Insecticidal O-phenyl S-aryl alkylphosphonodithioates
United States Patent 1 Chupp Apr. 29, 1975 INSECTICIDAL O-PHENYL S-ARYL ALKYLPHOSPHONODITHIOATES Related U.S. Application Data [60] Division of Ser. No. 258.969. June 2. I972. Pat. No 3.816.569. which is 21 continuation-in-part of Ser. No. 11.9l2. Fch. l6. I970. abandoned.  
 [521 U.S. Cl. 424/222 [51] Int. Cl. A01N 9/36 [58] Field of Search 424/222; 260/961 [561 References Cited UNITED STATES PATENTS 2.769.743 11/1956 Mattson 424/222 3.099.597 7/l963 Chupp et ul. 424/222 3.361.855 l/l968 Schradcr 260/96l X 3.794.700 2/1974 Sehring et al 260/96l Primary E.\&#39;aminerAlbert T. Meyers Assistanl E.\&#39;uminerLe0nard Schenkman Attorney. Agent, or Firm--John L. Young; Donald W. Peterson [57] ABSTRACT S-aryl O-phenyl alkylphosphonodithioates are useful as insecticides. In particular. S-(p-tolyl) O-phenyl methylphosphonodithioate for use in combating soil insects of the genus Diabrotica.  
 20 Claims, No Drawings INSECTICIDAL O-PHENYL S-ARYL ALKYLPHOSPHONODITHIOATES This a division of application Ser. No. 258,969, filed June 2, 1972, now US. Pat. No. 3,816,569, which in turn is a continuation-in-part of Ser. No. 11,912, filed Feb. 16, 1970, now abandoned.  
  This invention relates to S-aryl O-phenyl alkylphosphonodithioates of the formula wherein R is methyl or tertiary butyl, n is an integer from O to 2, and R is lower alkyl provided that when R is tertiary butyl, R is ethyl. It is preferred than when n is 2, R is methyl.  
  As employed herein, the term lower alkyl designates those groups wherein the aliphatic chain is straight or branched and has from 1 through 4 carbons inclusive. Preferred lower alkyl are ethyl and methyl.  
  As employed herein, the term aryl designates those groups which are phenyl or alkyl-substituted phenyl, such as tolyl, xylyl, or tertiary-butyl phenyl.  
  A preferred embodiment of this invention relates to S-(p-tolyl) O-phenyl methylphosphonodithioate CH3 s P o The white solid compound is prepared by known methods, for example, by refluxing a substantially equimolecular mixture of O-phenyl ethylphosphonothionochloride, p-thiocresol and triethyl amine in benzene. It has a melting point of about 46 to 48 Centigrade (C.), is insoluble in water and soluble in acetone.  
  S-(m-tolyl) O-phenyl ethylphosphonodithioate has the formula T, o c 11 c2115 11 s 1 0 c ns CH3 C2115 The white solid compound is prepared by known methods, for example, by refluxing a substantially equimolecular mixture of O-phenyl ehtylphosphonothionochloride, m-thiocresol and triethyl amine in benzene. It is identified by nuclear magnetic resonance and elemental analysis and found to be insoluble in water and soluble in acetone.  
  Some of the other compounds of this invention which may be prepared similarly by reacting the appropriate thiophenol or alkyl-substituted thiophenol with the appropriate phosphonothionochloride are as follows:  
 S--(2, lxylyl) O-phenyl ethylphosphonodithioate s- (m--toly1) O-phenyl methylphosphonodithioate n S- P- O-- Col-I I CH3 white solid m.p. 616 IC.  
 8- (o--to.l.yl) 0-pheny1 mcthylphosphonoditgh ioate S O-cliplienyl lh&#39;i; s lid O S v 1 e o e thy lpl&#39;iosplionod i th Lottie white solid .m.p. 105-112 C.  
 S- (o--tolyl) O-phenyl ethylphosphonodithioate white solid m.p. 53.565 C.  
