CN111072541A - Preparation method of echinenone - Google Patents
Preparation method of echinenone Download PDFInfo
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- CN111072541A CN111072541A CN201911082234.4A CN201911082234A CN111072541A CN 111072541 A CN111072541 A CN 111072541A CN 201911082234 A CN201911082234 A CN 201911082234A CN 111072541 A CN111072541 A CN 111072541A
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- carotenal
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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
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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
- C07C403/14—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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- 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
Abstract
The invention discloses a preparation method of echinenone, which comprises the steps of oxidizing β -apo-12 '-carotenal into 4-oxo- β -apo-12' -carotenal through regioselective oxidation, and connecting C through Witting reaction15The fragments can be synthesized into echinenone through a short route under the conditions of mild reaction conditions and simple process operation. The method has the advantages of short synthetic route, considerable product purity and yield, easily available raw materials, low cost, good industrial value, easy operation in the production process, no generation of toxic and harmful intermediates, and accordance with the concept of green and environment-friendly chemistry.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a preparation method of echinenone.
Background
Sea urchin ketene, also called β -carotene-4-ketone, is an orange red solid, is an oxygen-containing carotenoid compound in carotenoids, has antioxidant activity, has the activity of 54 percent of previtamin A, can be extracted from sea urchins and other marine organisms by using a modern biological extraction technology, and is a key precursor for synthesizing astaxanthin or canthaxanthin.
There are few methods reported for synthesizing echinenone, and there are two main methods:
in 1970, J.D.Surmatis et al reported a C20-alcohol is used as a raw material, and the echinenone is obtained through five steps of reactions, wherein the reaction formula is as follows:
the above synthesis method has the following disadvantages: firstly, the reaction steps are multiple, and the operation is complicated; secondly, the yield of the target product is low; thirdly, the raw materials are very common chemicals, and industrialization is difficult to realize.
Secondly, β -carotene is used as a raw material, and under the action of an oxidant, the echinenone is obtained by local oxidation, and the reaction formula is as follows:
in the synthesis method, the raw material β -carotene is high in price, so that the raw material cost is high, in addition, the consumption of the oxidant is high, the reaction is not easy to control, the transition oxidation is easy to be carried out to canthaxanthin, and the separation and purification difficulty is increased.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of echinenone with short synthetic route and high product yield.
The purpose of the invention is realized by adopting the following technical scheme:
a preparation method of echinenone comprises the following steps:
1) β -apo-12' -carotenal in an oxidant and KI/I under the protection of inert gas2Generating 4-oxo- β -apo-12' -carotenal under the action of inorganic acid, wherein the reaction formula is as follows:
2) under the protection of inert gas, 4-oxo- β -apo-12' -carotenal and [ 3-methyl-5- (2,6, 6-trimethyl-1-cyclohexenyl) -2, 4-pentadienyl ] triphenyl phosphonium salt are subjected to Witting reaction to obtain a target product echinenone, wherein the reaction formula is as follows:
namely, the application firstly oxidizes methylene at the 4-position of β -apo-12' -carotenal into ketone group without influencing aldehyde group through regioselective oxidation, and then C is oxidized into C through Witting reaction15The quaternary phosphonium salt of the fragment reacts with the aldehyde group of 4-oxo- β -apo-12' -carotenal to obtain echinenone through connection.
Essential in this application is that in step 1) the oxidizing agent is sodium chlorate. The oxidation properties are moderate to ensure that oxidation occurs at the 4-position without adversely affecting the aldehyde groups.
In order to improve the specificity of the regioselective oxidation, in the step 1), the oxidant and β -apo-12 '-carotenal are dissolved in advance to avoid the direct and large-scale contact of the oxidant with the reaction substrate, i.e. the oxidant is dissolved by adding water, β -apo-12' -carotenal and organic solvent are added, and KI/I is added under stirring2Adding inorganic acid, and reacting at 25-60 deg.C.
The organic solvent used in step 1) may be one or more selected from dichloromethane, chloroform and cyclohexane.
More specifically, in the step 1), 4 to 10mol of oxidant is added with water to be dissolved, 1mol of β -apo-12' -carotenal solution is added, and 0.06 to 0.15mol of KI/0.06 to 0.15mol of I is added under stirring2Adding inorganic acid until the pH value is 1-2 and reacting at 25-60 ℃. Wherein the inorganic acid is sulfuric acid or hydrochloric acid, and the concentration of the inorganic acid is 1-10%.
