JPS63277664A - N-phenyl-n'-benzoylurea compound and insecticidal and miticidal agent containing same - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [X1 is halogen, (halo)alkyl, etc.; X2 is halogen or (halo)alkyl; n is 0-4; Y1 and Y2 are H, halogen or alkyl; Z is O or S; A1 and A2 and N or CX3 (X3 is H or halogen); R1 is alkyl; R2 is alkyl, halogen or (substituted)phenyl; excluding the case that both Y1 and Y2 are H and A1 and A2 are N]. EXAMPLE:Isopropyl 4-[4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl]-7-( 2,6- difluorophenyl )-2-methyl-5,7-dioxo-3-thia-2,4,6-triazaheptanoate. USE:Insecticidal and miticidal agent. PREPARATION:The compound of formula I can be produced e.g. by reacting a compound of formula II with a compound of formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to novel N-phenyl-N'-benzoylurea compounds and insecticides and acaricides containing them.

(Disclosure of the Invention) The present invention relates to the general formula (1): [wherein, Xl is a halogen atom, an alkyl group, a haloalkyl group, or an alkoxycarbonyl group, O
or an integer of 1 to 4, Yl and Yt are a hydrogen atom, a halogen atom, or an alkyl group, Z is an oxygen atom or a sulfur atom, and 8.

and A2 is -N= or -〇'' (X3 is a hydrogen atom or a halogen atom), R+ is an alkyl group, and R
1 is an alkyl group or a phenyl group which may be substituted with a halogen atom, an alkyl group, a haloalkyl group, a nitro group or a cyano group.

Regarding N-phenyl-N'-benzoyl urea compounds represented by the following formula (excluding cases where Y and Y2 are hydrogen atoms and A1 and At are -N-) and insecticides and acaricides containing them. It is something.

In the general formula (1), Xl, Xz, '1'+, Y
z, alkyl group contained in R1 and R2 or Xl, Xz
The alkyl moiety constituting the haloalkyl group contained in R1 or the alkoxycarbonyl group represented by
Butyl group, isobutyl group, tert 7' thyl group, n
-pentyl group, n-hexyl group, n-octyl group, etc., but -C is preferably a lower alkyl group having 1 to 4 carbon atoms, halogen atoms contained in xl, XtSXl, Yl, Yt and R2, Xl , Xx and R8 include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.

The number of substituents on the phenyl group substituted with a halogen atom, alkyl group, haloalkyl group, nitro group or cyano group in R3 may be one or more, and in the case of two or more, they may be different or different. , furthermore Xl, Xt and R2
The haloalkyl group contained in is an alkyl group substituted with one or two or more halogen atoms, preferably a trifluoromethyl group.

Novel N-phenyl-N represented by the general formula (1)
The '-benzoyl urea compound can be produced, for example, by the following method.

(A) (where Xl, X, Y, , Y, , Z, AI, Ax,
(R+ and Ri are as described above) The reaction of the above reaction formula (A) is carried out in the presence of a solvent, if necessary. Examples of solvents include aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; cyclic or acyclic aliphatic hydrocarbons such as hexane and isoclohexane; ethers such as diethyl ether, methyl ethyl ether, dioxane, and tetrahydrofuran; and niacetonitrile. , propionitrile, acrylonitrile and other nitriles, dimethylformamide, dimethyl sulfoxide, sulfolane,
Examples include aprotic solvents such as hexamethylphosphoric triamide.

The raw material compound represented by the general formula (U) in the reaction formula (A) can be produced, for example, by the following method.

CB) (In the formula, X+, Xz, Z, At, At, R+ and R2 are as described above.) (Table 1 lists representative examples of the raw material compounds represented by the general formula (■)).

Table 1 Next, specific synthesis examples of the compounds of the present invention will be described.

Synthesis Example l Isopropyl 4- (4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl)-7-(2,6-difluorophenyl)-2-methyl-5,7-thioxo 3- Synthesis of thia-2,4,6-triazahebutanoate (compound 1).

(1) 4.0 g of 4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)aniline and 2.1+s of triethylamine dissolved in methylene chloride & 40III, isopropylphenyl-N-
A methylene chloride solution containing 3.1 g of methylcarbame was added dropwise to the mixture under water cooling, and the mixture was reacted with stirring for 1 hour.

After the reaction, methylene chloride in the reaction product was distilled off under reduced pressure and subjected to silica gel column chromatography (developing solvent/n
-hexane:ethyl acetate-8:2) to give isopropyl N- [ [ (
3.7 g of 4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl]amino]thio]-N-methylcarbame) was obtained.

