JPH03197467A - Pyrimidinone derivative, preparation thereof and insecticide-acaricide containing the same as active ingredient - Google Patents

Abstract

NEW MATERIAL:A pyrimidine derivative of formula I (R1 is H, 1-4C alkyl, alkenyl or alkynyl; R2 is 1-3C alkyl; R3 and R4 are H, 1-6C alkyl which may be substituted, or substituted phenyl; or R3 and R4 are alkyls which may be combined with each other to form a ring). EXAMPLE:6-Diethylamino-2-methylthio-5-trifluoromethyl-4(3H)-pyrimidinone. USE:Useful as an insecticidal acaricide and an antimicrobial agent in rice fields, upland fields, fruit gardens, forests and environmental hygienic fields. PREPARATION:A compound of formula II is made to react with a compound of formula III (X is halogen) in the presence of a base in a non-reactive solvent and the prepared compound of formula IV is allowed to react with a compound of formula V in the presence of a base such as pyridine is an inert solvent to provide the compound of formula I.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The insecticidal, acaricidal, and fungicidal composition according to the present invention can be used as an insecticidal, acaricidal, or bactericidal agent in rice fields, fields, orchards, forests, and environmental hygiene hot water surfaces. can do.

[Conventional technology]

The fact that certain pyrimidinone derivatives have insecticidal, acaricidal, and bactericidal activity is described in, for example, JP-A-63112-566 and JP-A-1-190670. However, pyrimidinone derivatives having a trifluoromethyl group at the 5th position and an alkylamino group at the 6th position are not known.

[Problem to be solved by the invention]

However, these compounds are not necessarily sufficient as active ingredients for insecticides, acaricides, or fungicides.

[Means to solve the problem]

In view of the above situation, the present inventors have conducted extensive research and found that
Formula (wherein, R1 represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkenyl group, an alkynyl group,
2 represents a lower alkyl group having 1 to 3 carbon atoms, Ra,
R4 is a hydrogen atom or a pyrimidinone derivative represented by a branched alkyl group having 1 to 6 carbon atoms, or a substituted phenyl group or an alkyl group in which R3 and R may be linked together to form a ring; It was discovered that the compound has strong insecticidal, acaricidal, or bactericidal activity, leading to the completion of the present invention.

The compound of general formula (1) of the present invention can be produced by the following method. That is, by the method described in JP-A-63-216877, using the general formula (in the formula, R2 represents a lower alkyl group having 1 to 3 carbon atoms) as a starting material, a suitable base (for example, The following general formula A compound represented by formula (3) is produced, and the compound represented by general formula (3) is further mixed with a compound represented by general formula (4) above and an appropriate base (
For example, the compound represented by general formula (1) can be produced by reacting in the presence of triethylamine, biridine, sodium bicarbonate, potassium carbonate, etc.) in a solvent that does not affect the reaction. When two or more equivalents of the compound represented by general formula (4) are used, the presence of a base is not necessarily required.

Further, the compound represented by general formula (2) can be prepared using a suitable base (for example,
Triethylamine, pyridine, sodium bicarbonate, potassium carbonate, etc.) in a solvent that does not affect the reaction, react with a compound represented by general formula (4) to form the following general formula (5).
The compound represented by formula (5) and RIX (2) (X is a halogen atom) were further mixed with a suitable base (
For example, the compound represented by general formula (1) can be produced by reacting in the presence of sodium hydroxide, potassium hydroxide, potassium carbonate, sodium hydrogen carbonate, triethylamine, pyridine, etc.) in a solvent that does not affect the reaction. .

