CN112979464B - Resveratrol conjugated linoleate and preparation method thereof - Google Patents
Resveratrol conjugated linoleate and preparation method thereof Download PDFInfo
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- 229940016667 resveratrol Drugs 0.000 title claims abstract description 145
- 235000021283 resveratrol Nutrition 0.000 title claims abstract description 145
- LUKBXSAWLPMMSZ-OWOJBTEDSA-N Trans-resveratrol Chemical compound C1=CC(O)=CC=C1\C=C\C1=CC(O)=CC(O)=C1 LUKBXSAWLPMMSZ-OWOJBTEDSA-N 0.000 title claims abstract description 134
- 229940049918 linoleate Drugs 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OYHQOLUKZRVURQ-HZJYTTRNSA-M 9-cis,12-cis-Octadecadienoate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O OYHQOLUKZRVURQ-HZJYTTRNSA-M 0.000 title claims abstract 8
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 claims abstract description 105
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- JBYXPOFIGCOSSB-GOJKSUSPSA-N 9-cis,11-trans-octadecadienoic acid Chemical compound CCCCCC\C=C\C=C/CCCCCCCC(O)=O JBYXPOFIGCOSSB-GOJKSUSPSA-N 0.000 claims abstract description 63
- 229940108924 conjugated linoleic acid Drugs 0.000 claims abstract description 63
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- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 46
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
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- 206010028980 Neoplasm Diseases 0.000 description 1
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
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- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/115—Fatty acids or derivatives thereof; Fats or oils
- A23L33/12—Fatty acids or derivatives thereof
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
Abstract
The invention discloses a preparation method of resveratrol conjugated linoleate, which comprises the following steps: using dichloromethane as a reaction medium, using N, N' -carbonyldiimidazole as a condensing agent to activate conjugated linoleic acid, and synthesizing the conjugated linoleic acid with resveratrol under certain conditions. The method adopts N, N' -carbonyldiimidazole and conjugated linoleic acid as raw materials for the first time, has short reaction time (1.5h), high conversion rate of resveratrol (96.87%), generates no toxic and harmful substances in the reaction, can complete purification only by washing with water, overcomes the problems of a large amount of acidic waste and difficult purification in the traditional chemical method, is suitable for industrialization, improves the lipid solubility of the resveratrol, and has the beneficial effects of the resveratrol and the conjugated linoleic acid.
Description
Technical Field
The invention relates to the technical field of esterification modification of resveratrol. More specifically, the invention relates to a novel preparation method of resveratrol conjugated linoleate.
Background
Resveratrol (Res), also known as resveratrol, is a non-flavonoid polyphenol compound, has the effects of resisting inflammation, reducing blood fat, resisting oxidation, resisting tumor, protecting liver and the like, has higher biological activity, but is easy to oxidize and decompose by light and is unstable to heat; resveratrol has the characteristics of high melting point, poor fat solubility and water solubility and the like, so that the bioavailability is low, the resveratrol is easy to crystallize and separate out when being directly applied to food, the food has unacceptable mouthfeel, and particularly in a system with high resveratrol content, the food quality is seriously influenced. Conjugated Linoleic Acid (CLA) as long-chain unsaturated fatty acid has the effects of resisting atherosclerosis, reducing blood fat and the like, but is easy to oxidize after long-term exposure to air, so that the lipid solubility of the resveratrol is improved, the oxidation speed of the conjugated linoleic acid is reduced, and the effects of the conjugated linoleic acid and the resveratrol are exerted. Therefore, in order to increase the stability and lipid solubility of resveratrol and improve the bioavailability of resveratrol and conjugated linoleic acid, the efficient preparation of the resveratrol conjugated linoleate has important theoretical and application values.
At present, the esterification modification method of resveratrol mainly comprises an acyl chloride method, a Steglich method and an enzyme method, the existing resveratrol ester comprises resveratrol aromatic ester, resveratrol long-chain fatty acid ester, resveratrol medium-chain fatty acid ester and resveratrol short-chain fatty acid ester, wherein the preparation of long-chain unsaturated fatty acid ester is particularly difficult, and the existing methods can not synthesize resveratrol long-chain fatty acid ester with high conversion rate. Although the acyl chloride method has the strongest esterification capacity (the conversion rate is 78-92%, and the reaction time is 2-5 h), acid gases such as sulfur dioxide and hydrogen chloride are generated in the reaction process to pollute the environment, and equipment is seriously corroded; the Steglich esterification method has mild reaction conditions and simple modification route, but N, N-dicycloethylurea can be generated after the reaction, and is difficult to remove cleanly; the enzyme method has the advantages of mild reaction conditions, no pollution, capability of realizing directional esterification and the like, but has the defects of overlong reaction time (24-96 h), low conversion rate (less than 45%), high enzyme price, difficult activity maintenance and the like, so that the industrial production is difficult to realize. The existing chemical method adopts 4-dimethylamino pyridine as a catalyst, and is difficult to separate during purification, so that the obtained product has certain hidden danger on food safety. Conjugated linoleic acid as long-chain unsaturated fatty acid has a plurality of beneficial effects, but the steric hindrance is large, and no reports related to resveratrol esterification are found.
