CN109665977B - Efficient production method of ionone-alpha sodium hydroxysulfonate adduct - Google Patents
Efficient production method of ionone-alpha sodium hydroxysulfonate adduct Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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Abstract
The invention discloses a high-efficiency production method of an ionone-alpha sodium hydroxysulfonate adduct, which comprises the following steps: putting the ionone isomer mixture and 30-40% sodium bisulfite aqueous solution into a reaction kettle according to a certain proportion, mixing, adding lower aliphatic alcohol with the carbon number within a certain proportion within 5, uniformly stirring, heating to 78-90 ℃, carrying out reflux reaction for 4-8 hours, recovering the solvent, cooling to room temperature, and forming a reaction system into a viscous crystalline material, namely the ionone-alpha hydroxysulfonic acid sodium adduct. The production method has the advantages that: the addition reaction speed of methyl ketone such as ionone isomer and the like and sodium bisulfite is greatly accelerated by adding the low-grade aliphatic alcohol solvent, the production efficiency is improved, and the energy consumption is reduced, so that the synthesis of the ionone-alpha sodium hydroxysulfonate addition compound is realized by a simple, economic and practical method. Provides a new purification and separation production method for the subsequent high-purity ionone product.
Description
Technical Field
The invention belongs to the field of organic chemical synthesis, and particularly relates to a high-efficiency production method of an ionone-alpha sodium hydroxysulfonate adduct. The ionone-alpha hydroxy sodium sulfonate adduct is beneficial to separating ionone isomers and simultaneously producing high-purity alpha ionone and high-purity beta ionone; and extracting and purifying the ionone product from the low-content ionone system.
Background
At present, ionone is a fine chemical with wide application value, and mainly comprises alpha, beta and gamma 3 isomers, wherein the chemical name of the ionone is as follows: 4- (2,6, 6-trimethyl-2-cycloocten-1-yl) -3-buten-2-one. The alpha body has excellent and rich violet and flower fragrance and has little warm wood-like iris fragrance; the high-purity alpha-ionone refers to a product with alpha-I88-92% and beta-I1-5%, and can be widely used as a high-grade spice in various types of blended essences for daily use chemicals, foods and cigarettes. In addition, the more important application is as a starting material for preparing other high-grade spices (such as methyl damascone, damascone and megastigmatrienone). The high-purity beta-ionone is beta-ionone product with beta-I97% and alpha-I1%, and is used in preparing various kinds of essence and as medicine intermediate for preparing vitamin A, retinoic acid and other important chemical matter. The structural formula is shown on the right:
the existing synthesis process route of ionone is as follows: condensing citral and acetone under alkaline condition to obtain pseudo ionone. The pseudo ionone is acidified and cyclized in the presence of 60% sulfuric acid, phosphoric acid, zinc chloride and other moderate-strength acidic catalysts and organic solvents, and an ionone product is obtained through reaction. Rectifying to obtain an ionone isomer mixture (usually 60-70% of alpha-isomer, 16-30% of beta-isomer and 1-5% of gamma-isomer). If the pseudo-ionone is cyclized in strong acid-concentrated sulfuric acid under the condition of dilution in solvent such as ethanol and intense stirring at low temperature, the beta-ionone with the purity of more than 97 percent is obtained.
Under the conditions of the existing production technology and the production and preparation process of high-purity ethyl ionone, a great deal of sulfuric acid wastewater which is difficult to recycle is generated, so that the great problem of environmental treatment is caused. Meanwhile, the market demand of high-purity ionone A/B monomer products also enables manufacturers to actively carry out separation and purification research on ionone isomers. And the production process of the ionone series products also produces ionone waste with lower content and needs purification and refining.
The ionone isomers are all methyl ketone, all isomers of the ionone and NaHSO3 are subjected to nucleophilic addition reaction to generate water-soluble alpha-hydroxysodium sulfonate by utilizing the principle that the methyl ketone can be subjected to addition reaction with sodium bisulfite, and then the separation of the alpha-ionone and the beta-ionone is realized by utilizing the difference of the decomposition and regeneration speeds of NaHSO3 addition products of the ionone isomers in alkali liquor. Thereby realizing the production of high-purity A-ionone or B-ionone commodities. Of course, the water-solubility characteristic of the ionone alpha-hydroxysulfonic acid sodium salt addition compound can also be utilized to remove other non-methyl ketone or aldehyde compound impurities, thereby achieving the purpose of purifying ionone related products.
