JPH02223555A - Pyridine derivative and salt thereof - Google Patents

Abstract

NEW MATERIAL:A compound of formula I, II or III (X is halogen, 1-4C alkyl, 1-4C alkoxy, 1-4C haloalkyl or 1-4C haloalkoxy; R<1>-R<3> are H or 1-4C alkyl; n is 0-5; etc.) and a salt thereof. EXAMPLE:1-(2-Chlorophenyl)-3-(4-pyridinyl)-butane. USE:An insecticidal, acaricidal agent. Especially effective for preventing injurious insects especially such as swarms and leafhoppers having resistance against conventional agents. The agent has no fear to cause problems such as the persistence and accumulation thereof. PREPARATION:A substituted phenetyl halide of formula IV (Y is halogen) is addition-reacted with a substituted pyridine of formula V in the presence of a base (e.g. lithium diisopropylamine) in a solvent such as benzene at -100-50 deg.C to provide the compound of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel pyridine derivative and a salt thereof, and more particularly to a pyridine derivative with a novel structure and a salt thereof having insecticidal and acaricidal activity.

(Problems to be solved by the conventional technology and the invention) Insecticides have traditionally been used to control pests in agricultural and horticultural crops and to control sanitary pests, and have greatly contributed to increasing the production of agricultural and livestock products and improving the sanitary environment. Conventionally used insecticides include chlorine-based, organophosphorus-based carbamate-based, and pyrethroid-based insecticides.However, in recent years, these insecticides have become more susceptible to pollution problems such as environmental pollution due to spraying, persistence, and There are safety problems such as accumulation and problems of drug resistance.Therefore, there is a need for the development of new insecticides and acaricides that are highly effective and do not have the problems mentioned above.

JP-A-55-1137], No. 5 describes 1-phenyl-3-(4-pyridyl)-propane as a raw material for antidepressants. Also 1, 1.0C, 34, 2
11, 3, 1969, a compound in which the hydrogen of the propylene group of 1-phenyl-3-(4-pyridyl)-propane was replaced with an alkyl group was reported, and further J, 1
leterocyc1. Chem, 24377.
In 1987, 1-phenyl-3-(4-pyridyl)-1-7', in which the phenyl group was substituted with a halogen or methoxycarbonyl group, was published. However, this document does not describe anything about the physiological activities of these compounds.

The present inventors aimed to develop pyridine derivatives that have high insecticidal and acaricidal effects and do not cause problems of persistence or accumulation when used as active ingredients of insecticides and acaricides.
I have done extensive research.

(Means for solving the problem) As a result, a pyridine derivative or a salt thereof in which a carbon atom constituting a carbon chain connecting a phenyl group and a pyridine ring or a pyridine ring is substituted with at least one alkyl group is excellent. The present invention was completed based on these findings.

That is, the present invention provides -Form (I) [where x is a haloken atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or a haloalkyl group having 1 to 4 carbon atoms] ~4 haloalkoxy group, Rl and RII each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 0 to 5.

Note that R and R', R2 and R5, and R3 and R6 may be bonded to each other to form an alkylene group having a carbon-carbon double bond. Further, when n is 2 or more, X may be the same or different. However, the case where R1-R11 are all hydrogen atoms is excluded. Moreover, when R7 and R8 are hydrogen atoms,
n is any one of 1 to 5. ] General formula (II) [wherein, X, R'-R', R7, RB and n are the same as above. However, the case where R1-R4 and R7, R1+ are all hydrogen atoms is excluded. Further, when R7 is a hydrogen atom, n is any one of 1 to 5. ] or general formula III) [wherein, X, R'-R3, R6-R8 and n are the same as above. However, the case where Rl, R3 and R6-Re are all hydrogen atoms is excluded (In addition, when R7 and Re are hydrogen atoms, n is any one of 1 to 5.) A pyridine derivative represented by or It provides the salt.

In the above general formulas (I), (U) and (III), 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, and specific examples thereof include methyl group, ethyl group, n-
Propyl group Examples include isopropyl, 14In-dityl group, isobutyl W, S-butyl group, and t-butyl group. Examples of the alkoxy group having 1 to 4 carbon atoms represented by There is a base. Carbon number 1 indicated by X
~4 haloalkyl group refers to one of the hydrogen atoms of the alkyl group
It means an alkyl group having 1 to 4 carbon atoms, in which at least 5 are substituted with halogen, specifically, for example, monochloromethyl group 2
Dichloromethyl group, trichloromethyl group, 1,000 chloroethyl group, dichloroethyl group.

Trichloroethyl group, tetrachloroethyl group, monochloropropyl group, dichloropropyl group, trichloropropyl group, tetrachloropropyl group, pentachloropropyl group, monochlorobutyl group, cyclobutel group, trichlorobutyl group, tetracrobutyl group, pencchlorobutyl group Alternatively, a hexachlorobutyl group, etc., and a corresponding haloalkyl group in which one or more of the chlorine atoms of the above group are substituted with fluorine, bromine and/or iodine can be mentioned.

The C1-C4 haloalkoxy group represented by X means an alkoxy group in which one or more of the hydrogen atoms of the alkoxy group is substituted with a halogen atom, such as a monochloromethoxy group and a dichloromethoxy group.

Trichloromethoxy group, monochloroethoxy group, dichloroethoxy group, trichloroethoxy group, monochloropropoxy group, dichloropropoxy group, trichloropropoxy group, tetrachloropropoxy group, pentachloropropoxy group, monochlorobutoxy group, cyclobutoxy group, trichlorobutoxybutoxy group Alternatively, examples thereof include a hexachlorobutyl group and a corresponding haloalkoxy group in which one or more of the chlorines in the above groups are substituted with fluorine, bromine and/or iodine.

In the above general formulas (I), (IT) and (III), the alkyl group having 1 to 6 carbon atoms represented by R l and Re is the same as the alkyl group having 1 to 4 carbon atoms represented by X. It may be either linear or branched.

In the pyridine derivative represented by the above general formula (I), X R' to R8 represent various groups as described above, and R1 and R4, R2 and ■75. R3 and R6 may each be combined to form an alkylene group having a carbon-carbon double bond. Further, when n is 2 or more, X may be the same or different, except when R to R8 are all hydrogen atoms at the same time.

Furthermore, when R7 and Ro are hydrogen atoms, nba1-5
(that is, the phenyl group has a substituent)
Requires.

In the pyridine derivative represented by the above general formula (II), when X R' to R8 represent various groups as described above, and R7 and R8 are hydrogen atoms, n
must be 1 to 5. Also, when n is 2 or more, X may be the same or different, but RI-R', R7
and R8 are all hydrogen atoms at the same time except (.

In the pyridine derivative represented by the above general formula (IIT), when XR'-R8 represents various groups such as "-" and R7 and Ro are hydrogen atoms, n
must be between 1 and 5. Further, when n is 2 or more, X may be the same or different, except when R1 to R'' and R6 to R8 are all hydrogen atoms at the same time.

The pyridine derivative represented by the above general formula (I) can be produced by various methods, but for example, the -format (
TV) [In the formula, χ, n, R', R2 and R4 are the same as above, and Y represents a halogen atom. ] The substituted phenethyl halide represented by the general formula (V) H2R3 [wherein R3, R7 and R11 are the same as above.

It can be produced by addition reaction with a substituted pyridine represented by ] in a solvent in the presence of a base.

