JPH03163052A - New quaternary ammonium-type carboxylic acid internal salt and production thereof - Google Patents

Abstract

NEW MATERIAL:The quaternary ammonium-type carboxylic acid internal salt of formula I (R<1> is 1-21C alkyl or alkenyl; R<2> and R<3> are same or different 1-6C alkyl; R<4> is 1-22C alkyl, alkenyl or arylalkyl; n is 1-6). EXAMPLE:3-[(Carboxyethyl)(lauroyl)amino]-N,N,N-trimethyl-1-propanaminium internal salt. USE:Useful as an ampholytic surfactant. It gives mild feeling to the skin, has excellent frothing power and hard water resistance and extremely high bio- degradability and solubility in water and is usable over a wide application range such as cosmetics, various detergents, pharmaceuticals, coating materials and textile-treating agents. PREPARATION:The objective compound of formula I can be produced by reacting a compound of formula II with a halogen compound of formula III (X is halogen) and hydrolyzing the resultant quaternary salt-type nitrile compound.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a novel quaternary ammonium type carboxylic acid internal salt, more specifically, a novel quaternary ammonium type carboxylic acid internal salt, which is hypoallergenic, has excellent foaming power and hard water resistance, and has good The present invention relates to a quaternary ammonium type carboxylic acid internal salt useful as a surfactant with biodegradability and a method for producing 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.

In addition, in recent years, surfactants have been required to have even more diverse properties depending on their use, and in particular, when used in shampoos and body cleansers, they have excellent foaming properties and hard water resistance, are mild to the skin, and are It is required to have good biodegradability and be non-polluting.

Recently, mildly irritating surfactants such as monoalkyl phosphate (MAP), sodium acylglutamate (AGS), and imidazoline active agents have been used as such surfactants. Although acylated amino acids and the like have been used as such, there has not yet been one that satisfactorily satisfies all of the above requirements.

[Means to solve the problem]

Under such circumstances, the present inventors conducted intensive research and found that the compound represented by the general formula (I) below is particularly relevant to
It has an excellent boosting effect on surfactants, is mild to the skin, has excellent hard water resistance, has good biodegradability, and can be produced with high purity by simple imitation from easily available raw materials. It was discovered that it can be produced in high yield, and the present invention was brought to fruition.

That is, the present invention relates to the following general formula (I) [wherein R' represents an alkyl group or alkenyl group having 1 to 21 carbon atoms, and 1<2 and R3 are the same or different and represent an alkyl group having 1 to 6 carbon atoms] , R4 represents an alkyl group, alganyl group, or arylalkyl group having 1 to 22 carbon atoms, and n represents a number of 1 to 6] and a method for producing the same. This is what we provide.

In the compound (I) of the present invention, R1 is an alkyl group or alkenyl group having 1 to 2 l of carbon atoms, and specific examples thereof include an acetyl group, a propylene group, a butyryl group, imbutyryl group, valeryl group, isovaleryl group, hexanoyl group, ectanoyl group, decanoyl group, lauroyl group, myristoyl group,
palmitoyl group, stearoyl group, arachidinoyl group,
Examples include a behenoyl group, an oleoyl group, a linoleyl group, an instearoyl group, a 2-ethylhexanoyl group, a 2-octyldecanoyl group, and a neodecanoyl group.

In addition, R2 and R3 include a methyl group, an ethyl group, a probyl group, an isoprobyl group, a butyl group, an isobutyl group,
Examples include pentyl group and hexyl group. Furthermore, R4
Examples include methyl group, ethyl group, probyl group, isopropyl group, butyl group, isobutyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, benzyl group,
Octyl group, decyl group, dodecyl group, tetradecyl group,
Examples include hexadecyl group, octadecyl group, eicosyl group, and docosyl group.

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

(■) (IV) (I) In the formula c, RI%R2, R3, R4 and 0 have the same meanings as above, and X represents a halogen atom] That is, 3-(N-acyl-N-(dialkylamino) By using probionitrile (II) as a raw material, reacting it with a halogen compound (lI[), and then hydrolyzing the obtained quaternary salt type nitrile (IV), Ammonium type carboxylic acid internal salt (I) is produced.

The reaction between the raw material compound (If) and the halogen compound (III) is carried out in the presence of a deoxidizer in a solvent such as water and methanol, ethanol, or isopropanol.
This is done by heating together with I). This quaternization reaction is carried out at 20-150°C, further at 40-130°C, especially at 60°C.
It is preferable to carry out the reaction at a reaction temperature of 0 to 110°C. Also,
The reaction time varies depending on the reactivity of the raw material compound (n), but is usually 2 to 48 hours. As the counter ion (X) of the halogen compound (R'X) used in the reaction, fluorine,
Examples include chlorine, oxaline, iodine, etc., and raw material compounds (
The molar ratio of the halogen compound to n) is 0.8 to 5
mol, more preferably 0.9 to 2 mol, especially 1 to 1.1 mol. In addition, as a deoxidizing agent, sodium carbonate etc. can be mentioned, and the amount used is 1 of the raw material compound (n).
It is preferably 5 to 5 mol%, especially 2 to 4 mol%.

After the reaction is completed, the product is cooled, and insoluble materials are filtered off, and the solvent is removed. If necessary, the product can be purified by methods such as recrystallization or column chromatography.

Next, the obtained quaternary salt type nitrile compound (IV) is hydrolyzed. Here, the hydrolysis reaction is carried out under alkaline conditions at 60%
It is preferred to carry out the reaction at a temperature of -105°C, especially 80-95°C. This invention! In the III manufacturing method,
For the purpose of smoothly proceeding the hydrolysis reaction, a quaternary ammonium type carboxylic acid internal salt (I), which is the final product, can be added to the reaction system. This amount is the fourth
It is preferably 0.05 to 10% by weight, particularly 0.5 to 5% by weight of the class salt type nitrile compound (IV). Furthermore, an alcoholic solvent such as ethanol may be added for the purpose of making the reaction proceed smoothly. Examples of the alkali include sodium hydroxide, and the amount used is at least equivalent to the quaternary salt type dihydroxide (TV), especially 1.2
It is preferred that the amount is 2 to 2 times equivalent.

After the reaction is complete, adjust ρH to the neutralization point of each target substance using hydrochloric acid, etc., then desalt by electrodialysis, etc., and then dehydrate (remove solvent) or desalt by filtration after dehydration (remove solvent). death,
Further, if necessary, the compound (I) of the present invention can be obtained by purification by recrystallization from a solvent or column chromatography.

〔Effect of the invention〕

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

〔Example〕

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

Example 1 Synthesis of 3-((carboxyethyl)(lauroyl)amino]-N,N.N-}limethyl-1-propanaminium inner salt (Ia): (I) 3-[(cyanoethyl)(lauroyl) )amino)
-N,N,N-}Remethyl-l-propanaminium chloride (Vla) synthesis: 500mj! In an autoclave of
a) 150 g (0.444 mol>,
39.1 g of isopropyl alcohol, 18.4 g of water 1 sodium carbonate 5. 7 g (0.0533 mol) and methyl chloride 26. 9g (0.533mo
j! ) and reacted at 100°C for 7 hours. After cooling, by-product common salt was removed by filtration (amine conversion rate 98.4%). The solvent was then evaporated under reduced pressure to obtain 138.6 g of solid material (crude yield 80.4%).
. Further, it was recrystallized from 8 times the amount of acetone to obtain 3-[(cyanoethyl)(lauroyl)amino) -N,N. N-}limethyl-1-propanaminium chloride (VI a
) 100.52 g was obtained (yield 58.3%).

m. p. :99~100℃ HPLC :Purity 99.0% Elemental analysis (%): Analytical value Calculated value C 64.95 65.00H 10
,99 10.91N 10.76 1
0.830 4,23 4.12 Cl 9J5 9.14 IR (KBr.c+a-'): 3450.
3000. 2920. 2840.2250.
1650. 1470. 1420.1385
, 1330, 1295. 1270.124
0. 1200, 1180. 1140.10
80. 1060,・1035.965,910,8
70,820,765.715 NMR (CDC/3, δppm): 0. 66
~2. 00 (23H, m). 2. 00-2
．． 60 (2H, m). 2. 90 (2H.
t, J=6. 0Hz) ,3. 43 (9H.s
). 3.30-4. 05 (611.m) (2) 3-
[(ruboxyethyl) (lauroyl)amino)-N
．． N. N-}limethyl-1-propanaminium internal salt (
Synthesis of Ia): 300mj! Put the 31 [(
cyanoethyl) (lauroyl)amino] -N. N.
N-trimethyl-l-propanaminium chloride (V
l a ) 60 g (0.155mof)
, 92.71g (0.232g) of 10% sodium hydroxide
mof), water 55. Prepare 27g and heat to 90-95℃
The mixture was reacted for 4 hours, and after cooling, the pH was adjusted to 7 with 36% hydrochloric acid. Ethanol was added to the obtained solution for azeotropic dehydration, and then insoluble materials were removed by filtration. The ethanol solution was then evaporated under reduced pressure to obtain 56.71 g of solid material (crude yield 99.0%). II P L of this thing
Purity by C was 90.1%. 50g of this
was purified by silica gel force column chromatography (developing solvent: chloroform/methanol = 2/1), the solvent was completely removed, and 3-((carboxyethyl)( lauroyl) amino)
-N. N. 17.44 g of N-trimethyl-1-propanaminium internal salt (Ia) were obtained.

m. p, : 1 5? ~159℃ HPLC:
Purity 98.5% Elemental analysis (%): Analysis value Calculated value C 67.79 68.06+1
11. 56 11. 43N 7.28
7.56ro 13.17
12.95IR(KBr,c
o+-'): 3450, 2910. 2850
．． 1630.1575. 1480. 1400
．． 1310.1265. 1240. 119
0. 1130.1070. 1040. 96
0, 920, 860,720.620 NMR (CDCj! 3.δppm): 0. 6
7-1. 87 (2111.m). 1. 87~
2. 73 (611, m). 3. 30 (9fl
, s), 3.03-3. 93 (6H, m) Example 2 Foaming power test: The foaming power of the compound (Ia) of the present invention obtained in Example 1 and the comparative compounds shown in Table 1 was determined by an inversion stirring method. .2%, lanolin 0.5%, pH 7, 4
Measured under the conditions of 40°C. Note that the foaming power was expressed as a relative value when the foam volume when using monolauryl phosphate triethanolamine salt as a test compound was set to 1.00. 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 100 rpm, and the amount of foam is determined 30 seconds after the end of stirring.

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

Example 3 Foaming power test: The foaming power of the compound (Ia) of the present invention obtained in Example 1 and the comparative compounds shown in Table 2 was tested using the same reverse stirring method as in Example 1. Triethanolamine salt 0.15%, test compound 0. 05%,
Measurement was carried out under the conditions of lanolin 0.5%, pH 7, 4°El}l, 140°C. Foaming power was determined by measuring the amount of foam when monolauryl phosphate triethanolamine salt was used as the test compound. It is expressed as a relative value when it is set to 00. The results are shown in Table 2.

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

Example 4 Skin irritation test: Regarding the compound of the present invention obtained in Example 1 (Ia>) and the comparative compounds shown in Table 3, the skin irritation test
I looked into gender. That is, in a 24-hour closed patch method using guinea pigs (Group I, 5 animals), each test compound was diluted with distilled water to a concentration of 5% or 1%, and the patch was removed 48 hours later. 0 points for no skin irritation, 1 point for slight erythema, 2 points for erythema,
A score of 3 points was given for a case showing clear erythema, and a score of 4 points was given for a case showing erythema accompanied by exfoliation, and the weighted average value was determined as the skin irritation reaction intensity. The results are shown in Table 3.

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

Example 5 Hard water resistance test: The hard water resistance of the compound of the present invention ([a) obtained in Example 1 and the comparative compounds shown in Table 4 was evaluated according to test compound 1.
Ca(j!2
CalJil degree (ppm) when the solution becomes cloudy
). The results are shown in Table 4.

Margin below As is clear from Table 4, The compounds of the present invention are very Shows excellent hard water resistance.

Below Up

Claims (1)

[Claims] 1. The following general formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1 represents an alkyl group or 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 an alkyl group having 1 to 6 carbon atoms.
22 alkyl group, alkenyl group or arylalkyl group, and n is a number from 1 to 6. 2. The following general formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (II) [In the formula, R^1 represents an alkyl group or alkenyl group having 1 to 21 carbon atoms, and R^2 and R^ 3 is the same or different and represents an alkyl group having 1 to 6 carbon atoms.] The following general formula (
III) Reacting a halogen compound represented by R^4X(III) [wherein R^4 represents an alkyl group, alkenyl group, or arylalkyl group having 1 to 22 carbon atoms, and X represents a halogen atom], 2. The method for producing a quaternary ammonium type carboxylic acid internal salt according to claim 1, wherein the obtained quaternary salt type nitrile compound is then hydrolyzed.