CN108101817B - β method for preparing cantharis yellow by oxidation of carotene - Google Patents

β method for preparing cantharis yellow by oxidation of carotene Download PDF

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CN108101817B
CN108101817B CN201711415029.6A CN201711415029A CN108101817B CN 108101817 B CN108101817 B CN 108101817B CN 201711415029 A CN201711415029 A CN 201711415029A CN 108101817 B CN108101817 B CN 108101817B
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carotene
canthaxanthin
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oxidant
hydrogen peroxide
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CN108101817A (en
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黄聿魏
赵家宇
肖亮
苏清菊
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Xiamen Kingdomway Vitamin Co ltd
Xiamen Kingdomway Group Co
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Xiamen Kingdomway Group Co
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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 invention discloses a method for preparing canthaxanthin by oxidizing β -carotene, which comprises the following steps of adding β -Dissolving carotene in organic solvent, and oxidizing β -carotene into canthaxanthin by using oxidant capable of generating oxygen atom under allyl oxidation catalyst shown as compound I and cocatalyst capable of generating iodine anion;

Description

β method for preparing cantharis yellow by oxidation of carotene
Technical Field
The invention relates to a preparation method of canthaxanthin, in particular to a method for preparing canthaxanthin by oxidizing β -carotene.
Background
Canthaxanthin is prepared by synthesizing canthaxanthin and adding the canthaxanthin into chicken feed in 1950. the canthaxanthin is found to exist in yolk and can make yolk produce orange red color which is favored by consumers.FDA and WHO approve the canthaxanthin to be added into food additive and set quality standard in 1984. according to the pharmacological research in recent years, canthaxanthin has pharmacological actions of resisting oxidation, improving blood fat change and the like.
Regarding the two-liquid phase oxidation method, various methods for preparing canthaxanthin by using β -carotene through two-liquid phase oxidation method have been reported in chinese patent publication No. CN1793098A, chinese patent publication No. CN101633633A and published academic literature (chemical bulletin 2006, 57(5)), however, the above methods all disclose that halate is used as an oxidizing agent, the amount of the used halate is large, the waste of the used halate is not easily treated, the environment is polluted to a certain extent, and the yield is low.
Disclosure of Invention
The invention aims to provide a method for preparing canthaxanthin by oxidizing β -carotene, which avoids generating halogen acid salt waste which is difficult to treat and has the advantages of environmental protection and high yield.
The technical purpose of the invention is realized by the following technical scheme:
a method for preparing canthaxanthin by oxidizing β -carotene comprises the following steps:
β -carotene is dissolved in an organic solvent, under the allyl oxidation catalyst shown as a compound I and a cocatalyst capable of generating iodine anions, β -carotene is oxidized into canthaxanthin by using an oxidant capable of generating oxygen atoms;
Figure BDA0001521361910000021
by adopting the technical scheme, the cocatalyst can generate iodine negative ions to activate β -carotene molecular double bonds, the catalyst can activate oxygen atoms generated by the oxidant, so that the activated oxygen atoms have energy for oxidizing β -carotene into canthaxanthin, the organic solvent has the effect of dissolving β -carotene and canthaxanthin, and the β -carotene is oxidized into canthaxanthin by the oxidant under the catalytic action of the catalyst and the cocatalyst, so that the problem that the generated halate waste is difficult to treat due to the fact that halate is used as the oxidant is avoided, and the method has the advantages of being green and environment-friendly.
The invention is further configured to: the oxidant is air, oxygen, hydrogen peroxide or hydrogen peroxide compound.
By adopting the technical scheme, the compounds of air, oxygen, hydrogen peroxide and hydrogen peroxide are all common oxidants capable of providing oxygen atoms, so that the production cost is reduced as far as possible on the premise of avoiding using halide as an oxidant.
The invention is further configured to: the compound of the hydrogen peroxide is urea peroxide, alkali metal peroxycarbonate or alkyl hydrogen peroxide.
By adopting the technical scheme, the urea peroxide, the alkali metal peroxycarbonate and the alkyl hydrogen peroxide are all compounds of hydrogen peroxide which are commonly used and can provide oxygen atoms, so that the production cost is reduced as far as possible on the premise of avoiding using halide as an oxidant.
