CN111099979A - Preparation method of β -ionone - Google Patents
Preparation method of β -ionone Download PDFInfo
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- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
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Abstract
The invention provides a preparation method of β -ionone, which comprises feeding and isomerization reaction, wherein the reaction has high conversion rate and selectivity, the raw material conversion rate is 98.1-99.3%, the selectivity is 94.1-99.3%, the yield is 93.3-98%, β -ionone product has high purity, β content is 98.61-99.12%, α content is 0.36-0.51%, gamma content is 0.07-0.19%, dihydro- β -ionone is not detected, tetrahydro-ionone is not detected, the catalyst can be suitable for the isomerization reaction of raw materials with different contents of α -ionone, gamma-ionone and β -ionone, especially the catalyst can be used for independently preparing the former raw material source when α -ionone/β -ionone pure product is distilled industrially, the raw material source is wide, the price is low, the catalyst accounts for less than 0.5% of the feeding time, and the reaction time is less than 15 h.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing β -ionone from α -ionone or α -ionone and gamma-ionone mixture or α -ionone, gamma-ionone and β -ionone mixture through isomerization reaction.
Background
β -ionone [4- (2,6, 6-trimethyl-1-cyclohexenyl) -3-buten-2-one ] is a valuable perfume, has certain biological activity, shows strong anticancer effect and especially has obvious inhibition effect on tumor occurrence, and in addition, the product is widely applied in industry, is a quite important medical intermediate and is an important raw material for synthesizing vitamin A, E, β -carotene, carotenoid, retinoic acid, phytol and the like.
At present, processes for preparing β -ionone generally comprise two methods, namely a cyclization method and an isomerization method, wherein the cyclization method is generally adopted in industry to produce β -ionone, the cyclization method takes pseudoionone as a raw material and generates a cyclization reaction under the action of concentrated sulfuric acid, a product of the cyclization reaction is generally a mixture of three isomers of α -ionone, β -ionone and gamma-ionone, wherein two isomers of α -ionone and β -ionone are mainly used, the isomerization method takes α -ionone which is relatively easy to prepare as a raw material, and the non-conjugated double bond is converted into the conjugated double bond through catalytic isomerization, so that the β -ionone is obtained.
In the cyclization process, strong acid and low temperature conditions are used for facilitating the generation of β -ionone, but the exothermic quantity of the reaction is large, and a great deal of research is focused on how to quickly remove heat generated by the cyclization reaction, so that the selectivity of β -ionone is improved.CN 1508113 discloses a method for reducing the reaction temperature by adding dry ice in the cyclization reaction process, wherein the method can ensure that the content of β -ionone in a final product is not less than 96% and the yield is 72.0-85.0% in a small test scale in a laboratory, although the method has better effect in a small test experiment, the defect is obvious when the method is applied to large-scale production, the production cost is increased and the complexity of process operation is improved, rapid and uniform contact reaction cannot be ensured after the dry ice is added, the local overheating of a reaction system is probably caused, but the side reaction is increased, US4565894 discloses a method for preparing β -ionone by instant contact of pseudo-ionone and sulfuric acid, but the method can easily reduce the heat transfer rate of a micro-capillary heat transfer reaction, and the micro-reaction technology is not suitable for controlling the micro-heat transfer reaction, and micro-micro reaction technology is more easily applied to a micro reactor, and the micro reactor is more easily controlled in a micro reactor, and the micro reactor is more easily.
The main defects of the prior cyclization process are that a large amount of sulfuric acid wastewater is generated in the ① production process, the impurity content in the wastewater is high, the treatment cost is high, the heat transfer and mass transfer are required to be enhanced in the ② process, the control difficulty is high, the energy consumption is high, the ③ reaction can not avoid the generation of α -ionone and gamma-ionone isomers, the separation difficulty is high, and the product purity is not high, so the improvement of the β -ionone production process is necessary.
In recent years, the research on the process for preparing β -ionone by an isomerization method is continuously increased, patent CN101381293B introduces a method for converting α -ionone into high-content β -ionone under the irradiation of 300-325nm ultraviolet light by using cuprous chloride as a catalyst and methanol as a solvent, the purity of the obtained β -ionone can reach more than 98%, the process is simple and convenient, but the design difficulty of a photocatalytic reaction device is high, the production efficiency is low, the industrial difficulty is high, patent CN108031476A introduces a preparation method using a supported Pd-Sm-S-K/gamma-Al 2O3 catalyst, the preparation method is applied to the reaction for preparing β -ionone by isomerization, when the catalyst prepared by using an ionone pure product as a raw material under the conditions of a reaction temperature of 50-100 ℃ and continuous introduction of hydrogen, the total yield of α -ionone and gamma-ionone can reach more than 99%, the yield of β -ionone reaches more than 95%, the disadvantage that the pure ionone prepared by using a traditional isomerization reaction kettle and an oil phase hydrogenation reaction method which has high cost of oxidizing catalyst, the same as a catalyst, the cost of tetrahydrofuran is higher than that when the isomerization reaction of an ionone by adding hydrogen peroxide, the conventional isomerization catalyst, the isomerization reaction method has no need to recover and the isomerization reaction under the advantages of an isomerization reaction of an isomerization catalyst under the isomerization reaction of an isomerization catalyst under the isomerization reaction method of an isomerization catalyst under the isomerization reaction of a high cost of a high isomerization catalyst of an isomerization catalyst of a high isomerization catalyst of an isomerization catalyst of crude catalyst under the isomerization catalyst of crude catalyst of 8102380-tetrahydrofuran, the isomerization catalyst under the isomerization reaction of a high cost of crude oil phase of.
The reaction equation for preparing β -ionone by cyclization in the prior art is as follows:
the reaction equation for preparing β -ionone by isomerization in the prior art is as follows:
disclosure of Invention
The invention aims to provide a method for preparing β -ionone by an isomerization method aiming at the defects of the prior art, the catalyst has high activity and selectivity, mild reaction conditions, convenient operation, realization of the application of the catalyst and low production cost.
The raw material used by the invention is α -ionone or α -ionone, gamma-ionone and β -ionone mixture, wherein α -ionone, gamma-ionone and β -ionone mixture is derived from the first fraction obtained by rectification in the industrial preparation of α -ionone and β -ionone, the traditional treatment method is to burn the mixture as hazardous waste, and the mixture can be converted into β -ionone by the process of the invention, thereby increasing the added value, reducing the cost and simultaneously reducing the discharge of three wastes.
In order to realize the purpose, the invention adopts the following technical scheme:
a preparation method of β -ionone is characterized by comprising the following steps:
the method comprises the following steps: feeding, isomerization reaction and rectification.
The feeding comprises 1 part of raw materials, 0-5 parts of solvent, preferably 0.02-0.03 part of solvent, 0.001-0.01 part of metal Pd catalyst precursor compound, 0-0.001 part of metal La catalyst precursor compound, 0.001-0.1 part of phosphine ligand compound, preferably 0.006-0.1 part of phosphine ligand compound; 0.0001 to 0.0055 part of a silane compound is added to the reaction vessel.
The content of α -ionone, gamma-ionone and β -ionone in the raw materials is 55.5-95.2%;
the specific raw materials contain α -ionone 52.6-91.8%, gamma-ionone 1.2-2.7%, and β -ionone 0.5-17.1%.
The metal Pd catalyst precursor compound is one or more of palladium dichloride, palladium acetate, palladium nitrate, bis (triphenylphosphine) palladium dichloride, (1, 5-cyclooctadiene) palladium dichloride and palladium acetylacetonate.
The metal La catalyst precursor compound is one or more of lanthanum nitrate, lanthanum trichloride and lanthanum acetylacetonate.
