IL46688A - Thionophosphoric acid esters their preparation and their use as insecticides and acaricides - Google Patents

Thionophosphoric acid esters their preparation and their use as insecticides and acaricides

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IL46688A
IL46688A IL46688A IL4668875A IL46688A IL 46688 A IL46688 A IL 46688A IL 46688 A IL46688 A IL 46688A IL 4668875 A IL4668875 A IL 4668875A IL 46688 A IL46688 A IL 46688A
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compound
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ethyl
active
halogen
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Bayer Ag
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing aromatic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/173—Esters of thiophosphoric acids with unsaturated acyclic alcohols

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Molecular Biology (AREA)
  • Agronomy & Crop Science (AREA)
  • Biochemistry (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

1457395 Unsaturated thiophosphate esters BAYER AG 26 Feb 1975 [27 Feb 1974] 8036/75 Headings C2P and C2C The invention comprises thionophosphate esters of the general formula which encompasses the cis and trans isomers and wherein R is H, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or halogen and R<SP>1</SP> is C 1 -C 4 alkyl, C 1 -C 4 alkoxy or halogen. They may be obtained by reacting a diester halide in which Hal is halogen with an #-cyanoacetophenone derivative of the formula or its enol form of the formula wherein M is an alkali metal-, alkaline earth metal-, or ammonium equivalent, optionally in the presence of an acid acceptor and/or a solvent. The products have pesticidal properties and may be used as active ingredients in conventional pesticidal formulations. The compound is obtained by adding a solution of NaCN in water and ethanol dropwise to 2<SP>1</SP>,5<SP>1</SP>-dichloro-2- bromoacetophenone in ethanol. Several other specific compounds of Formula V or Va are stated to be obtainable in an analogous manner. 2<SP>1</SP>,5<SP>1</SP> - Dichloro - 2 - bromoacetophenone is prepared from p-dichlorobenzene and acetyl chloride by the Friedel-Crafts method followed by bromination in ether. [GB1457395A]

Description

,ηι»*η9οΐ9ΐ-ΐικ*η nis&in © ο*»*ιη ο»ηβοκ ni*npsi o«p"ir» * ei a ona ©¾a«©ni onssn Hovel thionophosphoric acid esters, their preparation and their use as insecticides and acaricides Type la The present invention relates to certain new O-ethyl-0-n-propyl-O-vinyl-thionophosphoric acid esters, to a process for their preparation and to their use as insecticides and acaricides.
It is already known that certain 0,O-dialkyl-O-cyano-vinyl (thiono)-phosphoric acid esters, for example 0,0-diethyl-0-[1 -(4 *-methyl- or 4 '-chlorophenyl)-2-cyano-vinyl]-phosphoric acid ester and 0,0-diethyl-0-[l -(2 '-methyl- or 2 '-chloro- or 2 · , 51-dichloro- or '-methoxy henyl)-2-cyano-vinyl]-thionophosphoric acid ester, possess insecticidal and acaricidal properties (see German Offenlegungsschrift (German Published Specification) 2,030,509).
The present invention provides, as new compound, the 0-ethyl-O-n-propyl-O-vinyl-thionophosphoric acid esters of the general formula in which R is hydrogen, Cj-O^ alkyl, C-j-C^ alkoxy or halogen, and R' is C^-C^ alkyl, — alkoxy or halogen.
The new compounds (I) have been found to possess an excellent insecticidal, including soil-insecticidal, and acaricidal action. ' Preferably R is hydrogen, methyl, ethyl, methoxy, ethoxy, chlorine, bromine or fluorine and R' is methyl, ethyl, methoxy, ethoxy, chlorine, bromine or fluorine. BBpecially preferred are compounds in which R is hydrogen and R' is methyl, ethyl, methoxy, ethoxy, chlorine, bromine or fluorine or in which R is methyl or ethyl and R' is methyl, ethyl, chlorine, bromine or fluorine; or in which R and R1 are each selected from chlorine, bromine and fluorine.
