KR820000080B1 - Process for the preparation of n-substituted phenylcarbamoyl methyl thio phosphonates - Google Patents

Abstract

Title compds. I(R = halo, C2-6 alkyl, C1-3 halogenoalkyl, NO2, C1-4 thioalkyl, OCH3; R1,R2,R3 = C1-6 alkyl; X = O, S; n = 1, 2, 3), useful as insecticides and nematocides, were prepd. by the reaction of compds, II and phosphorous compds. III(one of A and B is Cl or Br, the other SY; Y = H or metal cation). Thus, chloro acetylanilide II(A = Cl) and ammonium salt of phosphorous compds. III(B = SNH4) was stirred in glycolmethylether for 3-5 hr at 50≰C to give I.

Description

[Name of invention]

Process for preparing N-substituted phenyl carbamoyl methylthio phosphonate derivative

Detailed description of the invention

The present invention relates to a process for the preparation of compounds of the general formula (I) which are useful as insecticides, acaricides and nematicides.

Wherein R is the same selected from halogen, (C ₂ -C ₆ ) -alkyl, (C ₁ -C ₃ ) -halogenoalkyl, NO ₂ , (C ₁ -C ₄ ) -thioalkyl, or OCH ₃ group Or represents a different substituent and R ₁ , R ₂ and R _{3 represent} (C ₁ -C ₆ ) -alkyl (identical or different), X represents oxygen or sulfur and n is an integer of 1-3, provided that R is _{When 1} is methyl, (R) n cannot be 4-chlorine.

Compounds of formula (I) wherein R = CH ₃ and R ₂ = alkyl are disclosed in US Pat. No. 3,057,744 but no details are described. Some phosphate esters of almost the same general formula are also known in German Publication No. 1,122,935 but have a lower pesticidal and acaricide activity than the compounds according to the invention. Reference: Example VI

Preferred residues in formula (I) are as follows:

R is F, Cl, Br, (C ₂ -C ₄ ) -alkyl, CF ₃ , NO ₂ and S-CH ₃ , R ₁ , R ₂ , and R ₃ is (C ₁ -C ₄ ) -alkyl, in particular , R is preferably F, C1, Br, (C ₂ -C ₃ ) -alkyl, NO ₂ and S-CH ₃ .

The present invention also relates to pesticides containing a compound of formula (I) as an active ingredient in addition to the usual auxiliaries and inerts.

The compound of general formula (I) is obtained by the following method.

The compound of formula (II) is reacted with the phosphorus compound of formula (III) in the presence of an acid binder if necessary.

Wherein one of the A and B radicals represents a halogen, in particular chlorine or bromine, the other represents a SY-group where Y is hydrogen or a metal cation.

The phosphorus compound of general formula (III) (B = SY) may be reacted with chloro acetanilide of general formula (II) (A = hal) in a temperature range of 0 ° to + 120 ° C, preferably + 10 ° to + 80 ° C. React at a temperature in the range.

The process according to the invention is advantageously carried out in the presence of a solvent or diluent that is inert to the reactants. They are mainly lower aliphatic ketones such as acetone or methyl ethyl ketone, alkanols such as methanol, ethanol or isopropanol, esters such as ethyl acetate, N-alkylated acidamides such as nitrile, dimethylformamide, dioxane, glycol dimethyl Ethers such as ether or tetra hydrofuran, chlorinated hydrocarbons such as chloroform or carbon tetrachloride and water, as well as mixtures of these solvents and the like.

The halogen atom of chloroacet anilide is substituted during the reaction. The reaction therefore proceeds by addition of acid binders or salts of phosphorus compounds, in particular alkali metal salts and ammonia salts.

Alkali metal hydroxides and carbonates are suitable as acid binders. However, it is also possible to use tertiary nitrogen bases such as pyridine or triethylamine.

Haloacetic anhydride of formula (II) and its preparation are described in the literature.

SY-compounds according to formula (II) are known and can be readily prepared by conventional methods.

Conversely, thioglycolic acid anilide (formulas II and A = SY) may be reacted with a halophosphorus compound (formulas III and B = hal). At this time, when R ₄ = SH, the reaction is carried out in the presence of an acid binder. Generally, the reactants use approximately the formula weight, but it is advantageous to use excess (5-10%) of the compound of formula III. The reaction is preferably carried out in the presence of a solvent which is inert under the reaction conditions. As such a solvent, any solvent mentioned above can be used, for example. The reaction temperature is wide but preferably uses a temperature in the range of + 50 ° C to + 120 ° C. As the acid binder, any of those mentioned above may be used.

