CS216224B2 - Insecticide and acaricide means and method of making the synergically active substance - 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

The invention relates to an insecticidal and acaricidal composition based on known carbamates and / or carboxylic acid esters, including natural as well as synthetic pyrethroids and / or phosphoric acid esters and / or halocycloalkanes and / or haloalkanes, which contains novel methanephosphonic acid esters as synergistically active substance . The invention further relates to a process for the preparation of these novel methanephosphonic acid esters which contain propargyl residues.

A number of phosphorus compounds containing propargyl groups have been described in the literature as insecticide synergists. For example, benzyl and phenylphosphonic acid monopropargylalkyl or alkynyl esters are disclosed in DOS 2,551,257 and U.S. Patents 3,944,666, 3,885,031, 3,70,888, 3,652,741 and 3,555,123; in US Defensive Publication T 860 711 phenylphosphonic acid dipropargyl ester is disclosed. Among the phosphoric acid esters are described, for example: mono- or dipropargylester (thiono) phosphoric acid, the introduction of halogenated cycloalkyl radicals as the third phosphoric acid ester group (U.S. Pat. No. 2,693,483) and alkyl dipropargylesters of phosphoric acid (European patent application 78,100). 117.7).

Alkanephosphonic acid mono- and dipropargyl esters have also been described; propargylester of chloromethanephosphonic acid in U.S. Pat. No. 4,001,405, propargyl esters of alkane- or alkenephosphonic acid having at least 2 carbon atoms in U.S. Pat. No. 3,656,896 and in DOS 2,406,783.

These compounds are all synergistically highly active; only Chloromethanephosphonic acid dipropargyl ester is a less potent synergist. In general, dipropargyl esters are somewhat more effective than monopropargyl esters. However, these compounds have not yet found practical application for two main reasons: the mostly described propargyl esters of aromatic or aromatic-aliphatic phosphonic acids must be produced via phosphonic acid dichlorides, which are only available in multi-step syntheses and are therefore expensive; secondly, the reaction products must then be purified to separate often highly toxic by-products, such as pyrophosphonates. This purification of all oily substances is preferably carried out by distillation and, due to the very high boiling point and the lack of thermal stability of these compounds, is a difficult problem for chemical engineering. So

213224 for the production of O-propargyl-O-propyl benzylphosphonic acid, describes an apparatus for molecular distillation in DOS 2 551 257. The distillation is carried out at a bath temperature of 120 ° C and at a pressure of 133 to 200.10 ^-4 Pa. Obviously, such conditions cannot be realized with a large-scale plant. Phenylphosphonic acid dipropargylester boils according to U.S. Pat. No. 3,860,711 at a temperature of 141-142 ° C / 18.6 Pa, but it has already decomposed in the distillation according to experience.

In contrast, the aliphatic phosphates or phosphonates containing propargyl groups disclosed in U.S. Pat. No. 3,856,896 and in European Patent Application 78,100,117.7 have substantially lower boiling points. Nevertheless, the synthesis of larger amounts of product is difficult here. The process described in DOS 2 926 652 succeeds in the synthesis of alkyldipropargyl phosphate esters in good purity, so that distillation of the reaction mixture is not necessary. However, for higher production, uniform product quality can only be ensured if a purification operation, such as distillation, is carried out.

It turns out that the distillation of dipropargyl phosphate and propyldipropargyl phosphate, i.e. the compounds described in European Patent Application No. 78 100 117.7, in the temperature range between 110 and 140 ° C at a pressure of 10 to 1500 Pa cannot be carried out without thermal decomposition. decomposition polluting distillation. apparatus and distillate. Nevertheless, the differential thermoanalysis shows a strongly exothermic start of decomposition only at 221 ° C or 229 ° C at a heating rate of 4 ° C / min. Methanephosphonic acid dipropargylester and methanephosphonic acid methylpropargylester, for example, exhibit a slightly lower start of decomposition at 219 ° C or 198 ° C, for example, under the same experimental conditions.

Surprisingly, however, it has been found that these compounds can be distilled in a pressure range between 10 and 1500 Pa without remarkable decomposition. In general, methanephosphonic acid propargyl esters are better distillable than the corresponding phosphoric acid propargyl esters with the same number of propargyl groups and the same total number of carbon atoms.

The present invention provides an insecticidal and acaricidal composition based on known carbamates and / or carboxylic acid esters, including natural as well as synthetic pyrethroids and / or phosphoric acid esters and / or halocycloalkanes and / or haloalkanes, which is characterized as being synergistically effective the additive comprises at least one methanephosphonic acid propargyl ester of the formula I,

X OCH 2 —C = CH

II /

HsC — p \

Y - R (I) in which they are

R is an alkyl group of up to 4 carbon atoms, an alkenyl group of up to 4 carbon atoms or an alkynyl group of up to 4 carbon atoms or a phenyl group, and

X and Y are oxygen or sulfur, wherein in the active compound combination the weight ratio of the compounds of the formula I to the active compounds is between 0.1: 10 and 10: 0.1.

