JPH0713063B2 - New diamines - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to novel diamines useful as intermediates for insecticidal nitromethylene derivatives and a process for producing the same.

[0002]

2. Description of the Related Art West German Patent Publication No. 2, known before the filing date of the present application,
514,402 has the following general formula

[0003]

[Chemical 9]

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.

[0006]

[Chemical 10]

[0007]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The insecticidal nitromethylene derivative of the following formula (I) proposed in Japanese Patent Application No. 60-106853, which is the parent application of the present application, has a strong insecticidal activity and , Pests resistant to these insecticides resulting from the use of organophosphorus and carbamate insecticides for many years, especially the Hemiptera (Hemiptera).
ptera) and other puncture-absorbing pests such as aphids, planthoppers, leafhoppers, etc.

[0008]

[Chemical 11]

In the formula, R represents a hydrogen atom or an alkyl group, Z represents a hetero 6-membered cyclic group containing at least two nitrogen atoms, wherein the ring is an alkyl group, a halogen atom, a haloalkyl group or an alkoxy group. A group, an alkylthio group, a haloalkoxy group, a haloalkylthio group, an oxo group, a nitro group, a cyano group and a dialkylamino group, and m may be 2
Or 3 is shown.

The diamines of the following formula (II) of the present invention are
It is a novel compound and is useful as an intermediate for the production of the compound of the above formula (I).

[0011]

[Chemical 12] In the formula, R represents a hydrogen atom or an alkyl group, Z represents a hetero 6-membered cyclic group containing at least two nitrogen atoms, wherein the ring is an alkyl group, a halogen atom, a haloalkyl group,
It may be substituted with at least one selected from an alkoxy group, an alkylthio group, a haloalkoxy group, a haloalkylthio group, an oxo group, a nitro group, a cyano group and a dialkylamino group, and m represents 2 or 3 .

The compound of the above formula (II) can be prepared by the following methods a) and b), that is, the method a) of the general formula:

[0013]

[Chemical 13] In the formula, R, Z and Hal are the same as the above, and a compound represented by the general formula:

[0014]

Embedded image H ₂ N— (CH ₂ ) m—NH ₂ (IV) In the formula, m is the same as above, or a compound represented by the following formula b) is used.

[0015]

[Chemical 15] In the formula, R and Z are the same as defined above,
The compound of the general formula:

[0016]

[Chemical 16] In the formula, R, Z and m are the same as defined above, and the compound is obtained by reducing the compound.

In the compound of general formula (II) of the present invention,
Preferably, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Z represents a hetero 6-membered cyclic group containing 2 or 3 nitrogen atoms, wherein the ring has 1 to 4 carbon atoms. Alkyl group, fluor atom, chloro atom, bromine atom, fluoro, chloro and / or bromine-substituted alkyl group having 1 to 2 carbon atoms, alkoxy group having 1 to 4 carbon atoms, alkylthio group having 1 to 4 carbon atoms, fluoro And / or substituted by at least one selected from a chloro-substituted C1 to C2 alkoxy group, a fluoro and / or a chloro-substituted C1 to C2 alkylthio group, an oxo group, a nitro group, a cyano group and a dimethylamino group. And m represents 2 or 3.

In the general formula (II), particularly preferably, R represents a hydrogen atom or a methyl group, Z represents a hetero 6-membered cyclic group containing 2 nitrogen atoms, wherein the ring is a methyl group, It may be substituted by at least one selected from a fluoro atom, a chloro atom and a trifluoromethyl group, and m represents 2 or 3.

In the general formula (II) of the present invention, examples of Z include heterocycles such as a pyrimidine ring having 2 nitrogen atoms, a pyrazine ring, a pyridazine ring, and a nitrogen atom 3.
A triazine ring (1,2,3-, 1,2,4- or 1,3,5-) having a ke atom and a tetrazine ring (1,2,4,5-) having 4 nitrogen atoms as a basic ring Examples of the heterocyclic group are

