CN106076191A - A kind of anionic surfactant utilizing monosodium glutamate to prepare and preparation method thereof - Google Patents
A kind of anionic surfactant utilizing monosodium glutamate to prepare and preparation method thereof Download PDFInfo
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- CN106076191A CN106076191A CN201610393973.5A CN201610393973A CN106076191A CN 106076191 A CN106076191 A CN 106076191A CN 201610393973 A CN201610393973 A CN 201610393973A CN 106076191 A CN106076191 A CN 106076191A
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- anionic surfactant
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- glutamic acid
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The present invention relates to a kind of surfactant, be specifically related to a kind of anionic surfactant utilizing monosodium glutamate to prepare and preparation method thereof, belong to cosmetic field.This anionic surfactant is to be prepared via a method which to obtain: monosodium glutamate first utilizes esterification carry out carboxy protective, and recycling Long carbon chain fatty acid carries out amido modified, and finally hydrolysis is removed the protection group of carboxyl and i.e. be can get anionic surfactant.Described Long carbon chain fatty acid is the carbochain fatty acid that contains more than 8 carbon atoms or oils and fats alkaline hydrolysis product in alcoholic solution.The anionic surfactant that the present invention provides is to have a long hydrophobic chain and the anionic surfactant of two hydrophilic carboxyls, it can apply in cosmetic formulations, can also be as novel surfactant for industrial circle, extend the application of sodium glutamate, and preparation method is simple, it is simple to expand application.
Description
Technical field
The present invention relates to cosmetic field and industrial circle, particularly to a kind of anionic surface utilizing monosodium glutamate to prepare
Activating agent and preparation method thereof.
Background technology
Monosodium glutamate is the sodium salt of a kind of aminoacid (glutamic acid), is the necessary nutrient substance of human body, mainly with cheap sugar source
Being obtained by fermentation process and prepared by method for crystallising, purity can reach more than 99%.The development of large scale fermentation technology with
The lifting of crystallization technique makes China's msg output be significantly increased, and produces preparation cost and constantly declines, current 1 kilogram of packaging monosodium glutamate
Market price be 14.8 yuans, the serious development restricting glutamate production enterprise, need to open up new monosodium glutamate application.
Summary of the invention
In order to extend the application of monosodium glutamate, the invention provides a kind of anionic surface activity utilizing glutamate production
Agent and preparation method thereof, the anionic surfactant of preparation may be used for cosmetics, it is also possible to as novel surface activity
Agent is used for industrial circle.
Technical scheme is as follows: a kind of anionic surfactant utilizing monosodium glutamate to prepare, and is by as follows
Method prepares: monosodium glutamate first utilizes esterification carry out carboxy protective, re-uses Long carbon chain fatty acid and carry out amido modified,
The esterification protection group of carboxyl, described monosodium glutamate i.e. sodium glutamate are removed in finally hydrolysis.
Further, described Long carbon chain fatty acid is that the carbochain fatty acid that contains more than 8 carbon atoms or oils and fats are at alcohol
Alkaline hydrolysis product in solution, it is also possible to utilize other oil resources to carry out the preparation of fatty acid, oils and fats is preferably vegetable oil or dynamic
Thing oil, more preferably soybean oil, its low cost, described Long carbon chain fatty acid can also can carry without double bond with double bond
Some double bonds can also more than one.
Further, described esterification includes ethyl esterified or esterification.
Further, described amido modified be Long carbon chain fatty acid with glutamate diethyl ester or glutamic acid dimethyl ester in contracting
Under the effect of mixture, reaction completes, described condensing agent be 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimine (EDC),
Dicyclohexylcarbodiimide (DCC), N, N-DIC (DIC) or O-BTA-tetramethylurea hexafluoro phosphorus
Hydrochlorate (HBTU).
Further, described amido modified can also is that Long carbon chain fatty acid reacts with thionyl chloride after, then with paddy ammonia
Diethyl phthalate or glutamic acid dimethyl ester have reacted.
The present invention is claimed the preparation method of described anionic surfactant simultaneously, and the method includes walking as follows
Rapid: (1) carboxy protective: monosodium glutamate to be added in dehydrated alcohol or absolute methanol, monosodium glutamate and dehydrated alcohol or the quality of absolute methanol
Volume ratio is 1:(5-20), it is placed in the environment of less than 0 DEG C, thionyl chloride is slowly added to, the molal quantity of thionyl chloride
Be 2-6 times of monosodium glutamate, stir after adding, then carry out oil bath be heated to reflux, react after cool down, cooled and filtered, then will filter
Liquid is evaporated, and i.e. obtains glutamate diethyl ester or glutamic acid dimethyl ester；(2) amido modified: glutamate diethyl ester or glutamic acid diformazan
Ester and Long carbon chain fatty acid response, complete amido modified after obtain fatty acyl glutamate diethyl ester or fatty acyl paddy through isolated and purified
Propylhomoserin dimethyl ester；(3) carboxyl-protecting group is removed: fatty acyl glutamate diethyl ester step (2) obtained or fatty acyl glutamic acid
Dimethyl ester uses methanol to dissolve, and is added thereto to the sodium hydroxide solution of 2mol/L, and wherein the molal quantity of sodium hydroxide is fat
Acyl glutamate diethyl ester or 10 times of fatty acyl glutamic acid dimethyl ester molal quantity, after reaction terminates, remove first alcohol and water, use 1N salt
PH 5 is adjusted in acid, and makes to be extracted with ethyl acetate, and combining extraction liquid drying, evaporates and i.e. obtains monosodium glutamate surfactant-fatty acyl paddy
Propylhomoserin.
