JPH07258186A - Production of acylamino acid derivative - Google Patents

Abstract

PURPOSE:To readily produce an N-long chain acyamino acid useful as a low- stimulating activator, etc., or the derivative as its raw material at a low cost by reacting a fatty acid amide with a (meth)acrylic acid derivative in the presence of a base catalyst in an aprotic solvent. CONSTITUTION:This method for production of an acylamino acid derivative of the formula III (R<4> is H, a 1 to 4C alkyl or a group of the formula IV) is carried out by reacting (A) a fatty acid amide of the formula I (R<1>CO is a 8 to 22C fatty acid residue; R<2> is H, a 1 to 4C alkyl) with (B) a (meth)acrylic acid derivative (e.g. acrylonitrile, acrylic acid or acrylic acid amide) of the formula II (X is CO2R<2>, CN or CONH2; R<3> is H or CH3) in the presence of (C) a base catalyst [e.g. an alkaline (earth) metal alcoholate (1 to 3C), a hydroxide, etc.] in (D) an aprotic solvent (e.g. a hydrocarbon solvent or a halogenated hydrocarbon solvent). In addition, the amount of the component (B) is 0.6 to 2.0 times mole, preferably 0.8 to 1.5 time mole based on the component (A).

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 an N-long chain acylamino acid or an acylamino acid derivative which can be used as a raw material thereof, and more specifically, it is a simple method which is not restricted by the material of the reactor and The present invention relates to a method for producing a highly pure acylamino acid derivative using an inexpensive raw material.

[0002]

2. Description of the Related Art N-long-chain acylamino acids and salts thereof have excellent surfactant activity, bacteriostatic activity, etc. and are hypoallergenic, and are therefore used in various fields. ing. Conventionally, as a method for producing an N-long chain acylamino acid salt, Schotten-Baumann (Sc
hotten-Baumann) reaction is known (Japanese Patent Publication No. 46-8685).
JP-B-51-38681, JP-A-4-368378 and JP-A-5-7041). However, when the Schotten-Baumann reaction or an improved method thereof is used, it is necessary to use amino acids and fatty acid halides as raw materials in any case,
All of them have the drawbacks that they are expensive to obtain industrially, and that the materials for handling fatty acid halides are limited.

On the other hand, it has been proposed to use an acylamino acid derivative which is an inexpensive raw material in place of the amino acid and fatty acid halide having such a defect, and the acylamino acid derivative is obtained from a fatty acid amide and an acrylic acid derivative. It is already known that it will be (USP 3138606
, USP 302133, FP 1392760, BP 875134, BP 87
5135), this method uses a protic solvent such as methanol or formamide as a solvent, and has a drawback that the reaction rate is low.

Therefore, an object of the present invention is to provide an efficient production method suitable for industrial production of N-long chain acylamino acids or acylamino acid derivatives useful as raw materials thereof.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above problems can be solved by using an aprotic solvent when reacting a fatty acid amide with an acrylic acid derivative in the presence of a basic catalyst. The inventors have found out and completed the present invention. That is, the present invention, the general formula (1)

[0006]

[Chemical 5]

(In the formula, R ¹ CO- represents a saturated or unsaturated fatty acid residue having 8 to 22 carbon atoms, and R ² represents H or a linear or branched alkyl group having 1 to 4 carbon atoms. ) A fatty acid amide represented by the general formula (2)

[0008]

[Chemical 6]

[In the formula, X represents —CO ₂ R ² (R ² has the above meaning), —CN or —CONH ₂ , and R ³ represents H or —CH ₃ . ] The (meth) acrylic acid derivative represented by the formula (3) is characterized by reacting in the presence of a basic catalyst in an aprotic solvent.

[0010]

[Chemical 7]

[Wherein R ¹ , R ³ and X have the above-mentioned meanings, R ⁴ is H, a linear or branched alkyl group having 1 to 4 carbon atoms, or

[0012]

[Chemical 8]

(Wherein R ³ and X are as defined above). ] The manufacturing method of the acyl amino acid derivative represented by these is provided.

In the general formula (1), R ¹ CO is a linear or branched saturated or unsaturated fatty acid residue having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms. R ² is H or 1 carbon
To 4, preferably an alkyl group having 1 to 3 carbon atoms. Specific examples of the fatty acid amide represented by the general formula (1) include lauric acid amide, palmitic acid amide, stearic acid amide, oleic acid amide, N-methyllauric acid amide and N-ethyllauric acid amide. Examples include fatty acid amides having a single composition and amides of mixed fatty acids such as coconut oil fatty acid amide and tallow fatty acid amide. Although these may be produced by any method, for example, a fatty acid and an amine or ammonia are added to silica gel (oil chemistry,
15 , 406 (1966)) and Ti (O-iC ₃ H ₇ ) ₄ (JP-A-47-168)
It can be obtained by reacting in the presence of a catalyst such as.

In the general formula (2), X represents --CO ₂ R ² (R ² has the above meaning), --CN or --CONH ₂ , and R ³
Represents H or -CH ₃ , but preferably R ³ is H. Specific examples of the (meth) acrylic acid derivative represented by the general formula (2) include acrylonitrile, acrylic acid, acrylic acid amide, methyl acrylate, acrylic acid derivatives such as ethyl acrylate, methacrylonitrile, methacrylic acid, Methacrylic acid amide, methyl methacrylate, ethyl methacrylate, and other methacrylic acid derivatives are mentioned, but acrylic acid derivatives are preferable, and acrylonitrile, methyl acrylate, and ethyl acrylate are particularly preferable, and acrylonitrile is more preferable. These can be commercially available products.

The basic catalyst used in the present invention includes
Any of those showing basicity may be used, but from the viewpoints of ease of handling, price, etc., an alkali metal or alkaline earth metal alcoholate (having 1 to 3 carbon atoms, preferably 1 to 3 carbon atoms).
2), hydroxides or carbonates are preferred, and sodium methylate, sodium ethylate, potassium methylate, sodium hydroxide, potassium hydroxide are particularly preferred. The amount of the basic catalyst used is preferably 5 to 30 mol% and more preferably 10 to 20 mol% based on the (meth) acrylic acid derivative represented by the general formula (2). When the amount of the basic catalyst used is less than 5 mol%, the reaction time increases and the efficiency is industrially deteriorated. When the amount used exceeds 30 mol%, the reaction time is hardly shortened and it is economically wasteful.

The aprotic solvent used in the present invention is not a solvent such as water, alcohols and carboxylic acids which forms a hydrogen bond between molecules, but a solvent which cannot form a hydrogen bond between molecules. That is, hydrocarbon-based solvents and halogenated hydrocarbon-based solvents are preferred, and aliphatic hydrocarbons, aromatic hydrocarbons and their halides are preferred. As a preferred specific aprotic solvent,
Benzene, toluene, xylene, chlorobenzene, o-
Examples thereof include dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, hexane and cyclohexane.

According to the method of the present invention, the fatty acid amide represented by the general formula (1) is represented by the general formula (2), preferably 0.6 to 2.0 mol times, more preferably 0.8 to 1.5 mol times thereof. (Meth) acrylic acid derivative in the presence of a basic catalyst to the fatty acid amide represented by the general formula (1) in an amount of 0.1 to
It is possible to obtain an acylamino acid derivative represented by the general formula (3) by reacting in an aprotic solvent of 20 times by weight, preferably 0.5 to 10 times by weight, at 60 to 140 ° C, preferably 80 to 120 ° C. I can. When the reaction temperature is higher than 140 ° C, the acylamino acid derivative is decomposed, which is not preferable. When the basic catalyst is added to the reaction system as an aqueous solution or alcohol solution, after addition, the fatty acid amide represented by the general formula (1) and the general formula (2) (meta) are added.
Before the reaction of the acrylic acid derivative, it is preferable to remove the protic solvent such as water or alcohol by distilling under reduced pressure until the amount of the protic solvent does not impair the effects of the present invention.

