JP2000053625A - New amide compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound excellent in biodegradability. SOLUTION: This compound is shown by formula I [(m) is 2-10; (n+1) is 8-20; X is at least one of H ion, monovalent and divalent alkali metal ions, alkaline earth metal ions, ammonium ion and organic ammonium ions, e.g. a diacylated product of [S, S] ethylenediaminedisuccinic acid. The compound of formula I is obtained, as a compound of formula III when X=H, by adding to and dissolving in a mixed solvent of water and acetone a diamine of formula II and sodium hydroxide at four equivalent times the diamine, adding an acid chloride at two equivalent times to the diamine dropwise under stirring at 10-60 deg.C for reaction. The compound of formula I is significantly excellent in biodegradability and can be used e.g. as one of various cleansing agents for the skin, hair, tableware, clothing items and so on and as an emulsifier for cosmetics for the skin and hair. In these cases, this compound is pref. compounded at 0.1-80 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel amide compound having excellent biodegradability.

[0002]

2. Description of the Related Art Various anionic surfactants useful as detergents, emulsifiers and conditioning agents have hitherto been known. In recent years, multi-chain and multi-hydrophilic group-containing anionic surfactants have attracted attention due to their excellent surface activity. But,
As a matter of fact, there is still no biodegradable material that is satisfactory in terms of environmental protection, and improvement has been desired.

[0003]

An object of the present invention is to provide a novel amide compound having excellent biodegradability.

[0004]

The present inventors have SUMMARY OF THE INVENTION As a result of intensive research in view of the above circumstances, found significantly superior thing below certain novel amide compounds biodegradability, the present invention has been completed.

That is, claim 1 of the present invention is a general formula

[0006]

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(Where m is 2 to 10 and n + 1 is 8 to 2)
0 and X are novel amide compounds represented by one or more of hydrogen ion, monovalent or divalent alkali metal ion, alkaline earth metal ion, ammonium ion and organic ammonium ion).

[0008]

Next, an embodiment of the present invention will be described. The novel amide compound of the present invention can be obtained, for example, according to the reaction scheme of Chemical formula 3.

[0009]

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That is, a mixed solvent of water and acetone (6:
(4, volume ratio), a raw material diamine ([S, S] ethylenediaminedisuccinic acid) and 4 times equivalent of sodium hydroxide are added and dissolved. Thereafter, at 10 to 60 ° C., acid chloride in an amount equivalent to twice the amount of the diamine is gradually added dropwise with stirring. At this time, the pH of the system is kept alkaline by adding sodium hydroxide dropwise. After completion of the dropwise addition of the acid chloride, stirring is continued at room temperature for several hours to complete the reaction. Then, the system p
The precipitate formed with H as 1 is filtered, washed with water and dried. The reaction product is recrystallized using a mixed solvent of benzene / acetone. Thus, a diacylated [S, S] ethylenediaminedisuccinic acid was obtained. The method for synthesizing [S, S] ethylenediaminedisuccinic acid is described in Chem. Zvesti, 20
(6): 414-422 (1966).

Further, [S, S] ethylenediaminedisuccinic acid tetramethyl ester is used in place of [S, S] ethylenediaminedisuccinic acid in a mixed solvent of water and diethyl ether (6: 4, volume ratio). After the reaction with acid chloride by the method described above, the pH is adjusted to 1 with hydrochloric acid and the mixture is allowed to stand to separate a diethyl ether layer. After washing with water, it is dried over anhydrous potassium carbonate. The diethyl ether is removed under reduced pressure, and the mixture is stirred at 90 ° C. for 3 hours in an aqueous sodium hydroxide solution equivalent to 4 times the equivalent of the obtained [S, S] ethylenediaminedisuccinic acid tetramethyl ester diacylate. Then, at room temperature,
After adjusting the pH to 1 with hydrochloric acid, the mixture was allowed to cool and the precipitated crystal was filtered to obtain a diacylated [S, S] ethylenediaminedisuccinic acid.

