CN1827612B - New process for synthesizing daphnetin - Google Patents
New process for synthesizing daphnetin Download PDFInfo
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- CN1827612B CN1827612B CN2006100167310A CN200610016731A CN1827612B CN 1827612 B CN1827612 B CN 1827612B CN 2006100167310 A CN2006100167310 A CN 2006100167310A CN 200610016731 A CN200610016731 A CN 200610016731A CN 1827612 B CN1827612 B CN 1827612B
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- 238000000034 method Methods 0.000 title claims abstract description 17
- ATEFPOUAMCWAQS-UHFFFAOYSA-N 7,8-dihydroxycoumarin Chemical compound C1=CC(=O)OC2=C(O)C(O)=CC=C21 ATEFPOUAMCWAQS-UHFFFAOYSA-N 0.000 title claims abstract description 10
- YBGKGTOOPNQOKH-UHFFFAOYSA-N daphnetin Natural products OC1=CC=CC2=C1OC(=O)C=C2O YBGKGTOOPNQOKH-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 230000008569 process Effects 0.000 title abstract description 7
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 16
- 230000007935 neutral effect Effects 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 230000008021 deposition Effects 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 229940079877 pyrogallol Drugs 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- 235000012255 calcium oxide Nutrition 0.000 claims description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 2
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 239000000047 product Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000011949 solid catalyst Substances 0.000 abstract description 2
- 239000005457 ice water Substances 0.000 abstract 2
- 239000002244 precipitate Substances 0.000 abstract 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 abstract 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 abstract 1
- 239000011449 brick Substances 0.000 abstract 1
- 239000002274 desiccant Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 235000011090 malic acid Nutrition 0.000 abstract 1
- 239000001630 malic acid Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 206010002660 Anoxia Diseases 0.000 description 1
- 241000976983 Anoxia Species 0.000 description 1
- 208000033386 Buerger disease Diseases 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 206010043540 Thromboangiitis obliterans Diseases 0.000 description 1
- 230000000202 analgesic effect Effects 0.000 description 1
- 230000007953 anoxia Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000002785 anti-thrombosis Effects 0.000 description 1
- 239000003146 anticoagulant agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 208000029078 coronary artery disease Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000002107 myocardial effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 208000010110 spontaneous platelet aggregation Diseases 0.000 description 1
- 230000024883 vasodilation Effects 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Catalysts (AREA)
Abstract
The invention provides a new process for synthesizing daphnetin, which comprises the steps of uniformly mixing pyrogallic acid and malic acid, adding concentrated sulfuric acid, adding a drying agent and an organic solvent, slowly stirring and gradually heating, pouring into ice water after the reaction is carried out, standing, precipitating, filtering, obtaining precipitate, washing the precipitate by the ice water to be neutral, and drying to obtain brick red powder. The invention has the advantages that: the reaction condition is mild, the reaction process is easy to operate and control, the by-products are few, the appearance quality and the purity of the product are high, and the purification is easy. The solid catalyst and organic solvent used in the production can be recycled, thereby reducing the production cost and the pollution to the environment. Especially, compared with the traditional synthesis process, the yield and the purity are greatly improved, the yield can be increased by more than 30 percent, and the purity can be increased to more than 93 percent, so that the method is more suitable for industrial production.
Description
Technical field
The present invention discloses a kind of novel process of synthetic Daphnetin, has characteristics such as productive rate and purity height, belongs to chemicals synthesis technology field.
Background technology
Daphnetin is one of cardio-cerebrovascular medication; Anti-inflammatory, platelet aggregation-against and antithrombotic, vasodilation, increase coronary flow, anoxia are arranged, improve effect such as myocardial metabolism through pharmacology proof; Be used to clinically treat thromboangiitis obliterans and coronary heart disease, and analgesic activity is preferably arranged.Its common name is: Daphnetin, and chemistry is by name: 7, the 8-dihydroxycoumarin, its chemical structure is following:
Document (Aust.J.; Chem.) synthesis technique of report Daphnetin is to be raw material with pyrogallol and oxysuccinic acid, does at the vitriol oil that generation Pechman condensation comes synthetic under the situation of catalyzer, dewatering agent, and the shortcoming of this method is that productive rate is low; Purity is low; Raw material is prone to charing, and the product visual appearance is poor, and caking phenomenon very easily takes place reaction system.
