CN106083801A - A kind of preparation method of 3,5 pairs of (methylol) 6 methoxyl group 1H different .alpha.-5:6-benzopyran 1 ketone - Google Patents
A kind of preparation method of 3,5 pairs of (methylol) 6 methoxyl group 1H different .alpha.-5:6-benzopyran 1 ketone Download PDFInfo
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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
- C07D311/76—Benzo[c]pyrans
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
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- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
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Abstract
The invention discloses the preparation method of a kind of 3,5 pairs of (methylol) 6 methoxyl group 1H different .alpha.-5:6-benzopyran 1 ketone, belong to technical field of phytochemistry.First Nicotiana tabacum L. Herb ultrasound wave is carried out supersound extraction, then use CO2Supercritical extraction extracts, obtain isocoumarin compounds, isocoumarin compounds organic acid is modified, liquid nitrogen cooling, some isocoumarin compounds are made to form precipitation, filtrate is modified with organic base again, liquid nitrogen cooling, some isocoumarin compounds are made to form precipitation again, by solution by liquid nitrogen gradient cooling, produce precipitation, until being precipitated as 3, 5 pairs (methylol) 6 methoxyl group 1H different .alpha.-5:6-benzopyran 1 ketone, then recrystallization is passed through, it is dried to obtain 3, 5 pairs (methylol) 6 methoxyl group 1H different .alpha.-5:6-benzopyran 1 ketone, extraction process is made to become simple, extraction ratio increases, extraction time more common extracting method decreases 24～26h, the more conventional extracting method of purity of product adds 20%～30%.
Description
Technical field
The invention discloses a kind of 3, the preparation method of double (the methylol)-6-methoxyl group-1H-different .alpha.-5:6-benzopyran-1-ketone of 5-,
Belong to technical field of phytochemistry.
Background technology
Nicotiana tabacum L. is the plant that chemical composition is the most complicated in the world, and secondary metabolite is the abundantest, according to nineteen eighty-two Dube
Reporting with Green etc., the chemical composition identified in Nicotiana tabacum L. is just more than 2549 kinds, by 2008, Rodgman and perfetti
Report, in Nicotiana tabacum L., tobacco and cigarette smoke find compound sum be about 8700 kinds.At present, people
The monomer chemistries material identifying out from Nicotiana tabacum L. is just more than kind more than 3000, and also has many compositions not yet to identify out.Cigarette
Grass, in addition to being mainly used in cigarette smoking purposes, also can therefrom extract the multiple chemical composition having value, therefrom be found to have out
Send out the guiding compound of value.
Isocoumarin is the basic structure of some natural products, is distributed widely in nature, and of a great variety, people once used
This compounds is synthesized by multiple method.Find that its derivant has antibacterial, antiinflammatory, anticancer, suppression the most recently
The physiology such as protease and weeding and biological activity.Owing to there being obvious active anticancer, more active to the research of this compounds.For
Study the structure activity relationship of this compounds, find cancer therapy drug people with practical value and this compounds has also been carried out greatly
The bioactivity research of amount.For in frequently seen plants about the extraction of isocoumarin compounds, traditional method use backflow,
Percolations etc., these methods are required for ethanol or organic solvent extraction, then carry out follow-up technical study, when its shortcoming is to extract
Between longer, technique is loaded down with trivial details and purity is low.The patent application document of Application No. 201410603525 discloses a kind of an unusually sweet smell bean
The extracting method of chlorins compound, is with Nicotiana tabacum L. Herb as raw material, divides through extractum extraction, silica gel column chromatography, high pressure liquid chromatography
From step, the method needs to use multiple organic solvent extraction, and, the loaded down with trivial details purity of technique is low, therefore, finds one efficiently
The extracting method of isocoumarin compounds is necessary.
Summary of the invention
The technical problem that present invention mainly solves: for current 3, double (the methylol)-6-methoxyl group-1H-different benzo pyrrole of 5-
Mutter preparation method time of-1-ketone is long, the problem that technique is loaded down with trivial details and purity is low, it is provided that double (the methylol)-6-first of a kind of 3,5-
The extracting method of Oxy-1 H-different .alpha.-5:6-benzopyran-1-ketone, first carries out supersound extraction by Nicotiana tabacum L. Herb ultrasound wave, then will carry
After taking liquid removing insoluble matter, continue to use CO2Supercritical extraction extracts, and obtains isocoumarin compounds, by isocoumarin
Compounds organic acid is modified, and passes through liquid nitrogen cooling so that it is in some isocoumarin compounds formed precipitation, mistake
Filter, filtrate is modified with tetraethyl ammonium hydroxide again, passes through liquid nitrogen cooling so that it is in some isocoumarin compounds
Forming precipitation, start be cooled to-70 DEG C with 20 DEG C for falling temperature gradient from-20 DEG C by liquid nitrogen by solution, each cooling all can obtain
To precipitation, solution is formed sediment and continues cooling, until produce is precipitated as 3, double (the methylol)-6-methoxyl group-1H-different benzo pyrrole of 5-
Mutter-1-ketone, then by recrystallization, be dried to obtain 3, double (the methylol)-6-methoxyl group-1H-different .alpha.-5:6-benzopyran-1-ketone of 5-, this
Ultrasound wave and CO are used in invention2Supercritical extraction is collaborative to be extracted so that extraction process becomes simple, and extraction ratio increases, and carries
The time that takes more common extracting method decreases 24～26h, and the present invention is suitable for commercial production, the highest to equipment requirements, produces
The more conventional extracting method of purity of product adds 20%～30%.
In order to solve above-mentioned technical problem, the technical solution adopted in the present invention is:
(1) take dry Nicotiana tabacum L. Herb, smash with disintegrating machine, sieve, obtain 100～200 mesh powder, weigh 100～200g powder
Put in flask, add 600～700mL dehydrated alcohol, be placed on 3000～3200W ultrasonic extracting machines, supersound extraction 30
～40min, filter, obtain filtrate, filtrate is carried out decompression distillation, is concentrated into the 1/4 of filtrate volume, stand, filter, remove precipitation
Thing, again carries out filtrate decompression distillation, obtains extractum a；
(2) above-mentioned extractum a is placed in CO2In supercritical extraction instrument, adding 600～700mL dehydrated alcohol, controlling extracting pressure is
25～30MPa, extraction temperature is 50～60 DEG C, CO2Flow be 20～25kg/h, extract 2～3h, obtain isocoumarin class
Compound；
(3) above-mentioned isocoumarin compounds solution is joined fill in single port flask, in flask, add 3～5g Malaysias
Acid, stirring reaction 1～2h, by 1.0～1.2L liquid nitrogen sprayings to flask, make flask temperature be down to-110～-90 DEG C, filter,
Obtain filtrate, naturally cool to room temperature, filtrate is placed in two mouthfuls of flasks with thermometer, in flask, add 6～8g tetrems
Base ammonium hydroxide, stirring reaction 2～3h, by 0.8～1.0L liquid nitrogen spraying to flask, make flask temperature be down to-90～-80
DEG C, filter, obtain filtering residue；
(4) above-mentioned filtering residue is placed in beaker, in beaker, adds 300～400mL dehydrated alcohol, by 0.1～0.3L liquid nitrogen spray
Pour on beaker, make beaker temperature be down to-30～-20 DEG C, stir 10～20min, filter, obtain filtrate, by filtrate with 0.4～
0.6L liquid nitrogen spraying, makes solution temperature be down to-50～-40 DEG C, filters, obtain filtrate, by filtrate with 0.6～0.8L liquid nitrogen spraying,
Make filtrate temperature be down to-70～-60 DEG C, filter, obtain filtering residue, double (the methylol)-6-methoxyl group-1H-different benzo pyrrole of i.e. 3,5-
Mutter-1-ketone；
(5) by above-mentioned 3, double (the methylol)-6-methoxyl group-1H-different .alpha.-5:6-benzopyran-1-ketone of 5-joins in beaker, in beaker
Add 200～300mL dehydrated alcohol, stir 20～30min, by 0.6～0.8L liquid nitrogen spraying to beaker, make beaker temperature drop
To-70～-60 DEG C, stir 10～20min, filter, obtain filtering residue, in filtering residue is placed in 95～105 DEG C of baking ovens, be dried 2～3h,
To 3, double (the methylol)-6-methoxyl group-1H-different .alpha.-5:6-benzopyran-1-ketone of 5-.
