CN102627626A - Preparation method of 2, 3-thiophenedicarboxaldehyde - Google Patents
Preparation method of 2, 3-thiophenedicarboxaldehyde Download PDFInfo
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- CN102627626A CN102627626A CN201210072960XA CN201210072960A CN102627626A CN 102627626 A CN102627626 A CN 102627626A CN 201210072960X A CN201210072960X A CN 201210072960XA CN 201210072960 A CN201210072960 A CN 201210072960A CN 102627626 A CN102627626 A CN 102627626A
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- thiophene
- brooethyl
- dialdehyde
- lucidol
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Abstract
The invention discloses a preparation method of 2, 3-thiophenedicarboxaldehyde and belongs to the field of organic synthesis. The preparation method is characterized in that 2, 3-thiophenedicarboxaldehyde as a raw material and N-bromosuccinimide undergo a bromination reaction in the presence of benzoyl peroxide as a catalyst and carbon tetrachloride or trichloromethane as a solvent at a certain temperature to produce 2, 3-di(bromomethyl)thiophene; and 2, 3-di(bromomethyl)thiophene and hexamethylenetetramine undergo a Sommelet reaction in the presence of trichloromethane as a solvent at a certain temperature to produce 2, 3-thiophenedicarboxaldehyde. Compared with the prior art, the preparation method has the advantages that raw materials are cheap and easily available; reaction conditions are mild and can be controlled easily; and a product yield is high.
Description
Technical field
The present invention relates to a kind of working method of Chemicals, relate in particular to 2, a kind of working method of 3-dialdehyde-based thiophene belongs to the organic synthesis field.
Background technology
Thiophene has good reaction activity, can carry out reactions such as nitrated, sulfonation, alkylation, acidylate and halo, and thiophene derivant is widely used in fields such as medicine, agricultural chemicals, dyestuff, pluronic polymer.Aspect medical, the microbiotic phenyl homologue of band thiphene ring has better therapeutic, and some anti-inflammatory drug are as being thiophene derivant to hydroxyephedrine, sufentanil etc.; In addition, in other field of fine chemical, it also is widely used, and can be used for the white dyes of plastics, injection moulding material, EVA foaming and rubber item, synthon, coating etc. etc.
2, and 3-dialdehyde-based thiophene (2,3-Thiophenedicarboxaldehyde), claim 2 again, 3-thiophene dicarbaldehyde, yellow needle-like crystal, molecular formula C
6H
4O
2S, molecular weight 140.16,76 ~ 78 ℃ of fusing points.2; 3-dialdehyde-based thiophene has the character of thiophene and aldehyde radical, has the character of α-thiophene derivant and β-thiophene derivant simultaneously concurrently, contains two aldehyde radicals; Can pass through the aldol reaction closed loop; Make a series of that contain thiphene ring and encircle macromolecular cpd, verivate is varied, is widely used in superconducting material, microelectronic material, photonic material, information material, Energy conversion and energy storage material, ecological environment material nd and bio-medical material.
Present 2,3-dialdehyde-based thiophene working method bibliographical information seldom, mainly through 2,3-dimethanol thiophene obtains through the method that alcohol is oxidized to aldehyde, severe reaction conditions, expensive raw material price is not easy to obtain, production cost is high, makes it be difficult to be applied to suitability for industrialized production.
Summary of the invention
The object of the invention is to provide a kind of reaction conditions gentle, and raw material is easy to get, and production cost is low, can be applied to 2 of suitability for industrialized production, 3-dialdehyde-based thiophene novel preparation method.
For realizing the object of the invention, technical scheme of the present invention is following:
With 2, the 3-thioxene is a starting raw material, and Lucidol is made catalyzer; Tetracol phenixin or trichloromethane are made solvent, under heating condition, generate 2,3-two (brooethyl) thiophene with N-bromo-succinimide generation bromination reaction; Obtain 2,3-two (brooethyl) thiophene through underpressure distillation; With the trichloromethane is solvent, 2, and the Sommelet reaction takes place and generates 2,3-dialdehyde-based thiophene in 3-two (brooethyl) thiophene same urotropin (HMTA) under heating condition; Washing adds acidifying, after the extraction; Evaporating solvent, drying, crystallisation by cooling; Cross post and purify, get 2,3-dialdehyde-based thiophene.Benzoylperoxide catalyst adds in batches.
