Novel 3-(phosphoryloxy) or (phosphonyloxy)-thiophenes of the formula ##STR1## wherein R is alkyl of 1 to 4 carbon atoms, R.sub.1 is selected from the group consisting of alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms and ##STR2## wherein R' and R" are individually selected from the group consisting of hydrogen and alkyl of 1 to 4 carbon atoms, R.sub.2 is selected from the group consisting of cyano, alkoxy carbonyl of 2 to 4 carbon atoms and ##STR3## wherein Z is selected from the group consisting of phenyl and alkyl of 1 to 4 carbon atoms, R.sub.3 is selected from the group consisting of alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, alkylthio of 1 to 6 carbon atoms, phenyl, morpholino, piperidinyl and alkoxy carbonyl of 2 to 4 carbon atoms and X is selected from the group consisting of oxygen and sulfur having pesticidal properties and their preparation.

STATE OF THE ART 
Commonly assigned U.S. application Ser. No. 357,820 filed May 7, 1973 
describes 3-phosphoryloxy-isothiazoles as having insecticidal and 
acaricidal properties. 
OBJECTS OF THE INVENTION 
It is an object of the invention to provide the novel 3-phosphoryloxy and 
(phosphonyloxy)-thiophenes of formula I and to provide a process for their 
preparation. 
It is another object of the invention to provide novel pesticidal 
compositions and to provide a novel process for killing pests, 
particularly insects, nematodes and acariens. 
These and other objects and advantages of the invention will become obvious 
from the following detailed description. 
THE INVENTION 
The novel 3-(phosphoryloxy) and (phosphonyloxy)thiophenes of the invention 
have the formula 
##STR4## 
wherein R is alkyl of 1 to 4 carbon atoms, R.sub.1 is selected from the 
group consisting of alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon 
atoms and 
##STR5## 
wherein R' and R" are individually selected from the group consisting of 
hydrogen and alkyl of 1 to 4 carbon atoms, R.sub.2 is selected from the 
group consisting of cyano, alkoxy carbonyl of 2 to 4 carbon atoms and 
##STR6## 
wherein Z is selected from the group consisting of phenyl and alkyl of 1 
to 4 carbon atoms, R.sub.3 is selected from the group consisting of alkyl 
of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, alkylthio of 1 to 6 
carbon atoms, phenyl, morpholino, piperidinyl and alkoxy carbonyl of 2 to 
4 carbon atoms and X is selected from the group consisting of oxygen and 
sulfur. 
Suitable examples of R and R.sub.1 are methyl, ethyl and straight or 
branched chain propyl or butyl while R.sub.1 may further be methoxy, 
ethoxy, branched or straight chain propoxy or butoxy, amino, methylamino, 
ethylamino, propylamino, isopropylamino, butylamino, dimethylamino, 
diethylamino, dipropylamino or dibutylamino. Suitable examples of R.sub.2 
are cyano, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, 
butoxycarbonyl, acetyl, propionyl, butyryl or benzoyl and suitable 
examples of R.sub.3 are methyl, ethyl, straight or branched-chain propyl 
or butyl or pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy, methylthio, 
ethylthio, propylthio, butylthio, phenyl, morpholino, piperidinyl, 
methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl or butoxycarbonyl. X is 
either oxygen or sulfur. 
Among the preferred compounds of formula I, R is alkyl of 1 to 4 carbon 
atoms, R.sub.1 is alkoxy of 1 to 4 carbon atoms, R.sub.2 is cyano, R.sub.3 
is alkyl of 1 to 6 carbon atoms or alkoxy of 1 to 6 carbon atoms and X is 
oxygen. 
The novel process of the invention for the preparation of thiophenes of 
formula I comprises reacting a thiophene of the formula 
##STR7## 
wherein R.sub.2 and R.sub.3 have the above definitions with a phosphorus 
reactant of the formula 
##STR8## 
wherein X, R and R.sub.1 have the above definitions. The reaction is 
preferably effected in an organic solvent such as acetone, acetonitrile, 
dimethylformamide or tetrahydrofuran and in the presence of a basic agent 
such as potassium carbonate, sodium hydride or triethylamine. 
The starting materials of formula II are described in the literature or can 
be made by known procedures. For example, 
2-cyano-3-hydroxy-5-methyl-thiophene and 
2-cyano-3-hydroxy-5-phenyl-thiophene are described by Hedegaard et 
al/Tet., Vol. 27 (1971), p. 3853 and p. 3858/, 
2,5-dicarbomethoxy-3-hydroxy-thiophene is described by Fiesselmann et 
al/Ber., Vol. 89 (1936), p. 1897/, 
2-methoxycarbonyl-3-hydroxy-5-methyl-thiophene is described by Jacobsen et 
al/Tet., Vol. 21 (1965), p. 3331/ and 
2-benzoyl-3-hydroxy-5-methoxythiophene and 
2-methoxy-carbonyl-3-hydroxy-5-methoxy-thiophene have been described by 
Raap/Can. J. Chem., Vol. 46 (1968), p. 2255-58/, 
2-cyano-3-hydroxy-5-methoxy-thiophene, 
2-cyano-3-hydroxy-5-(N-morpholino)-thiophene, 
2-cyano-3-hydroxy-5-ethylthio-thiophene, 
2-cyano-3-hydroxy-5-n-butoxy-thiophene and 
2-cyano-3-hydroxy-5-n-propyl-thiophene can be made by known procedures 
such as illustrated in the examples. 
The novel pesticidal compositions of the invention are comprised of an 
effective amount of at least one compound of formula I and an inert 
carrier. The compositions may be in the form of powders, granules, 
suspensions, emulsions or solutions containing the active ingredient 
admixed, for example, with a vehicle and/or a cationic, anionic, or 
nonionic surface active agent to ensure a uniform dispersion of the 
substances in the compositions. The vehicle may be a liquid such as water, 
alcohols, hydrocarbon or other organic solvents, a mineral, animal or 
vegetable oil or a powder such as talc, clays, silicates or kieselguhr. 
The liquid or powder compositions for foliar spraying preferably contain 10 
to 80% by weight of the active material when used for insecticidal 
purposes and 20 to 80% by weight of the active material when used for 
acaricidal purposes. The liquids or powders used to treat soil for 
nematocidal purposes preferably contain 20 to 80% by weight of active 
material. 
The novel method of the invention for combatting pests comprises contacting 
the pests with a lethal amount of at least one compound of formula I.

In the following examples there are described several preferred embodiments 
to illustrate the invention. However, it should be understood that the 
invention is not intended to be limited to the specific embodiments. 
