HK1142494A - Synergistic pesticidal mixtures - Google Patents

Description

Synergistic insecticidal mixtures

Cross reference to related applications

Priority of U.S. provisional application 60/927,119 filed on 5/1/2007, the disclosure of which is incorporated herein by reference in its entirety.

Technical Field

The invention disclosed in this document relates to the field of pesticides (pestides) and their use in controlling pests (control pest).

Background

Pests cause millions of deaths worldwide each year. In addition, there are more than ten thousand pest species that cause agricultural losses. These agricultural losses amount to billions of dollars each year. Termites (termite) cause damage to various structures such as houses. These termite damage losses amount to billions of dollars each year. Finally, it is noted that many pests in stored foods eat and adulterate them. These stored food losses amount to billions of dollars each year, but more importantly, deprive people of their food needs.

New insecticides are urgently needed. Insects develop resistance to currently used insecticides. Hundreds of insect species are resistant to one or more insecticides. It is well known to develop resistance to some older insecticides (e.g., DDT, carbamates, and organophosphates). However, resistance has developed even with some newer pesticides. Thus, there is a need for new pesticides, in particular for pesticides with a new mode of action.

Substituents (non-exhaustive list)

The examples given for substituents (other than for halogens) are non-exhaustive and should not be construed as limiting the invention disclosed in this document.

"alkoxy" means an alkyl group further containing a carbon-oxygen single bond, such as methoxy, ethoxy, propoxy, isopropoxy, 1-butoxy, 2-butoxy, isobutoxy, tert-butoxy, pentyloxy, 2-methylbutyloxy, 1-dimethylpropoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy and decyloxy.

"alkyl" denotes acyclic, saturated, branched or unbranched substituents consisting of carbon and hydrogen, such as methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, isobutyl, tert-butyl, pentyl, 2-methylbutyl, 1-dimethylpropyl, hexyl, heptyl, octyl, nonyl and decyl.

"halogen" means fluorine, chlorine, bromine and iodine.

"haloalkyl" means alkyl groups further containing from one to the maximum possible number of the same or different halogens, for example fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoromethyl, 2-fluoroethyl, 2, 2, 2-trifluoroethyl, chloromethyl, trichloromethyl and 1, 1, 2, 2-tetrafluoroethyl.

Disclosure of Invention

The compounds of the formula are synergistic with various other insecticides:

wherein

X represents NO₂CN or-COOR⁴；

L represents a single bond, or R¹S and L together represent a 5 or 6 membered ring;

R¹represents methyl or ethyl;

R²and R³Independently represents hydrogen, methyl, ethyl, fluorine, chlorine or bromine;

n is an integer of 0 to 3;

when n-0-3 and L represent a single bond, Y represents 6-halopyridin-3-yl, 6- (C)₁-C₄) Alkylpyridin-3-yl, 6-halo (C)₁-C₄) Alkyl pyridin-3-yl, 6- (C)₁-C₄) Alkoxypyridin-3-yl, 6-halo (C)₁-C₄) Alkoxypyridin-3-yl, 2-chlorothiazol-4-yl or 3-chloroisoxazol-5-yl, or when n ═ 0-1 and R¹When S and L together represent a 5-or 6-membered ring, Y represents hydrogen, C₁-C₄Alkyl, phenyl, 6-halopyridin-3-yl, 6- (C)₁-C₄) Alkylpyridin-3-yl, 6-halo (C)₁-C₄) Alkyl pyridin-3-yl, 6- (C)₁-C₄) Alkoxypyridin-3-yl, 6-halo (C)₁-C₄) Alkoxypyridin-3-yl, 2-chlorothiazol-4-yl or 3-chloroisoxazol-5-yl; and

R⁴represents C₁-C₃An alkyl group.

Methods for preparing sulfoximines (in addition to the method described in scheme H) have been previously disclosed in U.S. patent publication 20050228027, the teachings of which are incorporated herein.

A compound of formula (Ia) wherein R¹、R²、R³、R⁴X and Y are as previously defined, and L is a single bond, may be prepared by the method set forth in scheme a:

scheme A

In scheme a, step a, the sulfide of formula (a) is oxidized with m-chloroperoxybenzoic acid (mCPBA) in a polar solvent at 0 ℃ or less to provide the sulfoxide of formula (B). In most cases, methylene chloride is the preferred solvent for oxidation.

In scheme a, step B, sulfoxide (B) is iminated with sodium azide in the presence of concentrated sulfuric acid in an aprotic solvent under heating to provide sulfoximine of formula (C). In most cases, chloroform is the preferred solvent for this reaction.

In step C of scheme A, the nitrogen in the sulfoximine (C) can be cyanated with cyanogen bromide in the presence of a base, or nitrated with nitric acid at moderately elevated temperatures in the presence of acetic anhydride, or with an alkyl chloroformate (R) in the presence of a base such as 4-Dimethylaminopyridine (DMAP)⁴) Carboxylation of the ester affords an N-substituted sulfoximine of formula (Ia). Base is required for efficient cyanation and carboxylation, and the preferred base is DMAP, while sulfuric acid is used as a catalyst for efficient nitration.

A compound of formula (Ia) wherein X represents CN, and R¹、R²、R³、R⁴And Y are as previously defined, can be prepared by a mildly effective method as set forth in scheme B.

Scheme B

In scheme B, step a, the sulfide is oxidized with iodobenzene diacetate (PhI (OAc)2, iodobenzene diacetate) in the presence of cyanamide at 0 ℃ to provide sulfilimine (F). The reaction may be carried out in a polar aprotic solvent such as dichloromethane.

In step B of scheme B, sulfimine (F) is oxidized with mCPBA. The acidity of the mCPBA is neutralized using a base such as potassium carbonate. Protic polar solvents such as ethanol and water are used to increase the solubility of the sulfilimine starting material and the base used. The sulfilimine (F) can also be oxidized with an aqueous solution of sodium periodate or an aqueous solution of potassium periodate in the presence of a catalyst of ruthenium trichloride hydrate or the like. The organic solvent used for the catalytic reaction may be a polar aprotic solvent such as dichloromethane, chloroform or acetonitrile.

As shown in scheme C, an N-substituted sulfoximine of formula (Ia) (i.e., N ═ 1 and adjacent to the N-substituted sulfoximine functional group (CR)²R³) In the radical R³H) may be further alkylated or halogenated in the presence of a base such as potassium hexamethyldisilazide (KHMDS) to provide N substituted sulfoximines of formula (Ib) wherein R is N¹、R²、R³、R⁴X, L and Y are as previously defined and Z is a suitable leaving group. Preferred leaving groups are iodo groups (R)⁵Alkyl), benzenesulfonylimide group (R)⁵═ F), a tetrachloroethylene group (R)⁵═ Cl) and tetrafluoroethylene group (R)⁵＝Br)。

Scheme C

The starting sulfide (a) in scheme a can be prepared by different methods as set forth in schemes D, E, F, G, H and I.

In scheme D, formula (A)₁) Sulfide of formula (I), wherein R¹、R²And Y is as previously defined, n ═ 1, and R³H, from formula (D)₁) The chloride is prepared by nucleophilic substitution with the sodium salt of an alkyl thiol.

Scheme D

In scheme E, formula (A)₂) Sulfide of formula (I), wherein R¹、R²And Y is as previously defined, n ═ 3, and R³H, can be prepared as follows: general formula (D)₂) The chloride is reacted with 2-monosubstituted methyl malonate in the presence of a base such as potassium tert-butoxide to give 2, 2-disubstituted malonate, hydrolyzed under basic conditions to form a diacid which is decarboxylated by heating to give a monoacid which is reduced with borane-tetrahydrofuran complex to give an alcohol which is tosylated with tosyl chloride (tosyl chloride or tosyl chloride) in the presence of a base such as pyridine to give a tosylate and the tosylate is replaced with the sodium salt of the desired thiol.

Scheme E

In scheme F, formula (A)₃) Sulfide of formula (I), wherein R¹、R²And Y is as previously defined, n ═ 2, and R³H, can be prepared as follows: deprotonation of a nitrile of formula (E) with a strong base and alkylation with an alkyl iodide to give an α -alkylated nitrile, hydrolysis of the α -alkylated nitrile in the presence of a strong acid (e.g., HCl) to give an acid, reduction of the acid with a borane-tetrahydrofuran complex to give an alcohol, tosylation of the alcohol with tosyl chloride in the presence of a base (e.g., pyridine) to give a tosylate, and displacement of the tosylate with the sodium salt of the desired thiol.

Scheme F

In scheme G, formula (A)₄) Sulfide of formula (I), wherein R¹S and L together form a ring, n ═ 0, and Y ═ isopropyl or phenyl, can be prepared from unsubstituted cyclic sulfides (where m ═ 0 or 1). The desired sulfide (A) can be obtained in satisfactory yield by chlorinating the cyclic sulfide starting material with N-chlorosuccinimide (NCS) in benzene followed by alkylation with a Grignard reagent (Grignard reagent)₄)。

Scheme G

Preparation of formula (A)₄) Sulfide (wherein R¹S and L together form a ring, n ═ 0, m ═ 0, and Y ═ 6-halo-substituted pyridin-3-yl, 6- (C)₁-C₄) Alkyl-substituted pyridin-3-yl, 6- (C)₁-C₄) Haloalkyl-substituted pyridin-3-yl or 6- (C)₁-C₄) Alkoxy substituted pyridin-3-yl) is highlighted in scheme H. Accordingly, the corresponding appropriately substituted chlorineThe picoline is treated with thiourea, hydrolyzed, followed by alkylation with 1-bromo-3-chloropropane under aqueous base conditions, and then cyclized in a polar aprotic solvent such as Tetrahydrofuran (THF) in the presence of a base such as potassium tert-butoxide.

Scheme H

In scheme I, formula (A)₅) Sulfide of formula (I), wherein R¹As previously defined, L is a bond, n ═ 0, and Y is 6-chloropyridin-3-yl, can be prepared as follows: 2-chloro-5-bromopyridine was subjected to halogen-metal exchange followed by substitution with disulfide (disulfide).

Scheme I

Sulfoximine compounds of type Ib, in which R is¹S and L together form a saturated 5 or 6 membered ring, and n ═ 1, can be prepared by the methods set forth in scheme J, wherein X and Y are as previously defined and m is 0 or 1.

Scheme J

In step a of scheme J (which is analogous to step b of scheme a), the sulfoxide is imidized with sodium azide in the presence of concentrated sulfuric acid or O-Mesitylenesulfonylhydroxylamine (MSH) in a polar aprotic solvent to give sulfoximine. Chloroform or dichloromethane are preferred solvents.

In step b of scheme J (which is analogous to step c of scheme a), the nitrogen in the sulfoximine can be cyanated with cyanogen bromide, or nitrated with nitric acid followed by treatment with acetic anhydride under reflux conditions, or carboxylated with methyl chloroformate in the presence of a base (e.g., DMAP) to give an N-substituted cyclic sulfoximine. Base is required for efficient cyanation and carboxylation, and the preferred base is DMAP, while sulfuric acid is used as a catalyst for efficient nitration.

In step c of scheme J, the α -carbon of the N-substituted sulfoximine can be alkylated with a heteroaromatic methyl halide in the presence of a base, such as KHMDS or butyl lithium (BuLi), to give the desired N-substituted sulfoximine. Preferred halides may be bromides, chlorides or iodides.

Alternatively, the compounds of formula (Ib) may be prepared as follows: using steps c, a, and b, respectively, as described above for scheme J, the sulfoxides are first alpha-alkylated to give alpha-substituted sulfoxides, which are then imidized, followed by N-substitution of the resulting sulfoximines.

Compounds (in which Y represents the required substituent instead of 6- (C)₁-C₄) Haloalkyl-pyridin-3-yl and 6- (C)₁-C₄) Haloalkoxypyridin-3-yl) has been disclosed in U.S. patent publication 20050228027, the teachings of which are incorporated herein.

Detailed Description

The examples are for illustrative purposes and should not be construed as limiting the invention disclosed in this document to only the embodiments disclosed in these examples.

