Pesticides based on 2-halogenoalkylthio-substituted pyrimidine derivatives

A method of combating pests which comprises applying to such pests or to a pest habitat a pesticidally effective amount of a 2-halogenoalkylthio-substituted pyrimidine of the formula ##STR1## in which R.sup.1 represents halogenoalkyl, PA0 R represents hydrogen, alkyl, alkylthio, alkoxy, halogenoalkyl, halogenoalkylthio, halogenoalkoxy, optionally substituted aryl or halogen and PA0 m represents a number 0, 1, 2 or 3. Those compounds other than 2-(difluoromethylthiomethylthio)-4,6-dimethyl-pyrimidine, 2,4-bis(difluoromethylthio)-6-methylpyrimidine and 4-(difluoromethoxy)-2-(difluoromethylthio(-6-methylpyrimidine are new.

The invention relates to the use of 2-halogenoalkylthio-substituted 
pyrimidine derivatives, some of which are known, as active compounds in 
pesticides, novel 2-halogenoalkylthio-substituted pyrimidine derivatives, 
and a process for the preparation thereof. 
It has already been disclosed that 2-halogenoalkylthio-substituted 
pyridines, such as, for example, 2-(dibromofluoromethylthio)-pyridine, 
possess insecticidal properties (cf. DE-A No. 3,510,178). 
However, the action of these compounds is not always entirely satisfactory 
in all fields of application, in particular at low application rates and 
application concentrations. 
Furthermore, 2-halogenoalkylthio-substituted pyrimidines, such as, for 
example, 2-(chloromethylthio)-5-chloropyrimidine and 
2-(iodomethylthio)-5-chloropyrimidine, are known as intermediates for the 
preparation of pharmaceutical products (cf. EP-A No. 0,033,195). 
In addition, 2-substituted thio-4,5-diarylpyrimidines are known, such as, 
for example, 
2-(1,1,2,2-tetrafluoromethylthio)-4,5-bis(4-methoxyphenyl)-pyrimidine and 
2-trifluoromethylthio-4,5-bis(4-fluorophenyl)-pyrimidine. These compounds 
have, inter alia, a powerful anti-inflammatory and analgesic action (cf. 
U.S. Pat. No. 4,438,117). 
Moreover, a large number of syntheses for 2-halogenoalkylthio-substituted 
pyrimidine derivatives are known (cf. J. Heterocycl. Chem., 23, 1079-84; 
J. Heterocyl. Chem. 22, 1077-80;J. Chem. Soc., Perkin Trans., 1, 2499-503; 
Chem. Scr., 20, 11-13; Deposited Doc., VINITI 910, 5; Zh. Org. Khim., 15, 
396-400; J. Org. Chem., 42, 3094-3096; Ukr. Khim. Zh. 42, 500-504; Ukr. 
Khim. Zh. 41, 498-500; Khim. Geterotsihl. Soedin., 1087-1088). 
No biological actions are described for these compounds. 
It has been found that the 2-halogenoalkylthio-substituted pyrimidine 
derivatives, some of which are known, of the general formula (I) 
##STR2## 
in which R.sup.1 represents halogenoalkyl, 
R represents hydrogen, alkyl, alkylthio, alkoxy, halogenoalkyl, 
halogenoalkylthio, halogenoalkgxy, optionally substituted aryl or halogen, 
and 
m represents a number 0, 1, 2 or 3, 
are highly effective against animal pests, in particular against insects, 
arachnids and nematodes. They are therefore suitable as active compounds 
in pesticides, in particular as insecticides, acaricides and nematicides. 
Surprisingly, the 2-halogenoalkylthio-substituted pyrimidine derivatives of 
the general formula (I) which are to be used according to the invention 
show a better action as pesticides, in particular as insecticides, 
acaricides and nematicides, than 2-(dibromo-fluoromethylthio)-pyridine, 
which is known from the prior art. 
The 2-halogenoalkylthio-substituted pyrimidine derivatives which are to be 
used according to the invention therefore represent a valuable enrichment 
of the art. 