Solvents used in this reaction include aromatic hydrocarbons such as Hensentoluene, and diethyl ether.

Examples include ethers such as tetrahydrofuran, dimethoxyethane, and diglyme, polar aprotic solvents such as dimethylbormamide, dimethyl sulfoxide, and hexamethylphosphoric acid 1-lyamide, and liquid ammonia.

In addition, as a base, lithium diisopropylamine,
Potassium 1-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.

In the general formula (I), when it is desired to substitute a dialkyl group to the α carbon bonded to the γ position of pyridine, the above general formula (
The substituted phenethyl halide of IV) is represented by the general formula (TV) [wherein R3 and R6-R8 are the same as above. ]
The addition reaction may be carried out with a substituted pyridine represented by: At this time, lithium aluminum hydride may be used as a catalyst, and other conditions may be the same as in the case of the above addition reaction.

In addition, metallic sodium or potassium is added to the substituted pyridine of the above general formula (Vl), and the reaction is completed for 3 to 5 hours to form -form (■) [wherein R3 and R6-R8 are as above. Same, M
indicates sodium or potassium. ] A metal compound represented by the formula (■) R' -C=CH-R2 is formed, where X, n, R' and R2 are the same as above.

] Pyridine derivatives of general formula (I) in which R4 and R5 represent hydrogen atoms can also be produced by reacting with a compound represented by the following. This reaction proceeds rapidly at 0-25°C.

In addition, the pyridine derivative of the general formula (I) in which R5 represents an alkyl group has the -form (■'') [wherein, X, n, R', R2, R' and Y are the same as above, and R50 is It is an alkyl group having 1 to 6 carbon atoms.

] In the presence of magnesium, a substituted phenethyl halide represented by the general formula (IX) is formed. In the formula C, R7 and R8 are the same as above. ] by reacting with a compound represented by the general formula (X) [wherein, X, n
, 'R', R2, R', R'', R' and R8 are the same as above. It can also be produced by reduction.

This reaction is similar to ethylene glycol, diethylene glycol, triethylene glycol, etc. Preferably, the reaction is carried out in a medium.

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.

Furthermore, the pyridine derivative of general formula (II) of the present invention can be produced by the following steps (a) to (c) including a Grignard reaction. That is, (a) the substituted phenethyl halide represented by the above general formula (IV) is reacted with magnesium in a solvent to form -form (x1) [wherein X, n, R', R2 and R4 are the above-mentioned , and Y represents a halogen atom. ] A Grignard reagent is prepared. Examples of solvents that can be used in this reaction include ethers such as diethyl ether, 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 (XII) [wherein R3, R7 and RB are the same as above. ] by reacting with pyridyl ketones represented by -form (XI
II) [In the formula, X, nR' to R' + R7 and Ro are the same as above. ] An alcohol compound represented by the following is produced. This reaction is (
a) Using the same solvent used in step 50°C to 1
The temperature range is preferably from -10°C to 20°C. Other reaction conditions can be selected as appropriate depending on the situation.

(C) The alcohol obtained in the above step (b) is dehydrated using a dehydrating agent in the presence or absence of a solvent to obtain the formula (II)
) get the object. Here, as a solvent, benzene,
1. Using an aromatic solvent such as toluene, xylene, or pyridine. As a dehydrating agent, dilute sulfuric acid, concentrated sulfuric acid, diline pentoxide,
Thionyl chloride, phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, etc. can be used. The dehydration reaction is usually -3
It is carried out at a temperature of 0°C to 150°C.

Moreover, the pyridine derivative represented by -form (II) is
-Form (X IV) 4 [In the formula, χ, n, R' and R4 are the same as above, and R9 represents an alkyl group. ] The substituted phenylacetic acid ester represented by the above general formula (V) is subjected to a condensation reaction with the substituted pyridine of the general formula (V) in a solvent in the presence of a base, resulting in a general formula (XV) [wherein X, n, R',
R3, R', R' and R8 are the same as above. ] The ketone represented by is reduced to produce an alcohol form, which is further dehydrated.

Examples of solvents used in the condensation reaction between substituted phenylacetic acid ester and substituted pyridine include aromatic hydrocarbons such as benzene and toluene, ethers such as diethyl ether, tetrahydrofuran, and dimethoxyethane diglyme, dimethylbormamide, and dimethyl sulfur. Examples include polar aprotic solvents such as oxide, -\xamethylphosphoric acid triamide, liquid ammonia, and the like.

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 70°C, more preferably 10 to 20°C.

In addition, the dehydration reaction of the above alcohol is carried out using dilute sulfuric acid, concentrated sulfuric acid, diline pentoxide, thionyl chloride, phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, etc., and is carried out without a solvent. However, aromatic solvents such as Hensen, toluene, xylene, and pyridine may also be used.

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

Furthermore, the pyridine derivative represented by the general formula Ul) of the present invention has the -form (XVI) [wherein X, nR' and R2 are the same as above. ] The substituted epoxide represented by the general formula (Vl) [wherein,
R3 and R6-R11 are the same as above. ] with the substituted pyridine in a solvent in the presence of a base, resulting in a general formula (X■) [where X, n,
R'-R3, R'-RI] are the same as above. ] Dehydrate the alcohol body represented by.

Examples of solvents used in the addition reaction between the above-mentioned substituted epoxide and substituted pyridine include aromatic hydrocarbons such as henzene and toluene, ethers such as diethyl ether, tetrahydrofuran, dimethoxyethane, and diglyme, dimethylform 1, amide IS, and dimethyl sulfoxide. , polar aprotic solvents such as hegisamethylphosphoric acid l.lyamide, liquid ammonia, and the like.

In addition, as a base, lithium diisopropylamine,
Potassium L-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.

Further, the dehydration reaction of the alcohol obtained by the addition reaction of -1= is carried out using dilute sulfuric acid, concentrated sulfuric acid, diline pentoxide, thionyl chloride, phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, etc. At this time, the reaction may be carried out without a solvent, but an aromatic solvent such as benzene, toluene, xylene, or pyridine may also be used.

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

In addition, general formulas (I), (II) and (TI
In I), compounds in which X is an alkyl group or a haloalkyl group can also be produced by reacting a compound in which X is hydrogen with an alkylating agent or a haloalkylating agent. This reaction can be carried out by a known alkylation method or haloalkylation method.

Here, as the alkylating agent, methyl chloride; methyl fluoride; ethyl chloride; nityl bromide; j-propyl chloride; i-propyl bromide; t-butanol; L-butyl chloride; t-butyl bromide; ; 5ec
-Butyl bromide; 2t-butyl-p-cresol;
Examples include 2,6-sheet t-butyl-p-cresol. 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 a 1-butyl group is obtained.

Specific examples of the pyridine derivatives of the general formulas (IL (I) and (■)) produced as described above include, for example, 1
-(2-chlorophenyl)-3-(4-pyridyl)-bukun; I-(2-fluorophenyl)3-(4-pyridyl)-bukun1l-(3-chlorophenyl)-3-(4
-pyridyl)-butane; 1-(3-trifluoromethylphenyl)-3(4-(pyridyl)-butane; 1-(4
-fluorophenyl)-3-(4-pyridyl)-butane; 1-(4-chlorophenyl)-3-(4-pyridyl)
-butane; 1-(4-methylphenyl)-3(4-pyridyl)-butane; 1-(4-bromophenyl)-3-(
4-pyridyl)-butane; 1(2,4-dichlorophenyl)-3-(4-pyridyl)-butane 1f-(34-
dichlorophenyl) -3-(4-pyridyl)-butane; 1(26-dichlorophenyl)-3-(4-pyridyl)-butane; 1-phenyl-3-(3-ethyl-4-pyridyl)-propane; I- Phenyl 3-(3-ethyl-
4-pyridyl)-butane; 1 phenyl-3-(3-methyl-4-pyridyl)propane; 1-(2-chlorophenyl)-3(3-ethyl-4-pyridyl)-propane; 1
(3-chlorophenyl)-3-(3-ethyl-4pyridyl)-propane; 1-phenyl-3(3-methyl-4-
1-phenyl-3-(
4-pyridyl)2-butene; 4-phenyl-2-(4-
2-phenyl-4-(4-pyridyl)-2-pentene; 1-phenyl-3-( 3-n-butyl-4-pyridyl)-butane; 1
-Phenyl-3-(3-isobutyl-4-pyridyl)-
Butane; 1-phenyl 3-(3-n-hexyl-4-pyridyl)-butane i 1(2-methylphenyl)-3-
(3-ethyl-4-pyridyl)-propane; 1-(3-
methylphenyl)-3-(3-ethyl-4-pyridyl)
-Propane; 1-(3-ethyl-4-pyridyl)-3-
Phenylbutane i 1-(3-10 4-methylphenyl)-3-(3-ethyl-4pyridyl)-propane; 1-phenyl-3-(3-ethyl-5-methyl-4-
pyridyl)-furopane; 1-phenyl-3-(3-ethyl-4-pyridyl)-5-methylhexane; 1-(
Examples include 4-t-methylphenyl)-3-(3-ethyl-4-pyridyl)-propane 11-(3-ethyl-4-pyridyl)-2-methyl-3-phenylpropane.

The pyridine derivatives of the above general formulas (II) and (III) include cis (Z) and trans (8) stereoisomers, both of which have insecticidal and acaricidal activity. 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.

Examples include lactic acid, oxalic acid, maleic acid, tartaric acid, benzoic acid, nicotinic acid, and dodecylbenzenesulfonic acid.

The pyridine derivatives and salts thereof of the present invention have strong insecticidal and acaricidal effects, and because they have a different structure from conventional insecticides, they are thought to act on insects through a different mechanism of action.

Insects for which the pyridine derivatives (including salts thereof) of the present invention exhibit activity include Hemiptera +
Coleoptera + Lepidoptera
doptera) and Acarina. A typical insect is the green peach aphid (My
zus persicae), cotton aphid (Aph
is gossypii) - Lipaphis erysimi, Nephotettix cincticeps
), brown planthopper (Nilaparvata Iu)
gens), white-legged planthopper (Sogatellafur)
cifera), Japanese brown planthopper ((, aode
lphaxstriatellus), whitefly (Trialeurodes vaporarior)
um) - llenosep
ilachna vigintioctopuncta
ta) + Oulema oryza
e) + Rice weevil (Lissorhoptr)
us oryzophilus) + Kubno borer moth (Cn
aphalocrocis medinalis L Two-spotted spider mite (Tetranychus urticae)
, citrus spider mite (Panonychus i tri)
etc. can be mentioned.

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, vegetables, petals, trees, cotton, fruit trees, turf grass,
It is effective in controlling pests on harvested grain, timber, and wooden products.

〔Example〕

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

Example 1 l-(2-chlorophenyl)-3-(4-pyridyl)-
Synthesis of Butane In a 200 ml flask, add 0.0 ml of diisopropylamine.
94 g (9.35 mmol) and 15 m of tetrahydrofuran! and cooled to -50°C. Add n-butyllithium (I5% n-hexane solution) to this under a nitrogen stream.
6.5m! (I0.3 mmol) was added, and after stirring for 10 minutes, 1.0 g (9.35 mmol) of 4-ethylpyridine was added to tetrahydrofuran. The solution was added dropwise. -3 at 50″C
After stirring for 0 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 2.05 g of 2-chlorophenethyl bromide (9,35
A solution of -50 mmol) in tetrahydrofuran was added dropwise to
After stirring at °C for 30 minutes, the mixture 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 dried over anhydrous sodium sulfate. The oil obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography to obtain 1
．． 35 g (yield 58.2%) of the target product was obtained.

The obtained compound has a melting point, an infrared absorption spectrum (IR
), 1-(2-chlorophenyl)3-(4-pyridyl) by nuclear magnetic resonance spectroscopy (NMR) and elemental analysis.
-butane (hereinafter referred to as compound 1).

Oily substance IR (cm-') at room temperature: 2900-3100, 1610°4
9O NMR (CDCl2.) δ (ppm): 1.22. 3
H, d; 1.6-2.1 2Hm; 2.2-2.8.
3H, m; 6.8-7.3, 6Hm; 8.46, 2H
, dd elemental analysis (%) CHCI! , N Calculated value 73.31 6.56 14.43 5.7
0 Actual value 73.74 6.37 14.27 5.
63 Example 2 l-(2-fluorophenyl)-3-(4-pyridyl)
- Synthesis of butane 1.0 g (9.35 mmol) of 4-ethylpyridine and 2
- 1.90 g of fluorophenethyl bromide (9,35
mmol) in the same manner as in Example 1, and the product was purified to obtain 0.74 g (yield: 39.2%) of the target compound.

The obtained compound was identified as 1(2-fluorophenyl)-3-(4-pyridyl)butane (hereinafter referred to as compound 2) from the following analysis results.

Oily substance at room temperature TR (c+n-'): 2880-3080.16005
0O NMR (CDCffi3) δ (ppm): 1.21,
3H,d; 1.65-2. ] 5.2H,m
;2.3~2.9.3 H,m;6.6~7.3.
6H, m; 8.4], 2H, d elemental analysis (
%) CHF N Calculated value 78.57 7.03 B, 29 6.
11 Actual measurement value 79.02 6.56 8.31 6
．． 11 Example 3 l-(3-chlorophenyl)-3-(4-pyridyl)-
Synthesis of butane 1.0 g (9.35 mmol) of 4-ethylpyridine and 3
2.05 g (9.35 mmol) of -chlorophenethyl bromide was reacted in the same manner as in Example 1, and the product was purified to obtain 0.65 g (yield 28.2%) of the target compound.

The obtained compound was determined to be 1(3-chlorophenyl)-:3-(4-pyridyl)butane (hereinafter referred to as
It was identified as compound 3).

Oily substance IR (cm-') at room temperature: 2900-3100.161049
O NMR (CD(43)δ(ppm): 1.22.3
H, d; 1.6-2.1. 2H, m; 2.2-2.
8. 3H, m; 6.7-7.2, 6H, m; L39,
2H, dd elemental analysis (%) CHC1! , N Calculated value 73.31 6.56 14.43 5.7
0 Actual value 73.72 6.12 14.46 5.
70 Example 4 Synthesis of l-(3-trifluoromethylphenyl)-3(4-pyridyl)-butane 1.0 g (9.35 mmol) of 4-ethylpyridine and 3
-Trifluoromethylphenethyl bromide 2.37g
(9.35 mmol) in the same manner as in Example 1,
The product was purified to give the target compound 0.40g (yield 15.3
%) was obtained.

The obtained compound was identified as 1(3-trifluoromethylphenyl)-3-(4pyridyl)-butane (hereinafter referred to as compound 4) from the analysis results below.

Oily substance IR (cu+-') at room temperature: 2900-3100 16155
1O NMR (CDCI23) δ (ppm): 1.23. 3
H, d; 17-2.15, 2H, m; 2.2-3.
25.3Hm; 6.9-7.5.6H,m; 8.35,
2H, dd elemental analysis (%) CHF N Calculated value 6B, 81 5.77 20.41 5.0
1 Actual measurement value 6B, 65 5.70 20.60 5.
05 Example 5 l-(4-fluorophenyl)-3-(4-pyridyl)
-Synthesis of butane 4-ethylpyridine 1. Og (9,35 mmol) and 4
- 1.90 g of fluorophenethyl bromide (9,3
5 mmol) in the same manner as in Example 1, and the product was purified to obtain 1.67 g (yield: 77.9%) of the target compound.

The obtained compound was identified as 1(4-fluorophenyl)-3-(4-pyridyl)butane (hereinafter referred to as compound 5) from the following analysis results.

Oily substance at room temperature IR (cm-'): 2B80-3100.160B.

52O NMR (CD(I!3)δ(ppm): 1.20.3
) T, d; 1.5~2.1 2H, m; 2.2~
2.9,3H,m;6.9-7.4,6H,m;8.4
3,2H,dd elemental analysis (%) CHF N Calculated value 78.57 7.03 8.29 6.1
1 Actual value 78.67 6.84 8.36 6.
14 Example 6 l-(4-chlorophenyl)-3-(4-pyridyl)
- Synthesis of butane 1.0 g (9.35 mmol) of 4-ethylpyridine and 4
2.05 g (9.35 mmol) of -chlorophenethyl bromide was reacted in the same manner as in Example 1, and the product was purified to obtain 1.37 g (yield 59.8%) of the target compound.

The obtained compound was identified as 1(4-chlorophenyl)-3-(4-pyridyl)butane (hereinafter referred to as compound 6) from the following analysis results.

Oily substance IR (cm-') at room temperature: 2B70~3100, 1605°5
0O NMR (CDCI23) δ (ppm): 1.20. 3
H, d; 1.6-2.05, 2H, m; 2. :2-
2.85,3H.

m; 6.7-7.3, 6H, m; 8.41, 2H, dd
Elemental analysis (%) CH (l N Calculated value 73.31 6.56 14.43 5.7
0 Actual value 73.36 6.3 B 14.54
5.72 Example 7 l-(4-methylphenyl)-1-(4-pyridyl)-
Synthesis of butane 4-ethylpyridine 1. Og (9,35 mmol) and 4
-Methylphenethyl bromide (1.86 g, 9.35 mmol) was reacted in the same manner as in Example 1, and the product was purified to obtain 2.07 g (yield: 98.4%) of the target compound.

The obtained compound was identified as 1(4-methylphenyl)-3-(,1-pyridyl)butane (hereinafter referred to as compound 7) from the following analysis results.

Oily substance TR (c++r') at room temperature: 2850-3050.1600N
MR (CDC1ff) δ (ppm): 1.17. 3
H, d; 1.6-2.05, 3H, m; 2.22.3
H, S; 2.2-2.8. 3H, rrB6.8-7
．． 1. 6H, m; 8.37 2Hdd Elemental analysis (%) CHN Calculated value 85.29 B, 50 6.22 Actual value 85. I4 8.63 6.24 Example day 1-(4-bromophenyl)-3-(4-pyridyl)-
Synthesis of butane 4-ethylpyridine 1.0 g (9.35 mmol)
and 2.47 g of 4-bromophenethyl bromide (9,
35 mmol) in the same manner as in Example 1, and the product was purified to obtain 1.10 g (yield: 40.7%) of the target compound.

The obtained compound was identified as 1-(4-bromophenyl)-3-(4-pyridyl)butane (hereinafter referred to as compound 8) from the following analysis results.

Oily substance IR (cm-') at room temperature: 2900-3100.161050
O NMR (CDCl2.l) δ (ppm): 1.30.
3H,d; 1.6-2.1. 2Hm; 2.25~
2.9. 3H, m; 6.85. 2H,d,6.
97. 2H, dd i7.2B2H, d, 8.39
2Hdd Elemental analysis (%) CHBr N Calculated value 62.08 5.56 27.53 4.8
3 Actual measurement value 62.56 5.40 27.27 4.
78 Example 9 Synthesis of 1,-(2,4-dichlorophenyl)-3-(4pyridyl)-butane 1.0 g (9.35 mmol) of 4-ethylpyridine and 2
,4-dichlorophenethyl bromide 2.37g (9
, 35 mmol) in the same manner as in Example 1, the product was purified, and 0.67 g (yield 25.6%) of the target compound was obtained.
I got it.

The obtained compound was identified as 1(2,4-dichlorophenyl)-3-(4-pyridyl)-butane (hereinafter referred to as compound 9) from the following analysis results.

Oily substance IR (c++r') at room temperature: 2900-3100 1620
NMR (CDCI!, 3) δ (ppm): 1.24.
3H,d; 1.6-2.1,2H,m; 2.3-2
．． 9.3Hm; 7.0-7.3. 5H, m; 8.43
2Hdd elemental analysis (%) CH x N Calculated value 64.30 5.40 25.31 5.0
0 Actual value 64.2B 5.26 25.44 5
．． 02 Example 10 Synthesis of 1-(3,4-dichlorophenyl)-3-(4pyridyl)-butane 1.0 g (9.35 mmol) of 4-ethylpyridine and 3
．． 2.37 g of 4-dichlorophenethyl bromide (9
, 35 mmol) in the same manner as in Example 1, and the product was purified to obtain 1.17 g of the target compound (yield 44.6%).
) was obtained.

The obtained compound was identified as 1(3,4-dichlorophenyl)-3-(4-pyridyl)-butane (hereinafter referred to as compound 1o) from the following analysis results.

Oily substance IR (cm-') at room temperature: 2900-3100.1610
NMR (CD(I3)δ(ppm): 1.23.3
H, d; 1.6-2.1, 2H, m; 2.2-2.9
, 3H, m; 6.7-7.35, 5H, m; 8.44,
2H, dd original search analysis (%) CHC/2 N Calculated value 64.30 5.40 25.31 5.0
0 Actual value 64.77 5.23 25.05 4.
95 Example 11 Synthesis of 1-(2,6-dichlorophenyl)-1-(4pyridyl)-butane 4-ethylpyridine 1. Og (9.35 mmol)
and 2.37 g (9
, 35 mmol) in the same manner as in Example 1, and the product was purified to obtain 145 g (yield: 55.3%) of the target compound.

The obtained compound was identified as 1(2,6-dichlorophenyl)-3-(4-pyridyl)-butane (hereinafter referred to as compound 11) from the following analysis results.

