CH621795A5 - Process for the preparation of novel O-pyrazolopyrimidin(thiono)-phosphates/phosphonates/phosphoramidates/p hosphonamidates and their use in insecticides, acaricides and nematicides - Google Patents

Description

The present invention relates to a process for the preparation of new 0-pyrazolopyrimidine (thiono) -phosphorus (phos-phon) acid esters or ester amides which have insecticidal, acaricidal and nematicidal properties.

It is already known that 0-pyrazolopyrimidine (thiono) phosphorus (phosphonic) acid esters, e.g. 0.0-dimethyl- or 0.0-diethyl-0- [7-methylpyrazolo (l, 5-a) -pyrimidine (2) y] -] or 0.0-dimethyl- or 0.0-diethyl -0- [3-chloro-7-methyl-pyrazolo (l, 5-a) pyrimidin (2) yl] thionophosphoric acid ester and 0-sec.-butyl-0- [3-bromo-7-methylpyrazoIo (l , 5-a) pyrimidin- (2) yl] thionomethanephosphonic acid esters have a pesticidal, in particular insecticidal and acaricidal, action (cf. Belgian patent specification 769 702).

It has now been found that the new O-pyrazolopyrimi-din (thiono) -phosphorus (phosphon) acid esters or ester amides of the formula

35

40

45

50

55

(I)

in which

Ri for alkoxy with 1 to 6 carbon atoms,

R2 for alkyl or alkoxy each having 1 to 4 carbon atoms, furthermore for an alkylamino group with a maximum of 6 carbon atoms,

R3 for hydrogen or halogen,

R4 for alkyl with 2 to 6 carbon atoms and

X represents oxygen or sulfur,

possess strong insecticidal, acaricidal and nematicidal properties.

Furthermore, it was found that the new O-pyrazolopyrimidine (thiono) phosphorus (phosphonic) acid esters or ester amides of constitution (I) are obtained according to the invention if (thiono) phosphorus (phosphonic) acid esters or ester amide halides of the formula

Ri X

\ ll

60

P-Hal

(II)

R2

65

in which

Ri, R2 and X have the meaning given above and Hai is halogen, preferably chlorine or bromine, with 2-hydroxypyrazolopyrimidine derivatives of the formula

3rd

621795

in which

R3 and R4 have the meaning given above, in the presence of an acid acceptor or in the form of the corresponding alkali metal, alkaline earth metal or ammonium salts, if appropriate in the presence of a solvent. / j j j \ Surprisingly, the new O-pyrazolopyrimi-din (thiono) -phosphor (phosphon) acid esters or ester amides s have a significantly higher insecticidal, acaricidal and nematicidal activity than the previously known compounds of analogous constitution and the same direction of action. The fabrics mentioned are a real asset to the technology.

If you use e.g. 0,0-diethyl-phosphoric acid ester chloride io and 2-hydroxy-7-ethyl-pyrazolo (1,5-a) pyrimidine as starting materials, the course of the reaction can be represented by the following formula:

c ^ o N rt d 3. P-Cl c2h5o /

+ HO 'N' ""

Acid acceptor

-HCl

CgHjO

2H5

The starting materials to be used are clearly defined in general terms by formulas (II) and (III).

However, R 1 is preferably straight-chain or branched alkoxy having 1 to 4 carbon atoms,

R2 for straight-chain or branched alkoxy or alkyl each with 1 to 3, furthermore for monoalkylamino with 1 to 4 carbon atoms,

R3 for hydrogen, chlorine or bromine,

R4 for straight-chain or branched alkyl having 2 to 4 carbon atoms and X for sulfur.

The (thiono) phosphorus (phosphonic) acid ester or ester amide halides (II) to be used as starting materials are known and can be prepared by generally customary processes. The following are examples of this:

0.0-dimethyl, 0.0-diethyl,

0.0-di-n-propyl-, 0.0-di-isopropyl ~,

O-ethyl-on-butyl-, O-ethyl-O-iso-butyl-, O-ethyl-O-sec-butyl-, O-ethyl-O-tert-butyl-, on-propyl-O- sec-butyl,

O-ethyl-O-n-propyl-phosphoric acid diester chloride or

R4 has the meaning given above.

The products halogenated in the 3-position are usually obtained therefrom by halogenation.

