DE2262189A1 - O-PHOSPHATOXIMES AND PESTICIDES - Google Patents

Description

The present invention relates to new compounds, in particular O-phosphate oximes of the general formula I.

(D

in which X and -Y are each a hydrogen or halogen atom, one Mean cyano or nitro group or a lower alkyl radical, Z is an oxygen or sulfur atom, R is a cyano group

·] Or a lower alkyl radical, R is an oxygen

2 λ
or sulfur atom and R and R each represent a lower alkyl or lower alkoxy radical.

The invention also relates to the use of the phosphate oximes of the general formula I for combating insect pests and

- 1 -

309 8 26/1188

- mites as well as new pesticides, which these O-phosphate oximes as an obligatory active ingredient in combination with various excipients acting as diluents contain.

The new O-phosphate oximes of the general formula I can be prepared by various processes. However, their preparation is most conveniently carried out in the following manner: A substituted or unsubstituted thiophene or furan is halomethylated. In order to prepare those compounds according to the invention in which R is a C.yangruppe, the halomethyl derivative obtained is then reacted with potassium cyanide to give the corresponding cyanomethyl derivative. This derivative in turn is reacted with a base and a nitrosating agent such as butyl nitrite to form a JL -oximino-heterylacetonitrile. This class of compounds is finally substituted with a Brought chlorophosphate to react, the compounds according to the invention (R = CN) now being obtained as end products.

The overall reaction scheme is thus as follows:

XfI HCl X / i-CH ₉ Cl KCN ν

X ₂ X CTCJCT X _z / ^ά acetone ^}

= NOH

-P-R

Cl-PR ³ ν

The other reaction sequence involves making those compounds in which R is a lower alkyl radical. In this case one brings a substituted or unsubstituted one Thiophene or furan with an acid chloride or acid anhydride

3098? R / 1188

for the implementation and. Receives the corresponding 2-ketofuran or -thiophene. This derivative is used in turn with hydroxylamine hydrochloride to the corresponding ketoxime, which is finally reacted with a substituted chlorophosphate to give the respective end product. The general reaction scheme is the following (R = lower alkyl radical).

RC-Cl ν X- / ~% -4i ~ RH ₂ NOH .HCl

I / - jh i>

C = NOH Cl-PR- ⁵ ν X- # -WJ = NO-PT.

ζ / £ ~ - ·> Vi -V

Several of the intermediates used to prepare the compounds (end products) according to the invention are to be regarded as new. These are the oximes of the general formula II.

V-C = N-OH. (II)

C = N

in which X and Y each represent a hydrogen or halogen atom, a cyano or nitro group or a lower alkyl radical and Z represents an oxygen or sulfur atom.

The following examples describe typical compounds according to the invention and the process for their preparation? these However, examples are not intended to limit the invention in any way.

Example 1

2-A c et yl t h io ph en-0- (di a thy It hio pho spho r yl) -ke to xim A mixture of "7» 05 g (0.05 mol) 2-acetylthiophenketoxime, 2g

.309R? Fi / 1t8 8

(0.05 mol) sodium hydroxide and 9.4 g (0.05 mol) diethyl orthiophosphate is stirred for 16 hours in a mixture of 100 ml of water and 10 ml of ethanol. 300 ml of water are then added and the mixture is extracted with dietary ether. The ether extract is then washed successively with water, dilute potassium hydroxide solution and again with water. After drying the ether extract over magnesium sulfate, the filtrate is concentrated until an oil is obtained, which then crystallizes. After recrystallization from cyclohexane, 55 to obtain a white solid of mp. 56.5 to ⁰ C. The compound has the formula III

(III)

Analysis:
ber .:
found:

94 Γ y S. C = N- H i? 78 % 3 , 49 -0-P (OC ₂ H ₅ B. , 55 C. 5 P i N 40, 5 4.77 40, 4.79 e i el 2

2-Acetyl-5-chlorothiophene-0 - (diethy1thiophoaphpryl) -ketpxim A mixture of 17.5 g (0.1 mol) 2-acetyl-5-chlorothiophenketoxime, 18.8 g (0.1 mol) diethylchlorothiophosphate and 4.8 g (0.12 mol) of sodium hydroxide is stirred for 16 hours at room temperature in a mixture of 200 ml of water and 25 ml of ethanol. Then 250 ml of water are added and the mixture is extracted with dietary ether. The ether extract is then washed successively with water, 5% potassium hydroxide solution and again with water and then dried (HgSO.). The drying agent is filtered off and the filtrate is concentrated until an oil is obtained. The oil is dried in a high vacuum; it is found to be essentially pure based on nuclear magnetic resonance analysis. The compound has the formula IV

- 4th

309826/1188

2855 S '■ ^2282189

H ₅ ) ₂ "(IV)

he

N 27 CH-. ber .: 4, 24 found: 4,

B eis Ji ₁ ie 1 3 ct -oximino-2-thienylacetonitrile

This compound is produced as an intermediate for the synthesis of several compounds according to the invention (end products).

