CN110078650A - A method of oxidation beta carotene prepares canthaxanthin - Google Patents
A method of oxidation beta carotene prepares canthaxanthin Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/24—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by six-membered non-aromatic rings, e.g. beta-carotene
Abstract
The advantages that present invention discloses a kind of method that oxidation beta carotene prepares canthaxanthin, and beta carotene one step oxidation in the presence of catalyst and oxidant sodium nitrate and carbon dioxide prepares canthaxanthin, has reaction condition mild, environmental-friendly, high income.
Description
Technical field
The invention belongs to chemosynthesis technical fields, are related to a kind of method that oxidation beta carotene prepares canthaxanthin.
Background technique
Canthaxanthin (or be canthaxanthin) is a Carotenoids, be present in certain mushrooms, shell-fish, fish, algae,
In egg, blood and liver.FDA/WHO approval canthaxanthin is included in food additives and has worked out quality standard within 1984.Canthaxanthin
Food additives be can be used as beverage, ice cream, waffle without auxiliary material biscuit, sauce, tomato processing product and meat packing
Product etc..Canthaxanthin is added in the feeds of poultry such as chicken, duck, generates a kind of favorite crocus of consumer in yolk.
1980, Joachim Paust (US4212827) et al. reported the side that oxidation beta carotene prepares canthaxanthin
Method.This method is to aoxidize beta carotene with chlorate or bromate in the presence of a catalyst, and this method is the disadvantage is that when reacting
Between it is too long, cause it is more difficult, technique is unstable, uses more iodide.
2000, gloomy pretty tree (CN1277191) et al. oxidation of beta-Hu under alkali metal chlorate or bromate acid condition
Radish element, the catalyst of addition are halogenation iodine, iodine or metal iodide.Halogenation iodine used includes lodine chloride, iodine trichloride, bromine
Change iodine and tribromide iodine, halogenation iodine can be used with single kind or is used in mixed way with a variety of.This method is the disadvantage is that oxidizing
Too strong, the product canthaxanthin oxidation deterioration of property, causes canthaxanthin yield not high；Used halogenation iodine has specific toxicity and volatilization
Property, and halogenation iodine is unstable, causes reaction yield unstable.
2001, Quesnel (EP1253131) research report used H2O2Make oxidant, I2For catalyst, chloroform or chlorine are selected
Benzene is solvent, and under room temperature, yield is up to 40%, oxidant H2O2It is pollution-free, but this method yield is not high.
Toshiki Mori (US6313352) et al. carried out on the basis of Joachim Paust (US4212827) compared with
Good improvement, the preparation of this method canthaxanthin are divided into three steps: beta carotene a) being dissolved in methylene chloride, by chlorate or bromic acid
The aqueous solution of salt is added in flask.B) add halogenation iodine or iodine.C) add potassium iodide or sodium iodide.The reaction time contracts significantly after improvement
It is short, the yield of canthaxanthin up to 76%, this method the disadvantage is that the halogenation iodine used have special toxicity and volatility and yield compared with
Low and halogenation iodine has unstability.
2003, it was with sulfurous acid, bisulfites or acid that GC, which applies the method for strangling Gadamer (CN1417207) invention,
The hypobromous acid that sulphite and bromate combine generation makees oxidant, so that canthaxanthin obtains good yield, while obvious
Ground shortens the reaction time.The disadvantages of the method are as follows the hypobromous acid generated is unstable, it is difficult to be applied in industrialization.
2003, Dubner Frank (EP1371642) et al. reported that oxidant NaClO solution is suitble to beta carotene oxygen
Change prepares canthaxanthin, I2For catalyst, this method reaction yield is up to 71%, but catalyst iodine highly volatile, stability are poor.Wu's generation
Woods (CN1793098) et al. invention mixes up the aqueous oxidizing agent solution that pH value is 2-5 with acid, in the light-illuminating condition of 200-800W
Lower oxidation beta carotene prepares canthaxanthin, and the easy decomposed metamorphic of illumination condition canthaxanthin product is reacted unstable, it is difficult to be used for work
Industry metaplasia produces.