Concrete reactions step is following:
(1) with 2,3-thioxene and part Lucidol are dissolved in the organic solvent, under refluxad slowly add the mixture of N-bromo-succinimide and Lucidol in batches; Reinforced finishing continues the reaction postcooling to room temperature, removes by filter the succimide of generation; Behind the washing organic layer, drying, organic layer steams and desolventizes; Underpressure distillation gets 2,3-two (brooethyl) thiophene.
(2) urotropin is dissolved in the trichloromethane, stir, splash into 2,3-two (brooethyl) thiophene refluxes; The reflux when stopping of waiting to reflux, be cooled to room temperature after, add entry and all dissolve, separatory, washing organic layer to the salt that generates; Heating is distilled to the reaction solution clarification, uses acidifying, extraction, drying; Evaporating solvent, crystallisation by cooling, bullion with sherwood oil do developping agent cross post purify 2,3-dialdehyde-based thiophene.
Reactant molar ratio: 2, the 3-thioxene: Lucidol is 1: 0.02 ~ 0.03; 2, the 3-thioxene: the N-bromo-succinimide is 1: 2; 2,3-two (brooethyl) thiophene: urotropin is 1: 2.1 ~ 2.4.
The present invention 2, and 3-dialdehyde-based thiophene preparing method's innovative point and advantage are: reaction conditions is gentle, and raw material is easy to get, and production cost is low, can be applied to suitability for industrialized production.
Embodiment
For better the present invention being elaborated, give an actual example as follows:
Embodiment 1
2,3-thioxene (11.22 g, 0.10 mol), Lucidol (0.24 g; 1.0 mmol), be dissolved in the 80 mL tetracol phenixin, after vigorous stirring and the reflux, slowly add N-bromo-succinimide (35.60 g in batches; 0.2 mol) and the mixture of Lucidol (0.24 g, 1.0 mmol), reinforced finishing; Continue reaction 3 h postcooling to room temperature, remove by filter the succimide of generation, add water washing filtrating; Organic layer is with sodium hydrogen carbonate solution, sodium chloride solution washing, and is dry with Anhydrous potassium carbonate, and rotatory evaporator steams and desolventizes; Bullion is purified through underpressure distillation, gets solid phase prod 2,3-two (brooethyl) thiophene 20.3 g (yield 76%).Fusing point: 49 ~ 50 ℃,
1H NMR (solvent C DCl3), δ: 5.50 (2H, s), 5.29 (2H, s), 3.00 (1H, d, J=6.0 Hz), 2.72 (1H, d, J=6.0 Hz).
Urotropin (29.44 g, 0.21 mol) dissolves in 100 mL trichloromethanes, slowly splashes into 2 under the vigorous stirring, 3-two (brooethyl) thiophene (27 g; 0.1 mol), the spontaneous backflow of exothermic heat of reaction, reflux 30 min when stopping that waiting to reflux, be cooled to room temperature after; Add entry, be stirred to all insolubles dissolvings, tell organic layer, washing; The organic layer heating is distilled to the distillate clarification, and the residue raffinate is used acidifying, uses extracted with diethyl ether, and anhydrous calciumsulphate is dry; Revolve to steam and remove ether, crystallisation by cooling, bullion are made of 30 ~ 60 ℃ of sherwood oils and are got white needle-like crystals 2,3-dialdehyde-based thiophene 10.5 g (yield 74.8%) after developping agent is crossed the pillar purification.Fusing point: 78 ~ 79 ℃.
1H NMR (solvent C DCl
3), δ: 10.50 (1H, s), 10.39 (1H, s), 7.76 (1H, d, J=5.1 Hz), 7.65 (1H, d, J=5.1 Hz); EI-MS (70 eV)
M/z(%): 286 ([M-H]
+, 1), 140 (31), 111 (100), 83 (22).
Embodiment 2
2,3-thioxene (22.44 g, 0.20 mol), Lucidol (0.72 g; 3.0 mmol), be dissolved in the 160 mL trichloromethanes, after vigorous stirring and the reflux, slowly add N-bromo-succinimide (71.20 g in batches; 0.4 mol) and the mixture of Lucidol (0.72 g, 3.0 mmol), reinforced finishing; Continue reaction 3 h postcooling to room temperature, remove by filter the succimide of generation, add water washing filtrating; Organic layer is with sodium hydrogen carbonate solution, sodium chloride solution washing, and is dry with Anhydrous potassium carbonate, and rotatory evaporator steams and desolventizes; Bullion is purified through underpressure distillation, gets solid phase prod 2,3-two (brooethyl) thiophene 42.7 g (yield 79%).
Urotropin (61.69 g, 0.44 mol) dissolves in 200 mL trichloromethanes, slowly splashes into 2 under the vigorous stirring, 3-two (brooethyl) thiophene (54 g; 0.2 mol), the spontaneous backflow of exothermic heat of reaction, reflux 30 min when stopping that waiting to reflux, be cooled to room temperature after; Add entry, be stirred to all insolubles dissolvings, tell organic layer, washing; The organic layer heating is distilled to the distillate clarification, and the residue raffinate is used acidifying, uses extracted with diethyl ether, and anhydrous calciumsulphate is dry; Revolve to steam and remove ether, crystallisation by cooling, bullion are made of 30 ~ 60 ℃ of sherwood oils and are got white needle-like crystals 2,3-dialdehyde-based thiophene 21.33 g (yield 76.0%) after developping agent is crossed the pillar purification.
Embodiment 3
2,3-thioxene (11.22 g, 0.10 mol), Lucidol (0.36 g; 1.5 mmol), be dissolved in the 80 mL tetracol phenixin, after vigorous stirring and the reflux, slowly add N-bromo-succinimide (35.60 g in batches; 0.2 mol) and the mixture of Lucidol (0.36 g, 1.5 mmol), reinforced finishing; Continue reaction 3 h postcooling to room temperature, remove by filter the succimide of generation, add water washing filtrating; Organic layer is with sodium hydrogen carbonate solution, sodium chloride solution washing, and is dry with Anhydrous potassium carbonate, and rotatory evaporator steams and desolventizes; Bullion is purified through underpressure distillation, gets solid phase prod 2,3-two (brooethyl) thiophene 19.2 g (yield 71%).
Urotropin (32.66 g, 0.23 mol) dissolves in 100 mL trichloromethanes, slowly splashes into 2 under the vigorous stirring, 3-two (brooethyl) thiophene (27 g; 0.1 mol), the spontaneous backflow of exothermic heat of reaction, reflux 30 min when stopping that waiting to reflux, be cooled to room temperature after; Add entry, be stirred to all insolubles dissolvings, tell organic layer, washing; The organic layer heating is distilled to the distillate clarification, and the residue raffinate is used acidifying, uses extracted with diethyl ether, and anhydrous calciumsulphate is dry; Revolve to steam and remove ether, crystallisation by cooling, bullion are made of 30 ~ 60 ℃ of sherwood oils and are got white needle-like crystals 2,3-dialdehyde-based thiophene 10.59 g (yield 75.5%) after developping agent is crossed the pillar purification.
Embodiment 4
2,3-thioxene (22.44 g, 0.20 mol), Lucidol (0.48 g; 2.0 mmol), be dissolved in the 160 mL trichloromethanes, after vigorous stirring and the reflux, slowly add N-bromo-succinimide (71.20 g in batches; 0.4 mol) and the mixture of Lucidol (0.48 g, 2.0 mmol), reinforced finishing; Continue reaction 3 h postcooling to room temperature, remove by filter the succimide of generation, add water washing filtrating; Organic layer is with sodium hydrogen carbonate solution, sodium chloride solution washing, and is dry with Anhydrous potassium carbonate, and rotatory evaporator steams and desolventizes; Bullion is purified through underpressure distillation, gets solid phase prod 2,3-two (brooethyl) thiophene 40.5 g (yield 75%).
Urotropin (67.30 g, 0.48 mol) dissolves in 200 mL trichloromethanes, slowly splashes into 2 under the vigorous stirring, 3-two (brooethyl) thiophene (54 g; 0.2 mol), the spontaneous backflow of exothermic heat of reaction, reflux 30 min when stopping that waiting to reflux, be cooled to room temperature after; Add entry, be stirred to all insolubles dissolvings, tell organic layer, washing; The organic layer heating is distilled to the distillate clarification, and the residue raffinate is used acidifying, uses extracted with diethyl ether, and anhydrous calciumsulphate is dry; Revolve to steam and remove ether, crystallisation by cooling, bullion are made of 30 ~ 60 ℃ of sherwood oils and are got white needle-like crystals 2,3-dialdehyde-based thiophene 21.1 g (yield 75.2%) after developping agent is crossed the pillar purification.
