CN116854576A - Preparation method of aporate intermediate C25 aldehyde - Google Patents
Preparation method of aporate intermediate C25 aldehyde Download PDFInfo
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- -1 C25 aldehyde Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000007787 solid Substances 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000011575 calcium Substances 0.000 claims abstract description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 150000004714 phosphonium salts Chemical class 0.000 claims abstract description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 19
- 239000012295 chemical reaction liquid Substances 0.000 claims description 18
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 18
- 239000002585 base Substances 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 159000000007 calcium salts Chemical class 0.000 claims description 10
- 239000007791 liquid phase Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- 239000011775 sodium fluoride Substances 0.000 claims description 9
- 235000013024 sodium fluoride Nutrition 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 150000008282 halocarbons Chemical class 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 6
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 claims description 6
- 150000003754 zirconium Chemical class 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 150000003017 phosphorus Chemical class 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000009776 industrial production Methods 0.000 abstract 1
- 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 description 12
- 235000013734 beta-carotene Nutrition 0.000 description 12
- 239000011648 beta-carotene Substances 0.000 description 12
- 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 description 12
- 229960002747 betacarotene Drugs 0.000 description 12
- 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 description 12
- 239000000047 product Substances 0.000 description 11
- 238000007239 Wittig reaction Methods 0.000 description 9
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 7
- UIXZFZFOUVFQLU-UHFFFAOYSA-N methanol phosphane Chemical compound P.CO UIXZFZFOUVFQLU-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- UPYKUZBSLRQECL-UKMVMLAPSA-N Lycopene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1C(=C)CCCC1(C)C)C=CC=C(/C)C=CC2C(=C)CCCC2(C)C UPYKUZBSLRQECL-UKMVMLAPSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 206010040829 Skin discolouration Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 235000005473 carotenes Nutrition 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 235000013330 chicken meat Nutrition 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 235000015094 jam Nutrition 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 235000013310 margarine Nutrition 0.000 description 1
- 239000003264 margarine Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 235000013594 poultry meat Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- NCYCYZXNIZJOKI-UHFFFAOYSA-N vitamin A aldehyde Natural products O=CC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C NCYCYZXNIZJOKI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of an aporate intermediate C25 aldehyde, which comprises the steps of reacting deca-dialdehyde with C15 phosphonium salt under the action of a solid base catalyst, wherein the solid base catalyst is a supported catalyst loaded with fluorine, calcium, zirconium and cobalt; compared with the preparation method of the kettle-type reactor in the prior art, the preparation method of the invention obviously improves the conversion rate of raw materials and the selectivity of products, and has a yield of 90-95 percent and a better application prospect in large-scale industrial production.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to a preparation method of an aporate intermediate C25 aldehyde.
Background
The beta-apo-8' -ethyl carotene, also called apo ester, is mainly applied to margarine, jam, jelly and beverage foods in industry, and is also widely applied to skin coloring of meat poultry, especially edible chickens. As a class of chemically synthesized carotenoids, the synthesis method known at present (GB 1137429A, US5773635 a) adopts the c15+c10+c5 route for the synthesis of apoesters, but this process generates 10-15% of β -carotene during the synthesis of C25 aldehydes, which impurities are very similar to C25 aldehydes in nature and are difficult to remove, resulting in a reduced quality of the apoester product produced.
Therefore, a preparation method of an apoester intermediate C25 aldehyde with mild reaction conditions and simple and easy operation is sought, and the preparation method belongs to the difficult problem which needs to be solved in the industry.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a preparation method of an aporate intermediate C25 aldehyde, which can solve the problems of complex reaction operation and difficult impurity purification in the prior art, and provides a practical and efficient method for synthesizing the C25 aldehyde.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a preparation method of an aporate intermediate C25 aldehyde comprises the following steps: the deca-dialdehyde and the C15 phosphonium salt react under the action of a solid base catalyst.
Preferably, the solid base catalyst is a supported catalyst loaded with fluorine, calcium, zirconium and cobalt.
Preferably, the carrier of the solid base catalyst is activated carbon.
In the invention, the preparation method of the solid base catalyst comprises the following steps:
1) Adding calcium salt, cobalt salt, zirconium salt and active carbon into deionized water, stirring to obtain suspension, dropwise adding a mixed solution of hydrazine hydrate and sodium fluoride under the conditions of heating and stirring, and continuously stirring after the dropwise adding to obtain the mixed solution.
2) Transferring the mixed solution into a reaction kettle for reaction, cooling and filtering, washing with water, drying and roasting the filter cake to obtain the active carbon solid base catalyst loaded by fluorine, calcium, zirconium and cobalt.
Preferably, the calcium salt, cobalt salt and zirconium salt are soluble salts of calcium, cobalt and zirconium respectively.
Preferably, in the step 1), the mixed solution of hydrazine hydrate and sodium fluoride is dropwise added after heating to 90-120 ℃ for 2-10h.
Preferably, the reaction temperature in the step (2) is 80-120 ℃, the reaction pressure is 0.3-0.5MPa, and the reaction time is 10-20h.
Preferably, the roasting temperature in the step (2) is 500-600 ℃ and the roasting time is 10-20h.
Preferably, the mass ratio of the calcium salt, the cobalt salt, the zirconium salt and the activated carbon is 1:0.01-0.2:0.5-2.0:2.0 to 4.0;
preferably, the mass ratio of the calcium salt to the hydrazine hydrate is 1:0.2-1.0, and the mass ratio of the calcium salt to the sodium fluoride is 1:0.1-1.0;
preferably, first, mixing deca-dialdehyde, a halogenated hydrocarbon solvent and a solid base catalyst to obtain a material A; mixing C15 phosphate and alcohols to obtain a material B; then mixing the material A and the material B for reaction to obtain a reaction liquid;
preferably, the reaction is carried out in a microchannel reactor.
In the invention, the mass ratio of the deca-dialdehyde to the solid base catalyst is 1:0.1-2.0, and the preferred mass ratio is 1:0.2-0.5;
in the invention, the halogenated hydrocarbon solvent is one or more of dichloromethane, chloroform, dichloroethane and chlorobenzene;
wherein the mass ratio of the halogenated hydrocarbon solvent to the deca-dialdehyde is 6-10:1, preferably 7-8:1;
in the present invention, the alcohol is one or more selected from methanol, ethanol, isopropanol, n-butanol, etc.
The addition amount of the alcohol is 2-10 times, preferably 3-5 times of the mass of the C15 phosphate.
In the invention, the structural formula of the deca-dialdehyde is shown as a formula (1):
the structural formula of the C15 phosphorus salt is shown in the formula (2):
wherein X is Cl - Or Br (Br) - 。
Preferably, the molar ratio of the decanal to the C15 phosphate is 1:1.0-2.0, preferably 1:1.3-1.8;
preferably, the structural formula of the aporate intermediate C25 aldehyde is shown in a formula (3):
in the invention, the deca-dialdehyde, the halohydrocarbon solvent and the alkali solution are mixed and then are injected into a microchannel reactor through a metering pump 1; mixing the C15 phosphate and alcohols, and pumping the mixture into a microchannel reactor through a metering pump 2.
Preferably, the volume flow ratio of the material A to the material B is 0.8-1.5:1, preferably the flow ratio is 0.9-1.1:1.
according to the invention, the temperature of the microchannel reactor is controlled by circulating heat conducting oil of the refrigerating and heating integrated machine.
Preferably, the reaction temperature of the decadialdehyde and the C15 phosphonium salt is from 0 to 120℃and preferably from 20 to 50 ℃.
In the present invention, the reaction residence time is 10 to 50s, preferably 20 to 30s.
Washing the reaction liquid obtained after the reaction is finished, and then crystallizing and separating impurities such as beta-carotene and the like, wherein the liquid phase obtained is a C25 aldehyde solution system.
Wherein the washing solvent is pure water, the washing temperature is 20-45 ℃, and the mass of the pure water is 2-10 times of that of the deca-dialdehyde; adding a poor solvent to crystallize the impurities, wherein the poor solvent is preferably n-hexane, the crystallization temperature is 5-25 ℃, and the dosage of the poor solvent is 10-25 times of the mass of the deca-dialdehyde.
The invention has the beneficial effects that:
1. reaction aspects; using F-Co/CaO-ZrO supported 2 The active carbon solid alkali can effectively improve the reaction selectivity, reduce the generation of beta-carotene, effectively enrich the alkali catalytic site Ca by doped fluoride ions, and improve the catalyst alkalinity; the doped Co element can effectively improve the all-trans ratio of the C25 aldehyde product.
2. The process comprises the following steps: through the reaction mode of the micro-channel, the Wittig reaction can be effectively realized, and the excessive reaction can be controlled, so that the impurity content of beta-carotene in the system is less than 0.5%.
3. The cost aspect is as follows: compared with the prior kettle type reactor, the micro-channel reactor can complete all the works by 1-2 persons, the post-reaction treatment flow is simple, the reaction time is shortened from 3.0h to 20min, and the method has great advantages in the aspects of reaction cost and labor cost.
Detailed Description
The following examples will further illustrate the method provided by the present invention, but the invention is not limited to the examples listed and should include any other known modifications within the scope of the claimed invention.
Characterization by liquid chromatography: agilent 1260 type liquid chromatograph, column Sphermosorb C18 column (4.6X250 mm), UV visible spectroscopic detector Hitachi L7420, chromatographic workstation data processing system Chomatopac C-RIA, stationary phase Zorbax-SIL. Chromatographic conditions: the mobile phase is methanol/acetonitrile=8/2 (v/v) mixed solvent, the detection temperature is 40 ℃, the flow rate is 1ml/min, and the wavelength is 455nm. And carrying out qualitative and quantitative analysis on the composition of the product.
The main raw material information used in the following examples and comparative examples is as follows:
c15 phosphorus salt, homemade, prepared in the same way as step (1) of example 1 in patent CN109651150 a;
decanal (purity 99%) was purchased from Hubei optical company.
Sodium hydroxide, potassium hydroxide, triethylamine, sodium tert-butoxide, sodium methoxide, analytically pure, aletin;
the present invention will be described in detail with reference to specific examples.
Preparation example 1
50g of calcium chloride, 5g of cobalt chloride, 100g of zirconium chloride and 200g of active carbon are added into 500g of deionized water, the mixture is stirred to obtain a suspension, and under the conditions of heating in a water bath at 100 ℃ and stirring, a mixed solution of 30g of hydrazine hydrate and 10g of sodium fluoride is dropwise added, and after 2h of dropwise addition, the stirring is continued to obtain a mixed solution.
Transferring the mixed solution to a high pressure reactorIn a reaction kettle, the reaction temperature is 110 ℃, the reaction pressure is 0.4MPa, cooling and filtering are carried out after the reaction is carried out for 20 hours, 30g of deionized water is used for washing, then the filter cake is dried in vacuum, and the obtained solid is roasted in a muffle furnace at the high temperature of 600 ℃ for 15 hours to obtain F-Co/CaO-ZrO 2 Activated carbon solid base catalyst I.
Preparation example 2
50g of calcium chloride, 1.5g of cobalt chloride, 50g of zirconium chloride and 200g of active carbon are added into 500g of deionized water, the mixture is stirred to obtain a suspension, and under the conditions of heating in a water bath at 100 ℃ and stirring, a mixed solution of 25g of hydrazine hydrate and 10g of sodium fluoride is dropwise added into the suspension, and after 2 hours of dropwise addition, the stirring is continued to obtain a mixed solution.
Transferring the mixed solution into a high-pressure reaction kettle, reacting at 110 ℃ under 0.4MPa for 20 hours, cooling and filtering, washing the filter cake with 30g deionized water, vacuum drying, and roasting the obtained solid in a muffle furnace at 600 ℃ for 15 hours to obtain F-Co/CaO-ZrO 2 Activated carbon solid base catalyst II.
Preparation example 3
100g of calcium chloride, 10g of cobalt chloride, 80g of zirconium chloride and 350g of active carbon are added into 800g of deionized water, the mixture is stirred to obtain a suspension, and under the conditions of heating in a water bath at 100 ℃ and stirring, a mixed solution of 50g of hydrazine hydrate and 25g of sodium fluoride is dropwise added, and after 2 hours of dropwise addition, the stirring is continued to obtain a mixed solution.
