RU2540868C1 - Method for production of tetrahydrofurfurylamides of vegetable oil fatty acids - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to the field of organic chemistry and surfactant chemistry, namely, to a method of production of new heterocyclic amides displaying foam stabiliser properties which may be used as part of detergent compositions. The method for production of tetrahydrofurfurylamides of vegetable oil fatty acids involves production of fatty acid amides through immediate interaction of natural triglycerides (those of sunflower, soya, palm kernel and coconut oil) with amine in the presence of an alkaline catalyst represented by sodium hydroxide in an amount of 0.2 wt % of the reaction mixture; the reaction mixture is maintained at 130°C for 3 hours with further washing with a saturated solution of sodium chloride; in the reaction with triglycerides tetrahydrofurfurylamine is used; the reaction proceeds with the stoichiometric proportion of the initial reagents oil:amine is 1:3; the alkaline catalyst is introduced after the reaction mixture has been heated to 100°C.

EFFECT: production of tetrahydrofurfurylamides with formula

, where R - radicals of vegetable oil fatty acids (C8-C22) possessing a foam stimulation action with usage of a stoichiometric amount of the reagents.

4 ex, 1 dwg

Description

The invention relates to the field of organic chemistry and chemistry of surfactants, and in particular to a method for producing new heterocyclic amides exhibiting the properties of foam stabilizers, which can be used as components of detergent compositions.

Fatty acid amides possess the properties of blowing agents, defoamers, etc., which allows their use in various industries, from cosmetic to construction (Synthesis and characterization of the monoethanolamide from palm oil / D. Dzylkefly [et al.] // J. Elaeis. - 1997. - Vol. 9, No. 2. - P. 61-68. Kolancilar H. Preparation of Laurel Oil Alkanolamide from Laurel Oil / H. Kolancilar // J. Am. Oil Chem. Soc. - 2004 . - Vol.81, No. 6. - P.597-598). Higher fatty acid alkanolamides are widely used as nonionic surfactants in liquid detergents, personal care products as foam stabilizers, paint dispersants, thickeners, and solubilizers. In the metalworking industry, these surfactants are used as lubricants, viscosity control agents, corrosion inhibitors, etc. The introduction of a heterocyclic fragment into the amide molecule allows us to expand the range of practically useful properties.

The tetrahydrofurfuryl cycle is a part of compounds with various properties, including antibacterial (Design and synthesis of some azole derivatives as potential antimicrobial agents / D. Sahin [et al.] // Med. Chem. Res. - 2012. - V.21 .- P.4485-4498). This cycle is also a structural fragment of natural compounds (Synthesis of functionalized bisphosphonates via click chemistry / H. Skarpos [et al.] // Org. And bioorg. Chem. - 2007. - V.5. - P.2361-2367).

Currently known methods for producing fatty acid amides, both individual and mixtures containing residues of carboxylic acids that are part of vegetable and animal fats. Most often, mono- and diethanolamines are introduced into such transformations. Alkanolamides are obtained by direct interaction of fatty acids with amines [JPH 08301827, IPC C07C 231/02; C07C 233/18; C07C 233/20, publ. 1996.11.19]. The disadvantages of this method are the synthesis at high temperatures and the complexity of the process. Acid esters can also act as an acylating agent [CN 10267213 8, RU 2415125, IPC C07C 43/13, C07C 41/16, C07C 41/40, C11B 11/00, publ. 03/27/2011]. Thus, derivatives of saturated and unsaturated fatty carboxylic acids with different hydrocarbon radical lengths are obtained. The disadvantages of these methods include carrying out an additional stage of obtaining fatty acid esters from triglycerides, carrying out reactions at elevated pressure.

The closest is the method of producing alkanolamides of higher carboxylic acids of animal fats, described by the authors of patent RU 2070878 [IPC C07C 233/18, C07C 231/02, publ. 12/27/1996]. A method of producing fatty acid monoethanolamides by saponification of a fatty acid ester with monoethanolamine when heated in the presence of alkali, characterized in that animal fat is used as a fatty acid ester, anhydrous sodium hydroxide and saponification are used in an animal fat: monoethanolamine mass ratio of 4: 1, a temperature of 120-140 ° C for 1 h, followed by the addition of caustic soda taken in an amount of 0.2-0.5% wt. from the reaction mass, and keeping the mixture for 30 minutes

The disadvantages of this method include the presence of free amine and glycerol impurities in the obtained alkanolamides (about 10%).

An object of the present invention is to provide a method for producing higher fatty acid amides having a foam stabilizing effect and not containing amine and glycerol impurities without using an excess amount of amine.

