CN1074249C - Method for preparing protodrug of bio-insecticide contg hypocrelline A - Google Patents
Method for preparing protodrug of bio-insecticide contg hypocrelline A Download PDFInfo
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- CN1074249C CN1074249C CN96120600A CN96120600A CN1074249C CN 1074249 C CN1074249 C CN 1074249C CN 96120600 A CN96120600 A CN 96120600A CN 96120600 A CN96120600 A CN 96120600A CN 1074249 C CN1074249 C CN 1074249C
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- 239000002917 insecticide Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims description 27
- VANSZAOQCMTTPB-SETSBSEESA-N hypocrellin Chemical compound C1[C@@](C)(O)[C@@H](C(C)=O)C2=C(OC)C(O)=C3C(=O)C=C(OC)C4=C3C2=C2C3=C4C(OC)=CC(=O)C3=C(O)C(OC)=C21 VANSZAOQCMTTPB-SETSBSEESA-N 0.000 claims abstract description 56
- BQJKVFXDDMQLBE-UHFFFAOYSA-N shiraiachrome A Natural products COC1=C2C3=C(OC)C=C(O)C4=C3C3=C5C(CC(C)(O)C(C(C)=O)C3=C(OC)C4=O)=C(OC)C(=O)C(C(O)=C1)=C25 BQJKVFXDDMQLBE-UHFFFAOYSA-N 0.000 claims abstract description 56
- YDLBDQPPRTYAIG-UHFFFAOYSA-N hypocrellin A Natural products COC1C2CC(C)(O)C(C(=O)C)C3=C(OC)C(=O)c4c(O)cc(OC)c5c6c(OC)cc(O)c(C1=O)c6c2c3c45 YDLBDQPPRTYAIG-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000007788 liquid Substances 0.000 claims abstract description 45
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
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- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compounds Of Unknown Constitution (AREA)
Abstract
The present invention relates to a production method of the original drug of insecticide containing hypocrellin A (HA). The original drug can be used for preparing various kinds of insecticide formulation. The production method comprises the following steps: the identification, the pulverization and the preparation of the raw material of hypocrellin, extraction, solid-liquid separation, concentration, secondary solid-liquid separation, the washing, the purification and the desiccation of intermediate bodies, the analysis of product purity and the measurement of overall recovery rate. Longfute insecticide formulation which is prepared from the original drug of biological pesticide insecticide containing the HA of the present invention has superior performance proved by field pharmacodynamic tests, and is insecticide with the advantages of strong toxicity for killing cotton bollworms, long residual action, protection for natural enemies, no environmental pollution and no harm for people and livestock.
Description
The invention relates to the production technology of novel agrochemical, be specially the raw insecticide medicine production method that contains hypocrellin A (HA).
The English name of known natural products hypocrellin A is " Hypocrellin A ", belongs to 4,9-dihydroxy-3,10 perylene quinone derivative, and its molecular formula is C
30H
26O
10, molecular weight 546, structural formula are down:
The physicochemical property of its standard items is: red crystals; Odorless, tasteless; Purity 98%; Fusing point 209-210 ℃; Be soluble in chloroform, acetone, ethyl acetate, be dissolved in methyl alcohol, ethanol, be slightly soluble in benzinum, water-soluble hardly, but make behind the micella in the water soluble; Be difficult for taking place hydrolysis; In alkaline environment, can be from quick photooxidation, that continues is decomposed into various molecular fragments; Qualitative spectrogram comprises infrared spectrum, ultraviolet spectra, mass spectrum, nuclear magnetic resoance spectrum.
Hypocrellin A is to extract the native compound that obtains the natural resources natural microbial fungi Hypocrella bambusae (Bet Br). Sace [hypocrella bambusae (B.et Br.) sacc.] from peculiar the enriching of China.Among the people once in order to its treatment stomachache and arthritis, now developed into treatment skin stubborn disease, anti-Aids, antitumor potential effective photosensitive drug.The present invention continues in the past to the basic research of HA, first HA is developed to the novel biopesticide of control cotton bollworm.Look into newly through the domestic and foreign literature retrieval, do not see the research report of relevant hypocrellin A as agricultural chemical insecticide, bactericide.