A solution of 2.3 g (0.1 mol) of sodium metal in 50 ml of ethanol, which was ^{cooled to 0} ° C. in an ice bath, is mixed with 12.3 g (0.1 mol) of 2-thienylaeetonitrile while stirring. When the addition is complete, 10.3 g (0.1 mol) of butyl nitrite are added. The reaction mixture is stirred for 1 hour at ⁰ ° C. and for 3 hours at room temperature. The mixture is then evaporated to dryness in vacuo and the residue obtained is washed with ether. The sodium salt of the product is dissolved in water and the solution is acidified with concentrated hydrochloric acid (up to a value of 3). The solid portion is filtered off, washed with water, dried and recrystallized from chloroform. This gives the end product (melting point 136 to 138 ° C) with the formula V '

(V)

CH N

calc .: -47.37 2.65 18.42

Found: 47.51 2.63 18.60

For EyPJ e 1

-2-thienylacetonitrile

Han makes this connection essentially according to the procedure from Example 3, but using 5-chloro-2-thienylacetonitrile as the starting compound. You get a brown

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309826/1188

yellow pest that is recrystallized from chloroform; Pp. 174 to 176 ^° C. The compound has the formula VI

(VI)

CHN
calc .: 38.61 1.61 15.00

Found: 38.82 1.61 15.27

example

g £ -oximino-2-furylacetone itril

To produce this further intermediate product is added to a cooled solution of 6.9 g (0.3 mole) of sodium metal in 200 ml ethanol at 1O ⁰ C was treated dropwise with 30.9 g (0.3 mol) of butyl nitrite and then 32.1 g (0.3 mole) 2-furan acetonitrile. The mixture is stirred for 1 hour at 10 ^° C. and then for 3 hours at room temperature. Then you steam the dark

colored mixture in a vacuum. The sodium salt is then washed with ether and dissolved in water. The solution is acidified with concentrated hydrochloric acid (up to a Ρττ value of 3). The solid is filtered off, washed with water, dried and recrystallized from chloroform. 21 g of product with a mp. 122 to 124 ^° C. are obtained

C. H N ber .: 52.94 2.96 20.58 found: 53.18 2.91 20.85

This intermediate has the formula VII

(VII)

309826/1188

Example 6 ■

O , O-diethylphosphoryl-T ^ -oximino-2-thienylacetonitrile A solution of 4 g (0.026 mol) of oi.-oximino-2-thienylacetonitrile and 2.1 g (0.027 mol) of triethylamine in 200 ml of dietary ether is added with stirring 4.47 g (0.026 mol) of diethyl chlorophosphate in 25 ml of dietary ether. The triethylamine hydrochloride is washed out of the mixture with water. The organic layer is then washed successively with dilute sodium hydroxide solution and water. The ethereal solution is dried over magnesium sulphate, filtered and the piltrate is concentrated until an oil is obtained. After drying in a high vacuum, the brown oil solidifies. The product melts at 37 to 40 ^° C. The compound has the formula VIII

Q
J = NOP (OCoHr-) ο (VIII)

calc .: 9.71
found: 9.48

example

2 _? 5-Dichlo r-p (, - oximino-3 - -thienylaceto nitrile A solution of 3.45 g (0.15 mol) of sodium in 200 ml of ethanol is ^{added to a solution, cooled to 0} ° C. in an ice bath, with 29 g of (0 , 15 mol) 2,5-dichloro-3-thienylacetonitrile After the addition has ended, 15.5 g (0.15 mol) butyl nitrite are added. The reaction mixture is ^{stirred at 0} ° C. and then for 3 hours at room temperature is filtered off and dried; 15 g of the sodium salt of the product are obtained. The piltrate is evaporated to dryness in vacuo and the residue is washed with ether. The sodium salt obtained from the piltrate is dissolved in water and the solution is acidified with concentrated hydrochloric acid (up to to a _pH value of 3) · the Peststoff is filtered off, washed with water, dried and recrystallized from chloroform umkriotallisiert; obtained 8.6 g of product Pp to 165 ° C 163. the Verbindimg has the Pormel IX..

- 7 3 0 9 8 2 6/1188

(IX)

C. 60 H s ρ 1 N 8th ber .: 32, 51 0.90 1 2.66 found: 32, 0.96 i 2.90 at e 1

0 _f O -Diäthylthionoph osphoryl - ^ - oyiinino-P-furylacet o.nitril A mixture of 6.8 g (0.05 mol) o ^ -oximino-2-furylacetonitrile and 5.05 g (0, 05 mol) triethylamine in 200 ml of diethyl ether with stirring with a solution of 9.4 g (0.05 mol) of diethyl chlorothiophosphate in 25 ml of diethyl ether. The reaction mixture is stirred for 8 hours and then washed successively with water, dilute sodium hydroxide solution and again with water. The mixture is then dried over magnesium sulfate. The drying agent is filtered off and the resulting piltrate is evaporated in vacuo. This gives a solid product which, after recrystallization from pentane, gives a solid with a point of from 46 to 48 ^° C. The product has the formula X

4th V C. C = N S.
Il r \ rt N 71 4th 1.66 H 9, 81 1.83 4.54 9, ber .: 4.58 found:

(X)

B c i π ρ i e 1

0,0 -Diet h ν 1 / th i ono £ hj3j \ pho ryj ^^^ xi mino-P -th i nnyln.ce t onj 1; rji_1. An ether solution of 5.05 g (0.05 KoI) triethylamine and 7.6 c (0.05 I.Tol) ot-oximino-P-thionylacetonitrile with a solution of 9.4 β (0.05 Mο3 Diethylchiorthioplionph.'t in? 5 ml diethyl ether. Wan riiliert, mixture 4 hours and v / H see it "n.'iclioi Ji; in; lor with V / nr.r.or, vov" liinn Ίο.ν ] -Jii1 van ~ \ nu.'vi! and ΐ) θπΤιι: ι; .ι] η nit \ '\' iir, r.oT. Drmii troclinet ni; m dir

"8 - 3 Π ΜίΓ / 1 1 ß R

Diethyl ether solution over magnesium sulfate, filtered and concentrated the filtrate until an oil is obtained. The oil solidifies as it cools. The residue yields after recrystallization from pentane a white, solid substance of m.p. 62 to 63 C., The compound has the formula XI

I \\ _ f! ₌ NOP (OC ₂ H ₅ ) ₂ , (XI)

C. H N ber .: 36.46 4.30 9.21 found: 36.70 4.36 9.31

Example 10

0,0-diethylthionophosphoryl-pi-oximino-5-chloro -? - th ienylacetone itri l A solution of 11.3 g (0.06 mol) diethyl chlorothiophosphate is added dropwise with stirring to a solution of 11.16 g (0, 06 mol) of oi-oximino-5-chloro-2-thienylacetonitrile and 6.06 g (0.06 mol) of triethylamine in 200 ml of diethyl ether. The mixture is stirred for 4 hours and then washed successively with Y / ater, dilute sodium hydroxide solution and again with water. The solution is then dried over magnesium sulfate, filtered and the filtrate is concentrated until an oil is obtained. After standing, the oil is caused to crystallize. Recrystallization from pentane gives a pure substance with a melting point of 46 to 47.degree. The compound has the formula XII

0 9 8 2 6/1188

calc .: 35.45 3.56 8.26

found: 36.19 3.69 8.21

For π ρ ie 1 11

O ^ O- Dimethylthionoph os phoryl - ^ - oximino- ^ -1 hi eny1ac e t ο nitr i 1 Han carries a solution of 8 g (0.05 mol) Dimethylchlorthiophosphnt in 25 ml diethyl ether dropwise with stirring into a solution of 5, 05 g (0.05 mol) of triethylarain and 7.6 g (0.05 mol) of et-oximino-2-thienylacetonitrile in 200 ml of diethyl ether. After 4 hours, the reaction mixture is washed successively with water, dilute sodium hydroxide solution and again with water. The resulting solution is dried over magnesium sulfate, filtered and the filtrate is concentrated until an oil is obtained. After drying under high vacuum, the yellow oil is essentially pure as shown by thin layer chromatography. The compound has the formula XIII ■

(XIII)

