JPH0532600A - Production of betaine compound - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful as surfactants, etc., in excellent yield by reacting an aliphatic primary amine with a quaternary ammonium compound having a specific structure at a specified pH and then reacting the reaction product with a halogenated lower carboxylic acid. CONSTITUTION:An aliphatic primary amine (e.g. octylamine) expressed by the formula R<1>NH2 (R<1> is 8-22C alkyl, alkenyl or hydroxyalkyl) is reacted with a compound (e.g. 3-chloro-2-hydroxypropyltrimethylammonium chloride) expressed by formula I (Y us halogen; X is H or OH; R<2> to R<4> are 1-4C alkyl; Z is OH, halogen or 1-4C alkylsulfuric acid) at pH 6-8 to provide a compound expressed by formula II, which is then reacted with halogenated lower alkylenecarboxylic acids (e.g. sodium monochloroacetate) expressed by the formula Y(CH2)nCOOH ((n) is 1-5; M is H, alkyl or alkali metal) to afford the objective betaine compound expressed by formula III.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a betaine compound which has a mild action on the skin and which has excellent foaming power and detergency and is useful as a surfactant for washing hair or body. Is.

[0002]

2. Description of the Related Art In recent years,
Surfactants used for detergents and the like are required to have excellent properties such as biodegradability, safety, and low irritation to eyes and skin, in addition to the surfactant ability. Acylamino acid type surfactants and imidazoline type surfactants have been widely used as the surfactants satisfying these requirements. However, while these surfactants are generally excellent in safety and the like, they are inferior in foaming power and detergency, which are particularly important as surface activity, and therefore, they cannot be used alone as a component of shampoo or the like. However, it is generally used in combination with an anionic surfactant such as alkyl ether sulfate or alkyl sulfate. Since such an anionic surfactant is highly irritating to the skin, it may damage the skin. Therefore, it is strongly desired to develop an active agent having excellent foaming power and cleaning power and high safety.

[0003]

In view of the above situation, the present inventors have excellent cleaning power and foaming power for cleaning hair and body,
As a result of intensive studies on a surfactant having high safety, the following general formula (1)

[0004]

[Chemical 7]

(In the formula, R ¹ is a linear or branched alkyl group having 8 to 22 carbon atoms, an alkenyl group or a hydroxyalkyl group, X is H or a hydroxyl group, and R ² , R ³ and R ⁴ are carbon atoms. 1 to 4 alkyl groups, n is a number of 1 to 5), and found that the betaine compound represented by
Such a compound is reacted with an aliphatic primary amine and a quaternary ammonium compound having a specific structure at a pH of 6 or more and less than 8 and the resulting reaction product is reacted with a specific halogenated lower carboxylic acid at a pH of 6 or more and less than 8 It was found that the production can be efficiently performed by the above, and the present invention has been completed.

That is, the present invention has the general formula (1)

[0007]

[Chemical 8]

(Wherein R ¹ is a linear or branched alkyl group having 8 to 22 carbon atoms, a hydroxyalkyl group or an alkenyl group, X is H or a hydroxyl group, and R ² , R ³ and R ⁴ are carbon atoms. The present invention provides a method for producing a novel betaine compound represented by 1 to 4 alkyl groups and n is a number of 1 to 5).

The present invention will be described in detail below.

The betaine compound of the present invention can be produced by the following two production methods <1> and <2>.

Production method <1> Aliphatic group represented by aminated R ¹ NH ₂ (R ¹ represents a linear or branched alkyl group having 8 to 22 carbon atoms, an alkenyl group or a hydroxyalkyl group) General formula (2) for primary amines

[0012]

[Chemical 9]

(Wherein Y is a halogen atom, X is H or a hydroxyl group, R ² , R ³ and R ⁴ are alkyl groups having 1 to 4 carbon atoms, Z is OH, a halogen atom or 1 to 4 carbon atoms. The compound represented by the formula (3) is used to react the reaction system at a pH of 6 to 12 using 1 to 3 moles of the compound represented by the general formula (3)

[0014]

[Chemical 10]

(In the formula, R ¹ is a straight or branched chain carbon number of 8 to
22 an alkyl group, a hydroxyalkyl group, an alkenyl group, X is H or a hydroxyl group, and R ² , R ³ and R ⁴ are each a carbon number of 1 to 1.
4 alkyl group, Z is OH, halogen atom or 1 to 1 carbon atoms
4 shows an alkylsulfate group of 4. ) Compound (3)
Is generated. Betaining Then, the compound (3) and the general formula (4) Y (CH ₂ ) _n COOM (4) (wherein Y is a halogen atom, n is a number of 1 to 5, M is H,
A lower alkyl group and an alkali metal are shown. ) The halogenated lower alkylene carboxylic acid represented by the formula (1) or an ester or metal salt thereof is used at 1 to 3 times the molar amount of the compound (3) to react the reaction system at a pH of 6 to 12,
The betaine compound (1) can be easily produced. The above reaction example is as follows.

