WO1993021161A1

WO1993021161A1 - Arthropodical nitroethylenes and nitroguanidines

Info

Publication number: WO1993021161A1
Application number: PCT/US1993/002165
Authority: WO
Inventors: Stephen Frederick Mccann
Original assignee: E.I. Du Pont De Nemours And Company
Priority date: 1992-04-13
Filing date: 1993-03-10
Publication date: 1993-10-28
Also published as: AU3800793A; CN1077451A; JPH07505652A; BR9306266A; EP0636122A1

Abstract

Methyl-substituted cyclic nitroethylenes and nitroguanidines of formula (I) wherein: R1 is H, CH¿2?CN, C1-C4 alkyl, C1-C4 haloalkyl, formyl, C2-C4 alkylcarbonyl, C2-C3 alkoxycarbonyl, C2-C4 alkoxyalkyl, C3-C6 dialkoxyalkyl, C1-C3 alkoxy, C1-C3 alkylsulfonyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkylamino, C2-C4 dialkylamino or benzyl optionally substituted with R?2; R2¿ is halogen, C¿1?-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, C1-C2 alkylthio, C1-C2 haloalkylthio, C1-C2 haloalkoxy, NO2 or CN; and Z is CHNO2 or NNO2; and agricultural compositions containing them which are useful for the control of arthropods in both agronomic and nonagronomic environments are disclosed.

Description

TITLE

ARTHROPODICAL NITROETHYLENES AND NITROGUANIDINES

This invention pertains to methyl-substituted cyclic nitroethylenes and nitroguanidines as arthro- podicides, particularly for the control of planthoppers and leafhoppers.

GB 1,483,633 generically discloses compounds of the present invention as insecticides. WO 91/17659

generically discloses a method to control planthoppers and leafhoppers with the compounds of the present invention. U.S. 4,880,933 generically discloses compounds of the present invention as intermediates for insecticides. There are no specific disclosures in these references to compounds of the present invention.

SUMMARY OF THE INVENTION

The invention comprises compounds of Formula I, including all geometric and stereoisomers,

agriculturally suitable salts thereof, agricultural compositions containing them and their use for the control of arthropods, particularly planthoppers and leafhoppers, in both agronomic and nonagronomic

environments. The compounds of Formula I comprise:

wherein:

R¹ is H, CH₂CN, C₁-C₄ alkyl, C₁-C₄ haloalkyl,

formyl, C₂-C₄ alkylcarbonyl, C₂-C₃ alkoxycarbonyl, C₂-C₄ alkoxyalkyl, C₃-C₆ dialkoxyalkyl, C₁-C₃ alkoxy, C₁-C₃ alkylsulfonyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₄ alkylamino, C₂-C₄ dialkylamino or benzyl optionally substituted with R²;

R² is halogen, C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂ alkylthio, C₁-C₂ haloalkylthio,

C₁-C₂ haloalkoxy, NO₂ or CN; and

Z is CHNO₂ or NNO₂.

Preferred Compounds A are compounds of Formula I wherein R¹ is H, C₁-C₄ alkyl, formyl, CH₃S(O)₂ or

CH₃C(O). Preferred Compounds B are Compounds A wherein Z is CHNO₂. Preferred Compounds C are Compounds A wherein Z is NNO₂.

Specifically preferred for biological activity and ease of synthesis are the compounds of Preferred

Compounds B and Preferred Compounds C respectively, which are:

5-methyl-1-[2-(methylthio)ethyl]-2-(nitro- methylene)-imidazolidine; and

5-methyl-1-[2-(methylthio)ethyl]-N-nitro-2- imidazolidinimine.

Preferred compositions of the present invention are those containing the above designated preferred

compounds. Preferred methods for controlling foliar and soil inhabiting anthropods and nematode pests are those employing the above designated compounds and compositions.

DETAILED DESCRIPTION OF THE INVENTION

In the above definitions, the term "alkyl", used either alone or in compound words such as "alkythio" or "haloalkyl", denotes straight chain or branched alkyl such as methyl, ethyl, n-propyl, isopropyl or the different butyl isomers. Alkoxy denotes methoxy, ethoxy, n-propyloxy and isopropyloxy. Alkenyl denotes straight chain or branched alkenes such as vinyl, 1-propenyl, 2-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 and ethylthio. Alkylsulfonyl and alkylamino are defined analogously to the above examples.

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 may be partially or fully substituted with halogen atoms, which may be the same or different. Examples of haloalkyl include CH₂CHF₂, CF₂CF₃ and CH₂CHFCl.

