JPS5835174A - Benzoylurea compound and fungicide containing it - Google Patents

Abstract

NEW MATERIAL:A benzoylurea compound shown by the formulaI(A is a group shown by the formula II, formula III, formula IV, etc.; X1-X5 are H, or halogen; Y is halogen, nitro, or lower alkyl; Z1 and Z2 are halogen). EXAMPLE:N-(2,6-Difluorobenzoyl)-N'-(2-chloro-3-trifluoromethyl-6-pyrid yl)urea. USE:Useful as an insecticide. Especially effective against noxious insects, for example, particularly Lepidoptera such as diamondback moth, Mamestra brassicae, etc., Diptera such as Musca domestica Linne , Culex pipiens pallens Conquillett, etc. PROCESS:A benzoyl isocyanate compound shown by the formula V is reacted with an amine compound shown by the formula VI in the presence of a solvent such as benzene, water, etc. at 0-120 deg.C for 0.1-24hr, to give a compound shown by the formulaI.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel benzoylurea compounds and insecticides containing them.

Specifically, the present invention provides a group represented by the general formula (1), X, X, X, X, x
,.

Xs, X., AJ), Rlj: hydrogen atom or lower alkoxy group, T is a halogen atom or trifluoromethyl group), and insecticides containing them.

The general formula (11(DX, Xs~Xs, Ye ZhZ
The halogen atom represented by * and T is fluorine.

Examples of the lower alkyl group and the alkyl moiety of the lower alkoxy group represented by Y and R include chlorine, odorant IA, and iodine. Examples include l-7'thyl, t@rt-butyl, and the like.

The benzoyl urea compound of the present invention is usually (in the formula,
and Y is the above-mentioned commutation), and a benzoyl isocyanate-based compound represented by the general formula (2)) % formula % () (wherein A is the above-mentioned commuting). It is produced by reacting K with a series compound. This reaction is carried out in the presence of a solvent such as benzene, toluene, xylene, pyridine, dioxane, dimethyl sulfoxide, water, etc., and the reaction temperature is 0 to 120°C and the reaction time is 0.
．． 1 to 24 hours.

Specific examples of compounds produced by the above-mentioned general production method will be described.

AI N-(2,6-difluorobenlyl)-N'
-(2-trifluoromethyl-6-pyridyl)urea p, 2HI~239℃ 42 N-(2,6-difluorobenyl)-N'
-(2-bromo-3-trifluoromethyl-6'-pyridyl)urea style, p, 223-228°C 43N-(2-benzoyl)-N'-(2-chloro-3-)! J Fluoromethyl-6-pyridyl)urea wing, p, 210-212℃ 44N-(2-nitrobenzoyl)-N'-(2-chloro-3-trifluoromethyl-6-pyridyl)urea Frag-pull-415 ℃A
5N-(2-bromobenzoyl)-1f-(2-ri0
3-trifluoromethyl-6-pyridyl)urea
Shoulder p, 219~221'CA6N-(2-methylbenzoyl)-N'-(3-ricostEl-3-)refluoro■methyl-6-bily/l)riL/7 a<p, 311~!
11℃47N-(2-fluorotetrabenzoyl), N/-(
2-chloroWi-)lifluoromethyl-6-biridyl)urea, p, 2151-217℃
48 N-(2,6-difluorobenzoyl)-N'
-(3,!S-dichloro4(S-trifluoromethyl-3-chloro4-xol-hyridon-1-yl)phenyl)
Flare shoulder, p, 176-180°C Genus 9N-(2,6-difluorobenyl)-N'-(
4-α-(6-re-3-pyridyl)-a, α-difluoromethoxyphenyl)urea, p, 20
Fs~215℃Todoroki 1ON-(2-chloroben-diyl)
-N'-(3-(3,5-dichloro-2-biridyl))tsu11〃]Urea Kame 9.151-155℃ 411 N'-(2-libenzoyl)-N'-
(3-(5-)Lifluorotetramethyl-6-chloro-2-pyridyloxy)phenylcochlear book, p.
166-168℃AIl N-(2,6-difluorobenzoyl)-N'-(3-(5-)lifluoroImethyl-2-pyridyloxy)-4-chlorophenyl]urea 凰P 188-b/! 13 N-(2,6-difluorobenzoyl)-
N'-(3-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-6-medoxyphenyl]creano 111.9. 203-220°C 414 N-(2,6-/fluorobenzoyl)-N
'-(3-(3-chloro-5-trifluoromethyl-2
-pyridyloxy)-2,4-dichloro7el] urea class, 192-193°C 415 N-(2-Ioobey14l)-N'-(3
-(a-5-trifluoromethyl-2-pyridyloxy)-z, 4-dichlorophenylturea, p, 201-203°C Al6N-(2-methylbenzoyl)-N'-(3- (
3-ri120-5-)lifluoromethyl-2-pyridyloxy)-2,4-dichloro7el] urea-o, 9.219~! 21'C Next, a specific synthesis example of the compound of the present invention will be described below.

