METHOD FOR THE CONTROL OF INSECTS WHICH ATTACK PLANTS WITH PHOSPHORUS DERIVATIVES OF CARBAMIMIDOTHIOIC ACID ESTERS

Abstract: Phosphorus derivatives of carbamimidothioic-acid es­ ters of the formula wherein R and R¹ are each independently a methyl or ethyl group or R and R¹ when taken together represent an alkylene group containing 4 to 6 carbon atoms or a group of the formula -[-CH₂CH₂-]-₂A- wherein A is oxygen, sulfur or -R; R² and R³ are each independently an alkyl group con­ taining 1 to 4 carbon atoms and X and Y represent oxygen or sulfur, with the proviso that X and Y are not the same; employed as plant systemic in­ secticides for the control of sucking and boring-type insects which attack plants of economic importance.

Description: METHOD FOR THE CONTROL OF INSECTS WHICH ATTACK PLANTS WITH PHOSPHORUS DERIVATIVES OF CARBAMIMIDOTHIOIC ACID ESTERS Various phosphorus derivatives of carbamimidothioic acid esters having pesticidal activity are known, such as those taught in Czechoslovakian Patent No. 172,676. The present invention is directed to a method for the kill and control of sucking and boring-type insects which attack rice, fruit and nut trees, cotton, corn and vegetable plants employing compositions containing, as the active insecticide, at least one compound of the formula EMI1.1 wherein R and R1 are each independently a methyl or ethyl group or R and R1 when taken together represent an alkylene group containing 4 to 6 carbon atoms or a group of the formula EMI2.1 wherein A is oxygen, sulfur or -NR; R2 and R3 are each independently an alkyl group containing 1 to 4 carbon atoms and X and Y represent oxygen or sulfur with the proviso that X and Y are not the same By the term "alkyl" as used herein is meant alkyl groups which are either straight chained,-branched chained or cyclic. Such groups are for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, cyclopropyl and cyclobutyl. The preferred compounds of the present invention are those wherein Rê is methyl or ethyl. More preferred compounds are those wherein Rê is methyl or ethyl and R and R1 are independently either methyl or ethyl. Even more preferred compounds are those wherein Rê is methyl or ethyl, R and RÚ are independently either methyl or ethyl and R3 is methyl. The active compounds employed in the method of the present invention are either oils or crystalline solids and are soluble in many common organic solvents. In addition, the active compounds employed in the present invention are highly effective as plant systemic insecticides for the kill and control of such insects. The compounds employed in the present invention can be prepared by a variety of methods as follows: Method A: Substantially equimolar amounts of an appropriate substituted carbamimidothioic acid ester of the formulae EMI3.1 and an appropriate phosphorochloridothioic acid ester of the formulae EMI3.2 are reacted together in the presence of a solvent and a HC1 acceptor. In carrying out the reaction, the substituted carbamimidothioic acid ester and the phosphorus chloride reactants, the solvent and the HC1 acceptor are mixed together in any convenient manner. The mixture is then stirred at a temperature between 150C and gentle reflux until all of the phosphorus reactant is consumed. Representative solvents include, for example, acetonitrile, cyclohexane, benzene, toluene, xylene, acetone, methylene chloride, methylethyl ketone, diethyl ether, dioxane and tetrahydrofuran. Representative hydrogen chloride absorbers (acid-binding agents) include for example, alkali metal carbonates such as sodium and potassium carbonate and tertiary amines such as, for example, trimethylamine, triethylamine and pyridine. At the completion of the reaction, the reaction mixture is filtered to remove any insolubles and the filtrate concentrated under reduced.pressure. The residue is then taken up in ethyl ether, benzene, toluene, methylene chloride or chloroform and washed thoroughly with water and then with a saturated sodium chloride solution and dried. The solvent is removed by evaporation under reduced pressure leaving the desired product. It should be noted that when using phosphorochloridothioic acid O,O-dimethyl ester, as a starting material, the expected reaction product, where X is sulfur and Y is oxygen), is contaminated with from 1 to 3 percent of the corresponding rearrangement product where X is oxygen and Y is sulfur. Method B: Compounds wherein X is sulfur, Y is oxygen and R3 is methyl can be prepared employing this method: One mole of an appropriate N'-(dichlorophosphinothioyl)-N,N-substituted carbamimidothioic acid ester of the formulae EMI4.1 and substantially 2 moles of methanol are reacted together in the presence of a solvent and a HC1 acceptor. The reaction is conducted in a manner substantially the same as the reaction of Method A employing a temperature in the range of minus (-) 50C to plus (+) 800C. The solvents, the HC1 acceptors and the method of recovery are the same as set forth in Method A. Method C: Compounds wherein X is sulfur, and Y is oxygen can be prepared employing this method: Substantially equimolar amounts of an appropriate N'(chloromethoxyphosphinothioyl)-N,N-substituted carbamimidothioic acid ester of the formula EMI5.1 and a compound corresponding to the formula HOR are reacted together in the presence of a solvent and a HC1 acceptor. The reaction is conducted in a manner substantially the same as the reaction of Method A employing a temperature in the range of minus (-) 50C to plus (+) 800C. The solvents, the HC1 acceptors and the method of recovery are the same as set forth in Method A. Method D: Substantially equimolar amounts of N-(chloro (methylthio )methylene-N-methylmethanaminium chloride of the formula EMI6.1 and a compound corresponding to the formula EMI6.2 are reacted together in the presence of a solvent and a HC1 acceptor. The reaction is carried out in an inert solvent such as benzene, toluene or dioxane employing a temperature in the range of minus 50C to plus (+) 300C using triethylamine as the HC1 acceptor. The method of recovery is the same as set forth in Method A. Method E: Compounds wherein X is oxygen and Y is sulfur can be prepared by the rearrangement of the corresponding thiono compounds with the aid of an alkyl iodide or bromide. The reaction scheme is as follows: EMI7.1 wherein R, R1, R2 and R3 are as hereinbefore defined (the R3 in the R3 I or R3Br is the same as the R3 in 11SR311). In carrying out this reaction, one mole of an appropriate N'-dimethoxyphosphinothioyl-N,Nsubstituted carbamimidothioic acid ester is mixed with from 1 to 3 moles of the appropriate alkyl indide or bromide and the mixture heated under reflux for from 1 to 6 hours until the reaction is complete. The excess alkyl iodide or bromide is removed by distillation and the product purified