The total number of carbon atoms in a substituent group is indicated by the "C_i-C_j" prefix where i and j are numbers from 1 to 6. For example, C₁-C₃ alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C₂ alkoxy designates OCH₂CH₃ and C₃ alkoxy designates OCH₂CH₂CH₃ and OCH(CH₃)₂; C₂ alkylcarbonyl designates C(O)CH₃ and C₄ alkylcarbonyl designates C(O)CH₂CH₂CH₃ and C(O)CH(CH₃)₂; and as a final example, C₃ alkoxycarbonyl designates C(O)OCH₂CH₃ and C₄

alkoxycarbonyl designates C(O)CH₂CH₂CH₃ and

C(O)CH(CH₃)₂.

The compounds of Formula I where R¹ is a group other than hydrogen can be prepared from the analogous Formula I compounds where R¹ is equal to hydrogen as illustrated in Scheme 1.

SCHEME 1

wherein: II is an alkylating, acylating or

sulfonylating reagent.

Typical conditions involve the combination of I (R¹=H) with an alkylating, acylating or sulfonylating agent, denoted -as II, in a suitable solvent in the presence of a proton acceptor. The Formula II

compounds are typically used in equimolar or

stoichiometric excess amounts and include alkylating ^"agents such as alkyl halides and sulfonates, acylating agents such as acyl halides and anhydrides, and sulfonylating agents such as sulfonyl halides and anhydrides. The proton acceptor species is typically used in amounts ranging from 1 to 20 molar equivalents and include metal hydrides such as NaH and KH, amide bases such as lithium diisopropylamide, amine bases such, as pyridine and triethylamine, inorganic

carbonates such as lithium, sodium, potassium and cesium carbonate, metal alkoxides such as sodium methoxide and potassium tert-butoxide, and hydroxides such as NaOH and KOH. Typical solvents include polar, aprotic solvents such as dimethylformamide, N-methyl pyrrolidone and acetonitrile, ethers such as diethyl ether and tetrahydrofuran, and protic solvents such as methanol, ethanol, propanol and water. Typical reaction temperatures range from 0°C to the reflux temperature of the solvent and reaction times range from 5 minutes to several days.

Compounds of Formula I wherein R¹ is equal to H can be prepared by the reaction of Formula III compounds with 2-chloroethyl methyl sulfide (IV) in the presence of a proton acceptor as shown in Scheme 2.

SCHEME 2

The reactions depicted in Scheme 2 typically involve the mixture of equimolar amounts of III and IV in the presence of one equivalent of a base such as NaH in a polar, aprotic solvent such as DMF at a

temperature ranging from room temperature to 150°C, with 100°C being preferred. The product is typically isolated by removal of the solvent followed by column chromatography on silica gel using a suitable solvent or solvent mixture including, but not limited to, chloroform, methylene chloride, methanol, ethanol, ethyl acetate, triethylamine, saturated aqueous

ammonium hydroxide or mixtures of these solvents.

Alternatively, Formula I compounds, wherein R¹ is equal to H and Z is equal to CHNO₂ can be prepared by the reaction of diamine V with a compound of Formula VI as depicted in Scheme 3. SCHEME 3

wherein: X is a leaving group such as SCH₃, OC₆H₅ or halogen.

Scheme 3 reactions typically involve the mixture of equimolar amounts of V and VI (usually 1,1-bis(methyl thio)-2-nitroethylene) in a polar solvent such as, but not limited to, methanol, ethanol, acetonitrile, tetrahydrofuran or water at a temperature ranging from room temperature to the reflux temperature of the solvent. A proton acceptor such as, but not limited to, NaOH, sodium carbonate or triethylamine can be used.

Alternatively, compounds of Formula I wherein R¹ is H and Z is CHNO₂ can be prepared by the reaction of diamine V with a 2,2,2-trihalonitroethane of

Formula VII as depicted in Scheme 4 using conditions analogous to those described for Scheme 3 reactions. Scheme 4 reactions typically involve the use of between 1 and 10 molar equivalents of a base such as, but not limited to, amines such as triethylamine and pyridine, carbonates such as Na₂CO₃, K₂CO₃ and NaHCO₃ or

hydroxides such as LiOH, NaOH or KOH. SCHEME 4

wherein: X¹, X² and X³ are halogen.

Formula I compounds wherein R¹ is H and Z is NNO₂ can be prepared by the reaction of diamine V with either nitroguanidine VIII, (wherein Y is NH₂) or

S-methyl-N-nitroisothiourea VIII, (wherein Y is SCH₃) using procedures that are completely analogous to those described for Scheme 3. The formation of Formula I compounds wherein R¹ is H and Z is NNO₂ is depicted in Scheme 5.

