DD152715A5 - SCHAEDLINGSBEKAEMPFUNGSMITTEL - Google Patents

Abstract

1. Process for the preparation of propargyl methanephosphonates of the general formula (I) see diagramm : EP0025179,P5,F2 in which R denotes an alkyl, alkenyl or alkinyl radical having a maximum of 4 carbon atoms or an aryl radical, and X and Y denote oxygen or sulphur, characterized in that the relevant ester of methanephosphonyl monochloride or methanephosphonyl dichloride is reacted with at least the equivalent amount of propargyl alcohol in an aqueous two-phase system in the presence of an inorganic base, preferably with sodium hydroxide solution, as the acid-binding agent, in at least the equivalent amount.

Description

~ Λ " Berlin, 29. 1. 81 AP C 07 F 57 874 18

2 2 O / AP C 07 F / 223 723

Schädlingsbekmittmittittel the field of application of the invention

The present invention relates to pesticides containing propargyl-containing Methanphosphonsäureestern, a process for their preparation Γ) and their use in synergistic mixtures with known pesticides, in particular with insecticidal, acaricidal and pesticidal agents.

Characteristic of the known technical solutions

A number of phosphorus compounds containing propargyl groups are described in the literature as insecticide synergists. For example, DE-OS 2 551 257 and US Pat. No. 3,944,666, US Pat. No. 3,885,031, US Pat. No. 3,709,888, US Pat 3,652,741 and US Pat. No. 3,555,123 claimed benzyl- and phenylphosphonic acid monopropargylalkyl or alkynyl esters? in US Defense Publication T 860 711 Phenylphosphon- - '' is called diazepiparpargylester. Examples of phosphoric esters are: (thiono) phosphoric acid mono- or dipropargyl esters, where halogenated cycloalkyl radicals are introduced as the third ester group onto phosphoric acid, in US Pat. No. 2,693,483 and in

2 2 3 7 2 3

acid alkyldipropargyl ester in European Patent Application 78 100 117.7. Alkanephosphonic acid mono and dipropargyl esters have also been described; Prochloryl chloromethane phosphonate in US Pat. No. 4,001,405, alkyl or alkenyl phosphonic acid propargyl ester having at least 2 C atoms in US Pat. No. 3,856,896 and DE Pat. No. 2,406,783.

These compounds are all synergistically highly effective; only the chloromethanephosphonic dipropargyl ester is a less effective synergist. In general, dipropargyl esters are slightly more effective than monopropargyl esters. Nevertheless, these compounds have not yet found their way into practice. There are two main reasons for this: the majority of the aromatic or aromatic-aliphatic phosphonic acid propargyl esters described above must be prepared by the phosphonic acid dichlorides, which are only accessible in multistep syntheses and therefore expensive. secondly, the end products must be purified to separate from the often highly toxic by-products, such as pyrophosphonates. This is done with the consistently oily substances, preferably by distillation and is due to the very high boiling point and the insufficient thermal stability of these compounds for the chemical technology is a difficult problem to solve. Thus, for the preparation of benzylphosphonic O-propargyl-O-propyl ester in DE-OS 2,551,257 discloses a molecular distillation

Le A 19 872

29. 1. 81

AP C 07 F / 223 723

57 874 18

2237 23 - 3-

prescribed device · "There will torr distilled at a bath temperature of 120 ⁰ C and a pressure of 1 to 1.5 x 10 ~. It is obvious that such conditions in a large system may not be realized Phenylphosphonsäuredipropargylester boiling US-P 3. 860,711 torr at 141 "\ to 142 ⁰ C at 0.14, However, experience has shown already decomposes in the distillation.

In contrast, the aliphatic propargyl group-containing phosphates or phosphates mentioned in US Pat. No. 3,856,896 and European Patent Application 78 100 117,7 have significantly lower boiling points. Nevertheless, the synthesis of larger amounts of product is difficult here, too. "The synthesis of phosphoric acid alkyldipropargyl esters is achieved in good purity by the preparation process described in German Offenlegungsschrift No. 2,926,652, so that optionally a distillation of the reaction mixture is unnecessary. Nevertheless, a constant product quality J can only guarantee at a large-scale production when defined cleaning operations, such as distillation, be made.

It can be seen that the distillation of, for example, the compounds described in the European patent application 78 100 117.7 Phosphorsäureethyldipropargylester and Phosphorsäurepropyldipropargylester in the temperature range between 110 and 140 ⁰ C at 0.1 to 15 mbar pressure can not be carried out without thermal decomposition, the decomposition products smear the distillation apparatus and contaminate the distillate, Nevertheless, the differential thermal analysis shows a strong exothermic decomposition

29, 1. 81

AP C 07 F / 223 723

57 874 18

2237 23 - 4-

beginning or only at 221 ⁰ C, 229 ° C at a heating rate of 4 C / min "The compounds Methanphosphonsäuredipropargylester Methanphosphonsauremethylpropargylester and show, for example, under the same experimental conditions as a still lower decomposition starting at 219 C and 198 ⁰ C.

Surprisingly, however, it has been found that these compounds can be distilled without appreciable decomposition in the pressure range between 0.1 and 15 times. In general, methanphosphonic acid propargyl esters are more readily distillable than the corresponding phosphoric acid propargyl esters having the same number of propargyl groups and the same total number of carbon atoms.

of the invention

The aim of the invention is the provision of new pesticides which, with good plant tolerance and favorable iVarmblütertotoxicity significantly higher insecticidal and / or acaricidal activity than known pesticides,

the essence of the invention

The invention has for its object to find a simple and economically producible new compound, which has an excellent synergistic efficacy in drugs from various chemical classes «

2237 23

29 · 1. 81 723 AP C 07 F / 223 57 874 18 S • 4 © -

The present invention therefore relates to active compound combinations of methanephosphonic acid propargyl esters of the formula I,

H ₃ CP,

OCH ₂ -C ₃ CH. YR

(I)

2237 23

wherein

R is an alkyl, alkenyl or alkynyl radical with

at most 4 C atoms or an aryl radical and

X and Y mean oxygen or sulfur and

A. carbamates, and / or

As carboxylic acid esters, including natural and synthetic pyrethroids and / or

C. phosphoric acid esters and / or D. halocycloalkanes and / or

E. Haloalkanes.

  The synergistic effect of the compounds of the general formula (I) is shown preferably in the

A. Carbamates of the general formula (II)

" Λ

> N-C-O-IT (II)

Le A 19 872

2 2 3 7 2 3 - 5

in which .

R is aryl, heterocycle or an oxime radical which may be substituted,

R is hydrogen or alkyl having 1 to 4 C atoms and

R is alkyl, alkylcarbonyl having 1 to 6 carbon atoms in the alkyl radical, which may optionally be substituted by hydroxy or methylthio, or the radical -S-W, where

W is an optionally substituted by halogen aliphatic radical having 1 to 4 C-atoms, in particular CCl ₃ and CF ₃ , and optionally optionally by CN, halogen, in particular chlorine, methyl, trihalomethyl, trifluoromethylmercapto or NO ₂ substituted aryl, in particular phenyl, or for methoxycarbonyl or

is the radical V-SO ₃ -N-, where. V represents alkyl, haloalkyl or an aryl or alkyl radical optionally substituted by halogen, trihalomethyl, CN, methyl or nitro.

₂₀ Particularly preferred are carbamates in which

R is phenyl or naphthyl, which are optionally substituted by alkyl, alkenyl, alkoxy, Alky! Mercapto each having 1 to 5 carbon atoms, dialkyl

Le A 19 872

2 2 3 7 2 3 - χ -

amino, dialkenylamino up to 3 C atoms, each Al.kyl or alkenyl moiety, halogen, in particular chlorine, dioxolanyl or the radical -N = CH-N (C 1-4 -alkyl) -

Furthermore, carbamates are particularly preferred in which

R ^{4 is} 2,3-dihydrobenzofuranyl, ßenzodioxolyl, benzothienyl, pyrimidyl or pyrazolyl, which are optionally substituted by C,.-Alkyl, in particular methyl or dialkylamino having 1 to 4 carbon atoms per alkyl moiety.

Furthermore, carbamates are particularly preferred in which

4 R for an oxime radical of the general formula (Ha)

R ⁸

< ^IIa >

stands,

in which

7 8

<c R and R are the same or different and are alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkylmercapto, alkoxycarbonyl, carbonylamide, alkylmercaptoalkyl having in each case up to 5 C atoms, CN, aryl, in particular phenyl, aralkyl, an optionally substituted, heterocyclic

Le A 19 872

223 7 23

A radical or alkyl which is substituted by a heterocyclic radical, stand or together represent an optionally C ₁ , -alkyl-substituted dioxolanyl or dithiolanyl radical;

B. carboxylic acid esters of the general formula (III)

OH ¹⁰

QM I

R ^ -C-O-CH-R

in which

R is alkyl, aralkyl, aryl or cycloalkyl, which may optionally be substituted and

R is hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, CN and

R is aryl or a heterocycle, or together with R forms an optionally substituted cyclopentenone ring;

Particular preference is given to carboxylic acid esters in which

R is alkyl of 1 to 6 carbon atoms, which is optionally substituted by optionally halogen-substituted phenyl, cyclopropyl, which is optionally substituted by alkyl, alkenyl, halogen

Le A 19 872

223723

alkyl or haloalkenyl having in each case up to 6 carbon atoms or is phenyl, which is optionally substituted by halogen;