by treatment with a solvent such as hexane or further distillation. Method F: The compounds wherein X is oxygen and Y is sulfur can also be prepared by thermal rearrangement of the corresponding thiono compounds: The reaction scheme is as follows: EMI7.2 In carrying out this reaction, the appropriate N'-(alkoxy(methoxy)phosphinothioyl)-N,N-substituted carbamimidothioic acid ester is distilled at a temperature of from 1100 to 1900C and a reduced pressure of from 0.5 to 1.5 millimeters of mercury. The following examples further illustrate the present invention. Example I A. Methyl N'-(dimethoxyphosphinothioyl)-N,N-dimethyl- carbamimidothioate EMI8.1 A mixture of 11.8 g of methyl N,N-dimethylcarbamimidothioate, 15 g of finely powdered potassium carbonate, 100 ml of acetonitrile and.l6 g of O,O-dimethyl phosphorochloridothioate was stirred and heated to 350C until all of the starting material was consumed. The insoluble salts which formed were then removed by filtration, the filtrate was concentrated under vacuum and the residue taken up in ether The ether solution was washed twice with water, once with a saturated sodium chloride solution and then dried over anhydrous sodium sulfate. The ether was removed in a rotary evaporator, leaving 14.6 g (60% of theoretical) of the methyl N' - (dimethoxyphosphinothioyl ) -N, N-dimethyl- carbamidothioate product as a nearly colorless oil. The product has a refreactive index of nd25 = 1.5677 (Compound 1). B. The above product was also prepared by an alternative procedure. A solution of 305 g of thiophosphoryl chloride in 700 ml of methylene chloride was cooled to OOC and 213 g of methyl N,N-dimethylcarbamimidothioate was added dropwise, followed by a dropwise addition of 185 g of triethylamine. After the addition was complete, the mixture was stirred for one hour at room temperature and 900 ml of methanol was added and 400 g of triethylamine was introduced dropwise. The temperature was kept below 450C during this reaction. After the addition was complete, the mixture was stirred at room temperature overnight. The triethylamine hydrochloride by-product was removed by filtration and the filtrate concentrated under vacuum. Ether was added to the residue and additional triethylammonium chloride thus formed was removed by filtration. The ether solution was then washed thrice with water, once with 5% aqueous sodium hydroxide, once with a saturated sodium chloride solution and then dried over anhydrous sodium sulfate. The ether was removed in a rotary evaporator, leaving 379 g (87% of theoretical) of the methyl N'-(dimethoxyphosphinothioyl)-N,N-dimethylcarbamimidothioate product as a nearly colorless oil. The oil was filtered through silica gel to remove a trace turbidity. The product 25 had a refractive index of nd = 1.5677. The oil solidified to a white crystalline solid which melted at 30-310C. Analysis: found: C, 29.85; H, 6.16; N, 11.55. Calculated for C6H15N202PS2: C, 29,74; H, 6.24; N, 11.56. Example II A. Methyl N'-(methoxy(methylthio)phosphinyl)-N,N -dimethylcarbamimidothioate EMI10.1 A mixture of 17.3 g of methyl N'-(dimethoxyphos phinothioyl ) -N, N-dimethylcarbamimidothioate and 100 ml of methyl iodide was heated under reflux for approximately 6 hours. The excess methyl iodide was then removed in a rotary evaporator. The residual oil was taken up in ether and the ether solution washed once with water, once with a saturated sodium chloride solution and then dried over anhydrous sodium sulfate. The ether was removed in a rotary evaporator leaving 13.0 g (75% of theoretical) of the methyl N'-(methoxy(methylthio) phosphinyl)-N,N-dimethylcarbamimidothioate product as a pale amber colorled oil. The product was recovered in a purity by GLC of 96% and had a refractive index of nd25 = 1.5762. The NMR and IR spectra are in agreement with the assigned structure. Analysis: Found: C, 28.32; H, 5.91; N, 11.85. Calculated for C6H15N202PS2: C, 29.74; H, 6.24; N, 11.56 (Compound 2). B. The above product was prepared by an alternative procedure. Methyl N'-(dimethoxyphosphinothioyl)-N,N -dimethylcarbamimidothioate (39.5 g) was twice distilled in a Kugelrohr distillation unit at a bath temperature of 1600 and a pressure of 0.5 mm. After the first distillation 85% of the product was rearranged, after the second distillation, rearrangement was virtually complete. Yield, 34.5 g (87% of theoretical) of a 25 colorless oil, having a refractive index of nod5 = 1.5700. Analysis: Found: C, 29.89; H, 6.19; N, 11.52. Calculated for C6H15N2O2PS2: C, 29.74; H, 6.24; N, 11.56. Example III 1-Methylethyl N'-(dimethoxyphosphinothioyl)-N,N dimethylcarbamimidothioate EMI11.1 A mixture of 6.0 g of 1-methylethyl N,N-dimethylcarbamimidothioate, 8.5 g of finely powdered potassium carbonate, 120 ml of acetonitrile and 6.6 g of O,O-dimethyl phosphorochloridothioate was stirred and heated to 400C for four hours. The insoluble salts which formed were then removed by filtration and the filtrate concentrated under vacuum. The residue was taken up in methylene chloride and the methylene chloride solution washed thrice with water and once with saturated sodium chloride solution and then dried over anhydrous magnesium sulfate. The solvent was removed in a rotary evaporator and a small amount of starting material was removed by heating the material in a Kugelrohr distillation unit to 80-850C at a pressure of 0.2 mm. The 1-methylethyl N'-(dimethoxy phosphinothioyl)-N,N-dimethylcarbamimidothioate product was recovered in a yield of 6.2 g as an amber colored oil. This oil was extracted with hexane and the hexane removed under vacuum to give a nearly colorless oil. The product had a refractive index of nd25 = 1.5507. Analysis: Found: C, 35.68; H, 7.05; N, 10.18. Calculated for C8H1gN202PS2: C, 35.54; H, 7.08; N, 10.36. (Compound 3) Example IV A. l-Methylethyl N'-(methoxy(methylthio)phosphinyl) -N,N-dimethylcarbamimidothioate EMI12.1 A mixture of 10.0 g of 1-methylethyl N,N -dimethylcarbamimidothioate, 15 g of finely powdered potassium carbonate, 100 ml of acetonitrile and 11.3 g of O,S-dimethyl phosphoiochloridothioate was stirred without heating for 72 hours. The insoluble salts which formed were removed by filtration and the filtrate concentrated under vacuum. The residue was dissolved in ether and the ether solution washed twice with water and once with saturated sodium chloride solution and then dried over anhydrous magnesium sulfate. The ether was removed in a rotary evaporator, leaving 10.0 g of the 1-methylethyl N'-(methoxy(methylthio)phosphinyl) -N,N-dimethylcarbamimidothioate product as a yellow oil which was purified by chromatography on Florisil (60-100 mesh, ethanol/hexane 50/50) to give a colorless oil. Purity by GLC 97%. The IR and NMR spectra were in agreement with the structural assignment (Compound 4). B. The above product was prepared by