CN104592178B - Preparation method of internal dehydroabietate - Google Patents
Preparation method of internal dehydroabietate Download PDFInfo
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- CN104592178B CN104592178B CN201410836684.9A CN201410836684A CN104592178B CN 104592178 B CN104592178 B CN 104592178B CN 201410836684 A CN201410836684 A CN 201410836684A CN 104592178 B CN104592178 B CN 104592178B
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- dehydroabietic acid
- preparation
- reaction
- acid lactone
- resulting material
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
Abstract
The invention discloses a preparation method of internal dehydroabietate. The structural formula of the internal dehydroabietate is disclosed in the specification. The internal dehydroabietate is prepared by reacting 7-carbonyl-dehydroabietic acid and selenium dioxide. The method implements one-step preparation of the internal dehydroabietate, has the advantages of fewer byproducts and high yield, and brings in inestimable economic benefits.
Description
Technical field
The present invention relates to a kind of preparation method of dehydroabietic acid lactone (picealactone), belong to Synthetic Organic Chemistry neck
Domain.
Background technology
Dehydroabietic acid lactone compound (picealactone) is compound present in a kind of natural resources, in Taiwan cloud
It is found first in the wood extractive of China fir.
Dehydroabietic acid lactone compound, as natural product, has the superior of the structure that general organic compound does not possess
Property, has the advantages that toxic and side effects are low, effect on environment is little.With dehydroabietic acid lactone compound as lead compound, synthesis
A series of compounds have significant biological activity, because it has many potential pharmacologically actives, can be used for pesticide and medicine
Field is as insecticide, antiviral drugs etc..Therefore, the research of such compound receives the extensive pass of Chinese scholars
Note.
Content of the invention
The present invention provides a kind of preparation method of dehydroabietic acid lactone, one-step synthesis dehydroabietic acid lactone, and preparation is simple, bar
Part is gentle, by-product is few, yield is high.
For solving above-mentioned technical problem, the technical solution adopted in the present invention is as follows:
A kind of preparation method of dehydroabietic acid lactone, the structural formula of dehydroabietic acid lactone is:
Dehydroabietic acid lactone is obtained by 7- carbonyl dehydroabietic acid and selenium dioxide reaction.
Said method achieves the one-step method preparation of dehydroabietic acid lactone, and by-product is few, yield is high, brings inestimable
Economic benefit.
For reaction efficiency and yield, above-mentioned dehydroabietic acid lactone is reacting molten by 7- carbonyl dehydroabietic acid and selenium dioxide
In agent, in the presence of catalyst, reaction is obtained；Wherein, reaction dissolvent is water, Isosorbide-5-Nitrae-dioxane or both any proportionings
Mixture.
Preferably, reaction dissolvent be water and Isosorbide-5-Nitrae-dioxane volume ratio be 1:(0-3.5) mixture；Further preferably,
Reaction dissolvent is water and Isosorbide-5-Nitrae-dioxane volume ratio is 1:(2.5-3.5) mixture, it is further preferred that reaction dissolvent is water and 1,
4- dioxane volume ratio is the mixture of 1:3.
The reaction scheme of said method particularly as follows:
For 8 methylene of selective oxidation, oxidant used is selenium dioxide to the application.
In order to improve reaction efficiency further, described catalyst be trifluoromethane sulfonic acid ytterbium, ytterbium perfluorooctanesulfonate or
Amberlyst a26 resin.
In order to improve reaction efficiency, the ratio of the amount of material of 7- carbonyl dehydroabietic acid, selenium dioxide and catalyst further
For 1:(1～2): 0.1.
It is preferable that reaction temperature is 60-100 DEG C, the response time is 12-24 hour to above-mentioned preparation method.Said method is not only
Reaction is gentle, and can guarantee that the yield of products obtained therefrom.
Above-mentioned preparation method purifies as follows it is preferable that resulting material will be reacted:
A, reaction resulting material is cooled to room temperature, adds the acetic acid that quality consumption is reaction resulting material quality 5-20 times
Ethyl ester, is filtered to remove unreacted oxidant by kieselguhr；It is reaction resulting material quality that gained filtrate passes through quality consumption
After 5-20 times of ethyl acetate extraction, organic faciess, after saturated nacl aqueous solution washs, is dried, concentrating, obtain dehydroabietic acid
Lactone crude product；
B, with ethyl acetate, dehydroabietic acid lactone crude product is carried out after recrystallization, be 50～55 DEG C, vacuum in temperature
It is vacuum dried under conditions of 0.01～0.1mpa, obtained dehydroabietic acid lactone.
Above-mentioned reaction resulting material refers to the thing of gained after the completion of 7- carbonyl dehydroabietic acid, selenium dioxide and catalyst reaction
Material, in above-mentioned steps b, drying time is preferably 10-14h.
The purity of products obtained therefrom can be further ensured that by above-mentioned method of purification.
The NM technology of the present invention is all with reference to prior art.
The preparation method of dehydroabietic acid lactone of the present invention it is achieved that the one-step synthesis of dehydroabietic acid lactone, and prepare simple,
Reaction condition is gentle, and by-product is few, yield is high, purity high (more than 99%), brings immeasurable economic worth.
Brief description
The hydrogen spectrogram of Fig. 1 embodiment 1 gained compound a.
The mass spectrum of Fig. 2 embodiment 1 gained compound a.
The crystal structure figure of Fig. 3 embodiment 1 gained compound a.
Specific embodiment
For a better understanding of the present invention, it is further elucidated with present disclosure with reference to embodiment, but the present invention
Content is not limited solely to the following examples.
