JPS61212547A - Dehydroabiethylamino acid, salt thereof, and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula [X is reside of amino acid (with the proviso that no sulfur-containing amino acid is included) or its alkali salt], or its salt. EXAMPLE:N-Dehydroabiethyl-glycine-sodium salt. USE:A surface active agent having high solubility in hard water, and high active effect when it is used in hard water. PREPARATION:Dehydroabietic acid chloride is reacted with an amino acid (e.g., glycine, D,L-alpha-alanine, L-valine, L-phenylalanine, sarcosine, D,L-serine, D,L-methionine, L-tryptophan, L-aspartic acid, etc.) in the presence of an alkali, and optionally hydrolyzed to give a compound shown by the formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to dehydroabiethyl amino acid or a salt thereof, and to the substance and a method for producing the same.

Dehydroabiethyl amino acid in the present invention is an amide of dehydroabietic acid and an amino acid, and its salt is an alkali salt of 11121 in the amino acid component. The alkali salts can thus be used as surfactants, and the amides have utility as intermediates for preparing the alkali salts.

BACKGROUND ART As conventional rosin-based surfactants, alkali metal salts of rosins such as gum rosin and tall oil rosin are known.

Problems to be Solved by the Invention However, these surfactants have a low effect on hard water and may form precipitates or become cloudy.

The present invention has been made in view of the above circumstances, and provides a novel substance that is easily soluble in hard water and useful as a rosin-based surfactant that has high surface activity when used in hard water. The purpose is to

As a means to solve the problems, the substance of the present invention is represented by the general structural formula (wherein X represents the residue of amino II (including sulfur-containing amino acids) or an alkali salt thereof). .

Amino acid residues in the present invention include glycine, D,
L-α-alanine, L-valine, L-phenylalanine, sarcosine, D, L-serine D, L-methionine, L
Examples include residues of amino acids such as -t-ributofun, L-aspartic acid, and L-glutamic acid, and also include residues such as taurine, which is a sulfur-containing amino acid.

Further, the invention of the 1m method for dehydroabietyl amino acid or a salt thereof in the present application is characterized in that dehydroabietyl chloride is reacted with an amino acid in the presence of an alkali, and hydrolyzed as necessary.

Dehydroabietic acid is obtained by dehydrogenating abietic acid, which is the main component of rosin, and dehydroabietic acid chloride is obtained by reacting thionyl chloride with this dehydroabietic acid.

Effect: According to the method of the present invention, the carboxylic acid or sulfonic acid in the amino acid reacts with an alkali in the reaction atmosphere to form a salt,
The amine group in the amino acid salt reacts with the chlorocarbonyl group of the dehydroabietic acid chloride to form an amide bond, yielding the dehydroabietyl amino acid salt. Furthermore, dehydroabiethyl amino acid can be obtained by hydrolyzing this dehydroabiethyl amino acid salt with an acid.

Dehydroabiethyl amino acid produces a salt by reacting with an alkali again.

The dehydroabiethyl amino acid salt of the present invention has a lipophilic skeleton and contains a hydrophilic carboxylate or sulfonate in a part thereof, so that it acts as a good surfactant. - Effects of the Invention The dehydroabiethyl amino acid salt of the present invention dissolves well even in hard water, does not cause precipitation or turbidity, has a good surfactant effect, and has excellent foaming properties.

Examples of amino acids include glycine, D, L-α-alanine,
L-valine, phenylalanine, sarcosine, D,
Dehydro-ethyl amino acid was synthesized using L-serine, D, L-methionine, L-tryptophan, L-aspartic acid, L-glutamic acid, and taurine by the procedure described below.

First, dehydroabietic acid chloride was synthesized from dehydroabietic acid. Dehydroabietin m50Q with a purity of 90% was dissolved in toluene and thionyl chloride 29(+
was added and reacted for 2 hours while stirring at 80 to 85°C. After the reaction was completed, the solvent and remaining thionyl chloride were distilled off. The obtained product was then dissolved in ether, washed with water, and further washed with a 0.2N aqueous caustic soda solution.

Next, it was washed with water until the washing solution became neutral, further washed with saturated saline, dried over anhydrous sodium sulfate, and the solvent was distilled off. Dehydroabietic acid chloride manufactured by W was obtained.

Next, this dehydroabietic acid chloride and an amino acid were reacted. After dispersing 0.0144 mol of each of the above amino acids (reagent grade) in a mixed solvent of 20 d of water and 10 d of acetone, 5.86 d of a 6N caustic soda aqueous solution (
When the amino acid is L-glutamic acid or L-aspartic acid, add 8.06+d) and dissolve uniformly.

Next, a solution prepared by dissolving 5 g of dehydroabietic acid chloride in acetone 101e was added to this solution under water cooling (
(1 to 3°C) over about 10 minutes. Stirring was continued for 2 hours under water cooling, and then the temperature was raised to room temperature. If there is a precipitate in the solution, add an appropriate amount of water/acetone mixed solvent to dilute and dissolve.

After stirring for 1 hour at room temperature, add about 6 d of 6N-hydrochloric acid (about 811 when the amino acid is L-glutamic acid or L-aspartic acid) to make the hydrochloric acid acidic with I) H of about 1; The reaction is completed by hydrolyzing the salt.

The obtained dehydroabiethyl amino acid solution is purified.

When the amino acid is an aminocarboxylic acid, first, acetone in the solvent is distilled off under reduced pressure, followed by ether extraction to remove the aqueous layer. After further washing with water, the mixture was extracted with a saturated aqueous solution of sodium bicarbonate and the ether layer was removed.

Add 6N hydrochloric acid to bring the I)H to about 1 and hydrolyze the remaining salt. Further, the mixture is extracted with ether to remove the aqueous layer, washed with water, dried over anhydrous sodium sulfate, and the ether is distilled off under reduced pressure to obtain purified dehydroabiethyl amino acid.

When the amino acid is aminosulfonic acid (taurine), first, acetone in the solvent is distilled off under reduced pressure, neutralized with Amberlite IRA-45, and salted out with common salt. The precipitate is collected by centrifugation, and the precipitate is dissolved in ethyl alcohol.

After drying over anhydrous sodium to sulfuric acid, insoluble materials are removed by filtration, and ethyl alcohol is distilled off under reduced pressure to obtain purified dehydroabiethyl amino acid.

Table 1 shows the properties of the obtained dehydroabiethyl amino acid.

Next, we will investigate the properties of dehydroaedyl amino acid salt as a surfactant.

N-dehydroabiethyl-glycine-sodium salt, N
Each dehydroabiethyl amino acid salt was tested: -dehydroabiethyl-D, L-alanine-sodium salt, N-dehydroabiethyl-L-glutamic acid-sodium salt, and N-dehydroabiethyl-taurine-sodium salt. As a comparative example, a sodium salt of gum rosin was also tested.

0.2% aqueous solution 101i of each sample and 50 ppm and 300 pf calcium chloride dissolved in water) III
of hard water was mixed with 10 mQ of hard water, and the degree of turbidity and precipitate was examined.

The test results are shown in Table 2.

Claims (1)

[Claims] 1. A dehydroavian represented by the general structural formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, Ethyl amino acid or its salt 2 General structural formula ▲ Numerical formula, chemical formula, table, etc. ▼ (Formula (X represents the residue of an amino acid (including sulfur-containing amino acids) or an alkali salt thereof)