JP2004155692A - Method for producing amino group-substituted 1,3,5-triazines - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for industrially producing a high-purity amino group-substituted 1,3,5-triazine compound in a high yield, with which water is used as a solvent. <P>SOLUTION: In the method for producing the amino group-substituted 1,3,5-triazine by replacing the chlorine atom of a cyanuric chloride with an amino group-containing compound, the method comprises a process for simultaneously adding a deacidifying agent and an amino group-containing compound to a water-containing solution of the cyanuric chloride and carrying out the substitution in the presence of an alkali metal halide. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an improved process for producing amino-substituted 1,3,5-triazine compounds useful as reactive dyes, optical brighteners or intermediates thereof.
[0002]
[Prior art]
The condensation reaction between cyanuric chloride and an amino group-containing compound is carried out, for example, in the case of a reaction with 4,4′-diaminostilbene-2,2′-disulfonic acid or a salt thereof, usually in an aqueous solvent or an organic solvent such as acetone. In a solvent-water solvent, a cyanuric chloride finely suspended in the presence of a small amount of a nonionic surfactant as necessary is reacted with an amino group-containing compound in the presence of a phase transfer catalyst as necessary. It is known that it is advantageous to neutralize hydrogen chloride produced by the reaction with a deoxidizing agent and to proceed from weakly acidic to weakly alkaline.
As the deoxidizing agent, hydroxides, carbonates, acid carbonates, phosphates, borates, formates, acetates, etc. of alkali metals, oxides and carbonates of alkaline earth metals or zinc, Examples include tertiary amines such as phosphates and borates, and urea, which are used after hydrogen chloride is produced or in some cases, before hydrogen chloride is produced.
The temperature of the substitution reaction is desirably in the range of 0 to 15 ° C, 20 to 40 ° C, and 70 to 100 ° C for the first chlorine atom, the second chlorine atom, and the third chlorine atom of cyanuric chloride, respectively. It has been known. (See Patent Documents 1 to 8)
[0003]
[Patent Document 1]
JP-A-49-32923 [Patent Document 2]
JP-A-47-39217 [Patent Document 3]
JP-A-48-7922 [Patent Document 4]
JP-A-56-2975 [Patent Document 5]
Japanese Patent Publication No. 45-772 [Patent Document 6]
JP-B-53-6170 [Patent Document 7]
JP-A-47-39210 [Patent Document 8]
JP-A-49-5126
[Problems to be solved by the invention]
However, in the method in which the deoxidizing agent is added after the addition of the amino group-containing compound, when the scale is increased, the viscosity of the reaction system increases and stirring becomes difficult. There is a problem that a substituent such as a chlorine atom is partially hydrolyzed.
In the method of reacting a deoxidizing agent with an amino group-containing compound in the presence of cyanuric chloride, it is necessary to carry out the reaction in a two-phase system using an organic solvent so that the cyanuric chloride is not hydrolyzed. To be used, which is industrially disadvantageous.
An object of the present invention is to provide a method in which water can be used as a solvent and an amino-substituted 1,3,5-triazine compound can be industrially produced with high yield and purity.
[0005]
Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, searched for an additive that suppresses an increase in viscosity by devising a method of adding an amino group-containing compound and a deoxidizing agent to cyanuric chlorides. As a result, they have found that the above problems can be solved, and have completed the present invention.
[0006]
That is, the present invention
(1) A method for producing an amino-substituted 1,3,5-triazine by substituting a chlorine atom of a cyanuric chloride with an amino group-containing compound, wherein a deoxidizer and an amino group-containing compound are added to a water-containing solution of the cyanuric chloride. A method for producing an amino-substituted 1,3,5-triazine characterized by having a step of simultaneously adding
(2) In the step of simultaneously adding a deoxidizing agent and an amino group-containing compound to a water-containing solution of cyanuric chlorides, the pH is adjusted to 7 or less, and the step is carried out. , 3,5-triazine production method,
(3) a step of adding 40 to 90% of a necessary equivalent of an amino group for substituting a chlorine atom to a water-containing solution of cyanuric chloride in advance, and then simultaneously adding a deoxidizing agent and an amino group-containing compound. The method for producing an amino-substituted 1,3,5-triazine according to (1) or (2), wherein
(4) The method according to any one of (1) to (3), wherein the water-containing solution of cyanuric chlorides is a suspension in which cyanuric chlorides are dispersed in an aqueous solvent in the presence of a surfactant. The present invention relates to a method for producing an amino-substituted 1,3,5-triazine.
