US3057774A - Carbamoylalkyl phosphonothioates - Google Patents

Carbamoylalkyl phosphonothioates Download PDF

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US3057774A
US3057774A US1419360A US3057774A US 3057774 A US3057774 A US 3057774A US 1419360 A US1419360 A US 1419360A US 3057774 A US3057774 A US 3057774A
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ethyl
methylphosphonodithioate
water
weight
phosphonothioates
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Joseph W Baker
John P Chupp
Peter E Newallis
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Monsanto Chemicals Ltd
Monsanto Chemical Co
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02Phosphorus compounds
    • C07F9/547Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6536Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and sulfur atoms with or without oxygen atoms, as the only ring hetero atoms
    • C07F9/6544Six-membered rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02Phosphorus compounds
    • C07F9/28Phosphorus compounds with one or more P—C bonds
    • C07F9/38Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/40Esters thereof
    • C07F9/4071Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4075Esters with hydroxyalkyl compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02Phosphorus compounds
    • C07F9/547Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576Six-membered rings
    • C07F9/59Hydrogenated pyridine rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02Phosphorus compounds
    • C07F9/547Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6527Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07F9/6533Six-membered rings

Description

United States Pater O 3,057,774 CARBAMOYLALKYL PHOSPHONOTHIOATES Joseph W. Baker and John P. Chupp, Kirkwood, and

Peter E. Newallis, Crestwood, Mo., assignors to Monsanto Chemical Company, St. Louis, Mo., :1 corporation of Delaware No Drawing. Filed Mar. 11, 1960, Ser. No. 14,193 19 Claims. (Cl. 167-22) This invention relates to new and useful phosphonothioates and to methods of making same. Additionally this invention relates to insecticidal compositions containing the new phosphonothioates as an active ingredient.

The new compounds of this invention can be termed carbamoylalkyl phosphonothiates and can be represented by the structure wherein R is phenyl or an alkyl radical containing from 1 to carbon atoms (i.e. methyl, ethyl, propyl, butyl, amyl, and the various isomeric forms thereof); wherein R is an alkyl radical containing from 1 to 4 carbon atoms (i.e. methyl, ethyl, propyl, butyl, and the various isomeric forms thereof); wherein X is a chalkogen of atomic weight less than 40 (i.e. sulfur or oxygen); wherein A is a divalent aliphatic hydrocarbon radical having the empirical formula C T-I wherein n is a whole number from 1 to 3; and wherein N is (1) NH or (2) a primary amine residue NHR" wherein R is a hydrocarbon radical containing not more than 7 carbon atoms or (3) a secondary amine residue NRR" wherein R" and R are hydrocarbon radicals containing not more than 7 carbon atoms or (4) a saturated single ring heterocyclic secondary amine residue containing not more than 5 carbon atoms (e.g. morpholinyl, C H ON, thiamorpholinyl, C H SN, piperidyl, C H N, pyrrolidyl, C H N, etc.).

By the expression hydrocarbon radicals containing not more than 7 carbon atoms is meant to include the aryl, alkaryl, aralkyl, cycloalkyl, alkenyl and alkyl radicals as exemplified by phenyl, tolyl, benzyl, cyclohexyl, methylcyclohexyl, allyl, methallyl, methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, and the various isomeric hydrocarbon forms thereof containing not more than 7 carbon radicals. In general it is preferred that R" and R' be aliphatic hydrocarbon radicals containing not more than 3 carbon atoms (i.e. methyl, ethyl, n-propyl, isopropyl, and allyl) and it is preferred that R and R be alkyl radicals containing not more than 3 carbon atoms (i.e., methyl, ethyl, n-propyl, or isopropyl).

The phosphonothioates of this invention can be prepared by reacting a salt (i.e. ammonium or alkali metal such as sodium, potassium, or lithium) of a phosphonothioic acid of the structure RO X wherein X, R and R have the aforedescribed significance in an anhydrous system with a substantially equimolecular amount of an amide of the structure wherein A and N have the aforedescribed significance and wherein the term halogen means a halogen having an atomic number above 9 but not higher than 35 in the presence of an inert organic liquid or solvent (e.g. acetone, methyl ethyl ketone, benzene, toluene, xylene, etc.), at a temperature above the freezing point of the system and "ice up to and including the boiling point of the system, but preferably at a temperature in the range of 20 C. to 120 C.

