JP3486669B2 - Tetraamino compound and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a tetraamino compound and a method for producing the same.

[0002]

2. Description of the Related Art The inventors of the present invention are novel compounds 1, 4, 5, 8 which can be used as monomers for polysulfides and polythioesters, raw materials for producing surfactants, and materials for collecting heavy metals. -Invented a tetrakis (mercaptomethyl) naphthalene compound (Patent No. 1771)
No. 811, Japanese Patent Publication No. 4-63063). Similarly, 1,4,5,8-tetrakis (hydroxymethyl)
Invented a naphthalene compound (Patent No. 2099138
No. 8-2821). These compounds are
Both of them have a mercaptomethyl group (—CH ₂ SH) and a hydroxymethyl group (—CH ₂ O) as a substituent at the peri position of the naphthalene ring (positions 1, 8 and 4,5 of naphthalene).
H). However, as the substituent, an aminomethyl group (-CH ₂ N as a hetero substituent) is used.
H ₂ ), or N, N further substituted with an aminomethyl group
The tetraamino compound in which the two peri-positions of the naphthalene ring are substituted with a di-substituted aminomethyl group is expected to have a wide range of uses as various chemical raw materials and functional materials as described above, It is still unknown, mainly due to the existence of difficulties in synthetic chemistry.

[0003]

An object of the present invention is to provide a tetraamino compound which is a novel compound and a method for producing the same.

[0004]

Means for Solving the Problems The present inventors have diligently studied the above-mentioned problems, and when a tetrahalogeno compound, which is a bisperi-substituted form of naphthalene, is reacted with a secondary amine represented by HNR ₂ , It has been found that a tetraamino compound in which the alkenylation reaction can be smoothly proceeded and an aminomethyl group or an N, N-disubstituted aminomethyl group as a hetero substituent is substituted at the peri position of the naphthalene ring is obtained. Has been completed.

According to the present invention, the following inventions are provided. (1) A tetraamino compound represented by the following general formula (I).

[Chemical 4] (In the formula, R represents a butoxycarbonyl group, or
Two R's combine to represent a phthaloyl group . X represents an atom or a group selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkenyl group, an aralkyl group, an alkoxy group, an aryloxy group, a nitro group and a carboxyl group. ) (2) A tetrahalogeno compound represented by the following general formula (II) is used as a secondary amine represented by HNR ₂ in the presence of a base, or a secondary amine in which a hydrogen atom of the secondary amine is replaced with a metal atom. A method for producing a tetraamino compound, which comprises reacting with a secondary amine salt to produce a tetraamino compound represented by the above general formula (I).

[Chemical 5] (In the formula, Y represents a halogen atom. X is selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkenyl group, an aralkyl group, an alkoxy group, an aryloxy group, a nitro group, and a carboxyl group. Indicates an atom or group.)

[Chemical 6] (In the formula, R represents a butoxycarbonyl group, or
Two R's combine to represent a phthaloyl group . X represents an atom or group selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkenyl group, an aralkyl group, an alkoxy group, an aryloxy group, a nitro group and a carboxyl group. )

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The novel tetraamino compound of the present invention is represented by the following general formula (I).

[Chemical 7] (In the formula, R represents a butoxycarbonyl group, or
Two R's combine to represent a phthaloyl group . X represents an atom or a group selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkenyl group, an aralkyl group, an alkoxy group, an aryloxy group, a nitro group and a carboxyl group. )

The characteristic feature of the tetraamino compound represented by the general formula (I) is that the two peri-positions of the naphthalene ring are substituted with aminomethyl groups or N, N-disubstituted aminomethyl groups.

Next, the tetraamino compound of the present invention will be specifically described. The N, N-disubstituted aminomethyl group of the tetraamino compound represented by the general formula (I) (-
R which is a substituent of CH ₂ NR ₂ ) is butoxycarboni
Group, or two R's are joined to represent a phthaloyl group .