The molar ratio of the metal Pd catalyst precursor compound to the phosphine ligand compound is 1: 5-1: 30.
The molar ratio of the metal Pd catalyst precursor compound to the silane compound is 1: 1-1: 5.
The phosphine ligand is one or more of triphenylphosphine, triphenyl phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, 1, 2-bis (diphenylphosphino) ethane and 2, 2-bis (diphenylphosphino) -1, 1-binaphthyl.
The silane compound is one or more of trialkane silane or triaryl silane. Such as: triethylsilane, triethoxysilane, triisopropylsilane and triphenylsilane.
The solvent is polyethylene glycol 200, polyethylene glycol 400 and polyethylene glycol 600.
The isomerization reaction comprises the steps of replacing nitrogen for three times, stirring at the rotating speed of 200-1000 rpm, reacting at the temperature of 30-150 ℃ for 2-15 hours until the total conversion rate of α bodies and gamma bodies is more than 98.0%, cooling to below 30 ℃, and rectifying.
The rectification step comprises the steps of rectifying in two towers, wherein in the former tower, under the condition of absolute pressure of 300-500Pa, under the condition of 30 theoretical plate packings, the reflux ratio is 3-5, the former tower top is collected, until the content of β -ionone in the tower bottom is more than 99.1%, the rectification is stopped, the material in the tower bottom of the former tower is removed to a finished product tower for rectification, under the condition of absolute pressure of 300-500Pa, under the condition of 10 theoretical plate packings, the reflux ratio is 0.5-1, a finished product is collected at the tower top, the content of β -ionone in the tower top is controlled to be more than 98.5%, the rectification is stopped after the temperature of the finished product tower bottom is raised to 120 ℃, and the mother liquor is applied to the next isomerization.
When the content of active ingredients of α -ionone, gamma-ionone and β -ionone in the raw materials is more than 95%, wherein the content of α -ionone is more than 75%, the yield of the product β -ionone is more than 97.6-98%, and the final industrial yield is 91.5-91.9%.
The preferred technical scheme is as follows:
the feeding comprises the following steps of 1 part of raw materials, 0.02-0.03 part of solvent, 0.001-0.01 part of metal Pd catalyst precursor compound, 0-0.001 part of metal La catalyst precursor compound and 0.04-0.07 part of phosphine ligand compound; 0.0006 to 0.0055 part of a silane compound is added to the reaction vessel.
The raw materials contain α -ionone, gamma-ionone, β -ionone with an effective component content of more than 95%, wherein α -ionone with an effective component content of more than 75%;
the metal Pd catalyst precursor compound is one or more of palladium dichloride, palladium acetate, palladium nitrate, bis (triphenylphosphine) palladium dichloride, (1, 5-cyclooctadiene) palladium dichloride and palladium acetylacetonate.
The metal La catalyst precursor compound is one or more of lanthanum nitrate, lanthanum trichloride and lanthanum acetylacetonate.
The phosphine ligand is one or more of triphenylphosphine, triphenyl phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, 1, 2-bis (diphenylphosphino) ethane and 2, 2-bis (diphenylphosphino) -1, 1-binaphthyl.
The silane compound is one or more of trialkane silane or triaryl silane. Such as: triethylsilane, triethoxysilane, triisopropylsilane and triphenylsilane.
The solvent is polyethylene glycol 200, polyethylene glycol 400 and polyethylene glycol 600.
The isomerization reaction comprises the steps of replacing nitrogen for three times, stirring at the rotating speed of 800-1000 rpm, reacting at the temperature of 30-50 ℃ for 5-8 hours until the total conversion rate of α bodies and gamma bodies is more than 98.0%, cooling to below 30 ℃, and rectifying.
Compared with the prior art, the invention has the following advantages:
1. the invention has high conversion rate and selectivity of the reaction, the conversion rate of the raw material is 98.1-99.3%, the selectivity is 94.1-99.3%, the yield is 93.3-98%, and the preferable technical proposal is that the yield of the product β -ionone is more than 97.6-98%.
2, β -ionone product has high purity, β body content of 98.61-99.12%, α body content of 0.36-0.51%, gamma body content of 0.07-0.19%, no dihydro- β -ionone detected, and no tetrahydro-ionone detected.
3. The catalyst is suitable for the isomerization reaction of raw materials with different contents of α -ionone, gamma-ionone and β -ionone, especially the former part of pure α -ionone/β -ionone product rectification can be prepared separately in industry.
4. The catalyst has high activity, the catalyst feeding amount accounts for less than 5.0%, and the reaction time is less than 15 h.
5. The catalyst has long service life, high activity and selectivity after 10 batches of the catalyst are applied, low production cost and contribution to industrial production, and after 10 batches of the catalyst are applied, the conversion rate has no obvious change, the selectivity is reduced by 0.5-0.6 percent, and the yield is reduced by 0.4-0.5 percent.
6. The industrial yield of the method is 47-91.9%, and the final industrial yield of β -ionone is 91.5-91.9% by adopting the preferred technical scheme.
Detailed Description
Attached: the calculation formula of the yield in the example is as follows:
the yield of β -ionone = α and the total conversion rate of gamma bodies × β -ionone selectivity calculated by α -ionone and gamma-ionone in the raw materials;
the calculation formula of the yield in the examples is:
based on the total raw materials, the β -ionone yield is the mass of the β -ionone finished product obtained by rectification divided by the mass of the reaction raw materials.
EXAMPLE 1A method for the preparation of β -ionone
The method comprises the following steps:
(1) charging of
672.0g of a raw material (content: α -ionone: 91.8%, γ -ionone: 2.7%, β -ionone: 0.6%), 13.5g of polyethylene glycol 400, 0.672g of palladium dichloride, 0.05g of lanthanum trichloride, 29.5g of triphenylphosphine and 0.43g of triethylsilane were charged into a 1000ml reaction vessel.
(2) Isomerization reaction
And (3) pressurizing the reaction kettle to 0.3MPa by using nitrogen, then emptying to 0.05MPa, repeatedly operating for three times, reacting at the reaction temperature of 50 ℃ and the stirring speed of 800rpm, detecting the content of the reaction liquid after 5.0h, reducing the temperature, and stopping stirring, wherein the total residual quantity of α bodies and gamma bodies is less than 2.0%.
Through gas chromatographic analysis, the total conversion rate of α bodies and gamma bodies is 98.3 percent, the selectivity of β -ionone is 99.3 percent, and the yield of β -ionone is 97.6 percent.
(3) Rectifying to obtain β -ionone
Transferring 716g of reaction liquid into a 1000ml three-neck flask, vacuumizing by a rotary vane vacuum pump, rectifying by a 100cm glass spring packed tower, controlling the reflux ratio to 3-5 to collect the former part, finishing the rectification of the former part after the impurity content in the front of a tower kettle is less than 0.2 percent, rectifying by a 30cm glass spring packed tower to collect a finished product, finally rectifying to obtain 614.9g of β -ionone finished product, and mechanically applying the kettle liquid to the next batch of reaction, wherein the kettle liquid is 50.2 g.
Based on the total raw materials, the yield of β -ionone is 91.5%, the content of finished products detected by GC is β -body content of 99.12%, α body of 0.36%, gamma body of 0.07%, no dihydro- β -ionone is detected, and no tetrahydro-ionone is detected.
Example 2A method for the preparation of β -ionone
The method comprises the following steps:
(1) charging of
672.0g of a starting material (content: α -ionone: 75.8%, γ -ionone: 2.3%, β -ionone: 17.1%), 20.0g of polyethylene glycol 400, 6.72g of palladium acetate, 46.7g of triphenyl phosphite and 3.5g of triethylsilane were charged into a 1000ml reaction vessel.
(2) Isomerization reaction
And (3) pressurizing the reaction kettle to 0.3MPa by using nitrogen, then emptying to 0.05MPa, repeatedly operating for three times, reacting at the reaction temperature of 30 ℃ and the stirring speed of 800rpm, detecting the content of the reaction liquid after 8.0h, reducing the temperature, and stopping stirring, wherein the total residual quantity of α bodies and gamma bodies is less than 2.0%.
Through gas chromatographic analysis, the total conversion rate of α bodies and gamma bodies is 98.9 percent, the selectivity of β -ionone is 99.1 percent, and the yield of β -ionone is 98.0 percent.
(3) Rectifying to obtain β -ionone
The reaction solution was rectified to obtain 617.6g of β -ionone.
The rectification method was the same as in example 1.
Based on the total raw materials, the yield of β -ionone is 91.9%, the content of finished products detected by GC is β -body content 98.77%, α body 0.49%, gamma body 0.14%, no dihydro- β -ionone is detected, and no tetrahydro-ionone is detected.
EXAMPLE 3A method for the preparation of β -ionone
The method comprises the following steps:
(1) charging of
672.0g of a raw material (content: α -ionone: 52.6%, γ -ionone: 2.3%, β -ionone: 0.6%), 20.0g of polyethylene glycol 400, 6.72g of palladium nitrate, 0.454g of lanthanum acetylacetonate, 67.2g of tris (2.4-di-t-butylphenyl) phosphite and 0.067g of triethoxysilane were charged into a 1000ml reaction vessel.
(2) Isomerization reaction
And (3) pressurizing the reaction kettle to 0.3MPa by using nitrogen, then emptying to 0.05MPa, repeatedly operating for three times, reacting at the reaction temperature of 150 ℃ and at the stirring speed of 800rpm, detecting the content of the reaction liquid after 2.0h, reducing the temperature, stopping stirring, wherein the total residual quantity of α bodies and gamma bodies is less than 2.0%.
Through gas chromatographic analysis, the total conversion rate of α bodies and gamma bodies is 99.2%, the selectivity of β -ionone is 94.1%, and the yield of β -ionone is 93.3%.
(3) Rectifying to obtain β -ionone
The reaction solution was rectified to obtain 316.1g of β -ionone.
The rectification method was the same as in example 1.
Calculated by the total raw materials, the yield of β -ionone is 47.0%, the content of finished products detected by GC is β -body content 99.03%, α -body content 0.38%, gamma body 0.08%, no dihydro- β -ionone is detected, and no tetrahydro-ionone is detected.
Example 4A method for the preparation of β -ionone
The method comprises the following steps:
(1) charging of
672.0g of the raw material (content: α -ionone: 52.6%, γ -ionone: 2.3%, β -ionone: 0.6%), 20.0g of polyethylene glycol 600, 2.5g of bis (triphenylphosphine) palladium dichloride, 0.672g of lanthanum acetylacetonate, 26.3g of triphenylphosphine and 0.59g of triisopropylsilane were charged into a 1000ml reaction vessel.
(2) Isomerization reaction
And (3) pressurizing the reaction kettle to 0.3MPa by using nitrogen, then emptying to 0.05MPa, repeatedly operating for three times, reacting at the reaction temperature of 100 ℃ and the stirring speed of 800rpm, detecting the content of the reaction liquid after 15.0h, reducing the temperature, and stopping stirring, wherein the total residual quantity of α bodies and gamma bodies is less than 2.0%.
Through gas chromatographic analysis, the total conversion rate of α bodies and gamma bodies is 99.3 percent, the selectivity of β -ionone is 95.7 percent, and the yield of β -ionone is 95.0 percent.
(3) Rectifying to obtain β -ionone
The reaction solution was rectified to obtain 303.7g of β -ionone.
The rectification method was the same as in example 1.
Based on the total raw materials, the yield of β -ionone is 45.2%, the content of finished products detected by GC is β -body content 98.76%, α body 0.45%, gamma body 0.07%, no dihydro- β -ionone is detected, and no tetrahydro-ionone is detected.
EXAMPLE 5A method for preparing β -ionone
The method comprises the following steps:
(1) charging of
672.0g of raw material (content: α -ionone: 62.2%, γ -ionone: 1.2%, β -ionone: 0.5%), 20.0g of polyethylene glycol 600, 0.67g of palladium acetylacetonate, 0.1g of lanthanum trichloride, 4.36g of 1, 2-bis (diphenylphosphino) ethane and 0.57g of triphenylsilane were charged into a 1000ml reaction vessel.
(2) Isomerization reaction
And (3) pressurizing the reaction kettle to 0.3MPa by using nitrogen, then emptying to 0.05MPa, repeatedly operating for three times, reacting at the reaction temperature of 120 ℃ and the stirring speed of 1000rpm, detecting the content of the reaction liquid after 6.0h, reducing the temperature, and stopping stirring, wherein the total residual quantity of α bodies and gamma bodies is less than 2.0%.
Through gas chromatographic analysis, the total conversion rate of α bodies and gamma bodies is 98.6%, the selectivity of β -ionone is 97.1%, and the yield of β -ionone is 95.7%.
(3) Rectifying to obtain β -ionone
The reaction solution was rectified to obtain 377.8g of β -ionone.
The rectification method was the same as in example 1.
Based on the total raw materials, the yield of β -ionone is 56.2%, the content of finished products detected by GC is β -body content 98.72%, α body 0.44%, gamma body 0.16%, no dihydro- β -ionone is detected, and no tetrahydro-ionone is detected.
Example 6A method for preparing β -ionone
The method comprises the following steps:
(1) charging of
672.0g of the starting material (content: α -ionone: 62.2%, γ -ionone: 1.2%, β -ionone: 0.5%), 20.0g of polyethylene glycol 200, 2.85g of (1, 5-cyclooctadiene) palladium dichloride, 0.05g of lanthanum acetylacetonate, 32.0g of 2, 2-bis (diphenylphosphino) -1, 1-binaphthyl and 13.0g of triphenylsilane were charged into a 1000ml reaction vessel.
(2) Isomerization reaction
And (3) pressurizing the reaction kettle to 0.3MPa by using nitrogen, then emptying to 0.05MPa, repeatedly operating for three times, reacting at the reaction temperature of 100 ℃ and the stirring speed of 800rpm, detecting the content of the reaction liquid after 12.0h, reducing the temperature, stopping stirring, wherein the total residual quantity of α bodies and gamma bodies is less than 2.0%.
Through gas chromatographic analysis, the total conversion rate of α bodies and gamma bodies is 98.1 percent, the selectivity of β -ionone is 95.1 percent, and the yield of β -ionone is 93.3 percent.
(3) Rectifying to obtain β -ionone
The reaction solution was rectified to obtain 359.5g of β -ionone.
The rectification method was the same as in example 1.
Based on the total raw materials, the yield of β -ionone is 53.5%, the content of finished products detected by GC is β -body content 98.61%, α body 0.51%, gamma body 0.19%, no dihydro- β -ionone is detected, and no tetrahydro-ionone is detected.
The invention uses homogeneous complex catalyst, adjusts the selectivity of the catalyst by lanthanide metal compound, adjusts the activity of the catalyst by silane compound, realizes homogeneous reaction by screening different phosphine ligands, and ensures the service life of the catalyst.
Example 7
The residue (catalyst mother liquor) separated by rectification in example 1 was used repeatedly, and the results are shown in table 1 after 10 times of use of the catalyst under the same process conditions as in example 1.
TABLE 1 conversion selectivity for catalyst application
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A preparation method of β -ionone is characterized by comprising feeding and isomerization reaction.
