CA2014268A1 - Oximinophosphoric and -phosphonic acid derivatives, precursors for the preparation thereof, and the use thereof for controlling pests - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE: Oximinophosphoric and -phosphonic acid derivatives of the general formula I

Description

2~
O.Z. 0050/40806 Oximinophosphoric and -phosphonic acid derivatives, precursors for the preparation thereof, and the use thereof for controlling pests . . _ . . . _ . _ . _ S The present invention relates to oximinophos-phoric and -phosphonic acid derivatives of the general formula I

R~ ~C~2 11 oRI
C--CH--I =N~P~ ( I ) where 0 Rl is unbranched or branched alkyl of 1 to 4 carbon atom~, R2 is unbranched or branched alkyl of 1 to 4 carbon atoms, unbranched or branched alkoxy or alkylthio of 1 to 4 carbon atoms, phenyl, amino or unbranched or branched alkylamino or dialkylamino each with 1 to 4 carbon atoms in each alkyl, R3 and R4 are hydrogen, methyl or chlorine and x is oxygen or sulfur.
The present invention also relates to precursors for the preparation of compounds I and pest-control agents which contain these compounds as active ingredi-ents.
Oximinophosphoric and -phosphonic acid deriva-tives are disclosed in DE-B 1,052,981, DE-B 1,238,902, DE-A 2,952,738, DE-A 3,135,182, EP 115,318 and EP
150,822. Thionopkosphoric acid oxime derivatives with a C5- or C~-cycloalkyl and a cyano on the oxime double bond are disclosed in DE-A 23 04 848 for controlling insects and mites. Since the action of the compounds of the abovementioned prior art is not always satisfactory under certain conditions, eq. low application rates or action on certain problem pests, the ob~ect of the present inventionwas to provide oximinophosphoric and -phosphonic - 2 - o.z. OOS0/40806 acid deri~atives with an improved action.
We have accordingly found the oximinophosphoric and -phosphonic acid derivatives I defined in the first paragraph and precursors for the preparation of the compounds I. Pest-control agents containing the active ingredient I have a potent insecticidal, nematicidal and acaricidal action and are superior to known active ingredients of similar structure and the same type of action.
Examples of unbranched or branched alkyl for are methyl, ethyl, propyl, isopropyl, butyl and isobutyl, and examples of unbranched or branched alkyl, alkoxy or alkylthio for R2 are methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, propoxy and butoxy, methylthio, ethyl-thio, n-propylthio, isopropylthio, n-butylthio, sec.-bLtylthio and isobutylthio. Examples of alkylamino and dialkylamino for R2 are methylamino, dimethylamino, ethylamino, diethylamino, methylethylamino, n-butylamino and di-n-butylamino.
Preferred substituents for R1 are methyl and ethyl; preferred substituents for R2 are methoxy, ethoxy, methyl, ethyl, phenyl, amino, methylamino, dimethylamino and isopropylamino.
The oximinophosphoric and -phosphonic acid derivatives of the formula I can be obtained by reacting appropriate ~-oximino nitriles II with appropriate (thio)phosphoric and -phosphonic ester or amide halides III in the presence of an acid acceptor:

C--C~ X ORI R3 CH2 X ORI
R~ ~C=~OH ~ Hal-P \C/--\C 11/

(Il) (III) (I) -Chlorine is preferred for halogen (Hal=Cl) for economic rea~ons.
Acid acceptors used for the phosphorylation are . . , ~ .
.
. . . .

~ .:

