ARTHROPODICIDAL NITROETHYLENES AND NITROGUANIDINES

Abstract: Arthropods are controlled in agronomic and nonagronomic environments by contacting them or their environment with an effective amount of a compound of formula (I), wherein R<1> to R<4>, X, A, and Z are as defined in the text, including arthropodicidal compositions containing said compound(s).

Description: HE E ARTHROPODICIDAL NITROETHYLENES AND NTTROGUANIDINES BACKGROUND OF THE INVENTION Fiel of the Invention This invention concerns nitroethylene and nitroguanidine compositions and a method for using the nitroethylene and nitroguanidine compounds of Formula I to control arthropods in agronomic and nonagronomic environments. State of the Art Insecticidal nitroethylene compounds are disclosed in EPA 302,389 and EPA 302,833. Insecticidal alkylenediamines are disclosed in U.S. 4,025,529 and U.S. 4,806,553. Heterocyclic alkylenediamine insecticides are disclosed in EPA 254,859. Insecticidal l-nitro-2,2-diaminoethylenes are disclosed in AU 88/20510. U.K. 1,483,633 discloses 2- (nitromethylene)-l,3-diazocycloalkanes as insecticides. SUMMARY OF THE INVENTION The invention pertains to use of compounds of Formula I, including all geometric and stereoisomers, agriculturally suitable salts thereof, and agricultural compositions containing them, for the control of planthoppers and leafhoppers. The compounds are: I wherein: Z is selected from the group CHNO2 and NNO2; X is selected from S(0) n ; A is selected from the group C1-C4 alkylene optionally substituted with C1-C3 alkyl, C2-C3 alkoxycarbonyl, halogen and CN; 5 R! is selected from the group C1-C4 alkyl, C1-C4 haloalkyl, C3-Cg cycloalkyl and C4-C6 cycloalkylalkyl; nis 0, l or 2; R2 and R^ are independently selected from the group H, CH2CN, C1-C4 alkyl, CHO, C2-C4 alkylcarbonyl, C2-C3 10 alkoxycarbonyl C2-C4 alkoxyalkyl, C3-C6 dialkoxyalkyl, C1-C3 alkoxy, C1-C3 alkylsulfonyl, C3-C4 alkenyl, C3-C4 alkynyl, C1-C4 alkylamino, C2-C4 dialkylamino and benzyl substituted with R^; 4 is selected from the group C1-C4 alkyl, C1-C4 haloalkyl, * ■ ** C3-C6 cycloalkyl and C4-C6 cycloalkylalkyl; or R2 and R^ can be taken together as C2-C3 alkylene or C2-C3 alkenylene each optionally substituted with 1-4 C1-C2 alkyl; and R5 i s selected from the group halogen, C1-C2 alkyl, C1-C2 20 haloalkyl, C1.C2 alkoxy, C1-C2 thioalkyl, C1-C2 halothioalkyl, C1-C2 haloalkoxy, NO2 and CN. Preferred Method A for controlling plant and leaf hoppers 9 _ comprises use of compounds of Formula I wherein Z is CENO2. Preferred Method B employs compounds of Formula I wherein Z is NNO2. Preferred Method C employs compounds A wherein: Ais CH 2 CH ; ! is selected from the group C1-C4 alkyl; 30 ^ and R^ are independently selected from the group H, C1-C4 alkyl, C2-C3 alkoxycarbonyl and C2-C4 alkylcarbonyl; and R4 is selected from the group C1-C4 alkyl. 35 Preferred Method D employs compounds A wherein: R2 and R^ are taken together and independently selected from the group C2-C3 alkylene and C2-C3 alkenylene, each optionally substituted by 1-4 C1-C4 alkyl. Preferred Method E employs compounds C wherein X is S. Preferred Method F employs compounds D wherein X is S. This invention also concerns novel arthropodicidal compositions comprising an effective amount of a compound of Formula I and a carrier therefor which is effective to deliver the compound to agronomic and nonagronomic arthropods, particularly planthoppers and leafhoppers, and their environment so that said arthropods are controlled. In the above definitions, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl", denotes straight chain or branched alkyl such as methyl, ethyl, a-propyl, isopropyl or the different butyl isomers. Alkoxy denotes methoxy, ethoxy, a-propyloxy and isopropyloxy. Alkenyl denotes straight chain or branched alkenes such as vinyl, 1-propenyl, 2-propenyl, 3-propenyl and the different butenyl isomers. Alkynyl denotes straight or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl isomers. Alkylthio denotes methylthio, ethylthio and the different propylthio and butylthio isomers. Alkylsulfonyl and alkylamino are defined analogously to the above examples. Cycloalkyl denotes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term "halogen", either alone or in compound words as "haloalkyl", denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl" said alkyl can be partially or fully substituted with halogen atoms, which can be the same or different. Examples of haloalkyl include CH2CHF2, CF2CF3 and CH2CHFCI. The total number of carbon atoms in a substituent group is indicated by the "Ci-Cj" prefix where i and j are numbers from 1 to 6. For example, C1-C3 alkylsufonyl designates methylsulfonyl through propylsulfonyl; C2 alkoxy designates OCH2CH3 and C3 alkoxy designates OCH2CH2CH3 and OCH(CH3>2; C2 alkylcarbonyl designates C(0)CH3 and C4 alkylcarbonyl designates C(0)CH2CH2CH3 and C(0)CH(CH3)2; C3 alkoxyalkyl designates CH2OCH2CH3 and CH2CH2OCH3; C4 alkoxyalkyl designates CH2OCH2CH2CH3, CH2CH2OCH2CH3 and CH2θCH(CH3)2; and as a final example, C4 dialkoxyalkyl designates CH2OCH2CH2OCH3. DETAILS OF THE INVENTION The compounds of Formula I can be prepared by the reaction of nitroethenes and nitroimines of Formula