JPH0193566A - N-acyl-n-(2-hydroxypropyl)-beta-alanine and salt thereof - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (n is 8-16). EXAMPLE:N-lauroyl-N-(2-hydroxypropyl)-beta-alanine. USE:A surfactant. Useful for cleaning agent for the hair and skin of infants and kitchen detergent, etc., because of its low irritation and high resistance to hard water. PREPARATION:The compound of formula I can be produced by reacting a fatty acid chloride of formula II with N-(2-hydroxypropyl)-beta-alanine sodium salt according to the reaction formula. Concretely, the reaction is performed by dripping the compound of formula II at room temperature to an aqueous solution of the compound of formula III while controlling the pH of the solution to 10-12 with an aqueous solution of NaOH.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides novel N-acyl-
This invention relates to N-(2-hydroquinepropyl)-β-alanine and its salts.

[Conventional technology]

Conventionally, as N-acylamino acids and their salts, N-7
Silglycine, N-acylsarcosine, N-acyl-β
-alanine, N-acyl-N-alkyl-β-alanine, N-acylglycylglycine, N-acylglutamine [, N-7flu N-(2-hydroxyethyl)glycine and their salts, etc. are known] There is. These compounds have characteristics such as having surfactant ability, mild effects on the skin, hair, eyes, etc., and good biodegradability, and are used in detergents, shampoos, toothpastes, emulsifiers, etc. It is used as an irritating base.

[Problem that the invention seeks to solve]

However, these known N-acylamino acid salts have insufficient basic performance as a surfactant, resulting in economical problems, high crystallinity, poor water solubility, etc. Due to problems, its use was limited.

In particular, the presence of divalent or higher metal ions, such as calcium ions, creates N-acylamino acid metal salts, which become insoluble in water and lose their original properties, which is a problem in terms of hard water resistance. Rarely.

In addition, N-acyl amino acids such as sodium and potassium
Even in the case of valent metal salts and organic salts such as ammonium and triethanolamine, as the number of carbon atoms in the acyl group increases, the solubility in water decreases, that is, the Krafft point increases, resulting in restrictions on the temperature range in which they can be used.

[A precautionary measure to resolve the problem]

Under these circumstances, the present inventors have developed N, which has excellent surfactant ability, is hypoallergenic, and is not limited in use.
As a result of extensive research aimed at developing -acyl amino acid derivatives, it was discovered that a β-alanine derivative into which a 2-hydroxypropyl group was introduced met the objective, and the present invention was completed.

That is, the present invention provides an N-acyl-N-(2- and Zoro♂
1)-β-alanine and its salt.

Preferred specific examples of the compounds of the present invention include - formula (
Among 1), compounds in which the group CHsCCH*)n and C- are lauroyl, miIristoyl, norQlumitoyl, and steamiyl groups are mentioned. In addition, as the salt of the compound of the present invention,
Alkali metals such as sodium and potassium; calcium,
Alkaline earth metals such as magnesium; ammonium; alkanolamines having a hydroxyalkyl group having 1 to 3 carbon atoms; alkyl-substituted ammonium having 1 to 3 carbon atoms;
Examples include salts of basic amino acids such as lysine and arginine.

Among these, N-5 uroyl N-(2-hydroxypropyl)-β-alanine, its sodium salt, or its triethanolamine salt is particularly preferred.

The compound of the present invention (11) is produced, for example, according to the following reaction formula.

Hs (II) [I[l] (wherein n has the same meaning as above), i.e. fatty acid chloride (Ill and N-(2-hydroxypropyl)
The compound (1) of the present invention is produced by reacting -β-alanine sodium salt @) in the presence of a base.

For example, the reaction is N-(2-hydroxypropyl)-β-
This is carried out by adding fatty acid chloride TIE) dropwise to an aqueous solution of alanine sodium salt 011) at room temperature while adjusting the pH to 10 to 12 with an aqueous sodium hydroxide solution.

Fatty acid chlorides (Ill) can be obtained by reacting the corresponding fatty acids with, for example, phosphorus trichloride.

In addition, N-(2-hydroxypropyl)-β-alanine (sodium salt dish) can be prepared by adding an appropriate amount of acrylonitrile dropwise to an aqueous monoingrononolamine solution at 60°C, stirring for several hours after the dropwise addition, and completing the reaction. -Hydroquinepropyl)-β-aminozolopionyl was obtained, which was then added dropwise to an appropriate amount of an aqueous sodium hydroxide solution under heating under reflux, and after the dropwise addition, it was hydrolyzed by heating under reflux while stirring for several hours. , by completely distilling off unreacted monoisochrono9olamine with water and by-product ammonia under reduced pressure.