The following are examples:

3-chloro-7-ethyl-, 3-chloro-7-n-propyl-,

3-chloro-7-iso-propyl-, 3-chloro-7-n-butyl-, 3-chloro-7-iso-butyl-, 3-chloro-7-sec-butyl-, 3-chloro-7 -tert.-butyl-, 3-bromo-7-ethyl-,

3-bromo-7-n-propyl-, 3-bromo-7-iso-propyl-,

3-bromo-7-n-butyl-, 3-bromo-7-isobutyl-, 3-bromo-7-sec.-butyl-or. 3-bromo-7-tert-butyl-2-hydroxypyrazolo (1,5-a) pyrimidine.

The production process is preferably carried out using suitable solvents or diluents. Practically all inert organic solvents can be considered as such. These include above all aliphatic and aromatic, optionally chlorinated, hydrocarbons,

-bromide and the corresponding thiono analogues,

also O-methyl, O-ethyl, on-propyl, O-iso-propyl, on-butyl, O-iso-butyl, O-sec.-butyl, O-tert.-butyl methane or ethane,

25-n-propane, iso-propane-phosphonic acid ester chloride or bromide and the corresponding thiono analogs, furthermore O-methyl-N-methyl, O-ethyl-N-ethyl, on-propyl-Nn-propyl, O-iso-propyl-N-iso-propyl-, on-butyl-Nn-butyl-, O-ethyl-Nn-propyl-, 30 O-ethyl-N-iso-propyl-, O-ethyl-Nn-butyl -, O-ethyl-N-iso-butyl, O-ethyl-N-sec-butyl, on-propyl-N-ethyl, on-propyl-Nn-butyl, on-propyl-N-iso -butyl-, on-propyl-N-sec.-butyl-, O-iso-propyl-N-ethyl -, O-iso-propyl-Nn-butyl-, 35 O-iso-propyl-N-iso-butyl - or O-iso-propyl-N-sec-butylphosphoric acid ester amide chloride or bromide and the corresponding thiono analogues.

The 2-hydroxy-pyra-40 zolo (l, 5-a) pyrimidine derivatives (III) to be used as starting materials are new. They can be prepared, for example, by reacting 3-aminopyrazo-ion (5) in ethanol-hydrogen-saturated ethanol with 1-chlorovinyl (2) alkyl ketones.

such as benzene, toluene, xylene, gasoline, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, ether, e.g. Diethyl and dibutyl ether, dioxane, furthermore ketones, acetone, methyl 55 ethyl, methyl isopropyl and methyl isobutyl ketone, furthermore nitriles, e.g. Acetonitrile and propionitrile, also formamides, especially dimethylformamide.

All customary acid binders can be used as acid acceptors. Alkalicar-60 bonates and alcoholates, such as sodium or potassium carbonate, methylate or ethylate, and furthermore aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine and pyridine, have proven particularly useful.

The reaction temperature can be varied within a relatively wide range. In general, between 0 and 100 ° C, preferably at 15 to 35 ° C.

The reaction is generally carried out at normal pressure.

621795

4th

To carry out the process, the starting materials are usually used in equimolar ratios. An excess of one or the other reaction component has no significant advantages. The reaction is preferably carried out in the presence of one of the abovementioned solvents and in the presence of an acid acceptor at the temperatures indicated; after stirring for one to several hours at the stated temperatures, the reaction mixture is generally worked up by adding ice water. The product either precipitates in solid form, is filtered off with suction, washed and optionally recrystallized, or the mixture can be extracted with an organic solvent, preferably methylene chloride. After washing and drying the extract, the solvent is e.g. removed under reduced pressure.

The new substances mostly occur in crystalline form and are characterized by their melting point. However, if they are obtained in the form of mostly yellowish-reddish oils, which cannot be distilled without decomposing, they can be distilled by so-called «distillation», i.e. H. Prolonged heating under reduced pressure to moderately elevated temperatures is freed of the last volatile components and can be cleaned in this way. In this case, the refractive index is used to characterize them.

As already mentioned several times, the new O-pyrazolopyrimidine (thiono) -phosphorus (phosphon) acid esters or ester amides are distinguished by their excellent insecticidal, acaricidal and nematicidal activity. They act against plant, hygiene and storage pests. They are both effective against sucking and biting insects and mites (Acarina).

For these reasons, the new products are successfully used as pesticides in plant and stock protection as well as in the hygiene sector.

With good plant tolerance and favorable warm-blood toxicity, the active substances are suitable for combating animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stocks and materials, and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The pests mentioned above include:

From the order of the Isopoda e.g. Oniscus asellus, Arma-dillidium vulgare, Porcellio scaber.

From the order of the Diplopoda z. B. Blaniulus guttulatus.

From the order of the Chilopoda e.g. Geophilus carpopha-gus, Scutigera spec.

From the order of the Symphyla e.g. Scutigerella immaculata.

From the order of the Thysanura e.g. Lepisma saccharina.

From the order of the Collembola e.g. Onychiurus armatus.

From the order of the Orthoptera e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

From the order of the Dermaptera e.g. Forficula auricularia.

From the order of the Isoptera e.g. Reticulitermes spp.

From the order of the anoplura e.g. Phylloxéra vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.

From the order of the Mallophaga e.g. Trichodectes spp., Damalinea spp.

From the order of the Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.

From the order of the Heteroptera e.g. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of the Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phoraon-emiphasum bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax stria-tellus, Nilaparvata lugens, Aonidiella aurantii, aspidiotus hede-rae, Pseudococcus spp., Psylla spp.

From the order of the Lepidoptera e.g. Pectinophora gossy-piella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberistiisellappellappiappellappiapplppellappl , Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Caulacoacoanaella, Galleria mellellaella, Galleria mellellaella fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

From the order of the Coleoptera e.g. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Philyllusppas, Atomicusususpp. , Otior-rhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Giptusibibium sium ., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Coste-lytra zealandica.

From the order of the Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera e.g. Aëdes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., GastropMus spp., Hyppobosca spp., Stomoxys Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

From the order of the Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp.

From the order of the Arachnida e.g. Scorpio maurus, Latrodectus mactans.

From the order of the Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,. Chori ., Tarsonemus spp., Bryo-bia praetiosa, Panonychus spp., Tetranychus spp.

Plant-parasitic nematodes include Pratylen-chus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchu-lus semipenetrans, Heterodera spp., Meloidogyne spp., Aphe-lenchoides spp., Longidorus spp., Xiphinema spp.,.

The new active compounds are usually used in the form of their commercially available formulations and / or the use forms prepared from these formulations.

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

5

10th

15

2 «

25th

30th

35

40

45

50

55

60

65

5

621795

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

When used against hygiene pests and pests of stored products, the active ingredients are distinguished by an excellent residual action on wood and clay and by a good stability to alkali on limed substrates.

The new active ingredients can be converted into the usual formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, suspension emulsion concentrates, seed powders, active ingredient-impregnated natural and synthetic Substances, very fine encapsulation in polymeric substances and in coating compositions for seeds, also in formulations with fuel sets, such as smoking cartridges, cans, spirals and the like. Ä. as well as ULV cold and warm fog formulations.

These formulations can be prepared in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water; liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and pressure, e.g. Aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; as solid carriers: natural rock flour, such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates; as solid carriers for granules: broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foaming agents: nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates; as a dispersant: e.g. Lignin, sulfite liquor and methyl cellulose.

Adhesives such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.

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

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

Example A Phaedon larva test 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 and the stated amount of emulsifier 10 and the concentrate is diluted with water to the desired concentration.

With the preparation of active substance, cabbage leaves (Brassica oleracea) are sprayed to runoff point and populated with horseradish leaf beetle larvae (Phaedon cochleariae).

After the specified times, the kill is determined in%. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae have been killed.

Active substances, active substance concentrations, times of evaluation and results are shown in Table 1 below:

Table 1 (Phaedon larval test)

25 active ingredient

Drug killing concentration in% tionin%

3 days

30th

(OTjOt jP-O-jp

(known)

35

40

45

»

0.01 0.001

100 0

CH.

s

II yCl

(CH30) 2P ~ ° ~ Tj

(known)

0.01 100 0.001 0

(C2H50) 2P-0

(known)

0.01 100 0.001 0

60

JC1

(CH 3 °) 2p-07rnf

0.01 100 0.001 100

65

621795

Table 1 (continued) (Phaedon larval test)

Active ingredient

Table 1 (continued) (Phaedon larval test)

Active ingredient killing degree in%

tion in% according to S

3 days

Active ingredient

Drug killing concentration in% tion in%

3 days

(CH30) 2P-0

V.

