CN104059081B - A kind of method that catalysis sesamolin prepares sesamin phenol - Google Patents
A kind of method that catalysis sesamolin prepares sesamin phenol Download PDFInfo
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- CN104059081B CN104059081B CN201410300150.4A CN201410300150A CN104059081B CN 104059081 B CN104059081 B CN 104059081B CN 201410300150 A CN201410300150 A CN 201410300150A CN 104059081 B CN104059081 B CN 104059081B
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- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
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Abstract
The present invention relates to a kind of method that catalysis sesamolin prepares sesamin phenol, particularly as follows: sesamolin reacts 1～6h in 70～110 DEG C under the effect of catalyst in non-interactive hydrogen solvent, after reaction terminates, the post-treated acquisition sesamin phenol of reactant liquor; Described catalyst is heteropoly acid, heteropolyacid salt, carried heteropoly acid or carried heteropoly acid salt. In the method, catalyst only needs simple washing, dry and activation processing to reuse, and has that cost is low and environment-friendly advantage. Having raw material compared with traditional method to be easy to get, conversion process is stable, and sesamin phenol productivity is high, separates the advantages such as purification is simple, technique is green.
Description
Technical field
The invention belongs to sesamin phenol preparing technical field, be specifically related to the method that one utilizes heteropoly acid (salt) or carried heteropoly acid (salt) catalysis sesamolin to prepare sesamin phenol.
Background technology
Sesamin phenol, molecular formula is C20H18O7, it is the one of Semen Sesami lignanoids natural anti-oxidation active component, with other oxidation-resistant active ingredient (structural formula is as follows) existed in Oleum sesami as compared with sesamol, sesamin and sesamolin, its oxidation resistance is the strongest, simultaneously also stable. Sesamin phenol not only has antioxygenic property; as the Natural antioxidant, can also have biological activity widely simultaneously, be possible not only to protection and strengthening liver function, regulate blood pressure, reduce cholesterol; more can directly act on histoorgan, play the oxidation resistance of its excellence.
Being substantially free of sesamin phenol in Semen Sesami and Semen Sesami slightly oil, it is mainly come by other converting compounds in course of oil processing. In the course of processing roasting Oleum sesami, roast the sesamin phenol glycoside hydrolysis that operation can make to contain in Semen Sesami and become its glucosides part sesamin phenol, and be present in and roast in Oleum sesami and grouts. In the course of processing of another kind of refined sesame oil, use the bleaching process of Emathlite that sesamolin can be made to change into sesamin phenol and sesamol. But the sesamin phenol amount that both approaches obtains is limited, such as ShigenoriKumazawa, MihoKoike, YumikoUsut, etc.IsolationofSesaminolsasAntioxidativeComponentsfromRo astedSesameSeedOil [J] .J.OleoSci., 2003,52 (6): 303-307 it is directly separating from sesame seed, extracts the amount obtaining sesamin phenol and be only 0.002%;MasayasuNagata, ToshihikoOsawa, MitsuoNamiki, etc.StereochemicalStructuresofAntioxidativeBisepoxyligna ns, SesaminolandItsIsomers, TransformedfromSesamolin [J] .Agric.Biol.Chem., 1987, method described in 51 (5): 1285-1289, after decolouring with Emathlite, Oleum sesami is for raw material, and separating-purifying obtains the amount of sesamin phenol and is also only 0.015%. The method step that above two prepares sesamin phenol is complicated, and equipment and technology level requirement is high, and purification efficiency is low, it is impossible to meet the requirement of industrialized production. The preparation method of a patent ZL00910065650.3(sesamin phenol) disclose a kind of H of utilization type strongly acidic styrene type cation exchange resin and make the catalyst method that catalysis sesamolin prepares sesamin phenol in benzene series solvent, although the method conversion process compared with traditional method is stable, sesamin phenol productivity is high, separate the advantages such as purification is simple, technique is green, but reaction dissolvent used is benzene series solvent, toxicity is big, limits the use scope of product to a certain extent.
Summary of the invention
It is an object of the invention to provide the method that one utilizes heteropoly acid (salt) or carried heteropoly acid (salt) catalysis sesamolin to prepare sesamin phenol, the method step is succinct, and conversion yield is high, and product separation purification is simple, and technique green is easy to industrialized production.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of method that catalysis sesamolin prepares sesamin phenol, particularly as follows: sesamolin reacts 1～6h in 70～110 DEG C under the effect of catalyst in non-interactive hydrogen solvent, after reaction terminates, the post-treated acquisition sesamin phenol of reactant liquor; Described catalyst is heteropoly acid, heteropolyacid salt, carried heteropoly acid or carried heteropoly acid salt.
Concrete, described non-interactive hydrogen solvent is petroleum ether, ethyl acetate, acetone, benzene, toluene, ethylbenzene or dimethylbenzene.
Described heteropoly acid is one or more the mixture in phosphorus heteropoly tungstic acid, phosphorus tungsten vanada polyacid, phosphato-molybdic heteropolyacid, phosphorus molybdenum vanadium heteropolyacid, silicotungstic heteropolyacid, silicon tungsten vanada polyacid, silicon-molybdenum heteropoly acid, silicon molybdenum vanada polyacid, germanotungstic acid, borotungstic acid and cobalt wolframic acid.
Described heteropolyacid salt is preferably the cesium salt of heteropoly acid, ammonium salt, lithium salts, sodium salt or potassium salt etc.; As, it is possible to it is the cesium salt of phosphorus heteropoly tungstic acid, ammonium salt, lithium salts, sodium salt or potassium salt; The cesium salt of phosphato-molybdic heteropolyacid, ammonium salt, lithium salts, sodium salt or potassium salt; The cesium salt of silicotungstic heteropolyacid, ammonium salt, lithium salts, sodium salt or potassium salt; The cesium salt of silicon-molybdenum heteropoly acid, ammonium salt, lithium salts, sodium salt or potassium salt; The cesium salt of phosphorus molybdenum vanadium heteropolyacid, ammonium salt, lithium salts, sodium salt or potassium salt; The cesium salt of silicon tungsten vanada polyacid, ammonium salt, lithium salts, sodium salt or potassium salt; The cesium salt of silicon molybdenum vanada polyacid, ammonium salt, lithium salts, sodium salt or potassium salt.
Described carried heteropoly acid or carried heteropoly acid salt can be carried on carrier by heteropoly acid or heteropolyacid salt according to this area routine techniques, and load capacity is 5～30%(percentage by weight), described carrier is attapulgite, montmorillonite, SiO2、γ-Al2O3, activated carbon, TiO2、ZrO2, H-ZSM5 molecular sieve, H beta-molecular sieve, HY molecular sieve, MCM-41 molecular sieve or SBA-15 molecular sieve etc.
In the present invention, sesamolin initial concentration in non-interactive hydrogen solvent is 6～60mmol/L; Catalyst amount is 4～30g/mmol relative to sesamolin.Reaction carries out under anhydrous conditions. Drying and dehydrating process is carried out before sesamolin, catalyst and non-interactive hydrogen solvent reaction.
Raw material sesamolin used both can be sesamolin sterling, it is also possible to be the mixture containing sesamolin.
After reaction terminates, the post processing of reactant liquor may is that centrifugal or sucking filtration isolates catalyst, washing catalyst, cleaning mixture merges with sucking filtration or the centrifugal organic facies obtained, it is prepared the purification such as liquid chromatograph, column chromatography or thin layer chromatography again, collect the component containing sesamin phenol, remove non-interactive hydrogen solvent under reduced pressure and namely obtain target product. Catalyst can wash with the non-polar solven such as normal hexane, petroleum ether, dries, activation processing recycles. Washing catalyst solvent for use can be ethyl acetate or acetone etc. Chromatography purification is with silica gel for filler, and eluent is normal hexane and ethyl acetate volume ratio is the mixed solvent of 8～3:1.
The mixture that product sesamin phenol is sesamin phenol and isomer thereof finally prepared.
Sesamolin is to be connected with the double; two of central authorities oxolane ring by two methylenedioxyphenyl structures to form, one of them phenyl structure is connected to form acetal groups by 1 oxo bridge and central authorities furan core, and in the Oleum sesami course of processing, character is unstable and be converted into other lignanoid's materials such as sesamin phenol (including isomers). From molecular structure, it is " oxo bridge fracture molecular orientation in acetal place is reset " that sesamolin is converted into the core procedure containing free phenolic hydroxyl group sesamin phenol.
Heteropoly acid is a class by central atom (i.e. hetero atom, such as P, Si etc.) and coordination atom (i.e. polyatom, such as Mo, W etc.) carries out many oxygen clusters metal complex of spatial organization by oxygen atom bridging mode. Heteropoly acid and its esters are a kind of to have very much development potentiality, have the catalyst of superpower acidity and oxidation-reduction quality, and when not changing heteropolyanion structure, by selecting component (coordination atom, central atom and gegenion etc.), catalytic performance can systematically regulate and control, and develops quickly in recent years in applied research and exploitation. From catalysis angle, heteropoly acid molecular structure is determined, and the architectural feature of existing coordination compound and metal-oxide, there are again acidity and redox characteristic; Can not only be used for homogeneous or heterogeneous catalyst, again can as the bifunctional catalyst that can transmit proton and electronics simultaneously. Heteropoly acid can dissolve in the reaction system that water and other polar organic matter exist, and to having reacted catalysis in a homogeneous system, reaction condition is gentle, and toxicity and volatility are little, and catalytic efficiency is high, but due to the only small (< 10m of heteropoly acid specific surface area2/ g), in homogeneous catalysis, especially it is soluble in polar solvent causes recovery difficulty. Therefore heteropoly acid is immobilized on high specific surface carrier, not only can solve the separation problem of catalyst in homogeneous catalytic reaction, and the catalytic efficiency of catalyst in heterogeneous catalytic reaction can be improved.
The present invention establishes sesamolin and changes into the reaction system of sesamin phenol, carries out sesamolin conversion using heteropoly acid (salt) or carried heteropoly acid (salt) as catalyst and prepare the reaction of sesamin phenol in non-interactive hydrogen series solvent. The precursor substance sesamolin of sesamin phenol content in sesame seed and Semen Sesami slightly oil respectively 0.1～0.3% and 0.2～0.5%, its content is significantly larger than the content of the sesamin phenol roasted in Oleum sesami and refined sesame oil.Separating purification sesamolin from sesame seed relatively simple, it is not necessary to TLC and preparative hplc etc. are difficult to the means of industrial applications, this is that the preparation of sesamin phenol provides material guarantee. With sesamolin for raw material, the process changing into sesamin phenol in non-interactive hydrogen series solvent is easier to control, and conversion yield is up to more than 70%. Catalyst heteropoly acid (salt) or carried heteropoly acid (salt) stable chemical nature, in non-interactive hydrogen solvent, dissolubility is relatively low, product is substantially free of absorption, therefore the isolation and purification method of product is also more simple, and conversion reaction product only need to pass through the operations such as simple filtration, washing and concentrating under reduced pressure can obtain the concentrate (containing sesamin phenol and isomer 2-episesamin phenol) containing a large amount of sesamin phenols. Simultaneously catalyst only needs simple washing, dry and activation processing to reuse, and has that cost is low and environment-friendly advantage. The method has raw material compared with traditional method and is easy to get, and conversion process is stable, and sesamin phenol productivity is high, separates the advantages such as purification is simple, technique is green.
Detailed description of the invention
Below in conjunction with embodiment, technical scheme is described further, but protection scope of the present invention is not limited thereto.
Embodiment 1
A kind of method that catalysis sesamolin prepares sesamin phenol, particularly as follows: take sesamolin crude product (containing sesamolin 62.9% and sesamin 36.2%) 0.5g(containing sesamolin 0.85mmol) and 20mL petroleum ether joins in 50mL three-neck flask, and (sesamolin initial concentration is 42.5mmol L-1), stir and be previously heated to 100 DEG C, the silicotungstic heteropolyacid catalyst 15g(being subsequently adding 200 DEG C of activation 3h is 17.6g mmol relative to initial sesamolin-1), continuously stirred and keep 100 DEG C reaction 2h, HPLC assaying reaction 2h time reactant liquor, the productivity being converted into sesamin phenol is 90.2%. Sucking filtration after cooling, catalyst uses washing with acetone twice again, preparative liquid chromatography is adopted to collect 295nm place containing sesamin phenol component together with merging the cleaning mixture obtained for twice organic facies that obtains with sucking filtration, remove solvent under reduced pressure and namely obtain yellowish-brown sesamin phenol solid 0.22g, it is 98.63% that HPLC measures total sesamin phenol content, and yield is 73.3%. Wherein sesamin phenol content is 1.25 times of its isomer 2-episesamin phenol.
Embodiment 2
A kind of method that catalysis sesamolin prepares sesamin phenol, particularly as follows: take sesamolin sterling (purity is 98%) 80mg(0.216mmol) and 20mL ethylbenzene joins in 50mL three-neck flask, and (sesamolin initial concentration is 10.8mmol L-1), stir and be previously heated to 90 DEG C, the silicon-molybdenum heteropoly acid 3g being subsequently adding 200 DEG C of activation 3h (is 13.89g mmol relative to initial sesamolin-1), continuously stirred and keep 90 DEG C reaction 1.5h, HPLC assaying reaction 1.5h time reactant liquor, the productivity being converted into sesamin phenol is 87.9%. Sucking filtration after cooling, catalyst washes twice by ethyl acetate again, carry out removing solvent under reduced pressure together with merging the cleaning mixture obtained for twice organic facies that obtains with sucking filtration and obtain yellowish-brown cream solid, purification by silica gel column chromatography, normal hexane and ethyl acetate are with 5:1 eluting, and TLC detects, collect sesamin phenol component, remove under reduced pressure solvent namely obtain yellowish-brown sesamin phenol solid 58.6mg, HPLC measure total sesamin phenol content be 98.8%, yield is 73.2%.
Embodiment 3
A kind of method that catalysis sesamolin prepares sesamin phenol, particularly as follows: taking sesamolin sterling 66mg(purity is 98%, 0.18mmol) and 10mL benzene joins in 25mL three-neck flask, and (sesamolin initial concentration is 18mmol L-1), stir and be previously heated to 70 DEG C, being subsequently adding the phosphorus heteropoly tungstic acid cesium salt (Cs of 200 DEG C of activation processing 2h2.5H0.5PW12O40) 0.72g(is 4g mmol relative to initial sesamolin-1), continuously stirred and keep 70 DEG C reaction 4h, HPLC measure 4h time reactant liquor, the productivity being converted into sesamin phenol is 82.5%.Then processing by the method for embodiment 2, obtaining yellowish-brown sesamin phenol solid 43.5mg, the HPLC total sesamin phenol content of mensuration is 98.2%, and yield is 63.6%. Sesamolin sterling, benzene is first dehydrate before the reaction.
Embodiment 4
A kind of method that catalysis sesamolin prepares sesamin phenol, particularly as follows: take sesamolin crude product (containing sesamolin 62.9% and sesamin 36.2%) 0.7g(containing sesamolin 1.2mmol) and 20mL ethyl acetate joins in 50mL three-neck flask, and (sesamolin initial concentration is 60mmol L-1), stir and be previously heated to 70 DEG C, the phosphotungstic acid catalyst 20g(phosphotungstic acid load capacity being subsequently adding attapulgite loaded is 30wt%, and the amount of phosphotungstic acid is 5g mmol relative to initial sesamolin-1), continuously stirred and keep 70 DEG C reaction 3h, HPLC assaying reaction 3h time reactant liquor, the productivity being converted into sesamin phenol is 84.6%. Then according to the method for embodiment 1 processes, obtaining yellowish-brown sesamin phenol solid 0.48g, the HPLC total sesamin phenol content of mensuration is 96.5%, and yield is 75.6%. Sesamolin crude product, ethyl acetate be first dehydrate before the reaction, and catalyst uses front 180 DEG C of activation 2h.
Embodiment 5
A kind of method that catalysis sesamolin prepares sesamin phenol, particularly as follows: take sesamolin sterling (purity 98%) 132mg (containing sesamolin 0.36mmol) and 20mL petroleum ether joins in 50mL three-neck flask that (sesamolin initial concentration is 18mmol L-1), stir and be previously heated to 70 DEG C, being subsequently adding the phosphorus molybdenum vanadium heteropolyacid 1.44g(H of 200 DEG C of activation processing 2h4PMo11VO40, it is 4g mmol relative to initial sesamolin-1), continuously stirred and keep 70 DEG C of reactions 3h, HPLC to measure the reactant liquor after 3h, the productivity being converted into sesamin phenol is 79.5%. Then processing by embodiment 2 method, obtaining yellowish-brown sesamin phenol solid 40.5mg, the HPLC total sesamin phenol content of mensuration is 97.2%. Sesamolin sterling, petroleum ether be first dehydrate (90 ~ 120 DEG C) before the reaction.
Embodiment 6
A kind of method that catalysis sesamolin prepares sesamin phenol, particularly as follows: take sesamolin sterling (purity 98%) 66mg (0.18mmol) and 10mL toluene joins in 25mL three-neck flask that (sesamolin initial concentration is 18mmol L-1), stir and be previously heated to 95 DEG C, being subsequently adding the phosphomolybdic acid sodium salt 0.72g(Na of 200 DEG C of activation processing 2h3PMo12O40, it is 4g mmol relative to initial sesamolin-1), continuously stirred and keep 95 DEG C of reaction 3h, HPLC assaying reaction liquid are converted into the productivity of sesamin phenol being 80.5%. Then processing by embodiment 2 method, obtaining yellowish-brown sesamin phenol 40.5mg, the HPLC total sesamin phenol content of mensuration is 96.2%. Sesamolin sterling, toluene is first dehydrate before the reaction.
Embodiment 7
A kind of method that catalysis sesamolin prepares sesamin phenol, particularly as follows: take sesamolin crude product (containing sesamolin 62.9% and sesamin 36.2%) 0.7g(sesamolin 1.2mmol) and 20mL acetone joins in 50mL three-neck flask, and (sesamolin initial concentration is 60mmol L-1), stir and be previously heated to 85 DEG C, being subsequently adding silicon tungsten vanadium heteropolyacid catalyst 20g(silicon tungsten vanada polyacid load capacity molecular sieve carried for MCM-41 is 30wt%, and the amount of silicon tungsten vanada polyacid is 5g mmol relative to initial sesamolin-1), continuously stirred and reactant liquor when keeping identical thermotonus 3h, HPLC assaying reaction 3h, the productivity being converted into sesamin phenol is 81.4%.Then according to the method for embodiment 1 processes, obtaining yellowish-brown sesamin phenol solid 0.40g, the HPLC total sesamin phenol content of mensuration is 94.5%. Sesamolin crude product, acetone is first dehydrate before the reaction, and catalyst uses front 180 DEG C of activation 2h.
Claims (4)
1. the method that a catalysis sesamolin prepares sesamin phenol, it is characterised in that sesamolin reacts 1～6h in 70～110 DEG C under the effect of catalyst in non-interactive hydrogen solvent, after reaction terminates, the post-treated acquisition sesamin phenol of reactant liquor; Described catalyst is heteropoly acid, heteropolyacid salt, carried heteropoly acid or carried heteropoly acid salt;
Described non-interactive hydrogen solvent is petroleum ether, ethyl acetate, acetone.
2. the method that catalysis sesamolin prepares sesamin phenol as claimed in claim 1, it is characterized in that, described heteropoly acid is one or more the mixture in phosphorus heteropoly tungstic acid, phosphorus tungsten vanada polyacid, phosphato-molybdic heteropolyacid, phosphorus molybdenum vanadium heteropolyacid, silicotungstic heteropolyacid, silicon tungsten vanada polyacid, silicon-molybdenum heteropoly acid, silicon molybdenum vanada polyacid, germanotungstic acid, borotungstic acid and cobalt wolframic acid.
3. the method that catalysis sesamolin prepares sesamin phenol as claimed in claim 1, it is characterised in that described heteropolyacid salt is the cesium salt of heteropoly acid, ammonium salt, lithium salts, sodium salt or potassium salt.
4. the method that catalysis sesamolin prepares sesamin phenol as claimed in claim 1, it is characterized in that, described carried heteropoly acid or carried heteropoly acid salt are to be carried on carrier by heteropoly acid or heteropolyacid salt, and load capacity is 5～30wt%, and described carrier is attapulgite, montmorillonite, SiO2、γ-Al2O3, activated carbon, TiO2、ZrO2, H-ZSM5 molecular sieve, H beta-molecular sieve, HY molecular sieve, MCM-41 molecular sieve or SBA-15 molecular sieve.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4774343A (en) * | 1986-03-31 | 1988-09-27 | Takemoto Yushi Kabushiki Kaisha | Method of producing active antioxidant |
| CN101648957A (en) * | 2009-08-05 | 2010-02-17 | 河南省农科院农副产品加工研究所 | Preparation method of sesamin phenol |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4774343A (en) * | 1986-03-31 | 1988-09-27 | Takemoto Yushi Kabushiki Kaisha | Method of producing active antioxidant |
| CN101648957A (en) * | 2009-08-05 | 2010-02-17 | 河南省农科院农副产品加工研究所 | Preparation method of sesamin phenol |
Non-Patent Citations (5)
| Title |
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| A novel conversion of sesamolin to sesaminol by acidic cation exchange resin;Jinian Huang，等;《Eur. J.Lipid Sci.Technol.》;20121231;第842-848页，第2.2节和第3节，尤其第3.7节，第4节，以及Figure 6 * |
| Acidic transformation of sesamolin, the sesame-oil constituent, into an antioxidant bisepoxylignan, sesaminol;Fukuda, Yasuko,等;《HETEROCYCLES》;19861231;第24卷(第4期);第923-926页，尤其是第923-924页 * |
| 杂多酸催化剂在烷基化反应中的研究现状;邓佩佩，等;《广州化工》;20091231;第37卷(第2期);第16-20页 * |
| 杂多酸催化剂在烷基化反应中的研究进展;申凤善，等;《分子科学学报》;20060228;第22卷(第1期);第28-30页 * |
| 杂多酸催化剂研究进展;王德胜，等;《分子催化》;20120831;第26卷(第4期);第366-375页 * |
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