an alternative procedure. A solution of 6.6 g of 1-methylethyl N' - (dimethoxyphosphinothioyl ) -N, N-dimethylcarbamimido- thioate in 70 g of iodomethane was heated under reflux for 4 hours. The excess iodomethane was removed by distillation and the residual oil was extracted with hexane. The hexane was removed in a rotary evaporator to give the 1-methylethyl N'-(methoxy(methylthio)phosphinyl)-N,Ndimethylcarbamimidothioate product as a colorless oil. The product had a refractive index of n25 = 1.5499. Analysis: Found: C, 35.71; H, 6.96; N, 10.15. Calculated for C8H19N2O2PS2: C, 35.54; H, 7.08; N, 10.36. Example V Methyl N'-(dimethoxyphosphinothioyl)-N,N -diethylcarbamimidothioate EMI13.1 A mixture of 7.3 g of methyl N,N-diethylcarbamimidothioate, 8.0 g of finely powdered potassium carbonate, 70 ml of acetonitrile and 8.0 g of O,O-dimethyl phosphorochloridothioate was stirred and heated at 400C for four hours. The insoluble salts which formed were then removed by filtration and the filtrate concentrated under vacuum. The residue was taken up in ether and the ether solution washed twice with water and once with saturated sodium chloride solution and then dried over anhydrous sodium sulfate. The ether was removed under vacuum, leaving the methyl N'-(dimethoxyphosphinothioyl)-N,N-diethylcarbamimidothioate as a pale amber 25 colored oil which has a refractive index of nd = 1.5514 (Compound 5). Example VI Methyl N' -(ethylthio(methoxy)phosphinyl )-N,N- -dimethylcarbamimidothioate EMI14.1 A mixture of 5.0 g of methyl N'-(dimethoxy phosphinothioyl)-N,N-dimethylcarbamimidothioate and 75 g of iodoethane was heated under reflux for 2¸ hours. The excess iodoethane was removed in a rotary evaporator and the residual oil was distilled in a Kugelrohr distillation unit (bath temperature 1500C, pressure 0.1 mm) to give a colorless oil having a refractive index of nd25 = 1.5576. GLC and NMR indicated that the oily material is a mixture of about 75% of the desired methyl N'-(ethylthio(methoxy)phosphinyl)-N,N -dimethylcarbamimidothioate product and approximately 25% of methyl N'-(methoxy(methylthio)phosphinyl)-N,Ndimethylcarbamimidothioate (Compound 6). Example VII Methyl N'-(ethoxy(methoxy)phosphinothioyl)-N,N -dimethylcarbamimidothioate EMI14.2 A mixture of 5.9 g of methyl N,N-dimethylcarbamimidothioate, 8 g of finely powdered potassium carbonate, 50 ml of acetonitrile and 8.7 g of O-ethyl O-methyl phosphorochloridothioate was stirred and heated to 400C for 3 hours. The insoluble salts which formed were then removed by filtration and the filtrate concentrated under vacuum. The residue was taken up in ether and the ether solution washed twice with 5% aqueous sodium hydroxide and once with saturated sodium chloride solution and then dried over anhydrous sodium sulfate. The ether was removed in a rotary evaporator and the residue was distilled in a Kugelrohr distillation unit (bath temperature 950C, pressure 0.2 mm) leaving 10.0 g (78% of theoretical) of the desired methyl N' -(ethoxy(methoxy)phosphinothioyl )-N,N-dimethylcarb- amimidothioate product as an amber colored oil having a refractive index of nd25 = 1.5597. Analysis: Found: C, 32.49; H, 6.35; N, 11.02. Calculated for C7H17N2O2PS2: C, 32.80; H, 6.69; N, 10.93 (Compound 7). By following the preparative procedures as outlined in the above methods of preparation and the above examples and employing the appropriate starting materials, the following compounds were prepared. TABLE I EMI16.1 EMI16.2 <SEP> R <SEP> Physical <SEP> Property <tb> <SEP> N <SEP> Refractive <SEP> Index <SEP> or <tb> Compound <SEP> No. <SEP> Rê <SEP> RÚ <SEP> X <SEP> YR <SEP> Melting <SEP> Point <SEP> C <tb> <SEP> 8 <SEP> -CH3 <SEP> (C2H5)2N- <SEP> O <SEP> -SCH3 <SEP> nd25=1.5550 <tb> <SEP> 9 <SEP> -n-C3H7 <SEP> (CH3)2N- <SEP> O <SEP> -SCH3 <SEP> nd25=1.5557 <tb> <SEP> 10 <SEP> -Sec. <SEP> -C4H9 <SEP> (CH3)2N- <SEP> S <SEP> -OCH3 <SEP> nd25=1.5461 <tb> <SEP> 11 <SEP> -C2H5 <SEP> (CH3)2N- <SEP> O <SEP> -SCH3 <SEP> nd25=1.5601 <tb> <SEP> 12 <SEP> -C2H5 <SEP> (CH3)2N- <SEP> S <SEP> -OCH3 <SEP> nd25=1.5606 <tb> TABLE I (Continued) EMI17.1 <SEP> R <SEP> Physical <SEP> Property <tb> <SEP> N <SEP> Refractive <SEP> Index <SEP> or <tb> Compound <SEP> No. <SEP> Rê <SEP> RÚ <SEP> X <SEP> YR <SEP> Melting <SEP> Point <SEP> C <tb> <SEP> 13 <SEP> -C4H9 <SEP> (CH3)2N- <SEP> S <SEP> -OCH3 <SEP> nd25=1.5424 <tb> <SEP> 14 <SEP> -n-C3H7 <SEP> (CH3)2N- <SEP> S <SEP> -OCH3 <SEP> nd25=1.5553 <tb> <SEP> 15 <SEP> -CH3 <SEP> #- <SEP> O <SEP> -SCH3 <SEP> nd25=1.5802 <tb> <SEP> 16 <SEP> -CH(CH3)2 <SEP> #- <SEP> O <SEP> -SCH3 <SEP> oil <tb> <SEP> 17 <SEP> -n-C4H9 <SEP> #- <SEP> S <SEP> -OCH3 <SEP> oil <tb> TABLE I (Continued) EMI18.1 <SEP> R <SEP> Physical <SEP> Property <tb> <SEP> N <SEP> Refractive <SEP> Index <SEP> or <tb> Compound <SEP> No. <SEP> Rê <SEP> RÚ <SEP> X <SEP> YR <SEP> Melting <SEP> Point <SEP> C <tb> <SEP> 18 <SEP> -CH3 <SEP> # <SEP> S <SEP> -OCH3 <SEP> nd25=1.5666 <tb> <SEP> 19 <SEP> -CH3 <SEP> # <SEP> S <SEP> -OCH3 <SEP> nd25=1.5720 <tb> The compounds of the present invention are very effective for the control of the many sucking and boring-type insects found on the roots or aerial portions of growing rice plants. Representative of the various sucking and boring-type insects which attack rice plants and which are killed and controlled by the active compounds employed in the present invention are members of the orders Homoptera, Thysanoptera, Hemiptera, Coleoptera, and Acarina. More specifically, kill and control is obtained for insects such as aphids (Aphididae) such as the green peach aphid (Myzus persicae), the bean aphid (Aphis fabae), the black cherry aphid (Myzus ceraci), the pea aphid (Acythorsiphum pisum) and the potato aphid (Macrosiphum euphorbiae), the currant gall aphid (Cryptomyzus ribis), the mealy dapple aphid (Sappaphis mali), the mealy plum aphid (Hyalopterus pruni), the cotton aphid (Aphis gossypii); the whiteflies (Aleyrodidae) including the banded wing whitefly (Trialeurodes abutilonea), grape whitefly (Trialeurodes vittata), greenhouse whitefly (Trialeurodes vaporarium) and sweet potato white fly (Bemisia tabacii); scales such as the San Jose scale (Aspidiotus perniciosus), oyster scale (Lepidosaphes ulnii), the California red scale (Aonidiella aurantii), black scale (Saissetia olea), Terapin scale (Lecanium sp) and the oleander scale (Aspidiotus hederae); mealybugs (coccidae) such as the grape mealybug (Pseudococcus maritimus), greenhouse mealybug (Pseudococcus sp) and citrus mealybug (Planococcus sp); thrips (Thysanoptera) such as (Hercinothrips femoralis), gladiolus thrips (Taeniothrips sup), onion thrips (Thrips tabacii), greenhouse thrips (Heliothrips sup), flower thrips (Frankliniella sp) and rice thrips (Chloethrips oryzae); bugs, for example the beet bug (Piesma quadrata), squash bug (Anasa sup), harlequin bugs (Murgantia histriconica), (Trigonotylus sp), Corbett ricebug (Leptocorixa corbetti), slender ricebug (Cletus trigonus), black ricebug (Scotinophora lurida), plant bugs (Lygus sup), fleahoppers (Halticus sup), cotton fleahoppers (Psallus E), the cotton bug (Dysdercus intermedius) and stinkbugs such as the southern green stinkbug (Nezara viridulla); leafhoppers and planthoppers, such as aster leafhopper (Macrosteles fascifrons), rice green leafhopper (Nephotettix virescens), zig zag leafhopper (Recilia dorsalis), (Nephotettix apicalis), white back planthopper (Sogattella furcifera), brown planthopper (Nilaparvata lugens), smaller brown planthopper (Laodelphax striatellus), grape leafhopper (Erythroneura sp), potato leafhopper (Empoasca fabae), apple sucker (Psylla mali), pear psylla (Psylla pyricola), potato psillid (Paratrioza cockerlelli) and the like as well and rice water weevil (Lissorhoptrus oryzophilus); the mites (Acarina) in particular, the spider mites (Tetranychidae) such as the two-spotted spider mite (Tetranychus urticae), carmine spider mite (Tetranychus cinnabarinus) and the European red mite (Panonychus ulmi), blister mites, for example the currant blister mite (Eriophyes ribis) and tarsonemids, for example the broad mite (Hemitarsonemus latus), the cyclamen mite (Tarsonemus pallidus); borers such as the rice stemborer (Chilo sp), pink borer (Sesamia sp) and the paddy borer (Tryporyza sp), and the like. In the present specification and claims, the term "systemic" defines the translocation of the active compound employed in the present method through the plant. The active compound can be applied either to the above-ground or preferably to below-ground portions of the plant. The application of an insecticidally effective amount of an active compound of the present invention is critical to the method of the present invention. The active compound can sometimes be employed in unmodified form. Frequently, however, for easier application, the compound is modified by the employment with it of an adjuvant or inert carrier therefor. Thus, for example, many of the present compounds are very soluble in water and they are also relatively soluble in oils, including plant essential oils. Therefore, the practical enjoyment of the beneficial utilities of the present compound often requires that tne compound be composited with one or more adjuvant substances which are chemically inert to the active compound, and the resulting compositions are comprehended within the present invention. The compositions can be formulated in various forms, such as emulsifiable concentrates, wettable powders, flowable suspension dusts, granules, microencapsulated granules, fine granules, oil sprays, aerosols, and the adjuvant employed can be any one or a plurality of materials including aromatic solvents, petroleum distillates, water, or other liquid carriers, propellant substances, surface-active dispersing agents, light absorbers, and finely divided carrier solids. In such compositions, the adjuvant cooperates with the active compound so as to obtain a composition to facilitate the method of the present invention, and to obtain an improved result. The use of either a surface-active dispersing agent or a finely divided carrier solid and the use of both a surface-active dispersing agent and a finely divided carrier solid, simultaneously, constitute preferred embodiments of the method of the present invention. Another preferred embodiment of the present invention is a composition comprising one or more of the presently claimed compounds, an organic liquid as a solvent and carrier therefor, and a propellant material. Numerous other embodiments will become available to those skilled in the art in view of the teachings set forth hereinbelow. The exact concentration of the active compound in a composition thereof with an adjuvant therefor can vary; it is only necessary that the active compounds be present in a sufficient amount so as to make possible the application of an insecticidally effective dosage. Generally, for practical applications, the active compounds can be broadly applied to the plants or to the soil around the roots of the plants or to water, such as in broadcast rice paddy applications in compositions containing from 0.00001 percent to 98 percent by weight of the active compound. In preparation of dust compositions, the product can be compounded with any of the finely divided carrier solids such as prophyllite, diatomaceous earth, gypsum and the like. In such operations, the finely divided carrier is ground or mixed with the active compound, as active agent, or wetted with a solution of the active agent in a volatile organic solvent. Similarly, dust compositions containing the active product can be similarly compounded from various of the solid dispersing agents, such as fullers earth, attapulgite and other clays.- These dust compositions can be employed as treating compositions or can be employed as concentrates and subsequently diluted with additional solid dispersing agent or with pyrophyllite, diatomaceous earth, gypsum and the like to obtain the desired amount of active agent in a treating composition. Also, such dust compositions can be dispersed in water, with or without the aid of surfactant, to form spray mixtures. Further, the active compound or a dust concentrate composition containing said compound can be incorporated in intimate mixture with surface active dispersing agents such as ionic and nonionic emulsifying agents to form spray concentrates. Such concentrates are readily dispersible in liquid carriers to form sprays containing the toxicant in any desired amount. The choice of dispersing agent and amount thereof employed are determined by the ability of the agent to facilitate the dispersion of the concentrate in the liquid carrier to produce the desired spray composition. In the preparation of liquid compositions, the active compound can be compounded with a suitable water-immiscible organic liquid and a surface-active dispersing agent to produce an emulsifiable liquid concentrate which can be further diluted with water and oil to form spray mixtures in the form of oil-in-water emulsions. In such compositions, the carrier comprises an aqueous emulsion, that is, a mixture of water -immiscible solvent, emulsifying agent and water. Preferred dispersing agents to be employed in these compositions are oil-soluble and include the nonionic emulsifiers such as the polyoxyethylene derivatives of sorbitan esters, complex ether alcohols and the like. However, oil-soluble ionic emulsifying agents such as mahogany soaps can also be used. Suitable organic liquids to be employed in the compositions include petroleum oils and distillates, toluene liquid halohydrocarbons and synthetic organic oils. The surfaceactive dispersing agents are usually employed in liquid