JPH0676381B2 - New diamines and their production method - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to novel diamines and a method for producing the same.

[0002]

2. Description of the Prior Art West German Patent Publication No. 2,514,402 known prior to the filing date of the present application has the following general formula:

[0003]

[Chemical 4]

It is described that the 2-nitromethylene-imidazolidine derivative represented by and the 2-nitromethylene-hexahydropyrimidine derivative have insecticidal activity. Then, n = 2, R ₁ = phenyl- (C ₁ ~
The case of a C ₂ ) alkyl group and R ₂ = R ₃ = hydrogen atom is included, and the specification describes a compound represented by the following formula.

[0005]

[Chemical 5]

[0006]

DISCLOSURE OF THE INVENTION Problem to be Solved by the Invention
Pests resistant to these insecticides resulting from the use of organophosphorus and carbamate insecticides for many years than before, particularly puncture-absorbing pests represented by Hemiptera, such as aphids. A nitromethylene derivative represented by the following formula (I), which exhibits a remarkable controlling effect on mosquitoes, planthoppers, leafhoppers and the like, has been separately proposed (Japanese Patent Application No. 60-186,592 = Japanese Patent Laid-Open No. 62-48). 680
issue).

Formula:

[0008]

[Chemical 6]

In the formula, R represents a hydrogen atom or an alkyl group, X represents a haloalkyl group, a haloalkoxy group, a haloalkylthio group, a haloalkylsulfinyl group, a haloalkylsulfonyl group, a nitro group, a cyano group, a thiocyanato group, a haloalkenyl group, A haloalkynyl group, a hydroxy group, an alkoxycarbonyl group, an amino group, an acyl group, a dialkylamino group, an acylamino group or an alkoxy group, 1 represents 1, 2 or 3, provided that when 1 is 1, X is an alkoxy Does not represent a group, and l is 2 or 3
, All Xs do not represent an alkoxy group,
m represents 2, 3 or 4, and n represents 0 or 1.

The compound of formula (I) above has the formula:

[0011]

[Chemical 7]

Wherein R, X, l, m and n are the same as defined above, and a compound of the formula:

[0013]

[Chemical 8] Wherein R ′ represents a lower alkyl group or a benzyl group, or two R ′ together represent a C ₂ or lower alkylene group, which may form a ring together with the adjacent sulfur atom, It is obtained by reacting with a compound represented by

The diamines of the above formula (II) are novel compounds which have not been described in the known publications prior to the filing date of the present application, and the present invention relates to the compounds.

The compound of the formula (II) of the present invention can be obtained, for example, by the following method:

[0016]

[Chemical 9]

In the formula, R, X, l and n are the same as defined above, and Y represents a halogen atom or a group —OS ₂ R ″, wherein R ″ represents a lower alkyl group or an aryl group. The compound and formula:

[0018]

Embedded image H ₂ N— (CH ₂ ) m—NH ₂ (V) In the formula, m 2 is the same as the above, and is obtained by reacting.

In the formula (II) of the compound of the present invention, preferably R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X represents 1 to 4 carbon atoms, a fluoro, chloro and / or bromine substituted alkyl group, Fluoro and / or chloro-substituted alkoxy groups having 1 to 4 carbon atoms, fluor and / or chloro-substituted alkylthio groups having 1 to 4 carbon atoms, fluor and / or chloro-substituted alkylsulfinyl groups having 1 to 4 carbon atoms,
Fluoro and / or chloro-substituted alkylsulfonyl group having 1 to 4 carbon atoms, nitro group, cyano group, thiocyanato group,
Fluoro- and / or chloro-substituted alkenyl groups having 2 to 3 carbon atoms, fluoro- and / or chloro-substituted alkynyl groups having 2 to 3 carbon atoms, hydroxy group, alkoxycarbonyl group having alkyl having 1 to 2 carbon atoms, amino group, acetyl Group, a dialkylamino group having 1 to 2 carbon atoms, an acetamido group or a methoxy group, and 1 represents 1 or 2, provided that when 1 is 1, X does not represent a methoxy group, and When 2 is 2, all Xs do not represent a methoxy group, m represents 2 or 3, and n represents 0.
Indicates.

