CN1149584A - Preparing matrine and matrine oxide from sophora alopecuroide and its producing technology - Google Patents
Preparing matrine and matrine oxide from sophora alopecuroide and its producing technology Download PDFInfo
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Abstract
The stalks and leaves or seeds of the sophora alopecuroides are used to obtain the coarse matrine separately through the processes of crushing, leaching, solvent extracting, form inversion, precipitation, catalytic hydrogenation and water phase organic extracting. Then the product matrine is obtained through recrystallization drying. The matrine oxide product is obtained from the matrine through oxydation by hydrogen peroxide, dewatering, vacuum distilling, filtering, crystallizing, washing and drying. The above mentioned two kinds of products are the raw materials for preparing the medicines to cure the diseases of gynopathy, hepatitis B, and leucocytosis.
Description
The present invention relates to a kind of matrine with pharmaceutical value, Oxymatyine and production technique thereof from the Herba Sophorae alopecuroidis preparation.
Herba Sophorae alopecuroidis Sophora alopecuroides L. is a kind of per nnial herb that cattle and sheep do not eat on China's desert steppe, belongs to the Sophora leguminous plants, and the output of China accounts for 62% of world wide production, in China North China, northwest growth is arranged all.Its root, stem, leaf, seed contain more than 20 kind of alkaloid, especially to be called in the sophora alopecuroide alkaloid higher for its seed, wherein great majority are identical with the contained alkaloid of herbal medicine kuh-seng SophoraflavescensAit, and kuh-seng is a kind of the most ancient, one of the most frequently used Chinese medicine, it is widely used in clinical, prove not only have anticancer, press down cancer, suppress and kill various microbial processs, and immunity system, neural system, cardiovascular systems are had pharmacological action widely.Therefore since the thirties just to Herba Sophorae alopecuroidis, kuh-seng is studied, various alkaloids have therefrom been found, only did structural research at that time, and do not carry out applicating and exploitation, in recent years, the world of medicine pays much attention to the applied research of Herba Sophorae alopecuroidis both at home and abroad, active development wherein has the alkaloid of pharmaceutical use, at present verified pharmaceutical use arranged matrine matrine arranged, sophocarpine Sophocapine, sophorine Sophoridine, sophoramine Sophoramine, Oxymatyine N-oxymatrine, Cytisine N-methylcyticine, and from Herba Sophorae alopecuroidis, extract alkaloid, majority is in the in the majority of laboratory study at present, because the problem of process aspect at present can't scale production.Therefore, still can not provide and meet bitter alkali and the Oxymatyine of giving birth to of the medicine of producing medicine.
Purpose of the present invention is just in order to solve the problem of above-mentioned existence, and through doing painstaking research for many years, provide a kind of possessing skills to go up the advanced person, reasonably extract the production technique of preparation matrine, Oxymatyine economically from Herba Sophorae alopecuroidis, thereby obtain the matrine that meets pharmaceutical production of the high yield of high purity, the Oxymatyine product is for medicinal career has been started a new road again.
The objective of the invention is to realize by following technical proposal:
A kind of matrine from the Herba Sophorae alopecuroidis preparation, it is characterized in that containing in this product molecular formula is C
15H
24N
2O, structural formula is
The matrine component content more than 98%, surplus is the white needles or the granular crystal of water.
A kind of Oxymatyine from the Herba Sophorae alopecuroidis preparation, it is characterized in that containing in this product molecular formula is C
15H
24N
2O
2, structure is
The Oxymatyine component content more than 98%, surplus is white powdery or the needle-like or the granular crystal of water.
Production technique of the present invention is to be that form with salt exists according to the biology total alkali that contains in the Herba Sophorae alopecuroidis plant, when leach sophora alopecuroide or stem and the Ye Shi that pulverizes with diluted alkaline, can be converted into the alkaloid of unbound state, carry out enrichment by organic solvent extraction, and then make the transition with acid, make alkaloid go into aqueous phase from the organic phase transfer, and exist with the form of salt, when precipitating with alkali, because various alkaloid chemical property differences, wherein sophocarpine and small part matrine precipitation is separated out, and most of matrine of aqueous phase, sophorine and other alkaloid are stayed in the mother liquor of precipitation of ammonium, because sophocarpine structurally has a two key, but this pair key hydrogenation is opened, therefore, behind the sophocarpine hydrogenation, just change into matrine, and the most of matrine in the mother liquor of precipitation of ammonium, sophorine and other alkaloid optionally extract with organic extractant, making matrine be extracted the back separates again with other alkaloid with sophorine and extracts, the matrine of organic extractant phase is removed organic phase through underpressure distillation, reclaim again and reuse, obtain the matrine of solid matrine and hydrogenation conversion, merge the back and carry out recrystallization with sherwood oil, can obtain the matrine product through vacuum-drying, also can the water after transition be regulated pH value directly extract matrine with preparing matrine with production technique in the step, sophorine can reach same effect.
Matrine is after peroxidation, therefore can generate Oxymatyine, Oxymatyine of the present invention is to be raw material with the crystalline matrine, earlier with carrying out oxidizing reaction with excessive hydrogen peroxide after the water dissolution, can obtain, and excessive hydrogen peroxide heats generation oxygen G﹠W under alkaline condition, concentrates through underpressure distillation and removes most of water, remove surplus water with organic solvent azeotropic again, through filtration, recrystallization, washing, vacuum-drying obtain the Oxymatyine product.
Concrete preparation method is as described below:
A kind ofly prepare the production technique of matrine, it is characterized in that it is made up of following operation from Herba Sophorae alopecuroidis:
A) seed of selection fine Herba Sophorae alopecuroidis or stem and leaf are that material is pulverized, and its granularity is the 10-80 order, and in the container of packing into, the alkaline solution that adds 1-10% concentration leaches, and the alkaline solution consumption is the 20-30% of weight of material, extraction time 24-48 hour;
B) (a) being leached the material that finishes packs in the enamel reaction still of chuck heating, the compound or the haloalkane organic solvent that add weight of material 1-5 benzene doubly simultaneously, and stirring heating 70-120 ℃, the pump around circuit of carrying out more than at least seven sections is extracted alkaloid, each 2-6 hour pump around circuit time, lifeless matter alkali in material extracts and finishes, and its material slag tail is abandoned.Each organic solvent extraction liquid changes in the container, with 5-10% concentration consumption is that 1/2 acid solution of organic solvent extraction liquid makes the transition, transition, the back was precipitated with 30% alkali lye adjusting PH=7-9, will precipitate through centrifugation to obtain matrine and sophocarpine mixture and aqueous solution mother liquor again;
C) matrine of (b) and sophocarpine mixture are packed in the reactor,, add the metallic nickel catalyzer with less water or dissolve with ethanol, catalyst levels and sophocarpine weight ratio are 1: 5-15, seal still then,, feed 0.2-1.0Kg/cm with rare gas element argon gas or nitrogen excluding air
2The hydrogen of pressure till thin-layer chromatography does not have sophocarpine, stops hydrogenation in reactant, reaction finishes.Through centrifugation, underpressure distillation concentrates, and is solvent-free in reactant, obtains rough matrine then, reuses behind the catalyst regeneration that separation obtains;
(d) again the aqueous solution mother liquor of (b) is regulated PH=7-11 with alkali lye after, compound or haloalkane with benzene carry out extracting more than at least seven sections matrine, consumption is 0.5-1.0 a times of mother liquor, the water tail is abandoned, extracted organic phase is through vacuum distillation recovered solvent, and solid is rough matrine and (c) the rough matrine merging of item, carries out recrystallization with 5-10 sherwood oil doubly again, obtain refining matrine crystal, last vacuum-drying obtains final matrine product.
Wherein PH=7-11 is regulated with alkali lye in leach liquor back transition, compound or haloalkane with benzene carry out extracting more than at least seven sections matrine, the water tail is abandoned, extracted organic phase is through vacuum distillation recovered solvent, and solid is the mixture of rough sophocarpine, matrine, and mixture is packed into and dissolved with small amount of ethanol in the reactor, add the metallic nickel catalyzer with above-mentioned method, carry out hydrogenation reaction, till no sophocarpine, reaction finishes.Through centrifugation, underpressure distillation is concentrated into solvent-free then, obtains rough matrine, and rough matrine obtains final matrine product through recrystallization, washing, vacuum-drying.
A kind of production technique of the Oxymatyine from Herba Sophorae alopecuroidis preparation is characterized in that it is made up of the following step:
A) the purified matrine is soluble in water, the hydrogen peroxide that adds 30% concentration carries out oxidizing reaction, and the mol ratio of hydrogen peroxide consumption and matrine is 3-5: 1, until reactant till thin-layer chromatography does not have the matrine color spot;
B) regulate PH＞7 with liquid caustic soda again, and heat 30-80 ℃, the hydrogen peroxide of decomposing excessive overflows until no oxygen, and underpressure distillation concentrates and removes most of water, is incorporated as matrine weight 5-10 ethylene dichloride component distillation doubly again and removes residual moisture, filters;
C) filtrate distillation concentrate make filtrate volume be matrine weight 3-5 doubly, weight of toluene heating for dissolving such as adding again, naturally cooling occurs until the Oxymatyine crystallization, carries out the centrifugation crystallization, toluene wash twice is used in crystallization again, obtains white Oxymatyine product through vacuum-drying;
The metallic nickel catalyzer is that single nickel salt, nickelous nitrate, nickelous chloride and four kinds of any one nickel salt waters of nickelous acetate or dissolve with ethanol add the water of 1M POTASSIUM BOROHYDRIDE or sodium borohydride or the product that the ethanolic soln reaction obtains.The catalyzer that obtains is separated in the reaction back can add less water, adds the water or the ethanolic soln reaction regeneration of 1M POTASSIUM BOROHYDRIDE or sodium borohydride again, reuses; The compound of benzene be three kinds of benzene,toluene,xylenes wherein any one, haloalkane be two kinds of ethylene dichloride, trichloromethane wherein any one; Leaching alkali lye be four kinds in sodium hydroxide, potassium hydroxide, ammonium hydroxide, yellow soda ash wherein any one; The acid that diluted acid makes the transition is sulfuric acid or hydrochloric acid.
Matrine of the present invention adopts thin layer chromatography to measure.
Concrete grammar is: get hydrogenation reaction testing sample and matrine standard model and be made into 0.5% solution respectively with dehydrated alcohol, get the 10 microlitres different positions o'clock on 1% carboxymethyl cellulose, 200 order silica gel G chromatoplates respectively, with the inclination ascending method with benzene: acetone: diethylamine=mixture launched in 5: 2: 0.2, with rare Dragendorff's reagent colour developing, sophocarpine colour developing spot must not be arranged after the reduction.
Oxymatyine of the present invention adopts the thin-layer chromatography measuring method to be:
Get the oxidizing reaction testing sample, be made into 0.2% solution respectively with dehydrated alcohol with the Oxymatyine standard model, draw 20 microlitres and put different positions on chromatoplate same as described above respectively, use chloroform: methyl alcohol: diethylamine=mixture launched in 6: 4: 0.3, with rare Dragendorff's reagent colour developing, in the sample matrine spot must not be arranged after the oxidizing reaction.
The sophora alopecuroide that the present invention adopts contains biology total alkali 2.2-2.7%, and wherein matrine is 0.6-0.8%, sophocarpine 0.6-0.8%, and sophorine 0.7-0.9%, other alkaloid is below 0.1%.Stem and leaf contain biology total alkali 0.5-1.2%, and wherein matrine is 0.1-0.3%, sophocarpine 0.1-0.3%, and sophorine 0.2-0.4%, other alkaloid is below 0.05%.
Adopt production technique of the present invention, sophocarpine transforms the transformation efficiency 70-80% of matrine, and total alkaloids reclaims the rate of recovery 80-85% of matrine.
Owing to take technique scheme to make the technology of the present invention compared with the prior art have following advantage and effect.
A) product matrine, the Oxymatyine of the present invention's preparation meet the medicinal raw material of producing medicine fully, purity height, good, the inclusion-free of quality are used to prepare the medicine of multiple diseases such as leukopenia that treatment gynecopathy, hepatitis B, a variety of causes cause, diarrhoea;
B) production technique of the present invention, owing to adopt the advanced catalysis agent to carry out low-voltage hydrogenation, technical process is simplified, and reduces facility investment, improves the rate of recovery, has improved benefit.
C) make full use of the Herba Sophorae alopecuroidis natural resources, the people have broken away from poverty for Desert Area, have improved standard of living; can also accelerate simultaneously the vegetation protection of Desert Area and sand ground, check winds and fix drifting sand, improve environment; nourishing moisture, improve environment, is the immeasurable eternal lasting matter of fundamental importance of merit fringe that benefits future generations.
D) product nontoxic, have no side effect, produce the three wastes and meet national environmental standard.
Description of drawings:
Fig. 1 is preparation matrine process flow sheet;
Fig. 2 prepares the matrine process flow sheet for adopting a step neutralisation;
Fig. 3 is preparation Oxymatyine process flow sheet.
Embodiment further specifies the technology of the present invention below in conjunction with accompanying drawing:
Embodiment 1,
Prepare matrine by technical process shown in the accompanying drawing 1, select for use North China to produce sophora alopecuroide 1000Kg, contain matrine 0.8%, sophocarpine 0.8%, sophorine 0.9%, other alkaloid 0.1%, be crushed to and add 1% potassium hydroxide alkali lye 200Kg in the container of packing into behind 10 orders and leached 48 hours, the sophora alopecuroide material that then leaching is finished is packed into and is added the dimethylbenzene organic solvent simultaneously in the enamel reaction still of chuck heating, and its consumption is 1000Kg, be heated with stirring to 80-90 ℃, begin to carry out the solvent refluxing circulation and extract alkaloid, each return time 2 hours is through 10 reflux cycle, lifeless matter alkali afterreaction finishes in the material, and sophora alopecuroide slag tail is abandoned.Gained solvent extraction liquid makes the transition with 10% hydrochloric acid, the dilute hydrochloric acid consumption is 500Kg, transition, the back transferred pH value=7 to precipitate with 30% concentration liquid caustic soda, emit precipitation, precipitation obtains matrine and sophorine mixture 9.8Kg and aqueous solution mother liquor 500Kg through centrifugation, mixture is packed in the still again, dissolves with small amount of ethanol, add metallic nickel catalyzer 0.5Kg, catalyzer is taken from by the product of 1Kg single nickel salt water 10Kg dissolving back with the POTASSIUM BOROHYDRIDE reactant aqueous solution of 1M.Seal still then, logical nitrogen exhausted air feeds 0.2Kg/cm
2The hydrogen of pressure till thin-layer chromatography is measured no sophocarpine, stops hydrogenation in reactant, reaction finishes.Carry out centrifugation again, underpressure distillation concentrates, make in the reactant solvent-free, obtain rough matrine 9.8Kg, reuse behind the isolating catalyst regeneration, obtained aqueous solution mother liquor 500Kg transfers pH value=7 with 30% sodium hydroxide, stirring extraction water tail after seven sections extractions with xylene solvent 200Kg abandons, extracted organic phase is through vacuum distillation recovered solvent, solid is that rough matrine 5.1Kg and aforesaid rough matrine merge 14.9Kg altogether, carries out recrystallization with the 75Kg sherwood oil again, the refining matrine crystal that obtains, last vacuum-drying, be matrine product 11.98Kg of the present invention, matrine content is 98.6%, water 1.4%, sophocarpine transformation efficiency 90%, the rate of recovery 84.5% of recovery matrine from biology total alkali.
Embodiment 2,
Extract matrine by technical process shown in Figure 2, select for use the northwest to produce sophora alopecuroide 1000Kg, contain matrine 0.65%, sophocarpine 0.7%, sophorine 0.75%, other alkaloid 0.1% is pulverized 40 orders, add 5% sodium hydroxide solution 250Kg and leach after 36 hours, the sophora alopecuroide material that then leaching is finished is packed in the enamel still of chuck heating, adds ethylene dichloride solvent 1500Kg simultaneously, be heated with stirring to 110-120 ℃ of temperature examination, begin to carry out solvent refluxing circulation and extract alkaloid, each 4 hours time is through after 8 reflux cycle, make lifeless matter alkali reaction end in the material, sophora alopecuroide slag tail is abandoned.Gained solvent extraction liquid makes the transition with 10% sulphuric acid soln 500Kg, transition, pH value=8 were transferred with 30% concentration liquid caustic soda potassium hydroxide in the back, use ethylene dichloride 250Kg, carry out cycling extraction 8 times, the water tail is abandoned, organic phase is through underpressure distillation, solvent recycled is used, the rough matrine of the solid that obtains, sophocarpine mixture, again this material is packed into and use water dissolution in the still, the nickel salt that adding nickel catalyzator 0.7Kg takes from by nickelous nitrate is the product of the POTASSIUM BOROHYDRIDE ethanolic soln reaction of 1.4Kg adapted water 12Kg dissolving back and 1M, seals still then.Use the argon gas excluding air, feed 0.6Kg/cm
2The hydrogen of pressure does not have sophocarpine until reactant, stops hydrogenation reaction and finishes.Carry out centrifugation, underpressure distillation concentrates, and is solvent-free to the reactant, obtains rough matrine, returns use behind the isolating catalyst regeneration, and rough matrine 13Kg with 130Kg sherwood oil recrystallization, obtains matrine 11.5Kg of the present invention after the vacuum-drying.Matrine content 98.7%, moisture 1.3%, sophocarpine turnover ratio 85%, the matrine rate of recovery 80% from total alkaloids.
Embodiment 3:
Press accompanying drawing 1, technical process shown in 3 prepares matrine and Oxymatyine, stem and the leaf of selecting for use the northwest to produce Herba Sophorae alopecuroidis are raw material 1000Kg, contain matrine 0.2%, sophocarpine 0.15%, sophorine 0.3%, other alkaloid 0.05% is crushed in the container of packing into behind 80 orders, adding 10% ammonium hydroxide alkali lye 300Kg leached 24 hours, stem that leaching is finished and leaf material are packed into and are added the trichloromethane organic solvent simultaneously in the enamel reaction still of chuck heating then, its consumption is 2000Kg, begin to be heated with stirring to 70-80 ℃, carry out the solvent refluxing circulation and extract alkaloid, each return time 6 hours.Through 7 sections reflux cycle, lifeless matter alkali afterreaction finishes in the material.Stem and leaf slag tail are abandoned, gained solvent extraction liquid makes the transition with 5% sulfuric acid, the dilute sulphuric acid consumption is 500Kg, transition, the back transferred pH value=9 to precipitate with 30% concentration liquid caustic soda, emit precipitation, precipitation obtains matrine and sophorine mixture 2.1Kg and aqueous solution mother liquor 500Kg through centrifugation, again mixed biologic alkali is packed in the still, dissolve with small amount of ethanol, add metallic nickel catalyzer 0.1Kg, catalyzer take from by behind the 0.5Kg nickelous acetate water 6Kg dissolve with ethanol with the product of the ethanol solution of sodium borohydride reaction of 1M.Seal still then, logical nitrogen exhausted air feeds 1.0Kg/cm
2The hydrogen of pressure till thin-layer chromatography is measured no sophocarpine, stops hydrogenation in reactant, reaction finishes.Carry out centrifugation again, underpressure distillation concentrates, and makes in the reactant solvent-freely, obtains rough matrine 2.1Kg, reuses behind the isolating catalyst regeneration.Obtained aqueous solution mother liquor 500Kg transfers pH value=11 with 30% sodium hydroxide, 300Kg stirs extraction with the trichloromethane solvent, the water tail is abandoned after eight sections extractions, and extracted organic phase is through vacuum distillation recovered solvent, and solid is that rough matrine 1.2Kg and aforesaid rough matrine merge 3.3Kg altogether.Carry out recrystallization with the 33Kg sherwood oil again, obtain refining matrine crystal, last vacuum-drying, be matrine product 2.64Kg of the present invention, matrine content is 98%, water 2%, sophocarpine transformation efficiency 70%, the rate of recovery 85% of recovery matrine from biology total alkali.
The matrine crystal 10Kg for preparing undried as stated above, the preparation Oxymatyine.
It is soluble in water to get matrine earlier, the hydrogen peroxide 30Kg that adds 30% concentration, carry out oxidizing reaction, till thin-layer chromatography does not have the matrine color spot, regulate PH＞7 with liquid caustic soda until reactant again, and heat 30-40 ℃, the hydrogen peroxide of decomposing excessive overflows until no oxygen, underpressure distillation concentrates and removes most of water, adds ethylene dichloride 50Kg component distillation again and removes residual moisture, filters; Filtrate is concentrated into 30Kg, adds 30 kilograms of toluene again and adds dissolving, and naturally cooling occurs until the Oxymatyine crystallization.Toluene wash twice is used in the centrifugation crystallization again, through vacuum-drying, obtains white Oxymatyine 8.4Kg, and product contains Oxymatyine 98.7%.
Embodiment 4:
It is soluble in water to get the 10Kg matrine earlier, adds the hydrogen peroxide 40Kg of 30% concentration, carries out oxidizing reaction, until reactant till thin-layer chromatography does not have the matrine color spot.Regulate PH＞7 with liquid caustic soda again, and heat 50-60 ℃, the hydrogen peroxide of decomposing excessive overflows until no oxygen.Underpressure distillation concentrates and removes most of water, adds ethylene dichloride 80Kg component distillation again and removes residual moisture, filters; Filtrate is concentrated into 40Kg, adds 40 liter toluene heat again and adds dissolving, and naturally cooling occurs until the Oxymatyine crystallization, and the centrifugation crystallization with toluene wash twice, through vacuum-drying, obtains white Oxymatyine 8.0Kg, and product contains Oxymatyine 98.2%.
Embodiment 5:
It is soluble in water to get the 10Kg matrine earlier, adds the hydrogen peroxide 50Kg of 30% concentration, carries out oxidizing reaction, until reactant till thin-layer chromatography does not have the matrine color spot, regulate PH＞7 with liquid caustic soda again, and heat 70-80 ℃, the hydrogen peroxide of decomposing excessive overflows until no oxygen.Underpressure distillation concentrates removes most of water, add ethylene dichloride 100Kg component distillation again and remove residual moisture, filter, filtrate is concentrated into 50Kg, adds 50 liter toluene again and adds dissolving, naturally cooling occurs until the Oxymatyine crystallization, the centrifugation crystallization is with toluene wash twice, through vacuum-drying, obtain white Oxymatyine 8.0Kg, product contains Oxymatyine 98.1%.
Claims (9)
1, a kind of matrine from the Herba Sophorae alopecuroidis preparation, it is characterized in that containing in this product molecular formula is C
15H
24N
2O, structural formula is
The matrine component content more than 98%, surplus is the white needles or the granular crystal of water.
2, a kind of Oxymatyine from the Herba Sophorae alopecuroidis preparation, it is characterized in that containing in this product molecular formula is C
15H
24N
2O
2, structure is
The Oxymatyine component content more than 98%, surplus is white powdery or the needle-like or the granular crystal of water.
3, a kind ofly prepare the production technique of matrine, it is characterized in that it is made up of following operation from Herba Sophorae alopecuroidis:
A) seed of selection fine Herba Sophorae alopecuroidis or stem and leaf are that material is pulverized, and its granularity is the 10-80 order, and in the container of packing into, the alkaline solution that adds 1-10% concentration leaches, and the alkaline solution consumption is the 20-30% of weight of material, extraction time 24-48 hour;
B) (a) being leached the material that finishes packs in the enamel reaction still of chuck heating, the compound or the haloalkane organic solvent that add weight of material 1-5 benzene doubly simultaneously, and stirring heating 70-120 ℃, the pump around circuit of carrying out more than at least seven sections is extracted alkaloid, each 2-6 hour pump around circuit time, lifeless matter alkali in material, extract and finish, its material slag tail is abandoned, each organic solvent extraction liquid changes in the container, with 5-10% concentration consumption is that 1/2 acid solution of organic solvent extraction liquid makes the transition, and the back was regulated PH=7-9 with 30% alkali lye and precipitated transition, will precipitate the process centrifugation again and obtain matrine and sophocarpine mixture and aqueous solution mother liquor;
C) matrine of (b) and sophocarpine mixture are packed in the reactor,, add the metallic nickel catalyzer with less water or dissolve with ethanol, catalyst levels and sophocarpine weight ratio are 1: 5-15, seal still then,, feed 0.2-1.0Kg/cm with rare gas element argon gas or nitrogen excluding air
2The hydrogen of pressure till no sophocarpine behind the thin-layer chromatography, stops hydrogenation in reactant, reaction finishes.Through centrifugation, underpressure distillation concentrates, and is solvent-free in reactant, obtains rough matrine then, reuses behind the catalyst regeneration that separation obtains;
(d) again the aqueous solution mother liquor of (b) is regulated PH=7-11 with alkali lye after, compound or haloalkane with benzene carry out extracting more than at least seven sections matrine, consumption is 0.5-1.0 a times of mother liquor, the water tail is abandoned, extracted organic phase is through vacuum distillation recovered solvent, and solid is rough matrine and (c) the rough matrine merging of item, carries out recrystallization with 5-10 sherwood oil doubly again, obtain refining matrine crystal, last vacuum-drying obtains final matrine product.
4, production technique according to claim 3, it is characterized in that regulating PH=7-11 with alkali lye after leach liquor makes the transition, compound or haloalkane with benzene carry out extracting more than at least seven sections matrine, the water tail is abandoned, extracted organic phase is through vacuum distillation recovered solvent, solid is rough sophocarpine, the mixture of matrine, mixture is packed in the reactor with less water or dissolve with ethanol, adds the metallic nickel catalyzer with above-mentioned method, carries out hydrogenation reaction, till no sophocarpine, reaction finishes, and then through centrifugation, underpressure distillation is concentrated into solvent-free, obtain rough matrine, rough matrine is through recrystallization, washing, vacuum-drying obtains final matrine product.
5, a kind ofly prepare the production technique of Oxymatyine, it is characterized in that it is made up of following operation from Herba Sophorae alopecuroidis:
A) purified crystallization matrine is soluble in water, the hydrogen peroxide that adds 30% concentration carries out oxidizing reaction, and the mol ratio of hydrogen peroxide consumption and matrine is 3-5: 1, until reactant till thin-layer chromatography does not have the matrine color spot;
B) regulate PH＞7 with liquid caustic soda again, and heat 30-80 ℃, the hydrogen peroxide of decomposing excessive overflows until no oxygen, and underpressure distillation concentrates and removes most of water, is incorporated as matrine weight 5-10 ethylene dichloride component distillation doubly again and removes residual moisture, filters;
C) filtrate distillation concentrate make filtrate volume be matrine weight 3-5 doubly, the toluene heating for dissolving of weight such as add again, naturally cooling occurs until the Oxymatyine crystallization, carry out the centrifugation crystallization, toluene wash twice is used in crystallization again, obtains white Oxymatyine product through vacuum-drying
6,, it is characterized in that the metallic nickel catalyzer is that single nickel salt, nickelous nitrate, nickelous chloride and four kinds of any one nickel salt waters of nickelous acetate or dissolve with ethanol add the water of 1M POTASSIUM BOROHYDRIDE or sodium borohydride or the product that the ethanolic soln reaction obtains according to claim 3,4 described production technique.The catalyzer that obtains is separated in the reaction back can add less water, adds the water or the ethanolic soln reaction regeneration of 1M POTASSIUM BOROHYDRIDE or sodium borohydride again, reuses.
7, according to claim 3,4 described production technique it is characterized in that the compound of benzene be three kinds of benzene,toluene,xylenes wherein any one, haloalkane be two kinds of ethylene dichloride, trichloromethane wherein any one.
8, according to claim 3,4 described production technique, it is characterized in that leaching alkali lye and be four kinds in sodium hydroxide, potassium hydroxide, ammonium hydroxide, yellow soda ash wherein any one.
9,, it is characterized in that the acid that diluted acid makes the transition is sulfuric acid or hydrochloric acid according to claim 3,4 described production technique.
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| CN96109730A CN1044475C (en) | 1996-09-10 | 1996-09-10 | Preparing matrine and matrine oxide from sophora alopecuroide and its producing technology |
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| CNB991091876A Division CN1148370C (en) | 1999-06-22 | 1999-06-22 | Process for preparing oxymatrine from sophora alopecuroide |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1111533C (en) * | 2000-11-18 | 2003-06-18 | 宁夏药物研究所 | The preparation technology of Oxymatyine |
| CN1119347C (en) * | 2000-06-19 | 2003-08-27 | 宁夏药物研究所（有限公司） | Preparation of matrine from foxtail-like sophora seed |
| CN1325495C (en) * | 2000-11-18 | 2007-07-11 | 宁夏药物研究所（有限公司） | Preparation process of sophoridine |
| CN1325496C (en) * | 2000-11-18 | 2007-07-11 | 宁夏药物研究所（有限公司） | Preparation process of sophora alopecuroides series alkaloid salts substances |
| CN101130541B (en) * | 2007-09-11 | 2010-09-29 | 重庆大学 | Method for extracting and separating matrine and oxymatrine from trialkyl phosphine oxide inverse micellar solution |
| CN102633798A (en) * | 2012-04-26 | 2012-08-15 | 宁夏紫荆花制药有限公司 | Method for preparing high-purity matrine from sophora alopecuroides |
| CN102786523A (en) * | 2012-07-19 | 2012-11-21 | 宁夏紫荆花制药有限公司 | Technology for preparing sophocarpine from Sophora alopecuroides L |
| CN102850352A (en) * | 2012-07-26 | 2013-01-02 | 宁夏紫荆花制药有限公司 | Preparation method high-purity high-yield oxysophocarpine |
| CN102875552A (en) * | 2012-10-12 | 2013-01-16 | 塔里木大学 | Composite solvent for efficiently extracting alkaloids |
| CN112047946A (en) * | 2020-09-08 | 2020-12-08 | 北方民族大学 | A method for preparing matrine from oxymatrine by transfer hydrogenation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1030078C (en) * | 1991-12-23 | 1995-10-18 | 傅维芳 | Freezing vacuum extracting method for matrine |
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1996
- 1996-09-10 CN CN96109730A patent/CN1044475C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1119347C (en) * | 2000-06-19 | 2003-08-27 | 宁夏药物研究所（有限公司） | Preparation of matrine from foxtail-like sophora seed |
| CN1111533C (en) * | 2000-11-18 | 2003-06-18 | 宁夏药物研究所 | The preparation technology of Oxymatyine |
| CN1325495C (en) * | 2000-11-18 | 2007-07-11 | 宁夏药物研究所（有限公司） | Preparation process of sophoridine |
| CN1325496C (en) * | 2000-11-18 | 2007-07-11 | 宁夏药物研究所（有限公司） | Preparation process of sophora alopecuroides series alkaloid salts substances |
| CN101130541B (en) * | 2007-09-11 | 2010-09-29 | 重庆大学 | Method for extracting and separating matrine and oxymatrine from trialkyl phosphine oxide inverse micellar solution |
| CN102633798A (en) * | 2012-04-26 | 2012-08-15 | 宁夏紫荆花制药有限公司 | Method for preparing high-purity matrine from sophora alopecuroides |
| CN102786523A (en) * | 2012-07-19 | 2012-11-21 | 宁夏紫荆花制药有限公司 | Technology for preparing sophocarpine from Sophora alopecuroides L |
| CN102850352A (en) * | 2012-07-26 | 2013-01-02 | 宁夏紫荆花制药有限公司 | Preparation method high-purity high-yield oxysophocarpine |
| CN102875552A (en) * | 2012-10-12 | 2013-01-16 | 塔里木大学 | Composite solvent for efficiently extracting alkaloids |
| CN112047946A (en) * | 2020-09-08 | 2020-12-08 | 北方民族大学 | A method for preparing matrine from oxymatrine by transfer hydrogenation |
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