CN109678764A - A kind of oxybenzene disulfonic acid and its calcium salt and preparation method - Google Patents
A kind of oxybenzene disulfonic acid and its calcium salt and preparation method Download PDFInfo
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
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Abstract
A kind of oxybenzene disulfonic acid preparation method includes that hydroquinone is reacted with aqueous sulfuric acid and should be generated containing phenolsulfonic acid liquid, reacts containing phenolsulfonic acid liquid with oleum and generates oxybenzene disulfonic acid；A kind of oxybenzene disulfonic acid calcium preparation method is that hydroquinone with sulfuric acid generates the liquid containing phenolsulfonic acid, the liquid containing phenolsulfonic acid and react generation with oleum and contains oxybenzene disulfonic acid liquid, contains oxybenzene disulfonic acid liquid and calcium carbonate reaction generation oxybenzene disulfonic acid calcium.It is an advantage of the invention that a kind of oxybenzene disulfonic acid preparation method and oxybenzene disulfonic acid calcium and preparation method thereof, to synthesize oxybenzene disulfonic acid and oxybenzene disulfonic acid calcium on a large scale by certain technology.
Description
Technical field
The present invention relates to the impurity oxybenzene disulfonic acids and its calcium salt and preparation method in a kind of Calcium Dobesilate preparation process.
Background technique
Calcium Dobesilate (Calcium dobesilate monohydrate) chemical name is 2,5- dihydroxy benzenes sulfonic acid
Calcium was by French Carroin company in Initial Public Offering in 1971, is clinically used as microcirculation improver, can reduce capillary
Vascular hyperpermeability reduces blood-high-viscosity, reduces blood platelet high activity, to mitigate retina exudation, bleeding, reduces micro-
Hemangioma etc. is mainly used for a variety of diseases caused by preventing and treating microcirculation obstacle.
Calcium Dobesilate preparation process is measured by the analysis of many years there are a variety of unknown impurities, it was found that a kind of new
Unknown impuritie oxybenzene disulfonic acid calcium, specific structure are as follows:
Summary of the invention
For newfound oxybenzene disulfonic acid calcium preparation method, the invention patent proposes a kind of oxybenzene disulfonic acid preparation side
Method and oxybenzene disulfonic acid calcium and preparation method thereof, to synthesize oxybenzene disulfonic acid and oxybenzene pair on a large scale by certain technology
Sulfoacid calcium.
Realizing the technical solution on foregoing invention mesh ground is, a kind of oxybenzene disulfonic acid preparation method include hydroquinone with it is aqueous
Sulfuric acid reaction should be generated containing phenolsulfonic acid liquid, reacted containing phenolsulfonic acid liquid with oleum and generated oxybenzene disulfonic acid；
Reaction equation are as follows:
Preferably, hydroquinone is added in the reactor for placing aqueous sulfuric acid 70-80 DEG C, reaction 2.5-4 hours, is obtained
Phenolsulfonic acid, phenolsulfonic acid are reacted with oleum, 100-120 DEG C of reaction temperature, reaction time 25-45 minute, dry purity
Oxybenzene disulfonic acid more than or equal to 95%.
A kind of oxybenzene disulfonic acid calcium molecular formula is C6H4CaO8S2；Molecular structure is
A kind of oxybenzene disulfonic acid calcium preparation method is that hydroquinone and sulfuric acid generate the liquid containing phenolsulfonic acid, contain hydroxyl
The liquid of benzene sulfonic acid reacts generation with oleum and contains oxybenzene disulfonic acid liquid, anti-containing oxybenzene disulfonic acid liquid and calcium carbonate
Oxybenzene disulfonic acid calcium, reaction equation should be generated are as follows:
Preferably, hydroquinone is added in the reactor for placing aqueous sulfuric acid a kind of oxybenzene disulfonic acid calcium preparation method,
It at 70-80 DEG C, reacts 2.5-4 hours, obtains containing phenolsulfonic acid liquid, phenolsulfonic acid liquid is reacted with oleum, reaction
Warm 100-120 DEG C, reaction time 25-45 minute obtains containing oxybenzene disulfonic acid liquid；
Calcium carbonate is added containing oxybenzene disulfonic acid liquid, tune pH value is 4.5-5, stirs 2-3 hours, filters, and filtrate is dense
Contracting, vacuum drying obtain white solid oxybenzene disulfonic acid calcium.
It is an advantage of the invention that having found oxybenzene disulfonic acid industrial production process, and propose that a kind of oxybenzene of high-purity is double
Sulfoacid calcium salt production process.
The structural analysis of oxybenzene disulfonic acid: nuclear magnetic resonance spectroscopy (400MHz) test shows that (see Fig. 1), compound only goes out
There are two groups of absorption peaks (9.76ppm, 2H in low field；6.82ppm, 2H), peak type be it is unimodal, do not occur splitting point, show on phenyl ring
A possibility that two hydrogen atoms are in 1/4 is larger, and structure is answered are as follows:
Carbon-13 nmr spectra (100MHz) test shows that compound only three groups of NMR signals occurs in low field, shows
Molecule has preferable symmetry, and further proving its structure is the disubstituted benzene sulfonic acid of Isosorbide-5-Nitrae-, mutually confirms with hydrogen spectrum result.
The high-resolution electrospray ionization mass spectrum test of negative ion mode shows that (see Fig. 2), the ion adduction peak of compound meets M-H
Feature, calculate C6H5O8S2=268.9426, measured value 268.9438, within the allowable range, molecular formula should be error
C6H6O8S2 meets with hydrogen spectrum analysis result.
The structural analysis of oxybenzene disulfonic acid calcium: nuclear magnetic resonance spectroscopy (400MHz) test shows that compound only goes out (see Fig. 3)
There is multiple groups coincidence absorption peak (6.92-6.77ppm, 4H) in low field, because 6.82ppm is one sharp unimodal, do not occur splitting point,
Show that a possibility that two hydrogen atoms are in 1/4 on phenyl ring is larger, structure is answered are as follows:
(note: containing ethyl alcohol in sample, in 3.44ppm and
1.05ppm；Locate appearance)
Carbon-13 nmr spectra (100MHz) test show only to occur between 114~146ppm three groups of absorption peaks (145.6,
133.2,114.4ppm), only there are three groups of NMR signals in low field in compound, shows that molecule has preferable symmetry,
Further proving its structure is the disubstituted benzene sulfonic acid of Isosorbide-5-Nitrae-, is mutually confirmed with hydrogen spectrum result, and structure and hydrogen spectrum supposition coincide；
The high-resolution electrospray ionization mass spectrum test of negative ion mode shows (100mL to be settled to water, with 0.22 μm of miillpore filter
Filtering carries out mass spectrograph and detects determining molecular weight.Mass Spectrometry Conditions: the positive/negative ion mode of full scan, scanning quality range m/z
200~1 000, resolution ratio 25 000, scanning speed 4Hz, automatic growth control (AGC) target value 10e6, spray voltage
3500V, 320 DEG C of ion transfer tube temperature, sheath gas air pressure 35au, assist gas pressure 10au, 300 DEG C of ion source temperature, 1 μ of sample volume
L obtains mass spectrogram), the ion adduction peak of compound meets the feature of M-H, calculates C6H5O8S2=268.9426, and measured value is
268.9436, within the allowable range, molecular formula should be C6H4CaO8S2 to error, meet with hydrogen spectrum analysis result.
Detailed description of the invention
Fig. 1 is oxybenzene disulfonic acid nuclear magnetic resonance spectroscopy (400MHz) test chart.
Fig. 2 is the high-resolution electrospray ionization mass spectrum test chart of oxybenzene disulfonic acid negative ion mode.
Fig. 3 is oxybenzene disulfonic acid calcium nuclear magnetic resonance spectroscopy (400MHz) test chart.
Fig. 4 is the high-resolution electrospray ionization mass spectrum test chart of oxybenzene disulfonic acid calcium negative ion mode.
Fig. 5 is the nucleus magnetic hydrogen spectrum test chart of Calcium Dobesilate.
Specific embodiment
A kind of oxybenzene disulfonic acid preparation method
Example 1, a kind of oxybenzene disulfonic acid preparation method include placing aqueous sulfuric acid (concentration being to hydroquinone to be added
85%) in reactor, reaction temperature is 70 DEG C, reacts 2.5 hours, is obtained containing phenolsulfonic acid liquid, phenolsulfonic acid and hair
Cigarette sulfuric acid reaction, 105 DEG C of reaction temperature, the reaction time 25 minutes, ethyl alcohol recrystallization was precipitated, the oxybenzene that dry purity is 95%
Disulfonic acid；
Reaction equation are as follows:
Example 2, a kind of oxybenzene disulfonic acid preparation method include placing aqueous sulfuric acid (concentration being to hydroquinone to be added
85%) in reactor, reaction temperature is 70 DEG C, reacts 3 hours, is obtained containing phenolsulfonic acid liquid, phenolsulfonic acid and smoke
Sulfuric acid reaction, 110 DEG C of reaction temperature, the reaction time 30 minutes, ethyl alcohol recrystallization was precipitated, dry that purity is double for 96% oxybenzene
Sulfonic acid, reaction equation is the same as example 1.
