JPH02306964A - Pyridine derivative and insecticide-miticide with same as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound of formula I or II [X is H, halogen, 1-4C (halo) alkyl, 1-4C (halo)alkoxy, phenyl, 1-4C haloalkylsulfonyl, etc.; R<1> to R<4> are each H, halogen or 1-4C (halo)alkyl; R<5> is 1-6C alkyl; n is integer 0-5, in case n is >=2, Xs may differ from one another; but excepting that (1) R<1> to R<4> are H at the same time in the formulas I and II, (2) in the formula I, n is 0, R<2> is H and R<1> and R<5> are CH3, and (3) in the formula II, n is 0, R<2> to R<4> are H, and R<1> and R<5> are CH3]or its salt. EXAMPLE:1-(3-ethyl-4-pyridyl)-2-phenyl-1-propene. USE:Insecticides and/or miticides. PREPARATION:An addition reaction is made between a compound of formula III and a compound of formula IV in a solvent in the presence of a base, and the resultant compound of formula V is dehydrated, thus obtaining the objective compound of the formula I.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to novel pyridine derivatives, salts thereof, and insecticides and acaricides, and more specifically to pyridine derivatives and salts thereof having insecticidal and acaricidal effects, and the derivatives thereof. Or it relates to insecticides and acaricides containing the salt as an active ingredient.

[Prior art and problems to be solved by the invention] Insecticides have traditionally been used to control insect pests in agricultural and horticultural crops and to control insect pests, and have greatly contributed to increasing the production of agricultural and livestock products and improving the 'S' living environment. I've been doing it. The conventionally used insecticides are chlorine-based and organophosphorus-based.

There are carbamate types, pyrethroid types, etc. However, in recent years, these insecticides have caused pollution problems such as environmental pollution due to chemical spraying, safety problems such as persistence and accumulation, and problems of drug resistance. Therefore, there is a need for the development of new insecticides and acaricides that are highly effective and free from the problems mentioned above.

US Pat. No. 2,427,286 discloses the use of 4-styrylpyridine as an insecticide, which has a significantly different structure from the conventional insecticides mentioned above.

However, this compound can be used as a 0.5% solution to kill, for example, green cabbage.
aphid), which can kill 96.3% of
It has low activity.

In addition, Pe5ticide 5science volume 6,
645 (1975) describes a quaternary ammonium salt of 4-styrylpyridine, but this compound shows no insecticidal or acaricidal activity against house flies, German cockroaches, or mites.

Also, The Journal of Organic
ChemisLry volume 31, 4322. (1966)
describes 1-(3-methyl-4-pyridyl)-2-phenyl-1-propene and 1-(3-methyl-4-pyridyl)-2-phenylpropane, but these compounds are insecticidal.・It is not stated that it has acaricidal effect.

Therefore, the present inventors have conducted extensive research in order to develop a new insecticide that is highly active and does not cause the problems of persistent 2 accumulation and drug resistance.

[Means to solve the problem]

As a result, it was found that pyridine derivatives with specific structures and salts thereof exhibit high insecticidal and acaricidal effects. The present invention was completed based on this knowledge.

That is, the present invention is directed to -fune formula [wherein X is a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a haloalkyl group having 1 to 4 carbon atoms].

Alkoxy group having 1 to 4 carbon atoms 4 Haloalkoxy group having 1 to 4 carbon atoms, phenyl group, alkyl-substituted phenyl group having 1 to 4 carbon atoms, alkyl group having 1 to 4 carbon atoms substituted with a phenyl group, or HafR represents a haloalkylsulfonyl group having a prime number of 1 to 4; R+, R1, Rz and R4 each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a haloalkyl group having 1 to 4 carbon atoms; RS represents a haloalkyl group having 1 to 4 carbon atoms; represents an alkyl group having 1 to 6 carbon atoms, n is an integer of 0 to 5,
When n is 2 or more, each X may be the same or different. However, ■ Formula (1), [R1 in formula R3
When -R4 is hydrogen at the same time, in the formula ■CI),
When n is 0, R2 is a hydrogen atom, and R' and Rs are methyl groups, and (1) in formula (11), n is 0, R2, R3, and R' are hydrogen atoms, and R1 and R5
except when is a methyl group. ] or a salt thereof, as well as a pyridine derivative or a salt thereof represented by the above general formula (1) or ([I) (note that the above cases ① to ② are also included here). The present invention provides an insecticide/acaricide containing as an active ingredient.

In the above general formulas (+) and (II), the halogen atom represented by X includes chlorine, fluorine, bromine and iodine. Further, the alkyl group having 1 to 4 carbon atoms represented by X may be linear or branched,
Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-
There are butyl groups, etc. The haloalkyl group having 1 to 4 carbon atoms represented by X means an alkyl group having 1 to 4 carbon atoms in which one or more of the hydrogen atoms of the alkyl group is substituted with a halogen,
Specifically, for example, monochloromethyl group, dichloromethyl group, trichloromethyl group, monochloroethyl group, dichloroethyl group, trichloroethyl group, tetrachloroethyl group, monochloropropyl group, dichloropropyl group, trichloropropyl group, tetrachloropropyl group. , pentachloropropyl group, monochlorobutyl group, dichlorobutyl group, trichlorobutyl group, tetrachlorobutyl group, pentachlorobutyl group or hexachlorobutyl group, etc.
Furthermore, one or more of the chlorine in the above group is fluorine,
Mention may be made of the corresponding haloalkyl groups substituted with bromine and/or iodine.

Further, the alkoxy group having 1 to 4 carbon atoms represented by X means an alkoxy group in which a linear or branched alkyl group having 1 to 4 carbon atoms is bonded to an oxygen atom, and specifically,
Methoxy group, ethoxy group.

Ω-propoxy group, isopropoxy group, n-butoxy group,
Examples include imbutoxy group and t-butoxy group. Further, the haloalkoxy group having 1 to 4 carbon atoms represented by Methoxy group, dichloromethoxy group, trichloromethoxy group, monochloroethoxy group, dichloroethoxy group, trichloroethoxy group, tetrachloroethoxy group, monochloropropoxy group, dichloropropoxy group,
trichloropropoxy group, tetrachloropropoxy group,
pentachloropropoxy group, monochlorobutoxy group, dichlorobutoxy group, trichlorobutoxy group, tetrachlorobutoxy group, pentachlorobutoxy group, hexachlorobutoxy group, etc. Furthermore, one or more of the chlorine of the above groups is fluorine, bromine, / or corresponding haloalkoxy groups substituted with iodine.

Furthermore, the phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, represented by X, is a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms at the o-, m-, and/or p-positions. , the alkyl group as this substituent is the same as that shown in the above specific example.

X represents an alkyl group having 1 to 4 carbon atoms which is further substituted with a phenyl group, and the alkyl group here is the same as that shown in the above specific example.

