DD210599A5 - SCHAEDLINGSBEKAEMPFUNGSMITTEL - Google Patents

Abstract

The present invention relates to the partially novel Carbamidsaeureester of the general formula (I) in which R is optionally substituted alkyl having 4 and more carbon atoms or optionally substituted cycloalkyl and R is high 1, R is high and R 2 are the same or different and individually are hydrogen or optionally substituted alkyl which can be used as synergists in pesticides containing additionally arthropodicides, which are preferably active against insects and arachnids, in particular against insects.

Description

Field of application of the invention

The present invention relates to pesticides containing an active ingredient combination of at least one arthropod active substance and a synergist, processes for their preparation and their use as pesticides, preferably for controlling arthropods, in particular insects, mites and arachnids.

Characteristic of the known technical solutions

Synergistic mixtures of insecticidal active ingredients, eg. B. of pyrethroids with certain methylenedioxyphenyl derivatives, eg. B. Piperonylbuto3Ö.d as synergists have already become known (see, for example, K. Naumann, Chemistry of Crop Protection and Pest Control, Springer Verlag Berlin, Volume 7 (1981) pages 3-6). Further, certain N-arylcarbamic acid alkynyl esters (see DB-A 2 041 986) and certain W-alkylcarbamic acid alkynyl esters (see BB-A 633 594) have been described as synergists. However, the efficacy of these compounds is not always fully satisfactory under the conditions encountered in practice.

Object of the invention

The aim of the invention is the provision of new pesticides with improved efficacy.

Explanation of the essence of the invention

The invention has for its object to find new compounds with improved synergistic properties.

It has been found that the carbamic acid esters of the general formula (I)

R ¹

R-NH-CO-OCC ^ CR ³ (I).

R ² -

in which

R is optionally substituted alkyl having 4 or more carbon atoms or optionally substituted cycloalkyl and

12 R, R and R are the same or different and individually represent hydrogen or optionally substituted alkyl,

 - can be used as synergists in pesticides which additionally contain arthropodicides, which are preferably active against insects and arachnids, in particular against insects.

As arthropodicides (substances effective against arthropods), virtually all customary active substances are suitable (compare, for example, K. H. Büchel, Pflanzenschutz und-Schädlingsbekungsmittel, Thieme Verlag Stuttgart, 1977, and Farm Chemicals Handbook 1979, Meister Publishing Co, Willougby, 1979).

The carbamic acid esters of the general formula (Ia)

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- ^; 3 '1

G 12

R-NH-CO-OCC = CR ^3. , C (Ia)

in which

R is optionally substituted alkyl having 4 or more carbon atoms or optionally substituted cycloalkyl and ^; ,

R, R and R are the same or different and individually represent hydrogen or optionally substituted alkyl,

except the compound in which R is .n-butyl

12 and R, R and R are hydrogen, are novel and form part of the invention. ..

The compound of formula (Ia) with R = η-butyl and

12 3 R, R and R = hydrogen became known from EP-A 14032 as a synthetic intermediate (without mention of direct utility).

Furthermore, it has been found that the new carbamic acid esters of the general formula (Ia).

R ¹

R-NH-CO-OCC → CR ³ (Ia)

R ²

in which

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R is optionally substituted alkyl having 4 or more carbon atoms or optionally substituted cycloalkyl and

12 3 R, R and R are the same or different and are individually

are hydrogen or optionally substituted alkyl ',

except the compound in which R is η-butyl and

12 3 '

R ,, R and R stand for hydrogen, if one receives

Alkylisocyanates of the general formula (II) R - NCO (II)

in which

R has the meaning given above with alkynyl alcohols of the general formula (III)

R ¹

HO-C ^ CR ³ (III)

, 'R ²

in which .

1 2 3 R, R and R have the abovementioned meaning,

optionally in the presence of an aprotic diluent. and optionally in the presence

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of a catalyst at temperatures between 0 and 12O ⁰ C (the compound with R = nC ₄ EL · and R, R and R = H, can be obtained by the same method).

Optionally substituted alkyl R is preferably straight-chain or branched unsubstituted or substituted alkyl having 4-20, in particular 4-12, and particularly preferably 4-8 carbon atoms. Examples are optionally substituted η-, iso- and tert-butyl, neopentyl and hexyl called. Especially emphasized is the neopentyl radical.

As optionally substituted cycloalkyl R is mono-, bi- and tricyclic cycloalkyl having preferably 4 to 10, in particular 4, 5 or 6 atoms carbon atoms. Examples include optionally substituted cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo / 2,2, V-heptyl, bicyclo / 2,2,27-octyl and adamantyl called. Particularly preferred is the optionally substituted cyclohexyl radical.

As optionally substituted alkyl R, R and R 0 is straight-chain or branched optionally substituted alkyl having preferably 1-8, in particular 1-5 and particularly preferably 1-3 carbon atoms. Examples include optionally substituted methyl, ethyl, η- and i-propyl and n-, iso- and tert-butyl, wherein these radicals are preferably unsubstituted s ind.

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The alkyl and cycloalkyl radicals mentioned in the definition of R can carry one or more, preferably 1 to 3, in particular 1 or 2, identical or different substituents. As substituents, for example. listed:.