Therefore, a preparation method of resveratrol fatty acid ester with high efficiency, low cost and high conversion rate needs to be urgently proposed, and technical support is provided for industrial application of the resveratrol fatty acid ester.
Disclosure of Invention
The invention aims to provide resveratrol conjugated linoleate and a preparation method thereof, and the method has the advantages of greenness, safety, no generation of harmful substances, high reaction efficiency and the like.
To achieve these objects and other advantages in accordance with the purpose of the invention, according to one aspect of the present invention, there is provided a method for preparing resveratrol conjugated linoleate, comprising:
dissolving conjugated linoleic acid and N, N' -carbonyl diimidazole with a solvent, and collecting reaction liquid after the reaction is finished; dripping the reaction liquid into resveratrol for esterification reaction to obtain the resveratrol conjugated linoleate.
Further, in the preparation method of the resveratrol conjugated linoleate, the molar ratio of the resveratrol to the conjugated linoleic acid is 1: 1-7.
Further, in the preparation method of the resveratrol conjugated linoleate, the molar ratio of the conjugated linoleic acid to the N, N' -carbonyldiimidazole is 1: 0.8-1.1.6.
Further, in the preparation method of the resveratrol conjugated linoleate, the conjugated linoleic acid and the N, N' -carbonyl diimidazole are dissolved by dichloromethane.
Further, in the preparation method of the resveratrol conjugated linoleate, the reaction time of conjugated linoleic acid and N, N' -carbonyldiimidazole is 15-180 minutes.
Furthermore, in the preparation method of the resveratrol conjugated linoleate, the reaction time of the conjugated linoleic acid and the N, N' -carbonyldiimidazole is 30 minutes.
Further, in the preparation method of the resveratrol conjugated linoleate, the reaction time of the esterification reaction is 1-5 hours.
Further, in the preparation method of the resveratrol conjugated linoleate, the reaction time of the esterification reaction is 1 hour.
Further, the preparation method of the resveratrol conjugated linoleate comprises the steps of washing, drying and rotary evaporation after the esterification reaction is finished, so that the resveratrol conjugated linoleate is obtained.
According to another aspect of the invention, the resveratrol conjugated linoleate is provided, and is prepared by the preparation method of the resveratrol conjugated linoleate.
The invention at least comprises the following beneficial effects:
(1) the resveratrol is insoluble in grease, the conversion rate of the resveratrol conjugated linoleate prepared by taking the resveratrol and the conjugated linoleic acid as raw materials is up to more than 96 percent, the purity is up to 98 percent, and the fat solubility problem of the resveratrol is solved;
(2) the invention uses N, N' -carbonyldiimidazole as the condensing agent to prepare the resveratrol conjugated linoleate for the first time, and the condensing agent has low cost, small using amount, high catalytic activity, less side reaction and no generation of toxic and harmful substances;
(3) the resveratrol conjugated linoleate is simple in preparation process, short in reaction time (1.5h), free of organic solvent residue, green, free of harmful substance generation and suitable for industrial production, and reacts at room temperature;
(4) the resveratrol conjugated linoleate prepared by the invention has the functions of resveratrol and conjugated linoleic acid, is light yellow viscous in color, has light fragrance, fat solubility which is about 20 times that of resveratrol, acid value of 0.13mgKOH/g, peroxide value of 0.21mmol/kg, good product quality, suitability for wide application in food, and good nutrition strengthening function, application value and market prospect.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a reaction scheme of the present invention;
FIG. 2 is a graph of the effect of different alkyd molar ratios on conversion;
FIGS. 3-5 are FTIR spectra for different alcohol to acid ratios;
FIG. 6 shows the effect of different amounts of N, N' -carbonyldiimidazole added on the conversion;
FIG. 7 is a graph showing the effect of varying amounts of 4-dimethylaminopyridine added on conversion;
FIG. 8 is a graph of the effect of different esterification modification times on conversion;
FIG. 9 is a graph of the effect of different carboxylic acid activation times on conversion;
FIG. 10 is a thin layer chromatogram of resveratrol conjugated linoleate during reaction.