2008, it was H that the beta carotene oxidation of Pi Shiqing (CN101633633) et al. invention, which prepares canthaxanthin method,2O2
Make catalyst, oxidant is alkali metal chlorate or bromate.This method reaction yield is up to 78%.This method is the disadvantage is that H2O2Make
There is strong oxidizing property for catalyst, cause reaction end uncontrollable, easy overreaction makes product canthaxanthin oxidation deterioration.
The above analysis has the following disadvantages: the catalyst halogenation iodine or elemental iodine used in existing preparation process, surely
Qualitative difference, and easily cause environmental pollution；The strong oxidizer used such as chlorate, hypochlorite or hydrogen peroxide etc. are in sulfuric acid, phosphorus
The strong acid such as acid are directly added into reaction system and form chloric acid, the hypochlorous acid etc. with strong oxidizing property, and too strong oxidisability will lead to production
Product canthaxanthin is oxidized simultaneously, and then causes product yield low.
Summary of the invention
For disadvantages mentioned above existing in the prior art, the present invention provides a kind of oxidation beta carotenes to prepare canthaxanthin
Method.It with sodium nitrate and carbon dioxide is for oxidant, using active metal iodide as catalyst in catalytic oxidation
Catalysis oxidation beta carotene synthesizes canthaxanthin, has reaction condition mild, high income, advantages of environment protection.
To solve the above problems, The technical solution adopted by the invention is as follows:
A method of oxidation beta carotene prepares canthaxanthin, in the presence of a catalyst, with sodium nitrate and carbon dioxide
For oxidant, beta carotene carries out oxidation reaction and prepares canthaxanthin.
In the present invention, the catalyst is active metal iodide, preferably potassium iodide and/or sodium iodide, more preferable iodate
Potassium；The dosage of the catalyst is 1~8%, preferably the 3~6% of beta carotene quality.
In the present invention, the weight ratio of the sodium nitrate and catalyst is 1~4:1, preferably 2~3:1.It is preferred that using sodium nitrate
Aqueous solution, the weight ratio of sodium nitrate and water is 1:1~10, preferably 1:6~8 in the sodium nitrate aqueous solution.It is highly preferred that
First catalyst is mixed with the aqueous solution of sodium nitrate before reaction, is formulated as the mixed aqueous solution of catalyst and sodium nitrate.
In the present invention, the carbon dioxide reaction process is continually fed into reaction solution, with every 10mmol beta carotene
For calculating benchmark, gas flow is controlled in 200~400mL/min.It is anti-by the controllable oxygenerating of control carbon dioxide flow rate
Rate is answered, so that reaching keeps oxidation reaction more stably and controllable.
In the preparation reaction of existing canthaxanthin, after oxidant is directly added into system, catalysis generates canthaxanthin product
It will lead to canthaxanthin product simultaneously further to aoxidize, the present invention is in catalyst system (active metal iodide), using nitric acid
Sodium and carbon dioxide are oxidant, and sodium nitrate non-oxidative itself acts synergistically with carbon dioxide auxiliary agent, in faintly acid system
It is interior, iodide ion can be aoxidized and consume iodination reaction generation hydrogen ion, maintenance system stablize, while protect canthaxanthin not by
Oxidation improves canthaxanthin yield.
As a preferred embodiment, oxidation reaction of the present invention carries out in carbon dioxide atmosphere, first will before reaction
Gas displacement is carbon dioxide in reactor, and carbon dioxide can not only be used for reaction protection gas, and can be slightly soluble in reaction system, is provided
Weak acid environment participates in oxidation reaction.
As a preferred embodiment, oxidation reaction of the present invention carries out in organic solvent, and the organic solvent is selected from
One of methylene chloride, dichloroethanes, ether, n-hexane are a variety of, preferably methylene chloride, and the consumption of organic solvent is former
20~25 times for expecting beta carotene weight.
It further include filtering, washing, desolventizing, recrystallization, filtering, the rear place such as dry in the present invention, after oxidation reaction
Reason process.
