CN107698478B - A method of it prepares different with oil viscosity beta carotene - Google Patents
A method of it prepares different with oil viscosity beta carotene Download PDFInfo
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- CN107698478B CN107698478B CN201711036792.8A CN201711036792A CN107698478B CN 107698478 B CN107698478 B CN 107698478B CN 201711036792 A CN201711036792 A CN 201711036792A CN 107698478 B CN107698478 B CN 107698478B
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- 235000013734 beta-carotene Nutrition 0.000 title claims abstract description 60
- 239000011648 beta-carotene Substances 0.000 title claims abstract description 60
- OENHQHLEOONYIE-UKMVMLAPSA-N all-trans beta-carotene Natural products CC=1CCCC(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C OENHQHLEOONYIE-UKMVMLAPSA-N 0.000 title claims abstract description 57
- TUPZEYHYWIEDIH-WAIFQNFQSA-N beta-carotene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CCCC1(C)C)C=CC=C(/C)C=CC2=CCCCC2(C)C TUPZEYHYWIEDIH-WAIFQNFQSA-N 0.000 title claims abstract description 57
- 229960002747 betacarotene Drugs 0.000 title claims abstract description 57
- OENHQHLEOONYIE-JLTXGRSLSA-N β-Carotene Chemical compound CC=1CCCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C OENHQHLEOONYIE-JLTXGRSLSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000006482 condensation reaction Methods 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 20
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims abstract description 10
- 150000004714 phosphonium salts Chemical class 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 4
- 238000010992 reflux Methods 0.000 claims abstract description 4
- 150000001579 beta-carotenes Chemical class 0.000 claims abstract description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical group [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- -1 sodium alkoxide Chemical class 0.000 claims 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims 1
- 230000005945 translocation Effects 0.000 claims 1
- 239000003921 oil Substances 0.000 description 35
- 235000019198 oils Nutrition 0.000 description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 17
- 238000009835 boiling Methods 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 235000019486 Sunflower oil Nutrition 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002600 sunflower oil Substances 0.000 description 4
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 3
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 description 3
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 235000019155 vitamin A Nutrition 0.000 description 3
- 239000011719 vitamin A Substances 0.000 description 3
- 229940045997 vitamin a Drugs 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000220259 Raphanus Species 0.000 description 2
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 201000009030 Carcinoma Diseases 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 208000002177 Cataract Diseases 0.000 description 1
- 235000004237 Crocus Nutrition 0.000 description 1
- 241000596148 Crocus Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 235000013376 functional food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000012053 oil suspension Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000004552 water soluble powder Substances 0.000 description 1
Classifications
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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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/045—Hydroxy compounds, e.g. alcohols; Salts thereof, e.g. alcoholates
- A61K31/047—Hydroxy compounds, e.g. alcohols; Salts thereof, e.g. alcoholates having two or more hydroxy groups, e.g. sorbitol
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/44—Oils, fats or waxes according to two or more groups of A61K47/02-A61K47/42; Natural or modified natural oils, fats or waxes, e.g. castor oil, polyethoxylated castor oil, montan wax, lignite, shellac, rosin, beeswax or lanolin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Veterinary Medicine (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- Organic Chemistry (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fodder In General (AREA)
- Lubricants (AREA)
Abstract
The different methods for matching oil viscosity beta carotene are prepared the invention discloses a kind of, include the following steps: (1) under the action of alkali catalyst, C15 phosphonium salt and C10 dialdehyde carry out condensation reaction in reaction dissolvent, obtain condensation reaction solution by neutralization after fully reacting；(2) step (1) resulting condensation reaction solution is added to turn device, infinite reflux indexing is carried out under heating condition；(3) stirring rate is reduced after indexing completely, adds crystalline seed, carry out crystallisation by cooling, the beta carotene is obtained by filtration.In the present invention, the different beta carotenes for matching oil viscosity can be obtained, technological operation is simple, and purpose is strong by the adding manner of adjusting condensation reaction solution.
Description
Technical field
The present invention relates to the preparation methods of beta carotene more particularly to a kind of prepare to meet difference with oil viscosity demand
The method of beta carotene.
Background technique
Beta carotene is a Carotenoids most generally existing in nature, is crocus fat-soluble compound.
