DE1792436A1 - Schaedlingskämpfmittel with depot effect - Google Patents

Description

VEB PAEBEHFABEIK WOLi ¹ EIf Wolfen, May 2, 1968

(0.Z.1056)

Inventor: Dr. Walter Steinke, Wolfen Dr. Eeinhard Bachmann, Engelsdorf Dr. Dieter Meißner, Leipzig Dipl.-Chem. Roland Schelle, Wolfen Dr, Manfred Born, Dessa-j-Haideburg Dipl.-Agr. EaIf Kleiner, Leipzig

Pesticides with a depot effect

The invention relates to pesticides with a depot effect, which are crosslinked, high molecular weight carrier materials Porous organic substances with an inner surface and, as active substances, the phosphoric acid derivatives known per se the general formula

contain, in the A and B ■ lower alkoxy groups with 1-4 carbon atoms, lower alkyl amino groups, lower dialkylamino groups and the amino group, where A and B can be identical or different and

C µ -CH-GCl ₃ , -0-0H-CCl ₂ , -OCHBr-CCl ₂ Br, -0-C-CH-CO-CH ₃ , OH

-OC-CC1-CON (C ₂ H ₅ ) ₂ , -OC-CH-CO ~ N (CH ₃ ) ₂ , -OC-CHCl

Au 'Arr

CH ₃ CH ₃ i

109846/1760 egg

CO.Z.1056)

-Y-CH ₂ -CH ₂ -S-CH ₃ , -

-Y-CH ₂ -CH ₂ -SO-CH ₃ , -Y-CH-CH ₂ -SO-C ₂ H ₅ , -;

CH ₃

-S-CH-COOC ₂ H ₅ , -S-CH ₂ -CO-HH-CH ₃ , -S-CHg-CH-CHg, CH ₂ -COOC ₂ H ₅

-0- / X CH

jind

-Br and X and T

0 or S mean »

It is known that many derivatives of phosphoric acid have excellent biocidal properties, which they incorporate into the Put animal souls such as insects and theirs Different stages of development, spider mites and fiematoden effectively su fight · Most of these! phosphoric acid derivatives are relatively unstable, they decompose in the presence of water quickly or evaporate owing to their high vapor pressures ο, so that after a relatively short time a strong Decrease in effect occurs

The aim of the present invention is to create preparations which, in the vicinity of the objects to be protected, have a have a much longer effect without it the application rate expected to be increased

109846/1760

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The preparations according to the invention particularly contain those active ingredients which are either easily released into the environment due to their high vapor pressure or those which due to their ability to penetrate into the nature of the plants to be protected, where they can be absorbed from the surrounding soil. The stabilization of the phosphoric acid derivatives is achieved by attaching them to crosslinked macromolecular, porous organic substances which have ionizable groups such as SCLH, SO ₃ Me, C (XH, COOMe, QH, QMe and

Ο) Λ
QH E ₃

and in which Me - Ha, K, Y2 Ca, Y2 Mg or Y3 Al and E ₁ , E ₂ and E ₃ - H, -CH ₃ , -C ₂ H ₅ , -OH ₂ CH ₂ HH ₂ and -CH ₂ CH ₂ OH mean, are adsorbed

By varying the degree of crosslinking and the content of ionizable groups have absorption and desorption properties and change the hydrophilicity of the preparations according to the invention within wide limits and thus to the desired Adjust intended use. For example, by increasing the number of ionizable groups in the macromolecule the carrier substance improves the wettability of the preparations with water and thereby the delivery of the active ingredients to a watery environment can be facilitated. Conversely, by reducing or eliminating the content of ionizable

1 Ü9846 / 17R0

Groups are obtained a hydrophobic carrier, the specific Weight can be adjusted so that the preparation in water remains buoyant! A great advantage of the preparations according to the invention is that they can be easily and Can be prepared by mixing the carrier substances with the liquid or liquefied active ingredients without having to do so plasticizing is necessary. B · by polymerizing styrene in Presence of crosslinking substances such as divinylbenzene in a suitable solvent and, if necessary, subsequent Sulphonation or chloromethylation and reaction with tertiary Amines or by polymerization of unsaturated compounds which carry carboxyl or OH groups and with crosslinking ! Divinylbenzene in a manner known per se · Such solvents are preferably aliphatic ^ hydrocarbons · Duroh variation the amount of solvent the degree of porosity of the carrier can be changed

The following examples are intended to explain the invention without restricting it to these examples:

•Example 1:

80 g of a porous cation exchanger in the Ha ⁺ loading and with a surface area of the above were used. 35 m ² / g with 20 g of dimethyl dichlorovinyl phosphate and mixed with one another by shaking briefly. A completely dry, free-flowing granulate was obtained.

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Example 2:

There were 70 g of a porous crosslinked with divinylbenzene Styrene polymer with a surface area of 50 m / g with 30 g Dimetnyldiohlorvinylph.osph.at added and by short Shake mixed together. A completely dry, free-flowing and stable granulate was obtained, which is buoyant

Example 3:

40 g of a porous cation exchanger in the Mg ⁺⁺ ~ charge were mixed with 60 g of dimethyldiochlorovinyl phosphate and mixed with one another by briefly shaking. A dry, stable and free-flowing granulate was obtained.

Example 4:

40 g of 0,0-dimethyl-1-0-2,5-dichloro-4-bromophenyl-thiophosphate and 10 g of an oxethylated alkylphenol were liquefied duroh slight heating and with 50 g of one with Divinylbenzene crosslinked, porous styrene polymer mixed. A trooken, stable and free-flowing Granules received.

