DE2415979A1 - PHOSPHORIC ACID ESTER - Google Patents

Description

wherein R _{1 represents} alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkoxyalkyl with 3 to 6 carbon atoms, alkoxyalkylthio with 3 to 6 carbon atoms, alkylthio with 1 to 4 carbon atoms, phenyl or NR ₅ R ₆ , R_ alkyl with 1 to 4 carbon atoms, R _{3 is} hydrogen, alkyl with 1 to 4 carbon atoms, mono-, di- or trihaloalkyl with 1 to 4 carbon atoms or phenyl, R _{4 is} alkyl with 1 to 4 carbon atoms

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or R ₃ and R ₄ together with the carbon atom denote an alicyclic ring with 3 to 8 carbon atoms, Rc and R each denote hydrogen or alkyl with 1 to 4 carbon atoms, A denotes sulfur or oxygen, η denotes an integer of 0 to 2, X and Y each represent hydrogen, alkyl with 1 to 4 carbon atoms (straight-chain or branched). or halogen and Z represents hydrogen, alkyl with 1 to 4 carbon atoms (straight-chain or branched), cyano, halogen, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, trichloromethyl, trifluoromethyl, carblower alkoxy with 1 to 4 carbon atoms, nitro or sulfamoyl.

The new phosphoric acid esters are prepared by adding an alpha-substituted thiol of the formula II and a correspondingly substituted phosphoric acid of the formula III with formaldehyde or a formaldehyde source (CII ₂ O) with possibly subsequent oxidation (Ox), if η stands for 1 or 2 is, using m-chloroperbenzoic acid or a corresponding equivalent thereof. These reactions go as follows:

? 3

HSC

R,

(ID

wherein n, R _{1 have a} direction.

Il

P-SH (III)

DCH ₂ O

R ₂ O

(D

-S (0) -C- η,

R., A, X, Y and Z above meaning

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2A15979

The condensation reaction is preferably carried out in a single stage by reacting equimolar amounts of the thiol and the phosphoric acid at temperatures between about 0 C and TOO ⁰ C with a formaldehyde source such as methanol-free formalin. 1 mol of formaldehyde goes together with the thiol and the phosphoric acid.

The method can be modified several times, and such modifications also fall within the scope of protection of the invention. The reactions between the formaldehyde and the thiol or the phosphoric acid can be carried out in sequence. Alternatively, you can first produce a stable methylene derivative of thiol or phosphoric acid and then convert this later. For example, an S-chloromethyl-substituted phosphoric acid ester of the formula IV can be used to prepare the new compounds in a base-catalyzed reaction with the alpha-substituted arylmethylthiol in the form of the potassium salt in formula V. This is preferably done using an alkali alkoxide having 1 to 8 carbon atoms as the base in a saturated alcohol having 1 to 8 carbon atoms as the solvent. Alternatively, you can also use sodium or potassium hydroxide as the base and work in a solvent such as dimethyl sulfoxide or dimethylformamide. Regardless of the particular solvent system used, the reaction can over a wide temperature range between the freezing point and the boiling point of the solvent used to carry out, and normally between 0 ⁰ C and 100 ° C.

R ^R -

.PS-CH ₀ Cl HS-C- _λ ,

R ₇ O \ rzj ^ z

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wherein R ₁ , R_, R,, R., X, Y, Z and A have the above meanings. If you want to use the phosphoric acid in a base-catalyzed reaction, then you would use a stable methylene derivative of the thiol, such as the chloromethyl thioether of the following formula VI. The derivative would preferably be reacted with the alkali or aresalt of phosphoric acid of the formula VII:

X R

Cl-CILS-C- <

^R 4 " ² "

(VI) (VII),

wherein M stands for an alkali or ammonium ion, and R ₁ , R_, R_, R-, X, Y, Z or A have the above meaning.

This reaction is preferably carried out in a solvent such as a ketone, a chlorinated hydrocarbon, a polyether or an aromatic hydrocarbon. Typical solvents are acetone, ethyl methyl ketone, methylene chloride, Dichloroethane, xylene, toluene, benzene and the like. Mixtures such as water and an insoluble organic solvent can also be used. The implementation is normally used at temperatures between 0 and 100 ° C or between the freezing point and boiling point of the solvent carried out.

The methylene derivatives can be prepared from the phosphoric acid or the thiol by a number of processes which are readily familiar to those skilled in the art of organic chemistry.

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To convert the S- (alpha-substituted arylmethylthio) methylphosphoric acid esters of the formula I, in which η is 0, into the corresponding sulfoxide, these esters can be reacted with an equivalent amount of m-chloroperbenzoic acid in the presence of a solvent such as methylene chloride. The reactants are preferably mixed at temperatures between about 0 and 10 ° C., after which the mixture is heated ^{to temperatures between 20 and 40 ° C. until the end of the reaction.}

A conversion of an S- (alpha-substituted arylmethylthio) methylphosphoric acid ester of the formula I, in which η is 0, can easily be added to the corresponding sulfon Achieve by mixing this ester with either potassium permanganate in aqueous tert-butyl alcohol using magnesium sulfate as a buffer or with two equivalents of m-chloroperbenzoic acid in a solvent such as methylene chloride.

The formation of the desired sulfoxides and sulfones of the corresponding Phosphoric acid ester can also be achieved by using other known oxidizing agents, such as sodium metaperiodate, Hydrogen peroxide, monoperoxyphthalic acid, other peracids and chromic acid.

The compounds of the invention are highly effective insecticides and acaricides. As mentioned above, the The invention further directed to the use of the phosphoric acid esters of the formula I for controlling insects and Acaricids. These esters can be used alone or in combination with each other. They are preferably in Combination with customary pesticidal adjuvants including solid and liquid carriers or diluents as well as formulation auxiliaries, preferably in the form of granular formulations, emulsifiable concentrates, Powders, powder concentrates and the like.

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The invention is accordingly also directed to a method for controlling insects and acarids, which is characterized in that an effective amount of a phosphoric acid ester of the formula I to be controlled Insects or acarids. The application can be made directly to these insects or acarids or their habitat. It is used to protect living plants, including agricultural fruits and ornaments on their foliage or on the ground where they grow. To protect living animals, especially to control fleas and ticks, an effective amount of the phosphoric acid esters is applied topically to the host animal to be protected.

The active ingredients can initially be in the form of a concentrated preparation, which consists of a substantial amount of the active ingredient and a smaller amount consist of a solid or liquid adjuvant as a formulation aid or conditioning agent is used, whereby the concentrates with a suitable solid or Let the liquid carrier mix further.

Suitable liquid adjuvants in which the · according to the invention Active ingredients to dissolve, suspend or distribute are, for example, xylene, benzene and lower aliphatic Alcohols, fuel oil and the like, with or without a dispersing, a surface-active and / or an emulsifying agent. It is used that contains about 5 to 95 percent by weight of the active phosphoric acid ester Concentrate usually diluted with water or a relatively "cheap organic diluent, such as odorless kerosene, and in the form of a dilute spray with about 0.5 ppm to about 5000 ppm of the active compound applied.

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Suitable solid adjuvants are, for example, atapulgite, kaolin, talc, diatomaceous earth, silicon dioxide, ground Corn on the cob, coconut shells and the like, in granular or finely ground form. The solid leaves with the solid adjuvants easily to powders, powder concentrates, wettable powders, granules and the like formulate.

Dustable powders are generally prepared by mixing about 1 to 10 percent by weight of the active ingredient with the finely divided solid inert diluent mixed or ground. These formulations can then be used with suitable dusting devices on the foliage of agricultural crops or fields, meadows, forests and raise the like that you want to protect against insect attack. In practice it is generally one An amount of about 0.141 to 9 kg per hectare (0.125-8 pounds per acre) of active ingredient is sufficient.

Dust concentrates are usually made in the same way as dusts themselves. In general, however, about 25 to 75 percent by weight of active ingredient and about 75 to 25 percent by weight of diluent are used.

