JPH08311003A - New amide compound and its production - Google Patents

Abstract

PURPOSE: To obtain a new amine compound having low stimulation to skin and hair, giving good feeling, excellent in foamability and emulsion stability and useful as a component for various detergents, cosmetics, etc., emulsifiers, conditionings, etc. CONSTITUTION: This new amide compound is a compound expressed by formula I [R is an (OH substituted) 1-24C (branched) alkyl or alkenyl; A is an (OH or carboxyl substituted) 1-6C (branched) alkylene; B is an (OH substituted) 2-6C (branched) alkylene; Y is carboxyl, a sulfonic acid group, a sulfuric acid ester group or a salt thereof]. E.g. 4,7-dioctanoyl-4,7-diazadecane-1,10-disulfonic acid disodium salt. The compound of formula I can be obtained by reacting a compound of formula II [Y' is a carboxyl, a sulfonic acid group, a sulfuric acid ester group, an alkoxycarbonyl (F1 ), nitrile (F2 ) or OH] with a compound of formula III [X is a halogen, OH or a 1-3C (branched) alkoxyl] and further hydrolyzing the reaction product when Y' is F1 or F2 or esterifying with sulfuric acid when Y' is OH.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has little irritation to the skin and the like, is excellent in foaming property, and can give a favorable touch to the skin and the like, and is a base and a cleaning agent for hair and skin cosmetics.
The present invention relates to an amide compound useful as an emulsifier, a conditioning agent, etc. and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, surfactants such as alkyl sulfates, polyoxyethylene alkyl sulfates, and alkylbenzene sulfonates have been used as detergents and emulsifiers. However, many of these have the problem that the skin irritation during use is rather strong. For this reason, surfactants such as alkyl phosphates and acylated amino acid salts, which have low skin irritation, are being used as a base for hair and skin cosmetics, an emulsifier, or a cleanser for skin and the like.

However, recently, along with the diversification of consumers' demands and the trend toward high-grade products, in addition to less irritation to the skin and the like, good foaming properties and the ability to impart a pleasant feel to the skin and the like have been achieved. The above surfactants have not been able to sufficiently meet these requirements.

[0004]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to solve the above-mentioned problems, to cause less irritation to the skin and the like, excellent foaming property, and further to give a pleasant feeling to the skin and the like, And a compound useful as a base for skin cosmetics, a detergent, an emulsifier, a conditioning agent, and the like.

[0005]

Under the circumstances, as a result of intensive studies, the present inventors have found that the novel amide compound represented by the following general formula (1) has a favorable feeling to skin and the like with low irritation. In addition, the present invention was completed by finding out that it has excellent foamability and emulsion stability.

That is, the present invention provides the following general formula (1)

[0007]

[Chemical 4]

[In the formula, two Rs are the same or different and each represents a linear or branched alkyl or alkenyl group having 1 to 24 carbon atoms, which may be substituted with a hydroxyl group, and A is a hydroxyl group. Represents a linear or branched alkylene group having 1 to 6 carbon atoms which may be substituted by a group or a carboxyl group, and B represents a linear or branched carbon number 2 to 6 which may be substituted by a hydroxyl group. And an Y is a carboxyl group, a sulfonic acid group, a sulfuric acid ester group or a salt thereof. ] The present invention relates to an amide compound represented by

In the general formula (1), the number of carbon atoms of the linear or branched chain which may be substituted by the hydroxyl group represented by R is 1
Specific examples of the alkyl group or alkenyl group of
The following can be mentioned.

Examples of the linear alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, Henicosyl, docosyl, tricosyl and tetracosyl can be mentioned, and examples of the branched chain alkyl group include groups such as methylhexyl, ethylhexyl, methylheptyl, ethylheptyl, methylnonyl, methylundecyl, methylheptadecyl, hexyldecyl and octyldecyl. Can be mentioned.