As illustrative of the phosphonothioates of this invention is the following:

O-methyl S-(carbamoylmethyl) methylphosphonodithioate O-ethyl S-(carbamoylmethyl) methylphosphonodithioate O-ethyl S-(carbamoylmethyl) methylphosphonothiate O-ethyl S-(carbamoylmethyl) isopropylphosphonothioate O-ethyl S-(carbamoylmethyl) phenylphosphonodithioate O-isopropyl S[2-(carbamoyl)ethyl] ethy-lphosphonodithioate V O-n-butyl S-[3-(carbamoyl)propyl] methylphosphonodithioate O-methyl S-(N-methylcarbamoylmethyl) phonothioate O-ethyl S-(N-ethylcarbamoylmethyl) methylphosphono thioate O-ethyl S-(N-allylcarbamoylmethyl) isopropylphosphonodithioate O-ethyl S-(N-isopropylcarbamoylmethyl) phenylphosphonodithioate O -ethyl S- (N-isoamylcarbamoylmethyl) methylphosphonodithioate O-ethyl S-(N-phenylcarbamoylmethyl) methylphosphonodithioate O ethyl S (N-cyclohexylcarbamoylmethyl) ethylphosphonodithioate Omethyl S-(N,N-dimethylcarbamoylmethyl) methylphosphonothioate O-methyl S-(N,N-dimethylcarbamoylmethyl) methylphosphonodithioate O-ethyl S-(N,N-dimethylcarbamoylmethyl) methylphosphonodithioate O-ethyl S-[2-(N,N-diethylcarbamoyl)ethyl] ethylphosphonodithioate O-ethyl S-(N,N-diallylcarbamoylmethyl) methylphosphonodithioate O- ethyl S-(N,N-diallylcarbamoylmethyl) phenylphosphonodithioate O -isopropyl S-(N,N-diisopropylcarbamoylrnethyl) methylphosphonothioate O-methyl S-(N,N-diphenylcarbamoylmethyl) methylphosphonodithioate O-methyl S-(N-ethyl-N-phenylcarbamoylmethyl) ethylphosphonothioate O-methyl S-(4-morpholinylcarbonylmethyl) methylphosphonodithioate O-methyl S-(1-piperidinylcarbonylmethyl) methylphosphonodithioate O-ethyl S-(4-thiamorph0linylcarbonylmethyl) phosphonodithioate O-methyl S-(N-methyl-N- phenylcarbamoylmethyl) methylphosphonothioate methyl-phosmethyl- As illustrative of the preparation of the compounds of this invention is the following:

To a suitable reaction vessel equipped with a thermometer, agitator and reflux condenser is charged parts by weight of acetone, 13.5 parts by weight (substantially 0.10 mol) of 2-chloro-N-isopropylacetamide, and 19.0 parts by Weight (substantially 0.11 mol) of ammonium O-ethyl methylphosphonodithioate and the mass refluxed for 4 hours. The reaction mass is then cooled to room temperature and filtered. The filter cake is then washed with acetone and the washings combined with the original filtrate. The liquid mass is then subjected to vacuum distillation to remove the acetone. The residue is then taken up with 75 parts by weight of methylene chloride and the organic solution washed first with aqueous sodium carbonate and then twice with water and the washings discarded. The so-washed organic solution is then subjected to vacuum distillation to remove the solvent. The residue, an amber oil, is O-ethyl S-(N-isopropylcarbamoylmethyl) methylphosphonodithioate which is soluble in ethanol and chloroform but insoluble in water. Analysis.--Theory: 5.6% N, 11.9% P, 24.6% S. Found: 5.5% N, 12.1% P, 25.1% S.

Example ll CH3 i H PSCHrC-NHCH 031150 Employing the procedure of Example I but replacing 2-chloro-N-isopropylacetamide with an equimolecular amount of 2-chloro-N-methylacetamide there is obtained ethyl S (N methylcarbamoylmethyl) methylphosphonodithioate, a brown solid soluble in chloroform but insoluble in water.

Employing the procedure of Example I but replacing 2-chloro-N-isopropylacetamide with an equimolecular amount of 2-chloro-N-methylacetamide and replacing ammonium O-ethyl methylphosphonodithioate with an equimolecular amount of ammonium O-methyl methylphosphonodithioate there is obtained O-methyl S-(N- methylcarbamoylmethyl) methylphosphonodithioate, an oil soluble in chloroform but insoluble in water.

Example IV CH3 S CgHsO Employing the procedure of Example I but replacing 2-chloro-N-isopropylacetamide with an equimolecular amount of N-allyl-2-chloroacetamide there is obtained O-ethyl S-(N-allyl-carbamoylmethyl) methylphosphonodithioate which is soluble in chloroform and isopropyl alcohol but insoluble in water.

Example V CH ISI Employing the procedure of Example I but replacing 2-ch1oro-N-isopropylacetamide with an equimolecular amount of 2-chloro-acetamide there is obtained O-ethyl S-(carbamoylmethyl) methylphosphonodithioate which is soluble in chloroform but insoluble in water.

Example VI OH; S

CzHsO Employing the procedure of Example I but replacing 2-chloro-N-isopropylacetamide with an equimolecular amount of N,N-diallyl alpha-chloro acetamide there is obtained S-(N,N-diallyl-carbamoylmethyl) O-ethyl methylphosphonodithioate which oil is soluble in chloroform but insoluble in water.

Employing the procedure of Example I but replacing ammonium O-ethyl methylphosphonodithioate with an equimolecular amount of sodium O-ethyl phenylphosphonothioate there is obtained O-ethyl S-(N-isopropylcarbamoylmethyl) phenylphosphonothioate which is soluble in chloroform but insoluble in water.

Example IX Employing the procedure of Example I but replacing ammonium O-ethyl methylphosphonodithioate With an equimolecular amount of ammonium O-ethyl methylphosphonothioate there is obtained O-ethyl S-(N-isopropylcarbamoylmethyl) methylphosphonothioate which is soluble in ethanol, carbon tetrachloride and chloroform but insoluble in water.

Example X CH3 0 O l 'SCEhi'JNHC/H;

Employing the procedure of Example I but replacing ammonium O-ethyl methylphosphonodithioate with an equimolecular amount of ammonium O-ethyl methylphosphonothioate and replacing 2-chloro-N-isopropylacetarnide with an equimolecular amount of 2-chloro-N-methylacetamide there is obtained O-ethyl S-(N-methylcarbamoylmethyl) methylphosphonothioate which is insoluble in water, but soluble in chloroform, ethanol and butanone.

The phosphonothioates of this invention can also be prepared by reacting a phosphonothioic acid of the structure Kit P-SH

wherein R, R and X have the aforedescribed significance in an anhydrous system with a substantially equimolecular amount of an acrylamide of the structure wherein a and b are unlike integers from 0 to 1, inclusive, and wherein N has the aforedescribed significance in the presence of an inert organic liquid or solvent (e.g. acetone, methyl ethyl ketone, dioxane, benzene, toluene, xylene, etc.) at a temperature above the freezing point of the system and up to and including the boiling point of the system, but preferably in the range of 20 C. to C. This reaction can be accelerated by the use of a catalyst, e.g. a tertiary organic amine such as pyridine, triethylamine, choline and their equivalents. Any catalytic amount can be employed which amount usually will be in the range of 0.1 to 2.5% by Weight based on the total weight of the respective reactants. Because of the tendency of acrylamides to polymerize the reaction is most advantageously carried out in the presence of a polymerization inhibitor, e.g. hydroquinone. As illustrative of this means of preparing the compounds of this invention is the following:

EXAMPLE XI CH3 S H il P SOHzOHzCNHz To a suitable reaction vessel equipped with a thermometer, agitator and reflux condenser and containing approximately 80 parts by weight of dioxane, approximately 15.6 parts by weight (substantially 0.10 mole) of O-ethyl methylphosphonodithioic acid approximately 0.3 part by weight of triethylamine and approximately 0.2 part by weight of hydroquinone is added slowly with external cooling approximately 6.4 parts by weight (substantially 0.09 mole) of acrylamide. The temperature is raised slowly to the refluxing temperature and held there for ten hours. The resulting organic solution is then subjected to vacuum distillation to remove the dioxane. The residue is then taken up with methylene chloride and the organic solution washed first with aqueous sodium carbonate and then twice with water and the washings discarded. The so-washed organic solution is then subjected to vacuum distillation to remove the solvent. The residue, (21.0 parts by weight) is S-(Z-carbamoylethyl) O-ethyl methylphosphonodithioate, which is soluble in acetone, ethanol and chloroform but insoluble in water.

EXAMPLE XII CH3 S Employing the procedure of Example XI but replacing acrylamide with an equimolar quantity of methacrylamide there is obtained S-(Z-carbamoylpropyl) O-ethyl methylphosphonodithioate which is soluble in acetone, carbon tetrachloride and methanol, but insoluble in water.

EXAMPLE XIII PSCHzOH-CNHGH(GH5)2 CzHsQ H3 Employing the procedure of Example XI but replacing acrylamide with an equimolar quantity of N-isopropylmethacrylamide there is obtained O-ethyl S-(Z-N-isopropylcarbamoylpropyl) methylphosphonodithioate which is soluble in chloroform and acetone but insoluble in water.

EXAMPLE XIV \fi l PSOHOHz-(iNHz O2H O H3 Employing the procedure of Example XI but replacing acrylamide with an equimolar amount of crotonamide there is obtained O-ethyl S-(Z-carbamoylisopropyl) methylphosphonodithioate which is insoluble in water.

EXAMPLE XV (CH3)2GEO Employing the procedure of Example XI but replacing O-ethyl methylphosphonodithioic acid with an equimolar quantity of O-isopropyl ethylphosphonodithioic acid there is 7 obtained s-(carbamoylethyl) O-isopropyl ethylphosphonodithioate which is soluble in chloroform and acetone but insoluble in water.

EXAMPLE XVI onmono s i -SGHB( iNHCHa CH3 OHQCHZ Employing the procedure of Example I but replacing 2-chloro-N-isopropylacetamide with an equimolar amount of 4-morpholinylcarbonylmethyl chloride there is obtained O-ethyl S(4-rnorpholinylcarbonylmethyl) methylphosphonodithioate which is insoluble in Water.

In the processes of this invention any inert organic liquid or mixture of inert organic liquids can be used provided at least one of the reactants is soluble therein. The methods by which the phosphonothioates of this invention are isolated will vary slightly with the reactants employed and the product produced. Further purification by selective solvent extraction or by absorptive agents such as activated carbon or clays can precede the removal of the inert organic liquid or solvent. Additionally an inert organic solvent can be added to and in the purification by absorptive agents. However, the product is generally satisfactory for insecticidal purposes without further purification.