Wettable powders are produced in the same way as the dust concentrates. However, such formulations contain ' usually also about 1 to 5 percent by weight of an emulsifier or surfactant and about 1 to 5 percent by weight of a dispersant. About surface-active agents, emulsifiers and dispersants, that can be used for such formulations include polyethylene glycols, methoxypolyethylene glycols, Sodium lignosulfonate, calcium dodecylbenzenesulfonate, polyoxyethylated vegetable oils, alkylphenoxypolyoxyethylene ethanol and the same. In practice, the wettable powders are usually dispersed in water and as

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diluted spray applied to the vegetation, the soil or the habitat, v / o one the insects and / or acarids respectively want to control.

A control of insects and acaricide as well as a plant protection on fields, wooded areas, plantings and the like can normally be with the compounds according to the invention when using insecticid and acaricid, effective amounts of about 0.28 to. about 9 kg / ha (0.25 - 8 pounds per acre) brings up.

The compounds of the invention have the advantage that they have an extended or improved residual insecticide and acaricidal effect and consequently a better control of insects and acarids over a longer period of time as the compounds closest to them '. Besides the fact that the new compounds are more pesticidal, they are less toxic to mammals. The increased margin of safety in relation to manufacture, handling and storage for the compounds according to the invention is particularly noteworthy, since these can therefore also be applied by spraying can, which does not apply to the closest known known compounds or is far more dangerous.

The invention is illustrated in more detail by means of the following examples. Information on parts and percentages relate to weight, unless otherwise stated.

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- Q _

example 1

Production of the intermediate product alpha, alpha-Dimethy1-alpha-

toluene thiol

227 ml of 48 percent hydrobromic acid (2.00 mol), cooled to 0 to 5 ^° C., are mixed with 76.1 g (1.0 mol) of thiourea. A considerable amount of thiourea goes into solution. The resulting paste is carefully mixed with 136 g (ί, ΟΟ mol) of alpha, alpha-dimethy1-benzyl alcohol while stirring for two hours. The temperature of the reaction mixture is kept at 25 to 30 ° C. with an ice bath during the addition. After adding about 1/3 of the alcohol, the mixture becomes extremely thick. At this point, another 114 ml of concentrated acid are added (total amount = 341 ml, 3.00 moles) and the alcohol addition is stopped. 400 g of crushed ice are added to the viscous mixture, which leads to a strongly endothermic reaction, and the mixture is stirred until the ice has melted. The mixture is filtered while still at a temperature of about 0 ⁰ G over a sintered glass funnel, and the filter cake is washed with ether and picks it up overnight in vacuo over potassium hydroxide. The solid of the isothiouronium salt obtained in this way weighs 280 g, is apparently still somewhat moist and melts in the region
is practically quantitative.

moist and melts in the range of 85 to 94 C. The yield

To prepare a corresponding solution, 60 g (1.5 mol) of sodium hydroxide are dissolved in 1.2 liters of water, whereby a solution with a temperature of 40 ° C. is obtained. The isothiouronium salt prepared above is added immediately - without causing an exothermic reaction - and the mixture is stirred overnight. The mixture thus obtained 200 ml of ether are added with rapid stirring, whereupon it is concentrated by slowly adding 50 ml Hydrochloric acid makes it strongly acidic while cooling. The organic

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Layer is separated and the aqueous layer is extracted twice with 200 ml of ether each time. The three organic layers were combined, washed twice with 100 ml of saturated sodium chloride solution each time and dried over magnesium sulfate. After evaporation of the 'ether from the dried solution at 30.degree. C./12 mm Hg, 128 g (84.3% based on alcohol) of a clear, mobile, pale yellow liquid are obtained. The distillation by a simple head results in boiling to 64 ⁰ C, the pure product, namely, alpha, alpha-dimethyl-alpha-toluenethiol, the mm Hg at 2.3 at the 63rd

Example 2

Production of S- (alpha, alpha-dimethylbenzylthio) methyΙ Ο , O-diethylphosphorodithionate

15.2 g (0.100 mol) of alpha, alpha-dimethyl-alpha-toluene thiol in 50 ml of tert-butyl alcohol are mixed with 11.2 g (0.100 mol) of potassium tert-butoxide. The resulting solution is cooled to room temperature and slowly added to a solution of 23.5 g (0.100 mol) of S-chloromethy1-0, O-diethylphosphorodithionate in 50 ml of tert-butyl alcohol. A slow, mild exothermic reaction occurs. The temperature of the reaction mixture is kept at 25 to 30 ^° C. with a water bath. The reaction mixture is stirred for 20 hours at room temperature, after which the solvent is stripped off at 35 ° C. and 12 mm Hg. The residue is distributed between 150 ml of methylene chloride and 75 ml of 1.7 percent potassium hydroxide solution. The organic phase is mixed with a solution of 25 ml of 5 percent potassium hydroxide and 25 ml of saturated sodium chloride, then with three times 25 ml of saturated sodium chloride, with twice 25 ml of 5 percent hydrochloric acid, with three times 25 ml of saturated sodium chloride, with 25 ml of 5 percent Potassium hydroxide and finally with

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washed three times 25 ml of saturated sodium chloride. The organic phase is dried with magnesium sulfate followed, and finally 30.9 g (88.3%) of the solvent was removed at 60 ⁰ C / 0.5 mm Hg to a moderately viscous clear straw-colored liquid. This material is dissolved in carbon tetrachloride and the solution obtained is placed in a column which has an internal diameter of 5.71 cm and a length of 51 cm and is filled with magnesium silicate with a grain size of 0.250 to 0.150 mm clear mesh size. The column is eluted with 1.5 liters of carbon tetrachloride, then in sequence with 1 liter of 5, 10, 15, 20 and 25 percent by volume of methylene chloride in carbon tetrachloride and finally with 1 liter of methylene chloride. The residue obtained after removing the solvents from the last three fractions is a clear, pale straw-colored, moderately viscous liquid with a refractive index η ' = 1.5706, a theoretical proton magnetic resonance integral with the following analysis:

Analysis for C ₁₄ H ₃₃ O ₂ PS ₃ :

Calculated: C, 47.98; H 6.61; S 27.73;

found: C, 48.19 and 48.24; H 6.57 and 6.63; S 27.73 and 27.71

The solvents are then removed from the three fractions that precede the above-worked-up fractions and from a 1.5 liter methylene chloride fraction that follows the above-worked-up fractions, whereby further material is obtained which, according to thin-layer chromatographic analysis, shows the quality of the material obtained above seems to correspond. The total yield is 13.9 g (40%).

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Example 3

Production of S- (alpha, alpha-dimethylbenzylthio) methyΙΟ, O-diethylphosphordithionate

A solution of 43.7 g (O _r 234 mol) of 0,0-Diätnylphosphordithiosäure and 47.0 (0.234 mol) of chloromethyl-alpha, alpha-dimethylbenzylsulfid (the lower, for example, by reacting the thiol of paraformaldehyde and gaseous hydrochloric acid in methylene chloride at Temperature is established) in 200 ml of methylene chloride is added dropwise with a solution of 23.7 g (32.7 mm, 0.234 mol) of triethylamine in 5O ml of methylene chloride. The addition takes place over a period of 20 minutes, and the reaction mixture is kept at a temperature of 20 to 25 ^° C. with an ice bath. The reaction mixture obtained is stirred for 2.5 hours at room temperature (where it becomes an extremely mild, slowly exothermic Reaction occurs in the early part of this time), whereupon the mixture is refluxed for 30 minutes. The cooled reaction mixture is washed with 50 ml of water, 25 ml of 5 percent hydrochloric acid, 25 ml of saturated sodium chloride solution, 25 ml of 5 percent potassium hydroxide solution and twice 25 ml of saturated sodium chloride each time. The solution is dried over magnesium sulfate, and after removing the solvent, 76.0 g (92.7%) of a pale yellow liquid are obtained. A comparison of the proton magnetic resonance spectrum of this material with that of the above analytical sample shows that the present material consists of about 95 percent by weight of the desired product.

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Example 4

Production of S- (alpha, alpha-dimethylbenzylthio) methylol O-diethyl phosphorodithionate

A mixture of 37.2 g (0.200 mol) of 0,0-diethylphosphorodithioic acid, 30.5 g (0.200 moles) alpha, alpha-dimethyl-alpha-toluene thiol and 16.5 ml (0.220 mol) of methanol-free formalin is stirred vigorously for 3 days at room temperature. The received The mixture is extracted with 205 ml of methylene chloride, and this solution is washed twice with 30 ml of saturated sodium chloride solution each time, four times with 30 ml of 5 percent sodium hydroxide solution each time and three times with 30 ml of saturated sodium chloride each time. The resulting solution is dried with magnesium sulfate and, after evaporation of the solvent, is obtained a colorless, medium-viscosity liquid residue. The proton magnetic spectrum of this material shows that in the desired product is included as the predominant component.

Example 5

Production of S- (alpha _f alpha-dimethylbenzylthio) methyΙΟ, 0-dimethylphosphorodithionate

0.078 moles of chloromethyl-alpha, alpha-dimethylbenzyl sulfide in 100 ml of acetone v / earth with 15.3 g (0.078 mol) of sodium 0,0-dimethylphosphorodithionate added, stirring overnight. The reaction mixture is at a temperature of Maintained 25 to 30 ° C.

The acetone is then evaporated off, whereupon the residue is suspended in 200 ml of methylene chloride and the organic Wash the solution with water and 5 percent sodium hydroxide solution. The organic solution is washed with magnesium sulfate. Evaporation of the solvent gives

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25.0 g (99%) of a colorless liquid. This material is chromatographed on a silica gel dry column cleaned using 25 percent by volume methylene chloride in hexane as the eluent. You get so 9.2 g colorless liquid, the structure of which is confirmed by magnetic resonance and infrared spectra.

Analysis for C ₁₂ H ₁₉ O ₂ PS ₃ : ■ ■ · ■

calculated: C, 44.72; H 5.90;
Found: C, 44.54; H 6.00.

Example 6

Manufacture of S- (p-chloro-alp hafalpha-dimethylbenzylthip) -methyl-OyO - diethylphosphorodithionate

32.5 g chloromethyl-p-chloro-alpha / alpha-dimethylbenzyl sulfide (made from p-chloro-alphajalpha-dimethyl-alpha-toluene thiol, that according to Example 1 from p-chloro-alpha, alphadimethy! benzyl alcohol obtained) in 250 ml of acetone are mixed with 23.4 g of potassium 0,0-diethylphosphordithionate. That The mixture is stirred for several hours at room temperature, after which the majority of the acetone is removed under vacuum and the residue mixed with methylene chloride. The methylene chloride mixture is washed with water and then with Dried magnesium sulfate. After removing the solvent in vacuo, 38.2 g of crude product remain, which is obtained by dry column chromatography above a column filled with silica gel, which has a diameter of about 3.8 cm, and below Use of 25% methylene chloride in hexane as a solvent for development and ultraviolet light for detection cleans. A main band, cut out of the column and eluted with ethyl acetate, yields 12.8 g of colorless,

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Product when constricting. It is thin-layer chronographical homogeneous, and its structure thus agrees with the infrared spectrum and the nuclear magnetic resonance spectrum.

Analysis for C ₁₄ H ₂₂ ClO ₃ PS:

calculated: C, 43.70; H 5.7 2; found: C, 43.59; H 5.72. · ....

Example 7

Production of S- (p-chloro-alphayalpha-dimethylbenzylthio) - methyl 1-0,0-dimethyl phosphorodithionate

You work the same way as in Example 1, but instead of of potassium 0,0-diethylphosphorodithionate but potassium-0,0-dimethylphosphorodithionate is used, and thus receives a colorless oil as a purified product.

Analysis for Cj 2H ₁ QClO ₂ PS ₃ :

calculated: C 40.40; H 5.05; Found: C, 40.13; H 5.12.

Example 8

Production of S- (3 ^ -Dichlor-alphayalpha-dimethylbenzylthio) -methy1-0, O-diethylphosphorodithionate

Using one made from 3,4-dichloro-alpha, alpha-dimethylbenzyl alcohol 3,4-dichloro-alpha, alpha-dimethyl-alphatoluene thiol prepared according to the procedure described in Example 1 and following the procedure described in Example 6

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nan arrives at the desired product in the form of a colorless oil.

Analysis for C ₁₄ H ₃₁ Cl ₂ O ₂ PS ₃ :

calculated: C, 40.11; H 5.01; Cl 16.92; P 7.39; S 22.94; found: C 39.97; H 5.07; Cl 17.06; P 7.30; S 23.04.

Example 9

Production of S- (3,4-dichloro-alpha, alpha-dimethylbenzylthio) - iu ethyl-Q, Q-dime thy Iphosphorodithionate

Using that according to Example 1 from 3,4-dichloro-alpha, alphadiniethy! Benzyl alcohol 3, 4-dichloro-alpha, alphadiraethyl-alpha-toluene thiol produced and use of potassium O, O-dimethylphosphorodithionate instead of potassium O, O-diethyIphosphorodithionate the procedure described in Example 6 gives a colorless oil of the desired product.

Analysis for C ₁₂ H ₁₇ Cl ₂ O ₂ PS ₃ :

calculated: C, 36.84; H 4.35; Found: C, 36.83; H 3.34.

Example 10

Production of S- (alpha, alpha-dimethylbenzylthio) methyl-O-ethyl-S-propyIphosphorodithionate

According to the procedure described in Example 5 and using sodium O-ethyl-S-propylphosphorodithionate instead of Ο, Ο-dimethyl phosphorodithionate, this is obtained

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expected product in the form of an oil,

Analysis for C ₁₅ H ₂₅ PO ₂ S ₃ :

calculated: C, 49.45; H 6.86; Found: C, 49.23; H 6.84.

.. Example. .11.

Preparation of S- (p-bromo-alpha, alpha-dimethylbenzylthio) ~ methyl 0 »0-dimethyl phosphorodithionate

Using the according to Example 1 from p-bromo-alpha, alphadime thy! benzyl alcohol produced p-bromo-alpha, alpha-dimethyl-alpha-toluene thiol and using potassium 0,0-dimethyl phosphorodithionate instead of potassium 0,0-diT ethyl phosphorodithionate is obtained according to the method in Example 6 described procedure to the desired product in the form of a colorless oil.

Analysis for

Calculated: C, 35.92; H 4.49; found: C, 35.95; H 4.63.

Example 12

Production of S- (m, alpha, alpha-trimethylbenzylthio) methyΙΟ, O-diethylphosphordithionate

Using the according to Example 1 from m, alpha, alpha-trimethyl benzyl alcohol produced m, alpha, alpha-trimethyl-.alpha-toluene thiol and following the procedure described in Example 6, the desired product is obtained as colorless oil.

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Analysis for ^c i2 ^H 25 ° 2 ^PS 3 ^:

calculated: C, 49.45; H 6.86; Found: C, 49.54; H 6.35.

example

Production of S- (al pha -Hethylbenzylthio) methyl-0,0-diethyl-

phosphorodithionate

Following the procedure described in Example 4 and using alpha-methyl-alpha-toluene thiol instead of alpha, alpha-dimethyl-alpha-toluene thiol and column chromatography After cleaning, the desired product is obtained in the form of a colorless oil.

Analysis:

calculated: C, 46.43; H 6.24; Found: C, 46.42; H 6.05.

example

Production of S- (p-chloro-alpha, alpha-dimethylbenzylthio) -methyl-O-methyl-S-iaethylphosphorodithionate

According to the procedure described in Example 6, however
obtained using potassium O-raethyl-S-methylphosphorodithionate instead of potassium C ^ O-diethylphosphorodithionate
the purified product of the title compound in the form of a colorless oil.

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2A15979

Analysis for C ₁₂ H ₁₈₂₃

calculated: C 40.40; H 5.05;
Found: C, 41.18; H 5.17.

Example .15

Production of S- (alpha, alpha-dimethylbenzylthio) methyl-O-methyl-

phosphorus cxmidothionate

After the procedure described in Example 5 and using potassium O-methylphosphoramidothionate arrives to the desired product. ■ · *

Example 16

Manufacture of S- (alpha, alpha-dimethylbenzylthio) methy1-0-methyl-S-2-ethoxyethylphosphorus chloride

Following the procedure described in Example 5, one obtains using potassium S-2-methoxyethyl-O-methylphosphorodithionate the desired product. Compounds of this type can also be obtained by demethylating the 0,0-dimethyl ester, of S- (alpha, alpha-dimethylbenzylthio) methylphosphorodithionic acid (Example 5) by known processes (for example with hydrogen sulfide ions, tertiary amine bases, 0,0-diisopropylphosphorodithionate ions, Iodide ions) and realkylation of the intermediate product O-methyl-S- (alpha, alpha-dimethylbenzylthio) Prepare methyl phosphorodithionate with an appropriate alkyl or substituted alkyl halide.

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Example 17

Manufacture of S- (alpha, alpha-dimethylbenzylthio) methyl-O-isopropyl-O-ir.ethylphosohordithionate

Following the procedure described in Example 5, the desired is obtained from potassium 0-methyl-O-isopropylphosphorodithionate Product. Optionally, this compound can also be prepared by adding the 0,0-diethy! Ester of S- (alpha / alpha-dimethy1-benzylthio) methylphosphoroditionic acid of Example 2 hydrolyzed (for example with aqueous metal hydroxide) and that (alpha, alpha-dimethylbenzylthio) methanethiol obtained then with O-Ilethyl-O-isopropylphosphorochlorodithionate in the presence of, for example, alkali alkoxides or tertiary amines.

Example 18

Production of S- (alpha, alpha-dimethylbenzylthio) methyΙΟ, 0-diisopropylph.osphorus thionate

According to the procedure described in Example 5, but using Xalium-O, 0 ~ diisopropylphosphorodithionate instead of potassium 0,0-dimethylphosphorodithionate, the desired product is obtained.

Analysis:

calculated: C, 50.79; H 7.14; found: C, 50.47; H 7.18.

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Example 19

Preparation of S- (alpha-ethyl-alpha-yn.ethylbenzylthio) methyl-

O, 0-diethy lphos phordithionate

0.091 mol of chloromethyl-alpha-ethyl-alpha-methylbenzyl sulfide and 16.9 g (0.091 mol) of a phosphorodithionate of the FOrIUeI (C ₂ H ₅ O in 100 ml of ether are added dropwise with 9.2 g of triethylamine, the temperature being raised to 25 ⁰ C. The mixture is stirred for several hours, after which it is washed with water and 5 percent strength sodium hydroxide solution, the washed solution is dried over magnesium sulfate and then evaporated to give 31.3 g (95%) of a colorless liquid Material is chromatographically purified over a silica gel dry column using 10 volume percent methylene chloride in hexane as the eluent.

This initially gives 6.3 g of a liquid which is analytically pure according to its nuclear magnetic resonance and infrared spectra.

Analysis for C _1n -H ₀₁ -O-PS- ,:
15 Zb 2 3

calculated: C, 49.45; H 6.86; Found: C, 49.32; H 6.91.

In addition, 6.0 g of a liquid which is approximately 85 to 90% pure is obtained.

Example 20

Production of S- (alpha, alp h a-diethyIbenzylthio) methyl-0, O-

diethyl phosphorodithionate

In a manner analogous to the above procedure, but using chloroethyl-alphajalpha-diethylbenzyl sulfide instead of

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Chlorraethyl-alpha-ethyl-alpha, alpha-methylbenzyl sulfide is obtained you get the product you want.

Analysis:

calculated: C, 50.79; H 7.14; Found: C, 50.81; H 7.31.

Example 21

\ Production of S- (alpha, alpha-dimethylbenzylsulfinyl) methyl-

0, Q-diethyl phosphorodithionate

A solution of 20 g (0.057 mol) of the phosphorodithionate obtained according to Example 2 in 100 ml of methylene chloride is ^{cooled to 5 to 10 °} C. and 11.6 g of 85 percent n-chloroperbenzoic acid are added in portions over the course of 15 to 20 minutes. The reaction mixture is kept at 10 ° C. during the addition.

The heterogeneous mixture is stirred at room temperature overnight and then filtered. The filtrate is made with sodium carbonate solution washed and dried with magnesium sulfate. After evaporation of the solvent, 20.9 g of a pale yellow color are obtained Liquid (100% yield). This material is dried over a silica gel column using methylene chloride purified by chromatography as eluent.

7.5 g of a colorless liquid are obtained, the nuclear magnetic resonance and infrared spectra of which confirm the assumed structure.

Analysis for C ₁₄ H ₂₃ O ₃ PS ₃ :

calculated: C 45.90; H 6.28; Found: C, 44.67; H 6.06.

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Example 22

Production of S- (alpha, alpha-dimethylbenzylsulfinyl) methyΙΟ, O-diisopropyl phosphorodithionate

According to the procedure described in the above example and using 0,0-diisopropyl-S- (alpha, alpha-dimethylbenzylthio) methyl phosphorodithionate instead of O, O-diethyl-S- (alpha, alpha-diiaethylbenzylthio) methyl phosphorodithionate you get the desired product.

Analysis:

calculated: C, 48.73; H 6.85; '· _

Found: C, 48.87; H 6.85.

Example 23

Manufacture of S- (alpha, alpha-dimethylbenzyl sulfonyl) methyΙΟ, O-diethylphosphorodithionate

A solution of 0,0-diethyl-S- (alpha, alpha-dimethylbenzylthio) -raethylphosphorodithionate (0.050 mol) in 100 ml of methylene chloride is cooled to 0 to 5 C and for one hour with solid m-chloroperbenzoic acid (20.4 g with 85% assumed purity, 17.3 g actually, 0.10 mol) added. The temperature the exothermic reaction is kept at 5 to 10 ° C. by external cooling during the addition. The reaction mixture The mixture is stirred for several minutes at about 5 ° C., after which it is allowed to warm up and then stirred at room temperature overnight. The received The reaction mixture is filtered and the filtrate is washed one with 50 ml of 2N sodium hydroxide, 25 ml of 2N sodium hydroxide, twice 25 ml of saturated sodium chloride each time, whereupon the Whole dries over magnesium sulfate. From the dried

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Solution is then reduced to the solvent Pressure removed leaving a moderately viscous liquid.

Example 24

Analogously to Example 3 and using the information given below Sulphides instead of chloromethyl-alphajalpha-dimethylbenzyl sulphide the following products are obtained:

sulfide

Chlorine thy 1-p-chlor-malpha _r alpha-triniethylbenzyisuiüid

Chlorine thy 1-p-cyanoalpha, alpha-dimethylbenzyl sulfide

Chlorine thyl-alpha, alphadime ethyl 2,4,5-trichlorobenzyl sulfide

product

Phosphorodithioic acid-S- (p-chlorom-alpha, alpha-trimethylbenzy1-thio) methyl-O _f O-diethyl ester

Phosphorodithioic acid S- (p-cyanoalpha / alpha-dimethylbenzylthio) -methyl-O, O-diethyl ester

Phosphorodithioic acid S- (alpha, alphadimethyl-2 , 4 , 5-trichlorobenzylthio) methyl-O, O-diethyl ester

Example, 1 25

Analogously to Example 5 and using the sulfides mentioned below instead of chloromethyl-alpha ^ alpha-dimethylbenzyl sulfide the following products are obtained:

sulfide

Chlormethyl-alpha , alphadiraethyl-p-nitrobenzyl sulfide

product

Phosphorodithioic acid-S- (alpha, alphadime thy1-p-nitrobenzylthio) methyΙΟ , O-dimethy! Ester

409841/1059

Substituent instead of p-tlitro benzyl

1 . p-Tri fluorine thy I.

2. m-fluorine

3. p-isopropyl

4. m-carbethoxy

5. n-Methylthio-6 - n-Trichloromethyl-

Substituent instead of p-nitrobenzyl

p-trifluoromethyl m-fluorine

p-isopropyl

m-carbethoxy n-methylthio-.

n-trichloromethyl

Example 26

Production of S- (alpha, alpha-dimethylbenzylthio) methy1-N, N, 0-

triiuethylphosphoramldodithlonat

The title compound is obtained according to the procedure described in Example 5 , but using potassium N _/ N _/ O-trimethylphosphoramidodithionate instead of sodium OjO-dimethylphosphorodithionate.

Example 27

Production of S- (3 , 4-dichloro-alpha, alpha-dimethylbenzylthio) methyl-O-ethylphenyl phosphorodithionate

By reacting chloromethyl 1-3,4-dichloro-alpha, alpha-dimethylbenzyl sulfide obtained with sodium O-ethylphenyl phosphorodithionate one the title compound.

409841 / 105a

Example 28

Assessment of the insecticidal effect (control of false wireworm)

The compounds are prepared as dusts on talc. The compounds are dissolved in acetone, and from these solutions corresponding concentrations are established by serial dilution here. 1.25 ml of a solution are pipetted onto a standard dust volume in a 30 ml (one ounce) vessel, and the acetone is left in owe. Then 25 ml of moist earth and given about 3 grains of wheat, before closing it and mixing the contents thoroughly. In every vessel thereupon 10 false wireworm larvae (Eleodes suturalis), which are 10 days old, were given. After 6 days, the respective dead Count larvae and determine the percentage mortality. The values obtained are summarized in Table I.

Southern corn rootworm

The compounds are prepared in the form of dusts on talc, The compounds are dissolved in acetone, and by serial dilution appropriate concentrations are established. 1.25 ml of solution are added to a standard dust volume in 30 ml vessels pipetted, whereupon the acetone is allowed to evaporate. Each jar is filled with 25 ml of moist soil and about 200 millet seeds filled, whereupon you close it and mix the contents thoroughly. 10 larvae are then extracted into each vessel the second form of the southern corn rootworm (Diabrotica undecimpunctata). Takes place after 6 days a count of the larvae killed, thereby determining the percentage mortality. The results obtained are shown in Table I.

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Tabel

link R ₂ ■ η V ^R 4 A. X Y Z applied ü
kg / ha (IbS./ Potting soil 50 10 1 X
^R 1 \ ^AR i / -K
P-SCH ₂ S (O) -C- {f ^)
^R 2 R ₄ lenge
'Acre) ^R 1

C ₂ H ₅ Percent control on H CH ₃ wrong I-M I II Drnhtv / urm 100 100!
1 0 C ₂ H ₅ O ^C 2 ^H 5 0 CII ₃ CH ₃ S. H H 100 100 I.
I. 0 C ₂ H ₅ O CII ₃ 1 ^CI5 3 CH ₃ ^s II II 100 I.
100 i 100 ^CH 3 ° 0 CiI ₃ CH ₃ S. II H 100 •
j - (CH ₃ J ₂ CHO C ₂ H ₅ 0 CH ₃ CH ₃ S. H II 100 )
loo j 0 ^C 2 ^H 5 ° ^{0 s} H II H H H

Percent control of southern malworm worm from (cont.)

Table I (cont.) Percent control in southern corn rootworm

^R 1 ^R 2; η ^R 3 ^R 4 A. X Y Z 50 10 1 C ₂ H ₅ O C ₂ H ₅ 0 H CH ₃ S. H H H 100 100 80 C ₂ H ₅ O ^C 2 ^H 5 1 CH ₃ CII ₃ S. H H H 100 100 0 CH ₃ O CH ₃ " 0 CH ₃ CH ₃ S. II H H 100 100 ' 100 (CH ₃ ) ₂ CHO (CH ₃ J ₂ CII 0 CH ₃ . CH ₃ S. H H H 100 0 - C ₂ H ₅ O C ₂ H ₅ 0 CH ₃ CH ₃ S. H H H 100 100 90 C ₃ H ₅ O C ₂ II ₅ 0 CH ₃ C ₂ H ₅ S. H H H 100 100 ⁰ £ C ₂ H ₅ O ' C ₂ H ₅ 0 C ₂ H ₅ C ₂ H ₅ S. H H H 100 100 50 11-C ₃ H ₇ S C ₂ H ₅ 0 CH ₃ CH ₃ 0 H . H H 100 100 0 C ₂ H ₅ O C ₂ II ₅ 0 CH ₃ CH ₃ S. H 4Cl H 100 90 0 C ₂ II ₅ O C ₂ H ₅ 0 ' ^CH 3 CH ₃ S. II 3CH ₃ II 100 100 100

Table I (cont.) Percent control in southern corn rootworm

^R 1 ^R 2 η R ₃ ^R 4 A. X Y Z - 50 10 1 ^CH 3 ° CH ₃ 0 CH ₃ CH ₃ S. 3Cl 4Cl H 100 100 100 CH3O CH ₃ 0 CH ₃ CH ₃ S. H ; 4C1 H 100 100 100
i CH ₃ S CH ₃ 0 CH ₃ CH ₃ 0 H 4Cl H 100 100 k
0 CH3O CH ₃ 0 CH ₃ CH ₃ S. H 4Br H '100. 100 .90

Example 29 Control of Insects and Acarids

The effectiveness of the compounds according to the invention for controlling of insects and acarids is shown by the following studies. The following are used for these investigations Procedures A to H listed are used and the results obtained are shown in Table II.

A. Spotted plant beetle - Lygus lineolaris (Palisot de Beauvois)

The test compounds are prepared in the form of 1000 ppm solutions in 10% acetone, 0.2% Alrodyn 315 and 89.8% water. The whole is diluted tenfold with 65% acetone and 35% water. Primary leaves of Sieva lima bean plants are immersed in the test solutions for 3 to 5 seconds and then placed in a hood to dry. After drying, each leaf is placed in a 10 cm Petri dish with a moist filter paper on the bottom. Then 10 adult Lygus beetles are removed from the stock culture and placed in the respective Petri dishes. The trays are covered and then maintained at about 26.7 ⁰ C and 50% relative humidity. The dead beetles are counted after 2 days.

B. Cotton Boll Beetle - Anthonomus grandls (Boheman)

The test compounds are in the form of 1000 ppm solutions in 10% acetone, 0.2% Alrodyn 315 and 89.8% water. The whole thing is tenfold with 65% acetone and 35% water diluted. The first or the second real leaf of young cotton plants is then dipped into the for 3 to 5 seconds

409841/1059

Test solution and place it in a hood to dry. After drying, each leaf is placed on a Petri dish about 10 cm in size, on the bottom of which there is a moist filter paper. 10 adult cotton rag beetles are then removed from a stock culture and each placed in a Petri dish. The cups are covered and maintained relative at about 26.7 ⁰ C and 50% humidity. A mortality count is carried out after 2 days. ·. . . ·.

E. Bean aphid - Aphis fabae (Scopoll)

The compounds are tested in concentrations of 100, 10 and 1 ppm in solution or suspension in 65% acetone and 35% water. About 5 cm large fiber pots, each containing an approximately 5 cm large Nasturtium plant, which 2 days beforehand with about 150 aphids infected are placed on a turntable (4 revolutions per minute) and during 2 revolutions with a # 154 DeVilbiss atomizer at air pressure

2
sprayed at 1.41 kg / cm. The spray nose is held about 15 cm from the plants and the spray is directed so that the aphids and plants are completely covered. The sprayed plants are then placed with their sides on white enamel sheets. It leaves the whole 2 days at 21.1 ⁰ C and about 50% relative humidity, is made after which a mortality count.

