WO1995033711A1 - Phenyl benzoyl(nicotinoyl) urea derivatives - Google Patents

Phenyl benzoyl(nicotinoyl) urea derivatives Download PDF

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Publication number
WO1995033711A1
WO1995033711A1 PCT/KR1995/000072 KR9500072W WO9533711A1 WO 1995033711 A1 WO1995033711 A1 WO 1995033711A1 KR 9500072 W KR9500072 W KR 9500072W WO 9533711 A1 WO9533711 A1 WO 9533711A1
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spp
bromo
nicotinoyl
formula
urea
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PCT/KR1995/000072
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French (fr)
Inventor
Jung Goo Lee
Je Wan Woo
Seung Hoe Kim
Yong Woo Shin
Kong Hyun Whang
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Hanwha Corporation
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Publication of WO1995033711A1 publication Critical patent/WO1995033711A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C07D213/82—Amides; Imides in position 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/46—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups containing any of the groups, X being a hetero atom, Y being any atom, e.g. acylureas
    • C07C275/48—Y being a hydrogen or a carbon atom
    • C07C275/54—Y being a carbon atom of a six-membered aromatic ring, e.g. benzoylureas
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
    • C07C273/06—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds from cyanamide or calcium cyanamide

Definitions

  • the present invention relates to a novel phenyl benz- oyl(or nicotinoyl) urea derivative having a strong pesti ⁇ cidal activity. More specifically, the present invention relates to a novel N-phenyl-N'-benzoylfor nicotinoyl) urea derivative represented by the following formula (I) :
  • X represents C- or N
  • R R 2 , R 3 , R 4 and R 5 independently of one another repre ⁇ sent fluoro, chloro, bro o or hydrogen.
  • the present invention also relates to a process for preparing the compound of formula (I) , as defined above, and a pesticidal composition comprising the compound of formula (I) as an active ingredient.
  • Patent Nos. 3,992,533 and 4,041,177 disclose benzoylurei- do-diphenyl ethers having a pesticidal activity; and U.S. Patent No. 4,148,902 discloses substituted ( (phenylamino) - carbonyl)pyridine carboxamides. These U.S. Patent Speci- fications also disclose a composition containing said compounds and a method for combating pests using the same.
  • U.S. Patent Nos. 4,166,124, 4,083,977 and 4,123,449 German Early Published Patent Nos. 2,901,334 (European Patent No. 013-414) and 3,104,407 (European Patent No. 57-888) , and the like disclose numerous benzoy- lurea derivatives having a pesticidal activity.
  • X represents C-R 4 or N
  • R 1 , R 2 , R 3 , R 4 and R 5 independently of one another repre ⁇ sent fluoro, chloro, bro o or hydrogen.
  • X represents C-R 4 or N; and R 1 , R , R 3 , R 4 and R 5 independently of one another repre ⁇ sent fluoro, chloro, bromo or hydrogen, characterized in that 2-bromo-3 , 5-bis (trifluoromethyl) aniline having the folowing formula (II) ,
  • It is a further object of the present invention to provide a pesticidal composition comprising the phenyl benzoyl(or nicotinoyl) urea derivative of formula (I) as an active ingredient, in combination with an agricultur ⁇ ally acceptable carrier.
  • the present invention relates to a novel N-phenyl-N'-benzoyl(or nicotinoyl) urea derivative having the following formula (I) , which has a superior pesticidal activity :
  • X represents C-R 4 or N
  • R 1 , R 2 , R 3 , R 4 and R 5 independently of one another repre ⁇ sent fluoro, chloro, bromo or hydrogen.
  • the preferred one includes those where ⁇ in X represents CH, CF or N, R 1 represents H, F, Cl or Br, R 2 represents H or F, R 3 represents H, Cl, F or Br, and R 5 represents H, F or Cl.
  • More preferred compound of formula (I) includes those wherein X represents CH or CF, R 1 represents H, F, Cl or Br, R 2 represents H or F, R 3 represents H, F, Cl or Br, and R 5 represents H, F or Cl.
  • Typical examples of the compound of formula (I) ac ⁇ cording to the present invention are as follows :
  • the present invention relates to a process for preparing the compound of formula (I) as defined above.
  • the desired N-phenyl-N'-benzoyl(or nicotinoyl) urea derivative of formula (I) can be prepared by reacting 2-bromo-3,5- bis(trifluoromethyl)aniline of formula (II) with a benz ⁇ oyl(or nicotinoyl) isocyanate of formula (III) in a suit ⁇ able diluent or solvent, as shown in the following reac ⁇ tion scheme:
  • reaction of the compound of formula (II) with the compound of formula (III) according to the present invn- tion can be carried out in the presence of a diluent including a solvent.
  • a diluent including a solvent.
  • any inert organic solvent can be used unless it adversely affect the reac ⁇ tion.
  • the solvent which can be preferably used in this reaction includes optionally chlorinated aliphatic or aromatic hydrocarbons such as benzene, tol ⁇ uene, xylene, methylene chloride, chloroform, carbon tetrachloride, dichloroethane or chlorobenzene; ethers such as diethyl ether, dibutyl ether, tetrahydrofuran or dioxane; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone or methyl isobutyl ketone; ni- triles such as acetonitrile or propionitrile, and the like.
  • the reaction can be generally carried out at the temperature of 0°C to 120°C, preferably 10°C to 50°C, under normal pressure.
  • the reactants are preferably used in an equimolar amount. Although any one of the reactants may be used in an excessive amount, it is not advantageous in view of economics in either industrial scale or labora ⁇ tory.
  • the reaction is conducted by stirring the reactants for 24 hours or more in the solvent as mentioned above at the temperature as defined above and then filtering the resulting product in vacuo.
  • the filtered product is washed with the solvent used in the reaction and alcohols such as methanol, dried and, if required, recrystallized to obtain the desired pure benzoylurea compound according to the present invention. All the obtained products are present in the form of a crystal and thus have a definite melting point.