As a kind of antioxidant, beta carotene has detoxication, is the maintenance indispensable nutrient of human health, anti-
Cancer, prevention cardiovascular disease, cataract and it is anti-oxidant on have significant function, a variety of as caused by aging and aging move back can be prevented
The property changed disease.When required, beta carotene can be changed into vitamin A after entering human body, do not have and ingest because excessive
Vitamin A and cause vitamin A progressive poisoning phenomenon.Meanwhile beta carotene has well UV-induced cutaneum carcinoma
Therapeutic effect.Therefore, functional food, cosmetics and in terms of be with a wide range of applications.
Existing beta carotene preparation method mainly includes chemical synthesis, salt algae cultivation, plant extraction method and life
Object fermentation method etc..Wherein chemical synthesis yield is maximum, for the preparation method of main product currently on the market.Common β-Hu
Radish element preparation has: crystallization, 30% oil suspension, 10% water-soluble dry powder, 1% aqueous suspensions and 1.5%
Water-soluble powder.It is 30% beta carotene vegetable oil with oil that wherein main dosage form, which is content,.In general, being prepared by chemical synthesis
Resulting 30% beta carotene vegetable oil fluctuates between 500~50000CP with oil, viscosity, and floatability is very big, mesh
Before, the prior art there are no document disclose which kind of technology can efficient, high purpose control beta carotene with oil viscosity.And
When being greater than 10000CP with oil viscosity, the mobility with oil weakens, and formulation spray treatment is seriously affected, therefore, in order to meet
The demand of the manufacture craft of beta carotene microcapsules can stablize the beta carotene prepared and match oil viscosity with different size
It is most important.
The correlative study of rheology shows that fine grain ratio in dispersion is too high or too low can all increase the viscous of slurry
Degree.Therefore correlation technique is had to look for, the average crystal size size of required beta carotene can be clearly controlled, to meet difference
Needs with oil viscosity.
Summary of the invention
First technical problem to be solved by this invention are as follows: a kind of preparation method of beta carotene, this method are provided
It is easy to operate, oil viscosity can be matched with stability contorting product beta carotene, beta carotene is avoided to match the floating of oil viscosity, and
According to different need that viscosity is adjusted.
A method of difference is prepared with oil viscosity beta carotene, is included the following steps:
(1) under the action of alkali catalyst, C15 phosphonium salt and C10 dialdehyde carry out condensation reaction in reaction dissolvent, reaction
Condensation reaction solution is obtained by neutralization after completely；
(2) step (1) resulting condensation reaction solution is added to turn device, infinite reflux indexing is carried out under heating condition；
In step (2), the difference of oil viscosity is matched according to the beta carotene of required preparation, to the addition side of condensation reaction solution
Formula is adjusted；
(3) stirring rate is reduced after indexing completely, adds crystalline seed, carry out crystallisation by cooling, the β-is obtained by filtration
Carrotene.
Wherein, the structural formula of C15 phosphonium salt isThe structural formula of C10 dialdehyde is
The present inventor has found that the factor with oil viscosity for influencing beta carotene essentially consists in indexing by long-term research
When β-carrot condensation reaction solution adding manner, the present invention goes the drop of turn device by adjusting β-carrot condensation reaction solution
Add mode and time for adding simultaneously optimize crystallization mode after indexing, can stably obtain the various different β-Hu Luo for matching oil viscosity
Bu Su, efficiently avoids the fluctuation with oil viscosity of beta carotene, to meet the needs of different occasions.
In step (2), the different dropwise addition modes are to be added at one time or be added dropwise in batches condensation reaction solution.
It is added at one time when condensation reaction solution is used to prepare the beta carotene with oil viscosity greater than 10000 and first adds 10%
~15% indexable solvent, is then directly put into turn device for condensation reaction solution entirely, puts Bi Shengwen indexing.
When condensation reaction solution being added dropwise in batches, need that 10% indexable solvent and 10% contracting is added in turn device in advance
Reaction solution is closed, after being heated to required temperature starts that remaining condensation reaction solution is added dropwise.
In industrial application, the beta carotene with oil viscosity lower (being less than 10000CP, more preferably less than 1000CP) exists
There is higher application value during formulation, but preparation is not easy, another problem to be solved by this invention is to provide
A kind of preparation method of the low beta carotene with oil viscosity.
When preparation is with 200~1000CP of oil viscosity beta carotene, preferably, remaining condensation liquid time for adding control is
10~20 hours.The beta carotene with oil viscosity is not easy to prepare using other methods, and uses preparation method of the invention
It can efficiently prepare.