D. Southern Army Worm - Prodenia eridanie (Cramer)

The compounds are tested in concentrations of 1000 and 100 ppm in solution or suspension in 65% acetone and 35% water. Primary leaves of Sieva lima bean plants are then immersed in the test solution for 3 seconds, after which they are treated in this way Let plants dry in a hood on a net. After drying, place each leaf in a 10 cm Petri dish, on the bottom of which there is a damp filter paper, and then

409841/1059

then give 10 about 9.5 now long army worm larvae of the third form. The trays are covered and lifted relative at 26.7 ⁰ C and 60% humidity. After 2 days, a mortality count is carried out and the amount of feed consumed is determined. Compounds that give only partial kill and / or feed inhibition are observed for a day longer.

E. Two-spotted spider mite - Tetranychus urticae (Koch)

Sieva liitia plants, the primary leaves of which are 7.6 to 12.7 cm long , are infected with approximately 100 adult mites per leaf 4 hours before they are used for the experiment. The plants infected with mites and eggs are then immersed for 3 seconds in the same solutions as those used in the aphid test, after which the individual plants are left to dry in the fume cupboard. They are lifted then 2 days at 26.7 ⁰ C and 60% relative humidity, after which determined the mortality of adult mites on a leaf under a stereo microscope. The other leaf is left to a further 5 days on the plant and then tested it at 1o-fold magnification in order to determine the destruction of eggs and newly hatched nymphs, obtaining a measure of ovicidal and residual effect.

F. Mexican bean beetle - Epilachna varivestis (MuIs.)

The compounds are examined in the form of 100 ppm or 10 ppm solutions in 65% acetone and 35% water. Sieva lima bean plants are dipped into the test solutions and then dried in a hood. The dried leaves are then placed in 10 cm Petri dishes, on the bottom of which there is a moist filter paper, and 10 bean beetles of the third instar are then placed in each Petri dish. The trays are covered and lifted relative at 26.7 ⁰ C and 60% humidity. A mortality count is carried out after 2 days and

409841/1059

Determination of the amount of feed consumed. Connections that lead to a kill of more than 75%, are examined further at 10-fold dilution in 65% acetone and 35% water.

G. Western potato leafhopper - Empoasca abrupta (Say)

Sieva lima bean plants with primary sheet about 7 to 12.7 cm _f6 1-ang is to be immersed in 0 * 10 ppm or 10 ppm solution of 50% acetone and 50% water and then dried in a fume hood. A piece about 2.5 cm long is then cut from the tip of the treated leaf and placed in a 10 cm Petri dish with a moist filter paper on the bottom. 3 to 10 nymphs from the second appearance are then removed from the cultivated plants and placed in the Petri dishes, whereupon they are quickly covered. It leaves the whole 2 days at 26.7 ⁰ C and 50% relative humidity, after which determines the mortalities.

H. Malaria Mosquito - Anopheles quadrimaculatus (Say) - Adult Test

Solutions of 65% acetone and 35% water that contain 10 ppm test compounds

3 dung are placed in about 60 cm wide neck flasks, each containing a microscope slide. The slides are removed from the test solution with tweezers and placed horizontally on a 120 ml wide-necked bottle to dry. After drying, the slides are placed in the same 120 ml wide-necked bottle, and 10 4 to 5-day-old mosquitoes of different sex are placed in each bottle. A piece of cotton gauze held in place with an elastic band serves as a closure, and a cotton plug soaked with 10 percent honey solution serves as food. It leaves the whole day at 26.7 ⁰ C and 50% relative humidity, is made after which a mortality count.

409841/1059

The values obtained by the above process can be seen in Table II.

(R)
Alrodyne 315 is a surface-active agent based on a polyethylene glycol fatty acid ester.

(R)
Tween 80 is a surfactant based on a

Polyoxyethylene sorbitan monooleate.

409841/1059

Table II

- Control ^ of insects ι and Acariclene 100 10 1 - percent ι 100 mortality 10 Mexi
kanischer
Beans
Beetle ' 10 western Kar-
, toff-
sheet-
hopper 10 malaria
mosquito link NS,
/ ρ τι (Λ \ _w p _w cpu "θ — p · .// \
\> _ - ^ * t ~ ^ 'O ¹ ^ WW Il λ OV »\
CH ₃ camouflaged
plants
Beetle Tree-
where 11-
capsule
Beetle Bean ε
aphid. 100 100 85 iüdl .Heer
worm 100 two
spotty
be crazy
mite
ι 75 ■ ppm 40 ppm 100 ppm ppm ppm ppm 100 100 100 ppir 30th ppm 0 100 0 100 100 10 S 0 CH,
Il Il I / "" T ¹
(C ₀ H ₁ -O)., - P-SCH ₀ -SC - </ \
2 5 2 2, \ -
CH ₃ 100 100 100 100 100 1000 80 100 100 100 100 100 100 100 ) 94 95 100 100 ■ 90 100 100 ^ 70 90 100 100 100 100 - > ° 100 100 100

Table II (cont.)

(O OO

to

Control of insects and Acarids 100 I 10 11 0 - percent 100 ■ 0 I. mortality 10 j I. ₀ Mexi
kanischer
Beans
Beetle 10 0 western Kar-
potato
sheet-
hopper 10 100 0 malaria
mosquito ι
1 V » 70 link
1 camouflaged
plants
Beetle tree
want
capsule
Beetle Beans
aphid 100 100 I.
I.
j
ί 80
t Southern Army
worm 100 two
spotty
be crazy
mite 100 ppm 80 ppm j 100 ppm ppm ppm ppm I.
i 0 ppm ppm 100 I.
90 ' 100 ί
j "]
0 I.
t
t
1
I.
i
0 10 0 C / IT]
(CH ₃ O) ₂ -P-SCH ₂ -SC- ^ ^N 100 100 1000 100 100 100 CH ₃ \ 90 100. 100 100 100 0 100 S ^CH 7 / - 11 1 -y /
A *) 4 & * · f \ —— 100 100 50 60 C ₂ H ₅ \\
M 0 - 100 (C ₉ H ₁ -O), -P-SCIU-SC- (' 100 ^C 2 ^H 5 ^ λ 0 90 100 ___y
ί

cn CD - «J co

Table II

(Cont.)

Control of insects and acarids - percent mortality

link

camouflaged plant beetle

Cotton boll

Beetle

Bean aphid

southern army worm

two-spotted spider mite

Mexico-western Karkanischerj potato bean leaf beetle ; hopper

Malaria mosquito

ppm

ppm

ppm

ppm

ppm

ppm

100

100 J100

1000

100

100

10

ppm

100

10

ppm

10

O CH P-SCH ₂ -SC-

CH.

70. 100

100

100 '100

100

90

80

100

(C ₂ H ₅ O) -P-SCH ₂ -

CH,

CH \ ι ■

CH,

70

1100 p

100 0

100

20th

0 100

(C ₂ H ₅ O) ₂ -P-SCH ₂

CH,

Cl

CH.

90 1100

100

100,100

100 I 100 80

100 j 100 I.

75

link cn
to NS,
• ι ι ^a fr $
(C ₀ H ₁ -O) ₀ P-SCH ₀ -SC- U \
Δ O Δ Z ι \ ~ j steering T away e 1 1 e II iPnrts. ) : Bean
I aphid I.
i 100 10 I. 1 Southern Army
worm 90 ι 0 100 100 two-
spotty
be crazy
mite 10 100 Mexi-
'kanischer
Bean
; Beetle 10 i western Kar-
'' teffel-
:sheet-
! hoppers 10 malaria
mosquito fO 0 • CH ₃ camouflaged
plants
Beetle ι PP ^ ppm ppm I.
! ¹ PPm ^; ppm ppm 75 - *
cn ο S CH,. ppm 100 1000 100 100 100: '100
i . 100 - 100 0 10 CO CO (CH ₃ O) ₂ P-SCH ₂ -SC- ^ . 100 of insects and acarids - percent mortality 100 CH : Tree-
woolly
capsule]
Beetle 100; 100 '100 - 100 -Br ο ppm i
!
j 100 100 0 0 100 ί 30th 100 Cl
) -Cl 0 100; 100

Example 30 studies on mammalian toxicity (LD ₅₀ for rats)

20 male albino rats or mice from Carworth Farms, Nelson strain (CFI strain for mice) (or other suitable strain) that is about 90 to. 120 g (18 to 20 g for mice) are difficult are selected. The animals are starved for 24 hours before the examination. The mice are not left starve.

A 20 percent solution or suspension in an aqueous solution of 0.2% agar or 0.1% Tween 80 is used to prepare materials that dissolve or are easily dispersed in an aqueous medium. The same dosage range (grams or milliliters of material per kilogram of animal body weight) is used for all materials in this experiment. If there is no prior information about the compound or its analogues, then a maximum dose of 10 g / kg is used, each diluted by a factor of 2 from the previous dose, ie 10, 5, 2.5, 1.25 g / kg. A sufficient number of doses are given to give a 50 percent response. The animals are observed several hours after administration and daily over a 14-day observation period. After this time has elapsed, the surviving animals are sacrificed, weighed and subjected to a gross autopsy. The results obtained are written down and the respective LD ₅ values are determined by the method of moving averages using the table from Weil / Weil, CS., Biometrics, 8: (3), 249-263, 195V.

Samples obtained in the form of liquids can be diluted or administer as suspensions in aqueous agar-tween, and

409841/1059

depending on the viscosity of the material. If you think the material is relatively non-toxic, then you choose an initial maximum dose of 10 ml / kg and choose the following Doses depending on the severity of the gross signs of toxicity.

Used for organic phosphate anticholinesterase insecticide a slightly modified "procedure. The phosphates are prepared for administration by using a Solution or dispersion in corn oil (Mazola), the concentration of which is adjusted so that the total volume of the Dose is 20 ml / kg (0.5 ml / kg for the mouse) in each case. The starting solution is prepared by first adding the The maximum dose to be administered is determined in mg / kg and then 50 ml (10 ml for the test on the mouse) of this solution in such a concentration that the desired dosage in mg / kg is obtained if you add 2 ml (0.5 ml for the Mouse) of the solution per 100 g body weight of the rat (20 g body weight of the mouse). For each lower one Dosage value is established serial dilutions, each differing by a factor of 2.

LD ₅₀ for the mouse

20 male albino mice of the CFI strain, weighing about 18 to 20 g, are used. The phosphates are used for administration prepared by making a solution or dispersion in corn oil (mazola), the concentration of which is so adjusted is that the total volume of the dosage is in each case 0.5 ml / kg. The starting solution is prepared by first determining the maximum dose to be administered in mg / kg and then 10 ml of this solution with a concentration which results in the desired dose in mg / kg if 0.5 mg of the solution per 20 g of mouse body weight administered. For any lower dose value

409841/1059

serial dilutions are made, each differing by a factor of 2.

_{The LD 5} values obtained by the above process are summarized in Table III below. From this table it can be seen that compounds of the above formula in which R ₃ and R _{4 are} methyl are generally much less toxic to mammals than compounds in which R and R _{4 are} hydrogen. If these values are combined with the insecticidal and acaricidal action of the test compound, it can also be seen that of the compounds of the formula mentioned at the beginning, in which R ₃ , R ₄ , A and η have the meaning mentioned at the beginning, those are preferred where R- and R. are methyl and at least one of the substituents X,, Y and Z is a substituent other than hydrogen.

_{The LD 5} values obtained by the above procedure are summarized in Table III.

409841/1059

CJ -H Ό

O ιη Q

C. in r— CM CU OO • I. CJ in T- • Ρ I. CM U cn I. + J Ui pi I. ρ} I. pi -Γ ¹ C. O in U Q - W. I. T_ OO W ⁼ CU OO in CM CM 33 33 O pi Mr.
IN THE VO in 33 a 33 33 CO 33 * QJ CM 33 ro to U 33 CO ! B U η 33 • cn 33 HM U m U O τ— O 33 Γ " 1 Oi U CC O CM U I. in " in to 33 S3 I. CM in CN U 33 U IN THE U r_) U W. O I. Pm ⁼ Pj CM O O O in in in 33 33 O 33 CM CM in CM U O 33 U CM U

409841/1059

Table III (cont.)

CD 00

^R 1 R ₂ η t
^R 3 ^R 4
I. Λ X Y Z 1
Mice Rats CH3O CH ₃ 0 CH ₃ !
CH ₃ S. H H H ■ 117 28 (CH _{3) 2} CH0 (CH ₃ J ₂ CH 0 CH ₃ CH3 S. H II H > 500 -_ (CH ₃ J ₂ CHO (CH ₃ ) ₂ CH 1 CH ₃ CH ₃ S. Η ' H II > 500 - -C ₃ H ₇ S ^C 2 ^H 5 0 CH ₃ CH ₃ O H H H - 34 C ₂ H ₅ O ^C 2 ^H 5 0 CH ₃ CH ₃ S. H- 4 cl H - 79 CH ₃ O CH ₃ 0 CH ₃ CH ₃ S. 3 cl 4 cl H - > 200 CH3O CH ₃ 0 CH ₃ CH ₃ S. H 4 cl H- - > 200 C ₂ H ₅ O ^C 2 ^H 5 ' 0 CH ₃ CH ₃ S. 3 cl 4 cl H - > 100

CO CD

Values given in the literature

Example 31 S ysteian test on a cut trunk (southern army worm)

The compound to be examined is an emulsion with 0.1 g test material, 0.2 g Alrodyn 315 as emulsifier, 10 ml acetone and 90 ml of water. The whole thing is diluted tenfold with water, which makes one for the first examination Receives emulsion with 100 ppm active ingredient. ·

A Sieva lima bean plant, in which only the primary leaves have not sprouted, is cut off just above the bottom surface and placed in a 60 cm bottle containing 100 ppm emulsion, in which it is held by a piece of cotton tied around the trunk. The bottle is then placed in a ventilated box with the leaves looking out of the box so that any fumes will drain from the compound at the end of the box and thereby not flush the leaves to be examined. The whole thing is kept for 3 days at 26.7 ° C. and 60% relative humidity, after which a leaf from each plant is placed on a moist filter paper on the bottom of a Petri dish. In each petri dish then Ί0 Southern armyworm larvae are given from the third aspect of what is left the whole thing for another 3 days at 26.7 ⁰ C and 60% relative humidity and then performs a corresponding mortality count.

Mites

The same procedure as above is used for the systemic examination of mites with the only exception that the Sieva lima bean leaves become infected with mites, and with both adult mites and nymphs while the leaves are in the ventilated box. To

409841 / 1O5S

3 days the leaves are removed and examined under a microscope to determine the percentage mortality. the
The values obtained are summarized in Table IV below, from which it can be seen that the compounds according to the invention are systematically effective insecticidal agents.

4098-1 / 1059

Table IV

Formula:

P-SCH S (O) -C-

«£ Γι *

CO CO

CD

Systeinic ijisekticide Viirksamkext ^R 2 A. η ^R 3 ^R 4 X Y Z % Mortality southern
Armyworms ^R 1 ^C 2 ^H 5 S. 0 CH ₃ CH ₃ H H H Mites 100 C ₂ H ₅ O ^C 2 ^H 5 S. 0 ^CH 3 CH ₃ H H H 80 0 11-C ₃ H ₇ S ^C 2 ^H 5 S. 0 ^CH 3 CH ₃ 3-Cl 4-Cl H 90 90 C ₂ H ₅ O CH ₃
» S. 0 CH ₃ CH ₃ H 4-Br H 30th 100 CH ₃ O CH ₃ S. 0 CH ₃ CH ₃ H 4-Cl H 100 100 CH ₃ O CH ₃ 0 0 CH ₃ CH ₃ H 4-Cl H 100 4th
0 CH ₃ S C ₂ H ₅ S. 0 CH ₃ CH ₃ H 3-Cl 4-Cl 30th 100 C ₂ H ₅ O 100

cn co -J CO

Claims (1)

