US3717690A - N,n-dialkylamidoxime phosphates - Google Patents

N,n-dialkylamidoxime phosphates Download PDF

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US3717690A
US3717690A US00051688A US3717690DA US3717690A US 3717690 A US3717690 A US 3717690A US 00051688 A US00051688 A US 00051688A US 3717690D A US3717690D A US 3717690DA US 3717690 A US3717690 A US 3717690A
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N Newman
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ExxonMobil Technology and Engineering Co
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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
    • C07F9/409—Compounds containing the structure P(=X)-X-acyl, P(=X) -X-heteroatom, P(=X)-X-CN (X = O, S, Se)
    • C07F9/4096—Compounds containing the structure P(=X)-X-N (X = O, S, Se)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
    • C07C259/12—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. N-hydroxyamidines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • 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
    • 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
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/095—Compounds containing the structure P(=O)-O-acyl, P(=O)-O-heteroatom, P(=O)-O-CN
    • C07F9/097—Compounds containing the structure P(=O)-O-N
    • 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
    • C07F9/1654—Compounds containing the structure P(=X)n-X-acyl, P(=X)n-X-heteroatom, P(=X)n-X-CN (X = O, S, Se; n = 0, 1)
    • C07F9/1657—Compounds containing the structure P(=X)n-X-N (X = O, S, Se; n = 0, 1)
    • 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
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/32—Esters thereof
    • C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/3264—Esters with hydroxyalkyl compounds

Definitions

  • R and R can be the same or different and are C -C alkyl or C C, cycloalkyl or taken together can form a cyclic ring. Similarly, R and R taken together can form a cyclic ring.
  • This invention relates to novel N,N-dialkylamidoximes and their derivatives.
  • this invention relates to N,N-dialkylamidoxime phosphate esters.
  • this invention relates to N,N-dialkylarylamidoxime phosphate esters.
  • this invention relates to the use of these novel N,N-dialkylamide and; arylamidoxime phosphate esters as herbicides.
  • R can be hydrogen, C C, alkyl or C C cycloalkyl, C C mono or C --C dialkyl carbamoyl, C --C aryl carbamoyl, C,--C monoor C ---C dialkyl or C -C aryl thiocarbamoyl, C -C aryl, C C acyl, C,C alkylsulfonyl, C,,C arylsulfonyl, or a phosphorus-containing moiety defined below; wherein R is C,C, alkyl, C C alkoxyalkyl, C C alkylthioalkyl, C -C haloalkyl, C C aryl, C ,C halo-substituted aryl, C-,-C arylalkyl and C,C halo-substituted arylalkyl, C -C alkenyl, and C C C alkyl
  • the phosphorylated compounds when R, is limited to C -C aryl, the phosphorylated compounds have been shown to possess an exceptionally good herbicidal activity.
  • dichlorobenzamidooximino) thiophosphate 0,0-diethyl-0-(N,N-dimethyl-p-toluamidoximino) phosphate 10 0,0-diethyl-0-(N,N-dimethylbenzamidoximino) thiophosphate 0,0-dimethyl-0-(N,N-dimethylbenzamidoximino) thiophosphate l2 0,0-diethyl-O-(N,N-dimethyl-3-chloro-5- methylbenzamidoximino) phosphate 13 0,0-diethyl-0-(N,N-dimethylmethacrylamidoximino) phosphate 14 0,0-diethyl-0-(N,N-dimethylpropiolamidoximino) phosphate 15 0,0-diethyl-0-(N,N-dihexylbenzamidoximino) phosphate 16 0,0-diethyl-0-( N,N-dihexylbenzamidoximino
  • 0,0-diallyl-0-(N,N-dimethylbenzamidoximino) phosphate 25
  • N,N-dimethylbenzamidoxime N,NO-trimethylbenzamidoxime
  • O-(N-methylcarbamoyl)-N,N-dimethylbenzamidoxime 29 0-(N-3-chlorophenylcarbamoyl)-N,N-dimethylbenzamidoxime 29 0-(N-3-chlorophenylcarbamoyl)-N,N-
  • dimethylbenzamidoxime 30 O-(N,N-dimethylcarbamoyl)-N,N-dimethylbenzamidoxime 0-( N-methylthiocarbamoyl)-N,N-dimethylbenzamidoxime 32 O-(methylsulfonyl)-N,N-dimethylbenzamidoxme 33 O-(p-toluenesulfonyl)-N,N-dimethylbenzamidoxime 34 -(1,5-dinitro-4-trifluoromethylphenyl)-N,N-
  • the compounds of the invention have general herbicidal properties. They are especially useful in certain types of weed control such as, for example, in application to crop lands to give control of the common weeds, without harming the crop plants; and for the control of crabgrass in lawns.
  • Herbicidal compositions of the invention are prepared by admixing one or more of the active ingredients defined heretofore, in herbicidally effective amounts with a conditioning agent of the kind used and referred to in the art as a pest control adjuvant or modifier to provide formulations adapted for ready and efficient application to soil or weeds (i.e., unwanted plants) using conventional applicator equipment.
  • a conditioning agent of the kind used and referred to in the art as a pest control adjuvant or modifier to provide formulations adapted for ready and efficient application to soil or weeds (i.e., unwanted plants) using conventional applicator equipment.
  • the herbicidal compositions or formulations are prepared in the form of solids or liquids.
  • Solid compositions are preferably in the form of granulars or dusts.
  • compositions can be compounded to give homogeneous free-flowing dusts by admixing the active compound or compounds with finely divided solids preferably talc, natural clays, pyrophyllite, diatomaceous earth, or. flours such as walnut shell, wheat, redwood, soya bean, and cotton-seed flours. Other inert solid conditioning agents or carriers of the kind conventionally employed in preparing pest control compositions in powdered form can be used.
  • Granulars can be compounded by absorbing the compound in liquid form onto a preformed granular diluent.
  • diluents as natural clays, pyrophyllite, diatomaceous earth, flours such as walnut shell, as well as granular sand can be employed.
  • granulars can also be compounded by ad-mixing the active ingredient with one of the powdered diluents described hereinabove, followed by the step of either pelleting or extruding the mixture.
  • Liquid compositions of the invention are prepared in the usual way by admixing one or more of the active ingredients with a suitable liquid diluent medium. In the cases where the compounds are liquids, they may be sprayed in ultra low volume as such. With certain solvents, such as alkylated naphthalene or other aromatic petroleum solvents, dimethyl formamide, cyclic ketones, relatively high up to about 50 percent by weight or more concentration of the activeingredient can be obtained in solution.
  • solvents such as alkylated naphthalene or other aromatic petroleum solvents, dimethyl formamide, cyclic ketones
  • compositions of the invention whether in the form of dusts or liquids, preferably also include a surface-active agent sometimes referred to in the art as a' wetting, dispersing, or emulsifying agent.
  • a surface-active agent sometimes referred to in the art as a' wetting, dispersing, or emulsifying agent.
  • These agents which will be referred to hereinafter more simply as surface-active dispersing agents, cause the compositions to be easily dispersed in water to give aqueous sprays which, for the most part, constitute a desirable composition for application.