It will be understood that the terms insect and insecticide are used herein in their broad common useage to include spiders, mites, ticks, and like pests which are not in the strict biological sense classed as insects. Thus the useage herein conforms to the definitions provided by Congress in Public Law 104, the Federal Insecticide, Fungicide, and Rodenticide Act of 1947, Section 2, subsection h, wherein the term insect is used to refer not only to those small invertebrate animals belonging mostly to the class Insecta, comprising six-legged, usually winged forms, as beetles, bugs, bees, flies, and so forth, but also to other allied classes of arthropods Whose members are Wingless and usually have more than six legs, as spiders, mites, ticks, centipedes, and wood lice.

The phosphonothiates of this invention are effective against a wide variety of insect pests. As illustrative of the activity but not lirnitative thereof is the following:

One gram of O-ethyl S-(N-isopropylcarbamoylmethyl) methylphosphonodithioate was dissolved in sufficient acetone to make a concentrate solution thereof. Approximately 0.1 co. of sorbitan monolaurate polyoxyethylene derivative (a commercial water-soluble nonionic emulsifying agent containing 20 moles of ethylene oxide per mole of sorbitan monolaurate) is then mixed with the concentrate. To this mixture and with agitation is added sufficient Water to provide an aqueous emulsion A having a concentration of 0.004% by Weight of O-ethyl 7 sults against the mobile, resting and ova stages of the same mite were obtained employing instead of O-ethyl S-(N- isopropylcarbamoylmethyl) methylphosphonodithioate the following:

O-methyl S- (N-methylcarbamoylmethyl) methylphosphonodithioate, and O-ethyl S-(N-methylcarbamoylmethyl) methylphosphonodithioate at like concentrations.

Contact activity was also observed employing the compounds of this invention against the red flour beetle, e.g. a 100% kill was observed employing O-ethyl S-(N-methylcarbamoylmethyl) methylphosphonodithioate at a concentration of 0.25% by weight.

Employing O-ethyl S (N methylcarbamoylmethyl) methylphosphonodithioate at a concentration of 2.5 p.p.m. against yellow fever mosquito larvae, Ades aegypti, 100% kill was observed.

Contact activity was also observed against the southern armyworm, Prodenia eridania, employing the compounds of this invention.

Systemic activity was also observed against a wide variety of insects. For example against the two-spotted spider mite, Tezranychus telarius (L.), a 100% kill was observed employing O-ethyl S-(N-isopropylcarbamoylmethyl) methylphosphonodithioate at a concentration of 0.004% by weight. Also for example against the southern armyworm, Prodenia cridania, a 100% kill was observed employing O-ethyl S-(N-rnethylcarbamoylmethyl) methylphosphonodithioate at a concentration of 0.016% by weight.

Although the phosphonothioates of this invention are useful per se in controlling a wide variety of insect pests, it is preferable that they be supplied to the pests or to the environment of the pest or pests in a dispersed form in a suitable extending agent.

In the instant specification and appended claims it is to be understood that the term dispersed is used in its widest possible sense. When it is said that the phosphonothioates of this invention are dispersed, it means that particles of the phosphonothioates of this invention may be molecular in size and held in true solution in a suitable organic solvent. It means further, that the particles may be colloidal in size and distributed throughout a liquid phase in the form of suspensions or emulsions or in the form of particles held in suspension by wetting agents. It also includes particles which are distributed in a semi-solid viscous carrier such as petrolatum or soap or other ointment base in which they may be actually dissolved in the semi-solid or held in suspension in the semi-solid with the aid of suitable wetting or emulsifying agents. The term dispersed also means that the particles may be mixed with and distributed throughout a solid carrier providing a mixture in particulate form, e.g. pellets, granules, powders, or dusts. The term dispersed also includes mixtures which are suitable for use as aerosols including solutions, suspensions, or emulsions of the phosphonothioates of this invention in a carrier such as dichloro-difluoromethane and like fluorochloroalkanes which boil below room temperature at atmos pheric pressure.

In the instant specification and appended claims it is to be understood that the expression extending agent" includes any and all of those substances in which the phosphonothioates of this invention are dispersed. It includes, therefore, the solvents of a true solution, the liquid phase of suspensions, emulsions or aerosols, the semi-solid carrier of ointments and the solid phase of particulate solids, e.g. pellets, granules, dusts and powders.

The exact concentration of the phosphonothioates of this invention employed in combatting or controlling insect pests can vary considerably provided the required dosage (i.e., toxic or lethal amount) thereof is supplied to the pests or to the environment of the pests. When the extending agent is a liquid or mixture of liquids (e.g. as in solutions, suspensions, emulsions, or aerosols) the concentration of the phosphonothioate employed to supply the desired dosage generally will be in the range of 0.001 to 50 percent by weight. When the extending agent is a semi-solid or solid, the concentration of the phosphonothioate employed to supply the desired dosage generally will be in the range of 0.1 to 25 percent by weight. From a practical point of view, the manufacturer must supply the agriculturist with a low-cost concentrate or spray base or particulate solid base in such form that, by merely mixing with water or solid extender (e.g., powdered clay or talc) or other low-cost material available to the agriculturist at the point of use, he will have an easily prepared insecticidal spray or particulate solid. In such a concentrate composition, the phosphonothioate generally will be present in a concentration of 5 to 95 percent by weight, the residue being any one or more of the well known insecticidal adjuvants, such as the various surface active agents (e.g., detergents, a soap or other emulsifying or wetting agent), surfaceactive clays, solvents, diluents, carrier media, adhesives, spreading agents, humectants, and the like.

There are a large number of organic liquids which can be used for the preparation of solutions, suspensions or emulsions of the phosphonothioates of this invention. For example, isopropyl ether, acetone, methyl ethyl ketone, dioxane, cyclohexanone, carbon tetrachloride, ethylene dichloride, tetrachloroethane, hexane, heptane and like higher liquid alkanes, hydrogenated naphthalenes, solvent naphtha, benzene, toluene, xylene, petroleum fractions (e.g. those boiling almost entirely under 400 F. at atmospheric pressure and having a flash point above about F., particularly kerosene), mineral oils having an unsulfonatable residue above about 80 percent and preferably above about percent. In those instances wherein there may be concern about the phytotoxicity of the organic liquid extending agent a portion of same can be replaced by such low molecular weight aliphatic hydrocarbons as dipentene, diisobutylene, propylene trimer, and the like or suitable polar organic liquids such as the aliphatic ethers and the aliphatic ketones containing not more than about 10 carbon atoms as exemplified by acetone, methyl ethyl ketone, diisobutyl ketone, dioxane, isopropyl ether, and the like. In certain instances, it is advantageous to employ a mixture of organic liquids as the extending agent.

When the phosphonothioates of this invention are to be supplied to the insect pests or to the environment of the pests as aerosols, it is convenient to dissolve them in a suitable solvent and disperse the resulting solution in dichlorodifluoromethane or like chlorofluoroalkane which boils below room temperature at atmospheric pressure.

The phosphonothioates of this invention are preferably supplied to the insect pests or to the environment of the insect pests in the form of emulsions or suspensions. Emulsions or suspensions are prepared by dispersing the phosphonothioate of this invention either per se or in the form of an organic solution thereof in water with the aid of a water-soluble surfactant. The term surfactant as employed here and in the appended claims is used as in volume II of Schwartz, Perry and Berchs Surface Active Agents and Detergents (1958, Interscience Publishers, Inc., New York) in place of the expression emulsifying agent to connote generically the various emulsifying agents, dispersing agents, wetting agents and spreading agents that are adapted to be admixed with the active compounds of this invention in order to secure better wetting and spreading of the active ingredients in the water vehicle or carrier in which they are insoluble through lowering the surface tension of the water (see also Frear, Chemistry of Insecticides, Fungicides and Herbicides, second edition page 280). These surfactants include the well-known capillary-active substances which may be anion-active (or anionic), cation active (or cationic), or non-ionizing (or non-ionic) which are described in detail in volumes I and II of Schwartz, Perry and Berchs Surface Active Agents and Detergents (1958, Interscience Publishers, Inc., New York), and also in the November 1947 issue of Chemical Industries (pages 811-824) in an article entitled Synthetic Detergents, by John W. McCutcheon, and also in the July, August, September and October 1952 issues of Soap and Sanitary Chemicals under the title Synthetic Detergents. The disclosures of these articles with respect to surfactants, i.e. the anion-active, cation-active and non-ionizing capillary active substances, are incorporated in this specification by reference in order to avoid unnecessary enlargement of this specification. The preferred surfactants are the water-soluble anionic surface-active agents and the water soluble non-ionic surface-active agents set forth in US. 2,846,398 (issued August 5, 1958). In general it is preferred that a mixture of water-soluble anionic and water-soluble non-ionic surfactants be employed.

The phosphonothioate's of this invention can be dispersed by suitable methods (e.g., tumbling or grinding) in solid extending agents either of organic or inorganic nature and supplied to theinsect pests environment in particulate form. Such solid materials include for example, tricalcium phosphate, calcium carbonate, kaolin, bole, kieselguhr, talc, bentonite, fullers earth, pyrophyllite, diatomaceous earth, calcined magnesia, volcanic ash, sulfur and the like inorganic solid materials, and include for example, such materials of organic nature as powdered cork, powdered wood, and powdered walnut shells. The preferred solid carriers are the adsorbent clays, e.g. bentonite. These mixtures can be used for insecticidal purposes in the dry form, or, by addition of water-soluble surfactants or wetting agents the dry particulate solids can be rendered wettable by water so as to obtain stable aqueous dispersions or suspensions suitable for use as sprays.

For special purposes the phosphonothioates of this invention can be dispersed in a semi-solid extending agent such as petrolatum or soap (e.g., sodium stearate or oleate or palmitate or mixtures thereof) with or without the aid of solubility promoters and/or surfactants or dispersing agents.

