JPH02138247A - Benzoylurea derivative, its production, its use, its intermediate and production of the intermediate - Google Patents

Abstract

NEW MATERIAL:The benzoylurea derivative of formula I (R<1> is F or Cl; R<2> is F when R<1> is F and R<2> is H when R<1> is Cl; X is CF2Br, CCl2H, CBr2H. CFHCI, OFUCF3, CFROCF3, CFHOC2F5 or CFHOC3H7-n). EXAMPLE:N-2,6-difluorobenzoyl-N,-[2-fluoro-4-(2-chloro-1,1,2-trifluoro ethoxy) phenyl]urea. USE:Insecticide. Ovicide for insect. It has extremely high activity against larva, nymph and egg of vermin and is producible at a relatively low cost. PREPARATION:The compound of formula I can be produced e.g. by reacting a benzoyl isocyanate compound of formula II with an aniline compound of formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides - coinage (1) [wherein R1 represents a fluorine atom or a chlorine atom, R
2 represents a fluorine atom when R1 is a fluorine atom, R
When 1 is a chlorine atom, it represents a hydrogen atom. X is the formula CF2B
r, CC12H, CBr2H.

CFHCl, CFHCF8. CFHOCF8. C
Represents a group represented by FHOC2F6 or CFHOC8F7-n. The present invention relates to a benzoyl urea derivative represented by (hereinafter referred to as the compound of the present invention), a method for producing the same, an insecticide containing the same as an active ingredient, an intermediate thereof, and a method for producing the intermediate.

It has been known that certain benzoyl urea compounds have insecticidal activity (USP 8988908, USP 4189686, USP 445).
No. 7948 specification, EP71279A specification, EP2
oa618A@specification, EP226642A specification,
EP285089A specification and JP-A-59-106
454, etc.), some of which are already commercially available.

However, these compounds are not necessarily satisfactory, as they are insufficiently effective and have problems in terms of production cost.

In view of this situation, the present inventors have conducted intensive studies to develop benzoyl urea compounds with superior insecticidal activity. It was discovered that it has extremely high efficacy against pest larvae, nymphs, and eggs, and can be produced at a relatively low cost, leading to the present invention.

Specific pest insects and eggs to which the compounds of the present invention are particularly effective include, for example, lepidopteran larvae and their eggs such as the diamondback moth, the Japanese caterpillar moth, the armyworm, the caterpillar, the cabbage moth, the burr, and the carp moth; species, Aedes species, Chironomid species, House flies, Black flies, Black flies,
Diptera larvae such as flies and blackflies and their eggs; Reclidoptera nymphs such as the German cockroach, black cockroach, brown cockroach, American cockroach and their rabbits; Eggs etc. can be given.

In addition, the compound of the present invention has low toxicity to warm-blooded animals, so it can be mixed into animal feed, etc., and can be used in cattle, pigs, horses, sheep, etc.
It can be orally administered to livestock such as goats and chickens. As a result, the compounds are excreted from the animal's body undecomposed, allowing insects living in livestock excrement (
For example, it is possible to exterminate the larvae and eggs of house flies, giant house flies, common house flies, black flies, black flies, black flies, etc.).

Among the compounds of the present invention, preferred compounds include those of the formula X CFHC1, CFHCF B , CFHOCF B
'lt: 1. Compounds representing a group represented by tCFHOC8F 7-n can be mentioned, and even more preferred compounds include compounds in which X represents the above-mentioned group and R1 and R2 are both fluorine atoms.

The compound of the present invention represented by general formula (1) can be obtained by the following method! IIJLi can be done.

(Manufacturing method A) General formula (If) [In the formula, R1 and 1<2 represent the same meanings as above.

] A benzoyl isocyanate compound represented by the general formula (
1) [In the formula, X represents the same meaning as above. A method of reacting with an aniline compound shown in ].

(Manufacturing method B) - Throwing money (IV) [In the formula, R1 and R2 represent the same meanings as above. ] A benzamide compound represented by the general formula (D [wherein, X
has the same meaning as above. ] A method of reacting with an isocyanate compound represented by.

In the above production methods A and B, the reaction is usually carried out in the presence of an inert solvent. Examples of solvents that can be used include aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as chlorobenzene, carbon tetrachloride, chloroform, methylene chloride, and 1,2-dichloroethane, diethyl ether, tetrahydrofuran,
Examples include ethers such as dioxane, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, dimethyl sulfoxide, dimethyl formamide, nitromethane, and mixed solvents thereof.

In production methods A and B, the reaction can generally be carried out under normal pressure, and the objective can usually be achieved within a range of 10 minutes to 50 hours.

