EP0000127A1 - Insecticidal and acaricidal compositions, their manufacture and their use - Google Patents

Abstract

Insecticidal and acaricidal compositions containing an active ingredient combination consisting of: 1) phosphorus-containing compounds of the general formula <IMAGE> in which R¹, R² and R³ are, independently of one another, the radicals alkyl, alkenyl or aryl, which may be substituted, where at least one of the radicals is an optionally substituted alkenyl radical which is unsaturated in the 2-position, X is oxygen or sulfur, Y and Z independently of one another are oxygen, sulfur or a simple bond; if both Y and Z are oxygen or sulfur or a simple bond, then R¹, R² and R³ can additionally mean propargyl in the radicals indicated above; and 2) A carbamates, and / or B carboxylic acid esters, including the natural and synthetic pyrethroids and / or C phosphoric acid esters and / or D halocycloalkanes and / or E haloalkanes, are prepared by mixing the above-mentioned component with extenders and / or surface-active agents.

Description

The present invention relates to new insecticidal and acaricidal synergistic active substance combinations of partially known phosphorus-containing compounds and pesticidal active substances.

• A. Carbamate, wie z. B. das 2-iso-Prophyl-phenyl-N-methyl- carbamat, 2-(1-Methyl-allyl)-phenyl-N-Methyl-carbamat, 3-iso-Propyl-4-methoxy-phenyl-N-methyl-carbamat, 2-[1 ,3-Dioxolan(2)yl-phenyl]-N-methyl-carhamat, 2,2-Dimethyl-1,3-benzodiol(4)yl-N-methyl-cartamat, 2,2-Dimethyl- bzw. 2-Methyl-2,3-dihydrobenzofurar(4)yl-N-methyl-carbamat und 2,3-Dihydro-2,2-dimethylbenzofuran( ):ly-N-acetyl-N-methyl- carbamat, 3,4,5-Trimethyl-phenyl-N-methylcarbamat, 1-Naphthyl-N-methyl-carbamat
• 3. Carbonsäurester, wie z. B.
  
  methyl-
  
  -trichlor-1-(3,4-
  
  -2.2-dimethyl-3-(2,2-dichlorvinyl)-cyclopropancarboxylat
• C. Phospohorsäureester, wie z. B. 0,0-Dimethyl-0-(2,2-dichlor- vinyl)-phosphorsäureester und O,O-Dimethyl-O-[3-methyl-4-methylthio-phenyl]-thionophosphorsäureester
• D. Halogencycloalkane, wie z. B. Hexachlorcyclohexan und
• E. Halogenalkane, wie z. B. 1,1,1-Trichlor-2,2-bis-(4-methoxyphenyl)-äthan.

It has already become known that the following active ingredients or groups of active ingredients have pesticidal, in particular insecticidal and acaricidal properties:

• A. carbamates such as e.g. B. the 2-iso-propyl-phenyl-N-methyl-carbamate, 2- (1-methyl-allyl) -phenyl-N-methyl-carbamate, 3-iso-propyl-4-methoxy-phenyl-N-methyl carbamate, 2- [1,3-dioxolane (2) yl-phenyl] -N-methyl-carhamate, 2,2-dimethyl-1,3-benzodiol (4) yl-N-methyl-cartamate, 2,2 -Dimethyl- or 2-methyl-2,3-dihydrobenzofuran (4) yl-N-methyl-carbamate and 2,3-dihydro-2,2-dimethylbenzofuran (): ly-N-acetyl-N-methyl-carbamate , 3,4,5-trimethyl-phenyl-N-methyl carbamate, 1-naphthyl-N-methyl carbamate
• 3. Carboxylic acid esters, such as. B.
  
  methyl-
  
  -trichlor-1- (3,4-
  
  -2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate
• C. phosphoric acid esters such as e.g. B. 0.0-Dimethyl-0- (2,2-dichloro-vinyl) phosphoric acid ester and O, O-dimethyl-O- [3-methyl-4-methylthio-phenyl] thionophosphoric acid ester
• D. Halogencycloalkane, such as. B. hexachlorocyclohexane and
• E. Haloalkanes, such as. B. 1,1,1-trichloro-2,2-bis (4-methoxyphenyl) ethane.

Furthermore, synergistic mixtures of carbamates, e.g. B. 2-iso-propoxyphenyl-N-methyl carbamate or phosphoric acid esters, e.g. B. 0.0-diethyl-0- (2-isopropyl-4-methyl-pyrimidinyl- [6]) - phosphorothioate, or of natural or synthetic pyrethroids with piperonyl ethers, such as. B.α- [2- (2-butoxy-ethoxy) -ethoxy] -4,5-methylenedioxy-2-propyl-toluene, known (see Bull, Org.-Health Org. 1966, 35, pages 691-708 , Schrader G .: The development of new insecticidal phosphoric acid esters 1963, p. 158; Perkov, W .: Die Insektizide, 1966, pages 516-524). The effectiveness of these synergists is unsatisfactory; only α- [2- (2-butoxy-ethoxy) ethoxy] -4,5-methylenedioxy-2-propyl-toluene (piperonyl butoxide) has achieved a certain importance. In addition, the known synergists can only be produced in a complex and expensive manner, which limits their possible uses. Finding easily accessible and inexpensive synergists is therefore desirable.

in welcher

• R¹, R² und R³ unabhängig voneinander
  
  Reste Alkyl, Alkenyl oder Aryl
  
  gegebenenfalls substrtuiert sein
  
  mindestens einen der Reate für einen
  
  ungesättigten gegebenfalls
  
  Alkenylrest steht,
• für Sauerstoff oder Schweist steht
• Y und Z imabhänging voneinander für Sauerstoff, Schwefel oder eine einfache Bindung stehen; stehen sowohl Y als auch Z für Sauerstoff oder für Schwefel oder für eine eirfache Bindung, so können R¹ und R² und R³ zusätzlich zu den oben angegebenen Resten Propargyl bedeuten;

und

• A. Carbamaten, und/oder
• B. Carbonsäureestern, einschließlich der natürlichen sowie synthetischen Pyrethroide und/oder
• C. Phosphorsäureestern und/oder
• D. Halogencycloalkanen und/oder
• E. Halogenalkanen

eine besonders hohe insektizide und

aufwei - sen. Die synergistische Wirkung der

nen Formel (I) zeigt sich bevorzugt be den

• A. Carbamaten der allgemeinen Formel (II)
  
  in welcher
  • R⁴ für Aryl, Heterocyclus oder einen Oximrest steht,
  • R⁵ für Wasserstoff oder Alkyl mit 1 bis 4 C-Atomen steht und
  • R⁶ für Alkyl, Alkylcarbonyl mit 1 - 6 C-Atomen im Alkylrest, der gegebenenfalls auch durch Hydroxy oder Methylthio substituiert sein kann, oder den Rest -S-W, steht, wobei für einen gegebenenfalls durch Halogen substituierten aliphatischen Rest mit 1 bis 4 C-Atomen, insbesondere CC1₃ und CF₃, sowie für gegebenenfalls bevorzugt durch CN, Halogen, insbesondere Chlor, Methyl, Trihalogenmethyl, Trifluormethylmercapto oder N0₂ substituierten Arylrest, insbesondere Phenyl, oder für Methoxycarbonyl oder für den Rest V-S0₂-N-_R ⁵ steht, wobei V für Alkyl, Halogenalkyl oder Halogen, Trihalogenmethyl, CN, Methyl oder Nitro substituierten Arylrest steht.
  