(n) 2,6-cyfluoropenzoyl isocyanate 1
．． 88g of carbamate obtained in step (1) above.3.
30-l of a 1,4-dioxane solution in which 7 g was dissolved was added dropwise at room temperature, and the mixture was reacted for 3 hours with stirring.

After the reaction, 1,4-dioxane in the reaction product was distilled off under reduced pressure and purified by silica gel column chromatography (developing solvent/n-hexane: ethyl acetate = 8:2) to give a melting point of 50-56°C. The desired product (amorphous solid) was obtained.

Synthesis Example 2 Isopropyl 4- (4-(5-bromo-2-pyrimidinyloxy)-3-chlorophenyl)-
7-(2-chlorophenyl)-5,7-thioxo-2-
Synthesis of n-propyl-3-thia-2°4.6-)riazaheptanoate (compound 3).

(1) 4-(5-bromo-2-pyridinyloxy)-3-chloroaniline5. 50ml of methylene chloride solution in which Og and triethylamine 2.5+++j2 are dissolved
(l is isopropyl N-chlorosulfenyl-N-
A propyl carbamate methylene chloride solution was added dropwise under water cooling, and the mixture was stirred at room temperature for 3 hours.
Allowed time to react.

After the reaction, methylene chloride in the reaction product was distilled off under reduced pressure and purified by silica gel column chromatography (developing solvent/n-hexane: ethyl acetate = 6:4) to obtain isopropyl N-[, which is a highly viscous product. ((4-(5-bromo-2-pyrimidinyloxy)-3-chlorophenyl)
Amino]thio]-N-n-propyl carbamate 6,3
I got g.

[■] 2-chlorobenzoyl isocyanate 0, 4
1.0 g of carbamate obtained in the above step (+) in 6 g
10 mj of 1,4-dioxane! A solution dissolved in was added, and the mixture was reacted at room temperature for 2 hours with stirring.

After the reaction was completed, 1,4-dioxane in the reaction product was distilled off under reduced pressure, and silica gel column chromatography (developing solvent/
0.14 g of the target product (amorphous solid) with a melting point of 52 to 57°C after purification with n-hexane; ethyl acetate = 6:4)
I got it.

Table 2 lists examples of representative compounds of the present invention that can be synthesized according to the above synthesis examples.

The compound of the present invention exhibits excellent activity as an active ingredient of insecticides and acaricides, as shown in the test examples below. For example, the diamondback moth
armyworm, fall armyworm, codling moth, ball worm, tobacco budworm (ta)
bacco budwor+w), gypsy moth 1 Colorado potato beetle, ball w'eevi
l), Huff class 9, agricultural pests such as bee flies, scarab beetles, tamanaya moths, kaburaya moths, plant-parasitic spider mites, sanitary pests such as cockroaches, houseflies, Culex mosquitoes, black moths, bacterium moths, white rice beetles,
It is effective against grain storage pests such as the white-spotted beetle, clothing and household pests such as burs, burrs, and termites, as well as flies and mites that parasitize livestock. It is also effective against various chemically resistant insect pests such as the house fly, which is resistant to organophosphates.

All of them are highly effective against the larvae, but if the adult insects ingest the compounds of the present invention, they will be unable to lay eggs, or even if they are able to lay eggs, they will prevent the eggs from turning into four. Demonstrates high safety against beneficial organisms, including non-wire beneficial insects.

When this product is used as the active ingredient of the i-based agent, it can be formulated into various forms such as emulsions, powders, wettable powders, liquids, and pastes together with agricultural chemical adjuvants, as in the case of conventional agricultural chemical formulations. I can do it.

The blending ratio of these is usually 0.5 to 9゜ffl of active ingredients.
The amount of agricultural chemical adjuvant is 10 to 99.5 parts by weight.

When these preparations are actually used, they can be used as is or diluted to a predetermined concentration with a diluent such as water.

Examples of the agrochemical auxiliary agents herein include carriers, emulsifiers, suspending agents, dividing agents, spreading agents, penetrants, wetting agents, thickeners, stabilizers, etc., which may be added as appropriate. Carriers are divided into solid carriers and liquid carriers, and solid carriers include starch, activated carbon, soybean flour, wheat flour, wood flour, fish meal,
Examples include animal and vegetable powders such as milk powder, mineral powders such as talc, kaolin, bentonite, calcium carbonate, zeolite, diatomaceous earth, white carbon, clay, alumina, and sulfur powder. Liquid carriers include water, methyl alcohol, and ethylene. Alcohols such as glycols, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane and tetrahydrofuran, aliphatic hydrocarbons such as kerosene and kerosene, aromatics such as xylene, trimethylbenzene, tetramethylbenzene, cyclohexane, and solvent naphtha. Hydrocarbons, halogenated hydrocarbons such as chloroform and chlorobenzene, acid amides such as dimethylformamide, esters such as ethyl acetate and glycerin ester of fatty acids, nitriles such as acetonitrile, and sulfur-containing compounds such as dimethyl sulfoxide. Examples include.

