The present invention relates to trifluoromethoxyphenyl-(di)thiophosphoric acid esters, pesticides containing these compounds as active ingredients, and methods of controlling pests using these active ingredients and agents.

It has been disclosed that O,O-dialkyl O-phenylphosphorothioates have an insecticidal and acaricidal action (German Patent 814,152), and that O,O-dialkyl O(S)-(haloethylphenyl) (di)(thio)phosphates have an insecticidal action (U.S. Pat. No. 3,755,511).

We have found that trifluoromethoxyphenyl-(di)thiophosphoric acid esters of the formula ##STR2## where R¹ is alkyl of 1 to 3 carbon atoms, R² is alkyl or haloalkyl of 1 to 5 carbon atoms, alkoxyalkyl or alkylthioalkyl of 2 to 6 carbon atoms, or cycloalkyl of 3 to 6 carbon atoms, R³, R⁴ and R⁵ independently of one another are each hydrogen, halogen, nitro, cyano or alkyl, alkoxy or alkylthio of 1 to 4 carbon atoms and X is oxygen or sulfur, effectively control pests of the insect, arachnid and nematode classes. They have a superior action to that of the known O,O-dialkyl O-phenylphosphorothioates.

In formula I, R¹ is alkyl of 1 to 3 carbon atoms, such as methyl, ethyl, n-propyl or i-propyl, R² is alkyl or haloalkyl of 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec.-butyl, i-butyl, n-pentyl, 1-methyl-n-butyl, 2-chloroethyl or 3-chloro-n-propyl, or is alkoxyalkyl or alkylthioalkyl of 2 to 6 carbon atoms, such as 2-methoxyethyl, 2-ethoxyethyl, 2-isopropoxyethyl, 2-methylthioethyl or 2-ethylthioethyl, or is cycloalkyl of 3 to 6 carbon atoms, such as cyclopentyl or cyclohexyl, and R³, R⁴ and R⁵, which may differ, are each hydrogen, halogen, such as chlorine, bromine or fluorine, nitro, cyano or alkyl, alkoxy or alkylthio of 1 to 4 carbon atoms, preferably of 1 to 2 carbon atoms, such as methyl or ethyl.

Preferred compounds of the formula I are those where R¹ is ethyl, R² is alkyl of 3 or 4 carbon atoms, such as n-propyl, i-propyl, sec.-butyl or i-butyl, R³,R⁴ and R⁵ independently of one another are each hydrogen or chlorine and X is oxygen or sulfur.

The trifluoromethoxyphenyl-(di)thiophosphoric acid esters of the formula I are obtained by reacting a thiophosphoric acid ester chloride of the formula ##STR3## where R¹, R² and X have the above meanings, with a trifluoromethoxyphenol of the formula ##STR4## where R³, R⁴ and R⁵ have the above meanings, in the presence or absence of an acid acceptor and of a diluent, or with a salt of a trifluoromethoxyphenyl of the formula III in the presence or absence of a diluent.

The course of the reaction can be represented by the following equation: ##STR5##

The reaction of a thiophosphoric acid ester chloride of the formula II with a phenol of the formula III can be carried out in an organic diluent, such as acetonitrile, toluene or methyl ethyl ketone, or in a two-phase system, such as toluene/water or methylene chloride/water.

Advantageously, 1 to 2 moles of an acid acceptor per mole of phenol of the formula III are added. An excess of about 10% is preferably used. Suitable acid acceptors are bases, such as alkali metal carbonates, eg. potassium carbonate, alkali metal hydroxides, eg. sodium hydroxide, and tertiary amines, eg. triethylamine. Instead of a base and the phenol, it is equally possible to react a salt of the phenol with the phosphoric acid ester chloride. Suitable salts are the alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts, such as alkyl-substituted ammonium salts, for example the sodium, potassium, calcium, ammonium and trimethylammonium salts.

The reaction temperature can be varied within a relatively wide range. In general the reaction is carried out at from 0° to 100° C., preferably at from 20° to 70° C., under atmospheric pressure.

The starting materials are employed in an equimolar ratio. An excess of one or other of the reactants may provide advantages in some cases, but 0.9 to 1.1 moles of phosphoric acid ester chloride are preferably used per mole of phenol.

The reaction mixture is worked up in a conventional manner, for example by adding water and separating the phases. The crude products can be purified by distillation or column chromatography.

O,S-Dialkyl phosphate chlorides are known and can be prepared in a conventional manner (German Laid-Open Application (DOS) 2,642,982; and J. Org. Chem. 30, (1965), 3217). The trifluoromethoxyphenols of the formula III can also be prepared by processes disclosed in the literature (U.S. Pat. Nos. 3,265,741 and 4,157,344; and Zh. Obshch. Khim. 31, (1961), 915-924).

The following processes also lead to compounds of the formula I:

Trifluoromethoxyphenyl-thiophosporic acid esters of the formula Ia can be prepared by subjecting a phosphorous acid ester of the formula IV to an Arbusow reaction with a sulfenyl chloride of the formula R² SCl in accordance with the following equation: ##STR6##

The trifluoromethoxyphenyl-thiophosphoric acid esters of the formula Ia can also be obtained by alkylating a phosphoric acid ester salt of the formula V with an alkylating agent of the formula R² Y: ##STR7##

Moreover, a phosphoric acid ester dichloride of the formula VI can be reacted with an alcohol or mercaptan of the formula R¹ OH or R² SH to give a compound of the formula I: ##STR8##

In these equations, R¹, R², R³, R⁴, R⁵ and X have the above meanings, Me.sup.⊕ is a metal cation or a substituted or unsubstituted ammonium ion and Y is halide, for example iodide, bromide or chloride, or alkylsulfate, for example methylsulfate.

PREPARATION EXAMPLE

0.05 part by weight of diphenyl sulfide is added to a solution of 8.9 parts by weight of 4-trifluoromethoxyphenol in 30 parts by weight of glacial acetic acid, and 6.8 parts by weight of sulfuryl chloride are then added dropwise, without cooling. The mixture is subsequently stirred at room temperature for 3 hours, the solvent is stripped off and the residue is taken up in 50 parts by weight of methylene chloride. This solution is twice washed with 50 parts by weight of saturated bicarbonate solution, and is dried and concentrated. Distillation of the residue under reduced pressure gives 9.8 parts by weight (92% of theory) of 2-chloro-4-trifluoromethoxyphenol of boiling point 70° C./13 mbar.

4.6 parts by weight of potassium carbonate are added to 7.0 parts by weight of 2-chloro-4-trifluoromethoxyphenol in 100 parts by weight of acetonitrile, and the mixture is refluxed for one hour, with stirring. 6.5 parts by weight of O-ethyl S-sec.-butyl phosphorothioate chloride are then added dropwise at 50° C., and the mixture is stirred at 50° C. for 2 hours and then at room temperature for 24 hours. The solvent is removed in a rotary evaporator, 300 parts by weight of toluene and 100 parts by weight of water are added to the residue, the phases are separated, the organic phase is washed with 2 N sodium hydroxide solution and then with water and dried with sodium sulfate and the solvent and volatile impurities are removed at 40° C. under a pressure of 0.1 mbar. 8.7 parts by weight of O-ethyl S-sec.-butyl O-(2-chloro-4-trifluoromethoxyphenyl)-thiophosphate of n_D ²³ =1.4795 are obtained as the residue.

The following compounds of the formula I can be obtained, for example, by a similar method or by one of the other processes described above:

__________________________________________________________________________ ##STR9##                  PositionNo. R1  R2       X of OCF3                       R3                           R4                               R5                                   nD__________________________________________________________________________1   CH3  n-C3 H7                S 2    H   H   H2   CH3  n-C3 H7                O 3    H   H   H3   CH3  n-C3 H7                S 4    H   H   H4   CH3  n-C3 H7                O 2    H   H   H5   CH3  n-C3 H7                O 3    H   H   H6   CH3  n-C3 H7                O 4    H   H   H7   CH3  sec-C4 H9                S 2    H   H   H8   CH3  sec-C4 H9                S 3    H   H   H9   CH3  sec-C4 H9                S 4    H   H   H10  CH3  sec-C4 H9                O 2    H   H   H11  CH3  sec-C4 H9                O 3    H   H   H12  CH3  sec-C4 H9                O 4    H   H   H13  CH3  n-C3 H7                O 2    H   4-Cl                               H14  CH3  n-C3 H7                O 3    H   4-Cl                               H15  CH3  n-C3 H7                O 4    H   H   2-Cl16  CH3  n-C3 H7                O 2    H   4-Br                               H17  CH3  n-C3 H7                O 3    H   4-Br                               H18  CH3  n-C3 H7                O 4    H   H   2-Br19  CH3  sec-C4 H9                O 2    H   4-Cl                               H20  CH3  sec-C4 H9                O 3    H   4-Cl                               H21  CH3  sec-C4 H9                O 4    H   H   2-Cl22  C2 H5  n-C3 H7                O 2    H   H   H23  C2 H5  n-C3 H7                O 3    H   H   H24  C2 H5  n-C3 H7                O 4    H   H   H25  C2 H5  n-C3 H7                O 2    H   4-Cl                               H26  C2 H5  n-C3 H7                O 3    H   H   H27  C2 H5  n-C3 H7                O 4    H   H   H28  C2 H5  n-C3 H7                O 2    H   H   H29  C2 H5  n-C3 H7                O 3    H   H   H   nD 27 = 1.467030  C2 H5  n-C3 H7                O 4    H   H   H31  C2 H5  n-C3 H7                O 2    H   4-Cl                               H32  C2 H5  n-C3 H7                O 3    H   4-Cl                               H33  C2 H5  n-C3 H7                O 4    H   H   2-Cl                                   nD 25 = 1.479534  C2 H5  n-C3 H7                O 2    H   4-Br                               H35  C2 H5  n-C3 H7                O 3    H   4-Br                               H36  C2 H5  n-C3 H7                O 4    H   H   2-Br37  C2 H5  n-C3 H7                O 2    6-Cl                           4-Cl                               H38  C2 H5  n-C3 H7                O 3    6-Cl                           4-Cl                               H39  C2 H.sub. 5  n-C3 H7                O 4    6-Cl                           4-Cl                               H40  C2 H5  n-C3 H7                O 2    6-Br                           4-Br                               H41  C2 H5  n-C3 H7                O 3    6-Br                           4-Br                               H42  C2 H5  n-C3 H7                O 4    6-Br                           H   2-Br43  C2 H5  n-C3 H7                O 2    H   5-CH3                               H44  C2 H5  n-C3 H7                O 3    H   5-CH3                               H45  C2 H5  n-C3 H7                O 4    H   5-CH3                               H46  C2 H5  n-C3 H7                O 2    H   4-CN                               H47  C2 H5  n-C3 H7                O 3    H   4-CN                               H48  C2 H5  n-C3 H7                O 4    3-CN                           H   H49  C2 H5  n-C3 H7                S 2    H   H   H50  C2 H5  n-C3 H7                S 3    H   H   H   nD 26 = 1.497551  C2 H5  n-C3 H7                O 4    H   H   H52  C2 H5  n-C3 H7                S 2    H   4-Cl                               H53  C2 H5  n-C3 H7                S 3    H   4-Cl                               H54  C2 H5  n-C3 H7                S 4    2-Cl                           H   H   nD 24 = 1.510055  C2 H5  n-C3 H7                S 2    H   4-Br                               H56  C2 H5  n-C3 H7                S 3    H   4-Br                               H57  C2 H5  n-C3 H7                S 4    2-Br                           H   H58  C2 H5  i-C3 H7                O 2    H   H   H59  C2 H5  i-C3 H7                O 3    H   H   H60  C2 H5  i-C3 H7                O 4    H   H   H61  C2 H5  i-C3 H7                O 2    H   4-Cl                               H62  C2 H5  i-C3 H7                O 3    H   4-Cl                               H63  C2 H5  i-C3 H7                O 4    2-Cl                           H   H64  C2 H5  i-C3 H7                O 2    H   4-Br                               H65  C2 H5  i-C3 H7                O 3    H   4-Br                               H66  C2 H5  i-C3 H7                O 4    H   H   2-Cl67  C2 H5  sec-C4 H9                O 2    H   H   H68  C2 H5  sec-C4 H9                O 3    H   H   H   nD 26 = 1.468369  C2 H5  sec-C4 H9                O 4    H   H   H70  C2 H5  sec-C4 H9                O 2    H   4-Cl                               H71  C2 H5  i-C3 H7                O 3    H   4-Cl                               H72  C2 H5  i-C3 H7                O 4    Cl  H   H   nD 23 = 1.479573  C2 H5  i-C3 H7                O 2    H   4-Br                               H74  C2 H5  i-C3 H7                O 3    H   4-Br                               H75  C2 H5  i-C3 H7                O 4    2-Br                           H   H76  C2 H5  i-C3 H7                O 2    H   4-Cl                               6-Cl77  C2 H5  i-C3 H7                O 3    H   4-Cl                               6-Cl78  C2 H5  i-C3 H7                O 4    2-Cl                           H   6-Cl79  C2 H5  i-C3 H7                O 2    H   4-Br                               6-Br80  C2 H5  i-C3 H7                O 3    H   4-Br                               6-Br81  C2 H5  i-C3 H7                O 4    2-Br                           H   6-Br82  C2 H5  i-C3 H7                O 2    H   H   4-CN83  C2 H5  i-C3 H7                O 3    2-CN                           H   H84  C2 H5  i-C3 H7                O 4    H   4-CN                               H85  C2 H5  i-C3 H7                O 2    H   H   5-CH386  C2 H5  sec-C4 H9                O 3    H   H   5-CH387  C2 H5  sec-C4 H9                O 4    H   H   5-CH388  C2 H5  sec-C4 H9                O 2    H   4-F H89  C2 H5  sec-C4 H9                O 3    H   4-F H90  C2 H5  sec-C4 H9                O 4    2-F H   H91  C2 H5  sec-C4 H9                S 2    H   H   H92  C2 H5  sec-C4 H9                S 3    H   H   H93  C2 H5  sec-C4 H9                S 4    H   H   H94  C2 H5  sec-C4 H9                S 2    H   4-Cl                               H95  C2 H5  sec-C4 H9                S 3    H   4-Cl                               H96  C2 H5  sec-C4 H9                S 4    2-Cl                           H   H97  C2 H5  i-C4 H9                S 2    H   H   H98  C2 H5  i-C4 H9                O 3    H   H   H99  C2 H5  i-C4 H9                O 4    H   H   H100 C2 H5  i-C4 H9                O 2    H   4-Cl                               H101 C2 H5  i-C4 H9                O 3    H   4-Cl                               H102 C2 H5  i-C4 H9                O 4    2-Cl                           H   H   nD 23 = 1.4780103 C2 H5  i-C4 H9                O 2    H   4-Br                               H104 C2 H5  i-C4 H9                O 3        4-Br                               H105 C2 H5  i-C4 H9                O 4    2-Br                           H   H106 C2 H5  i-C4 H9                S 2    H   H   H107 C2 H5  i-C4 H9                S 3    H   H   H108 C2 H5  i-C4 H9                S 4    H   H   H109 C2 H5  i-C4 H9                S 2    H   4-Cl                               H110 C2 H5  i-C4 H9                S 3    H   4-Cl                               H111 C2 H5  i-C4 H9                S 4    2-Cl                           H   H112 C2 H5  CH3 O(CH2)2                O 2    H   H   H113 C2 H5  CH3 O(CH2)2                O 3    H   H   H114 C2 H5  CH3 O(CH2)2                O 4    H   H   H115 C2 H5  CH3 O(CH2)2                O 2    H   4-Cl                               H116 C2 H5  CH3 O(CH2)2                O 3    H   4-Cl                               H117 C2 H5  CH3 O(CH2)2                O 4    2-Cl                           4   H118 C2 H5  CH3 O(CH2)2                O 2    H   4-Br                               H119 C2 H5  CH3 O(CH2)2                O 3    H   4-Br                               H120 C2 H5  CH3 O(CH2)2                O 4    2-Br                           H   H121 C2 H5  C2 H5 O(CH2)2                O 2    H   H   H122 C2 H5  C2 H5 O(CH2)2                O 3    H   H   H123 C2 H5  C2 H5 O(CH2)2                O 4    H   H   H124 C2 H5  C2 H5 O(CH2)2                O 2    H   4-Cl                               H125 C2 H5  C2 H5 O(CH2)2                O 3    H   4-Cl                               H126 C2 H5  C2 H5 O(CH2)2                O 4    H   H   2-Cl127 C2 H5  C2 H5 O(CH2)2                O 2    H   4-Br                               H128 C2 H5  C2 H5 O(CH2)2                O 3    H   4-Br                               H129 C2 H5  C2 H5 O(CH2)2                O 4    2-Br                           H   H130 C.sub. 2 H5  i-C3 H7 O(CH2)2                O 2    H   H   H131 C2 H5  i-C3 H7 O(CH2)2                O 3    H   H   H132 C2 H5  i-C3 H7 O(CH2)2                O 4    H   H   H133 C2 H5  i-C3 H7 O(CH2)2                O 2    H   4-Cl                               H134 C2 H5  i-C3 H7 O(CH2)2                O 3    H   4-Cl                               H135 C2 H5  i-C3 H7 O(CH2)2                O 4    2-Cl                           H   H136 C2 H5  i-C3 H7 O(CH2)2                O 2    H   4-Br                               H137 C2 H5  i-C3 H7 O(CH2)2                O 3    H   4-Br                               H138 C2 H5  i-C3 H7 O(CH2)2                O 4    2-Br                           H   H139 C2 H5  CH3(CH2)2CH(CH3)                O 2    H   H   H140 C.sub. 2 H5  CH3(CH2)2CH(CH3)                O 3    H   H   H141 C2 H5  CH3(CH2)2CH(CH3)                O 4    H   H   H142 C2 H5  C5 H9                O 2    H   H   H143 C2 H5  C5 H9                O 3    H   H   H144 C2 H5  C5 H9                O 4    H   H   H145 C2 H5  ClCH2(CH2)2                O 2    H   H   H146 C2 H5  ClCH2(CH2)2                O 3    H   H   H147 C2 H5  ClCH2(CH2)2                O 4    H   H   H__________________________________________________________________________