The synergistic effect of the compounds of the formula I is advantageous in the case of

A. Carbamates. of formula II,

R6 O \ II

N — C — O — R ⁴ /

R5 [II] v. which means

R 4 is an aryl group, a heterocycle residue or an oxime residue which is optionally substituted,

R5. hydrogen or (C1-C4) -alkyl, and

R 6 is alkyl, C 1 -C 6 alkylcarbonyl optionally substituted by hydroxy or methylthio, or -S-W, wherein:

W represents an optionally halogenated aliphatic radical having 1 to 4 carbon atoms, in particular a trichloromethyl radical and a trifluoromethyl radical, as well as an optionally preferably cyano-substituted halogen, in particular. . chloro, methyl, trihalomethyl, trifluoromethylmercapto or nitro substituted aryl, especially phenyl, or is

V — SO2 — N—,.

R5 where

V represents an alkyl group, a haloalkyl group, or optionally a halogen, a trihalomethyl group, a cyano group, a methyl group or a nitro group substituted with an aryl group or an alkyl group.

Particularly preferred are carbamates in which

R 4 is phenyl or naphthyl, optionally substituted with alkyl, alkenyl, alkoxy, C 1 -C 5 alkylmercapto, dialkylamino, dialkenylamino of up to 3 carbon atoms in each of the alkyl, especially chlorine, dioxalanyl or radical - N = CH - N - (alkyl) wherein alkyl contains 1 to 4 carbon atoms;

carbamates in which

R ⁴ is 2,3-dihydrobenzofuranyl, benzodioxolyl, benzothienyl, pyrimidyl or pyrazolyl which are optionally substituted with C 1 -C 4 alkyl, especially methyl or C 1 -C 4 dialkylamino in each alkyl moiety.

Further particularly preferred are carbamates in which

R ⁴ is the residue of an oxime of the formula IIa,

(Ha) where

R ⁷ and R ⁸ are the same or different and are alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkylmercapto, alkoxycarbonyl, carbonylamide, alkylmercaptoalkyl of up to 5 carbon atoms, cyano, aryl, especially phenyl , an aralkyl group, an optionally substituted heterocyclic radical or an alkyl group which is optionally substituted with a heterocyclic radical, or together represent an optionally C1 -C4 alkyl group substituted with a dioxolanyl group or a dithiolanyl group;

B. carboxylic acid esters of formula III,

OR ¹⁰

R ⁹ —C — O — CH — RH '- (III) wherein is

R ^{9 is} an alkyl group, an aralkyl group, an aryl group or a cycloalkyl group which may be optionally substituted, and

R ^{10 is} hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, cyano and

R ^{11 is an} aryl or heterocyclic group, or together with R ¹⁰ forms an optionally substituted cyclopentene ring;

particularly preferred are carboxylic acid esters in which

R ⁹ represents an alkyl group having 1 to 6 carbon atoms which is optionally substituted by an optionally substituted phenyl radical, a cyclopropyl group optionally substituted by an alkyl, alkenyl, haloalkyl or haloalkenyl group of up to 6 carbon atoms each, or is phenyl a group optionally substituted by halogen;

preferred are carboxylic acid esters in which

R ¹⁰ is hydrogen, C 1 -C 6 alkyl, C 1 -C 4 haloalkyl, C 3 -C 4 haloalkyl, cyano or ethynyl;

further preferred are carboxylic acid esters in which

R ¹¹ is phenyl optionally substituted by C 1 -C 4 alkyl, halogen, especially fluoro or chloro, phenoxy optionally substituted by halogen or methyl, optionally substituted by benzyl, furanyl, tetrahydrophthalimido, benzodioxolyl group optionally substituted by halogen, especially chlorine, alkyl or alkenyl of up to 4 carbon atoms, or benzyl, and further represents a cyclopentenone group which is optionally substituted by alkyl of 1 to 4 carbon atoms, furfuryl, alkenyl C 1 -C 5;

natural pyrethroids are particularly preferred;

C. phosphoric acid esters of the general formula IV,

XX — R ¹⁵ liz

R12— x — P \

X — R ¹⁴ (IV) wherein

X is independently oxygen or sulfur,

A represents oxygen, sulfur, NH or a direct bond between the central phosphorus atom and the radicals R ¹⁴ _{and R} i3 Riz j _SOU same or different and are alkyl or aryl, and

R ¹⁴ represents an alkyl, aryl, heteroaryl, aralkyl, alkenyl, dioxanyl or oxime radical or the same radical to which it is attached.