In addition, other agricultural chemicals such as insecticides, acaricides, nematicides, fungicides, antiviral agents, attractants, herbicides,
It can be mixed or used in combination with plant growth regulators, etc., and may exhibit even better effects in this case.

For example, as an insecticide, acaricide, or nematicide,
0-(4-promo-2-chlorophenyl)0-ethyl
S-propyl phosphorothioate, 2,2-dichlorovinyldimethyl phosphate, ethyl 3-methyl-
4-(Methylthio)phenyl isopropylphosphoramidate, 0.0-dimethyl 0-4-nitro-m-)
Lyle phosphoro-rt ate, 0-ethyl 0-4-
Nitrophenyl phenylphosphonothiony), O, O
-diethyl 0-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate, 0. 〇-Dimethyl O-(3,5,6-)dichloro-2-pyridyl)
Phosphorothioate, 0. Organic phosphate ester compounds such as S-dimethyl acetyl phosphoramidothioate, 0-(2,4-dichlorophenyl) 〇-ethyl S-propyl phosphorodithioate; 1-naphthyl
Methyl carbamate, 2-isopropoxyphenyl
Methyl carbamate, 2-methyl-2-(methylthio)
Propionaldehyde 0-methylcarbamoyloxime, 2,3-dihydro-2,2-dimethylbenzofuran-7-ylmethylcarbamate, dimethyl N, N'
-(thiobisC(methylimino)carbonyloxy)
] Bisethanimidothioate, S-methyl N-(methylcarbamoyloxy)thioacetimidate, N,
N-dimethylcarbamoyloxyimino-2-(methylthio)acetamide, 2-(ethylthiomethyl)phenyl methylcarbamate, 2-dimethylamino-5,6
Carbamate-based compounds such as -dimethylpyridin-4-yl dimethylcarbamate, S, S' -2-dimethylaminotrimethylene bis(thiocarbamate);
2. 2. 2-) Licoro 1.1-bis(4-chlorophenyl)ethanol, 4-chlorophenyl 2,4
．． Organochlorine compounds such as 5-1-dichlorophenyl sulfone; organometallic compounds such as tricyclohexyldine hydroxide; (R3)-α-cyano-3
-phenoxybenzyl (R3)-2-(4-chlorophenyl)-3-methylbutyrate, 3-phenoxybenzyl (IR3)-cis, trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclo Propane carboxylate, (R3)-α-cyano-3-phenoxybenzyl (IR5)-cis, trans-3-(2,2
-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, (S) -α-cyano-3-phenoxybenzyl (IR)-cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclo Propane carboxylate, (R5)-α-cyano-3-phenoxybenzyl (IR3)-cis, trans-3-(2-chloro-3
, 3,3-trifluoropropenyl)-2,2-dimethylcyclopropanecarboxylate, 4-methyl-2,
3,5,6-titrafluorobenzyl-3-(2-chloro-3゜3.3-1-lifluoro-1-propene-1-
1-(4-chlorophenyl)-3-(2,6-'; fluorobenzoyl)
Urea, l-[3,5-dichloro-4-(3-chloro-
5-trifluoromethyl-2-pyridyloxy)phenyl)-3-(2,6-difluorobenzoyl)urea,
Benzoyl urea compounds such as 1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea; 2-tert-butyl, minnow 3-isopropyl-5-phenyl- 3゜4.
5.6-tetrahydro-2H-1,3,5-thiadiazin-4-one, trans-5-(4-chlorophenyl)
-N-cyclohexyl-4-methyl-2-oxothiazolidinone-3-carboxamide, N-methylbis(2,
Compounds such as 4-xylyliminomethyl)amine, N'-(4-chloro-0-tolyl)-N,N-dimethylformamidine; isopropyl (2E,4B)-11-
Juvenile hormone-like compounds such as methoxy-3,7,11-)dimethyl-2,4-dodecadienoate; and other compounds such as dinitro compounds, organic sulfur compounds, urea compounds, and triazine compounds. Examples include. Furthermore, it can also be used in combination with microbial pesticides such as BT agents and insect pathogenic virus agents.