Example 5:

A mixture of 42 g of methyldemeton-methyl and 18 g 4Q g of a porous styrene polymer crosslinked with divinylbenzene were added to chlorobenzene and dried through brief shaking mixed together. A trooken, stable and free-flowing granulate was obtained,

109846/1760

Example 6:

It contains 50 g of 0.0% dimethyl-S- (S-methyl) -carbaaioylinetnyllithiophosphat liquefied with 5 ml of methanol and with 50 g of one with Diviny! benzene crosslinked porous Styrofoam polymerisates added and mixed together by brief shaking. This produced a dry, stable and free-flowing granulate obtain.

Example 7:

40 g of 0,0-dimethyl-S- (li ^ ethyl) -oarbaiaoylmethyldithiophosphat were melted by briefly heating to 40 ⁰ C and with 60 g of a porous ion exchanger in the 3Sa -load and with a surface of about 35 m / g and mixed with each other by shaking briefly

The prolonged biological action of the compounds according to the invention can be seen from the following examples:

Example 8:

50 mg of the granules described in Example 1 were hung in a gas-permeable paper bag in a 15.1 capacity bottle. 6 flies (Musoa dornestioa) 2 to 4 days old (Musoa dornestioa) were placed in this container at 20 to 25 ° after the times described in the table below introduced, and the time after which 50 # of the introduced flies were unable to fly (EiD ₅ Q values) was determined. Between the individual tests, the vessel was ventilated each time and thereby freed from the active substance contained in gaseous form. 109846/1760

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position after the start of the experiment 1 6 24 28 56 ET ₅₀ ~ values (min.) 17 25 40 46 80.

Example 9:

100 mg of the preparation according to Example 2 were placed in a glass vessel with 3 liters of water. JTaeh the ones in the table below times described were 0.8 ml of the water treated in this way in Petrisohalen, in each of which there are 20 flies on one Paper filters were placed, and the ETcQ values were determined from multiple repetitions was made using 40 mg of a 50 $ liquid DDVP emulsion concentrate instead of the preparation Example 2 carried out

EI ₅₀ ~ values (min.) Days after the start of the experiment 1 14 35 49

Preparation according to example 2 35 32 70 190 180 liquid DDVP emulsion
concentrate 23 23 62 > 360 > 24 h

Example 10t

50 mg of the preparation according to Example 5 and 10 beans (Vicia faba) each were introduced into flower pots measuring 9 cm β 2 to 3 cm below the surface of the earth. The pots were poured with 80 ml of water every 3 days, and after the beans had emerged, 50 aphids (Aphis fabae) were placed on the plants at the specified times. The efficiency was determined 24 hours later. The following resulted

^Values: '.09846 / 1760

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Days after application, o _{on 00 o} c of the preparation ^{Ί0 ά άά} ^

Efficiency (in <f) 100 100 100 60

Example 11:

Using the method described in Example 10, the systemic action of the preparation according to Example 7 against spider mites (letranychus urtioae) on bean plants was determined
(Phaseolus vulgariß) checked · The efficiency · was
about 48 hours determined.

Days after spreading. _{ft 00} .- _K , of the preparation ^{1Ö άά} ^ ^ ⁴

Efficiency (in #) 100- 100 80 40

INÄPSOTS)

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Claims (1)

Patent claims: 1. Pest control agent 1 with depot effect, which as carrier derivatives are porous crosslinked polymerized vinyl groups Compounds with a large surface area and, as active ingredients, the phosphoric acid derivatives known per se of the general Pormel A X B C contain, in which A and B "" lower alkoxy groups with 1 to 4 carbon atoms, lower alkylamino groups, lower dialkylamino groups and the amino group, where A and B can be the same or different, and C * -CH-CCl ₃ , -0-CH-CCl ₂ , -OCHBr-CCl ₂ Br, -0-C-CH-CO-CH ₃ , OH CH ₃ CH ₃ OH ₃ H 0
, -0-CCC-tl (CH ₃ ) ₂ , -OC- Y-CH ₂ CH ₂ -S-CH ₃ , -Y-CH ₂ CH ₂ -SC ₂ H ₅ , -Y-CH ₂ CH ₂ -SO-C ₂ H ₅ , Y-CH ₂ CH ₂ -SO-CH , -Y-CHCH ₂ -SO-C ₂ H ₅ , -Y-CH ₂ CH ₂ N (C ₂ H ₅ ) ₂ , 10 9 8 4 6/1760 ^{0Rl01NAL INftPECTED} - 10 - (O.Z.1056) -S-CH-COOC ₀ H, -S ~ CH -CO-NH-CH-, -S-CH -CH- »CH, I <£ ^ « J Gt CL CH ₀ -COOC ₀ H-. 2 2 5 HH ₂ ■ • »0- / \ _r SCH _Q ., S-CH ₀ ^Λ HH ₀ * CH ₇ ^ ¹ ^ -f Cl
-0— / Λ «Br and Y and X« mean 0 or S, Cl 2 · Pesticides with a depot effect, which are porous, crosslinked, polymerized vinyl group-containing carrier materials Compounds with a large surface which have ionizable groups such as SO-H, SO-Me, COOH, COOMe, OH, OMe and ω / ⁱ carry and where Me ■ Na, K, V2 Ca, V2 Hg or V3 Al and R., Rp and R ₃ * mean alkyl groups, as well as a phosphoric acid derivative of formula I contain « Pe / Pl. 109846/1760