CN103351376B - Synthetic method of 2-thiophene ethylamine - Google Patents
Synthetic method of 2-thiophene ethylamine Download PDFInfo
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Abstract
The invention provides a synthetic method of 2-thiophene ethylamine. The synthetic method is characterized in that: the 2-thiophene ethylamine is obtained through esterification, ammonification and dissociation in non-aqueous medium by using 2-thiopheneethanol as initial raw materials. The synthetic method comprises the following steps of: (1) an esterification reaction, i.e., generating an esterified substance under the condition of solid base catalysis from 2-thiopheneethanol and p-toluenesulfonyl chloride in an organic solvent; (2) an ammonification reaction, i.e., injecting liquid ammonia into the esterified substance, pressurizing and ammonifying so as to generate 2-thienylethamino-4-toluenesulfonate; (3) a dissociation reaction, i.e., reacting the 2-thienylethamino-4-toluenesulfonate with a solid base in the organic solvent by the dissociation so as to prepare the 2-thiophene ethylamine. The whole preparation process of the 2-thiophene ethylamine is completed in the non-aqueous medium so that no waste water is discharged, solid waste materials are recycled and reused, and the purpose of green production is achieved. Besides, reaction conditions are milder, post treatment process is simpler, yield is high, and industrial production is facilitated.
Description
Technical field
The invention belongs to medicine and chemical technology field, specifically a kind of synthetic method of 2 thiophene ethyl amine.
Background technology
2 thiophene ethyl amine can be used for the synthesis of multi-medicament, the critical medication intermediate of the sick and new drug for anti-inflammatory analgesic of the multiple cardiovascular relevant with thrombocyte and thrombus of preparation, such as, for the synthesis of the important drugs ticlopidine hydrochloride of cardiovascular and cerebrovascular diseases, bisulfate clopidogrel and prasugrel hydrochloride.Along with continually developing of its derived product, the prospect of 2 thiophene ethyl amine and derivative will be more wide.
Synthesising process research report about 2 thiophene ethyl amine is more, wherein industrialization or there is industrial applications prospect have four kinds of synthetic routes, concrete synthesis technique is as follows: 1, Nitromethane 99Min. method: this method is by thiophene and N, cationoid reaction is there is and obtains 2 thiophene carboxaldehyde in dinethylformamide (DMF) under phosphorus oxychloride exists, 2-(nitro) thiofuran ethylene prepared by 2 thiophene carboxaldehyde and Nitromethane 99Min. under sodium hydroxide existent condition, the diborane generated with the diethyl ether solution of sodium borohydride and boron trifluoride is for reductive agent, reductase 12-(nitro) thiofuran ethylene is 2 thiophene ethyl amine.This route has the high and advantage of good product quality of productive rate, but the subject matter existed is the diethyl ether solution of boron trifluoride is severe toxicity, is easy to volatilization; require higher to the protection of operator; and sodium borohydride is expensive, and large usage quantity in reaction, cause production cost higher.2, isopropyl chloracetate method: this method is with thiophene and N, dinethylformamide (DMF) and thiophene are obtained by reacting 2 thiophene carboxaldehyde under phosphorus oxychloride exists, Mono Chloro Acetic Acid and Virahol esterification obtain isopropyl chloracetate, there is Darzens and be obtained by reacting 2-thiophene aldehyde in 2 thiophene carboxaldehyde and isopropyl chloracetate, be obtained by reacting with oxammonium hydrochloride and obtain 2-thiophene aldehyde oxime, the reduction of 2-thiophene aldehyde oxime obtains 2 thiophene ethyl amine.The raw material that this method adopts is cheap and easy to get, smaller to the pollution of environment, but this reaction conditions is harsher, reductive agent and catalyzer price comparison expensive, yield is lower.3,2 thiophene acetonitrile method: take thiophene as Material synthesis 2-chloromethyl thiophene, carrying out being obtained by reacting 2 thiophene acetonitrile with sodium cyanide, prepares 2 thiophene ethyl amine in reduction.This method synthesis step is few, and reaction conditions is gentle, and product yield is higher, but shortcoming uses severe poisonous chemicals sodium cyanide, and produces a large amount of cyanide wastewater, and environmental pollution is comparatively serious.4,2-thiophene ethanol method: China national intellecture property board web discloses 2-thiophene ethanol and (to first) benzene sulfonyl chloride in the presence of a phase transfer catalyst, under inorganic base aqueous solution catalysis, generate carboxylate, then carboxylate and liquefied ammonia carry out aminating reaction, generate 2 thiophene ethyl amine.The method synthesis 2 thiophene ethyl amine, reaction conditions is gentle, and product yield is higher, and be comparatively applicable to suitability for industrialized production, but product aftertreatment is more loaded down with trivial details, creates a large amount of waste water and spent acid in reaction, environmental pollution is comparatively serious; China national intellecture property board web also discloses 2-thiophene ethanol and liquefied ammonia reacts, at load Al
2o
3metal catalytic under synthesize 2 thiophene ethyl amine.The aftertreatment of same the method synthesis 2 thiophene ethyl amine product is more loaded down with trivial details, and create a large amount of waste water and spent acid in reaction, also create the residual of noble metal, environmental pollution is comparatively serious simultaneously.
Summary of the invention
Problem to be solved by this invention proposes one for the deficiencies in the prior art with 2-thiophene ethanol for starting raw material, in non-aqueous media, by esterification, ammonification with free obtain 2 thiophene ethyl amine, in whole building-up process, all complete in non-aqueous media, achieve the zero release of waste water and the recycling of solid waste, reach the object that greenization is produced, and reaction conditions milder, aftertreatment technology is simpler, reduce production cost, and the synthetic method of the high 2 thiophene ethyl amine of yield.
The technical solution adopted in the present invention is: a kind of synthetic method of 2 thiophene ethyl amine, comprises following steps:
(1) preparation of carboxylate: in organic solvent, adds 2-thiophene ethanol, Tosyl chloride, adds solid alkali in batches, controlling temperature of reaction is-10 ~ 50 DEG C, soaking time is 2 ~ 12 hours, after reaction terminates, and stratification, filter, filter cake organic solvent drip washing, suction filtration, to dry, obtains solid wet product chlorate, filtrate decompression removes organic solvent, obtains carboxylate crude product;
(2) preparation of 2 thiophene ethyl amine tosilate: in methanol solvate, add carboxylate crude product, pass into liquefied ammonia and carry out aminating reaction, control reaction pressure 0.2 ~ 1.0Mpa, temperature of reaction is 0 ~ 80 DEG C, and soaking time is 4 ~ 12 hours, after reaction terminates, after opening ammonia compressor recovery ammonia, then methyl alcohol is reclaimed in air distillation, obtains 2 thiophene ethyl amine tosilate;
(3) the free and finished product preparation of 2 thiophene ethyl amine tosilate: in organic solvent, add 2 thiophene ethyl amine tosilate, after adding solid alkali, be heated to 50 ~ 120 DEG C, soaking time is 3 ~ 15 hours, after reaction terminates, is cooled to 40 ~ 45 DEG C, filter, filter cake organic solvent drip washing, suction filtration, to dry, obtains solid wet product tosilate, after filtrate is concentrated, more namely rectification under vacuum collection 99 ~ 102 DEG C/2.2Kpa cut obtains finished product 2 thiophene ethyl amine.
The chemical equation of the synthetic method of above-described 2 thiophene ethyl amine is as follows:
As preferably: the organic solvent in described step (1) is methylene dichloride, trichloromethane, ethyl acetate, tetrahydrofuran (THF), 2-methyltetrahydrofuran, benzene,toluene,xylene, chlorobenzene, dichlorobenzene, 1,2-monochloroethane, Isosorbide-5-Nitrae-dioxane or acetone.
Further, the solid alkali in described step (1) is sodium bicarbonate, saleratus, sodium carbonate, salt of wormwood, sodium hydroxide, potassium hydroxide or calcium hydroxide.
Further, in described step (1), 2-thiophene ethanol, Tosyl chloride and solid alkali mol ratio are 1:1-10:1-10.
Further, in described step (1), the envelope-bulk to weight ratio of organic solvent and 2-thiophene ethanol is 2 ~ 10:1(ml/g).
Further, in described step (2), the envelope-bulk to weight ratio of methyl alcohol and carboxylate is 2 ~ 10:1(ml/g).
Further, the organic solvent in described step (3) is ethyl acetate, tetrahydrofuran (THF), 2-methyltetrahydrofuran, benzene,toluene,xylene, chlorobenzene, dichlorobenzene or Isosorbide-5-Nitrae-dioxane.
Further, in described step (3), 2 thiophene ethyl amine tosilate and solid alkali mol ratio are 1:1 ~ 10.
Further, in described step (3), the envelope-bulk to weight ratio of organic solvent and 2 thiophene ethyl amine tosilate is 3 ~ 10:1(ml/g).
Further, the solid alkali in described step (3) is sodium methylate, sodium ethylate, sodium bicarbonate, saleratus, sodium carbonate, salt of wormwood, sodium hydroxide, potassium hydroxide or calcium hydroxide.
Compared with prior art, the present invention has the following advantages:
(1) in whole building-up process, all complete in non-aqueous media, achieve the zero release of waste water and the recycling of solid waste, simultaneous reactions mild condition, aftertreatment technology is simpler, avoids the dissolving of 2 thiophene ethyl amine in water, total recovery is higher, and is conducive to suitability for industrialized production;
(2) building-up process of carboxylate, reacts in non-aqueous media, and product only needs filtering separation, concentrated rear acquisition, and filter cake chlorate solid is by recycling after recrystallization, and aftertreatment technology is simple, also reduces production cost;
(3) building-up process of carboxylate, reacts in nonhomogeneous system, does not need additionally to add phase-transfer catalyst, and reaction yield is high;
(4) in the free process of 2 thiophene ethyl amine tosilate, also be react in non-aqueous media, product only needs filtering separation, concentrated rear acquisition, and filter cake tosilate solid can directly be recycled, aftertreatment technology is simple, also reduces production cost.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art are as made various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's elaboration.
Embodiment 1: the preparation of carboxylate:
In the 250ml four-hole boiling flask that drying tube is housed, 35.0g (0.184mol) Tosyl chloride, 45ml toluene is added successively under normal temperature, 22.5g (0.176mol) thiophene ethanol is added after stirring and dissolving, after being cooled to 0-5 DEG C, add 8.5g (0.213mol) sodium hydroxide, 0-5 DEG C of stirring reaction 5 hours, reaction terminates rear suction filtration, filter cake 30ml toluene drip washing, drains wet product solid sodium chloride and sodium hydroxide are about 12.9g.Filtrate decompression removes toluene, until without underpressure distillation 30 minutes again after flow, obtain sulphonate concentrated solution 49.8g, it is 99.4% that high performance liquid chromatography (HPLC) analysis records sulphonate content, yield 99%.
Embodiment 2: the preparation of carboxylate:
In the 250ml four-hole boiling flask that drying tube is housed, 35.0g (0.184mol) Tosyl chloride, 45ml toluene is added successively under normal temperature, 22.5g (0.176mol) thiophene ethanol is added after stirring and dissolving, after being cooled to 0-5 DEG C, add 14.4g (0.360mol) sodium hydroxide, 0-5 DEG C of stirring reaction 5 hours, reaction terminates rear suction filtration, filter cake 30ml toluene drip washing, drains wet product solid sodium chloride and sodium hydroxide are about 20.1g.Filtrate decompression removes toluene, until without underpressure distillation 30 minutes again after flow, obtain sulphonate concentrated solution 50.0g, it is 99.0% that high performance liquid chromatography (HPLC) analysis records sulphonate content, yield 99%.
Embodiment 3: the preparation of carboxylate:
In the 250ml four-hole boiling flask that drying tube is housed, 35.0g (0.184mol) Tosyl chloride, 45ml toluene is added successively under normal temperature, 22.5g (0.176mol) thiophene ethanol is added after stirring and dissolving, 8.5g (0.213mol) sodium hydroxide is added at about 25 DEG C, 25 DEG C of stirring reactions 5 hours, reaction terminates rear suction filtration, filter cake 30ml toluene drip washing, drains wet product solid sodium chloride and sodium hydroxide are about 12.9g.Filtrate decompression removes toluene, until without underpressure distillation 30 minutes again after flow, obtain sulphonate concentrated solution 49.6g, it is 98.6% that high performance liquid chromatography (HPLC) analysis records sulphonate content, yield 98%.
Embodiment 4: the preparation of carboxylate:
In the 250ml four-hole boiling flask that drying tube is housed, 35.0g (0.184mol) Tosyl chloride, 45ml toluene is added successively under normal temperature, 22.5g (0.176mol) thiophene ethanol is added after stirring and dissolving, 8.5g (0.213mol) sodium carbonate is added at about 25 DEG C, 25 DEG C be stirred to reaction terminate after suction filtration, filter cake 30ml toluene drip washing, drains wet product solid sodium chloride and sodium hydroxide are about 12.9g.Filtrate decompression removes toluene, until without underpressure distillation 30 minutes again after flow, obtain sulphonate concentrated solution 49.3g, it is 97.2% that high performance liquid chromatography (HPLC) analysis records sulphonate content, yield 97.5%.
Embodiment 5: the preparation of carboxylate:
In the 250ml four-hole boiling flask that drying tube is housed, 35.0g (0.184mol) Tosyl chloride, 45ml dimethylbenzene is added successively under normal temperature, 22.5g (0.176mol) thiophene ethanol is added after stirring and dissolving, after being cooled to 0-5 DEG C, add 8.5g (0.213mol) sodium hydroxide, 0-5 DEG C of stirring reaction 5 hours, reaction terminates rear suction filtration, filter cake 30ml toluene drip washing, drains wet product solid sodium chloride and sodium hydroxide are about 12.9g.Filtrate decompression removes toluene, until without underpressure distillation 30 minutes again after flow, obtain sulphonate concentrated solution 50.1g, it is 99.1% that high performance liquid chromatography (HPLC) analysis records sulphonate content, yield 99%.
The preparation of embodiment 6:2-thiophene ethamine tosilate
In methanol solvate, add 50.0g sulphonate crude product, pass into liquefied ammonia and carry out aminating reaction, control reaction pressure 0.5Mpa, temperature of reaction is 50 DEG C, soaking time is 8 hours, after reaction terminates, after opening ammonia compressor recovery ammonia, then methyl alcohol is reclaimed in air distillation, obtain 52.0g2-thiophene ethamine tosilate, yield 98%;
The preparation of embodiment 7:2-thiophene ethamine tosilate
In methanol solvate, add 50.0g sulphonate crude product, pass into liquefied ammonia and carry out aminating reaction, control reaction pressure 1.0Mpa, temperature of reaction is 50 DEG C, soaking time is 8 hours, after reaction terminates, after opening ammonia compressor recovery ammonia, then methyl alcohol is reclaimed in air distillation, obtain 52.2g2-thiophene ethamine tosilate, yield 98.5%;
Free and the finished product preparation of embodiment 8:2-thiophene ethamine tosilate:
50.0g(0.167mol is added successively in 500ml four-hole boiling flask) 2 thiophene ethyl amine tosilate, 200ml toluene and 7.0g(0.175mol) sodium hydroxide, be heated to 90 DEG C, insulated and stirred is after 3 hours, be cooled to 40 DEG C of filtrations, filter cake 100ml toluene drip washing, obtains solid wet product paratoluenesulfonic acid sodium salt, dries 12 hours to obtain white paratoluenesulfonic acid sodium salt pulverulent solids 30.9g in 80 DEG C of normal pressures, (HPLC content is 98.30%, residual 2 thiophene ethyl amine 0.03%); After filtrate decompression removes toluene, then reduce pressure and just heat up in a steamer collection 99 ~ 102 DEG C/2.2Kpa cut and namely obtain finished product 2 thiophene ethyl amine 19.5g, yield is 92.5%, GC content is 99.64%.
Free and the finished product preparation of embodiment 9:2-thiophene ethamine tosilate:
50.0g(0.167mol is added successively in 500ml four-hole boiling flask) 2 thiophene ethyl amine tosilate, 200ml toluene and 7.0g(0.175mol) sodium hydroxide, be heated to backflow, insulated and stirred is after 3 hours, be cooled to 40 DEG C of filtrations, filter cake 100ml toluene drip washing, obtains solid wet product paratoluenesulfonic acid sodium salt, dries 12 hours to obtain white paratoluenesulfonic acid sodium salt pulverulent solids 31.3g in 80 DEG C of normal pressures, (HPLC content is 97.95%, residual 2 thiophene ethyl amine 0.01%); After filtrate decompression removes toluene, then reduce pressure and just heat up in a steamer collection 99 ~ 102 DEG C/2.2Kpa cut and namely obtain finished product 2 thiophene ethyl amine 19.1g, yield is 90%, GC content is 99.60%.