The general formula (I) here encompasses the corresponding cis- and trans-isomers of the structures (II) and (III) below and mixtures of these components: (III) (ID This invention also provides a process for the preparation of an 0-ethyl-O-n-propyl-O-vinyl-thionophosphoric acid ester of the formula (I), in which an 0-ethyl-O-n-propylthionophosphoric acid diester halide of the general formula in which Hal is halogen, preferably chlorine, is reacted with an ω-cyanoacetophenone derivative (benzoyl- or its enol form of the general formula in which formulas R and R1 have the above-mentioned meanings, and M is an alkali metal equivalent, alkaline earth metal equivalent or ammonium equivalent, optionally in the presence of an acid acceptor and optionally in the presence of a solvent.
Surprisingly, the O-ethyl-O-n-propyl-O-vinyl-thiono-phosphoric acid esters (I) according to the invention are distinguished, relative to previously known compounds of analogous structure and of the same type of action, by having a better insecticidal, including soil-insecticidal, and acaricidal action, coupled with low toxicity to warm-blooded animals. The compounds according to the invention thus represent a genuine enrichment of the arto If, for example, 0-ethyl-O-n-propyl-thionophosphoric acid diester chloride and oj-cyano-2-methylacetophenone, or the corresponding sodium salt, are used as starting materials, the course of the reaction can be represented by the following Acid- binding -HC1 agent The O-ethyl-O-n-propyl-thionophosphoric acid diester chloride (IV) to be used as starting materials are described in the literature and are obtainable according to customary methods. Similarly, the ω-cyanoacetophenones (V) and their enol forms (Va) (see German Offenlegungsschrift (German Published Specification) 2,030,509) can be prepared according to processes which are known in principle, for example by (a) reacting acetonitrile with phenylcarboxylic acid. esters in the presence of alcoholates at elevated temperatures, optionally in a solvent, and subsequently treating the reaction mixture with acids, thus: or (b) reacting the corresponding phenyl compounds with acetyl chloride in the presence of aluminium chloride, brominating the intermediate and finally replacing the bromine by the nitrile group, thus: or (c) reacting appropriately substituted aromatic nitriles with acetonitrile in the presence of an alkali metal and splitting the resulting ketimine with acid, thus: The following may be mentioned as examples of the ω-cyanoacetophenone derivatives (V) or their enol forms (Va) : 2-meth l-, 2-ethyl-, 2-methoxy-, 2-ethoxy-, 2-chloro-, 2-bromo-, 2-fluoro-, 3-methyl-, 3-ethyl-, 3-methoxy-, 3-ethoxy-, 3-chloro-, 3-bromo-, 3-fluoro-, 4-methyl-, 4-ethyl-, 4-methoxy-, 4-ethoxy-, 4-chloro-, 4-bromo-, 4-fluoro-, 2.5-dichloro-, 2 , 5-dibromo-, 4, -dibromo-, 4, 6-dimeth l- and 4.6-diethyl-a)~cyano-acetophenones as well as the corresponding sodium salts of the enol forms.
The process of preparation is preferably carried out in the presence of suitable solvents and diluents. Practically all inert organic solvents can be used for this purpose, especially aliphatic and aromatic, optionally chlorinated hydrocarbons, such as benzene, toluene, xylene, benzine, methylene chloride, chloroform, carbon tetrachloride and chlorobenzene ; ethers, for example diethyl ether, dibutyl ether and dioxan; ketones, for example acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; and nitriles, such as acetonitrile and propionitrile.
All customary acid-binding agents can be used as the acid acceptors. Alkali metal carbonates and alkali metal aleoholates, such as sodium carbonate and potassium carbonate, sodium methylate and ethylate and potassium methylate and ethylate, have proved particularly suitable, as have aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline , dimethylbenzylamine and pyridineβ The reaction temperature can be varied within a fairly wide range. In general, the reaction is carried out at from The reaction is in general allowed to take place under normal pressure.
To carry out the reaction, the starting materials are in general employed in equimolar amounts. An excess of one or other reactant in general produces no significant advantages. The reaction is preferably carried out in the presence of one of the above-mentioned solvents, optionally in the presence of an acid acceptor, at the stated temperatures. After a reaction time of one or more hours, in most cases at elevated temperature, the batch is cooled and the reaction mixture is poured into an organic solvent, for example toluene. Thereafter, the reaction mixture is worked up in the usual manner by washing with a saturated sodium bicarbonate solution and water, drying the organic phase, and evaporating the solvent.