5 preferred are carboxylic acid esters in which

R is hydrogen, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 4 carbon atoms and up to 3 halogen atoms, CN or ethynyl;

furthermore, particular preference is given to carboxylic acid esters in which

R is phenyl, optionally substituted by

C. alkyl, halogen, in particular fluorine or chlorine, optionally halogen- or methyl-substituted phenoxy, optionally substituted. Benzyl is substituted, further for

Furanyl, tetrahydrophthalimido, benzodioxolyl / which are optionally substituted by halogen, in particular chlorine, alkyl or alkenyl having up to 4 carbon atoms or benzyl, and is also cyclopentenone, optionally

is substituted by C 1-6 alkyl, furfuryl, C 1-6 alkenyl;

furthermore, the natural pyrethroids are particularly preferred;

Le A 19 872

20

223723 -il-

C. Phosphoric esters * of the general formula (IV)

in which

X are independently 0 or S and

A is O, S, NH- or a direct bond

between the central P atom and the radical R ¹⁴ is and

12 13

R and R are the same or different and for

Alkyl or aryl and

R ^{14 is} alkyl, aryl, heteroaryl, aralkyl,

Alkenyl, dioxanyl or an oxime residue or a same residue to which it is attached.

15

Particularly preferred are phosphorus esters in which

12 13

R and R are the same or different and for

C, .alpha.-alkyl or phenyl and

Le A 19 872

223 7 23

R is alkyl of 1-4 C atoms optionally substituted by halogen, OH, CN, optionally halogen-substituted phenyl, carbonylamide, sulfonylalkyl, sulfoxyalkyl, carbonylalkyl, alkoxy, alkylmercapto, alkoxycarbonyl; is alkenyl having up to 4 carbon atoms, which is optionally substituted by halogen, optionally halogen-substituted phenyl or alkoxycarbonyl, or for • JO the oxime radical of the general formula (HA)

stands,

'R ⁸

in which

7 8

R and R have the abovementioned meaning, but in particular are cyano or phenyl, or dioxanyl

which is supported by the same remainder

1 4 is tethered to which R is bound

14 or R stands for the same remainder

1 to which it is bound, or R stands

phenyl, optionally substituted by methyl, nitro, CN, halogen, methylmercapto;

Le A 19 872

2237 23

moreover, it is particularly preferred to use C, .alpha.-alkyl or halogen-substituted heteroaromatics, such as pyridine, quinoline, quinoxaline, pyrimidine, diazinon, benzo-1,2,4-triazine; ,

D. Cycloalkanes of the formula (V)

(V)

in which

Hal is halogen, preferably chlorine;

E. Haloalkanes of Formula (VI)

^R18 -C Hal

(VI)

in which

Le A 19 872

2237 23

Hal ¹ . for chlorine or bromine

R for hydrogen or hydroxyl 1 (\ 17

R and R are the same or different for

halogen, alkyl or alkoxy and

R is hydrogen or halogen,

Particularly preferred are haloalkanes / in which

R is hydrogen or hydroxyl, 1 a 17

R and R are the same halogen, alkyl or

Alkoxy having 1 to 4 carbon atoms TO are each alkyl or alkoxy radical and

18 R is halogen.

The insecticidal and / or acaricidal action of the active compound combinations according to the invention is substantially higher than the effect of the individual components. It is also substantially higher than the effect of the already known active compound combinations of 2-iso-propoxy-phenyl-N-methylcarbamate and piperonyl butoxide and corresponds to that of already known Phosphorsäurealkyldipropargylester according to the European Patent 78 100 117.7.

In addition, the phosphonium usable according to the invention

Le A 19 872

223723

ester synergists excellent synergistic efficacy not only in one class of drugs, but in drugs from various chemical groups.

Thus, the phosphonic esters of the formula (I) according to the invention and the synergistic mixtures obtained therefrom represent a valuable enrichment of the art.

The compounds of general formula (I) are new. Only methanephosphonic acid dipropargyl ester is from AG Makhsumov, AM Sladkov and VV Korshak; Izv. Akad. Nauk. SSSr, Ser. Kim 1964 , 733-6 have already been synthesized and methanthionophosphonic acid S-propargyl-O-alkyl esters are mentioned in US Pat. No. 3,065,125.

The invention further provides methanephosphonic acid prepolymers of the formula (I)

X.OCH ₀ -C = CH

H ₃ CP,

YR in which

R is an alkyl, alkenyl or alkynyl radical having at most 4 C atoms or an aryl radical and

20 X and Y mean oxygen or sulfur

Le A 19 872

223723 -il

except Methanphosphonsäuredipropargylester and Methanthionophosphonsäure S-propargyl-O-aikylester.

