CN105646311A - Method for preparing beta-Apo-8'-carotenal - Google Patents
Method for preparing beta-Apo-8'-carotenal Download PDFInfo
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- 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
- C07C403/14—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 doubly-bound oxygen atoms
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Abstract
The invention discloses a method for preparing beta-Apo-8'-carotenal. The method includes steps of (1) synthesizing raw materials 2, 6, 6-trimethyl-1- cyclohexanemethanol and triphenylphosphine as raw materials into 2, 6, 6-trimethyl-1-cyclohexene methyl triphenylphosphine salt; (2) subjecting 2, 6, 6-trimethyl-1-cyclohexene methyl triphenylphosphine salt and 2, 6, 11, 15-tetramethyl-2, 4, 6, 8, 10, 12, 14-hexadecanoyl heptaene dialdehyde to wittig reaction to obtain beta-Apo-8'-carotenal. The method using 2, 6, 6-trimethyl-1- cyclohexanemethanol as raw materials is safe in reaction and is a novel method.
Description
Technical field
The present invention relates to organic synthesis field, more particularly, relate to one and prepare β-A PiaoThe method of-8 '-carrot aldehyde.
Background technology
β-A Piao-8'-carrot aldehyde (structural formula I) is the one of carotenoid,Be widely used in feed industry. β-A Piao-8'-carrot aldehyde also can be used for synthesizing simultaneouslyOther carotenoid. Therefore, the synthetic method of research β-A Piao-8'-carrot aldehyde hasPractical value.
The method of existing synthetic β-A Piao-8'-carrot aldehyde is as follows:
1. document (Xu, PingjunChengduKejiDaxueXuebao, (3), 77-84;1992) reported the preparation method of β-A Piao-8'-carrot aldehyde, its synthetic route is as reactionFormula one:
The beta carotene oxidation scission containing 40 carbon atoms is become β-A Piao-8'-by the methodCarrot aldehyde, generates some accessory substances in addition, does not have economy.
2. patent (RuttimannEur.Pat.Appl.07Jan1998) has been described and has been used β-A Piao-12'-carrotene dimethylacetal is prepared the method for β-A Piao-8'-carrot aldehyde,Its synthetic route is as reaction equation two:
β-A Piao for the method-12'-carrotene dimethylacetal and 1-methoxyl group-2-methylThe condensation of-1,3-butadiene, uses BFEE compound, obtains β-A Piao-8'-trailing plants recklesslyForetell aldehyde.
In sum, the method 1 of the above-mentioned β of preparation-A Piao-8'-carrot aldehyde adopts existing HuRadish element product, a part of structure is removed in oxidation, and generates accessory substance, does not have economy;Method 2 is used BFEE compound, and this compound is met moisture aloft and is hydrolyzed immediately,When decomposition, generate hypertoxic hydrogen fluoride smog, be unfavorable for industrialization, therefore neither be preferably squareMethod. The new method of studying a kind of β of preparation-A Piao-8'-carrot aldehyde has actual application value.
Summary of the invention
The technical problem to be solved in the present invention is, for the above-mentioned defect of prior art, providesA method for synthetic β-A Piao-8'-carrot aldehyde, the method is with 2,6,6-trimethyl-1-Cyclohexene methyl alcohol is raw material, and course of reaction safety, without dangerous, is preparation β-A Piao-8'-A kind of new method of carrot aldehyde.
The technical solution adopted for the present invention to solve the technical problems is: provide one prepare β-The method of A Piao-8 '-carrot aldehyde, comprises the steps:
(1) with 2,6,6-trimethyl-1-cyclohexene methyl alcohol and triphenylphosphine for raw material, denseUnder hydrochloric acid or concentrated sulfuric acid condition, synthesize 2,6,6-trimethyl-1-cyclohexene methyl triphenyl quaternary phosphineSalt;
(2) by step (1), make 2,6,6-trimethyl-1-cyclohexene methyl triphenylQuaternary alkylphosphonium salt and 2,6,11,15-tetramethyl-2,4,6,8,10,12,14-, 16 carbon seven alkene dialdehyde warpsCross Wittig reaction, obtain β-A Piao-8 '-carrot aldehyde.