  Besonders bevorzugt sind Carbamate, in denen
  • R⁴ für Phenyl oder Naphthyl steht, die gegebenenfalls substituiert sind durch Alkyl, Alkenyl, Alkoxy, Alkylmercapto mit jeweils 1 bis 5 C-Atomen, Dialkylamino, Dialkenylamino bis zu 3 C-Atomen je Alkyl- bzw. Alkenylteil, Halogen, insbesondere Chlor, Dioxolanyl oder den Rest -N=CH-N (C_1-4-Alkyl)₂;
  
  weiterhin sind besonders bevorzugt Carbamate, in denen
  • _R ⁴ für 2,3-_Dihydrobenzofuranyl, Benzodioxol, Benzothienyl, Pyrimidyl oder Pyrazolyl steht, die geqepenenfalls durch C_1-4-Alkyl, insbesondere Methyl cder Dialkvlamino mit 1 bis 4 C-Atomen je
    
    sind;
  
  Weiterhin sind bescriders bevorsugt Carbamate, in denen R⁴ für einen
  
  der allgemeinen Formel (II a)
  
  steht,
  in welcher
  • R⁷ und R³ gleic, oder verschieden sind und für Alkyl, Cyclcalkyl, Alkenyl, Alkinyl, Alkoxy, Alkylmercaptc, Alkoxycarbonyl, Carbonylamid, Alkylmercaptoalkyl mit jeweils bis zu 5 C-Atomen, CN, Aryl, insbesondere Phenyl, Aralkyl, einen gegebenenfalls substituierten heterocyclischen Rest cder für Alkyl, das durch einen heterocyclischen Rest substituiert ist, stehen oder gemeinsam für einen gegebenenfalls durch C_1-4-Alkyl substituierten Dicxclanyl oder Dithiolanylrest arehen;
• B. Carbonsaareestern der allgemeinen vormal (III)
  
  in welcher
  • R⁹ für Alkyl, Aralkyl, Aryl oder Cycloalkyl steht, die gegepenenfalls substituiert sein können und
  • R¹⁰ für Wasserstoff, Alkyl,
    
    , Alkenyl, Alkinyl,
    
    steht und
  • _R ¹¹ für Aryl oder einen Heterocyclus steht, oder gemeinsam mit R¹⁰ einen gegebenenfalls substituierten Cyclopentenonring bildet;
  
  besonders bevorzugt sind Carbonsäureester, in denen
  • _R ⁹ für Alkyl mit 1 bis 6 C-Atomen, das gegebenenfalls durch gegebenenfalls halogensubstituiertes Phenyl substituiert ist, Cyclopropyl, das gegebenenfalls durch Alkyl, Alkenyl, Halogenalkyl oder Halogenalkenyl mit jeweils bis zu 6 C-Atomen substituiert ist oder für Phenyl, das gegebenenfalls durch Halogen subsituiert ist, steht;
  
  bevorzugt sind Carbonsäureester, in denen
  • R¹⁰ für Wasserstoff, Alkyl mit 1 bis 6 C-Atomen, Halogenalkyl mit 1 bis 4 C-Atomen und bis zu 3 Halogenatomen, CN oder Äthinyl steht;
  
  weiter sind besonders bevorzugt Carbonsäureester, in denen
  • _R ¹¹ für Phenyl steht, das gegebenenfalls durch C_1-4-Alkyl, Halogen, insbesondere Fluor oder Chlor, gegebenenfalls halogen- oder methylsubstituiertes Phenoxy, gegebenenfalls substituiertes Benzyl substituiert ist, ferner für Furanyl, Tetrahydrophthalimido, Benzodioxol, die gegebenenfalls durch Halogen, insbesondere Chlor, Alkyl der Alkenyl mit bis zu 4 C-Atomen oder Benzyl substituiert sind, steht und ferner für Cyclopentenon steht, das gegebenenfalls durch C_1-4-Alkyl, Furfuryl C_1-5-Alkenyl substituiert ist;
  
  weiter sind besonders bevorzugt die natürlichen Pyrethroide;
• C. Phosphorsäureestern der allgemeinen Formel (IV)
  
  in welcher X unabnängig voneinander sur O oder S stehen und
  
  
  zentralen
  
  und dem Rest R¹⁴ stent und
  • R¹² und R¹³ gleich oder verschieder sind und für Alkyl oder Aryl stehen und
  • R¹⁴ für Alkyl, Aryl, Heteroaryl, Aralkyl, Alkenyl, Dioxanyl oder einen Oximrest oder für den glei- chen Rest steht, an das as gebunden ist; mit der Maßgabe, daß R¹⁴ -A- nicht den 2-Methoxy-4- cyanc-phenoxyrest bedesten soll, wenn als Synergist Chlormethanphosphonsäuredipropargylester verwendet wird.
  
  Besonders bevorzugt sind Phosphorsäureester, in denen
  • R¹² und R¹³ gleich oder verschieden sind und für C_1-4-Alkyl oder Phenyl stehen und
  • R¹⁴ für Alkyl mit 1 - 4 C-Atomen sceht, das
    
    fails durch Halogen,
    
    gegebenenfalls a
    
    Carbonylaimd,
    
    fonylakyl, Sulfoxyalkyl, Carbonylalkyl, Alkoxy. Alkylmercapto,
    
    substituiert ist; für Alkenyl mit bis zu 4 C-Atomen steht, das gegebenenfalls
    
    gegebenenfalls halogensubstituiertes
    
    oder Alkoxycarbo- nyl dilstituiert ist,
    
    für den Oximrest der allgemeine Formel
    
    steht,
    
    wobei
  • R⁷ und R die oben angegebene Bedeutung besitzen, insbesondere jedoch für Cyan oder Phenyl stehen, oder für Dioxanyl steht, das durch denselben Rest substituiert ist, an den R¹⁴ gebunden ist, oder R¹⁴ steht für den gleichen Rest,an den es gebunden ist, oder R¹⁴ steht für Phenyl, das gegebenenfalls durch Methyl, Nitro, CN, Halogen, Methylmercapto substituiert ist;
  • R¹⁴ steht außerdem besonders bevorzugt für gegebenenfalls durch C_1-4-Alkyl oder Halogen substituierte Heteroaromaten wie Pyridin, Chinolin, Chinoxalin, Pyrimidin, Diazinon, Benzo-1,2,4-triazin;
• D. Cycloalkane der Formel (V)
  
  in welcher Hal, Halogen, vorzugsweise Chlor bedeutet;
• E. Halogenalkanen der Formel (VI)
  
  in welcher Hal' für Chlor oder Brom
  • _R ¹⁵ für Wasserstoff oder Hydroxyl
  • _R ¹⁶ und _R ¹⁷ gleich oder verschieden sind und für Halogen, Alkyl oder Alkoxy und
  • R¹⁸ für Wasserstoff oder Halogen stehen.
  
  Besonders bevorzugt sind Halogenalkane, in denen
  • R¹⁵ Wasserstoff oder Hydroxyl bedeutet,
  • R¹⁶ und R¹⁷ für gleiches Halogen, Alkyl bzw. Alkoxyl mit 1 bis 4 Kohlenstoffatomen je Alkyl bzw. Alkoxyrest stehen und
  • _R ¹⁸ Halogen bedeutet.

It has now been found that active ingredient combinations of phosphorus-containing compounds of the general formula I

in which

• R ¹ , R ² and R ³ independently of one another
  
  Residues alkyl, alkenyl or aryl
  
  may be substituted
  
  at least one of the reate for one
  
  unsaturated if necessary
  
  Alkenyl radical stands,
• stands for oxygen or sweat
• Y and Z are, independently of one another, oxygen, sulfur or a simple bond; if both Y and Z are oxygen or sulfur or a simple bond, then R ¹ and R ² and R ³ can mean propargyl in addition to the radicals indicated above;

and

• A. carbamates, and / or
• B. carboxylic acid esters, including natural and synthetic pyrethroids and / or
• C. phosphoric acid esters and / or
• D. Halogencycloalkanes and / or
• E. Haloalkanes

a particularly high insecticide and

exhibit. The synergistic effect of

NEN formula (I) is preferably shown

• A. Carbamates of the general formula (II)
  
  in which
  • R ^{4 represents} aryl, heterocycle or an oxime radical,
  • R ^{5 represents} hydrogen or alkyl having 1 to 4 carbon atoms and
  • R ^{6 represents} alkyl, alkylcarbonyl having 1-6 C atoms in the alkyl radical, which can optionally also be substituted by hydroxy or methylthio, or the radical -SW, where an aliphatic radical optionally substituted by halogen having 1 to 4 C- Atoms, in particular CC1 ₃ and CF ₃ , and for aryl radicals, in particular phenyl, which are preferably substituted by CN, halogen, in particular chlorine, methyl, trihalomethyl, trifluoromethylmercapto or N0 ₂ , or for methoxycarbonyl or for the radical V-S0 ₂ -N- _R ⁵ is where V is alkyl, haloalkyl or halogen, trihalomethyl, CN, methyl or nitro substituted aryl.
  