Thioglycolic acid anilide according to formula (I) may be prepared according to methods known in the literature.

Halophosphorus compounds of general formula (III) are known and can be obtained according to conventional methods.

Compounds of formula (I) have insecticidal, acaricide and nematicidal action.

The compound of general formula (I) is an effective acaricide that is effective in both contact and oral penetration, and is suitable for controlling various pests, and at the same time, plants have good resistance.

The compounds can control several different types of mites, such as Metatatetranychus ulmi, Panorychus citri, and Tetranychus urticae, as well as fungi resistant to phosphate esters.

To some extent, compounds of general formula (I) have good penetration in plants. As a result, for example, even if the agent is treated only at the top, it can kill pests on the back of the leaves.

The compounds according to the invention can be used to control various pests which damage crops by absorption and chewing.

These pests are as follows; Epilapna rarivestis, Lepitinotarsa decemlineata, Epi co-metis nirta, Phyllotreta spp., Coenohrhi Butterflies such as North Germanicus (Coenorrhinus germanicus), and Antonomus grandis, Earias isulana, and Heliothis armisgera, and their larvae, Tortorisida, In particular, Carpocapsa pomonella, Tortrix riridana, Ado xophyes retrculana, Ostrinia nubilalis, and Operophtera brumata ), Soybean aphids (Doralis fabae) peach aphids (Hy zodes persicae) and cotton aphids (Aphis gossypi) and plant-pests, such as Onco-peltus and Dysderus subspecies, special Paz Asia tooth (Fasciatus).

Moreover, ticks with protective color of livestock, such as Hyalomm marginatum, Rhipice phalus evertsi, Amblyomma Hebraeum, and Buprus Michael Rope Ruth (Boophilus microplus).

Furthermore, the compounds of the present invention have an excellent action against plant damage nematodes, for example meloidogy ne, hetero-dera, ditylenchus and aphelench oid.

In particular, halogen-substituted compounds are less toxic to warm-blooded animals than their cognate phosphate esters with unsubstituted aromatic nuclei.

The preparations according to the invention generally contain 2 to 80% of the active compound of general formula (I). These compounds can be used in the form of a hydrating agent, an emulsion concentrate, a spraying solution, a powder or granules.

Hydrating agents may be used in addition to active substances, diluents or inerts, wetting agents such as polyox ethylated alkylphenols, polyox ethylated oleyl or stearylamines, alkyl or alkylphenyl sulfonates and dispersants such as sodium of lignin sulfonic acid. It is an agent which can be uniformly dispersed in water containing a salt and a sodium salt of 2,2'-dinaphthylmethyl-6,6'-disulfonic acid or a sodium salt of oleylmethyl taurine.

Emulsion concentrates are obtained by dissolving the active materials in organic solvents such as butanol and cyclohexane in dimethylformamide, xylene or high boiling aromatic compounds.

Powders are obtained by grinding the active material with a natural review such as talc, kaolin, bentonite, filophyllite or diatomaceous earth as a fine powder. The spray solution contains the active ingredient dissolved in an additive mixture of fluorochlorohydrocarbon as an organic solvent or a spray agent.

Granules may be sprayed with an active material onto an adsorbent granulated inert material or surface of a carrier such as sand, kaolin or granulated inert material using an adhesive such as polyvinyl alcohol, sodium salt of polyacrylic acid or mineral oil. It is made by spraying a concentrate of the active substance on the surface. In addition, suitable active substances can be prepared by conventional methods of making fertilizers, and can be prepared by mixing with fertilizers as necessary.

The concentration of active substance in the hydrating agent varies, for example, in the range of approximately 10% to 80%, with the remainder being the formulation additives described above. In emulsion concentrates the concentration of active substance is approximately 10 to 70%. Powders usually contain 5-20% of active material and sparse liquids contain approximately 2-20% of active material.

The content of the active substance in the granules depends on the extent to which the active compound is a liquid or a solid and also the use of granule aids, fillers and the like.

Conventional concentrates in use can be diluted in a conventional manner as needed, for example, with water in the case of hydrating and emulsion concentrates. The spray solution as well as the form of powder and granulated preparations are no longer diluted with inert materials prior to use.