SCHEME 5

wherein: Y=NH₂ or SCH₃,

Formula III compounds wherein Z equals CHNO₂ can be prepared by the reaction of 1, 2-diaminopropane IX with Formula VI compounds as depicted in Scheme 6.

Conditions for carrying out these reactions are

completely analogous to those described for Scheme 3. SCHEME 6

wherein: X is a leaving group such as SCH₃ or OC₆H₅.

Formula III compounds wherein Z equals NNO₂ can be prepared by the reaction of 1,2-diaminopropane IX with Formula VIII compounds in a completely analogous manner to that described for the preparation of Formula I compounds (R¹=H, Z=NNO₂) in Scheme-5.

The preparation of diamine V can be achieved using the two step procedure shown in Scheme 7.

SCHEME 7

Step i:

Step ii :

In Step i of Scheme 7, 2-(methylthio)ethylamine (X) is treated with potassium cyanide and acetaldehyde in the presence of one to two equivalents of acid in a solvent to form aminonitrile XI. Other cyanide salts as well as HCN can be used in the procedure. Hydrohalide and other acid salts of X can be used in the procedure. Suitable solvents include, but are not limited to,, methanol, ethanol, isopropanol and water, as well as combinations of solvents. Many alternative procedures for the preparation of amino nitriles such as XI can be found in the literature (see, e.g., Synth . Commun . , 1985, 15, 157; Synthesis, 1979, 127).

In Step ii of Scheme 7 , aminonitrile XI is reduced to form diamine V. This reduction is most conveniently achieved using lithium aluminum hydride in amounts ranging from 0.75 to 3 molar equivalents in a solvent such as diethyl ether or THF at a temperature ranging from -10°C to the reflux temperature of the solvent. Alternatively, the reduction of XI to form V can be achieved using hydrogenation over a catalyst such as palladium on carbon.

The following Examples further illustrate the invention.

EXAMPLE 1

Step A: 2-[2-(Methylthio)ethylaminolpropanenitrile

A solution of 24.4 g (0.27 moles) of 2-(methylthio) ethylamine and 100 mL of methanol was treated with 294 mL of 1 M aqueous HCl added dropwise with ice-bath cooling over 15 min. at 5-10°C. The resulting solution was treated with a solution of 17.4 g (0.27 moles) of potassium cyanide and 150 mL of water at 5-10°C

followed by the addition of 13 g (0.29 moles) of acetaldehyde at 5-10°C. The resulting solution was stirred at room temperature for 6 hours and was then poured into a mixture of 1 L of saturated aqueous sodium bicarbonate and 300 mL of CH₂Cl₂. The aqueous layer was extracted with two additional 200 mL portions of CH₂Cl₂ and the combined organic layers were washed with 500 mL of saturated aqueous NaHCO₃, dried overanhydrous MgSO₄, filtered and concentrated to give 37.6 g (97%) of a pale yellow oil. ¹HNMR (200 MHz, CDCl₃) 53.78-3.60 (m, 1H), 3.17-2.97 (m, 1H),

2.94-2.74 (m, 1H), 2.71-2.62 (m, 2H), 2.12 (s, 3H), 1.67 (br s, 1H), 1.52 (d, J=7 Hz, 3H).

Step B: N²-[2-(Methylthio)ethyl]-1,2-propanediamine A vigorously stirred (mechanical stirrer) solution of lithium aluminum hydride (84 mL of a 1 M solution in (CH₃CH₂)₂O, 0.084 moles) and (CH₃CH₂)₂O (163 mL) was treated with a solution of 6.04 g (0.042 moles) of the product from Step A and 82 mL of (CH₃CH₂)₂O added dropwise at 0°C. The resulting white heterogeneous mixture was stirred at 0°G for 1 h, at room temperature for 1 h and then cooled to 0°C and quenched by the careful, sequential addition of a solution of 3.1 mL H₂O in 10 mL of tetrahydrofuran, 3.1 mL of 15% NaOH and 9.3 mL of H₂O at 0°C. The resulting mixture was diluted with 155 mL of (CH₃CH₂)₂O and stirred at room temperature overnight. The resulting mixture was filtered and the filtrate was concentrated to give 6.4 g of a dark yellow oil. ¹HNMR (200 MHz, CDCl₃) δ 2.97-2.45 (m, 7H), 2.11 (s, 3H), 1.75 (br s, 3H), 1.05 (d, J=6 Hz, 3H).