Embodiment 1:
The preparation of compound a:
7- carbonyl dehydroabietic acid 10mmol, selenium dioxide 20mmol, trifluoromethyl is sequentially added in 10ml single-necked flask
Sulfonic acid ytterbium 0.1mmol, Isosorbide-5-Nitrae-dioxane 3ml, water 1ml, are warming up to 80 DEG C, and react 24h under agitation.Reactant liquor is cooled down
To room temperature and add ethyl acetate 15ml, filtered by kieselguhr and unreacted selenium dioxide is removed by absorption.Filtrate is used
15ml ethyl acetate extracts three times, merges organic faciess, washs three times with 15ml saturated sodium-chloride.Organic faciess through drying, concentrate,
And with after re-crystallizing in ethyl acetate, temperature be 50～55 DEG C, vacuum be 0.02～0.03mpa under conditions of carry out vacuum and do
Dry 12h, obtains compound a, and purity is 99%.Yield: 78%, white solid；mp:182-184℃.ms(esi)m/z 311[m
+h]+.1H nmr (400 mhz, dmso) δ 7.96 (d, j=1.9 hz, 1h), 7.75 (d, j=8.2 hz, 1h), 7.63 (dd, j
=8.2,2.0 hz, 1h), 3.10 2.89 (m, 1h), 2.43 (d, j=12.8 hz, 1h), 2.09 (d, j=14.1 hz, 1h),
1.95 (d, j=12.6 hz, 1h), 1.72 (d, j=14.7 hz, 2h), 1.57 (d, j=8.0hz, 6h), 1.24 (d, j=6.9
hz,6h).
Embodiment 2:
The preparation of compound a:
7- carbonyl dehydroabietic acid 10mmol, selenium dioxide 10mmol, perfluoro capryl is sequentially added in 10ml single-necked flask
Sulfonic acid ytterbium 0.1mmol, water 1ml, are warming up to 100 DEG C, and react 15h under agitation.Reactant liquor is cooled to room temperature and adds second
Acetoacetic ester 10ml, is filtered by kieselguhr and removes unreacted selenium dioxide by absorption.Filtrate is extracted with 10ml ethyl acetate
Take three times, merge organic faciess, wash three times with 10ml saturated sodium-chloride.Organic faciess are through being dried, concentrating and use ethyl acetate weight
After crystallization, temperature be 50～55 DEG C, vacuum be 0.06～0.07mpa under conditions of carry out be vacuum dried 11h, obtain chemical combination
Thing a, purity is 99%.Yield: 70%, white solid；mp:182-184℃.ms(esi)m/z311[m+h]+.1h nmr(400
Mhz, dmso) δ 7.96 (d, j=1.9 hz, 1h), 7.75 (d, j=8.2 hz, 1h), 7.63 (dd, j=8.2,2.0 hz,
1h), 3.10 2.89 (m, 1h), 2.43 (d, j=12.8 hz, 1h), 2.09 (d, j=14.1hz, 1h), 1.95 (d, j=12.6
Hz, 1h), 1.72 (d, j=14.7 hz, 2h), 1.57 (d, j=8.0 hz, 6h), 1.24 (d, j=6.9 hz, 6h).
Claims (5)
1. a kind of preparation method of dehydroabietic acid lactone it is characterised in that: the structural formula of dehydroabietic acid lactone is:
Dehydroabietic acid lactone, in the presence of catalyst, is reacted by 7- carbonyl dehydroabietic acid and selenium dioxide in reaction dissolvent
It is obtained；Wherein, reaction dissolvent is the mixture of water, Isosorbide-5-Nitrae-dioxane or both any proportionings；Catalyst is trifluoromethyl sulphur
Sour ytterbium or ytterbium perfluorooctanesulfonate.
2. preparation method as claimed in claim 1 it is characterised in that: 7- carbonyl dehydroabietic acid, selenium dioxide and catalyst
The ratio of the amount of material is 1:(1～2): 0.1.
3. preparation method as claimed in claim 1 or 2 it is characterised in that: reaction temperature is 60-100 DEG C, and the response time is
12-24 hour.
4. preparation method as claimed in claim 1 or 2 it is characterised in that: reaction dissolvent be water and Isosorbide-5-Nitrae-dioxane volume
Than for 1:(0-3.5) mixture.
5. preparation method as claimed in claim 1 or 2 it is characterised in that: resulting material will be reacted and purify as follows:
A, reaction resulting material is cooled to room temperature, adds the acetic acid second that quality consumption is reaction resulting material quality 5-20 times
Ester, is filtered to remove unreacted oxidant by kieselguhr；It is reaction resulting material quality 5- that gained filtrate passes through quality consumption
After 20 times of ethyl acetate extraction, organic faciess, after saturated nacl aqueous solution washs, is dried, concentrating, obtain in dehydroabietic acid
Ester crude product；
B, with ethyl acetate, dehydroabietic acid lactone crude product is carried out after recrystallization, temperature be 50～55 DEG C, vacuum be
It is vacuum dried under conditions of 0.01～0.1mpa, obtained dehydroabietic acid lactone.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410836684.9A CN104592178B (en) | 2014-12-29 | 2014-12-29 | Preparation method of internal dehydroabietate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410836684.9A CN104592178B (en) | 2014-12-29 | 2014-12-29 | Preparation method of internal dehydroabietate |
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| CN104592178A CN104592178A (en) | 2015-05-06 |
| CN104592178B true CN104592178B (en) | 2017-01-25 |
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