The substituent X substituted on the naphthalene nucleus of the tetraamino compound represented by the general formula (I) is
It represents an atom or a group selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkenyl group, an aralkyl group, an alkoxy group, an aryloxy group, a nitro group and a carboxyl group. Specific examples of the halogen atom include chlorine, iodine, bromine, and fluorine. The alkyl group has a general formula C having 1 to 10 carbon atoms.
It is a group represented by _n H _{2n + 1} . These are linear or branched and may be substituted with an alkyl group. Specifically, methyl, ethyl, n- or i-propyl, n- or i-butyl, n-
Alternatively, an i-pentyl group, a neopentyl group, or the like can be given. The aryl group is an aromatic hydrocarbon group. Specifically, a phenyl group, a tolyl group, a xylyl group,
Examples thereof include cumenyl group, mesityl group, biphenyl group and naphthyl group. The heterocyclic group is a group composed of a cyclic compound containing nitrogen, sulfur, oxygen and the like as different atoms constituting the ring. Specifically, a pyrrolyl group, a pyrrolinyl group, a pyrrolidinyl group, a pyridyl group, a pyrimidinyl group,
Examples thereof include pyridazinyl group, pyrazolyl group, pyrazolidinyl group, pyrazolinyl group, imidazole group, quinazolinyl group, quinolyl group, acridinyl group, triazinyl group, indolyl group, thienyl group, furyl group and pyranyl group. The alkenyl group _is a group represented by C _{n H 2n-1.} It may be linear or branched. The position of the double bond may be at the end or in the middle thereof. The number of carbon atoms can be appropriately set and used as necessary, but usually about 1 to 10 is used. The aralkyl group is a group in which a hydrogen atom of an aromatic hydrocarbon is replaced with an aliphatic hydrocarbon, and specific examples thereof include a benzyl group and a phenethyl group. The alkoxy group is a group represented by C _n H _{2n + 1} O in which an alkyl group is bonded to oxygen, and specifically, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group. Etc. can be mentioned. The aryloxy group is a group in which an O atom is bonded to an aromatic hydrocarbon, and specific examples thereof include a phenyloxy group, a tolyloxy group and a xylyloxy group. The nitro group is a group represented by NO ₂ . The carboxyl group is a group represented by COOH.

The tetraamino compound, the method for producing the same, and the method for producing the tetraamino compound of the present invention will be described below. The raw material is a tetrahalogeno compound represented by the following general formula (II), which is a known compound.

[Chemical 8] (In the formula, Y represents a halogen atom. X is selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkenyl group, an aralkyl group, an alkoxy group, an aryloxy group, a nitro group, and a carboxyl group. An atom or a group is shown.) The method for producing the tetrahalogeno compound is as follows. Naphthalene tetracarboxylic acid is esterified by treating it with dimethyl sulfate in an alkaline solution to give naphthalene tetracarboxylic acid tetramethyl ester.
It can be obtained by reduction treatment to produce tetrakis (hydroxymethyl) naphthalene and halogenating it (1,4,5,8-tetrakis (halogenomethyl) naphthalene. JP-B-4-63063). In the halogen atom of the tetrahalogeno compound, which is the raw material,
It is used by appropriately selecting from chlorine, bromine, iodine and fluorine. Usually, bromine and chlorine are used in consideration of easy availability of raw materials and convenience of handling.

The other raw material is a secondary amine represented by the general formula HNR ₂ . The NR ₂ group constitutes the N, N-di-substituted aminomethyl group of the tetraamino compound which is the target substance of the present invention. As the R group,
Represents a butoxycarbonyl group or two R are bonded
Represents a phthaloyl group .

The tetraamino compound of the present invention is obtained by adding the above-mentioned general formula NHR to the tetrahalogeno compound which is the starting material.
The secondary amine represented by ₂ is reacted, by dehydrohalogenation, can be produced. The reaction formula is shown below.

[Chemical 9] As the reaction temperature, a temperature in a state of being heated from room temperature is adopted. Specifically, a temperature in the range of room temperature to 130 ° C. is adopted. The reaction time is generally 20 to 30 hours. During the reaction, it is preferable to constantly stir the reaction solution in order to improve the reaction yield.

This reaction is for dehydrohalogenation, and it is effective to allow a base to exist in the reaction system.
Examples of the base include metal hydrides such as sodium hydride and potassium hydride, sodium methoxide, potassium-
Examples thereof include metal alkoxides such as t-butoxide and metal amides such as sodium amide and potassium amide. Also, instead of using a base and a secondary amine,
A secondary amine in which the hydrogen atom of a secondary amine is replaced with a metal atom.
A primary amine salt (for example, phthalimido potassium or the like) can be used. As the organic solvent, alcohols, ethers, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, aprotic polar solvents, and mixed solvents thereof are used. Specific examples of alcohols include methanol, ethanol, 2-propanol, t-butanol, and t-pentanol. Examples of ethers include dimethoxyethane, dioxane, tetrahydrofuran and the like. Examples of the aromatic hydrocarbon solvent include benzene and toluene. Examples of the halogen-based hydrocarbon solvent include dichloromethane and chloroform. Examples of the aprotic solvent include dimethylformamide, acetonitrile, HMPA and the like.

For the purification of the reaction product obtained by the above method and the confirmation of the target product, a method appropriately selected from conventionally known methods is used. An example of a specific method is as follows. After completion of the reaction, the reaction product is taken out, and recrystallization is repeated using an extraction solvent to carry out a purification treatment. A known solvent is appropriately used for the extraction solvent. To give an example thereof, specifically, a methanol-water solvent is used. The target product purified by such a method has a colorless fine needle-like shape and is confirmed by melting point measurement, infrared absorption measurement and NMR measurement.

