US3928508A - S-(n-acyl-n-alkyl or phenyl-amidocarbonyl)-methyl-thio-phosphoric and- -phosphonic acid esters - Google Patents

S-(n-acyl-n-alkyl or phenyl-amidocarbonyl)-methyl-thio-phosphoric and- -phosphonic acid esters Download PDF

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US3928508A
US3928508A US384676A US38467673A US3928508A US 3928508 A US3928508 A US 3928508A US 384676 A US384676 A US 384676A US 38467673 A US38467673 A US 38467673A US 3928508 A US3928508 A US 3928508A
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amidocarbonyl
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Claus Stolzer
Ingeborg Hammann
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    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4075—Esters with hydroxyalkyl compounds
    • 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
    • A01N57/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having alternatively specified atoms bound to the phosphorus atom and not covered by a single one of groups A01N57/10, A01N57/18, A01N57/26, A01N57/34
    • 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
    • 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
    • C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl

Definitions

  • R is alkyl or alkoxy of l to 6 carbon atoms
  • R" is alkyl of Ho 6 carbon atoms or phenyl
  • Acyl is (C -Cgalkyhcarbonyl or phenylcarbonyl
  • X is oxygen or sulfur
  • the present invention provides, as new compounds, the S-( N-acylamidocarbonyl)-methyl-monoor -dithio-phosphoric or -phosphonic acid esters of the general formula R is alkyl of 1 to 6 carbon atoms,
  • R is alkyl or alkoxy of l to 6 carbon atoms
  • R" is alkyl of 1 to 6 carbon atoms or phenyl
  • Acyl is (C -C -alkyl) carbonyl or phenylcarbonyl
  • X is oxygen or sulfur.
  • R is straight-chain or branched lower alkyl with 1 to 4 carbon atoms (namely methyl, ethyl, isoor n-propyl, or n-, iso-, sec.- or tert.-butyl); R is straightchain or branched lower alkyl as R or lower alkoxy with, in either case, 1 to 4 carbon atoms (such as methoxy, ethoxy, isoor n-propoxy or n-, iso, sec.- or tert.-butoxy); R" is straightchain or branched lower alkyl with l to 4 carbon atoms or phenyl; and Acyl is acetyl, propionyl, butyryl, isobutyryl or benzoyl.
  • 1 to 4 carbon atoms namely methyl, ethyl, isoor n-propyl, or n-, iso-, sec.- or tert.-butyl
  • R is straightchain or
  • the S-(N-acyl-amidocarbonyl)-methylthiophosphoric acid esters and thiophosphonic acid esters of the formula (I) possess a substantially better insecticidal and acaricidal action than the prior art S-( N-acyl-amidocarbonyl)-methyl-thiophosphoric acid esters which are not only the nearest comparable compounds with regard to structure and type of activity but also the best-known commercially available products of this class of substance, and from which the compounds according to the invention differ in respect of the nature of the acyl radical.
  • the new compounds thus represent an enrichment of the art.
  • the present invention also provides a process for the preparation of an S-(N-acylamidocarbonyl)-methyl- 2 monoor -di-thiophosphoric acid ester or thiophosphonic acid ester of the formula (I) in which an 0,0- dialkyl-monoor -di-thiophosphoric acid salt or thiophosphonic acid salt of the general formula &
  • Hal is a halogen atom, preferably bromine or chlorine, and
  • M is an alkali metal equivalent, alkaline earth metal equivalent or optionally alkyl-substituted ammonium equivalent.
  • halogenoacetic acid N-acylamides (III) are: chloroacetic acid or bromoacetic acid N-acetyl-N-ethyl-, N-acetyl-N-n-butyl-, N-acetyl-N- sec.-butyl-, N-propionyl-N-methyl-, N-propionyl-N- ethyl-, N-propionyl-N-isopropyl-, N-propionyl-N-sec.- butyl-, N-isobutyryl-N-ethyL, N-isobutyryl-N-isopropyl-, N isobutyryl-N-sec.-butyl-, N-benzoyl-N-ethyl-, N-benzoyl-N-isopropyl-, N-benzoyl-N-sec.-butyl-, N- isobutyryl-N-phenyland N-benzo
  • the preparative process for the new compounds (I) is preferably carried out with conjoint use of a suitable solvent or diluent.
  • a suitable solvent or diluent for example, practically all inert organic solvents can be used, especially aliphatic and aromatic, optionally chlorinated, hydrocarbons such as benzene, toluene, xylenes, benzine, methylene chloride, chloroform, carbon tetrachloride and chlorobenzene; ethers, for example diethyl ether, dibutyl ether and dioxane; ketones, for example acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; nitriles, such as acetonitrile and propionitrile; and alcohols, for example methanol, ethanol and isopropanol.
  • water is also suitable as a solvent.
  • the reaction temperature can be varied within a fairly wide range. In general, the reaction is carried out at from to 120C, preferably at from to 60C.
