Note: Descriptions are shown in the official language in which they were submitted.
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 )
R4 CN R 2
where0 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:
R3 CH2
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:
CH2 0
/\ ~
R 3--C--CH--C
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.
EXAMPLE 1
/ \
H2C--C~ 11 OC2H5
C=N~P~
CN OC 2H5
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.
S EXAMPLE 2
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.
EXAMPLE 3
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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~- ~ 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.
... . ~ ~
~ r~
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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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.
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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
H5C20 CN
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.
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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.
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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.