34 C. B. 3 H P. N 13th 1 2 ber .: 34 .77 3 .28 10, 04 found: , 16 e , 30 10, 1 i ο i e

0 ₁ 0-Dinethy It hi ο no p ho ° pho ryl-o (.- oy im ino-5-chloro-2-thienyloc otonitriI A solution of 6.1 g (0.033 mol) o6-oximino-5- Chloro- -2-thienylacetonitrile and 3.4 g (0.033 mol) of triethylamine in 200 ml of diethyl ether with a solution of 5.2 g (0.033 mol) of dimethyl chlorothiopnosphate in 25 ml of diethyl cup Sodium hydroxide solution and again with water. The solution is dried over r.iagnesium isation off

- 10 -

3 CH) Π 7 R / 1 1 ß 8

BAD ORIGiNAi.

2855. - '■■' ■

Pentane gives a product of pp. 48 to 50 G. The compound has the formula XIV

J ₂ (XIV)

J = N ■ "■

C. 92 B. H 59 P. N ber .: 30, 07 2, §7 9.01 found: 31, 2, i s 9.06 e i e 1

Il

2,5-dichloro-O _t O-diethyl.thionophosphoryl-T ^ -oxiTnino-.l-thieriyl ac eto nitrile

A mixture of 14.58 g (0.06 mol) of the sodium salt of 2,5-dichloro-i (- oximino-3-thienylacetonitrile in 150 ml of acetone is added with stirring to a solution of 9.4 g (0 , 05 mol) diethyl orthiophosphate in 10 ml acetone. The mixture is stirred for 2 hours and then poured into 400 ml v / water. The separated oil is taken up with benzene and the benzene solution is washed with water and 2 η sodium hydroxide solution to remove the. The solution is then dried over magnesium sulfate, and after the solvent has been distilled off, 9.8 g of 2,5-dichloro-0,0 ^{-diethylthionophosphoryl-y [-oximino k} -3-thienylacetonitrile are obtained in the form of a orange oil

25th

of the refractive index n ^ 1.5625. The compound has the formula XV. -,. -

Cl

8.18 7, H λ

- 11

Γ-! 0 9 '■ - :? (W 1 1 fl β

The erf indungsgeraäßen active compounds possess advantageous enough, a strong insecticidal and acaricidal efficacy at a relatively low toxicity to warm-blooded animals and low phytotoxicity at the same time. Their effect sets in quickly and lasts for a long time. When the active compounds of the invention are used to control harmful sucking and biting insects, diptera and mites (acarina), therefore, favorable results are achieved.

The insects, which with the help of the compounds according to the invention The chewing insects such as the Mexican bean beetle (Epilachna varivestis MuIs.) and the southern army worm, the boring and sucking insects, such as the green pea aphid (Acyrthosiphon pisi Kalt .; Acyrthosiphon onobrychis BDP.), the grain beetle, the red flea (Chaetochema avidtila), the housefly (Musca domestica Linnaeus), the Vine leafhoppers, the grain bug (Blissus leucopterus), the Lygus bug (Lygus spp.), The yellow oyster-shaped scale insect (Aspidiotus ostreaeformis Curt.), the red California scale insect (Aspidiotus aurantii), the red Florida scale insect (Aspidiotus ficus), the citrus scale insect (Coccus hesperidium L.) and mosquitoes, as well as pests looking for food inside the host, for example certain larvae and caterpillars, such as the European corn borer caterpillar (Pyrausta nubilalis Huebn.), The caterpillar, the peach cabbage OVnarsia lineatella Zeil.) And the cotton bollworm (Heliothis zea), certain maggots or larvae of e.g. weevils or seed beetles (Curculionidae) - like the fruit maggot (larva of the codling moth; Carpocapsa / Cydia / pomonella L-), the Liizernenblattrager (Phytonomus variabilis; Otiorrhynchus ligustici L.), the cotton boll beetle (Anthonomus grandin), the red capsule worm (Pectinophora gossypiella), the plum cutter (Conotrachelus nenuphar), the red ribbon cutter (Genus Rhynchites), the TTeloncn-nade (melon worm), the cabbage caterpillar (Trichoplusia ni Hübn.) and the Larva of the apple fly (Rhagoletis pomonella), leaf miners or flies (Fern. Agromycidae and Anthomyiidae), such as the fruit growing mini moth (Lyonetia clerkella L.), the biricennine moth and the Carrot leaf miner, and gall wasps or larvae, such as the Wheat knot worm, as well as the Rebltiuo (Phylloxera varstatrix Planch.) Insects, which have their harmful effects below the earth's surface

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BATH ORIGINAL

before unfold are classified as "subterranean insects". Examples but such harmful insects are like the blood louse (Eriosoma lanigerum Hausm.f Schizoneura lanigera Hausm.), The Japanese beetle (Popilla japomca), the larva of the onion fly (Hylemyia antiqua Meig.) and the "corn root worms" (Diabrotica spp.).