  Carbamates in which
  • R ^{4 represents} phenyl or naphthyl, which are optionally substituted by alkyl, alkenyl, alkoxy, alkyl mercapto each having 1 to 5 carbon atoms, dialkylamino, dialkenylamino up to 3 carbon atoms per alkyl or alkenyl part, halogen, in particular chlorine, Dioxolanyl or the radical -N = CH-N (C _1-4 alkyl) ₂ ;
  
  furthermore, carbamates in which
  • _R ^{4 represents} 2,3- _D ihydrobenzofuranyl, benzodioxole, benzothienyl, pyrimidyl or pyrazolyl, which geqepenenfalls by C _1-4 alkyl, especially methyl or dialkvlamino with 1 to 4 carbon atoms each
    
    are;
  
  Furthermore, bescriders are prevented carbamates in which R ^{4 is} for one
  
  of the general formula (II a)
  
  stands,
  in which
  • R ⁷ and R ^{3 are the} same or different and are optionally substituted for alkyl, cyclcalkyl, alkenyl, alkynyl, alkoxy, alkyl mercaptc, alkoxycarbonyl, carbonylamide, alkylmercaptoalkyl each having up to 5 carbon atoms, CN, aryl, in particular phenyl, aralkyl heterocyclic radical or alkyl which is substituted by a heterocyclic radical, or together are a dicxclanyl or dithiolanyl radical optionally substituted by C _1-4 -alkyl;
• B. carbonic acid esters of the general vormal (III)
  
  in which
  • R ^{9 represents} alkyl, aralkyl, aryl or cycloalkyl, which can optionally be substituted and
  • R ¹⁰ for hydrogen, alkyl,
    
    , Alkenyl, alkynyl,
    
    stands and
  • _R ^{11 represents} aryl or a heterocycle, or together with R ¹⁰ forms an optionally substituted cyclopentenone ring;
  
  carboxylic acid esters in which
  • _R ⁹ for alkyl with 1 to 6 C atoms, which is optionally substituted by optionally halogen-substituted phenyl, cyclopropyl, which is optionally substituted by alkyl, alkenyl, haloalkyl or haloalkenyl, each having up to 6 C atoms, or for phenyl, which is optionally substituted by Halogen is substituted;
  
  carboxylic acid esters are preferred in which
  • R ^{10 represents} hydrogen, alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 4 carbon atoms and up to 3 halogen atoms, CN or ethynyl;
  
  further preferred are carboxylic acid esters in which
  • _R ^{11 represents} phenyl, which is optionally substituted by C _1-4 -alkyl, halogen, in particular fluorine or chlorine, optionally halogen- or methyl-substituted phenoxy, optionally substituted benzyl, furthermore furanyl, tetrahydrophthalimido, benzodioxole, optionally by halogen, in particular Chlorine, alkyl of alkenyl with up to 4 carbon atoms or benzyl are substituted, and furthermore stands for cyclopentenone which is optionally substituted by C _1-4 alkyl, furfuryl C _1-5 alkenyl;
  
  natural pyrethroids are particularly preferred;
• C. phosphoric acid esters of the general formula (IV)
  
  in which X are independent of each other sur O or S and
  
  
  central
  
  and the rest R ¹⁴ stent and
  • R ¹² and R ^{13 are the} same or different and represent alkyl or aryl and
  • R ^{14 represents} alkyl, aryl, heteroaryl, aralkyl, alkenyl, dioxanyl or an oxime radical or the same radical to which as is bonded; with the proviso that R ¹⁴ -A- should not be a problem for the 2-methoxy-4-cyanc-phenoxy radical if chloromethanephosphonic acid dipropargyl ester is used as a synergist.
  
  Phosphoric acid esters in which
  • R ¹² and R ^{13 are the} same or different and are C _1-4 alkyl or phenyl and
  • R ^{14 is} for alkyl with 1 to 4 carbon atoms, that
    
    fails by halogen,
    
    if applicable a
    
    Carbonylaimd,
    
    fonylakyl, sulfoxyalkyl, carbonylalkyl, alkoxy. Alkylmercapto,
    
    is substituted; stands for alkenyl with up to 4 carbon atoms, which, if appropriate
    
    optionally halogen-substituted
    
    or alkoxycarbonyl is diluted,
    
    for the oxime residue of the general formula
    
    stands,
    
    in which
  • R ⁷ and R have the meaning given above, but in particular represent cyano or phenyl, or represents dioxanyl which is substituted by the same radical to which R ^{14 is} bonded, or R ¹⁴ represents the same radical to which it is bonded or R ¹⁴ represents phenyl which is optionally substituted by methyl, nitro, CN, halogen, methylmercapto;
  • R ¹⁴ also particularly preferably represents heteroaromatics which are optionally substituted by C _1-4 -alkyl or halogen, such as pyridine, quinoline, quinoxaline, pyrimidine, diazinon, benzo-1,2,4-triazine;
• D. Cycloalkanes of Formula (V)
  
  in which Hal means halogen, preferably chlorine;
• E. Haloalkanes of Formula (VI)
  
  in which hal 'for chlorine or bromine
  • _R ^{15 is} hydrogen or hydroxyl
  • _R ¹⁶ and _R ^{17 are the} same or different and are halogen, alkyl or alkoxy and
  • R ^{18 represents} hydrogen or halogen.
  
  Halogenalkanes in which
  • R ¹⁵ denotes hydrogen or hydroxyl,
  • R ¹⁶ and R ^{17 represent the} same halogen, alkyl or alkoxyl with 1 to 4 carbon atoms per alkyl or alkoxy radical and
  • _R ¹⁸ means halogen.

Surprisingly, the insecticidal and / or acaricidal action of the active compound combinations according to the invention is substantially higher than the action of the individual component or the sum of the actions of the individual components. It is also significantly higher than the effect of the already known combinations of active substances consisting of 2-iso-propoxy-phenyl-N-methyl-carbamate and piperonyl butoxide. In addition, the phosphorus-containing compounds which can be used according to the invention as synergists show excellent synergistic activity not only with one class of active compound, but with active compounds from a wide variety of chemical groups.

Thus, synergistic mixtures which contain the phosphorus-containing compounds of the formula I which can be used according to the invention are a valuable addition to the technology.

• R² für Alkyl mit 1 bis 4 C-Atomen, insbesondere für Alkenyl mit 2 bis 4 C-Atomen, insbesondere für Alkyl, die durch Halogen oder Alkoxyreste substituiert sein können, ferner für Phenyl steht, und
• R³ für Alkenyl mit 3 bis 4 C-Atomen steht, das in 2-Stellung eine Doppelbindung trägt und durch Methyl substituiert sein kann; insbesondere steht R jedoch für Alkyl;
• X steht für Sauerstoff oder Schwefel und Y und Z stehen unabhängig voneinander für Sauerstoff, Schwefel oder eine einfache Bindung.

The majority of the phosphorus-containing compounds of the formula I are known and can be obtained by customary processes. The phosphorus-containing compounds of the general formula I which can be used according to the invention include phosphoric acid esters, thiophosphorus

• R ^{2 represents} alkyl having 1 to 4 carbon atoms, in particular alkenyl having 2 to 4 carbon atoms, in particular alkyl, which may be substituted by halogen or alkoxy radicals, furthermore represents phenyl, and
• R ^{3 represents} alkenyl having 3 to 4 carbon atoms, which bears a double bond in the 2-position and can be substituted by methyl; in particular, however, R represents alkyl;
• X stands for oxygen or sulfur and Y and Z independently of one another for oxygen, sulfur or a simple bond.

However, at least one of the radicals R ¹ , R ² and R ³ must stand for a radical which is unsaturated in the 2-position; the allyl radical is particularly preferred.

Also preferred are compounds in which both Y and Z are oxygen or sulfur or a single bond and _R ¹ , _R ² and _R ³ are propargyl in addition to the meanings given above.

• Allylphosphonsäuredimethylester
• Allylphosphonsäurediäthylester
• Allylphosphonsäuredi-n-propylester
• Allylphosphonsäuredi-i-propylester
• Allylphosphonsäuredi-2-chloräthylester
• Allylphosphonsäuredi-2-bromäthylester
• Allylphosphonsöuredi-2-chlorpropylester
• Allyyphosphonsäuredi-2-brompropylester
• Allylphosphonsäurediallylester
• Allylphosphonsäureallyläthylester
• Allylphosphonsäureallylpropylester
• Allylphosphonsauredibutylester
• Allyphosphonsäurediisobutylaster
• Allylphosphonsäuredi-2-butylaster
• Allylphosphosäurediamylester
• Allylphosphonsäurediisoamlester
• Allylphosphonsäuredihexylester
• Allylphosphonsäure-di-2-äthylhexylester
• Allylphosphonsäuremethylbenzylester
• Allylphosphonsäureäthylbenzylester
• Allylphosphonsäurepropylbenzylester
• Allylphosphonsäuredibenzylester
• Allylphosphonsäurediphenylester
• Allylphosphonsäuremethylphenylester
• Allylphosphonsäureäthylphenylester
• Allylphosphonsäuremethyl-4-chlorphenylester
• Allylphosphonsäuremethyl-4-methoxyphenylester
• Allylphosphonsäuredi-2-chloräthylester
• Allylphosphonsäuredi-2-chlorpropylester
• Allylphosphonsäureäthylpropylester
• Allylphosphonsäurepropylbutylester
• Allylphosphonsäure-bis-2,3-dichlorpropylester
• Allylphosphonsäuremethyl-2,2-dichlorvinylester
• Allylphosphonsäureäthyl-2,2-dichlorvinylester
• Allylphosphonsäurepropyl-2,2-dichlorvinylester
• Allylphosphonsäureisopropyl-2,2-dichlorvinyleater
• Allylphosphonsäurebutyl-2,2-dichlorvinylester
• Allylphosphonsäureisobutyl-2,2-dichlorvinylester
• Allylmonothiophosphonsäure-0-äthyl-S-methylester
• Sllylmonothiophosphonsäure-0-propyl-S-methylester
• Allylmonothiophosphonsäure-0-butyl-S-methylester
• Allylmonothiophosphonsäure-0-äthyl-S-butylester
• Allylmonothiophosphonsäure-0-propyl-S-butylester
• Allylmorothiophosphonsäure-0-butyl-S-butylester
• Allylmonothiophosphonsäure-0-äthyl-O-2,2-dichlorvinylester
• Allylmonothiophosphonsäure-0-propyl-0-2,2-dichlorvinylester
• Allylmonothiophosphonsäure-0-isopropyl-0-2,2-dichlorvinylester
• Allylmonothiophosphonsäure-0-butyl-0-2,2-dichlorvinylester
• Allylmonothiophoephonsäure-0-isobutyl-0-2,2-dichlorvinylester
• Allylmonothiophosphoneäure-0,0-dimethylester
• Allylmonothiophosphonsäure-0,0-diäthylester
• Allylmonothiophosprionsäure-dichloräthylester
• Allylmonothiophosphonsäure-di-n-propylester
• Allylmonothiophosphonsäure-di-isopropylester
• Allylmonothiophosphonsäure-di-n-butylester
• Allylmonothiophosphonsäure-di-2-butylester
• Allylmonothiophosphonsäure-O,S-dimethylester
• Allylmonothiophosphonsäure-0,S-diäthylester
• Allylmonothiophosphonsäure-0-äthyl-S-2-hydroxyäthylester
• Allyldithiophosphonsäure-O-äthyl-S-methylester
• Methanphosphonsäurediallylester
• Methanphosphonsäuremethylallylester
• Methanphosphonsäureäthylallylester
• Methanphosphonsäurepropylallylester
• Methanphosphonsäurebutylallylester
• Methanphosphonsäureallyl-2,3-dichlorpropylester
• Methanphosphonsäureallyl-2,3-dibrompropylester
• Chlormethanphosphonsäurediallylester
• Chlormethanphosphonsäuremethylallylester
• Chlormethanphosphonsäureäthylallylester
• Chlormethanphosphonsäurepropylallylester
• Chlormethanphosphonsäurebutylallylester
• Chlormethanphosphonsäureallyl-2,3-dichlorpropylester
• Chlormethanphosphonsäureallyl-2,3-dibrompropylester
• 2-Buten-1-phosphonsäuredimethylester
• 2-Buten-1-^phosphonsäurediäthylester
• 2-Buten-1-phosphonsäuredipropylester
• Triallylphosphat
• Tripropargylphosphat
• Äthanphosphonsäurediallylester
• Äthanphosphonsäuremethylallylester
• Äthanphosphonsäureäthylallylester
• Äthanphosphonsäure-n-propylallylester
• Äthanphosphonsäure-i-propylallylester
• Äthanphosphonsäure-n-butylallylester
• Äthanphoaphonsäure-i-butylallylecter
• Propanphosphonsäurediallylester
• Propanphosphonsäuremethylallylester
• Propanphosphonsäureäthylallylester
• Propanphosphonsäure-n-propylallylester
• Propanphosphonsäure-i-propylallylester
• Propanphosphonsäure-n-butylallylester
• Propanphosphonsäure-i-butylallyleater
• Vinylphosphonsäurediallylester
• Vinylphosphonsäuremethylallylester
• Vinylphosphonsäureäthylallylester
• Vinylphosphonsäure-n-propylallylester
• Vinylphosphonsäure-i-propylallyleater
• Vinylphosphonsäure-n-butylallylester
• Vinylphoephonsäure-i-butylallylester
• 1-Methylvinylphosphonsäurediallylester
• 1-Methylvinylphosphonsäuremethylallyester
• 1-Methylvinylphosphonsäureäthylallylester
• 1-Methylvinylphosphonsäure-n-propylallylester
• 1-Methylvinylphosphonsäure-i-propylallylester
• 1-Methylvinylphosphonsäure-n-butylallylester
• 1-Methylvisylphosphonsäure-i-butylallylester
• 2,2-Dimethylvinylphosphonsäurediallylester
• 2,2-Dimethylvinylphosphensäuresmethylallylester
• 2,2-Dimethylvinylphosphonsäureäthylallylester
• 2,2-Dimethylvinylphosphonsäure-n-propylallylester
• 2,2-Dimethylvinylphesphonsäure-1-propylallylester
• 2,2-Dimethylvinylphosphonsäure-n-butylallylester
• 2,2-Dimethylvinylphosphonsäure-i-butylallylester
• Benzylphosphonsäurediallylester
• Benzylphosphonsäuremethylallylester
• Benzylphosphonsäureäthylallylester
• Benzylphosphonsäure-n-propylallylester
• Benzylphosphonsäure-i-propylallylester
• Benzylphosphonsäure-n-butylallylester
• Benzylphosphonsäure-i-butylallylester
• 2-Phenylvinylphosphonsäurediallylester
• 2-Phenylvinylphosphonsäuremethylallylester
• 2-Phenylvinylphosphonsäureäthylallylester
• 2-Phenylvinylphosphonsäure-n-propylallylester
• 2-Phenylvinylphosphonsäure-i-propylallylester
• 2-Phenylvinylphosphonsäure-n-butylallylester
• 2-Phenylvinylphosphonsäure-i-butylallylester
• Phenylphosphonsäurediallylester
• Phenylphosphonsäuremethylallylester
• Phenylphosphonsäureäthylallylester
• Phenylphosphonsäure-n-propylallylester
• Phenylphosphonsäure-i-propylallylester
• Phenylphosphonsäure-n-butylallylester
• Phenylphosphonsäure-i-butylallylester
• Phenylthiophosphonsäurediallylester
• Phenylthiophosphonsäuremethylallylester
• Phenylthiophosphonsäureäthylallylester
• Phenylthiophospnonsäure-n-propylallylester
• Phenylthiophosphonsäure-i-propylallylester
• Phenylthiophospnonsäure-n-butylallylester
• Phenylthiophosphonsäure-i-butylallylester
• 2-Äthoxyäthylenphosphonsäurediallylester
• 2-Äthoxyäthylenphosphonsäuremethylallylester
• 2-Äthoxyäthylenpaosphonsäureäthylallylester
• 2-Äthoxyäthylenphosphosäure-n-propylallylester
• 2-Äthoxyäthylenphosphonsäure-i-propylallylester
• 2-Äthoxyäthylenphosphonsäure-n-butylallylester
• 2-Athoxyäthylenphosphonsäure-i-butylallylester
• Phosphorsäuradimethylallylester
• Phosphorsäurediäthylallylester
• Phonphorsäuredipropylallylester
• Phosphorsäurediisopropylallylester
• Phosphorsäuredibutylallylester
• Phosphorsäuredichloräthylallylester
• Phosphorsäuredibenzylallylester
• Phosphorsäuremethylaiallylester
• Phosphorsäureäthyldiallylester
• Phosphorsäurepropyldiallylester
• Phosphorsäureisopropyldiallylester
• Phosphorsäurebutyldiallylester
• Phosphorsäureonloräthyldiallylester
• Phosphorsäureallyl-bis-2,3-dichlorpropylester
• Phosphorsäureallyl-bis-2,3-dibrompropylester
• Phosphorsäurediallyl-2,3-di-chlorpropylester
• Phosphorsäurediallyl-2,3-di-brompropylester
• Phosphorsäureallylmethyl-2,2-di-chlorvinylester
• Phosphorsäureallyläthyl-2,2-di-chlorvinylester
• Phosphorsäuresallylpropyl-2,2-di-chlorvinylester
• Phosphorsäureallylisopropyl-2,2-di-chlorvinylester
• Phosphorsäureallybutyl-2,2-di-chlorvinylester
• Phosphorsäureallylisobutyl-2,2-di-chlorvinylester
• Phosphorsäurediallyl-2,2-dichlorvinylester
• Phosphorsäureallyl-bis-2,2-dichlorvinylester
• 0,0,0-Triallylthiophosphat
• O,O,O-Tripropyrgylthiophosphat
• Thiophosphorsäure-0-allyl-0,0-dimethylester
• Thiophosphorsäure-0-allyl-0,0-diäthylester
• Thiophosphorsäure-0-allyl-0,0-dipropylester
• Thiophosphorsäure-0-allyl-0,0-dipropylester
• Thiophosphorsäure-0-allyl-0,0-diisopropylester
• Thiophosphorsäure-0-allyl-0,0-dibutylester
• Thiiophosphorsäure-0-allyl-0,0-di-2-chleräthylester
• Thiophosphorsäure-0,0-diallyl-0-methylester
• Thiophosphorsäure-0,0-diallyl-0-äthylester
• Thiophosphorsäure-0,0-diallyl-0-propylester
• Thiophosphorsäure-0,0-diallyl-0-isopropylester
• Thiophosphorsäure-0,0-dially-dibutylester
• Thiophosphorsäure-0,0-diallyl-0-di-2-chloräthylester
• Phosphorsäuremethyldipropargylester
• Phosphorsäureäthyldipropargylester
• Phosphorsäurepropyldipropargylester
• Phosphorsäureisopropyldipropargylester
• Phosphorsäurebutyldipropargylester
• Phosphorsäureisobutyldipropargylester
• Phosphorsäureamyldipropargylester
• Phosphorsäureisoamyldipropargylester
• Phoaphorsäurehexyldipropargylester
• Phosphorsäure-2-äthylhexyldipropragylester

