JPH04164072A - Oxypyrimidine derivative, its production and pest control agent therefrom - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R<1> is 1-4C alkyl or halogen; R<2> is 1-4C alkyl; R<1> and R<2> is, together with C, condensed with pyrimidine ring into a five-membered ring; A is -CH2CH2- or -CH(CH3)-). EXAMPLE:dl-5-Chloro-6-ethyl-[1-(4-tert-butylphenyl)ethoxy] pyrimidine. USE:A pest control agent. Having excellent control effects on Hemiptera, Lepidoptera, Coleoptera, mite, sanitary insect pests, stored grain insect pests, etc. Also having control effects on agricultural/horticultural pathogenic bacteria such as for wheat brown rust, downy mildew, and neck rot. PREPARATION:The objective compound of the formula I can be obtained by reaction between a compound of formula II (X is eliminable group) and another compound of formula III pref. in a solvent (e.g. DMF) in the presence of a base (e.g. NaH) at room temperature to the boiling point.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a pest control agent containing a novel oxypyrimidine derivative as an active ingredient. [Prior Art] In recent years, due to the development of drug resistance to pest control agents, a decrease in the efficacy of the drugs has become a serious problem. Among these, it has become particularly important to solve the problem of drug resistance to acaricides, and there is a desire for the development of new compounds that are effective against drug-resistant mites. Therefore, since the oxypyrimidine derivative discovered by the present inventors based on the above-mentioned reasons is a new compound, its pest control activity is completely unknown. [Problems to be Solved by the Invention] An object of the present invention is to provide a novel oxypyrimidine derivative, a method for producing the same, and a pest control agent containing the same as an active ingredient. [Means for Solving the Problems] As a result of intensive research to solve the above problems, the present inventors discovered that a novel oxypyrimidine derivative has remarkable pest control activity, and the present invention I was able to complete it. That is, the present invention provides the following formula:
and R1 are fused to the pyrimidine ring together with the carbon atom to which they are bonded, and represent a saturated or unsaturated 5-membered ring which may have one sulfur atom; A is -CH(CHs)
, or represents CH2CH2-. ) Oxypyrimidine derivative (2) represented by the following formula: (In the formula, R1 and R1 have the same meanings as described above; X represents a leaving group.) A compound represented by the following formula: (In the formula, A is the same as the above description.) A method for producing an oxypyrimidine derivative represented by the above formula (I), characterized by reacting the oxypyrimidine derivative represented by the above formula (I). The present invention relates to a pest control agent containing an oxypyrimidine derivative as an active ingredient. The present invention will be explained in detail below. Novel pyrimidine derivative (I) which is the above-mentioned target compound
, in the compounds (U) to (V) which are raw materials for their production, R1 is a straight or branched alkyl group of Cl to 4 (e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 5ec). -butyl,
t-butyl, etc.), halogen atoms (e.g., fluorine, chlorine, bromine, iodine, etc.); C1-4
As the linear or branched alkyl group, CIy 1
An alkyl group is preferred; as a halogen atom, a chlorine atom is preferred. Examples of R2 include 01-4 linear or branched alkyl groups (for example, the alkyl groups described above); C, 4-linear or branched alkyl groups; As 'SC+~, an alkyl group is preferable. Alternatively, R1 and R1 may be fused together with the carbon atom to which they are bonded to a pyrimidine ring to form a saturated or unsaturated 5-membered ring that may have one sulfur atom. Preferably, the ring fused to the pyrimidine ring with a carbon atom is: -CH(CH3)+ More preferably, *A is -CH(CH3)+. Examples include CH3CO--. 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.). When the carbon atom marked with * in the starting compound is an asymmetric carbon atom, the obtained target compound (I) includes any of the individual optical isomers, racemic compounds, or mixtures thereof. The object compound (I) of the present invention can be obtained, for example, by production methods A and H as shown below. (Manufacturing method A) (n) (III)->(I
) (In the formula, R', R', Usually, it is preferable to produce by reacting the starting compound (n) and the starting compound (III) in a solvent in the presence of a base,
It can be obtained by reacting without adding a base, or it can be obtained by heating and dissolving raw material compounds (n) and (III) without solvent. 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.; 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; triethylamine, pyridine, N,N-
an organic base such as dimethylaniline; l. Examples include 3-dimethyl-2-imidazolidinone; dimethyl sulfoxide; and mixtures of the above solvents. Examples of the base include triethylamine, pyridine,
Organic bases such as N,N-dimethylaniline, 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 the temperature range from room temperature to the boiling point of the solvent used, and is preferably heated within the temperature range below the boiling point. The reaction time varies depending on the concentration and temperature mentioned above, but is usually 3 to 8 hours. (Production method B) (IV) (V)->(1) (In the formula, R', R'', ) can be obtained by reacting for 3 to 8 hours in the same manner as in Production Method A, using starting compound (V) instead of starting compound (V) and using starting compound (IV) instead of starting compound (III) The target compound (I) produced by production method A or B as described above can be appropriately purified by known means such as recrystallization and various chromatography. ) can be easily produced, for example, according to the method described in Journal of the Chemical Society (J.C.S.), 3478-3481 (1955). ) are effective in controlling agricultural and horticultural pests [e.g., Hemiptera (planthoppers, leafhoppers, aphids, whiteflies, etc.), Lepidoptera (army caterpillars, mealybugs, leaf beetles, mealybugs, cabbage butterflies, etc.), Coleoptera (drug beetles, weevils,)\bugs, etc.)
