KR100498268B1 - Amphoteric surfactant having pyrrolidone group - Google Patents

Abstract

The present invention relates to a pyrrolidone-based amphoteric surfactant and a preparation method thereof, wherein the pyrrolidone-based amphoteric surfactant is an amphoteric surfactant having a pyrrolidone ring represented by the following formula (2), and the method for preparing the same is A first step of preparing an intermediate through dehydration condensation of konic acid and dialkylaminoalkylamine; Dissolving the intermediate in a solvent and neutralizing it with a base, and then preparing a pyrrolidone-based amphoteric surfactant represented by Chemical Formula 2 through quaternization with an alkyl halide. .

Formula 2

(Wherein n is an integer from 1 to 6, R1 and R2 are the same or different lower alkyl groups having 1 to 5 carbon atoms, R3 represents a straight-chain or branched alkyl group having 8 to 22 carbon atoms, cycloalkyl group or alkenyl group)

Description

Amphiphilic surfactant having pyrrolidone group

The present invention relates to a pyrrolidone-based amphoteric surfactant and a method for producing the same, and in particular, a dehydration condensation reaction using an amphoteric surfactant having a pyrrolidone ring having high solubility in hard water, and dibasic itaconic acid and diamine. The present invention relates to a method for preparing a pyrrolidone-based amphoteric surfactant by synthesizing N-dialkylaminoalkyl pyrrolidone 4-carboxylic acid by quaternization and quaternizing with an alkyl halide to a terminal amine group of a pyrrolidone substituent.

Pyrrolidone rings are γ -lactams and are classified into homologues such as β -lactams such as penicillin and cephalosporin. It is well known that β -lactam substances are widely used as antibacterial agents, antibiotics, and various medicines. Pyrrolidone substances, which are γ -lactam substances, which form one of the homologues, can be expected to have such biological activities. .

The pyrrolidone ring is a planar pentagonal lactam, which has a relatively large dipole moment of 4.06 for N-methyl pyrrolidone. The N-alkyl pyrrolidone ring has a resonance stabilizing structure due to a nitrogen atom and an oxygen atom as shown in the following formula (1).

[Formula 1]

Therefore, it is a general solvent that shows great resistance to hydrolysis by acids, bases, etc., and is easily mixed with water because of its high polarity, and can be hydrogen-bonded with water. For this reason, the pyrrolidone ring itself has the advantage of being hydrophilic and easily soluble and dispersed in water. The pyrrolidone ring has a partial charge due to resonance, and exhibits different physical properties from general ionic surfactants having full charge, and has a greater polarity than acyclic amides.

The pyrrolidone ring is reported to be structurally biologically active and biocompatible due to the fact that these compounds have structures derived from glutamic acid derived from living bodies and also contain heteroatoms like many alkaloids. Here are characteristic examples of compounds containing several pyrrolidone rings.

Pyrrolidone 5-carboxylic acid is one of the natural moisturizing factors and is known as one of the essential elements for maintaining human skin moisturizing. It is basically a form produced by thermal dehydration of glutamic acid, which is present in the skin of the human body to prevent the skin from drying out by controlling the access of moisture like other substances. If this is lacking, the skin is easily dried and roughened, causing a condition that is easy to cause skin diseases.

Variotin is a fungus-derived substance with a long chain unsaturated alkyl group bound to the nitrogen atom of the pyrrolidone ring. It has antimicrobial activity and is effective for fungal infections. Foreign substances have low toxicity and are particularly effective against athlete's foot. The foreign substance is a condensed condensation of an unsaturated acid moiety via a polyketide chain and a pyrrolidone ring derived from glutamic acid (S. Takeuchi, H. Yonehara, J. Antibiot, 17A, 267, 1964).

N-methyl pyrrolidone is the starting material for industrial use of compounds with pyrrolidone rings and can be synthesized industrially by the Lepe process (W. Reppe, Bibliogr. Tech. Rep. 10: 348, 1948). It is known to be a solvent that is started and has little toxicity. This material has a high solvation effect on cationic compounds and has a relatively large dielectric constant, so that various intrinsic binding compounds and ionic compounds can be easily solubilized, and gelling solvents such as polymers, which are the main uses of aprotic solvents. Is being used.