Example I.[ (6-trifluoromethylpyridin-3-yl) methyl](methyl) -oxy-lambda ⁴ Sulfoxonium nitriles (1)

[ (6-trifluoromethylpyridin-3-yl) methyl](methyl) -oxy-lambda⁴-thioiminonitrile (1) was prepared from 3-chloromethyl-6- (trifluoromethyl) pyridine according to the following three-step sequence:

to a solution of 3-chloromethyl-6- (trifluoromethyl) pyridine (5.1g, 26mmol) in dimethyl sulfoxide (DMSO; 20mL) was added sodium methyl mercaptide (1.8g, 26mmol) in one portion. A vigorous exothermic reaction was observed, which resulted in the reaction mixture turning dark. The reaction mixture was stirred for 1 hour, then additional sodium methyl mercaptide (0.91g, 13mmol) was added slowly. The reaction mixture was stirred overnight, after which it was poured into H₂To O, then a few drops of concentrated HCl were added. Et mixture₂O (Ether) (3X 50mL), the combined organic layers were washed with brine and MgSO₄Dried and concentrated. The crude product was purified by chromatography (Prep 500, 10% acetone/hexanes) to give sulfide (a) as a light yellow oil (3.6g, 67%).¹HNMR(300MHz，CDCl₃)：δ8.6(s，1H)，7.9(d，1H)，7.7(d，1H)，3.7(s，2H)，2.0(s，3H)。GC-MS：C₈H₈F₃NS[M]⁺Calculated value 207, observed value 207.

Iodobenzene diacetate (11.0g, 34mmol) was added in one portion to a solution of sulfide (A) (3.5g, 17mmol) and cyanamide (1.4mg, 34mmol) in dichloromethane (30mL) at 0 deg.C. The reaction mixture was stirred for 30 minutes and then allowed to warm to room temperature overnight. The mixture was diluted with dichloromethane (50mL) and thenBy H₂And O washing. The aqueous layer was extracted with ethyl acetate (4X 50mL), and the combined dichloromethane and ethyl acetate layers were over MgSO₄Dried and concentrated. The crude product was triturated with hexane then purified by chromatography (Chromatotron, 60% acetone/hexane) to give thioimine (B) as a yellow gum (0.60g, 14%). IR (film) 3008, 2924, 2143, 1693cm^-1。¹H NMR(300MHz，CDCl₃)：δ8.8(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)：C₉H₉F₃N₃S[M+H]⁺Mass calculation 248.04, observed value 248.

To a solution of m-chloroperoxybenzoic acid (mCPBA; 80%, 1.0g, 4.9mmol) in EtOH (ethanol) (10mL) at 0 deg.C was added K₂CO₃(1.4g, 10mmol) in H₂Solution in O (7 mL). The solution was stirred for 20 minutes, then a solution of thioimine (B) (0.60g, 2.4mmol) in EtOH (20mL) was added in one portion. The reaction mixture was stirred at 0 ℃ for 30 minutes and then allowed to warm to room temperature over 1 hour. The reaction mixture was quenched with aqueous sodium bisulfite solution and the mixture was concentrated to remove ethanol. The resulting mixture was extracted with dichloromethane and the combined organic layers were MgSO₄Dried and concentrated. The crude product was purified by chromatography (Chromatotron, 50% acetone/hexanes) to give sulfoximine (1) as an off-white solid (0.28g, 44%). Mp (melting point) 135-.¹H NMR(300MHz，CDCl₃)：δ8.8(s，1H)，8.1(d，1H)，7.8(d，1H)，4.7(m，2H)，3.2(s，3H)。LC-MS(ELSD)：C₉H₉F₃N₃OS[M+H]⁺Mass calculation 264.04, observed value 263.92.

Example II.[1- (6-trifluoromethylpyridin-3-yl) ethyl group](methyl) -oxy-lambda ⁴ Sulfoxonium nitrile (2)

[1- (6-trifluoromethylpyridin-3-yl) ethyl group](methyl) -oxy-lambda⁴Thioiminonitrile (2) prepared from [ (6-trifluoromethylpyridin-3-yl) methyl group using the procedure outlined in scheme C]- (methyl) -oxy-lambda⁴-sulfoximine (1) to prepare:

to a solution of sulfoximine (1) (50mg, 0.19mmol) and hexamethylphosphoramide (HMPA; 17. mu.L, 0.10mmol) in tetrahydrofuran (THF; 2mL) was added dropwise potassium hexamethyldisilazide (KHMDS; 0.5M in toluene, 420. mu.L, 0.21mmol) at-78 ℃. The solution was stirred at-78 ℃ for a further 20 minutes, after which methyl iodide (13. mu.L, 0.21mmol) was added. The reaction mixture was allowed to warm to room temperature over 1 hour, after which it was washed with saturated NH₄Aqueous Cl was quenched and then extracted with dichloromethane. The organic layer was washed with Na₂SO₄Drying, concentrating, and subjecting the crude product to chromatography (Chromatotron, 70% acetone/CH)₂Cl₂) Purification gave sulfoximine (2) as a 2: 1 mixture of diastereomers (colorless oil; 31mg, 59%).¹H NMR(300MHz，CDCl₃): δ (major 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); (minor 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): c₁₀H₁₀F₃N₃OS[M+H]⁺Mass calculation 278.06, observed value 278.05.

Example III.2- (6-trifluoromethylpyridin-3-yl) -1-oxo-tetrahydro-1H-1 lambda ⁴ -thiophen-1-ylideneamino Nitrile (3)

2- (6-trifluoromethylpyridin-3-yl) -1-oxo-tetrahydro-1H-1 lambda⁴-thiophen-1-ylidene-cyanamide (3) was prepared from 3-chloromethyl-6- (trifluoromethyl) -pyridine according to the 5-step sequence outlined below:

to a suspension of thiourea (1.2g, 16mmol) in EtOH (25mL) 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 as a white solid (2.4g, 58%). Mp 186-. No further attempts were made to purify the product.¹H NMR(300MHz，CDCl₃)：δ8.9(bs，4H)，8.4(s，1H)，7.6(d，1H)，7.3(d，1H)，4.2(s，2H)。LC-MS(ELSD)：C₈H₈F₃N₃S[M+H]⁺Mass calculation 236.05, observed value 236.01.

To amidine hydrochloride (A) (1.8g, 6.8mmol) in H at 10 deg.C₂To a solution in O (12mL) was added 10NNaOH (0.68mL, 6.8mmol), which resulted in the formation of a white precipitate. The suspension was heated at 100 ℃ for 30 minutes and then cooled back to 10 ℃. Additional 10N NaOH (0.68mL, 6.8mmol) was added, followed by 1-bromo-3-chloropropane (0.67mL, 6.8mmol) in one portion. The reaction mixture was stirred at room temperature overnight and then extracted with dichloromethane. The combined organic layers were washed with brine, over Na₂SO₄Drying and concentration gave sulfide (B) as a colorless oil (1.7g, 96%). No further attempts were made to purify the product.¹H NMR(300MHz，CDCl₃)：δ8.6(s，1H)，7.8(d，1H) 7.6(d, 1H), 3.8(s, 2H), 3.6(t, 2H), 2.6(t, 2H), 2.0 (quintuple, 2H).

To a suspension of potassium tert-butoxide (1.5g, 13mmol) in THF (12mL) was added HMPA (1.7mL, 10mmol) followed by dropwise addition of a solution of sulfide (B) (1.8g, 6.7mmol) in THF (3 mL). The reaction mixture was stirred at rt overnight, then concentrated and purified by chromatography (Biotage, 40% EtOAc (ethyl acetate)/hexanes) to give the cyclized product (C) as an orange oil (230mg, 15%).¹H NMR(300MHz，CDCl₃)：δ8.7(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)。

Iodobenzene diacetate (350mg, 1.1mmol) was added in one portion to a solution of sulfide (C) (230mg, 0.99mmol) and cyanamide (83mg, 2.0mmol) in dichloromethane (5mL) at 0 deg.C. The reaction mixture was stirred for 3 hours, then concentrated and the crude product was purified by chromatography (Chromatotron, 50% acetone/hexanes) to give sulfilimine (D) as an orange oil (150mg, mixture of diastereomers, 56%).¹HNMR(300MHz，CDCl₃)：δ8.8(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 mCPBA (80%, 180mg, 0.82mmol) at 0 deg.CTo a solution in EtOH (3mL) was added K₂CO₃(230mg, 1.7mmol) in H₂Solution in O (1.5 mL). The solution was stirred for 20 minutes, then a solution of thioimine (D) (150mg, 0.55mmol) in EtOH (2mL) was added in one portion. The reaction mixture was stirred at 0 ℃ for 45 minutes, after which the solvent was decanted into another flask and concentrated to give a white solid. Dissolving the solid in CHCl₃Slurried, filtered and concentrated to give pure sulfoximine (3) as a colorless oil (72mg, 44%).¹H NMR(300MHz，CDCl₃): delta (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, 8H). LC-MS (ELSD): c₁₁H₁₁F₃N₃OS[M+H]⁺Mass calculation 290.06, observed value 289.99.

Example IV.[ (6-Chloropyridin-3-yl) methyl](methyl) oxy-. lambda. ⁴ -sulfoximine (4)

[ (6-Chloropyridin-3-yl) methyl](methyl) oxy-. lambda.⁴Thioiminonitrile (4) was prepared from 3-chloromethyl-6-chloropyridine via the same 3-step sequence outlined in example I. The product was a white solid. mp 115-.¹H NMR(300MHz，CD₃OD/CDCl₃)δ8.5(d，1H)，8.0(dd，1H)，7.6(d，1H)，5.0(s，2H)，3.4(s，3H)。LC-MS(ELSD)：C₈H₉ClN₃OS[M+H]⁺A mass calculated value 230, an observed value 230.

Example V.[1- (6-Chloropyridin-3-yl) ethyl group](methyl) oxy-. lambda. ⁴ Sulfoxonium nitriles (5)

[1- (6-Chloropyridin-3-yl) ethyl group](methyl) oxy-. lambda.⁴Thioiminonitrile (5) derived from [ (6-chloropyridin-3-yl) methyl](methyl) oxy-. lambda.⁴Sulfoximine (4) was prepared via the same scheme as described in example II. The final product (isolated as a 3: 2 mixture of diastereomers) was an off-white solid. mp ═ 155-. LC-MS (ELSD): c₉H₉ClN₃OS[M-H]⁺Mass calculated values 242, observed values 242. (5) The diastereoisomers of (a) are isolated as follows: recrystallization (2: 1 MeOH/H)₂O), followed by Chromatotron chromatography of the supernatant to give (6) and (7) (stereochemistry arbitrarily assigned).

Compound (6) was isolated as a white solid. mp is 163-165 ℃.¹H NMR(300MHz，CDCl₃)：δ8.4(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)：C₉H₁₁ClN₃OS[M+H]⁺Mass calculation 244, observed value 244.

Compound (7) was isolated as a colorless oil.¹H NMR(300MHz，CDCl₃)δ8.4(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)：C₉H₁₁ClN₃OS[M+H]⁺Mass calculation 244, observed value 244.

Example VI.2- (6-Chloropyridin-3-yl) -1-oxo-tetrahydro-1H-1 lambda ⁴ -thiophen-1-ylidene cyanamide (8)

2- (6-Chloropyridin-3-yl) -1-oxo-tetrahydro-1H-1 lambda⁴-thiophen-1-ylidenecyanamide (8) was prepared from 3-chloromethyl-6-chloropyridine according to the same five-step sequence as described in example III. The product was a colourless gum which was a 1: 1 ratio of diastereoisomers. Diastereomer 1: IR (film) 3439, 3006, 2949, 2194cm^-1；¹H NMR(300MHz，CDCl₃)：δ8.4(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：C₁₀H₁₁ClN₃OS[M+H]⁺Mass calculated 256, observed 256. Diastereomer 2: IR (film) 3040, 2926, 2191cm^-1；¹H NMR(300MHz，CDCl₃)：δ8.4(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：C₁₀H₁₁ClN₃OS[M+H]⁺Mass calculated 256, observed 256.

