A process for the preparation of dibutyl lauroyl glutamide and uses thereof

Abstract

The application discloses a method for preparing dibutyl lauroyl glutamine and application, wherein long-chain alkyl acyl glycine and acetic anhydride are added into a first reaction container containing cyclohexane, a long-chain alkyl cyclization product is prepared by warming and refluxing reaction; the prepared long-chain alkyl cyclization product is added into a second reaction container containing cyclohexane, an alkaline substance and N-butyl acrylamide are further added for reaction, the alkaline substance and solvent are removed after the reaction, and a long-chain alkyl butylamide propenyl oxazolone is prepared; the prepared long-chain alkyl butylamide propenyl oxazolone is put into a third reaction container containing cyclohexane, n-butylamine is further added into the third reaction container for refluxing reaction, and the solvent is evaporated to prepare long-chain alkyl glutamic acid dibutylamide. The application firstly performs ring-closing reaction, then performs Michael addition on a reserved site of the structure, and ingeniously performs chain extension reaction on the structure, and finally obtains a target compound.

Description

Technical Field

[0001] This invention relates to the field of butyllauroyl glutamine, and particularly to a method for preparing butyllauroyl glutamine and its uses. Background Technology

[0002] In recent years, various small molecule gelling agents have been discovered, among which amide compounds are one. These amide gelling agents form gels through hydrogen bonding of the amide groups. N-lauroyl-L-glutamic acid derivatives are commonly used as amino acid surfactants.

[0003] Currently, there is a method for preparing dibutyllauroyl glutamine on the market. This method involves reacting glutamic acid with lauroyl chloride, followed by an amidation reaction with n-butylamine to obtain the product. This product was developed by Ajinomoto Co., Ltd. of Japan and is used as an oil gelling agent. This reaction requires reagents such as concentrated sulfuric acid and n-butanol. The reaction conditions are relatively harsh, and a large amount of wastewater, waste gas, and waste residue will be generated.

[0004] Other reported methods mostly employ similar approaches, synthesizing lauroylglutamic acid from glutamic acid and then dibutyllauroylglutamic acid, only using different catalysts or solvents.

[0005] To address the above problems, a new technical solution is urgently needed. Summary of the Invention

[0006] To address at least one of the aforementioned technical problems, this invention provides a method for preparing dibutyllauroyl glutamine and its application. This method involves pre-treating the starting material with a cyclization reaction, followed by Michael addition at a reserved site in the structure, cleverly achieving chain extension to ultimately obtain the target compound. Compared to traditional processes, the method described in this invention is simpler and more controllable, yields higher product conversion rates and more stable quality, facilitates the synthesis of products with this type of structure, and is easily scalable for industrial production. The specific scheme is as follows:

[0007] On one hand, the present invention provides a method for preparing dibutyllauroyl glutamine, comprising the following steps:

[0008] S1: Long-chain hydrocarbon acyl glycine and acetic anhydride are added to the first reaction vessel containing cyclohexane, and the reaction is heated to reflux to obtain the long-chain hydrocarbon cyclization product.

[0009] S2: Add the long-chain hydrocarbon cyclization product obtained in step S1 to a second reaction vessel containing cyclohexane, then add an alkaline substance and N-butylacrylamide to the second reaction vessel for reaction. After the reaction is completed, remove the alkaline substance and solvent to prepare the long-chain hydrocarbon butylacrylamide oxazolone.

[0010] S3: The long-chain hydrocarbon butylamide propenyl oxazolone obtained in step S2 is put into a third reaction vessel containing cyclohexane, and then n-butylamine is added to the third reaction vessel for reflux reaction. The solvent is evaporated to obtain long-chain hydrocarbon glutamic acid dibutylamide, which is the target compound of the present invention.

[0011] In step S1, the long-chain hydrocarbon acyl glycine is N-lauryl acyl glycine;

[0012] In steps S2 and S3, the long-chain hydrocarbon butylamide propenyl oxazolone is N-laurylbutylamide propenyl oxazolone;

[0013] The structural formula of N-laurylylglycine is as follows:

[0014]

[0015] The structure of N-laurylbutylamide propenyloxazolone is as follows:

[0016]

[0017] The reaction principle of this reaction is as follows:

[0018]

[0019] In a preferred embodiment of the method for preparing dibutyllauroyl glutamine according to the present invention, in step S1, the molar ratio of long-chain hydrocarbon acyl glycine to acetic anhydride is 1:1 to 1:1.5.

[0020] In a preferred embodiment of the method for preparing dibutyllauroyl glutamine according to the present invention, in step S2, the molar ratio of the long-chain hydrocarbon cyclization product to the base and N-butylacrylamide is 1:(1-1.5):(1-1.5).

[0021] In a preferred embodiment of the method for preparing dibutyllauroyl glutamine according to the present invention, in step S3, the molar ratio of the long-chain hydrocarbon butylamide propenyl oxazolone to n-butylamine is 1:(1-1.2). In another preferred embodiment of the method for preparing dibutyllauroyl glutamine according to the present invention, the alkaline substance is one or more of potassium carbonate, sodium carbonate, and cesium carbonate.

[0022] As a preferred embodiment of the method for preparing dibutyllauroyl glutamine according to the present invention, in step S1, after the reaction is refluxed at high temperature, a certain amount of cyclohexane is added, heated to dissolve, and then recrystallized to obtain a long-chain hydrocarbon cyclized product.

[0023] As a preferred embodiment of the method for preparing dibutyllauroyl glutamine according to the present invention, in step S2, after the reaction is completed, the solid base is removed by filtration, the solvent is removed by rotary evaporation, water and ethyl acetate are added for extraction and separation, the aqueous phase is extracted with ethyl acetate, the extracted phases are combined with the organic phase, and then dried with anhydrous sodium sulfate and concentrated to obtain the crude product.

[0024] On one hand, the present invention provides a method for using butylated lauroyl glutamine synthesized as described above as a small molecule gelling factor, which is applied to cosmetics. Preferably, the cosmetics include lipsticks, lip balms, or creams, etc.

[0025] Compared with the prior art, the present invention has at least one or more of the following beneficial effects:

[0026] The method for preparing dibutyllauroyl glutamine provided by the present invention firstly prepares a long-chain hydrocarbon cyclization product by reacting long-chain hydrocarbon acyl glycine with acetic anhydride, then adds an alkaline catalyst and N-butylacrylamide to react and obtain long-chain hydrocarbon butylamide acryloxazolone, and then adds n-butylamine to react and obtain the target compound of the present invention, dibutyllauroyl glutamine.

[0027] The method provided by this invention cleverly performs a chain-extending reaction on the structure by first subjecting the starting material to a ring-closing reaction, and then performing Michael addition on the reserved sites of the structure, ultimately obtaining the target compound. Compared with traditional processes, the process route of this invention is simple and controllable, with high product conversion rate, stable quality, and is conducive to the synthesis of products of this type of structure, making it easy to realize industrial production.

[0028] The dibutyllauroyl glutamine prepared by this invention has good oleogelation characteristics.

[0029] This invention discloses a method for synthesizing a structure with organic gelling properties from dicarboxylic acid starting materials, achieving specific selectivity. This structure can be used as a small molecule gelling agent, possessing the ability to form organic gels with organic solvents, and acts as an oil-phase thickener in cosmetic products, primarily for lipsticks, lip balms, creams, and similar products.

[0030] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Detailed Implementation

[0031] The embodiments of the present invention will be described in detail below, and the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0032] This embodiment provides a method for preparing dibutyllauroyl glutamine, characterized by comprising the following steps:

[0033] S1: Long-chain hydrocarbon acyl glycine and acetic anhydride are added to the first reaction vessel containing cyclohexane, and the reaction is heated to reflux to obtain the long-chain hydrocarbon cyclization product.