Especially preferred are phosphoric acid esters in which

R ¹² and R ¹³ are the same or different and are C 1 -C 4 alkyl or phenyl, and

R14 is C1-C4alkyl optionally substituted by halogen, hydroxy, cyano, optionally substituted by phenyl, carbonylamide, sulfonylalkyl, sulfoxyalkyl, carbonylalkyl, alkoxy, alkylmercapto, alkoxycarbonyl; alkenyl of up to 4 carbon atoms optionally substituted by halogen, optionally substituted by phenyl or alkoxycarbonyl, or by an oxime radical of formula (IIa),

R ⁸ / —N- = C \

R7 (IIa) wherein

R ⁷ and R ⁸ are as defined above, but in particular are cyano or phenyl, or dioxanyl which is substituted with the same radical as that bound to R ¹⁴ , or R 14 is the same radical as that to which it is bound, or ^R is phenyl which is optionally substituted by methyl, nitro, cyano, halogen, methylmercapto;

R14 is particularly preferably C1 -C4 alkyl or halogen-substituted heteroaromatic radicals, such as pyridine, quinoline, quinoxaline, pyrimidine, diazinone or benzo-1,2,4-triazine;

D. cycloalkanes of formula V,

in which

Hal represents halogen, preferably chlorine;

E. haloalkanes of formula VI '• IT OFO-C- Hal' ² (VI) in which

Ha! means chlorine or bromine,

R15 is hydrogen or hydroxyl,

R 17 _and R _{17 are the} same or different and are halogen, alkyl or alkoxy, and

R 18 is hydrogen or halogen.

Particularly preferred are the haloalkanes in which they are

R15 is hydrogen or hydroxyl,

R16 and R47 are the same halogen, alkyl or alkoxy group having from 1 to 4 carbon atoms, and

R18 halogen.

The insecticidal and / or acaricidal effect of the active compound combinations according to the invention is considerably higher than that of the individual components. Furthermore, it is substantially higher than the effect of the known active ingredient combination, which consists of 2-isopropoxyphenyl N-methylcarbamate and piperonyl butoxide and corresponds to the combination of the already known phosphoric acid alkyl dipropargyl ester according to European Patent Specification No. 78 100 117.7. In addition, the synergistically active compounds based on the phosphonic acid esters to be used according to the invention exhibit excellent synergistic activity not only for one active substance group, but also for active substances from a wide variety of chemical substances.

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

The compounds of formula I are novel. Only dlpropargylester of methanephosphonic acid was already synthesized by A.G. Makhsumov, A.M. Sladkov and V.V. Korshak, Izv. Akad. Nauk USSR, Ser. Kim. 1964, 733-6 and methanthionophosphonic acid S-propargyl-O-alkyl esters are known from U.S. Pat. No. 3,065,125.

Methanephosphonic acid propargyl esters of formula I,

X OCH 2 —C = CH

Н3С — P \ Y — R (I) in which they represent

R is an alkyl, alkenyl or alkynyl group having at most 4 carbon atoms or a phenyl group,

X and Y oxygen or sulfur, with the exception of methanephosphonic acid dipropargyl ester and methanthionophosphonic acid S-propargyl-O-alkyl esters, are novel compounds.

According to the invention, the phosphonates of the formula I are preferably produced from the corresponding methanephosphonic acid chlorides or from methanthionophosphonic acid chlorides. The methods known from the literature using tertiary amines as an acid binding agent have proved to be of little use, as shown by the synthesis result of the synergistically active substance 1 described in ( ^a) .

According to the invention, the compounds of the formula I are prepared by treating the corresponding methanephosphonic acid monochloride or dichloride with at least equivalent amounts of propargyl alcohol in a two-phase system in the presence of an inorganic base, preferably sodium hydroxide, in at least equivalent amounts as an acid binding agent.

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

Suitable organic solvents are halogenated hydrocarbons such as methylene. chloroform, chloroform, carbon tetrachloride,. 'Dichloroethane, trichlorethylene, tetrachlorethylene, chlorobenzene and dichlorobenzene; hydrocarbons such as benzene, toluene, xylene and mixtures thereof with aliphatic hydrocarbons; ethers such as. diethyl ether, dipropyl ether, dibutyl ether; ketones such as methylpropyl ketone, methylbutyl ketone, methyl isobutyl ketone, and esters such as ethyl acetate, propyl and butyl acetate, ethyl and butyl propionate.

A selection of suitable catalysts for the process of the invention is given below:

benzyldimethylamln, dibenzylmethylamin, benzyldiethylamine, benzyl-di- (2-cyanoethyl] amine, tributylamine, tris-2-ethylhexylamine, stearyldimethylamine, tetrabutylammonium chloride, tricaprylmethylammonium chloride, tris-2-ethylhexylmethylamoniumchlorid,; trioktylmethylamoniumchlorid, trimethylfenylamoniumchlorid, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, trimethylbenzylammonium, benzyldodecyldimethylamoniumchlorid, stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, myristyltrimethylammonium chloride, tetrabutylphosphonium chloride, triphenylmethylphosphonium bromide.

