阅读说明：本技术 双酰胺基有机凝胶因子及其制备方法 (Bisamide-based organogelator and preparation method thereof ) 是由 袁霖 李中燕 周耀 邓邵文 于 2019-09-19 设计创作，主要内容包括：本发明公开了一种双酰胺基有机凝胶因子及其制备方法,该化合物可以用于煤油凝胶。本发明解决现有小分子凝胶因子的制备方法复杂,成本高,胶凝时间长以及胶凝过程中需要借助辅助溶剂或其他手段的问题。本发明所提供的具有双酰胺结构的小分子凝胶因子,能够,其最小凝胶浓度MGC值为0.11％w/v。(the invention discloses a bisamide-based organogelator and a preparation method thereof, and the compound can be used for kerosene gel. The invention solves the problems of complex preparation method, high cost, long gelation time and the need of auxiliary solvent or other means in the gelation process of the existing micromolecule gel factor. The small molecule gel factor with the bisamide structure provided by the invention has the advantages that the minimum gel concentration MGC value is 0.11% w/v.)

1. A compound having the structure of formula (I)

Wherein R is¹denotes the Val, Phe, Ile, Leu, Ala group, R²Is represented by C₆-C₁₆linear or branched alkyl.

2. The compound of claim 1, wherein R¹Val, Phe, Ile, Leu, Ala.

3. The compound of claim 1 or 2, wherein R¹represents Phe.

4. The compound of any one of claims 1-3, wherein R²represents-C₁₂H₂₅。

5. A process for the preparation of a compound of formula (I) as claimed in any one of claims 1 to 4, characterized by comprising the following steps:

Step (1):

step (2):

And (3):

Wherein R is¹、R²As defined in any one of claims 1 to 4.

6. The process of claim 5, wherein the reaction of step (1) is carried out in the presence of a condensing agent selected from the group consisting of BOP (benzotriazole-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate), DCC (dicyclohexylcarbodiimide), DIC (diisopropylcarbodiimide), EDC (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide); the alkali is selected from triethylamine and N, N-diisopropylethylamine; the solvent is selected from one or any combination of dichloromethane, DMF, chloroform, methanol, tetrahydrofuran and dioxane.

7. The method of claim 5, wherein the reaction of step (2) is carried out under the catalysis of a solvent, a base, and the solvent is selected from one of dichloromethane, DMF, chloroform, methanol, tetrahydrofuran, dioxane, or any combination thereof; the base catalyst is selected from piperidine, triethylamine and N, N-diisopropylethylamine.

8. The process of claim 5, wherein the reaction of step (3) is carried out in the presence of a condensing agent selected from the group consisting of BOP (benzotriazole-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate), DCC (dicyclohexylcarbodiimide), DIC (diisopropylcarbodiimide), EDC (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide); the alkali is selected from triethylamine and N, N-diisopropylethylamine; the solvent is selected from one or any combination of dichloromethane, DMF, chloroform, methanol, tetrahydrofuran and dioxane.

9. The method of any one of claims 5-8, wherein steps (1) to (3) of the method are performed at room temperature.

10. Use of a compound according to any one of claims 1 to 4 as a kerosene gelator, wherein the compound has a minimum gelling concentration of 0.11% w/v.

Technical Field

The invention belongs to the field of chemical industry, and particularly relates to an organogelator with a bisamide structure and a preparation method thereof.

Background

Gels are soft substances with both solid mechanical strength and liquid fluidity, and recently, gel systems with certain specific performance are receiving more and more attention. The organogelator is assembled into a three-dimensional network or a fiber structure through hydrogen bonds, pi-pi accumulation, van der waals force and other non-covalent bond interaction between molecules to form a cavity, and can gel solvent molecules which are thousands of times of the number of the organogelator. However, the current preparation method of the gelator is complex, high in cost, long in gelling time and limited in further application of the organogel material in practice due to the need of auxiliary solvents and the like. Therefore, it is of great importance to design and develop a gel factor that is low in cost, high in performance, and does not require an auxiliary solvent or means for gelling contaminants.

Chinese patent application with the application number of CN201811573611.X discloses a diureide organic micromolecule gel factor, a preparation method, a thixotropic hydrocarbon fuel gel material and a preparation method.

Application No. CN201810790802.5 discloses a material of gel formed with methyl benzoate, which can realize fast and effective removal of phenol contaminant by adsorption and filtration.

However, the current preparation method of the gel factor is complex, high in cost, long in gelling time and limited in further application of the supramolecular gel material in practice by the aid of auxiliary solvents and the like. Therefore, it is of great importance to design and develop a gel factor that is low in cost, high in performance, and does not require an auxiliary solvent or means for gelling contaminants.

Disclosure of Invention

The invention provides an organic small molecule gelator with a bisamide structure, a preparation method and application of the organic small molecule gelator as a kerosene gelator, and aims to solve the problems that the existing small molecule gelator is complex in preparation method, high in cost, long in gelling time and needs auxiliary solvents or other means in a gelling process. The small molecule gel factor with the bisamide structure provided by the invention has the advantages that the minimum gel concentration MGC value is 0.11% w/v.

The invention provides a compound with a structure of formula (I)

Wherein R is¹Denotes the Val, Phe, Ile, Leu, Ala group, R²Is represented by C₆-C₁₆Linear or branched alkyl.

Preferably, in the compounds of the present invention, R¹Val, Phe, Ile.

More preferably, R in the compounds of the invention¹represents Phe;

Preferably, R in the compounds of the invention²represents-C₁₂H₂₅。

In addition, the present invention provides a process for the preparation of a compound of formula (I), characterized in that it comprises the following steps:

Step (1):

Step (2):

And (3):

in the technical scheme of the invention, the reaction in the step (1) is carried out in the presence of a condensing agent, alkali and a solvent, wherein the condensing agent is selected from BOP (benzotriazole-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate), DCC (dicyclohexylcarbodiimide), DIC (diisopropylcarbodiimide) and EDC (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide); the alkali is selected from triethylamine and N, N-diisopropylethylamine; the solvent is selected from one or any combination of dichloromethane, DMF, chloroform, methanol, tetrahydrofuran and dioxane; wherein said F-Val-OH and R-NH₂The feed ratio of1: 1; the ratio of the condensing agent to the alkali is 1: 2;

In the technical scheme of the invention, the reaction in the step (2) is carried out under the conditions of a solvent and a catalyst, wherein the solvent is selected from one or any combination of dichloromethane, DMF, chloroform, methanol, tetrahydrofuran and dioxane; the catalyst is selected from piperidine, triethylamine and N, N-diisopropylethylamine; wherein the dosage ratio of the F-Val-Alkyl to the catalyst is 1: 2;

In the technical scheme of the invention, the reaction in the step (3) is carried out in the presence of a condensing agent, alkali and a solvent, wherein the condensing agent is selected from BOP (benzotriazole-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate), DCC (dicyclohexylcarbodiimide), DIC (diisopropylcarbodiimide) and EDC (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide); the alkali is selected from triethylamine and N, N-diisopropylethylamine; the solvent is one or any combination of dichloromethane, DMF, chloroform, methanol, tetrahydrofuran and dioxane, N (OH)₂-OH，NH₂-Val-C12 in a ratio of 1: 1; the ratio of the condensing agent to the alkali is 1: 2.

In the technical scheme of the invention, the steps (1) to (3) of the method are carried out at room temperature.

in addition, the invention also provides the application of the compound as a kerosene gelling factor, which is characterized in that the minimum gelation concentration of the compound is 0.11% w/v.

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In order to better illustrate the invention, the following examples are given by way of further illustration.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION