DE1954894A1 - Alkyl-O-phenyl-thiono-thiolphosphonic acid esters, process for their preparation and their use as insecticides and acaricides - Google Patents

Description

FARBENFABRIKEN BAYER AG ^1954894

LEVE RKU S E N - Beyerwerk P «em department *

3 0. OKI.

Alkyl-O-phenyl-thiono-thiolphosphonic acid ester, Process for their preparation and their use as insecticides and acaricides'

The present invention relates to new alkyl-O-phenyl-thionothiolphosphonic acid esters of the general constitution (I)

L-R "(D

R ¹ O

which have insecticidal and acaricidal properties and a process for their preparation.

In the aforementioned formula (I), R stands for a lower alkyl radical, R ¹ means a phenyl, mono-, di- and trihalophenyl, lower alkylphenyl, lower alkyl mercaptophenyl, lower alkyl lower alkyl mercaptophenyl, lower alkoxyphenyl or lower alkyl halophenyl and R "means a lower alkyl mercapto or the cyano radical, while η is 1 or 2.

From the German patents 949.231 and 1.018.053 as well as the USA patent 3 156 718 are inter alia. already if necessary chlorinated S-benzyl esters of 0,0-dialkylthiolphosphoric acids known. According to the information in the publications mentioned above, these products are characterized by good quality insecticidal and acaricidal effectiveness with simultaneous low toxicity to warm-blooded animals; therefore they find

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as pesticides in crop protection and in the hygiene sector.

It has now been found that alkyl-O-phenyl-thiono-thiolphosphonic acid ester of the above constitution (I) can be obtained if one of the alkyl-O-phenyl-thiono-thiolphosphonic acids general formula (II)

ρ ^s

P-SH (II)

R'0 ^/

in the form of the corresponding alkali or ammonium salts or in the presence of acid binders with alkyl halides the general structure (III)

Hal- (CH ₂ ) _n -H "(III) converts.

In the latter formulas, the symbols have R; R ¹ , R "and η have the meaning given above, while Hai stands for a halogen atom.

As has also been found, the products of constitution (I) are distinguished by outstanding insecticidal and acaricidal properties Properties from; they have both a very good action against both biting and sucking insects and an excellent one Effectiveness against spider mites.

The course of the production process for the new substances according to the invention is explained in more detail using the following equation (IV) explained:

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Hal- (CH _P ) -R «^ Je-S- (CH ₂ ) -E"

(IV)

In the above equations, R, R ¹ , R ″, Hal and η have the meanings given above.

However, R preferably denotes an alkyl radical with 1 to 4 Carbon atoms »-like methyl, n- and isopropyl, n-, iso- and sec-butyl and especially ethyl.

R 'preferably represents phenyl, mono- and dichlorophenyl, methyl mercaptophenyl, Methyl-methyl-mercaptophenyl, methyl-chlorophenyl, ToIy1 or tert-butylphenyl.

R "preferably denotes an alkyl mercapto radical having 1 to 4 carbon atoms, e.g. the methyl, ethyl or isopropyl mercapto radical or the cyano group.

The alkyl-O-phenyl-thiono-thiolphosphonic acids of the formula (II) required as starting materials for the reaction are z. T. known from the literature. You can also technically in the form of their salts by customary methods, for example by Implementation of the corresponding alkyl-O-phenyl-thionophosphonic acid halides with alkali (preferably potassium or sodium) hydrogen sulfides. The implementation takes place preferably in alcoholic solution at room or slightly elevated temperature.