 S- a-tertiary butylphenyl) O-phenyl ethylphosphonodithioate II (CH3)3C--S P o c ns white solid m.p. 6l66.50.  
 S- (2 l-xyly1) O-phenyl methylphosphonodithioate Various important crop plants are subject to attack by the larval stage of soil insects of the genus Diabrotica, for example, the northern corn rootworm, Diabrotica longicornis and the western corn rootworm, Diabrotica virgifera, which feed specifically on the root system of corn plants, the southern corn rootworm (or spotted cucumber beetle), Diabrotica undecimpunctata howardi which attacks cucurbits, peanut pods, and also roots of corn plants, and the banded cucumber beetle, Diabrotica balteata which attacks root systems of sweet potatoes. The larval stage of these insects attack or eat all of the smaller roots of infested plants and form tunnels in the larger roots, thereby weakening or destroying them. Corn plants growing in fields infested with the northern or western corn rootworms exhibit poor growth and often die and the larger plants because of their weakened root system often fall down during or after a heavy rainfall or a strong wind. In addition these soil insects seriously affect the quality of the harvested crop, particularly corn.  
  In accordance with this invention it has been found that soil insect species of the genus Diabrotica are successfully combated by bringing into contact with the larval stage thereof, as for example, applying to the surface or sub-surface of the host soil such as cornfields, peanut fields, etc., an insecticidally effective amount of a phosphonodithioate of this invention.  
 To illustrate this invention is the following:  
  120 grams of unsterilized Ray silt-loam soil (St. Charles, Missouri) having a moisture content of l l percent by weight is placed in a shallow pan. A 0.01 percent by weight acetone solution of S-(p-tolyl) O-phenyl methylphosphonodithioate is prepared and 7.2 ml. thereof is pipetted into a Devilbiss atomizer, and sprayed evenly over said soil, the soil being worked during the spraying to provide an even distribution of the chemical in the soil, which provides a concentration of 6 ppm. of S-(tolyl) O-phenyl methylphosphonodithioate in the so treated soil. Thereupon to yellow liquid each of 8 No. 5175 plastic creamer cups is added 18 grams of the so treated soil. These so filled cups are then grouped in respective pairs (a), (b), (c) and (d).  
  To each cup of pair (a) is added an intimately mixed with the treated soil therein two freshly cut one inch long sections of the roots of healthy young corn plants (Zea mays), the length of the roots thereof being about 10 inches. Immediately thereafter, on the surface of the soil of each cup of pair (a) is placed five 10 day old western corn rootworm larvae, Diabrotica virgifera, and each cup capped with a plastic top pin-holed for aeration purposes. This pair (a) is then placed in a constant temperature humidity box (25C, relative humidity). At the same time respective cup pairs (b), (c) and (d) above described are capped and placed in the same humidity box.  
  Forty-eight hours immediately after placement in the humidity box pair (a) cups are removed, and the contents of each cup poured into separate 600 ml. glass beakers each containing 200 ml. of a saturated aqueous magnesium sulfate solution. The contents of each beaker is swirled about for about 5 minutes, and then the beaker is permitted to stand. The soil settles to the bottom of the beaker, while the larvae whether alive or dead rise to and float on the top surface. Thereupon the live larvae in each beaker are counted and averaged. In each beaker it was observed that of the five floating larvae there were no live larvae, all five were dead, in other words a percent kill in each instance.  