  • the surface-active dispersing agents employed can be of the anionic, cationic, or nonionic type and include, for example, sodium and potassium oleate, the amine salts of oleic acid, such as morpholine and dimethylamine oleates, the sulfonated animal and vegetable oils, such as sulfonated fish and castor oils, sulfonated petroleum oils, sulfonated acyclic hydrocarbons, sodium salt of lignin sulfonic acid (goulac), alkylnaphthalene sodium sulfonate, sodium salts of sulfonated condensation products of naphthalene and formalde-hyde, sodium lauryl sulfate, disodium monolauryl phosphate, sorbitol laurate, pentaerythritol monostearate, glycerol monostearate, diglycol oleate, polyethylene oxides, ethylene oxide condensation products with stearyl
  • the herbicidal compositions are applied either as a spray, granular or a dust to the locus or area to be protected from undesirable plant growth, commonly called weeds, i.e. plants growing where they are not wanted.
  • weeds i.e. plants growing where they are not wanted.
  • Such application can be made directly upon the locus or area and the weeds thereon during the period of weed infestation in order to destroy the weeds, or alternatively, the application is made in advance of an anticipated weed infestation to prevent such infestation.
  • the compositions can be applied as aqueous foliar sprays but can also be applied as sprays directly to the surface of the soil.
  • the dry powdered compositions can be dusted directly on the plants or on the soil.
  • the compositions of the invention are preferably applied after emergence of the seedlings.
  • the applications are of the post-emergence type although preemergence applications may also be effective.
  • the active compound is, of course, applied in an amount sufficient to exert the desired herbicidal action.
  • the amount of the active compound present in the compositions as actually applied for destroying or preventing weeds will vary with the manner of application, the particular weeds for which control is sought, the purpose for which the application is being made, and like variables.
  • the herbicidal compositions as applied in the form of a spray, dust or granular will contain from about 0.1 to 100 percent by weight of the active compound.
  • Fertilizer materials other herbicidal agents, and other pest control agents such as insecticides and fungicides can be included in the herbicidal compositions of the invention if desired.
  • carrier or diluent means a material, which can be inorganic or organic and synthetic or of natural origin, with which the active ingredient is mixed or formulated to facilitate its storage, transport, and handling and application to the plants to be treated.
  • the carrier is preferably biologically and chemically inert and, as used, can be a solid or fluid.
  • solid carriers are preferably particulate, granular, or pelleted; however, other shapes and sizes of solid carrier can be employed as well.
  • Such preferable solid carriers can be natural occurring minerals although subsequently subjected to grinding, sieving, purification, and/or other treatments including, for example, gypsum; tripolite; diatomaceous earth; mineral silicates such as mica, vermiculite, talc, and pryophyllite; clays of the montmorillonite, kaolinite, or attapulgite groups; calcium or, magnesium limes, or calcite and dolomite; etc.
  • Carriers produced synthetically, as for example, synthetic hydrated silica oxides and synthetic calcium silicates can also be used, and many proprietary products of this type are available commercially.
  • the carrier can also be an elemental substance such as sulfur or carbon, preferably an activated carbon.
  • the carrier possesses intrinsic catalytic activity such that it would decompose the active ingredient, it is advantageous to incorporate a stabilizing agent, as for example, polyglycols such as diethylene glycol, to neutralize this activity and thereby prevent possible decomposition of the derivatives of the present invention.
  • a stabilizing agent as for example, polyglycols such as diethylene glycol
  • a resinous or waxy carrier can be used, preferably one which is solvent soluble or thermoplastic, including fusible.
  • examples of such carriers are natural or synthetic resins such as a coumarone resin, rosin, copal, shellac, dammar, polyvinyl chloride, styrene polymers and copolymers, a solid grade of polychlorophenol such as is available under the registered trademark Aroclor, a bitumen, an asphaltite, a wax for example, beeswax or a mineral wax such as paraffin wax or montan wax, or a chlorinated mineral wax, or a microcrystalline wax such as those available under the registered trademark Mikrovan Wax.
  • Compositions comprising such resinous or waxy carriers are preferably in granular or pelleted form.
  • Fluid carriers can be liquids, as for example, water or an organic fluid, including a liquefied normally vaporous or gaseous material, or a vaporous or gaseous material, and can be solvents or nonsolvents for the active material.
  • the horticultural petroleum spray oils boiling in the range of from about 275 to about 575 F., or boiling in the range of about 575 to about l,000 F. and having an unsulfonatable residue of at least about percent and preferably of at least about 90 percent, or mixtures of these two types of oil, are particularly suitable liquid carriers.
  • the carrier can be mixed or formulated with the active material during its manufacture or at any stage subsequently.
  • the carrier can be mixed or formulated with the active material in any proportion depending on the nature of the carrier.
  • One or more carriers moreover, can be used in combination.
  • compositions of this invention can be concentrates, suitable for storage or transport and containing, for example, from about 5 to about 90 percent by weight of the active ingredient, preferably from about 20 to about wt. percent. These concentrates can be diluted with the same or different carrier to a concentration suitable for application.
  • the compositions of this invention may also be dilute compositions suitable for application. In general, concentrations of about 0.1 to about 10 percent by weight, of active material based on the total weight of the composition are satisfactory,
  • the powdered carriers can be oil-treated to improve adhesion to the surface to which they are applied. These dusts can be concentrates, in which case a highly sorptive carrier is preferably used. These require dilution with the same or a different finely powdered carrier, which can be of lower sorptive capacity, to a concentration suitable for application.
  • compositions of the invention can be formulated as wettable powders comprising a major proportion of the active ingredient mixed with a dispersing, i.e., deflocculating or suspending agent, and if desired, a finely divided solid carrier and/or a wetting agent.
  • a dispersing i.e., deflocculating or suspending agent
  • the active ingredient can be in particulate form or adsorbed on the carrier and preferably constitutes at least about 10 percent, more preferably at least about 25 percent, by weight of the composition.
  • concentration of the dispersing agent should in general be between about 0.5 and about percent by weight of the total composition, although larger or smaller amounts can be used if desired.
  • the dispersing agent used in the composition of this invention can be any substance having definite dispersing, i.e., deflocculating or suspending, properties as distinct from wetting properties, although these substances can also possess wetting properties as well.
  • the dispersant or dispersing agent used can be protective colloids such as gelatin, glue, casein, gums, or a synthetic polymeric material such as polyvinyl alcohol and methyl cellulose.
  • the dispersants or dispersing agents used are sodium or calcium salts of high molecular weight sulfonic acids, as for example, the sodium or calcium salts of lignin sulfonic acids derived from sulfite cellulose waste liquors.
  • the calcium or sodium salts of condensed aryl sulfonic acid for example, the products known as Tamol 731, are also suitable.
  • the wetting agents used can be nonionic type surfactants, as for example, the condensation products of fatty acids containing at least 12, preferably 16 to 20, carbon atoms in the molecule, or abietic acid or naphthenic acid obtained in the refining of petroleum lubricating oil fractions with alkylene oxides such as ethylene oxide or propylene oxide, or with both ethylene oxide and propylene oxide, as for example, the condensation product of oleic acid and ethylene oxide containing about 6 to 15 ethylene oxide units in the molecule.
  • Other nonionic wetting agents like polyalkylene oxide polymers, commercially known as Pluronics can be used. Partial esters of the above acids with polyhydric alcohols such as glycerol, polyglycerol, sorbitol, or mannitol can also be used.
  • Suitable anionic wetting agents include the alkali metal salts, preferably sodium salts, of sulfuric acid esters or sulfonic acids containing at least 10 carbon atoms in a molecule, for example, the sodium secondary alkyl sulfates, dialkyl sodium sulfosuccinate available under the registered trademark Teepol, sodium salts of sulfonated castor oil, sodium dodecyl benzene sulfonate.