[Effect]

The compound (1) of the present invention is excellent not only in surface activity and hypoallergenicity but also in hard water resistance, and the mechanism of the effect of improving hard water resistance is estimated as follows.

In general, surfactants fully demonstrate their surfactant ability when used at temperatures above the melting point of the surfactant solid, that is, the Kraft temperature, and anionic surfactants generally have a Kraft temperature. In particular, the presence of divalent or higher metal ions, such as calcium ions, causes counterion exchange of the surfactant, which greatly increases the Krafft point. Within the temperature range of actual use, the surfactant is precipitated in water as a water-containing solid such as calcium salt, which is insoluble in water, and its surfactant ability is lost. Therefore, in order to improve hard water resistance, it is necessary to lower the kraft point of surfactant calcium salts, etc. below the operating temperature.
As a result, good surfactant ability can be obtained even in hard water.

Conventional N-acylamino acid salts have a -()tide bond (-C-N-) t- in the molecule, so that intermolecular hydrogen bonds are formed at the peptide bond, resulting in a high craft point.

On the other hand, N-acyl-N-alkyl amino acid salts that have lost intermolecular hydrogen bonding properties by replacing hydrogen atoms in peptide bonds with alkyl groups, t, N-acylsarcosine salts, N-acyl-N-methyl - Although the Krafft point of β-alanine salts etc. decreases, in the presence of divalent metal ions such as calcium ions, 2 moles of surfactant associate with 1 mole of calcium ions, resulting in an apparent cyacyl type. , their hydrophobicity becomes so strong that they cannot be dissolved in water in the form of micelles, and they aggregate with each other and phase separate from the aqueous phase, resulting in a decrease in surfactant ability.

N-acyl-N-(2-hydroxypropyl) of the present invention
-β-Alanine and its salts reduce the crystallinity of the F surfactant water solid by introducing a sterically hindered 2-human mixizolobyl group into the peptide bonding moiety, which significantly lowers its craft point. In addition, even if a divalent metal salt such as a calcium salt is formed, it is dissolved in a micellar form due to the hydrophilicity imparted by the hydroxyl group, so it is presumed that it sufficiently exhibits its surfactant ability even in hard water.

〔Effect of the invention〕

The compound fl) of the present invention has excellent hard water resistance, low irritation, and excellent surfactant ability, so it can be used as a hair and skin cleanser for infants, a kitchen detergent for housewives who tend to get rough hands, and a detergent for daily hair washing. Suitable for use in people's daily shampoo, etc. It is also suitable for use in hypoallergenic beauty and beauty shampoos for people who are forced to come into contact with shampoos for long periods of time due to their occupation.

Furthermore, the effect is maintained not only when using tap water but also when using water with high hardness such as groundwater, hot spring water, seawater, etc. Also, by using it as an additive for other surfactants,
A foam increasing effect can be obtained in hard water. Furthermore, it can be used in the same applications as general surfactants, such as metal surface cleaning agents, antistatic agents, fiber treatment agents, penetrants, and emulsifiers for emulsion polymerization.

〔Example〕

Next, the present invention will be described in more detail with reference to Examples.0 Example 1 (300ge of monoinzolonoQ-nolamine was charged into a four-bottle flask of 111At, and after raising the temperature to 60°C, 212g of acrylonitrile was added from a dropping funnel for 1 hour while stirring. The reaction was then further stirred at 60°C for 3 hours to complete the reaction, and N-(2-hydroxyzologyl)-β
- Obtain aminode a bionitrile.

(2) N-(2-hydroxypropyl)-β-aminode-a-bionitrile obtained in (1) was added to a 4-bottle flask containing 176 g of sodium hydroxide and 2,600 g of water under heating under reflux for 1 hour. The mixture was added dropwise, and stirring was continued for 5 hours under reflux to effect hydrolysis. Then water,
Unreacted monoisozoro, 9-nolamine, and by-product ammonia were completely distilled off under heating and reduced pressure to obtain 670 g of N-(2-hydroxypropyl)-β-alanine sodium salt. Although this product also contained sodium N-(2-hydroxypropyl)iminozoderopionate and sodium hydroxide, they did not pose a problem during acylation and were used as they were in the next acylation.

