JPH0426680A - Pyrimidine derivative, production thereof and noxious organism controlling agent - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R<1> us H; R<2> is 1-4C alkyl or halogen; R<3> is halogen or 1-5C alkyl or R<2> and R<3>, together with C to which they are linked, are condensed with the pyrimidine ring to form 5- to 6-membered ring which may have S; R<4> is H; R<5> is 1-4C alkyl; m is 1-10; n is 0-2). EXAMPLE:5-Chloro-6-ethyl-4-(8-methylthiooctyloxy) pyrimidine. USE:A noxious organism controlling agent. PREPARATION:A compound expressed by formula II (X is leaving group) is reacted with a compound expressed by formula III, preferably in the presence of a base (e.g. triethylamine) in an inert solvent (e.g. benzene).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a pest control agent containing a novel pyrimidine derivative as an active ingredient.

[Conventional technology]

Since the pyrimidine derivative of the present invention is a new compound, its biological activity is completely unknown.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a novel pyrimidine derivative, a method for producing the same, and a pest control agent containing the same as an active ingredient.

[Means for solving problems]

As a result of intensive research to solve the above-mentioned problems, the present inventors discovered that a new pyrimidine derivative has remarkable pest control activity, and completed the present invention.

That is, the present invention has the following formula: (In the formula, R1 represents a hydrogen atom, and R2 has 1 to
4 represents an alkyl group or a halogen atom; R3 represents a halogen atom or an alkyl group having 1 to 5 carbon atoms; or R2 and R3 are fused together with the carbon atom to which they are bonded to a pyrimidine ring; represents a saturated or unsaturated 5- or 6-membered ring which may have 1 sulfur atom, and 1 to 2 alkyl groups having 1 to 4 carbon atoms or halogen atoms are substituted on the ring. R4 represents a hydrogen atom, R5 represents an alkyl group having 1 to 4 carbon atoms;
m represents an integer of 1 to 10; n represents 0°1 or 2;

) A pyrimidine derivative represented by

(2) A compound represented by the following formula: (wherein, R1, RZ and R'' have the same meanings as described above; X represents a leaving group) and a linear formula; 1(' (wherein, R , , R5, R6 and n have the same meanings as described above.) Method for producing a pyrimidine derivative represented by the above formula (I) (3) The following formula: : (wherein, R1, R2, R3, R4 and m have the same meanings as above) and the following formula: R'-X (V) (
In the formula, R5 and X have the same meanings as above. ) The above formula (I) is characterized in that it is reacted with a compound represented by
(4) A pyrimidine derivative represented by the above formula (I-1) In the above formula (I), which is characterized by reacting with a peroxide, the following formula: (wherein R', R2, R3, R' and m have the same meanings as above; 1 or 2) (5) This relates to a pest control agent containing the pyrimidine derivative represented by formula (1) as an active ingredient.

The present invention will be explained in detail below.

A novel pyrimidine derivative (■) that is the target compound described above
In the compounds (If) to (V) which are the raw materials for their production, R1 includes a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a halogen atom, etc. However, a hydrogen atom is preferable.

R2 is an alkyl group having 17-4 carbon atoms.

Examples include halogen atoms; Preferably, linear or branched alkyl groups having 1 to 4 carbon atoms (
For example, methyl, ethyl, propyl.

Isopropyl, butyl, isobutyl, 5ec-butyl,
t-butyl, etc.); more preferably, an ethyl group or a methyl group.

Examples of R3 include a halogen atom and an alkyl group having 1 to 5 carbon atoms; preferably a halogen atom (e.g., fluorine, chlorine, bromine, iodine, etc.); more preferably , a chlorine atom is preferable.

Alternatively, R2 and R3 are fused to a pyrimidine ring together with the carbon atom to which they are bonded, and represent a saturated or unsaturated 5- or 6-membered ring that may have one sulfur atom, and The ring may be substituted with an alkyl group having 1 to 2 carbon atoms or a halogen atom.