IE with an amine of Formula HI (Scheme 1). Alternatively, compounds of Formula I can be prepared by the reaction of nitroethenes and nitroimines of Formula IV with amines of Formula V (Scheme 2) using procedures which are analogous to those used for reactions of compounds of Formula H with compounds of Formula HI; therefore, for brevity only reactions of compounds of Formula IE with compounds of Formula IH are described. Typical conditions involve combination of II with a stoichiometric excess of HI in a suitable solvent or combination of solvents at temperatures generally in the range of about 0 to 100°C. Suitable solvents typically have sufficient polarity to effect solution of the Formula IE compound and the Formula UI amine and include, but are not limited to, alcohols such as methanol, ethanol and isopropanol; ethers such as diethyl ether, tetrahydrofuran and dioxane; esters such as ethyl acetate; water; and polar and aprotic solvents such as dimethylformamide and dimethylacetamide. Amine m can also be used as its hydrochloride salt and in these cases an equivalent amount of a base (such as potassium hydroxide) is added to the reaction mixture. SCHEME 1 wherein: A, X, Z, Rl, R2, R3, and R^ are as previously defined. {SCHEME 2 IV wherein: A, X, Z, Rl, R2, R3, and R^ are as previously defined. Compounds of Formula I include both geometrical and optical isomers as well as Z and isomers around the nitroethene or imine double bond. These isomers may vary in their biological activity. In some instances, it may be desirable to obtain compounds which are geometrically and/or optically pure or which are enriched in one or more of the possible isomers. All such isomers are included within the scope of the invention. They, as well as all salts, are included within the term "compound(s)". For the sake of simplifying the description of this invention, the generic formula (Formula I) encompasses certain compounds that may have long term stability problems and/or are difficult to prepare. For example, haloalkylamines when R^ is Cj to C4 haloalkyl are unstable when the halo substituent is directly adjacent to nitrogen. These generally decompose to the corresponding hydrogen halides and imine. Similarly, Formula I compounds where A is a Cj haloalkyl would be expected to be hydrolytically unstable. These compounds, however, are relatively few; their identity would be obvious to one skilled in the art, and their excision from the scope would unduly compUcate and lengthen the description of the invention. Compounds of Formula II where Z is CHNO2 can be prepared using processes known in the art involving reaction of nitroethene VI with an amine of Formula V (Scheme 3). Compounds of Formula IV where Z is CHNO2 can be prepared by procedures which are analogous to those for compounds of Formula II; therefore, for brevity, only the compounds of Formula II are described. Typical conditions involve the combination of equimolar amounts of V and VI in a suitable solvent or solvent mixture at temperatures in the range of about 0 to 100°C. Suitable solvents typically have sufficient polarity to effect solution of V and VI and include, but are not limited to, alcohols such as methanol, ethanol and isopropanol; ethers such as diethyl ether, tetrahydroniran and dioxane; esters such as ethyl acetate; polar aprotic solvents such as dimethylformamide and dimethylacetamide; water as well as mixtures of solvents. SCHEME ? VI Amines of Formula V can be prepared by reaction of an alkylating agent of Formula VII with an amine of Formula m (Scheme 4). Typical conditions involve combination of VH with a stoichiometric excess of VΩI in a suitable solvent or combination of solvents at temperatures in the range of about 0 to 100°C. Suitable solvents or solvent mixtures typically have sufficient polarity to effect solution of the Formula " VTH amine and the Formula V product and include, but are not limited to, alcohols such as methanol, ethanol and isopropanol; ethers such as tetrahydrofuran and dioxane; water and acetonitrile. Amine VIH can also be used as its hydrochloride salt and in these cases an equivalent amount of a base (such as potassium hydroxide) is added to the reaction mixture. SCHEME 4 5 H-XAY + R 2 NH 2 ► v vii vπi wherein: I Q Y is a leaving group; and A, X, R1 and R^ are as previously defined. Compounds of Formula I where R^ and R^ are taken together as an optionally substituted C2-C3 alkylene or C2-C3 alkenylene group can 25 be prepared using the analogous procedures illustrated by Schemes 5 and 6. SCHEME 5 rx 25 SCH M D z 30 __ wherein: 00 B is C2-C3 alkylene or C2-C3 alkenylene each optionally substituted with 1-4 C1-C2 alkyl; Y is a leaving group; and A, X, Ri, R3, and Z are as previously defined. Reactions such as those shown in Scheme 5 are typically carried out by treatment of a solution of Formula IX and VΩ compounds in a suitable solvent with a proton acceptor such as, but not limited to, sodium hydride at a temperature of about 0 to 100°C. Suitable solvents include, but are not limited to, dimethylformamide and THF. Completely analogous procedures can be used to effect the reactions illustrated by Scheme 6, and, for the sake of brevity, will not be discussed