[0016]

[Chemical 11]

(In the formula, R ¹ , X, and n have the above-mentioned meanings.) The reaction between the primary amine and the compound (2) is usually carried out by adding an aqueous solution of the compound (2) to the primary amine and then adjusting the pH. Is preferably maintained at 6 to 12, and for that purpose an alkaline solution such as sodium hydroxide or potassium hydroxide is charged into the reaction solution if necessary. During the reaction, the pH of the reaction system is maintained within the above range in order to react the primary amine with the compound (2). It is preferably pH 6 or above,
When it exceeds 12, hydrolysis of the compound (2) occurs, which is not preferable. The reaction proceeds even at room temperature, but the higher the temperature, the faster the reaction. However, when temperature and pH are high, compound (2)
The reaction temperature is 100 ° C. or lower, preferably 90 ° C. or lower, since the hydrolysis of the above is accelerated. In the production method <1>, the molar ratio of the compound (2) and the primary amine is usually 1/1 to 3
/ 1, preferably 1.1 / 1 to 1.5 / 1. If the molar ratio is less than 1/1, the reaction rate will decrease and
If it exceeds, a large amount of the hydrolyzate of the compound (2) remains in the reaction mixture, which is not preferable. The end point of the reaction between the primary amine and the compound (2) can be confirmed by analyzing the residual amount of the primary amine in the reaction solution using high performance liquid chromatography. Then, a betaine is prepared by dropping an aqueous solution of the compound represented by the general formula (4) prepared in advance. Then, the above-mentioned alkaline aqueous solution is charged so as to have a pH of 6 to 12, while maintaining the temperature at 50 to 100 ° C, preferably 70 to 90 ° C. When the temperature is below 50 ° C, the rate of betaine formation is slow and
At a temperature of not lower than ° C, hydrolysis of the compound represented by the general formula (4) is promoted. In the production method of the present invention, the molar ratio of the halogenated lower alkylenecarboxylic acid or its ester or alkali metal salt (4) and the betaine precursor compound (3) is usually 1/1 to 3/1, preferably Is 1.1 / 1 ~
It is 1.5 / 1. The reaction time between the primary amine and the compound (2) in the production method of the present invention varies depending on the applied temperature and pH, but it generally takes 1 to 12 hours. Similarly, the reaction time in the latter stage generally depends on the applied temperature and pH, but it generally takes 1 to 12 hours. The reaction solution in the production method of the present invention is an aqueous solution, or water and a lower alcohol such as ethanol or isopropyl alcohol,
A mixed solution with diols such as 1,3-propanediol and propylene glycol may be used.

Of the compounds of the general formula (1), the compound (1) 'in which X is a hydroxyl group can be produced by the following method. Production Method <2> Amination The primary amine used in Production Method <1> and the general formula (5)

[0019]

[Chemical 12]

(In the formula, R ² , R ³ and R ⁴ have 1 to 4 carbon atoms.
Alkyl group, Z is OH, a halogen atom or 1 to 4 carbon atoms
Shows an alkylsulfate group of. ) And the glycidyltrialkylammonium salt represented by

[0021]

[Chemical 13]

(Wherein R ¹ is a linear or branched alkyl group having 8 to 22 carbon atoms, a hydroxyalkyl group or an alkenyl group, R ² , R ³ and R ⁴ are alkyl groups having 1 to ⁴ carbon atoms, Z is O
H, a halogen atom or an alkylsulfate group having 1 to 4 carbon atoms is shown. To obtain the compound (3) '. Then, betaine formation is carried out under the same conditions as in production method <1> to obtain the desired betaine compound (1) ′. The production method <2> will be described below with a specific example.

[0023]

[Chemical 14]

(In the formula, R ¹ and n have the above-mentioned meanings.) In the reaction of the glycidyl trialkylammonium salt represented by the general formula (5) with the primary amine, the general formula (5) is represented. The molar ratio of the compound to the primary amine is 1/1 to 3
It is / 1. If the molar ratio is less than this range, the reaction rate decreases, and if the molar ratio exceeds this range, a large amount of the hydrolyzate of the compound represented by the general formula (5) remains in the reaction mixture. Not preferable. The reaction temperature is 50 ~
The temperature is 120 ° C, preferably 60 to 100 ° C. If the reaction temperature is below this range, the reaction rate is slow, and if it is above this range, coloring or the like occurs, which is not preferable. The reaction between the primary amine and the glycidyltrialkylammonium salt (5) ensures the reactivity, and in order to proceed a certain reaction, an appropriate amount of alkaline aqueous solution is charged to maintain the pH at 6-12. It is preferable. If the pH is below this range, the reaction proceeds slowly, and if it exceeds this range, by-products are produced and the yield is reduced. The conditions for betaine formation in the production method <2> are as described in the production method <1>.