Alkoxy having preferably 1 to 4, in particular 1 or carbon atoms, such as methoxy, ethoxy, n- and iso-propyloxy and n-, iso- and tert-butyloxy; Alkylthio having preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methylthio, ethylthio, n- and iso-: 'Propylthio and n-, iso- and tert-butylthio; Halogen. ". ' > V alkyl with preferably 1 to 4, in particular 1 or

.ν carbon atoms and preferably 1 to 5, in particular; : ...-, ^.. , 1 to 3 halogen atoms, wherein the halogen atoms are the same or different and are halogen atoms, preferably fluorine, chlorine or bromine, in particular fluorine, such as trifluoromethyl; Halogen, preferably fluorine, chlorine, ',; Bromine and iodine, especially chlorine and bromine; cyano; nitro; ... ^{: l} '. '. Alkoxycarbonyl having preferably 2 to 4, in particular; v: °: 2 or 3 carbon atoms, such as methoxycarbonyl and,; ^; ;,: ^; Ethoxy carbonyl and Phenoxyben zyloxycarbonyl. ^:;

.. :: ..; The alkyl radicals mentioned in the definition of R and R can carry one or more, preferably 1 to 3, in particular 1 or 2, identical or different substituents. As substituents may be at: -: '/,. for example: on led: '

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Alkoxy having preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methoxy, ethoxy, n- and iso-propyloxy and n-, iso- and tert-butyloxy; Alkylthio having preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methylthio, ethylthio, n- and iso-Propylthio and η-, iso- and tert-butylthic; Haloalkyl having preferably 1 to 4, in particular 1 or 2 carbon atoms and preferably 1 to 5, in particular 1 to 3 halogen atoms, wherein the halogen atoms are the same

1P or are different and are halogen atoms, preferably fluorine, chlorine or bromine, in particular fluorine, such as trifluoromethyl; Halogen, preferably fluorine, chlorine, bromine and iodine, in particular chlorine and bromine; cyano; nitro; Alkoxycarbonyl having preferably 2 to 4, in particular

Ί5 is 2 or 3 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl. .

The alkyl radical mentioned in the definition of R may carry one or more, preferably 1 to 3, in particular 1 or 2, identical or different substituents. As substituents are listed by way of example:

Alkoxy having preferably 1 to 4, in particular 1 or 2, carbon atoms, such as methoxy, ethoxy, n- and isc-propyloxy and n-, isc- and tert-butyloxy; Alkylthio having preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methylthio, ethylthio, n- and iso-Propylthio and n-, iso- and.tert.-butylthio; Haloalkyl having preferably 1 to 4, in particular 1 or 2

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Carbon atoms and preferably 1 to 5, in particular

1 to 3 halogen atoms, wherein the halogen atoms are identical or different and are halogen atoms, preferably fluorine, chlorine or bromine, in particular fluorine, such as trifluoromethyl; Halogen, preferably fluorine, chlorine, bromine and iodine, in particular chlorine and bromine; cyano; nitro; Alkoxycarbonyl having preferably 2 to 4, in particular

2 or 3 carbon atoms, such as methoxycarbonyl and ethoxycarbony1.

1.0 A preferred substituent of the alkyl radical R is halogen (fluorine, chlorine and bromine, preferably chlorine) and the cycloalkyl radical R is haloalkyl (preferably trifluoromethyl).

1 2

Preferably, the radicals R, R and R are unsubstituted.

Preference is given to the carbamic acid esters of the general formula (I) in which

R is an optionally substituted by alkoxy (C. -C ₄ ), halogen, cyano, nitro and / or trifluoromethyl substituted alkyl radical having 4-12 carbon atoms or for one optionally by alkoxy (C.-C.), halogen, cyano * Is nitro and / or trifluoromethyl-substituted cycloalkyl radical having 4-10 carbon atoms and

1 ? 3 R, R ~, R are the same or different and are individually hydrogen or an optionally

by halogen, cyano, C.-C, -alkoxy, CC ₄ -

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Alkylthio or trifluoromethyl substituted alkyl radical having 1-2 carbon atoms.

The invention particularly preferably relates to carbamic acid esters of the general formula (I) in which

R is an optionally substituted by fluorine, chlorine or cyano substituted alkyl radical having 4-8 Kohlenstpffatomen or represents a substituted by fluorine, chlorine, cyano or trifluoromethyl cycloalkyl having 5-6 carbon atoms, and .

R, R, R are the same or different and are individually for

Is hydrogen or an optionally substituted by fluorine, chlorine, methoxy or methylthio substituted alkyl radical having 1 to 3 carbon atoms

 .. atoms atoms, stand.

.1.5. Especially emphasized are the carbamic acid esters of the general formula (I) in which

R is optionally substituted by chlorine or cyano-substituted alkyl having 4 to 6 carbon atoms or optionally substituted by trifluoromethyl-substituted cyclohexyl and

12 3 R, R and R are hydrogen.

As novel carbamoyl esters of the formula (Ia), particular preference is given to the compounds in which

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R is neopentyl or optionally substituted by trifluoromethyl substituted cyclohexyl and

R, R and R are hydrogen.