Further, in the step 2), the [ 3-methyl-5- (2,6, 6-trimethyl-1-cyclohexenyl) -2, 4-pentadienyl ] triphenyl phosphonium salt is dissolved, 4-oxo- β -apo-12' -carotenal is added, the alkali liquor is dripped at the temperature lower than 40 ℃, and after the dripping is finished, the temperature is raised to reflux.
Further, the alkali solution is an organic alkali solution, such as sodium ethoxide or sodium methoxide solution. The alkali solution is inorganic alkali solution, such as solution of sodium hydroxide or potassium hydroxide.
Furthermore, the molar ratio of 4-oxo- β -apo-12' -carotenal to [ 3-methyl-5- (2,6, 6-trimethyl-1-cyclohexenyl) -2, 4-pentadienyl ] triphenyl phosphonium salt to alkali liquor is 1 (1.10-1.30) to (1-3).
Further, the [ 3-methyl-5- (2,6, 6-trimethyl-1-cyclohexenyl) -2, 4-pentadienyl ] triphenyl phosphonium salt is a chloride salt, a bromide salt, a sulfate salt or an acetate salt of [ 3-methyl-5- (2,6, 6-trimethyl-1-cyclohexenyl) -2, 4-pentadienyl ] triphenyl phosphonium.
Further, [ 3-methyl-5- (2,6, 6-trimethyl-1-cyclohexenyl) -2, 4-pentadienyl ] triphenyl phosphonium salt is dissolved with one or both of dichloromethane, ethanol, and methanol.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of echinenone, which comprises the steps of oxidizing β -apo-12 '-carotenal into 4-oxo- β -apo-12' -carotenal through regioselective oxidation, and connecting C through Witting reaction15The fragments can be synthesized into echinenone by short path under the conditions of mild reaction condition and simple process operation;
the reaction raw materials used in the invention are β -apo-12' -carotenal, [ 3-methyl-5- (2,6, 6-trimethyl-1-cyclohexenyl) -2, 4-pentadienyl]Triphenyl phosphonium salt (abbreviation C)15-quaternary phosphonium salt) and the like are large industrial products, so that the raw materials are easy to obtain, the cost is low, and the industrial value is high;
the method does not use toxic and harmful raw materials with unpleasant smell in the process of preparing the echinenone, does not generate toxic and harmful intermediates, does not generate a large amount of waste water and waste residues, accords with the green chemical concept, and is beneficial to environmental protection.
Drawings
FIG. 1 is an HPLC chart of echinenone of example 2;
FIG. 2 is a UV map of echinenone of example 2.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific embodiments, and it should be noted that any combination of the embodiments or technical features described below can be used to form a new embodiment without conflict.
The following are specific examples of the present invention, and raw materials, equipments and the like used in the following examples can be obtained by purchasing them unless otherwise specified.
In the present application, the amounts of reactants described are to be understood only as representing relative molar proportions and not as any given experimental scale which limits the scope of protection. The following percentages, unless otherwise specified, are to be understood as percentages by weight.
In the following embodiments, the purity of the echinenone product is measured by HPLC on a HPLC, the retention time is compared with a standard sample, and the content is calculated by an area normalization method.
HPLC conditions:
a chromatographic column: shimadzu VP-ODSC18Column, 150 L.times.4.6
Mobile phase: methanol: 85:15 parts of methylene chloride
Flow rate: 1.0mL/min
Column temperature: 30 +/-5 DEG C
Detection wavelength: 460nm
Collecting time: and 20 min.
Example 1:
a preparation method of echinenone comprises the following steps:
step 1) preparation of 4-oxo- β -apo-12' -carotenal:
under the protection of nitrogen, 0.16mol of sodium chlorate and 75mL of water are added into a 500mL reaction bottle, after the sodium chlorate and the water are completely dissolved by mechanical stirring, 0.02mol of β -apo-12' -carotenal and 150mL of dichloromethane are added, and 0.0024mol of I is added under the stirring20.0024mol of KI, 5.8g of 1% sulfuric acid water is added, and the reaction is carried out for 54 hours at the temperature of 28-31 ℃.
After the reaction is finished, transferring the reaction solution into a 500mL separating funnel, standing for layering, separating an organic layer, extracting a water layer with 50mL of dichloromethane for 2 times, combining organic phases, decompressing and concentrating to remove dichloromethane to obtain a purple black sticky substance, adding 50mL of ethanol for dissolving, and directly using in the next reaction.