compositions in the amount of from 0.1 to 20 percent by weight of the combined weight of the dispersing agent and active compound. When operating in accordance with the present invention, the active compound or a composition containing the active compound is applied to the plants or to their habitat in any convenient manner, for example, by means of hand dusters or sprayers. Application to the foliage of the plants is conveniently carried out with power dusters, boom sprayers and fog sprayers. In such foliar applications, the employed compositions should not contain any appreciable amounts of any phytotoxic diluents. In large scale operations, dusts, or low-volume sprays can be applied from an airplane. In further embodiments, one of the compounds of the present invention or compositions containing the same, can be advantageously employed in combination with one or more additional pesticidal compounds. Such additional pesticidal compounds may be insecticides, nematocides, arthropodicides, herbicides, fungicides or bactericides that are compatible with the compounds of the present invention in the medium selected for application and not antagonistic to the activity of the present compounds. Accordingly, in such embodiments, the pesticidal compound is employed as a supplemental toxicant for the same or for a different pesticidal use, or as an additament. The compounds in combination can generally be present in the ratio of from 1 to 99 parts of the compound of the present invention with from 99 to 1 part of the additional compound(s). Dosage amounts are generally from 15-1,000 grams (g) preferably frbm 40-600 g of active compound and most preferably from 125-500 g of active compound per hectare. However, in special cases, it is possible to exceed or reduce the amount and this may sometimes be necessary. Example VIII Aqueous dispersions were prepared by admixing one of the hereinafter set forth compounds, dissolved in a suitable inert solvent with a predetermined quantity of water and a predetermined amount of a surfactant to give aqueous dispersions containing varying predetermined amounts of one of the compounds as the sole toxicant. Separate chili pepper plants were infested with green peach aphids. A predetermined volume of chemical was injected into the root zone area of the plant. In a like manner, green peach aphids were placed on control plants and the root zone area of the plants was injected with a solution containing only water and surfactant. The plants were maintained under conditions conducive to the growth of the plants and aphids. After a period of three days, the plants were examined to determine the minimum concentration in parts of the active compound per million parts of the ultimate dispersion necessary to give at least a 95 percent systemic kill and control of the green peach aphids. The results of this examination are set forth below in Table II. TABLE II Minimum Concentration in ppm of active compound in dispersion to Number of give LC for the systemic active Compound control o green peach aphid 1 25 2 > 6.2 to < 25 3 400 5 > 400 Example IX Aqueous dispersions were prepared by admixing one of the hereinafter set forth compounds, dissolved in a suitable inert solvent, with a predetermined quantity of water and a predetermined amount of a surfactant to give aqueous dispersions containing varying predetermined amounts of one of the compounds as the sole toxicant. Separate cotton plants were infested with 20 two-spotted spider mites and the plants sprayed with one of the dispersions to run off. In a like manner, 20 two-spotted spider mites were placed on control plants and the plants sprayed to run off with a solution containing only water and surfactant. The plants were maintained under conditions conducive to the growth of the plants and mites. After a period of five days, the plants were examined to determine the minimum concentration in parts of the active compound per million parts of the ultimate dispersion necessary to give at least 95 percent kill and control of the two-spotted spider mites. The results of this examination are set forth below in Table III. TABLE III Minimum Concentration in ppm of active compound in dispersion to give Number of LC for foliar control of active Compound tao-spotted spider mite 1 < 25 to > 100 2 100 3 > 400 4 100 5 > 400 6 > 100 to < 400 7 > 400 8 < 400 9 400 10 < 400 11 < 400 12 > 400 13 < 400 14 < 400 15 100 16 > 400 Example X Aqueous dispersions were prepared by admixing one of the hereinafter set forth compounds, dissolved in a suitable inert solvent, with a predetermined quantity of water and a predetermined amount of a surfactant to give aqueous dispersions containing varying predetermined amounts of one of the compounds as the sole toxicant. Separate cotton plants were infested with 20 two-spotted spider mites and a predetermined volume of the test dispersion was injected into the root zone of the plants to determine systemic insecticidal effects. In a like manner, 20 two-spotted spider mites were placed on control plants and a solution containing only water and surfactant was injected to the root zone. The plants were maintained under conditions conducive to the growth of the plants and mites. After a period of five days, the plants were examined to determine the minimum concentration in parts of the active compound per million parts of the ultimate dispersion necessary to give at least 95 percent kill and control of the two-spotted spider mites. The results of this examination are set forth below in Table IV. TABLE IV Minimum Concentration in ppm of active compound in dispersion to give Number of LC for systemic control of active Compound two-spotted spider mite 1 > 25 to < 100 2 > 25 to < 100 3 > 400 4 > 25 to < 100 5 > 400 6 400 7 100 8 < 400 9 < 400 10 < 400 11 < 400 TABLE IV (Continued) Minimum Concentration in ppm of active compound in dispersion to give Number of LC for systemic control of active Compound two-spotted spider mite 12 > 400 13 < 400 14 < 400 15 > 25 to < 100 16 > 400 Example XI Aqueous dispersions were prepared by admixing one of the hereinafter set forth compounds with a predetermined quantity of water and a predetermined amount of a surfactant to give aqueous dispersions containing varying predetermined amounts of one of the compounds as the sole toxicant. Separate rice plants were dipped into one of the dispersions and permitted to dry. A plastic cylinder was placed around each of the plants and 10 adult Aster leafhoppers were placed in the cylinder and the cylinder capped. In a like manner, 10 adult Aster leafhoppers were placed on control plants which had been dipped in a solution containing only water and surfactant. The plants were maintained under conditions conducive to the growth of the plants and leafhoppers. After a period of three days, the cylinder and plants were examined to determine the minimum concentration in parts of the active compound per million parts of the ultimate dispersion necessary to give at least 95 percent kill and control of the Aster leafhopper. The results of this examination are set forth below in Table V. TABLE V Minimum Concentration in ppm of active compound in dispersion to give Number of LD for foliar control of active Compound Aster leafhoppers 1 25 2 6.2 3 100 4 25 5 100 6 6.2 7 150 8 25 9 25 10 400 11 6.2 12 > 25 to < 100 13 100 14 100 15 25 Example XII Aqueous dispersions were prepared by admixing one of the hereinafter set forth compounds with a predetermined quantity of water and a predetermined amount of a surfactant to give aqueous dispersions containing varying predetermined amounts of one of the compounds as the sole toxicant. Separate rice plants were treated by adding a predetermined amount of one of the test dispersions to the root of the plant to determine systemic activity. A plastic cylinder was placed around each of the plants and 10 adult Aster leafhoppers were placed in the cylinder and the cylinder capped. In a like manner, 10 adult Aster leafhoppers were placed on control plants which were treated at the root zone with a solution containing only water and surfactant. The plants were maintained under conditions conducive to the growth of the plants and leafhoppers. After a period of three days, the cylinder and plants were examined to determine the minimum concentration in parts of the active compound per million parts of the ultimate dispersion necessary to give at least 95 percent kill and control of the Aster leafhopper. The results of this examination are set forth below in Table VI. TABLE VI Minimum Concentration in ppm of active compound in dispersion to give Number of LD for systemic control active Compound o Aster leafhoppers 1 25 2 0.38 3 100 4 25 TABLE VI (Continued) Minimum Concentration in ppm of active compound in dispersion to give Number of LD for systemic control active Compound o Aster leafhoppers 5 400 6 < 1.5 7 200 8 25 9 25 10 400 11 1.5 12 > 25 to < 100 13 > 25 to < 100 14 > 25 to < 100 15 > 6:2 to < 25 Example XIII Aqueous dispersions were prepared by admixing one of the hereinafter set forth compounds with a predetermined quantity of water and a predetermined amount of a surfactant to give aqueous dispersions containing varying predetermined amounts of one of the compounds as the sole toxicant. Separate rice plants were dipped into one of the dispersions and permitted to dry. A plastic cylinder was placed around each of the plants and 10 adult brown planthoppers were placed in the cylinder and the cylinder capped. In a like manner, 10 adult brown planthoppers were placed on control plants which had been dipped in a solution containing only water and surfactant. The plants were maintained under conditions conducive to the growth of the plants and planthoppers. After a period of three days, the cylinder and plants were examined to determine the minimum concentration in parts of the active compound per million parts of the ultimate dispersion necessary to give at least 90 percent kill and control of the brown planthopper. The results of this examination are set forth below in Table VII. TABLE VII Minimum Concentration in ppm of active compound in dispersion to give Number of LD for foliar control of active Compound Brown Planthoppers 1 25 2 6.25 Example XIV Aqueous dispersions were prepared by admixing one of the hereinafter set forth compounds with a predetermined quantity of water and a predetermined amount of a surfactant to give aqueous dispersions containing varying predetermined amounts of one of the compounds as the sole toxicant. Separate rice plants were treated by adding a predetermined amount of one of the test dispersions to the root of the plant to determine systemic activity. A plastic cylinder was placed around each of the plants and 10 adult brown planthoppers were placed in the cylinder and the cylinder capped. In a like manner, 10 adult brown planthoppers were placed on control plants which were treated at the root zone with a solution containing only water and surfactant. The plants were maintained under conditions conducive to the growth of the plants and planthoppers. After a period of three days, the cylinder and plants were examined to determine the minimum concentration in parts of the active compound per million parts of the ultimate dispersion necessary to give at least 90 percent kill and control of the brown planthopper. The results of this examination are set forth below in Table VIII. TABLE VIII - Minimum Concentration in ppm of active compound in dispersion to give Number of LD O for systemic control active Compound of Brown Planthoppers 1 6.25 2 1.6 Example XV Aqueous dispersions were prepared by admixing one of the compounds of the present invention, dissolved in a suitable inert solvent, with a predetermined quantity of water and a predetermined amount of a surfactant to give aqueous dispersions containing varying predetermined amounts of the compound as the sole toxicant. Separate cotton plants were infested with several hundred one week old, banded-wing whitefly nymphs. Plants were sprayed to run off with each of the dispersions. In a like manner several hundred nymphs were infested onto a control plant and the plants sprayed to run off with a solution containing only water and surfactant. The plants were maintained under conditions conducive to the growth of the plants and insects. After a period of 21 days, the plants were examined to determine the percent control at the various concentrations of the toxicant applied. Percent control was determined by the number of nymphs which did not successfully emerge as adults. The results of this examination are set forth below in Table IX. TABLE IX Percent Control of banded-wing white fly nymphs by foliar appli Number of cation to cotton plants at the active Compound indicated dosage rate in PPM 2 25 6.2 3.1 0 100 97 75 0 Example XVI Aqueous dispersions were prepared by admixing one of the compounds of the present invention, dissolved in a suitable inert solvent, with a predetermined quantity of water and a predetermined amount of surfactant to give aqueous dispersions containing varying predetermined amounts of the compound as the soil toxicant. Separate cotton plants were infested with several hundred one week old banded-wing white fly nymphs and a predetermined volume of the test dispersion was injected into the root zone of plants to determine systemic insecticidal effects. In like manner, several hundred nymphs were infested onto control plants and a solution containing only water and surfactant was injected into the root zone. The plants were maintained under conditions conducive to the growth of the plants and whitefly nymphs. After