DE2243612A1 - THIOPHEN-GLYOXYLONITRIL-OXIM-PHOSPHORIC ACID DERIVATIVES AND THEIR USES - Google Patents

Description

LAWYERS

DR. ! Vi]. ßik.-CHEM. WALTER BEfL

DK. ju & .f:. · '.- c. ·; -. .. R-T. WOLFF

FRA M. κ / iJ β JAM tAAt (4 - H OCHST AU £ lüfl5)) <Ajifc SM

Our No. 18 053

Stauffer Chemical Company Westport, Conn., V. St. A.

Thiophene-glyoxylonitrile-oxime-phosphoric acid derivatives and

their use

The invention relates to a group of compounds generally called thiophene-glyoxylonitrile-oxime-phosphoric acid derivatives can be designated and are effective insecticides.

The compounds according to the invention are given by the general formula

-C = NO- ^b C = N ^R l

in which R is a lower alkyl radical having 1 to 4 carbon atoms and R. is a lower alkyl or a lower alkoxy radical having 1 to 4 carbon atoms. [) ic the above compounds let see that the thiophene-glyoxylonitrile-oxime-sodium

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salt is treated with a dialkylphosphoryl halide or an alkoxyalkylphosphony halide. The sodium thiophene glyaxylonitrile oxime salt can be synthesized by treating sodium methylate in the presence of a solvent with a mixture of thiophene acetonitrile and amyl nitrite. acts.

The following examples are the preferred embodiments of the invention serve to explain the invention.

example 1 Synthesis of the thiophene-2-glyoxylonitrile oxime trium salt

45.3 g (0.21 mol) of a 25% strength sodium methylate solution in methanol and 200 ml of methanol were combined in a 500 ml three-necked flask equipped with a stirrer, thermometer, dropping funnel and a condenser fitted with a calcium chloride drying tube. The solution was stirred with cooling in an ice bath at 10 ° C. A mixture of 24.6 g (0.21 mol) isoamyl nitrite and 24.6 g (0.2 MoDThiophen-2-acetonitrile was added slowly through the dropping funnel, that the reaction temperature did not rise above 15 ⁰ C. After the addition the ice bath was removed and the reaction mass was stirred for four hours at room temperature. The reaction mass was then vacuum stripped of all volatiles, the back pressure was triturated with 300 ml of anhydrous diethyl ether and the desired product was filtered off.

Example 2

. S.

Γ J-C = N-O-

|| / ° - ^C 2 ^H 5

np η

3 0 9 811/119 0 ^{BAD 0RJG [NAL}

8.3 g (0.05 mol) of thiophene-2-glyoxylonitrile oxime sodium salt was dissolved in 150 ml of acetone in a 250 ml flask. Then 9, k g CO, 05 mol) O, 0-diethylthiophosphoryl chloride were added and immediately afterwards the salt precipitated. The reaction mass was allowed to stand at room temperature for one hour. Then it was poured into 300 ml of benzene. The benzene mixture was washed with three 200 ml portions of water, dried over anhydrous magnesium sulfate and evaporated in vacuo to give 13.5 g (99% of theory) of the desired product; n ^ ⁰ = 1.5372. -

Example 3

C = NO-Pf ^ό
C = N ^0CH 3

In a manner similar to Example 2, 8.2 g (0.05 mol) of thiophene-2-glyoxylonitrile oxime sodium salt was 8.2 g (0.05 mol) 0, O-dimethylthiophosphoryl chloride combined,

30 whereby the desired product was obtained; n ~. = 1.5517,

Example H

h / 2
- C = NO-PC ^L

I

C =, N ^υ 2 5

In a manner similar to Example 2, 8.3 g (0.05 Moles) thiophene-2-glyoxylonitrile oxime sodium salt at 8.6 g (0.05 mol) 0-ethyl, äthylthiophosphonylchlorid combined,

30 whereby the desired product was obtained; n .. = 1.5665,

3098 1 17 1 190

Entomological test methods

I. Housefly (Musca domestica (L.)) (HF) A. Film residue

A stock solution containing 100 mg / nil of the toxin was prepared in a suitable solvent. Aliquots of this solution were combined with 1 ml. Of an acetone-peanut oil solution in a Petri dish with a diameter of 55 mm. The solution was then allowed to dry. The aliquots were varied to give the desired concentrations of toxin, ranging from 100 µg per dish to the concentration at which 50% igG mortality was achieved. The dishes were placed in a circular cardboard cage, which was closed with cellophane at the bottom and covered with a fabric net at the top. Twenty-five female houseflies were placed in the cage and the percent mortality was determined after 48 hours. The LD _5Q values are given in mg per 25 female flies.

II. German cockroach (Blattella germanica (Linne)) (GR)

Ten one-month-old nymphs were placed in a circular cardboard cage, which was closed with cellophane on one side and covered with a cloth net on the other. Aliquots of the toxin, dissolved in a suitable solvent, were diluted with water containing 0.0002% of a conventional wetting agent such as e.g. B. Polyoxyäthylensorbitanmonolauratäther of alkylated phenols, mixed with organic sulfonates, were added. The test concentrations ranged from 0.1% down to the concentration at which 50% mortality was achieved. Each of these aqueous suspensions was sprayed onto the insects through the cloth net using a hand spray gun. The percent mortality was recorded after 72 hours and the LD_ _n values were expressed as the percentage of the toxin in the aqueous spray.

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III. Salt marsh caterpillar (Estigmene acrea (Drury)) (SMC)

Test solutions were made in the same way and in the same Concentrations as prepared for the German cockroach (II). Pieces of sorrel leaves (Rumex obtusifolius) 2.5 to 4 cm in length were immersed in the test solutions for 10 to 15 seconds and left to dry laid a wire mesh. The dried sheet was placed on a moistened piece of filter paper in a Petri dish and with five larvae in the 3rd instar stage (thirdinstar larvae). The mortality of the larvae was recorded after 72 hours and the LD ^ Q values were recorded as Percentage of the active ingredient in the aqueous suspensions' expressed.

IV. Black bean aphid (Aphis fabae (Scop.)). (BA)

Watercress plants (Nasturtium Tropaeolum sp.) With a size of about 5 to 8 cm were planted in 8 cm clay pots in sandy loam and were populated with 50-75 lice of different ages. After 24 hours they were sprayed with aqueous suspensions of the toxin until they drained off. The suspensions were prepared as in experiments (II, III) described above. The test concentrations ranged from 0.05% to the concentration at which · nine 50% mortality was achieved. Mortality was noted after 4-8 hours; The LD ₅₀ values were expressed as the percentage of active ingredient in the aqueous oucpensions.

V. Ly ^ uG-V / anze (Lygus hesperus (Knight)) (LB)

/ JLa b '.; I of the German cockroach (II), with the exception that the test concentrations ranged from 0.05% to di, r concentration at which 50% mortality was achieved.

Vl Tdbdk buttonworm (Heliothis virescens (F.)) (TBW)

As for -lor Salzsumpf-R.-iupe (III), but with the exception ihme, -laß ann part "of sorrel, leaves of Roman

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Lettuce (Latuca sativa) were used as the host plant.

VII. Beet Army Worm (Spodoptera exigua (JUbner)) (BAW)

As with the salt marsh caterpillar (III), but with the exception that instead of sorrel leaves of romaine lettuce (Latuca sativa) were used as the host plant.

VIII. Mosquito (Culex pipiens quinquefasciates)

(Mos)

100 ml of an aqueous solution of the test compound with a Concentrations of 0.5 ppm were poured into a 17 g Dixie # 67 wax paper cup. 10 mosquito larvae (Culex pipiens quinquefasciates) in the late 3rd or early 4th instar stage were placed in each beaker, and the Beakers were kept at 21.1 C for 3 days after which time the mortality was determined. The connections, which were effective at 0.5 ppm were tested again at ever decreasing concentrations until the LD ^ "value had been determined.

Tabel

Connection HF GR connection

SMC BA

TBW Mos

BAW

Example 1 30 0.02 0.03 0.008 0.0008 0.05 0.03 0.005 Example 2 25 0.08 0.05 0.000 0.0008 0.03 0.008 0.01 Example 3 10 0.005 0.03 0.003 0.002 0.05 0.05 0.03

The compounds of the invention are generally brought into a form in dev it easily can be applied. For example, the compounds can be incorporated into peticide preparations which are in the form of emulsions, suspensions, solutions, dusts and aerosol sprays. In general, such preparations contain, in addition to the active ingredient dia auxiliaries, which are normally found in pesticide

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Preparations are used. In these preparations, the active compounds according to the invention are the only ones that can be used as pesticides Component are used, or they can be used in a mixture with other compounds of similar usability will. The pesticidal preparations according to the invention can use organic solvents as auxiliaries, e.g. B. Sesame oil, xylene solvents, heavy gasoline and the like, water, emulsifying agents, surface active agents Agents, talc, pyrophyllite, diatomite, gypsum, clays, propellants, e.g. B. Diohlordifluormethani and the like. Contain. If necessary, the active ingredients can be applied directly to feed, Saal well and the like, which are affected by the insecticides, are applied. In such an application it is advantageous to use a non-mandatory connection. The pesticidal compounds of the invention need not necessarily be effective as such, of course. The purposes of the present Invention will be fully satisfied when the compound by external influences, e.g. B. light, or through physiological action that occurs when the Compound gets into the body of the insect, takes effect.

The exact way in which the pesticides of the invention Connections are related to the person skilled in the art easily seen. Preferably, the pesticidally active compound is in the form of a liquid preparation, z. B. an emulsion, suspension or an aerosol spray applied. The concentration of the pesticidally effective Compound in the preparation can vary within fairly wide limits, but generally does the pesticidally active compound comprises no more than about 50% by weight of the preparation. *

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Claims (5)

Claim «;
11 compounds of the general formula -C = N-O-P ^R i in which R is a lower alkyl radical having 1 to 4 carbon atoms and R _{1 is} a lower alkyl radical or a lower alkoxy radical having 1 to H carbon atoms. 2. A compound according to claim 1, characterized in that R is a methyl radical and R _{1 is} a methoxy radical. 3. A compound according to claim 1, characterized in that R is an ethyl radical and R _{1 is} an ethoxy radical. 4. A compound according to claim 1, characterized in that R and R _{1 represent} ethyl radicals. 5. Agent for controlling insects, characterized by a content of a compound according to one of the claims 1 to 4. For Stauffer Chemical Company Westport, Conn., V. St. A. (Dr. W. Beil) Lawyer Tr (19 8 1 1 / m 0 BAD OR] QtNAi.