Examples of the straight chain alkenyl group include ethenyl, propenyl, butenyl, pentenyl, hexenyl,
Heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl,
Examples thereof include groups such as pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icosenyl, henicosenyl, docosenyl, tricosenyl, and tetracosenyl, and examples of the branched chain alkenyl group include, for example, methylhexenyl, ethylhexenyl, methylheptenyl, ethylheptenyl, methylnonenyl, methylnonenyl. Mention may be made of groups such as cenyl, methylheptadecenyl, hexyldecenyl, octyldecenyl and the like.

The linear or branched alkyl group substituted with a hydroxyl group is not particularly limited in the substitution position of the hydroxyl group, and examples thereof include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, Hydroxyheptyl, hydroxyoctyl, hydroxynonyl, hydroxydecyl, hydroxyundecyl, hydroxydodecyl, hydroxytridecyl, hydroxytetradecyl,
Hydroxypentadecyl, hydroxyhexadecyl, hydroxyheptadecyl, hydroxyoctadecyl, hydroxynonadecyl, hydroxyicosyl, hydroxyhenicosyl, hydroxydocosyl, hydroxytricosyl, hydroxytetracosyl, hydroxymethylhexyl, hydroxyethylhexyl, hydroxymethyl Examples thereof include groups such as heptyl, hydroxyethylheptyl, hydroxymethylnonyl, hydroxymethylundecyl, hydroxymethylheptadecyl, hydroxyhexyldecyl and hydroxyoctyldecyl.

The linear or branched alkenyl group substituted with a hydroxyl group is not particularly limited in the substitution position of the hydroxyl group, and examples thereof include hydroxyethenyl, hydroxypropenyl, hydroxybutenyl, hydroxypentenyl, hydroxyhexenyl and hydroxy. Heptenyl, hydroxyoctenyl, hydroxynonenyl, hydroxydecenyl, hydroxyundecenyl, hydroxydodecenyl, hydroxytridecenyl, hydroxytetradecenyl, hydroxypentadecenyl, hydroxyhexadecenyl, Hydroxyheptadecenyl, hydroxyoctadecenyl, hydroxynonadecenyl, hydroxyicosenyl, hydroxyhenicosenyl, hydroxydocosenyl, hydroxytricosenyl, hydroxytetracosenyl, hydroxy Groups such as methylhexenyl, hydroxyethylhexenyl, hydroxymethylheptenyl, hydroxyethylheptenyl, hydroxymethylnonenyl, hydroxymethylundecenyl, hydroxymethylheptadecenyl, hydroxyhexyldecenyl, hydroxyoctyldecenyl. Can be mentioned.

Of these, R is a linear or branched alkyl or alkenyl group having 1 to 18 carbon atoms which may be substituted with a hydroxyl group, from the viewpoint of performance such as foaming power and detergency. Further, a linear or branched alkyl group having 6 to 18 carbon atoms, particularly a linear alkyl group having 8 to 12 carbon atoms is preferable. The two R's in one molecule may be the same or different, but are preferably the same.

Further, the linear or branched alkylene group having 1 to 6 carbon atoms which may be substituted with the hydroxyl group or the carboxyl group represented by A includes methylene, ethylene, trimethylene, propylene, tetramethylene and penta. Methylene, hexamethylene, 2-hydroxytrimethylene, 1-carboxyethylene, 2-carboxyethylene and the like can be mentioned. Of these, an alkylene group having 1 to 3 carbon atoms which may be substituted with a hydroxyl group or a carboxyl group, an alkylene group having 1 to 3 carbon atoms which may be further substituted with a hydroxyl group, and particularly an unsubstituted carbon number 1-3 alkylene groups are preferred.

As the linear or branched alkylene group having 2 to 6 carbon atoms which may be substituted with the hydroxyl group represented by B, ethylene, trimethylene, propylene,
Tetramethylene, pentamethylene, hexamethylene, 2-
Examples include hydroxytrimethylene. Of these, an unsubstituted alkylene group having 2 to 6 carbon atoms, particularly ethylene is preferable.