The new compounds are obtained in the form of oils which in most cases cannot be distilled without decomposition but can be freed from the last volatile constituents by so-called "slight distillation", that is to say prolonged heating under reduced pressure to moderately elevated temperatures, and can be purified in this way. They are characterised by the refractive index.
As already mentioned, the 0-ethyl-O-n-propyl-O-vinyl-thionophosphoric acid esters according to the invention are distinguished by an outstanding insecticidal, including soil-insecticidal, and acaricidal activity. They are active against plant pests, pests harmful to health and pests of stored products and couple a very low phytotoxicity with good action against both sucking and biting insects.
For t in the hygiene field and the field of protection of stored products.
To the sucking insects there belong, in the main, aphids (Aphididae) such as the green peach aphid (M zus persicae) . the bean aphid (Doralis fabae) , the bird cherry aphid (Rhopalo-siphum padi) , the pea aphid (Macrosiphum pisi) and the potato aphid (Macrosiphum solani olii) , the currant gall aphid (Cryptomyzus korschelti) , the rosy applie aphid (Sappaphis mali) , the mealy plum aphid (Hyalopterus arundinis) and the cherry black-fly (Myzus cerasi) ; in addition, scales and mealybugs (Coccina), for example the oleander scale (Aspidio-tus hederae) and the soft scale (Lecanium hesperidum) as well as the grape mealybug (Pseudococcus maritimus) ; thrips (Thysanoptera) . such as Hercinothrips femoralis , and bugs, for example the beet bug (Piesma quadrata) , the red cotton bug (Dysdercus intermedius) , the bed bug (Cimex lectularius) , the assassin bug (Ehodnius prolixus) and Ghagas' bug (Triatoma infestans) and, further, cicadas, such as Euscelis bilobatus and Nephotettix bipunctatus.
In the case of the biting insects, above all there should be mentioned butterfly caterpillars (Lepidoptera) such as the diamond-back moth (Plutella maculipennis) . the gipsy moth (Lymantria dispar) . the brown-tail moth (Euproctis chrysorrhoea). and tent caterpillar (Malacosoma neustria) ; further, the cabbage moth (Mamestra brassicae) and the cutworm (Agrotis segetum), the large white butterfly (Pieris brassicae) . the small winter moth (Cheimatobia brumata) , the green oak tortrix moth (Tortrix viridana) , the fall armyworm (Laphygma frugiperda) and cotton worm (Prodenia litura) , the ermine (Epheatia kuhniella) and greater wax moth (Galleria mellonella).
Also to be classed with the biting insects are beetles (Coleoptera) , for example the granary weevil (Sitophilus granarius = Calandra granaria) . the Colorado beetle (Leptino-tarsa decemlineata) . the dock beetle (Gaatrophysa viridula) , the mustard beetle (Phaedon cochleariae ) , the blossom beetle Meligethes aeneus) , the raspberry beetle (Byturus tomentosus) , the bean weevil (Bruchidius = Acanthoscelides obtectus) , the leather beetle (Dermestes frischi) , the khapra beetle (Trogo-derma ranarium), the flour beetle (Tribolium castaneum) , the northern corn billbu (Calandra or Sitophilus zeamais). the drugstore beetle (Stegobium paniceum) . the yellow mealworm (Tenebrio molitor) and the saw-toothed grain beetle (Oryzae-philus surinamensis) . but also species living in the soil, for example wireworms (Agriotes spec.) and larvae of the cockchafer (Melolontha melolontha) : cockroaches, such as the German cockroach (Blattella germanica)« American cockroach (Periplaneta americana) , Madeira cockroach (Leucophaea or Bhyparobia maderae) , oriental cockroach (Blatta orientalis) , the giant cockroach (Blaberus gjganteua) and the black giant cockroach (Blaberus fuscus) as well as Henschoutedenia flexi-vitta; further, Orthoptera. for example the house cricket (Gryllus domesticus) ; termites such as the eastern subterranean termite (Reticulitermes flavipes) and Hymenoptera such as ants, for example the garden ant (Lasius niger).
The Diptera comprise essentially the flies, such as the vinegar fly (Drosophila melanogaster) . the Mediterranean fruit fly (Ceratitis capitata) , the house fly (Musea domestica) , the little house fly (Fannia canicularis) , the black blow fly as well as the stable fly (Stomoxys calcitrans ; further, gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypti) , the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles stephensi) .
With the mites (Acarina) there are classed, in particular, the spider mites (Tetranychidae ) such as the two-spotted spider mite (Tetranychus urticae) and the European red mite (Paratetranvchus pilosus = Panonychus ulmi) , gall mites, for example the blackcurrant gall mite (Eriophye3 ribis) and tarsonemids, for example the broad mite (Hemitarsonemus latus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, such as the relapsin fever tick (Ornithodorus mouba a) .
When applied against pests harmful to health and pests of stored products, particularly flies and mosquitoes, the present compounds are also distinguished by an outstanding residual activity on wood and clay, as well as a good stability to alkali on limed substrates.
The active compounds according to the present invention can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, pastes and granulates. These may be produced in known manner, for example by mixing the active compounds with extenders, that is, liquid or solid or liquefied gaseous diluents or carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents« As liquid diluents or carriers, there are preferably used alkyl naphthalenes, chlorinated aromatic or aliphatic hydrocarbons, such as chlorobenzenes , chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl iso-butyl ketone or cyclohexanone , or strongly polar solvents, such as dimethyl formamide, dimethyl sulphoxide or aceto-nitrile, as well as water.
By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperatures and pressures, for example aerosol propellants, such as halo— genated hydrocarbons, for example freon» As solid diluents or carriers, there are preferably used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, or ground synthetic minerals, such as highly-dispersed silicic acid, alumina or silicates.
Preferred examples of emulsifying and foaa-forming agents include non-ionic and anionic emulsifiers, such as polyoxy-ethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alk larylpolyglycol ethers, alkyl sulphonates, alkyl sulphates and aryl sulphonates as well as albumin hydolyzation products; and preferred examples of dispersing agents include lignin sulphite waste liquors and methyl cellulose.
The active compounds according to the invention can be present in the formulations as a mixture with other active compounds.
In general, the formulations contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom, such as ready-to-use solutions, emulsions, foams, suspensions, powders, pastes, soluble powders, dusting agents and granules. They may be used in the customary manner, for example by squirting, spraying, atomising, dusting, scattering, fumigating, gassing* watering, dressing or encrusting.
The active-compound concentrations in the ready-to-use preparations can be varied within fairly wide ranges. In general, they are from 0.0001 to 10#, preferably from 0.01 to 1#, by weight.
The active compounds can also be used with good success in the ultra-low-volume (ULV) method where it is possible to apply formulations of up to 9 active compound or even to use the active compound by itself.
The present invention also provides an insecticidal or acaricidal composition containing as active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
The present invention also provides a method of combating insects or acarids which comprises applying to the insects oracarids or to a habitat thereof a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.
The present invention further provides crops protected whic immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier. It will be seen that the usual methods of providing a harvested crop may be improved by the present invention. ....
In the biotest Examples A to P which follow, active compounds according to the invention were tested for their activity against a range of plant pests, in comparison to the. known O,0-dialkyl-0-cyano-vinyl(thiono)phosphoric acid esters of the formulas shown below, which are designated (A) to (F): The active compounds according to the present invention are identified by the numbers of the corresponding preparative Examples hereinaftere Example A Drosophila test Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier, and the concentrate was diluted with water to the desired concentration. 1 ml of the preparation of the active compound was applied with a pipette to a filter paper disc of 7 cm diameter. The wet disc was placed over a glass vessel containing 50 vinegar flies (Drosophila melanogaster) and covered with a glass plate.
After the specified periods of time, the destruction was determined as a percentage: 100$ means that all the flies were killed.
The active compounds, their concentrations, the evaluation times and the degree of destruction can be seen from the following table: Table A (Drosophila test) Active Active compound con- Degree of destruct-compound centration in i» ion in # after 1 day (A) 0.01 20 (5) 0.01 100 0.001 100 (2) 0.01 100 0.001 100 Example B Plutella test Solvent: 3 parts by weight of acetone Emulsifier: 1 par by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, stated amount of solvent containing the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.
Cabbage leaves (Brassica oleracea) were sprayed with the preparation of the active compound until dew moist and were then infested with caterpillars of the diamond-back moth (Plutella maculipennis ) .
After the specified periods of time, the degree of destruction was determined as a percentage: 100$ means that all the caterpillars were killed, whereas Oo means that none of the caterpillars were killed.
The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following table: T b l e B (Plutella test) Active Active compound con- Degree of destruct- compound centration in > ion in i after 3 ■ days ' (c) 0.01 100 ( 1 ) 0.01 100 0.001 90 (7) 0.01 100 0.001 100 (5) 0.01 100 0.001 100 (8) 0.01 100 0.001 100 (2) 0.01 100 0.001 90 (4) 0.01 100 0.001 100 Example C Myzus test (contact action) Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polygl col ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.
Cabbage plants (Brassica oleracea) which had been heavily infested with peach aphids (Myzus persicae) were sprayed with the preparation of the active compound until dripping wet.
After the specified periods of time, the degree of destruction was determined as a percentage: 100S means that all the aphids were killed whereas 0$ means that none of the aphids were killed.
The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the followin table: a b l e C (Myzus test) Active Active compound con- Degree of destruct- (B) 0.1 98 0.01 50 (3) 0.1 100 0.01 100 0.001 100 (1) 0.1 100 0.01 100 0.001 95 T a b l e C (continued) (Mvzus test) (2 ) 0.1 100 0.01 1 00 0.001 95 (4) 0. 1 1 00 0.01 100 0.001 90 ( 6) 0.1 1 00 0.01 1 00 0.001 95 Example D Tetranvchus test (resistant) Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.
Bean plants (Phaseolus vulgaris ) . which had a height of approximately 10-30 cm, were sprayed with the preparation of the active compound until dripping wet. These bean plants were heavily infested with the two-spotted spider mite (Tetranychus urticae) in all stages of development.
After the specified periods of time, the effectiveness of the preparation of active compound was determined by counting the dead mites. The degree of destruction thus the spider mites were killed whereas 0 means that none of the spider mites were killed.
The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following table: a b l e D (Tetranvchus test) Active Active compound con- Degree of destruct- compound centration in > ion in i» after 2 days (?) 0.1 90 0.01 0 (E) 0.1 60 0.01 0 (3) 0.1 98 0.01 95 (5) 0.1 100 0.01 98 (2) 0.1 95 0.01 90 (4) 0.1 99 0.01 95 Example E Critical concentration test/soil insects Test insect: Tenebrio molitor larvae in the soil Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amount of solvent, the stated amount of emulsifier was added and the concentrate was diluted with water to the desired concentration.
The preparation of active compound was intimately mixed preparation was of practically no importance; only the amount by weight of active compound per unit volume of soil, which is given in ppm (for example mg/l),was decisive. The soil was filled into pots and the pots were left to stand at room temperature. After 24 hours, the test insects were introduced into the treated soil and after a further 48 hours the degree of effectiveness of the active compound was determined in $> by counting the dead and the live test insects. The degree of destruction is 100?6 if all test insects had been killed and is 0# if just as many test insects were still alive as in the case of the control.
The active compounds, the amounts used and the results can be seen from the table which follows: a b l e E (Soil insecticide test/Tenebrio molitor larvae in the soil) Active Degree of destruction in i» compound at an active compound con- centration of 20 ppm (F) 0 (5) 100 (7) 100 (8) 100 Example F Critical concentration test/soil insects Test insect: Phorbia antiaua grubs in the soil Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amount of solvent, the stated amount of emulsifier was added and the concentrate was diluted with water to the desired The preparation of active compound was intimately mixed with soil. The concentration of the active compound in the preparation was of practically no importance; onl the amount by weight of active compound per unit volume of soil, which is given in ppm (for example mg/l) was decisive. The soil was filled into pots and the pots were left to stand at room temperature. After 24 hours, the test insects were introduced into the treated soil and after a further 48 hours the degree of effectiveness of the active compound was determined in # by counting the dead and the live test insects. The degree of destruction is 100$ if all test insects had been killed and is Ofo if just as many test insects were still alive as in the case of the controle The active compounds, the amounts used and the results can be seen from the table which ollows: ab l e F (Soil insecticide test/Phorbia antiqua larvae in the soil) .(F) 0 (2) 100 (5) 100 (7) 100 (8) 100 The process of this invention is illustrated by the following preparative Examples.
Example 1 20.2 g (0.1 mole) of 0-ethyl-O-n-propyl-thionophosphoric acid diester chloride were added dropwise to a mixture of 15.9 g (0.1 mole) of w-cyano-2-methyl-acetophenone, 14.2 g (0.11 mole) of potassium carbonate and 150 ml of acetonitrile.
The reaction mixture was then warmed to 50°C for 3 hours and cooled, and the batch was poured into 300 ml of toluene. The toluene solution was washed with saturated sodium bicarbonate solution and water and dried over sodium sulphate, and the solvent was then stripped off under reduced pressure. 28 g (86# of theory) of 0-ethyl-0-n-propyl-0-[l-(2l-methylphenyl)- 2-cyanovinyl]-thionophosphoric acid ester were obtained as a 5 yellow oil having a refractive index n^ of 1.5320.
The following compounds could be prepared analogously : Example No. Formula Refractive index Example 4 20.2 g (0.1 mole) of 0-ethyl-0-n-propyl- hionophosphoric acid diester chloride were added dropwise to a, solution of 23.6 g (0.1 mole) of the sodium salt of o)-cyano-2,5-dichloro-' acetophenone in 200 ml of acetonitrile. The reaction mixture was warmed to 50°C for 3 hours and cooled, and the batch was poured into 300 ml of toluene. The toluene solution was, washed with saturated sodium bicarbonate solution and water and dried over sodium sulphate, and the solvent was then stripped off under reduced pressure. 28.5 g (75$ of theory) of 0-ethyl-0-n-propyl-0-[1 -(21 , 5 '-dichlorophenyl)-2-cyano-vinylj-thionophosphoric acid ester were obtained as an oil having a refractive index of 1.5245· The following compounds were prepared analogously: Φ Example Ho. Formula Refractive index The ω-cyanoacetophenone derivatives (V) or their enol forms (Va) to be used as starting compounds, could be obtained, for example, in accordance with the following method: A solution of 10.8 g of sodium cyanide in 20 ml of water and 20 ml of ethanol was added dropwise, whilst stirring, to 26.8 g (0.1 mole) of 21 , 5 *-dichloro-2-bromoaceto-phenone (prepared from jD-dichlorobenzene and acetyl chloride by the Friedel-Crafts method, followed by bromination in ether) in 30 ml of ethanol, during which the temperature of the mixture rose to 50°C. The batch was stirred for a further 15 minutes and cooled to 10°C, and the salt which had precipitated was thoroughly suction-drained. It was rinsed with ether and dried for 5 hours at 100° to 110°C under reduced pressure. 19.5 g (83$ of theory) of a beige powder of melting point 300°C were thus obtained.
The following ω-cyanoacetophenones or their sodium salts were also obtainable analogously: Formula Yield Physical properties (# of (boiling point, C/mm theory) Eg. or melting point, C Formula Yield Physical properties of (boiling point, °C/mm theory) gg. or melting point, ¾ NaO UC-CH-υ __ (decomposition) tlen)

Claims (28)

What we claim is:
1. O-Ethyl-O-n-propyl-O-vinyl-thibnophosphoric acid esters of the general formula in which R is hydrogen, Cj-C^ alkyl, ^-C^ alkoxy or halogen, and R* is C^-C^ alkyl, Cj-C^ alkoxy or halogen.
2. Compounds according to claim 1, in which R is hydrogen, methyl, ethyl, methoxy, ethoxy, chlorine, bromine or fluorine and R* is methyl, ethyl, methoxy, ethoxy, chlorine, bromine or fluorine,
3. The compound of the formula
4. · The compound of the formula
5. The compound of the formula
6. The compound of the formula
7. The c
8. The compound of the formula
9. The
10. The
11. A process for the preparation of an 0-ethyl-O-n-propyl-O-vinyl-thionophosphoric acid ester according to claim 1 , in which an 0-ethyl-O-n-propylthionophosphoric acid diester halide of the general formula in which Hal is halogen, is reacted with an ω-cyanoacetophenone derivative of the general formula or an enol form thereof of the general formula in which formulas R and R* have the meanings stated in claim 1 and M is an alkali metal equivalent, alkaline earth metal equivalent or ammonium equivalent.
12. A process according to claim 11, in which Hal is chlorine.
13. A process according to claim 11 or 12, in which the reaction is effected in the presence of a solvent.
14. A process according to claim 11, 12 or 13, in which the reaction is effected in the presence of an acid acceptor.
15. · A process according to claim 14, in which the acid acceptor is an alkali metal carbonate, an alkali metal alcoholate or an aliphatic, heterocyclic or aromatic amine.
16. A process according to any of claims 11 to 15, in which the reaction is effected at from 0° to 100°C.
17. A process according to claim 16, in which the reaction is effected at from 20° to 55°C.
18. A process according to any of claims 11 to 17, in which the reactants are used in substantially equimolar amounts.
19. A process for the preparation of a compound according to claim 1 substantially as described in Example 1 or 4.
20. Compounds according to claim 1 whenever prepared by a process according to any of claims 11 to 19.
21. An insecticidal or acaricidal composition containing as active ingredient a compound according to any of claims 1 to 10 and 20 in admixture with a solid or liequefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
22. A composition according to claim 20 containing from 0.1 to 9 of the active compound, by weight.
23. A composition according to claim 21 containing from 0.5 to 0$ of the active compound, by weight.
24. A method of combating insects or acarids which comprises applying to the insects or acarids or to a habitat thereof a compound according to any of claims 1 to 10 and 20 alone or in the form of a composition containing as active ingredient a compound according to any of claims 1 to 10 and 20 in admixture with a diluent or carrier.
25. A method according to claim 24 in which a composition is used containing from 0.0001 to 10 of the active compound,
26. A method according to claim 25 in which a composition is used containing from 0.01 to 1$ of the active compound, by weight.
27. A method according to any of claims 24 to 26, in which the active compound is one of those hereinbefore mentioned in any of Examples A to P.
28. Crops protected from damage by insects or acarids by being grown in areas in which immediately prior to and/or during the time of the growing a compound according to any of claims 1 to 10 and 20 was applied alone or in admixture with a diluent or carrier.
IL46688A 1974-02-27 1975-02-24 Thionophosphoric acid esters their preparation and their use as insecticides and acaricides IL46688A (en)

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DE2409462A DE2409462A1 (en) 1974-02-27 1974-02-27 0-AETHYL-0-N-PROPYL-0-VINYL-THIONOPHOSPHORIC ACID ESTER, METHOD FOR THEIR MANUFACTURING AND THEIR USE AS INSECTICIDES AND ACARICIDES

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AR (1) AR206422A1 (en)
AT (1) AT329079B (en)
AU (1) AU7855075A (en)
BE (1) BE825995A (en)
BR (1) BR7501071A (en)
DD (1) DD118513A5 (en)
DE (1) DE2409462A1 (en)
DK (1) DK133988C (en)
FR (1) FR2262043B1 (en)
GB (1) GB1457395A (en)
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DE2819825A1 (en) * 1978-05-05 1979-11-08 Bayer Ag PROCESS FOR THE PREPARATION OF 0,0-DIAETHYL-0- (1-PHENYL-2-CYANO-PROPEN (1) YL) -THIONOPHOSPHORIC ACID ESTER
US4197312A (en) 1978-05-09 1980-04-08 American Cyanamid Company Alkali metal and alkaline earth metal salts of benzoylacetonitriles
DE3001519A1 (en) * 1980-01-17 1981-07-30 Bayer Ag, 5090 Leverkusen ENDOPARASICICIDAL AGENTS

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GB1457395A (en) 1976-12-01
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ZA751200B (en) 1976-01-28
JPS50117940A (en) 1975-09-16
AU7855075A (en) 1976-08-26
AT329079B (en) 1976-04-26
DD118513A5 (en) 1976-03-12
DK76575A (en) 1975-10-27
BR7501071A (en) 1975-12-02
IL46688A0 (en) 1975-04-25
DK133988B (en) 1976-08-23
SE7502157L (en) 1975-08-28
LU71912A1 (en) 1975-12-09
AR206422A1 (en) 1976-07-23
BE825995A (en) 1975-08-26
FR2262043A1 (en) 1975-09-19
FR2262043B1 (en) 1978-07-13
DE2409462A1 (en) 1975-10-02

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