Specific examples of the compound represented by the general formula (II) include N- (4-pyrimidinylmethyl) ethylenediamine, N- (2-methyl-4-pyrimidinylmethyl) ethylenediamine, N- (2-methyl-). 6-oxo-1H, 6H-dihydropyrimidin-4-ylmethyl)
Trimethylenediamine, N- (5-pyrimidinylmethyl) ethylenediamine, N- (2-methyl-5-pyrimidinylmethyl) ethylenediamine, N- (2-dimethylamino-5-pyrimidinylmethyl) ethylenediamine,
N- (2-dimethylamino-5-pyrimidinylmethyl)
Trimethylenediamine, N- (2,4,6-trichloro-
5-pyrimidinylmethyl) ethylenediamine, N- (pyrazinylmethyl) ethylenediamine, N- [1- (pyrazinyl) ethyl] ethylenediamine, N- (2-methyl-5-pyrazinylmethyl) ethylenediamine, N- (3
-Pyridazinylmethyl) ethylenediamine, N- (2-
Chloro-4-pyrimidinylmethyl) ethylenediamine,
N- (4-chloro-6-pyrimidinylmethyl) ethylenediamine, N- (4-methyl-6-pyrimidinylmethyl) trimethylenediamine, N- (2-fluoro-5-
Pyrimidinylmethyl) ethylenediamine, N- [1-
(2-Fluoro-5-pyrimidinyl) ethyl] ethylenediamine, N- (2-chloro-5-pyrimidinylmethyl) ethylenediamine, N- (2-chloro-5-pyrimidinylmethyl) trimethylenediamine, N- (2-isopropyl- 5-pyrimidinylmethyl) ethylenediamine, N- (2-chlorodifluoromethyl-5-pyrimidinylmethyl) ethylenediamine, N- (2-trifluoromethyl-5-pyrimidinylmethyl) ethylenediamine, N- (2-bromodifluoromethyl-5- Pyrimidinylmethyl) ethylenediamine, N- (2-methoxy-
5-pyrimidinylmethyl) ethylenediamine, N- (2
-Difluoromethoxy-5-pyrimidinylmethyl) ethylenediamine, N- (2-trifluoromethoxy-5-
Pyrimidinylmethyl) ethylenediamine, N- [2-
(2,2,2-Trifluoroethoxy) -5-pyrimidinylmethyl] trimethylenediamine, N- (2-methylthio-5-pyrimidinylmethyl) ethylenediamine, N-
(2-Ethylthio-5-pyrimidinylmethyl) ethylenediamine, N- (2-difluoroethylthio-5-pyrimidinylmethyl) ethylenediamine, N- (2-trifluoromethylthio-5-pyrimidinylmethyl) ethylenediamine, N- [2- ( 2,2,2-trifluoroethylthio) -5-pyrimidinylmethyl] ethylenediamine,
N- (2-nitro-5-pyrazinylmethyl) ethylenediamine, N- (2-cyano-5-pyrazinylmethyl) trimethylenediamine, N- (2-chloro-5-pyrazinylmethyl) ethylenediamine, N- (2-trifluoromethyl- 5-pyrazinylmethyl) ethylenediamine, N
-(3-Fluoro-6-pyridazinylmethyl) ethylenediamine, N- (3-methyl-6-pyridazinylmethyl) trimethylenediamine, N- (4-pyridazinylmethyl) ethylenediamine, N- (3-chloro-6-pyridazinylmethyl) ethylenediamine, N- (4-pyridazinylmethyl) trimethylenediamine, N- (3-trifluoromethyl-6-pyridazinylmethyl) ethylenediamine, N -(1,3,5-triazin-2-ylmethyl) ethylenediamine, N- (3-chloro-1,2,4-
Triazin-6-ylmethyl) ethylenediamine, N-
(3,5-dichloro-1,2,4-triazin-6-ylmethyl) ethylenediamine, N- (3-chloro-1,2,
Examples include 4,5-tetrazin-6-ylmethyl) ethylenediamine and the like.

When pyrazinylmethyl chloride and ethylenediamine are used as the raw materials in the above-mentioned production method a), the reaction can be represented by the following reaction formula.

[0022]

[Chemical 17]

In the above production method b), for example, when 5-pyrimidine carbaldehyde and ethylenediamine are used as raw materials, the reaction can be represented by the following reaction formula.

[0024]

[Chemical 18]

In the above-mentioned production method a), the compound of the general formula (III) which is a raw material means a compound based on the definition of R and Z described above, and preferably R and Z have the same meaning as defined above. In addition, Hal represents a chlorine atom or a bromine atom.