[0007]
(5) A method for producing an amino-substituted 1,3,5-triazine by reacting a chlorine atom of cyanuric chloride with an amino group-containing compound and a deoxidizing agent in a water-containing solvent in the presence of an alkali metal halide A method for producing an amino-substituted 1,3,5-triazine characterized by performing
(6) The method for producing an amino-substituted 1,3,5-triazine according to any one of (1) to (5), wherein the deoxidizing agent is an alkali metal hydroxide.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
The cyanuric chloride used in the present invention refers to cyanuric chloride or a 1,3,5-triazine compound in which one or two chlorine atoms of cyanuric chloride are substituted, and as such a substituent, a methoxy group An ethoxy group, an n-propoxy group, an alkoxy group such as an isopropoxy group, an aryloxy group such as a phenoxy group and a naphthyloxy group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, and an N- group such as anilino group. Examples thereof include a substituted amino group. In particular, the method of the present invention can be suitably used for a substituent which is susceptible to hydrolysis by a deoxidizing agent.
[0009]
The amino group-containing compound used in the present invention is not particularly limited as long as it has a primary or secondary amino group capable of substituting for a chlorine atom of cyanuric chloride in the molecule. Is not particularly limited. Specifically, aniline, 1-aminobenzene-2,5-disulfonic acid or a salt thereof, metanilic acid or a salt thereof, 4,4′-diaminostilbene-2,2′-disulfonic acid or a salt thereof, sulfamine, etc. Examples can be given.
[0010]
The production method of the present invention is characterized by including a step of simultaneously adding a deoxidizing agent and an amino group-containing compound to a water-containing solution of cyanuric chlorides. By using such an addition method, an increase in the viscosity of the reaction system can be suppressed, and the pH in the reaction system can be easily adjusted by adding a deoxidizing agent.
As the water-containing solution of cyanuric chlorides, specifically, as a solvent, water or a solution using a mixed system of water and an organic solvent such as acetone can be exemplified. Since it is desirable to use a system that does not use water, it is preferable to use only water as the solvent. In the case where water is used as a solvent, it is preferable to disperse cyanuric chlorides finely in water by using a surfactant in order to perform the reaction more smoothly. Further, as such a surfactant, a nonionic surfactant can be exemplified.
The pH of the reaction system is preferably adjusted to 7 or less, and more preferably to 6 or less in order to prevent hydrolysis of the raw materials and products.
[0011]
As the deoxidizing agent to be used, specifically, the above-mentioned known compounds can be used. However, industrially inexpensive raw materials such as sodium hydroxide and alkali metal hydroxide such as potassium hydroxide are used in the present invention. Is industrially advantageous.
[0012]
Simultaneous addition shall include the operation of adding both without a considerable interval, other than the case of adding at the same time. The method of addition is not particularly limited, and examples thereof include a method of dropping and a method of introducing a reaction solution with a pump or the like. The addition may be continuous or may be a method of dividing and adding at considerable intervals. In any case, as described above, it is preferable to add the reaction system while controlling the pH of the reaction system to 7 or less, preferably 6 or less.
[0013]
The production method of the present invention may optionally include, before the above-mentioned simultaneous addition step, a step of adding 40 to 90% of a necessary equivalent of an amino group for substituting a chlorine atom to a water-containing solution of cyanuric chlorides in advance. Is preferred. In particular, when a compound obtained by substituting the first chlorine atom of cyanuric chloride is used, the method of the present invention can be suitably used. In this case, since the reactivity of the second chlorine atom is reduced, only the amino group-containing compound is added and reacted in advance, and then the deoxidizing agent and the amino group-containing compound are added to adjust the pH of the reaction system. It can be suppressed to 7 or less, preferably 6 or less, and the influence of the deoxidizing agent on the raw materials and products can be reduced. If the amount added in advance is 40% or less of the required equivalent, the effect of the deoxidizing agent cannot be suppressed, and if it is 90% or more, the viscosity of the reaction solution increases, and the effect of the deoxidizing agent can be similarly suppressed. Can not.
[0014]
The reaction temperature is preferably as low as possible to suppress side reactions, especially when a large amount of reactive chlorine atoms is contained. However, when the reactivity of chlorine atoms is low, it is necessary to maintain the reaction temperature at a certain level, and in that case, the production method of the present invention can be suitably used.
[0015]
Further, the production method of the present invention is characterized in that the reaction is carried out in the presence of an alkali metal halide in a reaction system. By coexisting the alkali metal halide, the viscosity of the reaction solution can be reduced, and the influence of the added deoxidizing agent can be suppressed. Specific examples of the alkali metal halide to be used include sodium chloride, sodium bromide, potassium chloride, potassium bromide and the like. The amount used is not particularly limited, but is preferably in the range of 0.05 to 0.3 g, more preferably in the range of 0.1 to 0.2 g, based on 1 g of cyanuric chloride. The alkali metal halide may be mixed with the cyanuric chloride before reacting with the amino group-containing compound, or mixed with the amino group-containing compound, or added to the cyanuric chloride at the same time as the amino group-containing compound and reacted. You may.
[0016]
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples.
[0017]
【Example】
Example 1
300 kg of cyanuric chloride (2,4,6-trichloro-1,3,5-triazine) was dispersed in 2600 l of water at 0 ° C in the presence of 0.2 kg of a nonionic surfactant, and cooled to 0 ° C. 40 kg of sodium chloride is added, and 3089 kg of a 10.5% by weight aqueous solution of sodium 4,4′-diaminostilbene-2,2′-disulfonate (DAS) and 3.9% by weight are added at 0 ° C. to 10 ° C. under stirring. % Sodium hydroxide aqueous solution was simultaneously added dropwise so that the pH of the reaction solution was in the range of 2-3. Thereafter, the temperature of the reaction solution was raised to 25 ° C. and a 3.9% by weight aqueous solution of sodium hydroxide was added dropwise so as to be in the range of pH 4 to 6, and the mixture was stirred at the same temperature for 1 hour to ripen. Was. The 3.9% by weight aqueous sodium hydroxide solution used was 1670 kg in total. There was no increase in the viscosity of the reaction solution, and sufficient stirring was possible.
A part of the reaction solution was collected, adjusted to pH 2 with sulfuric acid, sodium chloride was added, and the precipitated crystals were filtered. Various spectra were measured, and 4,4′-bis ((4,6-dichloro- It was confirmed that 1,3,5-triazin-2-yl) amino) stilbene-2,2′-disulfonic acid was almost quantitatively produced.
[0018]
An aqueous solution of sodium hydroxide was added dropwise to the reaction solution to adjust the pH to 8.5, and the temperature of the solution was raised to 60 ° C. Thereafter, 380 kg of a 15.5% by weight aqueous sodium hydroxide solution and 211.6 kg of sulfamine were simultaneously added dropwise at the same temperature so that the pH was in the range of 5 to 6, and the temperature was further raised to 70 ° C. and stirred for 1 hour. did. At the time of the dropwise addition, no increase in the viscosity of the reaction solution was observed, and the stirring was successfully performed.
Thereafter, 357 kg of diethanolamine (purity: 80%) was added dropwise, then 460 g of a 15.5% by weight aqueous sodium hydroxide solution was added dropwise, and the mixture was heated to 100 ° C. and stirred for 3 hours. The pH of the reaction solution was in the range of 7.5 to 8.5.