Further, the raw material compounds may be used in an equimolar ratio within the shell, but one of the raw material compounds may be used in an excess amount. That is, the amount of penzoyl isosyl dianate compound (1) is in the range of 0.8 to 1.2 per mole of aniline compound (1),
Further, the amount of the isocyanate compound (V) is in the range of 0.8 to 1.2 mol per 1 mol of the benzamide compound (IV).

In production methods A and B, the reaction temperature is not particularly limited, but in production method A, it is generally 0 to 80
°C1 usually ranges from room temperature (approximately 20°C) to 60°C, and in production method B, generally room temperature (approximately 20"C)
) to 160°C, usually between 80 and 180°C.

The compound of the present invention thus obtained can be purified by means such as column chromatography, recrystallization, etc., if necessary.

The compounds of the present invention produced in this manner include the following.

N-2,6-difluorobenzoyl-N'-[2-fluoro-4-(2-chloro-1,1°2-trifluoroethoxy)phenyl]urea N-2-chlorobenzoyl-N
'-[2-fluoro-4-(2-chloro-1,1,2-
)difluoroethoxy)phenyl]urea N-2,6-difluorobenzoyl-N'-[2-fluoro-4-(2-bromo-1,1°2.2-tetrafluoroethoxy)phenyl]urea N-2- Chlorobenzoyl-N'-[2-fluoro-
4-(2-bromo-1,1,2,2-tetrafluoroethoxy)phenyl]urea N-2,6-difluorobenzoyl-N'-(2-fluoro-4-(2,2-dibromo-1, 1-difluoroethoxy)phenyl]urea N-2-chlorobenzoyl-N'-[2-fluoro-
4 (212-dibromo-1,1-difluoroethoxy)
phenyl]urea N-2,6-difluorobenzoyl-N'-[2-fluoro-4-(1,1,2-trifluoro-trifluoromethoxy)lifluoromethoxy)ethoxy]phenyl]
Urea N-2-chlorobenzoyl-N'-[2-fluoro-4
-[1,1,2-trifluoro-trifluoromethoxytrifluoromethoxy)ethoxy]phenyl]urea N-
2,6-difluorobenzoyl-N'-[2fluoro-
4-(2,2-dichloro-1,1-difluoroethoxy)phenyl]urea N-2-chlorobenzoyl-N'-(
2-Fluoro-4-(2,2-dichloro-1,1-difluoroethoxy)phenyl]urea N-2,6-difluorobenzoyl-N'-[2-fluoro-4-[1,1,2-tri Fluoro-trifluoromethoxypentafluoroethoxy)ethoxy]phenylurea N-2-chlorobenzoyl-N'-[2-fluoro-4
-(1,1,2-1lifluoro-trifluoromethoxypentafluoroethoxy)ethoxy]phenyl]urea N-'! , 6-difluorobenzoyl-N'-(2fluoro-4-(1,1,2-trifluoro-trifluoromethoxyheptafluoropropoxy)ethoxy]phenyl]urea N-2-chlorobenzoyl-N'-(2- Fluoro-
4-[1,1,2-)lifluoro-2-(heptafluoropropoxy)ethoxy]phenyl]urea N-2,6-difluorobenzoyl-N'-[2-fluoro-4-(1,1,2 ,8,8,R-hexafluoropropoxy)phenyl]urine N-2-chlorobenzoyl-N-[2-fluoro-4-(1,1,2,8,8,8
-hexafluoropropoxy)phenyl]urea Next, an example of its production will be shown.

Production Example 1 0.812 2-fluoro-4-(2-chloro-1,1゜2-trifluoroethoxy)aniline was added to 5 m of toluene.
A solution prepared by dissolving 0.281 of 2,6-cyfluoropenzoyl isocyanate in 8 ml of toluene was added dropwise to the solution while stirring under water cooling. After the dropwise addition was completed, the reaction solution was stirred at room temperature overnight, 5 ml of n-hexane was added thereto, the resulting crystals were separated from P, and dried to give N-2.
,6-difluorobenzoyl-N'-[2-fluoro-
4-(2-chloro1.1.2-trifluoroethoxy)
Phenyl]urea 0.89F was obtained as white crystals.

Yield near 2% m, 1): 178.4°C Production Example 2 2-Fluoro-4-(2-bromo-1,1゜2.2-tetrafluoroethoxy)aniline 0,8 Of was dissolved in 5% phosgene. - It was added to 88 ml of toluene solution and heated under reflux for 8 hours. After concentrating the reaction solution, the resulting residue was diluted with xylene 20
ml of 2,6-cyfluorobenzamide.
152 was added and stirred under reflux for 24 hours. The reaction solution was then cooled and concentrated to obtain a crude product. This crude product was subjected to silica gel chromatography.
-difluorobenzoyl-N'=[2-fluoro-4-
(2-Bromo-1,1,2,2-tetrafluoroethoxy)phenyl]urea 0.41N was obtained as white crystals.