Now insecticides such as chemical pesticide nuvacron that uses and acephatemet (high poison) and methomyl milk oil pollute the environment, endanger the person poultry safety, natural enemy that simultaneously can killing heliothis armigera; Existing commercially available biopesticide bacillus thuringiensis suspending agent (BT) and viral insecticide, the drug effect of control cotton bollworm is undesirable, is still proceeding research of technique, improves its virulence.Hypocrellin A raw insecticide medicine (HA 〉=60%) and the preparations " Long Fute " etc. of containing of the present invention through animal test results, prove to belong to low toxicity level, be actually little poison level, and nothing causes prominent effect, and is all non-stimulated to eyes and skin, do not use and can cause environmental pollution; Through three provinces, five ground, the effect of the control cotton bollworm of 2 years these medicaments of field control effectiveness test is better than commercially available biopesticide bacillus thuringiensis suspending agent (BT), also be better than nuvacron and acephatemet height and poison the medicine of learning to farm (50ml medicament/mu), though a little less than 20% methomyl milk oil (50ml medicament/mu), but be persistent pesticide, and can protect natural enemy; Other advantages comprise: cotton is not had poisoning, protect terminal bud and protect bell rate height, to killing not dead cotton bollworm the diapause effect is arranged, cotten aphid is also had inhibitory action.By lab scale and pilot scale, process route is simple and feasible on production technology for former medicine and preparation.
The present invention contains the raw material Hypocrella bambusae (Bet Br). Sace or the bamboo parasitic fungus of the raw insecticide medicine production of hypocrellin A, is to abound with the NW YUNNAN in China, and the southeast is hidden in southwest, river, and wild resource is abundant.Hypocrella bambusae (Bet Br). Sace belongs to son bundle Gammaproteobacteria, Hypocreaceae, inferior meat seat Pseudomonas, belongs to fungi.Its proterties is: the stroma meat, do back cork matter, and maroon, dome-type has the aperture, diameter 1-2 centimetre; Son bundle cylindrical shape, 20-30 * 300-360 micron, 8 in son bundle spore, worm shape has separation, little yellow, the dextrorotation distortion is rope form, 7.5-10 * 260-360 micron, lateral filament is very thin, inner mycelia dark brown.
The Hypocrella bambusae (Bet Br). Sace host is the arrow bamboo, and January in every year, red bamboo fungus stroma began to form, and August is ripe in a large number, drops after October.Therefore, in every year 8,9, October, collection was advisable.Because of place of production difference, the HA content is little, and stores the Hypocrella bambusae (Bet Br). Sace in the different places of production of 1-5 respectively, and its HA content also changes between 3.47-3.94%.
The report that hypocrellin A (HA) is only had structural behaviour at present both at home and abroad, and there is not report as agricultural chemical insecticide, bactericide, and, the extraction of relevant hypocrellin A (HA), has only breadboard fragment overview, and from Hypocrella bambusae (Bet Br). Sace, extracting the separating method of hypocrellin A (HA), Shang Weijian is as being the relevant report of purpose suitability for industrialized production with production.
For example Chinese scholar once to its physics, chemical property, optical physics, photochemistry, photoproduction thing characteristic and the mechanism of action thereof carried out comprehensively, systematic research [Jiang Lijin, the structure of hypocrellin, character, photochemical reaction and reaction mechanism (I, II), " Science Bulletin ", the 21st phase, the 22nd phase, nineteen ninety].Hypocrellin A, extract are extracted in common laboratory research from Hypocrella bambusae (Bet Br). Sace separation, method for preparing purified are as follows:
The Hypocrella bambusae (Bet Br). Sace 160g that pulverizes is placed in the Sha Shi extractor, use acetone extraction, the stickiness solid that obtains after extract drained places the beaker that fills benzinum (60 ℃-90 ℃), heat while stirring to boiling, cooling, suction filtration, aforesaid operations heavily covers several times and is transformed into loose shape solid up to the stickiness solid, use benzene one benzinum (60 ℃-90 ℃) recrystallization again, get 3.5g hypocrellin A crude product (HA) [citing document: Zhao Kaihong, Jiang Lijin, organic chemistry, 1989,9, P.252-254, research notes].Shortcoming belongs to sample to be handled, and lacks concrete technological parameter, is difficult to be used in suitability for industrialized production HA according to said procedure.
The purpose of this invention is to provide the process that a kind of suitability for industrialized production contains the insecticide of hypocrellin A, the manufacturing technique method that particularly contains the former medicine of formulation of insecticides of hypocrellin A, make this novel biopesticide be applied to agricultural production, in particular as the insecticide of killing cotton bollworm.
The present invention for producing the preparation that novel biopesticide contains the insecticide of hypocrellin A, has developed the manufacturing technique method of the raw insecticide medicine that contains HA, and through lab scale and pilot plant trial production checking, confirms that this production technology is simple and feasible.The technology content comprises that raw material is selected for use and quality index, processing step (operation), technological parameter, examination and test of products method, product result of use and example etc.
The present invention contains the production technology of the raw insecticide medicine of hypocrellin A, comprise that following order respectively goes on foot operation: 1. the identification of raw material Hypocrella bambusae (Bet Br). Sace, 2. the pulverizing of raw material preparation, 3. leaching process, 4. Separation of Solid and Liquid, 5. concentrating under reduced pressure, 6. Separation of Solid and Liquid for the second time, 7. intermediate washs purifying, 8. intermediate drying, 9. product purity analysis and overall recovery mensuration.Formulation of insecticides " Long Fute " intermediate (HA) technological process of production sketch is attached.Now each step operation is described in detail as follows:
One, the identification of raw material Hypocrella bambusae (Bet Br). Sace: meet to turn biochemical reaction such as green behind the alkali and to have according to Hypocrella bambusae (Bet Br). Sace tool maroon and twist 8 morphological features such as worm shape spore that are rope form, can accurately discern crude drug.
Two, raw material pulverizing preparation: will deposit dry Hypocrella bambusae (Bet Br). Sace body naturally, after pulverizing, sieve, get the fraction 100% of granularity-20 order (sieving), need prevent " cross and pulverize ", promptly require wherein-180 order person＜5% with standard screen with cracker.
Three, leaching process
Hypocrellin A (HA) generally is water or alcohol extract as if the production process as traditional Chinese medicine.And the former medicine production of biopesticide insecticide of the present invention is to extract with organic solvent-acetone, chloroform, ethyl acetate and alcohols, and preferably acetone is solvent and adopts special technology and parameter.Acetone extraction engineer testing (lab scale and pilot scale) comparativity example can be referring to last subordinate list.
1. soak: the present invention selects for use industrial acetone to soak in extractor at normal temperatures and pressures Hypocrella bambusae (Bet Br). Sace body raw material.The solid-liquid volume ratio of raw material and solvent (S: L)=1: 10-1: 8, time＜12 hour were generally 6-12 hour.
2. extract: be with acetone or alcohols (comprising methyl alcohol and ethanol), preferred acetone is solvent, extracts 2-3 time.Its solid-to-liquid ratio (S: L)=1: 10-1: 6, extraction time 4-1 hour, temperature kept 50 ± 5 ℃.Selecting for use and extract for twice or three times, is to decide on the economic comparativity of preceding twice recovery rate and solvent consumption.
For the first time, in extractor, with the solid-to-liquid ratio of raw material and acetone=1: 10, keep that reflux state is little to boil about 4 hours, temperature remains on 50 ± 2 ℃.Observe liquid level and little boiling occur, condenser the backflow of liquid stream shape occurs and is advisable.
For the second time, also in extractor, extract.The solid-liquid volume ratio of raw material and acetone (S: L)=1: 8, about 50 ℃ or 50 ± 2 ℃ keep little reflux states that boil, count through 2-4 hour from little reflux state that boils.
For the third time: solid-to-liquid ratio (S: L)=1: 6, count from little reflux state that boils, extracted through 1-2 hour.
Four, Separation of Solid and Liquid: after extracting through twice or three times, carry out the Separation of Solid and Liquid deslagging.Separation of Solid and Liquid can be utilized three kinds of methods.
1. Lu rod filters, and makes the dregs of a decoction continue to finish extraction can to adopt filter stick to filter Lu rod hole 0.5-5 μ m to being extracted as for the first time.
2. sedimentation and filtration requires extract to pass through 100 purpose double-layer stainless steel mesh screen sedimentations and filters.
3. plate-frame filtering requires extract to pass through 2# filter cloth (φ=0.5 μ m).
Five, concentrating under reduced pressure: make the extract that obtains after the Separation of Solid and Liquid enter concentration tank and concentrate with the reduced-pressure backflow state, temperature is controlled at 50-60 ℃, best 55 ℃, it is concentrated into paste.The discharge solid-to-liquid ratio (S: L)=1: 2 or big slightly.Before extract enters concentration tank, but the sampling and measuring recovery rate.In the process of concentrating under reduced pressure, reclaim solvent.
Six, Separation of Solid and Liquid: through after concentrating, need carry out Separation of Solid and Liquid once more at extract.Separation of Solid and Liquid is to carry out in the centrifuge of＞1000rpm, and the filter bag aperture is φ=0.5 μ m.Get its solids and be intermediate, reclaim solvent simultaneously.
Seven, intermediate washing: the intermediate washing is slurrying washing, purifying.Washing can be adopted two kinds of schemes:
1. this scheme is generally adopted in benzinum (60 ℃-90 ℃ of boiling points) washing in the laboratory.The solid-to-liquid ratio of washing (S: L)=1: 6-1: 10, can select for use 1: 8.Carry out in heating and stirring tank, temperature is-50 ℃, and general 40-50 ℃, washing times is 2 times-3 times, all carries out Separation of Solid and Liquid after each washing in centrifuge.
2. second kind of washing scheme, this scheme be the present invention according to the special-purpose new washing scheme that experimental result proposes, specifically be divided into for two steps:
(1) with 90 ℃ of hot washes, (S: L)=1: 10 or big slightly, or with the hot wash that contains surfactant (neutrality) 5 ‰, temperature is about 60 ℃ to solid-to-liquid ratio, to remove stearic acid and stearate impurity.
(2) kerosene washing: 40 ℃-50 ℃, best 50 ℃, solid-to-liquid ratio (S: L)=1: 6, further to remove stearate impurity.
The washing back is with the centrifugal Separation of Solid and Liquid of carrying out.The present invention adopts hot wash first, to remove the stearic acid impurity of water dissolvable, also initiates simultaneously with kerosene and washs to remove stearate impurity, and is not only effective, and can reduce production costs.
Eight, intermediate drying
The intermediate drying is to carry out in drying baker, and temperature is controlled at 60 ℃ of the bests, is generally 55-62 ℃.Be generally 4 hours about 3-5 hour drying time, makes wherein moisture＜5%, at last to the product weighing and bagging.
Nine, analytic product purity and mensuration overall recovery
Generally require content 〉=60% of hypocrellin A (HA) in the raw insecticide medicine product; All the other＜40% impurity mainly is fatty acid (for gaidic acid and octadecenoic acid), fatty glyceride (triglyceride), belong to 4 in addition, hypocrelline B (the Hypocrellin B of 9-dihydroxy-3,10 perylene quinone derivative, be called for short HB, molecular formula is C
30H
24O
9, molecular weight 528), these impurity do not influence the insecticidal effect of HA.
Former medicine technical indicator:
Hypocrellin A (HA) content, % 〉=60%
Water content≤5%
Acidity is (with H
2SO
4Meter) 0.1%
14 days resolution ratio≤5.0% of heat endurance (50 ± 1 ℃)
Natural daylight exposes 1 all resolution ratios≤5.0% to the open air under the normal temperature
In view of HA is by extracting the native compound that obtains in the natural microbial fungi Hypocrella bambusae (Bet Br). Sace, producing quality control standard HA content 〉=60% of former medicine, wherein impurity content≤40%.The impurity chemical composition is more, use conventional chemical method, gas-chromatography, liquid chromatogram that HA is separated, measures, disturbing factor is many, be difficult to analyze, adopt the thin-layer chromatography good separating effect, particularly main interfering component hypocrelline B (HB) can be separated well, and other major impurity stearic acid, stearate, tristerin, do not have light absorption at 464nm, all do not influence accurate mensuration HA content with colorimetric method.Therefore selecting thin-layer chromatography-colorimetric method is suitable selection.Measuring HA content in former medicine and the preparation with the method, is conveniently accurately.
Separate by rotating thin layer chromato-graphy, red pigments HA and HB and fatty acid, fatty glyceride can be separated, except that center of circle red pigments (HA and HB), under UV illumination, can also detect two important fluorescent bands, through mass spectrum, infrared, nuclear-magnetism, and with standard spectrum contrast, proving conclusively them is respectively gaidic acid and octadecenoic acid and tri-fatty glyceride.Because they all do not have light absorption at 464nm, so their existence does not influence the accurate mensuration of HA content in the former medicine.Measure the absorbance of ethanol extract, can obtain HA content in former medicine and the preparation by calculating at 464nm.
The accuracy of test method: the mensuration (V%:3.36% of (1) precision; (2) the mensuration average recovery rate of accuracy: 95.95%; (3) range of linearity: point sample is good linear relation with the 464nm absorbance in 1.97 μ g-11.82 μ g scopes.
Embodiment 1
Get Hypocrella bambusae (Bet Br). Sace body raw material in extractor with acetone with solid-liquid volume ratio=at normal temperatures and pressures soak 12 hour at 1: 10; Use acetone to extract red 4 hours for 50 ± 2 ℃ in temperature then, extracted 1 hour in 50 ± 2 ℃ with solid-to-liquid ratio=1: 8 for the second time with solid-to-liquid ratio=1: 10; After this carry out Separation of Solid and Liquid, utilize plate filter, make solution pass through the 2# filter cloth, φ=0.5 μ m; Extract is carried out concentrating under reduced pressure, temperature is controlled at about 55 ℃ thereupon, makes it be condensed into paste; Carry out the Separation of Solid and Liquid second time (in centrifuge); Intermediate washing purifying adopted for two steps: the first step is with 90 ℃ hot wash or with the hot water that contains surfactant 5 ‰, and about 60 ℃ of temperature is to remove stearic acid impurity, second step was washed 55 ℃ of temperature, solid-to-liquid ratio=1: 6 with kerosene, to remove stearate impurity, carry out centrifugation after the washing; At last with intermediate in baking oven in 60 ℃ of oven dry 4 hours, obtain former medicine product, wherein HA content is 60% after measured, former medicine technology is censured and is met the table scope.
Embodiment 2
According to the method for making of embodiment 1, difference is: extraction is to use methyl alcohol; The intermediate washing is that the employing benzinum is a washing agent, and solid-to-liquid ratio=1: 8 is carried out in heating and stirring tank, and temperature keeps about 50 ℃, washs 3 times, all carries out Separation of Solid and Liquid after each washing in centrifuge.
Embodiment 3
The method for making of former medicine is that difference only is according to embodiment 1: carry secondary with ethanol.
Embodiment 4
The method for making of former medicine is by embodiment 1, and difference only is that the washing methods of intermediate is identical with embodiment 2.
Subordinate list acetone extraction technology test (lab scale and pilot scale) comparativity example
HA intermediate technological process of production sketch
| Number of times | Inventory | Soak time | Extract for the first time | Extract for the second time | Sterling % in the raw material | Throw material and contain sterling % | Extract liquid measure L | Extract concentration * 10-2M | Productive rate % | Total rate of recovery % | |||||
| Quantity of solvent Kg | Time Hr | Temperature ℃ | Quantity of solvent Kg | Time Hr | Temperature ℃ | ||||||||||
| Lab scale | 1 | 8 | 12 | 80 | 4 | -50 | 80 | 4 | -50 | 4 | 0.32 | 38 | 1.26 | 3.27 | 81.7 |
| 2 | 7 | 12 | 70 | 4 | -50 | 70 | 4 | -50 | 4 | 0.28 | 22 | 1.70 | 2.96 | 74 | |
| 3 | 7 | 12 | 70 | 4 | -50 | 70 | 2 | -50 | 4 | 0.28 | 25 | 1.67 | 3.26 | 81.5 | |
| 4 | 7 | 12 | 70 | 4 | -50 | 70 | 2 | -50 | 4 | 0.28 | 28 | 1.87 | 4.12 | 103 | |
| 5 | 9 | 24 | 90 | 4 | -73 | 90 | 2 | -73 | 4 | 0.36 | 43 | 1.02 | 2.27 | 63 | |
| Pilot scale | 1 | 105 | 12 | 1050 | 2 | -50 | 840 | 4 | -50 | 4 | 4.20 | 850 | 6.45 | 3.11 | 74 |
| 2 | 107 | 12 | 1070 | 2 | -50 | 856 | 4 | -50 | 4 | 4.28 | 860 | 6.50 | 3.03 | 71 | |
| 3 | 150 | 12 | 1500 | 2 | -50 | 1200 | 4 | -50 | 4 | 6.0 | 1080 | 8.19 | 4.08 | 68 | |
| 4 | 128 | 12 | 1280 | 2 | -50 | 1024 | 4 | -50 | 4 | 5.12 | 910 | 6.90 | 3.87 | 75 | |
| 5 | 104 | 12 | 1040 | 2 | -50 | 832 | 4 | -50 | 4 | 4.16 | 840 | 6.37 | 2.90 | 69 | |
| 6 | 103 | 12 | 1030 | 2 | -50 | 824 | 4 | -50 | 4 | 4.12 | 870 | 6.60 | 2.98 | 72.4 | |
Claims (7)
1. the production method of a biopesticide raw insecticide medicine, the production method that it is characterized in that containing the raw insecticide medicine of hypocrellin A is made up of the following operation that respectively goes on foot: the pulverizing preparation of (1) raw material Hypocrella bambusae (Bet Br). Sace body, (2) leaching process of hypocrellin A, (3) Separation of Solid and Liquid, (4) concentrating under reduced pressure, the centrifugation of (5) concentrating under reduced pressure thing; (6) intermediate washing purifying, and (7) intermediate drying; It is to pulverize, sieve with cracker that wherein said raw material Hypocrella bambusae (Bet Br). Sace body is pulverized preparation, chooses granularity 20 purpose fractions 100%; The leaching process of described hypocrellin A, be with solvent acetone at normal temperatures and pressures with solid-to-liquid ratio=1 of raw material and solvent: 10-1: 8 soaked 6-12 hour, were solvent with acetone or alcohol again, with solid-to-liquid ratio=1: 10-1: 6, extracted 1-4 hour at 50 ± 5 ℃, extract 2-3 time; Described Separation of Solid and Liquid is to adopt filter stick filtration, sedimentation and filtration or plate-frame filtering; Described concentrating under reduced pressure, temperature range are 50-60 ℃, discharge solid-to-liquid ratio=1: 2; The Separation of Solid and Liquid of concentrate is to carry out in the centrifuge of＞1000rpm, and the filter bag aperture is φ=0.5 μ m; Described intermediate washing purifying, be to use petroleum ether, with solid-to-liquid ratio=1: 6-1: 10, the temperature of agitator tank is generally 40-50 ℃, can wash 2-3 time, all carries out Separation of Solid and Liquid after each washing, described intermediate drying is to carry out in baking oven, temperature is 55-62 ℃, dry 3-5 hour, makes wherein moisture＜5%.
2. the production method of the former medicine of agricultural chemical insecticide as claimed in claim 1, it is characterized in that extracting used solvent alcohol is methyl alcohol or ethanol.
3. the production method of the former medicine of agricultural chemical insecticide as claimed in claim 1, it is characterized in that Separation of Solid and Liquid, wherein extract employing first time filter stick is filtered, the filter stick hole is 0.5-5 μ m, sedimentation and filtration requires the double-deck sedimentation filter of extract by 100 meshes, and plate-frame filtering requires the 2# filter cloth of extract by φ=0.5 μ m.
4. the production method of the former medicine of agricultural chemical insecticide as claimed in claim 1 is characterized in that described intermediate washing purifying is earlier with 90 ℃ hot wash, washs solid-to-liquid ratio=1: 6, temperature 40-50 ℃ then with kerosene.
5. the production method of the former medicine of agricultural chemical insecticide as claimed in claim 1, it is characterized in that described intermediate washing purifying is earlier with 55-60 ℃ the hot wash that contains 5/10000ths neutral surface active agent, then with kerosene washing, solid-to-liquid ratio=1: 6, temperature 40-50 ℃.
6. the production method of the former medicine of agricultural chemical insecticide as claimed in claim 5 is characterized in that intermediate washing purifying is that temperature is 60 ℃ with the hot wash that contains the neutral surface active agent, and the wash temperature of kerosene is 50 ℃.
7. the production method of the former medicine of agricultural chemical insecticide as claimed in claim 1 is characterized in that dry temperature is 60 ℃, 4 hours time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96120600A CN1074249C (en) | 1996-11-22 | 1996-11-22 | Method for preparing protodrug of bio-insecticide contg hypocrelline A |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96120600A CN1074249C (en) | 1996-11-22 | 1996-11-22 | Method for preparing protodrug of bio-insecticide contg hypocrelline A |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1183216A CN1183216A (en) | 1998-06-03 |
| CN1074249C true CN1074249C (en) | 2001-11-07 |
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| CN96120600A Expired - Fee Related CN1074249C (en) | 1996-11-22 | 1996-11-22 | Method for preparing protodrug of bio-insecticide contg hypocrelline A |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1133612C (en) * | 2000-08-22 | 2004-01-07 | 云南医药工业股份有限公司 | Bamboo parasitic fungus extract and its preparation and application |
| CN1389110A (en) * | 2002-05-10 | 2003-01-08 | 张红雨 | Photosensitive biological germicide of perylene quinone and its prepn. |
| CN102696703B (en) * | 2012-05-29 | 2015-08-19 | 浙江农林大学 | A kind of insecticides and purposes of preventing and treating agriculture and forestry injurious insect |
| CN113424913A (en) * | 2021-07-15 | 2021-09-24 | 吉林大学 | Preparation method of hypocrellin nano bactericidal emulsion as natural photosensitizer |
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Non-Patent Citations (3)
| Title |
|---|
| 有机化学1989.9 1989.1.1 赵开弘蒋丽金竹红菌研究简报 * |
| 科学通报1990.21期 1990.1.1 蒋丽金竹红菌素的结构，性质光化学反应及反应机1608 * |
| 科学通报1990.21期 1990.1.1 蒋丽金竹红菌素的结构，性质光化学反应及反应机1608;有机化学1989.9 1989.1.1 赵开弘蒋丽金竹红菌研究简报 * |
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