Use of a mixture of sulfoximines and selected insecticides against green peach aphid (Myzus) Persicae) insecticidal test

A dose-response leaf spray assay was designed and performed to evaluate the synergistic effect of a mixture between the following compounds on myzus persicae:

compound 1, compound 2,

Spinosad (spinosad), spinetoram (spinetoram), gamma-cyhalothrin (gamma-cyhalothrin), methoxyfenozide (methoxyfenozide) or chlorpyrifos (chlorpyrifos).

Measurement 1: concentration ofA standard solution (master solution) at 1000ppm was prepared by dissolving the technical material (technical material) at 1mg/ml in acetone: MeOH (1: 1). For the mixture between the two test compounds, 0.047ml of standard solution from each component was combined and diluted 32-fold with acetone: MeOH (methanol) solvent (0.094ml of combination +2.906ml of solvent to give a concentration of 15.6ppm of each active ingredient (ai)), followed by 0.025% Tween 20/H₂O (12ml) was diluted 5-fold to give a solution having a concentration of 3.125 ppm. For the non-mixture, the standard solution was diluted 64 times with acetone: MeOH (0.047ml +2.953ml of solvent to give a concentration of 15.6ppm), followed by 0.025% Tween 20/H₂O (12ml) was diluted 5-fold to give a solution having a concentration of 3.125 ppm. For the mixtures and non-mixtures, lower concentrations (0.78, 0.195, 0.049 and 0.012ppm) were prepared as follows: 4ml of higher concentration (starting from 3.125 ppm) were serially diluted with 12ml of diluent consisting of 80 parts of 0.025% Tween 20/H₂O and 20 parts of acetone: MeOH.

Measurement 2: a standard solution with a concentration of 1000ppm was prepared by dissolving the technical substance at 1mg/ml in acetone: MeOH (1: 1). For mixtures between compound 2 and compound 3, 4 or 5, 0.047ml of standard solution from each component was combined and diluted 32-fold with acetone: MeOH (0.094ml of combination +2.906ml giving a concentration of 15.6ppm per active ingredient) followed by 0.025% Tween 20/H₂O (12ml) was diluted 5-fold to give a solution having a concentration of 3.125 ppm. For the mixture between Compound 2 and Compound 6 or 7, 0.047ml of standard solution from Compound 2 and 0.752ml of standard solution from Compound 6 or 7 were combined and diluted 3.755-fold with acetone: MeOH (0.799ml of combination +2.201ml of solvent to give a concentration of 15.6ppm for Compound 2 and 250ppm for Compound 6 or 7), followed by 0.025% Tween 20/H₂O (12ml) was diluted 5-fold to give a solution having a concentration of 3.125ppm for Compound 2 and 50ppm for Compound 6 or 7. For non-mixtures of compounds 2, 3, 4 or 5, the standard solution was diluted 64-fold with acetone: MeOH (0.047ml +2.953ml of solvent, resulting in a concentration of 15.6ppm) and then with 0.025% spit-upTemperature 20/H₂O (12ml) was diluted 5-fold to give a solution having a concentration of 3.125 ppm. For the non-mixtures of compounds 6 or 7, the standard solution was 3.989-fold diluted with acetone: MeOH (0.752ml +2.248ml solvent to give a concentration of 250ppm) followed by 0.025% Tween 20/H₂O (12ml) was diluted 5-fold to obtain a solution having a concentration of 50 ppm. Lower concentrations (0.78, 0.195, 0.049 and 0.012ppm for compounds 2, 3, 4 and 5; 12.5, 3.125, 0.78 and 0.195 for compounds 6 and 7) were prepared as follows for mixtures and non-mixtures: 4ml of higher concentration (starting from 3.125 or 50ppm) were serially diluted with 12ml of diluent consisting of 80 parts of 0.025% Tween 20/H₂O and 20 parts of acetone: MeOH (1: 1).

For assays 1 and 2, cabbage seedlings (with 2-3 small (3-5cm) true leaves) grown in 3-inch pots (pots) were used as test substrates. The seedlings were infested with 20-50 myzus persicae (wingless adults and nymphs) for 1 day and then chemically applied. Four seedlings were used for each treatment. The solution was sprayed onto both sides of the cabbage leaves using a hand-held Devilbiss sprayer until runoff (runoff) was formed. Control plants (solvent test) were sprayed with diluent only. The treated plants were kept in a nursery for three days at about 23 ℃ and 40% RH and then rated. Evaluation was performed by counting the number of live aphids on each plant under a microscope. Insecticidal activity was measured by using Abbott's correction formula: corrected percent control (%) ═ 100 (X-Y)/X, where X ═ solvent detects the number of live aphids on the plants and Y ═ number of live aphids on the treated plants.

TABLE 1 results

^*Colby formula (100- ((100-percent of compound a) x (100-compound)2) per 100(Colby, s.r.1967. working synergistic and antagonistic responses of antibiotic combinations. seeds 15: 20-22).

Acid and salt derivatives and solvates

The compounds disclosed herein may be in the form of pesticidally acceptable acid addition salts.

By way of non-limiting example, the amine functional group may form a salt with: hydrochloric, hydrobromic, sulfuric, phosphoric, acetic, benzoic, citric, malonic, salicylic, malic, fumaric, oxalic, succinic, tartaric, lactic, gluconic, ascorbic, maleic, aspartic, benzenesulfonic, methanesulfonic, ethanesulfonic, hydroxymethanesulfonic, and hydroxyethanesulfonic acids.

Further, by way of non-limiting example, the acid functional groups may form salts, including those derived from alkali or alkaline earth metals and those derived from ammonia and amines. Examples of preferred cations include sodium cation, potassium cation, magnesium cation, and ammonium cation.

The salt was prepared as follows: the free base form is contacted with a sufficient amount of the desired acid to provide a salt. The free base form can be recovered as follows: the salt is treated with a suitable dilute aqueous base such as dilute aqueous NaOH, dilute aqueous potassium carbonate, dilute aqueous ammonia and dilute aqueous sodium bicarbonate.

For example, in many cases, pesticides are modified to be more water soluble forms (more water soluble forms), such as 2, 4-dichlorophenoxyacetic acid dimethylamine salt, which is a more water soluble form of the well known herbicide 2, 4-dichlorophenoxyacetic acid.

The compounds disclosed herein may also form stable complexes (complexes) with solvent molecules that remain intact after non-complexed solvent molecules are removed from the compound. These complexes are commonly referred to as "solvates".

Stereoisomers

Certain compounds disclosed herein may exist as one or more stereoisomers. The various stereoisomers include geometric isomers, diastereomers and enantiomers. Thus, the compounds disclosed herein include racemic mixtures, single stereoisomers, and optically active mixtures.

It will be appreciated by those skilled in the art that one stereoisomer may be more active than the other. The single stereoisomers and optically active mixtures can be obtained as follows: a selective synthetic method, a conventional synthetic method using a resolution of the starting material or a conventional resolution method.

Pest pests

In another embodiment, the invention disclosed in this document can be used to control pests.

In another embodiment, the invention disclosed in this document can be used to control pests of the phylum nematoda (xylumnematoda).

In another embodiment, the invention disclosed in this document can be used to control a pest of the Phylum Arthropoda (Phylum Arthropoda).

In another embodiment, the invention disclosed in this document can be used to control pests of the Subphylum chelidata (subpahylum chemera).

In another embodiment, the invention disclosed in this document can be used to control arachnid (classmarcachnida) pests.

In another embodiment, the invention disclosed in this document can be used to control pests of the Subphylum podophyllum (subpahylum Myriapoda).

In another embodiment, the invention disclosed in this document can be used to control pests of the class synephrine (classssymphyla).

In another embodiment, the invention disclosed in this document can be used to control pests of the subphyla Hexapoda (subpahylum Hexapoda).

In another embodiment, the invention disclosed in this document can be used to control insects from class insecta (classsinsta).

In another embodiment, the invention disclosed in this document can be used to control Coleoptera (Coleoptera). A non-exhaustive list of such pests includes, but is not limited to, the species Vibrio sp (Acanthoscelides spp.) (weevil), Phaseolus vulgaris (Acanthoscelides spec.) (common bean weevil), Ceratoxylum gracile (Agrilus planipenis) (emerald asper), Straus sp (Agrostis sporus spp.) (wireworm), Anoplophora glabripennis (Anopyraglibri pendula (Asian Longhorned beetle)), Anopyracea sp (Anthromonas sp.), Ananadis (Anthromonas grandis) (Apocynus weevil), Anopneumothus glopennis (Aphidius spp.) (Aphidius), Coccinum sp., Periploca species (Spirochaeta.) (Periplus nigra), Cochlothria nigra species (Marasmius), Cochlothrix sp. (Athyriopsis nigra sp.) (Athyrea), Cochlothrix (Periplaneta indica (Athyriopsis), Cochlothria purpurea chinensis (Athyriopsis), Neurospora Pea weevil (Bruchus pisorum) (pea weevil), Cacoesia spp, Callosobruchus maculatus (Callosobruchus masculinus) (southern cowpea weevil), yellow spot dew beetle (carpopophilius hemsleyanus) (dried fruit beetle), beet tortoise shell (Cassida viteta), longicorn beetle (Cereus spp), yellow spot beetle (Cereus wenshu) spop, yellow spot beetle (chrysomeid), yellow spot trifolium trifoliate (Ceromorpha), yellow spot (cabbage beetle) triocta (bean leaf beetle), yellow spot (Ceratopterus flavus), yellow spot (cabbage beetle), red beetle (cabbage beetle), yellow beetle (cabbage beetle) sporum (coriaria), yellow rice beetle (cabbage beetle) sporus (cabbage beetle), yellow beetle (cabbage beetle) sporum (cabbage beetle), yellow beetle (cabbage beetle) rice beetle (cabbage beetle, red beetle (cabbage beetle), yellow beetle (cabbage beetle) rice beetle (cabbage beetle, yellow beetle (cabbage beetle) and yellow beetle (yellow beetle) are also included in the family rice beetle, yellow beetle variety (yellow beetle, yellow beetle (yellow rice beetle, rice beetle (yellow rice beetle, rice beetle, Beetles (Cryptolepis pusillus) (flat grain beetles), Orthosiphon (Cryptolepis turcicus) or (Cryptolepis turcicus) (Turkish grain beetles), Ctenocerasus (nematode), weevil (Curculio spp) (weevil), Rhizopus (Cycleophthalamus) or (grub), Meloidogyne (Cylindroceus) or (Cylindroceus spades) (sunflowers stefly), Rhizopus (Deporus) or (Bacillus grandis) (horseweed), bark beetles (Degrees bugs) (Hildene), Melothria (beetle) or (beetle), Meloidea (beetle) or (beetles) or (beetles), Bark beetle species (ipspp.) (engraver), tobacco beetle (Lasioderma sericorne) (cigarette beetle), potato beetle (leptotrichu decemlineata) (Colorado patato beetle), liogyns fuscus, liogyssularis, rice weevil (Lissorhoptrus oryzae) flower beetle (rice water weevil), bark beetle species (lichen beetle), wood beetle (rice water beetle), maize beetle (meotlannis), bark beetle (theft beetle), rape flower beetle (Meliges americana), yellow beetle (yellow beetle), black beetle (yellow beetle), yellow beetle (yellow beetle), black beetle (yellow beetle), yellow beetle (yellow beetle) shell (yellow beetle), yellow beetle (yellow beetle, the plant species of the rose Brachypodium species (Pantomerus sp.) (elephant), the leaf-eating Brachyrhizia species (Phylophaga spp.) (May/June beetle), the Phylophaga cuyana, the yellow striped beetle species (Phylophora spp.) (Chrysomyiama punctata), the apple tiger elephant species (Phynchymes spp.), the Japanese striped beetle (Popilia japonica) (Japanese beetle), the large grain beetle (Grating beetle), the bark beetle (Rhizophora dominica) (lein beetle), the root bark beetle species (Rhizophyllum beetle.) (Euzophyllum husk), the leaf beetle (bark beetle), the root bark beetle variety (bark beetle), the leaf beetle (bark beetle) and the leaf beetle (bark beetle), the root bark beetle species (leaf) (yellow rice beetle) of the root bark beetle variety (yellow rice husk beetle) of the genus, the leaf beetle species (yellow beetle variety (yellow beetle) of the genus, the leaf beetle variety (yellow rice husk beetle variety (yellow beetle), the leaf) (yellow beetle variety (yellow rice husk), the leaf) (yellow beetle variety (yellow rice husk), the leaf) (yellow rice husk variety of the root bark beetle variety of the yellow rice husk variety (yellow rice husk variety of the root bark beetle variety (yellow rice husk), the yellow rice husk variety of the yellow rice husk variety (yellow rice husk variety of the, Tribolium castaneum (red flow beer), Tribolium confluense (confluented flow beer), bark beetle (Trogoptermavariabilie) (greenhouse beer) and Zabrus teneboiides.