The method of preparing β-A Piao-8 '-carrot aldehyde of the present invention, wherein, this preparationThe method of β-A Piao-8 '-carrot aldehyde also comprises respectively carries out pure to the product of step (1)The process of changing, concrete operations are as follows: treat step (1) after completion of the reaction, are cooled to room temperature,Add water, with n-hexane extraction twice, water layer dichloromethane extraction three times, merge organic layer,Then use anhydrous Na2SO4Dry, removal of solvent under reduced pressure, removes by cyclohexane or petroleum etherImpurity, or separate and obtain thick solid through silica gel column chromatography, 2,6,6-trimethyl-1-ringHexene methyl triphenyl quaternary alkylphosphonium salt.
The method of preparing β-A Piao-8 '-carrot aldehyde of the present invention, wherein, this preparationThe method of β-A Piao-8 '-carrot aldehyde also comprises respectively carries out pure to the product of step (2)The process of changing, concrete operations are as follows: after step (2) reaction, add saturated ammonium chloride solution,CH2Cl2Extract three times, merge organic layer, use anhydrous Na2SO4Dry organic layer, decompression is removedSolvent, through silica gel column chromatography or recrystallization, obtains β-A Piao-8 '-carrot aldehyde.
The method of preparing β-A Piao-8 '-carrot aldehyde of the present invention, wherein, described siliconElution system in plastic column chromatography is benzinum: ethyl acetate=10:1.
The method of preparing β-A Piao-8 '-carrot aldehyde of the present invention, wherein, described stepSuddenly the concrete operations of (1) are as follows: in reaction bulb, add methyl alcohol, add 2,6,6-trimethyl-1-cyclohexene methyl alcohol and triphenylphosphine, after mixing and stirring, drip at lower than 15 DEG C denseHydrochloric acid or the concentrated sulfuric acid add hot reflux 6-10 hour under nitrogen protection after dropwising, to obtain final product2,6,6-trimethyl-1-cyclohexene methyl triphenyl quaternary alkylphosphonium salt.
The method of preparing β-A Piao-8 '-carrot aldehyde of the present invention, wherein, described ringThe mol ratio of lemon alcohol and triphenylphosphine is 1:(1-1.5).
The method of preparing β-A Piao-8 '-carrot aldehyde of the present invention, wherein, described stepSuddenly in (1) 2,6, the mol ratio of 6-trimethyl-1-cyclohexene methyl alcohol and concentrated hydrochloric acid or the concentrated sulfuric acidFor 1:(1-1.5).
The method of preparing β-A Piao-8 '-carrot aldehyde of the present invention, wherein, described stepSuddenly the concrete operations of (2) are as follows: by step (1), make 2,6,6-trimethyl-1-ringHexene methyl triphenyl quaternary alkylphosphonium salt, stirs at ambient temperature, adds the methanol solution of sodium methoxide,After dropwising, under nitrogen protection, stir 0.5-1h, then add again 2,6,11,15-tetramethylBase-2,4,6,8,10,12,14-, 16 carbon seven alkene dialdehyde, room temperature reaction 1-4 hour.
The method of preparing β-A Piao-8 '-carrot aldehyde of the present invention, wherein, described in2,6,6-trimethyl-1-cyclohexene methyl triphenyl quaternary alkylphosphonium salt, sodium methoxide and 2,6,11,15-tetra-Methyl-2, the mol ratio of 4,6,8,10,12,14-, 16 carbon seven alkene dialdehyde is 1:(1-2):(1-1.5)。
Implement the method for preparing β-A Piao-8 '-carrot aldehyde of the present invention, have following usefulEffect:
The present invention by with 2,6,6-trimethyl-1-cyclohexene methyl alcohol and triphenylphosphine for raw material,First synthetic corresponding 2,6,6-trimethyl-1-cyclohexene methyl triphenyl quaternary alkylphosphonium salt, recycling2,6,6-trimethyl-1-cyclohexene methyl triphenyl quaternary alkylphosphonium salt and 2,6,11,15-tetramethyl-2,4,6,8,10,12,14-, 16 carbon seven alkene dialdehyde, through Wittig reaction, obtain β-A Piao-8 '-carrot aldehyde.
