JP4412635B2 - Process for producing amino group-substituted 1,3,5-triazines - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an improved process for producing amino group-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, for example, in the case of reaction with 4,4′-diaminostilbene-2,2′-disulfonic acid or a salt thereof, usually in an aqueous solvent or organic 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 a compound containing an amino group in the presence of a phase transfer catalyst as necessary. It is known that it is advantageous to neutralize the hydrogen chloride produced by the reaction with a deoxidizer and proceed from weakly acidic to weakly alkaline.
Examples of the deoxidizer include alkali metal hydroxides, carbonates, acid carbonates, phosphates, borates, formates, acetates, alkaline earth metal or zinc oxides, carbonates, Examples thereof include phosphates, borates and the like, tertiary amines, urea and the like, which are used after the production of hydrogen chloride or, if necessary, more coexisting before the production.
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 1-8)
[0003]
[Patent Document 1]
JP-A-49-32923 [Patent Document 2]
JP 47-39217 A [Patent Document 3]
Japanese Patent Laid-Open No. 48-7922 [Patent Document 4]
JP-A-56-2975 [Patent Document 5]
Japanese Patent Publication No. 45-772 [Patent Document 6]
Japanese Patent Publication No. 53-6170 [Patent Document 7]
JP 47-39210 A [Patent Document 8]
JP-A-49-5126 [0004]
[Problems to be solved by the invention]
However, in the method in which the deoxidizer is added after the addition of the amino group-containing compound, when the scale-up is performed, the viscosity of the reaction system increases and stirring becomes difficult. There was a problem that substituents such as chlorine atoms were partially hydrolyzed.
The method of reacting an amino group-containing compound with a deoxidizer coexisting with cyanuric chloride requires a reaction in a two-phase system using an organic solvent so that the cyanuric chloride is not hydrolyzed. There was an industrial disadvantage.
An object of the present invention is to provide a method which can use water as a solvent and can produce an amino group-substituted 1,3,5-triazine compound industrially with a high yield and purity.
[0005]
As a result of intensive studies to solve the above problems, the present inventors have devised a method for adding an amino group-containing compound and a deoxidizer to cyanuric chlorides, and have also searched for an additive that suppresses an increase in viscosity. As a result, the present inventors have found that the above problems can be solved, and have completed the present invention.
[0006]
That is, the present invention
(1) In a method for producing an amino group-substituted 1,3,5-triazine by replacing the chlorine atom of cyanuric chloride with an amino group-containing compound, a deoxidizer and an amino group-containing compound are added to an aqueous solution of cyanuric chloride. A method for producing an amino group-substituted 1,3,5-triazine, comprising the step of simultaneously adding
(2) Amino group substitution 1 as described in (1), wherein the pH is adjusted to 7 or less in the step of simultaneously adding a deoxidizer and an amino group-containing compound to a water-containing solution of cyanuric chlorides. , 3,5-triazine production method,
(3) A step of simultaneously adding a deoxidizer and an amino group-containing compound after performing a step of previously adding 40 to 90% of a required equivalent of an amino group replacing a chlorine atom to a water-containing solution of cyanuric chlorides. A process for producing an amino group-substituted 1,3,5-triazine according to (1) or (2),
(4) The water-containing solution of cyanuric chlorides is a suspension solution in which cyanuric chlorides are dispersed in an aqueous solvent in the presence of a surfactant, as described in any one of (1) to (3) The present invention relates to a method for producing an amino group-substituted 1,3,5-triazine.
[0007]
(5) A method for producing an amino group-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 process for producing an amino group-substituted 1,3,5-triazine, characterized in that
(6) The method for producing an amino group-substituted 1,3,5-triazine according to any one of (1) to (5), wherein the deoxidizer is an alkali metal hydroxide.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The cyanuric chlorides used in the present invention represent cyanuric chloride or a 1,3,5-triazine compound in which one or two chlorine atoms of cyanuric chloride are substituted, and such substituents include methoxy group , Alkoxy groups such as ethoxy group, n-propoxy group and isopropoxy group, aryloxy groups such as phenoxy group and naphthyloxy group, N-amino groups such as methylamino group, dimethylamino group, ethylamino group, diethylamino group and anilino group A substituted amino group and the like can be exemplified. In particular, in the case of a substituent that is susceptible to hydrolysis by a deoxidizer, the method of the present invention can be suitably used.
[0009]
The amino group-containing compound used in the present invention is not particularly limited as long as it is a compound having in its molecule a primary or secondary amino group that can be substituted with a chlorine atom of cyanuric chloride. There is no particular limitation. 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. It can be illustrated.
[0010]
The production method of the present invention includes a step of simultaneously adding a deoxidizer 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 deoxidizer.
Specifically, the water-containing solution of cyanuric chlorides may be exemplified by a solution using water or a mixed system of water and an organic solvent such as acetone as the solvent. Since a system not used is desirable, it is preferable to use only water as a solvent. When water is used as a solvent, it is preferable to finely disperse cyanuric chlorides in water using a surfactant in order to perform the reaction more smoothly. Moreover, a nonionic surfactant can be illustrated as such surfactant.
Further, the pH of the reaction system is preferably adjusted to 7 or less, preferably 6 or less, in order to prevent hydrolysis of the raw materials and products.
[0011]
As the deoxidizer used, specifically, the above-mentioned known compounds can be used, but alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, which are industrially cheaper raw materials, are used in the present invention. This method is industrially advantageous.
[0012]
Adding at the same time includes not only adding at the same time but also an operation of adding both without a considerable interval. The addition method is not particularly limited, and examples thereof include a dripping method, a method of introducing a pump into a reaction solution, and the like. The addition may be continuous or divided and added at a considerable interval. In any case, as described above, it is preferable to add by controlling the pH of the reaction system to 7 or less, preferably 6 or less.
[0013]
In some cases, the production method of the present invention includes a step of previously adding 40 to 90% of the required equivalent of the amino group replacing the chlorine atom to the water-containing solution of cyanuric chloride before the above-described simultaneous addition step. Is preferred. In particular, when a compound in which the first chlorine atom of cyanuric chloride is substituted is used, the method of the present invention can be suitably used. In this case, since the reactivity of the second chlorine atom is lowered, after reacting by adding only the amino group-containing compound in advance, the pH of the reaction system is lowered by adding the deoxidizer and the amino group-containing compound. It can be suppressed to 7 or less, preferably 6 or less, and the influence of the deoxidizer on the raw materials and products can be reduced. When the amount added in advance is 40% or less of the required equivalent, the influence of the deoxidizer cannot be suppressed, and when it is 90% or more, the viscosity of the reaction solution increases, and similarly the influence of the deoxidizer can be suppressed. Can not.
[0014]
The reaction temperature is preferably as low as possible in order to suppress side reactions, particularly when many reactive chlorine atoms are contained. However, when the reactivity of chlorine atoms is lowered, it is necessary to keep the reaction temperature at a certain level, and in this case, the production method of the present invention can be suitably used.
[0015]
The production method of the present invention is characterized in that the reaction is carried out in the presence of an alkali metal halide. By coexisting an alkali metal halide, the viscosity of the reaction solution can be reduced, and the influence of the added deoxidizer 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 to be 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, with respect to 1 g of cyanuric chloride. Alkali metal halides may be mixed with cyanuric chlorides before reacting with amino group-containing compounds, mixed with amino group-containing compounds, or added to cyanuric chlorides simultaneously with amino group-containing compounds. May be.
[0016]
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to an Example.
[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. Add 40 kg of sodium chloride, and in the range of 0 ° C. to 10 ° C. with stirring, 3089 kg and 3.9 wt of 40.5 ′ aqueous solution of 4,4′-diaminostilbene-2,2′-disulfonic acid sodium salt (DAS) % 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 is raised to 25 ° C. and adjusted by dropping a 3.9 wt% aqueous sodium hydroxide solution so that the pH is in the range of 4 to 6, followed by aging for 1 hour at the same temperature. It was. The total amount of 3.9 wt% sodium hydroxide aqueous solution used was 1670 kg. The viscosity of the reaction solution was not increased, and the reaction solution could be sufficiently stirred.
A part of the reaction solution was collected, adjusted to pH 2 with sulfuric acid, sodium chloride was added, 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 produced almost quantitatively.
[0018]
Sodium hydroxide aqueous solution was dripped at the said reaction liquid, pH was adjusted to 8.5, and liquid temperature was heated up to 60 degreeC. Thereafter, 380 kg of a 15.5 wt% sodium hydroxide aqueous 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 dropping, no increase in the viscosity of the reaction solution was observed, and stirring could be performed satisfactorily.
Thereafter, 357 kg of diethanolamine (purity 80%) was added dropwise, then 460 g of a 15.5 wt% aqueous sodium hydroxide solution was added dropwise, 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.
The reaction solution was filtered while hot to remove insolubles, then 625 kg of sodium chloride was added at a solution temperature of 80 ° C., and 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 removal of the supernatant was repeated twice to remove sodium chloride, followed by filtration and drying to obtain 780 g of white crystals. When various spectra of the obtained crystals were measured, 4,4'-bis ((4- (bishydroxyethylamino) -6- (4-aminosulfonylanilino) -1,3,5-triazine-2- Yl) amino) stilbene-2,2'-disulfonic acid disodium salt. (Yield 90%)
[0019]
Example 2
293 kg of 2,4, -dichloro-6-methoxy-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. Add 40 kg of sodium chloride, drop 1545 kg of DAS 10.5 wt% aqueous solution in the range of 0 ° C. to 10 ° C. with stirring, and further react DAS 10.5 wt% 1544 kg with 3.9 wt% sodium hydroxide aqueous solution. The solution was dropped simultaneously so that the pH of the solution was in the range of 4-6 and the temperature was in the range of 10-25 ° C. Thereafter, the temperature of the reaction solution is raised to 60 ° C., 3.9 wt% aqueous sodium hydroxide solution is added dropwise so that the pH is in the range of 4 to 6, and the mixture is stirred at the same temperature for 1 hour for aging. It was. The total amount of 3.9 wt% aqueous sodium hydroxide used was 1670 kg. 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, the precipitated crystals were filtered, various spectra were measured, and 4,4′-bis ((4-chloro-6-6 It was confirmed that methoxy-1,3,5-triazin-2-yl) amino) stilbene-2,2′-disulfonic acid was produced almost quantitatively.
[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 influence of the deoxidizer used can be suppressed. it can. Further, carbonates have been conventionally used as a deoxidizing agent, but there is a problem that the pressure in the reaction tank rises during the reaction and the pressure of the reaction vessel increases. An oxide can be used. As described above, the method of the present invention is a method capable of industrially and efficiently producing 2-position amino group-substituted 1,3,5-triazines useful as optical brighteners and intermediates thereof. The utility value is high.

Claims (4)

Cyanuric chloride or a chlorine atom of cyanuric chloride, which is cyanuric chloride in which one or two of the chlorine atoms are substituted with an alkoxy group, an aryloxy group or an N-substituted amino group, is substituted with aniline, 1-aminobenzene-2,5- Substitution with an amino group-containing compound such as disulfonic acid or a salt thereof, metanilic acid or a salt thereof, 4,4′-diaminostilbene-2,2′-disulfonic acid or a salt thereof or sulfamine, and amino group substitution 1,3,5 -In a process for producing a triazine,
After performing the step of adding an amino group-containing compound in an amount corresponding to 40 to 90% of the required equivalent of the amino group replacing the chlorine atom to the water-containing solution of cyanuric chloride in advance, A method for producing an amino group-substituted 1,3,5-triazine, comprising a step of simultaneously adding a deoxidizer and an amino group-containing compound, and performing in the presence of an alkali metal halide. The amino group-substituted 1,3, 3, characterized in that, in the step of simultaneously adding a deoxidizer and an amino group-containing compound to a water-containing solution of cyanuric chlorides, the pH is adjusted to 7 or less. A method for producing 5-triazine. 3. The amino group-substituted 1, 3, 5 according to claim 1, wherein the water-containing solution of cyanuric chloride is a suspension solution in which cyanuric chloride is dispersed in an aqueous solvent in the presence of a surfactant. -Method for producing triazine. The method for producing an amino group-substituted 1,3,5-triazine according to any one of claims 1 to 3, wherein the deoxidizer is an alkali metal hydroxide.