JPH0258577A - Manufacturing method of disazo compound - Google Patents

Abstract

PURPOSE:To obtain the title compound useful as blue reactive dye, etc., industrially and advantageously by alkoxylating part of chlorine of a trichlorotriazine, reacting the resultant substance with a specific diamine and subjecting the resulting substance and a diazo bonded material of a specific amine and H acid to a diazo coupling. CONSTITUTION:2,4,6-Trichlorotriazine is reacted in a lower alcohol solvent in the presence of a basic catalyst at 10-40 deg.C to give 2,4-dichloro-6- alkoxytriazine, which is reacted with an aqueous solution of a diamine shown by formula I at 0-25 deg.C at pH 4-6 to give a compound shown by formula II (R is lower alkyl). Then the compound is diazotized with an alkali nitrite and an inorganic acid and coupled at pH6-7.5 with a monoazo compound shown by formula IV which is prepared by diazotizing an amine shown by formula III (X is vinyl or group shown by formula CH2CH2OSO3H) and coupling the diazotized substance with a H acid to give the aimed compound shown the formula V.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to the production of a disazo compound, and more particularly, to an industrially advantageous method for producing a water-soluble disazo compound useful as a blue reactive dye. It is related to.

(Conventional technology) In the form of free acid, the following general formula [1] (In the formula, R is a lower alkyl group, XU-CH=CH.

A disazo compound represented by a group (-CH, CH, 08OaH group) is known as a blue reactive dye with excellent dyeing rate and dyeing reproducibility. This compound is usually λ
, ≠, A-) Lichlortriazine 7 # Near #7
A compound represented by the following general formula [1l] (wherein R is the same as defined above) is prepared from the 2μm diC7#-6-alkoxytriazine obtained by the reaction in the form of a free acid. After diazotizing an amine represented by the following general formula (]] (wherein, X is the same as defined above) in the form, and coupling it with H acid, the following general formula (V) A monoazo compound represented by the following general formula [111] (wherein, X is the same as defined above) is produced in the form of a free acid by reacting with a diamine represented by It can be produced by diazotizing the compound represented by [ ] and then coupling it with a monoazo compound represented by the general formula [v].

However, in the dye synthesis reaction, it is necessary to obtain a target product with high purity from the viewpoint of color tone. .4'-Cyclo-t-alkoxytriazine, a compound represented by the general formula Cu1l), and a monoazo compound represented by the general formula [■]. Once these intermediate products are separated from the reaction mixture, It was supplied to the next reaction step. Therefore, in the above-mentioned production method, not only the reaction steps are long, but also the separation operations in each reaction step are troublesome. In particular, the front leg general formula [■] and [
Compound Viζ is a water-soluble compound, and requires salting out in order to separate it from the reaction medium. Furthermore, 2.4t-dichloro-6-alkoxytriazine is conventionally supplied to the next reaction after drying the separated cake. Dry powder of Hiro-dichloro-2-alkoxytriazine is highly irritating to the skin, so care must be taken when handling it.

Moreover, for example, Soviet patent no. , No. 7rt, etc., the alkoxylation reaction of J,4t,J-trichlorotriazine is carried out in an acetone solvent, followed by the reaction with a diamine represented by the forefoot general formula (II). Although the reaction is carried out at a temperature of ≠0° C., the yields of these desired products are not satisfactory.

(Problems to be Solved by the Invention) In view of the above-mentioned circumstances, the present inventors have repeatedly studied various methods for industrially advantageous production of the disazo compound represented by the general formula [I] useful as a reactive dye. As a result, when the reaction is carried out according to the method of the present invention, even if the reaction mixture containing the compounds represented by the forefoot general formulas [I] and [■] is directly fed to the next reaction step, the final product cannot be obtained. It does not adversely affect the quality of the disazo compound as a reactive dye, and x,p,6-trichlorotriazine is subjected to an alkoxylation reaction in an alcohol sole solvent,
The obtained 1,≠-dichloro-t-alkoxytriazine is not separated and dried, but is fed as a reaction mixture containing the target product or in a wet state to the next reaction step with diamine, and reacted at a temperature of 2t°C or less. By carrying out this method, there are fewer separation steps, and also
-We have discovered that it is possible to produce the desired disazo compound while avoiding the skin irritation of dry alkoxytriazine powder and maintaining high yields in each reaction step, and have completed the present invention.

[Means to solve the problem]

The gist of the present invention is to synthesize a disazo compound represented by the general formula [I] in the form of a free acid: (1) 2,4L, t
- trichlortriazine in substantially the sole solvent of an aliphatic lower alcohol in the presence of a basic catalyst at 1o-ao°C.
to produce 2,44-dichloro-t-alkoxytriazine by alkoxylation at a temperature of
] A reaction mixture containing the 21 μm cyclo-t-alkoxytriazine obtained in step (1) above in an aqueous solution of the diamine shown in ] or 2,≠-dichloro-t-alkoxytriazine obtained by mixing water with the mixture and recovering it. o,2s”ccDtNl
Then, the reaction is carried out under the conditions of L Camol I) H4t~B to produce a compound represented by the general formula [11f) in the form of a free acid, and ■ the compound represented by the general formula [11f] in the form of a free acid.
After adding an alkali nitrite and an inorganic acid to an aqueous solution of the amine represented by to diazotize it, the diazo mixture and 11 acids are subjected to a campling reaction to form a free acid represented by the general formula [V]. producing a monoazo compound;
■Forepaws obtained in above ■After diazotization by adding alkali nitrite and inorganic acid to the reaction mixture containing the compound represented by the general formula [I[), this mixture is then converted into the reaction mixture containing the compound represented by the general formula [I[]. A disazo compound represented by the general formula (CI) is produced by adding the compound as it is into a reaction mixture containing the compound represented by the general formula (V), and performing a coupling reaction under conditions of pH 6 to 7 in the evening. The invention consists in a method for producing a disazo compound.

The present invention will be explained in detail below.

In the present invention, a disazo compound represented by the general formula [■] is produced. In the formula, the lower alkyl group represented by R is usually a methyl group, an ethyl group, or an n-
Examples include alkyl groups having a carbon number of /F, such as a propyl group, 1So-propyl group, and n-butyl group. Note that the compounds in each general formula of the present invention usually exist in the form of a free acid or a sodium salt, potassium salt, or lithium salt.

First, in the present invention, λ, u, G-trichlorotriazine is alkoxylated with fatty acid lower alcohol to obtain 2.4
Although t-dichloro-t-alkoxytriazine is produced, it is essential in the present invention that the alkoxylation reaction be carried out using substantially the sole solvent of the aliphatic lower alcohol. In short, only the aliphatic lower alcohol, which is the raw material for alcokylation, is used as a solvent without using other organic solvents such as acetone or mixed solvents such as hydrous alcohol. The type of aliphatic lower alcohol is determined by the R of the disazo compound represented by the general formula Cr), and examples include methanol, ethanol, n-
Examples include 7' lovanol, 19o-gropanol, n-butanol, and the like. The amount of alcohol used is 2, I
For t,lr-trichlortriazine, usually j,
/ 6 times by mole, preferably 7 to 12 times by mole.

The alkoxylation reaction is carried out in the presence of a basic catalyst, and the basic catalysts usually include alkali hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, etc. Examples include trialkaline hydrogen phosphate, etc., and the amount used is usually 2. Jt
-) f~7.5 times mole relative to dichlorotriazine. The temperature of the alkoxylation reaction is 10-≠θ℃,
Further, the reaction time is usually about 30 to 0 minutes. If the reaction temperature is too low, alkoxylation will not be carried out well,
On the other hand, if it is too high, by-products such as dialkoxy compounds will be produced, which is not preferable. K for carrying out the alkoxylation reaction is usually 1. This can be carried out by dispersing trichlortriazine powder and a basic catalyst and maintaining the mixture at a predetermined temperature while stirring. Note that this reaction is exothermic, so usually λ,
It is desirable that the chlortriazine be supplied in portions depending on the heat removal rate of the reactor.

The reaction mixture after the alcokylation reaction is usually

This is a slurry in which λ, p-dichloro-t-alkoxytriazine is partially dissolved, but in the present invention, this mixture is used as it is, or 2, p-dichloro-6- is dissolved by mixing water with this mixture. After the alkoxytriazine has been precipitated, it is recovered and the resulting wet cake is fed to the next reaction with the diamine. In short, the present invention has the advantage that irritation to the skin can be avoided by always handling the λ,≠-dichloro-6-alkoxytriazine in a wet state without drying it. The amount of water mixed here is usually
For the reaction mixture, 2~? It is about twice the weight. Also,
The cake can be recovered according to a conventional method using a solid-liquid separator such as a filter press, center or decanter.

Next, the diamine represented by the forefoot general formula [[1] is 2, μ
A compound represented by the forefoot general formula C11l) is produced by reacting with mdichloro-6-alkoxytriazine,
This reaction is carried out by adding the reaction mixture or wet cake containing the above-mentioned λ,≠-dichloro-2-alcoquine triazine to an aqueous solution (usually an alkaline aqueous solution) of the diamine. The concentration of the diamine aqueous solution at this time is usually 3 to 10 weight ratios, and the amount of 2,It-dichloro-6-alkoxytriazine used relative to the diamine is usually 1 to 10/Oj (mole times). In this reaction, the raw material triazine compound is not sufficiently dissolved, resulting in a heterogeneous reaction, so it is desirable to add a small amount of a dispersant to the reaction, if necessary.

React above 0,2! For example, at a temperature of 30
The event will last approximately 60 minutes. If the reaction temperature is too low, the reaction will not proceed well; on the other hand, if the reaction temperature is too high, the formation of by-products will increase, which is undesirable.

In addition, it is necessary to adjust the reaction pH to a range of μ to B, and a particularly good reaction can be expected within this range. In addition, as a pH adjuster, for example, sodium hydrogen carbonate,
Aqueous solutions of inorganic acid salts of alkali metals such as sodium carbonate, potassium carbonate, and sodium hydroxide are used.

The compound represented by the forepaw general formula (III) is diazotized and then subjected to a coupling reaction with a monoazo compound represented by the forepaw general formula [■] obtained by the method described below. In the present invention, the forepaw general formula [1] ) from the reaction mixture obtained as described above without recovering it by salting out. It is then subjected to the subsequent diazotization reaction. That is, according to the method of the present invention, even if intermediate products are not separated and purified, the color tone and performance of the finally obtained disazo compound as a reactive dye are not adversely affected.

On the other hand, after diazotizing the amine represented by the general formula (fV), this is coupled with I (acid) to produce a monoazo compound represented by the general formula [V]. The amount of alkali nitrite and hydrochloric acid used in the aqueous solution of the amine is usually the same as for the amine.
Each is about equimolar. The diazotization reaction is usually 0 to r
The process is carried out at a temperature of 1 to 3 hours. Further, the alkali nitrite is usually sodium nitrite or potassium nitrite.

The mixture after the above diazotization reaction is mixed with H acid and subjected to a coupling reaction to produce a monoazo compound represented by the general formula [V]. The amount of H acid used is usually based on the general formula (IV). The amount is approximately equimolar to the amine represented by . The coupling reaction is usually performed at pH/~3
The temperature is adjusted to 0 to isC for 3 to IO hours.

In this way, a reaction mixture containing the monoazo compound represented by the general formula [V] is obtained, but in the present invention, the monoazo compound is not recovered from this mixture by salting out, and is used in the next coupling reaction. It is a requirement that it be used as is. That is, numerically, various by-products are produced in a coupling reaction, and it is normal to isolate the desired product from the reaction mixture, but in the case of the present invention,
In this step, a good reactive dye can be finally obtained without separating the monoazo compound, and as a result, the process can be simplified and the production method can be industrially advantageous.

In the final step of the present invention, an alkali nitrite and an inorganic acid are added to the reaction mixture containing the compound represented by the forefoot general formula (III) obtained as described above to diazotize it, and then this is diazotized as described above. The general formula for the front legs obtained as follows:
■] By adding it to a reaction mixture containing the compound represented by and causing a coupling reaction, the forepaw general formula (I) can be obtained.
A disazo compound represented by is produced. Front leg general formula (
The diazotization reaction of the compound represented by III) is carried out according to a conventional method, and may be substantially the same as the diazotization method of the amine represented by the above-mentioned general formula CIV).

The pH of the mixture of both of the above reaction mixtures is usually l
As shown below, the coupling reaction between the forefoot general formula (III) and the compound represented by [■] is carried out at pHA to 7. Since the process progresses well, preferably between t and 7, it is necessary to adjust the pH of the mixture to the above range using a pH regulator such as, for example, an inorganic acid salt of an alkali metal such as sodium bicarbonate, sodium carbonate, or sodium hydroxide. There is. The temperature of the coupling reaction is usually θ to 10'C, and the reaction time is about /-j hours.

As described above, a reaction mixture containing a disazo compound represented by the general formula (H), which is the target compound of the present invention, is obtained, but since the target compound is a water-soluble compound and is dissolved in the reaction mixture, Usually, the target compound can be recovered by salting out the reaction mixture, then separating the precipitated cake and, if necessary, drying it, or by directly spray-drying the reaction mixture.

In addition, examples of salts used for salting out include inorganic salts such as sodium sulfate, sodium chloride, and potassium chloride.

(Examples) Next, the present invention will be described in more detail, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Example I [Production of 4t-dichloro-2-methoxytriazine] In a /l glass reactor equipped with a stirrer and a temperature controller,
After charging 203ml of methanol, the temperature was heated to about 3θ℃ while stirring.
Add 2. to this while maintaining the temperature at . ≠, 6-dolychlortriazine 92.39 and sodium bicarbonate r r,
ry was added over a period of 60 minutes, and the mixture was further maintained at the same temperature for 0 minutes to carry out a methoxylation reaction.

After the reaction was completed, 1/d of water was added to the mixture, and the mixture was then filtered to recover a wet cake of u,9-dichloro-2-methoxytriazine. This cake was analyzed to determine the yield and purity of 21 μm cyclo-6-medoxytriazine, and the results shown in Table 1 were obtained.

For comparison, the results obtained when the same methoxylation reaction was carried out by reducing the amount of methanol used and adding acetone or water in the amount shown in Table 7 as a solvent are shown in Table 1.
/ Shown in /.

Table-! [Production of a compound represented by the general formula (1)] In a 2t glass reactor equipped with a stirrer, 3. ♂ff1-jt% of /,3-diaminobenzene-6-sulfonic acid dissolved in hydroxylated solution) IJum aqueous solution lrOtsu2 was charged, and λ,≠-dichlorofluoride obtained in the above reaction (A/) was charged. B - No methoxy triazine cake (liquid content 3!%) 1
03? and fatty acid ester highly sulfated oil (Sanyo Chemical Co., Ltd.,
King Oil S-1o) (trade name) and isy were added, and the reaction was carried out at a temperature of about 10° C. for 60 minutes with stirring while adjusting the pH in the system to jj with an aqueous sodium hydroxide solution.

After the reaction, the mixture was analyzed and the yield of the product, a compound represented by the following structural formula (/, 3-diaminobenzene-
As a result, the results shown in Table 2 were obtained.

Table 2 shows the results of a similar reaction.

Table No. [Manufacture of monoazo compound] 2t glass reactor VC equipped with a stirrer and temperature controller
,tA-(J-sulfatoethylsulfonyl)aniline! , 6! A weight ratio aqueous solution 10002 was charged, and to this was added sodium nitrite 1 μ, 32 and 3 weight ratio hydrochloric acid Jr 3.
Add 2.1 and reduce to 0~! while stirring. After carrying out the diazotization reaction for 2 hours at a temperature of 63.degree. ♂2
was added, the pH was adjusted to λ~2.5, and the coupling reaction was carried out at a temperature of 0-10°C for g hours.

After the reaction, the mixture was analyzed and the yield of the product, a monoazo compound represented by the following structural formula (relative to ≠-(cosulfateethylsulfonyl)aniline), was found to be in the Tata range.

After the reaction was completed, the mixture was directly spray-dried to recover the generated disazo compound powder.

What was the yield (relative to the monoazo compound) of the disazo compound represented by the structural formula below obtained in this manner? 4ttI), and the purity was 5%.

[Manufacture of disazo compound]

To the reaction mixture obtained in the above [Production of a compound represented by the general formula CII [) ()ffi/), nitrous acid, 32 and 3, and hydrochloric acid by weight! Add 3.2ml,
After carrying out the diazotization reaction for 1 hour at a temperature of o - t 'c under stirring, this was subsequently added as it was to the reaction mixture obtained in the above [manufacture of monoazo compound],
Furthermore, /j weight-related sodium carbonate aqueous solution was added to adjust the pH in the system to 6 to 7, and the mixture was heated at a temperature of 0.1 to 10° C. with stirring.
The coupling reaction was carried out for a period of time.

The disazo compound obtained here is useful as a navy blue reactive dye for cellulose fibers, and its color tone and dyeability are good. For example,
After salting out and isolating intermediate products such as the compound represented by the general formula [■] and the monoazo compound, there was no difference in performance from the reactive dye produced when a disazo compound was produced.

It can be said that this method is industrially extremely advantageous.

■ There are fewer salting-out processes and intermediate product separation steps, and
It is economically advantageous because the number of reactors is small.

■ 1. ≠-There is no concern about chemical harm to the skin due to the dichloro-6-alkoxytriazine powder.

(2) Since the yield of the compound represented by λ, cucyclo-6-alkoxytriazine and the general formula [■] is high, the yield of the final disazo compound obtained is also high.

(2) Despite the fact that there are fewer complicated intermediate product processing steps, the final disazo compound obtained has excellent suitability as a reactive dye.

Claims (1)

[Claims] (1) In the form of a free acid, the following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
When synthesizing the disazo compound represented by [I] (wherein R is a lower alkyl group and X represents a -CH=CH_2 group or a -CH_2CH_2OSO_3H group), [1] 2, 4
, producing 2,4-dichloro-6-alkoxytriazine by alkoxylating 6-trichlorotriazine in a substantially sole solvent of an aliphatic lower alcohol in the presence of a basic catalyst at a temperature of 10 to 40°C; [2] In the form of free acid, the following general formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
[II] A reaction mixture containing the 2,4-dichloro-6-alkoxytriazine obtained in [1] above in an aqueous solution of the diamine represented by [II] or a mixture obtained by mixing water with the mixture and then separating and collecting the mixture. A wet cake containing 2,4-dichloro-alkoxytriazine was added, and the reaction was carried out at a temperature of 0 to 25°C and under conditions of pH 4 to 6 to form the following general formula [III] in the form of a free acid. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
[III] (In the formula, R is the same as defined above) [3] In the form of a free acid, the following general formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...・・・・・・〔I
V] (wherein, The following general formula [V] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・[I
V] producing a monoazo compound represented by the formula (wherein X is the same as defined above); [4] in a reaction mixture containing the compound represented by the general formula [III] obtained in [2] above; is diazotized by adding an alkali nitrite and an inorganic acid, and then this mixture is directly added to the reaction mixture containing the compound represented by the general formula [V] obtained in [3] above, and the pH is adjusted to 6 to 6. The coupling reaction is carried out under the conditions of 7.5 and the general formula shown above [
A method for producing a disazo compound, characterized by: producing a disazo compound represented by [I]].