Formula (I) provides a general definition of the 
2-halogenoalkylthio-substituted pyrimidine derivatives to be used 
according to the invention. Compounds of the formula (I) which are 
preferably used as pesticides are those in which 
R.sup.1 represents halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 
identical or different halogen atoms, 
represents hydrogen, in each case straight-chain or branched alkyl, 
alkylthio, alkoxy, halogenoalkyl, halogenoalkylthio or halogenoalkoxy, in 
each case having 1 to 4 carbon atoms and, in the case of halogenoalkyl, 
halogenoalkylthio and halogenoalkoxy, having 1 to 9 identical or different 
halogen atoms, furthermore represents phenyl which is optionally 
monosubstituted or polysubstituted by identical or different substituents 
from the series comprising halogen, nitro, alkyl or alkoxy, in each case 
having 1 to 4 carbon atoms, or halogenoalkyl having 1 to 4 carbon atoms 
and 1 to 9 identical or different halogen atoms, or also represents 
halogen, and 
m represents a number 0, 1, 2 or 3. 
Compounds of the formula (I) which are particularly preferably used are 
those in which 
R.sup.1 represents halogenomethyl having 1 to 3 identical or different 
halogen atoms, 
R represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or 
t-butyl, methylthio, methoxy, halogenoalkyl, halogenoalkylthio or 
halogenoalkoxy, in each case having 1 to 2 carbon atoms and 1 to 5 
identical or different halogen atoms; furthermore represents phenyl which 
is optionally monosubstituted to trisubstituted by identical or different 
substituents from the series comprising fluorine, chlorine, bromine, 
nitro, methyl, ethyl, methoxy, ethoxy or trifluoromethyl, or also 
represents halogen, and 
m represents a number 0, 1, 2 or 3. 
Some of the 2-halogenoalkylthio-substituted pyrimidine derivatives of the 
formula (I) which are to be used according to the invention are known (cf. 
J. Heterocycl. Chem., 23, 1079-84; J. Heterocyl. Chem. 22, 1077-80; J. 
Chem. Soc., Perkin Trans., 1, 2499-503; Chem. Scr., 20, 11-13; Deposited 
Doc., VINITI 910, 5; Zh. Org. Khim., 15, 396-400; J. Org. Chem., 42, 
3094-3096; Ukr. Khim. Zh. 42, 500-504; Ukr. Khim. Zh. 41, 498-500; Khim. 
Geterotsihl, Soedin., 1087-1088; EP-OS No. 0,033,195 and U.S. Pat. No. 
4,438,117). 
Substituted 2-halogenomethylthio)-pyrimidine derivatives of the formula 
(Ia) 
##STR3## 
in which R represents hydrogen, alkyl, alkylthio, alkoxy, halogenoalkyl, 
halogenoalkylthio, halogenoalkoxy, optionally substituted aryl, or 
represents halogen, 
m represents a number 0, 1, 2 or 3 and 
R.sup.2 represents hydrogen, chlorine, bromine or iodine, 
with the exception of the compounds 
2-(difluoromethylthio)-4,6-dimethyl-pyrimidine, 
2,4-bis(difluoromethylthio)-6-methyl-pyrimidine and 
4-(difluoromethoxy)-2-(difluoromethylthio)-6-methyl-pyrimidine, were 
hitherto unknown. 
Formula (Ia) provides a general definition of the 
2-halogenoalkylthio-substituted pyrimidine derivatives according to the 
invention Preferred compounds of the formula (Ia) are those in which 
R represents hydrogen, in each case straight-chain or branched alkyl, 
alkylthio, alkoxy, halogenoalkyl, halogenoalkylthio or halogenoalkoxy, 
each having 1 to 4 carbon atoms and, in the case of halogenoalkoxyl, 
halogenoalkylthio and halogenoalkoxy, having 1 to 9 identical or different 
halogen atoms, furthermore represents phenyl which is optionally 
monosubstituted or polysubstituted by identical or different substituents 
from the series comprising halogen, nitro, alkyl or alkoxy, each having 1 
to 4 carbon atoms, or halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 
identical or different halogen atoms, or also represents halogen, 
R.sup.2 represents hydrogen, chlorine or bromine and 
m represents a number 0, 1, 2 or 3, with the exception of the compounds 
2-(difluoromethylthio)-4,6-dimethyl-pyrimidine, 
2,4-bis(difluoromethylthio)-6-methylpyrimidine and 
4-(difluoromethoxy)-2-(difluoromethylthio)-6-methylpyrimidine 
Particularly preferred compounds of the formula (Ia) are those in which 
R represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or 
t-butyl, methylthio, methoxy, halogenoalkyl, halogenoalkylthio or 
halogenoalkoxy, each having 1 to 2 carbon atoms and 1 to 5 identical or 
different halogen atoms; furthermore represents phenyl which is optionally 
monosubstituted to trisubstituted by identical or different substituents 
from the series comprising fluorine, chlorine, bromine, nitro, methyl, 
ethyl, methoxy, ethoxy or trifluoromethyl, or also represents halogen, 
R.sup.2 represents hydrogen, chlorine or bromine and 
m represents a number 0, 1, 2 or 3, with the exception of the compounds 
2-(difluoromethylthio)-4,6-dimethyl-pyrimidine, 
2,4-bis(difluoromethylthio)-6-methyl-pyrimidine and 
4-(difluoromethoxy)-2-(difluoromethylthio)-6-methyl-pyrimidine. 