The application process of the present invention is: weighs isocoumarin compounds prepared by the 20～30mg present invention and joins beaker
In, in beaker, add 200～300mL dehydrated alcohol, stir 20～30min, make isocoumarin compounds dissolve, 5～6
Age flue-cured tobacco plant on, choose the blade (leaf row normal, anosis without worm) being applicable to test, first blade uniformly sprinkled thin Buddha's warrior attendant
Sand, is uniformly put on standby tobacco mosaic virus (TMV) source sprinkled with on the blade of corundum with brush pen, treats that the blade of all middle choosings connects
After poison terminates, it is immediately placed in the culture dish filling medicinal liquid process 20～30 min, takes out, wipe the globule and medicinal liquid on blade,
Two and half leaves are restored and are emitted in the glass jar being covered with toilet paper moisturizing, and cover glass cover, control temperature at 21～25 DEG C,
It is placed on greenhouse natural light irradiation, the most visible withered speckle of 2～3 d, the relative inhibition being calculated this compound is more than 42.6%,
The present invention has good activity of resisting tobacco mosaic virus.
The invention has the beneficial effects as follows:
(1) present invention uses ultrasound wave and CO2Supercritical extraction is collaborative to be extracted so that extraction process becomes simple, extracts
Rate increases, and extraction time more common extracting method decreases 24～26h, and the present invention is suitable for commercial production, equipment
Asking the highest, the more conventional extracting method of purity of product adds 20%～30%；
(2) present invention has good activity of resisting tobacco mosaic virus.
Detailed description of the invention
First take dry Nicotiana tabacum L. Herb, smash with disintegrating machine, sieve, obtain 100～200 mesh powder, weigh 100～200g
Powder is put in flask, adds 600～700mL dehydrated alcohol, is placed on 3000～3200W ultrasonic extracting machines, ultrasonic carries
Take 30～40min, filter, obtain filtrate, filtrate is carried out decompression distillation, is concentrated into the 1/4 of filtrate volume, stand, filter, remove
Precipitate, again carries out filtrate decompression distillation, obtains extractum a；Above-mentioned extractum a is placed in CO2In supercritical extraction instrument, add
600～700mL dehydrated alcohol, controlling extracting pressure is 25～30MPa, and extraction temperature is 50～60 DEG C, CO2Flow be 20～
25kg/h, extracts 2～3h, obtains isocoumarin compounds；Above-mentioned isocoumarin compounds solution is joined and fills list
In mouth flask, in flask, add 3～5g maleic acids, stirring reaction 1～2h, by 1.0～1.2L liquid nitrogen sprayings to flask, make
Flask temperature is down to-110～-90 DEG C, filters, obtains filtrate, naturally cool to room temperature, filtrate is placed in two mouthfuls with thermometer
In flask, adding 6～8g tetraethyl ammonium hydroxides in flask, stirring reaction 2～3h, by 0.8～1.0L liquid nitrogen spraying to burning
On bottle, make flask temperature be down to-90～-80 DEG C, filter, obtain filtering residue；Above-mentioned filtering residue is placed in beaker, adds in beaker
300～400mL dehydrated alcohol, by 0.1～0.3L liquid nitrogen spraying to beaker, make beaker temperature be down to-30～-20 DEG C, stirring
10～20min, filter, obtain filtrate, by filtrate with 0.4～0.6L liquid nitrogen spraying, make solution temperature be down to-50～-40 DEG C, mistake
Filter, obtains filtrate, by filtrate with 0.6～0.8L liquid nitrogen spraying, makes filtrate temperature be down to-70～-60 DEG C, and filtration obtains filtering residue, i.e.
3,5-double (methylol)-6-methoxyl group-1H-different .alpha.-5:6-benzopyran-1-ketone；By above-mentioned 3, double (the methylol)-6-methoxyl group-1H-of 5-
Different .alpha.-5:6-benzopyran-1-ketone joins in beaker, adds 200～300mL dehydrated alcohol, stir 20～30min in beaker, will
0.6～0.8L liquid nitrogen spraying on beaker, makes beaker temperature be down to-70～-60 DEG C, stirs 10～20min, filter, obtain filtering residue,
It is dried 2～3h in filtering residue is placed in 95～105 DEG C of baking ovens, obtains 3, double (the methylol)-6-different .alpha.-5:6-benzopyran of methoxyl group-1H-of 5--
1-ketone.
Example 1
First take dry Nicotiana tabacum L. Herb, smash with disintegrating machine, sieve, obtain 100 mesh powder, weigh 100g powder and put into flask
In, add 600mL dehydrated alcohol, be placed on 3000W ultrasonic extracting machine, supersound extraction 30min, filter, obtain filtrate, by filtrate
Carry out decompression distillation, be concentrated into the 1/4 of filtrate volume, stand, filter, disgorging, filtrate is carried out again decompression distillation,
Obtain extractum a；Above-mentioned extractum a is placed in CO2In supercritical extraction instrument, adding 600mL dehydrated alcohol, controlling extracting pressure is
25MPa, extraction temperature is 50 DEG C, CO2Flow be 20kg/h, extract 2h, obtain isocoumarin compounds；By above-mentioned an unusually sweet smell
Legumin compounds solution joins and fills in single port flask, adds 3g maleic acid in flask, and stirring reaction 1h, by 1.0L liquid
Nitrogen sprays on flask, makes flask temperature be down to-110 DEG C, filter, obtain filtrate, naturally cool to room temperature, filtrate is placed in
In two mouthfuls of flasks of thermometer, adding 6g tetraethyl ammonium hydroxide in flask, stirring reaction 2h, by 0.8L liquid nitrogen spraying to burning
On bottle, make flask temperature be down to-90 DEG C, filter, obtain filtering residue；Above-mentioned filtering residue is placed in beaker, in beaker, adds 300mL
Dehydrated alcohol, by 0.1L liquid nitrogen spraying to beaker, makes beaker temperature be down to-30 DEG C, stirs 10min, filters, obtains filtrate, will
Filtrate uses 0.4L liquid nitrogen spraying, makes solution temperature be down to-50 DEG C, filters, obtains filtrate, filtrate is used 0.6L liquid nitrogen spraying, makes filter
Liquid temp is down to-70 DEG C, filters, obtains filtering residue, double (the methylol)-6-methoxyl group-1H-different .alpha.-5:6-benzopyran-1-ketone of i.e. 3,5-；Will
Double (the methylol)-6-methoxyl group-1H-different .alpha.-5:6-benzopyran-1-ketone of above-mentioned 3,5-joins in beaker, adds 200mL in beaker
Dehydrated alcohol, stirs 20min, by 0.6L liquid nitrogen spraying to beaker, makes beaker temperature be down to-70 DEG C, stirs 10min, filters,
Obtain filtering residue, be dried 2h in filtering residue is placed in 95 DEG C of baking ovens, obtain 3, double (the methylol)-6-different .alpha.-5:6-benzopyran of methoxyl group-1H-of 5--
1-ketone.
Weigh isocoumarin compounds prepared by the 20mg present invention and join in beaker, add in beaker 200mL without
Water-ethanol, stir 20min, make isocoumarin compounds dissolve, 5 age flue-cured tobacco plant on, choose be applicable to test leaf
Sheet (leaf row is normal, anosis without worm), first uniformly sprinkles fine emery powder, with brush pen by equal for standby tobacco mosaic virus (TMV) source by blade
Even it is put on sprinkled with on the blade of corundum, connects after poison terminates until the blade of all middle choosings, be immediately placed at the culture dish filling medicinal liquid
Middle process 20 min, takes out, wipes the globule and medicinal liquid on blade, is restored by two and half leaves and is emitted on the glass being covered with toilet paper moisturizing
In glass cylinder, and covering glass cover, control temperature, at 21 DEG C, is placed on greenhouse natural light irradiation, the most visible withered speckle of 3d, is calculated this
The relative inhibition of compound is 42.6%, and the present invention has good activity of resisting tobacco mosaic virus.
Example 2
First take dry Nicotiana tabacum L. Herb, smash with disintegrating machine, sieve, obtain 150 mesh powder, weigh 150g powder and put into flask
In, add 650mL dehydrated alcohol, be placed on 3100W ultrasonic extracting machine, supersound extraction 35min, filter, obtain filtrate, by filtrate
Carry out decompression distillation, be concentrated into the 1/4 of filtrate volume, stand, filter, disgorging, filtrate is carried out again decompression distillation,
Obtain extractum a；Above-mentioned extractum a is placed in CO2In supercritical extraction instrument, adding 650mL dehydrated alcohol, controlling extracting pressure is
28MPa, extraction temperature is 55 DEG C, CO2Flow be 23kg/h, extract 2.5h, obtain isocoumarin compounds；By above-mentioned different
Coumarin kind compound solution joins and fills in single port flask, adds 4g maleic acid in flask, and 1.5h is reacted in stirring, will
1.1L liquid nitrogen spraying, on flask, makes flask temperature be down to-100 DEG C, filters, obtains filtrate, naturally cool to room temperature, filtrate put
In two mouthfuls of flasks with thermometer, adding 7g tetraethyl ammonium hydroxide in flask, stirring reaction 2.5h, by 0.9L liquid nitrogen
Spray on flask, make flask temperature be down to-85 DEG C, filter, obtain filtering residue；Above-mentioned filtering residue is placed in beaker, in beaker
Add 350mL dehydrated alcohol, by 0.2L liquid nitrogen spraying to beaker, make beaker temperature be down to-25 DEG C, stir 15min, filter,
Obtain filtrate, filtrate is used 0.5L liquid nitrogen spraying, makes solution temperature be down to-45 DEG C, filter, obtain filtrate, filtrate is used 0.7L liquid nitrogen
Spray, makes filtrate temperature be down to-65 DEG C, filters, obtains filtering residue, double (the methylol)-6-methoxyl group-1H-different benzo pyrrole of i.e. 3,5-
Mutter-1-ketone；By above-mentioned 3, double (the methylol)-6-methoxyl group-1H-different .alpha.-5:6-benzopyran-1-ketone of 5-joins in beaker, in beaker
Add 250mL dehydrated alcohol, stir 25min, by 0.7L liquid nitrogen spraying to beaker, make beaker temperature be down to-65 DEG C, stirring
15min, filters, obtains filtering residue, is dried 2.5h, obtains 3 in filtering residue is placed in 100 DEG C of baking ovens, and double (the methylol)-6-methoxyl group of 5--
1H-different .alpha.-5:6-benzopyran-1-ketone.
Weigh isocoumarin compounds prepared by the 25mg present invention and join in beaker, add in beaker 250mL without
Water-ethanol, stir 25min, make isocoumarin compounds dissolve, 5 age flue-cured tobacco plant on, choose be applicable to test leaf
Sheet (leaf row is normal, anosis without worm), first uniformly sprinkles fine emery powder, with brush pen by equal for standby tobacco mosaic virus (TMV) source by blade
Even it is put on sprinkled with on the blade of corundum, connects after poison terminates until the blade of all middle choosings, be immediately placed at the culture dish filling medicinal liquid
Middle process 25min, takes out, wipes the globule and medicinal liquid on blade, is restored by two and half leaves and is emitted on the glass being covered with toilet paper moisturizing
In glass cylinder, and covering glass cover, control temperature, at 23 DEG C, is placed on greenhouse natural light irradiation, the most visible withered speckle of 2.5 d, calculates
Relative inhibition to this compound is 43.1%, and the present invention has good activity of resisting tobacco mosaic virus.
Example 3
First take dry Nicotiana tabacum L. Herb, smash with disintegrating machine, sieve, obtain 200 mesh powder, weigh 200g powder and put into flask
In, add 700mL dehydrated alcohol, be placed on 3200W ultrasonic extracting machine, supersound extraction 40min, filter, obtain filtrate, by filtrate
Carry out decompression distillation, be concentrated into the 1/4 of filtrate volume, stand, filter, disgorging, filtrate is carried out again decompression distillation,
Obtain extractum a；Above-mentioned extractum a is placed in CO2In supercritical extraction instrument, adding 700mL dehydrated alcohol, controlling extracting pressure is
30MPa, extraction temperature is 60 DEG C, CO2Flow be 25kg/h, extract 3h, obtain isocoumarin compounds；By above-mentioned an unusually sweet smell
Legumin compounds solution joins and fills in single port flask, adds 5g maleic acid in flask, and stirring reaction 2h, by 1.2L liquid
Nitrogen sprays on flask, makes flask temperature be down to-90 DEG C, filter, obtain filtrate, naturally cool to room temperature, filtrate is placed in
In two mouthfuls of flasks of thermometer, adding 8g tetraethyl ammonium hydroxide in flask, stirring reaction 3h, by 1.0L liquid nitrogen spraying to burning
On bottle, make flask temperature be down to-80 DEG C, filter, obtain filtering residue；Above-mentioned filtering residue is placed in beaker, in beaker, adds 400mL
Dehydrated alcohol, by 0.3L liquid nitrogen spraying to beaker, makes beaker temperature be down to-20 DEG C, stirs 20min, filters, obtains filtrate, will
Filtrate uses 0.6L liquid nitrogen spraying, makes solution temperature be down to-40 DEG C, filters, obtains filtrate, filtrate is used 0.8L liquid nitrogen spraying, makes filter
Liquid temp is down to-60 DEG C, filters, obtains filtering residue, double (the methylol)-6-methoxyl group-1H-different .alpha.-5:6-benzopyran-1-ketone of i.e. 3,5-；Will
Double (the methylol)-6-methoxyl group-1H-different .alpha.-5:6-benzopyran-1-ketone of above-mentioned 3,5-joins in beaker, adds 300mL in beaker
Dehydrated alcohol, stirs 0min, by 0.8L liquid nitrogen spraying to beaker, makes beaker temperature be down to-60 DEG C, stirs 20min, filters,
Obtain filtering residue, be dried 3h in filtering residue is placed in 105 DEG C of baking ovens, obtain 3, double (the methylol)-6-different .alpha.-5:6-benzopyran of methoxyl group-1H-of 5--
1-ketone.
Weigh isocoumarin compounds prepared by the 30mg present invention and join in beaker, add in beaker 300mL without
Water-ethanol, stir 30min, make isocoumarin compounds dissolve, 6 age flue-cured tobacco plant on, choose be applicable to test leaf
Sheet (leaf row is normal, anosis without worm), first uniformly sprinkles fine emery powder, with brush pen by equal for standby tobacco mosaic virus (TMV) source by blade
Even it is put on sprinkled with on the blade of corundum, connects after poison terminates until the blade of all middle choosings, be immediately placed at the culture dish filling medicinal liquid
Middle process 30 min, takes out, wipes the globule and medicinal liquid on blade, is restored by two and half leaves and is emitted on the glass being covered with toilet paper moisturizing
In glass cylinder, and covering glass cover, control temperature, at 25 DEG C, is placed on greenhouse natural light irradiation, the most visible withered speckle of 2 d, is calculated
The relative inhibition of this compound is 44.7%, and the present invention has good activity of resisting tobacco mosaic virus.
Claims (1)
1. one kind 3, the preparation method of double (the methylol)-6-methoxyl group-1H-different .alpha.-5:6-benzopyran-1-ketone of 5-, it is characterised in that concrete
Preparation process is:
(1) take dry Nicotiana tabacum L. Herb, smash with disintegrating machine, sieve, obtain 100～200 mesh powder, weigh 100～200g powder
Put in flask, add 600～700mL dehydrated alcohol, be placed on 3000～3200W ultrasonic extracting machines, supersound extraction 30
～40min, filter, obtain filtrate, filtrate is carried out decompression distillation, is concentrated into the 1/4 of filtrate volume, stand, filter, remove precipitation
Thing, again carries out filtrate decompression distillation, obtains extractum a；
(2) above-mentioned extractum a is placed in CO2In supercritical extraction instrument, adding 600～700mL dehydrated alcohol, controlling extracting pressure is
25～30MPa, extraction temperature is 50～60 DEG C, CO2Flow be 20～25kg/h, extract 2～3h, obtain isocoumarin class
Polymer solution；
(3) above-mentioned isocoumarin compounds solution is joined fill in single port flask, in flask, add 3～5g Malaysias
Acid, stirring reaction 1～2h, by 1.0～1.2L liquid nitrogen sprayings to flask, make flask temperature be down to-110～-90 DEG C, filter,
Obtain filtrate, naturally cool to room temperature, filtrate is placed in two mouthfuls of flasks with thermometer, in flask, add 6～8g tetrems
Base ammonium hydroxide, stirring reaction 2～3h, by 0.8～1.0L liquid nitrogen spraying to flask, make flask temperature be down to-90～-80
DEG C, filter, obtain filtering residue；
(4) above-mentioned filtering residue is placed in beaker, in beaker, adds 300～400mL dehydrated alcohol, by 0.1～0.3L liquid nitrogen spray
Pour on beaker, make beaker temperature be down to-30～-20 DEG C, stir 10～20min, filter, obtain filtrate, by filtrate with 0.4～
0.6L liquid nitrogen spraying, makes solution temperature be down to-50～-40 DEG C, filters, obtain filtrate, by filtrate with 0.6～0.8L liquid nitrogen spraying,
Make filtrate temperature be down to-70～-60 DEG C, filter, obtain filtering residue, double (the methylol)-6-methoxyl group-1H-different benzo pyrrole of i.e. 3,5-
Mutter-1-ketone；
(5) by above-mentioned 3, double (the methylol)-6-methoxyl group-1H-different .alpha.-5:6-benzopyran-1-ketone of 5-joins in beaker, in beaker
Add 200～300mL dehydrated alcohol, stir 20～30min, by 0.6～0.8L liquid nitrogen spraying to beaker, make beaker temperature drop
To-70～-60 DEG C, stir 10～20min, filter, obtain filtering residue, in filtering residue is placed in 95～105 DEG C of baking ovens, be dried 2～3h,
To 3, double (the methylol)-6-methoxyl group-1H-different .alpha.-5:6-benzopyran-1-ketone of 5-.
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