FIG. 11 is a thin layer chromatogram of resveratrol conjugated linoleate obtained by the optimal process.
Detailed Description
The present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The embodiment of the application provides a preparation method of resveratrol conjugated linoleate, which comprises the following steps: dissolving conjugated linoleic acid and N, N' -carbonyl diimidazole with a solvent, and collecting reaction liquid after the reaction is finished; dripping the reaction liquid into resveratrol for esterification reaction to obtain the resveratrol conjugated linoleate. The solvent may be selected from any suitable organic solvent. Conjugated linoleic acid reacts with N, N' -carbonyldiimidazole to generate acyl imidazoles, then reaction liquid containing the acyl imidazoles is dripped into resveratrol for esterification, and reaction products are treated by a conventional separation method to obtain the resveratrol conjugated linoleate, which is shown in figure 1. In the embodiment, the resveratrol and the conjugated linoleic acid are used as raw materials, the N, N' -carbonyldiimidazole is used as a condensing agent, and the conjugated linoleic acid and the resveratrol are esterified, so that the method is low in reaction process cost, green and pollution-free, mild in reaction conditions and free of waste generation. The N, N' -carbonyl diimidazole used in the reaction process is low in price and cost and is suitable for industrial production. The obtained resveratrol conjugated linoleate improves the lipid solubility, stability and functionality of resveratrol and increases the bioavailability thereof.
In other embodiments, the molar ratio of resveratrol to conjugated linoleic acid is 1: 1-7, preferably 1: 3. The conversion rate tends to increase and then decrease with the increase of the proportion of the conjugated linoleic acid. When the ratio of the alcoholic acid, namely the molar ratio of the resveratrol to the conjugated linoleic acid, reaches 1:3, the conversion rate reaches the maximum, and the conversion rate begins to decrease when the ratio of the acid is continuously increased. Probably because the contact area of the resveratrol and the proper acid can be increased, the reaction is more sufficient; however, too much carboxylic acid reduces the substrate concentration and slows down the reaction rate.
In other embodiments, the conjugated linoleic acid and the N, N' -Carbonyldiimidazole (CDI) are present in a molar ratio of 1:0.8 to 1.6, preferably in a molar ratio of 1:1. As the amount of CDI added increases, the conversion rate tends to increase first and then decrease. Conversion is maximized when the acid CDI molar ratio, i.e., the molar ratio of conjugated linoleic acid to CDI, reaches 1:1, and conversion begins to decrease as the proportion of CDI continues to increase. Since proper CDI can play a role in activating carboxylic acid, when the ratio exceeds 1:1, redundant CDI can react with resveratrol, so that side reactions are increased, and the conversion rate is reduced.
In other embodiments, the conjugated linoleic acid and the N, N' -carbonyldiimidazole are dissolved with methylene chloride.
In other embodiments, the reaction time of the conjugated linoleic acid and the N, N' -carbonyldiimidazole is 15 to 180 minutes, preferably 30 minutes. When the reaction time of the carboxylic acid activation reaction is 15-180 minutes, the conversion rate is high, the conversion rate is increased and then decreased along with the carboxylic acid activation time, and when the activation time is 30 minutes, the conversion rate reaches the maximum value.
In other embodiments, the reaction time of the esterification reaction is 1 to 5 hours, preferably 1 hour. The reaction has higher conversion rate for more than 1 hour, when the esterification modification is carried out for 1 hour, the conversion rate of the resveratrol reaches 96 percent, the reaction basically tends to be stable, and the conversion rate is not obviously improved when the time is continuously increased.
In other embodiments, after the esterification reaction is finished, performing rotary evaporation treatment to remove the volatile solvent to obtain the resveratrol conjugated linoleate. Further, washing the reacted crude product with water for 3 times, passing through a layer of anhydrous sodium sulfate, and freeze-drying to remove excessive water to obtain a pure resveratrol ester product.
Embodiments of the present application provide a resveratrol conjugated linoleate prepared by the method for preparing the resveratrol conjugated linoleate described in any one of the above embodiments.
The following embodiments are described in detail.