X also represents a haloalkylsulfonyl group having 1 to 4 carbon atoms, and haloalkyl here means a group in which one or more hydrogen atoms of an alkyl group are substituted with a halogen atom, as described above. Specific examples of the haloalkylsulfonyl group having 1 to 4 carbon atoms include monochloromethylsulfonyl group, dichloromethylsulfonyl group, trichloromethylsulfonyl group,
Monochloroethylsulfonyl group, dichloroethylsulfonyl group, trichloroethylsulfonyl group, tetrachloroethylsulfonyl group, monochloropropylsulfonyl group, dichloropropylsulfonyl group.

trichloropropylsulfonyl group, tetrachloropropylsulfonyl group, pentachloropropylsulfonyl group,
Monochlorobutylsulfonyl group, dichlorobutylsulfonyl group, trichloro7'thi/L, sulfonyl group, tetrachlorobutylsulfonyl group.

Examples include a pentachlorobutylsulfonyl group or a hexachlorobutylsulfonyl group, as well as corresponding haloalkylsulfonyl groups in which one or more of the chlorines of the above groups are substituted with fluorine, bromine and/or iodine.

In the above general formulas (N and (II)), n indicating the number of substituents represented by χ is an integer of 0 to 5.

When n is 2 or more, each X may be the same substituent or different substituents.

In the above general formulas (1) and (II), R1゜RZ
, R3 and R4 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a haloalkyl group having 1 to 4 carbon atoms; The haloalkyl group of ~4 is the same as that explained for the halogen atom, the alkyl group having 1 to 4 carbon atoms, and the haloalkyl group having 1 to 4 carbon atoms, represented by X above.

In the above general formulas N) and (11), the alkyl group having 1 to 6 carbon atoms represented by R5 is a linear or branched alkyl group having 1 to 6 carbon atoms, such as a methyl group. , ethyl group, n-propyl group, isopropyl group,
n-butyl group, isobutyl group, t-butyl group, n-pentyl group, impentyl group, t-pentyl group, n-hexyl group, isohexyl group, L-hexyl group, ■-methyl-2-dimethylpropyl group, Examples include 1-dimethyl-2-methylpropyl group.

In the pyridine derivatives represented by general formulas (I) and (IN, Here, the pyridine derivative or its salt of the present invention has the following formula (■-General formula (■)).

In (II), when R1-R4 are hydrogen at the same time,
■-General formula (■)], when n is O, R2 is a hydrogen atom, and R1 and R5 are methyl groups, and ■-General formula (U), n is 0, R2, R2, and R4
is a hydrogen atom and R' and R5 are methyl groups.

The pyridine derivative of the above general formula (I) can be produced by various methods, but for example, the pyridine derivative of the general formula (wherein X, R' and n are the same as above). ] The ketone represented by the general formula [wherein R2 and R5 are the same as above]. ] with the substituted pyridine in a solvent in the presence of a base, resulting in a general formula (V) [wherein X, R', R'',
RS and n are the same as above. ] It can be produced by dehydrating the alcohol represented by

The solvent used in the addition reaction between the above ketone and substituted pyridine includes aromatic hydrocarbons such as benzene and toluene,
Examples include ethers such as diethyl ether, tetrahydrofuran, dimethoxyethane 5 and diglyme, polar aprotic solvents such as dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, and liquid ammonia.

In addition, as a base, lithium diisopropylamine,
Potassium t-butoxy, sodium phenyl, sodium amide, etc. can be used.

The reaction conditions may be appropriately selected depending on the situation, and the reaction temperature is preferably -100°C to 50°C.

The dehydration reaction of the alcohol obtained by the above addition reaction is carried out using dilute sulfuric acid, concentrated sulfuric acid, diline pentoxide, thionyl chloride, phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, etc. It may be carried out using a solvent such as benzene, toluene, or xylene.

Aromatic solvents such as pyridine may also be used.

Other conditions for the dehydration reaction may be appropriately selected depending on the situation, but the temperature is preferably in the range of -30°C to 150°C.

Furthermore, the pyridine derivative of the general formula (1) of the present invention can be produced by the following steps (a) to (C) including a Grignard reaction. That is, (a) general formula (Vl) I [wherein, X, n, and R' are the same as above, and Y represents a halogen. ] A substituted benzyl halide represented by
indicates a halogen atom. ] A Grignard reagent represented by is produced. Solvents that can be used in this reaction include diethyl ether,
Examples include ethers such as tetrahydrofuran and dimethoxyethane.

Other reaction conditions may be appropriately selected depending on the situation, but the temperature is preferably in the range of 30 to 80°C.

(b) The above Grignard reagent is expressed by the general formula [■] [wherein,
Rz and R5 are the same as above. [In the formula, χ, n, R', R and R5 are the same as above. ] An alcohol compound represented by is produced. This reaction is (
a) -50'C- using the same solvent used in step
Other reaction conditions can be selected as appropriate depending on the situation.

(C) The alcohol obtained in step (b) above is dehydrated using a dehydrating agent in the presence or absence of a solvent, and the general formula CI)
Obtain the desired object. Here, as a solvent, an aromatic solvent such as benzene, toluene, xylene, pyridine, etc. is used,
As the dehydrating agent, dilute sulfuric acid, concentrated sulfuric acid, diline pentoxide, thionyl chloride, phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, etc. can be used. Dehydration reaction is usually carried out at -30℃
Perform at a temperature of ~150″C.

Further, the pyridine derivative represented by the general formula (1) is represented by the general formula (X) [wherein X and n are the same as above, and R6 represents an alkyl group]. ] The substituted benzoic acid ester represented by the above general formula (
A condensation reaction is carried out with the substituted pyridine of IV) in a solvent in the presence of a base, and the resulting ketone represented by the general formula (XN [wherein, X, n, R'' and R% are the same as above] It is reduced, producing alcohol, and then dehydrated.

Examples of the solvent used in the condensation reaction between the substituted phenylacetic acid ester and the substituted pyridine include aromatic hydrocarbons such as benzene and toluene, diethyl ether, tetrahydrofuran, and dimethoxyethane.

Examples include ethers such as diglyme, polar aprotic solvents such as dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, and liquid ammonia.

In addition, as a base, lithium diisopropylamine,
Potassium t-butoxy, sodium phenyl, sodium amide, etc. can be used.

The reaction conditions may be appropriately selected depending on the situation, and the reaction temperature is preferably -100°C to 50°C.

When synthesizing alcohol from ketones, sodium borohydrite, sodium borocyanohydride, lithium aluminum hydride, etc. are used as catalysts. As the solvent, the former two include tetrahydrofuran,
Ether etc. are used, and alcohols, hydrous alcohols etc. are preferably used for the latter. Further, the reaction temperature at that time is preferably 0 to 7.0°C, and more preferably 10 to 20°C.

Further, the dehydration reaction of the alcohol may be carried out in the same manner as described above.

Specific examples of the pyridine derivative of general formula (1) produced as described above include, for example, I-(3-ethyl-4-
pyridyl)-2-phenyl-1-propene; I-phenyl-2-(3-methyl-4-pyridyl)-1-propene: 1-phenyl-2-(3-ethyl-4-pyridyl)-
1-propene; 1-(3-methyl-4-pyridyl)-2
-Phenyl-3,3,3-trifluoro-1-propene; 1-(3-ethyl-4-pyridyl)-2-phenyl-
3,3,3-1-lifluoro-1-propene; 1-(2
-chlorophenyl)-2-(3-methyl-4-pyridyl)-1-propene; 1-(3-trifluoromethylphenyl)-2-(3-methyl-4-pyridyl)-1-propene; l-( 3-ethyl-4-pyridyl)-2-(2
-fluorophenyl)-1-propene; 1- (3-
Methyl-4-pyridyl)-2-(2-chlorophenyl)
-1-broben; 1-(3-ethyl-4-pyridyl)-
2-(2-chlorophenyl)-1-propene; 1-(3
-ethyl-4-pyridyl)-2-(3,4-cyclophenyl)-1-7"lopen;1-(3-methyl-4-pyridyl")-2-(3,4-dichlorophenyl)-1-
Propene; 1-(3,4-dichlorophenyl)-2
-(3-ethyl-4-pyridyl)-1-propene; 1-
(3-trifluoromethylphenyl)-2-(3-ethyl-4-pyridyl)-1-propene; 1- (3-ethyl-4-pyridyl) to 2-(4-t-butylphenyl)-1- Propene; 1-(3-ethyl-4-pyridyl)
2 (4-sec-butylphenyl)-I-propene 1l-(3-ethyl-4-pyridyl)-2-(4-
phenethyl phenyl)-1-propene; 1-(3,4-
Dichlorophenyl)-2-(3-methyl-4-pyridyl)-1-propene; 1-(3-methyl-4-chlorophenyl)-2-(3-ethyl-4-pyridyl)-1-propene, etc. .

Next, the pyridine derivative represented by the above general formula (I[) can be produced by various methods, but for example, the fftA benzyl halide of the above general formula (Vl) is converted into the general formula (Xn) CH,R'' [ In the formula, Rχ and R5 are the same as above.

Benzene is used as a solvent for this reaction.

Aromatic hydrocarbons such as toluene, diethyl ether.

Examples include ethers such as tetrahydrofuran, dimethoxyethane, and diglyme, polar aprotic solvents such as dimethylformamide, dimethylsulfoxide, and hexamethylphosphoric triamide, and liquid ammonia.

Further, as the base, lithium chloride propylamine, t-butoxypotassium, phenyl sodium, sodium amide, etc. can be used.

The reaction conditions may be appropriately selected depending on the situation, and the reaction temperature is preferably -100'C to 50C.

In the general formula (n), if you want to substitute a dialkyl group on the α carbon bonded to the 1-position of pyridine, use
[2] The substituted benzyl halide of the general formula (XI[[) [wherein, Hz, R4 and R5 are the same as above]. ] The addition reaction may be carried out with a substituted pyridine represented by the following. At this time, lithium aluminum hydride (
LiA/! H4) and other conditions may be the same as in the case of the addition reaction described above.

In addition, the pyridine derivative of the general formula (II) in which R3 represents an alkyl group is a substituted benzyl halide represented by the general formula (XIV) (X, n, R', R3 and Y are the same as above). is reacted with a compound represented by general formula (XV) [wherein R5 is the same as above] in the presence of general formula (XVI) [wherein, X, n, R', R'', R3 .

This reaction is preferably carried out in a solvent such as ethylene glycol, diethylene glycol, triethylene glycol or the like.

The reaction conditions may be appropriately selected depending on the situation, and the reaction temperature is preferably in the range of 180°C to 220°C.

In the above general formula (n), a compound in which X is hydrogen is reacted with an alkylating agent or a haloalkylating agent,
Compounds can also be prepared in which X is an alkyl group or a haloalkyl group. This reaction can be carried out using a known alkylation method,
This can be carried out by a haloalkylation method.

Here, as the alkylating agent, methyl chloride; methyl bromide; ethyl chloride; ethyl bromide; i-propyl chloride; i-propyl bromide;
L-butanol; t-butyl chloride; L-butyl bromide; 5ec-butyl chloride; 5ec-butyl bromide; 2-L-butyl-p-cresol; 2
, 6-di-L-butyl-p-cresol and the like. For example, when a solution of this 2,6-di-t-butyl-p-cresol dissolved in nitromethane is reacted in the presence of aluminum chloride as a catalyst, a pyridine derivative in which X is an L-butyl group is obtained.

Specific examples of the pyridine derivative of general formula (II) produced as described above include, for example, 1-(2-chlorophenyl)-1-(3-ethyl-4-biridyl)-ethane; 2-(3-ethyl-4-pyridyl)-
Propane; 1-(2-chlorophenyl)-2-(3-methyl-4-pyridyl)-propane 1f-(3
,4-dichlorophenyl)-2-(3-ethyl-4-pyridyl)-propane; 1-(3,4-dichlorophenyl)-2-(3-methyl-4-pyridyl)-propane;
1-(3-ethyl-4-pyridyl)-2-phenyl)-
2-phenyl-3,3,3-1-lifluoropropane;
1-(2-trifluoromethylphenyl)-2-(3
-ethyl-4-pyridyl)-propane; 1 (4je
rt-butylphenyl)-2=(3-n-propyl-4
-pyridyl)-propane; 1 (4tert-butylphenyl)-2-(3-n-butyl-4-pyridyl)
-Propane; 1-(3-methylphenyl)-2-(3-
Examples include ethyl-4-pyridyl)-1-propene.

The pyridine derivatives of the general formula (+) above include cis and trans stereoisomers, both of which have insecticidal and
Acaricidal activity is observed. In this specification, unless otherwise specified, one or both isomers are meant.

The pyridine derivatives of the present invention can form pyridinium salts with acids. Accordingly, the present invention further provides salts of pyridine derivatives. Examples of acids include hydrochloric acid, hydrobromic acid, hydriodic acid, hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, citric acid, and lactic acid.

Examples include oxalic acid, maleic acid, tartaric acid, benzoic acid, nicotinic acid, dodecylbenzenesulfonic acid, and various fatty acids.

The pyridine derivatives of the present invention represented by the above general formulas (1) and (II) and their salts have strong insecticidal and acaricidal effects, and because they have a different structure from conventional insecticides, they are different from conventional insecticides. It is thought to act on insects through its mechanism of action. In addition, ■- In general formulas 1) and (II), R'-R' are simultaneously hydrogen pyridine derivatives, ■- In general formula 13, n is 0, R2 is a hydrogen atom, and R1 and R5 are methyl groups. Certain pyridine derivatives and pyridine derivatives in which n is 0 in the general formula II), Rz, Rz and R' are hydrogen atoms, and R1 and R5 are methyl groups, may also be used together with the pyridine derivatives of the present invention and salts thereof. , which exhibits insecticidal and acaricidal effects.

Insects for which the pyridine derivatives (including salts thereof) of the present invention exhibit activity include Hemiptera, Coleoptera, and Lepidoptera.
optera) + Acarina, etc. A typical insect is the green peach aphid (M
yzus persicae), cotton aphid (A
phis gossypii), radish aphid (Lipaphis erysimi) + black leafhopper (Nephotettix cinctice)
ps), ) Nilaparvata
lugens) + white-legged planthopper (Soga te)
Iafurcifera) + Laodea I phaxsLriatellus
+ Trialeurodesv
aporariorum) - Ilenosepi Iachnaν1g1ntio
ctopunctata) + rice beetle (
Oulemaoryzae) + rice weevil (L
jssorhoptrus oryzophilus)
.

Cnaphalocrocis med
inalis), two-spotted spider mite (Tetranychus)
urticae) + citrus spider mite (Panonych)
US ciLri), etc.

The pyridine derivatives of the present invention can be used to control rice field pests (planthoppers represented by the brown planthopper, white-backed planthopper, and brown planthopper, etc., or leafhoppers represented by the black leafhopper), which have become a problem in recent years due to the emergence of resistant species. It is effective for Moreover, the pyridine derivative of the present invention is applied to wheat.

Corn, vegetable 5 petals, trees, cotton, fruit trees, grass.

It is effective in controlling pests on grass, harvested grain, timber, and wood products.

Therefore, the present invention further provides an insecticide/acaricide containing the pyridine derivative of the present invention or a salt thereof as an active ingredient.

The insecticide/acaricide of the present invention may be in the form of a solid, liquid or paste preparation containing the active ingredient, specifically as a two-grain powder, a fine granule, a wettable powder, or an oil solution.

It may be in the form of an emulsion, a spray, a flowable, or the like.

Solid preparations in the form of powders are prepared by mixing the active ingredient with a solid carrier;
It can be manufactured by grinding. Granules or microgranules are produced, for example, by coating or impregnating preformed granular solid carriers with the active ingredient or by binding the active ingredient to the solid carrier by agglomeration techniques.

Here, as the solid carrier, vegetable powders such as grains,
Soybean, wood, bark, bran, etc.; mineral powder.

Examples include clay, talc, bentonite, acid clay, kaolin, talc, diatomaceous earth, synthetic silicate, pumice, activated carbon, fly ash, and synthetic resin.

A solid preparation is a dispersible or aqueous preparation in which, in addition to the active ingredient and a solid carrier, one or more surfactants that act as wetting agents, emulsifiers, and/or dispersants are mixed to promote the dispersion of the active ingredient in a liquid. It may also be in the form of a solid formulation, for example a wettable powder.

Examples of the surfactant include cationic, anionic, and nonionic surfactants. Examples of cationic surfactants include quaternary ammonium salts such as cetyltrimethylammonium bromide. In addition, examples of anionic surfactants include alkylaryl sulfonates, lignin sulfonates, etc., and examples of nonionic surfactants include polyoxyethylene alkylaryl ether, polyoxyethylene higher fatty acid ester, sorbitan ester, and sucrose. Examples include esters.

Liquid preparations consist of a solution or dispersion of the active ingredient in a liquid carrier, optionally containing wetting agents, such as those mentioned above.
It contains one or more surfactants that act as emulsifiers and/or dispersants.

Liquid carriers include water, alcohols 2 such as methanol, ethanol, and ethylene glycol, ketones 5 such as methyl ethyl ketone, diisobutyl ketone, cyclohexanone, and hydrocarbons.

Examples include kerosene, solvent naphtha, toluene, xylene, etc., esters 1 such as dioctyl phthalate, amides 1 such as dimethylformamide, nitriles 1 such as acetonitrile, dimethyl sulfoxide, oils and fats.

The insecticide/acaricide of the present invention may further contain adjuvants such as fixing agents, thickeners, stabilizers, etc. Examples of such adjuvants include casein and gelatin.

Examples include alginic acid, carboxymethylcellulose, gum arabic, and polyvinyl alcohol.

The insecticide/acaricide of the present invention may be a formulation that can be used as is or a concentrated formulation that requires dilution before use.
It may contain the pyridine derivative of the present invention or its salt in an amount of 0.1 to 99% by weight, preferably 0.5 to 80% by weight. For example, it is appropriate for a single powder tablet to contain 0.5 to 20% by weight of the pyridine derivative or its salt of the present invention, and for an emulsion or a wettable powder to contain 5 to 50% by weight.

Next, examples of formulations for each form are shown below.

Example U of 050% emulsion Formula 11) Compound of the present invention 50xylene
40 Mixture of polyoxyethylene nonyl phenyl ether and potassium alkylbenzene sulfonate 10 The above components are thoroughly stirred and mixed to form an emulsion.

■Example of 3% powder Compound of the present invention 3 clay powder
97 Thoroughly crush and mix the above ingredients to make a powder.

020% Hydrating Agent Compound of the Invention 20 Anionic Surfactant 5 Diatom ±
75 Thoroughly crush and mix the above ingredients to make a wettable powder.

Example of 02% oil agent Compound of the present invention 2 Kerosene
9B Mix the above ingredients well to make an oil agent.

■Example of 5% granules Compound of the present invention 5 Bentonite 53 Talc
40 Calcium lignin sulfonate
2. Thoroughly crush and mix the above acid components, add water and knead well, then granulate and dry to form granules.

The amount of the insecticide/acaricide of the present invention to be generally used depends on various factors, such as the target pest, its occurrence, and the weather.

Although it varies depending on the dosage form, method of application, place of application, and time of application,
Generally, 1 powder tablet is 1 to 10 k of preparation per 10 ares.
Let it be g. Furthermore, in the case of products that are ultimately used in liquid form, such as emulsions and wettable powders, the concentration of active ingredients is generally 0.
A spray solution is prepared by diluting the solution to a concentration of 0.001% by weight or more.

In addition to the insecticide/acaricide of the present invention, other known insecticides, acaricides, insect hormones, fungicides, nematicides, herbicides,
By mixing plant growth regulators, fertilizers, etc., it is possible to create a multipurpose composition with even better effects, and further synergistic effects can be expected.

Specific examples of insecticides that can be mixed include pyrethroids,
For example, permethrin, fenvalerate.

Nisfenvalerate, cycloprothrin 1 Bifenthrin, fenpropathrin, etofenpronox, etc., organic phosphorus such as Bisit, Ersan, Diazinon, MEP, DDVP, Marathon, Dimethoate, D
MTP, acephate, etc., carbamates, e.g. NA
C, MTMC, PHC, MPMC, BPMC, methomyl, carbosulfan, cartap, oxamyl, etc., benzoyl urine i, such as chlorfluazuron, teflubenzuron, etc., other fenbutazin oxides, amitraz,
Examples include chlorbenzilate, phenoxycarb, and buprofezin.