The following alkyl-O-phenyl-thionothiolphosphonic acids are suitable starting materials named as an example:

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0-ethyl-O-phenyl-,

-0- (2-chlorophenyl) -, -Ο- (3-chlorophenyl) -, -Ο- (4-chlorophenyl) -, _Ο- (2,4- and 2,5-dichlorophenyl) -, -0- (2 ~ chloro-4-methylphenyl) -, _0- (3-chloro-4-aethylphenyl) -, -0- (3-methyl-4-chlorophenyl) -, -0- (2-methyl-4-chlorophenyl) -, -0- (4-tolyl) -,

-0- (4-tert-butylphenyl) -, _0- (4-methylmercaptophenyl) - and _0-3-methyl-4-methylmercapto-phenyl) -thiono-

thiolphosphonic acid

and the corresponding O-methyl, ~ n-propyl and isopropyl compounds. The alkyl halides of structure (III) which are used as the second reaction component are also from the literature known.

As examples of the starting materials (III) are mentioned in detail:

ß-ithylmercapto-ethyl-, ß-methylmercapto-ethyl-, Methylmercapto-methyl-, methylmercapto-ethyl and Cyanomethyl chloride (monochloroacetonitrile).

The reaction is preferred in the presence of solution or Diluents carried out. Practically all organic solvents or mixtures thereof are suitable for this. These include aliphatic or aromatic, possibly chlorinated hydrocarbons, such as gasoline, methylene chloride, Benzene, toluene, chlorobenzene, xylene; Ether, e.g. B. diethyl or Di-n-butyl ether, dioxane or tetrahydrofuran, as well as low

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boiling aliphatic alcohols, ketones and especially nitriles, for example methanol, ethanol, isopropanol, butanol, acetone, methylethyl-, methylisopropyl-, methylisobutyl ketone, Aceto- and propionitrile.

The reaction can be carried out within a relatively wide temperature range. Generally, is preferably carried out between 10 and 100 ° (or the boiling point of the mixture) at 20 to 80 ⁰ C.

As can be seen from the above formula scheme (IV), per mole Alkyl-O-phenyl-thiono-thiolphosphonic acid in each case 1 mol of acid binder and 1 mole of alkyl halide is required. It has proven to be advantageous to add the solution or suspension of the relevant alkyl-O-phenyl-thiono-thiolphosphonic acid Salt in one of the above-mentioned solvents, preferably acetonitrile, add the undiluted alkyl halide while stirring and the reaction mixture then for a longer time to complete the reaction (1 to 3 hours) post-heating to the temperatures given above. You get in this procedure, the products with excellent yields and excellent purity.

The batch is worked up in the customary manner, i. H. by cooling and taking it up in a suitable one solvent, preferably a hydrocarbon, e.g. B. benzene, separation of the phases, washing and drying of the organic layer, evaporation of the solvent and optionally fractional distillation of the residue.

The alkyl-O-phenyl-thiono-thiolphosphonic acid esters according to the invention usually occur in the form of colorless to slightly yellow colored water-insoluble oils, which can also be found under strong Do not allow to distill under reduced pressure without decomposition. You can, however, by so-called "incipient distillation", i.e. H.

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Short-term heating in a vacuum to moderately elevated temperatures, freed from the last volatile components and on them Way to be cleaned.

As already mentioned above, the inventive Products are characterized by an excellent insecticidal and acaricidal effectiveness. They have only a low phytotoxicity. The pesticidal effect sets in quickly and lasts for a long time. Based on these properties, the new ones find Alkyl-O-phenyl-thiono-thiolphosphonic acid esters in crop protection for combating harmful sucking and biting insects as well as mites.

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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 lice (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 scale and mealybugs (Coccina), e.g. the Ivy shield (Aspidiotus hederae) and cup scale (lecanium hesperidum) and the mealybug (Pseudococcus maritimus); Bladder feet (Thysanoptera) such as Hercinothrips fermoralis and bedbugs, for example beet (Piesma quadrata), cotton (Dysdercus intermedius), bed (Cimex lectularius), predatory (Rhodnius prolixus) and Chagaswahze (Triatoma infestans), furthermore cicadas, like Euscelis bilobatus and Nephotettix bipunctatus.