further. Scheme 7 illustrates the formation of Formula IX compounds. Procedures for this transformation are analogous to those previously described for Scheme 5. SCHEME 7 A Proton HN NH + X ► IX f 1 Acceptor -B- XI wherein: B and Z are as previously defined. When B is equal to C2 alkenylene and Z is equal to NNO2, Formula XL compounds may exist as the amino-imidazole tautomer, XII. Scheme 8 illustrates the formation of Formula IX nitroguanidines using the precursors of Formula XU. Scheme 9 illustrates the formation of Formula I compounds where Z is NO2 and B is an optionally substituted C2 alkenylene using the precursors of Formula XII. The procedures illustrated by Schemes 8 and 9 are completely analogous to those described previously for Scheme 5. n optionally ituted C 2 alkenylene XII and Z is NNO 2 ) wherein: R 6 and R 7 are H, or C1-C2 alkyl. SCHEME 9 Proton XII + VII Acceptor (B is an optionally substituted C 2 alkenylene and Z is NNO 2 ) Formula XII nitroaminoimidazoles can be formed by the reaction of S-methyl-N-nitro-isothiourea with amino-acetals of Formula 2.111. Typical reaction conditions involve the treatment of a mixture of XIU and S-methyl-N-nitroisothiourea in a suitable solvent with 0 to 5 equivalents of an acid catalyst such as hydrochloric acid at a temperature of 0°C to the reflux temperature of the solvent. Typical solvents include, but are not limited to, methanol, ethanol and isopropanol. Scheme 10 illustrates this transformation. SCHEME 10 XIII Q wherein: R° is an alkyl or aryl group; and R and R are as previously defined. One skilled in the art will recognize Formula XIIL compounds as acetals of α-amino aldehydes and α-amino-ketones, whose syntheses are well precedented. Compounds of Formula XE where B is an optionally substituted C2-C3 alkylene and Z is CHNO2 can be prepared by the reactions of diamines of Formula XIV with V in a suitable solvent at temperatures in the range of about 0 to 100°C. Suitable solvents include, but are not limited to, alcohols such as methanol, ethanol and isopropanol, and water, as well as other polar solvents. Typical reactions involve the use of equimolar amounts of V and XEV. Scheme 11 illustrates this transformation. XIV C 2 -C 3 alkylene and Z is CHNO 2 Compounds of Formula XI where B is an optionally substituted C2-C3 alkylene and Z is NNO2 can be prepared by the reactions of Formula XEV diamines with nitroguanidine using procedures completely analogous to those described for Scheme 11 and, for the sake of brevity, will not be discussed further. Formula XEV compounds are 1,2- and 1,3-diamines whose preparations are known in the art. Compounds of Formula II where Z is NO2 can be prepared by the reaction of N-nitroimines of Formula XV with an alkylating agent of Formula VII in a suitable solvent in the presence of a proton acceptor (Scheme 12). Typical proton acceptors are metal hydrides such as sodium hydride, metal alkoxides such as sodium methoxide or potassium t- butoxide and carbonates such as cesium carbonate. Suitable solvents for reactions using metal hydride include DMF and THF. Suitable solvents for reactions using metal alkoxides include alcohols such as methanol, ethanol and t-butanol and THF. Suitable solvents for reactions using carbonate bases include methanol, ethanol and acetonitrile. The reactions are typically run at temperatures that range from 0 to 100°C. Typical reactions involve the use of equimolar amounts of VH and XV. SCHEME 12 ft- N0 2 Proton 2 A + ™ A — → H ^NH SMe "Pf (Z is NNθ2) XV wherein: R2 is as previously defined. Compounds of Formula IV where Z is NNO2 can be prepared by the reaction of N-nitroimines of Formula XVI with an alkylating agent of Formula XVII (Scheme 13) using procedures that are analogous to those described for Scheme 12. Compounds of Formula XV can be prepared by the reaction of an alkylating agent of Formula XVHE with S-methyl-N-nitroisothiourea (Scheme 14) using procedures that are analogous to those described for Scheme 12. Compounds of Formula XVI can be prepared by the reaction of an alkylating agent of Formula X with S-methyl-N-nitroisothiourea (Scheme 15) using procedures that are analogous to those described for Scheme 12. SCHEME 13 XVI XVII SCHEME 14 XVIII SCHEME 15 wherein: R2, R3 f R4 and Y are as previously defined. Compounds of Formula I where X is SO can be obtained by reaction of the corresponding compound of Formula I where X is S with a variety of oxidants including, but not limited to, peracids, periodates and hydroperoxides in a suitable solvent. Compounds of Formula I where X is SO2 can be obtained using analogous reaction conditions wherein the amount of oxidant used is greater than or equal to two oxidizing equivalents. The following Examples further illustrate the invention. EXAMPLE 1 Step A: N-Metbyl'3^mefaylttoo)et-hfrøflτηiτι* Solid 85% potassium hydroxide (54 g, 0.81 moles) was added in portions to a solution of methylamine hydrochloride (50 g, 0.74 moles) and water (200 mL), maintaining the temperature below 30°C. The resulting solution was treated with a solution of 2-chloroethyl methyl sulfide (15 mL, 0.15 moles) and ethanol (50 mL) at room temperature. After 1 hour, the temperature of the initially