According to the present invention, the compound of the general formula (III) includes both known and novel compounds and can be synthesized by a known method. And as specific examples thereof, for example, 4-pyrimidinylmethyl-, 2-methyl-4-pyrimidinylmethyl-, 2-methyl-6-oxo-1H, 6H-dihydropyrimidin-4-ylmethyl-, 5-pyrimidinylmethyl- , 2-methyl-5-pyrimidinylmethyl-, 2-dimethylamino-5-pyrimidinylmethyl-, 2,4,6-trichloro-5-pyrimidinylmethyl-, pyrazinylmethyl-, 1- (pyrazinyl) ethyl-, 2-methyl -5-pyrazinylmethyl-,
3-pyridazinylmethyl-, 2-chloro-4-pyrimidinylmethyl-, 4-chloro-6-pyrimidinylmethyl-, 4-methyl-6-pyrimidinylmethyl-, 2-fluoro-5-pyrimidinylmethyl-, 1 -(2-Fluoro-5-pyrimidinyl) ethyl-, 2-chloro-5-pyrimidinylmethyl-, 2-isopropyl-5-pyrimidinylmethyl-, 2-chlorodifluoromethyl-5-pyrimidinylmethyl-, 2-trifluoromethyl -5-pyrimidinylmethyl-, 2-bromodifluoromethyl-5-pyrimidinylmethyl-, 2-methoxy-5-pyrimidinylmethyl-, 2-difluoromethoxy-5-pyrimidinylmethyl-, 2-trifluoromethoxy-5-pyrimidinylmethyl -, 2- (2,2,2-trifluoroethoxy)
-5-pyrimidinylmethyl-, 2-methylthio-5-pyrimidinylmethyl-, 2-ethylthio-5-pyrimidinylmethyl-, 2-difluoroethylthio-5-pyrimidinylmethyl-, 2-trifluoromethylthio-5-pyrimidinylmethyl- , 2-nitro-5-pyrazinylmethyl-, 2-cyano-5-pyrazinylmethyl-, 2-chloro-5-pyrazinylmethyl-, 2-trifluoromethyl-
5-pyrazinylmethyl-, 3-fluoro-6-pyridazinylmethyl-, 3-methyl-6-pyridazinylmethyl-, 4-pyridazinylmethyl-, 3-chloro-6-pyridazinyl Methyl-, 4-pyridazinylmethyl-, 3-trifluoromethyl-6-pyridazinylmethyl-, 1,3,
5-triazin-2-ylmethyl-, 3-chloro-1,
2,4-triazin-6-ylmethyl-, 3,5-dichloro-1,2,4-triazin-6-ylmethyl-, 3-chloro-1,2,4,5-tetrazin-6-ylmethyl-, etc. Examples thereof include chloride and bromide.

The compounds of the general formula (III) exemplified above are
Generally, the corresponding alcohols are halogenated by a conventional method with a halogenating agent such as thionyl chloride, or the corresponding methyl-substituted compounds are halogenated such as N-bromosuccinimide and N-chlorosuccinimide. It can be easily synthesized by halogenating the side chain methyl group with an agent.

Further, the above alcohols can be easily synthesized by reducing the aldehydes or carboxylic acids of the general formula (V) exemplified below by a conventional method. As a specific example, 5-pyrimidinylmethyl alcohol is obtained from 5-pyrimidine carbaldehyde, and 2-chloro-5-pyrimidinyl methyl alcohol is obtained from 2-chloro-5-pyrimidine carbaldehyde. 3-Pyridazinylmethyl alcohol can also be synthesized from furfuryl acetate (Acta Chem. Scand., Vol. 1, 619).
page). For pyrazinylalkyl halides, easily available methylpyrazine and dimethylpyrazine are used as N-
Chlorosuccinimide can be converted to chloromethylpyrazine (Synthesis, 1984 , 676-6).
P. 79). This reaction is performed with methylpyrazine having another substituent, halo-substituted methylpyridazines such as 3-chloro-
6-Methylpyridazine (J. Chem. Soc., 1947 , 24
(See page 2) etc., and by this reaction,
3-Chloro-6-pyridazinylmethyl chloride can be synthesized, and 2-chloro-5-methylpyrimidine (Reacts.Sposobnost.Org.Soedin., 5: 824-).
(See page 837) and N-bromosuccinimide, 2
-Chloro-5-pyrimidinylmethyl bromide can be obtained.