Beneficial effects of the present invention is as follows: the inventive point of the present invention is by the method by chemical modification of the amino in monosodium glutamate
Long carbon chain fatty acid in connection, becomes and has a long hydrophobic chain and the anionic surfactant of two hydrophilic carboxyls.This
Invention has the molecular structure feature of two carboxyls and an amino according to monosodium glutamate, carries out carboxy protective first with esterification,
Prevent carboxyl from reacting in follow-up chemical modification；The amino of monosodium glutamate is modified by recycling Long carbon chain fatty acid；?
The blocking group of carboxyl is removed afterwards, it is thus achieved that target product-anionic surfactant, can apply to by hydrolysis
In cosmetic formula, it is also possible to as novel surfactant for industrial circle, extend the application of monosodium glutamate, and preparation side
Method is simple, it is simple to expand application.
Detailed description of the invention
The present invention will be described by the following examples, but is not limited to the scope of the present invention, former used by the present invention
Material is without specified otherwise, the most commercially.
Embodiment 1
(1) 4.0g monosodium glutamate (21mmol) is incorporated with in the round-bottomed flask of dehydrated alcohol 30ml, is placed in cryosel bath, will
6.0mL thionyl chloride (80mmol) is slowly dropped into constant voltage separatory funnel, controls uniformly to drip off, after dripping off in 2 hours
Magnetic agitation 30min under room temperature, 85 DEG C of oil baths are heated to reflux 6 hours, have Precipitation after cooling, are used by the supernatant after cooling
Buchner funnel sucking filtration, is evaporated filter liquor Rotary Evaporators, obtains diethyl glutamate hydrochloride.
(2) take oleic acid 0.565g (2mmol), dissolve with 20mL dichloromethane, be separately added into the 1-hydroxy benzo three of 2mmol
Azoles (HOBT), 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimine (EDC) of 2mmol, the N of 2mmol, N-diisopropyl
After ethamine (DIEA), stir 30 minutes under ice bath, then the step (1) dissolved by 10mL dichloromethane with constant voltage separatory funnel obtains
To diethyl glutamate hydrochloride 0.48g (2mmol) and after the DIEA of 2mmol is slowly dropped into, stir 1 hour under ice bath,
After removing ice, room temperature reaction is overnight, terminates, with the isolated and purified acquisition of silicagel column to reaction with thin layer chromatography (TLC) detection reaction process
Oils and fats acyl glutamate diethyl ester.
(3) take oils and fats acyl glutamate diethyl ester 0.936 gram (2mmol) 10mL methanol to dissolve, add the hydrogen-oxygen of 2mol/L
Change sodium solution (wherein the molal quantity of sodium hydroxide is 20mmol), determine that second fat blocking group removes completely by TLC detection.Instead
After should terminating, the method distilled by decompression removes methanol and major part aqueous solvent, is transferred to pH 5 with dilute hydrochloric acid, uses ethyl acetate
Extract.Combining extraction liquid, is dried with anhydrous sodium sulfate, utilizes Rotary Evaporators to obtain target product-oils and fats acyl glutamic acid.
Embodiment 2
(1) 4.0g monosodium glutamate (21mmol) is incorporated with in the round-bottomed flask of dehydrated alcohol 80ml, is placed in cryosel bath, will
9.0mL thionyl chloride (126mmol) is slowly dropped into constant voltage separatory funnel, controls uniformly to drip off, after dripping off in 2 hours
Magnetic agitation 30min under room temperature, 95 DEG C of oil baths are heated to reflux 9 hours, have Precipitation after cooling, are used by the supernatant after cooling
Buchner funnel sucking filtration, is evaporated filter liquor Rotary Evaporators, obtains diethyl glutamate hydrochloride.
(2) take oleic acid 0.565g (2mmol), dissolve with 20mL dichloromethane, be separately added into the 1-hydroxy benzo three of 2mmol
Azoles (HOBT), the N of 2mmol, N-DIC (DIC), 2mmol DIPEA (DIEA) after,
Stir 30 minutes under ice bath, then the glutamic acid diethyl that the step (1) dissolved by 10mL dichloromethane with constant voltage separatory funnel obtains
After the DIEA of ester hydrochloride 0.48g (2mmol) and 2mmol is slowly dropped into, stirs 1 hour under ice bath, remove ambient temperature overnight after ice
Reaction, terminates, with silicagel column isolated and purified acquisition oils and fats acyl glutamic acid two to reaction with thin layer chromatography (TLC) detection reaction process
Ethyl ester.
(3) take oils and fats acyl glutamate diethyl ester 0.936 gram (2mmol) 10mL methanol to dissolve, add the hydrogen-oxygen of 2mol/L
Change sodium solution (wherein the molal quantity of sodium hydroxide is 20mmol), determine that second fat blocking group removes completely by TLC detection.Instead
After should terminating, the method distilled by decompression removes methanol and major part aqueous solvent, is transferred to pH 5 with dilute hydrochloric acid, uses ethyl acetate
Extract.Combining extraction liquid, is dried with anhydrous sodium sulfate, utilizes Rotary Evaporators to obtain target product-oils and fats acyl glutamic acid.
Embodiment 3
(1) 4.0g monosodium glutamate (21mmol) is incorporated with in the round-bottomed flask of dehydrated alcohol 20ml, is placed in cryosel bath, will
3.15mL thionyl chloride (42mmol) is slowly dropped into constant voltage separatory funnel, controls uniformly to drip off, after dripping off in 2 hours
Magnetic agitation 30min under room temperature, 80 DEG C of oil baths are heated to reflux 3 hours, have Precipitation after cooling, are used by the supernatant after cooling
Buchner funnel sucking filtration, is evaporated filter liquor Rotary Evaporators, obtains diethyl glutamate hydrochloride.
(2) take oleic acid 0.565g (2mmol), dissolve with 20mL dichloromethane, be separately added into the 1-hydroxy benzo three of 2mmol
Azoles (HOBT), 2mmol dicyclohexylcarbodiimide (DCC), 2mmol DIPEA (DIEA) after, under ice bath
Stir 30 minutes, then the glutamate diethyl ester hydrochloric acid that the step (1) dissolved by 10mL dichloromethane with constant voltage separatory funnel obtains
After the DIEA of salt 0.48g (2mmol) and 2mmol is slowly dropped into, stirs 1 hour under ice bath, remove room temperature reaction overnight after ice, use
Thin layer chromatography (TLC) detection reaction process terminates, with silicagel column isolated and purified acquisition oils and fats acyl glutamate diethyl ester to reaction.
(3) take oils and fats acyl glutamate diethyl ester 0.936 gram (2mmol) 13mL methanol to dissolve, add the hydrogen-oxygen of 2mol/L
Change sodium solution (wherein the molal quantity of sodium hydroxide is 20mmol), determine that second fat blocking group removes completely by TLC detection.Instead
After should terminating, the method distilled by decompression removes methanol and major part aqueous solvent, is transferred to pH 5 with dilute hydrochloric acid, uses ethyl acetate
Extract.Combining extraction liquid, is dried with anhydrous sodium sulfate, utilizes Rotary Evaporators to obtain target product-oils and fats acyl glutamic acid.
Embodiment 4
(1) 4.0g monosodium glutamate (21mmol) is incorporated with in the round-bottomed flask of absolute methanol 30ml, is placed in cryosel bath, will
6.0mL thionyl chloride (80mmol) is slowly dropped into constant voltage separatory funnel, within 2 hours, drips off magnetic agitation 30min under rear room temperature, and 85
DEG C oil bath is heated to reflux 6 hours, has Precipitation after cooling.By the supernatant buchner funnel sucking filtration after cooling, by filter liquor
It is evaporated with Rotary Evaporators, obtains glutamic acid dimethyl ester hydrochlorate.
(2) by myristic acid 0.457 gram (2mmol) back flow reaction 4 hours in 10mL thionyl chloride, reaction generates myristoyl
Chlorine, dissolves standby with 10mL dichloromethane after steaming thionyl chloride.
(3) amino-reactive completes in the reactor, is joined by 0.424 gram of (2mmol) glutamic acid dimethyl ester hydrochlorate
In 15mL dichloromethane, it is slow added into triethylamine and all dissolves to glutamic acid dimethyl ester hydrochlorate, complete amino-reactive, will step
The dichloromethane solution of the Fructus Amomi Rotundus acyl chlorides that (2) obtain suddenly is added drop-wise in reactor, with TLC monitoring reaction, reacts molten after terminating
Agent i.e. obtains myristoyl glutamic acid dimethyl ester after being evaporated off.
(4) take myristoyl glutamic acid dimethyl ester 0.772 gram (2mmol) 10mL methanol to dissolve, add the hydrogen-oxygen of 2mol/L
Change sodium solution (wherein the molal quantity of sodium hydroxide is 20mmol), determine that formicester blocking group removes completely by TLC detection.Instead
After should terminating, the method distilled by decompression removes methanol and major part aqueous solvent, is transferred to pH 5 with dilute hydrochloric acid, uses ethyl acetate
Extract.Combining extraction liquid, is dried with anhydrous sodium sulfate, utilizes Rotary Evaporators to obtain target product-myristoyl glutamic acid.
Embodiment 5
(1) 4.0g monosodium glutamate (21mmol) is incorporated with in the round-bottomed flask of dehydrated alcohol 20ml, is placed in cryosel bath, will
3.15mL thionyl chloride (42mmol) is slowly dropped into constant voltage separatory funnel, within 2 hours, drips off magnetic agitation 30min under rear room temperature,
80 DEG C of oil baths are heated to reflux 6 hours, have Precipitation after cooling.By the supernatant buchner funnel sucking filtration after cooling, will leach
Liquid Rotary Evaporators is evaporated, and obtains diethyl glutamate hydrochloride.
(2) by myristic acid 0.457 gram (2mmol) back flow reaction 4 hours in 10mL thionyl chloride, reaction generates myristoyl
Chlorine, dissolves standby with 10mL dichloromethane after steaming thionyl chloride.
(3) amino-reactive completes in the reactor, is joined by 0.480 gram of (2mmol) diethyl glutamate hydrochloride
In 2.4mL dichloromethane, it is slow added into triethylamine and all dissolves to diethyl glutamate hydrochloride, complete amino-reactive, will
The dichloromethane solution of the Fructus Amomi Rotundus acyl chlorides that step (2) obtains is added drop-wise in reactor, and with TLC monitoring reaction, reaction will after terminating
Solvent i.e. obtains myristoyl glutamate diethyl ester after being evaporated off.
(4) take myristoyl glutamate diethyl ester 0.828 gram (2mmol) 10mL methanol to dissolve, add the hydrogen-oxygen of 2mol/L
Change sodium solution (wherein the molal quantity of sodium hydroxide is 20mmol), determine that second fat blocking group removes completely by TLC detection.Instead
After should terminating, the method distilled by decompression removes methanol and major part aqueous solvent, is transferred to pH 5 with dilute hydrochloric acid, uses ethyl acetate
Extract.Combining extraction liquid, is dried with anhydrous sodium sulfate, utilizes Rotary Evaporators to obtain target product-myristoyl glutamic acid.
Embodiment 6
(1) 4.0g monosodium glutamate (21mmol) is incorporated with in the round-bottomed flask of absolute methanol 80ml, is placed in cryosel bath, will
9.45mL thionyl chloride (126mmol) is slowly dropped into constant voltage separatory funnel, within 2 hours, drips off magnetic agitation 30min under rear room temperature,
95 DEG C of oil baths are heated to reflux 6 hours, have Precipitation after cooling.By the supernatant buchner funnel sucking filtration after cooling, will leach
Liquid Rotary Evaporators is evaporated, and obtains glutamic acid dimethyl ester hydrochlorate.
(2) by myristic acid 0.457 gram (2mmol) back flow reaction 4 hours in 10mL thionyl chloride, reaction generates myristoyl
Chlorine, dissolves standby with 10mL dichloromethane after steaming thionyl chloride.
(3) amino-reactive completes in the reactor.0.424 gram of (2mmol) glutamic acid dimethyl ester hydrochlorate is joined
In 19.2mL dichloromethane, it is slow added into triethylamine and all dissolves to glutamic acid dimethyl ester hydrochlorate, complete amino-reactive, will
The dichloromethane solution of the Fructus Amomi Rotundus acyl chlorides that step (2) obtains is added drop-wise in reactor, and with TLC monitoring reaction, reaction will after terminating
Solvent i.e. obtains myristoyl glutamic acid dimethyl ester after being evaporated off.
(4) take myristoyl glutamic acid dimethyl ester 0.772 gram (2mmol) 13.74mL methanol to dissolve, add the hydrogen of 2mol/L
By TLC detection, sodium hydroxide solution (wherein the molal quantity of sodium hydroxide is 20mmol), determines that formicester blocking group removes completely.
After reaction terminates, the method distilled by decompression removes methanol and major part aqueous solvent, is transferred to pH 5 with dilute hydrochloric acid, uses acetic acid second
Ester extracts.Combining extraction liquid, is dried with anhydrous sodium sulfate, utilizes Rotary Evaporators to obtain target product-myristoyl paddy ammonia
Acid.
Embodiment 7
(1) prepared by soybean oil alkali solution liquid: take 85.091g (100mL) soybean oil, calculates fat by molal weight 300g/mol
The content of acid, fatty acids 284mmol.Preparation molar concentration is 1mol/L potassium hydroxide-methanol solution, by 100mL
(85.091g) ratio of soybean oil hydro-oxidation potassium-methanol solution 284mL is by soybean oil alkaline hydrolysis, and reaction temperature is 60 DEG C, backflow
30min.Preparing the soybean oil alkali solution liquid containing free fatty for follow-up reaction, the preparation of soybean oil alkali solution liquid is this
Field routine operation, each proportioning raw materials can change within the specific limits.
(2) 4.0g monosodium glutamate (21mmol) is incorporated with in the round-bottomed flask of dehydrated alcohol 30ml, is placed in cryosel bath, will
6.0mL thionyl chloride (80mmol) is slowly dropped into constant voltage separatory funnel, within 2 hours, drips off magnetic agitation 30min under rear room temperature, and 80
DEG C oil bath is heated to reflux 3 hours, has Precipitation after cooling.By the supernatant buchner funnel sucking filtration after cooling, by filter liquor
It is evaporated with Rotary Evaporators, obtains diethyl glutamate hydrochloride.
(3) the soybean oil alkaline hydrolysis product 20mL dichloromethane taking 2.7mL (2mmol) dissolves, and adds the 1-hydroxyl of 2mmol
Benzotriazole (HOBT), 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimine (EDC) of 2mmol, the N of 2mmol, N-bis-
After wopropyl ethyl amine (DIEA), under ice bath, stir 30min, complete activated carboxylic.
(4) diethyl glutamate hydrochloride 0.48g (2mmol) joins in 10mL dichloromethane, adds under stirring
Enter DIEA alkali and make material dissolution.Gained solution is added drop-wise in the reactant liquor that step (3) obtains by constant voltage separatory funnel, overnight
Reaction, detects reaction process with TLC, and reaction uses silicagel column isolated and purified acquisition soybean oil fatty acyl glutamic acid diethyl after terminating
Ester.
(5) take soybean oil fatty acyl glutamate diethyl ester 0.936 gram (2mmol) 10mL methanol to dissolve, add 2mol/L
Sodium hydroxide solution (wherein the molal quantity of sodium hydroxide is 20mmol), by TLC detection determine that second fat blocking group is complete
Removing.After reaction terminates, the method distilled by decompression removes methanol and major part aqueous solvent, is transferred to pH 5 with dilute hydrochloric acid, uses
Ethyl acetate extracts.Combining extraction liquid, is dried with anhydrous sodium sulfate, utilizes Rotary Evaporators to obtain target product-Semen sojae atricolor
Oil and fat acyl glutamic acid.
Embodiment 8
(1) prepared by soybean oil alkali solution liquid: take 85.091g (100mL) soybean oil, calculates fat by molal weight 300g/mol
The content of acid, fatty acids 284mmol；Preparation molar concentration is 1mol/L potassium hydroxide-methanol solution, by 100mL soybean oil
The ratio of hydro-oxidation potassium-methanol solution 312.4mL is by soybean oil alkaline hydrolysis, and alkali is little over amount, and reaction temperature is 90 DEG C, backflow
30min.Prepare the soybean oil alkali solution liquid containing free fatty for follow-up reaction.
(2) 4.0g monosodium glutamate (21mmol) is incorporated with in the round-bottomed flask of absolute methanol 80ml, is placed in cryosel bath, will
9.45mL thionyl chloride (126mmol) is slowly dropped into constant voltage separatory funnel, within 2 hours, drips off magnetic agitation 30min under rear room temperature,
85 DEG C of oil baths are heated to reflux 6 hours, have Precipitation after cooling.By the supernatant buchner funnel sucking filtration after cooling, will leach
Liquid Rotary Evaporators is evaporated, and obtains glutamic acid dimethyl ester hydrochlorate.
(3) the soybean oil alkaline hydrolysis product 20mL dichloromethane taking 2.9mL (2mmol) dissolves, and adds the 1-hydroxyl of 2mmol
Benzotriazole (HOBT), 2mmol dicyclohexylcarbodiimide (DCC), 2mmol DIPEA (DIEA) after,
Stir 30min under ice bath, complete activated carboxylic.
(4) glutamic acid dimethyl ester hydrochlorate 0.424g (2mmol) joins in 10mL dichloromethane, adds under stirring
Enter DIEA alkali and make material dissolution.Gained solution is added drop-wise in the reactant liquor that step (3) obtains by constant voltage separatory funnel, overnight
Reaction, detects reaction process with TLC, and reaction uses silicagel column isolated and purified acquisition soybean oil fatty acyl glutamic acid diformazan after terminating
Ester.
(5) take soybean oil fatty acyl glutamic acid dimethyl ester 0.880 gram (2mmol) 10mL methanol to dissolve, add 2mol/L
Sodium hydroxide solution (wherein the molal quantity of sodium hydroxide is 20mmol), by TLC detection determine that formicester blocking group is complete
Removing.After reaction terminates, the method distilled by decompression removes methanol and major part aqueous solvent, is transferred to pH 5 with dilute hydrochloric acid, uses
Ethyl acetate extracts.Combining extraction liquid, is dried with anhydrous sodium sulfate, utilizes Rotary Evaporators to obtain target product-Semen sojae atricolor
Oil and fat acyl glutamic acid.
Embodiment 9
(1) prepared by soybean oil alkali solution liquid: take 85.091g (100mL) soybean oil, calculates fat by molal weight 300g/mol
The content of acid, fatty acids 284mmol；Preparation molar concentration is 1mol/L potassium hydroxide-methanol solution, by 100mL soybean oil
The ratio of hydro-oxidation potassium-methanol solution 340.8mL is by soybean oil alkaline hydrolysis, and alkali is little over amount, and reaction temperature is 90 DEG C, backflow
30min.Prepare the soybean oil alkali solution liquid containing free fatty for follow-up reaction.
(2) 4.0g monosodium glutamate (21mmol) is incorporated with in the round-bottomed flask of dehydrated alcohol 20ml, is placed in cryosel bath, will
3.15mL thionyl chloride (42mmol) is slowly dropped into constant voltage separatory funnel, within 2 hours, drips off magnetic agitation 30min under rear room temperature,
85 DEG C of oil baths are heated to reflux 6 hours, have Precipitation after cooling.By the supernatant buchner funnel sucking filtration after cooling, will leach
Liquid Rotary Evaporators is evaporated, and obtains diethyl glutamate hydrochloride.
(3) the soybean oil alkaline hydrolysis product 20mL dichloromethane taking 3.1mL (2mmol) dissolves, and adds the 1-hydroxyl of 2mmol
Base benzotriazole (HOBT), the N of 2mmol, N-DIC (DIC), the N of 2mmol, N-diisopropylethylamine
(DIEA), under ice bath, stir 30min, complete activated carboxylic.
(4) diethyl glutamate hydrochloride 0.48g (2mmol) joins in 10mL dichloromethane, adds under stirring
Enter DIEA alkali and make material dissolution.Gained solution is added drop-wise in the reactant liquor of step (3) gained by constant voltage separatory funnel, overnight
Reaction, detects reaction process with TLC, and reaction uses silicagel column isolated and purified acquisition soybean oil fatty acyl glutamic acid diethyl after terminating
Ester.
(5) take soybean oil fatty acyl glutamate diethyl ester 0.936 gram (2mmol) 10mL methanol to dissolve, add 2mol/L
Sodium hydroxide solution (wherein the molal quantity of sodium hydroxide is 20mmol), by TLC detection determine that second fat blocking group is complete
Removing.After reaction terminates, the method distilled by decompression removes methanol and major part aqueous solvent, is transferred to pH 5 with dilute hydrochloric acid, uses
Ethyl acetate extracts.Combining extraction liquid, is dried with anhydrous sodium sulfate, utilizes Rotary Evaporators to obtain target product-Semen sojae atricolor
Oil and fat acyl glutamic acid.
Embodiment 10
(1) prepared by animal oil alkali solution liquid: the Animal fat of purchase is squeezed acquisition animal oil, by molal weight 300g/
Mol calculates the content of fatty acid in animal oil, weighs animal oil 30.0 grams, fatty acids 100mmol；Preparation molar concentration
For 1mol/L potassium hydroxide-methanol solution, in fatty acid, (potassium hydroxide-methanol is molten with the ratio that potassium hydroxide mole is 1:1.2
Liquid 120mL) by animal oil alkaline hydrolysis, alkali is little over amount, and reaction temperature is 90 DEG C, and reflux 30min.Prepare containing free-fat
The animal oil alkali solution liquid of acid is for follow-up reaction.
(2) 4.0g monosodium glutamate (21mmol) is incorporated with in the round-bottomed flask of absolute methanol 80ml, is placed in cryosel bath, will
9.45mL thionyl chloride (126mmol) is slowly dropped into constant voltage separatory funnel, within 2 hours, drips off magnetic agitation 30min under rear room temperature,
85 DEG C of oil baths are heated to reflux 6 hours, have Precipitation after cooling.By the supernatant buchner funnel sucking filtration after cooling, will leach
Liquid Rotary Evaporators is evaporated, and obtains glutamic acid dimethyl ester hydrochlorate.
(3) the animal oil alkaline hydrolysis product 20mL dichloromethane taking 4.5mL (2mmol) dissolves, and adds the 1-hydroxyl of 2mmol
Base benzotriazole (HOBT), 2mmol dicyclohexylcarbodiimide (DCC), 2mmol DIPEA (DIEA) after,
Under ice bath, stir 30min, complete activated carboxylic.
(4) glutamic acid dimethyl ester hydrochlorate 0.424g (2mmol) joins in 10mL dichloromethane, adds under stirring
Enter DIEA alkali and make material dissolution.Gained solution is added drop-wise in the reactant liquor that step (3) obtains by constant voltage separatory funnel, overnight
Reaction, detects reaction process with TLC, and reaction uses silicagel column isolated and purified acquisition animal oil fatty acyl glutamic acid diformazan after terminating
Ester.
(5) take animal oil fatty acyl glutamic acid dimethyl ester 0.880 gram (2mmol) 10mL methanol to dissolve, add 2mol/L
Sodium hydroxide solution (wherein the molal quantity of sodium hydroxide is 20mmol), by TLC detection determine that formicester blocking group is complete
Removing.After reaction terminates, the method distilled by decompression removes methanol and major part aqueous solvent, is transferred to pH 5 with dilute hydrochloric acid, uses
Ethyl acetate extracts.Combining extraction liquid, is dried with anhydrous sodium sulfate, utilizes Rotary Evaporators to obtain target product-animal
Oil and fat acyl glutamic acid.
Embodiment 11
(1) 4.0g monosodium glutamate (21mmol) is incorporated with in the round-bottomed flask of dehydrated alcohol 20ml, is placed in cryosel bath, will
3.15mL thionyl chloride (42mmol) is slowly dropped into constant voltage separatory funnel, controls uniformly to drip off, after dripping off in 2 hours
Magnetic agitation 30min under room temperature, 80 DEG C of oil baths are heated to reflux 3 hours, have Precipitation after cooling, are used by the supernatant after cooling
Buchner funnel sucking filtration, is evaporated filter liquor Rotary Evaporators, obtains diethyl glutamate hydrochloride.
(2) take oleic acid 0.565g (2mmol), dissolve with 10mL dichloromethane, be separately added into the 1-hydroxy benzo three of 2mmol
Azoles (HOBT), the O-BTA-tetramethylurea hexafluorophosphate (HBTU) of 2mmol, the N of 2mmol, N-diisopropylethylamine
(DIEA) after, stir 30 minutes under ice bath, then the step (1) dissolved by 10mL dichloromethane with constant voltage separatory funnel obtains
After the DIEA of diethyl glutamate hydrochloride 0.48g (2mmol) and 2mmol is slowly dropped into, stirs 1 hour under ice bath, remove ice
Rear room temperature reaction overnight, terminates, with silicagel column isolated and purified acquisition oils and fats to reaction with thin layer chromatography (TLC) detection reaction process
Acyl glutamate diethyl ester.
(3) take oils and fats acyl glutamate diethyl ester 0.936 gram (2mmol) 13mL methanol to dissolve, add the hydrogen-oxygen of 2mol/L
Change sodium solution (wherein the molal quantity of sodium hydroxide is 20mmol), determine that second fat blocking group removes completely by TLC detection.Instead
After should terminating, the method distilled by decompression removes methanol and major part aqueous solvent, is transferred to pH 5 with dilute hydrochloric acid, uses ethyl acetate
Extract.Combining extraction liquid, is dried with anhydrous sodium sulfate, utilizes Rotary Evaporators to obtain target product-oils and fats acyl glutamic acid.
Embodiment 12
(1) prepared by animal oil alkali solution liquid: the Animal fat of purchase is squeezed acquisition animal oil, by molal weight 300g/
Mol calculates the content of fatty acid in animal oil, weighs animal oil 30.0 grams, fatty acids 100mmol；Preparation molar concentration
For 1mol/L potassium hydroxide-methanol solution, in fatty acid, (potassium hydroxide-methanol is molten with the ratio that potassium hydroxide mole is 1:1.2
Liquid 120mL) by animal oil alkaline hydrolysis, alkali is little over amount, and reaction temperature is 90 DEG C, and reflux 30min.Prepare containing free-fat
The animal oil alkali solution liquid of acid is for follow-up reaction.
(2) 4.0g monosodium glutamate (21mmol) is incorporated with in the round-bottomed flask of absolute methanol 80ml, is placed in cryosel bath, will
9.45mL thionyl chloride (126mmol) is slowly dropped into constant voltage separatory funnel, within 2 hours, drips off magnetic agitation 30min under rear room temperature,
85 DEG C of oil baths are heated to reflux 6 hours, have Precipitation after cooling.By the supernatant buchner funnel sucking filtration after cooling, will leach
Liquid Rotary Evaporators is evaporated, and obtains glutamic acid dimethyl ester hydrochlorate.
(3) the animal oil alkaline hydrolysis product 20mL dichloromethane taking 4.5mL (2mmol) dissolves, and adds the 1-hydroxyl of 2mmol
Base benzotriazole (HOBT), the O-BTA-tetramethylurea hexafluorophosphate (HBTU) of 2mmol, the N of 2mmol, N-bis-is different
After propylethylamine (DIEA), under ice bath, stir 30min, complete activated carboxylic.