For example, as a fungicide, S-benzyl 0゜0-diisopropyl phosphorothioate, 0-ethyl S, S
- Organophosphorus compounds such as diphenyl phosphorodithioate and aluminum ethyl hydrogen phosphonate; Organochlorine compounds such as 4,5,6゜7-tetrachlorophthalide and tetrachloroisophthalonitrile; Manganese ethylene bis(dithiocarbamate) ), zinc ethylene bis (dithiocarbamate polymer), complex compound of zinc and maneb, dizinc bis (dimethyldithiocarbamate), ethylene bis (dithiocarbamate), zinc propylene bis (dithiocarbamate) polymer, etc. Carbamate compounds;
3a, 4,7゜7a-tetrahydro-N-()dichloromethanesulfenyl)phthalimide, 3a, 4.7.7
N- such as a-tetrahydro-N-(1,1,2,2-tetra-chloroethanesulfenyl)phthalimide, N-(trichloromethylsulfenyl)phthalimide, etc.
Halogenothioalkyl compound; 3-(3,5-dichlorophenyl)-N-isopropyl-2,4-dioxoimidazolidine-1-carboxamide, (R3)-3-(
3,5-dichlorophenyl)-5-methyl-5-vinyl-1,3-oxazolidine-2,4-dione, N-(3
, 5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide; methyl 1-(butylcarbamoyl)benzimidazol-2-yl carbamate, dimethyl 4.4°- Benzimidazole compounds such as (o-phenylene)bis(3-thioallophanate) i 1-
(,,4-chlorophenoxy)-3,3-dimethyl-
1-(IH-1゜2.4-)riazol-1-yl)butanone, 1-(biphenyl-4-yloxy)-3,3
-dimethyl-1-(IH-1,2,4-triazole-
1-yl)butan-2-ol, 1-(N-(4-chloro-2-trifluoromethylphenyl)-2-propoxyacetimidoyl)imidazole, 1-(2-(2
,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylmethyl)-1H-1,2,4-)riazole, 1-(2-(2,4-dichlorophenyl)-
4-propyl-1,3-dioxolan-2-ylmethyl]-IH-1.2.4-triazole, 1-(2-(2
,4-dichlorophenyl)pentyl)-1H-1,2,
4-) Azole compounds such as lyazole; 2,4°-
Dichloro-α-(pyrimidin-5-yl)benzhydryl alcohol, (±)-2,4′-difluoro-α-
(1) Carbinol compounds such as 1-1.2.4-triazol-1-ylmethyl)benzhydryl alcohol; 3′-isoproboxy-0-toluanilide, α, α
.

Benzanilide compounds such as α-trifluoro-3′-isopropoxy-O-toluanilide; methyl N-
(2-methoxyacetyl)-N-(2゜6-xylyl)
-Acylalanine compounds such as DL-alaninate; 3-chloro-N-(3-chloro-2,6-sinitro-4-α,α,α-trifluorotolyl)-5-trifluorotolyl)-5- Pyridinamine compounds such as trifluoromethyl-2-pyridinamine; other compounds include piperazine compounds, morpholine compounds, anthraquinone compounds, quinoxaline compounds, crotonic acid compounds, sulfenic acid compounds, urea compounds, Examples include antibiotics.

The insecticide and acaricide of the present invention is effective for controlling various pests, and the application is generally from 1 to 20. The concentration of active ingredient is OOOppm, preferably 20 to 2,000 ppm.

The concentration of these active ingredients can be appropriately changed depending on the form of the preparation, the method of application, purpose, timing, location, pest outbreak status, etc. For example, in the case of water-living pests, it is possible to control them by spraying a chemical solution in the above concentration range at the location where they occur.
The active ingredient concentration range in water is below the above.

The application per unit area is about 0.1 to 5.000 g of active ingredient compound per 102, preferably 5 to 1
,000 g is used. However, deviations from these ranges are possible in special cases.

The various formulations containing the compounds of the present invention or their dilutions can be applied by commonly used application methods, such as spreading (e.g., spraying, misting, misting, atomizing, water surface application, etc.), soil application ( It can be carried out by mixing, irrigation, etc.), surface application (painting, powder coating, coating, etc.), immersed poison bait, etc.

It is also possible to feed livestock with the above-mentioned active ingredient mixed with their feed, and use the excrement to control the growth and development of harmful insects, particularly harmful insects. It can also be applied by the so-called ultra low-volume method. In this method, the active ingredient is
It is possible to contain 0%.

Next, test examples of the compounds of the present invention will be described.