J. Heterocycl. Chem., Vol. 19, 40
P. 7 and Chem. Pherm. Bull., 28, 3057-30.
As described on page 63, ethyl 2-chloropyrazine-
It is also possible to synthesize 5-carboxylate and reduce it to convert it to the corresponding methanol (West German Patent Publication No. 2,910,824).

Triazinylalkyl halides such as 1,3,5-triazin-2-ylmethyl chloride are
Obtained by the reaction of 2-methyl-1,3,5-triazine with N-chlorosuccinimide (J. Org. Chem., 29.
Vol., Pp. 1527-1537), 3,5-dichloro-6-
Methyl-1,2,4-triazine (J. Med. Chem., 10
Vol., Pp. 883-887), 3-chloro-6-methyl-1,2,4,5-tetrazine (J. Org. Chem., Vol. 46, 5
Similarly, pp. 102-5109) can be chlorinated by reaction with N-chlorosuccinimide.

Compounds of the general formula (IV) are described in West German Patent Publication No. 2,732,660 and French Patent No. 1,499,
The compound described in No. 785. Specific examples thereof include ethylenediamine and trimethylenediamine (also known as 1,3-diaminopropane).

In the above production method b), the compound of the general formula (V) as a raw material includes both known and novel compounds. And as specific examples thereof, for example, 4-pyrimidine carbaldehyde, 2-methyl-4-pyrimidine carbaldehyde, 2-methyl-6-oxo-1H, 6H-dihydropyrimidine-4-carbaldehyde, 5-pyrimidine carbaldehyde , 2-methyl-5-pyrimidine carbaldehyde, 2-dimethylamino-5-pyrimidine carbaldehyde, 2,4,6-trichloro-5-pyrimidine carbaldehyde, pyrazyl carbaldehyde, acetylpyrazine, 2-methyl-5- Pyrazine carbaldehyde, 3-pyridazine carbaldehyde, 2-chloro-4-pyrimidine carbaldehyde, 4-chloro-6-pyrimidine carbaldehyde, 4-methyl-6-pyrimidine carbaldehyde,
2-fluoro-5-pyrimidine carbaldehyde, 5-acetyl-2-fluoropyrimidine, 2-chloro-5-pyrimidine carbaldehyde, 2-isopropyl-5-pyrimidine carbaldehyde, 2-chlorodifluoromethyl-
5-pyrimidine carbaldehyde, 2-trifluoromethyl-5-pyrimidine carbaldehyde, 2-bromodifluoromethyl-5-pyrimidine carbaldehyde, 2-methoxy-5-pyrimidine carbaldehyde, 2-difluoromethoxy-5-pyrimidine carbaldehyde , 2-tolufluoromethoxy-5-pyrimidine carbaldehyde, 2-
(2,2,2-tolufluoroethoxy) -5-pyrimidine carbaldehyde, 2-methylthio-5-pyrimidine carbaldehyde, 2-ethylthio-5-pyrimidine carbaldehyde, 2-difluoroethylthio-5-pyrimidine carbaldehyde, 2-trifluoromethylthio-5-pyrimidine carbaldehyde, 2-nitro-5-pyrazine carbaldehyde, 2-cyano-5-pyrazine carbaldehyde, 2-chloro-5-pyrazine carbaldehyde, 2-trifluoromethyl-5- Pyrazine carbaldehyde, 3-
Fluoro-6-pyridazine carbaldehyde, 3-methyl-6-pyridazine carbaldehyde, 4-pyridazine carbaldehyde, 3-chloro-6-pyridazine carbaldehyde, 3-trifluoromethyl-6-pyridazine carbaldehyde, 1,3, 5-triazine-2-carbaldehyde,
3-chloro-1,2,4-triazine-6-carbaldehyde, 3,5-dichloro-1,2,4-triazine-6-carbaldehyde, 3-chloro-1,2,4,5-tetrazine- 6-carbaldehyde etc. can be illustrated.

