DE2605649A1 - NEW PHOSPHORYLATED THIOPHENE COMPOUNDS, PROCESS FOR THEIR PREPARATION AND PESTICIDAL COMPOSITIONS CONTAINING THESE - Google Patents

Description

Dr. F. Zumstein Sr. - Dr. E. Assmann - Dr. R. Koenigsberger Dfpl.-Phys. R. Holzbauer - Dipl.-Ing. F. Klingseisen - Dr. F. Zumstein jun.

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New phosphorylated thiophene compounds, methods for their

Manufacture and pesticidal compositions containing them

The present invention relates to new phosphorylated thiophene compounds of the general formula I.

4 ^

where R. is an alkyl radical having 1 to 4 carbon atoms, R _{2 is} an alkyl radical having 1 to 4 carbon atoms, an alkyloxy radical having 1 to 4 carbon atoms, a radical -N ^^ "* where R 'and R" are a hydrogen atom or an alkyl radical 1 to 4 carbon atoms represents, R represents a cyano group, an alkyloxycarbonyl group having 2 to 4 carbon atoms, a group -CZ, in which Z is an alkyl radical having 1 to 4 carbon atoms or a phenyl radical, Rk is an alkyl radical having 1 to 6 carbon atoms , an alkyloxy group with 1 to 6 carbon atoms, an alkylthio group with 1 to 6 carbon atoms, a phenyl group, a morpholinyl or piperidinyl group or an alkyloxycarbonyl group with 2 to 4 carbon atoms and X is an oxygen or sulfur

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- 2 - represents atom.

In formula I, R ₁ and Rp denote in particular a methyl, ethyl, linear or branched propyl or linear or branched butyl radical, Rp denotes in particular a methoxy, ethoxy, linear or branched propoxy, linear or branched butoxy radical, a Amino group, a methylamino, ethylamino, propylamino, isopropylamino, butylamino, dimethylamino, diethylamino, dipropylamino or dibutylamino group, R-, means in particular a cyano, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxyearbonycarbonyl Acetyl, propionyl, butyryl or benzoyl group, Rj, means a methyl, ethyl, linear or branched propyl, linear or branched butyl, linear or branched pentyl, linear or branched hexyl, methoxy, ethoxy , Propoxy, butoxy, methylthio, ethylthio, propylthio, butylthio, phenyl, morpholinyl or piperidinyl radical, a methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl or butoxycarbonyl group and X is an oxygen or sulfur atom.

Compounds of the formula I that should be mentioned are, in particular, the compounds of the formula I in which R _{1 is} an alkyl radical having 1 to 4 carbon atoms, Rp is an alkyloxy radical having 1 to 4 carbon atoms, X is an oxygen atom, R- is a cyano group, R ₂ ^ denotes an alkyl radical having 1 to 6 carbon atoms or an alkyloxy radical having 1 to 6 carbon atoms and in particular the compounds described in the examples.

The compounds of the formula I have remarkable insecticidal and / or acaricidal and / or nematocidal properties which they make useful in agriculture for combating harmful organisms and in particular insects and / or mites.

These properties have been shown in the following tests with insects, mites and nematodes.

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-? - 26P5649

The invention also relates to a process for the preparation of compounds of the general formula I, which is characterized in that is that with a compound of formula II

wherein R ₅ and R ₂ , as defined above, are a reactive phosphorus compound of the formula III

wherein R ₁ , Rp and X have the meaning given above, is reacted.

The esterification with the reactive chlorophosphorus compound is preferably carried out in an organic solvent medium such as acetonitrile, acetone, dimethylformamide and tetrahydrofuran.

This reaction is preferably carried out in the presence of a basic reagent, especially potassium carbonate, sodium hydride and Triethylamine carried out.

The compounds of the formula II are generally described in the literature.

Such is the 2-cyano-3-hydroxy-5-niethylthiophene from B. Hedegaard et al. in Tet. 27, 3853 (1971).

The 2-cyano-3-hydroxy-5-phenyl-thiophene is from B. Hedegaard et al. in Tet. 2J, 3858 (1971).

The 2,5-dicarbomethoxy-3-hydroxy-thiophene is from H. Fiesseimann and P. Schippark in Ber. 89, 1897 (1936).

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The 2-methoxycarbonyl-3-hydroxy-5-methylthiophene is from HJ Jacobsen et al. in Tet. 2A_, 3331 (1965). The 2-benzoyl-3-hydroxy-5-methoxythiophene is described by R. Raap in Can. J. Chem. Jjj>, 2255 (1968). The 2-methoxycarbonyl-3-hydroxy-5-methoxythiophene is described by R. Raap in Can. J. Chem. K6 _s 2258 (1968).

The other compounds of the formula II can be prepared analogously to the manner indicated in the literature references mentioned above getting produced.

The following compounds of the formula II are not described in the literature:

2-cyano-3-hydroxy-5-methoxythiophene, 2-cyano-3-hydroxy-5- (N-morpholino) -thiophene, 2-cyano-5-ethylthio-3-hydroxythiophene, 2-cyano-3-hydroxy-5-n-butoxythiophene and the 2-cyano-3-hydroxy-5-n-propylthiophene.

Methods for preparing these compounds are given in the experimental section.

The 2-fithoxycarbonyl-imido-acetic acid methyl ester hydrochloride and the 2-ethoxycarbonyl-thioacetic acid-O-methyl ester, for required the production of 2-cyano-3-hydroxy-5-methoxy-thiophene Intermediate products, the 2-sthoxycarbonyl-acetic acid imido-O-n-butyl ester hydrochloride and Äer 2-Kthoxycarbonylthioessigsäure-O-n-butyl ester, intermediate products required for the production of 2-cyano-5-hydroxy-5-n-butoxy-thiophene, are not described in the literature.

Methods for preparing these compounds are given in the experimental section.

The invention also includes insecticidal, acaricidal or nematocidal compositions which contain at least one active ingredient of the compounds of formula I.

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These compositions can be in the form of powders, granules., Suspensions, emulsions and solutions are present, for example in a mixture with a carrier and / or an anionic, cationic or nonionic surfactant which, among other things, provides a uniform dispersion of the substances ensured by the composition. The carrier used can be a liquid such as water, Alcohol, hydrocarbons or other organic solvents, a mineral oil, an animal or vegetable oil or a powder such as talc, the clays, the silicates and diatomaceous earth.