Yield: 85% m, p,: I B 64°C Production Example 8 0.269 of 2-fluoro-4-[1,1,2-trifluoro-trifluoromethoxy)lifluoromethoxy)ethoxycoaniline was added to toluene. A solution prepared by dissolving 0.16 F of 2,6-cyfluorobenzoyl isocyanate in 4 liters of toluene was added dropwise to the resulting solution while stirring under water cooling. After the dropwise addition, the reaction solution was stirred at room temperature overnight, and 5 ml of n-hexane was added thereto. The resulting crystals were filtered and dried to give N-2,6-difluorobenzoyl-N'-[2 -Fluoro-4-(1
,1,2-)lifluoro=trifluoromethoxy)lifluoromethoxy)ethoxy)phenyl]urea 0.26
F was obtained as white crystals.

Yield: 68% m, p,: 125.6°C Next, the compounds of the present invention obtained according to these production methods are shown in Table 1 below.

Table 1 Note that in this production method, the benzoyl isocyanate compound represented by the general formula (1) and the penzamide compound represented by the general formula (IV) used as the raw material compounds are known compounds. The aniline compound represented by ) is a new compound, and can be produced, for example, by the method shown below.

Production method (1) [In the above formula, XI is the formula CCA' 2) (, CB r 2
II, CFHCl-CFIOCF, , CFHO
C2F6 or CF)IOC8F7-n, and Y is of the formula CCl2. CBr2.

CFC7/, CFOCF8. Represents a group represented by CFOC2F or CFOC8F7n. ] A method for obtaining an aniline compound (Ill') by reacting 8-fluoro-4-aminophenol and an olefin compound (Vl) in the presence of a base.

Examples of the base used in this reaction include caustic alkalis such as caustic potash, carbonate alkalis such as potassium carbonate,
Alkali metals such as sodium metal or hydrides of alkali metals such as sodium hydride are used, preferably XI has the formula CFHOCF8. If it is not a group represented by CFHOC2F or CFHOC8F7-n, it is caustic potash, and xl is of the formula CF) (OCF, , CF
HOc2F6 or CFHOC8F7. In the case of the group represented by -n, sodium hydride is used.

This reaction is usually carried out in an inert solvent, and the solvents used include, for example, dimethylformamide, or dimethylformamide and other inert solvents (toluene,
A mixture of acetonitrile, dioxane, etc. is used, and dimethylformamide is preferably used.

The reaction temperature is θ~150'C, preferably xl is of the formula CF
I(OCF8.CFHOC2F, or CFHOC
70-100' if it is not a group represented by 8F7°
C, and X is the formula CFHOCF8. CFHOC2
In the case of a group represented by F6 or CFHOC8F7-11, the temperature range is 0 to room temperature (about 20°C). When carrying out this reaction (i), the olefin compound is used in an equal mole or more per mole of a-fluoro-4-aminophenol, and 1.1 groups are 3 times the mole of the catalyst mill, preferably xl is the formula % Formula % Uses that are not groups shown are F!!k IBS pl, X
When I is a group represented by these formulas, about 1 mole amount is used.

After completion of the reaction, the reaction solution is poured into water, subjected to conventional treatments such as organic solvent extraction and concentration, and, if necessary, purified by operations such as chromatography, -1 distillation, and recrystallization.

Production method (11) (V milk) [In the above formula, X and Y represent the same meanings as above. ] 3-fluoro-4-ditrophenol and an olefin compound (Vl), hexafluoropropylene or 1.2
- A nitrobenzene f-hybrid compound (Tori) obtained by reacting with dibromotetrafluoroethane in the presence of a base,
For example, a method of obtaining aniline compound ill by a method of reduction with iron in the presence of an acid or a method of catalytic reduction with hydrogen in the presence of platinum dioxide.

In this reaction, the reaction temperature is as follows: 8-fluoro-4-nitro (1). When reacting 1,2-dibromotetrafluoroethane, the base used is, for example, an alkali metal hydride such as sodium hydride or potassium hydride, and sodium hydride is preferably used.

The reaction is usually carried out in an inert solvent, and examples of the solvent used include dimethylformamide, dimethylsulfoxide, tetrahydrofuran, etc., and dimethylformamide is preferably used. The reaction temperature is 0 to 100°C, preferably 0 to 80°C.

The amounts of the base and 1.2-q bromotetrafluoroethane to be used are both 0.5 to 8 moles per mole of 8-fluoro-4-nitrophenol, preferably about 1 mole each, Equimolar or more.

After the reaction is completed, the reaction solution is poured into water, subjected to conventional treatments such as organic solvent extraction and concentration, and, if necessary, purified by operations such as chromatography, distillation, and recrystallization.

