CN112876353A - 2- (3-propylphenoxy) propionic acid and preparation method and application thereof - Google Patents
2- (3-propylphenoxy) propionic acid and preparation method and application thereof Download PDFInfo
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- CN112876353A CN112876353A CN202110159277.9A CN202110159277A CN112876353A CN 112876353 A CN112876353 A CN 112876353A CN 202110159277 A CN202110159277 A CN 202110159277A CN 112876353 A CN112876353 A CN 112876353A
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- propylphenoxy
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
- C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
- C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
- C07C59/68—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings the oxygen atom of the ether group being bound to a non-condensed six-membered aromatic ring
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- 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
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/30—Artificial sweetening agents
- A23L27/39—Addition of sweetness inhibitors
Abstract
The invention discloses 2- (3-propylphenoxy) propionic acid and a preparation method and application thereof. The structural formula of the 2- (3-propylphenoxy) propionic acid is as follows:
the 2- (3-propylphenoxy) propionic acid has good sweet suppression effect, and the preparation method has the advantages of simple operation, short reaction time, high reaction conversion rate, high product purity and the like, and is convenient for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to 2- (3-propylphenoxy) propionic acid and a preparation method and application thereof.
Background
Sugar is one of essential nutrients for human body and is the main energy supply substance for human. Sugar, as a sweetener, has the effect of improving the texture of the product, providing flavor, color and smooth mouthfeel to the product, in addition to providing sweetness to the product. Furthermore, sugar can also be used as a natural binder and preservative in food production. In the specific food production process, the added sugar must reach a certain amount to ensure the product quality and realize the effects of sugar preservation, bonding and shaping, color enhancement and the like, but the problem of over-sweet food is often caused.
At present, the problem of food over-sweetness is often solved by adding sweetness inhibitors to the food. The sweetness inhibitor can effectively inhibit sweetness, can be widely applied to high-sugar foods such as moon cake stuffing, candies, chocolates, jam, ice cream and the like, and plays roles in reducing sweetness, improving mouthfeel, improving quality and reducing cost.
Therefore, the sweet taste inhibitor has a wide application prospect, and it is necessary to develop a new sweet taste inhibitor.
Disclosure of Invention
The invention aims to provide 2- (3-propylphenoxy) propionic acid and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
2- (3-propylphenoxy) propionic acid, having the formula:
the preparation method of the 2- (3-propylphenoxy) propionic acid comprises the following steps:
1) dispersing 3-propylphenol, 2-chloropropionic acid and sodium hydroxide in water to prepare a water phase, dispersing a phase transfer catalyst in an organic solvent to prepare an organic phase, mixing the water phase and the organic phase, and carrying out Williamson reaction;
2) adjusting the pH value of the reaction solution obtained in the step 1) to 1-2, standing, separating and collecting an organic phase;
3) evaporating and removing the solvent in the organic phase collected in the step 2), and purifying the solid obtained by evaporation through acid-base recrystallization to obtain the 2- (3-propylphenoxy) propionic acid.
Preferably, the mass ratio of the 3-propylphenol, the 2-chloropropionic acid, the sodium hydroxide and the phase transfer catalyst in the step 1) is 1: 2-3: 1.0-1.5: 0.02-0.05.
Preferably, the phase transfer catalyst in step 1) is at least one of tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, chain polyethylene glycol dialkyl ether, pyridine and tributylamine.
Further preferably, the phase transfer catalyst in step 1) is tetrabutylammonium bromide.
Preferably, the volume ratio of the aqueous phase to the organic phase in the step 1) is 1: 0.8-1: 1.2.
Preferably, the organic solvent in step 1) is at least one of benzene, diethyl ether, petroleum ether, acetone and carbon tetrachloride.
Further preferably, the organic solvent in step 1) is benzene.
Preferably, the Williamson reaction in step 1) is carried out at 40-60 ℃ for 3-5 h.
Preferably, the pH of the reaction solution is adjusted to 1-2 by adopting an HCl solution with the mass fraction of 10% -30% in the step 2).
Preferably, the specific operation of the acid-base recrystallization in the step 3) is as follows: and adding the solid obtained by evaporation into a NaOH solution for dissolving, adjusting the pH value to 9-10, adding an HCl solution for adjusting the pH value to 1-2, standing, adjusting the temperature to 0-5 ℃, and then performing suction filtration and drying.
Preferably, the acid-base recrystallization time in the step 3) is 2-4 times.
The invention has the beneficial effects that: the 2- (3-propylphenoxy) propionic acid has good sweet suppression effect, and the preparation method has the advantages of simple operation, short reaction time, high reaction conversion rate, high product purity and the like, and is convenient for large-scale industrial production.