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, are preferably used as inorganic bases. Also, alkaline earth bases that are poorly soluble in water, such as magnesium carbonate, magnesium oxide, calcium oxide, calcium carbonate, barium oxide and barium carbonate, may be used, but are preferably used together with propargyl alcohol, water and a catalyst such that are placed in a reaction vessel and then suspended.

The preferred synthesis of the methanephosphonic acid propargyl esters of the invention starts from methyldichlorophosphine [see Reaction Scheme II]. By oxidation with oxygen or sulfur, methanephosphonic acid dichloride or methanthionophosphonic acid dichloride can be readily prepared therefrom, which can then be reacted with propargyl alcohol and optionally other aliphatic alcohols to form dipropargyl ester of methanphosphonic acid or methanthophosphonic acid or propargyl phosphonic acid ester, respectively. .

Reaction Scheme II:

X X ‘II

CHs — PC12 -> H3C — PC12

X

II

H3C — PC12 + HOCH2 — C = CH + HYR X OCH2 — C = CH 11 /

- НзС — P + 2 HCl

Y — R

R, X and Y. have the same meaning as in Formula I.

A further preferred process is to proceed from the dialkyl methanesulfonate or diphenyl ester of methanephosphonic acid, which is reacted with thionyl chloride or phosphorus pentachloride to form methanephosphonic acid dichloride or methanthionophosphonic acid dichloride (see Reaction Scheme III).

Reaction Scheme III (using thionyl chloride):

X X

II II

CH3 - P (OR2) 2 + 2 SOC12 -> CH3 - PC12 + + 2 SO2 + 2 RCl.

X and R are as defined in Formula I.

Another preferred process for the preparation of methanephosphonic acid monopropargyl ester also starts from methanphosphonic acid diesters or methanthionophosphonic acid diesters, and these compounds are reacted with phosgene or oxalyl chloride to form methanphosphonic acid or methanthionophosphonic acid chlorides which can be easily propargyl alcohol corresponding propargyl esters (see Reaction Scheme IV).

X ORX OR

1 // 1Z

H3C — P + HOCH2 — C = CH - HsC — P \ \

ClOCH2

X and R are as defined in formula I:

Particularly preferred synergistic substances based on propargyl esters of methanphosphonic acid of formula I include, for example: dipropargyl methane phosphonate, methylpropargyl methane phosphonate:

acids ,:

Methanephosphonic acid ethylpropargyl ester:

acids ,:

methanephosphonic acid n-propylpropargyl ester 2,2, methanephosphonic acid isopropylpropargyl ester methanphosphonic acid allylpropargyl ester, methanephosphonic acid methophenyl ester 0-methylpropargyl ester, methanphosphonic acid 0-methylpropargyl ester, phenyl methophosphonic acid ester, methanthionophosphonic acid, O, O-eShyrppopararlestet methanthionophosphonic acid, O, O-p-propyrpropar ₍ methanthionophosphonic acid methyl ester, O-propargyl-S-methyl ester of methanthionophosphonic acid, O-propagyl-S-ehionyl ester) methanesulfonophosphonic acid methyl ester.

To carbamates (group A) of formula. II which are used as a component of the mixtures preferably comprise:

2-Methylphenyl-

2-ethylphenyl-,

2-n-propylphenyl-,

2-methoxyphenyl,

Reaction scheme IV (using phosgene):

X .X OR

II 'liz

H5C — P (OR) 2 + COCl2 -> CH3 — P + \

.Cl + CO2 -I- RC1

- C = CH! -Ethoxyfenyl-, N- isopropoxyfenyl- or 2, -methylfenyl-, _{-ethylfenyl-,:} n-proprlfenrl-, -methoxyfenyl-, -ethoxyfenyl-, -n-propoxyfenyl-, -allylfenyl (1-m (4-methyl-4-methoxyphenyl) -1,5-trimethylphenyl- dihydro-2,2-dimethylbenzofuran) -7-yl-, [1,3-dioxolan-2-ylphenyl.] -, 2-dimethyl-1,3-benzodioxol-1-yl-,

2,2-dimethyl- or 1-methyl-2,3-dihydrobenzofuran-4-yl-N-methylcarbamate, and the corresponding -N-methyl-N-acetyl-, -N-methyl-N-trifluoromethylthio-, -N -methyl-N-dichlorormonofluoromethylthio-, optionally

-N-methyl-N-dimethylaminothiocarbamates.