Claims R ₂ O wherein R _{1 represents} alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkoxyalkyl with 3 to 6 carbon atoms, alkoxyalkylthio with 3 to 6 carbon atoms, alkylthio with 1 to 4 carbon atoms, phenyl or -NR ₅ R, R ₂ Alkyl with 1 to 4 carbon atoms is R ₃ for hydrogen, alkyl with 1 to 4 carbon atoms, mono-, di- or trihaloalkyl with 1 to 4 carbon atoms or phenyl, R. is alkyl with 1 to 4 carbon atoms and, or R ₃ and R ₄ together with the carbon atom form an alicyclic ring with 3 to 8 carbon atoms, R ₅ and R _ß each represent hydrogen or alkyl with 1 to 4 carbon atoms, A denotes sulfur or oxygen, η denotes an integer of 0.1 or 2, X and Y each represent hydrogen, alkyl having 1 to 4 carbon atoms or halogen and Z represents hydrogen, alkyl having 1 to 4 carbon atoms, cyano, halogen, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 Carbon atoms, trichloromethyl, trifluoromethyl, carbon-lower alkoxy with 1 to 4 carbon atoms, nitro or sulfamoyl. Connection according to claim 1 , characterized in that that the substituents R ₁ , R ₂ , R ₃ , R ₄ , A, X, Y and Z have the meaning given in claim 1 and η is 0. 409841/1059 3. A compound according to claim T, characterized in that. that the substituents R ₁ , R ~, R ₃ , R., A, X, Y and Z have the meaning given in claim 1 and η is 1. 4. A compound according to claim 1, characterized in that the substituents R .., R ,, R ₃ , R., A, X, Y and Z have the meaning given in claim 1 and η is 2. 5. O, O-diethyl S- (alpha, alpha-dimethylbenzylthio) methyl phosphorodithionate according to claim 2. 6. 0,0-Dimethyl-S- (alpha, alpha-dimethylbenzylthio) methyl phosphorodithionate according to claim 2. 7. S- (p-chloro-alpha, alpha-dimethylbenzylthio) methyΙΟ , 0-dimethyl phosphorodithionate according to claim 1. 8. S- (p-chloro-alpha, alpha-dimethylbenzylthio) methyl 1-0-methyl-S-methyl phosphorodithionate according to claim 1. 9. S- (3,4-dichloro-alpha, alpha-dimethylbenzylthio) methyΙΟ, O-diethyl phosphorodithionate according to claim 1. 10-S- (3,4-dichloro-alpha, alpha-dimethylbenzylthio) methyl-0,0-dimethylphosphorodithionate according to claim 1. 409841/1059 11. S- (p-bromo-alpha / alpha-dimethylbenzylthioJmethyl-OfO-dimethylphosphorodithionate according to claim 1. 12. Process for the preparation of an organophosphoric acid ester of the formula .P-SCH-S (O) -C- (Z 'A) (I), R ₂ o y ^{2 n} , ^R 4 wherein R _{1 represents} alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkoxyalkyl with 3 to 6 carbon atoms, alkoxyalkylthio with 3 to 6 carbon atoms, alkylthlo with 1 to 4 carbon atoms, phenyl or -NR ₅ R, R “alkyl with 1 to 4 carbon atoms, R _{3 is} hydrogen, alkyl with 1 to 4 carbon atoms, mono-, di- or trihaloalkyl with 1 to 4 carbon atoms or phenyl, R _{4 is} alkyl with 1 to 4 carbon atoms or R ₃ and R. together with the carbon atom form an alicyclic ring with 3 to 8 carbon atoms, R ₅ and R _ß each represent hydrogen or alkyl with 1 to 4 carbon atoms, A denotes sulfur or oxygen, η denotes an integer of 0, 1 or 2, X and Y each represent hydrogen, alkyl having 1 to 4 carbon atoms or halogen and Z represents hydrogen, alkyl having 1 to 4 carbon atoms, cyano, halogen, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms omen, trichloromethyl, trifluoromethyl, carbon-lower alkoxy with 1 to 4 carbon atoms, nitro or sulfamoyl, 409841/1059 characterized in that a thiol of the formula II -Y
HSC - ('■ ^N ) (II), wherein R_, R., X, Y and Z have the above meaning, and a a phosphoric acid of the formula III R A Il P-SH (III), R ₂ O ' wherein R., R- and A have the above meaning, with formaldehyde or a formaldehyde source with possible oxidation of the organophosphorus compound obtained to the corresponding one Sulfone or sulfoxide of the formula I mentioned at the beginning. 13. The method according to claim 12, characterized in that the thiol and the phosphoric acid with methanol-free Formalin converts at temperatures between 0 and 100 ° C. 14. The method according to claim 12, characterized that an organophosphoric acid compound of the formula I, where η is 0, with an equivalent amount of an oxidizing agent, such as m-chloroperbenzoic acid, in a solvent, such as methylene chloride, to form the corresponding sulfoxide. 409841/1059 15. The method according to claim 12, characterized in that that an organophosphorus compound of the formula I, in which η is 0, with an oxidizing agent such as potassium permanganate, tert-butyl alcohol buffered with magnesium sulfate or two equivalents of m-chloroperbenzoic acid in a solvent such as methylene chloride to form the corresponding sulfon implements. 16. Modification of the method according to claim 12 for production of the organophosphorus compounds of the formula I, characterized in that a stable methylene derivative of a Phosphoric acid of formula IV R ₁ A, ^^ PS-CH ₀ Cl (IV), wherein R ₁ , R_ and A have the above meaning with the alpha-substituted arylmethylthiol of the formula V. R ₃ X HS-C -M ^ f (V) ^R 4 wherein R., R., X, Y and Z have the above meanings, in the form of a base-catalyzed reaction using an alkali alkoxide with 1 to 8 carbon atoms in a saturated alcohol with 1 to 8 carbon atoms as a solvent or of sodium or potassium hydroxide as a base in a solvent such as dimethyl sulfoxide or dimethylformamide. 17th modification of the method according to claim 12 for producing the organophosphorus compound of the formula I, wherein _r to obtain a stable methyl derivative of the thiol, as the Chlormethylthioäther of formula VI R ₃ X (VI) R, wherein R ,, R., X, Y and Z have the above meaning, with a Phosphoric acid of formula VII -P-SM (VII), ^R 2 ° wherein R-, R- and A have the above meaning and M is a Alkali or ammonium ion is converted. 18. Methods for controlling insects and acarids, characterized in that the insects or acarids to be controlled with an effective amount of a compound treated according to claim 1. 19. The method according to claim 18, characterized in, that the active ingredient Ο, Ο-dimethyl-S- (3,4-dichloro-alpha, alphadimethy benzylthio) methyl phosphorodithionate, Ό, Ο-dimethyl-S- (p-chloro-alpha-alpha-dimethylbenzylthio) methyl phosphorodithionate, , S- (p-chloro-alpha, alpha-dimethylbenzylthio) methyl-0,0-dimethyl-phosphorodithionate, S- (p-chloro-alpha, alpha-dimethylbenzylthio) -methyl-O-methyl-S-methylphosphorodithionate, S- (3,4-dichloro-alpha, alpha-dimethylbenzylthio) methyl-0,0-dimethylphosphorodithionate, S- (3,4-dichloro-alpha, alpha-dimethylbenzylthio) methyl-0,0-di- \ ethyl phosphorodithionate or S- (p-bromo-alpha, alpha-dimethy1-benzylthio) -methy1-0, O-dimethylphosphorodithionate used. 409841/1053 20. The method according to claim 18, characterized in that the active ingredient on the habitat of the to be controlled
Insects or acarids. 21. The method according to claim 20, characterized in that that a compound according to claim 19 is used as the active ingredient. ■ .... 22. The method according to claim 18, characterized in that the active ingredient on the foliage of plants or
on the soil in which these plants grow, in order to protect the plants against attack by insects or acarids
to protect. 23. The method according to claim 22, characterized in that a compound according to claim 19 is used as the active ingredient .