In the present invention, solvents that do not affect the reaction include aromatic hydrocarbons such as badruene and xylene, alcohols such as methanol and ethanol, ketones such as acetone, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, dichloromethane, etc. halogenated hydrocarbons and ethers such as diisopropyl ether can be used. Water may also be used. A mixed solvent of these solvents or a mixed solvent with water can also be used. The temperature can range from -20°C to the boiling point of the solvent used in the reaction. Although the molar ratio of the raw materials can be set arbitrarily, it is advantageous to carry out the reaction at an equimolar ratio or a ratio close to it. A phase transfer catalyst (eg, tetraammonium salt, etc.) may be added to the reaction system as a catalyst.

Hereinafter, the method for producing the compound of the present invention will be specifically explained with reference to Examples. The present invention is not limited to these.

When the compound of general formula (1) of the present invention is used as a pest control agent, depending on the purpose of use, it may be used as it is,9 or it may be mixed with a pesticide auxiliary to enhance or stabilize the effect, which is generally used in the field of pesticide manufacturing. Depending on the method used, it can be used in the form of powders, fine granules, granules, wettable powders, flowables, emulsions, poison baits, and the like.

In actual use, these various formulations can be used directly or diluted with water to a desired concentration.

The agrochemical auxiliary agents mentioned herein include carriers (diluents) and other auxiliary agents such as spreading agents, emulsifiers, wetting agents, dispersants, fixing agents, and disintegrants. Examples of liquid carriers include aromatic hydrocarbons such as toluene and xylene, alcohols such as butanol, octatool, and glycol, ketones such as acetone, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide,
Examples include methylnaphthalene, cyclohexanone, animal and vegetable oils, fatty acids, fatty acid esters, petroleum fractions such as kerosene and light oil, and water.

10- Solid carriers include clay kaolin, Merck, diatomaceous earth,
Examples include silica, calcium carbonate, montmorillonite, bentonite, feldspar, quartz, alumina, and sawdust.

In addition, surfactants are usually used as emulsifiers or dispersants, such as anionic surfactants such as higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether, lauryl betaine, and cationic surfactants. , nonionic surfactants, and amphoteric surfactants.

In addition, examples of spreading agents include polyoxyethylene nonylphenyl ether and l-'IJ oxyethylene lauryl ether, examples of wetting agents include polyoxyethylene nonylphenyl ether dialkyl sulfosuccinate, and examples of fixing agents include polyoxyethylene nonylphenyl ether dialkyl sulfosuccinate. Examples include carboxymethyl cellulose and polyvinyl alcohol, and examples of disintegrants include sodium atomyl sulfonate and sodium lauryl sulfate.

Any of the preparations can be used not only alone, but also in combination with fungicides, insecticides, acaricides, herbicides, plant growth regulators, soil conditioners, or nematicides, and can be used as fertilizers or other agricultural chemicals. It can also be used in combination with

Furthermore, the efficacy can be increased several times by adding known synergists for pyrethroids, such as piveronyl butoxide, sulfoxide, safroxan, etc.

The content of the active ingredient in the composition of the present invention varies depending on the formulation form, method of application, and other conditions. In some cases, it may be only the active ingredient compound, but it is usually 02 to 95% (by weight), preferably 05 to 30% (by weight). is within the range of

The amount of the composition of the present invention to be used, the dosage form, the method and timing of application,
Although it varies depending on other conditions, the amount of active ingredient for agricultural and horticultural agents, forest pest control agents, and pasture pest control agents is usually 01 to 1.00 to 10 cm per 10 are, preferably 002 to 5 r.
r@ is used. For example, the active ingredient for a powder is 01 to 50 g per 10 ares, and the active ingredient for one granule is 02 to io.

g, emulsions and hydrating agents range from 01 to 100 g of active ingredient. However, in special cases it is possible, and sometimes even necessary, to exceed or fall below these ranges.

Next, typical examples of pests to which the pest control agent of the present invention can be applied are listed.

(1) Lepidoptera: For example, phyllonory terrin
goniolla), diamondback moth (plutella x
ylostelle), cotton moth (Promalac)
tis inonisema), Kokakumon Hamaki (
, Adoxophyes orana ), Leguminivora glycinivo
relle), Cnaphalocr
ocis medinalis), Nikamay moth (Ch.
il.

Qst.
rinia furnacalis), armyworm (M
amestra brassicae), foxtail armyworm (pseudaletia 5eparata)
), Spodoptera Iitur
a), Parnara guttat
a), Pieris rapaec
rucivora).

(2) Coleoptera]: For example, Anomala cuprea
), Poptllia japonica
), rice weevil (Echinocnemus sq.
uameus), rice weevil (Li5sorh
optrus oryzophilus), Qulema Oryzae, Anthrenus verba
sci), Cocnust ('I'enebroides)
mauritanicus), brown weevil (5it
ophillus zeamais), Enosepila-chna vi (:F(enosepila-chna vi)
gintioctopunctata), adzuki bean weevil (Callosobruchus chinens
is ), Monochamu
s alternatus ), cucumber beetle (, Au
1acophora femoralis).

(3) Diptera [])iptera]: For example, Cu1ex pipiensfatiga
ns ), Aedes aegypt
i), 4 Soybean pod x (Asphondylia sp.
, ), Tanever C (I-(ylemya platur
a), Muscadames Lica
v+cina), urimiba-c (]) acus c
ucurbitae), Rice leafminer x (Agr
omyza oryzae).

(4) Orthoptera [: Qrthoptera):
For example, Gryllotalpa africa
na ), ) Nosamabanota (Locustami)
gratoria), Kobane Locust (Qxya ye)
zoensis), German cockroach (Blatte)
-11a germanica), black cockroach (P
eriplaneta fuliginosa).

(5) Hymenoptera:
For example, turnip babachi (Athalia rosae)
japone-nsls), Ruriteyurenji Sawfly (Arge 51m11ia).

(6) Tylenchida: For example, Hetero-dera g.
lycines), Inesist Senteyu (Hete
-rodera oryzae), Meloidogyne incogni
ta), Pratylen
chus neglectus), Aphelenchoides ritzem
abosi), Bursap
helenehus 11gn1colus).

(7) Hemiptera, such as the black leafhopper (Nephotettixo)
incticeps), white-legged planthopper (Sogate)
lla furcife-ra), brown-bottomed planthopper (
Laodelphax 5triatellus),
Brown planthopper (Ni1aparvata lugen)
Riptortus cl), Riptortus cl.
avatus), southern stink bug (Nezara
viridula), Nasigunbai (J3teph
antis nashi), the whitefly (Trialeurodes vaporarioru)
m), cotton aphid (Aphis gossypi)
i), green peach aphid (Myzuspersic
ae ), TJnaspis y
ano-nesis).

(8) Acarina: For example, Tetranychus urtic.
ae ), orangefin = (panonychus c
itri), false namihada = (Tetranych
us cinnabarinus), Kanzawahada
=-(Tetranychus kanzawai)
, apple spider mite (Panonychus ulmi)
, Tetranychus vie
nnensis), Citrus savida (Aculu
spelekassi), Teyanochorida = (Po
Lyphagota-rsonemus Iatus
), Suginohada = (Oligonychusbond)
oensis), Nasisabida = (Epitrime)
rus pyri), Cyclamenhocorida = (St
eneotarsonemus pallidus)
, Tenuipalpus zhi
zhilas-hviliae), Teyanohimehada =
(Brevipalpusobovatus), Cloverhada =- (Bryobia praetios)
a), Grape Savida =- (Calepitrimer
us vitis), woolly konada = (Tyrop
hagus putrescenticae), Rhizoglyphus echinopus
).

〔Effect of the invention〕

The pyrimidine derivatives of the present invention have excellent insecticidal and acaricidal effects, as is clear from the Examples below.

〔Example〕 The present invention will be explained below.

