PL192142B1 - Novel surface-acting aldonamidoamines and method of obtaining them - Google Patents

Abstract

1. New surfactants of aldonamidoamines named N-alkyl-N, N-bis [3- (aldonamido) propyl] amine and general formula 1, in which R is straight or branched, saturated or an unsaturated hydrocarbon chain containing from 8 to 20 carbon atoms, preferably from 12 to 18 carbon atoms, while X represents a sugar residue, preferably a D-glucone represented by the formula 2, D-glucohepton represented by formula 3, lactobion represented by pattern 4 and maltobion depicted pattern 5.

Description

The invention relates to new, surfactant aldonamidoamines named N-alkyl-N, N-bis [3- (aldonamido) propyl] amines and the general formula I, in which R is a straight or branched, saturated or unsaturated hydrocarbon chain containing from 8 to 20 carbon atoms, preferably from 12 to 18 carbon atoms, and X is a monosugar or disaccharide residue, preferably a D-gluconate represented by the formula 2, D-glucohepton represented by the formula 3, lactobionic represented by the formula 4 and maltobionic represented by the formula 5.

The invention also relates to a process for the preparation of the said compounds.

The new surfactants of aldonamidoamines show surface activity at interfaces, which allows them to be used as surface-active ingredients in washing, washing, cleaning, wetting, solubilizing, foaming, antifoaming, emulsifying and dispersing agents, alone or in mixtures and mixtures with other surfactants. anionic, cationic, amphoteric and non-ionic, in household chemicals and cosmetics, as well as in auxiliary agents for the textile and metal industry, metal ore processing, in lubricating oils and greases, etc.

For the production of new generations of surfactants, characterized by low environmental impact and human-friendly physiological properties, a renewable resource base is increasingly used. In addition to the long-used oleochemicals obtained from vegetable and animal fats, simple sugars and oligosaccharides began to be used, which gave rise to a group of so-called "sugar surfactants". The oldest representatives of these are sucrose and sorbitan esters. According to the literature reports: K. Kosswig, H. Stache (Eds), Die Tenside, Carl Hanser Verlag, Miinchen, 1993, the synthesis of such esters is non-selective and leads to a multi-component mixture of products, which usually worsens their properties. The recently introduced alkyl polyglucosides (WvRybinski, K. Hill, in: Novel Surfactants, K. Holmberg, Ed., Marcel Dekker Inc., New York, 1998) are a complex mixture of compounds, differing in the length of the alkyl chain and the degree of oligomerization of residues sugar. The processes of their synthesis pose a number of difficulties related to both the chemistry of the glycosidation reaction of simple sugars and the technical implementation of this process. There are reports of a new group of sugar surfactants in the patent and scientific literature in which the hydrophobic fragment, represented by a sufficiently long hydrocarbon chain, is linked through an amide group with the hydrophilic fragment, which is a sugar unit. These compounds are obtained by reacting amines with aldonolactones or aldonic acids, and the latter are obtained by oxidation of the aldehyde group of a simple sugar belonging to aldoses. Such selection of substrates allows for obtaining products with a defined molecular structure, as the reaction is selective and does not require the protection of free hydroxyl groups of the sugar molecule. There are many reports in the patent literature claiming structures and methods for the preparation of such amides. The most commonly used hydrophobic intermediates are primary amines (e.g. U.S. Patent No. 2,752,334, French Patent No. FR 2,523,962), or secondary amines containing two of the same or two different hydrocarbon chains in the molecule (e.g. European Patent No. EP 0550278, German DE 4406160).

The synthesis of aldonamides by the reaction of δ-D-gluconolactone or gluconic and lactobionic acids with α, ω-diamines has also been described (French patent application No. FR 2683223), as a result of which surfactants from the group of bolaamprophilic compounds containing sugar hydrophilic groups at the ends of the hydrophobic chain were obtained. Surfactants were also obtained by reacting aldonolactones with mono- and dialkyl diamines with a structure different than α, ω-diamines (e.g. US patent No. 4,892,806; publication: T.Kida, K.Isokawa, N.Morishima, W.Zhang, A.Masuyama , Y.Nakatsuji, I.Ikeda, Nihon Yukagakkaishi, 1998, 47, 41), obtaining surfactants containing two sugar moieties and one or two alkyl chains per molecule.

It has surprisingly been found that N-alkyl-N, N-bis (3-aminopropyl) amines are preferred intermediates suitable for the synthesis of sugar surfactants with aldonamide moieties. Such tertiary amines contain two primary amine groups capable of reacting with aldonolactones or aldonic acids.

The invention relates to new surfactant aldonamidoamines named N-alkyl-N, N-bis [3- (aldonamido) propyl] amine and the general formula I, wherein R is a straight or branched, saturated or unsaturated hydrocarbon chain containing from 8 to 20 atoms. carbon, preferably

PL 192 142B1 has 12 to 18 carbon atoms, and X is a monosugar or disaccharide residue: D-glucone of formula 2, D-glucohepton of formula 3, lactobionic of formula 4 or maltobion of formula 5.

The invention also relates to a process for the preparation of N-alkyl-N, N-bis [3- (aldonamido) propyl] amines of general formula I, in which R is a straight or branched, saturated or unsaturated hydrocarbon chain containing from 8 to 20 carbon atoms, and X represents a sugar residue given by formulas 2, 3, 4 or 5.

The essence of the invention is that N-alkyl-N, N-bis (3-aminopropyl) amines of the general formula 6, in which R is a straight or branched, saturated or unsaturated hydrocarbon chain containing from 8 to 20 carbon atoms, preferably from 12 to 18 carbon atoms, in a polar solvent medium, preferably methanol or ethanol, at room or elevated temperature, but not exceeding the boiling point of the solvents used, are reacted with aldonolactones, preferably with δ-D-gluconolactone or D-glucoheptone-Y -lactone, or with aldonic acids, preferably lactobionic acid or maltobionic acid, for a period not exceeding 24 hours, after which the reaction mixture is cooled to the temperature necessary to crystallize the formed N-alkyl-N, N-bis [3- (aldonamido) propyl] amines, which, after filtering, are optionally purified by generally accepted methods.

The main advantages of the invention lie in the use of tertiary amines having one long hydrocarbon chain and two free, primary amino groups for the synthesis of surfactant aldonamidoamines, thanks to which the surfactants obtained contain two or four sugar units in the molecule, which significantly increases the solubility of these aldonamides in water and eliminates the need to subject the alkylaldonamides to further reactions such as the ethoxylation of French Patent No. FR 2,523,962 or the sulfation of US Patent No. 5,312,934 to improve their solubility. Alkylaldonamides, like alkyl polyglucosides, are readily biodegradable in the environment. Moreover, numerous reports, including: I. Ricco-Lattes, A. Lattes, Colloids Surfaces A, 1997, 123-124, 37, show that amphiphilic compounds from the aldonamide group may find potential applications in drug formulations as antibacterial agents. and antiviral as well as in extractive processes of secreting proteins from cell membranes. The synthesis of the aldonamidoamines according to the invention takes place under mild conditions and the product yields are high.

The subject of the invention is explained in the examples of preparation of the new N-alkyl-N, N-bis [3- (aldonamido) propyl] amine surfactants of tertiary N-alkyl-N, N-bis (3-aminopropyl) amines and in the figure wherein Scheme 1 shows the reaction of the amines of Formula 6 with an aldonolactone and Scheme 2 shows the reaction of the amines of Formula 6 with aldonic acids.

