A method for preparing ethylvinylionol

Abstract

The present application relates to a preparation method of vinylionone, the preparation method comprises the following steps: carrying out Grignard reaction and quenching reaction on beta-ionone and vinyl magnesium salt in sequence, ending the quenching reaction when the magnesium ion content in the reaction solution is less than or equal to 700 ppm, and obtaining the vinylionone. The preparation method has simple process, the obtained vinylionone has high purity, low colority and good storage stability, the corresponding technical effects can be achieved by controlling the magnesium ion content in the preparation, and the method is suitable for industrial production.

Description

Technical Field

[0001] This invention relates to the field of vinyl ionol technology, and more particularly to a method for preparing vinyl ionol. Background Technology

[0002] Vinyl-β-ionol is a key intermediate in the synthesis of vitamin A and isotretinoin. Currently, vinyl-β-ionol is produced by acetylation hydrogenation and Grignard reaction.

[0003] The literature “Synthesis of Vinyl-β-ionol, Shanghai University of Applied Technology” describes its preparation method, which is an intermittent process. It does not mention the specific production process of vinyl-β-ionol. This method uses saturated ammonium chloride as a quenching agent, the post-processing is complicated, the separation of the product generates a large amount of wastewater, and the cost is high.

[0004] CN108002981A discloses a continuous method for producing vinyl-β-ionol. Using β-ionone as a raw material, a solution of β-ionone and magnesium vinyl chloride is introduced into a static mixer to react and generate an intermediate. The intermediate reacts with water in a quenching reactor to generate vinyl-β-ionol and basic magnesium chloride. After centrifugation and filtration, a vinyl-β-ionol solution is obtained. The solution is then distilled to obtain the product, vinyl-β-ionol. However, the product obtained by this disclosed method has poor storage stability.

[0005] The paper "Research on a New Process for the Synthesis of Vitamin A by the Wittig Method" discloses the acetylation hydrogenation of β-ionone, which requires the use of raw materials such as acetylene and liquid ammonia, placing high demands on the equipment and presenting a high degree of difficulty in the production process.

[0006] In conclusion, it is crucial to develop a simple preparation method that yields vinyl ionol with good storage stability. Summary of the Invention

[0007] To address the shortcomings of existing technologies, the present invention aims to provide a method for preparing vinyl ionol. The preparation method is simple, and the resulting vinyl ionol has high purity, low color, and good storage stability.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] This invention provides a method for preparing vinyl ionol, the method comprising the following steps:

[0010] β-ionone and vinyl magnesium salt are subjected to Grignard reaction and quenching reaction in sequence until the magnesium ion content in the reaction solution is ≤700ppm (e.g., 650ppm, 600ppm, 550ppm, 500ppm, 450ppm, 400ppm, 300ppm, 200ppm, 100ppm, 50ppm, 10ppm, 5ppm, etc.), and the quenching reaction is stopped to obtain the vinyl ionol.

[0011] In this invention, the preparation method is simple. By controlling the content of magnesium ions in the system after the quenching reaction, vinyl ionol with high purity and low color can be prepared, and the storage stability of vinyl ionol can also be significantly improved.

[0012] Preferably, after the quenching reaction, the magnesium ion content in the reaction solution is 10-700 ppm, such as 650 ppm, 600 ppm, 550 ppm, 500 ppm, 450 ppm, 400 ppm, 300 ppm, 200 ppm, 100 ppm, 50 ppm, 10 ppm, etc., and more preferably 10-200 ppm.

[0013] In this invention, controlling the magnesium ion content in the vinyl ionol reaction solution to be less than 10 ppm is also applicable. However, since the lower the magnesium ion content is, the more complex the post-processing becomes, significantly increasing the cost of post-processing; the key is that once the magnesium ion content is controlled to be less than 10 ppm, further reducing the magnesium ion content has little impact on the storage stability of the product. Therefore, this invention preferably controls the magnesium ion content to be between 10 and 700 ppm.

