JP2551466B2 - 3- [N-acyl-N- (alkyl) amino] -2-hydroxy-1-propanesulfonic acid and salts thereof, and methods for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel acylated aminosulfonic acid and a salt thereof, and more specifically, 3- [N-acyl-N, which is useful as a mild surfactant. -(Alkyl) amino] -2-
TECHNICAL FIELD The present invention relates to hydroxy-1-propanesulfonic acid and salts thereof and methods for producing them.

[Conventional technology and problems to be solved]

A surfactant is a compound having a hydrophobic group and a hydrophilic group in the molecule, and by taking advantage of basic performance such as wetting, washing, emulsifying, dispersing, and foaming, cosmetics, detergent raw materials, pharmaceuticals, paints,
Widely used in fiber treatment agents, emulsifiers, etc.

However, surfactants are required to have various properties depending on the intended use, and especially when used in shampoos, body wash, etc., they have excellent foaming and hard water resistance and are mild and biodegradable to the skin. , It is required to be pollution-free, and for this purpose, hypoallergenic bases such as monoalkyl phosphate (MAP), sodium acylglutamate (AGS) and imidazoline activators are used, and boosters (foaming agents) Although an acylated amino acid or the like is used as the above, it is not always sufficient to satisfy the above requirements.

[Means for solving the problem]

Under these circumstances, the inventors of the present invention have conducted extensive studies and found that the compound represented by the following general formula (I) is particularly MAP.
It has an excellent booster effect against surfactants, is mild to the skin, has excellent hard water resistance, has good biodegradability, and is highly pure and high in yield from easily available raw materials. The present invention has been completed by finding that it can be manufactured by.

That is, the invention has the general formula (I) (Wherein R represents an alkyl or alkenyl group having 1 to 21 carbon atoms, R'represents an alkyl group having 1 to 22 carbon atoms, and M represents hydrogen, an alkali metal, an alkaline earth metal or an ammonium compound). The present invention provides 3- [N-acyl-N- (alkyl) amino] -2-hydroxy-1-propanesulfonic acid represented by the formula, a salt thereof and a method for producing the same.

In the compound of the present invention in (I), the alkyl or alkenyl group of R may be linear or branched, and specific examples include:
For example Is acetyl, propionyl, butyryl, isobutyryl,
Examples thereof include compounds such as valeryl, isovaleryl, hexanoyl, octanoyl, decanoyl, lauroyl, myristoyl, balmitoyl, stearoyl, arachidinoyl, behenoyl, oleoyl, linoleoyl, isostearoyl, 2-hexyl-decanoyl, neodecanoyl groups. Examples of R'include methyl, ethyl, propyl, butyl, amyl, hexyl, hebutyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and docosyl groups.

Examples of M include alkali metals such as sodium and potassium; alkaline earth metals such as calcium and magnesium; ammonium compounds such as ammonium, alkanolammonium, alkylammonium, arylammonium, arylalkylammonium, pyridinium, lysine and arginine. .

3- [N-acyl-N- (alkyl) amino] -2-hydroxy-1-propanesulfonic acid and its salt (I) of the present invention are obtained by reacting sodium bisulfite with epichlorohydrin according to the following reaction formula, for example. To give sodium 3-chloro-2-hydroxy-1-propanesulfonate (II), which is reacted with a monoalkylamine to give sodium 3- (N-alkylamino) -2-hydroxy-1-propanesulfonate ( III), followed by acylation and optionally salt exchange.

(Wherein R and R ′ are the same as above) The reaction of sodium bisulfite with epichlorohydrin in the present method is carried out at a temperature of 20 to 100 ° C., preferably 40 to 90 ° C., more preferably 60 to 80 ° C. .

The reaction of the compound (II) with the monoalkylamine is carried out by dropping an aqueous solution of the compound (II) into the monoalkylamine. The ratio of the monoalkylamine to the compound (II) is 1 to 20 times, preferably 2 to 10 times, more preferably 5 to 10 times. The reaction is carried out at a temperature of 20 to 90 ° C., but it is preferable to appropriately determine the optimum temperature depending on the physical properties of the monoalkylamine used. For example, when an amine having a low boiling point such as monomethylamine is used, a reaction at around room temperature is preferable, and when a higher amine which is solid at room temperature such as laurylamine is used, a reaction at a temperature above its melting point is preferable. This reaction can also be carried out in the presence of an alkali such as NaOH or KOH.

Acylation of compound (III) is carried out by reacting with acyl chloride in the presence of an alkali such as NaOH, KOH, NaHCO ₃ at a temperature of 0 to 60 ° C, preferably 20 to 50 ° C. After completion of the reaction, the pH is adjusted to the neutralization point of each target compound, desalting is performed by electrodialysis or the like, and dehydration is performed to obtain the target product (I). ) Get.
If necessary, salt exchange is performed.

〔The invention's effect〕

Thus obtained 3- [N-acyl-N- of the present invention
(Alkyl) amino] -2-hydroxy-1-propanesulfonic acid and its salt (I) are novel surfactants having a hydroxyl group at the β-position of sulfonic acid and are mild to skin. It has excellent decomposability, excellent foaming power, hard water resistance, and extremely good solubility in water, and can be widely used in various fields.

[Examples] Next, examples will be described, but the present invention is not limited thereto.

Example 1. 3- [N-lauroyl-N- (methyl) amino] -2-
Sodium hydroxy-1-propanesulfonate (Ia)
Synthesis of: (1) Synthesis of sodium 3-chloro-2-hydroxy-1-propanesulfonate (IIa): 273.9 g of sodium bisulfite in a two-necked flask (2.
63 mol) and 1000 g of water were charged, and epichlorohydrin 231.
9g (2.51mol) was added dropwise at 60-80 ℃ for 1 hour, then at 80 ℃ for 1 hour.
Aged for hours. After cooling to 40 ℃, methanol 400g
Was added, the mixture was further cooled to 3 ° C., and the precipitated crystals were passed through,
After drying, 326.1 g of sodium 3-chloro-2-hydroxy-1-propanesulfonate (IIa) was obtained (yield 66.2
%). mp258-259 ° C (decomposition) The liquid is further concentrated, and methanol is added to the second crystal 104.
0 g and 36.3 g of the third crystal were obtained (yield 94.
6%).

(2) 3- (N-methylamino) -2-hydroxy-1
-Synthesis of sodium propanesulfonate (IIIa): 40% monomethylamine aqueous solution 17 in a 14 neck flask
Put 9.9g (2.32mol), compound (IIa) 50.0g (0.25mo
l) dissolved in 200 g of water and 30% NaOH 35.6 g (0.27
mol) were simultaneously added dropwise at 30 ° C. for 30 minutes. 40
After aging at 5 ° C. for 5 hours, monomethylamine and water were removed under reduced pressure, and the mixture was concentrated to 89.4 g. Methanol was added to remove the precipitated salt, and the liquid was further concentrated, and the precipitated crystals were collected, dried and sodium 3- (N-methylamino) -2-hydroxy-1-propanesulfonate ( IIIa) 35.2g was obtained (yield 72.5%). mp2
15 ° C- (decomposition) (3) 3- [N-lauroyl-N- (methyl) amino]
Synthesis of sodium 2-hydroxy-1-propanesulfonate (Ia): In a 14-neck flask, 164.7 g of compound (IIIa) (0.25
mol) and 330.0 g of water, and while maintaining pH 10-11 at 25 ° C, 54.8 g (0.25 mol) of lauric chloride, 30% NaOH 3
6.7 g (0.28 mol) was added dropwise over 2 hours. The mixture was aged for 1 hour, neutralized to pH 7 with 36% hydrochloric acid, cooled to 10 ° C., and the precipitated crystals were collected to obtain 186.8 g of crude crystals. Water this 37
Recrystallization from a mixture of 4 g and 374 g of methanol gave 3- [N-
80.5 g of sodium lauroyl-N- (methyl) amino] -2-hydroxy-1-propanesulfonate (Ia) was obtained (yield 88%). mp209 to 210 ° C Elemental analysis (%): Analytical value Calculated value C 51.15 51.45 H 8.70 8.64 N 3.60 3.75 O 21.70 21.42 S 8.28 8.58 Na 5.90 6.16 IR (KBr, cm ^-1 ): 3370,2920,2850,1645,1470 , 1420,1360,
1235,1175,1090,1050,790,725,635 NMR (DMSO-d ₆ , δppm): 0.58 to 1.50 (21H, m), 2.07 to 2.
43 (2H, m), 2.60 (2H, d, J = 4.0Hz), 2.90 (3H, d, J = 11.
0Hz), 3.37 (2H, d, J = 5.0Hz), 3.77-4.20 (1H, m), 5.0
3 (1H, s) Example 2 3- [N-balmitoyl-N- (methyl) amino] -2
-Hydroxy-1-propanesulfonic acid sodium salt (I
Synthesis of b): A 14-necked flask was charged with 20 g (0.11 mol) of the compound (IIIa) synthesized in Example 1 (2) and 400 ml of water, and the pH was adjusted to 1 at 25 ° C.
Keeping at 0-11, 28.76 g (0.1
1 mol) and 16.55 g (0.12 mol) of 30% NaOH were added dropwise over 2 hours, each was aged at 50 ° C for 4 hours, neutralized to pH 7 with 36% hydrochloric acid, and then cooled to 2 ° C to precipitate crystals. Collected to obtain 41.39 g of crude crystals. This was recrystallized from a mixed solution of 250 ml of water and 250 ml of methanol to give 3- [N-palmitoyl-N- (methyl) amino] -2-hydroxy-1.
-34.81 g of sodium propanesulfonate (Ib) was obtained (yield 77.2%). pm206-207 ℃ Elemental analysis (%): Analytical value Calculated value C 55.90 55.92 H 9.43 9.39 N 3.14 3.26 O 18.75 18.62 S 7.40 7.46 Na 5.39 5.35 IR (KBr, cm ^-1 ): 3360,2920,2850,1640,1470 , 1430,1410,
_{1360,1235,1175,1090,1050,790,725,635 NMR (DMSO-d 6,} δppm): 0.71~1.63 (29H, m), 2.07~2.
47 (2H, m), 2.59 (2H, d, J = 3.0Hz), 2.91 (3H, d, J = 11.
0Hz), 3.35 (2H, d, J = 5.0Hz), 3.71 to 4.14 (1H, m), 5.0
7 (1H, s) Example 3 3- [N-lauroyl-N- (butyl) amino] -2-
Sodium hydroxy-1-propanesulfonate (Ic)
Synthesis of (1) 3- (N-butylamino) -2-hydroxy-1
-Synthesis of sodium propanesulfonate (IIIb): In a 14-neck flask, n-butylamine 186.03 g
(2.54 mol) was added, and 100 g (0.51 mol) of the compound (IIa) synthesized in Example 1 (1) was dissolved in 400 g of water.
% NaOH 71.22g (0.53mol) at the same time at 60-70 ℃
Then, it was added dropwise for 30 minutes. After aging at 70 ° C. for 6.5 hours, N-butylamine and water were removed under reduced pressure, and the mixture was concentrated to 218 g. After methanol was added to remove the precipitated salt, the liquid was further concentrated, and the precipitated crystals were collected and dried to give 3- (N-butylamine) -2-hydroxy-1.
-91.21 g of sodium (IIIb) propanesulfonate was obtained (yield 76.8%). mp230 ° C- (decomposition) (2) 3- [N-lauroyl-N- (butyl) amino]
Synthesis of sodium 2-hydroxy-1-propanesulfonate (Ic): Compound (IIIb) 30g (0.129mo
l), put 300 ml of water, while keeping pH 10-11 at 25 ℃, 28.14 g (0.129 mol) of lauric acid chloride, 23.02 g of 30% NaOH
(0.173 mol) was added dropwise over 2 hours. After aging at 50 ° C. for 3 hours, the mixture was neutralized to pH 7 with 36% hydrochloric acid, ethanol was added to remove the solvent under reduced pressure, and 73.72 g of solid matter was obtained. After adding ethanol to remove the precipitated crystals,
The obtained liquid was concentrated and dried to obtain 38.87 g of sodium 3- [N-lauroyl-N- (butyl) amino] -2-hydroxy-1-propanesulfonate (Ic) (yield 7
2.7%). mp257-259 ℃ Elemental analysis (%): Analytical value Calculated value C 54.65 54.92 H 9.25 9.22 N 3.17 3.37 O 19.50 19.25 S 7.50 7.71 Na 5.45 5.53 IR (KBr, cm ^-1 ): 3450,2925,2850,1630,1465 , 1430,1380,
1200,1090,1050,780,720,620 NMR (CDCl ₃ , δppm): 0.63 to 1.93 (28H, m), 1.93 to 2.67
(4H, m), 2.76 to 3.80 (5H, m), 4.10 to 4.60 (1H, m) Example 4 3- [N-palmitoyl-N- (butyl) amino] -2
-Hydroxy-1-propanesulfonic acid sodium salt (I
Synthesis of d): A 14-necked flask was charged with 20 g (0.0857 mol) of the compound (IIIb) synthesized in Example 3 (1) and 700 ml of water, and p
23.57 g of palmitic acid chloride while maintaining H10-11
(0.0857 mol) and 30% NaOH 15.32 g (0.1149 mol) were added dropwise over 2 hours. After aging for 5 hours, use 35% hydrochloric acid
After neutralizing to pH 7, ethanol was added and the solvent was removed under reduced pressure to obtain 48.86 g of a solid product. Ethanol was added to remove precipitated crystals, and the obtained liquid was concentrated to dryness under reduced pressure. Further, after dissolving in n-hexane to remove insoluble matter, n-hexane was removed from the solution and dried to give 3- [N
-Palmitoyl-N- (butyl) amino] -2-hydroxy-1-propanesulfonic acid sodium salt (Id) 31.64 g
Was obtained (yield 78.3%). mp242〜244 ℃ Elemental analysis (%): Analytical value Calculated value C 58.45 58.57 H 9.90 9.83 N 2.83 2.97 O 17.05 16.96 S 6.50 6.80 Na 4.71 4.87 IR (KBr, cm ^-1 ): 3440,2920,2850,1630,1460 , 1430,1380,
1200,1090,1050,785,720,620 NMR (CDCl ₃ , δppm): 0.57 to 1.97 (36H, m), 1.97 to 2.70
(4H, m), 2.70 to 3.73 (4H, m), 4.03 to 4.67 (2H, m) Example 5 3- [N-lauroyl-N- (dedosyl) amino] -2
-Hydroxy-1-propanesulfonic acid sodium salt (I
Synthesis of e): (1) 3- (N-dedosylamino) -2-hydroxy-
Synthesis of sodium 1-propanesulfonate (IIIc): Laurylamine 188.58 g (1.017 g) in a 14-necked flask.
mol), and the compound (IIa) synthesized in Example 1 (1)
100g (0.509mol) dissolved in 400g water and 30% NaOH
71.22 g (0.534 mol) were simultaneously added dropwise at 80 ° C. for 30 minutes. After aging at 90 ℃ for 5 hours, add methanol to 5 ℃
After cooling, the precipitated crystals were collected, thoroughly washed with methanol, and dried to obtain 107.38 g of sodium 3- (N-dodecylamino) -2-hydroxy-1-propanesulfonate (yield 61.1%). . mp237-238 ° C (2) Synthesis of sodium 3- [N-lauroyl-N- (dodecyl) amino] -2-hydroxy-1-propanesulfonate (Ie): Compound (IIIc) 30 g (0.0868) in a 14-necked flask. mo
l), 200 ml of methanol and 300 ml of water, and add pH 10 ~ 1 at 50 ℃.
Lauric acid chloride 19g (0.0868mo
l) and 30% NaOH 14.88 g (0.1116 mol) were added dropwise over 2 hours. After aging for 4 hours, the mixture was neutralized to pH 7 with 36% hydrochloric acid, cooled to 4 ° C, and the precipitated crystals were collected and dried.
37.82 g of crude crystals were obtained. Purified by silica gel column chromatography (developing solvent hexane / acetone) to give 3- [N-lauroyl-N- (dodecyl) amino] -2.
-Hydroxy-1-propanesulfonic acid sodium salt (I
e) 27.8 g was obtained (yield 60.7%). mp251-253 ℃ (decomposition) Elemental analysis (%): Analytical value Calculated value C 61.15 61.45 H 10.27 10.31 N 2.53 2.65 O 15.29 15.16 S 5.96 6.07 Na 4.21 4.36 IR (KBr, cm ^-1 ): 3450,2925,2850, 1630,1470,1430,1380,
1200,1095,1050,790,725,620 NMR (CDCl ₃ , δppm): 0.63 to 1.92 (44H, m), 1.92 to 2.55
(4H, m), 2.55 to 3.77 (4H, m), 4.12 to 4.54 (1H, m), 5.1
3 (1H, s) Example 6 3- [N-palmitoyl-N- (dodecyl) amino]-
Synthesis of sodium 2-hydroxy-1-propanesulfonate (If): 25 g (0.0724 mol) of compound (IIIc) synthesized in Example 5 (1), 200 ml of methanol, 300 ml of water in a 14-necked flask.
ml, and keep the pH at 10-11 at 50 ℃, palmityl chloride 19.89g (0.0724mol) 30% NaOH 12.35g (0.09263
mol) was added dropwise over 2 hours. After aging for 5 hours, the mixture was neutralized to pH 7 with 36% hydrochloric acid, cooled to 4 ° C., and the precipitated crystals were collected and dried to obtain 34.86 g of crude crystals. This was dissolved in ether to remove insolubles, and then the ether was removed to give 3- [N-palmitoyl-N- (dodecyl)
22.81 g of sodium amino] -2-hydroxy-1-propanesulfonate (If) was obtained (yield 54.0%). mp235
C- (decomposition) Elemental analysis (%): Analytical value Calculated value C 63.48 63.77 H 10.73 10.70 N 2.44 2.40 O 13.92 13.70 S 5.27 5.49 Na 3.43 3.49 IR (KBr, cm ^-1 ): 3450,2920,2850,1630, 1460,1430,1380,
1200,1090,1050,790,720,620 NMR (CDCl ₃ , δppm): 0.64 to 1.97 (52H, m), 1.97 to 2.64
(4H, m), 2.64 ~ 3.61 (4H, m), 4.14 ~ 4.52 (1H, m), 5.2
4 (1H, s) Test Example 1 Test compound 0.2%, lanolin 0.5%, pH by inversion stirring method ^*
The measurement was performed at 7, 4 ° DH and 40 ° C. The foaming force was expressed as a relative value when the amount of foam was 1.00 when monolauryl phosphate triethanolamine salt was used as a test compound. Table 1 shows the results. ^* Inverting stirring method: The flat propeller is rotated every 1000 seconds for 6 seconds to stir the sample solution in the cylinder for 5 minutes, and after the stirring is completed, the amount of bubbles is measured 30 seconds later.

As is clear from Table 1, the compounds of the present invention have excellent foaming power.

Test Example 2 Mono-lauryl phosphate triethanolamine salt 0.15%, test compound 0.05%, lanolin 0.5 by the inversion stirring method for the foaming power of the compound of the present invention and the comparative compound
%, PH 7, 4 ° DH, 40 ° C. The foaming force was expressed as a relative value when the amount of foam was 1.00 when monolauryl phosphate triethanolamine salt was used as a test compound. The results are shown in Table 2.

As is clear from Table 2, the compounds of the present invention have excellent foaming power.

Test Example 3 The skin irritation of the compound of the present invention and the comparative compound was determined as an average reaction intensity 48 hours after the removal of the patch by the patch application method using a guinea pig (5 animals in 1 group) for 24 hours. Test compound diluted with distilled water to 5% concentration and 1%
The results of evaluation by concentration are shown in Table 3.

As is clear from Table 3, the compounds of the present invention are surfactants at the same level as or lower than that of the comparative compound which is well known as a mild surfactant.

Test Example 4 With respect to the compounds of the present invention and the comparative compound, the hard water resistance thereof was gradually changed to an aqueous solution of pH 7 containing 1.0% of the test compound.
Cl ₂ was added, and it was determined as the CaCl ₂ concentration (ppm) when the solution became cloudy. Table 4 shows the results.

As is clear from Table 4, the compounds of the present invention show extremely excellent hard water resistance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C11D 1/28 C11D 1/28

Claims (2)

(57) [Claims] 1. A general formula (I) (Wherein R is an alkyl or alkenyl group having 1 to 21 carbon atoms, R'is an alkyl group having 1 to 22 carbon atoms, and M is hydrogen, an alkali metal, an alkaline earth metal or an ammonium compound). 3- [N-acyl-N- (alkyl) amino] -2-hydroxy-1-propanesulfonic acid and salts thereof. 2. Sodium bisulfite is reacted with epichlorohydrin to form sodium 3-chloro-2-hydroxy-1-propanesulfonate, which is then R'-NH.
By reacting a monoalkylamine represented by ₂ (R 'is the same as above) (In the formula, R ′ is the same as above), sodium 3- (N-alkylamino) -2-hydroxy-1-propanesulfonate is obtained, which is then acylated and, if necessary, salt-exchanged. The method for producing 3- [N-acyl-N- (alkyl) amino] -2-hydroxy-1-propanesulfonic acid and a salt thereof according to claim 1.