JP2011523939A - Synergistic insecticidal mixture - Google Patents

Abstract

Provide a synergistic insecticidal mixture.
[Selection figure] None

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application claims priority to US Provisional Patent Application No. 60 / 927,119, filed May 1, 2007, the entire disclosure of which is incorporated herein by reference. .

  The invention disclosed herein relates to the field of insecticides and to its use in controlling pests.

  Pests cause millions of deaths worldwide every year. Furthermore, there are over 10,000 species of pests that cause losses in agriculture. These agricultural losses are worth billions of dollars each year. Termites cause losses to various structures such as homes. These termite losses can amount to billions of dollars each year. Lastly, many stored food pests eat stored food and degrade quality. These stored food losses can cost billions of dollars each year, but more importantly, deprive humans of the food they need.

  There is a serious need for new insecticides. Insects are acquiring resistance to currently used insecticides. Hundreds of insects are resistant to one or more insecticides. Acquiring resistance to several older insecticides, such as DDT, carbamates, and organophosphorus, is well known. However, it has also gained resistance to several new insecticides. Therefore, there is a need for new insecticides, particularly insecticides with new mechanisms of action.

Substituents (NON-EXHAUSTIVE LIST)
Examples of substituents are non-exhaustive (except halo) and should not be construed as limiting the invention disclosed herein.

  “Alkoxy” means an alkyl further comprising a carbon-oxygen single bond, for example, methoxy, ethoxy, propoxy, isopropoxy, 1-butoxy, 2-butoxy, isobutoxy, tert-butoxy, pentoxy, 2-methylbutoxy, There are 1,1-dimethylpropoxy, hexoxy, heptoxy, octoxy, nonoxy, and decoxy.

  “Alkyl” means an acyclic, saturated, branched or unbranched substituent consisting of carbon and hydrogen, such as methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, There are isobutyl, tert-butyl, pentyl, 2-methylbutyl, 1,1-dimethylpropyl, hexyl, heptyl, octyl, nonyl, and decyl.

  “Halo” means fluoro, chloro, bromo, and iodo.

  “Haloalkyl” means the maximum number of alkyls consisting of the same or different halo as possible from one, eg, fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoromethyl, 2-fluoroethyl, 2, There are 2,2-trifluoroethyl, chloromethyl, trichloromethyl, and 1,1,2,2-tetrafluoroethyl.

  The compounds of the following formula are synergistic with various other insecticides.

[Where:
X represents NO ₂ , CN, or COOR ⁴ ;
L represents a single bond, or R ¹ , S and L together represent a 5-membered or 6-membered ring;
R ¹ represents methyl or ethyl,
R ² and R ³ independently represent hydrogen, methyl, ethyl, fluoro, chloro, or bromo;
n is an integer from 0 to 3,
When n = 0 to 3 and L represents a single bond, Y is 6-halopyridin-3-yl, 6- (C ₁ -C ₄ ) alkylpyridin-3-yl, 6-halo (C _1- C ₄₎ alkyl-3-yl, 6- _(C 1 _{~C 4)} alkoxy-3-yl, 6- halo _(C 1 _{~C 4)} alkoxy-3-yl, 2-chloropyridin-4-thiazole Y, or 3-chloroisoxazol-5-yl, or when n = 0 to ¹ and R ¹ , S, and L together represent a 5- or 6-membered ring, Y is _hydrogen, C 1 -C ₄ alkyl, phenyl, 6-halopyridine-3-yl, 6- _(C 1 ~C ₄₎ alkyl-3-yl, 6- halo _(C 1 ~C ₄₎ alkyl pyridine -3 - yl, 6- _(C 1 ~C ₄₎ alkoxy pyridine - - Represents yl, 6-halo _(C 1 _{~C 4)} alkoxy-3-yl, 2-chloro-4-yl, or 3-chloro-isoxazol-5-yl,
R ⁴ represents C ₁ -C ₃ alkyl].

  Methods for preparing sulfoximines other than those described in Scheme H have been previously disclosed in US Patent Application Publication No. 20050228027, the teachings of which are incorporated herein.

Compounds of formula (Ia) in which R ¹ , R ² , R ³ , R ⁴ , X, and Y are as defined above and L is a single bond are prepared by the method illustrated in Scheme A be able to.

  In step a of Scheme A, the sulfide of formula (A) is oxidized with meta-chloroperoxybenzoic acid (mCPBA) in a polar solvent below 0 ° C. to give the sulfoxide of formula (B). In most cases, dichloromethane is the preferred solvent for oxidation.

  In step b of Scheme A, the sulfoxide (B) is imidized with sodium azide in the presence of concentrated sulfuric acid in an aprotic solvent under heating to give the sulfoximine of formula (C). In most cases, chloroform is the preferred solvent for this reaction.

In step c of Scheme A, the nitrogen of the sulfoximine (C) is cyanated with cyanogen bromide in the presence of a base, or nitrated with nitric acid in the presence of acetic anhydride at a mildly elevated temperature, or 4- Carboxylation with alkyl (R ⁴ ) chloroformate in the presence of a base such as dimethylaminopyridine (DMAP) provides N-substituted sulfoximine (Ia). A base is required for efficient cyanation and carboxylation, the preferred base is DMAP, and sulfuric acid is used as a catalyst for efficient nitration reactions.

Compounds of formula (Ia) where X represents CN and R ¹ , R ² , R ³ , R ⁴ , and Y are as previously defined were prepared by a mild and efficient method illustrated in Scheme B can do.

  In Step B of Scheme B, oxidation of sulfide with iodobenzenediacetic acid in the presence of cyanamide at 0 ° C. yields sulfilimine (F). The reaction can be carried out in a polar, aprotic solvent such as dichloromethane.

  In step b of Scheme B, sulfilimine (F) is oxidized with mCPBA. A base such as potassium carbonate is used to neutralize the acidity of mCPGA. Protic polar solvents such as ethanol and water are used to increase the solubility of the sulfilimine starting material and base used. Sulfilimine (F) can also be oxidized with an aqueous solution of periodinate sodium or potassium periodate in the presence of a ruthenium trichloride hydrate catalyst or similar catalyst. The organic solvent for the catalyst may be a polar aprotic solvent such as dichloromethane, chloroform, or acetonitrile.

The α-carbon of the N-substituted sulfoximine of formula (Ia), i.e. n = 1 and R ³ = H in the (CR ² R ³ ) group adjacent to the N-substituted sulfoximine functional group is In the presence of a base such as potassium hexamethyldisilamide (KHMDS), and further alkylated or halogenated (R ⁵ ) to produce an N-substituted sulfoximine of formula (Ib), wherein R ¹ , R ² , R ³ , R ⁴ , X, L, and Y are as defined above, and Z is a suitable leaving group as illustrated in Scheme C. Preferred leaving groups are iodide (R ⁵ = alkyl), benzenesulfonimide (R ⁵ = F), tetrachloroethene (R ⁵ = Cl), and tetrafluoroethene (R ⁵ = Br).

  The starting sulfide (A) in Scheme A can be prepared in different ways as illustrated in Schemes D, E, F, G, H, and I.

In Scheme D, the sulfide of formula (A ₁ ) in which R ¹ , R ² , and Y are as defined above, n = 1, and R ³ = H is obtained with a sodium salt of alkylthiol. It can be prepared from the chloride of formula (D ₁ ) by nuclear substitution.

In Scheme E, the sulfide of formula (A ₂ ) where R ¹ , R ² , and Y are as defined above, n = 3, and R ³ = H is a base such as potassium tert-butoxide. In the presence, it reacts with 2-monosubstituted methyl malonate to produce 2,2-disubstituted malonate, which is hydrolyzed under basic conditions to form a diacid and heated to Decarboxylation of monovalent acid to produce monoacid, and monoacid is reduced with borane-tetrahyrofuran complex to produce alcohol, which is then toluenesulfonyl chloride (tosyl) in the presence of a base such as pyridine. Chloride) to prepare the tosylate, which can be prepared from the chloride of formula (D ₂ ) by replacing the tosylate with the sodium salt of the desired thiol.

In Scheme F, the sulfide of formula (A ₃ ) where R ¹ , R ² , and Y are as previously defined, n = 2, and R ³ = H is deprotonated with a strong base and alkylated Alkylation with iodide produces an α-alkylated nitrile, hydrolysis of the α-alkylated nitrile in the presence of a strong acid such as HCl to produce an acid, and reduction of the acid with a borane-tetrahydrofuran complex Prepared from a nitrile of formula (E) by tosylating the alcohol with tosyl chloride in the presence of a base such as pyridine to produce a tosylate, and replacing the tosylate with the sodium salt of the desired thiol. can do.

In Scheme G, R ¹ , S, and L together form a ring, the sulfide of formula (A ₄ ) where n = 0 and Y = isopropyl or phenyl is m = 0, It can be prepared from substituted cyclic sulfides. The starting materials of cyclic sulfide is chlorinated in benzene N- chlorosuccinimide, subsequently may provide desired sulfide (A ₄₎ of sufficient yield alkylated with a Grignard reagent.

R ¹ , S, and L together form a ring, n = 0, m = 0, Y = 6-halo, 6- (C ₁ -C ₄ ) alkyl, 6- (C ₁ -C An alternative to the preparation of sulfides of formula (A ₄ ) that is ₄ ) haloalkyl, or 6- (C ₁ -C ₄ ) alkoxy substituted 3-pyridyl is highlighted in Scheme H. Accordingly, the corresponding, suitably substituted chloromethylpyridine is treated with thiourea, hydrolyzed and subsequently alkylated with 1-bromo-3-chloropropane under aqueous basic conditions, such as tetrahydrofuran (THF) Cyclization in the presence of a base such as potassium tert-butoxide in a polar, aprotic solvent.

In Scheme I, a sulfide of formula (A ₅ ) wherein R ¹ is as defined above, L is a bond, n = 0, and Y is 6-chloropyridin-3-yl is 2- It can be prepared from chloro-5-bromopyridine by halo-metal exchange and subsequent substitution with disulfide.

R ¹ , S, and L together form a saturated 5- or 6-membered ring and n = 1 type sulfoximine compound in which n = 1 is as defined above, and m is It can be prepared by the method illustrated in Scheme J, which is 0 or 1.

  In step a of scheme J, analogous to step b of scheme A, the sulfoxide is imidized with sodium azide in the presence of concentrated sulfuric acid or with O-mesitylsulfonylhydroxyamine in a polar aprotic solvent to give the sulfoximine. It is done. Chloroform or dichloromethane is the preferred solvent.