If, for example, neopentyl isocyanate and propargyl alcohol are used as starting materials, the process according to the invention can be illustrated by the following formula 1:

"3

CH ₃ -C-CH ₂ -NCO + HO-CH ₂ -C = CH

CH.

Ch ₃ -C-CH ₂ -NH-CO-O-CH ₂ -C =CH

10 In the inventive method, the output. materials, preferably in equimolar amounts. However, it is also possible to use one of the components simultaneously as a diluent. , ', 7- ^:. '. '. · ·' .- ......

When ^he: findun.gsgemäßeh procedures are virtually all solvents aprotischeri overall diluent Λ is "V ^ Preferred here are ketones such as acetone aliphatisehe, gegebehenfalls halogenated" or aromatic hydrocarbons, such as methylene chloride or toluene, Nitrile7;.. Wie.Acetonitril as well as their mixtures, but it is also possible to work without a diluent.

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Triethylamine, diazabicyclooctane (DABCO) or dibutyltin laurate are optionally added as catalysts to the reaction mixture.

The reaction temperature is maintained in the process according to the invention between about 0 and 120 ⁰ C, preferably between about 0 and 60 ⁰ C. The process is preferably carried out at atmospheric pressure.

The starting compounds of the formula (II) are known and / or can be prepared in a customary manner by processes and methods known per se (cf., for example, methods of organic chemistry (Hcuben-Weyl-Muller) 4th Edition, Volume 8 (1952) p 119 ff.).

The starting compounds of the formula (III) are known and / or can be prepared in the customary manner by processes known per se (cf., W. Reppe J. Liebigs Ann. Chem. 569 , 1 (1955), W. Ried, used. Chem. 7_6, (1964), W. Ried et al., Chem. Ber. 9_8, 245 (1965)).

The carbamic acid esters of general formula (I), when admixed with substances of any constitution which are active against arthropods, have potent synergistic effects which enable their use in pesticides. (In the following, the reference to the general formula (I) should include in each case also the compounds of the general formula (Ia)).

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The carbamic acid esters of the general formula (I) are preferred together with aithropodicides

1. Carbamic acid esters and / or

2. Carboxylic esters including natural and synthetic pyrethroids and / or

3. Phosphorus compounds, such as phosphoric acid and phosphonic acid esters, including the thio and dithio compounds and / or

4. halo (cyclo) alkanes, such as e.g. hexachlorocyclohexane

used.

Surprisingly, the effect of the new active compound combinations according to the invention against arthropods is substantially higher than the effect of the individual components or the sum of the effects of the individual components. It is also much higher than the effect of • drug combinations with the known commercial synergist piperonyl butoxide. The carbamic acid esters which can be used according to the invention additionally exhibit excellent synergistic activity not only in the case of an active substance class, but also in the case of active substances from a wide variety of chemical substance groups.

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The synergistic effect of the compounds of the general formula (I) is particularly preferred

1) carbamic acid esters of the formula (IV)

R ⁴ -O-CO-N (IV)

R ⁶

in which .

R is an optionally substituted carbocyclic or heterocyclic aromatic

Remainder or for an optionally substituted

  tuierten oxime residue (with the radicals R explained below 4 are preferred),

~ R ^{5 is} C ₁ -C ₄ -Al] CyI and

R is hydrogen, C.-C ₄ -alkyl or a radical Y, wherein

Y is the radical -CO-R in which

R is halogen, C.-C.-alkyl, C... C. Alkoxy, ^C 3 ~Cc

Alkenoxy, C ₃ -C ₅ -alkynoxy, C ₁ -C -alkylthio, C ₁ -C 4 -alkylamino, C ₁ -C 4 -alkylamino, C ₁ -C ₅ -alkyl-hydroxylamino,

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optionally substituted by halo, nitro, cyano, trifluoromethyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C 6 alkylenedioxy, C ₁ -C ₄ alkylthio, C -C . Alkoxy-carbonyl-substituted phenoxy, phenylthio or phenylamino, for 2,3-dihydro-2 ^ -dimethyl-T-benzofuranyl or the radical

-0-N = C ^ f

^X R ⁹

stands in which

R ^{8 is} hydrogen, C ₁ -C ₄ -alkyl or di-C ₁ -C ₄ -alkyl-

₁ -C ₄ amino-carbonyl and

R ⁹ is C ₁ -C ₄ -AIk ^ l, Cj-C ^ alkylthio, cyano-C ₁ -C ₄ alkylthio, C.-C ~ ₄ alkylene ItIiIO-C ₁ -C ₄ -alkyl,

^s 8 9

or the two radicals R and R together are optionally interrupted by oxygen, sulfur, SO or SO ^ interrupted C ₂ -Cg alkanediyl, or

in which .

Y is the radical -S (O) -R, in which

η m

η for 1 or 2 and

m stands for 0, 1 or 2 and

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R is optionally substituted by halogen

Cj-Cg-Alkenyl / C ₃ -C ₅ -alkyl or C 1 -C 8 -cycloalkyl, optionally substituted by halogen, cyano, nitro, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, C ₁ -C ₄ -alkyl, or C ₁ -C _4- alkyl-substituted phenyl, benzyl or phenylethyl, or for the radical,:. :

R ¹¹

stands in which

R ^{11 is} C ₁ -C ₄ alkyl, C ₃ -C ₅ alkenyl, C ₃ -C ₅ C ₃ -C 9 cycloalkyl or benzyl and

R ^{12 is} C ₁ -C ₄ -alkyl, C ₃ -C ₅ -alkenyl, C ₃ -C ₅ -C 12 -cycloalkyl, benzyl, phenylethyl, halocarbonyl, formyl, C ₁ -C ₄ -alkyl-carbonyl, C ₁ -C ₄ -alkoxy-carbonyl, C ₁ -C.-alkoxyphenoxy-carbonyl, C ₃ -C _5-carbony1 alkynoxy, C ₃ -C ₅ -Alkenoxycarbony1, C ₁ -C ₄ alkylthiocarbonyl, C ₁ -C _4- alkyl-amino-carbonyl, C ₁ -C ₄ -alkyl-hydroxylamino-carbonyl, C ₁ -C ₁₀ -alkyl-phenoxycarbonyl, di-C ₁ -C ₄ -alkyl-aminocarbonyl, phenylthiocarbonyl, phenoxycarbonyl, 2,3- dihydro-2,2-dimethyl-7-benzofuranyloxycarbonyl, ₄ -alkoxy-substituted phenylsulphenyl, phenylsulfinyl, phenyl sulfonyl or represents phenyl which is optionally substituted by halogen, cyano, nitro, trifluoromethyl, C ₁ -C alkyl or C ₁ -C or for the rest

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-16 "13

-CO-O-N = C

in which ·; ',,. , ":

118 R the meaning given above for R and

14 9

R has the meaning given above for R,

^: R ^11:

s * 11 12

furthermore, in the "-N" radical, the radicals R and R

together for an optionally interrupted by oxygen or sulfur Kohlenwasserstcffkette with 3 bis

Carbon atoms, wherein further R is also for

may be the same radical to which the radical -S (O) -R is attached. , _: , ' ...-. .-- ' ^: . , : ': /.

Very particularly preferred active ingredient components are carbamic acid esters of the formula (IV) in which

    4 '' '

R is optionally C ₁ -C ₄ -Al] CyI, C ₂ -C ₄ -alkenyl, C ₁ -C ₄ -alkoxy-methyl, C ₁ -C ₄ -alkylthio, 5 "C ₁ -C ₄ - Alkylthio-methyl, C ₁ -C ₄ -alkylamino, di- (C ₁ -

C ₄ alkyl) amino, di- (C ₃ -C ₄ alkenyl) amino, halogen,. '..:. Dioxolanyl, methylenedioxy and / or by the radical -N = CH-N (CH_) ₀ substituted radicals from the series phenyl, naphthyl, 2,3-dihydro-7-benzofuranyl, pyrazolyl or pyrimidinyl, or in which

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4 R for an alkylidene amino radical of the formula (IVa)

(IVa)

stands in which

R and R have the meaning given above for R and R, respectively, and / and

R ^{5 is} C _1-4 -alkyl and

R is hydrogen or C.-C.-alkyl (before

preferably for hydrogen) ·

Examples of the carbamic esters of the formula (IV) are: 2-methyl-phenyl, 2-ethyl-phenyl, 2-isc-propyl-phenyl, 2-sec-butyl-phenyl, 2-methoxyphenyl, 2-ethoxy-pher-.yl, 2-isopropoxy-phenyl, 4-methyl-phenyl, 4-ethyl-phenyl, 4-n-propyl-phenyl, 4-methoxy-phenyl, 4 Ethoxy-phenyl, 4-n-propoxyphenyl, 3,4,5-trimethyl-phenyl, 3,5-dimethyl-4-methylthic-phenyl, 3-methyl-4-dimethylamino-phenyl, 2-ethyl-thiomethyl-phenyl -, 1-Naphthyl-, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl, 2,3- (dimethyl-methylenedioxy) -phenyl, 2- (4, Ξ-dimethyl-I, 3-dioxolane -2-yl) -phenyl, 1-methylthio-ethylidene-amino, 2-methyl- ^ -thic-2-methylpropylideneamino, 1- (2-cyano-ethylthio) -ethylideneamino- and 1-methylthiomethyl-2, 2-dime.thylpropylidenamino-N-methyl-carbamic acid ester.

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The synergistic effect of the compounds of general formula (I) is further preferred.

2) carboxylic esters of the formula (V)

R ¹⁷ ^ -CO-O-CH-R ¹⁹ (V)

in which

R is an open-chain or cyclic alkyl radical which is optionally substituted by halogen, alkyl, cycloalkyl, alkenyl optionally substituted by halogen, alkyl and / or alkoxy, by phenyl or styryl, which are optionally substituted by halogen, optionally halogen-substituted radicals of the Alkyl, alkoxy, alkylenedioxy and / or alkylthio are substituted by spiro-cyclic, optionally halogen-substituted cycloalk (en) yl, which is optionally benzannellated, in which further

R 8 represents hydrogen, alkyl, haloalkyl, alkenyl, alkynyl or cyano, and

9 0 R is an optionally substituted alkyl or aryl radical or a heterocycle,

1 8

or together with R and the carbon atom to which both radicals are bonded form a cyclopentenone ring.