Further, in the formula (II), it is particularly preferable that R represents a hydrogen atom or methyl, and X represents 1 to 2 carbon atoms.
Fluoro-substituted alkyl group, C1-C2 fluoro-substituted alkoxy group, C1-C2 fluoro-substituted alkylthio group, C1-C2 fluoro-substituted alkylsulfinyl group, C1-C2 fluoro-substituted alkylsulfonyl Group, nitro group, cyano group, thiocyanato group, chloro-substituted vinyl group, fluoro-substituted propargyl group, hydroxy group, methoxycarbonyl group, amino group, acetyl group,
It represents a dimethylamino group or an acetamide group, 1 represents 1 or 2, m represents 2 or 3, and n represents 0.

The following compounds can be given as specific examples of the compound of the formula (II) of the present invention.

N- (2-fluoromethoxy-5-pyridylmethyl)-, N- (2-difluoromethoxy-5-pyridylmethyl)-, N- (2-trifluoromethoxy-)
5-pyridylmethyl)-, N- [1- (2-trifluoromethoxy-5-pyridyl) ethyl]-, N- [2-
(2-Fluoroethoxy) -5-tridylmethyl]-,
N- [2- (2-chloroethoxy) -5-pyridylmethyl]-, N- [2- (2-bromoethoxy) -5-pyridylmethyl]-, N- [2- (2,2,2- Trifluoroethoxy) -5-pyridylmethyl]-, N- [2-
(1,1,2,2-Tetrafluoroethoxy) -5-pyridylmethyl]-, N- [2- (1,1,1,3,3,3-hexafluoro-2-propoxy) -5-pyridyl Methyl]-, N- (2-difluoromethylthio-5-pyridylmethyl)-, N- (2-trifluoromethylthio-5
-Pyridylmethyl)-, N- [2- (2,2,2-trifluoromethylthio) -5-pyridylmethyl]-, N-
(5-trifluoromethylthio-2-pyridylthio)
-, N- [2- (2-fluoroethylthio) -5-pyridylmethyl]-, N- (2-nitro-5-pyridylmethyl)-, N- (3-methoxy-2-nitro-6-pyridyl Methyl)-, N- (2-cyano-5-pyridylmethyl)-, N- (2-thiocyanato-5-pyridylmethyl)-, N- [1- (2-cyano-5-pyridyl) ethyl]-, N- (2-hydroxy-5-pyridylmethyl)
-, N- (2-methoxycarbonyl-5-pyridylmethyl)-, N- (5-methoxycarbonyl-2-pyridylmethyl)-, N- (2-ethoxycarbonyl-5-pyridylmethyl)-, N- [ 2- (2,2-dichlorovinyl) -5-pyridylmethyl]-, N- [2- (3-fluoropropargyl) -5-pyridylmethyl]-, N-
(2-Amino-5-pyridylmethyl)-, N- (2-dimethylamino-5-pyridylmethyl)-, N- (2-acetyl-5-pyridylmethyl)-, N- (2-acetamido-5- Pyridylmethyl)-, N- (2-trifluoromethylsulfonyl-5-pyridylmethyl)-, N-
(2-trifluoromethylsulfinyl-5-pyridylmethyl)-, N- (2-fluoromethyl-5-pyridylmethyl)-, N- (2-difluoromethyl-5-pyridylmethyl)-, N- (2- Trifluoromethyl-5-pyridylmethyl)-, N- (2-chlorodifluoromethyl-5-pyridylmethyl)-, N- [1- (2-trifluoromethyl-5-pyridyl) ethyl]-, N- ( 2-bromodifluoromethyl-5-pyridylmethyl)-, N-
(5-trifluoromethyl-2-pyridylmethyl)-,
N- [2- (2-fluoroethyl) -5-pyridylmethyl]-, N- [2- (2-chloroethyl) -5-pyridylmethyl]-, N- [2- (2,2,2-tri Fluoroethyl) -5-pyridylmethyl]-, N- [2- (1,1,
2,2-Tetrafluoroethyl) -5-pyridylmethyl]-, N- [2- (1,1,2,2,2-pentafluoroethyl) -5-pyridylmethyl]-, N- (3-methoxy -Ethylenediamine and -trimethylenediamine such as 2-nitro-6-pyridylmethyl)-.