[0034] S2: Add the long-chain hydrocarbon cyclization product obtained in step S1 to a second reaction vessel containing cyclohexane, then add an alkaline substance and N-butylacrylamide to the second reaction vessel for reaction. After the reaction is completed, remove the alkaline substance and solvent to prepare the long-chain hydrocarbon butylacrylamide oxazolone.

[0035] S3: The long-chain hydrocarbon butylamide propenyl oxazolone obtained in step S2 is put into a third reaction vessel containing cyclohexane, and then n-butylamine is added to the third reaction vessel for reflux reaction. The solvent is evaporated to obtain long-chain hydrocarbon glutamic acid dibutylamide, which is the target compound of the present invention.

[0036] In step S1, the long-chain hydrocarbon acyl glycine is N-lauryl acyl glycine;

[0037] In steps S2 and S3, the long-chain hydrocarbon butylamide propenyl oxazolone is N-laurylbutylamide propenyl oxazolone;

[0038] The structural formula of N-laurylylglycine is as follows:

[0039]

[0040] The structure of N-laurylbutylamide propenyloxazolone is as follows:

[0041]

[0042] The reaction principle of this reaction is as follows:

[0043]

[0044] Preferably, in step S1, the molar ratio of long-chain hydrocarbon acyl glycine to acetic anhydride is 1:1 to 1:1.5; in step S2, the molar ratio of long-chain hydrocarbon cyclization product to base and N-butylacrylamide is 1:(1 to 1.5):(1 to 1.5); in step S3, the molar ratio of long-chain hydrocarbon butylamide acryloxyzolone to n-butylamine is 1:(1 to 1.2).

[0045] Preferably, the alkaline substance is one or more of potassium carbonate, sodium carbonate, and cesium carbonate.

[0046] Preferably, in step S1, after the reaction is refluxed at elevated temperature, a certain amount of cyclohexane is added, heated to dissolve, and then recrystallized to obtain a long-chain hydrocarbon cyclized product.

[0047] Preferably, in step S2, after the reaction is complete, the solid base is removed by filtration, the solvent is removed by rotary evaporation, water and ethyl acetate are added for extraction and separation, the aqueous phase is extracted with ethyl acetate, the extracted phases are combined with the organic phase, and then dried with anhydrous sodium sulfate and concentrated to obtain the crude product.

[0048] The dibutyllauroyl glutamine synthesized according to the above-described technical solution provided by this invention is used as a small molecule gelling factor, which is applied in cosmetics. Preferably, the cosmetics include lipsticks, lip balms, or creams.

[0049] Example 1: Synthesis of dibutyllauroyl glutamine

[0050] 5.15 g (0.02 mol) of N-laurylyl glycine, 2.45 g (0.024 mol) of acetic anhydride and 100 ml of cyclohexane were added to a 250 ml three-necked reaction flask and heated to reflux for 2 hours. The reaction was monitored by TLC (thin-layer chromatography) until the reactants were completely reacted. After cooling to room temperature, the solvent was removed by vacuum distillation to obtain the crude product. 50 ml of cyclohexane was added, heated to dissolve, and then recrystallized to obtain 4.0 g (83% yield) of the cyclized product lauryloxazolone.

[0051] 4.79 g (0.02 mol) of lauryl oxazolone, 3.05 g (0.024 mol) of N-butylacrylamide, 100 mL of cyclohexane, and 3.31 g (0.024 mol) of potassium carbonate were added to a 250 mL three-necked flask. The mixture was stirred at room temperature for 12 hours. The reaction was monitored by TLC until the reactants were completely reacted. The solid base was removed by filtration, the solvent was removed by evaporation, and 50 mL of water and 100 mL of ethyl acetate were added for extraction and separation. The aqueous phase was extracted twice with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated to obtain the crude product. The crude product was then subjected to column chromatography (ethyl acetate: petroleum ether = 1:50) to obtain 4.99 g of N-lauryl butylacrylamide propenyl oxazolone (yield 68%).