Synthesis example 1. N-(2,6-difluorobenzoyl)
-N'-(2-ri9μm2-3-)lifluoromethyl-
Synthesis of 6-pyridyl)urea (compound ^1) (1) Synthesis of 2-amino-5-trifluoromethyl-6-chloropyridine 5.0 g of urea and 2.6-dichloro-3-trifluoromethylpyridine4. 2 g and 30 dimethyl sulfoxide
111, heated to 100°C, and gradually added 2.5 g of potassium hydroxide. After that, 130YIJl
! The reaction product was moistened and reacted for 2 hours with stirring, and the reaction product was poured into water and extracted with methylene chloride. The extracted layer was washed with water and dried for 9 minutes, and then methylene chloride was distilled off to obtain crystals, which were recrystallized from methanol to obtain 16 g of the desired product having a maximum temperature of 109°C.

(2) N-(2,6-difluorobenzoyl)-N'-
Synthesis of (2-chloro-3-trifluoromethyl-6-pyridyl)urea 2-Aino-5-trifluoromethyl-6-chloropyridine Ig was dissolved in dioxane 20-, and LOy
A solution of 1.5 g of 2,6-cyfluorobenzoylinocyanate dissolved in sl of dioxane was gradually added dropwise at 20"C and reacted for 8 hours with stirring. After the reaction was completed,
The reaction product was poured into water to precipitate crystals, and recrystallized with methanol to obtain the desired product 1.4 with a melting point of 236-239°C.
I got g.

Synthesis example 2. N-(2,8-difluorobenzoyl)-N
Synthesis of '-(3,5-dichloroEl-4-(5-trifluoromethyl-3-chloro-2-pyridon-1-yl)7enyl]urea (compound genus 8) +1) 3.5- Dichloro■~4-(5-)Lifluoromethyl-3-chloro-2-'lJton-11l)Nitrobenzeno synthesis 2-Hydroxy-3-chloro-5-trifluoromethylpyridine 0.58g, 3,4゜5-) IJ / 0.6 g of loronitrobenzene and 0.73 g of potassium carbonate
was added to N,N-dimethylformamide 10-, and 12
The reaction was allowed to proceed at 0° C. for 2 hours with stirring. After the reaction was completed, the reaction product was poured into water, and the precipitated crystals were dried separately from P to obtain 0.6 g of the target product.

(2) 3,5-diclo-4-(5-)lifluoromethyl-3-chloro-2-pyridone-! Synthesis of -yl)aniline 0.5 g of the substituted nitrobenzene obtained in the above (1) was added to 1011j of ethanol, and 1.5 g of the substituted nitrobenzene obtained in the above (1) was added to 1011j of ethanol under reflux.
Hydrochloric acid bath i [11j containing 16 g was added dropwise to the solution at reflux temperature for 3
The reaction was allowed to proceed for 0 minutes.