Detailed description of the invention
Below, in conjunction with detailed description of the invention, the present invention is described further:
One is prepared the method for β-A Piao-8 '-carrot aldehyde, comprises the steps:
(1) with 2,6,6-trimethyl-1-cyclohexene methyl alcohol and triphenylphosphine for raw material, denseUnder hydrochloric acid or concentrated sulfuric acid condition, synthesize 2,6,6-trimethyl-1-cyclohexene methyl triphenyl quaternary phosphineSalt; In reaction bulb, add methyl alcohol, add 2,6,6-trimethyl-1-cyclohexene methyl alcohol and threePhenylphosphine, the mol ratio of 2,6,6-trimethyl-1-cyclohexene methyl alcohol and triphenylphosphine is 1:(1-1.5); After mixing and stirring, at lower than 15 DEG C, drip concentrated hydrochloric acid or the concentrated sulfuric acid,Wherein, the mol ratio of ring lemon alcohol and concentrated hydrochloric acid or the concentrated sulfuric acid is 1:(1-1.5). DripAfter under nitrogen protection, add hot reflux 6-10 hour. Treat step (1) after completion of the reaction,Be cooled to room temperature, add water, with n-hexane extraction twice, water layer dichloromethane extraction three times,Merge organic layer, then use anhydrous Na2SO4Dry, removal of solvent under reduced pressure, with cyclohexane or stoneImpurity is removed in oil ether washing, or separates and obtain thick solid through silica gel column chromatography, and 2,6,6-Trimethyl-1-cyclohexene methyl triphenyl quaternary alkylphosphonium salt.
(2) by step (1), make 2,6,6-trimethyl-1-cyclohexene methyl triphenylQuaternary alkylphosphonium salt and 2,6,11,15-tetramethyl-2,4,6,8,10,12,14-, 16 carbon seven alkene dialdehyde warpsCross Wittig reaction, obtain β-A Piao-8 '-carrot aldehyde. By making in step (1)2,6,6-trimethyl-1-cyclohexene methyl triphenyl quaternary alkylphosphonium salt, at ambient temperature stir,Add the methanol solution of sodium methoxide, after dropwising, under nitrogen protection, stir 0.5-1h, connectAnd add again 2,6,11,15-tetramethyl-2,4,6,8,10,12,14-, 16 carbon seven alkene dialdehyde,Room temperature reaction 1-4 hour. Described 2,6,6-trimethyl-1-cyclohexene methyl triphenyl quaternary phosphineSalt, sodium methoxide and 2,6,11,15-tetramethyl-2,4,6,8,10,12,14-, 16 carbon seven alkene twoThe mol ratio of aldehyde is 1:(1-2): (1-1.5). After step (2) reaction, add saturated chlorineChange ammonium salt solution, CH2Cl2Extract three times, merge organic layer, use anhydrous Na2SO4Dry organic layer,Removal of solvent under reduced pressure, through silica gel column chromatography or recrystallization, obtains β-A Piao-8 '-carrot aldehyde.Wherein, the elution system in described silica gel column chromatography is benzinum: ethyl acetate=10:1.
The synthetic route of β-A Piao-8 ' of the present invention-carrot aldehyde is as follows:
In all embodiment,1H-NMR、13C-NMR is by BrukerAV-400 type NMRMeasure, with deuterochloroform (CDCl3) be solvent, tetramethylsilane (TMS) is interior mark; MatterSpectrum is measured with Agilent6210 (DOF-MAS) mass spectrograph.