a period of 21 days, the plants were examined to determine the percent control at the various concentrations of the toxicant applied. Percent control was determined by the number of nymphs which did not successfully emerge as adults. The results of this examination are set forth below in Table X. TABLE X Percent control of banded-wing whitefly nymphs by root zone application to cotton plants Number of at the indicated dosage rate active Compound in PPM 2 100 25 6.2 0 100 97 95 o Example XVII Aqueous dispersions were prepared by admixing one of the compounds of the present invention, dissolved in a suitable inert solvent, with a predetermined quantity of water and a predetermined amount of surfactant to give aqueous dispersions containing varying predetermined amounts of the compound, as the sole toxicant. Separate corn plants were infested with 50-75 adults and nymphs of the corn leaf aphid, Aphis maidis. These aphids generally feed and aggregate only on the lower portion of the corn stalk. A sufficient quantity of each chemical dispersion was sprayed onto the upper leaf portions of the corn plant, taking care not to contaminate the lower portion of stalk with the chemical spray. Plants were then allowed to dry upside down to prevent run-off onto aphid feeding zone. In a like manner a set of control plants were also treated using a solution containing only water and surfactant. The treated plants were maintained under conditions conducive to the growth of the plants and insects. After a period of 12 days the plants were examined to determine the percent control at the various concentrations of the toxicant applied. Percent control was determined by the number of live aphids on the test plants versus the number of live aphids on the control. The results of this examination are set forth below in Table XI. TABLE XI Percent control of the corn leaf aphid, Aphis maidis, through downward translocation of the Number of insecticide on corn at the active Compound indicated dosage in PPM 2 400 200 100 0 100 50 0 0 When applied at a dosage level as hereinabove set forth, each of the compounds of the present invention, the utility of which is not specifically exemplified hereinabove, has the ability to kill, inhibit or otherwise control one or more of the above said or other fungal or insect pests. The substituted carbamimidothioic acid esters corresponding to the formula EMI38.1 wherein R, R1, and R2 are as hereinbefore defined are for the most part known compounds and can be prepared by the reaction of an appropriate carbothioamide corresponding to the formula EMI38.2 with the appropriate alkyl halide followed by treatment of the corresponding S-alkyl-N,N-substituted isothiourea hydrogen halide salt thus formed with a base to obtain the desired carbamimidothioic acid ester as the free base. In carrying out this reaction, the alkylhalide reactant is slowly added to a mixture of the carbothioamide reactant and a solvent such as methanol, ethanol or toluene. The mixture is then heated under reflux until the reaction is complete (from 1 to 4 hours or more). The reaction mixture is heated under reduced pressure to remove most of the solvent and the product is recovered by filtration. The product which is in the form of the hydrogen halide salt can be treated directly with a base such as, a dilute aqueous sodium or potassium hydroxide solution or if desired, the product can be separated and purified by recrystallization from one of the solvents listed above and then treated with the base to obtain the product as the free base. The substituted carbothioamides corresponding to the formula EMI39.1 wherein R and R1 are as hereinbefore defined are for the most part known compounds and can be prepared in a two-step process. In the first step, substantially equimolar amounts of tertiary butyl isothiocyanate and an appropriate amine are reacted together in the presence of a solvent. The thus formed tertiary butyl thiourea is then treated with concentrated hydrochloric acid to remove the tertiary butyl group leaving the desired compound. In carrying out this reaction, the tertiary butyl isothiocyanate is very slowly added to a stirred solution of the amine reactant in a solvent such as hexane, benzene or toluene which is at a temperature of from -10 to 200C. The stirring mixture is allowed to warm up to room temperature ( to 2 hours) and the product precipitates out and is recovered by filtration. The product can be purified if desired by recrystallization from a solvent such as ethanol, hexane, benzene or toluene. The thiourea product, prepared as above, is admixed with from 2 to 4 moles of concentrated hydrochloric acid and the mixture heated to a temperature of from 500 to 950C. The heating is conducted until all of the thiourea reactant is dissolved. The tertiary butyl chloride is then distilled off. The solution is cooled to 200C and made basic by the addition of aqueous sodium hydroxide. The desired product is then recovered by filtration. The product can be purified, if desired, by water washing and/or recrystallization of from a solvent such as ethanol or hexane. The N'-(disubstitutedphosphinyl)-N,N -substituted carbamimidothioic acid esters which correspond to the formula EMI40.1 wherein R, Rl, R2, and X are as hereinbefore defined and R4 is Cl or OCH3 and which are employed as starting materials can be prepared by a method wherein substantially equimolar amounts of an appropriate substituted carbamimidothioic acid ester of the formula EMI40.2 and either a thiophosphoryl halide EMI41.1 a phosphorus oxyhalide EMI41.2 are reacted together in the presence of a solvent and a HCl acceptor. The reaction is conducted in a manner substantially the same as the reaction of Method A employing temperatures in the range of minus (-) 100 to 500C. The solvents, the HCl acceptors and the method of recovery are the same as set forth in Method A. Example XVIII Methyl N-( dichlorophosphinyl) -N, N-dimethylcarba- mimidothioate EMI41.3 A solution of 11.8 g of methyl N,N-dimethylcarbamimidothioate in 125 ml of methylene chloride was stirred, cooled to -100C and first 15.3 g of phosphorus oxychloride and then 10.1 g of triethylamine were added dropwise. Stirring was continued at -100C for one hour and at room temperature for another hour. The mixture was filtered, the filtrate washed thrice with 75 ml portions of ice-water and dried over anhydrous magnesium sulfate. The solvent was removed in a rotary evaporator leaving 18.2 g of a clear oil. The NMR spectra indicated the desired product containing a small amount of an impurity. To obtain high purity product, the oil was dissolved in a small amount of methylene chloride and reprecipitated by the addition of hexane. The solvent layer was decanted and the residue freed from solvent in a rotary evaporator, leaving 13.0 g of a