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

In another embodiment, the invention disclosed in this document can be used to control vein-winged (Dictyoptera) (cockroaches). A non-exhaustive list of these pests includes, but is not limited to, German cockroach (B latella germanica) (German cockroach), blattaria orientalis (orientalis), Periplaneta palustris (parachloroaca), Periplaneta palustris (parachloroa americana), Periplaneta americana (Periplaneta americana), Periplaneta australis (Periplaneta australiana), Periplaneta australiana (australia australiana), Periplaneta fusca (brown cockroach), Periplaneta fumosa (Periplaneta fuliginosa) (cockowyboach), and Periplaneta canescens (brown aggregated Periplaneta).

In another embodiment, the invention disclosed in this document can be used to control Diptera (Diptera). A non-exhaustive list of such pests includes, but is not limited to, Aedes species (Aedespp.), lucerne fly (Agromya frontella), Adenophora species (Agromya spp.), Leaf minute fly (leaf fly), Engracilis species (Anastrephe spp.), Drosophila melanogaster (fruit fly), Caribean fly (Anastrephe spp.), Anseria Bactrocera subsp (fruit fly), Bactrocera species (Bactrocera spp.), Bactrocera melon fly (Bactrocera curvata) (meal fly), Bactrocera dorsalis (Orientia fasciata) (Oriental fly, Spirosoma platyphylla (mosquito), Bactrocera fly (fruit fly), Haemophilus flavus (fruit fly), Haemateria (horse fly), Haemateria fly (horse fly), Haemateris fly (horse fly), Haematerina fly (horse fly), Haemateris fly (horse fly), Haematerina) species (horse fly), Haemateris (horse fly), Haematerina (horse fly), Haematerina) and Haematerina) species (horse fly), Haematerina, Leaf gall mosquito species (Dasineura spp.) (gallomidge), leaf gall midge (Dasineura brassiccus) (capture ga midge), subterranean fly species (Delia spp.), gray fly (Delia platura) (seed corn plot), Drosophila species (Drosophila pp.) (vinegar fly), latrine fly species (Fannia spp.) (housefly (fly), yellow belly fly (wheat belly fly) (little fly), gray belly fly (wheat belly fly) (ladder fly), stomach fly (stomach fly) (fly nest fly), Gracillia leaf, blood disturbance (Hakkia) (fly), black fly (cabbage fly) (seedling fly), black fly (cabbage fly) (seedling fly (fly), black fly (fly, cabbage fly (fly), black fly (cabbage fly) (seedling fly), black fly (cabbage fly (leaf fly), black fly (leaf fly ), black fly (black fly, leaf fly, Fall flies (Musca australis) (face fly), house flies (Musca domestica) (house fly), sheep flies (oestrumus ovis) (sheet bot fly), european straw flies (Oscinella front) (front fly), beet spring flies (pegoma beta), Phorbia spp.

In another embodiment, the invention disclosed in this document can be used to control Hemiptera (Hemiptera) (true bug). A non-exhaustive list of such pests includes, but is not limited to, Lygus lucorum (Acrosternum hierare) (green stink bug), Orthosiphon aristatus (Blissus leucopterus) (chinchbug), Buctopus laevis (Calocis norvegicus) (potatoto mirid), Cimexhemithus tropicalis (Tripterical bed bug), Cimex lectus (bed bug), Dagbertussa fasciatus, Dichelops furcatus, Trigonella gossypii (Dysdercus sutus), Edessa meditataristatus, Euonymus platanus (Eurygeus) masura (Centrona), Euschistus schistus, Euschistus (eustis), Euschistus (Lepidorum), Lepidorum purpurum (Lepidorum), Lepidorum (Lepidorum, Lepidium, Le, Neuroolpus longirostris, rice green bug (Nezara virula) (southern greenstink bug), lygus planterum (phytooris spp.) (plant bug), phytooris californica, phytooris relativus, Piezodorus guilidinggi, Tetramustarus (Poecilocussuseus) (fourrounded bug), Psallius vaccinicola, Pseudacysta plateae, Scaptocoris tanea and Convolvulus species (Triatospora spp.) (blodsulfing connosu/kissing bug).

In another embodiment, the invention disclosed in this document can be used to control Homoptera (Homoptera) (aphid, scale), whitefly, leafhopper (leafhopper). A non-exhaustive list of these pests includes, but is not limited to, the species Piperi pisum (Acrythosiphin pisum) (pea aphid), the species Globium globosum (Adelges spp.) (adelgid), Beeuglena brassicae (Aleurodesis proteella) (cab whitefly), Beeuglena spiralis (Aleurodermis dispers), Beorthothrix fimbriae (Aleurothrix floreus) (woodwhitly), the species Beorthosticella albedodes (Aluaspis spp.), Amrasca biguella, the species Bryophora (Aphrphora spp.) (leafhopper), the species Rhodococcus rubella (Amidophila randis) (Califlavia rei), the species Aphiophaga (Aphiophaga), the species Beorthostichopsis (Beorthostichopsis), the species Apphalus nilla aphid (Aphylla), the species Beorthostichopsis (Beorthostichopsis), the species Aphyllum punctatus) (Beorthostichopsis), the species Apphalus (Beorthostichophyta), the species Aphyllum punctatus (Beorthostichophyta), the plant (Beorthosticus) (Beorthostichophyta), the plant), the species Aphyllum purpureus (Beorthostichophyta), the plant (Beorthostichophyta), the species Aphyllum purpureus (Beorthosticus) (Beorthostichophyta), the species Apphalus) and the species Apphophorus (Beorthostichophyta), the species Apphalus (Beorthostichophyta), the species Appho, Cabbage aphid (Brevibacterium brassicae) (cabbage aphid), Cericerus sp (Ceroplases spp.), red ceroplas (Cericerus rubens) (red wax scale), Ceonospora sp (Chionaspis spp.), Lecanis sp (Lecanis viridula), Lecanis sp (Lecanis viridans), Lecanis sp (Lecanis viridans), Lecanis viridans (Lecanis viridans), Lecanis viridans (Lecanis viridae), Lecanis viridae (Lecanis viridis viridae) (Lecanis spp), Lecanis (Lecanis spp), Lecanis viridis (Lecanis spp) (Lecanis (L), Lecanis (Lecanis spp) (Lecanis (L) (Lecanis spp) (Leoni (L) (Lecanis spp) (Lecanis (L) (Leoni), Le, Macrosteles quadratus (ash leaf hopper), Mahanarva frimbriata, Myzus persicae (green leaf hopper), Nephophora melanostictus (Nephotettix dirhodium), Nephophora melanostictus (leaf hopper), Nephotettcinia melanostictus (Nephophora nigricans) (green leaf hopper), Niphoteus niloticus (Nilaparata variegatus) (brown leaf hopper), Pieris furfurula (Parameria giganteus) (charles), Pieris nigra (paraphyllum), Pieris nigra (maize leaf hopper), Phosphaericoides (maize leaf hopper), Phosphaericus nigra (leaf hopper) (maize leaf hopper), Phosphaericoides (leaf hopper) Maize aphids (Rhapalacium maida) (corn leaf aphid), cereal ductus (Rhapalacium padi) (oat bird-cherry aphid), Lecanicillium species (Saissetiaspp), Terminalia lechleri (Saissetiae oleae) (black scale), Schizophilus graminum (Schizaphilum gramminum) (greenbug), Physalis graminis (Sitobion avenae) (English grain aphid), Sogatella furcifera (Sogatella furcifera) (white-backed planthopper), Phytophthora species (Thereoaphis) (aphid), Toumeyella sp. (Lecanis), Phytopsis sp. (acoustic aphid), Trialeuroptera leaf beetle) (green leaf aphid), Trigonococcus (Trigonococcus) (green), and Trigonococcus (aphid), and Trigonococcus (green leaf beetle).

In another embodiment, the invention disclosed in this document can be used to control Hymenoptera (Hymenoptera) (ants, wasps and bees). A non-exhaustive list of such pests includes, but is not limited to, species of the genus Clerodendrum (Acrommerx spp.), Sinkiang Blastus (Athalia rosae), Melastoma species (Attasipp.) (leafcutting ant), Melastoma species (Camplotus spp.) (carpenter ant), Trichoplusia species (Diprion spp.) (sawflies), Formica species (Formica spp.) (ants), Argentina ant (Iridomymexhumis) (Argentine ant), Coptochlamys species (Monoorium spp.), Monomorium microphyllum (littlel black ant), termites (monariom pharaonis) (Pharaoh ant), neophyllus species (neodipion spp.) (sawflies), harvest termites species (podomomycex spp.) (harvesterant), hornet species (Polistes spp.) (paper wasp), fire termites species (Solenopsis spp.) (fire ant), domesticated termites (Tapoinoma sessile) (odorous beetle ant), migratory termites species (Tenomorium spp.) (paper ant), wasp spp.) (yellow wasp spp.) (wasp.) (yelljacket), and trichogramma species (Xylocopa spp.) (carpentbee).

In another embodiment, the invention disclosed in this document can be used to control Isoptera (Isoptera) (termites). A non-exhaustive list of such pests includes, but is not limited to, Coptotermes spp (Coptotermes spp.), Triplophora formosanus (Coptotermes curcevigathus), Coptotermes formosanus (Coptotermes ffenichii), Coptotermes formosanus (Coptotermes formosanus) (Formosan termiteran termite), Coptotermes spp (Cornittermes spp.) (Nasutte termite), Coptotermes spp (Cryptotermes spp.) (Triptotermes spp.), Coptotermes spp (Heterotermes spp.) (Desertrerubrerum termes), Coptotermes formosanus (Heterotermes spp.) (Microptotermes spp.)), Coptotermes spp (Microtermes spp.) (Microptotermes spp.) (Microtermes spp.) (Micropterus termes spp.) (Microptotermes spp.) (Micropterus spp.)), Coptotermes spp.) (Microtermes spp.) (Microptotermes spp.) (Microtermes spp Reticulitermes batyulensis, Reticulitermes grassei, Reticulitermes flavipes (Reticulitermes flavipes) (eastern subterranean term), Reticulitermes hagenii (Reticulitermes hagenii), Reticulitermes coensis (Reticulitermes heperus) (western subterranean term), Reticulitermes santonensis (Reticulitermes santonensis), Reticulitermes sphaericus chinensis (Reticulitermes speratus), Reticulitermes nigripes (Reticulitermes tibialis), Reticulitermes virginicus (Reticulitermes virginicus), Reticulitermes species (Schedulitermes spep), and Reticulitermes species (Zootiopsis sporus speratus) (Zoousspiotryveromyces paludis) species.