Examples of R4 include a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a cycloalkyl group having 3 to 6 carbon atoms; preferably, it is a hydrogen atom.

R5 is an alkyl group having 1 to 5 carbon atoms which may be substituted with an alkoxy group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms.

Alkenyl group having 3 to 5 carbon atoms, alkynyl group having 3 to 5 carbon atoms, benzyl group which may have a substituent,
Examples include a phenyl group which may have a substituent; preferably, a carbon atom which may be substituted with an alkoxy group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. An alkyl group having 1 to 5 atoms is preferred; an alkyl group having 1 to 5 carbon atoms is more preferred; a linear or branched alkyl group having 1 to 4 carbon atoms is even more preferred.

m represents an integer of 1 to 10; preferably, an integer of 1 to 7.

n represents 0.1 or 2.

X is not particularly limited, and for example, a halogen atom (
chlorine, bromine, iodine, etc.), alkylthio groups (methylthio, ethylthio, propylthio).

butylthio, etc.), alkanesulfonyloxy groups optionally substituted with halogen (methanesulfonyloxy,
ethanesulfonyloxy, trifluoromethanesulfonyloxy, etc.), arylsulfonyloxy groups (benzenesulfonyloxy, etc.).

p-, toluenesulfonyloxy, etc.), hydroxyl group, etc.

When the carbon atom marked with * in the starting compound is an asymmetric carbon atom, the obtained target compound (I) includes individual optical isomers, racemic compounds, or mixtures thereof.

The object compound (1) of the present invention can be obtained, for example, by the production method (A-C) shown below.

(Manufacturing method A) (n) (I) 1111÷ (I) (wherein R', R2, R', R', R5, m, n and
is synonymous with the above description. ) The target compound (1) is usually preferably produced by reacting the starting compound (n) and the starting compound (I It can also be obtained by heating and dissolving raw material compounds (n) and (III) without a solvent and reacting them.

The solvent is not particularly limited as long as it is not directly involved in this reaction, and examples thereof include benzene, toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, and chloroform.

Chlorinated or non-chlorinated aromatic, aliphatic, cycloaliphatic hydrocarbons such as dichloroethane, trichlorethylene, cyclohexane; ethers such as diethyl ether, tetrahydrofuran, dioxane, etc.; such as acetone, methyl ethyl ketone, etc. alcohols or their hydrates such as methanol, ethanol, ethylene glycol, etc.; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, etc.; triethylamine, pyridine, N,N-diethylaniline Organic bases such as 1゜3-dimethyl-
Examples include 2-imidazolidinone; dimethyl sulfoxide; and mixtures of the above solvents.

Examples of the base include triethylamine, pyridine,
Organic bases such as N,N-diethylaniline, etc.; Alkali metal alkoxides such as sodium methoxide, sodium ethoxide, etc.; sodium amide, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydride, etc. Examples include inorganic bases.

The reaction temperature is not particularly limited, but is usually within a temperature range from room temperature to the boiling point of the solvent used, and the reaction time can be shortened by heating within the temperature range below the boiling point.

(Production method B) In the above formula (1), the compound (1) in which n is 0 can be produced by the following method.

(IV) (V) p+ (In the formula, R', R2, R', R', R', m and X have the same meanings as described above.) The target compound (I-1) is usually a raw material. It is preferable to produce the compound (TV) by reacting the starting compound (V) with the starting compound (V) in a solvent in the presence of a base, but it can also be produced by the reaction without adding a base, and it is also possible to produce the starting material without a solvent. It can also be obtained by heating and dissolving compounds (IV) and (V) and reacting them.

Examples of the solvent and base include those described in Production Method A.

Similarly to Production Method A, the reaction temperature is not particularly limited, and is usually within the temperature range from room temperature to the boiling point of the solvent used,
The reaction time can be shortened by heating at a temperature below the boiling point.

(Production method C) Compound Cl-2 in which n is 1 or 2 in the formula (I)
) can be produced by the following method.

(In the formula, R', R2, R3, R', RS, m and X are as defined above; n' represents 1 or 2.) The target compound (I-2) is a starting compound ( 1-1) and peroxide (VI).

As the solvent, those described in Production Method A can be mentioned.

The peroxide is not particularly limited, and examples thereof include hydrogen peroxide, m-chloroperbenzoic acid, sodium metaperiodate, potassium permanganate, and sodium hypochlorite.

The reaction temperature is not particularly limited as long as it is carried out within the temperature range from -10°C to the boiling point of the solvent used, but usually -1
0°C to room temperature is preferred.

As described above, the target compound (1) produced by Production Methods A to C can be appropriately purified by known means such as recrystallization and various chromatography.

The raw material compound (I[) used in the present invention is described, for example, in the Journal of Chemical Society (J.

C,S), 3478-3481 (1955), by performing as shown in the following formula,
It can be easily manufactured.

(In the formula, R1, R2, and R3 have the same meanings as described above.) The raw material compound (DI) used in the present invention can be easily produced, for example, by performing as shown in the following formula.

(Hereinafter, blank space) E4 (I[[-1) (■ (In the formula, l and It can be appropriately produced by known means such as various chromatography methods.

Pests for which the compound (I) of the present invention can be controlled include agricultural and horticultural pests [e.g., Hemiptera (planthoppers, planthoppers,
leafhoppers, aphids, whiteflies, etc.), Lepidoptera (armyptera, mealybugs, etc.).

(e.g. leaf beetles, beetles, cabbage moths, etc.), Moptera (e.g. meal beetles, weevils, potato beetles, etc.),
Examples include acarinae (citrus red spider mite, two-spotted spider mite, etc.), sanitary pests (e.g., flies, spider mites, cockroaches, etc.), grain storage pests, cat nematodes in the soil, pine wood nematodes, mites, etc., and agricultural and horticultural pathogens (e.g. , wheat rust, barley powdery mildew, cucumber rot, rice blast, tomato late blight, etc.).

The pest control agent of the present invention contains one or more types of compound (I) as an active ingredient.

Compound (1) can be used alone, but it is usually mixed with a carrier, a surfactant, a dispersant, an auxiliary agent, etc. (for example, a powder, an emulsion) by a conventional method.

It is preferable to use it as a composition (prepared as a composition such as two fine granules, a wettable powder, an oily suspension, an aerosol, etc.).

Examples of carriers include talc and bentonite.

Clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate.

Solid carriers such as urea; hydrocarbons (kerosene, mineral oil, etc.)
, aromatic hydrocarbons (benzene, toluene.

xylene), chlorinated hydrocarbons (chloroform, etc.).

carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, etc.).

cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene glycol acetate, etc.).

Liquid carriers such as dibutyl maleate, etc.), alcohols (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethyl sulfoxide, etc.), and water; air, nitrogen, carbon dioxide, Freon, etc. Examples include gas carriers (in this case, they can be mixed and injected).

Examples of surfactants and dispersants that can be used to improve properties such as adhesion to animals and plants, absorption, dispersion, emulsification, and spreading of drugs include alcohol sulfate esters, alkyl sulfonates, lignin sulfonate,
Examples include polyoxyethylene glycol ether.

In order to improve the properties of the preparation, for example,
Carboxymethyl cellulose, polyethylene glycol, gum arabic, etc. can be used as adjuvants.

In the standard production, the carrier, surfactant, dispersant, and auxiliary agent may be used alone or in appropriate combinations depending on the purpose.

When the compound (I) of the present invention is formulated, the concentration of the active ingredient is usually 1 to 50% by weight in an emulsion, and usually 0.3% in a powder.
For ~25% weight additives, it is usually 0.5~5% by weight for 1~90% weight additives, for oil agents it is usually 0.5~5% by weight, and for aerosols it is usually 0゜1~5% by weight. be.

These preparations can be diluted to an appropriate concentration and sprayed on plant foliage, soil, or the water surface of paddy fields, depending on the purpose.
Alternatively, it can be applied directly for various purposes.

〔Example〕

The present invention will now be illustrated by examples. Note that these Examples do not limit the scope of the present invention.

Example 1 ■ [Synthesis of 5-chloro-6-nityl-4-(8-methylthioctyloxy)pyrimidine (Compound 1)] The target compound (1) was synthesized using Production Method A as described below.
) was able to be obtained.

3.0 g (17.0 mmo j2) of 8-methylthiooctyl alcohol, which is the starting compound (I[[), was dissolved in 30 ml of tetrahydrofuran, and sodium hydride (
60% in oil) 0.82 g (20.4m
Add the molasses slowly.

After the addition, the mixture was stirred at room temperature for 30 minutes, and 4,5-dichloro-6-ethylpyrimidine, which is the starting compound (II), was added. Og
(17.0 mmo 42) was added, and the mixture was heated under reflux for 3 hours while stirring.

After the reaction was completed, water was added, and the separated oil was extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure.

The obtained oil was subjected to silica gel column chromatography (Wakogel C-200, toluene:ethyl acetate-9:
1 elution) and is a colorless oil (shown as Compound 1 in Table 1 below).
3.9g of was obtained.

■[5-chloro-6-nityl-4-(8-methylsulfinyloctyloxy)pyrimidine (compound 7) and a
-5-Chloro-6-ethyl 4-(8-methylsulfonyloctyloxy)pyrimidine (Compound 8)] The target compound (1
) was able to be obtained.

Raw material compound (I-1) (Example 1-■) 2.4
g (7,6 mmol l) J 30
2.8 g (70 w%, 11.4 mm) of m-chloroperbenzoic acid.

2) was added and stirred for 1 hour.

After the reaction was completed, the reaction solution was washed with an aqueous IN sodium hydroxide solution, washed with water, dried over anhydrous sodium sulfate, and then dichloromethane was distilled off under reduced pressure.

The obtained oil was subjected to silica gel column chromatography (Wakogel C-200, toluene:ethyl acetate-2:
The target compound (shown as Compound 8 in Table 1 below) was isolated as colorless powdery crystals.

) was obtained.

Then toluene:ethyl acetate:ethanol-10:1
Isolated by 0:1 elution, 1.2 g of the desired compound (shown as Compound 7 in Table 1 below) was obtained as colorless powdery crystals.

■ [Synthesis of compounds 2 to 6 and 9 to 36 in Table 1] ■ to ■
The target compound (I) as shown in Table 1 (indicated as compounds 2-6.9-36 in Table 1 below) is obtained in the same manner as any of the synthesis methods. I was able to do that.

(Hereafter, margin) 61 Example 2 ■ [Preparation of granules] 5 parts by weight of Compound 1 and 35 parts by weight of bentonite.

57 parts by weight of talc, Neoperex powder (product name;
(manufactured by Kao Atlas) and 2 parts by weight of sodium ligninsulfonate were uniformly mixed, and then a small amount of water was added and kneaded, followed by granulation and drying to obtain granules.

■ [Preparation of hydrating powder] 10 parts by weight of Compound 1, 70 parts by weight of kaolin.

18 parts by weight of white carbon, 1.5 parts by weight of Neoperex powder (trade name; manufactured by Kao Atlas Co., Ltd.) and 0.5 parts by weight of Demol (trade name; manufactured by Kao Atlas Co., Ltd.) are uniformly mixed, and then pulverized and hydrated. obtained the drug.

(2) [Preparation of emulsion] 10 parts by weight of Toxanone (trade name; manufactured by Sanyo Chemical Industries, Ltd.) was added to 20 parts by weight of Compound 1 and 70 parts by weight of xylene, mixed uniformly, and dissolved to obtain an emulsion.

■ [Preparation of powder] 5 parts by weight of compound 1, 50 parts by weight of talc and 4 parts of kaolin
A powder was obtained by uniformly mixing 5 parts by weight.

Example 3 ■ [Efficacy test against sweet potato nematode] The target compound shown in Table 1 prepared according to Example 2 (I
) was diluted with water to 20 PPm. Then, put 0.5 d of the drug solution into the examiner, and add 30 to 40 d
A solution containing 0.5 liters of sweet potato nematode head was added.

Two days after being left in a constant temperature room at 25°C, the number of live and dead insects was counted under a microscope to determine the mortality rate.

Evaluation of drug efficacy is divided into four stages (A) depending on the range of mortality rate.
:100~90%, B:89~80%, C near 9~60
%, D=59% or less).

The results are shown in Table 2.

Table 2 Compounds Activity against sweet potato nematode ■ [Control efficacy test against wheat rust (preventive effect)
] Wheat (variety: Kobushi wheat) was grown in plastic flower pots with a diameter of 6 cm and 10 m (variety: Kobushi wheat) per pot, and seedlings at the 1.5 leaf stage were prepared according to Example 2 and shown in Table 1. The hydrating agent of the target compound (I) is mixed with a surfactant (0,0
It was diluted to 200 ppm with water containing 1%) and sprayed at 20 ml per pot.

After spraying, the plants were cultivated in a glass greenhouse for 2 days, and then a spore suspension (7×10′ spores/ml) of Puccinia dispersa was spray-inoculated uniformly onto the plants.

After inoculation, the plants were grown in a glass greenhouse for one week, and the extent of wheat rust lesions that appeared on the first leaves was examined.

The drug effect was evaluated by comparing the degree of lesions in the untreated area.
6 stages (0: whole disease affected, 1: lesion area approximately 60%,
2: Lesion area is approximately 40%, 3: Lesion area is approximately 20%, 4: Lesion area is 10% or less, 5: No lesion).

The results are shown in Table 3.

Table 3 Wheat rust Preventive effect against chemical compounds 〔Effect of the invention〕 The novel pyrimidine derivatives of the present invention are It is a useful pesticide as a pest control agent.

pest

Claims (5)

[Claims] (1) The following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R^1 represents a hydrogen atom; R^2 represents an alkyl group having 1 to 4 carbon atoms or a halogen atom. ; R^3 represents a halogen atom or an alkyl group having 1 to 5 carbon atoms; or R^2 and R^3 are fused to a pyrimidine ring together with the carbon atom to which they are bonded, and a sulfur atom is formed; represents a saturated or unsaturated 5- or 6-membered ring which may have one or more saturated or unsaturated rings, and may be substituted with 1 to 2 alkyl groups having 1 to 4 carbon atoms or halogen atoms on the ring. Good; R^
4 represents a hydrogen atom; R^5 represents an alkyl group having 1 to 4 carbon atoms; m represents an integer of 1 to 10; n is 0, 1
Or represents 2. ) pyrimidine derivatives. (2) The following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^1, R^2 and R^3 have the same meanings as described in claim 1; X represents a leaving group. ) and the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R^4, R^5, m and n have the same meanings as in claim 1.) A method for producing a pyrimidine derivative represented by formula (I) according to claim 1, characterized in that the pyrimidine derivative is reacted with a compound represented by formula (I). (3) The following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (IV) (In the formula, R^1, R^2, R^3, R^4 and m have the same meanings as in claim 1. ) and a compound represented by the following formula: R^5-X(V) (wherein R^5 and X have the same meanings as in claims 1 and 2). In the formula (I) according to claim 1, there are ▲mathematical formulas, chemical formulas, tables, etc.▼( I -1) (In the formula, R^1, R^2, R^3, R^4 and m has the same meaning as in claim 1.) A method for producing a pyrimidine derivative. (4) In the formula (I) according to claim 1, which is characterized by reacting the pyrimidine derivative represented by formula (I-1) according to claim 3 with a peroxide, the following formula: ▲ Formula, There are chemical formulas, tables, etc. ▼ (I-2) (In the formula, R^1, R^2, R^3, R^4 and m have the same meaning as in claim 1; n' stands for 1 or 2. A method for producing a pyrimidine derivative represented by (5) A pest control agent containing the pyrimidine derivative represented by formula (I) according to claim 1 as an active ingredient.