DE1545787A1 - Process for the production of phosphonic or thionophosphonic acid esters - Google Patents

Description

FARBENFABRIKEN BAYER A LEVERKUSEN -Bayerwerk

Hu / Ks "

Process for the production of phosphonic or thionophosphonic acid esters

The present invention relates to methods of manufacture of phosphonic or thionophospaic acid esters of 3-0xypyridines with biocides, especially insecticides and acaricides Properties.

German Patent 910 052 already describes, inter alia, 0,0-dialkylthionophosphoric acid esters of 2-, 3- and 4-oxypyridines. According to the information in the aforementioned patent, such compounds have a good insecticidal and acaricidal activity} they are therefore suitable for the production of pesticides, in particular for the destruction of aphids and acarids. Phosphonic acid derivatives of 3-oxypyridines, ie compounds of the general constitution _Y

(I)

are not yet known from the literature,

... ^ BAD ORIGINAL

In the above formula, R and R ¹ stand for identical or different lower alkyl groups with 1 to 6 carbon atoms, R ¹ can also represent an aryl radical optionally substituted one or more times by halogen atoms and / or lower alkyl or alkoxy groups; X represents an oxygen or sulfur atom and Y represents a halogen atom or a lower alkyl group; the index η has a value of Mull, one or two.

It has been found that compounds ier the above constitution in a smooth reaction and good yields obtained when using 3-hydroxypyridines of the general formula

(II)

with phosphonic or thionophosphonic acid ester halides of the general structure

RO Ϊ

^ P-shark
- R '/

(III)
implements *

In the last-mentioned formulas, the symbols R, K ¹ , X, Y and η have the meaning given above, while Hal stands for a halogen, preferably chlorine, atom.

Furthermore, it was found that the products are generally

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nen constitution (I) due to excellent insecticidal, especially but have acaricidal and nematocidal properties; in this respect they are those from German patent specification 910 well-known analog built and then next comparable Thionophosphoric acid esters are clearly superior and thus represent a real asset to technology.

The course of the process according to the invention will be explained in more detail using the following reaction diagram:

i ^ OR

+ HaI-P ^ Saurebi.1- (yw-i- "^ ■ R ¹ demittel

Civ)

In the above equation, R, R ¹ , X, Y, Hai and η have the same meaning as given above.

Preferably, however, R and R ¹ stand for straight-chain or branched, lower alkyl groups with 1 to 4 carbon atoms, such as the ethyl, ethyl, n-propyl, isopropyl, n-, see- and tert-butyl radical; R ¹ also preferably denotes a phenyl, mono- and dichlorophenyl, i'olyl, Lilethylchlorphenyl- or anisyl radical, while Y represents a methyl group or a chlorine atom and the index η preferably aen has the value zero or 2.

cd The method according to the invention is preferably carried out in the presence of

co erter organic solution or. Diluent carried out.

° Low-boiling ones in particular have proven themselves for this purpose in aliphatic ethers, such as diethyl and Llbutyl ethers, * J aromatic hydrocarbons, e.g. benzene, toluene, Xylene, chlorobenzene, and also low molecular weight aliphatic ke-

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tone, ζ. B. Acetone, iviethyläthyl-, oiethy 1 isopropyl- and lü isobutyl ketone and kitriles, e.g. B. aceto- and propionitrile.

. In and iiiäthylaniiin questioned Mach a preferred Auslührur.gslom the claimed;. "In addition, taking the process to transpose, expediently in the presence of Säureaa-receptors before As such, particularly coming alkali metal hydroxides or carbonates as well as tertiary amines such as pyridine, ^f irimethylan In the process, the solution or suspension of a salt, preferably an alkali or ammonium salt, of the relevant> oxypyridime is first produced and this is then generally made to react with the corresponding exidic (thiono) phosphonic acid ester halide for the purposes of the present invention.

It has always been used to achieve good yields and recovery pure procedural issues proven to be advantageous, di? Reaction at elevated temperature (preferably 30 to 80 0 or the boiling point of the reaction mixture). In the end it is useful to complete the implementation that Mixing after the unification of the Ausgarxgskompo. 'Are still longer Time (1 to 8 hours) after heating to the specified temperatures to stir before you can use methods that are known in principle worked up.

Lie as the starting material for the inventive method required 3-Hyaroxypyriaine tir.d in the literature beucr.rieueri According to the information available there can also be in technical form Jkafcsstabe can be easily made.

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The present invention available (thiono) phosphonic usually fall in the form of colorless to slightly yellow-colored UIE _t the laeeen not be distilled without decomposition, even under greatly reduced pressure, but increased by "incipient distillation", that is to say prolonged heating under reduced pressure to weak to moderate Temperatures can be freed from the last residues of solvent and other volatile vine components and can be kept pure in this way.

The process products are characterized by relatively low heat release toxicity and phythotoxicity - as already mentioned above - with excellent biocidal, especially insecticidal and acaricidal properties; they are therefore found as pests Kämpfungeirittel, especially in the plant protection, against sucking and biting insects, dipteras, beetles and mites use. Particularly noteworthy is their excellent action against Phosphoric acid ester-resistant spider mites.

The products of the process are used for the aforementioned purpose by known methods, i.e. in the form of the customary ones Formulations such as solutions, emulsions, powders, pastes and Granules. These are produced in a known manner, e.g. by stretching the active substances with solvents and / or Carriers, optionally with the use of emulsifiers and / or dispersants. In the case of using Water as a solvent can optionally be organic liquids be used as auxiliary solvents (see e.g.

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"Agricultural Chemicals", March 1960, pages 35 to 38). As auxiliaries for the production of such formulations come essentially in question: organic solvents, such as optionally chlorinated, aromatic hydrocarbons, e.g. Benzene, toluene, xylene, chlorobenzene, paraffin hydrocarbons, for example petroleum fractions, alcohols such as methanol, butanol, Amines, e.g. B. ethanolamine, dimethylformamide and water; solid carriers, such as natural and synthetic minerals, e.g. B. kaolin, clays, talc, chalk, highly dispersed silica, Silicates; Emulsifiers, such as non-ionic or anionic emulsifiers (e.g. polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ether), alkyl and aryl sulfonates, also Dispersing agents, such as lignin, waste liquor and methylcellulose.

The active ingredients which can be prepared according to the invention can be present in the formulations alone or in a mixture with other known bioids.

The active substances are generally in one concentration from 0.1 to 95 #, preferably 0.5 and 90 #, are used.

The use as a pesticide takes place in the form; the pure active ingredients and their formulations or the application forms prepared therefrom, for example ready-to-use Solutions, emulsions, suspensions, powders and granules. The application is done in the usual way, for. B. by Pouring, spraying, atomizing, gasifying, smoking,

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scatter and deaden.

The excellent biological properties of the process products when used against various types of animal Pests and their technical superiority over the closest comparable compounds of the state of the art from the test results compiled in the following table:

Insecticidal and acaricidal effectiveness

Active ingredient (constitution) Warm-blooded animals application Active ingredient

torlicity (DLc _Q rat per os inmfi4 {g)

against

concentration in $>

Al degree of pest kill in *

(according to the procedure, Example 1)

Spider mites
(resistant)

Aphids

0.1 0.01

0.01 0.001

100 95

100 70

(according to the procedure, example 2)

Spider mites 0.01 100 (resistant)

Horseradish leaf beetle 0.01 100

0.001 30

(ν according to the procedure Example 3)

1000 without findings

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Mosquitoes

0.1

100

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Warm-blooded - / ---_- killing f

,., ^ ₁ toxicity Q active ingredient grade of

15 4. · 'j / ( ^DL <i0 ^rat ' application concentra- pest

Active ingredient (constitution) per ^ os in mg / kg) against tion in # in 1 »

0-P

OC

(according to the procedure, Example 4>

(known from DBP '910,652fr page 7, Connection 24)

5 O-CH

CH ₂ -CH-

(according to the procedure, Example 5)

Spider mites 0, 01 100 (reelstent) Horseradish ... o> T. . TOO Mattiäfer / " ^v στ 90 · Aphids O, 01 100 Or 0OT 0

Aphids

0.01 O _r 00T

Individual experiments to determine the biological properties

the products of the process were carried out as follows:

A) Testing the effectiveness against horseradish leaf beetles Purpose of producing a suitable active ingredient preparation is mixed

1 part by weight of the active substance in question with parts by weight of acetone or dimethylformamide as auxiliary solvent adds one part by weight to this premix

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a commercially available non-ionic emulsifier based on an aryloxy polyglycol ether and finally dilutes the concentrate obtained with water to the desired active ingredient ! concentration.

Hit the active ingredient solution prepared in the manner indicated above, horseradish leaves (Cochlearia aromatics) are sprayed to runoff and then they are populated with horseradish leaf beetles (Phaedon cochleariae). The evaluation is carried out after 72 hours by determining the degree of death of the beetles in tons.

B) Testing of the effectiveness against spill mites Bcüoenpflaneen (Phaseolus vulgaris) from about 10 to 30 cm in height are sprayed to the drip point with an active ingredient preparation prepared as described under A. The plants are heavily infested with all developmental states with a resident strain of the common spider mite (letranychus urticae). The evaluation of the experiment is carried out after 48 hours by counting the dead animals, the degree of destruction being given as usual in j (.

C) Testing of the effectiveness against aphids

Bean plants (Viola faba) which are strong infested by the black bean aphid (Doralis fabae) are splashed to the point of dripping wet.

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VerBUchaauevaluation takes place after 24 hours by counting of the pests that were either on the surface of the earth or still on the plants. The mortification §R "d is auegecrüekt as usual in Jt"

D) Test: the effectiveness against SteehaueRen About 8 ble 12 mosquitoes of the species aedes Egypti are brought under ebgtdeöfete patriachals, in which there are drip-nasal filter papers which have been sprayed with an active substance solution that has been quietly prepared in the above mentioned.

After 180 minutes, the test is evaluated by determining the degree of destruction of the pests in percent.