  In step b of scheme J, analogous to step c of scheme A, the sulfoxyimine nitrogen is cyanated with cyanogen bromide or nitrated with nitric acid, followed by treatment with acetic anhydride under reflux conditions, or DMAP and the like Carboxylation with methyl chloroformate in the presence of a base yields an N-substituted cyclic sulfoximine. A base is required for efficient cyanation and carboxylation, the preferred base is DMAP, and sulfuric acid is used as a catalyst for efficient nitration reactions.

  In step c of Scheme J, the α-carbon of the N-substituted sulfoximine is alkylated with a heterocyclic aromatic methyl halide in the presence of a base such as KHMDS or butyllithium (BuLi) to give the desired N- Substituted sulfoximines can be obtained. Preferred halides may be bromide, chloride, or iodide.

  Alternatively, the compound of formula (Ib) can be obtained by first α-alkylating the sulfoxide to obtain an α-substituted sulfoxide by using steps c, a, and b, respectively, described above for Scheme J, The sulfoxide can then be iminized and subsequently prepared by N-substitution of the resulting sulfoximine.

Compounds in which Y represents a claimed substituent other than 6- (C ₁ -C ₄ ) haloalkylpyridin-3-yl and 6- (C ₁ -C ₄ ) haloalkoxypyridin-3-yl are taught in their teachings. Is disclosed in US Patent Application Publication No. 20050228027, which is incorporated herein.

  The examples are for illustrative purposes only and should not be construed to limit the invention disclosed herein to the embodiments disclosed in the examples.

[Example I]
[(6-Trifluoromethylpyridin-3-yl) methyl] (methyl) -oxide-λ ⁴ -sulfanilidenecyanamide (1)

[(6-Trifluoromethylpyridin-3-yl) methyl] (methyl) -oxide-λ ⁴ -sulfanilidenecyanamide (1) is converted into 3-chloromethyl-6- (trifluoro Prepared from methyl) pyridine.

To a solution of 3-chloromethyl-6- (trifluoromethyl) pyridine (5.1 g, 26 mmol) in dimethyl sulfoxide (DMSO; 20 mL) was added sodium thiomethoxide (1.8 g, 26 mmol) in one portion. A vigorous exothermic reaction was observed and the reaction became dark. The reaction was stirred for 1 hour and then further sodium thiomethoxide (0.91 g, 13 mmol) was added slowly. The reaction was stirred overnight, after which the reaction was poured into H ₂ O and a few drops of concentrated HCl were added. The mixture was extracted with Et ₂ O (3 × 50 mL) and the organic layers were combined, washed with brine, dried over MgSO ₄ and concentrated. The crude product was purified by chromatography (Prep 500, 10% acetone / hexanes) to give the pale yellow oil sulfide (A) (3.6 g, 67%). ¹ H NMR (300 MHz, CDCl ₃ ): δ 8.6 (s, 1H), 7.9 (d, 1H), 7.7 (d, 1H), 3.7 (s, 2H), 2.0 (s, 3H); GC-MS : Calculated mass of C ₈ H ₈ F ₃ NS [M] ⁺ 207.

To a solution of sulfide (A) (3.5 g, 17 mmol) and cyanamide (1.4 mg, 34 mmol) in dichloromethane (30 mL) at 0 ° C. was added iodobenzenediacetic acid (11.0 g, 34 mmol) in one portion. The reaction was stirred for 30 minutes and then allowed to warm to room temperature overnight. The mixture was diluted with dichloromethane (50 mL) and washed with H ₂ O. The aqueous layer was extracted with ethyl acetate (4 × 50 mL), and the combined dichloromethane and ethyl acetate layers were dried over MgSO ₄ and concentrated. The crude product was triturated with hexane and purified by chromatography (chromatotoron, 60% acetone / hexane) yellow gum sulfilimine (B) (0.60 g 14%). IR (film) 3008, 2924, 2143, 1693 cm ^-1 _; ¹ H NMR (300 MHz, CDCl ₃ ): δ 8.8 (s, 1H), 8.0 (d, 1H), 7.8 (d, 1H), 4.5 ( d, 1H), 4.3 (d, 1H), 2.9 (s, 3H); LC-MS (ESI): Calculated mass of C ₉ H ₉ F ₃ N ₃ S [M + H] ⁺ 248.04. .

To a solution of m-chloroperbenzoic acid (mCPBA; 80%, 1.0 g, 4.0 mmol) in EtOH (10 mL) at 0 ° C. was added K ₂ CO ₃ (1.4 g, 10 mmol) in H ₂ O (7 mL). The solution was added. The solution was stirred for 20 minutes and then a solution of sulfilimine (B) (0.60 g, 2.4 mmol) in EtOH (20 mL) was added in one portion. The reaction was stirred at 0 ° C. for 30 minutes and then allowed to warm to room temperature over 1 hour. The reaction was quenched with aqueous sodium bisulfite and the mixture was concentrated to remove ethanol. The resulting mixture was extracted with dichloromethane and the organic layers were combined, dried over MgSO ₄ and concentrated. The crude product was purified by chromatography (Chromatotron, 50% acetone / hexanes) to give sulfoxyimine (1) (0.28 g, 44%) as an off-white solid. Mp = 135-137 ° C. ¹ H NMR (300 MHz, CDCl ₃ ): δ 8.8 (s, 1H), 8.1 (d, 1H), 7.8 (d, 1H), 4.7 (m, 2H), 3.2 (s, 3H); LC-MS (ELSD): Calculated mass of C ₉ H ₉ F ₃ N ₃ OS [M + H] ⁺ 264.04.

Example II
[1- (6-Trifluoromethylpyridin-3-yl) ethyl] (methyl) -oxide-λ ⁴ -sulfanilidenecyanamide (2)

[1- (6-Trifluoromethylpyridin-3-yl) ethyl] (methyl) -oxide-λ ⁴ -sulfanilidenecyanamide (2) was obtained using the method outlined in Scheme C [(6-Trifluoro Prepared from methylpyridin-3-yl) methyl] (methyl) -oxide-λ ⁴ -sulfanilidenecyanamide (1).

To a solution of sulfoximine (1) (50 mg, 0.19 mmol) and hexamethylphosphoramide (HMPA; 17 μL, 0.10 mmol) in tetrahydrofuran (THF; 2 mL) at −78 ° C. in potassium hexamethyldisilazane (KHMDS; toluene) 0.5M, 420 μL, 0.21 mmol) was added dropwise. The solution was stirred at −78 ° C. for an additional 20 minutes, after which iodomethane (13 μL, 0.21 mmol) was added. The reaction was warmed to room temperature over 1 hour, then quenched with saturated aqueous NH ₄ Cl (aq.) And extracted with dichloromethane. The organic layer was dried over Na ₂ SO ₄ , concentrated and the crude product was purified by chromatography (chromatotron, 70% acetone / CH ₂ Cl ₂ ) sulfoximine (2: 1 mixture of diastereomers (2 ) (Colorless oil; 31 mg, 59%). ¹ H NMR (300 MHz, CDCl ₃ ): δ (main diastereomer) 8.8 (s, 1H), 8.1 (d, 1H), 7.8 (d, 1H), 4.6 (q, 1H), 3.0 (s, (3H), 2.0 (d, 3H); (Sub-diastereomer) 8.8 (s, 1H), 8.1 (d, 1H), 7.8 (d, 1H), 4.6 (q, 1H), 3.1 (s, 3H) , 2.0 (d, 3H); LC-MS (ELSD): Calculated mass of C ₁₀ H ₁₀ F ₃ N ₃ OS [M + H] ⁺ 278.06. Found 278.05.

Example III
2- (6-Trifluoromethylpyridin-3-yl) -1-oxide-tetrahydro-1H-1λ ⁴ -thien-1-ylidenocyanamide (3)

2- (6-Trifluoromethylpyridin-3-yl) -1-oxide-tetrahydro-1H-1λ ⁴ -thien-1-ylidenocyanamide (3) according to the 5-step sequence outlined below, Prepared from chloromethyl-6- (trifluoromethyl) -pyridine.

To a suspension of thiourea (1.2 g, 16 mmol) in EtOH (25 mL) was added a solution of 3-chloromethyl-6- (trifluoromethyl) pyridine in EtOH (10 mL). The suspension was stirred at room temperature for 2 days, during which time a white precipitate formed. The precipitate was filtered to give the desired amidine hydrochloride (2.4 g, 58%) as a white solid. Mp = 186-188 ° C. No further attempt was made to purify the product. ¹ H NMR (300 MHz, CDCl ₃ ): δ 8.9 (bs, 4H), 8.4 (s, 1H), 7.6 (d, 1H), 7.3 (d, 1H), 4.2 (s, 2H); LC-MS (ELSD): Mass calculated for C ₈ H ₈ F ₃ N ₃ S [M + H] ⁺ 236.05.

To a solution of amidine hydrochloride (A) (1.8 g, 6.8 mmol) in H ₂ O (12 mL) at 10 ° C. is added 10N NaOH (0.68 mL, 6.8 mmol) resulting in the formation of a white precipitate. It was done. The suspension was heated at 100 ° C. for 30 minutes and then cooled back to 10 ° C. Additional 10N NaOH (0.68 mL, 6.8 mmol) was added, followed by 1-bromo-3-chloropropane (0.67 mL, 6.8 mmol) in one portion. The reaction was stirred at room temperature overnight and then extracted with dichloromethane. The organic layers were combined, washed with brine, dried over Na ₂ SO ₄ and concentrated to give colorless oil sulfide (B) (1.7 g, 96%). No further attempt was made to purify the product. ¹ H NMR (300 MHz, CDCl ₃ ): δ 8.6 (s, 1H), 7.8 (d, 1H), 7.6 (d, 1H), 3.8 (s, 2H), 3.6 (t, 2H), 2.6 (t , 2H), 2.0 (quintage, 2H).

HMPA (1.7 mL, 10 mmol) was added to a suspension of potassium tert-butoxide (1.5 g, 13 mmol) in THF (12 mL), followed by a solution of sulfide (B) (1.8 g, 6.7 mmol) in THF (3 mL). ) Was added dropwise. The reaction was stirred at room temperature overnight and subsequently concentrated and purified by chromatography (Biotage, 40% EtOAc / hexanes) to give the orange oil cyclic product (C) (230 mg, 15%). ¹ H NMR (300 MHz, CDCl ₃ ): δ 8.7 (s, 1H), 8.0 (d, 1H), 7.6 (d, 1H), 4.6 (dd, 1H), 3.2 (m, 1H), 3.1 (m , 1H), 2.5 (m, 1H), 2.3 (m, 1H), 2.1-1.9 (m, 2H).