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

To carboxylic acid esters (group B). of the formula III which are further optionally used as a component of the mixture include, for example:

Acetic acid [2,2,2-trichloro-1- (3,4-4-chlorophenyl) ethyl] ester, 2,3,4,5-tetrahydroftaimidomethylchrysanthemate,

3-Phenoxybenzyl [2,2-dimethyl-3- (2,2-dichlorvinyl) cyclopropane] carboxylate, (5-benzenfuryl) methyl 2,2-dimethyl-3- (2-methylpropenyl) cyclopropanecarboxylate, ( ±) -cis, trans-3-phenoxrbenzyl-2,2-dimethyl-3- (2-methylpropenrl) cyclopropanecarboxylate, α-cyano-3'-phenoxy-4'-fluorobenzylssr 2,2-dimethyl-4-dichlorvinyl - cis / trans-cyclopropanecarboxylic acid,

5-benzyl-3-furylmethyl-d-cis (1R, 3S, E) -2,2-dimethyl-3- (2-oxo-2,2,4,5-fetrahydrothiophenylmethylmethyl) cyclopropanecarboxylate, (R, S) 1α-Cyano-3-phenoxybenzyl (R, S) -2- (4-chlorophenyl) -3-methylbutyrate, (±) -3-allyl-2-methyl-4-oxocyclopent 2-enyl- (+) - cis-trans-chrysanthemate, 2,2-dimethyl-3-dichloro-vinyl-cyclopropenecarboxylic acid pentafluorobenzyl ester, [R, S] -afkyanf3phenoxybenzylf (IR, 1S) mis, trans-3- (2,2-dichlorvinyl) (S) -α-cyano-m-phenoxybenzyl (1R, 3R) -3- (2,2-dibromvinyl) -2,2-dimethyl-cyclopropanecarboxylate.

These compounds are known and are mostly commercial products [cf. R. Wegler 'Chemie der Pflanzenschutz- und Schadlingsbekampfungsmitter Vol. 1, pp. 87-118, Heidelberg (1940)].

The phosphoric acid esters (group C) of the formula IV which are further optionally used as a component of the mixture include, for example:

Ο, Ο-dimethylf and optionally O, O-diethyl-O- (2,2-diceloro- or -2,2-dibromvinyl) esters of phosphoric acid or thionophosphoric acid,

Ο, Ο-dimethyl-, optionally

O, O-diethyl 1-O- (3-methyl-4-methylthiophenyl) phosphoric acid or thionophosphoric acid esters.

The compounds of formula IV are known and are readily available by methods known in the literature (cf., for example, U.S. Patent 2,956,073, DAS 1,167,324, German Patent 633,478).

The cycloalkanes (group D) of formula V, which are further optionally used as a component of the mixture, preferably include:

1,2,3,4,5,6-hexxchlorocyclohexane.

This compound is known, as is the method for its preparation, and its use is known (cf., for example, U.S. Pat. No. 2,502,258; Chem. + Industr. 1945, p. 314).

The haloalkanes (group E) of the formula VI, which are further optionally used as a component of the mixture, preferably comprise:

1,1,1-trichloro-2,2-bis- (4-chloro-), optionally

4-methoxyphenyl) ethane,

1,1,14-chloro-1, 2,2-48- (4-chlorophenyl) -2-eyedroxyethene; and

1.1-dichler-2,2-2fs- (flxylllnyl ^ пип.

These compounds are known (cf. U.S. Patents 2,420,928, 2,464,600, 2,883,428 and 2,917,553).

As already mentioned, the novel combinations of methanephosphonic acid esters of the formula I to be used according to the invention with carbamates, carboxylic acid esters, phosphoric acid esters, halocycloalkanes and haloalkanes show an excellent increase in activity over the individual active substances or, respectively, substances.

The weight ratios of the groups of active substances can vary within relatively wide limits. In general, phosphorus-containing compounds which are used as synergistically active compounds are mixed with the other active compounds in a ratio of 0.1: 10 to 10: 0.1. The weight ratios of 0.5: 1.0 to 3.0: 1.0 have proven to be particularly advantageous.

The active substances have good plant compatibility and favorable warm-blood toxicity and are suitable for controlling pests, in particular insects, spider mites and nematodes in agriculture, forestry, in the protection of stocks and materials, as well as in hygiene. They are active against normally sensitive and resistant species as well as against all or only individual developmental stages of pests. The above mentioned pests include:

from the order of the Isopods, for example Oniscus asellus, Armadillidium vulgare, Porcellio scaber;

from the class of the millipedes (Dipplopoda), for example, the blind millipede (Blaniulus guttulatus);

from the class of the centipede (Chilopoda), for example, Geophilus carpophagus], Scutigera spec.

from the class of the Centipede (Symphyla) for example

Scutigerella immaculata;

from the order of the Thysanura, for example Lepisma saccharina;

from the order of the Collembola, for example Onychiurus armatus;

from the order of the Orthoptera, such as the cockroach (Blatta orientalis), the cockroach (Beriplaneta americana), Leucophaea maderae, the Russian russet (Blattella germanica), the Cricket (Acheta domesticus), the Gryllotalpa spec., Locusta migratoria migratorioides),

Melanoplus differentialis, Schistocerca grxgaria; from the order of the Dermaptera, for example Forficula auricularia; from the order of the Isoptera, for example, Reticulitermes spec. from the order of the Anoplura, for example Phylloxera vastatrix, Pxmphigus spec., Pediculus humanus corporis, Haxmatopinus spec.