EXAMPLE 1 
2-cyano-3-(dimethoxyphosphoryloxy)-5-methyl-thiophene 
14 g of potassium carbonate and 8.9 ml of 0,0-dimethyl chlorophosphate were 
added to a solution of 14 g of 2-cyano-3-hydroxy-5-methyl-thiophene in 300 
ml of acetone and the mixture was stirred for 15 hours at 20.degree. C. 
and was evaporated to dryness. The residue was added to water and the 
aqueous phase was extracted with ether. The ether extracts were washed 
with 0.1N sodium hydroxide, dried, treated with activated carbon and was 
filtered. The filtrate was evaporated to dryness to obtain 12 g of product 
which was chromatographed over silica gel. The product was eluted with an 
8-2 cyclohexane-ethyl acetate mixture and was washed with 0.1N sodium 
hydroxide to obtain a microanalytical sample of 
2-cyano-3-(dimethoxyphosphoryloxy)-5-methyl-thiophene with a refractive 
index n.sub.D.sup.20 = 1.5165. 
Analysis: C.sub.8 H.sub.10 NO.sub.4 PS. Calculated: %C, 38.86; %H, 4.08; 
%N, 5.67; %P 12.53. Found: %C, 39.5; %H 4.2; %N, 5.7; %P, 12.2. 
EXAMPLE 2 
2-cyano-3-(dimethoxythiophosphoryloxy)-5-methyl-thiophene 
11.2 g of potassium carbonate and 12.8 g of 0,0-dimethyl 
chlorothiophosphate were added to a solution of 11.2 g of 
2-cyano-3-hydroxy-5-methyl-thiophene in 200 ml of acetone and the mixture 
was stirred for 15 hours at 20.degree. C. and was then filtered. The 
filtrate was evaporated to dryness and the residue was chromatographed 
over silica gel. Elution with a 7-3 cyclohexane-ethyl acetate mixture 
yielded 18.7 g of 
2-cyano-3-(dimethoxythiophosphoryloxy)-5-methyl-thiophene with a 
refractive index of n.sub.D.sup.20 = 1.539. 
Analysis: C.sub.8 H.sub.10 NO.sub.3 PS.sub.2. Calculated: %C, 36.50; %H, 
3.84; %N, 5.32; %P 11.76. Found: %C, 36.4; %H 4.0; %N, 5.4; %P, 11.4. 
EXAMPLE 3 
2-cyano-3-diethoxythiophosphoryloxy)-5-methyl-thiophene 
7 g of potassium carbonate and 9.5 g of 0,0-diethylchlorothiophosphate were 
added to a solution of 7 g of 2-cyano-3-hydroxy-5-methyl-thiophene in 100 
ml of acetone and the mixture was stirred for 15 hours at 20.degree. C. 
and was then filtered. The filtrate was evaporated to dryness and the 
residue was chromatographed over silica gel. Elution with an 8-2 
cyclohexane-ethyl acetate mixture yielded 11.2 g of 
2-cyano-3-(diethoxythiophosphoryloxy)-5-methyl-thiophene with a refractive 
index of n.sub.D.sup.20 = 1.534. 
Analysis: C.sub.10 H.sub.14 NO.sub.3 PS.sub.2. Calculated: %C, 41.23; %H, 
4.85; %N, 4.81; %P, 10.63. Found: %C, 41.5; %H, 4.9; %N, 4.7; %P, 10.5. 
EXAMPLE 4 
2-cyano-3-(dimethoxyphosphoryloxy)-5-methoxy-thiophene 
STEP A: methyl 2-ethoxycarbonylimido acetate hydrochloride 
Hydrochloric gas was bubbled through a solution of 45.2 g of ethyl 
cyanacetate in 400 ml of ethyl ether at 20.degree. C. until 20 g had been 
absorbed and 12.8 g of methanol were added thereto. The mixture was 
stirred at 20.degree. C. for 8 hours and was then vacuum filtered. The 
recovered crystals were washed with ether to obtain 39 g of methyl 
2-ethoxycarbonylimido acetate hydrochloride melting at 95.degree. to 
100.degree. C. The product was used as is for the next step but a dried 
sample of the product had a melting point of 100.degree.-105.degree. C. 
(with decomposition). 
STEP B: 0-methyl 2-ethoxycarbonyl-thioacetate 
250 ml of pyridine at 0.degree. C. were saturated with hydrogen sulfide and 
after the addition of 39 g of the product of Step A thereto, the hydrogen 
sulfide was bubbled through the mixture for 2 hours at 0.degree. C. The 
mixture was then stirred at room temperature for 6 hours and the reaction 
mixture was poured over ice. The mixture was acidified to a pH of 3 with 
concentrated hydrochloric acid and was extracted with methylene chloride. 
The organic extracts were dried and filtered and the filtrate was 
evaporated to dryness. The residue was rectified to obtain 31 g of 
0-methyl 2-ethoxycarbonyl thioacetate with a boiling point of 79.degree. 
C. at 5 mm Hg. 
STEP C: 2-cyano-3-hydroxy-5-methoxy-thiophene 
81 g of 0-methyl 2-ethoxycarbonyl-thioacetate and then 38 g of acetonitrile 
were added to a solution of 27 g of sodium methylate in 250 ml of methanol 
and the mixture was refluxed for one hour. A solution of 27 g of sodium 
methylate in 100 ml of methanol were added to the reaction which was 
cooled to 20.degree. C. and concentrated to dryness. The residue was 
dissolved in water and the solution was washed with ether, acidified with 
concentrated hydrochloric acid and was vacuum filtered. The recovered 
crystals were dried to obtain 42 g of 
2-cyano-3-hydroxy-5-methoxy-thiophene with a melting point of 
138.degree.-140.degree. C. A microanalytically pure sample obtained by 
crystallization from isopropyl ether melted at 140.degree. C. 
Analysis: C.sub.6 H.sub.5 NO.sub.2 S. Calculated: %C, 46.44; %H, 3.25; %N, 
9.03; %S, 20.67. Found: %C, 46.5; %H, 3.02; %N, 8,7; %S, 20.5. 
STEP D: 2-cyano-3-(dimethoxyphosphoryloxy)-5-methoxy-thiophene 
8.4 g of potassium carbonate and 7.1 g of 0,0-dimethyl-chlorophosphate were 
added to a solution of 9.3 g of 2-cyano-3-hydroxy-5-methoxy-thiophene in 
100 ml of acetonitrile and after stirring for 16 hours, the mixture was 
filtered. The filtrate was evaporated to dryness and the residue was taken 
up in ether. The ether phase was washed with water and 0.1 sodium 
hydroxide and dried. The ether phase was evaporated to dryness to obtain 
12 g of 2-cyano-3-(dimethoxyphosphoryloxy)-5-methoxy-thiophene with a 
refraction index of n.sub.D.sup.20 = 1.523. 