  • the reaction is in general carried out under normal pressure.
  • the starting materials are in most cases employed in equimolar amounts. An excess of one or other reactant produces no substantial advantages.
  • the reaction is preferably carried out in the presence of one of the above-mentioned solvents, at the indicated temperatures, and the reaction mixture is worked up in the usual manner after stirring for several hours.
  • the compounds according to the invention are in most cases obtained in the form of colorless to slightly colored viscous, water-soluble oils or crystalline products which in general cannot be distilled without decomposition but can be freed of the last volatile constituents by so-called slight distillation, that is to say prolonged heating to moderately elevated temperatures under reduced pressure, and can be purified in this way. They are characterized, in particular, by the refractive index and, in the case of solid compounds, by the melting point.
  • the new S-(N- acylamidocarbonyl)-methylthiophosphoric acid esters and thiophosphonic acid esters are distinguished by an excellent insecticidal, acaricidal and soil-insecticidal activity against plant pests, pests of stored products and pests harmful to health. They possess a good action against both sucking and biting insects and against mites (Acarina). At the same time, they show only a slight phytotoxicity.
  • the compounds according to the invention may be successfully employed as pesticides in plant protection and in the hygiene field.
  • aphids such as the green peach aphid (Myzus persicae), the bean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum padi), the pea aphid (Macrosiphum pisi) and the potato aphid (Macrosiplzum solanifolii), the current gall aphid (Cryptomyzus korschelti), the rosy apple aphid (Sappaphis mall), the mealy plum aphid (Hyalopterus aruna'inis) and the cherry black-fly (Myzus cerasi); in addition, scales and mealybugs (Coccina), for example the oleander scale (Aspidiotus hederae) and the soft scale (Lecanium hesperidum) as well as the grape mealybug (Pseudoc)
  • butterfly caterpillars such as the diamond-back moth (Plutella maculipennis), the gypsy moth (Lymantria dispar), the brown tail moth (Euproctis clzrysorrhoea) and tent caterpillar (Malacosoma neustria); further, the cabbage moth (Mameslra brassz'cae) and the cutworm (Agrotis segetum), the large whitebutterfly (Pieris brassicae), the small winter moth (Cheimatobia brumata), the green oak tortrix moth (Tortrix viridana), the fall armyworm (Lapliygma frugiperda) and cotton worm (Prodenia litura), the ermine moth (Hyponomeuta padella), the Mediterranean flour moth (Ephestia kuhniella) and greater wax moth (Galleria
  • beetles Colding insects
  • beetles Colding insects
  • the granary weevil Seroplzilus granarius Calandra granaria
  • Colorado bettle Colorado bettle
  • the dock beetle Gastrophysa viridula
  • the mustard beetle Phaedon cochleariae
  • the blossom beetle Meligethes aeneus
  • the raspberry beetle Byturus tomenrosus
  • the bean weevil Bruchidius Acanthoscelides obtectus
  • the leather beetle Demestes frisclzi
  • the khapra beetle Trogoderma granarium
  • the flour beetle Tribolium castaneum
  • the northern corn billbug Calandra or Sitophilus zeamais
  • the drugstore beetle Stegobium paniceum
  • the yellow mealworm Ten
  • the Diptera comprise essentially the flies, such as the vinegar fly (Drosophz'la melanogaster), the Mediterranean fruit fly (Ceratitis capilata), the house fly (Musca domestica the little house fly (Fannia canicularis), the black blow fly (Phormia regina) and bluebottle fly (Calliphora erythrocephala) as well as the stable fly (Stomoxys calcitrans); further, gnats, for examples mosquitoes such as the yellow fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles steplzensi).
  • mosquitoes such as the yellow fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles steplzensi).
  • mites there are classed, in particular, the spider mites (Tetranychidae) such as the twospotted spider mite (Tetranychus urticae) and the European red mite (Paratetranychus pilosus Panonyclius ulmi), gall mites, for example the blackcurrent gall mite (Eriophyes ribis) and tarsonemids, for example the broad mite (Hemitarsonemus latus) and the cyclamen mite (Tarsonemus pallia'us); finally, ticks, such as the relapsing fever tick (Ornithoa'orus moubata).
  • the spider mites such as the twospotted spider mite (Tetranychus urticae) and the European red mite (Paratetranychus pilosus Panonyclius ulmi)
  • gall mites for example the blackcurrent gall mite (Eriophyes ribis)
  • tarsonemids for example the broad
  • the present compounds 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 instant invention can be utilized, if desired,iinthe form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticidediluents or extenders; i.e. diluents, carriers or extenders of the type usable in conventional pesticide formulations'or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, s'pray powders, pastes, solublepowde'rs', dusting agents, granules, etc.
  • conventional inert i.e. plant compatible or herbicidally inert
  • pesticidediluents or extenders i.e. diluents, carriers or extenders of the type usable in conventional pesticide formulations'or compositions
  • conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, e
  • carrier vehicle assistants e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents.
