KR0173084B1 - Method for the purification of triamine compound - Google Patents

Abstract

The present invention relates to a method for purifying 1,17-diamino-9-azaheptadecane represented by the following structural formula (I).

Description

Purification Method of Triamine Compound

The present invention relates to a method for purifying a triamine compound, and more particularly, to a method for purifying 1,17-diamino-9-azaheptadecane represented by the following structural formula (I).

The compound of formula (I) is 1,1`-aminodi represented by the following structural formula (II), which is well known as a fungicide useful for controlling black star pattern disease of apples, gray mold disease of grapes, gray ash pattern of peach, etc. As a synthetic intermediate of octamethylene) diguanidium triacetate, it is prepared by reacting octamethylenediamine represented by the following structural formula (III) under an acid catalyst.

However, since the reaction generates not only Structural Formula (I), which is a submer of Structural Formula (III), but also other by-products including the following Structural Formula (IV), which is a trimer, the purification method of Structural Formula (I) is very important.

For example, in European Patent Publication No. 013554, the compound of formula (I) is purified by distillation under reduced pressure, but since its boiling point and melting point are high, distillation requires high temperature and high vacuum, and it is accompanied by other problems. There are many inadequate methods.

That is, one of the methods for purifying the patent publication is a high vacuum apparatus and a high temperature reactor because the high boiling point of the compound of formula (I) is purified by distillation of the compound of formula (I) at high temperature under reduced pressure at a temperature of 190-220 ° C. and a pressure of 4 mmHg. An apparatus is required, and due to the high melting point of the compound of formula (I), a distillation tube and a thermostat of various equipment are required.

Therefore, the present inventors have been researching to solve the problems according to the above-mentioned known methods and to find a more suitable purification method, and to prepare the target compound in high yield using the difference in solubility and the inorganic salts generally used in organic solvents. It has been found that the surprising fact that it can be completed to complete the present invention.

In the present invention, impure triamine (tri / tetra = 80/20) is added to toluene, heated to completely dissolve it, and then an inorganic salt is added, and the resulting tetramine solid is removed by filtration to obtain 1, the following structural formula (I). A method for purifying 17-diamino-9-azaheptadecane.

Hereinafter, the purification method of the present invention will be described in detail.

The present invention utilizes a general inorganic salt which helps the triamine represented by the following structural formula (I) to assist in the solubility difference of the organic solvent and the crystallinity of impurities.

Impure triamine (tri / tetra = 80/20) is placed in an appropriate amount of toluene, heated to complete dissolution, and gradually cooled to remove impurities (tetra) produced by filtration.

At this time, it is used as a catalyst to increase the crystallization of impurities by adding a general inorganic salt.

Toluene is used as the organic solvent according to the present invention, and the amount of toluene is used in a weight ratio of 4 to 10 times based on the mixture with the following formula (I) before purification, preferably in a weight ratio of 5 to 7 times. do.

The inorganic salt may be sodium chloride, sodium bromide, sodium nitrate, sodium carbonate, sodium sulfate, sodium chloride, potassium chloride and the like, but sodium chloride or sodium nitrate is particularly preferred. The amount of the inorganic salt used is 0.3 to 3.0% of the organic solvent, preferably 0.5 to 1.5%.

Purification may be carried out in a temperature range of 20 ~ 40 ℃, preferably, it is carried out at 25 ~ 35 ℃.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1

Purification of Pure Triamine (I) from Triamine (I) and Tetramin (IV) Mixtures

150 g of toluene was added to 25 g of a mixture containing 80% of 1,17-diamino-9-azaheptadecane and 20% of the subcomponent including Structural Formula (IV). 1.0 g of sodium chloride was added thereto, stirred for 30 minutes, and then slowly cooled to 4 DEG C for 30 hours.

At this time, confirm that the compound of the structural formula (IV) and the other minor components are solidified, and further stirred for 1 hour. The resulting solid was filtered to distill the filtrate toluene to obtain 19.1 g of the target compound as white crystals (yield: 95.5%, gas chromatography purity: 95.4%).

Example 2

Purification of Pure Triamine (I) from Triamine (I) and Tetramin (IV) Mixtures

Purification was carried out in the same manner as in Example 1, and 1.0 g of sodium nitrate was used instead of sodium chloride to obtain 19.2 g of the target compound as white crystals (yield: 96.1%, gas chromatography purity: 95.8%).

Example 3

Purification of Pure Triamine (I) from Triamine (I) and Tetramin (IV) Mixtures

150 g of toluene contains 70 g of 1,17-diamino-9-azaheptadecane and 30 g of a mixture containing 30% of the minor components including Structural Formula (IV), followed by purification in the same manner as in Example 1). 16.5 g of 17-diamino-9-azaheptadecane was obtained as white crystals. (Yield: 94.3%, gas chromatography purity: 94.8%)

Claims (8)

Impure triamine (tri / tetra = 80/20) was added to toluene and heated to complete dissolution. Then, an inorganic salt was added, and the resulting tetramine solid was removed by filtration to give 1,17-dia of formula (I) Method for Purifying Mino-9-Azaheptadecane. The method according to claim 1, wherein the amount of toluene used is 4 to 10 times by weight based on the mixture with structural formula (I) before purification. The method according to claim 2, wherein the amount of toluene used is 5 to 7 times by weight based on the mixture with the structural formula (I) before purification. The method of claim 1 wherein the inorganic salt is sodium chloride, sodium bromide, sodium nitrate, sodium carbonate, sodium sulfate, sodium chloride or potassium chloride. The method according to claim 1, wherein the amount of the inorganic salt used is 0.3 to 3.0% of toluene. The method according to claim 5, wherein the amount of the inorganic salt used is 0.5 to 1.5% of toluene. The method of claim 1 wherein the purification is carried out in a temperature range of 20-40 ° C. 8. The process of claim 7, wherein the purification is carried out at 25-35 ° C.