J Test Example 1 Disperse each formulation of the acaricidal test active ingredient compound in water,
The concentrations were adjusted to 00 ppm and 200 ppm. Cup (diameter 7cm) of kidney beans with only one first leaf remaining
cm5 and 4 cm in height), and inoculated with about 30 two-spotted spider mite larvae. This product was immersed in the chemical solution of the predetermined concentration for about 10 seconds, air-dried, and then left in an illuminated incubator at 26°C. On the 5th day after treatment, survival was determined, and the mortality rate was calculated using the following formula, and the results shown in Table 3 were obtained.

Table 3: Dispersing each formulation of the active ingredient compound in water,
Cabbage leaf pieces were immersed in the chemical solutions adjusted to concentrations of 2.5 pp- and 1.25 pp- for about 10 seconds, and air-dried. A moist filter paper was placed in a 9 cm diameter veterinary dish, and the air-dried leaf pieces were placed on top of the moist filter paper. 2nd to 3rd instar diamondback moth larvae were released there, the lid was placed, and the container was left in a lighted incubator at 26°C. The survival rate was determined at the 5th molar after adulthood, and the mortality rate was calculated using the following formula, and the results shown in Table 4 were obtained.

Bud 3 Spodoptera japonica The test was carried out in the same manner as in Test Example 2 above, except that the 2nd to 3rd instar of the armyworm was replaced with the 2nd to 3rd instar of the armyworm, and the results shown in Table 5 were obtained.

Table 5 Next, formulation examples of the present invention are described, but the compounds, formulation amounts, and dosage forms of the present invention are not limited to the described examples.

Formulation Example 1 (a) 20 parts by weight of compound 5 (b) 72 parts by weight of dicrite (c) 8 parts by weight or more of sodium ligninsulfonate are uniformly mixed to prepare a wettable powder.

Formulation example 2 (a) Compound fish 7 5ffi amount (b)
95 parts by weight or more of talc are uniformly mixed to form a powder.

Formulation example 3 (a) Compound 6 20 parts by weight (b) N, N
' - 70 parts by weight of dimethylformamide (c) Polyoxyethylene alkylphenyl ether
10 parts by weight or more are uniformly mixed and dissolved to form an emulsion.

Formulation Example 4 (a) 78 parts by weight of gicrite (b) β-
Naphthalene sulfonic acid sodium formalin condensate
2 parts by weight (c) Polyoxyethylene alkylaryl sulfate 5 parts by weight (d) White carbon A mixture of 15 or more parts of each component and Compound No. 9 are mixed in a weight ratio of 4:1 to form a hydrating agent. shall be.

Formulation Example 5 (a) Compound Magnetic 1 5 parts by weight (b) Xylene 85 parts by weight (c) Polyoxyethylene alkylphenyl ether 10
Parts by weight or more are uniformly mixed and dissolved to form an emulsion.

Claims (1)

[Claims] 1. General formula: ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, X_1 is a halogen atom, an alkyl group, a haloalkyl group, or an alkoxycarbonyl group, and is a haloalkyl group, n
is 0 or an integer from 1 to 4, Y_1 and Y_2 are hydrogen atoms, halogen atoms, or alkyl groups, Z is oxygen atom or sulfur atom, A_1 and A_2 are -N= or ▲ mathematical formula, chemical formula, table etc. ▼ (X_3 is a hydrogen atom or a halogen atom), R_1 is an alkyl group, and R_2 may be substituted with an alkyl group or a halogen atom, an alkyl group, a haloalkyl group, a nitro group or a cyano group It is a phenyl group. However, Y_1 and Y_2 are hydrogen atoms, A_1 and A
An N-phenyl-N'-benzoyl urea compound represented by [except in each case where _2 is -N=]. 2. General formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X_1 is a halogen atom, an alkyl group, a haloalkyl group, or an alkoxycarbonyl group,
is 0 or an integer from 1 to 4, Y_1 and Y_2 are hydrogen atoms, halogen atoms, or alkyl groups, Z is oxygen atom or sulfur atom, A_1 and A_2 are -N= or ▲ mathematical formula, chemical formula, table etc. ▼ (X_3 is a hydrogen atom or a halogen atom), R_1 is an alkyl group, and R_2 may be substituted with an alkyl group or a halogen atom, an alkyl group, a haloalkyl group, a nitro group or a cyano group It is a phenyl group. However, Y_1 and Y_2 are hydrogen atoms, A_1 and A
An insecticide and acaricide characterized by containing an N-phenyl-N'-benzoyl urea compound represented by the following formula (except in each case where _2 is -N=) as an active ingredient.