  • aerosol propellants which are gaseous at normal temperatures and pressures, such as freon
  • inert dispersible liquid diluent carriers including inert organic solvents, such as aromatic hydrocarbons (e.g.
  • amides e.g. dimethyl formamide, etc.
  • sulfoxides e.g. dimethyl sulfoxide, etc.
  • acetonitrile ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g.
  • ground natural minerals e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.
  • ground synthetic minerals e.g.
  • emulsifying agents such as non-ionic and/or anionic emulsifying agents (e. g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, albumin hydrolyzates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc. and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.
  • non-ionic and/or anionic emulsifying agents e. g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, albumin hydrolyzates, etc., and especially alkyl arylpolyglycol ethers, magnesium
  • Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other insecticides, and acan'cides, or rodenticides, fungicides, bactericides, nematocides, herbicides, fertilizers, growth-regulating agents, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.
  • plant protection agents such as other insecticides, and acan'cides, or rodenticides, fungicides, bactericides, nematocides, herbicides, fertilizers, growth-regulating agents, etc.
  • composition mixtures in which the active compound is present in an amount substantially between about 01-95 percent by weight, and preferably 0.5 percent by weight, of the mixture
  • carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0001-10 percent, preferably 0.0ll percent, by weight of the mixture.
  • the present invention contemplates over-all compositions which comprises mixtures of a conventional dispersible carrier vehicle such as (l) a dispersible inert finely divided carrier solid, and/or (2) a dispersiblelcarrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g.
  • a 'surfaceactive agent such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0001- percent, and preferably 0.01-95 percent, by
  • the active compounds can also be used in accordance with thewell known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in f nely divided form, e.g. average particle diameter of frdrnSO-IOO microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only to at most about a few liters/hectare are needed, and often amounts only up to about 15 to 1000 g/hectarefipreferably 40 to 600 g/hectare, are sufficient. In thisprocess it ispossible to use highly concentrated liquid compositions with said liquid car rier vehicles containing from about 20 to about 95 percent by weight of the active compound or even the percent active substance alone, e.g. about 20-100 percent by weight of the active compound.
  • the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. insects and acarids, which comprises applying to at least one of correspondingly (a) such insects, (b) such acarids, and (.c) the corresponding habitat thereof, i.e. the locus to be protected, a correspondingly combative or toxic amount, i.e. and insecticidally or acaricidally. effective amount, of the particular active compound of the invention alone or together with a carrier vehicle as noted above.
  • pests e.g. insects and acarids
  • the instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, dressing, encrusting, and the like.
  • EXAMPLE I Plutella 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.
  • 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).
  • the degree of destruction was determined as a percentage: 100% means that all the caterpillars were killed whereas means that none of the caterpillars were killed.
  • 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.
  • Cabbage plants (Brassica oleracea) which had been heavily infested with peach aphids (Myzus persicae) 10 were sprayed with the preparation of the active compound until dripping wet.
  • the degree of destruction was determined as a percentage: 100 perecent means that all the aphids were killed, whereas 0 (Plurellu test) concentration in 70 Degree of destruction in after 3 days i (CH;,O) -P-SCH2CONCHO 0.1 100 0.01 0 CH3 (known) (A) s. (C. ,H5O)2PSCH. .CON-CHO 0.1 70 0.01 0 C11, (known) (B) c,11 ,o P s CH3 c11, 0,1 100 ,1-1 s-c11 -NC-CH 0.01 100 c,1-1,,o s
  • Oat plants (Avena saliva) which had been strongly infested with the bird cherry aphid (Rhopalosiphum padi) we're'watered with the preparation of the active compound softhat the preparation penetrated into the soil without wetting the leaves of the oat plants.
  • the active compound was taken up by the oat plants from the soiland thus reached theinfestecl leaves;
  • the degree of destruction was determined as a percentage: 100 percent means that all the aphids were killed whereas 0 percent means that none of the a phids were killed.
  • Table 3 1 Rhupalosiplmm test/systemic action) I Activewcompound con- Degree of destruction in after 4 days 1 1 CH3 (known) (C) CH;,O ⁇ s c11 0.1 100 0.01 100 c11 SCH. .-fiN-fi-CH;, 0.001 60 o 0 1) c n o o c": 0.1 100 P 0.01 -100 C2H-,O -011 .-fiNf-CH, 0.001 100 (4) c n o s CHI, 01 100 ⁇ P 0.01 100 (311 S-CH -fi-Nfi-CH;, 0.001 1 0, H5O 0 C11 CH,
  • Active compound g (known) (A) 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 obtained is expressed as a percentage: percent means that all the spider mites were killed whereas 0 percent means that none of the spider mites were killed. v

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Abstract

S-(N-acyl-N-alkyl or phenyl-amidocarbonyl)-methyl-thiophosphoric and -phosphonic acid esters of the formula

in which R is alkyl of 1 to 6 carbon atoms, R'' is alkyl or alkoxy of 1 to 6 carbon atoms, R'''' is alkyl of 1 to 6 carbon atoms or phenyl, Acyl is (C1-C6-alkyl)carbonyl or phenylcarbonyl, and X is oxygen or sulfur, WHICH POSSESS INSECTICIDAL AND ACARICIDAL PROPERTIES.