The substituted 2-(halogenomethylthio)-pyrimidine derivatives of the 
formula (Ia), which were hitherto unknown, are obtained when 
2-mercaptopyrimidines of the formula (II) 
##STR4## 
in which R and the index m have the abovementioned meanings, or the salts 
thereof, are alkylated with alkyl halides of the formula (III) 
EQU R.sup.2 --CF.sub.2 --X (III) 
in which 
R.sup.2 has the abovementioned meaning and 
X represents halogen, preferably chlorine or bromine, 
if appropriate in the presence of diluents and if appropriate in the 
presence of strong bases. 
The known compounds of the formula (I) may be prepared analogously to the 
process indicated above, for the preparation of the novel compounds of the 
formula (Ia). 
If, for example, 2-mercaptopyrimidine and dibromodifluoromethane are used 
as starting substances, the course of the reaction of the preparation 
process may be represented by the following equation: 
##STR5## 
Formula (II) provides a general definition of the 2-mercaptopyrimidines 
required as starting materials for carrying out the preparation process In 
this formula (II), R and the index m represent those meanings which have 
been indicated above in the description of the novel 
2-(halogenomethylthio)-pyrimidine derivatives of the formula (Ia) for R 
and the index m. 
The 2-mercaptopyrimidines of the formula (II) are known and/or can be 
prepared in a simple, analogous manner by known processes (cf. Coll. 
Czech. Chem. Commun., 24, 1667 (1959); Chem. Ber. 104, 2975 (1971) and 
U.S. Pat. No. 4,438,117). 
Formula (III) provides a general definition of the alkyl halides 
furthermore required as starting materials for carrying out the 
preparation process. In this formula (III), R.sup.2 and X have those 
meanings which have been indicated above in the description of the novel 
2-(halogenomethylthio)-pyrimidine derivatives of the formula (Ia) for 
R.sup.2 and X. 
The compounds of the formula (III) are generally known compounds of organic 
chemistry. 
The novel compounds of the formula (Ia) are preferably prepared using 
diluents. 
Suitable diluents in this process are water and virtually all inert organic 
solvents which are customary for the reaction. These preferably include 
aliphatic and aromatic, optionally halogenated hydrocarbons, such as 
pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, 
benzene, toluene, xylene, methylene chloride, ethylene chloride, 
chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, 
ethers, such as diethyl ether and dibutyl ether, glycol dimethyl ether and 
diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones, such as 
acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl 
ketone, esters, such as methyl acetate and ethyl acetate, nitriles, such 
as acetonitrile and propionitrile, alcohols, such as methanol, ethanol, 
n-propanol, isopropanol and butanol, amides, such as, for example, 
dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone, and also 
dimethyl sulphoxide, tetramethylene sulphone and hexamethylphosphoric 
triamide. 
Possible bases which are employed in excess are alkali metal hydroxides, 
such as, for example, sodium hydroxide and potassium hydroxide, alkaline 
earth metal hydroxides, such as, for example, calcium hydroxide, alkali 
metal carbonates and alkali metal alcoholates, such as sodium carbonate 
and potassium carbonate, sodium methylate, potassium methylate, sodium 
ethylate and potassium ethylate, hydrides, such as, for example, sodium 
hydride, furthermore aliphatic, aromatic or heterocyclic amines, for 
example triethylamine, trimethylamine, dimethylaniline, 
dimethylbenzylamine, pyridine, 1,5-diazabicyclo-[4,3,0]-non-5-ene (DBU), 
1,8-diazabicyclo-[5,4,0]-undec-7-ene (DBU) and 
1,4-diazabicyclo-[2,2,2]-octane (DABCO). 