At present, the production method of the ionone-alpha sodium hydroxysulfonate adduct is to carry out reflux reaction on ionone and a saturated sodium bisulfite solution (with the concentration of more than 35%) at 104-110 ℃ for 24-36 hours, and all ionone isomers can completely react with sodium bisulfite to form water-soluble liquid, so that the ionone isomers can be continuously purified and separated. The disadvantages of this method are evident: the production consumes long time and high energy and material consumption. Milovahafu et al (JP, 40-7183.1965) add ammonium chloride in a certain proportion to accelerate the reaction process, and reflux reaction is carried out at 104-110 ℃ for 8 hours under the optimal condition, so that the addition reaction of ionone can be completed. However, the experimental effect shows that in the reflux process of the method, the peculiar smell of ammonia influences the body health of production operators, and also influences the fragrance quality of the final ionone monomer product.
Disclosure of Invention
The invention aims to solve the problems and the defects, and provides a method for efficiently completing addition reaction of an ionone isomer and sodium bisulfite, which has simple and safer process; the solvent can be recycled, the reaction time is short, and the energy consumption and the material consumption of the production are obviously reduced. Is favorable for realizing the separation of ionone isomers and the industrial production of high-purity monomer products by applying the ionone-alpha hydroxy sodium sulfonate adduct.
The technical scheme of the invention is realized as follows:
the invention relates to a method for producing an efficient ionone-alpha sodium hydroxysulfonate adduct, which is characterized by comprising the following steps: the method comprises the following steps: mixing the ionone isomer mixture with 30-40% sodium bisulfite aqueous solution, adding a certain proportion of lower aliphatic alcohol solvent with less than 5 carbon atoms, stirring uniformly, heating to 78-90 ℃, refluxing and reacting for 4-8 hours (until all oily liquid enters a water layer), and converting all ionone isomers into alpha-sodium hydroxysulfonate addition compounds. Standing to obtain a clear, transparent and uniform solution without floating oil. Recovering solvent, cooling to room temperature to obtain viscous crystal material, and obtaining the ionone-alpha hydroxy sodium sulfonate adduct.
The lower aliphatic alcohol solvent added for reaction can be one or more of lower aliphatic alcohols within C5 such as methanol, ethanol, isopropanol, n-butanol, etc., and can be well mixed with water. Ethanol is preferred.
In the invention, the sodium bisulfite aqueous solution can be subjected to addition reaction by using an unsaturated solution (the concentration is less than 35% and more than or equal to 30%) or a saturated solution (the concentration is more than 35%), and the addition reaction time (generally within 8 hours) in the invention is obviously shortened by a lot compared with the reaction time (24-36 hours) in the prior art, and the reaction can be finished, which is a great innovation of the invention.
Ionone mixture in the above reaction: sodium bisulfite: the molar ratio of the ethanol feeding proportion is as follows: 1: 0.5-2: 0.5-5. Preferably 1: 1-1.5: 2.5-4.
Because the ratio of sodium bisulfite is lower than 1: when the ratio is more than 1:2, the using amount of the sodium bisulfite is large, and the economy is not good; when the feeding proportion of the solvent ethanol is lower than the range, the time required by the addition reaction is correspondingly prolonged and is lower than 1: 2.5, the addition reaction time is 9 hours or more, and is higher than 1: 4 hours, the addition reaction time is not obviously better than 4 hours, and the optimal selection range is 1: 2.5-4.
The solvent ethanol and the like charged into the above reaction can be recovered and recycled without purification.
The sodium bisulfite required for the above reaction includes, but is not limited to, sodium bisulfite freshly prepared by a simple reaction of sodium metabisulfite, or boric acid with sodium sulfite with water.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
the method greatly accelerates the addition reaction speed of the methyl ketone such as ionone isomer and the like and the sodium bisulfite by adding the low-grade fatty alcohol solvent, shortens the reaction time, improves the production efficiency and reduces the energy consumption. Meanwhile, the solvent can be recovered and reused without refining. Moreover, the reaction system has no other bad odor and bad odor to influence the production operation environment and the quality of subsequent products. The addition product of ionone-alpha sodium hydroxysulfonate can be used for realizing the separation of ionone isomers by the prior art and extracting high-purity ionone products from low-content ionone waste materials.
Detailed Description
The invention relates to a method for producing a high-efficiency ionone-alpha sodium hydroxysulfonate adduct, which comprises the following steps:
mixing the ionone isomer mixture with 30-40% sodium bisulfite aqueous solution, adding a certain proportion of lower aliphatic alcohol solvent with less than 5 carbon atoms, stirring uniformly, heating to 78-90 ℃, and carrying out reflux reaction for 4-8 hours to completely convert the ionone isomer into alpha-hydroxysulfonic acid sodium salt; recovering solvent, cooling to room temperature to obtain viscous crystal material to obtain ionone-alpha hydroxy sodium sulfonate adduct;
wherein the molar ratio of the sodium bisulfite to the charging amount of the ionone isomer mixture is 0.5-2:1; the molar ratio of the lower aliphatic alcohol solvent to the charging amount of the ionone isomer mixture is 0.5-5: 1.
the lower aliphatic alcohol can be one or more of methanol, ethanol, isopropanol, and n-butanol. Ethanol is preferred.
The further scheme is as follows: mixture of ionone isomers in the above reaction: sodium bisulfite: the molar ratio of the feeding proportion of the lower aliphatic alcohol is 1: (1-1.5): (2.5-4).
The low-grade fatty alcohol solvent can be recycled continuously without refining.
The sodium bisulfite includes, but is not limited to, sodium bisulfite freshly prepared by the simple reaction of sodium metabisulfite, or boric acid with sodium sulfite and water.
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention in any way, and any limited number of modifications which can be made by anyone within the scope of the claims are still within the scope of the claims.
Example 1
Adding 78g of sodium bisulfite, 126g of water (preparation concentration is 38%), 96g of ionone isomer mixture (total ketone 92%, alpha-I50%, beta-I40%, gamma-I2%) into a 1000ml three-neck flask, and uniformly stirring; adding 96g of ethanol, stirring uniformly, heating to 82 ℃, keeping the reflux temperature, stirring for reacting for 4 hours, stopping stirring, standing, and converting the solution into a clear and transparent uniform system without floating oil and all ionone isomers into alpha-hydroxysulfonic acid sodium salts. Recovering ethanol to 96 deg.C, accounting for about 90% of ethanol input amount, stopping heating and stirring, standing for 15min, and observing to obtain a uniform transparent system. Stirring and cooling to room temperature to obtain a viscous crystalline material, namely the ionone-alpha sodium hydroxysulfonate adduct.
The ionone-alpha hydroxysulfonic acid sodium salt adduct can be subsequently subjected to experimental operation for separating ionone isomers by the existing known technology.
In this example, ionone: sodium bisulfite: ethanol molar ratio ═ 1: 1.5: 4, the sodium bisulfite solution is in a saturated state, the reaction temperature is 82 ℃, the reaction is carried out for 4 hours, the ionone raw material is completely reacted, and the proportion ensures that the addition reaction takes the shortest time to completely carry out the addition reaction, which is a preferred embodiment.
Example 2
Adding 78g of sodium bisulfite, 182g of water (preparation concentration is 30%), 96g of ionone isomer mixture (total ketone 92%, alpha-I50%, beta-I40%, gamma-I2%) into a 1000ml three-neck flask, and uniformly stirring; and adding 58g of ethanol, stirring uniformly, heating to 84 ℃, keeping the reflux temperature, stirring, reacting for 8 hours, stopping stirring, and standing to obtain a clear and transparent uniform system without floating oil. Recovering ethanol to 96 deg.C, accounting for about 90% of ethanol feed amount, stopping stirring, standing for 15min, and observing to obtain a uniform transparent system. Stirring and cooling to room temperature to obtain a viscous crystalline material, namely the ionone-alpha sodium hydroxysulfonate adduct.
In this example, ionone: sodium bisulfite: ethanol molar ratio ═ 1: 1.5: 2.5, the sodium bisulfite solution is in an unsaturated state, the reaction temperature is 84 ℃, and the reaction is carried out for 8 hours, because the mixture ratio is in the moment, compared with the example 1, the ethanol feeding amount is reduced a little, the sodium bisulfite solution is also in an unsaturated state, therefore, the addition reaction temperature is increased, the required time is longer, compared with the example 1, the reaction time is doubled, and the addition reaction of the ionone and the sodium bisulfite can be completed.
Example 3
Adding 52g of sodium bisulfite, 94g of water (preparation concentration is 35%), 96g of ionone isomer mixture (total ketone 92%, alpha-I50%, beta-I40%, gamma-I2%) into a 1000ml three-neck flask, and uniformly stirring; and adding 58g of ethanol, stirring uniformly, heating to 84 ℃, keeping the reflux temperature, stirring for reacting for 7 hours, stopping stirring, and standing to obtain a clear and transparent uniform system without floating oil. Recovering ethanol to 96 deg.C, accounting for about 90% of ethanol feed amount, stopping stirring, standing for 15min, and observing to obtain a uniform transparent system. Stirring and cooling to room temperature to obtain a viscous crystalline material, namely the ionone-alpha sodium hydroxysulfonate adduct.
In this example, ionone: sodium bisulfite: ethanol molar ratio ═ 1: 1: 2.5, the sodium bisulfite solution is saturated, the reaction temperature is 84 ℃, and the reaction is carried out for 7 hours, because the proportion is in this case, the ethanol input amount is reduced by a little compared with the example 1, and the sodium bisulfite solution is in a saturated state compared with the example 2, therefore, the addition reaction temperature is increased, the time required is longer compared with the example 1, and the reaction time is reduced compared with the example 2, which shows that the saturated sodium bisulfite solution enables the addition reaction of the ionone and the sodium bisulfite to be completed more easily.