Examples of particularly advantageous phosphorus-containing compounds of the formula (I) to be used as synergists are:

• Allylphosphonic acid dimethyl ester
• Allylphosphonic acid diethyl ester
• Allylphosphonic acid di-n-propyl ester
• Di-i-propyl allylphosphonic acid
• Allylphosphonic acid di-2-chloroethyl ester
• Allylphosphonic acid di-2-bromoethyl ester
• Allylphosphonic acid di-2-chloropropyl ester
• Allyyphosphonic acid di-2-bromopropyl ester
• Allylphosphonic acid diallyl ester
• Allylphosphonsäureallyläthylester
• Allyl propyl allyl propyl ester
• Allylphosphonic acid dibutyl ester
• Allyphosphonic acid diisobutylaster
• Allylphosphonic acid di-2-butylaster
• Allylphosphonic acid diamine ester
• Diisocyanate allylphosphonic acid
• Allylphosphonic acid dihexyl ester
• Allylphosphonic acid di-2-ethylhexyl ester
• Allylphosphonic acid methyl benzyl ester
• Allylphosphonic acid ethyl benzyl ester
• Propylbenzyl allylphosphonic acid
• Allylphosphonic acid dibenzyl ester
• Allylphosphonic acid diphenyl ester
• Allylphosphonic acid methylphenyl ester
• Allylphosphonic acid ethyl phenyl ester
• Methyl 4-chlorophenyl allylphosphonate
• Methyl 4-methoxyphenyl allylphosphonate
• Allylphosphonic acid di-2-chloroethyl ester
• Allylphosphonic acid di-2-chloropropyl ester
• Allylphosphonic acid ethyl propyl ester
• Propylbutyl allylphosphonate
• Allylphosphonic acid bis-2,3-dichloropropyl ester
• Allylphosphonic acid methyl 2,2-dichlorovinyl ester
• Allylphosphonic acid ethyl 2,2-dichlorovinyl ester
• Propyl-2,2-dichlorovinyl allylphosphonate
• Allylphosphonic acid isopropyl-2,2-dichlorovinyl theater
• Butyl 2,2-dichlorovinyl allylphosphonate
• Allylphosphonic acid isobutyl-2,2-dichlorovinyl ester
• Allylmonothiophosphonic acid-0-ethyl-S-methyl ester
• Sllylmonothiophosphonic acid-0-propyl-S-methyl ester
• Allyl monothiophosphonic acid-0-butyl-S-methyl ester
• Allylmonothiophosphonic acid-0-ethyl-S-butyl ester
• 0-propyl-S-butyl allyl monothiophosphate
• Allylmorothiophosphonic acid-0-butyl-S-butyl ester
• Allylmonothiophosphonic acid-0-ethyl-O-2,2-dichlorovinyl ester
• Allyl monothiophosphonic acid 0-propyl-0-2,2-dichlorovinyl ester
• Allylmonothiophosphonic acid-0-isopropyl-0-2,2-dichlorovinyl ester
• Allylmonothiophosphonic acid-0-butyl-0-2,2-dichlorovinyl ester
• Allylmonothiophoephonic acid-0-isobutyl-0-2,2-dichlorovinyl ester
• Allyl monothiophosphonic acid 0.0-dimethyl ester
• Allyl monothiophosphonic acid 0.0-diethyl ester
• Allyl monothiophosprionic acid dichloroethyl ester
• Allyl monothiophosphonic acid di-n-propyl ester
• Allyl monothiophosphonic acid di-isopropyl ester
• Allyl monothiophosphonic acid di-n-butyl ester
• Allyl monothiophosphonic acid di-2-butyl ester
• Allyl monothiophosphonic acid-O, S-dimethyl ester
• Allylmonothiophosphonic acid-0, S-diethyl ester
• Allylmonothiophosphonic acid-0-ethyl-S-2-hydroxyethyl ester
• Allyldithiophosphonic acid-O-ethyl-S-methyl ester
• Methanephosphonic acid diallyl ester
• Methyl allyl methanephosphonate
• Ethyl methanephosphonate
• Propyl allyl methanephosphonic acid
• Butyl allyl methanephosphonic acid
• Allyl-2,3-dichloropropyl methanephosphonate
• Allyl-2,3-dibromopropyl methanephosphonate
• Diallyl chloromethanephosphonic acid
• Chloromethanephosphonic acid methyl allyl ester
• Chloromethanephosphonic acid ethyl allyl ester
• Chloromethanephosphonic acid propyl allyl ester
• Butyl allyl chloromethanephosphonic acid
• Allyl-2,3-dichloropropyl chloromethanephosphonate
• Allyl-2,3-dibromopropyl chloromethanephosphonate
• 2-butene-1-phosphonic acid dimethyl ester
• 2-butene-1- ^p- phosphonic acid diethyl ester
• 2-butene-1-phosphonic acid dipropyl ester
• Triallyl phosphate
• Tripropargyl phosphate
• Ethylphosphonic acid diallyl ester
• Ethylphosphonic acid methyl allyl ester
• Ethylphosphonic acid ethyl allyl ester
• Ethanephosphonic acid n-propylallyl ester
• Ethanephosphonic acid-i-propylallyl ester
• Ethane phosphonic acid n-butyl allyl ester
• Ethane phoaphonic acid i-butylallylecter
• Propanephosphonic acid diallyl ester
• Methyl allyl propanephosphonate
• Ethyl propanephosphonate
• Propanephosphonic acid n-propylallyl ester
• Propanephosphonic acid i-propylallyl ester
• Propanephosphonic acid n-butyl allyl ester
• Propanephosphonic acid i-butylallyleater
• Vinylphosphonic acid diallyl ester
• Vinylphosphonic acid methyl allyl ester
• Vinylphosphonic acid ethyl allyl ester
• Vinylphosphonic acid n-propylallyl ester
• Vinylphosphonic acid i-propylallyleater
• Vinylphosphonic acid n-butyl allyl ester
• Vinylphoephonic acid i-butylallyl ester
• 1-Methylvinylphosphonic acid diallyl ester
• 1-methylvinylphosphonic acid methyl allyester
• 1-Methylvinylphosphonic acid ethyl allyl ester
• 1-methylvinylphosphonic acid n-propylallyl ester
• 1-methylvinylphosphonic acid i-propylallyl ester
• 1-methylvinylphosphonic acid n-butyl allyl ester
• 1-Methylvisylphosphonic acid i-butylallyl ester
• 2,2-Dimethylvinylphosphonic acid diallyl ester
• 2,2-Dimethylvinylphosphensäuresmethylallylester
• 2,2-Dimethylvinylphosphonic acid ethyl allyl ester
• 2,2-dimethylvinylphosphonic acid n-propylallyl ester
• 2,2-Dimethylvinylphesphonic acid 1-propylallyl ester
• 2,2-Dimethylvinylphosphonic acid n-butyl allyl ester
• 2,2-Dimethylvinylphosphonic acid i-butyl allyl ester
• Benzylphosphonic acid diallyl ester
• Methyl allyl benzylphosphonate
• Ethyl allyl benzylphosphonate
• Benzylphosphonic acid n-propylallyl ester
• Benzylphosphonic acid i-propylallyl ester
• Benzylphosphonic acid n-butyl allyl ester
• Benzylphosphonic acid i-butyl allyl ester
• 2-Phenylvinylphosphonic acid diallyl ester
• 2-phenylvinylphosphonic acid methyl allyl ester
• 2-phenylvinylphosphonic acid ethyl allyl ester
• 2-phenylvinylphosphonic acid n-propylallyl ester
• 2-phenylvinylphosphonic acid i-propylallyl ester
• 2-phenylvinylphosphonic acid n-butyl allyl ester
• 2-phenylvinylphosphonic acid-i-butylallyl ester
• Phenylphosphonic acid diallyl ester
• Phenylphosphonic acid methyl allyl ester
• Phenylphosphonic acid ethyl allyl ester
• Phenylphosphonic acid n-propylallyl ester
• Phenylphosphonic acid i-propylallyl ester
• Phenylphosphonic acid n-butyl allyl ester
• Phenylphosphonic acid i-butylallyl ester
• Phenylthiophosphonic acid diallyl ester
• Phenylthiophosphonic acid methyl allyl ester
• Phenylthiophosphonic acid ethyl allyl ester
• Phenylthiophosphonic acid n-propylallyl ester
• Phenylthiophosphonic acid i-propylallyl ester
• Phenylthiophosphonic acid n-butyl allyl ester
• Phenylthiophosphonic acid i-butylallyl ester
• 2-ethoxyethylene diallyl ester
• 2-Ethoxyethylenephosphonic acid methyl allyl ester
• 2-Äthoxyätäthylenpaosphonsäureäthylallylester
• 2-Ethoxyethylenephosphonic acid n-propylallyl ester
• 2-Ethoxyethylenephosphonic acid-i-propylallyl ester
• 2-Ethoxyethylenephosphonic acid n-butyl allyl ester
• 2-ethoxyethylene phosphonic acid i-butyl allyl ester
• Dimethyl phosphoric acid ester
• Diethyl phosphoric acid
• Phonophorsäuredipropylallylester
• Diisopropyl allyl phosphorate
• Phosphoric acid dibutyl allyl ester
• Phosphoric acid dichloroethyl allyl ester
• Phosphoric acid dibenzyl allyl ester
• Methyl phosphoric acid ester
• Phosphoric acid ethyl diallyl ester
• Propyl diallyl phosphoric acid
• Phosphoric acid isopropyl diallyl ester
• Phosphoric acid butyl diallyl ester
• Phosphoric acid, chloroethyl diallyl ester
• Allyl-bis-2,3-dichloropropyl phosphoric acid
• Allyl-bis-2,3-dibromopropyl phosphoric acid
• Phosphoric acid diallyl-2,3-di-chloropropyl ester
• Phosphoric acid diallyl-2,3-di-bromopropyl ester
• Allylmethyl-2,2-di-chlorovinyl vinyl phosphorate
• Allyl-phosphoric acid 2,2-di-chloro vinyl ester
• Sallylpropyl-2,2-di-chlorovinyl vinyl phosphorate
• Allyl isopropyl-2,2-di-chlorovinyl vinyl phosphorate
• Phosphoric acid allybutyl-2,2-di-chlorovinyl ester
• Allyl isobutyl-2,2-di-chlorovinyl vinyl phosphorate
• Phosphoric acid diallyl-2,2-dichlorovinyl ester
• Allyl phosphoric acid to 2,2-dichlorovinyl ester
• 0,0,0-triallyl thiophosphate
• O, O, O-tripropyrgylthiophosphate
• Thiophosphoric acid-0-allyl-0,0-dimethyl ester
• Thiophosphoric acid-0-allyl-0.0-diethyl ester
• Thiophosphoric acid-0-allyl-0.0-dipropyl ester
• Thiophosphoric acid-0-allyl-0.0-dipropyl ester
• Thiophosphoric acid-0-allyl-0.0-diisopropyl ester
• Thiophosphoric acid-0-allyl-0,0-dibutyl ester
• Thiiophosphoric acid-0-allyl-0,0-di-2-chleräthylester
• Thiophosphoric acid-0.0-diallyl-0-methyl ester
• Thiophosphoric acid 0.0-diallyl-0-ethyl ester
• Thiophosphoric acid 0.0-diallyl-0-propyl ester
• Thiophosphoric acid 0.0-diallyl-0-isopropyl ester
• Thiophosphoric acid 0.0 dially dibutyl ester
• Thiophosphoric acid 0.0-diallyl-0-di-2-chloroethyl ester
• Methyl phosphorodipropargylester
• Phosphoric acid ethyl dipropargylester
• Phosphoric acid propyl dipropargylester
• Phosphoric acid isopropyl dipropargyl ester
• Phosphoric acid butyl dipropargylester
• Phosphoric acid isobutyl dipropargyl ester
• Phosphoric acid amyl dipropargylester
• Phosphoric acid isoamyl dipropargylester
• Phoaphoric acid hexyl dipropargyl ester
• Phosphoric acid 2-ethylhexyl dipropragyl ester

• 2-Methylphenyl-, 2-Äthylphenyl-, 2-n-Propylphenyl-, 2-Methoxyphenyl-, 2-Äthoxyphenyl-, 2-n- oder -iso-Propoxyphenyl-, 4-Methyl-phenyl-, 4-Äthylphenyl-, 4-n-Propylphenyl-, 4-Methoxyphenyl-, 4-Äthoxyphenyl-, 4-n-Propoxyphenyl-, 2-Allalphenyl-, 2-(1-Methylallyl)-phenyl-, 3-iso-Propyl-4-methoxyphenyl-, 3,4, 5-Trimethylphenyl-, 2,3-_Dihydro-2,2-dimethylbenzufuran(7)-yl-, 2- [1,3-Dioxolan(2)yl-phenyl]-, 2,2-Dimethyl-1,3-benzodioxol (4)yl-, 2,2-Dimethyl- bzw. 1-Methyl-2,3-dihydro-benzofuran (4) yl-N-Methyl-carbamat, die entsprechenden -N-methyl-N-acetyl-, -N-methyl-N-trifluormethylthio-, -N-methyl-N-dichlormonofluormethylthio- bzw. -N-methyl-N-dimethylaminothio-carbamate.

The carbamates (group A) of the formula (II) to be used as mixing components include:

• 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-methoxyphenyl, 2-ethoxyphenyl, 2-n or iso-propoxyphenyl, 4-methylphenyl, 4-ethylphenyl, 4-n-propylphenyl-, 4-methoxyphenyl-, 4-ethoxyphenyl-, 4-n-propoxyphenyl-, 2-allalphenyl-, 2- (1-methylallyl) -phenyl-, 3-iso-propyl-4-methoxyphenyl- , 3,4, 5-trimethylphenyl-, 2,3- _D ihydro-2,2-dimethylbenzufuran (7) -yl-, 2- [1,3-dioxolane (2) yl-phenyl] -, 2,2- Dimethyl-1,3-benzodioxol (4) yl-, 2,2-dimethyl- or 1-methyl-2,3-dihydro-benzofuran (4) yl-N-methyl-carbamate, the corresponding -N-methyl- N-acetyl-, -N-methyl-N-trifluoromethylthio-, -N-methyl-N-dichloromonofluoromethylthio- and -N-methyl-N-dimethylaminothio-carbamates.

These compounds, their preparation and their use are known (compare, for example, US Pat. Nos. 3,009,855; 2,903,478 and 3,111,539).

• Essigsäure-[2,2,2-trichlor-1-(3,4-dichlorphenyl)-äthyl]-ester, 2,3,4,5-Tetrahydrophthalimidomethylchrysanthemat, 3-Phenoxy- benzyl-[2,2-dimethyl-3-(2,2-dichlorvinyl)-cyclopropan]-carboxylat und (5-Benzyl-furyl)-methyl-2,2-dimethyl-1-3-(2-methylpro- penyl)-cyclopropancarboxylat.

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

• Acetic acid [2,2,2-trichloro-1- (3,4-dichlorophenyl) ethyl] ester, 2,3,4,5-tetrahydrophthalimidomethyl chrysanthemum, 3-phenoxybenzyl- [2,2-dimethyl-3 - (2,2-dichlorovinyl) cyclopropane] carboxylate and (5-benzyl-furyl) methyl 2,2-dimethyl-1-3- (2-methylpropenyl) cyclopropane carboxylate.

The listed compounds are known and for the most part well-known commercial products (compare R. Wegler "Chemistry of Plant Protection and Pest Control" Volume 1, pages 87-118, Heidelberg (1970).

The cycloalkanes (group D) of the formula (v) which may also be used as mixture components are included

1,2,3,4,5,6-hexachlorocyclohexane. This connection, its production and its use is known, compare e.g. B. U.S. Patent No. 2,502,258; Chem. + Industry, 1945, p. 314).

These compounds, their preparation, and their use are known (see, e.g., U.S. Patents 2,420,928, 2,464,500, 2,883,428 and 2,917,553).

As already mentioned, the new active compound combinations of the phosphorus esters of the formula (I) which can be used according to the invention show with carbamates, encycloalkanen Carbonsäureestern, Phosphorsäureestern, halo and ^g haloalkanes excellent WIR kun ^g ssteigerung compared to the single active ingredients or with respect to their sum.

Can irkstoffgruppen the weight ratios of _W vary within relatively wide ranges. In general, the phosphorus-containing compounds used as synergists are used in a ratio of 0.1: 10 to 10: 0.1 with the other active ingredients. Mixing ratios of 0.5: 1.0 to 3.0: 1.0 have proven to be particularly suitable. The active compound combinations according to the invention not only bring about a quick knock-down effect, but also bring about the sustainable killing of animal pests, in particular insects and mites, which occur in agriculture, in forests, in the protection of stored products and materials and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.

• Aus der Ordnung der Isopoda z. B. Oniscuc asellus, Armadillidium vulgare, Porcellio scaber.
• Aus der Ordnung der Diplopoda z. B. Blaniulus guttulatus.
• Aus der Ordnung der Chilopoda z. B. Geophilus carpophagus, Scutigera spec.
• Aus der Ordnung der Symphyla z. B. Scutigerella immaculata. Aus der Ordnung der Thysanura z. B. Lepisma saccharina.
• Aus der Ordnung der Collembola z. B. Onychiurus armatus.
• Aus der Ordnung der Orthoptera z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blatella germanica, Aceta demoesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
• Aus der Ordnung der Dermaptera z. B. Forfigula auricularia.
• Aus der Ordnung der Isoptera z. B. Reticulitermes spp.,
• Aus der Ordnung der Anoplura z. B.
  
  phigus spp., Pediculus humanus corporis.
  
  Linognathus spp.
• Aus der Ordnung der Mallophaga z. B.
  
  linea spp.
• Aus der Ordnung der Thysanoptera z. B.
  
  Thrips tabaci.
• Aus der Ordnung der Heteroptera z. B.
  
  cus intermedius, Piesma quadrata, Cimex lectularius, Rhoomius prolixus, Triatoma spp.
• Aus der Ordnung der Homoptera z. B. Aleurodes brassicae, Bemisda tabaci, Trialeurodes vaporariurum,
  
  Brevicornyne brassicae, Cryptomyzus ribis, Doralis labae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis. Macorsiphum avenae, Myzus spp., Phorodon humuli,
  
  padi, Empoasca spp., Euscelis bilobatus,
  
  Lecanium corni, Saissetia oleae, Laodelphax strimcellus, Nilaparvata lugens, Aonidiella auroantii, Aspidiotus hederse, Pseudo- coccus spp., Psylla spp.
• Aus der Ordnung der Lepidoptera z. B. Peptinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancar- della, Hyponomeuta padella, Plutella maculipennis Melanosoma neutria, Euproctis chrysorrhoea, Lymantria spp.
  
  thurberiella, Phillocnistis citrella, Agrotis spp.,
  
  Feltia spp., Earias insulana, Heliothis spp., Laphygma oxigua, Mamestra brassicae, Panolis flammea,
  
  Spodoptera spp., Trichoplusia ni, Carpocapsa pomonalle, Pieris sp., Chilo spp., Pyrausta nubilalis, Ephestia. kuchniella, Calleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima,
  
  viridana.
• Aus der Ordnung der Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postuca, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp.,Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.
• Aus der Ordnung der Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
• Aus der Ordnung der Diptera z. B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., C terebra spp., Gastrophilus spp., Hyppobosca spp., Stomocxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.
• Aus der Ordnung der Siphonaptera z. B. Xenopsylla cheopis, 'Ceratophyllus spp..
• Aus der Ordnung der Arachnida z. B. Scorpio maurus, Latrodectus mactans.
• Aus der Ordnung der Acarina z. B. Acarus siro, Argas spp.,Or- nithodoros 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..

The pests mentioned above include:

• From the order of the Isopoda z. B. Oniscuc asellus, Armadillidium vulgare, Porcellio scaber.
• From the order of the Diplopoda z. B. Blaniulus guttulatus.
• From the order of the Chilopoda z. B. Geophilus carpophagus, Scutigera spec.
• From the order of the Symphyla z. B. Scutigerella immaculata. From the order of the Thysanura z. B. Lepisma saccharina.
• From the order of the Collembola z. B. Onychiurus armatus.
• From the order of the Orthoptera z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blatella germanica, Aceta demoesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
• From the order of the Dermaptera z. B. Forfigula auricularia.
• From the order of the Isoptera z. B. Reticulitermes spp.
• From the order of the Anoplura z. B.
  
  phigus spp., Pediculus humanus corporis.
  
  Linognathus spp.
• From the order of the Mallophaga z. B.
  
  linea spp.
• From the order of the Thysanoptera z. B.
  
  Thrips tabaci.
• From the order of the Heteroptera z. B.
  
  cus intermedius, Piesma quadrata, Cimex lectularius, Rhoomius prolixus, Triatoma spp.
• From the order of Homoptera z. B. Aleurodes brassicae, Bemisda tabaci, Trialeurodes vaporariurum,
  
  Brevicornyne brassicae, Cryptomyzus ribis, Doralis labae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis. Macorsiphum avenae, Myzus spp., Phorodon humuli,
  
  padi, Empoasca spp., Euscelis bilobatus,
  
  Lecanium corni, Saissetia oleae, Laodelphax strimcellus, Nilaparvata lugens, Aonidiella auroantii, Aspidiotus hederse, Pseudococcus spp., Psylla spp.
• From the order of the Lepidoptera z. B. Peptinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis Melanosoma neutria, Euproctis chrysorrhoea, Lymantria spp.
  
  thurberiella, Phillocnistis citrella, Agrotis spp.,
  
  Feltia spp., Earias insulana, Heliothis spp., Laphygma oxigua, Mamestra brassicae, Panolis flammea,
  
  Spodoptera spp., Trichoplusia ni, Carpocapsa pomonalle, Pieris sp., Chilo spp., Pyrausta nubilalis, Ephestia. kuchniella, Calleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima,
  
  viridana.
• From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephppis, Orphusus spp. , Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postuca, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Nidesusibbium ps molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.
• From the order of the Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
• From the order of the Diptera z. B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., C terebra spp., Gastrophilus spp., Hyppoboscaxpp., Stomoc 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 the Siphonaptera z. B. Xenopsylla cheopis, 'Ceratophyllus spp ..
• From the order of the Arachnida z. B. Scorpio maurus, Latrodectus mactans.
• From the order of Acarina z. B. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoropopes spp ., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..

The active substance combinations can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, suspension emulsion concentrates. Seed powder, active ingredient-impregnated natural and synthetic substances, very fine encapsulation in polymeric substances and in coating compositions for seeds, also in formulations with fuel sets, such as smoking cartridges, cans, spirals and the like. Ä. and ULV cold and heat mist formulations.

These formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. In the case of the use of water as an extender, e.g. B. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene; Toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. B. 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; Liquefied gaseous extenders or carriers mean those liquids which are gaseous at normal temperature and pressure, e.g. B. aerosol propellants such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; as solid carriers; natural rock flours, such as kaolins, alumina, talc .. Kreido, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic Rock powders such as finely divided silica, aluminum oxide and silicates; as solid carriers for granules: broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foam-generating agents: nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ether, e.g. B., alkylaryl -polyglykol ether, alkyl sulfonates, _A lkylsulfate, arylsulphonates and protein hydrolysates; as a dispersant: e.g. B. lignin, sulfite and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin. Azo metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

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

The active compound combinations according to the invention are used in the form of their commercially available formulation and / or the use forms prepared from these formulations.