Mites and ticks are not real insects. Using the compounds of the invention many economically important species of mites and ticks can combated v / ground, for example, the Eibischspinnmilbe (Tetranychus altliaeae / telariusT 'v.Hanst.), The citrus spider mite _t (Panonychus citri), the common or spotted spider mite (Tetranychus urticae), the strawberry spider mite (Tarsonemus pallidus) and the fruit tree spider mite (Panonychus ulmi). Chemicals suitable for controlling mites are often referred to as "miticides", while chemicals which can be used to control both mites and ticks are specifically known as "acaricides".

The novel compounds of the present invention can be used in various ways to control insects or mites. Insecticides or acaricides, which are to be used as stomach poisons or preservatives _s can be applied to the area v / ground on which the insects or mites or migrate in search of food. Insecticides or acaricides, which are to be used as contact poisons or pesticides, can be brought into direct contact with the body of the insect or the mite. For this purpose, the surface on which the insect or the mite moves or tends to crawl can be treated by applying the agent, or the air inhaled by the insect or the mite can be treated with a suitable fumigant. In some cases, the compounds applied to the soil or to plant areas are absorbed by the plant, as a result of which the insects or mites are systematically poisoned. The above-described methods for using the insecticides or acaricides are essentially based on the fact that almost all of them are caused by insects or Damage caused by mites is a direct or indirect result of these pests' attempts to forage.

- 1.3 309826/1188

4i

The active compounds of the invention can if desired is, in the form of the usual preparations or compositions with conventional inert pesticide diluents or extenders, i.e. conventional dispersible carrier media for pesticides. Examples of these common forms of use are solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusts and granular preparations (granules). The means described are prepared by known methods, for example by stretching the active compounds with conventional ones for pesticides suitable dispersible, liquid, diluent-acting carriers and / or dispersible, solid carriers. If necessary, auxiliaries for the carrier medium are also used, e.g. conventional ones suitable for pesticides surface active agents such as emulsifiers or dispersants. These auxiliaries allow for example when using from water as a diluent to the suspension of organic solvents as a solution aid. The following substances can mainly to be considered for use as conventional carrier media for the stated purpose: inert, dispersible, liquid carriers acting as diluents, for example inert organic solvents such as aromatic hydrocarbons (e.g. benzene, toluene or xylene), halogenated (especially chlorinated) aromatic hydrocarbons (e.g. chlorobenzenes), paraffinic hydrocarbons (e.g. petroleum fractions), chlorinated aliphatic hydrocarbons (e.g. methylene dichloride) Alcohols (e.g. methanol, ethanol, propanol or butanol), amines (e.g. xthanolamine), ethers, ether alcohols (e.g. glycol monomethyl ether), Amides (e.g. dimethylformamide), sulfoxides (e.g. dimethyl sulfoxide) and ketones (e.g. acetone), and / or water; also inert, dispersible, finely divided, solid carriers, for example ground, naturally occurring minerals such as kaolins, aluminum oxide, Silica, chalk (i.e. calcium carbonate), talc and diatomaceous earth, and ground synthetic minerals such as highly dispersed ones Silicic acid and silicates (e.g. alkali silicates). The after-

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309826/1188

/ Γ

standing substances can mainly be used as conventional Carrier medium auxiliaries, for example as surface-active agents, can be used for the stated purpose: Emulsifiers, for example non-ionic and / or anionic Emulsifiers, such as polyethylene oxide esters of fatty acids, Polyethylene oxide ethers of fatty alcohols, alkyl sulfonates and aryl sulfonates and in particular alkylaryl polyglycol ethers, magnesium stearate, Sodium oleate, etc., and / or dispersants such as lignin, sulphite waste liquors and methyl cellulose. ·

The active compounds of the invention can be used alone or in admixture with each other and / or with the aforesaid as desired solid and / or liquid, dispersible carrier media and / or with other known, compatible active ingredients, in particular Plant protection agents, such as other acaricides, insecticides, molluscicides, nematicides, fungicides, herbicides, bactericides can be used, among others. The compounds according to the invention can be used can also be used in the form of preparations containing a certain dose for special purposes, e.g. as ready-to-use Solutions, emulsions, suspensions, powders, pastes and granulates.

f.

