JPH0558988A - Production of sulfobeataine - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful as a bleaching activator, etc., in high purity and yield by reacting a specific sulfonated derivative with a specified amine derivative. CONSTITUTION:A compound expressed by formula I (X is halogen; R<4> is 1-10C alkylene) is reacted with one or more sulfonating agents selected from SO3, XSO3H and their complexes to provide a sulfonated derivative, which is then brought into contact and reacted with an amine expressed by formula II (R<1> is 1-20C alkyl, alkenyl, phenyl, etc.; R<2> and R<3> are 1-3C alkyl; A is O, NHCO, CO, COO, etc.; Y is 1-10C alkylene, etc.; (n) is 0-10) at 50-160 deg.C temperature to afford a mixture of a compound expressed by formula III with a compound expressed by formula IV. The compound expressed by formula III is further separated and removed to provide the objective compound expressed by formula IV.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing sulfobetaine having an ester bond, which is useful as a bleach activator in an oxygen bleach.

[0002]

2. Description of the Related Art Sodium percarbonate and sodium perborate are used as oxygen-based bleaching agents, but they have a weaker bleaching power than chlorine-based bleaching agents, and therefore have a bleaching activity. Agents are used in combination. As the bleach activator, the present inventors have proposed in Japanese Patent Application No. 1-150758 that sulfobetaine having an ester group is extremely suitable.

As a method for producing this sulfobetaine, there is a method involving a reaction between an alkylcarboxylic acid halide which may have a substituent (hereinafter referred to as carboxylic acid halide) and phenolsulfonic acid sodium salt. There was such a problem. That is, since sodium phenolsulfonic acid salt is poorly soluble in an aprotic organic solvent, if this is used as a reaction solvent, the reaction system becomes heterogeneous, so that the target sulfobetaine can be obtained only in a low yield. I couldn't get it. Further, it is possible to dissolve phenolsulfonic acid sodium salt only in water or a highly polar solvent such as dimethylformamide (DMF).
Etc. are expensive, and it is not preferable to use them as a solvent from the viewpoint of manufacturing economy. On the other hand, if water is present in the reaction system, hydrolysis of the carboxylic acid halide, which is the reaction raw material, and the ester bond formed will occur, and a decrease in the yield of the desired sulfobetaine is unavoidable. Further, in the method using sodium salt of phenol sulfonic acid as a raw material, an inorganic salt such as sodium halide is unavoidable as a by-product, and there is a problem that this inorganic salt causes corrosion of the reactor and narrowing of the piping.

Therefore, an object of the present invention is to provide a method for economically producing phenylsulfobetaine having an ester group in a high yield and high purity without accompanying by-products of inorganic salts. Is.

[0005]

In order to solve the above problems, the present inventors have made earnest studies and found that the above problems can be solved by using a specific raw material and a specific reaction method. The present invention has been completed. That is, the present invention provides a method for producing sulfobetaine represented by the general formula (I), which comprises performing the following steps (a) to (c).

[0006]

[Chemical 6]

[Wherein R ^{1 is a} linear or branched carbon number 1 to 1
20 represents an alkyl group or an alkenyl group, a phenyl group, or an alkyl-substituted aryl group having 1 to 20 carbon atoms in total. R ² and R ^{3 are the} same or different and each represents an alkyl group having 1 to 3 carbon atoms. R ⁴ : represents an alkylene group having 1 to 10 carbon atoms which may have a branched chain.

[0008]

[Chemical 7]

M: Indicates a number of 0 or 1. ] Step (a) A compound represented by the following general formula (II), SO ₃ , XSO ₃ H
(Wherein X represents a halogen atom) and at least one sulfonating agent selected from these complexes,
A step of obtaining a sulfonated product.

[0010]

[Chemical 8]

(Wherein R ⁴ and X have the above-mentioned meanings) Step (b) The sulfonated compound obtained in Step (a) and the following general formula (III)
Reacting with an amine represented by the formula (1) to obtain a mixture of the sulfobetaine represented by the general formula (I) and a compound represented by the following general formula (IV).

[0012]

[Chemical 9]

(In the formula, R ¹ , R ² , R ³ , A, Y and m have the above-mentioned meanings.)

[0014]

[Chemical 10]

(Wherein R ¹ , R ² , R ³ , A, Y, X and m have the above-mentioned meanings) Step (c) In the mixture obtained in Step (b), the above-mentioned general formula ( I)
A step of obtaining the sulfobetaine represented by the general formula (I) by separating the sulfobetaine represented by the formula (I) from the compound represented by the general formula (IV).

Each step will be described below. Step (a) This step is a sulfonation step, and as a sulfonating agent,
At least one selected from SO ₃ , XSO ₃ H (X is a halogen atom) and complexes thereof is used. The complex referred to here is a complex formed by SO ₃ and XSO ₃ H (X is a halogen atom) with a Lewis base such as amide, amine, ether or sulfide. Examples of the Lewis base include N, N-dimethylformamide, triethylamine, pyridine, dioxane and the like. The use of sulfuric acid and fuming sulfuric acid as the sulfonating agent is not preferable because water generated by the sulfonation reaction causes hydrolysis.

The sulfonation is carried out using either the liquid membrane sulfonation method or the stirred batch sulfonation method. When the liquid film method is used, SO ₃ is diluted to 1 to 20% with an inert gas such as nitrogen, helium, or argon or dry air and used as a gas phase reaction reagent. In the sulfonation of the present invention,
The contact between the sulfonating agent and the compound represented by the general formula (II) is carried out at a temperature as low as possible, preferably at -50 to 60 ° C.
The molar ratio of the sulfonating agent to the compound represented by the general formula (II) is preferably 0.9 to 1.4, 1.0 to 1.1
Is more preferable. Also, after this contact, 10-8
It is aged at 0 ° C for 0.1 to 24 hours, preferably at 15 to 60 ° C for 0.1 to 10 hours.

In this step, it is preferable to use a solvent because the contact temperature can be lowered and stirring can be facilitated. As the solvent, a halogen solvent such as dichloroethane or dichloromethane, or a complex forming solvent such as DMF can be used. The object of this step is the sulfonating agent and the general formula (II).
It is a 1: 1 adduct of the compound represented by. When the sulfonating agent is insufficient, the compound represented by the general formula (II) remains. In this case, the final product is the unsulfonated general formula (V)

[0019]

[Chemical 11]

(Wherein R ¹ , R ² , R ³ , R ⁴ , A, Y, X, m
Indicates the above meaning. ) The compound represented by
It releases phenol at the time of use and is not environmentally preferable. Therefore, the molar ratio of the sulfonating agent to the compound represented by the general formula (II) is preferably 0.9 or more. Conversely, when the sulfonating agent becomes excessive, the sulfonating agent and the general formula (I
Since the 2: 1 adduct of the compound represented by I) is produced as a by-product and the yield of the target compound decreases, the sulfonating agent of the general formula (II)
The molar ratio to the compound represented by is 0.9 to 1.4, especially
Most preferably, the reaction is carried out between 1.0 and 1.1.

When the contact between the sulfonating agent and the compound represented by the general formula (II) is carried out at the low temperature as described above, the reaction rate is slow, and it is confirmed that the reaction proceeds even after the contact is completed. To be done. Such slow reaction progress is not preferable from a commercial point of view. Therefore, aging at an appropriate temperature is required to finish the reaction quickly. Aging temperature is 10-80 ℃
It is preferable that it is in the range of 1. Since the side reaction, decomposition, etc. are promoted at a higher temperature than that and the yield is lowered, it is not preferable.

The sulfonation of the present invention is more preferably carried out in the presence of an acidic substance. As the acidic substance, inorganic acids such as sulfuric acid and phosphoric acid, and short chain fatty acids such as acetic acid are used. When 1 to 10% by weight is added to the compound represented by the general formula (II) and the reaction is carried out, the yield is 1 to 8
Improve about%.

Step (b) This step is a quaternization step, and is carried out by bringing the amine represented by the general formula (III) into contact with the sulfonated product obtained in step (a). The feature of the present invention is that after the sulfonation step (step (a)) is completed, the quaternization step (step (b)) is continued.
Is performed, and isolation of an intermediate product is not required on the way.

The problem in this step is that the target product, sulfobetaine, is decomposed at the end of the reaction and the yield is reduced. Therefore, the combination of reaction temperature and reaction time must be chosen to minimize yield loss due to decomposition. For this purpose, it is desirable to carry out the reaction at a high temperature within a short time. In particular, by adding the sulfonated compound obtained in step (a) to the amine of the general formula (III) which has been heated in advance, the initial reaction rate is increased and the reaction time is shortened.

In the quaternization reaction in this step, the molar ratio of the amine represented by the general formula (III) to the sulfonated compound is such that neutralization of the halogen acid generated during quaternization and the step
Considering the neutralization of the sulfonating agent used in excess in (a), 1.8
It is preferably set to 3.5. A slight excess of the amine represented by the general formula (III) improves the yield, but an excessive amount of the amine promotes decomposition. Therefore, the molar ratio of amine to sulfonated compound is most preferably 2.0 to 3.0.
When using a solvent, it is necessary to avoid solvolysis. Further, since the reaction temperature is high, a reaction solvent having a high boiling point is required to carry out the reaction under normal pressure, and an aprotic polar solvent such as dimethylformamide or dimethylacetamide is desirable. The yield of sulfobetaine is low in a low polarity solvent.

On the other hand, when the reaction is carried out in the absence of a solvent, the quaternization reaction proceeds at a yield equal to or higher than that when the reaction is carried out using a polar solvent. This is because the excess amount of the amine represented by the general formula (III) in the first half of the reaction is
In addition, in the latter stage of the reaction, it is speculated that the compound represented by the general formula (IV) exerts the same effect on the reaction as the polar solvent. When the reaction solvent is not used, there is no need to recover the solvent, and in addition to that, the reaction volume becomes small, which brings about a great commercial advantage.

In this step, the contact between the amine represented by the general formula (III) and the sulfonated product obtained in step (a) can be carried out by any method, but more preferably in step (a). The sulfonated product thus obtained is added to the amine of the general formula (III) heated to 50 to 160 ° C. This is because according to this method, the desired sulfobetaine represented by the general formula (I) can be obtained in a higher yield and in a shorter time.

Step (c) This step is a step of separating the sulfobetaine represented by the general formula (I) from the reaction mixture obtained in the step (b). After completion of the quaternization reaction in step (b), the resulting mixture consists of the desired product, sulfobetaine represented by the general formula (I), the compound represented by the general formula (IV), and other by-products. The target substance, sulfobetaine represented by the general formula (I), usually has good crystallinity and has different solubility to other compounds in an organic solvent or water. Therefore, purification can be easily performed by washing with a solvent or recrystallization. ..

When a solvent is used in the quaternization reaction of step (b), it is equivalent to recrystallization if crystals are precipitated by cooling, but if crystals are not precipitated, the solvent is distilled. It is necessary to carry out purification with other solvent. A solvent having a higher polarity is superior in purification ability, and as the aprotic solvent, acetone, acetonitrile, dimethylformamide, and as the protic solvent, an alcohol solvent such as methanol, ethanol, isopropanol, or water is used. ..

In the quaternization reaction of the step (b), a compound represented by the general formula (IV) is by-produced in an equimolar amount with the objective sulfobetaine represented by the general formula (I). General formula
The compound represented by (IV) is neutralized to give an amine represented by the general formula (III), and is recovered along with an excess of the amine represented by the general formula (III) which has not been used in the reaction in the step (b). It is preferable to reuse. Neutralization is performed with an alkaline aqueous solution such as an alkali metal hydroxide or an alkaline earth metal hydroxide. After the completion of neutralization, the amine represented by the general formula (III) is recovered by distillation.

[0031]

INDUSTRIAL APPLICABILITY According to the present invention, phenylsulfobetaine having an ester group, which is useful as a bleach activator in a high yield and a high purity without economically forming an inorganic salt such as sodium chloride as a by-product. Can be manufactured.

[0032]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Examples of Step (a) Examples 1 to 7 226.8 g (1.0 mol) of chlorocaproic acid phenyl ester were equipped with a stirrer, a cooling tube, a dropping funnel and a thermometer.
Liquid SO ₃ was added dropwise while the contact temperature was kept constant by ice cooling. After completion of dropping, aging was carried out at a constant temperature. The effects of contact temperature, molar ratio of SO ₃ to phenyl chlorocaproic acid ester, and aging temperature on the yield of sulfonated compounds were investigated. The results are shown in Table 1. The yield is the molar yield based on chlorocaproic acid phenyl ester, which was determined by liquid chromatography.

[0033]

[Table 1]

Example 8 113.4 g (0.5 mol) of chlorocaproic acid phenyl ester and 200 ml of dichloroethane as a solvent were mixed with a stirrer, a cooling tube,
40g of liquid SO ₃ was added to a 500ml four-necked round bottom flask equipped with a dropping funnel and a thermometer, stirred, and cooled with a dry ice-acetone bath to keep the temperature constant at -30 to -20 ° C. (0.5 mol) was added dropwise. After the completion of dropping, aging was carried out at 40 ° C. for 2 hours. After completion of the aging, quantification by liquid chromatography gave a sulfonated product in a yield of 95%. The solvent dichloroethane is
It was distilled off before the next quaternization reaction.

