FR2686341A1 - N-Pyridylcarbonyl-N'-phenylureas, processes for their preparation and their use as pesticides - Google Patents

Abstract

The present invention relates to new N-pyridylcarbonyl-N'-phenylureas of formula (I) in which X1 and X2 independently represent a hydrogen atom or a halogen atom; Z1 and Z2 independently represent a hydrogen atom, a halogen atom, a C1-C6 alkyl group or a C1-C6 haloalkyl group; Y1 and Y2 independently represent a nitrogen atom or a =CX3- group, in which X3 is a hydrogen atom or a halogen atom; and Z3 represents a halogen atom or a trifluoromethyl group, useful as pesticidal active substances.

Description

N-pvridvlcarbonyl-N'-phenvlurée. processes for their
preparation and their use as pesticides
The present invention relates to new N-pyridylcarbonyl-N'-phenylureas, and methods for their preparation. It also relates to pesticide compositions containing these compounds as active substances, and a method of combating parasites by means of these active substances.

Prior to the invention, certain N-pyridylcarbonyl
N'-phenylureas have been described and used in pesticidal compositions. Various substituents have been introduced onto the phenyl ring, such as halogens or alkyl, haloalkyl, haloalkylthio, haloalkoxy, hydroxy alkylthio or bicyclophenoxy groups, as described in US Pat. Nos. 4,426,385, 4,468,405 and 4,271,111. N-pyridylcarbonyl-N'-phenylureas are generally included in the general formula of acylurea compounds, as described in patent application WO 86/03941, however, the N-pyridylcarbonyl -N '-phenylureas according to the present invention have never neither described nor synthesized.

dans laquelle X1 et X2 représentent indépendamment un atome d'hydrogène ou un atome d'halogène ; Z1 et Z2 représentent indépendamment un atome d'hydrogène, un atome d'halogène, un groupe alkyle en C1 - C6 ou un groupe haiogénoalkyle en C1 - C6;
Y1 et Y2 représentent indépendamment un atome d'azote ou un groupe =CX3- dans lequel X3 est un atome d'hydrogène ou un atome d'halogène ; et Z3 représente un atome d'halogène ou un groupe trifluorométhyle, présentent d'excellentes propriétés pesticides.We have now found that the N-pyridylcarbonyl-N'- phenylureas of formula (I)

wherein X1 and X2 independently represent a hydrogen atom or a halogen atom; Z1 and Z2 independently represent a hydrogen atom, a halogen atom, a C1-C6 alkyl group or a C1-C6 haloalkyl group;
Y1 and Y2 independently represent a nitrogen atom or a group = CX3- in which X3 is a hydrogen atom or a halogen atom; and Z3 represents a halogen atom or a trifluoromethyl group, have excellent pesticidal properties.

 It should be noted for formula (I) that the halogen atoms can be chosen from fluorine, chlorine, bromine and iodine atoms and that the alkyl groups can be chosen from methyl, ethyl, propyl, butyl, pentyl and hexyl. Preferably, X1 and / or X2 are independently a chlorine atom or a fluorine atom, X3 is a hydrogen atom or a chlorine atom, Z1 and Z2 are independently a hydrogen atom, a chlorine atom, a fluorine atom or a methyl group, Y1 is a group = CX3-, Y2 is a group = CX3- or a nitrogen atom and Z3 is a trifluoromethyl group.

 Typical examples of the compounds according to the present invention represented by the formula (I) will be indicated below.

dans laquelle Al est un groupe -NH2 ou un groupe -NCO, avec un composé phényle de formule (III)

dans laquelle A2 est un groupe -NH2 ou un groupe -NCO, étant entendu que lorsque A1 est un groupe -NH2, A2 est un groupe -NCO, et lorsque Al est un groupe -NCO, A2 est un groupe -NH2, et Yi1 Y2,
Z1, Z2 et Z3 sont définis comme ci-dessus, en présence d'un solvant inerte.Compound A N- (2-chloronicotinoyl) -N '-L3, 5-dichloro-4- (3-chloro-5-trifluoromethyl 2-pyridyloxy) phenyl] urea. pf 203 "C
Compound B N- (2-chloronicotinoyl) -N '- [3-chloro-4- (5-trifluoromethyl-2-pyridyloxy) phenyl] urea. pf 200-202 "C
Compound C N-nicotinoyl-N '- [3 -chloro-4- (5 -trifluoromethyl-2-pyridyloxy) phenyl] urea. pf 250-2550C
Compound D N- (6-chloronicotinoyl) -N '- [3,5-dichloro-4- (3 -chloro-S - trifluoromethyl-2-pyridyloxy) phenyl] urea. pf 255 C
Compound E
N- (2-chloronicotinoyl) -N '- [3 -chloro-4- (3 -chloro-5-trifluoromethyl 2-pyridyloxy) phenyl] urea. pf 182-1890C
Compound F N- (2-chloronicotinoyl) -N'- [4- (3 -chloro-5 -trifluoromethyl-2-pyridyloxy) phenyl] urea. pf 170-178 C
Compound G N- (2-chloronicotinoyl) -N '- [4- (2-chloro-4-triflu oromethyl - phenoxy) phenyl] urea. pf 156-1610C
Compound H N- (2-chloronicotinoyl) -N'- [3 -methyl-4- (5 -chloro-2-pyrimidinyloxy) phenyl] urea. pf 204-209 "C
Compound I
N- (2-chloronicotinoyl) -N '- [3-methyl-4- (5-bromo-2-pyrimidinyl oxy) phenyl) urea. pf 212-2180C
Compound J N- (2-fiuoronicotinoyl) -N'- [3,5-dichloro-4- (3 -chioro-5- trifluoromethyl-2-pyridyloxy) phenyl] urea mp 173-177 "C
Compound K N- (2-fluoronicotinoyl) -N '- [4- (3 -chloro-5-trifluoromethyl-2-pyridyloxy) phenyl] urea pf 171-1750C
Compound L
N- (2-fluoronicotinoyl) -N '- [3 -methyl-4- (5-chloro-2pyrimidinyloxy) phenyl] urea pf 175-1870C
Compound M N- (2-chloronicotinoyl) -N'- [3 -chloro-4- (5-bromo-2-pyrimidinyl oxy) phenyljurea pf 223-2250C
The N-pyridylcarbonyl-N'-phenylureas of formula (I) can be prepared by reaction of a pyridylcarbonyl compound of formula (II)

in which Al is a group -NH2 or a group -NCO, with a phenyl compound of formula (III)

in which A2 is a group -NH2 or a group -NCO, it being understood that when A1 is a group -NH2, A2 is a group -NCO, and when Al is a group -NCO, A2 is a group -NH2, and Yi1 Y2,
Z1, Z2 and Z3 are defined as above, in the presence of an inert solvent.

 Examples of suitable inert solvents are aromatic solvents such as benzene, toluene, xylenes and chlorobenzenes, aliphatic solvents such as chloroform, 1,2-dichloroethane, methylene chloride, carbon tetrachloride and n-hexane, cyclic or non-cyclic ethers such as dioxane, tetrahydrofuran and diethyl ether, cyclic or non-cyclic ketones such as acetone, nitriles such as acetonitrile and benzonitrile and esters such as ethyl acetate and butyl acetate. Mixtures of these solvents can also be used.

 For the reaction of a pyridylcarboxamide of formula (II), in which Al is a group -NH2, with an isocyanate of formula (III), in which A2 is a group -NCO, the following can be noted.

 The reaction temperature is generally between 0 C and the reflux temperature of the solvent; most often, it is higher than 400C.

 It is preferable to choose a solvent having a high boiling point, in particular a solvent such as toluene, xylene or chlorobenzene.

 The starting compounds are generally used in stoichiometric proportion.

 Pyridylcarboxamides are compounds which are known or which can be prepared according to known methods, for example as described in US Pat. Nos. 4,252,957, No. 4081451 and in J. Chem. Soc., 3512 (1951).

Isocyanates are known or can be prepared according to known methods, for example those described in the patents
US No. 4,173,637, No. 4310530 and No. 4677 110.

 For the reaction of a pyridylcarbonylisocyanate of formula (II), in which Ai represents a group -NCO, with a substituted aniline of formula (III), in which A2 is a group -NH2, the following can be noted.

 The reaction temperature is generally between 0 C and the reflux temperature of the solvent, preferably between 0 C and 300 C.

 The starting compounds are preferably used in stoichiometric amount.

 Some ureas can be obtained instantly. The reaction time is generally less than 24 hours.

Substituted anilines are known compounds which can be prepared, for example, as described in the patents
US No. 4,173,637, No. 4,310,530 and No. 4,677,110.

 The pyridylcarbonylisocyanates can be prepared by reacting the corresponding pyridylcarboxamides of formula (here), which are mentioned above, with oxalyl chloride, as described in the publication J. Org. Chem., 28, 1805 - 1811, 1963.