2. The method of claim 1, wherein the β -ionone comprises, by weight, 1 part of raw materials, 0-5 parts of solvent, 0.001-0.01 part of Pd metal catalyst precursor compound, 0-0.001 part of La metal catalyst precursor compound, 0.001-0.1 part of phosphine ligand compound, and 0.0001-0.0055 part of silane compound.
3. The method for preparing β -ionone according to claim 2, wherein the raw material, α -ionone, gamma-ionone, β -ionone, has an effective component content of 55.5-95.2%;
the method for preparing β -ionone according to claim 2, wherein the raw material comprises α -ionone 52.6-91.8%, gamma-ionone 1.2-2.7%, and β -ionone 0.5-17.1%.
4. The preparation method of β -ionone according to claim 2, wherein the metal Pd catalyst precursor compound is one or more of palladium dichloride, palladium acetate, palladium nitrate, bis (triphenylphosphine) palladium dichloride, (1, 5-cyclooctadiene) palladium dichloride, and palladium acetylacetonate.
5. The method for preparing β -ionone according to claim 2, wherein the metal La catalyst precursor compound is one or more of lanthanum nitrate, lanthanum trichloride and lanthanum acetylacetonate, and the silane compound is one or more of trialkane silane and triarylsilane.
6. The method for preparing β -ionone according to claim 2, wherein the phosphine ligand is one or more of triphenylphosphine, triphenyl phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, 1, 2-bis (diphenylphosphino) ethane, and 2, 2-bis (diphenylphosphino) -1, 1-binaphthyl, the silane compound is one or more of triethylsilane, triethoxysilane, triisopropylsilane, and triphenylsilane, and the solvent is one or more of polyethylene glycol 200, polyethylene glycol 400, and polyethylene glycol 600.
7. The method for preparing β -ionone according to claim 2, wherein the molar ratio of the metal Pd catalyst precursor compound to the phosphine ligand compound is 1: 5-30, and the molar ratio of the metal Pd catalyst precursor compound to the silane compound is 1: 1-5.
8. The preparation method of β -ionone according to claim 2, wherein the isomerization reaction and nitrogen substitution are carried out for three times, the reaction temperature is 30-150 ℃ under the condition of stirring rotation speed of 200-1000 rpm, the reaction time is 2-15 hours until the total conversion rate of α bodies and gamma bodies is more than 98.0%, the temperature is reduced to below 30 ℃, and the rectification treatment is carried out.
9. The preparation method of β -ionone as claimed in claim 1, characterized in that the preparation method further comprises rectification treatment, wherein the rectification treatment comprises rectification in two columns, wherein the process conditions of the first column are that under the absolute pressure of 300-500Pa, 30 theoretical plate packings, the reflux ratio is 3-5, the first column is collected at the top of the column, until the content of β -ionone in the bottom of the column is more than 99.1%, the rectification is stopped, the material in the bottom of the first column is distilled in a finished product column, the process conditions of the finished product column are that under the absolute pressure of 300-500Pa, under 10 theoretical plate packings, the reflux ratio is 0.5-1, the finished product is collected at the top of the column, the content of β -ionone in the top of the column is more than 98.5%, the rectification is stopped after the temperature in the bottom of the finished product column is raised to 120 ℃, and the mother liquor is used in the next isomerization reaction.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111718251A (en) * | 2020-08-04 | 2020-09-29 | 李金国 | Preparation method of beta-ionone for cosmetics |
| CN113979848A (en) * | 2021-10-21 | 2022-01-28 | 上海应用技术大学 | Method for reducing polymerization of beta-ionone in kettle in rectification process |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111718251A (en) * | 2020-08-04 | 2020-09-29 | 李金国 | Preparation method of beta-ionone for cosmetics |
| CN113979848A (en) * | 2021-10-21 | 2022-01-28 | 上海应用技术大学 | Method for reducing polymerization of beta-ionone in kettle in rectification process |
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