In another embodiment, the invention disclosed in this document can be used to control Lepidoptera (Lepidoptera) (moths and butterflies). A non-exhaustive list of such pests includes, but is not limited to, Achoeajanata, Trichoplusia species (Adoxophyes spp.), Trichoplusia lanuginosa (Adoxophyes orana), Gekko sp (Agrostis spp.), Phlebia sp (Rhizophora cutworm), Bombyx mori (Agrostis ipsilon) (black cutword), Trichoplusia gossypii (Albama argillacea) (cotton leaf word), Amorbia cuneata, Amylosis trashitella (Navelogragrange), Anacoptidia degertaria, Trichoplusia (Anacardis linella) (peach twigs borygur borrelia), Trichoplusia (Annulata) (bud), Trichoplusia (Boscholaria), Pseudoptera (Occidenta) and Spodoptera (Boletia), Pseudoptera (Occidula (Boletia) and Gracilaria), Pseudoptera (Bodinaria) and Gracilaria (Bodinaria) and Spodopterocarpus (Bodinaria), Spinosa) and Spirochaeta (Bodinaria) species (Bodinaria), Spinacia (Bodinaria) and Bodinaria (Bodinaria) can, Capua reticulana, peach fruit moth (Carposina niponensis) (peach fruit moth), graminea species (Chilo spp.), mango lateral tail moth (Choumeta transversas) (mango shoot borre), rose leaf roller moth (Choristeuropaea) (ostrinia rosea), armyworm (ostrinia nubilalis), Spodoptera species (Choristodiella spp.), rice leaf roller (Cnaphaloceras medinalis) (grass leaf roller), butterfly species (collagen spp.), litchi grain borer (Conpomorpha crassula), aromatic wood moth (Cossus) (moth) (diaphora punctata), diaphora punctata (diaphora punctata), borer ostrinia punctata (diaphora punctata), borer (diaphora punctata), corn leaf moth (diaphora punctifera), corn leaf moth (borer (diaphora punctata), corn borer (borer punctata) (corn borer), corn borer (corn borer), corn leaf moth) (corn borer spongiosa (corn borer), corn borer (corn borer) and corn borer (corn borer), corn borer (corn borer) can (corn borer) and corn borer (corn borer) are, Diamond species (Earias spp.) (Helicoverpa armigera), Egyptia diamond (Egyptia insulata) (Egyptian bollworm), Egyptia diamond (Eariastella), Rough northern bollworm (Rough northern bollworm), Ecdytopha aurantianum, southern corn borer (Elastmopsis lignosollus) (leiser cornstem bor), Epiphysistratta strattata (light brown apple bud), Epithroma species (Ephemeraceae), Ostrinia furnacalis (Hedysia punctata), Ostrinia furalis (Hedysenta), Ostrinia furalis (Hedysentaea), Ostrinia furalis) (European moth), Ostrinia (Hedysarus armorida), Ostrinia furalis (Hedysarus punctata), Ostrinia punctata (Hedysenta), Ostersize (Hedysia punctata), Ostersize moth (Ostersize), Ostertagia punctifera webber, Ostersize (Fabricius), Osteria punctifera webea), Osterea fructica (Fabricius) and Egyptica (Fabricius) species (Fabricius), Ostrinia punctifera (Ostrinia armywia armyworm (Fabricius), Ostrinia armyworm (Fabricius), Eudragia armyworm (Fabricius) and Egyo (Grapholus plusia), Euschist, Sporina), Euschist The species of the genus Helicoverpa (Helicoverpa spp.) (Spodoptera exigua), Helicoverpa armigera (Helicoverpa armigera) (cotton bollworm), Helicoverpa zea (Helicoverpa armigera) (bollworm/corn earworm), Helicoverpa armigera (Heliotis spp.) (Spodoptera), Helicoverpa virescens (Heliotis virescens) (tobaco budworm), Helicoverpa sinensiformis (Hellula undalis) (cabbagwebworm), Indorella spp. (Roots burgers), Lycopersicon esculentus (Keifida), Helicoverpa virescens (tomato yellow corn earella) (tomato pinocephalia), Helicoverpa armigera (Helicoverpa armigera) (cabbage), Helicoverpa armigera (Helicoverpa armigera) and Spodoptera (Spodopterocarpa), Spodopterocarpa armyworm (Spodopterocarpa punctata) (looper), Spodopterocarpa punctifera (Spodopterocarpa), Spodopterocarpa punctata (Spodoptera), Spodopterocarpa indica (Spodopterocarpa) and Spodopterocarpa (Spodopterocarpa) Spodopterocarpa Pod borer (Maruca testularis) (sugared borre), bagworm (moth planna) (bagwork), Mythimna uniipuncum (trueramyworm), Neocallinodoides elegans (small tomato borre), Ostrinia nubilalis (European corn borre), Oxydia vesula, Pandemia cerana (common citrus), apple leaf moth (Indian cabbage), apple leaf moth (apple leaf moth) (cabbage leaf moth), apple leaf moth (apple leaf moth) (apple leaf moth), African leaf moth (cabbage leaf moth) (cabbage leaf moth (apple leaf moth), apple leaf moth (apple leaf moth) (cabbage leaf moth) (apple leaf moth (cabbage leaf moth), apple leaf moth (cabbage leaf moth) (apple leaf moth) (cabbage leaf moth) Cabbage moth (Plutella xylostella) (diamondback moth), Polychrosis viteana (grapefero moth), orange moth (Prays endocarpa), olive moth (Prays oleae) (olivemoth), pseudolitea spp (noctuid), pseudolitea unipunctata (armyworm), soybean looper (pseudolitea includens) (soybean looper), looper (Rachiplusia nu), tryporyza incertulas (Sciphora incertulas), moth (Sesamia spp.) (hemoglobulus), Spodoptera (Spodoptera), Spodoptera (Spodoptera Spodoptera), Spodoptera trichogramma (Spodoptera), Spodoptera frugium (Spodoptera), Spodoptera (Spodoptera) and Spodoptera (Spodoptera) for preventing rice Thermoidia gemmatalis, Chlamydia armyworms (Teneola bisseliella) (webbings move), Trichoplusia ni (cab looper), Nematomyza sativae (Tuta absoluta), Nematoda species (Yponomeuta spp.), Periploca coffea pini (Red branch borer) and Periploca pipa (Zeuzera pyrina) (leopard move).

In another embodiment, the invention disclosed in this document can be used to control Mallophaga (curlicue). A non-exhaustive list of such pests includes, but is not limited to, and sheep lice (sheep biting louse), turkey cubeba (chicken body louse) and chicken feather lice (chicken feather louse).

In another embodiment, the invention disclosed in this document can be used to control Orthoptera (Orthoptera) (grasshoppers, locusts, and crickets). A non-exhaustive list of such pests includes, but is not limited to, arana nigra (anaerobe simplex) (mormonn cricket), mole cricket (gryllotalpidate) (molectrricket), Locusta migratoria (Locusta migratoria), grasshopper species (Melanoplus spp.) (grasshopper), philoxera pterospora spinosa (Microcentrum retrierve) (angularged wicked katydid), pterophalla spp. (kaydids), desert locust (schistoserca gregaria), cauda guiqu (scudderiafurata) (trunk katyized), and branchonia burmanica (valanginivoria).

In another embodiment, the invention disclosed in this document can be used to control Phthiraptera (sucking lice). A non-exhaustive list of such pests includes, but is not limited to, Haematopinus spp (cattle and pig lice), sheep jaw lice (Linoganathus ovillus) (sheet louse), head lice (Pediculus humanus capitis) (human body louse), body lice (Pediculus humanus humanus) (human body lice), and pubic lice (Pthirus pubis) (crablouse).

In another embodiment, the invention disclosed in this document can be used to control Siphonaptera (daphnaptera). A non-exhaustive list of such pests includes, but is not limited to, Ctenocephalides canis (dog flea), Ctenocephalides felis (cat flea) and human fleas (Pulex irliteans) (human flea).

In another embodiment, the invention disclosed in this document can be used to control Thysanoptera (thrips). A non-exhaustive list of such pests includes, but is not limited to, Frankliniella fusca (Tobacco's), Frankliniella occidentalis (Western flower Thrips), Frankliniella shultzii (Frankliniella Williams), Frankliniella wilsonii (Frankliniella williamis), Frankliniella glasshouse Thrips (Helothricinus) greenthicis (Greenhouse Thrips), Riphipestris cruentatus, Cirsium species (Scothricinus spp.), Citrinium aurantium (Scothricinus spp.), Cirsium tea (Scothricinus spp.), Cirsium japonicum (Pseudosium japonicum) and Thrombinalis species.

In another embodiment, the invention disclosed in this document can be used to control thysanoptera (Thysanura) (bristletail). A non-exhaustive list of such pests includes, but is not limited to, the species chlamydomonas spp (silverfish) and the species chlamydomonas microplus spp (fireburst).

In another embodiment, the invention disclosed in this document can be used to control Acarina (Acarina) (mites (mite) and ticks (tick)). A non-exhaustive list of such pests includes, but is not limited to, Apis cerana gracilis (Acarapsis woodi) (trap of honeybes), Dermatophagoides farinae (Acarus spp.) (food mites), Dermatophagoides pteronyssinus (Acarus sreatae) (grain mite), Aceria mangifera (mangobund mite), Acrophaga spinosa (Acrophagus spp.), Acrophagus solanacearus (Acrophagoides pteronyssinus) (tomatous russiae), Acrophagus pelekasi, Acrophagus dermestoides (Acrophagus pekinensis), Acrophagus schlegeli (Acrophagus schlegeli) (apple mite), Decarminella pallidiflora (Dermatophagus pallens (Dermatophagus spp.), Dermatophagus sp., Acrophagoides pterus sp., Boophilus sp. (Barbarbus sp.), Dermatophagus sp.), Dermatophagoides pterus dermatus (Bruna purpureus (Acarus sp.), Dermatophagus sp.), Dermatophagoides (Acarus sp.), Dermatophagoides pterus sp.), Dermatophagoides (Acarus sp.), Dermatophagus sp.), Dermatophagoides pterus sp.), Dermatophagus sp. (Acarus sp.), Dermatophagoides (Acarus sp.), Derma, Tetranychus species (Eotetranychus spp.), carpinus tetranyensis (Eotetranychus carpini) (yellow spider mite), Tetranychus sp (Epitimerus spp.), Tetranychus sp (Eriophus spp.), hard tick species (Ixodespp), Tetranychus sp (Metatrox spp.), Catathyris feldianus (Notoedres cat), Tetranychus parvus species (Oligonychus spp.), Calycoides (Oligonurus comatus), Tetranychus coffeensis (Oligonurus comatus), Tetranychus parvus (Oligonus comatus) (southern mite), Tetranychus urticae (Ochronus), Tetranychus sp (Tetranychus urticae) (European red mite), Tetranychus sp (Tetranychus), Tetranychus urticae (Tetranychus urticae), Tetranychus sp) (Tetranychus urticae) (Tetranychus sp), Tetranychus urticae (Tetranychus), Tetranychus urticae) (Tetranychus sp), Tetranychus urticae (Tetranychus sp) Tetranychus spp, Tetranychus urticae (twospotted spider mite), and Varroa destructor (honeybee mite).

In another embodiment, the invention disclosed in this document can be used to control Nematoda (nematodes). A non-exhaustive list of such pests includes, but is not limited to, Aphelenchoides spp (bud and leaf & pine wood) species, Heterodera spp (Belolaimus spp.) (sting wood), Cyclotella spp (Criconema spp.), Dirofilaria immitis (dog heart worm), Ditylenchus spp (stalk and bulb) species, Heteropanacea spp (Heterodera spp.) (Cyst wood), Heterocladospora maydis (Heterodera zeyla) (corn kernel nest) species, Heteropanama spp (Hierodendronella spp.) (Roylella sp.) (Romene graft), Nematoda (Pentaphylla nematode) species, Meloidogyne spp (Meloidogyne graft), Meloidogyne spp (Meloidogyne graft, Meloidogyne incognita, Meloidogyne spp.) (Meloidogyne spp (Meloidogyne graft), Meloidogyne spp (Meloidogyne spp.) (Meloidogyne spp.) (Meloidog), Meloidogyne spp (Meloidogyne spp.) (Meloidog), Meloidog (Meloidog) species, Meloidog (Meloidog, Meloidogyne spp. (Meloidog, the species Radophora (piercing nematode) and the species Rotylenchus reniformis (kidney-shaped nematode).

In another embodiment, the invention disclosed in this document can be used to control symphytum (symphylla). A non-exhaustive list of such pests includes, but is not limited to, white pine (Scutigerella immacula).