To a solution of sulfide (C) (230 mg, 0.99 mmol) and cyanamide (83 mg, 2.0 mmol) in dichloromethane (5 mL) at 0 ° C. was added iodobenzenediacetic acid (350 mg, 1.1 mmol) in one portion. The reaction was stirred for 3 hours, then concentrated, and the crude product was purified by chromatography (Chromatotron, 50% acetone / hexane) orange oil sulfilimine (D) (150 mg, mixture of diastereomers). 56%). ¹ H NMR (300 MHz, CDCl ₃ ): δ 8.8 (s, 1H), 7.9 (d, 1H), 7.8 (d, 1H), 4.8 (dd, 1H), 3.5 (m, 2H), 2.9-2.7 (m, 2H), 2.6 (m, 1H), 2.3 (m, 1H).

To a solution of mCPBA (80%, 180 mg, 0.82 mmol) in EtOH (3 mL) at 0 ° C. was added a solution of K ₂ CO ₃ (230 mg, 1.7 mmol) in H ₂ O (1.5 mL). The solution was stirred for 20 minutes and then a solution of sulfilimine (D) (150 mg, 0.55 mmol) in EtOH (2 mL) was added in one portion. The reaction was stirred at 0 ° C. for 45 minutes, after which the solvent was decanted into a separate flask and concentrated to give a white solid. The solid was slurried in CHCl ₃ , filtered and concentrated to give pure sulfoximine (3) (72 mg, 44%) as a colorless oil. ¹ H NMR (300 MHz, CDCl ₃ ): δ (1.5: 1 mixture of diastereomers) 8.8 (s, 2H), 8.0 (d, 2H), 7.8 (d, 2H), 4.7 (q, 1H) , 4.6 (q, 1H), 4.0-3.4 (m, s, 4H), 3.0-2.4 (m, 8 H); LC-MS (ELSD): C ₁₁ H ₁₁ F ₃ N ₃ OS [M + H] ⁺ the calculated mass 290.06. Found 289.99.

[Example IV]
[(6-Chloropyridin-3-yl) methyl] (methyl) oxide-λ ⁴ -sulfanilidene-cyanamide (4)

[(6-Chloropyridin-3-yl) methyl] (methyl) oxide-λ ⁴ -sulfanilidenecyanamide (4) is prepared according to the same three-step sequence outlined in Example I to give 3-chloromethyl- Prepared from 6-chloropyridine. The product was a white solid. mp = 115-117 ° C. ¹ H NMR (300 MHz, CD ₃ OD / CDCl ₃ ) δ 8.5 (d, 1H), 8.0 (dd, 1H), 7.6 (d, 1H), 5.0 (s, 2H), 3.4 (s, 3H); LC-MS (ELSD): Calculated mass of C ₈ H ₉ ClN ₃ OS [M + H] ⁺ 230. Found 230.

[Example V]
[1- (6-Chloropyridin-3-yl) ethyl] (methyl) oxide-λ ⁴ -sulfanilidene-cyanamide (5)

[1- (6-Chloropyridin-3-yl) ethyl] (methyl) oxide-λ ⁴ -sulfanilidenecyanamide (5) was prepared by the same protocol as described in Example II [[6-Chloropyridine]. Prepared from -3-yl) methyl] (methyl) oxide-λ ⁴ -sulfanilidenecyanamide (4). The final product, isolated as a 3: 2 mixture of diastereomers, was an off-white solid. mp = 155-164 ° C. _{LC-MS (ELSD): C} 9 C 9 ClN 3 OS [M-H] + mass calcd 242. Actual value 242. The diastereomers of (5) can be separated by recrystallization (2: 1 MeOH / H ₂ O), followed by chromatotron chromatography of the supernatant (6) and (7) (stereochemical structure assigned arbitrarily) ) Was brought about.

Compound (6) was isolated as a white solid. mp = 163-165 ° C. ¹ H NMR (300 MHz, CDCl ₃ ): δ 8.4 (d, 1H), 7.9 (dd, 1H), 7.5 (d, 1H), 4.6 (q, 1H), 3.1 (s, 3H), 2.0 (d , 3H); LC-MS (ELSD): Calculated mass of C ₉ H ₁₁ ClN ₃ OS [M + H] ⁺ , 244.

Compound (7) was isolated as a colorless oil. ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.4 (d, 1H), 7.9 (dd, 1H), 7.5 (d, 1H), 4.6 (q, 1H), 3.0 (s, 3H), 2.0 (d, 3H); LC-MS (ELSD): Calculated mass of C ₉ H ₁₁ ClN ₃ OS [M + H] ⁺ , 244. Found 244.

[Example VI]
2- (6-Chloropyridin-3-yl) -1-oxide-tetrahydro-1H-1λ ⁴ -thien-1-ylidenocyanamide (8)

2- (6-Chloropyridin-3-yl) -1-oxide-tetrahydro-1H-1λ ⁴ -thien-1-ylidenocyanamide (8) is prepared according to the same five-step sequence described in Example III. Prepared from 3-chloromethyl-6-chloropyridine. The product was a colorless gum and was a 1: 1 ratio of diastereomers. Diastereomer 1: IR (film) 3439, 3006, 2949, 2194 cm ^-1 ; ¹ H NMR (300 MHz, CDCl ₃ ): δ 8.4 (d, 1H), 7.8 (dd, 1H), 7.4 (d, 1H), 4.6 (dd, 1H), 3.6 (m, 2H), 2.4-2.7 (m, 4H); GC-MS: Calculated mass of C ₁₀ H ₁₁ ClN ₃ OS [M + H] ⁺ 256. Value 256. Diastereomer 2: IR (film) 3040, 2926, 2191 cm ^-1 ; ¹ H NMR (300 MHz, CDCl ₃ ): δ 8.4 (d, 1H), 7.8 (dd, 1H), 7.4 (d , 1H), 4.7 (dd, 1H), 3.8 (ddd, 1H), 3.4 (m, 1H), 2.8 (m, 1H), 2.6 (m, 2H), 2.3 (m, 1H); GC-MS: Calculated mass of C ₁₀ H ₁₁ ClN ₃ OS [M + H] ⁺ 256.

Insecticidal test against the peach aphid (Myzus persicae) using a mixture of sulphoximine and selected insecticides

The following compounds:
A dose-responsive, leaf spray assay was designed and performed to evaluate the synergistic effect of a mixture of spinosad, spinetoram, γ-cyhalothrin, methoxyphenozide, or chlorpyrifos against peach aphids.

  Assay 1: A 1000 ppm master solution was made by dissolving technical material in 1 mg / ml acetone: MeOH (1: 1). For a mixture between two test compounds, combine 0.047 ml of the master solution from each component and dilute 32 × with acetone: MeOH solvent (combine 0.094 ml + solvent 2.906 ml, 15.6 ppm for each. Obtained) and then diluted 5 × with 0.025% Tween 20 in H 2 O (12 ml) to give a 3.125 ppm solution. For the unmixed, the master solution is diluted 64 × with acetone: MeOH (0.047 ml + 2.953 ml solvent, 15.6 ppm is obtained), then diluted 5 × with 0.025% Tween 20 in H 2 O (12 ml) 3 A 125 ppm solution was obtained. For both the mixture and the non-mixture, 4 ml of high concentration (starting from 3.125 ppm) is serially diluted with 12 ml of a diluent consisting of 80 parts of 0.025% Tween 20 in H2O and 20 parts of acetone: MeOH. Thus, low concentrations (0.78, 0.195, 0.049, and 0.012 ppm) were prepared.

  Assay 2: A 1000 ppm master solution was made by dissolving technical material in 1 mg / ml acetone: MeOH (1: 1). For the mixture between compound 2 and compound 3, 4, or 5, combine 0.047 ml of the master solution from each component and add acetone: MeOH (0.094 ml combination + 2.906 ml, 15.15 ml for each. Was diluted 32 × with 0.025% Tween 20 in H 2 O (12 ml) to give a 3.125 ppm solution. In the mixture between compound 2 and compound 6 or 7, combine 0.047 ml of the master solution from compound 2 and 0.752 ml of the master solution from compound 6 or 7 and dilute 3.755 × with acetone: MeOH (0 799 ml combination + solvent 2.201 ml, 15.6 ppm for compound 2 and 250 ppm for compound 6 or 7), then diluted 5 × with 0.025% Tween 20 in H 2 O (12 ml) to give compound 2 A 3.125 ppm solution was obtained for Compound 6 or 7 and a 50 ppm solution was obtained for Compound 6 or 7. For an unmixed solution with compound 2, 3, 4, or 5, the master solution is diluted 64 × with acetone: MeOH (0.047 ml + 2.953 ml solvent, 15.6 ppm is obtained), then H 2 O (12 ml) Diluted 5 × with 0.025% Tween 20 in medium to give a 3.125 ppm solution. For the unmixed solution with compound 6 or 7, the master solution was diluted 3.989 × with acetone: MeOH (0.752 ml + solvent 2.248 ml, yielding 250 ppm), then 0.025% in H 2 O (12 ml) Diluted 5 × with Tween 20 to give a 50 ppm solution. For both mixture and non-mixture, 4 ml of high ratio (starting from 3.125 ppm or 50 ppm) is diluted in 80 parts 0.025% Tween 20 in H2O and 20 parts acetone: MeOH (1: 1). Low concentrations (0.78, 0.195, 0.049, and 0.012 ppm for compounds 2, 3, 4, and 5; 12.5 for compounds 6 and 7 by serial dilution with 12 ml 3.125, 0.78, and 0.195 ppm).

  For both assays 1 and 2, 2-3 small (3-5 cm) true leaf cabbage seedlings grown in 3 inch pots were used as test substrates. The seedlings were infested with 20-50 peach aphids (an adult and cocoon) one day before the chemical application. Four seedlings were used for each treatment. A hand-held Devilsiss nebulizer was used to spray the solution on both sides of the cabbage leaf until it flowed out. Control plants (solvent check) were sprayed with only the diluent. Treated plants were kept in a waiting room at about 23 ° C., RH 40% for 3 days prior to grading. Evaluation was carried out by counting the number of aphids per plant under a microscope. Insecticidal activity, Abbott's correction formula: Corrected% Control = 100 × (XY) / X (where X = number of aphids alive on the solvent check plant, Y = Number of living aphids on the treated plants).

^* Colby formula = 100-((100-% control of compound A) x (100-% control of compound 2)) / 100 (Colby, SR, 1967, Calculating synergistic responses of herbicides combibin. (Weed, Vol. 15, p. 20-22)

Acid and salt derivatives, and solvates (ACID & SALT DERIVATIVES, AND SOLVATES)
The compounds disclosed in the present invention may be in the form of pesticide acceptable acid addition salts.

  According to non-limiting examples, the amine functional groups are hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, acetic acid, benzoic acid, citric acid, malonic acid, salicylic acid, malic acid, fumaric acid, oxalic acid, succinic acid, Salts with tartaric acid, lactic acid, gluconic acid, ascorbic acid, maleic acid, aspartic acid, benzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, hydroxymethanesulfonic acid, and hydroxyethanesulfonic acid may be formed.

  Further, according to non-limiting examples, the acid functional group may form salts including salts derived from alkali or alkaline earth metals, and salts derived from ammonia and amines. Examples of preferred cations include sodium, potassium, magnesium, and aminium cations.

  Salts are prepared by contacting the free base form with a sufficient amount of the desired acid to produce a salt. The free base form can be regenerated by treating the salt with a suitable dilute aqueous base solution such as aqueous dilute NaOH, potassium carbonate, ammonia, and sodium bicarbonate.

  As an example, in many cases, the insecticide is modified to a more water-soluble form (eg, 2,4-dichlorophenoxyacetic acid dimethylamine salt is the well-known herbicide 2,4-dichloro A more water-soluble form of phenoxyacetic acid).

  The compounds disclosed in the present invention may form stable complexes with solvent molecules that remain intact after removal of unconjugated solvent molecules from the compound. Such complexes are often referred to as “solvates”.

Stereoisomers (STEREOISOMERS)
Certain compounds disclosed in the present invention can exist as one or more stereoisomers. Various stereoisomers include geometric isomers, diastereomers, and enantiomers. Accordingly, the compounds disclosed in the present invention include racemic mixtures, individual stereoisomers, and optically active mixtures.

  One skilled in the art will understand that certain stereoisomers may be more active than other stereoisomers. Individual stereoisomers and optically active mixtures can be obtained by selective synthetic procedures, by conventional synthetic procedures with separated starting materials, or by conventional resolution procedures.

PESTS
In another embodiment, the invention disclosed herein can be used to control pests.

  In another embodiment, the invention disclosed herein can be used to control Phylum Nematoda pests.

  In another embodiment, the invention disclosed herein can be used to control Phylum Arthropoda pests.

  In another embodiment, the invention disclosed herein can be used to control Subphylum Chelicerata pests.

  In another embodiment, the invention disclosed herein can be used to control pests of the class Arachnida.

  In another embodiment, the invention disclosed herein can be used to control Subphylum Myriapoda pests.

  In another embodiment, the invention disclosed herein can be used to control Class Symphyla pests.

  In another embodiment, the invention disclosed herein can be used to control Subphylum Hexapoda pests.

  In another embodiment, the present invention disclosed herein can be used to control Class Insecta pests.

  In another embodiment, the invention disclosed herein can be used to control Coleoptera (beetles). A non-exhaustive list of these pests includes, but is not limited to, Acanthoscelides spp. (Weevil), Acanthoscelides obectus (Harius weevil), Agrilus prapennis (Aoraga beetle), Agriotes spp. (Rice beetle), Anoplophora glabripennis (Anthropis cricket), Anthonomus spp. (Weevil), Anthonomus grandis (Watami weevil), Aphidius spp. , Apion spp. (Weevil), Apogonia spp. (Uzi), Ataenius spretulus (Black Turgeras Ataenius), Atomaria linearis (pygmy mango beetle), Auracophore spp. Bothynoderes puntiveris (beet root wevil), Bruchus spp. (Weevil), Bruchus pisorum (pea weevil), Cacoesia spp. Callosobruchus maculatus, Carpophilus hemopteras, Cassida vittata, Cerostanna spp. Cerotoma spp. (Potato beetle), Cerotoma trifurcata (bean leaf beetle), Ceutorhynchus spp. (Weevil), Ceutorhynchus assimilis (cabbage seedpod wevil), Ceutorhynchus napi (cabbage curculio), Chaetocnema spp. (Potato beetle), Collaspis spp. (Soil beetle), Conoderus scalaris, Conoderus stigmosus, Conotrachelus nenuphar (plum weevil), Cotinus nitidis (Green June beetle), Crioceris asparagi (asparagus neck Naga beetle), Cryptolestes ferrugineus (rust Kaku breast grain beetle), Cryptolestes pusillus (Kakumune Slat beetle), Cryptolestus turicus (Turkey scallop), Ctenicera spp. (Click beetle), Curculio spp. (Weevil), Cyclocephala spp. (Uji), Cylindropturus adspersus (sunflower stem wevil), Deporous marginatus (mango leaf-cutting weibill), Dermests lardus sturm (Obikatsushimushi) (Potato beetle), Epilacna varivestis (green beans), Faustinus cubae, Hyrobius pales (pales weevil), Hypera spp. (Weevil), Hypera postica (Alfalfa weevil), Hyperdoes spp. (Osae weevil), Hypothenemus hampei (Coffea flea), Ips spp. (Coleoptera), Lasioderma serricorne, Leptinotarsa decemlineata (Colorado beetle), Liogenys fuscus, Liogenys suturis, Lissohoptrusus olizophyllus pylori (Stained Beetle / Spiral Beetle), Maecolaspis joliveti, Megascelis spp. Melanotus communis, Meligethes spp. , Meligethes aeneus (blossom beetle), Melolontha melolontha (common European cockchafer), Oberea brevis, Oberea linearis, Oryctes rhinoceros (date palm beetle), Oryzaephilus mercator (multiview sawtooth grain beetle), Oryzaephilus surinamensis (Saw grain beetle), Otiorhynchus spp. (Weevils), Oulema melanopus (Coleoptera cricket), Oulema oryzae, Pantomorus spp. (Weevil), Phyllophaga spp. (May / June beetle), Phyllophaga cuybana, Phyllotreta spp. (Potato beetle), Phynchites spp. Poplaria japonica, Prostephanus trancates, Rhizopertha dominica, Rhizotrogus spp. (Kofukikogane), Rhynchophorus spp. (Weevil), Scolytus spp. (Stained Beetle), Shenophorus spp. (Osaka weevil), Sitona lineatus (Red-tailed weevil), Sitophilus spp. (Butterfly weevil), Sitophilus granaries (Granaria weevil), Sitophilus oryzae (Still beetle), Stegobium panicium, Tribolium spp. (Four beetle), Tribolium castaneum, Tribolium confusum, Troderma variabile, and Zaburid teneb.

  In another embodiment, the invention disclosed herein can be used to control Dermaptera (earwigs).

  In another embodiment, the invention disclosed herein can be used to control Dictyoptera (cockroaches). The non-exhaustive list of these pests includes, but is not limited to, Blattella germanica (Brown cockroaches), Blattella orientalis (Rossel cockroaches), Parcobrata pennylla nica, Periplanet america Crocodiles), Periplaneta fuliginosa, Pyncoselus suninamensis, and Superella longipalpa.

  In another embodiment, the invention disclosed herein can be used to control Diptera (true flies). A non-exhaustive list of these pests includes, but is not limited to, Aedes spp. (F), Agromyza frontella (alfalfa blotch leafminer), Agromyza spp. (Clam fly), Anastrepha spp. (Flyflies), Anastrepha suspensa (Caribbean fruit flies), Anopheles spp. (F), Batrocera spp. (Flyflies), Bacterocera cucurbitae (Flyflies), Bactrocera dorsalis (Cultiva), Ceratitis spp. (Flyflies), Ceratitis capitata (Chrysalis flies), Chrysops spp. (Abu), Cochliomyia spp. (Golden fly), Contarinia spp. (Tall fly), Culex spp. (F), Dasineura spp. (Tamaflies), Dasineura brassicae (Daeconta flies), Delia spp. , Delia platera (Drosophila), Drosophila spp. (Drosophila), Fannia spp. (Flyfly), Fannia canarisalis, Fannia scararis, Gasterophilus intestinalis, Gracilia perseae, Haematobiasae. (Neak beetle), Hypoderma lineatum (Liquididae), Liriomyza spp. (Spotted fly), Liriomyza brassica (bean winged fly), Melophagas ovinus (sheep ked), Musca spp. (Housefly), Musca autumalis (face fly), Musca domestica (housefly), Oestrus ovis (sheep fly), Oscinella frit (flies fly), Pegomia betae (be) p. , Psila rosae (carrot fly), Rhagoletis cerasi (Flyflies), Rhagoletis pomonella, Sitodiplosis mosella (Smale caterpillar), Stomoxys sp. (Fountain), and Tipula spp. Is included.

  In another embodiment, the invention disclosed herein can be used to control Hemiptera (true bug). A non-exhaustive list of these pests includes, but is not limited to, Acrostern hillare (green stick bug), Blissus leucopterus (Coleoptera crisp), Calocoris norvegicus (Potato mirimu), Cimito cinp electrarius (bedbug), Dagbertus fascituus, Dichelops furcatus, Dysdercus suturellus (cotton stainer), Edessa medidubunda, Eurygaster maura (cerealus) tus servus (brown stink bug), Helopeltis antonii, Helopeltis theivora (tea blight plantbug), Lagynotomus spp. (Stink bugs), Leptocorisa oratorius, Leptocorisa varicornis, Lygus spp. (Molecula beetle), Lygus hesperus (Western tannised plant bug), Macconellicoccus hirsutus, Neurocolpus longirostris, Nezara viridula, Minamio spruce c. (Phytocoris californicus, Phytocoris relativus, Piezodorus aspira pu s a s p e s p e s e n e p e s e p e n e p e s e p e n e p e s e p e n e p e n e n a p e n e p e n a p e n e p e n e n e n e p e n e n e p e n e n e p e n e n e p e n. (Heading Turtle / Squid Turtle) is included.