Specific insecticides or acaricides with which the compounds according to the invention can be used in the insecticidal or acaricidal compositions for combating insects or mites are halogenated compounds such as DDT (ρ, ρ'-dichlorodiphenyltrichloromethylmethane), methoxychlor (ρ, ρ'-dimethoxydiphenyltrichloromethylmethane) , TDE / Ϊ, 1-dichloro-2,2-bis- (p-chlorophenyl) -ethane7, lindane (contains at least 99 ° ^ -hexachlorocyclohexane), chlordane (1,2,4,5,6,7,8 , 8-octachloro-4,7-methano-3a, 4,7,7a- tetrahydroindane), isobenzane (1,3,4,5,6,7,8,8-octachlor-i, 3,3a, 4 , Ί, - 7a-hexahydro-4,7-methanoisobenzofuran), Aldrin (insecticide, containing at least 95 f ° 1,2,3,4,10, IO-hexachlor-1,4,4a, 5,8,8a- hexa-.hydro-1,4,5,8-endo, exodimethanonaphthalene), dieldrin (insecticide, containing at least 85 1 ° 1,2,3,4,10,10-hexachloro-6,7-epoxy- -1, -q ^ a ^ je ^ öjSa-octahydro-i, 4-endo, exo-5 _? 8-dimetlia.nonaphthalene), heptachlor (1 ^^, o ^^ jS-He

- 15 309828/1188

- ^ tT-methanoindene), endrin (1,2,3,4,10,1C-hexa2hlor- "6,7-opoxy- -1,4,4a, 5,6,7,8,8a-octahydro-1,4-endo, endo-5,8-dimethanonaphthalene), Mirex (Dodekachloroctahydro-1, S ^ -methaiv- ^ H-cyclobutyl / c, d / pentalen), Endosulfan (free, international name for insecticides, such as thiodane = 1,2,3,4,7,7-HexachlorbicyclQ- - (2,2, 1) -hepten ~ 5, 6-bis-oxymethylene sulfite) or Dicofol / 1,1'- -Bis- (p-chlorophenyl) -2,2,2-trichloroethanol /, organic phosphorus compounds, such as TEPP (tetraethyl pyrophosphate), Schradan (octamethylpyrophosphoramide), Ethion / Äcaricid from bis (dithiophosphoric acid-0,0-diethyl-S) -methylester /, Parathion (O, O ~ diethyl-O- -p-nitrophenylthiophosphate), methyl parathion (0,0-dimethyl-O-p- -nitrophenylthiophosphate), EPN (ethyl-p-nitrophenylthionobenzene ~ phosphonate), demeton, carbophenothione / Ö, 0-diethyl-S- (p-chloro ~ phenylthiomethyl) dithiophosphate7, phorates (O, O-diethyl-S- - / Jäthylthio) -methyl / -dithiophosphat), Zinophos (insecticide / nematicid with thionazine as the active ingredient; Thionazine = 0,0-diethyl-0-2-

-pyrazinylthiophosphate), diazinon (^ -Isopropyl ^ -methylpyrimidylthiophosphoric acid), Malathion / insecticide; Active ingredient 0,0-dimethyl-S- (1,2-dicarbathoxyethyl) -dithiophosphate /, Mevinphos (2-carbomethoxy-1-methylvinyldimethy! Phosphate), dimethoate / insecticide from dithiophosphoric acid-fN-methylamidocarboxymethyl) -0.0- -dimethylester /, DBD, Ronnel / Ö, 0-dimethyl-0- (2,4,5-trichlorophenyl) -thiophosphate /, Oxydemetonmethyl (S- / 2- (ethylsulfinyli-ethyl / - -0,0-dimethylthiophosphate, dicapthon (p-nitro-o-chlorophenyldimethylthionophosphate), Chlorothione (dimethyl ~ 3-chloro-4-nitrophenylthiophosphate), Phosphamidon ^ -Chlor ^ -diethylcarbamoyl-i- -methylvinyldiraethylphosphate), Naled (1,2-dibromo-2,2-dichloroethyldimethylphosphate), Fenthion (free, international name for insecticides, such as Lebaycid = O, O-dimethyl-O- (4-methylmercapto) -3-methy! Phenylthiophoaphat), Trichlorfon / Ö, O-dimethyl- - (2,2,? - trichloro-1-hydroxyethyl) -phosphonate / or DDVP (dimethyldichlorovinyl phosphate), organic nitrogen compounds such as dinitro-o-cresol, dinitrocyclohexylphenol, DNB, DNP, binapacryl (2,4-dinitro-6-sec.-butylphenyl-ß-methylcrotonate) or Λüobonzol, organic carbamate compounds, like carbaryl (free abbreviation for insecticides, such as serine = 1-naphthyl-N-ynethylearbamate), organic sulfur compounds such as phenothiazine, rhenoxathin, Lauryl thiocyanate, bis (2-thiocyanathyl) -ithcr or

cyanoacetate, as well as substances which are usually called "fumigants" (Fumigants) such as hydrogen cyanide, carbon tetrachloride, calcium cyanide, carbon disulfide, ethylene dichloride, Propylene dichloride, ethylene dibromide, ethylene oxide, methyl bromide or p-dichlorobenzene.

The commercialized products are generally carrier-containing mixtures containing the active compound or the active compound in an amount of about 0 _r 1 to 95 wt .- ^, preferably from about 0.5 to 90 wt .- ^ (based in each case on the mixture). Carrier-containing mixtures which are suitable for direct application or for use by Peld, on the other hand, generally contain the active ingredient in a proportion of from about 0.00001 to 20% by weight, preferably from about 0.0002 to 20% by weight, in particular from about 0.01 to 2% by weight (based in each case on the mixture). The present invention thus extends to compositions consisting of a total of suitable components, which are mixtures of the conventional dispersible carrier medium, such as (1) a dispersible, inert, finely divided pesticide and / or (2) a dispersible carrier liquid (for example an inert, organic pesticide substance and / or of water), with an effective amount of active ingredient for the required purpose. This amount of active ingredient ■ is generally about 0.00001 to 95 fo _t preferably from 0.01 to 95%. The mixtures preferably additionally contain a surface-active amount of a carrier medium auxiliary, for example a surface-active agent, such as an emulsifier and / or dispersant.

Some compounds according to the invention are tested for their insecticidal activity. The test insects are the house, fly (Musca domestica Linnaeus), the bean spider mite (Tetranychus urticae) and the beet worm (Spodoptera exigua) used. In each case the connections are tested at different doses. The evaluations (see Tables I to III) have the following meaning:

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309826/1188

VA: more than 80 # killed; -

A: 50 to 80 % killed;

SA: 25 to 49 % killed; and

I: 0 to 25 # killed.

In detail, the following test methods are used for classification the insecticides according to the invention applied. As for the test on the housefly, adults become 3 days old Houseflies used. About 50 flies are used for each degree of dilution of the chemical substance tested. the Flies are anesthetized with carbon dioxide and placed in a Buchner carrier. Then the respective degree of dilution is determined exhibiting sample poured onto the flies. The contact time is about 5 seconds. Then the chemical agents sucked off. The flies are transferred to beakers; after 1 hour, the mortality is determined.

In the case of the spider mite, a flat disc bioanalysis method is used to determine the harmful effectiveness of the compounds according to the invention. In particular, leaf disks with a diameter of about 15 ram are cut out of fresh Hendersen Busch-Lima bean plants. The discs are then immersed in the sample of the chemical substance to be tested, which has the respective degree of dilution. The leaf disks are allowed to dry and then placed on dampened filter paper or in suitably labeled Petri dishes. 10 adult mites are placed on each disc. Use 9 washers for each connection. The mortality (in <f <>) is then determined after 48 hours.

For the beet army worm, a modification of the above for the immersion method described in the housefly. 5 to 7 day old larvae of S. exigua are immersed for 5 seconds in the preparation of the test to be tested which has the respective degree of dilution Immersed insecticids. The chemical is then aspirated and the larvae are placed in petri dishes. 24 hours later mortality is determined.

