JP2001181245A - Method for producing n-substituted beta-alanine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an N-substituted β-alanine excellent in odor and hue. SOLUTION: An aliphatic primary amine is subjected to addition reaction with acrylic acid and the addition reaction product is brought into contact with an absorbent or the above amine is subjected to addition reaction with an acrylic acid derivative and the addition reaction product is brought into contact with an absorbent before or after subjecting the addition reaction product to hydrolytic treatment to produce the objective N-substituted β-alanine represented by the general formula: R1(R2)NCH2CH2COOM1 wherein R1 is a 6-24C hydrocarbon group which may contain a substituted group; R2 is hydrogen atom or a group of the formula: CH2CH2COOM2; M1 and M2 are each hydrogen atom, an alkali metal ion, an alkaline earth metal ion, mono, di or tri- alkanolammonium ion having a 2-3C alkanol group, a 1-5C alkyl group- substituted ammonium ion or ionized basic amino acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing N-substituted β-alanine (including a salt form).

[0002]

2. Description of the Related Art Recently, amino acid-based surfactants have been used as mild surfactants. N-substituted β-alanine represented by the following general formula (1) is classified as an amino acid-based amphoteric surfactant, for example, US Pat. No. 2,787,633, JP-A-6-116596.
And JP-A-9-3485.

R ¹ (R ² ) NCH ₂ CH ₂ COOM ¹ (1) (wherein R ¹ has 6 to ² carbon atoms which may contain a substituent.
And R ² is a hydrogen atom or —CH ₂ C
Shows the H ₂ COOM ^2, mono- having M ¹ and M ² are a hydrogen atom, an alkali metal ion, alkaline earth metal ions, ammonium ions, alkanol group having 2 to 3 carbon atoms,
A di- or trialkanol ammonium ion, an alkyl group-substituted ammonium ion having 1 to 5 carbon atoms or an ionized basic amino acid, wherein M ¹ and M ² may be the same or different. )

As described in the above-mentioned US Pat. No. 2,787,633, N-substituted β-alanine can be obtained by Michael addition of acrylic acid, acrylic acid ester, acrylonitrile or the like to an aliphatic primary amine. Can be produced by hydrolyzing the resulting addition reaction product.

Also, Japanese Patent No. 2511776 discloses that
A detergent composition comprising an N-substituted β-alanine-based surfactant and a hydroxycarboxylic acid is disclosed in JP-A-9-348.
No. 5 discloses a detergent composition in which an N-substituted β-alanine-based surfactant and an ether carboxylic acid-based surfactant are combined.

[0006]

However, the N-substituted β-alanine surfactant produced by such a conventional method has a bad odor when used as a detergent or a surfactant composition, for example. In addition, there is a problem that coloring occurs over time. In particular, when used in kitchen cleaners, hair cleaners, skin cleaners, and the like, unpleasant odor and coloring become problems, and the value as a product is significantly impaired.

Accordingly, an object of the present invention is to provide a method for producing an N-substituted β-alanine having good odor and hue.

[0008]

In order to achieve the above-mentioned object, the present inventors have made a first method for producing N-substituted β-alanine (including a salt form) and a second method for producing N-substituted β-alanine as described below. The manufacturing method was developed.

A first production method of the present invention is a method for producing an N-substituted β-alanine represented by the following general formula (1), wherein acrylic acid and an aliphatic primary amine are subjected to an addition reaction,
This is a method in which the obtained addition reaction product is brought into contact with an adsorbent. R ¹ (R ² ) NCH ₂ CH ₂ COOM ¹ (1) (wherein, R ¹ has 6 to ² carbon atoms which may contain a substituent.
And R ² is a hydrogen atom or —CH ₂ C
Shows the H ₂ COOM ^2, mono- having M ¹ and M ² are a hydrogen atom, an alkali metal ion, alkaline earth metal ions, ammonium ions, alkanol group having 2 to 3 carbon atoms,
A di- or trialkanol ammonium ion, an alkyl group-substituted ammonium ion having 1 to 5 carbon atoms or an ionized basic amino acid, wherein M ¹ and M ² may be the same or different. )

In a second production method of the present invention, in the first production method, an acrylic acid derivative is replaced with an aliphatic primary amine in place of acrylic acid, and the resulting addition reaction product is adsorbed. And then hydrolyzing the obtained addition reaction product and then contacting the hydrolyzate with an adsorbent. The acrylic acid derivative is preferably an acrylate or acrylonitrile.

