DE1667986C3 - Benzylthiophosphonic acid -O-alkyl-sphenyl ester, process for their preparation and fungicides containing them - Google Patents

Description

in which Y, R and η have the meaning given above, with a compound of the general formula III

MS

wherein X has the meaning given above and M έϊη is a hydrogen atom or an alkali atom means to be implemented in a manner known per se.

3. Fungicides for agriculture and horticulture, characterized by the content a fungicidally effective amount of at least one benzylthiophosphonic acid - O - alkyl - S - phenyl ester the general formula

P-S- ^

(1)

RO

wherein R is an alkyl group having 1 to 4 carbon atoms, the radicals X and Y are each a hydrogen atom, chlorine atom or methyl group and η Ο or 1 is.

2. Process for the preparation of benzylthiophosphonic acid O-alkyl-S-phenyl ester of the general formula I.

atoms, the radicals X and Y are each a hydrogen atom, chlorine atom or methyl group and η is O or 1.

1, Benzylthiophosphonic acid O-alkyl-S-phenyl ester of the general formula I The invention relates to benzylthiophosphonic acid O-alkyl-S-phenyl ester, a process for their production and for the fungicides containing these esters for agriculture and horticulture.

According to the invention there are benzylthiophosphonic acid O-alkyl-S-phenyl esters of the general formula I.

created, in which R is an alkyl group having 1 to 4 carbon atoms, the radicals X and Y are each a hydrogen atom, chlorine atom or methyl group and η is O or 1.

Furthermore, according to the invention, fungicides for

Agriculture and horticulture created by the content of a fungicidally effective amount at least one benzylthiophosphonic acid O-alkyl-S-phenyl ester of the general formula I.

X ~ \ -H ₂ CO

P-S

RO

wherein R denotes an alkyl group having 1 to 4 carbon, wherein R denotes an alkyl group having 1 to 4 carbon atoms, the radicals X and Y each a hydrogen atom, chlorine atom or a methyl group and η means 0 or 1.

To combat fire or powdery mildew (Piricuralia oryzae) and leaf sheath blight (Hypochnus sasakii), d. H. Diseases that are particularly common in rice have become compounds such as phenylmercuric acetate and methylarsonic acid metal salts

and the like on a large scale for their superior fungicidal effectiveness and for economic reasons Reasons applied.

However, it has been found that the application of organic mercury compounds to rice plants in their growing stage due to their direct toxicity and their indirect remaining Toxicity are harmful to health. There is therefore an urgent need for the development of chemical Compounds for agriculture and horticulture that do not harm humans or animals Contain heavy metals and which are highly effective in combating the above Possess rice diseases and are available at low cost.

According to the invention, various organic phosphorus compounds have been investigated in order to Compounds of the type indicated above to arrive, and it was found that the

3 4

enzvlthiophosphonic acid-O-alkyl-S-phenyl ester of diseases such as fire (Piricularia oryza), brown

Shend given formula I valuable fungicidal stains (Cochliobolus miyabeanus) and Blatuchei-

e are agriculture and horticulture, and own denbrand (Hypochnus sasakh). ,

Changes have been found to be an excellent choice. The following Table I are examples of

• Found activity against the important rice compounds according to the invention.

'abelle I

connection Structural formula Chemical name

No. 6

No. 7

No. 8

No. 9

P-S-

CH, O

CH ₃ O

Benzylthiophosphonic acid-O-methyl-

S-phenyl ester

(nff 1.5974)

CH ₃ benzylthiophosphonic acid- O-methyl-

S- (4-methyiphenyl) ester (n? 1.5948)

Benzylthiophosphonic acid-O-ethyl-

S-phenyl ester

{nf 1.5860)

CH ₃ benzylthiophosphonic acid O-ethyl-S- (4-methylphenyl) ester (nff 1.5828)

Benzylthiophosphonic acid O-isopropyl-S-phenyl ester

(η? 1.5755)

4-chlorobenzylthiophosphonic acid-O-ethyl-

S-phenyl ester

{n'S 1.5880)

\ ll

CH ₃ O

^ AH ₂ CO \ = / \ ll

\ ll

ρ _ _s _ ^ fy- ei Benzylthiophosphonic acid-O-methyl-

S- (4-chlorophenyl) estersΓ (n> 0 ° 1.6161); Kp. T7rC / 0, lmmHg

P-S_s / Vci

C ₂ H ₅ O

H ₁ C-

/ SH ₂ CO

\ ll

p — s

CH ₃ O benzylthiophosphonic acid-O-ethyl-

S- (4-chlorophenyl) estersΓ

(nff 1.5920); Bp 182 ° C / 0.15 mm Hg

4'-methylbenzyl-thiophosphonic acid

O-methyl-S-phenyl ester

(ni ° 1.6129)

The benzylthiophosphonic acid O-alkyl-S-phenyl ester are produced according to the invention by a method which is characterized in that benzylphosphonic acid alkyl ester chloride of the general Formula II

in which Y ₁ R and η have the meaning given above, with a compound of the general formula III

<C

wherein X is as defined above and M is a hydrogen atom or an alkali atom means to be implemented in a manner known per se, the reaction according to the following reaction scheme runs:

(ID

(HD

RO

(D

35

40

45

If appropriate, the reaction can be carried out in the presence of an organic solvent are, preferably the reaction is carried out with heating.

In this reaction, a commonly used acid binding agent such as a organic base, such as triethylamine, benzyldimethylamine, pyridine or 2-methyl-5-ethylpyridine, or an inorganic base, such as. B. sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate, be used. When using a compound of the formula III in which, if M is a hydrogen atom means, the use of an acid-binding agent is appropriate. ho

The reaction can usually be carried out at a temperature ranging from 0 to 80 ° C will. If necessary, higher or lower temperatures can also be used.

If h as the reaction medium an organic solu- ₅ is used solvents can include liquid chlorinated hydrocarbons, ethers and ketones used as such a solvent for example, liquid hydrocarbons (benzene, xylene, hexane)

^{W <} Dir The reaction time is suitably selected depending on the reaction temperature, the reaction components and other reaction conditions, but the reaction is usually carried out for 1 to 10 hours.

If necessary, the reaction can be carried out in a nitrogen gas stream.

After the reaction has ended, the product can be further removed by filtering off the salts formed Washing the filtrate with water or an aqueous carbonic acid and drying with anhydrous sodium sulfate and removal of the solvent, whereupon the product is purified if necessary

^W1 Most of the compounds of the formula I obtained by this process are oily substances which are generally insoluble in water, but which are in organic solvents, for example alcohols. Benzene, xylene, hexane, ethers, ketones, chlorinated hydrocarbons and hydrocarbons, are soluble. . L-Li-L.

When using them, they can be used according to the usual Working methods in the field of agriculture and horticulture are used

When the compounds according to the invention are used as fungicides in agriculture and horticulture are used, they are diluted with water used directly or in a mixture with carrier substances and to wettable powders, emulsifiable concentrates, Dusts, granules or pastes according to known and usually m chemical Industry for agriculture formulated procedures applied. Examples of solid carriers: are inactive substances such as talc, clay, kaolin, Montmonllor.it. Diatomaceous earth and calcium carbonate. As liquid carriers, either solvents or also nonsolvents, in which the active ingredients dispersed or dissolved by auxiliaries can be used, for example alcohols, Benzene, xylene, dimethylnaphthalene, heavy aromatic gasoline, dimethylformamide and surfactants Medium. . ..

To ensure their effectiveness, they can in a mixture with such auxiliaries used in the chemical industry for agriculture, such as general spreading agents, emulsifiers, wetting agents or adhesives can be used. They can also be mixed with insecticides. Acaricides and nematocides such as B. organophosphorus compounds. Carbamate compounds, chlorine-containing compounds, dinitro compounds, with fungicides, such as organophosphorus compounds, organic sulfur, copper compounds, dithiocarbamate bonds, dinitro compounds, antibiotics, with herbicides such as substituted phenoxyyerbine fertilize carbamate compounds, urea compounds, triazine compounds, chlorophenols, substituted « Diphenyl ether, aniline compounds and with changed chemicals or fertilizers for the farmer shaft can be used.

When used, the fungicides according to the invention can be used directly in the case of a powder material can be sprayed with an atomizer onto the leaves or stems of plants or the seeds be treated with it. In the case of emulsifiable concentrations, these can be reduced with water

in the formula I standing sulfur atom by a Oxygen atom is replaced. Trial results for the fungicidal activity with regard to such compounds are given below as comparisons brought.

In the following examples, the preparation process for the active compounds according to FIG Invention described for example.

example 1

14.6 g of benzylphosphonic acid ethyl ester chloride and 7.5 g of 4-methylphenol were dissolved in ISO ml of benzene. 6 g of triethylamine was added dropwise with cooling, and then the mixture was stirred at 60 ° C. for 3 hours. After cooling, the benzene solution was washed with cold water and dried over anhydrous sodium.

desired concentration can be diluted and sprayed onto the leaves or stems of the plants can be applied with a sprayer, and in the case of wettable powders these can be applied through Spray with a sprayer as a suspension s of the desired concentration with water and the like can be applied, and in the case of granules, these can be applied to the floor as such or be spread by means of a sprayer.

The fungicides according to the invention are usually used in an amount of 25 to 100 g, preferably 40 to 100 g, especially 60 to 80 g of the active ingredient used per 10 ares, if desired however, they can also be used in smaller or larger quantities. The amounts used ι s vary depending on the type of active ingredients, the application method, the application period and the purpose of the application or the composition of the fungicides.

In contrast to the usual so far to combat most of the major diseases of Rice plants applied fungicides, which have serious disadvantages in that they are due to direct and indirect toxicity to humans and animals due to the content of heavy metals such as mercury and Arsenic, showing adverse effects, the fungicides according to the invention completely lack this disadvantage and moreover, they have excellent fungicidal activity when applied to rice diseases, especially burn, brown spots and leaf sheath burn.

One of the characteristic properties of the active ingredients (benzylthiophosphonic acid ester) according to of the invention is that it has excellent fungicidal activity against Pincuralia oxyzae, Cochliobolus miyabeanus and Hypochnus sasakii compared to compounds (phosphates) have at which that between the phosphorus atom and the group

40 X

• 15th

sulfate dried. After the benzene had been distilled off, 14.9 g of one which could not be distilled at 150 ° C./0.1 mm Hg were obtained pale yellow oily product, namely benzylthiophosphonic acid - O - alkyl - S - (4 - methylphcnyO-ester receive.

Manufacture of the raw materials

Benzylphosphonic acid alkyl ester chlorides, the starting materials, were produced according to the following reaction scheme:

V-

CH ₂ Cl + PCl ₃

AlCl ₃

-CH, - P

O Cl

Ii /

Cl

"O-

H ₂ CO

P-Cl

RO

R, Y and π have the same meaning as for Formula II.

H ₂ CO

P-Cl
C ₂ H ₅ O

A. 133.5 g of aluminum trichloride were suspended in 303 g of phosphorus trichloride and 63.3 g of benzyl chloride were gradually added with stirring until a uniform reaction mixture was obtained. After the excess trichloride had been distilled off under reduced pressure, the mixture was dissolved in 4 to 6 times the amount of dichloromethane and water was gradually added at -20 to -SO ⁰ C until the crystals of the aluminum chloride hydrate were added

say goodbye. After the aluminum trichloride hydrate has been removed by filtration and distilling off the dichloromethane, 66 g of benzylphosptionyl dichloride were obtained obtained at 107 to 108 ° C / 0.4 mm Hg.

B. 26 g of the benzylphosphonyl dichloride obtained were dissolved in 100 ml of ether and cooled to OT.

6 g of ethanol and 13 g of triethylamine were in 100 ml Ether dissolved and the ethereal mixture added dropwise to the cooled ether solution with stirring below admitted by OC. After the addition was complete, stirring was continued at OC for 2 hours proceeded and the precipitate formed removed by filtration. The filtrate was made by distillation concentrated and distilled dor residue, wherein

17.6 g of ethyl benzylphosphonate chloride
98 ° C / 0.1 mm Hg were obtained.

Example 2

■ _ / V-

H ₂ CO

CI-

C ₂ H ₅ O

17.0 g of ethyl 4-chlorobenzylphosphonate chloride and 6.6 g of thiophenol were dissolved in 150 ml of benzene. 6 g of triethylamine were added dropwise with cooling and further stirred for 10 hours at room temperature. Then the benzene solution was washed with cold water and dried over anhydrous sodium sulfate. After distilling off benzene, 15.1 g of pale yellow oily 4'-chlorobenzylthiophosphonic acid [O-ethyl-S-phenyij-cäier which could not be distilled ^{at 140 3 C / 0.1 mm Hg were obtained.}

Example 3

H ₂ C _-

CH ₁ O

J!
PS

13.6 g of methyl benzylphosphonate chloride and 8.7 g of 4-chlorothiophenol were dissolved in 150 ml of benzene. While cooling, 6 g of triethylamine were added dropwise and the mixture was further stirred for 2 hours at 70 ° C. After cooling, the benzene solution was washed with cold water and dried over anhydrous sodium sulfate. After the benzene had been distilled off, 14.4 g of 1'4 ¹ O ⁰ C ¹ O, f mm Hg non-distillable pale yellow oily benzylphosphonic acid [O-methyl-S- (4-chlorophenyl)] _s ester.

Example 4

H ₁ C

C ₂ H ₁ O

15.5 g of 4-methylbenzyl chloride and 66 thiophenol were dissolved in 160 nut benzene

Polyoxyethylene nonylphenol ethers (emulsifier) were broken into a wettable powder formulated and mixed and applied diluted with water.

Example 6

50 parts of benzylthiophosphonic acid [O-ethyl-S-phenyl] ester. 30 parts of xylene and 20 parts of an emulgalor (mixture of calcium alkyl sulfonate, polyoxyethylene phenyl phenol ether and polyoxyethylene sorbitan alkylate) were formulated into emulsifiable concentrates by mixing and stirring and with Diluted water applied.

Example 7

2 parts of benzylthiophosphonic acid - [O - methyl-

S-phenyl] ester, 98 parts of a mixture of talc and clay turned into a dust by breaking and Mix the formulated and the product as it is

ίο was applied.

Example 8

5 parts of 4'-chlorobenzylthiophosphonic acid [O-ethyl-S-phenyl] ester, dissolved in a solvent, 95 parts of powdered clay granules of 0.2 to 2 mm diameter sprayed in a V -shaped mixer while rotating and after Drying granules obtained. These were applied as they were.

^{} 0} example 9

30 parts of benzylthiophosphonic acid - [O - methyl-

S- (4-chlorophenyl)]: - ester, 68 parts clay and 2 parts Polyoxyäthylennonylphenoläther were by Bre-

Chen and mix to a wettable powder formulated and applied diluted with water.

Example 10

50 ¹ part of 4'-methylbenzylthiophosphonic acid [O-methyl-S-phenyOhester. 30 parts of xylene and 20 parts of an emulsifier ^ (mixture of calcium alkyl sulfonate, polyoxyethylene phenylphenol ether and polyoxyethylene sorbilane alkytot) were applied by mixing and stirring to dilute concentrates with water.

geWet. 6.0 g of triethylamine were added dropwise Add cooler and continue the mixture «! Stirred for 10 hours at room temperature. then the Berao solution was washed with pressed water and dried over anhydrous sodium sulfate. After the benzene had been removed, 14.0 g of pale which cannot be distilled at 15G ° C / Qtl mm Hg yellow Ugem 4'-methylben * ytthiophosphonic acid [O »ätrtyI * -S-pBrcniyr | f. ester.

In the following examples iat the preparation of Fungicides and their application are described.

Example S

40 parts of benzylthtophosphonic acid [Q-methyl * S- (4-methylphenyD> ester, 58 parts clay and 2 parts

Example Il

2 parts of 4'-chlorobenzy! Thiophosphonic acids 0-mc-

lhy ^ S - (. 4-eblwpheiiy! »ester and 9 *" file a »Ge

mechcs au »Talk and sound were broken through and blending into a dust and such. as they were, applied.

Example 12

5 parts of benzylthiophosphonic acid | O-methyl-S- (4-chlorophenyl) i> ester. toasted in a solvent were to 95 parts of powdered clay granules about 0.2 to 2 mm in diameter in Spray on a V-shaped mixer while rotating and granules received after drying. This was applied to the floor in this form

Application example c

Test results about dl < fungicidal effectiveness of the foundational compounds ver Indications in the following »Tables II and H! called.

a) Tests against fire (pot test)

Paddy rice (variety Jukkoku) was grown in pots 12 cm in diameter and the suspensions of the test chemicals were sprayed onto the rice plants at their young early stage of growth. From the next day on, the treated rice plants were kept in greenhouses under high humidity at a temperature of 25 ^° C. for 48 hours. During this period, a suspension of rice blight pathogen spores was sprayed twice for inoculation. After the inoculated rice plants had been kept in the greenhouse for 7 days, the disease infestation assessment per pot was carried out and rated to the extent of 0 (no infestation) to 5 (severe infestation).

The comparative values for the test chemicals were determined by the index number derived from the disease infestation score of the rice plants in the treated

Pots compared to those received in the Vetgleich pots were calculated.

b) Attempts against plant pathogens
(Agar dilution method)

The test chemicals were mixed with the agar culture medium from potatoes mixed to the prescribed concentration. After the medium is in Shells 9 cm in diameter cast and coagulated was. the plant pathogens were inoculated. After cultivation at 27 ° C for 4 days the growth conditions of the plant pathogens and the minimum concentration were examined the growth inhibition noted.

Also set out in Table II are comparisons made in the same manner as above were, however, compounds with the similar structures, compounds according to the invention, however, in which the sulfur atom was replaced by an oxygen atom, was used.

Table U

Test results of the fungicidal effectiveness against fire (pot test)

Yorhiiulim)! concentration Case Phylotoxicity t'ischlüxi / ita't as a. i. evaluation (ppml number 1 500 1.2 > 0.5 No. 2 SOO 1.4 __ > 0.5 No. 3 500 1.2 > 0.5 Benzylthiophosphonic acid [0-ethyl-0- (4-chloro- 500 3.0 > 0.5 phenyl)] - ester (comparison) No. 4 500 1.2 - > 0.5 No. 5 500 1.6 - > 0.5 No. 6 500 1.6 - > 0.5 No. 7 500 0.9 - > 0.5 No. 8 500 1.6 - > 0.5 No. 9 500 2.0 - > 0.5 Benzylthiophosphonic acid [0-iUhyl-Opheny!] - ester 500 4.0 (Comparison) Phenylmercuric acetate (hand-held product, comparison) 20th 1.5 0.084 Not treated (control) 5.0 Zwwsb ^ comparison) 500 4.5 > 40 O-Mcthyt-O-cyclohexyl SOO 2.2 0.055

Tabcttc 111

Concentration of inhibition of the growth of pathogen pathogens

Vetbtnilunts

No. t No. 2 No. 3 No. 4 No. S 'does"

Pirieurulln oxyuic C'uvhhobutua
mivubciMua

(ppm)

SO
100

so

100
100

(ppm)

200
100
200
200

tlypochnwt

(ppm)

200
200
200
SOO
SOO

Alictnurln

klkuchlnnu

llirbsc)

(ppm)

200 200 200 200 200

Myvosphnerollii l-'usurlum mclonls oxyspoftum (nurke) (ppm) (ppm) 100 too 100 100 100 100 100 too 100 too

. "._ ..- JHMl MtotmaJs Wuahitumsiiammuiiigskeiucntruun.
') m / jiMn dar VnMmMingm »HmIi dia» Wehen «te in Tntwlk I.

') ppm means minimal growth inhibition / ciiltatioii. ') The numbers of connections are the same as in Table 1.

continuation l'iricuralia oxy / ac C'tichliobiilus
inivabeamis llypoehnu-.
sasakii Allcinaria
kikuehiana
Il rbsel Mycosphaerella
inelonis
((toad) lusarium
oxysporium connection (ppm) (ppm) (ppm) I ppm I (ppm) (ppm) 50 100 200 200 100 100 No. 6 50 100 200 200 100 100 No. 7 50 100 200 200 100 100 No. 8 50 100 200 200 100 100 No. 9 200 > 200 500 > 200 100 500 Zineb
(Default)

Claims (1)

Patent claims: in which R is an alkyl group with 1 to 4 carbon atoms, the radicals X and Y are each a hydrogen atom, chlorine atom or methyl group and η 0 or 1, characterized in that benzylthiophosphonic acid alkyl ester chloride of the general formula I