The insecticidal liquids or powders for spraying on the foliage preferably contain 10 to 80 wt -.% Of active substance.

The acaricidal liquids or powders for spraying on the foliage preferably contain 20 to 80 wt -.% Of active substance.

The nematocidal liquids or powders for the treatment of the soil preferably contain 20 to 80 wt .- ^ of the active ingredient.

The following examples illustrate the invention.

example 1 2-cyano-3- (dimethoxyphosphoryloxy) -5-methyl-thiophene

Is added to a solution of 14 g of 2-cyano-3-hydroxy-5-methylthiophene in 300 cm of acetone, 14 g of potassium carbonate, 8.9 cm 0.0-dimethyl chlorophosphate, stirred at 20 ⁰ C for 15 hrs., Concentrated to dryness , poured into water, extracted with ether, the ethereal phase was washed with 0.1 N sodium hydroxide solution, dried, treated with activated charcoal, filtered, concentrated to dryness and obtained 12 g of 2-cyano-3- (dimethoxyphosphoryloxy) -5-methylthiophene.

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~ ⁶ ~ 2805649

Chromatography on silica gel eluting with a mixture of cyclohexane and ethyl acetate (2-8) and subsequent washing of the product obtained with 0.1 N sodium hydroxide solution gives a microanalytical sample, n ^ ° = 1.5165.

Analysis: CgH ₁₀ NO ₄ PS

calc .: C % 38.86 H % 4.08 N % 5.67 P % 12.53 found: 39.5 4.2 5.7 12.2

Example 2

2-Cyano-3- (dimethoxythiophosphoryloxy) -5-methyl-thiophene is added to a solution of 11.2 g of 2-cyano-3-hydroxy-5-methylthiophene in 200 cnr acetone, 11.2 g of potassium carbonate, 12.8 g 0,0-dimethyl chlorothiophosphate, stirred for 15 hours at 20 ° C., filtered, the filtrate concentrated to dryness, the residue chromatographed on silica gel eluting with a mixture of cyclohexane and ethyl acetate (7-3) and obtained 18.7 g 2-cyano-3- (dimethoxythiophosphoryloxy) -5-methyl-

20th
thiophene, nf ^u = 1.539-

H % 3.84 N % 5.32 P % 11.76 4.0 5.4 11.4

2-Cyano-3- (diethoxythiophosphoryloxy) -5-methyl-thiophene is introduced into a solution of 7 g of 2-cyano-3-hydroxy-5-methylthiophene in 100 cnr acetone 7 g of potassium carbonate and 9.5 g of 0.0 -Diäthylchlorthiophosphat a, stirred for 15 hrs. at 20 ⁰ C and filtered, the Piltrat concentrated to dryness, the residue is chromatographed on Siliciumdioxydgel eluting with a mixture of cyclohexane and ethyl acetate (8-2) to yield 11.2 g of 2-cyano -3- (diethoxythiophosphoryloxy) 5-methyl-thiophene, nj = 1.534.

Analysis: C 5 NO calc .: C % 50 found: 4th Example j JoH ₁₀ 36, 36,

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Analysis: C ₁ -H ₁ calc .: C % t
41 , 23 found: 41 , 5 Example 4

H % 4.85 N % 4.81 P % 10.63 4.9 4.7 10.5

2-Cyano-3- (dimethoxyphosphoryloxy) -5-methoxy-thiophene is added to a solution of 9.3 g of 2-cyano-3-hydroxy-5-methoxythiophene in 100 ml of acetonitrile, 8.4 g of potassium carbonate and 7 * 1 g 0,0-dimethylchlorophosphate, stirred for 16 hours, filtered, the filtrate concentrated to dryness, ether added to the residue, washed with water and 0.1N sodium hydroxide solution, dried, concentrated the organic phase to dryness and obtained 12 g 2-cyano-j5- (dimethoxyphosphoryloxy) -5-methoxy-thiophene, 4 ° = 1.523.

Analysis: C ₈ H ^ ₀ NO ₅ ^{1 3} pp 83 N. % 5, 32 P % 11 , 76 calc .: C % 36, 52 H. % 3, 0 5, 6th 11 , 5 found: 36, 8th 4,

The 2-cyano-3-hydroxy-5-methoxy-thiophene used as a starting material in the example can be as follows Way to be made:

a) Production of 2-ethoxycarbonyl-itnido-acetic acid methyl ester hydrochloride;

Is passed into a solution of 45.2 g of cyanoacetic acid ethyl ester to the absorption of 20 g in 400 cnr ethyl ether at 20 ° C gaseous hydrogen chloride, add 12.8 g of methanol is added, stirred at 20 ⁰ C for 8 hrs., Isolated by suction, the crystals formed, this is washed with ether and obtains 39 g of 2-ethoxycarbonyl-acetic acid imido-methylesterhydrochlorid (P = 95-100 ⁰ C), which is used as such in the following step. A dried sample of this compound melts at 100-105 ° C (dec.);

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b) Preparation of 2-Kthoxycarbonyl-thioessigsä'ure-0-methyl-5ter

The mixture is saturated at ⁰ ° C 250 cnr pyridine with hydrogen sulfide, added 59 g of 2-Kthoxycarbonyl-acetic acid imido-methylester hydrochloride added, introducing sets of hydrogen sulphide for 2 hrs. At 0 ⁰ C continued stirring for 6 hrs. At room temperature , Pour the reaction solution over ice, acidify with concentrated hydrochloric acid to pH 5, extract with methylene chloride, dry, filter, concentrate to dryness, rectify the residue and obtain 51 g of 2-ethoxycarbonyl-thioacetic acid-O-methyl ester, bp . = 79 ° C at 5 mm Hg;

c) Production of 2-cyano-5-hydroxy-5-ethoxy-thiophene

One adds to a solution of 27 g of sodium methylate in 250 cnr Methanol 81 g of 2-ethoxycarbonyl-thioacetic acid O-methyl ester and then 58 g of chloroacetonitrile, brought to reflux, refluxed for 1 hour, adds to the reaction. suspension 27 g of sodium methylate in solution in 100 cnr of methanol, lets the temperature return to 20 C, concentrated to dryness, dissolves the residue in water, washes the aqueous solution Phase with Xther, acidified by adding conc. Hydrochloric acid, isolates the crystals formed by suction, dries them and receives 42 g of 2-cyano-5-hydroxy-5-methoxy-thiophene, F = 158 - i4o ° e.

Recrystallization in isopropyl ether gives a Sample of microanalytical purity, F = 140 ° C.

Analysis: C. 6 ^H 5 NO ₂ S 25th N % 9, 05 O Jb 67 calc .: C % ; 46, 44 tr oil
η jo 02 8th, 7th 5 found: 46, 5 ; 20, '< 5, 20, 5,

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Example 5 2-cyano-3- (dimethoxyphosphoryloxy) -5- (N-morpholino) -thiophene

Place 6.3 g of 2-cyano-3-hydroxy-5- (N-morpholino) thiophene in a solution 4.2 g of potassium carbonate and 4.3 g of 0,0-dimethylchlorophosphate in 125 cnr acetonitrile, stirred for 8 hours at 20 ° C., filtered, the filtrate concentrated to dryness, ethyl acetate added to the residue, washed with Water ^ with 0.1 N sodium hydroxide solution, the organic phase dries, treated with activated charcoal, filtered, concentrated to dryness, the residue crystallized from a mixture of ethyl ether and ethyl acetate (10-2) and receives 8 g of 2-cyano-3- (dimethoxyphosphoryloxy) -5- (N-morpholino) -thiophene, P = 80 ° C.

Analysis; C ₁₁ H ₁₁ -N ₂ OcPS

calc .: C & 41.51 H # 4.75 N % 8.80 P % 9.73 found: 41.6 4.8 8.8. 9.7

The 2-cyano-3-hydroxy-5- (N-morpholino) -thiophene found in the Example used as the starting material can be prepared in the following way:

500 cnr of tetrahydrofuran and 10 g of a suspension of 50 % sodium hydride in mineral oil are mixed, and 40.6 g of methyl N- (morpholino-thiocarbonyl) -acetate are added in several portions (the compound is described by R. Raap in Can. J. Chem. described _46, 2255 (1968)) is added, leaving for 2 hrs. at 20 ⁰ C, adding 15.5 g of chloroacetonitrile in 500 cnr · solution in tetrahydrofuran added, adds 500 cnr methanol, stirred for 3 hrs. at 20 ⁰ C , brings 14 g of potassium methylate in solution in 300 cnr of methanol, the suspension is stirred for 3 hours at 20 ° C., concentrated to dryness, the residue is dissolved in water, the aqueous solution is washed with methyl acetate, acidified with acetic acid, cooled, isolated the crystals formed by suction, washing them with water, drying them and obtaining 22 g of 2-cyano-3-hydroxy-5-N-morpholino-thiophene, P = 180-182 ° C.

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Analysis;

calc.i C # 51.41 H ^ 4.80 N # 13.32 S% 15.25 found: 51 * 1 4.9 13.2 15.2

Example 6

2-cyano-3- (dimethoxythiophosphoryloxy) -5-phenyl-thiophene

Bringing into a solution of 10.5 g of 2-cyano-3-hydroxy-5-phenyl-thiophene in 120 cm of acetone, 7 g of potassium carbonate and 8 g 0,0-a dimethylchlorothiophosphate, stirred for 15 hrs. At 20 ⁰ C, filtered, the filtrate concentrated to dryness, thickened the crystals obtained with petroleum ether and recrystallized them from isopropyl ether. 12.8 g of 2-cyano-3- (dimethoxythiophosphoryloxy) -5-phenyl-thiophene, melting point = 95 ° C., are obtained.

analysis • % C ₁₅ H ₁ 2 ^N0 3 PS ₂ 71 ber .: C 48.00 H % 3, 9 found: 7th 48.2 3, example

N % 4.31 P % 9.52 4.4 9.4

2,5-dicarbomethoxy-3- (dimethoxythiophosphoryloxy) thiophene

14 g of potassium carbonate and 16 g of 0,0-dimethylchlorothiophosphate are introduced into a solution of 21.6 g of 2,5-dicarbomethoxy-3-hydroxy-thiophene in 500 cnr acetone, stirred for 15 hours at 20 ° C., filtered, the filtrate evaporates to dryness, the residue obtained is thickened with isopropyl ether, cooled, the crystals formed are isolated by suction filtration, washed with petroleum ether, the product obtained recrystallized in methanol and 21 g of 2> 5-di.carbomethoxy-3 are obtained - (dimethoxythiophosphoryloxy) thiophene, F = 71 " ⁰ C.

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Calc .: C # 35.30 H ^ 3.85 P # 9.10 found: 35.4 3.9 9.1

Example 8

2,5-dicarbomethoxy - ^ - (dimethoxy-phosphoryloxy) -thiophene

5.6 g of potassium carbonate and 5.7 g of 0,0-dimethylchlorophosphate are introduced into a solution of 8.6 g of 2,5-dicarbomethoxy-3-hydroxythiophene in 100 cnr acetone, and the mixture is stirred at 20 ° C. for 15 hours , filtered, the filtrate concentrated to dryness, the residue dissolved in ethyl ether, the ethereal solution was washed with 0.1 N sodium hydroxide solution, dried, concentrated to dryness, the residue crystallized from ethyl ether and obtained 5.2 g of 2.5 Dicarbomethoxy-3- (dimethoxy-phosphoryloxy) thiophene, m.p. 60 ° C. Analysis: C ₁₀ H ₁ ^ OqPS

calc .: C % 37.13 H % 4.03 P % 9.51 found: 37.4 4.1 9.4

Example 9

2,5-dicarbomethoxy-3- (diethoxythiophosphoryloxy) thiophene

7 g of potassium carbonate and 8.9 g of 0,0-diethylchlorothiophosphate are introduced into a solution of 10.9 g of 2,5-dicarbomethoxy-3-hydroxy-thiophene in 500 cnr acetone, and the mixture is stirred at 20 ° C. for 15 hours, filtered, the filtrate concentrated to dryness, the residue was thickened with a mixture of petroleum ether and isopropyl ether (10-1), the precipitate formed was isolated by suction, recrystallized from ethanol and obtained 8.5 g of 2,5-dicarbomethoxy-3- (diethoxythiophosphoryloxy) thiophene, F = 50 ° C.
Analysis: C ₁₂ H ₁₇ -O ₇ PS ₂

calc .: C % 39.12 H % 4.65 P % 8.41 found: 39.4 4.9 8.4.

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Example 10

2-carbomethoxy-3- (diethoxythiophosphoryloxy) -5-methyl-thiophene

4.7 g of a suspension of 60% sodium hydride in mineral oil are slowly added to a solution of 20 g of 2-methoxycarbonyl-3-hydroxy-5-methyl-thiophene in 200 cnr dimethylformamide, and the mixture is stirred ^{at 20 °} C. for 1 hour rapidly added a solution of 22.4 g of 0,0-Diäthylchlorthiophosphat in 50 cnr dimethylformamide is added, stirred for 15 hrs. at 20 ⁰ C, the suspension is poured over an ice-water mixture, extracted with ether, dried, concentrated to dryness, chromatographed the residue on silica gel eluting with a mixture of cyclohexane and ethyl acetate (9-1) and obtained 11.5 g of 2-carbomethoxy-3-

22 (diethoxythiophosphoryloxy) -5-methyl-thiophene, η _β = 1.5272.

Analysis; C ₁₁ H ₁₇ O ₅ PS ₂

calc .: C % 40.74 H % 5.19 P % 9.55 found: 40.7 5A 9.0

Example 11

2-benzoyl-3- (dimethoxyphosphoryloxy) -5-methoxy-thiophene

4.2 g of potassium carbonate and 4.3 g of 0,0-dimethylchlorophosphate are introduced into a solution of 7.9 g of 2-benzoyl-3-hydroxy-5-methoxy-thiophene in 100 ml of acetonitrile, and the mixture is stirred for 16 hours 20 ⁰ C, filtered, the filtrate was concentrated to dryness, added to the residue, ethyl acetate hinz-u, washes the "organic solution with water, decanted, with an aqueous 0.1 N sodium hydroxide solution, saturated with sodium chloride, drying the organic Phase, treated with activated charcoal, filtered, concentrated to dryness by distillation under reduced pressure, the residue crystallized from ether, the crystals formed were isolated by suction and 8.2 g of 2-benzoyl-3- (dimethoxyphosphoryloxy) -5-methoxy-thiophene were obtained , F - 76 C.

Analysis: 49, ^H 15 OgPS 4, 47 P. Si 9 , 05 calc .: C % 49, 12th ti et
η yo 4, 5 9 , 0 found: 4th

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Example 12 2-carbomethoxy-3- (dimethoxyphosphoryloxy) -5 - methoxy-thiophene

7 g of potassium carbonate and 7.2 g of 0,0-dimethylchlorophosphate are introduced into a solution of 9.5 g of 2-methoxycarbonyl-3-hydroxy-5-methoxy-thiophene in 125 cn of acetonitrile, and the mixture is stirred for 16 hours at 20 ° C ⁰ C, filtered by vacuum distillation to dryness, the residue is taken with ethyl acetate, washed the organic solution with water, with a 0.1 N ^ with sodium chloride saturated sodium hydroxide solution, dried ·, concentrated to, dryness, the residue from isopropyl ether crystallizes and receives 12 g of 2-carbomethoxy-3- (dimethoxyphosphoryloxy) -5-methoxythiophene, mp = 35 ° C.

Analysis: CqH ₁ - * OjPS

calc .: C % 36.49 H % 4.42 P % 10.45 found: 36.7 4.5 10.3

Example 13

2-cyano-3- (diethoxythiophosphoryloxy) -5-ethylthlo-thiophene

Is added to a solution of 9.3 g of 2-cyano-5-ethylthio-3-hydroxythiophene in 150 CRRR acetonitrile 7 g of potassium carbonate and 9.4 g of 0,0-Diäthylchlorthiophosphat, stirred for 24 hrs. At 20 ⁰ C, filtered , concentrated to dryness, chromatograph, the residue on silica gel while eluting with a mixture of cyclohexane and ethyl acetate (8-2) and obtained 14.6 g of 2-cyano-3- (diethoxythiophosphoryloxy) -5-ethylthiophene, ° = 1.5635.

Analysis: C ₁₁ H ₁ / ςΝΟ- ¹ I S-, 78 N. 5ί 4 , 15 p % ■ 9 s 18th calc .: C % 39 16 H. % 4, 9 4th , 0 9, 3 found: 39 6th 4,

The 2-cyano-5-ethylthio-3-hydroxy-thiophene can be prepared in the following way:

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Is added to a solution of 70 g of potassium methoxide in one liter of methanol at 20 ⁰ C 192 g et-carbethoxy-dithioacetic acid ethyl ester (described in Berichte 100, 1420 (1967)), stirred for 5 min. At 20 ⁰ C, adding 76 g chloroacetonitrile is added, stirred for 1 hr. at 45 ° C, then for 2 hrs. at 20 ⁰ C, a solution added of 70 g of potassium methylate in 500 cnr methanol is added, stirred for 4 hrs. at 20 ⁰ C, concentrated by distillation to dryness under reduced pressure, dissolve the residue in water, add toluene, acidify with conc. Hydrochloric acid and quickly separates the organic phase by decantation. This is cooled, the crystals formed are isolated by suction, dried and 97 g of 2-cyano-3-hydroxy-5-ethylthiophene, mp = 105 ° C., are obtained.

Recrystallization from benzene gives a sample of microanalytical purity, P = 105 ° C.

Analysis;

calc .: C % 4-5.38 H % 3.81 N % 7.56 S % 34.6 found: 45.6 4.0 7.5 34.4

Example 14 2-cyano-3- (diethoxyphosphoryloxy) -5-ethylthio-thiophene

7 g of potassium carbonate and 8.6 g of 0,0-diethyl chlorophosphate are introduced into a solution of 10.1 g of 2-cyano-5-ethylthio-3-hydroxy-thiophene in 150 cnr acetonitrile, and the mixture is stirred for 24 hours 20 ^° C., filtered, concentrated to dryness, ether added, the ethereal solution was washed with 0.1 N sodium hydroxide solution, dried, treated with activated charcoal, concentrated to dryness and received 13 g of 2-cyano-3- (diethoxyphosphoryloxy) -5 -ethylthiothiophene, n ^ ⁰ = 1.538.