The connecting group of the novel amide compound of the present invention is a polymethylene chain having 2 to 10 carbon atoms. From the viewpoint of surface activity, the linking group is preferably an ethylene chain having 2 carbon atoms. As the hydrophobic group, one having 8 to 20 carbon atoms (n + 1) is applied, and for the purpose of washing, 12 or 14 is preferable, and a linear or branched one is selected depending on the use.
The counter ion is appropriately selected from one or more of a hydrogen ion, a monovalent or divalent alkali metal ion, an alkaline earth metal ion, an ammonium ion and an organic ammonium ion.

The novel amide compound of the present invention is remarkably excellent in biodegradability. Further, the amide compound of the present invention can adjust the neutralization rate, for example, when neutralizing only two carboxyls at the α-position with respect to an asymmetric carbon, a normal two-chain two-hydrophilic group-containing negative surfactant. Expresses the same surface activity. Therefore, it can be used as various cleaning agents for skin, hair, tableware, clothing, etc., emulsifiers for skin and hair cosmetics, conditioning agents and the like. The blending amount in this case is not particularly limited, and may be 0.1 to 8 depending on the use or the like.
It can be used in an amount of 0% by weight, preferably 1 to 50% by weight.

When the novel amide compound of the present invention is used for these purposes, various surfactants, humectants, bactericides, viscosity agents, divalent metal ion sequestering agents, inorganic salts, pigments, fragrances, etc., if necessary. The known raw materials for cosmetics can be blended.

[0015]

The present invention will be described below with reference to examples.

Example 1 (Production of diacylated [S, S] ethylenediaminedisuccinic acid (C12)) [S, S] ethylenediaminedisuccinic acid 29.0 g
(0.11 mol) was added to 500 ml of a mixed solvent of water / acetone (4: 6), and then 17.6 g (0.44 mol) of sodium hydroxide dissolved in 100 ml of water was added and stirred [S, S] Dissolve ethylenediaminedisuccinic acid. 95.9 g (0.44 mol) of dodecanoyl chloride are added dropwise with stirring. At this time, the pH of the system is kept alkaline by adding sodium hydroxide dropwise. After the completion of the dropwise addition of the acyl chloride, the stirring is continued at room temperature for several hours to complete the reaction. Thereafter, the precipitate formed with hydrochloric acid at a pH of 1 was filtered and washed with water. dry. The reaction product is recrystallized using a mixed solvent of benzene / acetone. The results of elemental analysis of the purified product were as follows. Carbon: 62.15 (6
2.17), hydrogen 9.20 (9.21), nitrogen 4.26
(4.27). The values in parentheses are theoretical values.

Example 2 (Production of diacylated [S, S] ethylenediaminedisuccinic acid (C12)) Tetramethyl (S, S) ethylenediaminedisuccinic acid (200 ml) in water / diethyl ether (1: 1) 0.01 mol) and sodium hydroxide (0.04
Mol), and lauric chloride (0.02 mol) was added dropwise at room temperature with stirring. Thereafter, the mixture was stirred for 1 hour. The pH was adjusted to acidic with hydrochloric acid and allowed to stand. The ether layer was separated and the solvent was removed by an evaporator. The obtained residue was purified by column chromatography using silica gel as the stationary phase and chloroform as the mobile phase to obtain a purified product. The amidated (S, S) ethylenediaminedisuccinic acid tetramethyl ester (0.1 mol) and sodium hydroxide (0.4 mol) were added to 200 ml of water, and the mixture was stirred at 80 ° C. for 3 hours. Thereafter, the pH was adjusted to 1 with hydrochloric acid, and the mixture was cooled. The resulting precipitate was filtered and dissolved with heating using a mixed solvent of tetrahydrofuran and water. After standing, the resulting precipitate was filtered. The obtained amorphous crystals were further recrystallized under the same conditions. After drying, the molecular structure of the diacylated [S, S] ethylenediaminedisuccinic acid (C12) was confirmed by the elemental analysis results. The numbers in parentheses are theoretical values. Carbon: 62.15% (62.17%), hydrogen: 9.10
(9.21%), nitrogen: 4.10 (4.27%). still,
In the infrared absorption spectrum, the amide carbonyl and α,
The carboxycarbonyl at the β-position is 1608.8 cm ⁻¹ , 1
It was observed at 743.9 cm ^-1 and 1718.8 cm ^-1 , respectively.