The phosphonates of the formula (I) according to the invention are preferably prepared from the corresponding methanephosphonic acid chlorides or methanthionophosphonic acid chlorides. The methods known from the literature using tertiary amines as acid scavengers prove to be of little use, as the result a) shows in the synthesis of synergist 1. Prefers

IQ is the synthesis in a two-phase system from the

aqueous solution of an inorganic base and a volatile, inert, sparingly water-soluble solvent is carried out as an organic phase. The yield of this reaction can be improved by using from 0.001 to 100 mol%, preferably from 0.1 to 10 mol%, based on phosphonic acid chloride, of a tertiary amine or quaternary ammonium or phosphonium salt having at least 9 carbon atoms. The tertiary amine is used preferably in amounts of from 1 to 10 mol%, based on methanephosphonate, as a catalyst, while 0.01 to mol% of the quaternary ammonium or phosphonium salts are sufficient.

Suitable organic solvents are halohydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichlorethylene, tetrachlorethylene, chlorobenzene and dichlorobenzene, hydrocarbons such as benzene, toluene, xylene and blends thereof with aliphatic hydrocarbons;

Le A 19 872

223 7 23 - «

Ethers, such as diethyl ether, dipropyl ether, dibutyl ether; * Ketones such as methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone and esters such as ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, butyl propionate.

A selection of suitable catalysts for the process according to the invention is listed below:

Benzyldimethylamine, dibenzylmethylamine, benzyldiethylarain, benzyldi (2-cyanoethyl) -amine, tributylamine, tris-2-ethylhexylamine, stearyldimethylamine, tetrabutylamitium chloride, tricaprylmethylammonium chloride, tris-2-ethylhexylmethylammonium chloride, trioctylmethyl-aramonium chloride, trimethylphenyl-ammonium chloride, trimethylbenzylamine chloride, triethylbenzylammonium chloride , Trimethylbenzylaminoniourine hydroxide, benzyldodecyldimethylammonium chloride, stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, myristyltrimethylammonium chloride, tetrabutylphosphonium chloride, triphenylmethylphosphonium bromide. As inorganic bases are preferably water-soluble alkali metal or alkaline earth metal hydroxides and carbonates such as sodium hydroxide, potassium hydroxide, barium hydroxide, sodium bicarbonate, sodium carbonate and potassium carbonate. Also, slightly water-soluble alkaline earth bases such as magnesium carbonate, magnesium oxide, calcium oxide, calcium carbonate, barium oxide and barium carbonate can be used, but they are advantageously presented together with propargyl alcohol, water and catalyst in the reaction vessel and slurried.

Le A 19 872

223 7 23

-to-

A preferred synthesis of the methanephosphonic acid propargyl esters of the invention is based on methyldichlorophosphine, see formula (II). Oxidation with oxygen or sulfur can easily be used to prepare methanephosphonic acid dichloride or methanthionophosphonic acid dichloride, which can be reacted with propargyl alcohol and, if appropriate, other aliphatic alcohols to give methanephosphonic acid or methanthionophosphonic acid dipropargyl esters or propargylalkyl esters.

Formula (II)

4- HIGH ₂ -C 1 Ch + HYR

π .OCH ₂ -C = CH + 2 HCl

R, X and Y

have the meaning given in formula (I).

Another preferred preparation process starts from methanethionophosphoric acid dialkyl esters or methanephosphonic acid diphenyl esters which are reacted with thionyl chloride or phosphorus pentachloride to give methanephosphonic acid dichloride or methanthionophosphonic acid dichloride, see formula (III):

Le A 19 872

2237 23 \ Z

Formula (III) (formulated with thionyl chloride)

X X

CH ₃ -P (OR) ₂ + 2 SOCl ₂ > CH, -PC1 ₂ + 2SO ₂ + 2 R Cl

X and R have the meaning given in formula (I).

In a further preferred preparation process for Methanphosphonsäuremonopropargylester is also based on Methanphosphonsäurediestern or Methanthionophosphonsäurediestern and sets them with phosgene or oxalyl chloride to Methanphosphonsäure- or Methanthionophosphonsäureesterchloriden from which with Propargylalkohol the corresponding propargyl esters are readily available, see formula (IV).

Formula (IV): (formulated for phosgene)

^X η ν OR

H, CP (0R) _o + Cocio> CH-x-pf + CO ₀ + R Cl

2 ^{2 2} ? \ _C i ²

DT? "X

- ^ ^0R

DT? "

HjC-P ^ + HIGH ₂ -C ₂ CH -> H ₅ CP

^N Cl "

₅ ^ Cl "CCH ₂ -C =CH

X and R have the meaning given in formula (I).