Free and the finished product preparation of embodiment 10:2-thiophene ethamine tosilate:
50.0g(0.167mol is added successively in 500ml four-hole boiling flask) 2 thiophene ethyl amine tosilate, 200ml2-methyltetrahydrofuran and 7.0g(0.175mol) sodium hydroxide, be heated to backflow, insulated and stirred is after 5 hours, be cooled to 40 DEG C of filtrations, filter cake 100ml2-methyltetrahydrofuran drip washing, obtain solid wet product paratoluenesulfonic acid sodium salt, white paratoluenesulfonic acid sodium salt pulverulent solids 31.7g is dried 12 hours to obtain in 80 DEG C of normal pressures, (HPLC content is 99.71%, residual 2 thiophene ethyl amine 0.04%); After filtrate decompression removes 2-methyltetrahydrofuran, then reduce pressure and just heat up in a steamer collection 99 ~ 102 DEG C/2.2Kpa cut and namely obtain finished product 2 thiophene ethyl amine 19.4g, yield is 91.5%, GC content is 99.59%.
Free and the finished product preparation of embodiment 11:2-thiophene ethamine tosilate:
50.0g(0.167mol is added successively in 500ml four-hole boiling flask) 2 thiophene ethyl amine tosilate, 200ml ml toluene and 18.6g(0.175mol) sodium carbonate, be heated to 90 DEG C, insulated and stirred is after 12 hours, be cooled to 40 DEG C of filtrations, filter cake 100ml toluene drip washing, obtains solid wet product paratoluenesulfonic acid sodium salt, dries 12 hours to obtain white paratoluenesulfonic acid sodium salt pulverulent solids 29.8g in 80 DEG C of normal pressures, (HPLC content is 95.27%, residual 2 thiophene ethyl amine 0.19%); After filtrate decompression removes toluene, then reduce pressure and just heat up in a steamer collection 99 ~ 102 DEG C/2.2Kpa cut and namely obtain finished product 2 thiophene ethyl amine 18.8g, yield is 89%, GC content is 99.57%.
Free and the finished product preparation of embodiment 12:2-thiophene ethamine tosilate:
50.0g(0.167mol is added successively in 500ml four-hole boiling flask) 2 thiophene ethyl amine tosilate, 300ml toluene and 9.8g(0.175mol) potassium hydroxide, be heated to 90 DEG C, insulated and stirred is after 3 hours, be cooled to 40 DEG C of filtrations, filter cake 100ml toluene drip washing, obtains solid wet product tosic acid potassium, dries 12 hours to obtain white paratoluenesulfonic acid sodium salt pulverulent solids 34.5g in 80 DEG C of normal pressures, (HPLC content is 98.53%, residual 2 thiophene ethyl amine 0.02%); After filtrate decompression removes toluene, then reduce pressure and just heat up in a steamer collection 99 ~ 102 DEG C/2.2Kpa cut and namely obtain finished product 2 thiophene ethyl amine 19.5g, yield is 92%, GC content is 99.68%.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., be all included within protection scope of the present invention.
