JPH03220170A - New amidosulfonic acid or salt thereof, its production and surfactant containing the same - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R is 1-21C alkyl or alkenyl; R' is 3-22C alkyl, 1-22C alkenyl or hydroxyalkyl or 2-25C alkoxyalkyl; M is H, alkali metal, alkaline earth metal or ammonium compound) or salt thereof. EXAMPLE:Sodium 3-[N-lauroyl-N-(2'-hydroxypropyl)amino]-2-hydroxyl-1- propanesulfonate. USE:A surfactant, mild to the skin, good in biodegradability, improved in foaming power and hard water resistance and excellent in solubility in water. PREPARATION:A compound expressed by formula II (M' is alkali metal; X is halogen) is allowed to react with a primary amine expressed by the formula R'-NH2 and the resultant compound is then acylated with an acyl chloride in the presence of an alkali (e.g. NaOH) at 0-60 deg.C to afford the compound expressed by formula I.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel "amidosulfonic acid or its salt,"
More specifically, 3-[
N-acyl-N-(substituted)amino]2-hydroxy-1
-Propanesulfonic acid or a salt thereof, a method for producing the same, and a surfactant containing the same.

[Prior art and problems to be solved by the invention] Surfactants are compounds that have hydrophobic groups and hydrophilic groups in their molecules, and they can be used to make use of their basic properties such as wetting, cleaning, emulsification, dispersion, and foaming. It is widely used in cosmetics, detergent raw materials, pharmaceuticals, paints, textile processing agents, emulsifiers, etc.

However, surfactants are required to have various properties depending on their usage, and especially when used in shampoos, body cleansers, etc., they have excellent foaming properties and hard water resistance, are mild to the skin, and have good biodegradability. , which is required to be non-polluting and for this purpose
, sodium 7-silk glutamate (ΔGS), imidacillin activators, and other hypoallergenic bases are used, and acylated amino acids and the like are used as boosters (foaming agents), but in order to satisfy the above requirements, is not necessarily sufficient.

[Means for Solving the Problems] Under these circumstances, the present inventors conducted intensive research and found that the compound represented by Funagura (1) below is particularly effective in MAP.
It exhibits an excellent boosting effect compared to surfactants, is mild to the skin, has excellent hard water resistance, and has good biodegradability.It also has high purity and high purity with simple operations from easily available raw materials. The present invention was completed by discovering that it can be produced with high yield.

That is, the present invention relates to general formula (I) R' R-C-N-CH, CHCII, SO3M
(1) 10 leaves (wherein R is a straight chain, branched or cyclic alkyl or alkenyl group having 1 to 21 carbon atoms, R' is a branched or cyclic alkyl group having 3 to 22 carbon atoms, 1 carbon number -22 straight chain, branched or cyclic alkenyl or hydroxyalkyl group or straight chain, branched or cyclic alkoxyalkyl group having 2 to 25 carbon atoms, M represents hydrogen, alkali metal, alkaline earth metal or ammonium compound ), a method for producing the same, and a surfactant containing the same.

In the compound of the present invention represented by the general formula (1), the alkyl group or alkenyl group of R may be linear, branched, or cyclic, and specific examples thereof include, for example, R [- group is acetyl, propionyl, butyl isobutyryl, valeryl, isovaleryl, hexanoyl, octanoyl, dicarboxyl, lauroyl, myristoyl, balmitoyl, stearoyl, arachidinoyl, behenoyl, oleoinoberyl oil, isostearoyl, 2-hexyl-butyryl, neodecanoyl, cyclohexanecarbonyl, cyclo Examples include hexylacetyl group.

In addition, examples of the branched or cyclic alkyl group for R' include isopropyl, isobutyl, 5ec-butyl, cyclohexyl, 2-ethylhexyl, 2-octyldecyl,
Examples of straight chain, branched or cyclic alkenyl groups include allyl, methallyl, 4-pentenyl, 2-cyclohexenyl, 3-cyclohexylmethyl, elaidyl, and oleyl groups. ; Straight chain, branched or cyclic hydroxyalkyl groups include, for example, hydroxyethyl, 2-hydroxypropyl, ■-methyl-2-hydroxyethyl, 3
-hydroxypropyl, 2-hydroxycyclohexyl groups, etc.; linear, branched or cyclic alkoxyalkyl groups include, for example, 3-methoxypropyl, 3-
Examples include octadecyloxypropyl, 3-isobutoxypropyl, 3(2-ethylhexyloxy)propyl, and 3-sichexyloxypropyl groups.

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

The amidosulfonic acid and its salt (I) of the present invention can be produced by reacting an alkali metal bisulfite with epihalohydrin according to the following reaction formula, for example, to produce 3-halo-2-hydroxy-1
- Propanesulfonic acid alkali metal salt (II) and pear,
This is reacted with a primary amine to form 3-(N-substituted amino).
-2-hydroxy 1-propanesulfonic acid alkali gold I
It is produced by forming Fs salt (III), then acylating this, and further performing salt exchange if necessary.

Below is the margin (II) R' Kano (III) (In the formula, R and R' are the same as above. M' is an alkali metal, and X is a halogen atom.) In this method, the alkali metal salt of bisulfite is bisulfite. Examples of the epihalohydrin include sodium and the like, and examples of the epihalohydrin include epichlorohydrin. The reaction between such an alkali metal bisulfite salt and epihalohydrin is 20 to 1
00°C, preferably 40-90°C, more preferably 60°C
It is carried out at a temperature of ~80°C.

The reaction between compound (n) and primary amine is compound (It)
It is carried out by dropping an aqueous solution of into a primary amine. The ratio of primary amine to compound (n) 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 primary amine used. For example, when using an amine with a low boiling point such as isopropylamine, the reaction occurs at around room temperature, and when using a higher amine that is solid at room temperature such as 3-octadecyloxypropylamine, the reaction occurs at a temperature above its melting point. The reaction is preferred. This reaction can also be carried out in the presence of an alkali such as NaOH or KOH.

Acylation of compound (I[I) is performed using NaOH, KOH, N
This is carried out by reacting with an acyl chloride in the presence of an alkali such as aHCO3 at a temperature of 0 to 60°C, preferably 20 to 50°C. After the reaction, the pH is adjusted to the neutralization point of each target product, and the target product (I) is desalted and dehydrated by electrodialysis or the like, or the target product (I) is obtained by recrystallization as the case requires. ). In addition, salt exchange is performed if necessary.

The amidosulfonic acid or its salt (I) of the present invention thus obtained has an excellent surfactant effect and can be used alone as a surfactant, but since it has an excellent booster effect, Its foaming power can be enhanced by using it in combination with other commonly used surfactants.

Other surfactants used here include soap,
Anionic surfactants such as sulfate ester surfactants, sulfonate surfactants, MAP surfactants; Ampholytic surfactants such as amino acid surfactants and betaine surfactants Glyceryl nistearate Examples include nonionic surfactants such as ester surfactants, 5pan surfactants, and Tween surfactants, but especially MA
It has excellent effects on P-based surfactants.

In the present invention, it is preferable that the total amount of amidosulfonic acid or its salt (I) is 0.1 to 100% by weight in the surfactant.

〔Effect of the invention〕

The novel amidosulfonic acid and its salt (I) of the present invention are:
A new surfactant with a hydroxyl group at the β-position of sulfonic acid, it is mild to the skin, has good biodegradability, has excellent foaming power, hard water resistance, and is extremely soluble in water. In addition to having the excellent feature of good foaming properties, it also shows even better foaming power when used in combination with other surfactants, and can be used in a wide range of fields.

〔Example〕

Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto.

Example 1 Synthesis of sodium 3-[N-lauroyl-N-(2'-hydroxypropyl)aminoco-2-hydroxy-1-propanesulfonate (I a): (1) 3-40 l~
2-Hydrochemical 1 ~ Sodium propane sulfonate (
]Ia) Synthesis: 2I! 273.9 g (2,63 mo7) of sodium bisulfite and 100 g of water in 3-loaf flasks
0g and 231.9g of epichlorohydrin (
2,51 mof) was added dropwise at 60 to 80°C for 1 hour.
It was aged for 1 hour at 0°C.

After cooling to 40°C, add 400g of methanol,
The mixture was further cooled to 3°C, and the precipitated crystals were filtered and dried to obtain 326.1 g of sodium 3-chloro-2-hydroxy-1-propanesulfonate (IIa) (yield: 66.2%). ). m, 2.258-259°C (decomposition) The filtrate was further concentrated, methanol was added and the second crystal 104
．． 0 g and 36.3 g of the third crystal were obtained (yield 94.6% including the third crystal).

(2) Synthesis of sodium 3-[N-lauroyl-N-(2'-hydroxypropyl)amino]-2-hydroxy-1-propanesulfonate (I a): 214 monoisopropane amine: /263J7 g
(3,507 mof) and 245 g of water were added, and 137.82 g (0,701 mof) of compound (II a) was added.
dissolved in 350g of water and 30% NaOH94,
0g (0,705mol!) at the same time for 25~
The mixture was added dropwise at 30°C for 30 minutes. After aging at 30℃ for 4 hours,
Monoisopropanolamine and water were removed under reduced pressure, and the mixture was concentrated to 440 g. After washing with acetone and drying the solid portion, 162.03 g of (la) was obtained as a powder (purity 26.4%).

Subsequently, compound (]IIa) 1 was added to 11 four-bottle flasks.
Add 35.0 g (0,152 moi') of 226 g of water and add 33.31 g (0,152 mol) of lauric acid chloride while maintaining the pH at 10.5 to 11 at 20°C.
20.4 g (0,153 mol) of 30% Na08 was added dropwise over 1 hour.

After aging for 3 hours, it was neutralized to p)17 with 3G% hydrochloric acid (
reaction rate 99%). Water was removed by azeotropic dehydration, dissolved in methanol to remove insoluble materials, and then evaporated to obtain 116.21 g of a viscous liquid. Purified by silica gel column chromatography (developing solvent: hexane:ethanol = 8:2) to obtain 58.63 g of 3-[N
-Lauroyl-N-(2'hydroxypropyl)aminocousodium 2-hydroxy-1-propanesulfonate (Ia) was obtained. Yield 92.4%. m, p, 200
~207°C HPLC: Purity 85.1% IR (KBr, am-'): 3432.2932
．． 2860, 1626.1470゜1425, 1380
．． H98, 1100, 1046°NMR"(CD['
J 3゜938, 840.788.720.622.532δp
pm): 0.74-1.92 (24) l, m)
.

1,92-2.92 (4H, m).

2.92-4.02 (6H, m).

4.24-4.92 (2 tl, m) Example 2 Synthesis of 3-[N-lauroyl-N-(3'-methoxypropyl)aminocousodium 2-hydroxy-1-propanesulfonate (I b) = 214 3 in one flask
-Methoxypropylamine 312.30g (3,50
Example 1
Compound (IIa) synthesized in (1) 137.82g
(0,701mof) dissolved in 350g of water and 93.47g of 30% NaDH (0,701moj'
) were simultaneously added dropwise at 25 to 30°C for 30 minutes. After aging at 25-30°C for 3 hours, 3-methoxypropylamine and water were removed under reduced pressure and concentrated to 344.23 g. After washing n- with 500g of beef sun and drying the solid part, 214. (IIIb) was obtained as a powder of OOg (purity 69.7%). Yield 85.4%0 followed by 1
Compound (Ib) 85.0 g (
Add 333 g of water (0,238 mol) and adjust the pH to 1 at 20°C.
Lauric acid chloride while maintaining the range from 0.5 to 11.52.
25g (0,238 mob), 30% NaOH33
, 97 g (0,255 mol) were each added dropwise over 1 hour.

After aging for 3 hours, it was neutralized to p) 17 with 36% hydrochloric acid (
reaction rate 95%). Water was removed by azeotropic dehydration, dissolved in acetone to remove insoluble matter, and then evaporated to give 1
00.96 g of 3-[N-lauroyl-N-(3'-
Sodium methoxypropyl)aminoco-2hydroxy-1-propanesulfonate (I b) was obtained (yield 98
．． 3%). m, p, 216-219°C HPLC: Purity 82.4% IR (KBr, cm-'): 3472.2928
．． 2B60,1628.1468°1435,1382
．． 1200.1120.1050゜915,888.8
60.792.722.622゜532,482 NMR (CDtl! 3+δppm): 0.63~
2.78 (27)1. m).

2,78-3.95 (7H, m).

3, 30 (3H, s).

4,18-4.63 (L H, m) Example 3 Synthesis of sodium 3-[N-lauroyl-N-(cyclohexyl)aminocou 2-hydroxy-1-propanesulfonate (I c): Into 214 round flasks Cyclohexylamine 347.7
Compound (II a) synthesized in Example 1 (1) by adding 3,505 moj of water (273 g) 137.8
2g (0,701moi) dissolved in 350g of water and 93.47g (0,701moi) of 30% NaOH.
1) were simultaneously added dropwise at 25 to 30°C over 30 minutes. After aging at 25-30°C for 3 hours, cyclohexylamine and water were removed under reduced pressure and concentrated to 413.42 g. After washing with 500 g of n-hexane and drying the solid portion, 229.19 g of (IIIc) was obtained (purity 60.
3%). Yield 76.1%.

Subsequently, compound (II[c)9 was added to 1104 flasks.
7. Add 312g of 3g (0,226mof) water,
49.75 g of lauric acid chloride (0,227 moji
, 30% NaOH 33, 87 g (0,254 mol each) was added dropwise over 1 hour. After aging for 3 hours,
It was neutralized to p) 17 with 6% hydrochloric acid (reaction rate 84%). Water was removed by azeotropic dehydration, and the residue was dissolved in acetone to remove insoluble matter, followed by evaporation to obtain 60.57 g of a white solid. Purification by silica gel column chromatography (developing solvent; hexane:ethanol = 8:2) yielded 51.68 g of sodium 3-[N-lauroyl-N-(cyclohexyl)aminocou-2-hydroxy-1-propanesulfonate ( Ic) was obtained. Yield: 51.
8%.

HPLC: Purity 83.0% IR (neat, cm-'): 3428.2932
．． 2860, 1624.1464゜1420, 1380
．． 1318.1194.1096°1048,896.
852.802.780.722°620,536 NMR (CDCβ2.δppm): 0.74-2.
61 (34H, m).

2.61-3,94 (5H, m).

3,94-4.70 (I H, m) Test Example 1 The foaming power of the compound of the present invention and the comparative compound was determined by the reverse stirring method 0. Monolauryl phosphate triethanolamine salt 0.15%, test compound 0.05% %, lanolin 0.5%, pH 7, 4°DH, 40°C. The foaming power is determined by measuring the foam volume to 1.0 when monolauryl phosphate triethanolamine salt is used as the test compound.
It is expressed as a relative value when it is set to 0. The results are shown in Table 1.

This reversal stirring method: The sample solution is stirred in the cylinder for 5 minutes by reversing the flat propeller every 6 seconds at a rotational speed of 1100 Orp, and the amount of bubbles is measured 30 seconds after the end of stirring.

Margin below

Claims (1)

[Claims] 1. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R is a linear, branched or cyclic alkyl or alkenyl group having 1 to 21 carbon atoms. , R' is a branched or cyclic alkyl group having 3 to 22 carbon atoms, a linear, branched or cyclic alkenyl or hydroxyalkyl group having 1 to 22 carbon atoms, or a linear, branched or cyclic alkoxy group having 2 to 25 carbon atoms. An amidosulfonic acid or its salt represented by an alkyl group, M represents hydrogen, an alkali metal, an alkaline earth metal, or an ammonium compound. 2. An alkali metal bisulfite salt is reacted with epihalohydrin to form an alkali metal salt of 3-halo-2-hydroxy-1-propanesulfonic acid, which has the general formula R'-NH_2 (wherein, R' has 3 carbon atoms). -22 branched or cyclic alkyl group, C1-22 linear, branched or cyclic alkenyl or hydroxyalkyl group, or C2-25 linear, branched or cyclic alkoxyalkyl group) The primary amine is reacted with a sulfonic acid alkali metal salt represented by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R' is the same as above. M' is an alkali metal) 2. The method for producing amidosulfonic acid or a salt thereof according to claim 1, characterized in that this is then acylated and further salt-exchanged if necessary. 3. A surfactant containing the amidosulfonic acid or its salt according to claim 1.