~Q~&~3 - 3 - O.Z. 0050/40806 conventional bases, especially aliphatic, aromatic or heterocyclic amines such as dimethylamine, triethylamine, diisopropylamine, piperidine, dimethylaniline, dimethyl-benzylamine, pyridine and 4-dimethylaminopyridine, alkali metal or alkaline earth metal carbonates such as sodium carbonate, potassium carbonate or calcium carbonate, alkali metal or alkaline earth metal alcoholates such as sodium methylate, sodium ethylate, calcium ethylate or potassium ter~.-butylate, alkali metal or alkaline earth metal hydrides such as sodium hydride, potassium hydride and calcium hydride.
In place of the addition of an acid acceptor, it is also possible before the reaction of the ~-oximino nitriles II to prepare the alkali metal or alkaline earth metal salts such as sodium, potassium or calcium salts or ammonium salts and to react the lat~er with phosphoryl halides III. Suitable solvents or diluents are aliphatic or aromatic and possibly chlorinated hydrocarbons such as petroleum e~her, n-pentane, n-hexane, mixtures of hexane isomers, benzene, toluene, xylenes, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene; ethers such as diethyl ether, di-n-butyl ether, methyl tert.-butyl ether, tetrahydrofuran, diox-ane; ketones and esters such as acetone, methyl ethyl ketone, methyl isopropyl ketone, ethyl acetate; nitriles such as acetonitrile and propionitrile; aprotic dipolar solvents such as dimethylformamide, dimethyl sulfoxide, pyridine. It is also possible to use mixtures of these substance~ as solvents and diluents. The starting mater-ials are normally used in the stoichiometric ratio. Anexcess of one component may be quite advantageous in a few cases.
The reaction generally takes place at from 10C
to 120C, preferably at room temperature (20C) to 70C.
The reactions generally take place under atmospheric pressure.
The active ingredient according to the invention ~o~6~

- 4 - O.Z. 0050/40806 is obtained from the reaction mixture in a conventional manner, for example by the addition of water, separation of the phases and distillation and/or column chromato-graphy. The ~-oximino nitriles II used as starting materials for the preparation of the compounds of the formula I are new. They can be prepared in a conventional manner (cf. DE-B 15 67 142) by chlorination of the relevant oxime~3 IV and subsequent reaction with sodium or potassium cyanide as shown in the following equation:

\C/--\CH 1. C12(-HCl) R~ ~ ~2 R 4 C=N-OH ' R 4 C=N--OH
H 2 KCN(--KCl ) CN
(IV) (II) The oximes of the formula IV are obtained by reacting the corresponding cyclopropanecarbaldehyde of ~he formula V with hydroxylamine hydrochloride in accor-dance with the following equation:

/\ ~

1 \ H2NOH-HCI
R4 H ~ ( IV) --HC 1, --H 2 (V) Cyclopropanecarbaldehyde (R3,Ri=H) is commerc1ally available, and l,1-dichlorocyclopropanecarbaldehyde (R3,R~=Cl) is known from the literature (cf. A. Xh.
Khusid, Zh. Org. Rhim. 22 (1986) 1195-1200).
The (thio)phosphoric and -phosphonic Qster or amide halides III also required for the synthesis of the compounds of the formula I are known from Houben-Weyl, Nethoden der organischen Chemie, Volume 12/2, pp. 274 et sQq.~ Georg-Thieme-Verlag, Stuttgart 1964, and can be prepared by the synthetic rOutQs dQscribed therein.
Some of the novel compounds of the formula I are produced in the form of colorless or pale brown oil~

.

2~ 4;~

- 5 - O.Z. 0050/40806 which can be purified by lengthy heating under reduced pressure at a moderately elevated temperature (~incipient distillation~) to remove the last residues of volatile~.
Those compounds of the formula I which are crystalline can be purified by recrystallization.
Since the compounds of the formula I usually occur as mixture~ of the syn and anti forms, their melting or boiling ranges are unsuitable for identifying them. This is why the absorption maxima in the finger-print region in the IR spectra below 1500 cm~~ are repor-ted for each of the prepared substances.