^ C1

C ^ H ^ -iso

0.01 100 0.001 100

10th

c2h5 ° \ II

/ p ~ ° -rr — 1

n-c, H_o ^ II | i 0,

3 'NvtT> ^ N 0.1

C_H

01 001

100 100

<C2H50) ■ - Cl

0.01

N ^ PÎ 0.001 CN

C2H5

S

II

(C ~ HcO) oP-0-

, C1

JU

c3H7-n

S

II Cl

(C2H5 °) 2P-0 * ^ p—

Nv

C3H ^ -iso

S

II

(c2H50) 2p- ° -n

'4H9-iso

C0H..O. II

2 5 ^ p-o C H ^

2 5

X1

Cl

N

C2H &

0.01 0.001

0.01 0.001

0.01

N v1} 0.001

0.01 0.001

100 100

100 100

100 100

100 100

100 100

2 «c H o II

p-o.

n-CjH ^ O

Cl

25th

0.01 0.001

100 100

C2H $

30th

Example B Myzus test (contact effect) Solvent: 3 parts by weight of acetone emulsifier: 1 part by weight of alkylaryl polyglycol ether

35

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

40 and dilute the concentrate with water to the desired concentration.

Cabbage plants (Brassica oleracea) which are heavily infested with peach aphids (Myzus persicae) are sprayed to runoff point with the preparation of active compound.

45 After the specified times, the kill is determined in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.

Active substances, active substance concentrations, evaluation times and results are shown in Table 2 below:

50

55

Table 2 (Myzus test)

Active ingredient

Drug concentration in%

Degree of kill in% after IT day

S II

(CH30) 2p-0— [j—

(known)

■ Cl

• N

0.01

0.001

0.0001

99 40 0

65

CH.

7

621795

Table 2 (continued) (Myzus test)

Active ingredient

Active ingredient concentration in%

s II

(ch3o) 2p-o-

0.01

... 0.001

0.0001

C2H5

s II

(CH30) 2P "° T

. ^ Cl

».

0.01

0.001

0.0001

C ^ H ^ - ^ SO

S

II

(C2H5 °) 2p- ° -rr

N.

A

0.01

0.001

0.0001

C2H5

s

II Cl

(c2H50) 2p- ° -fnf

0.01

c3h7-11

0.001 0.0001

C2H5

0.01 0.001 0.0001

Degree of killing in% after 1 day

100 97 35

100 100 55

100 100 75

100 95 50

100 100 75

Example C Doralis test (systematic action) Solvent: 3 parts by weight

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 specified 1 “quantity of solvent and the specified quantity of emulsifier, and the concentrate is diluted with water to the desired concentration.

Bean plants (Vicia faba), which are heavily infested with black bean louse (Doralis ls fabae), are watered on with the active substance preparation, so that the active substance preparation penetrates into the soil without wetting the leaves of the bean plants. The active ingredient is taken up from the soil by the bean plants and thus reaches the infected leaves.

20 After the specified times, the kill is determined in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.

Active substances, active substance concentrations, evaluation times and results are shown in Table 3 below:

25th

30th

Table 3 (Doralis test / systemic effect)

Active ingredient

35

Drug concentration in%

Degree of killing in% after 4 days s

il

40

lc2H50) 2p- ° -r

(known)

45

0.1

II O-C .HQ-sek CHU-P q *

so 3rd

^ Br

(known)

0.1

• n n ch.

C2H5 ° \ "

p-o-

n-C3H70 ^

Trl

/ W *

/ n 1

C2H5

0.01 001 0.0001

100 100 40

60

65

s

. H

(ch30) 2p-0-

/

C2H5

0.1

100

621795

8th

Table 3 (continued) (Doralis test / systemic effect)

Active ingredient

Active ingredient concentration in%

Table 4 (Tetranychus test)

Degree of killing in% after 4 days

Active ingredient

Drug concentration in%

Degree of killing in% after 2 days

(C2h5 °) jP-O-tî-I

N »

0.1

C2H5

0

II

(CjHsOJP-O-j-

1

0.1

N N

d2 "5

0

II

Cl

(C2H50) 2p-0-r

I.

Nv

A,

0.1

C2H5

100

100

100

, 0 ch3-p.

// ° "C4H9 ~ sec 'Br

(known)

a cf.

(CH30) 2P-0-

vi n

25th

30th

c2h5

s

II

Cl

(CH30) 2P-0-

35

St.