In the method of obtaining the aniline compound (Ml) by reducing the compound (■), the reaction conditions are similar to conventional methods, such as reduction with iron in the presence of an acid, or contact with hydrogen in the presence of platinum dioxide. Examples include ways to give back.

In the case of iron reduction, etc., the reaction solution after the completion of the reaction is poured into sodium bicarbonate water etc. to make the liquid almost neutral, and then subjected to usual treatments such as organic solvent extraction and concentration.In the case of catalytic reduction, The metal catalyst etc. are removed by passing through and the p liquid is concentrated. If necessary, it is purified by operations such as chromatography, distillation, and recrystallization.

Production method (lit) Acetyl acetanilide compound (VW) obtained by reacting 4-acetylamino-8-fluorophenol with an olefin compound (■) or 1,2-dibromotetrafluoroethane in the presence of a base. A method of obtaining an aniline compound (1!I") by subjecting an amino group to a conventional hydrolysis treatment.

In this reaction, 8-acetylamino-8-(IK) (■ [in the above formula, X2 is the formula CF2Br, CCf12H, C
Br2H.

CFHC/, CFHOCF8. CFHOC2F,
or CFHOC8F7-n, and Y has the same meaning as above. ] In the case of reacting 2-dibromotetrafluoroethane, it follows the manufacturing method (11).

In the method of hydrolyzing the acetanilide compound (Vllll) to obtain the aniline compound (1''), the reaction conditions are according to the usual method, that is, a method of reacting in a solvent in the presence of an acid or a base, etc. Examples of acids used include mineral acids such as hydrochloric acid and sulfuric acid; examples of bases used include caustic alkalis such as caustic potash and caustic soda; or alkalis carbonates such as potassium carbonate and soda carbonate; examples of solvents used include ethanol; , methanol, alcohol such as ethylene glycol, water or a mixture thereof.The reaction temperature is room temperature (approximately 20°C) to 200°C.The amount of acid or base is 1 mole of the acetanilide compound. It is used in 1 to 10 times the molar amount.

After the reaction is completed, the reaction solution is poured into sodium bicarbonate water etc. to make the liquid almost neutral, and then subjected to usual treatments such as organic solvent extraction and concentration, and if necessary, chromatography,
Purify by distillation, recrystallization, etc.

The aniline compound (1) can then be reacted with phosgene in accordance with a conventional method to form an isocyanate compound represented by the symbol (V), and the reaction is usually carried out under the following conditions. It is done.

The amount of phosgene used in this reaction is usually 1 to 5 times the mole of aniline compound 01), and at this time, an inert solvent is usually used. For example, hydrocarbons such as hexane, heptane, benzene, and toluene, halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and chlorobenzene, and mixed solvents of two or more thereof are used. In this reaction, the reaction proceeds sufficiently from room temperature to the boiling point of the solvent. The reaction product isocyanate compound (V) thus obtained can be easily purified by distillation or the like, if necessary.

The novel intermediates of the present invention produced in this manner include the following.

Aniline compound (I): 2-fluoro-4-(2-bromo-1,1,2゜2-tetrafluoroethoxy)aniline 2-fluoro-4-(
1,1-difluoro-2゜2-dichloroethoxy)aniline 2-fluoro-4-(1,1-difluoro-2゜2-dibromoethoxy)aniline 2-fluoro-4-(2-chloro-1,1, 2-trifluoroethoxy)aniline 2-fluoro-4(1,L L 8,8.a-hexafluoropropoxy)aniline 2-fluoro-4-(1,1,2-)lifluoro-trifluoromethoxy)lifluoro methoxy)ethoxycoaniline 2-fluoro-4-[1,1,2-)lifluoro-trifluoromethoxypentafluoroethoxy)ethoxy]
Aniline 2-fluoro-4-(1,1,2-trifluoro-trifluoromethoxyheptafluoropropoxy)ethoxycoaniline isocyanate compound (D 2-fluoro-4-(2-bromo-1,1,2゜2- Tetrafluoroethoxy) phenyl isocyanate 2-fluoro-4-(1,1-difluoro-2゜2-dichloroethoxy) phenyl isocyanate 2-fluoro-4-(1,1-difluoro-2゜2-dibromoethoxy) phenyl isocyanate 2-Fluoro-4-(2-
Chloro-1,1,2-trifluoroethoxy) phenyl isocyanate 2-fluoro-4-(1,1,2,8, a, a -hexafluoropropoxy) phenyl isocyanate 2-fluoro-4-[1,1, 2-) Lifluoro-trifluoromethoxytrifluoromethoxy)ethoxy] phenyl isocyanate 2-fluoro-4-[1,1,2-trifluoro-trifluoromethoxypentafluoroethoxy)ethoxy]
Phenyl isocyanate 2-fluoro-4-[1,1,
2-) Lifluoro-trifluoromethoxyheptafluoropropoxy)ethoxy]phenyl isocyanate nitrobenzene compound (■): 1-nitro-2-fluoro-4-(2-bromo-1,l
, 2.2-tetrafluoroethoxy)benzene 1-nitro-2-fluoro-4-(1,1-difluoro-2,2-dichloroethoxy)penzene 1-nitro 2
-fluoro-4-(1,1-difluoro-2,2-dibromoethoxy)benzene l-nitro-2-fluoro-4
-(2-chloro-1,1,2-)lifluoroethoxy)
Benzene l-nitro-2-fluoro-4-(1,1,2
゜3.8.8-hexafluoropropoxy)benzene l-nitro-2-fluoro-4-[1,1,2-trifluoro-trifluoromethoxy)trifluoromethoxy)
ethoxy]benzene l-nitro-2-fluoro-4-[1,1,2=trifluoro-trifluoromethoxytantafluoroethoxy)ethoxy]benzene l-nitro-2-fluoro-4-[1,1,2 Trifluoro-trifluoromethoxyheptafluoropropoxy)ethoxy]benzeneacetanilide compound (■): 2-fluoro-4-(2-bromo-1,1,2゜2-tetrafluoroethoxy)acetanilide 2-fluoro-
4-(1,1-difluoro-2°2-dichloroethoxy)acetanilide 2-Fluoro-4-(1,1-difluoro-2°2-dibromoethoxy)acetanilide 2-
Fluoro-4-(2-chloro-1,1,2-trifluoroethoxy)acetanilide 2-fluoro-4-(1,
1,2-trifluoro-trifluoromethoxy)lifluoromethoxy)ethoxy]acetanilide 2-fluoro-4-(1,1,2-trifluoro-trifluoromethoxypentafluoroethoxy)ethoxy]
Acetanilide 2-Fluoro-4-[1,1,2-trifluoro-trifluoromethoxyheptafluoropropoxy)ethoxy]acetanilide Next, production examples of these intermediates will be shown.

Production example 4 8-fluoro-4-aminophenol 0.60f1 potassium hydroxide 0.05F and dimethylformamide 1
0 resistance was placed in a reaction vessel and stirred for 20 minutes at an oil bath temperature of 60 to 70°C. This solution was then added to the phenol and vigorously stirred for 2 hours at the same temperature under a stream of excess chlorotrifluoroethylene gas. After cooling the reaction solution, water was added to it, and then extracted twice with 150 ml of diethyl ether. The ether layers were combined, washed with water, dried, and concentrated.
A crude product was obtained. This crude product was subjected to silica gel chromatography, and 2-fluoro-4-(2-chloro-1
,1,2-trifluoroethoxy)aniline 0.67N
I got it.

Yield: 58% IHNMR (CDC#8): δ (ppm) 8.68 (28, br, ) 6.16 (I
H, dt, J=4.48Hz) 6.47-7.07
(8H, m, ) The intermediate aniline compounds thus obtained are listed below.

2-Fluoro-4-(1,1-difluoro-2,2-dichloroethoxy)aniline 1) INMR (CDCg8): δ (ppm) 8.69 (2H, br,) 5.84
(IH, t, J=5Hz) 6.60-7.10 (8H
, m,) 2-fluoro-4-(1,1-difluoro-2,2-dibromoethoxy)aniline 1) (NMR (CDC1,)
: δ(pm)m) 8.61(2)1. br, )5
．． 76 (LH, t, J=6Hz)6.50-7.2
1 (8H, Tortoise) Production Example 5 0.522 8-fluoro-4-aminophenol and 8 ml of dimethylformamide were placed in a reaction vessel, and while stirring under water cooling, sodium hydride (oil-based, 60%) was added.
．． 181 was added slowly. After the generation of hydrogen gas has stopped, perfluorovinylpropyl ether (CF2=C
FOC8F 21,82 f/ was added slowly. After stirring for 10 minutes under water cooling, the mixture was returned to room temperature. After 10 minutes, the reaction solution was poured into water, and then extracted twice with ethyl acetate 150 ml. The organic layers were combined, washed with water, dried and concentrated to obtain a crude product. This crude product was subjected to silica gel chromatography to obtain 1.06N of 2-fluoro-4-El, 1.2-trifluoro-trifluoromethoxyheptafluoropropoxy)ethoxycoaniline.

Yield: 65% IHNMR (CDC58) δCrpa 8.70. (2H4br, )5-
974 (I H# d t, J=54.8Hz)
6.59-7.10 (8H, m) Production Example 6 8-Fluoro-4-ditrophenol 2. After dissolving Of in 15 g of dimethylformamide, the solution was vigorously stirred at about 60"C for 15 minutes under a stream of hexafluoropropene in large excess with respect to the phenol. Then, 0.0 g of potassium hydroxide was added to the solution. After rapidly adding 25 F, vigorous stirring was continued under the same conditions for 2 hours.

After cooling the reaction solution, water was added to it, and then extracted twice with 100 ml of diethyl ether. Together with the ether layer,
After drying, it was concentrated to obtain a yellow oily residue. This oil was subjected to silica gel chromatography to obtain 1.20f of 2-fluoro-4-(1,1,2,8,3,8-hexafluoropropylene)nitrobenzene.

Yield: 81% 1.20 f of 2-fluoro-4-(1,1,2,8,88-hexafluoroproxy)nitrobenzene, 0.05 f of platinum dioxide and 10 yml of ethyl acetate were placed in a reaction vessel and stirred. After purging the reaction vessel with a hydrogen stream, stirring was continued at room temperature for 2 hours while introducing hydrogen gas. The reaction solution was then filtered, and the filtrate was concentrated to obtain 1.0y of 2-fluoro-4-(1,1,2.8.8.8-hexafluoropropoxy)aniline.

Yield: 92% n22Js: 1.4219 Production Example 7 In a reactor, 0.52 F of 4-acetylamino-8-fluorophenol and 1.60 F of 1,2-dibromodifluoroethane were dissolved in 10 m/dimethylformamide, After cooling to o'c, sodium hydride (
60%.

Oil-based) 0.14 f was added little by little. After the addition, stirring was continued for 12 hours at room temperature. The reaction solution was added to 5% aqueous hydrochloric acid to make it slightly acidic, and then extracted twice with 100 ml of diethyl ether. The ether layers were combined and dried to give a yellow oil as a residue. This oil was subjected to silica gel chromatography and 4-acetylamino-3-
Fluoro-1-(2-bromo-1,1°2.2-tetrafluoroethoxy)benzene 0.42 f was obtained.

Yield: 48% IHNMR (CDC/8): δ (ppm) 2.21 (8H, s, )6.85-
7.20 (2H) 7.60 (IH, br, ) 8.80 (IH, t, J = 9.0Hz) 19F-NMR
(CDC18/CF3CO2H): δ (ppm) −
47(IF,S,)-7,5(2F,8.) 10(2F*8.) 4-acetylamino-8-fluoro-1-(2-bromo-1,1,2,2-tetrafluoro ethoxy) benzene 0.4Bf and 20% hydrochloric acid water 10s+? was placed in a reaction vessel and stirred under reflux for 2 hours. Then, after cooling the reaction solution,
The mixture was poured into a 5% aqueous sodium hydrogen carbonate solution to make it slightly alkaline, and then extracted twice with 100 ml of diethyl ether. The ether layers were combined, dried and concentrated to give a yellow oily residue. This oil was subjected to silica gel chromatography, and 2-fluoro-4-(2-bromo-1゜1.2.2-tetrafluoroethoxy)aniline o, a
I got the op.

Yield: 80% 19F-NMR (CDCg8.'CF3CO2H):
δ(ppm) −52(IF, S, )F3 (
2F,S,) 10 (2F,s,) When the compound of the present invention is used as an active ingredient of an insecticide,
It is usually mixed with solid carriers, liquid carriers, gaseous carriers, feeds, etc., and if necessary, surfactants and other formulation auxiliaries are added to produce oils, emulsions, wettable powders, flowables, granules, etc. Used in powders, aerosols, fumes (fogging, etc.), poison baits, etc.

These preparations usually contain 0.01% to 95% by weight of the compound of the present invention as an active ingredient.

Examples of solid carriers used in formulation include clays (kaolin clay, diatomaceous earth, synthetic hydrated silicon oxide, bentonite, fupasamiclay, acid clay, etc.), talcs, ceramics, and other inorganic minerals (sericite, quartz,
Sulfur, activated carbon, calcium carbonate, hydrated silica, etc.), chemical fertilizers (ammonium sulfate, ammonium phosphorus, ammonium nitrate, urea, ammonium chloride, etc.), fine powders or granules, etc. Liquid carriers include water, alcohol, etc. (methanol, ethanol, etc.),
Ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amides (N,
(N-dimethylformamide, N,N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, vegetable oils such as soybean oil, cottonseed oil, etc.; Examples of propellants include chlorofluorocarbon gas, butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide, and the like.

Examples of surfactants include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkylaryl ethers and polyoxyethylenized products thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol i conductors, etc. Power,
b can be given.