The solvent that the recrystallization uses is being selected from acetone, methylene chloride, ethyl alcohol, ether, n-hexane, hexamethylene, acetic acid just
One of propyl ester is a variety of, preferably acetone.The solvent usage is the 5 of canthaxanthin crude product (canthaxanthin before recrystallization) quality
~10 times.
Preferably, the recrystallization operation condition are as follows: then 70~75 DEG C of 8~12h of reflux are cooled to 20~30 DEG C, institute
Stating rate of temperature fall is preferably 8~15 DEG C/h.
The desolventizing condition is that temperature is 25~35 DEG C, and pressure is 6KPaA~2KPaA
The drying condition is that 50PaA~100PaA is dried in vacuo 8~15h；
As a preferred solution of the present invention, post-processing specific steps are as follows: canthaxanthin reaction solution 6KPaA~
2KPaA, 30 DEG C of condition of water bath heating backspins are evaporated off solvent, obtain canthaxanthin crude product, and the acetone of 8 times of quality is added (relative to angle
Flavine crude product quality) it dissolves, 70~75 DEG C of oil bath heatings reflux isomery 12h, 10 DEG C/h are cooled to 25 DEG C, and sand core funnel filters,
100PaA vacuum drying oven dries 12h, obtains aubergine canthaxanthin sterling.
As a kind of specific scheme of the invention, preparation method step are as follows: in carbon dioxide atmosphere, first by β-carrot
Element is dissolved in organic solvent, then passes to carbon dioxide, adds the mixed aqueous solution of catalyst and sodium nitrate, is uniformly mixed,
Stirring is lower to occur oxidation reaction, generates the product including canthaxanthin, and using filtering, washing takes organic phase to remove solvent, ties again
Crystalline substance, filtration drying obtain canthaxanthin product.
In the present invention, the oxidation reaction, reaction temperature is -10~50 DEG C, and the reaction time is 1~4h, reaction system
PH6.5~6.8.
In the present invention, the oxidation reaction is to reaction pressure without specific requirement, normal pressure.
In the present invention, the oxidation reaction preferably uses Temperature Programmed Processes, specifically: it is first -10~0 in reaction temperature
DEG C, preferably -9~-5 DEG C reactions 1~3h, preferably 1.5~2h；Then heat to 40~50 DEG C, preferably 41~48 DEG C heat preservations 1~
3h, preferably 1.5~2h.Further, the heating rate is preferably 1~5 DEG C/min, more preferable 1~3 DEG C/min.Continue height
Raw material beta carotene is perishable under warm environment, generates impurity, and first low-temp reaction generates after intermediate program liter again for a period of time
Temperature reaction generates canthaxanthin, both ensure that higher production efficiency in turn ensured the high yield of canthaxanthin, and had reduced the life of impurity
At.
In preparation method of the present invention, beta carotene can react completely, and for conversion ratio up to 100%, the selectivity of canthaxanthin can
Up to 99%, yield can reach 98% or more.
Rotten, halogenation iodine is easily oxidized based on canthaxanthin has the problems such as toxic pollutant, and the present invention is with sodium nitrate and dioxy
Change carbon as oxidizer system, active metal iodide prepare canthaxanthin as catalyst, catalysis oxidation beta carotene, anti-
Answer mechanism are as follows:
1) iodination reaction is different from chlorination and bromination reaction, since the average bond energy of C-I key is minimum in C-X key, simultaneously
The hydrogen iodide of generation has very strong reproducibility, and therefore, iodination reaction all has invertibity, for the generation for avoiding reversible reaction,
It should try except the hydrogen iodide generated in dereaction, to use the stronger three anion I of iodine of electrophilicity3-.The method for removing hydrogen iodide
Oxidant is exactly added, so that the stronger hydrogen iodide of reproducibility is oxidized to iodine, then with active metal iodide (with potassium iodide
For) complexing, form three anion I of iodine3-, to repeat to participate in reaction:
2) nitrate ion is under the solutions of weak acidity that carbon dioxide provides and iodide ion carries out redox reaction, production
Iodine.Iodine is complexed with potassium iodide again, forms three anion I of iodine3-Catalyst system:
3) by the iodination reaction of the above beta carotene, the iodide of allylic are generated, the type iodide have
Reaction can be directly hydrolyzed in stronger activity, obtain the pure and mild hydrogen iodide of C40:
4) C40 alcohol generates iodide again through iodination reaction:
5) iodide generate the bis- alcohol of C40 by hydrolysis:
6) the bis- alcohol of C40 pass through dehydration in acid condition, to generate canthaxanthin:
The positive effect of the present invention is: reaction condition is mild, and low-temperature atmosphere-pressure is environmental-friendly, raw material and product pair
Environment nonhazardous, canthaxanthin acid system stabilization are not easy oxidation deterioration, improve production efficiency and yield using temperature programming, can
It is less than yield in 4h in reaction total duration and is up to 98% or more.
Specific implementation method
The present invention will be further described below by way of examples, but is not limited only to the present embodiment.
Primary raw material source:
Raw material: beta carotene (96% is pure, Zhejiang medicine Xinchang pharmaceutical factory)
Reagent: methylene chloride (AR, western Gansu Province), acetone (AR, western Gansu Province), carbon dioxide (woods moral space division), potassium iodide (AR, Ah
Latin).
Analysis Instrument equipment and method:
The efficient liquid of high performance liquid chromatograph (HPLC (VIS)) or multiwavelength detector with visible spectrophotometric detector
Chromatography (HPLC), liquid chromatogram -- mass spectrum (LC/MS)
Analysis method:
1)HPLC
Detector: VIS or DAD (wavelength: 470nm wavelength greatest around)
Filler: octadecylsilyl SiClx glue (2~5 μm of partial size), 2.0~6.0mm of internal diameter, long 100~250mm
Column temperature: 40 DEG C
Mobile phase: 0.05% trifluoroacetic acid: methanol (3:97) mixed solution
Retention time standard: 7~10 minutes
2)LC/MS
Filler: octadecylsilyl SiClx glue (2~5 μm of partial size), 2.0~6.0mm of internal diameter, long 100~250mm
Column temperature: 40 DEG C
Mobile phase: 0.05% trifluoroacetic acid: methanol (3:97) mixed solution
Main ion (m/z): ESI+565
Retention time standard: 7~10 minutes
Embodiment 1
Beta carotene 5.36g (10mmol) will be taken to be placed in 500ml three-necked flask, carbon dioxide gas is replaced 3 times, is added
Enter 125g methylene chloride, -5 DEG C of stirrings are passed through carbon dioxide into reaction system with 300ml/min, catalyst potassium iodide is added
0.17g (1mmol) then takes sodium nitrate aqueous solution 3.18g (sodium nitrate: water=1:6), is then added in flask, -5 DEG C, reaction
Pressure normal pressure, reaction time 2h, 1 DEG C/min heating rate rise to 45 DEG C of heat preservation 2h, reaction process system PH6.5~6.8, mistake
Filter, is washed with water 3 times, separates organic phase, is spin-dried for that 50mL acetone is then added except solvent under 5KpaA, 30 DEG C of condition of water bath heating
Dissolution, 75 DEG C of oil bath heatings reflux isomery 10h, 15 DEG C/h are cooled to 25 DEG C, and sand core funnel filters, and 100PaA vacuum drying oven is dry
12h obtains aubergine canthaxanthin 5.53g, beta carotene conversion ratio 100.00%, canthaxanthin selectivity 98.05%, yield
98.05%.
Embodiment 2
Beta carotene 5.36g (10mmol) will be taken to be placed in 500ml three-necked flask, carbon dioxide gas is replaced 3 times, is added
Enter 125g methylene chloride, -10 DEG C of stirrings are passed through carbon dioxide into reaction system with 300ml/min, catalyst potassium iodide is added
0.17g (1mmol) then takes auxiliary agent sodium nitrate aqueous solution 3.18g (sodium nitrate: water=1:8), is then added in flask, -10
DEG C, reaction pressure normal pressure, reaction time 2h, 2 DEG C/min heating rate rises to 45 DEG C of heat preservations 2h, reaction process system PH6.5
~6.8, filtering is washed with water 3 times, separates organic phase, is spin-dried for then using and adding except solvent under 2KpaA, 25 DEG C of condition of water bath heating
Enter 60mL acetone solution, 70 DEG C of oil bath heatings reflux isomery 8h, 10 DEG C/h are cooled to 30 DEG C, and sand core funnel filters, and 100PaA is true
Empty oven drying 12h obtains aubergine canthaxanthin 5.36g, beta carotene conversion ratio 100.00%, canthaxanthin selectivity
95.04%, yield 95.04%.