According to the first and second manufacturing methods,
By treating the addition reaction product or the hydrolyzate with an adsorbent, an N-substituted β-alanine free from the problem of off-odor and coloring can be obtained. Such an N-substituted β-alanine exhibits excellent properties that it does not generate off-flavors or coloring even when stored in a liquid state for a long period of time, and is therefore useful as, for example, a cleaning agent for kitchens, hair, and skin. It is.

In the first and second production methods of the present invention, the N-substituted β-alanine produced is, for example, one in which R ^{2 in the} above formula (1) is a hydrogen atom, ie, primary amine 1
One mole of acrylic acid or the like may be added to one mole (hereinafter, referred to as “1 mole adduct”), or the above formula (1)
Wherein R ² is —CH ₂ CH ₂ COOM ^2, that is, one in which 2 mol of acrylic acid or the like is added to 1 mol of primary amine (hereinafter, referred to as “2 mol adduct”), but is preferably 1 mole adduct.

In the first and second production methods of the present invention, the adsorbent is preferably an adsorbent containing at least one substance selected from the group consisting of activated carbon, silica, magnesia and alumina.

The N-substituted β-alanine produced by the first or second production method of the present invention is preferably used for a surfactant composition. Further, such a surfactant composition is preferably used for a detergent composition, and may further be used in combination with an anionic surfactant. As described above, by incorporating the N-substituted β-alanine according to the production method of the present invention, a detergent composition and a surfactant composition excellent in odor and hue can be obtained.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS One example of the first manufacturing method of the present invention will be described below.

First, an addition reaction between an aliphatic primary amine and acrylic acid is performed to produce N-substituted β-alanine. An example of this addition reaction is shown in the following formula (2).

R ¹ NH ₂ + CH ₂ ＣＨCHCOOH → R ¹ (R ² ) NCH ₂ CH ₂ COOH (2)

The formula (2) is not a formula representing only an equimolar addition reaction between the primary amine and acrylic acid, but includes, for example, a reaction of adding 2 moles of acrylic acid to 1 mole of the primary amine. . In the above formula (2), when N-substituted β-alanine is a 1-mol adduct, R ² represents a hydrogen atom, and when N-substituted β-alanine is a 2-mol adduct, R ² is
² shows a -CH ₂ CH ₂ COOH.

R ¹ NH ₂ shown in the above formula (2) is the above aliphatic primary amine, and R ¹ is a hydrocarbon group having 6 to 24 carbon atoms which may contain a substituent as described above. Show. The hydrocarbon group may be, for example, linear or branched, and may be saturated or unsaturated. Further, for example, it may optionally contain a substituent such as a hydroxyl group. The hydrocarbon group is preferably an alkyl or alkenyl group having 10 to 22 carbon atoms, and more preferably an alkyl or alkenyl group having 10 to 14 carbon atoms. Specifically, as R ¹ , for example, a hydrocarbon group derived from capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, etc .;
And hydrocarbon groups derived from tallow fatty acid and the like. These aliphatic primary amines can be produced using, for example, corresponding fatty acids or alcohols as raw materials.

The addition ratio (molar ratio) of the aliphatic primary amine to the acrylic acid is, for example, in the range of 1 to 2 moles of acrylic acid to the aliphatic amine, preferably 1.2 to 2 times.
The molar amount is 1.8 times, particularly preferably 1.4 to 1.6 times. If the molar ratio of acrylic acid to aliphatic primary amine is more than twice, the amount of residual acrylic acid will increase and the 2-mol adduct will tend to increase. When the molar ratio is less than 1, the unreacted aliphatic primary amine tends to increase.

The addition reaction is preferably carried out at a temperature in the range of 20 to 95 ° C, more preferably in the range of 40 to 90 ° C, particularly preferably in the range of 60 to 80 ° C. If the reaction temperature is lower than 20 ° C, the reaction time may take a long time. If the reaction temperature is higher than 95 ° C, the odor and hue of the N-substituted β-alanine may be deteriorated.

The reaction between the acrylic acid and the aliphatic primary amine is not particularly limited. For example, it is preferable to drop acrylic acid onto the aliphatic primary amine and then ripen (addition reaction). The time required for dropping is preferably 0.1 to 2 hours, more preferably 0.2 to 1.5 hours,
Particularly preferably, it is 0.5 to 1 hour. Aging time,
0.5 to 24 hours is preferable, and 1 to 12 is more preferable.
And particularly preferably 5 to 8 hours.