  • the benzoyl(or nicotinoyl) isocyanate compound of formula (III) used for preparing the compound of formula (I) according to the present invention can be prepared from a substituted benzamide represented by the following general formula (IV) or a nicotinamide represented by the following general formula (V) and oxalyl chloride accord ⁇ ing to the known method, for example, by a mathod dis ⁇ closed in references, J. Org. Chem. 27, 3742 (1962) and J. Pesticide Sci. 17, 7 (1992).
  • R R 2 , R- R 4 and R 5 are defined as previously described.
  • benzamide compounds of formula ( IV) used as the starting material for preparing the compound of formula (III ) can include 2-chloro , 2 , 4- dichloro , 2 , 4-dif luoro , 2 , 6-dichloro , 2 , 3 , 4 , 5 , 6-penta- fluoro , 2-f luoro, 2-bromo or 2 , 3 , 6-trichlorobenzamide.
  • the nicotinamide compound of formula (V) which can also be used as the starting material for preparing the compound of formula (III) can be, for example, 2-chloro, 6-chloro, 2-fluoro, 6-fluoro, 2,6-dichloro or 2-bromo- nicotinamide.
  • the compound according to the present invention can be effectively used as a pesticide in agricultural field.
  • the compound of the present invention com ⁇ bats the pest through a mechanism to inhibit a chitin synthesis which results in the inhibition of peeling off the insect skin, and therefore, is less toxic to mammals.
  • the compound of the present invention can also be utilized for protection of farm lands, forests, stored goods, and the like.
  • the compound of the present invention is active generally against not only sensitive species and resistant species but also insects under every growth stages.
  • the active compound of the present invention can be formulated into a pesticidal composition in combination with an agriculturally acceptable carrier according to a conventionl manner.
  • a pestici ⁇ dal composition constitutes the third object of the present invention.
  • Isopoda for example, Onisicus asellus, Armadillidium vulgare and Porcellio scaber
  • Diplopoda for example, Blaniulus guttulatus
  • Chilopoda for example, Geophilus carpophagus and Scurig- era spec
  • Symphila for example, Scutigerel- la immaculata
  • Thysanura for example, Lepis- a saccharina
  • Collembola for example, Onychiurus armatus
  • Orthoptera for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blatella germanica, Acheta domesticus, Gryllotal- pa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria
  • the order of Dermaptera for example, For
  • Lepidoptera for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hypono- langeta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thur- beriella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Lap- hygma exigua, Mamestra brassicae, Panolis flammea, Prode- nia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Fieris
  • Oestrus spp. Hypodrema spp. , Tabanus spp. , Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis captitata, Dacut oleae and Tipula paludosa; the order of Siphonaptera, for exam- pie, Xenopsylla cheopis and Ceratophyllus spp.
  • Arachnida for example, Scorpio maurus and Latrodectus actans
  • Acarina for example, Acarus siro, Argas spp., Ornithodorus spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ioxodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetopsa, Panonychus spp., and Tetranychus spp.
  • 2-chlorobenzoyl isocyanate was synthesized according to the same procedure as Example 1 except that 1.56g of 2- chlorobenzamide is used instead of 2-f luorobenzamide .
  • the synthesized isocyanate was reacted with the equivalent amount of 2-bromo-3 , 5-bis (trif luoromethyl) aniline accord ⁇ ing to the same procedure as Example 1 to obtain 3 .77g (Yield 77%) of the title compound as a white solid (m.p . 170-171°C) .
  • 2-bromobenzoyl isocyanate was synthesized according to the same procedure as Example 1 except that 2 . Og of 2- bromobenzamide is used instead of 2-f luorobenzamide. The synthesized isocyanate was reacted with the equivalent amount of 2-bromo-3 , 5-bis (trif luoromethyl) aniline accord ⁇ ing to the same procedure as Example 1 to obtain 4 .49g (Yield 84%) of the title compound as a white solid (m.p. 185-186°C) .
  • 2,6-dichlorobenzoyl isocyanate was synthesized accord ⁇ ing to the same procedure as Example 1 except that 1.90g of 2,6-dichlorobenzamide is used instead of 2-fluorobenza ⁇ mide.
  • the synthesized isocyanate was reacted with the equivalent amount of 2-bromo-3,5-bis(trifluoromethyl)ani ⁇ line according to the same procedure as Example 1 to obtain 4.77g (Yield 91%) of the title compound as a white solid (m.p. 203-204°C) .
  • 2,4-dichlorobenzoyl isocyanate was synthesized accord ⁇ ing to the same procedure as Example l except that 1.90g of 2,4-dichlorobenzamide is used instead of 2-fluorobenza ⁇ mide.
  • the synthesized isocyanate was reacted with the equivalent amount of 2-bromo-3,5-bis(trifluoromethyl)ani ⁇ line according to the same procedure as Example 1 to obtain 4.09g (Yield 78%) of the title compound as a white solid (m.p. 169-170°C) .
  • 4-fluorobenzoyl isocyanate was synthesized according to the same procedure as Example 1 except that l.39g of 4- fluorobenzamide is used instead of 2-fluorobenzamide.
  • the synthesized isocyanate was reacted with the equivalent amount of 2-bromo-3,5-bis(trifluoromethyl)aniline according to the same procedure as Example 1 to obtain 4.21g (Yield 89%) of the title compound as a white solid (m.p. 209- 210°C) .
  • 4-chlorobenzoyl isocyanate was synthesized according to the same procedure as Example 1 except that 1.56g of 4- chlorobenzamide is used instead of 2-f luorobenzamide .
  • the synthesized isocyanate was reacted with the equivalent amount of 2-bromo-3 , 5-bis (trif luoromethyl) aniline accord- ing to the same procedure as Example l to obtain 4 .21g (Yield 86%) of the title compound as a white solid (m.p. 222-223°C) .
  • 4-bromobenzoyl isocyanate was synthesized according to the same procedure as Example 1 except that 2 . Og of 4- bro Tavernz amide is used instead of 2-f luorobenzamide. The synthesized isocyanate was reacted with the equivalent amount of 2-bromo-3 , 5-bis (trif luoromethyl) aniline accord ⁇ ing to the same procedure as Example 1 to obtain 4 . 97g (Yield 93%) of the title compound as a white solid (m. p . 217-218°C) .
  • 3-fluorobenzoyl isocyanate was synthesized according to the same procedure as Example 1 except that 1.39g of 3 - fluorobenzamide is used instead of 2-fluorobenzamide.
  • the synthesized isocyanate was reacted with the equivalent amount of 2-bromo-3,5-bis(trifluoromethyl)aniline accord ⁇ ing to the same procedure as Example 1 to obtain 4.2lg (Yield 89%) of the title compound as a white solid (m.p. 203-205°C) .
  • 2,3,4,5,6-pentafluorobenzoyl isocyanate was synthe ⁇ sized according to the same procedure as Example 1 except that 2.11g of 2, 3,4 ,5, 6-pentafluorobenzamide is used instead of 2-fluorobenzamide.
  • the synthesized isocyanate was reacted with the equivalent amount of 2-bromo-3,5- bis(trifluoromethyl)aniline according to the same proce ⁇ dure as Example 1 to obtain 4.42g (Yield 81%) of the title compound as a white solid (m.p. 188-189°C) .
  • 2-chloronicotinoyl isocyanate was synthesized accord ⁇ ing to the same procedure as Example 1 except that 1.56g of 2-chloronicotinamide is used instead of 2-fluorobenza ⁇ mide.
  • the synthesized isocyanate was reacted with the equivalent amount of 2-bromo-3,5-bis(trifluoromethyl)ani- line according to the same procedure as Example 1 to obtain 4.12g (Yield 84%) of the title compound as a white solid (m.p. 174-175°C) .
  • Example 12 Preparation of l-r2-bromo-3.5-(bistrifluoromethyl)phenyll- 3-(6-chloronicotinoyl)urea 6-chloronicotinoyl isocyanate was synthesized accord ⁇ ing to the same procedure as Example 1 except that 1.39g of 6-chloronicotinamide is used instead of 2-fluorobenza ⁇ mide. The synthesized isocyanate was reacted with the equivalent amount of 2-bromo-3,5-bis(trifluoromethyl)ani ⁇ line according to the same procedure as Example 1 to obtain 3.83g (Yield 78%) of the title compound as a white solid (m.p. 212-213°C) .
  • the benzoylurea derivatives prepared according to the method of the present invention as mentioned above show an excel lent pestic ida l activity against diamond-back moth (Plutella maculipennis) , Spodoptera spp. , brown plan- thopper(Nilaparvata lugens), and the like.
  • Such pestici ⁇ dal activity of the active compound of the present inven ⁇ tion can be determined by the following experiments.
  • Fresh cabbage leaves were cut off in the form of a round disk having a diameter of 5 cm. 25mg of the test compound was dissolved in 50ml of a mixture containing acetone and lOOppm aqueous solution of Triton X 100 in the ratio of 1:9 to produce a test preparation containing the test compound in the concentration of 500ppm.
  • Cabbage leaf disks as prepared above were treated by being dipped into the test preparation for 30 seconds and then dried in a hood. The dried cabbage leaf disks were put into a dispersible petri dish having 5cm diameter and then 20 three-aged larvae of diamond-back moth(Plutella maculipen ⁇ nis) were inoculated thereto using a fine brush. Then, the dish was tightly closed with a lid to prevent the escape of larvae.
  • the inoculated cabbage disk was maintained at 25°C under 60% humidity. After 120 hours, abnormal growth and lethality of Plutella maculipennis were examined.
  • the control value of the test compound was calculated according to the following equation. Number of destructed larvae
  • control value 4 80% to less than 95% control value 3 50% to less than 80% control value 2 30% to less than 50% control value 1 10% to less than 30% control value 0 less than 10% control value
  • Example 6 Compound of Example 1 5 5 5 Example 2 5 5 5 Example 3 5 5 5 Example 4 5 3 Example 5 1 Example 6 1 i Example 7 2 1
  • Fresh cabbage leaves were cut off in the form of a round disk having a diameter of 5 cm. 25mg of the test compound was dissolved in 50ml of a mixture containing acetone and lOOpp aqueous solution of Triton X 100 in the ratio of 1:9 to produce a test preparation containing the test compound in the concentration of 500ppm.
  • Cabbage leaf disks as prepared above were treated by being dipped into the test preparation for 30 seconds and then dried in a hood. The dried cabbage leaf disks were put into a dispersible petri dish having 5cm diameter and then 20 three-aged larvae of Spodoptera spp. were inoculated thereto using a fine brush. Then, the dish was tightly closed with a lid to prevent the escape of larvae.
  • the inoculated cabbage disk was maintained at 25°C under 60% humidity. After 120 hours, abnormal growth and lethality of Spodoptera spp. were examined.
  • Example 5 5 5
  • Example 6 5 5
  • Example 7 3 3
  • Example 8 0
  • Example 9 1 ⁇ 1
  • Example 10 5 5
  • Example 11 1 1
  • Example 12 2 1
  • the roots of 5 seedlings of rice plant (variant : Dongjin) after 7 to 8 days from the sowing were wound with a sanitary cotton band and then inserted into the bottom of a glass test tube having 3cm diameter and 15cm length.
  • 20 adults of brown planthopper(Nilaparvata lugens) after 3 to 5 days from emergence were collected from breeding cage using a vaccum pump equipped with suction apparatus and introduced into the test tube having the inserted rice seedlings.
  • the test preparation prepared according to the same manner as Experiment 1 was sprayed directly to adult brown planthopper attached to the rice seedlings using a mi- crospray from the top end of the test tube. After treat ⁇ ment, the top end of the test tube was covered with nylon gauze to prevent the escape of brown plnathopper and then the test tube was maintained at 25°C under 60% humidity. After 120 hours, the lethality of the test insect was examined.