Linognathus spec .;

from the order of the Mallophaga, for example, the Trichodectes spec.,

Damalinea spec .;

from the order of the Thysanoptxra, for example Hercinothrips femoralis, Thrips tabaci; from the order of the Heter-optera, for example, Eurygaster spec., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spec .;

from the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis fabae), Apple aphid [Doralis pomi], Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spec., Phorodon humuli, Phopalosiphum speci, Emperor psp. , Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidlola aurantii, Aspodiotus hederae, Pssela spec.

from the order of the butterflies (Lepidoptera), for example Pectinophora gossypiella, Bupalus piniarius,

Cheimatobia brumata, Lithocolletis blancardella, Apple Plutella maculipennis, Malacosoma neustria, Musk Euproctis chrysorrhoea, Lymantria spec. .), Euxoa spec., Feltia spec., Earias insulana, Heliothis spec., Laphygma exigua, Mamestra brassicae, Panolis flammea, Proderia litura, Spodoptera spec. ., Trichoplusia ni, Carpocapsa pomonella, White (Pieris spec.), Chilo spec., Corn moth (Pyrausta nubilalis), Moth moth (Ephestia kožhniella), Wax moth (Galleria mellonella), Fruit moth (Cacoecia podana),

Capua reticulana,

Choristoneura fumiferana,

Clysia ambiguella,

Homona magnanima, Tortrix viridana;

from the order of the beetles (Coleoptera), for example, Anobium punctatum, Rhizoperta dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica potato, Leptinoteae Colorado beetle (Phaedon cochleariae),

Diabrotica spec., Psylliodes chrysocephala,

Epilachna varivestis, Atomaria spec., Oryzaephilus surinamensis, Anthonomus spec., Sitophilus spec., Otiorrhynchus sulcatus,

Coamopolites sordidus, Ceuthorrhynchus assimilis,

Hypera, Dermestes spec.

Trogoderma spec., Anthrenus spec., Attagenus spec., Lyctus spec., Meligethes aeneus, Ptinus spec., Nibbus hollyucus, Gibbium psylloides (Tribolium spec.) Mealworm (Tenebrio molitor), Beetle (Agriotes spec.),

Conoderus spec., Common Cockchafer (Melolontha melolontha), Common Cockchafer (Amphimallon solstitialis),

Costelytra zealandica;

from the order of the Hymenoptera, for example Diprion spec., Hoplocampa spec., Lasius spec.

Monomorium pharaonis, Hornet (Vespa spec.);

from the order of the diptera (Diptera), for example, the mosquito (Aedes spec.), anofeles (Anopheles spec.), mosquito (Culex spec.), fruit fly (Drosopliila melanogaster), fly (Musea spec.), sunflower (Fannia spec.) (Calliphora erythrophala), buzzer (Lucilia spec.),

Chrysomyia spec., Cuterebra spec., Hamster (Gastrophilus spec.), Hyppobosca spec., Thistle (Stomoxys spec.), Hamster (Oestrus spec.], Hamster (Hypoderma spec.], Horsefly (Tabanus spec.), Tannia spec. , Garden Flycatcher (Bibio hortulanus), Barberry (Oscinella frit), Phorbia spec., Pegomyia hoyscyami, Ceratitis capitata], Dacus oleae, Tipula paludosa;

from the order of the order S for example fleas (Xenopxylla cheopís], fleas (Ceratophyllus spec.);

from the order of Arachnida, for example

Scorpio maurus; Latrodectus mactans;

from the order of the mites (Acarina), for example Acarus sulfur, Argas spec., Ornithodoros spec., Dermanyssus gallinae, E-riophyes ribis, Phyllocoptruta oleivora, Boophilus spec. , drinker (Rhipicephalus spec.), drinker (Amblyomma spec.), Hyalomma spec., tick (Ixodes spec.), flax (Psoroptes spec.), scab (Chorioptes spec.), Sarcoptes secp., mite (Tarsonemus spec.) , Currant Spider (Bryobia praetiosa), Spider Mite (Panonychus spec.), Spider Mite (Tetranychus spec.).

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, concentrates based on suspensions and emulsions, seed dressing powders, natural and synthetic active-impregnated substances, small particles coated with polymeric substances and seed coatings, flame retardants such as smoke cartridges, smoke trays, smoke spirals and the like, as well as formulations of active substance concentrates for mist dispersion cold or hot.