: The most biting insects are caterpillars (lepidoptera) such as the cabbage moth (Plutella maculipennis), the gypsy moth (Lymantria dispar), gold juicer (Euproctis ehrysorrlioea) and ring moth (Malacosoma neustria), furthermore the colli (Mamestra brassicae) and the seed owl (Agrotis segetum), the large cabbage white butterfly (Pieris brassicae), small cheetahs (Cheimatobia bruisata), oak moth (Tortrix viridana), the army (Laphygma frugiperda) imd Egyptian Cotton worm (Prodenia litura), also the web (Hyponomeuta padella), flour (Ephestia kühniella) and large wax moth (Galleria mellonella),

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The biting insects also include beetles (Coleoptera) e.g. grain (Sitophilus grararius = Calandra granaria), Potato (Leptinotarsa decemlineata), dock (Gastrophysa viridula), horseradish leaf (Phaedon cochleariae), rapeseed (• Meligethes aeneus), raspberry (Byturus tomentosus), table beans (Bruchidius = Acanthoscelides obtectus), bacon (Dermestes frischi), khapra (Trogoderma granarium), red-brown rice flour (Tribolium castaneum), corn (Galandra or Sitophilus zeamais), bread (Stegobium paniceum), common flour (Tenebrio molitor) and grain flat beetles (Oryzaephilus surinamensis), but also species living in the ground, e.g. wireworms (Agriotes spec.) and White grubs (Melolontha melolontha); Cockroaches like the German (Blatella germanica), American (Periplaneta americana), Madeira (Leacophaea or Rhyparobia madeirae), oriental (Blatta orientalis), giant (Blaberus giganteus) and black Giant cockroach (Blaberus fuscus) and Henschoutedenia flexivitta; also Orthoptera e.g. the cricket (Acheta 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), Parlor (Musca domestica), small parlor (Pannia canicularis), Glossy fly (Phormia aegina) and blowfly (Calliphora erythrocephala) as well as the calf stick (Stomoxys calcitrans); also mosquitoes, e.g. mosquitoes such as the yellow fever (Aedes aegypti), house mosquito (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 Fruit tree spider mite (Paratetranychus pilosus = Panonychus ulmi), Gall mites, e.g. the Johari blackberry gall mite (Eriophyes ribis) and tarsonemids, for example the shoot tip mite (Hemitarsonemus latus) and oyelamen mite (Tarsonemus pallidus); finally ticks like the leather tick (Ornithodorus moubata).

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Depending on their intended use, the new active ingredients can be added to the Conventional formulations are converted, such as solutions, emulsions, suspensions, powders, pastes and granules. These will produced in a known manner, e.g. by mixing the active ingredients with extenders, i.e. liquid solvents and / or carriers, optionally with the use of surface-active substances Agents that are emulsifying and / or dispersing agents, e.g. in the case of using water as an extender organic solvents can optionally be used as auxiliary solvents. As a liquid solvent are essentially possible: aromatics (e.g. xylene, Benzene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), strongly polar solvents such as dimethylformamide and dimethyl sulfoxide as well as water; as solid carriers: natural Ground rock (e.g. kaolins, clays, talc, chalk) and synthetic ground rock (e.g. highly dispersed silica, Silicates); as emulsifiers: non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g., alkyl aryl polyglycol ethers, alkyl sulfonates, and aryl sulfonates; as a dispersant: e.g. lignin, Sulphite liquors and methyl cellulose.

The active compounds according to the invention can be present in the formulations as a mixture with other known active compounds.

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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 #.

Thus, the products can also be used successfully ultra-low-volume process (ULV) in which it is possible to apply formulations i or up to 95 ° even the $ 100 pure active compound alone "

The active ingredient concentrations can be varied over a wide range. In general, from concentrations of 0.00001 i> to 20 #, preferably from 0.01 i "to $ 5.

The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use Solutions, emulsifiable concentrates, emulsions, suspensions, wettable powders, pastes, soluble powders, dusts and Granules. It is used in the usual way, for. B. by pouring, spraying, atomizing, gasifying, Smoking, scattering, dusting, etc.