B) testing the efficacy against flies f- Bow ttiäfifle worketh described under A) off Preparation: is pipetted onto a filter paper disc of 7 cm DurBhinesBer. Letctere is placed wet on a glass in which there are 50 fruit flies (Drosophila melanogaster) and covered with a glass plate> H & oh 24 hours the degree of destruction is determined in percent.

F) Testing for effectiveness against caterpillars. Km sprayed cabbage leaves (Brasaica oleracea) with an active ingredient removal prepared as indicated under A) and covered the leaves with a neutral coat of cabbage cockroach (Plutella maEculipenniB). The evaluation is carried out after 4 days by determining the killing level as a percentage

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- tPa ..- ■■■ ·

6) Testing of the 'effectiveness against mosquito larvae To produce an appropriate preparation of the active substance, 2 parts by weight of the active substance are left in 1,000 parts by volume of acetone which contains 1 part by volume of benzyl hydroxydiphenyl polyglycol ether. The solution obtained in this way is diluted with water to the desired concentration in each case.

The aqueous active ingredient preparations are then filled into glasses and about 25 yellow fever mosquito larvae (Aedes aegypti) are placed in each glass. The degree of destruction is determined in percent after 24 hours.
The following examples illustrate the claimed ancestor:

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example 1 χ

28.5 g (0.3 mol) of 3-hydroxypyridine are dissolved in 150 ecm of methyl ethyl ketone solved. This solution is mixed with the equivalent amount (0.3 mol) of Natriumine thy lat, then stirred for another Hour at 50 ^ and then 66 g (0.3 Mol) Phenylthionophosphonaaure-O-ethyl ester chloride to the reaction mixture. The latter is then heated to 60 ° C for about 5 hours and then stirred in the cold for several hours. Finally, the insoluble particles are sucked off and shaken the piltrate with a little water / benzene and dries the benzene Layer over sodium sulfate. That solvent is not used removed under reduced pressure and the reaction product, phenylthionophosphonic acid-0-ethyl-0- / pyridyl- (3i7ester, distilled in a high vacuum.

The yield is 47 g (57% of theory). Analysis;

Calculated for "in Kol weight of 279"

M 5.02 *,
Found; H 5 '£ 10.

to example 2t

Ξ V ^N OC ₂ H ₅

~ * In an analogous manner as described in Example 1 °> reaction of 3-HydroxJpyridin and Methylthionophosphonsäure-O-äthyleeterchlorid the Methylthionophoephonsäuro-O-ethyl-O- ^ J'yri-

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* yl- (3); 7e8ter obtained.

Analysis;

Calculated for a molecular weight of 217: N 6.45 #; S 14,? 5

Found: N 6.57 *; S 14.39

Example 3 »

By Umset2ung of 3-hydroxypyridine and lüethylphosphonsäure-O-äthylesterci.lorid as described in Example 1, the theory is obtained in a yield of 38 $> the Methylphoophonsäure-O-ethyl-O ^ pyridyl (3l7 ^{esi he} ·

Analysis:

Calculated for a molecular weight of 20 ".

N 6.96 i> \
Found: N 7.48 ^;

Example 4:

The abovementioned compound is prepared in a manner analogous to that described under Example 1 by reacting
1-hydroxypyridine and i-thylthionophosphonic acid O-ethyl ester chloride.

The yield of ethylthionophosphonic acid-0-ethyl-0- / pyridyl- (i27 ester is £ 38 of theory.

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0 «corresponds to a molecular weight« * »2311

H 6.06 % i iefundent N 6.74 ^ i

Example 5 *

Under similar reaction conditions as described in Example 1 is obtained in a yield of 82 i "of the theory by reacting 3-hydroxypyridine _un <j Phenylthionophoaphonßäure-0-eec.-butyl3Bterohlorid the PhenylthionophoaphonBäure-O-eec-

Analysis"

Calculated for a molecular weight of 307 »

N 4.56 J6 $ P 10.1 *; S 10.44 Foundi N 4.53 * 5 P 10.13 5 ^ 1 S 10.53

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Claims (5)

Patent claims: 1) Process for the production of phosphonic or thionophosphonic acid esters, characterized in that there are 3-oxypyridines the general formula with Phoephon- or Thionophosphonsäu.reesterhalogeniden of the general formula RO ^ H ^ P-HaI R "" reacted, where in the aforementioned form / .n R and R ¹ stand for identical or different lower alkyl groups having 1 to 6 carbon atoms, R 'also an aryl radical optionally substituted one or more times by halogen atoms and / or lower alkyl or alkoxy groups X represents an oxygen or sulfur atom, Y a halogen atom or a lower alkyl group and Hal a Haxogen atom, while the index η has the value zero, one or two. 2) Phosphonic or thionophosphonic acid esters of the general formula X _nD (Y) ₁ in which R, R ¹ , X, Y and η have the meaning given in claim 1. ., 9 0 & 86 &> 16βΐ ' Le A 9224 3) Pesticides consisting of or containing Compounds according to claim 2. 4) method for combating pests, characterized in that that one uses compounds according to claim 2 as an active ingredient. 5) processes for the manufacture of pesticides, characterized in that compounds according to Claim 2 are used. 9 09 ^ 60 / 16.8 ^ Le A 9224