The reactions of the present invention described above as the production methods <1> and <2> may be carried out in air or in an inert gas atmosphere, but they are inert in view of coloration prevention. It is preferably performed in a gas atmosphere.

Primary amine R ¹ NH ₂ used in the present invention
(R ¹ represents the above meaning), for example, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, oleylamine, behenylamine, isostearylamine,
Examples thereof include coconut fatty amine.

The above formula obtained by the manufacturing method of the present invention
The betaine compound of (1) has surface activity, and a surfactant containing such a compound as a main component is excellent in foaming power and detergency,
Moreover, since it is hypoallergenic, it can be used not only as a hair washing base but also as a body washing base.

[0028]

EXAMPLES Next, the present invention will be explained in detail based on examples, but the scope of the present invention is not limited by these.

Example 1 Amination (Synthesis of Compound (3)) Dodecylamine (MW 185) 185 was placed in a 2 liter-4 neck flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel.
g, ion-exchanged water 200 g, and ethanol 100 g were charged. Then the mixture was heated to 75 ° C. with stirring. Next, a 50% aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride (MW 188) 489
g was added dropwise over 2 hours. During this period, 40% sodium hydroxide was appropriately added dropwise to maintain pH 7.5. After the addition of 3-chloro-2-hydroxypropyltrimethylammonium chloride was completed, heating and stirring were continued while maintaining pH 7.5, and the remaining amount of dodecylamine was confirmed by high performance liquid chromatography every hour. . 3-chloro-
Six hours after the dropwise addition of 2-hydroxypropyltrimethylammonium chloride was completed, the in-system concentration of dodecylamine reached 0.1%, and the process proceeded to the next step of betaine formation.

Betaining (Synthesis of Compound (1)) Next, after heating the above mixture to 80 ° C., a previously prepared 40% aqueous solution of sodium monochloroacetate (MW 116.5) was prepared.
g was added dropwise over 2 hours. In order to maintain pH 7.5 during this period, 40
% Aqueous sodium hydroxide solution was added dropwise. While maintaining pH 7.5 and continuing heating and stirring, the reaction was carried out by high performance liquid chromatography until the in-system concentration of compound (3) reached 0.1%, and then the reaction was terminated. After the reaction solution was purified using an electrodialysis device, a part thereof was evaporated to dryness, and the compound of the general formula (1) N-dodecyl-N- (3-trimethylammonio-2) was analyzed by IR analysis and mass spectrometry. It was confirmed that -hydroxypropyl) aminoacetate was obtained.

Results of IR analysis and mass analysis <IR analysis> At 1590 cm ⁻¹ (6.25 μ), strong absorption peculiar to carboxylate ion was observed. <Mass Spectrometer> Equipment: JEOL Ltd. SX-102 type mass spectrometric measurement condition; introduction method direct; ionization method FAB (Fast Atom Bombardment) analysis result; molecular weight of fragment ion 359 300 256 3 main peaks It was observed, and 359 was a parent ion peak of (M + 1), which confirmed that the compound had the structure of the betaine compound of the present invention.

Example 2 A betaine compound was obtained by performing the same reaction as in Example 1 except that 3-chloropropyltrimethylammonium chloride was used as a raw material. Results of IR analysis and mass analysis <IR analysis> At 1570 cm ^-1 (6.45μ), strong absorption peculiar to carboxylate ion was observed. <Mass Spectrometry> The same conditions as in Example 1 were used. A parent ion peak of 343 (M + 1) was observed, confirming that it is the betaine compound of the present invention.

Example 3 Amination (Synthesis of Compound (3) ') Dodecylamine (MW 185) 185 was placed in a 2 liter-4 neck flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel.
g, ion-exchanged water 200 g, and ethanol 100 g were charged. Then the mixture was heated to 75 ° C. with stirring. Then, a 50% aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride (MW 188) 489
g and 40 g of a 40% aqueous sodium hydroxide solution were simultaneously added dropwise from a microtube pump connected to a pH controller, and 40% sodium hydroxide was appropriately added dropwise during this period to maintain the pH at 7.5. After the addition of 3-chloro-2-hydroxypropyltrimethylammonium chloride was completed, heating and stirring were continued while maintaining pH 7.5, and the remaining amount of dodecylamine was confirmed by high performance liquid chromatography every hour. . 6 hours after the addition of 3-chloro-2-hydroxypropyltrimethylammonium chloride was completed, the concentration of dodecylamine in the system was
It became 0.1% and proceeded to the next step, betaineization.