The compound (1) of the present invention comprises a carboxyl group (-C
OOH), sulfonic group (-SO ₃ H), or because they have a sulfate group (-OSO ₃ H), can form salts between the various basic substances. Examples of such salts include alkali metal salts, alkaline earth metal salts, amine salts, basic amino acid salts, ammonium salts, and the like.
Salts with sodium, potassium, lithium, magnesium, calcium, trimethylamine, triethylamine, tributylamine, monoethanolamine, diethanolamine, triethanolamine, lysine, arginine, choline, ammonia and the like can be mentioned, and among these, sodium salt and potassium. Salts and ammonium salts are preferred.

The amide compound (1) of the present invention can be produced, for example, according to the following reaction.

[0019]

Embedded image

[Wherein R, A, B and Y have the same meanings as described above, X represents a halogen atom, a hydroxyl group, or a linear or branched alkoxyl group having 1 to 3 carbon atoms, and Y ' Represents a carboxyl group, a sulfonic acid group, a sulfuric ester group, an alkoxycarbonyl group, a nitrile group or a hydroxyl group. ]

That is, when Y '= Y, the amide compound (1) of the present invention is obtained by reacting the amino compound (2) with the acyl compound (3), and Y'is an alkoxycarbonyl group or a nitrile group. Alternatively, when it is a hydroxyl group, the amide compound of the present invention can be obtained by further converting Y ′ to Y after the reaction of the amino compound (2) with the acyl compound (3).
(1) is obtained.

The amino compound (2) is, for example, a diamine,
It can be produced by a known method such as reacting with a halide, an olefin compound, an epoxy compound, a sultone or the like.

Here, specific examples of the diamine include ethylenediamine, trimethylenediamine, propylenediamine, hexamethylenediamine and 2-hydroxytrimethylenediamine, and specific examples of the halide include sodium chloroacetate and sodium bromoacetate. , Sodium chloropropionate, sodium bromopropionate, sodium 3-chloro-2-hydroxypropanesulfonate, 2-chloroethanol, 3-chloropropanol and the like are specific examples of the olefin compound, methyl acrylate, ethyl acrylate. , Propyl acrylate, acrylonitrile, methyl maleate, ethyl maleate, propyl maleate, methyl fumarate, ethyl fumarate,
Specific examples of sultone include propyl fumarate and the like, and propane sultone, butane sultone and the like can be mentioned.

In the general formula (3), examples of the halogen atom represented by X include a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a chlorine atom is preferable. Examples of the alkoxyl group represented by X include a methyl group, an ethyl group and a propyl group.

When the amino compound (2) is soluble only in water, the reaction between the amino compound (2) and the acyl compound (3) (acyl halide) in which X is a halogen atom can be carried out, for example, in an aqueous inert solvent, 0 to 50 ° C, preferably 10 to 30 ° C,
It is carried out by reacting the amino compound (2) with a 2 to 5 times molar amount of an acyl halide. Examples of the aqueous inert solvent include water, water / acetone, water / methyl ethyl ketone, and the like. Among them, a mixed solvent of water and acetone is preferable.

When the amino compound (2) is soluble in an organic solvent other than water, the reaction of the amino compound (2) with an acyl halide is carried out without solvent or in an inert solvent at 0 to 50 ° C., preferably Is carried out by reacting 2 to 5 times mol of an acyl halide with respect to the amino compound (2) at 0 to 30 ° C.
The reaction of the amino compound (2) with an acyl compound (3) in which X is a hydroxyl group or an alkoxyl group (carboxylic acid or carboxylic acid ester) is carried out without a solvent or in an inert solvent at 50 to 200 ° C. It is preferably carried out at 80 to 160 ° C. Examples of the inert solvent include toluene and xylene. Here, when the acyl compound (3) is a carboxylic acid ester, the reaction can be performed at a lower temperature by allowing a basic catalyst such as an alkoxide to be present in the system.

When the amino compound (2) in which Y '= Y is used, the compound of the present invention (1) is directly obtained by the above reaction, but the amino compound (2) in which Y'is an alkoxycarbonyl group or a nitrile group. In the case of using an amino compound (2) in which Y ′ is converted to a carboxyl group by hydrolysis in the presence of a basic catalyst after the above reaction, and Y ′ is a hydroxyl group, After the above reaction,
Furthermore, the compound (1) of the present invention can be obtained by converting Y'to a sulfate ester group by reacting with a sulfate esterifying agent such as chlorosulfonic acid or SO ₃ gas.

The compound (1) of the present invention thus obtained can be converted into a salt by neutralizing with a basic substance, if necessary. As the basic substance, sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, ammonia, trimethylamine, triethylamine, tributylamine, alkanolamine (monoethanolamine, diethanolamine, triethanolamine, etc.) , Lysine, arginine, choline, etc., among which sodium hydroxide,
Alkali metal hydroxides such as potassium hydroxide are preferred.

After completion of the above reaction, the reaction mixture contains not only the desired amide compound (1) of the present invention but also inorganic salt, unreacted amino compound (2), ester derivative, fatty acid and other compounds. There is. In the present invention, the reaction product can be used as it is, but if necessary, purified by a known method such as a solvent fractionation method, an ion exchange chromatography method, a recrystallization method, an electrodialysis method, etc. You can also

The amide compound (1) of the present invention gives a pleasant sensation to the skin and the like with a low irritation, and an excellent detergency,
Since it has a foaming power, it can be applied to various cleaning agents for skin, hair, tableware, clothing, etc., various cleaning agents such as clothing cleaning agents, and also because it has a stable emulsifying ability, it can be applied to skin and hair cosmetics. It can be used as an emulsifier, a conditioning agent and the like. In this case, the compounding amount of the compound (1) of the present invention is not particularly limited, and it can be used in the range of 0.1 to 80% by weight, preferably 1 to 50% by weight, depending on the use and the like.

When the compound (1) of the present invention is used for these purposes, various known surfactants, humectants, and
Bactericide, emulsifier, thickener, pearlizing agent, divalent metal ion scavenger, alkali agent, inorganic salt, anti-redeposition agent, enzyme, scavenger of available chlorine, reducing agent, bleaching agent, fluorescent dye, solubilizing agent Agents, fragrances, anti-caking agents, enzyme activators, antioxidants, preservatives, dyes, bluing agents, bleach activators, enzyme stabilizers, phase regulators, penetrants, etc. can be added. .

[0032]

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 3 g (0.05 mol) of ethylenediamine and 50 g of water were placed in a four-necked flask, and 12.3 g (0.1 mol) of propane sultone was added dropwise over 30 minutes. After stirring for 2 hours, add ethanol, filter, and wash with ethanol to remove N, N′-bis (3-sulfopropyl) ethylenediamine.
13.5 g was obtained (isolated yield: 88%). Next, N, N′-bis (3-
Sulfopropyl) ethylenediamine 5 g (0.016 mol),
Put 30g of water and 13g of acetone in a 4-neck flask and put in 4N
The pH was adjusted to 8.5 with aqueous sodium hydroxide solution. After cooling to 10 ° C., 5.3 g (0.033 mol) of caprylic acid chloride was added dropwise. During the process, the pH dropped, so a 4N aqueous sodium hydroxide solution was added at an appropriate time to keep the pH at 9-10. After completion of dropping, the mixture was stirred for 1 hour, and water was distilled off with an evaporator while azeotropically distilling with ethanol. Then, 250 g of water was added and filtered to remove the insoluble portion. After desalting by electrodialysis, it was freeze-dried to obtain 3.0 g of 4,7-dioctanoyl-4,7-diazadecane-1,10-disulfonic acid disodium salt (isolated yield: 31
%).

Mass spectrometry (FAB ionization method) m / z: 601 (M +
H ⁺ ), m = C ₂₄ H ₄₆ S ₂ O ₈ N ₂ Na ₂ ¹ H-NMR (CDCl ₃ , δppm): 0.83 (t, 6H, a), 1.27 (broad, 16H,
b), 1.58 (m, 4H, c), 2.00 (m, 4H, d), 2.34 (t, 4H, e), 2.89
(t, 4H, f), 3.40-3.62 (m, 8H, g)

[0035]

[Chemical 6]

Example 2 3 g of ethylenediamine (0.05 mol) and 50 g of water were placed in a four-necked flask, and then 11.7 g of sodium chloroacetate (0.
1 mol) aqueous solution was added dropwise over 30 minutes. After stirring at 60 ° C. for 2 hours and washing with ethanol, 8.8 g of N, N′-bis (carboxymethyl) ethylenediamine was obtained (isolated yield: 88%). Next, 5 g (0.028 mol) of N, N'-bis (carboxymethyl) ethylenediamine, 30 g of water and 13 g of acetone were placed in a four-necked flask and the pH was adjusted to 8.5 with a 4N aqueous sodium hydroxide solution. After cooling to 10 ° C, 9.3 g (0.057 mol) of caprylic acid chloride was added dropwise. During the process, the pH dropped, so a 4N aqueous sodium hydroxide solution was added at an appropriate time to keep the pH at 9-10. After the dropping is completed,
The mixture was stirred for 1 hour, and water was distilled off with an evaporator while azeotropically boiling with ethanol. Then add 250g of water and filter,
The insoluble portion was removed. After desalting with electrodialysis, lyophilize
4.6 g of 3,6-dioctanoyl-3,6-diazaoctanedioic acid disodium salt was obtained (isolated yield: 35%).

Mass spectrometry (FAB ionization method) m / z: 473 (M +
H ⁺ ), m = C ₂₂ H ₃₈ O ₆ N ₂ Na ₂ ¹ H-NMR (CDCl ₃ , δppm): 0.85 (t, 6H, a), 1.29 (broad, 16H,
b), 1.61 (m, 4H, c), 2.34 (t, 4H, d), 3.40-3.62 (m, 4H, e),
4.11 (s, 4H, f)

[0038]

[Chemical 7]

Example 3 5 g (0.034 mol) of N, N'-bis (2-hydroxyethyl) ethylenediamine, 30 g of water and 13 g of acetone were placed in a 4-necked flask, and the pH was adjusted with a 4N aqueous sodium hydroxide solution. Was adjusted to 8.5. After cooling to 10 ° C., 11.6 g (0.071 mol) of caprylic acid chloride was added dropwise. During the process, the pH dropped, so a 4N aqueous sodium hydroxide solution was added at an appropriate time to keep the pH at 9-10. After completion of dropping, the mixture was stirred for 1 hour and at room temperature for 3 hours. After the solvent was distilled off, the residue was dissolved in dichloromethane and chlorosulfonic acid was added dropwise under ice cooling. After stirring for 1 hour, the mixture was stirred at room temperature for 3 hours.
After that, 250 g of water was added to adjust the pH to 7, and the insoluble portion was removed by filtration. After desalting by electrodialysis, lyophilization was performed to disodium 3,6-dioctanoyl-3,6-diazaoctane-1,8
-6.0 g of disulfate was obtained (isolated yield: 29%).

Mass spectrometry (FAB ionization method) m / z: 605 (M +
H ⁺ ), m = C ₂₂ H ₄₂ S ₂ O ₁₀ N ₂ Na ₂ ¹ H-NMR (CDCl ₃ , δppm): 0.88 (t, 6H, a), 1.29 (broad, 16H,
b), 1.66 (m, 4H, c), 2.30 (t, 4H, d), 3.41-3.66 (m, 8H, e),
4.44 (broad, 4H, f)

[0041]

Embedded image

Formulation Example 1 A shampoo having the following composition was produced using the compound of the present invention.

[Table 1] (Composition) (wt%) Compound of Example 1 15.0 Lauroyldiethanolamide 3.0 Lauryl dimethylamine oxide 0.5 Hydroxyethyl cellulose (manufactured by Daicel) 0.1 Sodium benzoate 0.3 Dye proper amount Perfume proper amount Citric acid proper amount water balance meter 100.0

Formulation Example 2 A shampoo was prepared in the same manner as in Formulation Example 1 except that the compound of Example 2 or 3 was used in place of the compound of Example 1.

The shampoos of Formulation Examples 1 and 2 were both excellent in foaming property and detergency, and had a good feel at the time of washing hair and rinsing.

Formulation Example 3 A body shampoo having the following composition was produced using the compound of the present invention.

[Table 2] (Composition) (wt%) Compound of Example 1 17.0 Polyoxyethylene (EO3) lauryl glucoside 5.0 Lauryl dimethylamine oxide 3.0 Glycerin 4.0 Sucrose fatty acid ester 1.0 Methyl paraben 0.3 Dye proper amount Perfume proper amount Citric acid proper amount Water balance meter 100.0

Formulation Example 4 A shampoo was prepared in the same manner as in Formulation Example 3, except that the compound of Example 2 or 3 was used in place of the compound of Example 1.

The body shampoos of Formulation Examples 3 and 4 were all excellent in foamability and detergency, and had a moist and good feeling after washing.

[0048]

EFFECT OF THE INVENTION The novel amide compound (1) of the present invention provides a pleasant feeling with low irritation to the skin and hair, has excellent foaming power and emulsion stability, and is suitable for various detergents and cosmetics. And the like, and is useful as an emulsifier, a conditioning agent, and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07C 231/02 C07C 231/02 303/22 303/22 303/24 303/24 305/04 7419- 4H 305/04 309/15 7419-4H 309/15 C11D 1/52 C11D 1/52

Claims (3)

[Claims] 1. The following general formula (1): [In the formula, two Rs are the same or different and each represents a linear or branched alkyl group or alkenyl group having 1 to 24 carbon atoms which may be substituted with a hydroxyl group, and A is a hydroxyl group or a carboxyl group. Represents a linear or branched alkylene group having 1 to 6 carbon atoms which may be substituted by a group, and B represents a linear or branched alkylene group having 2 to 6 carbon atoms which may be substituted by a hydroxyl group. And Y represents a carboxyl group, a sulfonic acid group, a sulfuric ester group or a salt thereof. ] The amide compound represented by these. 2. In the general formula (1), each of two R's is a linear or branched alkyl group having 6 to 18 carbon atoms,
And A has 1 carbon atom which may be substituted with a hydroxyl group
The amide compound or a salt thereof according to claim 1, which is an alkylene group of 3 to 3. 3. The following general formula (2): [In the formula, A represents a linear or branched alkylene group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group or a carboxyl group, and B is a linear or branched group which may be substituted with a hydroxyl group. An alkylene group having 2 to 6 carbon atoms is shown, and Y'is a carboxyl group, a sulfonic acid group, a sulfuric ester group, an alkoxycarbonyl group, a nitrile group or a hydroxyl group. ] And an amino compound represented by the following general formula (3): [In the formula, R represents a linear or branched alkyl or alkenyl group having 1 to 24 carbon atoms which may be substituted with a hydroxyl group, and X represents a halogen atom, a hydroxyl group, or a linear or branched chain. An alkoxyl group having 1 to 3 carbon atoms is shown. ] One or two kinds of acyl compounds represented by the following are reacted, and when Y'is an alkoxycarboxyl group or a nitrile group, it is hydrolyzed in the presence of a basic catalyst,
The method for producing an amide compound according to claim 1 or 2, wherein when Y'is a hydroxyl group, a sulfuric acid esterifying agent is reacted.