CN106892895A - A kind of preparation method of 2 acetyl thiophene - Google Patents
A kind of preparation method of 2 acetyl thiophene Download PDFInfo
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- CN106892895A CN106892895A CN201710128526.1A CN201710128526A CN106892895A CN 106892895 A CN106892895 A CN 106892895A CN 201710128526 A CN201710128526 A CN 201710128526A CN 106892895 A CN106892895 A CN 106892895A
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- thiophene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A kind of preparation method of 2 acetyl thiophene, the preparation method is that thiophene, acetic anhydride and catalyst first are added into reaction kettle for reaction, then direct rectifying obtains product, and the remaining substrate of reactor is used for next batch reaction, and next batch reaction no longer needs to add catalyst.This method realizes recycling for catalyst during the course of the reaction, not only reduces production cost, reduces technical process, and makes non-waste-emission in whole production process, realizes the green production of 2 acetyl thiophenes.
Description
Technical field
The present invention relates to a kind of 2- acetyl thiophenes preparation method, especially first thiophene, acetic anhydride and catalyst are added instead
Reaction in kettle is answered, then direct rectifying obtains a kind of 2- acetyl thiophene preparation methods of green of product.
Background technology
2- acetyl thiophenes are important industrial chemicals intermediates, in biological medicine, agricultural chemicals, macromolecular material and conductive material
Etc. aspect be widely used.
Medical domain：It is the intermediate 2- thiophene second for synthesizing broad spectrum antibiotic cefoxitin, cefaloridine and Cefoxitin
Acid, non-steroidal anti-inflammatory analgesics Tiaprofenic Acid and 2- acetyl thiophenes azine and its transition metal Cu2+ with antitumor activity,
The important source material of Fe2+ complexs etc..
Chemical field：It is important chemical reagent；Due to its gas-chromatography peak and pharmaceutical intermediate 3- thiophenecarboxaldehydes
Peak value is closer to, therefore can be used to the internal standard compound for making to determine 3- thiophenecarboxaldehydes；It is also synthesis organic intermediate thiophene chalcone
Important source material.
Field of food：Food aromatizing agent is widely used as by foreign countries due to the taste of its special similar onion.
Just there are the synthesis of document report 2- acetyl thiophenes in foreign countries successively：
Howard D.Hartough etc. are by 168g thiophene and the zinc chloride of 95% acetic anhydride 107g and 4g molten（ZnCl2）
94-103 DEG C of heating 4h, obtains 87% 2- acetyl thiophenes.
The reaction of the 2mol thiophene such as Howard D.Hartough, the acetic anhydride of 1mol95% and 50g superfiltrols can obtain 72%
2- acetyl thiophenes, when making catalyst with the solution containing 13% superfiltrol, yield increases to 82%, and being catalyzed with SiO2-Al2O3 to obtain
84% 2- acetyl thiophenes.
Ted R. Norton are by the copolymer sulphur of PhCH=CH284%, EtC6H4CH=CH28% and C6H4 (CH=CH2) 28%
Change and cationic ion-exchange resin particle catalyst is obtained, 51 g acetic anhydrides, 126 g thiophene and 0.5 g catalyst, 96 DEG C of stirrings
Flow back 15 min, cooling, filters catalyst, and filtrate distillation must reclaim thiophene and 85.2% 2- acetyl thiophenes.
Thiophene and the acetic anhydride backflow 0.5h of 20% excess that G.N.Dorofeen co etc. will be catalyzed with Mg (ClO4) 2, obtain
The 2- acetyl thiophenes of 90%-95%.
With 2mLHClO4 be catalyzed for 84g thiophene and 155g acetic anhydrides by Michel Sy etc., and 54 DEG C of reaction 2h, mixture is poured into
In mixture of ice and water, oil reservoir is poured out, and water layer is extracted with CH2Cl2, obtains 2- acetyl thiophenes, yield 85%.
The catalyst that Guo Haifeng is used is molecular sieve carried phosphotungstate（Phosphotungstic acid is loaded on aluminum nitrate）, optimum response bar
Part is 85 DEG C of reaction temperature, and reaction time 4h, catalyst quality fraction 3.0%-3.5%, catalyst reuse number of times 3 times, three
Secondary product yield is more than 85%.
G.STADNIKOV etc. has found, in butter of tin（SnCl4）In the presence of, thiophene can be acylated immediately.
YAl. GOLDFARB is reacted with 1 mol thiophene, 1 mol chloroacetic chlorides and 0.5 mol SnCl4, and product yield is
96%。
But these process routes use soda acid and organic solvent solution because a large amount of, a large amount of trade effluents, environmental protection pressure are produced
Power is larger.
Therefore it provides a kind of synthetic method of the 2- acetyl thiophenes of environmental protection is the responsibility of those skilled in the art,
Be prepare 2- acetyl thiophenes in the urgent need to.
The content of the invention
It is an object of the invention to provide a kind of 2- acetyl thiophenes preparation method, to reduce the influence to environment, and it is adapted to work
Industryization is mass produced.
A kind of 2- acetyl thiophenes preparation method provided by the present invention, the preparation method be first by thiophene, acetic anhydride and
Catalyst is added in reactor, and 70-80 DEG C is reacted 3-5 hours, and then direct rectifying obtains product；The reactor bottom for being remained
Thing, can directly cover for next group reaction, and next batch reaction no longer needs to add catalyst.
In a preferred embodiment of the invention, the 2- acetyl thiophenes preparation method is in solvent-free or organic solvent
In, thiophene is reacted with acetic anhydride.This reaction can be without solvent, and having can be with thiophene, acetic anhydride, second
The halogenated hydrocarbons such as acid, dichloromethane, chloroform, 1,2- dichloroethanes are reacted as solvent, preferably do not use solvent.
In a preferred embodiment of the invention, thiophene is matched somebody with somebody with feeding intake for acetic anhydride in the 2- acetyl thiophenes preparation method
Than for：Arbitrary proportion, wherein being preferably：1:1.0-1:1.1.
In a preferred embodiment of the invention, methods described further includes subsequent following steps：Reaction temperature is
10 degree to 120 DEG C, more preferably reaction temperature is：60-100 DEG C, most preferably reaction is 70-80 DEG C.
In a preferred embodiment of the invention, methods described further includes subsequent following steps：Previous batch reaction
The kettle residue that thing is completed after distillation can be directly covered for next group reaction, and no longer needs addition another in next batch reaction
Outer catalyst.
Above-mentioned preparation method is reacted during thiophene, acetic anhydride and catalyst first are added into reactor, then direct rectifying
Obtain product, the product meets product quality indicator requirement through researching and analysing, and whole invention process operation is easy, yield compared with
It is high；Remaining substrate is directly covered for next group reaction, and next batch reaction no longer adds catalyst, it is to avoid the product of a large amount of waste liquids
The pollution of raw and environment, and the production cost of product is significantly reduced, it is especially suitable for industrialization large-scale production.
Brief description of the drawings
Fig. 1 is 2- acetyl thiophene structure charts prepared by this method.
Specific embodiment
In the present invention, if without particularly illustrating, percentage（%）Or part all refers to the weight relative to composition
Percentage or weight portion.
In the present invention, if without particularly illustrating, involved each component or its preferred ingredient can be mutually combined
Form new technical scheme.
In the present invention, if without particularly illustrating, all implementation methods mentioned in this article and the side of being preferable to carry out
Formula can be mutually combined to form new technical scheme.
In the present invention, if without particularly illustrating, all technical characteristics mentioned in this article and preferred feature can
New technical scheme is formed to be mutually combined.
In the present invention, if without opposite explanation, the content sum of each component is 100% in composition.
In the present invention, if without opposite explanation, the number sum of each component can be 100 weight in composition
Part.
In the present invention, unless otherwise indicated, number range " a-b " represents the contracting of any real combinings between a to b
Sketch form shows that wherein a and b is real number.Such as number range " 0-5 " represented and all listed herein between " 0-5 "
Whole real numbers, " 0-5 " is that the breviary of these combinations of values is represented.