In all of the forms described above the dispersions can be provided ready for use in combatting insect pests or they can be provided in a concentrated form suitable for mixing with or dispersing in other extending agents. As illustrative of a particularly useful concentrate is an intimate mixture of phosphonothioate of this invention with a water-soluble surfactant which lowers the surface ten sion of water in the weight proportions of 0.1 to 15 parts of surfactant with sufficient of the phosphonothioate of this invention to make 100 parts by weight. Such a concentrate is particularly adapted to be made into a spray for combatting various forms of insect pests (particularly mites) by the addition of water thereto. As illustrative of such a concentrate is an intimate mixture of 95 parts by weight of O-ethyl S-(N-methylcarbamoylmethyl) methylphosphonodithioate and parts by weight of a water-soluble non-ionic surfactant such as the polyoxyethylene derivative of sorbitan monolaurate.

Another useful concentrate adapted to be made into a spray for combatting insect pests (particularly mites) is a solution (preferably as concentrated as possible) of a phosphonothioate of this invention in an organic solvent therefor. The said liquid concentrate preferably contains dissolved therein a minor amount (e.g., 0.5 to percent by weight of the weight of the new insecticidal agent) of a surfactant (or emulsifying agent), which surfactant is also water-soluble. As illustrative of such a concentrate is a solution of O-ethyl S-(N-isopropylcarbamoylmethyl) methylphosphonodithioate in benzene which solution contains dissolved therein a water-soluble polyoxyethylene glycol non-ionic surfactant and a watersoluble alkylaryl sulfonate anionic surfactant.

Of the surfactants aforementioned in preparing the various emulsifiable, wettable or dispersible compositions or concentrates of this invention, the anionic and nonionic surfactants are preferred. Of the anionic surfactants, the particularly preferred are the well known watersoluble alkali metal alkylaryl sulfonates as exemplified by sodium decylbenzene sulfonate and sodium dodecylbenzene sulfonate. Of the non-ionic surfactants, the particularly preferred are the water-soluble polyoxyethylene derivatives of alkylphenols (particularly isooctylphenol) and the water-soluble polyoxyethylene derivatives of the mono-higher fatty acid esters of sorbitan containing 15 to 30 moles of ethylene oxide per mole of sorbitan monoester or alkylphenol.

In all of the various dispersions described hereinbefore for insecticidal purposes, the active ingredient can be one or more of the compounds of this invention. The compounds of this invention can also be advantageously employed in combination with other pesticides, including, for example, nematocides, bactericides, and herbicides. In this manner it is possible to obtain mixtures which are effective against a wide variety of pests and other forms of noxious life.

In controlling or combatting insect pests the O-aryl phosphonothioates of this invention either per se or compositions comprising same are supplied to the insect pests or to their environment in a lethal or toxic amount. This can be done by dispersing the new insecticidal agent or insecticidal composition comprising same in, on or over an infested environment or in, on or over an environment the insect pests frequent, e.g. agricultural soil or other growth media or other media infested with insect pests or attractable to the pests for habitational or sustenance or propagational purposes, in any conventional fashion which permits contact between the insect pests and the phosphonothioates of this invention. Such dispersing can be brought about by applying sprays or particulate solid compositions to a surface infested with the insect pests or attractable to the pests, as for example, the surface of an agricultural soil or other media such as the above ground surface of plants by any of the conventional methods, e.g. power clusters, boom and hand sprayers, and spray dusters. Also for sub-surface application such dispersing can be carried out by simply mixing the new insecticidal agent per se or insecticidal spray or particulate solid compositions comprising same with the infested environment or with the environment the insect pests frequent, or by employing a liquid carrier for the new insecticidal agent to accomplish sub-surface penetration and impregnation therein.

While this invention has been described with respect to certain'embodiments, it is to be understood that it is not so limited and that variations and modifications thereof obvious to those skilled in the art can be made without departing from the spirit and scope thereof.

What is claimed is:

1. Carbamoylalkyl phosphonothioates of the structure RO X o hsautn wherein R is selected from the group consisting of phenyl and alkyl radicals containing from 1 to 5 carbon atoms; wherein R is an alkyl radical containing from 1 to 4 carbon atoms; wherein X is a chalkogen of atomic weight less than 40; wherein A is a divalent aliphatic hydrocarbon radical having the empirical formula C H wherein n is a whole number from 1 to 3; and wherein N is selected from the group consisting of (l) NH (2) NHR wherein R" is a hydrocarbon radical containing from 1 to 7 carbon atoms and are selected from the group consisting of aryl, alkaryl, aralkyl, cycloalkyl, alkenyl and alkyl radicals, (3) NR"R wherein R" and R are hydrocarbon radicals containing from 1 to 7 carbon atoms, and (4) saturated single ring heterocyclic secondary amine residues containing not more than carbon atoms in the ring.