A specific example of a fungicide is Kasugamayren. Plasticidin S, Fusaride, IBP, EDDP, l-lycyclazole, Viloquilon, Isobrothiolane, Validamycin, Polyoxin, Mepronil, Flutolanil,
Benziclone, diclomedine, thiophanate methyl,
Procymidone, iprodione, triadimefon, bitertanol, fenarimol, prochloraz, triflumizole.

Examples include birifenox, metalaxyl, fosetyl, guazathine, etc.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Example 1 l-(3-ethyl-4-pyridyl)-2-phenyl-1
- Synthesis of propene 4.21 diisopropylamine in a 200d flask
g (42 mmol) and 15 d of tetrahydrofuran were added thereto, and the mixture was cooled to -50°C. To this was added 29 ml (46 ml) of n-butyllithium (15% n-hexane solution) under a nitrogen stream.
, 2 mmol) and stirred for 10 minutes, 3-ethyl-4
- A solution of 5.09 g (42 mmol) of methylpyridine in tetrahydrofuran was added dropwise. After stirring at -50"C for 30 minutes, the reaction temperature was gradually raised, maintained at -10°C for 30 minutes, and then cooled again to -50"C.To this, 5.0g (42 mmol) of acetophenone was added to tetrahydrofuran. The solution was added dropwise and stirred at -50°C for 30 minutes, then returned to room temperature.Next, water was added, tetrahydrofuran was distilled off under reduced pressure, extracted with ethyl acetate, and washed with saturated brine. , and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 8.97 g (yield: 88.5%) of an oily substance.

This oily substance, namely 6.0 g (25
mmol) was added with 65% sulfuric acid 3rd, and heated at 100°C for 2 hours. After cooling, water was added, the mixture was made alkaline with sodium carbonate, and then extracted with ethyl acetate. Then,
After drying the ethyl acetate layer over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting oily substance was purified by silica gel column chromatography to obtain the target compound 2.1.
7 g (yield 38.9%) was obtained.

The obtained compound has a melting point, an infrared absorption spectrum (IR
), nuclear magnetic resonance spectrum (NMR) and elemental analysis revealed the trans isomer of 1-(3-ethyl-4-pyridyl)-2-phenyl-1-propene (hereinafter referred to as compound 1).
It was identified that

Oily substance IR (cm-') at room temperature: 2900-3100,1643
゜1600.1507 NMR (CDCIs) δ (ppm): 1.1 B,
3 Ht.

2.10,3Hd, 2.62,2Hq, 6.78゜IH
brs, 7°09. IHd, 7.2-7.6.5Hm.

8.43. IHd, 8.47. IHs Elemental analysis (%) CHN Calculated value 86.06 7.67 6.27 Actual value 85.61 7.97 6.42 Example 2 ■-Phenyl-2-(3-methyl-4-pyridyl)-1
-Synthesis of propene 4.57 g (37,7
4.0 g (37.7 mmol) of benzaldehyde were reacted in the same manner as in Example 1 to obtain 8.13 g (yield 95.0%) of the alcohol.

6.0 g (26 mmol) of this alcohol was dehydrated using 65% sulfuric acid 8d in the same manner as in Example 1, and the product was purified to obtain 2.40 g (yield 43.4%) of the target compound. Ta.

The obtained compound is 1-phenyl-
It was identified as a trans form of 2-(3-methyl-4-pyridyl)-1-propene (hereinafter referred to as compound 2).

Oily substance TR (c+r') at room temperature: 2900-3100, 1600°N
MR (CDCf3) δ (ppm): 2.17, 3
HD.

2.34, 3Hs, 6.40. IHbrs, 7.091
Hd, 7.36.5Hs, 8.36. lHd, 8.44
゜IHs Elemental analysis (%) CHN Calculated value 86.08 7.22 6.69 Actual value 86.41 6.87 6.72 Example 3 1-phenyl-2-(3-ethyl-4-pyridyl)-1
-Synthesis of propene 5.09 g (37.7 mmol) of 4-diethylpyridine and 4.0 g (37.7 mmol) of benzaldehyde were reacted in the same manner as in Example 1 to obtain 4.73 g (yield: 5
2.1%) alcohol was obtained.

4.0 g (16.6 mmol) of this alcohol is added to 65
The product was purified by dehydration using 6Id% sulfuric acid in the same manner as in Example 1 to obtain 1.10 g (yield 29.6%) of the target compound.

The obtained compound is 1-phenyl-
It was identified as a trans form of 2-(3-ethyl-4-pyridyl)-1-propene (hereinafter referred to as compound 3).

Oily substance IR (cr') at room temperature: 2890-3100, 1598°NM
R (CDCfx) δ (ppm): 1.08. 3 Ht
.

2.14, 3Hd, 2.4 B, 2Hq, 6.51. l
Hbr s, 6.75~? , 2. 6 Hm, 8.4
3. I Hd.

8.4B, IHs Elemental analysis (%) CHN Calculated value 86.08 7.67 6.27 Actual value 86.02 7.75 6.23 Example 4 l-(3-methyl-4-pyridyl)-2- phenyl-3
, 3,3-trifluoro-1-propene 2.93 diisopropylamine in a 200-liter flask
g (29 mmol) and 15 II dl of tetrahydrofuran
and cooled to -50°C. This was then heated under a nitrogen stream.
-Butyllithium (15% n-hexane solution) 20d
(31.9 mmol) was added, and after stirring for 10 minutes, 3.4-
A solution of 3.11 g (29 mmol) of dimethylpyridine in tetrahydrofuran was added dropwise. After stirring at -50°C for 30 minutes, the reaction temperature was gradually raised, maintained at -10°C for 30 minutes, and then cooled again to -50°C. A solution of 5.0 g (29 mmol) of 2,2,2-trifluoroacetophenone in tetrahydrofuran was added dropwise to the mixture, and the mixture was stirred at -50°C for 30 minutes and then returned to room temperature. Next, water was added, tetrahydrofuran was distilled off under reduced pressure, and extracted with ethyl acetate.
After washing with saturated brine, it was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 4.45 g (yield 54.6
%) alcohol was obtained.

4.2 g (15 mmol) of this alcohol and 4 g (33.6 mmol) of thionyl chloride were mixed, and
Heat to °C for 2 hours. After the reaction, the mixture was cooled, excess thionyl chloride was distilled off under reduced pressure, water was added, and the mixture was made alkaline with sodium carbonate. It was extracted with ethyl acetate, washed with saturated brine, and then dried over anhydrous sodium sulfate. Distillation was carried out with ethyl acetate under reduced pressure, and the obtained oily substance was purified by silica gel column chromatography to obtain 0.60 g (
The target compound was obtained with a yield of 15.2%.

The obtained compound was determined to be 1-(3-methyl-4-pyridyl)-2-phenyl-3.3.3-1- from the following analysis results.
It was identified as a trans form of refluoro-1-propene (hereinafter referred to as compound 4).

Melting point 79.0~so, o"c IR (cm-'): 2900~3100.1602
°NMR (CDCL) δ (ppm): 2.24, 3
Hs.

6.60. I Hd, 7.0-7.6. 6Hm
, 8.11゜IHd, 8.3B, IHs Elemental analysis (%) CHF N Calculated value 68,44 4.59 21.65 5.3
2 Actual value 68.70 4,25 21.70 5.
35 Example 5 l-(3-ethyl-4-pyridyl)-2-phenyl-3
, 3.5 g (29 mmol) of 3-ethyl-4-methylpyridine and 5.0 g of 2,2,2-trifluoroacetophenone.
5. g (29 mmol) was reacted in the same manner as in Example 4.
36 g (yield 62.6%) of alcohol was obtained.

4.5 g (15 mmol) of this alcohol was dehydrated using 4 g of thionyl chloride in the same manner as in Example 4, the product was purified, and 0.88 g (yield 20.6%) of the target compound was obtained. .

The obtained compound was identified as the trans isomer of 1=(3-ethyl-4-pyridyl)-2-phenyl-3,3,3-trifluoro-1-propene (hereinafter referred to as Compound 5) from the following analysis results.
) was identified.

Melting point 47.0~48.5°C IR (cm-'): 2900~3090, 1602°N
MR (CDCl2.) δ (ppm): 1.26, 3
Ht.

2.70, 2Hq, 6.60. lHd, 7.0-7.4
゜6Hm, 8.10. IHd, 8.42. IHs elemental analysis (%) CHF N Calculated value 69.30 5.09 20.56 5.0
5 Actual measurement value 69.56 5.13 20.31 5.
00 Example 6 The following compound (trans form) was produced in the same manner as in Example 1.

(1) 1-(3-methyl-4-pyridyl)-2-phenyl-1-propene (hereinafter referred to as compound 6) I R (
cm-'): 2880~3100, 1640°1600
．． 1502 NMR (CCDl2.) δ (ppm): 2.14,
3 Hd.

2.2B, 3Hs, 6.72. IHbr s 7.1
5°IHd, 7.2-7.6, 5Hm, 8.42. IH
d.

8.47. IHs Elemental analysis (%) HN Calculated value 86.08? , 22 6.69 Actual value 86.50 6.61 6.89 (2) 1-
(2-chlorophenyl)-2-(3-methyl-4-pyridyl)-1-propene (hereinafter referred to as compound 7) IR (CI+-'): 2890-30B0,1600°NMR CCDCl2) δ (ppm): 2 .06,3Hd
.

2.39, 3Hs, 6.47. IHbrs, 6.5-7
．． 5°5Hm, 8.37. IHd, 8.46. IHs(
3) 1-(3-trifluoromethylphenyl)-2-(
3-Methyl-4-pyridyl)-1-propene (hereinafter referred to as compound 8) IR (cm-li: 2890-30 B 0. 1598
°NMR (CDCl23) δ (ppm): 2.17,
3 Hd.

2.35.3Hs, 6.42. IHbr s, 7.10
゜I Hd, 7.3~? ,7. 4 Hm, 8.4
3. I Hd.

8.46. IHs (4) 1-(3-ethyl-4-pyridyl)-2-(2-
fluorophenyl)-1-7'ropene (hereinafter, compound 9
) IR (cm-'): 2900-3100. 1600°150O NMR (CDC/l!3) δ (ppm) 21.
19, 3 Ht.

2.0B, 3Hd, 6.58. IHbrs, 6
．． 7-7.55Hm, 8.37. 1) (d, 8.41
．． IHs (5) 1-(3-methyl-4-pyridyl)-2-(2-10lophenyl)-1-7'robene (hereinafter referred to as compound 10) I R (cm-'): 2950-3100, 1605°NMR (CDCff,) δ (ppm): 2.06,
3 Hd.

2°30,3Hs, 6.39. IHbrs, 7.15~
? , 5,5Hm, 8.44. IHd, 8.45. IHs
(6) 1-(3-ethyl-4-pyridyl)-2-(2-
Chlorophenyl)-1-propene (hereinafter referred to as compound 11) IR (cl'): 2900-3100, 1600°50O NMR (CDCjl!) δ (ppm): 1.19,
3 Ht.

2.0B, 3Hd, 2.64, 2Hq, 6.58. IH
brs, 6.7-7.5. 5 Hm, 8.
37. I Hd.

8.41. IHs (7) l-(3-ethyl-4-pyridyl)-2=(3,
4-dichlorophenyl)-1-7'CIC7 (hereinafter referred to as compound 12) I R(CIO-'): 2900-3120,160
0°NMR (CDC1,) δ (ppm): 1.20,
3 Ht.

2.08,3Hd, 2.66.2F(q, 6.80.1
[(br s, 1.0-1.6.4 Hm, 8.
47. I Hd.

8.49. IHs (8) 1-(3-methyl-4-pyridyl)-2-(3,
4-dichlorophenyl)-1-7"robene (hereinafter referred to as compound 13) IR (cn+-'): 2860-3110, 1592° NMR (CD (/!,) δ (ppm): 2.09,
3 Hd.

2.27, 3Hs, 6.73. IHbrs, 7.0
~? , 7°4Hm, 8.43. IHd, 8.46. IH
s(9)1-(3,4-dichlorophenyl)-2-(
3-ethyl-4-pyridyl)-1-propene (hereinafter referred to as compound 14) IR (cm-'): 2900-3070, 1600°4
8O NMR (CDCfs) δ (ppm): 1.26, 3
Ht.

2.17,3Hd, 2.71,2Hq, 6.31. IH
brs, ? . O ~ 7.6, 4Hm, 8.42. IH
d.

8.48. IHs (10) 1-(3-trifluoromethylphenyl)-2
-(3-ethyl-4-pyridyl)-1-propene (hereinafter referred to as compound 15) IR (cm-'): 2900-3070, 1600°5
0O NMR (CDCffi,) δ (ppm): 1.27,3
Ht.

2.19,3Hd, 2.73,2Hq, 6.42. IH
brs, 7.08. l Hd, 7.3~? ,
8. ．． 4 Hm.

8.42. lHd, 8.49. IHs (11)1-(3-ethyl-4-pyridyl)-2-(
4-t-7'tylphenyl)-1-propene (hereinafter referred to as compound 16) IR (cm-'): 2890-3100. 1600° 52O NMR (CD(43)δ (ppm): 1.1 B,
3 Ht.

1.35. 9Hs, 2.1 1,3Hd, 2.65.
2Hq.

6.80. IHbr s,? , 12. IHD
, 7.4 1°2Hd, 7.51. 2Hd, 8.42
．． IHd.

8.45. IHs (12) 1-(3-ethyl-4-pyridyl)-2(45
ec-butylphenyl)-1-propene (hereinafter referred to as compound 17) IR (c+r'): 2890-3050, 1600°5
2O N M R (CD Cl : l) δ (ppm): 0.
8 6, 3 Hm.

1.20,3Ht, 1.26,3Hd, 1.4-1.8
゜2Hm, 2.12,3Hd, 2.4~2.8,3Hm
.

6.80. IHbr s, 7. 13. IH
d, 7.21°2Hd,? ,48,2Hd,8.43
．． IHd, 8.46°IHs (13) 1-(3-ethyl-4-pyridyl)-2-(4
-phenethylphenyl)-1-bropene (hereinafter referred to as compound 18) IR (cm-'): 2880-3110.1598°5
2O NMR (CDCfz) δ (ppm): 1.18, 3
Ht.

2.09,3Hd, 2.63,2Hq, 2.93,4H
s.

6.77, IHbrs, 7.0~? , 6,10Hm.

8.42. IHd, 8.45. IHs (14) l-(3,4-dichlorophenyl)-2-(3
-Methyl-4-pyridyl)-1-propene (hereinafter referred to as compound 19) IR (cm-'): 2B90-30B0,1600°4
8O NMR (CDCf3) δ (ppm): 2.16. 3
Hd.

2.33, 3Hs, 6.31. IHbrs, 7.0
7°IHd, 7.1-7.55.3Hm, 8.42. I
Hd.

8.45. IHs (15) 1-(3-chloro-4-methylphenyl)-2
-(3-ethyl-4-pyridyl)-1-propene (hereinafter referred to as compound 20) IR(c+++-'): 2880-3060.1590
NMR (CD(11)δ(ppm): 1.25, 3
Ht.

2.17. 3Hd, 2.39. 3Hs, 2.7 1
．． 2Hq.

6.31. I Hbr s, 7.0~? , 45
．． 4 Hm, 8.4 1. IHd, 8.4B,
IHs(16)1-(3-methylphenyl)-2-(
3-ethyl-4-pyridyl)-1-propene (hereinafter referred to as compound 21) IR (cm-'): 2900-3060, 1605°N
MR (CDCl2.) δ (ppm): 1.26, 3
Ht.

2.1B, 3Hd, 2.39,3Hs, 2.75,2H
q.

6.37. I Hbr s, 7.0-7.4.
5) (m, 8.42°IHd, 8.49.IHs Example 7 Synthesis of 1-phenyl-2-(3-ethyl-4-pyridyl)-propane 0.95% of diisopropylamine in a 200d flask
g (9.35 mmol) and tetrahydrofuran 15 were added thereto, and the mixture was cooled to -50'C. This was then subjected to n-
Butyllithium (15% n-hexane solution) 6.2d (
After stirring for 10 minutes, 1.3 g (9.35 mmol) of 3,4-diethylpyridine in tetrahydrofuran was added. The solution was added dropwise. After stirring at -50°C for 30 minutes, the reaction temperature was gradually raised, maintained at -10°C for 30 minutes, and then cooled again to -50°C. To this was added 1.2 g (9.35 mmol) of phenethyl chloride. A tetrahydrofuran solution of was added dropwise. After stirring at -50"C for 30 minutes, the temperature was returned to room temperature.

Next, water was added, tetrahydrofuran was distilled off under reduced pressure, extracted with ethyl acetate, washed with saturated brine, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting oily substance was purified by silica gel column chromatography to obtain 0.64 g (yield: 31%) of the target compound.

The obtained compound is 1-phenyl-
2-(3-ethyl-4-pyridyl)-propane (hereinafter referred to as
The chin (denoted as compound 22) was identified.

IR (c+r'): 2B80-3070. 1597°NMR (CDCL) δ (ppm): 1. l 0 ,
3 H.

1.22. 3Hd, 2.52. 2Hq, 2.7~3
．． 5°3Hm, 6.9~7.4. 6Hrn, 8.3
1. IHs.

8.40.　IHd Example 8 The following compounds were produced in the same manner as in Example 7.

(1) 1-(3-methyl-4-pyridyl)-2-phenyl-ethane (hereinafter referred to as compound 23) IR (cm-'
):2860-3100,1597°NMR (CD(1
, ) δ (ppm): 2.21, 3 Hs.

2.89, 4Hs, 7.09. IHd, 7.22.5H
s.

8.29. lHd, 8.31. IHs (2) 1-(3-ethyl-4-pyridyl)-2-phenyl-ethane (hereinafter referred to as compound 24) IR (cm-'
): 2910-3100, 1610゜l 513 NMR (CDCffi: +) δ (ppm): 1.20
, 3 Ht.

2.6 1. 2Hq, 2.89. 3Hs,? ,0
1. IHd.

7, 1-7.4. 5 Hm, 8.32. I
Hd, 8.37°IHs (3) 1-(3-methyl-4-pyridyl)-2-(2-
Chlorophenyl)-ethane (hereinafter referred to as compound 25) Melting point 43.4-44.4°C IR (cm-'): 2880-3110, 1595° NMR (CDCffi,) δ (ppm): 2.26,
3 Hs.

2.7-3.2.4Hm, 6.95-7.5.5Hm.

8.36. IHd, 8.37. IHs (4) 1-(3-ethyl-4-pyridyl)-2=(2-
Chlorophenyl)-ethane (hereinafter referred to as compound 26) IR (cn+-'): 2910-3100, 1612° NMR (CDCj2.) δ (ppm): 1.19,
3 Ht.

2.61.4Hs, 6.95-7.45.5Hm, 8.
32°I Hd,, 8.37. I H5 (5)
1-(3-methyl-4-pyridyl)-2-phenyl-propane (hereinafter referred to as compound 27) f R (cm-')
: 2890-3110,1603°NMR (CDCj
2:+)δ (ppm): 1.27, 3Hd.

2.14.3Hs, 2.7-3.15.3Hm, 6.8
4゜IHd, 6.95~? , 4,5Hm, 8.24. I
Hd.

8.28.1l-Ts (6) 1-(3-ethyl-4-pyridyl)-2-phenyluproban (hereinafter referred to as compound 28) I R(c
m-'): 2 B 90-3070,1598° 5
0O NMR (CD(43)δ(ppm): 1.38, 3
Ht.

1.49,3Hd, 2.77,2Hq, 2.9-3.4
゜3Hm, 7.05. IHd, 1.2-1.6.5Hm
.

8.46. I Hd, 8.55. I H5 (
7) 1-phenyl-2-(3-methyl-4-pyridyl)
-Propane (hereinafter referred to as compound 29) IR (cl')
:2860~3080. 1590°N MR (CD
Cl3)δ (ppm): 1.22, 3Hd
.

2, l 3. 3 Hs, 2.7-2.9. 2
Hm, 3.0~3.4゜1, Hm, 6.9
~7.4. 6 Hm, 8.29. I Hs.

8.39. IHd (8) 1-(2-chlorophenyl)-2-(3-methyl-4-pyridyl)-propane (hereinafter referred to as compound 30) I R (cm-'): 2890-3080,1600
゜50O NMR (CDC/l!,) δ (ppm): 1.24,
3 Hd.