To control nematodes, the active substances are used in the form of powder, granules or water-soluble suspensions in the soil and then dug with a hoe or processed into the soil using a rotary hoe.

If volatiles are used, the soil must be treated appropriately.

The active substances according to the invention can be mixed with other pesticides, fungicides, nematicides and herbicides.

The following examples illustrate the invention.

Example A

Easily dispersed in water is 25 parts by weight of methanedithiophosphonic acid -S [N- (4-chlorophenyl) -N-isopropylcarbamoyl-methyl] -0-ethyl ester as an active substance, 64 weight as an inert substance. Obtained by grinding the mixture in a pin mill by mixing quartz containing negative kaolin, 10 parts by weight of a calinium salt of ligninsulfonic acid, and 1 part by weight of sodium salt of oleylmethyl taurine as a wetting and dispersing agent.

Example B

The powder is mixed with 10 parts by weight of methanedithiophosphonic acid-S- [N- (4-chlorophenyl) -N-isopropylcarbamoyl-methyl] -0-ethylester as the active substance and 90 parts by weight of malk as the inert substance. Obtained by grinding the mixture in a hammer mill.

Example C

Emulsions are 15 parts by weight of methanedithiophosphonic acid-S- [N- (4-chlorophenyl) -N-isopropylcarbamoyl-methyl] -0-ethyl ester as active substance, 75 parts by weight of cyclopentane and emulsifier as solvent. 10 parts by weight of oxetylated nonylphenol (10EO).

Example D

Granules are, for example, 2-15 parts by weight of methanedithiophosphonic acid-S- [N- (4-chlorophenyl) -N-isopropylcarbamoyl] -0-ethylester as the active substance, for example, attapulkit. And inert granular carriers such as pumice granules and / or quartz sand.

Production Example

A) 0.1 mole of chloroacetanilide of general formula II (A = Cl) in 0.10-0.11 moles of ammonium salt of a phosphorus compound of general formula III (B = SNH ₄ ) in 200 ml of glycol methyl ether at room temperature with stirring Add.

Stirring is carried out at approximately 50 ° C. for 3-5 hours, and the precipitated salt is filtered off with suction and the filtrate is diluted with about 40 ml of benzene. The organic layer is washed thoroughly with water and dehydrated with sodium sulfate. After distilling off the solvent, the product of the process is obtained in oil form which is partially crystallized on a mill. The same results can be obtained when using the solvent mentioned in a) instead of glycol dimethyl ether or when carried out at elevated temperature (+ 80 ° C.).

B) 0.10-0.11 mol solution or suspension of (thio) phosphonic acid chloride of the general formula III (B = C1) in 200 ml of glycol dimethyl ether in the presence of an acid binder, 0.1 mol of thioglycolic acid anilide of formula II (A = SH) Add at 50-120 ° C. with stirring.

Stirring is carried out at 80-120 ° C. for several hours and then the process is carried out as in a). The same result can be obtained when using the solvent mentioned in page 7 a) instead of glycol dimethyl ether.

C) first step

0.2 mol of thioglycolic acid methyl ester and 0.2 mol of methyl-0-ethyl-thiophosphonic acid chloride are dissolved in 250 ml of toluene and 0.21 mol of triethylamine is added dropwise with stirring at 0-5 占 폚. Once the dropping is complete, it is stirred for 2 hours at room temperature. The precipitated triethylamine hydrochloride is aspirated and the filtrate is washed with water and then dehydrated and concentrated in vacuo. The required compound of formula V is obtained in the form of a yellow oil (R ₄ = CH ₃ , R ₂ = CH ₃ , R ₃ = C ₂ H ₃ ).

Compound V can also be prepared by the following method.

0.2 mol of chloroacetic acid methyl ester is added dropwise at 10-15 占 폚 to a 0.21 mol solution of ammonium-methyl-0-ethyl-dithiophosphate in 250 ml of glycol dimethyl ether. The mixture is stirred at room temperature for 3 hours and then 0.1 L of toluene is added and the whole is washed three times with water. The organic layer is dehydrated with Na ₂ SO ₄ and concentrated in vacuo.

[Second step]

A 0.2 mol solution of 4-chloro-N-isopropylaniline is added dropwise to a 0.2 mol solution of compound V in 300 ml of glycol dimethyl ether. The whole is boiled at reflux for 5 hours. The whole is then concentrated under vacuum and 0.3 L of toluene is added to the residue. The mixture is then washed with 10% aqueous hydrochloric acid solution, washed with water until neutral, dehydrated with Na ₂ SO ₄ and concentrated in vacuo.

The required compound 15 in the table is obtained in this manner.

The compounds of general formula (I) reported in the following table are obtained according to the process described above, the composition of which can be identified by elemental analysis and characterized by refractive index and / or melting point.

TABLE A

TABLE b

[Application Example]

Example I

Soybean plants (Phaseolus vulgaris) severely infected with Tetronychus urticae (normal sensitivity) are sprayed with a dilute emulsion containing 0.0015% by weight of the active substance of Example (1) until the water drops. Subsequently, the sprayed plants are left in the greenhouse at about 20 ° C. Microscopic observation 8 days after spraying showed that all flow and immobilization had been killed.

When tested in the same manner, the compounds given in Table 1 demonstrated the same effect.

TABLE I

Example II

Phaseolus vulgaris, which is resistant to mites, is sprayed into the aqueous suspension of the compounds given in the following table II until the water drops. The plants were observed 8 days after being left in the greenhouse at 20 ° C.

TABLE II

1) = Tetranicus Urticae-species "Birdse" = (B)

2) = concentration for 99-100% killing of total sea layer

Dimethone-S-methyl = 0,0-dimethyl-S- (3-thiapentyl) -monothiophosphate

Dimethoate = 0,0-dimethyl-S- (N-methyl-carbamoyl-methyl) -dithiophosphate

Azinfosmethyl = 0,0-dimethyl-S- (4-oxo-1,2,3-benzotriazine-3-methyl) -dithiophosphate

Example III

50 leaves of Epilacna varivestis oil layer (Step 4) and leaves of Paseolus vulgaris contain a certain amount (in air) of an emulsion containing 0.002% by weight of the active substance of Example 15. 600 liters per hectare). The leaves with the beetle larvae were transferred to a vessel in a container at 22 ° C. and observed 48 hours after spraying, indicating that the test pests were 100% killed. The compounds of the examples given in Table III proved to be equally effective in this test.

TABLE III

Example IV

The action on ticks was demonstrated by the following test.

Vicia faba, infected with soybean aphid (Doralis fabae), was sprayed with a water suspension of powdered concentrate containing the amount of active substance given in Table IV until the water droplets dropped.

The plants are transferred to the greenhouse at 22 ° C.

Table IV

Example V

Powdered formulations were mixed with soil contaminated with nematode nematodes (Meloidogyne incognita), and the soil was filled in pots and grown in tomatoes. After 4 weeks at 25 ° C. and 70% atmospheric humidity, Chung Rin water was measured according to the following chart.

[Rating chart]

Table V shows the effect of the following compounds.

TABLE V

Example VI

German publication 1,122,935 shows that the compounds mentioned in DAS Table I (Examples 7 and 8) have a lower acaricide in tests conducted by spray tests when compared to the corresponding phosphonic acid esters according to the invention. Can be.

Table VI

Tu = Tetranicus Urtica

EXAMPLE VII

Oncopeltus fagocias is sprayed with a thin powder concentrate containing the given amount of active substance on the surface until the water drops, and then the pests are airtight at room temperature. Transfer to a container. The results are reported in Table VIII.

[Table VII]

Claims (1)

A process for preparing an N-substituted phenyl carbamoylmethylthio phosphonate derivative of formula (I), wherein the compound of formula (II) is reacted with a phosphorus compound of formula (III).

Wherein R is the same selected from halogen, (C ₂ -C ₆ ) -alkyl, (C ₁ -C ₃ ) -halogenoalkyl, NO ₂ , (C ₁ -C ₄ ) -thioalkyl or OCH ₃ group or Different substituents, R ₁ , R ₂ and R ₃ represent (C ₁ -C ₆ ) -alkyl (identical or different), X represents oxygen or sulfur, n is an integer from 1 to 3, provided that When R ₁ is methyl, (R) _n cannot be 4-chlorine, one of the A and B radicals represents a halogen, in particular chlorine or bromine, the other represents a SY-group, where Y represents hydrogen or Metal cations.