Description

United States Patent 191 Stiilzer et al.
[ Dec. 23, 1975 S-(N-ACYL-N-ALKYL OR PHENYL-AMIDOCARBONYU-METHYL- THIO-PHOSPHORIC AND- -Pll0SPHONlC ACID ESTERS [76] Inventors: Claus Stiilzer, c/o Bayer Aktiengesellschaft, Wuppertal-Elberfeld; Ingeborg Hammann, c/o Bayer Aktiengesellschaft, Leverkusen, both of Germany [22] Filed: Aug. 1, 1973 [21] Appl. No.: 384,676
[30] Foreign Application Priority Data V 220,284 2/ 1959 Australia 260/943 Primary ExaminerRichard L. Raymond [57] ABSTRACT S-(N-acyl-N-alkyl or phenyl-amidocarbonyl)-methylthiophosphoric and -phosphonic acid esters of the formula 1 I R is alkyl of l to-6 carbon atoms,
R is alkyl or alkoxy of l to 6 carbon atoms,
R" is alkyl of Ho 6 carbon atoms or phenyl,
Acyl is (C -Cgalkyhcarbonyl or phenylcarbonyl, and
X is oxygen or sulfur,
which possess insecticidal and acaricidal properties.
'4 Claims, No Drawings S-(N-ACYL-N-ALKYL OR PHENYL-AMIDOCARBONYL)-METHYL-THIO- PHOSPHORIC AND- -PHOSPHONIC ACID ESTERS The present invention relates to and has for its objects the provision of particular new S-(N-acyl-N-alkyl or phenylamidocarbonyl)-methyl-thiophosphoric and -phosphonic acid esters, i.e. S-(N-alkanoylor '-benzoyl-N-alkylor -phenyl-amidocarbonyl)-methyl-mnoor di-thiophosphoric acid alkyl esters or the alkanephosphonic acid ester counterparts thereof, which are optionally halogen-substituted on the benzene ring, which possess insecticidal and acaridical properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles and methods for producing such compounds and for using such compounds in a new way especially for combating pests, e.g. insects and acarids, with other and further objects becoming apparent from a study of the within specification and accompanying examples.
It is known from German Published DAS Nos. 1,148,806 and 1,143,052, and British Patent Specification 867,780 that the reaction products of 0,0-dialkylthiophosphoric acid salts with certain halogenoacetic acid N-acylamides are distinguished by insecticidal and acaricidal activity.
The present invention provides, as new compounds, the S-( N-acylamidocarbonyl)-methyl-monoor -dithio-phosphoric or -phosphonic acid esters of the general formula R is alkyl of 1 to 6 carbon atoms,
R is alkyl or alkoxy of l to 6 carbon atoms, R" is alkyl of 1 to 6 carbon atoms or phenyl,
Acyl is (C -C -alkyl) carbonyl or phenylcarbonyl,
and
X is oxygen or sulfur.
Preferably, R is straight-chain or branched lower alkyl with 1 to 4 carbon atoms (namely methyl, ethyl, isoor n-propyl, or n-, iso-, sec.- or tert.-butyl); R is straightchain or branched lower alkyl as R or lower alkoxy with, in either case, 1 to 4 carbon atoms (such as methoxy, ethoxy, isoor n-propoxy or n-, iso, sec.- or tert.-butoxy); R" is straightchain or branched lower alkyl with l to 4 carbon atoms or phenyl; and Acyl is acetyl, propionyl, butyryl, isobutyryl or benzoyl.
Surprisingly, the S-(N-acyl-amidocarbonyl)-methylthiophosphoric acid esters and thiophosphonic acid esters of the formula (I) possess a substantially better insecticidal and acaricidal action than the prior art S-( N-acyl-amidocarbonyl)-methyl-thiophosphoric acid esters which are not only the nearest comparable compounds with regard to structure and type of activity but also the best-known commercially available products of this class of substance, and from which the compounds according to the invention differ in respect of the nature of the acyl radical. The new compounds thus represent an enrichment of the art.
The present invention also provides a process for the preparation of an S-(N-acylamidocarbonyl)-methyl- 2 monoor -di-thiophosphoric acid ester or thiophosphonic acid ester of the formula (I) in which an 0,0- dialkyl-monoor -di-thiophosphoric acid salt or thiophosphonic acid salt of the general formula &
is reacted with a halogenoacetic acid N-acylamide of the general formula in which formulas R, R, R", Acyl and X have the above-mentioned meanings,
Hal is a halogen atom, preferably bromine or chlorine, and
M is an alkali metal equivalent, alkaline earth metal equivalent or optionally alkyl-substituted ammonium equivalent.