As particularly advantageous Methanphosphonsäurepropargylestersynergisten according to formula (I) may be mentioned, for example:

Le A 19 872

223723

Methanphosphonic acid dipropargyl ester Methanphosphonsäuremethylpropargy! Ester. Methanephosphonic acid ethylpropargyl ester methanephosphonic acid n-propylpropargyl ester methanephosphonic acid i-propylpropargyl ester methanephosphonic acid allylpropargyl ester methanephosphonic acid n-butylpropargyl ester methanephosphonic acid i-butyl propargyl ester methanephosphonic acid 2-butyl propargyl ester methanephosphonic acid phenyl propargyl ester

Methanthionophosphonic acid O, 0 ~ dipropargyl ester methanthionophosphonic acid CO-methylpropargyl ester

Methanethionophosphonic acid CO-ethyl propargyl ester Methanthionophosphonic acid O, O-propyl propargyl ester Methanthiophosphonic acid O-propargyl S-methyl ester Methanthiophosphonic acid O-propargyl S-ethyl ester Methanothionophosphonic acid O-propargyl S-methyl ester

20 The carbaruates (group A) of the formula (II) to be used as mixed components include:

2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-methoxyphenyl, 2-ethoxyphenyl, 2-n or iso-propoxyphenyl, 4-methylphenyl, 4-ethylphenyl, 25 4-n-propylphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-n-propoxyphenyl, 2-allylphenyl, 2- (1-methylallyl) phenyl, S-isopropyl) - methoxyphenyl, 3,4,5-trimethylphenyl, 2,3-dihydro-2,2-dimethylbenzofuran (7) -yl,

Le A 19 872

223 7 23 - »-

2-ϊ _f 3-dioxolane (2) yl-phenyl 7 "/ 2,2-dimethyl-1,3-benzodioxole (DyI, 2,2-dimethyl or 1-methyl-2,3-dihydrobenzofuran (4 ) yl-N-methyl-carbamate, the corresponding -N-methyl-N-acetyl, -N-methyl-N-trifluoromethylthio / -N-methyl-N-dichloromonofluoromethylthio and -N-methyl-N-dimethylamino, respectively -thiocarbamate.

These compounds, their preparation and their use are known (see, for example, U.S. Patents 3,009,855, 2,903,478 and 3,111,539).

The carboxylic acid esters (group B) of the formula (III) which may optionally be used as mixture components include:

Acetic acid - / ^ , 2,2-trichloro-1- (3,4-dichlorophenyl) ethyl 17-ester, 2,3,4, S-tetrahydrophthalimidomethylchrysanthemate, S-phenoxybenzyl Z ^^ - dimethyl-S- (2, 2-dichlorovinyl) -Cyclo-

15 propan-7-carboxylate, (5-benzyl-furyl) -methyl-2,2-

dimethyl-3- (2-methylpropenyl) cyclopropanecarboxylate, (±) ice, trans-3-phenoxybenzyl-2,2-dimethyl-3- (2-methyl-propenyl) cyclopropanecarboxylate) _# 2,2-dimethyl-3-dichlorovinylcis / Trans-cyclopropanecarboxylic acid s6-cyano-3'-phenoxy-4 · fluoro-benzyl ester, 5-benzyl-3-furylmethyl-d-cis (1R, 3S, E) 2,2-dimethyl-3- (2- oxo-2,2,2,5,5-tetrahydrothiophenylidenemethyl) cyclopropanecarboxylate, (R, S) -i-cyano-3-phenoxybenzyl (R, S) -2- (4-chlorophenyl) -3-methyl-butyrate, (-) -3-

Le A 19 782

Il

223723 -

Allyl-methyl-oxocyclopent-enyl- (+) - cis-trans-chrysanthemate, 2-dimethyl-3-dichlorovinyl-cyclopropanecarboxylic acid pentafluorobenzyl ester, / R, S_7 - <-6-cyano-3-phenoxybenzyl ( IR, 1S) -cis, trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate, (S) - <-? - cyano-m-phenoxybenzyl- (1R, 3R) -3- (2, 2-dibromovinyl) -2,2-dimethyl-cyclopropanecarboxylate.

The counted compounds are known and mostly well-known commercial products (see R · Wegler "Chemistry of Crop Protection and Pest Control" Volume 1, pages 87-118, Heidelberg (1970)).

The phosphoric acid esters (group C) of the formula (IV) which may optionally be used as mixture components include:

0,0-dimethyl- or 0,0-diethyl-O- (2,2-dichloro- or 2,2-dibromovinyl) -phosphoric acid ester or thionophosphoric acid ester and O, O-dimethyl- or O, O-diethyl -O- (3-methyl-4-methylthiophenyl) phosphoric or -thionophosphorsäureester.

The compounds of the formula (IV) are known and are readily available by processes known from the literature (cf., for example, US Pat. No. 2,956,073, DE-AS 1 167 324, DE-PS 633 478).

To the still used as blending components

Le A 19 8 72

223 7 23 - ** -

if cycloalkanes (group D) of formula (V) to be used include:

1,2,3,4,5,6-hexachlorocyclohexane. This compound, its preparation and its use is known (see, for example, U.S. Patent 2,502,258, Chem. + Industr., 1945, p. 314).

The halogen alkanes (group E) of the formula (VI) which may optionally be used as the mixture components include:

1,1,1-Trichloro-2,2-bis (4-chloro- or 4-methoxyphenyl) -ethane, 1,1,1-trichloro-2,2-bis- (4-chlorophenyl) -2- hydroxyethane and 1, i-dichloro-2,2-bis (4-ethylphenyl) -ethane. These compounds are known (see U.S. Patents 2 4 20 928, 2 464 6OO, 2 883 428 and 2 917 553).

As already mentioned, the novel active compound combinations of the methanephosphonic esters of the formula (I) which can be used according to the invention with carbamates, carboxylic acid esters, phosphoric esters, halocycloalkanes and haloalkanes show an outstanding increase in activity compared with the individual active compounds or with respect to their sum.

The weight ratios of the active ingredient groups can be considered in relatively large areas. In general, the phosphorus-containing compounds used as synergists with the other active ingredients in a ratio of 0.1: 1.0 to 10: 0.1 are used. However, mixing ratios of 0.5: 1.0 to 3.0: 1.0 have proven particularly suitable. The invention

Le A 19 872

223723

The active substances are suitable for good plant tolerance and favorable toxicity to warm-blooded animals for controlling animal pests, in particular insects, arachnids and nematodes, which are found in agriculture, in forests, in the protection of stored products and in the hygiene sector. They are against normally sensitive and resistant species as well as against all or individual stages of development. The above mentioned pests include:

From the order of isopods e.g. Oniscus asellus, Armadilli

dium vulgare, Porcellio scaber.

From the order of diplopoda e.g. Blaniulus guttulatus.

From the order of Chilopoda e.g. Geophilus carpophagus, Scutigera spec

 From the order of Symphyla e.g. Scutigerella immaculata.

From the order of Thysanura e.g. Lepisma saccharina.

From the order of Collembola e.g. Onychiurus armatus.

From the order of Orthoptera e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis,

Schistocerca gregaria.

From the order of the Dermaptera e.g. Forficula auricularia.

From the order of Isoptera e.g. Reticulitermes spp. From the order of anoplasia e.g. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus

spp., Linognathus spp.

From the order of Mallophaga e.g. Trichodectes spp.,

Damalinea spp. 30 From the order of Thysanoptera, for example, ' Herculothrips femoralis, Thrips tabaci.

Le A 19 872

223723 _

From the order of Heteroptera, e.g. Eurygaster spp.,. Dysdercus intermedius, Piesma quadrata, Cimex lectularivs, Rhodnius prolixus, Triatoma spp.

From the order of Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psylla spp. From the order of Lepidoptera e.g. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoeä, Lymantria spp. Bucculatrix thurberiella, Phyllocnis citrella, Agrotis spp., Euxoa spp., Feltia spp. Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, choristoneura fumiferana, clysia ambiguella, homona mag-

25 nanima, Tortrix viridana.

From the order of Coleoptera e.g. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelid2s obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysoc.ephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp. , Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp

Le A 19 872

2 2 3 7 2 3 - it -

varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postuca, Dermestes spp., Trogoderma spp., Anthrenus spp., 5 Attagenus spp., Lyctus spp., Meligethes aeneus,

Ptinus spp., Niptus hololeucus, Gibbium psylloides Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphiinallon solstitialis, Costelytra zealandica.

From the order of Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of Diptera e.g. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp.

15 Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus , Oscinella frit, Phorbia spp., Pegomyia

hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

From the order of siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp.

From the order of the arachnids, e.g. Scorpio maurus, Latrodectus mactans.

From the order of Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp , Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp

Le A 19 872

223723

The active compound combinations can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, suspension emulsion concentrates. Seed powders, natural and synthetic substances impregnated with active substances, ultra-fine encapsulations in polymeric substances and in coating compositions for seeds, and also in formulations with fuel assemblies, such as smoked cartridges, doses, spirals and the like. as well as ULV-KaIt- and heat-mist formulations.

These formulations are prepared in a known manner, e.g. by mixing the active compounds with extenders, that is to say liquid solvents, liquefied gases under pressure and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as an extender, e.g. also organic solvents can be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water; with

Le A 19 872

223 7 23

liquid gaseous extender !! or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, e.g. Aerosol propellants, such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide; as solid carriers: natural minerals, such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; as solid carriers for granules: crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules. of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foam-forming agents: nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; as a dispersing agent: e.g. Lignin, liquors and methylcellulose.

Adhesives such as carboxymethylcellulose, natural and synthetic pilgrim, granular or latex polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate may be used in the formulations.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic

Le A 19 872

29. 1. 81 '

AP C 07 F / 223 723

57 874 18

223723

- 2Ö -

Dyes such as alizarin, azo metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90 %,

The application of the active compound combinations according to the invention takes place in the form of their commercially available formulations and / or the use forms prepared from these formulations »

The active substance content of the application forms prepared from the commercial formulations can vary within wide ranges. The active compound concentration of the use form can be from 0.0000001 to 100 percent by _o -% by weight of active compound, preferably between 0.01 and 10, - lie%.

The application is done in a custom forms adapted to the application.

When used against hygiene pests and pests, the active compound combinations are distinguished by an excellent residual action on wood and clay and by good stability to alkali on limed substrates.

embodiment

The invention is explained in more detail below with reference to some examples. ,

³⁰ 223 7 23 - 2ft -

_Λ Examples ·

Preparation of the synergistic Methanphosphonsäurepropargylester.

Synergist 1: methanephosphonic acid dipropargyl ester

Methanephosphonic acid dichloride is according to LD Quin, CH. Rolston; J. Org. Chem. J23 _f 1693 (1958) by oxidation of methyldichlorophosphine.

1 a) Reaction in the presence of pyridine

1 mole of methanephosphonic dichloride and 2 g of phenothiazine are dissolved in 300 ml of toluene and '

a 10-20 ⁰ C to a mixture of 2.2 mol of pyridine or triethylamine and 112 g (2 mol) of propargyl alcohol added dropwise. The mixture is stirred for 3 hrs. At 20-30 ⁰ C and filtered from the hydrochloride 15 from. The filtrate is fractionated in a good vacuum. Bp .: 76 ° C / 0.1 mbar n ° 1: 1,464 7

Yield: 24%, based on 100% pure. Purity by GC: 84%

20 1b) Reaction in the two-phase system with NaOH as acid scavenger

224 g of propargyl alcohol, 250 ml of methylene chloride and 0.2 g of tricaprylic acid are placed in a stirred flask.

Le A 19 872

223 7 23

methyl ammonium chloride at 0 ⁰ C before and can be in separate feeds a solution of 133 g Methanphosphonsäuredichlorid in 250 ml of methylene chloride and 156 g of 5t% sodium hydroxide solution at the same time. The pH is kept between 9 and 10. The precipitated sodium chloride is filtered off, the organic phase is concentrated and fractionated in vacuo. Bp.: 87 ° C / 0.2 mbar n ° °: 1.4655

Purity by GC: 98.5% yield: 86.6%

Start of decomposition after differential thermal analysis: 219 ° C (conditions: closed vessel, N ₂ atmosphere, heating rate: 4 ° C / min.).

c) Example 1b) is repeated without the addition of Tricapry! methylammonium chloride

 Yield: 80.5% "

Synergist 2: Methanephosphonic Acid Methyl Propargyl Ester 20

According to the instructions in "Houben-Weyl, Methods of Organic Chemistry", Vol. 12/1, page 462, trimethyl phosphite is isomerized to Methanphosphonsäuredimethylester.

Le A 19 8 72

223723

300 g of phosgene are introduced into 288 g of dimethyl methanephosphonate at 5-10 ^° C. The mixture is heated to 25 ⁰ C and allowed to react for 2 hours. The volatiles are removed in vacuo at 25 ⁰ C. The total amount of crude Methanphosphonsäuremethylesterchlorids is neutralized with a little pyridine and added dropwise at 10 ⁰ C to a mixture of 123 g of propargyl alcohol, 174 g of pyridine and 1 1 of methylene chloride. It is boiled for 3 hours at reflux temperature.

IQ The organic phase is washed extensively with water and concentrated on a Rotavapor. The product is purified by distillation in vacuo. Bp .: 100 ° C / 0.3 mbar n ° °: 1.4540

Start of decomposition after differential thermal analysis: 198 ^° C; (Conditions: closed vessel, N ₂ atmosphere, heating rate: 4 ⁰ C / min.).

Synergist 3: methanthionophosphonic dipropargyl ester

According to the instructions in "Houben-Weyl, Methods of Organic Chemistry", Vol. 12/1, page 555, methanethionophosphonic acid dichloride is prepared from methyldichlorophosphine and sulfur.

The reaction to Methanthionophosphonsäuredipropargylester is carried out according to the method given for Synergist 1b) in a two-phase system of water and methylene chloride phase with tricaprylmethylammonium chloride as

Le A 19 872

22 3 7 23 - »

Phase transfer catalyst by. To achieve complete conversion, the reaction at 4O ⁰ C must

to finish.

kp .: 60 ° C / 0.05 mbar

n £ °: 1.5103

Yield: 67.4% purity by GC: 98.9%

analysis

C% H% S% P%

Calculated: 44 7 4 ,8th 17 0 16 , 5 Found: 45, 1 5 ,1 17 3 16 3

Le A 19 872

22 3 7 23

Test animals: Musca domestica (resistant to phosphoric esters and carbamates)

Solvent: acetone

Solutions are prepared from the active ingredients, synergists and mixtures of active ingredients and synergists, and 2.5 ml of these are pipetted into Petri dishes on filter paper discs of 9.5 cm diameter. The filter paper absorbs the solutions. The Petri dishes remain open until the solvent has completely evaporated. Then you give 25 test animals in the Petri dishes and cover them with a glass lid.

The condition of the test animals is continuously monitored for up to 6 hours. It determines the time required for a 100% knockdown effect. If the LT _{100 is} not reached after 6 hours, the% set of knocked-down test animals is determined.

Concentrations of the active substances, synergists and mixtures and their effects are shown in the table below.

Le A 19 872

table

LT 100 test with phosphoric acid ester and carbamate resistant Musca domestica (strain Weymanns oo)

Active ingredient () code letter

or synergist () Example no.

Concentrations in% active ingredient synergist

LT 100 after minutes

0-C-NHCH.

OCH

propoxur

1.0

360 ¹ = 20%

Cl ₂ C =

CO-CH ₂ -N

0.04

360 * = 70%

(B) Te tr ame thr in

Table (continued)

LT 100 test with phosphoric acid ester and carbamate resistant Musca domestica (strain Weymanns oo)

Active ingredient () code letter

or synergist () Example no.

Concentrations in % active ingredient synergist

LT 100 after

minutes

(C) permethrin

0,008

360 * = 70%

0 H-O-C-CH,

CCl

1.0

360 ¹ = 65%

(D) Penfenate

Active substance () Ke nnbuchstabe

or synergist () Example no.

0 ti

H ₅ CP (OCH ₂ -C =CH) ₂ (1)

H ₃ CP (OCH ₂ -C =CH) ₂

Known: 0 Cl-CH ₂ -P (OCH ₂ -C = CH) ₂

C ₂ H ₅ OP- (OCH ₂ -C = CH) ₂ (5) Concentrations in% LT 100 after active ingredient synergist minutes

1.0

0.2

1.0

1.0

56O - 25 %

36Ο ¹ - 20

560 '- 25 y

tr * active substance or · synergist Concentrations in% LT 100 to () Code letter () For game no. Active ingredient synergist minutes

£ ^A t ί , 0.008 + 0.008 360 '= 85 ^ i

A + 5 (known) 0.008 + ₀ , 008 360 '= »40 % j

A + 3 0.008 + 0.008 360 'j

0, 0, 008 oo8 0 oo8 0, 0, 04 04

^B * '? fbekannM °> ° ⁴ + 0,04 120 «! W

B + 1 (known) ^ _{04 + Q} ; _{o4 12Q |} -

S ⁺ ? known ^ ° '°° ^{8 +} O / OO8 12O ¹ '. ' ^! '

^{c +} 1 ί known) ^ _{008 + 0} * _{0 £) 8} ^ ₅₁ ,, ^

s ⁺ έ, · ° ' ² . + 0.2 360 · «90 %

^{D +} 5 (known) 0.2 + o, 2 36Ο ¹

^{D +} 5 0.2 + 0.2 210 '

Claims (5)

223723 invention claim 1, pest control agent, characterized by a content of a combination of active substances consisting of phos phorhaltigen compounds of the general formula (I) OCH ₂ -C = CH
H, CP.r (I) 2. pesticides, in particular insecticidal and acaricidal agents according to item I _1, characterized in that in the active ingredient combination, the weight ratio of phosphorus-containing compounds to active ingredients 29 · 1. 81 AP C 07 F / 223 723 57 874 18 22 3 7 23 - 59.- between 0.1: 10 and 10: 0.1. 3 «Method for controlling pests, in particular of insects and arachnids, characterized in that a combination of active substances according to item 1 or 2 is allowed to act on pests, in particular insects and arachnids and / or their habitat» * 3 Y R in which R is an alkyl, alkenyl or alkynyl radical having at most 4 C atoms or an aryl radical and X and Y mean oxygen or sulfur, and A, carbamates, and / or B, carboxylic acid esters, including natural and synthetic pyrethroids and / or C, phosphoric acid esters and / or D, halocycloalkanes and / or E »haloalkanes. 4 «Use of active substance combinations according to item 1, characterized in that they are used for controlling pests, in particular of insects and arachnids» 5 * A process for the preparation of pesticides, in particular insecticides and acaricides, characterized by mixing an active ingredient combination according to item 1 or 2 with extenders and / or surface-active agents.