CN113481247B - Preparation method of medium-carbon-chain triglyceride - Google Patents
Preparation method of medium-carbon-chain triglyceride Download PDFInfo
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- CN113481247B CN113481247B CN202110818322.7A CN202110818322A CN113481247B CN 113481247 B CN113481247 B CN 113481247B CN 202110818322 A CN202110818322 A CN 202110818322A CN 113481247 B CN113481247 B CN 113481247B
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6436—Fatty acid esters
- C12P7/6445—Glycerides
- C12P7/6454—Glycerides by esterification
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/39—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing halogen atoms bound to the carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
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Abstract
The invention relates to the field of organic synthesis, and particularly relates to a preparation method of medium-carbon-chain triglyceride. The preparation method comprises the step of reacting glycerol, medium-chain fatty acid and lipase in an ionic liquid to obtain medium-chain triglyceride, wherein the ionic liquid has a structure shown in the formula I. When the formula I is used as a solvent in lipase catalytic synthesis, the lipase has higher reaction activity, so that the reaction efficiency and the reaction rate are higher, and the reaction is more complete.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a preparation method of medium-carbon-chain triglyceride.
Background
Fatty acid radicals are divided into short chains, medium chains and long chains according to the length of the carbon chain, and fatty acid containing 6-12 carbon atoms as a carbon chain is generally called Medium Chain Fatty Acid (MCFA), and three hydroxyl groups of glycerol form ester to form medium chain fatty acid triglyceride (or medium chain triglyceride, MCT). Typically MCT refers to saturated caprylic triglyceride or saturated capric triglyceride or a mixed saturated caprylic-capric triglyceride.
MCT is a low-calorie structural lipid and has wide applications in foods, pharmaceuticals, and cosmetics. Currently, MCT synthesis is classified into chemical methods and biological methods according to the types of catalysts, and the reaction types mainly include esterification reaction and alcoholysis reaction.
Chinese patent application CN108383722A discloses a method for industrially preparing medium carbon chain triglycerides, comprising: taking glycerol, caprylic acid and capric acid as raw materials, adding an acidic solid catalyst under the conditions of heating and decompression, continuously heating and stirring to complete esterification reaction, and generating a lipid mixture containing the solid catalyst; filtering the solid catalyst by a filter to obtain a crude product of the medium carbon chain triglyceride; and refining and purifying the medium carbon chain triglyceride crude product by using an industrial molecular distillation device to obtain a medium carbon chain triglyceride finished product. Wherein the mass ratio of the glycerol to the caprylic acid to the capric acid is 1: 2.5-4.5: 1.0 to 2.0. The acidic solid catalyst is macroporous strong-acid cation exchange resin, the adding amount of the acidic solid catalyst is 4-10% of the total mass of the glycerol, the caprylic acid and the capric acid, the purity of the obtained medium-carbon chain triglyceride is more than 98%, and the method is green, pollution-free and suitable for continuous industrial production.
Chinese patent application CN108893500A discloses a method for preparing medium-long chain triglycerides, which is characterized by comprising the following steps: (1) placing the immobilized enzyme in a reactor, and preheating the reactor; (2) adding long-chain triglyceride and medium-chain triglyceride into a reactor trough as reaction materials, preheating, putting into a reactor, adding a transesterification catalyst, introducing nitrogen, uniformly mixing the materials, and performing transesterification reaction at constant temperature; (3) subjecting the product mixture of the transesterification reaction obtained in the step (2) to molecular distillation to obtain medium-long chain triglyceride; (4) putting the medium-long chain triglyceride and the medium-chain fatty acid obtained in the step (3) into a reactor with built-in immobilized enzyme, adding an activated enzyme catalyst, and introducing nitrogen to perform acidolysis reaction on the uniformly mixed material at a constant temperature; (5) and (4) distilling and refining the acidolysis reaction product obtained in the step (4) to obtain medium-long chain triglyceride.
Chinese patent application CN102492743A discloses a method for preparing medium carbon chain triglyceride in ionic liquid: mixing glycerol and caprylic acid according to the mass ratio of 1: 3-5, taking ionic liquid as a reaction medium, reacting for 2-48 h at 40-80 ℃ under the catalysis of lipase, centrifuging reaction liquid after the reaction is finished, precipitating and drying to obtain medium-carbon chain triglyceride; the ionic liquid is C4-C16 alkyl imidazole ionic liquid containing PF6-, Tf 2N-or BF 4-anions; the lipase is immobilized lipase Novozyme435 or immobilized lipase lipozyme RMIM; the preparation process is green, efficient, simple, convenient for large-scale production and easy for large-scale production.
Disclosure of Invention
The invention aims at solving the problem that no suitable ionic liquid system and method for producing medium-carbon chain triglyceride exist in the prior art, provides a method for preparing medium-carbon chain triglyceride by using an ionic liquid, and also provides a preparation method of the ionic liquid.
A method for preparing medium-chain triglyceride, which comprises the step of reacting glycerol, medium-chain fatty acid and lipase in an ionic liquid to obtain the medium-chain triglyceride, wherein the ionic liquid has a structure shown in the following formula I:
further, the medium carbon chain fatty acid is selected from C6-C12Fatty acids, preferably C6-C10Fatty acids, more preferably C8-C10A fatty acid.
Further, the lipase is selected from at least one of candida lipase.
Further, the activity of the lipase is 5000-10000U/g, preferably 5000U/g.
Wherein the candida lipase is selected from the group consisting of: candida Antarctica (Candida Antarctica) lipase A, Candida Antarctica (Candida Antarctica) lipase B, Candida cylindracea (Candida cylindracae) lipase, Candida malformation (Candida deformans) lipase, Candida lipolytica (Candida lipolytica) lipase, Candida parapsilosis (Candida parapsilosis) lipase, Candida rugosa (Candida rugosa) lipase; preferably Candida Antarctica lipase B.
Further, the lipase is an immobilized lipase.
Further, the immobilized lipase is selected from one of acrylic resin immobilized lipase, multi-wall carbon nanotube immobilized lipase or IL magnetic nanoparticle immobilized lipase.
Further, the molar ratio of glycerol to medium carbon chain fatty acids may be 1:3-4, alternatively 1:3, 1:3.03, 1:3.1, 1:3.3, 1:3.5 or 1: 4. Preferably 1: 3-3.3, more preferably 1: 3.1.
Further, the lipase is used in an amount of 1-3 wt% of the total amount of medium-chain fatty acids and glycerol, by weight.
Further, the ionic liquid is used in an amount of 20 to 30 wt% of the total amount of medium-chain fatty acids and glycerin.
Further, the reaction temperature is 60-70 ℃.
Further, the reaction time is 12-24 h.
The invention also provides a preparation method of the formula I, which comprises the following steps:
s1: reacting benzyl alcohol with 4-trifluoromethylbenzenesulfonyl chloride to obtain 4-trifluoromethylbenzenesulfonic acid benzyl ester;
s2: and reacting the 4-trifluoro toluene sulfonic acid benzyl ester with pyridine to obtain the ionic liquid.
The invention has the advantages that:
1. the invention unexpectedly discovers that when the formula I is used as lipase for catalyzing and synthesizing medium-chain fatty glyceride, the lipase can have higher reaction activity, so that the reaction efficiency and the reaction rate are higher, and the reaction is more complete.
2. When the ionic liquid of the formula I is used as a reaction medium, a higher esterification rate can be obtained in a shorter time and with a smaller amount of enzyme when the amount of the formula I is smaller.
3. The ionic liquid prepared by the method disclosed by the invention can be obtained without anion replacement, and the operation is simpler and more efficient.
Detailed Description
The enzymes used in the following examples were purchased from Novozymes, Novozym 435 was an immobilized enzyme, lipozyme CALB was obtained by freeze-drying a solution of Novozymes lipozyme CALBL enzyme, and the activity of the enzyme used was adjusted to 5000U/g using glycerol.
Example 1
Preparation of formula I
S1: benzyl alcohol (1mol) and triethylamine (1.5mol) were dissolved in 8L 2-MeTHF, 4-trifluoromethylbenzenesulfonyl chloride (1.02mol) was added dropwise, and the complete reaction of benzyl alcohol was monitored by TLC using 2LHCl (1M), 2L NaOH (1M) and 2LH in that order2And (4) extracting, concentrating and drying an organic phase to obtain 4-trifluoro toluene sulfonic acid benzyl ester (0.95mol, HPLC purity is 99.7%).
S2: dissolving 4-trifluoro-toluene sulfonic acid benzyl ester (0.5mol) in pyridine (1mol), heating and refluxing, and after TLC monitoring that 4-trifluoro-toluene sulfonic acid benzyl ester (0.5mol) completely reacts, removing redundant pyridine under reduced pressure to obtain the ionic liquid (0.5mol, HPLC purity is 99.5%) of the formula I.
Preparation example
Preparation method of medium-carbon-chain triglyceride
Mixing glycerol, medium-chain fatty acid, lipase and the ionic liquid of the formula I, and heating for reaction to obtain the compound.
Specific parameters and experimental results of the inventive and comparative examples are shown in table 1.
TABLE 1 preparation parameters and results
The lipase dosage and the ionic liquid dosage in the invention are calculated based on the total mass of glycerol and fatty acid.
As can be seen from Table 1, the scheme of the invention has better universality in the esterification reaction of medium-chain fatty acid and glycerol, and can be used for synthesizing glycerol fatty acid ester with single composition and also can be used for synthesizing glycerol fatty acid ester with mixed composition.
Comparative example 1
In contrast to preparation example 1, use is made of [ C4MIM]PF6As the ionic liquid, the final esterification rate of the reaction was 45%.
Comparative example 2
The difference from preparation example 1 is that 1-butyl-3-methylimidazole p-toluenesulfonate was used as an example liquid, and the final esterification rate was 63%.
The method can show that different ionic liquids have larger influence on the final esterification rate, and the ionic liquid provided by the invention can enable the reaction to obtain higher esterification rate in the catalytic synthesis of MCT.
Finally, it should be noted that the above-mentioned contents are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, and that the simple modifications or equivalent substitutions of the technical solutions of the present invention by those of ordinary skill in the art can be made without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A method for preparing medium-chain triglyceride, which comprises the step of reacting glycerol, medium-chain fatty acid and lipase in an ionic liquid to obtain the medium-chain triglyceride, wherein the ionic liquid has a structure shown in the following formula I:
2. the process according to claim 1, wherein the medium-chain fatty acid is selected from C6-C12A fatty acid.
3. The process according to claim 1, wherein the lipase is at least one lipase selected from the group consisting of Candida lipase.
4. The method according to claim 1, wherein the lipase activity is 5000-10000U/g.
5. The process according to claim 3, wherein the Candida lipase is selected from the group consisting of: candida antarctica lipase A, candida antarctica lipase B, candida cylindracea lipase, candida malformation lipase, candida lipolytic lipase, candida parapsilosis lipase and candida rugosa lipase.
6. The method according to claim 1, wherein the lipase is an immobilized lipase.
7. The production method according to claim 1, wherein the molar ratio of the glycerin to the medium-chain fatty acid is 1: 3-4.
8. The method according to claim 1, wherein the lipase is used in an amount of 1 to 3 wt% based on the total amount of medium-chain fatty acids and glycerin; the dosage of the ionic liquid is 20-30 wt% of the total amount of the medium-chain fatty acid and the glycerol.
9. The method of claim 1, wherein the reaction temperature is 60-70 ℃; the reaction time is 12-24 h.
10. A method for preparing an ionic liquid represented by formula I, comprising the following steps:
s1: reacting benzyl alcohol with 4-trifluoromethylbenzenesulfonyl chloride to obtain 4-trifluoromethylbenzenesulfonic acid benzyl ester;
s2: and reacting the 4-trifluoro toluene sulfonic acid benzyl ester with pyridine to obtain the ionic liquid.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033210A (en) * | 2007-04-06 | 2007-09-12 | 中国科学院新疆理化技术研究所 | Functionalization acidic ionic liquid based on pyridine cation and its synthetic method and application |
| CN102492743A (en) * | 2011-11-28 | 2012-06-13 | 浙江工业大学 | Method for preparing medium-chain triglyceride from ionic liquid |
| CN112280810A (en) * | 2020-10-30 | 2021-01-29 | 江南大学 | Preparation method of medium-long chain triglyceride rich in polyunsaturated fatty acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102676304B (en) * | 2011-03-15 | 2013-06-19 | 清华大学 | Preparation method for biodiesel fuel |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033210A (en) * | 2007-04-06 | 2007-09-12 | 中国科学院新疆理化技术研究所 | Functionalization acidic ionic liquid based on pyridine cation and its synthetic method and application |
| CN102492743A (en) * | 2011-11-28 | 2012-06-13 | 浙江工业大学 | Method for preparing medium-chain triglyceride from ionic liquid |
| CN112280810A (en) * | 2020-10-30 | 2021-01-29 | 江南大学 | Preparation method of medium-long chain triglyceride rich in polyunsaturated fatty acid |
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