Oily substance IR (cm-') at room temperature: 2900-3100, 1610°N
MR (CDCj2s) δ (ppm): 1.26,
3H,d;1.5-2.1,2H,m;2.4-3
．． 0.3H,m; 6.7-7.35, 5H,m; 8.4
2,2H,dd elemental analysis (%) CHCI N Calculated value 64.30 5.40 25.31 5.0
0 Actual value 64.64 5.06 25.31 5.
00 Example 12 Synthesis of 1-phenyl-3-(3-ethyl-4-pyridyl)-propane 1.13 g of 3-ethyl-4-methylpyridine (9,3
5 mmol) and phenethyl bromide 1.73 g (9,
35 mmol) in the same manner as in Example 1, and the product was purified to obtain 1.95 g (yield: 92.8%) of the target compound.

The obtained compound is 1-phenyl-
3-(3-ethyl-4-pyridyl)-furopane (hereinafter referred to as
It was identified as compound 12).

Oily substance IR (cm-') at room temperature: 2900-3100, 1600°N
MR (CDCl2) δ (ppm): 1.20.3 H
, t; 1.5-2.2. 2H,m; 2.25~
2.8. 6 H,m; 6.88. LH,d;
7.10. 5H,br s ;8.2 LIJ(,d
;8.25. IH,s Elemental analysis (%) CHN Calculated value 85.29 B, 50 6.22 Actual value 85.28 8.45 6.27 Example 13 1-phenyl-3-(3-ethyl-4-pyridyl)- Synthesis of butane 3.4-diethylpyridine 1.26 g (9,35 mm 40
~ Rimol) and phenethylpromyF1.73g (9,35
mmol) in the same manner as in Example 1, and the product was purified to obtain 1.28 g (yield: 57.2%) of the target compound.

The obtained compound is 1-phenyl-
It was identified as 3-(3-ethyl-4-pyridyl)-butane (hereinafter referred to as compound 13).

Oily substance TR (cm-') at room temperature: 2900-3100, 1607°5
1O NMR (CDCffi3) δ (ppm): 1.14,
3H,t;1.24. 3H,d; 1.7-2
．． 1. 2H, m; 2.3-3.2. 5H,m;6.
9-7.4. 6H, m; 8.35IH, s; 8.3
8. LH, d Elemental analysis (%) CHN Calculated value 85.31 8.84 5.85 Actual value
85.58 8.62 5.80 Example 14 Synthesis of 1-phenyl-3-(3-methyl-4-pyridyl)-propane 1.0 g (9.35 mmol) of 34-dimethylpyridine
and 1.73 g (9.35 mmol) of phenethyl bromide were reacted in the same manner as in Example 1, and the product was purified,
1.82 g (yield 92.4%) of the target compound was obtained.

The obtained compound is 1-phenyl-
3-(3-methyl-4-pyridyl)-propane (hereinafter referred to as
It was identified as compound 14).

Oily substance IR (cm-') at room temperature: 2880-3100, 1600°N
MR (C'DC)j23) δ (ppm): 1.7-2.
1, 2 Hm; 2.20 3Hs; 2.45-2
．． 8,4H,m;7.02 11-1 d;7.1
~7.45. 51(, m; 8.2-8.4 2Hm Elemental analysis (%) CHN Calculated value 85.26 B, 11 6.63 Actual value 85.58 7.88 6.54 Example 15 1-(2-chlorophenyl )-3-(3-ethyl-4-
Synthesis of 3-ethyl-4-methylpyridine (1.13 g (9,3
5 mmol) and 2-chlorophenethyl bromide 2.0
5 g (9.35 mmol) was reacted in the same manner as in Example 1, the product was purified, and the target compound was 1.04 g (yield: 42 mmol).
．． 8%).

The obtained compound was identified as 1(2-chlorophenyl)-3-(3-ethyl-4pyridyl)-propane (hereinafter referred to as compound 15) from the following analysis results.

Oily substance IR (cm-') at room temperature: 2B60-3050.159047
O NMR (CDCj23) δ (ppm): 1.20. 3
H,t; 1.7-2.15 2Hm; 2.4-2.
9. 6H, m; 7.0-7.4 5Hm; 8.33
．． LH, d; 8.36 IH, s Elemental analysis (%) CI-I Cl1N Calculated value 73.98 6.9B 13.65 5.
39 Actual value 74.29 6.96 13.44 5
．． 31 Example 16 ■-(3-chlorophenyl)-3-(3-ethyl-4-
Synthesis of 3-ethyl-4-methylpyridine (pyridyl)-propane1. ．． 13g (9,3
5 mmol) and 3-chlorophenethyl bromide 2.0
5 g (9.35 mmol) in the same manner as in Example 1 to purify the product, yielding 1.23 g (yield: 50 mmol) of the target compound.
．． 7%).

The obtained compound was identified as 1(3-chlorophenyl)-3-(3-ethyl-4pyridyl)-propane (hereinafter referred to as compound 16) from the following analysis results.

Oily substance IR (cm-') at room temperature: 2B80~3070, 1600°N
MR(CD(I,)δ(ppm): 1.20.3Ht
;1.7~2.15,2H,m;2.4~2.9.6
Hm; 6.9-7.35. 5 H,m;8.33.
L H,d ;8.37. IHs Elemental analysis (%) CHen N Calculated value 73.98 6.98 13.65 5.3
9 Actual value 74.37 6.43 13.77 5.
43 Example 17 Synthesis of 1-phenyl-3-(3-methyl-4-pyridyl)-butane 1.13 g of 3-methyl-4-ethylpyridine (9,3
5 mmol) and phenethyl bromide 1.73 g (9
, 35 mmol) in the same manner as in Example 1, and the product was purified to obtain 1.36 g (yield 64.5%) of the target compound.
I got it.

The obtained compound is 1-phenyl-
It was identified as 3-(3-methyl-4-pyridyl)-butane (hereinafter referred to as compound 17).

Oily substance at room temperature JR (c+n-'): 2890-3090, 1602°NMR (CDC/!3) δ (ppm): 1.22. 3
H, d; 1.7-2.1. 2H,m;2.18.
3H,s;2.4~3.1,3H,rr17.0~
7.4,6H,m; 8.34°IH,s; 8.39.
LH, d Elemental analysis (%) CHN Calculated value 85.29 8.50 5.22 Actual value
85.0=7 8.79 6.14 Example 18 Synthesis of 1-phenyl-3-(3-n-propyl-4-pyridyl)-butane 1-phenyl-3-(3-methyl-4-pyridyl) -2.1 g (9.35 mmol) of butane and 1.4 g of ethyl iodide
The reaction was carried out in the same manner as in Example 1 using 6 g (9.35 mmol) of lithium diisopropylamine and 2 parts of lithium diisopropylamine, and the product was purified to obtain 0.37 g (yield: 15.6%) of the target compound.

The obtained compound is 1-phenyl-
It was identified as 3-(3-n-propyl-4-pyridyl)butane (hereinafter referred to as compound 18).

Oily substance IR (cm-') at room temperature: 2890-3100.1600°5
0O NMR (CDCI!, 3) δ (ppm): 0.8 B,
3H,t;1.21. 3H,d; 1.3~
2.05. 4H, m; 2.2-2.7. 4H, m;
2.8~3.15 18 m; 7゜θ~7.45,6
H,m;8.30. LH,s; 8.35°LH,d Elemental analysis (%) CHN Calculated value 85.32 9.15 5.53 Actual value
85.17 9.07 5.76 Example 19 (E) Synthesis of -1-phenyl-3-(4-pyridyl)-2-butene and 4-phenyl-2-(4-pyridyl)-1-butene (3) 0.4 g of magnesium powder (I6,2
Add 10 mmol of dry ether and 3.0 g of phenethyl bromide (I6.2 mmol) under a nitrogen atmosphere.
An ether solution of was gradually added dropwise. When the reaction started, the ether began to reflux, so phenethyl bromide was added to the extent that the reflux continued. After finishing dropping, heat under reflux for 1 hour.
After that, it was cooled in a water bath, and 4-acetylpyridine 1.78
g (4.8 mmol) of Aether J. solution was added.