The aldehydes exemplified above are generally obtained by reducing the corresponding carboxylic acid and its ester, or by the Vilsmeyer reaction, which is a conventional method. In many cases, the compound of general formula (V) can be directly synthesized by ring synthesis. For example, for 4-pyrimidinecarbaldehyde, the reaction of diethoxyacetylacetone with S-methylisothiourea gives the corresponding 2-methylthio-4-methyl-6-pyrimidinecarbaldehyde acetal, which is further reduced and Treatment with hydrochloric acid gives 4-methyl-6-pyrimidinecarbaldehyde. In this reaction, if a derivative of diethoxyacetylacetone is used, similar compounds such as 4-pyrimidine carbaldehyde, 2-methyl-4-pyrimidine carbaldehyde, 2-trifluoromethyl-4-pyrimidine carbaldehyde and the like can be synthesized. You can (Chem.B
er., 97, 3407-3417). Many known synthetic methods of 5-pyrimidine carbaldehydes are known in the field of organic chemistry. For example, 4-hydroxy-6
The -oxodihydropyrimidine was introduced into the 5-position by a Vilsmeyer reaction to introduce a formyl group, which was then halogenated to give 4,6-dichloro-5-formylpyrimidine, which was further dehalogenated to give 5 -Pyrimidine carbaldehyde can be synthesized (Liebig
s Ann. Chem., 766, 73-83, Monatsh, Che
m., 96, pp. 1567-1572). By applying this reaction, 2-alkyl-substituted or 2-haloalkyl-substituted 5-pyrimidinecarbaldehyde can be synthesized. 2-
5-Pyrimidinecarbaldehyde having another substituent at the position is described in JP-A-59-59669.

For example, {2-[(dimethylamino) methylene] propanediylidene} bis [dimethylaminoperchlorate] (Collect. Czech, Chem. Comm., Vol. 30, 21
(Described on page 25) with a suitable amidine hydrochloride,
5-Pyrimidinecarbaldehydes having a substituent such as alkyl, alkoxy, alkylthio and alkylamino at the 2-position can be obtained.

5-Pyrimidinecarbaldehydes having a halogen at the 2-position are, for example, ethyl 2-oxo-1,2.
-Dihydro-5-pyrimidine carboxylate was chlorinated with phosphorus oxychloride to give ethyl 2-chloro-5-pyrimidine carboxylate (Chem.Pharm.Bull., 12
Vol., Pp. 804-808, similar example J. Org. Chem., Vol. 29,
1740-1743), and by reducing it by a conventional method, 2-chloro-5-pyrimidinecarbaldehyde can be obtained. Furthermore, since the 2-position chloro atom is active,
With potassium fluoride, it can be converted into another substituent such as a 2-fluoro compound.

For pyridazine carbaldehydes,
3- and 4-pyridazine carbaldehyde is Monastsh.Ch
Em., 108, 213, methyl-substituted pyridazine carbaldehydes, J. Heterocycle. Chem .., 17, 15
It is described on page 01.

As the reducing agent in the production method b), complex metal hydrides such as sodium borohydride and lithium aluminum hydride can be mentioned.

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, is
o-propanol, butanol, ethylene glycol:
Mention may be made of esters such as ethyl acetate, amyl acetate: acid amides such as dimethylformamide, dimethylacetamide; sulfones, sulfoxides such as dimethylsulfoxide, sulfolane; and bases such as pyridine.

The above method can be carried out within a wide temperature range. Further, the reaction is preferably carried out under normal pressure, but it is also possible to operate under increased pressure or reduced pressure.

In carrying out the above-mentioned production method a), for example, by reacting 1 mol of the compound of general formula (III) with the compound of general formula (IV) in excess, for example, about 5-fold molar amount, and The reaction temperature is, for example, 0 to 50 ° C.
It can be easily carried out by carrying out within the range.

In carrying out the above-mentioned production method b), as shown in the Examples below, the mixture is heated to reflux in an inert solvent (benzene or the like), and then the Schiff base or imines as an intermediate product is separated. The desired compound of general formula (II) can be obtained by directly reducing the compound by a conventional method without performing the above.

In carrying out the above-mentioned production method b), for example, 1 mol of the compound of the general formula (V) is used for the general formula (I).
It is preferable to react the compound of V) in excess, for example, to react it in a molar amount of about 5 times, and the reaction temperature is usually in the range of 0 to 100 ° C. under normal pressure.

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.