two-phase reaction had risen to about 40°C and the reaction became homogeneous. After stirring for 10 hours at room temperature, the reaction was saturated with solid sodium chloride and the aqueous layer was extracted with ether (3 x 100 mL). The combined organic layers were washed with brine made basic with potassium hydroxide, dried over potassium carbonate and concentrated under vacuum to yield 11.1 g (70%) of a clear oil that was used without further purification. iH NMR (200 MHZ, CDC1 3 ) δ: 2.80 (t, 2H), 2.65 (t, 2H), 2.46 (s, 3H), 2.11 (s, 3H), 1.5 (br s, IH). step B: Methyl N'm?thyl-N-r2-( gthylthio)ethyn-2-MtrQ- et.hanimidothioate A solution of the amine from Step A (1.0 g, 9.5 mmoles), 1,1- bis(methylthio)-2-nitroethylene (1.9 g, 11.4 mmoles) and ethanol (34 mL) was heated at reflux for 5 hours and then cooled to room temperature. The resulting mixture was dissolved in acetone, silica gel (5 g) was added and the solvent was removed under vacuum. The residue was chromatographed on silica gel eluting with 1:1 hexanes-ethyl acetate to give 0.76 g (30%) of a yellow oil. iH NMR (200 MHz, CDCI3) δ: 6.72 (s, IH), 3.78 (t, 2H), 3.15 (s, 3H), 2.75 (t, 2H), 2.49 (s, 3H), 2.16 (s, 3H). Step C: N.N'-Dimethyl-N-r2-(methylthio)ethvn-2-mtro-l.l- fit ' hftne<tiλτniτ)e Aqueous sodium hydroxide (50%, 0.5 mL, 9.0 mmoles) was added to a solution of the product of Step B (0.4 g, 1.8 mmoles), methylamine hydrochloride (0.6 g, 9 mmoles), ethanol (5 mL), tetrahydrofuran (2 mL) and water (1 mL). The resulting solution was stirred for 20 hours at room temperature and then silica gel (2 g) was added and the solvent was removed. Flash chromatography of the residue on silica gel using 5% ethanol in methylene chloride gave 0.36 g (98%) of the title compound as a yellow oil. iH NMR (200 MHz, CDC1 3 ) δ: 9.8 (br s, IH), 6.56 (s, IH), 3.42 (t, 2H), 3.05 (d, 3H), 2.94 (s, 3H), 2.73 (t, 2H), 2.13 (s, 3H). Step A: 2-(Nitromethvlene)-iτm<fazolidiπe A solution of 4.0 mL (0.06 moles) of ethylene diamine, 10 g (O.Oβmoles) of 2,2 bis(methylthio)nitroethylene and 60 mL of ethanol was heated at reflux for 12h and then concentrated to give 7.6 g of a beige solid. iH NMR (200 MHz, DMSO-d 6 ) δ: 6.33 (s, IH), 3.58 (s, 4H). Step B: l-r2-(Methvlthio)ethvll-2-(nitroetbvlftτ.p τni fl7.n1itlinP The product from Step A (2.0 g, 0.016 moles) was added to a suspension of 60% sodium hydride (0.7 g, 0.017 moles) and 31 mL of DMF at room temperature. The resulting mixture was stirred for 10 min and then 1.5 mL (0.016 moles) of 2-chloroethyl methyl sulfide was added. Resulting mixture was heated at 100°C for 12 h and then cooled to room temperature. Ethanol, 20 ml, was added and the reaction was concentrated at 70°C. The residue was dissolved in 50 mL of EtOH; 5 g of silica gel was added, and the mixture was concentrated. The residue was chromatographed on 100 g silica gel eluting with CH2Cl2-EtOH-48% NH4OH (20:1:0.1) to give 1.0 g of a brown oil that solidified on standing. Trituration of the solid with MeOH gave a light yellow solid; mp = 102- 104°C. iH NMR (400 MHz, CDCI3) δ: 8.65 (br s, IH), 6.55 (s, IH), 3.78 (m, 4H), 3.38 (t, 2H), 2.70 (t, 2H), 2.16 (s, 3H). In Tables 1 through 33, the following notations have been used: allyl - CH 2 CH=CH 2 propargyl = CH2CsCH Me = -CH 3 Et = -CH2-CH3 n-Pr - -CH2-CH2-CH3 n-Bu -CH2-CH2-CH2-CH3 CH 3 t-Bu -CH 3 CH 3 6 E c-Pr -y ' c-Bu -0 c-pentyl c-hexyl XAS E-l E 1 E 3 E 4 E 1 E 3 E 4 TABLE2 E 1 E £ E 4 E 1 E 3 E 4 TΔB £L2 TABLE4 IΔBLELS E 1 E 3 E 4 E 3 E* E 4 IAELE_S TABLE 7 TABLES TABLE 9 TABLE 10 TABLE 11 TABLE 12 TABLE 13 TABLE 14 TABLE IB TABLE 16 XABLEIZ TABLE-IS TABLE 19 TAB ED TABLE 21 ΪΔBLEJ22 2ABLE22 TABLE ai XAELE& Δ E 1 E 2 E 3 E 4 Δ E 1 E 2 E 3 E 4 TABLE 25 TABLE 27 E 3 E 3 E 1 E 3 Me CH 2 CH 2 H Me (CH 2 ) 3 CHO Me CH 2 CH 2 Me Me (CH 2 ) 3 COMe Me CH 2 CH 2 Et Me ( CH 2 ) 3 CH 2 CN Me CH 2 CH 2 n-Pr Me (CH 2 ) 3 CH 2 NMe Me CH 2 CH 2 CHO Me (CH 2 ) 3 OMe Me CH 2 CH 2 COMe Me (CH 2 ) 3 allyl Me CH 2 CH 2 CH 2 CN Me (CH 2 ) 3 CH 2 CCH Me CH 2 CH 2 CH 2 NMe Me CH 2 CH 2 CH 2 CCH Me CH 2 CH 2 OMe Et (CH 2 ) 3 H Me CH 2 CH 2 S0 2 Me Et (CH 2 ) 3 Me Me CH 2 CH 2 allyl Et (CH 2 ) 3 Et Et CH 2 CH 2 H Et (CH 2 ) 3 CHO Et CH 2 CH 2 Me Et (CH 2 ) 3 CH 2 CN Et CH 2 CH 2 Et Et (CH 2 ) 3 CH 2 NMe 2 Et CH 2 CH 2 CHO n-Pr CH 2 CH 2 H Et CH 2 CH 2 CH 2 CN n-Pr CH 2 CH 2 Me Et CH 2 CH 2 CH 2 NMe 2 n-Pr CH 2 CH 2 CHO Me ( CH 2 ) 3 H n-Pr CH 2 CH 2 CH 2 CN Me (CH 2 ) 3 Me n-Pr CH 2 CH 2 CH 2 NMe 2 Me (CH 2 >3 Et c-Pr CH 2 CH 2 H Me ( CH 2 ) 3 n-Pr c-Pr CH 2 CH 2 CH 2 CN E 3 £ E 3 E 1 £ E 3 TABLE 28 E 3 £ E a E 1 £ E a E 3 £ E a E 3 £ E 3 TAEL£2a E 3 A E 3 E 1 a A E 3 TABLE 31 E 3 A E fi TABLE 32 E 1 A E 3 TABLE 33 E 3 A E a TABLE 34 E 1 A E a a Recrystallization from ethanol provided material identical to the compound melting at 131.5-133°C by !H and 13 C NMR but with a melting point of 115-116°C. CMPP E m&°Q 14 CH 2 CH 2 102-104 15 CH 2 CH 2 CH2 120-122 Formulation and Use The compounds of this invention will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent or an organic solvent. Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like. Many of these can be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain from less than about 1% to 99% by weight of active ingredient(s) and at least one of a) about 0.1% to 20% surfactant(s) and b) about 5% to 99% solid or liquid diluent(s). More specifically, they will contain effective amounts of these ingredients in the following approximate proportions: Percent bv Weight Active Ingredient Diluent ( s ) Surfftctant(g) Wettable Powders 25-90 0-74 1-10 Oil Suspensions, 5-50 40-95 0-15 Emulsions, Solutions, (including Emulsifiable Concentrates) Dusts 1-25 70-99 0-5 Granules, Baits 0.01-95 5-99 0-15 and Pellets High Strength 90-99 0-10 0-2 Compositions Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are some¬ times desirable, and are achieved by incorporation into the formulation or by tank mixing. Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, New Jersey. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide," 2nd Ed., Intersdence, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0°C. "McCutcheon's Detergents and Emulsifiers Annual", Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formula¬ tions can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc. Preferably, ingredients should be approved by the U.S. Environmental Protection Agency for the use intended. The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, U.S. 3,060,084). Granules and pellets can be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", f-h^fηiffll Engineering. December 4, 1967, pages 147 and following, and Terry's Chemical Engineer's Handbook", 4th Ed., McGraw-Hill, New York, 1963, pages 8 to 59 and following. Temple A Emulsifiable Concentrate N-methyl-N'-[2-(methylthio)ethyl]-2-nitro- 1,1-ethenediamine 20% blend of oil soluble sulfonates and polyoxyethylene ethers 10% isophorone 70% The ingredients are combined and stirred with gentle warming to speed solution. A fine screen filter is included in packaging operation to insure the absence of any extraneous undissolved material in the product. Example B Wettable Powder N-methyl-N'-[2-(methylthio)ethyl]-2-nitro- 1,1-ethenediamine 30% sodium alkylnaphthalenesulfonate 2% synthetic amorphous silica 3% kaolinite 63% The active ingredient is mixed with the inert materials in a blender. After grinding in a hammermill, the material is re-blended and sifted through a 50 mesh screen. Example C Dust Wettable powder of Example B 10% pyrophyllite (powder) 90% The wettable powder and the pyrophyllite diluent are thoroughly blended and then packaged. The product is suitable for use as a dust. Kxampte p Granule N-methyl-N'-[2-(methylthio)ethyl]-2-nitro- 1,1-ethenediamine 10% attapulgite granules (low volative matter, 0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90% The active ingredient is dissolved in a volatile solvent such as acetone and sprayed upon dedusted and pre-warmed attapulgite granules in a double cone blender. The acetone is then driven off by heating. The granules are then allowed to cool and are packaged. The ingredients are blended in a rotating mixer and water sprayed on to accomplish granulation. When most of the material has reached the desired range of 0.1 to 0.42 mm (U.S.S. No. 18 to 40 sieves), the granules are removed, dried, and screened. Oversize material is crushed to produce additional material in the desired range. These granules contain 4.5% active ingredient. E-ram lg V Solution N-methyl-N'-[2-(methylthio)ethyl]-2-nitro- 1,1-etnenediamine 25% N-methyl-pyrrolidone 75% The ingredients are combined and stirred to produce a solution suitable for direct, low volume application. Example G Aqueous Suspension N-methyl-N * -[2-(methylthio)ethyl]-2-nitro- 1,1-ethenediamine 2.0% Isopropyl phosphoric ester 0.2% White Carbon l.( Finely powdered talc 96.8% The ingredients are thoroughly blended and pulverized to make a driftless dust. The material can then be packaged. Ex mple fir Oil Suspengjop N-methyl-N'-[2-(methylthio)ethyl]-2-nitro- 1,1-ethenediamine 35.0% blend of poly alcohol carboxylic 6.0% esters and oil soluble petroleum sulfonates xylene range solvent 59.0% The ingredients are combined and ground together in a sand mill to produce particles substantially all below 5 microns. The product can be used directly, extended with oils, or emulsified in water. xλirpte I Bait Granules N-methyl-N'-[2-(methylthio)ethyl]-2-nitro- 1,1-ethenediamine 3.0% blend of polyethoxylated nonyl- 9.0% phenols and sodium dodecyl- benzene sulfonates ground up corn cobs 88.0% The active ingredient and surfactant blend are dissolved in a suitable solvent such as acetone and sprayed onto the ground corn cobs. The granules are then dried and packaged. Compounds of Formula I can also be mixed with one or more other insectiddes, fungicides, nematoddes, bactericides, acariddes, or other biologically active compounds to form a multi-component pestidde giving an even broader spectrum of effective agricultural protection. Examples of other agricultural protectants with which compounds of this invention can be formulated are: Insectiddes: 3-hydroxy-N-methylcrotonamide(dimethylphosphate)ester (monocrotophos) methylcarbamic add, ester with 2,3-dihydro-2,2- dimethyl-7-benzofuranol (carbofuran) 0-[2,4,5-trichloro-a-(chlorometiιyl)benzyI]phosphoric add, O'jO'-dimethyl ester (tetxacUorvinphos) 2-mercaptosuccinic add, diethyl ester, S-ester with thionophosphoric add, dimethyl ester (malathion) phosphorothioic add, 0,0-dimethyl, O-p-nitrophenyl ester (methyl parathion) methylcarbamic add, ester with a-naphthol (carbaryl) methyl 0-(methylcarbamoyl)thiolacetohydroxamate (methomyl) N'-(4-chloro-fi-t»lyl)-N,N-diπιet^ylformamidine (chlordimeform) 0,0-dietiιyl-0-(2-isopropyl-4-metiιyl-6-pyriιmdylphos- phorothioate (diazinon) octachlorocamphene (toxaphene) 0-ethyl-O-p-nitrophenyl phenylphosphonothioate (EPN) (S)-a-cyano-m-pheno--ybenzyl-(lR,3R)-3-(2,2-dibromo- vinyl)-2,2-dimet-hylcyclopropanecarboxylate (deltamethrin) MeΛyl-I^^'-dimetihyl-N-Kmethylcarbamoy oxy]-!