These compositions are prepared in a known manner, for example by mixing the active ingredient with fillers, i.e. liquid solvents, with liquefied gases under pressure and / or solid carriers, optionally using surfactants, i.e. emulsifiers and / or dispersants and / or foaming agents. If water is used as a filler, it is also possible to use, for example, organic solvents as co-solvents. Suitable liquid solvents are in particular: arolates, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol, as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethylsulfoxide, and water. By liquefied gaseous fillers or carriers is meant those liquids which are gaseous at normal temperature and pressure, for example aerosol propellants such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: natural stone meal, such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic stone meal, such as highly disperse silica, alumina and silicates. Suitable solid carriers for the preparation of granulates are crushed and fractionated natural stone materials such as limestone, marble, pumice, sepiolite and dolomite, as well as 1 synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells , corn sticks and tobacco stalks. Suitable emulsifiers and / or foaming agents are non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, fatty alcohol polyoxyethylene ethers, e.g.

The compositions of the invention may include adhesives such as carboxymethylcellulose, natural and synthetic powdered, granular or latex polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate.

In addition, these compositions may contain coloring agents such as inorganic pigments, for example iron oxide, titanium dioxide and ferrocyanide blue, and organic dyes such as alizarin and metallic azo-phthalocyanine dyes, as well as trace elements such as iron, manganese, boron, copper, cobalt salts. of molybdenum and zinc.

The concentrates generally contain between 0.1 and 95% by weight, preferably between 0.5 and 90% by weight, of active ingredient.

The active compounds according to the invention can be used in the form of commercial preparations and / or in dosage forms prepared from these preparations.

The content of active ingredient in dosage forms prepared from commercial preparations may vary within wide limits. The concentration of the active ingredient in the dosage forms may range from 0.0000001 to

21G224

100% by weight, preferably from 0.01 to 10% by weight.

The application is carried out in a conventional manner adapted to the application form used.

When used against hygiene pests and against storage pests, the active compounds according to the invention are distinguished by an excellent residual effect on wood and clay and good stability to alkali on lime substrates.

Examples

Production of synergistically active methanphosphonic acid propargyl esters

Synergically active substance 1: methanephosphonic acid dipropargyl ester.

Methanephosphonic acid dichloride was prepared according to L. D. Quin and C.I-I. Roloton: J. Org. Chem. 22, 1693 (1958) by oxidation of methyldichlorophosphine.

1a] Reaction in the presence of pyridine mol of methanephosphonic acid dichloride and 2 g of phenothiazine is dissolved in 300 ml of toluene and at 10-20 ° C this solution is added to a mixture of 2.2 mol of pyridine or triethylamine and 112 g (2 mol) of propargyl alcohol ( The mixture was stirred at 20-30 ° C for 1 hour and the hydrochloride was filtered off, and the filtrate was fractionated in a good vacuum Boiling point: 76 ° C / 10 Pa, nD ²⁰ = 1.4657 Yield 24% based on 100% pure by gas chromatogram purity: 84%.

1b] Reaction in a two-phase system using sodium hydroxide as an acid binding agent

A flask equipped with a stirrer was charged with 224 g of propargyl alcohol, 250 ml of methylene chloride and 0.2 g of tricaprylmethylammonium chloride at 0 DEG C. and a solution of 133 g of methanesulfonic acid dichloride in 250 ml of methylene chloride and 156 g of 51% hydroxide solution was flowed. sodium. The pH is maintained between 9 and 10. The precipitated sodium chloride is filtered off, the organic phase is concentrated and traction distilled under vacuum. Boiling point: 87 ° C / 20 Pa, nD ²⁰ = 1.4655, purity by gas chromatogram: 98.5%. Yield

86.6%.

Decomposition start according to differential thermoanalysis: 219 ° C (conditions: closed vessel, nitrogen atmosphere, heating rate:

° C / min).

1c] The procedure described in Example 1b] was repeated without the addition of tricaprylmethylammonium chloride.

Yield 80.5%,

Synergically active substance 2: methanephosphonic acid methylpropargyl ester.

As prescribed in the 'Houben-Weyl', Methoden der Organischen Chemie, Vol. 12/1, p. 462, trimethylphosphite isomerized to methanephosphonic acid dimethyl ester.

300 g of phosgene are introduced into 288 g of methanephosphonic acid dimethyl ester at 5-10 ° C. The mixture was then warmed to 25 ° C and allowed to react for a further 2 hours. The volatiles were removed in vacuo at 25 ° C. All of the crude methyl methosphoric acid chloride is neutralized with a small amount of pyridine and added dropwise to a mixture of 123 g of propargyl alcohol, 174 g of pyridine and 1 liter of methylene chloride at 10 ° C. The reaction mixture was refluxed for 3 hours. The organic phase is washed extensively with water and concentrated on a rotary evaporator. The product is purified by distillation under vacuum. Boiling point: 100 ° C / 30 Pa, nD ²⁰ = 1.4540.

Onset of decomposition by differential thermonalysis: 198 ° C (conditions: closed vessel, nitrogen atmosphere, heating rate: 4 ° C / min).