- 18 309826/1188

2855

The results of the insectic effectiveness are given in the tables I, II and III can be seen. The respective of the connection associated grief corresponds to the relevant example number *

Table 1

; No. · Bean spider mite 0.025? 0.025 i « 0.0125 fo link 0.25 fo 0.05 fo VA I. SA XI VA VA - "VA I. SA XII VA VA VA I. VA IX VA VA VA VA VA X VA VA , 00625 Table II SA Connect 0.5 * Housefly 0125 fo O SA f _a 0.003 fo application no. VA - 0.05 fo 0.025 fo O, A. I. I. XI VA VA VA A. A. I. XII VA VA VA " I. I. IX VA SA SA A. SA X VA VA Table III Connection no. Beet worm 0.0125 f * XI 0 _t 5 fo ' 0.05 fo I. XII VA I I. IX VA I I. X VA I VA VA VA

, 19 _ ■ 309876/1188

Claims (35)

to claims 1., compound of general formula I. in which X and Y each represent a hydrogen or halogen atom, a Mean cyano or nitro group or a lower alkyl radical, Z is an oxygen or sulfur atom, R is a cyano group or represents a lower alkylrene, R is an oxygen or sulfur atom and R and R are each lower Mean alkyl or lower alkoxy radical. 2. A compound according to claim 1, characterized in that Z and R each represent a sulfur atom. 3. A compound according to claim 2, characterized in that R "and R each represent an alkoxy radical. 4. A compound according to claim 3, characterized in that R "and R each represent an ethoxy group. 5. A compound according to claim 2, characterized in that at least one of X and Y is a halogen atom. 6. A compound according to claim 2, characterized in that X is a Is halogen atom and Y represents hydrogen atom. 7. A compound according to claim 2, characterized in that R is a cyano group i st. 8. A compound according to claim 2, characterized in that dai.> R is an alkyl radical. -ZO- 3 09876/1188 9. A compound according to claim 1, characterized in that R is an oxygen atom and Z 'represents a sulfur atom. 10. A compound according to claim 9 »characterized in that R is a cyano group. 11. A compound according to claim 10, characterized _s that X and Y each represents a hydrogen atom. 12. Method of combating insect and mite pests, thereby characterized in that ma.n such pests with an effective amount of at least one compound of the general Formula I, ^ RR ³ in which X and Y are each a hydrogen or halogen atom, one Mean cyano or nitro group or a lower alkyl radical, Z is an oxygen or sulfur atom, R is a cyano group or a lower alkyl radical, R, an oxygen 2 is λ or sulfur atom and R and R each represent a lower alkyl or lower alkoxy radical, brings into contact. 13 · The method according to claim 12, characterized in that Z and R each represent a sulfur atom. 14. The method according to claim 13 »characterized in that R and R each represent an alkoxy radical. 15. Verfuhren according to claim 14, characterized in that R and R ^ each represent an ethoxy group. 16. The method according to claim 13, characterized in that at least one of the radicals X and Y is a halogen atom '. - 21 - SAO o * ^. 3 0 9 8 26/11 pp 17 · The method according to claim 13, characterized in that da2 X is a halogen atom and Y represents a hydrogen atom. 18. The method according to claim 13, characterized in that R is a cyano group. 19. The method according to claim 13, characterized in that R is an alkyl radical. 20. The method according to claim 12, characterized in that R is an oxygen atom and Z represents a sulfur atom. 21. The method according to claim 20, characterized in that R is a cyano group. 22. The method according to claim 21, characterized in that X and Y each represent a hydrogen atom. 23 · Pesticide composition containing a compound according to Claim 1 as an active ingredient and a diluent. 24. Composition according to claim 23, characterized in that that the diluent is a solid diluent. 25. Composition according to claim 24, characterized in that the solid diluent is an inert substance in
Is powder form. 26. Composition according to claim 24, characterized in that the solid diluent is an inert substance in
granular shape is. 27. Composition according to claim 23, characterized in that that the diluent is a liquid. - 22 - 309826/1188 fc ■ 28. Composition according to claim 27, d £ .by KernzeLchoet, that the liquid is water. 29. Composition according to claim 26, characterized in that that the "liquid is an organic solvent. 30. Composition according to claim 23, characterized in that it additionally contains a wetting agent. 31. Composition according to claim 23, characterized in that it contains 0.00001 Ms 95 wt .- ^ of the active ingredient. 32. Cyanoxime intermediate for the preparation of the compounds according to claim 1, with the general formula II Y
X - # ^ \ - C = N-OH (II) in which X and Y each represent a hydrogen or halogen atom, a Mean cyano or nitro group or a lower alkyl radical and Z represents an oxygen or sulfur atom. 33 · Connection according to claim 32, characterized in that X and Y each represent a hydrogen atom and Z is a sulfur atom. ■ 34 · Connection according to claim 32, characterized in that X is a halogen atom, Y is a hydrogen atom, and Z is a Represents sulfur atom. 35. A compound according to claim 32, characterized in that X and Y each represent a hydrogen atom and Z represents an oxygen atom is. _ ₂₃ - 30-9R76 / TTÖ-8