/ \
H2C--C~ 11 OC2H5 C=N~P~

3.3 g (0.03 mol) of 2-cyclopropyl-2-hydroximino-acetonitrile are dissolved in 35 cm3 of acetonitrile, 4.14 g of potassium carbonate are added, and 6.56 g of O,O-diethyl chlorothiophosphate are added dropwise. The mixture is stirred at room temperature for 14 h, then insolubles are removed by filtration with suction, and the filtrate is concentrated under reduced pressure. The residue is taken up in methyl tert.-butyl ether, the solution is washed with 5% strength aqueous sodium hydroxide solution and with water and dried over sodium sulfate, and the solvent is stripped off. Remaining after incipient distillation at 50C and 0.1 mbar are 7.6 g of (O,O-diethylthiophosphoryl)oximino-2-cyclopropylaceto-nitrile as a slightly viscous oil.
Yields 97% of theory Elemental analysiss C3H~5N2O3PS
calc.: Cs 41.22; Hs 5.77; N: 10.68;
found: Cs 41.4 ; H: 6.0 ; N: 11.3 ;
300 MHz lH NMR spectrum in CDCl3 (6 in ppm from ~ .. . .
.. . . . . . .

. . . . . . : .- , : . .

2~?~B

- 6 - O.Z. 0050/40~06 tetramethylsilane as internal standard): 1.01-1.20 (m,4H), 1.39 (t,6H); 2.03-2.13 (m,lH); 4.20-4.36 (m,4H) Infrared absorptions (cm~l): 1164, 1045, 1022, 975, 933, 904, 852.

C/c\f H 2 C I C\ Il/OCH 3 C=N~P
CN O-n-C 3H~
2.69 g (15 mmol) of 2-(1,1-dichlorocyclopropyl)-2-hydrox-iminoacetonitrile are dissolved in 25 cm3 of acetonitrile, 2.07 g of potassium carbonate are added, and 2.83 g of O-methyl O-n-propyl chlorothiophosphate are added dropwise.
The mixture i~ stirred at room temperature for about 50 h and then filtered, the acetonitrile is removed by distillation, the residue i~ taken up in methyl tert.-butyl ether, and the solution i3 washed with 5% strength -aqueous sodium hydroxide solution and with water, dried over sodium sulfate and concentrated under reduced pre~sure. Column chromatography with 1,2-dichloroethane/-cyclohexane as mobile phase yields 4.4 g of (O-methyl-O-n-propylthiophosphoryl)oximino-2-(1,1-dichloro-cyclopropyl)acetonitrile as a 31ightly viscou~ oil.
Yield~ 89% of theory.
Elemental analysiss CgHl3C12N2O3PS
calc.s Cs 32.64; Hs 3.96; Ns 8.46 founds Cs 32.8 ; Hs 4.0 ; Ns 8.8 250 MHz lH NMR spectrum in CDCl3 (~ in ppm from tetra-methyl~ilane)s 0.95 (t,3H); 1.70-1.85 (m,2H); 2.09-2.28 (m,2H); 2.83 (dd,lH), 3.90 (d,3H); 4.10-4.27 (m,2H).
Infrared absorptions (cm~~)s 1109, 1044, 1017, 976, 917, 865, 828, 774.

Preparation of 2-cyclopropyl-2-hydroximinoacetonitrile 19.84 g of chlorine ga~ are introduced over about 2~*~

- 7 - O.Z. 0050/40806 50 min into 21.6 g (0.254 mol) of cyclopropane-carbaldoxime and 35 g of potassium carbonate in 0.9 1 of dry methylene chloride at -20C. After the mixture has warmed to room temperature the methylene chloride is stripped of f, and the residue is taken up in 0.5 1 of diethyl ether.
This ethereal solution is added dropwise at 10 to 15C to a suspension of 18.2 g of potassium cyanide in 190 ml of methanol, and the reaction mixture is then stirred at room temperature for 3 h. The precipitate is filtered off, and the filtrate i~ evaporated to dryness.
The residue i8 taken up in methyl tert.-butyl ether, washed with water and dried over ~odium sulfate, and the solvent is removed by distillation. The crude product obtained in this way is purified by column chromatography (silica gel, cyclohexane/methyl tert.-butyl ether as mobile phase).
Yield: 22.1 g, corresponding to 79% of theory, of a pale yellow oil, boiling point 134C/0.4 mbar.
The product is a syn/anti mixture.
250 MHz lH NMR spectrum in d~-DMSO (6 in ppm from tetra-methylsilane as internal standard):
0.72-1.16 (m, 4H), 1.85-2.0 and 2.3-2.4 (m, lH), 12.8 and 13.0 (s, lH).
IR absorptions (cm~l): 1583, 1~26, 1337, 1271, 1062, 1030, 993.
The compounds listed in the table which follows were obtained by the routes described in Example 1 and Example 2 where at least one physical datum is provided for their identification; other compounds corresponding to the formula I can be obtained in the -qame way with appropriate modification of the methods, if necessary after a preliminary test to find the best reaction conditions.