Claims (8)
1. a synthetic method for 2 thiophene ethyl amine, is characterized in that, comprises following steps:
(1) preparation of carboxylate: in organic solvent, adds 2-thiophene ethanol, Tosyl chloride, adds solid alkali in batches, controlling temperature of reaction is-10 ~ 50 DEG C, soaking time is 2 ~ 12 hours, after reaction terminates, and stratification, filter, filter cake organic solvent drip washing, suction filtration, to dry, obtain solid wet product chlorate and recycles, filtrate decompression removes organic solvent, obtains carboxylate crude product;
(2) preparation of 2 thiophene ethyl amine tosilate: in methanol solvate, add carboxylate crude product, pass into liquefied ammonia and carry out aminating reaction, control reaction pressure 0.2 ~ 1.0Mpa, temperature of reaction is 0 ~ 80 DEG C, and soaking time is 4 ~ 12 hours, after reaction terminates, after opening ammonia compressor recovery ammonia, then methyl alcohol is reclaimed in air distillation, obtains 2 thiophene ethyl amine tosilate;
(3) the free and finished product preparation of 2 thiophene ethyl amine tosilate: in organic solvent, add 2 thiophene ethyl amine tosilate, after adding solid alkali, be heated to 50 ~ 120 DEG C, soaking time is 3 ~ 15 hours, after reaction terminates, be cooled to 40 ~ 45 DEG C, filter, filter cake organic solvent drip washing, suction filtration, to dry, obtain solid wet product tosilate and recycles, after filtrate is concentrated, more namely rectification under vacuum collection 99 ~ 102 DEG C/2.2Kpa cut obtains finished product 2 thiophene ethyl amine;
Solid alkali in described step (1) is sodium bicarbonate, saleratus, sodium carbonate, salt of wormwood, sodium hydroxide, potassium hydroxide or calcium hydroxide;
Solid alkali in described step (3) is sodium methylate, sodium ethylate, sodium bicarbonate, saleratus, sodium carbonate, salt of wormwood, sodium hydroxide, potassium hydroxide or calcium hydroxide.
2. the synthetic method of 2 thiophene ethyl amine according to claim 1, it is characterized in that, organic solvent in described step (1) is methylene dichloride, trichloromethane, ethyl acetate, tetrahydrofuran (THF), 2-methyltetrahydrofuran, benzene,toluene,xylene, chlorobenzene, dichlorobenzene, 1,2-monochloroethane, Isosorbide-5-Nitrae-dioxane or acetone.
3. the synthetic method of 2 thiophene ethyl amine according to claim 1, is characterized in that, in described step (1), 2-thiophene ethanol, Tosyl chloride and solid alkali mol ratio are 1:1 ~ 10:1 ~ 10.
4. the synthetic method of 2 thiophene ethyl amine according to claim 1, is characterized in that, in described step (1), the envelope-bulk to weight ratio of organic solvent and 2-thiophene ethanol is 2 ~ 10:1ml/g.
5. the synthetic method of 2 thiophene ethyl amine according to claim 1, is characterized in that, in described step (2), the envelope-bulk to weight ratio of methyl alcohol and carboxylate is 2 ~ 10:1ml/g.
6. the synthetic method of 2 thiophene ethyl amine according to claim 1, it is characterized in that, organic solvent in described step (3) is ethyl acetate, tetrahydrofuran (THF), 2-methyltetrahydrofuran, benzene,toluene,xylene, chlorobenzene, dichlorobenzene or Isosorbide-5-Nitrae-dioxane.
7. the synthetic method of 2 thiophene ethyl amine according to claim 1, is characterized in that, in described step (3), 2 thiophene ethyl amine tosilate and solid alkali mol ratio are 1:1 ~ 10.
8. the synthetic method of 2 thiophene ethyl amine according to claim 1, is characterized in that, in described step (3), the envelope-bulk to weight ratio of organic solvent and 2 thiophene ethyl amine tosilate is 3 ~ 10:1ml/g.
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| CN101333223A (en) * | 2008-07-28 | 2008-12-31 | 台州市知青化工有限公司 | Method for preparing clopidogrel and salts thereof |
| CN101885720A (en) * | 2010-07-19 | 2010-11-17 | 连云港宏业化工有限公司 | Method for synthesizing 2-thiophene ethylamine |
| CN102020631A (en) * | 2010-11-18 | 2011-04-20 | 余朝鹤 | Synthetic method of 2-thiophene ethylamine |
| CN102432590A (en) * | 2011-11-23 | 2012-05-02 | 洛阳师范学院 | Method for synthesizing thiophene ethylamine |
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| CN101333223A (en) * | 2008-07-28 | 2008-12-31 | 台州市知青化工有限公司 | Method for preparing clopidogrel and salts thereof |
| CN101885720A (en) * | 2010-07-19 | 2010-11-17 | 连云港宏业化工有限公司 | Method for synthesizing 2-thiophene ethylamine |
| CN102020631A (en) * | 2010-11-18 | 2011-04-20 | 余朝鹤 | Synthetic method of 2-thiophene ethylamine |
| CN102432590A (en) * | 2011-11-23 | 2012-05-02 | 洛阳师范学院 | Method for synthesizing thiophene ethylamine |
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