U! I

C2H5

(CH3O) 2I-OT 'C1

N / A

Example D Tetranychus test (resistant) 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 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 stages of development of the common spider mite or bean spider mite (Tetrany-chus urticae) are sprayed to runoff point with the preparation of active compound.

After the specified times, the kill is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.

Active substances, active substance concentrations, evaluation times and results are shown in Table 4 below:

C ^ H ^ iio

50

55

s *

II

(C2H50) 2P-0 ^ - yy

0.1

N

c2H5

O

{C2H50) 2P- ° f | "

65

n n

C2H5

0.1

0.1

0.1

0.1

0.1

99

95

90

98

80

9

621795

Table 4 (continued) (T etranychus test)

Active ingredient

Active ingredient concentration in%

Example E

Limit Concentration Test / Soil Insects I Kill test insect: Phorbia antiqua maggots in the soil degree in% solvent: 3 parts by weight of acetone after 2 days 5 emulsifier: 1 part by weight of alkylaryl polyglycol ether

(c2h50) 2p-o-

Cl

0 II

C2H5

(c2h5oi2p-o.

II

./

Cl

N

'tî

C2H5

0.1

0.1

98

98

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the specified amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

The active ingredient preparation is intimately mixed with the soil. The concentration of the active ingredient in the preparation is practically irrelevant, the only decisive factor is the amount of active ingredient per unit volume of soil, which is given in ppm (= mg / 1). You fill the bottom in pots and leave them at room temperature.

After 24 hours, the test animals are placed in the treated soil and after a further 2 to 7 days, the effectiveness of the active ingredient is determined in% by counting the dead and live test insects. The efficiency is 100% when all test insects have been killed, it is 0% when as many test insects are still alive as in the 2s untreated control.

Active ingredients, application rates and results are shown in Table 5 below:

^ C1

(C2H50) 2P-01T

C ^ H ^ -iso

C2H5 ° II 3 xP-0

C2H5 ^

Cl>

/

C2H5

C H 0 H

s

II

P-O-

n-C3H70 /

Nv

N N

C F U2K5

0.1

0.1

0.1

99

99

30th

80

Table 5

Limit concentration test / soil insects I (Phorbia antiqua maggots in the soil)

Active ingredient

Degree of killing in% with an active ingredient concentration of 5 ppm

C2H5 ° \

C2H5 °

p-o-

N.

N N

(known)

CH-rpC

50 -3 \

55 (known)

/ CH.

O-C ^ Hg-sec

Ii jT

CH.

C2H5 ° \

n-C3H70 /

P-O

0.1

90

60 c2H5O C2H50 '

65

N P-O

N 100

621795

10th

Table 5 (continued) Limit concentration test / soil insects I (Phorbia antiqua maggots in the soil)

Active ingredient

Degree of killing in% with an active ingredient concentration of 5 ppm

C2H5 ° from C2H5 ° -

p-o-

C2H5 ° X 11

x p-o

C2H5 ° ^

c, h 0 | l

3 XP-0

C2H50 ^

C2h50 II 5 xP-0

C2H5 ° "

I.

n-

• n

C3H7 ~ n rH2cH3

C2H5 ° V »z x p-o-

100

100

100

100

C3H7-iSO

C2V

100

N

• n

C2H5

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 active ingredient preparation is intimately mixed with the soil. The concentration of the active ingredient in the preparation is practically irrelevant, the only decisive factor is the weight of the active ingredient per unit volume of soil, which is given in ppm (= mg / 1). You fill the bottom in pots and leave them at room temperature.

After 24 hours, the test animals are added to the treated soil and after a further 2 to 7 days, the effectiveness of the active ingredient is determined in% by counting the number of dead and ls test insects. The efficiency is 100% when all test insects have been killed, it is 0% when as many test insects are still alive as in the untreated control.

Active ingredients, application rates and results are shown in Table 20 below:

Table 6

Limit concentration test / soil insects II (Tenebrio molitor larvae in the soil)

25th

Active substance (constitution)

Degree of killing in% with an active ingredient concentration of 5 ppm c9h [.o Ii ^ .p-o-

C2h5O

(known)

n

ch.

40

II O-C.H ~ -sec «ch - p 4 9

3 ^ 0.