[0052] 7.33 g (0.02 mol) of N-laurylbutylamide propenyloxazolone and 1.6 g (0.022 mol) of n-butylamine and 50 mL of cyclohexane were added to a 100 mL three-necked flask and heated to reflux. The water produced in the reaction was removed from the reaction system through a water separator, and the disappearance of the starting material was monitored by TLC. The reaction solution was cooled to room temperature, washed three times with water, dried over anhydrous sodium sulfate, and concentrated to obtain a crude product. The crude product was then extracted with 50 mL of ethyl acetate, dried, concentrated, and subjected to column chromatography (ethyl acetate: petroleum ether = 1:50) to obtain 6.86 g of dibutyllauroyl glutamine (yield 78%).

[0053] Example 2 Synthesis of dibutyllauroyl glutamine

[0054] 5.15 g (0.02 mol) of N-laurylyl glycine, 2.04 g (0.02 mol) of acetic anhydride and 100 ml of cyclohexane were added to a 250 ml three-necked reaction flask and heated to reflux for 2 hours. The reaction was monitored by TLC (thin-layer chromatography) until the reactants were completely reacted. After cooling to room temperature, the solvent was removed by vacuum distillation to obtain the crude product. 50 ml of cyclohexane was added, heated to dissolve, and then recrystallized to obtain 3.88 g (81% yield) of the cyclized product lauryloxazolone.

[0055] 4.79 g (0.02 mol) of lauryl oxazolone, 2.54 g (0.02 mol) of N-butylacrylamide, 100 mL of cyclohexane, and 2.76 g (0.02 mol) of potassium carbonate were added to a 250 mL three-necked flask. The mixture was stirred at room temperature for 12 hours. The reaction was monitored by TLC until the reactants were completely reacted. The solid base was removed by filtration, the solvent was removed by rotary evaporation, and 50 mL of water and 100 mL of ethyl acetate were added for extraction and separation. The aqueous phase was extracted twice with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated to obtain the crude product. The crude product was then subjected to column chromatography (ethyl acetate: petroleum ether = 1:50) to obtain 4.76 g of N-lauryl butylacrylamide propenyl oxazolone (yield 65%).

[0056] 7.33 g (0.02 mol) of N-laurylbutylamide propenyloxazolone and 1.46 g (0.02 mol) of n-butylamine and 50 mL of cyclohexane were added to a 100 mL three-necked flask and heated to reflux. The water produced in the reaction was removed from the reaction system through a water separator, and the disappearance of the starting material was monitored by TLC. The reaction solution was cooled to room temperature, washed three times with water, dried over anhydrous sodium sulfate, and concentrated to obtain a crude product. The crude product was then extracted with 50 mL of ethyl acetate, dried, concentrated, and subjected to column chromatography (ethyl acetate: petroleum ether = 1:50) to obtain 6.6 g of dibutyllauroyl glutamine (yield 75%).

[0057] Example 3 Synthesis of dibutyllauroyl glutamine

[0058] 5.15 g (0.02 mol) of N-laurylyl glycine, 3.06 g (0.03 mol) of acetic anhydride and 100 ml of cyclohexane were added to a 250 ml three-necked reaction flask and heated to reflux for 2 hours. The reaction was monitored by TLC (thin-layer chromatography) until the reactants were completely reacted. After cooling to room temperature, the solvent was removed by vacuum distillation to obtain the crude product. 50 ml of cyclohexane was added, heated to dissolve, and then recrystallized to obtain 4.16 g (87% yield) of the cyclized product lauryloxazolone.