- thioox amimidate (oxamyl) cyano(3-phenoxyphenyl)-methyl-4-chloro-a-(l-methyl- ethyDbenzeneacetate (fenvalerate) (3-phenoxyphenyl)nιet-hyl(±)-sia^23ia-3-(2,2-dichloro ethenyl)-2,2-dimetiιylcyclopropanecarboxylate (perme- thrin) a-cyano-3-phenoxybenzyl 3-(2,2-dicMorovinyl)-2,2- dimethylcyclopropanecarboxylate (cypermet-hrin) 0-ethyl-S-(p.-chlorophenyl)ethylphosphonodithioate (profenofos) phosphorothiolothionic add, 0-ethyl-0-[4-(methylthio)-phenyl]-S-fl-propyl ester (sulprofos). Additional insectiddes are listed hereafter by their common names: triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fonophos, isofenphos, methidathion, metha mi diphos, monocrotphos, phosmet, phosphamidon, phosalone, pirimicarb, phorate, terbufos, trichlorfon, methoxychlor, bifenthrin, biphenate, cyfluthrin, fenpropathrin, fluvalinate, flucythrinate, tralomethrin, metal- dehyde and rotenone. Fungiddes: methyl 2-benzimidazolecarbamate (carbendazim) tetramethylthiuram disulfide (thiuram) n-dodecylguanidine acetate (dodine) manganese ethylenebisdit iocarbamate (maneb) 1 ,4-dichloro-2,5-dimethoxybenzene (chloroneb) methyl l-(butyIcarbamoyl)-2-benzimidazolecarbamate (benomyl) l-[2-(2 ,4-dichlorophenyl)-4-propyl-l ,3-dioxolan-2- ylmethyl]-lH-l,2,4-triazole (propiconazole) 2-cyano-N-ethylcarbamoyl-2-methoxyiminoacetamide (cymoxanil) l-(4-cMorophenoxy)-3,3-dimethyl-l-(lH-l,2,4-triazol-l- yl)-2-butanone (triadimefon) N-(tricUoromethylthio)tetrahydropht-halimide (captan) N-(tricMoromet_hylttoo)phthalunide (folpet) l-[[[bis(4-fluorophenyl)][methyl]silyl]methyl]-lH- 1,2,4-triazole. Nematoddes: S-methyl-l-(di-methylcarbamoyl)-N-(metJhylcarbamoyloxy)- thioformimidate S-methyl l-carbamoyl-N-(methylcarbamoyloxy)ti io- formimidate N-isopropylphosphoramidic add O-ethyl 0'-[4-(methylthio)-B_l-tolyl]diester (fenamiphos) Bagteriddeg: tribasic copper sulfate streptomycin sulfate Acariddes: senedoic add, ester with 2-sec-butyl-4.6-dinitro- phenol (binapacryl) 6-methyl-l,3-cit olo[4,5-β]quinoxalin-2-one (oxytiiioquinox) ethyl 4,4'-dichlorobenzilate (chlorobenzilate) 1 ,l-bis(p-chlorophenyl)-2 ,2 ,2-trichloroethanol (dicofol) bis(pentachloro-2 ,4-cyclopentadien-l-yl) (dienochlor) tricyclohexyltin hydroxide (cyhexatin) trans-5-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2-oxo- thiazolidine-3-carboxamide (hexythiazox) amitraz propargite fenbutatin-oxide Biological Bacillus tfouringiensis Avermectin B. Utility The compounds of this invention exhibit activity in agricultural and non-agricultural environments against a wide spectrum of foliar and soil-inhabiting arthropods which are pests of growing and stored agronomic crops, forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health. The compounds are particularly useful against planthoppers and leafhoppers. Those skilled in the art will recognize that not all compounds are equally effective against all pests but the compounds of this invention display activity against: Larvae of the order l^epidoptera including fall and beet armyworm and other Spodoptera spp., tobacco budworm, corn earworm and other Hehothis spp., European corn borer, navel orangeworm, stalk/stem borers and other pyralids, cabbage and soybean loopers and other loopers, codling moth, grape berry moth and other tortridds, black cutworm, spotted cutworm, other cutworms and other noctuids, diamondback moth, green cloverworm, velvetbean caterpillar, green cloverworm, pink bollworm, gypsy moth, and spruce budworm; Foliar feeding larvae and adults of the order Coleoptera including Colorado potato beetle, Mexican bean beetle, flea beetle, Japanese beetles, boll weevil, leaf beetles including rice beetle, and root-feeding insects such as the rice water and rice root weevils, Diabrotica spp., Japanese beetle, European chafer and other ol o teran grubs and wireworms; Adults and nymphs of the orders < ?P ^P tfirfl and Homoptera including brown planthopper, small brown planthopper, green leafhopper and other rice plant and leafhoppers, other leafhoppers (Cicadelϋdae) and planthoppers ( fi perfflTWlY Fttlgoroidea espedally Ci iidae. Delphaddae. flatidae, Fulgoridae. Issidas and Meenopϋdae). tarnished plant bugs (Miridae). stink bugs fPeatatomitifleX cinch, rice and other seed bugs (Lvgaeidae). squash bugs (Coreidae) r rice bugs (Alvdidae). red bugs and cotton stainers (Pyrrhocoridae). aphids (Aphididae). scales (Cocddae and Piagpididae), lace bugs (T ngidae). dcadas (Cicadidae). spittlebugs (Cercopidae). whiteflies (Aleurodidae). psyllids (Psvllidae). phylloxerans (Phvlloxeridae) and mealybugs (Pseudococddae): Adults and nymphs of the order