Examples of formulation auxiliaries such as fixing agents and dispersants include casein, gelatin, polysaccharides (starch powder, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, sugars, synthetic water-soluble polymers (polyvinyl alcohol, etc.) , polyvinylpyrrolidone, polyacrylic acids, etc.), and examples of stabilizers include PAP (isopropyl acid phosphate), BIT (2°6-sheet
t-butyl-4-methylphenol), BHA (2-t
ert-butyl-4-methoxyphenol and 8-te
mixture with rt-butyl-4-methoxyphenol),
Examples include vegetable oil, mineral oil, surfactant, fatty acid or ester thereof.

Examples of base materials for poison bait include grain flour, vegetable essential oil, sugar,
Ingredient-free materials such as crystalline cellulose, antioxidants such as dibutylalhydroxytoluene, nordihydrolentifutic acid, preservatives such as dehydroacetic acid,
Examples include agents to prevent accidental ingestion such as capsicum powder, attractants such as cheese flavoring, onion flavoring, and peanut oil.

The preparation thus obtained is used as it is or diluted with water or the like. It can also be mixed with pond insecticides, nematicides, acaricides, soil pest control agents, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil conditioners, animal feed, etc. , or can be used simultaneously without mixing.

When the compound of the present invention is used as an agricultural insecticide, the application rate is usually 0.51 to 500 f per 10 ares, and when using an emulsion, wettable powder, flowable agent, etc. diluted with water, the application concentration is is 1 pPm to 1000 ppt
Granules, powders, etc. are applied as they are without any dilution.

In addition, when used as an insecticide for epidemic prevention, emulsions, wettable powders, flowable agents, etc. should be used at lppm to 1000 ppm in water.
For oils, aerosols, fogs, poison baits, etc., apply as is.

These application amounts and application changes vary depending on the type of formulation, application time, application location, application method, type of pest, degree of damage, etc., and may be increased or decreased regardless of the above range. You can

Examples of formulations are shown below. The area is 'M' affected area.

? Agent Example 1 10 parts each of the compounds (1) to (12) of the present invention, 14 parts of polyoxyethylene styrylphenyl vinyl, 6 parts of calcium dodecylbenzenesulfonate, 85 parts of xylene and 86 parts of dimethylformamide were thoroughly mixed. to obtain each emulsion.

i) Formulation Example 2 Compounds of the present invention (1), (8), (6), (7),
20 parts each of ('J) or (11), 10 parts of fenitrothion, 8 parts of calcium lignosulfonate, 2 parts of sodium lauryl sulfate, and 65 parts of synthetic hydrous silicon oxide are thoroughly ground and mixed to obtain a wettable powder.

Formulation Example 8 Compounds of the present invention (1), (2), (8), (7),
1 part each of (10) or (12), 2 parts of carbaryl
1 part, 87 parts of kaolin clay, and 10 parts of talc are thoroughly ground and mixed to obtain a powder.

Formulation Example 4 Compounds of the present invention (1), (8), (4), (7),
5 parts each of (9) or (11), 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 80 parts of bentonite and 62 parts of kaolin clay were thoroughly ground and mixed, and after adding water and kneading well, Granulate and dry to obtain granules.

Formulation Example 5 Compounds of the present invention (1), (8), (5), (7),
(20 parts each of 1 or (12), 8 parts of a formalin condensate of sodium naphthalene sulfonate, and 75 parts of water were thoroughly ground and mixed, and then 20 parts of methyl cellulose was added as a thickener.
% and mix to obtain a flowable agent.

Next, a test example is shown. The compounds of the present invention are indicated by the compound numbers in Table 1, and the compounds used for comparison are indicated by the compound symbols in Table 2.

Table 2 Table 8 Test Example 1 The following emulsion of the present compound obtained according to Formulation Example 1:
2 8,600 times diluted with water (equivalent to 8.5 ppm)
100++ rt was placed in a 180 ml polycup, and 20 last instar larvae of the second instar were released. The animals were fed and reared until emergence, and the inhibition rate of emergence was investigated (2 repetitions).

The results are shown in Table 8.

Test Example 2 The following compound of the present invention obtained according to Formulation Example 1 was sprayed on a turntable on a 5-plant orchid planted in a plastic cup one month after planting. After air drying, five 4th instar Spodoptera larvae were released, and 5 days later, the mortality rate was determined by examining whether they were alive or dead (8 repetitions).
.

The results are shown in Table 4.

Table 4 Test Example 8 An 80,000-fold dilution (1,25
radish sprouting 5 to 6 days after sowing 2
After the wood was soaked for 80 seconds and air-dried for about 1 hour, it was placed in a cage containing a large number of field-type diamondback moth adults aged 1 to 8 days after emergence, and eggs were collected. The number of eggs laid per sprout is 100.
When the eggs reach ~150, remove them from the cage and sprout two 5.6 cm in diameter! 11 polyethylene cups, and the salmon conversion rate after 6 days was determined (2 repetitions).