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.Q . . ~ ~ ~ u~ ~o 1~ o~ a~ o ~ o 1~ a~ a~ o _4 ~- ~ z 11 O.Z. 0050/40806 The oximinophosphoric (phosphonic) acid derivatives of the formula I are suitable for effectively combating pests such as insects, arachnids and nematodes. They may be used as pesticides in crop protection and in the hygiene, stores protection and veterinary sector.
Examples of injurious insects belonging to the Lepidoptera order are Agrotis ypsilon, Agrotis segetum, Alabdma argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura 10 ~umiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholita funebrana, Grapholita molesta, Heliothis armigera, Heliothis virescens, Heliothis 15 zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keifferia Iycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blan-cardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra 20 brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flamea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scarbra, Plutella xylostella, Pseudoplusia includens, Phyacionia frustrana, Scrobi-palpula absoluta, Sitotroga cerelella, Sparganothis pilleriana, Spodoptera 25 frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis.
Examples from the Coleoptera order are Agrilus sinuatus, Agriotes tineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, 30 Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, 81itophaga undata, Bruchus rufimanus, Bruchus pisorum, SruchuS
lentis, Byctlscus betulae, Cassida nebulosa, Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, 35 Diabrotica 12-punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, IpS typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha 40 hlppocastani, Melolontha melolontha, Onlema oryzae, Ortiorrhynchus sulcatus, Ortiorrhynchus ovatus, Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria.

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12 O.Z. 0050/40806 Examples from the Diptera order are Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, 5 Dacus oleae, Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis, Glossia morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Musca domestica, MuScina 10 stabulans, Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhago-letis pomonella, Tabanus bovinus, Tipula oleracea and Tipula paludosa.
Examples from the Thysanoptera order are Frankliniella fusca, 15 Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci.
Examples from the Hymenoptera order are Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, 20 Monomorium pharaonis, Solenopsis geminata and Solenopsis invicta.
Examples from the Heteroptera order are Acrosternum hilare, 81issus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euchistus impictiventris, 25 Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis and Thyanta perditor.
Examples from the Homoptera order are Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, AphiS pomi, Aphis sambuci, 30 Brachycaudus cardui, Brevicoryne brassicae, Cerosipha gossypii, Dreyfusia nordmannianae, Dreyfusia piceae, Dyasphis radicola, Dysaulacorthum pseudosolani, Empoasca fabae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum, Myzodes persicae, Myzus cerasi, Nilaparvata lugens, Pemphigus bursarius, 35 Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Trialeurodes vaporariorum and Viteus vitifolii.
40 Examples from the Isoptera order are Calotermes flavicollis, Leucotermes ftavipes, Reticulitermes lucifugus and Termes natalensis.

. .

2~ 8 13 O.z. 0050/40806 Examples from the Orthoptera order are Acheta domestica, Blatta orientalis, ~lattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus birittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus 5 spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asynamorus.
Examples from the Acarina order are Amblyomma americanum, Amglyomma 10 variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, ~revipalpus phoenicis, Bryobia praetiosa, Dermacentor silvarum, Eotetranychus carpini, Eriophyes sheldoni, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, Otobins megnini, Paratetranychus pilosus, PermanyssuS gallinae, Phyllocaptrata oleivora, 15 Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Saccoptes scabiei, Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae.
20 Examples from the nematodes class are root-knot nematodes, e.g., Meloi-dogyne hapla, Meloidogyne incognita and Meloidogyne javanica, cyst-forming nematodes, e.g., Globodera rostochiensis, Heterodera avenae, Hetrodera glycinae, Heterodera schachtii and Heterodera trifolii, and stem and leaf eelworms, e.g., Belonolaimus longicaudatus, Ditylenchus destructor, Dity-25 lenchus dipsaci, Heliocotylenchus multicinctus, Longidorus elongatus,Radopholus similis, Rotylenchus robustus, Trichodorus primitivus, Tylen-chorhynchus claytoni, Tylenchorhynchus dubius, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus and Pratylenchus goodeyi.
30 The active ingredients may be applied for instance as such, or in the form of formutations or application forms prepared therefrom, e.g., directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application 35 depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients accord-ing to the inventlon as possible.
For the preparation of solutions, emulsions, pastes and oil dispersions to 40 be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vege-table or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, ~ylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, ., .

2~4~S~

14 O.Z. 0050/40806 butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc.
are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing 10 agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and 15 ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutyl-naphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of 20 sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation proaucts of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctyl-25 phenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenolpolyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated poly-oxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, 30 lignin, sulf~te waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
35 Examples of formulations are given below.
I. 5 parts by weight of compound no. 1 is intimately mixed with 95 parts by weight of particulate kaolin. A dust is obtained containing 5~ by weight of the active ingredient.
II. 30 parts by weight of compound no. 2 is intimately mixed with a mix-ture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

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1 5 O . Z . 0050/40806 III. 10 parts by weight of compound no. 4 is dissolved in a mixture ~on-sisting of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanol-amide, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic 5 acid, and 2 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mote of castor oil.
IV. 20 parts by weight of compound no. 13 is dissolved in a mixture consisting of 60 parts by weight of cyclohexanone, 30 parts by weight of 10 isobutanol, 5 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil.
V. 80 parts by weight of compound no. 19 is well mixed with 3 parts by 15 weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel, and triturated in a hammer mill.
20 Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium 25 sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
30 The formulations generally contain from 0.1 to 95, and preferably 0.5 to 90, ~ by weight of active ingredient.
The active ingredient concentrations in the finished formulations may vary over a wide range. Generally, they are from 0.0001 to 10, and preferably 35 from 0.01 to 1, ~.
The active ingredients may also successfully be used in the ultra-low-volume (ULV) method, where it is possible to apply formulations containing more than 95wt% of active ingredient, or even the active ingredient with-40 out additives.
In the open, the amount of active ingredient applied is for example from0.02 to 10, particularly from 0.02 to 2, kg/ha.

-2~

16 O.z. 0050/40806 There may be added to the active ingredients (if desired, immediatelybefore use ttankmix)) oils of various types, herbicides, fungicides, other pesticides and bactericides. These agents may be added to the active in-gredients according to the invention in a weight ratio of from 1:10 to 5 10:1.
Use examples In the following examples, the action of the compounds according to the 10 invention, or of agents containing them, on pests was compared with that of compounds A and B known from DE-A-23 04 848:
H5C 2~ C 3H7 ~P~N=C~ A

H 3CO~ i -C 3H7 ~P~N=C~ B
ll-C3H70 CN
The concentrations at which the compounds investigated achieved 100% kill or inhibition are the minimum concentrations in each case. At least two 15 experiments were carried out for each concentration.
The purity of the active ingredients was >95%. The active ingredient was used either as an acetonic solution or as a 10% emulsion concentrate obtained by emulsifying the active ingredient in a mixture consisting of 20 70wt~ of cyclohexanone, 20wt~ of Nekanil~ LN (5 Lutensol AP6, a spreader-sticker with an emulsifying and dispersing action based on ethoxylated alkylphenols) and lOwt% of Emulphor~ EL (3 Emulan~ EL, an emulsifier based on ethoxylated fatty alcohols). The concentrations given in the exa~ptes were obtained by diluting the formulated active ingredient with water.
Contact action on oriental cockroaches (Blatta orientalis) The bottoms of 1-liter jars were treated with acetonic solutions of the active ingredients. After the solvent had evaporated, 5 adult cockroaches 30 were placed in each jar. The kill rate was determined after 48 hours.