Process a) for obtaining the compound of formula (II) is represented by the following reaction scheme.

[0024]

[Chemical 11]

(In the formula, R, X, l, m, n and Y are the same as the above.) The compound of the formula (IV) as the raw material in the production method a) is the above-mentioned R, X, l, n and It means that it is based on the definition of Y, preferably R, X, l and n have the same meanings as defined above, and Y represents a chlorine atom or a bromine atom.

According to the present invention, the starting compound of the formula (IV) can be synthesized by a known method.

Specific examples thereof include 2-fluoromethoxy-5-pyridylmethyl-, 2-difluoromethoxy-5-pyridylmethyl-, 2-trifluoromethoxy-5-pyridylmethyl-, 1- (2- Trifluoromethoxy-5-pyridyl) ethyl-, 2- (2-fluoroethoxy) -5-pyridylmethyl-, 2- (2-chloroethoxy) -5-pyridylmethyl-, 2- (2-bromoethoxy)- 5-pyridylmethyl-2- (2,2,2
-Trifluoroethoxy) -5-pyridylmethyl-2
-(1,1,2,2-tetrafluoroethoxy) -5-pyridylmethyl-, 2- (1,1,1,3,3,3-hexafluoro-2-propoxy) -5-pyridylmethyl-, Two
-Difluoromethylthio-5-pyridylmethyl-, 2-
Trifluoromethylthio-5-pyridylmethyl-2,-
(2,2,2-Trifluoromethylthio) -5-pyridylmethyl-5-trifluoromethylthio-2-pyridylthio-, 2- (2-fluoroethylthio) -5-pyridylmethyl-2,2-nitro-5 -Pyridylmethyl-, 3-
Methoxy-2-nitro-6-pyridylmethyl-, 2-cyano-5-pyridylmethyl-, 1- (2-cyano-5-
Pyridyl) ethyl-, 1- (2-thiocyanato-5-pyridyl) methyl-, 2-hydroxy-5-pyridylmethyl-, 2-methoxycarbonyl-5-pyridylmethyl-, 5-methoxycarbonyl-2-pyridylmethyl- ,
2-ethoxycarbonyl-5-pyridylmethyl-2-
(2,2-dichlorovinyl) -5-pyridylmethyl-,
2- (3-Fluoropropargyl) -5-pyridylmethyl-, 2-amino-5-pyridylmethyl-, 2-dimethylamino-5-pyridylmethyl-, 2-acetyl-5-
Pyridylmethyl-, 2-acetamido-5-pyridylmethyl-, 2-trifluoromethylsulfonyl-5-pyridylmethyl-, 2-trifluoromethylsulfinyl-
5-pyridylmethyl-, 2-fluoromethyl-5-pyridylmethyl-, 2-difluoromethyl-5-pyridylmethyl-, 2-trifluoromethyl-5-pyridylmethyl-, 2-chlorodifluoromethyl-5-pyridylmethyl -, 1- (2-trifluoromethyl-5-pyridyl) ethyl-, 2-bromodifluoromethyl-5-pyridylmethyl-, 5-trifluoromethyl-2-pyridylmethyl-, 2- (2-fluoroethyl) -5-pyridylmethyl-, 2- (2-chloroethyl) -5-pyridylmethyl-, 2- (2,2,2-trifluoroethyl) -5-pyridylmethyl-, 2- (1,1,2, 2-Tetrafluoroethyl) -5-pyridylmethyl-, 2- (1,1,2,2,2
-Pentafluoroethyl) -5-pyridylmethyl-3
-Methoxy-2-nitro-6-pyridylmethyl-, etc.-
Examples are chloride or -bromide.

In the halides exemplified above, chloride can be easily synthesized by a conventional method in which the corresponding alcohol is chlorinated with, for example, thionyl chloride, and the side chain methyl group is N-bromosuccinimide, N-. It can also be synthesized by halogenating with a halogenating agent such as chlorosuccinimide.

Some of the trifluoromethyl, trifluoromethoxy substituted pyridylmethyl alcohols are described in J. M
ed. Chem., 13: 1124-1130. Using these synthetic methods, 2-methyl-5-trifluoromethylpyridine obtained by the reaction of 6-methylnicotinic acid with hydrofluoric acid and sulfur tetrafluoride is converted into N-oxide, and the N-oxide The rearrangement reaction can lead to 5-trifluoromethyl-2-pyridylmethyl alcohol.

This reaction can also be applied to the synthesis of 5-methyl-2-trifluoromethylpyridine from 5-methylpicolinic acid. The desired starting material, novel 2-trifluoromethyl-5-pyridylmethyl bromide (or chloride), was prepared by converting the above-mentioned 5-methyl-2-trifluoromethylpyridine into N-bromosuccinimide and N-chlorosuccinimide. It can be synthesized by monohalogenating the methyl group at the-position.

2-Trifluoromethoxy-5-pyridylmethyl bromide (or chloride) is likewise obtained from 2-hydroxy-5-methylpyridine 5-methyl-
Obtained by reacting 2-trifluoromethoxypyridine with N-bromosuccinimide, N-chlorosuccinimide.

Since the halogen at the ortho position of the pyridine ring is active, for example, 6-haloalkoxynicotinic acid can be synthesized by the reaction of 6-chloronicotinic acid with an excess amount of sodium alkoxide, which can be reduced. As a starting material, 2-haloalkoxy-5-pyridylmethyl alcohol can be synthesized.

As an alternative method for synthesizing haloalkyl-substituted pyridines, it is also possible to directly synthesize haloalkyl-substituted pyridines by condensation reaction of methylbutadiene and haloalkanenitrile, for example, trifluoroacetonitrile. For example, 5-methyl-2-trifluoromethylpyridine can be obtained from methylbutadiene and trifluoroacetonitrile (JAC.
S., 78, 978-979, J. Org. Che
m., 29, 569-571.

Haloalkylthio-substituted pyridines include, for example, 5-methylpyridine-2-thione (Syn
th. Commun., Vol. 11, pp. 273-280) is reacted with an appropriate alkylating agent in the presence of an alkali to give 2-haloalkylthio-5-methylpyridine,
As described above, N-bromosuccinimide or N-chlorosuccinimide can be used as the starting material pyridylmethyl chloride (or bromide).

Nitropyridylmethyl bromide can be synthesized with nitropicolinic acid and N-bromosuccinimide. For example, 2-nitro-3-pyridylmethyl bromide can be obtained from 3-methyl-2-nitropyridine (J. Chem. Soc., 1966 , 315-3).
21). Similar pyridylmethyl halides can also be synthesized using this reaction. Cyano-substituted pyridyl alkyl halides can be obtained, for example, by reacting 3-hydroxymethylpyridine-N-oxide with trimethylsilyl cyanide to give 2-cyano-5-hydroxymethylpyridine (PCT Int. Appl. WO8,30
1,446), and further treatment with a halogenating agent gives pyridylmethyl halides. (Gazz. Chi
m. Ital., 105, 1001-1099).

The compound of formula (V) is a compound described in West German Patent Publication No. 2732660 and French Patent No. 1,499,785. Specific examples thereof include, for example, ethylenediamine and trimethylenediamine (also known as 1,3
-Diaminopropane).

In carrying out the process (a) mentioned above, use may be made, as suitable diluent, of any inert solvent.

Examples of such diluents are water; aliphatic,
Cycloaliphatic and aromatic hydrocarbons (optionally chlorinated), for example hexane, cyclohexane,
Petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride and trichloroethylene, chlorobenzene; other ethers such as diethyl ether, methyl ethyl ether, di-iso-propyl ether, dibutyl ether, Propylene oxide,
Dioxane, tetrahydrofuran; Ketones such as acetone, methyl ethyl ketone, methyl-iso-propyl ketone, methyl-iso-butyl ketone; Nitriles such as acetonitrile, propionitrile, acrylonitrile; Alcohols such as methanol, ethanol, iso-propanol, butanol, Ethylene glycol; esters such as ethyl acetate, amyl acetate;
Examples thereof include acid amides such as dimethylformamide and dimethylacetamide; sulfones and sulfoxides such as dimethylsulfoxide and sulfolane; and bases such as pyridine.

In carrying out the above-mentioned preparation method a), for example, 1 mol of the compound of the formula (IV) is reacted with an excessive amount of the compound of the formula (V), for example, about 5 times, and the reaction temperature is usually. It can be easily carried out by carrying out in the range of 0 to 50 ° C.

In the formula (II), when n = 0,
Alternatively, it can be produced by the following method.

Production method b):-

[0042]

[Chemical 12]

(In the formula, X, R, l and m are the same as above.) In the above production method b), most of the compounds of the general formula (VI) are, for example, those of the same applicant as the present application. No. 61-178982 (Japanese Patent Application No. 60-18628)
No.), and the compounds described in J. Me
d. Chem., Vol. 13, pages 1124-1130. And, in general, these substituted pyridine carbaldehydes are described in J. Org. Chem.,
26, pages 4912 to 4914, or a reaction in which the corresponding pyridinecarboxylic acid and its derivative are reduced to an aldehyde by a conventional method (Org. Reaction, Volume 8, 218 to 25).
It can be synthesized by using (7). And the said manufacturing method b), as shown by a reaction formula, with the pyridine carbaldehyde of Formula (VI), or a pyridyl alkyl ketone,
Imines are synthesized by reaction with compounds of formula (V), to which, for example, sodium borohydride (NaBH ₄ )
By reacting with a reducing agent such as
Can be synthesized.

In the formula (II), when R = H, n
In the case of = 0, it can be manufactured by the following method as an alternative method.

Manufacturing method c):-

[0046]

[Chemical 13]

(In the formula, X, l and m are the same as above.) As shown in the above reaction formula, by the reaction of the pyridylcarbonyl chloride of the formula (VII) and the compound of the formula (V),
A compound of formula (II ″) can be synthesized by synthesizing nicotinamide or picolinamide and reacting it with a reducing agent such as lithium aluminum hydride (LialH ₄ ).

In the compound of the above formula (II),
In the case of R = H, n = 0, and m = 3, it can be produced by the following method as another method.

Production method d):-

[0050]

[Chemical 14]

In the formula, X and l are the same as above.

As shown in the above reaction scheme, acrylonitrile is added to the compound of formula (VIII), and this adduct is reduced in the same manner as in the above production method b) to give the compound of formula (I
The compound of I ″ ″) can be synthesized.

Further, in the compound of formula (II) above,
When m = 2, as an alternative method,
It can be manufactured.

Production method e):-

[0055]

[Chemical 15]

In the formula, R, X, l and n are the same as above.

As shown in the above reaction scheme, a compound of formula (II ″ ″) can also be synthesized by reacting a pyridylalkylamine of formula (IX) with ethyleneimine.

The nitromethylene derivative of the formula (I) obtained by using the diamines of the formula (II) of the present invention as a raw material has been proposed as described above (Japanese Patent Application No. 60-186,592).
As described in detail in No. 8,680), it exhibits a strong insecticidal action.

Next, the contents of the present invention will be specifically described with reference to examples, but the present invention should not be limited to these.

[0060]

【Example】

 Example 1

[0061]

[Chemical 16]

A solution of 2-cyano-5-pyridylmethyl chloride (4.6 g) in acetonitrile (20 ml) was added 5 times.
Add dropwise to a solution of ethylenediamine (9 g) in acetonitrile (50 ml) at -10 ° C. After completion of dropping, 3 at room temperature
After stirring for an hour, acetonitrile and excess ethylenediamine are distilled off from the contents under reduced pressure. Dichloromethane is added to the residue, and the dichloromethane-soluble component is collected. Dichloromethane was distilled off under reduced pressure, and volatile matter was removed at 50 ° C. and 1 mmHg to give N- (2-cyano-5) as colorless oil.
-Pyridylmethyl) ethylenediamine (4.5 g) is obtained.

N ²⁰ _D 1.5718 Example 2

[0064]

[Chemical 17]

5-Trifluoromethylpicolinaldehyde (3.5 g) was added dropwise to a solution of trimethylenediamine (7.4 g) in benzene (70 ml) at room temperature. After completion of the dropping, the mixture is gradually heated with stirring and then refluxed for 2 hours while separating azeotropic water. After distilling off benzene under reduced pressure, the residue was dissolved in ethanol (100 ml), and 10
Sodium borohydride (0.9g) is added in portions with stirring at ~ 15 ° C. After that, the content is stirred at room temperature for 2 hours, and then ethanol is distilled off at an internal temperature of 30 ° C. or lower. Dichloromethane was added to the residue to separate the dichloromethane-soluble component, and the dichloromethane was distilled off under reduced pressure.
When the stirred product is removed at 1 mmHg and an internal temperature of 60 ° C. or lower, colorless oily N- (5-trifluoromethyl-2-pyridylmethyl) trimethylenediamine (3.5 g) is obtained.

N ²⁰ _D 1.4651 The formula (I) of the present invention is prepared by the same method as in Examples 1 and 2 above.
The compounds of I) are specifically shown in Table 1 below.

[0067]

[Table 1]

[0068]

[Table 2]

[0069]

[Table 3]

Example 3

[0071]

[Chemical 18]

3-methoxy-6-methyl-2-nitropyridine (Acta Chem. Scand., Vol. 23,
1791 to 1796) (7.1 g), N-bromosuccinimide (7.1 g), carbon tetrachloride (80 ml)
A catalytic amount of α, α'-azobis (isobutyronitrile) is added therein and the mixture is refluxed for 16 hours. After the reaction, suction filtration is performed while still hot to separate insoluble succinimide. When the filtrate was cooled to room temperature, unreacted 3-methoxy-
6-Methyl-2-nitropyridine crystallizes and precipitates, which is filtered off and the residue is concentrated, followed by
Vacuum distillation gives 3-methoxy-2-nitro-6-pyridylmethyl bromide (2.1 g).

Bp 128 to 131 ° C./0.6 mmHg Example 4

[0074]

[Chemical 19]

2-Cyano-5-hydroxymethylpyridine (13.4 g) and pyridine (8.7 g) were added to toluene (1
50 ml) and p-toluenesulfonyl chloride (19.1 g) in toluene (50 m) was added to this solution at room temperature.
l) Add the solution dropwise. After dropping, gradually warm to 70-8
Stir at 0 ° C. for 4 hours. After cooling to room temperature, the contents are washed with water and the organic layer is dried. After the toluene was distilled off under reduced pressure, the residue was purified by silica gel column chromatography to give 2-cyano-5-pyridylmethyl chloride as colorless crystals (7.7 g).

Mp 45-47 ° C Example 5

[0077]

[Chemical 20]

5-Methyl-2-trifluoromethylpyridine [J. Org. Chem., Volume 29, 569-57.
(See page 1) (8.1 g) in 50 ml of carbon tetrachloride, N-bromosuccinimide (8.9 g) and a catalytic amount of benzoyl peroxide are added and the mixture is stirred and refluxed for 7 hours. After cooling, the insoluble material was filtered off, the filtrate was concentrated under reduced pressure, and the residue was purified by silica gel chromatography to give colorless crystals of 2-trifluoromethyl-5-pyridylmethyl bromide [alias 5-bromomethyl-2- Trifluoromethylpyridine] (7.3 g)
Is obtained.

Mp 36-37 ° C. Example 6

[0080]

[Chemical 21]

N- (2-cyano-5-pyridylmethyl)
Trimethylenediamine (1.9g), 1-nitro-2,2
A mixture of -bis (methylthio) ethylene (1.6 g) and ethanol (30 ml) is refluxed for 5 hours with stirring. After cooling to room temperature, the precipitated crystals were collected by filtration and washed with ethanol to give pale yellow 1- (2-cyano-5-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine (1.6g). To be

Mp 214-216 ° C Example 7

[0083]

[Chemical formula 22]

Nitromethylene imidazolidine (1.3
g) is dissolved in dry dimethylformamide (15 ml), sodium hydride (0.26 g) is added and stirred at room temperature until evolution of hydrogen stops. Subsequently, a solution of 3-methoxy-2-nitro-6-pyridylmethyl bromide (2.4 g) in 5 ml of dimethylformamide is added in one portion and the contents are stirred at 60 ° C. for 15 minutes. After cooling to room temperature, the contents are added to 50 ml of ice water and extracted with dichloromethane. Dichloromethane is distilled off under reduced pressure, and ethanol is added to the residue to precipitate crystals. The crystals were collected by filtration and washed with ethanol to give 1- (3-methoxy-2
-Nitro-6-methylpyridylmethyl) -2-nitromethyleneimidazolidine (0.4 g) is obtained.

Mp 177-181 ° C. Example 8

[0086]

[Chemical formula 23]

2,2,2-trifluoroethanol (3.
6 g) is dissolved in toluene (20 ml), sodium hydride (0.7 g) is added to prepare a sodium salt of 2,2,2-trifluoroethanol. Then 1-
(2-Bromo-5-pyridylmethyl) -2- (nitromethylene) imidazolidine [Japanese Patent Application No. 59-132,943
No. Known compound] (3 g) and dry dimethylformamide (10 ml) are added, and the contents are heated at 80 ° C. for 8 hours. After the toluene is distilled off under reduced pressure, the content is poured into 20 ml of ice water and then neutralized. The aqueous solution was extracted with dichloromethane, and the extract was purified by silica gel column chromatography to give 1- [2- (2,2,2-trifluoroethoxy) -5-pyridylmethyl] -2- (nitromethylene) imidazo. Lysine (0.4 g) is obtained.

Mp 132-135 ° C. Examples of compounds of the formula (I) prepared by the same method as in Example 6, 7 or 8 are shown in Table 2 below.

[0089]

[Table 4]

[0090]

[Table 5]

[0091]

[Table 6]

Biological test: -Comparative compound A-1:

[0093]

[Chemical formula 24]

Compound described in West German Patent Publication No. 2,514,402 Example 9 (Biological test) Test for organic phosphorus agent-resistant leafhopper leafhopper Preparation of reagent solution Solvent: xylol 3 parts by weight Emulsifier: polyoxyethylene alkylphenyl 1 part by weight of ether 1 part by weight of the active compound is mixed with the stated amount of solvent containing said amount of emulsifier in order to make a suitable active compound formulation and the mixture is diluted with water to the given concentration.

Test method: To a rice plant having a plant height of about 10 cm planted in a pot having a diameter of 12 cm, 10 ml of a diluted solution of the active compound prepared as above at a predetermined concentration was sprayed per pot. After the sprayed chemical solution was dried, a wire net with a diameter of 7 cm and a height of 14 cm was covered, and 30 female adults of the leafhopper leafhopper, which is a strain that is resistant to the organophosphorus agent, were released in it and placed in a temperature-controlled room for 2 days to determine the number of dead insects. Insect kill rates were calculated.

The results are shown in Table 3 with a representative example.

[0097]

[Table 7]

Example 10 (Biological test) Test for planthoppers Test method: Plant height 10 cm planted in pot with diameter 12 cm
10 ml of a pot of a diluted solution of the active compound prepared in the same manner as in Example 8 at a predetermined concentration was sprayed on the rice plant at the top.
After spraying the chemical solution, cover it with a wire net with a diameter of 7 cm and a height of 14 cm, release 30 female adult planthoppers of the strain resistant to the organophosphorus agent, and place them in a temperature-controlled room for 2 days to determine the number of dead insects. Insect kill rates were calculated.

In the same manner as the above method, the insecticidal rate for the sedge brown planthopper and the organophosphorus drug-resistant velvetgrass planter was calculated. The results are shown in Table 4 with a representative example.

[0100]

[Table 8]

Example 11 (Biological test) Test for organic phosphorus agent and carbamate-resistant peach aphid Test method: Height about 20c planted in a clay pot with a diameter of 15 cm.
Approximately 200 heads of the organic phosphonate and carbamate-resistant peach aphid, which had been bred in eggplant seedlings (genuine black eggplant) of m, were inoculated per seedling, and one day after the inoculation, one of the active compounds prepared as in Example 8 was prepared. A water-diluted solution having a predetermined concentration was used in a spray gun to spray the original amount. After spraying, leave at 28 ° C,
The insecticidal rate was calculated 24 hours after the application. The test was repeated twice.

The results are shown in Table 5 with a representative example.

[0103]

[Table 9]

The above-mentioned Examples 9, 10 and 11 are representative examples of insecticidal use, and the compounds of the present invention exemplified here are also representative examples thereof, and the present invention should be limited thereto. Not a thing.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C07D 213/65 213/70 213/73 213/74 213/75 213/79 213/80 213/84 (72) Inventor Bernde Basner Federal Republic of Germany Löfelkusen Opladen-Hambergerstraße 27de (56) References JP 61-12682 (JP, A) JP 60-172976 (JP, A)

Claims (4)

[Claims] 1. The formula: In the formula, R represents a hydrogen atom or an alkyl group, X represents a haloalkyl group, a haloalkoxy group, a haloalkylthio group, a haloalkylsulfinyl group, a haloalkylsulfonyl group, a nitro group, a cyano group, a thiocyanato group, a haloalkenyl group, a haloalkynyl group. , A hydroxy group, an alkoxycarbonyl group, an amino group, an acyl group, a dialkylamino group, an acylamino group or an alkoxy group, 1 represents 1, 2 or 3, provided that when 1 is 1, X represents an alkoxy group. Never, when l is 2 or 3,
Not all X represents an alkoxy group, m represents 2, 3 or 4, and n represents 0 or 1.
Diamines represented by. 2. R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X is a fluoro, chloro and / or bromine-substituted alkyl group having 1 to 4 carbon atoms, and fluoro and / or chloro having 1 to 4 carbon atoms. Substituted alkoxy group, C1-C4 fluoro and / or chloro-substituted alkylthio group, C1-C4
Fluoro and / or chloro-substituted alkylsulfinyl group, C1-C4 fluoro- and / or chloro-substituted alkylsulfonyl group, nitro group, cyano group, thiocyanato group, C2-C3 fluoro- and / or chloro-substituted alkenyl group A fluoro- and / or chloro-substituted alkynyl group having 2 to 3 carbon atoms, a hydroxy group, an alkoxycarbonyl group having an alkyl group having 1 to 2 carbon atoms, an amino group, an acetyl group, a dialkylamino group having an alkyl group having 1 to 2 carbon atoms , Acetamide group or methoxy group, and 1 is 1 or 2
However, when l is 1, X does not represent a methoxy group, when l is 2, all X do not represent a methoxy group, and m is 2 or 3, and n is 0. A compound according to claim 1. 3. R is a hydrogen atom or methyl, X is a fluoro-substituted alkyl group having 1 to 2 carbon atoms, a fluoro-substituted alkoxy group having 1 to 2 carbon atoms, a fluoro-substituted alkylthio group having 1 to 2 carbon atoms, and a carbon number. 1-2 fluoro-substituted alkylsulfinyl group, C1-C2 fluoro-substituted alkylsulfonyl group, nitro group, cyano group, thiocyanato group, chloro-substituted vinyl group, fluoro-substituted propargyl group, hydroxy group, methoxycarbonyl group, amino Group, acetyl group, dimethylamino group or acetamide group, where l is 1
Or 2, m is 2 or 3, and n is 0.
The described compound. 4. The formula: Wherein R, X, l and n are the same as above, and Y represents a halogen atom or a group —OS ₂ R ″, where R ″ represents a lower alkyl group or an aryl group, The compound of the formula: H ₂ N- (CH ₂ ) m-NH ₂ wherein m is the same as defined above is reacted with the diamines according to claim 1. Manufacturing method.