JPS62155265A - N-benzoyl-n'-pyrimidylurea and insecticide containing same - Google Patents

Abstract

NEW MATERIAL:An N-benzoyl-N'-pyrimidylurea of formula I (X1 is H, halogen, nitro; X2 is halogen, nitro; Y1-Y3 are H, halogen). EXAMPLE:N-(2-Nitrobenzoyl)-N'-(5-bromo-2-pyrimidinyl)urea. USE:Insecticide. PREPARATION:For example, a benzoyl isocyanate of formula II is allowed to react with an aminopyrimidine of formula III to give the compound of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to novel N-benzoyl-N'-pyrimidinyl urea compounds and insecticides containing them.

(Disclosure of the Invention) The compound of the present invention is a novel N-benzoyl-No-pyrimidinyl urea compound represented by the following general formula (1).

[In the formula, Xl is a hydrogen atom, a halogen atom: or a nitro group, and X2 is a halogen atom] or a nitro group,
Y, , Y2 and Y3+ are hydrogen atoms or halogen atoms.

The halogen atom represented by Y2 and Y3 and j include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

The N-benzoyl-N"-pyrimivinyl urea compound of the present invention can be, for example, combined with a hendiyl isocyanate-based anastomosis represented by [wherein Xl and X2 are as described above] and [wherein, Y, , y, and Y are as described above].

This reaction is carried out in the presence of a solvent such as benzene, toluene, xylene, octane, chlorobenzene, pyridine, dioxane, dimethyl sulfoxide, ethyl acetate, etc., and the reaction temperature range is 0 to 120'C1, and the reaction time is 0.
1 to 24 hours.

Next, synthesis examples related to the compounds of the present invention will be described.

Synthesis Example I N-(2-nitrobenzoyl)-N'-(
Synthesis of 5-bromo-2-pyrimidinyl)urea 2.66
2-amino-5-
Bromopyrimidine 2.00g-t-suspended 20mA
A dioxane solution of was added at room temperature and stirred for 21 hours to complete the reaction.

After the reaction, the reactant was poured into water, the precipitated crystals were collected by filtration, washed with warm water at 40-50°C, then dissolved in a small amount of dimethyl sulfoxide, and further poured into water to remove the precipitated crystals. It was filtered. After filtering, dry under reduced pressure to obtain a melting point of 22.
N-(2-nitrobenzoyl)-N' at 0-225°C
-(5-bromo-2-pyrimidinyl)urea 2.72g
I got it.

Synthesis Example 2 N-(2,6-difluorobenzoyl)-
Synthesis of N''-(4,6-difluoro-2-pyrimidinyl)urea 2.14 g of oxalyl chloride was added to 20 ml of methylene chloride in which 0.96 g of 6-cyfluoropenzamide was dissolved. The mixture was stirred under reflux for about 1 hour, and then methylene chloride was distilled off to obtain 2,6-cyfluorohenzoyl isocyanate.
g of 2-amino-4,6-difluoropyrimidine dissolved in 10ml! A dioxane solution of was removed and stirred at 50° C. for 1.5 hours to complete the reaction.

After the reaction, the reaction product was poured into water, extracted with methylene chloride, and the extract was dried over anhydrous sodium sulfate. Subsequently, methylene chloride was distilled off and purified by silica gel column chromatography to obtain N-(2.,
6-cyfluorobenzoyl)-N'-(4゜6-
1.4 g of difluoro-2-pyrimidinyl)urea was obtained.

The following compounds can be synthesized according to the general production method and Synthesis Examples 1 and 2.

Compound N11. N-(2,6-difluorobenzoyl)
-N''-(4,6-difluoro-2-pyrimidinyl)
Urea melting point 159.5-161”C Compound m2 N-(2,6-difluorobenzoyl)
-N'-(5-chloro-2-pyrimidinyl)urea Melting point 207-209°C Compound N13 N-(2,6-difluorobenzoyl)-N'-(5-bromo-2-pyrimidinyl)urea Melting point 209-213°C Compound 1'h4 N-(2-nitrobenzoyl)-N
' -(5-bromo-2-pyrimidinyl)urea
Melting point 220-225 °C Compound 1711 to 5 N-
(2-nitrobenzoyl)-N' (5-chloro-
2-pyrimidinyl) urea Melting point 221-228
°C compounded proboscis Na 6 N (2-chlorobenzoyl)
-N'-(5-Chloro-2-pyrimidinyl)urea The compound of the present invention exhibits excellent activity as an active ingredient of insecticides, especially insecticides, as seen in the late-stage test examples. For example, diamondback moth, armyworm, armyworm, codling moth, pole worm (no Japanese name), tobacco budworm (no Japanese name), gypsy moth, Colorado potato beetle, ballweevil (no Japanese name), grasshoppers, wasp flies, scarab beetles, tamanaya moth, Agricultural pests such as the cabbage moth, sanitary pests such as cockroaches, houseflies, Culex mosquitoes,
Against storage insect pests such as the Japanese brown moth, brown rice beetle, brown rice beetle, and the Japanese white beetle, as well as clothing and household pests such as bur moths, white beetles, termites, and flies that parasitize livestock, etc. is also valid. It is also effective against various insect pests that are resistant to organophosphates, such as the house fly.

All of them are highly effective against the larvae, but when the adult insects ingest the compound of the present invention, they have the effect of making them unable to lay eggs, or even if they are able to lay eggs, preventing the eggs from becoming fertile.

When using this product as an active ingredient in insecticides, it can be formulated in various forms such as emulsions, powders, wettable powders, liquids, and pastes together with pesticide adjuvants, just as in the case of conventional pesticide formulations. I can do it. The blending ratio of these ingredients is usually 0.5 to 90 parts by weight of the active ingredient and 10 to 99.5 parts by weight of the pesticide auxiliary.
Parts by weight. When actually using these preparations,
It can be used as is or diluted to a predetermined concentration with a diluent such as water.

The agrochemical auxiliary agents mentioned herein include carriers, emulsifiers, suspending agents, dispersants, spreading agents, penetrants, wetting agents, thickeners, stabilizers, etc., and may be added as appropriate if necessary. Carriers are divided into solid carriers and liquid carriers, and solid carriers include starch, activated carbon, soybean flour, wheat flour, wood flour, fish meal, animal and vegetable powders such as milk powder, talc, kaolin, bentonite, calcium carbonate, zeolite, Examples include mineral powders such as diatomaceous earth, white carbon, clay, alumina, and sulfur powder. Liquid carriers include water, alcohols such as methyl alcohol and ethylene glycol, ketones such as acetone and methyl ethyl ketone, dioxane,
Ethers such as tetrahydrofuran, aliphatic hydrocarbons such as kerosene and kerosene, aromatic hydrocarbons such as xylene, trimethylbenzene, tetramethylhenzene, cyclohexane and solvent naphtha, halogenated hydrocarbons such as chloroform and chlorohenzene. , acid amides such as dimethylformamide, esters such as ethyl acetate and glycerin ester of fatty acids, nitrites such as acetonitrile, and money-making metals such as dimethyl sulfoxide.

In addition, other agricultural chemicals such as insecticides, acaricides, nematicides, fungicides, antiviral agents, attractants, herbicides,
It can be mixed or used in combination with plant growth regulators, etc., and may exhibit even better effects in this case.

For example, as an insecticide, acaricide, or nematicide,
0-(4-bromo-2-chlorophenyl)O-ethyl
S-propyl phosphorothioate, 2,2-dichlorovinyldimethyl phosphate, ethyl 3-methyl-4-(methylthio)phenyl isopropyl phosphoramidate, 0.0-dimethyl 0-4-nitro-m-tolyl phosphorothioate, 0-ethyl 0 -4-Nitrophenyl phenylphosphonothioate, 0,0-diethyl ○-2-isopropyl-6-methylpyrimidine-
4-yl phosphorothioate, 0. ○-dimethyl O
-(3,5,6-dolichloro-2-pyridyl) phosphorothioate, O,S-dimethyl acetylphosphoramidothioate, O-(2,4-dichlorophenyl)
Organic phosphate ester compounds such as 0-ethyl S-propyl phosphorodithioate; l-naphthyl methyl carbamate, 2-isopropoxyphenylmethyl carbamate, 2-methyl-2-(methylthio)propionaldehyde 0-methylcarbamoyl Oxime, 2.
3-dihydro-2,2-dimethylbenzofuran-7-ylmethylcarbamate, dimethyl N,N'-[thiobis[(methylimino)carbonyloxy]]bisethanimidothiothiol, S-methyl N-(methylcarbamoyloxy) ) Thioacetimidate, N,N-dimethylcarbamoyloxyimino-2-(methylthio)acetamide, 2-(ethylthiomethyl)phenyl methylcarbamate, 2-dimethylamino-5,6-dimethylpyridin-4-yl dimethyl Carbamate, S, S'
Carbamate compounds such as -2-dimethylaminotrimethylene bis(thiocarbamate); 2.2.
2-Trichloro-1,1-bis(4-chlorophenyl)ethanol, 4-chlorophenyl-2,4,5-t'J
Organochlorine compounds such as chlorophenylsulfone; organometallic compounds such as tricyclohexultine hydroxide, (R3)-α-cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3- Methyl butyrate, 3-phenoxybenzyl (IR3)
-Sith.