[0014] Preferably, the vinyl magnesium salt comprises any one or a combination of at least two of vinyl magnesium bromide, vinyl magnesium chloride, or vinyl magnesium iodide, wherein typical but non-limiting combinations include: a combination of vinyl magnesium bromide and vinyl magnesium chloride, a combination of vinyl magnesium chloride and vinyl magnesium iodide, a combination of vinyl magnesium bromide, vinyl magnesium chloride, and vinyl magnesium iodide, etc.

[0015] Preferably, the vinyl magnesium salt comprises vinyl chloride magnesium.

[0016] Preferably, the mass ratio of β-ionone to vinyl magnesium salt is 1:(1.0-1.5), wherein 1-1.5 can be 1.1, 1.2, 1.3, 1.4, etc., and more preferably 1:(1-1.4).

[0017] Preferably, the Grignard reaction is carried out in a system containing an organic solvent.

[0018] Preferably, the organic solvent includes any one or a combination of at least two of diethyl ether, tetrahydrofuran, or methyltetrahydrofuran, wherein typical but non-limiting combinations include: a combination of diethyl ether and tetrahydrofuran, a combination of tetrahydrofuran and methyltetrahydrofuran, a combination of diethyl ether, tetrahydrofuran, and methyltetrahydrofuran, etc.

[0019] In this invention, the types of organic solvents are not limited to those described above.

[0020] Preferably, the mass ratio of β-ionone to organic solvent is 1:(10-80), wherein 10-80 can be 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, etc., and more preferably 1:(20-50).

[0021] Preferably, the temperature of the Grignard reaction is -15 to 30°C, for example -10°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, etc., and more preferably -10 to 20°C.

[0022] Preferably, the Grignard reaction time is 1-10 hours, such as 2 hours, 4 hours, 6 hours, 8 hours, etc., and more preferably 2-6 hours.

[0023] Preferably, the Grignard reaction is carried out at atmospheric pressure.

[0024] Preferably, the material used in the quenching reaction comprises an aqueous solution of a water-soluble polymer.

[0025] In this invention, the aqueous solution of the water-soluble polymer material is used as a quenching agent. Compared with conventional quenching agents in the prior art, the advantage of the generated basic magnesium chloride is that it is adsorbed on the polymer material, reducing the residual magnesium ions in the organic phase.

[0026] Preferably, the water-soluble polymeric material includes cyclodextrin and / or lignin sulfonate.

[0027] In this invention, the water-soluble polymer material is preferably cyclodextrin and / or lignin sulfonate because the basic magnesium chloride generated by quenching is encapsulated with cyclodextrin and lignin sulfonate through electrostatic adsorption.

[0028] Preferably, the mass ratio of the β-ionone to the aqueous solution of the water-soluble polymer is 1:(1-50), wherein 1-50 can be 5, 10, 15, 20, 25, 30, 35, 40, 45, etc.

[0029] In this invention, when the amount of aqueous solution of water-soluble polymer material is 1-5 times that of β-ionone, the magnesium ion content can be reduced to below 700 ppm; when it is 5-15 times that of ionone, the magnesium ion content can be reduced to below 200 ppm; and when it is 15-50 times that of ionone, the magnesium ion content can be reduced to 10-100 ppm.

[0030] Preferably, in the aqueous solution of the water-soluble polymer material, the mass ratio of the water-soluble polymer material to water is 1:(1-100), wherein 1-100 can be 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 30, 40, 50, 60, 70, 80, 90, etc.

[0031] Preferably, the mass ratio of β-ionone, water-soluble polymer material and water is 1:(0.2-2):(2-20), wherein 0.2-2 can be 0.3, 0.4, 0.6, 0.7, 0.8, 0.9, 1, 11, 1.2, 1.3, 1.4, 1.6, 1.8, etc.; 2-20 can be 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, etc., and more preferably 1:(0.5-1.5):(4-10).

[0032] Preferably, the temperature of the quenching reaction is -15 to 30°C, such as -10°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, etc., and more preferably -10 to 20°C.

[0033] Preferably, the quenching reaction time is 1-10 hours, such as 2 hours, 4 hours, 6 hours, 8 hours, etc., and more preferably 2-6 hours.

[0034] Preferably, the pressure of the quenching reaction is 10-100 kPaG, such as 20 kPaG, 30 kPaG, 40 kPaG, 50 kPaG, 60 kPaG, 70 kPaG, 80 kPaG, 90 kPaG, etc.

[0035] Preferably, after the quenching reaction is completed, centrifugation, washing, and solvent removal are also included.

[0036] In this invention, the centrifugation, washing, and solvent removal processes can adopt industry-known methods without particular limitations. For example, the organic phase obtained by centrifuging the reaction solution is washed with 0.5-1.5 times (e.g., 0.6 times, 0.8 times, 1 times, 1.2 times, 1.4 times, etc.) of water to separate the phases; then the separated organic phase is desolvated by vacuum distillation to remove the solvent.

[0037] As a preferred technical solution, the preparation method includes the following steps:

[0038] (1) Mix β-ionone, vinyl magnesium salt and organic solvent in a mass ratio of 1:(1-1.5):(10-80) and carry out Grignard reaction at a temperature of -15 to 30℃ for 1-20 h.

[0039] (2) The reaction solution obtained in step (1) is mixed with the aqueous solution of water-soluble polymer material, and the mass ratio of water-soluble polymer material, water and β-ionone before Grignard reaction is controlled to be (0.2-2):(2-20):1. The quenching reaction is carried out for 1-10 hours at a temperature of -15 to 30℃ and a pressure of 10-100KpaG until the magnesium ion content in the reaction solution is ≤700ppm.

[0040] (3) The reaction solution obtained in step (2) is centrifuged, washed and desolventized, wherein the vinyl ionool is.

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] (1) The vinyl ionol prepared by the method described in this invention has high purity, low color, good storage stability, and simple process. The corresponding technical effect can be achieved by controlling the magnesium ion content in the preparation process, which is suitable for industrial production.

[0043] (2) The vinyl ionol obtained by the preparation method of the present invention has a purity of more than 98.6% and a color of less than 7.4 hazen. After being stored in a nitrogen atmosphere for 30 days, the purity decreases by less than 6.8% and the color increases by less than 3.4 hazen. Detailed Implementation

[0044] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0045] In this invention, the organic solvents involved in each embodiment were purchased from Bailingwei Technology Co., Ltd.; unless otherwise specified, all other raw materials were purchased from Aladdin Reagent Network.

[0046] Example 1

[0047] This embodiment provides a method for preparing vinyl ionol, the method comprising the following steps:

[0048] (1) β-ionone, vinyl magnesium chloride and tetrahydrofuran were mixed in a mass ratio of 1:1.2:20 and subjected to a Grignard reaction at 20°C for 10 h.

[0049] (2) The reaction solution obtained in step (1) was mixed with an aqueous solution of water-soluble polymer material (named cyclodextrin, purchased from Shandong Binzhou Zhiyuan Biotechnology). The mass ratio of water-soluble polymer material, water and β-ionone before Grignard reaction was controlled to be 1.0:10:1. The quenching reaction was carried out at a temperature of 10℃ and a pressure of 50KpaG for 6 hours until the magnesium ion content in the reaction solution was 15ppm.

[0050] (3) Centrifuge the reaction solution obtained in step (2), wash the obtained organic phase with 1 times the mass of water, separate the phases, and remove the solvent from the separated organic phase by vacuum distillation, namely vinyl ionool.

[0051] Example 2

[0052] (1) β-ionone, vinyl magnesium bromide and methyltetrahydrofuran were mixed in a mass ratio of 1:1.2:60 and subjected to a Grignard reaction at 10°C for 6 h.

[0053] (2) The reaction solution obtained in step (1) was mixed with an aqueous solution of a water-soluble polymer material (named lignin sulfonate, purchased from Paulig, brand name CY-CA), and the mass ratio of the water-soluble polymer material, water and β-ionone before the Grignard reaction was controlled to be 0.2:20:1. The quenching reaction was carried out at a temperature of 10℃ and a pressure of 100KpaG for 3 hours until the magnesium ion content in the reaction solution was 200ppm.

[0054] (3) Centrifuge the reaction solution obtained in step (2), wash the obtained organic phase with 1 times the mass of water, separate the phases, and remove the solvent from the separated organic phase by vacuum distillation, namely vinyl ionool.