, Acarinae (such as citrus mites of the spider mite family, two-spotted spider mites, and citrus rust mites of the fushidae family)], sanitary pests (e.g., flies, flies, cockroaches, etc.), grain storage pests, nematode nematodes, pine nematodes, nedanii, etc. in the soil. In addition, agricultural and horticultural pathogens (eg, wheat rust, barley powdery mildew, cucumber mildew, rice blast, tomato late blight, etc.) can also be mentioned. The pest control agent of the present invention has remarkable insecticidal, acaricidal, and bactericidal effects, and contains one or more types of compound (I) as an active ingredient. The pest control agent of the present invention contains one or more types of compound (I) as an active ingredient. Compound (I) can be used alone, but it is usually mixed with a carrier, a surfactant, a dispersant, an auxiliary agent, etc. (e.g., powder, emulsion, one fine granule, hydrated) by a conventional method. It is preferable to prepare a composition such as a drug, 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, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters ( Ethyl acetate, ethylene glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethyl sulfoxide, etc.), liquid carriers such as water; air, nitrogen, carbon dioxide gas , a gas carrier such as Freon (in this case, it can be mixed and injected), and the like. Examples of surfactants and dispersants that can be used to improve the adhesion and absorption of water preparations to animals and plants, as well as the dispersion, emulsification, and spreading of drugs, include alcohol sulfate esters, alkyl sulfonates, etc. , 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 production of aqueous preparations, the carrier, surfactant, dispersant, and auxiliary agent described above can be used individually 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.
~25% by weight, usually 1 to 90% by weight for wettable powders, usually 0.5 to 5% by weight for single granules, usually 0.5 to 5% by weight for oil solutions, and usually 0.1 to 5% by weight for aerosols. be. These preparations can be diluted to an appropriate concentration and sprayed on plant foliage, soil, or the water surface of rice fields, depending on the purpose.
Alternatively, it can be applied directly for various purposes. (Hereinafter, blank spaces) [Examples] The present invention will be illustrated below by reference examples and examples. Note that these Examples do not limit the scope of the present invention. Reference Example 1 Starting compound (III) was synthesized as described below. ■

[Synthesis of dl-4-tert-butyl-α-phenethyl alcohol] 2.5 g (104 mmoj') of ground magnesium was added to anhydrous tetrahydrofuran lO-, and the mixture was heated under a nitrogen stream for 6 hours.
Heated to 0°C. While stirring, a solution of 22 g (103 mmof) of 4-terL-butyl-bromobenzene in anhydrous tetrahydrofuran (50 m/) was gradually added dropwise, and the mixture was stirred for 30 minutes. After cooling this to room temperature, 6 g of acetaldehyde (136
mmoj anhydrous tetrahydrofuran solution (50rd)
was gradually added dropwise, the mixture was stirred for 30 minutes, and the reaction mixture was poured into ice water. Toluene was added to this, and insoluble materials were removed by celite filtration to perform toluene extraction. After washing this extract with water and drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. By distilling the obtained oil under reduced pressure (b, p,
(120-125°C, 74 mmHg), the desired raw material compound as a colorless oil was obtained. (2) [Synthesis of 4-tert-butyl-β-phenethyl alcohol] 2.5 g (104 mmoj7) of magnesium chips were added to 100 rIl of anhydrous tetrahydrofuran and heated to 60° C. under a nitrogen stream. While stirring, a solution of 22 g (103 mmol) of 4-tert-butyl-bromobenzene in anhydrous tetrahydrofuran (50 td) was gradually added dropwise, followed by stirring for 30 minutes. After cooling this to room temperature, 6 g of ethylene oxide (1
36mmol> of anhydrous tetrahydrofuran solution (50y
After gradually dropping d), the mixture was stirred for 30 minutes and the reaction mixture was poured into ice water. Toluene was added to this, and insoluble materials were removed by celite filtration to perform toluene extraction. After washing this extract with water and drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. By distilling the obtained oil under reduced pressure (b, p,
(120-124°C/4mmHg), the desired raw material compound as colorless crystals was obtained. Example 1 ■

[dl-5-chloro-6-nithylu[1-(4-te
Synthesis of rt-butylphenyl)ethoxy]pyrimidine (compound 3) The target compound (1
) was able to be obtained. The starting compound (I[[), dl-
4-LerL-butyl-α-phenethyl alcohol 1g
(5,6 mmol was added with N,N-dimethylformamide 1
0-3 g of 60% sodium hydride (
7.5 mmof) was gradually added. After stirring this at room temperature for 1 hour, 4.5-dichloro-6
-Nitylpyrimidine 1 g (5,6 mmol 1) was added and stirred at 60-70°C for 5 hours. After the reaction was completed, the reaction solution was poured into water, and the target compound was extracted with toluene. Then, wash this toluene layer with water,
After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained oil was subjected to silica gel column chromatography (Wakogel C-200, toluene: ethyl acetate; 8:
The target compound (shown as Compound 3 in Table 1 below) was isolated as a colorless oil (shown as Compound 3 in Table 1 below).
0.6g of was obtained. ■

[5-chloro-6-nithylu(2-(4-tert-
[Synthesis of butylphenyl)ethoxy]pyrimidine (compound 4)] The target compound (I
) was able to be obtained. 4-t, the raw material compound (III) obtained in Reference Example 1 (■)
ert-butyl-β-phenethyl alcohol 1 g (5,
6 mmof') was dissolved in N,N-dimethylformamide IO, and 0.3 g of 60% sodium hydride (7.5 m
mof) was added gradually. After stirring this at room temperature for 1 hour, 4.5-dichloro6
-x tilpyrimidine Ig (5°6 mmof+) was added,
The mixture was stirred at 60-70°C for 5 hours. After the reaction was completed, the reaction solution was poured into water, and the target compound was extracted with toluene. Then, wash this toluene layer with water,
After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained oil was subjected to silica gel column chromatography (Wakogel C-200, toluene:ethyl acetate-8:
The desired compound (shown as Compound 4 in Table 1 below) was isolated as a colorless oil (shown as Compound 4 in Table 1 below).
0.5 g of was obtained. ■

[5-methyl-6-nityl-(2-(4-tert-
[Synthesis of butylphenyl)ethoxy]pyrimidine (compound 8)] The target compound (I
) was able to be obtained. 4-t, the raw material compound (III) obtained in Reference Example 1 (■)
ert-butyl-β-phenethyl alcohol 1 g (5,
6 mmof) was dissolved in 10-tetrahydrofuran,
0% sodium hydride 0.3g (7,5mmo j2)
was added gradually. After stirring this at room temperature for 1 hour, 0.8 g (5.1 mmof) of 4-chloro-5-methyl-6-ethylpyrimidine was added.
was added and stirred at 60 to 70°C for 5 hours. After the reaction was completed, the reaction solution was poured into water, and the target compound was extracted with toluene. Then, wash this toluene layer with water,
After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained oil was subjected to silica gel column chromatography (Wakogel C-200, toluene:ethyl acetate-8:
The target compound (shown as Compound 8 in Table 1 below) was isolated as a colorless oil (shown as Compound 8 in Table 1 below).
0.9g of was obtained. ■[4-(2-(4-tert-butylphenyl)ethoxy]cheno(2,3-d)pyrimidine (compound 12
) Synthesis of the target compound (I
) was able to be obtained. 4-t, the raw material compound (III) obtained in Reference Example 1 (■)
0.7 g of ert-butyl-β-phenethyl alcohol (
3°9mmof) was dissolved in 10i of tetrahydrofuran, and 0.3g (7,smmol) of 60% sodium hydride was added.
was added gradually. After stirring this at room temperature for 1 hour, 4-chlorocheno (
2,3-d) Pyrimidine 0.7g (4,1mmof
> and stirred at 60 to 70°C for 5 hours. After the reaction was completed, the reaction solution was poured into water, and the target compound was extracted with toluene. Then, wash this toluene layer with water,
After drying over anhydrous sodium sulfate, 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) to obtain 0.5 g of the target compound (shown as Compound 12 in Table 1 below) as colorless crystals. (The following is a blank space) Example 2 ■ [Preparation of granules] 5 parts by weight of compound 4, 35 parts by weight of bentonite, 57 parts by weight of talc, 1 part by weight of Neoperex powder (trade name; manufactured by Kao), and sodium lignin sulfonate. Two parts by weight were uniformly mixed, then a small amount of water was added and kneaded, followed by granulation and drying to obtain granules. ■ [Preparation of wettable powder] 10 parts by weight of Compound 4, 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) and 0.5 parts by weight of Demol (trade name; manufactured by Kao) are mixed uniformly, and then crushed to form a wettable powder. Obtained. (2) [Preparation of emulsion] 10 parts by weight of toxanone (trade name; manufactured by Kochu Kasei Kogyo Co., Ltd.) was added to 20 parts by weight of Compound 4 and 70 parts by weight of xylene, mixed uniformly, and dissolved to obtain an emulsion. ■ [Preparation of powder] 5 parts by weight of compound 4, 50 parts by weight of talc and kaolin 4
A powder was obtained by uniformly mixing 5 parts by weight. Example 3 ■ [Efficacy test against adult two-spotted spider mites] Each hydrating agent of the target compound (I) shown in Table 1 prepared according to Example 2 was mixed with water containing a surfactant (0.01%). 300ppm
Each kidney bean leaf piece (diameter 20 mm) in which 10 female adult two-spotted spider mites were parasitized in each of these chemical solutions was diluted to 15
Dipped for seconds at a time. Next, each of these leaf pieces was left in a constant temperature room at 25°C, and after 3 days, the number of live and dead insects on each leaf piece was counted to determine the acaricidal rate. Evaluation of drug efficacy is divided into four stages (
A: 100%, B: 99-80%, C near 9-60%,
D=59% or less). The results are shown in Table 2. Table 2 ■ [Control efficacy test against wheat rust (preventive effect)
] Wheat (variety: Kobushi wheat) was grown in plastic flower pots with a diameter of 6 cm, 10 plants per pot, and the target compounds shown in Table 1 prepared according to Example 2 were added to the seedlings at the 1.5 leaf stage. The hydrating agent (I) is combined with a surfactant (0,01
%) per pot to 500 ppm.
0mI! It was sprayed with. After spraying, the plants were cultivated in a glass greenhouse for two days, and then a spore suspension of the wheat rust fungus was evenly sprayed and inoculated 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: Untreated area 0 ■ [Control efficacy test against rice blast disease (preventive effect)] Ten rice plants (variety: Nipponbare) were grown per pot in plastic flower pots with a diameter of 6 cm, and young plants at the 15-leaf stage were grown. Each hydrating agent of the target compound (I) shown in Table 1 prepared according to Example 2 was diluted to 500 ppm with water containing a surfactant (0.01%) and placed in a l pot. Sprayed 20 times a day. After spraying, the plants were cultivated in a glass greenhouse for two days, and then a conidial suspension of rice blast fungus prepared from diseased leaves was uniformly sprayed and inoculated onto the plant leaves. After inoculation, the plants were grown in a humid room at 28°C for 5 days, and the extent of rice blast lesions that appeared on the leaves was examined. The results are evaluated using the 6-level evaluation method described in (■) above.
It is shown in Table 4. Table 4: Untreated Area O [Effects of the Invention] The novel oxypyrimidine derivatives of the present invention are agricultural chemicals useful as pest control agents.

Claims (3)

[Claims] (1) The following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R^1 represents a C_1-_4 alkyl group or a halogen atom; R^2 represents a C_1-_4 alkyl group;
Alternatively, R^1 and R^2 are fused to a pyrimidine ring with the carbon atom to which they are bonded, and represent a saturated or unsaturated 5-membered ring that may have one sulfur atom; A represents -CH(CH_3)-, -CH_2, CH_2-. ) An oxypyrimidine derivative represented by (2) The following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R^1 and R^2 have the same meaning as described in claim 1; X represents a leaving group.) A claim characterized by reacting a compound represented by the following formula: ▲Mathematical formula, chemical formula, table, etc.▼(III) (In the formula, A has the same meaning as in claim 1) A method for producing an oxypyrimidine derivative represented by formula (I) according to item 1. (3) A pest control agent containing the oxypyrimidine derivative represented by formula (I) according to claim 1 as an active ingredient.