Step C: 5-Methyl-1-[2-(methylthio)ethyl]-2-(nitromethylene)-imidasplidine (Compound 1) A solution of 2.6 g (0.018 moles) of the product from Step B, 2.9 g (0.018 moles) of 2,2-bis- (methylthio)-1-nitroethylene and 18 mL of absolute ethanol was heated at reflux for 5 h, cooled to room temperature and concentrated to give 4.8 g of a brown oil. Flash chromatography of the oil on silica gel using 40:1:0.1 CH₂Cl₂:CH₃CH₂OH:48% NH₄OH gave 1.8 g of a yellow oil that solidified on standing, m.p. 60-62°C. Trituration of the solid with 1-chlorobutane gave an off-white solid that melted at 66-68°C. ¹HNMR (200 MHz, CDCl₃) δ 8.63 (br s, 1H), 6.53 (s, 1H), 4.21-4.03 (m, 1H), 3.90 (t, 1H), 3.40-3.28 (m, 3H), 2.78-2.58 (m, 2H), 2.16 (s,3H), 1.36 (d, 3H). EXAMPLE 2

5-Methyl-1-[2-(methylthio)ethyl]- N-nitro-2-imidazolidinimine (Compound 2) A solution of 2.6 g (0.018 moles) of the product of Step B of Example 1, 2.4 g of S-methyl-N-nitroisothiourea and 18 mL of absolute ethanol was heated at reflux for 18 h. The resulting mixture was cooled to room temperature and concentrated to give 3.5 g of a brown oil. Flash chromatography of the oil on silica gel using 40:1:0.1 CH₂Cl₂:CH₃CH₂OH:48% NH₄OH gave

1.25 g of a light yellow oil. ¹HNMR (200 MHz, CDC1₃) δ 8.08 (br s, 1H), 4.18 4.00 (m, 1H), 3.92 (t, 1H), 3.78 (dd, 1H), 3.42-3.24 (m, 2H), 2.84-2.60 (m, 2H), 2.17 (s, 3H), 1.37 (d, 3H).

By the general procedures described herein, or obvious modifications thereof, the compounds of

Tables 1, 2-and Index Table A can be prepared.

In Tables 1, 2, and Index Table A the following notations have been used:

Me = CH₃ n-Bu = (CH₂)₃CH₃

Et = CH₂CH₃ i-Bu = CH₂CH(CH₃)₂ n-Pr = (CH₂)₂CH₃ s-Bu = CH(CH₃)CH₂CH₃ i-Pr = CH(CH₃)₂ t-Bu = C(CH₃)₃

CH₂(2-Cl-Ph) =

CH₂(3-Cl-Ph) =

CH₂(4-Cl-Ph) =

Formulation/Utility

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. Thus, the arthropodicidal compositions of the present invention comprise an effective amount of a compound of Formula I and at least one of (a) a

surfactant, (b) an organic solvent, and (c) at least one solid or liquid diluent, useful formulations can be prepared in conventional ways. They include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The

formulations will typically contain effective amounts of an active ingredient, diluent and a surfactant within the following approximate ranges wherein the active ingredient plus surfactant and/or diluent equals 100 weight percent.

Weight Percent

Active

Ingredient Diluent Surfactant

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 and 0.01-99 5-99.99 0-15 Pellets

High Strength 90-99 0-10 0-2

Compositions 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., Interscience, 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 formulations 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, or a similar governmental agency in the country of use, for the use intended.

Methods for formulating 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 mill or fluid energy mill. Water-dispersible granules can be produced be agglomerating a fine powder composition; see for example, Cross et al., Pesticide Formulations, Washington, D.C, 1988, pp. 251-259. 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

Browning, "Agglomeration", Chemical Engineering,

December 4, 1967, pages 147 and following. Perry 's Chemical Engineer 's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8 to 57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in DE 3,246,493.

For further information regarding the art of formulation, see U.S. Patent 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41;

U.S. Patent 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S.

Patent 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp. 81-96; and Hance et al.. Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.

In the following Examples, all parts are by weight percent. Compound numbers refer to Index Table A.

Example A

Emsulifiable Concentrate

Compound 1 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

Compound 1 30% sodium alkylnaphthalenesulfonate 2% sodium ligninsulfonate 2% synthetic amorphous silica 3% kaolinite 63% The active ingredient is mixed with the inert materials in a blender. After grinding in a hammer- mill, 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.

Example D

Granule

Compound 1 2% montmorillonite granules (low volatile

matter, 0.71/0.30 mm;

U.S.S. No. 25-50 sieves) 98%

The active ingredient is dissolved in a volatile solvent such as acetone and sprayed upon

montmorillonite granules in a double cone blender. The acetone is then driven off by heating. The granules are then allowed to cool and are packaged.

Example E

Granule

Wettable powder of Example B 15% gypsum 69% potassium sulfate 16%

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. Example F

Solution

Compound 1 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

Compound 2 40.0% polyacrylic acid thickener 0.3% dodecyclophenol polyethylene glycol ether 0.5% disodium phosphate 1.0% monosodium phosphate 0.5% polyvinyl alcohol 1.0% water 56.7%

The ingredients are blended and ground together in a sand mill to produce particles substantially all under 5 microns in size.

Example H

Pre-formed Granule

Talc 85%

Calcium ligninsulfonate 12%

Sodium ligninsulfonate 3%

The ingredients are blended and the moistened with. about 20% water. The mixture is extruded as cylinders about 1 mm diameter which break into pieces generally ranging from 1 to 10 mm in length. These are dried and used as described in Example I.

Example I

Granule

Compound 1 2%

Pre-formed granule from Example H 98%

Compound 1 is dissolved in acetone and sprayed upon the pre-formed granules in a mixer. The acetone is driven off by heating. The granules are then allowed to cool and are packaged. Example J

Bait Grannles

Compound 1 3.0% blend of polyethoxylated nonylphenols

and sodium dodecylbenzene sulfonates 9.0% 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.

The compounds of this invention exhibit activity against a wide spectrum of foliar-feeding, fruit-feeding, seed-feeding, aquatic and soil-inhabiting arthropods (term includes insects, mites and nematodes) 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. Those skilled in the art will appreciate that not all compounds are equally effective against all pests. Nevertheless, all of the compounds of this invention display activity against pests that include: eggs, larvae and adults of the Order Lepidoptera; eggs, foliar-feeding, fruit-feeding, root-feeding, seed-feeding larvae and adults of the Order Coleoptera; eggs, immatures and adults of the

Orders Hemiptera and Homoptera; eggs, larvae, nympths and adults of the Order Acari; adults and immatures of the Orders Thysanoptera, Orthoptera and Dermaptera;

eggs, immatures and adults of the Order Diptera; and adults and immatures of the class Nematoda. The compounds of this invention are also active against pests of the Orders Hymenoptera, Isoptera,

Phthiraptera, Siphonoptera, Blattaria, Thysanaura and Pscoptera; pests belonging to the class of Arachnida; and Helminthes. The compounds are particularly active against southern corn rootworm (Diabrotica undecimpunctata howardi), aster leafhopper

(Mascrosteles fascifrons) , boll weevil {Anthonomus grandis), two-spotted spider mite ( Tetranychus

urticae) , fall armyworm (Spodoptera frugiperda), black bean aphid (Aphis fabae), tobacco budworm (Heliothis virescens), rice water weevil (Lissorhoptrus

oryzophilus), rice leaf beetle ( Oulema oryzae),

whitebacked planthopper (Sogatella furcifera), green leafhopper (Nephotettix cincticeps), brown planthopper (Nilaparvata lugens), small brown planthopper

{Laodelphax striatellus) rice stem borer ( Chilo suppressalis), rice leafroller (Cnaphalocrocis

medinalis) , black rice stink bug (Scotingphara lurida) , rice stink bug (Lagynotomus elongatus), rice bug

{Leptocorisa chinensis), slender rice bug {Cletus puntiger), and southern green stink bug (Nezara

viridula) . See WO 90/10623 and WO 92/00673 for more detailed pest descriptions.

Compounds of this invention can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, semiochemicals, repellants, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection. Examples of other

agricultural protectants with which compounds of this invention can be formulated are: insecticides such as monocrotophos, carbofuran, tetrachlorvinphos,

malathion, parathion-methyl, methomyl, chlordimeform, diazinon, deltamethrin, oxamyl, fenvalerate,

esfenvalerate, permethrin, profenofos, sulprofos, triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fonophos, isofenphos, methidathion, methamidophos, phosmet, phosphamidon, phosalone, pirimicarb, phorate, terbufos, trichlorfon, methoxychlor. bifenthrin, biphenate, cyfluthrin, fenpropathrin, fluvalinate, flucythrinate, tralomethrin, metaldehyde and rotenone; fungicides such as carbendazim, thiuram, dodine, maneb, chloroneb, benomyl, cymoxanil,

fenpropidine, fenpropimorph, triadimefon, captan, thiophanate-methyl, thiabendazole, phosethyl-Al, chlorothalonil, dichloran, metalaxyl, captafol,

iprodione, oxadixyl, vinclozolin, kasugamycin, myclobutanil, tebuconazole, difenoconazole, diniconazole, fluquinconazole, penconazole, propiconazole, uniconzole, flutriafol, procfrloraz, pyrifenox, fenarimol, triadimenol, diclobutrazol, copper oxychloride,

furalaxyl, folpet and flusilazol; nematocides such as aldoxycarb, fenamiphos and fosthietan; bactericides such as oxytetracyline, streptomycin and tribasic copper sulfate; acaricides such as binapacryl,

oxythioquinox, chlorobenzilate, dicofol, dienochlor, cyhexatin, hexythiazox, amitraz, propargite and

fenbutatin oxide; and biological agents such as

bacillus thuringiensis and bacculovirus.