  In another embodiment, the invention disclosed herein may be used to control Homoptera (aphids, scales, whiteflies, leafhoppers) it can. A non-exhaustive list of these pests includes, but is not limited to, Acrythosiphon pisum, Adelges spp. (Casa aphid), Aleurodes proletella (cabbage whitefly), Aleurodicus disperses, Aleuthotricus floccusus (Woolley whitefly), Aluacaspis spp. , Amrasca bigutella bigutella, Aphrophora spp. (Leaf beetle), Aonidiella aurantii (Aphididae), Aphis spp. (Aphids), Aphis gossapii (coton aphid), Aphis pomi (apple aphids), Aulacorthum solani (potato aphids), Bemisia spp. (Whiteflies), Bemisia argentifolii, Bemisia tabaci (Tobacco whitefly), Brachycolus noxius (Russian aphid), Brachycorinella asparagium (asparagus) (Scale insect), Ceroplasts rubens (ruby wax scale), Chionaspis spp. (Scale insect), Chrysomphalus spp. (Scale insect), Cocus spp. (Scale insects), Dyphaphis plantaginea (Lepidoptera: Coccoliidae), Empoasca spp. (Leaf beetle), Eriosoma lanigerum (apple beetle), Icerya purchasi (Iseria scale), Idioscopus nidudurus (mango leafhopper), Laodelphax straphidos, Himetobipo sp. Macrosiphum spp. , (Macrosiphum euphorbiae (potato aphid), Macrosiphum granarium (wheat aphid), Macrosiphum rosae (thorns aphid), Macrosteles quadrilineatus (aster leafhopper), Mahanarva frimbiolata, Metopolophium dirhodum (rose grain aphid), Mictis longicornis, Myzus persicae ( Peach aphid), Nephotettis spp. (Leaf beetle), Nephotettix cintipes (leaf beetle), Nilaparvatta lugens (Tobii) Rounka), Parlatoria pergandii (chaff scale), Parlatoria ziziphi (ebony scale), Peregrinus maidis corn delphacid, Philaenus spp. (Spittle bugs), Phylloxera vitifoliae (grape phylloxera), Physokermes piceae (spruce bud scale), Planococcus spp. (Mealybug ), Pseudococcus spp., Pseudococcus brevipes, Pinedra spidiiotus perniciosus, San Jose scale. Rhapalosiphum spp. (Aphid), Rhapalosiphum maida (corn leaf aphid), Rhapalosiphum padi (oat bird-cherry aphid), Saissetia spp. (Scale insects), Saissetia oleae (black scale), Schizaphis graminum (wheat green aphid), Sitobion avenae ( English grain aphid), Sogataella furcifera (Shiroloka), Therioophis spp. (Aphid), Tomeyella spp. (Scale insect), Toxoptera spp. (Aphids), Trialeurodes spp. (Whitefly), Trialeurodes vaporiorum (Onshirako whitefly), Trialeurodes abutilenes (bandedwing whitefly), Unaspis spp. (Scale scales), Unaspis yanonensis (scale scales), and Zulia enterriana.

  In another embodiment, the invention disclosed herein can be used to control Hymenoptera (ants, wasps, and bees). A non-exhaustive list of these pests includes, but is not limited to, Acrymyrmex spp. , Atari Rosae, Atta spp. (Hachiriari), Camponotus spp. (Giant ant), Diprion spp. (Hachibee), Formica spp. (Ant), Iridomyrex humilis (Argentina ant), Monomorium spp. , Monomorium minimum (little black ant), Monomorium phalaonis (Pharaoh Ali), Neodipion spp. (Bee), Pogonomymex spp. (Shukakari), Polistses spp. (Apidae), Solenopsis spp. (Camiari), Tapinooma sessile (odorous house ant), Tetanomorium spp. (Pavement ant), Vespula spp. (Wasp), and Xylopopa spp. (Bumblebee) is included.

  In another embodiment, the present invention disclosed herein can be used to control Isoptera (termites). A non-exhaustive list of these pests includes, but is not limited to, Coptothermes spp. , Copttermes curvignathus, Coptothermes frenchii, Coptothermes formosanus (Formosan subterranean termite), Cornitermes spp. (Nause termite), Cryptometers spp. (Kansai termites), Heterotermes spp. (Desert subterranean term), Heterotermes aureus, Karotermes spp. (Termite termites), Incisitermes spp. (Kansai termite), Macrotermes spp. (Fungus growing termite), Marginitemes spp. (Kansai termites), Microceremes spp. (Harvester term), Microtermes obesi, Procornermites spp. Reticulitermes spp. (Subterranean termite), Reticulitermes banyulensis, Reticulitermes grassei, Reticulitermes flavipes (eastern subterranean termite), Reticulitermes hageni, Reticulitermes hesperus (western subterranean termite), Reticulitermes santonensis, Reticulitermes speratus, Reticulitermes tibialis, Reticulitermes virginicus, Schedorhinotermes spp. , And Zootermosis spp. (Rotten-wood term).

  In another embodiment, the invention disclosed herein can be used to control Lepidoptera (moths and butterflies). A non-exhaustive list of these pests includes, but is not limited to, Achoea janata, Adoxophys spp. Adoxophys orana, Agrotis spp. (Armyworm), Agrotis ipsilon (black cutworm), Alabama argillacea (cotton leafworm), Amorbia cuneana, Amyelosis transitella (navel orangeworm), Anacamptodes defectaria), Anarsia lineatella (Momokibaga), Anomis sabulifera (jute looper), Anticarsia gemmatalis (velvetbean caterpillar) , Archips argyrospira (fruittree leafroller), Archips rosana (rose leaf roller), Argyrotania pp. (Angiospermia), Argyrotaenia citrana (Ranunculaceae), Autographa gamma, Bonagota cranaodes, Borbo cinnalo (tillfish), Bucculatrix thurberiperp. (Buprestidae), Caputa reticulana), Carposina nipponensis (Peach moth), Chilo spp. , Chlumetia transversa (Mangofusayaga), Choristoneura rosaceana (Husobihamaki), Chrysodeixis spp. Cnaphacerus medinalis (glass leafroller), Collias spp. , Commorpha kramerella, Cossus cossus (carter moth), Crambus spp. (Sod website), Cydia funebrana (Prunus spp.), Cydia molesta (Pear moth), Cydia nignana (Pea moth), Cydia pomonella (codlinga), Darna, co. (Stem borer), Diatraea spp. (Stalk borer), Diatraea saccharalis (sugarcane borer), Diatraea graniosella (southwester corn borer), Earias spp. (Watakibaga), Earias insulata (Egyptian bollworm), Earias vitella (rough northern bollworm), Ecdytopopha aurantianum, Elasmopalpus lignosellus (sorghum moth), Epiphysias postruttana (light brown apple moth), Ephestia spp. (Floor moth), Ephestia cautella (Shiromadara maiga), Ephestia elutella (Chamadala maiga), Ephesia kühniella (Sujikonamara maiga), Epimeces spp. , Epinotia aporema, Erionota thrax (Togari banana seri), Eupoecilia abiguella (Grape Hosohamaki), Euxoa auxiliaris (army cutworm), Feltia spp. (Nechirimushi), Gortyna spp. (Stemborer), Grapholita molesta (Nashihime Shinkui), Heylepta indicator (bean leaf webber), Helicoverpa spp. (Yaga), Helicoverpa armigera (Otobacco moth), Helicoverpa zea (bollworm / corn earrm), Heliothis spp. (Yaga), Heliothis virescens (Tobacco moth), Hellula undalis (Hydra medicae), Indarbela spp. (Root borer), Keiferia lycopersicella (Tomato Gyochu), Leucinodes orbonalis (Nasnomeiga), Leucoptera malifoliella, Lithocollectis spp. , Lobesia botrana (graphe fruit moth), Loxagrotis spp. (Yaga), Loxagrotis albicosta (Western bean cutworm), Lymantria dispar (Maiiga), Lyonetia clarkella (Gimmon hosoga), Mahasena corbetta, Mole palmpo. (Tenmakukemushi), Mamestra brassicae (cabbage armyworm), Maruca testulalis (legume pod borer), Metisa plana (Minoga), Mythimna unipuncta (true armyworm), Neoleucinodes elegantalis (small tomato borer), Nymphula depunctalis (rice caseworm), Operophthera brumata (winter moth) , Ostrinia nubilalis, Oxydia vesulia, Pandemis cerasana, Pandemis heparana (brown apple tortrix), Pap lio demodocus, Pectinophora gossypiella (Watakibaga), Peridroma spp. (Coleoptera), Peridroma saucia (Niseta Manayaga), Perileucoptera coffella (White coffee leafaminer), Phthorimaea percylella. (Hamogurimushi), Pieris rapae (imported cabbageworm), Plathypena scabra, Plodia interpunctella (Indian meal moth), Plutella xylostella (diamondback moth), Polychrosis viteana (grapes Hime moth), Prays endocarpa, Prays oleae (olive moth), Pseudaletia spp. (Yaga), Pseudoletia unipunctata, Pseudoplusia inclusions (Soybean looper), Rachiplusia nu, Scirophaga incertulas, Sesamispasse sp. (Stemborer), Sesameia inferens, Sesamia nonagrioides, Setora nitens, Sittroga cerialella (Bakuga), Spaganothis pillariana, Spodopoter. (Awayoto), Spodoptera exigua (Shirochimonmontoto), Spodoptera fugiperda (fall armyworm), Spodoptera oridania (southern armyworm), Synpanthed. (Root borer), Thecla basilides, Thermisia gemmatalis, Tinola bisselliella (Coiga), Trichoplusia ni (Iracusaginawaba), Tuta absoluta, Yponomespap. , (Zeuzera coffeae), and Zeuzera pyrina (leopard moth).

  In another embodiment, the invention disclosed herein can be used to control Mallophaga (chewing lice). Non-exhaustive listings of these pests include, but are not limited to, Bovicola ovis (sheep lice), Menacanthus stramineus (chicken lice), and Menopon gallinea (common hen house).

  In another embodiment, the invention disclosed herein can be used to control Orthoptera (grasshoppers, locusts, and crickets). A non-exhaustive list of these pests includes, but is not limited to, Anabrus simplex, Gryllotalpidae (Kera), Locusta migratoria, Melanoplus spp. (Grasshopper), Microcentrum retinave (angularwinged katydid), Pterophylla spp. (Grasshopper), chistocerca gregaria, Scudderia furcata (forktailed bush katidid), and Valanga nigricorni.

  In another embodiment, the invention disclosed herein can control Phythiraptera (sucking lice). A non-exhaustive list of these pests includes, but is not limited to, Haematopinus spp. (Cattle and hog lics), Linognatus ovillus (sheep louse), Pediculus humanus capitis (head lice), Pediculus humus humanus (cold lice), and Pthulus burs.

  In another embodiment, the present invention disclosed herein can be used to control fleas (Siphonaptera) (fleas). A non-exhaustive list of these pests includes, but is not limited to, Ctenocephalides canis, Ctenocephalides felis, and Pulex irritans.

  In another embodiment, the invention disclosed herein can be used to control Thysanoptera (thrips). A non-exhaustive list of these pests includes, but is not limited to, Frankliniella fusca (tobacco thrips), Frankliniella occidentalis (western flower thrips), Frankliniella shultzei, Frankliniella williamsi (corn thrips), Heliothrips haemorrhaidalis (greenhouse thrips), Riphiphorothrips clientitus), Scirtotrips spp. , Scirtotrips citri (citrus trips), Scirtotrips dorsalis, Taeniotrips rhopalantenalis, and Trips spp. Is included.

  In another embodiment, the invention disclosed herein can be used to control Thysanura (bristletails). A non-exhaustive list of these pests includes, but is not limited to, Lepisma spp. (Stain) and Thermobia spp. (Madara Shimi) is included.

  In another embodiment, the invention disclosed herein can be used to control Acarina (mites and ticks). A non-exhaustive list of these pests includes, but is not limited to, Acarapsis woody (tracheal mite of honeybees), Acarus spp. (Food mites), (Acarus siro (acarid mites), Aceria mangiferae (mango bud mite), Aculops spip. Ambrioma), Boophilus spp. (Tick), Brevipalpus obovatus (private mite), Brevipalpus phoenitis (red and black flat mite), Demodex spp. (Mite mite), Dermacentor variabilis (American Indigo Tick), Dermatophagoides pteronyssinus (Mite mite), Eottranycus spp., E. tetany es p, p , Notoderes cati, Oligonychus spp., Oligonychus coffee, Oligonychus ilicus (southern red mite), Panonychus spp., (Pananychus citri) Panonychus ulmi (Ringohadani), Phyllocoptruta oleivora (citrus rust mite), Polyphagotarsonemun latus (Chanohokoridani), Rhipicephalus sanguineus (Rhipicephalus sanguineus), Rhizoglyphus spp. (Nedani), Sarcoptes scabiei (mange mites), Tegolophus perseaflorae, Tetranychus spp., Tetranychus urticae, and Varroa destructor are included.

  In another embodiment, the invention disclosed herein can be used to control Nematoda (nematodes). A non-exhaustive list of these pests includes, but is not limited to, Aphelenchoides spp. (Bud and leaf & pinewood nematode), Belonolaimus spp. (Sting nematode), Critonemella spp. (Ring nematode), Dirofilaria immitis (dogworm), Ditylenchus spp. (Stem and bulb nematode), Heterodera spp. (Cyst nematode), Heterodera zeae (corn cyst nematode), Hirschmanniella spp. (Root nematode), Hopolaimus spp. (Lance nematode), Meloidogyne spp. (Root-knot nematode), Meloidogyne incognita (root-knot nematode), Onchocerca volvulus (rotated filamentous worm), Pratylenchus spp. (Nexale nematode), Radophorus spp. (Nemoglycenchu), and Rotylenchus reniformis (kidney-shaped nematode).

  In another embodiment, the invention disclosed herein can be used to control Symphyla (symphylans). A non-exhaustive list of these pests includes, but is not limited to, Scutigella imamaculata.

  For more information, see Arnold Mallis, “Handbook of Pest Control-The Behavior, Life History, and Control of Household Pests”, 9th Edition, Copyright 2004, GIE Media.

Mixtures
Some of the insecticides that can be advantageously used in combination with the invention disclosed herein include, but are not limited to, the following.
1,2 dichloropropane, 1,3 dichloropropene,
Abamectin, acephate, acequinosyl, acetamiprid, acethione, acetoprole, acrinatrin, acrylonitrile, alanic carb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, alixicarb, α-cypermethrin, α-ecdysone, amidithionamidocarbido Anabasine, arsenic trioxide, atidachione, azadilactin, azamethiphos, azinephosethyl, azinephosmethyl, azobenzene, azocyclotin, azotoate,
Hexafluorosilicate barium, barthrin, bencrothiaz, bendiocarb, benfuracarb, benomyl, benoxafos, bensultap, benzoximate, benzyl benzoate, β-cyfluthrin, β-cypermethrin, biphenazate, bifenthrin, binapacryl, bioaresulin, bioethanomethrin, bioethanomethrin Permethrin, bistrifluron, borax, boric acid, bromofenvin fos, bromo DDT, bromocyclene, bromophos, bromophosethyl, bromopropylate, bufencarb, buprofezin, butacarb, butathiophos, butocarboxyme, butonate, butoxycarboxym,
Cadusafos, calcium arsenate, calcium polysulfide, camfechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothione, carbosulfan, cartap, quinomethionate, chlorantranylprole, chlorbenside, chlorbicyclene, Chlordan, Chlordecone, Chlordimeform, Chlorethoxyphos, Chlorfenapyr, Chlorphenetol, Chlorfenson, Chlorfensulfide, Chlorfenvinphos, Chlorfluazuron, Chlormefos, Chlorobenzylate, Chloroform, Chloromebform, Chloromethyurone, Chloropicrine , Chloropropylate, Chloropoxime, Chlorprazophos, Chlorpyrofos, Chlorpyrofosmethyl, Chlorthiofos, Chroma Enozide, Cineline I, Cineline II, Cismethrin, Chloetocarb, Clofentadine, Crosanthine, Clothianidin, Cupric arsenous arsenite, Copper arsenate, Copper naphthenate, Copper oleate, Coumafos, Cumitoate, Crotamiton, Crotoxyphos, cruenthalenes A and B, culfomate, cryolite, cyanophenphos, cyanophos, cyanatoate, cicletrin, cycloprotorin, sienopyrafen, cyflumethofene, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, ciphenothrin, cyromazine, cythioate,
d-limonene, dazomet, DBCP, DCIP, DDT, decarbofuran, deltamethrin, demefion, demefion O, demefion S, demeton, demeton methyl, demeton O, demeton O methyl, demeton S, demeton S methyl, demeton S methyl sulfone, diaphene Thiuron, diarifos, diamidafos, diazinon, dicapton, diclofenthion, diclofluanide, dichlorvos, dicophore, dicresyl, dicrotofos, dicyclanil, dierdoline, dienochlor, difluvidazine, diflubenzuron, dirol, dimethortoline, dimetholine, dimetholine, dimetholine , Dimethylvinphos, dimethylane, dinex, dinobutone, zinocup, dinocup 4, dinocup 6, Nokuton, Jinopenton, Jinopuroppu, Jinosamu, Jinosurufon, dinotefuran, Jinoterubon, diofenolan, dioxazine benzo Foss, Jiokisakarubu, DIOXATHION, diphenyl sulfone, disulfiram, Jisurufoton, Jichikurohosu, DNOC, Dofenapin, doramectin,
Ecdysterone, emamectin, EMPC, empentrin, endosulfan, endothione, endrin, EPN, epofenonane, eprinomectin, esfenvalerate, etaphos, etiophencarb, ethion, ethiprole, ethoate methyl, etoprophos, ethyl DDD, ethyl formate, ethylene dibromide , Ethylene dichloride, ethylene oxide, etreneprox, etoxazole, etrimphos, EXD,
Famfur, fenamifos, fenazaflor, fenazaquin, fenbutatin oxide, fenchlorphos, phennetacarb, fenfluthrin, fenitrothion, fenobucarb, phenothiocarb, phenoxacrime, phenoxycarb, fenpyrithrin, fenpropatoline, fenpyroximate , Fenson, Fensulfothione, Fentione, Fentioneethyl, Fentriphanyl, Fenvalerate, Fipronil, Flonicamid, Fluacrylpyrim, Fluazuron, Flubendiamide, Flubenzimine, Flucofuron, Flucycloxuron, Flucitrinate, Fluenetil, Fluphenelon , Flufenprox, flumethrin, fluorbenside, flubenside Valinate, fonofos, formetanate, formothion, Holm para sulphonate (formparanate), Hosumechiran, Hosupireto (fospirate), fosthiazate, fosthietan, fosthietan, furathiocarb, Furesurin, furfural,
γ-cyhalothrin, γHCH,
Halofenprox, halofenozide, HCH, HEOD, heptachlor, heptenophos, heterophos, hexaflumuron, hexythiazox, HHDN, hydramethylnon, hydrogen cyanide, hydroprene, hyquincarb,
Imisiaphos, imidacloprid, imiprothrin, indoxacarb, iodomethane, IPSP, isamidophos, isazophos, isobenzan, isocarbophos, isodoline, isofenphos, isoprocarb, isoprothiolane, isothioate, isoxathion, ivermectin,
Jasmolin I, jasmolin II, jodfenphos, juvenile hormone I, juvenile hormone II, juvenile hormone III,
Keleban, Kinoprene,
λ cyhalothrin, lead arsenate, lepimectin, leptophos, lindane, lirimfos, lufenuron, ritidathione,
Malathion, malonoben, majidox, mecarbam, mecarphone, menazone, mephospholane, mercuric chloride, mesulfen, methulfenphos, metaflumizone, metam, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methomil, methoprene Methoxyphenozide, methyl bromide, methyl isothiocyanate, methyl chloroform, methylene chloride, metfurthrin, metorcarb, methoxadiazone, mevinphos, mexacarb, milbemectin, milbemycin oxime, mipafox, mirex, MNAF, monocrotophos, morphothion, Moxidectin,
Naphthalophos, naredo, naphthalene, nicotine, niflulidide, nikkomycin, nitenpyram, nithiazine, nitriracarb, nobarulone, nobiflumuron,
Ometoate, oxamyl, oxydemetone methyl, oxydeprophos, oxydisulfotone,
Paradichlorobenzene, parathion, parathion methyl, penflurone, pentachlorophenol, permethrin, fencapton, phenothrin, phentoate, folate, hosalone, phospholane, phosmet, phosnichlor, phosphamidone, phosphine, phosphocarb, oxime, phoximephos, pyrimicarb, Pirimiphosethyl, pyrimifosmethyl, potassium arsenite, potassium thiocyanate, pp'DDT, praletrin, plecocene I, plecocene II, plecocene III, primidophos, prochronol, propenophos, profluthrin, promacyl, promecarb, propaphos, propargite, propetanephos, propoxur , Procidathione, Prothiophos, Protoate, Protolife But-, pyraclofos, pyrafluprole, pyrazophos, Piresumetorin, pyrethrin I, pyrethrin II, pyridaben, pyridalyl, pyridaphenthion, pyrifluquinazon, pyrimidifen, Pirimiteto (pyriminate), pyriprole, pyriproxyfen,
Cassia, quinalphos, quinalphos, quinalphosmethyl, quinothion, quantifies,
Rafoxanide, resmethrin, rotenone, riania,
Sabadilla, shuradan, ceramectin, silafluophene, sodium arsenite, sodium fluoride, sodium hexafluorosilicate, sodium thiocyanate, sofamid (sophamide), spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulcofuron, Sulfiram, sulframide, sulfotep, sulfur, sulfuryl fluoride, sulfrophos,
Taufulvalinate, tadimcarb, TDE, tebufenozide, tebufenpyrad, tebupyrimphos, teflubenzuron, tefluthrin, temefos, TEPP, teraretrin, terbufos, tetrachloroethane, tetrachlorobinphos, tetradiphone, tetramethrin, tetranactin, tetrasul, θ cypermethothiline, thiaclopridam Thicrofos, thiocarboxyme, thiocyclam, thiodicarb, thiophanox, thiometone, thionazine, thioquinox, thiosultap, thuringiensin, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, trialatin, triazamate , Trichlorphone, trichlormetaphos 3 (trichl ormetaphos 3), trichloronat, trifenophos, triflumuron, trimetacarb, triprene,
Bamidithione, bamidithione, vaniliprole, vaniliprole
XMC, Xilicarb,
ζ cypermethrin, and zolaprophos are included.