The desired product of the present invention is a novel compound. This compound is used as a raw material for producing a compound having a new skeleton, a raw material for producing a polyamino compound, a monomer for producing a polyamide, a raw material for a heavy metal scavenging material composed of a cation and an amphoteric surfactant or a cyclic compound having a host function. It can be used. An example of the case of using as a raw material for producing a compound having a new skeleton is to react with an acylating agent to produce a bispericyclic compound. Similarly, as an example of producing a polyamino compound, it is possible to produce a polyamine compound in which a polyamide is acylated to reduce the polyamide and the peri bond is crosslinked to reduce the polyamide.

[0016]

EXAMPLES Examples showing the contents of the present invention will be shown below. The present invention is not limited to this. Example 1 0.50 g of 1,4,5,8-tetrakis (bromomethyl) naphthalene (wherein Y is Br in the compound represented by the general formula (II)) was treated with a secondary amine ( HN (COOt-Bu) ₂ ) 1.20 g and sodium hydride 0.23 g together with dimethylformamide 2
The mixture was added to 4 ml, and the reaction was continued for 20 hours while stirring at 55 ° C. for 24 hours and then at room temperature. After the reaction was completed, a reddish brown solution was obtained. The product thus obtained was recrystallized from a mixed solvent of methanol and water to obtain 0.62 g (yield 60%) of colorless fine needle-shaped crystalline substance. The properties of the obtained substance were as described below. As a result, the target product is a tetraamino compound (when R is C00t-Bu in the general formula (I)).
Was confirmed. Mp: 188 ° C. Rf (SiO ₂ / benzene / ethyl acetate): 0.
38 IR (Nujo1): 1756, 1698, 137.
^{0,1115,855 cm -1 1 H-NMR (} CDCl 3): δ = 1.33s (72
_{H, CH 3) 5.25s (8H} , ArCH 2 N) 7.27s (4H, ArH) 13 C-NMR (CDCl 3): δ = 27.86 (C
_{H 3) 82.52 (C) 50.11} (CH 2) 152.29 (C = O) 134.15 132.95 122.72 (Ar)

Example 2 0.250 g of 1,4,5,8-tetrakis (bromomethyl) naphthalene (a compound of the general formula (II) in which Y represents Br) was added to a secondary amine salt (phthalimide). _{Cali, KN (-CO-C 6 H} 4 -CO-) 0.530g
Together with 30 ml of dimethylformamide,
The mixture was stirred at 70 ° C for 17 hours. After the reaction was completed, the resulting light brown suspension was treated with water, and the precipitated colorless solid product was filtered and collected to give a Tetraamino compound (by the general formula (I), R ₂ is a compound which represents a phthaloyl group.) 0.364 g (yield 96%) was obtained. The properties of the obtained substance were as described below. As a result, it was confirmed that the target product was a tetraaminotraamino compound (when R ₂ represents a phthaloyl group in the general formula (I)). Mp> 360 ° C. Rf (SiO ₂ / benzene / ethyl acetate): 0.
38 IR (Nujo1): 1776, 1710 cm ^-1

[0018]

According to the present invention, a novel tetraamino compound and a method for producing the same can be obtained. This compound can be used as a raw material for producing a compound having a new skeleton, a raw material for producing a polyamino compound, a monomer for producing a polyamide, a raw material for a surfactant or a heavy metal trapping material.

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Claims (2)

(57) [Claims] 1. A tetraamino compound represented by the following general formula (I). [Chemical 1] (In the formula, R represents a butoxycarbonyl group, or
Two R's combine to represent a phthaloyl group . X represents an atom or a group selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkenyl group, an aralkyl group, an alkoxy group, an aryloxy group, a nitro group and a carboxyl group. ) 2. A tetrahalogeno compound represented by the following general formula (II) is a secondary amine represented by HNR ₂ in the presence of a base, or a hydrogen atom of the secondary amine is replaced with a metal atom. By reacting with a secondary amine salt, the following general formula (I)
The manufacturing method of the tetraamino compound characterized by manufacturing the tetraamino compound represented by these. [Chemical 2] (In the formula, Y represents a halogen atom. X is a hydrogen atom,
Halogen atom, alkyl group, aryl group, heterocyclic group,
An atom or group selected from an alkenyl group, an aralkyl group, an alkoxy group, an aryloxy group, a nitro group and a carboxyl group is shown. ) [Chemical 3] (In the formula, R represents a butoxycarbonyl group, or
Two R's combine to represent a phthaloyl group . X represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkenyl group, an aralkyl group, an alkoxy group, an aryloxy group, a nitro group or a carboxyl group. )