JPH09235270A - Production of n-substituted dicarboxylic acid imide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high-purity N-substituted dicarboxylic acid imide in high yield by halogenating a dicarboxlic acid imide under specific conditions. SOLUTION: An aqueous solution of a dicarboxylic acid imide of the formula (one of R1 to R4 are each H, CH3 or C2 H5 ) is adjusted to pH1 to 7, preferably pH3.5 to 5.5 by adding an inorganic base (e.g. NaOH) and reacted with chlorine or bromine at 15-30 deg.C and subjected to Nhalogenation to give an N-substituted dicarboxylic acid imide. The N-substituted dicarboxylic acid imide (e.g. Nchlorosuccinic acid imide) is left in the most stable pH region and is obtained in high yield and in high purity without inducing the decomposition of the reaction product.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an N-substituted dicarboxylic acid imide such as N-chlorosuccinimide from a dicarboxylic acid imide such as succinimide.

[0002]

BACKGROUND OF THE INVENTION N-chlorosuccinimide is useful as a reagent for a reaction requiring a positively charged chlorine source, such as a disinfectant or a chlorinating agent, particularly an antibiotic. Widely used as a special chlorinating agent. As a method for producing this N-chlorosuccinimide, a method of dissolving succinimide in a sodium hydroxide solution and blowing chlorine into this aqueous solution [J. S.
C. , 121, 2169-2178 (1922)] is known. However, in this method, since the aqueous solution is basic at the initial stage of the reaction, not only the succinimide is hydrolyzed but also the product N-chlorosuccinimide is decomposed, and there is a problem that the yield is reduced. It was There is also a problem that nitrogen trichloride generated by decomposition of N-chlorosuccinimide is explosive and toxic (Japanese Patent Publication No. 62-
20983).

Further, Japanese Patent Application Laid-Open No. 6-56772 discloses that
A method of blowing chlorine into an aqueous solution of succinimide having a pH of 3 or less is disclosed. However, even in this method, since the aqueous solution is strongly acidic, there is a problem that a part of the produced N-chlorosuccinimide is decomposed and the yield is reduced. Particularly in the production of N-chlorosuccinimide on an industrial scale, the longer the reaction time, the more remarkable the decrease in yield.

Further, Japanese Patent Laid-Open No. 4-28362 discloses a method in which sodium hypochlorite is allowed to act on an inorganic acidic aqueous solution of succinimide. In this method also, the pH of the aqueous solution is 1 or less. It was strongly acidic and part of the product decomposed, lowering the yield. Further, since the raw material sodium hypochlorite is a dilute aqueous solution having a concentration of about 12%, the amount of aqueous solution in the entire reaction system increases. For this reason, not only the produced N-chlorosuccinimide is partially dissolved to cause a decrease in yield, but also the amount of product obtained from a reaction vessel having a fixed capacity is reduced. That is, the volume efficiency of the reaction tank is lowered, and the above method is industrially disadvantageous.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have conducted diligent research to halogenate dicarboxylic acid imides and obtain N-substituted dicarboxylic acid imides in high yield and high purity. The inventors have found that the above object can be achieved by controlling the pH, reaction temperature, etc., and have completed the present invention.

That is, according to the present invention, the general formula (I):

[0007]

Embedded image

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ are the same or different and H, CH ₃ , C ₂ H ₅ ) An inorganic base is added to an aqueous solution of a dicarboxylic imide. While maintaining the pH of the aqueous solution at 1 to 7 and at a temperature of 15 to 30 ° C,
Provided is a method for producing an N-substituted dicarboxylic acid imide, which comprises reacting chlorine or bromine for N-halogenation.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION A typical dicarboxylic acid imide used in the present invention is succinimide, and a typical N-substituted dicarboxylic acid imide is N-chlorosuccinimide. You can
The pH of the reaction solution of the present invention is adjusted to 3.5 to 7, more preferably 3.5 to 5.5. This is pH 3.5-7
In the above, the dicarboxylic acid imide which is a reaction product and the N-substituted dicarboxylic acid imide which is a product are chemically most stable. That is, when the pH is within the above range, the decomposition of the dicarboxylic acid imide and the N-substituted dicarboxylic acid imide under a basic condition and the decomposition of the N-substituted dicarboxylic acid imide under a strong acidic condition are suppressed, resulting in a high yield. Is obtained.

An inorganic base can be used to adjust the pH of the solution. Examples of the inorganic base include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and magnesium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkali metal hydrogen carbonates such as sodium hydrogen carbonate. , And particularly preferably sodium hydroxide and sodium carbonate.

When a strong base is used for pH adjustment, the dicarboxylic acid imide is decomposed at the same time when it contacts the base, and the yield of the N-substituted dicarboxylic acid imide is reduced. However, there is no problem if the concentration is relatively low. In this case, the base concentration is practically 10 to 10.
It can be used at 30%, preferably 10 to 20%.

The N-halogenation reaction of the present invention has the general formula:

[0013]

Embedded image

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are of the formula (I)
Synonymous with, X is chlorine atom or bromine atom), and chlorine or bromine is introduced into an aqueous solution of dicarboxylic acid imide. At this time, 1 mol of hydrogen halide is by-produced with respect to 1 mol of dicarboxylic acid imide. The addition of the inorganic base maintains the pH of the aqueous solution of dicarboxylic acid imide within a predetermined range, and at the same time, functions as an acid acceptor of the hydrogen halide.

The amount of the inorganic base added is required to be an equivalent amount necessary for receiving, ie, neutralizing, the hydrogen halide produced as a by-product. The inorganic base is added continuously or at intervals so that the reaction solution has a predetermined pH value. The temperature in the N-halogenation reaction of the present invention is 15 to 30.
C., preferably 15 to 20.degree. In order to suppress the decomposition of the N-substituted dicarboxylic acid imide which is the product, the reaction temperature is preferably 10 ° C or lower. However,
When the reaction is carried out at 10 ° C or lower, the produced N-substituted dicarboxylic acid imide becomes fine powder and causes filter clogging in the recovery step, which makes solid-liquid separation operation difficult. In addition, the washing operation of the product becomes difficult, and the product purity decreases. Furthermore, since the water content of the N-substituted dicarboxylic acid imide after filtration increases, the decomposition of the product due to moisture increases, and the product yield and product purity decrease. Therefore, the reaction temperature is preferably 15 ° C or higher. Further, the reaction temperature is preferably 30 ° C. or lower in order to suppress the decomposition of the N-substituted dicarboxylic acid imide. Further, the reaction temperature may be lowered stepwise during the reaction in order to suppress decomposition of the product.

Further, the dicarboxylic acid imide aqueous solution used in the present invention is preferably a saturated aqueous solution. When the halogenation is carried out in a heterogeneous solution, that is, in a state where the dicarboxylic acid imide is deposited, it is difficult to complete the reaction and the yield is reduced. Further, it is preferable to carry out the reaction with a saturated aqueous solution of dicarboxylic acid imide, because the volume efficiency of the reaction tank is industrially improved.

N obtained by the N-halogenation reaction of the present invention
Examples of the -substituted dicarboxylic acid imide include N-chlorosuccinimide, N-bromosuccinimide and N-chloro-
3,4-Dimethylsuccinimide, N-bromo-3,4
-Dimethylsuccinimide, N-chloro-3,4-diethylsuccinimide, N-bromo-3,4-diethylsuccinimide and the like.

[0018]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but these examples do not limit the scope of the present invention. Example 1 A stirrer, a thermometer, a dropping funnel, a gas introduction port, and a gas outlet were attached to a 1-liter 6-necked flask, and water 331 was added thereto.
g and 99 g (1 mol) of succinimide were added, and the mixture was cooled to 20 ° C. The aqueous solution at this time was a saturated homogeneous solution of succinimide. Then, chlorine gas was introduced into the aqueous solution while maintaining the liquid temperature at 20 ° C. Simultaneously with the introduction of chlorine gas, 200 g of 20% sodium hydroxide that had been adjusted in advance was added from a dropping funnel to carry out the reaction while adjusting the pH of the aqueous solution to 3.5 to 5.5. From the time when 7.1 g of chlorine gas was introduced, the aqueous solution was cooled to 15 ° C. and the reaction was continued. 71.9 g (1.01 mol) of chlorine gas was introduced in 3 hours.

After the introduction of chlorine gas, the mixture was aged for 30 minutes while cooling it to 5 ° C., and then the contents were filtered,
After washing with 166 g of water and drying, 122.8 g of N-chlorosuccinimide which is a reaction product (yield 9
2.0%) was obtained. Effective chlorine is 26.53% (theoretical value 2
6.55%) and the product purity calculated from this is 99.
It was 9%.

The available chlorine was obtained by adding a mixture of water and acetic acid (volume ratio 1: 2), 10% potassium iodide solution to the product, leaving it for 10 minutes, and using a starch solution as an indicator, 1/10 normal thiol. It was determined by titration with a sodium sulfate solution. Table 1 shows the reaction conditions and results.

[0021]

[Table 1]

Example 2 Using 282 g of water and 133 g of 30% sodium hydroxide,
In the same manner as in Example 1 except that the liquid temperature was 25 ° C., N
-Chlorosuccinimide 119.1 g (yield 89.2)
%) Was obtained. However, the amount of chlorine gas introduced was 74.
It was 4 g (1.05 mol). Effective chlorine of N-chlorosuccinimide is 26.50% (theoretical value is 26.55%)
The product purity calculated from this was 99.8%.

The reaction conditions and results are shown in Table 1. Example 3 A 1-liter six-necked flask was equipped with a stirrer, a thermometer, a dropping funnel, a gas introduction port, and a gas outlet, and water 331 was added thereto.
g and 99 g (1 mol) of succinimide were added, and the mixture was cooled to 20 ° C. The aqueous solution at this time was a saturated homogeneous solution of succinimide. Then, chlorine gas was introduced into the aqueous solution while maintaining the liquid temperature at 20 ° C. Simultaneously with the introduction of chlorine gas, 80 g of 30% sodium hydroxide, which had been adjusted in advance, was added from a dropping funnel to carry out the reaction while adjusting the pH of the aqueous solution to 3 or less. Chlorine gas 86.5g (1.22mol)
Was introduced in 3 hours.

After the introduction of chlorine gas, the same treatment as in Example 1 was carried out to obtain 120.2 g of N-chlorosuccinimide (yield 90.0%). The available chlorine is 26.31% (theoretical value is 26.55%), and the product purity calculated from this is 9
9.1%. Table 1 shows the reaction conditions and results. Example 4 Using 200 g of 20% sodium hydroxide, the pH was adjusted to 5.5.
N was carried out in the same manner as in Example 3 except that the N was adjusted to 7.0.
-Chlorosuccinimide 114.3 g (yield 85.6)
%) Was obtained. However, the amount of chlorine gas introduced was 81.
It was 0 g (1.14 mol). Effective chlorine of N-chlorosuccinimide is 26.37% (theoretical value is 26.55%)
The product purity calculated from this was 99.3%.

The reaction conditions and results are shown in Table 1. Example 5 112.4 g (yield 84.2%) of N-chlorosuccinimide was obtained in the same manner as in Example 4 except that the liquid temperature was adjusted to 30 ° C. and the pH was adjusted to 3.5 to 5.5. It was However, the amount of chlorine gas introduced was 72.3 g (1.02 mol) in 3 hours. The available chlorine of N-chlorosuccinimide is 26.4.
The product purity was 7% (theoretical value: 26.55%), and the product purity calculated from this was 99.7%.

The reaction conditions and results are shown in Table 1. Comparative Example 1 The same procedure as in Example 5 was repeated except that the liquid temperature was changed to 10 ° C.
-Chlorosuccinimide 105.9 g (yield 79.3)
%) Was obtained. However, the aqueous solution of succinimide is an unsaturated heterogeneous solution, and the amount of chlorine gas introduced is 89.3 g in 3 hours.
(1.26 mol). The available chlorine of N-chlorosuccinimide is 26.15% (theoretical value is 26.55%),
The product purity calculated from this was 98.5%.

The reaction conditions and results are shown in Table 1. Comparative Example 2 N-chlorosuccinimide 100.2 was prepared in the same manner as in Example 3 except that 268 g of water was used and the liquid temperature was 10 ° C.
g (yield 75.1%) was obtained. However, the aqueous solution of succinimide was an unsaturated heterogeneous solution, and the amount of chlorine gas introduced was 98.8 g (1.39 mol) in 3 hours. The available chlorine of N-chlorosuccinimide is 26.24% (theoretical value 26.
55%), and the product purity calculated from this is 98.8%.
Met.

The reaction conditions and results are shown in Table 1.

[0029]

According to the present invention, the N of the dicarboxylic acid imide is
The halogenation reaction is added to a saturated aqueous solution of dicarboxylic acid imide with an inorganic base to maintain the pH of the aqueous solution at 3.5 to 7, preferably pH 3.5 to 5.5, and 15 to 3
Since it is carried out by reacting chlorine or bromine at a temperature of 0 ° C., preferably 15 to 20 ° C., the product N-substituted dicarboxylic acid imide is placed in the most stable pH region and induces decomposition of the product. It is possible to produce a high-yield and high-purity N-substituted dicarboxylic acid imide without having to do so.

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[Procedure amendment]

[Submission date] March 18, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction contents]

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION A typical dicarboxylic acid imide used in the present invention is succinimide, and a typical N-substituted dicarboxylic acid imide is N-chlorosuccinimide. You can
The pH of the reaction solution of the present invention is 1 to 7, preferably pH.
The pH is adjusted to 3.5 to 7, more preferably 3.5 to 5.5 . It should be noted that if the pH is 3.5 to 7, the dicarboxylic acid imide as the raw material and the N-substituted dicarboxylic acid imide as the product can be caused to exist chemically most stably.
Wear. That is, if the pH is above range, minute <br/> solution of dicarboxylic acid imide and N- substituted dicarboxylic acid imide in basic under and decomposition of N- substituted dicarboxylic acid imide of the strongly acidic under suppression And a high yield is obtained.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction contents]

The amount of the inorganic base would require an equivalent amount required hydrogen halide by-produced receptor, i.e. to neutralize. The inorganic base is added continuously or at intervals so that the reaction solution has a predetermined pH value. The temperature in the N-halogenation reaction of the present invention is 15 to 30.
C., preferably 15 to 20.degree. In order to suppress the decomposition of the N-substituted dicarboxylic acid imide which is the product, the reaction temperature is preferably 10 ° C or lower. However,
When the reaction is carried out at 10 ° C or lower, the produced N-substituted dicarboxylic acid imide becomes fine powder and causes filter clogging in the recovery step, which makes solid-liquid separation operation difficult. In addition, the washing operation of the product becomes difficult, and the product purity decreases. Furthermore, since the water content of the N-substituted dicarboxylic acid imide after filtration increases, the decomposition of the product due to moisture increases, and the product yield and product purity decrease. Therefore, the reaction temperature is preferably 15 ° C or higher. Further, the reaction temperature is preferably 30 ° C. or lower in order to suppress the decomposition of the N-substituted dicarboxylic acid imide. Further, the reaction temperature may be lowered stepwise during the reaction in order to suppress decomposition of the product.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction contents]

[0029]

According to the present invention, the N of the dicarboxylic acid imide is
The halogenation reaction is carried out by adding an inorganic base to a saturated aqueous solution of dicarboxylic acid imide to adjust the pH of the aqueous solution to 1 to 7,
PH 3.5 to 7, more preferably pH 3.5 to 5.
5 to 15 and 30 ° C., preferably 15 to 2
Since it is carried out by reacting chlorine or bromine at a temperature of 0 ° C,
The product N-substituted dicarboxylic acid imide is placed in the most stable pH region, and it is possible to produce a high yield and high purity N-substituted dicarboxylic acid imide without inducing decomposition of the product.

Claims (5)

[Claims] 1. A compound of the general formula (I): (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are the same or different,
H, to an aqueous solution of the dicarboxylic acid imide represented by _{CH 3, C 2 H 5)} , by adding an inorganic base the pH of the aqueous solution 1-7
N-halogenated by reacting chlorine or bromine with maintaining the temperature at 15 to 30 ° C.
-A method for producing a substituted dicarboxylic acid imide. 2. The method according to claim 1, wherein the pH is 3.5 to 7. 3. The pH is 3.5 to 5.5.
Or the method of 2. 4. The temperature is 15 to 20 ° C.
3. The method according to 3. 5. The method according to claim 1, wherein the aqueous solution of dicarboxylic acid imide is a saturated aqueous solution.