The addition reaction may be carried out in the presence of a solvent or in the absence of a solvent. As the solvent, for example, lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, and butanol, water, and the like, and a mixture thereof can be used. Among these solvents, methyl alcohol, ethyl alcohol and water are preferred. The amount of the solvent used is, for example, preferably 0.001 to 50 times, more preferably 0.1 to 5 times, and more preferably 1 to 5 times by weight the aliphatic primary amine.
4 times.

Next, after the addition reactant is brought into contact with the adsorbent, the adsorbent is removed.

As the adsorbent, activated carbon,
A material containing silica, magnesia, alumina, or the like can be used.
It is preferable to contain it in the range of 0% by weight. It is more preferably in the range of 20 to 80% by weight, particularly preferably 3 to 80% by weight.
It is in the range of 0 to 70% by weight. As the adsorbent containing at least one of silica, magnesia and alumina, for example, zeolite, silica / alumina, activated alumina,
Kyoward (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.), activated clay, and the like.

[0026] The adsorbent is, with respect to the addition reactant,
It is preferably added to be in the range of 0.1 to 10% by weight, more preferably in the range of 0.2 to 5% by weight, and particularly preferably in the range of 0.5 to 2% by weight. The treatment temperature is, for example, in the range of room temperature to 100 ° C, preferably in the range of 40 to 90 ° C, and more preferably in the range of 50 to 90 ° C.
~ 80 ° C. The processing time is, for example, 0.1 to
5 hours, preferably in the range of 0.5 to 3 hours, more preferably in the range of 1 to 2 hours. This treatment with the adsorbent is preferably performed while stirring.

The removal of the adsorbent can be performed by filtering the addition reaction product after the treatment. The filtration treatment is preferably performed under pressure or reduced pressure after adding a filter aid to the addition reaction product. Examples of the filter aid include Celite, Perlite, Hyflo Super Cell, K
C-floc (trade name, manufactured by Nippon Paper Industries) or the like may be used, and these may be used alone or in combination of two or more. The addition ratio of the filter aid is not particularly limited,
For example, 0.001 to 100 ml of the addition reaction product.
The range is 10 g, more preferably 0.01 to 2 g, and particularly preferably 0.05 to 1 g.

If the filtrate is recovered by the above-mentioned filtration, an N-substituted β-alanine in the acid form (M ¹ and M ² in the above formula (1) are hydrogen atoms) is obtained.

The N-substituted β-alanine may be in the form of a salt. For example, the N-substituted β-alanine may be neutralized with an alkali as shown in the following formula (3).

R ¹ (R ² ) NCH ₂ CH ₂ COOH → R ¹ (R ² ) NCH ₂ CH ₂ COOM ¹ (3)

In the above formula (3), R ¹ is the same as in the above formulas (1) and (2). R ² before neutralization reaction
Is the same as in the above formula (2), and R ² after the neutralization reaction is N ²
When the substituted β-alanine is a 1-mol adduct, it represents a hydrogen atom, and when the N-substituted β-alanine is a 2-mol adduct, it is —CH
₂ CH ₂ COOM ² is shown. M ¹ and M ² are an alkali metal ion, an alkaline earth metal ion, an ammonium ion, a mono-, di- or trialkanol ammonium ion having an alkanol group having 2 to 3 carbon atoms,
5 to 5 represent alkyl group-substituted ammonium ions or ionized basic amino acids. Examples of the alkali metal ion include ions such as lithium, potassium, and sodium. As alkaline earth metal ions,
For example, ions such as calcium and magnesium can be mentioned. Examples of the ionized basic amino acid include:
Cations such as lysine and arginine; When the N-substituted β-alanine is a 2 molar adduct, M ¹ and M ²
May be the same ion or different ions. Further, ^one of M ¹ and M ² may be a hydrogen atom.

In the case of producing such a salt-form N-substituted β-alanine, for example, the filtrate after the adsorption treatment may be neutralized with an alkali. Examples of the alkali include sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate,
Sodium bicarbonate and the various ammonium ions described above can be used. The reaction temperature is, for example, 20 to 90C, preferably 25 to 80C, more preferably 30 to 6C.
0 ° C. The reaction time is, for example, 0.01 to 2 hours, preferably 0.02 to 1 hour, and more preferably 0.1 to 0.5 hour.

The method for producing the N-substituted β-alanine in the form of a salt is not particularly limited to the above method. For example, when or after acrylic acid is added to the primary amine, the above-mentioned alkali is further added to the alkali. It can also be produced by adding and performing an addition reaction. In this case, the addition ratio of the alkali is, for example, in the range of 0.1 to 2 moles, preferably in the range of 0.2 to 1.5 moles, more preferably 0.5 mole, relative to the primary amine. It is in the range of 1 to 1 mole.

Next, an example of the second manufacturing method of the present invention will be described below.

First, an addition reaction is performed between an aliphatic primary amine and an acrylic acid derivative. An example of this addition reaction is shown in the following formula (4).

R ¹ NH ₂ + CH ₂ ＣＨCHX → R ¹ (R ² ) NCH ₂ CH ₂ X (4)

In the formula (4), R ¹ represents a hydrocarbon group having 6 to 24 carbon atoms which may contain a substituent, similarly to the formulas (1) to (3). When N-substituted β-alanine is a 1-mol adduct, R ² represents a hydrogen atom;
When the N-substituted β-alanine is a 2 mol adduct, R ² is —C
H ₂ CH ₂ X is shown. X represents an ester group (—COOR ³ ) or a cyano group (—CN), and R ³ represents, for example, a hydrocarbon group having 1 to 8 carbon atoms. R ³ preferably has 1 to 4 carbon atoms, and more preferably 1 to 2 carbon atoms.

The acrylic acid derivative (CH ₂ CHX)
For example, acrylonitrile (X is a cyano group in the above formula (4)), acrylate (X is an ester group in the above formula (4)) and the like can be used. Among the acrylates, methyl acrylate and ethyl acrylate are preferred. An N-substituted aminopropionate is obtained by an addition reaction of an acrylate ester, and an N-substituted aminopropionitrile is obtained by an addition reaction of acrylonitrile.

The conditions for the addition reaction are the same as those in the first production method except that an acrylic acid derivative is used instead of acrylic acid.

Next, the addition reaction product is hydrolyzed with an acid or an alkali. The acid hydrolysis produces an N-substituted β-alanine in the acid form, and the alkali hydrolysis produces an N-substituted β-alanine in the salt form. One example of the acid hydrolysis reaction is shown in the following formula (5), and one example of the alkali hydrolysis reaction is shown in the following formula (6).

(Acid Hydrolysis) Acid R ¹ (R ² ) NCH ₂ CH ₂ X → R ¹ (R ² ) NCH ₂ CH ₂ COOH (5)

In the above formula (5), R ¹ is the same as in the above formulas (1) to (4), and X is the same as in the above formula (4). R ² before hydrolysis is the same as in formula (4),
R ² after hydrolysis represents a hydrogen atom when N-substituted β-alanine is a 1-mol adduct, and represents —CH ₂ CH ₂ COOH when N-substituted β-alanine is a 2-mol adduct.

(Alkaline Hydrolysis) Alkali R ¹ (R ² ) NCH ₂ CH ₂ X → R ¹ (R ² ) NCH ₂ CH ₂ COOM ¹ (6)

In the above formula (6), R ¹ is the same as in the above formulas (1) to (4), and X is the same as in the above formula (4). R ² before hydrolysis is the same as in formula (4),
R ² after hydrolysis represents a hydrogen atom when the N-substituted β-alanine is 1 mol adduct, and represents —CH ₂ CH ₂ COOM ² when the N-substituted β-alanine is 2 mol adduct. M ¹ and M ² are the same as in the above formula (3).

This hydrolysis reaction can be carried out, for example, by adding an alkali or an acid dropwise to the addition reaction product and aging it. The temperature of the hydrolysis treatment is, for example, 20 to 1
In the range of 00 ° C, preferably in the range of 40 to 90 ° C,
More preferably, it is in the range of 60 to 80 ° C. The time required for the dropping is, for example, 0.1 to 3 hours, preferably 0.2 to 2 hours, and particularly preferably 0.1 to 2 hours.
The range is 5 to 1 hour. The aging time is, for example, 0.
The range is 5 to 12 hours, preferably 1 to 6 hours, and particularly preferably 2 to 4 hours. In particular, when acrylonitrile is used, it is preferable that the hydrolysis treatment is performed under a flow of an inert gas. Examples of the inert gas include a nitrogen gas and a helium gas. The flow rate of the gas is preferably 0.05 to 20 liters per liter of the processing liquid per minute (0.05 to 20 L / L / min), more preferably 0.1 to 10 L / L / min. Yes, particularly preferably 1 to
5 L / L / min.

