CN103980150B - A kind of synthetic method of fatty alcohol ether alkanoylamino acid sodium - Google Patents
A kind of synthetic method of fatty alcohol ether alkanoylamino acid sodium Download PDFInfo
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Abstract
The invention discloses the synthetic method of a kind of fatty alcohol ether alkanoylamino acid sodium, after fatty alcohol ether and sodium hydroxide carry out alkali process reaction, react with the mixture of fatty alcohol ether and alkylcarboxylic acid sodium, the fatty alcohol ether sodium carboxylate generated with acid solution acidifying, the most extracted, wash and be dried, obtain fatty alcohol ether alkyl carboxylic acid, the fatty alcohol ether alkyl carboxylic acid being dried and thionyl chloride carry out acylation reaction, its product fatty alcohol ether alkyl acyl chloride oxolane being dried dissolves, last and amino acid sodium carries out condensation reaction, prepare fatty alcohol ether alkanoylamino acid sodium, product has good antibacterial and sterilization and compatibility performance, and there is stability in hard water energy.
Description
Technical field
The present invention relates to amino acid surfactant synthesis technical field, the synthetic method of a kind of fatty alcohol ether alkanoylamino acid sodium.
Background technology
Surfactant is a kind of material that target solution surface tension can be made to be remarkably decreased, the surface tension between two kinds of liquid or liquid-solid can be reduced, surfactant as industry monosodium glutamate, because of in the unique effects produced and in life, it is widely used in the every field of the national economic development, it is considered as that one is the most wide in variety, purposes is wide, the fine chemical product that demand is big, but, substantial amounts of surfactant enters in water sweetening of the soil, meeting welding, contaminated soil, so, we are while paying close attention to surfactant properties, also biodegradation and the biological adaptation ability of surfactant should be focused more on, therefore, increasing to the demand of the high performance surface activating agent researching and developing high biological degradability and biocompatibility.
Amino acid surfactant is not only high to the safety of environmental and biological materials, to hair and skin action temperature and, zest is little, low toxicity, and also have the compatibility that other various surfactants are good, and good antibacterial and bactericidal property, exactly because these excellent surface propertys that it is had, it is made not only to meet environment amenable requirement, and meet the requirement that product mildness and safety are improved constantly by people, surfactant is prepared with aminoacid, the response characteristic of amino acid whose amino or carboxyl must be utilized, introduce hydrophobic group, to a certain extent, the characteristic of hydrophobic group affects the performance of amino acid surfactant.
Summary of the invention
It is an object of the invention to provide the synthetic method of a kind of fatty alcohol ether alkanoylamino acid sodium.
The technical solution of the present invention is: after fatty alcohol ether and sodium hydroxide carry out alkali process reaction; react with the mixture of fatty alcohol ether and alkylcarboxylic acid sodium; the fatty alcohol ether sodium carboxylate generated with acid solution acidifying; the most extracted, wash and be dried; obtain fatty alcohol ether alkyl carboxylic acid; the fatty alcohol ether alkyl carboxylic acid being dried and thionyl chloride carry out acylation reaction; its product fatty alcohol ether alkyl acyl chloride oxolane being dried dissolves; last and amino acid sodium carries out condensation reaction; prepare fatty alcohol ether alkanoylamino acid sodium, specifically comprise the steps of
1). fatty alcohol ether (I) and sodium hydroxide, at 105 DEG C～115 DEG C, stir and lead to nitrogen protection, carry out after alkali under the conditions of reduced vacuum processes reaction 2～4 hours, being cooled to 50 DEG C～60 DEG C, generating fatty alcohol ether sodium (II)；Its main chemical reactions is:
2). fatty alcohol ether (I) mixes with mass ratio 11 in advance with alkylcarboxylic acid sodium (III), its mixture and fatty alcohol ether sodium (II) are under 50 DEG C～60 DEG C of temperature and stirring condition, proceed to react 3～5 hours, generate fatty alcohol ether sodium carboxylate (IV)；Its main chemical reactions is:
3). reaction product fatty alcohol ether sodium carboxylate (IV) is diluted with water, is slowly added to acid solution acidifying, adjusts PH to 1～2, acidizing product is extracted by ethyl acetate after acidifying, washing acidizing product with water the most neutral, anhydrous sodium sulfate is dried, and obtains fatty alcohol ether alkyl carboxylic acid (V)；Its main chemical reactions is:
4). the fatty alcohol ether alkyl carboxylic acid (V) being dried and thionyl chloride (VI), it is heated to 65 DEG C～75 DEG C, carry out reacting 2～3 hours, tail gas alkali liquor absorption, normal pressure boils off the thionyl chloride of excess afterwards, yellow liquid fatty alcohol ether alkyl acyl chloride (VI) obtained, with oxolane dissolved fat alcohol ether alkyl acyl chloride (VI) being dried, standby；Its main chemical reactions is:
5). in aminoacid (VII), add the sodium hydroxide solution of 20%, regulate PH=9～10, carry out reacting 1 hour, prepare amino acid sodium (VIII) solution, standby；Its main chemical reactions is:
6). at a temperature of 0～5 DEG C; drip the tetrahydrofuran solution of fat alcohol ether alkyl acyl chloride (VI) with the speed of 3～4 ml/min in amino acid sodium (VIII) solution; dropping limit, limit is sufficiently stirred for; it is simultaneously added dropwise the sodium hydroxide solution of 20%, to keep reaction system PH=9～10, after dropping; keep temperature of reaction system 0～5 DEG C; carry out reacting 3～5 hours, boil off tetrahydrofuran solvent, generate fatty alcohol ether alkanoylamino acid sodium (Ⅸ).Its main chemical reactions is:
Wherein, the R in reaction equation1Be carbon number be C12～C18Primary alconol or secondary alcohol；N is the integer of 3～9；R2Be carbon number be C1～C5Alkylidene；X is chlorine element or bromo element； R3The carbon number being is C1～C6Alkyl or hydrogen.
Further, described fatty alcohol ether preferred sec-12 carbocyclic aliphatic alcohol ether, sec-14 carbocyclic aliphatic alcohol ether and sec-16 carbocyclic aliphatic alcohol ether and sec-18 carbocyclic aliphatic alcohol ether and mixed alcohol ether thereof.
Described alkylcarboxylic acid sodium preferred 3-chloropropionic acid sodium and 4-bromo-butyric acid sodium.
The mol ratio of described fatty alcohol ether, sodium hydroxide and alkylcarboxylic acid sodium is 1 1.2～1.3 1.1～1.2.
Described fatty alcohol ether alkyl carboxylic acid is 1 2.5～3.0 with the mol ratio of thionyl chloride.
The preferred glycine of described aminoacid, alanine, valine, leucine and isoleucine.
Described fatty alcohol ether alkyl acyl chloride and amino acid sodium mol ratio are 1 1.6～1.8.
Described acid solution is dilution heat of sulfuric acid or the dilute hydrochloric acid solution of 4 mol/L.
The synthetic method of the present invention a kind of fatty alcohol ether alkanoylamino acid sodium; its feature and advantage be: synthetic is a kind of alkyl phenol ether acetylamino acids; to hair and skin action temperature and; zest is little, low toxicity; and also have the compatibility that other various surfactants are good; and good antibacterial and bactericidal property, there is stability in hard water energy.
Detailed description of the invention
Embodiment 1
In the four-hole bottle equipped with agitator and thermometer, add 35.8 grams of sec-14 carbocyclic aliphatic alcohol ethers (mean molecule quantity 508.4) and 4.8 grams of sodium hydroxide, logical nitrogen protection, it is heated to 105 DEG C～110 DEG C, under stirring condition, carry out after alkali under the conditions of reduced vacuum processes reaction 4 hours, it is cooled to 60 DEG C, generate sec-14 carbocyclic aliphatic alcohol ether sodium, by the sec-14 carbocyclic aliphatic alcohol ether 15 grams mixed in advance and 15 grams of 3-chloropropionic acid sodium, join in four-hole bottle, under 54 DEG C～58 DEG C of temperature and stirring condition, proceed to react 5 hours, generate sec-14 carbocyclic aliphatic alcohol ether sodium carboxylate；In four-hole bottle, 80 grams of water are diluted, it is slowly added to the dilution heat of sulfuric acid of 4 mol/L, adjust PH to 1～2, acidizing product is extracted by 150 grams of ethyl acetate after acidifying, wash acidizing product with water to neutral, anhydrous sodium sulfate is dried, obtain sec-14 carbocyclic aliphatic alcohol ether propanoic acid, the sec-14 carbocyclic aliphatic alcohol ether propanoic acid being dried joins equipped with agitator, thermometer, in four necks of reflux condenser and drying tube, add 355 grams of thionyl chlorides, it is heated to 65 DEG C～70 DEG C, carry out reacting 2.5 hours, tail gas alkali liquor absorption, normal pressure boils off the thionyl chloride of excess afterwards, the yellow liquid sec-14 carbocyclic aliphatic alcohol ether propionyl chloride the obtained oxolane 200 milliliters dissolving being dried, standby；The sodium hydroxide solution of 20% is added in 22 grams of leucines, regulation PH=9～10, carry out reacting 1 hour, prepare (S)-Leucine sodium salt solution, then this solution is joined equipped with agitator, thermometer, in four necks of reflux condenser, the bath of solution low-temp reaction is cooled to 0～5 DEG C, at a temperature of 0～5 DEG C, drip the tetrahydrofuran solution of sec-14 carbocyclic aliphatic alcohol ether propionyl chloride with the speed of 5 ml/min in four necks, dropping limit, limit is sufficiently stirred for, it is simultaneously added dropwise the sodium hydroxide solution of 20%, to keep reaction system PH=9～10, after dropping, keep temperature of reaction system 0～5 DEG C, carry out reacting 5 hours, boil off tetrahydrofuran solvent, generate sec-14 carbocyclic aliphatic alcohol ether propiono (S)-Leucine sodium salt.
Embodiment 2
In the four-hole bottle equipped with agitator and thermometer, add 15 gram of 16 carbocyclic aliphatic alcohol ether (mean molecule quantity 374.5) and 5.2 grams of sodium hydroxide, logical nitrogen protection, it is heated to 110 DEG C～115 DEG C, under stirring condition, carry out after alkali under the conditions of reduced vacuum processes reaction 3 hours, it is cooled to 55 DEG C, generate 16 carbocyclic aliphatic alcohol ether sodium, by the 16 carbocyclic aliphatic alcohol ether 22.6 grams mixed in advance and 22.6 grams of 4-bromo-butyric acid sodium, join in four-hole bottle, under 55 DEG C～60 DEG C of temperature and stirring condition, proceed to react 3 hours, generate 16 carbocyclic aliphatic alcohol ether sodium butyrates；In four-hole bottle, 100 grams of water are diluted, it is slowly added to the dilute hydrochloric acid solution of 4 mol/L, adjust PH to 1～2, acidizing product is extracted by 190 grams of ethyl acetate after acidifying, wash acidizing product with water to neutral, anhydrous sodium sulfate is dried, obtain 16 carbocyclic aliphatic alcohol ether butanoic acid, the 16 carbocyclic aliphatic alcohol ether butanoic acid being dried join equipped with agitator, thermometer, in four necks of reflux condenser and drying tube, add 330 grams of thionyl chlorides, it is heated to 60 DEG C～70 DEG C, carry out reacting 3 hours, tail gas alkali liquor absorption, normal pressure boils off the thionyl chloride of excess afterwards, the yellow liquid 16 carbocyclic aliphatic alcohol ether butyl chloride the obtained oxolane 240 milliliters dissolving being dried, standby；In 142.5 grams of alanine, add the sodium hydroxide solution of 20%, regulate PH=9～10, carry out reacting 1 hour, prepare Sodium L-alaninate solution, then this solution is joined equipped with agitator, thermometer, in four necks of reflux condenser, the bath of solution low-temp reaction is cooled to 0～5 DEG C
At a temperature of 0～5 DEG C; drip the tetrahydrofuran solution of 16 carbocyclic aliphatic alcohol ether butyl chlorides with the speed of 4 ml/min in four necks; dropping limit, limit is sufficiently stirred for; it is simultaneously added dropwise the sodium hydroxide solution of 20%, to keep reaction system PH=9～10, after dropping; keep temperature of reaction system 0～5 DEG C; carry out reacting 4 hours, boil off tetrahydrofuran solvent, generate 16 carbocyclic aliphatic alcohol ether bytyry Sodium L-alaninates.
Embodiment 3
In the four-hole bottle equipped with agitator and thermometer, add 40.6 grams of sec-12 carbon～sec-18 carbocyclic aliphatic alcohol ether (mean molecule quantity 605) and 5 grams of sodium hydroxide, logical nitrogen protection, it is heated to 108 DEG C～112 DEG C, under stirring condition, carry out after alkali under the conditions of reduced vacuum processes reaction 2 hours, it is cooled to 50 DEG C, generate sec-12 carbocyclic aliphatic alcohol ether sodium, by the sec-12 carbocyclic aliphatic alcohol ether 14.4 grams mixed in advance and 14.4 grams of 3-chloropropionic acid sodium, join in four-hole bottle, under 50 DEG C～55 DEG C of temperature and stirring condition, proceed to react 4 hours, generate sec-12 carbocyclic aliphatic alcohol ether alkylpropionic acids sodium；In four-hole bottle, 90 grams of water are diluted, it is slowly added to the dilution heat of sulfuric acid of 4 mol/L, adjust PH to 1～2, acidizing product is extracted by 170 grams of ethyl acetate after acidifying, wash acidizing product with water to neutral, anhydrous sodium sulfate is dried, obtain sec-12 carbocyclic aliphatic alcohol ether propanoic acid, the sec-12 carbocyclic aliphatic alcohol ether propanoic acid being dried joins equipped with agitator, thermometer, in four necks of reflux condenser and drying tube, add 300 grams of thionyl chlorides, it is heated to 70 DEG C～80 DEG C, carry out reacting 2 hours, tail gas alkali liquor absorption, normal pressure boils off the thionyl chloride of excess afterwards, the yellow liquid the obtained oxolane 220 milliliters dissolving being dried, standby；The sodium hydroxide solution of 20% is added in 135 grams of glycine, regulation PH=9～10, carry out reacting 1 hour, prepare sodium glycinate solution, then this solution is joined equipped with agitator, thermometer, in four necks of reflux condenser, the bath of solution low-temp reaction is cooled to 0～5 DEG C, at a temperature of 0～5 DEG C, drip the tetrahydrofuran solution of sec-12 carbocyclic aliphatic alcohol ether propionyl chloride with the speed of 4 ml/min in four necks, dropping limit, limit is sufficiently stirred for, it is simultaneously added dropwise the sodium hydroxide solution of 20%, to keep reaction system PH=9～10, after dropping, keep temperature of reaction system 0～5 DEG C, carry out reacting 3 hours, boil off tetrahydrofuran solvent, generate sec-12 carbon～sec-18 carbocyclic aliphatic alcohol ether propiono Glycine sodium.
The above; embodiment is only to be described the preferred embodiment of the present invention; not the scope of the present invention is defined; on the premise of without departing from the spirit of the technology of the present invention; various deformation that technical scheme is made by this area engineers and technicians and improvement, all should fall in the protection domain that claims of the present invention determines.
Claims (2)
1. the synthetic method of a fatty alcohol ether alkanoylamino acid sodium, it is characterized in that: after fatty alcohol ether and sodium hydroxide carry out alkali process reaction, react with the mixture of fatty alcohol ether and alkylcarboxylic acid sodium, the fatty alcohol ether sodium carboxylate generated with acid solution acidifying, the most extracted, wash and be dried, obtain fatty alcohol ether alkyl carboxylic acid, the fatty alcohol ether alkyl carboxylic acid being dried and thionyl chloride carry out acylation reaction, its product fatty alcohol ether alkyl acyl chloride oxolane being dried dissolves, last and amino acid sodium carries out condensation reaction, prepare fatty alcohol ether alkanoylamino acid sodium, specifically comprise the steps of
1). fatty alcohol ether and sodium hydroxide, at 105 DEG C～115 DEG C, stir and lead to nitrogen protection, carry out after alkali under the conditions of reduced vacuum processes reaction 2～4 hours, being cooled to 50 DEG C～60 DEG C, generating fatty alcohol ether sodium；
2). fatty alcohol ether mixes with mass ratio 11 in advance with alkylcarboxylic acid sodium, and its mixture and fatty alcohol ether sodium, under 50 DEG C～60 DEG C of temperature and stirring condition, proceed to react 3～5 hours, generates fatty alcohol ether sodium carboxylate；
3). reaction product fatty alcohol ether sodium carboxylate water is diluted, and is slowly added to acid solution acidifying, adjusts pH to 1～2, acidizing product is extracted by ethyl acetate after acidifying, washing acidizing product with water the most neutral, anhydrous sodium sulfate is dried, and obtains fatty alcohol ether alkyl carboxylic acid；
4). the fatty alcohol ether alkyl carboxylic acid being dried and thionyl chloride, it is heated to 65 DEG C～75 DEG C, carry out reacting 2～3 hours, tail gas alkali liquor absorption, normal pressure boils off the thionyl chloride of excess afterwards, the yellow liquid fatty alcohol ether alkyl acyl chloride obtained, with the oxolane dissolved fat alcohol ether alkyl acyl chloride being dried, standby；
5). in aminoacid, add the sodium hydroxide solution of 20%, regulate pH=9～10, carry out reacting 1 hour, prepare amino acid sodium solution, standby；
6). at a temperature of 0～5 DEG C; drip the tetrahydrofuran solution of fat alcohol ether alkyl acyl chloride with the speed of 3～4 ml/min in amino acid sodium solution; dropping limit, limit is sufficiently stirred for; it is simultaneously added dropwise the sodium hydroxide solution of 20%, to keep reaction system PH=9～10, after dropping; keep temperature of reaction system 0～5 DEG C; carry out reacting 3～5 hours, boil off tetrahydrofuran solvent, generate fatty alcohol ether alkanoylamino acid sodium.
The synthetic method of a kind of fatty alcohol ether alkanoylamino acid sodium the most according to claim 1, is characterized in that: described fatty alcohol ether is selected from sec-12 carbocyclic aliphatic alcohol ether, sec-14 carbocyclic aliphatic alcohol ether and sec-16 carbocyclic aliphatic alcohol ether and sec-18 carbocyclic aliphatic alcohol ether and mixed alcohol ether thereof；Described alkylcarboxylic acid sodium is selected from 3-chloropropionic acid sodium and 4-bromo-butyric acid sodium；The mol ratio of described fatty alcohol ether, sodium hydroxide and alkylcarboxylic acid sodium is 1 1.2～1.3 1.1～1.2；Described fatty alcohol ether alkyl carboxylic acid is 1 2.5～3.0 with the mol ratio of thionyl chloride；Described aminoacid is selected from glycine, alanine, valine, leucine and isoleucine；Described fatty alcohol ether alkyl acyl chloride and amino acid sodium mol ratio are 1 1.6～1.8；Described acid solution is dilution heat of sulfuric acid or the dilute hydrochloric acid solution of 4 mol/L.
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