JPH013159A - Insecticidal benzoyl urea - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to benzoyl urea derivatives having insecticidal activity, and more specifically, to benzoyl urea derivatives having insecticidal activity. The present invention relates to 1-benzoyl-3-aryl-urea derivatives having the present invention and uses of these derivatives.

The present invention further relates to methods for synthesizing these ureas.

Problems to be solved by the prior art invention 1-benzoyl-3-aryl- endowed with insecticidal activity
Several urea derivatives are known.

The first of these to be commercially available was Dirlubenzuron, which is a compound 1-(2,6-difluorobenzoyl) described in U.S. Pat. )−
It is the common name for 3-(4-chloro-phenyl)-urea.

However, difluorobenturon has 4-chloro-
Contains aniline units and is suspected of being carcinogenic [E
european chem, news 6(16),
29 (1978)].

Means for solving the problem We have here found a derivative of 1-benzoyl-3-aryl-urea, which is also an object of the invention, whose -formula is: R represents a chlorine or fluorine atom.

R1 represents hydrogen, chlorine or fluorine atom; R2 and R5 are the same or different, hydrogen atom, halogen atom,
Alkyl group containing 1 to 4 carbon atoms represents a haloalkyl group containing 1 to 4 carbon atoms: R3 and R4 are the same or different and represent a hydrogen atom, a halokene atom, an alkyl, haloalkyl, alkoxy or haloalkoxy group ; Z represents an oxygen or sulfur atom.

R6 and R9 are the same or different, hydrogen atom, H1
Represents a Ken atom, alkyl, haloalkyl, alkoxy, or a 1-core alkoxy group.

R7 and R8 are the same or different, hydrogen atom, haloken atom, alkyl, haloalkyl, alkoxy, ha1
Represents a core alkoxy group; X represents oxygen or a sulfur atom; Y is an alkylene group containing 2 to A carbon atoms, haloethylene or haloethenyl group; R+o is c, -c4 alkyl, c, -c4 haloalkyl, C3- C4 alkenyl, C3-C4 haloalkenyl,
9 represents a group of C3-C4 dichlorofurkyl, C3-C4 halocycloalkyl or C3-C4 cycloalkenyl. In the above definitions, halogen preferably means a fluorine, chlorine or bromine atom, furthermore R3R4, R6,
The alkyl moieties of R7, R8 and R9 are C, -C4 unless otherwise specified.

The compounds of formula (I) have insecticidal activity and are used for pest control in agriculture, forestry, civil life and veterinary medicine.

In the description of the production of the compound of formula (I) described below, unless otherwise specified, R, R,, R2, R3, R4, R5,
R, l? , R8,R9,R,o-X-V-
Z Compounds of formula (I>) having the meanings specified in formula (I>) can be obtained by reacting benzoyl isocyanate of the following formula with aromatic amine of the following formula.

This reaction requires the presence of a catalyst, in an inert solvent, O'
The reaction is carried out at a temperature between C and the boiling temperature of the mixture.

Aromatic hydrocarbons, hydrocarbon chlorides, ethers, ketones and acetonitrile are suitable solvents.

Benzoyl isocyanate of formula (n) is a known compound and is sometimes commercially available.

Amines of formula (I[[) can be prepared by known methods.

For example, the ethereal compound 20 "2=CF-OR1o (IV
) (wherein R1o has the meaning prescribed in formula (I)) can be prepared by reacting with the following equation at a temperature of 10 to 40°C. R5R, R9R8 (■ The ether of formula (rV) can be prepared by a known method. Prepared by

For example, when R7° is an alkyl or aryl group, J
, Am, Chem, Soc,, 82.5116 (1
900), when R1° is a polyhaloalkyl group, J, Org, CC11e, 4
8.242 (1983).

As will be apparent to those skilled in the art, several alternative methods of synthesizing the products and intermediates of formula (I) are possible.

One alternative method for the synthesis of compounds of formula (I>) consists, for example, in reacting a henzamide of the formula: with an incyanate of the formula:

Such reactions are carried out under conditions similar to those described for the reaction between benzoyl isocyanates of formula (II) and amines of formula (I[[) above.

However, the preparation of incyanates of formula (Vff') anticipates the preparation of amines of formula (I) and reaction of said amines with phosgene.