After stirring for 30 minutes, the water bath was removed and the mixture was heated to reflux for 1 hour. After cooling, 5% ammonium chloride was added and extracted with ether, and the organic layer was washed twice with 5% hydrochloric acid. The aqueous layer was made alkaline with sodium carbonate, extracted with ethyl acetate, and dried over anhydrous sodium sulfate. Ethyl acetate was distilled off under reduced pressure to obtain 1.42 g (42.4%) of alcohol.

This alcohol, namely 2-(4-pyridyl)-4
- 65% sulfuric acid 4 to 1.42 g of phenyl-2-butanol
mfl was added and stirred at 100"C for 2 hours. After cooling, water was added, made alkaline with sodium carbonate, and extracted with ethyl acetate. After drying with anhydrous sodium sulfate,
The solvent was distilled off under reduced pressure to obtain a viscous oil. This oily substance was purified by silica gel column chromatography to obtain (E) 0.44 g (yield 33.7%) of 1-phenyl-3-(4-pyridyl)-2-butene and 4-phenyl-2-
(4-pyridyl)-1-butene 0.15 g (yield 11
．． 5%).

The obtained compounds were identified as (E) -phenyl-3-(4-pyridyl)-2-butene (hereinafter referred to as compound 19) and 4-phenyl-2-(4-pyridyl) from the following analysis results.
It was identified as -1-butene (hereinafter referred to as compound 20).

Compound 19 Oily substance at room temperature IR (c++r'): 2880-30B0,1652°1600.1504 NMR (CDCp, f+) δ (ppm): 2.04,
3 H5S; 3.48 2 H,d; 6.07.
br, t, 7.0-7.37H, m; 8.4],
2H, dd Elemental analysis (%) CHN Calculated value 86.08 7.22 6.69 Actual value
86.42 6.98 6.60 Compound 20 Oily substance at room temperature IR (c+n-'): 2B80-30B0, 16401
602.1504 NMR (CD(43)δ(ppm): 2.70.4
H,s;5.1 1Hs;5.39. IH,s
;6.9-7.37Hm;8.43,2H,dd Elemental analysis (%) CHN Calculated value 86.08 7.22 6.69 Actual value
85.68 7,62 6.70 Example 20 Synthesis of (Z)-1-(2-fluorophenyl)-3(4-pyridyl)-2-butene In a 200 ml flask, diisopropylamine 5.
2 g (1.8 mmol of I) and 40 m of tetrahydrofuran
1 and cooled to -50°C. Add 34 m of n-butyllithium (I5% n-hexane solution) to this under a nitrogen stream.
! (56 mmol) was added thereto, and after stirring for 10 minutes, a solution of 5.0 g (53.8 mmol) of 4-methylpyridine in tetrahydrofuran was added dropwise.

After stirring at 50 °C for 30 minutes, the reaction temperature was gradually increased.
After being held at -10°C for 30 minutes, it was cooled again to -50°C. To this, 7.7 g of ethyl 0-fluorophenyl acetate
A solution of (42.3 mmol) in tetrahydrofuran was added dropwise thereto, 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, extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous sodium acetate. The solvent and 4-ethylpyridine were distilled off under reduced pressure to obtain 6.17 g (yield 60.0%) of an oily substance.

This oily substance, namely 1-(2-fluorophenyl:
l-3-(4-pyridyl)-butan-2one 1.65g
(6.79 mmol) was dissolved in 10 mR of methanol, and 130 μl of sodium borohydride was added little by little. After adding the entire amount, stir at room temperature for 1 hour, add 5% hydrochloric acid 10
m! was added to decompose excess sodium borohydride. Methanol was distilled off under reduced pressure, the mixture was made alkaline with sodium carbonate, and then extracted with ethyl acetate. After drying over anhydrous sodium sulfate, ethyl acetate was distilled off under reduced pressure to obtain 1.59 g of a white solid (yield: 95.6%).

This solid, i.e. 1-(2-fluorophenyl) -
3-(4-pyridyl)-2-butanol 1.59 g (6
, 49 mmol) was added with 2.5 ml of thionyl chloride.
Stirred at 0"C for 1 hour. After distilling off excess thionyl chloride under reduced pressure, water was added, made alkaline with sodium carbonate, and extracted with ethyl acetate. After drying over anhydrous sodium sulfate, the mixture was dried under reduced pressure. Ethyl acetate was distilled off to obtain a brown oily substance.The obtained oily substance was purified by silica gel column chromatography to give 0.54g (yield 31.6g).
%) of the target compound was obtained.

The obtained compound is (Z)1-(2
-fluorophenyl)-3-(4-pyridyl)-2-butene (hereinafter referred to as compound 21).

Oily substance IR (cm-') at room temperature: 2870-3100, 1604°5
0O NMR (CDCj23) δ (ppm): 1.99,
3 Hbrs, 3.27. 2H,d; 5.67,
IH, br t6.7~7.4 6Hm; 8.51
．． 2H, dd elemental analysis (%) CHF N Calculated value 79.27 6.21 8.36 6.1
6 Actual value 79.67 5.99 8.27 6.
08 Example 21 (E)-2-phenyl-4-(4-pyridyl)2-pentene and (z)-2-phenyl-4(4-pyridyl)
Synthesis of -2-pentene 3.74 g (37.0 mmol) of diisopropylamine in a 200 ml flask
and 30 ml of tetrahydrofuran were added and cooled to -50°C. This was added to n-butyllithium (I5) under a nitrogen stream.
% n-hexane solution) 25.6 mR (I2.9 mmol) was added, and after stirring for 10 minutes, 4-ethylpyridine 4.0
g (43.0 mmol) in tetrahydrofuran was added dropwise. After stirring at -50°C for 30 minutes, the reaction temperature was gradually raised and kept at -10°C for 30 minutes.
Cooled to °C. A solution of 5.0 g (37.0 mmol) of 2-phenylpropylene oxide in tetrahydrofuran was added dropwise thereto, 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, extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous sodium acetate. The solvent was distilled off under reduced pressure to obtain 8.83 g (yield 98.9%) of an oily substance.

To 8.83 g (36.6 mmol) of this oily substance, namely 2-phenyl-4(4-pyridyl)-2-pentanol, 15 d of 65% sulfuric acid was added, made alkaline with sodium carbonate, and extracted with ethyl acetate. . After drying the ethyl acetate layer over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure and purified by silica gel column chromatography to obtain (E)-2-phenyl-4-(4-pyridyl)2-pentene. .45g (17% yield) and (Z)
0.10 g (yield: 4%) of -2-phenyl-4-(4-pyridyl)-2-pentene was obtained.

The obtained compound was found to be (E) 2-phenyl-4-(4-pyridyl)-2-pentene (hereinafter referred to as compound 22) and (Z) = 2-phenyl-4-(
It was identified as 4-pyridyl)-2-pentene (hereinafter referred to as compound 23).