If the sodium salt of 0,0-dimethyldithiophosphoric acid and chloroacetic acid N-acetyl-N-methylamide are used as starting materials, the course of the reaction can be represented by the following equation:
The following may be mentioned as examples of the 0,0-dialkyl-monoor -di-thiophosphoric acid salts or thiophosphonic acid salts (II) which can be used: the alkali metal salts, alkaline earth metal salts and optionally alkylsubstituted ammonium salts of O-methyl-O- isopropyl-, O-ethyl-O-isopropyl-, 0,0-di-n-propyl, 0,0-di-isopropyland 0,0-di-sec.-butyl-monoand -di-thiophosphoric acids and the corresponding salts of O-methyl, O-ethyland O-isopropyl-methane-monoand -di-thiophosphonic acids and isopropane-monoand -di-thiophosphonic acids.
Examples of suitable halogenoacetic acid N-acylamides (III) are: chloroacetic acid or bromoacetic acid N-acetyl-N-ethyl-, N-acetyl-N-n-butyl-, N-acetyl-N- sec.-butyl-, N-propionyl-N-methyl-, N-propionyl-N- ethyl-, N-propionyl-N-isopropyl-, N-propionyl-N-sec.- butyl-, N-isobutyryl-N-ethyL, N-isobutyryl-N-isopropyl-, N isobutyryl-N-sec.-butyl-, N-benzoyl-N-ethyl-, N-benzoyl-N-isopropyl-, N-benzoyl-N-sec.-butyl-, N- isobutyryl-N-phenyland N-benzoyLN-phenyl-amides.
The (di)thiophosphoric and (di)thiophosphonic acid salts (II) and the halogenoacetic acid derivatives (III) are known and can be prepared according to customary methods.
The preparative process for the new compounds (I) is preferably carried out with conjoint use of a suitable solvent or diluent. As such, practically all inert organic solvents can be used, especially aliphatic and aromatic, optionally chlorinated, hydrocarbons such as benzene, toluene, xylenes, benzine, methylene chloride, chloroform, carbon tetrachloride and chlorobenzene; ethers, for example diethyl ether, dibutyl ether and dioxane; ketones, for example acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; nitriles, such as acetonitrile and propionitrile; and alcohols, for example methanol, ethanol and isopropanol. In certain cases, water is also suitable as a solvent.
The reaction temperature can be varied within a fairly wide range. In general, the reaction is carried out at from to 120C, preferably at from to 60C.
The reaction is in general carried out under normal pressure.
For carrying out the process, the starting materials are in most cases employed in equimolar amounts. An excess of one or other reactant produces no substantial advantages. The reaction is preferably carried out in the presence of one of the above-mentioned solvents, at the indicated temperatures, and the reaction mixture is worked up in the usual manner after stirring for several hours.
The compounds according to the invention are in most cases obtained in the form of colorless to slightly colored viscous, water-soluble oils or crystalline products which in general cannot be distilled without decomposition but can be freed of the last volatile constituents by so-called slight distillation, that is to say prolonged heating to moderately elevated temperatures under reduced pressure, and can be purified in this way. They are characterized, in particular, by the refractive index and, in the case of solid compounds, by the melting point.
As has already been mentioned, the new S-(N- acylamidocarbonyl)-methylthiophosphoric acid esters and thiophosphonic acid esters are distinguished by an excellent insecticidal, acaricidal and soil-insecticidal activity against plant pests, pests of stored products and pests harmful to health. They possess a good action against both sucking and biting insects and against mites (Acarina). At the same time, they show only a slight phytotoxicity.
For these reasons, the compounds according to the invention may be successfully employed as pesticides in plant protection and in the hygiene field.
To the sucking insects there belong, in the main, aphids (Aplzidae) such as the green peach aphid (Myzus persicae), the bean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum padi), the pea aphid (Macrosiphum pisi) and the potato aphid (Macrosiplzum solanifolii), the current gall aphid (Cryptomyzus korschelti), the rosy apple aphid (Sappaphis mall), the mealy plum aphid (Hyalopterus aruna'inis) and the cherry black-fly (Myzus cerasi); in addition, scales and mealybugs (Coccina), for example the oleander scale (Aspidiotus 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 guadrata), the red cotton bug (Dysdercus intermedius), the bed bug (Cimex lectularius), the assassin bug (Rhodnl'us prolixus) and Chagas bug (Triatoma infestans) and, further, cicadas, such as Euscelis bilobatus and Nepholettix bipunclatus.