This point of view, together with the fact that the benzoyl isocyanate of formula (II>) can be used in the same way as the amide of formula (■I),
The synthetic methods described above lead to reactions between compounds of formula (■) and formula (I[[) to be generally preferred.

As previously pointed out, the compounds of formula (I) are endowed with high insecticidal activity and are particularly potent against pest larvae and eggs.

Among living organisms, the compounds of formula (I) are particularly effective against those belonging to the orders Lepidoptera, Diptera, and Coleoptera. Contains several important species.

The compounds of formula (I>) are therefore suitable for a variety of applications, such as the protection of agricultural cultivation from herbivorous insects, the protection of the environment from insects and flies, and the prevention of parasites from livestock farming.

Furthermore, the compounds of formula (I) have a concomitant acaricidal action.

In use, the compound of formula (I) may be used alone or, even better, in the active form, the compound of formula (I)
It may be advantageous to use the composition in the form of a composition containing, in addition to one or more compounds, a solid or liquid inert medium and optionally other additives.

According to customary morphological applications, the compositions are in the form of wettable powders, emulsifiable concentrates, dispersible powders, aqueous dispersions, and the like.

The amount of active principle in the composition varies over a wide range (1-956A) depending on the type of composition and the intended use of the composition. If special circumstances require it or in order to widen the range of action, other active substances can be added to the composition, for example other insecticides or acaricides. The amount of active substance (compound 'PIJ of formula (I)) to be equally distributed for insecticidal treatment depends on various factors, such as the type and severity of the insect attack, the environmental conditions in which the insect attack occurred (agricultural cultivation, depressions and waterways, various biological substrates), types of compositions used,
Varies depending on weather and environmental factors, usage methods used, etc. Usually, an amount of active substance of 001 to IK (1/lla) is sufficient for effective insecticidal purposes.

EXAMPLES The following examples more fully illustrate the invention.

Proton nuclear magnetic resonance spectra (H
-NHR), the following abbreviations were adopted.

s=1 piece.

m - multiple or undetermined complex signals: [-3; b - (broad) - 1 for broad signal' N-2,6-cyfluorobenzoyl-N-3-chloro-
Preparation of 4-[4-(1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy)phenoxy]phenylurea (first compound).

3-chloro-4-[4-(1,1,2-trifluoro-
2-(trifluoromethoxy)ethoxy)phenoxy]
Aniline 1.0Q (prepared as described in Example 3) was dissolved in anhydrous ethyl ether 151, under a nitrogen atmosphere, in a condenser,
Capacity 5 (equipped with dropping funnel, thermometer and magnetic stirrer)
1 ml flask. Next, 046 g of 2,6-cyfluoropenzoyl isocyanate was dissolved in 45 ml of anhydrous chlorobenzene and added dropwise thereto at room temperature. The mixture is 60
Heat to 50° C. for at least 1 minute, cool, and filter. The furnace liquor was concentrated under reduced pressure and the product was separated by filtration.9 077 g of benzoyl urea with a melting point of 133-135'C was obtained.9 Example 2 Starting from the aniline described in Example 3, the procedure was carried out under the same conditions as described in Example 1. , 2,6-cyfluorohensoyl isocyanate to obtain the following compound.

-Second compound N-2,6-cyfluoropenzoyl-N-4-[/1-
(1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy)phenoxy]phenylurea-Third compound N-2,6-cyfluorobenzoyl-N'-2-fluoro-4-J/I- (1,1,2-trifluoro-2-
(Trifluoromethoxy)Hexy)phenoxy]phenylurea Melting point 118-120°C -Fourth compound N-2,6-cyfluoropenzoyl N'-4-[3-
Chloro-4-(1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy)phenoxy phenylurea\ Melting point 139-141°C -Fifth compound N-2,6-cyfluorohenzoyl N' −/I−[2
The following compound was prepared using -chloro-4-(1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy)phenoxy]phenylurea 2-chlorohenzoyl isocyanate.

1.6th compound N-2-chlorohenshiyl-N-3-chloro-4-[
/1-(1゜1.2-trifluoro-2-(trifluoromethoxy)ethoxy)phenoxy side phenyl urea melting point 130-132°C - 7th compound N-2-chlorobenzoyl-N-444-], ]1,
2-Trifluoro2-trifluoromethoxy)ethoxy)phenoxy]phenylurea Melting point 150-153°C -Eighth compound N-2-chlorobenzoyl-N-2-fluoro-/I
-[4-(1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy)phenoxy]phenylurea Melting point 103-104°C -9th compound N-2-chlorobenzoyl-N'-4-[3 -chloro-
4-(i.