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Especially preferred as active ingredient components are carboxylic acid esters of the formula (V) in which

R ¹⁷ for. the rest

CH = C

R is hydrogen, methyl, fluorine / chlorine or bromine

, "and. '...:'':'.;.'.:',:,' ^: -;:; ^: ."

1 . , ·. :

R is methyl, fluorine> chlorine, bromine, C 1 -C 4 fluoroalkyl. , or C ₁ -C ₄ -chlorofluoroalkyl or radicals optionally substituted by halogen and / or optionally halogen-substituted radicals of the series C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio and / or C C ₁ -C ₂ -alkylenedioxy-substituted phenyl, or in which both radicals R ²⁰ and R ^{21 are} C ₂ -C ₅ -alkanediyl (alkylene);

or in which ... ->! : \

R ^{17 is} the radical -CH-R ²² , wherein "' ^: '"<"'' - ^r : .: ';

    , ,

R is optionally substituted by halogen and / or by optionally halogen-substituted radicals of the. ' Series C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio or C ₁ -C 6 alkylenedioxy substituted. Phenyl stands and \. ^r r

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23

is isopropyl or cyclopropyl;

or in which

17

, 18

for one of the leftovers

H ₃ C CH ₃

H ₃ C CH ₃

H ₃ C CH ₃

wherein the dotted lines are intended to indicate possible Doppelbin applications, or is methyl, and in which further

R is hydrogen, C.-C ₄ -alkyl.,. C ₁ -C ₄ haloalkyl, cyano or ethynyl and

optionally substituted by halogen radicals of the series phenyl, furyl or tetrahydrophthalimido, 'wherein these radicals in turn may be substituted by optionally halogen and / or by an optionally halogen-substituted radical of the series C ₁ -C ₄ alkyl, C ₂ -C ₄ -alkenyl, C ₁ -C ₄ -alkoxy, C ₃ -C ₄ -alkenoxy, C ₁ -C.-alkylthio, _C1 ^ alkylenedioxy,

Phenoxy and / or benzyl, wherein for R. preferably pentafluorophenyl, 3,4-dichlorophenyl, phenoxyphenyl, which may be substituted in one or both phenyl rings by halogen or is tetrahydrophthalimido.

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Furthermore, the naturally occurring pyrethroids (such as pyrethreum) are particularly preferred as the carboxylic acid ester of the formula (V).

Examples of the carboxylic acid esters of the formula (V) include:

Acetic acid (2,2,2-trichloro-1 - (3, 4-dichloro-phenyl) -ethyl) -ester, 2,2-dimethyl-3- (2-methyl-propen-1-yl) - cyclopropane-carboxylic acid (3,4,5,6-tetrahydro-phthalimido-methyl) ester, 2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropane-carboxylic acid (3-phenoxy-benzyl) - ester, 2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid {'X- cyano-3-phenoxybenzyl) ester, 2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclicpropanecarboxylic acid (# -cyano-4-fluoro-3-phenoxybenzyl) ester, 2,2-di-, methyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid (pentafluoro-benzyl) ester, 2,2-Dimethy1-3- (2,2-dibromovinyl) -cyclopropanecarboxylic acid (<X-cyano-3-phenoxybenzyl) ester and 3-methyl-2- (4-chlorophenyl) -butanoic acid ( cyano-3-phenoxy-benzyl) ester.

Further, the synergistic action of the compounds of the general formula (I) is preferably added

3) Phosphoric acid and phosphonic acid esters of the general formula (VI)

X ..XR ²⁵

Ji Il -S ^

R-X-P. (VI)

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j η: ί O a. λ i \\ - \ i * t

in which

Each X is O or S and

Y is 0, S, -NH- or a direct bond between £

and

between the central P-AtOm and R stands

25 R and R are the same or different and for

optionally substituted alkyl or aryl stand /

R is optionally substituted for hydrogen

substituted alkyl, aryl, heteroaryl, aralkyl,

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

Particular preference is given to phosphoric acid and phosphonic acid esters of the formula (VI) in which

25 R and R are the same or different and for

C ₁ -C ₄ -alkyl or phenyl,

R is hydrogen, alkyl of 1 to 4 carbons

atoms optionally represented by halogen, hydroxyl, cyano

if halogen-substituted phenyl, carbamoyl, alkylsulfonyl, alkylsulfinyl, alkylcarbonyl, alkoxy, alkylmercapto,

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Alkoxycarbony1, alkylaminocarbonyl, the latter having in each case up to 6 carbon atoms / is substituted, alkenyl having up to 4 carbon atoms, which is optionally substituted by halogen, optionally halo-substituted phenyl or C ₁ -C ₄ alkoxycarbonyl, or the radical of the general Formula (VIa)

, R ²⁷

-N = C -. (Via)

27 28 8 9

wherein R and R have the meaning given above for R or R, or are cyano or phenyl, and in which

R further for dioxanyl substituted by the same radical to which R is attached, or R for the same radical to which it is attached. or R is phenyl optionally substituted by methyl, nitro, cyano, halogen and / or ^; methylthio

26 '

and R is also particularly preferably substituted by C.C.-alkoxy, C ₁ -C ₄ -alkylthiomethyl, C ₁ -C ₄ -alkyl and / or

Halo-substituted heteroaromatic radicals such as pyridinyl, quinolinyl, quinoxalinyl, 'pyriinidinyl or benzo-1,2,4-triazinyl.

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Specifically, may be mentioned:

0,0-dimethyl or 0,0-diethyl-O- (2,2-dichloro- or

2,2-dibromovinyl) -phosphoric acid ester, 0,0-diethyl-O- (4-nitrophenyl) -thionophosphoric acid ester 0,0-dimethyl-O- (3-ethyl-4-methylthio-phenyl) -thionophosphoric acid ester

0,0-dimethyl-O- (3-methyl-4-nitro-phenyl) -thionophosphoric acid ester,

0-ethyl-S-n-propyl-O- (2,4-dichlorophenyl) -thionophosphoric acid ester,.

O-ethyl-S-n-propyl-O- (4-raethylthio-phenyl) thionophosphate,

0,0-Dimethyl-S- (4-OXO-1,2,3-benzothriazine (3) yl-methyl) thionothiol phosphoric acid ester, 0-methyl-O- (2-iso-propyl-6-methoxy-pyrimidine (4 yl) -thionomethanephosphonic acid ester, O, O-diethyl-O- {2-iso-propyl-6-methyl-pyrimidin (4) yl) -thionophosphoric acid ester,

O, O-diethyl-O- (3-chloro-4-methyl-coumarin (7) yl) thionophosphate,

O, O-dimethyl-2,2,2-trichloro-1-hydroxy-ethane-phosphonic acid,

O, O-dimethyl-S- (methylaminocarbonyl-methyl) thionophosphate.

Furthermore, the synergistic effect of the compounds of the general formula (I) is preferred

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4) halo (cyclo) alkanes, e.g. Hexachlorocyclohexane, 1,1,1-trichloro-2,2-bis (4-chlorophenyl) ethane, T, 1,1-trichloro-2,2-bis (4-methoxyphenyl) ethane and 1, i- Dichloro-2,2-bis (4-ethylphenyl) -ethane.

The weight ratios of synergists and drugs can be varied within a relatively wide range. In general, the compounds of the formula (I) used as synergists with the other active ingredients are used in mixing ratios of between 1: 100 and 100: 1, preferably between 1: 5 and 5: 1 (parts by weight).

The active compound combinations according to the invention not only have a rapid knock-down effect, but also cause the lasting killing of animal pests, in particular of insects and mites, which occur in agriculture, in forests, in the protection of stored products and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.

The animal pests that can be controlled using ^: the compounds of formula (I) include, for example: '.

From the order of isopods e.g. Oniscus asellus, Porcellio scaber.

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

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From the order of Orthoptera e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, .Gryllotalpa spp., Locusta migratoria migratorioides, 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 the Anoplura e.g. Pediculus humanus corporis, Haematopinus spp., Linograthus spp.

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

From the order of the Heteroptera e.g. Cimex lectularius, Rhodnius prolixus, Triatoma spp

 From the order of Homoptera e.g. Myzus spp., And

Psylla spp. ,

From the order of Lepidcptera e.g. Ephestia kuehniella and Galleria mellonella. From the order of Coleoptera e.g. Anobium punctatum, Rhizopertha. dominica, Bruchidius obtectus, Acantho'scelides obtectus, Hylotrupes bajulus, Oryzaephilus sürinamensis, Sitophilus spp., Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Ptinus spp., Niptus hololeucus, Gibbium psylloides , Tribolium spp. and Tenebrio molitor.

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

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

Le A 21 8 88

Chrysorryia spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypderma spp. and.

Tabanus spp.

From the order of siphonaptera e.g. Xenopsylla 5 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, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp. , Psoroptes spp., Chorioptes spp., Sarcoptes spp.

The active compound combinations of the compounds of the formula (I) and the other active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, aerosols, suspension emulsion concentrates, active ingredient-impregnated nature - And synthetic materials, Feinstverkapselungen in polymeric materials, further in formulations with fuel packs, such as smoke cartridges, doses, spirals, etc., and ULV KaIt- and warm mist formulations.

These formulations are prepared in a known manner, e.g. by mixing the active substance mixtures with extenders, that is to say liquid solvents, under liquefied gases under pressure and / or solid

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Carriers, optionally with the use of surfactants, emulsifiers and / or dispersants and / or foam-forming agents. "-

In the case of using water as extender

can e.g. also organic solvents as auxiliary; solvents are used. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkyl naphthalenes, chlorinated

: T0 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; By liquefied gaseous diluents or carriers is meant those 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; solid carriers: ground natural minerals, such as kaolins, clays, 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: fractionated and fractionated

Le A 21 888

natural rocks such as calcite, marble, pumice, sepiolite, ν 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 foaming agents: nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkylsulfonates; as a dispersing agent: e.g. Lignin, liquor liquors and methylcellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-type 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 dyes such as alizarin, azo and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and

.20 zinc can be used.

The formulations generally contain between 0.1 and 95 wt .-% active ingredient combination, 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 formulated

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AP A 01 H / 253 900/1 62 594 11

lations and / or the use forms prepared from these formulations

The total active ingredient content (including synergist) of the use forms prepared from the commercial formulations may vary widely. The active ingredient concentration of the use forms can be from 0.001 to 100% by weight of active ingredient combination, preferably between 0.01 and 10% by weight.

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

When used against hygiene and storage pests, the drug combinations are characterized by an excellent Residualwirkung on wood and clay and by a good alkali stability on limed substrates.

Embodiment

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

The effectiveness of the compounds of the formula (I) which can be used according to the invention will be explained by means of the following biological examples:

Applied test method:

Test animals: Musca domestica, strain Weymanns (against carbamic acid ester and resistant to P-ester)

Solvent: acetone

Solutions are prepared from the active ingredients, synergists and mixtures of active ingredients and synergists, and 2.5 ml of them are pipetted into Petri dishes on 9.5 cm diameter filter paper discs. 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 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.

0 Active substances, synergists, concentrations of active substances, synergists and mixtures and their effects are shown in the tables below.

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Table I Examples of arthropodicides which can be used according to the invention

It

0-C-NHCH,

A.)

(Propoxur)

B.)

¹ O-CNHCH 0

t!

D.) CH ₅ -HN-CON = CS-CH

CH,

(Carbofuran)

(Bendiocarb) (Methorayl)

E.) Pyrethrins of natural origin as 25% extract

 F.)

(Tetramethrin)

CH

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L.) Cl ₂ C = CH

Il

(3ioallethrin)

(Fenfluthrin)

CN ι

0 »

CH,

-CH = CBr,

(Decamethrin)

0.)

Cl

egg (Penfenate) (. ^ - Hexachlorocyclohexane

It

P.) CCl ₂ = CH-OP- (OCH,) (DDVP)

OO CH, Q.) (CH-O) "- PS-CH ₉ -Cn / (omethoate)

It

R.) (CH, O) ₂ -P-CH-CC1,

OH- (trichlorfon)

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S Cl

S.) (C ₂ H ₅ O) ₂ -PO - ^) - Cl (Chlorpyrifos)

egg

S CH ₃

T.) (CH ₁ O) _n -POA- (penthione)

S CN

U.) (C ₂ H ₅ O) ₂ -P-O-N = C- <f ₃ (^ oxi _m )

S CN V.) (C ₂ H ₅ O) ₂ -PON = C ~ ^>. (Chlorphoxim)

Cl

' ^a \ _' (diazinon)

^X 3

X.) (CH ₃ O) ₂ -P-CH ₂ OOC ₂ H ₅ (malathion)

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Table ^; II Examples of synergists which can be used according to the invention

It

1.) CH, (CH ₂ ), - NH-CO-CH ₂ -C = CH

2.) CH ₃ -C-CH ₂ -NH-CO-O-CH ₂ -C = I OHj

^p ^ o

, ) - \ it 3.) <H> -NH-C-O-CH ₂ -C = CH

4.) Standard synergist:, Piper ony lbu t ox id (commercial product)

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Active ingredient code book. (see Table I) + Synergist No. (see Table ID Concentrations in% active ingredient + synergist - , 04 LT 100 after minutes or% after 360 ' A) - 1.0 - 2 360 '= 10% B) 1.0 - 2 360 '= 25% C) - 1.0 - , 0 360 '= 0% D) - 0.2 - , 04 360 '= 95% E) ..; ../; , / 0.04 - , 04 360 '= 65% F) ν 0.04 - , 04 360 '= 0% G) - 0.04 - , 04 90 ' L) - 0.00032 - 360 '= 50% M) - ' 0,008 - 75 ' N) - 1.0 - 360 '= 50% 0) - 0.04 - 105 ' P) - 0,008 - 210 ' Q) - 0.04 - 36O '= 45% R) - 1.0 - 360 ' S) - 1.0 - - 360 '= 45% T) 0.2 - 360 '= 90% U) - 1.0 - 360 '= 90% ^v > - 1.0 - 360 '= 20% W) - 0.04 - 360 '= 65% X) - 1.0 0 360 '= 45% - 1. - 0 180 ' - Second - 0 240 ' - Third - 1 360 '= 20% - 4th - 0 360 '= 0% A + 1 0.04 0 120 ' A +2 0.04 0 90 ' A +3 0.04 0 90 ' A +4 0.04 360 '= 80% Le A 21 888

Active substance code book (see Table I) + Synergist No. (see Table II) Concentrations in% active ingredient + synergist + 0.008 LT 100 after minutes or% after 360 ' B + 2 0,008 + 0.2 105 ' B + 4 0.2 + 0.008 360 '= 90% C + 2 0,008 + 0.2 150 ' C ':: + 4 0.2 t 0.04 360 '= 35% D + 2. 0.04 + 0.04 180 ' D 'i; + 4 '^; ö, 04 + 0.04 360 '= 20% E ^{: +} 2; 0.04 + 0.04 75 '' F + 2 0.04 + 0.04 150 '; F + 4 0.04 + 0.04 360 '= 95%,'. ', G + 2 0.04 + 0.04 60 ' G + 4 0.04 + _# 0,00032 60 ' L + 2 0.00032 + 0.00032 360 ' L , + 4 0.00032 + 0.008 360 '= 80% M + 2. 0,008 + 0.008 60 ' M + 4 0,008 + 0.04 75 ' N + 1 0.04 + 0.2 120 ' N + 2 0.2 + 0.04 120 ' N + 3 0.04 +0.2; 90 ' N + 4 0.2 + 0.04 360 '= 80% 0 + 2 0.04 + 0.04 60 ' 0 + 4 0.04 + 0,008 105 ' P + 2 0,008 + 0.008 90 ' P + 4 0,008 + 0.04 210 ' Q + 2 0.04 + 0.04 150 ' Q + 4 0.04 360 '

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Active ingredient code letter (cf.