After the reaction product was left to cool, it was made strongly alkaline with a freshwater potassium oxide aqueous solution, poured into water, and extracted with methylene chloride.

After washing the extracted layer with water and drying, methylene chloride was distilled off to obtain 0.4 g of the target product as an oil. PMR (・co
cja) Kyo) When I set the A value, each was 3.7.
88 (L 2H), 6.630 (8, 2H), 7.
Obtain the measured values of 993 (d, IH) and 8.222 (d, IH).

+3) N-(L 6-difluorobenzoyl)N
'-(385-dichloro-4-(5-trifluoromethyl-3-chloro-2-pyridoy-1-4k>7enyl)
Synthesis of urea Nine-substituted a, IJn0 obtained in (2) above
．． 4g and 0.6g of 2.6-difluorobenzoyl inocyanate in dioxane! il, reacted at room temperature with stirring for 1 day and the reaction product was poured into water,
The precipitated crystals were separated from P and dried to obtain 0.8 g of the desired product having a melting point of 176-180°C.

Synthesis N3. N-(2,″6-difluorobenzoyl)-
N'-(4-α-(6-chloro-3-pyridyl)-α,
Synthesis of α-difluoromethoxyphenyl]urea (compound genus 9) 4-α-(6-chloro-3-pyridyl)-α α-difluoromethoxyaniline 200g 1 dioxane 1
130 mg of 〇- and 2,6-cyfluorobenzoyl isocyanate was put into a flask and reacted at 50°C for 30 minutes with stirring. After the reaction is complete, the product is poured into water,
The precipitated crystals were washed with water and dried to give a melting point of 205 to 215'.
Obtained 150 mg of the target substance of C.

Synthesis? l14. N-(2-chlorobenzoyl)-N'-
(3-(5-)trifluoromethyl-6-trifluoro-2-pyridyloxy)phenyltourea (compound 11) (7) Synthesis 3-(6-·chloro-5-trifluoromethyl-2- 1.6 g of pyridyloxy)aniline was added to 20-
A dioxane solution containing 1.0 g of 2-chlorobenzoyl isocyanate was added dropwise over 5 minutes while maintaining the temperature at 20°C, and the mixture was reacted with stirring at 20°C for 5 hours. After the reaction is complete, the reaction product is poured into water, the resulting precipitate is washed with methanol, and the melting point is 166-16.
1.9 g of the target product was obtained at 8°C.

The compound of the present invention exhibits excellent killing activity as an insecticide, especially as an active ingredient of an insecticide, as shown in the test examples described below.

Among them, harmful insects belonging to Lepidoptera such as the diamondback moth, armyworm, and northern armyworm, Coleoptera such as the Colorado/S insect and the Japanese ladybug, and Diptera such as the house fly, Culex mosquito, Culex mosquito, etc. Effective against the center.

When the compound of the present invention is used as an active ingredient of an insecticide, it can be formulated into various forms such as emulsions, powders, irrigation agents, and solutions together with pharmaceutical adjuvants, just as in the case of conventional pesticide formulations. , I used these preparations for the first time]
Alternatively, it can be diluted with a diluent to a predetermined degree of chain before use).

The pesticide adjuvants mentioned here include solid carriers such as Merck, kaolin, bentonite, diatomaceous earth, white carbon, clay, and starch, water, xylene, toluene, dimethyl sulfoxide, dimethyl formamide, arytonitrile,
Can be used with liquid diluents such as alcohol, emulsifiers, dispersants, spreading agents, etc. Also, a must! ! Depending on the situation, it can be mixed or used in combination with other agricultural chemicals such as insecticides, acaricides, fungicides, plant growth regulators, etc., and in this case may show even better effects.

For example, as insecticides, organic phosphate compounds,
Carbamate compounds, dithio (or thiol) carnotmate compounds, organochlorine compounds, dinitro compounds, organic sulfur or metal compounds, antibiotics, substituted diphenyl ether compounds, urea compounds, triazine compounds, benzoyl urea compounds compounds, bibisroid compounds, and more specifically, benzoylurea compounds such as N-(z*6-difluorobenzoyl)-N'-(p-lyto-a-phenyl)urea, α-cyano-3- Examples include phenoxybay 2-(4-chlorophenyl) isopareley) (1)l 5' and pyrethroid compounds.

The centrifugal agent of the present invention is effective in controlling various harmful insects, especially harmful insects, and the application is generally from l to lo, o o o
active ingredient concentration of ppm, preferably 20 to 2.000 ppm. In addition, for livestock, it is possible to mix the above-mentioned active ingredients into preparations and reduce harmful insects in their excrement by 4%.
It can also control the emergence and growth of harmful insects. In the case of aquatic harmful insects, it is possible to control them by spraying a chemical solution in the above concentration range to the place where they occur, so it is effective even if the concentration range in water is below the above range.

Test Example 1: The active ingredient compound formulation was dispersed in water, and the concentration was 800 ppm.
Chemical solution K11 with a concentration of KIII4? Soak the leaf pieces of Yabetsu for about 10 seconds, then take them out and air dry them.

A Petri dish (diameter 9cm*) was covered with paper, and the leaf pieces were placed on top of it. 2nd to 3rd instar Naga larvae were released into the container, and the container was placed in a lighted incubator at 28.degree. C. with a lid.

On the 8th day after the insects were released, determine whether they were alive or dead, and calculate the mortality rate using the shipping calculation formula. Except for the above Test Example 1. The test was carried out in the same manner as in the case of , and the results of Table 2 were obtained.

M2 table test example 3° straight t! k 9 ag deep bottom petri dish K 500 p p
Approximately 250 d of the chemical solution that had been adjusted to K11M in step b was poured into the container, and 3rd instar Chicae larvae were released into the container.The container was covered with a lid and left in a lighted incubator at 28.degree. On the 10th day after release, the survival of the larvae was tested with w8, and Test Example 1. The insect mortality rate was determined in the same manner as in the case of , and the results shown in Table 3 were obtained.

Table 3 Formulation Example 1゜(a)N-(2,6-difluorobenzoyl)-N'-
(3,5-dichloromethyl-3-talolo-2-!9ton-1-yl)phenyl]urea 20 parts by weight h) N,N-dimethylformand 70 parts by weight E→ Phorioxyethylene alkylphenylethyl
10 parts by weight or more of -Km
The mixture was dissolved to form an emulsion.

Formulation example 2゜(a) N-(2-chlorobenzoyl)-N'-($-(
5-) IJ fluoromethyl-6-chloro-2-pyridyloxy)phenyltsuclef 5 parts by weight (b) Talc 95 parts by weight or more are uniformly ground and mixed to form a powder into balls.

Formulation example 3゜(a) N-(2-chlorobenzoyl)-N'-(II
-(5-)! jFluo Methyl-6-chloro-2-pyridyloxy) phenylcoclef 25 parts by weight 11 parts (b) Di-crite 70 parts by weight (c)
IJ / Sodium disulfonate 5111 parts or more can be uniformly crushed and mixed to make an aquarium.

Continuation of page 1 0 shots Akira Imai Osamu 502 Chimachi, Kusatsu City

Claims (2)

[Claims] (1) General formula (wherein M is a group represented by the formula, To'), X-Xs-Xi-Xs-X
i-Xi-Xs-Xv-Xs and X can be a hydrogen atom or a nologon atom, Y can be a gen atom, a nitro group or a lower alkyl group, Zt and z can be a gen atom A benzoyl urea compound represented by 1g atom or a lower alkoxy group, T is a halogen atom or a trifluoromethyl group. (2) As a group represented by the general formula, X, Xi, X, Xs*
X41Xs, Xi, chest, Xs and
``A halogen atom, R is a hydrogen atom, X is a lower alkoxy group), and T is a halogen atom or a trifluoromethyl group. Characteristic insecticide.