Drawings
FIG. 1 is a NMR chart of 2- (3-propylphenoxy) propionic acid of example 1.
FIG. 2 is an infrared spectrum of 2- (3-propylphenoxy) propionic acid of example 1.
Fig. 3 is a graph of the relationship between the electronic tongue response value and the sensory value.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
2- (3-propylphenoxy) propionic acid, the preparation method comprises the following steps:
1) dispersing 20kg of 3-propylphenol, 50kg of 2-chloropropionic acid and 20kg of sodium hydroxide in 60kg of water to prepare a water phase, dispersing 0.4kg of tetrabutylammonium bromide in 150L of benzene to prepare an organic phase, mixing the water phase and the organic phase, adding the mixture into a reaction kettle, and reacting for 3 hours at 50 ℃;
2) adjusting the pH of the reaction solution obtained in the step 1) to 2 by using an HCl solution with the mass fraction of 20%, standing, separating and collecting an organic phase;
3) evaporating and removing solvent benzene in the organic phase collected in the step 2), adding the solid obtained by evaporation into a NaOH solution with the mass fraction of 30% for dissolving, adjusting the pH to 9, dropwise adding an HCl solution with the mass fraction of 20% for adjusting the pH to 2, standing, adjusting the temperature to 5 ℃, separating out white flaky crystals, performing suction filtration and drying, and repeating the acid-base recrystallization operation for 2 times to obtain the 2- (3-propylphenoxy) propionic acid (the yield is 5.7%, and the purity is 99%).
The NMR spectrum of 2- (3-propylphenoxy) propionic acid is shown in FIG. 1, and the IR spectrum is shown in FIG. 2.
1H NMR(600MHz,Chloroform-d)：δ7.19(t,J＝7.9Hz,1H),6.83(ddt,J＝7.6,1.6,0.8Hz,1H),6.74(t,J＝2.0Hz,1H),6.70(dt,J＝8.2,1.7Hz,1H),4.84-4.74(m,1H),2.55(dd,J＝8.5,6.8Hz,2H),1.81-1.41(m,5H),0.92(t,J＝7.3Hz,3H)。
As can be seen from fig. 2: at 3000cm-1The sum of the intensity width of the left and right peaks and 1716cm-1Peaks at (D) were 2910cm, which are respectively the absorption of stretching vibration of O-H and C ═ O in the carboxyl group-1And 3060cm-1The peak is respectively the stretching vibration absorption of saturated C-H and benzene ring C-H, 1250cm-1The strong absorption peak is the stretching vibration of C-O bond in ether, 877cm-1、753cm-1And 700cm-1The peak at (a) indicates meta substitution of the benzene ring.
In conclusion: example 1 preparation gave the expected product, 2- (3-propylphenoxy) propionic acid.
Example 2:
2- (3-propylphenoxy) propionic acid, the preparation method comprises the following steps:
1) dispersing 10kg of 3-propylphenol, 21kg of 2-chloropropionic acid and 14kg of sodium hydroxide in 13kg of water to prepare a water phase, dispersing 0.3kg of tetrabutylammonium bromide in 40L of benzene to prepare an organic phase, mixing the water phase and the organic phase, adding the mixture into a reaction kettle, and reacting at 60 ℃ for 3.5 hours;
2) adjusting the pH of the reaction solution obtained in the step 1) to 2 by using an HCl solution with the mass fraction of 20%, standing, separating and collecting an organic phase;
3) evaporating and removing solvent benzene in the organic phase collected in the step 2), adding the solid obtained by evaporation into a NaOH solution with the mass fraction of 30% for dissolving, adjusting the pH to 9, dropwise adding an HCl solution with the mass fraction of 20% for adjusting the pH to 2, standing, adjusting the temperature to 3 ℃, separating out white flaky crystals, performing suction filtration and drying, and repeating the acid-base recrystallization operation for 2 times to obtain the 2- (3-propylphenoxy) propionic acid (the yield is 5.4%, and the purity is 99%).
Example 3:
2- (3-propylphenoxy) propionic acid, the preparation method comprises the following steps:
1) dispersing 8kg of 3-propylphenol, 20kg of 2-chloropropionic acid and 12kg of sodium hydroxide in 30kg of water to prepare a water phase, dispersing 0.24kg of tetrabutylammonium bromide in 70L of benzene to prepare an organic phase, mixing the water phase and the organic phase, adding the mixture into a reaction kettle, and reacting for 5 hours at 60 ℃;
2) adjusting the pH of the reaction solution obtained in the step 1) to 2 by using an HCl solution with the mass fraction of 20%, standing, separating and collecting an organic phase;
3) evaporating and removing solvent benzene in the organic phase collected in the step 2), adding the solid obtained by evaporation into NaOH solution with the mass fraction of 30% for dissolving, adjusting the pH to 9, dropwise adding HCl solution with the mass fraction of 20% for adjusting the pH to 2, standing, adjusting the temperature to 0 ℃, separating out white flaky crystals, performing suction filtration and drying, and repeating the acid-base recrystallization operation for 1 time to obtain the 2- (3-propylphenoxy) propionic acid (the yield is 5.3%, and the purity is 99%).
And (3) performance testing:
sweet taste suppression experiment of 2- (3-propylphenoxy) propionic acid:
mouth test for sucrose sweetness:
when the sweetness is tasted organoleptically, the sweetness is divided into 5 grades, and the 5 grades respectively correspond to the sweetness represented by sucrose solutions with different concentrations, which is specifically shown in table 1:
TABLE 1 concentration of sucrose solution at different sweetness levels
Selecting 20 healthy volunteers (9 male volunteers and 11 female volunteers) as subjects to carry out sweetness calibration, respectively taking 20mL of reference solution of each grade in a mouth-tasting cup, putting the reference solution in the mouth of the volunteers, timing for 15s, carrying out mouth rinsing action in the oral cavity so as to enable a sweet taste perception area at the tongue tip to feel the sweet taste of the sucrose solution, informing the volunteers of sweetness grading and specific sweetness value of the reference solution, spitting out, rinsing for 5 times till no sweet taste exists in the oral cavity, and measuring the reference solution of another concentration after 15 min.
And (3) after the taste evaluation of the volunteers is normalized, performing the taste evaluation of the sweetness of the sucrose solution with the concentration shown in the table 2, determining the sweetness level of a certain sample according to the taste feeling of the volunteers by combining the grade in the previous reference liquid, giving a specific sweetness value, recording the sweetness value in the sweetness level evaluation table, gargling till no sweetness exists in the oral cavity, and measuring another sample after 15 min.
Table 2 concentration of taste evaluation test point
Measuring the sweetness of the sucrose by an electronic tongue method:
taking a sucrose solution with a prepared concentration in the table 2, measuring by using a sweet taste sensor, taking 20mL of a sample with the same concentration, placing the sample in a special measuring cup for an electronic tongue, placing the sample on an automatic sample feeding disk for the electronic tongue, setting a sample measuring sequence, namely continuously measuring the same sample for 5 times, and selecting the last 4 times of results in the 5 times of measuring results to take an average value.
The data from the mouth taste and electronic tongue measurements were fitted and the fitted curves are shown in figure 3.
As can be seen from fig. 3: as the concentration of sucrose increases, the sweetness and the response value of the electronic tongue all increase gradually, the fitted curve also shows a positive correlation trend, and R2The sweet taste reaches 0.99, and the electronic tongue is proved to be capable of effectively reflecting the sweet taste change.
2- (3-propylphenoxy) propionic acid sweetness-suppressing effect assay:
adding into sucrose solution with mass fraction of 25%
The sweetness of the 2- (3-propylphenoxy) propionic acid is measured by using a sweetness sensor of the electronic tongue, 20mL of the sample is taken and placed in a special measuring cup of the electronic tongue and is placed on an automatic sample feeding disc of the electronic tongue, the sample measuring sequence is set, namely, the same sample is continuously measured for 5 times, the last 4 times of the 5 times of measuring results are selected and averaged, and the measuring results are shown in table 3.
Since the results of the electronic tongue assay sweet taste response value and the taste evaluation showed significant correlation, the sweet taste inhibitory effect of the substance was evaluated using the response value of the electronic tongue. The inhibitor has an inhibition rate delta r, and for the sweetener with the same concentration, the electronic tongue response value of the sweetener, namely the difference between the sweetener and pure water, is I0The response value of the sweetener electronic tongue after the sweet inhibitor is added is I, and the inhibition rate is calculated according to the formula: Δ r ═ I (I)0-I)/I0。
TABLE 32 inhibition of sucrose solution by 3-Propylphenoxy propionic acid
As can be seen from Table 3: the 2- (3-propylphenoxy) propionic acid has good sweet taste inhibiting effect.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
- 2- (3-propylphenoxy) propionic acid, characterized by the structural formula:
- 2. the process for producing 2- (3-propylphenoxy) propionic acid according to claim 1, which comprises the steps of:1) dispersing 3-propylphenol, 2-chloropropionic acid and sodium hydroxide in water to prepare a water phase, dispersing a phase transfer catalyst in an organic solvent to prepare an organic phase, mixing the water phase and the organic phase, and carrying out Williamson reaction;2) adjusting the pH value of the reaction solution obtained in the step 1) to 1-2, standing, separating and collecting an organic phase;3) evaporating and removing the solvent in the organic phase collected in the step 2), and purifying the solid obtained by evaporation through acid-base recrystallization to obtain the 2- (3-propylphenoxy) propionic acid.
- 3. The process for producing 2- (3-propylphenoxy) propionic acid according to claim 2, characterized in that: the mass ratio of the 3-propylphenol, the 2-chloropropionic acid, the sodium hydroxide and the phase transfer catalyst in the step 1) is 1: 2-3: 1.0-1.5: 0.02-0.05.
- 4. The process for producing 2- (3-propylphenoxy) propionic acid according to claim 2 or 3, characterized in that: the phase transfer catalyst in the step 1) is at least one of tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, chain polyethylene glycol dialkyl ether, pyridine and tributylamine.
- 5. The process for producing 2- (3-propylphenoxy) propionic acid according to claim 2 or 3, characterized in that: the volume ratio of the aqueous phase to the organic phase in the step 1) is 1: 0.8-1: 1.2.
- 6. The process for producing 2- (3-propylphenoxy) propionic acid according to claim 2 or 3, characterized in that: the Williamson reaction in the step 1) is carried out at the temperature of 40-60 ℃ for 3-5 h.
- 7. The process for producing 2- (3-propylphenoxy) propionic acid according to claim 2 or 3, characterized in that: and 2) adjusting the pH value of the reaction solution to 1-2 by adopting an HCl solution with the mass fraction of 10% -30%.
- 8. The process for producing 2- (3-propylphenoxy) propionic acid according to claim 2 or 3, characterized in that: the specific operation of the acid-base recrystallization in the step 3) is as follows: and adding the solid obtained by evaporation into a NaOH solution for dissolving, adjusting the pH value to 9-10, adding an HCl solution for adjusting the pH value to 1-2, standing, adjusting the temperature to 0-5 ℃, and then performing suction filtration and drying.
- 9. The process for producing 2- (3-propylphenoxy) propionic acid according to claim 2 or 3, characterized in that: and 3) recrystallizing the acid and the alkali for 2-4 times.
- 10. Use of 2- (3-propylphenoxy) propionic acid according to claim 1 as a sweetness inhibitor.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114516792A (en) * | 2022-01-28 | 2022-05-20 | 华南理工大学 | 2- (3,4, 5-trimethoxy phenoxy) propionic acid and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2157148A (en) * | 1984-04-12 | 1985-10-23 | Tate & Lyle Plc | Method of modifying taste |
| WO1995004476A1 (en) * | 1993-08-05 | 1995-02-16 | San-Ei Gen F.F.I., Inc. | Method of suppressing sweetness |
| WO2007059066A2 (en) * | 2005-11-15 | 2007-05-24 | General Mills, Inc. | Reduced sweetness confectionary compositions and coated/filled food products |
| CN102010326A (en) * | 2010-10-28 | 2011-04-13 | 华南理工大学 | Industrial method for synthesizing 2-(4-methoxyphenoxy)-propionic acid through phase transfer |
| CN112218543A (en) * | 2018-03-30 | 2021-01-12 | 三得利控股株式会社 | Sweet taste compositions that generate sweet taste responses in addition to sweet taste receptors (T1R2/T1R3) |
-
2021
- 2021-02-05 CN CN202110159277.9A patent/CN112876353B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2157148A (en) * | 1984-04-12 | 1985-10-23 | Tate & Lyle Plc | Method of modifying taste |
| US5045336A (en) * | 1984-04-12 | 1991-09-03 | Amstar Sugar Corporation | Method of modifying sweet taste |
| WO1995004476A1 (en) * | 1993-08-05 | 1995-02-16 | San-Ei Gen F.F.I., Inc. | Method of suppressing sweetness |
| WO2007059066A2 (en) * | 2005-11-15 | 2007-05-24 | General Mills, Inc. | Reduced sweetness confectionary compositions and coated/filled food products |
| CN102010326A (en) * | 2010-10-28 | 2011-04-13 | 华南理工大学 | Industrial method for synthesizing 2-(4-methoxyphenoxy)-propionic acid through phase transfer |
| CN112218543A (en) * | 2018-03-30 | 2021-01-12 | 三得利控股株式会社 | Sweet taste compositions that generate sweet taste responses in addition to sweet taste receptors (T1R2/T1R3) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114516792A (en) * | 2022-01-28 | 2022-05-20 | 华南理工大学 | 2- (3,4, 5-trimethoxy phenoxy) propionic acid and preparation method and application thereof |
| CN114516792B (en) * | 2022-01-28 | 2023-01-06 | 华南理工大学 | 2- (3, 4, 5-trimethoxy phenoxy) propionic acid and preparation method and application thereof |
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