2. Carbamoylalkyl phosphonothioates of the structure r t P S- CH2CNRR wherein R and R are alkyl radicals containing not more than 3 carbon atoms wherein R" and R are aliphatic hydrocarbon radicals containing not more than 3 carbon atoms and selected from the group consisting of alkyl and alkenyl radicals.

3. Canbamoylalkyl phosphonothioates of the structure wherein R and R are alkyl radicals containing not more than 3 carbon atoms and wherein R" is an aliphatic hydrocarbon radical containing not more than 3 carbon atoms and selected from the group consisting of alkyl and alkenyl radicals.

4. O-ethyl S-(N-isopropylcarbamoylmethyl) methylphosphonodithioate.

5. O-ethyl S-(N-methylcarbarnoylmethyl) methylphosphonondithioate.

6. O-ethyl S-(N,N-diallylcarbamoyalmethyl) methylphosphonodithioate.

7. O-ethyl S-(N-isopropylcarbamoylmethyl) methylphosphonothioate.

8. O-ethyl S-(carbamoylmethyl) methylphosphonodithioate.

9. The method of making the compounds of claim 1 which comprises reacting in an anhydrous system a salt selected from the class consisting of ammonium and alkali metals of a phosphonothioic acid of the structure.

where R, R and X have the same significance as in claim 1 with a substantially equimolar amount of a halide of the structure I halogen-AO-N wherein halogen means a halogen having an atomic number above 9 but not higher than 35 and wherein A and N have the same significance as in claim 1 in the presence of an inert organic liquid.

10. The method of making compounds of claim 1 WhlCh comprises reacting in an anhydrous system a phosphonothioic acid of the structure R O INC P-SH 12 wherein R, R and X have the same significance as in claim 1 with a substantially equimolecular amount of an amide of the structure wherein a and b are unlike integers from 0 to 1 and wherein N has the same significance as in claim 1 in the presence of an inert organic liquid and a catalytic amount of a tertiary organic amine.

11. An insecticidal composition comprising a compound of claim 1 dispersed in an extending agent.

12. An insecticidal composition comprising a compound of claim 1 dispersed in an extending agent, the composition containing 0.1 to 25 percent by weight of said compound of claim 1, the extending agent being selected from the group consisting of solid and semi-solid extending agents.

13. An insecticidal composition comprising a compound of claim 1 dispersed in a liquid extending agent, the composition containing 0.001 to percent by weight of said compound of claim 1.

14. An insecticidal composition comprising a compound of claim 2 dispersed in an adsorbent clay, the composition containing 0.1 to 25 percent by weight of said compound of claim 2.

15. An insecticidal concentrate comprising a compound of claim 2 and an insecticidal adjuvant, said concentratc containing from 5 to percent by weight of the compound of claim 2.

16. An insecticidal concentrate comprising a compound of claim 1 dispersed in an organic solvent therefor and having dissolved therein a minor amount of a surfactant, said concentrate forming an emulsion with water upon agitation therewith.

17. An insecticidal concentrate adapted to be made into a sprayable composition by the addition of water comprising a compound of claim 2 in admixture with a watersoluble surfactant in the weight proportion of 0.1 to 15 parts of surfactant and suflicient of said compound of claim 2 to make parts by weight.

18. The method of controlling insects which comprises contacting the insects with a toxic amount of a compound of claim 1.

19. The method of controlling insects which comprises contacting the insects with a toxic amount of a compound of claim 2.

References Cited in the file of this patent UNITED STATES PATENTS 2,668,831 Tolkrnith Feb. 9, 1954 2,712,029 Winkle June 28, 1955 2,864,849 Schrader Dec. 16, 1958 2,912,452 Schrader Nov. 10, 1959 2,915,429 Scherer Dec. 1, 1959 2,920,993 Fairchild Jan. 12, 1960 :UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,057,774 October 9, 1962 Joseph W. Baker et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 10, line 75, after "atoms, insert and are selected from the group consisting of aryl, alkaryl, aralkyl, cycloa l kyl, alkenyl and alkyl radicals Signed and sealed this 26th day of February 1963,

(SEAL) Attest:

ESTON co JOHNSON I DAVID L. LADD Commissioner of Patents Attesting Officer

Claims (1)