The technical result consists in obtaining tetrahydrofurfurylamides of the formula

where R is the residues of fatty acids (C8-C22) of vegetable oils with a foam-stabilizing effect when using a stoichiometric amount of reagents.

The technical result is achieved by the fact that in the method for producing tetrahydrofurfurilamides of fatty acids of vegetable oils, including the production of fatty acid amides directly by the interaction of natural triglycerides (sunflower, soybean, palm kernel and coconut oil) with an amine in the presence of an alkaline catalyst of sodium hydroxide in an amount of 0.2% by weight . the reaction mixture, keeping the reaction mass at 130 ° C for 3 hours, subsequent washing with a saturated solution of sodium chloride, according to the invention, tetrahydrofurfurylamine is used in the reaction with triglycerides; the reaction is carried out with stoichiometric amounts of the starting reagents oil: amine = 1: 3; the alkaline catalyst is introduced after heating the reaction mixture to 100 ° C.

Figure 1 shows a table of the results of foaming ability.

Fatty acid tetrahydrofurfurylamides of vegetable oils are formed as a result of the reaction of vegetable oil with tetrahydrofurfurylamine. The maximum conversion of the starting reagents is achieved by carrying out the reaction at 130 ° C for 3 hours in the presence of 0.2% of the mass. sodium hydroxide. Purification of the reaction products consists in washing the reaction products with a saturated solution of sodium chloride.

Below are examples of the implementation of the invention.

EXAMPLE 1

The synthesis of tetrahydrofurfurylamides containing residues of fatty acids of sunflower oil I proceeds according to the following scheme:

where R is the hydrocarbon fragments of fatty acids (C16-C22) of sunflower oil.

292 g of sunflower oil and 93 ml of tetrahydrofurfurylamine were placed in a three-necked round-bottom flask equipped with an overhead stirrer with a shutter, a reflux condenser and a thermometer. Heated to 100 ° C (heating rate of 1.3-1.4 ° C per minute) and 0.79 g of sodium hydroxide was added. The reaction mass was slowly heated to 130 ° C and kept at this temperature for 3 hours. The resulting sunflower oil fatty acid tetrahydrofurfurilamides were washed with saturated sodium chloride solution, filtered and dried. Yield 61%, mp = 42-44 ° C.

EXAMPLE 2

The synthesis of tetrahydrofurfurylamides containing soybean oil fatty acid residues is carried out according to the method described in Example 1, where R is the hydrocarbon moieties of the soybean oil fatty acids (C8-C18). The mass of soybean oil introduced into the interaction is 280 g. Yield 58%, mp = 40-42 ° C.

EXAMPLE 3

The synthesis of tetrahydrofurfurylamides containing residues of palm kernel oil fatty acids is carried out according to the method described in example 1, where R is the hydrocarbon fragments of palm kernel oil fatty acids (C8-C18). The mass of palm kernel oil introduced into the interaction is 245 g. Yield 64%, mp = 42-44 ° C.

EXAMPLE 4

The synthesis of tetrahydrofurfurylamides containing residues of coconut oil fatty acids is carried out according to the method described in example 1, where R is the hydrocarbon fragments of fatty acids (C6-C18) of coconut oil. The mass of coconut oil introduced into the interaction is 226 g. Yield 70%, mp = 46-48 ° C.

The foam-stabilizing ability of mixtures of fatty acid tetrahydrofurfurilamides of vegetable oils I was studied (Fig. 1). It was found that, regardless of the characteristics of the fatty acid composition (hydrocarbon radical length, degree of unsaturation of fatty acid residues), compounds I have a foam-stabilizing effect. We studied the foam-stabilizing effect on the example of the stability of the foam of a commercial foaming agent, cocoamidopropyl betaine with different amounts of tetrahydrofurfurylamides. It was found that even with the addition of 1% tetrahydrofurfurilamide by weight of cocobetaine, the foam-stabilizing effect of tetrahydrofurfurlamide is manifested.

Claims (1)

The method of obtaining tetrahydrofurfurylamides of vegetable oil fatty acids, including the production of fatty acid amides directly in the interaction of natural triglycerides (sunflower, soybean, palm kernel and coconut oil) with an amine in the presence of an alkaline catalyst of sodium hydroxide in an amount of 0.2 wt.% Of the reaction mixture, maintaining the reaction mass at 130 ° C for 3 hours, subsequent washing with a saturated solution of sodium chloride, characterized in that tetrahydrofurf is used in the reaction with triglycerides rilamin; the reaction is carried out with stoichiometric amounts of the starting reagents oil: amine = 1: 3; the alkaline catalyst is introduced after heating the reaction mixture to 100 ° C.

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