The active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges. The active substance concentration of the use form can be from 0.0000001 up to 100 wt .-% active ingredient, preferably between 0.01 and 10 wt .-%.

The application takes place in a customary manner adapted to the application forms.

When used against hygiene pests and pests of stored products, the active substance combinations are notable for an excellent residual action on wood and clay and for good stability to alkali on limed substrates.

Example A LT ₁₀₀ test Test animals: Phosphoric acid ester-resistant Musca domestica (Weymann strain) 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 with a diameter of 9.5 cm. The filter paper absorbs the solutions. The petri dishes remain open until the solvent has completely evaporated. Then 25 test animals are placed in the Petri dishes and covered with a glass lid.

The condition of the test animals is checked continuously for up to 6 hours. The time required for a 100% knock-down effect is determined. If the LT _{100 is} not reached after 6 hours, the percentage of the knock-down test animals is determined.

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

Example B ^LT ₁₀₀ test Test animals: Blattella germanica Tribolium confusum Trogoderma granarium 4. Larvae 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 of 9.5 cm diameter. The filter paper absorbs the solutions. The petri dishes remain open until the solvent has completely evaporated. Then put 20 test animals in the Petri dishes and cover them with a glass lid.

The condition of the animals is checked continuously for up to 6 hours and then after 24, 48 and 72 hours. The time required for a 100% knock-down effect is determined. If the LT _{100 is} not reached after 72 hours, the percentage of the knock-down test animals is determined.

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

General regulations for the production of allyl phosphonates.

1 mole of the trialkyl phosphite in question is placed under a nitrogen atmosphere together with 4 g of Raney nickel, nickel tetracarbonyl, π-allyl nickel chloride or nickel chloride. The allyl chloride or bromide is added dropwise at 80 to 120 ° C. and the resulting alkyl halide is distilled off. It is fractionated in vacuo after adding 1 g of phenothiazine.

The following table shows compounds obtainable by the above procedure.

Example 24: Allylthiophosphonic acid-O, O-di-ethyl ester

• Ausbeute: 60 g
• Kp.: 53-54° C/0,3 torr
• n_D ²⁰: 1,4738

1 mol of thiophosphoric acid O, O-diethyl ester is dissolved in 600 ml of absolute benzene and, with cooling at 0-5 ° C., 1 mol of sodium ethylate, dissolved in absolute ethanol, is added. 1.15 mol of allyl bromide are added dropwise to this mixture at 0-5 ° C. and the mixture is stirred for a further 2 hours at 10 to 20 ° C. and for 3 hours at 40 ° C. The NaBr which has separated out is filtered off with suction and distilled.

• Yield: 60 g
• Kp .: 53-54 ° C / 0.3 torr
• n _D ²⁰ : 1.4738

Example 6: Ethyl propanephosphonate

• Ausbeute: 124 g (60%)
• Kp.: 107,5 - 108,5° C/11 torr
• n_D ²⁰: 1,4348

200 g of phosgene are introduced into 1 mol of diethyl propanephosphonate at 70-80 ° C. The mixture is stirred at 70-80 ° C. for 1 hour and a dry N ₂ stream is passed through the reaction mixture at 50 ° C. overnight. It is completely degassed at 50 ° C. in a water jet vacuum in a rotavapor and the crude ethyl propanephosphonate chloride is obtained. This is made basic with absolute pyridine, dissolved in 300 ml of toluene and reacted at 20-30 ° C. with a mixture of 1.1 mol of pyridine and 1 mol of allyl alcohol. The mixture is left to react at 80 ° C. for 2 hours. The solution sucked off from the hydrochloride is concentrated and distilled.

• Yield: 124 g (60%)
• Kp .: 107.5 - 108.5 ° C / 11 torr
• n _D ²⁰ : 1.4348

Example 26: Allylphosphonic acid ethylphenyl ester (ARG 2048)

• Ausbeute: 60%
• Kp.: 96-98° C/0,07
• n_D ²⁰: 1,5036

Ethyl chloride of allylphosphonic acid produced in the same way as in synergistic example 16 is reacted with phenol to give ethylphenyl allylphosphate as in example 16.

• Yield: 60%
• Bp: 96-98 ° C / 0.07
• n _D ²⁰ : 1.5036

Example 1: Propyl allyl allylphosphonic acid

• Kp: 83°C/0,1 torr
• n_D ²⁰: 1,4460

Analogously to synergistic example 6, the product is prepared from dipropyl allylphosphonate and allyl alcohol.

• Kp: 83 ° C / 0.1 torr
• n _D ²⁰ : 1.4460

Example 2: Diallyl chloromethanephosphonic acid

• Kp: 100°C/0,18 torr
• n_D ²⁰: 1,4682

Prepared by reacting 1 mol of chloromethanephosphonic dichloride with 2 mol of allyl alcohol in the presence of excess pyridine in toluene.

• Kp: 100 ° C / 0.18 torr
• n _D ²⁰ : 1.4682

Example 34: Allyl phosphoric acid ester

• _Kp_: 73^o _C/2 torr
• n_D ²⁰: 1,4250

Analogously to Example 33, 1 mol of dimethyl phosphoric acid chloride is reacted with 1 mol of allyl alcohol.

• _K p _: 73 ^o _{C /} 2 torr
• n _D ²⁰ : 1.4250

Example 35: Phosphoric acid propyl dimethyl ester

• Kp: 71-72°C/0,2 torr
• n_D ²⁰: 1,4282

Analogously to Example 33, 1 mol of dimethyl phosphoric acid chloride is reacted with 1 mol of propargyl alcohol.

• Kp: 71-72 ° C / 0.2 torr
• n _D ²⁰ : 1.4282

Example 36: 1-methoxyvinylphosphonic acid diethyl ester

• Kp.: 77-79° C/0,1 torr 20
• ⁿ _D : 1,4427

1 mol of triethyl phosphite is added dropwise under an N ₂ atmosphere at 120 ° C. with 0.9 mol of methyl 1,2-dichloroethyl ether. After an 8-hour reaction time, the mixture is fractionated. 120 g of 1-methoxy-2-chloroethanephosphonic acid diethyl ester are obtained.

• Kp .: 77-79 ° C / 0.1 torr 20
• ⁿ _D : 1.4427

• Ausbeute: 140 g
• Kp.; 85° C/0,5 torr
• n_D ²⁰: 1,4412

1 mol of this compound is dissolved in 100 ml of alcohol. A solution of 1 mol FOH in 200 ml alcohol is slowly added at 20-30 ° C. The temperature is kept below 40 ° C by cooling. It is suctioned off and fractured after adding 0.5 g of phenothiazine.

• Yield: 140 g
• Kp .; 85 ° C / 0.5 torr
• n _D ²⁰ : 1.4412

Example 7: Allyl diphenyl phosphate

• Kp.: 148-50° C/0,15 mm
• n_D ²⁰: 1,5348

Made from allyl alcohol and phosphoric acid diphenyl ester chloride in the presence of pyridine

• Kp .: 148-50 ° C / 0.15 mm
• n _D ²⁰ : 1.5348

Example 27: Triailyl phosphate

• Kp.: 90° C/0,15 mm
• n_D ²⁰: 1,4482

Made from POCl ₃ and allylalkchol in toluene / triitylamine

• Kp .: 90 ° C / 0.15 mm
• n _D ²⁰ : 1.4482

General regulations for the production of allyl dialkyl phosphates or propargyl dialkyl phosphates

1 mol of dialkyl phosphite, 2 mol of CC1 ₄ and 1.05 mol of allyl alcohol or propargyl alcohol are added dropwise at 20-30 ° C with 1.2 mol of triethylamine. After the exothermic reaction has subsided, the mixture is refluxed for 3 hours, filtered off from the salt and fractionated.

The following table shows compounds obtainable by the above procedure:

Claims (1)

1.Insecticidal and acaricidal agents, characterized by a content of an active ingredient combination consisting of phosphorus-containing compounds of the general formula I.

in which _R ¹ , R ² and _R ^{3 are,} independently of one another, the radicals alkyl, alkenyl or aryl, which may optionally be substituted, at least one of the radicals representing an optionally substituted alkenyl radical which is unsaturated in the 2-position, X represents oxygen or sulfur, Y and Z independently of one another represent oxygen, sulfur or a simple bond; if both Y and Z are oxygen or sulfur or a simple bond, then R ¹ , R ² and R ³ in the radicals indicated above can also mean propargyl;
and A. carbamates, and / or B. carboxylic acid esters, including natural and synthetic pyrethroids and / or C. phosphoric acid esters and / or _D. Halogencycloalkanen and / or E. Haloalkanes