In the process for the preparation of the novel compounds of the formula 
(Ia), the reaction temperatures can be varied in a relatively wide range. 
In general, the process is carried out at temperatures between 0.degree. 
C. and 100.degree. C., preferably at temperatures between 10.degree. C. 
and 70.degree. C. 
For carrying out the preparation process of the novel compounds of the 
formula (Ia), 1.0 to 10.0 moles, preferably 1.0 to 6.0 moles, of 
alkylating agent of the formula (III) and 1.0 to 8.0 moles, preferably 1.0 
to 5.0 moles, of base are generally employed per mole of 
2-mercaptopyrimidine of the formula (II). 
The process for the preparation of the novel compounds of the formula (Ia) 
is generally carried out under atmospheric pressure. Under certain 
conditions, however, the process can also be carried out under increased 
or reduced pressure. 
If gaseous alkylating agents of the formula (III) are used, these compounds 
can be passed in through the mixture of diluent, compound of the formula 
(II) and base. In general, the reactions are carried out in a suitable 
diluent, and the reaction mixture is stirred for several hours at the 
particular temperature required The reaction products of the formula (Ia) 
are worked up and isolated in a generally customary manner. 
The preparation and the use of the active compounds according to the 
invention can be seen from the following examples.

PREATION EXAMPLES 
EXAMPLE 1 
##STR6## 
7.5 g (0.25 mol) of sodium hydride (80% strength oil 
suspension) are added in portions at 20.degree.-30.degree. C. to a stirred 
solution of 11.2 g (0.1 mol) of 2-mercaptopyrimidine in 200 ml of 
dimethylformamide. After the mixture has been stirred for 30 minutes at 
20.degree. C., 96 g (0.45 mol) of dibromodifluoromethane are added, and 
stirring is continued overnight, likewise at 20.degree. C. The 
dimethylformamide is removed under reduced pressure at 
20.degree.-30.degree. C., the residue is treated with methylene 
chloride/water, and the organic phase is separated off. After the organic 
phase has been dried over magnesium sulphate, the solvent is removed under 
reduced pressure, and the residue is distilled. 
15.2 g (25% of theory) of 2-(bromodifluoromethylthio)-pyrimidine of boiling 
point bp 100.degree. C./0.3 mm are obtained. 
EXAMPLE 2 
##STR7## 
At 40.degree.-50.degree. C., 100 g (1.2 mol) of chlorodifluoromethane are 
passed into a stirred solution of 25 g (0.22 mol) of 2-mercaptopyrimidine 
in 120 ml of isopropanol and 30 g (0.73 mol) of sodium hydroxide in 45 ml 
of water. The reaction is slightly exothermic After the reaction is 
complete, the mixture is diluted with approximately 400 ml of water, and 
the product is extracted using methylene chloride. The organic phase is 
concentrated under reduced pressure, and the residue is distilled under 
reduced pressure. 
17.7 g (49.7% of theory) of 2-(difluoromethylthio)-pyrimidine of boiling 
point bp 95.degree. C./20 mm are obtained. 
The compounds of the formula (I) which are mentioned in the following Table 
1 can be prepared analogously to Examples 1 and 2, i.e. the process 
according to the invention: 
TABLE 1 
______________________________________ 
##STR8## (I) 
Example No. 
##STR9## R.sup.1 constantsPhysical 
______________________________________ 
##STR10## CF.sub.2Br 
n.sub.D.sup.20 : 1.5255 
4 
##STR11## CF.sub.2Br 
n.sub.D.sup.24 : 1.5168 
5 
##STR12## CF.sub.2Br 
n.sub.D.sup.24 : 1.5055 
6 
##STR13## CF.sub.2Br 
n.sub.D.sup.22 : 1.5230 
7 
##STR14## CF.sub.2Br 
n.sub.D.sup.20 : 1.4700 
8 
##STR15## CF.sub.2Br 
n.sub.D.sup.22 : 1.4970 
9 
##STR16## CF.sub.2H n.sub.D.sup.23 : 1.4994 
10 
##STR17## CF.sub.2H n.sub.D.sup.23 : 1.5034 
11 
##STR18## CF.sub.2H b.p. 45.degree. C./ 0.1 mbar 
12 
##STR19## CF.sub.2H m.p.: 48.degree. C. 