Embodiment 1The preparation of β-A Piao-8 '-carrot aldehyde:
In 100mL reaction bulb, add methyl alcohol (50mL), 2,6,6-trimethyl-1-cyclohexeneMethyl alcohol (1.54g, 10mmol) and triphenylphosphine (3.14g, 12mmol), after mixing and stirring.At lower than 15 DEG C, drip 1.5g concentrated hydrochloric acid, after dropwising, under nitrogen protection, add hot reflux8 hours. TLC (benzinum: ethyl acetate=5:1) detection reaction terminal. Question response is completeAfter but to room temperature, add 20mL water, with n-hexane extraction (25mL × 2), water layer dichloromethaneAlkane extraction (25mL × 3), merges organic layer, anhydrous Na2SO4Dry, removal of solvent under reduced pressure,Wash and remove impurity with cyclohexane (or benzinum), or separate through silica gel column chromatography (ethanol)To thick solid, be 2,6,6-trimethyl-1-cyclohexene methyl triphenyl quaternary alkylphosphonium salt, produceRate 50%.
In reaction bulb, add 2,6,6-trimethyl-1-cyclohexene methyl triphenyl quaternary alkylphosphonium salt(4.34g, 10mmol) and methyl alcohol (20mL). Sodium methoxide (0.81g, 15mmol) is dissolved in 20mLIn methyl alcohol, under stirring at room temperature, join in reaction bulb, after dropwising, under nitrogen protection, stir0.5h, and then add 2,6,11,15-tetramethyl-2,4,6,8,10,12,14-, 16 carbon sevenAlkene dialdehyde (2.96g, 10mmol), room temperature reaction 4h. After having reacted, add saturated chlorinationAmmonium salt solution 40mL, CH2Cl2Extraction (25mL × 3), organic layer is with subtracting after anhydrous sodium sulfate dryingPress except desolventizing, through silica gel column chromatography (benzinum: ethyl acetate=10:1) or recrystallization,Obtain β-A Piao-8 '-carrot aldehyde, productive rate 38%.
Embodiment 2The preparation of β-A Piao-8 '-carrot aldehyde:
In 100mL reaction bulb, add methyl alcohol (50mL), 2,6,6-trimethyl-1-cyclohexeneMethyl alcohol (1.54g, 10mmol) and triphenylphosphine (2.62g, 10mmol), after mixing and stirring.At lower than 15 DEG C, drip 1.5g concentrated hydrochloric acid, after dropwising, under nitrogen protection, add hot reflux6 hours. TLC (benzinum: ethyl acetate=5:1) detection reaction terminal. Question response is completeAfter but to room temperature, add 20mL water, with n-hexane extraction (25mL × 2), water layer dichloromethaneAlkane extraction (25mL × 3), merges organic layer, anhydrous Na2SO4Dry, removal of solvent under reduced pressure,Wash and remove impurity with cyclohexane (or benzinum), or separate through silica gel column chromatography (ethanol)To thick solid, be 2,6,6-trimethyl-1-cyclohexene methyl triphenyl quaternary alkylphosphonium salt, produceRate 45%.
In reaction bulb, add 2,6,6-trimethyl-1-cyclohexene methyl triphenyl quaternary alkylphosphonium salt(4.34g, 10mmol) and methyl alcohol (20mL). Sodium methoxide (0.54g, 10mmol) is dissolved in 20mLIn methyl alcohol, under stirring at room temperature, join in reaction bulb, after dropwising, under nitrogen protection, stir0.5h, and then add 2,6,11,15-tetramethyl-2,4,6,8,10,12,14-, 16 carbon sevenAlkene dialdehyde (2.96g, 10mmol), room temperature reaction 1h. After having reacted, add saturated chlorinationAmmonium salt solution 40mL, CH2Cl2Extraction (25mL × 3), organic layer is with subtracting after anhydrous sodium sulfate dryingPress except desolventizing, through silica gel column chromatography (benzinum: ethyl acetate=10:1) or recrystallization,Obtain β-A Piao-8 '-carrot aldehyde, productive rate 23%.