Step 2) preparation of echinenone:
under the protection of nitrogen, 0.053mol of C is added into a 500mL dry three-neck bottle15Adding triphenyl phosphonium chloride and 100mL ethanol, adding the crude product of 4-oxo- β -apo-12' -carotenal in the step 1), controlling the dropping temperature or reducing the temperature by running water, dropping 0.05846mol ethanol solution of sodium ethoxide at the temperature of 24-29 ℃, and heating to about 80 ℃ after the dropping for reflux isomerization for 3.0 h.
After the isomerization, the temperature is reduced to room temperature, the red wet product is obtained by suction filtration, and the red wet product is dried in vacuum at 50 ℃ to obtain 12.02g of red dry product, the HPLC content is 81.74 percent, and the yield of β -apo-12' -carotenal is 89.18 percent.
Example 2
A preparation method of echinenone comprises the following steps:
step 1) preparation of 4-oxo- β -apo-12' -carotenal:
under the protection of nitrogen, 0.50mol of sodium chlorate and 100mL of water are added into a 500mL reaction bottle, after the sodium chlorate and the water are completely dissolved by mechanical stirring, 0.05mol of β -apo-12' -carotenal and 200mL of trichloromethane are added, 0.0060mol of iodine simple substance/0.0060 mol of KI and 20g of 1% sulfuric acid water are added under stirring, and the reaction is carried out for 16 hours at the temperature of 48-50 ℃.
After the reaction is finished, transferring the reaction solution into a 500mL separating funnel, standing for layering, separating an organic layer, extracting a water layer for 2 times by using 50mL of trichloromethane respectively, combining organic phases, concentrating under reduced pressure to remove the trichloromethane to obtain a purple black sticky substance, adding 60mL of ethanol, recrystallizing at 0-10 ℃, performing cold suction filtration to obtain 10.2g of a wet product, drying to obtain 7.04g of a red dry product, wherein the yield of β -apo-12' -carotenal is 38.62%.
Step 2) preparation of echinenone:
under nitrogen protection, 0.023mol C is added into a 500mL dry three-mouth bottle15Adding 0.01931mol of 4-oxo- β -apo-12' -carotenal crude product obtained in the step 1) into 50mL of methanol and triphenyl phosphonium bromide, slightly cooling, dropwise adding 0.0276mol of sodium methoxide methanol solution at 29-35 ℃, and heating to about 60-65 ℃ after adding, and carrying out reflux isomerization for 4.0 h.
After the isomerization, the temperature is reduced to room temperature, suction filtration is carried out, 16.99g of red wet product is obtained, vacuum drying is carried out at 50 ℃, 7.79g of red dry product with the HPLC content of 91.42 percent is obtained, the HPLC diagram is shown in figure 1, the retention time of echinenone is about 12.53min and is the same as that of a standard sample, the yield of 4-oxo- β -apo-12' -carotenal is 66.95 percent, the UV spectrogram of echinenone is shown in figure 2, wherein the absorption peak of echinenone is 460.12nm and is the same as that of the standard sample.
Example 3
A preparation method of echinenone comprises the following steps:
step 1) preparation of 4-oxo- β -apo-12' -carotenal:
under the protection of nitrogen, 0.150mol of sodium chlorate and 90mL of water are added into a 500mL reaction bottle, after the sodium chlorate and the water are completely dissolved by mechanical stirring, 0.03mol of β -apo-12' -carotenal and 150mL of cyclohexane are added, 0.0018mol of iodine simple substance/0.0018 mol of KI and 10g of 1% sulfuric acid water are added under stirring, and the reaction is carried out for 18.0 hours at the temperature of 58-60 ℃.
After the reaction, the reaction solution was transferred to a 500mL separatory funnel, and the mixture was allowed to stand for separation, an organic layer was separated, an aqueous layer was extracted with 50mL cyclohexane for 2 times, organic layers were combined and concentrated under reduced pressure to remove cyclohexane, and a purple-black sticky substance was obtained, which was separated and purified by column chromatography, and 8.19g of a pure 4-oxo- β -apo-12 '-carotenal was obtained by co-separation using petroleum ether and ethyl acetate 2:1 as an eluent, and the yield of β -apo-12' -carotenal was 74.86%.
Step 2) preparation of echinenone:
under nitrogen protection, 0.022mol C was added to a 500mL dry three-necked flask15Triphenylphosphonium sulfate and 50mL of methylene chloride, and a further additionSlightly cooling 0.01818mol of 4-oxo- β -apo-12' -carotenal pure product in the step 1), dripping 0.0484mol of sodium hydroxide aqueous solution between 20 and 25 ℃, and heating to about 40 to 45 ℃ after the addition for reflux isomerization for 6.0 h.
After the isomerization, the temperature was decreased to room temperature, and the red product was filtered under vacuum to obtain 17.58g of a wet red product, which was dried under vacuum at 50 ℃ to obtain 8.00g of a dry red product having HPLC content of 82.33% and yield of 4-oxo- β -apo-12' -carotenal of 65.77%.
Example 4
A preparation method of echinenone comprises the following steps:
step 1) preparation of 4-oxo- β -apo-12' -carotenal:
under the protection of nitrogen, 0.280mol of sodium chlorate and 120mL of water are added into a 500mL reaction bottle, after the sodium chlorate and the water are completely dissolved by mechanical stirring, 0.04mol of β -apo-12' -carotenal and 150mL of cyclohexane are added, 0.006mol of iodine simple substance/0.006 mol of KI and 10g of 1% hydrochloric acid water are added under stirring, and the reaction is carried out for 18.0 hours at the temperature of 58-60 ℃.
After the reaction is finished, transferring the reaction liquid into a 500mL separating funnel, standing for layering, separating an organic layer, extracting a water layer with 50mL of cyclohexane for 2 times, combining organic phases, concentrating under reduced pressure to remove the cyclohexane to obtain a purple black sticky substance, separating and purifying by column chromatography, and carrying out co-separation by using petroleum ether and ethyl acetate 2:1 as an eluent to obtain 6.74g of a pure product of 4-oxo- β -apo-12 '-carotenal, wherein the yield of β -apo-12' -carotenal is 46.23%.
Step 2) preparation of echinenone:
0.02327mol C was added to a 500mL dry three-necked flask under nitrogen15Adding 0.01849mol of pure 4-oxo- β -apo-12' -carotenal obtained in the step 1) into the mixture of triphenyl phosphonium sulfate hydride and 50mL of dichloromethane, slightly cooling, dripping 0.03679mol of sodium hydroxide aqueous solution at the temperature of between 20 and 25 ℃, and heating to about 40 to 45 ℃ after the addition for reflux isomerization for 6.0 h.
After the isomerization, the temperature is reduced to room temperature, and the red product is filtered by suction to obtain 10.45g of red wet product, and the red wet product is dried in vacuum at 50 ℃ to obtain 7.79g of red dry product, wherein the HPLC content is 82.16 percent, and the yield of the 4-oxo- β -apo-12' -carotenal is 62.84 percent.
Comparative example 1:
a preparation method of echinenone comprises the following steps:
step 1) preparation of 4-oxo- β -apo-12' -carotenal:
under the protection of nitrogen, 0.06mol of urea peroxide and 90mL of water are added into a 500mL reaction bottle, after mechanical stirring is carried out until the urea peroxide and the water are uniformly dispersed, 0.03mol of β -apo-12' -carotenal and 150mL of cyclohexane are added, 25g of 10% sodium hydroxide is added under stirring, and the reaction is carried out for 18.0h at the temperature of 58-60 ℃.
After the reaction is finished, transferring the reaction liquid into a 500mL separating funnel, standing for layering, separating an organic layer, extracting a water layer with 50mL of cyclohexane for 2 times, combining organic phases, decompressing and concentrating to remove the cyclohexane to obtain a purple black sticky substance, separating and purifying by column chromatography, and using petroleum ether and ethyl acetate which are 2:1 as an eluent to obtain 4.27g of 4-oxo- β -apo-12 '-carotenal pure product through co-separation, wherein the yield of β -apo-12' -carotenal is 39.05%.
Step 2) preparation of echinenone:
under nitrogen protection, 0.014mol of C was added to a 500mL dry three-necked flask15Adding 0.0117mol of crude 4-oxo- β -apo-12' -carotenal in the step 1) into the mixture of triphenyl phosphonium sulfate and 50mL of dichloromethane, slightly cooling, dropwise adding 0.0421mol of sodium hydroxide aqueous solution at the temperature of 20-25 ℃, and after the addition, heating to about 40-45 ℃ for reflux isomerization for 6.0 h.