  In addition, any combination of the above insecticides can be used.

  The invention disclosed herein can also be used with herbicides and fungicides for both economic and synergistic reasons.

  The invention disclosed herein can be used for economic and synergistic reasons, antimicrobial agents, bactericides, defoliants, safeners, synergists, algicides, attractants, desiccants, pheromones, repellents. It can also be used with agents, animal immersion fluids, birdicides, disinfectants, signaling chemicals, and molluscicides (these classifications are not necessarily mutually exclusive).

  For further information, see http: // www. alanwood. net / pesticides / index. Please refer to “Compendium of Pesticide Common Names” in html. See also CD S. Tomlin, Copyright 2006, British Crop Production Council, “The Pesticide Manual”, 14th edition.

SYNERGISTIC MIXTURES
The invention disclosed herein can be used with other compounds such as those mentioned under the heading “Mixtures” to form synergistic mixtures in which the mechanism of action of the compounds in the mixture is the same, similar, or different. can do.

  Examples of mechanisms of action include, but are not limited to, acetylcholinesterase inhibitors, sodium channel modulators, chitin biosynthesis inhibitors, GABA-gated chloride channel antagonists, GABA and glutamate-gated chloride channel agonists Acetylcholine receptor agonists, MET I inhibitors, Mg-stimulated ATPase inhibitors, nicotinic acetylcholine receptors, midgut disruptors, and oxidative phosphorylated disruptors.

  In addition, the following compounds are known as synergists and can be used with the invention disclosed herein: piperonyl butoxide, piperotal, propyl isome, sesamex, sesamolin, and sulfoxide.

Formulations
Insecticides are hardly suitable for application in their pure form. It is usually necessary to add other substances so that the pesticide can be used in the required concentration and in a suitable form to allow for application, handling, transport, ease of storage, and maximum insecticidal action. is there. Thus, pesticides are, for example, bait, concentrated emulsions, dust, emulsifiable concentrates, fumigants, gels, granules, microencapsulation, seed treatment, suspension concentrates, suspoemulsions, tablets, water-soluble Formulated in solutions, water-dispersible granules or dry flowables, wettable powders, and very small volume solutions.

  For further information on formulation types, see “Catalogue of pesticide formulation types and international coding system”, Technical Monograph 2, 5th edition, CropLife International (2002).

  Insecticides are most often applied as aqueous suspensions or emulsions prepared from concentrated formulations of such insecticides. Such water-soluble, water-suspendable or emulsifiable preparations are solids or emulsifiable concentrates or aqueous suspensions commonly known as wettable powders or water-dispersible granules. Any of the liquids commonly known as liquids. Wettable powders that may be condensed to form water-dispersible granules include a homogeneous mixture of insecticide, carrier, and surfactant. The concentration of the insecticide is usually from about 10% to about 90% by weight. The carrier is usually selected from attapulgite clay, montmorillonite clay, diatomaceous earth, or pure silicate. Effective surfactants containing from about 0.5% to about 10% wettable powders include non-sulfated lignins, concentrated naphthalene sulfonates, naphthalene sulfonates, alkyl benzene sulfonates, alkyl sulfates, and ethylene oxide adducts of alkyl phenols. Found in ionic surfactants.

  An emulsifiable concentrate of insecticide dissolves from about 50 to about 500 grams per liter of liquid in a carrier that is either a water miscible solvent or a mixture of water immiscible organic solvent and emulsifier. Convenient levels of pesticides are included. Useful organic solvents include aromatics, particularly xylenes and petroleum fractions, especially the high boiling naphthalene and olefinic portions of petroleum such as aromatic heavy naphtha. Other organic solvents such as terpene solvents including rosin derivatives, aliphatic ketones (eg, cyclohexanone), and complex alcohols (eg, 2-ethoxyethanol) may also be used. Suitable emulsifiers for the emulsifiable concentrate are selected from conventional anionic and nonionic surfactants.

  Aqueous suspensions include suspensions of water-insoluble insecticides dispersed in an aqueous carrier at concentrations ranging from about 5% to about 50% by weight. The suspension is prepared by finely grinding the insecticide and mixing vigorously in a carrier consisting of water and surfactant. Inorganic salts and components such as synthetic or natural rubber can also be added to increase the density and viscosity of the aqueous carrier. It is often most effective to simultaneously grind and mix the pesticides by preparing a mixed aqueous solution and homogenizing in an instrument such as a sand mill, ball mill, or piston type homogenizer.

  Insecticides may be applied as a granular composition that is particularly useful for application to soil. Granule compositions typically contain from about 0.5% to about 10% by weight of an insecticide dispersed in a carrier containing clay or similar material. Such compositions are usually prepared by dissolving an insecticide in a suitable solvent and applying it to a preformed granule carrier that is pre-formed to a suitable particle size ranging from about 0.5 mm to 3 mm. The Such compositions can also be formulated by making a dough or paste of the carrier and compound, crushing and drying to obtain the desired granule particle size.

  The dust containing the pesticide is prepared by intimately mixing the pesticide in powder form with a suitable dusty agricultural carrier such as kaolin clay, ground volcanic rock. The dust may suitably contain from about 1% to about 10% insecticide. These can be applied in dust blower equipment as seed dressing or as leaf applications.

  It is equally practical to apply an insecticide in the form of a solution in a suitable organic solvent (usually petroleum, such as spray oil, widely used in agricultural chemistry).

  Insecticides may be applied in the form of an aerosol composition. In such compositions, the insecticide is dissolved or dispersed in a carrier which is a pressure generating propellant mixture. The aerosol composition is packaged in a container from which the mixture is dispersed through a spray valve.

  Insecticide baits are formed when an insecticide is mixed with food or an attractant, or both. Insecticides are also taken when pests eat food. The bait can take the form of granules, gels, flowable powders, liquids, or solids. They are used in pest habitats.

  A fumigant is an insecticide that has a relatively high vapor pressure and can therefore be present as a sufficient concentration of gas to kill pests in the soil or enclosed space. The fumigant toxicity is proportional to its concentration and exposure time. They are characterized by good diffusion capacity and action by penetrating the pest respiratory system or being absorbed through the pest cuticle. Fumigants are applied to control stored product pests in gas-tight rooms or buildings, or in special rooms, under non-gas permeable sheets.

  Insecticides may be microencapsulated by suspending insecticide particles or droplets in various types of plastic polymers. By changing the polymer chemistry or by changing factors in processing, microcapsules of various sizes, solubility, wall thickness, and permeability can be formed. These factors govern the rate at which the internal active ingredient is released, which in turn affects the residual performance, rate of action, and odor of the product.

  Oil concentrates are made by dissolving the pesticide in a solvent that keeps the pesticide in solution. Insecticide oils usually kill insect pests faster than other formulations, because the solvent itself has an insecticidal effect, and dissolution of the outer shell wax-like coating increases the rate of insecticide uptake. Bring. Other benefits of the oil include better storage stability, better penetration into the gap, and better adhesion to fatty surfaces.

  Another embodiment is an oil-in-water emulsion, each emulsion comprising oily globules with a layered liquid crystal coating and dispersed in an aqueous phase, each oily globules comprising at least one compound that is agriculturally active. A monolayer comprising: (1) at least one nonionic lipophilic surfactant; (2) at least one nonionic hydrophilic surfactant; and (3) at least one ionic surfactant. Or it is individually coated with an oligo multilayer and the average particle diameter of the spheres is less than 800 nanometers. Further information on this embodiment is disclosed in US Patent Application Publication No. 2007027034, published February 1, 2007, having Patent Application No. 11 / 495,228. For ease of use, this embodiment is referred to as “OIWE”.

  For further information, see D.C. See Dent, “Insect Best Management”, 2nd edition, copyright CAB International (2000). For further information, see Arnold Mallis "Handbook of Pest Control-The Behavior, Life History, and Control of Household Pests", 9th Edition, Copyright, 2004, GIE Media. Please refer to.

Other formulation ingredients (OTHER FORMULATION COMPONENTS)
In general, when the invention disclosed herein is used in a formulation, such a formulation can also include other ingredients. These ingredients include, but are not limited to (this is a non-exhaustive and not mutually exclusive listing), wetting agents, spreaders, stickers, penetrants, buffers , Sequestering agents, drift reducing agents, compatibilizers, antifoaming agents, cleaning agents, and emulsifiers. List a few ingredients instantly.

  A wetting agent is a substance that, when added to a liquid, increases the diffusion and penetration forces of the liquid by reducing the interfacial tension between the liquid and the surface on which it spreads. Wetting agents are used for two main functions in agrochemical formulations: increasing the rate of wetting of the powder in water during processing and manufacturing to give a concentrate to soluble liquids or suspendable concentrates. To make as well as to reduce the wettability of the wettable powder during mixing of the product with water in a compressed air tank to improve water penetration into the water dispersible granules. Examples of wetting agents used in the preparation of wettable powders, suspension concentrates, and water dispersible granules are sodium lauryl sulfate, sodium dioctyl sulfosuccinate, alkylphenol ethoxylates, and aliphatic alcohol ethoxylates.