When preparation is with oil viscosity 3000CP or so beta carotene, preferably, remaining condensation liquid time for adding control is 7
Hour.
When preparation is with oil viscosity 5000CP or so beta carotene, preferably, remaining condensation liquid time for adding control is 5
Hour.
When preparation is with oil viscosity 7000CP or so beta carotene, preferably, remaining condensation liquid time for adding control is 3
Hour.
When preparation is with oil viscosity 9000CP or so beta carotene, preferably, remaining condensation liquid time for adding control is 1
Hour.
Contain part Z formula structure by the beta carotene that condensation reaction obtains, needs to be translated into corresponding E formula knot
Structure keeps the application value of product higher.
In step (2), the indexable solvent for supplementing addition is C1~C6Alcohols solvent or C1~C6Ketones solvent or its mixing
Object.Such as methanol, ethyl alcohol, acetone etc. and their mixture.
Preferably, the temperature of indexing is 40~80 DEG C, the indexable time is 8~24 hours, at this point, the efficiency of indexing
Height, the content of E formula structure is higher in obtained product.
It is adjusted stirring rate after indexing completely, carries out crystallisation by cooling, final filtration obtains the beta carotene.
Preferably, the stirring rate of crystallisation by cooling is reduced to original 10% in step (3), with cool down 5 per hour~
10 DEG C of rates are cooled to 10~25 DEG C and are crystallized.
The preparation method of the different beta carotenes with oil viscosity of the present invention, advantage have technological operation letter
Single, purpose is strong；30% β-Hu of different viscosities can be prepared by adjusting the dropwise addition mode of beta carotene condensation reaction solution
Radish element meets the demand of subsequent beta carotene microcapsules manufacture craft with oil, is highly convenient for realizing industrialization cleaning life
It produces.
Specific embodiment
Embodiment 1
It takes 84g (0.13mol) C15 phosphonium salt to be added in 1000ml four-hole boiling flask, adds 400ml methanol stirring and dissolving, be passed through nitrogen
Then four-hole boiling flask is put into thermostat and is cooled to 10 DEG C by gas shielded；10.83g (0.065mol) C10 dialdehyde is added four mouthfuls
It in flask, starts simultaneously at and sodium methoxide solution (30% sodium methoxide+50ml methanol dilution of 20g) is added dropwise, time for adding control exists
10min or so.Drop finishes, 10 DEG C of insulation reactions.TCL monitoring reaction, C10 residue disappear substantially, reach reaction end.Reaction
Finish, 20g water is added, is passed through CO2Neutralize excessive sodium methoxide.It neutralizes and finishes, reaction solution is fully transferred to containing 45ml acetone solvent
Indexable four-hole boiling flask in, directly heating carry out indexing for 24 hours, when indexable stirring rate be 225rpm.Indexing is finished, and stirring speed is lowered
Rate adds 0.057g beta carotene crystal seed, is down to 25 DEG C with the rate of temperature fall of 5 DEG C/h, filter to obtain β-Hu to original 10%
Radish element finished product 26.1g.Under the conditions of HPLC, AE.LICHROM-SiO is used2- 5 (250mm*4.6mm SN:C14080401) columns, stream
Dynamic is mutually n-hexane: acetone=95:5, flow velocity 1.5ml/min are detected at 455nm, and (E)-isomers is 98.56%,
(Z)-isomers is 1.35%.30% is carried out with oil to beta carotene to synthesized using commercially available sunflower oil, matches oil grinding
1h is tested, viscosity 11400CP using viscosity apparatus (instrument producer model: the permanent flat viscosimeter NDJ-5S in Shanghai).
Embodiment 2
It takes 84g (0.13mol) C15 phosphonium salt to be added in 1000ml four-hole boiling flask, adds 400ml methanol stirring and dissolving, be passed through nitrogen
Then four-hole boiling flask is put into thermostat and is cooled to 10 DEG C by gas shielded；10.83g (0.065mol) C10 dialdehyde is added four mouthfuls
It in flask, starts simultaneously at and sodium methoxide solution (30% sodium methoxide+50ml methanol dilution of 20g) is added dropwise, time for adding control exists
10min or so.Drop finishes, 10 DEG C of insulation reactions.TCL monitoring reaction C10 residue disappears substantially, reaches reaction end.Reaction
Finish, 20g water is added, is passed through CO2Neutralize excessive sodium methoxide.Neutralize finish, into indexable flask be added 45ml acetone solvent and
45ml reaction solution is warming up to indexable temperature, residual reaction liquid is added dropwise into indexable four-hole boiling flask by constant pressure funnel, when dropwise addition
Between about 10h.Drop finishes, and for 24 hours, stirring rate is 225rpm when indexable for indexing.Indexing is finished, and lowers stirring rate to original
10%, 0.057g beta carotene crystal seed is added, is down to 25 DEG C with the rate of temperature fall of 5 DEG C/h, filters to obtain beta carotene finished product
26.3g.Under the conditions of HPLC, AE.LICHROM-SiO is used2- 5 (250mm*4.6mm SN:C14080401) columns, mobile phase are positive
Hexane: acetone=95:5, flow velocity 1.5ml/min are detected at 455nm, and (E)-isomers is 98.43%, (Z)-isomery
Body is 1.44%.30% is carried out with oil to beta carotene to synthesized using commercially available sunflower oil, matches oil grinding 1h, using viscous
Degree instrument (instrument producer model: the permanent flat viscosimeter NDJ-5S in Shanghai) is tested, viscosity 670CP.
Embodiment 3
It takes 84g (0.13mol) C15 phosphonium salt to be added in 1000ml four-hole boiling flask, adds 400ml methanol stirring and dissolving, be passed through nitrogen
Then four-hole boiling flask is put into thermostat and is cooled to 10 DEG C by gas shielded；10.83g (0.065mol) C10 dialdehyde is added four mouthfuls
It in flask, starts simultaneously at and sodium methoxide solution (preparation of 30% sodium methoxide+50ml methanol of 20g) is added dropwise, time for adding control exists
10min or so.Drop finishes, 10 DEG C of insulation reactions.TCL monitoring reaction C10 residue disappears substantially, reaches reaction end.Reaction
Finish, 20g water is added, is passed through CO2Neutralize excessive sodium methoxide.It neutralizes and finishes, 45ml acetone is added into indexable flask and 45ml is anti-
Liquid is answered, is heated up, and remaining condensation reaction solution is added dropwise into 1000ml indexing four-hole boiling flask by constant pressure funnel, time for adding is about
It is 7 hours.Drop finishes, and for 24 hours, stirring rate is 225rpm when indexable for indexing.Indexing is finished, downward stirring rate to original 10%,
0.057g beta carotene crystal seed is added, is down to 25 DEG C with the rate of temperature fall of 5 DEG C/h, filters to obtain beta carotene finished product 25.9g.
Under the conditions of HPLC, AE.LICHROM-SiO is used2- 5 (250mm*4.6mm SN:C14080401) columns, mobile phase is n-hexane:
Acetone=95:5, flow velocity 1.5ml/min are detected at 455nm, and (E)-isomers is 98.29%, and (Z)-isomers is
1.51%.30% is carried out with oil to beta carotene to synthesized using commercially available sunflower oil, matches oil grinding 1h, using viscosity apparatus
(instrument producer model: the permanent flat viscosimeter NDJ-5S in Shanghai) is tested, viscosity 3100CP.
Embodiment 4
It takes 84g (0.13mol) C15 phosphonium salt to be added in 1000ml four-hole boiling flask, adds 400ml methanol stirring and dissolving, be passed through nitrogen
Then four-hole boiling flask is put into thermostat and is cooled to 10 DEG C by gas shielded；10.83g (0.065mol) C10 dialdehyde is added four mouthfuls
It in flask, starts simultaneously at and sodium methoxide solution (preparation of 30% sodium methoxide+50ml methanol of 20g) is added dropwise, time for adding control exists
10min or so.Drop finishes, 10 DEG C of insulation reactions.TCL monitoring reaction C10 residue disappears substantially, reaches reaction end.Reaction
Finish, 20g water is added, is passed through CO2Neutralize excessive sodium methoxide.It neutralizes and finishes, 45ml acetone is added into indexable flask and 45ml is anti-
Liquid is answered, is heated up, and condensation reaction solution is added dropwise into 1000ml indexing four-hole boiling flask by constant pressure funnel, time for adding is about 3
Hour.Drop finishes, and for 24 hours, stirring rate is 225rpm when indexable for infinite reflux.Indexing is finished, and is lowered stirring rate to original 10%, is mended
Add 0.057g beta carotene crystal seed, be down to 25 DEG C with the rate of temperature fall of 5 DEG C/h, filters to obtain beta carotene finished product 26.3g.?
Under the conditions of HPLC, AE.LICHROM-SiO is used2- 5 (250mm*4.6mm SN:C14080401) columns, mobile phase is n-hexane: third
Ketone=95:5, flow velocity 1.5ml/min are detected at 455nm, and (E)-isomers is 98.15%, and (Z)-isomers is
1.61%.30% is carried out with oil to beta carotene to synthesized using commercially available sunflower oil, matches oil grinding 1h, using viscosity apparatus
(instrument producer model: the permanent flat viscosimeter NDJ-5S in Shanghai) is tested, viscosity 7300CP.
Claims (7)
1. a kind of prepare the different methods for matching oil viscosity beta carotene, which comprises the steps of:
(1) under the action of alkali catalyst, C15 phosphonium salt and C10 dialdehyde carry out condensation reaction, fully reacting in reaction dissolvent
Condensation reaction solution is obtained by neutralization afterwards；
Highly basic is or mixtures thereof one kind of sodium hydroxide, potassium hydroxide and sodium alkoxide or potassium alcoholate；
(2) step (1) resulting condensation reaction solution is added to turn device, infinite reflux indexing is carried out under heating condition；
In step (2), the difference of oil viscosity is matched according to the beta carotene of required preparation, to the adding manner of condensation reaction solution into
Row is adjusted；
When required beta carotene is 10000cp or more with oil viscosity, in step (2), first it is added in turn device
Then the indexable solvent of 10%~15% mass is directly added into whole condensation reaction solutions and carries out heating indexing；
When required beta carotene matches oil viscosity between 1000~10000cp, the first addition 10% in turn device~
15% indexable solvent and 10% condensation reaction solution, heating start to be added dropwise remaining condensation reaction solution and carry out heating indexing；
(3) stirring rate is reduced after indexing completely, adds crystalline seed, carry out crystallisation by cooling, the β-Hu Luo is obtained by filtration
Bu Su；
Wherein, the structural formula of C15 phosphonium salt isThe structural formula of C10 dialdehyde is
2. preparation difference according to claim 1 matches the method for oil viscosity beta carotene, which is characterized in that step (1)
In, the reaction dissolvent is C1~C6Alcohols solvent or C1~C6Ketones solvent；
The molar ratio of the C15 phosphonium salt and C10 dialdehyde is 1.5~2.5:1.
3. preparation difference according to claim 1 matches the method for oil viscosity beta carotene, which is characterized in that step (1)
In, the alkali catalyst is sodium methoxide, sodium ethoxide, potassium ethoxide, or mixtures thereof one of sodium tert-butoxide；
The setting-up point is between 0 DEG C~40 DEG C；
Neutralization reaction Shi Xianjia water, the dosage of the water of addition is the 3%~8% of condensation reaction solution quality, and is passed through excessive CO2Into
Row neutralizes.
4. preparation difference according to claim 1 matches the method for oil viscosity beta carotene, which is characterized in that be added dropwise remaining
The time of condensation reaction solution is 0.5~10 hour.
5. preparation difference according to claim 1 matches the method for oil viscosity beta carotene, which is characterized in that translocation reaction
Temperature be 40~80 DEG C, index time be 8~24 hours.
6. the according to claim 1, method of 4~5 described in any item beta carotenes of the preparation difference with oil viscosity, feature
It is, the indexable solvent is C1~C6Alcohols solvent or C1~C6One or more kinds of mixing of ketones solvent.
7. preparation difference according to claim 1 matches the method for oil viscosity beta carotene, which is characterized in that step (3)
In, 10% of stirring rate when stirring rate when crystallization is indexing, stirring rate is 150~300rpm, cooling when indexable
Rate is 5~10 DEG C/h, is cooled to 10~25 DEG C and is crystallized.
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Application publication date: 20180216 Assignee: ZHEJIANG NHU PHARMACEUTICAL Co.,Ltd. Assignor: SHANGYU NHU BIO-CHEM Co.,Ltd. Contract record no.: X2023980043734 Denomination of invention: A method for preparing different oil blending viscosities b- Method for carotene production Granted publication date: 20190423 License type: Common License Record date: 20231019 |