(known)

v ~ i]

/ ch

55

Example F

Limit concentration test / soil insects II Test insect: Tenebrio molitor larvae in the soil Solvent: 3 parts by weight of acetone emulsifier: 1 part by weight of alkylaryl polyglycol ether

60

C2H5 ° \ II

p-o

C2H5 °

100

11

621795

Table 6 (continued) Limit concentration test / soil insects II (Tenebrio molitor larvae in the soil)

Active substance (constitution)

Degree of killing in% with an active ingredient concentration of 5 ppm

Table 7

Limit concentration test / nematodes (Meloidogyne incognita)

5 active ingredient

Degree of killing in% with an active ingredient concentration of 5 ppm

C H 0 Ii * 3 XP-0

W

Cl

N N

C ^ H ^ -iso

100

io CH3 ~ P>

15

, 0-C4H9-sec ■ os ^

(known)

I! -

N JL XN N

CH.

C2H5 ° -C2H5 '

Cl

20th

P-O •

I!

100

C2H5

s

CHJD | l ch3o p-o

100

C ^^ - iso

Example G Limit Concentration Test / Nematode Test Nematode: Meloidogyne incognita Solvent: 3 parts by weight acetone emulsifier: 1 part by weight 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 active ingredient preparation is intimately mixed with soil that is heavily contaminated with the test nematodes. The concentration of the active ingredient in the preparation is practically irrelevant; the decisive factor is the amount of active ingredient per unit volume of soil, which is given in ppm. The treated soil is filled into pots, seeds are sown and the pots are kept at a greenhouse temperature of 27 ° C.

After four weeks, the lettuce roots are examined for nematode infestation (root galls) and the effectiveness of the active ingredient is determined in%. The efficiency is 100% if the infestation is completely avoided, it is 0% if the infestation is as high as that of the control plants in untreated, but equally contaminated soil.

Active ingredients, application rates and results are shown in Table 7 below:

CH 0 H

p-o-

ch3O-

25th

(known)

TT

^ .IKSN

CH-

30th

C2H5 ° x Ii

\ p_0-

C2H5 ° ^

xcl

N

100

c2H5

40

c2h5o n

C2H5 °

p-o-

ri »

100

C2H5

50

Example H LDioo test Test animals: Sitophilus granarius 55 Solvent: acetone

2 parts by weight of active ingredient are taken up in 1000 parts by volume of solvent. The solution thus obtained is diluted to the desired concentration with further solvent.

2.5 ml of the active ingredient solution are pipetted into a petri dish. On the bottom of the Petri dish is a filter paper with a diameter of approximately 9.5 cm. The petri dish remains open until the solvent has completely evaporated. Depending on the concentration of the active ingredient solution, the amount of active ingredient per m2 of filter paper varies. Then add about 25 test animals to the Petri dish and cover them with a glass lid.

621795

12th

The condition of the test animals is 3 days after preparation of the o% means that no test animals have been killed. Trials controlled. The death rate is determined in%. Active substances, active substance concentrations, test animals and result

100% means that all test animals have been killed; The results are shown in Table 8 below:

Table 8 (LDioo test / Sitophilus granarius)

Active ingredient

Drug killing level concentration in%

Solution in%

<C2H50) 2P- °

(known)

n- ^ n

CH.

0.02 0.002

100 0

Cl

(C2H50) 2PN.

a

: - * r,

2 5

0.002

90

Cl

-, "O

(CH30) 2P-0- ^ N ^ vpJ

C2H5

0.002

100

Cl

(CH30) 2P ~ ° -

\

C3H7-iBO

0.002

100

Cl c2H5 ° \ c2H /

0.002

100

O

£ 1

(C2H50) 2-p- ° -

<I

c2h5

0.002

70

13

621795

Example I mosquito larvae test animals: Aedes aegypti solvent: 99 parts by weight of acetone emulsifier: 1 part by weight of benzylhydroxydiphenylpolyglycol ether diluted to desired lower concentrations.

The aqueous active substance preparations are poured into glasses and then about 25 mosquito larvae are inserted into each glass.

After 24 hours, the degree of destruction is determined in%.

100% means that all larvae have been killed,

". ". r • Tir-i 4th et u ■ *. 0% means that no larvae have been killed at all

For the preparation of a suitable active ingredient preparation. , 1 °

dissolve 2 parts by weight of active ingredient in 1000 parts by volume

Solvent containing emulsifier in the amount indicated above, active substances, active substance concentrations, test animals and results. The solution obtained in this way is diluted with water from Table 9 below:

Table 9

(Mosquito larva test / Aedes aegypti)

Active ingredient

(c2h50) 2-p-0

(known)

Nv n "

n

ch.