The invention is further provided that when the oxidant is gas, the reaction gauge pressure is controlled to be 0-0.2 Mpa, preferably 0-0.1 MPa, and when the oxidant is liquid or solid, the mixing molar ratio of the oxidant and β -carotene is 1-20: 1, preferably 1-10: 1, and more preferably 1-5: 1.
By adopting the technical scheme, when the oxidant is gas, the larger the gauge pressure is, the larger the volume concentration of the oxidant is, the proper reaction pressure avoids the waste of resources caused by the overlarge concentration of the oxidant and the too small dosage which causes that the β -carotene cannot be oxidized into the canthaxanthin.
The invention is further configured to: r in the compound I11And R12Is the same H, an electron withdrawing group or an electron donating group, R in the compound I21And R22The same H, electron withdrawing group or electron donating group.
By adopting the technical scheme, the electron cloud of the central ion in the compound I and the electron cloud of the ligand form conjugated electron cloud to form a large pi bond conjugated structure, and R is11And R12、R21And R22Can form conjugation with the large pi-bond conjugated structure.
The invention further relates toThe method comprises the following steps: r in the compound I11And R12、R21And R22Is H, halogen, OH, NO2、COR4、OCOR4、COOR4Or SO3R4。
By adopting the technical scheme, the electron cloud of the central ion in the compound I and the electron cloud of the ligand form conjugated electron cloud to form a large pi bond conjugated structure, and R is11And R12、R21And R22Can form conjugation with the large pi-bond conjugated structure.
The invention is further configured to: the R is4Is H or C1-C4 alkyl.
The invention is further configured to: r in the compound I31、R32Are the same hydrogen, electron withdrawing group or electron donating group.
By adopting the technical scheme, the electron cloud of the central ion in the compound I and the electron cloud of the ligand form conjugated electron cloud to form a large pi bond conjugated structure, and R is31、R32Can form conjugation with the large pi-bond conjugated structure.
The invention is further configured to: r in the compound I31And R32Is H, R5X，R5OH，R5NO2，R5COR6，R5OCOR6，R5COOR6Or R5SO3R6And X is halogen.
By adopting the technical scheme, the electron cloud of the central ion in the compound I and the electron cloud of the ligand form conjugated electron cloud to form a large pi bond conjugated structure, and R is31、R32Can form conjugation with the large pi-bond conjugated structure.
The invention is further configured to: the R is5Is C1-C4 alkyl, the R6Is H or C1-C4 alkyl.
The invention is further configured to: the central ion in the compound I is a transition metal ion.
By adopting the technical scheme, the electron cloud of the transition metal ions and the electron cloud of the ligand form a conjugated electron cloud, and the transition metal ions can activate oxygen atoms provided by the oxidant.
The invention is further configured to: the transition metal ions are chromium, manganese, cobalt, copper or palladium.
The invention is further provided that the mixing molar ratio of the catalyst and β -carotene is 0.001-0.1: 1.
By adopting the technical scheme, the catalyst is proper in dosage, so that the waste of resources caused by overlarge dosage is avoided, the phenomenon that the catalytic effect is too weak and the production efficiency is too low caused by too little dosage is avoided.
The invention is further provided that the mixing molar ratio of the catalyst and β -carotene is 0.01-0.1: 1.
By adopting the technical scheme, the catalyst is proper in dosage, so that the waste of resources caused by overlarge dosage is avoided, the phenomenon that the catalytic effect is too weak and the production efficiency is too low caused by too little dosage is avoided.
The invention is further configured to: the cocatalyst is iodine or a compound containing iodine negative ions.
By adopting the technical scheme, iodine or the compound containing iodine negative ions can generate iodine negative ions to activate β -carotene molecular double bonds.
The invention is further configured to: the cocatalyst is iodine, potassium iodide or sodium iodide.
By adopting the technical scheme, iodine, potassium iodide and sodium iodide can generate iodine negative ions to activate β -carotene molecular double bonds, and meanwhile, iodine, potassium iodide and sodium iodide are common substances, so that the production cost is reduced.
The invention is further provided that the mixing molar ratio of the cocatalyst and β -carotene is 0.001-0.1: 1.
By adopting the technical scheme, the consumption of the cocatalyst is proper, so that the waste of resources caused by overlarge consumption is avoided, the phenomenon that the cocatalyst effect is too weak and the production efficiency is too low caused by too little consumption is avoided.
The invention is further provided that the mixing molar ratio of the cocatalyst and β -carotene is 0.01-0.1: 1.
By adopting the technical scheme, the consumption of the cocatalyst is proper, so that the waste of resources caused by overlarge consumption is avoided, the phenomenon that the cocatalyst effect is too weak and the production efficiency is too low caused by too little consumption is avoided.
The invention is further configured to: the organic solvent is dichloromethane, trichloromethane, tetrachloromethane, ethyl acetate or petroleum ether.
By adopting the technical scheme, the dichloromethane, the trichloromethane, the tetrachloromethane, the ethyl acetate and the petroleum ether have higher solubility to the β -carotene and the canthaxanthin.
The invention is further provided that the mixing weight ratio of the β -carotene to the organic solvent is 1: 10-100.
By adopting the technical scheme, the mixing weight ratio refers to the weight ratio of different substances during mixing, and the organic solvent is proper in dosage, so that not only is the waste of resources caused by excessive dosage avoided, but also the situation that β -carotene and canthaxanthin cannot be dissolved caused by too little dosage is avoided.
The invention is further provided that the mixing weight ratio of the β -carotene to the organic solvent is 1: 40-60.
By adopting the technical scheme, the organic solvent is appropriate in dosage, so that not only is the waste of resources caused by excessive dosage avoided, but also the incapability of dissolving β -carotene and canthaxanthin caused by too little dosage is avoided.
The invention is further configured to: the reaction temperature is-20 to 60 ℃.
By adopting the technical scheme, the reaction temperature is proper, the reaction rate is high, the reaction selectivity is high, and the phenomenon that the resource waste of temperature regulation is overlarge due to overhigh or overlow reaction temperature is avoided.
The invention is further configured to: the reaction temperature is-10 to 30 ℃.
By adopting the technical scheme, the reaction temperature is proper, the reaction rate is high, the reaction selectivity is high, and the phenomenon that the resource waste of temperature regulation is overlarge due to overhigh or overlow reaction temperature is avoided.
In conclusion, the invention has the following beneficial effects:
1. the method adopts compounds of air, oxygen, hydrogen peroxide or hydrogen peroxide to replace halide as an oxidant, avoids the discharge of unreacted oxides and oxide reductants, and has the characteristics of environmental protection;
2. the allyl oxidation catalyst is adopted to catalyze β -carotene oxidation to prepare canthaxanthin, so that the yield of the β -carotene oxidation canthaxanthin is improved;
3. the using amount of the oxidant is less, the least using amount is 1 time of the mole number of β -carotene, and the resource consumption is reduced;
4. the cocatalyst can generate iodine negative ions to activate β -carotene double bonds;
5. the electron cloud of the transition metal ion can form a conjugated electron cloud with the electron cloud of the ligand to form a large pi-bond conjugated structure, and R11And R12、R21And R22、R31And R32The central transition metal ion can activate the oxidant, so that the energy for generating oxygen atoms after the oxidant is activated can reach the energy required by oxidizing the β -carotene into canthaxanthin.
Detailed Description
In examples 1 to 10, the canthaxanthin content in the reaction solution was examined by the NYT 2896-2016 method, and the content of β -carotene in the reaction solution was examined by the USP35 method.
The catalyst was prepared with reference to the following documents:
G.N.Tyson，JR.，S.C.Adams.The configuration of some cupric，nickelousand cobaltous complexes by means of magnetic measurements.J.Am.Chem.Soc.1940，62：1228-1229；
synthesis and bacteriostatic activity of zhao quan celery, willow green, marfan. 3, 5-dibromo salicylaldehyde Schiff base and its copper (II) complex chemical reagent, 2001, 23 (1): 30-31.
Example 1
Dissolving β -carotene 0.1mol in dichloromethane 1.8L in a 2L reactor, adding catalyst (compound Ia) 0.001mol and iodine 0.01mol, cooling the reaction solution to-20 deg.C under sealed condition, introducing oxygen while stirring, controlling the reaction gauge pressure at 0.1MPa, controlling the reaction temperature at-20 deg.C, stirring for reaction until the reaction solution β -carotene is completely converted, detecting the content of canthaxanthin in the reaction solution, and calculating to obtain the canthaxanthin yield of 75.53%.
Figure BDA0001521361910000061
(R11＝H R12＝H R21＝H R22＝H R31＝CH2CH2OH R32＝CH2CH2OH M＝Cu)
Example 2
Dissolving β -carotene 0.1mol in chloroform 1.5L in a 2L reactor, adding catalyst (compound Ib) 0.01mol and potassium iodide 0.01mol, cooling the reaction solution to 0 deg.C under sealed condition, adding hydrogen peroxide (30% W) containing hydrogen peroxide 2mol while stirring, controlling the reaction temperature to 0 deg.C, stirring for reaction until the reaction solution β -carotene is completely converted, detecting canthaxanthin content in the reaction solution, and calculating canthaxanthin yield to 80.07%.
Figure BDA0001521361910000071
(R11＝H R12＝H R21＝SO3H R22＝SO3H R31＝CH2CH2SO3HR32＝CH2CH2SO3H M＝Cu)
Example 3
Dissolving β -carotene 0.1mol in tetrachloromethane 1.5L in a 2L reactor, adding catalyst 0.01mol (compound Ic) and potassium iodide 0.01mol, heating the reaction solution to 60 deg.C under sealed condition, introducing air while stirring, controlling the reaction gauge pressure to 0.1MPa, controlling the reaction temperature to 60 deg.C, stirring for reaction until the reaction solution β -carotene is completely converted, detecting the content of canthaxanthin in the reaction solution, and calculating to obtain the canthaxanthin yield of 60.37%.
Figure BDA0001521361910000072
(R11＝H R12＝H R21＝H R22＝H R31＝CH2CH2OH R32＝CH2CH2OH M＝Mn)
Example 4
Dissolving β -carotene 0.1mol in chloroform 1.5L in a 2L reactor, adding catalyst (compound Id) 0.001mol and sodium iodide 0.01mol, cooling the reaction solution to-5 deg.C under sealed condition, adding hydrogen peroxide (30% W) containing hydrogen peroxide 1mol while stirring, controlling the reaction temperature to-5 deg.C, stirring for reaction until the reaction solution β -carotene is completely converted, detecting the content of canthaxanthin in the reaction solution, and calculating to obtain canthaxanthin yield of 88.07%.
Figure BDA0001521361910000081
(R11＝H R12＝H R21＝H R22＝H R31＝CH2CH2OH R32＝CH2CH2OH M＝pd)
Example 5
Dissolving β -carotene 0.1mol in petroleum ether 1.5L in a 2L reactor, adding catalyst (compound Ie) 0.001mol and potassium iodide 0.01mol, cooling the reaction solution to-5 deg.C under sealed condition, adding oxygen while stirring, controlling the reaction gauge pressure at 0.05MPa, controlling the reaction temperature at-5 deg.C, stirring for reaction until the reaction solution β -carotene is completely converted, detecting the content of canthaxanthin in the reaction solution, and calculating to obtain canthaxanthin yield of 83.58%.
Figure BDA0001521361910000082
(R11＝H R12＝H R21＝SO3H R22＝SO3H R31＝CH2CH2SO3H R32＝CH2CH2SO3H M＝pd)
Example 6
Dissolving β -carotene 0.1mol in chloroform 1.5L in a 2L reactor, adding catalyst (compound If) 0.001mol and potassium iodide 0.01mol, cooling the reaction solution to-5 deg.C under sealed condition, adding sodium percarbonate 0.5mol while stirring, controlling the reaction temperature to-5 deg.C, stirring for reaction until the reaction solution β -carotene is completely converted, detecting the content of canthaxanthin in the reaction solution, and calculating to obtain canthaxanthin yield of 85.58%.
Figure BDA0001521361910000091
(R11＝Cl R12＝Cl R21＝H R22＝H R31＝CH2CH2OH R32＝CH2CH2OH M＝pd)
Example 7
Dissolving β -carotene 0.1mol in chloroform 1.44L in a 2L reactor, adding catalyst (compound Ig) 0.01mol and potassium iodide 0.01mol, cooling the reaction solution to 0 deg.C under sealed condition, adding urea peroxide 0.5mol while stirring, controlling the reaction temperature to 0 deg.C, stirring for reaction until the reaction solution β -carotene is completely converted, detecting the content of canthaxanthin in the reaction solution, and calculating to obtain canthaxanthin yield of 88.78%.
Figure BDA0001521361910000092
(R11＝Cl R12＝Cl R21＝H R22＝H R31＝CH2CH2OH R32＝CH2CH2OH M＝Mn)
Example 8
Dissolving β -carotene 0.1mol in ethyl acetate 3.6L in a 2L reactor, adding catalyst 0.0001mol (compound Ih) and sodium iodide 0.0001mol, sealing, adjusting the temperature of the reaction solution to 30 deg.C, introducing oxygen while stirring, controlling the pressure of the reaction gauge to 0.2MPa, controlling the reaction temperature to 30 deg.C, stirring for reaction until the conversion of β -carotene is completed, stopping the reaction, detecting the content of canthaxanthin in the reaction solution, and calculating to obtain canthaxanthin yield of 89.05%.
Figure BDA0001521361910000101
(R11＝OH R12＝OH R21＝OCOCH3R22＝OCOCH3R31＝CH3OCOCH2CH3R32＝CH3OCOCH2CH3M＝Co)
Example 9
Dissolving β -carotene 0.1mol in dichloromethane 0.405L in a 2L reactor, adding catalyst (compound Ii) 0.001mol and sodium iodide 0.001mol, cooling the reaction solution to-10 deg.C under sealed condition, adding tert-butyl hydroperoxide 0.1mol while stirring, controlling the reaction temperature to-10 deg.C, stirring for reaction until the reaction solution β -carotene is completely converted, detecting the content of canthaxanthin in the reaction solution, and calculating to obtain canthaxanthin yield of 85.36%.
Figure BDA0001521361910000102
(R11＝H R12＝H R21＝COOCH3R22＝COOCH3R31＝CH2Cl R32＝CH2Cl M＝Cr)
Example 10
Dissolving β -carotene 0.1mol in dichloromethane 4.05L in a 2L reactor, adding catalyst (compound Ij) 0.001mol and sodium iodide 0.001mol, cooling the reaction solution to-10 deg.C under sealed condition, adding potassium peroxycarbonate 0.1mol while stirring, controlling the reaction temperature at-10 deg.C, stirring for reaction until the reaction solution β -carotene is completely converted, detecting the content of canthaxanthin in the reaction solution, and calculating to obtain canthaxanthin yield of 80.36%.
Figure BDA0001521361910000111
(R11＝H R12＝H R21＝SO3CH2CH2CH2CH3R22＝COOCH2CH2CH2CH3R31＝CH2CH2CH2CH2ClR32＝CH2CH2CH2COOCH2CH2CH2CH3M＝Cu)
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.

Claims (2)

1. A method for preparing canthaxanthin by oxidizing β -carotene is characterized by comprising the following steps:
β -carotene is dissolved in organic solvent, under the allyl oxidation catalyst and cocatalyst as shown in compound I, β -carotene is oxidized into canthaxanthin by using oxidant capable of generating oxygen atom;
Figure FDA0002404678870000011
the oxidant is air, oxygen, hydrogen peroxide or a hydrogen peroxide compound, and the hydrogen peroxide compound is urea peroxide, alkali metal peroxycarbonate or alkyl hydrogen peroxide; the co-catalystThe reagent is iodine, potassium iodide or sodium iodide, and R in the compound I11And R12、R21And R22Is the same H, halogen, OH, NO2、COR4、OCOR4、COOR4Or SO3R4Said R is4Is H or C1-C4 alkyl; r in the compound I31And R32Are the same H, R5X，R5OH，R5NO2，R5COR6，R5OCOR6，R5COOR6Or R5SO3R6Wherein X is halogen and R is5Is C1-C4 alkyl, the R6Is H or C1-C4 alkyl; the central ion in the compound I is chromium, manganese, cobalt or palladium;
when the oxidant is gas, the reaction gauge pressure is controlled to be 0.1-0.2 MPa, when the oxidant is liquid or solid, the mixing molar ratio of the oxidant and β -carotene is 1-20: 1,
the reaction temperature is-20-60 ℃, the mixing molar ratio of the catalyst to β -carotene is 0.001-0.1: 1, and the mixing molar ratio of the cocatalyst to β -carotene is 0.001-0.1: 1.
2. The method for preparing canthaxanthin by oxidizing β -carotene according to claim 1, wherein the organic solvent is dichloromethane, chloroform, tetrachloromethane, ethyl acetate or petroleum ether, and optionally, the weight ratio of the mixture of β -carotene and the organic solvent is 1: 10-100.
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