 Table I)

Synergist no.

(see Table II) Concentrations in% LT 100 after active ingredient + synergist minutes resp.

% to 360 '

R R S S

U V V W W X X

2 4 2 4 2 4 2 4 2 4 2 4 2 4

0.04

0.04

0.04

0.04 0.04

1.0 60 I 1/0 360 I 0.2 360 I 1/0 360 '= 85 0.04 180 I 0.2 360 '= 80 0.04 360 • 1/0 360 '= 60 0.04 180 t 1/0 360 '= 95 0.04 180 I 0.04 360 '= 70 0.2 180 I 1/0 360 '= 30

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The preparation of the compounds of the general formula (I) (or (Ia)) according to the invention is to be explained by the following preparation examples:

Preparation Examples

(CH ₃ ) C-CH ₂ -NH-CO-O-CH ₂ -C = CH (Example 2) N- (2,2-dimethyl-propyl) -carbamic acid O-2-propynyl ester

Variant with diluent :

11.3 g of N- (2,2-dimethyl-propyl) isocyanate are dissolved in 60 ml of acetone, and 10 mg of diazabicyclooctane (DABCO) (= "triethylenediamine) are added, 5.6 g of this reaction mixture are added dropwise at room temperature. After concentration of the mixture for one hour, the mixture is allowed to cool and, after concentration, the solid formed (Ν, Ν'-dineopentylurea, mp 100 ° C.) is filtered off and discarded.The residual oil is freed from the residual solvent in a high vacuum 11 g of N-neopentyl-carbamic acid-propargyl ester are obtained in the form of a colorless oil (65%).

on

theory yield) n ^: 1.4561.

Variant without diluent: ·

(22.6 g N- (2,2-dimethyl-propyl) isocyanate, 10 mg of diazabicyclooctane (DABCO) contain (= triethylenediamine) are 11.2 g propynyl alcohol was added dropwise at 6O ⁰ C. After 1 to After 2 hours, the IR spectrum of a sample no longer shows an NCO band, after distillation at 85 ° C./0.03 mbar, 32.0 g (95.4% of theory) of the above compound having a purity of 99.7% ( Gas chromatograms).

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Λ i \ i

The remaining compounds which can be used according to the invention are obtained in an analogous manner:

R-NH-CO-OCC ^ CR ³

1 2 "3

Example R RRR refractive index

Nr, n £ ° (or Fp ( ⁰ C))

1 CH ₃ (CH ₂ ) ₃ - HHH 1, 4560

H HH 1, 4450

(CH ₃ J ₃ C-CH-HH H 1, 4642

(CH ₃ J ₂ CH-CH ₂ --HHH 1.4576

H HH 1.4572

HHH (FpJ 54-56

Cl- (CH ₀ ) .- HHH 1, 4859

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Claims (6)

Pesticides containing an active ingredient combination of at least one arthropod active substance and a synergist, characterized in that the synergist is a carbamic acid ester having the general formula (I) R 1 R R -KH-GO-OCG = C-R3 (D in V / R is optionally substituted alkyl having 4 or more carbon atoms or optionally substituted cycloalkyl and 1 2 "3
R ₁ R and R- are the same or different and individually represent hydrogen or optionally substituted alkyl, represents. 2. Pesticides according to item 1, characterized in that in formula (I) AP A 01 N / 253 900/1 62 594 11 R is an optionally substituted by alkoxy (C ₁ -C *), halogen, cyano, nitro and / or trifluoromethyl substituted alkyl radical having 4 to 12 carbon atoms or an optionally alkoxy (C ₁ -C.), Halogen, cyano, nitro and or trifluoromethyl-substituted cycloalkyl radical having 4 to 10 carbon atoms and R, R, R ^{J are the} same or different and are individually hydrogen or an optionally substituted by halogen, cyano, C ₁ -C. Alkoxy, Cj-C-alkylthio or trifluoromethyl substituted alkyl having 1 to 2 carbon atoms. Pesticides according to item 1, characterized in that in formula (I) R is optionally substituted by chlorine or cyano-substituted alkyl having 4 to 6 carbon atoms or optionally substituted by trifluoromethyl-substituted cyclohexyl and R ¹ , R ² and R ^{3 are} hydrogen. 4. Use of the pesticides according to items 1 to 3, characterized in that they are used for controlling pests, in particular arthropods. AP A 01 N / 253 900/1 62 594 11 5 «A process for the preparation of pesticides, characterized in that a combination of active ingredients from at least one arthropod active ingredient and a synergist of the formula (I) (according to point 1) with the usual extenders and diluents and optionally Pormulierhilfsstoffen, such as emulsifiers, mixed. 6. A method for controlling pests, characterized in that one allows pesticides according to the items 1 to 4 to act on the pests and / or their habitat.