In addition, the salmonification rate was divided into the following four levels and displayed.

A: 0% B: 1-10% C: 11-20% D: 21% or more The results are shown in Table 5.

Table 1 <Effects of the Invention> The compounds of the present invention are highly effective against various insect pests of the orders Hymenoptera, Diptera, Lateroptera, Coleoptera, and Hymenoptera, especially their larvae, nymphs, and rabbits.

Claims (14)

[Claims] (1) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 represents a fluorine atom or a chlorine atom,
R^2 represents a fluorine atom when R^1 is a fluorine atom, and represents a hydrogen atom when R^1 is a chlorine atom. X is the formula CF_2Br, CCl_2H, CBr_2H, CFHC
l, CFHCF_8, CFHOCF_8, CFHOC_
Represents a group represented by 2F_6 or CFHOC_3F_7_-_n. ] A benzoyl urea derivative represented by. (2) X is the formula CFHCl, CFHCF_8, CFHOC
The benzoyl urea derivative according to claim 1, which is a group represented by F_8 or CFHOC_3F_7_-_n. (3) The benzoyl urea derivative according to claim 1 or 2, wherein R^1 and R^2 are both fluorine atoms. (4) N-2,6-difluorobenzoyl-N'-[2-fluoro-4-(2-chloro-1,1,2-trifluoroethoxy)phenyl]urea according to claim 1 or 2. (5) N-2,6-difluorobenzoyl-N'-[2-fluoro-4-(1,1,2
,3,3,3-hexafluoropropoxy)phenyl]
urea. (6) N-2,6-difluorobenzoyl-N'-[2-fluoro-4-[2-(trifluoromethoxy)-1,1,2-trifluoroethoxy]phenylurea according to claim 1 or 2 . (7) N-2,6-difluorobenzoyl-N'-[2-fluoro-4-[2-(heptafluoropropoxy)-1,1,2-trifluoroethoxy]phenyl] according to claim 1 or 2 urea. (8) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 represents a fluorine atom or a chlorine atom,
R^2 represents a fluorine atom when R^1 is a fluorine atom, and represents a hydrogen atom when R^1 is a chlorine atom. ] Benzoyl isocyanate compound shown by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, X is the formula CF_2Br, CCl_2H, CBr_
2H, CFHCl, CFHCF_3, CFHOCF_3
, CFHOC_2F_5 or CFHOC_3F_7_
- Represents a group represented by _n. 2. The method for producing a benzoyl urea derivative according to claim 1, wherein the benzoylurea derivative is reacted with an aniline compound represented by the following. (9) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 represents a fluorine atom or a chlorine atom,
R^2 represents a fluorine atom when R^1 is a fluorine atom, and represents a hydrogen atom when R^1 is a chlorine atom. ] Benzamide compound and general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X is the formula CF_2Br, CCl_2H, CBr_
2H, CFHCl, CFHCF_3, CFHOCF_3
, CFHOC_2F_5 or CFHOC_3F_7_
- Represents a group represented by _n. 2. The method for producing a benzoyl urea derivative according to claim 1, wherein the benzoylurea derivative is reacted with an isocyanate compound represented by the following. (10) An insecticide containing the benzoyl urea derivative according to claim 1 as an active ingredient. (11) An insect ovicide comprising the benzoyl urea derivative according to claim 1 as an active ingredient. (12) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X is the formula CF_2Br, CCl_2H, CBr_
2H, CFHCl, CFHCF_3, CFHOCF_3
, CFHOC_2F_5 or CFHOC_3F_7_
- Represents a group represented by _n. ] An aniline compound represented by (13) 3-fluoro-4-aminophenol and the general formula CF_2=Y [wherein, Y is the formula CCl_2, CBr_2, CFCl, C
FOCF_3, CFOC_2F_5 or CFOC_3
Represents a group represented by F_7_-_n. ] A general formula characterized by reacting an olefin compound represented by the following in the presence of a base ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X^1 is the formula CCl_2H, CBr_2H, CF
Represents a group represented by HCl, CFHOCF_3, CFHOC_2F_5 or CFHOC_3F_7_-_n. ] A method for producing an aniline compound represented by (14) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X is the formula CF_2Br, CCl_2H, CBr_
2H, CFHCl, CFHCF_3, CFHOCF_3
, CFHOC_2F_5 or CFHOC_3F_7_
- Represents a group represented by _n. ] There are general formulas characterized by reacting the aniline compound represented by the following with phosgene ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, X represents the same meaning as above. ] A method for producing an isocyanate compound shown in the following.