CN110256389A - The preparation method of gelsemium henbane pavilion - Google Patents
The preparation method of gelsemium henbane pavilion Download PDFInfo
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- CN110256389A CN110256389A CN201910484452.4A CN201910484452A CN110256389A CN 110256389 A CN110256389 A CN 110256389A CN 201910484452 A CN201910484452 A CN 201910484452A CN 110256389 A CN110256389 A CN 110256389A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
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Abstract
The invention discloses a kind of preparation methods of gelsemium henbane pavilion, 2 are used including step 1,4- dihydroxy -5- methoxybenzaldehyde is starting material, solvent and catalyst is added, in 0-300 DEG C of range of reaction temperature, malonic acid class compound progress insulation reaction is added and obtains reaction solution, the time 2h-10h of the insulation reaction, the dosage of the malonic acid class compound is 1-10 equivalent;Step 2 cools down reaction solution, and cooling temperature is -10 DEG C -35 DEG C, and a large amount of solids are precipitated after the reaction solution is cooling, carries out decompression suction filtration to the reaction solution that a large amount of solids are precipitated, obtains gelsemium henbane pavilion crude product and filtrate;Step 3 recrystallizes the gelsemium henbane pavilion crude product using ethyl acetate, obtains gelsemium henbane pavilion sterling.It is higher using yield, and cost is relatively low, less pollution.
Description
Technical field
The present invention relates to biochemical and field of medicaments, a kind of particularly preparation method of gelsemium henbane pavilion.
Background technique
Scopoletin is coumarin kind compound, is the phenolic substances being widely present in plant of Solanaceae, is distributed in plant wide
It is general, wherein in plant of Solanaceae henbane (Scopolia japonica Maxim) root, belladonna (Herba
AtropeaBelladonnas) and umbelliferae pacifies Xing Baizhi (Angelica dahurica Fisch.Ex Hoffin)
Content is higher in the root of equal plants.Scopoletin can be extracted from the plants such as artemisia annua and be obtained, and have important medical value, simultaneously
With the resistance etc. on a variety of agricultural biological activities, mainly including bacteriostatic activity, coordinate plant growth development and induction plant.
In addition, scopoletin can also be used for the Active oxygen release during detection oxidative burst, it is used as peroxide street cleaner and acetylcholinesterase
Inhibitor.Scopoletin clinically has wind-dispelling, anti-inflammatory, analgesic, phlegm-dispelling functions.
The product is using the method preparation extracted from plant Artemisia annua mostly at present, and extraction process is cumbersome, and
Extraction efficiency is low, leads to valuable product, does not have the market competitiveness.The giant of the current main world Dou Shi reagent industry is such as
Merck, match be silent to fly etc. to monopolize the product.In addition, the product traditional processing technology of foreign literature report has dirt
The significant drawbacks such as dye is big, and operation difficulty is big and yield is low, allow domestic corporation temporarily could not power realize the green of the product at home
Metaplasia produces, and the health for hindering China's biochemical diagnosis reagent industry and plant immune inducer industry is grown rapidly.
Existing gelsemium henbane pavilion production method, mainly there is following three kinds: the first is directly to extract from artemisia annua, first prepares Huang
Flower wormwood artemisia acetone extract uses petroleum ether-second after silica gel progress column chromatography for separation is then added in artemisia annua acetone extract
Acetoacetic ester mitigates solvent and is eluted.The available 30-50 milligrams of scopoletin sterling of the general 1 kilogram of artemisia annua of this method is extracted
Under efficiency is very low, and it can also generate a large amount of waste residue and liquid.This process and the requirement for not meeting green syt.
It is that raw material is synthesized through 2 footworks that second method, which is with 2,4- dihydroxy -5- methoxybenzaldehyde and malonic acid,
2,4- dihydroxy -5- methoxybenzaldehyde and malonic acid are subjected to cyclization using pyridine and aniline as solvent and reaction reagent, obtained
Carboxy intermediate;The carboxy intermediate obtains scopoletin (Bioorganic&Medicinal Chemistry through high temperature decarboxylation again
Letters,2016,26(23),5732-5735);
The synthetic method is at present using widest method, and used raw material is comparatively relatively cheap, and operation can
Control property is also relatively good;But the route of the synthetic method is comparatively long, needs to carry out 2 step independent operations;Reaction time
Comparatively also long, step 1 need to react 24 hours, and step 2 is also required to 3.5 hours, and overall reaction duration 27.5 hours;And
It requires in two-step reaction using the very big genotoxicity solvent pyridine of smell, to the health of operator, there are larger
Hidden danger does not meet the principle of green syt, it is difficult to be suitble to the demand of industrialized production.
The third method is passed through using 2,4- dihydroxy -5- methoxybenzaldehyde and (triphenylphosphine alkene) ethyl acetate as raw material
1 footwork is synthesized: by 2,4- dihydroxy -5- methoxybenzaldehyde and (triphenylphosphine alkene) ethyl acetate in N, N- diethylaniline
Middle heating reaction obtains scopoletin (Tetrahedron, 2002,58 (11), 2163-2166);
The synthetic method route is short, and operation comparatively can be easier;But the route is there is also obvious shortcoming,
This method conversion ratio is relatively low, and yield only has 27%;And (triphenylphosphine alkene) ethyl acetate molecular weight 348.37, and really add
The acetate moiety molecular weight closed on molecule only has 60.05, and Atom economy is very poor, and can generate in reaction process a large amount of
By-product triphen oxygen phosphorus is created great difficulties to subsequent purifying;This process and the principle for not meeting green syt, it is difficult to
It is suitble to the demand of industrialized production.
Summary of the invention
In order to overcome the defects of the prior art, the embodiment of the invention provides a kind of preparation method of gelsemium henbane pavilion, make
Higher with yield, cost is relatively low, less pollution.
To achieve the above object, the embodiment of the present application discloses a kind of preparation method of gelsemium henbane pavilion, comprising: step 1: makes
It is starting material with 2,4- dihydroxy -5- methoxybenzaldehyde, solvent and catalyst is added, in 0-300 DEG C of reaction temperature model
In enclosing, malonic acid class compound is added carries out insulation reaction and obtain reaction solution, the time 2h-16h of the insulation reaction, described third
The dosage of two acid compounds is 1-10 equivalent;
Step 2: reaction solution is cooled down, and cooling temperature is -10 DEG C -35 DEG C, is precipitated after the reaction solution is cooling a large amount of
Solid carries out decompression suction filtration to the reaction solution that a large amount of solids are precipitated, obtains gelsemium henbane pavilion crude product and filtrate;
Step 3: the gelsemium henbane pavilion crude product is recrystallized using ethyl acetate, obtains gelsemium henbane pavilion sterling.Preferably,
The malonic acid class compound is malonic acid, malonic acid monomethyl ester, monoethyl malonate, malonic acid list isopropyl ester, malonic acid two
One or more of methyl esters, diethyl malonate, Diisopropyl malonate.
Preferably, the filtrate can repeat to use or carry out the vacuum distillation extraction solvent as solvent.
Preferably, reaction temperature is 50 DEG C -250 DEG C in the step 1.
Preferably, cooling temperature is -5 DEG C -10 DEG C in the step 2.
Preferably, the solvent is N, one or both of N- dimethylaniline and N, N- diethylaniline.
Preferably, the catalyst is N, one or both of N- dimethylaniline and N, N- diethylaniline.
Preferably, the insulation reaction time is 4h-8h in the step 1.
Preferably, TLC monitoring reaction is carried out to the reaction solution in step 1, to monitor extent of reaction.
Beneficial effects of the present invention are as follows:
1, reaction step is few, easy to operate, is suitable for industrialized production;
2, intermediate treatment link is saved, reaction yield is improved, the cost of unit product reduces, so that cost is relatively low,
High income can be suitble to most relevant enterprises to be produced;
3, have solvent, a small amount of unreacted in the filtrate of step 2 completely excessive malonic acid class compound and does not have on a small quantity
The product that complete crystallization comes out, in addition, without other impurities;Solvent and malonic acid class compound can be in next secondary responses
It is applied, less pollution, is suitable for industrialized production;
4, the reagent in the present invention is also catalyst simultaneously, it may not be necessary to add additional catalyst, simplify simultaneously
Post-processing operation.
For above and other objects, features and advantages of the invention can be clearer and more comprehensible, preferred embodiment is cited below particularly,
And cooperate institute's accompanying drawings, it is described in detail below.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the nmr spectrum of gelsemium henbane pavilion sterling in the embodiment of the present invention 1;
Fig. 2 is the HPLC spectrogram of gelsemium henbane pavilion sterling in the embodiment of the present invention 2;
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Below in conjunction with specific embodiment to the detailed description of realization of the invention.
Embodiment 1 sequentially adds 2, the 4- dihydroxy -5- first of 336g into four mouthfuls of reaction flasks of 5L under mechanical stirring
The N of oxygroup benzaldehyde, the malonic acid monomethyl ester of 256g and 1.5L, N- dimethylaniline obtain reaction solution;Reaction solution is heated to 180
After DEG C, the insulation reaction as shown in following formula 1 of 6h is carried out to reaction solution, while TLC monitoring reaction is carried out to reaction solution,
To be monitored to extent of reaction, whether confirmation reaction is completed.
Chemical formula 1
After completing 6h insulation reaction, reaction solution is cooled to 10 DEG C, a large amount of greenish yellow solids are precipitated in reaction solution.It is yellow to being precipitated
The reaction solution of green solid carries out decompression suction filtration, is collected into a large amount of yellow green gelsemium henbane pavilion crude products and filtrate;Gelsemium henbane pavilion crude product is used
Re-crystallizing in ethyl acetate obtains 352g greenish yellow solid scopoletin sterling.
It is applied it is understood that filtrate can relay to continue in lower secondary response, recycling N, N- diformazan can also be evaporated under reduced pressure
Aniline.Solvent can reuse, and cost is relatively low, less pollution.
Referring to FIG. 1, being detected using Nuclear Magnetic Resonance to gelsemium henbane pavilion sterling, as described in Figure 1, in nmr spectrum
Showing is 8 groups of H in total, wherein 6 groups are gelsemium henbane pavilion, remaining is the H of water and deuterated solvent.Wherein, gelsemium henbane pavilion sterling at this time
Yield reach 91.6%, fusing point is 200 DEG C -204 DEG C, and HPLC purity is 99.23%.The gelsemium henbane pavilion sterling uses yield
It is higher, and reaction step is less.
In the present embodiment, the N, N- dimethylaniline are both solvent and catalyst, it may not be necessary to be added additional
Catalyst, while simplifying post-processing operation.
Under mechanical stirring, 2, the 4- dihydroxy -5- methoxyl group of 505g is sequentially added into tetra- mouthfuls of reaction flasks of 5L for embodiment 2
The N of benzaldehyde, the malonic acid of 400g and 2.5L, N- dimethylaniline obtain reaction solution;It is right after reaction solution is heated to back flow reaction
Reaction solution while monitoring the reaction solution TLC for carrying out insulation reaction anti-into the insulation reaction as shown in following formula 2 of 4h
It answers, to be monitored to extent of reaction, whether confirmation reaction is completed.
Chemical formula 2
After the insulation reaction for completing 4h, reaction solution is cooled to 5 DEG C, a large amount of greenish yellow solids are precipitated in reaction solution.To precipitation
The reaction solution of greenish yellow solid carries out decompression suction filtration, is collected into a large amount of yellow green gelsemium henbane pavilion crude products and filtrate, filtrate can be under
Continue to apply in secondary response, recycling N, N- dimethylaniline can also be evaporated under reduced pressure.By gelsemium henbane pavilion crude product re-crystallizing in ethyl acetate
Obtain 540g yellow green scopoletin sterling.
It is understood that in the present embodiment, the N, N- dimethylaniline is both solvent and catalyst, can be not required to
Additional catalyst is added, while simplifying post-processing operation.
The use yield 93.7% of gelsemium henbane pavilion sterling at this time, 200 DEG C -204 DEG C of fusing point.Referring to FIG. 2, using efficient liquid phase
Chromatography detects gelsemium henbane pavilion sterling, as shown in Fig. 2, HPLC spectrogram is shown, the peak area pole of miscellaneous peak in gelsemium henbane pavilion sterling
Small, HPLC purity 99.12%, the gelsemium henbane pavilion sterling uses yield higher, and reaction step is less.The gelsemium henbane pavilion sterling
Analysis result it is shown in table 1.
Table 1
Under mechanical stirring, 2, the 4- dihydroxy -5- methoxyl group of 505g is sequentially added into tetra- mouthfuls of reaction flasks of 5L for embodiment 3
The diethyl malonate and 2LN of benzaldehyde, 620g, N- diethylaniline obtain reaction solution;Reaction solution is heated to 210 DEG C of reactions
Afterwards, the insulation reaction as shown in following formula 3 of 8h is carried out to reaction solution, while TLC monitoring reaction is carried out to reaction solution, from
And extent of reaction is monitored, whether confirmation reaction is completed.
Chemical formula 3
After completing 8h insulation reaction, reaction solution is cooled to -5 DEG C, a large amount of greenish yellow solids are precipitated in reaction solution.It is yellow to being precipitated
The reaction solution of green solid carries out decompression suction filtration, is collected into a large amount of yellow green gelsemium henbane pavilion crude products and filtrate, filtrate can be in next times
Continue to apply in reaction, recycling N, N- diethylaniline can also be evaporated under reduced pressure;Gelsemium henbane pavilion crude product is obtained with re-crystallizing in ethyl acetate
To 510g greenish yellow solid scopoletin sterling.At this time gelsemium henbane pavilion sterling be yield 88.5%, 200-204 DEG C of fusing point, HPLC purity
98.76%.
It is understood that in the present embodiment, the N, N- diethylaniline is both solvent and catalyst, can be not required to
Additional catalyst is added, while simplifying post-processing operation.
Specific embodiment is applied in the present invention, and principle and implementation of the present invention are described, above embodiments
Explanation be merely used to help understand method and its core concept of the invention;At the same time, for those skilled in the art,
According to the thought of the present invention, there will be changes in the specific implementation manner and application range, in conclusion in this specification
Appearance should not be construed as limiting the invention.
Claims (9)
1. a kind of biochemical diagnosis reagent and plant immune inducer-gelsemium henbane pavilion preparation method, it is characterised in that:
Step 1: the use of 2,4- dihydroxy -5- methoxybenzaldehyde is starting material, solvent and catalyst is added, at 0-300 DEG C
Range of reaction temperature in, be added malonic acid class compound carry out insulation reaction obtain reaction solution, the time of the insulation reaction
2h-16h, the dosage of the malonic acid class compound are 1-10 equivalent;
Step 2: reaction solution is cooled down, and cooling temperature is -10 DEG C -35 DEG C, is precipitated after the reaction solution is cooling a large amount of solid
Body carries out decompression suction filtration to the reaction solution that a large amount of solids are precipitated, obtains gelsemium henbane pavilion crude product and filtrate;
Step 3: the gelsemium henbane pavilion crude product is recrystallized using ethyl acetate, obtains gelsemium henbane pavilion sterling.
2. the preparation method of gelsemium henbane pavilion as described in claim 1, which is characterized in that the malonic acid class compound is the third two
Acid, malonic acid monomethyl ester, monoethyl malonate, malonic acid list isopropyl ester, dimethyl malenate, diethyl malonate, malonic acid
One or more of diisopropyl ester.
3. the preparation method of gelsemium henbane pavilion as described in claim 1, which is characterized in that the filtrate can repeat to use as solvent
Or it carries out vacuum distillation and extracts the solvent.
4. the preparation method of gelsemium henbane pavilion as described in claim 1, which is characterized in that reaction temperature is 50 in the step 1
℃-250℃。
5. the preparation method of gelsemium henbane pavilion as described in claim 1, which is characterized in that cooling temperature is -5 in the step 2
℃-10℃。
6. the preparation method of gelsemium henbane pavilion as claimed in claim 5, which is characterized in that the solvent is N, N- dimethylaniline and N,
One or both of N- diethylaniline.
7. the preparation method of gelsemium henbane pavilion as described in claim 1, which is characterized in that the catalyst is N, N- dimethylaniline and
One or both of N, N- diethylaniline.
8. the preparation method of gelsemium henbane pavilion as described in claim 1, which is characterized in that the insulation reaction time is in the step 1
4h-8h。
9. the preparation method of gelsemium henbane pavilion as described in claim 1, which is characterized in that carry out TLC to the reaction solution in step 1
Monitoring reaction, to monitor extent of reaction.
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Publication number | Priority date | Publication date | Assignee | Title |
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CN111423450A (en) * | 2020-04-29 | 2020-07-17 | 上海天马有机发光显示技术有限公司 | Compound, display panel and display device |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102584762A (en) * | 2012-01-10 | 2012-07-18 | 中国药科大学 | Gelsemic acid derivative and preparation method and application thereof |
CN103896895A (en) * | 2013-12-31 | 2014-07-02 | 浙江工业大学 | Method for preparing coumarin derivative |
CN103965150A (en) * | 2014-05-28 | 2014-08-06 | 广州康臣药物研究有限公司 | Scopoletin derivative as well as preparation method and application thereof |
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2019
- 2019-06-05 CN CN201910484452.4A patent/CN110256389B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102584762A (en) * | 2012-01-10 | 2012-07-18 | 中国药科大学 | Gelsemic acid derivative and preparation method and application thereof |
CN103896895A (en) * | 2013-12-31 | 2014-07-02 | 浙江工业大学 | Method for preparing coumarin derivative |
CN103965150A (en) * | 2014-05-28 | 2014-08-06 | 广州康臣药物研究有限公司 | Scopoletin derivative as well as preparation method and application thereof |
Non-Patent Citations (1)
Title |
---|
BEATRIZ SEPULVEDA ET AL.: "Gastroprotective activity of synthetic coumarins: Role of endogenous prostaglandins, nitric oxide, non-protein sulfhydryls and vanilloid receptors", 《BIOORGANIC & MEDICINAL CHEMISTRY LETTERS》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111423450A (en) * | 2020-04-29 | 2020-07-17 | 上海天马有机发光显示技术有限公司 | Compound, display panel and display device |
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