  • Granulated or pelleted compositions comprising a suitable carrier having the active ingredient incorporated therein are also included in this invention. These can be prepared by impregnating a granular carrier with a solution of the inert ingredient or by granulating a mixture of a finely divided solid carrier and the active ingredient.
  • the carrier used can consist of or contain a fertilizer or fertilizer mixture, as for example, a superphosphate.
  • compositions of this invention can also be formulated as solutions of the active ingredient in an organic solvent or mixture of solvents, such as for example, alcohols; ketones, especially acetone; ethers; hydrocarbons; etc.
  • the toxicant itself is a liquid these materials can be sprayed on crops without further dilution.
  • Petroleum hydrocarbon fractions used as solvents should preferably have a flash point above 73 F., an example of this being a refined aromatic extract of kerosene.
  • Auxiliary solvents such as alcohols, ketones, and polyalkylene glycol ethers and esters can be used in conjunction with these petroleum solvents.
  • compositions of the present invention can also be formulated as emulsifiable concentrates which are concentrated solutions or dispersion of the active ingredient in an organic liquid, preferably a water-insoluble organic liquid, containing an added emulsifying agent.
  • organic liquids include, e.g., the above petroleum hydrocarbon frac- K tions previously described.
  • the emulsifying agent can be of the type producing water-in-oil type emulsions which are suitable for application by low volume spraying, or an emulsifier of the type producing oil-in water emulsions can be used, producing concentrates which can be diluted with relatively large volumes of water for application by high volume spraying or relatively small volumes of water for low volume spraying.
  • the active ingredient is preferably in a nonaqueous phase.
  • a solution of 1.8 moles of hydroxylamine hydrochloride and L8 moles of sodium hydroxide contained in 600 ml of water was prepared and cooled to a temperature of l0-l5 C.
  • To this solution was simultaneously added the chloroform solution prepared hereinabove and 2.6 moles of a 50 percent aqueous sodium hydroxide solution. The mixture was stirred at 25 C. for 2 hours after completion of the addition step.
  • the chloroform layer was separated and the aqueous phase was extracted twice with small portions of chloroform.
  • the combined organic layers were dried over magnesium sulfate and filtered.
  • the chloroform was removed on a rotary evaporator leaving 340 grams of an oil residue.
  • amides By following a procedure entirely analogous to that described hereinabove the following amides have been converted to their oximes.
  • the amides themselves are either commercially available or may be synthesized by known methods, e.g. reaction of an amine with an acyl halide or anhydride. The products of these reactions were all identified by either infrared or NMR spectra and an elemental analysis will be recorded for each compound.
  • EXAM PLE 2 Preparation of 0,0-Diphenyl-O-(N,N-Dimethylbenzamidoximino) phosphate N,N-dimethylbenzamidoxime obtained in Example 1 (15.2 millimoles) was dissolved in 100 ml of anhydrous tetrahydrofuran. Metallic sodium (15.2 mg-atoms) was added and the mixture was refluxed overnight. The suspension was cooled to a temperature of approximately 10 to C. and 15.2 millimoles of diphenyl chlorophosphate was added dropwise. The solution was stirred overnight at 25 C. Ether (25 ml) was added and the solution was filtered to remove sodium chloride. The filtrate was stripped on a rotary evaporator and 7.0 grams (92 percent) of yellow oil was obtained. The identity of the product was confirmed by IR and NM spectroscopy.
  • Amidoximes substituted at oxygen with N-alkyl or N- aryl carbamoyl moieties may be prepared via condensation of an amidoxime with an appropriate isocyanate as shown for step III-B below:
  • EXAMPLE 5 Representative derivatives of the various compounds of this invention were evaluated for post-emergence activity. The test procedure was as follows:
  • a compound according to claim 1 which is 0,0- diethyl--(N,N-dimethylethoxyacetamidoximino) phosphate.
  • a compound according to claim 1 which is 0,0- diethyl-0-(N,N-dimethylmethacrylamidoximino) phosphate.
  • a compound according to claim 1 which is 0,0- diethyl-O-(N,N-dihexylbenzamidoximino) phosphate.
  • a compound according to claim 1 which is 0,0- diphenyl-0-(N,N-dimethylbenzamidoximino) phosphate.
  • a compound according to claim 1 which is S,S- dihexyl-O-(N,N-dimethylbenzamidoximino) trithiophosphate.
  • a compound according to claim 1 which is phenyl-O-phenyl-O-(N,N-dimethylbenzamidoximino) thiophosphate.
  • a compound according to claim 1 which is dipropargyl-O-(N,N-dimethylbenzamidoximino) thiophosphinate.

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Abstract

N,N-dialkylamidoximes and their derivatives are biologically active compounds possessing exceptional herbicidal activity. These compounds can be characterized by the following structural formula: IN WHICH R can be hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 monoalkyl or C2-C6 dialkyl carbamoyl, C6-C10 aryl carbamoyl, C1C6 mono- or C2-C6 dialkyl or C6-C10 aryl thiocarbamoyl, C6-C10 aryl, C1-C6 acyl, C1-C6 alkylsulfonyl, C6-C10 arylsulfonyl, or a phosphorus-containing moiety defined below; wherein R5 is a C1-C6 alkyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C1-C6 haloalkyl, C6-C10 aryl, C6-C10 halo-substituted aryl, C7-C11 arylalkyl and C7-C11 halo-substituted arylalkyl, C2-C6 alkenyl and C2-C6 alkynyl; R1 and R2 can be the same or different and are C1-C6 alkyl or C3-C6 cycloalkyl or taken together can form a cyclic ring. Similarly, R1 and R5 taken together can form a cyclic ring. A preferred embodiment of these compounds is characterized by the following structural formula: R3 and R4 can be the same or different and are C1-C6 alkyl, C1C6 alkoxy, C6-C10 aryloxy, C1-C6 alkylthio, C6-C10 arylthio, C1C6 haloalkyl, C6-C10 aryl, C6-C10 halo-substituted aryl, C7-C11 arylalkyl and C7-C11 halo-substituted arylalkyl; C2-C6 alkenyl and C2-C6 alknynl; X is either O or S. In a preferred embodiment, when R5 is limited to C6-C10 aryl, the phosphorylated compounds have been shown to possess an exceptionally good herbicidal activity.

Description

United States Patent 1191 Newman [54] N,N-DIALKYLAMIDOXIME PHOSPHATES [75] Inventor:
[73] Assignee: Esso Research and Engineering Company [22] Filed: July 1, 1970 [21] Appl. No.: 51,688
Neil F. Newman, Matawan, NJ.
[52] US. Cl. ..260/945, 71/86, 71/87,
71/103, 71/121, 260/564 G, 260/944 [51] Int. Cl. ..C07f 9/08, C07f 9/16, C07f 9/32 [58] Field of Search ..260/944, 945, 564 G [56] References Cited UNITED STATES PATENTS 12/1957 Allen ..260/944 10/1966 Malz et a1. ..260/944 X Primary Examiner-Lewis Gotts Assistant Examiner--Richard L. Raymond Attorney-Chasan and Sinnock and John Paul Corcoran [57] ABSTRACT 1451 Feb. 20, 1973 in which R can be hydrogen, C C. alkyl, C C cycloalkyl, C,C. monoalkyl or C -C dialkyl carbamoyl, C,,C aryl carbamoyl, C C monoor C ---C dialkyl or C,C aryl thiocarbamoyl, C -C aryl, C,C acyl, C -C alkylsulfonyl, C,C arylsulfonyl, or a phosphorus-containing moiety defined below; wherein R is a C,C alkyl, C -C alkoxyalkyl, C,C alkylthioalkyl, C -C. haloalkyl, C -C aryl, C -C halo-substituted aryl, C-,-C arylalkyl and C C halo-substituted arylalkyl, C ---C alkenyl and C,--C, alkynyl; R and R, can be the same or different and are C -C alkyl or C C, cycloalkyl or taken together can form a cyclic ring. Similarly, R and R taken together can form a cyclic ring.