For more detailed information, see "Handbook of last Control-The Behavior, Life Histroy, and Control of Household pets" by Arnold Mallis，9^th Edition，copyright 2004by GIE Media Inc。

Mixture of

Some of the insecticides that can be beneficially used in combination with the invention disclosed in this document include, but are not limited to, the following:

1, 2-dichloropropane, 1, 3-dichloropropene,

Abamectin (abamectin), acephate (acephate), acequinocyl (acefenamic), acetamiprid (acetamiprid), housefly phosphorus (acetoson), acetoroll, flumethrin (acrinathrin), acrylonitrile (acrylonitril), gossypol (alanycarb), aldicarb (aldicarb), sulfoxylate (aldocarb), aldrin (aldrin), allethrin (allethrin), alodamin (allothrin), oxamidine (alloamidin), norcarb (alloxacarb), alpha-cypermethrin (alphacypermethrin), alpha-ecdysone (alpha-molysone), cyathion (amidinium), amidoflumet, methiocarb (amicarbazide), amifostine (amicarbazide), azathiophos (azophos), azaphos (azophos), azophos (azophos), azathion (azophos), azathiophos (azophos), azathion (azophos), azathiophos (azophos), azophos (azophos), indometha (azophos), azophos (azophos), indometha (azophos), azophos (azophos), and azophos (azophos,

Barium hexafluorosilicate (barnium hexafluorosilicate), fluthrite (barthrin), benclothianidin (barthirin), benclothiaz, bendiocarb (benfurocarb), benfuracarb (benfuracarb), benomyl (benomyl), benoxafos (benoxafos), bensultap (bensultap), benzoxate (benzoximate), benzyl benzoate (benzybenzobenzoate), beta-cyfluthrin (beta cyfluthrin), beta-cypermethrin (beta cypermethrin), bifenazate (bifenazate), bifenthrin (bifenthrin), binapacryl (binapacryl), pyrethrum (bioallegrophyte), allethrin (bioallethrin), bioxanthomethrin (bioxanthate), borax (bisflufenoxuron), bensulide (bisfenflurron), bensulide (biborocarb), bencarb (buticarb), butfenpropicarb (butyl bromide), buthiocarb (butyl bromide), buthoxycarb (butyl bromide), bromcarb (bromcarb), bromcarb (buthiocarb), bromcarb (buthiocarb), benomyl (buthiocarb), benomyl (buthiocarb (benomyl), benomyl (benomyl, buthiocarb (benomyl), ben,

Cadusafos, calcium arsenate, lime sulphur (calcium polysulphide), chlorfenapyr (carcinostat), chlorfenapyr (carcenocarb), carbaryl (carbaryl), carbofuran (carbofuran), carbon disulfide (carbon disulphide), carbon tetrachloride (carbotrrichloride), thiophosphoryl (thiophanate), carbosulfan (carbosulfan), cartap (carbomite), chlorfenapyr (carbomethionin), chlorantraniliprole (chlorambucil), chlorofenapyr (chlorofenamide), borneol (chlorofenamide), chlordane (chlorofenamide), chrysophanol (chlorofenapyr), chrysophamide (chlorofenapyr), chlorfenapyr (chlorofenapyr), chlorfenapyr (chlorofenapyr (chlorofena, Chlorpyrifos (chlorpyrifos), chlorpyrifos-methyl (chlorpyrifos methyl), chlorthion (chlorpyrifos), cycloxastream (chromafenozide), cyfluthrin I (cinerin I), cyfluthrin II (cinerin II), levo-tetramethrin (cimethrin), dichloethrocarb (cloethocarb), clofentezine (cloventezine), closantel (closantel), clothianidin (clothianidine), copper acetimidate (copperarsenite), copper arsenate (copperarsenate), copper naphthenate (copperphenazine), ketonic acid (copperolenate), (copumphos), coumarate (crotonone), crotamiton (crotonothion), crotonothion (crotonothion), cyfluthrin (cyfluthrin), cyfluthrin (cyhalothrin), cyhalothrin (cyhalothrin), cyhalothrin (cy, Cyphenothrin, cyromazine, sulfothion,

D-limonene (d-limonene), dazomet (dazomet), Dibromochloropropane (DBCP), dichloroisopropyl ether (DCIP), DDT (DDT), carbofuran (decamethrin), deltamethrin (deltamethrin), tianlephos (decaphion), tianlephos O (decaphion O), tianlephos S (decaphion S), demeton (decamethrin), demeton O (decamethrin O), demeton O-methyl (decamethrin O methyl), demeton S (decamethrin S), demeton S-methyl (decamethrin S methyl), demeton S-methyl sulfide (decathion), thion (dioxathion), dithiodiazine (dithiodiazine), dithion (dimethyldithion), dithion (dimethylthion), dithion (dimethylthion), dithion (dimethyldithion (dimethylthion, Chlorothalofos (dicrotophos), dicyclanil (dicyclanil), dieldrin (dieldrin), dichlorflufen (dineochlor), diflovidazin (diflubenzuron), diflorfluthrin (dimefluthrin), methoflurophos (dimefox), dimethoate (dimercaptan), dimethoate (dimethoate), permethrin (dimethrin), methoprene (dimethybrid), dinotefuran (dineobutton), dinocap (dinocop), dinocap 4 (dinocop 4), dinocap 6 (dinocop 6), dinocap (dinocoton), nitropentyl (dinopentonton), nitroprusol (dinopopp), pentofen (dineothion), octyl (dinetofen), dinocap (dinotefuran), dinotefuran (dinone), dinotefuran (dinoflagon), dinotefuran (dinone (dinotefuran), dinotefuran (dinone (dinotefuran), dinotefuran, dinone (dinone, dinotefuran, dinone, dinotefuran, dinone, dinotefuran, dinone, dinotefuran, dinone, dinotefuran,

ecdysterone (ecdysterone), emamectin benzoate (emamectin), spinosad (EMPC), empenthrin (empenthrin), endosulfan (endosulfan), thiophosphorum (endothion), endrin (endrin), thiophen (EPN), fenaminosulf (eponenane), eprinomectin (epimeridin), esfenvalerate (esfenvalerate), epaphos, bendiocarb (ethiofencarb), ethion (ethion), ethiprole (ethiprole), pomelo (ethofenprox), ethoprophos (ethoprop), ethopropyl (ethodddd), ethyl formate (ethopropiol formate), 1, 2-dibromoethane (ethyene dibromide), 1, 2-dichloroethane (ethyene), ethylene oxide (ethofenproxide), ethofenprox (ethofenprox), ethofenprox (ethyol), ethiofenprox (ethyol), ethion (ethoprophos), ethion (ethoprofen), ethiofenproxide (ethoprofen), ethiofenprox (ethoprofen), ethiprole (ethiofenproxide), ethiprole (ethion), ethiprolide (,

Amisulfos (famshur), fenamiphos (fenamiphos), fentrazole (fenazaflor), fenazaquin (fenazaquin), fenbutatin oxide (fenbutatin oxide), pyraflufen (fenchlophos), fenocarb (fennethacarb), fenfluthrin (fenfluthrin), fenitrothion (fentrothion), fenbutacarb (fenobucarb), fenothiocarb (fenothiocarbarb), fenoxacrem (fenoxacarb), fenoxacrim (fenoxycarb), fenoxycarb (fenoxycarb), fenpropathrin (fenpropathrin), fenpyrazothrin (fenpropathrin), fenpropathrin (fenflurazote), fenflurazote (fenflurazote), fenflurazon (fenflurazon), fenflurazote (fenflurazote), fenflurazote (fenflurazone), fenflurazote (fenflurazote), fenflurazote (fenflurazon), fenflurazon (fenflurazon), fenflurazon-methyl flufen), fenflurazon (fenflurazon ), fenflurazon (fenflurazon ), fenflurazon (fenflurazon, flubencide, fluvalinate, temephos (fonofos), varroate (formamidate), bensulide (formimidate), formoterol (formothion), carboxim (formpyranate), fenthion (fosmethialan), chlorpyrifos-methyl (fossililate), fosthiazate (foshiazate), vamuramidate (fosthietan), furathiocarb (furathiocarb), furfluthrin (furathirin), furfural (furfurfurfurfurfuel),

Gamma-cyhalothrin, gamma-hexachloro-cyclohexane (HCH),

Haloethrin (halofenprox), halofenozide (halofenozide), hexachloro-hexa (HCH), dieldrin (HEOD), heptachlor (heptachlor), heptenophos (heptanophos), flufenthion (heptapho), hexaflumuron (hexaflumuron), hexythiazox (hexythiazox), aldrin (HHDN), hydramethylnon (hydramethylnon), hydrogen cyanide (hydrocynide), monopentadiene (hydroprene), quinolinecarb (hydroquincarb),

Neonicotinoids (imicyafos), imidacloprid (imidacloprid), imidacloprid (imiprochlorrin), indoxacarb (indoxacarb), methyl iodide (iodomethane), profenofos (IPSP), isamidofos, isazofos (isazofos), carbochlorazol (isobenzan), isocarbophos (isocarbophos), isoaldrin (isodifrin), fosfamid (isofenphos), isoprocarb (isoprocarb), isoprothiolane (isoprothiolane), triazophos (isothionate), oxazofos (isoxathion), abamectin (ivermectin), abamectin (isoprothionin),

Jasminum sambac I (jasmolin I), jasminum II (jasmolin II), iodophors (jodfenphos), juvenile hormone I (juvenile hormon I), juvenile hormone II (juvenile hormon II), juvenile hormone III (juvenile hormon III),

Kelevan, meng qi (kineprene),

Lambda-cyhalothrin (lambda cyhalothrin), lead arsenate (lead arsenate), lepimectin, bromophenol (leprophos), lindane (lindane), pyrifos (liimfos), fluoropropoxy urea (lufenuron), fosthiazate (lythidathion),

Malathion (malathion), benomyl dinitrile (malonoben), triazophos (mazidox), triazophos (mecarbam), methidathion (mecarbun), methoxazone (menazon), dithianon (mephoslan), mercurous chloride (mercurous chloride), mechlorethamine (mesulfen), methidathion (mesulfenfos), metaflumizone (metaflumizone), metam (metam), chlorfenvinphos (methamphosphine), methidathion (methidathion), methiocarb (methiocarb), methamidophos (methacrophos), methoprene (methocarbamyl), methoprene (methyl chloride (methocarbamazepine), methoprene (methyl chloride (methoprene), methoprene (methocarbamazepine), methoprene (methoprene), metoclopramide (methyl chloride (methoprene), metoclopramide (methyl chloride (methochloride), metoclopramide (methochloride (methyl chloride (methochloride), metoclopramide (methochloride (methyl chloride), metoclopramide), mirex (mirex), MNAF (MNAF), monocrotophos (monocrotophos), Morpothion (morphosis), moxidectin (moxidectin),

Naphthylene phosphate (naftalofos), naled, naphthalene (naphthalene), nicotine (nicotinine), norfluridide (niflumide), delphamycin (nikkomyn), nitenpyram (nitenpyram), nithiazine (nithiazine), nitrilocarb (nitrilacarb), novaluron (novaluron), noviflumuron (noviflumuron),

Omethoate, oxamyl, oxydemethyl, oxydemeton methyl, oxydeprofos, oxydisulfoton, dimethoate, dimethoa,

P-dichlorobenzene (paradiclorobenzene), parathion (parathion), methyl parathion (parathion methyl), fluazuron (pentafluron), pentachlorophenol (pentachlorophenol), permethrin, fenthion (phenokapton), phenothrin (phenothrin), phenthoate (phenoxate), phorate (phorate), phosmet (phos), parathion (phos), phosphamidon (phosphamidon), phosphine (phosphine), phosphocarb (phosphocarb), oxime (phos), phosmet (phosmet methyl), phosmet (pyrimethan), pirimicarb (pyriproxyfen), ethephos (pyriproxyfen), promethidium (pyriproxyfen), promethamine (pyriproxyfen), promethazine (potassium chloride), promethazine (potassium thiocyanate, promethazine), promethazine (I), promethazine (potassium thiocyanate), promethazine (potassium chloride), promethazine (promethazine I, promethazine I (promethazine I), promethazine (promethazine I, promethazine (promethazine I) and promethazine (promethazine I), profluthrin, tick-lice-carbofuran (procycarb), promecarb (propaphos), propargite (propargite), methoprene (protista), propoxur (propcur), ethiprole (prothion), prothiocfos (prothiocfos), pomade (prothioconazole), prothioconazole (prothioconazole), pyrazofos (pyrafluxol), pyrazofos (pyrafluthrin), pyrethrin (pyrethrin), pyrethrin (pyrethirin I), pyrethrin II (pyrethirin II), pyridaben (pyridaben), pyridalyl (pyridalyl), pyrifluquinazon, pyrimethanil (pyrimethanil), pyriproxyfen (pyriproxyfen), pyriproxyfen (pyriproxyf,

Quassia, quinoxalines, methylquinoxalines, quintiflienes, quatifies, quasiporines, and quasiporines,

Iodoethersalicylamide (rafoxanide), resmethrin (resmethrin), rotenone (rotenone), ryania (ryania),

Sabadilla (sabadilla), octamethiphos (schradan), selamectin (selamectin), silafluofen (silafluofen), sodium arsenite (sodium arsenite), sodium fluoride (sodium fluoride), sodium hexafluosilicate (sodium hexafluosilicate), sodium thiocyanate (sodium thiocyanite), fructus Perillae (solanide), spinetoram, spinosad, spirodiclofen (spirodiclofen), spiromesifen (spiromesifen), spirotetramat (spirotetramat), sulforon (sulfofluron), sulfenom (sulfiram), sulfluramid (sulfluramid), thiotep (sulffotep), sulfur (sulflur), sulfluryl fluoride (fluoride), ethylene propylene glycol (ethylene propylene glycol), sulfur (sulffos),

Tau-fluvalinate (tau fluvalinate), thiofencarb (tazimcarb), Trichomonas (TDE), tebufenozide (tebufenozide), tebufenpyrad (tebufenpyrad), pyrifos (tebuformfos), tebufenozide (teflubenzuron), tefluthrin (tefluthrin), temephos (temephos), TEPP (TEPP), cyfluthrin (terethrin), terbufos (terbufos), tetrachloroethane (tetrachlorethane), fenvinphos (tetrachlphos), trichlorosulfone (tetradifon), tetramethrin (tetramethrin), tetramethrin (tetramactrin), acaricidal (tetramethrin), theta-cypermethrin (theta), thiocyclrin (thifenprox), thiocyclam (thiophosphate), thiofenthifenpyrad), thiocarb (thifenpyrad), thifenthiocarb (thifenprox), thiocarb (thiocarb), thifenprox (thifenprox), thiocarb (thifenprox), thifenthiocarb (thifenprox), thifenprox (thifenprox), thifenthiocarb (thifenprox (thiocarb), thifenprox), thifenthiocarb (thifenthion (thiocarb), thifenthion (thifenpyrol), thifenthion (thifenthiocarb, Transfluthrin, trialeurin, trialeurothiazine, triasulfuron, triazophos, trichlorfon, isopsorrel phosphorus 3, chlorfenapyr, chlorophenoxy, triflumuron, trimethacarb, thioacrylate, triptorezine, trimethacarb, triazophos, triflumuron, trimethacarb, triazenoate, triazophos,

aphidicolinide (vamidothion), pyrazoline (vanilprole),

Dimethylcarbofuran (XMC), propoxur (xylcarb),

Zeta-cypermethrin (zeta cypermethrin) and zolaprofos.

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

For economic and synergistic reasons, the invention disclosed in this document can also be used with herbicides and fungicides.

For economic and synergistic reasons, the invention disclosed in this document can be used with antibacterial agents (antimicrobial), germicides (bactericide), defoliants (defoliant), safeners (safers), synergists (synergists), algicides (algaecides), attractants (attractants), desiccants (desiccants), pheromones (pheromones), protectants (repellants), animal steepening agents (animal dip), avicides (avicides), disinfectants (disinfects), semiochemicals (semiochemicals) and molluscicides (moluscicides), which categories are not necessarily mutually exclusive.

For more information, see the "Complex of pesticide common Names" at the filing date of this documenthttp://www.alanwood.net/pesticides/index.html). Also please refer to "The Pesticide Manual" 14^th Edition，edited by C D S Tomlin，copyright 2006by British Crop Production Council。

Synergistic mixture (SYNERGISTIC MIXTURE)

The invention disclosed in this document can be used with other compounds (such as those mentioned under the heading "mixtures") to form synergistic mixtures in which the mode of action of each compound in the mixture is the same, similar or different.

Examples of modes of action include, but are not limited to: an acetylcholinesterase inhibitor; a sodium channel modulator; chitin biosynthesis inhibitors (chitin biosyntheses inhibitors); GABA-gated chloride channel antagonists (GABA-gated chloride channel antaconists); GABA and glutamate-gated chloride channel agonists (GABA and glutamate-gated chloride channel agonists); an acetylcholine receptor agonist; a MET I inhibitor; mg stimulated ATPase inhibitor (Mg-stimulated ATPase inhibitor); nicotinic acetylcholine receptors; midgut membrane disruptor (midgut membrane disruptor); and oxidative phosphorylation interrupters (oxidative phosphorylation disrupters).

In addition, the following compounds are known as synergists and can be used with the invention disclosed in this document: piperonyl butoxide (piperonyl butoxide), piperonal aldehyde (piprost), piperonal ester (propyl isome), piperonyl butoxide (sesamex), sesamolin (sesamolin) and sulfoxide (sulfoxide).

Preparation

Insecticides are hardly suitable for application in their pure form. It is often desirable to add other materials so that the pesticide can be used in the desired concentration and in the appropriate form for ease of application, handling, transportation, storage and to maximize the activity of the pesticide. Thus, pesticides are formulated, for example, as baits (baits), concentrated emulsions, powders (dumts), emulsifiable concentrates (emulsifiable concentrates), fumigants (fumigants), gels, granules, microencapsulated forms (microencapsulations), seed-treated forms (seed treatment), suspension concentrates, suspoemulsions (suspoemulsions), tablets, water-soluble liquids, water-dispersible granules or dry flowable (dry flowable), wettable powders (wettable powders) and ultra-low volume solutions (ultra low volume solutions).

For further information on formulation types see "Catalogue of peptides for formulations and International coding System" Technical Monograph n ° 2, 5^th Edition byCropLife International(2002)。

The insecticide is most commonly applied in the form of an aqueous suspension or emulsion prepared from a concentrated formulation of the insecticide. Such water-soluble, water-suspendable, or emulsifiable formulations are either solid (commonly known as wettable powders or water-dispersible granules) or liquid (commonly known as emulsifiable concentrates or aqueous suspensions). Wettable powders, which can be compressed to form water dispersible granules, contain an intimate mixture (insecticide mix) of insecticide, carrier and surfactant. The concentration of the insecticide is generally from about 10 wt% (weight percent) to about 90 wt%. The support is generally selected from attapulgite (attapulgite clay), montmorillonite (montmorillonite clay), diatomaceous earth (diatomous earth) or purified silicate (purified silicate). Effective surfactants (from about 0.5% to about 10% of the wettable powder) are selected from the group consisting of sulfonated lignins, concentrated naphthalene sulfonates, alkylbenzene sulfonates, alkyl sulfates, and nonionic surfactants (e.g., ethylene oxide adducts of alkylphenols).

Emulsifiable concentrates of the pesticide include a suitable concentration of the pesticide (e.g., about 50 to about 500 grams per liter of liquid) dissolved in a carrier that is a mixture of a water-miscible solvent or a water-immiscible organic solvent and an emulsifier. Useful organic solvents include aromatic solvents (particularly xylenes) and petroleum fractions (particularly the high boiling naphthalene portion and the olefinic portion of petroleum such as heavy aromatic naphtha). Other organic solvents such as terpene solvents (including rosin derivatives), aliphatic ketones (e.g., cyclohexanone) and complex alcohols (e.g., 2-ethoxyethanol) may also be used. Suitable emulsifiers for the emulsifiable concentrates are selected from the common anionic and nonionic surfactants.

Aqueous suspensions include suspensions of water-insoluble pesticides dispersed in an aqueous carrier at concentrations of from about 5% to about 50% by weight. The suspension was prepared as follows: the insecticide is finely ground and vigorously mixed into a carrier comprising water and surfactant. Ingredients such as inorganic salts and synthetic or natural gums may also be added to increase the density and viscosity of the aqueous carrier. It is generally most effective to simultaneously grind and mix the pesticide by preparing an aqueous mixture and homogenizing it in equipment such as a sand mill (sand mill), ball mill (ball mill) or piston-type homogenizer (piston-type homogenizer).

The insecticide may also be applied in the form of a granular composition which is particularly useful for application to soil. Particulate compositions typically contain from about 0.5 wt% to about 10 wt% of the pesticide dispersed in a carrier comprising clay (clay) or similar material. The above compositions are generally prepared as follows: the insecticide is dissolved in a suitable solvent and applied to a particulate carrier which has been pre-sized to a suitable particle size (range of about 0.5 to 3 mm). The above composition may also be prepared as follows: the carrier and compound are formed into a dough or paste which is then crushed and dried to obtain the desired particle size.

The pesticide-containing powder was prepared as follows: the powdered insecticide is thoroughly mixed with a suitable dusty agricultural carrier such as kaolin clay, ground volcanic rock, and the like. The dust may suitably contain from about 1% to about 10% insecticide. They can be used for seed dressing (seed dressing) or together with dust blowers for foliar application (leaf application).

It is also possible to apply the insecticide in the form of a solution in a suitable organic solvent (usually petroleum oil such as spray oil) widely used in agrochemicals.

The insecticide may also be applied in the form of an aerosol composition. In such compositions, the insecticide is dissolved or dispersed in a carrier which is a propellant mixture that can generate pressure. Packaging the aerosol composition in a container and dispensing the mixture from the container through an atomizing valve.

When the insecticide is mixed with the food or attractant or with the food and attractant, an insecticide bait is formed. When pests eat the bait, they also consume the insecticide. The bait may be in the form of a granule, gel, flowable powder, liquid, or solid. They are used in pest harborages.

Fumigants are pesticides with a relatively high vapour pressure and therefore may be present in gaseous form in sufficient concentration to kill pests in the soil or enclosed space. The toxicity of fumigants is proportional to their concentration and exposure time. They are characterized by having good spreading ability and acting by penetrating into the respiratory system of pests or being absorbed through the epidermis of pests. Fumigants are applied for the control of stored product pests (stored product pest) under gasproof sheets (gas proof sheet) in airtight rooms or airtight buildings or in special chambers.

The insecticide may be microencapsulated by suspending particles or droplets of the insecticide in various types of plastic polymers. Microcapsules of various sizes, various solubilities, various wall thicknesses, and various permeabilities can be formed by varying the chemistry of the polymer or by varying factors in the process. These factors control the release rate of the active ingredient therein, which in turn affects the residual properties, the speed of action and the odor of the product.

The oil solution concentrate is prepared by dissolving the pesticide in a solvent that maintains the pesticide in solution. Oil solutions of insecticides generally provide faster knockdown and kill action than other formulations due to the insecticidal action of the solvent itself and the increased rate of uptake of the insecticide by the (integral) waxy covering (waxy covering). Other advantages of oil solutions include better storage stability, better crack penetration and better adhesion to greasy surfaces.

Another embodiment is an oil-in-water emulsion, wherein the emulsion comprises oily globules (oil globules) each provided with a lamellar liquid crystalline coating (lamellar liquid crystalline) and dispersed in the aqueous phase, wherein each oily globule comprises at least one agriculturally active compound and is each coated with a single layer or layers of layers comprising (1) at least one nonionic lipophilic surfactant, (2) at least one nonionic hydrophilic surfactant, and (3) at least one ionic surfactant, wherein the globules have an average particle size of less than 800 nanometers. Further information regarding this embodiment is disclosed in U.S. patent publication 20070027034 (published date 2/1/2007 and patent application No. 11/495,228). For ease of use, this embodiment is referred to as "OIWE".

For further information see "Insect Pest Management" 2^ndEdition by D.Dent, copy CAB International (2000). In addition, for more details, see "Handbook of Pest Control-The Behavior, Life Histroy, and Control of Household pets" by Arnold Mallis, 9^th Edition，copyright 2004by GIE Media Inc。

Other formulation Components

Generally, when the invention disclosed in this document is used in a formulation, the formulation may also contain other components. These components include, but are not limited to (this is a non-exhaustive and non-mutually exclusive list) wetting agents, spreading agents (spreaders), stickers, penetrants, buffers, release agents (sequestrant agents), anti-drift agents (drift reduction agents), compatibility agents (compatibility agents), anti-foaming agents, detergents, and emulsifiers. Several components are described next.

Wetting agents are substances that, when added to a liquid, increase the spreading or penetration capacity of the liquid by reducing the interfacial tension between the liquid and the surface on which the liquid is spread. Wetting agents perform two main functions in agrochemical formulations: increasing the rate of wetting of the powder in water during processing and manufacture to produce a concentrate or suspension concentrate in a soluble liquid; and reducing the wetting time of the wettable powder and improving the penetration of water into the water dispersible granules during mixing of the product with water in the spray tank. Examples of wetting agents for use in wettable powders, suspension concentrates and water dispersible granule formulations are sodium lauryl sulphate, dioctyl sodium sulfosuccinate (sodium dioctyl sulfosuccinate), alkylphenol ethoxylates and fatty alcohol ethoxylates.

Dispersants are substances that adsorb onto the surface of particles and help to maintain the dispersed state of the particles and prevent the particles from reaggregating. Dispersants are added to agrochemical formulations to aid in dispersion and suspension during manufacture and to help ensure that the particles are redispersed in water in a spray tank. They are widely used in wettable powders, suspension concentrates and water dispersible granules. Surfactants used as dispersants have the ability to adsorb strongly to the surface of the particles and provide a charged or steric barrier against reaggregation of the particles. The most commonly used surfactants are anionic surfactants, nonionic surfactants or mixtures of the two types. For wettable powder formulations, the most common dispersant is sodium lignosulfonate (sodium lignosulphonate). For suspension concentrates, polyelectrolytes such as sodium naphthalene sulfonate formaldehyde condensate are used to achieve very good adsorption and stabilization. Tristyrylphenol ethoxylate phosphate ester (tristyrylphenol ethylatephosphite ester) was also used. Nonionic surfactants, such as alkylaryl ethylene oxide condensates (alkyl aryl ethylene oxide condensates) and EO-PO block copolymers, are sometimes combined with anionic surfactants as dispersants for suspension concentrates. In recent years, new classes of very high molecular weight polymeric surfactants have been developed as dispersants. These dispersants have a very long hydrophobic "backbone" and a large number of ethylene oxide chains forming the "teeth" of a "comb" surfactant. These high molecular weight polymers may provide very good long term stability to the suspension concentrate because the hydrophobic backbone has multiple anchor points to fix to the particle surface. Examples of dispersants used in agrochemical formulations are sodium lignosulfonates, sodium naphthalene sulfonate formaldehyde condensates, tristyrylphenol ethoxylate phosphate esters, fatty alcohol ethoxylates, alkyl ethoxylates, EO-PO block copolymers and graft copolymers.

Emulsifiers are substances which stabilize a suspension of droplets of one liquid phase in another. In the absence of an emulsifier, the two liquids would separate into two immiscible liquid phases. The most commonly used emulsifier blends contain an alkylphenol or fatty alcohol having 12 or more ethylene oxide units and an oil soluble calcium salt of dodecylbenzene sulfonic acid. Hydrophilic lipophilic balance ("HLB") values ranging from 8 to 18 will generally provide good stable emulsions. Emulsion stability can sometimes be improved by adding small amounts of EO-PO block copolymer surfactant.

Solubilizers are surfactants that form micelles in water at concentrations above the critical micelle concentration. The micelles are then able to solubilize or solubilize the water-insoluble material within the hydrophobic portions of the micelles. The type of surfactant commonly used for solubilization is a nonionic surfactant: sorbitan monooleate (sorbitan monooleate), sorbitan monooleate ethoxylate (sorbitan monooleate ethoxylate) and methyl oleate (methyl oleate ester).

Surfactants are sometimes used alone or sometimes in combination with other additives (such as mineral or vegetable oils as adjuvants to spray tank mixtures) to improve the biological performance of the pesticide on the target. The type of surfactant used for bioanhancement (bioenhancement) generally depends on the nature and mode of action of the pesticide. However, they are typically non-ionic, such as alkyl ethoxylates, linear fatty alcohol ethoxylates, fatty amine ethoxylates.

Carriers or diluents in agricultural formulations are materials that are added to pesticides to give products of desired strength. The carrier is generally a substance having a high absorption capacity (absorptive capacity), and the diluent is generally a substance having a low absorption capacity. Carriers and diluents are used in powder formulations, wettable powder formulations, granular formulations and water dispersible granular formulations.

Organic solvents are used primarily in emulsifiable concentrate formulations and ULV formulations and to a lesser extent in granular formulations. Mixtures of solvents are sometimes used. The first main group of solvents are aliphatic paraffinic oils (parafinic oils), such as kerosene or refined paraffins. The second main group and most common solvents include aromatic solvents such as xylene and the higher molecular weight fraction C₉And C₁₀An aromatic solvent. Chlorinated hydrocarbons may be used as co-solvents to prevent crystallization of the pesticide when the formulation is emulsified into water. Sometimes alcohols are used as co-solvents to increase solvent power.

Thickeners or gelling agents are used primarily in suspension concentrate formulations, emulsion formulations and suspoemulsion formulations to modify the rheology or flowability of the liquid and prevent separation or settling of the dispersed particles or droplets. Thickeners, gelling agents and anti-settling agents are generally divided into two categories, namely water-insoluble particles and water-soluble polymers. It is possible to use clays and silica to produce suspension concentrate formulations. Examples of these types of materials include, but are not limited to, montmorillonite, such as bentonite; magnesium aluminum silicate; and activated clay (attapulgite). Water-soluble polysaccharides have been used as thickening-gelling agents for many years. The most commonly used types of polysaccharides are natural extracts of seeds or seaweeds or synthetic derivatives of cellulose. Examples of these types of materials include, but are not limited to, guar gum, locust bean gum (locustbean gum), carrageenan (carrageenam), alginates, methylcellulose, sodium carboxymethylcellulose (SCMC), Hydroxyethylcellulose (HEC). Other types of anti-settling agents are based on destructured starch, polyacrylates, polyvinyl alcohols and polyethylene oxides. Another good anti-settling agent is xanthan gum.

The microorganisms cause spoilage (spoilage) of the formulated product. Preservatives are therefore used to eliminate or reduce the action of microorganisms. 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, parahydroxybenzoic acid sodium salt, methylparaben, and 1, 2-benzisothiazolin-3-one (BIT).

The presence of surfactants that reduce interfacial tension typically results in foaming of the water-based formulation during the mixing operation when produced and applied by the spray can. To reduce foaming tendency, antifoams are usually added at the production stage or before bottling. In general, there are two types of defoamers, namely silicone and non-silicone. The silicone is typically an aqueous emulsion of polydimethylsiloxane, while the non-silicone antifoam agent is a water-insoluble oil such as octanol and nonanol. In both cases, the function of the defoamer is to displace the surfactant from the air-water interface.

For further information see "Chemistry and Technology of agricultural formulations" edited by D.A. Knowles, copyright1998by Kluwer academic publishers. See also "antibiotics in Agriculture and environmental-retrospection and Prospectra" by A.S.Perry, I.Yamamoto, I.Ishaaya, and R.Perry, copyright1998by Springer-Verlag.

Administration of

The actual amount of pesticide applied to the locus of the pest is not critical and can be readily determined by one skilled in the art. Generally, concentrations of about 0.01 grams of insecticide per hectare to concentrations of about 5000 grams of insecticide per hectare are expected to provide good control.

The locus to which the pesticide is applied may be any locus occupied by pests, such as vegetable crops, fruit and nut trees, grapevines, ornamentals, livestock, the interior or exterior surfaces of buildings and the soil surrounding buildings.

Generally, in the case of baits, the bait is placed in a location where, for example, termites can come into contact with the bait. The bait may also be applied to surfaces of buildings (horizontal, vertical, or inclined surfaces) where, for example, ants, termites, cockroaches, and flies may come into contact with the bait.

Because of the unique ability of some pest eggs to resist pesticide action, repeated applications may be required to control emerging larvae.

Systemic movement of a pesticide in a plant can be used for pest control of another part of the plant by applying the pesticide to a different part of the plant. For example, control of foliar-feeding insects can be achieved by drip irrigation application or furrow application or by treating the seed prior to planting. Seed treatment may be applied to all types of seeds, including those that can be grown into plants genetically transformed to express a particular attribute. Representative examples include those seeds expressing proteins or other insecticidal toxins that are toxic to invertebrate pests (e.g., Bacillus thuringiensis), those seeds expressing herbicide resistance (e.g., "Roundup Ready" seeds), or those seeds having "stacked" exogenous genes that express an insecticidal toxin, herbicide resistance, a nutrient enhancing property, or any other beneficial property. Furthermore, said seed treatment with the invention disclosed in this document can further enhance the ability of plants to better withstand stressed growth conditions. This results in healthier, more vigorous plants, and thus higher yields at harvest.

The invention disclosed in this document is suitable for controlling endoparasites (endo-arasitites) and ectoparasites (ectoarasities) in veterinary medicine or in the field of animal feeding. The compounds according to the invention are applied here in a known manner, such as orally, for example in the form of tablets, capsules, drinks, granules, transdermally, for example in the form of dips, sprays, pours, spots and dusts, and parenterally, for example in the form of injections.

The invention disclosed in this document can also be advantageously used in livestock breeding (e.g., cattle, sheep, pigs, chickens, and geese). Suitable formulations are administered orally to animals along with drinking water or feed. The appropriate dosage and formulation depends on the species.

The invention disclosed in this document can also be used.

Before the pesticide can be used or sold commercially, it undergoes lengthy evaluation procedures by various governmental authorities (local, regional, state, national, international). The large data requirements (volumes data requirements) are specified by the authorities and must be given (address) by data generation (data generation) and submitted by the product registrant or by others on behalf of the product registrant. These government authorities then evaluate the data and, if a security decision is made, provide a product registration approval (product registration approval) to the potential user or seller. These insecticides can then be used or sold by the user or seller where product registration is authorized and supported.

Headings in this document are for convenience only and are not intended to be used in any way to explain any portion of this document.

Claims (8)

1. A composition, comprising:

(a)

wherein

X represents NO₂CN or-COOR⁴；

L represents a single bond, or R¹S and L together represent a 5 or 6 membered ring;

R¹represents methyl or ethyl;

R²and R³Independently represents hydrogen, methyl, ethyl, fluorine, chlorine or bromine;

n is an integer of 0 to 3;

when n-0-3 and L represent a single bond, Y represents 6-halopyridin-3-yl, 6- (C)₁-C₄) Alkylpyridin-3-yl, 6-halo (C)₁-C₄) Alkyl pyridin-3-yl, 6- (C)₁-C₄) Alkoxypyridin-3-yl, 6-halo (C)₁-C₄) Alkoxypyridin-3-yl, 2-chlorothiazol-4-yl or 3-chloroisoxazol-5-yl, or when n ═ 0-1 and R¹When S and L together represent a 5-or 6-membered ring, Y represents hydrogen, C₁-C₄Alkyl, phenyl, 6-halopyridin-3-yl, 6- (C)₁-C₄) Alkylpyridin-3-yl, 6-halo (C)₁-C₄) Alkyl pyridin-3-yl, 6- (C)₁-C₄) Alkoxypyridin-3-yl, 6-halo (C)₁-C₄) Alkoxypyridin-3-yl, 2-chlorothiazol-4-yl or 3-chloroisoxazol-5-yl; and

R⁴represents C₁-C₃An alkyl group; and

(b) at least one other insecticide.

2. The composition of claim 1, wherein

(a) Comprises the following steps:

and

(b) is Icidin, spinetoram, gamma-cyhalothrin, methoxyfenozide, chlorpyrifos or a mixture thereof.

3. A method comprising applying the composition of claim 1 to a locus to control pests.

4. A method of applying the composition of claim 1 to a seed.

5. A method of applying the composition of claim 1 to a seed that has been genetically transformed to express one or more specific attributes.

6. A method of applying the composition of claim 1 to a genetically transformed plant that has been genetically transformed to express one or more specific traits.

7. A method of orally administering or administering the composition of claim 1 to an animal.

8. A method comprising submitting data relating to the composition of claim 1 to a governmental authority in order to obtain product registration approval for a product comprising the composition of claim 1.