Compound 22 Oily substance at room temperature IR(an-'): 2880-3060.159B.

NMR (CDC13) δ (ppm): 1.2 B,
3H,d; 1.96. 3H, br s, 3.4~
4.1. IH, rrB5.77. I H,br
d, 6.7-7.4. 7H,m ;8.37.
IH, dd Elemental analysis (%) CHN Calculated value 86.06 7.67 6.27 Actual value
86.23 7.61 6. I6 Compound 23 Oily substance at room temperature IR (cm-'): 2870-3070, 1604°N
MR (CDCfi3) δ (ppm): 1.23, 3
H,d;2.00. 3H, br s, 3.1~
3.65. LH, m; 5.43 1Hbrd 6
．． 8-7.3 7Hm; 8.3], IHdd Elemental analysis (%) CHN Calculated value 86.06 7.67 6.27 Actual value
86.18 7.53 6.29 Example 22 Same as Example 18 except that n-propyl iodide, isopropyl iodide, or n-hair iodide was used instead of ethyl iodide. The following compound was obtained.

(I) 1-phenyl-3-(3-n-butyl-4-pyridyl)-butane (hereinafter referred to as compound 24) Oily substance at room temperature IR (cm-'): 2890-3110.1602NM
R (CDCI2.) δ (ppm): 0.90. 3H
, t ; 1.23,3H, d ; 1.1-1.6,4H
, m; 1.7-2.1, 2H, m; 2.35-2.7,
4H, m; 2.8-3.15. I H,m;7.
0-7.4. 6 H,m; 8.33. II-T,s
;8.3B, LH, d elemental analysis (%) CHN Calculated value 85.34 9.42 5.24 Actual value
84.66 10.12 5.22 (2) 1-phenyl-3-(3-isobutyl-4pyridyl)-butane (hereinafter referred to as compound 25) Oily substance at room temperature IR (c+n-'): 2B80-3110 , 1600°NMR (CDCj23) δ (ppm): 0.84,
6H,d; 1.23,3H,d; 1.4-2.0
5.3H, m; 2.2 to 3.1, 5H, m; 6.9 to 7
．． 5.6H, m; 8.2B.

IH,s ;8.39. IH, d Elemental analysis (%) CHN Calculated value 85.34 9.42 5.24 Actual value
85.37 9.39 5.22 (3) 1-phenyl-3-(3-n-hexyl 4-pyridyl)-butane (
Hereinafter referred to as compound 26) Oily substance at room temperature IR (cm'): 2890-3110, 1602.1
NMR (CD(I,)δ(ppm): 0.89.3H
,t;1.25. 3H,d; 1.0-1.6.
8H, m; 1.75-2.05, 2H, m; 2.3-2
．． 7,4H,m; 2.8~3.1 1Hm; 7°0~
7.4 6Hm; 8.33IH,s; 8.37.
IH, d elemental analysis (%) CHN Calculated value 85.37 9.89 4.74 Actual value
85.15 10.15 4.72 Example 23 The reaction was carried out in the same manner as in Example 1, except that the following compounds were used as raw materials in the amounts shown below, and the following compounds 27 to 31 were obtained. I got it.

Compound 27 Raw materials 3-ethyl-4-methylpyridine (I, 13g) 1-bromo-2-(2-methylphenyl)ethane
(I, 86g) Product 1-(2-methylphenyl)-3(3-ethyl-4-pyridyl)-propane (Compound 27) Oily substance at room temperature IR (c++r'): 2870-3050.1597°N M R(CD Cf! 3) δ (ppm)
:1.19. 3H,t; 1.8-2.1,2H,m
;2.26,3H,s;2.4-2.9,6H,m;
6.9-7.3,5H, m; 8.2B.

IH,d ;8.31. IH,s; Elemental analysis (%) CHN Calculated value 85.31 B, 84 5.85 Actual value
85.34 8.54 6.12 Yield 63.0% Compound 28 Raw material 3-ethyl-4-methylpyridine (I, 13 g) 1-bromo-2-(3-methylphenyl)ethane
(I, 86g) Product 1-(3-methylphenyl)-3(3-ethyl-4-pyridyl)-propane (Compound 28) Oily substance at room temperature IR (c+n-'): 2900-3050. 16
05° 50O NMR (CD Cl 3) δ (ppm):
1.19. 3Ht; 1.7-2.1. 2H,
m;2.33. 3H,s; 2.4-2.8. 6
H, m; 6.9-7.3. 5 H,m; 8.3
2. LH,d;8.36. IHs; elemental analysis (
%) CHN Calculated value 85.31 B, 84 5.85 Actual value
85.44 8.64 5.92 Yield 35.0% Compound 29 Raw material 3-ethyl-4-methylpyridine (I, 13g
) 1-Bromo-2-phenylpropane (I, 86 g) Product 1-(3-ethyl-4-pyridyl)3-phenylpukun (Compound 29) Oily substance at room temperature IR (cm-'): 21380-3070. 15
97°IR (cm-'): 2B70-3020.
1596°NMR (CDCl2) δ (ppm):
1.13. 3H.

t; 1.3 1. 3H,d; 1.7-2
．． 1. 2H, m; 2.3-2.9. 5 H,m;
6.9-7.45. 6 H,m; 8.30. I
H,d ;8.32. LH,s; Elemental analysis (
%) CHN Calculated value 85.3 ] 8.84 5.85 Actual value 85.12 9.22 5.65 Yield 40.0% Compound 30 Raw material 3-ethyl-4-methylpyridine (I, 13 g) ■- Bromo 2-(3-chloro-4-methylphenyl)
-Ethane (2,18 g) Product 1-(3-chloro-4-me-tylphenyl)-3-(3-ethyl-4-
pyridyl)-propane (Compound 30) Oily substance at room temperature NMR (CDCI!,,) δ (ppm): 1
．． 21, 3H.

t; 1.7-2.1. 2H, m; 2.35. 3
H,s;2.5-2.8,6H,m;6.9-7'
, 3.4H, m; 8.33. LH,d ;8.3
7. LH, S; Elemental analysis (%) C, HC deficient N Calculated value 74.58 7.36 12.95 5.1
1 Actual value 74.25 7.21 13.16 5.
37 Yield 9.0% Compound 31 Raw material 3.4-dimethyl-5-ethylpyridine (I,2
6g) 1-bromo-2-phenylethane (I, 73g) Product 1-phenyl-3-(3-ethyl-5methyl-
4-pyridyl)-propane (compound 31) Oily substance at room temperature IR (c++r'): 2B90-3070. 1593
゜N M R (CD Cl 3 ) δ (ppm)
:1.17. 3H.

t; 1.7-2.0. 2Hm; 2.19. 3H
,s;2.4-2.9. 6H, m; 7.1-7.
4. 5H, m; 8.16. IH,s;8゜1
9. LH,s: Elemental analysis (%) CHN Calculated value 85.31 8.84 5.85 Actual value
85.64 8.48 5.86 Yield 42.4% Example 24 Pyridine of compound 32 was prepared in the same manner as in Example 18 except that the following compounds were used as the raw materials and alkylating agent. A derivative was obtained.