2.11,3Hs, 2.8-3.05,2Hm, 3.1
~3.6゜IHm, 6.85~? , 45,5Hm, 8.
28. IHs.

8.41. IHd (9) 1-(3,4-dichlorophenyl)-2-(3
-ethyl-4-pyridyl)-propane (hereinafter, compound 3
1) IR (c+r'): 2B80~3060,1598°N
MR (CDCf3) δ (ppm): 1.08, 3
Ht.

1.22. 3Hd, 2.53. 2Hq, 2.7~2
．． 9°2 Hm, 3.0~3.45. I Hm
, 6.75-7.44Hm, 8.34. IHs
, 8.4 1. IHd(10)1-(3,4-dichlorophenyl)-2-(3-methyl-4-pyridyl)-
Propane (hereinafter referred to as compound 32) I R (cal-'): 2890-3080,160
0°NMR (CD(u3)δ(ppm): 1.22,
3 Hd.

2, 18. 3 Hs, 2.65-2.9. 2H
m, 3.0~3.4°I Hm, 6.75~7.4
．． 4 Hm, 8.30. I Hs.

8.41. IHd (11)1-(3-trifluoromethylphenyl)=2
-(3-ethyl-4-pyridyl)-propane (hereinafter referred to as compound 33) IR (c+r'): 2910-3100, 1611°N
MR (CDCffi3) δ (ppm): 1.09,
3 Ht.

1.26.3Hd, 2.50.2Hq, 2.8-3.5
゜3 Hm, 7.1~7.6. 5 Hm, 8
．． 32. I Hs.

8.42. IHd (12)1 (4-tert-butylphenyl)-2
-(3-propyl-4-pyridyl)-propane (hereinafter referred to as
(denoted as compound 34) rR (cm-'): 2890-3060, 1600°]
492 NMR (CDCj!+) δ (ppm): 0.90,
3 Ht.

1.21,3Hd, 1.29,9Hs, 1.35-1.
6゜2Hm, 2.49,2Ht, 2.7-2.9,2H
m.

3.0-3.4. I Hm, 6.9 B, 2
Hd, 7.21゜IHd,? ,26,2Hd,8.2
9. IHs.

8.40. IHd (] 3 ) 1 (4-tert-butylphenyl)-2-(3-butyl-4-pyridyl)-propane (
Hereinafter referred to as compound 35) IR (cm-'): 2900-30B0,1602°5
0O NMR (CDCex) δ (ppm): 0.90, 3
Ht.

1.21,3Hd, 1.29,9Hs, 1.3-1.5
゜4 Hm, 2.50. 2 Ht, 2.7~
2.9. 28m.

3.05-3.4. I Hm, 6.9 B,
2 Hd, 7.2 1°IHd, 7.26.
IHd, 8.29. LHs, 8.40°IHd Example 9 l-(3-ethyl-4-pyridyl)-2-phenyl-3
Synthesis of ,3,3-trifluoropropane 2.6 g (9,3
5 mmol) was dissolved in 30 ml of methanol, 500 μm of 5% palladium-carbon was added, and the solution was dissolved in 30 ml of methanol.
The mixture was stirred at room temperature for an hour. Filter to remove palladium-carbon and distill off ethanol under reduced pressure to obtain 2.6g
The target compound (yield: 100%) was obtained.

The obtained compound was identified as 1-(3-ethyl-4-pyridyl)-2-phenyl-3,3,3-trifluoropropane (hereinafter referred to as compound 36) from the following analysis results. It was done.

Melting point 181.1~1B2.2°C IR (c+r: 2900~3080.1603°N
MR(CD(13)δ(ppa+): 1.28, 3
Ht.

2.74. 2Hq, 3.0-3.8. 3Hm, 6.
9-7.6°6Hm, 8.36. IHd, 8.50
．． IHs test test 1 Effect on brown planthopper A length of 1.0cm is applied to a chemical solution with a concentration of 500ρρm for each test compound.
Rice stems cut into 500 m thick were soaked for 1 minute, air-dried, placed in a test tube filled with water, and brown planthopper larvae (3rd instar) were released, covered with cotton plugs, and left in a constant temperature room at 25°C. did. After 7 days of testing, we determined whether the larvae were alive or dead, and found that the test compound (
A high mortality rate as shown in Table 1 was achieved for Katanimono 1 to 36).

On the other hand, when a similar experiment was conducted using 4-styrylpyridine as a control, the mortality rate was 70%.

Table 1 [Effects of the Invention] As described above, the novel pyridine derivatives and salts thereof of the present invention exhibit strong insecticidal and acaricidal effects. Therefore, according to the present invention, it is possible to provide an excellent insecticide/acaricide containing a novel pyridine derivative and a salt thereof. Moreover, since the insecticide/acaricide of the present invention has a structure different from that of conventionally known insecticides, its action is also different, and it is particularly effective in controlling pests for which resistant species have emerged. Moreover, it decomposes quickly, quickly decomposes after application, and there is no risk of causing problems with persistence or accumulation.

Therefore, the insecticide/acaricide of the present invention is expected to be effective and widely used for controlling pests in agriculture and horticulture.

Claims (2)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (I) or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (II) [In the formula, X is a halogen atom, and the number of carbon atoms is 1 -4 alkyl group, C1-4 haloalkyl group, C1-4 alkoxy group, C1-4 haloalkoxy group, phenyl group, C1-4 alkyl-substituted phenyl group, phenyl group represents an alkyl group having 1 to 4 carbon atoms or a haloalkylsulfonyl group having 1 to 4 carbon atoms substituted with R^1,
R^2, R^3 and R^4 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a carbon number 1 to 4.
4 represents a haloalkyl group, R^5 represents an alkyl group having 1 to 6 carbon atoms, n is an integer of 0 to 5, and when n is 2 or more, X is the same or different. It's okay. However, in {1} [I] formula and [II] formula, R^1~R
When ^4 is hydrogen at the same time, in the {2}[I] formula, n is 0, R^2 is a hydrogen atom, and R^1 and R
When ^5 is a methyl group, and in formula {3}[II], n is 0, R^2, R^3 and R^4 are hydrogen atoms, and R^1 and R^3 are methyl except when it is a base. ] Pyridine derivative or its salt. (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ... [I] or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ... [II] [In the formula, X is a halogen atom, number of carbon atoms is 1 -4 alkyl group, C1-4 haloalkyl group, C1-4 alkoxy group, C1-4 haloalkoxy group, phenyl group, C1-4 alkyl-substituted phenyl group, phenyl group represents an alkyl group having 1 to 4 carbon atoms or a haloalkylsulfonyl group having 1 to 4 carbon atoms substituted with R^1,
R^2, R^3 and R^4 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a carbon number 1 to 4.
4 represents a haloalkyl group, R^5 represents an alkyl group having 1 to 6 carbon atoms, n is an integer of 0 to 5, and when n is 2 or more, X is the same or different. It's okay. ] An insecticide/acaricide containing a pyridine derivative or its salt as an active ingredient.