[0055] Example 3

[0056] (1) β-ionone, vinyl magnesium chloride and diethyl ether were mixed in a mass ratio of 1:1.1:80 and subjected to a Grignard reaction at -15℃ for 10 h.

[0057] (2) The reaction solution obtained in step (1) is mixed with an aqueous solution of a water-soluble polymer material (named cyclodextrin, purchased from Anaiji). The mass ratio of the water-soluble polymer material, water and β-ionone before the Grignard reaction is controlled to be 0.2:2:1. The quenching reaction is carried out at a temperature of 15℃ and a pressure of 10KpaG for 1h until the magnesium ion content in the reaction solution is 700ppm.

[0058] (3) Centrifuge the reaction solution obtained in step (2), wash the obtained organic phase with 1 times the mass of water, separate the phases, and remove the solvent from the separated organic phase by vacuum distillation, namely vinyl ionool.

[0059] Example 4

[0060] The difference between this embodiment and Embodiment 1 is that the aqueous solution of the water-soluble polymer material is replaced with an equal mass of water; otherwise, they are the same as in Embodiment 1.

[0061] Example 5

[0062] The difference between this embodiment and Embodiment 1 is that the water-soluble polymer material in the aqueous solution of the water-soluble polymer material is replaced by an equal mass of starch (purchased from Huahao Huafeng), instead of cyclodextrin. All other aspects are the same as in Embodiment 1.

[0063] Comparative Example 1

[0064] This embodiment provides a method for preparing vinyl ionol, the method comprising the following steps:

[0065] (1) β-ionone, magnesium chloride and tetrahydrofuran were mixed in a mass ratio of 1:1.2:20 and subjected to a Grignard reaction at 20°C for 10 h.

[0066] (2) The reaction solution obtained in step (1) was mixed with an aqueous solution of a water-soluble polymer material (named cyclodextrin, purchased from Shandong Binzhou Zhiyuan Biotechnology). The mass ratio of the water-soluble polymer material, water and β-ionone before the Grignard reaction was controlled to be 1:10:1. The quenching reaction was carried out at a temperature of 10℃ and a pressure of 50KpaG for 6 hours until the magnesium ion content in the reaction solution was 750ppm.

[0067] (3) Centrifuge the reaction solution obtained in step (2), wash the obtained organic phase with 1 times the mass of water, separate the phases, and remove the solvent from the separated organic phase by vacuum distillation, namely vinyl ionool.

[0068] Performance testing

[0069] The vinyl ionools obtained by the preparation methods described in Examples 1-5 and Comparative Example 1 were tested as follows:

[0070] (1) Purity: determined by gas chromatography under the following conditions:

[0071] Chromatographic column: Agilent WAX (30m × 0.32mm × 0.25mm);

[0072] Inlet temperature: 230℃;

[0073] Flow split ratio: 30:1;

[0074] Column flow rate: 1.5 mL / min;

[0075] Column temperature: Start at 180℃, increase to 230℃ at a rate of 5℃ / min, and hold for 15min;

[0076] Detector temperature: 280℃, H2 flow rate: 35mL / min, air flow rate: 350mL / min.

[0077] (2) Colorimetry: Tested using a CS-821N spectrophotometer.

[0078] (3) Storage stability: The vinyl ionol was stored in a nitrogen atmosphere for 30 days, and its purity and color were tested and the change value was statistically analyzed.

[0079] The test results are summarized in Table 1.

[0080] Table 1

[0081]

[0082]

[0083] Analysis of the data in Table 1 shows that the vinyl ionol obtained by the preparation method of the present invention has a purity of over 98.6% and a color of less than 7.4 hazen. After being stored in a nitrogen atmosphere for 30 days, the purity decreases by less than 6.8% and the color increases by less than 3.4 hazen. The vinyl ionol obtained by the preparation method of the present invention has high purity, low color, and good storage stability.

[0084] Within the preferred range (taking Examples 1-3 as examples), the vinyl ionool obtained by the preparation method of the present invention has a purity of more than 98.9%, a color of less than 5.0 hazen, and after being stored in a nitrogen atmosphere for 30 days, the purity decreases by less than 2.4% and the color increases by less than 0.6 hazen.