-4~

17 O.Z. 0050/40806 The compounds of Examples 1, 3, 6-8, 11-13, 16, 20-22, 28, 30-32, 35-36, 38-39, 43, 53 and 54 have a better action than comparative agents A and B.
Contact action on granary weevils (Sitophilus granaria) Roughened glass plates 8 x 8 cm square were treated with acetonic solutions of the active ingredients.
After the solvent had evaporated, 100 weevils were placed on each plate10 and covered with a watchglass (6 cm in diameter). After 4 hours the weevils were transferred to untreated vessels. The kill rate was de~ermin-ed after 24 hours by ascertaining how many weevils were able, after this period of time, to leave an untreated cardboard dish (40 mm in diameter and 10 mm high) within 60 minutes.
The compounds of Examples 1-3, 5-8, 11-13, 15-16, 18, 20-21, 30-32, 35-36, 38, 53 and 54 had a better action than comparative agents A and B.
Continuous contact action on Musca domestica (housefly) Both the tops and bottoms of Petri dishes 10 cm in diameter were lined with a total of 2 ml of acetonic solutions of the active ingredients.
After the solvent had evaporated (about 30 mins.), 10 flies were intro-duced into each dish. The kill rate was established after 4 hours.
The active ingredients of Examples 1-2, 6-8, 11-13, 16, 20-22, 28, 30-32, 35-36, 38-39, 43, 53 and 54 had a better action than comparative agents A
and B.
30 Action of ingested food on Plutella maculipennis (diamondback moth) Leaves of young cabbage plants were dipped for 3 seconds into aqueous emulsions of the active ingredients and placed, after excess liquid had been briefly allowed to drip off, on a moist filter paper in a Petri dish.
35 10 caterpillars of the fourth stage were placed on each leaf. The kill rate was determined after 48 hours.
The active ingredients of Examples 1-3, 5-8, 11-14, 16, 20-22, 28, 30-32, 35-36, 38-39, 53 and 54 had a better action than comparative agent A.

. . , ~ , . . :: . ::.
- .: . , .~

. .

2~

18 O.Z. 0050/40806 Contact action on Prodenia litura The bottoms of glass Petri dishes 10 cm in diameter were treated with acetonic solutions of the active ingredients. After the solvent had 5 evaporated, 5 caterpillars in the third larval stage were introduced and the dishes closed. The kill rate was assessed in % after 4 hours.
The compounds of Examples 1, 3, 6-8, 11, 14-15, 18, 20, 28, 30-32, 35-36, 38-39, 43 and 54 had a better action than comparative agents A and B.

Claims (6)

1. Oximinophosphoric and -phosphonic acid derivatives of the general formula I

(I), where R1 is unbranched or branched alkyl of 1 to 4 carbon atoms, R2 is unbranched or branched alkyl of 1 to 4 carbon atoms, unbranched or branched alkoxy or alkylthio of 1 to 4 carbon atoms, phenyl, amino or branched alkylamino alkylamino or dialkylamino, each with 1 to 4 carbon atoms in each alkyl, R3 and R4 are hydrogen, methyl or chlorine and X is oxygen or sulfur.

2. A process for the manufacture of oximinophosphoric and -phosphonic acid derivatives of the formula I as set forth in claim 1, wherein an .alpha.-oximinonitrile of the formula II
(II), where R3 and R4 have the meanings given in claim 1, is reacted in the presence or absence of an acid acceptor, or an alkali metal, alkaline earth metal or substituted or unsubstituted ammonium salt of such an .alpha.-oximinonitrile is reacted with a (thio)phosphoric or -phosphonic ester or amide hallde of the formula III
(III).

3. A pesticidal agent containing a solid or liquid carrier and at least one oximinophosphoric or -phosphonic acid derivative of the formula I
as set forth in claim 1.

4. A process for combating pests, wherein an oximinophosphoric or -phosphonic acid derivative of the formula I as set forth in claim 1 is allowed to act on the pests or their habitat.

5. The use of oximinophosphoric and -phosphonic acid derivatives of the formula I as set forth in claim 1 for combating pests.

6. .alpha.-Oximinonitriles of the formula II
(II), where R3 and R4 are hydrogen, methyl or chlorine.