  • the pesticidal activity of the compound of the present invention at low concentration was determined according to the same method as in Experiment 1 and 2 using the series dilutions of the SOOppm test preparation prepared in Experiment 1. In this test, diamond-back moth(Plutella maculipennis) and Spodoptera spp. were used as the test pest. The obtained results are described in the follow ⁇ ing Table 5.
  • EX.6 B 100 100 50 20
  • A diamond-back moth (Plutella maculipennis)
  • B Spodoptera spp.
  • the compound of the present invention exhibits a superior pesticidal activity even at low concentration.

Abstract

The present invention relates to a novel N-phenyl-N'-benzoyl(or nicotinoyl) urea derivative represented by formula (I), which has a strong pesticidal activity, in which X represents C-R4 or N; and R?1, R2, R3, R4 and R5¿ independently of one another represent fluoro, chloro, bromo or hydrogen.

Description

PHENYL BENZOYL(NICOTINOYL) UREA DERIVATIVES
TECHNICAL FIELD
The present invention relates to a novel phenyl benz- oyl(or nicotinoyl) urea derivative having a strong pesti¬ cidal activity. More specifically, the present invention relates to a novel N-phenyl-N'-benzoylfor nicotinoyl) urea derivative represented by the following formula (I) :
Figure imgf000003_0001
in which
X represents C- or N, and
R R2, R3, R4 and R5 independently of one another repre¬ sent fluoro, chloro, bro o or hydrogen.
The present invention also relates to a process for preparing the compound of formula (I) , as defined above, and a pesticidal composition comprising the compound of formula (I) as an active ingredient.
BACKGROUND ART
It has been already known that some benzoylurea deriv¬ atives exhibit a pesticidal activity. For example, U.S. O 95/33711 PC17KR95
Patent Nos. 3,992,533 and 4,041,177 disclose benzoylurei- do-diphenyl ethers having a pesticidal activity; and U.S. Patent No. 4,148,902 discloses substituted ( (phenylamino) - carbonyl)pyridine carboxamides. These U.S. Patent Speci- fications also disclose a composition containing said compounds and a method for combating pests using the same. In addition, U.S. Patent Nos. 4,166,124, 4,083,977 and 4,123,449, German Early Published Patent Nos. 2,901,334 (European Patent No. 013-414) and 3,104,407 (European Patent No. 57-888) , and the like disclose numerous benzoy- lurea derivatives having a pesticidal activity.
However, these known benzoylurea derivatives have some disadvantages in that some pests are resistant thereto and they do not provide a satisfactory pesticidal effect when they are applied in a low concentration.
DISCLOSURE OF INVENTION
Therefore, the present inventors have extensively studied to develop a benzoylurea derivatives showing a superior pesticidal activity against broad species of pests, including resistant species, even at low concentra¬ tion. As a result, we have identified that a certain benzoylurea derivative having 2-bromo-3,5-bis (trifluoro- methyl)phenyl substituent, which has never been disclosed in any prior publication, can satisfy such requirements, and thus completed the present invention.
Accordingly, it is an object of the present invention to provide a novel N-phenyl-N1 -benzoyl (nicotinoyl)urea derivative represented by the following formula (I) :
Figure imgf000005_0001
in which
X represents C-R4 or N; and
R1 , R2 , R3 , R4 and R5 independently of one another repre¬ sent fluoro, chloro, bro o or hydrogen.
it is another obj ect of the present invention to provide a process for preparing the novel phenyl benzoyl (or nicotinoyl) urea derivative of formula (I) :
Figure imgf000005_0002
in which
X represents C-R4 or N; and R1 , R , R3 , R4 and R5 independently of one another repre¬ sent fluoro, chloro, bromo or hydrogen, characterized in that 2-bromo-3 , 5-bis (trifluoromethyl) aniline having the folowing formula (II) ,
Figure imgf000006_0001
is reacted with a benzoyl (or nicotinoyl) isocyanate having the following formula (III) ,
Figure imgf000006_0002
in which X, R1, R2, R3 and R5 are defined as previously described.
It is a further object of the present invention to provide a pesticidal composition comprising the phenyl benzoyl(or nicotinoyl) urea derivative of formula (I) as an active ingredient, in combination with an agricultur¬ ally acceptable carrier.
BEST MODE FOR CARRYING OUT THE INVENTION
In one aspect, the present invention relates to a novel N-phenyl-N'-benzoyl(or nicotinoyl) urea derivative having the following formula (I) , which has a superior pesticidal activity :
Figure imgf000007_0001
in which
X represents C-R4 or N; and
R1, R2, R3, R4 and R5 independently of one another repre¬ sent fluoro, chloro, bromo or hydrogen.
Among the compound of formula (I) according to the present invention, the preferred one includes those where¬ in X represents CH, CF or N, R1 represents H, F, Cl or Br, R2 represents H or F, R3 represents H, Cl, F or Br, and R5 represents H, F or Cl.
More preferred compound of formula (I) includes those wherein X represents CH or CF, R1 represents H, F, Cl or Br, R2 represents H or F, R3 represents H, F, Cl or Br, and R5 represents H, F or Cl.
Typical examples of the compound of formula (I) ac¬ cording to the present invention are as follows :
1-[2-bromo-3,5-(bistrifluoromethyl)phenyl]-3-(2-fluoroben- zoyl)urea;
1-[2-bromo-3,5-(bistrifluoromethyl)phenyl]-3-(2-chloroben- zoyl)urea;
1-[2-bromo-3,5-(bistrifluoromethyl)phenyl]-3-(2-bromoben- zoyl)urea; 1-[2-bromo-3,5-(bistrifluoromethyl)phenyl]-3-(2,6-dichlo- robenzoyl)urea;
1-[2-bromo-3,5-(bistrifluoromethyl)phenyl]-3-(2,4-dichlo- robenzoyl)urea; and
1-[2-bromo-3,5-(bistrifluoromethyl)phenyl]-3-(2-chloroni- cotinoylbenzoyl)urea.
In another aspect, the present invention relates to a process for preparing the compound of formula (I) as defined above.
