CN103113452B

CN103113452B - Digitonin extraction and purification technology

Info

Publication number: CN103113452B
Application number: CN201110347081.9A
Authority: CN
Inventors: 邓雄飞
Original assignee: HEBEI BAILING WEICHAO FINE MATERIAL CO Ltd
Current assignee: HEBEI BAILING WEICHAO FINE MATERIAL CO Ltd
Priority date: 2011-11-07
Filing date: 2011-11-07
Publication date: 2015-06-03
Anticipated expiration: 2031-11-07
Also published as: CN103113452A

Abstract

The invention discloses a technology for extracting digitonin from digitalis seeds or leaves and purifying digitonin. The technology comprises the following steps: degreasing the digitalis seeds or leaves which are treated as a raw material with an ether solvent, extracting with an alcohol-water solution, purifying with a resin, eluting, and re-crystallizing to obtain digitonin which is the target product. The technology has the advantages of suitableness for enlarged production, easily available raw material, simplicity, environmental protection, and low cost; and the purity and the total yield of the obtained target product reach above 50% and above 1.5% respectively.

Description

A kind of extraction and purification process of digitonin

Technical field

The present invention the invention belongs to the processing method extracting digitonin from the seed or leaf of foxglove.

Background technology:

Digitonin (structural formula is as Fig. 1) is a kind of glycoside obtained from the leaf and seed of pale reddish brown foxglove, the one of steroidal Saponin/TSM.During hydrolysis, a part digitogenin (digitogenin) as aglycone (aglycone) part can be generated, and have the wood sugar of bimolecular D-Glucose and two molecule one semi-lactosis and a part as the part of sugar.These sugar moieties are attached on the hydroxyl of thricarbon atom of digitogenin.Because, the steroid (such as cholesterol) that it and can have free 3 β-OH forms the DIGITONIN glycoside compound (digitonide) being insoluble in the molecular compound of water with equimolecular ratio, this characteristic can be used to carry out the qualitative of sterol and be separated.

Foxglove is important obstinate psychological treatment, can be excited myocardium, strengthens the convergent force of cardiac muscle, improves blood circulation, or directly suppress heart conduction system, make decreased heart rate, cure mainly chronic heart failure, have remarkable inducing diuresis to remove edema effect to cardiac edema.Digitonin can promote the absorption of digitalis cardiac glycoside, thus strengthens the cardiotonic of foxglove.Simultaneously as important native protein solubilizing agent, cholesterol determination agent, digitonin has larger economic worth and social value.

There is the domestic and international report of the extraction process about digitonin very few.Soviet Union's document (Khimiya Prirodnykh Soedinenii (1992), (5), 587-588.) report the technique extracting digitonin from foxglove seed, but this process repeatability is poor, solvent for use tetracol phenixin toxicity is large, and cost is high.

Summary of the invention:

Technical problem to be solved by this invention is to provide a kind of applicable novel method of amplifying extraction purification digitonin (digitonin) the leaf from pale reddish brown foxglove or seed produced.Preparation technology of the present invention has raw material and is easy to get, and reactions steps is short, simple to operate, environmentally friendly, low cost and other advantages; The target product purity obtained reaches more than 50%, and total recovery is more than 1.5%.

This invention takes following extraction and purification process scheme:

A. after being pulverized by foxglove seed, and ether solvent is placed in diafiltration cylinder, diafiltration degreasing after soaking.After degreasing, fine powder loads extractor, extracts 1 ~ 4 time by alcohol water mixed solution heat.United extraction liquid, reclaim under reduced pressure alcohol, to 2/5 ~ 5/6 of extracting liquid volume, leaves standstill 3 ~ 7 hours.Then reclaim under reduced pressure alcohol is continued extremely without alcohol taste at 75 ~ 120 DEG C.Obtain digitonin crude product.

Wherein ether solvent can be selected from one of following: sherwood oil, ether, tetrahydrofuran (THF), isopropyl ether, methyl tertiary butyl ether, 2-methyltetrahydrofuran, glycol dimethyl ether, propylene-glycol ethyl ether etc.; Preferred ether solvent is: sherwood oil, ether or tetrahydrofuran (THF).Wherein alcoholic solvent is selected from one of following: methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol etc.Alcohol water mixed solution concentration can within the scope of 0-80%, and optimum concn is 40%-60%.

B. the crude product dress resin column will obtained, uses distilled water, 10 ~ 40% alcohol, 40 ~ 80% alcohol wash-outs successively.Collect 40 ~ 80% alcohol eluens, less than 75 ~ 100 DEG C underpressure distillation, except desolventizing, obtain eluate.Recrystallization is carried out with pure alcohol, dry with vacuum drying oven.Obtain target product.

Wherein resin column filler can be selected from one of following: AB-8, D101, D201, D280; 10 ~ 40% alcohol elution volumes are 1-5 column volume, and the best is 3; 40 ~ 80% alcohol elution volumes are 1-5 column volume, and the best is 3;

This fills out the visible Fig. 2 of column experiments brief description.

Embodiment:

Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in limit to scope of the present invention for illustration of the present invention.In addition should be understood that those skilled in the art can do various change and amendment to the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.

Embodiment 1

Use high speed disintegrator to pulverize to natural matter in batches.Fine powder after pulverizing is dipped to and fills (solvent usage quantity is 3 times of seed weight) in the diafiltration cylinder of sherwood oil.Afterwards with the speed diafiltration of 3ml/kg raw material, total ether solvents amount of diafiltration is 12 times of seed weight.After diafiltration completes, the fine powder of degreasing is evaporated into dry naturally.Obtain degreasing fine powder.Degreasing fine powder is loaded extractor, uses 60% methanol reagent refluxing extraction 3 times, often all over 1 hour.1st time alcohol usage quantity is 6 times of seed weight, and the 2nd time alcohol usage quantity is 10 times of seed weight, extracts successively.United extraction liquid, carries out underpressure distillation and reclaims methyl alcohol at temperature of reaction is 50 DEG C, until 2/5 of extracting liquid volume, leaves standstill 3 hours.Less than 90 DEG C are continued reclaim under reduced pressure methyl alcohol extremely without alcohol taste.Obtain digitonin crude product.

Embodiment 2

The foxglove crude product obtained in embodiment 1 is used for purifying.Resin D101 is filled post (consumption is 1 times of seed weight), with distillation washing 3 column volumes.Slowly add the foxglove crude product (pillar flow velocity 3ml/kg raw material) obtained in embodiment 1.After distillation washing post (eluent flow rate 5ml/kg raw material) by 2 times of cylinder accumulated amounts, by 25% methanol-eluted fractions (eluent flow rate 5ml/kg raw material) of 3 times of cylinder accumulated amounts.Afterwards, by 60% methanol-eluted fractions (eluent flow rate 5ml/kg raw material) of 4 times of cylinder accumulated amounts, collect 60% alcohol eluen, underpressure distillation, except desolventizing, obtains eluate.Recrystallization is carried out with pure methyl alcohol.Dry with vacuum drying oven.Obtain digitonin, yield 1.5%, purity is 52%.

Embodiment 3

Embodiment 1 PetroChina Company Limited. ether is replaced with ether, and other operations are all identical, also obtain digitonin crude product.

Embodiment 4

Methyl alcohol in embodiment 1 and 2 is replaced with ethanol, and other operations are all identical, also obtain digitonin crude product.

Embodiment 5

By 60% alcohol reagent concentration in embodiment 1, make 40% into, other operations are all identical, also obtain digitonin crude product.

Embodiment 6

Resin D101 in embodiment 2 is replaced with Resin A B-8, (consumption is 1 times of seed weight), with distillation washing 3 column volumes.Slowly add the foxglove crude product (pillar flow velocity 3ml/kg raw material) obtained in embodiment 1.After distillation washing post (eluent flow rate 5ml/kg raw material) by 4 times of cylinder accumulated amounts, with the 30% alcohol wash-out (eluent flow rate 5ml/kg raw material) of 2 times of cylinder accumulated amounts.Afterwards, with the 70% alcohol wash-out (eluent flow rate 5ml/kg raw material) of 4 times of cylinder accumulated amounts, collect 70% alcohol eluen, underpressure distillation, except desolventizing, obtains eluate.Recrystallization is carried out with pure alcohol.Dry with vacuum drying oven.Also obtain digitonin, yield 1.3%, purity is 51%.

Embodiment 7

Resin D101 in embodiment 2 is replaced with resin D201, (consumption is 1 times of seed weight), with distillation washing 3 column volumes.Slowly add the foxglove crude product (pillar flow velocity 3ml/kg raw material) obtained in embodiment 1.After distillation washing post (eluent flow rate 5ml/kg raw material) by 3 times of cylinder accumulated amounts, with the 30% alcohol wash-out (eluent flow rate 5ml/kg raw material) of 2 times of cylinder accumulated amounts.Afterwards, with the 65% alcohol wash-out (eluent flow rate 5ml/kg raw material) of 3 times of cylinder accumulated amounts, collect 65% alcohol eluen, underpressure distillation, except desolventizing, obtains eluate.Recrystallization is carried out with pure alcohol.Dry with vacuum drying oven.Also obtain digitonin, yield 1.3%, purity is 50%.

Accompanying drawing illustrates:

Fig. 1 is digitonin molecular results formula schematic diagram;

Fig. 2 is that purifying digitonin crude product fills out column experiments brief description.

Claims

1. an extracting and purifying method for digitonin, described method is made up of following step:

(1) use high speed disintegrator to pulverize to foxglove seed in batches;

(2) be dipped in the diafiltration cylinder filled as the sherwood oil of seed weight 3 times by the fine powder after pulverizing, afterwards with the speed diafiltration of 3ml/kg raw material, total ether solvents amount of diafiltration is 12 times of seed weight;

(3) after diafiltration completes, the fine powder of degreasing is evaporated into dry naturally, obtain degreasing fine powder;

(4) degreasing fine powder is loaded extractor, use 60% methanol reagent refluxing extraction 2 times, often all over 1 hour, the 1st time alcohol usage quantity is 6 times of seed weight, and the 2nd time alcohol usage quantity is 10 times of seed weight, extracts successively;

(5) united extraction liquid, carries out underpressure distillation and reclaims methyl alcohol at temperature of reaction is 50 DEG C, until 2/5 of extracting liquid volume, leaves standstill 3 hours;

Less than (6) 90 DEG C are continued reclaim under reduced pressure methyl alcohol to without alcohol taste, obtain digitonin crude product;

(7) be that the resin D101 of 1 times of seed weight fills post by consumption, with distillation washing 3 column volumes, slowly add the digitonin crude product obtained in step 6, described column flow rate is 3ml/kg raw material;

(8) with the distilled water of 2 times of cylinder accumulated amounts with after the flow velocity wash-out of 5ml/kg raw material, with 25% methyl alcohol of 3 times of cylinder accumulated amounts with the flow velocity wash-out of 5ml/kg raw material, afterwards, with 60% methyl alcohol of 4 times of cylinder accumulated amounts with the flow velocity wash-out of 5ml/kg raw material, collect 60% alcohol eluen, underpressure distillation, except desolventizing, obtains eluate;

(9) recrystallization is carried out with pure methyl alcohol, dry with vacuum drying oven, obtain digitonin.