[0045]

[Example] Example 1

[0046]

[Chemical 19]

Ethylenediamine (60 g) was dissolved in benzene (200 ml), and 5-formylpyrimidine (2
1.6 g) is added at room temperature. Then, it heats and it is made to heat and reflux for 3 hours, taking azeotropic water. After the reaction, benzene and excess ethylenediamine are distilled off under reduced pressure, and the residue is dissolved in ethanol (200 ml). Sodium borohydride (8.4 g) is added to this solution in small portions at room temperature, followed by stirring for 5 hours at room temperature. Ethanol is distilled off under reduced pressure, dichloromethane (100 ml) is added to the residue, and dichloromethane-soluble matter is separated. When dichloromethane was distilled off under reduced pressure from the dichloromethane layer, colorless oily N- (5-pyrimidinylmethyl) ethylenediamine (2
5.8 g) are obtained. n _D ²⁵ 1.5532 Example 2

[0048]

[Chemical 20]

Ethylenediamine (30 g) was dissolved in acetonitrile (200 ml), and this solution was added at 5-10 ° C.
At this point, pyrazinylmethyl chloride (12.9 g) is added dropwise. After the dropping, the mixture was stirred at room temperature for 1 hour, 50% aqueous sodium hydroxide solution (8 g) was then added, and then 5 mmH.
After removing the volatiles at a bath temperature of 60 ° C., the inorganic salt is filtered off to obtain colorless oily N- (pyrazinylmethyl) ethylenediamine (14.1 g). n _D ²⁰ 1.5359 Formula (II) according to the same method as in Example 1 or 2 above.
The following Table 1 shows typical examples of the compound.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

[Table 3]

[0053]

[Table 4]

[0054]

[Table 5]

Example 3 (reference example)

[0056]

[Chemical 21]

3-chloro-6-methylpyridazine (3.
9 g), N-chlorosuccinimide (4 g), carbon tetrachloride (30 ml) are added catalytic amount of α, α'-azobis (isobutyronitrile) and the mixture is refluxed for 8 hours. After cooling to room temperature, the insoluble material is filtered off, and the filtrate is concentrated under reduced pressure to give the desired 3-chloro-6-pyridazinylmethyl chloride (4.2 g). This is about 78% pure
It was. nmr (CDCl ₃ ) δ = 4.89 (2H),
7.56 (1H), 7.73 (1H) In the same manner as in Example 3 above, 2-chloro-5-pyrimidinylmethyl bromide was prepared from 2-chloro-5-methylpyrimidine and N-bromosuccinimide. Is obtained.
nmr (CDCl ₃ ) δ = 4.43 (2H), 8.66
(2H). In addition, 2-chloro-5-methylpyrazine and N
2-Chloro-5-pyrazinylmethyl chloride is obtained from -chlorosuccinimide. nmr (CDC
l ₃ ) δ = 4.73 (2H), 8.58 (2H) A synthesis example of an insecticidal nitromethylene derivative which can be produced using the diamine of the present invention is shown below.

Example 4 (reference example)

[0059]

[Chemical formula 22]

N- (5-pyrimidinylmethyl) ethylenediamine (15.2 g), 1-nitro-2,2-bis (methylthio) ethylene (14.9 g), ethanol (10
0 ml) of the mixture is refluxed with stirring until the evolution of methyl mercaptan ceased (about 3 hours). After cooling to room temperature, the formed crystals were collected by filtration, washed with ethanol, and dried to give pale yellow 1- (5-pyrimidinylmethyl) -2- (nitromethylene) imidazolidine (1
2.7 g) are obtained, which decomposes at 236 ° C.

Table 2 shows typical examples of the insecticidal nitromethylene derivatives obtained by using the diamines of the general formula (II) of the present invention as raw materials.

[0062]

[Table 6]

[0063]

[Table 7]

[0064]

[Table 8]

[0065]

[Table 9]

Next, as usefulness of the diamines of the present invention,
The insecticidal efficacy test of the obtained insecticidal nitromethylene derivative is illustrated by using it as a raw material.

Biological test: -Comparative compound A-1:

[0068]

[Chemical formula 23]

Compound described in West German Patent Publication No. 2,514,402 Example 5 (Biological test) Test for organophosphorus agent resistant leafhopper leafhopper Preparation of test reagent solution Solvent: xylol 3 parts by weight Emulsifier: polyoxyethylene alkylfru 1 part by weight of ether ether 1 part by weight of the active compound is mixed with said 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 above having 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. Insect kill rates were calculated.

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

[0072]

[Table 10] Example 6 (Biological test) Test for planthoppers Test method: Plant height 10 cm planted in pot with diameter 12 cm
10 ml of each pot was sprayed with a diluted solution of the active compound prepared in the same manner as in Example 5 in water.
After drying the sprayed drug solution, a wire net with a diameter of 7 cm and a height of 14 cm is covered, and 30 female adult planthoppers of the strain that are resistant to the organophosphorus agent are released into the wire net and the number of dead insects is set after 2 days in a temperature-controlled room. Insect kill rates were calculated.

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

[0074]

[Table 11] Example 7 (Biological test) Test for organophosphorus 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 phosphorus agent and carbamate-resistant peach aphid bred to eggplant seedlings (genuine long eggplants) of m were inoculated per seedling, and one day after the inoculation, one of the active compounds prepared as in Example 5 was prepared. A water-diluted solution having a predetermined concentration was sprayed using a spray gun. After spraying, leave it in a greenhouse 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.

[0076]

[Table 12]

[0077]

INDUSTRIAL APPLICABILITY The novel diamines of the present invention are useful as intermediates for producing insecticidal nitromethylene derivatives.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07D 239/34 8615-4C 239/36 8615-4C 239/38 8615-4C 239/42 Z 8615- 4C 241/12 241/16 241/24 251/16 253/06 257/02

Claims (3)

[Claims] 1. A general formula: In the formula, R represents a hydrogen atom or an alkyl group, Z represents a hetero 6-membered cyclic group containing at least two nitrogen atoms, wherein the ring is an alkyl group, a halogen atom, a haloalkyl group,
May be substituted with at least one selected from an alkoxy group, an alkylthio group, a haloalkoxy group, a haloalkylthio group, an oxo group, a nitro group, a cyano group and a dialkylamino group, and m represents 2 or 3. Diamines. 2. A general formula: In the formula, R represents a hydrogen atom or an alkyl group, Z represents a hetero 6-membered cyclic group containing at least two nitrogen atoms, wherein the ring is an alkyl group, a halogen atom, a haloalkyl group,
May be substituted with at least one selected from an alkoxy group, an alkylthio group, a haloalkoxy group, a haloalkylthio group, an oxo group, a nitro group, a cyano group and a dialkylamino group, and Hal represents a halogen atom. A compound represented by the following general formula: H ₂ N— (CH ₂ ) m—NH _{2 wherein} m is 2 or 3 is represented by the following general formula: [Chemical 4] In the formula, R represents a hydrogen atom or an alkyl group, and Z is a nitrogen atom.
6-membered heterocyclic group containing at least two children, wherein
The ring has an alkyl group, a halogen atom, a haloalkyl group,
Alkoxy group, alkylthio group, haloalkoxy group, ha
Roalkylthio group, oxo group, nitro group, cyano group and
At least one selected from dialkylamino groups
Optionally substituted , and m represents 2 or 3,
A method for producing the diamine represented. 3. A general formula: 5] In the formula, R represents a hydrogen atom or an alkyl group, and Z represents a 6-membered heterocyclic group containing at least two nitrogen atoms,
Here, the ring is substituted with at least one selected from an alkyl group, a halogen atom, a haloalkyl group, an alkoxy group, an alkylthio group, a haloalkoxy group, a haloalkylthio group, an oxo group, a nitro group, a cyano group and a dialkylamino group. A compound represented by
General formula: [Other 6 H ₂ N- (CH ₂₎ in m-NH ₂ formula, and m is reacting a shows a 2 or 3, a compound represented by the general formula: 7] Wherein, R, and Z and m yield a compound identical in represented above, and then, which comprises reducing this general
Formula: 8] In the formula, R represents a hydrogen atom or an alkyl group, and Z is a nitrogen atom.
6-membered heterocyclic group containing at least two children, wherein
The ring has an alkyl group, a halogen atom, a haloalkyl group,
Alkoxy group, alkylthio group, haloalkoxy group, ha
Roalkylthio group, oxo group, nitro group, cyano group and
At least one selected from dialkylamino groups
Optionally substituted , and m represents 2 or 3,
A method for producing the diamine represented.