(C ^ o ^ p-o-w ^, ^

C2H5

Drug killing level concentration in%

Solution in ppm

1

0.1

0.1

100 0

100

(c2h50) 2p-o-j

(c2h50) 2p-o

C3H7 "fso

Cl

S L_ / N \

'I j - M

(C2H50) 2P "°

0.1

0.1

0.1

100

100

100

C3H7-n

Br c2h5-

C2H5 °

° j h-h p-O-U,

G4H'9 ~ n

0.1

70

621795

14

Table 9 (continued) (mosquito larva test / Aedes aegypti)

Active ingredient

Drug killing level concentration in%

Solution in ppm

Cl s

II

(CH30) 2P-0

-N - N-

T

C2H5

Cl s II

(ch3o) 2P-0-

0.1

100

0.1 100

Cl

C ^ H ^ -iso

{C2H5 °) 2p-0 ^ N.> ^

C4H $ -n

Cl

C2H5 ° \ C2H5 ^

P-O-

Cl c2h5 ° \ II

P-O-

C2H5

n n-C3H70 '

C2H5

c2h 0 N

5 ^ P-O-W J ,.

n-C3H70 ^ N

C2H5

0.1 100

0.1

0.1

100

0.1 100

90

Cl

0 I s M

11 h ^ d

(C2H50) 2P-O4 ^

0.1

70

C2H5

15

621795

Manufacturing examples

W

c2h50

10th

In the mixture of 19.8 g (0.1 mol) of 2-hydroxy-3-chloro-7-

Ethyl-pyrazolo (l, 5-a) pyrimidine, 75 ml of dimethylformamide and 15.0 g of powdered potassium carbonate are added dropwise with stirring and gentle cooling at 20 ° C., 18.7 g (0.1 mol) of 0.0-diethyl-thionophosphoric diester chloride , the reaction mixture is then left to react for a further 3 to 4 hours at 20 ° C with further stirring and then 200 ml of ice-cold water flow in at an internal temperature below 10 ° C. The resulting crystals are filtered off, washed with water and dried. In this way, 32.4 g (93% of theory) of 0.0-diethyl-0- [3-chloro-7-ethyl-pyrazolo (1,5-a) pyrimidine (2) yl] thionophosphoric acid ester are obtained in the form of almost colorless crystals with a melting point of 51 to 52 ° C.

The following connections can be made in an analogous manner:

Example constitution physical. Data

No. (melting point ° C;

Refractive index)

CÎ

c2h5o c2h50

CnHcO

5) p-OAN ^ s ^

CpHcO / I

* C3H? -Iso

Br c2h5o

C ^ HcQ /

2H5 ° L h n

50

wn Lo / toO

C9Hc0 / I

C4Hg-iso

C ^ °) I-0 / ^ O 46

T2h5

CpH ^ O I

5 C4H9-n

Cl

61

70

By S

No.

8th

9

10th

11

12th

13

14

15

16

constitution

Physical. Data (melting point "C; refractive index)

C, H50 v® ^ 3, P-0

c2h5o '

C4 »9-

iso

CKjO. T

c2h5

Br

S • \

CH3 ° V »JTJ» ^ / P-o ch3o

P-0

Cl s y =

C2H5

C2H5 ° \ p_o

C2H5 't2H5

CH, 0 v S ^ n iso-C ^ Hy-NH

C3H7 ~ i

ISO

Cl c2h5 ° \ «\ r /

2 5 P-O ^ N ^ v ^

n-C ^ HyO '

> C2H5

^ 2 ^ 5 ^ \ x)

p, P-O

n-C ^ H? 0

c2h5

(Isolation of this compound by extraction instead of crystallization)

63

36

80

74.5

93.5

70

61.5

n «: 1.5415

17th

621 795

Example 16

Cl c2h50 n s d ^ J p-o c2h50 1

Into the mixture of 19.8 g (0.1 mol) of 2-hydroxy-3-chloro-7-ethyl-pyrazolo (1,5-a) pyrimidine, 70 ml of dimethylformamide and 11.6 g (0.115 mol) Triethylamine is added dropwise with stirring and external cooling at an internal temperature of 20 ° C., 17.3 g (0.1 mol) of 0.0-diethylphosphoric diester chloride and the mixture is left to react at 20 ° C. for 3 hours. When it is thinned with 300 ml of ice-cold water, a crystal is formed which is suctioned off, washed with water and dried. In this way, 27.1 g (81.2% of theory) of 0.0-diethyl-0- [3-chloro-7-ethyl-pyrazolo (l, 5-a) pyrimidin (2) yl] phosphoric acid ester of Melting point 67.5 ° C.