1.2-trifluoro-2-(trifluoromethoxy)
ethoxy) phenoxy side phenyl urea Melting point 119-122°C - 10th compound N-2-chlorobenzoyl-N-4-[2-chloro-4
−(+.

1.2-F-Lifluoro-2-(trifluoromethoxy)ethoxy)phenoxy]phenylurea Melting point 108-110°C Example 3 Preparation of intermediate aniline.

3-Chloo-4-(4-hydroxy-phenoxy)aniline 6.93! ll-dimethylsulfoxytro 1 ml.
1~24.4ml of toluene and powdered potassium hydroxide 165
g was placed in a 7-necked flask equipped with a thermometer, magnetic t18, and gas supply device.

The flask is evacuated and a container containing perfluoromethyl perfluorohinyl ether 4.6Q is connected to it.

The reaction mixture is stirred at room temperature for more than 60 minutes. Pour into water, extract with ethyl ether, dry and concentrate under vacuum.

The obtained raw material was purified by chromatography using a silica gel column to obtain 3-riL70-4-(4-(1,
1,2-trifluoro-2-(trifluoromethoxy)
653 g of (ethoxy)phenoquine coaniline was obtained.

'1I-NHR(CDCl2)', 7.4-6.15
(Ill, 7.5 H);53 (t, 05 H
); 3.5 (1)s, 211) Working under the same conditions as above, starting from 4-(4-hydroxy-phenoxy)aniline/I-[4-(1,1,2-1-lifluoro) -2-(trifluoromethoxy)ethoxy)phenoxy'aniline is obtained.

1H-NHR (CDCl2): 7,154.15 (
m, 8.5 H); 5, . 35 (t, 0.5H
): 4.0 (bs, 2+112-fluoro-4-
Starting from (4-hydroxy-phenoxy)aniline, 2-fluoro-/I-[4-(t, 1,2-trifluoro-2-trifluoromethoxy)ethoxy)-phenoxycoaniline is obtained.

'H-NOR(CDCl2): 71-61(m, 7
5 H): 5.35 ft, 0.5 H): 3.5
(bs, 2H) 4-(3-chloro-4-hydroxy-phenoxy)aniline, 4-13-chloro-4-(1,1,2-trifluoro-2-0 trifluoromethoxy)ethoxy) Obtain phenoxycoaniline.

'H-NHR (CDCl2): 7.3-6.2 (m
, 7.51+ 1:5.4 (t, 0.5 I+
): 3.5 (bs, 2H)4-(2-chloro-4
-hydroxy-phenoxy)aniline, 4-
[2-chloro-/1-(1,1,2-trifluoro-2
-(trifluoromethoxy)ethoxy)phenoxy1 to obtain aniline'H-NHR (CDCl2): 7.2-6.2 (m
, 7.510; 5.4 (t, 0.51-1);
3.5 (bs, 21+) Example 4 Insecticidal activity measurement test 1 Subotoptera litlaris 5podoptera Ii
Direct residual activity against larvae of [Lepidoptera].

Tobacco leaf G2, water containing surfactant and test product ~
An acetone solution (10% by volume of acetone) is sparged mechanically.

After the solvent has been completely removed, two-year lepidopteran larvae are deposited on the leaves.

Leaves free of larvae were kept in place under suitable conditions for the time required for the test.

For comparison (comparative test), tobacco leaves treated only with a water-acetone solution containing a surfactant (10% by volume of acetone) were also infested with larvae and kept in the same manner.

Ten days after incubating the larvae, replace the substratum of at least all of the treated tobacco leaves during that time, count the number of dead larvae, and compare that number with the number in the comparative test.

Test 2 Activity against Δedes aegypti (Diptera) larvae.

An acetone solution (3 m
1) was mixed with tap water (297ml+).

Twenty-five reared 4-day-old Diptera larvae were placed in the solution. As a comparative test, another larva was placed in a water-acetone solution (3 ml acetone, 297 ml tap water) without active product.

In comparative tests, the number of dead larvae and cocoons and the number of adults that successfully emerged from the cocoon were recorded every 2 to 3 days until the emergence of adults from the cocoon.

The activity of the test product is expressed as the percentage of dead individuals relative to the total number of treated individuals.

The insecticidal activity according to the above-mentioned test is indicated by the following rating scale: 5- Complete activity (mortality rate 98-100%) 4-
High activity (mortality rate 80-97%) 3- Good activity (1) 60-79%) 2- Adequate activity
(1) 40-59%) 1- Slight activity (horn
20-39%)〇 -No activity (!) 0-19
! ) Table 1 shows the insecticidal activity data for the indicated usage amounts using the above evaluation scale.

Table 1

Claims (1)

[Claims] 1. Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula: R represents a chlorine or fluorine atom; R_1 represents a hydrogen, chlorine or fluorine atom; R_2 and R_5 are the same or different, hydrogen atom, halogen atom, alkyl group containing 1 to 4 carbon atoms, 1 to 4 carbon atoms
Represents a haloalkyl group containing 4; R_3 and R_4
are the same or different and represent a hydrogen atom, a halogen atom, alkyl, haloalkyl, alkoxy or haloalkoxy group; Z represents an oxygen or sulfur atom; R_6 and R_9 are the same or different and represent a hydrogen atom,
halogen atom, alkyl, haloalkyl, alkoxy,
or represents a haloalkoxy group; R_7 and R_8 are the same or different, a hydrogen atom,
halogen atom, alkyl, haloalkyl, alkoxy,
or represents a haloalkoxy group; X represents oxygen or a sulfur atom; Y is an alkylene group containing 2 to 4 carbon atoms, haloethylene or haloethenyl group; R_1_0 is C_1-C_4 alkyl, C_1-C_4
Haloalkyl, C_3-C_4 alkenyl, C_3-C
_4 haloalkenyl, C_3-C_4 cycloalkyl,
C_3-C_4 halocycloalkyl or C_3-C_
represents a 4-cycloalkenyl group]. 2,N-2,6-difluorobenzoyl-N'-3-chloro-4-[4-(1,1,2-trifluoro-2-(
2. The compound according to claim 1, which is trifluoromethoxy)ethoxy)phenoxy]phenylurea. 3, N-2,6-difluorobenzoyl-N'-4-[
The compound according to claim 1, which is 4-(1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy)phenoxy]phenylurea. 4,N-2,6-difluorobenzoyl-N-2-fluoro-4-[4-(1,1,2-trifluoro-2-(
2. The compound according to claim 1, which is trifluoromethoxy)ethoxy)phenoxy]phenylurea. 5, N-2,6-difluorobenzoyl-N-4-[3
-chloro-4-(1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy)phenoxy]phenylurea. 6, N-2,6-difluorobenzoyl-N-4-[2
-chloro-4-(1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy)phenoxy]phenylurea. 7, N-2-chlorobenzoyl-N-3-chloro-4-
2. The compound according to claim 1, which is [4-(1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy)phenoxy]phenylurea. 8, N-2-chlorobenzoyl-N-4-[4-(1,
1,2-trifluoro-2-(trifluoromethoxy)
2. The compound according to claim 1, which is ethoxy)phenoxy]phenylurea. 9, N-2-chlorobenzoyl-N-2-fluoro-4
The compound according to claim 1, which is -[4-(1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy)phenoxy]phenylurea. 10, N-2-chlorobenzoyl-N-4-[3-chloro-4-(1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy)phenoxy]phenylurea according to claim 1. Compound. 11, N-2-chlorobenzoyl-N-4-[2-chloro-4-(1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy)phenoxy]phenylurea according to claim 1. Compound. 12. Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) The formula for benzoyl isocyanate: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) [In the formula, the symbols R, R_1, R_2, R_3, R_4 ,R
_5, R_6, R_7, R_8, R_9, R_1_0,
X, Y, Z have the meanings defined in claim 1] in an inert organic solvent at a temperature between 0° C. and the boiling temperature of the reaction mixture. 1. Method for producing the compound described in 1. 13. A pest control method comprising spraying an effective amount of one or more compounds according to claim 1 alone or in the form of a composition to an insect-infested area. 14. Pesticide compositions containing one or more compounds according to claim 1 as active ingredients, together with a liquid or solid inert medium and optionally other additives and/or other active substances.