Polyvinylpyrrolidone is a polymer compound developed by Lefe and is a polymer compound containing N-vinyl pyrrolidone as a unit. Polyvinylpyrrolidone is not only soluble in various organic solvents such as alcohols, acids and amines, but also well in water. Polyvinylpyrrolidone is chemically very stable and extremely low toxicity has been proved to be used in povidone-iodine solution, which is one of medical tablets and medical disinfectants. In addition, it is used in shampoos and styling agents, and is used as a phase stabilizer and a complex compound forming agent using a viscosity increasing effect and a large solvent effect.

As can be seen from the above examples, compounds containing pyrrolidone ring have excellent biocompatibility and low toxicity to the human body. In addition, since these compounds exhibit unique or general biological activities, various derivatives have been synthesized to utilize this activity, and various prescriptions have been sought as active ingredient additives. Here are some examples of recent resources.

According to US Patent USP5294644, N-alkylpyrrolidone easily forms micelle structures in neutral, acidic and basic aqueous solutions, and has a complex forming effect, which helps to improve the stability of surfactants or complexing agents. Alkylpyrrolidone is said to be used in the composition of physicochemical carriers to transport physiological chemicals through biofilms.

In addition, according to US Patent USP3085931, N-alkylpyrrolidone has an inhibitory effect of inhibiting the growth of the virus attacking the plant, in particular excellent effect in the range of 10 ^-5 to 10 ^-3 molarity. In USP5250194, N-alkylpyrrolidone can be used industrially as an antimicrobial or preservative, which is achieved by preventing microorganisms from entering the process during the production process and decomposing surface coatings, wood, plastics and fibers.

In addition, according to US Patent USP5206386, it is possible to release slowly in vivo by combining a pyrrolidone ring nitrogen-substituted organic acid, etc., which is one of the application methods for delivering drugs using the biocompatibility of the pyrrolidone ring This is an example.

According to US Patent USP4732990, cationic compounds synthesized by quaternization of tertiary amines with N-haloalkyl pyrrolidones are very effective in increasing the viscosity of aqueous solutions and are also complexed by complex formation with anionic surfactants. It can give conditioning effect to hair and skin without generating sediment. It shows biological activity and is useful for dandruff prescription, scalp and skin prescription. It can be shown. These compounds can be used as rinses or hair conditioners and can also be used as mouthwashes.

In US Patent USP2757125, salts formed by neutralizing N-alkyl-4-carboxy-2-pyrrolidone obtained by the dehydration condensation reaction of itaconic acid and primary alkylamine with alkali are causative agents of caries present in the oral cavity as anionic compounds. It inhibits carbohydrate fermentation of phosphorus lactobacilli and consequently decreases the growth of causative agents of caries, and N-lauryl-4-carboxy-2-pyrrolidone 0.1% solution inhibits the growth of Staphylococcus aureus. It can be applied to toothpaste, mouthwash, chewing gum and rinse.

Pyrrolidone-based surfactants thus far developed are mainly nonionic, cationic and anionic compounds. However, in the case of nonionic surfactants, there is a prescription problem that it is difficult to use alone due to low solubility in aqueous solutions. Cationic surfactants cannot be applied to mixed prescription because they form precipitates when used with anionic surfactants. There are disadvantages. In addition, anionic surfactants have a disadvantage in that they are easy to form salts with divalent metal ions included in hard water and have low stability to hard water.

Accordingly, the present invention is to solve the above-mentioned shortcomings, and to provide a pyrrolidone-based amphoteric surfactant having a pyrrolidone ring using various properties and biological activities of the pyrrolidone-based compounds and its preparation method have.

The present invention for achieving the above object provides a pyrrolidone-based amphoteric surfactant represented by the following formula (2).

[Formula 2]

(Wherein n is an integer from 1 to 6, R1 and R2 are the same or different lower alkyl groups having 1 to 5 carbon atoms, R3 represents a straight-chain or branched alkyl group having 8 to 22 carbon atoms, cycloalkyl group or alkenyl group)

Examples of the pyrrolidone-based amphoteric surfactant of the present invention include N '-(N, N-dimethyloctyl) ethyl ammonium pyrrolidone-4-carboxylate, N'-(N, N-dimethyldodecyl) Propyl Ammonium Pyrrolidone-4-carboxylate, N '-(N, N-dimethyloctyl) ethyl Ammonium Pyrrolidone-4-carboxylate, N'-(N, N-dimethyloctyl) propyl Ammonium Pyrroli Don-4-carboxylate, N '-(N, N-dimethyloctyl) butyl ammonium pyrrolidone-4-carboxylate, N'-(N, N-dimethyloctyl) pentyl ammonium pyrrolidone-4- Carboxylate, N '-(N, N-dimethyloctyl) hexyl ammonium pyrrolidone-4-carboxylate, N'-(N, N-dimethyloctyl) methyl ammonium pyrrolidone-4-carboxylate, N '-(N, N-dimethyldodecyl) methyl ammonium pyrrolidone-4-carboxylate, N'-(N, N-dimethyldodecyl) ethyl ammonium pyrrolidone-4-carboxylate, N ' -(N, N-dimethyldodecyl) propyl ammonium pyrrolidone-4-carboxylate, N '-(N, N-dimethyldodecyl) butyl Ammonium Pyrrolidone-4-carboxylate, N '-(N, N-dimethyldodecyl) pentyl Ammonium Pyrrolidone-4-carboxylate, N'-(N, N-dimethyldodecyl) hexyl Ammonium P Rollidone-4-carboxylate etc. are mentioned.

Examples of such a method for preparing a pyrrolidone-based amphoteric surfactant include the first step of preparing an intermediate through dehydration condensation of itaconic acid and dialkylaminoalkylamine; Dissolving the intermediate in a solvent and neutralizing it with a base, and then preparing a pyrrolidone-based amphoteric surfactant represented by Formula 2 through quaternization with an alkyl halide. Can achieve the purpose.

In the method for producing a pyrrolidone-based amphoteric surfactant, the compound represented by the following formula (3) can be obtained as the intermediate.

[Formula 3]

(Wherein n represents an integer of 1 to 6, R1 and R2 represent the same or different lower alkyl groups of 1 to 5 carbon atoms)

In the above method, the solvent used in the second step is preferably one selected from isopropyl alcohol, dioxane, tetrahydrofuran, and ethanol.

Hereinafter, the configuration and operation of the present invention will be described in detail.

As described above, the pyrrolidone-based amphoteric surfactant of the present invention is represented by Chemical Formula 2, and has a high solubility in hard water due to the pyrrolidone ring, and is well soluble in both acidic and alkaline aqueous solutions, and anionic. Or it can mix and use with cationic surfactant.

And because it is an amphoteric compound, it can be used in any pH range, and because it has a carboxylate group in its molecule, it does not form divalent metal ions and hardly soluble salts contained in hard water due to the large polarity of the pyrrolidone ring. It is a compound having various applicability.

In addition, the cationic and anionic properties at the same time has a low irritation to the skin.

A first step of preparing an intermediate through dehydration condensation of itaconic acid and dialkylaminoalkylamine as described above as a method for preparing the pyrrolidone-based amphoteric surfactant of the present invention: dissolving the intermediate in a solvent And neutralizing with a base, followed by a second step of preparing a pyrrolidone-based amphoteric surfactant represented by Chemical Formula 2 through quaternization with an alkyl halide. The dehydration condensation reaction of itaconic acid with dialkylaminoalkylani is applied to the present invention using the method described in USP2757125, and it is preferable to use toluene or benzene as a solvent to remove water generated during the reaction. The reaction temperature is preferably between 80 and 140 degrees Celsius, with 105 to 115 degrees Celsius being most preferred. After all the water is removed, the solvent is dried in vacuo to remove less than 10% and crystallized under acetonitrile or acetone. Among the dialkylaminoalkylamines used in the present invention are N, N-dialkylaminoalkylamines wherein R 1 and R 2 are lower alkyl groups having the same or different carbon atoms of 5 to 5 carbon atoms, and examples thereof include N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-dimethylaminobutylamine, N, N-dimethylaminopentylamine, N, N-dimethylaminohexylamine, N, N-di Ethylaminomethylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-di Ethylaminohexylamine and the like and are not limited thereto.

In the second step, the intermediate obtained in the first step is dissolved in a solvent, neutralized by treatment with a base such as sodium hydroxide or sodium methoxide, and then quaternized with an alkyl halide to synthesize a target compound. Examples of alkyl halides that are used include octyl chloride, octyl bromide, octyl iodide, decyl chloride, decyl bromide, decyl iodide, dodecyl chloride, dodecyl bromide, dodecyl iodide, tetradecyl chloride, tetradecyl bromide, tetradecyl iodide, hexa Decyl chloride, hexadecyl bromide, hexadecyl iodide, octadecyl chloride, octadecyl bromide, octadecyl iodine, eicosyl chloride, eicosyl bromide, eicosyl iodide, docosyl chloride, docosyl bromide, docosyl iodide, etc. It is limited to here No.