Example 17

0, =

2H5 °) iLoA *

c2h50

The compound is prepared analogously to Example 16, but 30 isolated by extraction with methylene chloride instead of crystallization. The yield is 74.5% of theory and the refractive index is ng: 1.5190.

The required starting products can be produced as follows, for example: 35

a)

C2H5

40

292 g of gaseous hydrogen chloride are passed into the mixture of 99.0 g (1 mol) of 3-amino-pyrazolone (5) and 600 g of ethanol at 20 ° C. Then 119 g (1 mol) of l-chlorovinyl (2) -ethyIketone from the boiling point 39 ° C. (3 Torr) at 15 to 20 ° C. are added dropwise in the course of 12 minutes. The batch is left to react for one hour at 20 to 25 ° C, then one hour at 50 ° C and finally for one hour with external cooling with ice water. The crystals formed are filtered off and washed with cold ethanol. The filter residue represents the hydrochloride of the desired compound and, after dissolution in 1.21 water, is converted into the free compound by adding concentrated sodium hydroxide solution to the final pH 4. By suction, washing and drying, 141.2 g (86.5% of theory) of 2-hydroxy-7-ethyl-pyrazolo- (1,5-a) -pyrimidine in the form of an almost colorless powder with a melting point of 192-193 ° C obtained.

20th

b)

25th

HO / ^ N- '

37.5 g are passed into the solution of 81.6 g (0.5 mol) of 2-hydroxy-7-ethyl-pyrazolo (l, 5-a) pyrimidine, heated to 70-80 ° C., in 500 g of acetic acid with stirring gaseous chlorine and stir the mixture at 70 ° C for one hour. After cooling, the crystals formed are filtered off with suction, washed with acetic acid and then suspended in 11 hot water. After cooling, the product is suctioned off and washed with water until the wash water is no longer acidic. After drying, 79.6 g (80.6% of theory) of 2-hydroxy-3-chloro-7-ethyl-pyrazolo (l, 5-a) -pyrimidine are obtained in the form of a light yellow powder with a decomposition point of 248 ° C. .

B

Claims (4)

621795 2. The method according to claim 1, characterized in that the Umsetzimg is carried out in the presence of a solvent. 2nd PATENT CLAIMS 1. Process for the preparation of new O-pyrazolopyrimidine (thiono) phosphorus (phosphonic) acid esters or ester amides of the formula * Vn (I) 10th in which Ri for alkoxy with 1 to 6 carbon atoms, R2 for alkyl or alkoxy each having 1 to 4 carbon atoms, furthermore an alkylamino group with a maximum of 6 carbon atoms, R3 for hydrogen or halogen, R4 for alkyl with 2 to 6 carbon atoms and X represents oxygen or sulfur, as an active ingredient in insecticidal, acaricidal or nematicidal agents. in which Ri for alkoxy with 1 to 6 carbon atoms, R2 for alkyl or alkoxy each having 1 to 4 carbon atoms, furthermore an alkylamino group with a maximum of 6 carbon atoms, R3 for hydrogen or halogen, R4 for alkyl with 2 to 6 carbon atoms and X represents oxygen or sulfur, characterized in that (Thiono) phosphorus (phos- phon) acid ester or ester amide halides of the formula Ri X \ I 20th 25th P — shark (II) Ri 30th in which Ri, R2 and X have the meaning given above and Hai stands for halogen, with 2-hydroxypyrazolopyrimidine derivatives of the formula (III) in which R3 and R4 have the meaning given above, in the presence of an acid acceptor or in the form of the corresponding alkali metal, alkaline earth metal or ammonium salts. 3. The method according to claim 1, characterized in that in compounds of formula II halogen is chlorine or bromine. 4. Use of new O-pyrazolopyrimides (thiono) -phosphorus (phosphon) acid esters or ester amides of the formula R3 x Nvp = - | / N ^ (I)