Analysis: C.sub.8 H.sub.10 NO.sub.5 PS. Calculated: %C, 36.52; %H, 3.83; 
%N, 5.32; %P, 11.76. Found: %C, 36.8; %H, 4.0; %N, 5.6; %P 11.5. 
EXAMPLE 5 
2-cyano-3-(dimethoxyphosphoryloxy)-5-(N-morpholino)-thiophene 
STEP A: 2-cyano-3-hydroxy-5-(N-morpholino)-thiophene 
40.6 g of methyl N-(morpholinothio-carbonyl)-acetate [Raap, Can. J. Chem., 
Vol. 46 (1968), p. 2255] were added in small fractions to a mixture of 500 
ml of tetrahydrofuran and 10 g of a suspension of 50% of sodium hydride in 
mineral oil and the mixture was allowed to stand at 20.degree. C. for 2 
hours. Then, a solution of 15.5 g of chloroacetonitrile in 500 ml of 
tetrahydrofuran followed by 500 ml of methanol were added to the reaction 
mixture which was stirred for 3 hours at 20.degree. C. A solution of 14 g 
of potassium methylate in 300 ml of methanol was added thereto and the 
mixture was stirred for 3 hours at 20.degree. C. The mixture was 
evaporated to dryness and the residue was dissolved in water. The solution 
was washed with ethyl acetate, was acidified with acetic acid, 
refrigerated and then vacuum filtered. The recovered crystals were washed 
with water and dried to obtain 22 g of 
2-cyano-3-hydroxy-5-N-morpholino-thiophene melting at 
180.degree.-182.degree. C. 
Analysis: C.sub.9 H.sub.10 N.sub.2 O.sub.2 S. Calculated: %C, 51.41; %H, 
4.80; %N, 13.32; %S, 15.25. Found: %C, 51.1; %H, 4.9; %N, 13.2; %S, 15.2. 
STEP B: 2-cyano-3-(dimethoxyphosphoryloxy)-5-(N-morpholino)-thiophene 
4.2 g of potassium carbonate and 4.3 g of 0,0-dimethyl chlorophosphate were 
added to a solution of 6.3 g of 
2-cyano-3-hydroxy-5-(N-morpholino)-thiophene in 125 ml of acetonitrile and 
the mixture was stirred for 8 hours at 20.degree. C. and then was 
filtered. The filtrate was evaporated to dryness and the residue was 
dissolved in ethyl acetate. The solution was washed with water and 0.1N 
sodium hydroxide, dried, treated with activated carbon, filtered and 
evaporated to dryness. The residue was crystallized from a 10-2 ethyl 
ether-ethyl acetate mixture to obtain 8 g of 
2-cyano-3-(dimethoxyphosphoryloxy)-5-(N-morpholino)-thiophene melting at 
80.degree. C. 
Analysis: C.sub.11 H.sub.15 N.sub.2 O.sub.5 PS. Calculated: %C, 41.51; %H, 
4.75; %N, 8.80; %P, 9.73. Found: %C, 41.6; %H, 4.8; %N, 8.8; %P, 9.7. 
EXAMPLE 6 
2-cyano-3-(dimethoxythiophosphoryloxy)-5-phenyl-thiophene 
7 g of potassium carbonate and 8 g of 0,0-dimethyl chlorothiophosphate were 
added to a solution of 10.5 g of 2-cyano-3-hydroxy-5-phenyl-thiophene in 
120 ml of acetone and the mixture was stirred at 20.degree. C. for 15 
hours and was then filtered. The filtrate was evaporated to dryness and 
the crystal residue was empasted with petroleum ether. The crystals were 
then crystallized from isopropyl ether to obtain 12.8 g of 
2-cyano-3-(dimethoxythiophosphoryloxy)-5-phenylthiophene melting at 
95.degree. C. 
Analysis: C.sub.13 H.sub.12 NO.sub.3 PS.sub.2. Calculated: %C, 48.00; %H, 
3.71; %N, 4.31; %P, 9.52. Found: %C, 48.2; %H, 3.9; %N, 4.4; %P, 9.4. 
EXAMPLE 7 
2,5-dicarbomethoxy-3-(dimethoxythiophosphoryloxy)-thiophene 
14 g of potassium carbonate and 16 g of 0,0-dimethylchlorothiophosphate 
were added to a solution of 21.6 g of 
2,5-dicarbomethoxy-3-hydroxy-thiophene in 500 ml of acetone and the 
mixture was stirred for 15 hours at 20.degree. C. and then was filtered. 
The filtrate was evaporated to dryness and the crystal residue was 
empasted with petroleum ether, iced and vacuum filtered. The crystals were 
washed with petroleum ether and were crystallized from methanol to obtain 
21 g of 2,5-dicarbomethoxy-3-dimethoxythiophosphoryloxy-thiophene melting 
at 71.degree. C. 
Analysis: C.sub.10 H.sub.13 O.sub.7 PS.sub.2. Calculated: %C, 35.30; %H, 
3.85; %P, 9.10. Found: %C, 35.4; %H, 3.9; %P, 9.1. 
EXAMPLE 8 
2,5-dicarbomethoxy-3-(dimethoxyphosphoryloxy)-thiophene 
5.6 g of potassium carbonate and 5.7 g of 0,0-dimethyl-chlorophosphate were 
added to a solution of 8.6 g of 2,5-dicarbomethoxy-3-hydroxy-thiophene in 
100 ml of acetone and the mixture was stirred for 15 hours at 20.degree. 
C. and was filtered. The filtrate was evaporated to dryness and the 
residue was dissolved in ethyl ether. The organic solution was washed with 
0.1N sodium hydroxide, dried and concentrated to dryness. The residue was 
crystallized from ethyl ether to obtain 5.2 g of 
2,5-dicarbomethoxy-3-(dimethoxyphosphoryloxy)-thiophene melting at 
60.degree. C. 
Analysis: C.sub.10 H.sub.13 O.sub.8 PS. Calculated: %C, 37.13; %H, 4.03; 
%P, 9.51. Found: %C, 37.4; %H, 4.1; %P, 9.4. 
EXAMPLE 9 
2,5-dicarbomethoxy-3-(diethoxythiophosphoryloxy)-thiophene 
7 g of potassium carbonate and 8.9 g of 0,0-diethyl chlorothiophosphate 
were added to a solution of 10.9 g of 
2,5-dicarbomethoxy-3-hydroxy-thiophene in 500 ml of acetone and the 
mixture was stirred for 15 hours at 20.degree. C. and was then filtered. 
The filtrate was evaporated to dryness and the residue was empasted with a 
10-1 petroleum ether-isopropyl ether mixture. The mixture was vacuum 
filtered and the precipitate was crystallized from ethanol to obtain 8.5 g 
of 2,5-dicarbomethoxy-3-(diethoxythiophosphoryloxy)-thiophene melting at 
50.degree. C. 
Analysis: C.sub.12 H.sub.17 O.sub.7 PS.sub.2. Calculated: %C, 39.12; %H, 
4.65; %P, 8.41. Found: %C, 39.4; %H, 4.9; %P, 8.4. 
EXAMPLE 10 
2-carbomethoxy-3-(diethoxythiophosphoryloxy)-5-methyl-thiophene 
4.7 g of a 60% suspension of sodium hydride in mineral oil were slowly 
added to a solution of 20 g of 
2-methoxycarbonyl-3-hydroxy-5-methyl-thiophene in 200 ml of 
dimethylformamide and after stirring the mixture for 1 hour at 20.degree. 
C., a solution of 22.4 g of O,O-diethyl-chlorothiophosphate in 50 ml of 
dimethylformamide was rapidly added thereto. The mixture was stirred for 
15 hours at 20.degree. C. and the resulting suspension was poured over a 
mixture of ice and water. The mixture was extracted with ether and the 
extracts were dried and concentrated to dryness. The residue was 
chromatographed over silica gel and elution with a 9-1 cyclohexane-ethyl 
acetate mixture gave 11.5 g of 
2-carbomethoxy-3-(diethoxy-thiophosphoryloxy)-5-methyl-thiophene with a 
refractive index of n.sub.D.sup.22 = 1.5272. 
Analysis: C.sub.11 H.sub.17 O.sub.5 PS.sub.2. Calculated: %C, 40.74; %H, 
5.19; %P, 9.55. Found: %C, 40.7, %H, 5.4; %P, 9.0. 
EXAMPLE 11 
2-benzoyl-3-(dimethoxyphosphoryloxy)-5-methoxy-thiophene 
4.2 g of potassium carbonate and 4.3 g of O,O-dimethyl-chlorophosphate were 
added to a solution of 7.9 g of 2-benzoyl-3-hydroxy-5-methoxy-thiophene in 
100 ml of acetonitrile and the mixture was stirred for 16 hours at 
20.degree. C. and was filtered. The filtrate was concentrated to dryness 
and the residue was added to ethyl acetate. The organic solution was 
washed with water and with 0.1N sodium hydroxide solution saturated with 
sodium chloride. The mixture was decanted and the organic phase was dried, 
treated with activated carbon, filtered and evaporated to dryness under 
reduced pressure. The residue was crystallized from ether and vacuum 
filtered to obtain 8.2 g of 
2-benzoyl-3-(dimethoxyphosphoryloxy)-5-methoxy-thiophene melting at 
76.degree. C. 
Analysis: C.sub.14 H.sub.15 O.sub.6 PS. Calculated: %C, 49.12; %H, 4.47; 
%P, 9.05. Found: %C, 49.4; %H, 4.5; %P, 9.0. 
EXAMPLE 12 
2-carbomethoxy-3-(dimethoxyphosphoryloxy)-5-methoxy-thiophene 
7 g of potassium carbonate and 7.2 g of O,O-dimethyl-chlorophosphate were 
added to a solution of 9.5 g of 
2-methoxycarbonyl-3-hydroxy-5-methoxy-thiophene in 125 ml of acetonitrile 
and the mixture was stirred for 16 hours at 20.degree. C. and was 
filtered. The filtrate was evaporated to dryness under reduced pressure 
and the residue was taken up in ethyl acetate. The organic soltuion was 
washed with water and with an 0.1N sodium hydroxide solution saturated 
with sodium chloride. The solution was dried and concentrated to dryness. 
The residue was crystallized from isopropyl ether to obtain 12 g of 
2-carbomethoxy-3-(dimethoxyphosphoryloxy)-5-methoxy-thiophene melting at 
35.degree. C. 
Analysis: C.sub.9 H.sub.13 O.sub.7 PS. Calculated: %C, 36.49; %H, 4.42; %P, 
10.45. Found: %C, 36.7; %H, 4.5; %P, 10.3. 
EXAMPLE 13 
2-cyano-3-(diethoxythiophosphoryloxy)-5-ethylthio-thiophene 
STEP A: 2-cyano-3-hydroxy-5-ethylthio-thiophene 
192 g of ethyl .alpha.-carbethoxy-dithioacetate [Ber., Vol. 100 (1967), p. 
1420] were added at 20.degree. C. to a solution of 70 g of sodium 
methylate in one liter of methanol and after stirring for 5 minutes at 
20.degree. C., 76 g of chloroacetonitrile were added thereto. The mixture 
was stirred for 1 hour at 45.degree. C. and 2 hours at 20.degree. C. and 
after the addition of a solution of 70 g of sodium methylate in 500 ml of 
methanol, the mixture was stirred for 4 hours at 20.degree. C. The mixture 
was evaporated to dryness under reduced pressure and the residue was 
dissolved in water. Toluene was added to the aqueous phase which was then 
acidified by addition of concentrated hydrochloric acid and the organic 
phase was rapidly separated by decanting. The organic phase was iced and 
vacuum filtered and the recovered crystals were dried to obtain 97 g of 
2-cyano-3 -hydroxy-5-ethylthio-thiophene melting at 105.degree. C. A 
microanalytically pure sample after crystallization from benzene melted at 
105.degree. C. 
Analysis: C.sub.7 H.sub.7 NOS.sub.2. Calculated: %C, 45.38; %H, 3.81; %N, 
7.56; %S, 34.6. Found: %C, 45.6; %H, 4.0; %N, 7.5; %S, 34.4. 
STEP B: 2-cyano-3-(diethoxythiophosphoryloxy)-5-ethylthiophene 
7 g of potassium carbonate and 9.4 g of O,O-diethyl chlorothiophosphate 
were added to a solution of 9.3 g of 
2-cyano-3-hydroxy-5-ethylthio-thiophene in 150 ml of acetonitrile and the 
mixture was stirred for 24 hours at 20.degree. C. and was filtered. The 
filtrate was evaporated to dryness and the residue was chromatographed 
over silica gel. Elution with an 8-2 cyclohexane-ethyl acetate mixture 
yielded 14.6 g of 
2-cyano-3-(diethoxythiophosphoryloxy)-5-ethylthio-thiophene with a 
refractive index of n.sub.D.sup.20 = 1.5635. 
Analysis: C.sub.11 H.sub.16 NO.sub.3 PS.sub.3. Calculated: %C, 39.16; %H, 
4.78; %N, 4.15; %P, 9.18. Found: %C, 39.6; %H, 4.9; %N, 4.0; %P, 9.3. 
EXAMPLE 14 
2-cyano-3-(diethoxyphosphoryloxy)-5-ethylthio-thiophene 
7.7 g of potassium carbonate and 8.6 g of O,O-diethyl-chlorophosphate were 
added to a solution of 10.1 g of 2-cyano-3-hydroxy-5-ethylthio-thiophene 
in 150 ml of acetonitrile and the mixture was stirred for 24 hours at 
20.degree. C. and was filtered. The filtrate was concentrated to dryness 
and the residue was dissolved in ether. The ether solution was washed with 
0.1N sodium hydroxide solution, dried, treated with activated carbon, 
filtered and evaporated to dryness to obtain 13 g of 
2-cyano-3-(diethoxyphosphoryloxy)-5-ethylthio-thiophene with a refractive 
index of n.sub.D.sup.20 = 1.538. 
Analysis: C.sub.11 H.sub.16 NO.sub.4 PS.sub.2. Calculated: %C, 41.11; %H, 
5.02; %N 4.36; %P, 9.64. Found: %C, 40.0; %H, 5.0; %N, 4.2; %P, 9.5. 
EXAMPLE 15 
2-cyano-3-(dimethoxyphosphoryloxy)-5-ethylthio-thiophene 
7.7 g of potassium carbonate and 7.7 g of O,O-dimethyl-chlorophosphate were 
added to a solution of 10.1 g of 2-cyano-3-hydroxy-5-ethylthio-thiophene 
in 125 ml of acetonitrile and the mixture was stirred for 8 hours at 
20.degree. C. and was filtered. The filtrate was evaporated to dryness and 
the residue was dissolved in ether. The ether solution was washed with 
water and 0.1N sodium hydroxide solution, dried, treated with activated 
carbon, filtered and evaporated to dryness to obtain 12 g of 
2-cyano-3-(dimethoxyphosphoryloxy)-5-ethylthio-thiophene with a refractive 
index of n.sub.D.sup.20 = 1.5570. 
Analysis: C.sub.9 H.sub.12 NO.sub.4 PS.sub.2. Calculated: %C, 36.85; %H, 
4.12; %N, 4.77; %P, 10.56. Found: %C, 37.1; %H, 4.1; %N, 4.7; %P, 10.3. 
EXAMPLE 16 
2-cyano-3-(dimethoxythiophosphoryloxy)-5-ethylthio-thiophene 
7 g of potassium carbonate and 8 g of O,O-dimethyl-chlorothiophosphate were 
added to a solution of 9.3 g of 2-cyano-3-hydroxy-5-ethylthio-thiophene in 
125 ml of acetonitrile and the mixture was stirred for 24 hours at 
20.degree. C. and was filtered. The filtrate was evaporated to dryness 
under reduced pressure and the residue was chromatographed over silica 
gel. Elution with an 8-2 cyclohexane-ethyl acetate mixture yielded 14 g of 
2-cyano-3-(dimethoxythiophosphoryloxy)-5-ethylthio-thiophene with a 
refractive index of n.sub.D.sup.20 = 1.5825. 
Analysis: C.sub.9 H.sub.12 NO.sub.3 PS.sub.3. Calculated: %C, 34.94; %H, 
3.91; %N, 4.53; %P, 10.01. Found: %C, 34.9; %H, 3.8; %N, 4.4; %P, 9.8. 
EXAMPLE 17 
2-cyano-3-(diethoxyphosphoryloxy)-5-methyl-thiophene 
11.42 g of potassium carbonate were added to a solution of 11.5 g of 
2-cyano-3-hydroxy-5-methyl-thiophene in 80 ml of acetonitrile and after 
stirring the mixture for 5 minutes, 12.08 g of O,O-diethyl-chlorophosphate 
were added thereto. The mixture was stirred for 24 hours at room 
temperature and was filtered. The filtrate was evaporated to dryness and 
the residue was chromatographed over silica gel. The product was eluted 
with a 6-4 cyclohexane-ethyl acetate mixture and was dissolved in ethyl 
acetate. The organic phase was washed with an aqueous sodium hydroxide 
solution and the organic phase was decanted, and concentrated to dryness 
to obtain 13 g of 2-cyano-3-(diethoxyphosphoryloxy)-5-methyl-thiophene 
with a refractive index of n.sub.D.sup.21 = 1.502. 
Analysis: C.sub.10 H.sub.14 NO.sub.4 PS. Calculated: %C, 43.63; %H, 5.12; 
%N, 5.09; %P, 11.25. Found: %C, 43.3; %H, 5.2; %N, 4.9; %P, 11.3. 
EXAMPLE 18 
2-cyano-3-(dimethoxyphosphoryloxy)-5-n-propyl-thiophene 
STEP A: ethyl 3-thioxo-hexanoate 
23.7 g of ethyl 3-oxo-hexanoate were added to 100 ml of ethanol saturated 
with hydrogen chloride gas at -10.degree. C. and then hydrogen sulfide was 
bubbled therethrough for 6 hours at -10.degree. C. The solvent was 
evaporated and the residue was dissolved in ether. The solution was washed 
with water and dried to obtain 25.8 g of ethyl 3-thioxo-hexanoate. 
STEP B: 2-cyano-3-hydroxy-5-n-propyl-thiophene 
A mixture of 77 g of ethyl 3-thioxo-hexanoate, 300 ml of methanol and 28 g 
of potassium methylate was stirred at 20.degree. C. for 15 minutes and 
after the addition of 30.2 g of chloroacetonitrile, thereto, the mixture 
was stirred for another 15 minutes at 20.degree. C. The mixture was 
refluxed for 4 hours and the solvent was then evaporated. The residue was 
dissolved in ether and the ether phase was washed with methylene chloride, 
acidified with concentrated hydrochloric acid and extracted with ethyl 
acetate. The solution was then treated with activated carbon, was dried 
and evaporated to dryness. The residue was dissolved in toluene and the 
solution was iced and vacuum filtered. The recovered crystals were 
crystallized from a 3-1 petroleum ether-benzene mixture to obtain 3.1 g of 
2-cyano-3-hydroxy-5-n-propyl-thiophene melting at 78.degree. C. 
Analysis: C.sub.8 H.sub.9 NOS. Calculated: %C, 57.45; %H, 5.42; %N, 8.37; 
%S, 19.17. Found: %C, 57.4; %H, 5.3; %N, 8.3; %S, 19.3. 
STEP C: 2-cyano-3-(dimethoxyphosphoryloxy)-5-n-propyl-thiophene 
2.76 g of potassium carbonate were added to a solution of 3.4 g of 
2-cyano-3-hydroxy-5-n-propyl-thiophene in 50 ml of acetonitrile and after 
stirring the mixture for 5 minutes at 20.degree. C., 2.6 g of 
O,O-dimethyl-chlorophosphate were added. The mixture was stirred for 20 
hours at 20.degree. C. and then filtered. The filtrate was evaporated to 
dryness and the residue was taken up in ethyl acetate. The solution was 
washed with 0.01N sodium hydroxide solution, was dried and concentrated to 
dryness to obtain 5 g of 
2-cyano-3-(dimethoxyphosphoryloxy)-5-n-propyl-thiophene with a refractive 
index of n.sub.D.sup.23.5 = 1.507. 
Analysis: C.sub.10 H.sub.14 NO.sub.4 PS. Calculated: %C, 43.63; %H, 5.12; 
%N, 5.09; %P, 11.25. Found: %C, 43.60; %H, 5.4; %N, 4.9; %P, 10.9. 
EXAMPLE 19 
2-cyano-3-(ethoxy methylthiophosphonyloxy)-5-methyl-thiophene 
14 g of potassium carbonate and 15.9 g of chloro (O-ethylphosphothionate) 
were added to a solution of 14 g of 2-cyano-3-hydroxy-5-methyl-thiophene 
in 150 ml of acetonitrile and the mixture was stirred for 24 hours at 
20.degree. C. and was then filtered. The filtrate was evaporated to 
dryness and the residue was chromatographed over silica gel. Elution with 
an 85-15 cyclohexane-ethyl acetate mixture yielded 19 g of 
2-cyano-3-(ethoxymethyl thiophosphonyloxy)-5-methyl-thiophene with a 
refractive index of n.sub.D.sup.20 = 1.5570. 
Analysis: C.sub.9 H.sub.12 NO.sub.2 PS.sub.2. Calculated: %C, 41.37; %H, 
4.63; %N, 5.36; %P, 11.85. Found: %C, 41.3; %H, 4.7; %N, 5.3; %P, 11.6. 
EXAMPLE 20 
2-cyano-3-(ethoxy-N-isopropylthiophosphoramidoxy)-5-methyl-thiophene 
14 g of potassium carbonate and 19 g of O-ethyl 
N-isopropyl-chlorothiophosphoramidate were added to a solution of 14 g of 
2-cyano-3-hydroxy-5-methyl-thiophene in 150 ml of acetonitrile and the 
mixture was stirred for 24 hours at 20.degree. C. and was then filtered. 
The filtrate was evaporated to dryness and the residue was chromatographed 
over silica gel. Elution with an 85-15 benzene-petroleum ether mixture 
yielded 23 g of 
2-cyano-3-(ethoxy-N-isopropylthiophosphoramidoxy)-5-methyl-thiophene with 
a refractive index of n.sub.D.sup.20 = 1.544. 
Analysis: C.sub.11 H.sub.17 N.sub.2 O.sub.2 PS.sub.2. Calculated: %C, 
43.41; %H, 5.63; %N, 9.20; %P, 10.18. Found: %C, 43.7; %H, 5.8; %N, 8.9; 
%P, 10.4. 
EXAMPLE 21 
2-cyano-3-(diethoxythiophosphoryloxy)-5-n-butoxy-thiophene 
STEP A: butyl 2-ethoxycarbonylimidoacetate hydrochloride 
A hydrogen chloride gas current was bubbled through a solution of 45.2 g of 
ethyl cyanacetate in 29.6 g of butanol until 16 g were absorbed and the 
mixture was then stirred for 18 hours at 15.degree. C. The mixture was 
evaporated to dryness under reduced pressure to obtain 90.5 g of raw butyl 
2-ethoxycarbonylimidioacetate hydrochloride which was used as is for the 
next step. 
STEP B: O-n-butyl 2-ethoxycarbonylthioacetate 
Hydrogen sulfide was bubbled through 400 ml of pyridine until 30 g were 
absorbed and then 90.5 g of butyl 2-ethoxycarbonylthioacetate 
hydrochloride were slowly added thereto at -15.degree. C. The mixture was 
stirred at 20.degree. C. for 24 hours and was then poured over ice. The 
mixture was acidified with concentrated hydrochloric acid and extracted 
with methylene chloride. The organic extracts were dried, filtered and 
concentrated to dryness. The residue was rectified under reduced pressure 
to obtain 62.3 g of O-n-butyl 2-ethoxycarbonylthioacetate with a boiling 
point of 100.degree. C. at 0.4 mm Hg. 
STEP C: 2-cyano-3-hydroxy-5-n-butoxy-thiophene 
205 g of O-n-butyl 2-ethoxycarbonylthioacetate were added at 30.degree. C. 
to a solution of 70 g of potassium methylate in a liter of methanol and 
the mixture was stirred for 10 minutes at 30.degree. C. 75.5 g of 
chloroacetonitrile were added all at once to the mixture which was stirred 
for an hour at 40.degree. C. and then a solution of 70 g of potassium 
methylate in 300 ml of methanol. The mixture was stirred for 6 hours at 
room temperature and was evaporated to dryness. The residue was washed 
with ethyl acetate and ether and was dried. The residue was then dissolved 
in water and the aqueous solution was acidified with concentrated 
hydrochloric acid and was vacuum filtered. The recovered precipitate was 
washed with water, dried and chromatographed over silica gel. Elution with 
6-4 cyclohexane-ethyl acetate yielded 81 g of 
2-cyano-3-hydroxy-5-n-butoxy-thiophene melting at 107.degree. C. 
Analysis: C.sub.9 H.sub.11 NO.sub.2 S. Calculated: %C, 54.80; %H, 5.62; %N, 
7.10; %S, 16.25. Found: %C, 55.1; %H, 5.7; %N, 7.0; %S, 16.3. 
STEP D: 2-cyano-3-(diethoxythiophosphoryloxy)-5-n-butoxy-thiophene 
7 g of potassium carbonate and 9.4 g of O,O-diethyl chlorothiophosphate 
were added to a solution of 9.8 g of 
2-cyano-3-hydroxy-5-n-butoxy-thiophene in 150 ml of acetonitrile and the 
mixture was stirred for 24 hours at 20.degree. C. and was filtered. The 
filtrate was evaporated to dryness under reduced pressure and the residue 
was chromatographed over silica gel. Elution with benzene yielded 14 g of 
2-cyano-3-(diethoxythiophosphoryloxy)-5-n-butoxy-thiophene with a 
refractive index of n.sub.D.sup.20 = 1.525. 
Analysis: C.sub.13 H.sub.20 NO.sub.4 PS.sub.2. Calculated: %C, 44.69; %H, 
5.77; %N, 4.01; %P, 8.85. Found: %C, 44.8; %H, 5.9; %N, 3.9; %P, 8.9. 
EXAMPLE 22 
2-cyano-3-(dimethoxythiophosphoryloxy)-5-n-butoxy-thiophene 
7 g of potassium carbonate and 8 g of O,O-dimethyl chlorothiophosphate were 
added to a solution of 9.8 g of 2-cyano-3-hydroxy-5-n-butoxy-thiophene in 
150 ml of acetonitrile and the mixture was stirred for 24 hours at 
20.degree. C. and was then filtered. The filtrate was evaporated to 
dryness and the residue was chromatographed over silica gel. Elution with 
benzene yielded 11 g of 
2-cyano-3-(dimethoxythiophosphoryloxy)-5-n-butoxy-thiophene with a 
refractive index of n.sub.D.sup.20 = 1.5375. 
Analysis: C.sub.11 H.sub.16 NO.sub.4 PS.sub.2. Calculated: %C, 41.11; %H, 
5.02; %N, 4.37; %P, 9.64. Found: %C, 41.1; %H, 5.0; %N, 4.3; %P, 9.5. 
EXAMPLE 23 
2-cyano-3-(diethoxyphosphoryloxy)-5-n-butoxy-thiophene 
7.7 g of potassium carbonate and 8.6 g of O,O-diethyl chlorophosphate were 
added to a solution of 11 g of 2-cyano-3-hydroxy-5-n-butoxy-thiophene in 
150 ml of acetonitrile and the mixture was stirred for 16 hours at room 
temperature and was then filtered. The filtrate was evaporated to dryness 
and the residue was taken up in ethyl ether. The ether phase was washed 
with an aqueous solution of 100 g/l of sodium chloride and then with an 
aqueous 0.1N sodium hydroxide solution containing 100 g/l of sodium 
chloride. The solution was dried, treated with activated carbon, filtered 
and evaporated to dryness under reduced pressure to obtain 15.5 g of 
2-cyano-3-(diethoxyphosphoryloxy)-5-n-butoxy-thiophene with a refractive 
index of n.sub.D.sup.20 = 1.500. 
Analysis: C.sub.13 H.sub.20 NO.sub.5 PS. Calculated: %C, 46.85; %H, 6.05; 
%N, 4.2; %P, 9.29. Found: %C, 47.0; %H, 6.1; %N, 4.1; %P, 9.0. 
EXAMPLE 24 
2-cyano-3-(dimethoxyphosphoryloxy)-5-n-butoxy-thiophene 
7.7 g of potassium carbonate and 7.7 g of O,O-dimethyl chlorophosphate were 
added to a solution of 11 g of 2-cyano-3-hydroxy-5-n-butoxy-thiophene in 
150 ml of acetonitrile and the mixture was stirred for 16 hours at 
20.degree. C. and was filtered. The filtrate was evaporated to dryness 
under reduced pressure and the residue was dissolved in ether. The ether 
solution was washed with water containing 100 g/l of sodium chloride and 
then with 0.1N sodium hydroxide solution containing 100 g/l of sodium 
chloride. The ether phase was dried and treated with activated carbon, 
filtered and concentrated to dryness to obtain 12.5 g of 
2-cyano-3-(dimethoxyphosphoryloxy)-5-n-butoxy-thiophene with a refractive 
index of n.sub.D.sup.20 = 1.511. 
Analysis: C.sub.11 H.sub.16 NO.sub.5 PS; molecular weight = 305.29. 
Calculated: %C, 43.28; %H, 5.28; %N, 4.59; %P, 10.15. Found: %C, 43.7; %H, 
5.4; %N, 4.6; %P, 9.6. 
EXAMPLE 25 
An emulsifiable insecticide concentrate was prepared containing 15% by 
weight of 2-cyano-3-(dimethoxyphosphoryloxy)-5-methyl-thiophene (compound 
A), 6.4% by weight of Atlox 4851 (oxyethylene triglyceride with a 
sulfonate- an acid No. of 1.5), 3.2% by weight of Atlox 4855 (oxyethylene 
triglyceride with a sulfonate- acid No. 3) and 75.4% by weight of xylene. 
EXAMPLE 26 
An emulsifiable acaricide concentrate was prepared containing 25% by weight 
of 2-cyano-3-(dimethoxyphosphoryloxy)-5-methyl-thiophene (compound A), 
6.4% by weight of Atlox 4851, 3.2% by weight of Atlox 4855 and 65.4% by 
weight of xylene. 
EXAMPLE 27 
An emulsifiable nematocide concentrate used to treat soil was prepared 
containing 45% by weight of 
2-cyano-3-(dimethoxyphosphoryloxy)-5-methyl-thiophene (compound A), 6.4% 
by weight of Atlox 4851, 3.2% by weight of Atlox 4855 and 45.4% by weight 
of xylene. 
Insecticidal activity of the 
2-cyano-3-(dimethoxyphosphoryloxy)-5-methyl-thiophene (compound A) and the 
2-cyano-3-(dimethoxyphosphoryloxy)-5-methoxy-thiophene (compound B). 
A. Drosophila melanogaster 
This test measured the activity of the vapors of 
2-cyano-3-(dimethoxyphosphoryloxy)-5-methyl-thiophene (compound A) and 
2-cyano-3-(dimethoxyphosphoryloxy)-5-methoxythiophene (compound B). The 
insects were placed in a Petri dish with a diameter of 10 cm connected 
with a tergal gauze to a crystallizer of the same diameter into which was 
placed an acetone solution of the test compound which was evaporated 
before introduction of the insects. Three tests were run for each 
concentration using 25 adult insects less than 48 hours old and the 
results were expressed as percent of mortality after 1 hour and 4 and 6 
hours. The results are reported in Table I. 
TABLE I 
______________________________________ 
Concentration 
in ppm/ 
Time 
Compound in hrs. 500 50 5 
______________________________________ 
1 100 100 40 
A 4 100 100 100 
6 100 100 100 
1 40 29 0 
B 4 100 100 82 
6 100 100 96 
______________________________________ 
B. Blattella germanica 
This was a topical application test in which adult males of Blattella 
germanica received 2 microliters of an acetone solution of the test 
compound between the second and third pair of feet. After treatment, the 
test insects were held in dim light at 20.degree. C. and were fed and the 
percent of mortality was determined at 24 and 48 hours and 6 days with the 
results being reported in Table II. 
TABLE II 
______________________________________ 
Concentration in ppm/ 
Compound time 5000 1250 62.5 
______________________________________ 
24 hrs. -- 45 5 
A 48 hrs. -- 65 10 
6 days -- 100 30 
24 hrs. 100 95 0 
B 48 hrs. 100 95 15 
6 days 100 95 35 
______________________________________ 
C. Sitophilus granarius 
This test was effected by topical application of the test compounds in 
acetone solution at a rate of 5000 or 500 mg of active compound per liter. 
0.2 .mu.l of the acetone solution was applied to the ventral thorax of 
Sitophilus Granarius of 50 insects per concentration and per test. The 
number of insects living and dead was determined after 4 and 24 hours and 
5 days. The results are reported in Table III. 
TABLE III 
______________________________________ 
Concentration in ppm/ 
Compound time 5000 500 
______________________________________ 
4 hrs 100 90 
A 24 hrs 100 90 
5 days 100 100 
4 hrs 100 49 
B 24 hrs 100 100 
5 days 100 100 
______________________________________ 
D. Musca domestica 
This topical application test comprised applying a microliter of an acetone 
solution of the test product to the dorsal thorax of flies which has been 
put to sleep with ether. The insects were held at 20.degree. C. and 50% 
relative humidity. The insects were fed milk and water and the percent of 
mortality was determined after one hour and 24 hours after treatment. The 
results were reported in Table IV. 
TABLE IV 
______________________________________ 
Concentration 
in ppm/ 
Compound Time 2500 500 100 50 
______________________________________ 
1 -- 100 100 95 
A 24 -- 100 100 95 
1 100 100 87 79 
B 24 100 100 94 92 
______________________________________ 
E. Alphis fabae 
This test was effected in the open air with plots of beans measuring 360 
.times. 120 cm with 4 rows of beans. When natural contamination with Aphis 
fabae was estimated to be sufficient, each plot was sprayed with an 
aqueous solution of compound A with two plots being used for each dose. 
The treatment was effected with a base of 2 liters of spray solution. The 
controls of the population was effected 1 hour before the treatment then 1 
day, 1,2 and 3 weeks after the treatment. 
The readings were made on the following scale with 20 plots being read for 
each of the doses. The results are in Table V (compound A at 50 g/hl). 
The notation was effected per class: 
0 corresponding at 0 aphis living per colony 
1 corresponding at 1 to 30 living aphids per colony 
2 corresponding at 30 to 50 living aphids per colony 
3 corresponding at 150 to 500 living aphids per colony 
4 corresponding at 500 living aphids per colony 
TABLE V 
______________________________________ 
Compound A Controls 
Average No. of Average No. of 
value aphids value aphids 
______________________________________ 
1 hour 1.47 84.8 1.53 101.8 
before test 
1 day 0 0 1.89 131.3 
after test 
1 week 0.14 1.3 2.93 314.3 
after test 
2 weeks 0.84 13.6 3.32 314.5 
after test 
3 weeks 2.28 140.9 2.26 197.0 
after test 
______________________________________ 
F. Systemic activity in bean stalk against Aphis fabae 
Vicia fabae stalks about 30 cm high were wrapped in hydrophilic cotton for 
a length of about 5 cm and the cotton was itself enclosed in a plastic 
envelope so as to avoid an eventual effect of the product by its vapors. A 
value of 2 ml of an aqueous solution of compound A at a concentration of 
0.1 and 1 g/liter was injected into the dressing with a syringe and 3 bean 
plants were used for each concentration. Each plant was then contaminated 
with about 20-25 apterous individual adult Aphis fabae and the number of 
dead insects was noted 1 and 2 days after contamination and their eventual 
decendents after one week. The dead insects necessarily resulted from the 
translation of the product from the stalk to the leaves and the results 
are reported in Table VI. 
TABLE VI 
______________________________________ 
Observations of 
Dose of A 
% Efficacy after 
Decendents after 
in g/l 24 hr. 48 hr. 1 week 
______________________________________ 
1 88.6 100 No decendents 
0.1 41.4 48.7 " 
______________________________________ 
The foregoing tests show that compounds A and B have an interesting 
insecticidal activity against the species tested. The systemic activity of 
compound A in bean plants against Aphis fabae is particularly noteworthy 
as systemic insecticides constitute a special useful class of 
insecticides. 
Acaricide activity of the 
2-cyano-3-(dimethoxyphosphoryloxy)-5-methyl-thiophene (compound A) on 
Tetranychus urticae. 
A. Ovicide test 
Bean leaves infested with 10 females of Tetranychus urticae per leaf were 
used and glue was placed about the edge thereof. The females were left for 
24 hours and then removed and the leaves infested with eggs were divided 
into 2 groups. The first group was treated by spraying each leaf with 0.5 
ml of an aqueous solution of compound A at concentration of 50 and 100 mg 
per liter and the second group was untreated and acted as controls. The 
number of eggs living after 9 days from the beginning of treatment and the 
percent of mortality of eggs was determined in Table VII. 
TABLE VII 
______________________________________ 
Product Concentration in mg/1 
% mortality 
______________________________________ 
A 50 54.3 
10 45.4 
Controls 0 9.9 
______________________________________ 
B. Adulticide test 
Bean leaves with glue about the edges and infested with 25 Tetranychus 
urticae acariens each were divided into 2 groups. The first group of 
leaves were sprayed with 2.5 ml each of an aqueous solution of 50, 10 and 
1 mg/l of compound A. The second group were untreated and acted as 
controls. The number of acariens living after 48 hours after the spraying 
and the results are reported in Table VIII. 
TABLE VIII 
______________________________________ 
Compound Concentration in mg/l 
% mortality 
______________________________________ 
A 50 94.0 
10 54.6 
Controls 0 5.0 
______________________________________ 
C. Larvicide test 
The procedure was the same as the ovicide test but the readings were taken 
9 days after treatment to determine the insects evolved in that time. The 
results are expressed in Table IX. 
TABLE IX 
______________________________________ 
Compound Concentration in mg/l 
% mortality 
______________________________________ 
A 50 100 
10 86.6 
Controls 0 12.5 
______________________________________ 
These three tests demonstrate that compound A has a good acaricide activity 
against Tetranychus urticae. 
Nematocide activity of the 
2-cyano-(3-dimethoxyphosphoryloxy-5-methyl-thiophene (compound A). 
A. Panagrellus silusae 
About 2000 nematodes of Panagrellus silusae suspended in 0.5 ml of water 
were placed in a container of about 50 ml and then 10 ml of an aqueous 
solution of compound A in concentrations of 1 or 0.1 g/l were added. Three 
tests were run for each concentration and after 24 hours, the aqueous 
media was homogenized. The number of nematodes living and dead in one ml 
of solution, with a Peter slide, were determined. The results are 
expressed as % of mortality as compared to the untreated controls and the 
results were 94.7% at a dose of 0.1 g/l and 21.4% at a dose of 0.01 g/l. 
This means that compound A shows an interesting nematocidal activity. 
Various modifications of the products and method of the invention may be 
made without departing from the spirit or scope thereof and it is to be 
understood that the invention is to be limited only as defined in the 
appended claims.