A preferred embodiment of these compounds is characterized by the following structural formula:
and C -C alkn n1; X is either 0 or S. In a preferred e bod1ment, when R, 1s l1m1ted to C,-
C aryl, the phosphorylated compounds have been shown to possess an exceptionally good herbicidal activity.
13 Claims, No Drawings N,N-DIALKYLAMIDOXIME PHOSPHATES This invention relates to novel N,N-dialkylamidoximes and their derivatives. In one aspect, this invention relates to N,N-dialkylamidoxime phosphate esters. In another aspect, this invention relates to N,N-dialkylarylamidoxime phosphate esters. In another aspect, this invention relates to the use of these novel N,N-dialkylamide and; arylamidoxime phosphate esters as herbicides.
It is an object of the present invention to provide new thiophosphoric and phosphoric N,N-dialkylamidoxime phosphate esters which possess improved herbicidal activity.
It is another object of the subject invention to provide a novel herbicidal use for said compound. Other objects and many of the attendant advantages of this invention will be readily aPpreciated as the same becomes better understood, by reference to the following detailed description.
The compounds falling within the scope of this invention are characterized by the following structural formula:
C=NOR RiRzN in which R can be hydrogen, C C, alkyl or C C cycloalkyl, C C mono or C --C dialkyl carbamoyl, C --C aryl carbamoyl, C,--C monoor C ---C dialkyl or C -C aryl thiocarbamoyl, C -C aryl, C C acyl, C,C alkylsulfonyl, C,,C arylsulfonyl, or a phosphorus-containing moiety defined below; wherein R is C,C, alkyl, C C alkoxyalkyl, C C alkylthioalkyl, C -C haloalkyl, C C aryl, C ,C halo-substituted aryl, C-,-C arylalkyl and C,C halo-substituted arylalkyl, C -C alkenyl, and C C alkynyl; R, and R can be the same or different and are C,-C alkyl or C --C cycloalkyl or taken together can form a cyclic ring. Similarly, R and R taken together can form a cyclic ring.
A preferred embodiment of these compounds is characterized by the following structural formula:
R5 X R:
o=N-o-i RIB-1N R4 R, and R, can be the same or different and are C -C alkyl, C -C alkoxy, C -C aryloxy, C,-C, thioalkyl, C -C thioaryl, C,--C haloalkyl, C ''c aryl, C -C halo-substituted aryl, C-,--C arylalkyl and C --C halo-substituted arylalkyl; C,-C alkenyl and C -C alkynyl; X is either 0 or S.
In a preferred embodiment, when R, is limited to C -C aryl, the phosphorylated compounds have been shown to possess an exceptionally good herbicidal activity.
It has also been found that phosphate esters of N,N- di-alkylarylamidoximes possessed marked herbicidal activity and possess also definite crop selectivity.
The specific examples of the novel compounds covered by this invention are as follows:
Compound No. l 0,0-diethyl-O-(N,N-dimethylacetamidoximino) phosphate 2 0,0-diethyl-0-(N,N-dimethylhcptanamidoximino) phosphate 3 0,0-diethyl-0-(N,N-dimethylethoxyacctamidoximino) phosphate 0,0-diethyl-0-(N,N-dimethylmethylthioacetamidoximino) phosphate 5 0,0-diethyl-0-(N,N-dimethyl-3- chloropropionamidoxi-mino) phosphate 0,0-diethyl-0-(N,N-dimethylbenxamidoximino) phosphate 0,0-diethyl-0-(N,N-dimethyl-B-naphthamidoximino) phosphate 8 0,0-diethyl-0-(N,N-dimethyl-3,4-
dichlorobenzamidooximino) thiophosphate 0,0-diethyl-0-(N,N-dimethyl-p-toluamidoximino) phosphate 10 0,0-diethyl-0-(N,N-dimethylbenzamidoximino) thiophosphate 0,0-dimethyl-0-(N,N-dimethylbenzamidoximino) thiophosphate l2 0,0-diethyl-O-(N,N-dimethyl-3-chloro-5- methylbenzamidoximino) phosphate 13 0,0-diethyl-0-(N,N-dimethylmethacrylamidoximino) phosphate 14 0,0-diethyl-0-(N,N-dimethylpropiolamidoximino) phosphate 15 0,0-diethyl-0-(N,N-dihexylbenzamidoximino) phosphate 16 0,0-diethyl-0-( N,N-
tetramethylenebenzamidoximino) thiophosphate l7 0,0-diphenyl-0-(N,N-dimethylbenzamidoximino) phosphate 18 Ethyl-O-ethyl-O-N(N,N-dimethylbenzamidoximino) phosphonate l9 S,S-dihexyl-0-(N,N-dimethylbenzamidoximino) trithiophosphate 20 Chloromethyl-0-methyl0-(N,N-dimethylbenzamidoximino) phosphonate Compound No. 21 Phenyl-0-phenyl-0-(N,N-dimethylbenzamidoximino) thiophosphonate 22 Divinyl-O-(N,N-dimethylbenzamidoximino) phosphinate 23 Dipropargyl-O-(N,N-dimethylbenzamidoximino) thiophosphinate 24 0,0-diallyl-0-(N,N-dimethylbenzamidoximino) phosphate 25 N,N-dimethylbenzamidoxime 26 N,NO-trimethylbenzamidoxime 27 N,N-dimethylbenzamidoximinopropionate 28 O-(N-methylcarbamoyl)-N,N-dimethylbenzamidoxime 29 0-(N-3-chlorophenylcarbamoyl)-N,N-
dimethylbenzamidoxime 30 O-(N,N-dimethylcarbamoyl)-N,N-dimethylbenzamidoxime 0-( N-methylthiocarbamoyl)-N,N-dimethylbenzamidoxime 32 O-(methylsulfonyl)-N,N-dimethylbenzamidoxme 33 O-(p-toluenesulfonyl)-N,N-dimethylbenzamidoxime 34 -(1,5-dinitro-4-trifluoromethylphenyl)-N,N-
dimethyl benzamidoxime The compounds falling within the scope of this invention may be prepared via the sequence given below starting with N,N-dimethylbenzamide (commercially available; Fisher Scientific Co.). Step I:
The conditions for this Step are:
Contact Mol Ratio Temp. P. Time,
COCl'IAmideSolvent C. Atm. Hrs.
Broad 1.00-5.00 hydrocarbons, 50 1- min.
to 10.0 to l00 Pre- 1.00-1.50 chloroform 10to 1- l-SO ferred +30 1.5
1 such as toluene, heptsne; chlorinated hydrocarbons, such as chloroform, carbontetrachloride; ethers, such as diethylether, THF
Step ll:
01 e @-o=mom)=01 union-H01 3NaOH HahN ahN O =N0l= (0 Cells) Base-H01 The reaction conditions for this Step are:
Mole chloro- Mole base/ phosphate] Temp. P. mole oxime moloxime Solvent Alm- B388 Broad 1.0-1.5 1.0-1.5 hydro- 0- l alkali carbons 100 10 metals 2) metal alkyls 3) metal amides Pre- 1.0- 1.0-1.1 tetrahy- 0- 1- sodium ferrcd -1.1 drofuran 100 1.5
such an benzene, toluene, hcptanc others. such as dicthyl other. THF. Dionne The compounds of the invention have general herbicidal properties. They are especially useful in certain types of weed control such as, for example, in application to crop lands to give control of the common weeds, without harming the crop plants; and for the control of crabgrass in lawns.
Herbicidal compositions of the invention are prepared by admixing one or more of the active ingredients defined heretofore, in herbicidally effective amounts with a conditioning agent of the kind used and referred to in the art as a pest control adjuvant or modifier to provide formulations adapted for ready and efficient application to soil or weeds (i.e., unwanted plants) using conventional applicator equipment.
Thus, the herbicidal compositions or formulations are prepared in the form of solids or liquids. Solid compositions are preferably in the form of granulars or dusts.
The compositions can be compounded to give homogeneous free-flowing dusts by admixing the active compound or compounds with finely divided solids preferably talc, natural clays, pyrophyllite, diatomaceous earth, or. flours such as walnut shell, wheat, redwood, soya bean, and cotton-seed flours. Other inert solid conditioning agents or carriers of the kind conventionally employed in preparing pest control compositions in powdered form can be used.
Granulars can be compounded by absorbing the compound in liquid form onto a preformed granular diluent. Such diluents as natural clays, pyrophyllite, diatomaceous earth, flours such as walnut shell, as well as granular sand can be employed. I
In addition, granulars can also be compounded by ad-mixing the active ingredient with one of the powdered diluents described hereinabove, followed by the step of either pelleting or extruding the mixture.
Liquid compositions of the invention are prepared in the usual way by admixing one or more of the active ingredients with a suitable liquid diluent medium. In the cases where the compounds are liquids, they may be sprayed in ultra low volume as such. With certain solvents, such as alkylated naphthalene or other aromatic petroleum solvents, dimethyl formamide, cyclic ketones, relatively high up to about 50 percent by weight or more concentration of the activeingredient can be obtained in solution.
The herbicidal compositions of the invention whether in the form of dusts or liquids, preferably also include a surface-active agent sometimes referred to in the art as a' wetting, dispersing, or emulsifying agent. These agents, which will be referred to hereinafter more simply as surface-active dispersing agents, cause the compositions to be easily dispersed in water to give aqueous sprays which, for the most part, constitute a desirable composition for application.
The surface-active dispersing agents employed can be of the anionic, cationic, or nonionic type and include, for example, sodium and potassium oleate, the amine salts of oleic acid, such as morpholine and dimethylamine oleates, the sulfonated animal and vegetable oils, such as sulfonated fish and castor oils, sulfonated petroleum oils, sulfonated acyclic hydrocarbons, sodium salt of lignin sulfonic acid (goulac), alkylnaphthalene sodium sulfonate, sodium salts of sulfonated condensation products of naphthalene and formalde-hyde, sodium lauryl sulfate, disodium monolauryl phosphate, sorbitol laurate, pentaerythritol monostearate, glycerol monostearate, diglycol oleate, polyethylene oxides, ethylene oxide condensation products with stearyl alcohol and alkyl-phenol, polyvinyl alcohols, salts, such as the acetate of polyamines from reductive amination of ethylene-carbon monoxide polymers, laurylamine hydrochloride, laurylpyridinium bromide, stearyl trimethylammonium bromide, cetyldimethylbenzyl ammonium chloride, lauryldimethylamine oxide, and the like. Generally, the surface-active agent will not comprise more than about 5 to percent by weight of the composition, and in certain compositions the percentage will be 1 percent or less. Usually, the minimum lower concentration will be 0.1 percent.
The herbicidal compositions are applied either as a spray, granular or a dust to the locus or area to be protected from undesirable plant growth, commonly called weeds, i.e. plants growing where they are not wanted. Such application can be made directly upon the locus or area and the weeds thereon during the period of weed infestation in order to destroy the weeds, or alternatively, the application is made in advance of an anticipated weed infestation to prevent such infestation. Thus, the compositions can be applied as aqueous foliar sprays but can also be applied as sprays directly to the surface of the soil. Alternatively, the dry powdered compositions can be dusted directly on the plants or on the soil.
In applying the herbicidal compositions of the invention for selective weed control as in the control of weeds in cotton or corn fields, the compositions are preferably applied after emergence of the seedlings. In other words, the applications are of the post-emergence type although preemergence applications may also be effective.
The active compound is, of course, applied in an amount sufficient to exert the desired herbicidal action. The amount of the active compound present in the compositions as actually applied for destroying or preventing weeds will vary with the manner of application, the particular weeds for which control is sought, the purpose for which the application is being made, and like variables. In general, the herbicidal compositions as applied in the form of a spray, dust or granular, will contain from about 0.1 to 100 percent by weight of the active compound.
Fertilizer materials, other herbicidal agents, and other pest control agents such as insecticides and fungicides can be included in the herbicidal compositions of the invention if desired.
The term carrier or diluent as used herein means a material, which can be inorganic or organic and synthetic or of natural origin, with which the active ingredient is mixed or formulated to facilitate its storage, transport, and handling and application to the plants to be treated. The carrier is preferably biologically and chemically inert and, as used, can be a solid or fluid. When solid carriers are used, they are preferably particulate, granular, or pelleted; however, other shapes and sizes of solid carrier can be employed as well. Such preferable solid carriers can be natural occurring minerals although subsequently subjected to grinding, sieving, purification, and/or other treatments including, for example, gypsum; tripolite; diatomaceous earth; mineral silicates such as mica, vermiculite, talc, and pryophyllite; clays of the montmorillonite, kaolinite, or attapulgite groups; calcium or, magnesium limes, or calcite and dolomite; etc. Carriers produced synthetically, as for example, synthetic hydrated silica oxides and synthetic calcium silicates can also be used, and many proprietary products of this type are available commercially. The carrier can also be an elemental substance such as sulfur or carbon, preferably an activated carbon. If the carrier possesses intrinsic catalytic activity such that it would decompose the active ingredient, it is advantageous to incorporate a stabilizing agent, as for example, polyglycols such as diethylene glycol, to neutralize this activity and thereby prevent possible decomposition of the derivatives of the present invention.
For some purposes, a resinous or waxy carrier can be used, preferably one which is solvent soluble or thermoplastic, including fusible. Examples of such carriers are natural or synthetic resins such as a coumarone resin, rosin, copal, shellac, dammar, polyvinyl chloride, styrene polymers and copolymers, a solid grade of polychlorophenol such as is available under the registered trademark Aroclor, a bitumen, an asphaltite, a wax for example, beeswax or a mineral wax such as paraffin wax or montan wax, or a chlorinated mineral wax, or a microcrystalline wax such as those available under the registered trademark Mikrovan Wax. Compositions comprising such resinous or waxy carriers are preferably in granular or pelleted form.
Fluid carriers can be liquids, as for example, water or an organic fluid, including a liquefied normally vaporous or gaseous material, or a vaporous or gaseous material, and can be solvents or nonsolvents for the active material. For example, the horticultural petroleum spray oils boiling in the range of from about 275 to about 575 F., or boiling in the range of about 575 to about l,000 F. and having an unsulfonatable residue of at least about percent and preferably of at least about 90 percent, or mixtures of these two types of oil, are particularly suitable liquid carriers.