After the reaction solution was filtered while hot to remove insolubles, 625 kg of sodium chloride was added at a liquid temperature of 80 ° C., the mixture was cooled to 55 ° C., and the precipitated crystals and the supernatant were separated by decantation. Thereafter, the operation of further heating to 80 ° C, cooling to 50 ° C, and removing the supernatant was repeated twice to remove sodium chloride, separated by filtration, and dried to obtain 780 g of white crystals. When various spectra of the obtained crystals were measured, it was found that 4,4'-bis ((4- (bishydroxyethylamino) -6- (4-aminosulfonylanilino) -1,3,5-triazine-2- Yl) amino) stilbene-2,2'-disulfonate disodium salt. (Yield 90%)
[0019]
Example 2
293 kg of 2,4, -dichloro-6-methoxy-1,3,5-triazine were dispersed in 2600 l of water at 0 ° C in the presence of 0.2 kg of a nonionic surfactant and cooled to 0 ° C. 40 kg of sodium chloride was added, and 1545 kg of 10.5 wt% aqueous solution of DAS was added dropwise at 0 ° C. to 10 ° C. with stirring, and 1544 kg of DAS and 13.9 kg of 3.9 wt% sodium hydroxide solution were further reacted. The solution was simultaneously dropped so that the pH of the solution was in the range of 4 to 6 and the temperature was in the range of 10 to 25 ° C. Thereafter, the temperature of the reaction solution was raised to 60 ° C., and a 3.9% by weight aqueous solution of sodium hydroxide was added dropwise to adjust the pH to a range of 4 to 6, and the mixture was stirred at the same temperature for 1 hour to ripen. Was. The 3.9% by weight aqueous sodium hydroxide solution used was 1670 kg in total. There was no increase in the viscosity of the reaction solution, and sufficient stirring was possible.
A part of the reaction solution was collected, adjusted to pH 2 with sulfuric acid, sodium chloride was added, and the precipitated crystals were filtered. Various spectra were measured, and 4,4′-bis ((4-chloro-6- It was confirmed that methoxy-1,3,5-triazin-2-yl) amino) stilbene-2,2′-disulfonic acid was almost quantitatively produced.
[0020]
【The invention's effect】
As described above, by using the method of the present invention, an increase in the viscosity of the reaction solution can be suppressed, so that side reactions such as hydrolysis of raw materials or products due to the effect of the deoxidizing agent used can be suppressed. it can. Conventionally, carbonates have been used as a deoxidizing agent. However, during the reaction, there is a problem that foaming occurs and the pressure in the reaction tank rises. In the method of the present invention, industrially less expensive alkali metal water is used. An oxide can be used. As described above, the method of the present invention is a method for industrially and efficiently producing a fluorescent whitening agent and a 1,3,5-triazine substituted at the 2-position amino group, which is useful as an intermediate thereof. It can be said that the utility value is high.

Claims (6)

In a method for producing an amino-substituted 1,3,5-triazine by substituting a chlorine atom of cyanuric chloride with an amino group-containing compound, simultaneously adding a deoxidizing agent and an amino group-containing compound to a water-containing solution of cyanuric chloride. A process for producing an amino-substituted 1,3,5-triazine. The amino group-substituted 1,3 according to claim 1, wherein the pH is adjusted to 7 or less in the step of simultaneously adding the deoxidizing agent and the amino group-containing compound to the water-containing solution of cyanuric chlorides. A method for producing 5-triazine. A step of adding 40 to 90% of a necessary equivalent of the amino group for substituting a chlorine atom to a water-containing solution of cyanuric chlorides in advance, and then providing a step of simultaneously adding a deoxidizing agent and an amino group-containing compound. A method for producing an amino-substituted 1,3,5-triazine according to claim 1 or 2. The amino group-substituted 1, according to any one of claims 1 to 3, wherein the water-containing solution of cyanuric chlorides is a suspension in which cyanuric chlorides are dispersed in an aqueous solvent in the presence of a surfactant. A method for producing 3,5-triazine. In a method of producing an amino-substituted 1,3,5-triazine by reacting a chlorine atom of cyanuric chloride with an amino group-containing compound and a deoxidizing agent in a water-containing solvent, in the presence of an alkali metal halide A method for producing an amino-substituted 1,3,5-triazine characterized by the following. The method for producing an amino-substituted 1,3,5-triazine according to any one of claims 1 to 5, wherein the deoxidizing agent is an alkali metal hydroxide.