 The following examples illustrate the invention, without however limiting its field.

Example 1
Preparation of N- (2-chloronicotinoyl) -N '- [3,5-dichioro- 4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenyl] urea (Compound A)

 A solution of 16.5 g (0.046 mol) of 4- (3-chloro-5trifluoromethyl-2-pyridyloxy) -3,5-dichloroaniline in 100 ml of 1,2-dichloroethane is introduced dropwise at 200C in a solution 8.4 g (0.046 mol) of 2-chloronicotinoyl-isocyanate in 100 ml of 1,2-dichloroethane, and the mixture is stirred for 1 hour at 200C.

 The precipitate is collected by filtration under reduced pressure and dried. 17 g of the expected urea (Compound A) are obtained in the form of a white solid (yield 68%), the melting point of which is 193 "C.

 The dry extract of the filtrate consists almost entirely of urea.

 To identify the product, part of it is purified by pressure chromatography on a column of silica gel using a hexane / ethyl acetate mixture (v: v, 7: 3) as elution solvent, which makes it possible to obtain white crystals having a melting point of 203 "C.

Elementary analysis
CHN Cl
Calculated 42.25 1.68 10.37 26.26
Found 42.32 1.89 10.38 26.37
1 H NMR: (solvent d6 -DMSO; Ref .: TMS)
5 (ppm): 7.6 (m, 1H); 8.0 (s, 2H)
8.15 (dd, 1H); 8.6 (m, 2H)
8.75 (m, 1H); 10.5 (s, 1H); 11.55 (s, 1H).

Example 2
Preparation of N- (6-chloronicotinoyl) -N-t3,5-dichloro- 4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenyl] urea (Compound D)

 The procedure of Example 1 is used, with 13.7 g (0.075 mol) of 6-chloronicotinoyl-isocyanate and 25.4 g (0.071 mol) of the substituted aniline. 30.5 g (80% yield) of the expected urea (Compound D) are obtained. This compound is purified by recrystallization from 1,2-dichloroethane, and a white solid is obtained, the melting point of which is 255 "C.

1 H NMR: (d6 -DMSO; Ref .: TMS)
5 (ppm): 7.75 (d, 1H); 7.95 (s, 2H)
8.4 (dd, 1H); 8.6 (m, 1H)
8.7 (d, 1H); 9.0 (d, 1H)
10.85 (s, 1H); 11.45 (broad s, 1H).

Elementary analysis:
CHN
Calculated 42.25 1.68 10.37
Found 41.73 1.56 10.70
Example 3
Preparation of N- (2-chloronicotinoyl) -N '- [3-chloro-4 (5-trifluoromethyl-2.pyridyloxy) phenyl] urea (Compound B)

 A solution of 1.1 g (0.007 mol) of 2-chloronicotinamide in 60 ml of toluene is added to a solution of 2.23 g (0.0069 mol) of 3.chloro-4- (5-trifluoromethyl-2- pyridyloxy) - phenylisocyanate in 20 ml of toluene, and the reaction mixture is brought to reflux for 17 hours.

 After evaporation of the toluene under reduced pressure, the reaction mixture is purified by chromatography on a column of silica gel (elution solvent: n-hexane / ethyl acetate v: v, 1: 1), and one obtains 1.6 g (yield 49%) of white solid with a melting point of 200-202 "C.

 Said compounds C and E to M according to the present invention were also prepared using methods similar to those described above in Examples 1 to 3.

 The compounds according to the present invention have excellent activity as active components of pesticides, in particular insecticides, acaricides and pesticides against slugs and snails. For example, they are effective against plant parasitic mites such as red spiders (Tetranvchus urticae), parasites encountered in agriculture such as cruciferous moth (Plutella xylostella), cabbage caterpillar (Mamestra brassicae), gray worm (Spodoptera litura), the Colorado potato beetle (Leptinotarsa decemlineata), the European corn borer (Laspeyresia pomonella), the caterpillar of the corn cobs (Heliothis zen !, the tobacco bud miner (Heliothis virescens), cotton beetle (Anthonomus grandis), domestic unhygienic parasites such as cockroaches, house flies (Musca domestica) or common house mosquito (Culex pipiens palles !; stored seed parasites such as ringworm of Anguman seeds (Sitotroga cerealella) ), tribolium (Tribolium confu sum) or wheat moths; domestic parasites such as the sheath mite (Tinea pellionella), anthracene (Anthrenus scrophulariae), or l underground termites; and other parasites of domestic animals such as flies.

These compounds are particularly effective against parasites such as cruciferous moth and housefly which exhibit resistance to organophosphorus and / or pyrethroid insecticides. In addition, they are also effective against slugs and snails.

 The compounds according to the present invention have a particularly excellent larvicidal activity with respect to the larvae of insects and mites.

 The pesticides according to the present invention are effective in combating various harmful insects, harmful mites and other harmful parasites. They are applied in a concentration of the active component ranging from 1 to 20,000 ppm, preferably 20 to 2,000 ppm. The concentration of active components may possibly vary depending on the formulation, the manner, the objective and the time or place of the application, and the state of the parasitic insect.

 The amount of application of active ingredient per unit area is generally about 0.1 to 5000 g, preferably 5 to 1000 g per 10 ares. However, in some special cases, the amount applied may be outside the above range.

 The compounds of the present invention can be used in combination with other chemicals used in agriculture, such as insecticides, acaricides, nematocides, fungicides, antiviral agents, attractants, herbicides or regulators of plant growth, as appropriate. In some cases, efficiency is improved by combinations of this type.

 As insecticides, acaricides or nematocides of this type, mention may be made, for example, of organophosphorus compounds, carbamate compounds, chlorinated organic compounds, organometallic compounds, pyrethroid compounds, benzoylurea compounds and compounds of the juvenile hormone type. In addition, microbial insecticides such as Bacillus thuringiensis or nuclear polyhedrosis virus can also be used in combination with the compounds according to the present invention.

 As for fungicides, mention may be made of organophosphorus compounds, chlorinated organic compounds, Nhalothioalkyl compounds, dicarboxyimide compounds, benzimidazole compounds, azole compounds, carbinol compounds, benzanilide compounds, acylalanine compounds, pyridinamine compounds.

 When used as active components of pesticides, the compounds according to the present invention can be formulated together with adjuvants used in agriculture, to be in various forms such as powders, granules, water dispersible granules, wettable powders, emulsifiable concentrates, suspension concentrates, fluids, aerosols, pastes or ultra-low volume formulations, just like conventional chemicals for agriculture. When these formulations are to be used in practice, they can be used as such or after dilution with suitable diluents such as water, at a predetermined concentration.

 These formulations generally consist of 0.5-90 parts by weight of active component and 10-99.5 parts by weight of agricultural adjuvants.

 Various formulations containing the compounds according to the present invention or their diluted compositions can be applied by conventional methods for usual applications such as spraying (for example spraying, spraying under pressure, spraying in mist, atomization, spraying powder or granules or dispersion in water). In addition, it is possible to feed pets with a diet containing the above active component and to control the hatching or growth of parasites, especially insects, with their droppings.

 An example of a test of the present invention will be described below.

TEST EXAMPLE
Gray worm insecticide test
Each of the formulations containing compounds A to L as active component is dispersed in water to obtain a dispersion of the active component having a concentration of 800 ppm. Cabbage leaves are immersed in the respective dispersions for about 10 seconds, and then air-dried. A sheet of moistened filter paper is placed in a Petri dish with a diameter of 9 cm, and the dried cabbage leaves are placed on the filter paper. Gray worm (Spodoptera litura) larvae, in the second or third stage, are released on the leaves, and the petri dishes are covered and stored at a constant room temperature, in the light and at a temperature of 260 C. The 5th day after their release, the number of dead insects is counted and mortality is calculated using the following equation
Number of dead insects
Mortality (%) = ~~~~~~~~~~~~~~~~~~~~~~~~~~ x 100
Total number of insects
Mortality is 100% with each of compounds A to H, J and K, 80% with each of compounds I and L.

 The examples of formulations according to the present invention will be described below. However, the compounds of the present invention, the amount of the active components or the types of formulations are not limited to these specific examples.

FORMULATION EXAMPLE i (a) Compound of the present invention 20 parts by weight (b) Kaolin 72 parts by weight (c) Sodium lignin sulfonate 8 parts by weight
The above components are mixed evenly to obtain a wettable powder.

FORMULATION EXAMPLE 2 (a) Compound of the present invention 5 parts by weight (b) Talc 95 parts by weight
The above compounds are mixed uniformly to obtain a powder.

FORMULATION EXAMPLE 3 (a) Compound of the present invention 20 parts by weight (b) N, N-dimethylformamide 20 parts by weight (c) Polyoxyethylenealkylphenyl ether 1 0 parts by weight (d) Xylene 50 parts by weight
The above components are mixed uniformly and dissolved to give an emulsifiable concentrate.

FORMULATION EXAMPLE 4 (a) Compound of the present invention 40 parts by weight (b) Ethoxylated tristyrylphenol phosphate
triethanolamine 2 parts by weight (c) Silicon 0.2 parts by weight (d) Xanthan gum 0.1 parts by weight (e) Ethylene glycol 5 parts by weight (f) Water 52.7 parts by weight
The above components are evenly mixed and sprayed to give a suspended concentrate.

Claims (8)

 1. N-pyridylcarbonyl-N'-phenylureas of formula (I)

 wherein X1 and X2 independently represent a hydrogen atom or a halogen atom; Z1 and Z2 independently represent a hydrogen atom, a halogen atom, a C1-C6 allyl group or a C1-C6 haloalkyl group; Y1 and Y2 independently represent a nitrogen atom or a group = CX3 in which X3 is a hydrogen atom or a halogen atom; and Z3 represents a halogen atom or a trifluoromethyl group.  2. Compounds according to claim 1, characterized in that X1 and / or X2 independently represent a chlorine atom or a fluorine atom.  3. Compound according to claim 1 or 2, characterized in that N-pyridylcarbonyl-N'-phenylurea is a compound chosen from the group consisting of N- (2-chloronicotinoyl) -N '- [3, 5-dichloro -4- (3 - chloro-5-trifluoromethyl-2-pyridyloxy) phenyl] -urea, N- (2-chloronicotinoyl) -N '- [3 -chloro4- (5-trffluoromethyl-2-pyridyloxy) - phenyl] urea, N-nicotinoyl-N '- [3-chloro-4- (5-trifluoromethyl-2-pyri-dyloxy) phenyl] urea, N- (6-chloronicotinoyl) -N' - [3,5-dichloro -4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenyl] urea, N- (2-chloroni cotinoyl) -N '- [3-chloro-4- (3-chloro-5-trifluoromethyl-2 -pyridyloxy) phenyl] urea, N- (2-chloronicotinoyl) -N '- [4- (3-chloro-5-trifluoromethyl- 2-pyridyloxy) phenyl] urea, N- (2-chloronicotinoyl) - N '- [4- (2-chloro-4-trifluoromethylphenoxy) phenyl] urea, N- (2-chloronicotinoyl) -N' - [3 methyl4 (5-chloro-2-pyrimidinyloxy) phenyl] urea, N- (2-chloronico tinoyl) -N '- [3-methyl-4- (5-bromo-2-pyrimidinyloxy) phenyl] urea, N (2-fluoronicotinoyl) -N '- [3, 5-dichloro-4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenyl] urea, N- (2-fluoronicotinoyl) -N' - [4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenyl] urea, N- (2-fluoronicotinoyl) N '- [3 -methyl-4- (5-chloro-2-pyrimidinyloxy) phenyl] urea and N - (2 chloronicotinoyl) -N '- [3 chloro-4- (5-bromo-2-pyrimidinyloxy) phenyl] urea.  4. Process for the preparation of N-pyridylcarbonyl-N'phenylureas of formula (I)

 wherein X1 and X2 independently represent a hydrogen atom or a halogen atom; Z1 and Z2 independently represent a hydrogen atom, a halogen atom, a C1-C6 alkyl group or a C1-C6 haloalkyl group; Y1 and Y2 independently represent a nitrogen atom or a group = CX3 in which X3 is a hydrogen atom or a halogen atom; and Z3 represents a halogen atom or a trifluoromethyl group, characterized in that a pyridylcarbonyl compound of formula (II)

 in which A1 is an -NH2 group or an -NCO group, is reacted with a phenyl compound of formula (here)

  in which A2 is a group -NH2 or a group -NCO, it being understood that when A1 is a group -NH2, A2 is a group -NCO, and when A1 is a group -NCO, A2 is a group -NH2 and Y1, Y2, ZI, Z2 and Z3 are defined as above, in the presence of an inert solvent.  5. Method according to claim 4, characterized in that A1 is an -NCO group and A2 is an -NH2 group.  6. Method according to claim 4, characterized in that A1 is a group -NH2 and A2 is a group -NCO.  7. Pesticide composition characterized in that it contains an effective amount, from the point of view of the pesticidal action, of at least one N-pyridylcarbonyl-N'-phenylurea as defined in any one of claims 1 to 3.  8. Method for combating parasites, characterized in that it consists in applying, to the place to be protected, an effective amount, from the point of view of the pesticidal action, of at least one N-pyridyl-carbonyl-N'-phenylurea as defined in any one of claims 1 to 3.