Example 1 50 ml of ethanol, 0.45x10 ^-2 kg (0.015 mol) of N-dodecyl-N, N-bis (3-aminopropyl) amine represented by the formula 6, in which R is a dodecyl chain, are introduced into the reactor and 0,55x10 ^-2 kg (0.031 mol) of δ-gluconolactone and the contents stirred for 24 hours at room temperature. Then the contents of the reactor are cooled to the temperature of + 5 ° C until the product is completely crystallized. The product was filtered off, washed with ethanol cooled to -15 ° C and dried at 20 mm Hg over solid KOH. After crystallization from ethanol, the yield of N-dodecyl-N, N-bis [3- (gluconamido) propyl] amine is obtained with the structure shown in formula 1, in which R is a dodecyl chain and X is a glucone residue in the formula 2. Summary formula C30H61N3O12, molecular weight = 655.8 gmol ^-1 ; C, H, N content calculated respectively: 54.94; 9.37; 6.40; appointed, respectively: 55.00; 9.48; 6.42; melting point = 167.4170.3 ° C; Krafft point = 47.7 ° C; surface tension of 0.1% aqueous solution made of distilled water = 39.5 mNm ^-1 .

Example II. 50 ml of methanol, 0.45 x 10 ^-2 kg (0.015 mol) of N-dodecyl-N, N-bis (3-aminopropyl) amine represented by the formula 6, in which R is the dodecyl chain and 0.64 x 10 ^-2 kg, are introduced into the reactor. (0.03 mol) D-glucoheptono-Y-lactone and the mixture was stirred for 24 hours at room temperature. Then the procedure is as in Example I. The product is obtained with a yield of 87%, the structure shown in the formula 1, in which R represents the dodecyl chain and X represents the glucohepton residue in the formula 3. Summary formula C32H65N3O14; molecular weight = 715.9 gmol ^-1 ; C, H, N content calculated respectively: 53.68; 9.15; 5.86; designated, respectively: 53.58; 8.99; 6.00; melting point = 167-170.0 ° C; Krafft point = 65.6 ° C; surface tension of 0.1% aqueous solution made of distilled water = 38, mNm ^-1 .

Example III. Introduced into the reactor 50 ml of methanol, 0,30x10 ^-2 kg (0.01 mol) of N-dodecyl-N, N-bis (3-aminopropyl) amine represented by the formula 6, wherein R is a chain dode4

GB-tetradecyl 192 142B1 and 0,72x10 ^-2 kg (0.02 mol) of lactobionic acid and the contents stirred at room temperature for 24 hours. Then the reaction mixture is cooled to -20 ° C, until the product crystallizes, 50 ml of ethanol are added and the whole is kept at this temperature for 24 hours, then the solid product is filtered off, washed with ethanol cooled to -15 ° C and dried under pressure. mm Hg. This product, obtained with a yield of 75%, is crystallized twice from a mixture of methanol and acetonitrile. The structure of the compound is represented by the formula 1, where R is the dodecyl chain and X is the formula 4 with the lactobion residue. Summary formula C42H81N3O22; molecular weight = 980.1 gmol ^-1 ; C, H, N content calculated respectively: 51.47; 8.33; 4.28; designated, respectively: 51.55; 8.40; 4.32; fuzzy melting point due to phase transitions with increasing temperature; Krafft point < 0 ° C; surface tension of 0.1% aqueous solution made from distilled water = 38.5 mNm ^-1 .

Example IV. 100 ml of methanol, 0.335 × 10 ^-2 kg (0.01 mol) of N-hexadecyl N, N-bis (3-aminopropyl) amine represented by the formula 6, in which R is a hexadecyl chain and 0.72 × 10, are introduced into the reactor. ^-2 kg (0.02 mol) of lactobionic acid and the contents are stirred for 19 hours at room temperature. The temperature is then raised to 50-55 ° C and the reaction mixture is kept for 8 hours, after which it is cooled first to room temperature and then to + 5 ° C. A solid precipitates, which is filtered off, washed with methanol cooled to -15 ° C, and dried at 20 mm Hg, yielding 69%. This product is recrystallized from a mixture of methanol and acetonitrile; the structure of the compound is represented by formula 1, where R is a hexadecyl chain, and X is represented by formula 4, a lactobion residue. Summary formula C46H89N3O22; molecular weight = 1036.2 gmol ^-1 ; C, H, N content calculated respectively: 53.31; 8.65; 4.05; determined, respectively: 53.87; 8.92; 4.15; fuzzy melting point due to the occurring phase transitions with increasing temperature; Krafft point < 0 ° C; surface tension of 0.1% aqueous solution made of distilled water = 36.5 mNm ^-1 .

EXAMPLE V To a reactor is charged with 100 ml of methanol, 0,383x1 0 ^-2 kg (0.01 mol) of N-octadecyl-N, N-bis (3-aminopropyl) amine represented by the formula 6, wherein R is octadecyl chain and 0, 72x10 ^-2 kg (0.02 mol) of lactobionic acid. Then the procedure of Example IV is followed and the product is obtained with a yield of 84%. Its structure is shown in formula 1, where R denotes the octadecyl chain and X represents the lactobion residue in formula 4. Summary formula

C48H93N3O22; molecular weight = 1064.3 gmol ^-1 ; C, H, N content calculated as: 54.16; 8.80; 3.94; designated, respectively: 54.25; 8.90; 3.90; fuzzy melting point due to the occurring phase transitions with increasing temperature; Krafft point < 0 ° C; surface tension of 0.1% aqueous solution made of distilled water = 36.7 = mNm ^-1 .

Claims (3)

1. New surfactants of aldonamidoamines named N-alkyl-N, N-bis [3- (aldonamido) propyl] amines and general formula 1, in which R is a straight or branched, saturated or unsaturated hydrocarbon chain containing from 8 to 20 atoms carbon, preferably from 12 to 18 carbon atoms, and X is a sugar residue, preferably D-glucone represented by formula 2, D-glucoheptonic represented by formula 3, lactobionic represented by formula 4 and maltobionic represented by formula 5. 2. A method for the preparation of new, surfactant aldonamidoamines named N-alkyl-N, N-bis [3- (aldonamido) propyl] amine and general formula 1, in which R is a straight or branched, saturated or unsaturated hydrocarbon chain containing from 8 up to 20 carbon atoms, preferably from 12 to 18 carbon atoms, while X is a monosaccharide or disaccharide residue represented by formulas 2, 3, 4 or 5, characterized by reacting N-alkyl-N, N-bis (3 -aminopropyl) amines of the general formula 6, in which R is as defined above, in an environment of a polar solvent, preferably methanol or ethanol, at room temperature or elevated but not exceeding the boiling point of the solvents used, with aldonolactones, preferably with a δ-D-gluconolactone or D-glucoheptono-Y-lactone, where the molar ratio of amine to aldonolactone ranges from 1: 1 to 1: 1.2 for a time not exceeding 24 hours, after which the reaction mixture is cooled to a temperature not not necessary for the crystallization of the formed N-alkyl-N, N, -bis [3- (aldonamido) propyl] amine surfactants, which, after filtration, are purified, if necessary, by generally accepted methods. PL 192 142 B1 3. A method for the preparation of new, surfactant aldonamidoamines named N-alkyl-N, N-bis [3- (aldonamido) propyl] amine and the general formula I, in which R is a straight or branched, saturated or unsaturated hydrocarbon chain containing from 8 to 20 carbon atoms, preferably from 12 to 18 carbon atoms, and X is a monosaccharide or disaccharide residue represented by formulas 2, 3, 4 or 5, characterized by reacting N-alkyl-N, N-bis [3 - (aminopropyl) amine of the general formula 6, in which R is as defined above, in a polar solvent medium, preferably methanol or ethanol, at room temperature or elevated temperature, but not exceeding the boiling point of the solvents used, with lactobionic or maltobionic acid, the molar ratio of amine to aldonic acid ranges from 1: 1 to 1: 1.2 for a time not exceeding 24 hours, after which the reaction mixture is cooled to the temperature necessary for crystallization to form of N-alkyl-N, N, -bis [3- (aldonamido) propyl] amine surfactants, which, after filtration, are purified, if necessary, by generally accepted methods.