Analysis: ^C 1 1 ^H. ₁₆ NO ₄ HP 2 5, 02 N % 4, 36 P. fo 9, 64 calc .: C % 41 ,1 1 H % 5, 0 4, 2 9, 5 found: 40 ,8th

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Example 15 2-cyano-3- (dimethoxyphosphoryloxy) -5-ethylthio-thiophene

7.7 g of potassium carbonate and 7.7 g of 0,0-dimethylchlorophosphate are introduced into a solution of 10.1 g of 2-cyano-5-ethylthio-3-hydroxy-thiophene in 125 cm of acetonitrile, and the mixture is stirred for 8 hours 20 ^° C., filtered, concentrated to dryness, ether added to the residue, the ethereal solution was washed with water ^ with 0.1 N sodium hydroxide solution, dried, treated with activated charcoal, concentrated to dryness and obtained 12 g of 2-cyano-3 - (dimethoxyphosphoryloxy) -5-ethylthio-thiophene, n _D = 1.5570.

Analysis: C ₉ H ₁₂ NO ^ PS ₂

calc .: 0% 36.85 E% 4.12 N # 4.77 P # 10.56 found: 37.1 4.1 4.7 ■ 10.3

Example 16

2-cyano-3- (dimethoxythiophosphoryloxy) -5-ethylthio-thiophene

In a solution of 9.3 g bringing 2-cyano-5-ethylthio-3-hydroxy-thiophene in 125 cnr acetonitrile J g of potassium carbonate and 8 g of 0,0-dimethylchlorothiophosphate a, stirred for 24 hrs. At 20 ⁰ C, filtered, concentrated to dryness by distillation under reduced pressure, the residue chromatographed on silica gel eluting with a mixture of cyclohexane and ethyl acetate (8-2) to give 14 g of 2-cyano-3- (dimethoxythiophosphoryloxy) -5-ethylthiophene, = 1.5825.

Analysis: CgH ₁₂ NO ₅ PS ₅

Calc .: C % 34.94 H % 3.91 N # 4.53 P # 10.01 found: 34.9 3.8 4.4 9.8

Example 17 2-Cyano-3- (dläthoxyphosphoryloxy) -5-methyl-thiophene

It is brought into a solution of 11.5 g of 2-cyano-3-hydroxy-5-methylthiophene in 80 οπκ acetonitrile 11.42 g potassium carbonate.

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stirs for 5 min., adds 12.08 g Ο, Ο-diethyl chlorophosphate, stir for 24 hrs. at room temperature, filtered, concentrated to dryness, the residue is chromatographed on silica gel while eluting with a mixture of cyclohexane and ethyl acetate (6-4), dissolve the product obtained in ethyl acetate, wash with an aqueous sodium hydroxide solution, separate the organic phase is removed by decantation, dries it, concentrates it to dryness and receives 15 g of 2-cyano-5 ~ (diethoxy-

21
phosphoryloxy) -5-methyl-thiophene, n_ = 1.502.

Analysis: % C ₁₀ H ₁ ber .: C 45, found: 18th 45, 5 example

5.12 N # 5.09 P £ 11.25 5.2 4.9 11.5

2-cyano-5- (dimethoxyphosphoryloxy) -5-n-propyl-thiophene

2.76 g of potassium carbonate are introduced into a solution of 5.4 g of 2-cyano-5-hydroxy-5-n-propylthiophene in 50 cnr acetonitrile, the mixture is stirred for 5 minutes at 20 ° C., and 2.6 g of O2 are added , 0-dimethyl chlorophosphate is added, stirred for 20 hrs. at 20 ⁰ C, filtered, concentrated to dryness, the residue is dissolved in ethyl acetate, the organic solution is washed with 0.01N sodium hydroxide solution, dried and concentrated to dryness to obtain 5 g 2 -Cyano-5- (dimethoxyphosphoryloxy) -5-n-propyl-thiophene, tijp * - * = 1.507. '

Analysis: ^C 1O ^H 14 NO ₄ P S. 5, 12th N % 5, 09 P % 11 25th calc .: C % 45.65 H % 5, 4th 4, 9 10, 9 found: 45.60

The 2-cyano 5-hydroxy-5-n-propyl-thiophene used as a starting material in the example can be prepared in the following manner will be obtained:

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Level a

3-Thioxo-hexanoic acid ethyl ester

100 cnr ethanol saturated with hydrogen chloride is cooled to -10 ° C. and 23.7 g of ethyl 3-oxo-hexanoate are added. Hydrogen sulfide is passed in at -10 ° C. for 6 hours, the solvent is evaporated, the residue is taken up in ether, washes with water and dries. 25.8 g of ethyl 3-thioxohexanoate are obtained.

Level B. 2-cyano-3-hydroxy-5-propyl-thiophene

The mixture is stirred a mixture of 77 g j5-thioxo hexansaureäthylester, 300 cnr methanol and 28 g of potassium methoxide for 15 hrs. At 20 ⁰ C. Is added 33.2 g of chloroacetonitrile are added and again stirred for 15 min. At 20 ⁰ C. The mixture is heated for 4 hrs. At reflux temperature, the solvent is evaporated, the residue is taken up in water, washed with methylene chloride ·, acidified by conc . Hydrochloric acid, extracted with ethyl acetate, treated with activated charcoal, dried and evaporated to dryness.

The residue is taken up in toluene, cooled, the crystals obtained are filtered off with suction and recrystallized from a mixture of petroleum ether and benzene (3-1). 3.1 g of 2-cyano-3-hydroxy-5-propyl-thiophene, F = 78 ^° C., are obtained

Analysis; CqHqNOS

calc .: C % 57, ^ 5 H % 5.42 N % 8.37 S % 19.17 found: 57.4 5.3 8.3 19.3

Example 19 2-cyano-3- (ethoxy-methyl-thiophosphonyloxy) -5-methyl-thiophene

It is brought into a solution of 14 g of 2-cyano-3-hydroxy-5-methylthiophene in 150 cm of acetonitrile 14 g of potassium carbonate and 15.9 g

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Chlorine (methyl-O-ethyl-phosphothionate), stirred for 24 hours. At 20 ° C, filtered, concentrated to dryness, the residue chromatographed on silica gel eluting with a mixture of cyclohexane and ethyl acetate (85-15) and obtained 19 g of 2-cyano-3- (ethoxy-methyl-thiophosphonyloxy) -5-methylthiophene, n _D ° = 1.5570.

Analysis: ^C 9 > ^H 12 ^N0 2 ^PS 2 4, 63 N % 5, 36 1 - 85 calc .: C % 41 .37 H % 4, 7th 5, 3 1 1, 6th found: 41 , 3 1,

Example 20

2-cyano-3- (ethoxy-N-isopropyl-thiophosphoramidoxy) -5-methyl-

thiophene

It is brought into a solution of 14 g of 2-cyano-3-hydroxy-5-methylthiophene in 150 cnr acetonitrile 14 g potassium carbonate and 19 g N-isopropyl-O-ethyl-chlorothiophosphoramidate, stirred during 24 hours at 20 ° C., filtered, concentrated to dryness, and the residue chromatographed on silica gel with elution with a mixture of benzene and petroleum ether (85-15) and receives 23 g of 2-cyano-3- (ethoxy-N-isopropyl-thiophosphoramidoxy) -5-methylthiophene, ng = 1.544.

N # 9.20 P % 10.18

8.9 10.4

2-cyano-3- (diethoxythiophosphoryloxy) -5-n-butoxy-thiophene

Bringing into a solution of 9.8 g of 2-cyano-3-hydroxy-5-n-butoxythiophen in 150 em ^ J acetonitrile g of potassium carbonate and 9> 4 g 0,0-a Diäthylchlorthiophosphat, stirred for 24 hours' at 20 ⁰ C, filtered, concentrated to dryness under reduced pressure, the residue chromatographed on silica gel

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Analysis: C ₁₁ H ₁₇ N ₂ O ^ ₂ PS ₂ 63 calc .: C % 43.41 H. % 5, 8th gef.r 43.7 5, Example 21

eluting with benzene and obtaining 14 g of 2-cyano-3- (diethoxy

20 thiophosphoryloxy) -5-n-butoxy-thiophene, n ^ = 1.525.

Analysis; C ₁₅ H ₂₀ ^ ₂

calc .: C % 44.69 H % 5.77 N % 4.01 P % 8.85 found: 44.8 5.9 3.9 8.9

The 2-cyano-3-hydroxy-5-n-butoxy-thiophene can be based on the following Way to be made:

a) Production of 2-ethoxy-carbonyl-imido-essiqsäurebutyl; ^ ester hydrochloride

A stream of dry hydrogen chloride is passed into a solution of 45.2 g of ethyl cyanoacetate in 29.6 g of butanol up to an absorption of 16 g. The mixture is stirred for 18 hrs. At 15 ⁰ C, concentrated in vacuo to dryness to obtain 90.5 g of crude 2-Xthoxy-carbonyl-acetic acid imidobutylester hydrochloride, which is used as such for the following step.

b) Production of 2-ethoxycarbonyl-thio-acetic acid ~ 0-n-butyl ester

Passing hydrogen sulfide in pyridine car 400 to the absorption of 30 g of the same one, is slowly added at -15 ⁰ C 90.5 g of 2-ethoxycarbonyl-acetic acid imidobutylester hydrochloride is added, stirred for 24 hrs. At 20 ° C, poured over Ice, acidified with conc. Hydrochloric acid, extracted with methylene chloride, the organic phase dried, filtered, concentrated to dryness, then rectified under reduced pressure and thus obtained 62.3 g of 2-A "thoxycarbonyl * -thio-acetic acid-0-n-butyl ester, boiling point = 100 ⁰ C at 0.4 mm Hg.

c) Production of 2-cyano-3-hydroxy-5-n-butoxy-thiophene

It is added to a solution of 70 g of potassium methylate in 1 1 of methanol. 30 ⁰ C 205 g of 2-sthoxycarbonyl-thio-acetic acid-on-butyl ester, stirred for 10 min. At 30 ⁰ C, brings all at once 75.5 g of chlorine

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acetonitrile, stirred for 1 hour. At 40 ° C, adds a Add a solution of 70 g of potassium methylate in 300 cm of methanol, stirs for 6 hours at room temperature, concentrated to Dry, wash the residue with stylacetate and ether, dry it, dissolve it in water, acidify the solution with it conc. Hydrochloric acid, isolate the precipitate formed by suction, wash it with water, dry it, and chromatograph pass it over silica gel, eluting with a mixture of cyclohexane and ethyl acetate (6-4), and obtain 81 g 2-cyano-3-hydroxy-5-n-butoxy-thiophene, P = 107 C.

Analysis: % CqH Ί Λ ber .: C 54, I ι
80 found: 22nd 55, 1 example

5.62 N # 7.10 S # 16.25 5.7 7.0. 16.3

2-cyano-3- (dimethoxythiophosphoryloxy) -5-n-butoxy-thiophene

It is brought into a solution of 9.8 g of 2-cyano-3-hydroxy-5-n-butoxythiophene in 150 cnr acetonitrile 7 g potassium carbonate and 8 g OiO-dimethylchlorothiophosphate, stirred for 24 hours 20 C, filtered, concentrated to dryness, the residue chromatographed on silica gel while eluting with benzene and receives 11g 2-cyano-3- (dimethoxythiophosphoryloxy) -5-n-

20th
butoxy-thiophene, n ^ = 1.5375-

H % 5.02 N % 4.37 P % 9.64 5.0 4.3 9.5

2-cyano-3- (diethoxy-phosphoryloxy) -5-n-butoxy-thiophene

It is brought into a solution of 11 g of 2-cyano-3-hydroxy-5-n-butoxy thiophene in 150 cnr acetonitrile, 7.7 g potassium carbonate and 8.6 g 0,0-diethyl chlorophosphate, stirred for 16 hours at room temperature, filtered, concentrated to dryness, adds to that

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Analysis: % C ₁ .H ₁ ber .: C 41 , 11 found: 41 ,1 BeisDiel

Ethyl ether residue is added, the ethereal solution is washed with an aqueous solution containing 100 g per liter of sodium chloride Solution, then with an aqueous 0.1 N sodium hydroxide solution containing 100 g per liter of sodium chloride, dried, treated with activated charcoal, filtered, concentrated to dryness under reduced pressure and in this way isolated 15.5 g of 2-cyano-

20 3- (diethoxy-phosphoryloxy) -5-n-butoxy-thiophene, τι ~ - 1,500.

P % 9.2 9.0

2-cyano-3- (dimethoxyphosphoryloxy) -5-n-butoxy-thiophene

7.7 g of potassium carbonate and 7.7 g of 0,0-dimethylchlorophosphate are introduced into a solution of 11 g of 2-cyano-3-hydroxy-5-n-butoxy thiophene in 150 cnr acetonitrile, and the mixture is stirred for 16 hours at 20 ⁰ C, filtered, concentrated under reduced pressure ", add ether to the residue, wash the ethereal solution with water containing 100 g sodium chloride per liter and with an aqueous 0.1 N sodium hydroxide solution containing 100 g sodium chloride per liter, dry, treat with activated charcoal, filtered, concentrated to dryness and obtained 12.5 g of 2-cyano-5- (dimethoxyphosphoryloxy) -5-n-butoxy-thiophene, n ^ ⁰ = 1.511.

Analysis: ^C 13 ^H 20 NO ₅ hp 6, 05 N % 4, 2 calc .: C % 46.85 H % 6, 1 4, 1 found: 47.0 Example 24

Analysis: % c _v s t 30th ber .: C 43, 5, 28 found: 25th 43 .. 5, 4th example insecticides , H ₁₆ NO ₅ P composition .28 H % , 7

N % 4.59 P % 10.15 4.6 9.6

An emulsifiable concentrate was prepared which, based on weight, contained 15% 2-cyano-3- (dimethoxyphosphoryloxy) -5-methyl-thiophene (compound A), 6.4% Atlox 4851 (oxyäthylenated

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Triglyceride combined with a sulfonate, acid number: 1.5), 3.2 % Atlox 4855 (oxyethylene triglyceride combined with a sulfonate, acid number: 3) and 75.4 % xylene.

Example 26 Acaricidal composition

An emulsifiable concentrate was produced which, based on the weight, contained 25 % 2-cyano-3- (dimethoxyphosphoryloxy) -5-methylthiophene (compound A), 6.4 % Atlox 4851 (oxyethylene triglyceride combined with a sulfonate, acid number: 1, 5), 3.2 % Atlox 4855 (oxyethylene triglyceride combined with a sulfonate, acid number: 3) and 65.4 % xylene.

Example 27 Nematocidal composition

An emulsifiable concentrate for the treatment of the soil was prepared which, based on weight, contained 45 % 2-cyano-3- (dimethoxyphosphoryloxy) -5-methyl-thiophene (compound A), 6.4 % Atlox 4851 (oxyethylene triglyceride combined with a sulfonate, acid number: 1.5), 3.2 % Atlox 4855 (oxyethylene triglyceride combined with a sulfonate, acid number: 3) and 45.4 % xylene.

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Investigation of the insecticides !! Activity of 2-cyano-3) - (dimethoxyphosphoryloxy) -5-roethyl-thiophene (compound A) and 2-cyano- ^ - (dimethQxyphosphoryloxy ^ S-methoxy-thiophene (compound B)

a) Drosophila test (Drosophila melanogaster)

This test determines the activity in relation to the vapor, it passes by placing the insects in a petri dish of 10 cm diameter, which is covered by a tergal veil (terylene fiber veil) is connected to a crystallization vessel of the same diameter, in which you put the compound in acetone solution, which you evaporated before introducing the insects. Three experiments are carried out with different concentrations and uses 25 individuals per concentration (adult individuals of at least 48 hours). The results are expressed as percent mortality after 1 hour, 4 hours and 6 hours. The following table shows the experimental results obtained:

Concentrations in
ppm 500 50 5 Connection A 1 H.
4 hours
6 hours 100
100
100 100
100
100 40
100
100 Connection B 1 H.
4 hours
6 hours 40
100
100 29
100
100 0
82
96 b) Blattella germanica test

This test is carried out by topical application. Adult male individuals of Blattella germanica are given 2 microliters of acetone solution of the product to be tested between the second and third pairs of legs. After the treatment, the “test insects” are kept in the penumbra at 20 ^° C

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- 45 5 - 65 10 - 100 30th 100 95 0 100 95 15th 100 95 35

and nourishes. The controls are carried out 24 hours, 48 hours and 6 days after the treatment.

The experimental results, expressed as a percentage Mortality rates are given in the table below:

Concentrations in

ppm 5000 1250 62.5

24 hours

Connection A 48 hours

6 days

24 hours

Connection B 48 hours

6 days

c) Sitophilus granarius test

This test is carried out by topical application. Man produces acetone solutions of compound A corresponding to 500 or 500 mg of active ingredient per liter.

0.2 microliters of the acetone solution of the compounds are added A and B on the ventral thprax of sitophilus granarius.

This test is carried out on 50 individuals per concentration and per product.

Determine the individuals remaining alive and those who were killed at different times.

The activity of the compounds is expressed in the percentage mortality expressed as a function of time. The results are

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the following: Concentrations in
ppm 5000 500 4 hours
24 hours
5 days 100
100
100 90
90
100 Connection A 4 hours
24 hours
5 days 100
100
100 49
100
100 Connection B d) Musca domestica test

This test is carried out by topical application. The flies get 1. Microliter aoetonic solution of the product to be examined on the back thorax after they have been anesthetized with ether. The insects are kept at 20 ^° C. and 50 % relative humidity. They are fed with milk and water. The controls are carried out 1 hour and then 24 hours after the treatment.

The experimental results, expressed as a percentage Mortality rates are given in the table below:

A. Concentrations in
ppm 2500 500 100 50 link B. 1 H.
24 hours - 100
100 100
100 95
95 link 1 H.
24 hours 100
100 100
100 87 79
92

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e.) Aphis fabae test

It is an experiment carried out outdoors using ParzeHai. Each broad bean parcel with a size of 56O χ 120 cm contains four rows of beans. After this one the natural infection by Aphis fabae for sufficient -. found, the aqueous solution containing the insecticide was atomized Solution over each of the parcels. Two plots (= 2 repetitions) are used per dose of the product. Treatment will performed using 2 liters of insecticidal broth per unit cell. The population controls are 1 hour before the Treatment and then carried out 1 day, 1 week, 2 weeks and 5 weeks after the treatment.

The determination is carried out according to classes:

0a / 0 live aphids per colony;

1ΟΊ - 50 live aphids per colony; 2 rj 50-150 live aphids per colony; 5A / 150 - 500 live aphids per colony; 4 ^ J y 500 live aphids per colony;

Identify 20 plants in each of the two rows.