In certain instances, combinations with other arthropodicides having a similiar spectrum of control but a different mode of action will be particularly advantageous for resistance management.

The present invention further comprises a method for the control of foliar and soil inhabiting

arthropods and nematode pests and protection of

agronomic crops, animal and human health comprising applying one or more of the compounds of Formula I, or compositions containing at least one such compound, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled. A preferred method of application is by spraying with equipment that

distributes the compound in the environment of the pests, on the foliage, animal, person, or premise, in the soil or animal, to the plant part that is infested or needs to be protected. Alternatively, granular formulations of these compounds can be applied to the foliage or applied to or incorporated into the soil or rice paddys. Other methods of application can also be employed including direct and residual sprays, aerial sprays, systemic uptake, baits, eartags, boluses, foggers, fumigants, aerosols, and many others. The compounds can be incorporated into baits that are consumed by the arthropods or in devices such as traps and the like which entice them to ingest or otherwise contact the compounds.

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 with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use. A preferred method of

application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, and synergists and other solvents such as piperonyl butoxide often enhance compound efficacy.

The rate of application required for effective control will depend on such factors as the species of arthropod to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like. In general, application rates of about 0.01 to 2 kg of active ingredient per hectare are sufficient to provide large-scale effective control of pests in agronomic

ecosystems under normal circumstances, but as little as 0.001 kg/hectare may be sufficient or as much as 8 kg hectare may be required. For nonagronomic

applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as

0.1 mg/square meter may be sufficient or as much as 150 mg/square meter may be required.

The following tests demonstrate the control

efficacy of compounds of Formula I on specific pests; see Index Table A for compound descriptions. The pest control protection afforded by the compounds of the present invention is not limited, however, to these species. Compounds not included were either not screened or gave mortality levels less than 80%.

Index Table A

Compound Z R¹ m.p. °C

1 CHNO₂ H 66-68

2 NNO₂ H oil

3 CHNO₂ CH₂CHCH₂ oil

4 NNO₂ C(O)CH₃ oil

Compound No. ¹H NMR Data¹

3² 6.41 (s , 1H), 5, .94-5.75 (m, 1H),

5.35-5.18 (m, 2H), 4.08-3.78 (m, 5H), 3.43 (dt, 1H), 3.12 (dd, 1H), 2.83-2.58 (m, 2H), 2.14 (s, 3H), 1.35 (d, 3H). 4³ 4.01 (dd, 1H), 3 . 84-3 .78 (m, 1H),

3 . 74-3 . 65 (m, 1H), 3 .38 (dd, 1H), 3 .27 (ddd, 1H), 2. 78-2 . 60 (m, 2H), 2 .51

(s , 3H) , 2 . 17 (s , 3H) , 1.29 (d, 3H) .

¹Unless indicated otherwise, spectra were obtained in CDCl₃.

s = singlet, d = doublet, t = triplet, m = multiplet.

2Spectrum obtained at 200 MHz.

3Spectrum obtained at 400 MHz.

Test A

Fall armyworm

Test units were high impact styrene trays with 12 cells. The cells contained water moistened filter paper and approximately 8 square cm of lima leaf.

15-20 third instar larvae of fall armyworm (Spodoptera frugiperda) were placed in an 8 ounce (230 ml) plastic cup. Solutions of each of the test compounds (75:25) acetone:distilled water solvent, were sprayed into the tray and cup. Spraying was accomplished by passing the tray and cup, on a conveyor belt, directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.5 pounds of active ingredient per acre (about 0.55 kg/ha) at 30 psi (207 kPa). The insects were then transferred into the tray (one larva per cell). The trays were covered and held at 27°C and 50% relative humidity for 48 hours, after which time readings were taken on the 12 cells with lima leaves. Of the compounds tested, the following gave mortality levels of 80% or higher: 1.