In the present invention, unless otherwise indicated, integer number range " a-b " represents the arbitrary integer combination between a to b
Breviary represent that wherein a and b is integer.For example integer number range " 1-N " represents 1,2 ... N, and wherein N is integer.
In the present invention, unless otherwise indicated, the multicomponent mixture of " its combination " described each element of expression, such as two
Kind, three kinds, four kinds and the multicomponent mixture until maximum possible.
If be not specifically stated, the term " one kind " used by this specification refers to " at least one ".
If be not specifically stated, percentage of the present invention（Including percetage by weight）Benchmark be all the combination
The gross weight of thing.
" scope " disclosed herein is in the form of lower and upper limit.One or more lower limits, and one can be respectively
Or multiple upper limits.Given range is defined by selecting a lower limit and a upper limit.Selected lower and upper limit limit
The border of special scope is determined.All scopes that can be defined by this way comprising and can be combined, i.e., any lower limit
Can combine to form a scope with any upper limit.For example, the scope of 60-120 and 80-110 is listed for special parameter,
The scope for being interpreted as 60-110 and 80-120 is also what is expected.If additionally, the minimum zone value 1 and 2 listed, and if
Maximum magnitude value 3,4 and 5 is listed, then following scope can be expected all：1-3,1-4,1-5,2-3,2-4 and
2-5.
Herein, unless otherwise indicated, the ratio or weight of each component all refer to dry weight.
One aspect of the present invention provides a kind of 2- acetyl thiophene preparation methods of green, the described method comprises the following steps：
First by thiophene, acetic anhydride and catalyst addition reactor, 70-80 DEG C is reacted 3-5 hours, and then direct rectifying is produced
Product.The reaction bottoms for being remained, can directly cover for next group reaction, and next batch reaction no longer needs to add catalyst.
In a preferred embodiment of the invention, the 2- acetyl thiophenes preparation method is in solvent-free or organic solvent
In, thiophene is reacted with acetic anhydride.This reaction can be without solvent, and having can be with thiophene, acetic anhydride, second
The halogenated hydrocarbons such as acid, dichloromethane, chloroform, 1,2- dichloroethanes are reacted as solvent, preferably do not use solvent.
In a preferred embodiment of the invention, thiophene is matched somebody with somebody with feeding intake for acetic anhydride in the 2- acetyl thiophenes preparation method
Than for：Arbitrary proportion, wherein being preferably：1∶1.0-1∶1.1.
In a preferred embodiment of the invention, methods described further includes subsequent following steps：Reaction temperature is
10 degree to 120 DEG C, more preferably reaction temperature is：60-100 DEG C, most preferably reaction is 70-80 DEG C.
In a preferred embodiment of the invention, methods described further includes subsequent following steps：Previous batch reaction
The kettle residue that thing is completed after distillation can be directly covered for next group reaction, and no longer needs addition another in next batch reaction
Outer catalyst
Detailed description is of the invention by the following examples, but what following examples were merely exemplary, the scope of the present invention is simultaneously
It is not limited to this.
Embodiment 1
And see accompanying drawing 1, by thiophene（84kg, purity 99%, ShanXi HengQiang Chemical Co., Ltd. provides）And acetic anhydride（102kg,）Plus
Enter reactor, add phosphoric acid 500g, be heated to 70-80 DEG C, react 2-3 hours.GC detections have been reacted, rectifying, according to fraction
Boiling point collect product.2- acetyl thiophenes 118kg is obtained（94% yield）.
Distillation is finished, and thiophene is thrown again toward reactor is interior（84kg, purity 99%, ShanXi HengQiang Chemical Co., Ltd. provides）With
Acetic anhydride（102kg,）Reactor is added, 70-80 DEG C is heated to, reacted 2-3 hours.GC detections have been reacted, rectifying, according to fraction
Boiling point collect product.2- acetyl thiophenes 120kg is obtained（95% yield）.GC：99.95%.