13 
##STR20## CF.sub.2H m.p.: 47.degree. C. 
14 
##STR21## CF.sub.2Br 
m.p.: 80.degree. C. 
15 
##STR22## CF.sub.2Br 
n.sub.D.sup.23 : 1.5420 
16 
##STR23## CF.sub. 2Br 
n.sub.D.sup.23 : 1.5258 
17 
##STR24## CF.sub.3 b.p.: 120.degree. C./ 220 mbar 
18 
##STR25## CHF.sub.2 m.p.: 42.degree. C. 
19 
##STR26## CF.sub.2 Br 
m.p.: 40.degree. C. 
20 
##STR27## 
______________________________________ 
The active substances are suitable for combating animal pests, preferably 
arthropods and nematodes, in particular insects and arachnids, which occur 
in agriculture, in forestry, in the protection of stored products and of 
materials, and in the hygiene field They are active against 
normally-sensitive and resistant species, and against all or individual 
development stages. The above-mentioned pests include: 
From the order of the Isopoda, for example, Oniscus asellus, Armadillidium 
vulgare and Porcellio scaber. 
From the order of the Diplopoda, for example, Blaniulus guttulatus. 
From the order of the Chilopoda, for example, Geophilus carpophagus and 
Scutigera spec. 
From the order of the Symphyla, for example, Scutigerella immaculata. 
From the order of the Thysanura, for example, Lepisma saccharina. 
From the order of the Collembola, for example, Onychiurus armatus. 
From the order of the Orthoptera, for example, Blatta orientalis, 
Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta 
domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, 
Melanoplus differentialis and Schistocerca gregaria. 
From the order of the Dermaptera, for example, Forficula auricularia. 
From the order of the Isoptera, for example, Reticulitermes spp. 
From the order of the Anoplura, for example, Phylloxera vastatrix, 
Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. and 
Linognathus spp. 
From the order of the Mallophaga, for example, Trichodectes spp. and 
Damalinea spp. 
From the order of the Thysanoptera, for example, Hercinothrips femoralis 
and Thrips tabaci. 
From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus 
intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and 
Triatoma spp. 
From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia 
tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, 
Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, 
Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, 
Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix 
cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, 
Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus 
spp. and Psylla spp. 
From the order of the Lepidoptera, for example, Pectinophora gossypiella, 
Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, 
Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis 
chrysorrhoea, Lymantria spp. Bucculatrix thurberiella, Phyllocnistis 
citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, 
Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, 
Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, 
Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria 
mellonella, Tineola bissilliella, Tinea pellionella, Hofmannophila 
pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura 
fumiferana, Clysia ambiguella, Homona magnanima and Tortrix viridana. 
From the order of the Coleoptera, for example, Anobium punctatum, 
Rhizopertha dominica, Acanthoscelides obtectus, Acanthoscelides obtectus, 
Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon 
cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varive 
stis, Atomaria spp., Oryzaephilus surinamensis, Antho nomus spp., 
Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, 
Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma 
spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, 
Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., 
Tenebrio molitor, Agriotes spp., Cono derus spp., Melolontha melolontha, 
Amphimallon solsti tialis and Costelytra zealandica. 
From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa 
spp., Lasius spp., Monomorium pharaonis and Vespa spp. 
From the order of the Diptera, for example, Aedes spp., Anopheles spp., 
Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora 
erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., 
Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma 
spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia 
spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula 
paludosa. 
From the order of the Siphonaptera, for example, Xenopsylla cheopis and 
Ceratophyllus spp.. 
From the order of the Arachnida, for example, Scorpio maurus and 
Latrodectus mactans. 
From the order of the Acarina, for example, Acarus siro, Argas spp., 
Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta 
oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma 
spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., 
Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.. 
The plant-parasitic nematodes include Pratylenchus spp., Radopholus 
similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., 
Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp. and 
Trichodorus spp.. 
The active compounds of the formula (I) to be used according to the 
invention are distinguished by an excellent insecticidal activity. In 
particular, for example, the excellent action against nematodes, such as, 
for example, Globodera rostochiensis and Meloidogyne incognita, is 
noteworthy. Moreover, the active compounds according to the invention also 
show an excellent action against plant-damaging insects, such as, for 
example, Tetranychus species and Plutella caterpillars. 
The active compounds can be converted to the customary formulations, such 
as solutions, emulsions, suspensions, powders, foams, pastes, granules, 
aerosols, natural and synthetic materials impregnated with active 
compound, very fine capsules in polymeric substances and in coating 
compositions for seed, and formulations used with burning equipment, such 
as fumigating cartridges, fumigating cans, fumigating coils and the like, 
as well as ULV cold mist and warm mist formulations. 
These formulations are produced in known manner, for example by mixing the 
active compounds with extenders, that is, liquid solvents, liquefied gases 
under pressure, and/or solid carriers, optionally with the use of 
surface-active agents, that is emulsifying agents and/or dispersing agents 
and/or foam-forming agents. In the case of the use of water as an 
extender, organic solvents can, for example, also be used as auxiliary 
solvents. As liquid solvents, there are suitable in the main: aromatics, 
such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or 
chlorinated aliphatic hydrocarbons, such as chlorobenzenes, 
chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as 
cyclohexane or paraffins, for example mineral oil fractions, alcohols, 
such as butanol or glycol as well as their ethers and esters, ketones, 
such as acetone, methyl ethyl ketone, methyl isobutyl ketone or 
cyclohexanone, strongly polar solvents, such as dimethylformamide and 
dimethyl sulphoxide, as well as water; by liquefied gaseous extenders or 
carriers are meant liquids which are gaseous at normal temperature and 
under normal pressure, for example aerosol propellants, such as 
halogenated hydrocarbons as well as butane, propane, nitrogen and carbon 
dioxide; as solid carriers there are suitable: for example ground natural 
minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, 
montmorillonite or diatomaceous earth, and ground synthetic minerals, such 
as finely divided silica, alumina and silicates; as solid carriers for 
granules there are suitable: for example crushed and fractionated natural 
rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as 
synthetic granules of inorganic and organic meals, and granules of organic 
material such as sawdust, coconut shells, corn cobs and tobacco stalks; as 
emulsifying and/or foam-forming agents there are suitable: for example 
non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid 
esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl 
polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as 
well as albumin hydrolysates; as dispersing agents there are suitable: for 
example lignin-sulphite waste liquors and methylcellulose. 
Adhesives such as carboxym-ethylcellulose and natural and synthetic 
polymers in the form of powders, granules or latices, such as gum arabic, 
polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, 
such as cephalins and lecithins, and synthetic phospholipids, can be used 
in the formulations. Other additives can be mineral and vegetable oils. 
It is possible to use colorants such as inorganic pigments, for example 
iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such 
as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dye-stuffs, 
and trace nutrients such as salts of iron, manganese, boron, copper, 
cobalt, molybdenum and zinc. 
The formulations in general contain between 0.1 and 95 per cent by weight 
of active compound, preferably between 0.5 and 90%. 
The active compounds to be used according to the invention can be present 
in their commercially available formulations and in the use forms, 
prepared from these formulations, as a mixture with other active 
compounds, such as insecticides, pheromones, sterilizing agents, 
acaricides, nematicides, fungicides, growth-regulating substances or 
herbicides. The insecticides include, for example, phosphoric acid esters, 
carbamates, carboxylates, chlorinated hydrocarbons, phenylureas and 
substances produced by microorganisms, inter alia. 
The active compounds to be used according to the invention can furthermore 
be present in their commercially available formulations and in the use 
forms, prepared from these formulations, as a mixture with synergistic 
agents. Synergistic agents are compounds which increase the action of the 
active compounds, without it being necessary for the synergistic agent 
added to be active itself. 
The active compound content of the use forms prepared from the commercially 
available formulations can vary within wide limits. The active compound 
concentration of the use forms can be from 0.0000001 to 95% by weight of 
active compound, preferably between 0.0001 and 1% by weight. 
The compounds are employed in a customary manner appropriate for the use 
forms. 
When used against hygiene pests and pests of stored products, the active 
compounds are distinguished by an excellent residual action on wood and 
clay as well as a good stability to alkali on limed substrates. 
The biological effectiveness of the compounds to be used according to the 
invention will be explained with reference to the examples below. 
USE EXAMPLES 
In the following Use Examples, the compound mentioned below is employed as 
comparison substance: 
##STR28## 
2-(dibromo-fluoromathylthio)-pyridine. 
Compound (A) is disclosed in DE-A No. 2,510,178. 
EXAMPLE A 
Test nematode: Meloidogyne incognita 
Solvent: 3 parts by weight of acetone 
Emulsifier: 1 part by weight of alkylaryl polyglycol ether 
To produce a suitable preparation of active compound, 1 part by weight of 
active compound is mixed with the stated amount of solvent, the stated 
amount of emulsifier is added and the concentrate is diluted with water to 
the desired concentration. 
The preparation of active compound is intimately mixed with soil which is 
heavily infested with the test nematodes. The concentration of the active 
compound in the preparation is of practically no importance here, only the 
amount of active compound per unit volume of soil, which is given in ppm, 
being decisive. The treated soil is filled into pots, lettuce is sown and 
the pots are kept at a greenhouse temperature of 27.degree. C. 
After four weeks, the lettuce roots are examined for infestation with 
nematodes (root galls), and the degree of effectiveness of the active 
compound is determined in %. The degree of effectiveness is 100% if 
infestation is completely avoided and is 0% if the infestation is just as 
high as in the case of the control plants in untreated soil which has been 
infested in the same manner. 
In this test, for example, the following compounds of Preparation Examples 
1, 3, 4, 5 ,6, 13, 14, 15 and 16 show a superior effectiveness compared 
with the prior art: 
TABLE A 
______________________________________ 
Nematicides 
Meloidogyne incognita 
Degree of destruction in % 
at an active compound 
Active compound concentration in ppm 
______________________________________ 
##STR29## 20 ppm = 0% 
##STR30## 20 ppm = 100% 
##STR31## 20 ppm = 95% 
##STR32## 20 ppm = 100% 
##STR33## 20 ppm = 95% 
##STR34## 20 ppm = 95% 
##STR35## 20 ppm = 0% 
##STR36## 20 pm = 100% 
##STR37## 20 ppm = 100% 
##STR38## 20 ppm = 100% 
______________________________________ 
EXAMPLE B 
Test nematode: Globodera rostochiensis 
Solvent: 3 parts by weight of acetone 
Emulsifier: 1 part by weight of alkylaryl polyglycol ether 
To produce a suitable preparation of active compound, 1 part by weight of 
active compound is mixed with the stated amount of solvent, the stated 
amount of emulsifier is added and the concentrate is diluted with water to 
the desired concentration. 
The preparation of active compound is intimately mixed with soil which is 
heavily infested with the test nematodes. The concentration of the active 
compound in the preparation is of practically no importance here, only the 
amount of active compound per unit volume of soil, which is given in ppm, 
being decisive. The treated soil is filled into pots, potatoes are planted 
and the pots are kept at a greenhouse temperature of 18.degree. C. 
After six weeks, the potato roots are examined for cysts, and the degree of 
effectiveness of the active compound is determined in %. The degree of 
effectiveness is 100% if infestation is completely avoided and is 0% if 
the plants in untreated soil which has been infested in the same manner. 
In this test, for example the following compounds of Preparation Examples 
1, 4, 5, 6, 14 and 15 show a superior effectiveness compared with the 
prior art: 
TABLE B 
______________________________________ 
Nematicides 
Globodera rostochiensis 
Degree of destruction in % 
at an active compound 
Active compound concentration in ppm 
______________________________________ 
##STR39## 20 ppm = 0% 
##STR40## 20 ppm = 100% 
##STR41## 20 ppm = 100% 
##STR42## 20 ppm = 100% 
##STR43## 20 ppm = 95% 
##STR44## 20 ppm = 100% 
##STR45## 20 ppm = 100% 
______________________________________ 
EXAMPLE C 
Tetranychus test (resistant) 
Solvent: 3 parts by weight of dimethylformamide 
Emulsifier: 1 part by weight of alkylaryl polyglycol ether 
To produce a suitable preparation of active compound, 1 part by weight of 
active compound is mixed with the stated amount of solvent and the stated 
amount of emulsifier, and the concentrate is diluted with water to the 
desired concentration. 
Bean plants (Phaseolus vulgaris) which are heavily infested with all 
developmental stages of the common spider mite or greenhouse red spider 
mite (Tetranychus urticae) are treated by dipping into the active compound 
preparation of the desired concentration. 
After the desired time, the destruction is determined in 100% means that 
all the spider mites have been killed; 0% means that none of the spider 
mites have been killed. 
In this test, for example the following compound of Preparation Example 4 
shows a superior effectiveness compared with the prior art. 
TABLE C 
______________________________________ 
(plant-damaging mites) 
Tetranychus (resistant) 
Active compound 
Degree of 
concentration 
destruction 
Active compound in % in % after 7 d 
______________________________________ 
##STR46## 0.1 0 
##STR47## 0.1 95 
______________________________________ 
EXAMPLE D 
Plutella test 
Solvent: 3 parts by weight of dimethylformamide 
Emulsifier: 1 part by weight of alkylaryl polyglycol ether 
To produce a suitable preparation of active compound, 1 part by weight of 
active compound is mixed with the stated amount of solvent and the stated 
amount of emulsifier, and the concentrate is diluted with water to the 
desired concentration. 
Cabbage leaves (Brassica oleracea) are treated by being dipped into the 
preparation of active compound of the desired concentration and are 
infested with caterpillars of the diamond-back moth (Plutella 
maculipennis), as long as the leaves are still moist. 
After the desired time, the destruction in % is determined. 100% means that 
all the caterpillars have been killed; 0% means that none of the 
caterpillars have been killed. 
In this test, for example the following compounds of Preparation Examples 
1, 4 and 5 show a superior effectiveness compared with the prior art: 
TABLE D 
______________________________________ 
(plant-damaging insects) 
Plutella test 
Active compound 
Degree of 
concentration 
destruction 
Active compound in % in % after 3 d 
______________________________________ 
##STR48## 0.1 0 
##STR49## 0.1 100 
##STR50## 0.1 100 
##STR51## 0.1 100 
______________________________________ 
EXAMPLE E 
Critical concentration test/soil insects 
Test insect: Diabrotica balteata-larvae in the soil 
Solvent: 3 parts by weight of acetone 
Emulsifier: 1 part by weight of alkylaryl polyglycol ether 
To produce a suitable preparation of active compound, 1 part by weight of 
active compound is mixed with the stated amount of solvent, the stated 
amount of emulsifier is added and the concentrate is diluted with water to 
the desired concentration. The preparation of active compound is 
intimately mixed with the soil. The concentration of the active compound 
in the preparation is practically immaterial, the only decisive factor 
being the amount by weight of active compound per unit volume of soil, 
which is quoted in ppm (=mg/l). The soil is filled into 0.5 l pots and the 
pots are left to stand at 20.degree. C. 
Immediately after the start of the test 6 pregerminated corn seeds are 
planted in each of the pots. After 2 days the appropriate test insects are 
inserted into the treated soil. After further 7 days the degree of 
effectiveness of the active compound is determined in % by counting the 
dead and the live test insects. The degree of effectiveness is 100% if all 
of the test insects have been killed and 0% if exactly as many insects are 
still alive as in the case of the untreated control. 
In this test, for example, the following compounds of preparative examples 
2, 7, 8, 10, 14 and 15 display superior effectiveness to the prior art. 
TABLE E 
______________________________________ 
soil insecticides 
Diabrotica balteata - larvae in the soil 
Degree of destruction 
in % at an active compound 
Active compound concentration in ppm 
______________________________________ 
##STR52## 20 ppm = 0% 
##STR53## 20 ppm = 100% 
##STR54## 20 ppm = 100% 
##STR55## 20 ppm = 100% 
##STR56## 20 ppm = 100% 
##STR57## 20 ppm = 100% 
##STR58## 20 ppm = 100% 
______________________________________ 
It is understood that the specification and examples are illustrative but 
not limitative of the present invention and that other embodiments with 
the spirit and scope of the invention will suggest themselves to those 
skill in the art.