  A dispersant is a substance that adsorbs onto the surface of the particles and helps preserve the state of dispersion of the particles, preventing them from re-aggregating. Dispersants are added to agrochemical formulations to facilitate dispersion and suspension during manufacture and to ensure that the particles are redispersed in water in a compressed air tank. They are widely used in wettable powders, suspension concentrates, and water dispersible granules. Surfactants used as dispersants have the ability to adsorb strongly on the particle surface and provide a charged or steric barrier to particle re-aggregation. The most commonly used surfactants are anionic, nonionic, or a mixture of the two types. In wettable powder formulations, the most common dispersant is sodium lignosulfonate. In suspension concentrates, polyelectrolytes such as sodium naphthalene sulfonate formaldehyde condensate are used to obtain very good adsorption and stabilization. Tristyrylphenol ethoxylate phosphate esters are also used. Nonionic materials such as alkylarylethylene oxide condensates and EO-PO block copolymers may be combined with anionic materials as dispersants for suspending concentrates. In recent years, new types of very high molecular weight polymeric surfactants have been developed as dispersants. They have a very long hydrophobic “backbone” and numerous ethylene oxide chains that form the “comb” “tooth” of the surfactant. Since the hydrophobic backbone has many anchoring points on the particle surface, these high molecular weight polymers can provide very good long-term stability to the suspension concentrate. Examples of dispersants used in agrochemical formulations are sodium lignosulfonate, sodium naphthalenesulfonate formaldehyde condensate, tristyrylphenol ethoxylate phosphate ester, aliphatic alcohol ethoxylate, alkyl ethoxylate, EO-PO block copolymer , And a graft copolymer.

  An emulsifier is a substance that stabilizes the suspension of droplets of one liquid phase in another liquid phase. Without an emulsifier, the two liquids separate into two immiscible liquid phases. The most commonly used emulsifier blends contain alkylphenols or fatty alcohols along with 12 or more ethylene oxide units and an oil-soluble calcium salt of dodecylbenzenesulfonic acid. A value of 8 to 18 for the hydrophilic / lipophilic balance (“HLB”) usually results in emulsions with good stability. Emulsion stability can be improved by adding a small amount of EO-PO block copolymer surfactant.

  Solubilizing agents are surfactants that form micelles in water at concentrations above the critical micelle concentration. The micelle can then dissolve or solubilize the water insoluble material inside the hydrophobic portion of the micelle. The types of surfactants commonly used for solubilization are nonionic substances: sorbitan monooleate, sorbitan monooleate ethoxylate, and methyl oleate.

  Surfactants, sometimes alone or together with other additives such as mineral or vegetable oils as adjuvants to the compressed air tank mixture to improve the biological performance of the pesticide against the target, It is used in either. The type of surfactant used for bioenhancement generally depends on the nature and mechanism of action of the insecticide. However, these are often nonionic substances such as alkyl ethoxylates, straight chain aliphatic alcohol ethoxylates, aliphatic amine ethoxylates.

  A carrier or diluent in an agricultural formulation is a material that is added to the pesticide to produce a product of the required strength. The carrier is usually a material with high absorption capacity, and the diluent is usually a material with low absorption capacity. Carriers and diluents are used in the formulation of dusts, wettable powders, granules, and water-dispersible granules.

Organic solvents are mainly used in granular formulations to a lesser extent in emulsifiable concentrate formulations, ULV formulations. A mixture of solvents may be used. The first main group of solvents are aliphatic paraffin oils such as kerosene or refined paraffin wax. The most common is the second main group, include xylene, and the C ₉ and C ₁₀ aromatic solvents such as high molecular weight fraction of aromatic solvents. When emulsifying the formulation in water, chlorinated hydrocarbons are useful as cosolvents to prevent crystallization of the insecticide. Alcohol is sometimes used as a co-solvent to increase the strength of the solvent.

  Thickeners or gelling agents are primarily suspension concentrates, emulsions to modify the rheology or flow properties of the liquid and prevent the separation and settling of dispersed particles or droplets. And in the formulation of suspoemulsion. Thickeners, gelling agents, and anti-settling agents are generally divided into two classes: water-insoluble particles and water-soluble polymers. It is possible to produce a suspension concentrate formulation using clay and silica. Examples of these types of materials include, but are not limited to, montmorillonite (eg, bentonite), aluminum magnesium silicate, and attapulgite. Water-soluble polysaccharides have been used as thickening-gelling agents for many years. The most commonly used polysaccharide types are natural extracts of seeds and seaweed, or synthetic cellulose derivatives. Examples of these types of materials include, but are not limited to, guar gum, locust bean gum, carrageenan, alginate, methylcellulose, sodium carboxymethylcellulose (SCMC), hydroxyethylcellulose (HEC). Other types of anti-precipitation agents are based on modified starch, polyacrylate, polyvinyl alcohol, and polyethylene oxide. Another good anti-precipitation agent is xanthan gum.

  Microorganisms cause damage to the formulated product. Therefore, preservation agents are used to remove or reduce these effects. Examples of such agents include, but are not limited to, propionic acid and its sodium salt, sorbic acid and its sodium or potassium salt, benzoic acid and its sodium salt, p-hydroxybenzoic acid sodium salt, p-hydroxybenzoic acid Methyl acid, and 1,2-benzisothiazolin-3-one (BIT) are included.

  The presence of surfactants that reduce interfacial tension often leads to foaming in water-based formulations during production and during mixing operations in applications through compressed air tanks. In order to reduce the tendency to foam, antifoaming agents are often added either during the production stage or before filling into the bottle. In general, there are two types of antifoaming agents: silicone and non-silicone. Silicones are usually aqueous emulsions of dimethylpolysiloxane and non-silicone antifoaming agents are water insoluble oils such as octanol and nonanol, or silica. In both cases, the function of the antifoam is to displace the surfactant from the air-water interface.

  For further information, see D.C. A. See Knowles, “Chemistry and Technology of Agrochemical Formations”, Copyright 1998, Kluwer Academic Publishers. A. S. Perry, I.D. Yamamoto, I. et al. Ishaaya, and R.A. See also Perry, “Insecticides in Agricultural and Environment-Retrospects and Prospects”, Copyright 1998, Springer-Verlag.

Application
The actual amount of insecticide applied to the pest site is not critical and can be readily determined by one skilled in the art. In general, a concentration of about 0.01 grams of insecticide per hectare to about 5000 grams of insecticide per hectare is expected to provide good control.

  In contrast, pesticides can be applied to any part where pests live, such as vegetable crops, fruits and nuts, grape vines, ornamental plants, livestock, the interior or exterior of buildings, and the soil around buildings. It may be.

  Generally, in bait, the bait is placed on the ground where, for example, termites can come into contact with the bait. Bait may also be applied to building surfaces (horizontal, vertical, or sloped surfaces) where, for example, ants, termites, cockroaches, and flies may come into contact with the bait.

  Since some pest eggs have a unique ability to resist pesticides, it may be desirable to apply repeatedly to control newly emerging larvae.

  By applying an insecticide to different parts of the plant, the overall movement of the insecticide in the plant may be used to control pests on a part of the plant. For example, foliar-feeding insect control can be controlled by drip irrigation or intercostal spraying or by treating the seeds before planting. Seed treatment can be applied to all types of seeds, including those from which plants genetically transformed to express specialized traits germinate. Representative examples include those that express proteins that are toxic to invertebrate pests (eg, Bacillus thuringiensis or other insecticidal toxins), those that express herbicide resistance (eg, “round-up ready” (Roundup Ready "seeds), or those with" stacked "foreign genes that express insecticidal toxins, herbicide resistance, nutrient enhancement, or any other beneficial trait. Furthermore, the seeds treated with the present invention disclosed herein can further enhance the ability of the plant to hold well under stressful growth conditions. This results in a healthier and more vibrant plant that can obtain higher yields during the harvest season.

  The invention disclosed herein is suitable for controlling endoparasites and ectoparasites in the veterinary sector or in the field of animal maintenance. The compounds according to the invention can be administered orally in the form of tablets, capsules, beverages, granules, for example, dermal application in the form of immersion, spraying, infusion, spotting and dusting, and parenteral, for example in the form of injections. Applied here in a known manner, such as by administration.

  The invention disclosed herein can be advantageously used to maintain livestock such as cows, sheep, pigs, chickens, and geese. Appropriate formulations are administered orally to animals along with drinking water or food. The appropriate dose and formulation will depend on the species.

  The invention disclosed herein can also be used.

  Before pesticides can be used or marketed, such pesticides are subject to a lengthy evaluation process by various (local, regional, state, national, international) government agencies. The need for large amounts of data is specified by the supervisory body, and the need for large amounts of data must be corrected by the generation and submission of data by the product registrant or others responsible for product registration. These agencies then review such data and provide product registration authorization to potential users or merchants if a safety decision is concluded. Such users or sellers can then use or sell such insecticides in the regions where product registration is accepted and supported.

  The titles herein are for convenience only and should not be used to interpret any part thereof.

Claims (8)

(A)
[Where:
X represents NO ₂ , CN, or COOR ⁴ ;
L represents a single bond, or R ¹ , S and L together represent a 5-membered or 6-membered ring;
R ¹ represents methyl or ethyl,
R ² and R ³ independently represent hydrogen, methyl, ethyl, fluoro, chloro, or bromo;
n is an integer from 0 to 3,
When n = 0 to 3 and L represents a single bond, Y is 6-halopyridin-3-yl, 6- (C ₁ -C ₄ ) alkylpyridin-3-yl, 6-halo (C _1- C ₄₎ alkyl-3-yl, 6- _(C 1 _{~C 4)} alkoxy-3-yl, 6- halo _(C 1 _{~C 4)} alkoxy-3-yl, 2-chloropyridin-4-thiazole Y, or 3-chloroisoxazol-5-yl, or when n = 0 to ¹ and R ¹ , S, and L together represent a 5- or 6-membered ring, Y is _hydrogen, C 1 -C ₄ alkyl, phenyl, 6-halopyridine-3-yl, 6- _(C 1 ~C ₄₎ alkyl-3-yl, 6- halo _(C 1 ~C ₄₎ alkyl pyridine -3 - yl, 6- _(C 1 ~C ₄₎ alkoxy pyridine - - Represents yl, 6-halo _(C 1 _{~C 4)} alkoxy-3-yl, 2-chloro-4-yl, or 3-chloro-isoxazol-5-yl,
R ⁴ represents C ₁ -C ₃ alkyl];
And (b) a composition comprising at least one other insecticide. (A)
And
(B) is spinosad, spinetoram, γ-cyhalothrin, methoxyphenozide, chlorpyrifos, or mixtures thereof,
The composition of claim 1.   A process comprising applying the composition of claim 1 to a site to control pests.   A process of applying the composition of claim 1 to seeds.   A process of applying the composition of claim 1 to seed that has been genetically transformed to express one or more specialized traits.   A process of applying the composition of claim 1 to a genetically transformed plant that has been genetically transformed to express one or more specialized traits.   A process for oral administration or application of the composition of claim 1 to an animal.   A process comprising submitting data related to the composition of claim 1 to a government agency to obtain product registration approval for a product comprising the composition of claim 1.