In the second step, the solvent for dissolving the intermediate is isopropyl alcohol, tetrahydrofuran, dioxane, ethanol and the like, and the reaction temperature is performed at 80 to 130 degrees Celsius and 105 to 115 degrees Celsius is most preferred.

As another method for preparing the pyrrolidone-based amphoteric surfactant of the present invention, the first step is the same as the preparation method, and in the second step reaction by using an autoclave To synthesize.

The advantage of this method is that the yield can be increased by about 5 to 10% over the production method described above, and the reaction time can be shortened. The reaction temperature at this time is performed between 110 and 150 degrees Celsius, and most preferably 120 to 130 degrees Celsius.

The following examples are only for the purpose of illustrating the present invention in detail and are intended to help understanding, but the scope of the present invention in any sense is not limited by the examples.

Example 1.Preparation of N '-(N, N-dimethylamino) propyl pyrrolidone-4-carboxylic acid

Place a Dean-Stark trap in a three-necked flask, add 112 g of N, N-dimethylaminopropylamine to 130 g of itaconic acid, add 200 g of toluene solvent, and stir the reaction mixture until the toluene and water are distilled together. After advancing, the removed water was removed by distillation so that only 10% of the solvent was left under vacuum and reduced pressure when it was 95% or more, and after cooling to crystallization in acetonitrile when it reached 70 degrees Celsius, it was filtered to obtain a white powder. 203 g of N '-(N, N-dimethylamino) propyl pyrrolidone-4-carboxylic acid was obtained.

Example 2. Preparation of N '-(N, N-dimethylamino) propyl pyrrolidone-4-carboxylic acid

Install a Dean-Stark trap in a three-necked flask, add 110 g of N, N-dimethylaminopropylamine to 130 g of itaconic acid, add 200 g of benzene solvent, and stir the reaction mixture until the benzene and water are distilled together. After the removal of water, the removed water is at least 95% by distillation to remove only 10% of the solvent under vacuum decompression, and then cooled to crystallize in acetone when the temperature reaches 50 degrees Celsius, and then filtered to white N'- 193 g of (N, N-dimethylamino) propyl pyrrolidone-4-carboxylic acid was obtained.

Example 3. Preparation of N '-(N, N-dimethylamino) propyl pyrrolidone-4-carboxylic acid

Place a Dean-Stark trap in a three-necked flask, add 112 g of N, N-dimethylaminopropylamine to 130 g of itaconic acid, add 200 g of benzene solvent, and stir the reaction mixture until the benzene and water are distilled together. After advancing, the removed water was removed by distillation so that only 10% of the solvent was left under vacuum and reduced pressure when it was 95% or more, and after cooling to crystallization in acetonitrile when it reached 70 degrees Celsius, it was filtered to obtain a white powder. 198 g of N '-(N, N-dimethylamino) propyl pyrrolidone-4-carboxylic acid was obtained.

Examples 1 to 3 are according to the first step of the production method of the pyrrolidone-based amphoteric surfactant of the present invention.

Example 4 Preparation of N '-(N, N-dimethyldodecyl) propyl Ammonium Pyrrolidone-4-carboxylate

A reflux condenser was installed in a three-necked flask, 107 g of N '-(N, N-dimethylamino) propyl pyrrolidone-4-carboxylic acid was suspended in 200 g of isopropyl alcohol, and 20 g of sodium hydroxide was added to neutralize the acid. Add 102 g of silchloride, heat the bath to reflux the isopropyl alcohol, cool to room temperature when the reaction is complete, filter the filtered sodium chloride to remove the sodium chloride, remove the solvent by vacuum drying under reduced pressure, and then in acetone Crystallization gave 153 g of N '-(N, N-dimethyldodecyl) propyl ammonium pyrrolidone-4-carboxylate.

Example 5 Preparation of N '-(N, N-dimethyltetradecyl) propyl Ammonium Pyrrolidone-4-carboxylate

A reflux condenser was installed in a three-necked flask, 107 g of N '-(N, N-dimethylamino) propyl pyrrolidone-4-carboxylic acid was suspended in 200 g of dioxane, and 27.5 g of sodium methoxide was added to neutralize the acid. Add 116 g of tetradecyl chloride and heat the bath to reflux the dioxane, cool to room temperature when the reaction is complete, filter the resulting sodium chloride to remove the sodium chloride, remove the solvent by vacuum drying under reduced pressure, and then in acetone Crystallization gave 165 g of N '-(N, N-dimethyltetradecyl) propyl ammonium pyrrolidone-4-carboxylate.

Example 6 Preparation of N '-(N, N-dimethylhexadecyl) propyl Ammonium Pyrrolidone-4-carboxylate

A reflux condenser was installed in a three-necked flask, 107 g of N '-(N, N-dimethylamino) propyl pyrrolidone-4-carboxylic acid was suspended in 250 g of ethanol, and 27.5 g of sodium methoxide was added to neutralize the acid. Add 130 g of decyl chloride, heat the bath to reflux ethanol, cool to room temperature when the reaction is complete, filter the resulting sodium chloride, remove the solvent by vacuum drying under reduced pressure, and crystallize in acetone. 176 g of N '-(N, N-dimethylhexadecyl) propyl ammonium pyrrolidone-4-carboxylate was obtained.

Example 7 Preparation of N '-(N, N-dimethyloctadecyl) propyl Ammonium Pyrrolidone-4-carboxylate

A reflux condenser was installed in a three-necked flask, 107 g of N '-(N, N-dimethylamino) propyl pyrrolidone-4-carboxylic acid was suspended in 300 g of dioxane, and 20 g of sodium hydroxide was added to neutralize the acid, followed by octadecyl. Add 144 g of chloride, heat the bath to reflux the dioxane, cool to room temperature when the reaction is complete, filter the resulting sodium chloride, remove the solvent by vacuum drying under reduced pressure, and crystallize in acetone. 179 g of N '-(N, N-dimethyloctadecyl) propyl ammonium pyrrolidone-4-carboxylate was obtained.

Example 8 Preparation of N '-(N, N-dimethyldodecyl) propyl Ammonium Pyrrolidone-4-carboxylate

107 g of N '-(N, N-dimethylamino) propyl pyrrolidone-4-carboxylic acid was placed in 50 g of dioxane and neutralized with 20 g of sodium methoxide, followed by 102 g of dodecyl chloride. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered, filtered, filtered to remove sodium chloride, and the solvent was removed by vacuum drying under reduced pressure, and then crystallized in acetone to obtain N '-(N, N 162 g of -dimethyldodecyl) propyl ammonium pyrrolidone-4-carboxylate was obtained.

Example 9 N '-(N, N-Dimethyltetradecyl) propyl Ammonium Pyrrolidone-4-carboxylate

107 g of N '-(N, N-dimethylamino) propyl pyrrolidone-4-carboxylic acid was placed in 50 g of isopropyl alcohol and neutralized by adding 20 g of sodium hydroxide to the autoclave apparatus. Then, 116 g of tetradecyl chloride was added and heated. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered, filtered, filtered to remove sodium chloride, and the solvent was removed by vacuum drying under reduced pressure, and then crystallized in acetone to obtain N '-(N, N 175 g of -dimethyltetradecyl) propyl ammonium pyrrolidone-4-carboxylate was obtained.

Examples 4 to 9 are according to the second step of the preparation method of the pyrrolidone-based amphoteric surfactant of the present invention, Examples 8 and 9 are the examples of preparing the target compound using an autoclave device to be.

As described above, the pyrrolidone-based amphoteric surfactant of the present invention has a high solubility in hard water due to the pyrrolidone ring, is well soluble in both acidic and alkaline aqueous solutions, and mixed with anionic or cationic surfactants. It can be used to effect.

Claims (3)

Pyrrolidone-based amphoteric surfactant represented by the following formula (2): [Formula 2]

In the formula (2), n is an integer from 1 to 6, R ₁ and R ₂ are the same or different lower alkyl groups having 1 to 5 carbon atoms, R <_3> is a C8-C22 linear or branched alkyl group, a cycloalkyl group, or an alkenyl group. A first step of preparing an intermediate represented by the following Chemical Formula 3 through dehydration condensation of itaconic acid and dialkylaminoalkylamine; A second step of dissolving the intermediate represented by Chemical Formula 3 in a solvent and neutralizing it with a base, and then preparing a pyrrolidone-based amphoteric surfactant represented by Chemical Formula 2 by quaternization with an alkyl halide; Method for preparing a pyrrolidone-based amphoteric surfactant consisting of: [Formula 2]

[Formula 3]

In Formula 2 and Formula 3, n is an integer from 1 to 6, R ₁ and R ₂ are the same or different lower alkyl groups having 1 to 5 carbon atoms, R <_3> is a C8-C22 linear or branched alkyl group, a cycloalkyl group, or an alkenyl group. The method of claim 2, wherein the solvent used in the second step is at least one selected from the group consisting of isopropyl alcohol, dioxane, tetrahydrofuran, and ethanol. .