[0085] Analysis of Comparative Example 1 and Example 1 shows that the performance of Comparative Example 1 is not as good as that of Example 1, proving that the performance of vinyl ionol formed by controlling the magnesium ion content at 700 ppm is better.

[0086] Analysis of Example 4 and Example 1 shows that the performance of Example 4 is not as good as that of Example 1, proving that the vinyl ionol formed by quenching reaction with an aqueous solution of the preferred water-soluble polymer material has better performance.

[0087] Analysis of Example 5 and Example 1 shows that the performance of Example 5 is not as good as that of Example 1, which proves that the water-soluble polymer material preferably formed from cyclodextrin and / or lignin sulfonate is vinyl ionol with better performance.

[0088] The present invention has been illustrated with the above embodiments to explain the detailed method of the present invention. However, the present invention is not limited to the detailed method described above, that is, it does not mean that the present invention must rely on the detailed method described above to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing vinyl ionol, characterized in that, The preparation method includes the following steps: β-ionone and vinyl magnesium salt were subjected to Grignard reaction and quenching reaction in sequence. The quenching reaction was stopped when the magnesium ion content in the reaction solution was ≤700 ppm to obtain the vinyl ionol. The material used in the quenching reaction is an aqueous solution of a water-soluble polymer, wherein the water-soluble polymer is cyclodextrin and / or lignin sulfonate.

2. The preparation method according to claim 1, characterized in that, The vinyl magnesium salt is selected from any one or a combination of at least two of vinyl magnesium bromide, vinyl magnesium chloride, or vinyl magnesium iodide.

3. The preparation method according to claim 2, characterized in that, The vinyl magnesium salt is vinyl magnesium chloride.

4. The preparation method according to claim 1, characterized in that, The Grignard reaction is carried out in a system containing an organic solvent.

5. The preparation method according to claim 1, characterized in that, The mass ratio of β-ionone to vinyl magnesium salt is 1:(1.0-1.5).

6. The preparation method according to claim 4, characterized in that, The mass ratio of β-ionone to organic solvent is 1:(10-80).

7. The preparation method according to claim 1, characterized in that, The Grignard reaction is carried out at temperatures ranging from -15°C to 30°C.

8. The preparation method according to claim 1, characterized in that, The Grignard reaction takes 1-10 h.

9. The preparation method according to claim 1, characterized in that, The pressure of the Grignard reaction is 10-100 kPaG.

10. The preparation method according to claim 1, characterized in that, The mass ratio of the β-ionone to the aqueous solution of the water-soluble polymer is 1:(1-50).

11. The preparation method according to claim 1, characterized in that, In the aqueous solution of the water-soluble polymer material, the mass ratio of the water-soluble polymer material to water is 1:(1-100).

12. The preparation method according to claim 1, characterized in that, The mass ratio of β-ionone, water-soluble polymer material and water is 1:(0.2-2):(2-20).

13. The preparation method according to claim 1, characterized in that, The quenching reaction occurs at temperatures ranging from -15°C to 30°C.

14. The preparation method according to claim 1, characterized in that, The quenching reaction takes 1-10 hours.

15. The preparation method according to claim 1, characterized in that, The pressure of the quenching reaction is 10-100 kPaG.

16. The preparation method according to claim 1, characterized in that, After the quenching reaction is completed, centrifugation, washing, and solvent removal are performed.

17. The preparation method according to claim 1, characterized in that, The preparation method includes the following steps: (1) β-ionone, vinyl magnesium salt and organic solvent are mixed in a mass ratio of 1:(1-1.5):(10-80) and subjected to Grignard reaction at a temperature of -15~30℃ and a pressure of 10-100 KpaG for 1-20 h. (2) The reaction solution obtained in step (1) is mixed with the aqueous solution of water-soluble polymer material. The mass ratio of water-soluble polymer material, water and β-ionone before Grignard reaction is controlled to be (0.2-2):(2-20):

1. The quenching reaction is carried out for 1-10 h at a temperature of -15~30℃ and a pressure of 10-100 KpaG until the magnesium ion content in the reaction solution is ≤700 ppm. (3) The reaction solution obtained in step (2) is centrifuged, washed and desolventized to obtain the vinyl ionol.

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