Embodiment 3
Beta carotene 5.36g (10mmol) will be taken to be placed in 500ml three-necked flask, carbon dioxide gas is replaced 3 times, is added
Enter 125g methylene chloride, 0 DEG C of stirring is passed through carbon dioxide into reaction system with 300ml/min, catalyst potassium iodide is added
0.34g (2mmol) then takes auxiliary agent sodium nitrate aqueous solution 4.24g (sodium nitrate: water=1:7), is then added in flask, -5 DEG C,
Reaction pressure normal pressure, reaction time 1.5h, 3 DEG C/min heating rate rise to 45 DEG C of heat preservations 1.5h, reaction process system PH6.5
~6.8, filtering is washed with water 3 times, separates organic phase, is spin-dried for then using and adding except solvent under 6KpaA, 30 DEG C of condition of water bath heating
Enter 55mL acetone solution, 72 DEG C of oil bath heatings reflux isomery 10h, 8 DEG C/h are cooled to 25 DEG C, and sand core funnel filters, and 100PaA is true
Empty oven drying 12h obtains aubergine canthaxanthin 5.41g, beta carotene conversion ratio 100.00%, canthaxanthin selectivity
95.92%, yield 95.92%.
Embodiment 4
Beta carotene 5.36g (10mmol) will be taken to be placed in 500ml three-necked flask, carbon dioxide gas is replaced 3 times, is added
Enter 125g methylene chloride, -10 DEG C of stirrings are passed through carbon dioxide into reaction system with 300ml/min, catalyst potassium iodide is added
0.34g (2mmol) then takes auxiliary agent sodium nitrate aqueous solution 1.06g (sodium nitrate: water=1:2), is then added in flask, -10
DEG C, reaction pressure normal pressure, reaction time 2h, 2 DEG C/min heating rate rises to 45 DEG C of heat preservation 1.5h, reaction process system
PH6.5~6.8, filtering, are washed with water 3 times, separate organic phase, are spin-dried under 5KpaA, 30 DEG C of condition of water bath heating except solvent, so
Afterwards with 50mL acetone solution is added, 75 DEG C of oil bath heatings reflux isomery 10h, 10 DEG C/h are cooled to 25 DEG C, and sand core funnel filters,
100PaA vacuum drying oven dries 12h, obtains aubergine canthaxanthin 5.47g, beta carotene conversion ratio 100.00%, canthaxanthin choosing
Selecting property 96.98%, yield 96.98%.
Embodiment 5
Beta carotene 5.36g (10mmol) will be taken to be placed in 500ml three-necked flask, carbon dioxide gas is replaced 3 times, is added
Enter 125g methylene chloride, -10 DEG C of stirrings are passed through carbon dioxide into reaction system with 300ml/min, catalyst potassium iodide is added
0.17g (1mmol) then takes auxiliary agent sodium nitrate aqueous solution 2.12g (sodium nitrate: water=1:6), is then added in flask, -10
DEG C, reaction pressure normal pressure, reaction time 1h, 3 DEG C/min heating rate rises to 45 DEG C of heat preservations 2h, reaction process system PH6.5
~6.8, filtering is washed with water 3 times, separates organic phase, is spin-dried for then using and adding except solvent under 6KpaA, 70 DEG C of condition of water bath heating
Enter 50mL acetone solution, 30 DEG C of oil bath heatings reflux isomery 10h, 10 DEG C/h are cooled to 25 DEG C, and sand core funnel filters, and 100PaA is true
Empty oven drying 12h obtains aubergine canthaxanthin 5.53g, beta carotene conversion ratio 100.00%, canthaxanthin selectivity
98.05%, yield 98.05%.
Embodiment 6
Beta carotene 5.36g (10mmol) will be taken to be placed in 500ml three-necked flask, carbon dioxide gas is replaced 3 times, is added
Enter 125g methylene chloride, -10 DEG C of stirrings are passed through carbon dioxide into reaction system with 300ml/min, catalyst potassium iodide is added
0.34g (2mmol) then takes auxiliary agent sodium nitrate aqueous solution 3.18g (sodium nitrate: water=1:2), is then added in flask, -10
DEG C, reaction pressure normal pressure, reaction time 3h, 3 DEG C/min heating rate rises to 45 DEG C of heat preservations 2h, reaction process system PH6.5
~6.8, filtering is washed with water 3 times, separates organic phase, is spin-dried for then using and adding except solvent under 6KpaA, 70 DEG C of condition of water bath heating
Enter 50mL acetone solution, 30 DEG C of oil bath heatings reflux isomery 10h, 10 DEG C/h are cooled to 25 DEG C, and sand core funnel filters, and 100PaA is true
Empty oven drying 12h obtains aubergine canthaxanthin 5.43g, beta carotene conversion ratio 100.00%, canthaxanthin selectivity
96.35%, yield 96.35%.
Comparative example 1
Beta carotene 5.36g (10mmol) will be taken to be placed in 500ml three-necked flask, carbon dioxide gas is replaced 3 times, is added
Enter 125g methylene chloride, -5 DEG C of stirrings are passed through carbon dioxide into reaction system with 300ml/min, catalyst sodium iodide is added
0.34g is uniformly mixed, and then takes pure water 3.18g, is then added in flask, -5 DEG C, reaction pressure normal pressure, reaction time 2h,
Reaction process system PH6.5~6.8 are generated without canthaxanthin.
Comparative example 2
Beta carotene 5.36g (10mmol) will be taken to be placed in 500ml three-necked flask, carbon dioxide gas is replaced 3 times, is added
Enter 125g methylene chloride, -5 DEG C of stirrings are passed through carbon dioxide into reaction system with 300ml/min, catalyst iodine 0.34g is added
It is uniformly mixed, sodium metaperiodate 2.12g (10mmol) was then added and is dissolved with 3.18g water, is added in flask, -5 DEG C, reaction pressure
Power normal pressure, reaction time 2h, reaction process system PH6.5~6.8, filtering are washed with water 3 times, separate organic phase, are spin-dried for,
Then acetone recrystallization is used, aubergine canthaxanthin 2.21g, beta carotene conversion ratio 100.00%, canthaxanthin selectivity are obtained
39.18%, yield 39.18%.
Comparative example 3
Beta carotene 5.36g (10mmol) will be taken to be placed in 500ml three-necked flask, carbon dioxide gas is replaced 3 times, is added
Enter 125g methylene chloride, -5 DEG C of stirrings are passed through carbon dioxide into reaction system with 300ml/min, catalyst potassium iodide is added
0.34g is uniformly mixed, and is then added and is saturated aqueous sodium hypochlorite solution 15g, -5 DEG C, reaction pressure normal pressure, reaction time 2h, instead
Process system PH6.5~6.8 are answered, filters, is washed with water 3 times, organic phase is separated, is spin-dried for, acetone recrystallization is then used, obtains purple
Red canthaxanthin 3.31g, beta carotene conversion ratio 100.00%, canthaxanthin selectivity 58.77%, yield 58.77%.
Comparative example 4
Beta carotene 5.36g (10mmol) will be taken to be placed in 500ml three-necked flask, carbon dioxide gas is replaced 3 times, is added
Enter 125g methylene chloride, -5 DEG C of stirrings are passed through carbon dioxide into reaction system with 300ml/min, catalyst potassium iodide is added
0.34g be uniformly mixed, then be added sodium chlorate aqueous solution (concentration 30wt%) 3.18g, -5 DEG C, reaction pressure normal pressure, reaction when
Between be 2h, reaction process system PH6.5~6.8, filtering, be washed with water 3 times, separate organic phase, be spin-dried for, then tied again with acetone
Crystalline substance obtains aubergine canthaxanthin 2.25g, beta carotene conversion ratio 100.00%, canthaxanthin selectivity 39.89%, yield
39.89%.
Comparative example 5
Beta carotene 5.36g (10mmol) will be taken to be placed in 500ml three-necked flask, nitrogen is replaced 3 times, and 125g bis- is added
Chloromethanes, -5 DEG C of stirrings, is added 5% sulfuric acid 0.05g, and catalyst potassium iodide 0.34g is added and is uniformly mixed, sodium chlorate is then added
Aqueous solution 3.18g, -5 DEG C, reaction pressure normal pressure, reaction time 2h, reaction process system PH6.5~6.8, filtering are washed with water
It washs 3 times, separates organic phase, be spin-dried for, then use acetone recrystallization, obtain aubergine canthaxanthin 4.50g, beta carotene conversion ratio
100.00%, canthaxanthin selectivity 79.78%, yield 79.78%.
Claims (10)
1. a kind of oxidation beta carotene method for preparing canthaxanthin, which is characterized in that in the presence of a catalyst, with sodium nitrate and
Carbon dioxide is oxidant, and beta carotene carries out oxidation reaction and prepares canthaxanthin.
2. the method according to claim 1, wherein the catalyst is active metal iodide, preferably iodine
Change potassium and/or sodium iodide, more preferable potassium iodide；The dosage of the catalyst be beta carotene quality 1~8%, preferably 3~
6%.
3. method according to claim 1 or 2, which is characterized in that the weight ratio of the sodium nitrate and catalyst is 1~4:
1, preferably 2~3:1；It is preferred that using the aqueous solution of sodium nitrate, the weight ratio of sodium nitrate and water is 1:1 in the sodium nitrate aqueous solution
~10, preferably 1:6~8.
4. method according to claim 1-3, which is characterized in that the carbon dioxide reaction process is continually fed into
Into reaction solution, using every 10mmol beta carotene as calculating benchmark, gas flow is controlled in 200~400mL/min.
5. method according to claim 1-4, which is characterized in that the oxidation reaction is in carbon dioxide atmosphere
It carries out.
6. method according to claim 1-5, which is characterized in that the oxidation reaction in organic solvent into
Row, the organic solvent are selected from one of methylene chloride, dichloroethanes, ether, n-hexane or a variety of, preferably methylene chloride,
The consumption of organic solvent is 20~25 times of beta carotene weight.
7. method according to claim 1-6, which is characterized in that include that recrystallization is handled after oxidation reaction
Process；The solvent that the recrystallization uses is selected from acetone, methylene chloride, ethyl alcohol, ether, n-hexane, hexamethylene, n-propyl acetate
One of or it is a variety of, preferably acetone, the solvent usage are preferably 5~10 times of canthaxanthin crude product quality；Preferably, described
Recrystallization operation condition are as follows: then 70~75 DEG C of 8~12h of reflux are cooled to 20~30 DEG C, and the rate of temperature fall is preferably 8~
15℃/h。
8. method according to claim 1-7, which is characterized in that the oxidation reaction, reaction temperature be -10~
50 DEG C, the reaction time is 1~4h, reaction system PH6.5~6.8.
9. method according to claim 1-8, which is characterized in that the oxidation reaction uses temperature programming
Journey, specifically: it is first -10~0 DEG C in reaction temperature, preferably -9~-5 DEG C reactions 1~3h, preferably 1.5~2h；It then heats to
40~50 DEG C, preferably 41~48 DEG C heat preservations 1~3h, preferably 1.5~2h.
10. according to the method described in claim 9, it is characterized in that, the heating rate be 1~5 DEG C/min, preferably 1~3
℃/min。
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| CN113735753A (en) * | 2021-08-25 | 2021-12-03 | 万华化学集团股份有限公司 | Method for preparing high-stability canthaxanthin in high yield |
Citations (2)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113735753A (en) * | 2021-08-25 | 2021-12-03 | 万华化学集团股份有限公司 | Method for preparing high-stability canthaxanthin in high yield |
| CN113735753B (en) * | 2021-08-25 | 2022-08-05 | 万华化学集团股份有限公司 | Method for preparing high-stability canthaxanthin in high yield |
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