The experimental results are given in the table below (compound A at 50 g / hl):

Compound A comparison.

average number of average number borrowed determinants. Aphids borrowed determiners mung mung sheet

1 hour before
attempt 1.47 84.8 1.5 1.55 101.8 24 hours after .... 0 0 15.6 1.89 151.5 1 week.... 0.14 2.95 0.84 5.52 514.5

5 weeks . 2.28 i40.9 2.26 197.0

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f) Systemic test on bean stalks (using Aphis fabae):

The plant stalks of Vicia fabae with a height of approx. 30 cm are covered with hydrophilic cotton over a length of wrapped around 5 cm. The cotton itself is covered with a plastic cover to prevent the product from working properly to avoid via the vapor phase. With the help of a syringe, a volume of 2 ml of aqueous insecticidal solution with concentrations of 0.1 and 1 g / l are injected into the "bandage" thus produced. Three bean plants are used per concentration. Each plant is then infected with a colony of approximately 20 to 25 adult apterous individuals of Aphis fabae. the Mortality of the insects will be 1 and 2 days after the infection and their possible offspring a week afterwards certainly. Insect mortality is thus necessarily due to product transfer from the stem the leaves.

The following table shows the experimental results obtained with compound A:

g / l % Effectiveness 48 hours observed offspring
1 week after treatment 1 24 hours 100 no offspring 0.1 88.6 48.7 no offspring 41.4

Conclusions;

The compounds A and B have an interesting insecticidal Activity in the species studied. The systemic activity of compound A on bean plants with respect to Aphis fabae is Particularly noteworthy as the systemic insecticides represent a category of particularly useful insecticides.

609835/107 2

Investigation of the acaricidal activity of 2-cyano-j5- (dimethoxyphosphoryloxy) -5-methyl-thiophene (compound A) on Tetranychus urticae

1) Qvicidal Trial;

One uses bean leaves. That with 10 Tetranychus urticae females each leaf is infected and covered with bird glue on their periphery. The females are left for 24 hours. Lay eggs, take them away and divide the leaves that have become infected with eggs into two groups.

a) A first group is treated with compound A. One atomizes 0.5 cnr of an aqueous solution on each leaf, whereby one uses concentrations of 50 and 10 mg of compound A per liter.

b) A second group of leaves is not dealt with and serves as a comparison group.

The living eggs are determined 9 days after the start of treatment. The results are in percent mortality Eggs expressed and indicated in the following table:

used product concentration in mg / 1 percentage mortality
speed 3
4th Connection A 50
10 54,
45, 9 comparison 0 9,

2) killing the adult animals

Bean leaves are used which are attacked by 25 mites per leaf and which are coated on the periphery with bird glue. The so Bean leaves infected with mites are divided into two groups:

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a) A first group is treated with compound A. 2.5 cnr of an aqueous solution of compound A are atomized Leaf, taking concentrations of 50, 10 and 1 mg per liter used.

b) A second group of leaves or comparison group is not dealt with.

The determination of the living mites takes place 48 hours after the atomization.

The results obtained are given in percentage mortality in the following table:

used product concentration in mg / 1 percentage mortality
speed Connection A 50
10 94.0
. 54.6 comparison 0 5.0

3) Attempt to kill larvae

The procedure is analogous to that in the ovicidal experiment, but the control is carried out 9 days after the treatment. to give the insects a time to develop.

The results obtained are expressed in percentage mortality and are given in the following table:

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- 50 - percentage deaths
opportunity used product Concentration in mg / 1 100
86.6 Connection A 50
10 12.5 comparison -

These experiments show that compound A has a good acaricidal action on Tetranychus urticae.

Investigation of the nematocidal effects of 2-cyano-3- (dimethoxyphosphoryloxy) -5-methyl-thiophene (compound A)

Panagrellus silusae test

One brings nematodes (approx. 2000) in suspension in 0.5 cm ^ of water. One adds to this Suspension 10 cm of an aqueous solution of the insecticide with Concentrations of 1 or 0.1 g / l. Perform three repetitions per concentration.

After 24 hours, the aqueous medium is homogenized and removed 1 ml and determines the living and dead nematodes on a plate from Peter.

The results are given as the percentage mortality in relation to the untreated control individuals.

The experimental results obtained for compound A are given in the following table:

dose 0 in g / l percentage mortality 0 ,1 94.7 , 01 21.4

Conclusions:

Compound-A has interesting nematocidal activity

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Claims (8)

Claims 1. j) Compounds of the formula I U) wherein R. is an alkyl radical having 1 to 4 carbon atoms, R _{2 is} an alkyl radical having 1 to 4 carbon atoms, an alkyloxy radical having 1 to 4 carbon atoms, a radical -N ^^ _H , wherein R 'and R "are a hydrogen atom or an alkyl radical Represent 1 to 4 carbon atoms, R means a cyano group, an alkyloxycarbonyl group having 2 to 4 carbon atoms, a group -Cj-Z, in which Z is an alkyl radical having 1 to 4 carbon atoms or a phenyl radical, R _{2 is} an alkyl radical having 1 to 6 carbon atoms, an alkyloxy radical having 1 to 6 carbon atoms, an alkylthio radical having 1 to 6 carbon atoms, a phenyl radical, a morpholinyl or piperidinyl radical or an alkyloxycarbonyl radical having 2 to carbon atoms and X is an oxygen or sulfur atom. 2.) Compounds of the formula I according to claim 1, wherein R _{1 is} an alkyl radical having 1 to 4 carbon atoms, Rp is an alkyloxy radical having 1 to 4 carbon atoms, X is an oxygen atom, R- is a cyano group, R ₁ . denotes an alkyl radical having 1 to 6 carbon atoms or an alkyloxy radical having t to 6 carbon atoms. 3.) 2-cyano-3- (dimethoxyphosphoryloxy) -5-methyl-thiophene. 4.) 2-cyano-5- (dimethoxyphosphoryloxy) -5-methoxy-thiophene. 609835/1072 5.) 2-cyano-3- (dimethoxythiophosphoryloxy) -5-ethylthio-thiophene. 6.) Process for the preparation of compounds of formula I according to claim 1, characterized in that one is with a Compound of formula II OH (II) wherein R, and R ₂ , the meaning given in claim 1 be seated, the phosphorus compound of the formula III wherein R., Rp and X are as defined in claim 1 sit, implement. 7.) Insecticidal, acaricidal or nematocidal composition, characterized in that it has at least one active ingredient the compounds according to claim 1 contains. 8.) Insecticidal, acaricidal or nematocidal composition, characterized in that it has at least one active ingredient the compounds according to claim 2 contains. 9) insecticidal, acaricidal or nematocidal composition, characterized in that it contains at least one of the compounds according to claims 3, 4 or 5 as active ingredient. 609835/1072