The carrier can be mixed or formulated with the active material during its manufacture or at any stage subsequently. The carrier can be mixed or formulated with the active material in any proportion depending on the nature of the carrier. One or more carriers, moreover, can be used in combination.
The compositions of this invention can be concentrates, suitable for storage or transport and containing, for example, from about 5 to about 90 percent by weight of the active ingredient, preferably from about 20 to about wt. percent. These concentrates can be diluted with the same or different carrier to a concentration suitable for application. The compositions of this invention may also be dilute compositions suitable for application. In general, concentrations of about 0.1 to about 10 percent by weight, of active material based on the total weight of the composition are satisfactory,
solid carrier such as aforedescribed. The powdered carriers can be oil-treated to improve adhesion to the surface to which they are applied. These dusts can be concentrates, in which case a highly sorptive carrier is preferably used. These require dilution with the same or a different finely powdered carrier, which can be of lower sorptive capacity, to a concentration suitable for application. I
The compositions of the invention can be formulated as wettable powders comprising a major proportion of the active ingredient mixed with a dispersing, i.e., deflocculating or suspending agent, and if desired, a finely divided solid carrier and/or a wetting agent. The active ingredient can be in particulate form or adsorbed on the carrier and preferably constitutes at least about 10 percent, more preferably at least about 25 percent, by weight of the composition. The concentration of the dispersing agent should in general be between about 0.5 and about percent by weight of the total composition, although larger or smaller amounts can be used if desired.
The dispersing agent used in the composition of this invention can be any substance having definite dispersing, i.e., deflocculating or suspending, properties as distinct from wetting properties, although these substances can also possess wetting properties as well.
The dispersant or dispersing agent used can be protective colloids such as gelatin, glue, casein, gums, or a synthetic polymeric material such as polyvinyl alcohol and methyl cellulose. Preferably, however, the dispersants or dispersing agents used are sodium or calcium salts of high molecular weight sulfonic acids, as for example, the sodium or calcium salts of lignin sulfonic acids derived from sulfite cellulose waste liquors. The calcium or sodium salts of condensed aryl sulfonic acid, for example, the products known as Tamol 731, are also suitable.
The wetting agents used can be nonionic type surfactants, as for example, the condensation products of fatty acids containing at least 12, preferably 16 to 20, carbon atoms in the molecule, or abietic acid or naphthenic acid obtained in the refining of petroleum lubricating oil fractions with alkylene oxides such as ethylene oxide or propylene oxide, or with both ethylene oxide and propylene oxide, as for example, the condensation product of oleic acid and ethylene oxide containing about 6 to 15 ethylene oxide units in the molecule. Other nonionic wetting agents like polyalkylene oxide polymers, commercially known as Pluronics can be used. Partial esters of the above acids with polyhydric alcohols such as glycerol, polyglycerol, sorbitol, or mannitol can also be used.
Suitable anionic wetting agents include the alkali metal salts, preferably sodium salts, of sulfuric acid esters or sulfonic acids containing at least 10 carbon atoms in a molecule, for example, the sodium secondary alkyl sulfates, dialkyl sodium sulfosuccinate available under the registered trademark Teepol, sodium salts of sulfonated castor oil, sodium dodecyl benzene sulfonate.
Granulated or pelleted compositions comprising a suitable carrier having the active ingredient incorporated therein are also included in this invention. These can be prepared by impregnating a granular carrier with a solution of the inert ingredient or by granulating a mixture of a finely divided solid carrier and the active ingredient. The carrier used can consist of or contain a fertilizer or fertilizer mixture, as for example, a superphosphate.
The compositions of this invention can also be formulated as solutions of the active ingredient in an organic solvent or mixture of solvents, such as for example, alcohols; ketones, especially acetone; ethers; hydrocarbons; etc.
Where the toxicant itself is a liquid these materials can be sprayed on crops without further dilution.
Petroleum hydrocarbon fractions used as solvents should preferably have a flash point above 73 F., an example of this being a refined aromatic extract of kerosene. Auxiliary solvents such as alcohols, ketones, and polyalkylene glycol ethers and esters can be used in conjunction with these petroleum solvents.
Compositions of the present invention can also be formulated as emulsifiable concentrates which are concentrated solutions or dispersion of the active ingredient in an organic liquid, preferably a water-insoluble organic liquid, containing an added emulsifying agent. These concentrates can also contain a proportion of water, for example, up to about 50 percent by volume, based on the total composition, to facilitate subsequent dilution with water. Suitable organic liquids include, e.g., the above petroleum hydrocarbon frac- K tions previously described.
The emulsifying agent can be of the type producing water-in-oil type emulsions which are suitable for application by low volume spraying, or an emulsifier of the type producing oil-in water emulsions can be used, producing concentrates which can be diluted with relatively large volumes of water for application by high volume spraying or relatively small volumes of water for low volume spraying. In such emulsions, the active ingredient is preferably in a nonaqueous phase.
The present invention is further illustrated in greater detail by the following examples, but it is to be understood that the present invention in its broadest aspects, is not necessarily limited in terms of the reactants, or specific temperatures, residence times, separation techniques and other process conditions, etc.; or dosage level, exposure times, test plants used, etc., by which the compounds and/or compositions described and claimed are prepared and/or used.
EXAMPLE 1 Preparation of N ,N-Dimethylbenzamidoxime l.2 moles of phosgene was bubbled into 500 ml of chloroform and cooled to 0 C. via a dry-ice/acetone bath. To the stirred phosgene solution at 1015 C. was added dropwise a solution of gms (1.2 moles) of N,N-dimethylbenzamide carried in 50 ml of chloroform. Carbon dioxide evolution was evident. After completing the addition, the solution was warmed to 25 C. and stirred overnight.
A solution of 1.8 moles of hydroxylamine hydrochloride and L8 moles of sodium hydroxide contained in 600 ml of water was prepared and cooled to a temperature of l0-l5 C. To this solution was simultaneously added the chloroform solution prepared hereinabove and 2.6 moles of a 50 percent aqueous sodium hydroxide solution. The mixture was stirred at 25 C. for 2 hours after completion of the addition step.
The chloroform layer was separated and the aqueous phase was extracted twice with small portions of chloroform. The combined organic layers were dried over magnesium sulfate and filtered. The chloroform was removed on a rotary evaporator leaving 340 grams of an oil residue.
The residue was taken up in 250 ml of hot cyclohexane and cooled to 8 to crystallize 44 grams of crude product. After recrystallizing from cyclohexane, 35.4 grams of white crystals were obtained having a melting point of 124 to 127 C.
The structure of the product was confirmed as N,N- dimethylbenzamidoxime by infrared and NMR spectroscopy. Calculated for C H N O: C, 65.9 H, 7.31 N,17.08
Found: C,66.2 H,7.39 N, 16.91
By following a procedure entirely analogous to that described hereinabove the following amides have been converted to their oximes. The amides themselves are either commercially available or may be synthesized by known methods, e.g. reaction of an amine with an acyl halide or anhydride. The products of these reactions were all identified by either infrared or NMR spectra and an elemental analysis will be recorded for each compound.