Thripidae: Adults, larvae and eggs of the order acari (mites) including European red mite, two spotted spider mite, rust mites, McDaniel mite, and foliar feed mites; Adults and immatures of the order Orthoptera induding grasshoppers; Adults and immatures of the order Diptera including leafminers, midges, fruit flies (tephritidae). and soil maggots; Adults and immatures of the order ThYffflP p ter including onion thrips and other foliar feeding thrips; Insect pests of the order Hymenoptera including carpenter ants, bees, hornets and wasps; Insect pests of the order Diptera including house flies, stable flies, face flies, horn flies, blow flies, and other muscoid fly pests, horse flies, deer flies and other Bradivcera. mosquitoes, black flies, biting midges, sand flies, sdarids, and Insect pests of the order Orthoptera including cockroaches and crickets; Insect pests of the order Isoptera including the Eastern subterranean termite and other termites; Insect pests of the order Mfllln hn fl and Anoplura induding the head louse, body louse, chicken head louse and other sucking and chewing parasitic lice that attack man and animals; and Insect pests of the order Siphonoptera including the cat flea, dog flea and other fleas. A more preferred spectrum of activity for the compounds of this invention are foliar and soil-inhabiting arthropods which are pests of agronomic crops, as well as greenhouse, ornamental, nursery and fruit crops. The compounds of this invention display activity against economically important agronomic, greenhouse, ornamental, fruit and nursery crop pests. The specific spedes for which control is exemplified are: aster leafhopper ( Macrosteles faaάfrΩns), rice planthopper (Sogatodes ojSLSQla), black been aphid ( Aphis fahag), and southern corn rootworm (Diabrotica The pest control protection afforded by compounds of the present invention is not limited, however, to these spedes. A lication Arthropod pests are controlled by applying one or more of the Formula I compounds of this invention, in an effective amount, to the 5 locus of infestation, to the area to be protected, or directly on the pests to be controlled. Because of the diversity of habitat and behavior of these arthropod pest spedes, many different methods of application are employed. A preferred method of application is by spraying with equipment that directs the compoτmd to the environment of the pests, on 10 the foliage, in the soil or paddy, to the plant part that is infested or needs to be protected. Alternatively, granular formulations of these compounds can be applied to or incorporated into the soil, paddy or nursery box. Other methods of application can also be employed including direct and residual sprays. 15 The compounds of this invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds in a carrier that may include diluents and/or surfactants in a formulation compatible with agronomic and nonagronomic utility. Preferred methods of application involve spraying 20 a water dispersion, refined oil solution or dust containing the compound. The rate of application of the Formula I compounds required for effective control will depend on such factors and the species of arthropod to be controlled, the pest's life cycle, life stage, location, time of year, host crop, feeding and mating behavior, ambient moisture and temperature, 25 and the like. ■ In general, application rates of 0.55-0.055 kg of active ingredient per hectare are suffident to provide large-scale effective control of pests in agronomic ecosystems under normal circumstances. Application rates as low as about 0.1 mg/sq meter or less up to about 150 mg/sq meter or more can be employed on arthropods in a nonagronomic 30 environment such as the household or other building or nonagronomic locus. The following Examples demonstrate the control efficacy of compounds of Formula I on specific pests; See Table 1 for compound I descriptions. Compounds not listed with data were either not screened i 35 on that test spedes or produced less than 80% mortality when tested as described in Examples 3 and 4. EXAMPLE 3 Afrfer 1 fl hopper Test units were prepared from a series of 12 oz. (350 ml) cups, each containing oat (Avena satavia) seedlings in a 1-inch layer of sterilized soil. Solutions of test compounds were prepared in a 75 acetone:25 water solvent and applied to the seedlings with a hydraulic sprayer by passing three sets of cups on a conveyor belt, beneath a flat-fan nozzle calibrated to deliver 0.055 kg HA at 30 psi (207 kPa). Approximately 1 hour after treatment, a thin layer of sand was placed over the soil in each cup, the units capped and 10-20 adult aster leafhoppers (Macrosteles fascifrons) each aspirated into the cups. The units were held at 27°C, 50% RH and 14L:10D for 48 hours, after which time mortality readings were taken. The following table lists the activity of the compounds against aster leafhopper. EXAMPLE 4 Rice Planthopper The test procedure of Example 3 was repeated for efficacy against adults of the rice planthopper (Sogatodes orzicola) except four sets of cups containing rice (Orvza satavia) seedlings were treated. The sprayer was calibrated to deliver 0.055 kg HA. The results are tabulated below.

Claims: CLAIMS What is claimed is: 1. An arthropodiddal composition comprising, as active ingredient, a compound of the formula: in an amount effective to control planthoppers and leafhoppers, and a carrier therefor, wherein: Z is selected from the group CH O2 and NNO2; X is selected from S(0) n ; A. is selected from the group C1-C4 alkylene optionally substituted with C1-C3 alkyl, C2-C3 alkoxycarbonyl, halogen and CN; R! is selected from the group C1-C4 alkyl, C1-C4 haloalkyl, Co-Cβ cycloalkyl and C4-C6 cycloalkylalkyl; n is 0, 1 or 2; R and R 3 are independently selected from the group H, CH2CN, C1-C4 alkyl, CHO, C2-C4 alkylcarbonyl, C2-C3 alkoxycarbonyl C2-C4 alkoxyalkyl, C3-C6 dialkoxyalkyl, C1-C3 alkoxy, C1-C3 alkylsulfonyl, C3-C4 alkenyl, C3-C4 alkynyl, C1-C4 alkylamino, C2-C4 dialkylamino and benzyl substituted with R^; R 4 is selected from the group C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl and C4-C6 cycloalkylalkyl; or R2 and R4 can be taken together as C2-C3 alkylene or C2-C3 alkenylene each optionally substituted with 1-4 C1-C2 alkyl; and 5 R5 is selected from the group halogen, C1-C2 alkyl, C1-C2 haloalkyl, C1.C2 alkoxy, C1-C2 thioalkyl, C1-C2 halothioalkyl, C1-C2 haloalkoxy, NO2 and CN. 2. A composition according to Claim 1 wherein Z is CHNO2. 0 3. A composition according to Claim 1 wherein Z is NNO2. 4. A composition according to Claim 2 wherein: Ais CH 2 CH 2 ; ® Rl is selected from the group C1-C4 alkyl; R and R 3 are independently selected from the group H, C1-C4 alkyl, C2-C3 alkoxycarbonyl and C2-C4 alkylcarbonyl; and R4 js selected from the group C1-C4 alkyl. 0 5. A composition according to Claim 2 wherein R2 and R 4 are taken together and independently selected from the group C2-C3 alkylene and C2-C3 alkenylene, each optionally substituted by 1-4 C1-C4 alkyl. 5 6. A composition according to Claim 4 wherein X is S. 7. A composition according to Claim 5 wherein X is S. 0 8. A method for controlling planthoppers and leafhoppers which comprises applying to them or to their environment an effective amount of a compound of the formula: 5 5 wherein: > 10 Z is selected from the group CHNO2 and NNO2; X is selected from S(0) n ; A is selected from the group C1-C4 alkylene optionally substituted with C1-C3 alkyl, C2-C3 alkoxycarbonyl, halogen and CN; R! is selected from the group C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl and C4-C6 cycloalkylalkyl; n is 0, 1 or 2; R and R 3 are independently selected from the group H, CH2CN, C1-C4 alkyl, CHO, C2-C4 alkylcarbonyl, C2-C3 alkoxycarbonyl C2-C4 alkoxyalkyl, C3-Cg dialkoxyalkyl, C1-C3 alkoxy, C1-C3 alkylsulfonyl, C3-C4 alkenyl, C3-C4 alkynyl, C1-C4 alkylamino, C2-C4 dialkylamino and benzyl substituted with R^; e R 4 is selected from the group C1-C4 alkyl, C1-C4 haloalkyl, C3-Cρ cycloalkyl and C4-C5 cycloalkylalkyl; or R and R 4 can be taken together as C2-C3 alkylene or C2-C3 alkenylene each optionally substituted with 1-4 C1-C2 alkyl; and 30 R5 is selected from the group halogen; Cχ-C2 alkyl, Cχ-C2 haloalkyl, C1.C2 alkoxy, Cχ-C2 thioalkyl, C1-C2 halothioalkyl, C1-C2 haloalkosy, NO2 and CN. 9. A method according to Claim 8 wherein Z is CHNO2. 35 10. A method according to Claim 8 wherein Z is NN02- 11. A method according to Claim 9 wherein: Ais CH 2 CH 2 ; R1 is selected from the group C1-C4 alkyl; R2 and ^ are independently selected from the group H, C1-C4 alkyl, C2-C3 alkoxycarbonyl and C2-C4 alkylcarbonyl; and R i selected from the group C1-C4 alkyl. 12. A method according to Claim 9 wherein R and R 4 are taken together and independently selected from the group C2-C3 alkylene and C2-C3 alkenylene, each optionally substituted by 1-4 C1-C4 alkyl. 13. A method according to Claim 11 wherein X is S. 14. A method according to Claim 12 wherein X is S.

Inventors: CHAPMAN JAMES MOOD, KOLLMEYER WILLY DIETRICH, KOSH JOSEPH WILLIAM, MCCANN STEPHEN FREDERICK, SOWELL JOSEPH WALTER, ZWICK FAITH BLERSCH, CHAPMAN, JAMES, MOOD, KOLLMEYER, WILLY, DIETRICH, KOSH, JOSEPH, WILLIAM, MCCANN, STEPHEN FREDERICK, SOWELL, JOSEPH, WALTER, ZWICK, FAITH, BLERSCH
Applicants: DU PONT, UNIV SOUTH CAROLINA, E.I. DU PONT DE NEMOURS AND COMPANY, UNIVERSITY OF SOUTH CAROLINA
Application year: 1991
Main classification: A01N51
IPC codes: A01N35, A01N37, A01N43, A01N47, A01N51, C07D233, C07D239