The trifluoromethoxyphenyl-(di)thiophosphoric acid esters of the formula I according to the invention are suitable for effectively combating pests from the classes of insects, arachnids and nematodes. They may be employed as pesticides for protecting crops, and in the hygiene, stores protection and veterinary sectors.

Examples of injurious insects from the Lepidoptera order are Plutella maculipennis, Leucoptera coffeella, Hyponomeuta malinellus, Argyresthia conjugella, Sitotroga cerealella, Phthorimaea operculella, Capua reticulana, Sparganothis pilleriana, Cacoecia murinana, Tortrix viridana, Clysia ambiguella, Evetria buoliana, Polychrosis botrana, Cydia pomonella, Laspeyresia molesta, Laspeyresia funebrana, Ostrinia nubilalis, Loxostege sticticalis, Ephestia kuehniella, Chilo suppressalis, Galleria mellonella, Malacosoma neustria, Dendrolimus pini, Thaumatopoea pityocampa, Phalera bucephala, Cheimatobia brumata, Hibernia defoliaria, Bupalus piniarus, Hyphantria cunea, Agrotis segetum, Agrotis ypsilon, Barathra brassicae, Cirphis unipuncta, Prodenia litura, Laphygma exigua, Panolis flammea, Earias insulana, Plusia gamma, Alabama argillacea, Lymantria dispar., Lymantria monocha, Pieris brassicae, and Aporia crataegi;

examples from the Coleoptera order are Blitophaga undata, Melanotus communis, Limonius californicus, Agriotes lineatus, Agriotes obscurus, Agrilus sinuatus, Meligethes aeneus, Atomaria linearis, Epilachna varivestris, Phyllopertha horticola, Popillia japonica, Melolontha melolontha, Melolontha hippocastani, Amphimalus solstitialis, Crioceris asparagi, Lema melanopus, Leptinotarsa decemlineata, Phaedon cochleariae, Phyllotreta nemorum, Chaetocnema tibialis, Phylloides chrysocephala, Diabrotica 12-punctata, Cassida nebulosa, Bruchus lentis, Bruchus rufimanus, Bruchus pisorum, Sitona lineatus, Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Hylobies abietis, Byctiscus betulae, Anthonomus pomorum, Anthonomus grandis, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Sitophilus granaria, Anisandrus dispar, Ips typographus, and Blastophagus piniperda;

examples from the Diptera order are Lycoria pectorialis, Mayetiola destructor, Dasyneura brassicae, Contarinia tritici, Haplodiplosis equestris, Tipula paludosa, Tipula oleracea, Dacus cucurbitae, Dacus oleae, Ceratitis capitata, Rhagoletis cerasi, Rhagoletis pomonella, Anastrepha ludens, Oscinella frit, Phorbia coarctata, Phorbia antiqua, Phorbia brassicae, Pegomya hyoscyami, Anopheles maculipennis, Culex pipiens, Aedes aegypti, Aedes vexans, Tabanus bovinus, Tipula paludosa, Musca domestica, Fannia canicularis, Muscina stabulans, Glossina morsitans, Oestrus ocis, Chrysomya macellaria, Chrysomya hominivorax, Lucilia cuprina, Lucilia sercata, and Hypoderma lineata;

examples from the Hymenoptera order are Athalia rosae, Haplocampa minuta, Monomorium pharaonis, Solenopsis geminata, and Atta sexdens;

examples from the Heteroptera order are Nezara viridula, Eurygaster integriceps, Blissus leucopterus, Dysdercus cingulatus, Dysdercus intermedius, Piesma quadrata, and Lygus pratensis;

examples from the Homoptera order are Perkinsiella saccharicida, Nilaparvata lugens, Empoasca fabae, Psylla mali, Psylla piri, Trialeurodes vaporariorum, Aphis fabae, Aphis pomi, Aphis sambuci, Aphidula nasturtii, Cerosipha gossypii, Sappaphis mali, Sappaphis mala, Dysaphis radicola, Brachycaudus cardui, Brevicoryne brassicae, Phorodon humuli, Rhopalomyzus ascalonicus, Myzodes persicae, Myzus cerasi, Dysaulacorthum pseudosolani, Acyrthosiphon onobrychis, Macrosiphon rosae, Megoura viciae, Schizoneura lanuginosa, Pemphigus bursarius, Dreyfusia nordmannianae, Dreyfusia piceae, Adelges laricis, and Viteus vitifolii;

examples from the Isoptera order are Reticulitermes lucifugus, Calotermes flavicollis, Leucotermes flavipes, and Termes natalensis;

examples from the Orthoptera order are Forficula auricularia, Acheta domestica, Gryllotalpa gryllotalpa, Tachycines asynamorus, Locusta migratoria, Stauronotus maroccanus, Schistocerca peregrina, Nomadacris septemfasciata, Melanoplus spretus, Melanoplus femur-rubrum, Blatta orientalis, Blattella germanica, Periplaneta americana, and Blabera gigantea.

Examples of mites and ticks (Acarina) belonging to the Arachnida class are Tetranychus telarius, Tetranychus atlanticus, Tetranychus pacificus, Paratetranychus pilosus, Bryobia praetiosa, Ixodes ricinus, Ornithodorus moubata, Ablyomma americanum, Dermacentor silvarum, and Boophilus microplus.

Examples from the Nemathelminthes class are root-knot nematodes, e.g., Meloidogyne incognita, Meloidogyne hapla, and Meloidogyne javanica, cyst-forming nematodes, e.g., Globodera rostochiensis, Heterodera schachtii, Heterodera avenae, Heterodera glycines, and Heterodera trifolii, and stem and leaf eelworms, e.g., Ditylenchus dipsaci, Ditylenchus destructor, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus goodeyi, Pratylenchus curvitatus and Tylenchorhynchus dubius, Tylenchorhynchus claytoni, Rotylenchus robustus, Heliocotylenchus multicinctus, Radopholus similis, Belonolaimus longicaudatus, Longidorus elongatus, and Trichodorus primitivus.

The active ingredients may be applied as such, in the form of formulations, or of ready-to-use 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 depend entirely on the purpose for which the agents are being used; in any case they should ensure as fine a distribution of the active ingredient as possible.

For the preparation of solutions, emulsions, pastes and oil dispersions to 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 vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, and strongly polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, and water 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 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 ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyester alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

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, Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium 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.

The formulations generally contain from 0.1 to 95, and preferably 0.5 to 90, % by weight of active ingredient.

The amount of active ingredient in the ready-to-use formulations may vary within a wide range; it is generally from 0.0001 to 10%, preferably from 0.01 to 1%.

Examples of formulations are given below.

I. 5 parts by weight of compound no. 18 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. 29 is intimately mixed with a mixture 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.

III. 10 parts by weight of compound no. 33 is dissolved in a mixture consisting of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 moles of ethylene oxide with 1 mole of oleic acid-N-monoethanolamide, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 2 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil.

IV. 20 parts by weight of compound no. 53 is dissolved in a mixture consisting of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol, and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil.

V. 80 parts by weight of compound no. 50 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-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.

The active ingredients may also be successfully used in the ultra-low volume method, where it is possible to apply formulations containing more than 95 wt% of active ingredient, or even the 100% active ingredient.

When the active ingredient are applied in the open, the rates are from 0.2 to 10, preferably 0.5 to 2.0, kg/ha.

There may be added to the active ingredients (if desired, immediately before use (tankmix)) oils of various types, herbicides, fungicides, other pesticides and bactericides. These agents may be added to the active ingredients according to the invention in a weight ratio of from 1:10 to 10:1.

Examples of active ingredients which may be admixed are as follows:

1,2-dibromo-3-chloropropane, 1,3-dichloropropene, 1,3-dichloropropene+1,2-dichloropropane, 1,2-dibromomethane, 2-sec-butylphenyl-N-methylcarbamate, o-chlorophenyl-N-methylcarbamate, 3-isopropyl-5-methylphenyl-N-methylcarbamate, o-isopropoxyphenyl-N-methylcarbamate, 3,5-dimethyl-4-methylmercaptophenyl-N-methylcarbamate, 4-dimethylamino-3,5-xylyl-N-methylcarbamate, 2-(1,3-dioxolan-2-yl)-phenyl-N-methylcarbamate, 1-naphthyl-N-methylcarbamate, 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N-methylcarbamate, 2,2-dimethyl-1,3-benzodioxol-4-yl-N-methylcarbamate, 2-dimethylamino-5,6-dimethyl-4-pyrimidinyldimethylcarbamate, 2-methyl-2-(methylthio)-propionaldehyde-O-(methylcarbamoyl)-oxime, S-methyl-N-[(methylcarbamoyl)-oxy]-thioacetimidate, methyl-N',N'-dimethyl-N-[(methylcarbamoyl)-oxy]-1-thiooxamidate, N-(2-methyl-4-chlorophenyl)-N,N'-dimethylformamidine, tetrachlorothiophene, 1-(2,6-difluorobenzyl)-3-(4-chlorophenyl)-urea, O,O-dimethyl-O-(p-nitrophenyl)-phosphorothioate, O,O-diethyl-O-(p-nitrophenyl)-phosphorothioate, O-ethyl-O-(p-nitrophenyl)-phenylphosphonothioate, O,O-dimethyl-O-(3-methyl-4-nitrophenyl)-phosphorothioate, O,O-diethyl-O-(2,4-dichlorophenyl)-phosphorothioate, O-ethyl-O-(2,4-dichlorophenyl)-phenylphosphonothioate, O,O-dimethyl-O-(2,4,5-trichlorophenyl)-phosphorothioate, O-ethyl-O-(2,4,5-trichlorophenyl)-ethyl-phosphonothioate, O,O-dimethyl-O-(4-bromo-2,5-dichlorophenyl)-phosphorothioate, O,O-dimethyl-O-(2,5-dichloro-4-iodophenyl)-phosphorothioate, O,O-dimethyl-O-(3-methyl-4-methylthiophenyl)-phosphorothioate, O-ethyl-O-(3-methyl-4-methylthiophenyl)-isopropylphosphoramidate, O,O-diethyl-O-[p-(methylsulfynyl)-phenyl]-phosphorothioate, O-ethyl-S-phenylethyl-phosphonodithioate, O,O-diethyl-[2-chloro-1-(2,4-dichlorophenyl)-vinyl]-phosphate, O,O-dimethyl-[-2-chloro-1-(2,4,5-trichlorophenyl)]-vinylphosphate, O,O-dimethyl-S-(1-phenyl)-ethylacetate phosphorodithioate, bis-(dimethylamino)-fluorophosphine oxide, octamethyl-pyrophosphoramide, O,O,O,O-tetraethyldithiopyrophosphate, S-chloromethyl-O,O-diethyl-phosphorodithioate, O-ethyl-S,S-dipropyl-phosphorodithioate, O,O-dimethyl-O-2,2-dichlorovinylphosphate, O,O-dimethyl-1,2-dibromo-2,2-dichloroethylphosphate, O,O-dimethyl-2,2,2-trichloro- B 1-hydroxyethylphosphonate, O,O-dimethyl-S-[1,2-biscarbethoxyethyl-(1)]-phosphorodithioate, O,O-dimethyl-O-(1-methyl-2-carbomethoxyvinyl)-phosphate, O,O-diimethyl-S-(N-methylcarbamoylmethyl)-phosphorodithioate, O,O-dimethyl-S-(N-methylcarbamoylmethyl)-phosphorothioate, O,O-dimethyl-S-(N-methoxyethylcarbamoylmethyl)-phosphorodithioate, O,O-dimethyl-S-(N-formyl-N-methylcarbamoylmethyl)-phosphorodithioate, O,O-dimethyl-O-[1-methyl-2-(methylcarbamoyl)-vinyl]-phosphate, O,O-dimethyl-O-[(1-methyl-2-dimethylcarbamoyl)-vinyl]-phosphate, O,O-dimethyl-O-[(1-methyl-2-chloro-2-diethylcarbamoyl)-vinyl]-phosphate, O,O-diethyl-S-(ethylthiomethyl)-phosphorodithioate, O,O-diethyl-S-[(p-chlorophenylthio)-methyl]-phosphorodithioate, O,O-dimethyl-S-(2-ethylthioethyl)-phosphorothioate, O,O-dimethyl-S-(2-ethylthioethyl)-phosphorodithioate, O,O-dimethylsulfynylethyl)-phosphorothioate, O,O-diethyl-S-(2-ethylthioethyl)-phosphorodithioate, O,O-diethyl-S-(2-ethylsulfynylethyl)-phosphorothioate, O,O-diethylthiophosphoryliminophenyl-acetonitrile, O,O-diethyl-S-(2-chloro-1-phthalimidoethyl)-phosphorodithioate, O,O-diethyl-S-[6-chlorobenzoxazolon-(2)-yl-(3)]-methyldithiophosphate, O,O-dimethyl-S-[2-methoxy-1,3,4-thiadiazol-5-onyl-(4)-methyl]-phosphorodithioate, O,O-diethyl-O-[3,5,6-trichloropyridyl-(2)]-phosphorothioate, O,O-diethylO-(2-pyrazinyl)-phosphorothioate, O,O-diethyl-O-[2-isopropyl-4-methylpyrimidinyl-(6)]-phosphorothioate, O,O-diethyl-O-[2-(diethylamino)-6-methyl-4-pyrimidinyl]-thionophosphate, O,O-dimethyl-S-(4-oxo-1,2,3-benzotriazin-3-[4H]-yl-methyl)-phosphorodithioate, O,O-dimethyl-S-[(4,6-diamino-1,3,5-triazin-2-yl)-methyl]-phosphorodithioate, O,O-diethyl-(1-phenyl-1,2,4-triazol-3-yl)-thionophosphate, O,S-dimethylphosphoroamidothioate, O,S-dimethyl-N-acetylphosphoramidothioate, α-hexachlorocyclohexane, 1,1-di-(p-methoxyphenyl)- 2,2,2-trichloroethane, 6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine-3-oxide, pyrethrins, DL-2-allyl-3-methyl-cyclopenten-(2)-on-(1)-yl-(4)-DL-cis,trans-chrysanthemate, 5-benzylfuryl-(3)-methyl-DL-cis,trans-chrysanthemate, 3-phenoxybenzyl(±)-cis,trans-2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylate, α-cyano-3-phenoxybenzyl(±)-cis,trans-2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropane carboxylate, (s)-α-cyano-3-phenoxybenzyl-cis(1R,3R)-2,2-dimethyl-3-(2,2-dibromovinyl)-cyclopropane carboxylate, 3,4,5,6-tetrahydrophthalimidoethyl-DL-cis,trans-chrysanthemate, 2-methyl-5-(2-propynyl)-3-furylmethylchrysanthemate, and α-cyano-3-phenoxybenzyl-α-isopropyl-4-chlorophenylacetate.

The following examples illustrate the biological action of the new compounds.

The active ingredients are numbered as in the foregoing table.

EXAMPLE 1

Continuous contact action on houseflies (Musca domestica)

Both covers and bottoms of Petri dishes 10 cm in diameter are lined with a total (per dish) of 2 ml of acetonic solutions of the active ingredients. After the solvent has evaporated (about 30 mins.), 20 4-day old flies are introduced into the dishes. The kill rate is determined after 4 hours.

In this test, a very high kill rate is achieved with compounds nos. 29, 33, 50, 54 and 68.

EXAMPLE 2

Contact action and the effect of ingested food on caterpillars of the diamondback moth (Plutella maculipennis)

Leaves of young cabbage plants are dipped for 3 seconds in aqueous emulsions of the active ingredients and, after excess liquid has been briefly allowed to drip off, placed on a moist filter paper in a Petri dish. 10 caterpillars of the 4th stage are then placed on each leaf.

The action is assessed after 48 hours.

In this test, the following compounds, for example, had a very good action: 29, 33, 50, 54, 68 and 102.

EXAMPLE 3

Contact action on oriental cockroaches (Blatta orientalis)

The bottoms of 1 liter preserving jars is lined with acetonic solutions of the active ingredients. After the solvent has evaporated, 5 adult cockroaches are introduced into each jar. The kill rate is determined after 48 hours.

In this test, compounds nos. 29, 33, 50, 54, 68, 72 and 102 have an excellent action.

EXAMPLE 4

Contact action on granary weevils (Sitophilus granarius)

Petris dishes 10 cm in diameter are lined with acetonic solutions of the active ingredients. After the solvent has evaporated, 100 granary weevils are placed in each dish.

After 4 hours, the weevils are transferred to untreated vessels. The kill rate is determined after 24 hours, by counting how many weevils are, after this period has elapsed, capable of leaving an untreated cardboard dish (40 mm in diameter, 10 mm high) within 60 minutes.

In this test, compounds nos. 29, 33, 50, 54, 68 and 72 have a very good action.

EXAMPLE 5

Contact action on ticks (Ornithodorus moubata)

Ticks in the 3rd larval stage are placed in paper bags and dipped for 3 seconds in the emulsion under investigation. The bags are then suspended. The action on the ticks is assessed after 48 hours.

In this test, compounds nos. 29, 33 and 68 have a very good action.

EXAMPLE 6

Systemic action on caterpillars (Prodenia litura)

200 ml of quartz sand is introduced into 250 ml plastic beakers in 8-vessel trays. 5 grains of Indian corn are placed in each beaker, about 1 cm below the surface. 50 ml of water is then added to each beaker, and transparent plastic covers are then fitted over the trays. The covers are removed after 8 days, and treatment is carried out after 10 days by pouring 40 ml of aqueous active ingredient formulations on to the plants; one day later, 50 ml of dry quartz sand is added so as to prevent the animals coming into contact with the treated surface.

A plastic cylinder (7 cm in diameter) is then placed on each beaker, 5 caterpillars in the 3rd larval stage are introduced, and the cylinders are covered with a wire gauze.

The damage caused, and the kill rate are assessed after 4 days.

In this test, compounds nos. 29, 30, 50, 54, 68, 72 and 102 have a good action.

EXAMPLE 7

Breeding experiment with houseflies larvae (Musca domestica)

50 g of a culture medium consisting of 10 parts of baker's yeast, 10 parts of dried milk, 100 parts of water and 1 part of agar is thoroughly mixed, while warm, with the aqueous active ingredient formulations. After the medium has cooled, approx. 0.1 ml of flies' eggs is placed on it and their development is observed for a week. The temperature is kept at 20° C.

In this test, compounds nos. 29, 33, 50, 54, 68, 72 and 102 have a good action.

EXAMPLE 8

Action on nematodes (Ditylenchus dipsaci)

Nematodes (Ditylenchus dipsaci) freshly extracted from living plant tissue are suspended in pure tapwater. Aqueous active ingredient formulations are added to such suspensions, and the kill rate is assessed after 4 and 24 hours.

In this test, compounds nos. 29, 33, 50, 54, 68, 72 and 102 have a good action.