The reagents used in the following examples are as follows:
resveratrol, 99%, Shanghai Mecang Biotech, Inc.;
conjugated linoleic acid, 80%, Shanghai Michelin Biotechnology, Inc.;
99% of N, N' -carbonyldiimidazole, Shanghai Allantin Biotechnology Ltd;
99% of 4-dimethylaminopyridine, Shanghai Michelin Biochemical technology Ltd;
dichloromethane, AR, shanghai mclin biochemistry science and technology limited;
the experimental apparatus used was as follows:
a rotary evaporator; an electronic balance; IKA multipoint heating magnetic stirrer
1. Effect of acid-alcohol molar ratio on conversion
1.1 Experimental methods: weighing five parts of proper amount (1eq) of resveratrol and 0.05eq of DMAP in a dry and clean conical flask; taking another conical flask, and respectively mixing the obtained mixture according to the weight ratio of resveratrol: the conjugated linoleic acid molar ratio is 1:1, 1:2, 1:3, 1:5, 1: 7, weighing the conjugated linoleic acid, and then according to the weight ratio of the conjugated linoleic acid: sequentially adding CDI in a CDI molar ratio of 1:1, adding a proper amount of dichloromethane to completely dissolve the CDI, and stirring and reacting for 60min at room temperature; dripping the reaction solution into a weighed resveratrol system, stirring and reacting for 4 hours at room temperature, and performing rotary evaporation to obtain the resveratrol conjugated linoleate. And (3) dissolving a sample by using methanol, detecting the content of the residual resveratrol in the reacted system by using UPLC, and calculating the conversion rate of the resveratrol.
1.2 UPLC detection conditions
A chromatographic column: HSS C18, 1.8um, 2.1 × 100 mm;
mobile phase: phase A: 0.05% aqueous formic acid; phase B: acetonitrile
Flow rate: 0.45 mL/min; detection wavelength: 306 nm; column temperature: 35 ℃; sample introduction amount: 1uL
TABLE 1 UPLC conditions
As can be seen from FIG. 2, the conversion rate increases and then decreases as the proportion of conjugated linoleic acid increases. When the ratio of alcoholic to acid, i.e. the molar ratio of resveratrol to conjugated linoleic acid, reached 1:3, the conversion reached a maximum (96.3%) and continued increase in the proportion of acid the conversion began to decrease. Probably because the contact area of the resveratrol and the proper acid can be increased, the reaction is more sufficient; however, too much carboxylic acid reduces the substrate concentration and slows down the reaction rate. From FIGS. 3-5, it is seen that resveratrol has not reacted completely (3340 cm) when the ratio of alcoholic acid to acid is 1:2-1Treating resveratrol hydroxyl peak), continuing to add conjugated linoleic acid until 1:3 resveratrol almost completely reacts, and 1759cm after alcohol acid ratio exceeds 1:3-1The peak of C ═ O at 1740cm is reduced-1The appearance of a nearby peak and a gradual rise indicate an excess of carboxylic acid; at 1759cm-1The strong peak of (A) is from the stretching vibration of C ═ O at 1124cm-1The signal at (A) is due to the tensile vibration of C-O (C-O-C) which indicates successful synthesis of resveratrol esters, so the ratio of alcoholic to acid is preferably 1: 3.
2. Effect of acid CDI molar ratio on conversion
2.1 Experimental methods: weighing five parts of proper amount (1eq) of resveratrol and 0.05eq of DMAP in a dry and clean conical flask; taking another conical flask, and mixing the materials according to the weight ratio of resveratrol: weighing conjugated linoleic acid according to the molar ratio of the conjugated linoleic acid to the conjugated linoleic acid of 1:3, and then respectively weighing the conjugated linoleic acid: sequentially adding CDI at the CDI molar ratio of 1:0.8, 1:1, 1:1.2, 1:1.4 and 1:1.6, adding a proper amount of dichloromethane to completely dissolve the CDI, and stirring and reacting at room temperature for 60 min; dripping the reaction solution into a weighed resveratrol system, stirring and reacting for 4 hours at room temperature, and performing rotary evaporation to obtain the resveratrol conjugated linoleate. And (3) dissolving a sample by using methanol, detecting the content of the residual resveratrol in the reacted system by using UPLC, and calculating the conversion rate of the resveratrol.
2.2 UPLC detection conditions
Refer to 1.2.