In the case of the biting insects, above all there should be mentioned butterfly caterpillars (Lepia'optera) such as the diamond-back moth (Plutella maculipennis), the gypsy moth (Lymantria dispar), the brown tail moth (Euproctis clzrysorrhoea) and tent caterpillar (Malacosoma neustria); further, the cabbage moth (Mameslra brassz'cae) and the cutworm (Agrotis segetum), the large whitebutterfly (Pieris brassicae), the small winter moth (Cheimatobia brumata), the green oak tortrix moth (Tortrix viridana), the fall armyworm (Lapliygma frugiperda) and cotton worm (Prodenia litura), the ermine moth (Hyponomeuta padella), the Mediterranean flour moth (Ephestia kuhniella) and greater wax moth (Galleria mellonella).
Also to be classed with the biting insects are beetles (Coleoptera), for example the granary weevil (Siroplzilus granarius Calandra granaria), the Colorado bettle (Leptinotarsa decemlineala), the dock beetle (Gastrophysa viridula), the mustard beetle (Phaedon cochleariae), the blossom beetle (Meligethes aeneus), the raspberry beetle (Byturus tomenrosus), the bean weevil (Bruchidius Acanthoscelides obtectus), the leather beetle (Dermestes frisclzi), the khapra beetle (Trogoderma granarium), the flour beetle (Tribolium castaneum), the northern corn billbug (Calandra or Sitophilus zeamais), the drugstore beetle (Stegobium paniceum), the yellow mealworm (Tenebrio molitor) and the sawtoothed grain beetle (Oryzaephilus surinamensis), and also species living in the soil, for example wireworms (Agriotes spec.) and larvae of the cockchafer (Melolontha melolontha); cockroaches, such as the German cockroach (Blatlella germanica), American cockroach (Periplaneta americana), Madeira cockroach (Leucophaea or Rhyparobia maderae), oriental cockroach (Blatta orientalis), the giant cockroach (Blaberus giganteus) and the black giant cockroach (Blaberus fuscus) as well as Henschoutedenia flexivitta; further, Orthoptera, for example the house cricket (Acheta 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 (Drosophz'la melanogaster), the Mediterranean fruit fly (Ceratitis capilata), the house fly (Musca domestica the little house fly (Fannia canicularis), the black blow fly (Phormia regina) and bluebottle fly (Calliphora erythrocephala) as well as the stable fly (Stomoxys calcitrans); further, gnats, for examples mosquitoes such as the yellow fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles steplzensi).
With the mites (Acari) there are classed, in particular, the spider mites (Tetranychidae) such as the twospotted spider mite (Tetranychus urticae) and the European red mite (Paratetranychus pilosus Panonyclius ulmi), gall mites, for example the blackcurrent gall mite (Eriophyes ribis) and tarsonemids, for example the broad mite (Hemitarsonemus latus) and the cyclamen mite (Tarsonemus pallia'us); finally, ticks, such as the relapsing fever tick (Ornithoa'orus moubata).
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 instant invention can be utilized, if desired,iinthe form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticidediluents or extenders; i.e. diluents, carriers or extenders of the type usable in conventional pesticide formulations'or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, s'pray powders, pastes, solublepowde'rs', dusting agents, granules, etc. These are prepared in known manner, for instance by'extending the active compounds withconventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the u se of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xy-. lene, alkyl naphthalenes, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), cycloalkanes (e.g. cyclohexane, etc.), paraffins (e.g. petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethers and esters thereof (e. g. glycol monomethyl ether, etc. amines (e.g. ethanolamine, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), acetonitrile, ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and/or anionic emulsifying agents (e. g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, albumin hydrolyzates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc. and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.
Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other insecticides, and acan'cides, or rodenticides, fungicides, bactericides, nematocides, herbicides, fertilizers, growth-regulating agents, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.
As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 01-95 percent by weight, and preferably 0.5 percent by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0001-10 percent, preferably 0.0ll percent, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprises mixtures of a conventional dispersible carrier vehicle such as (l) a dispersible inert finely divided carrier solid, and/or (2) a dispersiblelcarrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a 'surfaceactive agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0001- percent, and preferably 0.01-95 percent, by
weight of the mixture.
The active compounds can also be used in accordance with thewell known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in f nely divided form, e.g. average particle diameter of frdrnSO-IOO microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only to at most about a few liters/hectare are needed, and often amounts only up to about 15 to 1000 g/hectarefipreferably 40 to 600 g/hectare, are sufficient. In thisprocess it ispossible to use highly concentrated liquid compositions with said liquid car rier vehicles containing from about 20 to about 95 percent by weight of the active compound or even the percent active substance alone, e.g. about 20-100 percent by weight of the active compound.
Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. insects and acarids, which comprises applying to at least one of correspondingly (a) such insects, (b) such acarids, and (.c) the corresponding habitat thereof, i.e. the locus to be protected, a correspondingly combative or toxic amount, i.e. and insecticidally or acaricidally. effective amount, of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, dressing, encrusting, and the like.
It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or belowthe aforementioned concentration ranges.
The synthesis, unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without limitation, by the following examples:
EXAMPLE I Plutella 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.
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 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 1:
Table 1 8 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.
Cabbage plants (Brassica oleracea) which had been heavily infested with peach aphids (Myzus persicae) 10 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: 100 perecent means that all the aphids were killed, whereas 0 (Plurellu test) concentration in 70 Degree of destruction in after 3 days i (CH;,O) -P-SCH2CONCHO 0.1 100 0.01 0 CH3 (known) (A) s. (C. ,H5O)2PSCH. .CON-CHO 0.1 70 0.01 0 C11, (known) (B) c,11 ,o P s CH3 c11, 0,1 100 ,1-1 s-c11 -NC-CH 0.01 100 c,1-1,,o s
P c,H, s cH -c N -c-c11, 0.01 100 ercent means that none of the a bids were killed. EXAMPLE 2 p P Myzus test (contact action) Solvent: 3 parts by weight of acetone The active compounds, the concentrations of the active compounds, the evaluation times and the results Active compound (Myzus test) Active compound concentration in Degree of destruction in after 1 day (known) (:H o S CH O SCH C C H O S G l-I 0 Table 2-continued (Myzus test) Active compound Active compound D'egree'of destruction concentration in 70 in 70 after lday C ll-,0 S
P CH1, 0.1 100 0.01 100 c 11 s c1-1 fi--N--fi-cH 0.001 98 C,H,0 s
P CH CH, 0.1 100 C2H5O S-Cl-h-C-N-C-CH 0.01 99 0.001
cl-l- (9) C2H,O s
P c|-1 CH 0.1 100 0.01 100 c S-CH -C-N-C-CH 0.001 97 c 11,o s
P CH 0.1 100 0.01 100 CQHSO SCH2-C-N-C 0.001 95 II II 0 (5) c m-,0 s
P CH" 0.1 100 0.01 100 0,11 s-c11 c-N- G 0.001 100 ll 0.0001 0 0 (7) c mo s P i c,,H 0.1 100 .0.01 99 C 11 S-CH fiN-fiCH 0.001 80 c,H .,o s 0.1- x00 r 0.01 99 P v 0.001
v c u S CH C -NC-CH;,
EXAMPLE 3 Rhopalosiphum test (systemic action) 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.
Oat plants (Avena saliva) which had been strongly infested with the bird cherry aphid (Rhopalosiphum padi) we're'watered with the preparation of the active compound softhat the preparation penetrated into the soil without wetting the leaves of the oat plants. The active compound was taken up by the oat plants from the soiland thus reached theinfestecl leaves;
After the specified periods of time, the degree of destruction was determined as a percentage: 100 percent means that all the aphids were killed whereas 0 percent means that none of the a phids were killed.
The active compounds," the concentrationsof the active.compounds,'the evaluation times and the results can be seen from the following Table 3:
Table 3 1 Rhupalosiplmm test/systemic action) I Activewcompound con- Degree of destruction in after 4 days 1 1 CH3 (known) (C) CH;,O\ s c11 0.1 100 0.01 100 c11 SCH. .-fiN-fi-CH;, 0.001 60 o 0 1) c n o o c": 0.1 100 P 0.01 -100 C2H-,O -011 .-fiNf-CH, 0.001 100 (4) c n o s CHI, 01 100 \P 0.01 100 (311 S-CH -fi-Nfi-CH;, 0.001 1 0, H5O 0 C11 CH,
l 0.1 100 c. .1-1 -,o S-CH.fi-Nfi-CH 0.01 100 o 0 CH, 1141 c n o o C11,,
0.1 100 c. .1-1,,o S-CH (i-Nfi 0.01 100 c n o s CH c1-1, I
0;1 100 c 11, S-CH2 C-N-CCH 0.01 100 11 0 s C11 0.1 100 P 0.01 100 c 11 s c1-1 fi-1\1 c| G 0.001 a 40 o in (7) Ex MPLE 4 These bean plants were heavily infested with the twos'potted' spider mite (Tetranychus urticae) in all stages Tetranychus test (resistant) of development.
Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglyco 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 containingthe stated amount of emulsifier and the concentrate was diluted with water to, the desired concentration" Bean plants (PhaseolusvzilgarisJfwhih hadi' ah eight of approximately lO-30cm, were sprayed with preparation of the active compound untilldriipping wet.
Active compound g (known) (A) 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 obtained is expressed as a percentage: percent means that all the spider mites were killed whereas 0 percent means that none of the spider mites were killed. v
The active compounds, the; concentrations of the active compounds, the evaluation times and the. results can be seen from the following Table 42 Table 4 I 1 I '2 (Telranychus test/resistant) I l Table 4-continued TelranyC/HIS lest/resistant Active compound Active compound concentration in 7a Degree of destruction in 7: after 2 days lOO 95 The process of the:presentinvnilofi isillustratedin the following pr'parative Example.