In the fatty acid amide represented by the general formula (1), when R ² is H, the fatty acid amide and the general formula
When the molar ratio with the (meth) acrylic acid derivative represented by (2) ((meth) acrylic acid derivative / fatty acid amide) is 1.0 or more, particularly 2 or more, two substitutions represented by the general formula (4) are performed. A tertiary amide bearing a group is obtained. A tertiary amide having these two substituents can also be used as a raw material for producing an N-long chain acylamino acid.

[0020]

[Chemical 9]

(In the formula, R ¹ , R ³ and X have the same meanings as described above.) The acylamino acid derivative represented by the general formula (3) thus obtained is used as it is as a raw material for various reactions. However, if necessary, a purification step such as distillation or recrystallization may be performed. Generally, recrystallization requires facilities such as a filter and a dryer to be added industrially, and since a solvent is used, a recovery facility for the solvent is also required, and distillation purification is preferable.

The acylamino acid derivative represented by the general formula (3) thus obtained is hydrolyzed by a known method and is useful as a surfactant in the N-type represented by the following formula (5).
It can lead to long-chain acyl amino acids or salts thereof.

[0023]

[Chemical 10]

(In the formula, R ¹ , R ² and R ³ have the above-mentioned meanings, M represents H or a cation.) That is, for example, in the general formula (3), amidonitrile in which X is —CN. In the case of, the N-long-chain acylamino acid salt can be easily obtained by hydrolysis in the presence of a basic substance, and if necessary, the pH of the N-long-chain acylamino acid can be adjusted by adjusting the pH to 1 to 5 with a mineral acid. Amino acids can be obtained.

[0025]

EFFECTS OF THE INVENTION According to the production method of the present invention, an N-long chain acylamino acid which is extremely useful as a mild activator or the like, or an acylamino acid derivative which is useful as a raw material thereof, can be simply used without being restricted by the material of the reactor. Can be produced with good quality and industrially using various raw materials.

[0026]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
In the examples,% is based on weight unless otherwise specified. Unless otherwise specified, the yield was quantified by liquid chromatography and shown as a molar yield with respect to lauric acid amide.

Example 1 163.0 g of lauric acid amide (purity 97.5%: 0.80 mol), o
-Dichlorobenzene 1600g, 28% sodium methylate / methanol solution 23.0g (15mol% to lauric acid amide)
A stirrer, Dean Stark fractionating tube, cooling tube, thermometer,
The mixture was placed in a 5-liter 5-necked flask equipped with a nitrogen introducing tube and heated to 100 ° C. to form a uniform solution. While heating at 100 ° C., nitrogen was blown in to expel the methanol in the system out of the system. From there, heat the temperature to 120 ° C, add a small amount of hydroquinone as a polymerization inhibitor, and add acrylonitrile 63.3
g (1.5 equivalents to lauric acid amide) was added dropwise over 1 hour to react with N-lauroyl-β with a yield of 93.6%.
-Aminopropionitrile was obtained.

Example 2 120.0 g of lauric acid amide (purity 97.5%: 0.59 mol), o
-Dichlorobenzene 500g, 21% sodium ethylate / ethanol solution 28.5g (15mol% to lauric acid amide)
Was placed in a 1-liter 4-necked flask equipped with a stirrer, a Dean-Stark fractionating tube, a cooling tube, and a thermometer, heated to 120 ° C to make a uniform solution, and a small amount of hydroquinone as a polymerization inhibitor was added, and ethyl acrylate 88.1 When g (1.5 equivalents to lauric acid amide) was added dropwise for 1 hour to react, ethyl N-lauroyl-β-aminopropionate was obtained with a yield of 89.9%.

Example 3 20.5 g of lauric acid amide (purity 97.5%: 0.10 mol), 101.5 g of toluene, 3.5 g of 30% potassium methylate-methanol solution (15 mol% relative to lauric acid amide) were stirred and a Dean-Stark fractionating tube. Put it in a 300 ml four-necked flask equipped with a cooling tube and a thermometer, heat it to 90 ° C to make a uniform solution, and add 12.9 g of methyl acrylate (1.5 equivalents to lauric acid amide) dropwise for 0.5 hours to react. Where
Methyl N-lauroyl-β-aminopropionate was obtained with a yield of 90.1%.

Example 4 163.0 g of lauric acid amide (purity 97.5%: 0.80 mol), o
-Dichlorobenzene 90 g, 20% potassium hydroxide / methanol solution 67.3 g (30 mol% to lauric acid amide), a stirrer, a Dean-Stark fractionating pipe, a cooling pipe, a thermometer, a 5 liter 5 port equipped with a nitrogen inlet pipe. Put in a flask, 100
The mixture was heated to 0 ° C to form a uniform solution. While heating to 100 ℃,
Nitrogen was blown in to expel methanol in the system out of the system.
From there, heat the temperature to 120 ° C, add a small amount of hydroquinone as a polymerization inhibitor, and add 169.2 g of acrylonitrile.
When (4.0 equivalents to lauric acid amide) was added dropwise for 1 hour to react, N-lauroyl-bis (β-aminopropionitrile) was obtained with a yield of 89.9%. The yield was quantified by gas chromatography.

Comparative Example 1 Lauric acid amide 10.0 g (purity 97.5%: 0.049 mol), dimethylacetamide 100.3 g, 28% sodium methylate / methanol solution 1.4 g (15 mol%, relative to lauric acid amide) were added with a stirrer and Dean Stark. The mixture was placed in a 200 ml 5-necked flask equipped with a distillation tube, a cooling tube, a thermometer, and a nitrogen introduction tube, and heated to 100 ° C. to form a uniform solution. 100
With heating at ℃, nitrogen was blown in to expel the methanol in the system out of the system. From there, heat up to 120 ° C,
Add a small amount of hydroquinone as a polymerization inhibitor and add 3.9 g of acrylonitrile (1.5 equivalents to lauric acid amide).
When dropped and reacted for 0.5 hours, the yield was 36.2% and N
-Lauroyl-β-aminopropionitrile was obtained.

Comparative Example 2 N-lauroyl-β-aminopropionitrile was not detected in the same reaction as Comparative Example 1 except that 100.3 g of dimethylacetamide was changed to 100.3 g of methanol.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07C 255/29 // C07B 61/00 300

Claims (4)

[Claims] 1. A general formula (1): (In the formula, R ¹ CO- represents a saturated or unsaturated fatty acid residue having 8 to 22 carbon atoms, and R ² represents H or a linear or branched alkyl group having 1 to 4 carbon atoms.) And a general formula (2): [In the formula, X represents —CO ₂ R ² (R ² has the above-mentioned meaning), —CN or —CONH ₂ , and R ³ represents H or —CH ₃ . ] (Meth) acrylic acid derivative represented by, in the presence of a basic catalyst,
General formula (3): characterized by reacting in an aprotic solvent [Wherein R ¹ , R ³ and X have the above-mentioned meanings, R ⁴ is H, a linear or branched alkyl group having 1 to 4 carbon atoms, or a compound represented by the formula: (In the formula, R ³ and X have the above-mentioned meanings). ] The manufacturing method of the acyl amino acid derivative represented by these. 2. The production of an acylamino acid derivative according to claim 1, wherein the (meth) acrylic acid derivative represented by the general formula (2) is acrylonitrile, acrylic acid, acrylic acid amide, methyl acrylate or ethyl acrylate. Law. 3. The method for producing an acylamino acid derivative according to claim 1, wherein the basic catalyst is an alkali metal or alkaline earth metal alcoholate (having 1 to 3 carbon atoms), a hydroxide or a carbonate. 4. The method for producing an acylamino acid derivative according to claim 1, wherein the aprotic solvent is a hydrocarbon solvent or a halogenated hydrocarbon solvent.