Betaining (Synthesis of Compound (1) ′) Next, after heating the above mixture to 80 ° C., a previously prepared 40% aqueous solution of sodium monochloroacetate (MW 116.5) was prepared.
g and 40 g of a 40% aqueous sodium hydroxide solution were simultaneously added dropwise from a microtube pump connected to a pH controller. During this time, a 40% aqueous sodium hydroxide solution was appropriately added to maintain the pH at 7.5. After the reaction solution was purified using an electrodialysis device, a part thereof was evaporated to dryness, and the compound of the general formula (1) ′, N-dodecyl-N- (3-trimethylammonio-), was analyzed by IR analysis and mass spectrometry. It was confirmed that 2-hydroxypropyl) aminoacetate was obtained.

[0035]

INDUSTRIAL APPLICABILITY According to the present invention, a betaine compound useful as a surfactant can be obtained in extremely high yield.

Claims (2)

[Claims] 1. An aliphatic primary amine R ¹ NH ₂ (R ¹ represents a linear or branched alkyl group having 8 to 22 carbon atoms, an alkenyl group or a hydroxyalkyl group) and the general formula (2). [Chemical 1] (In the formula, Y is a halogen atom, X is H or a hydroxyl group, R ² , R ³ , and R ⁴ are alkyl groups having 1 to ⁴ carbon atoms, Z is OH, a halogen atom, or an alkyl sulfate group having 1 to 4 carbon atoms. The compound represented by the general formula (3): (In the formula, R ¹ is a linear or branched alkyl group having 8 to 22 carbon atoms, a hydroxyalkyl group or an alkenyl group, and X is
H ² or a hydroxyl group, R ² , R ³ and R ^{4 each} represent an alkyl group having 1 to ⁴ carbon atoms, and Z represents OH, a halogen atom or an alkylsulfate group having 1 to 4 carbon atoms. ) To produce a compound (3), and then the compound (3) and the general formula (4) Y (CH ₂ ) _n COOM (4) (wherein Y is a halogen atom and n is a number of 1 to 5). , M is H,
A lower alkyl group or an alkali metal is shown. ) The halogenated lower alkylene carboxylic acid or its lower alkyl ester or alkali metal salt represented by
Is represented by the general formula (1): (In the formula, R ¹ is a linear or branched alkyl group having 8 to 22 carbon atoms, a hydroxyalkyl group or an alkenyl group, and X is
H or a hydroxyl group, R ² , R ³ and R ⁴ are alkyl groups having 1 to ⁴ carbon atoms, and n is a number of 1 to 5. The manufacturing method of the betaine compound represented by these. 2. An aliphatic primary amine R ¹ NH ₂ (R ¹ represents a linear or branched alkyl group having 8 to 22 carbon atoms, an alkenyl group or a hydroxyalkyl group) and the general formula (5). [Chemical 4] (In the formula, R ² , R ³ and R ⁴ are alkyl groups having 1 to ⁴ carbon atoms, and Z is O.
H, a halogen atom or an alkylsulfate group having 1 to 4 carbon atoms is shown. ) Is reacted with the glycidyltrialkylammonium salt at a pH of the reaction system of 6 to less than 8,
General formula (3) ' (In the formula, R ¹ is a linear or branched alkyl group having 8 to 22 carbon atoms, a hydroxyalkyl group or an alkenyl group, R ² , R ³ and R ⁴
Represents an alkyl group having 1 to 4 carbon atoms, Z represents OH, a halogen atom or an alkylsulfate group having 1 to 4 carbon atoms. ) To produce a compound (3) ', then the compound (3)' and the general formula
(4) Y (CH ₂ ) _n COOM (4) (wherein Y is a halogen atom, n is a number of 1 to 5, M is H,
A lower alkyl group or an alkali metal is shown. ) The halogenated lower alkylene carboxylic acid or its lower alkyl ester or alkali metal salt represented by
Is represented by the general formula (1) ′ wherein (In the formula, R ¹ is a linear or branched alkyl group having 8 to 22 carbon atoms, a hydroxyalkyl group or an alkenyl group, R ² , R
³ , R ⁴ are alkyl groups having 1 to ⁴ carbon atoms, and n is a number of 1 to 5. The manufacturing method of the betaine compound represented by these.