+312A! N-
(2-Hydroxypropyl)-β-alanine sodium salt 170g and water 8409 were charged while stirring at 25°C.Dripping funnel J: 200g of lauric acid chloride total 2
It dripped in time. Meat, during this time the pH in the reaction system is 10-1.
30%-NaO from another dropping funnel to maintain a
The pH was adjusted by dropping the solution into H7. After the dropwise addition was completed, the mixture was stirred at HIO~11 for another hour to ensure that the reaction was complete.

The pH of the reaction product was adjusted to approximately 2 with hydrochloric acid, and the reaction product was extracted with ether. The ether layer was thoroughly washed with brine, then dehydrated with anhydrous sulfuric acid and IJum, and the ether was distilled off. The residue was 7'4 crystallized with Thn-hexane 7 to obtain 125 g of white powder of N-lauroyl-N-(2-hydroxypropyl)-β-alanine. When a small amount of the resulting white powder is added to water and heated, it becomes an emulsion and becomes acidic.

m, p,: 86°C IR (KBr): 3200-3400 F-1 (ν0H) 2850crlL-1 (νCH,) 292scIn-1 (νcH,) 1720c! rL-1 ("C=0) 1625cIrL-1 (SiC engineering O) Elemental analysis: Analysis value Calculated value C65,88% 65.65% H10,7410,64 019,2419,45 N 4.45 4.26 Total 100.31 100.00 Example 2 N-Myristoyl-
N-(2-hydroxyzolohyil)-β-alanine, N-
Norylmitoyl-N-(2-hydroxyzolopyl)-β
-Alanine, N-stearoyl-N (2-hydroxyzoroyl)-β-alanine was obtained.

Example 3 N-lauroyl-N (2-hydroquinzorogyl) obtained in Example 1 was placed in a reaction vessel with a capacity of 11 equipped with a stirrer.
-β-alanine (20 F CO 0,0607 mol) and 20 mol of ethanol were charged and stirred at room temperature to uniformly dissolve.

Next, 2.428 g (0,0607 g) of sodium hydroxide
Add 7001 de of acetone to the neutralized product. Add 7001 de of acetone to this neutralized product. After cooling to 0°C, the mixture was allowed to stand to precipitate N-lauroyl-N-(2-hydroxyzologyl)-β-alanine sodium salt. The precipitate was filtered off, and the solvent was completely distilled off under reduced pressure to obtain 14 g of N-lauroyl-N-(2-hydroxyzolopyl)-β-alanine sodium salt.

IR (KBr): 3200~a4oocrrL-1(νou)2850~
2950crrL-1(νCH2)162oatt-”
(uc=o) 155ocrIL-1('CO*-) 1410cIrL-1(ucOl-) Example 4 N-lauroyl-N-(2-hydroxyzolopyl)-β-alania sodium salt obtained in Example 3 Calcium chloride 59g after dissolving in 15g 1 200g ion exchange water
The mixture was added with sufficient stirring and then extracted with ether.

At this time, 50ml of methanol was added dropwise to improve the layering. Ether extract? 3 with 200p ion exchange water
After washing twice, it was dehydrated with anhydrous sodium sulfate. Separate the sodium sulfate tF, evaporate the solvent under reduced pressure, and dry.
5 g of lauroyl-N-(2-hydroxyzorohylic)-β-alanine calcium salt was obtained.

Example 5 N-lauroyl-N-(2-?:)”ax in a certain amount of water
Add dipropyl)-β-alanine, neutralize it by adding an equimolar amount of triethanolamine, and stir thoroughly. An aqueous amine salt solution was obtained.

Test Example A compound of the present invention and a comparative compound were added to ion-exchanged water or hard water at room temperature to a concentration of 1% by weight, and their solubility was examined. As a result, as shown in Table 1, the compound of the present invention showed good solubility even in hard water. It also showed good foaming properties.

The solubility was evaluated based on the following criteria.

O: Transparently dissolved Δ: Slightly opaque or dispersed ×
: Insoluble 1 = 1, bottom margin

Claims (1)

[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, n represents an integer from 8 to 16) N-acyl-N-( 2-hydroxypropyl)-β-alanine and its salts. 2. N-acyl-N-(2-hydroxypropyl)-β-alanine and its salts according to claim 1, wherein n is 8, 10, 12, 14 or 16.