Examples 9 to 12 Chlorocaproic acid phenyl ester 226.7 g (1.0 mol) was added with various acidic additives shown in Table 2 in the amounts shown in Table 2, and a stirrer, a cooling pipe, a dropping funnel and a thermometer were provided. The mixture was placed in a 4-neck round bottom flask and stirred. Contact temperature 40 by ice cooling
The temperature was kept at 0 ° C., and 80 g (1.0 mol) of liquid SO ₃ was dropped. After completion of dropping, aging was carried out at 40 ° C. The effect of the type and amount of the acidic additive on the yield of the sulfonated product was investigated. The results are shown in Table 2. The results of Example 4 above without addition of an acidic additive are also shown.

[0036]

[Table 2]

Note) *: wt% relative to chlorocaproic acid phenyl ester Example 13 The same reaction as in Example 2 was carried out using a falling membrane sulfonation apparatus having a tube having a length of 4 m and a diameter of 14 mm. Chlorocaproic acid phenyl ester was flowed down the inner surface of the tube at a flow rate of 80 ml / min. SO ₃ diluted to 2-3% with nitrogen gas
The gas was passed through at a flow rate of 3.0 liters / minute. The jacket temperature was kept at 20 ° C with running water. Gas-liquid separation was performed at the outlet of the tube, the liquid sulfonated product was received in the storage tank, and aging was carried out at 40 ° C for 0.5 hour. After completion of the aging, quantification by liquid chromatography gave a sulfonated product in a yield of 89%.

Example of Steps (b) and (c) Example 14 A 3 liter, 4-neck round bottom flask equipped with a stirrer, condenser, dropping funnel and thermometer was used to formula (III-1) below.

[0039]

[Chemical formula 12]

589.8 g (2.3 mol) of an amine represented by
1000 g of the solvent N, N-dimethylacetamide was added and preheated to 100 ° C. According to the method of Example 2, 306.8 g of the sulfonated reaction product obtained by reacting chlorocaproic acid phenyl ester with SO ₃ was added all at once, and the reaction was carried out while maintaining the reaction temperature at 140 ° C. After 2 hours, quantification by liquid chromatography revealed that sulfobetaine represented by the following formula (I-1) produced by quaternization of the sulfonated product was obtained in a yield of 82%.

[0041]

[Chemical 13]

Regarding the above reaction, the amount of the desired sulfobetaine represented by the above formula (I-1) was examined with time. The result is shown by the solid line in FIG. Contrary to this, the dotted line shows the change with time in the case where the amine represented by the above formula (III-1) was added to the sulfonated product and the quaternization reaction was carried out. The reaction start time was the time when the temperature rise ended and the system temperature became constant. The results in FIG. 1 show that the yield was increased by 4-5% and the reaction time was halved by taking the method of adding the sulfonated product to the heated amine.

Next, when the reaction finished product is cooled to room temperature, crystals start to precipitate. The solid matter obtained by filtering the slurry solution is slurried again with a solvent such as acetone and water, filtered, and N, N-dimethylacetamide is washed away. This was dried to obtain 360.0 g of white powder. The white powder contained 95% or more of the desired product, sulfobetaine represented by the formula (I-1). The white powder thus obtained was dissolved in a 1: 1 mixed solvent of acetonitrile and water.
% Solution. When the APHA value of this solution was measured, it was about 50, the hue was good, and there was no problem in commercial use.

Example 15 589.8 g (2.3 mol) of the amine represented by the above formula (III-1) was placed in a 2-liter four-necked round bottom flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer. Heat to 100 ° C. Here, the sulfonated product obtained by reacting chlorocaproic acid phenyl ester with SO ₃ according to the method of Example 2
306.8 g was added at once and the reaction was carried out while maintaining the reaction temperature at 140 ° C. After 1.5 hours, quantification by liquid chromatography revealed that sulfobetaine of the above formula (I-1), which was formed by quaternization of the sulfonated product, was obtained in a yield of 92%.

With respect to the above reaction, the amount of sulfobetaine of interest was examined over time. The result is shown by the solid line in FIG.
The dotted line shows the change with time when the quaternization was carried out in the presence of a solvent. The results in FIG. 2 show that the yield was improved by about 10% and the reaction time was shortened by carrying out the reaction in the absence of solvent.

1 liter of isopropanol as a refining solvent was placed in a 3 liter four-necked round bottom flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, and the mixture was stirred. g (effective content 48%) was added dropwise. Since the quaternized product was heated to 80 ° C. in order to improve the fluidity, the temperature of the system rose to 60 ° C. After cooling the slurry solution, it is filtered and the filtered solid is dried to 404.0%.
g of white powder was obtained. The white powder is the target compound of the above formula (I
It contained 95% or more of sulfobetaine represented by -1). The white powder thus obtained is dissolved in a 1: 1 mixed solvent of acetonitrile and water to give a 10% solution. When the APHA value of this solution was measured, it was about 40 and the hue was good, showing no problem in commercial use.

Similar purification can be performed with other solvents such as ethanol and acetone. Depending on the solvent, the quaternized product may be completely dissolved when heated, but it is possible to carry out the same operation by precipitating crystals by cooling to form a slurry.

Reuse Example of Recovered Amine Example 16 As a result of reaction and purification according to Example 15, about 1.5 kg of filtrate remained after removing the crystals by filtration. Their composition was as follows. Solvent (isopropanol) 67% Amine of formula (III-1) 5% Amine hydrochloride of formula (III-1) 20% Other components 8% The solvent was first recovered from this mixture by distillation. To the distillation residue was added 100 ml of 48% NaOH aqueous solution to release the amine represented by the formula (III-1) from the hydrochloride of the amine represented by the formula (III-1). About 90% of the content could be recovered by distillation. Using this recovered amine, Example 14,
As a result of carrying out the reaction in the same manner as in Example 15, Examples 14 and 15
Similar results were obtained as described in.

Example 17 When N, N-dimethyloctylamine was used in place of the amine represented by the formula (III-1) in Examples 14 to 16, the following formula (I-2) was obtained. The sulfobetaine represented was obtained.

[0050]

[Chemical 14]

Example 18 In Examples 14 to 16, the amine represented by the following formula (III-2) was used in place of the amine represented by the formula (III-1). The sulfobetaine represented by I-3) was obtained.

[0052]

[Chemical 15]

[Brief description of drawings]

FIG. 1 is a graph showing the time-dependent change in the yield of sulfobetaine with respect to the desired sulfonated product, which was obtained by the reaction performed in Example 14.

FIG. 2 is a graph showing the change with time of the yield of sulfobetaine with respect to the target sulfonated product, obtained by the reaction performed in Example 15.

Claims (4)

[Claims] 1. A method for producing sulfobetaine represented by the general formula (I), which comprises performing the following steps (a) to (c). [Chemical 1] [In the formula, R ^{1 represents a} linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms, a phenyl group, or an alkyl-substituted aryl group having 1 to 20 total carbon atoms in the alkyl substituent. R ² and R ^{3 are the} same or different and each represents an alkyl group having 1 to 3 carbon atoms. R ⁴ : represents an alkylene group having 1 to 10 carbon atoms which may have a branched chain. [Chemical 2] m: Indicates the number of 0 or 1. ] Step (a) A compound represented by the following general formula (II), SO ₃ , XSO ₃ H
(Wherein X represents a halogen atom) and at least one sulfonating agent selected from these complexes,
A step of obtaining a sulfonated product. [Chemical 3] (In the formula, R ⁴ and X have the above-mentioned meanings.) Step (b) The sulfonated compound obtained in Step (a) and the following general formula (III)
A step of reacting by contacting with an amine represented by the formula (1) to obtain a mixture of the sulfobetaine represented by the general formula (I) and the compound represented by the following general formula (IV). [Chemical 4] (In the formula, R ¹ , R ² , R ³ , A, Y, and m have the above-mentioned meanings.) (In the formula, R ¹ , R ² , R ³ , A, Y, X and m have the above-mentioned meanings.) Step (c) In the mixture obtained in the step (b), the compound represented by the general formula (I)
A step of obtaining the sulfobetaine represented by the general formula (I) by separating the sulfobetaine represented by the formula (I) from the compound represented by the general formula (IV). 2. The method of bringing the sulfonated product obtained in step (a) into contact with the amine represented by the general formula (III) in step (b) is the sulfone obtained in step (a). The method for producing sulfobetaine according to claim 1, which is a method of adding the compound to the amine represented by the general formula (III) heated to 50 to 160 ° C. 3. The sulfonated product obtained in step (a) is
The method for producing sulfobetaine according to claim 1 or 2, wherein the two are contacted in the absence of solvent when added to the amine represented by the general formula (III) heated to 50 to 160 ° C. 4. The general formula (III) used in the step (b):
4. The amine according to claim 1, wherein the amine represented by is obtained by neutralizing the compound represented by the general formula (IV) recovered in step (c). Method for producing sulfobetaine.