CN104327153A - Method for extracting limonin analogues from tangerine seeds - Google Patents

Abstract

The invention discloses a method for extracting limonin analogues from tangerine seeds. The method comprises the following steps: firstly, obtaining raw materials, wherein the raw materials are subjected to ultrasonic extraction with 90% ethanol for 1 hour to obtain an extract, the extract is directly detected, the content of limonin is required to be equal to or greater than 0.6% and the content of nomilin is equal to or greater than 0.3%; secondly, breaking hulls of the raw materials and pulverizing until the hulls of the raw materials are completely broken; thirdly, extracting the raw materials with 90% ethanol for three times and 1.5 hours each time and ultimately controlling that the active ingredients in the residue account for no more than 3% of the raw material total target, wherein the ratio of material to solvent is 1 to 4 to 4 to 3; fourthly, concentrating the extract until the degree of alcohol is 20%, standing for 12 hours and removing floating oil on the surface of the liquid; fifthly, continuously recovering the solvent from a concentrated solution, controlling the extraction specific gravity to be 1.03+/-0.1, standing and crystallizing for 12 hours; sixthly, extracting an upper layer supernatant, filtering the lower layer precipitate with filter cloth and centrifuging; and seventhly, after centrifuging, carrying out coarse crystallization and vacuum drying at a temperature of less than 80 DEG C.

Description

A kind of method extracting limonoids from tangerine core

Technical field

The invention belongs to natural drug extractive technique field, be specifically related to tangerine core as raw material, methyl alcohol circumfluence distillation, extracting solution removal of impurities process, extracting solution is adopted to concentrate specific gravity and separate out coarse crystallization, after degreasing is separated, obtain limonoids crude product, then obacalactone fine work can be obtained through recrystallization.

 

Background technology

Limonoids (Limlclis) is present in the class triterpenoid in Rutaceae (Rutaceae) and Meliaceae (Meliacace) plant.Recent study shows that obacalactone can swash in vivo main detoxication enzyme---the activity of Thiadiazolidine isomerase (GSH-transferase) strongly like thing, a large amount of experimentation on animals shows, limonoid has the cancer such as liver cancer, carcinoma of small intestine, oral carcinoma suppressing to be caused by chemical substance, is the physiologically active substance that a class Development volue is very high.

Extractive technique is the basis of researches on natural drugs work, the extraction raw material of limonoids is a lot, with Rutaceae citrus plant medicinal materials such as the dried immature fruit of citron orange, dried orange peel, tangerine seed, shaddock cores for raw material, the separation and purification of equal energy go out limonoids, but more difficult obacalactone (Limonin), the Nomilin (Nomilin) isolating high-content, further separation and purification research work is carried out less.The product of specification needed for market lacks, be badly in need of exploitation a kind of can rapidly and efficiently, clean cut separation purifying, extract the high limonoids technique of content.

Summary of the invention

Technical problem to be solved by this invention is as the exploitation of tangerine core provide a new way, to reduce raw-material waste, decrease environmental pollution, provide a kind of high efficiency extraction to be separated the technique of obacalactone, Nomilin composition in limonoids.

It is as follows that the present invention solves the problems of the technologies described above taked technical scheme:

From tangerine core, extract a method for limonoids, comprising:

Step one: obtain raw material, wherein, material content detects and adopts ultrasonic method 90% extraction using alcohol 1 hour, extracting solution direct-detection, and this material content requires obacalactone (Limonin) >=0.6%, Nomilin (Nomilin) >=0.3%;

Step 2: carry out broken shell pulverization process to raw material, requires the complete broken shell of raw material;

Step 3: raw material carries out 90% extraction using alcohol three times, each 1.5 hours, solid-liquid ratio 1:4:4:3, and final control effective ingredient in slag account for raw material general objective thing must not higher than 3%;

Step 4: extracting solution is concentrated into alcoholic degree 20% and leaves standstill 12 hours, the surperficial oil slick of liquid of going out;

Step 5: concentrated solution continues recycling design, goes out cream specific gravity control 1.03 ± 0.1;

Step 6: extract upper strata clear cream, lower sediment filter-cloth filtering, centrifugal;

Step 7: centrifugal coarse crystallization vacuum-drying, temperature is less than 80 degrees Celsius;

Step 8: coarse crystallization 5 times amount boiling range 60-90 degree sherwood oil takes off ester twice, and skimming processes fully grinds stirring, avoids apparatus sharp impacts in operating process;

Step 9: coarse crystallization is activated carbon decolorizing recrystallization under EtOH-EtOAc system;

Step 10: vacuum filtration crystallization, temperature is less than 80 degrees Celsius of vacuum-dryings, finally obtains obacalactone product.

After this invention takes aforesaid method, can reduce fully raw-material waste, decrease environmental pollution, it is a kind of method that high efficiency extraction is separated obacalactone, Nomilin composition in limonoids, has good technique effect.

Other features and advantages of the present invention will be set forth in the following description, and, partly become apparent from specification sheets, or understand by implementing the present invention.Object of the present invention and other advantages realize by structure specifically noted in write specification sheets, claims and accompanying drawing and obtain.

Accompanying drawing explanation

Below in conjunction with accompanying drawing, the present invention is described in detail, to make above-mentioned advantage of the present invention definitely.Wherein,

Fig. 1 is a kind of schematic diagram extracting the method for limonoids from tangerine core of the present invention;

Fig. 2 is a kind of schematic flow sheet extracting the method for limonoids from tangerine core of the present invention.

 

Embodiment

Describe embodiments of the present invention in detail below with reference to drawings and Examples, to the present invention, how utilisation technology means solve technical problem whereby, and the implementation procedure reaching technique effect can fully understand and implement according to this.It should be noted that, only otherwise form conflict, each embodiment in the present invention and each feature in each embodiment can be combined with each other, and the technical scheme formed is all within protection scope of the present invention.

Specifically, as shown in Figure 1, 2, a kind of method extracting limonoids from tangerine core, comprising:

Step one: obtain raw material, wherein, material content detects and adopts ultrasonic method 90% extraction using alcohol 1 hour, extracting solution direct-detection, and this material content requires obacalactone (Limonin) >=0.6%, Nomilin (Nomilin) >=0.3%;

Step 2: carry out broken shell pulverization process to raw material, requires the complete broken shell of raw material;

Step 3: raw material carries out 90% extraction using alcohol three times, each 1.5 hours, solid-liquid ratio 1:4:4:3, and final control effective ingredient in slag account for raw material general objective thing must not higher than 3%;

Step 4: extracting solution is concentrated into alcoholic degree 20% and leaves standstill 12 hours, the surperficial oil slick of liquid of going out;

Step 5: concentrated solution continues recycling design, goes out cream specific gravity control 1.03 ± 0.1;

Step 6: extract upper strata clear cream, lower sediment filter-cloth filtering, centrifugal;

Step 7: centrifugal coarse crystallization vacuum-drying, temperature is less than 80 degrees Celsius;

Step 8: coarse crystallization 5 times amount boiling range 60-90 degree sherwood oil takes off ester twice, and skimming processes fully grinds stirring, avoids apparatus sharp impacts in operating process;

Step 9: coarse crystallization is activated carbon decolorizing recrystallization under EtOH-EtOAc system;

Step 10: vacuum filtration crystallization, temperature is less than 80 degrees Celsius of vacuum-dryings, finally obtains obacalactone product.

In step 10, obtain the obacalactone product of 98%.

That is, as shown in Figure 2, in one embodiment, solve the problems of the technologies described above taked technical scheme to be made up of following step:

Raw materials quality standard, material content detects and adopts ultrasonic method 90% extraction using alcohol 1 hour, material content require obacalactone (Limonin), >=0.6%, Nomilin (Nomilin) >=0.3%

Raw material pulverizing require broken shell, extract slag sample, 90% methanol extraction 1 time, 1.5 hours, in slag effective ingredient account for raw material general objective thing must not higher than 3%;

Extracting solution goes out cream proportion and is strict controlled in 1.03 ± 0.1, and the less throw out of proportion is separated out not exclusively, and proportion is excessive, and throw out is difficult to be separated;

Throw out takes off ester process and fully grinds stirring, operates in the molten device of plastics, forbids apparatus sharp impacts in operating process;

Major product shines naturally extremely without sherwood oil taste, then puts vacuum drying oven drying, temperature≤80 DEG C;

After this invention takes aforesaid method, can reduce fully raw-material waste, decrease environmental pollution, it is a kind of method that high efficiency extraction is separated obacalactone, Nomilin composition in limonoids, has good technique effect.

In order to determine optimised process step of the present invention, inventors performed a large amount of experimental study work, specific experiment situation is as follows:

1, the degree extracting methyl alcohol is groped

Tangerine nuclear raw material adopts alcoholic degree to be 70%, 80% respectively, 90%, 98% methyl alcohol circumfluence distillation, determines that extracting link is 90% methyl alcohol circumfluence distillation 1.5 hours, 3 times.

2, extract concentrated proportion to grope

Extracting solution concentrates alcoholic degree or proportion 80%, 40%, 20%, 0%, 1.02%, 1.05%, 1.10%.According to this experiment, it is 1.02-1.05mg/ml that extracting solution concentrates proportion, is best coarse crystallization condition.

3, coarse crystallization process is groped

Coarse crystallization convection drying state is poor has a large amount of oily matter because of throw out surface, therefore does following skimming treatment process.Finally determine that degreasing scheme is that pelleting centrifugation dries, the direct degreasing of 60-90 sherwood oil, sherwood oil consumption is precipitation capacity about 5 times.Product limonin content 50%-60%, Nomilin 20%-25%, product yield 1.2-1.5% after degreasing.

4, crystallization condition is groped

According to obacalactone and Nomilin polarity difference, utilize opposed polarity solvent to be separated with Nomilin obacalactone, result is as follows, adopts dehydrated alcohol to add 5% needle-use activated carbon and refluxes 1 hour, 2 times, after the crystallization of alcohol liquid, obtain crystal (obacalactone 2.16% Nomilin 95.82%); Alcohol reflux insolubles ethyl acetate backflow extracts 2 times, and acetic acid ethyl acetate extract crystallization obtains (obacalactone 102.84% Nomilin 1.02%), obtains (obacalactone 68.14% Nomilin 28.46%) in mother liquor.

After this invention takes aforesaid method, can reduce fully raw-material waste, decrease environmental pollution, it is a kind of method that high efficiency extraction is separated obacalactone, Nomilin composition in limonoids, has good technique effect.

Last it is noted that the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment to invention has been detailed description, for a person skilled in the art, it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (2)

1. from tangerine core, extract a method for limonoids, comprising:

Step one: obtain raw material, wherein, material content detects and adopts ultrasonic method 90% extraction using alcohol 1 hour, extracting solution direct-detection, and this material content requires obacalactone (Limonin) >=0.6%, Nomilin (Nomilin) >=0.3%;

Step 2: carry out broken shell pulverization process to raw material, requires the complete broken shell of raw material;

Step 3: raw material carries out 90% extraction using alcohol three times, each 1.5 hours, solid-liquid ratio 1:4:4:3, and final control effective ingredient in slag account for raw material general objective thing must not higher than 3%;

Step 4: extracting solution is concentrated into alcoholic degree 20% and leaves standstill 12 hours, the surperficial oil slick of liquid of going out;

Step 5: concentrated solution continues recycling design, goes out cream specific gravity control 1.03 ± 0.1;

Step 6: extract upper strata clear cream, lower sediment filter-cloth filtering, centrifugal;

Step 7: centrifugal coarse crystallization vacuum-drying, temperature is less than 80 degrees Celsius;

Step 8: coarse crystallization 5 times amount boiling range 60-90 degree sherwood oil takes off ester twice, and skimming processes fully grinds stirring, avoids apparatus sharp impacts in operating process;

Step 9: coarse crystallization is activated carbon decolorizing recrystallization under EtOH-EtOAc system;

Step 10: vacuum filtration crystallization, temperature is less than 80 degrees Celsius of vacuum-dryings, finally obtains obacalactone product.

2. the method extracting limonoids from tangerine core according to claim 1, is characterized in that, in step 10, obtains the obacalactone product of 98%.