  Each cup of pair (b) above described is removed from the humidity box 3 weeks immediately after their initial placement therein as described above. To each cup of pair (b) is added and intimately mixed with the treated soil therein two freshly cut on inch long sections of the roots of healthy young corn plants (Zea mays), the length of the roots being about 10 inches. Immediately thereafter, on the surface of the soil of each cup of pair (b) is placed five 10 day old western corn rootworm larvae, Diabrotica virgifera, and each cup capped with a plastic top pin-holed for aeration purposes. This pair (b) is then placed back in the aforedescribed humidity box. Forty-eight hours immediately after this placement pair (b) cups are removed, and the contents of each cup is poured into separate 600 ml. glass beakers each containing 200 ml. of a saturated aqueous magnesium sulfate solution. The contents of each beaker is swirled about for 5 minutes and then contents of each cup is poured into separate 600 ml. 5 permitted to stand. The soil settles to the bottom of the glass beakers each containing 200 ml. of a saturated beaker, while the larvae whether dead or alive rise to aqueous magnesium sulfate solution. The Contents of and float on the top surface. Thereupon the live larvae each beaker is swirled about for 5 minutes, and then are counted d averaged I one b k i was bpermitted to stand. The soil settles to the bottom of the Served that f the fi fl i larvae, there was one beaker, while the larvae whether dead or alive rise to li (or 80% i while in the other beaker it was and float Oh the p surface- Thereupon the live larvae served that of the five floating larvae two were alive (or in each beaker are counted and averaged. In each bea- 60% km which averages a 70 percent m ker it was observed that of the five floating larvae there Along i the abovehescrihed evaluations f 48 were no live larvae, all five were dead, in other words hours 3 4 and 8 weeks Control pairs were also run that a 100 Percent kill in each ihstahceis everything was exactly the same except that the soil Each cup of pair (0) above described is removed Was not treated with -(plyl) -ph nyl m hylphosfrom the humidity box above described 4 weeks immephonodithioate. In all of these instances no kills of the diately after their initial placement therein as described ar a r dabove. To each cup of pair (c) is added and intimately AS iS vid nt S-(p-tolyU -p y m hylph mixed with the treated soil therein two freshly cut one phonodithioate is characterized by excellent soil stabilinch long sections of the roots of healthy young corn ity, that is its longevity in soil is sufficiently great to lant (Z the length f the root bei about cope with corn rootworm infestations occurring in the 10 inches. Immediately thereafter, on the surface of the soil at periods substantially later than its initial applicasoil of each cup of pair (0) is placed five 10 day old tion to the soil. western corn rootworm larvae, Diabrotica virgifera, and Following the above test procedure the insecticidal each cup capped with a plastic top pin-holed for aeraeffectiveness of other compounds of this invention is tion purposes. This pair (c) is then placed back in the shown by the results summarized in Table 1.  
 TABLE 1 Percent kill after weeks in test Example Compound Formula 0 2 4 6 8 l0 12 (a) S-(p-tolyl) O-phcnyl 10 percent by weight on I00 I00 80 I00 90 8O ethylphosphonodithioatc uttapulgite granules (b) S-(m-tolyl) O-phenyl 10 percent by weight on I00 90 100 90 100 80 ethylphosphonodithioatc attapulgitc granules (c) S,O-diphenyl ethyl- 0.0l percent by weight 100 80 90 8O 60 phosphonodithioate in acetone indicates no test.  
 aforedescribed humidity box. Forty-eight hours imme- The results in Table 1 indicate that the soil stability diately after this placement pair (0) cups are removed, of the designated compounds is also excellent. The and the contents of each cup is poured into separate compounds of Examples (a) and (b) have superior soil 600 ml. glass beakers each containing 200 ml. of a satustability and are particularly effective even after long rated aqueous magnesium sulfate solution. The conperiods of time. tents of each beaker is swirled about for 5 minutes and Insecticidal effectiveness against corn rootworm inthen permitted to stand. The soil settles to the bottom festations upon initial application at the rate of 10 ppm of the beaker, while the larvae whether dead or alive to the soil is observed for S-(m-tolyl) O-phenyl rise to and float on the top surface. Thereupon the live methylphosphonodithioate and S-(o-tolyl) O-phenyl larvae in each beaker are counted and averaged. In 0 th l ho honodithioate which give an 80 percent each beaker it was observed that of the five floating larkill and for s-(o-tolyl) O-phenyl ethylphosphonodithiovae, there was no live larvae, all five were dead, in ate, S-(2,4-xylyl) O-phenyl ethylphosphonodithioate, other words a 100 percent kill in each instance. S-(p-tertiary butyl phenyl) O-phenyl ethylphos- Each cup of pair ((1) above described is removed phonodithioate, and S-(2,4-xylyl) O-phenyl from the humidity box above described 8 weeks immediately after their initial placement therein as described above. To each cup of pair (d) is added and intimately mixed with the treated soil therein two freshly cut one inch long sections of roots of healthy young corn plants (Zea mays), the length of the roots being about 10 inches. Immediately thereafter on the surface of the soil of each cup of pair (d) is placed five 10 day old western corn rootworm larvae, Diabrotica virgzfera, and each cup capped with plastic top pin-holed for aeration purposes. This pair (d) is then placed back in the aforedescribed humidity box. Forty-eight hours immediately after this placement pair (d) cups are removed, and the methylphosphonodithioate which give a percent kill.  
