CN102659573B - Preparation method for 7-carbonyl group-8, 15-isopimaric acid - Google Patents
Preparation method for 7-carbonyl group-8, 15-isopimaric acid Download PDFInfo
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Abstract
The invention discloses a preparation method for 7-carbonyl group-8, 15-isopimaric acid. The preparation method comprises the following steps of: dissolving raw materials, i.e. isopimaric acid and an initiating agent in a solvent according to a mass ratio of the m isopimaric acid to the m initiating agent being 1: (0.01-0.20), uniformly mixing the raw materials and preparing into a solution, then coating the solution on a tinplate sheet, reacting under the ultraviolet illumination, leaching and collecting coatings obtained through reaction by using the solvent after ending the reaction, evaporating a collecting liquid to remove the solvent, adopting a column chromatography for seperation after redissolving, collecting eluted components, removing an eluant, and finally collecting the components with the strongest 1ma*254nm ultraviolet absorption by using a semi-preparation type high pressure liquid chromatography, thereby obtaining the target product 7-carbonyl group-8, 15-isopimaric acid. The initiating agent is one or any combination of 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone, 2, 2-dimethoxy-2-phenyl acetophenone and 2-hydroxyl-2- methyl phenyl ketone.
Description
Technical field
The present invention relates to 7-carbonyl-8,15-isopimaric acid and preparation method thereof, relate in particular to and a kind ofly in uv cure machine, isopimaric acid is carried out to the method that light-catalyzed reaction prepares 7-carbonyl-8,15-isopimaric acid.
Background technology
7-carbonyl-8,15-isopimaric acid is a kind of natural product resource, and its content at occurring in nature is less, only in the plant of minority, contain, and as arbor-vitae, Europe Juniperus formosana, western red cedar etc., be a kind of rare natural resources.Isopimaric acid is a kind of important natural resource, and the content in rosin especially slash pine rosin is more.[Song Zhanqian: Chinese rosin feature and Pinus classification, Beijing: China Forest press, 1998:34 ~ 120] according to the study, massfraction has 15 kinds more than in the pine tree more than 8%.According to another report [Zhao Zhendong: pimaric type acid resource distribution and composition research. biomass chemical engineering, 2008,42 (4): 9 ~ 12], in industrial rosin, slash pine rosin is maximum containing isopimaric acid, and content reaches as high as 19.5%.
At present, very few with the correlative study of 7-carbonyl-8,15-isopimaric acid building-up reactions and analysis aspect, in current correlative study, mainly concentrate on and extract the separation aspect from natural resource, also do not have 7-carbonyl-8,15-isopimaric acid to prepare the report of aspect.Main research report is as follows:
Wang Tao [Wang Tao, the chestnut peace. the research of abietic acid autoxidation product. chemistry of forest product and industry, 1991,11 (3): 173 ~ 181] etc. systematically summarized the research report of relevant abietic acid oxidation products both at home and abroad, and abietic acid autoxidation product is studied in detail, for the application of further carrying out the abietic acid oxidation products is laid a good foundation.Photosensitized oxidation can occur in the resinous acid that contains conjugated double bond in rosin, without pimaric acid and the isopimaric acid of conjugated double bond, also can photosensitized oxidation occur by ethylene linkage.But the oxidizing reaction of a small amount of composition isopimaric acid in rosin is not paid close attention in this research.
Relate to the earliest 7-carbonyl-8, the research report of 15-isopimaric acid is DE PASCUAL TERESA[DEPASCUAL TERESA J, BARRERO A F, MURIEL L, et al.New natural diterpeneacids from Juniperus communis.Phytochemistry, 1980,19,1153 ~ 1156.] be, from the Juniperus formosana of Europe, with the form of methyl esters, to extract to separate to obtain 7-carbonyl-8,15-isopimaric acid methyl esters, and by IR, UV,
1hNMR characterizes its structure.The method can not meet 7-carbonyl-8,15-isopimaric acid preparation and the requirement utilized.
Kuo[Yueh-Hsiung Kuo, Wen-Chin Chen.Chemical Constituents of the Pericarpof Platycladus orientalis.Journal of the Chinese Chemical Society.1999,46 (5): 819～824.] in the methyl alcohol leach liquor of arbor-vitae dry fruit skin, utilize column chromatography to separate and obtained 7-carbonyl-8, the 15-isopimaric acid, when further separation and purification process, be with 7-carbonyl-8, the form of 15-isopimaric acid methyl esters completes, and structural characterization is also that form with methyl esters completes.
Herz[WERNER H, PALANIAPPAN K.Ent-Pimaranes, ent-kauranes, heliangolides, and other constituents of three Helianthus species.Phytochemistry, 1984,23 (7): 1453～1459] extract and be separated to a kind of compound in a kind of Sunflower Receptacle, and the esterification product structure of this compound is identified, prove a kind of epimer of 7-carbonyl-8,15-isopimaric acid.
Chang[Leng Chee Chang, Lynda L.Song, Eun Jung Park, et al.Bioactiveconstituents of Thuja occidentalis.J.Nat.Prod.2000,63,1235～1238.] utilize column chromatography to separate and obtain containing 7-carbonyl-8 in western red cedar, the component of 15-isopimaric acid, then carried out purifies and separates by anti-phase half preparative high-performance liquid chromatographic to it, obtained the 7-carbonyl-8 of purifying, 15-isopimaric acid and 7-carbonyl-8, the 14-isopimaric acid.Bioactivity research finds that 7-carbonyl-8,15-isopimaric acid has inhibition mouse skin cell JB6 transition and suppresses the function that in mouse skin cell ME308, carcinogenic promoting agent (TPA) is induced ornithine decarboxylase (ODC).
Uromes[J.G.URONES, I.SANCHEZ MARCOS, J.
and P.BASABE BARCALA.Terpenoids from nepeta tuberosa subsp.reticulata (II) .Phytochemistry, 1988,27 (2): 523～526] extract and be separated to 7-hydroxyl-8 in a kind of Japanese Honeysuckle, two kinds of epimers of 15-isodextropimarinol, these two kinds of epimers have obtained 7-carbonyl-8,15-isopimaric acid through the Jones reagent oxidation, and the resterification reaction obtains 7-carbonyl-8,15-isopimaric acid methyl esters, and to its purification and structural characterization.
Severiano[Marcela E.Severiano, Marilia R.Simao, Thiago S.Porto, et al.Anticariogenic Properties of ent-Pimarane Diterpenes Obtained by MicrobialTransformation.Molecules, 20l0,15:8553～8566] synthesized a kind of steric isomer of 7-carbonyl-8,15-isopimaric acid from pimaric acid by the mode of microbial transformation, this isomer is identical with the epimer in Herz research.Synthesis path is that the pimaric acid isometry is the meso isopimaric acid, cyclic olefinic bond initial ring oxidizing reaction, and hydrogenation then, generate two hydroxyl structures.Elimination reaction first occurs and reoxidizes and generate 7-carbonyl-8,15-isopimaric acid in the isopimaric acid of two hydroxyl structures, or oxidizing reaction first occurs elimination reaction occurs again generates 7-carbonyl-8,15-isopimaric acid.Research finds that carbonyl-the 8,15-isopimaric acid biological activity is 2～3 times of its presoma to 7-.This reaction method complexity, need be by microbial transformation, severe reaction conditions.
Ulubelen[AYHAN ULUBELEN, GULACTI TOPCU, NUR TAN.Diterpenoidsfrom Salvia heldrichiana.Phytochemistry, 40 (5): 1473～1475] extract in a kind of Salvia japonica Thunb. root and be separated to a kind of new compound and five kinds of known compounds by column chromatography, 7-carbonyl-8,15-isopimaric acid is wherein a kind of.
Fraga[FRAGA B M,
m G,
p, etc.Thebiotransformation of 18-hydroxy-9-epi-ent-pimara-7,15-diene by Gibberella fujikuroi.Phytochemistry, 2000,53:395～399] [FRAGA B M,
p,
m G, etc.Microbial Transformation of 18-Hydroxy-9,13-epi-ent-pimara-7,15-dieneby Gibberella fujikuroi.J.Nat.Prod.2003,66:392～397] the research bio-transformation of part of compounds that contains hydrogenation phenanthrene ring structure, comprising 18-hydroxyl-7-carbonyl-15-vinyl-9-pimaric acid, the structure of the structure of this compound and 7-carbonyl-8,15-isopimaric acid is comparatively similar.
Although above these methods can obtain a small amount of 7-carbonyl-8,15-isopimaric acid, far can not meet 7-carbonyl-8,15-isopimaric acid is studied and the requirement utilized.
Summary of the invention
In order to solve 7-carbonyl-8,15-isopimaric acid resource scarcity, separation and Extraction difficulty, the difficult problem of synthesis technique complexity, the invention provides a kind of preparation method of 7-carbonyl-8,15-isopimaric acid, has synthetic route environmental protection, the advantage such as easy to operate.
The invention provides following technical scheme: a kind of preparation method of 7-carbonyl-8,15-isopimaric acid, it is characterized in that, by raw material isopimaric acid, initiator according to mass ratio m
isopimaric acid: m
initiator=1: the ratio of (0.01～0.20) is dissolved in solvent and mixes wiring solution-forming, then solution coat is reacted on the tinplate sheet under ultraviolet lighting, collection liquid is collected to obtain in the coating drip washing that reaction obtains reaction with solvent after finishing, reaction repeated to solution is finished using, and merges all collection liquid evaporations that obtain and obtains the pulverulent solids product except desolventizing.After products therefrom is dissolved with eluent, adopt column chromatography to be separated, collect different time wash-out component out, according to HPLC follow-up inspection result, merge λ
maxthe component that the 254nm uv-absorbing is the strongest, the pulverulent solids product that eluent obtains preliminary purification is removed in underpressure distillation.Finally, the product of getting part gained preliminary purification be take methanol-water again and is carried out semi-preparative high pressure liquid chromatography separation and purifying as the gradient elution solvent after dissolving with methanol solvate, collect λ
maxthe component that the 254nm uv-absorbing is the strongest, repetitive operation to the product 7-carbonyl-8,15-isopimaric acid of gained preliminary purification all separates and purifying, and after merging, evaporation is removed the methanol-water solvent and is obtained purpose product 7-carbonyl-8,15-isopimaric acid; Described initiator is 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone, 2, a kind of or any several mixture in 2-dimethoxy-2-phenyl methyl phenyl ketone, 2-hydroxy-2-methyl Propiophenone.
Mass ratio m
isopimaric acid: m
initiator=1: 0.04.
Described solvent is any one in tetrahydrofuran (THF), methyl-sulphoxide, turps, α-pinene, beta-pinene.
Described ultraviolet lighting obtains by uv cure machine, and the output rating of uv cure machine is 300 ~ 600W, reaction intensity of illumination 100%.
The luminous range of described uv cure machine is 4.5cm～22.5cm.
Be 0～1h the set time of described ultraviolet lighting reaction, but be not equal to 0.
Described column chromatography is separated.
Described eluent adopts the volume ratio normal hexane: ethyl acetate=(6 ~ 9.5): (4 ~ 0.5) normal hexane and the mixed solution of ethyl acetate.
In described column chromatography, weighting agent used is 200 ~ 300 order silica gel.
Beneficial effect:
(1) the present invention is raw materials used is isopimaric acid, separates and obtains the easy rosin very large from output, abundant raw materials.Be easy to get, UV-curing technology environmental protection used.
(2) the present invention uses UV-light as the reaction needed energy, and reaction process is simple, easy to operate, and the reaction times is short, environmental protection.
(3) reaction product can be separated and be purified by column chromatography methods, can meet preparation, the research of many 7-carbonyl-8,15-isopimaric acids and the demand of utilizing.
The accompanying drawing explanation:
The GC figure that Fig. 1 is 7-carbonyl-8,15-isopimaric acid of obtaining of embodiment 1.In figure, retention time is 5min peak (0 before
#) be solvent, the peak (1 of retention time 39.21min
#) be the raw material isopimaric acid, the peak (2 that retention time is 54.92min
#) be 7-carbonyl-8,15-isopimaric acid, other is unidentified impurity.
The FT-IR abosrption spectrogram that Fig. 2 is 7-carbonyl-8,15-isopimaric acid of obtaining of embodiment 1.
The UV abosrption spectrogram that Fig. 3 is 7-carbonyl-8,15-isopimaric acid of obtaining of embodiment 1.
Embodiment
Further illustrate by the following examples the present invention.
The raw material isopimaric acid is the self-control isopimaric acid, purity is 95.6%(GC), concrete preparation method is with reference to Chinese invention patent ZL 200810123831.2[Zhao Zhen east, Li Xingdi, Bi Liangwu, Deng. the preparation method of isopimaric acid] and document [Li Xingdi, Chen Yuxiang, Zhao Zhendong, etc. isopimaric acid separates the novel method of preparation. chemistry of forest product and industry, 2008,28 (5): 21 ~ 25].
Described semi-preparative high pressure liquid chromatography separation condition: Shim-pack PRC-ODS C
18reversed-phase column (250mm * 20mm, 15 μ m), the detector wavelength X
max254nm, 40 ℃ of sample size 0.5 ~ 1mL. column temperatures, moving phase is methyl alcohol (B) and water (A), the gradient program is 0 → 20min, 25%B → 35%B; 20 → 25min, 35%B → 60%B; 25-70min, 60%B → 100%B; 70 → 75min, 100%B → 100%B.
Embodiment 1
Isopimaric acid 0.5g and 0.02g light trigger 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone (be equivalent to raw materials quality 4%) are added in the 10mL beaker, add the 1.5g tetrahydrofuran (THF) as solvent, shake up wiring solution-forming.With the wet film preparing device of 75 μ m specifications by solution coat on the tinplate sheet of 120mm * 50mm * 0.28mm specification.Solidify 300s in the uv cure machine of 600W, lamp is apart from 4.5cm, intensity of illumination 100%.After having reacted, with tetrahydrofuran (THF) (THF) solvent, the coating drip washing on the tinplate sheet is collected.Reaction repeated operates until material is finished using.Merge all collection liquid that obtain, solvents tetrahydrofurane is wherein removed in pressure-0.05MPa evaporation by rotatory evaporator, obtain pulverous isopimaric acid photocuring product 0.409g.
Embodiment 2
Get the product 0.409g that embodiment 1 obtains, isopimaric acid photocuring product is dissolved to the solution that is made into 0.1g/mL with the mixed solution of 0.4mL eluent normal hexane and ethyl acetate, the column chromatography that is 200 ~ 300 order silica gel through weighting agent is separated, and collects different time wash-out component out.The employing volume ratio is normal hexane: ethyl acetate=(6 ~ 9.5): the normal hexane of (4 ~ 0.5) and the mixed solution of ethyl acetate are eluent, and the eluent optimum proportion is the volume ratio normal hexane: the mixing solutions of ethyl acetate=8: 2.Collect liquid and follow the tracks of and detect with HPLC-UV, merge and collect λ
maxthe component that the 254nm uv-absorbing is the strongest, evaporate and remove eluent by rotatory evaporator, 7-carbonyl-8,15-isopimaric acid that products therefrom is preliminary purification, get part and check by capillary gas chromatography that to obtain 7-carbonyl-8,15-isopimaric acid purity be the 49.2%(area normalization method).
Embodiment 3
Get the 7-carbonyl-8 of the resulting product preliminary purification of part embodiment 2, the 15-isopimaric acid, wiring solution-forming after dissolving with methanol solvate, and then take methanol-water and carry out semi-preparative high pressure liquid chromatography separation and purifying as the gradient elution solvent, ultraviolet wavelength λ collected
maxthe component that the 254nm uv-absorbing is the strongest, repetitive operation is to the product 7-carbonyl-8 of gained preliminary purification, the 15-isopimaric acid all separates and purifying, the evaporation of merging collection liquid is removed the methanol-water solvent and is obtained purpose product 7-carbonyl-8, the 15-isopimaric acid, the purpose product 7-carbonyl obtained-8,15-isopimaric acid purity 82.6%(GC).This material by UV-vis, FT-IR, MS,
1h-NMR,
13c-NMR etc. carry out structural characterization, and its Structural Identification is as follows:
UV-vis(λ
max)：249nm。
FT-IR(υ
max?cm
-1):3079.68，2928.79,1705.90,1654.30,1564.20,1241.77,912.83。
MS(m/z)：315[C
20H
27O
3]
+([M-1]
+,100),316[C
20H
28O
3]
+([M]
+,25)。
1H-NMR（δ,300MHz,CDCl
3）:1.0058(s，3H，C
10-CH
3)，1.1252(s，3H，C
13-CH
3)，1.2759(s，3H，C
4-CH
3)，1.2302~1.2550(m，1H，C
5-H)，1.3252~1.3818(m，2H)，4.8651(dd，1H，J
1=17.49Hz，J
2=1.25Hz，CH)，4.9367(dd，1H，J
1=10.74Hz，J
2=1.25Hz，CH)，5.6809(dd，1H，J
1=17.50Hz，J
2=10.75Hz，CH)。
13c-NMR (δ): the chemical displacement value of each carbon atom is listed in table 1.
Table 1
Embodiment 4
By isopimaric acid 0.5g and 0.1g(be equivalent to raw materials quality 20%) light trigger 2,2-dimethoxy-2-phenyl methyl phenyl ketone is added in the 10mL beaker, adds turps as solvent, shakes up wiring solution-forming.With the wet film preparing device of 75 μ m specifications by solution coat on the tinplate sheet of 120mm * 50mm * 0.28mm specification.Solidify 240s in the uv cure machine of 300W, lamp is apart from 9cm, intensity of illumination 100%.After having reacted, with solvent THF, the coating drip washing on the tinplate sheet is collected.Reaction repeated operates until material is finished using.Merge and collect liquid, by rotatory evaporator, in pressure-0.095MPa evaporation, remove desolventizing, obtain isopimaric acid photocuring product.The product that collection is obtained dissolves with the mixed solution of normal hexane and ethyl acetate, operation by column chromatography by embodiment 2 is separated, and then utilize semi-preparative high pressure liquid chromatography to carry out purifying by the operation of embodiment 3, obtain 7-carbonyl-8,15-isopimaric acid.
Embodiment 5
By isopimaric acid 0.5g and 0.005g(be equivalent to raw materials quality 1%) light trigger 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone and 2-hydroxy-2-methyl Propiophenone be added in the 10mL beaker, add the 1.5g methyl-sulphoxide as solvent, shake up wiring solution-forming.With the wet film preparing device of 75 μ m specifications by solution coat on the tinplate sheet of 120mm * 50mm * 0.28mm specification.Solidify 600s in the uv cure machine of 400W, lamp is apart from 12.5cm, intensity of illumination 100%.After having reacted, with solvent THF, the coating drip washing on the tinplate sheet is collected.Reaction repeated operates until material is finished using.Merge and collect liquid, by rotatory evaporator, in pressure-0.09MPa evaporation, remove desolventizing, obtain isopimaric acid photocuring product.The product that collection is obtained dissolves with the mixed solution of normal hexane and ethyl acetate, operation by column chromatography by embodiment 2 is separated, and then utilize semi-preparative high pressure liquid chromatography to carry out purifying by the operation of embodiment 3, obtain 7-carbonyl-8,15-isopimaric acid.
Claims (7)
1. the preparation method of a 7-carbonyl-8,15-isopimaric acid, is characterized in that, by raw material isopimaric acid, initiator according to mass ratio m
isopimaric acid: m
initiator=1: the ratio of (0.01～0.20) is dissolved in solvent and mixes wiring solution-forming, then solution coat is reacted on the tinplate sheet under ultraviolet lighting, collection liquid is collected to obtain in the coating drip washing that reaction obtains reaction with solvent after finishing, reaction repeated to solution is finished using, and merges all collection liquid evaporations that obtain and obtains Powdered isopimaric acid photocuring product except desolventizing; After gained isopimaric acid photocuring product is dissolved with eluent, adopt column chromatography to be separated, collect different time wash-out component out, follow the tracks of combining data detection according to HPLC-UV and collect λ
maxthe component that the 254nm uv-absorbing is the strongest, the pulverulent solids product 7-carbonyl-8 that eluent obtains preliminary purification is removed in underpressure distillation, the 15-isopimaric acid, finally, get the product 7-carbonyl-8 of part gained preliminary purification, the 15-isopimaric acid be take methanol-water again and is carried out semi-preparative high pressure liquid chromatography separation and purifying as the gradient elution solvent after dissolving with methanol solvate, collect λ
maxthe component that the 254nm uv-absorbing is the strongest, repetitive operation to the product 7-carbonyl-8,15-isopimaric acid of gained preliminary purification all separates and purifying, and after merging, evaporation is removed the methanol-water solvent and is obtained purpose product 7-carbonyl-8,15-isopimaric acid; Described initiator is 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone, 2, a kind of or any several mixture in 2-dimethoxy-2-phenyl methyl phenyl ketone, 2-hydroxy-2-methyl Propiophenone; Described solvent is any one in tetrahydrofuran (THF), methyl-sulphoxide, turps, α-pinene, beta-pinene.
2. the preparation method of 7-carbonyl-8,15-isopimaric acid as claimed in claim 1, is characterized in that, mass ratio m
different pimaric acid: m
initiator=1: 0.04.
3. the preparation method of 7-carbonyl-8,15-isopimaric acid as claimed in claim 1, is characterized in that, described ultraviolet lighting obtains by uv cure machine, and the output rating of uv cure machine is 300～600W, reaction intensity of illumination 100%.
4. the preparation method of 7-carbonyl-8,15-isopimaric acid as claimed in claim 3, is characterized in that, the luminous range of described uv cure machine is 4.5cm～22.5cm.
5. the preparation method of 7-carbonyl-8,15-isopimaric acid as claimed in claim 1, is characterized in that, be 0～1h the set time of described ultraviolet lighting reaction, but be not equal to 0.
6. the preparation method of 7-carbonyl-8,15-isopimaric acid as claimed in claim 1, is characterized in that, it is normal hexane that described eluent adopts volume ratio: ethyl acetate=(6～9.5): the normal hexane of (4～0.5) and the mixed solution of ethyl acetate.
7. the preparation method of 7-carbonyl-8,15-isopimaric acid as claimed in claim 1, is characterized in that, in described column chromatography, weighting agent used is 200～300 order silica gel.
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Non-Patent Citations (6)
| Title |
|---|
| Anticariogenic Properties of ent-Pimarane Diterpenes Obtained by Microbial Transformation;Marcela E. Severiano et al.;《Molecules》;20101125;第15卷;第8553-8566页 * |
| Bioactive Constituents of Thuja occidentalis;Leng Chee Chang et al.;《J. Nat. Prod.》;20000727;第63卷(第9期);第1235-1238页 * |
| Leng Chee Chang et al..Bioactive Constituents of Thuja occidentalis.《J. Nat. Prod.》.2000,第63卷(第9期),第1235-1238页. |
| Marcela E. Severiano et al..Anticariogenic Properties of ent-Pimarane Diterpenes Obtained by Microbial Transformation.《Molecules》.2010,第15卷第8553-8566页. |
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| 王涛 等.枞酸自动氧化产物的研究.《林产化学与工业》.1991,第11卷(第3期),第173-181页. |
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