Summary of the invention
The present invention provides a kind of novel process of synthetic Daphnetin, and purpose is intended to solve the above-mentioned shortcoming that exists in the traditional synthesis.
Technical solution of the present invention is following: existing processes is a catalyzer with the vitriol oil and solid drier on former technology basis, alleviates the charing phenomenon with organic solvent as solvent, synthetic Daphnetin, and its reaction formula is following:
The starting raw material pyrogallol that feeds intake in the above-mentioned reaction: oxysuccinic acid weight ratio 1: 0.8～5 is for best.
Reaction system uses the vitriol oil and organic solvent weight ratio 1: 0.2～2.5 to be advisable, and it is slowly suitable to heat up, and temperature of reaction is controlled at 90-140 ℃ for best, and the reaction times should be at 10 minutes-1 hour.
Concrete synthesis technique may further comprise the steps (mark ratio by weight):
Pyrogallol and oxysuccinic acid with 1: 0.8～5 mix, and adding with the pyrogallol portion rate is 1～10 part the vitriol oil, add again with vitriol oil portion rate be 0.1～10 part siccative and with vitriol oil portion rate be 0.2～2.5 part organic solvent; Slowly stir and heat temperature raising 90-140 ℃ gradually, reacted 10～60 minutes, pour in the frozen water; Placed 48 hours, deposition is filtered; Filter deposition through frozen water washing to being neutral, at 105 ℃ of dry brick-red powder.
Above-mentioned siccative can be silica gel, resin, Calcium Chloride Powder Anhydrous, quicklime, Vanadium Pentoxide in FLAKES, soda-lime, the vitriol oil, molecular sieve, anhydrous calciumsulphate, anhydrous cupric sulfate; In anhydrous magnesium sulfate, the SODIUM SULPHATE ANHYDROUS 99PCT one or more are mixed, can add fast response and carry out speed.
Above-mentioned organic solvent can be mixed in dioxane, tetracol phenixin, YLENE, vinyl acetic monomer, butanone, Virahol, butanols, acetone, methylethylketone, pimelinketone, THF, toluene, mono chloro benzene, methylene dichloride, the ethylene dichloride one or more, prevents charing.
Synthesis technique of the present invention is compared with traditional synthesis, has following advantage: reaction conditions is gentle, the reaction process easy operation control, and by product is few, and the visual appearance of product and purity are high, are prone to purify.Used solid catalyst and organic solvent are recyclable in the production utilizes again, thereby has reduced production cost and to the pollution of environment.Particularly compare with traditional synthesis technique, productive rate and purity have had very big raising, and yield can increase more than 30 percentage points, and purity can be increased to and be more suitable for suitability for industrialized production more than 93%.
Following experimental example further proves the product comparative result of production technique of the present invention and traditional processing technology:
Can draw independent use sulfuric acid from above-mentioned comparison test and make catalyzer, yield is between 25-35%, and purity is between the 60-80%, but when sulfuric acid and siccative coupling, yield can increase more than 15 percentage points, and purity can be increased to more than 90%.
Can draw independent use sulfuric acid from above-mentioned comparison test and make catalyzer, yield is between 25-35%, and purity is between the 60-80%, but when sulfuric acid and organic solvent coupling, yield can increase by 20 percentage points, and purity can be increased to more than 90%.
Can draw independent use sulfuric acid from above-mentioned comparison test and make catalyzer, yield is between 25-35%, and purity is between the 60-80%, but when sulfuric acid and siccative, solvent coupling, yield can increase by 30 percentage points, and purity can be increased to more than 93%.
In sum, this technology obviously is superior to traditional technology, and can obviously improve yield and purity.
Embodiment:
Through following examples the present invention is described for example further; And do not limit the present invention in any way; Under the prerequisite that does not deviate from technical solution of the present invention, any change or change that those of ordinary skills that the present invention did are realized easily all will fall within the claim scope of the present invention.
Embodiment 1:
In three mouthfuls of round-bottomed flasks, add the pyrogallol (37.8g) that mixes, oxysuccinic acid (67.5g) is with the 75g anhydrous magnesium sulfate; Add the 90ml dioxane and the 90ml vitriol oil again, slowly stir and heat temperature raising 100-130 ℃ gradually, reacted 40 minutes, pour in the frozen water; Placed 48 hours, deposition is filtered, and filters deposition and washs to being neutral through frozen water; At 105 ℃ of dry brick-red powder 31.5g, yield is 59%, and purity is 96.3%.
Embodiment 2:
In three mouthfuls of round-bottomed flasks, add the pyrogallol (37.8g) that mixes, oxysuccinic acid (53.6g) is with the 45g Vanadium Pentoxide in FLAKES; Add the 120ml tetracol phenixin and the 90ml vitriol oil again, slowly stir and heat temperature raising 110-140 ℃ gradually, reacted 1 hour, pour in the frozen water; Placed 48 hours, deposition is filtered, and filters deposition and washs to being neutral through frozen water; At 105 ℃ of dry brick-red powder 35.7g, yield is 66.9%, and purity is 94.2%.
Embodiment 3:
In three mouthfuls of round-bottomed flasks, add the pyrogallol (37.8g) that mixes, oxysuccinic acid (80.4g) is with the 100g molecular sieve; Add the 160ml THF and the 80ml vitriol oil again, slowly stir and heat temperature raising 110-140 ℃ gradually, reacted 1 hour, pour in the frozen water; Placed 48 hours, deposition is filtered, and filters deposition and washs to being neutral through frozen water; At 105 ℃ of dry brick-red powder 30.3g, yield is 56.7%, and purity is 97.6%.
Embodiment 4:
In three mouthfuls of round-bottomed flasks, add the pyrogallol (37.8g) that mixes, oxysuccinic acid (40.2g); With 60g molecular sieve and 50g Calcium Chloride Powder Anhydrous, add the 110ml toluene and the 100ml vitriol oil again, slowly stir and heat temperature raising 115-125 ℃ gradually, reacted 1 hour; Pour in the frozen water, placed 48 hours, deposition is filtered; Filter deposition through frozen water washing to being neutral, at 105 ℃ of dry brick-red powder 37.8g, yield is 70.8%, purity is 98.3%.
Embodiment 5:
In three mouthfuls of round-bottomed flasks, add the pyrogallol (63g) that mixes, oxysuccinic acid (73.7g); With 60g anhydrous cupric sulfate and 25g silica gel, add the 160ml vinyl acetic monomer and the 140ml vitriol oil again, slowly stir and heat temperature raising 105-140 ℃ gradually, reacted 30 minutes; Pour in the frozen water, placed 48 hours, deposition is filtered; Filter deposition through frozen water washing to being neutral, at 105 ℃ of dry brick-red powder 59.8g, yield is 67.2%, purity is 96.5%.
Embodiment 6:
In three mouthfuls of round-bottomed flasks, add the pyrogallol (63g) that mixes, oxysuccinic acid (89.3g); With the 200g molecular sieve, add 80ml toluene, 70ml dioxane and the 170ml vitriol oil again, slowly stir and heat temperature raising 90-105 ℃ gradually, reacted 45 minutes; Pour in the frozen water, placed 48 hours, deposition is filtered; Filter deposition through frozen water washing to being neutral, at 105 ℃ of dry brick-red powder 61.3g, yield is 68.9%, purity is 95.7%.
Embodiment 7:
In three mouthfuls of round-bottomed flasks, add the pyrogallol (50.4g) that mixes, oxysuccinic acid (103.5g); With the 70g SODIUM SULPHATE ANHYDROUS 99PCT, add 90ml methylene dichloride, 30ml ethylene dichloride and the 120ml vitriol oil again, slowly stir and heat temperature raising 95-120 ℃ gradually, reacted 25 minutes; Pour in the frozen water, placed 48 hours, deposition is filtered; Filter deposition through frozen water washing to being neutral, at 105 ℃ of dry brick-red powder 44.1g, yield is 61.9%, purity is 95.3%.
Embodiment 8:
In three mouthfuls of round-bottomed flasks, add the pyrogallol (63g) that mixes, oxysuccinic acid (107.2g); With 75g resin and 35g quicklime, add the 180ml toluene and the 160ml vitriol oil again, slowly stir and heat temperature raising 115-140 ℃ gradually, reacted 40 minutes; Pour in the frozen water, placed 48 hours, deposition is filtered; Filter deposition through frozen water washing to being neutral, at 105 ℃ of dry brick-red powder 62.5g, yield is 70.2%, purity is 94.9%
Embodiment 9:
In three mouthfuls of round-bottomed flasks, add the pyrogallol (37.8g) and the oxysuccinic acid (67g) that mix, add the 100ml dioxane and the 130ml vitriol oil again; Slowly stir and heat temperature raising 90-120 ℃ gradually, reacted 50 minutes, pour in the frozen water, placed 48 hours; Deposition is filtered, and filters deposition and washs to being neutral through frozen water; At 105 ℃ of dry brick-red powder 27.1g, yield is 50.7%, and purity is 94.3%.
Embodiment 10:
In three mouthfuls of round-bottomed flasks, add the pyrogallol (50.4g) that mixes, oxysuccinic acid (67g); With the 35g anhydrous cupric sulfate, add the 140ml vitriol oil again, slowly stir and heat temperature raising 115-140 ℃ gradually, reacted 30 minutes; Pour in the frozen water, placed 48 hours, deposition is filtered; Filter deposition through frozen water washing to being neutral, at 105 ℃ of dry brick-red powder 30.6g, yield is 43%, purity is 92.1%.
Claims (4)
1. the technology of a synthetic Daphnetin may further comprise the steps: by ratio of weight and the number of copies 1: 0.8～5 pyrogallol and oxysuccinic acid are mixed, add 1～10 part the vitriol oil; Adding and vitriol oil portion rate are 0.2～2.5 part organic solvent again, slowly stir and heat temperature raising 90-140 ℃ gradually, react 10～60 minutes; Pour in the frozen water, placed 48 hours, deposition; Filter, filter deposition through the frozen water washing to being neutral, at 105 ℃ of dry brick-red powder.
2. production technique according to claim 1 is characterized in that: described organic solvent is that in dioxane, tetracol phenixin, YLENE, vinyl acetic monomer, butanone, Virahol, butanols, acetone, methylethylketone, cyclohexanone, THF, toluene, mono chloro benzene, methylene dichloride, the ethylene dichloride one or more are mixed.
3. production technique according to claim 1 is characterized in that: with weight ratio is after 1: 0.8～5 pyrogallol and oxysuccinic acid mix, and adding with vitriol oil portion rate is 0.1～10 part siccative.
4. production technique according to claim 3; It is characterized in that: described siccative is silica gel, resin, Calcium Chloride Powder Anhydrous, quicklime, Vanadium Pentoxide in FLAKES, soda-lime, the vitriol oil, molecular sieve, anhydrous calciumsulphate, anhydrous cupric sulfate, and one or more in anhydrous magnesium sulfate, the SODIUM SULPHATE ANHYDROUS 99PCT are mixed.
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| CN2006100167310A CN1827612B (en) | 2006-03-31 | 2006-03-31 | New process for synthesizing daphnetin |
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| CN2006100167310A CN1827612B (en) | 2006-03-31 | 2006-03-31 | New process for synthesizing daphnetin |
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| CN1827612B true CN1827612B (en) | 2012-05-30 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562993A (en) * | 2004-03-26 | 2005-01-12 | 吉林省西点药业科技发展股份有限公司 | New technique for synthesizing 7,8 dihydroxyl coumarin |
-
2006
- 2006-03-31 CN CN2006100167310A patent/CN1827612B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562993A (en) * | 2004-03-26 | 2005-01-12 | 吉林省西点药业科技发展股份有限公司 | New technique for synthesizing 7,8 dihydroxyl coumarin |
Non-Patent Citations (4)
| Title |
|---|
| B. Ahmed 等.Synthesis and antihepatotoxic activity of some heterocyclic compounds containing the 1,4-dioxane ring system.《Pharmazie》.2003,第58卷(第3期),173-176. * |
| B.Ahmed等.Synthesisandantihepatotoxicactivityofsomeheterocycliccompoundscontainingthe1 4-dioxane ring system.《Pharmazie》.2003 |
| John K.Macleod 等.Synthesis of Benzofuranoid Systems.V Alternative Total Synthesis of Cyperaquinones.《Aust. J. Chem.》.1978,第31卷1545-1552. * |
| Russell J. Molyneux and Leonard Jurd.The Condensation of Some Phenols with Malic Acid, Maleic Acid and Maleic Anhydride.《Aust. J. Chem》.1974,第27卷2697-2702. * |
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| CN1827612A (en) | 2006-09-06 |
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