Example 1. Synthesis of 6-fluoro-2-methylthio-3propargyl-5-trifluoromethyl-4(3H)-pyrimidinone (synthesis of intermediate) 6-fluoro-2-methylthio-5-trifluoromethyl- 1.0 g of 4(3H)-pyrimidinone in 10 g of acetone
1.2 g of potassium carbonate and 0.63 g of propargyl bromide were added thereto, and the mixture was heated under reflux for 12 hours. After returning to room temperature, water was added and extracted with ethyl acetate, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by column chromatography (silica gel; developing solution: hexane: ethyl acetate: 5=1) to obtain the desired 6-fluoro-
0.38 g of 2-mefkf-3propargyl-5-trifluoromethyl-4(3H)-pyrimidinone was obtained.

'H-nmr data (CDCt3.TMS);
δ2.35 (t, J2.4Hz, IH), δ2.6
9 (s, 3H), δ4.86 (d, J=2.4H
z, 2H) Example 2. 6-dietheramino-2-methylthi-5-
Synthesis of torinefluoromethyl-4(3H)-pyrimidinone (inventive compound N1): 6-fluoro-2-,Ifruthio5-)! J Fu 8 fluoromethyl-4(3H)-pyrimidinone 1. Og was dissolved in 10 ml of acetonitrile, and 0.71 g of diethylamine was added dropwise in an ice water bath. After returning to room temperature and stirring overnight, water was added and extracted with ethyl acetate. After washing with saturated brine, it was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The crude product was washed with a mixed solvent of n-hexane and diethyl ether and passed through the mouth. After drying, the desired 6-
092 g of diethylamine-2-methylthio-5-trifluoromethyl-4(3H)-pyrimidinone was obtained.

Melting point 15'7-158°C.

Example 3. Synthesis of 3-allyl-6-diethylamino-2methylthio-5-trifluoromethyl-4(3H)-pyrimidinone (compound of the present invention 43): 6-diethylamino-2-methylthio-5trifluoromethyl- 0.9 g of 4(3H)-pyrimidinone in acetone Ion/! Dissolved in 0.88 g of potassium carbonate,
0.46 g of allyl bromide was added, and the mixture was heated under reflux for 12 hours. After returning to room temperature, water was added, extracted with ethyl acetate, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude product was subjected to column chromatography (silica gel; developing solution: n-hexane:
Ethyl acetate (3=1) was used to obtain 043 g of the desired 3-allyl-6-diethylamino-2-methylthio-5-trifluoromethyl-4(3H)-pyrimidinone.

Melting point 65-66°C.

Example 4.6-di-n-butylamino-2-methylthio-3-propargyl-5-trifluoromethyl-4(3
H)-Synthesis of pyrimidinone (compound of the present invention 1'1!1l
L56): 6-fluoro-2-methylthio-3-propargyl-5
−)! J Fluoromethyl-4(3H)pyrimidinone 0
．． 38 g was dissolved in 1 Q ml of acetonitrile, and 0.54 g of di-robenalamine was added dropwise in an ice water bath. After returning to room temperature and stirring for 6 hours, water was added and extracted with ethyl acetate.

After washing with 2.5% hydrochloric acid and saturated brine, it was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.

The crude product was washed with a 5=1 mixed solvent of n-hexane and ethyl acetate and passed through the mouth. After drying, the desired 6-J-n-
Butylamino-2-methylthio-3nipropargyl-5
0.41 g of -trifluoromethyl-4(31-()-pyrimidinone) was obtained.

Melting point; 135.5-137.0°C 1 Next, the effects of the present invention will be specifically explained using test examples.

Test example 1. Test for egg killing of red spider mites Ten adult red spider mites were inoculated onto the first leaves of potted French beans, and all adults were removed one day later. 20% emulsion of the compound of the present invention and the control compound (described in Formulation Example 5)
Or 500 pp of 50% Permanent Agent (described in Formulation Example 2)
The primary leaves were immersed for 10 seconds in an aqueous solution diluted to 500 ml, air-dried, and then left in a constant temperature room at 25° C. for 9 days to check whether the eggs were alive or dead. All death penalty rates were calculated using the Abbott formula. As a result, the following compound had a death penalty rate of 100%.

1'! l13. 14. 18. 19-25.27 to 33.37° 38.40-45.49-52° Test Example 2. Effect 3 or 4 on brown planthoppers
Five to six rice plants at the leaf stage were immersed for 15 seconds in a treatment solution diluted with water so that the active ingredient of each test chemical was 500 pI)m.

After air-drying, it was placed in a glass cylinder with a diameter of 4.5 cm and a height of 15 cm, and 10 female adult brown planthoppers (Kaseda dust) were released into the cylinder, which was then covered with a wire mesh lid and placed in a glass greenhouse. Eight days after the treatment, the number of live and dead insects was investigated, and the insect killing rate was calculated. As a result, the following compound had a 100% insecticidal rate.

%14. , 19, 33, 34-37.40.42.44
゜45゜Test Example 3. Effect on Chikaie force Pour 20Qml of well water into a plastic cup and release 10 Chikaeka 3rd instar larvae. Add 1 liter of a drug solution diluted with acetone so that the active ingredient of each test drug is 5 ppm.
rnl was added, and the mixture was covered with a lid and left in a constant temperature room at 25 degrees.

Seven days after treatment, the number of dead insects was measured to determine the insect killing rate. As a result, the following compound had a 100% insecticidal rate.

1'! 120,23~26.28,31.32.55°Test Example 4. Effect on diamondback moth A mid-sized cabbage leaf that had grown to about 10 true cabbage leaves was cut out and immersed for 15 seconds in a treatment solution diluted with water so that the active ingredient of each test chemical was 5001) pm. After air drying, it was placed in a plastic container with a diameter of 9 cm, and 15 third instar larvae of the diamondback moth were released into the container.

Cover the container with a lid with 5 to 6 small holes, and leave it in a constant temperature room at 25°C. Ten days after treatment and release of insects, the number of living and dead insects was investigated, and the killing rate was calculated. As a result, the following compound had a 100% insecticidal rate.

Nrt17.20.24゜

Claims (4)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (In the formula, R_1 represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkenyl group, an alkynyl group, and R_2
represents a lower alkyl group having 1 to 3 carbon atoms, R_3,
R_4 is a hydrogen atom, a pyrimidine derivative represented by a branched alkyl group having 1 to 6 carbon atoms, or a substituted phenyl group, or a substituted phenyl group in which R_3 and R_4 may be connected to each other to form a ring. (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) (In the formula, R_2 represents a lower alkyl group having 1 to 3 carbon atoms.) A compound represented by R_1X (2)' (formula (wherein, R_1 represents a lower alkyl group, alkenyl group, or alkynyl group having 1 to 4 carbon atoms, and X represents a halogen atom), and the resulting general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3 ) (However, in the above formula (3), R_1 and R_2 are the above formula (1)
) is the same as the general formula (4) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (4) (However, in the above formula (4), R_3 and R_4 are the same as the above formula (1
) is a general formula that is characterized by reacting with a compound represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. Preparation of the compound represented (3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_2 represents the same thing as above) and the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (4) (Formula (wherein, R_3 and R_4 represent the same things as above) are reacted to form a compound represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (5) (wherein R_2, R_3, R_4 represent the same things as above) This compound is prepared by formula R_1-X(2)' (wherein R_1 represents a lower alkyl group, alkenyl group, or alkynyl group having 1 to 4 carbon atoms, and X represents a halogen atom). A method for producing a compound represented by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (in the formula, R_1 to R_4 represent the same things as above), characterized by reacting with. (4) Contains one or more pyrimidine derivatives represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (In the formula, R_1 to R_4 represent the same as above) as an active ingredient. An agricultural and horticultural insecticide, acaricide, or bactericide characterized by: