CN108440286A - A kind of method for preparing acetylsalicylic acid - Google Patents
A kind of method for preparing acetylsalicylic acid Download PDFInfo
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- CN108440286A CN108440286A CN201810348975.1A CN201810348975A CN108440286A CN 108440286 A CN108440286 A CN 108440286A CN 201810348975 A CN201810348975 A CN 201810348975A CN 108440286 A CN108440286 A CN 108440286A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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Abstract
The invention discloses a kind of method for preparing acetylsalicylic acid, include the following steps：By salicylic acid, acetic anhydride and SO4 2‐/ZrO2After@GO mixing, it is reacted 4~10 hours at 60~70 DEG C, it is then fed into rectifying in rectifying column and recycles unreacted acetic anhydride, then plus elutriation is brilliant, then acetyl salicylic acid crude is recrystallized to give acetylsalicylic acid with ethyl alcohol and water mixed solvent, the method of the invention is simple, at low cost, equipment nocuity is small and non-environmental-pollution, passes through the conditions such as catalyst and reaction temperature, reaction time of optimization, so that the dosage of catalyst is few, and it is greatly improved the yield of product.
Description
Technical field
The present invention relates to organic chemical industry field, especially a kind of method for preparing acetylsalicylic acid.
Background technology
Acetylsalicylic acid also known as aspirin, aspirin are a kind of time-honored analgesic-antipyretic, are born in 1899
On March 6, in.For curing cold, generating heat, have a headache, have a toothache, arthralgia, rheumatism, moreover it is possible to inhibit platelet aggregation, for preventing
With treatment ischemic heart disease, angina pectoris, cardiopulmonary infraction, cerebral thrombosis, it is applied to revascularization and bypass grafting
Effectively.Not only there is purposes medically over 100 years, and also has extensive use in other field.It is that salicylic acid is antipyretic, town
The representative of pain medicine, for clinical existing one-hundred-year history.It is white needles or plate crystal or powder, 135 DEG C of fusing point, no gas
Taste, micro-strip tart flavour are stablized in dry air, salicylic acid and acetic acid are slowly hydrolyzed into humid air, can be dissolved in ethyl alcohol, second
Ether and chloroform, are slightly soluble in water, can be dissolved in sodium hydroxide solution or sodium carbonate liquor, but decompose simultaneously.
Classical preparation method is that bigcatkin willow acylating acid is made under sulfuric acid catalysis with acetic anhydride or chloroacetic chloride, the technique at
Ripe, yield is 60% or so, but side reaction is more, and equipment seriously corroded seriously pollutes environment.To develop raw catelyst, try out
P-methyl benzenesulfonic acid, niter cake etc., but repetitive cycling performance is poor.Thus find a new class of catalytic activity height, environment-friendly type
Catalyst come replace it is Protic Acid Catalyzed synthesis acetylsalicylic acid have become people research new issue.
Green synthesis process refers to using high activity and highly selective environmentally friendly catalyst, is reduced from source
The generation of poisonous and harmful by-product, to achieve the purpose that clean manufacturing.Solid super acid catalyst is in the mid 1970s
It is found and is studied, there is very wide prospects for commercial application because it is acid by force, activity is high, pollution is small, selectivity is good.
Solid super-strong acid overcomes the shortcomings that liquid strong acid, and catalyst is easily detached with liquid-phase reaction system, recyclable reuse.Cause
Solid super acid catalyst can be formed acetylsalicylic acid green synthesis process by this for salicylic acid acetylation, this has caused state
Inside and outside scholar more and more pays close attention to.
Acetylsalicylic acid synthesis technology is existing in recent years to apply SO4 2‐The report of/MxOy type solid super acid catalysts, but
In liquid-solid reaction system, SO4 2‐The sulfate radical of/MxOy type catalyst surfaces can be dissolved out slowly, and acid strength is made to be substantially reduced, and be lost
Speed living is accelerated, and thermal stability is bad, therefore commercial Application is limited to.And in heterogeneous catalytic reaction, the eighties in last century
The load oxide type solid super-strong acid (WO that later stage occurs3/ZrO2) its active component then not easily runs off, in solution and reproducibility
It is significantly better than that other same type solid catalysts in atmosphere and to the stability of heat, thus the solid super-strong acid is once occurring just
Cause people's great interest, people are to WO3/ZrO2The research work of catalyst preparation and catalytic performance etc. shows it to being permitted
More acid catalyzed reactions all have very high catalytic activity and selectivity, and the research and application of such solid super-strong acid, which just become, to be sought
One of the major domain of new green environment protection type catalyst.
Invention content
Present invention aims at propose a kind of environmentally protective acetylsalicylic acid synthetic method.
Technical scheme of the present invention includes the following steps：By salicylic acid, acetic anhydride and SO4 2‐/ZrO2@GO solid super-strong acids
In the reactor of catalyst, controlling reaction temperature is 60~70 DEG C, the filtering and removing solid superacid as catalyst first to the end of reaction
Agent is then fed into rectifying in rectifying column and recycles unreacted acetic anhydride, and distillation residual liquid adds water to stand cooling, and white crystal is precipitated,
It is cooled to and is fully crystallized with ice water；By white crystal through filtering, cold water washing obtains acetyl salicylic acid crude；By acetyl salicylic
Acid crude is recrystallized to give acetylsalicylic acid with ethyl alcohol and water mixed solvent.
The molar ratio of the salicylic acid and acetic anhydride is 1:2~3；The salicylic acid and SO4 2‐/ZrO2@GO solid super-strong acids
The mass ratio of catalyst is 70~80:1.The time of reaction is 4~10 hours, preferably 5~6 hours.Recrystallization ethyl alcohol used
Volume ratio with the in the mixed solvent second alcohol and water of water is 5~15: 1.
The SO that the present invention uses4 2‐/ZrO2The preparation method of@GO solid super-strong acids, includes the following steps：
I, graphite raw material, solvent and oxidant are uniformly mixed, are placed in closed reaction vessel, stirred at 40~120 DEG C
0.5~6h of reaction is mixed, decompression filters, after washing, by the vacuum drying of overanxious object, grinding；Product after drying is dispersed in
In deionized water, spray drying is graphene oxide, and by graphene oxide ultrasonic disperse in deionized water, reducing agent is added
After carrying out reduction reaction, graphene is made in washing and drying treatment.
II, by a certain amount of ZrCl4 and cetyl trimethylammonium bromide, be dissolved in absolute ethyl alcohol respectively, be mixed
Then the H of a concentration of 1.05mol/L is added in 1.5h2SO4With the HCl mixed solutions of 2.05mol/L, be eventually adding 1 part through upper
The graphene that I is obtained is stated, is stirred evenly at 35~40 DEG C, and 5h is heated at 115 DEG C, is cooled to room temperature through conventional side
Method washing filters, is dry, after roasting, obtains with SO4 2‐/ZrO2@GO super-strong acid mesoporous materials.
Step I) described in graphite raw material be crystalline flake graphite, graphite powder or expanded graphite.The solvent is the concentrated sulfuric acid, dense sulphur
The weight ratio of acid and graphite raw material is 10~50:1.The oxidant is potassium permanganate, the potassium permanganate and graphite raw material
Weight ratio is 3~8:1；The reducing agent is NaOH, KOH or hydrazine hydrate.The mass ratio of reducing agent and graphene oxide is 1~4:
1。
Compared with prior art, beneficial effects of the present invention are：The method of the invention is simple, at low cost, equipment injury
Property small and non-environmental-pollution, by optimize the conditions such as catalyst and reaction temperature, reaction time so that the dosage of catalyst
It is few, and it is greatly improved the yield of product.
Specific implementation mode
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
The every other embodiment that art personnel are obtained without making creative work belongs to the model that the present invention protects
It encloses.
【Embodiment 1】
I, take 1 part of graphite powder mixed as graphite raw material and 10 parts of concentrated sulfuric acids and 3 parts of potassium permanganate
Close uniform, be placed in closed reaction vessel, 6h is stirred to react under 40 DEG C of condition of water bath heating, through decompression, suction filtration,
After washing, by the vacuum drying of overanxious object, grinding.Product ultrasonic disperse after drying and grinding is sprayed in 10 parts of deionized waters and is done
It is dry to take 1 part of graphene oxide ultrasonic disperse in deionized water up to graphene oxide, 1 part of reducing agent NaOH is added and is gone back
After original reaction, the solution after reduction reaction is filtered, filtrate is taken do microwave heating treatment, handles postcooling pickling, water washed
Filter, filtrate drying are graphene..
II, by 1 part of ZrCl4 and 2 part of cetyl trimethylammonium bromide, be dissolved in respectively in 10 parts of absolute ethyl alcohols, mix
Stirring 1.5h is closed, the H of a concentration of 1.05mol/L is then added2SO4With the HCl mixed solutions of 2.05mol/L, it is eventually adding 1 part
The graphene obtained through above-mentioned I, stir evenly, and 5h is heated at 115 DEG C, be cooled to room temperature by normal at 35~40 DEG C
The method washing of rule filters, is dry, after roasting, obtains with SO4 2‐/ZrO2@GO super-strong acid mesoporous materials I, the number are
Parts by weight.
【Embodiment 2】
I, take 1 part of crystalline flake graphite mixed as graphite raw material and 10 parts of concentrated sulfuric acids and 3 parts of potassium permanganate
Close uniform, be placed in closed reaction vessel, 6h is stirred to react under 40 DEG C of condition of water bath heating, through decompression, suction filtration,
After washing, by the vacuum drying of overanxious object, grinding.Product ultrasonic disperse after drying and grinding is sprayed in 10 parts of deionized waters and is done
It is dry to take 1 part of graphene oxide ultrasonic disperse in deionized water up to graphene oxide, 1 part of reducing agent NaOH is added and is gone back
After original reaction, the solution after reduction reaction is filtered, filtrate is taken do microwave heating treatment, handles postcooling pickling, water washed
Filter, filtrate drying are graphene..
II, by 1 part of ZrCl4 and 2 part of cetyl trimethylammonium bromide, be dissolved in respectively in 10 parts of absolute ethyl alcohols, mix
Stirring 1.5h is closed, the H of a concentration of 1.05mol/L is then added2SO4With the HCl mixed solutions of 2.05mol/L, it is eventually adding 1 part
The graphene obtained through above-mentioned I, stir evenly, and 5h is heated at 115 DEG C, be cooled to room temperature by normal at 35~40 DEG C
The method washing of rule filters, is dry, after roasting, obtains with SO4 2‐/ZrO2@GO super-strong acid mesoporous materials II, the number are
Parts by weight.
【Embodiment 3】
I, take 1 part of expanded graphite graphite raw material and 10 parts of concentrated sulfuric acids and 3 parts of potassium permanganate mixed
Close uniform, be placed in closed reaction vessel, 6h is stirred to react under 40 DEG C of condition of water bath heating, through decompression, suction filtration,
After washing, by the vacuum drying of overanxious object, grinding.Product ultrasonic disperse after drying and grinding is sprayed in 10 parts of deionized waters and is done
It is dry to take 1 part of graphene oxide ultrasonic disperse in deionized water up to graphene oxide, 1 part of reducing agent NaOH is added and is gone back
After original reaction, the solution after reduction reaction is filtered, filtrate is taken do microwave heating treatment, handles postcooling pickling, water washed
Filter, filtrate drying are graphene..
II, by 1 part of ZrCl4 and 2 part of cetyl trimethylammonium bromide, be dissolved in respectively in 10 parts of absolute ethyl alcohols, mix
Stirring 1.5h is closed, the H of a concentration of 1.05mol/L is then added2SO4With the HCl mixed solutions of 2.05mol/L, it is eventually adding 1 part
The graphene obtained through above-mentioned I, stir evenly, and 5h is heated at 115 DEG C, be cooled to room temperature by normal at 35~40 DEG C
The method washing of rule filters, is dry, after roasting, obtains with SO4 2‐/ZrO2@GO super-strong acid mesoporous materials III, the number
For parts by weight.
【Embodiment 4】
Example 1 in molar ratio:1.2 salicylic acid, acetic anhydride are added in reactor, and it is made to be then respectively adding embodiment 1-3
Standby SO4 2‐/ZrO2@GO solid super acid catalysts, catalyst charge are the 1/70 of salicylic acid weight, controlling reaction temperature
It is 70 DEG C, reacts 5 hours, the filtering and removing solid super acid catalyst first to the end of reaction is then fed into rectifying in rectifying column
Unreacted acetic anhydride is recycled, distillation residual liquid adds water to stand cooling, and white crystal is precipitated, is cooled to and is fully crystallized with ice water；It will
White crystal obtains acetyl salicylic acid crude through filtering, cold water washing；It is 10 by acetyl salicylic acid crude volume ratio:1
Ethyl alcohol and water mixed solvent are recrystallized to give acetylsalicylic acid, and experimental result is listed in table 1.
Table 1
Above description has fully disclosed the specific implementation mode of the present invention.It should be pointed out that being familiar with the field
Technical staff is to any change for being done of specific implementation mode of the present invention all without departing from the range of claims of the present invention.
Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.
Claims (7)
1. a kind of method for preparing acetylsalicylic acid, it is characterised in that：By salicylic acid, acetic anhydride and SO4 2‐/ZrO2@GO solids are super
In the reactor of strong acid catalyst, controlling reaction temperature is 60~70 DEG C, the filtering and removing solid super-strong acid first to the end of reaction
Catalyst is then fed into rectifying in rectifying column and recycles unreacted acetic anhydride, and distillation residual liquid adds water to stand cooling, and it is brilliant that white is precipitated
Body is cooled to ice water and is fully crystallized；By white crystal through filtering, cold water washing obtains acetyl salicylic acid crude；By acetyl water
Poplar acid crude is recrystallized to give acetylsalicylic acid with ethyl alcohol and water mixed solvent.
2. method for preparing acetylsalicylic acid according to claim 1, which is characterized in that the salicylic acid and acetic anhydride
Molar ratio is 1:2~3；The salicylic acid and SO4 2‐/ZrO2The mass ratio of@GO solid super acid catalysts is 70~80:1.
3. method for preparing acetylsalicylic acid according to claim 1, which is characterized in that the time of reaction is 4~10 small
When, preferably 5~6 hours, the volume ratio for recrystallizing the in the mixed solvent second alcohol and water of second alcohol and water used was 5~15: 1.
4. method for preparing acetylsalicylic acid according to claim 3, which is characterized in that the SO4 2‐/ZrO2@GO solids
The preparation method of super acids, includes the following steps：
I, graphite raw material, solvent and oxidant are uniformly mixed, are placed in closed reaction vessel, stirred at 40~120 DEG C anti-
0.5~6h, decompression is answered to filter, after washing, by the vacuum drying of overanxious object, grinding；By the product after drying be dispersed in from
In sub- water, spray drying is graphene oxide, by graphene oxide ultrasonic disperse in deionized water, reducing agent is added and carries out
After reduction reaction, graphene is made in washing and drying treatment；
II, by a certain amount of ZrCl4 and cetyl trimethylammonium bromide, be dissolved in absolute ethyl alcohol respectively, be mixed 1.5h,
Then the H of a concentration of 1.05mol/L is added2SO4With the HCl mixed solutions of 2.05mol/L, it is eventually adding 1 part and is obtained through above-mentioned I
The graphene arrived stirs evenly at 35~40 DEG C, and heats 5h at 115 DEG C, be cooled to room temperature by conventional method washing,
It filters, is dry, after roasting, obtaining with SO4 2‐/ZrO2@GO super-strong acid mesoporous materials.
5. method for preparing acetylsalicylic acid according to claim 4, it is characterised in that：Step I) described in graphite raw material
For crystalline flake graphite, graphite powder or expanded graphite, the solvent is the concentrated sulfuric acid, the weight ratio of the concentrated sulfuric acid and graphite raw material is 10~
50:1。
6. method for preparing acetylsalicylic acid according to claim 4, it is characterised in that：The oxidant is permanganic acid
The weight ratio of potassium, the potassium permanganate and graphite raw material is 3~8:1.
7. method for preparing acetylsalicylic acid according to claim 4, it is characterised in that：The reducing agent is NaOH, KOH
Or hydrazine hydrate, the mass ratio of reducing agent and graphene oxide is 1~4:1.
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| CN201810348975.1A CN108440286A (en) | 2018-04-18 | 2018-04-18 | A kind of method for preparing acetylsalicylic acid |
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| CN201810348975.1A CN108440286A (en) | 2018-04-18 | 2018-04-18 | A kind of method for preparing acetylsalicylic acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110156602A (en) * | 2019-05-15 | 2019-08-23 | 华南理工大学 | A kind of aspirin crystal and its method for crystallising and application |
| CN114891048A (en) * | 2022-05-16 | 2022-08-12 | 浙江晟格生物科技有限公司 | Method for preparing 1-oxygen-fluoro-2, 3, 5-trioxybenzoyl-L-ribose |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104386679A (en) * | 2014-11-13 | 2015-03-04 | 苏州经贸职业技术学院 | Method for preparing graphene oxide and graphene |
-
2018
- 2018-04-18 CN CN201810348975.1A patent/CN108440286A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104386679A (en) * | 2014-11-13 | 2015-03-04 | 苏州经贸职业技术学院 | Method for preparing graphene oxide and graphene |
Non-Patent Citations (1)
| Title |
|---|
| 李耀宗等: "固体超强酸SO42-/ZrO2催化合成乙酰水杨酸", 《中国实用医药》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110156602A (en) * | 2019-05-15 | 2019-08-23 | 华南理工大学 | A kind of aspirin crystal and its method for crystallising and application |
| CN110156602B (en) * | 2019-05-15 | 2021-09-21 | 华南理工大学 | Aspirin crystal and crystallization method and application thereof |
| CN114891048A (en) * | 2022-05-16 | 2022-08-12 | 浙江晟格生物科技有限公司 | Method for preparing 1-oxygen-fluoro-2, 3, 5-trioxybenzoyl-L-ribose |
| CN114891048B (en) * | 2022-05-16 | 2024-03-26 | 浙江晟格生物科技有限公司 | Method for preparing 4-fluoro-2, 3, 5-tri-oxo-benzoyl-beta-L-ribofuranose |
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