According to the process of the present invention, the desired N-phenyl-N'-benzoyl(or nicotinoyl) urea derivative of formula (I) can be prepared by reacting 2-bromo-3,5- bis(trifluoromethyl)aniline of formula (II) with a benz¬ oyl(or nicotinoyl) isocyanate of formula (III) in a suit¬ able diluent or solvent, as shown in the following reac¬ tion scheme:
Figure imgf000008_0001
(ID (III)
Figure imgf000008_0002
In the above reaction scheme, X, R1, R2, R3 and R5 are defined as previously described.
The reaction of the compound of formula (II) with the compound of formula (III) according to the present invn- tion can be carried out in the presence of a diluent including a solvent. For this purpose, any inert organic solvent can be used unless it adversely affect the reac¬ tion. Particularly, the solvent which can be preferably used in this reaction includes optionally chlorinated aliphatic or aromatic hydrocarbons such as benzene, tol¬ uene, xylene, methylene chloride, chloroform, carbon tetrachloride, dichloroethane or chlorobenzene; ethers such as diethyl ether, dibutyl ether, tetrahydrofuran or dioxane; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone or methyl isobutyl ketone; ni- triles such as acetonitrile or propionitrile, and the like. The reaction can be generally carried out at the temperature of 0°C to 120°C, preferably 10°C to 50°C, under normal pressure.
In this reaction, the reactants are preferably used in an equimolar amount. Although any one of the reactants may be used in an excessive amount, it is not advantageous in view of economics in either industrial scale or labora¬ tory.
The reaction is conducted by stirring the reactants for 24 hours or more in the solvent as mentioned above at the temperature as defined above and then filtering the resulting product in vacuo. The filtered product is washed with the solvent used in the reaction and alcohols such as methanol, dried and, if required, recrystallized to obtain the desired pure benzoylurea compound according to the present invention. All the obtained products are present in the form of a crystal and thus have a definite melting point. The benzoyl(or nicotinoyl) isocyanate compound of formula (III) used for preparing the compound of formula (I) according to the present invention can be prepared from a substituted benzamide represented by the following general formula (IV) or a nicotinamide represented by the following general formula (V) and oxalyl chloride accord¬ ing to the known method, for example, by a mathod dis¬ closed in references, J. Org. Chem. 27, 3742 (1962) and J. Pesticide Sci. 17, 7 (1992).
Figure imgf000010_0001
(IV) (V)
In the above formulae, R R2 , R- R4 and R5 are defined as previously described.
Specific example of the benzamide compounds of formula ( IV) used as the starting material for preparing the compound of formula (III ) can include 2-chloro , 2 , 4- dichloro , 2 , 4-dif luoro , 2 , 6-dichloro , 2 , 3 , 4 , 5 , 6-penta- fluoro , 2-f luoro, 2-bromo or 2 , 3 , 6-trichlorobenzamide.
The nicotinamide compound of formula (V) which can also be used as the starting material for preparing the compound of formula (III) can be, for example, 2-chloro, 6-chloro, 2-fluoro, 6-fluoro, 2,6-dichloro or 2-bromo- nicotinamide.
The compound according to the present invention can be effectively used as a pesticide in agricultural field. Particularly, the compound of the present invention com¬ bats the pest through a mechanism to inhibit a chitin synthesis which results in the inhibition of peeling off the insect skin, and therefore, is less toxic to mammals. The compound of the present invention can also be utilized for protection of farm lands, forests, stored goods, and the like. The compound of the present invention is active generally against not only sensitive species and resistant species but also insects under every growth stages.
For practical use, the active compound of the present invention can be formulated into a pesticidal composition in combination with an agriculturally acceptable carrier according to a conventionl manner. Thus, such a pestici¬ dal composition constitutes the third object of the present invention.
As the pest on which the pesticidal composition of the present invention can be effectively used, the followings can be mentioned:
the class of Isopoda, for example, Onisicus asellus, Armadillidium vulgare and Porcellio scaber; the class of Diplopoda, for example, Blaniulus guttulatus; the class of Chilopoda, for example, Geophilus carpophagus and Scurig- era spec; the class of Symphila, for example, Scutigerel- la immaculata; the order of Thysanura, for example, Lepis- a saccharina; the order of Collembola, for example, Onychiurus armatus; the order of Orthoptera, for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blatella germanica, Acheta domesticus, Gryllotal- pa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria; the order of Dermaptera, for example, Forficula auricularia; the order of Isoptera, for example, Reticulitermes spp.; the order of Anoplura, for example, Phylloxera vastratrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. and Linognathus spp. ; the order of Mallophaga, for example, Trichodectes spp. and Da alinea spp. ; the order of Thysa- noptera, for example, Hercinothrips femoralis and Thrips tabaci; the order of Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Cimex lectularius, Rhodnius prolixus and Triato a spp.; the order of Homoptera, for example, Aleurodes brassicae, Piesma quadrata, Trialeu- rodes vaporariorum. Aphis gossypii, Brevicoryne brasicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparva- ta lugens, Aonidiella aurantii, Aspidiotus hederae, Pseu- dococcus spp. and Psylla spp.; the order of Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hypono- meuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thur- beriella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Lap- hygma exigua, Mamestra brassicae, Panolis flammea, Prode- nia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Fieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambi- guella, Ho ona magnanima and Tortrix viridana; the order of Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemli- neata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomiria spp., Ory- zaephilus surinamensis, Anthono us spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorr- hynchus assimilis, Hypera postica, Dermestes spp., Trogo- derma spp., Anthrenus spp., Attagenus spp., Lyctus spp.. Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra zealandica; the order of Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.; the order of Diptera, for example, Aedes spp., Anopheles spp., Cules spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucillia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hypobosca spp., Stomoxys spp. , Oestrus spp. , Hypodrema spp. , Tabanus spp. , Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis captitata, Dacut oleae and Tipula paludosa; the order of Siphonaptera, for exam- pie, Xenopsylla cheopis and Ceratophyllus spp. ; the class of Arachnida, for example, Scorpio maurus and Latrodectus actans; the order of Acarina, for example, Acarus siro, Argas spp., Ornithodorus spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ioxodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetopsa, Panonychus spp., and Tetranychus spp.
The present invention will be more specifically ex¬ plained by the following examples. However, it should be understood that the examples are intended to illustrate and not to limit the scope of the present invention in all its aspects.
Example 1
Preparation of l-r2-bromo-3 -5-(bistrifluoromethyl)phenyll-
3-(2-fluorobenzoyHurea
1.40g (10 mmole) of 2-fluorobenzamide and 15ml of dry dichloroethane were introduced into a 100ml flask and then 0.92ml (10.5 mmole) of oxalyl chloride was slowly added thereto through a syringe at normal temperature. In this case, the reaction was exothermally conducted with gener¬ ating hydrogen chloride gas. The reaction solution was refluxed for 8 hours and then cooled down to normal tem¬ perature. The reaction solvent and excessive oxalyl chloride were removed in vacuo to obtain 2-fluorobenzoyl isocyanate in an oily state. The oily 2-fluorobenzoyl isocyanate was dissolved in 20ml of dry dichloroethane and then 3.08g of 2-bromo-3,5-bis(trifluoromethyl)aniline dissolved in 20ml of dichloroethane was added dropwise thereto to obtain 3.8g (Yield 81%) of the title compound as a white powder (m.p. 170-171°C) .
Example 2
Preparation of l- r2-bromo-3 , 5- (bistrif luoromethyl^ phenyll - 3 - ( 2 -chlorobenzoyl) urea
2-chlorobenzoyl isocyanate was synthesized according to the same procedure as Example 1 except that 1.56g of 2- chlorobenzamide is used instead of 2-f luorobenzamide . The synthesized isocyanate was reacted with the equivalent amount of 2-bromo-3 , 5-bis (trif luoromethyl) aniline accord¬ ing to the same procedure as Example 1 to obtain 3 .77g (Yield 77%) of the title compound as a white solid (m.p . 170-171°C) .
Example 3
Preparation of l- r2-bromo-3 .5- (bistrif luoromethyl) phenyll - 3 - ( 2 -bro obenzoyl ) rea
2-bromobenzoyl isocyanate was synthesized according to the same procedure as Example 1 except that 2 . Og of 2- bromobenzamide is used instead of 2-f luorobenzamide. The synthesized isocyanate was reacted with the equivalent amount of 2-bromo-3 , 5-bis (trif luoromethyl) aniline accord¬ ing to the same procedure as Example 1 to obtain 4 .49g (Yield 84%) of the title compound as a white solid (m.p. 185-186°C) .
Example 4 Preparation of l-r2-bromo-3.5-(bistrifluoromethyl phenyll- 3-(2.6-dichlorobenzoyl urea
2,6-dichlorobenzoyl isocyanate was synthesized accord¬ ing to the same procedure as Example 1 except that 1.90g of 2,6-dichlorobenzamide is used instead of 2-fluorobenza¬ mide. The synthesized isocyanate was reacted with the equivalent amount of 2-bromo-3,5-bis(trifluoromethyl)ani¬ line according to the same procedure as Example 1 to obtain 4.77g (Yield 91%) of the title compound as a white solid (m.p. 203-204°C) .
Example 5
Preparation of 1-f2-bromo-3,5-(bistrifluoromethyl)phenyl1-
3-(2.4-dichlorobenzoγl)urea
2,4-dichlorobenzoyl isocyanate was synthesized accord¬ ing to the same procedure as Example l except that 1.90g of 2,4-dichlorobenzamide is used instead of 2-fluorobenza¬ mide. The synthesized isocyanate was reacted with the equivalent amount of 2-bromo-3,5-bis(trifluoromethyl)ani¬ line according to the same procedure as Example 1 to obtain 4.09g (Yield 78%) of the title compound as a white solid (m.p. 169-170°C) .
Example 6
Preparation of l-r2-bromo-3-5-(bistrifluoromethyl)phenyl1- 3-(4-fluorobenzoyl rea
4-fluorobenzoyl isocyanate was synthesized according to the same procedure as Example 1 except that l.39g of 4- fluorobenzamide is used instead of 2-fluorobenzamide.
The synthesized isocyanate was reacted with the equivalent amount of 2-bromo-3,5-bis(trifluoromethyl)aniline according to the same procedure as Example 1 to obtain 4.21g (Yield 89%) of the title compound as a white solid (m.p. 209- 210°C) .
Example 7
Preparation of l- r2-bromo-3 , 5- (bistrif luoromethyl ) phenyl ] -
3- (4-chlorobenzoyl) urea
4-chlorobenzoyl isocyanate was synthesized according to the same procedure as Example 1 except that 1.56g of 4- chlorobenzamide is used instead of 2-f luorobenzamide . The synthesized isocyanate was reacted with the equivalent amount of 2-bromo-3 , 5-bis (trif luoromethyl) aniline accord- ing to the same procedure as Example l to obtain 4 .21g (Yield 86%) of the title compound as a white solid (m.p. 222-223°C) .
Example 8 Preparation of l- r2-bromo-3 , 5- (bistrif luoromethyl) henyll - 3- (4-bromobenzoyl) urea
4-bromobenzoyl isocyanate was synthesized according to the same procedure as Example 1 except that 2 . Og of 4- bro obenz amide is used instead of 2-f luorobenzamide. The synthesized isocyanate was reacted with the equivalent amount of 2-bromo-3 , 5-bis (trif luoromethyl) aniline accord¬ ing to the same procedure as Example 1 to obtain 4 . 97g (Yield 93%) of the title compound as a white solid (m. p . 217-218°C) .
Example 9
Preparation of l- r2-bromo-3 . 5- (bistrif luoromethyl ) henyl ] -
3- ( 3-f luorobenzoyl) urea
3-fluorobenzoyl isocyanate was synthesized according to the same procedure as Example 1 except that 1.39g of 3- fluorobenzamide is used instead of 2-fluorobenzamide. The synthesized isocyanate was reacted with the equivalent amount of 2-bromo-3,5-bis(trifluoromethyl)aniline accord¬ ing to the same procedure as Example 1 to obtain 4.2lg (Yield 89%) of the title compound as a white solid (m.p. 203-205°C) .
Example 10
Preparation of l~r2-bromo-3 ,5-(bistrifluoromethyl)phenyl]- 3-(2.3,4.5.6-pentafluorobenzoyl)urea
2,3,4,5,6-pentafluorobenzoyl isocyanate was synthe¬ sized according to the same procedure as Example 1 except that 2.11g of 2, 3,4 ,5, 6-pentafluorobenzamide is used instead of 2-fluorobenzamide. The synthesized isocyanate was reacted with the equivalent amount of 2-bromo-3,5- bis(trifluoromethyl)aniline according to the same proce¬ dure as Example 1 to obtain 4.42g (Yield 81%) of the title compound as a white solid (m.p. 188-189°C) .
Example 11
Preparation of l-r2-bromo-3 ,5-(bistrifluoromethyl)phenyll-
3-f2-chloronicotinoyl)urea . .
2-chloronicotinoyl isocyanate was synthesized accord¬ ing to the same procedure as Example 1 except that 1.56g of 2-chloronicotinamide is used instead of 2-fluorobenza¬ mide. The synthesized isocyanate was reacted with the equivalent amount of 2-bromo-3,5-bis(trifluoromethyl)ani- line according to the same procedure as Example 1 to obtain 4.12g (Yield 84%) of the title compound as a white solid (m.p. 174-175°C) .
Example 12 Preparation of l-r2-bromo-3.5-(bistrifluoromethyl)phenyll- 3-(6-chloronicotinoyl)urea 6-chloronicotinoyl isocyanate was synthesized accord¬ ing to the same procedure as Example 1 except that 1.39g of 6-chloronicotinamide is used instead of 2-fluorobenza¬ mide. The synthesized isocyanate was reacted with the equivalent amount of 2-bromo-3,5-bis(trifluoromethyl)ani¬ line according to the same procedure as Example 1 to obtain 3.83g (Yield 78%) of the title compound as a white solid (m.p. 212-213°C) .
The compounds of the present invention prepared in Examples 1 to 12 are summarized in the following Table 1.
Table 1.
Figure imgf000019_0001
The benzoylurea derivatives prepared according to the method of the present invention as mentioned above show an excel lent pestic ida l activity against diamond-back moth (Plutella maculipennis) , Spodoptera spp. , brown plan- thopper(Nilaparvata lugens), and the like. Such pestici¬ dal activity of the active compound of the present inven¬ tion can be determined by the following experiments.
Experiment 1
Test for pesticidal activity against diamond-back moth
TPlutella maculipennis)
Fresh cabbage leaves were cut off in the form of a round disk having a diameter of 5 cm. 25mg of the test compound was dissolved in 50ml of a mixture containing acetone and lOOppm aqueous solution of Triton X 100 in the ratio of 1:9 to produce a test preparation containing the test compound in the concentration of 500ppm. Cabbage leaf disks as prepared above were treated by being dipped into the test preparation for 30 seconds and then dried in a hood. The dried cabbage leaf disks were put into a dispersible petri dish having 5cm diameter and then 20 three-aged larvae of diamond-back moth(Plutella maculipen¬ nis) were inoculated thereto using a fine brush. Then, the dish was tightly closed with a lid to prevent the escape of larvae.
The inoculated cabbage disk was maintained at 25°C under 60% humidity. After 120 hours, abnormal growth and lethality of Plutella maculipennis were examined.
The same procedure was conducted using a 250ppm test preparation which was prepared by diluting 500ppm test preparation as prepared above, two times with the same mixture of acetone and Triton X as used above.
The control value of the test compound was calculated according to the following equation. Number of destructed larvae
Control value (%) = X 100
Total number of test larvae
The efficacy of the test compound was estimated ac¬ cording to the following criterion and the results are desribed in the following Table 2.
5 95% to 100% control value 4 80% to less than 95% control value 3 50% to less than 80% control value 2 30% to less than 50% control value 1 10% to less than 30% control value 0 less than 10% control value
Table 2. Pesticidal activity against diamond-back moth (Plutella maculipennis)
Control value
Test compound
500 ppm 250 ppm
Compound of Example 1 5 5 Example 2 5 5 Example 3 5 5 Example 4 5 3 Example 5 1 Example 6 1 i Example 7 2 1
1 Example 8 4
4 Example 9 2 2 Example 10 4 4 Example 11 3 3 Example 12 1 Experiment 2
Test for pesticidal activity against Spodoptera spp.
Fresh cabbage leaves were cut off in the form of a round disk having a diameter of 5 cm. 25mg of the test compound was dissolved in 50ml of a mixture containing acetone and lOOpp aqueous solution of Triton X 100 in the ratio of 1:9 to produce a test preparation containing the test compound in the concentration of 500ppm. Cabbage leaf disks as prepared above were treated by being dipped into the test preparation for 30 seconds and then dried in a hood. The dried cabbage leaf disks were put into a dispersible petri dish having 5cm diameter and then 20 three-aged larvae of Spodoptera spp. were inoculated thereto using a fine brush. Then, the dish was tightly closed with a lid to prevent the escape of larvae.
The inoculated cabbage disk was maintained at 25°C under 60% humidity. After 120 hours, abnormal growth and lethality of Spodoptera spp. were examined.
The same procedure was conducted using a 250ppm test preparation which was prepared by diluting 500ppm test preparation as prepared above, two times with the same mixture of acetone and Triton X as used above.
The control value of the test compound was calculated as in Experiment 1 and the efficacy was estimated accord¬ ing to the same criterion as described in Experiment 1. The results are described in the following Table 3. Table 3. Pesticidal activity against Spodoptera spp.
Control value
Test compound
500 ppm 250 ppm i
Compound of Example 1 5 5 Example 2 5 5 Example 3 3 3 Example 4 5 5
1 Example 5 5 5 Example 6 5 5 Example 7 3 3 Example 8 0 Example 9 1 ~ 1 Example 10 5 5 Example 11 1 1 ' Example 12 2 1
1
Experiment 3 Test for pesticidal activity against brown planthopper (Nilaparvata lugens)
The roots of 5 seedlings of rice plant (variant : Dongjin) after 7 to 8 days from the sowing were wound with a sanitary cotton band and then inserted into the bottom of a glass test tube having 3cm diameter and 15cm length. 20 adults of brown planthopper(Nilaparvata lugens) after 3 to 5 days from emergence were collected from breeding cage using a vaccum pump equipped with suction apparatus and introduced into the test tube having the inserted rice seedlings. The test preparation prepared according to the same manner as Experiment 1 was sprayed directly to adult brown planthopper attached to the rice seedlings using a mi- crospray from the top end of the test tube. After treat¬ ment, the top end of the test tube was covered with nylon gauze to prevent the escape of brown plnathopper and then the test tube was maintained at 25°C under 60% humidity. After 120 hours, the lethality of the test insect was examined.
The control value of the test compound was calculated as in Experiment 1 and the efficacy was estimated accord¬ ing to the same criterion as described in Experiment 1. The results are described in the following Table 4.
Table 4. Pesticidal activity against brown planthopper (Nilaparvata lugens)
Control value
Test compound
500 ppm 250 ppm
Compound of Example 1 1 -
Example 2 3 2
Example 3 2 2
Example 4 1 -
Example 5 1 1
Example 6 1 -
Example 7 1 1
Example 8 1 1
Example 9 1 -
Example 10 1 -
Example 11 1 -
Example 12 1 - Experiment 4
Pesticidal activity at low concnetration
The pesticidal activity of the compound of the present invention at low concentration was determined according to the same method as in Experiment 1 and 2 using the series dilutions of the SOOppm test preparation prepared in Experiment 1. In this test, diamond-back moth(Plutella maculipennis) and Spodoptera spp. were used as the test pest. The obtained results are described in the follow¬ ing Table 5.
Table 5. Pesticidal activity against diamond-back moth and Spodoptera spp. at low concentration
Control value
Test Test comp. pest 500 250 16 1 0.25 0.063 0.016 0.004 (ppm)
A 100 100 100 100 20 10 -
EX.l
B 100 100 100 100 90 10 10
A 100 100 60 50 40 40 -
EX.2
B 100 100 100 100 80
EX.3 A 100 100 100 50 20 20
A 100 60 50 40
EX.4
B 100 100 100 50
EX.5 B 100 100 100 70
EX.6 B 100 100 50 20
Note : A = diamond-back moth (Plutella maculipennis) B = Spodoptera spp.
As can be seen from the above Table 5, the compound of the present invention exhibits a superior pesticidal activity even at low concentration.

Claims

WHAT IS CLAIMED IS :
1. A benzoyl(or nicotinoyl) urea derivative represented by the following formula (I) :
Figure imgf000027_0001
in which
X represents C-R4 or N; and
R1, R2, R3, R4 and R5 independently of one another repre¬ sent fluoro, chloro, bromo or hydrogen.
2. The benzoyl(or nicotinoyl) urea derivative of claim 1, wherein the compound of formula (I) is l-[2-bromo-3,5- (bistrifluoromethyl)phenyl]-3-(2-fluorobenzoyl)urea.
3. The benzoyl(or nicotinoyl) urea derivative of claim 1, wherein the compound of formula (I) is l-[2-bromo-3,5- (bistrifluoromethyl)phenyl]-3-(2-chlorobenzoyl)urea.
4. The benzoyl(or nicotinoyl) urea derivative of claim 1, wherein the compound of formula (I) is l-[2-bromo-3,5-
(bistrifluoromethyl)phenyl]-3-(2-bromobenzoyl)urea.
5. The benzoyl(or nicotinoyl) urea derivative of claim 1, wherein the compound of formula (I) is l-[2-bromo-3,5- (bistrifluoromethyl)phenyl]-3-(2,6-dichlorobenzoyl)urea.
6. The benzoyl(or nicotinoyl) urea derivative of claim 1, wherein the compound of formula (I) is 1-[2-bromo-3,5- (bistrifluoromethyl)phenyl]-3-(2,4-dichlorobenzoyl)urea.
7. The benzoyl(or nicotinoyl) urea derivative of claim 1, wherein the compound of formula (I) is l-[2-bromo-3,5-
(bistrifluoromethyl)phenyl]-3-(2-chloronicotinoyl)urea.
8. A process for preparing a benzoyl(or nicotinoyl) urea derivative of formula (I) :
Figure imgf000028_0001
in which X represents C-R4 or N; and
R1, R2, R3, R4 and R5 independently of one another repre¬ sent fluoro, chloro, bromo or hydrogen, characterized in that 2-bromo-3,5-bis(trifluoromethyl)ani¬ line having the folowing formula (II) ,
Figure imgf000028_0002
is reacted with a benzoyl(or nicotinoyl) isocyanate having the following formula (III), O 95/33711
27
Figure imgf000029_0001
in which X, R1, R2 , R3 and R5 are defined as above.
9. A pesticidal composition comprising as an active ingredient a benzoyl (or nicotinoyl) urea derivative repre¬ sented by the following general formula (I) :
Figure imgf000029_0002
in which X, R1, R2, R3 and R5 are defined as described in claim 1, in combination with an agriculturally acceptable carrier.
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WO1997024321A1 (en) * 1995-12-27 1997-07-10 Hanwha Corporation Aryl benzoyl urea derivative and pesticidal composition comprising the same
WO1998000394A1 (en) * 1996-06-29 1998-01-08 Hanwha Corporation 2-chloro-3,5-bis(trifluoromethyl)phenyl benzoyl urea derivative and process for preparing the same
CN102960356A (en) * 2012-12-12 2013-03-13 海利尔药业集团股份有限公司 Parasiticide composite containing bistrifluron and methoxyfenozide
CN102986700A (en) * 2012-12-18 2013-03-27 海利尔药业集团股份有限公司 Insecticide composition containing flutenzine and bistrifluron

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