  Although a compound of this invention is useful per se in destroying species of Diabrotica larvae, it is preferable that it be supplied to the larvae or to the environment of the larvae in a dispersed form in a suitable extending agent. The exact concentration of an insecticidal compound employed in destroying said larvae can vary considerably provided the required dosage (i.e. toxic or insecticidal amount) thereof is supplied to the larvae or to the environment of the larvae. When the extending agent is a liquid or mixture of liquids (e.g. as in solutions, suspensions, emulsions, or aerosols) the concentration of the insecticidal compound employed to supply the desired dosage generally will be in the range of 0.001 to 50 percent by weight. When the extending agent is semi-solid or solid, the concentration of the insecticidal compound employed to supply the desired dosage generally will be in the range of 0.1 to 75 percent by weight. From a practical point of view, the manufacturer must supply the user with a low cost concentrate or spray base or particulate solid base in such form that, by merely mixing with water or finely divided inert solid extender (e.g. powdered clay or talc) or other low cost material available to the user at the point of use, he will have an easily prepared insecticidal spray or particulate solid. In such a concentrate composition, the insecticidal compound generally will be present in a concentration of to 95 percent by weight, the residue being any one or more of the wellknown insecticidal adjuvants, such as the surfaceactive clays, solvents, diluents, carrier media, adhesives, spreading agents, humectants, and the like, but particularly a finely-divided soild extender.  
  There are a large number of organic liquids which can be used for the preparation of solutions, suspensions or emulsions of the insecticidal compounds of this invention. For example, isopropyl ether, acetone, methyl ethyl ketone, octanone, dioxane, cyclohexanone, carbon tetrachloride, ethylene dichloride, tetrachloroethane, hexane, heptane and like higher liquid alkanes, hydrogenated naphthalenes, solvent naphtha, benzene, toluene, xylene, petroleum fractions (e.g. those boiling almost entirely under 400F, and having a flash point above about 80F, particularly kerosene), mineral oils having an unsulfonatable residue above about 80 percent and preferably above 90 percent. In those instances wherein there may be concern about the phytotoxicity of the organic liquid extending agent a portion of same can be replaced by such low molecular weight aliphatic hydrocarbons as dipentene, diisobytylene, propylene trimer, and the like or suitable polar organic liquids such as the aliphatic ethers and the aliphatic ketones containing not more than about 10 carbon atoms as examplified by acetone, methyl ethyl ketone, diisobutyl ketone, dioxane, isopropyl ether, and the like. In certain instances, it is advantageous to employ a mixture of organic liquids as the extending agent, e.g. an aromatic hydrocarbon and an aliphatic ketone.  
  When an insecticidal compound of this invention is to be supplied to the larvae or to the environment of the larvae as aerosols, it is convenient to dissolve it in a suitable solvent and disperse the resulting solution in dichlorodifluoromethene or like chlorofluoroalkane which boils below room temperature at atmospheric pressure.  
  The insecticidal compounds of this invention are preferably supplied to the larvae or to the environment of the larvae in the form of emulsions or suspensions. Emulsions or suspensions are prepared by dispersing the insecticidal compounds of this invention either per se or in the form of an organic solution thereof in water with the aid of a water-soluble nonionic or anionic surfactant or mixtures thereof. The term surfactant as employed here and in the appended claims is used as in Volume II of Schwartz, Perry and Berchs Surface Active Agents and Detergents&#34; (1958, Interscience Publishers, Inc., New York) in place of the expression emulsifying agent, to connote generically the various emulsifying agents, dispersing agents, wetting agents and spreading agents that are adapted to be admixed with the active compounds of this invention in order to secure better wetting and spreading of the active ingredients in the water vehicle or carrier in which they are insoluble through lowering the surface tension of the water (see also Frear Chemistry of Insecticides, Fungicides and Herbicides, second edition, page 280). The surfactants contemplated are the wellknown capillary active substances which are non-ionic or anionic and which are described in detail in Volumes I and II of Schwartz, Perry and Berchs Surface Active Agents and Detergents, (1958, Interscience Publishers, Inc., New York) and also in the November 1947 issue of Chemical Industries (pages 81 1-824) in an article entitled Synthetic Detergents by John W. McCutcheon and also in the July, August, September and October, 1952 issues of Soap and Sanitary Chemicals under the title Synthetic Detergents. The disclosures of these articles with respect to non-ionizing capillary active substances are incorporated in this specification by reference in order to avoid unecessary enlargement of this specification. The preferred surfactants are the water soluble anionic and nonionic surface active agents set forth in US. Pat. No. 2,846,398 (issued Aug. 5, 1958).  
  The insecticidal compounds of this invention can be dispersed by suitable methods (e.g. tumbling or grinding) in solid extending agents either of organic or inorganic nature and supplied to the larvae environment in particulate form. Such solid materials include for example, tricalcium phosphate, calcium carbonate, kaolin, bole, kieselguhr, talc, bentonite, fullers earth, pyrophillite, diatomaceous earth, calcined magnesia, volcanic ash, sulfur and the like inorganic solid materials, and include for example, such materials of organic nature as powdered cork, powdered wood, and powdered walnut shells. The preferred solid carriers are the adsorbent clays, e.g. bentonite. These mixtures can be used for insecticidal purposes in the dry form, or by addition of water-soluble anionic or non-ionic surfactants the dry particulate solids can be rendered wettable by water so as to obtain stable aqueous dispersions or suspensions suitable for use as sprays.  
  For special purposes the insecticidal compounds of this invention can be dispersed in a semi-solid extending agent such as petrolatum with or without the aid of solubility promoters and/or surfactants.  
  In all of the forms described above the dispersions can be provided ready for use in combating the larvae or they can be provided in a concentrated form suitable for mixing with or dispersing in other extending agents. As illustrative of a particularly useful concentrate is an intimate mixture of S(p-tolyl) O-phenyl methylphosphonodithioate with a water-soluble anionic or nonionic surfactant or mixtures thereof which lowers the surface tension of water in the weight proportions of 0.1 to 15 parts of surfactant with sufficient of the insecticidal compound of this invention to make parts by weight. Such a concentrate is particularly adapted to be made into a spray for combating various forms of the aforedescribed larvae by the addition of water thereto. As illustrative of such a concentrate is an intimate mixture of 20 parts by weight of S-(p-tolyl) O- phenyl methylphosphonodithioate and from 2 to about 4 parts by weight of a water-soluble non-ionic surfactant such as the polyoxyethylene derivatives of C alkyl substituted phenols such as nonylphenol or dodecylphenol.  
  Another useful concentrate adapted to be made into a spray for combating the aforedescribed larvae is a solution (preferably as concentrated as possible) of the insecticidal compound of this invention in an organic solvent therefor. The said liquid concentrate preferably contains dissolved therein a minor amount (e.g. 0.5 to percent by weight of the weight of the new insecticidal agent) of non-ionic or anionic surfactant, which surfactant is also water-soluble. As illustrative of such a concentrate is a solution of S-(p-tolyl) O-phenyl methylphosphonodithioate in a mixture of xylene and 2-octanone which solution contains dissolved therein a water-soluble non-ionic surfactant such as the polyoxyethylene derivatives of C alkyl substituted phenols such as nonylphenol and dodecylphenol.  
  The insecticidal compounds of this invention can also be advantageously employed in combination with other pesticides, including, for example, nematocides, bactericides, fungicides, and herbicides. In this manner it is possible to obtain mixtures which are effective against a wide variety of pests and other forms of noxious life.  
  in the destruction of the aforedescribed larvae the insecticidal compounds of this invention either per se or compositions comprising same are supplied to the larvae or to their environment in a toxic or insecticidal amount. This can be done by dispersing the new insecticidal agents per se or compositions comprising same in, on or over an infested environment or in, on or over an environment the larvae frequent, e.g. agricultural soil or other growth media or other media attractable to the larvae for habitational or sustenance purposes, in any conventional fashion which permits the larvae to be subject to the insecticidal action of the insecticidal compound of this invention. Such dispersing can be carried out by simply mixing the new insecticidal agent per se or insecticidal spray or particulate solid compositions comprising same with the infested environment or with the environment the larvae frequent, or by employing a liquid carrier for the new insecticidal agent to accomplish sub-surface penetration and impregnation therein.  
 What is claimed is:  
  l. A method of destroying soil insects of the genus Diabrotica which comprises contacting the larval stage thereof with an insecticidally effective amount of an S- aryl O-phenyl alkylphosphonodithioate of the formula wherein R is methyl or tertiary butyl, n is an integer from 0 to 2, and R is lower alkyl provided that when R is tertiary butyl, R is ethyl.  
  2. The method of claim 1 wherein n is 2 and R is methyl.  
  3. The method of claim 1 wherein n is l and R is methyl.  
  4. The method of claim 3 wherein the alkylphosphonodithioate is S-(p-tolyl) O-phenyl methylphosphonodithioate.  
  5. The method of claim 3 wherein the alkylphosphonodithioate is S-(p-tolyl) O-phenyl ethylphosphonodithioate.  
  6. The method of claim 3 wherein the alkylphosphonodithioate is S-(m-tolyl) O-phenyl ethylphosphonodithioate.  
  7. A method of destroying soil insects of the genus Diabrotica which comprises applying to the host soil thereof an insecticidally effective amount of an S-aryl O-phenyl alkylphosphonodithioate of the formula X? S O 42 wherein R is methyl or tertiary butyl, n is an integer from O to 2, and R is lower alkyl provided that when R is tertiary butyl, R is ethyl.  
  8. The method of claim 7 wherein n is 2 and R is methyl.  
  9. The method of claim 7 wherein n is l and R is methyl.  
  10. The method of claim 9 wherein the alkylphosphonodithioate is S-(p-tolyl) O-phenyl methylphosphonodithioate.  
  11. The method of claim 9 wherein the alkylphosphonodithioate is S-(p-tolyl) O-phenyl ethylphosphonodithioate.  
  12. The method of claim 9 wherein the alkylphosphonodithioate is S-(m-tolyl) O-phenyl ethylphosphonodithioate.  
  13. The method of claim 10 wherein the soil insects are infesting corn fields.  
  14. The method of claim 13 wherein the species of Diabrotica is the western corn rootworm, D. virgifera.  
  15. An insecticidal concentrate comprising an S-aryl O-phenyl alkylphosphonodithioate of the formula wherein R is methyl or tertiary butyl, n is an integer from 0 to 2, and R is lower alkyl provided that when R is tertiary butyl, R is ethyl and an insecticidal adjuvant, the said concentrate containing from 5 to percent by weight of said phosphonodithioate.  
  16. The concentrate of claim 15 wherein n is 2 and R is methyl.  
 17. The concentrate of claim 15 wherein n is l and alkylphosphonodithioate ethylphosphonodithioate.  
 is S-(m-tolyl) O-phenyl.