pale yellow colored oil, RI(250) = 1.5690. The IR and NMR spectra are in agreement with the desired structure. Analysis: Calcd. for C4H9Cl2N2OPS: C, 20.44; H, 3.86; N, 11.92. Found: C, 20.70; H, 3.86; N, 12.12 Example XIX Methyl N- ( (dichlorophosphinothioyl ) -N, N-di- methylcarbamimidothioate EMI42.1 A solution of 11.8 g of methyl N,N-dimethylcarbamimidothioate in 200 ml of methylene chloride was stirred, cooled to 50C and first 16.9 g of thiophosphoryl chloride and then 10.1 g of triethylamine were added dropwise. Stirring at 50C was continued for one hour and at room temperature for 4 hours. The mixture was filtered, the filtrate washed thrice with 50 ml portions of water and dried over anhydrous magnesium sulfate. The solvent was removed in a rotary evaporator leaving 23.7 g of a brown colored oil, RI(250) = 1.6196. The NMR spectra was in agreement with the desired structure. Analysis: Calcd. for C4HgCl2N2PS2: C, 19.13; H, 3.61; N, 11.16. Found: C, 19.92; H, 3.76; N, 11.10. Example XX Methyl N-(chloromethoxyphosphinothioyl)-4morpholinecarboximidothioate EMI43.1 A solution of 17.5 g of O-methyl phosphorodichloridothioate in 125 ml of acetonitrile was stirred, cooled to 50C and 16.0 g of methyl 4-morpholinecarboximidothioate was added in portions. Cooling was discontinued after the addition was complete and the mixture was stirred at room temperature for 4 hours. The reaction mixture was concentrated under vacuum, the residue dissolved in methylene chloride, the methylene chloride solution washed twice with 100 ml portions of water, once with saturated sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was removed under vacuum leaving 18.9 g of a reddish colored oil. The NMR spectra indicated the desired product. Example XXI Methyl N-(dichlorophosphinyl)-4-morpholinecarboximidothioate EMI43.2 To a solution of 16.94 g of thiophosphoryl chloride and 16.0 g of methyl 4-morpholinecarboximidothioate in 250 ml of methylene chloride was added at 50C, 10.2 g of triethylamine. The mixture was stirred at room temperature for 4 hours, the triethylamine hydrochloride removed by filtration and the filtrate washed with three 50 ml portions of water. The solution was dried over anhydrous magnesium sulfate, the solvent removed under vacuum leaving an oil which crystallized on standing and was recrystallized from a small amount of methylene chloride and hexane. White crystals, m.p. 79-810 were obtained in 19.5 g yield. The IR and NMR spectra are in agreement with the desired structure. Analysis: Calcd. for C6HllC12N2OPS2: C, 24.58; H, 3.78; N, 9.56. Found: C, 25.20; H, 4.02; N, 9.69. Example XXII Methyl N-(chloromethoxyphosphinothioyl)-N,Ndimethylcarbamimidothioate EMI44.1 A stirred solution of 33 g of O-methyl phosphorodichloridothioate in 200 ml of acetonitrile was cooled to 50C and 23.64 g of methyl N,N-dimethylcarbamimidothioate was added dropwise. After the addition was complete, the mixture was stirred at approximately 50C for two hours. The solvent was then removed in a rotary evaporator, the residue dissolved in methylene chloride, the methylene chloride solution washed with four 50 ml portions of water and dried over anhydrous magnesium sulfate. The solvent was then removed under vacuum and the residue taken up in a minimum amount of methylene chloride. To this solution hexane was added to precipitate the product as an oil. The supernatant liquid was decanted and the remaining solvent was removed under vacuum leaving 10.4 g of an amber colorled oil, having a refractive index of nd25 = 1.5956. The NMR and IR spectra were in agreement with the desired structure. Example XXIII 1-Methylethyl N-(chloromethoxyphosphinothioyl) -N,N-dimethylcarbamimidothioate EMI45.1 To a solution of 14.3 g of O-methyl phosphorodichloridothioate in 120.ml of acetonitrile was added dropwise in a solution of 12.7 g of 1-methylethyl N,N-dimethylcarbamimidothioate in 25 ml of acetonitrile. The temperature during the addition was kept between 50 to 70C and was then allowed to rise to room temperature. After stirring overnight, the solvent was removed under vacuum, the residue dissolved in methylene chloride, the methylene chloride solution washed thrice with water, once with saturated sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was removed under vacuum and the residue was repeatedly extracted with hexane. The hexane extract was concentrated under vacuum to give 7.9 g of desired product. The NMR spectrum was in agreement with the structural assignment.

Claims: CLAIMS: 1. A method for the kill and control of insects which attack plants which comprises contacting the insects or their habitat with a composition which comprises an inert carrier in intimate admixture with an insecticidally effective amount of at least one active compound of the formula EMI47.1 wherein R and R1 are each independently a methyl or ethyl group or R and R1 when taken together represent an alkylene group containing 4 to 6 carbon atoms or a group of the formula EMI47.2 wherein A is oxygen, sulfur or -NR; Rê and R are each independently an alkyl group containing 1 to 4 carbon atoms and X and Y represent oxygen or sulfur, with the proviso that X and Y are not the same. 2. A method as claimed in claim 1 wherein X is oxygen in the compound of formula I. 3.. A method as claimed in claim 2 wherein the compound of Formula I is methyl N'-(methoxy(methylthio) phosphinyl)-N,N-dimethylcarbamimidothioate. 4. A method as claimed in claim 2 wherein the compound of Formula I is l-methylethyl N'-(methoxy(methyl thio) phosphinyl) -N,N-dimethylcarbamimidothioate. 5. A method as claimed in claim 2 wherein the compound of Formula I is methyl N'-(methoxy(ethylthio)- phosphinyl)-N,N-dimethylcarbamimidothioate. 6. A method as claimed in claim 2 wherein the compound of Formula I is n-propyl N'-(methoxy(methylthio)- phosphinyl)-N,N-dimethylcarbamimidothioate. 7. A method as claimed in claim 2 wherein the compound of Formula I is methyl N'-(methoxy(methylthio)- phosphinyl)-4-morpholinecarboximidothioate. 8. A method as claimed in claim 2 wherein the compound of Formula I is methyl N'-(methoxy(methylthio)- phosphinyl)-N,N-diethylcarbamimidothioate. 9. A method as claimed in claim 1 wherein X is sulfur in the compound of Formula I. 10. A method as claimed in claim 9 wherein the compound of Formula I is methyl N'-(ethoxy(methoxy)phosphinothioyl)-N,N-dimethylcarbamimidothioate. 11. A method as claimed in claim 9 wherein the compound of Formula I is methyl N-(dimethoxyphosphino thioyl)-4-morpholinecarboximidothioate. 12. A method as claimed in claim 9 wherein the compound of Formula I is methyl N'-(dimethoxyphosphinothioyl)-N,N-dimethylcarbamimidothioate.

Inventors: PAROONAGIAN, DORIS LUCY, REIFSCHNEIDER, WALTER
Applicants: THE DOW CHEMICAL COMPANY
Application year: 1983
Main classification: A01N57
IPC codes: C07F9, A01N57