Reference Example 1 (Production of diacylated [R, R] ethylenediaminedisuccinic acid (C12)) In place of [S, S] ethylenediaminedisuccinic acid used in Example 2, [R, R] ethylenediamine An acylated product of [R, R] ethylenediaminedisuccinic acid (C12) was obtained by the same operation except that disuccinic acid was used.

Reference Example 2 (Production of diacylated [S, R] ethylenediaminedisuccinic acid (C12)) Instead of [S, S] ethylenediaminedisuccinic acid used in Example 2, [S, R] ethylenediamine A diacylated [S, R] ethylenediaminedisuccinic acid (C12) was obtained by the same operation except that disuccinic acid was used.

[S, S] Diacylated ethylenediaminedisuccinic acid (C12), [R, R] Diacylated ethylenediaminedisuccinic acid (C12), [S, R] Diacylated ethylenediaminedisuccinic acid (C12) About biodegradability test (JIS biodegradability test method K-336)
3 method). As a result, diacylated [S, S] ethylenediaminedisuccinic acid (C12), diacylated [R, R] ethylenediaminedisuccinic acid (C12),
The biodegradation rates of the diacylated [S, R] ethylenediaminedisuccinic acid (C12) are 99.5% and 74.
2% and 45.8%. From these results, the biodegradability of the diacylated product of ethylenediaminedisuccinic acid was [S,
[S] isomer is found to be specific.

Example 2 (Production of acylated product of [S, S] propylenediaminedisuccinic acid (C12)) Instead of [S, S] ethylenediaminedisuccinic acid used in Example 2, [S, S] An acylated product of [S, S] propylenediaminedisuccinic acid (C12) was obtained in the same operation except that propylenediaminedisuccinic acid was used.
The results of elemental analysis of the purified product were as follows. Carbon: 6
2.67 (62.66), hydrogen 9.30 (9.32),
Nitrogen 4.17 (4.18). The values in parentheses are theoretical values. The biodegradation rate of this compound was 98.8%. These two-chain two-hydrophilic group-containing anionic surfactants having excellent biodegradability do not yet exist except for the amide compound of the present invention.

Formulation Example 1 A shampoo having the following composition was prepared using the compound of the present invention. The compounding amount is% by weight. (Composition) 2Na salt of the compound of Example 2 15.8 Lauroyldiethanolamide 2.5 Lauryldimethylamine oxide 0.5 Hydroxymethylcellulose 0.1 Sodium benzoate 0.2 Dye qs Citric acid qs Flavor qs Water balance

The shampoo of Formulation Example 1 was excellent in foaming properties and detergency.

Formulation Example 2 A shampoo having the following composition was prepared. (Composition) In JP-A-9-2931, 2Na salt of a two-hydrophobic group-two hydrophilic group type anionic surfactant represented by the general formula (B) (provided that R2CO is lauroyl, amino acid is glutamic acid, and X2 is ethylene) Group) 15.8 lauroyldiethanolamide 2.5 lauryldimethylamine oxide 0.5 hydroxymethylcellulose 0.1 sodium benzoate 0.2 dye proper amount citric acid proper amount perfume proper amount water residue

The shampoo of Formulation Example 1 was superior to the shampoo of Formulation Example 2 in foaming properties, detergency, and feel after washing.

[0026]

As described above, it is apparent that the present invention provides a novel amide compound having excellent biodegradability.

Claims (1)

[Claims] 1. A compound of the general formula (Wherein m is 2 to 10, n + 1 is 8 to 20, X is one or more of hydrogen ion, monovalent or divalent alkali metal ion, alkaline earth metal ion, ammonium ion or organic ammonium ion) The novel amide compound represented by the formula: