JPH0825975B2 - Novel quaternary ammonium type carboxylic acid inner salt and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention is a novel quaternary ammonium type carboxylic acid inner salt, more specifically, it is hypoallergenic, has excellent super-foaming power and hard water resistance, and is good. Relates to a quaternary ammonium type carboxylic acid inner salt useful as a surfactant having excellent biodegradability and a method for producing the same.

[Problems to be Solved by Prior Art and Invention]

Surfactants are compounds having a hydrophobic group and a hydrophilic group in the molecule, and make use of basic performance such as wetting, washing, emulsifying, dispersing, and foaming, cosmetics, detergent raw materials, pharmaceuticals, paints, fiber treatment agents and Widely used as an emulsifier.

Further, in recent years, surfactants have been required to have various properties depending on their use, and particularly when used in shampoos and body wash agents, they have excellent foaming properties and hard water resistance,
It is required to be mild to the skin, have good biodegradability, and be non-polluting.

Therefore, these surfactants have recently been used as mild surfactants such as monoalkyl phosphate (MAP), sodium acylglutamate (AGS), and imidazoline-based surfactants, and as a booster (foaming agent). Although modified amino acids and the like have been used, none have been able to sufficiently satisfy all of the above requirements.

[Means for solving the problem]

Under such circumstances, as a result of earnest studies by the present inventors, the compound represented by the general formula (I) described below is particularly MAP.
In addition to exhibiting an excellent booster effect against surfactants, it is mild to the skin and has excellent hard water resistance, good biodegradability, and highly pure and easily produced from easily available raw materials. The present invention has been completed by finding that it can be produced in a high yield.

That is, the present invention provides the following general formula (I) [In the formula, R ¹ represents an alkyl group or an alkenyl group having ¹ to 21 carbon atoms, R ² and R ³ are the same or different and represent an alkyl group having 1 to 6 carbon atoms, and R ⁴ is 1 to 22 carbon atoms. Represents an alkyl group, an alkenyl group or an arylalkyl group, and n is 1 to 6
The present invention provides a quaternary ammonium type carboxylic acid inner salt represented by the formula and a method for producing the same.

In the compound (I) of the present invention, R ¹ is an alkyl group or alkenyl group having ¹ to 21 carbon atoms, As specific examples thereof, for example, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group,
Isovaleryl group, hexanoyl group, octanoyl group, decanoyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, arachidinoyl group, behenoyl group, oleoyl group, linoleoyl group, isostearoyl group, 2-ethyl-hexanoyl group, 2- Examples thereof include an octyl-decanoyl group and a neodecanoyl group. Examples of R ² and R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group and a hexyl group. Further, as R ⁴ , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a neopentyl group,
Hexyl group, cyclohexyl group, benzyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, docosyl group and the like can be mentioned.

Such a quaternary ammonium type carboxylic acid inner salt of the present invention is produced, for example, according to the following reaction formula.

[Wherein, R ¹ , R ² , R ³ , R ⁴ and n have the same meanings as described above,
X represents a halogen atom] That is, 3- [N-acyl-N- (dialkylaminoalkyl) amino] propionitrile (II) was used as a raw material, and this was reacted with a halogen compound (III), and then obtained. By hydrolyzing the quaternary salt type nitrile compound (IV), the quaternary ammonium type carboxylic acid inner salt (I) is produced.

The reaction between the starting compound (II) and the halogen compound (III) is carried out in the presence of a deoxidizing agent in water and a solvent such as methanol, ethanol or isopropanol in the presence of a halogen compound (II).
I) by heating with. This quaternization reaction is preferably carried out at a reaction temperature of 20 to 150 ° C, more preferably 40 to 130 ° C, and particularly 60 to 110 ° C. In addition, the reaction time varies depending on the reactivity of the raw material compound (II), but is usually 2 to 48
Time. Examples of the counter ion (X) of the halogen compound (R ⁴ X) used in the reaction include fluorine, chlorine, arsenic and iodine, and the molar ratio of the halogen compound to the starting compound (II) is 0.8 to 5 It is preferably in moles, more preferably 0.9 to 2 moles, and especially 1 to 1.1 moles. Moreover, sodium carbonate etc. are mentioned as a deoxidizer, and the usage-amount is 1-5 mol% of the raw material compound (II), and it is preferable that it is especially 2-4 mol%.

After the completion of the reaction, the reaction mixture is cooled, the insoluble matter is filtered off, the solvent is removed, and if necessary, the product can be purified by a method such as recrystallization or column chromatography.

Next, the obtained quaternary salt type nitrile body (IV) is hydrolyzed. Here, the hydrolysis reaction is 60 to 60
It is preferably carried out at a reaction temperature of 105 ° C, especially 80 to 95 ° C. In the production method of the present invention, the final product, a quaternary ammonium type carboxylic acid internal salt (I), can be added to the reaction system for the purpose of smoothly proceeding the hydrolysis reaction. The blending amount is preferably 0.05 to 10% by weight, and more preferably 0.5 to 5% by weight of the quaternary salt type nitrile body (IV). Further, an alcohol solvent such as ethanol may be added for the purpose of allowing the reaction to proceed smoothly. Examples of the alkali include sodium hydroxide,
The amount used is preferably equivalent amount or more, particularly 1.2 to 2 times equivalent amount, relative to the quaternary salt type nitrile compound (IV).

After completion of the reaction, adjust the pH to the neutralization point of each target with hydrochloric acid, etc., and then desalting by electrodialysis, etc., and then dehydrate (desolvent) or dehydrate (desolvent) and then desalting by filtration. Then, if necessary, the compound (I) of the present invention can be obtained by purification from a solvent by recrystallization or column chromatography.

〔The invention's effect〕

The thus obtained quaternary ammonium type carboxylic acid inner salt (I) of the present invention has a quaternary alkyl-substituted amino group and a carboxyl group in the molecule, and is a novel amphoteric type which forms an inner salt. It is a surfactant, mild to the skin, excellent in foaming power and hard water resistance, and has excellent characteristics such as biodegradability and solubility in water, and cosmetics and various detergents. It can be widely used in various fields such as pharmaceuticals, paints, fiber treatment agents and emulsifiers.

〔Example〕

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

Example 1 3-[(carboxyethyl) (lauroyl) amino]-
N, N, N-trimethyl-1-propanaminium inner salt (I
Synthesis of a): (1) 3-[(cyanoethyl) (lauroyl) amino]
Synthesis of --N, N, N-trimethyl-1-propanaminium chloride (IVa): 3- [N-lauroyl-N was added to a 500 ml autoclave.
-(3'-Dimethylaminopropyl) amino] propionitrile (IIa) 150g (0.444mol), isopropyl alcohol 39.1g, water 18.4g, sodium carbonate 5.7g (0.0533mo
l) and 26.9 g (0.533 mol) of methyl chloride were charged,
The reaction was carried out at 100 ° C for 7 hours. After cooling, salt produced as a by-product was removed by filtration (reaction rate of amine: 98.4%). Then, the solvent was evaporated under reduced pressure to obtain 138.6 g of a solid product (crude yield 80.4%). Further recrystallized from 8-fold amount of acetone to give 3-[(cyanoethyl) (lauroyl) amino] -N,
N, N-trimethyl-1-propanaminium chloride (I
Va) 100.52 g was obtained (yield 58.3%).

mp: 99 to 100 ° C HPLC: Purity 99.0% Elemental analysis (%): Analytical value Calculated value C 64.95 65.00 H 10.99 10.91 N 10.76 10.83 O 4.23 4.12 Cl 9.35 9.14 IR (KBr, cm ^-1 ): 3450,3000,2920 , 2840,2250,1650,1470,
1420,1385,1330,1295,1270,1240,1200,1180,1140,1080,
1060,1035,965,910,870,820,765,715 NMR (CDCl ₃ , δppm): 0.66 to 2.00 (23H, m), 2.00 to 2.60
(2H, m), 2.90 (2H, t, J = 6.0Hz), 3.43 (9H, s), 3.30 ~
4.05 (6H, m) (2) 3-[(Carboxyethyl) (lauroyl) amino] -N, N, N-trimethyl-1-propanaminium inner salt (Ia) synthesis: in a 300 ml four neck flask 3-[(cyanoethyl) (lauroyl) amino] -N, N, N-trimethyl-1-propanaminium chloride (IVa) obtained in (1) 60 g (0.15
5mol), 10% sodium hydroxide 92.71g (0.232mol), water
Charge 55.27g, react at 90-95 ℃ for 4 hours, cool,
The pH was adjusted to 7 with 36% hydrochloric acid. Ethanol was added to the obtained solution for azeotropic dehydration, and insoluble materials were removed by filtration. Then the ethanol solution was evaporated under reduced pressure.
56.71 g of a solid product was obtained (crude yield 99.0%). HP of this thing
The purity by LC was 90.1%. 50 g of this was purified by silica gel column chromatography (developing solvent: chloroform / methanol = 2/1), and the solvent was completely removed to give pale yellow, highly hygroscopic crystals.
[(Carboxyethyl) (lauroyl) amino] -N, N,
N-trimethyl-1-propanaminium inner salt (Ia) 17.
I got 44g.

mp: 157-159 ° C HPLC: Purity 98.5% Elemental analysis (%): Analytical value Calculated value C 67.79 68.06 H 11.56 11.43 N 7.28 7.56 O 13.17 12.95 IR (KBr, cm ^-1 ): 3450,2910,2850,1630, 1575,1480,1400,
1310,1265,1240,1190,1130,1070,1040,960,920,860,72
0,620 NMR (CDCl ₃ , δppm): 0.67 to 1.87 (21H, m), 1.87 to 2.73
(6H, m), 3.30 (9H, s), 3.03 to 3.93 (6H, m) Example 2 Foaming power test: Regarding the compound (Ia) of the present invention obtained in Example 1 and the comparative compounds shown in Table 1. , The foaming power is reversed by the stirring method ^* ,
Test compound 0.2%, lanolin 0.5%, pH 7, 4 ° DH, 40 ° C
It was measured under the conditions. The foaming power 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.

* Inversion 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 30 seconds, the amount of foam is measured after 30 seconds.

As is clear from Table 1, the compound of the present invention has an excellent foaming power.

Example 3 Foaming power test: Regarding the compound (Ia) of the present invention obtained in Example 1 and the comparative compounds shown in Table 2, the foaming power was measured by the same reversal stirring method as in Example 1 for monolauryl phosphate triethanol. Amine salt 0.15%, test compound 0.05%, lanolin 0.5
%, 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.

Example 4 Skin irritation test: The skin irritation of the compound (Ia) of the present invention obtained in Example 1 and the comparative compounds shown in Table 3 was examined. That is, in the 24-hour closed patch method using guinea pigs (5 animals per group), each test compound was diluted with distilled water to give a 5% or 1% concentration, and 48 hours after removal of the patch. No skin irritation 0 points, slight erythema 1 point, erythema 2 points, clear erythema 3 points, drop erythema 4 points Then, the weighted average value was determined as the skin irritation reaction strength. The results are shown in Table 3.

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

Example 5 Hard water resistance test: With respect to the compound (Ia) of the present invention obtained in Example 1 and the comparative compounds shown in Table 4, the hard water resistance thereof was tested as a test compound 1.0.
CaCl ₂ was gradually added to an aqueous solution containing 10% of pH 7, and the concentration 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 very excellent hard water resistance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location B01F 17/22 C11D 1/90

Claims (2)

[Claims] 1. The following general formula (I): [In the formula, R ¹ represents an alkyl group or an alkenyl group having ¹ to 21 carbon atoms, R ² and R ³ are the same or different and represent an alkyl group having 1 to 6 carbon atoms, and R ⁴ is 1 to 22 carbon atoms. Represents an alkyl group, an alkenyl group or an arylalkyl group, and n is 1 to 6
The quaternary ammonium type carboxylic acid inner salt represented by the formula 2. The following general formula (II) [In the formula, R ¹ represents an alkyl group or an alkenyl group having ¹ to 21 carbon atoms, and R ² and R ³ are the same or different and represent an alkyl group having 1 to 6 carbon atoms] 3- [N- Acyl-N- (dialkylaminoalkyl) amino] propionitrile has the following general formula (III) R ⁴ (III) [wherein R ⁴ represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group or an arylalkyl group]. Wherein X represents a halogen atom], and then the resulting quaternary salt-type nitrile compound is hydrolyzed, and the quaternary ammonium-type carboxylic acid according to claim 1. Internal salt production method.