ // ι. 3

P + Cl-CH ₀ -CNC-CH,

CH ₃ O S-Na 0 0

^CH 3 ° v
- NaCl ^ ^p

^ S-CH-CNC-CH, "" 3

0 0

S-CH ₀ -CNC-CH 2

The starting materials to be used according to the process are s-ind the formulas (II) and (III) are clearly defined in general.

Preferably, however, R, R ¹ and R ″ therein denote identical or different, straight-chain or branched alkyl radicals having 1 to 4 carbon atoms, such as methyl, ethyl, ieo- or n-propyl, n-, iso-, sea- or tert-butyl R ¹ also preferably stands for straight-chain or branched alkoxy groups with 1 to 4 carbon atoms, such as methoxy, ethoxy, iso- or n-propoxy, n-, iso-, sea- or tert-butoxy, and R ″ stands for phenyl . Acyl preferably denotes a lower alkylcarbonyl radical, such as the acetyl, propionyl, butyryl, isobutyryl radical and the benzoyl radical.

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All examples of usable 0,0-dialkyl-mono- or -dithio = Phosphorus (phosphonic) acid salts (II) are mentioned in detail: The alkali, alkaline earth or optionally alkyl-substituted Ammonium salts of O-methyl-0-isopropyl-, O-ethyl-O-isopropyl-, 0,0-di-n-propyl-, Ο, Ο-di-isopropyl-, 0,0-di-sec ^ · butyl mono- and dithiophosphoric acid and the corresponding Salts of O-methyl-, O-ethyl-, O-isopropyl-methane-mono- and -dithiophosphon or -isopropane mono- and -dithiophosphon = acid.

Haloacetic acid-N-acyl-amides (III) come, for example in question: chloro- or bromoacetic acid-N-acetyl-N-ethyl-, -N-acetyl-N-n-butyl-, -N-acetyl-N-sec.-butyl-, -N-propionyl-N-methyl-, -N-propionyl-N-ethyl-, -N-propionyl-N-isopropyl-, -N-propionyl-N-sec.-butyl-, -N-isobutyryl-N-ethyl-, -N-iso = butyryl-N-isopropyl-, -N-isobutyryl-N-sec.-butyl-, -N-benzoyl-N-ethyl-, -N-benzoyl-N-isopropyl-, -N-benzoyl-N-eec.-butyl-, -N-isobutyryl-N-phenyl- and -N-benzoyl-N-phenyl-amide.

The (di) thiophosphorus (phosphonic) acid salts (II) and the haloacetic acid derivatives (III) are known and can be used according to usual methods are produced.

The production process for the new substances (I) is preferred with the use of suitable solvents or diluents carried out. Practically all inert organic solvents can be used as such. This includes in particular aliphatic and aromatic, optionally chlorinated hydrocarbons, such as benzene, toluene, xylene, gasoline, methylene = chloride, chloroform, carbon tetrachloride, chlorobenzene, ether, e.g. B. diethyl and dibutyl ethers, dioxane, also ketones, for example acetone, methylethyl, methylisopropyl and Methyl isobutyl ketone, also nitriles, such as aceto and propionitrile, and alcohols, e.g. B. methanol, ethanol, Ieopropanol.

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In certain cases, water is also suitable as a solvent.

The reaction temperature can be varied within a relatively wide range. In general, the reaction is preferably carried out at between O and 120, at 15 to 6O ⁰ C.

The reaction is generally carried out under normal pressure.

The starting materials are used to carry out the process mostly in equimolar proportions. An excess of one or the other reaction component does not bring about any significant Advantages. The reaction is preferably carried out in the presence of one of the abovementioned solvents for those specified Temperatures carried out and the reaction mixture worked up after several hours of stirring in the customary manner.

The substances according to the invention are mostly in the form of colorless to slightly colored, viscous, water-soluble oils or Crystals which in general cannot be distilled undecomposed, but by so-called "partial distillation", d. H. prolonged heating under reduced pressure to moderately elevated temperatures, of the last volatile components can be freed and purified in this way. The refractive index is primarily used to characterize them, in the case of solid compounds, the melting point.

As already mentioned several times, the new S-CN-acyl-amidocarbonylJ-methylthiophosphorus or -phosphon = stand out acid esters due to an excellent insecticidal, acaricidal and soil insecticidal effectiveness against plants, stocks and Hygiene pests. They have a good effect against sucking as well as eating insects and mites (Acarina). At the same time, they have only low phytotoxicity.

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For these reasons, the compounds according to the invention are successfully used as pesticides in crop protection as well as used in the hygiene sector.

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The sucking insects mainly include aphids
(Aphidae) such as the green peach aphid (Myzus persicae),
the black bean (Doralis fabae), oat (Rhopalosiphum
padi), pea (Macrosiphum pisi) and potato mouse (Macrosiphum solanifolii), also the currant gall (Cryptomyzus korschelti), floury apple (Sappaphis mali), floury plum (Hyalopterus arundinis) and black cherry aphid (Myzus cerasi), as well as shield - and mealybugs (Coccina), for example the ivy shield louse (Aspidiotus hederae) and cup scale louse (Lecanium hesperidum) as well as the mealybug (Pseudococcus maritimus);
Bladder feet (Thysanoptera) such as Hercinothrips femoralis and
Bed bugs, for example beet bugs (Piesma quadrata), cotton bugs (Dysdercus intermedius), bed bugs (Cimex lectularius), predatory bugs (Rhodnius prolixus) and chagas bugs (Triatoma infestans),
also cicadas such as Euscelis bilobatus and Nephotettix bipunctatus.

Among the biting insects, butterfly caterpillars (Lepidoptera) such as the cabbage moth (Plutella maculipennis), the gypsy moth (Lymantria dispar) and golden juices should be mentioned in particular
(Euproctis chrysorrhoea) and ring moth (Malacosoma neustria), furthermore the cabbage (Mamestra brassicae) and the seed owl (Agrotis segetum), the large cabbage white butterfly (Pieris brassicae), small frost moth (Cheimatobia brumata), oak moth (Tortrix vireryidana) (Laphygma frugiperda) and Egyptian cotton worms (Prodenia litura), also the web (Hyponomeuta padella), flour (Ephestia kühniella) and large ones
Wax moth (Galleria mellonella),

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The biting insects also include beetles (Coleoptera) e.g. grain (Sitophilus granarius = Calandra granaria), Potato (Leptinotarsa decemlineata), dock (Gastrophysa viridula), horseradish leaf (Phaedon cochleariae), rapeseed (Meligethes aeneus), raspberry (Byturus tomentosus), table bean (Bruchidius = Acanthoscelides obtectus), Bacon (Dermestes Frischi), Khapra- (Trogoderma granarium), red-brown Rice flour (Tribolium castaneum), corn (Calandra or Sitophilus zeamais), bread (Stegobium paniceum), common flour (Tenebrio molitor) and grain beetle (Oryzaephilus surinamensis), but also species living in the ground, e.g. B. Wireworms (Agriotes spec.) and grubs (Melolontha melolontha); Cockroaches like the German (Blattella germanica), American (Periplaneta americana), Madeira (Leucophaea or Rhyparobia maderae), Oriental (Blatte orientalis), giant cockroach (Blaberus giganteus) and black cockroach (Blaberus fuscus) as well as Henschoutedenia flexivitta; also Orthoptera e.g. the cricket (! Icheta domesticus); Termites such as the terrestrial termites (Reticulitermes flavipes) and Hymenoptera such as ants, for example the meadow ant (Lasius niger).

The Diptera essentially comprise flies like the Tau (Drosophila melanogaster), Mediterranean fruit (Ceratitis capitata), room (Musca domestica), small room (Fannia canicularis), glossy fly (Phormia regina) and blowfly (Calliphora erythrocephala) as well as the calf trigger (Stomoxys calcitrans); also mosquitoes, e.g. mosquitoes such as the yellow fever (Aedes aegypti), house (Culex pipiens) and malaria mosquito (Anopheles stephensi).

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The mites (Acari) include spider mites in particular (Tetranychidae) like the bean (Tetranychus telarius = Tetranychus althaeae or Tetranychus urticae) and the orchard spider mite (Paratetranychus pilosus. = Panonychus ulmi), gall mites, 2.3. the currant mite (Eriophyes ribis) and tarsonemids, for example the shoot tip mite (Hemitarsonemus latus) and cyclamen mite (Tarsonemus pallidus)? finally ticks like the Lederzec.ke (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 good alkali stability on limed substrates.

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The active compounds according to the invention can be used in the customary formulations such as solutions, emulsions, suspensions, powders, pastes and granulates. These will produced in a known manner, e.g. B. by mixing the active ingredients with extenders, i.e. liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surface-active substances Agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. In case of Use of water as an extender can be, for. B. also used organic solvents as auxiliary solvents will. The main liquid solvents that can be used are: aromatics, such as xylene, toluene, benzene or alkyl = naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes 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 cyclo = hexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; with liquefied gaseous Extenders or carriers are liquids which are meant, which at normal temperature and below Normal pressure are gaseous, e.g. B. aerosol propellants such as halogenated hydrocarbons, e.g. B. Freon; as solid carriers: natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or Diatomaceous earth, and synthetic minerals such as finely divided silica, aluminum oxide and silicates; as emulsifying and / or show-generating agents: non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ether, Alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates; as a dispersant: e.g. B. lignin, sulphite waste liquors and methyl cellulose.

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

The active ingredients can as such, in the form of their formulations or in the application forms prepared therefrom, such as ready-to-use Solutions, emulsifiable concentrates, emulsions, foams, suspensions, wettable powders, pastes, soluble powders, Dusts and granules. It is used in the usual way, for. B. by spraying, spraying, Fogging, dusting, scattering, smoking, gasifying, pouring, pickling or encrusting.

The active ingredient concentrations in the ready-to-use preparations can be varied in larger areas. Generally they are between $ 0.0001 and $ 10, preferably between $ 0.01 and $ 1.

The active ingredients can also be used with good success in the ultra-low-volume process (ULV) to be used where it is possible, formulations up to 95 5 * or even the 100 fig active ingredient to apply alone.

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Example A.
Plutella test

ι * -

Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the specified Amount of solvent that contains the specified amount of emulsifier and dilute the concentrate with water to the desired Concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation of active compound and they are populated with caterpillars Cabbage moth (Plutella maculipennis).

After the specified times, the degree of destruction is determined in % . 100% means that all of the caterpillars have been killed, while 0 % indicates that no caterpillars have been killed.

Active ingredients, active ingredient concentrations, evaluation tents and The results are shown in Table 1 below:

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(Plu-bella test)

Active ingredient Active ingredient fkon = degree of abortion in centratian in j * after 5 sayings

(CH _x O) ₉ CH _PB-9 -CO-Ir-CHO, 0 ₉ 1100

J C- C- (

(known)

CH ₅ Op 01 0

(G ₂ H ₅ O) ₂ PS-CH ₂ -GO-N-CHO 0 ₉ 1 70

CH ₅ 0 _s 01 0

(known)

₁ -VS> ΌΗ ,.

PS-GH ₀ -CO-H-GO-CH 0 ^ CH,

PS-CH ₂ -CO-N-CO-CH ₃

p.o / 'i-C, H »

0 3 7

0.1. 100 0 ₉ 01 100 0.1 100 0.01 100

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Example B.

Myzus test (contact effect)

Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ethers

To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the specified Amount of solvent that contains the specified amount of emulsifier and dilute the concentrate with water to the desired Concentration.

Cabbage plants (Brassica oleracea), which are strongly dependent on the peach aphid (Myzus persicae) are infected, sprayed dripping wet.

After the specified times, the degree of destruction is determined in % . 100% means that all aphids have been killed, 0 % means that none of the aphids have been killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in Table 2 below:

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ΑΪ

Tabe lle 2
(Myzus test)

Active ingredient ■ Active ingredient concentration Degree of destruction in concentration in fo after 1 day

S. O ₉ I 99

(C ₉ H ^ O) ₉ PS-CH ₉ -CO-N-CO-OC ₉ Hp 0.01 80

C. 2 C. C. ι C. y

(known)

CH, 0.001 0

v S * 0.1 100

PS-CH ₂ -Co-N-CO-CH ₅ 0.01 100

CH ₃ 0.001 99

C ₂ H ₅ Ov S 0.1 100

PS-CH ₂ -CO-N-CO-CH ₃ 0.01 100

C _o H _c 0 ^ CH- 0.001 100

C ₂ H ₅ Ov S '0.1 100

PS-CH ₂ -CO-N-CO-CH ₃ 0.01 100

C ₂ H ₅ / CH ₃ 0.001 98

CTT r \ c * fO Γ \ Λ Λ Γ \ Γ \

ο Xl1— Wv O S W Xi "» \ J · I ι \ J \ J

5 'X 3'.

PS-CH ₉ -CO-N-CO-CH 0.01 99

CH ₃ ^ CH ₃ 0.001 65

Ov S / ^GH 3 ° ' ^{1 10} °

PS-CH ₂ -CO-N-CO-CH 0.01 100

/ CH ₃ ^ CH ₃ 0.001 97

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continuation

Tabel

(Myzus test)

Active ingredient active ingredient concentration degree of destruction in concentration in yes after 1 day

v S

PS-CH ₂ -CO-N-CO- ^ CH ₃

0.1

0.01

0.001

100

100

95

C ₂ H ₅ Ov S

C ₂ H ₅

PS-CH ₂ -CO-N-CO- ^

CH

0.1

0.01

0.001

0.0001

100 100 100

90

v S Nu

PS-CH ₀ -CO-N-CO-CH, 0.1

0.01

0.001

100 99 80

C ₂ H ₅ Ov S

PS-CH ₀ -CO-N-CO-CH,

0.1

0.01

0.001

100 99 95

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Example C

Rhopalosiphum test (systemic effect)

Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

Mixed to produce an appropriate preparation of active ingredients 1 part by weight of active ingredient with the specified amount of solvent containing the specified amount of emulsifier, and dilutes the concentrate with water to the desired concentration.

Oat plants (Avena sativa) which are heavily infested by the oat louse (Rhopalosiphum padi) are used with the preparation of the active compound are poured on, so that the active ingredient preparation in the Bodan penetrates without wetting the leaves of the oat plants. The active ingredient is absorbed from the soil by the oat plants and so arrives at the infected leaves.

After the specified times, the degree of destruction is determined in % . 100% means that all aphids have been killed, 0 % means that none of the aphids have been killed.

Active ingredients, active ingredient concentrations, evaluation times and The results are shown in Table 3 below:

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22Α0031

Table 3 (Rhopalosiphum test / systemic effect)

Active ingredient Active ingredient con
centering in # 0.1 Degree of destruction in %
after 4 days ^C 2 ^H S ° \ ^S
C J \ h
TJ CJ Λ * ΤΙ 2 ~ ~, ~ 2 5 0 C ₂ H ₅ O ' CH ₅ (known) 0.1
0.01 J Xh
PS-CH CO-N-CO-CH, 0.001 100
100 CH ₅ O ^ CH ₅ 0.1
0.01 60 C ₉ Hp-Ov 0
² 5 χ «
PS-CH -CO-N-CO-CH, 0.001 100
100 C ₂ H ₅ O ^ CH ₅ 0.1
0.01
0.001 100 CpHcOv S
^c 5 Xh
PS-CH
C ₂ H ₅ / ₂ _CO-N-CO-CH ₅
CH ₅ 0.01 100
100
30th ^ P Xh
PS-CH -CO-N-CO-CH 100 C ₂ H ₅ Q / · X
riTj>. ritj

0.1 100

PS-CH ₂ -CO-N-CO - / \ 0.01 100

CH,

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4 * 5

OO / π π ¹ ^ ^ i

Table 3 continued (Rhopalosiphum test / systemic effect)

Active ingredient active ingredient concentration degree of destruction in concentration in jo . 4 days

J ₂ H ₅ Ov S '/ GH, 0.1 100

PS-CH ₀ -CO-IT-CO-CH 0.0-1 100

C _O H _K / CH,

0.1 100

iS-CH ₀ -CO-NO O -jT \

/ ^ά

^ PS-CH ₂ -CO-N-CO- ^ Λ 0.01 100

C ₀ H / CH ^^ 0.001 40

^l 5 ^w "3

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Example D 22 A 003 1

Tetranychus test (resistant)

Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ethers

For the production of an appropriate preparation of the active substance 1 part by weight of active ingredient is mixed with the stated amount of solvent containing the stated amount of emulsifier contains, and dilute the concentrate with water to the desired concentration.

Bean plants (Phaseolus vulgaris), which are approximately 10 - 30 cm high, sprayed dripping wet. These bean plants are strong at all stages of development the common spider mite or bean spider mite (Tetranychus urticae).

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

Active ingredients, active ingredient concentrations, evaluation times and The results are shown in Table 4 below:

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'' IT

A: r.2.

*: --r.rcrrai ir. <

C, H _e C _x O

0.1

? 9

PS-CH ₅ -CO-K-CO-CH-

0.1

ρ ν ⁰ Z ^ν 2 "5 \ ί

--CH ₀ -CO-E-CO-CH, CH,

0.1 0.01

100 95

^ PS-CH ₂ -CO-B-GO-CH CH, ^

0.1

100

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'. α 9 8 0 9/1 2 2 3

Continuation of table 4 2 2 AOO

(TetranychuB test / reactive)

Active ingredient active ingredient killing degree in f . centering in $> after 2 days

H ₅ ^ S

PS-CH ₂ -CO-N-CO-CH 0.01 85

CH,

^C 2 «5 ° \ S

PS-CH ₂ -CO-N-CO- / 0.1 98

5 ^ -j,

PS-CH ₂ -CO-N-CO- ^ Λ 0.1 100

C ₂ H ₅ O _x S
PS-CH ₂ PS-CH ₂ -CO-N-CO-CH ₃ 0
0 ,1
, 01 100
90 C ₂ H ₅ O ' C ₂ H ₅ O ^ 1-C ₃ H ₇ C ₉ HcOv 0
² 5 \ m
PS-CH ₂ -CO-N-CO-CH ₃ 0 ,1 98 C ₂ H ₅ O 1-C ₃ H ₇ -CO-N-CO-CH ₃ 0
0 ,1
, 01 100
70 1-0, H ₇

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Production examples fc ^ 22A0031

CH, QS J \ // ■

■ P CH,

/ \ ³ CH, 0 S-CH ₀ -CNC-CH,

J * - It 11 >

O O

139.4 g (0.93 mol) of chlorine = acetic acid-N-acetyl- are added dropwise at room temperature to a solution of 168.0 g (0.93 mol) of the sodium salt of 0,0-dimethyldithiophosphoric acid in 600 ecm of acetonitrile N-methylaraid '. The reaction is slightly exothermic. The mixture is stirred overnight at 40 to 50 ^° C., the precipitated inorganic salts are filtered off with suction, the solvent is removed, the residue is taken up in dichloromethane, the solution is washed twice with water, the organic phase is dried over sodium sulfate, filtered and concentrated Piltrat entered and received the S- (N-acetyl-N-methyl-amidocarbonyl) -methyl-dithiophosphoric acid-0,0-dimethyl ester as a brown oil that solidified after a short time. The crystals have a melting point of 48 to 49 ° G · The yield is 210.0 g · (64.8 % of theory).

The following compounds can be obtained in an analogous manner will:

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constitution

Refractive index or melting point

S-CH ₀ -CNC-CH,

^ - Il Il

O O

n ² ° 1.5292

0 _o H _K 0 S

Y
\

CH, ⁵

C ₀ H / S-CH ₀ -CNC-CH, 5 2 ""

0 0

n ² ° 1.5447

CH ₅ 5-CH ₀ -CNC-CH,

^ Il Il S

O O

n ² S 1.4927

C ₂ H ₅ OS
P.

nn 0 0

n ² ° 1.5664

C ₀ HcO S

⁵ V

S-CH ₀ -CNC-CH-,

^ Il Il J

O O m.p. 40 to 41 C

η it

0 0

1.5822

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22 ^ 0031

constitution

Refractive index "or, melting point

C ₂ H ₅ O 0

P.
C ₉ H _C -O ^/ S

OH

η ti 0 0

20th

1.5328

O ₉ H ₁ -O 'S
2 5 \ //

C _o H _c -0 ^/ ^ S-CH ₀ -CNO-CH ^ 5 2 ""

0 0

20th

1.5182

OH OH, , 3/3

σ «η / ⁿ s-ch ₀ -cnc-oh

2 P 2 "" ν

OO ^X CH ₃

20th

D 1.5325

20th

'J 1.5198

Il H

0 0

S-CH ₀ -CNC-CH,

^ Il H ->

ο ο

20th

1.5332

CpH _K O
2 5

0 0

η ² ° 1.4889

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2 2 L 0 0 3 1

constitution

Refractive index or melting point

C _o H _K 0 Ο

C ₉ H ₁ -O ^{7 X} S-CH ₉ -CNC-CH

^ 5 ² M Il \

0 0 ^X CH

CH, / CH,

I JS J

20 D

1.4855

S-CH ₉ -CNC-CH, ^d n Ii J OO

J 1.5313

C ₂ H ₅ /

S-CH ₉ -CNC-CH,

Il

Il

20th

1.5725

Claims (6)

Patent claims 1) S- (ϊΤ-Acyl-ami do carbonyl) -methyl-mono- or -dithiophosphor- or phosphonic acid esters of the formula R-O X \ * _R it 'R ^{f /} ^ S-OH ₀ -GN-acyl ^ It in which R, R ¹ and R ″ stand for identical or different, straight-chain or branched alkyl radicals with 1 Ms 6 carbon atoms, R ¹ can also mean a straight-chain or branched alkoxy group with 1 to 6 carbon atoms and R ″ can mean phenyl, acyl stands for represents a lower alkylcarbonyl or phenylcarbonyl radical and X represents an oxygen or sulfur atom. 2) Process for the preparation of S- (H-acyl-amidocarbonyl) -methyl-mono- or -dithiophosphoric or -phosphonic acid = esters, characterized in that 0,0-dialkylmono- or -dithiophosphorus (phosphonic) acid salts of the formula R-O X with haloacetic acid-N-acyl-amides of the formula R "Hal-CH ₉ -CN-acyl C. Il Le A 14 563 - 27 - 409809/1223 in which formulas R, R ' _f R ", acyl and X have the meaning given in claim 1, Hal is a halogen, preferably bromine or chlorine atom, and M is an alkali metal, alkaline earth metal or optionally alkyl-substituted ammonium equivalent stands, implements. 3) insecticidal and acaricidal agents, characterized by a content of compounds according to claim 1. 4) A method for combating insects and mites, characterized in that compounds according to claim 1 are on allows the pests mentioned or their habitat to act. 5) Use of compounds according to claim 1 for combating insects and mites. 6) Process for the preparation of insecticides and acaricidal agents, characterized in that compounds according to Claim 1 mixes with extenders and / or surface-active agents. Le AU 563 - 28 - 409809/1223