[0059] 4.79 g (0.02 mol) of lauryl oxazolone, 3.82 g (0.03 mol) of N-butylacrylamide, 100 mL of cyclohexane, and 4.15 g (0.03 mol) of potassium carbonate were added to a 250 mL three-necked flask. The mixture was stirred at room temperature for 12 hours. The reaction was monitored by TLC until the reactants were completely reacted. The solid base was removed by filtration, the solvent was removed by evaporation, and 50 mL of water and 100 mL of ethyl acetate were added for extraction and separation. The aqueous phase was extracted twice with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated to obtain the crude product. The crude product was then subjected to column chromatography (ethyl acetate: petroleum ether = 1:50) to obtain 5.04 g of N-lauryl butylacrylamide propenyl oxazolone (yield 68.8%).

[0060] 7.33 g (0.02 mol) of N-laurylbutylamide propenyloxazolone and 1.76 g (0.024 mol) of n-butylamine and 50 mL of cyclohexane were added to a 100 mL three-necked flask and heated to reflux. The water produced in the reaction was removed from the reaction system through a water separator, and the disappearance of the starting material was monitored by TLC. The reaction solution was cooled to room temperature, washed three times with water, dried over anhydrous sodium sulfate, and concentrated to obtain a crude product. The crude product was then extracted with 50 mL of ethyl acetate, dried, concentrated, and subjected to column chromatography (ethyl acetate: petroleum ether = 1:50) to obtain 6.95 g of dibutyllauroyl glutamine (yield 79%).

[0061] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing dibutyllauroyl glutamine, characterized in that, Includes the following steps: S1: Long-chain hydrocarbon acyl glycine and acetic anhydride are added to the first reaction vessel containing cyclohexane, and the mixture is heated to reflux to prepare the long-chain hydrocarbon cyclization product; wherein the molar ratio of long-chain hydrocarbon acyl glycine to acetic anhydride is 1:1 to 1:1.

5. S2: The long-chain hydrocarbon cyclization product obtained in step S1 is added to a second reaction vessel containing cyclohexane. Then, an alkaline substance and N-butylacrylamide are added to the second reaction vessel to react. After the reaction is completed, the alkaline substance and solvent are removed to prepare the long-chain hydrocarbon butylamide propenyl oxazolone. The molar ratio of the long-chain hydrocarbon cyclization product to the base and N-butylacrylamide is 1:(1~1.5):(1~1.5). The alkaline substance is one or more of potassium carbonate, sodium carbonate and cesium carbonate. S3: The long-chain hydrocarbon butylamide propenyl oxazolone obtained in step S2 is added to a third reaction vessel containing cyclohexane, and then n-butylamine is added to the third reaction vessel for reflux reaction. The molar ratio of long-chain hydrocarbon butylamide propenyl oxazolone to n-butylamine is 1:(1~1.2). The solvent is evaporated to obtain long-chain hydrocarbon glutamic acid dibutylamide, which is the target compound of this invention. In step S1, the long-chain hydrocarbon acyl glycine is N-lauryl acyl glycine; In steps S2 and S3, the long-chain hydrocarbon butylamide propenyl oxazolone is N-laurylbutylamide propenyl oxazolone; The structural formula of N-laurylylglycine is as follows: ； The structure of N-laurylbutylamide propenyloxazolone is as follows: 。 2. The method for preparing dibutyllauroyl glutamine according to claim 1, characterized in that, In step S1, after the reaction is refluxed at high temperature, a certain amount of cyclohexane is added, heated to dissolve, and then recrystallized to obtain the long-chain hydrocarbon cyclized product.

3. The method for preparing dibutyllauroyl glutamine according to claim 1, characterized in that, In step S2, after the reaction is complete, the solid base is removed by filtration, the solvent is removed by rotary evaporation, water and ethyl acetate are added for extraction and separation, the aqueous phase is extracted with ethyl acetate, the extracts are combined with the organic phase, and then dried with anhydrous sodium sulfate and concentrated to obtain the crude product.

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