Surprisingly, the products according to the invention stand out in comparison to those previously known from the literature Active ingredients of an analogous constitution and the same direction of action through a significantly better effectiveness; she thus represent a real enrichment of the technology. This unexpected superiority as well as the excellent effect of the new compounds is based on the following test results emerged:

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Example A.
Plutella test

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 level 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 in $ certainly. 100 ^ means that all caterpillars have been killed while $ 0 indicates no caterpillars were killed.

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

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Table 1

(Plutella test)

Active ingredient
(Constitution)

Drug concentration degree of killing in entered ion in yes after 3 days

(CH ₅ O) ₂ PS-CH ₂ -CH ₂ -SC ₂ H ₅ 0.1
0.01

100 0

(known comparator preparation)

Cl

-CH ₂ -S '

Cl

V-SCH,

C ₂ H ₅ S-CH ₂ -S

0.1 100 0.01 100 0.001 55 0.1 100 0.01 100 0.001 40 0.1 100 0.01 60

CH,

C ₂ H ₅ S-CH ₂ -S '

^X PO ^ V-SCH

Il

CIJ σ ητι ητι ο ' pH fQ "" VjHp "" O up "~ ΰ

P-O- / V-SCH

0.1 3 0.01 0.1 3 0.01

100 100

100 70

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Active ingredient
(Constitution)

$ 94

Table 1 (continued) (Plutella test)

Active ingredient concentration in i »

Degree of destruction in $> after 3 days

Cl

0.1 0.01 100 100

0.1

O _f O1

0.1 0.01 100 70

100 100

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Example B.

Rhopalosiphum test (systemic effect)

solvent: 3 parts by weight acetone emulsifier: ΐ parts by weight alkylaryl polyglycol ether

To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amount solvent that contains the specified amount of emulsifier, and dilute the concentrate with water to the desired level 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 compound preparation penetrates the soil without wetting the leaves of the oat plants. D3r The active ingredient is absorbed from the soil by the oat plants and thus reaches the infected leaves.

After the specified times, the degree of destruction is determined in % . 100 ^ means that all aphids have been killed, 0 56 means that none of the aphids have been killed.

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

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Table 2

(Rhopalosiphum test / systemic)

Active ingredient (constitution)

Active ingredient concentration degree of destruction in tration in yes after 4 days

Cl

(CELO) ₉ PO- /

0.1

(known comparator preparation)

C _n H. ft

Cl

^s P-0

C pH j-o -CHp-S

0.1
0.01

100 30

CpHp-S-CHp-CHp-S

Cl

0.1
0.01

100 50

-CHp-S

W SCH,

0.1

100

CHm p-CHp-S CH 3 VJl 0 ,1 100 C ₂ H ₅ "P C \
S-CH ₂ -S ' 525 NS 0 , 01 98 S. 3 3 0 ,1 100 Λ π η ΓΙΤ1
c- D NS 16 _ 0 , 01 60 Le A 12 _

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19548S4

Table 2 (port setting) (Rhopalosiphum test / systemic)

Active ingredient
(Constitution) Active ingredient concentration in i>

Degree of destruction in # after Days

Cl

^G 2 ^H 5 \ _p _

CN-CH ₂ -S

0.1
0.01

100 100

CN-CH ₂ -S

CH,

0.1

0.1
0.01

100

100 100

° 2 ^Η 5 S-CH ₂ -CH ₂ -S '

0.1

100

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Examples
Tetranychus test

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

For the production of an appropriate active ingredient preparation 1 part by weight of active ingredient is mixed with the stated amount of solvent which contains the stated amount of emulsifier, 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 attacked by the common spider mite (Tetranychus urticae).

After the times indicated, the effectiveness of the active ingredient preparation 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, ingredient concentrations, evaluation times and results are shown in Table 3 below:

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Table 3

(Tetranychus test)

Active ingredient (constitution) Active ingredient concentration degree of destruction in step ion in yes after 48 hours

(CH ₅ O) ₂ ^ -O

Eq

(known comparative preparation) 0.1

Cl

0.1

100

Cl

C ₉ Hp-S-CH ₀ -CH ₀ -S

0.1
0.01

100 40

0.1

80

C ₂ H ₅ S-CH ₂ -S

CH-t

⁵ VSCH 0.1

100

CH

C ₂ H ₅ S-CH ₂ -CH ₂ -S Le A 12525

SCH, 0.1

-19-

95

109819/2220

Table 5 (Porting) Tetranychus test

Active ingredient (constitution) Active ingredient concentration in #

Degree of destruction in % after hours

Cl

CN-CH ₂ -

0.1

98

CH

CN-CH ₂ -S 0.1

98

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example 1

CoHp-
- Κ /

C ₂ H ₅ S-CH ₂ -S 0 - // 0.25 molar approach;

73 g of ethyl-0- (3-chlorophenyl) -thionothiolphosphonic acid potassium (produced by reacting ethyl-O- (3-chlorophenyl) -thionophosphonic acid chloride with the equivalent amount of potassium hydrogen sulfide) are suspended in 250 ecm of acetonitrile. At 2O ⁰ C are added dropwise to this suspension with stirring, 29 g Äthylmercapto methyl chloride. The temperature rises to 40 ° C. during this process. To complete the reaction, the mixture was stirred for one hour at 55 - 6O ⁰ C to, then diluted the reaction mixture with 300 cc of benzene and the batch is poured into 200 cc of ice water. The benzene solution is shaken vigorously and then dried over sodium sulfate. After the solvent has been distilled off, 69 g (84 $ of theory) of the ithyl-O- (3-chlorophenyl) -S- (ethylmercaptomethyl) -thiono-thiolphosphonic acid ester remain as a pale yellow, water-insoluble oil with the

25th
Refractive index η £ = 1.5932.

P S Cl

Ber. for a molecular weight of 326.5: 9.5 ^, 29.5 #, 10.8 Found: $ 10.0, 30.0 ^, 10.6

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Example 2

C ₂ H ₅ S-CH ₂ -CH ₂ -S 0.25 molar approach;

To a Anschlämnrung of 73 g ethyl-0- (3-chlorophenyl) -thionothiolphosphonsaurem potassium in 250 cc of acetonitrile are added at 2O ⁰ C with stirring, 32 g of .beta.-Äthylmercapto-ethyl chloride. The temperature of the mixture rises to. 35 ⁰ C. The reaction mixture is then heated to 60 ^° C. for a further hour and then worked up as in Example 1. There are 80 g (94 1 ° of theory) of the ethyl-0- (3-chlorophenyl) -S- (ß-ethylmercapto-ethyl) -thiono-thiolphosphonic acid ester in the form of a pale yellow, water-insoluble oil with the Bre-

26th
chung index η ^ = 1.5867 obtained.

Ber. for a molecular weight of 340.5: Gef.:

PS Cl 9.1 <fo, 28.2 ^, 10.4 ^; 9.1 / o, 28.4 / o, 10.1 <fo.

Example 3

^C 2 ^H 5j? P.

C ₂ H ₅ S-CH ₂ -S

\-NS

0.25 molar approach:

76 g of ethyl-0- (4-methylmercaptophenyl) -thionothiolphosphonic acid are slurried Potassium (produced by reacting ethyl-Ö- (4-methylmercaptophenyl) -thionophosphonic acid chloride

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the calculated amount of potassium hydrogen chloride) in 250 cc of acetonitrile and this suspension is added subsequently "at 20 ⁰ C under stirring with 28 g Äthylmercaptomethylehlorid. The temperature of the mixture rises to 4-0 C. To complete the reaction the reaction mixture is still a hour at 55 ⁰ C is stirred and finally worked up as in example. 1, giving 58 g (69 fi of theory) of ethyl-0- (4-methylmercaptophenyl) -S- (äthylmercaptomethyl) -thiono-thiolphosphonsäureesters as a yellow

22 water-insoluble 01 with the refractive index η - ^ = 1.6157.

for • a Molecular weight from 338: 9 P. S. Ber. 9 , 17 io _p , 8 fa Found .00 io _s , 4 ^. ► 37 »37

Example 4

0.35 molar approach;

NS

115 g of ethyl-0- (3-methyl-4-methylmercaptophenyl) -thiono-thiolphosphonic acid potassium are suspended in 400 ecm of acetonitrile. To this suspension is added 39 g Äthylmercaptomethylehlorid with stirring at 2O ⁰ C. The temperature of the mixture rises to 40 ^° C. In order to complete the reaction, the reaction mixture is heated to 60 ° C. for a further 2 hours with further stirring and then worked up as in Example 1. 110 g (89 # of theory) of the ethyl-0- (3-methyl-4-methylmercaptophenyli-S-iäthylmercaptomethyli-thiono-thiolphosphonic acid ester as a pale yellow, water-insoluble oil with the

or
Refractive index η -β = 1.5829.

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PS

Ber. for a molecular weight of 352: 8.8 96, 36.4 Found: 9.0 #, 36.2

example

^C 2 ^H

/ N

C ₂ H ₅ ACH ₂ -CH ₂ -S

0.35 molar Anaatz:

Dissolve 115 g ethyl-0- (3-methyl-4-methylmercaptophenyl) - thiono-thiolphosphonsaures potassium in 400 cc of acetone and added to this solution with stirring "at 20 ⁰ C. 44 g of beta-Äthylmercaptoäthylchlorid The temperature of the mixture increases. Registered to 45 C. to complete the reaction the reaction mixture is heated with continued stirring for another 2 hours at 6O ⁰ C. it is then worked up as in example 1. this gives 110 g (86 $ of theory) of ethyl-0- ( 3-methyl-4-methylmercaptophenyl) -S- (ß-ethylmercaptoethyl) -thiono-thiolphosphonic acid ester in the form of a yellow, water-insoluble oil with the refractive index n ² -> = 1.5772.

for • a Molecular weight from 366: 8th P. 35 S. Ber. 8th , 5 34 , 0 Gef, ,1 ,8th

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4ε

Example 6:

CN-CH ₂ -S

0.3 molar approach;

87.5 g of ethyl-O- (3 ~ chlorophenyl) thiono-thiolphosphonic acid potassium are dissolved in 300 ecm of acetonitrile. 25 g of chloro-eetonitrile are added to this solution at 20 ^{° C. with stirring.} The temperature of the mixture rises to approx. 35 ° C. The mixture is stirred for another hour at 65 to 70 ⁰ C. and then pouring the reaction mixture into 300 cc of ice water. The precipitated oil is taken up in 300 ecm benzene, the benzene solution is washed with water and then dried over sodium sulfate. After distilling off the solvent, 78 g is obtained (87 $> of theory) of Ä'thyl-O- (3-ehlorphenyl) -S-cyanomethyl-thionothiolphOBphonsäureesters as a pale yellow water-insoluble oil of refractive index _oc

- ^{£ b} = 1.5906.

Calculated for a molecular weight of 291:

PS N Cl

10.6 i> 21.9 $ 4.8 £ 12.2 %

10.6 % $ 21.9 $ 4.9 > 12.1 %

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Example 7

C ₂ H ₅ S-CH ₂ -CH ₂ -S

0.25 molar approach:

To a solution of 76 g ethyl-0- (4-methylmereapto-phenyl) - thiono-thiolphophonsaurem potassium in 250 cc of acetonitrile are added at 20 ⁰ C with stirring, 32 g of .beta.-ithylmercapto-ethyl chloride, the mixture keeps Not one hour with stirring then at 65 ⁰ C and worked up as in Seispiel. 6 There are thus 36 g (41 i> of theory) of ethyl-0- (4-methylmercapto-phenyl) -S- (ß-äthylmercapt o-ethyl ^ thionothiolphosphonsäureesters a yellow form in weak, water-insoluble oil of refractive index

n25 = 1.6082 obtained. D.

Calculated for a molecular weight of 352:

8.8 % 36.4 #

9.0 # 36.1 pounds

Example 8

0 ft 25 molar approach;

Han dissolves 76 g of ethyl-0- (4-methylmercapto-phenyl) thionothiolphosphonic acid Potassium in 250 ecm of acetonitrile, add 20 g of chloroacetonitrile to this solution while stirring at 25 ° C,

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holds the mixture for another hour at 60 to 65 ⁰ C and then works it up as in Example 6. There are thus 61 g (80.5 % of theory) of ethyl-O- (4-methylmercaptophenyl) -S-cyanomethyl-thionothiolphosphonic acid ester as a colorless, water-insoluble oil with the refractive index _n 22 _ ^ ₆₁₇₅

obtain.

Calculated for a molecular weight of 303:

P S N

£ 10.2 31.7% 4.6 #. Found: $ 10.4 31.1 * 4.6 #

Example 9

CN-CH ₂ -S / - V 77Λ- _SCH _

Λ = / ³

0.35 molar approach;

115 g of ethyl-O- (3-methyl-4-methylmercapto-phenyl) -thionothiolphosphonic acid potassium are dissolved in 400 ecm of acetonitrile. 28 g of chloroacetonitrile are added to this solution at 25 ^° C. with stirring, the mixture is stirred for a further 1 to 11/2 hours at the specified temperature and then worked up as in Example 6. There are so 103 g (93 %> of theory) of the ethyl-0- (3-methyl-4-methylmercaptophenyl -) - S-cyanomethylthionothiolphosphonic acid ester in the form of a pale yellow, water-insoluble oil with the refractive index 25 _Λ

obtain.

Calculated for a molecular weight of 317:

P SN

9.8 £ 30.2 IL 4.4 Jt '. '

Found: 10.1 $ 30.0 # 4.6 pounds

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109819/2220

Claims (6)

Claims ίλ \ Alkyl-0-phenyl-thiono-thiolphosphonic acid ester of the formula R ¹ where R is a lower alkyl radical, R ^{1 is} a phenyl, mono-, di- and trihalophenyl, lower alkylphenyl, lower alkyl mercaptophenyl, lower alkyl-lower alkyl mercaptophenyl, lower alkoxyphenyl or lower alkyl halophenyl and R "is a lower alkyl mercapto or the cyano radical, while η is 1 or 2. 2) Process for the preparation of alkyl-O-phenyl-thionothiolphosphonic acid esters, characterized in that one alkyl-O-phenyl-thiono-thiolphosphonic acids the formula P-SH R ¹ O in the form of the corresponding alkali or ammonium salts or in the presence of acid binders with alkyl halides the formula HaI- (CH ₂ J _n -R " implements, where in the aforementioned formulas R, R ¹ , R "and η have the meaning given in claim 1, while Hal stands for a halogen atom. Le ^- A 12 525 - 28 - 109819/2220 3) insecticidal and acaricidal agents, characterized by a content of alkyl-O-phenyl-thiono-thiolphosphonic acid esters according to claim 1. 4) A method for combating insects and mites, characterized in that one alkyl-O-phenyl-thionothiolphosphonic acid ester according to claim 1 can act on insects and / or mites or their habitat. 5) Process for the preparation of insecticidal and acaricidal products Agents, characterized in that one alkyl-O-phenyl-thiono-thiolphosphonic acid ester according to claim 1 mixed with extenders and / or surface-active agents. 6) Use of alkyl-O-phenyl-thiono-thiolphosphonic acid esters according to claim 1 for combating insects and mites. Le A 12 525 - 29 - 109819/2220