Example 3, a kind of oxybenzene disulfonic acid preparation method include placing aqueous sulfuric acid (concentration being to hydroquinone to be added
85%) in reactor, reaction temperature is 75 DEG C, reacts 3 hours, is obtained containing phenolsulfonic acid liquid, phenolsulfonic acid and smoke
Sulfuric acid reaction, 110 DEG C of reaction temperature, the reaction time 30 minutes, ethyl alcohol recrystallization was precipitated, the oxybenzene that dry purity is 96.3%
Disulfonic acid, reaction equation is the same as example 1.
Example 4, a kind of oxybenzene disulfonic acid preparation method include placing aqueous sulfuric acid (concentration being to hydroquinone to be added
90%) in reactor, reaction temperature is 75 DEG C, reacts 3 hours, is obtained containing phenolsulfonic acid liquid, phenolsulfonic acid and smoke
Sulfuric acid reaction, 110 DEG C of reaction temperature, the reaction time 30 minutes, ethyl alcohol recrystallization was precipitated, the oxybenzene that dry purity is 98.2%
Disulfonic acid, reaction equation is the same as example 1.
Example 5, a kind of oxybenzene disulfonic acid preparation method include placing aqueous sulfuric acid (concentration being to hydroquinone to be added
90%) in reactor, reaction temperature is 80 DEG C, reacts 3 hours, is obtained containing phenolsulfonic acid liquid, phenolsulfonic acid and smoke
Sulfuric acid reaction, 110 DEG C of reaction temperature, the reaction time 30 minutes, ethyl alcohol recrystallization was precipitated, the oxybenzene that dry purity is 99.4%
Disulfonic acid, reaction equation is the same as example 1.
Example 6, a kind of oxybenzene disulfonic acid preparation method include placing aqueous sulfuric acid (concentration being to hydroquinone to be added
90%) in reactor, reaction temperature is 80 DEG C, reacts 3 hours, is obtained containing phenolsulfonic acid liquid, phenolsulfonic acid and smoke
Sulfuric acid reaction, 110 DEG C of reaction temperature, the reaction time 40 minutes, ethyl alcohol recrystallization was precipitated, the oxybenzene that dry purity is 99.2%
Disulfonic acid, reaction equation is the same as example 1.
Example 7, a kind of oxybenzene disulfonic acid preparation method include placing aqueous sulfuric acid (concentration being to hydroquinone to be added
90%) in reactor, reaction temperature is 80 DEG C, reacts 3 hours, is obtained containing phenolsulfonic acid liquid, phenolsulfonic acid and smoke
Sulfuric acid reaction, 110 DEG C of reaction temperature, the reaction time 45 minutes, ethyl alcohol recrystallization was precipitated, the oxybenzene that dry purity is 99.2%
Disulfonic acid, reaction equation is the same as example 1.
Example 8, a kind of oxybenzene disulfonic acid preparation method include placing aqueous sulfuric acid (concentration being to hydroquinone to be added
90%) in reactor, reaction temperature is 80 DEG C, reacts 3 hours, is obtained containing phenolsulfonic acid liquid, phenolsulfonic acid and smoke
Sulfuric acid reaction, 120 DEG C of reaction temperature, the reaction time 30 minutes, ethyl alcohol recrystallization was precipitated, the oxybenzene that dry purity is 98.1%
Disulfonic acid, reaction equation is the same as example 1.
Example 9, a kind of oxybenzene disulfonic acid preparation method include placing aqueous sulfuric acid (concentration being to hydroquinone to be added
90%) in reactor, reaction temperature is 75 DEG C, reacts 2.5 hours, is obtained containing phenolsulfonic acid liquid, phenolsulfonic acid and hair
Cigarette sulfuric acid reaction, 120 DEG C of reaction temperature, the reaction time 40 minutes, ethyl alcohol recrystallization was precipitated, the hydroxyl that dry purity is 98.2%
Benzene disulfonic acid, reaction equation is the same as example 1.
Example 10, a kind of oxybenzene disulfonic acid preparation method include placing aqueous sulfuric acid (concentration being to hydroquinone to be added
90%) in reactor, reaction temperature is 75 DEG C, reacts 3 hours, is obtained containing phenolsulfonic acid liquid, phenolsulfonic acid and smoke
Sulfuric acid reaction, 120 DEG C of reaction temperature, the reaction time 45 minutes, ethyl alcohol recrystallization was precipitated, the oxybenzene that dry purity is 98.3%
Disulfonic acid, reaction equation is the same as example 1.
Example 11, a kind of oxybenzene disulfonic acid preparation method include placing aqueous sulfuric acid (concentration being to hydroquinone to be added
90%) in reactor, reaction temperature is 75 DEG C, reacts 4 hours, is obtained containing phenolsulfonic acid liquid, phenolsulfonic acid and smoke
Sulfuric acid reaction, 120 DEG C of reaction temperature, the reaction time 45 minutes, ethyl alcohol recrystallization was precipitated, the oxybenzene that dry purity is 98.3%
Disulfonic acid, reaction equation is the same as example 1.
Example 12, a kind of oxybenzene disulfonic acid preparation method include placing aqueous sulfuric acid (concentration being to hydroquinone to be added
90%) in reactor, reaction temperature is 70 DEG C, reacts 2.5 hours, is obtained containing phenolsulfonic acid liquid, phenolsulfonic acid and hair
Cigarette sulfuric acid reaction, 120 DEG C of reaction temperature, the reaction time 45 minutes, ethyl alcohol recrystallization was precipitated, the hydroxyl that dry purity is 98.8%
Benzene disulfonic acid, reaction equation is the same as example 1.
Example 13, a kind of oxybenzene disulfonic acid preparation method include placing aqueous sulfuric acid (concentration being to hydroquinone to be added
90%) in reactor, reaction temperature is 70 DEG C, reacts 3 hours, is obtained containing phenolsulfonic acid liquid, phenolsulfonic acid and smoke
Sulfuric acid reaction, 120 DEG C of reaction temperature, the reaction time 45 minutes, ethyl alcohol recrystallization was precipitated, the oxybenzene that dry purity is 98.8%
Disulfonic acid, reaction equation is the same as example 1.
Example 14, a kind of oxybenzene disulfonic acid preparation method include placing aqueous sulfuric acid (concentration being to hydroquinone to be added
90%) in reactor, reaction temperature is 70 DEG C, reacts 4 hours, is obtained containing phenolsulfonic acid liquid, phenolsulfonic acid and smoke
Sulfuric acid reaction, 120 DEG C of reaction temperature, the reaction time 40 minutes, ethyl alcohol recrystallization was precipitated, the oxybenzene that dry purity is 98.6%
Disulfonic acid, reaction equation is the same as example 1.
A kind of oxybenzene disulfonic acid calcium molecular formula is C6H4CaO8S2；Molecular structure is
A kind of oxybenzene disulfonic acid calcium preparation method
Hydroquinone is added and places aqueous sulfuric acid (concentration 85%) by example 1, a kind of oxybenzene disulfonic acid calcium preparation method
In reactor, at 70 DEG C, reacting 2.5 hours, obtain containing phenolsulfonic acid liquid, phenolsulfonic acid liquid is reacted with oleum,
100 DEG C of reaction temperature, the reaction time 25 minutes, obtains the liquid containing oxybenzene disulfonic acid；
Calcium carbonate will be added in the liquid containing oxybenzene disulfonic acid, adjusting pH value is 4.5, is stirred 2 hours, filters, will filter
Liquid concentration, vacuum drying obtain white solid oxybenzene disulfonic acid calcium (purity 90%), reaction equation are as follows:
Hydroquinone is added and places aqueous sulfuric acid (concentration 85%) by example 2, a kind of oxybenzene disulfonic acid calcium preparation method
In reactor, at 75 DEG C, reacts 3 hours, obtain containing phenolsulfonic acid liquid, phenolsulfonic acid liquid is reacted with oleum, instead
100 DEG C of temperature is answered, the reaction time 30 minutes, obtains the liquid containing oxybenzene disulfonic acid；
Calcium carbonate will be added in the liquid containing oxybenzene disulfonic acid, adjusting pH value is 4.5, is stirred 2 hours, filters, will filter
Liquid concentration, vacuum drying obtain white solid oxybenzene disulfonic acid calcium (purity 91%), and reaction equation is with example 1.
Hydroquinone is added and places aqueous sulfuric acid (concentration 90%) by example 3, a kind of oxybenzene disulfonic acid calcium preparation method
In reactor, at 75 DEG C, reacts 3 hours, obtain containing phenolsulfonic acid liquid, phenolsulfonic acid liquid is reacted with oleum, instead
100 DEG C of temperature is answered, the reaction time 30 minutes, obtains the liquid containing oxybenzene disulfonic acid；
Calcium carbonate will be added in the liquid containing oxybenzene disulfonic acid, adjusting pH value is 4.5, is stirred 2 hours, filters, will filter
Liquid concentration, vacuum drying obtain white solid oxybenzene disulfonic acid calcium (purity 92%), and reaction equation is with example 1.
Hydroquinone is added and places aqueous sulfuric acid (concentration 90%) by example 4, a kind of oxybenzene disulfonic acid calcium preparation method
In reactor, at 75 DEG C, reacts 3 hours, obtain containing phenolsulfonic acid liquid, phenolsulfonic acid liquid is reacted with oleum, instead
100 DEG C of temperature is answered, the reaction time 40 minutes, obtains the liquid containing oxybenzene disulfonic acid；
Calcium carbonate will be added in the liquid containing oxybenzene disulfonic acid, adjusting pH value is 4.5, is stirred 3 hours, filters, will filter
Liquid concentration, vacuum drying obtain white solid oxybenzene disulfonic acid calcium (purity 92%), and reaction equation is with example 1.
Hydroquinone is added and places aqueous sulfuric acid (concentration 90%) by example 5, a kind of oxybenzene disulfonic acid calcium preparation method
In reactor, at 80 DEG C, reacting 3.5 hours, obtain containing phenolsulfonic acid liquid, phenolsulfonic acid liquid is reacted with oleum,
110 DEG C of reaction temperature, the reaction time 40 minutes, obtains the liquid containing oxybenzene disulfonic acid；
Calcium carbonate will be added in the liquid containing oxybenzene disulfonic acid, adjusting pH value is 4.5, is stirred 3 hours, filters, will filter
Liquid concentration, vacuum drying obtain white solid oxybenzene disulfonic acid calcium (purity 92%), and reaction equation is with example 1.
Hydroquinone is added and places aqueous sulfuric acid (concentration 90%) by example 6, a kind of oxybenzene disulfonic acid calcium preparation method
In reactor, at 80 DEG C, reacts 4 hours, obtain containing phenolsulfonic acid liquid, phenolsulfonic acid liquid is reacted with oleum, instead
110 DEG C of temperature is answered, the reaction time 45 minutes, obtains the liquid containing oxybenzene disulfonic acid；
Calcium carbonate will be added in the liquid containing oxybenzene disulfonic acid, adjusting pH value is 5, is stirred 3 hours, is filtered, by filtrate
Concentration, vacuum drying obtain white solid oxybenzene disulfonic acid calcium (purity 92%), and reaction equation is with example 1.
Hydroquinone is added and places aqueous sulfuric acid (concentration 90%) by example 7, a kind of oxybenzene disulfonic acid calcium preparation method
In reactor, at 80 DEG C, reacts 4 hours, obtain containing phenolsulfonic acid liquid, phenolsulfonic acid liquid is reacted with oleum, instead
110 DEG C of temperature is answered, the reaction time 45 minutes, obtains the liquid containing oxybenzene disulfonic acid；
Calcium carbonate will be added in the liquid containing oxybenzene disulfonic acid, adjusting pH value is 4.5, is stirred 3 hours, filters, will filter
Liquid concentration, vacuum drying obtain white solid oxybenzene disulfonic acid calcium (purity 95%), and reaction equation is with example 1.
Hydroquinone is added and places aqueous sulfuric acid (concentration 90%) by example 8, a kind of oxybenzene disulfonic acid calcium preparation method
In reactor, at 80 DEG C, reacting 3.5 hours, obtain containing phenolsulfonic acid liquid, phenolsulfonic acid liquid is reacted with oleum,
110 DEG C of reaction temperature, the reaction time 45 minutes, obtains the liquid containing oxybenzene disulfonic acid；
Calcium carbonate will be added in the liquid containing oxybenzene disulfonic acid, adjusting pH value is 4.5, is stirred 3 hours, filters, will filter
Liquid concentration, vacuum drying obtain white solid oxybenzene disulfonic acid calcium (purity 95%), and reaction equation is with example 1.
Identify that products therefrom is oxybenzene disulfonic acid calcium through nuclear-magnetism.
Claims (5)
1. a kind of oxybenzene disulfonic acid preparation method, it is characterized in that: the preparation method includes that hydroquinone and aqueous sulfuric acid are anti-
It should should generate containing phenolsulfonic acid liquid, be reacted containing phenolsulfonic acid liquid with oleum and generate oxybenzene disulfonic acid；
Reaction equation are as follows:
2. a kind of oxybenzene disulfonic acid preparation method according to claim 1 contains it is characterized in that: hydroquinone is added to place
70-80 DEG C in the reactor of water sulfuric acid, reaction 2.5-4 hour, obtain containing phenolsulfonic acid liquid, containing phenolsulfonic acid liquid and
Oleum reaction, 100-120 DEG C of reaction temperature are reaction time 25-45 minute, dry that oxybenzene of the purity more than or equal to 95% is double
Sulfonic acid.
3. a kind of oxybenzene disulfonic acid calcium, it is characterized in that: the oxybenzene disulfonic acid calcium molecular formula is C6H4CaO8S2；Molecular structure is
4. a kind of oxybenzene disulfonic acid calcium preparation method, it is characterized in that: the method is that hydroquinone and sulfuric acid generation contain oxybenzene
Sulfonic acid liquid reacts generation with oleum containing oxybenzene disulfonic acid liquid containing phenolsulfonic acid liquid, contains oxybenzene disulfonic acid
Liquid and calcium carbonate reaction generate oxybenzene disulfonic acid calcium, reaction equation are as follows:
5. a kind of oxybenzene disulfonic acid calcium preparation method according to claim 4 is placed it is characterized in that: hydroquinone is added
In the reactor of aqueous sulfuric acid, at 70-80 DEG C, react 2.5-4 hour, obtain the liquid containing phenolsulfonic acid, phenolsulfonic acid and
Oleum reaction, 100-120 DEG C of reaction temperature, reaction time 25-45 minute obtains the liquid containing oxybenzene disulfonic acid；
Calcium carbonate is added in liquid containing oxybenzene disulfonic acid, and tune pH value is 4.5-5, stirs 2-3 hours, filters, filtrate is concentrated,
Vacuum drying obtains white solid oxybenzene disulfonic acid calcium.
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Cited By (5)
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| CN110885300A (en) * | 2019-12-25 | 2020-03-17 | 江西博雅欣和制药有限公司 | Synthetic process of hydroxybenzene sulfonate compound |
| CN110981763A (en) * | 2019-12-25 | 2020-04-10 | 湖北欣泽霏药业有限公司 | Hydroxy benzene sulfonate compound and preparation method thereof |
| CN110981762A (en) * | 2019-12-25 | 2020-04-10 | 湖北欣泽霏药业有限公司 | 2, 5-dihydroxy benzene sulfonate compound and preparation method thereof |
| CN111018749A (en) * | 2019-12-31 | 2020-04-17 | 成都平和安康医药科技有限公司 | Phenolsulam and calcium dobesilate impurities as well as preparation method and application thereof |
| CN114539101A (en) * | 2020-11-26 | 2022-05-27 | 南京长澳医药科技有限公司 | Method for preparing calcium dobesilate genotoxic impurities |
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| CN110885300A (en) * | 2019-12-25 | 2020-03-17 | 江西博雅欣和制药有限公司 | Synthetic process of hydroxybenzene sulfonate compound |
| CN110981763A (en) * | 2019-12-25 | 2020-04-10 | 湖北欣泽霏药业有限公司 | Hydroxy benzene sulfonate compound and preparation method thereof |
| CN110981762A (en) * | 2019-12-25 | 2020-04-10 | 湖北欣泽霏药业有限公司 | 2, 5-dihydroxy benzene sulfonate compound and preparation method thereof |
| CN111018749A (en) * | 2019-12-31 | 2020-04-17 | 成都平和安康医药科技有限公司 | Phenolsulam and calcium dobesilate impurities as well as preparation method and application thereof |
| CN114539101A (en) * | 2020-11-26 | 2022-05-27 | 南京长澳医药科技有限公司 | Method for preparing calcium dobesilate genotoxic impurities |
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