Embodiment 2
By thiophene（84kg, purity 99%, ShanXi HengQiang Chemical Co., Ltd. provides）, acetic anhydride（102kg,）And acetic acid（100kg）
Reactor is added, phosphoric acid 500g is added, 70-80 DEG C is heated to, reacted 2-3 hours.GC detections have been reacted, rectifying, according to evaporating
The boiling point of part collects product.2- acetyl thiophenes 119kg is obtained（95% yield）.
Distillation is finished, and thiophene is thrown again toward reactor is interior（84kg, purity 99%, ShanXi HengQiang Chemical Co., Ltd. provides）, second
Acid anhydrides（102kg,）And acetic acid（100kg）Reactor is added, 70-80 DEG C is heated to, reacted 2-3 hours.GC detections have been reacted, essence
Evaporate, the boiling point according to fraction collects product.2- acetyl thiophenes 120kg is obtained（95% yield）.GC：99.95%.
Claims (6)
1. a kind of preparation method of 2- acetyl thiophenes, the preparation method is first to add thiophene, acetic anhydride and catalyst to react
In kettle, 60-100 DEG C is reacted 3-5 hours, and then direct rectifying obtains product；It is anti-that the reaction bottoms for being remained is used for next group
Should, and next batch reaction no longer needs addition catalyst.
2. preparation method as claimed in claim 1, the preparation method be in solvent-free or organic solvent, by thiophene with
Acetic anhydride is reacted.
3. preparation method as claimed in claim 2, the thiophene is with the charge ratio of acetic anhydride：1: 1.0~1: 1.1.
4. preparation method as claimed in claim 1, the thiophene, acetic anhydride and catalyst add the reaction temperature in reactor
It is further 70-80 DEG C.
5. preparation method as claimed in claim 1, side's catalyst is the stoichiometric 0.1%-100% of material.
6. preparation method as claimed in claim 5, side's catalyst is that material chemical equivalent is further 5%-10%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710128526.1A CN106892895A (en) | 2017-03-06 | 2017-03-06 | A kind of preparation method of 2 acetyl thiophene |
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| CN201710128526.1A CN106892895A (en) | 2017-03-06 | 2017-03-06 | A kind of preparation method of 2 acetyl thiophene |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111440140A (en) * | 2020-05-27 | 2020-07-24 | 甘肃盛世恒百药业有限公司 | Green process for synthesizing 2-acetylthiophene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544432A (en) * | 2003-11-27 | 2004-11-10 | 北京石油化工学院 | 2-acetyl thiophene synthetic method using thiophene in crude benzene as material |
| CN1660497A (en) * | 2004-12-30 | 2005-08-31 | 浙江工业大学 | Application of cesium phosphotungstic acid as catalyst for synthesizing acetyl thiophene |
| JP2012119195A (en) * | 2010-12-01 | 2012-06-21 | National Institute For Materials Science | Metal complex, dye-sensitized oxide semiconductor electrode, and dye-sensitized solar battery |
-
2017
- 2017-03-06 CN CN201710128526.1A patent/CN106892895A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544432A (en) * | 2003-11-27 | 2004-11-10 | 北京石油化工学院 | 2-acetyl thiophene synthetic method using thiophene in crude benzene as material |
| CN1660497A (en) * | 2004-12-30 | 2005-08-31 | 浙江工业大学 | Application of cesium phosphotungstic acid as catalyst for synthesizing acetyl thiophene |
| JP2012119195A (en) * | 2010-12-01 | 2012-06-21 | National Institute For Materials Science | Metal complex, dye-sensitized oxide semiconductor electrode, and dye-sensitized solar battery |
Non-Patent Citations (2)
| Title |
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| ALVIN I.KOSAK等: "2-Acetothienone", 《ORGANIC SYNTHESES》 * |
| 王登玉等: "超声波作用下合成2-乙酰噻吩", 《辽宁石油化工大学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111440140A (en) * | 2020-05-27 | 2020-07-24 | 甘肃盛世恒百药业有限公司 | Green process for synthesizing 2-acetylthiophene |
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Application publication date: 20170627 |
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