Claims (3)
1. produce 2 for one kind, the method for 3-dialdehyde-based thiophene is characterized in that; With 2, the 3-thioxene is a starting raw material, and Lucidol is made catalyzer; Tetracol phenixin or trichloromethane are made solvent, under heating condition, generate 2,3-two (brooethyl) thiophene with N-bromo-succinimide generation bromination reaction; Obtain 2,3-two (brooethyl) thiophene through underpressure distillation; With the trichloromethane is solvent, 2, and the Sommelet reaction takes place with urotropin and generates 2,3-dialdehyde-based thiophene, washing in 3-two (brooethyl) thiophene under heating condition; Add acidifying, after the extraction, evaporating solvent, drying; Crystallisation by cooling is crossed post and is purified, and gets 2,3-dialdehyde-based thiophene.
2. like the described production 2 of claim 2, the method for 3-dialdehyde-based thiophene is characterized in that, concrete reactions step is following:
(1) with 2,3-thioxene and part Lucidol are dissolved in the organic solvent, under refluxad add the mixture of N-bromo-succinimide and Lucidol in batches; Reinforced finishing continues the reaction postcooling to room temperature, removes by filter the succimide of generation; Behind the washing organic layer, drying, organic layer steams and desolventizes; Underpressure distillation gets 2,3-two (brooethyl) thiophene;
(2) urotropin is dissolved in the trichloromethane, stir, splash into 2,3-two (brooethyl) thiophene refluxes; The reflux when stopping of waiting to reflux, be cooled to room temperature after, add entry and all dissolve, separatory, washing organic layer to the salt that generates; Heating is distilled to the reaction solution clarification, splashes into acidifying, extraction, evaporating solvent; Drying, crystallisation by cooling, bullion with sherwood oil do developping agent cross post purify 2,3-dialdehyde-based thiophene.
3. like claim 1 or 2 described productions 2, the method for 3-dialdehyde-based thiophene is characterized in that reactant molar ratio: 2, and the 3-thioxene: Lucidol is 1: 0.02-0.03; 2, the 3-thioxene: the N-bromo-succinimide is 1: 2; 2,3-two (brooethyl) thiophene: urotropin is 1: 2.1-2.4.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105130952A (en) * | 2015-08-06 | 2015-12-09 | 杨海霞 | Pharmaceutical intermediate aldehyde substituted thiophene compound synthesis method |
| CN112574169A (en) * | 2020-12-10 | 2021-03-30 | 武汉至精诚医药技术有限公司 | Preparation method of 5-methyl-2-thiophenecarboxaldehyde |
| WO2023004964A1 (en) * | 2021-07-30 | 2023-02-02 | 海南海神同洲制药有限公司 | Method for synthesizing 3-bromomethyl-7-chlorobenzo[b]thiophene |
-
2012
- 2012-03-20 CN CN201210072960.XA patent/CN102627626B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 王岭: "苯并噻吩-3-甲醛的合成研究", 《中国优秀博硕士学位论文全文数据库 (硕士) 工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105130952A (en) * | 2015-08-06 | 2015-12-09 | 杨海霞 | Pharmaceutical intermediate aldehyde substituted thiophene compound synthesis method |
| CN112574169A (en) * | 2020-12-10 | 2021-03-30 | 武汉至精诚医药技术有限公司 | Preparation method of 5-methyl-2-thiophenecarboxaldehyde |
| WO2023004964A1 (en) * | 2021-07-30 | 2023-02-02 | 海南海神同洲制药有限公司 | Method for synthesizing 3-bromomethyl-7-chlorobenzo[b]thiophene |
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Effective date of registration: 20160120 Address after: 450002 Henan city of Zhengzhou Province Red Road No. 56 Patentee after: Henan Academy of SciencesChemistry Institute Co., Ltd. Patentee after: Puyang Huicheng Electronic Material Co., Ltd. Address before: 450002 Henan city of Zhengzhou Province Red Road No. 56 Patentee before: Henan Academy of SciencesChemistry Institute Co., Ltd. |