Compound 32 Raw material 1-phenyl-3-(3-ethyl-4-pyridyl)-propane (2,1 g) Alkylating agent Isobutyl bromide (I, 28 g) Product 1-phenyl-3-(3-ethyl-4-pyridyl )-5-Methylhexane (compound 32) Oily substance at room temperature IR (cm-1): 2900-3090.1602NM
R(CDC/!,)δ(ppm): 0.85,
3H.

a; 0.87,3H, d; 1.17.3H, t;
1.3-2.1,5H,m; 2.3-2.7,4H,m
;2.8-3.2. IH, m; 6.95-7.4,6H
,m;8.38IHs;8.44. IH, d; Elemental analysis (%) CHN Calculated value 85.36 9.67 4.97 Actual value
85.44 9.71 4.83 Yield 31.8% Example 25 1-(4-t-butylphenyl)-3-(3-ethyl-
Synthesis of 4-pyridyl)-propane 2.75 g (20.6 mmol) of anhydrous aluminum chloride and 4 mβ of dried nitromethane were placed in a flask and cooled in an ice bath containing salt. In this, 1-phenyl-3-(3-ethyl-4-
Add a solution of 2.1 g (9.35 mmol) of pyridyl-propane in nitromethane, stir for 30 minutes, and
A solution of 2.3 g (10 mmol) of -di-t-butyl-p-cresol in nitromethane was added dropwise.

After stirring at below 0°C for 1 hour, the water bath was removed and the mixture was stirred at room temperature for 1 hour. After the reaction was completed, water was added and the mixture was extracted with ethyl acetate. After drying 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 give 0.85 g (yield: 3
4.0%) of the target compound was obtained. The obtained compound was determined to be 1-(4-t-butylphenyl)- from the following analysis results.
3-(3-ethyl-4-pyridyl)-propane (hereinafter referred to as
It was identified as compound 33).

Oily substance IR (c+n-') at room temperature: 2890-3070 1600N
M R (CD Cl 3) δ (ppm): 1.1 B
, 3 H,t; 1.32. 9H,s;1.
8-2.1. 2H, m; 2.45-2.8. 6H,
m;7.03. IHd; 7.122H,d;
7.32,2H,d;8.32. IH,d ;8
．． 36. IH,s; Elemental analysis (%) CI]N Calculated value 85.36 9.67 4.97 Actual value 85.10 9.82 5.08 Example 26 ■-(3-ethyl-4-pyridyl)-2 -Methyl 3-phenyl-2-propatol 3.0 g (1.8 mmol I) were cooled to 0 °C and, with stirring, 3 m thionyl chloride.
Added l. After stirring for 1 hour, the mixture was returned to room temperature and stirred for 1 hour. Excess thionyl chloride was removed under reduced pressure, saturated aqueous sodium bicarbonate solution was added, and the mixture was extracted with ethyl acetate.

After drying over anhydrous sodium sulfate, ethyl acetate was distilled off under reduced pressure to give ■-phenyl-2-methyl-3-(
3-ethyl-4-pyridyl)-1 propene and 1. −(
2.1 g (75%) of 3-ethyl-4-pyridyl)2-methyl-3-phenyl-1-probenz mixture was obtained.

Next, 2.1 g of this mixture was added to 20 m of a solution of ethyl alcohol:acetic acid-1=1! Dissolved in 5% palladium-
500 mg of carbon was added, and the mixture was stirred for 6 hours under a hydrogen atmosphere. After the obtained solution was filtered and washed with ethyl alcohol, the filtrate and washing liquid were combined and the solvent was distilled off under reduced pressure. It was further dissolved in ethyl acetate, washed with 5% sodium hydroxide, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 2.1 g (yield: 98.6%) of the target product.

The obtained compound is 1-(3ethyl-4
-pyridyl)-2-methyl-3-phenylpropane (hereinafter referred to as compound 34).

Oily substance IR (cm-') at room temperature: 2B90~3070, 1608°5
0O NMR (CDCl2) δ (ppm): 0.88. 3
H,d;1.16. 2H,t; 2.4-2.9
．． 6H, md; 7.0-7.4 6H, m; 8.
36. IH,d; 8.39LH,s; Elemental analysis (%) HN Calculated value 85.31 8.84 5.85 Actual value
85.25 8.72 6.02 Example 27 1-phenyl-3-(3-n-butyl-
Oxalate of 1-phenyl-3(3-n-butyl-4-pyridyl)-butane (hereinafter referred to as compound 35) is obtained by reacting equimolar amounts of 4-pyridyl)-butane (compound 24) and oxalic acid.
I got it. The melting point of this product was 84.6-85.7°C.

Example 2 1-(2-methylphenyl)3-(3 obtained in Example 23)
-Ethyl-4-pyridyl)-propane (compound 27) and oxalic acid are reacted in equimolar amounts to form 1(2-methylphenyl)-
3-(3-ethyl-4pyridyl)-propane oxalate (
(hereinafter referred to as compound 36) was obtained. The melting point of this thing is 1
The temperature was 25.4-126.3°C.

Example 29 1-(2-methylphenyl), 3-( obtained in Example 23)
3-ethyl-4-pyridyl)-propane (compound 27)
and hydrochloric acid in equimolar reaction to form 1(2-methylphenyl)-
3-(3-ethyl-4pyridyl)-propane hydrochloride (
(hereinafter referred to as compound 37) was obtained. The melting point of this thing is 1
The temperature was 21.9-122.9°C.

Test example] Effect on brown planthopper A chemical solution with a concentration of 500 ppm of each test compound was applied to a length of 10 cm.
Cut rice stems were soaked in water for 1 minute, air-dried, placed in a test tube filled with water, and brown planthopper larvae (3rd instar) were released in the test tubes, covered with cotton plugs, and left in a thermostatic chamber at 25°C. . When the larvae were determined to be alive or dead after 7 days of testing, a dead weight rate of 100% was achieved for all of the test compounds (compounds 1 to 37).

[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 pyridine derivative of the present invention has a structure different from that of conventionally known derivatives, its action is also different, and it is particularly effective in controlling pests where resistant species have appeared. Moreover, it decomposes quickly, quickly decomposes after application, and there is no risk of causing problems with persistence or accumulation.

Therefore, the pyridine derivatives and salts thereof of the present invention are expected to be effective and widely used for controlling pests in agriculture and horticulture.

Claims (1)

[Claims] General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, X is a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. , represents a haloalkyl group having 1 to 4 carbon atoms or a haloalkoxy group having 1 to 4 carbon atoms, R^1 to R^8 each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is 0 to 5 is an integer. Furthermore, R^1 and R^4, R^2 and R^5, R^3 and R^
Each of 6 may be bonded to form an alkylene group having a carbon-carbon double bond. Further, when n is 2 or more, X may be the same or different. However, the case where R^1 to R^8 are all hydrogen atoms is excluded. Also, R^7 and R^8
When is a hydrogen atom, n is any one of 1 to 5. ]
, General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, X, R^1 to R^4, R^7, R^8 and n
is the same as above. However, R^1 to R^4, R^7 and R
Except when all ^8 are hydrogen atoms. Also, R^7
And when R^8 is a hydrogen atom, n is either 1 to 5. ] Or general formula (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) [In the formula, X, R^1 ~ R^3, R^6 ~ R^8 and n
is the same as above. However, R^1~R^3 and R^6~R
Except when all ^8 are hydrogen atoms. Also, R^7
And when R^8 is a hydrogen atom, n is either 1 to 5. ] A pyridine derivative or a salt thereof.