Test B

Southern corn rootworm

The units, each consisting of an 8-ounce (230 ml) plastic cup containing 1 one-inch square of a soybean-wheatgerm diet, were prepared. The test units were sprayed as described in Test A with individual solutions of the test compounds. After the spray on the cups had dried, five second-instar larvae of the southern corn rootworm (Diabrotic undecimpunctata howardi) were placed into each cup. The cups were then covered and held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher after 48 hours: 1, 2, 3, 4.

Test C

Aster leafhopper

Test units were prepared from a series of 12-ounce (350 ml) cups, each containing oat (Avena sativa) seedlings in a 1-inch (2.5 cm) layer of sterilized soil and a 1/2-inch layer of sand. The test units were sprayed as described in Test A with individual

solutions of the below-listed compounds. After the oats had dried from the spraying, between 10 and 15 adult aster leafhoppers (Macrosteles fascifrons) were aspirated into each of the cups covered with vented lids. The cups were held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 1 , 2, 4.

Test D

Boll weevil

Five adult boll weevils (Anthonomus grandis

grandis) were placed into each of a series of 9-ounce (260 ml) cups. The test units were sprayed as

described in Test A with individual solutions of the below-listed compounds. Each cup was then covered with a vented lid and held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 1, 2. Test E

Black bean aphid

Individual nasturtium leaves were infested with 10 to 15 aphids (all stages of Aphis fabae) and sprayed with their undersides facing up as described in Test A.

The leaves were then set in 3/8 inch diameter vials containing 4 ml of sugar water solution and covered with a clear plastic 1-ounce portion cup to prevent escape of aphids that drop from the leaves. The test units were held at 27°C and 50% relative humidity for 48 hours, after which tiiηe mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 1, 2, 3.

Test F

Solution Systemic Activity Against Green Leafhopper Nymphs

The test chemical is added directly into 10 mL of distilled water and dissolved completely. This

chemical solution is poured into a conical shaped test unit. Three rice seedlings are then positioned in the unit by a notched sponge disk. The sponge disk allows complete immersion of the seedling root systems in the chemical solution, while the aerial portion of the plant is isolated above the solution. The sponge also prevents the test nymphs from accidentally contacting the test solution. A 7 to 10 mm space, between the surface of the chemical solution and the bottom of the sponge disk, prevents accidental chemical contamination of the sponge. The concentration of the test chemical in the chemical solution is 100 ppm. The rice

seedlings are allowed to absorb the chemical from the solution for 24 hours in a growth chamber held at 27°C and 65% relative humidity. Eight to ten 3rd-instar nymphs of the green leafhopper (Nephotettix cincticeps) are transferred into the test units using an aspirator. The infested units are held under the same temperature and humidity conditions described above. Counts of the number of live and dead nymphs are taken at 24 and 48 hours post-infestation. Insects which cannot walk are classified as dead. Of the compounds tested, the following gave mortality levels of 80% or higher at 48 hours post-infestation: 1, 2.

Test G

Solution Systemic Activity Against Brown Planthopper

Nymphs

Same methods as used for Solution Systemic Activity against green leafhopper nymphs, except that the brown planthopper (Nilaparvata lugens) is the test species. Of the compounds tested, the following gave mortality levels of 80% or higher at 48 hours post-infestation: 1, 2.

Test H

Contact Activity Against Green Leafhopper Nymphs

Three rice (Oryza sativa) seedlings, 1.5 leaf stage and about 10 cm tall are transplanted into a 1/2 oz. plastic cup containing Kumiai Brown artificial soil. Seven milliliters of distilled water is then added to the cup. The test chemical is prepared by first dissolving the chemical in acetone and then adding water to produce a final test concentration of 75:25 (acetone:water). Four plastic cups, each cup serving as a replicate, are then placed on a spray chamber turntable. The cups are sprayed for 45 seconds with 50 mL of the chemical solution at a pressure of

2.0 kg/cm² with air atomizing spray nozzles. The turntable completes 7.5 rotations during the 45 second spray interval. After chemical application, treated cups are held in a vented enclosure to dry for about 2 h. After drying, the cups are placed into conical shaped test units and the surface of the soil coveredwith 2 to 3 mm of quartz sand. Eight to ten 3rd-instar nymphs of the green leafhopper (Nephotettix cincticeps) are transferred into the test units using an aspirator. The test units are held at 27°C and 65% relative humidity. Counts of the number of live and dead nymphs are taken at 24 and 48 h post-infestation. Insects which cannot walk are classified as dead. Of the compounds tested, the following gave mortality levels of 80% or higher at 48 h at 100 ppm: 1, 2, 4.

Test I

Contact Activity Against Brown Planthopper Nymphs

Three rice (Oryza sativa) seedlings, 1.5 leaf stage and about 10 cm tall are transplanted into a 1/2 oz. (14 mL) plastic cup containing Kumiai Brown artificial soil. Seven milliliters of distilled water is then added to the cup. The test chemical is prepared by first dissolving the chemical in acetone and then adding water to produce a final test concentration of 75:25 (acetone:water). Four plastic cups, each cup serving as a replicate, are then placed on a spray chamber turntable. The cups are sprayed for 45 seconds with 50 mL of the chemical solution at a pressure of 2.0 kg/cm² with air atomizing spray nozzles. The turntable completes 7.5 rotations during the 45 second spray interval. After chemical application, treated cups are held in a vented enclosure to dry for about 2 h. After drying, the cups are placed into conical shaped test units and the surface of the soil covered with 2 to 3 mm of quartz sand. Eight to ten 3rd-instar nymphs of the brown planthopper (Nilaparvata lugens) are transferred into the test units using an aspirator. The test units are held at 27°C and 65% relative humidity. Counts of the number of live and dead nymphs are taken at 24 and 48 h post-infestation. Insects which cannot walk are classified as dead. Of the compounds tested, the following gave mortality levelsof 80% or higher at 48 h at 100 ppm: 1, 2. Test J is a comparison of Compound 1 vs. the nor-methyl derivative which is generically disclosed in GB 1,483,633 and specifically disclosed in WO 91/17659 as compound 14 (page 96). The compounds were tested individually under the same conditions but not in a direct comparison.

Test J

Table 3 compares the observed activity of present Compound 1 with nor-methyl derivative (Compound A). The compounds were tested individually but not in a direct comparison under the conditions as described in the Tests H and I above except that the application rate was 2.5 ppm,

Table 3

(% observed mortality)

SPECIES Compound 1 Compound A

Contact Activity Against Green 100 59

Leafhopper Nymphs

Contact Activity Against Brown 90 24

Planthopper Nymphs

Claims

What is claimed is:

1. A compound of Formula I:

wherein:

R¹ is H, CH₂CN, C₁-C₄ alkyl, C₁-C₄ haloalkyl,

formyl, C₂-C₄ alkylcarbonyl, C₂-C₃

alkoxycarbonyl, C₂-C₄ alkoxyalkyl, C₃-C₆ dialkoxyalkyl, C₁-C₃ alkoxy, C₁-C₃ alkylsulfonyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₄ alkylamino, C₂-C₄ dialkylamino or benzyl optionally substituted with R²;

R² is halogen, C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂ alkylthio, C₁-C₂ haloalkylthio, C₁-C₂ haloalkoxy, NO₂ or CN; and

Z is CHNO₂ or NNO₂;

and agriculturally suitable salts thereof.

2. A compound of Claim 1 wherein R¹ is H, C₁-C₄ alkyl, formyl, CH₃S(O)₂ or CH₃C(O).

3. A compound of Claim 2 wherein Z is CHNO₂.

4. A compound of Claim 2 wherein Z is NNO₂.

5. A compound of Claim 3 which is 5-methyl-1-[2-(methylthio)ethyl]-2-(nitromethylene)-imidazolidine.

6. A compound of Claim 4 which is 5-methyl-1-[2-(methylthio)ethyl]-N-nitro-2-imidazolidinimine.

7. An arthropodicidal composition comprising an effective amount of a compound of Formula I

wherein:

R¹ is H, CH₂CN, C₂-C₄ alkyl, C₁-C₄ haloalkyl,

Z is CHNO₂ or NNO₂.

and at least one of (a) a surfactant, (b) an organic solvent, and (c) at least one solid or liquid diluent.

8. A method for controlling foliar and soil

inhabiting arthropods and nematode pests comprising applying to the locus of infestation, area to be protected, or directly onto said pests an effective amount of a compound of Formula I or an arthropodicidal composition comprising an effective amount of a

compound of Formula I and at least one of (a) a

surfactant, (b) an organic solvent, and (c) at least one solid or liquid diluent wherein Formula I is

wherein :

R¹ is H, CH₂CN, C₁-C₄ alkyl, C₁-C₄ haloalkyl,

formyl, C₂-C₄ alkylcarbonyl, C₂-C₃

alkoxycarbonyl, C₂-C₄ alkoxyalkyl, C₃-C₆ dialkoxyalkyl, C₁-C₃ alkoxy, C₁-C₃ alkylsulfonyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₃ alkylamino, C₂-C₄ dialkylamino or benzyl optionally substituted with R²;

Z is CHNO₂ or NNO₂;

and agriculturally suitable salts thereof.