As the alkali, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, sodium hydrogen carbonate, the above-mentioned various ammonium ions and the like can be used. Examples of the acid include an inorganic acid and an organic acid, and specific examples thereof include hydrochloric acid, sulfuric acid, benzoic acid, paratoluenesulfonic acid, boric acid, and phosphoric acid. The addition ratio of the alkali or acid is 100 ml for the addition reaction product.
Is, for example, in the range of 1 to 50 g, preferably in the range of 5 to 30 g, and more preferably in the range of 10 to 20 g.
g.

After the hydrolysis, if necessary, the pH of the treatment solution
May be adjusted to pH 7 to 12 with an acid or an alkali. The same acid or alkali as described above can be used. At this time, an inorganic salt or an organic salt is generated corresponding to the inorganic acid or the organic acid to be used, but may be removed by a desalting method such as electrodialysis if necessary.

Then, after the hydrolysis-added reaction product is brought into contact with the adsorbent in the same manner as in the first production method, the adsorbent is removed, whereby the formula (1) is obtained.
The N-substituted β-alanine shown in the following is obtained. In addition, the first
In the same manner as in the production method, N-substituted β-alanine in a salt form can be obtained.

The hydrolysis treatment step and the treatment step with the adsorbent are not limited to the above-mentioned order as described above.
For example, a hydrolysis treatment may be performed after the addition reactant is brought into contact with the adsorbent and the adsorbent is removed. In this case, the conditions for the addition reaction and the treatment of the hydrolyzate with the adsorbent are as follows:
Same as above.

The N-substituted β-alanine obtained by the production method of the present invention is excellent in that it does not contain components causing off-flavor and coloring due to the treatment with the adsorbent, and does not generate off-flavor or coloring even when stored. Show characteristics.

The N-substituted β-alanine obtained by the production method of the present invention is excellent in properties such as high detergency and high mildness in addition to the above-mentioned properties. Useful for things. Above all, the use of N-substituted β-alanine in various cleaning compositions such as a body cleaning agent, a kitchen cleaning agent, and a hard surface cleaning agent is very preferable.

When used in the cleaning composition, the N
The substituted β-alanine may be used alone, or may be mixed with another surfactant. As the N-substituted β-alanine, any of the above 1 mol adduct and 2 mol adduct can be used,
Although both may be used in combination, it is preferable to use only a 1-mol adduct. Examples of the other surfactant include an alkyl sulfate, an alkyl ethoxy sulfate, an α-sulfofatty acid ester, an alkylbenzene sulfonate, a soap, an alkyl ether carboxylate, an alkyl sulfosuccinate, and an alkyl phosphate. Anionic surfactants represented by ester salts, amino acid derivatives such as alkyl alaninate and alkyl taurate; polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, fatty acid alkanolamides, alkyl polyglucosides, short-chain alkyl glucoside lengths Nonionic surfactants represented by chain fatty acid esters, alkylmethylglucamides, sucrose fatty acid esters, etc .; alkylamine oxides, alkylcarbobetaines, alkylamidoalkylcarbobetaines, Kill sulfobetaines, alkyl hydroxy sulfobetaine,
Amphoteric and amphoteric surfactants typified by alkylimidazoline or derivatives thereof are preferred. Among these surfactants, anionic surfactants are preferred because they are particularly excellent in high detergency and foam performance. The mixing ratio of these surfactants is not particularly limited.
-1 to 10,000 parts by weight, more preferably 10 to 1000 parts by weight, particularly preferably 20 to 100 parts by weight, per 100 parts by weight of alanine.

The detergent composition containing the N-substituted β-alanine may contain, for example, components commonly used in general detergents, in addition to the surfactant. As the component, for example, alcohol-based hydrotropes such as lower alcohols and polyalkylene glycols,
Hydrotropes such as toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, benzoic acid and salicylic acid, low molecular aromatic compounds used as antibacterial agents, citric acid, malic acid, chelating agents such as EDTA, pigments, fragrances, Functional substances such as viscosity modifiers and inorganic compounds can be used, and the mixing ratio can be determined as appropriate.

[0054]

EXAMPLES Next, examples will be described together with comparative examples, but the present invention is not limited to the following examples. In the following examples, unless otherwise indicated,
“%” Is “% by weight”.

Examples 1 to 16, Comparative Examples 1 and 2
Table 1 and Table 2 below show the aliphatic primary amines, acrylic acid or acrylic acid derivatives, adsorbents and their addition ratios used in the above.

(Examples 1 to 3) (a) Addition reaction After charging 1.0 mol of alkylamine into a 1-liter four-necked flask, the mixture was heated and stirred at 60 ° C.
1.5 mol of acrylic acid was added dropwise from the dropping funnel over 1 hour, and aging was performed at the same temperature for 7 hours.

(B) Adsorbent treatment 100 g of the addition reaction product obtained by the above addition reaction and the adsorbent were added to a 1-liter four-necked flask, and the mixture was added at 60 ° C. for 1 hour.
Stirred for hours. The adsorbent is used for the alkylamine in a ratio of 1.
0% was added. Then, the adsorbent was removed by filtration to obtain N-substituted β-alanine.

(Examples 4 to 9) (a) Addition reaction After charging 1.0 mol of alkylamine into a 1-liter four-necked flask, the mixture was heated and stirred at 60 ° C.
1.5 mol of acrylic ester was added dropwise from a dropping funnel over 1 hour, and aging was performed at the same temperature for 7 hours.

(B) Hydrolysis reaction In a 1-liter four-necked flask, 100 g of the addition product obtained by the addition reaction, 100 g of ethyl alcohol and 70 g of water were added, and the temperature was raised to 70 ° C. with stirring. While maintaining the temperature at 70 ° C., a 40% NaOH aqueous solution 4
After dropping 5 g over 1 hour, aging was performed at the same temperature for 5 hours.

(C) Adsorbent treatment 100 g of the hydrolyzate and the adsorbent were added to a 1-liter four-necked flask and stirred at 60 ° C for 1 hour. The adsorbent was added so as to be 1.0% based on the alkylamine. Then, the adsorbent was removed by filtration to obtain N-substituted β-alanine.

Example 10 (a) Addition Reaction After charging 1.0 mol of alkylamine in a 1-liter four-necked flask, the mixture was heated and stirred at 60 ° C.
1.5 mol of acrylonitrile was added dropwise from a dropping funnel over 1 hour, and aging was performed at the same temperature for 7 hours.

(B) Hydrolysis reaction In a 1-liter four-necked flask, 100 g of the addition reaction product obtained by the addition reaction, 100 g of ethyl alcohol and 70 g of water were added, and the temperature was raised to 70 ° C. with stirring. While maintaining the temperature at 70 ° C., a 40% NaOH aqueous solution 4
5 g was added dropwise over 1 hour, and then under nitrogen flow (1 L / L
/ Min) and aging at the same temperature for 5 hours.

(C) Adsorbent treatment Into a 1-liter four-necked flask, 100 g of the hydrolyzate and the adsorbent were added, and the mixture was stirred at 60 ° C. for 1 hour. The adsorbent was added so as to be 1.0% based on the alkylamine. Then, the adsorbent was removed by filtration to obtain N-substituted β-alanine.

(Examples 11 to 16) (a) Addition reaction After charging 1.0 mol of alkylamine into a 1-liter four-necked flask, the mixture was heated and stirred at 60 ° C.
1.5 mol of acrylic ester was added dropwise from a dropping funnel over 1 hour, and aging was performed at the same temperature for 7 hours.

(B) Adsorbent treatment 100 g of the addition reaction product obtained by the above addition reaction and the adsorbent were added to a 1-liter four-necked flask, and the mixture was heated at 60 ° C. for 1 hour.
Stirred for hours. The adsorbent is used for the alkylamine in a ratio of 1.
0% (2.0% for Example 12). Thereafter, the adsorbent was removed by filtration.

(C) Hydrolysis reaction 100 g of the adsorbent-treated addition reaction product, 100 g of ethyl alcohol and 70 g of water were added to a 1-liter four-necked flask and heated to 70 ° C. with stirring. . While maintaining the temperature at 70 ° C., 45 g of a 40% NaOH aqueous solution was added dropwise over 1 hour, and then under a nitrogen flow (1 L /
(L / min) for 5 hours. After completion of the reaction, the pH was adjusted to 10 with hydrochloric acid to obtain N-substituted β-alanine.

(Comparative Example 1) An addition reaction was carried out in the same manner as in Example 1 except that the adsorbent treatment was not carried out.
-Alanine was obtained.

(Comparative Example 2) An addition reaction, a hydrolysis reaction and a pH adjustment were carried out in the same manner as in Example 4 except that the treatment with the adsorbent was not carried out to obtain N-substituted β-alanine.

Table 1 Acrylic acid or alkylamine acrylic acid derivatives Example 1 Laurylamine Acrylic acid Example 2 Laurylamine Acrylic acid Example 3 Myristylamine Acrylic acid Example 4 Laurylamine ethyl acrylate Example 5 Laurylamine Acrylic Ethyl acrylate Example 6 Laurylamine Ethyl acrylate Example 7 Laurylamine Ethyl acrylate Example 8 Myristylamine Ethyl acrylate Example 9 Laurylamine Methyl acrylate Example 10 Laurylamine acrylonitrile Example 11 Laurylamine Ethyl acrylate Example 12 Laurylamine ethyl acrylate Example 13 Laurylamine ethyl acrylate Example 14 Laurylamine ethyl acrylate Example 15 Myristylamine Ethyl acrylate Example 16 laurylamine methyl Comparative Example 1 laurylamine acrylate Comparative Example 2 laurylamine ethyl acrylate acrylate

(Table 2) Adsorbent Amount of adsorbent (%) Example 1 Kyoward KW600 1.0 Example 2 Activated carbon Shirasagi A 1.0 Example 3 Kyoward KW600 1.0 Example 4 Kyoward KW600 1. 0 Example 5 Kyoward KW700 1.0 Example 6 Example 6 Kyoword KW1000 1.0 Example 7 Activated carbon Shirasagi A 1.0 Example 8 Kyoword KW600 1.0 Example 9 Example Kyoword KW600 1.0 Example 10 Kyo Word KW600 1.0 Example 11 Kyoword KW600 1.0 Example 12 Kyoword KW600 2.0 Example 13 Kyoword KW700 1.0 Example 14 Activated carbon Shirasagi A 1.0 Example 15 Kyoword KW600 1.0 Example 16 Kyoword KW600 1.0

The product name “Kyoward KW600” (main component: silicon dioxide) and the product name “Kyoword KW70”
"0" (main component: silicon dioxide) and trade name "Kyoward KW1000" (main component: magnesium oxide) are manufactured by Kyowa Chemical Industry Co., Ltd., and trade name "Activated Carbon Shirasagi A" is manufactured by Takeda Pharmaceutical Company.

(Evaluation Experiment) The N-substituted β-alanine produced in Examples 1 to 16 and Comparative Examples 1 and 2 was
The odor and hue immediately after production and after storage at 50 ° C. for one month were evaluated according to the following evaluation criteria. The results are shown in Table 3 below.

(Evaluation of Odor) A sensory test was performed on each sample, and the odor was evaluated according to the following evaluation criteria. ：: good odor without off-flavors Δ: bad odor with slight off-odor ×: strong off-odor and extremely bad odor

(Hue Evaluation) The hue of each sample was visually evaluated according to the following evaluation criteria. ：: slight coloring △: coloring is observed X: marked coloring is observed

(Table 3) Immediately after production and storage for one month (50 ° C.) Odor Hue Odor Hue Example 1 ○ ○ ○ ○ Example 2 ○ ○ ○ ○ Example 3 ○ ○ ○ ○ Example 4 ○ ○ ○ ○ Example 5 ○ ○ ○ ○ Example 6 ○ ○ ○ ○ Example 7 ○ ○ ○ ○ Example 8 ○ ○ ○ ○ Example 9 ○ ○ ○ ○ Example 10 ○ ○ ○ ○ Example 11 ○ ○ ○ ○ Example 12 ○ ○ ○ ○ Example 13 ○ ○ ○ ○ Example 14 ○ ○ ○ ○ Example 15 ○ ○ ○ ○ Example 16 ○ ○ ○ ○ Comparative example 1 × △ × △ Comparative example 2 × △ × △

As shown in Table 3, the N-substituted β-alanine of Examples 1 to 16 exhibited excellent odor and hue even after storage for one month. On the other hand, the N-substituted β-alanine of Comparative Example 1 and Comparative Example 2 did not give good evaluation results in both odor and hue immediately after production.

(Examples 17 to 20, Comparative Examples 3 and 4) Using the N-substituted β-alanine produced in Examples 1, 4 and 11 and Comparative Example 1, the following Table 4 was used.
And the detergent composition was manufactured so that it might become the combination shown in Table 5. Then, for these cleaning compositions, the odor and hue immediately after production and after storage at 50 ° C. for one month,
The evaluation was performed according to the evaluation criteria. The results are shown in Tables 4 and 5 below. In both tables below,
POE lauryl sulfate Na salt is a lauryl sulfate Na salt of polyoxyethylene in which the addition mole number (n) of ethylene oxide is n = 3, and POE lauryl ether is
The addition mole number (n) of ethylene oxide is polyoxyethylene lauryl ether where n = 10, and the α-olefin sulfonic acid Na salt is an α-olefin sulfonic acid Na salt having 14 carbon atoms (n). In both tables below, the unit of the numerical value is part by weight, and the total of the composition is 100 parts.
Parts by weight.

(Table 4) Example Example Example Example Comparative Example 17 18 19 3 N-substituted β-alanine of Example 1 10 −−− N-substituted β-alanine of Example 4 −10 −− N of Example 11 Substituted β-alanine −− 10 − N-substituted β-alanine of Comparative Example 1 −− −10 POE lauryl sulfate Na salt −5 − − α-olefin sulfonic acid Na salt −55 −POE lauryl ether 5- −5-lauric acid Diethanolamide 5-55 Purified water Remaining Remaining Remaining Remaining Immediately after production Odor ○ ○ ○ × Hue ○ ○ ○ △ Odor after one month Odor ○ ○ ○ × (50 ° C) Hue ○ ○ ○ △

(Table 5) Example Comparative Example 20 N-substituted β-alanine 1.0 of Example 1 N-substituted β-alanine 1.0 of Comparative Example 1 Na salt of α-olefin sulfonic acid 1.0 1 0.0 Alkylbenzene sulfonic acid 1.0 1.0 Purified water Remaining Immediately after production Remaining odor ○ × Hue ○ △ After standing for one month Odor ○ × (50 ° C) Hue ○ △

As shown in Tables 4 and 5, the cleaning compositions of Examples 17 to 20 exhibited excellent odor and hue even after storage for one month. On the other hand, the cleaning compositions of Comparative Examples 3 and 4 did not give good evaluation results in both odor and hue immediately after production.

[0081]

As described above, according to the method for producing N-substituted β-alanine of the present invention, an adduct of a fatty acid primary amine with acrylic acid or an acrylic acid derivative or a hydrolyzate thereof is adsorbed. Thus, N-substituted β-alanine having no problem of odor and coloring can be produced. Such an N-substituted β-alanine, for example, has excellent odor when used in a detergent composition, and exhibits excellent characteristics of not causing coloring or off-odor even when stored for a long period of time. It is useful for cleaning agents for hair, hair, and skin.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H003 AB08 AB15 AB31 AC08 AC13 BA12 DA02 DA17 ED02 FA14 FA16 FA25 4H006 AA02 AC46 AC52 AD17 BD70 BE60 BS10 BS70 BU32

Claims (5)

[Claims] 1. An N-substituted β represented by the following general formula (1):
-A method for producing alanine, in which acrylic acid and an aliphatic primary amine are subjected to an addition reaction, and the resulting addition reaction product is brought into contact with an adsorbent. R ¹ (R ² ) NCH ₂ CH ₂ COOM ¹ (1) (wherein, R ¹ has 6 to ² carbon atoms which may contain a substituent.
And R ² is a hydrogen atom or —CH ₂ C
Shows the H ₂ COOM ^2, mono- having M ¹ and M ² are a hydrogen atom, an alkali metal ion, alkaline earth metal ions, ammonium ions, alkanol group having 2 to 3 carbon atoms,
A di- or trialkanol ammonium ion, an alkyl group-substituted ammonium ion having 1 to 5 carbon atoms or an ionized basic amino acid, wherein M ¹ and M ² may be the same or different. ) 2. The method according to claim 1, wherein in the general formula (1), R ² is a hydrogen atom. 3. An addition reaction of an acrylic acid derivative and an aliphatic primary amine in place of acrylic acid, and the resulting addition reaction product is contacted with an adsorbent and then hydrolyzed, or
The method according to claim 1, wherein after hydrolyzing the obtained addition reaction product, the hydrolysis product is brought into contact with an adsorbent. 4. The method according to claim 3, wherein the acrylic acid derivative is at least one of an acrylic ester and acrylonitrile. 5. The method according to claim 1, wherein the adsorbent is an adsorbent containing at least one substance selected from the group consisting of activated carbon, silica, magnesia and alumina.