As can be seen from fig. 6, as the amount of CDI added increases, the conversion rate tends to increase first and then decrease. Conversion reached a maximum (96.87%) when the acid CDI molar ratio, i.e., the conjugated linoleic acid to CDI molar ratio, reached 1:1, and continued increase in the proportion of CDI conversion began to decrease. Since proper CDI can play a role in activating carboxylic acid, when the ratio exceeds 1:1, redundant CDI can react with resveratrol, so that side reactions are increased, and the conversion rate is reduced.
Effect of DMAP addition on conversion
3.1 Experimental methods: weighing five parts of proper amount (1eq) of resveratrol and 0eq, 0.05eq, 0.1eq, 0.2eq and 0.4eq of DMAP respectively in a dry and clean conical flask; taking another conical flask, and mixing the materials according to the weight ratio of resveratrol: weighing conjugated linoleic acid according to the molar ratio of the conjugated linoleic acid being 1:3, and then, according to the molar ratio of the conjugated linoleic acid: adding CDI into the mixture according to the CDI molar ratio of 1:3, adding a proper amount of dichloromethane to completely dissolve the CDI, and stirring and reacting for 60min at room temperature; dripping the reaction solution into a weighed resveratrol system, stirring and reacting for 4 hours at room temperature, and performing rotary evaporation to obtain the resveratrol conjugated linoleate. And (3) dissolving a sample by using methanol, detecting the content of the residual resveratrol in the reacted system by using UPLC, and calculating the conversion rate of the resveratrol.
3.2 UPLC detection conditions
Refer to 1.2.
As can be seen from fig. 7, the conversion of resveratrol was substantially unchanged with increasing DMAP. DMAP is a widely used super nucleophilic acylation catalyst, it appears that CDI is sufficient to acylate the carboxylic acid, and DMAP is more difficult to remove by addition to the system, so DMAP is not added.
4. Effect of esterification modification time on conversion
4.1 Experimental methods: weighing five parts of proper resveratrol in a dry and clean conical flask; taking another conical flask, and mixing the obtained mixture according to the weight ratio of resveratrol: weighing five parts of conjugated linoleic acid according to the molar ratio of the conjugated linoleic acid being 1:3, and then mixing the conjugated linoleic acid: sequentially adding CDI with the CDI molar ratio of 1:1, adding a proper amount of dichloromethane to completely dissolve the CDI, and stirring and reacting for 60min at room temperature; dripping the reaction solution into a weighed resveratrol system, stirring and reacting for 1, 2, 3, 4 and 5 hours at room temperature, and performing rotary evaporation to obtain the resveratrol conjugated linoleate. And (3) dissolving a sample by using methanol, detecting the content of the residual resveratrol in the reacted system by using UPLC, and calculating the conversion rate of the resveratrol.
4.2 UPLC detection conditions
Refer to 1.2.
As can be seen from FIG. 8, when the esterification modification is carried out for 1h, the conversion rate of the resveratrol reaches 96%, the reaction basically tends to be stable, and the conversion rate is not obviously improved when the time is continuously increased. Considering that the reaction time is too long, which not only increases the probability of side reactions, but also the conjugated linoleic acid is long-chain polyunsaturated fatty acid and is easily oxidized by exposing air for a long time, the esterification modification time is selected to be 1 h.
5. Effect of Carboxylic acid activation time on conversion
5.1 Experimental methods: weighing five parts of proper resveratrol in a dry and clean conical flask; taking another conical flask, and mixing the obtained mixture according to the weight ratio of resveratrol: weighing five parts of conjugated linoleic acid according to the molar ratio of the conjugated linoleic acid being 1:3, and then mixing the conjugated linoleic acid: sequentially adding CDI in a CDI molar ratio of 1:1, adding a proper amount of dichloromethane to completely dissolve the CDI, and stirring and reacting for 15, 30, 60, 120 and 180min at room temperature; dripping the reaction solution into a weighed resveratrol system, stirring and reacting for 1h at room temperature, and performing rotary evaporation to obtain the resveratrol conjugated linoleate. And (3) dissolving a sample by using methanol, detecting the content of the residual resveratrol in the reacted system by using UPLC, and calculating the conversion rate of the resveratrol.
5.2 UPLC detection conditions
Refer to 1.2.
As can be seen from FIG. 9, the conversion rate tends to increase and then decrease with the carboxylic acid activation time, and when the activation time is 30min, the conversion rate reaches the maximum (96.18%), and the continuous delay time conversion rate decreases, so that 30min is the optimum carboxylic acid activation time.