(4) glutamic acid dimethyl ester hydrochlorate 0.424g (2mmol) joins in 10mL dichloromethane, adds under stirring
Enter DIEA alkali and make material dissolution.Gained solution is added drop-wise in the reactant liquor that step (3) obtains by constant voltage separatory funnel, overnight
Reaction, detects reaction process with TLC, and reaction uses silicagel column isolated and purified acquisition animal oil fatty acyl glutamic acid methyl ester after terminating.
(5) take animal oil fatty acyl glutamic acid dimethyl ester 0.880 gram (2mmol) 10mL methanol to dissolve, add 2mol/L
Sodium hydroxide solution (wherein the molal quantity of sodium hydroxide is 20mmol), by TLC detection determine that formicester blocking group is complete
Removing.After reaction terminates, the method distilled by decompression removes methanol and major part aqueous solvent, is transferred to pH 5 with dilute hydrochloric acid, uses
Ethyl acetate extracts.Combining extraction liquid, is dried with anhydrous sodium sulfate, utilizes Rotary Evaporators to obtain target product-animal
Oil and fat acyl glutamic acid.
Claims (10)
1. one kind utilizes the method that anionic surfactant prepared by monosodium glutamate, it is characterised in that the method comprises the steps:
Monosodium glutamate first utilizes esterification carry out carboxy protective, and recycling Long carbon chain fatty acid carries out amido modified, finally hydrolyzes removal
The esterification protection group of carboxyl.
The method preparing anionic surfactant the most as claimed in claim 1, it is characterised in that described esterification
Including ethyl esterified or esterification.
The method preparing anionic surfactant the most as claimed in claim 1, it is characterised in that described Long carbon chain fat
Fat acid is the carbochain fatty acid that contains more than 8 carbon atoms or oils and fats alkaline hydrolysis product in alcoholic solution.
The method preparing anionic surfactant the most as claimed in claim 3, it is characterised in that described oils and fats is for planting
Thing oil or animal oil.
The method preparing anionic surfactant the most as claimed in claim 1, it is characterised in that described Long carbon chain fat
Fat acid band has more than 1 double bond.
The method preparing anionic surfactant the most as claimed in claim 1, it is characterised in that described is amido modified
It is that Long carbon chain fatty acid has reacted under the effect of condensing agent with glutamate diethyl ester or glutamic acid dimethyl ester.
The method preparing anionic surfactant the most as claimed in claim 6, it is characterised in that described condensing agent is
1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimine (EDC), dicyclohexylcarbodiimide (DCC), N, N-diisopropyl carbon
Diimine (DIC) or O-BTA-tetramethylurea hexafluorophosphate (HBTU).
8. the preparation method of anionic surfactant as claimed in claim 1, it is characterised in that described is amido modified
It is after Long carbon chain fatty acid reacts with thionyl chloride, then has reacted with glutamate diethyl ester or glutamic acid dimethyl ester.
9. the preparation method of anionic surfactant as claimed in claim 1, it is characterised in that the method includes as follows
Step: (1) carboxy protective: monosodium glutamate is added in dehydrated alcohol or absolute methanol, monosodium glutamate and dehydrated alcohol or the matter of absolute methanol
Amount volume ratio is 1:(5-20), be placed in the environment of less than 0 DEG C, thionyl chloride be slowly added to, thionyl chloride mole
Number is 2-6 times of monosodium glutamate, stirs after adding, then carries out oil bath and be heated to reflux, cool down, cooled and filtered, then by filtrate
It is evaporated, i.e. obtains glutamate diethyl ester or glutamic acid dimethyl ester；(2) amido modified: glutamate diethyl ester or glutamic acid dimethyl ester
With Long carbon chain fatty acid response, complete amido modified after obtain fatty acyl glutamate diethyl ester or fatty acyl paddy ammonia through isolated and purified
Dimethyl phthalate；(3) carboxyl-protecting group is removed: fatty acyl glutamate diethyl ester step (2) obtained or fatty acyl glutamic acid two
Methyl ester methanol dissolves, and is added thereto to the sodium hydroxide solution of 2mol/L, and wherein the molal quantity of sodium hydroxide is fatty acyl paddy
Propylhomoserin diethylester or 10 times of fatty acyl glutamic acid dimethyl ester molal quantity, after reaction terminates, remove first alcohol and water, with the hydrochloric acid of 1N
Adjust pH5, and make to be extracted with ethyl acetate, combining extraction liquid drying, evaporate.
10. the anionic surfactant that a method according to claim 1 prepares.
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| 王多闻: "N-酰基氨基酸系表面活性剂", 《日用化学品工业》 * |
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