Example 4
Adding 52g of sodium bisulfite, 94g of water (preparation concentration is 35%), 96g of ionone isomer mixture (total ketone 92%, alpha-I50%, beta-I40%, gamma-I2%) into a 1000ml three-neck flask, and uniformly stirring; then 58g of the recovered ethanol in the above example 3 is added, stirred uniformly, heated to 84 ℃, kept at the reflux temperature, stirred and reacted for 7.5 hours, the stirring is stopped, and the solution is kept still to be a clear, transparent and uniform system without floating oil. Recovering ethanol to 96 deg.C, accounting for about 90% of ethanol feed amount, stopping stirring, standing for 15min, and observing to obtain a uniform transparent system. Stirring and cooling to room temperature to obtain a viscous crystalline material, namely the ionone-alpha sodium hydroxysulfonate adduct.
In this example, ionone: sodium bisulfite: ethanol molar ratio ═ 1: 1: 2.5, but using recovered ethanol, the other conditions were the same as in example 3. Compared with example 3, the reaction time was prolonged because the concentration of the sodium bisulfite solution was reduced due to the presence of a certain amount of water in the recovered alcohol. But indicates that the recovered ethanol can be reused.
Example 5
Adding 78g of sodium bisulfite, 145g of water (preparation concentration is 35%), 96g of ionone isomer mixture (total ketone 92%, alpha-I50%, beta-I40%, gamma-I2%) into a 1000ml three-neck flask, and uniformly stirring; adding 64g of methanol, stirring uniformly, heating to 82 ℃, keeping the reflux temperature, stirring for reacting for 8 hours, stopping stirring, and standing to obtain a clear and transparent uniform system without floating oil. And (3) beginning to recover the methanol, recovering the methanol to 88 ℃, wherein the methanol accounts for about 85% of the feeding amount of the methanol, stopping stirring, and standing for 15min to observe the methanol to be a uniform and transparent system. Stirring and cooling to room temperature to obtain a viscous crystalline material, namely the ionone-alpha sodium hydroxysulfonate adduct.
In this example, ionone: sodium bisulfite: methanol molar ratio of 1: 1.5: 4, the sodium bisulfite solution was saturated, the solvent was methanol instead of ethanol, the reaction temperature was 82 ℃, and the reaction time was 8 hours, because the mixture ratio was the same as that of example 1, but the addition reaction of ionone with saturated sodium bisulfite was accelerated after the solvent was changed to methanol, but the time required was longer and the addition reaction time was 8 hours, compared with example 1.
While the invention has been described with reference to specific embodiments, this description is not meant to be construed in a limiting sense. Other variations of the disclosed embodiments, as would be appreciated by those skilled in the art with reference to the description of the invention, are contemplated as falling within the scope of the appended claims.
Claims (5)
1. A production method of an ionone-alpha sodium hydroxysulfonate adduct is characterized by comprising the following steps:
mixing the ionone isomer mixture with 30-40% sodium bisulfite aqueous solution, adding a certain proportion of lower aliphatic alcohol solvent with less than 5 carbon atoms, stirring uniformly, heating to 78-90 ℃, and carrying out reflux reaction for 4-8 hours to completely convert the ionone isomer into alpha-hydroxysulfonic acid sodium salt; recovering solvent, cooling to room temperature to obtain thick crystal material to obtain ionone-alpha hydroxy sodium sulfonate adduct;
wherein the molar ratio of the fed amount of the sodium bisulfite to the fed amount of the ionone isomer mixture is 0.5-2:1, and the molar ratio of the fed amount of the lower aliphatic alcohol solvent to the fed amount of the ionone isomer mixture is 0.5-5: 1.
2. the method for producing an ionone-alpha hydroxysulfonic acid sodium salt adduct according to claim 1, characterized in that: the lower aliphatic alcohol is one or more of methanol, ethanol, isopropanol, and n-butanol.
3. The method for producing an ionone-alpha hydroxysulfonic acid sodium salt adduct according to claim 2, characterized in that: the lower aliphatic alcohol is ethanol.
4. The method for producing an ionone-alpha hydroxysulfonic acid sodium salt adduct according to claim 1, characterized in that: mixture of ionone isomers in the above reaction: sodium bisulfite: the molar ratio of the feeding proportion of the lower aliphatic alcohol is 1: 1-1.5: 2.5-4.
5. The method for producing an ionone-alpha hydroxysulfonic acid sodium salt adduct according to claim 1, characterized in that: the low-grade fatty alcohol solvent can be recycled continuously without refining.
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