EXAMPLE 5 CH=,0\ P 5 TH. c11 -,o s c1-1, fi 1\1 fi 'c11, "(11 139.4 g (0.93 mole) of chloroacetic acid N-acetyl-N- methylamide were added dropwise, at room temperature, to a solution of 168.0 g (0.93 mole) of the sodium salt of 0,0-dimethyl-dithiophosphoric acid in 600 ml of acetonitrile. The reaction was weakly exothermic. Stirring the mixture was continued overnight at 40 to 50C. The inorganic salts which had separated out were filtered off, the solvent was removed and the residue was taken up in dichloromethane. The solution was twice washed with water and the organic phase was dried over sodium sulfate and filtered. The filtrate was concentrated and S-(N-acetyl-N-methylamidocarbonyl)-methyl-dithiophosphoric acid 0,0-dimethyl ester was obtained as a brown oil which solidified after a short time. The crystalline product had a melting point of 48 to 49C. The yield was 210.0 g (64.8% of theory).
The following compounds were obtained by methods analogous to that above:
C H O 3 continued 1 Refractive index Formula or melting point .c,1 1,o s CH 1 C11,,
C,H s-CH,-C-N- -CH 11,,*= 1.5325
CHM (10) 2 s iC H CHO/P\S CH C N CH c,|-1,o s i c ,H
c,11, s c11, |c|-N-'cc11, 11,, 1.5332
c,1-1,o o i c,H, C /P\ 2o 11,0 s cH. c N c-c1-1 11,, -1.4ss9
II ll CgH5O\ CH3 CH3 /P\ c,H,o SCH- ,C-N-C-CH 11,, 1.4855
II II C2H5O\ o c. .11 ,o s c11 N-(I-CH,, 11,,== 1.5313
c,1-1,,o s
c 11 s cH (fi) N fi-c11, 11,,*"= 1.5725
Other compounds which can be similarly prepared include:
S-(N-propionyl-N-n-butyl-amidocarbonyl)-methyldithiophosphoric acid O-propyl-O-n-butyl ester, S-( N-be nzoyl-N-ethyl-amidocarbonyl )-methyl-isopropanethiolphosphonic acid O-isobutyl ester, S-( N-valeryl-N-isopropyl-amidocarbonyl )-methylmethanethiolphosphonic acid O-t-butyl ester, S-( N-be nzoyl-N-phenyl-amidocarbonyl )-methylbutanedithiophosphonic acid Q-isopropyl ester, and the like.
What is claimed is:
l.- The compound; .S N acetyl-Nrmethyl-amidocarbonyl) methyIdithiophQsphOric acid 0,0-dimethyl ester of the formula 17 18 .1 8 3 3. The compound S-(N-acetyl-N-methyl-amidocart bonyl)-methylthiolphosphoric acid 0,0-d1ethyl ester of the formula CH O S-CH2CN--C-CH,,
y) 2 s 0 H3 2. The compound S-(N-acetyl-N-methyl-amidocarbony])-methyl-dithiophosphoric acid 0,0-diethyl ester The compound Nbenzoy] N methyl amidocar of the formula bonyl)-methyl-ethanedithiophosphonic acid O-ethyl ester of the formula

Claims (4)

1. The compound S-(N-acetyl-N-methyl-amidocarbonyl)-methyldithiophosphoric acid O,O-dimethyl ester of the formula
2. The compound S-(N-acetyl-N-methyl-amidocarbonyl)-methyl-dithiophosphoric acid O,O-diethyl ester of the formula
3. THE COMPOUND S-(N-ACETYLN-METHYL-AMIDOCARBONYL)METHYLTHIOPHOSPHORIC ACID O,O-DIETHYL ESTER OF THE FORMULA
4. The compound S-(N-benzoyl-N-methyl-amidocarbonyl)-methyl-ethanedithiophosphonic acid O-ethyl ester of the formula
US384676A 1972-08-16 1973-08-01 S-(n-acyl-n-alkyl or phenyl-amidocarbonyl)-methyl-thio-phosphoric and- -phosphonic acid esters Expired - Lifetime US3928508A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2864849A (en) * 1955-09-07 1958-12-16 Bayer Ag Thiophosphoric acid esters and their production
US3176035A (en) * 1959-07-17 1965-03-30 Sandoz Ltd Aldehydo-substituted mono- and di-thiophosphoric acid esters
US3752871A (en) * 1970-07-30 1973-08-14 Bayer Ag O - alkyl - n-monoalkyl-s-(n'-acyl-carbamylmethyl) - thionothiolphosphoric acid ester amides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2864849A (en) * 1955-09-07 1958-12-16 Bayer Ag Thiophosphoric acid esters and their production
US3176035A (en) * 1959-07-17 1965-03-30 Sandoz Ltd Aldehydo-substituted mono- and di-thiophosphoric acid esters
US3752871A (en) * 1970-07-30 1973-08-14 Bayer Ag O - alkyl - n-monoalkyl-s-(n'-acyl-carbamylmethyl) - thionothiolphosphoric acid ester amides

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