Embodiment 3The preparation of β-A Piao-8 '-carrot aldehyde:
In 100mL reaction bulb, add methyl alcohol (50mL), 2,6,6-trimethyl-1-cyclohexeneMethyl alcohol (1.54g, 10mmol) and triphenylphosphine (3.85g, 15mmol), after mixing and stirring.At lower than 15 DEG C, drip 1.5g concentrated hydrochloric acid, after dropwising, under nitrogen protection, add hot reflux10 hours. TLC (benzinum: ethyl acetate=5:1) detection reaction terminal. Question response is completeAfter finishing, but to room temperature, add 20mL water, with n-hexane extraction (25mL × 2), water layer dichloroMethane extraction (25mL × 3), merges organic layer, anhydrous Na2SO4Dry, removal of solvent under reduced pressure,Wash and remove impurity with cyclohexane (or benzinum), or separate through silica gel column chromatography (ethanol)To thick solid, be 2,6,6-trimethyl-1-cyclohexene methyl triphenyl quaternary alkylphosphonium salt, produceRate 52%.
In reaction bulb, add 2,6,6-trimethyl-1-cyclohexene methyl triphenyl quaternary alkylphosphonium salt(4.34g, 10mmol) and methyl alcohol (20mL). Sodium methoxide (1.08g, 20mmol) is dissolved in 20mLIn methyl alcohol, under stirring at room temperature, join in reaction bulb, after dropwising, under nitrogen protection, stir0.5h, and then add 2,6,11,15-tetramethyl-2,4,6,8,10,12,14-, 16 carbon sevenAlkene dialdehyde (4.44g, 15mmol), room temperature reaction 2h. After having reacted, add saturated chlorinationAmmonium salt solution 40mL, CH2Cl2Extraction (25mL × 3), organic layer is with subtracting after anhydrous sodium sulfate dryingPress except desolventizing, through silica gel column chromatography (benzinum: ethyl acetate=10:1) or recrystallization,Obtain β-A Piao-8 '-carrot aldehyde, productive rate 35%.
Get β-A Piao-8 '-carrot aldehyde that embodiment 1-3 prepares and identify, as followsData result for its various spectrum:
Product β-A Piao-8 '-carrot aldehyde spectroscopic data:
1H-NMR(400MHz,CDCl3):δ9.45(s,1H),6.12-6.96(m,12H),2.06-2.02(m,2H),2.00(s,9H),1.90(s,3H),1.72(s,3H),1.60-1.64(m,2H),1.45-1.49(m,2H),1.03(s,6H)；
13C-NMR(100MHz,CDCl3)δ194.6,149.4,138.7,137.7,136.9,135.2,133.1,131.9,130.7,129.6,129.1,127.2,126.2,122.7,39.6,34.3,33.2,29.0,21.8,19.3,13.0,12.8,9.7。
HRMS-ESI:Calcd.For:C30H40O[M+Na]+:439.2977；Found:439.2972。
To one skilled in the art, can be according to technical scheme described above and structureThink, make other various corresponding changes and deformation, and all these changes and deformationWithin all should belonging to the protection domain of the claims in the present invention.
Claims (9)
1. a method of preparing β-A Piao-8 '-carrot aldehyde, is characterized in that, comprisesFollowing steps:
(1) with 2,6,6-trimethyl-1-cyclohexene methyl alcohol and triphenylphosphine for raw material, denseUnder hydrochloric acid or concentrated sulfuric acid condition, synthesize 2,6,6-trimethyl-1-cyclohexene methyl triphenyl quaternary phosphineSalt;
(2) by step (1), make 2,6,6-trimethyl-1-cyclohexene methyl triphenylQuaternary alkylphosphonium salt and 2,6,11,15-tetramethyl-2,4,6,8,10,12,14-, 16 carbon seven alkene dialdehyde warpsCross Wittig reaction, obtain β-A Piao-8 '-carrot aldehyde.
2. the method for preparing β-A Piao-8 '-carrot aldehyde according to claim 1,It is characterized in that, this method of preparing β-A Piao-8 '-carrot aldehyde also comprises respectively to step(1) product carries out the process of purifying, and concrete operations are as follows: treat that step (1) reacts completeAfter, be cooled to room temperature, add water, with n-hexane extraction twice, water layer dichloromethane extractionThree times, merge organic layer, then use anhydrous Na2SO4Dry, removal of solvent under reduced pressure, uses hexamethyleneAlkane or petroleum ether are removed impurity, or separate and obtain thick solid through silica gel column chromatography,2,6,6-trimethyl-1-cyclohexene methyl triphenyl quaternary alkylphosphonium salt.
3. the method for preparing β-A Piao-8 '-carrot aldehyde according to claim 1,It is characterized in that, this method of preparing β-A Piao-8 '-carrot aldehyde also comprises respectively to step(2) product carries out the process of purifying, and concrete operations are as follows: after step (2) reaction, addSaturated ammonium chloride solution, CH2Cl2Extract three times, merge organic layer, use anhydrous Na2SO4DryOrganic layer, removal of solvent under reduced pressure, through silica gel column chromatography or recrystallization, obtain β-A Piao-8 '-Carrot aldehyde.
4. the method for preparing β-A Piao-8 '-carrot aldehyde according to claim 3,It is characterized in that, the elution system in described silica gel column chromatography is benzinum: ethyl acetate=10:1。
5. the method for preparing β-A Piao-8 '-carrot aldehyde according to claim 1,It is characterized in that, the concrete operations of described step (1) are as follows: in reaction bulb, add methyl alcohol,Add ring lemon alcohol and triphenylphosphine, after mixing and stirring, drip at lower than 15 DEG C denseHydrochloric acid or sulfuric acid add hot reflux 6-10 hour under nitrogen protection after dropwising, to obtain final product2,6,6-trimethyl-1-cyclohexene methyl triphenyl quaternary alkylphosphonium salt.
6. the method for preparing β-A Piao-8 '-carrot aldehyde according to claim 5,It is characterized in that, the mol ratio of described ring lemon alcohol and triphenylphosphine is 1:(1-1.5).
7. the method for preparing β-A Piao-8 '-carrot aldehyde according to claim 5,It is characterized in that the mol ratio of ring lemon alcohol and concentrated hydrochloric acid or the concentrated sulfuric acid in described step (1)For 1:(1-1.5).
8. the method for preparing β-A Piao-8 '-carrot aldehyde according to claim 1,It is characterized in that, the concrete operations of described step (2) are as follows: by what make in step (1)2,6,6-trimethyl-1-cyclohexene methyl triphenyl quaternary alkylphosphonium salt, stirs at ambient temperature, addsEnter the methanol solution of sodium methoxide, after dropwising, under nitrogen protection, stir 0.5-1h, thenAdd again 2,6,11,15-tetramethyl-2,4,6,8,10,12,14-, 16 carbon seven alkene dialdehyde, chamberTemperature reaction 1-4 hour.
9. the method for preparing β-A Piao-8 '-carrot aldehyde according to claim 8,It is characterized in that, described 2,6,6-trimethyl-1-cyclohexene methyl triphenyl quaternary alkylphosphonium salt, methyl alcoholSodium and 2,6,11,15-tetramethyl-2,4,6,8,10,12,14-, 16 carbon seven alkene dialdehyde moleThan being 1:(1-2): (1-1.5).
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Cited By (3)
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| CN111072541A (en) * | 2019-11-07 | 2020-04-28 | 肇庆巨元生化有限公司 | Preparation method of echinenone |
| CN114890929A (en) * | 2022-04-11 | 2022-08-12 | 万华化学集团股份有限公司 | Method for removing and purifying beta-carotene solid phosphorus |
| CN115819306A (en) * | 2022-11-15 | 2023-03-21 | 肇庆巨元生化有限公司 | Preparation method of beta-apo-12' -carotenal formaldehyde and product and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111072541A (en) * | 2019-11-07 | 2020-04-28 | 肇庆巨元生化有限公司 | Preparation method of echinenone |
| CN114890929A (en) * | 2022-04-11 | 2022-08-12 | 万华化学集团股份有限公司 | Method for removing and purifying beta-carotene solid phosphorus |
| CN114890929B (en) * | 2022-04-11 | 2024-02-02 | 万华化学集团股份有限公司 | Method for dephosphorization and purification of beta-carotene solid |
| CN115819306A (en) * | 2022-11-15 | 2023-03-21 | 肇庆巨元生化有限公司 | Preparation method of beta-apo-12' -carotenal formaldehyde and product and application thereof |
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