After the isomerization, the temperature was reduced to room temperature, and the red product was filtered under vacuum to obtain 10.72g of a wet red product, which was dried under vacuum at 50 ℃ to obtain 4.88g of a dry red product having HPLC content of 82.07% and yield of p-4-oxo- β -apo-12' -carotenal of 62.14%.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (10)
1. A preparation method of echinenone is characterized by comprising the following steps:
1) β -apo-12' -carotenal in an oxidant and KI/I under the protection of inert gas2Generating 4-oxo- β -apo-12' -carotenal under the action of inorganic acid, wherein the reaction formula is as follows:
2) under the protection of inert gas, 4-oxo- β -apo-12' -carotenal and [ 3-methyl-5- (2,6, 6-trimethyl-1-cyclohexenyl) -2, 4-pentadienyl ] triphenyl phosphonium salt are subjected to Witting reaction to obtain a target product echinenone, wherein the reaction formula is as follows:
2. the method of claim 1, wherein in step 1), the oxidizing agent is sodium chlorate.
3. The process for producing echinenone according to claim 1, wherein in the step 1), the oxidizing agent is dissolved in water, β -apo-12' -carotenal and the organic solvent are added, and KI/I is added under stirring2Adding inorganic acid, and reacting at 25-60 deg.C.
4. The process for producing echinenone according to claim 3, wherein in the step 1), 4 to 10mol of the oxidizing agent is dissolved in water, 1mol of β -apo-12' -carotenal solution is added, and 0.06 to 0.15mol of KI/0.06 to 0.15mol of I is added under stirring2Adding inorganic acid until the pH value of the system is 1-2, and reacting at 25-60 ℃.
5. The process for the preparation of echinenone according to claim 4, wherein the inorganic acid is sulfuric acid or hydrochloric acid, and the concentration of the inorganic acid is 1 to 10%.
6. The process according to claim 1, wherein in step 2), the [ 3-methyl-5- (2,6, 6-trimethyl-1-cyclohexenyl) -2, 4-pentadienyl ] triphenyl phosphonium salt is dissolved, 4-oxo- β -apo-12' -carotenal is added, and the alkali solution is added dropwise at a temperature of less than 40 ℃, and after completion of the addition, the temperature is raised to reflux.
7. The method of claim 6, wherein the alkali solution is a solution of sodium ethoxide, sodium methoxide, sodium hydroxide or potassium hydroxide.
8. The process for producing echinenone according to claim 6, wherein the molar ratio of 4-oxo- β -apo-12' -carotenal to [ 3-methyl-5- (2,6, 6-trimethyl-1-cyclohexenyl) -2, 4-pentadienyl ] triphenyl phosphonium salt to the alkali solution is 1 (1.10-1.30): 1-3).
9. The process for producing echinenone according to claim 6, wherein the [ 3-methyl-5- (2,6, 6-trimethyl-1-cyclohexenyl) -2, 4-pentadienyl ] triphenyl phosphonium salt is a chloride salt, a bromide salt, a sulfate salt or an acetate salt of [ 3-methyl-5- (2,6, 6-trimethyl-1-cyclohexenyl) -2, 4-pentadienyl ] triphenyl phosphonium.
10. The method of claim 6, wherein the [ 3-methyl-5- (2,6, 6-trimethyl-1-cyclohexenyl) -2, 4-pentadienyl ] triphenyl phosphonium salt is dissolved in one or both of dichloromethane, ethanol and methanol.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4209450A (en) * | 1977-02-03 | 1980-06-24 | Bask Aktiengesellschaft | Introduction of a carbonyl group into a cyclohexene ring |
| CN105646311A (en) * | 2016-03-31 | 2016-06-08 | 广州巨元生化有限公司 | Method for preparing beta-Apo-8'-carotenal |
| WO2018050792A1 (en) * | 2016-09-16 | 2018-03-22 | Basf Se | Process for preparing esters of 12'-apocarotenals as building blocks for carotenoids |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4209450A (en) * | 1977-02-03 | 1980-06-24 | Bask Aktiengesellschaft | Introduction of a carbonyl group into a cyclohexene ring |
| CN105646311A (en) * | 2016-03-31 | 2016-06-08 | 广州巨元生化有限公司 | Method for preparing beta-Apo-8'-carotenal |
| WO2018050792A1 (en) * | 2016-09-16 | 2018-03-22 | Basf Se | Process for preparing esters of 12'-apocarotenals as building blocks for carotenoids |
| CN109689610A (en) * | 2016-09-16 | 2019-04-26 | 巴斯夫欧洲公司 | The method for preparing 12 '-apocarotenal esters of the structural unit as carotenoid |
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