Synergically active substance 3: dipropargyloster methanthionophosphonic acid.

As prescribed in the 'Houbon-Woyl, Methoden der Organischen Chemie', - Vol. 12/1, p. 555, methanthionophosphonic acid dichloride is prepared from methyldichlorophosphine and sulfur.

The reaction to obtain the methanthronophosphonic acid dipropargyl ester is carried out according to the method described for the preparation of the synergistically active 1b] in a two-phase system consisting of an aqueous phase and a methylene chloride phase using tricaprylmethylammonium chloride as a phase transfer catalyst. The reaction must be completed at 40 ° C to achieve complete conversion.

Boiling point 60 ° C / 5 Pa, nD ²⁰ = 1.5 103, yield 67.4%, purity by gas chromatogram 98.9%.

Analysis:

calculated:

44.7% C, 4.8% H, 17.0% S, 16.5% P, found:

45.1% C, 5.1% H, 17.3% S, 16.3% P.

LTioo - test

Experimental insects:

house fly (Musea domestica] (a strain resistant to phosphoric acid esters and carbamates).

Solvent: acetone.

Prepare solutions from the active substances, synergistic active substances and mixtures of active substances and synergistic active substances and pipette 2,5 ml of these solutions into petri dishes, the bottom of which is 9,5 cm filter paper. The solutions are soaked in filter papers. Leave the petri dishes open until all the solvent has evaporated completely. Then, 25 specimens of test insects are placed in each dish and the dishes are covered with a glass lid.

The condition of the test insects is continuously monitored for up to 6 hours. The time required for 100% knock down effect is determined. If LT10 is not attained after 6 hours, the% of paralyzed insects is detected.

The concentration of active substances, synergistic active substances and mixtures as well as their effect is shown in the following table:

TABLE

LTioo - housefly (Musea domestica) test, resistant to phosphoric acid esters and carbamates (strain Weymanns 99) Active substance Synergistic effective concentration, if applicable% LT100 () G Labeling substance () Example number effective synergistic po min

CD

CD

CO O O

CD

O

Active substance Where applicable, synergistically effective concentration in% LT 10o () label substance () Example number of effective synergistic substance of substance

OO X ID O it WHAT CM II II II _p . O O O CD what CD WHAT what WHAT

CD

Ή

CD C ⁴ !

rH cT

χθ χθ <=> O θ ' θ ' O LD LD O CM CM what II II II II - χ. x. X. O O O O O O O CD what CD what what CM CM WHAT what WHAT what what Ή tH

what what what

O O O -Φ 'Φ

СЭСО O Q. O, cd o o o o o

what what what ООО

О 'O ~ О' O ^ О 'o ^ гч ó ~ θ' d о * 'θ'

o -> O O O v> 'WITH = cu I СЛ = Ри 1 1 o bO 1 O bO 'CD X E with tí N

'cd s From G 'what 'CD Д tí tM N

Φ CO ID ΙΌ τΗ + - + · -η 4— + <<<ΧΧ) PQ

C + 5 (known) 0.008 + 0.008 120 ‘

C + 1 0.008 + 0.008 105 ‘

D + 4 0.2 + 0.2 360) = 90%

D + 5 0.8 + 0.360

D + 3 0.8 + 0.2 210 ‘

Claims (5)

SUBJECT OF THE INVENTION An insecticidal and acaricidal composition based on known carbamates and / or carboxylic acid esters including natural as well as synthetic pyrethroids and / or phosphoric acid esters and / or halocycloalkanes and / or haloalkanes, characterized in that it contains at least one synergistically active ingredient Methanephosphonic acid propargyl ester of formula (I) X OCH 2 —C = CH НзС — Р \ Y — R (I) wherein R is C1-C4alkyl, alkenyl or alkynyl of up to 4 carbon atoms or phenyl; and X a. Y is oxygen or sulfur, wherein in the active compound combination the weight ratio of the compounds of the formula I to the active compounds is between 0.1: 10 and 10: 0.1. 2. A process according to claim 1, wherein the methanephosphonic acid monochloride or dichloride is treated with at least an equivalent amount of propargyl alcohol in a two-phase system in the presence of an inorganic base, preferably sodium hydroxide, in at least an equivalent amount. as an acid binding agent. 3. The process according to claim 2, wherein the reaction is carried out in a two-phase system using 0.001 to 100 mol%, based on phosphoric acid chloride, tertiary amine, quaternary ammonium or phosphonium salts with at least 9 carbon atoms as catalyst. 4. A process according to claim 2 wherein the solvent is methylene chloride, chloroform or toluene. 5. Process according to claim 2, characterized in that 0.01 to 10 mol%, based on phosphorus, tertiary amine, quaternary ammonium or phosphonium salts of at least 9 carbon atoms is used as the catalyst.