6. Detection of Properties of resveratrol conjugated linoleate
The properties of resveratrol conjugated linoleate are shown in tables 2 and 3. Specifically, the physicochemical indexes of the purified sample (see figure 10) are measured, and the color refers to the method GB/T5009.37-20033.1; the acid value is measured by reference to the first method of GB 5009.229-2016; the peroxide number was determined by reference to the first method of GB 5009.227-2016. Fat-soluble measurement: accurately weighing about 0.5g of resveratrol and resveratrol conjugated linoleate in three parts respectively, putting into a 100ml triangular flask, heating in water bath to 60 ℃, dropwise adding the peanut oil into the triangular flask, and continuously stirring until the resveratrol and the resveratrol conjugated linoleate are completely dissolved by the peanut oil, so that the system is in a uniform phase. After cooling to 20 ℃ and standing for 24 hours, the flask was observed for the presence of precipitates or cloudiness, and the solubility (g/100ml, 20 ℃) was calculated on the basis of the amount of added peanut oil.
TABLE 2 physicochemical Properties of resveratrol conjugated linoleate
| Physical and chemical properties | Resveratrol conjugated linoleate |
| Traits | Pale yellow viscous oil |
| Acid value | 0.13mgKOH/g |
| Peroxide number | 0.21mmol/kg |
TABLE 3 solubility of resveratrol and resveratrol conjugated linoleate in peanut oil
| Resveratrol | Resveratrol conjugated linoleate | |
| Peanut oil | 30.2μg/kg | Mutual solubility |
Monitoring the esterification modification process by TLC (normal hexane-ethyl acetate-glacial acetic acid, 10:8:0.1, v/v/v), then respectively dissolving resveratrol and conjugated linoleic acid in dichloromethane, developing at the same developing agent proportion, developing under an ultraviolet lamp of 254nm, and comparing with the sample point after reaction. From the silica gel plate, it can be seen that the new substances (two resveratrol monoesters, conjugated linoleic acid, resveratrol diester and resveratrol triester in sequence from bottom to top) were successfully synthesized (fig. 11). The resveratrol conjugated linoleate prepared according to the optimal process is purified and then subjected to TLC analysis, the main products are resveratrol diester and triester, and the content of resveratrol and conjugated linoleic acid can be seen to be very small.
In conclusion, the best process for preparing resveratrol conjugated linoleate is as follows: the molar ratio of resveratrol to conjugated linoleic acid is 1:3, the molar ratio of CDI to conjugated linoleic acid is 1:1, DMAP is not added, the carboxylic acid activation time is 30min, and the esterification modification time is 1 h. And the condensation agent N, N' -carbonyldiimidazole is adopted to activate conjugated linoleic acid and carry out esterification with resveratrol, 4-dimethylaminopyridine is not needed to be added, the whole reaction can be completed at room temperature for 1.5h, the energy is greatly saved, the conversion rate of the resveratrol can reach more than 96%, and carbon dioxide and imidazole generated in the reaction process are nontoxic and harmless and are suitable for the food industry.
The number of apparatuses and the scale of the process described herein are intended to simplify the description of the present invention. The use, modifications and variations of the resveratrol conjugated linoleate and its preparation method of the present invention will be apparent to those skilled in the art.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (4)
1. The preparation method of the resveratrol conjugated linoleate is characterized by comprising the following steps:
dissolving conjugated linoleic acid and N, N' -carbonyl diimidazole with a solvent, and collecting reaction liquid after the reaction is finished; dripping the reaction liquid into resveratrol for esterification reaction to obtain resveratrol conjugated linoleate;
the molar ratio of the resveratrol to the conjugated linoleic acid is 1: 3;
the molar ratio of the conjugated linoleic acid to the N, N' -carbonyldiimidazole is 1: 1;
the reaction time of the conjugated linoleic acid and the N, N' -carbonyl diimidazole is 15-180 minutes;
the reaction time of the esterification reaction is 1-5 hours;
conjugated linoleic acid and N, N' -carbonyldiimidazole were dissolved with dichloromethane.
2. The method of producing resveratrol conjugated linoleate according to claim 1, wherein the reaction time of conjugated linoleic acid and N, N' -carbonyldiimidazole is 30 minutes.
3. The method of producing resveratrol conjugated linoleate according to claim 1, wherein the reaction time of the esterification reaction is 1 hour.
4. The method for preparing resveratrol conjugated linoleate according to claim 1, wherein after esterification reaction, washing with water, drying and rotary evaporation are performed to obtain resveratrol conjugated linoleate.
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