1. A CARBAMOYLAKYL PHOSPHONOTHIOATES OF THE STRUCTURE
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3233010A (en) * 1959-10-02 1966-02-01 Bayer Ag Dithiophosphonic acid esters and process for their production
US3238202A (en) * 1961-05-02 1966-03-01 Montedison Spa Amides of o, o-dialkyldithiophos-phorylacetic acids
US3351679A (en) * 1964-08-07 1967-11-07 Stauffer Chemical Co Substituted (nu-formyl-nu-alkylcarbamoyl methyl) phosphonothioates
US3401220A (en) * 1964-08-07 1968-09-10 Stauffer Chemical Co Methods of killing pests selected from the group consisting of mites and insects with phosphonothioates
US3691163A (en) * 1970-08-03 1972-09-12 Exxon Research Engineering Co Certain phosphorus-containing thiomorpholinones
US4016266A (en) * 1975-06-02 1977-04-05 Stauffer Chemical Company N-Alkylthiomethylacetamidephosphorodithioate insecticides
DE2604224A1 (en) * 1976-02-04 1977-08-11 Hoechst Ag herbicides medium
FR2361067A1 (en) * 1976-04-23 1978-03-10 Hoechst Ag Organophosphorus compounds has anilide groups and pesticide products containing
US4162279A (en) * 1977-09-28 1979-07-24 Stauffer Chemical Company Phosphonoxycarboxamides
US4223028A (en) * 1979-04-30 1980-09-16 Stauffer Chemical Company Butynylamide phosphate and phosphonates and method for controlling insects
US4283395A (en) * 1980-03-24 1981-08-11 Stauffer Chemical Company S-Alkyl and alkenyl-thiophenylacetamido thiophosphates and phosphonates and method of controlling insects
US4356022A (en) * 1980-03-24 1982-10-26 Stauffer Chemical Company S-Alkyl and alkenyl-thiophenylacetamido thiophosphates and phosphonates as plant growth regulants

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US2668831A (en) * 1953-04-21 1954-02-09 Dow Chemical Co O-ethyl s-(ethylxanthoyl) n, n-diethylamidothiophosphate
US2712029A (en) * 1953-07-20 1955-06-28 Shell Dev Monoamides of trihalomethanephosphonic acid monoesters
US2864849A (en) * 1955-09-07 1958-12-16 Bayer Ag Thiophosphoric acid esters and their production
US2912452A (en) * 1956-04-21 1959-11-10 Bayer Ag Thiophosphoric acid esters and their production
US2915429A (en) * 1957-09-17 1959-12-01 Hoechst Ag O, o'-diethyl-dithiophosphoric acid-s-(dimethyl-thiocarbamyl-mercaptomethyl)-ester insecticides
US2920993A (en) * 1957-12-09 1960-01-12 Du Pont Insecticidal composition and method of destroying insects

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2668831A (en) * 1953-04-21 1954-02-09 Dow Chemical Co O-ethyl s-(ethylxanthoyl) n, n-diethylamidothiophosphate
US2712029A (en) * 1953-07-20 1955-06-28 Shell Dev Monoamides of trihalomethanephosphonic acid monoesters
US2864849A (en) * 1955-09-07 1958-12-16 Bayer Ag Thiophosphoric acid esters and their production
US2912452A (en) * 1956-04-21 1959-11-10 Bayer Ag Thiophosphoric acid esters and their production
US2915429A (en) * 1957-09-17 1959-12-01 Hoechst Ag O, o'-diethyl-dithiophosphoric acid-s-(dimethyl-thiocarbamyl-mercaptomethyl)-ester insecticides
US2920993A (en) * 1957-12-09 1960-01-12 Du Pont Insecticidal composition and method of destroying insects

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3233010A (en) * 1959-10-02 1966-02-01 Bayer Ag Dithiophosphonic acid esters and process for their production
US3238202A (en) * 1961-05-02 1966-03-01 Montedison Spa Amides of o, o-dialkyldithiophos-phorylacetic acids
US3351679A (en) * 1964-08-07 1967-11-07 Stauffer Chemical Co Substituted (nu-formyl-nu-alkylcarbamoyl methyl) phosphonothioates
US3401220A (en) * 1964-08-07 1968-09-10 Stauffer Chemical Co Methods of killing pests selected from the group consisting of mites and insects with phosphonothioates
US3691163A (en) * 1970-08-03 1972-09-12 Exxon Research Engineering Co Certain phosphorus-containing thiomorpholinones
US4016266A (en) * 1975-06-02 1977-04-05 Stauffer Chemical Company N-Alkylthiomethylacetamidephosphorodithioate insecticides
US4278461A (en) * 1976-02-04 1981-07-14 Hoechst Aktiengesellschaft Herbicidal agents
DE2604224A1 (en) * 1976-02-04 1977-08-11 Hoechst Ag herbicides medium
FR2340047A1 (en) * 1976-02-04 1977-09-02 Hoechst Ag Herbicide products based on organophosphorus compounds
US4152428A (en) * 1976-04-23 1979-05-01 Hoechst Aktiengesellschaft Pesticidal agents
FR2361067A1 (en) * 1976-04-23 1978-03-10 Hoechst Ag Organophosphorus compounds has anilide groups and pesticide products containing
US4162279A (en) * 1977-09-28 1979-07-24 Stauffer Chemical Company Phosphonoxycarboxamides
US4223028A (en) * 1979-04-30 1980-09-16 Stauffer Chemical Company Butynylamide phosphate and phosphonates and method for controlling insects
US4283395A (en) * 1980-03-24 1981-08-11 Stauffer Chemical Company S-Alkyl and alkenyl-thiophenylacetamido thiophosphates and phosphonates and method of controlling insects
US4356022A (en) * 1980-03-24 1982-10-26 Stauffer Chemical Company S-Alkyl and alkenyl-thiophenylacetamido thiophosphates and phosphonates as plant growth regulants

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