TABLE I Starting Amide Oxime Analysis Theoretical Found N-methylpyrrol- N-methylpyrrolidone C 52.7 52.4 idone oxime H 8.78 8.52 N,N-dimethyl- N,N-dimethylacet- C 47.1 47.1 acetamide amide oxime H 9.80 10.07 Melting Point 50-54C. N,N-dimethyI-3,4- N,N-dimethyl-3,4- C 46.4 46.4 dichlorobenzamide dichlorobenzamide H 4.72 4.51 oxime N 12.02 12.07 Melting Point l46l48C. N-acetylpyrrol- N-acetylpyrrolidine C 56.3 56.7 iodine oxime H 9.38 9.30 N 21.9 21.8
EXAM PLE 2 Preparation of 0,0-Diphenyl-O-(N,N-Dimethylbenzamidoximino) phosphate N,N-dimethylbenzamidoxime obtained in Example 1 (15.2 millimoles) was dissolved in 100 ml of anhydrous tetrahydrofuran. Metallic sodium (15.2 mg-atoms) was added and the mixture was refluxed overnight. The suspension was cooled to a temperature of approximately 10 to C. and 15.2 millimoles of diphenyl chlorophosphate was added dropwise. The solution was stirred overnight at 25 C. Ether (25 ml) was added and the solution was filtered to remove sodium chloride. The filtrate was stripped on a rotary evaporator and 7.0 grams (92 percent) of yellow oil was obtained. The identity of the product was confirmed by IR and NM spectroscopy.
Using a reaction entirely analogous to the abovedescribed step the following phosphorylated oximes were prepared. Their structures were confirmed by IR and NMR spectroscopy.
TABLE II Phosphorylating Phosphorylated Physical Starting Oxime Agent Oxime Properties N-methylpyrrolidone oxime Diethylchlorothiophosphate 0,0-Diethyl-O- (MN-methylpyrrolicloximino) phosphate yellow oil N,N-dimethylbenzamidoxime Diethylchlorothiophosphate N,N-dimetliyl-0- (N,N-dimethylbenzamidoximino) thiophosphate yellow oil N,N-dimethylbenzamidoxime Diemthylchlorothiophosphate 0,0-dimethyl-O- (N,N-dimethylbenzamidoximino) thiophosphate N,N-dimethylbenzamidoxime Diethylchloro- 7 phosphate 0,0-diethyl-O- (N,N-dimethylbenazmidoximino) thiophosphate yellow oil N,N-dimethylacetamidoxime Diethylchlorothiophosphate 0,0-diethyl-O- (N,N-dimethylacetamidoximino) thiophosphate yellow oil N,N-dimethyl-3,4- dichlorobenzamidoxime Diethylchlorothiophosphate 0,0-diethyl-O- (N,N-dimethyl- 3,4-dichlorobenzamidoximino) thiophosphate yellow oil N-acetylpyrrolidine oxime Diethylchlorothiophosphate 0,0-diethyl-O- (N,N-methylpyrrolidinooximino) thicphosphate yellow oil Anal: Calcd. Found C 42.8 42.1 H 7.50 7.41
N,N-dimethylbenzamidoxime Diphenylchlorophosphate 0,0-diphenyl- O-(N,N-dimethylbenzamidoximino) phosphate yellow oil EXAMPLE 3 Amidoximes substituted at the oxygen with nonphosphorus moieties can be prepared via Step III-A described hereinbelow in which the reaction conditions are entirely analogous to the phosphorylating step described under Example 2.
Step III-A:
C=NOR Base HCI (CHalrN zlzN Identification (I R and N MR spectra) Calcd., percent Found, pcrccnt R Product C H C H i H C=NO(N(CHI)2 57.4 16.7 57.6 16.7 CN(CN3)2 ahN 0 Q ()I N(CH3): (l=NQJ:N(CII:)I 61.3 7.23 60.9 7.23
MN 0 0 II it 41011 /(l=NO Calls A 7.27 7.35
s :@CH: C=N0 s m-Gcm Q a)2N NO: NO:
C=N0 C F3 43.2 3.27 48. 7 3.23 -0 F3 (CHa)2N Amidoximes substituted at oxygen with N-alkyl or N- aryl carbamoyl moieties may be prepared via condensation of an amidoxime with an appropriate isocyanate as shown for step III-B below:
test chemicals were sprayed as acetone solutions .or acetone suspensions of very small particle size onto the test plants. Sprayers were calibrated to deliver a certain volume of liquid and the calculated amount of active O ll C=NOH R-lfICO C=NO NHR 3) 2 1!) 2N Identification (IR and NMR spectra) Calcd., percent Found, percent R Product degiees O H C H H 3 /C=I l O CNHCH; 108-114 57. 6 7. 15 57. 9 7. 07
v (CHahN 0 O1 O I c=N0dNH- O 120-122 60.4 5.03 60.5 5.00 ah EXA M PLE 4 ingredient which would give a rate corresponding to the indicated pounds/acre. The flats were then held in the greenhouse and'a response rated after 12 days to 16,
days. Response was rated by a scale of 0-10. The 0-10 scale is defined as: 0 no injury; 1-3 slight injury; 4-6 moderate injury, plants may die; 7-9 severe injury, plants will probably die; 10 all plants dead (complete kill). The results of this test as shown in Table III are indicative that many of these compounds show a high degree of herbicidal activity in many weed species, but may remain highly tolerant of desirable crop species.
EXAMPLE 5 Representative derivatives of the various compounds of this invention were evaluated for post-emergence activity. The test procedure was as follows:
3. A compound according to claim 1, which is 0,0- diethyl--(N,N-dimethylethoxyacetamidoximino) phosphate.
4. A compound according to claim 1, which is 0,0-
Flats were seeded, as described in the previous exam diethyl0'(NNdlmethy1'3'chlompmpionamidox' ple and held until the first true leaves had appeared on all plants which were then sprayed in the same fashion as in the preceding example at a rate corresponding to the indicated pounds per acre. The plant responses were rated 12 to 16 days after treatment on the same scale as described previously. The test results are shown in Table IV.
imino) phosphate.
5. A compound according to claim 1, which is 0,0- diethyl-O-(N,N-dimethyl-B-naphthamidoximino) hos hate. 0 P P TABLE III.-PRE-EMERGENCE IIERBICIDA L ACTWITY Lb./ Barnyard Crab- Yellow Morning Compound ucre grass grass foxtnil Zinnia Mustard glory 0,0-dlethyl-O-(N,N dlmcthylbenzamidoxlrnlno) thlophosphate 4 3 3 8 8 8 0,0-dlethyl-O-(N ,N-dirnethylbcnzamldoxlmlno) phosphate 1O 10 J 9 9 J 9 0,0-dlrnethyl-O-(N ,N-dlmethylbenzamidoximino) thlophosphatc 10 2 6 4 6 4 8 0,0-diphenyl-O-(N,N-dlmethylbenzamldoxlmino) phosphate 10 6 9 10 9 10 10 Do 2. 5 3 6 9 3 8 9 TABLE IV.POST-EMERGENCE HERBICIDAL ACTIVITY Lb./ Barnyard Crab- Yellow Morning Compound acre grass grass Ioxtail Zinnia Mustard glory O, O-diethyl-O-(N.N-dimethylbenzamldoximino) thiophosphat 1O 9 1O 10 10 10 l 0,0-diethyl-O-(N,N-dimethylbenzamidoximino) phosphate 10 10 9 10 10 10 10 0,0,-dimethy1-O-(N,N-dimethylbenzamldoximino) thiophosphate. 10 9 9 4 10 10 8 0,0,-diethyl-O-(N,N-dimethyl-3,4-d1chlorobenzamidoximino) thiophophat 10 10 7 6 7 6 5 0,0sflphenyl-O-(N,N-dimethylbenzamidoximino) phosphate 21(5) 13 1(7) 12 1g 18 f What is claimed is: l. A compound of the formula 7. A compound according to claim 1, which is 0,0- dimethyl-O-N,N-dimethylbenzamidoximino) thiophosphate.