Transferring the mixed solution into a high-pressure reaction kettle, reacting at 110 ℃ under 0.4MPa for 20 hours, cooling and filtering, washing the filter cake with 30g deionized water, vacuum drying, and roasting the obtained solid in a muffle furnace at 600 ℃ for 15 hours to obtain F-Co/CaO-ZrO 2 Activated carbon solid base catalyst III.
Example 1
The embodiment provides a preparation method of a deca-dialdehyde intermediate, which specifically comprises the following steps:
16.4g of decadialdehyde and 3.28g of F-Co/CaO-ZrO were loaded 2 Mixing the active carbon solid alkali I and 120g of dichloromethane solution, feeding the mixture into a micro-channel reactor by a metering pump, and feeding 200g of 20wt% C15 phosphonium salt methanol solution into the micro-channel reactor by the metering pump; metering pump 1 and metering pump 2 in feed volumeThe mixture enters a micro-channel reactor at a flow rate ratio of 1.5:1, wittig reaction is carried out at 30 ℃, the retention time of materials in the micro-channel reactor is 40s, reaction liquid is obtained, the reaction liquid is stored in a liquid storage tank 1, liquid phase analysis is carried out by sampling, the conversion rate of deca-dialdehyde of the raw material is 99.3%, the selectivity of C25 aldehyde of the product is 95.5%, the total trans-form ratio of C25 aldehyde is 98.6wt%, the content of beta-carotene is 0.3wt%, and the reaction yield is 94.8%.
Example 2
16.4g of decadialdehyde and 1.64g of F-Co/CaO-ZrO were charged 2 Mixing the active carbon solid alkali II and 110g of dichloromethane solution, feeding the mixture into a micro-channel reactor by a metering pump, and feeding 200g of 20wt% C15 phosphonium salt methanol solution into the micro-channel reactor by the metering pump; the metering pump 1 and the metering pump 2 enter a micro-channel reactor at a feed volume flow rate ratio of 1.3:1, wittig reaction is carried out at 30 ℃, the retention time of materials in the micro-channel reactor is 30s, a reaction liquid is obtained, the reaction liquid is stored in a liquid storage tank 1, sampling is carried out for liquid phase analysis, the conversion rate of the raw material deca-dialdehyde is 97.8%, the selectivity of the product C25 aldehyde is 96.7%, the total trans-form ratio of the C25 aldehyde is 99.1wt%, the content of beta-carotene is 0.1wt%, and the reaction yield is 94.6%.
Example 3
16.4g of decadialdehyde and 4.92g of F-Co/CaO-ZrO were loaded 2 Mixing active carbon solid alkali III and 100g of dichloromethane solution, feeding the mixture into a micro-channel reactor by a metering pump, and feeding 200g of 20wt% C15 phosphonium salt methanol solution into the micro-channel reactor by the metering pump; the metering pump 1 and the metering pump 2 enter a micro-channel reactor at a feed volume flow rate ratio of 0.95:1, wittig reaction is carried out at 30 ℃, the retention time of materials in the micro-channel reactor is 15s, a reaction liquid is obtained, the reaction liquid is stored in a liquid storage tank 1, sampling is carried out for liquid phase analysis, the conversion rate of the raw material deca-dialdehyde is 94.6%, the selectivity of the product C25 aldehyde is 95.9%, the total trans-form ratio of the C25 aldehyde is 98.7%, the content of beta-carotene is 0.15%, and the reaction yield is 90.7%.
Example 4
16.4g of decadialdehyde and 3.28g of F-Co/CaO-ZrO were loaded 2 The solid alkali II of activated carbon and 120g of methylene chloride solution are mixed and enter a micro-channel reactor by a metering pump, 190g of 20wt percent C15 phosphorusThe salt methanol solution enters a micro-channel reactor through a metering pump; the metering pump 1 and the metering pump 2 enter a micro-channel reactor at a feed volume flow rate ratio of 1.2:1, wittig reaction is carried out at 20 ℃, the retention time of materials in the micro-channel reactor is 25s, a reaction liquid is obtained, the reaction liquid is stored in a liquid storage tank 1, sampling is carried out for liquid phase analysis, the conversion rate of raw materials deca-dialdehyde is 99.0%, the selectivity of product C25 aldehyde is 96.5%, the total trans-form ratio of C25 aldehyde is 99.2wt%, the content of beta-carotene is 0.1wt%, and the reaction yield is 95.5%.
Example 5
16.4g of decadialdehyde and 3.28g of F-Co/CaO-ZrO were loaded 2 Mixing active carbon solid alkali III and 150g of dichloromethane solution, feeding the mixture into a micro-channel reactor by a metering pump, and feeding 205g of 20wt% C15 phosphonium salt methanol solution into the micro-channel reactor by the metering pump; the metering pump 1 and the metering pump 2 enter a micro-channel reactor at a feed volume flow rate ratio of 1.4:1, wittig reaction is carried out at 35 ℃, the retention time of materials in the micro-channel reactor is 30s, a reaction liquid is obtained, the reaction liquid is stored in a liquid storage tank 1, sampling is carried out for liquid phase analysis, the conversion rate of the raw material deca-dialdehyde is 98.3%, the selectivity of the product C25 aldehyde is 96.7%, the total trans-form ratio of the C25 aldehyde is 98.9wt%, the content of beta-carotene is 0.2wt%, and the reaction yield is 95.1%.
Example 6
16.4g of decadialdehyde and 8.2g of F-Co/CaO-ZrO were loaded 2 Mixing the active carbon solid alkali I and 120g of dichloromethane solution, feeding the mixture into a micro-channel reactor by a metering pump, and feeding 180g of 20wt% C15 phosphonium salt methanol solution into the micro-channel reactor by the metering pump; the metering pump 1 and the metering pump 2 enter a micro-channel reactor at a feed volume flow rate ratio of 1.5:1, wittig reaction is carried out at 45 ℃, the retention time of materials in the micro-channel reactor is 30s, a reaction liquid is obtained, the reaction liquid is stored in a liquid storage tank 1, sampling is carried out for liquid phase analysis, the conversion rate of the raw material deca-dialdehyde is 98.9%, the selectivity of the product C25 aldehyde is 94.2%, the total trans-form ratio of the C25 aldehyde is 98.5wt%, the content of beta-carotene is 0.4wt%, and the reaction yield is 93.2%.
Example 7
16.4g of decadialdehyde and 8.2g of F-Co/CaO-ZrO were loaded 2 Activated carbon solid alkali I120g of methylene dichloride solution is mixed and then added into a 1000mL 3-mouth flask, 180g of 20wt% C15 phosphonium salt methanol solution is added into a reaction system in a dropwise manner, wittig reaction is carried out at 45 ℃, liquid phase analysis is carried out by sampling, so that the raw material deca-di-aldehyde conversion rate is 92.6%, the product C25 aldehyde selectivity is 89.5%, the total trans-form ratio of C25 aldehyde is 98.8wt%, the beta-carotene content is 0.25wt%, and the reaction yield is 82.9%.
Comparative example 1
16.4g of deca-dialdehyde, 8.2g of activated carbon solid alkali loaded with potassium carbonate and 120g of methylene dichloride solution are mixed and enter a micro-channel reactor through a metering pump, and 180g of 20wt% C15 phosphonium salt methanol solution enters the micro-channel reactor through the metering pump; the metering pump 1 and the metering pump 2 enter a micro-channel reactor at a feed volume flow rate ratio of 1.5:1, wittig reaction is carried out at 45 ℃, the retention time of materials in the micro-channel reactor is 30s, a reaction liquid is obtained, the reaction liquid is stored in a liquid storage tank 1, sampling is carried out for liquid phase analysis, the conversion rate of raw materials deca-dialdehyde is 95.3%, the selectivity of product C25 aldehyde is 78.6%, the total trans-form ratio of C25 aldehyde is 90.5wt%, the content of beta-carotene is 5.9wt%, and the reaction yield is 74.9%.
Claims (9)
1. A method for preparing an aporate intermediate C25 aldehyde, which is characterized by comprising the following steps: the deca-dialdehyde and the C15 phosphonium salt react under the action of a solid base catalyst.
2. The preparation method according to claim 1, wherein the solid base catalyst is a supported catalyst on which fluorine, calcium, zirconium and cobalt are supported;
preferably, the carrier of the solid base catalyst is activated carbon.
3. The preparation method according to claim 1, wherein the preparation method of the solid base catalyst is as follows:
1) Adding calcium salt, cobalt salt, zirconium salt and active carbon into deionized water, stirring to obtain suspension, dropwise adding a mixed solution of hydrazine hydrate and sodium fluoride into the suspension under the conditions of heating and stirring, and continuously stirring after the dropwise adding to obtain a mixed solution;
2) Transferring the mixed solution into a reaction kettle for reaction, cooling and filtering, washing with water, drying and roasting the filter cake to obtain the active carbon solid base catalyst loaded by fluorine, calcium, zirconium and cobalt.
4. A method according to claim 3, wherein the calcium salt, cobalt salt, zirconium salt are soluble salts of calcium, cobalt, zirconium, respectively;
preferably, in the step 1), the mixed solution of hydrazine hydrate and sodium fluoride is dropwise added after heating to 90-120 ℃ for 2-10h;
preferably, the reaction temperature in the step (2) is 80-120 ℃, the reaction pressure is 0.3-0.5MPa, and the reaction time is 10-20h;
preferably, the roasting temperature in the step (2) is 500-600 ℃ and the roasting time is 10-20h.
5. The preparation method according to claim 3 or 4, wherein the mass ratio of the calcium salt, the cobalt salt, the zirconium salt and the activated carbon is 1:0.01-0.2:0.5-2.0:2.0 to 4.0;
preferably, the mass ratio of the calcium salt to the hydrazine hydrate is 1:0.2-1.0, and the mass ratio of the calcium salt to the sodium fluoride is 1:0.1-1.0.
6. The process according to any one of claims 1 to 5, wherein a decadialdehyde, a halogenated hydrocarbon solvent and a solid base catalyst are mixed to obtain a material a; mixing C15 phosphate and alcohols to obtain a material B; then mixing the material A and the material B for reaction to obtain a reaction liquid;
preferably, the reaction is carried out in a microchannel reactor;
preferably, the halogenated hydrocarbon solvent is one or more of dichloromethane, chloroform, dichloroethane and chlorobenzene;
preferably, the mass ratio of the halogenated hydrocarbon solvent to the deca-dialdehyde is 6-10:1, preferably 7-8:1;
preferably, the alcohol is selected from one or more of methanol, ethanol, isopropanol and n-butanol;
preferably, the alcohols are added in an amount of 2 to 10 times, preferably 3 to 5 times the mass of the C15 phosphonium salt.
7. The method according to any one of claims 1 to 6, wherein the decadialdehyde has a structural formula represented by formula (1):
the structural formula of the C15 phosphorus salt is shown in the formula (2):
wherein X is Cl - Or Br (Br) - ；
The mass ratio of the deca-dialdehyde to the solid base catalyst is 1:0.1-2.0, and the preferred mass ratio is 1:0.2-0.5;
preferably, the molar ratio of the decanal to the C15 phosphate is 1:1.0-2.0, preferably 1:1.3-1.8;
preferably, the structural formula of the aporate intermediate C25 aldehyde is shown in a formula (3):
8. the preparation method according to any one of claims 1 to 6, wherein the decadialdehyde, the halogenated hydrocarbon solvent and the alkali solution are mixed and then fed into the microchannel reactor through a metering pump 1; mixing C15 phosphate and alcohols, and pumping the mixture into a microchannel reactor through a metering pump 2;
preferably, the volume flow ratio of the material A to the material B is 0.8-1.5:1, preferably the flow ratio is 0.9-1.1:1, a step of;
preferably, the reaction temperature of the decadialdehyde and the C15 phosphonium salt is from 0 to 120 ℃, preferably from 20 to 50 ℃;
preferably, the reaction residence time is from 10 to 50s, preferably from 20 to 30s.
9. The process according to any one of claims 1 to 6, wherein the reaction liquid obtained after completion of the reaction is washed and then the impurities are separated by crystallization to obtain a liquid phase which is a C25 aldehyde solution system;
preferably, the washing solvent is pure water, the washing temperature is 20-45 ℃,
preferably, the mass of the pure water is 2-10 times of the mass of the deca-dialdehyde;
preferably, the impurity is crystallized by adding a poor solvent, preferably n-hexane, at a crystallization temperature of 5-25 ℃, wherein the dosage of the poor solvent is 10-25 times of the mass of the deca-dialdehyde.
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