trans-3-(2,2-dichlorovinyl)-2,2-
Dimethyl cyclopropane carboxylate, (RS)-
α-Cyano-3-phenoxybenzyl (IR3)-cis, trans-3-(2,2-dichlorovinyl)-2°2-dimethylcyclopropanecarboxylate, (S)
-α-cyano-3-phenoxybenzyl (IR)-cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate, (RS)-α-cyano-3-phenoxybenzyl (IRS )-cis, trans-3-(2-chloro-3,3°3-trifluoropropenyl)-2,2-'; methylcyclopropanecarboxylate, 4-methyl-2,3,5,6-titrafluoro Pyrethroid compounds such as benzyl-3-(2-chloro-3,3,3-trifluoro-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate; 1-(4-chlorophenyl) -3-(2,6-
difluorobenzoyl)urea, 1-(3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2)
-pyridyloxy)phenyl)-3-(2,6-difluorobenzoyl)urea, 1-(3,5-dichloro-
Benzoylurea compounds such as 2,4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea; 2-tert-butylimino-3-isopropyl-5-phenyl-3°4.5.6-titrahydro 2
H-1,3゜5-thiadiazin-4-one, trans-
5-(4-chlorophenyl)-N-cyclohexyl-4
-Methyl-2-oxothiazolidinone-3-carboxamide, N-methylbis(2,4-xylyliminomethyl)amine, N'-(4-chloro-〇-tolyl)-
Compounds such as N, N-dimethylformamidine;
Isopropyl (2E,4E)-11-methoxy-3,
Juvenile hormone-like compounds such as 7,11-)methyl-2,4-dodecasinoate; Other compounds include dinitro compounds, organic sulfur compounds, urea compounds, and triazine compounds. Can be mentioned. Furthermore,
It can also be used in combination with microbial pesticides such as BT agents and insect pathogen virus agents.

For example, as a fungicide, S-benzyl 0.0-diisopropyl phosphorothioate, 〇-ethyl S, S-
Organophosphorus compounds such as diphenyl phosphorodithioate, annokjium ethyl hydrogen phosphonate; 4+ 5.6.7-titrachlorophthalide;
Organochlorine compounds such as tetrachloroisofucronitrile; polymers of Manganese ethylene bis (dithiocarbamate), polymers of zinc ethylene bis (dithiocarbamate), complex compounds of zinc and pineapple, dizinc bis (dimethyldithiocarbamate) , ethylene bis(dithiocarbamate), zinc dithiocarbamate compounds such as polymers of propylene bis(dithiocarbamate); 3a, 4.7.7a-tetrahydro-N
-(trichloromethanesulfenyl)phthalimide, 3
a, 4. 7.7a-tetrahydro-N-(1,1
, 2,2-tetrachloroethanesulfenyl)phthalimide, N-(trichloromethylsulfenyl)phthalimide; 3-
(3,5-dichlorophenyl)-N-isopropyl-2
, 4-dioxoimidazolidine-1-carboxamide,
(RS)-3-(3゜5-dichlorophenyl)-5-
Methyl-5-vinyl-1,3-oxazolidine-2,4
-dione, N-(3,5-dichlorophenyl)-1,2
-'; Methylcyclopropane-1. Dicarboximide compounds such as 2-dicarboximide; methyl 1-
Benzimidazole-based compounds such as (butylcarbamoyl)benzimidazol-2-yl carbamate, dimethyl 4,4”-(0-phenylene)bis(3-thioallophanate); 1-(4-chlorophenoxy)-
, 3,3-dimethyl-1-(IH-1,2,4-triazol-1-yl)butanone, 1-(biphenyl-4-
yloxy)-3,3-dimethyl-1-(IH-1,2
,4-)riazol-1-yl)butan-2-ol,
1- (N-(4-chloro-2-trifluoromethylphenyl)-2-propoxyacetimidoylcoimidazole, 1- (2-(2,4-nidichlorophenyl)-
4-ethyl-1,3-dioxolan-2-ylmethyl)
-LH-1,2,4-) lyazole, 1- (2-(2
,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-ylmethyl)-LH-1,2,4-)
Azole compounds such as lyazole, 1-C2-(2,4-dichlorophenyl)pentyl)-1H-1,2,4-): 2゜4゛-dichloro-α-(
pyrimidin-5-yl)benzhito, lyl alcohol,
(±)-2゜4°-difluoro-α-(LH-1,2
, 4-triazol-1-ylmethyl)benzhydryl alcohol 'Th;3'
-isopropoxy-0-) luanilide, α, α, α-
Benzanilide-based compounds such as trifluoro-3°-isopropoxy-o-)ylanilide; methyl N-(
2-methoxyacetyl)-N-(2,6-xylyl)-
Acylalanine compounds such as DL-alaninate;
3-chloro-N-(3-chloro-2,6-sinitro 4
- Pyridinamine compounds such as -α, α, α-trifluorotolyl)-5-trifluorotolyl)-5-1-lifluoromethyl-2-viridinamine; other compounds include piperazine compounds, morpholine compounds, anthraquinone compounds, quinoxaline compounds, crotonic acid compounds, sulfenic acid compounds, urea compounds,
Examples include antibiotics.

The insecticide of the present invention is effective in controlling various harmful insects, and the application is generally from 1 to 20. O'00ppm, preferably 20-2. It is carried out at an active ingredient concentration of OOOppm.

The concentration of these active ingredients can be appropriately changed depending on the form of the preparation, the method of application, purpose, timing, location, pest outbreak status, etc. For example, in the case of aquatic harmful insects, it is possible to control them by spraying a chemical solution in the above concentration range at the place where they occur.
The active ingredient concentration range in water is below the above.

The application per unit area is about 0.1 to 5,000 g, preferably 5 to 1,0 g of active ingredient compound per 102
00g is used. However, deviations from these ranges are possible in special cases.

The various formulations containing the compounds of the present invention or their dilutions can be applied using commonly used application methods, such as spreading (e.g., spraying, spraying, misting, surface application of Atomycin gel, etc.), soil application ( It can be carried out by mixing, irrigation, etc.), surface application (painting, powder coating, coating, etc.), immersed poison bait, etc. It is also possible to feed livestock with the above-mentioned active ingredient mixed with their feed, and use their excrement to control harmful insects, particularly the growth and growth of harmful insects. Also, the so-called ultra-high concentration small amount spraying method (u
It can also be applied by lotn-volume). In this method, 100% of the active ingredient is
It is possible to contain.

Test Example 1 The preparations of active ingredient compounds No. 1.2 and 3 were dispersed in water, and cabbage leaf pieces were immersed in the drug solution adjusted to a concentration of 800 ppm for about 10 seconds, then taken out and air-dried. A Petri dish (9 cm in diameter) was lined with moist filter paper, and the leaf pieces were placed on top of it.

2nd to 3rd instar Spodoptera larvae were released there, the lid was placed, and the container was left in a lighted incubator at 26°C. The survival rate was determined at the 7th day after the imago became an adult, and the survival rate was calculated using the following formula, and all results were 100%.

Test Example 2 Replace the 2nd to 3rd instar Spodoptera japonica with the 2nd to 3rd instar diamondback moth,
When the same procedure as in Test Example 1 was carried out, the active ingredient compound'! ! The mortality rate of IJ No. 1 was 100%.

Formulation Example 1 (a) Compound No. 2 20 parts by weight (b)
Diocrite 72 parts by weight (c) 8 parts by weight or more of sodium ligninsulfonate were uniformly mixed to prepare a wettable powder.

Formulation Example 2 (a) Compound No. 3 5 parts by weight (b) Talc 95 parts by weight or more were uniformly mixed to prepare a powder.

Formulation Example 3 (a) Compound No. 1 20 parts by weight (b)
70 parts by weight of N,N'-dimethylformamide (c) 10 parts by weight or more of polyoxyethylene alkylphenyl ether were uniformly mixed and dissolved to form an emulsion.

Formulation example 4 (a) 78 parts by weight of Sikurite (b)
β-Naphthalenesulfonic acid soda formalin condensation proboscis
2 parts by weight (c) Polyoxyethylene alkylaryl sulfate 5 parts by weight (d) White carbon A mixture of 15 parts by weight or more of each component and Compound No. 2 are mixed at a weight ratio of 4:1 to form a hydrating agent. And so.

Patent applicant: Ishihara Sangyo Co., Ltd. Inside the office

Claims (1)

[Claims] 1. General formula: ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, X_1 is a hydrogen atom, a halogen atom or a nitro group, and X_2 is a halogen atom or a nitro group,
Y_1, Y_2 and Y_3 are hydrogen atoms or halogen atoms]. 2. General formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. or a halogen atom] as an active ingredient.