8. A compound according to claim 1, which is 0,0- diethyl-0-(N,N-dimethylmethacrylamidoximino) phosphate.
9. A compound according to claim 1, which is 0,0- diethyl-O-(N,N-dihexylbenzamidoximino) phosphate.
10. A compound according to claim 1, which is 0,0- diphenyl-0-(N,N-dimethylbenzamidoximino) phosphate.
11. A compound according to claim 1, which is S,S- dihexyl-O-(N,N-dimethylbenzamidoximino) trithiophosphate.
12. A compound according to claim 1, which is phenyl-O-phenyl-O-(N,N-dimethylbenzamidoximino) thiophosphate.
13. A compound according to claim 1, which is dipropargyl-O-(N,N-dimethylbenzamidoximino) thiophosphinate.

Claims (12)

1. A compound of the formulA wherein each of R1 and R2 is C1-C6 alkyl or C3-C6 cycloalkyl, each of R3 and R4 is C1-C6 alkyl, optionally substituted by chlorine, C1-C6 alkoxy, C1-C6 alkylthio, C2-C6 alkenyl, C2-C6 alkynyl, phenyl or phenoxy, R5 is C1-C6 alkyl optionally substituted by chlorine, C1-C4 alkoxy or C1-C4 alkylthio; C2-C6 alkenyl; C2-C6 alkynyl; phenyl optionally substituted by chlorine or methyl; or naphthyl, and X is oxygen or sulfur.
2. A compound according to claim 1, which is 0,0-diethyl-0-(N, N-dimethylacetamidoximino) phosphate.
3. A compound according to claim 1, which is 0,0-diethyl-0-(N,N-dimethylethoxyacetamidoximino) phosphate.
4. A compound according to claim 1, which is 0,0-diethyl-0-(N,N-dimethyl-3-chloropropionamidoximino) phosphate.
5. A compound according to claim 1, which is 0,0-diethyl-0-(N,N-dimethyl- Beta -naphthamidoximino) phosphate.
6. A compound according to claim 1, which is 0,0-diethyl-0-(N,N-dimethyl-p-toluamidoximino) phosphate.
7. A compound according to claim 1, which is 0,0-dimethyl-0-N,N-dimethylbenzamidoximino) thiophosphate.
8. A compound according to claim 1, which is 0,0-diethyl-0-(N,N-dimethylmethacrylamidoximino) phosphate.
9. A compound according to claim 1, which is 0,0-diethyl-0-(N,N-dihexylbenzamidoximino) phosphate.
10. A compound according to claim 1, which is 0,0-diphenyl-0-(N, N-dimethylbenzamidoximino) phosphate.
11. A compound according to claim 1, which is S,S-dihexyl-0-(N, N-dimethylbenzamidoximino) trithiophosphate.
12. A compound according to claim 1, which is phenyl-0-phenyl-0-(N,N-dimethylbenzamidoximino) thiophosphate.
US00051688A 1970-07-01 1970-07-01 N,n-dialkylamidoxime phosphates Expired - Lifetime US3717690A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3903204A (en) * 1973-04-21 1975-09-02 Celamerck Gmbh & Co Kg S-(N-methyl-N-phenyl-carbamoylmethyl) esters of certain thiophosphonic and dithiophosphonic acids
US3949023A (en) * 1972-12-08 1976-04-06 Sumitomo Chemical Co., Ltd. Novel oximino -phosphorothiolate derivatives
US4123255A (en) * 1977-01-03 1978-10-31 Chevron Research Company O-sulfonyl-alpha-cyano 2,6-dihalobenzaldoximes
US4125397A (en) * 1977-01-03 1978-11-14 Chevron Research Company O-Sulfonyl-alpha-halo-2,6-dihalobenzaldoximes
US4283220A (en) * 1979-08-23 1981-08-11 Monsanto Company Imidamides derived from 2-oxo-3-benzothiazoline acetic acid plant growth regulants
US4323686A (en) * 1979-08-23 1982-04-06 Monsanto Company Benzothiazoleethanimidamides
US4339444A (en) * 1981-04-01 1982-07-13 Union Carbide Corporation Novel oxime-phosphate compounds
US4405632A (en) * 1980-06-27 1983-09-20 Union Carbide Corporation Novel derivatives of bicyclic 2-iminothiazolidine oximes
US4479946A (en) * 1980-06-27 1984-10-30 Union Carbide Corporation Phosphorus esters of amidoximes, and compositions for and methods of controlling insects using them
US4525357A (en) * 1980-06-27 1985-06-25 Union Carbide Corporation Derivatives of bicyclic 2-iminothiazolidine oximes

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2816128A (en) * 1956-07-27 1957-12-10 Fmc Corp Phosphate esters of oximes
US3281321A (en) * 1962-08-23 1966-10-25 Bayer Ag Acetamidido-(thio)-phosphoric or phosphonic acid esters as rodenticides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2816128A (en) * 1956-07-27 1957-12-10 Fmc Corp Phosphate esters of oximes
US3281321A (en) * 1962-08-23 1966-10-25 Bayer Ag Acetamidido-(thio)-phosphoric or phosphonic acid esters as rodenticides

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3949023A (en) * 1972-12-08 1976-04-06 Sumitomo Chemical Co., Ltd. Novel oximino -phosphorothiolate derivatives
US3903204A (en) * 1973-04-21 1975-09-02 Celamerck Gmbh & Co Kg S-(N-methyl-N-phenyl-carbamoylmethyl) esters of certain thiophosphonic and dithiophosphonic acids
US4123255A (en) * 1977-01-03 1978-10-31 Chevron Research Company O-sulfonyl-alpha-cyano 2,6-dihalobenzaldoximes
US4125397A (en) * 1977-01-03 1978-11-14 Chevron Research Company O-Sulfonyl-alpha-halo-2,6-dihalobenzaldoximes
US4283220A (en) * 1979-08-23 1981-08-11 Monsanto Company Imidamides derived from 2-oxo-3-benzothiazoline acetic acid plant growth regulants
US4323686A (en) * 1979-08-23 1982-04-06 Monsanto Company Benzothiazoleethanimidamides
US4405632A (en) * 1980-06-27 1983-09-20 Union Carbide Corporation Novel derivatives of bicyclic 2-iminothiazolidine oximes
US4479946A (en) * 1980-06-27 1984-10-30 Union Carbide Corporation Phosphorus esters of amidoximes, and compositions for and methods of controlling insects using them
US4525357A (en) * 1980-06-27 1985-06-25 Union Carbide Corporation Derivatives of bicyclic 2-iminothiazolidine oximes
US4339444A (en) * 1981-04-01 1982-07-13 Union Carbide Corporation Novel oxime-phosphate compounds

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FR2098121A5 (en) 1972-03-03
BE769362A (en) 1972-01-03
IL37193A (en) 1974-05-16
NL7109048A (en) 1972-01-04
GB1353399A (en) 1974-05-15
BG18823A3 (en) 1975-03-20
DE2132598A1 (en) 1972-01-05
IL37193A0 (en) 1971-08-25
SU399092A3 (en) 1973-09-27
ZA714292B (en) 1972-03-29

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